Aspen Polymers+Vol1V7 1-Usr

Aspen Polymers
User Guide Volume 1
Version Number: V7.1 January 2009

Copyright (c) 1981-2009 by Aspen Technology, Inc. All rights reserved. Aspen Polymers, Aspen Custom Modeler, Aspen Dynamics, Aspen Plus, Aspen Properties, aspenONE, the aspen leaf logo and Plantelligence and Enterprise Optimization are trademarks or registered trademarks of Aspen Technology, Inc., Burlington, MA. All other brand and product names are trademarks or registered trademarks of their respective companies. This document is intended as a guide to using AspenTech's software. This documentation contains AspenTech proprietary and confidential information and may not be disclosed, used, or copied without the prior consent of AspenTech or as set forth in the applicable license agreement. Users are solely responsible for the proper use of the software and the application of the results obtained. Although AspenTech has tested the software and reviewed the documentation, the sole warranty for the software may be found in the applicable license agreement between AspenTech and the user. ASPENTECH MAKES NO WARRANTY OR REPRESENTATION, EITHER EXPRESSED OR IMPLIED, WITH RESPECT TO THIS DOCUMENTATION, ITS QUALITY, PERFORMANCE, MERCHANTABILITY, OR FITNESS FOR A PARTICULAR PURPOSE. Aspen Technology, Inc. 200 Wheeler Road Burlington, MA 01803-5501 USA Phone: (1) (781) 221-6400 Toll Free: (1) (888) 996-7100 URL: http://www.aspentech.com
Contents
Introducing Aspen Polymers ...................................................................................1 About This Documentation Set ......................................................................... 1 Related Documentation ................................................................................... 2 Technical Support .......................................................................................... 3 1 Polymer Manufacturing Process Overview...........................................................5 About Aspen Polymers .................................................................................... 5 Overview of Polymerization Processes ............................................................... 6 Polymer Manufacturing Process Steps...................................................... 6 Issues of Concern in Polymer Process Modeling .................................................. 7 Monomer Synthesis and Purification ........................................................ 8 Polymerization ..................................................................................... 8 Recovery / Separation........................................................................... 9 Polymer Processing............................................................................... 9 Summary ............................................................................................ 9 Aspen Polymers Tools ..................................................................................... 9 Component Characterization .................................................................10 Polymer Physical Properties ..................................................................10 Polymerization Kinetics ........................................................................10 Modeling Data.....................................................................................11 Process Flowsheeting ...........................................................................11 Defining a Model in Aspen Polymers.................................................................12 References ...................................................................................................14 2 Polymer Structural Characterization .................................................................15 Polymer Structure .........................................................................................15 Polymer Structural Properties .........................................................................19 Characterization Approach..............................................................................19 Component Attributes ..........................................................................19 References ...................................................................................................20 3 Component Classification ..................................................................................21 Component Categories...................................................................................21 Conventional Components ....................................................................22 Polymers............................................................................................22 Oligomers ..........................................................................................23 Segments ..........................................................................................24 Site-Based .........................................................................................24 Component Databanks...................................................................................25 Pure Component Databank ...................................................................25 Initiator Databank ...............................................................................26
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Segment Databank..............................................................................26 Polymer Databank ...............................................................................27 Segment Methodology ...................................................................................27 Specifying Components..................................................................................27 Selecting Databanks ............................................................................28 Defining Component Names and Types...................................................28 Specifying Segments ...........................................................................29 Specifying Polymers.............................................................................29 Specifying Oligomers ...........................................................................30 Specifying Site-Based Components ........................................................30 References ...................................................................................................31 4 Polymer Structural Properties ...........................................................................32 Structural Properties as Component Attributes ..................................................32 Component Attribute Classes ..........................................................................33 Component Attribute Categories......................................................................34 Polymer Component Attributes ..............................................................34 Site-Based Species Attributes ...............................................................44 User Attributes ...................................................................................45 Component Attribute Initialization ...................................................................46 Attribute Initialization Scheme ..............................................................46 Component Attribute Scale Factors ..................................................................50 Specifying Component Attributes.....................................................................51 Specifying Polymer Component Attributes...............................................51 Specifying Site-Based Component Attributes ...........................................51 Specifying Conventional Component Attributes ........................................51 Initializing Component Attributes in Streams or Blocks .............................51 Specifying Component Attribute Scaling Factors.......................................52 References ...................................................................................................52 5 Structural Property Distributions ......................................................................53 Property Distribution Types ............................................................................53 Distribution Functions ....................................................................................54 Schulz-Flory Most Probable Distribution ..................................................54 Stockmayer Bivariate Distribution ..........................................................56 Distributions in Process Models .......................................................................56 Average Properties and Moments...........................................................56 Method of Instantaneous Properties .......................................................58 Copolymerization ................................................................................61 Mechanism for Tracking Distributions ...............................................................62 Distributions in Kinetic Reactors ............................................................62 Distributions in Process Streams............................................................64 Verifying the Accuracy of Distribution Calculations ...................................65 Requesting Distribution Calculations ................................................................66 Selecting Distribution Characteristics......................................................66 Displaying Distribution Data for a Reactor ...............................................67 Displaying Distribution Data for Streams.................................................67 References ...................................................................................................68 6 End-Use Properties............................................................................................70 Polymer Properties ........................................................................................70
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Prop-Set Properties .......................................................................................71 End-Use Properties........................................................................................72 Relationship to Molecular Structure ........................................................72 Method for Calculating End-Use Properties ........................................................73 Intrinsic Viscosity ................................................................................74 Zero-Shear Viscosity............................................................................74 Density of Copolymer...........................................................................75 Melt Index..........................................................................................75 Melt Index Ratio..................................................................................76 Calculating End-Use Properties........................................................................76 Selecting an End-Use Property ..............................................................76 Adding an End-Use Property Prop-Set ....................................................76 References ...................................................................................................76 7 Polymerization Reactions ..................................................................................78 Polymerization Reaction Categories..................................................................78 Step-Growth Polymerization..................................................................80 Chain-Growth Polymerization ................................................................80 Polymerization Process Types..........................................................................81 Aspen Polymers Reaction Models .....................................................................82 Built-in Models ....................................................................................82 User Models........................................................................................83 References ...................................................................................................84 8 Step-Growth Polymerization Model ...................................................................85 Summary of Applications................................................................................85 Step-Growth Processes ..................................................................................86 Polyesters ..........................................................................................86 Nylon-6 .............................................................................................92 Nylon-6,6...........................................................................................94 Polycarbonate .....................................................................................96 Reaction Kinetic Scheme ................................................................................97 Nucleophilic Reactions..........................................................................97 Polyester Reaction Kinetics ................................................................. 101 Nylon-6 Reaction Kinetics ................................................................... 107 Nylon-6,6 Reaction Kinetics ................................................................ 111 Melt Polycarbonate Reaction Kinetics.................................................... 118 Model Features and Assumptions................................................................... 120 Model Predictions .............................................................................. 120 Phase Equilibria ................................................................................ 122 Reaction Mechanism ..........................................................................122 Model Structure ..........................................................................................123 Reacting Groups and Species .............................................................. 123 Reaction Stoichiometry Generation ...................................................... 128 Model-Generated Reactions ................................................................ 129 User Reactions..................................................................................134 User Subroutines...............................................................................136 Specifying Step-Growth Polymerization Kinetics............................................... 152 Accessing the Step-Growth Model ........................................................ 152 Specifying the Step-Growth Model ....................................................... 152 Specifying Reacting Components ......................................................... 153 Listing Built-In Reactions.................................................................... 153
Contents
Specifying Built-In Reaction Rate Constants .......................................... 154 Assigning Rate Constants to Reactions ................................................. 154 Including User Reactions .................................................................... 154 Adding or Editing User Reactions ......................................................... 155 Specifying Rate Constants for User Reactions ........................................ 155 Assigning Rate Constants to User Reactions .......................................... 156 Selecting Report Options .................................................................... 156 Selecting the Reacting Phase .............................................................. 156 Specifying Units of Measurement for Pre-Exponential Factors................... 157 Including a User Kinetic Subroutine...................................................... 157 Including a User Rate Constant Subroutine ........................................... 157 Including a User Basis Subroutine........................................................ 157 References ................................................................................................. 158 9 Free-Radical Bulk Polymerization Model..........................................................159 Summary of Applications.............................................................................. 159 Free-Radical Bulk/Solution Processes ............................................................. 160 Reaction Kinetic Scheme .............................................................................. 161 Initiation .......................................................................................... 167 Propagation ...................................................................................... 172 Chain Transfer to Small Molecules ....................................................... 174 Termination...................................................................................... 175 Long Chain Branching ........................................................................177 Short Chain Branching ....................................................................... 178 Beta-Scission.................................................................................... 179 Reactions Involving Diene Monomers ................................................... 179 Model Features and Assumptions................................................................... 182 Calculation Method ............................................................................ 182 Quasi-Steady-State Approximation (QSSA) ........................................... 184 Phase Equilibrium.............................................................................. 184 Gel Effect ......................................................................................... 185 Polymer Properties Calculated ....................................................................... 187 Specifying Free-Radical Polymerization Kinetics ............................................... 189 Accessing the Free-Radical Model ........................................................ 189 Specifying the Free-Radical Model........................................................ 190 Specifying Reacting Species ................................................................ 190 Listing Reactions ...............................................................................190 Adding Reactions............................................................................... 191 Editing Reactions............................................................................... 191 Assigning Rate Constants to Reactions ................................................. 192 Adding Gel-Effect ..............................................................................192 Selecting Calculation Options .............................................................. 192 Specifying User Profiles ...................................................................... 193 References ................................................................................................. 194 10 Emulsion Polymerization Model.....................................................................195 Summary of Applications.............................................................................. 195 Emulsion Polymerization Processes ................................................................ 196 Reaction Kinetic Scheme .............................................................................. 196 Micellar Nucleation ............................................................................ 197 Homogeneous Nucleation ................................................................... 200 Particle Growth .................................................................................202
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Radical Balance................................................................................. 203 Kinetics of Emulsion Polymerization ..................................................... 207 Model Features and Assumptions................................................................... 211 Model Assumptions............................................................................ 211 Thermodynamics of Monomer Partitioning............................................. 211 Polymer Particle Size Distribution ........................................................ 212 Polymer Particle Properties Calculated ............................................................ 214 User Profiles ..................................................................................... 214 Specifying Emulsion Polymerization Kinetics....................................................215 Accessing the Emulsion Model ............................................................. 215 Specifying the Emulsion Model ............................................................ 215 Specifying Reacting Species ................................................................ 216 Listing Reactions ...............................................................................216 Adding Reactions............................................................................... 217 Editing Reactions............................................................................... 217 Assigning Rate Constants to Reactions ................................................. 217 Selecting Calculation Options .............................................................. 218 Adding Gel-Effect ..............................................................................218 Specifying Phase Partitioning .............................................................. 218 Specifying Particle Growth Parameters ................................................. 219 References ................................................................................................. 219 11 Ziegler-Natta Polymerization Model ..............................................................220 Summary of Applications.............................................................................. 220 Ziegler-Natta Processes ...............................................................................221 Catalyst Types .................................................................................. 221 Ethylene Process Types ...................................................................... 222 Propylene Process Types .................................................................... 223 Reaction Kinetic Scheme .............................................................................. 225 Catalyst Pre-Activation ....................................................................... 232 Catalyst Site Activation ...................................................................... 232 Chain Initiation ................................................................................. 232 Propagation ...................................................................................... 233 Chain Transfer to Small Molecules ....................................................... 233 Site Deactivation ............................................................................... 234 Site Inhibition ................................................................................... 234 Cocatalyst Poisoning ..........................................................................235 Terminal Double Bond Polymerization................................................... 235 Model Features and Assumptions................................................................... 235 Phase Equilibria ................................................................................ 235 Rate Calculations .............................................................................. 236 Polymer Properties Calculated ....................................................................... 236 Specifying Ziegler-Natta Polymerization Kinetics .............................................. 237 Accessing the Ziegler-Natta Model ....................................................... 237 Specifying the Ziegler-Natta Model ...................................................... 237 Specifying Reacting Species ................................................................ 237 Listing Reactions ...............................................................................238 Adding Reactions............................................................................... 238 Editing Reactions............................................................................... 239 Assigning Rate Constants to Reactions ................................................. 239 References ................................................................................................. 239
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12 Ionic Polymerization Model ...........................................................................241 Summary of Applications.............................................................................. 241 Ionic Processes ...........................................................................................242 Reaction Kinetic Scheme .............................................................................. 242 Formation of Active Species ................................................................ 246 Chain Initiation ................................................................................. 247 Propagation ...................................................................................... 247 Association or Aggregation ................................................................. 248 Exchange ......................................................................................... 248 Equilibrium with Counter-Ion .............................................................. 248 Chain Transfer .................................................................................. 249 Chain Termination ............................................................................. 249 Coupling ..........................................................................................250 Model Features and Assumptions................................................................... 250 Phase Equilibria ................................................................................ 250 Rate Calculations .............................................................................. 250 Polymer Properties Calculated ....................................................................... 251 Specifying Ionic Polymerization Kinetics ......................................................... 252 Accessing the Ionic Model................................................................... 252 Specifying the Ionic Model .................................................................. 252 Specifying Reacting Species ................................................................ 252 Listing Reactions ...............................................................................253 Adding Reactions............................................................................... 253 Editing Reactions............................................................................... 253 Assigning Rate Constants to Reactions ................................................. 254 References ................................................................................................. 254 13 Segment-Based Reaction Model ....................................................................256 Summary of Applications.............................................................................. 256 Step-Growth Addition Processes .......................................................... 257 Polymer Modification Processes ........................................................... 257 Segment-Based Model Allowed Reactions ....................................................... 258 Conventional Species ......................................................................... 259 Side Group or Backbone Modifications .................................................. 260 Chain Scission .................................................................................. 260 Depolymerization .............................................................................. 260 Propagation ...................................................................................... 261 Combination .....................................................................................261 Branch Formation..............................................................................261 Cross Linking .................................................................................... 261 Kinetic Rate Expression ...................................................................... 261 Model Features and Assumptions................................................................... 263 Polymer Properties Calculated ....................................................................... 264 User Subroutines...............................................................................265 Specifying Segment-Based Kinetics ............................................................... 276 Accessing the Segment-Based Model.................................................... 276 Specifying the Segment-Based Model ................................................... 276 Specifying Reaction Settings ............................................................... 277 Building A Reaction Scheme................................................................ 278 Adding or Editing Reactions ................................................................ 279 Specifying Reaction Rate Constants ..................................................... 279 Assigning Rate Constants to Reactions ................................................. 280
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Including a User Rate Constant Subroutine ........................................... 280 Including a User Basis Subroutine........................................................ 281 References ................................................................................................. 281 14 Steady-State Flowsheeting............................................................................282 Polymer Manufacturing Flowsheets ................................................................ 282 Monomer Synthesis ........................................................................... 283 Polymerization .................................................................................. 284 Recovery / Separations ...................................................................... 284 Polymer Processing............................................................................ 284 Modeling Polymer Process Flowsheets ............................................................ 284 Steady-State Modeling Features .................................................................... 285 Unit Operations Modeling Features....................................................... 285 Plant Data Fitting Features ................................................................. 285 Process Model Application Tools........................................................... 285 References ................................................................................................. 285 15 Steady-State Unit Operation Models..............................................................286 Summary of Aspen Plus Unit Operation Models ................................................ 286 Dupl ................................................................................................288 Flash2 ............................................................................................. 290 Flash3 ............................................................................................. 290 FSplit .............................................................................................. 291 Heater ............................................................................................. 291 Mixer...............................................................................................291 Mult ................................................................................................ 291 Pump .............................................................................................. 292 Pipe ................................................................................................292 Sep ................................................................................................. 293 Sep2 ...............................................................................................293 Distillation Models .......................................................................................293 RadFrac ........................................................................................... 293 Reactor Models ........................................................................................... 294 Mass-Balance Reactor Models ....................................................................... 294 RStoic ............................................................................................. 294 RYield..............................................................................................295 Equilibrium Reactor Models........................................................................... 296 REquil..............................................................................................296 RGibbs............................................................................................. 296 Kinetic Reactor Models ................................................................................. 296 RCSTR .............................................................................................296 RPlug ..............................................................................................309 RBatch.............................................................................................319 Treatment of Component Attributes in Unit Operation Models ............................ 328 References ................................................................................................. 330 16 Plant Data Fitting ..........................................................................................331 Data Fitting Applications .............................................................................. 331 Data Fitting For Polymer Models .................................................................... 332 Data Collection and Verification ........................................................... 333 Literature Review .............................................................................. 333
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Preliminary Parameter Fitting .............................................................. 334 Preliminary Model Development........................................................... 335 Trend Analysis .................................................................................. 335 Model Refinement .............................................................................336 Steps for Using the Data Regression Tool ....................................................... 336 Identifying Flowsheet Variables ........................................................... 338 Manipulating Variables Indirectly ......................................................... 339 Entering Point Data ........................................................................... 341 Entering Profile Data.......................................................................... 342 Entering Standard Deviations .............................................................. 343 Defining Data Regression Cases .......................................................... 343 Sequencing Data Regression Cases ...................................................... 344 Interpreting Data Regression Results ................................................... 344 Troubleshooting Convergence Problems................................................ 345 17 User Models...................................................................................................351 User Unit Operation Models .......................................................................... 351 User Unit Operation Models Structure................................................... 351 User Unit Operation Model Calculations................................................. 352 User Unit Operation Report Writing ...................................................... 357 User Kinetic Models .....................................................................................357 User Physical Property Models ....................................................................... 361 References ................................................................................................. 365 18 Application Tools ...........................................................................................366 Example Applications for a Simulation Model ................................................... 366 Application Tools Available in Aspen Polymers ................................................. 367 CALCULATOR .................................................................................... 367 DESIGN-SPEC................................................................................... 368 SENSITIVITY .................................................................................... 368 CASE-STUDY .................................................................................... 368 OPTIMIZATION ................................................................................. 369 Model Variable Accessing.............................................................................. 369 References ................................................................................................. 371 19 Run-Time Environment..................................................................................372 Aspen Polymers Architecture.........................................................................372 Installation Issues ....................................................................................... 373 Hardware Requirements ..................................................................... 373 Installation Procedure ........................................................................ 373 Configuration Tips .......................................................................................373 Startup Files .....................................................................................373 Simulation Templates ........................................................................ 373 User Fortran ...............................................................................................374 User Fortran Templates ...................................................................... 374 User Fortran Linking .......................................................................... 374 Troubleshooting Guide ................................................................................. 374 User Interface Problems ..................................................................... 374 Simulation Engine Run-Time Problems ................................................ 376 References ................................................................................................. 377
Contents
A Component Databanks ....................................................................................378 Pure Component Databank ........................................................................... 378 POLYMER Databank .....................................................................................378 POLYMER Property Parameters ............................................................ 378 POLYMER Databank Components ......................................................... 379 SEGMENT Databank .................................................................................... 382 SEGMENT Property Parameters ........................................................... 382 SEGMENT Databank Components ........................................................ 383 B Kinetic Rate Constant Parameters...................................................................421 Initiator Decomposition Rate Parameters ........................................................ 421 Solvent Dependency .......................................................................... 421 Concentration Dependency ................................................................. 422 Temperature Dependency................................................................... 422 Pressure Dependency ........................................................................ 423 References ................................................................................................. 434 C Fortran Utilities ...............................................................................................435 Component Attribute Handling Utilities ........................................................... 436 CAELID ............................................................................................ 436 CAID ............................................................................................... 436 CAMIX .............................................................................................437 CASPLT............................................................................................ 438 CASPSS ........................................................................................... 438 CAUPDT ........................................................................................... 439 COPYCA ...........................................................................................440 GETCRY ...........................................................................................440 GETDPN ...........................................................................................441 GETMWN..........................................................................................442 GETMWW .........................................................................................443 GETPDI............................................................................................443 GETSMF ........................................................................................... 444 GETSWF .......................................................................................... 445 LCAOFF............................................................................................446 LCATT..............................................................................................446 NCAVAR........................................................................................... 447 Component Handling Utilities ........................................................................ 448 CPACK ............................................................................................. 448 IFCMNC ...........................................................................................449 ISCAT.............................................................................................. 449 ISINI ...............................................................................................450 ISOLIG ............................................................................................ 450 ISPOLY ............................................................................................451 ISSEG ............................................................................................. 451 SCPACK ...........................................................................................452 XATOWT .......................................................................................... 453 XATOXT ........................................................................................... 453 General Stream Handling Utilities .................................................................. 454 IPTYPE.............................................................................................454 LOCATS ........................................................................................... 455 LPHASE ...........................................................................................456
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NPHASE ...........................................................................................456 NSVAR.............................................................................................457 SSCOPY ........................................................................................... 457 Other Utilities ............................................................................................. 458 VOLL ............................................................................................... 458 D Input Language Reference ..............................................................................460 Specifying Components................................................................................ 460 Naming Components.......................................................................... 460 Specifying Component Characterization Inputs........................................ 461 Specifying Component Attributes................................................................... 464 Specifying Characterization Attributes .................................................. 464 Specifying Conventional Component Attributes ...................................... 464 Initializing Attributes in Streams.......................................................... 465 Specifying Attribute Scaling Factors ............................................................... 466 Specifying Component Attribute Scale Factors ....................................... 466 Requesting Distribution Calculations .............................................................. 467 Calculating End Use Properties ...................................................................... 468 Specifying Physical Property Inputs................................................................ 470 Specifying Property Methods ............................................................... 470 Specifying Property Data .................................................................... 471 Estimating Property Parameters .......................................................... 473 Specifying Step-Growth Polymerization Kinetics............................................... 474 Specifying Free-Radical Polymerization Kinetics ............................................... 482 Specifying Emulsion Polymerization Kinetics....................................................493 Specifying Ziegler-Natta Polymerization Kinetics .............................................. 499 Specifying Ionic Polymerization Kinetics ......................................................... 510 Specifying Segment-Based Polymer Modification Reactions ............................... 517 References ................................................................................................. 521 Index ..................................................................................................................522
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Introducing Aspen Polymers
Aspen Polymers (formerly known as Aspen Polymers Plus) is a generalpurpose process modeling system for the simulation of polymer manufacturing processes. The modeling system includes modules for the estimation of thermophysical properties, and for performing polymerization kinetic calculations and associated mass and energy balances. Also included in Aspen Polymers are modules for: Characterizing polymer molecular structure Calculating rheological and mechanical properties Tracking these properties throughout a flowsheet
There are also many additional features that permit the simulation of the entire manufacturing processes.
About This Documentation Set

The Aspen Polymers User Guide is divided into two volumes. Each volume documents features unique to Aspen Polymers. This User Guide assumes prior knowledge of basic Aspen Plus capabilities or user access to the Aspen Plus documentation set. If you are using Aspen Polymers with Aspen Dynamics, please refer to the Aspen Dynamics documentation set. Volume 1 provides an introduction to the use of modeling for polymer processes and discusses specific Aspen Polymers capabilities. Topics include: Polymer manufacturing process overview - describes the basics of polymer process modeling and the steps involved in defining a model in Aspen Polymers. Polymer structural characterization - describes the methods used for characterizing components. Included are the methodologies for calculating distributions and features for tracking end-use properties. Polymerization reactions - describes the polymerization kinetic models, including: step-growth, free-radical, emulsion, Ziegler-Natta, ionic, and segment based. An overview of the various categories of polymerization kinetic schemes is given. Steady-state flowsheeting - provides an overview of capabilities used in constructing a polymer process flowsheet model. For example, the unit
operation models, data fitting tools, and analysis tools, such as sensitivity studies. Run-time environment - covers issues concerning the run-time environment including configuration and troubleshooting tips.
Volume 2 describes methodologies for tracking chemical component properties, physical properties, and phase equilibria. It covers the physical property methods and models available in Aspen Polymers. Topics include: Thermodynamic properties of polymer systems describes polymer thermodynamic properties, their importance to process modeling, and available property methods and models. Equation-of-state (EOS) models provides an overview of the properties calculated from EOS models and describes available models, including: Sanchez-Lacombe, polymer SRK, SAFT, and PC-SAFT. Activity coefficient models provides an overview of the properties calculated from activity coefficient models and describes available models, including: Flory-Huggins, polymer NRTL, electrolyte-polymer NRTL, polymer UNIFAC. Thermophysical properties of polymers provides and overview of the thermophysical properties exhibited by polymers and describes available models, including: Aspen ideal gas, Tait liquid molar volume, pure component liquid enthalpy, and Van Krevelen liquid and solid, melt and glass transition temperature correlations, and group contribution methods. Polymer viscosity models describes polymer viscosity model implementation and available models, including: modified MarkHouwink/van Krevelen, Aspen polymer mixture, and van Krevelen polymer solution. Polymer thermal conductivity models - describes thermal conductivity model implementation and available models, including: modified van Krevelen and Aspen polymer mixture.
Related Documentation
A volume devoted to simulation and application examples for Aspen Polymers is provided as a complement to this User Guide. These examples are designed to give you an overall understanding of the steps involved in using Aspen Polymers to model specific systems. In addition to this document, a number of other documents are provided to help you learn and use Aspen Polymers, Aspen Plus, and Aspen Dynamics applications. The documentation set consists of the following:
Installation Guides
Aspen Engineering Suite Installation Guide
Aspen Polymers Guides

Aspen Polymers User Guide, Volume 1
Aspen Polymers User Guide, Volume 2 (Physical Property Methods & Models) Aspen Polymers Examples & Applications Case Book
Aspen Plus Guides

Aspen Plus User Guide Aspen Plus Getting Started Guides
Aspen Physical Property System Guides

Aspen Physical Property System Physical Property Methods and Models Aspen Physical Property System Physical Property Data
Aspen Dynamics Guides

Aspen Dynamics Examples Aspen Dynamics User Guide Aspen Dynamics Reference Guide
Help
Aspen Polymers has a complete system of online help and context-sensitive prompts. The help system contains both context-sensitive help and reference information. For more information about using Aspen Polymers help, see the Aspen Plus User Guide.
Third-Party
More detailed examples are available in Step-Growth Polymerization Process Modeling and Product Design by Kevin Seavey and Y. A. Liu, ISBN: 978-0470-23823-3, Wiley, 2008.
Technical Support
AspenTech customers with a valid license and software maintenance agreement can register to access the online AspenTech Support Center at: http://support.aspentech.com This Web support site allows you to: Access current product documentation Search for tech tips, solutions and frequently asked questions (FAQs) Search for and download application examples Search for and download service packs and product updates Submit and track technical issues Send suggestions Report product defects
Review lists of known deficiencies and defects
Registered users can also subscribe to our Technical Support e-Bulletins. These e-Bulletins are used to alert users to important technical support information such as: Technical advisories Product updates and releases
Customer support is also available by phone, fax, and email. The most up-todate contact information is available at the AspenTech Support Center at http://support.aspentech.com.
1 Polymer Manufacturing Process Overview
This chapter provides an overview of the issues related to polymer manufacturing process modeling and their handling in Aspen Polymers (formerly known as Aspen Polymers Plus). Topics covered include: About Aspen Polymers, 5 Overview of Polymerization Processes, 6 Issues of Concern in Polymer Process Modeling, 7 Aspen Polymers Tools, 9 Defining a Model in Aspen Polymers, 12
About Aspen Polymers

Aspen Polymers is a general-purpose process modeling system for the simulation of polymer manufacturing processes. The modeling system includes modules for the estimation of thermophysical properties, and for performing polymerization kinetic calculations and associated mass and energy balances. Also included in Aspen Polymers are modules for: Characterizing polymer molecular structure Calculating rheological and mechanical properties Tracking these properties throughout a flowsheet
There are also many additional features that permit the simulation of the entire manufacturing processes.
Overview of Polymerization Processes

Polymer Definition
A polymer is a macromolecule made up of many smaller repeating units providing linear and branched chain structures. Although a wide variety of polymers are produced naturally, synthetic or man-made polymers can be tailored to satisfy specific needs in the market place, and affect our daily lives at an ever-increasing rate. The worldwide production of synthetic polymers, estimated at approximately 100 million tons annually, provides products such as plastics, rubber, fibers, paints, and adhesives used in the manufacture of construction and packaging materials, tires, clothing, and decorative and protective products.
Polymer Molecular Bonds

Polymer molecules involve the same chemical bonds and intermolecular forces as other smaller chemical species. However, the interactions are magnified due to the molecular size of the polymers. Also important in polymer production are production rate optimization, waste minimization and compliance to environmental constraints, yield increases and product quality. In addition to these considerations, end-product processing characteristics and properties must be taken into account in the production of polymers (Dotson, 1996).
Polymer Manufacturing Process Steps

Polymer manufacturing processes are usually divided into the following major steps: 1 2 3 4 Monomer Synthesis and Purification Polymerization Recovery / Separation Polymer Processing
The four steps may be carried out by the same manufacturer within a single integrated plant, or specific companies may focus on one or more of these steps (Grulke, 1994). The four steps may be carried out by the same manufacturer within a single integrated plant, or specific companies may focus on one or more of these steps (Grulke, 1994). The following figure illustrates the important stages for each of the four polymer production steps. The main issues of concern for each of these steps are described next.
Issues of Concern in Polymer Process Modeling

There are modeling issues associated with each step in the production of polymers. The following table summarizes these issues along with the required tools:
Step Monomer synthesis and purification
Modeling Issues/Concerns Feedstock purity Monomer degradation Emissions Waste disposal
Tools Required Unit operations: separators Reaction kinetics Phase equilibria Characterization Reaction kinetics Phase equilibria Heat transfer Unit operations: reactors Transport phenomena Process dynamics Process control Unit operations: separators Phase equilibria Heat and mass transfer Heat and mass transfer Unit operations: separators
Polymerization
Temperature control Molecular weight control, polymer specifications Conversion yield Reaction medium viscosity Residence time Reactor stability Waste minimization
Recovery / Separation
Solvent removal Monomer recovery
Polymer processing
Solvent removal Solids handling
Monomer Synthesis and Purification

During monomer synthesis and purification, the engineer is concerned with purity. This is because the presence of contaminants, such as water or dissolved gases for example, may adversely affect the subsequent polymerization stage by: Poisoning catalysts Depleting initiators Causing undesirable chain transfer or branching reactions
Another concern of this step is the prevention of monomer degradation through proper handling or the addition of stabilizers. Control of emissions, and waste disposal are also important factors in this step.
Polymerization
The polymerization step is usually the most important step in terms of the economic viability of the manufacturing process. The desired outcome for this step is a polymer product with specified properties such as: Molecular weight distribution Melt index Composition Crystallinity/density Viscosity
The obstacles that must be overcome to reach this goal depend on both the mechanism of polymer synthesis (chain growth or step growth), and on the polymerization process used. Polymerization processes may be batch, semi-batch or continuous. In addition, they may be carried out in bulk, solution, slurry, gas-phase, suspension or emulsion. Batch and semi-batch processes are preferred for specialty grade polymers. Continuous processes are usually used to manufacture large volume commodity polymers. Productivity depends on heat removal rates and monomer conversion levels achieved. Viscosity of polymer solutions, and polymer particle suspensions and mixing are important considerations. These factors influence the choice of, for example, bulk versus solution versus slurry polymerization. Another example is the choice of emulsion polymerization that is often dictated by the form of the end-use product, water-based coating or adhesive. Other important considerations may include health, safety and environmental impact. Most polymerizations are highly exothermic, some involve monomers that are known carcinogens and others may have to deal with contaminated water. In summary, for the polymerization step, the reactions which occur usually cause dramatic changes in the reaction medium (e.g. significant viscosity increases may occur), which in turn make high conversion kinetics, residencetime distribution, agitation and heat transfer the most important issues for the majority of process types.
Recovery / Separation
The recovery/separation step can be considered the step where the desired polymer produced is further purified or isolated from by-products or residual reactants. In this step, monomers and solvents are separated and purified for recycle or resale. The important concerns for this step are heat and mass transfer.
Polymer Processing
The last step, polymer processing, can also be considered a recovery step. In this step, the polymer slurry is turned into solid pellets or chips. Heat of vaporization is an important factor in this step (Grulke, 1994).
Summary
In summary, production rate optimization, waste minimization and compliance to environmental constraints, yield increase, and product quality are also important issues in the production of polymers. In addition, process dynamics and stability constitute important factors primarily for reactors.
Aspen Polymers Tools

Aspen Polymers provides the tools that allow polymer manufacturers to capture the benefits of process modeling.
Aspen Polymers can be used to build models for representing processes in two modes: with Aspen Plus for steady-state models, and with Aspen Dynamics or Aspen Custom Modeler for dynamic models. In both cases, the tools used specifically for representing polymer systems fall into four categories: Polymer characterization Physical properties Reaction kinetics Data
Through Aspen Plus, Aspen Dynamics and Aspen Custom Modeler, Aspen Polymers provides robust and efficient algorithms for handling: Flowsheet convergence and optimization Complex separation and reaction problems User customization through an open architecture
Component Characterization
Characterization of a polymer component poses some unique challenges. For example, the polymer component is not a single species but a mixture of many species. Properties such as molecular weight and copolymer composition are not necessarily constant and may vary throughout the flowsheet and with time. Aspen Polymers provides a flexible methodology for characterizing polymer components (U.S. Patent No. 5,687,090). Each polymer is considered to be made up of a series of segments. Segments have a fixed structure. The changing nature of the polymer is accounted for by the specification of the number and type of segments it contains at a given processing step. Each polymer component has associated attributes used to store information on molecular structure and distributions, product properties, and particle size when necessary. The polymer attributes are solved/integrated together with the material and energy balances in the unit operation models.
Polymer Physical Properties

Correlative and predictive models are available in Aspen Polymers for representing the thermophysical properties of a polymer system, the phase equilibrium, and the transport phenomena. Several physical property methods combining these models are available. In addition to the built-in thermodynamic models, the open architecture design allows users to override the existing models with their own in-house models.
Polymerization Kinetics
The polymerization step represents the most important stage in polymer processes. In this step, kinetics play a crucial role. Aspen Polymers provides built-in kinetic mechanisms for several chain-growth and step-growth type polymerization processes. The mechanisms are based on well-established sources from the open literature, and have been extensively used and
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validated against data during modeling projects of industrial polymerization reactors. There are also models for representing polymer modification reactions, and for modeling standard chemical kinetics. In addition to the built-in kinetic mechanisms, the open-architecture design allows users to specify additional reactions, or to override the built-in mechanisms.
Modeling Data
A key factor in the development of a successful simulation model is the use of accurate thermodynamic data for representing the physical properties of the system, and of kinetic rate constant data which provide a good match against observed trends. In order to provide the physical property models with the parameters necessary for property calculations, Aspen Polymers has property parameter databanks available. These include: Polymer databank containing parameters independent of chain length Segment databank containing parameters to which composition and chain length are applied for polymer property calculations Functional group databank containing parameters for models using a group contribution approach is also included
This User Guide contains several tabulated parameters which may be used as starting values for specific property models. Property data packages are also being compiled for some polymerization processes and will be made available in future versions. In addition to physical property data, Aspen Polymers provides users with ways of estimating missing reaction rate constant data. For example, the data regression tool can be used to fit rate constants against molecular weight data.
Process Flowsheeting
Aspen Polymers provides unit operation models, flowsheeting options, and analysis tools for a complete representation of a process. Models for batch, semi-batch and continuous reactors with mixing extremes of plug flow to backmix are available. In addition, other unit operation models essential for flowsheet modeling are available such as: Mixers Flow splitters Flash tanks Devolatilization units
Flowsheet connectivity and sequencing is handled in a straightforward manner. Several analysis tools are available for applying the simulation models developed. These include tools for: Process optimization
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Examining process alternatives as case studies Analyzing the sensitivities of key process variables on polymer product properties Fitting process variables to meet design specifications
Defining a Model in Aspen Polymers

In order to build a model of a polymer process you must already be familiar with Aspen Plus. Therefore, only the steps specific to polymer systems will be described in detail later in this User Guide. The steps for defining a model in Aspen Polymers are as follows: Step 1. Specifying Global Simulation Options The first step in defining the model is the specification of: Global simulation options, i.e. simulation type Units to be used for simulation inputs and results Basis for flowrates Maximum simulation times Diagnostic options
Step 2. Defining the Flowsheet For a full flowsheet model, the next step is the flowsheet definition. Here you would specify the unit operation models contained in the flowsheet and define their connectivity. Chapter 4 describes the unit operation models available for building a flowsheet. Step 3. Defining Components Most simulation types require a definition of the component system. You must correctly identify polymers, polymer segments, and oligomers as such. All other components are considered conventional by default. Chapter 2 provides information on defining components. Step 4. Characterizing Components Conventional components in the system are categorized by type. Additional characterization information is required for other than conventional components. You must specify the: Component attributes to be tracked for polymers Type of segments present Structure of oligomers Type and activity of catalysts
In addition, you may wish to request tracking of molecular weight distribution. Component characterization is discussed in Chapter 2.
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Step 5. Specifying Property Models You must select the models to be used to represent the physical properties of your system. The Aspen Polymers User Guide, Volume 2, Aspen Polymers Physical Property Methods and Models, describes the options available for specifying physical property models. Step 6. Defining Polymerization Kinetics Once you have made selections out of the built-in polymerization kinetic models to represent your reaction system, you need to choose specific reactions from the sets available and enter rate constant parameters for these reactions. Chapter 3 describes the models available and provides descriptions of the input options. Step 7. Defining Feed Streams For flowsheet simulations, you must enter the conditions of the process feed streams. If the feed streams contain polymers, you must initialize the polymer attributes. Polymer attribute definition in streams is discussed in a separate section of Chapter 2. Step 8. Specifying UOS Model Operating Conditions You must specify the configuration and operating condition for unit operation models contained in the flowsheet. In the case of reactors, you have the option of assigning kinetic models defined in step 6 to specific reactors. Chapter 4 provides some general information regarding the use of unit operation models. Step 9. Specifying Additional Simulation Options For a basic simulation the input information you are required to enter in steps 1-8 is sufficient. However, there are many more advanced simulation options you may wish to add in order to refine or apply your model. These include setting up the model for plant data fitting, sensitivity analyses, etc. Many of these options are described in a separate section of Chapter 4. Information for building dynamic models is given in the Aspen Dynamics and Aspen Custom Modeler documentation sets. Note that for building dynamic models, users must first build a steady-state model containing: Definition of the polymer system in terms of components present Physical property models Polymerization kinetic models
Note: Aspen Polymers setup and configuration instructions are given in Chapter 5.
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References
Dotson, N. A., Galvn, R., Laurence, R. L., & Tirrell, M. (1996). Polymerization Process Modeling. New York: VCH Publishers. Grulke, E. A. (1994). Polymer Process Engineering. Englewood Cliffs, NJ: Prentice Hall. Odian, George. (1991). Principles of Polymerization (3rd Ed.). New York: John Wiley and Sons.
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2 Polymer Structural Characterization
One of the fundamental aspects of modeling polymer systems is the handling of the molecular structure information of polymers. This chapter discusses the approaches used to address this issue in Aspen Polymers (formerly known as Aspen Polymers Plus). Topics covered include: Polymer Structure, 15 Polymer Structural Properties, 19 Characterization Approach, 19
Included in this manual are several sections devoted to the specification of polymer structural characterization information. 3 Component Classification, 21 Polymer Structural Properties, 32 Structural Property Distributions, 53 End-Use Properties, 70
Polymer Structure
Polymers can be defined as large molecules or macromolecules where a smaller constituting structure repeats itself along a chain. For this reason, polymers tend to exhibit different physical behavior than small molecules also called monomers. Synthetic polymers are produced when monomers bond together through polymerization and become the repeating structure or segment within a chain. When two or more monomers bond together, a polymer is formed. Small polymer chains containing 20 or less repeating units are usually called oligomers. The fact that identifiable segments are found repeatedly along a polymer chain, provides convenient ways to categorize polymers. Polymers can be classified based on segment composition or sequence: Homopolymers - containing one type of repeating unit which can be mapped into one segment
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Copolymers - which have two or more repeating units. Copolymers can be in a random, alternating, block, or graft configuration
If we consider the arrangement of a given chain, another classification arises. Polymers may be: Linear Branched (with short or long chains) Star Ladder Network
Another classification that results from polymer structure has to do with physical state. A solid polymer may be: Amorphous - when the chains are not arranged in a particular pattern Crystalline - when the chains are arranged in a regular pattern
A related classification divides polymers by thermal and mechanical properties into: Thermoplastics (may go from solid to melt and vice versa) Thermosets (remain solid through heating) Elastomers (which have elastic properties)
Finally, polymers can be categorized based on the form they are manufactured into: plastics, fibers, film, coatings, adhesives, foams, and composites.
Polymer Types by Physical Structure

The following figure illustrates the various polymer types based on chain structure:
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Polymer Types by Property

The following table illustrates the various polymer types based on properties:
Classification Type Physical Property
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Thermal / Mechanical properties Fabrication
Thermoplastics Thermosets Elastomers Plastics Fibers Coatings Adhesives Foams Composites Elastomers
Can melt and solidify again Remain solid through heating Have elastic properties Very versatile in terms of application Most commonly used as textiles Used for both decorative and protective purposes Used for their bonding properties Used as packaging, upholstery, insulation, etc. Can be tailored to many applications Used for their elastic properties
In addition to these classifications, polymers can be categorized based on the type of constituting atoms on the chains. Homochains produced through chain-growth polymerization have only carbon atoms on the polymer backbone. Heterochains produced through step-growth polymerization have other types of atom incorporated into the polymer backbone.
Polymer Categories by Chemical Structure

The following table lists various homochain and heterochain polymers based on the type of atoms on the polymer backbone or the substituted side groups:
Polymer Category Description Examples
Polymers with carbon-carbon backbone Polyacrylics Ethylene backbone with one acrylic acid (or derivative) as side group per ethylene One double bond per repeat unit Fluorine or chlorine side group per ethylene Alphatic or aromatic substituents From vinyl monomers Polyacrylic acid, polymethyl methacrylate, polyacrylonitrile, polyacrylamide Polybutadiene Polyvinyl fluoride, polyvinylidene fluoride, polyvinylchloride, Polyethylene, polypropylene, polyisobutylene, polystyrene Polyvinyl acetate, polyvinyl alcohol
Polydienes Polyhalogen hydrocarbons Polyolefins Polyvinyls
Polymers with carbon-nitrogen backbone Polyamides Polyurethanes Polyureas Amide group on backbone Urethane group on backbone Urea group on backbone Nylon 6, nylon 6,6 Polyurethane foams Polyurea resins
Polymers with carbon-oxygen backbone Polyacetals Polyethers Acetal group on backbone Ether group on backbone Polyacetate Polyethylene oxide, polyphenylene oxide
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Polymer Category Polyesters
Description Ester group on backbone
Examples Polycarbonate polyethylene therephthalate, polybutylene therephthalate polylactide
Polymers with carbon-sulfur backbone Polysulfides Sulfide group on backbone Polysulfide fibers
Polymer Structural Properties

All the methods of categorizing polymers point to certain key characteristics that must be taken into account in order to fully define polymer molecules. Typical information needed to capture the structure and behavior of polymers includes: Chemical structure of segments: segment type, and configuration Chain size for the mixture of polymer chains Crystallinity Additional structural, thermal, and mechanical characteristics
Characterization Approach
Aspen Polymers allows for the different types of chemical species that may be found in a polymer system: Monomers Solvents Catalysts Oligomers Polymers
Polymer segments are introduced to identify the chemical structure of the polymer or oligomer repeat unit. In addition, they are used as building blocks within polymerization reactions, and in the determination of thermodynamic properties. More than the chemical structure of the segments is needed in order to define a polymer. Also needed is the segment composition of the chains. In addition, properties related to size are needed: degree of polymerization or number of segments.
Component Attributes
Within Aspen Polymers, component attributes are used to define these structural characteristics. Component attributes are available to track segment composition, degree of polymerization, molecular weight, etc. Because the polymer is a mixture of chains, there is normally a distribution of
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these structural characteristics. The component attributes are used to track the averages. There are additional attributes used to track information about the distribution of chain sizes. These are the moments of chain length distribution. For detailed information about component attributes, see Polymer Structural Properties on page 32. In addition to the component attributes, users have the option within Aspen Polymers to examine polymer molecular weight distribution. This feature is based on a method of instantaneous properties. For more information, see Method of Instantaneous Properties on page 58.
References
Grulke, E. A. (1994). Polymer Process Engineering. Englewood Cliffs, NJ: Prentice Hall. Munk, P. (1989). Introduction to Macromolecular Science. New York: John Wiley and Sons. Odian, G. (1991). Principles of Polymerization (3rd Ed.). New York: John Wiley and Sons. Rudin, A. (1982). The Elements of Polymer Science and Engineering. Orlando: Academic Press.
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3 Component Classification
This section discusses the specification of components in a simulation model. Topics covered include: Component Categories, 21 Component Databanks, 25 Segment Methodology, 27 Specifying Components, 27
Component Categories
When developing a simulation model in Aspen Polymers (formerly known as Aspen Polymers Plus), users must assign components present in process flow streams to one of the following categories: Conventional Polymer Oligomer Segment Site-based
The following figure illustrates the different categories of components and their input requirements:
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Conventional Components
Standard conventional components are molecular components such as water. These components have a fixed molecular structure and participate in phase equilibrium. Components falling into this category include: Monomers Initiators Chain transfer agents Solvents Catalysts
In order to fully specify conventional components, you need only specify pure component data required for the phase equilibrium calculations. This data may be entered or retrieved from component databanks. Note: Ziegler-Natta catalysts and ionic initiators require additional characterization information.
Polymers
In Aspen Polymers, polymer components represent a distribution of polymeric species. The average size and composition of the molecules in this distribution
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can change throughout the simulation. Each polymer molecule is considered to be made up of repeating units or segments. Typically, the segments correspond to the monomers that are used to grow the polymer. The structure of polymers depends on the number and type of segments they contain and the arrangement of segments in linear, branched, or cross-linked forms. Component attributes are used to track polymer structural properties (U.S. Patent No. 5,687,090) such as: Segment composition Copolymer composition and average sequence length Degree of polymerization Molecular weight Branching Moments of molecular weight distribution Molecular architecture (physical arrangement of segments within the polymer molecule)
Segments are specified independently from polymers. For each polymer, you must select the types of component attributes to be included in the simulation model. If the polymer is present in the process feed streams, you must provide its properties by initializing the component attributes while specifying input data for these feed streams. For more information on component attribute specification, see Polymer Structural Properties on page 32.
Oligomers
By convention, oligomers are defined as components with two or more segments and a fixed molecular structure. They can be defined as volatile or non-volatile. Typically, the oligomer feature is used to allow users to track the loss of volatile short-chain polymers. In order to specify oligomers, you must specify their composition in terms of the number and type of segments they contain. Oligomers do not require component attributes. For this reason, you may treat a polymer as an oligomer in cases where you want to process the polymer within a unit operation model which cannot handle polymer component attribute data. When using oligomer components, you may specify addition properties through the following unary property parameters:
Parameter POLDP POLPDI POLCRY Definition Number-average chain length Polydispersity index Mass fraction crystallinity Default Calculated * 1 **
* **
Calculated from the number of segments in the oligomer as specified in the Polymers form Oligomers subform. Used to calculate DPW and MWW.
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Note: Not all kinetic models track oligomers as separate components. If a model does not provide fields for specifying oligomers on its input forms, then these components are not tracked.
Segments
Segments are the structural units of a polymer or oligomer and are specified independently from these components. Their structure is fixed throughout a simulation. Segments typically correspond to the monomers used to grow the polymer. They are divided into types depending on their location on the polymer chain: Repeat units End groups Branch point (attached to three or four branches)
Site-Based
Site-based components pertain to multisite reaction kinetic models (ZieglerNatta and Ionic). Site-based components include Ziegler-Natta catalysts and ionic initiators.
Ziegler-Natta Catalysts
Ziegler-Natta catalysts are often used to initiate polymer chain formation in chain-growth polymerization reactions. Catalysts can be treated as standard conventional components. Ziegler-Natta catalysts or metallocene catalysts involve one or more polymerization site types which may be in an activated or deactivated state. In order to use Ziegler-Natta catalysts, you must specify the number of site types and the catalyst properties to be tracked, that is, the site activity. Catalyst properties are defined as component attributes. You must initialize the catalyst properties while specifying input data for the streams containing the catalysts. For more information on component attribute specification, see Polymer Structural Properties on page 32.
Ionic Initiators
Ionic initiators are used in anionic and cationic polymerization. The ionic initiators can be treated as standard conventional components. The propagating species in ionic polymerization can be: Free-ions Ion-pairs Dormant esters
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In Aspen Polymers, these different species are modeled as different sites of an ionic initiator. Three different site-based attributes are tracked for an ionic initiator. For more information, see Ionic Initiator Attributes on page 44.
Component Databanks
The thermodynamic and transport property models needed to perform the physical property and phase equilibrium calculations during a simulation require pure component property data. These include: Molecular weight Heat capacity Heat of formation Heat of vaporization Vapor pressure Density
Enter that information while selecting and specifying physical property models. Normally, you would make use of the pure component databanks and retrieve data from them for each of the components present in the simulation model: Data for conventional components are retrieved from the Pure Component databank Data for free-radical initiators are retrieved from the INITIATOR databank Data for polymers are retrieved from the POLYMER databank Data for oligomers are retrieved either from the pure component databank or from the POLYMER databank Data for segments are retrieved from the SEGMENT databank Data for PC-SAFT are retrieved from the PC-SAFT databank Data for POLYPCSF are retrieved from the POLYPCSF databank
Descriptions of the databanks, and the parameters they contain are given in Appendix A.
Pure Component Databank

In the Pure Component databank, components are named using a nomenclature developed for Aspen Plus. Each component is given an alias summarizing the number of each type of atom: C, H, O, N, P, S, CL, F, etc. (e.g. C2H4 for ethylene). For cases where the same alias matches several components, a counter is added to make the distinction (e.g. C2H4O2-1 for acetic acid). Note: Catalysts are often solid components and may not be found in the PURE11 databank. Normally, you do not need a rigorous representation of these components.
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An acceptable approach is to assign a monomer alias to the catalyst and then provide the correct molecular weight and certain parameters which will prevent the catalyst from vaporizing. If an activity coefficient model is being used for phase equilibrium representation, the catalysts can be assumed to be non-volatile by specifying -40 as the first Antoine parameter (PLXANT(1) = 40).
PC-SAFT Databank
The PC-SAFT databank contains pure and binary parameters used with the PC-SAFT property method. The parameters are taken from the literature, including many normal compounds, polar compounds and associating compounds.
POLYPCSF Databank
The POLYPCSF databank contains pure and binary parameters used with the POLYPCSF property method. The parameters are taken from the literature, including many normal compounds, but excluding polar compounds and associating compounds.
INITIATO Databank
The INITIATO databank contains data for initiator components. Rate constants in this databank are derived from half-life data in vendor datasheets published on public web sites. These datasheets generally contain data at several temperatures, allowing the activation energy and prefactor to be determined. These rate constants depend on the reaction environment, and may vary between polar and non-polar solvents. Where multiple sets of data were available, the data from monomer or organic solvents were used in preference to data from aqueous solutions. Molecular weight and other parameters are calculated from structure using estimation methods from Aspen Plus, except in those few cases where vapor pressure data was provided in the datasheets. In the INITIATO databank, components are named using industry-standard acronyms. Each component is given an alias summarizing the number of each type of atom: C, H, O, N, P, S, CL, F, etc. For cases where the same alias matches several components, a counter is added to make the distinction (e.g. 1,-2, etc).
Segment Databank
In the Segment Databank, a segment name comes from the name of the monomer from which it originates. Therefore, in this databank component names and aliases follow the same conventions as those for the Pure Component Databank. A label is added to the monomer name to identify the segment as either a repeat unit,-R, an end group,-E, or a branch point, -B (e.g. for butadiene segments: C4H6R1or BUTADIENER1 corresponding to the repeat unit
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CH2CH=CHCH2, C4H5E1 or BUTADIENEE1 corresponding to the end group CH=CHCH=CH2 and C4H5B or BUTADIENEB corresponding to the branch segment
CH2 CH CH CH
).
Polymer Databank
The Polymer Databank does not follow the conventional nomenclature. The polymer aliases are the typical acronyms used in industry or academia, and the polymer names consist of the repeat unit name enclosed in parentheses and preceded by the prefix Poly (e.g. PS or POLY(STYRENE) for polystyrene). Note: The MW property parameter used to store molecular weights in the component databanks is the true molecular weight for all component types except polymers. For polymers, the true polymer molecular weight is normally tracked as a component attribute only. The molecular weight stored in the databank is the apparent molecular weight calculated as the average segment molecular weight (See Appendix A).
Segment Methodology
The segment approach to characterizing components is a fundamental methodology which affects almost every functionality within Aspen Polymers. Segments are used as the building blocks for polymers. Once you have specified the types of segments in the polymer, the segment composition and degree of polymerization defined as component attributes may be used to define the size and composition of the polymer. For oligomers, although component attributes are not used, the number of each segment must be specified directly. Most of the Aspen Polymers physical property models calculate polymer and oligomer properties from segment properties. This is done by taking into account the degree of polymerization and the segment composition. The calculated properties should be the same for both oligomers and polymers, assuming that the oligomer structure and molecular weight were specified correctly. Note that this is true for mass-based properties only. Mole-based properties will be different between polymer and oligomer if their apparent molecular weights are different. Within the polymerization reaction models, segments also play a key role. As polymerization progresses, the models map the reacting monomers into the corresponding segments and return rates of change for the segment composition.
Specifying Components
To specify components within your model you need to know the following:
Item Component types For All the species in your system
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Property parameter databank selections IUPAC names
The species in the system All conventional components or you need their physical properties (molecular weight, boiling point, Antoine constants, etc.) All polymers and oligomers (define whether you want to include any end groups or branch points) All polymers, that is, degree of polymerization, segment composition All additional characteristics for catalysts, or ionic initiators
Segment structure Polymer properties to be tracked Additional characteristics
Selecting Databanks
For an Aspen Polymers simulation, you generally retrieve physical property data from the following databanks: Pure component databank (PURE12) Polymer databank (POLYMER) Polymer segment databank (SEGMENT) Initiator databank (INITIATOR)
You can also use other Aspen Plus databanks, user databanks, or in-house databanks. Appendix A provides descriptions of the polymer and segment databanks and the parameters they contain. If you selected a polymer template to start your simulation, the correct databanks are already specified. If you did not select a polymer template, or if you want to modify the databank selection: 1 2 3 From the Data Browser, click Components. From the Components folder, click Specifications. On the Selection sheet, click the Databanks tab to open the databank selection form.
Defining Component Names and Types

You must specify a: Name and a type for each component in the simulation Component name or identifier Databank name or formula that sets the pure component properties for the component Component type that sets the category to which the component belongs and determines the treatment of that component From the Data Browser, click Components. From the Components folder, click Specifications. On the Selection sheet, click the Databanks tab to set the databanks to be searched for pure component properties.
To access the components specifications input sheet: 1 2 3
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To define component names and types: 1 On the Selection sheet, in the Component ID field, specify an ID for each component. This ID is used to refer to the component in all subsequent input, and is also used to identify the component in the simulation report. 2 For polymers, oligomers, and segments, specify the component type in the Type field. By default, all components are assumed to be standard conventional components. For Aspen Polymers simulation you must correctly identify the component types:
Use Conventional Polymer Oligomer Segment For Standard conventional components Homo and copolymers Short chain polymer molecules Polymer or oligomer repeat units
If component property data is being retrieved from databanks, you must also supply either the databank component formula in the Formula field, or the databank name in the Component name field.
Specifying Segments
The Type of each polymer or oligomer segment must be specified on the Polymer Characterization Segments sheet. Segments can be repeat units, end groups or branch points attached to three or four branches. To access the segments definition input form: 1 2 3 From the Data Browser, click Components. From the Components folder, click Polymers. From the Polymers folder, click Characterization. On the Segments sheet, assign a type to the segments from the Type field.
To define segments:
Specifying Polymers
For each polymer you must define the component attributes to be tracked. All components specified Polymer in the Components Specifications folder require component attributes. To access the polymer input specifications: 1 2 3 4 From the Data Browser, click Components. From the Components folder, click Polymers. From the Polymers folder, click Characterization. From the Characterization form, click the Polymers tab.
To specify component attributes for the polymers in your simulation:
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1 2
In the Polymer ID field, select the polymer. If you want to retrieve a predefined set of component attributes, in Builtin attribute group select a grouping. The attribute summary table is filled in. For a complete discussion of Aspen Polymers component attributes, see Polymer Structural Properties on page 32. or If you do not want to use a predefined set of attributes, or if you want to change the attribute selection for a given group, click the attribute table or click Edit to open the attribute list.
Click specific attributes to add or remove them from the list.
Repeat these steps for each polymer.
Specifying Oligomers
For each oligomer you must specify an ID and a structure in terms of number and name of contained segments. To access the oligomers definition input form: 1 2 3 4 1 2 3 From the Data Browser, click Components. From the Components folder, click Polymers. From the Polymers folder, click Characterization. From the Characterization form, click the Oligomers tab. In the Oligomer field, select the oligomer. In the Segment field, enter the name of a segment contained in the oligomer. Repeat these steps for each oligomer.
To define oligomers:
You can define as many segments as needed for an oligomer.
Specifying Site-Based Components

Specify the structure and activity of site-based catalytic species such as Ziegler-Natta catalysts and ionic initiators. To access the site-based species definition form: 1 2 3 4 1 2 3 From the Data Browser, click Components. From the Components folder, click Polymers. From the Polymers folder, click Characterization. From the Characterization form, click the Site-Based Species tab. Select the component type: Ziegler-Natta catalyst, ionic initiator, etc. In the Comp ID field, specify the component name. Specify the number of site types in Number of sites for the component. For Ziegler-Natta catalysts, you must also specify the moles of sites per gram of catalyst.
To specify site-based species characteristics:
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4 5
Select the list of properties or component attributes to be tracked for that component. Click the attribute list table or Edit to open the attribute list. Click specific attributes to add or remove them from the list for the component.
References
Bailey, J., & Ollis, D. F. (1986) Biochemical Engineering Fundamentals (2nd Ed.). New York: McGraw-Hill. Brandrup, J., & Immergut, E. H. (Eds.). (1989). Polymer Handbook (3rd Ed.). New York: John Wiley & Sons. Danner R. P., & High, M. S. (1992). Handbook of Polymer Solution Thermodynamics. New York: American Institute of Chemical Engineers. Kroschwitz, J. (Ed.). (1990). Concise Encyclopedia of Polymer Science and Engineering. New York: John Wiley and Sons.
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4 Polymer Structural Properties
This section discusses the use of component attributes for tracking polymer structural properties in a simulation model. Topics covered include: Structural Properties as Component Attributes, 32 Component Attribute Classes, 33 Component Attribute Categories, 34 Component Attribute Initialization, 46 Component Attribute Scale Factors, 50 Specifying Component Attributes, 51
Structural Properties as Component Attributes

Component attributes provide a convenient framework to associate structural characterization data to components in a flow stream. They are carried throughout the flowsheet along with state and composition information, and effectively extend the stream structure. Aspen Polymers (formerly known as Aspen Polymers Plus) uses component attributes as a vehicle for tracking important modeling information for polymers, ionic initiators and Ziegler-Natta catalysts (U.S. Patent No. 5,687,090). For example, there are component attributes to store: Segment composition (segment fraction or segment flow) Copolymer composition and average sequence length Degree of polymerization (number, weight, and z-average) Molecular weight (number, weight, and z-average) Degree of branching (long and short) Degree of cross-linking (cross-link density) Molecular architecture (physical arrangement of segments within the polymer molecule)
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Live polymer properties Aggregate polymer properties
In the case of multi-site-type Ziegler-Natta catalyst polymerization, the attributes provide the structure to store the properties by site. Examples of catalyst attributes include the fraction of dead and potential sites. The catalyst attributes are used to track catalyst activity. There are also component attributes available to track user defined data. The complete list of available attributes is given in the Polymer Component Attributes, Site-Based Species Attributes, and User Attributes sections of this chapter (pages 34 through 45).
Component Attribute Classes

Component attributes are divided into classes to reflect the nature of various structural properties carried in process streams: Class 0 component attributes are derived quantities from other attributes. They are therefore recalculated from these attributes after they are updated. For example, number average degree of polymerization is a Class 0 component attribute. It is computed from the zeroth and the first moments of chain length distribution. Class 1 component attributes are structural properties per unit mass. They are not used for polymers. Class 2 component attributes are structural properties per unit time. Examples are zeroth and first moments of chain length distribution
The following table lists the differences between the Aspen Polymers component attribute classes:
Class 0 1 2 Conserved Quantity N/A Attribute component mass Attribute Convergence Treatment Recalculated Direct substitution Accelerated convergence Unit of Measurement Varies Attribute / component mass Attribute / time Examples Degree of polymerization None for polymers Segment flows, moments of chain length distribution
For a typical polymer process simulation, Class 0 and Class 2 component attributes are used. Since Class 0 component attributes are calculated from Class 2 attributes, users have the option of entering either of the two types for simulation models where polymer is present in the process feed streams. For this reason, an attribute initialization scheme has been designed. For more information, see Component Attribute Initialization on page 46.
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Component Attribute Categories

The main categories of component attributes available are: Polymer attributes Ziegler-Natta catalyst attributes Ionic initiator attributes User attributes
Polymer Component Attributes

The polymer properties tracked as component attributes include: Segment fraction Segment flow Flow and fraction of segment dyads (pairs) Number-average degree of polymerization and molecular weight Weight-average degree of polymerization and molecular weight Z-average degree of polymerization and molecular weight Zeroth through third moment of chain length distribution Number of long and short chain branches Long and short chain branching frequency Number and frequency of cross-links Number-average block length (sequence length) Several aspects of molecular architecture, including tacticity, head-tohead insertions (orienticity) Flow and fraction of terminal double bonds Flow and fraction of cis-, trans-, and vinyl- isomers associated with diene segments (internal and pendent double bonds)
There are component attributes available to track most of these properties for dead polymer, live polymer, and aggregate polymer. You may want to track information for live polymers for cases of free-radical polymerization where the quasi-steady-state approximation (QSSA) is not used. Site based component attributes are also available to accommodate multi-site type Ziegler-Natta catalyst polymerization. Composite attributes are summed over all site types. They represent the average properties of the polymer.
Polymer Attribute Sets

In summary, there are six sets of polymer component attributes. Composite Polymer Set contains the basic attributes that may be used for any type of polymerization, including the minimum required set for all simulation models. Composite Live Polymer Set contains the attributes required to track the characteristics of live polymer chains in chain growth polymerization.
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Composite Aggregate Polymer Set contains the attributes required to track the characteristics of aggregate polymer chain in ionic polymerization. Site-Based Polymer Set contains attributes corresponding to the composite set, but structured to track information for each catalyst site type. Site-Based Live Polymer Set contains attributes corresponding to the composite live polymer set, structured to track information by catalyst site type. Site-Based Aggregate Polymer Set contains attributes corresponding to the composite aggregate polymer set, structured to track information by ionic site type.
The tables that follow list the component attributes available in each set. Attributes must be associated from these sets to each of your polymer components when building a simulation model. To simplify this, the attributes in the tables were grouped by model usage, or polymerization reaction type (for example, physical property simulation model, free-radical polymerization model). Select a grouping and all the attributes needed are retrieved automatically. A table of the minimum required attributes by model usage is also provided.
Attribute Definitions Composite Polymer Attribute Set Name DPN Symbol Description Equation Class 0 Dimension Units 1 Unitless
D Pn
Number-average degree of polymerization Weight-average degree of polymerization Z-average degree of polymerization Polydispersity index Number-average molecular weight Weight-average molecular weight Z-average molecular weight Average segment molecular weight Zeroth moment of chain length distribution First moment of chain length distribution Second moment of chain length distribution
DPn = 1 / 0 DPw = 2 / 1 DPz = 3 / 2

PDI = DPw /D Pn
DPW
DPw DPz
PDI
Mn
Unitless
DPZ PDI MWN MWW MWZ MWSEG ZMOM
0 0 0 0 0 0 2
1 1 1 1 1 1 1
Unitless Unitless Unitless Unitless Unitless Unitless Mole flow Mole flow Mole flow Mole flow
M n = DPn M seg
Mw
Mz
M w = DPw M seg M z = DPz M seg

M seg =
----
M seg
F (i )M
p
0 1 2 3
FMOM SMOM
1 = 1 ( i )
----
0 2
1 1
TMOM
Third moment of chain ---length distribution
35
Name SFLOW
Symbol Description
Equation
Class
Dimension Units Mole flow
1 ( i )
Mole flow of segments ---2 NSEG of type i Attribute Definitions - Composite Polymer Attribute Set (continued) Equation Class 0 0 2
Name SFRAC EFRAC DYADFLOW
Symbol Description
Dimension Units NSEG NEND Unitless Unitless
Fp ( i ) Fe ( i )
Mole fraction of segments of type i Fraction of chain end segments of type i
Fp ( i ) = 1 ( i ) / 1 Fe ( i ) = 1 ( i ) / 1 ( i )
ends
i , j
Molar flow rate of ---dyads composed of type I and j segments Fraction of dyads composed of type I and j segments
(N (N
2 seg
+ N seg 2
) )
Mole flow Unitless
DYADFRAC
i, j
Bni
i , j = i , j / 1
i 1 i ii 1
2 seg
+ N seg 2
BLOCKN
Number-average block Bni = length for segment i
NSEG
Unitless
Attributes Related to Branching and Terminal Double Bonds LCB SCB FLCB
LCB SCB FLCB FSCB
Number of long chain branches
----
2 2
1 1 1
Mole flow Mole flow Unitless
Number of short chain ---branches Long chain branching frequency Short chain branching frequency
FLCB = FSLB =
103 LCB 1 103 SCB 1
FSCB
Unitless
TBDFLOW
= 0 (i )
Fp= (i )
Mole flow of terminal ---double bond segments of type i Mole fraction of terminal double bond segments of type i
NSEG
Mole flow Unitless
TBDFRAC
Fp= (i ) = = 0 (i ) / 1
NSEG
Attributes Related to Molecular Architecture (Tacticity and Orienticity) ATACFLOW ATACFRAC HTHFLOW
atactic 1
Apparent mole flow of ---atactic polymer Mass fraction of atactic polymer Mole flow rate of i-I dyads with head-tohead orientation
atactic F atactic = 1 / 1
2 0 2
1 1 NSEG
Mole flow Unitless Mole flow Unitless
F atactic
HTH ii
----
HTHFRAC
iiHTH
HTH Fraction of i-I dyads 0 NSEG iiHTH = ii / ii with head-to-head orientation Attribute Definitions - Composite Polymer Attribute Set (continued)
36
Name
Symbol Description
Equation
Class
Dimension Units
Attributes Related to Reactions with Diene Monomers XFLOW XDENSITY XFLOW Number of cross links Cross-linking density ---2 NSEG* NSEG* Mole flow Kmol/kg
XL
i , cis 1
XL =
----
XLFLOW M n 0
CIS-FLOW
Flow rate of diene segment i in cis configuration Flow rate of diene segment i in trans configuration Flow rate of diene segment i in vinyl configuration Fraction of diene segment i in cis configuration Fraction of diene segment i in trans configuration Fraction of diene segment i in vinyl configuration
NSEG*
Mole flow Mole flow Mole flow Unitless
TRANSFLO
i ,trans 1
----
NSEG*
VINYLFLO
i ,vinyl 1
----
NSEG*
CIS-FRAC
f i cis f i trans f i vinyl
i , cis i f i cis = 1 / 1
NSEG*
TRANSFRA
i ,trans i f i trans = 1 / 1
NSEG*
Unitless
VINYLFRA
i , vinyl i f i vinyl = 1 / 1
NSEG*
Unitless
Attributes Related to Particle Size (Emulsion Polymerization) PDV
PDv
Polydispersity for PSD (volume)
PDv =
Vn Vv
Unitless
PSDZMOM
0
1
Zeroth moment of the ---particle size distribution (volume) First moment of the PSD (volume)
# /s
m3 /s m6 /s m9 /s m3 m3 m3 m
PSDFMOM PSDSMOM PSDTMOM VOLN
1 = Mass /
0 2 2
1 1 1 1
2
3
Second moment of the ---PSD (volume) Third moment of the PSD (volume) Number average volume of the particles Volume average volume of the particles Z-average volume of the particles Volume average diameter ----
Vn Vv Vz
Dv
Vn = Vv = Vz =
1 0 2 1 3 2
6 1 0
VOLV
VOLZ
DIAV
Dv = 3
37
Segment index
Moments of the chain length distribution are defined as m Where:
= n mQn
m n Qn
*
= = =
0-3 Chain length Number of moles of polymer of length n.
Equation for recalculating class 0 attributes only. Class 2 attributes are integrated. Although the dimension is NSEG, these attributes only apply to diene segments, other elements will be set to zero. Attribute Definitions Composite Live Polymer Attribute Set
Name LDPN LDPW LPDI LMWN LMWW LMWSEG
Symbol Description
Equation
Class 0 0 0 0 0 0
Dimension 1 1 1 1 1 1
Units Unitless Unitless Unitless Unitless Unitless Unitless
DPnL DPwL PDI L M nL

L Mw L M seg
Number average DP of live polymer Weight average DP of live polymer Polydispersity index of live polymer Number average MW of live polymer Weight average MW of live polymer Average segment molecular weight of live polymer Zeroth moment of live polymer First moment of live polymer Second moment of live polymer
DPnL = 1 / 0 DPwL = 2 / 1 PDI L = DPwL / DPnL

L M nL = DPnL M seg L L Mw = DPwL M seg L M seg = LFp ( i ) M i
LZMOM LFMOM LSMOM LSFLOW LSFRAC
0 = 1
1
2 1 ( i )
LFp ( i )
(i) = (i)
0 1
0 0 2 2 0
1 1 1 NSEG NSEG
Mole flow Mole flow Mole flow Mole flow Unitless
----
Segment flow rates in ---live polymer Segment mole fraction in live polymer End segment flow rates in live polymer End segment mole fractions in live polymer Fraction of polymer that is live
LFp ( i ) = 1 ( i ) / 1
----
LEFLOW LEFRAC
0 (i)
LFe ( i ) Flp
2 0
NSEG NSEG
Mole flow Unitless
LFe ( i ) = 0 ( i ) / 0
LPFRAC
Flp =
0 0
Mole fraction
i = Segment index
38
Equation for recalculating class 0 attributes only. Class 2 attributes are integrated. Attribute Definitions Composite Aggregate Polymer Attribute Set
Name ADPN ADPW APDI AMWN AMWW AMWSEG
Symbol Description
Equation
Class 0 0 0 0 0 0
Dimension Units 1 1 1 1 1 1 Unitless Unitless Unitless Unitless Unitless Unitless
DPnA DPwA PDI A M nA

A Mw A M seg
Number average DP of aggregate polymer Weight average DP of aggregate polymer Polydispersity index of aggregate polymer Number average MW of aggregate polymer Weight average MW of aggregate polymer Average segment molecular weight of aggregate polymer Zeroth moment of aggregate polymer First moment of aggregate polymer Second moment of aggregate polymer Segment flow rates in aggregate polymer Segment mole fraction in aggregate polymer End segment flow rates in aggregate polymer End segment mole fractions in aggregate polymer Fraction of polymer that is aggregate
DPnA = 1 / 0 DPwA = 2 / 1 PDI A = DPwA / DPnA

A M nA = DPnA M seg A A Mw = DPwA M seg A M seg = AFp ( i ) M i
AZMOM AFMOM ASMOM ASFLOW ASFRAC AEFLOW AEFRAC
0 = 0 (i )
0 0 0 0 0 0 0
1 1 1 NSEG NSEG NSEG NSEG
Mole flow Mole flow Mole flow Mole flow Unitless Mole flow Unitless
1 2 1 ( i )
1 = 1 ( i ) 2 = 2 (i ) 1 ( i ) = 1 ( i, j )
AFp ( i )
0 (i)
AFp ( i ) = 1 ( i ) / 1
0 ( i ) = 0 ( i, j ) AFe ( i ) = 0 ( i ) / 0
AFe ( i )
Fap
APFRAC
Fap =
0 0
Mole fraction
i = Segment index Equation for recalculating class 0 attributes only. Class 2 attributes are integrated. Attribute Definitions Site-Based Polymer Attribute Set
Name SDPN
Symbol Description
Equation
Class Dimension Units 0 NSITE Unitless
DPn ( j )
Number average degree of polymerization at site j Weight average degree of polymerization at
DPn ( j ) = 1( j ) / 0 ( j )
SDPW
DPw ( j )
DPw ( j ) = 2 ( j ) / 1 ( j )
NSITE
Unitless
39
Name SDPZ
Symbol Description site j
Equation
DPz ( j )
PDI ( j )
Mn ( j) Mw ( j) M z ( j)
Z-average degree of polymerization at site j Polydispersity index at site j Number-average molecular weight at site j Weight-average molecular weight at site j Z-average molecular weight at site j Average segment molecular weight at site j Zeroth moment of chain length distribution at site j First moment of chain length distribution at site j Second moment of chain length distribution at site j Third moment of chain length distribution at site j Mole flow of segments of type I at site j Mole fraction of segments of type I at site j Fraction of chain end segments of type i at site j Number of long chain branches at site j Number of short chain branches at site j branching frequency at site j
DPz ( j ) = 3 ( j ) / 2 ( j ) PDI ( j ) = DPw ( j ) / DPn ( j )

M n ( j ) = DPn ( j ) M seg ( j ) M w ( j ) = DPw ( j ) M seg ( j ) M z ( j ) = DPz ( j ) M seg ( j )
M seg ( j ) =
----
SPDI SMWN
0 0
NSITE NSITE
Unitless Unitless
SMWW
NSITE
Unitless
SMWZ SMWSEG
0 0
NSITE NSITE
Unitless Unitless
M seg ( j )
F ( i, j ) M
p
SZMOM
0( j) 1 ( j ) 2( j) 3( j ) 1 ( i , j )
Fp ( i, j ) Fe ( i, j ) LCB( j ) SCB( j )
NSITE
Mole flow Mole flow Mole flow Mole flow Mole flow Unitless
SFMOM
1 ( j ) =
----
( i, j )
1
NSITE
SSMOM
NSITE
STMOM
----
NSITE
SSFLOW
----
NSEG, NSITE NSEG; NSITE
SSFRAC
Fp ( i, j ) = 1 ( i, j ) / 1 ( j )
SEFRAC
Fe ( i, j ) = 1 ( i, j ) / 1( i, j )
ends
NEND, NSITE
Unitless
SLCB
----
NSITE
Mole flow Mole flow Unitless
SSCB
----
NSITE
SFLCB
FLCB( j ) Long chain
FLCB( j ) = FSLB( j ) =
103 LCB( j ) 1 ( j ) 103 SCB( j ) 1 ( j )
NSITE
SFSCB
FSCB( j ) Short chain
NSITE
Unitless
branching frequency at site j
40
Name SPFRAC
Symbol Description
Equation
FSP( j )
Mass fraction of composite polymers at that site
i = Segment index j = Site number Equation for recalculating class 0 attributes only. Class 2 attributes are integrated. Attribute Definitions Site-Based Live Polymer Attribute Set
Name LSDPN
Symbol
Description Number average DP of live polymer Weight average DP of live polymer Polydispersity index of live polymer Number average MW of live polymer Weight average MW of live polymer Average segment molecular weight of live polymer Zeroth moment of live polymer First moment of live polymer Second moment of live polymer Segment flow rates in live polymer Segment mole fraction in live polymer
Equation
DPnL ( j ) DPwL ( j ) PDI L ( j ) M nL ( j )

L Mw ( j)
DPnL ( j ) = 1 ( j ) / 0 ( j ) DPwL ( j ) = 2 ( j ) / 1 ( j )
PDI L ( j ) = DPwL ( j ) / DPnL ( j )
L M nL ( j ) = DPnL ( j ) M seg ( j)
LSDPW
NSITE
Unitless
LSPDI
NSITE
Unitless
LSMWN
NSITE
Unitless
LSMWW
L L Mw ( j ) = DPwL ( j ) M seg ( j) L M seg ( j ) = LFp ( i, j ) M i
NSITE
Unitless
LSMWSEG
L M seg ( j)
NSITE
Unitless
LSZMOM LSFMOM LSSMOM LSSFLOW
0 ( j )
1 ( j )
2 ( j )
( i, j ) ( j ) = ( i, j )
0 ( j ) =
1 0 1
0 0 2 2
NSITE NSITE NSITE NSEG, NSITE
-------
1 ( i, j )
LFp ( i )
LSSFRAC
LFp ( i, j ) = 1 ( i, j ) / 1 ( j )
NSEG, NSITE
LSEFLOW
0 ( i, j )
LFe ( i, j )
End segment flow ---rates in live polymer End segment mole fractions in live polymer
NSEG, NSITE
Mole flow Unitless
LSEFRAC
LFe ( i, j ) = 0 ( i, j ) / 0 ( j )
NSEG, NSITE
41
Name LSPFRAC
Symbol
Description Fraction of polymer that is live
Equation
Class Dimension Units 0 NSITE Mole fraction
Flp ( j )
Flp ( j ) =
0( j) 0( j)
i = Segment index j = Site number Equation for recalculating class 0 attributes only. Class 2 attributes are integrated. Attribute Definitions Site-Based Aggregate Polymer Attribute Set
Name ASDPN
Symbol
Description Number average DP of aggregate polymer Weight average DP of aggregate polymer Polydispersity index of aggregate polymer Number average MW of aggregate polymer Weight average MW of aggregate polymer Average segment molecular weight of aggregate polymer Zeroth moment of aggregate polymer First moment of aggregate polymer
Equation
Class 0
Dimension Units NSITE Unitless
DPnA ( j ) DPwA ( j ) PDI A ( j ) M nA ( j )

A Mw ( j)
DPnA ( j ) = 1 ( j ) / 0 ( j ) DPwA ( j ) = 2 ( j ) / 1 ( j )
PDI A ( j ) = DPwA ( j ) / DPnA ( j )
A M nA ( j ) = DPnA ( j ) M seg ( j)
ASDPW
NSITE
Unitless
ASPDI
NSITE
Unitless
ASMWN
NSITE
Unitless
ASMWW
A A Mw ( j ) = DPwA ( j ) M seg ( j) A M seg ( j ) = AFp ( i, j ) M i
NSITE
Unitless
ASMWSEG
A M seg ( j)
NSITE
Unitless
ASZMOM ASFMOM ASSMOM ASSFLOW
0 ( j ) 1 ( j ) 2 ( j ) 1 ( i, j )
0 ( j ) = 0 ( i, j ) 1 ( j ) = 1 ( i, j )
0 0 2 2
NSITE NSITE NSITE NSEG, NSITE
Second moment of ---aggregate polymer Segment flow rates ---in aggregate polymer Segment mole fraction in aggregate polymer End segment flow rates in aggregate polymer End segment mole fractions in aggregate polymer
ASSFRAC
AFp ( i )
0 ( i, j )
AFp ( i, j ) = 1 ( i, j ) / 1 ( j )
----
NSEG, NSITE
ASEFLOW
NSEG, NSITE
Mole flow Unitless
ASEFRAC
AFe ( i, j )
AFe ( i, j ) = 0 ( i, j ) / 0 ( j )
NSEG, NSITE
42
Name ASPFRAC
Symbol
Description Fraction of polymer that is aggregate
Equation
Class 0
Dimension Units NSITE Mole fraction ---
Fap ( j )
Fap ( j ) =
0 ( j ) 0( j)
DSEFLOW
0 ( i, j )
End segment flow ---rates in dissociated (from aggregate) polymer ---Segment polymer flow rates in dissociated (from aggregate) polymer Second moment of ---dissociated (from aggregate) polymer
NSEG, NSITE
DSSFLOW
1 ( i, j )
NSEG, NSITE
---
DSSMOM
2 ( j )
NSITE
---
i = Segment index j = Site number Equation for recalculating class 0 attributes only. Class 2 attributes are integrated.
The following table lists the minimum required component attributes by model:
Model Property Models Emulsion Attributes MWN, DPN or both ZMOM and FMOM SFRAC or SFLOW MWN, DPN or both ZMOM and FMOM SFRAC or SFLOW DIAV or both PSDZMOM and PSDFMOM Other polymer particle attributes (optional) Free-Radical MWN, DPN or both ZMOM and FMOM SFRAC or SFLOW Other composite attributes (optional) Composite live attributes (optional) Step-Growth Ziegler-Natta MWN, DPN or both ZMOM and FMOM SFRAC or SFLOW MWN, DPN or both ZMOM and FMOM SFRAC or SFLOW Other composite attributes (optional) Composite live attributes (optional) Site based component attributes (optional) Site based live component attributes (optional) Ionic SZMOM, LSEFLOW ASEFLOW, DSEFLOW (if association reaction present) LSSFLOW, SSFLOW ASSFLOW, DSSFLOW (if association reaction
43
present)
Site-Based Species Attributes

There are two types of site-based species attributes: Zielger-Natta catalyst attributes Ionic initiator attributes
Zielger-Natta Catalyst attributes

Component attributes are used to track multi-site Ziegler-Natta catalyst site activity, in terms of mole flow and fraction of potential, inhibited, vacant, and dead sites. The occupied sites are not tracked since that information may be obtained from the live polymer zeroth moment of chain length distribution. The site types are defined as follows: Potential Sites - these are sites not yet activated. Vacant Site - these are activated sites without a growing polymer attached. Inhibited Sites - these are activated sites temporarily in an inactive state. Dead Sites - these are sites having permanently lost their catalytic activity. Occupied Sites - these are activated sites with a growing polymer attached.
Description Mole flow of potential sites Mole fraction of potential sites Mole flow of vacant sites of type k Mole fraction of vacant sites of type k Mole flow of inhibited sites of type k Mole fraction of inhibited sites of type k Mole flow of dead sites Mole fraction of dead sites Mole flow of metal hydride Mole fraction of metal hydride Class 2 0 2 0 2 0 2 0 2 0 Dimension NSITE NSITE NSITE NSITE NSITE NSITE NSITE NSITE NSITE NSITE
The following table lists the catalyst component attributes:

Attribute CPSFLOW CPSFRAC CVSFLOW CVSFRAC CISFLOW CISFRAC CDSFLOW CDSFRAC CMSFLOW CMSFRAC
Ionic Initiator Attributes

The component attributes are used to track various states of ionic initiator (free ions, ion pairs, dormant esters) using a multi-site model. The following table lists the three ionic component attributes:
44
Attribute P0FLOW PT0FLOW CIONFLOW
Description Mole flow of Mole flow of
Class
Dimension NSITE NSITE NSITE
P0 P T0
2 2 2
Mole flow of counter-ion
CI
For more information on ionic attributes, see Ionic Polymerization Model in Chapter 3.
User Attributes
Generic component attributes are available for tracking user-specified data. These may be used to track additional properties not available through the pre-defined attributes. User component attributes are available as Class 0 through Class 2 attributes. You must supply a Fortran subroutine to return rates of change for Class 2 attributes and recalculate Class 0 attributes. This would typically be a user kinetic routine. User attributes DPSDN and DPSDW are designed to hold data related to particle size distributions of solid polymers or monomers. The number flow rates (DPSDN) have units of inverse time. Since particle flow rates are often very high the user may wish to apply appropriate scaling to define this attribute on a relative basis (for example use this attribute to track flow rates in trillions of particles/sec). The DPSDW attribute tracks the mass flow rate of each element of the distribution. User subroutines are required to use this advanced feature. The following table lists the available user component attributes:
Attribute CACLASS0 CAUSR15 CAUSRAE DPSDN Description Class 0 user attribute Class 1 user attributes Class 2 user attributes Discrete particle size distribution, particle number flow rates. Class 2. Discrete particle size distribution, particle mass flow rates. Class 2. Unit Type Unitless Unitless Mole flow Inverse time Dimension 10 10 10 50
DPSDW
Mass flow
50
45
Component Attribute Initialization

In cases where polymer is present in the process feed streams, values for the polymer component attributes must be specified. Enter this information while specifying the feed stream conditions. Within Aspen Polymers, material streams are made up of substreams that carry the flow of material of different types: Conventional vapor/liquid flow goes into the Mixed substream type Solid polymer and other solid components which do not participate in phase equilibrium go into the Cisolid substream type
Most simulations only make use of the Mixed substream. In this substream, you would enter the conditions, such as temperature and pressure, the number of phases (2 if both vapor and liquid are present), and the composition in terms of component flows or fractions (along with the total stream flow). If one of the components for which you enter composition data is a polymer or a catalyst, you must specify its component attributes. Because users are allowed to specify either Class 0 or Class 2 component attributes, an initialization mechanism had to be defined to calculate the corresponding Class 2. Remember that the Class 2 attributes are the ones which are converged upon during simulation.
Attribute Initialization Scheme

The attribute initialization scheme performs several important functions. In addition to calculating the needed Class 2 attributes, it automatically calculates an expanded component attribute set from the minimum required and specified by the user. The minimum required attributes are: Segment flow rates (SFLOW), or segment fractions (SFRAC) Number average degree of polymerization (DPN), or both Zeroth and first moment of chain length distribution (ZMOM and FMOM)
From this set, several other attributes can be calculated using the definitions given in the attribute definition tables provided earlier in this chapter. The scheme uses priority rules to decide how to calculate each attribute. The following table describes the calculation methods and order of priority. The initialization scheme is also used for recalculating Class 0 attributes during flowsheet convergence. Finally, it can be considered as a method of ensuring consistency between interrelated attributes. The Aspen Polymers component attribute initialization methodology is:
Attribute Calculated from Priority
Composite Bulk Polymer Attribute Set
46
Attribute SFRAC
Calculated from SFRAC SFLOW / SUM (SFLOW) 1 / NSEG
Priority 1 2 3 1 2 3 4 1 2 1 2 3 4 5 1 2 3 1 2 1 2 1 1 2 1 1 1 2 3 1 2 3 1 2 3 1 2 3 1 2 3
ZMOM
ZMOM FMOM / DPN FMOM*MWSEG / MWN PDI*FMOM*FMOM / SMOM
FMOM SMOM
SUM (SFLOW) PMASS / MWSEG SMOM FMOM*DPW FMOM*MWW / MWSEG FMOM*FMOM*PDI / ZMOM ZMOM
TMOM
TMOM SMOM*DPZ SMOM*MWZ / MWSEG
LCB SCB PSDZMOM PSDFMOM PSDSMOM PSDTMOM VOLN
LCB FMOM*FLCB / 1.E3 SCB FMOM*FSCB / 1.E3 PSDZMOM PSDFMOM PMASS / PDENS PSDSMOM PSDTMOM VOLN PSDFMOM / PSDZMOM 0.0
VOLV
VOLV PSDSMOM / PSDSMOM / PSDFMOM 0.0
VOLZ
VOLZ PSDTMOM / PSDSMOM 0.0
DIAV
DIAV (6.0*PSDFMOM / / PSDZMOM) 0.0
PDV
PDV (PSDZMOM*PSDSMOM) / (PSDFMOM) 0.0
Attribute
Calculated from
Priority
47
Composite Live Polymer Attribute Set LSFRAC LSFRAC LSFLOW / SUM (LSFLOW) 1 / NSEG LZMOM LZMOM LPFRA*ZMOM LFMOM / LDPN LFMOM*LMWSEG / LMWN LPDI*LFMOM*LFMOM / LSMOM LFMOM SUM (LSFLOW) LZMOM*LDPN LZMOM*LMWN / LMWSEG LZMOM*LSMOM / LPDI LSMOM LSMOM LFMOM*LDPW LFMOM*LMWW / LMWSEG LFMOM*LFMOM*LPDI / LZMOM Composite Aggregate Polymer Attribute Set ASFRAC ASFRAC ASFLOW / SUM (ASFLOW) 1 / NSEG AZMOM AZMOM APFRA*ZMOM AFMOM / ADPN AFMOM*AMWSEG / AMWN APDI*AFMOM*AFMOM / ASMOM AFMOM SUM (ASFLOW) AZMOM*ADPN AZMOM*AMWN / AMWSEG AZMOM*ASMOM / APDI ASMOM ASMOM AFMOM*ADPW AFMOM*AMWW / AMWSEG AFMOM*AFMOM*APDI / AZMOM 1 2 3 1 2 3 4 5 1 2 3 4 1 2 3 4 1 2 3 1 2 3 4 5 1 2 3 4 1 2 3 4
Attribute
Calculated from
Priority
Site Based Bulk Polymer Attribute Set SSFRAC SSFRAC SSFLOW / SUM (SSFLOW) 1 / NSEG 1 2 3
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Attribute SZMOM
Calculated from SZMOM SFMOM / SDPN SFMOM*SMWSEG / SMWN SPDI*SFMOM*SFMOM / SSMOM
Priority 1 2 3 4 1 2 1 2 3 4 5 1 2 3 1 2 1 2
SFMOM SSMOM
SUM(SSFLOW) SPFRAC*PMASS / SMWSEG SSMOM SFMOM*SDPW SFMOM*SMWW / SMWSEG SFMOM*SFMOM*SPDI / SZMOM SZMOM
STMOM
STMOM SSMOM*SDPZ SSMOM*SMWZ / SMWSEG
SLCB SSCB
SLCB SFMOM*SFLCB / 1.E3 SSCB SFMOM*SFLCB / 1.E3
Site Based Live Polymer Attribute Set LSSFRAC LSSFRAC LSSFLOW / SUM (LSSFLOW) 1 / NSEG LSZMOM LSZMOM LSPFRA*SZMOM LFSMOM / SLDPN LSFMOM*LSMWSEG / SLMWN LSPDI*LSFMOM*LSFMOM / LSSMOM LSFMOM SUM (LSSFLOW) LSZMOM*LSDPN LSZMOM*LSMWN / LSMWSEG DSQRT (LSZMOM*LSSMOM / LSPDI) LSSMOM LSSMOM LSFMOM*LSDPW LSFMOM*LSMWW / LSMWSEG LSFMOM*LSFMOM*LSPDI / LSZMOM Site Based Aggregate Polymer Attribute Set ASSFRAC ASSFRAC ASSFLOW / SUM (ASSFLOW) 1 / NSEG 1 2 3 1 2 3 1 2 3 4 5 1 2 3 4 1 2 3 4
49
Attribute ASZMOM
Calculated from ASZMOM ASPFRA*SZMOM AFSMOM / SADPN ASFMOM*ASMWSEG / SAMWN ASPDI*ASFMOM*ASFMOM / ASSMOM
Priority 1 2 3 4 5 1 2 3 4 1 2 3 4
ASFMOM
SUM (ASSFLOW) ASZMOM*ASDPN ASZMOM*ASMWN / ASMWSEG DSQRT (ASZMOM*ASSMOM / ASPDI)
ASSMOM
ASSMOM ASFMOM*ASDPW ASFMOM*ASMWW / ASMWSEG ASFMOM*ASFMOM*ASPDI / ASZMOM
PMASS is polymer mass, PDENS is polymer density
Component Attribute Scale Factors

Aspen Plus uses numerical solvers to resolve flowsheet recycle streams and to solve the conservation equations in each of the kinetic reactor models (RCSTR, RPLUG, and RBATCH). The solver algorithms use scaled variables. Typically, the ideal scale factors for each type of variable should be on the same order of magnitude as the variable itself. In other words, the solvers work best when the scaled variables are all close to unity. In Aspen Polymers, default scaling factors are defined for each type of component attribute variable. These defaults are designed to address a wide range of problems, however they may not be ideal for any particular problem. The Attr-Scaling form lets you view and change the default scaling factors for each type of component attribute. Under some circumstances, you may be able to improve the reactor and/or flowsheet recycle stream convergence by optimizing the attribute scaling factors. For example, in a Ziegler-Natta polymerization process the live end flow rate (LEFLOW) and the related attributes LZMOM and LSZMOM are sensitive to the catalyst activity. Highly active catalysts result in very low live end flow rates. Further, the number of vacant and potential sites (CVSFLOW and CPSFLOW) may be very low for the catalyst. The Attr-Scaling form can be used to specify more accurate scaling factors for the component attributes for polymers, catalysts, and other types of attributed components. Reducing the scaling factors on this form tightens the tolerance on the selected variables. If the scaling factors are set too low, the tolerance will be unreasonably tight, leading to convergence problems or excessive CPU time. If the scaling factors are set too high, the problem may be loosely converged and the simulation accuracy may suffer.
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The reactor models and flowsheet recycle convergence algorithms currently ignore the attribute upper bound limits that appear on this form.
Specifying Component Attributes

There are several categories of components for which you can specify component attributes: Polymers Site-based components Conventional components
Specifying Polymer Component Attributes

See Specifying Polymers on page 29.
Specifying Site-Based Component Attributes

See Specifying Site-Based Components on page 30.
Specifying Conventional Component Attributes

You can associate attributes to conventional components by selecting user attributes. Typically, you do this if you have a user subroutine to return values for these attributes. To access the user component attribute selection form: 1 2 1 2 3 From the Data Browser, click Components. From the Components folder, click Attr-Comps. On the Selection sheet, specify the component name in the Component field. In the Attribute field, specify the attribute name. Continue adding as many attributes as needed.
To associate user attributes to conventional components:
Initializing Component Attributes in Streams or Blocks

If you have an attributed component present in a feed stream, you must specify component attribute values for that component. To access the component attribute input form for a stream:
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1 2 3 4 5
From the Process Flowsheet window, use the right mouse button to click the feed stream. Click Input. From the stream input specifications sheet, click the Component Attr. tab. On the Component Attr. sheet, select the Component ID. For each attribute, select the Attribute ID and enter the values for the attributes.
If you have an attributed component produced within a reactor, you can specify attribute values (product values or product value estimates) for that component. This is not available for all reactors. For a description of the treatment of component attributes in reactors, see Steady-State Unit Operation Models in Chapter 4. To access the component attribute input form for a reactor: 1 2 3 4 5 From the Process Flowsheet window, use the right mouse button to click the reactor. Click Input. From the reactor input specifications sheet, click the Component Attr. tab. On the Component Attr. sheet, select the Component ID. For each attribute, select the Attribute ID and enter the values for the attributes.
Specifying Component Attribute Scaling Factors

You can override default component attribute convergence parameters for polymer or catalyst components. Adjusting the scaling factor helps you improve flowsheet convergence and internal convergence in reactor models. Typically, the scaling factor should be the same order as the expected value of the variable. To access the component attribute scaling form: 1 2 1 2 3 4 From the Data Browser, click Components. From the Components folder, click Attr-Scaling. On the Input tab, specify the component name in the Component ID field. In the Attribute field, specify the attribute name. Continue adding as many attributes as needed. Adjust the Scaling factor and/or Upper bound as needed.
To adjust the default scaling factor and upper bound of defined attributes:
References
Aspen Plus User Guide. Cambridge, MA: Aspen Technology, Inc.
52 4 Polymer Structural Properties
5 Structural Property Distributions
This section discusses the mechanism available in Aspen Polymers (formerly known as Aspen Polymers Plus) for tracking structural property distributions, in particular chain size distribution, for chain-growth polymerization processes (U.S. Patent No. 6,093,211). Topics covered include: Property Distribution Types, 53 Distribution Functions, 54 Distributions in Process Models, 56 Mechanism for Tracking Distributions, 62 Requesting Distribution Calculations, 66
Property Distribution Types

The common polymer structural properties for which distributions are typically considered include: Chain size - molecular weight or chain length Copolymer composition Degree of branching Polymer particle size
In order to accurately characterize a polymer component, and maintain control of polymer product properties, engineers must concern themselves with these distributions. From a modeling standpoint, many theoretical and empirical functions have been developed to represent distributions. These functions tend to fall into categories derived from their formulation, or from their graphical representation. For example, distributions that consider two dependent parameters simultaneously (for example, chain size and copolymer composition) are termed bivariate distributions.
53
Distributions that mimic the normal bell-shaped graphical representation are called unimodal distributions. This is in contrast with distributions that reveal several peaks and are called bimodal or multimodal distributions. The following figure shows examples of unimodal and bimodal distributions:
Distribution Functions
In the majority of cases, the distribution functions proposed in the literature are based on a statistical approach and use one of three types of mathematical functions: binomial, Poisson or Gaussian. The parameters in these distribution functions can easily be calculated from the polymer average properties (degree of polymerization, polydispersity index, etc.). The following are the common distribution functions that have been applied to the calculation of polymer property distributions: Schulz-Flory Most Probable (Flory, 1936, 1953; Schulz, 1935, 1939) Schulz (Schulz, 1935, 1939) Weibull-Tung Generalized Exponential (Tung, 1956; Weibull, 1951) Normal (Biesenberger & Sebastian, 1983) Wesslau Logarithmic Normal (Wesslau, 1956) Lansing Logarithmic Normal (Lansing, 1935) Poisson (Biesenberger & Sebastian, 1983) Zimm (Zimm, 1948) Stockmayer Bivariate (Stockmayer, 1945)
In addition to these distribution functions, a method using the moments of distributions is also available (Tompa, 1976). Of these functions, two have greater importance for Aspen Polymers.
Schulz-Flory Most Probable Distribution

Schulz and Flory developed a one-parameter equation to represent the distribution of polymers falling into one of the following categories:
54
Addition polymers - formed by a constant rate of initiation, with invariant monomer concentration, with termination by disproportionation only, and with no chain transfer to monomer Linear condensation polymers - obeying the assumption of equal reactivities of chain ends or linear condensation polymers formed by random interchange of units Low molecular weight polymer - formed from a high molecular weight polymer by random scission
The Schulz-Flory distribution is also known as the Most-Probable distribution since it is dictated by the probability of random events, such as the location of a scission reaction on a long-chain molecule. The number or mole-fraction distribution and the weight fraction distribution are given by:
Mole-Fraction Distribution
F ( r ) = p r 1 (1 p )
(number distribution)
Weight-Fraction Distribution
W ( r ) = rp r 1 (1 p )2
Where: p r
(weight distribution)
= Extent of reaction = Size of the molecule or number of segments
For addition polymerizations p is the probability that a growing live polymer molecule will propagate. For step-growth reactions, p is the fractional conversion of monomer end groups. From these distributions, the number, weight, and z-average degree of polymerization are:
DPn =
DPw =
1 (1 p )
(1 + p ) (1 p )
F ( r ) = p r 1 (1 p ) PDI = 1 + p
To generate the distribution, p can be calculated from degree of polymerization as:
p = 1
1 DPn
Note that the polydispersity approaches two as p unity.
55
Stockmayer Bivariate Distribution

There are cases where two polymer property distributions must be considered simultaneously, which are called bivariate. Stockmayer developed a distribution function to consider both chain size and composition distribution for example (Stockmayer, 1945). This model may be extended to other combinations of polymer properties such as chain size and long chain branching distribution for the case of copolymers.
Distributions in Process Models

There is a great demand to know the full molecular weight distribution, particularly for complex distributions that may have a shoulder, or are even bimodal. This information is needed for optimization of rheological and mechanical properties of the final polymer product. Within Aspen Polymers a dual approach for determining polymer properties is used: Method of moments continues to be the preferred approach for calculating average properties. Method of instantaneous properties is used to calculate distributions. This method addresses the issue of data storage and computational complexity in tracking distributions.
Under special circumstances, the most general form of the instantaneous distribution function reduces to Florys most probable distribution. The instantaneous distribution functions are unimodal. However, the distribution functions for polymer accumulated in a multi-reactor system may be multimodal.
Average Properties and Moments

It is convenient to examine polymer molecular properties in terms of averages instead of considering the complete distribution. Average properties must be determined from the actual distributions either through distribution moments or through instantaneous properties. The average properties tracked for polymers were described in the Polymer Component Attributes section on page 34. These properties are calculated using the method of moments within kinetic models. For a given property s, the property distribution may be described by a frequency function f s when the property is a discrete variable, and by a density function f ( s) when the property s is continuous. Therefore, f s and f ( s) represent the portion (for example, number, weight, volume, fraction) of the population whose property is exactly s (discrete) or whose property lies between s and s + ds. The frequency and density distribution functions are respectively:
56
Frequency Function
FS = f s
s0
and
Density Function
F ( S ) = f ( s) ds
s0
Where:
s0
S
= =
Initial value of s Arbitrary higher value (Biesenberger & Sebastian, 1983)
Distribution moments may be defined from the origin of the average property, i.e. property is equal to 0, or from the mean value of that property. The moments employed in Aspen Polymers use the first approach. In this case, the generalized form of the relationship between distribution moment and distribution function is shown below:
s k f s all s k k s f ( s) ds all s
Where: k s = Moment
for the frequency function for the density function
= Moment order (e.g. 0-3 for zeroth through third moment) = Property value (e.g. chain length, molecular weight, particle size, etc.) = Frequency function
fs
f ( s) = Density function
Average Properties
The average properties can be calculated as ratios of the moments. Number average is the ratio of first to zeroth moment, 1 / 0 . Weight or Volume average is the ratio of second to first moment, of third to second moment, 3 / 2 .
2 / 1 . Z-average is the ratio
For the case of chain length distribution the moment frequency distribution is given by:
m = n mQn
5 Structural Property Distributions 57
Where: m n = Moment = Moment order = Chain length or degree of polymerization = Number of moles of polymer of length n
Qn
The average chain length properties are then:
DPn = 1 / 0
DPw = 2 / 1
DPz = 3 / 2 PDI = 2 0 / 2 1
A similar definition of moments for the frequency distribution can be applied to molecular weight. Typically, in Aspen Polymers it is applied to chain length. Then the average molecular weight values are determined using the average degree of polymerization and average segment molecular weight.
Method of Instantaneous Properties

Applying the method of moments for the calculation of property distributions has several drawbacks. In addition to CPU requirements and computational complexity, a larger number of moments than currently calculated would be required. Knowledge of leading moments of a distribution does not permit one to unambiguously construct a complex distribution. One must therefore look beyond the method of moments for a more powerful method to predict these complex distributions. A better approach for generating molecular weight distributions consists of storing reaction rate data throughout the kinetic calculations, and later using them to construct the full distribution of polymer accumulated in the reactor system. Such an approach was developed by Hamielec (Hamielec, 1992). In the simplest case, linear polymerization in a single CSTR reactor, the ratios of termination and chain transfer reaction rates to propagation reaction rates are stored. The instantaneous chain length distribution is expressed as a function of these ratios and chain length. For the case of two CSTRs in series, at steady-state, the outlet polymer distribution function is the weighted average of the distribution function in each CSTR taken separately. The case of a plug flow reactor can be approximated using multiple CSTRs, and similarly for a batch reactor. By looking at the treatment of such reactor configurations, it can be deduced that the final polymer distribution is a result of the entire system of reactors. For this reason, the MWD implementation in Aspen Polymers needs to consider the proper data structure to track distribution parameters at every point in the flowsheet. Users should be able to request MWD from any point in the flowsheet, and from this point the Aspen Plus flowsheet connectivity information can be used to track polymerization history.
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The calculation of chain length distribution for a batch reactor from reaction rate parameters for linear addition polymerization was described by Hamielec (Hamielec, 1992). Consider the equations for the generation and consumption of free radicals. A similar approach may be used for other active centers (Ziegler-Natta, metallocene, etc.):
Radical Generation and Consumption Rates
[R ] = K [M ] + K
o l p o r p
RI + K fm [ M ][ R o ] + K fT [T ][ R o ]
fm
[ M ] + K fT [T ] + (K tc + K td )[ R o ] [ M ] + K fT [T ] + (K tc + K td )[ R o ] K p [ M ][ R o r 1 ]
[R ] = K [M ] + K
Where:
fm
[ R ] = 2K
I
f [ I ] = Initiation rate
Instantaneous Distribution Parameters

Introducing two dimensionless parameters and .
Rtd + R f Rp
K td [ Ro ] + K fm [ M ] + K fT [T ] K p[ M ]
Rtc K tc [ Ro ] = Rp K p [ M ]
Where:
Rp = K p [ Ro ][ M ] = Propagation rate
Rtd = K td [ Ro ]2 Rtc = K tc [ Ro ]2
= Rate of termination by disproportionation = Rate of termination by combination reactions
R f = K fm [ Ro ][ M ] + K fT [ Ro ][T ] = Total rate of all chain transfer

If we assume that the stationary-state hypothesis holds, then the initiation rate is equal to the sum of the termination rates, RI = Rtd + Rtc . The equations for the rate of generation and consumption of radicals can be written as follows:
+ [R ] = 1+ [R ] +
o l o
[R ] = 1+ + [R ]
o r o r 1
59
Therefore:
[ R ] = [ R ]( + )
o r o
Where:
1 1+ +
The rate of production of polymer molecules of chain length r , RFp ( r ) is given by:
r 1 1 d V [ Pr ] 1 = K fm[ M ] + K fT [T ] + K td [ Ro ] [ R o r ] + K tc [ Ro s ][ Ro r s ] V dt 2 s =1
RFP ( r ) =
Substituting [ R o f ] gives:
RFP ( r ) = K p [ Ro ][ M ]( + ) + ( + )( r 1) r 2
Instantaneous Weight Chain Length Distribution
Therefore, the instantaneous weight chain length distribution can be calculated from production rate of polymer molecules as follows:
W (r ) =
rR
r =1
rRFP ( r )
FP
(r)
( + ) + ( + )( r 1) r 2 1+ +
= ( + ) + ( + )( r 1) r r +1 2
In other words, W(r) is the weight chain length distribution of dead polymer chains produced in a small time interval t to t+dt, in a batch reactor. W(r) is also the weight chain length distribution of dead polymer chains produced in a CSTR operating at steady-state. If << , which is the case when the polymer chains are formed by chain transfer or by termination by disproportionation, this equation reduces to:
W ( r ) = r
2
r +1
1 = r 1+
r 1
1+
Where:
1 / (1 + )
/ 1+
= =
Probability of growth for a polymer radical Probability that a polymer radical stops growing
Chain Length distribution equation

Since r is usually large, W(r) in the original equation on page 60 can be approximated as a continuous function with small error:
60
W ( r ) ( + ) + ( + )( r 1) r.exp ( + )r 2
{
(
For most free-radical polymerizations + << 1 and is of the order
10 10 .
The weight-average chain length for polymer produced instantaneously is given by:
Pw = rW ( r ) =
r =1
(2 + + ) + (3 + + )
( + )
( + )
2 + 3
2
The instantaneous number-average chain length distribution is given by:
Pn =
1 W (r ) r r 1
(1 + + )
+ 2
1 + 2
The polydispersity index for polymer produced instantaneously is given by:
Pw (2 + 3) + 2 PDI = Pn ( + )2
Copolymerization
The chain length distribution equation on page 61 applies to both homo- and co-polymerization with two or more monomer types. When chain growth polymerizations are done with active center types other than radicals (Ziegler-Natta, metallocene, etc.) = 0 in the equation, and the instantaneous chain length distribution becomes a single parameter distribution, which is Florys most probable distribution with a polydispersity index of 2.0. This equation is the main expression used in Aspen Polymers to generate chain length distribution. Within the context of a polymerization reactor, this expression is valid for the case of linear chains of a homopolymer produced in a single CSTR at steady-state.
CSTR in Series
For the case of two CSTRs in series, the end product polymer distribution is a composite that is a weighted average of the distributions of polymer produced in the first and the second reactor:
Wout ( r ) =
Where:
m1 m * W1 ( r ) + 2 * W2 ( r ) m m
m = m1 + m2 = Total mass of polymer produced in the first and second reactor

per unit time
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The distribution function in each reactor is given by the chain length distribution equation on page 61 with the and , varying from reactor 1 to reactor 2, and independent of time under steady-state operation.
Plug Flow & Batch Reactors

A plug flow reactor can be divided into several volume elements and treated as a series of CSTRs. The , , and polymer mass values are stored for each volume element and later used for the calculation of the composite chain length distribution function. A batch reactor is handled using a similar approach. In this case, the , , and polymer mass values are stored for each time element. For linear chains of a copolymer, the difference from the homopolymer case can be factored into the calculation of the reaction rates for propagation, termination, and transfer reactions, Rp , Rtc , Rtd , and R fm .
Mechanism for Tracking Distributions

The method of instantaneous properties is used to generate chain length distributions in Aspen Polymers. This method is applied at two levels: Reactor level for determining the distribution of polymer newly produced within the vessel (local distribution), and Flowstream level for determining the distribution of polymer produced up to that point in the flowsheet (cumulative distribution)
Distributions in Kinetic Reactors

Within kinetic reactors, the method of instantaneous properties is used to determine the distribution of newly produced polymer. The reaction models calculate the instantaneous properties and using the respective equations on page 59. In addition, the polymer mass corresponding to these values is saved.
Calculating Distribution Increments

The distribution increments are spaced in logarithmic steps between unity and the specified upper limit (Upper) using the following formula:
i log10 (upper ) ri = max i, alog N point

Where i varies between one and the specified number of points Npoint, and upper is the user-specified upper bound of the distribution. This spacing provides good resolution over the entire spectrum of molecular weights, with emphasis on the low molecular weight species that are more likely to be lost in fractionation steps. To ensure accuracy, the upper bound should be set at
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least five times higher than the observed weight-average degree of polymerization.
Calculating Local Distributions

For CSTR reactors, the values of and are stored during simulation. For multi-site kinetics (such as Ziegler-Natta kinetics), values of and and polymer mass generation are stored for each site j. These parameters are used to calculate the local distribution for the CSTR reactor. For single-site kinetics (free radical and emulsion):
Wrlocal = r ( + ) + ( + )(r 1) exp[ r ( + )] 2

For multi-site kinetics (Ziegler-Natta):
j ( j + j )(r 1) Wrlocal = r ( j + j ) j + exp r ( j + j ) ,j 2
local r
m j Wrlocal ,j
mj
For plug-flow reactors, the values of and are calculated at each axial step during the numerical integration. The local distribution for the reactor is calculated by summing the instantaneous distributions (from either equations given previously) at each step over all the steps from the reactor for Wr inlet (z = 0) to the reactor outlet (z = L). For single-site kinetics:
local
Wr , z = r ( z + z ) z + z ( z + z )(r 1) exp[ r ( z + z )] 2
local r
m
z =0 L
Wr , z
z
m
z =0
For multi-site kinetics:
j,z ( j , z + j , z )(r 1) Wr , j , z = r ( j , z + j , z ) j , z + exp r ( j , z + j , z ) 2
local r, j
m
z =0
j,z
Wr , j , z
j,z
m
z =0
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The local composite distribution is calculated using the equation given previously for Wr
local
for multi-site kinetics.
The local site-based and composite distributions are stored in the reactor results form and can be viewed from the Reactor folder Results subfolder, Distributions sheet and plotted using the Aspen Plot Wizard.
Calculating Cumulative Distributions

For a reactor with multiple feeds, the feed distribution is calculated as shown below:
N feeds
Wr
feed
k k =1 N feeds k =1
Wr ,k
k
The cumulative composite distribution is calculated by adding the feed distribution to the local composite distribution:
composite r
m feed Wr feed + m local Wrlocal m feed + m local
The composite cumulative distribution is stored in the outlet stream of the reactor and can be viewed through the stream results form.
GPC Distributions
If the user selects the GPC Distribution format, the distribution is calculated as rWr .
Distributions in Process Streams

The polymer distribution calculated within kinetic reactors is transferred into the outlet stream. This allows flowsheeting of the cumulative distribution data, i.e. the data follows the polymer component throughout the flowsheet. The cumulative distribution is stored within the stream. Aspen Plus provides several different vehicles for associating data with process streams. These include: Basic stream vector, which contains composition and state information Component attributes, which are a fundamental tool in Aspen Polymers Prop-Sets, which allow users to request additional properties for streams Other non-accessible storage space
The first two categories are processed during convergence calculations while the last two are not. The information used for calculating the distributions is derived from converged quantities. There is no need for applying convergence calculations
64
to the distribution data itself. Therefore, the polymer distribution data is carried in non-accessible storage space. The following figure illustrates the procedure followed to generate the distribution:
Verifying the Accuracy of Distribution Calculations

The molecular weight distributions calculations involve round-off error associated with the discretization into a finite number of elements and truncation error due to the upper bound imposed on the distribution. The following expressions can be used to verify the accuracy of the distribution. These expressions calculate the area under the distribution curve and the number- and weight-average molecular weight of the polymer in the distribution. For non-GPC curves:
W + Wi wi = (ri +1 ri ) i +1 2
For GPC curves (distribution stores rWi ):
wi =
(ri +1 ri ) W W i +1 + i
2 r i +1 ri
Where:
Wi = Y-axis value of distribution element i ri

= X-axis value of distribution element i
wi = Mass-fraction of polymer in the size range between ri and ri +1
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The total mass fraction of all elements in the distribution should sum to unity:
N points i =1
1.0
If the calculated area is below unity, the specified upper bound of the distribution may be too low. If the calculated area is greater than one, the number of points in the distribution may need to be increased to improve the accuracy of the distribution calculations. For chain-length distributions, the value r refers to the molecular size. The number average and weight average degree of polymerization can be calculated as:
N points Pn = i =1
wi 1 2 (ri +1 + ri )
Pw =
N points 1 2 i =1
w (r
i
i +1
+ ri )
For molecular-weight distributions, the term r refers to the molecular weight of each increment. The number and weight average molecular weights of the distributions are calculated as:
N points Mn = i =1
wi 1 ( ) r r + i 2 i +1
Mw =
N points 1 2 i =1
w (r
i
i +1
+ ri )
The area under the distribution curve and the number- and weight-average properties of the distribution can be generated by the plot wizard and displayed on the distribution plots. For unit operation blocks, the number- and weight-average properties of the distribution may be verified against the local polymer results, displayed on the Polymer Results sheet for each reactor. For streams, the number- and weight-average properties of the distribution may be verified against the polymer component attributes shown in the stream table.
Requesting Distribution Calculations

In order to track distributions in your simulation, you must select the distribution characteristics. After the simulation is complete you must retrieve the distribution data for plotting. You can display and plot the distribution data for the polymerization reactor, or you can display a distribution table for a stream or for the entire flowsheet.
Selecting Distribution Characteristics

To access the polymer distribution specifications: 1 2 From the Data Browser, click Components. From the Components folder, click Polymers.
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From the Polymers folder, click Distributions. The Selection sheet appears.
To request tracking of distributions, from the Selection sheet: 1 2 3 4 In the Polymer ID field, select the polymer for which you would like distributions tracked. In the Distribution type frame, select the type of distribution. Select the distribution plot characteristics: number of points for plot resolution, maximum for x-axis. For a GPC distribution, select Perform GPC Distribution Calculations. The distribution is calculated as rW(r) vs. r where r is number-average degree of polymerization.
Displaying Distribution Data for a Reactor

Once simulation calculations are complete, you can display and plot the distribution data for the polymerization reactor (RCSTR, RPLUG, or RBATCH) . To display the distribution data for a polymerization reactor: 1 2 3 4 1 2 3 4 5 From the Process Flowsheet window, use the right mouse button to click the reactor. Click Results. From the reactor Results form, click the Distributions tab. On the Distributions sheet, select the distribution to view. From the Plot menu, select Plot Wizard. Click Next. Click a distribution plot sample, then click Next. Change the plot settings as needed, then click Next or Finish to display the plot. Click the plot graphics to change the plot configuration: reconfigure axes, legends, or change titles. If you requested the GPC distribution format, you must set the x-axis to a log scale for the plot to display properly.
To plot the distribution data:
Displaying Distribution Data for Streams

To display a distribution data table for a stream: 1 2 3 4 1 2 3 From the Process Flowsheet window, use the right mouse button to click the feed stream. Click Results. From the Results form, click the Poly. Curves tab. On the Poly. Curves sheet, select the distribution to view. From the Data Browser, click Results Summary. From the Results Summary folder, click Streams. From the Streams form, click the Poly. Curves tab.
To display a distribution data table for the flowsheet:
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4 1 2 3 4 5
On the Poly. Curves sheet, select the distribution to view. From the Plot menu, select Plot Wizard. Click Next. Click a distribution plot sample, then click Next. Change the plot settings as needed, then click Next or Finish to display the plot. Click the plot graphics to change the plot configuration: reconfigure axes, legends, or change titles.
To plot the distribution data:
References
Biesenberger, J. A., & Sebastian, D. H. (1983). Principles of Polymerization Engineering. New York: Wiley-Interscience. Billmeyer, F. W. (1971). Textbook of Polymer Science. New York: WileyInterscience. Flory, P. J. (1936). Molecular Size Distribution in Linear Condensation Polymers. J. Am. Chem. Soc., 58, 1877. Flory, P. J. (1953). Principles of Polymer Chemistry. Ithaca, NY: Cornell University Press. Hamielec, A. E. (1992). Polymerization Processes. In B. Elvers, S. Hawkins, & G. Schulz (Eds.), Ullmanns Encyclopedia of Industrial Chemistry (5th Ed.) A21, (pp. 324-330). New York: VCH. Lansing, W. D., & Kramer, E.O. (1935). Molecular Weight Analysis of Mixtures by Sedimentation Equilibrium in the Svedberg Ultracentrifuge. J. Am. Chem. Soc., 57, 1369. Peebles, L. H., Jr. (1971). Molecular Weight Distribution in Polymers. New York: Wiley-Interscience. Rodriguez, F. (1989). Principles of Polymer Systems. New York: Hemisphere Publishing. Schulz, G. V. (1935). Uber die Beziehung zwischen Reaktionsgeschwindigkeit und Zusammensetzung des Reaktionsproduktes bei Makropolymerisationsvorgngen., Z. Physik. Chem., B30, 379. Schulz, G. V. (1939). Uber die Kinetik der kettenpolymerisationen. V. Der Einfluss verschiedener Reaktionsarten auf die Polymolekularitt. Z. Physik. Chem., B43, 25. Stockmayer, W. H. (1945). J. Chem. Phys., 13, 199. Tompa, H. (1976). The Calculation of Mole-Weight Distributions from Kinetic Schemes. In C.H. Bamford & C.F.H. Tipper (Eds.), Comprehensive Chemical Kinetics, 14A. New York: American Elsevier. Tung, L. H. (1956). Fractionation of Polyethylene. J. Polymer Sci., 20, 495. Weibull, W. (1951). A Statistical Distribution Function of Wide Applicability. J. Appl. Mech., 18, 293.
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Wesslau, H. (1956). Die Molekulargewichtsverteilung einiger Niederdruckpolythelene. Makromol. Chem., 20, 111. Zimm, B. H. (1948). Apparatus and Methods for Measurement and Interpretation of the Angular Variation of Light Scattering; Preliminary Results on Polystyrene Solutions. J. Chem. Phys., 16, 1099.
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6 End-Use Properties
This section describes polymer end-use properties. First, an overview of the properties of interest for polymers is given, followed by methods available in Aspen Polymers (formerly known as Aspen Polymers Plus) for calculating these properties. Topics covered include: Polymer Properties, 70 Prop-Set Properties, 71 End-Use Properties, 72 Method for Calculating End-Use Properties, 73 Calculating End-Use Properties, 76
Polymer Properties
Polymer properties fall into many categories: Structural properties Thermophysical properties - which provide an indication of the thermodynamic behavior of polymers Thermochemical properties - which provide information on thermal stability Transport properties Processing and end-use properties - which provide information about processability and performance during end-use
Polymer structural properties do not provide a direct measure of the performance of the polymer product during processing or during its end use. However, there is a relationship between polymer structural properties and the end use properties. For this reason, it is important to account for such properties within polymer process simulation models.
70
Prop-Set Properties
A property set is a collection of thermodynamic, transport, and other properties that you can use in: Stream reports Physical property tables and Analysis Unit operation model heating/cooling curve reports Distillation column stage property reports and performance specifications Reactor profiles Design specifications and constraints Calculator and sensitivity blocks Optimization and Data-Fit blocks
Aspen Plus has several built-in property sets that are sufficient for many applications. The list of built-in property sets is determined by the Template you choose when creating a new run. You can use a built-in property set and modify it to fit your needs, or you can create your own property sets. To see the built-in sets available or to select one, use the drop-down list on any property set list box. The list prompts describe the contents of each built-in property set. For information on defining a property set, see the Aspen Plus User Guide. The following table summarizes key property sets for the major thermophysical and transport properties of interest in polymer process simulations:
Property Set Name CP CPMX K KMX KINVISC MU MUMX RHO RHOMX TG TM TRUEFLO W TRUEFRA C TRUEMW Valid Qualifiers Description Pure component heat capacity Mixture heat capacity Pure component thermal conductivity Mixture thermal conductivity Mixture kinematic viscosity Pure component viscosity (zero shear) Mixture viscosity (at zero shear) Pure component density Mixture density Component glass transition temp. Component melt transition temp. Component true mole flow rate Component true mole fraction Component true molecular weight Phase X X X X X X X X X X X X X X X X X X X X X Comps. X Temp. X X X X X X X X X Pres. X X X X X X X X X
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End-Use Properties
The end-use or processing properties of interest for polymers include properties that describe their performance in the last stage of the polymer manufacturing process. Also of interest are properties relating to their performance when they reach the consumer. The following table summarizes some end-use properties:
Category Processing Property Melt index Melt index ratio (I10/I2) Moldability index Zero-shear viscosity Density of copolymer Polymer product Deformation Toughness/hardness Flammability Availability in Aspen Polymers Yes No No Yes Yes No No No
Relationship to Molecular Structure

The end-use properties such as rheological and mechanical properties are functions of the polymer structural properties and processing history. For example, long chain branching raises low shear viscosity, increases shear thinning, delays melt fracture, and increases extrudate swell. For example, one could relate end-use properties of polyethylene to density, molecular weight, or melt index (Foster, 1993). See the following table:
Properties Molecular weight Melt Index Impact strength Stress crack resistance Elongation Tensile strength Melt strength Orientation Elasticity Parision sag resistance Distortion resistance Weatherability Stiffness Heat Resistance Hardness Molecular Weight ------Melt Index ------Density ---- -- ----------
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Properties Permeation resistance Shrinkage Creep resistance Transparency Flexibility
Molecular Weight -----------
Melt Index ----------
Density
The basic structure-property relationship has attracted much research activity as the relationship is critical for product performance control. We recommended you follow the recent developments in structure-property relationship (Bicerano, 1996; Foster, 1993).
Method for Calculating End-Use Properties

Few end-use properties of interest for polymers are currently available in Aspen Polymers. However, the method used for implementing the ones available is a good mechanism for users to incorporate additional ones if they have the necessary correlations to molecular structure and/or thermophysical properties. Within Aspen Polymers, end-use properties are available as property sets (Prop-Set). A Prop-Set provides a method for calculating properties for components within process flowstreams or vessel contents. A number of built-in Prop-Sets are available (See your Aspen Plus User Guide documentation). In addition, Prop-Sets allow the specification of a property set with add-on user correlations. When doing this, a Fortran subroutine is required to perform the calculations. End-use polymer properties are available as user property sets. This is because the correlations available to calculate these properties are highly empirical and are often dependent on the type of polymer for which they are used. User property sets can easily be modified. Users can directly change the property correlation in the associated Fortran subroutine.
User Property Sets

The following table summarizes the Prop-Set name and Fortran subroutine name for the built-in user property sets:
Property Melt index Intrinsic viscosity Zero-shear viscosity Density of copolymer Prop-Set Name MI-KAR, MI-SIN IV ZVIS DENS Fortran Subroutine USRPRP USRPRP USRPRP USRPRP
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Intrinsic Viscosity
The intrinsic viscosity is given as:
= K M w + JM w
Where: = Intrinsic viscosity = Weight-average molecular weight
Mw
J and K = Correlation constants
Zero-Shear Viscosity
For some ethyl branched paraffinic monodisperse polymers, Arnett and Thomas reported an empirical correlation for zero-shear viscosity as a function of molecular weight, number of branched sites per 1000 carbon atoms, and temperature (Arnett & Thomas, 1980):
ln 0 = a ln M w +
Where:
d (1 + cn) bn e + B( n ) T
3
0 Mw
n a d c b B(n) B(0) B(0.02) B(0.13)
= Zero shear viscosity in Poise = Molecular weight = Number of branched sites per 1000 carbon atoms = 3.41 = 3523 = 0.832 = 2.368 = Function of number of branches with: = -35.78 = -37.04 = -40.88
B(0.069) = -38.11 B(0.183) = -43.54
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Density of Copolymer
Randall and Ruff presented an empirical correlation for semicrystalline copolymer density (Randall & Ruff, 1988):
n a 2 = a + b(1 ) i i c a i =1
Where: = Actual density = Crystalline density = Amorphous density
c a
n
a and b = Correlation constants = Minimum crystallization run length of monomer = Reaction probability that monomer is followed by similar monomer
Melt Index
Karol and colleagues suggested a Quackenbos equation for high density polyethylene prepared with chromocene-based catalysts (Karol et al., 1973; Quackenbos, 1969):
MI = a( bM w + cM n )
Where: MI a b c d
= Melt index =
10 . 1018
= 0.2 = 0.8 = -3.9 = Weight-average molecular weight = Number-average molecular weight
Mw Mn
Sinclair suggested a simpler correlation (Sinclair, 1983):
a b MI = Mw
Where: a = 111,525 b = 0.288
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Melt Index Ratio

The Quackenbos equation can also be used to correlate melt index ratio.
Calculating End-Use Properties

End-use properties are calculated as Prop-Sets. You must first select which end-use property to include in the simulation, then you must define this property as a Prop-Set.
Selecting an End-Use Property

To access end-use property Prop-Sets: 1 2 3 4 5 6 From the Data Browser, click Properties. From the Properties folder, click Advanced. From the Advanced folder, click User Properties. From the User Properties object manager, click New. If necessary, change the default ID for the user-property and click OK. From the User Properties Specifications sheet, choose the standard property as the type (default), then provide the subroutine name.
Create one User-Property for each end-use property.
Adding an End-Use Property Prop-Set

To access Prop-Sets: 1 2 3 4 5 From the Data Browser, click Properties. From the Properties folder, click Prop-Sets. From the Prop-Sets object manager, click New. If necessary, change the default ID for the Prop-set and click OK. From the Prop-Set Properties sheet, in the Physical Properties field, select the ID for the end-use property User-Property. You can have as many User-Properties as needed.
References
Arnett, R. L. & Thomas, C. P. (1980). Zero-Shear Viscosity of Some Ethyl Branched Paraffinic Model Polymers. J. Phys. Chem., 84, 649-652. Aspen Plus User Guide. Cambridge, MA: Aspen Technology, Inc. Bicerano, J. (1996). Prediction of Polymer Properties. New York: Marcel Dekker. Foster, G.N. (1993). Short Course: Polymer Reaction Engineering. Ontario, Canada: McMaster Institute for Polymer Production Technology.
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Grulke, E. A. (1994). Polymer Process Engineering. Englewood Cliffs, NJ: Prentice Hall. Hamielec, A. E. (1996), Polymer Reactor Modeling Technology (Course Notes). Cambridge, MA: Aspen Technology, Inc. Karol, F. J., Brown, G. L., & Davison, J. M. (1973) Chromocene-Based Catalysts for Ethylene Polymerization: Kinetic Parameters. J. of Polymer Science: Polymer Chemistry Edition, 11, 413-424. Quackenbos, H. M. (1969). Practical Use of Intrinsic Viscosity for Polyethylenes. J. of Applied Polymer Science, 13, 341-351. Randall, J. C. & Ruff, C. J. (1988). A New Look at the 'Run Number' Concept in Copolymer Characterization. Macromolecules, 21, 3446-3454. Rudin, A. (1982). The Elements of Polymer Science and Engineering. New York: Academic Press Inc., Harcourt Brace Jovanovich. Sinclair, K. B. (1983). Characteristics of Linear LPPE and Description of UCC Gas Phase Process, Process Economics Report. Menlo Park, CA: SRI International.
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7 Polymerization Reactions
This chapter discusses polymerization mechanisms and kinetics. Topics discussed in the introductory section include: Polymerization Reaction Categories, 78 Polymerization Process Types, 81 Aspen Polymers Reaction Models, 82
Following an introduction that provides background information of the subject, a separate section is devoted to each of the polymerization kinetic models available in Aspen Polymers (formerly known as Aspen Polymers Plus). Step-Growth Polymerization Model, 85 Free-Radical Bulk Polymerization Model, Emulsion Polymerization Model, Ziegler-Natta Polymerization Model, Ionic Polymerization Model, Segment-Based Reaction Model,
Polymerization Reaction Categories

Over the years, many classifications have been developed for polymerization reactions. One classification divides them into condensation and addition polymerization.
Condensation Polymerization
Condensation polymerization results in the elimination of a smaller molecule, water for example, through the reaction of bi- or polyfunctional monomers.
Addition Polymerization
Addition polymerization, on the other hand, does not produce small molecule byproducts. The repeating units within the polymer have the same structure as the monomers from which they originated.
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The problem with this classification is that while it describes differences in the molecular structure of the resulting polymer, it does not fully capture the differences in the reaction mechanism. Furthermore, a given polymer can be made by more then one pathway, one which would result in an addition polymer, and one which would result in a condensation polymer, by this classification. For example, Nylon-6 can be made through a caprolactam, and therefore be labeled an addition polymer, or through an -aminohexanoic acid, and in this case be labeled a condensation polymer.
Step Growth and Chain Growth Polymerization

A classification that is more useful for capturing the difference in the mechanisms through which polymers are produced divides polymerization reactions into step-growth and chain-growth polymerization. The differences between step-growth and chain-growth polymerization are summarized in the following tables:
Step Growth Polymerization Monomer type Reaction categories Reacting species Bi-, polyfunctional Single intermolecular reaction Any combination of monomers, oligomers, polymer chains Small molecule elimination product for condensation polymerization only Slow, chain lifetime of the order of hours High molecular weight at high conversion Chain Growth Polymerization No functionality Several consecutive reactions for initiation, growth, and termination Monomers and active centers (free-radical, ion, polymer, catalyst end) None
Elimination product Polymer growth rate Polymer size
Rapid, chain lifetime of the order of seconds High molecular weight at all conversion levels
Reaction Type Step Growth Condensatio n Pseudo condensatio n Ring Scission
Active Center
Initiation
Growth Reaction
Bi-, polyfunctional end groups Bi-, polyfunctional end groups Bi-, polyfunctional end groups
None None
Nucleophilic substitution Nucleophilic addition
Yes for ring opening
Nucleophilic addition or substitution
Chain Growth Free-radical Coordinatio Free radical Metal complex Chemical, thermal, radiative Catalyst Monomers add on to radical Monomers insert into metal
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n Ionic Anion or cation
activation Dissociation
complex carbon bond Monomers add on at ion pair
Step-Growth Polymerization
Step-growth polymerization retains the definition given for condensation polymers for the majority of cases. That is, monomers react with each other to eliminate small molecules. Step-growth polymers are formed through the same reaction type occurring between functional groups located on any combination of monomers, oligomers, or polymer chains. The polymer chains continue to grow from both ends as polymerization progresses. The reactions occur at a relatively slow rate and chains grow slowly. Some examples of step-growth polymers include polyamides, polyesters, polycarbonates, and polyurethanes (See Polymer Structure in Chapter 2 for a discussion of polymer types based on molecular structure).
Step Growth Polymer Categories

Step-growth polymerization can be sub-categorized as condensation, pseudocondensation, and ring-opening or ring-scission depending on the chemical pathways through which the reactions occur. The following table lists typical commercial step-growth polymers:
Polymer (Trade Name) Polyamide (Nylon 6,6) Polyester (PET) Monomers Repeat Unit Reaction Type
O NH
O C
Applications (Similar Polymers) Fiber, plastics (Lycra, Nylon 6) Fiber (PBT, Dacron, Nylon)
Adipic acid Hexamethylene diamine Terephthalic acid Ethylene glycol
(CH2)6NHC(CH2)4C
O C O CH2 CH2 O
Dicarboxylic acid + diamines Dicarboxylic onhydride + glycols Dihydroxy reactant + Phosgene Diisocyanate + dialcohol
Polycarbonate (Lexan) Polyurethane
Bisphenol-A Phosgene Toluene diisoyamate polyether diol
CH3 O C CH3
O O C
Lenses, packaging (Merlon) Foam, packaging
R NH CO O R1
Chain-Growth Polymerization
Chain growth polymers are formed through the addition of monomers to an active center (free-radical, ion, or polymer-catalyst bond), in a chain reaction, at a very fast rate. Furthermore, several different types of reaction occur to initiate, propagate, and terminate polymer growth. Examples of
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chain growth polymers include various polyolefins, polyvinyls, and several copolymers (styrenic copolymers, for example).
Chain Growth Polymer Categories

Chain-growth polymerization can be categorized as free-radical, coordination complex, or ionic, depending on the type and method of formation of the active center. The following table lists typical commercial chain-growth polymers:
Polymer Polyethylene Monomers Ethylene Repeat Unit
CH2 CH2
Reaction Types Bulk/solution (freeradical) Coordination complex (Ziegler-Natta)
Applications Film, packaging
Polystyrene
Styrene
CH2
CH
Bulk/solution/ suspension (freeradical) Coordination complex (Ziegler-Natta)
Containers, packaging, insulation Films, packaging, autoparts, sealants Films, plastic tubing Floor coverings, pipes Lenses, plastics
Polypropylene
Propylene
CH CH3
CH2
Polyisobutylene
Isobutylene
CH3 C CH3 CH2
Ionic
Polyvinyl chloride
Vinyl chloride Methyl Methacrylat e Styrene Butadiene
CH2
CH Cl
CH3
Bulk/solution/ suspension (freeradical) Bulk/solution (freeradical)
Polymethalmethacryl ate
CH2
C COOCH3
Styrene butadiene rubber
CH2
CH CH2
CH CH CH2
Emulsion (free-radical)
Tires, belting, shoe soles
Polymerization Process Types

Step Growth Reaction Sub-classes
In addition to chemical pathways, the environment or process conditions in which the polymerization reactions occur introduce more sub-classes of polymers. For example, step-growth reactions may take place as melt phase, solid-state, solution, or interfacial polymerization: Melt-phase processes are carried out above the melting point of the polymer Solid-state processes are carried out below the melting point of the polymer
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Solution processes are carried out in the presence of an inert solvent Interfacial processes are carried out in the interface between an organic phase and an aqueous phase
Chain Growth Reaction Sub-classes

Chain-growth polymerization may take place in bulk phase, solution, precipitation, suspension, or emulsion: Bulk polymerization is carried out in the bulk monomer phase without a solvent Solution polymerization is carried out in the presence of an inert solvent in which monomers and polymer are dissolved Precipitation polymerization is carried out using a solvent to precipitate out the polymer Suspension polymerization involves monomers suspended as droplets in a continuous phase (usually water) to which an oil-soluble initiator is added Emulsion polymerization involves monomers and micelles dispersed in a continuous water phase using surfactants. Initiator is added to the emulsion of partially water soluble monomers in the surfactant solution
There are additional process related classifications that have to do with reactor geometry. These are discussed in sections covering unit operation modeling later in this User Guide.
Aspen Polymers Reaction Models

There are two types of reaction models available in Aspen Polymers: Built-in models User models
Built-in Models
The polymerization reaction models available in Aspen Polymers are summarized in the following table:
Model Name Step-growth STEP-GROWTH Step-growth condensation Melt phase, solution, interfacial Melt phase, solution, interfacial PC, PBT, PET, Nylons Chemistry Processes Polymers
SEGMENT-BAS
Step-growth addition
Polyurethanes, polyimides, PPO, engineering plastics
Chain-growth FREE-RAD Free-radical Bulk, solution PS, PVAC, SAN, PMMA
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Model Name EMULSION ZIEGLER-NAT IONIC Generic SEGMENT-BAS
Chemistry Free-radical Ziegler-Natta / metallocene coordination complex Anionic/Cationic group transfer
Processes Emulsion Bulk, solution Solution
Polymers SBR, SBA HDPE, PP, LLDPE PIB, SBR, PEO
Segment-based power-law reaction model
N/A
PVA from PVAC
In addition to models for the chemistries and process types listed, there is one model available for generic polymer modification reactions. This model follows a standard power-law scheme and is used to represent reactions involving modifications to segments of polymers made through one of the conventional reaction schemes. One of the standard Aspen Plus reaction models can also be used in conjunction with the polymerization reaction models. The standard Aspen Plus reaction models are:
Model Name LHHW POWERLAW USER Description Langmuir-Hinshelwood-Hougen-Watson reaction rate expressions Power-law reaction rate expressions Kinetic rate expressions supplied by user, kinetic rate computed in user supplied subroutine
For more information about these models, consult the Aspen Plus User Guide and Aspen Plus User Models.
User Models
There are cases where the built-in models do not provide the features necessary to model specific polymerization kinetics. Some of the polymerization reaction models provide capabilities to incorporate user reactions. In addition, the USER reaction model provides the capabilities for defining user kinetic schemes. The USER reaction model is structured to allow the specification of the reaction stoichiometry. In addition, there are vectors for entering user real and integer parameters. This input information along with the reaction vessel contents, in the form of the stream structure, is made available to a user supplied Fortran subroutine during calculations. Note that component attributes are part of the stream structure. There is an update and initialization scheme to automatically process these attributes. The user supplied Fortran subroutine can return rates for components and component attributes. From the subroutine, Aspen Plus utilities including physical property routines, math utilities, and stream handling utilities can be accessed. Some of these utilities are documented in Appendix C.
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References
Aspen Plus User Models. Cambridge, MA: Aspen Technology, Inc. Aspen Plus User Guide. Cambridge, MA: Aspen Technology, Inc. Dotson, N. A, Galvn, R., Laurence, R. L., & Tirrell, M. (1996). Polymerization Process Modeling. New York: VCH Publishers. Grulke, E. A. (1994). Polymer Process Engineering. Englewood Cliffs, NJ: Prentice Hall. Hamielec, A. E. (1992). Polymerization Processes. In B. Elvers, S. Hawkins, & G. Schulz (Eds.), Ullmanns Encyclopedia of Industrial Chemistry (5th Ed.) A21, (pp. 324-330). New York: VCH. Odian, G. (1991). Principles of Polymerization, 3rd Ed. New York: John Wiley & Sons. Rudin, A. P. (1982). The Elements of Polymer Science and Engineering. Orlando, FL: Academic Press. Sun, S. F. (1994). Physical Chemistry of Macromolecules. New York: John Wiley & Sons.
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8 Step-Growth Polymerization Model
This section covers the step-growth polymerization model available in Aspen Polymers (formerly known as Aspen Polymers Plus). It begins with general background information on step-growth polymerization and covers some of the terms associated with these kinetics. Several industrial polymerization processes are examined in detail. A discussion of the model features and usage is also included. Topics covered include: Summary of Applications, 85 Step-Growth Processes, 86 Reaction Kinetic Scheme, 97 Model Features and Assumptions, 120 Model Structure, 123 Specifying Step-Growth Polymerization Kinetics, 152
The Aspen Polymers Examples & Applications Case Book illustrates how to use the step-growth model to simulate nylon-6 polymerization from caprolactam. More detailed examples are available in Step-Growth Polymerization Process Modeling and Product Design by Kevin Seavey and Y. A. Liu, ISBN: 978-0470-23823-3, Wiley, 2008.
Summary of Applications
Step-growth polymerization can be used to model various polycondensation and specialty plastic processes. Some of the applicable polymers are described below: Aliphatic polycarbonates - Transesterification of diols with lower dialkyl carbonates, dioxolanones, or diphenyl carbonate in the presence of catalysts such as alkali metal, tin, and titanium compounds. Aromatic polycarbonates - Reaction product of bisphenols with carbonic acid derivatives. May be prepared by transesterification, solution polymerization, and, most often by interfacial polymerization.
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Polyesters - Produced commercially in two steps: monomer formation by ester interchange of diesters with diols or esterification of diacids with diols, followed by polycondensation by removing excess diols to promote chain extension. This is accomplished commercially on a simple two-vessel batch process or on large-scale multi-vessel continuous-polymerization process. Polyamides - Produced via direct amidation, reaction of acid chlorides with amines, ring-opening polymerization, reaction of diacids and diisocyanates, etc. Commercially prepared by melt polycondensation, ringopening polymerization, and low temperature solution polymerization. Polyurethanes - Polyurethane isocyanates are usually produced commercially by the phosgenation of amines. Polyester polyols are prepared by step-growth polymerization.
Step-Growth Processes
Several commodity polymers, including polyesters, nylons, and polycarbonate, are manufactured through step-growth polymerization processes. This section examines some of the major processes that can be represented using the step-growth polymerization kinetics model.
Polyesters
Continuous Polyethylene-Terephthalate Processes
Polyethylene-terephthalate (PET) is produced by the step-growth polymerization of ethylene glycol, a diol, and either terephthalic acid, a diacid, or dimethyl terephthalate, a diester. Most processes are continuous although many older process lines operate in batch or semi-batch mode.
Direct Esterification
The direct esterification process involves the reaction of ethylene glycol with terephthalic acid. The terephthalic acid is mixed with excess ethylene glycol to form a solid-liquid paste. In the continuous process, the monomer paste is typically fed to a well-mixed reactor, the primary esterifier, which operates at temperatures of 250-290 C and pressures ranging from one to several atmospheres. Typical residence times range from one to four hours in this stage of the process. A solid at room temperature, terephthalic acid has limited solubility in the polymer solution, even at the relatively high process temperatures. Further, the dissolution rate of TPA may be limited by the solid-liquid mass transfer rate, especially if the average particle size is large, or when the reactor operates at high temperatures and pressures. The following figure illustrates a continuous direct esterification process for PET:
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Secondary Esterification
In most continuous plants, the primary esterifier is followed by secondary and, occasionally, a tertiary esterifier. These reactors range from single-tank CSTRs to a variety of multiple-stage CSTRs composed of vertical or horizontal vessels divided into two or more chambers by partitions. Secondary esterification reactors typically have residence times on the order of an hour, with temperatures similar to or slightly higher than the primary esterifier. The secondary esterification reactor is often run under atmospheric conditions, although slight positive pressure or vacuum pressures are also used in some processes. Vapor from the esterification reactors flows to one or more distillation columns which separate ethylene glycol from the reaction by-products which include water and acetaldehyde. In some processes, spray-condenser loops are used to wash entrained TPA and vaporized low-molecular weight oligomers from the vapor stream to prevent oligomer build-up in the distillation columns.
Glycol Recovery
The ethylene glycol from the esterification distillation columns can be recycled directly to the esterification reactors, to the paste mixing tank, or, in the case of high-quality products, it can be collected for further processing to remove contaminants. The companies which license PET technology use a wide variety of glycol recovery and recycling schemes. All of these recycling schemes can be simulated using conventional distillation, flash, and heat exchanger models available in Aspen Plus.
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Esterification Results
The product of the esterification reactors is composed of short-chain oligomers with some residual monomers. The main oligomer in the product is bis-hydroxyethyl-terephthalate (BHET), which is slightly volatile under typical operating conditions. The step-growth model includes an oligomer feature which can be used to account for evaporative loss of linear oligomers such as BHET.
Transesterification Process
In the transesterification process, dimethyl terephthalate (DMT) is used instead of terephthalic acid (TPA). One advantage of this process is the relatively high solubility of DMT, which eliminates the solid-liquid mass transfer problem in the first stage of the process. A second advantage is the low acidity of DMT, which reduces several of the side reaction rates and results in a higher quality polymer. The limitations of the transesterification process include increased monomer cost, production of methanol as a byproduct (instead of water), and reduced reactivity in the finishing stages. The transesterification process produces methanol as a reaction by-product. The methanol is distilled from ethylene glycol through distillation columns. Recovered glycol may be recycled to the reactor, the paste mixing tank, or accumulated for additional processing. It is desirable to minimize the concentration of methylester ends in the feed to the polymerization section. Obtaining high conversions is very important in the DMT process because the reverse reaction of methanol with PET is more highly favored than the reaction of water and PET. A wide variety of proprietary reactors are used to effect high end-group conversion during the transesterification process.
Continuous Polymerization
The continuous polymerization process is the same for the direct esterification and transesterification processes. Typically, the polymerization section consists of one or more CSTR reactors (pre-polymerization reactors) followed by one or more horizontal finishing reactors (polymerization reactors). These reactors consist of a series of rotating blades or disks which lift polymer from a pool at the bottom of the reactor into a vapor space over the pool. The design criteria of these reactors are to maximize surface area generation while minimizing back-mixing. In polyester processes, the finishing reactors are almost always limited by the liquid-vapor mass transfer rates. In some cases, the pre-polymerization reactors are also limited by mass transfer. The reactors in the polymerization section operate at increasingly higher temperatures and lower pressures to enhance the devolatilization of excess glycol and reaction byproducts such as water, methanol, and acetaldehyde. Reactor residence times range from thirty minutes to four hours depending on the number and type of reactors in the polymerization section. Vapor from the polymerization section is scrubbed by spray-condenser loops composed of a contacting vessel, accumulation tank, pump, and heat exchanger. In most plants, vacuum is generated through venturi jets operated by steam or vaporized glycol. In some process configurations, the
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condensed glycol and water mixture is recycled to the esterification columns. Otherwise, the condensate is accumulated and processed to recover glycol.
Operating Conditions
The esterification and transesterification sections of PET processes frequently operate below the melting point of the polymer. Under these operating conditions, the process can be considered solution polymerization. The polymerization reactors operate above the melting point of the polymer in a true melt-phase polymerization. The step-growth reaction model may be used for both modes of operation. In most cases, the same reaction kinetics apply to both solution- and melt-phase reaction processes.
Final Products
The continuous melt-phase PET processes generally produce polymer with an average intrinsic viscosity of approximately 0.6 dl/g, which corresponds to a number-average degree of polymerization near 100 units. This product may be directly spun as clothing fiber, partially oriented yarn (POY), film, or it may be cooled and chipped for on- or off-site use. Recent increases in consumer recycling programs and consumer preference for unbreakable bottles has created a very large market for polyester bottles. These bottles are molded from a higher molecular weight polyester chip which is produced by a solid state process. Fundamentally, the step-growth model can apply to solid-state polymerization. However, at this time, Aspen Polymers does not include a solid-state polymerization (SSP) reactor model. Semi-rigorous SSP models can be developed using a series of CSTR reactors. Solid phase polymer solutions can be treated as a liquid phase in Aspen Polymers. The property system switches between liquid-phase property models and solid-phase property models when the temperature drops below the melting point of the polymer component.
Batch Polyethylene-Terephthalate Processes

Polyethylene Terephthalate is also produced in batch and semi-batch processes, as shown in the following figure. Usually, the process consists of two batch reactors in series. The role of the first reactor is to reach high conversions of the terephthalate monomer while minimizing undesirable side reactions. The role of the second reactor is to raise the molecular weight of the polymer to appropriate levels.
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The first reactor is coupled to a column which separates the volatile reaction by-products from excess ethylene glycol and evaporated oligomers. The heavy components are continuously returned to the reactor during most of the batch cycle. Towards the end of the cycle, the evaporated ethylene glycol and residual monomers are removed and accumulated for re-use in the next batch. The batch esterification process commonly uses a semi-continuous feeding system for the solid TPA. In most batch esterification processes, the reaction rate is limited by the rate of dissolution of TPA. This is complicated by the relationship between the mass transfer rates and particle size. To enhance TPA solubility, a portion of the polymer product is retained in the reactor at the end of the cycle. The recycled product is used to start the next batch. This design allows the cycle to start at a higher temperature, reducing the cycle time for each batch. The trade off between the batch cycle time and the quantity of recycle polymer is one of the most interesting problems to examine using simulation technology. The batch transesterification process is typically operated in true-batch mode, without recycling polymer. In this process, the monomers, ethylene glycol and DMT, are charged to the reactor at the beginning of the cycle. The continuous removal of methanol from the batch reactor makes very high endgroup concentrations possible. This version of Aspen Plus does not include an appropriate reactor model to simulate batch polymerization reactors with overhead distillation columns. AspenTechs Polyester Technology Package includes several modeling solutions for representing these types of batch processes in the Aspen Plus and Aspen Custom Modeler environments.
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Second Batch Stage

The liquid product from the batch esterification or transesterification is charged to a second batch stage. In this stage, the reactor is evacuated as the temperature is increased. These operating profiles enhance the removal of excess ethylene glycol from the reaction mixture, allowing these highly reversible reactions to proceed. As the polymer viscosity increases, the reactions become limited by the rate of mass transfer from the liquid phase to the vapor phase due to decreased surface renewal rates and reduced agitator speeds.
Other Polyester Processes

Polybutylene-terephthalate (PBT) is an engineering plastic frequently used for machine parts, car body panels, and other applications. Polybutylene terephthalate is analogous to PET, except butylene glycol is used in place of ethylene glycol. Most PBT is manufactured from DMT through continuous transesterification processes, although batch processes and direct esterification processes are also found in industry. In the PBT process, tetrahydrofurane, THF, is formed from butylene glycol end groups as an undesirable reaction by-product. The transesterification process is favored over direct esterification because the acid end groups in TPA catalyze the formation of THF. Polypropylene-terephthalate (PPT) is used for carpet fiber and other applications. Like PET and PBT, PPT can be manufactured from terephthalic acid or dimethyl terephthalate. In the PPT process, propylene glycol is used as the diol monomer. Polyethylene-naphthalate (PEN) manufacturing processes are under development by several polyester producers. This new product has a higher melting point than PET, and is aimed at specific demands, such as hot-fill bottles, which are not well satisfied by other polyesters. The dimethyl ester naphthalate monomer is much more expensive than TPA or DMT, so PEN is frequently produced as a copolymer with PET. At this time, most PEN is produced in batch processes which are analogous to the batch PET process. Copolymers of PEN and PET are being used for some bottling applications already. The similarities in the chemical mechanism for PET and PEN make them relatively easy to copolymerize in various ratios, resulting in several product grades with properties intermediate between pure PET and pure PEN.
Polyester Technology Package

Aspen Technology offers several solutions for polyester processes. The AspenTech Polyester Technology Package provides steady-state simulation of melt-phase continuous processes and also includes process models for batch polyester processes. The Polyester Technology Package is designed for PET and PBT, but can be easily modified for analogous polyesters such as PEN, PTT, etc.
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Aspen PolyQuestSM, jointly developed with Hosokawa Bepex corporation, is a simulation package covering all varieties of solid-state PET processes. Aspen PolyQuest includes detailed and rigorous models for reaction kinetics, diffusion, heat transfer, and crystallization, as well as a library of detailed unit operation models for solid-state processing equipment. Aspen PolyQuest runs on the Aspen Custom Modeler platform. The underlying equation-based models can be used for dynamic or steady-state process simulation. The models in these packages account for all the major side reactions in the process, such as thermal scission, aldehyde formation, DEG formation, and cyclic trimer formation. The reaction kinetic models consider the influence of several common catalysts and additives as well as acid catalysis and uncatalyzed side reactions. The package includes reactor models which consider solid-liquid mass transfer for the direct esterification process, and liquid-vapor mass transfer limited kinetics for the polymerization reactors. The Polyester Technology Package includes models of several common process configurations, including both batch and continuous processes. The models predict various quality parameters such as the acid end group concentration (acid value), intrinsic viscosity, vinyl end content, DEG content, conversion, etc. Contact your Aspen Technology sales representative for more information about the Polyester Technology Package, Aspen PolyQuest, and advanced consulting services.
Nylon-6
Nylon-6 is produced by ring-opening polymerization of -caprolactam. Water and caprolactam are fed to a primary reactor where the ring-opening reaction takes place. The primary reactor may be a single (liquid) phase tubular reactor, CSTR, or one of a variety of proprietary reactors. The following figure illustrates a continuous melt-phase nylon-6 process:
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VK Column
One of the most well known of these proprietary designs is the Vereinfacht Kontinuierliches (or VK) column. The VK column is a reactor with a high aspect ratio which is filled to relatively high liquid levels. The reacting mixture boils vigorously near the top of the VK column, resulting in considerable radial and axial mixing. Below this well-mixed zone is a plug-flow zone in which the hydrostatic pressure is sufficient to suppress boiling. Reactors of this type can be simulated using one or more two-phase CSTR reactors (model RCSTR) in series with a single liquid-phase plug flow reactor (model RPlug). The top of the VK column typically operates near atmospheric pressure. Heat exchangers inside the upper section of the reactor bring the reactants to temperatures of 220-270C. Typical residence times are in the order of three to five hours. A reflux condenser or distillation column over the reactor returns the monomer and most of the water back to the VK column. Although the initial stages of Nylon-6,6 polymerization are catalyzed by water, the water must be removed in later stages to allow the condensation reactions to proceed to high conversion. Water removal is accomplished by carrying out the reaction in a series of stages at successively lower pressures. Secondary stages typically involve one or more CSTR reactors followed by vertical wiped-film evaporators. Inert gas may be used to strip water from the polymer melt. For some products, chain terminators are used to control the molecular weight of the product. Acetic acid is commonly used, but any monofunctional acid or alcohol can be used to control molecular weight build-up. Horizontal finishing reactors may be used to increase the polymer molecular weight and reduce the residual monomer and cyclic oligomer concentrations.
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In these devolatilization stages, the evaporation of water, excess caprolactam, aminocaproic acid, and cyclic oligomers is limited by the rate of mass transfer from the liquid phase to the vapor phase.
Nylon-6,6
Nylon-6,6 is manufactured by two types of processes. In the most common process, dyadic nylon salt is first produced by mixing adipic acid (ADA) in an aqueous solution of hexamethylene diamine (HMDA). A newer process involves the direct melt polymerization of the two monomers.
Salt Preparation
In the traditional salting process, the formation of nylon salt ensures stoichiometric ratios of the two monomers, allowing the production of high molecular weight polymers. In the salt solution process, solid adipic acid is dissolved in an aqueous solution of HMDA. The resulting aqueous salt solution is concentrated by further addition of the monomers and/or by partial evaporation. An alternative salting process uses methanol as the primary solvent. Solutions of adipic acid and HMDA in methanol are prepared separately in continuously stirred heated tanks. These solutions are mixed in a reactor where the nylon salt is generated. Most of the nylon salt precipitates out of solution due to the low solubility of the nylon salt in methanol. A small amount of the salt, however, remains dissolved in the reactor, resulting in the generation of some short-chain oligomers. The salt slurry is centrifuged to remove the solid salt. Methanol is used as a washing solution in the centrifuge to further purify the salt. The methanol is purified in a distillation column and recycled. The solid nylon salt is dried and collected for use on- or off-site.
Polymerization from Aqueous Salt Solutions

Most nylon-6,6 is produced in continuous processes made up of several stages. The primary stage operates at high pressures and temperatures to control the loss of volatile monomers and to accelerate the reactions. In the intermediate reactors, the operating pressure is reduced substantially and much of the excess water is evaporated. The finishing stages of the process are made up of one or more wiped-film evaporators which help to remove the remaining residuals. A typical nylon-6,6 continuous process is shown here:
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First Stage
In the first stage, aqueous salt solutions are fed to a reactor which operates at high temperatures (230-290C) and pressures (> 250 psig). High temperatures are required to dissolve the salt and to accelerate the reaction rates. The high pressure is required to avoid excess loss of HMDA, which is generated by polymerization reactions. In the first reactor, the nylon salt dissolves and condensation reactions take place between molecules of the dissolved salt and between the dissolved salt and polymer end groups. Much of the water which enters with the salt and is generated by the condensation reactions is boiled off in the first stage due to the high operating temperature. In some processes, the salt solution is fed to a column over the first reactor. As the solution flows down the column, excess water is driven off. Condensation reactions take place in the reactor at the bottom of the column as well as in the trays of the column. The column also condenses evaporated HMDA, returning it to the reactor vessel. Additives, such as titanium dioxide, are fed to the primary reactor vessel. The reactor vessel is made up of two parts: a separation vessel and a heat exchanger tube-bank. The separator vessel is located at the bottom of the column, where it receives the reflux from the column. The liquid at the bottom of the separator is pumped through the tube-bank heat exchanger, which acts as the reboiler for the column. The high circulation rates through the heat exchanger section of the reactor keep the reactor contents well mixed.
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Intermediate Stage
Liquid from the primary reactor must be throttled to lower pressures to remove water, which allows the reversible condensation reaction to proceed to higher conversions. The depressurization and devolatilization of the intermediate are carried out by several different techniques involving a series of degassing vessels connected by throttle valves. In some processes, a looptype reactor is used to reduce the pressure. Excess HMDA or adipic acid or monofunctional chain stoppers, such as acetic acid, may be added in the intermediate stages of the process to control the molecular weight build-up. Catalysts and thermal stabilizers are also added to the oligomer.
Final Stage
In the final stages of polymerization, wiped-wall evaporators are used to finish the reaction at high temperatures (up to 300C) and medium vacuum pressures (760-200 torr). Typical finishing reactor residence times range from 20-60 minutes. The removal of water and excess monomers from the liquid phase may be limited by the mass transfer rate.
Melt-Phase Polymerization
Recent developments in nylon-6,6 polymerization have led to the development of continuous melt-phase polymerization processes. Adipic acid and hexamethylene diamine solutions are fed to a tubular primary reactor, which operates at very high pressures (approximately 1000 psig), temperatures around 275C, and residence times of 15-30 minutes. Under these conditions, boiling does not occur in the reactor. The pressure is throttled down to 250-350 psig through a series of valves or tubes of successively larger diameter. The pressure profile must be adjusted to minimize cooling caused by the rapid evaporation of steam, which can cause the polymer solution to freeze. In the final stage, the polymer is brought close to chemical equilibrium (with dissolved water and excess monomers) in a wiped film evaporator.
Polycarbonate
Polycarbonate is a relatively strong polymer with good optical and mechanical properties. It is used in several applications including car body parts (frequently blended with PBT), specialty films, and laser disc media. Historically, most polycarbonate was produced by interfacial polymerization of bisphenol-A (BPA) with phosgene. In the interfacial process, the reactions are relatively fast, but the reaction rate is limited by the mass transfer rates of the reactants from the bulk liquid phases into the swollen polymer phase. A limited amount of polycarbonate is produced from BPA and phosgene in a solution polymerization process. The reaction is carried out by solution polymerization in pyridine. The pyridine solvent captures chlorine from the phosgene groups, resulting in pyridine chloride as a reaction by-product.
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Recently, the melt-phase polymerization of bisphenol-A with diphenyl carbonate (DPC) has become an important industrial process. The melt polymerization process has a significant safety advantage over the interfacial process because phosgene is highly volatile and extremely toxic. A typical melt-phase polycarbonate process is shown here:
The monomers, BPA and DPC, are fed in a carefully controlled ratio to a series of CSTRs. Phenol, which is generated as a reaction by-product, is vaporized in the reactors and must be condensed and recycled. Distillation columns are used to recover residual monomers from phenol. The CSTRs are followed by a series of wiped film evaporators and horizontal finishing reactors which operate at successively lower pressures to enhance the removal of residual monomers and phenol. These reactors are limited by the mass transfer rate of phenol from the melt.
Reaction Kinetic Scheme

This section gives a general overview of nucleophilic reactions and reaction nomenclature, as well as specific information on polyester, nylon-6, nylon6,6, and melt polycarbonate reaction kinetics.
Nucleophilic Reactions
Step-growth polymerization involves reactions between monomers containing nucleophilic and electrophilic functional groups. Nucleophilic groups are electron-strong groups, typically alcohols (~OH), amines (~ NH 2 ), or water.
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Electrophilic groups are electron-weak groups such as acids (~COOH), esters (~COO~), amides (~CONH~), and isocyanates (~NCO). When two chemical species react, the species with the strongest nucleophilic group is called the nucleophile; the other reactant bearing the strongest electrophilic group is called the electrophile. Nucleophiles and electrophiles participate in bimolecular reactions. Depending on the types of functional groups in each reactant, the reaction mechanism may be nucleophilic substitution or nucleophilic addition.
Nucleophilic Substitution
In nucleophilic substitution reactions, a nucleophilic group from one reactant (the nucleophile) displace a nucleophilic group in the other reactant (the electrophile), resulting in two new products. (Note: Electrophilic groups are highlighted in each of the following figures.) Nucleophilic substitution reactions tend to be highly reversible.
O CH OH + HO C 3 Nucleophilic Species Electrophilic Species O HOH + CH3O C Nucleophilic Species Electrophilic Species
Forward Reaction
Reverse Reaction
Nucleophilic Addition
In nucleophilic addition reactions, the electrophile and nucleophile combine to form a new functional group. These reactions are typically irreversible.
CH3 OH + O C N Nucleophilic Species Electrophilic Species O CH 3 O C NH
Currently, the step-growth reaction generation algorithm is limited to condensation reactions. Pseudocondensation reactions must be defined through the user reaction feature or through the segment-based power-law reaction model. In some reverse reactions and re-arrangement reactions, the electrophile may be a polymer or oligomer. These reactions occur at the bonds which link two segments together. To fully describe these reactions, the two segments in the electrophile must be identified. In this case, we refer to the electrophile as the victim reactant and the nucleophile as the attacking reactant. The victim reactant includes a nucleophilic segment and an electrophilic segment.
Attacking Nucleophilic Species Victim Victim Nucleophilic Electrophilic Species Species O O C CH3OH + O(CH2)2O C
O O(CH2)2OH + CH3O C
O C
The following table lists the role of electrophiles and nucleophiles in several step-growth polymerization processes, as well as the typical reacting
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functional groups, the characteristic repeat unit, and the by-product related to each polymerization process:
Polymer Class Polyester Nucleophile ~OH ~OH Electrophile ~COOH Repeat Unit ~(C=O)O~ ~(C=O)O~ ~(C=O)O~ ~(C=O)NH~ ~O(C=O)O~ ~O(C=O)O~ ~NH(C=O)O~ ~NH(C=O)O~ ~NH(C=O)NH ~ Condensate By-product
~COOCH3
~COOH ~COOH ~O(C=O)Cl ~O(C=O)Oph ~(C=O)Cl ~N=C=O ~N=C=O
H2O CH3OH CH3COOH H2O

HCl PhOH HCl none none none
~O(C=O)CH3
Polyamide Polyacetal (Polycarbonate) Polyurethanes
~NH2
~OH ~OH
~NH2
~OH
Polyurea Polyether
~NH2
~OH
O CH CH2
~OCH2C(OH)H~
Reaction Nomenclature
Polymerization reactions are classified by chemical mechanism, by the number of reacting components, and by the influence a reaction has on the chain length distribution. This section describes the basic types of reactions found in step-growth polymerization and serves as a glossary of reaction nomenclature. Intermolecular reactions involve two or more molecules. Intramolecular reactions involve two sites on the same molecule. Condensation reactions are polymerization reactions which produce a small molecule as a by-product. Typically, the condensate is a volatile compound such as water, methanol, acetic acid, or phenol. Step-growth reactions involving chlorine end groups result in hydrochloric acid or chlorinated hydrocarbon condensate products. Reverse condensation reactions are where condensate molecules cleave an existing polymer chain, producing two smaller chains. Reverse condensation reactions near the end of a polymer molecule can generate free monomers. Pseudocondensation reactions are nucleophilic addition reactions. These reactions involve rearrangement of atoms in two different functional groups, resulting in a new functional group. No by-products are produced by pseudocondensation reactions. Pseudocondensation reactions can involve two monomers, a monomer and a polymer end group, or two polymer end groups. Addition reactions are reactions in which small molecules, including free monomers, dyadic salts, and cyclic monomers and dimers react with the end
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of a growing polymer molecule. These reactions are responsible for the conversion of the monomers and most of the conversion of functional end groups. Combination reactions involve reactions between the end groups of two polymer molecules. In most systems, combination reactions play an important role in molecular weight growth. Rearrangement reactions occur between two polymer molecules, resulting in two new polymer molecules with different molecular weights. These reactions may involve the end group of one molecule and an internal site on another molecule, or they may involve internal sites on both molecules. Ring opening reactions are intermolecular reactions between condensate or monomer molecules and cyclic monomers or oligomers. Condensate molecules or monomers react with cyclic compounds, opening the ring structure to produce linear oligomers or cyclic monomers. Ring closing reactions are intramolecular reactions which occur between the two end groups of a linear molecule. Ring-closing reactions which occur between two end groups of a branched or network molecule are referred to here as intramolecular cyclization to differentiate them from reactions which form ring-shaped molecules. Ring addition reactions are intermolecular reactions between polymer end groups and cyclic monomers or oligomers. The end group of the polymer links to the cyclic compound, opening the ring and lengthening the chain of the linear molecule. Cyclodepolymerization reactions are intramolecular reactions in which a polymer end group reacts with a segment in the same molecule, forming a ring. The ring-shaped molecule is lost from the linear parent molecule, reducing the molecular weight of the parent. Terminal monomer loss involves the loss of a monomer unit at the end of a polymer chain due to thermal degradation mechanisms. Random scission involves the spontaneous cleavage of a polymer chain due to thermal degradation. End group reformation reactions are those reactions which convert one type of end group into another without influencing the chain length. The following table summarizes the reactions for step-growth polymerization:
Reaction Class Intermolecul ar Reaction Mechanism Nucleophilic Substitution Reaction Type Condensation Monomer Addition Condensation - Polymer Addition Reverse Condensation Terminal Monomer Loss Reverse Condensation Scission Reaction Scheme Included Yes Yes Yes Yes Yes Yes
M + M P2 + W
Pn + M Pn +1 + W Pn + Pm Pn + m + W
W + P2 M + M
W + Pn Pn 1 + M W + Pn Pn m + Pm
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Reaction Class
Reaction Mechanism
Reaction Type Forward Polycondensation Reverse Polycondensation Re-arrangement Ring Opening Ring Addition
Reaction Scheme
Included Yes Yes Yes No No No No No No No No No No No
Pn + Pm Pn + m1 + M
M + Pn Pn m + Pm+1
Pn + Pm Pn + m q + Pq
W + Cn Pn Pn + Cm Pn + m M + M P2
Pn + M Pn +1 Pn + Pm Pn + m P2 M + M
Nucleophilic Addition (Pseudo-condensation)
Monomer Addition
Polymer Addition Intramolecul ar Pseudo-condensation or Thermal mechanisms Terminal Monomer Loss
Pn Pn 1 + M
Scission
Pn Pn m + Pm Pn Cn + W
Pn Pn m + Cm Pn Cn
Nucleophilic Substitution
Ring-Closing Cyclodepolymerization
Nucleophilic Addition
Ring-Closing
Pn Cn
M W
= = = =
Linear polymer with n segments Cyclic polymer with n segments ( C1 = cyclic monomer, such as caprolactam) Monomer Condensate
Polyester Reaction Kinetics

In the direct esterification process, polyesters are produced by the reaction of diols, such as ethylene glycol, with diacids, such as terephthalic acid. The esterification reactions generate one mole of water for each mole of ester groups formed. The reactions are catalyzed by acid end groups in the polymer and diacid monomer.
Side Reactions
Several of the key side reactions are also acid-catalyzed. In the PET process, these reactions include the formation of diethylene glycol, or DEG, from ethylene glycol. The transesterification process does not involve acids, and substantially less DEG is produced. An analogous reaction generates tetrahydrofurane (THF) in the PBT process. Like DEG formation, THF formation is accelerated by acid end groups. Since
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THF poses environmental concerns, the generation of THF should be minimized. For this reason, PBT is usually produced by the transesterification route. Metal acetate catalysts are used to accelerate the reaction rates in the later stages of the direct esterification process and throughout the transesterification process. These catalysts accelerate the main reactions and several side reactions including thermal scission and aldehyde formation. In the transesterification process, acid end groups may be formed by thermal degradation reactions or by exchange reactions with water, which may be formed as a reaction by-product. These acid end groups participate in the reaction scheme, making transesterification kinetics a superset of esterification kinetics.
Polymerization Stage
The polymerization stage involves chain building reactions. There are two main growth mechanisms. Condensation reactions occur between two polymer end groups, releasing water or methanol. Polymerization reactions occur between diol end groups in different polymer molecules, generating a molecule of free glycol. The polymer end group distribution and molecular weight distribution are randomized by redistribution reactions.
Polyester Production Final Stages

In the final stages of polyester production, high temperatures lead to thermal degradation reactions. In the PET process, these reactions degrade glycol end groups, producing acid ends and free acetaldehyde. Thermal scission reactions generate acid end groups and oxyvinyl end groups. Analogous reactions in the PBT process yield butenol and 1,4-butadiene. Additional side reactions involving these vinyl groups are the main source of color bodies in polyesters. Cyclic compounds are formed by ring-closing and cyclodepolymerization reactions. Cyclic monomers, and some cyclic dimers do not form in terephthalic polyesters because of steric limitations. Trace amounts of larger cyclic oligomers, including trimers, tetramers, and pentamers, are commonly observed in terephthalate polyesters. These cyclic compounds reduce the quality of the polyester. Cyclic oligomers evaporate from the finishing reactors and condense in vapor vent lines, causing maintenance problems. The reaction kinetics of terephthalate polyesters are summarized in the tables that follow. The components involved in the reactions are:
Component ID TPA T-TPA Databank ID C8H6O4-D3 C8H5O3-E Component Structure
O HO C O C O C OH O C OH
Component Name Terephthalic acid Terephthalic acid end group
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Component ID B-TPA DMT T-DMT MMT H2O MEOH
Databank ID C8H4O2-R C10H10O4D2 C9H7O3-E none H2O CH4O
Component Structure
O C O CH3O C O C O HO C O C O C OCH3 O C OCH3 O C OCH3
Component Name Terephthalate repeat unit Dimethyl terephthalate Dimethyl terephthalate end group Monomethyl terephthalate Water Methanol
H2O CH3OH
Components In Polyethylene Terephthalate Processes EG T-EG B-EG DEG T-DEG B-DEG T-VINYL C3 C2H6O2 C2H5O2-E C2H4O2-R C4H10O3 C4H9O3-E C4H8O3-R C2H3O-E none
HO(CH2)2OH ~O(CH2)2OH ~O(CH2)2O~ HO(CH2)2O(CH2)2OH ~O(CH2)2O(CH2)2OH ~O(CH2)2O(CH2)2O~ ~OCH=CH2

O T= C G = O(CH2)2O O C T G T G T G
Ethylene glycol Ethylene glycol end group Ethylene glycol repeat unit Diethylene glycol Diethylene glycol end group Diethylene glycol repeat unit Oxyvinyl end group Cyclic trimer
Components In Polybutylene Terephthalate Processes BD T-BD B-BD T-BUTENOL THF C4H10O2 C4H9O2-E C4H8O2-R C4H11O2-E C4H8O-4
HO(CH2)4OH ~O(CH2)4OH ~O(CH2)4O~ ~O(CH2)2CH=CH2
1,4 Butane diol 1,4 Butane diol end group 1,4 Butane diol repeat unit Butenol end group Tetrahydrofurane
The following table summarizes the step-growth reactions associated with terephthalate polyesters. For brevity, the table shows a subset of the reactions which actually occur - an analogous set of reactions involving DEG are also generated by the step-growth model.
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Reaction Type Condensation
Stoichiometric Reactions - Direct Esterification Route
O HO(CH2)x OH + HO C O O(CH2) x OH + HO C O HO(CH2)x OH + HO C O O(CH2) x OH + HO C
O C OH O C OH O C O C
O C OH O C O C
1 2 3 4 5 6 7 8
9 10 11 12 13 14
O HO(CH2) x O C O O(CH2) x O C O HO(CH2) x O C O O(CH2) x O C

O O(CH2)x O C O O(CH2)x O C O O(CH2)x O C
O C OH + H2O O C OH + H2O O C O C + H2O + H2O
Polymerization
O O(CH2)x OH + HO(CH2)x O C O O(CH2)x OH + HO(CH2)x O C
O C OH + HO(CH2)x OH O C O C + HO(CH2)x OH
Rearrangement
O(CH2)x OH +
O O(CH2)x O C
+ HO(CH2)x O
Additional Reactions - Transesterification Route

O HO(CH2)x OH + CH3O C O O(CH2)x OH + CH3O C O HO(CH2) x OH + CH3O C O O(CH2)x OH + CH3O C O C OCH3 O C OCH3 O C O C
O C OCH3
15 16 17 18 19 20 21 22
23 24
O HO(CH2) x O C O O(CH2)x O C O HO(CH2)x O C O O(CH2)x O C

O O(CH2)x O C
O C OCH3 + CH3OH O C OCH3 + CH3OH O C O C + CH3OH + CH3OH
Polymerization End-group Exchange
O O(CH2)x OH + HO(CH2)x O C
O C OCH3 + HO(CH2)x OH
O H2O + CH3O C
O C
25 26
O HO C
O C
+ CH3OH
x = 2 for polyethylene-terephthalate x = 3 for polypropylene-terephthalate x = 4 for polybutylene-terephthalate
The following table describes how to assign rate constants to each of the reactions listed in the previous table:
Reaction No. 1 2 Attacking Nucleophilic Species EG H2O Victim Electrophilic Species TPA T-TPA Victim Nucleophilic Species none T-EG
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3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26
T-EG H2O EG H2O T-EG H2O T-EG EG T-EG EG T-EG T-EG EG MEOH T-EG MEOH EG MEOH T-EG MEOH T-EG EG H2O MEOH
TPA T-TPA T-TPA B-TPA T-TPA B-TPA T-TPA T-TPA B-TPA B-TPA B-TPA B-TPA DMT T-DMT DMT T-DMT T-DMT B-TPA T-DMT B-TPA T-DMT T-DMT T-DMT T-TPA
none B-EG none T-EG none B-EG T-EG B-EG T-EG B-EG B-EG B-EG none T-EG none B-EG none T-EG none B-EG T-EG B-EG none none
Many of the side reactions in the polyester process are not included in the reaction generation scheme, and must be added to the model as user reactions. These reactions are:
Reaction Type DEG Formation Reaction Stoichiometry
HO(CH2)2OH + HO(CH2)2OH HO(CH2)2OH + HO(CH2)2O O(CH2)2OH + HO(CH2)2O
U1 U2 U3
O C
HO(CH2)2O(CH2)2OH HO(CH2)2O(CH2)2O O(CH2)2O(CH2)2O

O C OH + H2C CHO
U5 U6 O C O C
+ H2O + H2O + H2O
Thermal Scission Acetaldehyde Formation
O C
O C O(CH2)2O
O C
U4
O C O(CH2)2OH O C OCH CH2
O O C OH + HCCH3 O C O(CH2)2O O + HCCH3
O(CH2)2OH +
O C
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Reaction Type Cyclic Trimer Formation
Reaction Stoichiometry
HOT G T G T GH HG T G T G T GH G T G T G T GH U7 U8 U9 U10 U11 U12 T T G T G T G T G T G + H2 O G + HO(CH2)2OH G T G T G
O(CH2)2OH + T
The recommended power-law exponents for the reactants in the side reactions are:
Reaction No. U1 U2 U3 U4 Power-Law Exponents; Modeling Notes EG = 2 (Multiply group-based pre-exponential factor by 4.0) EG = 1, T-EG = 1 (Multiply group-based pre-exponential factor by 2.0) T-EG = 2 (Multiply group-based pre-exponential factor by 1.0) Reaction is first order with respect to polyester repeat units, assume concentration of repeat units is approximately equal to the concentration of B-TPA, set power-law exponents B-TPA = 1.0 B-EG = 1x10-8 T-EG = 1 T-EG = 1, T-VINYL = 1 Reaction is first order with respect to linear molecule with the following segment sequence: T-TPA: B-EG : B-TPA : B-EG : B-TPA : T-EG option 1: assume this concentration = TPA concentration and use power-law constant TPA = 1* option 2: use the following equation, based on the most-probable distribution, to estimate the concentration of this linear oligomer. This equation can be implemented as a user-rate constant correlation
[T EG ] [ B TPA] [P ] = NUCL ELEC
2 2
U5 U6 U7
[ B EG ] [T TPA] NUCL ELEC 0
NUCL = [T EG ] + [T DEG ] + 2 *[ B EG ] + 2 *[ ELEC = [T TPA] + 2 *[ B TPA]
U8 U9
H2O = 1, C3 = 1 (Multiply group-based pre-exponential factor by 6.0) Reaction is first order with respect to linear molecule with the following segment sequence: T-EG : B-TPA : B-EG : B-TPA : B-EG : B-TPA : T-EG option 1: assume this concentration = TPA concentration and use power-law constant TPA = 1* option 2: use the following equation, based on the most-probable distribution, to estimate the concentration of this linear oligomer. This equation can be implemented as a user-rate constant correlation
[T EG ] [P ] = NUCL
2 2
[ B TPA] [ B EG ] ELEC NUCL 0
NUCL = [T EG ] + [T DEG ] + 2 *[ B EG ] + 2 *[ B DEG ] ELEC = [T TPA] + 2 *[ B TPA]
U10
EG = 1, C3 = 1 (Multiply group-based pre-exponential factor by 12.0)
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Reaction No. U11
Power-Law Exponents; Modeling Notes Reaction is first order with respect to linear molecule with the following segment sequence: ~B-EG : B-TPA : B-EG : B-TPA : B-EG : B-TPA : T-EG option 1: assume this concentration = T-EG concentration and use power-law constant T-EG = 1* option 2: use the following equation, based on the most-probable distribution, to estimate the concentration of this linear oligomer. This equation can be implemented as a user-rate constant correlation
[T EG ] [ B TPA] [P ] = NUCL ELEC
2 3
[ B EG ] NUCL 0
NUCL = [T EG ] + [T DEG ] + 2 *[ B EG ] + 2 *[ B DEG ] ELEC = [T TPA] + 2 *[ B TPA]
U12
T-EG = 1, C3 = 1 (Multiply group-based pre-exponential factor by 6.0)
To avoid numerical problems, set power-law exponents to 1 10 8 for reactants which do not appear in the rate expression
0 = Concentration zeroth moment, mol/L (approximately=0.5*([T-TPA]+[TEG]+[T-DEG]+[T-VINYL])
Nylon-6 Reaction Kinetics

Nylon-6 melt-phase polymerization reactions are initialized by the hydrolytic scission of caprolactam rings. The reaction between water and caprolactam generates aminocaproic acid. The reaction kinetics in the primary reactor are sensitive to the initial water concentration. The carboxylic and amine end groups of the aminocaproic acid molecules participate in condensation reactions, releasing water and forming polymer molecules. The resulting acid and amine end groups in the polymer react with each other and with aminocaproic acid, releasing more water. The amine end of aminocaproic acid and amine ends in polymer react with caprolactam through ring addition. This reaction is the primary growth mechanism in the nylon-6 process.
Cyclic Oligomers
As the reactions proceed, intramolecular reactions involving linear polymer molecules generate cyclic oligomers. Cyclic oligomers ranging from the dimer through rings ten units long are reported in the literature. The concentration of each successive cyclic oligomer (dimer, trimer, etc.) falls off sharply, in accordance with the most probable distribution. Reactions involving cyclic compounds are not considered in the reaction generation algorithm in the step-growth model. These reactions, including ring opening, ring closing, ring addition, and cyclodepolymerization, must be specified as user reactions.
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The following table summarizes key components in the nylon-6 melt polymerization process. The component names in this table are used in the tables that follow.
Component ID CL Databank ID C6H11NO Component Structure
O NH
Component Name -Caprolactam
ACA T-NH2 T-COOH R-NY6 CD H2O
none C6H12NO-E-1 C6H12NO2-E-1 C6H11NO-R-1 none H2O
O H2N (CH2)5 C OH O H2N (CH2)5 C O NH (CH2)5 C OH O NH (CH2)5 C NH (CH2)5 C O O C (CH2)5 NH
Aminocaproic acid Amine end group segment Acid end group segment Nylon-6 repeat segment Cyclic dimer Water
H2O
Major Reactions
The major reactions in the nylon-6 melt polymerization process are shown here:
Reaction Type Ring Opening / Ring Closing Ring Addition / Cyclodepolymerization User-Specified Reactions (Forward and Reverse Reactions Defined Separately) U1 U2 H2O + CL H2O + CD ACA T-COOH : T-NH2 (=P2)
U3 U4 U5 U6
ACA + CL T-NH2 + CL ACA + CD T-NH2 + CD
T-COOH : T-NH2 (=P2) R-NY6 : T-NH2 T-COOH : R-NY6 : T-NH2 (=P3) R-NY6 : R-NY6 : T-NH2
Model-Generated Step-Growth Reactions (Define Nylon-6 Repeat Unit as EN-GRP)
1. ACA + ACA 2. 3. 4. ACA + T-COOH T-NH2 + ACA T-NH2 + T-COOH T-NH2 + T-NH2 : T-COOH
T-COOH : T-NH2 + H2O T-COOH : R-NY6 + H2O R-NY66 : T-NH2 + H2O R-NY66 : R-NY6 + H2O T-NH2 : R-NY6 + ACA R-NY6 : R-NY6 + ACA R-NY6 : R-NY6 + T-NH2
Re-Arrangement
5. 6. 7.
T-NH2 + R-NY6 : T-COOH T-NH2 + R-NY6 : R-NY6
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In the reaction stoichiometry equations above, the colon (:) indicates connections between segments. Literature sources report rearrangement reactions are insignificant, these reaction rates can be set to zero
The reactions U1-U6, which involve cyclic monomer and dimer, are not generated by the current version of the Step-Growth model. These reactions must be defined as user reactions. However, the stoichiometry of each of these reactions is shown. Reactions 1-7 are considered in the reaction generation algorithm in the StepGrowth kinetics model. The rate constants for these reactions can be assigned according to the identifiers summarized here:
Reaction No. 1 forward 2 forward 3 forward 4 forward 5 forward 6 forward 7 forward 1 reverse 2 reverse 3 reverse 4 reverse 5 reverse 6 reverse 7 reverse Attacking Nucleophilic Species ACA ACA T-NH2 T-NH2 T-NH2 T-NH2 T-NH2 H2O H2O H2O H2O ACA ACA T-NH2 Victim Electrophilic Species T-ACA T-COOH ACA T-COOH T-NH2 T-NH2 R-NY6 T-NH2 R-NY6 T-NH2 R-NY6 T-NH2 R-NY6 R-NY6 Victim Nucleophilic Species none none none none T-COOH R-NY6 R-NY6 T-COOH T-COOH R-NY6 R-NY6 R-NY6 R-NY6 R-NY6
The suggested power-law exponents are shown here:

Reaction No. U1 forward U1 reverse U2 forward Power-Law Exponents; Modeling Notes H2O = 1, CL = 1 ACA = 1 H2O = 1, CD = 1 (Multiply group-based pre-exponential factor by 2.0)
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Reaction No. U2 reverse
Power-Law Exponents; Modeling Notes Reaction is first order with respect to linear dimer sequence: T-NH2 :T-COOH option 1: assume ACA = 1* option 2: use the following equation, based on the most-probable distribution, to estimate concentration of P2 The denominator in this equation can be implemented as a user rate constant, with first-order power-law constants for T-NH2 and T-COOH.
P2
with the following segment
P2
concentration = ACA concentration and use power-law constant
[T NH 2] [T COOH ] [P ] = [T NH 2] + [ R NY 6] [ T COOH ] + [ R NY 6]
2
U3 forward U3 reverse U4 forward U4 reverse U5 forward U5 reverse
ACA = 1, CL = 1 See U2 reverse reaction T-NH2 = 1, CL = 1 T-NH2 = 1 (this approximation assumes most T-NH2 end groups are attached to repeat units)* ACA = 1, CD = 1 Reaction is first order with respect to linear trimer sequence: T-NH2 : R-NY6 : T-COOH option 1: assume ACA = 1* option 2: use the following equation, based on the most-probable distribution, to estimate concentration of P 3 The denominator in this equation can be implemented as a user rate constant, with first-order power-law constants for T-NH2, R-NY6, and T-COOH.
P3
with the following segment
P3
concentration = ACA concentration and use power-law constant
[T NH 2] [ R NY 6] [T COOH ] [P ] = [T NH 2] + [ R NY 6] [T COOH ] + [ R NY 6] [T COOH ] + [ R NY 6]

2
U6 forward U6 reverse
T-NH2 = 1, CD = 1 T-NH2 = 1 (this approximation assumes most T-NH2 end groups are attached to repeat units)*
To avoid numerical problems, set power-law exponents to appear in the rate expression
110 8
for reactants which do not
0 = Concentration zeroth moment, mol/L (approximately = 0.5 * ([T-COOH] + [T-NH2])

The side reactions are thought to be catalyzed by acid end groups in aminocaproic acid and the polymer. A first-order power-law coefficient can be used to account for the influence of the acid groups in these components.
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Alternately, a user rate-constant subroutine can be developed to account for the influence of the acid end groups. Note that the forward and reverse terms of the reversible side reactions must be defined as two separate user reactions in the model.
Nylon-6,6 Reaction Kinetics

The salt process involves a preliminary reaction to form the salt, which precipitates from solution. During the salt formation, some of the salt remains in solution, leading to higher polymers. For a rigorous model, it is a good idea to consider these oligomerization reactions, even in the salt precipitation reactor. Accounting for these reactions is important when using the model to optimize the temperature, pressure, and water content of the nylon salt crystallizer. The model needs to consider three phase equilibrium (solid salt, liquid, and vapor). Three phase equilibrium can be considered in Aspen Plus using the electrolyte chemistry feature. In version 10.0, however, the CSTR model does not allow a component to appear simultaneously in chemistry reactions and kinetic reactions. Another way to represent the solid-liquid equilibrium is to define an equilibrium reaction between the components representing the dissolved and solid salt. Chemical equilibrium equations can be defined using the Power-Law reaction kinetics model in Aspen Plus. Apply the molegamma option to force the equilibrium equation to use the ratio of the molar activities as the basis of the equilibrium constant. By using this assumption, the equilibrium constant is the same as the solubility constant of the solid salt. To model the reaction kinetics of the salt process, the dissolved salt should be considered as a component in the reaction model. The models described in the open literature do this by considering the salt as an AB type monomer. This treatment, however, fails to consider some of the reverse reactions which can occur during polymerization. This approach assumes that reverse condensation reactions and re-arrangement reactions always generate products with an equal number of adipic acid and HMDA units. In reality, polymer chains with an unequal number of units can be formed because the reactions can occur inside the repeat units which originally came from the reacting salts. Further, the reverse reactions can generate free adipic acid or HMDA when the reaction occurs at the end of a polymer chain.
Reverse Rate Constant

The models in the literature use a reverse rate constant which is twice the reverse rate constant experienced by an individual amine group. This factor of two accounts for the fact that each repeat unit has two amine groups. In the approach described here, the reverse rate constants used in the model should be the rate constant between two functional groups, for example between water and a single amine group. Considering salt as a component, there are several reversible reactions which must be considered in the model. A number of condensation reactions occur including those between molecules of dissolved salt, dissolved monomers, and polymer end groups. These reactions can be implemented in the step-growth
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model through the user reaction feature. The step-growth model will generate the reactions which do not involve the salt component. The molecular weight distribution of nylon-6,6 is known to re-equilibrate when the polymer is exposed to HMDA under pressure. Further, as vacuum is applied, free HMDA appears to be generated. These facts indicate that rearrangement reactions are important in this process.
Modeling Approaches
There are two modeling approaches: Simplified Detailed
Databank ID Component Structure Component Name
The component definitions for both modeling approaches are:

Component ID
Components Common to Simplified and Detailed Approach ADA HMDA DIS-SALT SOL-SALT MEOH H2O C6H10O4-D1 C6H16N2 none none CH4O H2O
O O HO C (CH2)4 C OH
Adipic acid Hexamethylene diamine Dissolved nylon-6,6 salt Solid nylon-6,6 salt Methanol Water
H2N (CH2)6 NH2

O O HO C (CH2) 4 C NH (CH2) 6 NH2
O O HO C (CH2)4 C O- +H3N (CH2) 6 NH2
CH3OH H2O
Segments In Simplified Salt Process Model T-COOH T-NH2 R-NY66 none none none
O O HO C (CH2) 4 C NH (CH2)6 NH O O C (CH2)4 C NH (CH2)6 NH2 O O C (CH2)4 C NH (CH2) 6 NH
Acid end group segment Amine end group segment Repeat unit segment
Segments In Detailed Salt Process Model and Melt-Process Model T-ADA B-ADA T-HMDA B-HMDA C6H9O3-E C6H8O2-R C6H15N2-E C6H14N2-R
O O C (CH2)4 C OH
O C (CH2)4 O C
Adipic acid end group Adipic acid repeat unit HMDA end group HMDA repeat unit
HN (CH2)6 NH2 HN (CH2)6 NH
Note: The component names used in this table are used in the successive tables to document the reactions.
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In the simplified approach, the dissolved salt is treated as an AB monomer (a monomer with two different types of functional groups). This is accomplished by defining the repeat unit as an EN-GRP reactive group. The simplified approach is consistent with the modeling approach described in the open literature. Using this approach, the Step-Growth model will generate all of the main reactions. The solid-liquid phase equilibrium can be represented as a chemical equilibrium reaction using the Power-Law model or as two side reactions in the step-growth model. The equilibrium constant of this reaction corresponds to the solubility constant of the salt. The reactions for a simplified Nylon-6,6 salt process model are shown here:
Reaction Type Solid/Liquid Equilibrium Reaction Type Salt formation Reaction Type Condensation Phase Equilibrium Reactions (Use Power-Law Reaction Kinetics Model)
C1
DIS-SALT + H2O
SOL-SALT
User-Specified Reactions (Forward and Reverse Reactions Defined Separately)
U1
HMDA + ADA
DIS-SALT + H2O
Model-Generated Step-Growth Reactions (Define Nylon-6,6 Repeat Unit as EN-GRP)
1. 2. 3. 4.
DIS-SALT + DIS-SALT DIS-SALT + T-COOH T-NH2 + DIS-SALT T-NH2 + T-COOH T-NH2 + T-COOH : T-NH2 T-NH2 + T-COOH : R-NY66 T-NH2 + R-NY66 : R-NY66
T-COOH : T-NH2 + H2O T-COOH : R-NY66 + H2O R-NY66 : T-NH2 + H2O R-NY66 : T-NY66 + H2O R-NY66 : T-NH2 + DIS-SALT R-NY66 : R-NY66 + DIS-SALT R-NY66 : R-NY66 + T-NH2
Re-Arrangement
5. 6. 7.
In the reaction stoichiometry equations above, the colon (:) indicates connections between segments
The detailed modeling approach treats the HMDA and ADA segments as discreet molecular units. Using this assumption, the dissolved salt is a dimer made up of one hexamethylene diamine end group and one adipic acid end group. This approach is more rigorous because it considers every possible reverse reaction, including terminal monomer loss. To use this approach, define the HMDA repeat group as a bifunctional nucleophile (NN-GRP), and the ADA repeat group as a bifunctional electrophile (EE-GRP). The solid-liquid phase equilibrium (reaction C1) is represented as previously described. The reactions involving the dissolved salt, U1-U6, must be defined as user reactions. Reactions 1-7, which do not involve the salt, are generated by the model automatically. The reactions for a detailed Nylon-6,6 salt process model are shown here:
Reaction Type Phase Equilibrium Reactions (Use Power-Law
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Reaction Kinetics Model) Solid/Liquid Equilibrium Reaction Type Salt formation Condensation
C1
DIS-SALT + H2O
SOL-SALT
User-Specified Reactions (Forward and Reverse Reactions Defined Separately)
U1
U2 U3 U4 U5 U6
HMDA + ADA
DIS-SALT + DIS-SALT DIS-SALT + ADA HMDA + DIS-SALT DIS-SALT + T-ADA T-HMDA + DIS-SALT
DIS-SALT + H2O
T-HMDA : B-ADA : B-HMDA : T-ADA + H2O T-ADA : B-HMDA : T-ADA + H2O T-HMDA : B-ADA : T-HMDA + H2O T-ADA : B:HMDA : B-ADA + H2O B-HMDA : B-ADA : T-HMDA + H2O
Model-Generated Step-Growth Reactions (Define BHMDA as NN-GRP, B-ADA as EE-GRP)
1. 2. 3. 4.
HMDA + ADA HMDA + T-ADA T-HMDA + ADA T-HMDA + T-ADA
T-HMDA : T-ADA + H2O T-HMDA : B-ADA + H2O B-HMDA : B-ADA + H2O B-HMDA + B-ADA + H2O T-ADA : B-HMDA + HMDA B-ADA : B-HMDA + HMDA B-ADA : B-HMDA + T-HMDA
Re-Arrangement
5. 6. 7.
T-HMDA + T-ADA : T-HMDA T-HMDA + B-ADA : T-HMDA T-HMDA + B-ADA : B-HMDA
Rate Constant Identifiers

The rate constants can be assigned to model-generated reactions in the simplified model using the identifiers summarized here:
Reaction No. 1 forward 2 forward 3 forward 4 forward 5 forward 6 forward 7 forward 1 reverse 2 reverse 3 reverse Attacking Nucleophilic Species DIS-SALT DIS-SALT T-NH2 T-NH2 T-NH2 T-NH2 T-NH2 H2O H2O H2O Victim Electrophilic Species DIS-SALT T-COOH DIS-SALT T-COOH T-COOH T-COOH R-NY66 T-COOH T-COOH R-NY66 Victim Nucleophilic Species none none none none T-NH2 R-NY66 R-NY66 T-NH2 R-NY66 T-NH2
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4 reverse 5 reverse 6 reverse 7 reverse
H2O DIS-SALT DIS-SALT T-NH2
R-NY66 T-NH2 R-NY66 R-NY66
R-NY66 R-NY66 R-NY66 R-NY66
A subset of these identifiers can be used to assign the same rate constant to several different reactions. For example, reactions 3-7 can be lumped together by specifying T-NH2 as the attacking nucleophilic species and by leaving the victim species identifiers blank (unspecified). Rate constants can be assigned to reactions 1-7 in the detailed model using the identifiers summarized here:
Reaction No. Attacking Nucleophilic Species HMDA HMDA T-HMDA T-HMDA T-HMDA T-HMDA T-HMDA H2O H2O H2O H2O HMDA HMDA T-HMDA Victim Electrophilic Species ADA T-ADA ADA T-ADA T-ADA B-ADA B-ADA T-ADA B-ADA T-ADA B-ADA T-ADA B-ADA B-ADA Victim Nucleophilic Species none none none none T-HMDA T-HMDA B-HMDA T-HMDA T-HMDA B-HMDA B-HMDA B-HMDA B-HMDA B-HMDA
1 forward 2 forward 3 forward 4 forward 5 forward 6 forward 7 forward 1 reverse 2 reverse 3 reverse 4 reverse 5 reverse 6 reverse 7 reverse
A subset of these identifiers can be used to assign the same rate constant to several different reactions. For example, reactions 3-7 can be lumped together by specifying T-HMDA as the attacking nucleophilic species and by leaving the victim species identifiers blank (unspecified). Each reaction involving the dissolved salt must be defined as a user-reaction in the Step-Growth model. The forward and reverse reactions are treated as two separate reactions. The stoichiometry of each reaction was shown previously in the reactions table for the detailed modeling approach. The power-law exponents are in the following table. Several of the reverse reactions require a particular sequence of segments in order to occur. The concentration of molecules with these particular sequences can be assumed (for example, assume the linear trimer concentration is the same as the dissolved salt concentration) or they can be estimated from statistical arguments. The following table shows both techniques. The statistical approach is more rigorous, but it requires writing a
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user rate-constant or user kinetic subroutine to perform the calculations as shown. The power-law exponents for user-specified reactions in the detailed model are:
Reaction No. U1 forward U1 reverse U2 forward U2 reverse Power-Law Exponents; Modeling Notes HMDA = 1, ADA = 1 Multiply group-based pre-exponential factor by 4.0 H2O = 1, DIS-SALT = 1 DIS-SALT = 2 Reaction is first order with respect to water and polymer molecule following segment sequence: T-HMDA : B-ADA : B-HMDA : T-ADA option 1: assume H2O = 1* option 2: set power-law exponent for H2O = 1 and use the following equation, based on the most-probable distribution, to estimate concentration of P 4 (this equation can be implemented as a user rate constant).
P4
with the
P4
concentration = DIS-SALT concentration and use DIS-SALT = 1,
[P4 ] =
[T ADA] 2[ B HMDA] [T ADA] + 2[ B ADA] [T HMDA] + 2[ B HMDA]
2[ B ADA] [T HMDA] [T ADA] + 2[ B ADA] [T HMDA] + 2[ B HMDA] 0

U3 forward U3 reverse DIS-SALT = 1, ADA = 1, multiply group rate constant by 2.0 Reaction is first order with respect to water and polymer molecule following segment sequence: T-ADA : B-HMDA : T-ADA option 1: assume
P3,aa
with the
P3,aa
concentration = ADA concentration and use power-law
constants ADA = 1, H2O = 1* option 2: set power-law exponent for H2O = 1 and use the following equation, based on the most-probable distribution, to estimate concentration of P 3,aa (this equation can be implemented as a user rate constant).
[T ADA] 2[ B HMDA] [P ] = [T ADA] + 2[ B ADA] [T HMDA] + 2[ B HMDA]
3,aa 2 0
U4 forward
DIS-SALT = 1, HMDA = 1; multiply group rate constant by 2.0
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Reaction No. U4 reverse
Power-Law Exponents; Modeling Notes Reaction is first order with respect to water and polymer molecule following segment sequence: T-HMDA : B-ADA : T-HMDA option 1: assume
P3, BB
with the
P3, BB
concentration=HMDA concentration and use power-law
constants HMDA=1, H2O=1* option 2: set power-law exponent for H2O = 1 and use the following equation, based on the most-probable distribution, to estimate concentration of P 3, BB (this equation can be implemented as a user rate constant).
[T HMDA] 2[ B ADA] [P ] = [T HMDA] + 2[ B HMDA] [T ADA] + 2[ B ADA]
3,aa 2 0
U5 forward U5 reverse U6 forward U6 reverse
DIS-SALT = 1, T-ADA = 1 H2O = 1, T-ADA = 1, set power law constants for B-ADA, B-HMDA to 1E-10 to avoid numerical problems DIS-SALT = 1, T-HMDA = 1 H2O = 1, T-ADA = 1, set power law constants for B-ADA, B-HMDA to 1E-10 to avoid numerical problems
To avoid numerical problems, set power-law exponents to which do not appear in the rate expression
110 8
for reactants
0 = Concentration zeroth moment, mol/L (approximately = 0.5 * ([T-ADA] + [THMDA])
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Melt-Phase Polymerization
The best way to model the melt-phase polymerization of nylon-6,6 is to treat the HMDA and ADA segments as discreet molecular as shown in the components table on page 112. The following table shows the main reactions in the melt-phase polymerization of nylon-6,6:
Reaction Type Condensatio n Model-Generated Step-Growth Reactions (Define B-HMDA as NN-GRP, B-ADA as EE-GRP)
1. 2. 3. 4.
HMDA + ADA HMDA + T-ADA T-HMDA + ADA T-HMDA + T-ADA
T-HMDA : T-ADA + H2O T-HMDA : B-ADA + H2O B-HMDA : B-ADA + H2O B-HMDA + B-ADA + H2O T-ADA : B-HMDA + HMDA B-ADA : B-HMDA + HMDA B-ADA : B-HMDA + T-HMDA
ReArrangement
5. 6. 7.
T-HMDA + T-ADA : T-HMDA T-HMDA + B-ADA : T-HMDA T-HMDA + B-ADA : B-HMDA
These reactions are generated by the Step-Growth model if the HMDA repeat group is defined as a bifunctional nucleophile (NN-GRP), and the ADA repeat group as a bifunctional electrophile (EE-GRP). Side reactions that are not shown may be included in the model as user reactions. Rate constants can be assigned to reactions 1-7 using the identifiers for the detailed model summarized on page 115. A subset of these identifiers can be used to assign the same rate constant to several different reactions. For example, reactions 3-7 can be lumped together by specifying T-HMDA as the attacking nucleophilic species and by leaving the victim species identifiers blank (unspecified).
Melt Polycarbonate Reaction Kinetics

There is little information regarding melt-phase polymerization of polycarbonate available in the public domain. From what is available, it is clear that the chemistry of the melt-polycarbonate process follows the typical pattern for step-growth condensation involving two dissimilar monomers. The bisphenol-A monomer behaves as a bifunctional nucleophile, and the diphenyl carbonate monomer behaves as a bifunctional electrophile. The reactions generate phenol as a by-product. In later stages of the process, rearrangement reactions regenerate small amounts of bisphenol-A monomer. The following table summarizes the most convenient method for characterizing the components involved in the melt polycarbonate process:
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Component ID
Databank ID
Component Structure
Component Name
Components Common to Simplified and Detailed Approach DPC T-DPC B-DPC BPA T-BPA B-BPA PHOH none C7H5O2-E CO-R C15H16O2 C15H15O2-E C15H14O2-R C6H6O
O C O O C HO O O OH OH OH O O O C O
Diphenyl Carbonate Phenyl carbonate end group Carbonate repeat unit Bisphenol-A Bisphenol-A end group Bisphenol-A repeat unit Phenol
The following table shows the main reactions in this process. These reactions are generated by the model if the carbonate group is defined as a bifunctional electrophile (EE-GRP) and the BPA group as a bifunctional nucleophile (NN-GRP) .
Reaction Type Condensatio n Model-Generated Step-Growth Reactions (Define B-BPA as NN-GRP, B-DPC as EE-GRP)
1. 2. 3. 4.
BPA + DPC BPA + T-DPC T-BPA + DPC T-BPA + T-DPC
T-BPA : T-DPC + PHOH T-BPA : B-DPC + PHOH B-BPA : B-DPC + PHOH B-BPA + B-DPC + PHOH T-DPC : B-BPA + BPA B-DPC : B-BPA + BPA B-DPC : B-BPA + T-BPA
ReArrangement
5. 6. 7.
T-BPA + T-DPC : T-BPA T-BPA + B-DPC : T-BPA T-BPA + B-DPC : B-BPA
The following table shows how to assign rate constants to each of the reactions shown in the previous table:
Reaction No. Attacking Nucleophilic Species BPA BPA T-BPA Victim Electrophilic Species DPC T-DPC DPC Victim Nucleophilic Species none none none
1 forward 2 forward 3 forward
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4 forward 5 forward 6 forward 7 forward 1 reverse 2 reverse 3 reverse 4 reverse 5 reverse 6 reverse 7 reverse
T-BPA T-BPA T-BPA T-BPA PHOH PHOH PHOH PHOH BPA BPA T-BPA
T-DPC T-DPC B-DPC B-DPC T-DPC B-DPC T-DPC B-DPC T-DPC B-DPC B-DPC
none T-BPA T-BPA B-BPA T-BPA T-BPA B-BPA B-BPA B-BPA B-BPA B-BPA
Rate constants can be assigned to several by leaving some of the reaction identifiers unspecified. For example, the reverse reactions involving phenol can be lumped together by assigning phenol as the attacking nucleophilic species and by leaving the names of the victim species unspecified. The open literature does not describe the side reactions involved in this process, although side reactions are certainly known to exist. These side reactions can be added to the model as user reactions.
Model Features and Assumptions

Model Predictions
The step-growth model calculates the component reaction rates and the rate of change of the zeroth and first polymer moments ( 0 , 1 ) of the polymer chain length distribution. The number average polymer properties (Pn, Mn) are calculated from the moments. These component attributes can be used to calculate secondary properties, such as polymer viscosity, melting point, end group concentrations, intrinsic viscosity, melt flow index, etc. Correlations relating secondary properties to the polymer moments can be implemented using a User Prop-Set Property subroutine, as described in the Aspen Plus User Guide.
i
The rate of change of polymer mass is calculated as follows:

Nseg
Rp =
R
1
s ,i
* Mwi
Mw p
This is the sum of the rates of change of segment masses. Each segment type is assigned a value , which indicates the number of points of attachment connecting the segment to other segments in the polymer chain:
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Segment Type End Repeat Branch-3 Branch-4
1 2 3 4
The rate of change of the zeroth moment ( 0 ) is calculated from the rate of change of the first moment ( 1 ) and the segment type ():
0 1 1 = 2 t t t
The factor of accounts for the fact that each connection links two segments (without this correction the points of connection are counted twice). This method is best illustrated through these examples:
Valid Yes No Yes Yes Yes Yes Yes Yes Yes Reaction Type Initiation Initiation Propagation (addition) Propagation (insertion) Combination Combination Branching Branching Cross linking Stoichiometry
1
+2 +1 +1 +1 0 -1 +1 0 -1
+1 +1 +1 +1 +1 +0 +1 +1 +0
0
+1 0 0 0 -1 -1 0 -1 -1
M + M P2 M P1 Pn + M Pn +1
* * Pn + M Pn +1
M+ME+E MR E+MR+E MR E+ER+R E+ER R + M B3 + E R + E B3 + R R + R B4
Pn + Pm Pn + m Pn + Pm Pn + m Pn + M Pn +1 Pn + Pm Pn + m
Pn + Pm Pn + m
M = Monomer; E = End group segment; B3 = Branch-3 segment; B4 = Branch-4 segment
This method lets you specify most classes of reactions. However, special care must be taken to ensure that the reaction is defined in a manner that is consistent with the previous equation. By default, the model solves the zeroth moment (ZMOM) and segment flow rates (SFLOW attributes) as independent variables. This can cause a discrepancy between these variables, especially in flowsheets with high polymer recycle flow rates. This discrepancy, in turn, can lead to convergence problems in downstream reactors. To avoid this problem, you can force the model to calculate the zeroth moment directly from the segment flow rates by checking the explicitly solve
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zeroth moment option on the step-growth Options form. When this option is selected, the model calculates the zeroth moment as:
0 = 1 1 2
This option cannot be invoked if two or more reaction models are referenced from a single reactor block.
Phase Equilibria
The step-growth model can be used to simulate reactions in single-phase (vapor or liquid), two-phase (VL), or three-phase (VLL) systems. Each stepgrowth reaction model is associated with a particular reaction phase, specified on the Options sheet. The user can consider simultaneous reactions in multiple phases by referring to two or more reaction models in a reactor. Typical applications of this model include melt-phase polymerization and solution polymerization. Slurry, suspension, and emulsion processes involving step-growth kinetics can also be simulated with this model. Interfacial polymerization involves a solvent phase, an organic monomer phase, and a polymer phase. The reaction rate is usually limited by the rate of mass transfer of monomers from the organic phase to the reacting polymer phase. The mass-transfer limits across the liquid-liquid interface are not taken into account by the standard model. These systems can be simulated by developing a custom reactor model in Aspen Custom Modeler or Aspen Plus, or by writing an appropriate concentration basis subroutine for the stepgrowth model. Solid-state polymerization involves crystalline and amorphous solid polymer phases and a vapor phase. The reaction kinetics may be limited by the rate of mass transfer of volatile reaction by-products from the amorphous solid phase to the polymer phase. None of the standard reactor models in Aspen Polymers are designed for solid-state polymerization. Solid-state polymerization models can be developed in Aspen Custom Modeler and interfaced to the step-growth polymerization model through the Aspen Custom Modeler / Aspen Polymers Interface. Mass transfer limitations in thin-film or horizontal finishing reactors can be considered by customizing the Step-Growth model using the available concentration basis subroutine or by developing an appropriate user reactor model in Aspen Plus or Aspen Custom Modeler.
Reaction Mechanism
The Step-Growth reaction model applies to condensation polymerization. In the future the model will be extended to cover pseudocondensation and ringaddition polymerization. The model accounts for any combination of monofunctional and bifunctional monomers. Cyclic monomers and multifunctional monomers, however, are not included in the standard reaction scheme. User-defined stoichiometric reactions can be added to the model to account for reactions which are not included in the standard reaction scheme. These reactions use a power-law rate expression which can be extended to more
122
complex rate expressions through the application of a user-written Fortran subroutine.
Model Structure
This section outlines the structure of the Step-Growth kinetics model. It examines the theoretical framework in detail. The assumptions and limits of the algorithms are documented.
Reacting Groups and Species

The first step in the development of any process simulation model is to determine the list of components. In Aspen Polymers it is also important to decide how to characterize the polymer components. A polymer can be broken down into segments any number of ways. For example, the nylon-6 repeat unit can be treated as a segment, or it can be divided into two segments corresponding to the portions of the repeat unit which came from the diacid and diamine monomers.
Segments
The preferred method of segmenting the polymer component is to define segments corresponding to the monomers which are used to produce the polymer. This technique has two distinct advantages. First, the property models in Aspen Polymers use the monomer as a reference point for molecular size. Second, the reaction kinetics usually involve adding monomers to the end of growing polymer chains. Defining segments corresponding to the monomers makes it easy to write reactions corresponding to monomers and segments, for example monomer A segment A. The Step-Growth model assumes that the polymer is segmented in this manner. For monadic polymers such as nylon-6, this technique is straightforward. This method of segmenting the polymer is a bit unusual for dyadic polymers, such as PET, because it treats them as alternating copolymers. Thus, a molecule of PET with 100 PET units is defined as having a degree of polymerization of 200 in this model (100 terephthalate units and 100 glycol units). Monofunctional monomers, such as benzoic acid, always correspond to an end-group segment in the model. Bifunctional monomers can end up inside a linear polymer chain as a repeat unit, or may be located at the end of the chain as an end group. Each symmetric bifunctional monomer (diacids, diols, diamines, etc.) corresponds to one repeat segment and one end-group segment. Asymmetric bifunctional monomers (monomers with two different types of end groups) correspond to one repeat unit and two end-group segments. Multifunctional monomers can correspond to several segments, as shown:
Monomer Type Monomer Formula Corresponding Segment Formulas End-Groups Repeat Unit Branch-3 Branch-4
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Monomer Type Acid Ester Amine Alcohol Diacid Diester Carbonate Diamine Diol Amino acid
Monomer Formula
O R C OH O R C OR' R NH2 R OH O O HO C R C OH O O R'O C R C OR' O RO C OR H2N R NH2 HO R OH O H2N R C OH
Corresponding Segment Formulas End-Groups

O R C O R C R NH R O O O C R C OH O O C R C OR' O C OR HN R NH2 O R OH O H2N R C O HN R C OH O HO R C O O R C OH
Repeat Unit --------O O C R C O O C R C O C HN R NH O R O O HN R C
Branch-3 ---------------------
Branch-4 ---------------------
Lactic acid
O HO R C OH
O O R C
---
---
Branch agent Branch agent
R(OH)3 R(OH)4
~O-R(OH)2 ~O-R(OH)3
~O-R(OH)O~ ~O-R(OH)2O~
O O R O O O R O OH
--O O R O O
Reacting Functional Groups

The Step-Growth reaction model generates reactions based on the types of functional groups found in the reactants. The model includes a list of predefined group types, as shown:
Description Nucleophilic repeat units have two electron-strong sites. Electrophilic repeat units have two electron-weak sites. Mixed repeat units have one electrophilic site and one nucleophilic site. Type NN-GRP
HO(CH2)X OH HO OH
Examples
EE-GRP
O Cl C Cl O COH
HO C (CH2)X C OH EN-GRP O HO C (CH2)X OH HO
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Nucleophilic leaving groups are electron-strong end groups. Electrophilic leaving groups are electron-weak end groups. Nucleophilic modifiers are groups with a single nucleophilic site. Electrophilic modifiers are groups with a single electrophilic site.
N-GRP
O O HO C (CH2)X C OH
HO(CH2)X OH HO
O Cl C Cl
OH
E-GRP
NX-GRP OH OH
EX-GRP
O COH
O COH
Highlighted portion of component is the named reacting functional group.
Each functional group in the model is assigned a name and type. The names are used to distinguish between different groups with the same chemical functionality. The following table shows the types of functional groups found in common monomers and the condensate products:
Reacting Functional Groups Monomer Type Acid Ester Amine Alcohol Diacid Diester Carbonate Diamine Diol Amino acid Lactic acid Monomer Formula Leaving Groups Structure
O R C OH O R C OR' R NH2 R OH O O HO C R C OH O O R'O C R C OR' O RO C OR H2N R NH2 HO R OH O H2N R C OH O HO R C OH
Segment Groups Structure ------------------~OH (acid) ~OH (acid) Type ------------------N-GRP N-GRP Structure
O R C O R C R NH R O O O C R C O O C R C O C HN R NH O R O O HN R C O O R C
Type N-GRP N-GRP E-GRP E-GRP N-GRP N-GRP N-GRP E-GRP E-GRP E-GRP E-GRP
Type EX-GRP EX-GRP NX-GRP NX-GRP EE-GRP EE-GRP EE-GRP NN-GRP NN-GRP EN-GRP EN-GRP
~OH ~OR ~H ~H ~OH ~OR ~OR ~H ~H ~H (amine) ~H (alcohol)
Reacting Functional Groups In Common Types of Condensate Products
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Water Alcohol
H2O
RO-H
~H ~H
E-GRP E-GRP
~OH ~OR
N-GRP N-GRP
Reacting Species
Since polymer components do not have a fixed structure, polymerization reactions must be written in terms of the polymer segments. The segments and standard components that make up the step-growth reaction network are referred to as reacting species. Each of these reacting species is made up of one or more reacting functional groups. Once the reacting groups are defined, the structure of each reacting species is specified by defining the number of each reacting group in each reacting species. It is not necessary to specify a zero when a particular group is not in the species being defined.
Species Structure Validity

The model checks the species structures to verify they are valid and to see if there are any missing species. Species structures are considered valid if they follow these rules: Species may not be oligomer or polymer components. Species may include one EE-GRP, NN-GRP, or EN-GRP, but no species may have more than one of these three group types. Species may not contain more than one of any of these three groups. Species which are end group segments must include one E-GRP or one NGRP. Species which are repeat segments may not include an E-GRP or N-GRP. Species which are monomers must have a balanced number of electrophilic groups and nucleophilic groups. Structures are unique - no two species may have the same structure.
The model determines every valid combination of the specified functional groups. Any combination which is not represented by a species structure is assumed to be a missing component. The model reports a warning message describing the structure of the species which was not specified and drops all reactions which would have involved this component. You can choose to ignore this warning if the missing component is unimportant in the process being simulated.
Oligomer Fractionation
You can choose to include one or more oligomer components in the model. When this feature is used, the model will fractionate the polymer distribution between the polymer component and the various oligomer components. The fractionation algorithm assumes that the polymer follows the most probable distribution. These assumptions are valid when the reactions are reversible
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and when the rate of rearrangement reactions is faster than the rate of the condensation reactions. The oligomer feature can be used to track the loss of volatile short-chain oligomers from the polymer solution or melt. It can also be used to estimate oligomer concentrations to calculate reaction rates for ring closing reactions or other reactions that require a particular sequence of segments. Tracking oligomers, however, does require more simulation time and may make the model more difficult to converge. The Options form lets you adjust the tolerance for the oligomer fractionation calculations. When several oligomers are tracked simultaneously it may be necessary to reduce the tolerance to improve reactor convergence. The logic of the step-growth oligomer fractionation algorithm is summarized here:
Assumptions Polymer molecules consist of alternating nucleophilic and electrophilic segments Repeat segments in AB polymers, which are made up of EN-GRP groups, act as both a nucleophile and an electrophile. The end groups act as either electrophilic or nucleophilic segments, depending on which leaving group is attached to the end. The probability of a particular segment being in a given point in the segment sequence is determined by the concentration of that segment and the concentration of all other segments of that type (note: this assumption is equivalent to assuming the most-probable distribution). Equation Definition of probability factors used to determine probability of a given sequence of segments:
Pa =
fa N a i f i N i
Pb =
f b Eb j f jEj
Pa
= = = =
Probability that nucleophilic segment a occupies the next nucleophilic position Probability that electrophilic segment b occupies the next electrophilic Number of similar points of attachment in nucleophilic segment a (= 2 for Number of similar points of attachment in electrophilic segment b (= 2 for
in the chain
Pb fa
fb Na
position in the chain repeat segments which are composed of an NN-GRP) repeat segments which are composed of an EE-GRP) = Concentration of nucleophilic segment a = Concentration of electrophilic segment b
Eb
i j
= Index corresponding to list of all nucleophilic segments = Index corresponding to list of all electrophilic segments
Example 1: calculation of expected concentration of oligomer with a sequence ab
Cab=Pa Pb 0
Cab
= Expected oligomer concentration
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= Concentration zeroth moment of polymer (concentration of all polymer
molecules) Example 2: calculation of expected concentration of oligomer with a sequence aBABa
CaBABa=Pa2 PB2 PA 0
Reaction Stoichiometry Generation

The model predicts the stoichiometry of each step-growth reaction based on the structure of each of the reactants. The step-growth reaction generation algorithm is summarized here:
Reaction Type Condensation Monomer Addition Reaction Scheme Reaction Generation Algorithm Find every combination by which nucleophilic monomers, M xa , or end
M xa + M yb P2, xy + Wab Pn , xa + M yb Pn +1, xy + Wab M xa + Pn , yb Pn +1, yx + Wab
Pxa , can react with electrophilic monomers, M yb , or end segments, Pyb , to give a condensate molecule, Wab
segments Find every combination by which nucleophilic end segments, P xa , can react with end segments, condensate molecule,
Condensation Polymer Addition
Pn , xa + Pm, yb Pn + m, xy + Wab
Pyb , to give a
Wab
Reverse Condensation - Terminal Monomer Loss
Wab + P2, xy M xa + M yb Wab + Pn , xy Pn1, xa + M yb
Find every combination by which a condensate molecule, Wab , can react with a polymer molecule at the boundary between a nucleophilic repeat segment, x, and an electrophilic end group segment, y Find every combination by which a condensate molecule, Wab , can react with a polymer molecule at the boundary between a nucleophilic repeat segment, x, and an electrophilic repeat segment, y
Reverse Condensation - Scission
Wab + Pn , xy Pn m, xa + Pm, yb
Forward Polycondensation
Pn , za + Pm, yx Pn + m1, yz + M xa
Find every combination by which a nucleophilic end group segment, P za , can react with a polymer molecule at the boundary between a nucleophilic repeat segment, x, and an electrophilic end segment, y
Reverse Polycondensation
M za + Pn , yx Pn m, yz + Pm+1, xa
Find every combination by which a nucleophilic monomer, M xa , can react with a polymer molecule at the
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boundary between a nucleophilic repeat segment, x, and an electrophilic end segment, y Re-arrangement
Pn , za + Pm, xy Pn+ m q , yz + Pq , xa
Find every combination by which a nucleophilic end group segment, P za , can react with a polymer molecule at the boundary between a nucleophilic repeat segment, x, and an electrophilic repeat segment, y
By default, the step-growth model generates all types of step-growth reactions described above. You may turn off the reaction generation for a particular class of reactions by clearing the reaction from the Reaction Options section of the Options form.
Model-Generated Reactions
There are two steps required to assign rate constants to model generated reactions. First, the rate constant values are specified in the Step-Growth Rate Constant form (SG-RATE-CON sentence). Then each set of rate constants is assigned a number for identification. Once the rate constants sets are defined, they can be assigned to the generated reactions.
Rate Expression for Model Generated Reactions

The Step-Growth reactions model uses a modified power law rate expression, shown here:
Equation
Tref specified
rate = [ Nucl ][ Elec] f n f e P Ci ko i e

i
Eai 1 1 RT T Tref
T i T U ( flagi ) ref
Tref unspecified
Nomenclature Symbol [Nucl] [Elec] Description
rate = [ Nucl ][ Elec ] f n f e P Ci ko i e

i
Eai RT
T bi U ( flagi )
Concentration of the attacking nucleophilic species, mol/L* Concentration of the attacking electrophilic species, mol/L* Number of electrophilic leaving groups in the attacking nucleophilic species. This factor is 2 for diol and diamine monomers.
fn
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fe
In reactions involving two victim species,
fe fe
is the number of electrophilic
groups in the electrophilic species. This factor is 2 for repeat units which contain EE-GRP groups. In reactions involving one victim species, is the number of nucleophilic leaving groups in the electrophilic species. This factor is 2 for diacid, diester, and carbonate monomers. P In reactions involving two victim species, P is the probability of the victim nucleophilic species being adjacent to the victim electrophilic species. This probability factor is calculated by the model assuming the most probable distribution:
P=
f vns N vns i f i N i
= Number of similar points of attachment in victim nucleophilic segment (= 2 for NN-GRP repeat segments, 1 for all others) = Concentration of victim nucleophilic segment
where:
f vns
N vns
i Symbol
i = Index corresponding to list of all nucleophilic segments Index corresponding to the rate constant set number. The summation is performed over the specified list of rate constant set numbers. Description Catalyst concentration for rate constant set i. If the catalyst species is specified, this is the concentration of the species. If the catalyst group is specified, this the group concentration. If both species and group are specified, this is the concentration of the species times the number of the specified group in the specified species. If the catalyst is not specified, this factor is set to one. Pre-exponential factor in user-specified inverse-time units* Activation energy in user-specified mole-enthalpy units (default =0) Temperature exponent (default = 0) Universal gas constant in units consistent with the specified activation energy Temperature, K Optional reference temperature. Units may be specified, and they are converted to K inside the model. User flag for rate constant set i. This flag points to an element of the user rate constant array. User rate constant vector calculated by the optional user rate constant subroutine. The user flag indicates the element number in this array which is used in a given rate expression. When the user flag is not specified, or when the user rate constant routine is not present, this parameter is set to 1.0.
Ci
ko
Ea b R T
Tref
flag U
* The concentration basis may be changed to other units using the Concentration basis field on the Options sheet or using the optional concentration basis subroutine.
The reactions follow second order kinetics: one order with respect to the nucleophilic reactant and one order with respect to the electrophilic reactant.
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Catalysts may make the reaction third order (one order with respect to catalyst). The rate constants for the model-generated reactions are assumed to be on a functional group basis. The model applies correction factors to account for the number of like functional groups in each of the reactants. For example, in a reaction between a diol monomer and a diacid monomer, the specified rate constant is multiplied by four to account for the two acid groups in the diacid and the two alcohol groups in the diol. Some reactions occur inside polymer chains at the intersection of two segments. The model applies a probability factor to estimate the concentration of the given segment pair. This probability is based on the most probable distribution. It assumes that the segments in the polymer alternate between nucleophilic segments and electrophilic segments. Repeat segments composed of an EN-GRP functional group behave as both nucleophiles and electrophiles, so these segments can alternate with themselves. The standard rate expression is modified using the optional user rate constant feature. The rate constant form includes a parameter called the user flag which identifies an element in an array of user rate constants. This array is calculated by a user-written Fortran subroutine. The standard rate expression is multiplied by the user rate constants.
Assignment of Rate Constants to ModelGenerated Reactions

Six qualifiers are used to assign each set of rate constants to internallygenerated step-growth reactions, the: Attacking nucleophilic reactant name (A-NUCL-SPEC) Attacking electrophilic leaving group name (A-ELEC-GRP) Victim electrophilic reactant name (V-ELEC-SPEC) Victim nucleophilic group name (V-NUCL-GRP) Victim electrophilic species name (V-ELEC-SPEC) Victim electrophilic group name (V-ELEC-GRP)
The following table contains an example illustrating how these identifiers are used to distinguish between reactions. Note that the victim electrophilic species is only used for reactions which occur at the intersection of two segments in a polymer molecule.
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O HO(CH2)2OH + HOC O O(CH2)2OH + HOC O HO(CH2)2OH + HOC O O(CH2)2OH + HOC O HO(CH2)2OH + HOC O HO(CH2)2OH + HOC
O COH O COH O C O C O COCH3 O COCH3
1 2 3 4 5 6 7 8 9 10 11 12
O HO(CH2)2O C O O(CH2)2O C O HO(CH2)2O C O O(CH2)2O C O HO(CH2)2O C O HO(CH2)2O C
O COH O COH O C O C
+ H2O + H2O + H2O + H2O
O COCH3 + H2O O COH + CH3OH
Reaction Identifiers Attacking Species Reaction 1 2 3 4 5 6 7 8 9 10 11 12 A-NuclSpec A-Elec-Grp alcohol ~H ~H in alcohol ~H Victim Species V-Elec-Spec
O HOC O COH
V-Elec-Grp
O C O C O C O C
V-Nucl-Spec none
V-Nucl-Grp ~OH in acid
HO(CH2)2OH ~H in H2O ~O(CH2)2OH H2O
O C
O COH
~O(CH2)2OH
none
~O(CH2)2O~
~OH in acid
O HOC
O C O C O C O C O C
O HOC
O COH
O COH O COH O C O COH O C
O COCH3
O C
O C O C O C O C O C O C O C O C O C
O C
O C O C O C O C O C O C O C O C O C
~O(CH2)2O~
none
~O(CH2)2O~
~OH in acid
HO(CH2)2OH ~H in H2O ~O(CH2)2OH H2O

~H
alcohol
~O(CH2)2OH
none
~O(CH2)2O~
~OH in acid
~H in alcohol ~H
~O(CH2)2O~
none
~O(CH2)2O~
~OH in acid
HO(CH2)2OH ~H in H2O
~H
alcohol
O C O HOC O C
O COCH3 O COCH3 O COCH3
~O(CH2)2OH
none
~O(CH2)2O~ ~OCH3 ~O(CH2)2O~
HO(CH2)2OH ~H in CH3OH
~H
alcohol
~O(CH2)2OH
It is not necessary to specify all of the reaction identifiers. For example, the only time it is necessary to specify the attacking nucleophilic species and the attacking electrophilic group is when this species contains more than one type of group and the two groups are not equally reactive.
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Sets of reactions may be grouped together by making more general specifications. For example, if the attacking electrophilic group and victim nucleophilic group are the only two identifiers specified, then the rate constants are assigned to all reactions involving the named groups. When more than one reaction set is specified, the sets are processed in reaction set number order, for example, reaction set one is processed before reaction set two, three, etc. When a match is found for a given reaction, the rate constant assignment algorithm moves to the next reaction, ignoring the remaining reaction sets. The algorithm is designed to find the special cases first, and then move on to the general cases. Several examples illustrating the concept of rate constant assignment follow. These examples are based on the set of reactions provided previously.
Reaction Identifiers RxnSets Case 1 1 Case 2 RCSets 1, 2 A-NuclSpec unspecified A-ElecGrp unspecified V-ElecSpec unspecified V-ElecGrp unspecified V-NuclSpec unspecified V-NuclGrp unspecified
Assign rate constant sets 1 and 2 to all of the model-generated reactions Assign rate constant sets 1 and 2 to reactions between alcohol groups in ethylene glycol and any acid groups Assign rate constant sets 3 and 4 to reactions between alcohol groups in the polymer and any acid groups Assign rate constant set 5 to reverse reactions involving methanol Assign rate constant set 6 to reverse reactions involving water
1 2 3 4 Case 3
1, 2 3, 4 5 6
HO(CH2)2OH ~O(CH2)2OH H2O CH3OH
unspecified unspecified unspecified unspecified
~OH in acid ~OH in acid unspecified unspecified
Assign rate constant sets 1 and 2 to reactions between alcohol groups in ethylene glycol and terephthalic acid Assign rate constant sets 3 and 4 to all other reactions involving acid groups Assign rate constant set 5 to reactions between water and glycol end groups Assign rate constant set 6 to all other reverse reactions involving water Assign rate constant set 7 to reactions between ethylene glycol and the methylester end groups in the polymer Assign rate constant 8 to all other reactions
1 2 3 4 5
1, 2 3, 4 5 6 7
HO(CH2)2OH
unspecified
unspecified unspecified unspecified unspecified unspecified
O HOC
O COH
unspecified unspecified unspecified unspecified unspecified
unspecified unspecified
unspecified ~OH in acid unspecified unspecified
unspecified unspecified unspecified

O C O COCH3
H2O H2O HO(CH2)2OH
~O(CH2)2OH
unspecified unspecified
~OCH3
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unspecified
unspecified
unspecified
unspecified
unspecified
unspecified
User Reactions
The model cannot predict all types of reactions based on the specified structures. Reactions which are not predicted by the model can be included as user-specified reactions. These can include thermal scission reactions, monomer or segment reformation, end-group modification, etc. The user-specified reactions apply a modified power-law rate expression, as shown here:
Equation
Tref specified Tref unspecified
k net ,i = [Catalyst i ] ko i e
Eai 1 1 R T Tref
T T ref
U ( flag i )
bi
k net ,i = [Catalysti ] ko i e
Eai RT
T bi U ( flag i )
j
Assign User Rate Constants is used: Assign User Rate Constants is not used: Nomenclature Symbol m i j Description User reaction number Rate constant set number Component number Product operator
ratem = activitym
ratem
( C ) k = ( C )k (m = i)
amj j i net ,i
j amj j net ,i
Cj
Concentration* of component j, mol/L Catalyst order term for catalyst i (default = 1) Power-law exponent for component j in reaction m Pre-exponential factor in user-specified inverse-time and concentration units* Net rate constant for set i Activation energy in user-specified mole-enthalpy units (default =0) Temperature exponent (default = 0) Universal gas constant in units consistent with the specified activation energy Temperature, K Optional reference temperature. Units may be specified, they are converted to K in the model. User flag for rate constant set i. This flag points to an element of the user rate constant array. User rate constant vector calculated by the optional user rate constant subroutine. The
mj
ko knet ,i
Ea b R T
Tref
flag U
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user flag indicates the element number in this array which is used in a given rate expression. When the user flag is not specified, or when the user rate constant routine is not present, this parameter is set to 1.0.
The concentration basis may be changed to other units using the Concentration basis field on the Options sheet or using the optional concentration basis subroutine.
You can modify the standard rate expression using the optional user rate constant feature. The rate constant form includes a parameter called the user flag which identifies an element in an array of user rate constants. This array is calculated by a user-written Fortran subroutine. The standard rate expression is multiplied by the user rate constants as shown.
Assignment of Rate Constants to User Specified Reactions

There are two options for assigning rate constants to user-specified reactions. By default, the model assumes there is exactly one set of rate constants for each reaction (for example, rate constant set i is used for reaction i).
Alternately, you may use the Assign User Rate Constant sheet to assign one or more sets of rate constants to each reaction. This feature is convenient in two situations: Models with a large number of user side reactions when the rate constants of the various reactions are equal or are related to each other algebraically. Reactions catalyzed by several catalysts simultaneously.
Conventional and Power-Law Components

Conventional components and segments can appear as reactants or products in the reaction stoichiometry. Each reaction must be mass balanced (the mass of the products must be equal to the mass of the reactants). The power-law components can include conventional components, segments, or oligomers. Power-law coefficients can be specified for components which do not appear in the reaction stoichiometry, such as catalysts or inhibitors. The model allows the reactants to have power-law constants of zero, but this is not recommended because it can lead to numerical problems in the reactor models. For example, if a reaction AB is zeroth order with respect to component A, the reaction could have a positive rate even when component A is not present. This causes non-negativity violation integrator errors in RPlug and RBatch and causes convergence errors in RCSTR. To avoid these -8 problems, specify a very small power-law coefficient, such as 1 10 . A user-specified reaction can be accelerated by several different catalysts. In this situation, use the Assign User Rate Constants form to link multiple sets of rate constants to each reaction. Each set of rate constants may be associated with a particular catalyst.
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When the side reaction kinetics are complicated, it can be easier to write the kinetics in the context of the available user kinetic subroutine. This subroutine is called from the Step-Growth reaction model. The argument list for this user-written Fortran subroutine includes the step-growth rate constants, user rate constants, species concentrations, group concentrations, species structures (number of each group in each species), and others.
User Subroutines
The Step-Growth model can be customized by applying user-written subroutines. There are three types of subroutines available. The concentration basis for the model can be changed through a user basis subroutine. This subroutine can also be used to calculate the volume (RCSTR and RBatch) or area (RPlug) of the reacting phase. A user rate-constant subroutine can be used to extend the standard rate expression for model-generated or userspecified reactions. A user kinetics routine can be used to add reactions to the model which are too difficult to represent using the power-law approach, or to calculate user attributes for polymer characteristics which are not tracked by Aspen Polymers. These routines can be used together in any combination.
User Basis Subroutine

The user basis subroutine can be used to calculate the component concentrations and the reacting-phase volume (area) basis used in the component and attribute conservation equations. Use this subroutine when rate constants are available in unusual concentration units not found in Aspen Polymers, or when the reacting phase volume or area calculated by the reactor model is not consistent with the real reactor (for example, in plug flow reactors with fixed liquid level). This subroutine can also be used in conjunction with Fortran blocks and user component attributes to calculate mass-transfer rates and to account for the influence of mass-transfer limitations on the component concentrations in the reacting phase. The argument list for the user basis routine is provided here. This argument list is prepared in a Fortran template called USRMTS.F, which is delivered with Aspen Polymers.
User Subroutine Arguments
SUBROUTINE 1 2 3 4 5 6 7 8 9 * 1 2
USRMTS SOUT, IDSCC, NINTB, INTM, NWORK, X1, FLOWL1, VL1, VL1RX, IFLRTN, VBASIS, TIME
NSUBS, NPO, INTB, NREALM, WORK, X2, FLOWL2, VL2, VL2RX, CRATES, IPOLY,
IDXSUB, NBOPST, NREALB, REALM, NCPM, Y, FLOWV, VV, VVAPRX, NTCAT, NSEG,
ITYPE, NIDS, REALB, NIWORK, IDXM, DUM1, FLOWS, VSALT, VSLTRX, RATCAT, IDXSEG,
XMW, IDS, NINTM, IWORK, X, FLOWL, VLQ, VLIQRX, RFLRTN, CSS, AXPOS,
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Argument Descriptions
Variable SOUT NSUBS IDXSUB ITYPE Usage Input Input Input Input Type REAL*8 INTEGER INTEGER INTEGER NSUBS NSUBS Dimension (1) Description Stream vector Number of substreams in stream vector Location of substreams in stream vector Substream type vector 1=MIXED 2=CISOLID 3=NC XMW IDSCC NPO NBOPST NIDS NINTB INTB NREALB REALB NINTM INTM NREALM REALM NIWORK IWORK NWORK WORK NCPM Input Input Input Input Input Input Retention Input Retention Input Retention Input Retention Input Work Input Work Input REAL*8 HOLLERITH INTEGER INTEGER INTEGER INTEGER INTEGER INTEGER REAL*8 INTEGER INTEGER INTEGER REAL*8 INTEGER INTEGER INTEGER REAL*8 INTEGER NWORK NIWORK NREALM NINTM NREALB NINTB 6, NPO NCC 2,NCC Conventional component molecular weights Conventional component ID array Number of property methods Property method array Number of reaction model IDs User-specified length of INTB array Reactor block integer parameters (See Integer and Real Parameters, page 151) User-specified length of REALB array Reactor block real parameters (See Integer and Real Parameters, page 151) User-specified length of INTM array User subroutine integer parameters (See Integer and Real Parameters, page 151) User-specified length of REALM array User subroutine real parameters (See Integer and Real Parameters, page 151) Length of user subroutine integer work vector User subroutine integer work vector (See Local Work Arrays, page 151) Length of user subroutine real work vector User subroutine integer work vector (See Local Work Arrays, page 151) Number of components present in the mixed substream (See Packed Vectors, page 151) NCPM NCPM NCPM NCPM NCPM (1) Component sequence numbers (See Packed Vectors, page 151) Overall liquid mole fractions First liquid mole fractions Second liquid mole fractions Vapor phase mole fractions Argument reserved for future application Total liquid flow rate, kmol/sec
IDXM X X1 X2 Y Dum1 FLOWL
Input Input Input Input Input Dummy Input
REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8
137
Variable FLOWL1 FLOWL2 FLOWV FLOWS VL VL1 VL2 VV VSALT VLIQRX VL1RX VL2RX VVAPRX VSLTRX RFLRTN IFLRTN CRATES NTCAT RATCAT CSS VBASIS IPOLY NSEG IDXSEG AXPOS TIME
Usage Input Input Input Input Input Input Input Input Input Input Input Input Input Input Retention Retention Output Input Output Output Output Input Input Input Input Input
Type REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 INTEGER REAL*8 INTEGER REAL*8 REAL*8 REAL*8 INTEGER INTEGER INTEGER REAL*8 REAL*8
Dimension
Description First liquid flow rate, kmol/sec Second liquid flow rate, kmol/sec Vapor flow rate, kmol/sec Salt flow rate, kmol/sec Total liquid molar volume, m3/ kmol First liquid molar volume, m3/ kmol Second liquid molar volume, m3/ kmol Vapor molar volume, m3/ kmol Salt molar volume, m3/ kmol Volume* of liquid in reactor, m3 Volume* of first liquid in reactor, m3 Volume* of second liquid in reactor, m3 Volume* of vapor in reactor, m3 Volume* of salt in reactor, m3
(3, 1) (3, 1) NCC NTCAT NCC
Real retention for FLASH Integer retention for FLASH Component rates of change, kmol/m3-sec Number of component attributes Component attribute rates of change, cat/m3-sec Concentration vector for the active phase Holdup basis used to calculate reaction rates* Reacting polymer component index Number of segment components
NSEG
Segment component index vector RPlug only: axial position, m RBatch only: time, sec
When using molar concentrations, this parameter is volume of the reacting phase in m 3 in RCSTR and RBatch or the cross-sectional area of the reacting phase in m3 in RPlug.
Example 1 illustrates how to use the user basis routine to convert the concentration basis from the standard molar concentration basis (mol/L) to a mass concentration basis (mol/kg). (Note: the current version of Aspen Polymers supports several concentration basis through the CONC-BASIS keyword located on the Options form, we retain this example as a demonstration). Using these units, the reaction rates are calculated in units of mol/kg-sec. These rates are multiplied by the holdup basis (VBASIS) for the reactor in the Step-Growth model. For this reason, the holdup basis must be consistent with the concentration basis, e.g., it must be in kg. The holdup basis pertains to the reacting phase, it does not include the phases which do not react.
138
Example 1: A User Basis Routine For the Mass-Concentration Basis
Ci = Ci Xi
Xi M Liquid
= Mass-concentration of component i = Mole fraction of component i liquid phase
M Liquid = Average molecular weight of components in the

CALL PPMON_VOLL( TEMP, PRES, X, NCPMX, IDXM, 1 NBOPST, GLOBAL_LDIAG, 1, VLQ, DVS, KER) C-unpack the mole fraction vector into the molar concentrations... CALL SHS_UNPACK ( X , NCPMX, IDXM, CSS ) C --------------------------------------------------------------C C concentration (mole/kg)=(mole I / mole liquid )*( mole liquid/kg) C C --------------------------------------------------------------DO 10 I = 1, NCOMP_NCC CSS(I) = CSS(I) * 1.D3 / STWORK_XMWL 10 CONTINUE C --------------------------------------------------------------C C reacting phase basis must be consistent with concentration basis (kg) C liquid mass inventory = liquid volume * density C C --------------------------------------------------------------VBASIS = VLIQRX * STWORK_XMWL * 1.D-3 / VLQ RETURN Note: This excerpt does not include the argument list and declarations section of the user basis routine. The plug flow reactor model in Aspen Plus assumes that the vapor and liquid move at the same velocity through the reactor (e.g., no-slip conditions). This assumption is not consistent with the physical reality of polymer finishing reactors or wiped-film evaporators. The subroutine in Example 2 gets around the no-slip assumption in RPlug, allowing you to specify the volume occupied by the liquid phase. In this example, the user specifies the first integer argument in the RPlug block as 1 and specifies the first real argument as the volume fraction of the reactor occupied by the liquid phase. Example 2: A User Basis Routine to Specify Liquid Volume in RPlug UFRAC = 1.D0 IF ( REALB(1) .NE. RGLOB_RMISS ) UFRAC = REALB(1) IF ( INTB(1).EQ.1 ) THEN
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C - unpack the mole fraction vector into the molar concentrations... CALL SHS_UNPACK ( X , NCPMX, IDXM, CSS ) C - concentration = mole fraction divided by molar volume of phase DO 20 I = 1, NCOMP_NCC CSS(I) = CSS(I) / VLQ 20 CONTINUE C - multiply total reactor volume by user-specified volume fraction VBASIS = ( VLIQRX + VVAPRX ) * UFRAC C - this line makes RPlug calculate liquid residence time (not L+V) SOUT(NCOMP_NCC+8)=(SOUT(NCOMP_NCC+9)/ SOUT(NCOMP_NCC+6)) / VLQ RETURN END IF Note: This excerpt does not include the argument list and declarations section of the user basis routine.
User Rate-Constant Subroutine

The user rate constant subroutine can be used to modify rate constant parameters for model-generated and user-specified reactions. Use this routine to modify the standard power-law rate expression for non-ideal reaction kinetics. The user rate constant feature can be used to modify the standard power-law rate expression. This subroutine returns a list of real values which are stored in an array RCUSER. The length of this array is defined by the keyword NURC (number of user rate constants) in the user rate constant subroutine form (USER-VECS secondary keyword). Each of the elements in the user rate constant array can store a different user rate constant. The USER-FLAG keyword in the SG-RATE-CON and RATE-CON forms is used to specify which user rate constant is used with a particular set of rate constants. Elements 1-NURC of RCUSER are calculated by a user rate-constant subroutine. The standard rate expression is multiplied by the USER-FLAGth element of the user rate constant vector RCUSER. By default, the USER-FLAG keyword is set to zero. The zeroth element of the RCUSER array is set to a value of 1.0, so the rate expression remains unmodified unless the USERFLAG keyword is specified. The argument list for the subroutine is provided here. This argument list is prepared in a Fortran template called USRRCS.F, which is delivered with Aspen Polymers.
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SUBROUTINE USRRCS 1 2 3 4 5 6 7 8 9 * 1 SOUT, IDSCC, NINTB, INTR, NWORK, X1, VL1, NSEG, NGROUP, CSS, RCUSER, NSUBS, NPO, INTB, NREALR, WORK, X2, VL2, IDXSEG, IDGRP, CGROUP, CATWT IDXSUB, NBOPST, NREALB, REALR, NCPM, Y, VV, NOLIG, NSPEC, TEMP, ) ITYPE, NIDS, REALB, NIWORK, IDXM, DUM1, VSALT, IDXOLI, IDXSPC, PRES, XMW, IDS, NINTR, IWORK, X, VL, IPOLY, NSGOLG, NFGSPC, NURC,
Variable SOUT NSUBS IDXSUB ITYPE Usage Input Input Input Input Type REAL*8 INTEGER INTEGER INTEGER NSUBS NSUBS Dimension (1) Description Stream vector Number of substreams in stream vector Location of substreams in stream vector Substream type vector 1=MIXED 2=CISOLID 3=NC XMW IDSCC NPO NBOPST NIDS IDS Input Input Input Input Input Input REAL*8 HOLLERITH INTEGER INTEGER INTEGER HOLLERITH 2,NIDS 6, NPO NCC 2, NCC Conventional component molecular weights Conventional component ID array Number of property methods Property method array (used by FLASH) Number of reaction model IDs Reaction model ID list: i,1 reactor block ID i,2 reactor block type i,3 reaction block ID i,4 reaction block type i,5 user subroutine ID NINTB INTB NREALB REALB NINTR INTR Input Retention Input Retention Input Retention INTEGER INTEGER INTEGER REAL*8 INTEGER INTEGER NINTR NREALB NINTB User-specified length of INTB array Reactor block integer parameters (See Integer and Real Parameters, page 151) User-specified length of REALB array Reactor block real parameters (See Integer and Real Parameters, page 151) User-specified length of INTM array User subroutine integer parameters (See Integer and Real Parameters, page 151)
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Variable NREALR REALR NIWORK IWORK NWORK WORK NCPM
Usage Input Retention Input Work Input Work Input
Type INTEGER REAL*8 INTEGER INTEGER INTEGER REAL*8 INTEGER
Dimension NREALR
Description User-specified length of REALM array User subroutine real parameters (See Integer and Real Parameters, page 151) Length of user subroutine integer work vector
NIWORK
User subroutine integer work vector (See Local Work Arrays, page 151) Length of user subroutine real work vector
NWORK
User subroutine integer work vector (See Local Work Arrays, page 151) Number of components present in the mixed substream (See Packed Vectors, page 151)
IDXM X X1 X2 Y Dum1 VL VL1 VL2 VV VSALT IPOLY NSEG IDXSEG NOLIG IDXOLI NSGOLG
Input Input Input Input Input Dummy Input Input Input Input Input Input Input Input Input Input Input
REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 INTEGER INTEGER INTEGER INTEGER INTEGER INTEGER
NCPM NCPM NCPM NCPM NCPM (1)
Component sequence numbers (See Packed Vectors, page 151) Overall liquid mole fractions First liquid mole fractions Second liquid mole fractions Vapor phase mole fractions Argument reserved for future application Total liquid molar volume, m3/kmol First liquid molar volume, m3/kmol Second liquid molar volume, m3/kmol Vapor molar volume, m3/kmol Salt molar volume, m3/kmol Reacting polymer component index Number of segment components
NSEG NOLIG NSEG, NOLIG
Segment component index vector Number of oligomer components Oligomer component index vector Segment frequency vector: contains number of each segment in each oligomer Number of functional groups Functional group ID vector Number of reacting species Reacting species component index vector Group frequency vector: contains number of each functional group in each species Concentration vector for reacting species Concentration vector for reacting groups Temperature, K Pressure, Pa
NGROUP IDGRP NSPEC IDXSPC NFGSPC
Input Input Input Input Input
INTEGER HOLLERITH INTEGER INTEGER INTEGER NSPEC NSPEC, NGROUP NCC NGROUP NGROUP
CSS CGROUP TEMP PRES
Input Input Input Input
REAL*8 REAL*8 REAL*8 REAL*8
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Variable NURC RCUSER CATWT
Usage Input Output Input
Type INTEGER REAL*8 REAL*8
Dimension
Description Number of user rate constants (See User Rate-Constant Subroutine, page 140)
NURC
User rate constant vector (See User Rate-Constant Subroutine, page 140) Catalyst weight, kg (in RPLUG, weight/length)
Example 3 illustrates how to use this subroutine to implement complex rate expressions in the Step-Growth model. Example 3: Implementing a Non-Ideal Rate Expression Suppose a side reaction QZ is first order with respect to component Q and first order with respect to a catalyst C. The effectiveness of the catalyst is reduced by inhibitor I according to the following equation:
[C ] = 1 + ([aC+ bT])[ I ]
actual eff
Where:
[Ceff ]
= Effective catalyst concentration, mol/L
[Cactual ] = Actual catalyst concentration, mol/L
[I ]
T a,b
= Inhibitor concentration, mol/L = Temperature, K = Equation parameters
The net rate expression can thus be written as:
rate = [Q]
Where:
1 + ( a + bT )[ I ]
[C ]
actual
ko e
E* 1 1 R T Tref
ko
E* R
= Pre-exponential factor, (L/mol)/sec = Activation energy = Gas law constant = Reference temperature for
Tref
[Q]
ko
= Concentration of component Q, mol/L
The standard rate expression for side reactions is:
rate = koe
E* 1 1 R T Tref
Ci i * U ( j ) i
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Where: = Product operator = Concentration of component i = Power-law exponent for component i = User rate constant = User rate-constant flag
3
Ci i
U j
Suppose the rate constant for the uninhibited reaction is 3 10 (L/mol)/min at 150C, with an activation energy of 20 kcal/mol, and the inhibition rate constants are A=0.20 L/mol, B=0.001 L/mol-K. The stoichiometric coefficients and power-law exponents are specified directly in the Stoic and PowLaw-Exp keywords. The Arrehnius rate parameters and reference temperature are also specified directly in the model. The parameters for the user rate constant equation can be specified using the optional REALRC list. Including the parameters in the REALRC list allows the model user to adjust these parameters using the standard variable accessing tools, such as Sensitivity, Design-Specification, and Data-Regression. The resulting model input is summarized below: USER-VECS NREALRC=2 NUSERRC=1 REALRC VALUE-LIST=0.2D0 0.001D0 STOIC 1 Q -1.0 / Z 1.0 POWLAW-EXP 1 Q 1.0 / C 1.0 RATE-CON 1 3D-3<1/MIN> 20.000<kcal/mol> TREF=150.0<C> URATECON=1 The power-law term from this equation is:
rate = koe
Where:
E* 1 1 R T Tref
[C][ Q]
[Q] = Concentration of component Q, mol/L [C] = Catalyst concentration, mol/L
ko = Pre-exponential factor
Thus, the required user rate constant is:
U ( j = 1) =
Where: [I] T a, b
1 (1 + ( a + bT )[ I ]
An excerpt from the user rate constant subroutine for this equation is shown below:
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- Component Name INTEGER ID_IN(2) DATA ID_IN /'INHI','BITO'/ C ====================================================================== C EXECUTABLE CODE C ====================================================================== C - find location of inhibitor in the list of components DO 10 I = 1, NCOMP_NCC IF ( IDSCC(1,I).EQ.ID_IN(1).AND.IDSCC(2,I).EQ.ID_IN(2) ) I_IN=I 10 CONTINUE C - get the concentration of the inhibitor C_IN = 0.0D0 IF ( I_IN .GT.0 ) C_IN = CSS( I_IN ) C ---------------------------------------------------------------------C Parameters: each REALR element defaults to zero if not specified C ---------------------------------------------------------------------A = 0.0D0 IF ( NREALR .GT. 0 ) A = REALR( 1 ) B = 0.0D0 IF ( NREALR .GT. 1 ) B = REALR( 2 ) C ---------------------------------------------------------------------C User rate constant #1 U(1) = 1 / ( 1 + (A+BT)[I] ) C ---------------------------------------------------------------------IF ( NURC.LT.1 ) GO TO 999 RCUSER(1) = 1.0D0 / ( 1.0D0 + ( A + B*TEMP ) * C_IN ) END IF 999 RETURN
User Kinetics Subroutine

The user kinetics subroutine is used to supplement the built-in kinetic calculations. Use this subroutine when the side reaction kinetics are too complicated to represent through the user rate constant routine, or when previously written Fortran routines are to be interfaced to the Step-Growth model. The argument list for this subroutine is provided here. The argument list and declarations are set up in a Fortran template called USRKIS.F, which is delivered with Aspen Polymers.
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SUBROUTINE 1 2 3 4 5 6 7 8 9 * 1 2 3 4 5
USRKIS( SOUT, IDSCC, NINTB, NINTK, IWRK, X, FLOWL, VLQ, VLIQRX, IPOLY, NSGOLG, NFGSPC, RFLRTN, NRC, IUFLAG,
NSUBS, NPO, INTB, INTK, NWRK, X1, FLOWL1, VLQ1, VL1RX, NSEG, NGROUP, CSS, IFLRTN, PREEXP, NURC,
IDXSUB, NBOPST, NREALB, NREALK, WRK, X2, FLOWL2, VLQ2, VL2RX, IDXSEG, IDGRP, CGROUP, CRATES, ACTNRG, RCUSER )
ITYPE, NIDS, REALB, REALK, NCPMX, Y, FLOWV, VVP, VVAPRX, NOLIG, NSPEC, TEMP, NTCAT, TEXP,
XMW, IDS, NIWRK, IDXM, DUMXS, DUMFS, VOLSLT, VSLTRX, IDXOLI, IDXSPC, PRES, RATCAT, TREF,
Variable SOUT NSUBS IDXSUB ITYPE Usage Input Input Input Input Type REAL*8 INTEGER INTEGER INTEGER NSUBS NSUBS Dimension (1) Description Stream vector Number of substreams in stream vector Location of substreams in stream vector Substream type vector 1=MIXED 2=CISOLID 3=NC XMW IDSCC NPO NBOPST NIDS IDS Input Input Input Input Input Input REAL*8 HOLLERITH INTEGER INTEGER INTEGER HOLLERITH 2,NIDS 6, NPO NCC 2, NCC Conventional component molecular weights Conventional component ID array Number of property methods Property method array (used by FLASH) Number of reaction model IDs Reaction model ID list: i,1 reactor block ID i,2 reactor block type i,3 reaction block ID i,4 reaction block type i,5 user subroutine ID NINTB INTB NREALB REALB NINTK INTK NREALK Input Retention Input Retention Input Retention Input INTEGER INTEGER INTEGER REAL*8 INTEGER INTEGER INTEGER NINTK NREALB NINTB User-specified length of INTB array Reactor block integer parameters (See Integer and Real Parameters, page 151) User-specified length of REALB array Reactor block real parameters (See Integer and Real Parameters, page 151) User-specified length of INTM array User subroutine integer parameters (See Integer and Real Parameters, page 151) User-specified length of REALM array
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Variable REALK NIWORK IWORK NWORK WORK NCPM
Usage Retention Input Work Input Work Input
Type REAL*8 INTEGER INTEGER INTEGER REAL*8 INTEGER
Dimension NREALK
Description User subroutine real parameters (See Integer and Real Parameters, page 151) Length of user subroutine integer work vector
NIWORK
User subroutine integer work vector (See Local Work Arrays, page 151) Length of user subroutine real work vector
NWORK
User subroutine integer work vector (See Local Work Arrays, page 151) Number of components present in the mixed substream (See Packed Vectors, page 151)
IDXM X X1 X2 Y Dum1 FLOWL FLOWL1 FLOWL2 FLOWV FLOWS VL VL1 VL2 VV VSALT VLIQRX VL1RX VL2RX VVAPRX VSLTRX IPOLY NSEG IDXSEG NOLIG IDXOLI NSGOLG
Input Input Input Input Input Dummy Input Input Input Input Input Input Input Input Input Input Input Input Input Input Input Input Input Input Input Input Input
REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 INTEGER INTEGER INTEGER INTEGER INTEGER INTEGER
Component sequence numbers (See Packed Vectors, page 151) Overall liquid mole fractions First liquid mole fractions Second liquid mole fractions Vapor phase mole fractions Argument reserved for future application Total liquid flow rate, kmol / sec First liquid flow rate, kmol / sec Second liquid flow rate, kmol / sec Vapor flow rate, kmol / sec Salt flow rate, kmol / sec Total liquid molar volume, m3/kmol First liquid molar volume, m3/kmol Second liquid molar volume, m3/kmol Vapor molar volume, m3/kmol Salt molar volume, m3/kmol Volume* of liquid in reactor, m3 Volume* of first liquid in reactor, m3 Volume* of second liquid in reactor, m3 Volume* of vapor in reactor, m3 Volume* of salt in reactor, m3 Reacting polymer component index Number of segment components
NSEG NOLIG NSEG, NOLIG
Segment component index vector Number of oligomer components Oligomer component index vector Segment frequency vector: contains number of each segment in each oligomer Number of functional groups Functional group ID vector
NGROUP IDGRP
Input Input
INTEGER HOLLERITH 2,NGROUP
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Variable NSPEC IDXSPC NFGSPC
Usage Input Input Input
Type INTEGER INTEGER INTEGER
Dimension NSPEC NSPEC, NGROUP NCC NGROUP
Description Number of reacting species Reacting species component index vector Group frequency vector: contains number of each functional group in each species Concentration vector for reacting species Concentration vector for reacting groups Temperature, K Pressure, Pa
CSS CGROUP TEMP PRES RFLRTN IFLRTN CRATES NTCAT RATCAT NSGRC PREEXP ACTNRG TEXP TREF IUFLAG
Input Input Input Input Retention Retention Output Input Output Input Input Input Input Input Input
REAL*8 REAL*8 REAL*8 REAL* REAL*8 INTEGER REAL*8 INTEGER REAL*8 INTEGER REAL*8 REAL*8 REAL*8 REAL*8 Integer*8
3,(1) 3,(1) NCC
Real retention for FLASH Integer retention for FLASH Component rates of change, kmol / m3 sec Total number of component attributes Component attribute rates of change, cat / m3 - sec Number of sets of step-growth rate constants
NTCAT
NSGRC NSGRC NSGRC NSGRC NSGRC
Pre-exponential factors, 1/sec (See Step-Growth Rate Constants, page 149) Activation energies, J/kmol-K Temperature exponents, unitless Reference temperatures, K User rate constant flags (See User RateConstant Subroutine, page 140)
Variable NURC RCUSER
Usage Input Output
Type INTEGER REAL*8
Dimension NURC
Description Number of user rate constants User rate constant vector (See User Rate-Constant Subroutine, page 140)
Area in RPlug
The user kinetic subroutine returns the rate of change of the reacting species and the Class 2 component attributes (zeroth moment and segment flow rates). The subroutine may be applied to calculate user component attributes (CAUSRA etc.) to track color or other polymer properties which are related to the thermal history of the polymer. Example 4 illustrates how the concentration of a color body can be tracked through user kinetics routine. The example assumes that the polymer color is proportional to the amount of unknown color bodies which are generated by side reactions. These unknown side reactions are sensitive to the thermal history of the polymer, according to an Arrehnius rate expression. The activation energy and pre-exponential factors of this expression are stored as the first and second REAL parameters for the user kinetics model.
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Example 4: Tracking Polymer Color Using User Attributes in a StepGrowth User Kinetics Model INTEGER IDUSRA(2) DATA IDUSRA /'CAUS','RA '/ C.....GAS CONSTANT IN KCAL/MOL-K... RGASKC = 1.987D-3 C.....locate CAUSRA attribute: LUSRA points to location in SOUT... LUSRA = SHS_LCATT( 1, IPOLY, IDUSRA ) C.....LURAT points to this attribute in the RATCAT vector... LURAT = LUSRA - NCOMP_NVCP C ---------------------------------------------------------------------C Get the rate constants from the list of REAL parameters in the C user-kinetics section of the Step-Growth Subroutine form C REAL(1) A_CF Color Formation pre-exponential, 1/min C REAL(2) E_CF Color Formation activation energy, kcal/mol-K C ---------------------------------------------------------------------A_CF = 0.D0 E_CF = 0.D0 IF ( NREALK .GT. 1 ) THEN IF ( REALK( 1 ) .GE. RGLOB_RMISS ) REALK( 1 ) = 0.D0 IF ( REALK( 2 ) .GE. RGLOB_RMISS ) REALK( 2 ) = 0.D0 A_CF = REALK( 1 ) / 60.D0 E_CF = REALK( 2 ) END IF C Calculate color formation rate in color-units/cubic-meter/second RATCAT( LURAT ) = A_CF * DEXP( -E_CF / ( RGASKC*TEMP ) ) RETURN
Step-Growth Rate Constants

The step-growth reaction rate constants can be applied in the user kinetics subroutine. The rate constants are passed to this model as a set of arrays which are stored in rate constant set number order (the element number of the array corresponds to the reaction set number). These parameters are stored in SI units. The concentration basis for the pre-exponential factors are in molar concentration (mol/L) units. When a user concentration basis subroutine is used, the pre-exponential factors are assumed to be in units which are consistent with the user-calculated concentrations. The user rate constants are also passed to the user kinetic subroutine. These parameters can be used as is, or they can be used with the step-growth rate constants to build rate expressions consistent with those used by the standard model. The array UFLAG is used to designate which user rate constant (if any) is assigned to a given set of step-growth rate constants. For example, if IUFLAG(2) = 1, then user rate constant 1 is assigned to stepgrowth rate constant set 2, and the pre-exponential factor can be adjusted accordingly. Example 5 illustrates how to apply user rate constants and stepgrowth rate constants in a user kinetics model. Example 5: How to Apply User Rate Constants and Step-Growth Rate Constant in a Step-Growth User Kinetics Model
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set work space to calculate net rate constants LPREEX = 0 LNETRC = LPREEX + NSGRC C ---------------------------------------------------------------------C Multiply step-growth pre-exponential factors by user rate constants C and store the results in the work array. C ---------------------------------------------------------------------DO 10 IR = 1, NSGRC IRCU = IUFLAG( IR ) IF ( IRCU .EQ. 0 ) THEN WORK( LPREEX + IR ) = PREEXP( IR ) ELSE WORK( LPREEX + IR ) = PREEXP( IR ) * RCUSER( IRCU ) END IF 10 CONTINUE C ---------------------------------------------------------------------C Calculate the net rate constants C ---------------------------------------------------------------------DO 20 IR = 1, NSGRC IF ( TREF(IR) .EQ. 0 ) THEN TTERM1 = 1/TEMP TTERM2 = TEMP**TEXP(IR) ELSE TTERM1 = 1/TEMP - 1/TREF(IR) TTERM2 = ( TEMP / TREF )**TEXP(IR) END IF ETERM = DEXP( -ACTNRG(IR) * TTERM1 / PPGLOB_RGAS ) WORK( LNETRC+ IR ) = WORK( LPREEX+ IR ) * ETERM * TTERM2 20 CONTINUE
Note: The work array is used to store intermediate results in the calculations. The size of the work array must be specified in the subroutine form and must be large enough to avoid overwriting the end of the array.
INCL-COMPS List
The reactor models in Aspen Polymers use mass-balance equations for each reacting component. In order to make the reactor models fast, components which do not appear in the reactions are excluded from these calculations. The list of reacting components is automatically generated by the StepGrowth model. This list includes the polymer component, listed oligomers, components which appear in the list of reacting species, components which appear as products or reactants in the user-specified reactions, and components in the INCL-COMPS component list. When user concentration basis or user kinetics subroutines are applied in a model, these subroutines can include reactions involving components which do not otherwise appear in the list of reacting components. These components should be added to the INCL-COMPS list to ensure they appear in the mass-balance equations.
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Integer and Real Parameters

Each user model has two sets of integer and real parameters. The first set comes from the subroutine form of the reactor block. The second set comes from the subroutine form of the step-growth reactions model. Each of these parameters are retained from one call to the next, thus these parameters can be used as model inputs, outputs, or retention. The reactor block integer and real parameters can be used to specify data which are specific to a particular unit operation, such as reactor geometry, mass transfer coefficients, etc. The integer and real parameters in the subroutine forms can be used to specify global parameters, such as rate constants or physical property parameters.
Local Work Arrays

You can use local work arrays by specifying the model workspace array length on the STEP-GROWTH Subroutine form. These work areas are not saved from one call to the next. All three user subroutines share a common work area, so you must zero out the work space at the start of each subroutine.
Packed Vectors
Aspen Plus frequently uses a technique called packing to minimize simulation time. The user models previously described use packed vectors to track the mole fractions of each phase (vectors X, X1, X2, and Y). These vectors contain NCPM elements (Number of Components Present in the Mixed substream). The component index associated with each element is listed in the vector IDXM. All other vectors used by the model, including the rates vectors and the component concentration vectors, are unpacked. Example 6: Calculating Unpacked Component Concentrations Calculate unpacked component concentrations of the first liquid phase given the packed mole fractions of the first liquid phase and the molar volume of the first liquid phase. IF ( VL1 .GT. 0.D0 .AND. FLOWL1.GT.0.D0 ) THEN DO 10 I = 1, NCPM CSS(I) = X1( IDXM( I ) ) / VL1 CONTINUE END IF
10
Note: NCPM steps were required to load the concentration vector. Since NCPM is always less than or equal to NCC (total number of conventional components), there is a reduction in the required number of steps to perform the operation.
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Specifying Step-Growth Polymerization Kinetics

Accessing the Step-Growth Model
To access the Step-Growth polymerization kinetic model: 1 2 3 4 5 6 From the Data Browser, click Reactions. From the Reactions folder, click Reactions. The Reactions object manager appears. If the kinetic model already exists, double-click the desired Reaction ID in the object manager or click Edit to get to the input forms. To add a new model, from the Reactions object manager, click New. If necessary, change the default ID for the reaction. Select Step-Growth as the reaction type and click OK.
Specifying the Step-Growth Model

The Step-Growth model input forms are divided into two folders: Specifications and User Subroutines. Use the Specifications forms to define reacting species and functional groups, enter reaction rate constant parameters, and include user side reactions.
Use this sheet Species To Define reacting species and functional groups Specify the name of the polymer being produced Specify the names for linear oligomers (optional) Reactions Rate Constants User Reactions User Rate Constants Assign User Rate Constants Options Generate and display model-generated reactions Specify reaction rate constants for modelgenerated reactions Specify reaction stoichiometry and enter rate constants for user-specified reactions Specify catalysts and reaction rate constants for user-specified reactions Assign one or more sets of rate constants to each user-specified reaction Specify the reacting phase and concentration basis. Change reaction convergence parameters. Select report options.
Use the User Subroutines forms to specify the names and parameters for optional user subroutines.
Use this sheet To
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Kinetics
Specify the name of the user kinetics routine and give the integer and real arguments for the user arrays for this routine Specify the name of the user kinetics routine, the number of user rate constants calculated by the routine, and to give the integer and real arguments for the user arrays for this routine Specify the name of the user concentration and reacting phase volume basis routine and give the integer and real arguments for the user arrays for this routine
Rate Constants
Basis
Specifying Reacting Components

You must specify the reacting species and functional groups on the StepGrowth Specifications Species sheet. First specify the polymers and oligomers produced: 1 2 3 In the Polymer field, specify the polymer produced. In the Oligomers field, list oligomers that you want the model to track. In the species definition table, specify the functional groups contained in each reacting species and define each group type.
The structure of reacting species in terms of the reactive functional groups they contain must be defined. To do this: 1 2 3 In the Group field specify an ID name for each functional group type present in the reacting species. For each group, select a type from the group type field. List the species in the Species field. These species can be monomers, condensates, or segments. The resulting form is a spreadsheet, with each column representing a functional group and each row representing a reacting species. The cells in the spreadsheet correspond to the number of each functional group in each species. 4 In the number field for each species, specify the number of each defined functional group contained in that species. Unspecified fields are interpreted as zeros.
Listing Built-In Reactions

The step-growth model generates reactions based on the functional group definition of reacting species. You can view the system-generated reactions, by clicking the Generate Reactions button on the Specifications Reactions sheet. In the Reaction summary listing for each reaction, the first column indicates the reaction type. The second column lists the reactants, and the last column lists the products. The Data Browser window can be resized to better view the reaction listing.
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Specifying Built-In Reaction Rate Constants

You can define the catalysts and rate constants for system-generated reactions. The model applies a modified power-law rate expression, which can be customized through a user-written rate constant subroutine. By default, the model assumes concentrations are in mol/liter. Another concentration basis can be applied through a user-written basis subroutine. To specify rate constants: 1 2 3 Go to the Rate constants sheet. In the reaction No. field, assign a unique integer identifier for a set of rate constant parameters. In the Catalyst Species field, specify the name of a catalyst species associated with the rate constant set. You can leave this field unspecified if the reaction is uncatalyzed, or if the catalyst is defined as a functional group. 4 In the Catalyst Group field, specify the name of a catalyst functional group associated with the rate constant set. You can leave this field unspecified if the reaction is uncatalyzed, or if the catalyst is defined as a species. 5 Enter the rate constant parameters: ko for Pre-exponential factor, Ea for Activation energy, b for Temperature exponent, Tref for Reference temperature. Request any user rate constant expression in the User flag field. Repeat these steps as needed to specify the list of rate constant parameters.
6 7
Assigning Rate Constants to Reactions

You can assign rate constants to individual reactions using the reaction stoichiometry, or you can assign rate constants to sets or reactions using the appropriate reaction identifiers. To assign the rate constants set: 1 2 3 Click the Assign Rate Constants button on the Specifications Rate constants sheet. Click the Global tab to assign rate constants to a set of reactions or use the Individual sheet to assign rate constants to individual reactions. Go to the Rate Constant Sets field, select from the list of pre-defined rate constant sets for each reaction.
Including User Reactions

You can add user reactions to the built-in set. For this you must specify a reaction stoichiometry and the associated rate constants. The model applies a modified rate expression, which can be customized through a user-written rate constant subroutine. To add user reactions use the following options found on the Specifications User Reactions sheet:
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Click New Edit Rate Constants
To Add new reactions to the scheme Specify reaction stoichiometry and power-law exponents Specify reaction rate constant parameters for the reactions
Click to select a reaction. Click a reaction then Control-Click to include additional reactions for multiple selections. Double-click to edit a reaction. In addition, you can use the following buttons:
Click Hide/Reveal Delete To Exclude/Include a reaction from the calculations Permanently remove a reaction from the model
Adding or Editing User Reactions

In the User Reactions sheet, to add a new reaction to the scheme or edit an existing reaction, open the Edit subform. When you open the Edit subform, a unique number is assigned in the Reaction no. field, to the reaction being added. To add or edit your reaction: 1 On the Edit subform, specify the Component ID and stoichiometric Coefficient for the reactants. Reactants must have a negative coefficient. 2 Specify the Component ID and stoichiometric Coefficient for the products. Products must have a positive coefficient. 3 Click or Click Close to return to the reaction summary. to check the Completion Status
Specifying Rate Constants for User Reactions

All the rate constants for user-specified reactions are summarized in a grid on the User Rate Constants tab: 1 2 3 In the k o field, enter the pre-exponential factor. In the Ea field, enter the activation energy. In the b field, enter the temperature exponent.
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In the Tref field, enter the reference temperature.
Note: Use the Catalyst Species field to associate a rate constant with a particular catalyst. If you leave this field blank the model drops the catalyst term from the rate expression. Use the Catalyst Order field to specify the reaction order with respect to the catalyst (the model assumes first order by default).
Assigning Rate Constants to User Reactions

By default, the model assumes one set of rate parameters for each reaction. (For example, rate constants in row 1 apply to user reaction 1). Alternately, you may assign one or more rate constants to each reaction using the Assign User Rate Constants form. When several rate constants are assigned to a reaction the model calculates a net rate constant by summing all of the listed rate constants and multiplying the sum by a specified activity. To assign rate constants to user reactions: 1 2 On the Assign User Rate Constants form, use the Activity field to specify the activity factor. In the Rate Constant Sets field, select from the list of pre-defined rate constant sets for each reaction.
Selecting Report Options

You can select which format to use for the step-growth reactions in the report file. On the Options sheet, go to the Report frame to request a reaction report. Then, select a Summary or Detailed format.
Selecting the Reacting Phase

The Options form lets you specify the phase in which the reactions occur. Select the appropriate phase from the list in the Reacting Phase field. All of the reactions in a particular step-growth object are assumed to take place in the same phase. Note: You must specify the Valid Phases keyword for each reactor model referencing the kinetics to ensure the specified reacting phase exists. If the Reacting Phase option is set to Liquid-1 or Liquid-2 the model assumes two liquid phases exist. When the named phase is not present, the model prints a warning message and sets the reaction rates to zero. There are two options for handling phase collapse: Select the Use bulk liquid phase option to force the model to apply the specified reaction kinetics to the bulk phase when the named phase disappears. Select the Suppress warnings option to deactivate the warning messages associated with phase collapse.
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These options are especially convenient when modeling simultaneous reactions in two liquid phases using two step-growth models. In this situation, you would typically select the Use bulk liquid option for one phase and not the other (to avoid double-counting reactions when one phase collapses).
Specifying Units of Measurement for PreExponential Factors

Reaction rates are defined on a molar basis (moles per volume per time) . The time units for the pre-exponential factors are specified directly on the Rate Constant forms. By default, the concentration units are presumed to be in SI units (kmole/m3 or mole/L). You change the concentration basis to other units using the Concentration Basis field of the Options sheet. Alternately, you may apply a user basis subroutine.
Including a User Kinetic Subroutine

Use the User Subroutines Kinetics form to specify parameters for user kinetics calculations: 1 2 3 4 In subroutine Name, enter the name of the Fortran subroutine. Specify the size of vectors for Integer, Real in Number of parameters, and Length of work arrays. Enter integer and real parameter values in Values for parameters columns. Click Include Comps to specify components to be included in material balance convergence.
Including a User Rate Constant Subroutine

Use the User Subroutines Rate Constants form to specify parameters for user rate constants calculations: 1 2 3 4 In subroutine Name, enter the name of the Fortran subroutine. Specify the size of vectors for Integer, Real and No. const. in Number of parameters. Specify the size of vectors of Integer and Real in Length of work arrays. Enter integer and real parameter values in Values for parameters columns.
Including a User Basis Subroutine

Use the User Subroutines Basis form to specify parameters for basis calculations: 1 In subroutine Name, enter the name of the Fortran subroutine.
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2 3
Specify the size of vectors for Integer and Real in the Number of parameters and Length of work arrays. Enter integer and real parameter values in Values for parameters columns.
References
Billmeyer, F. W. (1971). Textbook of Polymer Science. New York: Wiley. Gupta, S. K, & Kumar, A. (1987). Reaction Engineering of Step-Growth Polymerization. New York: Plenum. Jacobsen, L. L., & Ray, W. H. (1992). Unified Modeling for Polycondensation Kinetics. J. Macromol. Sci.-Rev. Macromol. Chem. Phys. Kaufman, H. S., & Falcetta, J. J. (Eds). (1977). Introduction to Polymer Science and Technology: An SPE Textbook. New York: Wiley. McKetta, J. J. (Ed.). (1992). Encyclopedia of Chemical Processing and Design, 39 & 40. New York: Marcel Dekker. Rodriguez, F. (1989). Principles of Polymer Systems. New York: Hemisphere.
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9 Free-Radical Bulk Polymerization Model
This section covers the free-radical bulk/solution polymerization model available in Aspen Polymers (formerly known as Aspen Polymers Plus). Topics covered include: Summary of Applications, 159 Free-Radical Bulk/Solution Processes, 160 Reaction Kinetic Scheme, 161 Model Features and Assumptions, 179 Polymer Properties Calculated, 187 Specifying Free-Radical Polymerization Kinetics, 189
Several example applications of the free-radical bulk/solution polymerization model are given in the Aspen Polymers Examples & Applications Case Book. The Examples & Applications Case Book provide process details and the kinetics of polymerization for specific monomer-polymer systems.
The free-radical bulk/solution polymerization model is applicable to bulk and solution polymerization processes. Some examples of applicable polymers are: General purpose polystyrene - Made by polymerization of styrene monomer with or without solvent fed continuously to reactor. High impact polystyrene - Made by polymerization of an unsaturated rubber dissolved in styrene in a solution process. Also produced in masssuspension processes. Poly(vinyl chloride) - Produced in bulk polymerization using monomersoluble free radical initiators. Most of the homopolymers and copolymers of vinyl chloride, however, are produced by suspension polymerization. Poly(vinyl acetate) - Produced industrially by the polymerization of vinyl acetate in bulk or solution processes. Also produced in suspension and emulsion processes. Both batch and continuous processes are used.
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Poly(vinyl alcohol) - Poly(vinyl acetate) is converted into the corresponding poly(vinyl alcohol) by direct hydrolysis or catalyzed alcoholysis. The reaction can be catalyzed by strong acids or strong bases. Poly(methyl methacrylate) - The vast majority of commercially prepared acrylic polymers and methacrylic polymers are copolymers. Commercially they are prepared by solution polymerization. They are also produced by emulsion polymerization and suspension polymerization. Low density polyethylene - Made by high pressure, free radical processes in either a tubular reactor or a stirred autoclave. Typical commercial processes include staged compression, initiator injection, partial conversion of ethylene to polymer, separation of ethylene from polymer, extrusion of molten polymer, and cooling of ethylene. The Free-Radical model may also be used to simulate suspension polymerization processes in which the polymer is completely soluble in the organic (monomer) phase. Two reaction models can be applied together to represent reactions in each liquid phase. An example of this process is: Poly(styrene) - Poly(styrene) may be produced in a continuous suspension process in a series of CSTR type reactors.
Free-Radical Bulk/Solution Processes

Free-radical polymerization accounts for a large proportion (more than 40% by weight) of the commodity grade polymers. It is employed in the synthesis of countless homo- and copolymers using monomers that are either monosubstituted ethylenes ( RHC = CH 2 ) or 1,1-disubstituted ethylenes
( R1 R2C = CH2 ) .
Free-radical polymerization usually takes place with the monomer in the liquid phase. Several types of processes are used. A solvent or suspending medium may be used, and the polymer formed may be soluble, insoluble, or swelled by the monomer and solvent. Commercially important processes for freeradical polymerization include bulk, solution, suspension, and emulsion polymerization.
Bulk and Solution Polymerization

Bulk and solution polymerization processes are characterized by the fact that the reactions proceed in a single phase. Typically the monomers are fed to a reactor with or without a solvent. A small amount of initiator is also fed. At the reaction temperature, the initiator decomposes to form radicals that initiate the polymerization reactions. The polymer formed is usually soluble in the monomer/solvent mixture. However, in some systems, such as PVC, the polymer is insoluble and forms a separate phase. The most commonly used reactor types include batch, semi-batch, continuous stirred-tank and tubular reactors. Flowsheets consisting of several reactors in series are common. The main technical challenges with bulk/solution polymerization processes are heat removal, handling of the highly viscous
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liquid, and recovery of residual monomer/solvent. Several modes of heat removal can be employed, including jacket cooling, internal cooling coils/baffles, external heat exchangers and reflux condensors.

Most free-radical polymerizations have at least four basic reaction steps: Initiation Propagation Chain transfer to a small molecule (i.e. monomer, solvent or transfer agent) Termination
These reactions occur simultaneously during the polymerization. For branched polymers additional reactions for long and short chain branching can also be present. A comprehensive kinetic scheme for the free-radical homo- and copolymerization of up to N m monomers has been built into Aspen Polymers. The scheme includes most of the reactions commonly used for modeling freeradical polymerization. The model also includes several optional reactions: Terminal double bond polymerization Pendent double bond polymerization (for diene monomers) Head-to-head propagation (for asymmetric monomers) Cis- and trans- propagation (for diene monomers) Primary and secondary decomposition of bifunctional initiators
Reactions such as depropagation and random chain scission are not included in the current model. These reactions may be added to the built-in scheme in the future. The main reactions in the current built-in free-radical kinetic scheme is shown here :
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Built-in Free-Radical Polymerization Kinetic Scheme
The nomenclature used in the free-radical kinetic scheme is shown here:

Symbol Description
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Symbol
Description
Symbols Used in the Population Balance Equations
Ak
Chain transfer agent of type k Reaction by-products (optional for some reactions) Coinitiator or catalyst of type k Dead polymer chain of length n
B1 , B2
Ck Dn
( = n1, n2, ... nm )
Dnjk
i= Dn i ( vinyl ) Dn ij f TDB
Polymer chain of length n containing an undecomposed bifunctional initiator fragment of type k attached to penultimate segment of type j Polymer chain of length n containing a terminal double bond of type i Polymer chain of length n reacting at an internal double bond of type i (e.g., a diene segment of type i in the vinyl configuration) Fraction of reactions between species i and j resulting in the formation of a terminal double bond of type i Standard initiator of type k Bifunctional initiator of type k Monomer of type j Live polymer chain of length n having an active segment of type i Live polymer chain of length n having an active diene segment of type i in the cis configuration. Live polymer chain of length n having an active diene segment of type i in the trans configuration. Primary radicals Solvent of type k (for solution polymerization) Inhibitor of type k Stoichiometric coefficients for reaction by-products B1, B2 Initiator efficiency factor for initiator k Chain transfer agent of type k Reaction by-products (optional for some reactions) Coinitiator or catalyst of type k Dead polymer chain of length n
Ik
I kB
Mj Pni
Pni ( cis ) Pni ( trans )

R Sk Xk
1 , 2 k
Ak
B1 , B2
Ck Dn
( = n1, n2, ... nm )
Symbol
Description
Symbols Used in Reaction Rate and Moment Balance Equations
a , b, c
Coefficients for the induced (thermal, radiation) initiation rate Concentration of a reacting non-polymeric species. The following
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Symbol
Description subscripts are used to identify the component: Ak Ck Ik Mi Sk Xk Chain transfer agent k Catalyst or coinitiator k Initiator or bifunctional initiator k Monomer i Solvent k Inhibitor k
Net rate constant (see Equation 3.1 on page 166 ). The following subscripts are used to identify the reaction types: bs bid cis ic id hth p pdb pi scb si sid tc td tdbp tra trans trm trp trs x Beta scission Bifunctional initiator primary decomposition Cis-propagation Catalyzed initiation Standard initiator decomposition Head-to-head propagation Propagation (polymerization) Pendent double bond polymerization Primary chain initiation Short chain branching Special initiation (induced initiation) Secondary decomposition of bifunctional initiator Termination by combination Termination by disproportionation Terminal double bond polymerization Chain transfer to agent Trans-propagation Chain transfer to monomer Chain transfer to polymer (long chain branching) Chain transfer to solvent Inhibition
Number of (A=agents, BI=bifunctional initiators, C=catalysts, CI=coinitiators, I=standard initiators, M=monomers, S=solvents, X=inhibitors) Number of radicals (1 or 2) formed from the decomposition of initiator of type k Stoichiometric coefficients for reaction by-products B1, B2 Initiator efficiency factor for initiator k Fraction of reactions between species i and j resulting in the formation of a terminal double bond of type i Zeroth moment of live polymer with respect to active segment of type i First moment of live polymer with respect to segment j Zeroth moment of bulk polymer (live + dead)
N rk
1 , 2
k
ij fTDB
i 0
1j
0
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Symbol
Description First moment of bulk polymer (live + dead) with respect to segment j Second moment of bulk polymer (live + dead) Moment a (a=0, 1, 2, etc) of polymer molecules with terminal double bond of type j Flow rate of dyads consisting of i and j segments (these values are stored in the DYADFLOW attribute) Molar fraction of diene segment i in the vinyl configuration (zero for nondiene segments) (related to VINYLFRA attribute) Concentration of undecomposed initiator fragment k in the bulk polymer (live + dead) (related to FRAGFLOW attribute)
1j
2
aj = i, j i k
In the discussion that follows, a polymer chain is considered to be made up of monomer units or segments derived from the propagating monomers. Typically there will be one segment type associated with each monomer. However, it is possible to define several segment types associated with a single monomer. This may be necessary, for example, for modeling the tacticity of a polymer, or head-to-head versus head-to-tail incorporation of an asymmetric monomer ( RHC = CH 2) .
Polymer Chain Terms

The term live polymer chain ( Pni ) refers to growing polymer chains containing n segments, with a radical attached to a segment of type i, i.e., segment formed from monomer i. The term dead polymer chain ( Dn ) refers to terminated polymer chains that do not have an attached radical. The term bulk polymer chain is used to refer to the sum of the live and dead polymer chains. The subscript n refers to the chain length in terms of the number of segments or monomer units incorporated in the polymer chain. Live chains are reactive and can participate in the polymerization reactions while dead chains are usually considered inert, except when long chain branching reactions are important. The radical attached to one end of a live polymer chain is considered to be mobile and moves away from the initiator fragment with every addition of a monomer molecule. It is believed that after a few monomer additions the chemistry of the initiator fragment and developing chain microstructure will not have a strong influence on the mode of monomer addition. The free-radical kinetic model assumes that the reactivity of a live polymer chain depends only on the active segment containing the radical, and is independent of the polymer chain length and other structural properties. This assumption was used in writing the rate expressions for the reactions shown in the Built-in Free-Radical Polymerization Kinetic Scheme figure on page 162.
ij ) is For example, in the propagation reaction, the rate of propagation ( R p
independent of the polymer chain length. It depends only on the concentration of monomer j and the concentration of live polymer chains with active segments of type i. Models using this assumption are referred to as terminal models in the polymerization literature.
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For copolymerization, the built-in kinetics routine allows the user to specify the number of monomers used. Similarly, the user has the flexibility to specify the number of each type of reactive species used in the polymerization, e.g. initiators, chain transfer agents, solvents and inhibitors. The user can easily setup the built-in kinetics to model a specific free-radical polymerization by selecting a subset of the reactions shown in the Built-in Free-Radical Polymerization Kinetic Scheme figure on page 162. It is necessary that the subset include a chain initiation and a propagation reaction. Frequently, at least one termination, chain transfer, or inhibition reaction to produce dead polymer is also selected. The rate constants for each reaction in the built-in kinetics is calculated at the reaction temperature and pressure using the modified Arrhenius equation shown below with user specified parameters: pre-exponential (or frequency) factor, activation energy, activation volume, and reference temperature:
Rate Constant
Ea VP 1 1 k = ko exp R T Tref R
Where:
f g
(3.1)
ko
Ea P R
= Pre-exponential factor in l/sec for first order reactions, and m / kmol s for second order reactions
3
= Activation energy in mole-enthalpy units = Reaction pressure = Universal gas constant = Reference temperature = Gel effect factor from optional built-in or user-defined gel effect correlation
V = Activation volume in volume/mole units
Tref fg
The second term in the exponential function contains an activation volume that is important for high pressure polymerization systems. For low to moderate pressures, the activation volume is typically set to default value of zero. This term is used to account for the pressure dependence of the reaction rate constant. The free-radical model allows the rate expression to be modified by a gel effect term, g . The gel effect term can be calculated using one of several built-in correlations or it can be calculated by an optional user-defined gel effect subroutine. The model allows any number of bifunctional initiators, however the maximum number of unique bifunctional initiators (used throughout the flowsheet) must be specified on the Polymers, Options subform. This parameter is used to dimension the FRAGFLOW polymer component attribute, which is used to track the flow rate of undecomposed initiator fragments. The FRAGFLOW attribute must be included in the attribute list in the Polymers,
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Polymers subform. Bifunctional and standard initiators can be used in the same model.
Initiation
The initiation step involves the generation of reactive free-radicals followed by the addition of a monomer molecule (chain initiation) to form chain radicals of
i unit length ( P 1 ) . The non-chain or primary radicals ( R ) may be generated by the thermal decomposition of a chemical initiator, a catalyzed initiation reaction involving electron transfer from ions, or by thermal/radiation induced mechanisms. Three types of standard initiation reactions are included in the built-in kinetics:
Initiator decomposition reaction Induced initiation reaction Catalyzed initiation reaction
The initiator decomposition reaction accounts for primary radical generation from the thermal decomposition of chemical initiators. The induced initiation reaction can be configured to account for the generation of radicals by thermal and radiation induced mechanisms from the monomers themselves, with or without the use of a coinitiator or promoter. The catalyzed initiation reaction can be used to account for redox initiation, which has found wide application in aqueous emulsion polymerization systems. The most commonly used radical generation method is the thermal decomposition of chemical initiators (usually peroxide or azo compounds) which decompose to form radicals when heated to an appropriate temperature. Only small amounts of the chemical initiator (less than 1 wt. % based on monomer) are needed. However, due to their high activation energies chemical initiators have a relatively narrow useful temperature range (approx. 30C) over which the decomposition rates are neither too fast nor too slow. Some processes, notably bulk polystyrene polymerization, use initiators with two active sites. These bifunctional initiators decompose in two stages, providing greater control over the molecular weight distribution of the product. The free-radical model includes two reactions associated with bifunctional initiators: Bifunctional initiator decomposition (primary decomposition) Secondary initiator decomposition (primary decomposition) The primary decomposition reaction generates a pair of radicals, an undecomposed initiator fragment, and optional by-products. The undecomposed fragment is tracked using the FRAGFLOW polymer component attribute. The initiator fragment decomposes in the secondary decomposition reaction, generating a free radical and a polymeric radical.
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Initiator Decomposition Reaction

The initiator decomposition reaction is modeled as a first order thermal decomposition reaction:
I k k N rk R + 1,k B1 + 2,k B2
k
k k Rid = kid C Ik
This rate expression ( Rid ) describes the rate for the thermal decomposition of standard initiator k. The symbols B1 and B2 represent optional user-specified reaction by-products. This feature lets you track the formation of lowmolecular weight decomposition by-products, such as carbon dioxide, which may be generated as the initiators decompose. The byproduct formation rates are determined by:
k RB1 ,k = 1,k kid C Ik k RB2 ,k = 2,k kid C Ik
For mass balance purposes, the polymer mass generation rate is incremented by the initiator mass consumption rate, less the mass formation rate of byproducts. The rate expression for the formation of primary radicals from the thermal decomposition of standard initiators is given by:
rad k Rid = N rk k kid C Ik k =1 NI
There are a number of user specifiable parameters associated with this reaction. The user can specify more than one initiator to model systems where multiple initiators with different half-lives are used to control the initiation rate over the course of the polymerization. Depending on the initiator, either one or two primary radicals may be formed, hence the parameter N rk should be set to 1 or 2. Bifunctional initiators, which can produce up to four radicals, are handled explicitly using another set of reactions described below. A fraction of the radicals generated by decomposition undergo radical recombination in the radical-cage, leading to stable byproducts. The initiator efficiency factor, k , is used to specify the fraction of radicals which are not destroyed by the cage effect. The efficiency factor can be adjusted using an efficiency gel effect correlation as described later in the text. The rate constant k id is calculated using a modified Arrhenius equation (Equation 3.1 on page 166) with three parameters: pre-exponential factor, activation energy and activation volume. As noted previously, the activation volume accounts for the pressure dependence of the rate constant. This parameter is typically non-zero only at high pressures. Appendix B lists initiator decomposition rate constant parameters (pre-exponential factor and activation energies) for many commonly used initiators. These rate parameters are included in the INITIATOR databank and are automatically loaded into the model each time the reaction network is generated. The standard rate expression can be modified using an optional built-in or user-defined gel effect correlation as described later in the text.
k
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Induced Initiation Reaction

Free-radicals can also be generated from some monomers by thermal, radiative (UV, electron beam or gamma rays) or induced mechanisms. For example, styrene at temperatures above 120C has a significant thermal initiation rate. The thermal initiation mechanism for styrene is believed to be 3rd-order in monomer (Hui & Hamielec, 1972). This reaction results in the formation of significant amounts of cyclic dimers and trimers which have to be removed during devolatilization. Hence, thermal initiation is not favored commercially. Radiation initiation has been used mainly for polymer modification to induce branching, crosslinking or grafting reactions. The induced initiation reaction, shown below, can be configured to model both these initiation mechanisms:
kj kj j M j + Ck P1 + 1 B1 + 2 B2
R si = k si CCk CM j (h )
kj kj aj bj j j bj
cj
For thermal initiation, the rate should be Rsi = k si C Mj (set a j , c j to zero). For radiation initiation, the rate should be Rsi = k si C Mj ( h ) (set a j to zero)
j j bj cj
The induced initiation reaction can also account for the effects of using an initiator or promoter (Ck ) to increase the rate of radical generation. The parameters
1 and 2 are optional stoichiometric coefficients related to

kj kj j aj bj cj RB 2 = 2 k si CCk C Mj ( h )
by-products B1 and B2 . The byproduct formation rates are determined by:

kj kj j aj bj cj RB 1 = 1 k si CCk C Mj ( h )
The molar consumption rate of the monomer is equal to R si . If a promoter is specified in the reaction, its molar consumption rate is also set to R si . The mass generation rate of the polymer is set equal to the mass consumption rate of the monomer ( M j ) and promoter ( C k ). The special initiation reactions generate live polymer directly, thus this reaction does not contribute to radical generation.
kj
kj
Catalyzed Initiation Reaction

The catalyzed initiation reaction is similar to the initiator decomposition reaction except that a catalyst concentration term is included in the reaction rate expression:
I k + C j kj N rk R + C j + 1,kj B1 + 2,kj B2
kj ci
kj kj Rci = kci C Ik CCj
This rate
expression ( R ) describes the rate of consumption of initiator k. The catalyst rate is set to zero, assuming that the catalyst is not consumed by this reaction. The corresponding rate expression for the formation of primary radicals is given by:
rad kj Ric = kj N rkj kic C Ik CCj k =1 j =1 N I N CI
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The parameters
1 and 2 are optional stoichiometric coefficients related to

kj kj kj RB 2 = 2 kic C Ik CCj For mass balance purposes, the
by-products B1 and B2 . The byproduct formation rates are determined by:

kj kj kj RB 1 = 1 k ic C Ik CCj
polymer mass generation rate is incremented by the initiator mass consumption rate, less the mass formation rate of by-products.
Primary Chain Initiation

To complete the initiation process, the reactive primary radicals ( R ) react with monomer by the primary chain initiation reaction to form polymer chain radicals of unit length. The chain initiation reaction is shown below:
j R + M j P 1 j j Rpi = k pi CMj R
The chain radicals grow by successive addition of monomer molecules to form long chain polymer molecules. It is common practice to set the chain initiation rate constants equal to the propagation rate constant each monomer. The primary chain initiation reaction consumes primary radicals:
rad R pi = k ipi CMi R i =1 NM
Bifunctional Initiator Primary Decomposition Reaction

The bifunctional initiator decomposition reaction is modeled as a first order thermal decomposition reaction:
I kB k R + k Rk + 1,k B1 + 2,k B2
k
k k Rbid = kbid C Ik
This rate expression ( Rbid ) describes the rate for the primary decomposition of bifunctional initiator k. Each primary decomposition reaction generates an undecomposed fragment. The generation rate of undecomposed fragments is equal to the initiator decomposition rate:
k RF ( k ) = kbid C Ik
The symbols B1 and B2 represent optional user-specified reaction byproducts. This feature allows you to track the formation of low-molecular weight decomposition by-products, such as carbon dioxide, which may be generated as the initiators decompose. The byproduct formation rates are determined by:
k RB1 ,k = 1,k kbid C Ik k RB2 ,k = 2,k kbid C Ik
For mass balance purposes, the polymer mass generation rate is incremented by the bi-initiator mass consumption rate, less the mass formation rate of byproducts. The rate expression for the formation of primary radicals from the primary thermal decomposition of bifunctional initiators is given by:
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rad k Rbid = N rk k kbid C Ik k =1
N BI
The user can specify more than one bifunctional initiator to model systems where multiple initiators with different half-lives are used to control the initiation rate over the course of the polymerization. The model assumes that the each site in the bifunctional initiator generates two radicals. A fraction of the radicals generated by decomposition undergo radical recombination in the radical-cage, leading to stable byproducts. The initiator efficiency factor, k , is used to specify the fraction of radicals which are not destroyed by the cage effect. This factor can be adjusted using a built-in or user-defined efficiency gel effect correlation. The rate constant kbid is calculated using a modified Arrhenius equation (Equation 3.1 on page 166) with three parameters: pre-exponential factor, activation energy and activation volume. As noted previously, the activation volume accounts for the pressure dependence of the rate constant. This parameter is typically non-zero only at high pressures. The rate expression can be modified using an optional built-in or user-defined gel effect correlation as described later in the text. To complete the initiation process, the reactive primary radicals ( R , Rk ) react with monomer by the chain initiation reaction to form polymer chain radicals of unit length. Note that the undecomposed initiator fragment k is
k
) . This fragment is eventually destroyed conserved in the polymer chain ( P 1 by the secondary decomposition reaction described in the next sub-section. The chain initiation reactions are shown below:
j R + M j P 1 j j Rpi = k pi CMj R
j ,k
j ,k Rk + M j P 1
j j R pi = k pi CMj Rk
The chain radicals grow by successive addition of monomer molecules to form long chain polymer molecules.
Bifunctional Initiator Secondary Decomposition Reaction

The secondary bifunctional initiator decomposition reaction is modeled as a first order thermal decomposition reaction:
Dnj ,k k R + k Pnj + 1,k B1 + 2,k B2
k RF ( k ) = k sid k
This rate expression ( RF ( k ) ) describes the rate for the decomposition of bifunctional initiator fragment k. In this equation
( k ) is the concentration of
undecomposed fragments of type k, which is calculated from the FRAGFLOW polymer attribute. The model assumes that the secondary decomposition reaction generates a primary radical and a live end group (polymer radical). A fraction of the radical pairs generated by decomposition recombine in the radical-cage,
171
leading to stable byproducts. The initiator efficiency factor,
k , is used to
specify the fraction of radicals which are not destroyed by the cage effect. This factor can be adjusted using a built-in or user-defined efficiency gel effect correlation. The generation rate of primary radicals from this reaction can be written as:
rad k Rsid = k k sid k k =1 N BI
Each fragment decomposition event generates a new live end. The model assumes that the fragments are randomly distributed across the bulk polymer molecules and that the penultimate segment attached to the fragment becomes a live end. The generation rate of live ends of type i from the decomposition of initiator fragment k can be written as:
j d 0 ( j ) k k 1 = k k sid dt 0 1
The byproduct formation rates are determined by:

k RB1 ,k = 1,k k sid k k RB2 ,k = 2,k k sid k
The mass generation rate of polymer is adjusted to account for mass lost in the form of reaction by-products. The user can specify more than one bifunctional initiator to model systems where multiple initiators with different half-lives are used to control the initiation rate over the course of the polymerization. The rate constant k sid is calculated using a modified Arrhenius equation (Equation 3.1 on page 166) with three parameters: pre-exponential factor, activation energy and activation volume. As noted previously, the activation volume accounts for the pressure dependence of the rate constant. This parameter is typically non-zero only at high pressures. The rate expression can be modified using an optional built-in or user-defined gel effect correlation as described later in the text.
k
Propagation
The chain radicals grow or propagate by the addition of monomer molecules to form long polymer chains ( Pni ) . The propagation reaction is represented by:
Pni + M j Pnj+1
ij ij Rp = kp C Mj Pni
where monomer j is being added to a polymer chain of length n, with an active segment of type i. The resulting polymer chain will be of length n+1 and the active segment will be of type j. The active segment type usually represents the last monomer incorporated into the polymer chain. For copolymerization, there will be N m * N m propagation reactions having different reactivities. For example, with two monomers, the monomer being
172
added could be monomer 1 or monomer 2 while the active segment type could be segments from monomer 1 or monomer 2. Hence there will be four rate constants ( k11 , k12 , k21 , k22 ) where the first subscript refers to the active segment type while the second subscript refers to the propagating monomer type. For the terminal model the rate of propagation is dependent only on the active segment and propagating monomer concentrations. This copolymerization scheme can be adapted for modeling the stereoregularity (isotactic, syndyotactic or atactic) of monomer addition in homopolymerization.
Head-to-Head Propagation
When reactions occur between substituted vinyl monomers or 1,3 dienes, the repeat units usually join the chain in a head-to-tail configuration, as shown below (here HTT = head-to-tail). A portion of the monomers may join the chain in the head-to-head configuration, as shown in the second reaction below. Head-to-head unions can also result from termination by combination as described later.
H C R
CH2* + R
HTT Propagation
head-to-tail dyad
H C R H2 H C C R H C R CH2*
C CH* + H2 R
HTH Propagation
R
head-to-head dyad
H C C H2 R CH2*
The head-to-head dyads disturb the normal regularity of the chain. As a result, the head-to-head fraction of the polymer can have a strong influence on the crystallinity of the polymer, and thus influence the mechanical properties of the final product. The model can track head-to-head additions using the optional HTH Propagation reaction. The polymer attributes HTHFLOW and HTHFRAC (head-to-head flow and fraction) must be included in the list of attributes on the Polymers, Polymers subform. The model does not explicitly track normal head-to-tail additions. Instead, the standard propagation reaction is used to track the total (head-to-head and head-to-tail) propagation rate. The head-to-head propagation reaction explicitly tracks the head-to-head propagations. This design allows the user to fit the overall propagation rate first, and then refine the model by adding head-to-head additions. The HTHFLOW attribute is a scalar value. The overall rate of change of the head-to-head flow Rhth is calculated by summing the head-to-head additions across all pairs of monomers. Termination by combination also generates head-to-head pairs as discussed later. The net rate expression for head-tohead dyads can be written as:
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Rhth =
Nmon Nmon i =1 j =1
[(C
Mi
ij i ji ij ] 0j k hth + CMj 0 k hth ) + i j ktc
Chain Transfer to Small Molecules

Chain transfer to small molecules such as monomer, solvent or chain transfer agent usually involves the abstraction of hydrogen from the small molecule by the chain radical and leads to the termination of the live chain. At the same time, a new primary transfer radical is formed which can start chain polymerization. The effect of chain transfer on the polymerization kinetics depends on the reactivity of the transfer radical. When the transfer radical is very reactive, as is the case when the chain initiation rate constant is greater than the propagation rate constant, chain transfer will not lower the polymerization rate or conversion, but will reduce the molecular weight of the polymer. However, if the transfer radical is less reactive than the monomerbased propagating radical, as in the case of low chain initiation rate constant, both the conversion and molecular weight of the polymer will be lowered.
Chain Transfer to Solvent or Agent

Chain transfer to solvent and chain transfer to a transfer agent have the following rate expressions:
Pni + Ak Dn + R Pni + S k Dn + R
ij ij Rtra = ktra CAk Pni ij ij Rtrs = ktrs CS k Pni
For transfer to agent or solvent the transfer radicals are assumed to have the same reactivity as the primary radicals formed by initiation. The case where the transfer radical has a different reactivity than the primary radical may be added in a future version.
Chain Transfer to Monomer Generation of Terminal Double Bonds

In the chain transfer to monomer reaction, the live polymer end ( Pn ) abstracts a hydrogen from a monomer molecule, resulting in a dead polymer chain ( Dn ) . The monomer, which loses a hydrogen, becomes a live polymer end group with an unreacted double bond ( P 1= ) . Subsequent propagation reactions generate long-chain polymer radicals with a terminal double-bond segment at the opposite end of the chain (Pn = ) . These initial reaction steps are shown below:
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Pn + M
Chain Transfer to Monomer Dn Propagation + n-1 M P1= Pn= +
P1=
Terminal double bond segment
Terminal double bond segment
The terminal double bond segments can react with live end groups through terminal double bond polymerization reactions as described later in this section. These reactions lead to the formation of a molecule with a long chain branch. The model optionally tracks terminal double bonds using the polymer component attribute TDBFLOW, which contains one element for each type of segment. The chain transfer to monomer reaction does not always generate a terminal double bond. The terminal segment may undergo a re-arrangement reaction, which destroys the double bond site. The model parameter TDB fraction
( f ) can be used to specify the fraction of chain transfer to monomer

ij TDB ij j= ij j Pni + M j Dn + fTDB P + 1 fTDB P 1 1
reactions that generate a terminal double bond. The reaction rate of the chain transfer to monomer reaction is defined as:
ij ij Rtrm = ktrm CMj Pni
Where Rtrm
( ) is the rate of consumption of monomer j and live polymer end

ij
groups of type i and the generation rate of live ends of type j. The generation rate of terminal double bonds of type j Rtrm is defined by:
j= ij ij Rtrm = fTDB ktrm CMj Pni
( )
j=
Chain transfer to polymer, which is also included in the kinetic scheme, is discussed in the section that follows on Termination.
Termination
Bimolecular termination of radicals may involve primary radicals ( R ) and chain radicals ( Pnj ) . However, the concentration of primary radicals is usually much lower than the concentration of chain radicals. Hence, only bimolecular termination involving chain radicals is included in the built-in kinetic scheme. In termination, the chain radicals are destroyed and live chains are converted to dead polymer chains. Intermolecular termination occurs by one of two mechanisms, combination (coupling) or disproportionation. Many monomers (e.g. MMA) show both types
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of termination while other monomers (e.g. styrene) terminate predominantly by combination. The mode of termination has a strong influence on the average polymer chain length and chain length distribution, especially when chain transfer is not significant. When the combination reaction is dominant, the polydispersity (in a single CSTR) will approach 1.5. The polydispersity approaches 2.0 when disproportionation is dominant.
Termination by Combination
In termination by combination, two live polymer end groups react with each other, forming a single dead chain with a head-to-head segment pair. Each of these reactions, on average, doubles the molecular weight of the polymer. The figure below shows an example for poly(styrene).
Pn
C CH H2
Pm +
HC C H2 C H2
H C
Dn+m
H C
C H2
The reaction rate depends on the concentration of the live end groups:
Pni + Pmj Dn + m
ij ij j i Rtc = ktc Pn Pn
The formation of head-to-head segment dyads can be tracked by including the optional HTHFLOW and HTHFRAC (head-to-head flow and head-to-head fraction) attributes in the attribute list on the Polymers, Polymers subform. Head-to-head sequences can contribute to thermal instability and may cause degradation during storage or subsequent processing.
Termination by Disproportionation
In disproportionation reactions, the radical at the end of one chain attacks a hydrogen atom at the second-to-last carbon atom in the second chain, forming two dead polymer molecules with no net change in molecular weight. Disproportionation results in one of the dead chains having a saturated endgroup while the other will have an end-group with a terminal double bond. For example:
Pn
H CH CH3 C C
Pm
CH3 C H
Dn=
CH3 C C
Dm
CH3
+
O
C CH2 C O
+ HC CH2
O C O OCH3
OCH3
OCH3
OCH3
The reaction rate depends on the concentration of the live end groups:
ij i= ij Pni + Pmj fTDB Dn + 1 fTDB Dn + Dm
ij ij Rtd = ktd Pnj Pni
The formation of terminal double bonds can be tracked by including the TDBFLOW and TDBFRAC (terminal double bond flow and fraction) in the list
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of attributes on the Polymers, Polymers subform. Terminal double bonds can contribute to thermal instability and may cause degradation, branching and gelation during storage or subsequent processing. The chain transfer to monomer reaction does not always generate a terminal double bond. The terminal segment may undergo a re-arrangement reaction, which destroys the double bond site. The model parameter TDB fraction
( f ) can be used to specify the fraction of chain transfer to monomer

ij TDB i= i= ij ij i Rtd = fTDB ktd Pn Pnj
reactions that generate a terminal double bond. The generation rate of terminal double bonds of type i by disproportionation Rtd
( ) is defined by:
Inhibition
Inhibition is included as an additional termination mechanism. This involves reaction between a chain radical and a small molecule (inhibitor or impurities) to form a dead chain:
Pni + X k Dn
ik ik Rx = kx C Xk Pni
The model assumes that the inhibitor is consumed by the reaction; the polymer mass generation rate is adjusted accordingly.
Gel effect in Termination

Bimolecular termination reactions between chain radicals become diffusion controlled at high polymer concentration or high conversion. This leads to an increase in the polymerization rate and molecular weight. This condition is known as the gel effect or Trommsdorff effect. At high conversions the increased viscosity of the reaction medium imposes a diffusional limitation on the polymer chains, leading to lower effective termination rates. Eventually at high enough conversions, even the propagation, initiation, and chain transfer rates may be affected by the diffusional limitation. The diffusional limitation is modeled by multiplying the low conversion reaction rate coefficients by a gel-effect factor that will lower their effective value with increasing conversion. The free-radical model includes an option to modify the reaction rate expressions using a built-in or user-defined gel-effect correlation, as described later in this chapter.
Long Chain Branching

Chain Transfer to Polymer
The polymer radical in one chain can transfer to a repeat unit in a second chain. This chain transfer to polymer reaction always generates a long chain branch, since subsequent propagation from the live site causes the backbone molecule to grow a new branch. The chain transfer to polymer reaction can be written as:
Pni + Dm Dn + Pmj
ij ij Rtrp = ktrp m j Dm Pni
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Each transfer reaction generates one long chain branch. The optional polymer component attributes LCB and FLCB are used to track the molar flow rate of long chain branches and the long chain branching frequency (branch point per thousand repeat units).
Terminal Double Bond Polymerization

Polymer chains with terminal double bonds are formed by several reactions, including chain transfer to monomer, termination by disproportionation, betascission and beta-hydride elimination. These terminal double bond groups can participate in propagation reactions in much the same manner as a monomer molecule. The resulting terminal double bond propagation reactions generate a long chain branch since the propagation reaction goes through the terminal double bond, leaving the polymer molecule attached to the TDB group attached to the backbone of the growing live polymer molecule.
Pm + Dn=
Pn+m Molecule with long-chain branch
Propagation + Termination
Each terminal double bond propagation reaction generates one long chain branch. This reaction can also transfer the live end from one type of segment to another (e.g., from segment i to segment j). The optional polymer component attributes LCB and FLCB are used to track the molar flow rate of long chain branches and the long chain branching frequency (branch point per thousand repeat units). The rate of terminal double bond polymerization, Rtdbp between live end i and terminal double bond segment j can be written as:
j= Pni + Dm Pnj+ m ij ij j= Rtdbp = ktdbp Pni Dm ij
The concentration of terminal double bond segments is calculated from the optional polymer component attribute TDBFLOW.
Short Chain Branching

The radical in a live end group can undergo a backbiting reaction in which the radical in live end segment i is transferred to a hydrogen atom in segment j in the same chain, forming a short chain branch. Short chain branches, typically five or six carbon atoms in length, are quite morphologically different than long chain branches, which are formed by a number of reactions. The backbiting reaction leads to short chain branches if the backbone radicals are stable and can continue propagation. The total rate of short chain
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branching, RSCB , depends on the live end group concentrations, rate constants for the short chain branching reaction, k
i scb
i , and the
Pni Pnj
i RSCB = i k scb i
Short chain branching is tracked by the optional polymer component attribute SCB. The short chain branching frequency (short chain branches per thousand repeat units) is reported in the optional polymer attribute FSCB. For some polymers (e.g. polypropylene) the backbone radical can be highly unstable and will result in the scission of the chain into a dead polymer chain with a terminal double bond and a short live chain one to six carbon atoms long. Use the beta scission reaction (see below) to track these types of reactions.
Beta-Scission
A simplified beta-scission reaction is included in the built-in kinetics. It is limited to reactions where a live chain undergoes scission to form a dead chain of the same length and a primary radical:
i i= i Pni fTDB Dn + (1 fTDB ) Dn + R i i Rbs = kbs Pni
This reaction can be used to simulate backbiting reactions which form shortchain polymer radicals (see Short Chain Branching). The beta scission reaction usually generates a terminal double bond corresponding to the live end i. In some special cases, the double bond may not form or may be unstable. The terminal double bond fraction parameter,
i f TDB , can be used to specify the fraction of beta-scission reactions which
generate a terminal double bond (by default, this parameter is unity). Thus, the rate of generation of terminal double bonds from the beta-scission reaction, Rtd , can be defined as:
i= ij ij i Rtd = fTDB ktd Pn Pnj i=
Reactions Involving Diene Monomers

Cis and Trans Propagation
Propagation reactions involving 1,3-diene monomers, such as butadiene or isoprene, can generate three types of repeat segments as shown below.
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Normal Propagation * +
CH2 CH*
Vinyl Configuration
Cis Propagation * +
CH2 C H C
CH2*
Cis Configuration
H H
* +
Trans Propagation
CH2 C H C
Trans Configuration
CH2*
Although these segments may exhibit different physical properties, it is convenient to lump them together as a single repeat segment, and track the various segment configurations using the optional polymer component attributes CIS-FLOW and TRANSFLO. Likewise, the three types of propagation reactions are lumped together under the standard propagation reaction. Optional Cis-Propagation and Trans-Propagation reactions are used to specify the rate parameters for reactions that generate segments with the cis- or trans- configurations. This design is intended to keep the model development process as simple as possible. The user can add cis/trans/vinyl accounting a working model without changing any of the existing rate parameters. The new CIS-FLOW and TRANSFLO attributes are dimensioned NSEG and correspond to the bulk polymer. The flow rate of each diene segment in the vinyl configuration can be calculated by taking a mole balance across the various configurations taken by diene segments. The optional polymer attributes CIS-FRAC, TRANSFRA, and VINYLFRA report the molar fraction of each type of diene segment in each of the three configurations (an additional cross link configuration is also tracked as discussed later). The rate of formation of segments of type j with cis configuration, Rcis , is calculated by summing over all types of live end groups i:
j
Pni + M j Pnj+(1cis )
j ij i Rcis = i k cis CMj 0
Likewise, the rate of formation of segments of type j with trans configuration,

j Rtrans , is calculated by summing over all types of live end groups i: j ij i Rtrans = i ktrans CMj 0
Pni + M j Pnj+(1trans )
ij
In the equations above, k cis and k trans are, respectively, the net rate constants for cis and trans propagation of monomer j onto a chain with a live end i. The standard reaction scheme does not include any reactions which consume the cis and trans end groups. Further, the model does not constrain the cis and trans reaction rates in any manner; the model user must ensure that the cis and trans propagation rates are lower than the net propagation rate.
ij
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Pendent Double Bond Polymerization

Diene segments in the vinyl configuration contain a pendent double bond that hangs off the main polymer chain. Live chains can react with these double bonds in a pendent double bond polymerization reaction, analogous to normal propagation. These reactions generate a short cross-link between two long linear chains, as shown below.
Reaction Pathway Propagation * +

CH2 CH*
Pendent double bond PDB Polymerization Cross-linked molecule *

ij
*
i
The pendent double bond polymerization rate ( R PDB ) depends on the concentration of live ends of type i ( 0 ) and the concentration of pendent (vinyl) double bonds of type j in the bulk polymer phase ( 1
j ( vinyl ) Pni + Dm Pnj+ m ij i j ( vinyl ) RPDB = k ij pdb 0 1 j ( vinyl )
):
The model assumes the reaction generates a new live segment of type j. The reaction model does not distinguish between subsequent propagation from this new live site from normal propagation reactions involving live end groups. Each pendent double bond polymerization reaction involving diene segment j generates a new cross-link of type j. The flow rate of cross-links is tracked by the optional polymer component attribute XLFLOW. The cross-linking density is (moles of links per mass of polymer) is tracked by polymer attribute XDENSITY. The concentration of vinyl groups (pendent double bonds) is determined by a mole balance. The flow of pendent double bonds of type i ( PDB(i ) ) is calculated by subtracting the concentration of other possible configurations (cis, trans, or cross-link):
PDB(i) = SFLOW (i) (CIS _ FLOW (i) + TRANSFLO(i ) + XFLOW (i ))

This flow rate is used to determine the concentration of pendent groups. When the degree of cross-linking is extensive, the polymer can form a gel phase. The current version of the Free-Radical kinetics model does not account for gelation. This limits the model to situations with a low degree of cross-linking.
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Following are the model features and assumptions used in the free-radical polymerization model available in Aspen Polymers.
Calculation Method
In the Aspen Polymers free-radical bulk/solution polymerization model, the polymer chain length distribution averages and molecular structure properties are calculated using the population balance and method of moments approach, based on the built-in kinetics shown in the Built-in Free-Radical Polymerization Kinetic Scheme figure on page 162. Population balance equations are used to account for the concentration of live polymer chains and combined polymer chains of length n. The f-th live and combined polymer chain length distribution moments are defined as follows:
jf = n f Pnj
n=0 Nm f = n f Pnj + Dn j =1 n=0
For homopolymerization the index f is a scalar variable and the active segment superscript j may be dropped for the live polymer moment definition as there is only one segment type. Hence, for homopolymerization there will be one zeroth moment, one first moment, one second moment and so on for the live and combined polymer. However, for copolymerization, the index f will be a vector whose elements denote the monomer with respect to which the moment is defined. For copolymerization with respect to every active segment, there will be one zeroth moment, N m first moments,
Nm+
N m ( N m -1) second moments and so on. 2
For example, for copolymerization with three monomers, the vector index f can have the following values for the first moment:
1 f = 0 , 0
0 1 , 0
0 0 1
representing the first moment with respect to segment one, two and three respectively. The application of the moment definitions to the live and bulk polymer population balance equations yields the live and bulk polymer chain length distribution moment equations. The general moment equations are listed in the following figures. The various zeroth, first, second, etc. moment
182
equations can be generated from these by substituting the appropriate values for the index f. The live polymer chain length distribution moment equation is shown here:
d if
N CI NM b jk c f j ij i jk a jk k C R k C k si CCk C Mj (h ) jk = [ (n j )] + + pi Mj trm Mj 0 dt i =1 k =1 N BI i 0k 1 1 0
k + k k sid f k =1
NM NM f f f a i ( ) C + k ij k pji CMi fj j fj p Mj j a i =1 a =0 a i =1 ji i ij i + ktrp f + j 0 ktrp 1 fj i =1 i =1 NM NM NM NM
ij ji + k scb if k scb fj i =1 i =1 ij ij (ktd + ktc ) 0i fj NM i =1 NM f j= i ji i = j + k a a f a ktdb 0 f i =1 i =1 a =0 NM ij tdb f NM NM f f j ji i j i + k ij pdb a f a k pdb 1 f a i =1 i =1 a =0
where j contains some terms for reactions leading to the formation of dead polymer
jk jk jk ji i j ji j = kbs + ktrmCMi + ktrp 1 + ktra C Ak + ktrs CSk + k x C Xk
NM
NM
NA
NS
NX
i =1
i =1
k =1
k =1
k =1
The moments with respect to terminal double bonds are approximated:

i= 1 i0=
1 0
i2= i0=
2 0
etc...
i
In the final term of the equation, the symbol represents the molar fraction of diene segment i in the vinyl configuration (attribute VINYLFRA). This term is zero for all segments that are not dienes. The term
0k
represents the concentration of polymer molecules containing
an undecomposed initiator fragment associated with bifunctional initiator k. The bulk polymer chain length distribution moment equation is shown here:
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d f
NM NM f j cj ij i aj bj k C R ktrm C Mj 0 CMj (h ) = [ (n j )] + + k sij CC pi Mj dt j =1 i =1
NM f f ( f a ) i N M ji + k ij a k p CMi fj p C Mj a (j ) i =1 j =1 a =0 ij i ktc 0 fj + i =1 j =1 NM NM
1 N M f f ij i j a ktc a f a 2 i =1 a =0
NM NM f f j i = N M N M ij i j = N M N M ij i j = ji + ktdb f a a ktdb f 0 ktdb 0 f i =1 j =1 i =1 j =1 i =1 j =1 a =0 a NM NM NM NM NM NM f f j i j ij i j ji i + k pdb k k ij pdb 0 1+ f pdb f 1 a f a a +1 i =1 j =1 i =1 j =1 i =1 j =1 a =0
For copolymers, segment-segment dyad rate equation is:
d i , j dt
i ji j tc i j = k ij p 0 C Mj + k p 0 C Mi + k i , j 0 0
Quasi-Steady-State Approximation (QSSA)

Users may invoke the Quasi-Steady-State Approximation (QSSA) for the live moment equations. Invoking QSSA converts the live moment differential equations (ODE) to algebraic equations, which are solved internally in the kinetics routine. Assuming QSSA is equivalent to assuming that the live moments attain their steady-state values instantaneously. This approximation makes the system of ODEs much easier to integrate by reducing stiffness. Comparison of the results with and without QSSA for most free-radical polymerization systems, where the chain lifetimes are short compared to the residence time, show negligible differences. Therefore it is usually reasonable to use the QSSA. However, users should check the validity of this approximation by running cases with the QSSA switch set to YES and NO for their particular system. By default the QSSA is turned off (QSSA switch is set to NO). Users have the option of invoking the QSSA for all the live polymer moment equations, or selectively for only the zeroth, first, or second moment of live polymer.
Phase Equilibrium
The polymerization model currently considers a single-phase system (vapor or liquid), two-phase system (vapor and liquid), or three-phase (VLL) system when calculating concentrations for the reaction kinetics. For single-phase systems, the reacting phase may be either vapor or liquid. In multi-phase systems, reactions can occur in one or more phases simultaneously. Each reaction object is associated with a single reacting phase, identified on the options form.
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By default the reacting phase is assumed to be the liquid phase (for VLL systems, the reacting phase must be specified). Several reaction models can be referenced from a single reactor block to account for reactions in each phase.
Gel Effect
Bimolecular termination reactions between chain radicals become diffusion controlled at high polymer concentrations or high conversion leading to an initial increase in the polymerization rate and molecular weight. This condition is known as the gel effect or Trommsdorff effect. At high polymer concentrations, the increased viscosity of the reaction medium imposes a diffusional limitation on the polymer chains, which leads to lower effective termination rates. Typically the termination rate coefficients are affected first by the gel effect because they involve diffusion of two bulky polymer radicals. Eventually at high enough conversions, even the propagation, initiation, chain transfer reactions, and the initiator efficiency are lowered by the gel effect. Hence, in general it may be necessary to allow gel/glass effects for all the polymerization reactions in the built-in kinetic scheme.
Diffusional Limitation
The diffusional limitation is usually modeled by multiplying the low conversion reaction rate coefficients, ko , by a gel effect factor, GF, that decreases with increasing conversion. Hence the effective rate coefficient for a reaction is given by:
keff = koGF
Several empirical and semi-empirical correlations relating the gel effect factor to conversion and operating conditions are available in the literature. Currently two of these have been implemented as built-in correlations. Users will be able to use these gel effect correlations simply by specifying the correlation number and the parameters. The built-in correlations are: Correlation Number 1:
GF =
a1 a3 1 + a2 X p
= Weight fraction of polymer
Where:
Xp
This correlation has three user specified parameters, a1 , a2 , and a3 . Correlation Number 2:
A 2 3 GF = 1 a X exp BX p + CX p + DX p 9 p
[(
)]
a10
With:
A = a1 + a2T
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B = a3 + a 4 T
C = a5 + a6T D = a7 + a8T
Where:
X p = Weight fraction of polymer

T = Temperature in Kelvin
This correlation has ten user specified parameters, a1 to a10 . Users may also include their own gel effect correlation by specifying a correlation number greater than the number of built-in gel effect correlations (currently two) . In this case, users must provide the correlation for the gel effect factor in the form of a Fortran subroutine. The user gel effect subroutine argument list is documented here:
User Gel Effect Subroutine Arguments
Subroutine USRGEL ( ICORR, MAXGP , GPAR ,WFTFRP , GF, + + + + SOUT NPO NITG ,NSUBS ,IDXSUB,ITYPE , ,NREALK,REALK , ,NCK ,REA , ) ,NREA ,NBOPST,IDS ,ITG NINTK ,INTK
Variable ICORR MAXGP GPAR WTFRP GF SOUT NSUBS IDXSUB ITYPE I/O I I I I O I I I I Type-Spec I I R R R R I I I NSUBS NSUBS MAXGP Dimension Description Gel effect correlation number Maximum number of gel effect parameters Gel effect parameters Weight fraction of polymer Gel effect factor Outlet stream Number of substreams Location of substreams in stream vector Substream type vector 1 = MIXED 2 = CISOLID 3 = NC NINTK INTK NREALK REALK NPO I I/O I I/O I I I I R I NREAL NINT Number of integers for model Integer array for model Number of reals for model Real array for model Number of property methods
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Variable NBOPST IDS
I/O I I
Type-Spec I I
Dimension 6, NPO 2, 13
Description Property method array Block IDs i, 1 Block ID i, 2 to i, 4 used by system i, 5 kinetic subroutine name
NCK NITG ITG NREA REA
I I I I I
I I I I R NREA NITG
Total number of components Length of integer array for kinetics Integer array for kinetics Length of real array for kinetics Real array for kinetics
Polymer Properties Calculated

The following variables can be calculated by the built-in kinetics routine based on the polymer attributes and the subset of the built-in kinetics used for a specific simulation: Zeroth, first and second moments for the combined polymer Zeroth and first moments for the live polymer Number, weight and z-average degree of polymerization and polydispersity index for the combined polymer (DPN, DPW, DPZ, PDI) Number, weight and z-average molecular weight for the combined polymer (MWN, MWW, MWZ) Average molecular weight of segments in combined polymer (MWSEG) Copolymer segment composition for combined polymer (SFLOW, SFRAC) Mole fraction of combined polymer chains that are live (LDFRAC) Number average degree of polymerization for live polymer (LDPN) Live polymer active segment composition (LEFLOW, LEFRAC) Copolymer segment composition for live polymer (LSFLOW, LSFRAC) Copolymer dyad flow rates (DYADFLOW), fractions (DYADFRAC), and the number-average block length with respect to each type of monomer (BLOCKN). Total number of short and long chain branches (SCB, LCB) Short and long chain branching frequencies (FSCB, FLCB) Flow rate and fraction of head-to-head dyads (HTHFLOW, HTHFRAC) Flow rate of cis-, trans-, and cross-link segments configurations corresponding to each type of diene monomer (CIS-FLOW, TRANSFLO, XLFLOW) Fraction of diene segments in the cis-, trans-, and vinyl configuration (CIS-FRAC, TRANSFRA, VINYLFRA)
These parameters are stored as component attributes defined in Chapter 2. These variables, except for the branching frequencies, are related to the moments by the relationship shown here:
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DPN =
(i)
1 i =1
Nm
LDPN =
(i)
1
Nm
( j)
0 i =1
i =1 Nm
SFRAC( I ) =
1 ( i )
(i)
1 i =1
Nm
LSFRAC( I ) =
1 ( i )
(i)
1 i =1 0
Nm
PDI =
2 0 Nm i (1) i =1
LPFRAC =
( j)
j =1
Nm
LEFRAC( I ) =
0 ( j )
( j)
0 j =1
Nm
The branching frequencies are calculated from the rate of chain transfer to polymer and the rate of backbiting reactions. The branching frequencies are reported in terms of number of branches per thousand segments in the polymer.
Structural Properties
Frequently some of the polymer properties are reported in terms of other properties that are related to these structural properties. These include properties such as melt flow rate or melt index, viscosity numbers, or Kvalues, etc. User-property subroutines can be set up for calculating some of these polymer properties from the polymer moments and structural properties.
User Profile Properties

In addition to the polymer properties reported through the component attributes, additional results are reported through User Profile variables. The following user profile variables are currently available in the built-in freeradical kinetics routine:
Profile Number 1 2 3 4 5 Profile Type Conversion of monomer to polymer Rate of polymerization (propagation) Heat of polymerization Reacting phase volume (or volume flow) Reacting phase total moles Units Fraction KMOL/S/CUM KCAL/S/CUM CUM or CUM/S KMOL or
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Profile Number 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25
Profile Type (or mole flow) Reacting phase average molecular weight Rate of chain termination by combination Rate of chain termination by disproportionation Rate of chain termination by inhibition Rate of initiation of radicals Rate of induced initiation Rate of chain transfer to monomers Rate of chain transfer to polymer Rate of chain transfer to agents Rate of chain transfer to solvents Rate of beta scission Rate of short chain branching Concentration of initiators Concentration of catalysts Concentration of coinitiators Concentration of monomers Concentration of transfer agents Concentration of solvents Concentration of inhibitors Concentration of polymer
Units KMOL/S KG/KMOL KMOL/S/CUM KMOL/S/CUM KMOL/S/CUM KMOL/S/CUM KMOL/S/CUM KMOL/S/CUM KMOL/S/CUM KMOL/S/CUM KMOL/S/CUM KMOL/S/CUM KMOL/S/CUM KMOL/CUM KMOL/CUM KMOL/CUM KMOL/CUM KMOL/CUM KMOL/CUM KMOL/CUM KMOL/CUM
For more information, see Adding Gel-Effect on page 192.
Rates and Concentrations

The rates and concentrations reported via the user profiles can be used to calculate additional information, such as the kinetic chain length and fraction of dead chains with terminal double bond segments. These user profile variables can only be accessed if you are calling the free-radical kinetics from a batch reactor (RBatch) or a plug flow reactor (RPlug).
Specifying Free-Radical Polymerization Kinetics

Accessing the Free-Radical Model
To access the Free-Radical polymerization kinetic model: 1 From the Data Browser, click Reactions.
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2 3 4 5
From the Reactions folder, click Reactions. The Reactions object manager appears. If the kinetic model already exists, double-click the desired Reaction ID in the object manager or click Edit to get to the input forms. To add a new model, from the Reactions object manager, click New. If necessary, change the default ID for the reaction. Select Free-Rad as the reaction type and click OK.
Specifying the Free-Radical Model

The Free-Radical model input forms are listed below:
Use this sheet Species Reactions Rate Constants Options Gel Effect To Define reacting species Specify reactions and rate constant parameters Summarize rate constant parameters Specify reacting phase and select additional options Supply gel-effect correlation parameters
Specifying Reacting Species

You must specify the reacting species in the Species sheet: 1 2 In the Polymer field, specify the polymer produced. In the Monomers field, list the reacting monomers. For each monomer, in the goes to field, specify the polymer segment that the monomer converts to. Continue listing other types of reacting species, e.g. solvents, transfer agents, etc. Select the Generate Reactions option if you want the reactions to be generated automatically. After going through the reaction generation once, it is recommended that you turn off this feature. Otherwise, the reaction generation is performed repeatedly.
3 4
Listing Reactions
The Free-Radical model generates reactions based on the list of reacting species. You can view the system-generated reactions, then assign rate constant parameters to these reactions. You can view a list of the system-generated reactions on the Reactions sheet. In the Reaction summary listing for each reaction, the first column indicates the reaction type. The second column lists the reactants, and the last column lists the products. The Data Browser window can be resized to better view the reaction listing. Use the following options:
Click New To Add new reactions to the scheme
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Edit Rate Constants
Edit the current reaction indicated by the row selector Specify reaction rate constant parameters for the reactions
Adding Reactions
To add a new reaction to the scheme click New to open the Add Reaction subform: 1 2 3 4 In Reaction type, select a type for the new reaction. The Reaction scheme for that type is displayed. In the reactant fields (for example, Initiator, Catalyst) enter the reactants of the categories allowed for that reaction type. Where applicable, specify reaction by-products and stoichiometric coefficients. Click Cancel to discard the new reaction or Click New to add a new reaction or Click or Click Done to return to the reaction summary. to check the Completion status
Editing Reactions
To edit a reaction, click Edit to open the Edit Reaction subform: 1 2 3 Modify the Reaction type as needed. The Reaction scheme for that type is displayed. Modify reactants as needed. Click or Click Done to return to the reaction summary. to check the Completion status
191

To assign rate constants to user reactions, click Rate Constants to open the Rate Constant Parameters subform. Alternately, move to the Rate Constants summary form for a grid-style form displaying rate constants for all reactions. For each reaction, enter: 1 2 3 4 5 6 7 8 9 In the ko field, enter the pre-exponential factor. In the Ea field, enter the activation energy. In the V field, enter activation volume. In the Tref field, enter reference temperature. In the Efficiency field, enter initiator efficiency for initiation reactions. In the No. radicals field, enter the number of primary radicals formed in initiation reactions. In the TDB frac field, enter the fraction of reactions that generate a terminal double bond. In the Gel Effect field, specify the number of the gel-effect sentence number associated with the specified reaction rate. In the Efficiency Gel Effect field, specify the number of the gel-effect sentence associated with initiator efficiency.
10 Click the stoichiometry list and select a new reaction. Enter rate constants for the new reaction. You can use the Prev and Next buttons to select the previous or next reaction in the list (or move to another row when using the Rate Constants summary form). 11 Click or Click Close to return to the reaction summary. to check the Completion status
Adding Gel-Effect
Use the Gel-Effect sheet to add gel effect to reactions: 1 2 3 4 To activate the form, click Use Gel Effect. In Sentence ID, enter a unique integer identifier. In the Corr. No. field, specify a gel effect correlation number (use a number greater than 100 for user-defined gel effect correlations). In Parameters, list the parameters for the gel effect correlation. When the specified correlation number is larger than the number of builtin correlations, you must also enter the gel-effect subroutine name in the Subroutine box. 5 To repeat steps 1-4 for additional gel-effect correlations, in the Sentence ID field, click New.
Selecting Calculation Options

You can select additional simulation options for the model such as QSSA, special initiation options, and gel-effect on the Options sheet.
Option Field Description
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QSSA
Apply the quasi-steady-state approximation. This activates additional options in the Apply QSSA to frame on the right side of the form. Inside this frame, select the moments for which you would like to apply the QSSA approximation.
Special Initiation
Activate the Special Initiation Parameters frame at the bottom of the form. In this frame, list the monomers affected, and enter the special initiation coefficients and radiation intensity.
Reacting Phase
Specify the phase in which reactions occur. All of the reactions in the free-radical reaction object are assumed to take place in the same phase. You can use two (or more) free-radical models in the same reactor to account for simultaneous reactions in multiple phases (see the SuspensionEPS example).
If the Reacting Phase option is set to Liquid phase 1 or Liquid phase 2 the model assumes two liquid phases exist. When the named phase is not present, the model prints a warning message and sets the reaction rates to zero. There are two options for handling phase collapse: Select the Use bulk liquid phase option to force the model to apply the specified reaction kinetics to the bulk phase when the named phase disappears. Select the Suppress warnings option to deactivate the warning messages associated with phase collapse.
Note: You must specify the Valid Phases keyword for each reactor model referencing the kinetics to ensure the reactor models are consistent with the reaction models.
Specifying User Profiles

User profiles may be tabulated in RBatch and RPlug reactors. To specify user profiles, go the reactors User Subroutine form User Variables sheet: 1 In the Number of user variables field, enter the number of user variable profiles to be tabulated. For a list of user profiles available in the free-radical model, see Polymer Properties Calculated on page 188.
1
2 3
In the Variable No. field, list the profile numbers in order. You must enter the profiles sequentially, without omissions. For each profile, enter a profile Label and a Units Label. Although these labels are displayed, the reactor model does not perform unit conversions on the user profiles. The user profile variables are totals. For example, the reported propagation rate is summed over all propagation reactions.
To view user profile results, go to the User Variables sheet of the reactors Profiles form.
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References
Arriola, D. J. (1989). Modeling of Addition Polymerization Systems, Ph.D. Thesis. University of Wisconsin-Madison, WI. Biesenberger, J. A., & Sebastian, D. H. (1983). Principles of Polymerization Engineering. New York: Wiley. Billmeyer, F. W. (1971). Textbook of Polymer Science. New York: WileyInterscience. Choi, K.Y. & Kim, K.J. (1987). Steady State Behavior of a Continuous Stirred Tank Reactor for Styrene Polymerization with Bifunctional Initiators. Chemical Engineering Science. Choi, K.Y., Liang, W.R., and G.D. Lei (1988). Kinetics of Bulk Styrene Polymerization Catalyzed by Symmetrical Bifunctional Initiators. Journal of Applied Polymer Science Vol. 35, 1547-1562. Choi, K.Y., & Lei, G.D. (1987). Modeling of Free-Radical Polymerization of Bifunctional Initiators. AICHE Journal Vol. 33 No. 12, 2067-2076. Friis, N., & Hamielec, A. E. (1976). Gel-Effect in Emulsion Polymerization of Vinyl Monomers. ACS Symp. Ser., 24. Ham, G. E. (Ed.). (1967). Vinyl Polymerization Volume 1. New York: Marcel Dekker. Hui, A. E., & Hamielec, A. E. (1972). Thermal Polymerization of Styrene at High Conversion and Temperatures. An Experimental Study. J. of Applied Polym. Sci., 16, pp. 749-769. Kim, K.J., and Choi, K.Y. (1989). Modeling of Free Radical Polymerization of Styrene by Unsymmetrical Bifunctional Initiators. Chemical Engineering Science, Vol. 44 No. 2, pp. 297-312. Lenz, R. W. (1968). Organic Chemistry of Synthetic High Polymers. New York: Wiley-Interscience. Marten, F. L., & Hamielec, A. E. (1979). High Conversion Diffusion Controlled Polymerization. ACS Symp. Ser., 104. Ray, W. H., & Laurence, R. L. (1977). Polymerization Reaction Engineering. In Chemical Reactor Theory. New Jersey: Prentice-Hall. Villalobos, M.A., Hamielec, A.E., and P.E. Wood (1991). Kinetic Model for Short-Cycle Bulk Styrene Polymerization through Bifunctional Initiators. Journal of Applied Polymer Sciene V 42, 629-641.
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10 Emulsion Polymerization Model
This section covers the emulsion polymerization model available in Aspen Polymers (formerly known as Aspen Polymers Plus). Topics covered include: Summary of Applications, 195 Emulsion Polymerization Processes, 196 Reaction Kinetic Scheme, 196 Model Features and Assumptions, 211 Polymer Particle Properties Calculated, 214 Specifying Emulsion Polymerization Kinetics, 215
The Aspen Polymers Examples & Applications Case Book illustrates how to use the emulsion model to simulate styrene butadiene copolymerization.
The emulsion polymerization model is applicable to emulsion polymerization processes where nucleation occurs by both the micellar and homogeneous mechanisms or to seeded polymerization. Some of the applicable polymers are described below: Styrene - A component of synthetic rubber and paper coating Butadiene - Synthetic rubber, impact modifier in ABS and HIPS Tetrafluroethylene - Polytetrafluroethylene (PTFE), fluoropolymers Viton Vinylacetate - Polyvinylacetate (PVA) adhesives, paint formulation Methylmethacrylate - Surface coating applications. Acrylic Acid - Minor component in paints 2-chloro-1,3-butadiene (chloroprene) - Neoprene rubber Butyl Acrylate - Surface coatings Butyl Methacrylate - Comonomer in surface coatings Vinyl Chloride - PVC used in floor covering and coatings
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A wide variety of processes are used in emulsion polymerization. The processes that can be modeled using the Aspen Polymers emulsion polymerization model are those that follow micellar, homogeneous, or seeded polymerization. An example of a process that follows micellar nucleation and subsequent growth is the production of SBR latex in semi-batch reactors for paper coating applications. The following lists polymeric products made by emulsion polymerization: Emulsion paints, made from a number of monomers (styrene, butadiene, acrylates, etc.) and a variety of other ingredients Adhesives, from slightly plasticized poly(vinyl acetate) and poly(ethyleneco-vinyl acetate) - a pressure sensitive adhesive SBR, for carpet backing and for coating paper and card board along with china clay, thus facilitating printing on surfaces Non-woven fabrics, which have their fabrics pre-coated with polymer and then heat pressed (these are termed thermoformable felts) ABS (Acrylonitrile-Butadiene-Styrene), used in high impact strength material made by swelling of a polybutadiene latex with a mixture of styrene and acrylonitrile and polymerizing further. HIPS (High-Impact PolyStyrene) made from bulk polymerized polystyrene in the presence of polybutadiene
Emulsion Polymerization Processes

Emulsion polymerization is an industrially important process for the production of polymers used as synthetic rubber, adhesives, paints, inks, coatings, etc. The polymerization is usually carried out using water as the dispersion medium. This makes emulsion polymerization less detrimental to the environment than other processes in which volatile organic liquids are used as a medium. In addition, emulsion polymerization offers distinct processing advantages for the production of polymers. Unlike in bulk or solution polymerization, the viscosity of the reaction mixture does not increase as dramatically as polymerization progresses. For this reason, the emulsion polymerization process offers excellent heat transfer and good temperature throughout the course of polymer synthesis. This process is always chosen when the polymer product is used in latex form.

In emulsion polymerization, free-radical propagation reactions take place in particles isolated from each other by the intervening dispersion medium. This reduces termination rates, giving high polymerization rates, and simultaneously makes it possible to produce high molecular weight polymers.
196
One can increase the rate of polymerization without reducing the molecular weight of the polymer. Emulsion polymerization has more recently become important for the production of a wide variety of specialty polymers.
Particle Formation
To appreciate the complexities of emulsion polymerization, a basic understanding of the fundamentals of particle formation and of the kinetics of the subsequent particle growth stage is required. A number of mechanisms have been proposed for particle formation. It is generally accepted that any one of the mechanisms could be responsible for particle formation depending on the nature of the monomer and the amount of emulsifier used in the recipe. The two common mechanisms for particle formation are: Micellar nucleation Homogeneous nucleation
With micellar nucleation, micelles, which are aggregates of emulsifier molecules, act as the site of nucleation. With homogeneous nucleation, the radicals produced in the aqueous phase polymerize with dissolved monomer and precipitate out to form precursor particles. The precipitated precursor particles coagulate with each other until a stable particle is formed.
Micellar Nucleation
Micellar nucleation is considered to be the primary mechanism for particle formation (Harkins, 1945; Smith & Ewart, 1948) in those emulsion polymerization systems for which the monomer is very sparingly soluble in water, and where the concentration of emulsifier is above the critical micelle concentration (CMC). As the name implies, the micelles, which are formed when the emulsifier concentration is above the CMC, act as the site for particle nucleation. The reaction mixture consists of water, monomer, emulsifier and a watersoluble initiator. The monomer is dispersed in the form of droplets in the water by agitation. The droplets formed are stabilized by the emulsifier molecules which are adsorbed on the droplet surface. In addition to the droplets, monomer is also found dissolved in the aqueous medium and solubilized inside the micelles. Similarly, the emulsifier is found in three locations: in the micelles, dissolved in the aqueous medium, and adsorbed on the monomer droplets. Since a water soluble initiator is used, the initiator molecules will be mainly found dissolved in the water medium. When a typical emulsion polymerization recipe is heated, the initiator dissociates in the aqueous medium and produces initiator radicals. Upon propagating with monomer in the water phase the initiator radicals form oligomeric radicals and enter the micelles, which are aggregates of emulsifier molecules inside which a small amount of monomer is entrapped. The capturing of a radical by micelle and reaction with the entrapped monomer signifies the formation of a particle from a micelle. As the propagation takes
197
place in the newly created particle, a thermodynamic potential difference is created for the diffusion of the monomer from the monomer droplets into the growing particles. As the particles grow, some of the micelles disintegrate and cover the growing particles to stabilize them. Therefore, the micelles are not only consumed in the formation of polymer particles, but also in the stabilization of growing polymeric particles. In fact, approximately one percent of the micelles are used in the formation of particles. When no micelles remain in the reaction mixture, micellar nucleation ceases.
Stage I
The time required for particle nucleation to be complete is also called the nucleation time or the nucleation period, and usually lasts 10-15 minutes in conventional polymerization systems. This is commonly referred to as the seed stage, or Stage I, in the emulsion polymerization industry. After the nucleation or seed stage, the number of particles in the reaction mixture remains constant if particles do not agglomerate.
Stage II
The stage following the seed stage is called the growth stage or Stage II of the emulsion polymerization. In Stage II, the polymer particles grow through a steady diffusion of monomer from the monomer droplets to the particles. Since the number of particles remains constant and the particles are saturated with monomer, this stage is marked by a constant rate of polymerization and could easily be observed on a conversion vs. time plot. Stage II is considered complete when the monomer droplets are totally depleted.
Stage III
In Stage III, the monomer finishing stage, the reaction mixture consists of the monomer swollen polymer particles and the aqueous medium. Further polymerization of the monomer in the particles takes place. This results in a decrease of the particle size due to higher density of the polymer compared to the monomer. During Stage III, the concentration of monomer dissolved in the aqueous phase falls rapidly, as does the concentration in the polymer particles. The final product obtained at the end of Stage III is called latex. The following figure illustrates the stages in a micellar nucleation emulsion polymerization reaction:
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Particle Number and Nucleation Time

The number of particles, usually in the range of 10 to 10 per liter of latex, is an important parameter in emulsion polymerization. Smith and Ewart have derived mathematical expressions for the number of particles under the following assumptions (Smith & Ewart, 1948): Particles as well as micelles are equally effective in capturing radicals from the aqueous phase Temperature of the reaction is constant Volumetric growth rate of polymer particles is constant
16 18
With these assumptions, the particle number and nucleation time are given by the following equations:
199
RI N a N p = 0.37 v s tnuc
0.4
( As E )0.6
0.6
(3.2)
0 .4 1 A E = 0.65 s v RI N a
(3.3)
s is the RI N a is the rate of generation of radicals in the water phase, and v

volumetric growth rate of swollen polymer particles. They are determined from the following equations:
RI = 2 fkd I
s = v
(3.4) (3.5)
k p M p n MWm 1 Na dp p
Where: f = Initiator efficiency = Rate constant for initiator dissociation = Initiator concentration = Avogadro's number = Propagation constant = Monomer concentration inside the particles = Average number of radicals per particle
kd
I
Na
kp Mp n
dp p
MWm = Molecular weight of the monomer

= Density of polymer = Volume fraction of polymer in the particle phase
Homogeneous Nucleation
Homogeneous nucleation is the mechanism for particle formation when monomers are more water soluble and level of emulsifier is not high enough for the formation of micelles in the recipe. The following figure shows a detailed picture of kinetic events that take place during particle formation by homogeneous nucleation:
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When the reaction mixture is heated the initiator molecules dissolved in the water medium dissociate and produce the initiator radicals. These initiator radicals react with the dissolved monomer and quickly propagate into an oligomeric radical in the water phase. As the size of the oligomeric radical increases it becomes insoluble in water and precipitates out of the water phase. This event signifies the formation of a primary polymer particle from the growing oligomeric radical in the water phase. However, these primary particles are not stable, and, hence, coagulate with each other until enough surface charge is developed to stabilize the particles. These surface charges are provided by the ionic end of the initiator molecules. In addition, the coagulated particles are also stabilized by ionic and non-ionic emulsifier added to the emulsion recipe. Once a stabilized particle is formed, it grows by getting a steady supply of monomer from monomer droplets by diffusion. As the particles grow and
201
become large, the oligomeric radicals that are formed in the water phase are directly absorbed by the particles. After sufficient number of particles are formed that are able to absorb all of the radicals in the water phase, no new particles are formed in the water phase and the number of particles becomes constant. Also in homogeneous nucleation the particle number reaches a constant value, as in micellar nucleation. The subsequent growth stage is similar to the growth stage in the micellar nucleation.
Particle Formation Rate

The rate of particle formation by homogeneous nucleation can be derived by considering the water phase kinetics and rate of precipitation of the polymers at an assumed critical chain length (jcr). Assuming the aggregation number ( N agg ) for the formation of stable particles from the precipitated precursor particles, the rate of particle formation by homogeneous nucleation is given by:
Rhomo
k pw M w dN N a (i + kde nN / N a ) = = dt N agg k pw M w + ktw Rw + kap Ap + kam Am
jcr +1
In the above equation Rw refers to the concentration of live radicals in the water phase and is given by:
nN / N a ) 1 jcr +1 R = k pw M w + ktw R + kap Ap + kam Am 1

w i de w
( + k
Where:
k pw M w
+ kap Ap + kam Am k pw M w + ktw Rw
Refer to the table of page 204 for the explanation of the symbols in the above equations.
Particle Growth
Stage II, the growth stage, starts after the completion of the seed stage in the in situ seed process . In the in situ seed process, the micelles are used for the generation of the seeds. In the case of an external seed process, a well characterized seed is used as the starting material for emulsion production. If quality control tests indicate that the particle number and particle size distribution of the seed particles will not result in the desired end-product specifications, the batch is normally terminated. Therefore, in the growth stage it can be assumed that the desired number of particles, with the desired particle size distribution has already been formed. It is generally agreed that the growth process is a well understood process and amenable to control. The growth reaction is responsible for developing molecular properties (molecular weights, composition, etc.) and morphology (core-shell, particle size distribution). Since the growth reaction lasts about
202
10-12 hours, there is great potential for optimizing the reaction time by increasing temperature or by keeping the particles saturated with monomer. Once inside a particle, radicals induce the usual free-radical polymerization steps such as propagation, termination, chain transfer, etc. A growing radical can escape from a particle and return to the aqueous medium to participate in an aqueous phase termination reaction or enter into another particle. During Stage II, monomer continuously diffuses from the monomer droplets into the particle phase, providing a steady monomer supply for the growing polymer particle. As the particles grow, the emulsifier molecules are continuously adsorbed onto or desorbed from the particles to maintain thermodynamic equilibrium. This dynamic exchange between various phases when added to the regular polymerization kinetics makes emulsion polymerization a more complex process than bulk or solution polymerization processes. The following figure illustrates the transport processes and reactions in a latex particle:
Radical Balance
The radical balance in the aqueous phase is controlled by the kinetic events that are responsible for the radical generation and the radical consumption in
203
that phase. Radicals are generated in the dispersant phase by two kinetic events: Initiator decomposition in the aqueous phase Desorption of radicals from the particle phase into the aqueous phase Termination of a live radical with another live radical in the aqueous phase Diffusion of a radical from the aqueous phase into a particle or a micelle
Radicals are depleted from the aqueous phase by two kinetic events:
Aqueous Phase Rate

The rate of production of radicals in the aqueous phase is considered equal to the rate of depletion of the radicals from the aqueous phase. This is an application of the stationary state hypothesis or quasi-steady-state approximation (QSSA):
2 kde N p n + RI N a = ka Rw N a + 2 ktw Rw Na
(3.6)
The previous equation can also be written as:
= + mn Y 2
With:
(3.7)
2 k R N 2 v v s N a = a w a N p k tp N p k tp
= k a Rw
(3.8)
=
m= Y=
2 RI v s N a (3.9) N p ktp
kde v s N a ktp 2 N p ktp ktw

2 2 vsNa ka
(3.10)
(3.11)
The emulsion polymerization model nomenclature is shown here:

Symbol Description Area of a single micelle (m3) Area of a single particle (m3) Area of micelles (m2/m3 of aqueous phase) Area of particles (m2/m3 of aqueous phase) Area coverage by emulsifier (m2/kmol) Density of polymer (kg/m3) Emulsifier concentration (kmol/m3) Volume density function for particle size distribution (m-3)
am ap
Am
Ap
As dp E
F ( v, t )
204
Symbol
Description Initiator efficiency Initiator concentration in the aqueous phase (kmol/m3) Absorption constant for particles (s-1) Critical chain length Volume fraction of polymer in polymer particle Initiator dissociation constant (s-1) Rate constant for the desorption of radicals from the particles (m3/s) Rate constant for the absorption of radicals by micelles (m/s) Rate constant for the absorption of radical by the particles (m/s) Rate constant for propagation in particle phase (m3/kmol-s) Rate constant for propagation in the aqueous phase (m3/kmol-s) Rate constant for activated initiation (m3/kmol-s) Rate constant for oxidation (m3/kmol-s) Rate constant for reduction (m3/kmol-s) Rate constant for the termination in the aqueous phase (m3/kmol-s) Partition coefficient for the i-th component between polymer particles and monomer droplets Concentration of monomer in the polymer phase (kmol/m3) Molecular weight of monomer (kg/kmol) Monomer concentration in aqueous phase (kmol/m3) Average number of radicals per particle Number of particles per unit volume of aqueous phase (no./m3) Avogadro number Aggregation number Number of particles containing n radicals per unit volume (no./m3-s) Rate of particle generation by homogeneous nucleation (no./m3-s) Radical concentration in the aqueous phase (kmol/m3) Rate of initiator dissociation (kmol/m3-s) Nucleation time(s) Volume of a single unswollen particle (m3)
f [I ] ka
jcr
p kd kde
kam
kap kp
k pw
ij kact ij kox ij kre
ktw
K ipm Mp
Mwm Mw
n Np Na
N agg Nn
Rhomo
Rw
RI tnuc
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Symbol
Description Volume of a single micelle (m3) Volume of a single particle formed by homogeneous nucleation (m3) Volumetric growth rate of a single particle (m3/s) Volume of a swollen particle (m3) Volumetric growth rate of a swollen particle (m3/s) Rate of radical absorption by
vm vh
v vs s v
i
0
1
N p particles (Kmol/s)
Total rate of radical generation (Kmol/s- m3) Zeroth moment of the particle size distribution (no./m3 of aqueous phase) First moment of the particle size distribution (m3/m3 of aqueous phase) Second moment of the particle size distribution (m6/m3 of aqueous phase) Third moment of the particle size distribution (m9/m3 of aqueous phase)
2
3
Particles containing n radicals are produced by three kinetic events: Absorption of a radical from the aqueous phase by a particle containing (n-1) radical. The total rate of this event is given as:
N n 1 Np
Radical desorption from a particle containing (n+1) radicals. The total rate of this event is given as:
N n+1 k de (n+ 1)
Termination in a particle containing (n+2) radicals. The total rate of this reaction is given as:
N n + 2 ktp [(n + 2)(n + 1)]

v
Particle Phase
Particles containing n free-radicals are depleted in the particle phase in three analogous ways. By equating the rate of formation to the rate of depletion of particles containing n free-radicals the recurrence formula is obtained:
(n + 2)(n + 1) ( N a / N p ) + kde n + ktp n(n 1) = Nn N n 1 ( N a / N p ) + N n +1k de (n + 1) + N n + 2 ktp Nav Nav

(3.12) This recurrence formula was first developed by Smith and Ewart, in a slightly modified form (Smith & Ewart, 1948). Equation 3.12 can be solved for the
206
average number of radicals per particle, n . The general solution as given by O'Toole is as follows (O'Toole, 1965):
n=
aI m ( a ) (3.13) 4 I m1 ( a )
In Equation 3.13, I m ( a ) and I m1 ( a ) are modified Bessel functions of the first kind with parameters m and a. Equation 3.10 gives the definition of m. a is calculated as a function of , defined in Equation 3.8, according to:
a = 8
(3.14)
The simultaneous solution for n (Equation 3.13) and the stationary steady state equation for the radical balance in the aqueous phase (Equation 3.6) completely define the kinetics of the emulsion polymerization.
Kinetics of Emulsion Polymerization

A general emulsion polymerization kinetics scheme involves simultaneous free-radical polymerization taking place in the dispersant phase, particle phase and the monomer droplet phase. However, in general the monomer droplet phase is regarded as an inert phase supplying monomer to the particle phase during reaction. In conventional emulsion polymerization, initiator decomposition takes place in the dispersant phase and the initiator radicals enter the polymer particle phase. The polymer particle phase is considered to be the site for all the polymerization reactions. There is a dynamic exchange of radicals between the particle phase and the dispersion phase. The average number of radicals per particle is dependent on the steady state that is reached as a result of this exchange. The free-radical kinetics scheme used in the model is that used in the free-radical polymerization model. In addition to the kinetics previously described in the free-radical Reaction Kinetic Scheme section on page 161, emulsion polymerization can also handle activated initiation, redox initiation, absorption and desorption.
Activated Initiation
The mechanism for activated initiation is given as:
act I k + A j nkj R + x *
k kj
Where:
Ik
= Initiator molecule the initiator molecules
Aj = Activator molecules which promote the dissociation of R = Primary radical produced in the initiation reaction
x * = Waste products that do not participate in the
polymerization reactions
207
In emulsion polymerization water soluble persulfate initiators are normally employed as initiators. In addition, water soluble sodium bisulfite is used as an activator in many emulsion polymerization reactions for accomplishing activated initiation of persulfates. For the above given mechanism, Ract , the radical generation rate for activated initiation, is given by the following equation:
kj
kj act
dR kj = = nkj f kj kact CI k C A j dt
Where:
kj = Rate constant for activated initiation kact
CI k
= Concentration of initiator in the aqueous phase
CA j = Concentration of activator in the aqueous phase nkj f kj

= Number of radicals produced per initiator molecules = Efficiency factor
Redox Initiation
The mechanism for redox initiation is given as:
k ox I k + Fe + + nk R + Fe + + + + Y * (oxidationslow) k re Fe + + + + Re Fe + + + x * (reductionfast)
k
Similar to activated initiation, redox initiation is used in emulsion polymerization reactions to promote decomposition of initiators at a much lower temperature. For example, redox initiation is employed in cold rubber production. It is also used in emulsion polymerization reactions where high radical flux is needed.
I k (the initiator, oxidant, or sometimes catalyst) decomposes in the presence

of the reduced (ferrous) ions, Fe++, to form one free radical, R , and the oxidized (ferric) ion, Fe+++. The reductant, Re, reacts with the ferric Fe+++ ion reducing it to ferrous Fe++. x* and Y* are inactive byproducts of the reactions. The activator system (or redox couple), a Ferrous salt (e.g. ferrous sulfate heptahydrate) plus a reductant (e.g. SFS, Sodium Formaldehyde Sulphoxylate), activates the initiator and regenerates the ferrous ion as previously shown. Multiple initiators are common: for example, KPS (Potassium persulfate) and tBHP (tert -butyl hydroperoxide). KPS is used initially. At high conversion, the monomer concentration in the polymer phase is low and the S 2O4 radicals cannot diffuse into the polymer phase because they are hydrophyllic. tBHP,

208
on the other hand, partitions into both the aqueous and the polymer phases and is, therefore, used for finishing in redox systems. In the case of two initiators, two oxidation reactions and one reduction reaction should be specified. As the ferrous and ferric ions get regenerated in the redox reaction, it is assumed that the total iron concentration remains constant in the reaction. As the rate of reduction is much faster than the rate of oxidation, a stationary state hypothesis is assumed for the ferrous and ferric ions. Assuming stationary state hypothesis for the ferric and ferrous ion concentration in the redox initiation mechanism, one can derive an equation for the rate of generation of the radicals by the redox initiation as follows:
k dR k red CFet CRe k nk f k koxCI k = k dt CI k + k red CRe k kox
Where:
CFet = Total concentration of the iron in the aqueous phase

k kox
= Rate constant for oxidation step of initiator k
k red = Rate constant for reduction step CI k

= Concentration of initiator k in the aqueous phase
CRe = Concentration of reductant in the aqueous phase nk fk

= Number of radicals produced per initiator molecule, k (default=1) = Efficiency factor for initiator k (default=1)
In thermal decomposition, typically each initiator molecule produces two radicals. The cage effect is when the radicals annihilate each other before they are able to diffuse out of the cage into the aqueous phase. This effect is captured by the radical efficiency term for thermal decomposition. In redox initiation, only one radical is generated from the initiator. Consequently, there is no cage effect because there is only one radical in the cage. Therefore, in redox initiation, there is typically no need for the two parameters: nk (number of radicals per initiator molecule) and f k (radical efficiency). However, these parameters are provided and defaulted to a value of 1 to provide additional handles for the user to fit their model to plant data.
Absorption and Desorption

In addition, there is an exchange of radicals between the aqueous phase and the polymer phase. Radicals generated in the aqueous phase are absorbed by the micelles during micellar nucleation and by the particle during nucleation and subsequent growth. Radicals in the polymer phase can desorb from the
209
particle and enter the aqueous phase. The kinetics of absorption and desorption are described as follows: Absorption by particles:
ap R N i +1 j + Ni
Rap = kap a p CN i CR
j
Absorption by micelles:
am R j + N m N1
Ram = kamamCN m CR
j
Desorption:
de N i N i1 + R
Rde = kdeiCN i
Where:
am
ap Nm Ni
= Area of a single micelle = Area of a single particle = Number of micelles with i radicals per cubic meter of aqueous phase = Number of particles with i radicals per cubic meter of aqueous phase
Reaction Rate Constant

The rate constant for each reaction in the built-in kinetics is calculated at the reaction temperature and pressure using the modified Arrhenius equation with user specified parameters for frequency factor, activation energy, activation volume, and reference temperature:
1 1 Ea VP k = k o exp R R T Tref
Where:
ko
Ea
= Pre-exponential factor in l/sec for first order reactions, and m / kmol s for second order reactions
3
= Activation energy in mole-enthalpy units = Activation volume in volume/mole units = Reaction pressure = Universal gas constant = Reaction temperature = Reference temperature
V
P R T
Tref
The second term in the exponential function contains the activation volume and is important for high pressure polymerization systems. For detailed
210
information of the reactions, see the free-radical Reaction Kinetic Scheme section on page 161. Rate constants related to absorption by particles, absorption by micelles and desorption from particles are given by the Arrhenius expression as:
Ea k = ko exp RT
assuming zero activation volume.

Following are the model features and assumptions used in the emulsion polymerization model available in Aspen Polymers.
Model Assumptions
The emulsion polymerization process is extremely complex and involves phenomena for which a complete theoretical understanding has not been reached. Important assumptions are made in the emulsion polymerization model: The reaction mixture is perfectly mixed Particles are formed by the micellar or the homogeneous mechanism No agglomeration or breakage of particles occurs No secondary nucleation occurs All particles have the same average number of radicals and hence the same volumetric growth rate The particle size distribution is unimodal, with moments of PSD sufficient to describe the PSD There are no mass transfer limitations on the polymerization reactions Molecular weight is controlled by chain transfer reactions
Thermodynamics of Monomer Partitioning

Modeling of the kinetics involved in emulsion polymerization is complicated by the fact that the reaction mixture is multiphase. It is important to account for partitioning of the components among various phases. Up to four coexisting phases may be present in the reaction mixture. After the consumption of the monomer droplets, only three phases will remain in the system. A short-cut partition coefficient methodology was used to handle the four phases. One benefit of using this approach is that NRTL parameters are not required for the polymer or its segments. The method assumes the polymer solubility is zero in the monomer, aqueous, and vapor phases and performs a rigorous 3-phase flash calculation to yield: Vapor phase - if present, contains water and monomers
211
Dispersion phase - contains water, initiators, emulsifiers, activators and some dissolved monomer Monomer phase - contains monomer and some dissolved water
The user provides a partition coefficient for each component that may be present in the polymer phase. Following the rigorous 3-phase flash, an iterative algorithm calculates the amount of each component to transfer from the monomer phase, if present, and the aqueous phase to the polymer phase in order to satisfy the partition coefficient constraints. As monomer is transferred to the polymer phase, water is transferred from the monomer phase to the aqueous phase so that its concentration in the monomer phase is the saturation concentration calculated by the rigorous flash. The user-supplied partition coefficients are provided as either: Monomer (L1) basis
x pi = k i1 x1i
Aqueous (L2) basis
x pi = k i2 x 2i
In either case, the partition coefficients are on a mass basis. This scheme works equally well for monomer starved or monomer saturated situations. When the monomer phase collapses, the algorithm transfers monomer from the aqueous phase to the polymer phase. If the user provided partition coefficients on a monomer basis, the partition coefficient with respect to the aqueous phase is calculated as:
k i2 = k i1 / k iLL k iLL values are only available when there is sufficient monomer present in the
swollen polymer particles to form a separate monomer phase if polymer were removed. If the 3-phase flash does not detect a separate monomer phase,
k iLL values will not be available, and the algorithm will transfer all monomer
from the aqueous phase to the polymer phase. In addition, there are two rigorous phase equilibrium approaches to handle the thermodynamics of monomer partitioning. The first rigorous approach assumes the presence of two liquid phases. The distribution of water, monomers, and polymers is determined by isofugacity relationships, and the fugacities of various species are computed by the physical property option set chosen for the system. The second approach performs rigorous four phase (vapor-liquid-liquid-polymer) flash calculations based on a newly available flash algorithm.
Polymer Particle Size Distribution

Polymer particle size and size distribution, among other factors, determine the rheological properties of the latex . Although actual particle size distribution is important, it is often measured in terms of certain averages such as number average and weight average diameters. Further, rigorous tracking of the particle size distribution by discrete methods is computationally expensive.
212
In conventional emulsion polymerization where unimodal distributions are normally encountered, the moments of the particle size distribution give sufficient information about the nature of the particle size distribution. The particle size distribution can be described in terms of different independent variables such as diameter or volume of the particle. Since volumetric growth rate of the particle in emulsion polymerization remains almost constant in Stage I and Stage II of the process, the population balance equation is formulated in terms of the volume of the particles.
General Population Balance Equation

The general population balance equation for the emulsion polymerization is given as follows:
F ( v, t )) F ( v, t ) ( v + = kam Am N a [ R ]w ( v v m ) + Rhomo( v v h ) t v
(3.15)
In Equation 3.15 the right-hand side represents the nucleation of particles from miceller and homogeneous nucleation. Refer to the table on page 204 for for an explanation of the variables used. The volumetric growth rate is v a single unswollen particle (Equation 3.5):
= v
k p M p n MWm Na dp
(3.16)
The general population balance equation can be converted to the equivalent moment equations. The j-th moment of the particle size distribution is given as:
j = j F ( , j )d
0
(3.17)
Applying moment definition in Equation 3.17 to the general population balance equation in Equation 3.15, the first four moments of the particle size distribution are given as:
d0 = kam Am N a [ R ]w + Rhomo (3.18) dt
d1 0 + v m kam Am N a [ R ]w + v h Rhomo =v dt d2 2 1 + v 2 = 2v m kam Am N a [ R ]w + v h Rhomo dt d3 3 2 + v 3 = 3v m kam Am N a [ R ]w + v h Rhomo dt

Where:
(3.19) (3.20) (3.21)
kam
Am
= Kinetic constant for the absorption of the oligomeric radicals into the micelles = Area of the micelles
213
Rhomo = Rate of particle formation by homogeneous

nucleation
Polymer Particle Properties Calculated

The emulsion model is designed to generate the following results that are of interest for the emulsion polymerization process: Copolymer composition Number average molecular weight Particle size distribution averages for unswollen particles
The results are available as component attributes under the names listed here:
Name PSDZMOM Symbol Description Zeroth moment of the particle size distribution (volume) First moment of the PSD (volume) Second moment of the PSD (volume) Third moment of the PSD (volume) Number average volume of the particles Volume average volume of the particles Z-average volume of the particles Volume average diameter Polydispersity for PSD (Volume) Copolymer composition Number average molecular weight Class 2 Units no./s
0
1 2
PSDFMOM PSDSMOM PSDTMOM VOLN VOLV VOLZ DIAV PDV SFRAC MWN
0 2 2 0 0 0 0 0 0 0
m3/s m6/s m9/s m3 m3 m3 m ----kg/kmol
3
Vn
Vv
Vz Dv
PDv
-----
User Profiles
In addition to the polymer properties reported through the component attributes, other model calculations are reported through User Profile variables. The following user profile variables may be requested from the model:
214
Glass transition temperature of the polymer (C) Average number of radicals per particle % Soap coverage of the polymer particles Volume of the monomer droplet phase (m3) Concentration of monomers in the monomer droplets (kmol/m3) Volume of the aqueous phase (m3) Monomer concentration in the aqueous phase (kmol/m3) Volume of the polymer particle phase (m3) Monomer concentration in the polymer particles (kmol/m3) Monomer conversion
One profile is reported for each monomer. User profiles are only accessible if the reaction model is called from a batch reactor (RBatch) or a plug flow reactor (RPlug). The user profiles are returned in the order shown. A label must be provided to differentiate the profile variables. For the monomer concentrations in the aqueous, monomer, and polymer phases one profile is returned for each monomer.
Specifying Emulsion Polymerization Kinetics

Accessing the Emulsion Model
To access the Emulsion polymerization kinetic model: 1 2 3 4 5 From the Data Browser, click Reactions. From the Reactions folder, click Reactions. The Reactions object manager appears. If the kinetic model already exists, double-click the desired Reaction ID in the object manager or click Edit to get to the input forms. To add a new model, from the Reactions object manager, click New. If necessary, change the default ID for the reaction. Select Emulsion as the reaction type and click OK.
Specifying the Emulsion Model

The Emulsion model input forms are divided into two folders: Specifications and Phases. Use the Specifications forms to define reacting species and enter reaction rate constant parameters. Use the following options:
Use this sheet Species Reactions Rate Constants To Define reacting species Specify reactions and rate constant parameters Summarize rate constant parameters
215
Options Gel Effect
Select additional options Gel-effect correlation parameters
Use the Phases forms to enter information related to phase partitioning and particle growth. Use the following options:
Use this sheet Phase Equilibria Particles To Specify component phase split Specify emulsifiers and define particle radical exchange information

You must specify the reacting species in the Specifications Species sheet: 1 In the Polymer field, specify the polymer produced. Also specify Dispersant and the Redox couple (ferrous salt and reductant) if redox initiation is used. In the Monomers field list the reacting monomers. For each monomer, in the goes to field, specify the polymer segment that the monomer converts to. Continue listing other types of reacting species, e.g. initiators, transfer agents, etc. Select the Generate Reactions option if you want the reactions to be generated automatically. After going through the reaction generation once, it is recommended that you turn off this feature. Otherwise, the reaction generation is performed repeatedly.
3 4
Listing Reactions
The Emulsion model generates reactions based on the list of reacting species. You can view the system-generated reactions, then assign rate constant parameters to these reactions. You can view a list of the system-generated reactions on the Specifications Reactions sheet. In the Reaction summary listing for each reaction, the first column indicates the reaction type. The second column lists the reactants, and the last column lists the products. The Data Browser window can be resized to better view the reaction listing. Use the following options:
Click New Edit Rate Constants To Add new reactions to the scheme Edit the current reaction indicated by the row selector Specify reaction rate constant parameters for the reactions
Click to select a reaction. Click a reaction then Control-Click to include additional reactions for multiple selections. Double-click to edit a reaction.
216
In addition, you can use the following buttons:

Adding Reactions
To add a new reaction to the scheme, click New to open the Add Reaction subform: 1 2 3 In Reaction type, select a type for the new reaction. The Reaction scheme for that type is displayed. In other reactant (for example, Initiator, Catalyst) fields, enter the reactants of the categories allowed for that reaction type. Click Cancel to discard the new reaction or Click New to add a new reaction or Click or Click Done to return to the reaction summary. to check the Completion status
Editing Reactions

To assign rate constants to user reactions, click Rate Constants to open the Rate Constant Parameters subform: 1 2 3 4 5 In the Ko field, enter the pre-exponential factor. In the Ea field, enter the activation energy. In the V field, enter activation volume. In the Tref field, enter reference temperature. In the Efficiency field, enter initiator efficiency for initiation reactions.
217
6 7
In the No. radicals field, enter the number of primary radicals formed in initiation reactions. Click the stoichiometry list and select a new reaction. Enter rate constants for the new reaction. You can use the Prev and Next buttons to select the previous or next reaction in the list. Click the Summary tab to see a listing of all the rate constant parameters. Click or Click Close to return to the reaction summary. to check the Completion status
8 9
Selecting Calculation Options

You can select additional simulation options for the model, such as gel-effect, on the Options sheet. For Gel effect, you need to specify parameters on the Gel Effect sheet.
Adding Gel-Effect
Use the Gel-Effect sheet to add gel effect to reactions: 1 2 3 4 Enter a unique integer identifier in No. In the Reaction field, specify the reaction to which you would like to apply gel effect. In the Corr. No. field, specify a gel effect correlation number. In Parameters, list the parameters for the gel effect correlation.
Specifying Phase Partitioning

Use the Phases Phase Equilibria sheet to specify phase partitioning for the components in the emulsion system: 1 2 3 If you select a Rigorous approach, specify a Method. If you select the Partition Coefficients approach, in the Basis field select the phase partitioning basis, for example, MONOMER or AQUEOUS For each component present in the polymer phase (except the polymer), specify the split fraction using the Component and Coefficient fields.
218
Specifying Particle Growth Parameters

Use the Phases Particles sheet to specify data for particle generation and particle related events: 1 2 Define Emulsifier, and specify critical micelle concentration, CMC, and surfactant Area. For homogeneous nucleation, specify Aggregat no. and Critical length.
You must specify radical absorption and desorption rate constant parameters for micelles and particles.
References
Barton, J., & Capek, I. (1994). Radical Polymerization in Disperse Systems. New York: Ellis Harwood. Blackley, D. C. (1975). Emulsion Polymerization: Theory and Practice. London: Applied Science Publishers Ltd. Gilbert, R. G. (1995). Emulsion Polymerization: A Mechanistic Approach. Boston: Academic Press. Hamielec, A. E., & Tobita, H. (1992). Polymerization Processes. In Ullmans Encyclopedia of Industrial Chemistry, A21, 305. New York: VCH Publishers. Harkins, W. D. (1945). J. Chem. Phys., 13, 301. Odian, G. (1991). Principles of Polymerization, 3rd. Ed. New York: John Wiley & Sons. OToole, J. T. (1965). Kinetics of Emulsion Polymerization. J. Appl. Polym. Sci., 9, 1291. Poehlein, G. W. (1986). Emulsion Polymerization. In H.F. Mark, N. M. Bikales, C. G. Overberger, and G. Menges, (Eds.). Encyclopedia of Polymer Science & Technology, 6, 1. New York: Wiley-Interscience. Ponnuswamy, S. R., & Hamielec, A. E. (1997). Emulsion Polymerization: Theory and Practice. Lecture notes for intensive short course on polymer reaction engineering held at Burlington, ON, Canada, April 28-30. Smith, W. V., & Ewart, R. H. (1948). J. Chem. Phys., 16, 592.
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11 Ziegler-Natta Polymerization Model
This section covers the Ziegler-Natta polymerization kinetic model available in Aspen Polymers (formerly known as Aspen Polymers Plus). The term ZieglerNatta polymerization is used here to describe a variety of stereospecific multisite and single site catalyzed addition polymerization systems including the traditional Ziegler-Natta catalyzed systems, chromium based catalyzed systems (Phillips type) and the more recent metallocene based catalyzed systems. Topics covered include: Summary of Applications, 220 Ziegler-Natta Processes, 221 Reaction Kinetic Scheme, 225 Model Features and Assumptions, 235 Polymer Properties Calculated, 236 Specifying Ziegler-Natta Polymerization Kinetics, 237
Several example applications of the Ziegler-Natta polymerization model are given in the Aspen Polymers Examples & Applications Case Book. Additionally, the Examples & Applications Case Book provides process details and the kinetics of polymerization for specific monomer-polymer systems.
The Ziegler-Natta polymerization model is applicable to processes utilizing coordination catalysts for the production of stereospecific polymers. Some examples of applicable polymers are: Linear low density polyethylene - Ethylene is copolymerized with an alphaolefin, such as 1-butene, 1-hexene, or 1-octene. Commercial processes include low pressure, slurry-phase processes, solution-phase processes, low pressure, gas phase processes. High density polyethylene - Ethylene homopolymers or copolymers with high alpha olefins with density 0.940
g / cm 3 and higher. Commercial
220
processes include solution, slurry or suspension, and gas phase polymerization. Ethylene-propylene elastomers - Polymerization proceeds by solution or slurry processes. Both are operated continuously in liquid-phase backmixed reactors. Polypropylene - Commercial processes include liquid pool, diluent slurry, and gas phase polymerization.
Ziegler-Natta Processes
Ziegler-Natta polymerization accounts for a significant fraction of the polyethylene polymers and all the polypropylene homopolymers and copolymers produced commercially. The commercial production of these polyolefins is done exclusively by continuous processes using several different processes and reactor types operating over a wide range of conditions. High density polyethylene (HDPE) and linear low density polyethylene (LLDPE) are produced via catalyzed polymerization processes. The operating conditions for the catalyzed processes are relatively less severe compared to the high pressure processes for LDPE production. The pressure generally ranges from 10-80 atm while the temperatures range from 80-110C. The pressure and temperature may be as high as 200 atm and 250C in some of the solution polymerization processes.
Catalyst Types
There is a variety of catalysts used for ethylene polymerization including supported and unsupported heterogeneous catalyst systems and homogeneous catalyst systems. The Ziegler-Natta transition metal (Ti) based catalysts are the most widely used. However, there are numerous variations of these catalysts. Some vanadium based catalysts are also used. Chromic oxide on silica catalysts are used in the Phillips loop reactor process, while the Union Carbide Unipol process may use either Ziegler-Natta (Ti) or chromium compounds on silica catalysts. More recently, several manufacturers have been developing commercial processes using metallocene based catalysts, mainly zirconium and titanium. These catalysts are believed to be single site catalysts that are capable of producing high yields, combined with narrow molecular weight and copolymer composition distributions. All commercial isotactic polypropylene homopolymer (PP) is manufactured using heterogeneous Ziegler-Natta catalyst systems. The catalyst consists of a solid transition metal halide, usually TiCl3 , with an organoaluminum compound cocatalysts, such as diethylaluminum chloride (DEAC), or a MgCl2 supported TiCl4 . AlEt3 catalyst.
221
Ethylene Process Types

There are three types of catalyzed ethylene polymerization processes in commercial use today: Liquid slurry Solution Gas-phase
A partial list of HDPE and LLDPE processes, along with a summary of their characteristics is shown here:
Process Reactor Diluent / Solvent i-butane n-hexane CSTR n-hexane Catalyst Temp. (C) 80-100 80-90 Press. (atm) 30-35 8-35 Residence Time (hr) 1.5-2.5 2.0-2.7 Company
Liquid slurry
Loop
Supported Ti or Cr Supported Ti
Phillips Solvay Dow Hoechst Nissan Mitsubishi Montedison
Solution
CSTR
n-hexane cyclohexane -----
Ti/V
130250 70-110 85-100
30-200
0.08-0.17
Dow Dupont Stamicarbon
Gas
Stirred bed Fluidized bed
Supported Ti or Cr Supported Ti or Cr
20-35 20-30
3-5 3-5
AMOCO BASF BP Union Carbide
In the slurry process, a hydrocarbon diluent is used, typically a C4 C7 paraffin, isoparaffin or cycloparaffin. Under the conditions used the polyethylene is essentially insoluble in the diluent. As a result a slurry is formed. In the solution process, the conditions used are such that the polyethylene is completely dissolved in the solvent. In gas-phase processes, gaseous ethylene and comonomers are contacted with a polymer-catalyst powder. Polymerization occurs in the monomerswollen polymer particles which contain embedded catalyst fragments with active sites. Ethylene polymerization processes have been reviewed extensively. More detailed descriptions of these processes are available in the open literature (Albright, 1985; Choi & Ray, 1985a; Nowlin, 1985; Short, 1983).
222
Propylene Process Types

There are three types of catalyzed polypropylene homopolymerization processes in commercial use today: Liquid slurry Liquid pool (bulk) Gas-phase
A partial listing of propylene homopolymerizatio processes, along with a summary of their characteristics is shown here:
Process Reactor Diluent / Catalyst Solvent Liquid monomer Liquid monomer Supported Ti Tacticit y (%) Up to 99 Temp. (C) 60-80 Press. (atm) 30-40 Residenc e Time (hr) 1-2 Company
Bulk (Liquid Pool)
Loop
Himont Mitsui
CSTR
Unsupported or supported Ti
Up to 98
60-75
30-40
Dart El Paso Montedison Sumitomo
Diluent Slurry Gas
CSTR
n-hexane, Unsupported n-heptane or supported Ti N2 Supported Ti
Up to 98
60-80
15-20
3-4
Montedison
Fluidized bed
Up to 98
60-80
20
3-5
Sumitomo Union Carbide
Vertical stirred bed Horizontal compartmente d stirred bed
---
Unsupported or supported Ti Unsupported or supported Ti
Up to 98
70-90
20
BASF ICI USI
---
Up to 98
70-90
20
AMOCO
In the slurry process, a hydrocarbon diluent, typically butane, hexane or heptane, is used at operating temperatures of 70-90C. Under these conditions the isotactic polypropylene is essentially insoluble in the diluent. As a result a slurry is formed. In the liquid pool process, liquid propylene is used in place of the diluent. In this process also, the polypropylene is insoluble in the liquid propylene and a slurry is formed. The higher monomer concentrations in this process allow for smaller reactors and lower operating temperatures compared to the slurry process. In the gas-phase processes, gaseous propylene is contacted with a polymercatalyst powder. Polymerization occurs in the monomer-swollen particles which contain embedded catalyst fragments with active sites.
223
Propylene polymerization processes have been reviewed extensively in the literature. More detailed descriptions of these processes are available in the open literature (Albright, 1985; Brockmeier, 1983; Choi & Ray, 1985b). Besides polypropylene homopolymer (PP), high impact polypropylene (HIPP) and some ethylene-propylene (EP) copolymers are produced by including an additional reaction stage to the polypropylene homopolymerization process. A summary of catalyst processes for propylene copolymerization is shown here:
Press. (atm) Process Bulk (Liquid Pool) + Second Stage CSTR CSTR CSTR stirred horizontal bed Diluent Slurry CSTR ----Supported Ti 60-75 Unsupported 40-75 or supported Ti 0-20 30-40 30-40 30-40 20 2 2-5 Ethylene Ethylene Sumitomo Dart El Paso 5-20 --1 Ethylene, Butene, dienes Ethylene & others Ethylene & others Montedison Dutral Sumitomo Union Carbide BASF ICI USI 20 20 4 Ethylene & others AMOCO Chisso Reactor Diluent / Solvent Catalyst Temp. Stage 1 (C) 30-40 Stage 2 20 Residence Time (hr) 1-2
Comonomers Ethylene & others
Company Himont Mitsui
Loop - fluid --bed
Supported Ti 60-80
Liquid Ti/V monomers & diluents
Multistage Fluid bed - --Gas fluid bed --Vertical stirred bed - stirred bed Horizontal --stirred bed horizontal stirred bed
Supported Ti 60-80
20
20
3-5
Unsupported 70-90 of supported Ti Supported Ti 70-90
20
20
In the EP process, last reaction stage is designed to introduce the desired amount of EP copolymer into the PP product. For example, the Himont spheripol process uses liquid pool loop reactors followed by a gas-phase fluidized bed reactor for the copolymerization stage. The residence time distribution of the polymer particles leaving each stage should be as narrow as practical to ensure that the weight ratio of EP to PP for particles leaving the second stage is as uniform as possible. The Amoco/Chisso process has largely met this requirement.
224

The built-in catalyst/polymerization kinetic scheme represents the typical scheme described in the open literature (Xie et al., 1994). Although a number of reaction mechanisms have been proposed to describe stereospecific Ziegler-Natta polymerization, there is still no definitive reaction mechanism to completely describe the kinetic behavior of these complex catalyst/polymerization systems. Most of the proposed mechanisms include a detailed set of reactions. However, not all of these reactions apply to every catalyst system nor can they be verified. The kinetic scheme for chromium and metallocene catalyzed systems can be considered to be a subset of a comprehensive Ziegler-Natta kinetic scheme.
Reaction Steps
There are a few key elementary reactions that apply to almost all catalyzed addition polymerization systems. These include the three basic reaction steps: Chain initiation Propagation Chain transfer (spontaneous and to small molecules such as monomer, solvent and chain transfer agents)
For chromium and metallocene catalyst systems, additional reactions for long chain branching via terminal double bond polymerization must also be included. In addition to the polymerization reactions, there are reactions affecting the catalyst active sites on which the polymerization reactions take place. These include catalyst site activation, inhibition and deactivation. The catalyst reactions and the polymerization reactions occur simultaneously during the polymerization. A comprehensive kinetic scheme for the catalyzed multi-site homo- and copolymerization of any number of monomers has been built into Aspen Polymers.
Catalyst States
The multi-site catalyst states and the types of reactions affecting them are shown here:
225
In setting up a simulation, the user specifies the catalyst flow rate for the feed streams, and a catalyst parameter, the moles of sites per unit mass of catalyst. This parameter together with the catalysts flow rate is used to compute the total moles of sites. The total moles of sites are made up of potential sites, active sites of different reactivities, and dead sites. Site activation reactions convert potential sites to active sites, while site deactivation reactions convert active sites to dead sites. There are several different site activation/deactivation reactions built into the kinetic scheme and these are discussed later in this section.
Site Types
In the figure, potential sites and dead sites are considered to be independent of site type. The user specifies the number of site types to be included for a particular simulation. A vacant site is an active site that does not have a polymer or other molecule attached to it. A propagation site has a growing polymer molecule attached to it. Inhibited sites have small molecules such as hydrogen or poisons attached, temporarily blocking it from becoming propagation sites. The small molecule may dissociate from an inhibited sited, which then becomes a vacant site once again. Therefore, the site inhibition reaction is considered reversible.
226
When a vacant site is involved in a chain initiation reaction it is converted to a propagation site. When a propagation site is involved in a chain transfer reaction, a vacant site and a dead polymer molecule are formed. The built-in scheme includes most of the reactions commonly used for modeling Ziegler-Natta polymerization. Reactions such as depropagation, internal double-bond polymerization with diene comonomers, and site transformation reactions (Debling et al., 1994; Xie et al., 1994) have not been included in the current model. These reactions may be added to the built-in scheme in the future. The current built-in Ziegler-Natta catalyst and polymerization kinetic scheme is shown here:
Built-In Ziegler-Natta Catalysts and Polymerization Kinetic Scheme (continued)
227
Built-In Ziegler-Natta Catalysts and Polymerization Kinetic Scheme (continued) continued
228
Built-In Ziegler-Natta Catalysts and Polymerization Kinetic Scheme (continued)
Kinetic Scheme Nomenclature

The nomenclature used in the Ziegler-Natta polymerization kinetic scheme is given here:
Symbol Description Cocatalysts m Electron donor m
Am
Em
229
Cds C ps
k Cis k Dn
Dead catalyst sites Potential catalyst sites Inhibited catalyst sites of type k Dead polymer chain of length n Hydrogen Monomer j Number of monomers Number of active site types Reaction order for the non-polymer component at site type k Vacant catalyst sites of type k Live polymer chain of length n having an active segment of type i attached to a active site of type k Solvent m (for solution or slurry polymerization) Chain transfer agent m Inhibitor n Zeroth moment of live polymer with respect to active segment of type i and active site of type k
( = n1, n2, ..., nm ) for
copolymerization produced from a catalyst site of type k
H2 Mj
Nm N sites
Ok P0k
Pnk,i
Sm Tm Xn
k 0 ,i
In the following discussion: A polymer chain is considered to be made up of monomer units or segments derived from the propagating monomers Live chain ( Pnk,i ) refers to growing polymer chains containing n segments or monomer units, with an active segment of type i attached to a catalyst active site of type k
k Dead chain ( Dn ) refers to a terminated polymer chain
The superscript k refers to the active site type from which the dead polymer chain was formed The subscript n refers to the chain length in terms of the number of segments or monomer units incorporated in the polymer chain
Live chains are reactive and can participate in the polymerization reactions while dead chains are usually considered inert, except in cases where long chain branching reactions are important.
Polymerization Mechanism
The catalyst active site is attached to one end of a live polymer chain via a metal-carbon bond. It is generally accepted that polymerization proceeds via a two-step mechanism. In the first step, monomer is complexed to the transition metal site. The second step is the coordinated insertion of the
230
monomer into the metal-carbon bond. As a result, the polymer chain and the previously added segments grow away from the active site with every addition of a monomer molecule. It is believed that the chain microstructure will not have a strong influence on the mode of monomer addition. For this reason, the built-in kinetic model assumes that the reactivity of a live polymer chain depends only on the active segment and the active site type, and is independent of the polymer chain length and other structural properties. Meaning in the propagation reaction,
k the rate of propagation R p ,ij is independent of the polymer chain length. It
depends only on the concentration of monomer j, and the concentration of live polymer chains with active segments of type i attached to an active site of type k. Models using this assumption are referred to as terminal models in the polymerization literature.
Copolymerization Mechanism
For copolymerization, the built-in kinetic scheme allows the user to specify the number of monomer types used. Similarly the user has the flexibility to specify the number of each type of reactive species present in the polymerization: catalysts, cocatalysts, chain transfer agents, solvents, etc. The user is able to tailor the built-in kinetics to model a specific catalyzed polymerization system by selecting a subset of the reactions shown in the Built-In Ziegler-Natta Catalysts and Polymerization Kinetic Scheme figure on page 227. However, it is important that the subset include a chain initiation, propagation, and at least one chain transfer or active site deactivation reaction to produce dead polymer.
Rate Expressions
The rate expression for each reaction is generally written as a product of the rate constant and the concentrations of the reacting species. In many of the reactions, one of the reacting species is a polymer chain while the other is a small molecule such as monomer, chain transfer agent, cocatalyst, etc. A reaction order with respect to the small reacting molecule is included for some of the reactions. This reaction order has a default value of one. The rate constants for each reaction at sites of type k are calculated at the reaction temperature using the Arrhenius equation shown below. The user
k ) , activation specified rate constant parameters are pre-exponential factor ( ko
energy ( Ea k ) at sites of type k, and the reference temperature.
Rate Constant
E ak 1 k k 1 k = k o exp R T Tref
Where:
ko
= Pre-exponential factor in 1/sec for first order reactions
231
and m 3 / kmol sec for second order reactions Ea R = Activation energy in mole enthalpy units = Universal gas constant
Tref = Reference temperature in Kelvin
Catalyst Pre-Activation
Some of the chromium catalysts used in these processes exhibit slow activation with induction period. This slow activation can be modeled by catalyst preactivation reaction. The precatalyst goes to catalyst that further undergoes site activation, initiation and propagation.
Catalyst Site Activation

The catalyst site activation step involves the generation of reactive vacant active sites from potential sites. Depending on the catalysts system, the activation may be done before the catalyst is fed to the reactor or within the reactor. There are several different site activation reactions included in the built-in kinetic scheme. They include site activation by cocatalyst, by electron donors, by hydrogen, by monomer, and spontaneous site activation. Different catalyst systems tend to be activated by a different subset of the reactions in this scheme. For example, TiCl3 catalyst systems are usually activated with an organoaluminum cocatalyst such as diethylaluminum chloride (DEAC), in the reactor. Chromic oxide catalysts are calcined by heating with air for several hours at temperatures of 400C to 975C and cooled in dry air. Some of these catalysts may be activated with a reducing agent before introduction into the reactor, while others are activated within the reactor.
Site Activation Reactions

Some of the site activation reactions (activation by monomer, electron donor, hydrogen) have been proposed to explain the observed rate enhancement behavior in different catalyst systems. For example, the activation of additional sites by comonomer has been proposed to explain the rate enhancement observed with the addition of a comonomer to ethylene and propylene homopolymerization reactors.
Chain Initiation
Chain initiation involves the reaction of a monomer molecule at a vacant active site to form a live polymer molecule of unit length at that site. This reaction converts a vacant active site to a propagation site. The chain initiation reaction is shown below:
i Pok + M i P 1 k k k Rci = kci Po ( C Mi )
k O Mi
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k The rate of chain initiation at site type k ( Rci ) is dependent on the concentration of vacant sites of type k and the concentration of monomer i. The user can also specify the reaction order with respect to the monomer concentration. The live polymer chains grow by successive addition of monomer molecules to form long polymer molecules.
Propagation
The live polymer at each active site type grow or propagate through the addition of monomer molecules to form long polymer chains. The propagation reaction is represented by:
Pnk, i + M j Pnk+1, j
k k k Rp n , i (main propagation) , ij = k p , ij C Mj P
Where monomer j is being added to a polymer chain of length n, with an active segment of type i at an active site of type k. The resulting polymer chain will be of length n+1 and the active segment will be of type j. The active segment type usually represents the last monomer type incorporated into the polymer chain. For copolymerization, there will be N m * N m * N site propagation reactions that may have different reactivities. For example, with two monomers and three site types, the monomer being added could be monomer 1 or monomer 2 while the active segment type could be segments from monomer 1 or monomer 2 at each site type.
k As a result, there will be twelve rate constants ( k p ,ij ) , where the subscript i
refers to the active segment type while the second subscript j refers to the propagating monomer type. The superscript k refers to active site type. For the terminal model the rate of propagation is dependent only on the concentration of live polymer with active segment i at active site k and the concentration of the propagating monomer j. In Aspen Polymers Version 3.0 and higher, another propagation reaction has been added to account for formation of atactic polymer. This reaction has the same form as the main propagation reaction:
Pnk, i + M j Pnk+ i ,i
k k R paij = k paij 0k, j (CMi ) k
Ok paMi
(atactic propagation)
but uses a different rate constant ( k paij ) . When the atactic propagation reaction is included in the simulation, the main propagation reaction should be considered to account for the formation of all polymer whether it is isotactic or atactic. Hence the main propagation reaction is also termed the total propagation. The atactic propagation reaction only accounts for the formation of atactic polymer. The atactic content of the polymer is then calculated from the ratio of atactic to total polymer.
Chain Transfer to Small Molecules

Chain transfer to small molecules such as monomer, solvent or chain transfer agent usually involves the extraction of hydrogen from the small molecule by the active site and leads to the termination of the live chain. At the same
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time, a new vacant site is formed which can undergo chain initiation to start polymerization. The effect of chain transfer on the polymerization kinetics depends on the reactivity of the transfer sites. When the transfer site is very reactive, as is the case when the chain initiation rate constant is greater than the propagation rate constant, chain transfer will not lower the polymerization rate or conversion, but will reduce the molecular weight of the polymer. However, if the transfer site is less reactive, as in the case of low chain initiation rate constant, both the conversion and molecular weight of the polymer will be lowered. In the built-in kinetics, chain transfer to hydrogen, cocatalysts, solvent, transfer agent, electron donor, monomer and spontaneous chain transfer are included as shown in the Built-In Ziegler-Natta Catalysts and Polymerization Kinetic Scheme figure on page 227.
Chain Transfer to Monomer

For chain transfer to monomer a new polymer chain of unit length is generated while for the other transfer reactions a vacant site of that type is generated. The dead polymer chain formed by some of the chain transfer reactions will have an end-group with a terminal double bond. In addition to the rate constant parameters and the reaction order, the user may also specify a parameter to track the fraction of dead polymer chains with terminal double bonds that are generated from the chain transfer reactions. The default value for this parameter is zero.
Site Deactivation
The catalyst site deactivation step involves the deactivation of active sites, vacant and propagation, to form dead sites. Depending on the catalyst system and operating conditions, the deactivation rate may be high or low. There are several different site deactivations reactions included in the built-in kinetic scheme. They include site deactivation by cocatalyst, by electron donors, by hydrogen, by monomer, by poisons, and spontaneous site deactivation. Different catalyst systems tend to be deactivated by a different subset of the reactions. The deactivation rate constants are assumed to be dependent only on the site type and not on the polymer segment attached to a site. Therefore, the same rate constant is applied to both vacant and propagation sites of the same type. Note that deactivation rates shown in the Built-In Ziegler-Natta Catalysts and Polymerization Kinetic Scheme figure on page 227 are per unit of active (vacant and propagation) site concentration.
Site Inhibition
Inhibited sites have small molecules such as hydrogen or poisons attached. As a result, inhibited sites are temporarily blocked from becoming propagation sites. The site inhibition reaction is considered reversible. Therefore, the small molecule may dissociate from an inhibited site which then becomes a vacant site once again. The user must specify rate constant
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parameters for both the forward (inhibition) and reverse (dissociation) reactions.
Cocatalyst Poisoning
For some catalyst systems, additional amounts of cocatalysts are fed to the reactor to counteract the effect of any poisons present . This is modeled as a cocatalyst poisoning reaction in the built-in kinetics. The product of this reaction is designated as a byproduct in the list of reactive species. The byproduct is considered to be inert and does not participate in any reaction.

For some catalyst systems, primarily metallocene, polymer chains with long chain branches are formed. However, the long chain branching frequency is usually small. The long chain branches are believed to be due to propagation reactions involving a live chain and a terminal double bond on a dead polymer chain. Polymer chains with terminal double bonds are formed by some of the chain transfer reactions. To form long chain branches, the metal center must be open to provide a favorable reactivity ratio for the macromonomer. The concentration of terminal double bond (TDB) end-groups on the dead polymer chains are tracked through an additional segment called the TDBSegment. TDB-Segments are generated through the chain transfer reactions and are consumed through the TDB polymerization reaction. When the TDB reaction is used, one additional segment needs to be defined in the Components form for the TDB-Segment. Typically, for a copolymerization system with N monomers, N repeat segments would be defined in the Components form. However, with the TDB polymerization reaction, N repeat segments and one end segment should be defined in the Component form. The end segment must be specified as the TDB-Seg species in the Species folder of the Ziegler-Natta kinetics.

Following are the model features and assumptions used in the Ziegler-Natta polymerization model available in Aspen Polymers.
Phase Equilibria
The polymerization model currently considers a single-phase system (vapor or liquid), two-phase system (vapor and liquid), or three-phase (VLL) system when calculating concentrations for the reaction kinetics. For single-phase systems, the reacting phase may be either vapor or liquid. In multi-phase systems, reactions can occur in one or more phases simultaneously. Each reaction object is associated with a single reacting phase, identified on the options form.
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By default the reacting phase is assumed to be the liquid phase (for VLL systems, the reacting phase must be specified). Several reaction models can be referenced from a single reactor block to account for reactions in each phase.
Rate Calculations
The Ziegler-Natta polymerization kinetic model supplies to the reactor models the reaction rates for the components and the rate of change of polymer attributes (e.g. the chain length distribution moments) . The component reaction rates are computed from the kinetic scheme by summing over all reactions that involve the component. The site based moment rates are derived from a population balance and method of moments approach similar to that described in the Calculation Method section on page 182.

The following variables can be calculated by the built-in kinetics routine based on the polymer attributes selected, and the subset of the built-in kinetics used for a specific simulation: Zeroth, first and second moments for the composite and site based combined polymer Zeroth and first moments for the composite and site based live polymer Number and weight degree of polymerization and polydispersity index for the composite and site based bulk polymer (DPN, DPW, PDI and SDPN, SDPW, SPDI) Number and weight average molecular weight for the composite and site based bulk polymer (MWN, MWW and SMWN, SMWW) Copolymer segment composition for composite and site based bulk polymer (SFRAC and SSFRAC segment mole fractions) Total number long chain branches (LCB) Long chain branching frequencies (FLCB) Mole fraction of live bulk polymer chains (LPFRAC and LSPFRAC) Number average degree of polymerization for live polymer (LDPN and LSDPN) Copolymer segment composition for live polymer (LSFRAC and LSSFRAC) Live polymer active segment composition (LEFRAC and LSEFRAC)
These variables are stored as component attributes (See Chapter 2). It is assumed that attributes needed for the kinetic scheme are selected. The specification of the Ziegler-Natta Model is described later in this section. In many cases, users may need to know polymer product properties related to the above structural properties. For example, users may be interested in melt flow rate or melt index, viscosity, density, etc. These properties can be calculated in user-supplied Fortran subroutines which take the polymer moments and structural information and return the desired property. An example use of a user supplied subroutine to return melt index is shown in the HDPE section of the Aspen Polymers Examples & Applications Case Book.
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Specifying Ziegler-Natta Polymerization Kinetics

Accessing the Ziegler-Natta Model
To access the Ziegler-Natta polymerization kinetic model: 1 2 3 4 5 From the Data Browser, click Reactions. From the Reactions folder, click Reactions. The Reactions object manager appears. If the kinetic model already exists, double-click the desired Reaction ID in the object manager or click Edit to get to the input forms. To add a new model, from the Reactions object manager, click New. If necessary, change the default ID for the reaction. Select Ziegler-Nat as the reaction type and click OK.
Specifying the Ziegler-Natta Model

The Ziegler-Natta model input forms are as listed below. Use these forms to define reacting species and enter reaction rate constant parameters.
Use this sheet Species Reactions Rate Constants Options To Define reacting species Specify reactions and rate constant parameters Summarize rate constant parameters Specify the reacting phase

You must specify the reacting species on the Species sheet: 1 2 In the Polymer field, specify the polymer produced. In the Monomers field list the reacting monomers. For each monomer, in the goes to field, specify the polymer segment that the monomer converts to. If you select the terminal double bond polymerization reaction, in the T.D.B.-Seg field, list TDB segment that is formed by the chain transfer reactions and is consumed by the terminal double bond polymerization reaction. Otherwise, go to step 4.
Note: The TDB segment should be of type end segment and should not be used as a repeat segment for a particular monomer (see Step 2). 4 5 Continue listing other types of reacting species, for example, solvents, transfer agents, etc. Select the Generate Reactions option if you want the reactions to be generated automatically.
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After going through the reaction generation once, it is recommended that you turn off this feature. Otherwise, the reaction generation is performed repeatedly.
Listing Reactions
The Ziegler-Natta model generates reactions based on the list of reacting species. You can view the system-generated reactions, then assign rate constant parameters to these reactions. You can view a list of the system-generated reactions on the Reactions sheet. In the Reaction summary listing for each reaction, the first column indicates the reaction type. The second column lists the reactants, and the last column lists the products. The Data Browser window can be resized to better view the reaction listing. Use the following options:
Adding Reactions
To add a new reaction to the scheme, click New to open the Add Reaction subform: 1 2 3 In Reaction type, select a type for the new reaction. The Reaction scheme for that type is displayed. In other reactant (for example, Initiator, Catalyst) fields, enter the reactants of the categories allowed for that reaction type. Click Cancel to discard the new reaction or Click New to add a new reaction or Click or to check the Completion status
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Click Done to return to the reaction summary.
Editing Reactions

To assign rate constants to user reactions, click Rate Constants to open the Rate Constant Parameters subform: 1 2 3 4 5 6 7 In the Site No. field, enter the site number. In the ko field, enter the pre-exponential factor. In the Ea field, enter the activation energy. In the Order field, enter the order for component in reaction. In the Fraction field, enter terminal double bond fraction. In the Tref field, enter reference temperature. Click the stoichiometry list and select a new reaction. Enter rate constants for the new reaction. You can use the Prev and Next buttons to select the previous or next reaction in the list. Click the Summary tab to see a listing of all the rate constant parameters. Click or Click Close to return to the reaction summary. to check the Completion status
8 9
References
Albright L. F. (1985). Processes for Major Addition-Type Plastics and Their Monomers, 2nd Ed. Florida: Krieger Pub. Brockmeier, N. F. (1983). Latest Commercial Technology for Propylene Polymerization. In R.P. Quirk (Ed.), Transition Metal Catalyzed Polymerizations - Alkenes and Dienes. New York: Academic Pub. Choi, K-Y, & Ray, W. H. (1985a). Recent Developments in Transition Metal Catalyzed Olefin Polymerization - A Survey. I. Ethylene Polymerization. J. Macromol. Sci. Rev. Macromol. Chem. Phys., C25 (1), 1.
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Choi, K-Y, & Ray, W. H. (1985b). Recent Developments in Transition Metal Catalyzed Olefin Polymerization - A Survey. II. Propylene Polymerization. J. Macromol. Sci. Rev. Macromol. Chem. Phys., C25 (1), 57. Debling, J. A., Han, G. C., Kuijpers, F., Verburg, J., Zacca, J., & Ray, W. H. (1994). Dynamic Modeling of Product Grade Transition for Olefin Polymerization Processes. AIChE J., 40, No. 3, 506. Nowlin, T. E. (1985). Low Pressure Manufacture of Polyethylene. Prog. Polym. Sci., 11, 29. Short, J. N. (1983). Low Pressure Ethylene Polymerization Processes. In R.P. Quirk (Ed.), Transition Metal Catalyzed Polymerizations - Alkenes and Dienes. New York: Academic Pub. Xie, T., McAuley, K.B., Hsu, J. C. C., & Bacon, D. W. (1994). Gas Phase Ethylene Polymerization: Production Processes, Polymer Properties, and Reactor Modeling. Ind. Eng. Chem. Res., 33, 449.
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12 Ionic Polymerization Model
This section covers the ionic polymerization kinetic model available in Aspen Polymers (formerly known as Aspen Polymers Plus). The cationic, anionic and group transfer addition polymerization kinetics can be modeled using this model. Topics covered include: Summary of Applications, 241 Ionic Processes, 242 Reaction Kinetic Scheme, 242 Model Features and Assumptions, 250 Polymer Properties Calculated, 251 Specifying Ionic Polymerization Kinetics, 252
Some examples of applicable polymers are given in below: Polystyrene - Anionic polymerization is used to produce narrow molecular weight distribution polystyrenes in small quantities. Cationic polymerization is used to produce low molecular weight polystyrenes for coatings and glues. Block copolymers of styrene and butadiene are produced commercially with anionic polymerization. Polyisobutylene - Low-to-medium molecular weight poly isobutylene is produced commercially by polymerization of high purity isobutylene in isobutane or hexane diluent using aluminum chloride or hexane trifluoride as a catalyst. Polybutene - Polybutenes are produced in solution by copolymerizing isobutylene and n-butene using aluminum chloride or hexane trifluoride as a catalyst. Polybutadiene - Block copolymers of styrene and butadiene are produced commercially with anionic polymerization. Polyoxides - Examples are poly ethylene oxide (PEO) and poly propylene oxide (PPO). Continuous tubular or column reactors or semibatch
241
autoclaves are used. The polymerization can be carried out with different mechanisms: anionic (base catalysis), cationic (acid catalysis), or coordinate.
Ionic Processes
Many specialty polymers are manufactured by ionic polymerization processes. For the description of a specific ionic process, refer to the References section. Ionic polymers fall in the category of addition polymers, i.e., the reactive species grow in length by continuous addition of monomer units. However, there are several features that distinguish the ionic polymerization processes from other addition polymerization processes like free-radical and ZieglerNatta: Different propagating species are often present in ionic processes. These species may be free ions, tight ion pairs, loose ion pairs, dormant esters, etc. Moreover the propagating species are often in equilibrium. Association or aggregation phenomena is common in BuLi type of initiators for anionic polymerization. The associated initiator is not reactive and is in equilibrium with its dissociated form. The association phenomena also takes place with growing polymer chains, which reduces the actual number of chains growing at any given time. This phenomena affects both the conversion and polymer properties. Exchange reaction takes place between live and dormant polymer. The active species transfer from one polymer to another. This reaction controls the molecular weight distribution of the final polymer. If the exchange reaction rate constant >> propagation rate constant, then for increasing monomer conversion the polydispersity approaches a limiting value of 1.0. Ionic reactions are a strong function of solvent, initiator and operating conditions and are susceptible to poisons. Chain transfer and termination reactions may be negligible or absent in certain polymerization processes thus leading to formation of living polymers.

In the following sections, the general chemistry of ionic polymerization and the built-in initiator / polymerization kinetic scheme are described. The kinetic scheme is based on literature survey of ionic polymerization mechanisms. Ionic kinetic scheme can model either cationic, anionic or group-transfer polymerization. The ionic kinetic scheme in Aspen Polymers is a super-set of all the above mentioned reactions.
Reaction Steps
There are a few key elementary reactions that apply to all ionic polymerization systems. These include the three basic reaction steps: Formation of active species Chain initiation
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Propagation
There is almost no chain transfer in living polymerization. There are additional reactions for each chemistry which will be discussed later. There can be different forms of propagating species, e.g., free-ions, ion-pairs, and dormant esters. A given ionic polymerization system can have different combinations of these propagating species. To account for different propagating species, the same framework is used as the Ziegler-Natta multi-site kinetics model. In the ionic model, each site refers to a unique type of active species. To model three propagating species for an initiator, the model will have three sites with each site corresponding to the unique propagating active species type. In this framework, the polymer produced by dormant esters will be stored in live polymer attributes for the selected dormant ester site.
Polymer Molecules Tracked

There are three different types of polymer molecules tracked by ionic kinetic scheme:
i Pn,k - live polymer molecule chains of length n with active segment k
attached to the active center of type i. For example, free-ions can be site 1, ion-pairs as site 2 and dormant esters as site 3. The propagation rate constant for dormant esters ( k p for site 3) may be zero.
i Qn - associated (or aggregate) polymer molecule chains of length n
formed by association of propagating species of type i. The site based aggregate polymer attributes contain the information about polymer formed by association of different propagating species. For example, only the ion pairs propagating species may associate in case of BuLi type of initiators.
i Dn - dead polymer molecule chains of length n formed by active
propagating species of type i. The site based bulk polymer attributes contain information about the bulk polymer which is a sum of live, aggregate and dead polymer.
Initiator Attributes
The initiator in ionic model has three attributes which are solved along with moment equations:
P0i = P0FLOW; P0t ,i = PT0FLOW; CIi = CIONFLOW

These variables are provided as attributes so that they can be used in user kinetics to add side reactions. For example, a transfer species ( P0 ) may undergo a side reaction with other components; addition of a salt with same counter ion ( CI ) may tilt the polymerization in one direction by allowing counter-ion to be in equilibrium with ion concentrations from other salts. The initiator decomposition reactions (involving
i t, i
P0i or I m ) can also be modeled in
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Aspen Plus as user reactions which can be solved simultaneously with built-in ionic kinetics in Aspen Polymers. The built-in initiator and polymerization kinetic scheme is shown in here :
Built-In Ionic Polymerization Kinetic Scheme
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The nomenclature used in the ionic polymerization kinetic scheme is shown here:
Symbol Description Chain transfer agent, m Associated initiator, m Coefficient (= 0 when catalyst does not participate in the reaction) Coefficient (= 0 when C-ion does not participate in the reaction) Counter ion (C-ion) corresponding to active species of type i Catalyst, n Dead polymer chain length of n produced by active species of type i Coefficient (= 0 when C-ion does not participate in the reaction) Coefficient (= 0 when Po does not participate in the reaction) Coefficient (= 0 when C-ion does not participate in the reaction) Coefficient (= 0 when C-ion is not formed in the reaction) Initiator, p Monomer, j Association number for initiator dissociation reaction Active species of type i (chain length 0) Transfer active species of type i (chain length 0) Active species of type i with active segment j (chain length 1) Growing species chain of length n of type i with active segment k Associated polymeric species of chain length n with active segment k Terminating agent, m Exchange agent, m
Am AI m bFC
bTCI
CIi Cn
i Dn
d EQL
d EXA
d FC
dI 2
Ip
Mj
n m,p
P0i P0t,i Pi
j,j
i Pn,k
i Qn, k
Tm Xm
The ionic model is a terminal model, implying that the rate constants are functions of only terminal segment of the polymer chain.
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Copolymerization
For copolymerization, the built-in kinetic scheme allows the user to specify the number of monomer types used. Similarly the user has the flexibility to specify the number of each type of reactive species present in the polymerization: Associated initiators Initiators Catalysts Exchange agents Chain transfer agents Termination agents
The user is able to tailor the built-in kinetics to model a specific polymerization system by selecting a subset of the reactions shown in the Built-in Ionic Polymerization Kinetic Scheme figure on page 244. The rate constants for each reaction for active species of type i are calculated at the reaction temperature using the Arrhenius equation shown below. The user specified rate constant parameters are pre-exponential factor the activation energy
i ( ko ) and
( Ea i ) at active species of type i:
Rate Constant
Eai 1 1 k i = k io exp R T T ref
Where:
ko
Ea R T
= Pre-exponential factor in 1/sec for first order reactions and m3/kmol-sec for second order reactions = Activation energy in mole enthalpy units = Universal constant = Reaction temperature in Kelvin 1E38)
Tref = Reference reaction temperature in Kelvin (default is
Formation of Active Species

The active species are the initiator in dissociated form:
AI m n m,p I p
The association and dissociation of initiator is observed in alkyl-Lithium type of initiators in nonpolar solvents for anionic polymerization. n-butyl-Li exists as hexamer whereas s-BuLi and t-BuLi exist as tetramers for styrene polymerization. The dissociated initiator further reacts with monomer to form growing polymer with unit chain length in chain initiation step. This reaction can also be used to represent self-ionization of some strong acids
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(AlCl3 , AlBr3 , TiCl3 ) in cationic polymerization, with n m,p being the degree of
ionization:
I m + bFC Cn P0i + d FC CIi

The active species
P0i is formed by this reaction. Several initiators
(KNH 2 , NaNH 2 ) decompose to form an active species (or dissociate into d FC = 1) . Polystyrene is ions) in anionic polymerization ( bFC = 0, manufactured using KNH 2 initiator.
With no reverse reaction, the electron transfer initiation with light (electrochemical initiation) is also a special case of the above scheme for anionic polymerization. Initiator and catalyst are used in cationic polymerization with no counter-ion ( d FC = 0) . In case of anionic polymerization, a starter may be used to generate an active species. For polyether polyols (polypropylene oxide), initiator is ROH and catalyst is KOH (weak base) and the reaction is only in forward direction. The above scheme can also represent donar-accepter equilibria and self dissociation of acids in cationic initiation
( A+B A-+B+ ) .
Chain Initiation
The active species incorporate monomer to form propagating species with unit chain length:
P0i + M j P i
j,j
The initiator (in dissociated form) directly reacts with monomer to form propagating species with unit chain length. A counter-ion may be formed ( d I 2 = 1) :
I m + M j Pi j,j + d I 2 CIi
The transfer active species incorporate monomer to form propagating species with unit chain length:
P0t,i + M j P i
j,j
Propagation
The growing polymer with an active species at the end of the chain may grow or propagate through the addition of monomer molecules to form long polymer chains. The propagation reaction is represented by:
i i Pn,k + M j Pn+ j,j
where monomer j is being added to a polymer chain of length n, with an active segment of type k and active species of type i. The resulting polymer chain will be of length n+1 and the active segment will be of type j. The
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active segment type usually represents the last monomer type incorporated into the polymer chain.
Copolymerization
For copolymerization, there will be
N m * N m * N site propagation reactions that
may have different reactivities. For example, with two monomers and three site types, the monomer being added could be monomer 1 or monomer 2 while the active segment type could be segments from monomer 1 or monomer 2 at each site type. As a result, there will be twelve rate constants
i (k p , kj ) , where the subscript k refers to the active segment type while the
second subscript j refers to the propagating monomer type. The superscript i refers to active species type. For the terminal model the rate of propagation is dependent only on the concentration of live polymer with active segment k on active species i and the concentration of the propagating monomer j.
Association or Aggregation
The propagating species initiated by alkyl-Lithium type of initiators in anionic polymerization also exhibit the association phenomena like the initiator. The association of live polymeric species is usually dimeric in nature. The associated polymer
i i i Pn, k+P m, k Qn + m, k
i Qn + m, k is tracked as a separate polymer and does not
participate in any other reactions:
Exchange
Exchange reactions exchange the growing active species between two different growing polymers. If both free ions and ion pairs are growing, then the counter-ion can exchange between the two polymeric species. There can be exchange reaction between dormant polymer (with ester as growing species which does not propagate) and ion pairs/free ions. The exchange reaction can also take place between an exchange agent (e.g., alcohol end group in solvent or starter) and a growing polymer. If exchange reaction with a small molecule does not produce a P 0 species, then d EXA = 0 . The exchange between growing species and dormant species takes place in polyether polyols (propylene oxide). The dormant species can be an alcohol:
i j j i Pn,k + Pm,p Pn,k + Pm,p i j Pn,k + X m Pn,k + d EXA P0i
Equilibrium with Counter-Ion

The following reaction represents the equilibrium between free ions and ion pairs, hence the name equilibrium with counter-ion ( d EQL = 1) . The
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spontaneous ionization reaction can also be represented by this reaction when d EQL = 0 :
i j Pn,k Pn,k + d EQL CIj
Chain Transfer
There are four types of chain transfer reactions: Spontaneous Monomer Dormant polymer formation Chain transfer agent
Spontaneous chain transfer can lead to formation of a dead polymer molecule and an active species caused by proton loss, e.g., cationic polymerization of poly isobutylene: Spontaneous
i i Pn,k Dn + P0i
Chain transfer to monomer can take place with hydride abstraction from an olefin, for example, cationic polymerization of polyisobutylene and butyl rubber: Monomer
i i Pn,k + M j Dn + P ij, j
Chain transfer to monomer in polyethers (propylene oxide) can form dormant species (alcohol) . The dormant species is modeled as a live polymer with a different site type but it does not have the usual chain initiation and propagation reactions. This dormant polymer can participate in exchange reactions: Form dormant polymer
i j Pn,k + M p Pn,k + Pi p, p
The growing polymer chain can also be transferred to a chain transfer agent, A, leading to formation of a transfer active species of the same type, i. The reaction rate order wrt. to chain transfer agent can be specified by the user: Chain transfer agent
i i Pn,k + Am Dn + P0t,i
Chain Termination
The growing polymer chain with ion pairs as active species can be spontaneously terminated by combination with counter ion (bTCI = 0) , e.g., cationic polymerization of polystyrene, tetrahydrofuran, polyisobutylene. A growing free ion active species can terminate by reacting with its own counter ion (bTCI = 1) : Counter-ion
i i Pn,k + bTCI CIi Dn
The chain can terminate after reacting with a chain terminating agent to form a dead polymer. Any small molecule can act as a chain terminating agent.
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The reaction rate order wrt. to terminating agent can be specified by the user: Terminating agent
i i Pn,k +Tm Dn
Coupling
Coupling reactions are encountered in thermo-plastic elastomer production. For example, to make styrene-butadiene-styrene (SBS) TPE, styrene is added first, and then half of the butadiene is added. Introducing a coupling agent to this reaction system will form SBS polymer. In this example i=j=1 and k=2.
Pni + Pmj Pnk+m

Another mechanism represented by this reaction is higher order association of polymeric chain. Dimeric association can be modeled by the association reaction, but the coupling reaction should be used to model higher order association of polymer chains. In a given simulation, the coupling and association reactions are mutually exclusive.

Following are the model features and assumptions used in the ionic polymerization model available in Aspen Polymers.
Phase Equilibria
The polymerization model currently considers a single-phase system (vapor or liquid), two-phase system (vapor and liquid), or three-phase (VLL) system when calculating concentrations for the reaction kinetics. For single-phase systems, the reacting phase may be either vapor or liquid. In multi-phase systems, reactions can occur in one or more phases simultaneously. Each reaction object is associated with a single reacting phase, identified on the options form. By default the reacting phase is assumed to be the liquid phase (for VLL systems, the reacting phase must be specified). Several reaction models can be referenced from a single reactor block to account for reactions in each phase.
Rate Calculations
The ionic polymerization kinetic model supplies to the reactor models the reaction rates for the components and the rate of change of polymer attributes (e.g. the chain length distribution moments) : The component reaction rates are computed from the kinetic scheme by summing over all reactions that involve the component.
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The site based moment rates are derived from a population balance and method of moments approach similar to that described in the Calculation Method section on page 182.
Additionally, the moment definitions are modified to include the aggregate polymer as separate and as a part of bulk polymer. The attributes calculate and report up to third moments of live, aggregate and bulk polymer. The moment definitions are:
Polymer Live Polymer,
i Pn,k
Moment Definition
i Qn,k
i f ,k
= n f Pni,k
n n
Aggregate Polymer,
i if ,k = n f Qn ,k i if ,k = n f Qn + m, k n m
Dissociated Aggregate Polymer,
i n + m, k
Bulk Polymer
if = n f {Pni,k + Qni ,k } + Dni

k
Nseg
k
Nseg
i f ,k
i + if ,k + n f Dn k n
Nseg

The following variables can be calculated by the built-in kinetics routine based on the polymer attributes selected, and the subset of the built-in kinetics used for a specific simulation: Zeroth, first and second moments for the composite and site based bulk polymer Zeroth and first moments for the composite and site based live polymer and aggregate polymer Number and weight degree of polymerization and polydispersity index for the composite and site based bulk polymer (DPN, DPW, PDI and SDPN, SDPW, SPDI) Number and weight average molecular weight for the composite and site based bulk polymer (MWN, MWW and SMWN, SMWW) Copolymer segment composition for composite and site based bulk polymer (SFRAC and SSFRAC segment mole fractions) Mole fraction of bulk polymer chains that are live (LPFRAC and LSPFRAC) Mole fraction of bulk polymer chains that are aggregated (APFRAC and ASPFRAC) Number average degree of polymerization for live polymer (LDPN and LSDPN) Number and weight average degree of polymerization for aggregate polymer (ADPN, ADPW, ASDPN and ASDPW)
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Copolymer segment composition for live and aggregate polymer (LSFRAC, ASFRAC, LSSFRAC and ASSFRAC) Live polymer active segment composition (LEFRAC and LSEFRAC)
These variables are stored as component attributes. See Chapter 2 for a description of these component attributes. It is assumed here that attributes needed for the kinetic scheme are selected. For each live polymer attribute, there is also a corresponding aggregate polymer attribute.
Specifying Ionic Polymerization Kinetics

Accessing the Ionic Model
To access the Ionic polymerization kinetic model: 1 2 3 4 5 From the Data Browser, click Reactions. From the Reactions folder, click Reactions. The Reactions object manager appears. If the kinetic model already exists, double-click the desired Reaction ID in the object manager or click Edit to get to the input forms. To add a new model, from the Reactions object manager, click New. If necessary, change the default ID for the reaction. Select Ionic as the reaction type and click OK.
Specifying the Ionic Model

The Ionic model input forms are as listed below. Use these forms to define reacting species and enter reaction rate constant parameters:
Use this sheet Species Reactions Rate Constants Options To Define reacting species Specify reactions and rate constant parameters Summarize rate constant parameters Specify the reacting phase

You must specify the reacting species on the Species sheet: 1 2 In the Polymer field, specify the polymer produced. In the Monomers field, list the reacting monomers. For each monomer, in the goes to field, specify the polymer segment that the monomer converts to. 3 Continue listing other types of reacting species, for example, solvents, transfer agents, etc.
252
Listing Reactions
You can build a list of reactions on the Reactions sheet. In the Reaction summary listing for each reaction, the first column indicates the reaction type. The second column lists the reactants, and the last column lists the products. The Data Browser window can be resized to better view the reaction listing. Use the following options:
Adding Reactions
To add a new reaction to the scheme, click New to open the Add Reaction subform: 1 2 3 In Reaction type, select a type for the new reaction. The Reaction scheme for that type is displayed. In other reactant (for example, Initiator, Catalyst) fields enter the reactants of the categories allowed for that reaction type. Click Cancel to discard the new reaction or Click New to add a new reaction or Click or Click Done to return to the reaction summary. to check the Completion status
Editing Reactions
To add or edit a reaction, click Edit to open the Edit Reaction subform: 1 2 Modify the Reaction type as needed. The Reaction scheme for that type is displayed. Modify reactants as needed.
253
Click or
to check the Completion status
Click Done to return to the reaction summary.

To assign rate constants to user reactions, click Rate Constants to open the Rate Constant Parameters subform: 1 2 3 4 5 6 7 In the ko(fwd) or (rev) field, enter the pre-exponential factor for forward or reverse reaction. In the Ea(fwd) or (rev) field, enter the activation energy for forward or reverse reaction. In the Tref field, enter reference temperature. In the Order field, enter the order. In the Asso. No. field, enter the polymer association number. In the Coeff. b and Coeff. d fields, enter coefficients b and d. Click the stoichiometry list and select a new reaction. Enter rate constants for the new reaction. You can use the Prev and Next buttons to select the previous or next reaction in the list. Click the Summary tab to see a listing of all the rate constant parameters. Click or Click Close to return to the reaction summary. to check the Completion status
8 9
References
Biesenberger, J. A., & Sebastian, D. H. (1983). Principles of Polymerization Engineering. New York: Wiley. Bikales, M., Overberger, & Menges. (1985). Encyclopedia of Polymer Science and Engineering, 2nd Ed. New York: Wiley Interscience. Chang, C. C., Miller, J. W., & Schorr, G. R. (1990). Fundamental Modeling in Anionic Polymerization Processes. J. of Appl. Pol. Sci., 39, 2395-2417. Chang, C. C., Halasa, A. F., & Miller, J. W. (1993). The Reaction Engineering of the Anionic Polymerization of Isoprene. J. of Appl. Pol. Sci., 47, 1589-1599. Compton, R. G. (Ed.). (1992). Mechanism and Kinetics of Addition Polymerizations. Comprehensive Chemical Kinetics, 31. Fathi, H., Hamielec, A. E., & Davison, E. J. (1996). Modelling of Anionic Solution Polymerization of Butadiene - The Effects of Chain Termination and Long Chain Branching on Molecular Weight Distribution Development. Polymer Reaction Eng., 4, No. 4.
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Kennedy, J. P., & Squires, R. G. (1967). Contributions to the Mechanism of Isobutene Polymerization I. Theory of Allylic Termination and Kinetic Considerations. J. Macromol. Sci., A1(5), 805-829. Kirk-Othmer. (1991). Encyclopedia of Chemical Technology, 4th Ed. New York: Wiley Interscience. Moore, J. G., West, M. R., & Brooks, J. R. (1979). The Anionic Solution Polymerization of Butadiene in a Stirred-Tank Reactor. ACS Symp. Ser., 104. Muller, et. al. (1995). Kinetic-analysis of Living Polymerization Processes exhibiting slow equilibria. Application to group transfer and cationic polymerizations. 5th International Workshop on Polymer Reaction Engineering, 131, 9-11 October, Berlin: DECHEMA. Odian, G. (1981). Principles of Polymerization, 3rd Ed. New York: Wiley Interscience. Pepper, G. C. (1957). Cationic Polymerization. Proc. of the Intl. Symp. on Macromol. Chemistry. Prague. Szwarc, M. (1996). Ionic Polymerization Fundamentals. New York: Hanser. Treybig, M. N., & Anthony, R. G. (1979). Anionic Styrene Polymerization in a Continuous Stirred-Tank Reactor. ACS Symp. Ser., 104.
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13 Segment-Based Reaction Model
This section describes the segment-based power-law reaction model available in Aspen Polymers (formerly known as Aspen Polymers Plus). Topics covered include: Summary of Applications, 256 Segment-Based Model Allowed Reactions, 258 Model Features and Assumptions, 263 Polymer Properties Calculated, 264 Specifying , 276
The segment-based power-law reaction model can be used to simulate polymerization reactions using a simple power-law type rate expression. This may be useful when simulating new processes that do not fit well into the other built-in models in Aspen Polymers, or when a very detailed mechanistic reaction model is not necessary. The segment-based power-law model is the best choice for simulating stepgrowth addition processesfor example, the production of polyurethane. This model may also be used to represent processes involving changes to polymer segments. The underlying kinetics are basic power law reactions in which segments and monomeric components may participate. Some examples of applicable polymers are: Polyvinyl alcohol (PVA) - Alcoholysis of polyvinylacetate Chlorinated polyethylene (CPE) - Chlorination of polyethylene Polymethylmethacrylate (PMMA) - Recovery of methylmethacrylate from PMMA Polyisobutylene - Chain scission of polyisobutylene
256
Step-Growth Addition Processes

Step-growth addition processes involve reactions between two functional groups to produce a new functional group without the loss of low molecular weight condensates. For example, in the production of polyurethane polymers a diol is reacted with a diisocyanate to produce an alternating copolymer with urethane linkages between the monomer units:
O HO R OH + O=C=N X N=C=O R OCNH X
O NHCO
diol
diisocyanate
polyurethane
These reactions are usually irreversible. The individual reaction steps can be simulated using the segment-based power-law model.
Polymer Modification Processes

The conventional route for synthesizing commercial polymers is through the polymerization of a monomeric compound. These polymerization reactions fall under different categories depending on the nature of the monomer and its growth mechanism. However, once synthesized, polymers may undergo further reactions. In some instances, these reactions may be undesirable side reactions, in which case they may be considered as degradation reactions. In other cases, the only mechanism for producing certain polymers may be through the modification of a starting polymer. Typically, this situation occurs if a monomer is not readily available for that polymer. For example, polyvinyl alcohol is produced by alcoholysis of polyvinyl acetate. Modification reactions are often used to improve polymer properties such as oil resistance (chlorosulfonation of polyethylene), heat resistance (chlorination of polyethylene), solubility ("-cellulose), and flammability (natural rubber). There are also a few cases where it is economically desirable to react scrap polymer for monomer recovery (methyl methacrylate from polymethyl methacrylate) (Rodriguez, 1989).
Reaction Categories
Regardless of the end effect of the polymer modification reaction, the events taking place fall into one of two categories based on the site where they occur on the polymer chain. The reactions may take place on: Side groups Polymer backbone: scission, depolymerization, cross-linking, or bond changes
There are some fundamental issues that distinguish reacting polymers from their low molecular weight counterparts. One obvious characteristic of reacting polymers is the potential for steric hindrance. A reacting side group may be too close to the polymer chain, for example. There may also be changes in solubility as reaction progresses. Furthermore, crystallinity has an effect on the polymer reactivity; in general, for a semicrystalline polymer, only the amorphous region is able to react.
257
Finally, an important difference that characterizes polymers is the fact that a higher local concentration of reacting functional groups is observed than that indicated by the overall polymer concentration (Odian, 1991).
Segment-Based Model Allowed Reactions

The reaction categories allowed in the segment-based reaction model, along with a brief summary of the conditions where each of these reactions may occur, is shown here:
258
Segment Based Model Reaction Categories
Conventional Species
Reactions involving all non polymeric species fall under this category. Monomeric components may react among themselves to produce intermediate species. These reactions are represented as Category I in the Segment Based Model Reaction Categories figure on page 259.
259
Side Group or Backbone Modifications

Polymer modification reactions aimed at altering end properties involve in most cases side group or backbone modifications. In such reactions, groups attached to the polymer chain are substituted. One example is that of the alcoholysis of polyvinyl acetate to produce polyvinyl alcohol:
CH3 C O O CH CH2
+ CH3OH
OH CH CH2
+ CH3CO2CH3
Another example is the chlorination of polyethylene to produce chlorinated polyethylene (CPE):
CH2
+ Cl2
CHCl
+ HCl
Side group and backbone reactions are illustrated as reaction Category II in the Segment Based Model Reaction Categories figure on page 259.
Chain Scission
A common polymer degradation reaction is chain scission. In this case, bonds are broken along the polymer chain resulting in shorter polymer molecules with lower molecular weight. Chain scission may be induced by several factors. One example is the scission of polyisobutylene upon oxidation:
CH2
CH3 C CH2 CH2
CH2
CH3 C + CH2 CH2
Some scission reactions may involve a monomeric component, such as an acid or base:
CH2 CH2
+ HCl
CH2Cl + CH3
Chain scission reactions are represented as Category III reactions in the Segment Based Model Reaction Categories figure on page 259.
Depolymerization
Depolymerization is the reverse of the propagation step of a polymerization reaction. In such reactions, monomer molecules are lost from the polymer chain. Depolymerization is often considered a degradation reaction. There are, however, cases where it is brought on by design to recover monomer from scrap polymer. An example depolymerization reaction is that of polymethyl methacrylate to regenerate methyl methacrylate:
260
CH3 CH2 C CH2 C O O CH3
CH3 C C O O CH3
CH3 CH2 C + CH2 C O O CH3
CH3 C C O O CH3
Depolymerization is illustrated as Category IV in the Segment Based Model Reaction Categories figure on page 259.
Propagation
Propagation reactions involve the addition of monomers to the end of a growing polymer chain. Propagation is illustrated as Category V in the Segment Based Model Reaction Categories figure on page 259.
Combination
There are other mechanisms through which polymer segments react with each other. Some of these reactions, grouped as combination reactions, include kinetic events where two polymer molecules combine into one. These reactions are represented as Category VI in the Segment Based Model Reaction Categories figure on page 259.
Branch Formation
Branch formation occurs when a polymer molecule attaches to another polymer chain, converting a repeat unit to a branch point. Monomers can also react with repeat units to initiate branch formation. Branch formation is illustrated as Category VII in the Segment Based Model Reaction Categories figure on page 259.
Cross Linking
Cross linking occurs when a repeat unit in one chain reacts with a repeat unit in another chain, forming a cross link (branch 4) segment. Cross linking is illustrated as Category VIII in the Segment Based Model Reaction Categories figure on page 259.
Kinetic Rate Expression

The segment-based reaction model uses a modified power-law rate expression where the rate of reaction is calculated as the product of the reacting species concentrations with a rate constant representing the specific reactivity of the reaction. The kinetic rate expression in the segment-based model is described below:
261
Equation
Tref specified Tref unspecified

*
k net ,i = [Catalysti ] k o i e k net ,i = [Catalysti ] k o i e

i
Eai 1 1 R T Tref
T T ref
U ( flag i )
bi
Eai RT
T bi U ( flag i )
k C
j a mj j i net ,i
Assign User Rate Constants is used: Assign User Rate Constants is not used:
ratem = activity m ratem =
C
j
amj j
k net ,m
Nomenclature
Symbol m i j Description User reaction number Rate constant set number Component number Product operator Concentration* of component j, mol/L Catalyst order term for catalyst i (default = 1) Power-law exponent for component j in reaction m Pre-exponential factor in user-specified inverse-time and concentration units** Net rate constant for set i assigned to reaction m Net rate constant for reaction m Activation energy in user-specified mole-enthalpy units (default =0) Temperature exponent (default = 0) Universal gas constant in units consistent with the specified activation energy Temperature, K Optional reference temperature. Units may be specified, they are converted to K in the model. Defaults to global reference temperature (Global Tref) specified on the Specs sheet. User flag for rate constant set i. This flag points to an element of the user rate constant array. User rate constant vector calculated by the optional user rate constant subroutine. The user flag indicates the element number in this array which is used in a given rate expression. When the user flag is not specified, or when the user rate constant routine is not present, this parameter is set to 1.0.
Cj
i mj
ko knet ,i
k net , m
Ea b R T
Tref
flag U
* **
The concentration basis may be changed to other units using the Concentration basis field on the Specs sheet or using the optional concentration basis subroutine. The reference temperature may be specified globally on the Specs sheet or locally for each rate constant set on the Rate-Constants sheet. If global and local reference temperatures are both unspecified then this form of the equation is applied.
262
Customizing the Rate Expression; User Rate Constant Subroutine

You can modify the standard rate expression using the optional user rate constant feature. The rate constant form includes a parameter called the user flag that identifies an element in an array of user rate constants. This array is calculated by a user-written Fortran subroutine. The standard rate expression is multiplied by the user rate constants as shown above. See Program Files\Aspen Plus <version>\engine\user\USBRCN.f for a template for this routine.
Concentration Basis for Rate Calculations

Component concentrations depend on the calculation basis: molarity, mole fraction, mass fraction, mass concentration, etc. The polymer mole fraction is converted into its segment mole fractions according to the following equation:
Fracs,i = Frac p * SFRAC( i )*

Where:
Mw p Mwsegavg
Fracs,i
= Segment mole fraction
SFRAC( i ) = Polymer segment fraction (component attribute)

Mw p
= Polymer molecular weight
Nseg
Mwsegavg =
Average segment molecular weight =
SFRAC(i )* Mw
1
User Concentration Basis Subroutine

Alternately, a user basis subroutine can be used to calculate the component concentrations and the reacting-phase holdup basis used in the component and attribute conservation equations. Use this subroutine when rate constants are available in unusual concentration units not found in Aspen Polymers, or when the reacting phase volume or area calculated by the reactor model is not consistent with the real reactor (for example, in plug flow reactors with fixed liquid level). The segment-based model and step-growth model can use the same basis routine. See Program Files\Aspen Plus <version>\engine\user\USRMTS.f for a template for this routine.

The following assumptions are built into the segment-based reaction model: All reactions between two segments are intermolecular; ring formation reactions are specifically excluded unless the ring molecules are tracked as separate oligomer components
263
Reactions may occur anywhere in the polymer chain Mass balance holds for components involved in the reactions on segment basis Moment of chain length distribution calculations cover up to the first moment (ZMOM, SFLOW, FMOM). Higher moments (SMOM, TMOM) are not predicted by the current version of the model Since higher moments not covered, segment-based model should be last in reaction block sequencing

The segment-based reaction model calculates and returns the following information: Rate of change for all components involved in reaction scheme, and rate of change for all segments Polymer segment composition (SFLOW, SFRAC, EFRAC) Zeroth moment of chain length distribution (ZMOM) First moment of chain length distribution (FMOM) Number average degree of polymerization (DPN) Number average molecular weight (MWN) When the Reacting Site is specified on the Specifications form, the model will calculate rates for the zeroth moment, first moment, and segment flow rates at the specified site (attributes SZMOM, SFMOM, and SSFLOW for the specified site number). These attributes are used to calculate the composite attributes listed above.
This information is returned through the stream compositions for the component rate of change, and through the polymer component attributes for the segment rate of change and moment calculations. The rate of change of polymer mass is calculated as follows:
Nseg
Rp =
R
1
s ,i
* Mwi
Mw p
This is the sum of the rates of change of segment masses. Each segment type is assigned a value , which indicates the number of points of attachment connecting the segment to other segments in the polymer chain:
Segment Type End Repeat Branch-3 Branch-4 1 2 3 4
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The rate of change of the zeroth moment ( 0 ) is calculated from the rate of change of the first moment ( 1 ) and the segment type ():
0 1 1 = 2 t t t
The factor of accounts for the fact that each connection links two segments (without this correction the points of connection are counted twice). This method is best illustrated through these examples:
Valid Yes No Yes Yes Yes Yes Yes Yes Yes Reaction Type Initiation Initiation Propagation (addition) Propagation (insertion) Combination Combination Branching Branching Cross linking Stoichiometry
1
+2 +1 +1 +1 0 -1 +1 0 -1
+1 +1 +1 +1 +1 +0 +1 +1 +0
0
+1 0 0 0 -1 -1 0 -1 -1
M + M P2 M P1 Pn + M Pn +1
* * Pn + M Pn +1
M+ME+E MR E+MR+E MR E+ER+R E+ER R + M B3 + E R + E B3 + R R + R B4
Pn + Pm Pn + m
Pn + Pm Pn + m Pn + M Pn +1 Pn + Pm Pn + m Pn + Pm Pn + m
M = Monomer; E = End group segment; B3 = Branch-3 segment; B4 = Branch-4 segment
This method lets you specify most classes of reactions, however special care must be taken to ensure that the reaction is defined in a manner that is consistent with the previous equation. In particular, the segment-based model does not allow initiation reactions of the type M P1 since the equation does not account for the initial formation of polymer molecules through this mechanism. Note, however, that this mechanism is valid since the same reaction can represent an insertion type propagation step in which the active polymer end group is conserved.
User Subroutines
The segment-based power-law model can be customized by applying userwritten subroutines. There are two types of subroutines available. The concentration and holdup basis for the model can be changed through a user basis subroutine. A user rate-constant subroutine can be used to extend the standard reaction rate expression. These routines can be used together in any combination.
265
User Basis Subroutine

The user basis subroutine can be used to calculate the component concentrations and the reacting-phase holdup (typically volume in a CSTR or batch reactor or active area in a PFR). This routine can also be used to calculate rates of change of components and component attributes. Use this subroutine when rate constants are available in unusual concentration units not found in Aspen Polymers, or when the reacting phase volume or area calculated by the reactor model is not consistent with the real reactor (for example, in plug flow reactors with fixed liquid level). This subroutine can be used in conjunction with Fortran blocks and user component attributes to calculate mass-transfer rates and to account for the influence of mass-transfer limitations on the component concentrations in the reacting phase. The argument list for the user basis routine is provided here. This argument list is prepared in a Fortran template called USBBAS.F, which is delivered with Aspen Polymers.
SUBROUTINE USBBAS 1 2 3 4 5 6 7 8 9 * 1 2 SOUT, IDSCC, NINTB, INTM, NWORK, X1, FLOWL1, VL1, VL1RX, IFLRTN, VBASIS, TIME ) NSUBS, NPO, INTB, NREALM, WORK, X2, FLOWL2, VL2, VL2RX, CRATES, IPOLY, IDXSUB, NBOPST, NREALB, REALM, NCPM, Y, FLOWV, VV, VVAPRX, NTCAT, NSEG, ITYPE, NIDS, REALB, NIWORK, IDXM, DUM1, FLOWS, VSALT, VSLTRX, RATCAT, IDXSEG, XMW, IDS, NINTM, IWORK, X, FLOWL, VLQ, VLIQRX, RFLRTN, CSS, AXPOS,
Variable SOUT NSUBS IDXSUB ITYPE Usage Input Input Input Input Type REAL*8 INTEGER INTEGER INTEGER NSUBS NSUBS Dimension (1) Description Stream vector Number of substreams in stream vector Location of substreams in stream vector Substream type vector 1=MIXED 2=CISOLID 3=NC
266
Variable XMW IDSCC NPO NBOPST NIDS NINTB INTB
Usage Input Input Input Input Input Input Retention
Type REAL*8 HOLLERITH INTEGER INTEGER INTEGER INTEGER INTEGER
Dimension NCC 2,NCC 6, NPO
Description Conventional component molecular weights Conventional component ID array Number of property methods Property method array Number of reaction model IDs User-specified length of INTB array
NINTB
Reactor block integer parameters (See Integer and Real Parameters, page 151) User-specified length of REALB array
NREALB REALB
Input Retention
INTEGER REAL*8 NREALB
Reactor block real parameters (See Integer and Real Parameters, page 151) User-specified length of INTM array User subroutine integer parameters (See Integer and Real Parameters, page 151) User-specified length of REALM array User subroutine real parameters (See Integer and Real Parameters, page 151) Length of user subroutine integer work vector
NINTM INTM
Input Retention
INTEGER INTEGER NINTM
NREALM REALM
Input Retention
INTEGER REAL*8 NREALM
NIWORK IWORK NWORK WORK NCPM
Input Work Input Work Input
INTEGER INTEGER INTEGER REAL*8 INTEGER NWORK NIWORK
User subroutine integer work vector (See Local Work Arrays, page 151) Length of user subroutine real work vector User subroutine integer work vector (See Local Work Arrays, page 151) Number of components present in the mixed substream (See Packed Vectors, page 151)
IDXM X X1 X2 Y Dum1 FLOWL FLOWL1 FLOWL2 FLOWV FLOWS
Input Input Input Input Input Dummy Input Input Input Input Input
REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8
Component sequence numbers (See Packed Vectors, page 151) Overall liquid mole fractions First liquid mole fractions Second liquid mole fractions Vapor phase mole fractions Argument reserved for future application Total liquid flow rate, kmol/sec First liquid flow rate, kmol/sec Second liquid flow rate, kmol/sec Vapor flow rate, kmol/sec Salt flow rate, kmol/sec
267
Variable VL VL1 VL2 VV VSALT VLIQRX VL1RX VL2RX VVAPRX VSLTRX RFLRTN IFLRTN CRATES NTCAT RATCAT CSS VBASIS IPOLY NSEG IDXSEG AXPOS TIME
Usage Input Input Input Input Input Input Input Input Input Input Retention Retention Output Input Output Output Output Input Input Input Input Input
Type REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 INTEGER REAL*8 INTEGER REAL*8 REAL*8 REAL*8 INTEGER INTEGER INTEGER REAL*8 REAL*8
Dimension
Description Total liquid molar volume, m3/ kmol First liquid molar volume, m3/ kmol Second liquid molar volume, m3/ kmol Vapor molar volume, m3/ kmol Salt molar volume, m3/ kmol Volume* of liquid in reactor, m3 Volume* of first liquid in reactor, m3 Volume* of second liquid in reactor, m3 Volume* of vapor in reactor, m3 Volume* of salt in reactor, m3
(1) (1) NCC
Real retention for FLASH Integer retention for FLASH Component rates of change, kmol/m3sec Number of component attributes Component attribute rates of change, cat/m3-sec Concentration vector for the active phase Holdup basis used to calculate reaction rates* Reacting polymer component index Number of segment components
NTCAT NCC
NSEG
Segment component index vector RPlug only: axial position, m RBatch only: time, sec
When using molar concentrations, this parameter is volume of the reacting phase in m 3 in RCSTR and RBatch or the cross-sectional area of the reacting phase in m 2 in RPlug.
Note: The argument lists for the segment-based user basis routine and stepgrowth user basis routine are identical. Both types of models can reference the same basis routines. Example 1 illustrates how to use the user basis routine to convert the concentration basis from the standard molar concentration basis (mol/L) to a mass concentration basis (mol/kg). (Note: the current version of Aspen Polymers supports several concentration basis through the BASIS keyword located on the Specs sheet. This example is a demonstration). Using these units, the reaction rates are calculated in units of mol/kg-sec. These rates are multiplied by the holdup basis (VBASIS) for the reactor in the segment-based power-law model. The holdup basis must be consistent with the concentration basis, e.g., in this case it must be in kg. The holdup basis pertains to the reacting phase, it does not include the phases that do not react. Example 1: A User Basis Routine For the Mass-Concentration Basis
268
Ci =
Xi M Liquid
= Mass-concentration of component i = Mole fraction of component i liquid phase
Ci Xi
M Liquid = Average molecular weight of components in the

CALL PPMON_VOLL( TEMP, PRES, X, NCPMX, IDXM, 1 NBOPST, GLOBAL_LDIAG, 1, VLQ, DVS, KER) C-unpack the mole fraction vector into the molar concentrations... CALL SHS_UNPACK ( X , NCPMX, IDXM, CSS ) C --------------------------------------------------------------C C concentration (mole/kg)=(mole I / mole liquid )*( mole liquid/kg) C C --------------------------------------------------------------DO 10 I = 1, NCOMP_NCC CSS(I) = CSS(I) * 1.D3 / STWORK_XMWL 10 CONTINUE C --------------------------------------------------------------C C reacting phase basis must be consistent with concentration basis (kg) C liquid mass inventory = liquid volume * density C C --------------------------------------------------------------VBASIS = VLIQRX * STWORK_XMWL * 1.D-3 / VLQ RETURN Note: This excerpt does not include the argument list and declarations section of the user basis routine. The plug flow reactor model in Aspen Plus assumes that the vapor and liquid move at the same velocity through the reactor (e.g., no-slip conditions). This assumption is not consistent with the physical reality of polymer finishing reactors or wiped-film evaporators. The subroutine in Example 2 circumvents the no-slip assumption in RPlug, allowing you to specify the volume occupied by the liquid phase. In this example, you specifiy the first integer argument in the RPlug block as 1 and the first real argument as the volume fraction of the reactor occupied by the liquid phase. Example 2: A User Basis Routine to Specify Liquid Volume in RPlug UFRAC = 1.D0 IF ( REALB(1) .NE. RGLOB_RMISS ) UFRAC = REALB(1) IF ( INTB(1).EQ.1 ) THEN C - unpack the mole fraction vector into the molar concentrations... CALL SHS_UNPACK ( X , NCPMX, IDXM, CSS ) C - concentration = mole fraction divided by molar volume of phase DO 20 I = 1, NCOMP_NCC
269
CSS(I) = CSS(I) / VLQ 20 CONTINUE C - multiply total reactor volume by user-specified volume fraction VBASIS = ( VLIQRX + VVAPRX ) * UFRAC C - this line makes RPlug calculate liquid residence time (not L+V) SOUT(NCOMP_NCC+8)=(SOUT(NCOMP_NCC+9)/ SOUT(NCOMP_NCC+6)) / VLQ RETURN END IF Note: This excerpt does not include the argument list and declarations section of the user basis routine.
User Rate-Constant Subroutine

The user rate constant subroutine can be used to modify rate constant parameters for model-generated and user-specified reactions. Use this routine to modify the standard power-law rate expression for non-ideal reaction kinetics. The user rate constant feature can be used to modify the standard power-law rate expression. This subroutine returns a list of real values, which are stored in an array RCUSER. The length of this array is defined by the keyword NURC (number of user rate constants) in the user rate constant subroutine form (USER-VECS secondary keyword). Each of the elements in the user rate constant array can store a different user rate constant. The USER-FLAG keyword in the Rate Constants form is used to specify which user rate constant is used with a particular set of rate constants. Elements 1 through NURC of RCUSER are calculated by a user rate-constant subroutine. The standard rate expression is multiplied by the USER-FLAGth element of the user rate constant vector RCUSER. For example, if the USER-FLAG field contains the number 4, the power-law rate term will be multiplied by the fourth element of array RCUSER. By default, the USER-FLAG keyword is set to zero. The zeroth element of the RCUSER array is set to a value of 1.0, so the rate expression remains unmodified unless the USERFLAG keyword is specified. The argument list for the subroutine is provided here. This argument list is prepared in a Fortran template called USBRCN.F, which is delivered with Aspen Polymers.
270
SUBROUTINE USBRCN 1 2 3 4 5 6 7 8 9 SOUT, IDSCC, NINTB, INTR, NWORK, X1, VL1, NSEG, PRES, NSUBS, NPO, INTB, NREALR, WORK, X2, VL2, IDXSEG, NURC, 1 IDXSUB, NBOPST, NREALB, REALR, NCPM, Y, VV, NCC, RCUSER, ITYPE, NIDS, REALB, NIWORK, IDXM, DUM1, VSALT, CSS, CATWT XMW, IDS, NINTR, IWORK, X, VL, IPOLY, TEMP, )
Variable SOUT NSUBS IDXSUB ITYPE Usage Input Input Input Input Type REAL*8 INTEGER INTEGER INTEGER NSUBS NSUBS Dimension (1) Description Stream vector Number of substreams in stream vector Location of substreams in stream vector Substream type vector 1=MIXED 2=CISOLID 3=NC XMW IDSCC NPO NBOPST NIDS IDS Input Input Input Input Input Input REAL*8 HOLLERITH INTEGER INTEGER INTEGER HOLLERITH 2,NIDS 6, NPO NCC 2, NCC Conventional component molecular weights Conventional component ID array Number of property methods Property method array (used by FLASH) Number of reaction model IDs Reaction model ID list: i,1 reactor block ID i,2 reactor block type i,3 reaction block ID i,4 reaction block type NINTB INTB Input Retention INTEGER INTEGER NINTB User-specified length of INTB array Reactor block integer parameters (See Integer and Real Parameters, page 151) User-specified length of REALB array NREALB Reactor block real parameters (See Integer and Real Parameters, page 151) User-specified length of INTM array
NREALB REALB
Input Retention
INTEGER REAL*8
NINTR
Input
INTEGER
271
Variable INTR
Usage Retention
Type INTEGER
Dimension NINTR
Description User subroutine integer parameters (See Integer and Real Parameters, page 151) User-specified length of REALM array
NREALR REALR
Input Retention
INTEGER REAL*8 NREALR
User subroutine real parameters (See Integer and Real Parameters, page 151) Length of user subroutine integer work vector
NIWORK IWORK NWORK WORK NCPM
Input Work Input Work Input
INTEGER INTEGER INTEGER REAL*8 INTEGER NWORK NIWORK
User subroutine integer work vector (See Local Work Arrays, page 151) Length of user subroutine real work vector User subroutine integer work vector (See Local Work Arrays, page 151) Number of components present in the mixed substream (See Packed Vectors, page 151)
IDXM X X1 X2 Y Dum1 VL VL1 VL2 VV VSALT IPOLY NSEG IDXSEG NCC CSS TEMP PRES NURC
Input Input Input Input Input Dummy Input Input Input Input Input Input Input Input Input Input Input Input Input
REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 REAL*8 INTEGER INTEGER INTEGER INTEGER REAL*8 REAL*8 REAL*8 INTEGER
Component sequence numbers (See Packed Vectors, page 151) Overall liquid mole fractions First liquid mole fractions Second liquid mole fractions Vapor phase mole fractions Argument reserved for future application Total liquid molar volume, m3/kmol First liquid molar volume, m3/kmol Second liquid molar volume, m3/kmol Vapor molar volume, m3/kmol Salt molar volume, m3/kmol Reacting polymer component index Number of segment components
NSEG NCC
Segment component index vector Number of components (unpacked) Concentration vector for reacting species Temperature, K Pressure, Pa Number of user rate constants (See User Rate-Constant Subroutine, page 140)
RCUSER
Output
REAL*8
NURC
User rate constant vector (See User Rate-Constant Subroutine, page 140)
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Variable CATWT
Usage Input
Type REAL*8
Dimension
Description Catalyst weight, kg (in RPLUG, weight/length)
Example 3 illustrates how to use this subroutine to implement complex rate expressions in the segment-based power-law model. Example 3: Implementing a Non-Ideal Rate Expression Suppose a side reaction QZ is first order with respect to component Q and first order with respect to a catalyst C. The effectiveness of the catalyst is reduced by inhibitor I according to the following equation:
[C ] = 1 + ([aC+ bT])[ I ]
actual eff
Where:
[Ceff ]
= Effective catalyst concentration, mol/L
[Cactual ] = Actual catalyst concentration, mol/L [I ]

T a,b = Inhibitor concentration, mol/L = Temperature, K = Equation parameters
The net rate expression can thus be written as:
rate = [Q]
Where:
1 + ( a + bT )[ I ]
[C ]
actual
ko e
E* 1 1 R T Tref
ko
E* R
= Pre-exponential factor, (L/mol)/sec = Activation energy = Gas law constant = Reference temperature for
Tref
[Q]
ko
= Concentration of component Q, mol/L
The standard rate expression for side reactions is:
rate = koe
Where:
E* 1 1 R T Tref
Ci i * U ( j ) i
= Product operator = Concentration of component i
Ci
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i
U j
= Power-law exponent for component i = User rate constant = User rate-constant flag
3
Suppose the rate constant for the uninhibited reaction is 3 10 (L/mol)/min at 150C, with an activation energy of 20 kcal/mol, and the inhibition rate constants are A=0.20 L/mol, B=0.001 L/mol-K. The stoichiometric coefficients and power-law exponents are specified directly in the Stoic and PowLaw-Exp keywords. The Arrehnius rate parameters and reference temperature are also specified directly in the model. The parameters for the user rate constant equation can be specified using the optional REALRC list. Including the parameters in the REALRC list allows the model user to adjust these parameters using the standard variable accessing tools, such as Sensitivity, Design-Specification, and Data-Regression. The resulting model input is summarized below: USER-VECS NREALRC=2 NUSERRC=1 REALRC VALUE-LIST=0.2D0 0.001D0 STOIC 1 Q -1.0 / Z 1.0 POWLAW-EXP 1 Q 1.0 / C 1.0 RATE-CON 1 3D-3<1/MIN> 20.000<kcal/mol> TREF=150.0<C> URATECON=1 The power-law term from this equation is:
rate = koe
Where:
E* 1 1 R T Tref
[C][ Q]
[Q] = Concentration of component Q, mol/L [C] = Catalyst concentration, mol/L
ko = Pre-exponential factor
Thus, the required user rate constant is:
U ( j = 1) =
Where: [I] T a, b
1 (1 + ( a + bT )[ I ]
An excerpt from the user rate constant subroutine for this equation is shown below: C - Component Name INTEGER ID_IN(2) DATA ID_IN /'INHI','BITO'/ C ====================================================================== C EXECUTABLE CODE
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C ====================================================================== C - find location of inhibitor in the list of components DO 10 I = 1, NCOMP_NCC IF ( IDSCC(1,I).EQ.ID_IN(1).AND.IDSCC(2,I).EQ.ID_IN(2) ) I_IN=I 10 CONTINUE C - get the concentration of the inhibitor C_IN = 0.0D0 IF ( I_IN .GT.0 ) C_IN = CSS( I_IN ) C ---------------------------------------------------------------------C Parameters: each REALR element defaults to zero if not specified C ---------------------------------------------------------------------A = 0.0D0 IF ( NREALR .GT. 0 ) A = REALR( 1 ) B = 0.0D0 IF ( NREALR .GT. 1 ) B = REALR( 2 ) C ---------------------------------------------------------------------C User rate constant #1 U(1) = 1 / ( 1 + (A+BT)[I] ) C ---------------------------------------------------------------------IF ( NURC.LT.1 ) GO TO 999 RCUSER(1) = 1.0D0 / ( 1.0D0 + ( A + B*TEMP ) * C_IN ) END IF 999 RETURN
Integer and Real Parameters

Each user model has two sets of integer and real parameters. The first set comes from the subroutine form of the reactor block. The second set comes from the subroutine form of the step-growth reactions model. Each of these parameters are retained from one call to the next, thus these parameters can be used as model inputs, outputs, or retention. The reactor block integer and real parameters can be used to specify data which are specific to a particular unit operation, such as reactor geometry, mass transfer coefficients, etc. The integer and real parameters in the subroutine forms can be used to specify global parameters, such as rate constants or physical property parameters.
Local Work Arrays

You can use local work arrays by specifying the model workspace array length on the Subroutine forms. These work areas are not saved from one call to the next. Both user subroutines share a common work area. User subroutines are responsible for initializing the work space at the start of each subroutine.
Packed Vectors
Aspen Plus frequently uses a technique called packing to minimize simulation time. The user models previously described use packed vectors to track the mole fractions of each phase (vectors X, X1, X2, and Y). These vectors contain NCPM elements (Number of Components Present in the Mixed substream). The component index associated with each element is listed in the vector IDXM. All other vectors used by the model, including the rates vectors and the component concentration vectors, are unpacked.
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Calculating Unpacked Component Concentrations Calculate unpacked component concentrations of the first liquid phase given the packed mole fractions of the first liquid phase and the molar volume of the first liquid phase. IF ( VL1 .GT. 0.D0 .AND. FLOWL1.GT.0.D0 ) THEN DO 10 I = 1, NCPM CSS(I) = X1( IDXM( I ) ) / VL1 10 CONTINUE END IF Note: NCPM steps were required to load the concentration vector. Since NCPM is always less than or equal to NCC (total number of conventional components), there is a reduction in the required number of steps to perform the operation. Using packed arrays for calculations reduces overhead by eliminating the need to check for zero values when carrying out mathematical operations.
Specifying Segment-Based Kinetics

Accessing the Segment-Based Model
To access the Segment-based power-law kinetic model: 1 2 3 4 5 From the Data Browser, click Reactions. From the Reactions folder, click Reactions. The Reactions object manager appears. If the kinetic model already exists, double-click the desired Reaction ID in the object manager or click Edit to get to the input forms. To add a new model, from the Reactions object manager, click New. If necessary, change the default ID for the reaction. Select Segment-Bas as the reaction type and click OK.
Specifying the Segment-Based Model

The Segment-Based model input forms are as listed below. Use these forms to specify reaction conditions and build a reaction scheme. Use the Specifications forms to define reaction stoichiometry, enter reaction rate constant parameters, assign rate constants to reactions, and to specify the concentration, reacting phase, reacting site, and other model options.
Use this sheet Specs Reactions To Define reacting phase, concentration basis, and reacting polymer Define reaction stoichiomerty and enter reaction rate constant parameters
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Use this sheet Rate Constants Assign Rate Constants
To Specify reaction rate parameters and catalysts Associate each reaction with one or more sets of rate constants
Use the User Subroutines forms to specify the names and parameters for optional user basis and rate constant subroutines.
Use this sheet Rate Constants To Specify the name of the user kinetics routine, the number of user rate constants calculated by the routine, and to give the integer and real arguments for the user arrays for this routine Specify the name of the user concentration and holdup basis routine and give the integer and real arguments for the user arrays for this routine
Basis
Specifying Reaction Settings

Use the Specs sheet to define the reaction model settings: 1 2 3 In the Reacting polymer field, specify the reacting polymer. In the Reference temperature field, specify the default global reference temperature for rate constant parameters. In the Phase field, specify the phase in which reactions occur. If the specified phase is Liquid phase 1 or Liquid phase 2 you may also choose to specify additional options (under the Options frame) to control how calculations are performed when the phases collapse into a single liquid phase. For details, see Selecting the Reacting Phase next. 4 In the Basis field, specify the basis for component concentrations in the reaction rate calculation. Optionally, you can apply a user subroutine to calculate the concentration and holdup basis. For details, see User Basis Subroutine on page 266. 5 If desired, specify a site number in the Reacting Site field, and specify which method to use in the Segment concentration basis frame. For details, see Selecting the Reacting Site on page 278.
Selecting the Reacting Phase

The Specs form lets you specify the phase in which the reactions occur. Select the appropriate phase from the list in the Reacting Phase field. All of the reactions in the segment-based reaction object are assumed to take place in the same phase. You can use two (or more) segment-based models in the same reactor to account for simultaneous reactions in multiple phases. Note: You must specify the Valid Phases keyword for each reactor model referencing the kinetics to ensure the specified reacting phase exists. If the Reacting Phase option is set to Liquid phase 1 or Liquid phase 2 the model assumes two liquid phases exist. When the named phase is not present, the model prints a warning message and sets the reaction rates to zero. There are two options for handling phase collapse:
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Select the Use bulk liquid phase option to force the model to apply the specified reaction kinetics to the bulk phase when the named phase disappears. Select the Suppress warnings option to deactivate the warning messages associated with phase collapse.
These options are especially convenient when modeling simultaneous reactions in two liquid phases using two step-growth models. In this situation, one would typically select the Use bulk liquid option for one phase and not the other (to avoid double-counting reactions when one phase collapses).
Selecting the Reacting Site

The segment-based power-law reaction model can be used in conjunction with other Aspen Polymers reaction models to define side reactions. When combining the segment-based model with a Ziegler-Natta or ionic polymerization model, use the Reacting Site field on the Specs form to assign the reaction rates to a particular active site.
Note: The Segment Concentration Basis field lets you select the calculation method for the concentrations used within the reaction model. When you select Use composite segment concentration the segment mole fractions used to calculate the reaction rates are calculated from the following equation:
Fracs,i = Frac p * SFRAC( i )*
Mw p Mwsegavg
When you select Use segment concentration at specified site the following equation is applied:
Fracs ,i = Frac p * SSFRAC (i, j ) *
Mw p Mwseg avg
Where j refers the specified reacting site number. In both cases the attribute rates of change are mapped to the component attributes associated with the user-specified reacting site number (e.g., SSFLOW(i,j), SZMOM(i,j), etc.)
Building A Reaction Scheme

You can build a list of reactions on the Reactions sheet. To do this you must specify a reaction stoichiometry. The Data Browser window can be resized to better view the reaction listing. Use the following options:
Click New Edit Rate Constants To Add new reactions to the scheme Edit the current reaction indicated by the row selector Specify reaction rate constant parameters for the
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reactions
Click Hide/Reveal To Activate or de-activate a set of reactions. Inactive reactions are highlighted with a gray background. Permanently remove a reaction from the model
Delete
Adding or Editing Reactions

To add a new reaction to the scheme or to edit an existing reaction, click New or Edit to open the Edit Stoichiometry subform: Note that in the Reaction no. field, a unique number is assigned to the reaction being added. 1 Specify the Component ID and stoichiometric Coefficient for the reactants. Reactants must have a negative coefficient. 2 Specify the Component ID and stoichiometric Coefficient for the products. Products must have a positive coefficient. 3 Click or Click Close to return to the reaction summary. to check the Completion status
Specifying Reaction Rate Constants

The rate constants are summarized in a grid on the Rate Constants sheet: 1 In the k o field, enter the pre-exponential factor.
Note: Reaction rates are defined on a molar basis (moles per volume per time). The time units for the pre-exponential factors are specified directly on the Rate Constant form. By default, the concentration units are assumed to be in SI units (kmole/m3 or mole/L). You can change the concentration basis to other units using the Concentration Basis field of the Specs sheet. Alternately, you may apply a user basis subroutine. 2 3 4 In the Ea field, enter the activation energy. In the b field, enter the temperature exponent. In the Tref field, enter the reference temperature. If this field is left blank the reference temperature will default to the user-specified global reference temperature on the Specs form.
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5 6
If desired, specify a Catalyst Species and Catalyst Order. If desired, specify a user rate constant element number on the User Flag field (For details, see the User Rate-Constant Subroutine on page 140).
Note: Use the Catalyst Species field to associate a rate constant with a particular catalyst. If you leave this field blank (empty) the model drops the catalyst concentration term from the rate expression. Use the Catalyst Order field to specify the reaction order with respect to the catalyst (the model assumes first order by default).

There are two options for assigning rate constants to reactions. By default, the model assumes there is exactly one set of rate constants for each reaction (for example, rate constant set i is used for reaction i). Alternately, you may use the Assign User Rate Constant sheet to assign one or more sets of rate constants to each reaction. This feature is convenient in two situations: Models with a large number of user side reactions when the rate constants of the various reactions are equal or are related to each other algebraically. Reactions catalyzed by several catalysts simultaneously. You can enter several sets of rate constants for each reaction without reentering the reaction stoichiometry. You can assign a set of rate constants to multiple reactions, reducing the number of adjustable parameters in the model, which makes it easier to fit against data.
The assignment option is recommended for two reasons:
When several rate constants are assigned to a reaction the model calculates a net rate constant by summing all of the listed rate constants and multiplying the sum by a specified activity. To assign rate constants to reactions: 1 2 On the Assign User Rate Constants form, use the Activity field to specify the activity factor (default value is unity). In the Rate Constant Sets field, select from the list of pre-defined rate constant sets for each reaction. These numbers refer to the row numbers on the Rate Constants form.
Including a User Rate Constant Subroutine

Use the User Subroutines Rate Constants form to specify parameters for user rate constants calculations: 1 2 3 In subroutine Name, enter the name of the Fortran subroutine. Specify the size of vectors for Integer, Real and No. const. in Number of parameters. Specify the size of vectors of Integer and Real in Length of work arrays.
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Enter integer and real parameter values in Values for parameters columns.
Including a User Basis Subroutine

Use the User Subroutines Basis form to specify parameters for basis calculations: 1 2 3 In subroutine Name, enter the name of the Fortran subroutine. Specify the size of vectors for Integer and Real in the Number of parameters and Length of work arrays. Enter integer and real parameter values in Values for parameters columns.
References
Biesenberger, J. A., & Sebastian, D. H. (1983). Principles of Polymerization Engineering. New York: Wiley. Kroschwitz, J. (Ed.). (1990). Concise Encyclopedia of Polymer Science and Engineering. New York: Wiley. Odian, G. (1991). Principles of Polymerization, 3rd Ed. New York: Wiley. Rodriguez, F. (1989). Principles of Polymer Systems. New York: Hemisphere. Rudin, A. (1982). The Elements of Polymer Science and Engineering. New York: Academic Press Inc.
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14 Steady-State Flowsheeting
Aspen Polymers (formerly known as Aspen Polymers Plus) allows you to model polymerization processes in both steady-state and dynamic mode. In this chapter, flowsheeting capabilities for modeling processes in steady-state mode are described. Topics covered include: Polymer Manufacturing Flowsheets, 282 Modeling Polymer Process Flowsheets, 284 Steady-State Modeling Features, 285
Following this introduction, Aspen Polymers flowsheeting capabilities for modeling steady state processes are discussed in several sections. 15 Steady-State Unit Operation Models, 286 Plant Data Fitting, 331 User Models, 351 Application Tools, 366
Polymer Manufacturing Flowsheets

Polymer production processes are usually divided into the following major steps: Monomer synthesis and purification Polymerization Recovery/separation Polymer processing
The modeling issues of interest in each of these steps were discussed in Chapter 1, and are summarized in the following figure. The focus here is on the various unit operations required in these processing steps.
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Monomer Synthesis
During monomer synthesis and storage the engineer is concerned with purity since the presence of contaminants, such as water or dissolved gases, may
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adversely affect the subsequent polymerization stage by poisoning catalysts, depleting initiators, causing undesirable chain transfer or branching reactions which would cause less effective heat removal. Another concern is the prevention of monomer degradation through proper handling or the addition of stabilizers. Control of emissions, and waste disposal are also important factors.
Polymerization
The polymerization step is the most important step in terms of capital and operating costs. The desired outcome for this step is a polymer product with specified properties (e.g. molecular weight distribution, melt index, viscosity, crystallinity) for given operating conditions. The obstacles that must be overcome to reach this goal depend on the type of polymerization process. Polymerization processes may be batch, semi-batch, or continuous. In addition, they may be carried out in bulk, solution, suspension, or emulsion. Bulk continuous systems provide better temperature and molecular weight control at the expense of conversion; batch systems offer less control over molecular weight. In addition, they may result in a high viscosity product and require high temperatures and pressures. Solution systems also provide good temperature control but have associated with them the cost of solvent removal from the polymer. In summary, for the polymerization step, the mechanisms that take place during the reaction introduce changes in the reaction media which in turn make kinetics and conversion, residence time, agitation, and heat transfer the most important issues for the majority of process types.
Recovery / Separations
The recovery/separation step is the step where the desired polymer produced is further purified or isolated from by-products or residual reactants. In this step, monomers and solvents are separated and purified for recycle or resale. The important issues for this step are phase equilibrium, heat and mass transfer.
Polymer Processing
The last step, polymer processing, can also be considered a recovery step. In this step, the polymer slurry is turned into solid pellets or chips. Heat of vaporization is an important issue in this step (Grulke, 1994).
Modeling Polymer Process Flowsheets

The obvious requirement for the simulation of process flowsheets is the availability of unit operation models. Once these unit operation models are configured, they must be adjusted to match the actual process data. Finally,
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tools must be available to apply the fitted model to gain better process understanding and perform needed process studies. As a result of the application of the process models, engineers are able to achieve goals such as production rate optimization, waste minimization and compliance to environmental constraints. Yield increase and product purity are also important issues in the production of polymers.
Steady-State Modeling Features

Aspen Polymers has tools available for addressing the three polymer process modeling aspects.
Unit Operations Modeling Features

A comprehensive suite of unit operations for modeling polymer processes is available in Aspen Polymers. These include mixers, splitters, heaters, heat exchangers, single and multistage separation models, reactors, etc. For more information on available unit operation models, see 15 Steady-State Unit Operation Models on page 286.
Plant Data Fitting Features

Several tools are available for fitting process models to actual plant data. Property parameters may be adjusted to accurately represent separation and phase equilibrium behavior. This can be done through the Data Regression System (DRS). See the Aspen Plus User Guide for information about DRS. Another important aspect of fitting models to plant data has to do with the development of an accurate kinetic model within the polymerization reactors. The powerful plant data fitting feature (Data-Fit) can be used for fitting kinetic rate constant parameters. For more information, see Plant Data Fitting on page 331.
Process Model Application Tools

The tools available for applying polymer process models include capabilities for performing sensitivity and case studies, for performing optimizations, and for applying design specifications. For more information, see Application Tools on page 366.
References
Dotson, N. A, Galvn, R., Laurence, R. L., & Tirrell, M. (1996). Polymerization Process Modeling. New York: VCH Publishers. Grulke, E. A. (1994). Polymer Process Engineering. Englewood Cliffs, NJ: Prentice Hall.
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15 Steady-State Unit Operation Models
This section summarizes some typical usage of the Aspen Plus unit operation models to represent actual unit operations found in industrial polymerization processes. Topics covered include: Summary of Aspen Plus Unit Operation Models, 286 Distillation Models, 293 Reactor Models, 294 Mass-Balance Reactor Models, 294 Equilibrium Reactor Models, 296 Kinetic Reactor Models, 296 Treatment of Component Attributes in Unit Operation Models, 328
Summary of Aspen Plus Unit Operation Models

Aspen Plus includes a number of basic unit operation models that are typically used to represent one or more unit operations found in real processes. These models may be used alone to represent equipment such as pumps, heaters, valves, mixers, etc., or they may be used as generic tools to build models of more complex unit operations. The following table summarizes the available unit operation models:
Basic Unit Operation Models and Stream Manipulators Dupl Flash2 Flash3 FSplit Copies inlet stream to any number of outlet streams Performs two-phase (vapor-liquid) or three-phase (vapor-liquid-solid) phase equilibrium calculations Performs three-phase (vapor-liquid-liquid) phase equilibrium calculations Splits inlet stream to any number of outlet streams
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Basic Unit Operation Models and Stream Manipulators Heater Mixer Mult Pipe Pump Represents heaters, coolers, or mixers with known heat duty or specified temperature Adiabatic mixing of any number of feed streams Multiplies stream flow rates by a constant Calculates pressure drop through pipelines Represents pumps or liquid standpipes (pressure must be specified)
Distillation and Fractionation Models Sep Sep2 RadFrac MultiFrac Mass-balance model for separation operations with any number of product streams Mass-balance model for separation operations with two product streams Predictive multistage distillation model Predictive model for complex distillation operations with multiple columns
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Basic Unit Operation Models and Stream Manipulators Reactor Models RStoic RYield REquil RGibbs RCSTR RPlug RBatch Mass-balance model based on specified conversion for any number of stoichiometric reactions Mass-balance model based on specified product yield for any number of stoichiometric reactions Chemical equilibrium calculated from user-specified equilibrium constants Chemical equilibrium calculated by Gibbs free-energy minimization Predictive, reaction rate-based model to simulate continuous stirred tank reactors Predictive, reaction rate-based model to simulate continuous plug-flow reactors Predictive, reaction rate-based model to simulate batch and semi-batch stirred tank reactors
Dupl
The Dupl block copies one inlet stream to two or more outlet streams. By design, the mass flow rate and attribute rates out of this block will be greater than the flow rates into the block, violating mass and attribute conservation principles. Frequently, the Dupl block is used as a shortcut to reduce the simulation time required to model a process consisting of two or more parallel process lines. For example, consider the process shown here: Operating Conditions R1A Temperature, 250 C Pressure, torr 760 Volume, liter 2000 R1B 250 760 2000 R2A 260 1200 1500 R2B 260 1200 1500 R3A 270 1500 1000 R3B 265 1700 1200
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The second unit (R2A and R2B) in the A and B lines consist of identical unit operations operating at the same conditions. The third unit (R3A and R3B) operates differently in the two lines. Since the process lines are identical up to the third unit, there is no need to include both process lines in the model. Instead, we can consider one line, such as A and duplicate the outlet stream at the point where the process conditions diverge from each other. Another application of the Dupl model is to carry out simple case studies. For example, assume there are two proposed scenarios for carrying out a given reaction. In the first scenario, the reaction is carried out at a high temperature in a small reactor with a short residence time. In the second scenario, the reaction is carried out at a low temperature in a large reactor
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with high residence times. The two reactors can be placed in a single flow sheet model. The duplicator block is used to copy one feed stream to both reactors. The two cases can be compared by examining the stream summary.
Flash2
The Flash2 block carries out a phase-equilibrium calculation for a vapor-liquid split. The chemistry feature of this block can be used to extend the phase equilibrium to vapor-liquid-solid systems. The free-water option can be used to extend the phase equilibrium calculations to include a free water phase in addition to the organic liquid phase. The Flash2 model can be used to simulate simple flash drums with any number of feed streams. The model is also a good tool for representing spray condensers, single-stage distillations, knock-back condensers, decanters, and other types of equipment which effectively operate as one ideal stage. The Flash2 model assumes a perfect phase split, but an entrainment factor can be specified to account for liquid carryover in the vapor stream. The entrainment factor is specified by the user, it is not calculated by the model. If a correlation between the vapor flow rate and the entrainment rate is available, this correlation can be applied to the model using a Fortran block which reads the vapor flow rate calculated by the Flash block, calculates the entrainment rate, and writes the resulting prediction back to the Flash block. Note that this approach creates an information loop in the model which must be converged. The Flash2 block does not fractionate the polymer molecular weight distribution. Instead, the molecular weight distribution of the polymer in each product stream is assumed to be the same as the feed stream.
Flash3
The Flash3 block carries out phase-equilibrium calculations for a vapor-liquidliquid splits. The liquid phases may be organic-organic (including polymermonomer) or aqueous-organic. For aqueous-organic systems, the Flash3 model is more rigorous than the Flash2/free water approach described above. The key difference is that the Flash3 model considers dissolved organic compounds in the aqueous phase while the free water approach assumes a pure water phase. Generally, three-phase flashes are more difficult to converge than two-phase flashes. Three-phase flash failures may indicate bad binary interaction parameters between the components. The problem may also stem from bogus vapor pressures or heats of formation. In general, it is a good idea to study two-phase splits for the system in question before attempting to model a three-phase decanter or reactor. As with the two-phase flash, the three-phase flash is more stable if temperature and pressure are specified. Other options, such as duty and vapor fraction, are more difficult to converge. Temperature estimates may aid convergence in duty-specified reactors.
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The Flash3 block does not fractionate the polymer molecular weight distribution. Instead, the molecular weight distribution of the polymer in each product stream is assumed to be the same as the feed stream.
FSplit
The flow splitter block, FSplit, is used to represent valves or tanks with several outlets. The outlet flow rates can be specified on a mass, mole, or volume basis, or they can be specified as a fraction of the feed stream. In general, the fraction specifications are best because they are independent of the feed stream flow rates. This makes the model more flexible and reliable when using tools like SENSITIVITY or DESIGN-SPEC which might directly or indirectly manipulate the stream which is being split. The FSplit block can also be used with reactor models to account for back-mixing. The FSplit block assumes that the class 2 polymer attributes split according to mass mixing rules. For example, if the outlet stream is split 60:40, then the class 2 attributes, such as the segment flow rates, are also split 60:40. This approach is identical to assuming that the properties of the polymer in each outlet stream are the same as the properties of the polymer in the inlet stream.
Heater
Heater can be used to represent heaters, coolers, mixers, valves, or tanks. The Heater block allows you to specify the temperature or heat duty of the unit, but does not carry out rigorous heat exchange equations. Any number of feed streams can be specified for the Heater block. This block follows the same mixing rules as the Mixer model.
Mixer
The mixer block, Mixer, is used to mix two or more streams to form a single mixed outlet. The mixer block can be used to represent mixing tanks, static mixers, or simply the union of two pipes in a tee. The Mixer model assumes ideal, adiabatic mixing. The pressure of the mixer can be specified as an absolute value or as a drop relative to the lowest feed stream pressure. The Mixer model is functionally equal to the Heater model, except it only allows adiabatic mixing. For this reason, the Heater model may be a better choice for modeling mixing tanks. The Mixer block assumes that the class 2 polymer attributes are additive. For example if stream A and B are mixed to form stream C, and the zeroth moments of a polymer in stream A and B are 12 kmol/sec and 15 kmol/sec, then the polymer in the product stream has a zeroth moment of 12+15=27 kmol/sec.
Mult
The Mult block is used to multiply the flow rate of a stream. A common application of this block is to collapse two parallel process line models into a
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single line to avoid unnecessary duplicate calculations. For example, consider the process shown here:
In this process, the A and B lines consist of identical equipment with the same operating conditions. The Mult blocks HALF and TWICE are used to divide the feed stream flow rate by two after R1, representing the split between lines, and to double the product flow rate, representing the junction of the parallel lines into a single line at R3. This technique avoids the duplicate calculations for R2 A and B reactors, which should give the same results. This technique can save a great deal of simulation time.
Pump
The Pump block changes the pressure of a stream. This block can be used to represent an actual pump, or it can be used to represent pressure increases due to liquid head in standpipes.
Pipe
The Pipe model is used to calculate pressure drops in pipelines. The algorithms in this model are not designed for non-ideal fluids such as polymers, so the pipe model should be used with caution in polymer process models. A better option to calculate pressure drops in polymer pipelines is to use RPlug with a user-written pressure-drop subroutine.
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Sep
The Sep block is a generic separation model that allows component fractionation between two or more product streams. The products can be split according to flow rate or fractional specifications. The Sep block is commonly used to represent distillation columns or other separation equipment when the product stream purity is well known and the details of the separation process are not important. The Sep block does not fractionate the polymer molecular weight distribution. Instead, the molecular weight distribution of the polymer in each product stream is assumed to be the same as the feed stream.
Sep2
The Sep2 block is a generic separation model that allows component fractionation between two product streams. The products can be split according to flow rate or fractional specifications. The Sep2 block is commonly used to represent distillation columns or other separation equipment when the product stream purity is well known and the details of the separation process are not important. Compared to the Sep block, the Sep2 block has more flexible input options, but it only allows two outlet streams. The Sep2 block does not fractionate the polymer molecular weight distribution. Instead, the molecular weight distribution of the polymer in each product stream is assumed to be the same as the feed stream.
Distillation Models
Aspen Plus includes several shortcut distillation models (DISTL, SFRAC, etc.) which can be used to represent distillation columns. These blocks do not fractionate the polymer molecular weight distribution. Instead, the molecular weight distribution of the polymer in each product stream is assumed to be the same as the feed stream. The class-2 component attributes in each product stream are set proportional to the mass flow rate of the attributed component in each product stream. With the exception of the RadFrac model, the rigorous distillation models in Aspen Plus do not account for component attributes.
RadFrac
The RadFrac block is a rigorous multistage distillation model for two- and three-phase systems. RadFrac allows polymer feed streams at any tray, but it does not account for polymerization reaction kinetics. The molecular weight distribution and other polymer properties are not fractionated between the phases. Instead, the class-2 component attributes of the polymer components are split at each stage in proportion to the polymer component mass fractions. For example, if 90% of the polymer fed to a given tray goes to the liquid phase leaving that tray, then 90% of the zeroth moment and other class-2 attributes are assigned to the liquid phase on that tray.
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Reactor Models
Aspen Plus includes three classes of reactor models which include various levels of rigor and predictive capability. These classes are: (1) mass-balance models; (2) equilibrium models; and (3) rigorous kinetic models. The least predictive models, RStoic and RYield, calculate output flow rates based on user-specified input flow rates. If polymer components are involved in the reactions, then the component attributes associated with the polymer components must be specified for the product stream. These models calculate the mass and energy balances, but they do not perform rigorous kinetic calculations. The RGibbs and REquil models assume chemical and phase equilibrium. When polymer components are involved in the reactions, then the specified stoichiometry must be consistent with the reference molecular weight of the polymer component. In addition, the component attribute values for the polymer product must be specified by the user. Since the solution algorithms for these models do not consider the influence of the segmental composition of polymer components, they cannot be applied to copolymers. Rigorous kinetic models include RCSTR (continuous stirred tank reactor), RPlug (plug-flow reactor model), and RBatch (batch stirred tank reactor). Each of these models can consider one, two, or three reacting phases. These reactor models are with the reaction kinetic models to predict product stream composition and flow rates based on calculated reaction rates.
Mass-Balance Reactor Models

RStoic
The RStoic reactor model is used to represent reaction equipment when reaction kinetics are unknown or are unimportant, for example when reactions are very fast and proceed until the limiting reagent is exhausted. RStoic requires knowledge of the net reaction stoichiometry, and the extent of reaction or conversion of a key component. RStoic calculates the product stream flow rates based on user-specified reaction stoichiometries and extent of reaction or conversion of a key component. The reaction stoichiometry statements may include monomers, oligomers, or polymers, but may not include segments. Instead, the segment information (SFLOW or SFRAC) must be specified as component attributes in the COMP-ATTR sentence.
Reactions Involving Polymers

If polymer components are involved in any of the reactions, use the COMPATTR form to specify molecular weight values (MWN, MWW or PDI) or degree of polymerization (DPN, DPW or PDI ) for the polymer products. Specify the SFRAC attribute for homopolymers or copolymers with a known product polymer composition. For copolymers with product compositions which
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depend on the feed flow rates of monomers or polymer segments, specify dummy values for the SFLOW attribute and use a user-written Fortran block to predict product segment flow rates which are consistent with the calculated product flow rates. Write the calculated results into the product stream of the RStoic block. When some of the specified reactions involve polymers, the reaction stoichiometry must be written in a manner consistent with the reference molecular weight of the polymer component. Otherwise, the mass and energy balance calculations will not be consistent.
Simulating Polymer Phase Change

The RStoic model may be used with the substream feature to simulate phase changes in polymers. For example, the user may define a reaction to convert polymer from the liquid or amorphous state (in the MIXED substream) to crystalline polymer (in the CISOLID) substream. Conversely, melting can be simulated as a reaction that converts polymer in the CISOLID substream to polymer in the MIXED substream. When RStoic is used in this manner, the model automatically fractionates the component attributes between the product substreams. If the user does not specify the product component attributes, the model sets the values of the class-2 attributes in each substream proportional to the flow rate of the attributed component in the substream. In effect, the model assumes that there is no selectivity of properties between the product phases. The polymer in each product phase will have the same characteristics (segment composition, mole weight, etc) as the polymer in the feed stream.
RYield
The RYield reactor model is used to represent reaction equipment when reaction kinetics are unknown or are unimportant, and the reactions result in a product distribution with a known yield. RYield calculates the product stream flow rates based on user-specified reaction stoichiometries and yield distributions. The reaction stoichiometry statements may include monomers, oligomers, or polymers, but may not include segments. Instead, the segment information (SFLOW or SFRAC) must be specified as component attributes in the COMP-ATTR sentence. If polymer components are involved in any of the reactions, use the COMPATTR form to specify molecular weight values (MWN, MWW or PDI) or degree of polymerization (DPN, DPW or PDI ) for the polymer products. Specify the SFRAC attribute for homopolymers or copolymers with a known product polymer composition. For copolymers with product compositions which depend on the feed flow rates of monomers or polymer segments, specify dummy values for the SFLOW attribute and use a user-written Fortran block to predict product segment flow rates which are consistent with the calculated yield. Write the calculated results into the product stream of the RYield block. When some of the specified reactions involve polymers, the reaction stoichiometry must be written in a manner consistent with the reference
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molecular weight of the polymer component. Otherwise, the mass and energy balance calculations will not be consistent.
Equilibrium Reactor Models

REquil
The REquil model calculates product stream flow rates using equilibrium constants determined from Gibbs free energy. The equilibrium constants are based on user-specified reaction stoichiometries and yield distributions. The reaction stoichiometry statements may include monomers or oligomers, but may not include polymers or segments. If the feed stream includes polymer components, the attributes of the polymer components will be copied to the outlet stream.
RGibbs
The RGibbs model uses the Gibbs free energy minimization technique to determine the composition of each phase. This algorithm cannot predict the product of equilibrium polymerization reactions. Polymer phase equilibrium, however, can be predicted by the model. The RGibbs phase equilibrium algorithm assumes that the composition and molecular weight distribution of a polymer component is equal in each of the product phases. The class-2 component attributes of the polymer component are set in proportion to the mass flow of the polymer component in each of the product phases. The mass flow rates in the product phases are set by the Gibbs free energy minimization algorithm. To properly split component attributes among the RGibbs solution phases, use the "Phase equilibrium only" option. With this the model can predict multiple liquid phases such as three liquid phases. Surface tension effects are not considered. If you are certain that there will be no vapor phase, uncheck the "Include vapor phase" box to speed up calculations. Use one outlet stream for each predicted phase, to separate out the component attributes of that phase.
Kinetic Reactor Models

RCSTR
The RCSTR model represents a continuous stirred tank reactor with one or more phases. The model assumes perfect mixing within and between the phases, phase equilibrium, and isothermal, isobaric operation. Non-ideal mixing can be represented using a network of RCSTR models.
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Temperature
The CSTR model allows you to specify duty or temperature. If duty is specified, it is a good idea to provide a temperature estimate, T-EST, to improve the convergence of the model. The maximum temperature step size, T-STEP, may also influence the CSTR convergence. This parameter defaults to 50C, which results in substantial changes in reaction rates for reactions with typical activation energies. The temperature/duty iteration loop is referred to as the Energy Balance or EB-LOOP in the CSTR diagnostics.
Pressure
Pressure can be specified as an absolute value or as a pressure drop relative to the feed stream with the lowest pressure. In Aspen Plus, pressure drops are expressed as non-positive pressure specifications given in absolute pressure units.
Residence Time
The RCSTR model allows you to specify the effective hold-up in several different ways. For single-phase reactors, you can specify the total reactor volume or the total residence time. If the residence time is specified, then the estimated reactor volume should be specified to improve the residencetime/volume loop convergence (RT-LOOP). When two or more condensed phases are present, the RCSTR model assumes that each condensed phase has the same residence time. This no-slip assumption implies that the volume ratios of the condensed phases in the reactor are equal to the volume flow ratios of the condensed phases exiting the reactor. For multiphase reactors, specify the condensed phase volume or residence time in addition to the total reactor volume. Do not specify the total residence time, as this residence time is the average of the vapor and liquid phases. If the reacting phase residence time is specified, provide an estimate for the reacting phase volume. This will improve the reactor convergence. If residence time convergence is troublesome, try adjusting the volume step size.
Multiphase Reactors
The RCSTR model can be used to simulate single- or multiple-phase reactors. The valid-phases keyword is used to define the number and type of fluid phases present in the reactor. Amorphous solid polymers are treated as a liquid phase in Aspen Polymers (formerly known as Aspen Polymers Plus). Crystalline solids can be addressed by defining a CISOLID substream to track the flow rate of each inert crystalline solid. Dissolving or crystallizing solids can be captured using the Chemistry feature to define chemical equilibrium reactions between the solid and fluid phases. Note, however, that the current version of RCSTR does not allow components to appear in both kinetic reactions and in chemistry equilibrium reactions.
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The user may attach multiple outlet streams directly to the reactor model. The phase or phases flowing to these streams are identified on the streams form. When solids are present the solid phases will be added to the liquid outlet. In older releases of Aspen Plus, the RCSTR model had one process fluid outlet stream containing all of the phases exiting the reactor. This option is still supported in the current release for upward compatibility. As shown in the following figure, a Flash2 or Flash3 block can be used to split the mixed outlet stream of the reactor:
Reactors with Non-Ideal Mixing

Networks of RCSTR and RPlug blocks can be used to account for non-ideal mixing found in industrial reactors. For example, many industrial reactors are divided into zones by vertical or horizontal baffles. In addition, some reactors have poor mixing characteristics which result in dead zones. The figures that follow demonstrate ways to model some types of real reactors. Since many of the network models involve recycle loops, they may require substantially more simulation time than a single RCSTR block. In addition, the recycle loop convergence may make the model more difficult to converge. For these reasons, the simplest model that agrees with process data is always the best choice. This figure shows a two-phase CSTR with horizontal partitions:
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This figure shows a two-phase CSTR with vertical partitions:
This figure shows a two-phase CSTR with an external heat exchanger:
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This figure shows a two-phase CSTR with a dead-zone:
RCSTR Algorithm
The RCSTR model uses a trial-and-error technique to solve the mass and energy balance equations. Trial-and-error solutions are difficult to reach when the reaction rates are high, the variables cover several orders of magnitude, when many equations must be solved simultaneously, and when the variables are strongly related to each other. All of these conditions are found in polymerization reaction kinetics, making reactor convergence especially challenging. A good understanding of the design of the RCSTR model is required in order to troubleshoot convergence problems. Otherwise, it may be difficult to
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understand how to apply the various convergence parameters to improve the reliability of the model. The RCSTR algorithm consists of a series of nested loops, as shown in the following figure. The loops are solved from the inside to the outside using various trial-and-error solver algorithms. Some convergence parameters are associated with each of these loops.
The outer-most loop involves the volume and residence time of the CSTR. There are many options for specifying the characteristic volume of a multiphase CSTR. The following table shows the various calculations for volume and residence times in RCSTR:
Specifications: Total reactor volume (Vol)
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R =
VR F vj f j
j
Vj =
fv
k
f jv j
VR
j =
Vj Ff j v j
k k
Specifications: Total residence time (Res-time)
VR = R F v j f j **
j
Vj =
f v
k
f jv j
VR
j =
Vj Ff j v j
k k
Specifications: Total reactor volume (Vol), key phase volume (Ph-vol)
R =
VR Fvj f j
j
V j = specifed *
j =
Vj Ff j v j
Specifications: Total reactor volume (Vol), key phase volume fraction (Phvol-frac)
R =
VR Fvj f j
j
V j = rjVR
j =
Vj Ff j v j
Specifications: Total reactor volume (Vol), key phase residence time (Phres-time)
R =
VR F vj f j
j
V j = j Ff j v j **
j = specified
Specifications: Total residence time (Res-Time), key phase volume fraction (Ph-vol-frac)
VR = R F v j f j **
j
V j = rjVR
j =
Vj Ff j v j
VR = Total reactor volume; V j = Volume of phase j; v j = Molar volume of

phase j
r j = Volume fraction of phase j; R = Total residence time; j = Residence

time of phase j F = Total molar flow rate at reactor outlet; f j = Molar fraction of phase j * ** If more than one condensed phase is present, and the key phase is liquid, then the specified volume applies to the sum of the condensed phase volumes. This equation is solved by trial-and-error technique.
When residence time is specified instead of volume, the RCSTR model adjusts the volume to satisfy the residence time specification.
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Convergence problems in the residence time loop can be alleviated by providing initial volume estimates in the ESTIMATES form. If convergence problems persist, then the maximum volume step size (Max-Vstep) should be reduced. If the key phase residence time is specified, then the RCSTR model uses the specified reactor volume as an upper limit for the key phase volume.
EB LOOP
The second loop is the energy balance conservation equation (EB-LOOP). In this loop, the reactor temperature is adjusted to match the specified reactor duty. If the temperature is specified instead of the duty, this loop is bypassed. Since the reaction rates are very sensitive to temperature, large changes in the reactor temperature between energy-balance iterations (EB-ITER) may cause the mass-balance loop (MB-LOOP) to diverge. This problem can be solved by providing a good temperature estimate (T-EST) in the ESTIMATES form. If the problem persists, the maximum temperature step size (MaxTstep) should be reduced (the default, 50C, is rather large).
MB-LOOP
The next loop is the mass-balance loop (MB-LOOP). This loop uses a multivariable solver to converge the conservation equations for component mole flow and for the class two component attributes. Two solvers are available: Broyden and Newton. The Broyden algorithm tends to be relatively fast, but it may be unstable if the number of components and attributes is large and the reaction rates are high. The Newton algorithm tends to be slower, but more stable for many classes of problems. The Newton algorithm calculates the response of each variable to each other variable by perturbing the variables one at a time by a very small amount. These perturbation steps require lots of simulation time, which makes each iteration of the Newton algorithm slow. The number of mass-balance iterations (MB-Maxit) is defined on the convergence form. By default, the model allows 50 mass-balance iterations. This default is sufficient for the Newton algorithm, but is usually too small for the Broyden algorithm. For polymer reaction kinetics, the number of required mass-balance iterations may be as high as 500.
Using a Damping Factor

The stability of the Broyden algorithm can be adjusted using a damping factor (DAMP-FAC) defined on the Convergence form. Decreasing the damping factor decreases the step-size, resulting in a larger number of smaller, more stable steps. Thus, the maximum number of iterations should be increased as the damping factor is decreased. The damping factor is sensitive on a log scale. If the Broyden algorithm appears unstable, try setting the damping factor to 0.5, 0.3, 0.1, 0.05 etc. Optimum damping factors for polymerization kinetics typically fall between 0.1 and 0.001. The conservation equations have the form:
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accumulation = input output + Generation Ri Fi in Fi out j Gi , jV j = + For the component mole balance equations: Si Si Si Si Ri Aiin Aiout j G 'i , j V j = + For the class-2 component attributes equations: Si Si Si Si
Where:
Ri
= Residual value for equation i, kmol/sec
Fi in = Molar flow rate of component i into the reactor, kmol/sec Fi out = Molar flow rate of component i out of the reactor, kmol/sec Gi , j = Molar generation rate of component i in phase j, kmol/m3
sec
Aiin = Flow rate of attribute i into the reactor, kmol/sec or

particle/sec
Aiout = Flow rate of attribute i out of the reactor, kmol/sec or

particle/sec rate of attribute i in phase j, kmol/m3 sec or Gi, j = Generation 3 particle/m sec
Vj Si
= Volume of phase j in the reactor = Scaling factor for equation i
The mass-balance loop is converged when the maximum scaled residual of the conservation equations falls below the specified tolerance (MB-TOL):
R Maximum error = MAX i i < MB TOL Si

A secondary criteria is the root-mean-square scaled error, or RMS error:
RMS Error =
1 Ni
Ri i Si
The CSTR mass-balance algorithm iterates until the maximum error falls below the specified mass-balance tolerance or the maximum number of massbalance iterations is reached. If the maximum error criteria is reached, and the RMS error is decreasing by a factor of ten on each iteration, the CSTR model continues to iterate until the RMS error reaches the specified function tolerance (FUNC-TOL). This allows the model to reach very tight convergence tolerances when the convergence behavior is good. Scaling Factors The scaling factors play an important role in the convergence behavior of the model. If the scaling factors are large, and the variables are small, then the
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model will be loosely converged. If the scaling factors are small, and the variables are large, the convergence criteria will be unacceptably tight, and the model will not converge. There are two scaling options in the RCSTR model, as shown here:
Variable Type Enthalpy Component Mole Flows Component Scaling Estimated outlet stream enthalpy The larger of: Estimated component mole flow in outlet stream (or retention value if available) (Trace) x (Substream flow rate) Class 2 Attributes The larger of: Estimated attribute value in outlet stream (or retention value if available) (Attribute scaling factor from the TBS table) x (Estimated mole flow rate of the attributed component) (Trace) x (Total estimated outlet mole flow rate) x (Attribute scaling factor from the TBS table) (Attribute scaling factor from the TBS table) x (Substream flow rate) Substream Scaling
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Total estimated outlet stream mole flow rate
10 11
Note: If the estimated component flow or attribute value is zero or missing, the default scaling factor is applied.
By default, the component scaling option is used. With this option, the minimum scaling factors depend on the value of the TRACE parameter. The trace scaling factor is effectively a minimum mole fraction. For components with concentrations below the trace level, the scaling factors are set to a minimum value. The default scaling factors for component attributes are defined as constants in an Aspen Plus Table Building System (TBS) data file, COMPATTR.DAT. Although the default scaling factors are set to appropriate values for most classes of reaction kinetics, the optimal values for a particular type of kinetics may be different than the defaults. The default attribute scaling factors can be adjusted using the Components Attr-Scaling form. The scaling factors should make the scaled values as close to unity as possible. For this reason, the scale factors are set to the predicted values from previously converged passes through the RCSTR block. On the first pass through the flowsheet, the scaling factors will be set to the estimated value for the variable. Thus, component flow and component attribute estimates can be used to set the initial scale factors. The scaling factors for component attribute values are normalized with the total mole flow rate of the outlet stream. This keeps the scaling factors reasonable for models of any type of process, from bench scale to production scale units. The inner-most loop is the phase equilibrium loop, or flash equations. For this reason, it is essential to have accurate physical properties over the entire range of temperatures and pressures found in the process.
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The flash calculations start from retention values once the mass-balance error falls below the retention threshold (Ret-Thresh) specified in the convergence form. If the retention threshold is set very high, then the flash may fail, resulting in step-size cuts in the mass balance loop. If the retention threshold is reduced, the reactor calculations may require more time. For most simulation problems, setting the retention threshold to 1 10 results in fast flash convergence without errors. If errors occur, try using the default value,
10
1 105 . If errors persist, the most likely cause is a physical property problem.
Initialization Options The convergence behavior of the RCSTR model depends on how the model is initialized. There are three initialization options for the RCSTR model. Solver InitializationDo not use integration By default, the solver algorithm initializes itself using previously saved simulation results (retention). This saves time if the RCSTR block is inside a flowsheet recycle loop, where the block will be run several times in succession. It also saves time if the block is inside a sensitivity, optimization, design-spec, or data-fit study. Alternately, the user can force the model to restart from estimates every time by checking the restart flag on the block-options form. When retention is not available, or when the restart option is active, the model uses user-specified estimates to initialize the solver algorithm. Estimates can be provided for the reactor volume, phase volume, reactor temperature, component flow rates, and component attribute values. The component attribute estimates can be specified using class-2 or class-0 attribute values. If estimates are not provided, the model initializes the variables using the mixed feed stream (for example, the initial value of a component flow rate may be set to the total flow rate of that component in all feed streams to the reactor). Integration InitializationAlways use integration In the integration algorithm, the RCSTR is treated as a dynamic stirredtank reactor. The conservation equations are numerically integrated from an initial condition to the steady-state condition. The initial compositions in the reactor are set equal to those in the feed stream. If temperature is specified in the reactor, then the temperature profile during initialization can be ramped from the feed stream temperature to the specified temperature over the interval of several residence times. If duty is specified, then the duty can be ramped from adiabatic conditions to the specified duty. Ramping allows the reactor to cold-start for improved integration performance. The numerical integration carries forward until the residual terms (accumulation terms) drop below the specified mass-balance tolerance. At this point, the model enters the solver and continues until the model converges. Note that initial guesses for component flow rates and component attributes should not be provided when using the integration initialization option unless the reactor exhibits multiple steady-state solutions. In this case, initial estimates may be used to force the reactor towards a particular solution.
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Hybrid InitializationInitialize using integration The hybrid option takes advantage of the robust integration algorithm to initialize the reactor during the first pass. On subsequent passes, when a previously converged solution is available, the solution algorithm bypasses integration and jumps directly into the trial-and-error solver. Since the solver algorithm is much faster than the integration algorithm, the hybrid option offers improved performance for most problems.
Note: By default, the RCSTR model does not use integration (e.g., the trial and error solution algorithm starts directly from the user-specified initial guesses or from retention values). Optionally, the RCSTR model can be initialized using an integration approach or a hybrid approach that uses integration only when retention values are not available.
Troubleshooting Convergence Problems

To diagnose RCSTR convergence problems, set the terminal reporting level to 7 in the Block-Options form. This causes the RCSTR model to report the residence time iterations (RT-ITER), energy balance iterations (EB-ITER), and mass-balance iterations (MB-ITER) to the control panel. In addition, the model reports the maximum and root-mean-square errors for each loop. The Simulation diagnostic reporting level controls the diagnostic messages written to the history file (.HIS file). The maximum mass-balance error is reported at level 5. At level 6, the model reports the value of each reacting component flow rate and each component attribute. At level 7, the model reports values and rates of change (reaction rates) for components and attributes. At level 8, the model reports the values, rates, and residuals (error) of each solved variable. When troubleshooting convergence problems, simplify the problem by specifying temperature and volume instead of duty and residence time. If convergence problems persist, they must be related to the mass-balance loop, the reaction kinetic model or rate constants, or the underlying physical property calculations. Numerical integration is much more reliable than trial-and-error solvers. If the RCSTR mass-balance fails to converge, try running the same kinetics in an RPlug model. If possible, set the phase criteria liquid-only to eliminate physical property problems from the list of possible sources of error. If the RPlug model cannot converge with the specified kinetics, then the problem is almost certainly related to reaction kinetics. Possible sources of error in the reaction kinetics include: Errors in the molecular weight of a product or reactant Errors in the specified stoichiometry of a reaction (mass balance is violated) Unreasonable rate constants, especially activation energies (verify the units) Reactions with zeroth-order reactants which are not present Unreasonable concentrations of catalysts or inhibitors (put the feed stream in a flash block and verify that the concentrations in the reacting phase make sense).
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Errors in user-written Fortran subroutines.
If these sources of error are eliminated, and convergence problems persist, try simplifying the model by removing unnecessary side reactions or trace components from the model. Convergence is much easier if the number of equations is reduced, the speed of most convergence algorithms varies with the cube of the number of equations (the number of equations equals the number of reacting components plus the number of class-2 component attribute elements). Common Problems The following table summarizes solutions for some common problems encountered when using RCSTR:
Problem Initial flash failure Solution This is usually a physical property problem. Check the heat of formation (DHFORM) and ideal gas heat capacity parameters (CPIG) of the polymer and oligomer components. If supercritical components are present, consider treating them as Henrys law components Verify that the property method you are using is appropriate for the specified temperature and pressure Verify the specified phases are consistent with the specified temperature and pressure Verify the specified local and global flash tolerance Mass balance not converged in maximum number of iterations, but the error is decreasing from one iteration to the next. Mass balance not converged in maximum number of iterations, the maximum error is varying erratically between iterations, and the history file shows reasonable rates. Mass balance is not converging, the maximum error appears to oscillate between values or gets stuck and does not change. Mass balance not converged in maximum number of iterations, the maximum error is varying erratically between iterations, and the history file shows some reaction rates or attribute rates are much larger than others (or are erratic between iterations). Mass balance not converged in maximum number of iterations. Reaction rates are very high, as expected. Increase the maximum number of iterations. If more than 500 iterations are required for the Broyden algorithm, try adjusting the damping factor. Provide better initial guesses. If using the Broyden algorithm, try decreasing the damping factor by logarithmic steps (0.5, 0.3, 0.10.0001) until the problem converges. If the problem persists, try using the Newton algorithm. Provide better initial guesses. If using Newton algorithm, change the stabilization strategy from dogleg to line search. This works especially well for ionic and Ziegler-Natta kinetics. Check the specified rate constants in the kinetic models, especially activation energies. Verify the units of the activation energies. Verify flow rates of catalysts and initiators in the feed streams to the reactor. If using user kinetics, check your subroutine for errors. Verify the reactor volume (residence time). Try using the Newton algorithm with good initial guesses. If this fails, delete the initial guesses and try using the integration initialization.
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Problem Mass balance not converged in maximum number of iterations. Some reacting components (catalysts, initiators) are present in very small quantities. Energy balance loop does not converge, or mass-balance loop does not converge after the second energy balance loop iteration, or temperature step-size cutting (T-CUT) iterations appear in the diagnostic messages
Solution Try adjusting the trace parameter in order-ofmagnitude steps from the default ( 1 103 ) down to the concentration of the trace components. If this fails, reset trace to the default value and try integration initialization. Verify that the reactor converges with the temperature specified. If not, see items listed above, otherwise, provide a better temperature estimate (T-Est). If the problem persists, try adjusting the maximum temperature step-size (Max-Tstep) from 50C to 10C or even 5C. Verify that the reactor converges with the residence time specified. If not, see items listed above, otherwise, provide better volume estimates. If the problem persists, try adjusting the maximum volume step-size (Max-Vstep). Verify that the correct residence time is specified (condensed-phase residence time for two-phase reactors). Verify two phases exist if the reactor valid phases=vapor-liquid.
Residence time loop does not converge, or mass-balance loop does not converge after the second residence-time loop.
Flash failures appear during the mass-balance loop; the step-size cutting (X-CUT) diagnostic message appears.
This may be a physical property problem; it may reflect overly-tight flash tolerances; or the flash may be unstable when starting from retention values Loosen the local and global flash tolerance levels or increase the maximum number of flash iterations. Check the molecular weights of each reactant and product. Verify that reaction stoichiometry is correct.
Reactor converges but an error message says that the mass-balance does not close
RPlug
The RPlug model represents an ideal plug-flow reactor with one or more phases. The model assumes perfect radial mixing within and between the phases, phase equilibrium, and no-slip conditions between the phases (e.g., the phases all have the same residence time). Dead zones, back-mixing, and other types of non-ideal plug-flow behavior can be represented using RPlug in combination with other blocks. The RPlug model does not allow multiple feed streams. A mixer block must be used in conjunction with the RPlug block to account for multiple feed streams.
Temperature
RPlug allows many options for specifying the reactor duty or temperature:
Type Specifications Calculations
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Type ADIABATIC
Specifications None
Calculations Temperature is calculated at each axial position based on the enthalpy balance. Duty is integrated along the length of the reactor. The model reports the net duty across the reactor Duty is integrated along the length of the reactor. The temperature of the process stream is determined from the energy balance. The model reports the net duty across the reactor Duty is integrated along the length of the reactor and is reported as a net value. The temperature of the process and coolant streams are determined from the energy balance. Duty is integrated along the length of the reactor and is reported as a net value. The temperature of the process and coolant streams are determined from the energy balance. A design specification may be used to fit coolant feed temperature by adjusting coolant outlet temperature.
T-SPEC
Process stream temperature as a function of axial position (linear interpolation between the points) Heat media stream temperature (assumed constant along length of reactor). Overall heat-transfer coefficient. Area is determined from length, diameter , and number of tubes: A=NDL Heat media (coolant) stream temperature, composition, and flow rate. Overall heat-transfer coefficient. Area is determined from length, diameter, and number of tubes: A=NDL. Heat media (coolant) composition, flow rate and effluent temperature. Overall heat-transfer coefficient. Area is determined from length, diameter, and number of tubes: A=NDL.
T-COOL-SPEC Heat transfer routine optional
CO-COOL Coolant stream required Heat transfer routine optional COUNTER-COOL Coolant stream required Heat transfer routine optional
RPlug allows one process stream and one heat media stream. Reactions can occur only in the process stream. Heat transfer calculations are carried out between the process stream and the heat media stream. The heat media stream represents a coolant stream or a heating stream and the heat media stream flows co- or counter-current to the process stream. If a heat media stream is not specified, the model assumes a constant heat media temperature and solve for the process fluid temperature. The heat transfer rate or heat transfer coefficient value is calculated as a function of axial position, stream conditions, etc., by a user-written Fortran subroutine. This feature is used to develop rigorous models non-reactive heat exchangers.
Pressure
The pressure at the reactor entry can be specified as an absolute value or as a pressure drop relative to the feed stream. In Aspen Plus, pressure drops are expressed as non-positive pressure specifications given in absolute pressure units.
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The pressure drop across the reactor can be specified as a constant or calculated in a user-written Fortran subroutine. If the pressure drop is specified, the model assumes it is linear along the length of the reactor.
Residence Time
The RPlug model assumes a cylindrical geometry. The length, diameter, and number of tubes are specified. The process fluid is assumed to move through the tubes, and the coolant is assumed to flow on the outside of the tubes. The total reactor volume cannot be specified, but the aspect ratio (length/diameter) has no influence on the model predictions. Thus, the diameter can be set to 1.12838 units, which corresponds to an area of 1.0000 numerical value, thus the specified length is equal to the volume.
units2 . With this area, the length in units and volume in units3 have the same
The phase volumes cannot be specified independently. Instead, the RPlug model assumes that the phases move through the reactor without slipping past each other. This assumption is valid for situations where one phase is dispersed as droplets or bubbles in a second, continuous phase, such as dew in a vapor phase or small gas bubbles in a liquid phase. This assumption is not valid for multiphase plug flow reactors with controlled levels. With this assumption in place, the reactor residence time is equal to the residence time of each phase present in the reactor. The residence time is calculated by numerical integration. One work-around for the no-slip assumption is to write a user kinetic subroutine (or a step-growth mass-transfer routine) which calls the flash model directly. Then, specify the reactor as liquid-only and set the diameter to the hydraulic diameter of the reactor. Calculating Residence Time Equation to Calculate Residence Time in RPlug:
z=L
D 2 N
4
z=0
F
z
dz j f j,z v j,z
Where: D N Z = Reactor residence time = Tube diameter = Number of tubes = Axial position in reactor of length L = Total molar flow rate of process stream at axial location z = Molar fraction of phase j at axial location z = Molar volume of phase j at axial location z
Fz
f j ,z v j,z
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Multiphase Reactors
The RPlug models have one process fluid outlet stream that contains all of the phases exiting the reactor. As shown here, a flash block is used in conjunction with these blocks to split the liquid and vapor phases from the mixed outlet stream of the reactor:
In this application, it is good practice to specify PRES=0 (no pressure drop) and DUTY=0 in the flash block to ensure that the phase split occurs at conditions which are consistent with the reactor outlet. Another option is to specify temperature and to use a transfer block to copy the RPlug outlet stream temperature to the flash specifications.
Reactors with Non-Ideal Mixing

Back-mixed plug flow reactors can be modeled using a recycle stream or by breaking the reactor down into a series of RCSTR blocks. For example:
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The recycle-stream approach has the advantage of RPlugs profile-based input and output plotting, but it requires a flowsheet convergence loop that may be difficult to converge, especially if the circulation ratio is large. The series-ofCSTRs approach does not require recycle loop convergence, but the results are not as easily interpreted as the RPlug model. Reactors with dead zones can be represented using parallel plug-flow reactors, as shown here:
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The dead zone is represented by a plug-flow reactor with a large residence time. The active zone is represented as a plug-flow reactor with a shorter residence time. The volumes of the two reactors sum to the total volume of the real reactor. This approach assumes the dead zone reaches steady state. As always, the simplest model which agrees with process data is the best choice. The following figure shows a reactor with injection ports:
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To diagnose numerical problems in RPlug, set the terminal reporting level to 7 in the Block-Options form. With this setting, the RPlug block will report the normalized axial location, residence time (in seconds), pressure (in Pascal), temperature (in K), and vapor molar fraction at each converged step. The Simulation diagnostic reporting level controls the diagnostic messages written to the history file (.HIS file). The maximum mass-balance error is reported at level 5. At level 6, the model reports reacting component flow rates and component attribute values. At level 7, the model also reports the rates of change of these variables. At level 8, the model also reports initial scale factors for all variables. First, simplify the problem by specifying temperature instead of duty or heattransfer parameters (coolant temperature, U, or coolant stream). Specify the reactor as liquid-only. This will eliminate many possible sources of error and help focus the problem on kinetics and integration parameters. Scaling Factors RPlug uses Gears variable-step-size algorithm to numerically integrate the mass, energy, and attribute conservation equations along the axial dimension of the reactor. At each axial step, the conservation equations are solved by a trial-and-error technique. Like RCSTR, RPlug solves the conservation equations using scaling factors to normalize the variables. The values of these scaling factors can have a strong influence on the speed and reliability of the integration. The Gear integrator in Aspen Plus offers three error scaling options (ERRMETHOD in RPlug): Static scaling Dynamic scaling Hybrid scaling
The RPlug static and dynamic scaling options are summarized in the following table:
Variable Type Enthalpy Static Scaling Dynamic Scaling The larger of: Enthalpy at 2 Cutoff Component Mole Flows The scaling factor at z = 0 to 1.0 is set to 0.1 x total mass flow The scaling factor at z = z + z is set to the larger of: Component mass flow at z Cutoff Scaling factors are updated at each step
105 (SI units) x total mass flow
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Variable Type Class 2 Attributes
Static Scaling The scaling factor at z = 0 to 1.0 is set to the larger of: Attribute value in inlet stream (Attribute scaling factor from the TBS table) x (mole flow rate of the attributed component in the inlet) (Cutoff) x (total mole flow rate at the inlet) x (Attribute scaling factor from the TBS table) Scaling factors are held constant
Dynamic Scaling The scaling factor at z = z + z is set to the larger of: Attribute value at z Cutoff Scaling factors are updated at each step
The static scaling method uses a constant set of scaling factors throughout the reactor. The dynamic scaling method updates the scaling factors based on the previously converged step. The scaling factors are never set lower than the specified minimum scale factor. The static scaling method may result in faster integration for many types of problems, but there are potential numerical problems when using this method. Consider an irreversible reaction A B in a plug-flow reactor in which component B is not present in the feed. The scaling factor for component A will be set very large and the scaling factor for B will be set to the minimum scaling factor. This will result in relatively loose tolerance for the mass balance in A and tight tolerance for the mass balance in B. Further, as the reaction approaches completion the component B will have a large flow rate but a small scaling factor. This makes the conservation equation for B difficult to solve, which will result in small integration steps. Consider the same situation with dynamic scaling. The initial scaling factors are the same as the static case. With each new step, however, the scaling factors are updated to the variable values from the previous step. This keeps the scaled variables close to one throughout the integration. For example:
One pitfall of dynamic scaling, however, occurs when a variable value decreases and approaches zero. As the value and the scaling factor get
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progressively smaller, small absolute errors become large scaled errors. This also makes the solution difficult, and leads to small steps in the integrator. This problem can be controlled by setting the minimum scaling factor to a reasonable value. The default value,
-5
10-10 is much too small for most
problems. A value of 10 is reasonable for most situations, and will result in better model performance. The hybrid option uses static scaling for all variables except enthalpy, which is scaled dynamically. This option may be the best choice when the stream enthalpy is far from the default scale factor,
105 .
In general, the dynamic scaling method results in tighter convergence, but it requires more simulation time than the static scaling method. This does not apply to every case, however, and it may also depend on the solver algorithm. It is a good idea to experiment with these parameters to find the most reliable convergence strategy for each reactor in each model. When component attributes are present, as in polymerization kinetics, dynamic scaling is used by default. Solver Method At each step during the integration, the energy, mass, and attribute conservation equations are solved by trial-and-error. One of the two corrector algorithms, direct substitution or Newtons method, can be selected. The Newton algorithm perturbs each variable to determine the slope, resulting in a smaller number or larger steps compared to the Direct algorithm. Since the perturbation passes require some time, it is difficult to predict if the Newtons method or the Direct method is best for a given problem. In general, the Newtons method appears to give the best performance with polymerization kinetics, but it is a good idea to try using each algorithm with both dynamic and static scaling to determine the best combination of convergence parameters for a particular problem. The corrector tolerance is set as a ratio from the integration tolerance (CorrTol-Ratio). By default, the corrector tolerance is ten times tighter than the integration tolerance (the corrector tolerance ratio is 0.1). For some problems, especially those involving reactors with heat transfer calculations, the optimal corrector tolerance ratio may be higher than 0.1, but this ratio should not be set larger than 1.0. The flash tolerance should be tighter than the corrector tolerance. Otherwise, round-off errors in the flash calculations make the corrector tolerance difficult to achieve. The model always uses the smaller of the specified RPlug flash tolerance (in the convergence form) or the global flash tolerance. Other Integration Parameters By default, the initial step size in RPlug is set to one percent of the reactor length (Hinit=0.01). If the solver cannot converge the equations with this step size, it will cut the step size by a factor of ten. This process will repeat up to six times. If the solver still cannot converge, the reactor calculation fails with an error message solver cannot converge with minimum step size. Frequently, reaction rates or heat transfer rates are much faster near the entrance of the reactor than at the exit of a reactor due to step changes in temperature or pressure or due to the high concentrations of reactants at the inlet of the reactor. For these types of problems, the minimum step size may
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need to be reduced. For step-growth kinetics, try using an initial step size of especially if quasi-steady-state approximations are not applied.
1 10-4 . Smaller initial step-sizes may be required for addition kinetics,
The maximum number of integration steps defaults to 1000. For very stiff kinetics, e.g., kinetics with fast reaction rates involving trace components, the maximum number of steps may need to be increased, especially if the corrector is using direct substitution. If more than 5000 steps are required, try changing the corrector method, scaling method, or increase the cutoff level. RPlug stores many types of results at regular intervals (printing points). The number of intervals defaults to ten, but the number of print points can be increased to get smoother plots. Since the integration steps do not necessarily correspond to the print points, the model uses polynomial interpolation to determine the results for a print point based on the steps before and after this point. If the integration step sizes are very large, the interpolation algorithm may give strange results, such as sine waves. This problem can be fixed by reducing the maximum step size (Max-StepSize) to a value smaller than the increments between print points (this forces the model to use linear interpolation). By default, the maximum step size is much larger than the reactor length. When hybrid scaling is used, the tolerance of the energy balance is controlled by the energy balance tolerance ratio. Common Problems The following table summarizes common problems encountered when using the RPlug unit operation block:
Problem Solver cannot converge for initial step Solution Try reducing the initial step size by orders of magnitude from the default ( 10-2 ) to 10-8 . If the problem persists, try increasing the cutoff parameter from 10-10 to 10-5 . If the problem still persists, verify the values and units of the rate constants in the kinetic model. Verify the heat-transfer coefficient if applicable. Verify the temperature, composition, and flow rates of the feed streams. Check the history file diagnostics for unusually high reaction rates. This problem is usually related to infeasible reaction kinetics. If using a user kinetic routine, verify the code, otherwise, a zeroth-order reactant may be completely consumed. Check the history file diagnostics; look for the component flow rate or attribute element which has a value of zero and a negative rate of change. Try increasing the cutoff parameter from 10-10 to 10-5 . If the problem persists, try different combinations of scaling method and corrector method. As a last resort, try increasing the number of steps to 5000. If the problem still continues, search for errors in the kinetics; check the diagnostics for unreasonable reaction rates. Tighten the flash tolerance to a value below the corrector tolerance. Loosen the integration tolerance to 1 10-3 . Increase the corrector tolerance ratio to 0.2, 0.3, 0.5. If the problem continues, verify the kinetics and heat-transfer parameters. Check history diagnostics. This may be a physical property problem; it may reflect overly-tight flash tolerances, loosen the local and/or global flash tolerance levels or increase the maximum number of flash iterations.
Integration error: nonnegativity violation.
Integration error: maximum number of steps is reached
Integration error: corrector tolerance cannot be achieved Flash failures appear during the integration
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Reactor converges but an error message says that the mass-balance does not close
Check the molecular weights of each reactant and product. Verify that reaction stoichiometry is correct.
RBatch
RBatch is a rigorous model for batch and semi-batch reactors. Any number of continuous feed streams can be specified in addition to a batch charge stream. Optionally, a vapor vent may be considered. The RBatch model does not have a vent condenser option; Aspen Custom Modeler is required to rigorously model batch polymerization reactors with vent condensers or overhead columns. The RBatch model assumes feed and product accumulator holding tanks with continuous outlets. The accumulator concept provides a bridge between the continuous steady-state modeling environment in Aspen Plus and the inherently dynamic nature of batch reactors. The conversion between continuous streams and discreet charges and dynamic product accumulations is controlled by specified cycle times and continuous feed stream profiles specified in the reactor.
Temperature
RBatch allows many options for specifying the reactor duty or temperature, as summarized here:
Type T-SPEC Specifications Reactor temperature Calculations The model reports the temperature profile, and the instantaneous and cumulative duty profiles. The model reports the temperature profile, and the instantaneous and cumulative duty profiles.
T-PROFILE
Reactor temperature as a function of time. Linear interpolation is used to determine temperatures between specified points. Heat media stream temperature. Overall heat-transfer coefficient. Heat exchange surface area.
T-COOL-SPEC
The temperature of the reactor is determined from the energy balance at each time step. The model reports the temperature profile, and the instantaneous and cumulative duty profiles. The temperature of the reactor is determined from the energy balance at each time step. The model reports the temperature profile. The temperature of the reactor is determined from the energy balance at each time step. The model reports the temperature profile, and the instantaneous and cumulative duty profiles.
DUTY-SPEC
Instantaneous heat duty (assumed constant for entire cycle). Set the duty to zero to model an adiabatic reactor. Instantaneous heat duty as function of time. Linear interpolation is used to determine duty between specified points.
DUTY-PROFILE
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USER-DUTY
Heat transfer subroutine name
The user routine returns the instantaneous heat duty at each time step. The temperature of the reactor is determined from the energy. The model reports the temperature profile, and the instantaneous and cumulative duty profiles.
The temperature or duty can be specified as a time-varying function. Heat transfer can be accounted for by assuming a constant coolant temperature, heat transfer area, and heat transfer coefficient, or by writing a Fortran routine that returns the instantaneous duty at each time step. If the temperature or temperature profile is specified, RBatch assumes a temperature controller. If the reactor is single-phase, or if the reactor volume is specified, the model assumes perfect temperature control, otherwise, the model uses a proportional-integral-derivative (PID) controller equation to represent a temperature controller:
K Qt = M treactor K ( Tt Tt s ) + I
Where:
( Tt Tt s ) dt + KD
0
d ( Tt Tt s ) dt
Qt
= Instantaneous heat duty (J/sec)
M treactor = Mass in reactor at time t (kg) Tt Tt s

t K I D = Temperature in reactor at time t (K) = Temperature setpoint at time t (K) = Time (sec) = Proportional gain (J/kg-K) = Integral time (sec) = Derivative time (sec)
By default, the proportional gain is 2500 J/kg-K, which results in very tight control at the expense of excessive simulation time. The speed of the model can be increased by reducing the gain (try a value of 25 J/kg-K).
Pressure
If the reactor volume is not specified, the RBatch model assumes the reactor operates as a closed system with a variable volume. The pressure at the reactor is specified as constant value or as a time-varying profile. If the reactor volume is specified, and there is a vent stream attached to the reactor, the flow rate of the vent stream is determined from the specified pressure or pressure profile. The vent flow is positive when the calculated reactor pressure exceeds the specified reactor pressure.
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If the reactor volume is specified, there is no vent stream attached to the reactor, and the pressure profile is not specified, then the pressure is determined by the temperature and molar volume of the material inside the reactor. If the reactor volume is controlled, a pressure controller model can be linked to a continuous feed stream. The flow rate of the feed stream is adjusted to maintain a constant pressure inside the vessel. The continuous feed stream flow rate can decrease to zero, but it cannot reverse direction if the pressure exceeds the specified setpoint. The model uses a proportional-integralderivative (PID) controller equation to represent the pressure controller:
t d ( Pt Pt s ) K s s Ft = K ( Pt Pt ) + ( Pt Pt )dt + KD I dt 0
Where:
Ft
Pt
= Instantaneous flow rate (kmol/sec) = Pressure in reactor at time t (Pa)
Pt s = Pressure setpoint at time t (Pa)

t K I D = Time (sec) = Proportional gain (kmol/sec)/Pa = Integral time (sec) = Derivative time (sec)
Reactor Volume
If the reactor pressure is not specified, then RBatch will predict the reactor pressure based on a specified reactor volume. The pressure will be manipulated by a trial-and-error algorithm to satisfy the specified volume. If pressure and volume are both specified, you must either attach a vent stream to the reactor or attach a continuous make-up stream and pressure controller to the reactor.
Residence Time
The residence time of the reactor is controlled by user-specified stop criteria. You can specify whether RBatch should halt the reaction when the stop criterion variable is approached from above or below. If several stop criteria are specified, RBatch stops at the first stop criteria it reaches. In addition to stop criteria, you must specify a maximum time for the reactor. This prevents runaway calculations in the event that none of the stop criteria are feasible. The stop criteria may include one or more of the following: A maximum reaction time A maximum or minimum component mole or mass fraction in the reactor
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The amount of material (mass, moles, or volume) in the reactor or vent accumulator A maximum vent flow rate A maximum or minimum reactor temperature, pressure, or vapor fraction The value of a Prop-Set property (includes user Prop-Set properties or system properties such as viscosity, etc.)
Batch Operations
RBatch can represent batch or semi-batch reactors, depending on what streams are connected to it in the flowsheet. If a vent stream or time-varying continuous feed stream is connected to the RBatch block, then the model operates in semi-batch mode. The batch reactor model is interfaced into the Aspen Plus continuous flow, steady-state modeling environment through the concept of holding tanks, as shown here:
The holding tanks convert the: Continuous batch charge stream to a discreet batch charge Final vent accumulator inventory to a continuous, time-averaged vent stream Final reactor inventory to a continuous, time-averaged reactor product stream Continuous Batch Charge Time-Varying Continuous Feed Time-averaged Continuous Reactor Product Time-averaged Continuous Vent Product
Four types of streams are associated with RBatch:
Continuous Batch Charge: The material transferred to the reactor at the start of the cycle. The mass of the batch charge equals the flow rate of the batch charge stream, multiplied by the batch cycle time. The mass of the
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batch charge is equivalent to accumulating the batch charge stream in a holding tank during a reactor cycle. The contents of the batch charge holding tank are instantaneously transferred to the reactor at the start of each batch cycle. Time-Varying Continuous Feed: Streams that are fed to the reactor over some discreet interval during the batch cycle. The composition, temperature, pressure, component attribute values, and time-averaged flow rate of the stream are specified in the flowsheet. The flow rate of the continuous feed streams can be specified as a constant value, a time-varying profile, or manipulated by the pressure controller model to meet a time-varying pressure setpoint. Time-averaged Continuous Reactor Product: This stream is determined by dividing the final reactor inventory by the cycle time. This is analogous to instantaneously dumping the reactor contents to a large holding tank at the end of the cycle, and continuously draining the tank throughout each cycle. Time-averaged Continuous Vent Product: This stream is determined by dividing the final vent accumulator inventory by the cycle time. During the batch cycle, the time-varying continuous vent stream is accumulated in the vent accumulator. The model assumes the vent accumulator contents are instantly drained to a large holding tank at the end of the cycle, and the holding tank contents are continuously removed throughout the cycle.
Cycle Time
RBatch is a dynamic batch reactor model that is interfaced into the Aspen Plus continuous steady-state modeling environment. The interface requires converting batch charges and accumulator inventories into continuous stream flow rates. The cycle time is used to convert the batch charge flow rate into the initial reactor inventory. The cycle time is also used to convert the vent accumulator inventory and the reactor inventory into vent and reactor product streams. For example, assuming a reactor has a cycle time of two hours and that no continuous feed streams are specified, then: If the batch charge stream is set to 50 kg/hour, the initial reactor inventory is 100 kg. If at the end of the reaction cycle, the vent accumulator contains 30 kg of material, the time-averaged continuous vent stream flow rate is 15 kg/hr. The composition of the time-averaged vent stream will be the same as the final composition in the vent accumulator. The final reactor inventory will be 70 kg, and the time-averaged reactor product flow rate will be 35 kg/hr.
RBatch allows you to specify a feed time and down time instead of the cycle time. In this case, the time-averaged batch charge stream is divided by the feed time to calculate the initial batch inventory. The time-averaged product flow rates are based on the cycle time, which is calculated from the sum of the feed time, the down time, and the reaction time. This option is not recommended unless it is used to correct the mass balance for the influence of time-varying continuous feed streams.
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To diagnose numerical problems in RBatch, set the terminal reporting level to 7 in the Block-Options form. With this setting, RBatch reports the time (in seconds), pressure (in Pascal), temperature (in K), and vapor mole fraction at each converged integration step. The Simulation diagnostic reporting level controls the diagnostic messages written to the history file (.HIS file). The maximum mass-balance error is reported at level 5. At level 6, the model reports reacting component flow rates and component attribute values. At level 7, the model also reports the rates of change of these variables. At level 8, the model reports initial scale factors for all integrated variables. First, simplify the problem by specifying temperature instead of duty or heattransfer parameters (coolant temperature, U, or heat transfer subroutine). Specify the reactor as liquid-only. Specify the reactor pressure, but not the reactor volume. This will eliminate many possible sources of error and help focus the problem on kinetics and integration parameters. Once the model works with these settings, then revert the settings to duty, volume, and so on, making sure the model converges with each new specification. Scaling Factors RBatch uses Gears variable-step-size algorithm to numerically integrate the mass, energy, and attribute conservation equations for the reactor and the mass-balance equations for the vent condenser (if applicable). At each time step, the conservation equations are solved by a trial-and-error technique. RBatch solves the conservation equations using scaling factors to normalize the variables. The values of these scaling factors have a strong influence on the speed and reliability of the integration. The Gear integrator in Aspen Plus offers three error scaling options (ERRMETHOD):
Variable Type Enthalpy Component Mass Inventory In Reactor and Vent Accumulator
Static scaling Dynamic scaling Hybrid scaling

Dynamic Scaling Enthalpy at previous time step The scaling factor at t = t + t is set to the larger of: Component mass flow at t Cutoff Scaling factors are updated at each step The scaling factor at t = t + t is set to the larger of: Attribute inventory at time = t Cutoff Scaling factors are updated at each step
The RBatch static and dynamic scaling factors are summarized here:
Static Scaling
105 (SI units) x mass holdup

The scaling factor for each component inventory equation is set to: 0.1 * (mass of batch charge stream) Scaling factors are held constant The scaling factor of each component attribute is set to: (Attribute scaling factor from the TBS table) x (cycle time) (this is the attribute inventory at time = 0) Scaling factors are held constant
Class 2 Attribute Inventory in Reactor and Vent Accumulator
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The static scaling method uses a constant set of scaling factors throughout the reactor. The dynamic scaling method updates the scaling factors based on the previously converged step. The cutoff parameter is the minimum scaling factor used in dynamic scaling. The static scaling method may result in faster integration for many types of problems, but there are potential numerical problems when using this method. Consider an irreversible reaction A B in a plug-flow reactor in which component B is not present in the feed. The scaling factor for component A will be set very large and the scaling factor for B will be set to the minimum scaling factor. This will result in relatively loose tolerance for the mass balance in A and tight tolerance for the mass balance in B. Further, as the reaction approaches completion the component B has a large flow rate but a small scaling factor. This makes the conservation equation for B difficult to solve, which will result in small integration steps. The hybrid option uses static scaling for all variables except enthalpy, which is scaled dynamically. This option may be the best choice when the stream enthalpy is far from the default scale factor,
105 .
Consider the same situation with dynamic scaling. The initial scaling factors are the same as the static case. With each new step, however, the scaling factors are updated to the variable values from the previous step. This keeps the scaled variables close to unity throughout the integration. For example:
One pitfall of dynamic scaling, however, occurs when a variable value decreases and approaches zero. As the value and the scaling factor get progressively smaller, small absolute errors become large scaled errors. This also makes the solution difficult, and leads to small steps in the integrator. This problem can be controlled by setting the minimum scaling factor (cutoff in the convergence form) to a reasonable value. The default value,
-5
10-10 is
much too small for most problems. A value of 10 is reasonable for most situations, and results in better model performance. In general, the dynamic scaling method results in tighter convergence, but it requires more simulation time than the static scaling method. This does not
325
apply to every case, however, and it may also depend on the solver algorithm. It is a good idea to experiment with these parameters to find the most reliable convergence strategy for each reactor in each model. When component attributes are present, as in polymerization kinetics, dynamic scaling is used by default. Solver Method At each step during the integration, the energy, mass, and attribute conservation equations are solved by trial-and-error. Two corrector algorithms, direct substitution and Newtons method, can be selected. The Newton algorithm perturbs each variable to determine the slope, resulting in a smaller number or larger steps compared to the Direct algorithm. Since the perturbation passes require some time, it is difficult to predict if Newtons method or the Direct method is best for a given problem. In general, Newtons method appears to give the best performance with polymerization kinetics, but it is a good idea to try using each algorithm with both dynamic and static scaling to determine the best combination of convergence parameters for a particular problem. The corrector tolerance is set as a ratio from the integration tolerance (CorrTol-Ratio). By default, the corrector tolerance is ten times tighter than the integration tolerance (the corrector tolerance ratio is 0.1). For some problems, especially those involving reactors with heat transfer calculations, the optimal corrector tolerance ratio may be higher than 0.1, but this ratio should not be set larger than 1.0. The flash tolerance should be tighter than the corrector tolerance. Otherwise, round-off errors in the flash calculations make the corrector tolerance difficult to achieve. The model always uses the smaller of the specified RPlug flash tolerance (in the convergence form) or the global flash tolerance. Other Integration Parameters By default, the initial step size in RBatch is set to one tenth of a second (Hinit=0.1). If the solver cannot converge the equations with this step size, it will cut the step size by a factor of ten. This process will repeat up to six times. If the solver still cannot converge, the reactor fails with an error message solver cannot converge with minimum step size. Frequently, initial reaction rates or heat transfer rates are very fast, so the minimum step size may need to be reduced. For step-growth kinetics, the default value should be sufficient. Smaller initial step-sizes may be required for addition kinetics, especially if quasi-steady-state approximations are not applied. The maximum number of integration steps defaults to 1000. For very stiff kinetics, e.g., kinetics with fast reaction rates involving trace components, the maximum number of steps may need to be increased, especially if the corrector is using direct substitution. If more than 5000 steps are required, try changing the corrector method, scaling method, or increase the cutoff level. RBatch stores many types of results at regular intervals (printing points). The number of intervals depends on the reaction time. Since the integration steps do not necessarily correspond to the print points, the model uses polynomial interpolation to determine the results for a print point based on the steps before and after this point. If the integration step sizes are very large, the
326
interpolation algorithm may give strange results, such as sine waves. This problem can be fixed by reducing the maximum step size (Max-StepSize) to a value smaller than the increments between print points (this forces the model to use linear interpolation). By default, no maximum step size is enforced. RBatch has the option to stop exactly at print points and vent accumulator points instead of interpolating these points. When the exact option is set to yes, the model adjusts the integration steps to exactly match these points. This requires extra steps in the integrator that may slow down the model, but it results in more accurate simulations. When hybrid scaling is used, the tolerance of the energy balance is controlled by the energy balance tolerance ratio. Common Problems The following table summarizes common problems encountered when using RBatch:
Problem Solver cannot converge for initial step Solution Try reducing the initial step size by orders of magnitude from the default ( 10-1 ) to 10-8 . If the problem persists, try increasing the cutoff parameter from 10-10 to 10-5 . If the problem still persists, verify the values and units of the rate constants in the kinetic model. Verify the heat-transfer coefficient if applicable. Verify the temperature, composition, and flow rates of the feed streams. Check the history file diagnostics for unusually high reaction rates. This problem is usually related to infeasible reaction kinetics. If using a user kinetic routine, verify the code, otherwise, a zeroth-order reactant may be completely consumed. Check the history file diagnostics; look for the component flow rate or attribute element that has a value of zero and a negative rate of change. Try increasing the cutoff parameter from 10-10 to 10-5 . If the problem persists, try different combinations of scaling method and corrector method. As a last resort, try increasing the number of steps to 5000. If the problem still continues, search for errors in the kinetics; check the diagnostics for unreasonable reaction rates. Tighten the flash tolerance to a value below the corrector tolerance. Loosen the integration tolerance to 1 10-3 . Increase the corrector tolerance ratio to 0.2, 0.3, 0.5. If the problem continues, verify the kinetics and heat-transfer parameters. Check history diagnostics. This may be a physical property problem; it may reflect overly-tight flash tolerances, loosen the local and/or global flash tolerance levels or increase the maximum number of flash iterations. Set the cycle time instead of the feed time. Check the molecular weights of each reactant and product. Verify that reaction stoichiometry is correct.
Integration error: nonnegativity violation.
Integration error: maximum number of steps is reached
Integration error: corrector tolerance cannot be achieved Flash failures appear during the integration Reactor converges but an error message says that the mass-balance does not close
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Treatment of Component Attributes in Unit Operation Models

As described in previous chapters, Aspen Polymers includes two classes of component attributes. Class-2 attributes are primary conserved quantities and always have flow-type units (attribute value / unit time). These attributes include the zeroth moment of the polymer (polymer molecule flow rate), the segment flow rates, etc. Class-0 attributes are secondary quantities that can be derived from the primary quantities. The class-2 attributes follow flow-based mixing rules. In other words, if two streams are mixed, the product stream class-2 attributes are equal to the sum of the feed stream class-2 attributes. These mixing rules apply to each unit operation that allows multiple feeds of the same type (for example, multiple process fluid feeds). In the distillation models, these mixing rules apply on a tray-by-tray basis (e.g., if two or more feed streams enter the same tray). The blocks with more than one outlet (Flash2, Flash3, Sep, etc.) assume that the class 2 polymer attributes split according to mass mixing rules. For example, if 90% of the mass of the polymer flows to the liquid phase, then 90% of the polymer molecules also flow with the liquid phase. This approach is identical to assuming that the properties of the polymer, such as the molecular weight distribution, are not fractionated in any way; instead, the molecular weight distribution of each polymer component in each of the product phases is identical to that of the polymer in the feed stream. The following table summarizes the attribute handling for the different models:
Block Component Attribute Handling
Basic Unit Operation Models Dupl FSplit SSplit Sep Sep2 All attributes in feed stream are copied to each outlet stream. Class 2 attributes divide in proportion to flow rate of attributed component. Class 0 attributes are recalculated for each outlet stream. Equation to calculate outlet stream attributes:
Aout =
Fout A Fin in
F = Flow rate of attributed component (in = mixed feed, out = outlet) A = Class-2 component attribute value (in = mixed feed, out = outlet)
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Block Flash2 Flash3
Component Attribute Handling Class 2 attributes divide in proportion to flow rate of attributed component. Class 0 attributes are recalculated for each outlet stream. Polymer components are not fractionated by the phase equilibrium models used by these blocks. Equation to calculate outlet stream attributes:
Aout =
Fout A Fin in
F = Flow rate of attributed component (in = mixed feed, out = outlet) A = Class-2 component attribute value (in = mixed feed, out = outlet) When multiple substreams exist, the model distributes polymer attributes between substreams using the same rule. Mult Class 2 attributes multiply in proportion to flow rate of attributed component. Class 0 attributes are recalculated for each outlet stream. Equation to calculate outlet stream attributes:
Aout =
Fout A Fin in
F = Flow rate of attributed component (in = mixed feed, out = outlet) A = Class-2 component attribute value (in = mixed feed, out = outlet) Mixer Heater* Class 2 attributes are summed across all feed streams. Class 0 attributes are recalculated for the outlet stream. Equation to calculate outlet stream attributes:
Aout =
A
feeds
in
A = Class-2 component attribute value (in = mixed feed, out = outlet) Distillation Models Block RadFrac Component Attribute Handling Component attribute conservation equations are included in this model at the tray-bytray level. The class-2 attributes are calculated at each tray by the following equation:
Aout =
Fout A Fin in
F = Flow rate of attributed component (in = mixed feed to tray, out = outlet from tray) A = Class-2 component attribute value (in = mixed feed to tray, out = outlet from tray) The RadFrac model does not allow polymer reaction kinetics. MultiFrac / BatchFrac These unit operation blocks do not consider component attributes. Polymers must be converted to oligomer components if polymer fractionation is to be considered in these models.
Reactor Models RStoic RYield If user specified attributes in the COMP-ATTR form, they are used for the product stream. Otherwise, class 2 attributes divide in proportion to the flow rate of the attributed component. Class 0 attributes are recalculated for each outlet stream. Equation to calculate outlet stream attributes:
Aout =
Fout A Fin in
F = Flow rate of attributed component (in = mixed feed, out = outlet) A = Class-2 component attribute value (in = mixed feed, out = outlet)
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Block RGibbs REquil
Component Attribute Handling Polymer and heterogeneous catalyst components may not participate in the reactions in these blocks. The class 2 attributes divide in proportion to the flow rate of the attributed component. Class 0 attributes are recalculated for each outlet stream. Equation to calculate outlet stream attributes:
Aout =
Fout A Fin in
F = Flow rate of attributed component (in = mixed feed, out = outlet) A = Class-2 component attribute value (in = mixed feed, out = outlet) RCSTR RPlug RBatch When using Aspen Polymers reaction kinetics, these models calculate the class-2 component attributes using standard conservation equations. These models can be used with a user-written Fortran subroutine through the USER reaction option. If the user kinetics include component attributes, then the COMP-ATTR field in the user kinetics form of the reactor model must be set to yes. In RCSTR, initial guesses for the outlet attribute values can be specified in the COMP-ATTR form.
This also applies to any block that allows multiple feed streams and uses an implied mixer to calculate the net feed stream.
References
Chan, W.-M., Gloor, P. E., & Hamielec, A. E. (1993). A Kinetic Model for Olefin Polymerization in High-Pressure Autoclave Reactors. AIChE J., 39, No. 1. Chaudhari, R. V., & Shah, Y. T. (1986). Recent Advances in Slurry Reactors, Concepts and Design of Chemical Reactors. S.A. Whitaker & A. Cassano (Eds.). Switzerland: Gordon and Breach Science Publishers. Henderson, J. N., & Bouton, T. C. (Eds.). (1979). Polymerization Reactors and Processes. ACS Symp. Ser. Rodriguez, F. (1996). Principles of Polymer Systems. New York: Taylor & Francis. Trambouze, P., van Landeghem, H., & Wauquier, J. P. (1988). Chemical Reactors: Design/Engineering/Operation. Paris: Editions Technips. Walas, S. M. (1988). Chemical Process Equipment Selection and Design. Boston: Butterworths.
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16 Plant Data Fitting
Aspen Polymers (formerly known as Aspen Polymers Plus) simulation models can be fit to plant or laboratory data using Data-Fit. One or more sets of measured data are provided which may include model inputs or results. DataFit adjusts or estimates input parameters to find the best match between the model predictions and data. Data-Fit can also reconcile measured data against the model. Data-Fit minimizes the weighted sum of square errors, where each error is the difference between a reconciled input or calculated output and the data. In statistical terms, Data-Fit performs either ordinary least squares or maximum likelihood (errors-in-variables) estimation. Topics covered include: Data Fitting Applications, 331 Data Fitting For Polymer Models, 332 Steps for Using the Data Regression Tool, 336 (including troubleshooting tips)
This section emphasizes using the Data-Fit tool to fit process reaction kinetic parameters. A more general description of this tool is available in the Aspen Plus User Guide.
Data Fitting Applications

The data regression tool in Aspen Plus can be used to fit model parameters and reconcile process data. These applications may be carried out simultaneously. Parameter regression usually involves adjusting model parameters to improve the agreement between model predictions and process data. For example, reaction rate constants may be manipulated to match the measured polymer molecular weight and monomer conversion. Manipulated parameters may include reaction rate or equilibrium constants, physical property constants, or equipment specifications. Fitted parameters may include model predictions such as reactant conversion, product yield, by-product content, polymer component attributes, stream compositions or flow rates, or equipment heat duty, temperature, pressure, or holdup.
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Data reconciliation runs involve manipulating one or more sets of model inputs to match model predictions to process data. For example, the average feed rate of a makeup stream can be estimated based on the flow rate and composition of the feed and product streams. Manipulated data typically includes feed stream flow rates and compositions, equipment operating conditions, heat transfer coefficients, etc. The Data-Fit model can be used to reconcile input data and fit model parameters simultaneously. Simultaneous regression and reconciliation is typically used to fine-tune models which already match process data and trends relatively well.
Data Fitting For Polymer Models

Polymer process models frequently include non-ideal phase equilibrium, reaction kinetics, and complicated unit operations. Fitting these complex models against process and laboratory data is not a trivial task. A great deal of consideration must be given to the way this problem is approached. A detailed example describing how to fit a free-radical reaction kinetics problem is included in the Aspen Polymers Examples & Applications Case Book. A general procedure for fitting complex models is given below. Step 1. Process Data Review Collect data for the process. Sources of data include process information management system (PIMS), process design documents (PDDs), process flow diagrams (PFDs). Verify reproducibility / standard deviations of data by collecting multiple data sets for each case. Verify steady state by collecting data at regular intervals over several plant residence times. Verify data feasibility against mass and energy balance calculations. Step 2. Literature Search Collect information about the process. Sources of data include in-house lab data, databanks, trade journals, conference notes, polymer handbooks, online electronic databases, experimental designs, etc. Step 3. Preliminary Model Fitting Carry out physical property data regression, property constant parameter estimation runs. Test the parameters against all pertinent data from steps 1 and 2. To the extent possible, verify pure component physical properties and phase equilibrium predictions using Property Analysis tools. Step 4. Preliminary Model Development Develop a basic model of the process, ignoring details such as non-ideal mixing, heat transfer, etc. Specify temperature instead of duty, volume instead of residence time. Use parameters from steps 1-3. Step 5. Trend Analysis
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Use the sensitivity feature to evaluate trends between model outputs (conversion, polymer attributes, etc.) and model inputs (rate constants, operating conditions, etc.) Compare the predicted trends against available process or lab data. If the trends are not well matched, adjust specific model parameters to improve the predicted trend. Model fitting may be carried out using Sensitivity, Design-Specification, Data-Fit, or by trial and error. Step 6. Model Refinement Use the Data-Fit tool to carry out simultaneous parameter estimation and data reconciliation. Relax model assumptions, such as perfect mixing, as needed. Bring model up to the appropriate level of detail, fitting key parameters at each development step.
Data Collection and Verification

The first step in fitting a model is to collect and review data. Sources of data may include process information management system (PIMS), process design documents (PDDs), and process flow diagrams (PFDs), shift log sheets, and laboratory analysis reports. It is important to verify the reproducibility of the data by collecting several duplicate sets of each datum. Duplicate data are especially important for analytical measurements such as melt flow index and intrinsic viscosity. For continuous processes, it is a good idea to verify that the process operates under steady-state conditions by collecting data at regular intervals. The data should be collected at regular intervals over a period that exceeds the cumulative residence time of the key unit operations in the process. Verify data feasibility against mass and energy balance calculations. It is impossible to force a rigorous model to match data that violates the fundamental conservation equations. When possible, obtain calibration data for unit operating conditions, especially level calibration data for reactors and flow rate calibration data for flow meters. The method and assumptions used to calibrate these instruments must be taken into consideration for data reconciliation runs.
Literature Review
Before you regress process data, it is a good idea to collect information about the process. Sources of data include in-house lab data, databanks, trade journals, conference notes, polymer handbooks, on-line electronic databases, experimental designs, and so on. The open and in-house process literature may contain a wealth of information about key model parameters. Further, these sources may provide additional sources of fundamental data which can be used to independently evaluate model parameters. Simulation studies described in trade journals are an excellent source of insight and know-how related to model development. These studies frequently point out which assumptions are valid and which parameters are important. In addition, these papers may elucidate reaction mechanisms or physical phenomena that should be considered in a rigorous process model.
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The physical property and rate constant data reported in the open literature are never perfect, but they do serve as a good starting point for fitting the model.
Preliminary Parameter Fitting

It is important to determine as many of the model parameters as possible early in the model development process. Try to decouple the parameters from each other whenever possible. For example, find ways to establish phase equilibrium parameters independently of reaction equilibrium constants. Make simplifying assumptions to reduce the number of unknown parameters. Physical property parameters should be firmly established before fitting rate constants. When data are available, use the physical property data regression system (DRS) to fit the density, enthalpy, heat capacity, and vapor pressure of pure components. If phase equilibrium data are available, use DRS to regress phase equilibrium parameters. When property data are unavailable for a component, the property constant estimation system (PCES) can be used to estimate property parameters from molecular structure. These estimations, however, should be checked against process data. If data are available for components with similar structures, they can be used to estimate the properties of components that are not found in the databank. The following table lists some of the key physical property parameters in Aspen Polymers and describes how they influence polymerization kinetics:
Property Density Vapor pressure Parameters DNLRKT, DNLVK PLXANT, HENRY Influence on Polymerization Reaction Kinetics Concentration is proportional to density. Reaction kinetics depend on component concentrations. The vapor pressure controls phase equilibrium of volatile components in vapor-liquid systems. The phase equilibrium strongly influences concentrations, which controls kinetics. The component enthalpies influence the predicted heat duties and temperatures in the model.
Enthalpy
DHFORM, DHFVK, DHFVKM, DHSUB, DHCON, DHFMDP CPIG, CPL, CPLVK, CPCVK TMVK, TGVK
Heat capacity Transition temperature s Phase equilibrium Solubility (of a solid)
The heat capacity controls the influence of temperature on enthalpy. Phase transitions occur at the melting point and glass point. Predicted enthalpy, density, and heat capacity for polymer and oligomer components depend on the phase regime. In multiphase reactors the phase equilibrium determines the component concentrations in each phase, which influences the reaction rates.
K-SALT
The solubility parameter influences the concentration of partially soluble solids in the liquid phase. When catalysts, inhibitors, or monomers are fed as solids, this parameter
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controls their concentration, which in turn controls their reaction rate.
If reaction kinetic parameters are unavailable from in-house or open literature, it may be necessary to carry out experiments to determine the magnitude of the rate constants. Carry out the reactions under controlled conditions to isolate the influence of reaction kinetics from phase equilibrium, mass transfer, heat transfer, etc. For example, carry out the experiments in sealed tubes so the liquid phase concentrations are unaffected by phase equilibrium. Reaction experiments should be performed over a range of temperatures to allow determination of the activation energies.
Preliminary Model Development

Once the preliminary parameter fitting is complete, these parameters can be used to develop a preliminary model. At this stage of the model development process, it may be best to use simplified models for some of the ancillary operations that are not directly involved in the polymerization reactors. For example, it may be more convenient to represent distillation columns using the non-predictive Sep or Sep2 models instead of the RadFrac or MultiFrac rigorous distillation models. The most important rule for model development is to keep it simple. Model development must be carried out in several stages. Add detail to the model one step at a time. Each generation of the model can yield valuable insights into the process and can provide substantial benefit to the model developer. At each stage in the process, fit the appropriate model parameters and validate the model against all sources of available data. Verify the predicted trends against process data, operator experience, and engineering know-how. Over time, the level of detail and power of the model can be increased. During the preliminary development, use the most basic specifications possible. For example, in the RCSTR model specify temperature and reacting phase volume instead of duty and residence time. This approach will make the model run faster and will help to isolate the influence of property parameters from reaction kinetic parameters. Once the preliminary model is complete, it can be tested against process data. Major discrepancies between the data and the model predictions should be addressed during this step.
Trend Analysis
Use the preliminary model to carry out trend evaluation studies. The sensitivity feature can be used to examine the influence of process variables on the model predictions. Compare these trends against process data. If the predicted trends are not consistent, adjust the appropriate model parameters to improve the match. For example, if the predicted slope of the monomer conversion versus temperature curve is less than the measured slope, the activation energy of the polymerization reaction may be too low. Use the sensitivity tool to examine the influence of the model parameters on the model predictions and to determine which parameters are important in
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the model. Parametric studies can be carried out by manipulating two or more variables in a sensitivity study. It is good practice to include as many model predictions as possible in each sensitivity study. The simulation runs take the same amount of time regardless of the number of defined variables. It is much easier to understand the predicted trends when the sensitivity results are detailed. Once you know which parameters are critical to the model predictions, the data regression tool can be used to adjust these parameters to match specific trends. Keep the number of manipulated parameters to a minimum until all of the key parameters are established independently.
Model Refinement
The Data-Fit tool is the best choice for refining the fit between the model predictions and the process data, especially when several sets of data are available. Data-Fit can adjust several model parameters simultaneously, capturing subtle interactions among the parameters to get the best overall match between the process data and model predictions. When the model predictions cannot match the process data, the assumptions in the model may be too broad. Perhaps the process is limited by heat- or mass-transfer, or a reactor is not ideally mixed. Maybe there are additional side reactions that should be considered in the model, or the rate expression needs to be modified to account for some unusual aspect of reaction kinetics. These issues can be addressed during the model refinement process by adding new layers of detail to the model. Avoid adding more detail than necessary, however, because model fitting is a process of diminishing returns. Model refinement is an open-ended process. The model parameters can be tuned more accurately as more data become available from the process. Bad data points are easier to spot when there are more sets of data to compare. It is impossible for a simulation model to match process data perfectly. There are several sources of error that lead to differences between the model results and process data, including: Variations in process operating conditions due to disturbances, excursions from steady state, control system actions, etc. Imperfect calibration of flow meters, level controllers, etc. Analytical error in lab measurements Simplifications and assumptions in the model, such as ideal mixing, isothermal and isobaric vessels, phase equilibrium, etc. Errors in the model parameters.
Steps for Using the Data Regression Tool

There are three steps involved in using the data regression tool: Creating a base-case model
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Entering lab or process data and operating conditions into data sets Defining regression cases
Step 1. Creating a base-case model If the regression tool is being used to fit reaction kinetic parameters from lab batch reactor data, use the RBatch model with an appropriate reaction kinetic model. If the model parameters are being regressed from process data, develop a model of the process. Before setting up the data fit run, make sure the model predictions are reasonable and that the model is robust (converges without errors) over the ranges of each manipulated parameter. You can use sensitivity blocks to screen the model for accuracy and to test how robust the model is. The rate constants and property parameters entered into the base case model become the initial estimates for the regression. Step 2. Entering lab or process data and operating conditions into data sets There are two types of data sets used with the regression tool, Point-Data and Profile-Data:
Use Point-Data To specify Operating conditions for steady-state unit operation models. Feed streams for continuous processes or batch charge streams. Analytical data, measured flow rates, or composition data for product streams. Polymer or catalyst component attribute data for product streams. Profile-Data Operating profiles for batch reactors or plug-flow reactors, including temperature, pressure, and duty profiles, continuous feed stream profiles, etc. Time-series measured data for a batch reactor or data along the axial profile of a plug-flow reactor. Note: Component attribute profiles and user variable profiles are not available as profile data in this release of Aspen Polymers. To fit profile data for these types of variables, treat each data point in the profile as a point datum, and specify the coinciding stop-time (RBatch) or length (RPlug) of the reactor as another point datum in the same data set.
Step 3. Defining regression cases For each case, specify the parameters to be adjusted and the data sets to be fitted. Several regression cases can be included in the same simulation run. The cases are run sequentially; a prompt will appear on the screen that lets you specify which cases to include in the run, and the sequence order of the cases. Each successive case uses the fitted parameters and reconciled data from the previous case. If the data regression is run again, the previously fit values are used as initial estimates unless the simulation is reinitialized.
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Identifying Flowsheet Variables

You must identify each measured and manipulated variable considered in the regression. Most types of variables, such as stream flow rates, equipment operating conditions, and component attribute values can be accessed directly using the variable accessing system. In the data regression and data set forms, you cannot access vector data, such as the stream vector and component attribute vector. You must access each stream variable or component attribute element as a separate scalar variable. When specifying feed stream data, avoid using mole, mass, or volume fractions as variables in the data set. If the composition of the feed stream changes from one validation case to another, specify the flow rates of the components in the stream. If the composition is constant but the flow rate changes, specify the composition and base-case flow rate in the model, and specify the total stream flow rate as a point-data variable. This avoids problems with normalizing fractions and reduces the number of variables handled by the data-fit algorithm. Some unit operation models have both input and results variables for the same operating condition. For example, in the RCSTR model you can access the specified heat duty (DUTY), or the calculated reactor duty (QCALC). If a variable is an INPUT variable in the regression it must be specified in the unit operation model. For example, if the reactor duty is a manipulated INPUT variable in the regression, it must be specified as an input variable (DUTY), and the reactor duty must be specified in the reactor model. If the reactor duty is a measured RESULTS variable, it must be specified as a results variable (QCALC), and is usually not specified in the model (the temperature is specified instead). The following table provides a cross-reference of commonly-used INPUT and RESULTS variables for key specifications related to several unit operation models:
Model RBatch RCSTR with one phase Operating Condition Cumulative reactor duty Duty Pressure Temperature Reactor volume Reactor residence time RCSTR with multiple phases Reacting phase volume Input Variable DUTY DUTY PRES* TEMP VOL RES-TIME REACT-VOL Results Variable QCALC QCALC use outlet stream pressure TCALC VOL-CALC RT-CALC VOLL-CALC for liquid volume VOLV-CALC for vapor volume VOLLS-CALC for total liquid+solid volume Reacting phase residence time PH-RES-TIME VOLL-CALC for liquid residence time RTV-CALC for vapor residence time RTLS-CALC for liquid or solid residence time
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Model RPlug
Operating Condition Duty Pressure (process fluid) Temperature (process fluid) Residence time (process fluid)
Input Variable DUTY PRES* (feed) SPEC-TEMP** RES-TIME
Results Variable QCALC REAC-PRES** REAC-TEMP** RT-CALC (entire reactor) REAC-RESTIM** (residence time at a profile point)
Flash2 and Flash3 RadFrac and MultiFrac
Duty Pressure Temperature Condenser duty Reboiler duty Reflux ratio Boilup ratio Stage temperature Stage pressure Design specification setpoint
DUTY PRES* TEMP Q1 QN basis-RR*** basis-BR*** STAGE-TEMP STAGE-PRES VALUE
QCALC use outlet stream pressure use outlet stream temperature COND-DUTY REB-DUTY RR BR TEMP PRES various - it depends on the specification
* ** ***
The pressure variable is treated as a pressure drop if the specified value is nonpositive. Specify location (RPlug) or stage number (RadFrac / MulitFrac) Basis can be MOLE, MASS, or STDVOL - the variable specified in the data set must match the variable specified in the column .
Some measured data, such as polymer melt index and intrinsic viscosity, are not predicted by the standard property sets in Aspen Polymers. The best way to include these properties in a data regression is to write a user Prop-Set property subroutine. Each user property can be linked to a property set. Property sets can be accessed as stream-property variables.
Manipulating Variables Indirectly

In-line Fortran blocks can be used to enforce assumptions in the model or to manipulate variables indirectly. Using these techniques to reduce the number of manipulated variables can greatly enhance the speed and reliability of the regression. Example 1: Using Fortran Blocks to Enforce Modeling Assumptions Suppose: Your process involves a catalyst and an initiator. The key variables involved in the regression cases are the process operating conditions and the monomer feed rate. The catalyst and initiator flow rates are always proportional to the monomer feed rate.
Create a Fortran block and define the monomer, catalyst, and initiator flow rates as flowsheet variables. Specify the monomer flow rate as a read
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variables and the catalyst and initiator flow rates as write variables as shown below: FORTRAN SETCAT DEFINE FLOMON MASS-FLOW STREAM=FEED COMPONENT=MONOMER DEFINE FLOINI MASS-FLOW STREAM=ADDITIVE COMPONENT=PEROXIDE DEFINE FLOCAT MASS-FLOW STREAM=CATALYST COMPONENT=METAL READ-VARS FLOMON WRITE-VARS FLOINI FLOCAT C Specify the base-case flow rates in kg/hr below F BCMON = 1200.0 F BCCAT = 20.0 F BCINI = 5.0 C Calculate the flow rates of initiator and catalyst F FLOINI = FLOMON * BCINI / BCMON F FLOCAT = FLOMON * BCCAT / BCMON Define the monomer flow rate as a variable in a point-data set. During the data regression run, the regression model will write the monomer flow rate for each case. The Fortran block will be executed each time the regression block manipulates the monomer flow rate. The Fortran block will read the new monomer flow rate, calculate the initiator and catalyst flow rates, and write their values. Using this technique to indirectly manipulate the additive flow rates reduces the number of variables in the regression, making the regression faster and more reliable. The cost of this approach is that the indirectly manipulated variables (catalyst and initiator flow rates) cannot be reconciled (the model has no information regarding the standard deviations of these variables). Example 2: Using Parameters and Fortran Blocks to Indirectly Manipulate Process Variables Suppose: Your polymerization process uses two monomers. The key variables involved in the regression cases are the monomer ratio and the polymer production rate. You want to vary these parameters in the data regression.
In the base-case model, define the monomer ratio and production rate as parameter variables in a Fortran block. Specify the base-case monomer ratio and production rate in the same Fortran block. Specify this block to sequence first, as shown below: FORTRAN INITIAL DEFINE RATIO PARAMETER 1 DEFINE PRODRT PARAMETER 2 SEQUENCE FIRST C specify monomer mole ratio F RATIO = 1.05 C specify polymer production rate, kg/hr F PRODRT = 2000.0 Create a second Fortran block. Define the monomer flow rates as flowsheet variables. Access the monomer mole ratio and production rate parameters. Specify the parameter variables as read variables and the monomer flow rate variables as write variables. After solving the algebra, the Fortran block can be defined as shown below:
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FORTRAN ADJUST DEFINE RATIO PARAMETER 1 DEFINE PRODRT PARAMETER 2 DEFINE FLOM1 MOLE-FLOW STREAM=FEED COMPONENT=MONO-1 DEFINE FLOM2 MOLE-FLOW STREAM=FEED COMPONENT=MONO-2 READ-VARS RATIO PRODRT WRITE-VARS RATEM1 RATEM2 C w = mole weight of each monomer F WM1 = 150.23 F WM2 = 230.30 C calculate average molecular weight of monomers F RATINV = 1.0 / RATIO F WMAVG = ( 1.0 + RATINV ) * ( WM1 + WM2*RATINV ) C calculate monomer flow rates in kmol/hr F FLONET = PRODRT / WMAVG F FLOM1 = FLONET / ( 1.0 + RATINV ) F FLOM2 = FLONET - RATEM1 The production rate and mole ratio parameters can be accessed as parameter variables in the data-set. The standard deviation for the production rate and mole ratio variables may be specified; the units of the standard deviations are the same as the units of the parameters.
Entering Point Data

There are two types of point data: input variables and result variables. Input variables include feed stream flow rates, equipment operating conditions, and other parameters that are inputs to the simulation model. Result variables include product stream flow rates or composition, polymer or catalyst component attributes, stream properties, or any other simulation calculation that can be compared to measured process data. If some results data are missing from one or more sets of data, they can be left blank on the input forms. The model will estimate the values of these results and tabulate them after the regression run. Unknown input data may also be estimated. Leave the input field blank and specify large standard deviations (for example, 50%) for each missing datum. Supply a realistic initial guess and make sure the standard deviation results in reasonable bounds for each missing variable. The upper and lower bounds for reconciled unknown input variables are determined from the specified standard deviation and the bound factor, which defaults to ten: Lower bound = Measured value - (Bound Factor)*(Standard Deviation) Upper bound = Measured value + (Bound Factor)*(Standard Deviation)
Make sure these limits are reasonable. In particular, the limits for a stream flow rate must not allow the stream flow rate to become zero or negative.
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Entering Profile Data

The plug-flow reactor model (RPlug) predicts results at various points along its length axis. The batch reactor model (RBatch) predicts results at various points in time during the batch cycle. You can define profile data sets to specify the operating profiles as input data, or to fit the model to measured results data. To do this, specify the time and value for each datum in the profile. You can specify standard deviations for results variables. Data reconciliation is not allowed for input profile data. The following table lists the profile data sets that are currently available for these reactor models. Other types of profiles, including component attribute, user variable, and user Prop-Set property profiles are planned for a future releases of Aspen Polymers.
Model RBatch, RPlug Variable Type Input Description Temperature of process fluid Pressure of process fluid Instantaneous reactor duty Results Partial pressure of a component Molar concentration of a component in the liquid phase Molar concentration of a component in the vapor phase Mole fraction of a component in the liquid phase Molar fraction of a component in the vapor phase Mass concentration of a component in the liquid phase Mass concentration of a component in a slurry phase Mass fraction of a component in the liquid phase Cumulative reactor heat duty Instantaneous vent mole flow rate Instantaneous vent volume flow rate RBatch Input Feed stream component flow rates Profile Name TEMPERATURE PRESSURE DUTY PARTIAL-PRES MOLECONC-L MOLECONC-V MOLEFRAC-L MOLEFRAC-V MASSCONC-L MASSCONC-LS MASSFRAC-L CUM-DUTY VENT-MOLFLOW VENT-VOLFLOW not applicable
If you are fitting component attribute or user Prop-Set property profiles, you must treat the measured variables as point data for the reactor outlet stream. Use the reactor length or stop-time as an additional point data. Each profile point must be treated as a separate data case in the data set. If some results data are missing from one or more sets of profile data, they can be left blank on the input forms. The model will estimate the values of these results and tabulate them after the regression run.
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Entering Standard Deviations

Standard deviations may be specified for input and result variables. The standard deviation is the level of uncertainty in the measurement. You can enter the value as an absolute or percent error (append a percentage sign, %, to the value). Statistically determined standard deviations may be available from an on-line process information management system (PIMS), from lab databases, or from other information resources. When the standard deviations are not available, you can enter your best estimate of the expected error based on your experience or the specifications of the instrument. The objective function of the data regression is to minimize the sum of weighted square errors. For results variables, each error is defined as the difference between the reconciled or specified datum and the value calculated by the model. Each error is scaled against the square of the standard deviation:
Objective function =
Measurement i Prediction i (Standard deviation) 2 i
If the specified standard deviation of a variable is too small, the model overemphasizes the importance of the variable during the fitting process. This may cause the model to make unreasonable adjustments in some parameters to force good fits to variables with small standard deviations. You must be careful to consider both the precision and accuracy of each variable. For example, a variable may have a low standard deviation because it is very precise (it reproduces well in successive trials), but the measurement may be inaccurate (it may not reflect the true value of the measured parameter). Consider the case where a level controller may show little deviation in the liquid volume in a reactor, but the calibration of the level transducer may not be accurate to within ten percent of the real liquid volume. In this case, the standard deviation of the specified liquid volume should be large enough to reflect the accuracy of the volume, not the deviation of the liquid level. If standard deviations are specified for input variables, the model reconciles these variables. If you do not specify the standard deviation of an input variable, the model assumes the specified values are exact. Reconciling input variables accounts for measurement errors in the operating conditions and can lead to better models, but it can substantially increase how long the run takes to complete. Standard deviations must be specified for each of the result variables. Specify reasonable standard deviations to keep the model from forcing a match by making wild adjustments to the parameters. The specified standard deviations are probably too small (or the data quality is poor) if several of the parameters reach their upper or lower bounds.
Defining Data Regression Cases

You can fit any number of data sets in the same regression case. Point-Data and Profile-Data may both be included. Each regression case must involve at least one estimated parameter and at least one reconciled input variable.
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There are no upper limits to the number of estimated parameters and reconciled inputs, however the required simulation time is very sensitive to the number of variables included in each regression case. Each input variable with a non-zero standard deviation is reconciled (adjusted). The reconciled inputs are tabulated in the regression results. Each estimated parameter must be defined in the base case, or have a default value (such as a physical property parameter). The specified values for the base case run are used as the initial guesses for the regression. If the basecase value lies outside the specified bounds, the boundary condition closest to the base case value is used.
Sequencing Data Regression Cases

For data fit problems, Aspen Plus will: Run the base-case simulation Execute the data regression Replace the base-case parameter values with the estimated parameter values and rerun the base-case simulation
If Case-Study or Sensitivity blocks are present, Aspen Plus runs them after the regression is complete. The estimated parameter values are used to calculate the results for these blocks. Flowsheet convergence loops and Design-Specification loops are used in the preliminary and final base-case simulations and they are sequenced inside the data regression loop. The sequencing of Fortran blocks and Transfer blocks depends on which variables are accessed. If more than one regression is included in a simulation, the regressions can be affected sequentially. Each successive regression uses the estimated parameters from the previous regression. Regression blocks can be manually sequenced if the automatic sequence does not meet the needs of a particular run, however automatic sequencing is usually the best choice.
Interpreting Data Regression Results

The key results of the data regression tool are: The Chi-square statistic and critical Chi-square value for the fit. Estimates and standard deviations for each estimated parameter. A table of the measured values, estimated values, and normalized residuals for each data set.
The Chi-square value is an indicator of the quality of the fit. A model is considered well fit if the Chi-square value falls below the critical Chi-square value. The reliability of different fits or different modeling approaches can be tested by comparing the Chi-square values of the fits. For example, suppose a reactor is thought to have non-ideal mixing. This assumption can be evaluated by developing two models, one which assumes ideal mixing (one CSTR stage) and one which assumes non-ideal mixing (a series of CSTR stages). The two models can be fit against the same data using the same
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parameters. The model with the lower Chi-square statistic represents the data more accurately, and can be considered the most realistic. Ideally, the standard deviations of the estimated parameters are small, and the confidence interval of each parameter is narrow. In practice, however, the standard deviation of the parameters may be relatively large. This does not necessarily indicate a poor fit. For example, if the activation energy and preexponential factor for a reaction are both included as estimated parameters in the data regression, then the standard deviation of the estimated preexponential factor will be large. In this example, small differences in one parameter (the activation energy) requires large differences in another parameter (the pre-exponential factor) to keep the model predictions relatively constant. The residual values are indicative of the difference between the measured data and model predictions. For fitted data, the residuals are defined as:
Residual i = (Measured value i - Predicted value i )2 / (Standard deviation i )

For reconciled data, the residuals are defined as:
Residual i = (Measured valuei - Estimated valuei )2 / (Standard deviation i )

Review the residual values to verify they are sensible. Large residual values may indicate a major problem with the model or data, or may reflect an unreasonably tight standard deviation. Never specify extremely tight standard deviations. This causes the data regression algorithm to waste time attempting to obtain tight fits on some variables. If some data are considered extremely accurate, they should be assigned standard deviations of zero. The regression results may be plotted against the initial estimates and measured data. Plots of this type include a 45 dotted line that indicates a perfect fit, e.g., each prediction is exactly equal to the measured data. Points which fall far from this line are the least well fit. Verify these outliers to make sure the data is correctly entered into the model and that the units of measurement are consistent.

If the data regression tool fails to converge, check the objective function. A large objective function value indicates a poor fit between the model predictions and measured data. If the objective function is large, review the residual values for each type of measured data. Large residual values may indicate a very basic error in the data entry. For example, the data may be entered in the wrong units or there may be typing errors in the specified values. Always review the model thoroughly to eliminate these types of problems before adjusting convergence parameters or making other major changes to the regression. Convergence errors can occur for a number of reasons. When a problem occurs, ask: Does the base case model converge well and give reasonable results? Is the base case model formulated to handle data that may be out of mass or energy balance? Are the initial estimates of the parameters good enough?
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Are the specified standard deviations reasonable? Do the model inputs completely determine the measured results? Do the specified bounds allow the regression to take the model into infeasible regions, causing the unit operation blocks or flowsheet convergence to fail? Are the assumptions and simplifications in the model reasonable?
Regression runs with many variables and runs for highly non-linear models may still be difficult to converge. In some cases, the convergence criteria may be unnecessarily tight. The following table summarizes several convergence parameters that can be used to tune a regression run. It is not necessary to adjust the convergence parameters for most regressions.
Parameter ALG-ITERATION MAX-PASSES Description Maximum number of algorithm iterations. The default value is sufficient for nearly all problems Maximum number of flowsheet passes. This parameter may need to be increased for regressions involving a large number of variables. Convergence tolerance for sum of weighted square errors (Absolute objective function tolerance) This is the absolute tolerance for the objective function. The default tolerance is very tight, so regressions that converge to this tolerance should be reviewed thoroughly. Verify that the specified standard deviations are sensible. Change the default value of this parameter if you which to fit the model to achieve a particular objective function value. RFCTOL Relative objective function tolerance. The problem is considered converged if the model predicts that the maximum possible objective function is less than the product of the relative function tolerance and the current value of the objective function. For example, if RFCTOL is 0.1, then the model is converged when the predicted change in the objective function is less than ten percent of the objective function value for the current iteration. Minimum variable step-size tolerance. The problem is converged if the relative step size in the variables falls below XCTOL and the objective function is decreasing slowly (less than 50% per iteration). Minimum objective step-size tolerance Factor used to determine initial step sizes. This factor can profoundly affect the performance of the algorithm. If the initial steps are too large or too small, the model must adjust the step size until appropriate step sizes are determined. During the regression, the model determines the response of each variable to each other variable by making small adjustments, or pertubations, to the variables. The size of these adjustments is determined by the algorithm, this parameter is used to determine the maximum pertubation step sizes for each variable. You may need to increase this value when the fitted data are not very sensitive to the manipulated parameters, or decrease this value when the sensitivity is very strong. Factor used to determine lower and upper bounds for reconciled
SSQTOL
XCTOL
XFTOL INIT-STEP
PERT-FACTOR
BOUND-
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Parameter FACTOR
Description inputs. If the value is too large, the model may enter an infeasible region, for example a stream flow rate may go to zero. If the value is too small, the parameter ranges may be too narrow to fit the data. Method used to initialize the regression. Specify BASE-CASE to use the base case values to initialize the reconciled input parameters. Specify MEASUREMENTS to use the measured data to initialize the reconciled inputs.
INIT-METHOD
Ensuring Well-Formulated Regressions

Poorly formulated regressions may result in large residual values and a large objective function. Before starting a regression run, use sensitivity studies to test the model. Verify that the manipulated parameters have a strong influence on the measured data. Dont try to fit parameters which have only a weak impact on the model predictions. Make sure the parameter ranges are sensible. It is a waste of time to fit a parameter within a narrow range (less than 5%). On the other hand, if the range is too large, the regression algorithm may push the model into an infeasible region. For example, if the distillate to feed ratio in a column is allowed to decrease to zero, the column model will fail. The way the data regression is formulated has a major influence on how quickly and easily the problem converges. De-couple the manipulated variables as much as possible. For example, dont fit the rate constants and phase equilibrium parameters at the same time if the two sets of parameters can be fit independently in two smaller data regression runs. Use the weighing factors if some sets of data are more reliable than others. A larger weight may be assigned to a set of data that are based on long-term averages from the process information management system, lower weights might be assigned to data based on poorly kept records from the distant past. Make sure the manipulated parameters can be determined from the available data. For example, the activation energy of a reaction cannot be determined from isothermal data. The base-case file needs to be formulated in a robust manner. If the base case model does not converge reliably away from the base case condition, then it is likely that the regression run will fail. Use the sensitivity tool to verify that the model is stable over the entire range of each manipulated parameter and to verify that the model is sensitive to each parameter. Where possible, use relative or normalized inputs instead of absolute inputs. For example, in column models use the distillate to feed ratio (D:F) instead of distillate flow rate. Use pressure drop specifications instead of pressure. These specifications make the model more reliable and help to avoid problems that occur if the measured data are inconsistent.
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Fitting Activation Energy

It is tempting to try to fit activation energies and pre-exponential factors in the same regression run. This can lead to significant headaches if the problem is not approached right. Consider, for example, the standard Arrehnius rate expression:
knet = ko exp
Eact RT
Using this expression, the net rate constant,
knet , is sensitive to the activation
energy, Eact . If the activation energy is adjusted a little bit, a large adjustment must be made to the pre-exponential factor to offset this difference. In other words, the activation energy controls the magnitude of the reaction rate as well as the temperature sensitivity of the reaction rate. A better approach is to use the modified Arrehnius expression:
knet = ko exp
Eact 1 1 R T Tref
The parameter
Tref is a reference temperature that typically represents the
middle of the temperature range used to estimate the activation energy. Using this formula, the net rate constant, knet , remains constant at the reference temperature regardless of the value of the activation energy. With this approach, the pre-exponential factor, ko , controls the magnitude of the reaction rate at the reference temperature. The activation energy, Eact , controls the temperature sensitivity of the rate constant. This makes it much easier to fit the model.
Scaling the Fitted Parameters

When several types of parameters are adjusted in the same run, the magnitude of the manipulated parameters may influence how well the data regression converges. Ideally, the manipulated parameters should be within several orders of magnitude of each other. Suppose, for example, the manipulated parameters include rate constants for several different types of reactions. These expected values of the rate constants may differ by several orders of magnitude. In this situation, the regression procedure may over-emphasize the manipulated variables with the smallest magnitude. You can get around this problem using two CALCULATOR blocks as shown in Example 3. Use one CALCULATOR block to define a PARAMETER variable for each manipulated variable in the regression. Initialize each parameter to one. Use a second CALCULATOR block to READ these parameter values, to multiply them by base case values, and then WRITE the results to the manipulated variables. In the data regression block, manipulate the PARAMETER variables. This technique allows the data regression to operate on normalized variables instead of absolute variables which makes it much easier for the regression algorithm to choose appropriate step sizes and ensures that the variables are given equal weighting by the algorithm.
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Example 3: Using Fortran Blocks to Scale Manipulated Parameters Problem Description: Suppose two pre-exponential factors are adjusted to match conversion and intrinsic viscosity, which are defined as user Prop-Set properties. The pre-exponential factors have very different magnitudes, so scaling is required to get a good fit. Instead of manipulating the rate constants directly, use PARAMETER variables to define and manipulate correction factors for the rate constants. Use a CALCULATOR block to initialize these correction factors to unity. Manipulate these PARAMETER variables in the regression. Use a second CALCULATOR block to adjust the pre-exponential factors using the correction factors manipulated by the data regression model. USER-PROPERTY INT-VISC SUBROUTINE=USRPSP FLASH=YES USER-PROPERTY CONVERSN SUBROUTINE=USRPSP FLASH=YES PROP-SET INT-VISC INT-VISC PROP-SET CONVERSN CONVERSN DATA-SET DS-1 DEFINE CAT MASS-FLOW STREAM=CATALYST SUBSTREAM=MIXED COMPONENT=CAT DEFINE TEMP BLOCK-VAR BLOCK=CSTR1 SENTENCE=PARAM VARIABLE=TEMP DEFINE VISC STREAM-PROP STREAM=PRODUCT PROPERTY=INT-VISC DEFINE CONV STREAM-PROP STREAM=PRODUCT PROPERTY=CONVERSN USE STD-DEV 0.001 0.1 0.002 0.0050 / DATA 0.025 290.0 0.844 0.8550 / DATA 0.023 295.0 0.842 0.8700 / DATA 0.055 280.0 0.850 0.9050 / DATA 0.033 292.0 0.835 0.9000 STEP-GROWTH MYMODEL RATE-CON 1 PRE-EXP=9.67D14 ACT-ENERGY=41.0 RATE-CON 2 PRE-EXP=3.25D0 ACT-ENERGY=0.0 etc CALCULATOR INITIAL DEFINE P1 PARAMETER 1 DEFINE P2 PARAMETER 2 P1 = 1.0D0 P2 = 1.0D0 EXECUTE FIRST CALCULATOR ADJUST DEFINE P1 PARAMETER 1 DEFINE P2 PARAMETER 2 DEFINE EXP1 REACT-VAR REACTION=MYMODEL VAR=PRE-EXP SENT=RATE-CON ID1=1 DEFINE EXP2 REACT-VAR REACTION=MYMODEL VAR=PRE-EXP SENT=RATE-CON ID2=2 C specify base case pre-exponential factors for side rxn 1 and 2 F BASE1 = 9.67D14 F BASE2 = 3.25D0 C calculate pre-exponential factors using correction factors C manipulated by the data regression block F EXP1 = BASE1 * P1 F EXP2 = BASE2 * P2 READ-VARS P1 P2 WRITE-VARS EXP1 EXP2
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REGRESSION FIT-1 DATA DS-1 VARY PARAMETER 1 LABEL=CORRECT FACTOR RXN #1 LIMITS 0.1 10.0 VARY PARAMETER 2 LABEL=CORRECT FACTOR RXN #2 LIMITS 0.1 10.0
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17 User Models
This section discusses the features available in Aspen Polymers (formerly known as Aspen Polymers Plus) for incorporating user modules into a simulation model. Topics covered include: User Unit Operation Models, 351 User Kinetic Models, 357 User Physical Property Models, 361
Note: For more information on user models, see your Aspen Plus User Models documentation.
User Unit Operation Models

There are cases where users may need to create special models to represent a process. Usually these models can be configured by combining several of the standard unit operation building blocks. For more complex reactor geometries or in order to represent highly non-ideal systems users may need to provide their own model as a Fortran subroutine. There are two user unit operation blocks available: USER and USER2. The first allows a limited number of inlet and outlet streams. The second allows multiple inlet and outlet streams. Both unit operations take full advantage of the Aspen Plus flowsheeting capabilities. The required Fortran subroutine must process the feed streams and return the condition and composition of the outlet streams.
User Unit Operation Models Structure

There are three stages to the execution of Aspen Plus unit operation models: input processing, simulation calculations, and report writing. Normally, the implementation of a new model requires that all three stages be accounted for. However, in the case of USER2 models, a generic framework handles the input setup and processing stage. A Fortran subroutine must be written to perform the simulation calculations and for writing the report. If no report
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writer is provided Aspen Plus automatically echoes the input data in the report. The following figure summarizes the simulation sequence of a unit operation model:
User Unit Operation Model Calculations

A user unit operation model can be programmed to represent any unit operation. Most applications would include combinations of the following: separations, reactions, heat transfer, mass transfer, mixing and splitting. There are some common steps that are found in the simulation calculations within unit operation models, including user models. These steps include: Feed processing Physical properties and phase equilibrium calculations Unit operation calculations (kinetics, heat transfer, mass transfer, etc) Results storage and outlet stream initialization
Utilities are available to facilitate each of these steps. The available Fortran utilities and monitors are:
Stream Handling NPHASE LPHASE SSCOPY NSVAR Determines number of substreams Finds the location of a substream within a stream Copies a substream from one stream to another Determines the size of the stream vector
Component Attribute Handling GETDPN GETMWN Find the number average degree of polymerization Find the number average molecular weight
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GETPDI GETSMF GETSWF CAUPT LCATT
Find the polydispersity Find the segment mole fractions Find the segment weight fractions Load attributes into physical property system Finds the location of a component attribute in the stream vector
Component Handling (See Appendix C) CPACK ISPOLY ISSEG ISOLIG ISCAT ISINI KCCID Packs out trace components Determines if a component is a polymer Determines if a component is a segment Determines if a component is an oligomer Determines if a component is a catalyst Determines if a component is an ionic initiator Finds the component index (position in stream vector)
Property Monitors (See Aspen Plus User Models)
KVL
KLL ENTHL VOLV FUGLY IDLGAS VISCL
Calculates vapor-liquid equilibrium ratio (K-value)

Calculates liquid-liquid equilibrium ratio Calculates liquid mixture enthalpy Calculates liquid mixture molar volume Calculates liquid mixture fugacity coefficient Performs ideal gas calculations Calculates liquid mixture viscosity
Flash Routine (See Aspen Plus User Models) FLASH Flash monitor
Error Handling (See Aspen Plus User Models) IRRCHK ERRPRT WRTTRM Function to check diagnostic level Error printing routine Writer to terminal file or control panel
Report Writer (See Aspen Plus User Models) RPTHDR Report pagination /header writer
Stream Processing
In order to perform its calculations the user model must be able to read and process the Aspen Plus stream structure. The stream structure is documented in Aspen Plus User Models. Example 1 shows a USER2 model routine. Note: The data in the streams coming in and out of the model are stored in SI units. There are several utilities available for stream processing. These perform functions such as finding the number of stream variables, i.e. the size of the stream vector, copying one stream to another, finding the total number of substreams, and finding specific substreams within a stream. Several stream handling utilities are documented in Appendix C of this User Guide.
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In addition to the standard composition and state information found in the stream structure, there are also component attributes. If the user model processes polymers, then component attributes must be processed and their outlet stream values must be calculated and stored. The attributes available include polymer properties such as degree of polymerization, molecular weight, polydispersity, and copolymer composition. These are documented in the Polymer Structural Properties section of Chapter 2. In order to process attributes, there are Fortran utilities available that perform functions such as copying attributes from one stream to another, retrieving number average molecular weight and degree of polymerization, retrieving copolymer composition, locating specific component attributes within the stream vector, and determining the size of a vector component attribute. The component attribute handling utilities are documented in Appendix C. There are also utilities for processing components: for excluding trace components, for determining component type (polymer, oligomer, segment, catalyst), etc. These can be found with the component attribute processing utilities. Example 1: USER2 Model Routine C---------------------------------------------------------------------SUBROUTINE USRMOD (NMATI, SIN, NINFI, SINFI, NMATO, 2 SOUT, NINFO, SINFO, IDSMI, IDSII, 3 IDSMO, IDSIO, NTOT, NSUBS, IDXSUB, 4 ITYPE, NINT, INT, NREAL, REAL, 5 IDS, NPO, NBOPST, NIWORK, IWORK, 6 NWORK, WORK, NSIZE, SIZE, INTSIZ, LD) C---------------------------------------------------------------------C IMPLICIT NONE C C DECLARE VARIABLES USED IN DIMENSIONING C INTEGER NMATI, NINFI, NMATO, NINFO, NTOT, + NSUBS, NINT, NPO, NIWORK,NWORK, + NSIZE C #include "ppexec_user.cmn" EQUIVALENCE (RMISS, USER_RUMISS) EQUIVALENCE (IMISS, USER_IUMISS) C #include "dms_plex.cmn" EQUIVALENCE (IB(1), B(1)) REAL*8 B(1) C #include "dms_rglob.cmn" C #include "dms_global.cmn" C #include "dms_ipoff1.cmn" C #include "dms_ncomp.cmn" C C DECLARE FUNCTIONS C INTEGER SHS_LCATT, DMS_KCCIDC
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C C C
INTEGER XMW, LMW DECLARE ARGUMENTS INTEGER IDSMI(2,NMATI), IDSII(2,NINFI), + IDSMO(2,NMATO), IDSIO(2,NINFO), + IDXSUB(NSUBS),ITYPE(NSUBS), INT(NINT), + IDS(2,3), NBOPST(6,NPO), + IWORK(NIWORK),INTSIZ(NSIZE),NREAL, LD, INTEGER KH2O REAL*8 SIN(NTOT,NMATI), SINFI(NINFI), + SOUT(NTOT,NMATO), SINFO(NINFO), + WORK(NWORK), SIZE(NSIZE) DECLARE LOCAL VARIABLES INTEGER IMISS REAL*8 REAL(NREAL), RMISS, WATER
C C C C C
INTEGER IDXP, LZMOM, LMWN, IMWN(2), IZMOM(2) REAL*8 AMWP, ZMOM INITIALIZE ARRAY OF ATTRIBUTE NAMES DATA IZMOM / "ZMOM"," " / DATA IMWN / "MWN "," " /
C C---------------------------------------------------------------------C C BEGIN EXECUTABLE CODE C C---------------------------------------------------------------------C OFFSETS TO COMPONENT MOLECULAR WEIGHTS XMW(I) = DMS_IFCMNC('MW') + I C C FIRST COPY FIRST INLET TO FIRST OUTLET C DO 100 I = 1, NTOT SOUT(I,1) = SIN(I,1) 100 CONTINUE C C INITIALIZE THE SECOND OUTLET C DO 200 I = 1, NCOMP_NCC+1 SOUT(I,2) = 0D0 200 CONTINUE C DO 300 I = NCOMP_NCC+2, NCOMP_NCC+9 SOUT(I,2) = RMISS 300 CONTINUE C C FIND LOCATION OF COMPONENT ATTRIBUTES C IDXP is position of polymer component in component list. C Can be obtained with ispoly function C find location of attributes in stream LZMOM = SHS_LCATT( 1, IDXP, IZMOM ) LMWN = SHS_LCATT( 1, IDXP, IMWN ) IF (LZMOM .NE. 0) ZMOM = SOUT(LZMOM+1,1) C
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C C C C C C C C
EXAMPLE OF FINDING A COMPONENT POSITION BY NAME KH2O = DMS_KCCIDC ( 'H2O' ) CAN ALSO PASS POSITION AS PARAMETER IN INT VECTOR E.G. KH2O = INT(2) IF ( KH2O .EQ. 0 ) GO TO 999 PUT COMPONENT (WATER) IN THE SECOND OUTLET WATER = SIN(KH2O,1) SOUT(KH2O,1) = 0D0 SOUT(NCOMP_NCC+1,1) = SIN(NCOMP_NCC+1,1) - WATER SOUT(KH2O,2) = WATER SOUT(NCOMP_NCC+1,2) = WATER RETURN END
C 999
Physical Property Calculations

Physical properties and phase equilibrium calculations can be performed within a user model. Property methods, models, and parameters specified in the input either through a built-in or a user-defined property method, can be used for the user model calculations. This can be done through property monitors. The user model requests the property of interest by calling a specific monitor, sets the state information and calculation codes in the call to the monitors, and in turn obtains thermodynamic properties such as fugacity coefficients, enthalpies, entropies, molar volumes, etc. A flash calculation routine is also available. See the table on page 352 for a listing of frequently used property monitors. The FLASH routine and the property monitors are documented in Aspen Plus User Models. See also User Physical Property Models on page 361.
Unit Operation Calculations

The purpose of a user unit operation block is to allow the flexibility to program user correlations or algorithms to represent a process. Independently from the physical property calculations for which monitors are provided, users can take advantage of the Fortran subroutine structure to incorporate the calculations needed to represent their process. Aspen Plus System Management documents programming guidelines to be followed when defining the model calculations. The calculations performed within a user unit operator model for a polymer system are similar to those that could be performed within a kinetic model. See User Kinetic Models on page 357.
Diagnostics
Throughout the simulation calculations, a user model may call the Aspen Plus error handler to issue diagnostic messages ranging from fatal errors to warnings and information. The error handler is documented in Aspen Plus
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User Models. These diagnostics can be written to the terminal or the control panel. The USER labeled commons contains output file numbers through which the terminal, control panel and simulation files can be accessed. See Aspen Plus User Models for a description of the USER labeled common.
User Unit Operation Report Writing

A report section can be included for a user model in the Aspen Plus simulation report. This requires a Fortran report writer subroutine. To write the report a report pagination utility is available. This utility is documented in Aspen Plus User Models. Note that in the user interface the integer and real arrays for the user model are displayed on the results screen of the user model.
User Kinetic Models

User kinetic models are primarily intended for situations where the polymerization phenomena taking place are highly complex and cannot be represented by the built=in models. Users can write their own equations for the rate of change of components and the attributes of the polymer that they are intending to track. This is done through a USER reaction block. The USER block can be used in conjunction with built-in models. The user model gives the basic framework for specifying the reaction stoichiometry and the rate constant parameters. The user kinetic model requires a Fortran subroutine which performs all the computations that are required for computing the rates of change for components in the reactive phase and rates of change for polymer attributes. The structure of this subroutine is documented in Aspen Plus User Models. For polymerization kinetics user model, there are specific calculations that are typically performed. These include: Locating the polymer component attributes within the stream vector. This is done through the utility routine SHS_LCATT. Users need to determine and provide IDXP which is the component index for the polymer. = SHS_LCATT( 1, IDXP, ICATYP( 1, IDPN ) ) = SHS_LCATT( 1, IDXP,ICATYP( 1, IZMOM ) )
LDPN LZMOM
Retrieving the polymer attribute values from the stream vector SOUT. The following code shows how to retrieve DPN from SOUT. Other attributes can be similarly obtained. Calculating the specific volume of the reacting phase from the stream vector SOUT. From the stream vector, calculate the total number of moles and volume of the reacting phase. This example assumes that the reacting phase is a single liquid phase.
IF( LDPN .GT. 0 .AND. SOUT(LDPN+1) .GT. 0D0) DPN = SOUT(LDPN+1)
CALL SHS_CPACK (SOUT, NCK, IDXX, XX, TOTFLO) CALL PPMON_VOLL ( + TEMP, PRES, XX, NCK, IDXX, NBOPST, 4, 1, + SVOL, DV, KER) VFLOW1 = SLIQRX VFLOW = SVOL * SOUT(NCK+1) Calculating molar concentration of each component and class 2 attributes in the reacting phase. This is obtained by dividing the mole fraction of the
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component in the reacting phase by the molar volume of the reacting phase. It is also shown how to compute concentration of ZMOM, a class 2 attribute for the polymer. DO 50 I = 1, NC CONC(I) = XX(I)/SVOL 50 CONTINUE IF(LZMOM .GT. 0 .AND. VFLOW .GT. RGLOM_RMIN) ZMOM=SOUT(LZMOM+1)/VFLOW
Loading the rate constants for each reaction in the reacting phase. The vector REALR will hold the values of the kinetic constants.
DO 200 I = 1, NR AK(I) = REALR(I) 200 CONTINUE Calculating the rate of reaction for each component and returning that information to the reactor. The rate equations are user derived. For example assume that the following user reactions are to be included in the user kinetics:
A1 + A2 A3 + Waste1 A3 Waste2
k2
k1
k1
The rate constants for user reactions are obtained as: AK(1) = k1 AK(2) = k2 The reaction rate for the components ( 1=A1, 2=A2, 3=A3 ) are calculated as: RATES(1) = -AK(1)*CONC(1)*CONC(2)*VFLOW RATES(2) = -AK(1)*CONC(1)*CONC(2)*VFLOW RATES(3) = (AK(1)*CONC(1)*CONC(2) - AK(2)*CONC(3))*VFLOW Calculating rate of change for Class 2 attributes for the polymer. The user is responsible for deriving the expression for the rate of change of attribute values.
DO 400 I = 1, NTCAT RATCAT(I) = 0D0 400 CONTINUE C The following example code explains the above steps in greater detail. Note: The data coming in and out of the model are stored in SI units. Example 2: User Kinetic Subroutine C-----------------------------------------------------------------------SUBROUTINE USRKIP (SOUT, NSUBS, IDXSUB, ITYPE, NINT, 2 INT, NREAL, REAL, IDS, NPO, 3 NBOPST, NIWORK, IWORK, NWORK, WORK, 4 NC, NR, STOIC, RATES, FLUXM, 5 FLUXS, XCURR, NTCAT, RATCAT, NTSSAT,
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6 RATSSA, KCALL, KFAIL, KFLASH, NCOMP, 7 IDX, Y, X, X1, X2, 8 NRALL, RATALL, NUSERV, USERV, NINTR, 9 INTR, NREALR, REALR, NIWR, IWR, * NWR, WR, NRL, RATEL, NRV, 1 RATEV) C-----------------------------------------------------------------------IMPLICIT NONE C C DECLARE VARIABLES USED IN DIMENSIONING C INTEGER NSUBS, NINT, NPO, NIWORK,NWORK, + NC, NR, NTCAT, NTSSAT,NCOMP, + NRALL, NUSERV,NINTR, NREALR,NIWR, + NWR C #include "ppexec_user.cmn" EQUIVALENCE (RMISS, USER_RUMISS) EQUIVALENCE (IMISS, USER_IUMISS) C C C C.....RCSTR... #include "rcst_rcstri.cmn" #include "rxn_rcstrr.cmn" C C.....RPLUG... #include "rplg_rplugi.cmn" #include "rplg_rplugr.cmn" EQUIVALENCE (XLEN, RPLUGR_UXLONG) EQUIVALENCE (DIAM, RPLUGR_UDIAM) C C.....RBATCH... #include "rbtc_rbati.cmn" #include "rbtc_rbatr.cmn" C C.....PRES-RELIEF... #include "prsr_presri.cmn" #include "rbtc_presrr.cmn" C C.....REACTOR (OR PRES-RELIEF VESSEL OR STAGE) PROPERTIES... #include "rxn_rprops.cmn" EQUIVALENCE (TEMP, RPROPS_UTEMP) EQUIVALENCE (PRES, RPROPS_UPRES) EQUIVALENCE (VFRAC, RPROPS_UVFRAC) EQUIVALENCE (BETA, RPROPS_UBETA) EQUIVALENCE (VVAP, RPROPS_UVVAP) EQUIVALENCE (VLIQ, RPROPS_UVLIQ) EQUIVALENCE (VLIQS, RPROPS_UVLIQS) C C INITIALIZE RATES C C C DECLARE ARGUMENTS C INTEGER IDXSUB(NSUBS),ITYPE(NSUBS), INT(NINT), + IDS(2),NBOPST(6,NPO),IWORK(NIWORK),
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C C C
+ + + REAL*8 + + + + REAL*8 + +
IDX(NCOMP), INTR(NINTR), IWR(NIWR), NREAL, KCALL, KFAIL, KFLASH,NRL, NRV, I SOUT(1), WORK(NWORK), STOIC(NC,NSUBS,NR), RATES(1), FLUXM(1), FLUXS(1), RATCAT(NTCAT), RATSSA(NTSSAT), Y(NCOMP), X(NCOMP), X1(NCOMP), X2(NCOMP) RATALL(NRALL),USERV(NUSERV), REALR(NREALR),WR(NWR), RATEL(1), RATEV(1), XCURR
DECLARE LOCAL VARIABLES INTEGER IMISS, IDPN(2), IZMOM(2), XMW REAL*8 REAL(NREAL), RMISS, XLEN, DIAM, TEMP, + PRES, VFRAC, BETA, VVAP, VLIQ, + VLIQS DATA IDPN / "DPN ", " " / DATA IZMOM / "ZMOM", " " / BEGIN EXECUTABLE CODE ASSUME WE ARE USING A BATCH REACTOR. FOR OTHER REACTORS THE PROCEDURE IS SIMILAR OFFSETS TO COMPONENT MOLECULAR WEIGHTS XMW(I)=DMS_IFCMNC('MW')+I FIND INDEX OF SPECIES BY NAME IDXP=DMS_KCCIDC('POLY') DETERMINE POINTERS TO POLYMER ATTRIBUTES LDPN LZMOM = SHS_LCATT( 1, IDXP, IDPN ) = SHS_LCATT( 1, IDXP, IZMOM )
C C C C C C C C C
C C C
GET POLYMER ATTRIBUTES VALUES FROM SOUT IF( LDPN .GT. 0 .AND. SOUT(LDPN+1) .GT. 0D0) DPN = SOUT(LDPN+1)
C-----------------------------------------------------------------C GET REACTING PHASE SPECIFIC MOLAR VOLUME, SVOL ASSUMING IT IS C LIQUID C CALL SHS_CPACK (SOUT, NCK, IDX, X, TOTFLO) CALL PPMON_VOLL ( + TEMP, PRES, X, NCK, IDX, NBOPST, 4, 1, SVOL, DV, KER) VFLOW1 = SLIQRX C C C GET VOLUME OF REACTING PHASE, VFLOW C VFLOW = SVOL * SOUT(NCK+1) C C----------------------------------------------------------------C
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C.....CALCULATE MOLAR CONCENTRATIONS OF COMPONENTS AND CLASS 2 C ATTRIBUTES DO 50 I = 1, NC CONC(I) = XX(I)/SVOL 50 CONTINUE IF(LZMOM .GT. 0 .AND. VFLOW .GT. RGLOM_RMIN) ZMOM=SOUT(LZMOM+1)/VFLOW C-----------------------------------------------------------------C INITIALIZE THE RATES FOR COMPONENTS TO ZERO C DO 100 I = 1, NC RATES(I) = 0D0 100 CONTINUE C C-----------------------------------------------------------------C LOAD REACTION RATE CONSTANTS FROM THE REALR DO 200 I = 1, NR AK(I) = REALR(I) 200 CONTINUE C C-----------------------------------------------------------------C CALCULATE REACTION RATES FOR COMPONENTS C DO 300 I = 1, NC DO 310 J = 1, NC M = COMPUTE CORRECT INDEX RATES(I) = RATES(I) - AK(M) * CONC(I)*CONC(J)*VFLOW 300 CONTINUE C C C CALCULATE RATES FOR CLASS-2 ATTRIBUTE EXAMPLE C-----------------------------------------------------------------DO 400 I = 1, NTCAT RATCAT(I) = 0D0 400 CONTINUE C C C C INITIALIZE ATTRIBUTES OF INTEREST IN THIS WAY FOR ARRAY ATTRIBUTES THIS GIVES FIRST LOCATION IN ARRAY RACAT(LZMOM - (NC+9) + 1) = 0 RETURN END
User Physical Property Models

There is often a need among industrial users to calculate one or more physical properties based on in-house or literature correlations and expressions that
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are not available in Aspen Polymers. In such cases, users can take advantage of physical property user models. A user subroutine needs to be supplied for each user model that will calculate the desired property. For each physical property, a fixed subroutine name and argument list exists; these can be found in Aspen Plus User Models. An example of a simple user subroutine that calculates and returns the liquid molar enthalpy of a mixture (HLMX) is provided below. For instructions on how to use user physical property models from the graphical user interface, see Volume 2 of this User Guide, Aspen Polymers Physical Property Methods and Models. User model development in polymer simulation is very similar to that in the simulation of standard components. In case some polymer attributes are needed for the calculation of a user property, these can be retrieved by calling the appropriate utility routine (see the table on page 352 for a summary of the utilities available). The following can be helpful while developing a physical property user model in Aspen Polymers: The index vector, IDX, contains the indexes of the components present in the current calculation run. For example, if the first component present currently is listed third in the component list, then: IDX(1) = 3. Parameter values are retrieved using the utility DMS_IFCMNC. For example, suppose you want to pick up the molecular weight of a component. You need to define an integer array with elements the locations of the molecular weights of all the components in the component list on the plex vector, B: Then, the molecular weight of the component listed third in the component list is B(XMW(3)). In polymer user models, it is often necessary to identify whether a particular component is polymer, oligomer, or segment. This is done by the utility logical functions SHS_ISPOLY, SHS_ISOLIG, and PPUTL_ISSEG. For instance, suppose you want to perform a certain manipulation on the polymer components present in your run: Which will send the calculation to line number 10 if the component with index I is a polymer component. The mole fraction vector X (or Z) is based on the apparent molecular weight of the polymer components. If you need to perform calculations for a polymer run where the mole fractions are needed, then you must use the true mole fractions (which are based on the true molecular weight of the polymer) rather than the apparent mole fractions X. This is done by a conversion utility routine called POLY_XATOXT: Where: XMW is the vector of the apparent molecular weights, IDX is the index vector, X is the stream apparent mole fraction vector, and XTRUE is the vector that contains the mole fractions based on the true molecular weight of the polymer. Polymer attributes needed for calculations in user physical property models are retrieved using utility subroutines. For a list of available utilities see the table on page 352. As an example, to get the number
XMW(I) = DMS_IFCMNC('MW') + I
IF (SHS_ISPOLY(I)) GO TO 10
CALL POLY_XATOXT( N, IDX, XMW, X, XTRUE)
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average degree of polymerization, DPn, for a particular component you must give: CALL POLY_GETDPN( 1, 1, I, DPN ) Where I is the component index. For a detailed description of all the polymer utilities available see Appendix C. Users can call several Aspen Plus subroutines to perform specific tasks. For example, routine IDLGAS will return the ideal-gas properties of the components and their mixture, while PL001 will return the vapor pressure of the desired components (see Aspen Plus User Models). After calculating a molar property, the appropriate conversion must be made so that the returned property is based on the apparent mole basis. For instance, after the calculation of the liquid enthalpy of a polymer component based on the true molecular weight, the following conversion should be made:
HL_app = HL_true * MW_app / MW_true A sample user subroutine that calculates and returns the mixture liquid enthalpy is given in the Example 3. Note: The data coming in and out of the model are stored in SI units. Example 3: User subroutine for mixture liquid enthalpy calculation C---------------------------------------------------------------------SUBROUTINE HL2U (T ,P ,Z ,N ,IDX , 1 IRW ,IIW ,KCALC ,KOP ,NDS , 2 KDIAG ,QMX ,DQMX ,KER ) C C---------------------------------------------------------------------C HV2U IS A USER MIXTURE ENTHALPY SUBROUTINE C C THIS USER SUBROUTINE CALCULATES THE LIQUID ENTHALPY OF A BINARY C MIXTURE CONTAINING ONE POLYMER AND ONE SOLVENT. C C C NAME OF MODULE: HL2U C C IMPLICIT NONE C DIMENSION Z(N), IDX(N), KOP(10) DIMENSION D(15) C... USER DIMENSION DIMENSION XTRUE(10) C C #include "dms_ncomp.cmn" #include "ppexec_user.cmn" #include "dms_plex.cmn" C EQUIVALENCE (IB(1), B(1))
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C C---------------------------------------------------------------------C C STATEMENT FUNCTIONS FOLLOW C XMW(I) = DMS_IFCMNC('MW') + I DHFORM(I) = DMS_IFCMNC('DHFORM') + I CPIG(I,J) = DMS_IFCMNC('CPIG') + 11*(J - 1) + I C C *** NOTE ******************************************* C C PARAMETERS ARE LOCATED USING THE UTILITY DMS_IFCMNC C AND THE NAME OF THE PARAMETER. FOR EXAMPLE, C DMS_IFCMNC('MW') RETRIEVES THE LOCATIONS WHERE THE C COMPONENT MOLECULAR WEIGHTS ARE STORED. C C **************************************************** C DO 100 I=1,10 XSEG(I) = 0.D0 100 CONTINUE C TREF = 298.15 C C---------------------------------------------------------------------C C *** NOTE ******************************************* C COMPONENT ID FOR MONOMER *HARD-WIRED* AT POSITION 2 C COMPONENT ID FOR POLYMER *HARD-WIRED* AT POSITION 3 C **************************************************** C IMON = 2 IPOL = 3 ISEG = 4 C C C## BOTH Z AND XSEG ARE PACKED: XSEG(IPOL) CONTAINS MOLE FRAC OF SEGMENT C CALL XATOXT(N, IDX, B(XMW(1)), Z, XTRUE) C C POLYMERIC SPECIES PROP-SET PROPERTIES C DELT1 = T - TREF DELT2 = (T**2 - TREF**2)/2.D0 DELT3 = (T**3 - TREF**3)/3.D0 DELT4 = (T**4 - TREF**4)/4.D0 H_MON = B(DHFORM(IMON)) + B(CPIG(1,IMON))*DELT1 + + B(CPIG(2,IMON))*DELT2 + B(CPIG(3,IMON))*DELT3 + B(CPIG(4,IMON)) +*DELT4 H_POL = B(DHFORM(IPOL)) + B(CPIG(1,IPOL))*DELT1 + + B(CPIG(2,IPOL))*DELT2 + B(CPIG(3,IPOL))*DELT3 + B(CPIG(4,IPOL)) +*DELT4 C
INTEGER XMW, DHFORM, CPIG, II, DMS_IFCMNC INTEGER IMON, IPOL, IIMON, IIPOL, I, N, J, ISEG REAL*8 DELT1, DELT2, DELT3, DELT4, H_MON, H,POL, * HM_MIX, AVG_MW, T, TREF, QMX
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C C C C C C C C C C C C C C C C C C C C C C
*** NOTE ******************************************* IN CASE A COMPONENT ATTRIBUTE WAS NEEDED FOR THE CALCULATION OF THE POLYMER ENTHALPY, THE APPROPRIATE UTILITY ROUTINE SHOULD BE CALLED. FOR EXAMPLE, SUPPOSE THE NUMBER-AVERAGE DEGREE OF POLYMERIZATION (DPn) OF THE POLYMER WAS NECESSARY. THE UTILITY ROUTINE GETDPN CAN BE USED TO RETURN THE DESIRED ATTRIBUTE: CALL POLY_GETDPN (1, 1, IPOL, DPN) THE ARGUMENTS HAVE THE FOLLOWING MEANING: 1 1 IPOL DPN = = = = CONVENTIONAL SUBSTREAM DPN FOR 1 COMPONENT IS REQUESTED (NCP=1) POLYMER COMPONENT INDEX RETURNED VALUE OF THE NUMBER AVERAGE DEGREE OF POLYMERIZATION
**************************************************** IIMON = 0 IIPOL = 0 DO 10 I=1,N II = IDX(I) IF (II.EQ.IMON) IIMON = I IF (II.EQ.IPOL) IIPOL = I CONTINUE HM_MIX AVG_MW = H_MON*XTRUE(IIMON) + H_POL*XTRUE(IIPOL) = B(XMW(IMON))*Z(IIMON) + B(XMW(IPOL))*Z(IIPOL)
10 C C C C C C 999
CONVERT FROM TRUE TO APPARENT MOLE BASIS QMX = HM_MIX * AVG_MW / B(XMW(ISEG)) CONTINUE RETURN END
References
Aspen Plus User Models. Cambridge, MA: Aspen Technology, Inc. Aspen Plus System Management. Cambridge, MA: Aspen Technology, Inc.
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18 Application Tools
This section discusses the tools available for applying Aspen Polymers (formerly known as Aspen Polymers Plus) features to solve real-life problems. The topics covered include: Example Applications for a Simulation Model, 366 Application Tools Available in Aspen Polymers, 367 Model Variable Accessing, 369
Example Applications for a Simulation Model

The main purpose of a simulation model is to provide the engineer with a deeper understanding of the molecular and macroscopic processes which are vital to a polymer manufacturing process. This understanding will eventually lead to improvements in various aspects of the process related to safety, productivity, and polymer product quality. These are some typical scenarios in which a simulation model is used to meet this objective. A model may be used to: Identify superior grade transition policies and better plant startup and shutdown procedures which minimize offspec polymer product Reduce the number of lengthy and costly experiments on bench, pilot, and plant scale for polymer product and polymerization process development Train process engineers, chemists, plant operators Identify sources of variance in polymer product quality Provide data for the design of rupture discs and vent lines Find optimal temperature profiles for a continuous reactor train which minimize reaction medium viscosity while meeting product specifications Investigate monomer feed policies for a semi-batch copolymerization process for keeping the chemical composition distribution narrow Design a free-radical initiator mix to maximize productivity under the constraints of safe reactor operations
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Application Tools Available in Aspen Polymers

Several analysis and flowsheeting tools are available in Aspen Polymers to configure a model for performing analyses and studies of a process. These include: CALCULATOR - used to incorporate Fortran or Microsoft Excel calculations in the simulation DESIGN-SPEC - used to apply specifications on process variables SENSITIVITY - used to examine the effect of varying one or more process variables CASE-STUDY - used to compare between different sets of operating conditions OPTIMIZATION - used to perform optimization calculations
For each of these tools, with the exception of CALCULATOR, Aspen Plus sets a loop around a model, flowsheet section, or entire flowsheet. Within this loop, selected operating variables are manipulated and key process variables are sampled. The calculation procedure for analysis and flowsheeting tools is illustrated here:
The categories of accessible flowsheet variables are described in Model Variable Accessing on page 369. Note that in most cases Aspen Plus automatically generates the calculation sequence. You can also specify a sequence manually. For details on how use these tools in your simulations, see the Aspen Plus User Guide. Example uses of these features are given in the Aspen Polymers Examples and Applications Case Book.
CALCULATOR
Calculator blocks provide a mechanism for you to incorporate Fortran statements or Microsoft Excel spreadsheets into the flowsheet calculations. This can be used to calculate and set input variables based on special user
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inputs. For this reason, calculator blocks can be used as feed-forward controllers. You can also use calculator blocks to calculate and write results to the Aspen Plus report, control panel, or external file. Calculator blocks can be used to display charts, tables, or graphs through Excel. To use this block you must specify which model variables to sample or manipulate, enter the Fortran statements or create the Excel sheet, and set the sequence in which the block must be executed during the flowsheet calculations. An example use of a calculator block as a feed-forward controller would be to hold the flowrate of a catalyst proportional to a monomer flow for a situation where that monomer flow varies.
DESIGN-SPEC
Design-Spec blocks allow you to set a process variable that is normally calculated during the simulation. For each specification, you must identify which process variable can be adjusted to meet that specification. For this reason, Design-Spec blocks can be used as feedback controllers. To use this block you must specify which model variables must be fixed, what values they must be fixed at, and which model input variables can be manipulated. You can include Fortran statements in Design-Spec blocks. An example use of a Design-Spec block would be to set a maximum amount for impurities in a product stream.
SENSITIVITY
Sensitivity blocks provide a mechanism for you to analyze the effect of operating variables, which you select on the process. This block generates a matrix of manipulated variables versus sampled variables. If there is more than one manipulated variable, the sensitivity analysis is performed for each combination of manipulated variables. It is recommended that you use multiple Sensitivity blocks if you do not want to combine the manipulated variables. To use this block you must specify which are the manipulated variables, which are the sampled variables, and how they must be tabulated. You can include Fortran statements in Sensitivity blocks. An example use of a Sensitivity block would be to determine the effect of reactor temperature or pressure on the polymer product properties.
CASE-STUDY
Case-Study blocks provide another mechanism for you to analyze the effect of operating conditions on process variables. They allow you to make several runs in series for the entire flowsheet. Since a report is generated for the whole flowsheet for each case, you do not need to specify output variables to be sampled.
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To use this block you must identify the case study variables, assign values for these variables, and specify reporting options. An example use of Case-Study would be to investigate the effect of changing feed conditions and composition on key process variables.
OPTIMIZATION
Optimization blocks provide a mechanism for you to minimize or maximize an objective function calculated using key process variables. To define the objective function you would use Fortran statements. To use this block you must define the objective function, specify manipulated variables, and define constraints, if any. An example use of Optimization would be to find the optimal reactor temperature to meet polymer product property specifications while minimizing reaction medium viscosity.
Model Variable Accessing

When using the various model analysis tools to perform sensitivity studies, optimization studies, case studies, or data fitting, or when applying design specifications, or adding calculator blocks to a simulation model, users must access many different flowsheet variables. These flowsheet variables are grouped by type: Unit operation block variable Stream variable (including polymer component attributes) Reaction variable Physical property variable
Variable Type Block Stream Identifier BLOCK-VAR STREAM-VAR MOLE-FLOW MOLE-FRAC MASS-FLOW MASS-FRAC STDVOL-FLOW STDVOL-FRAC STREAM-PROP STREAM-VEC SUBSTRM-VEC Stream COMPATTR-VAR COMPATTR-VEC Description Unit operation block variable Unit operation block vector Non component dependent stream variable Component mole flow Component mole fraction Component mass flow Component mass fraction Component standard volume flow Component standard volume fraction Stream Prop-Set property Entire stream vector Entire substream vector Component attribute element (Notes 1-4) Component attribute (Notes 1-4)
A partial list of accessible variables is given here:
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Variable Type
Identifier SUBSATTR-VAR SUBSATTR-VEC
Description Substream attribute element Substream attribute Reaction variable (Note 5) Unary physical property parameter Binary physical property parameter
Reaction Physical Properties
REACT-VAR UNARY-PARAM BI-PARAM
Notes: 1. Component attributes may be accessed in several ways. They may be accessed through STREAM-VEC or through SUBSTRM-VEC. In this case, users are responsible for locating the desired attribute and attribute element within the stream or substream vector. See the table that follows for the MIXED substream vector structure. 2. Component attributes may also be accessed with COMPATTR-VAR. With COMPATTR-VAR, users must provide the element number for attributes having more than one element. See the Polymer Structural Properties section of Chapter 2 to find out the dimensions of polymer component attributes. If the attribute is dimensioned by number of polymer segments, NSEGS, (e.g. SFLOW, or SFRAC polymer attributes), the ordering of elements follows the order in which the list of polymer segments was specified (See the Component Classification section of Chapter 2). For component attributes dimensioned by number of catalytic sites, each element represents a site number, i.e. site no. 1, no. 2, etc. For twodimensional component attributes dimensioned by number of segments and number of catalytic sites (NSEGS*NSITES), the first dimension is NSEG, therefore, the ordering of elements is as follows: the list of specified segments is repeated for each site beginning with site no. 1. 3. Component attributes may also be accessed with COMPATTR-VEC. In this case, users are not required to provide an element number since the whole component attribute is returned as a vector having one or more elements. The ordering of elements within the attribute vector follows the description given in Note 2. 4. COMPATTR-VAR and COMPATTR-VEC are equivalent for component attributes having only one element. 5. REACT-VAR may be used to access kinetic constant parameters for reaction kinetic models, including free-radical, step-growth and Ziegler-Natta. The type of information required to access these parameters is model dependent. For free-radical, the reaction type (INIT-DEC, for example), and the reacting species are required, in addition to the name of the parameter to be accessed. The same is true for Ziegler-Natta which also requires a catalyst site type number. For step-growth, a reaction number is required. For the standard Aspen Plus reaction models, a reaction number, and/or substream identifier may be needed to locate the parameters. The MIXED substream structure is summarized here:
Array Index Description
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1, ..., NCC NCC + 1 NCC + 2 NCC + 3 NCC + 4 NCC + 5 NCC + 6 NCC + 7 NCC + 8 NCC + 9 NCC + 10
Component mole flows (kgmole/sec) Total mole flow (kgmole/sec) Temperature (K) Pressure (N/m2) Mass enthalpy (J/kg) Molar vapor fraction Molar liquid fraction Mass entropy (J/kg-K) Mass density (kg/m3) Molecular weight (kg/kgmole)
valuencat1 value1
Values for component attribute 1 of component 1 (polymer or other attributed component)
valuencat1 value1 valuencat1 value1
Note: NCC is the number of conventional components (including polymers, segments and oligomers) entered on the Components Specifications Selection sheet. This parameter is stored as NCOMP_NCC in labeled common DMS_NCOMP (See Aspen Plus User Models, Appendix A).
References
Aspen Plus User Guide. Cambridge, MA: Aspen Technology, Inc. Convergence and Optimization in Aspen Plus, Course notes. Cambridge, MA: Aspen Technology, Inc.
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19 Run-Time Environment
This chapter discusses various topics related to working in the Aspen Polymers (formerly known as Aspen Polymers Plus) environment. The topics covered include: Aspen Polymers Architecture, 372 Installation Issues, 373 Configuration Tips, 373 User Fortran, 374 Troubleshooting Guide, 374
Aspen Polymers Architecture

Aspen Polymers is a layered product. In other words, this product works in conjunction with a main program. This main program is Aspen Plus for steady-state simulation and Aspen Dynamics or Aspen Custom Modeler for dynamic simulation. Aspen Polymers brings to these simulators the polymer process technology in the form of component characterization, physical property models and databanks, kinetic models, and the associated input forms. As a result of this layered architecture the installation and configuration of Aspen Polymers is closely tied to that of Aspen Plus for steady-state simulation and that of Aspen Dynamics and Aspen Custom Modeler for dynamic simulation. In this chapter we will focus on topics related to the Aspen Plus environment. The overall Aspen Polymers architecture is shown here:
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Installation Issues
Hardware Requirements
Aspen Polymers is available on all the hardware platforms supported by Aspen Plus. For the user interface and engine, these are Windows 2000 with Service Pack 1 and Windows XP. Consult the Aspen Engineering Suite Installation Guide for the hardware requirements.
Installation Procedure
Refer to the Aspen Engineering Suite Installation Guide, Aspen Polymers chapter for information on how to install Aspen Polymers on your system.
Configuration Tips
Startup Files
The information needed to launch the main Aspen Plus application window is recorded in startup files. These files define the type of simulation, default settings for the user interface, hosts for the simulation engine, run settings, etc. One type of startup file is used to define defaults for the type of simulation. This is the simulation template.
Simulation Templates
Simulation templates are available to help you get started setting up your model. These templates typically contain options such as unit sets, physical property method selection, and Table File Format (TFF) selection for stream result tables. Polymer simulation templates are available. You can create your own personal template to allow faster definition of a new simulation model.
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To use a simulation template, after starting Aspen Plus, on the startup box select the template startup option. Then choose one of the polymer simulation templates. This will automatically setup a global unit set, an appropriate polymer property method, and a polymer TFF for the stream tables. To learn more about TFF files see the Aspen Plus System Management.
User Fortran
User Fortran Templates
There are several ways for you to customize your models by adding calculations in Fortran. The End-Use Properties section of Chapter 2 described how to setup a user Prop-Set for calculating end-use properties. Chapter 4 described how to setup user unit operation models, user kinetic models, and user property models. Templates are available for your use in creating the Fortran files used in these features. You will find these templates in the following location:
Version Windows Location %asptop%\user
User Fortran Linking

User Fortran calculations in the form of user routines are linked dynamically to Aspen Polymers during a simulation. Within user Fortran, you will often access utilities located within Aspen Polymers. In order to access these utilities, you will need to know the name of the object libraries where they are located. This applies to the utilities described in Appendix C. The name of the utility as shown in the example call sequence includes the name of the object library where it is located. You can also create your own dynamic link libraries to hold your user Fortran files. The Aspen Plus System Management guide describes how to work with Fortran code modifications.
Troubleshooting Guide
Following are tips to help you diagnose and resolve problems you may run into while setting up or running Aspen Polymers.
User Interface Problems

A list of symptoms relating to problems you may encounter when using the user interface is provided below. Possible causes and solutions are given for each symptom.
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Symptom The polymer input forms cannot be found on the GUI.
Cause The installation was not complete.
Solution You must locate your installation CD and do an incremental installation of Aspen Polymers. Select Aspen Polymers from the product list and chose the subcomponents button to select the Aspen Polymers steady state installation option. Enable Aspen Polymers. From the Tools menu, select Options. On the Startup tab there is a box entitled Enable forms for layered products. Make sure you select Aspen Polymers You must enable Aspen Polymers (From the Tools menu, Select Options, click on the Startup tab). In the Data Browser, select Polymers (Polymers will appear as incomplete), right mouse click, select Delete. Usually, when you crash, a backup file is created. Startup Aspen Plus again, then you should be able to recover your file. If the invalid operation was caused by Aspen Plus, repeat the input steps that lead to the crash, verify that it is reproducible, and submit the problem to Technical Support. Export an input summary. Run the input summary alone, then examine the run history for simulation errors. Change the input specifications associated with the error and rerun. Free-up some disk space and run again. Also, consult the Aspen Plus System Management reference manual. An entire section is devoted to managing virtual memory on Win95/98 and WinNT. Make some disk space available or increase the amount of memory available to the application, then run again. If you are running on a remote hosts, there may have been a communication failure at the end of the simulation calculations. You can submit the run again or you can manually load the results file (.SUM) from the remote host. If you are running on a local PC host, Aspen Plus may have run out of memory to load the results. Make some disk space available or increase the amount of memory available to the application and run again.
Aspen Polymers is installed but not enabled.
A file created without using polymer features appears incomplete in the components record. Windows crashes during input specifications.
You visited the polymer record while creating the file, then later switched off Aspen Polymers.
An invalid operation was performed either by the Aspen Plus program or by another program running simultaneously.
Windows crashes during simulation calculations.
The simulation engine encountered an error that could not be transferred to the GUI.
Aspen Plus ran out of resources to create run files. This can happen especially for large simulations. You may see error messages referring to the amount of virtual memory available. Aspen Plus ran out of memory to load dynamic link libraries. Windows crashes after simulation is complete. Aspen Plus could not load the simulation results.
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Symptom
Cause
Solution If the load failure was not due to any of the above, there may be some information recorded in the results file (.SUM) that is causing the problem. Contact Technical Support and be prepared to supply the results file and/or your saved simulation file.
Simulation Engine Run-Time Problems

A list of symptoms relating to problems you may encounter with the simulation engine at run-time are provided below. Possible causes and solutions are given for each symptom.
Symptom During simulation calculations an error message occurs for a license failure. Cause The application could not find a valid free license to complete the simulation. Solution If the license error message refers to "Feature 10". This means that you do not have a license for Aspen Plus itself. If you are using a licensed installation, then this could be a temporary license failure. This can happen for multi-user sites, or if you are using a license manager located on a network. In that case, you simply need to try again later. If you are using an installation with a single activator, then your license key file may be corrupted, the port where the activator is plugged in could be damaged, or the activator could be damaged. To correct your license key files, perform a license key installation again. If the problem is your activator, contact Technical Support to have it replaced. If the license error message refers to another feature number, you may still have run into a temporary license failure (see above). In that case, try again. If this was not a temporary license failure, then you created a simulation file which uses features for which you are not licensed. If the message refers to "Feature 15", then you are trying to use Aspen Polymers without a valid license. Other feature numbers refer to specific add-on products. You must contact AspenTech to obtain a valid Aspen Polymers license. A message box comes up stating that an error occurred in the Aspen Plus engine. See "Windows crashes during simulation calculations" under User Interface Problems. See also "After one run a subsequent run following an input change crashes" later in this section. Aspen Plus ran out of resources to load dynamic link libraries. See "Windows crashes during simulation calculations" under User Interface Problems. See also "After one run a subsequent run following an input change crashes" later in this section.
A run history message appears referring to a dynamic load module error.
See "Windows crashes during simulation calculations" under User Interface Problems.
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Symptom
Cause You are referencing user Fortran and do not have the compiled object file in your working directory. The working directory is the location from which you opened an existing file. If you created a file from a template or opened an existing file from a floppy or a write protected area (e.g. \xmp or \app) the working directory is as specified in Tools Options Startup.
Solution Compile the user Fortran and place it in your run directory.
A run history message appears which refers to "Virtual Memory Exhausted". After one run a subsequent run following an input change crashes.
You ran out of virtual memory space to load the run files.
See the Aspen Plus System Management, which discusses virtual memory management.
The problem size has changed as a result of the input or for other reasons Aspen Plus unsuccessfully tried to reuse the previous run data space. Usually an error message appears which states that a "Fatal error has been encountered".
Usually after the crash you should be able to recover your file and run with the input change. To prevent this from happening for the same run, reinitialize the simulation before making repeated runs. This is still a problem that should be reported to Technical Support.
References
Aspen Engineering Suite Installation Guide for Windows. Cambridge, MA: Aspen Technology, Inc. Aspen Plus System Management. Cambridge, MA: Aspen Technology, Inc. Aspen Plus User Guide. Cambridge, MA: Aspen Technology, Inc.
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A Component Databanks
This appendix documents the Aspen Polymers (formerly known as Aspen Polymers Plus) component databanks. There are currently two databanks available: POLYMER Databank - containing polymer pure component parameters SEGMENT Databank - containing segment pure component parameters
In addition users may retrieve parameters from the Aspen Plus databanks.
Pure Component Databank

The pure component databanks contain pure component data for over 1500 species. Typically components such as monomers, solvents, catalysts, initiators, etc. would be retrieved from the pure component databanks. The parameters in these databanks include those listed in POLYMER Property Parameters on page 378.
POLYMER Databank
POLYMER contains property parameters for polymers. Note that a generic polymer component is available in the databank for custom designed polymers.
POLYMER Property Parameters

The following table shows the parameters stored in the POLYMER databank:
Parameter CPIG DGFVK DHFVK DHVLWT No. Element 11 1 1 5 Description Ideal gas heat capacity Free energy of formation, ideal gas reference state Heat of formation, ideal gas reference state Heat of vaporization
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MW* OMEGA PC PLXANT TC VC VLTAIT ZC *
1 1 1 9 1 1 9 1
Polymer reference molecular weight Acentric factor Critical pressure Antoine coefficient Critical temperature Critical volume Tait molar volume model coefficients Critical compressibility factor
MW is a reference molecular weight calculated as the average segment molecular weight using:
MW =
MWSEG
NSEG
For the generic polymer component MW is set to 1.
POLYMER Databank Components

The following table shows the polymers contained in the POLYMER databank:
Alias ABS BR-1 CA-1 Cellulose Chitosan CPE CTA Dextran EVA EEA EPR HDPE Heparin Hyaluronic I-PB I-PMMA I-PP Keratan LDPE LLDPE NBR NYLON6 Polymer Name Acrylonitrile-butadiene-styrene Poly(butadiene) Cellulose-acetate Cellulose Chitosan Chlorinated-Poly(ethylene) Cellulose-triacetate Dextran Ethylene-vinyl-acetate Ethylene-ethyl-acrylate Ethylene-propylene High-density-Poly(ethylene) Heparin Hyaluronic-Acid Isotactic-Poly(1-butene) Isotactic-Poly(methyl-methacryl) Isotactic-Poly(propylene) Keratan-Sulfate Low-density-poly(ethylene) Linear-low-density-poly(ethylene) Nitrile-butadiene-rubber Nylon-6
379
Alias NYLON66 PAA P(ACA&S) PALA PAMIDE PAMS P(AMS&AN) PAN PARA PARG PASN PASP PB-1 PBA PBMA P(BMA&S) PBS-1 PBT PC-1 P(C&DMS) PCHMA PCYS PD-1 PDMA PDMS P(DMS&S) PE PEA PEEK PEG P(EG&PG) PEMA PEO P(EO&POX) P(E&P) PET P(E&VAC) PGLN PGLU PGLY PH PHA PHENOXY
Polymer Name Nylon-66 Poly(acrylic-acid) Poly(acrylamide-styrene) Poly(alanine) Poly(amide) Poly(alpha-methylstyrene) Poly(a-methylstyrene-AN) Poly(acrylonitrile) Poly(acrylamide) Poly(arginine) Poly(asparagine) Poly(aspartic-acid) Poly(1-butene) Poly(n-butyl-acrylate) Poly(n-butyl-methacrylate) Poly(n-butyl-methac-styrene) Poly(butadiene-styrene) Poly(butylene-terephthalate) Poly(carbonate) Poly(carbonate-dimet-siloxane) Poly(cyclohexyl-methacrylate) Poly(cysteine) Poly(decene-1) Poly(decyl-methacrylate) Poly(dimethylsiloxane) Poly(dimethylsiloxane-styrene) Poly(ethylene) Poly(ethyl-acrylate) Poly(ether-ether-ketone) Poly(ethylene-glycol) Poly(eth-glycol-prop-glycol) Poly(ethyl-methacrylate) Poly(ethylene-oxide) Poly(eth-oxide-prop-oxide) Poly(ethylene-propylene) Poly(ethylene-terephthalate) Poly(ethylene-vinyl-acetate) Poly(glutamine) Poly(glutamic-acid) Poly(glycine) Poly(heptene-1) Poly(n-hexyl-acrylate) Phenoxy
380
Alias PHIS PHMA PI PIB PIBMA PILE PIP-1 PLEU PLYS PMA P(MAA&MMA) P(MAA&S) P(MAA&VAC) PMET PMMA PMMS PMP PMVPD PNA POCS POE POLYMER POM POMS POP PP PPA PPBRS PPEMA PPG PPHE PPO PPMA PPMOS PPMS PPOX PPRO PPS PS-1 PSBMA PSER PSF P(S&VP)
Polymer Name Poly(histidine) Poly(n-hexyl-methacrylate) Poly(imide) Poly(isobutylene) Poly(isobutyl-methacrylate) Poly(isoleucine) Poly(isoprene) Poly(leucine) Poly(lysine) Poly(methyl-acrylate) Poly(methac-acid-met-methac) Poly(methac-acid-styrene) Poly(methac-acid-vin-acetate) Poly(methionine) Poly(methyl-methacrylate) Poly(m-methylstyrene) Poly(4-methyl-1-pentene) Poly(2-methyl-5-vinylpyridine) Poly(sodium-acrylate) Poly(o-chlorostyrene) Poly(oxyethylene) Generic polymer component Poly(oxymethylene) Poly(o-methylstyrene) Poly(oxypropylene) Poly(propylene) Poly(n-propyl-acrylate) Poly(p-bromostyrene) Poly(n-pentyl-methacrylate) Poly(propylene-glycol) Poly(phenylalanine) Poly(phenylene-oxide) Poly(n-propyl-methacrylate) Poly(p-methoxystyrene) Poly(p-methylstyrene) Poly(propylene-oxide) Poly(proline) Poly(phenylene-sulfide) Poly(styrene) Poly(sec-butyl-methacrylate) Poly(serine) Poly(sulfone) Poly(sytrene-vinylpyrrolidone)
381
Alias P(S&VPD) PT-1 PTFE PTHR PTRP PTYR PU-1 PVA PVAC P(VAC&VAL) PVAL PVAM PVC PVCAC PVDC PVDF PVF PVI PVME PVO PVP PVPD SAN SBR UF
Polymer Name Poly(styrene-4-vinylpyridine) Poly(tetrahydrofuran) Poly(tetrafluoroethylene) Poly(threonine) Poly(tryptophan) Poly(tyrosine) Poly(urethane-fiber) Poly(vinyl-alcohol) Poly(vinyl-acetate) Poly(vin-acetate-vin-alcohol) Poly(valine) Poly(vinyl-amine) Poly(vinyl-chloride) Poly(vin-chloride-vin-acetate) Poly(vinylidene-chloride) Poly(vinylidene-fluoride) Poly(vinyl-fluoride) Poly(vinyl-isobutyl-ether) Poly(vinyl-methyl-ether) Poly(vinylpropionate) Poly(vinylpyrrolidone) Poly(4-vinyl-pyridine) Styrene-acrylonitrile Styrene-butadiene-rubber Urea-formaldehyde
SEGMENT Databank
SEGMENT contains property parameters for polymer segments. Note that a special nomenclature was devised to identify polymer segments. The segment name consists of the name of the monomer from which it originates, followed by a label to identify it as a repeat unit (-R) or an end group (-E). In cases where several molecular structures are possible, a numeric subscript is used to differentiate the isomers. A similar convention is used for assigning component aliases.
SEGMENT Property Parameters

The following table shows the parameters stored in the SEGMENT databank:
Parameter No. Element Description
382
ATOMNO
10
Vector of atomic number of chemical elements in segment (used with NOATOM) Crystalline heat capacity Ideal gas heat capacity* Liquid heat capacity Free energy of formation, ideal gas reference state Enthalpy of condensation Enthalpy of formation, ideal gas reference state Enthalpy of sublimation Crystalline density Glass density Liquid density Molecular weight Vector of number of each type of chemical element in segment (used with ATOMNO) Glass transition temperature Melt transition temperature Van Krevelen functional groups Van der Waals volume UNIFAC functional groups
CPCVK CPIG CPLVK DGFVK DHCON DHFVK DHSUB DNCVK DNGVK DNLVK MW NOATOM
6 11 6 1 1 1 1 4 5 4 1 10
TGVK TMVK VKGRP VOLVW UFGRP
1 1 24 1 24
Estimated from Joback functional group.
SEGMENT Databank Components

The following table shows the SEGMENT databank components:
Alias CF2-R CO-R CHF2-E CH2O-R C2O2-R Segment Name Methylene-fluoride-R Carbonyl-R Methylene-fluoride-E Oxymethylene-R Oxalic-acid-R Molecular Structure
CF2
O C
CHF2 OCH2
O O C C O O
C2HO3-E
Oxalic-acid-E
C COH
383
Alias C2H2-R-1
Segment Name cis-Vinylene-R
Molecular Structure
C2H2-R-2
trans-Vinylene-R
C2H2-R C2H2CL-E C2H2F-E C2H2CL2-R C2H2F2-R C2H3-E C2H3CL-R C2H3F-R C2H3NO-R C2H3O-E C2H3O-E-1
Vinylidene-R Vinyl-chloride-E Vinyl-fluoride-E Vinylidene-chloride-R Vinylidene-fluoride-R Vinyl-E Vinyl-chloride-R Vinyl-fluoride-R Glycine-R Acetate-E Oxyvinyl-E
C CH2
CH CHCl
CH CHF
CH2 CCl2 CH2 CF2 CH CH2 CH2 CHCl CH2 CHF

O NH CH2 C
~COCH3
O CH CH2
C2H3O-E-2
Vinyl-alcohol-E
CH CH OH
C2H4-R
Ethylene-R
CH2 CH2
CH CH NH2
C2H4N-E
Vinylamine-E-1
C2H4NO-E
Glycine-E-1
O NH2 CH2 C
O
C2H4NO2-E Glycine-E-2
NH CH2 C
CH2 CH2 O
OH
C2H4O-R-1
Ethylene-oxide-R
384
Alias C2H4O-R-2
Segment Name Oxyethylene-R
Molecular Structure
O CH2 CH2
CH2 CH OH
C2H4O-R-3
Vinyl-alcohol-R
C2H4O2-R C2H5-E
Ethylene-glycol-R Ethylene-E
O CH2 CH2 O
CH2 CH3
CH2 CH NH2
C2H5N-R
Vinylamine-R
C2H5O-E-1
Ethylene-oxide-E-1
CH2 CH2 OH
C2H5O-E-2 C2H5O2-E
Ethylene-oxide-E-2 Ethylene-glycol-E
CH3 CH2 O
O CH2 CH2 OH
CH2 CH2 NH2
CH3
C2H6N-E
Ethyleneamine-E
C2H6OSi-R
Dimethyl siloxane-R
Si O CH3 CH3
C2H7OSi-E
Dimethyl siloxane-E
Si OH CH3
O O CCH2C
C3H2O2-R
Malonic -acid-R
CH CH
C3H2O2Na-E Sodium acrylate-E-1
ONa
385
Alias
Segment Name
Molecular Structure
C3H3N-R
Acrylonitrile-R
CH2 CH C N
CH CH
C3H3NO-R Acrylamide-R-1
C NH
CH CH
C3H3O2-E Acrylic acid-E-1
OH
CH2 CH
C3H3O2Na-R Sodium-acrylate-R
O
C3H303-E Malonic-acid-E
C
O
ONa
CCH2COH
CH CH
C3H4NO-E Acrylamide-E-1
C NH2
CH2 CH
C3H4NO-B Acrylamide-B
O
O N C
C NH
C3H4N2O-B
Urea-formaldehyde-R
N CH2 CH2
C3H4O2-R
Acrylic-acid-R
CH2 CH C O OH
CH2
C3H4O2Na-E Sodium-acrylate-E-2
CH2 C O ONa
386
Alias
Segment Name
Molecular Structure
C3H5-E
Propylene-E-1
CH CH CH3
C3H5Cl-R
2-chloropropylene-R
CH2 CHCl CH2 CH2 CH2 C O CH2 CH NH
C3H5NO-R-1
Acrylamide-R-2
C3H5NO-R-2
Acrylamide-R-3
C O NH2
O
C3H5NO-R-3
Alanine-R
NH CH C CH3
O
C3H5NOS-R Cysteine-R
NH CH C CH2 SH
O
C3H5NO2-R Serine-R
NH CH C CH2 OH
CH2
C3H5O2-E Acrylic-acid-E-2
CH2 C O OH
C3H6-R
Propylene-R
CH2 CH CH3
CH2 CH2
C3H6NO-E-1
Acrylamide-E-2
NH2
387
Alias
Segment Name
Molecular Structure
O
C3H6NO-E-2 Alanine-E-1
NH2 CH C CH3
O
C3H6NOS-E
Cysteine-E-1
NH2 CH C CH2 SH
O
C3H6NO2-E-1 Alanine-E-2
NH CH C CH3 OH O
C3H6NO2-E-2
Serine-E-1
NH2 CH C CH2 OH
O
C3H6NO2S-E
Cysteine-E-2
NH CH C CH2 SH OH
O
C3H6NO3-E Serine-E-2
NH CH C CH2 OH
O CH2 CH CH3
CH2 CH O CH3
OH
C3H6O-R-1
Oxypropylene-R
C3H6O-R-2
Propylene-oxide-R
388
Alias
Segment Name
Molecular Structure
C3H6O-R-3
Vinyl-methyl-ether-R
CH2 CH O CH3
O CH2 CH O CH3
~O(CH2)3O~
C3H6O2-R C3H6O2-R-1 C3H6O2-R-2
Propylene-glycol-R 1,3-Propanediol-R 1,2-Propanediol-R
OCHCH2O CH3
C3H7-E
Propylene-E-2
CH2 CH2 CH3 HO CH2 CH CH3 CH2 CH OH CH3

~OCH(CH3)2 ~O(CH2)2CH3
C3H7O-E-1
Oxypropylene-E
C3H7O-E-2 C3H7O-E-i C3H7O-E-n C3H7O2-E C3H7O2-E-1 C3H7O2-E-P
Propylene-oxide-E i-Propanol-E n-Propanol-E Propylene-glycol-E 1,3-Propanediol-E 1,2-Propanediol-E-P
O CH2 CH OH CH3
~O(CH2)3OH
OCHCH2OH CH3
C3H7O2-E-S
1,2-Propanediol-E-S
OCH2CHCH3 OH
O O C C H C H C
C4H2O2-R-cis
Maleic-acid-R
O H
C4H2O2-R-tra Fumaric-acid-R
C C C H O
389
Alias
Segment Name
Molecular Structure
O O
C4H3O3-E-cis Maleic-acid-E
C C H C
COH H
O H
C4H3O3-E-tra Fumaric-acid-E
COH C C H O
O
C
O
C4H4O2-R C4H5-B C4H5-E-1 C4H5-E-2
Succinic-acid-R Butadiene-B Butadiene-E-1 Butadiene-E-2
C(CH2)2C
CH2 CH CH CH
CH CH CH CH2
CH2 CH C CH2
NH CH C
C4H5NO3-R Aspartic-acid-R
CH2 C O OH
C CH2
C4H5O2-E-1 Methyl-acrylate-E-1
OCH3
C4H5O2-E-2
Methyl-acrylic-acid-E-1
CH3 CH C C O OH
CH CH O C CH3 O
O O C(CH2)2COH
C4H5O2-E-3
Vinyl-acetate-E-1
C4H5O3-E C4H6-R-1
Succinic-acid-E Butadiene-R-1
CH2 CH CH CH2
390
Alias
Segment Name
Molecular Structure
C4H6-R-2
Butadiene-R-2
CH2
CH CH CH2
NH2 CH C
C4H6NO3-E Aspartic-acid-E-1
CH2 C O OH NH CH C O OH
C4H6NO4-E
Aspartic-acid-E-2
CH2 C O OH NH CH C
C4H6N2O2-R
Asparagine-R
CH2 C NH2 O
CH2
C4H6O2-R-1 Methyl-acrylate-R
CH C O CH3
C4H6O2-R-2
Methyl acrylic-acid-R
CH2 O
CH3 C C OH
CH2 CH
C4H6O2-R-3 Vinyl-acetate-R
O O
C CH3
C4H7-E-1
1-Butene-E
CH CH C2H5
391
Alias
Segment Name
Molecular Structure
C4H7-E-2
Isobutylene-E
CH C
CH3 CH3
C4H7-E-3 C4H7-E-4
Butadiene-E-3 Butadiene-E-4
CH2 CH2 CH CH2 CH2 CH CH CH3

NH CH C O
C4H7NO2-R
Threonine-R
CHOH CH3
O NH2 CH C
C4H7N2O2-E
Asparagine-E-1
CH2 O C NH2
O NH CH C
C4H7N2O3-E Asparagine-E-2
CH2 O C NH2
OH
C4H7O2-E-1
Methyl-acrylate-E-2
CH2 CH2 C O O CH3

CH3
C4H7O2-E-2
Methyl-acrylic-acid-E-2
CH2 CH C O OH
CH3
C4H7O2-E-3 Methyl-acrylic-acid-E-3
C CH3 C O OH
392
Alias
Segment Name
Molecular Structure
CH2 CH2
C4H7O2-E-4 Vinyl-acetate-E-2
C O O CH3
C4H8-R-1
1-Butene-R
CH2 CH C2H5
CH3 CH2 C CH3
C4H8-R-2
Isobutylene-R
NH2 CH C
C4H8NO2-E Threonine-E-1
CHOH CH3
NH CH C O OH
C4H8NO3-E
Threonine-E-2
CHOH CH3
C4H8O-R C4H8O2-R C4H8O3-R C4H9O-E-1 C4H9O-E-2 C4H9O2-E C4H9O3-E
Tetrahydrofuran-R Butylene-glycol-R Diethylene-glycol-R Tetrahydrofuran-E-1 Tetrahydrofuran-E-2 Butylene-glycol-E Diethylene-glycol-E
CH2 CH2 CH2 CH2 O
O C4H8 O
O C2H4 O C2H4 O
C4H8 OH
C4H9 O
O C4H8 OH
O C2H4 O C2H4 OH
O O C(CH2)3C
C5H6O2-R
Glutaric-acid-R
C5H7NO-R
Proline-R
O C
393
Alias
Segment Name
Molecular Structure
NH CH C
C5H7NO3-R Glutamic-acid-R
C2H4 C O OH
CH3
C5H7O2-E-1
Methyl-methacrylate-E-1
CH C C O O CH3
CH CH C O O C2H5
CH CH O C C2H5 O
O O C(CH2)3COH
C5H7O2-E-2
Ethyl-acrylate-E-1
C5H7O2-E-3
Vinyl-propionate-E-1
C5H7O3-E
Glutaric-acid-E
C5H8-R
Isoprene-R
CH2 C CH CH2 CH3 O C
C5H8NO-E
Proline-E-1
HN
C5H8NO2-E
Proline-E-2
O C OH
394
Alias
Segment Name
Molecular Structure
O NH2 CH C
C5H8NO3-E Glutamic-acid-E-1
C2H4 C O OH
O NH CH C
C5H8NO4-E
Glutamic-acid-E-2
C2H4 OH C O OH
O NH CH C
C5H8N2O2-R-1 Glutamine-R
C2H4 C O
O
NH2
O
C5H8N2O2-R-2
Trimethylene-diisocyanate-R
NH C3H6 NH
C5H8O2-R-1
Methyl-methacrylate-R
CH3 C CH2 O C OCH3
C5H8O2-R-2
Ethyl-acrylate-R
CH2 CH C O O C2H5
C5H8O2-R-3
Vinyl-propionate-R
CH2 CH O C C2H5 O
CH CH C3H7
C5H9-E
1-Pentene-E-1
395
Alias
Segment Name
Molecular Structure
O
C5H9NO-R Valine-R
NH CH C CH CH3 CH3
O NH CH C
C5H9NOS-R Methionine-R
C2H4 S CH3
O NH2 CH C
C5H9N2O2-E Glutamine-E-1
C2H4 C O NH2
C5H9N2O3-E
Glutamine-E-2
C5H9O2-E-1
CH3 CH2 CH C O O CH3 CH3 C CH3 C O OCH3

CH2 CH2
C5H9O2-E-2
C5H9O2-E-3
Ethyl-acrylate-E-2
C O
O C2H5
396
Alias
Segment Name
Molecular Structure
CH2 CH2
C5H9O2-E-4 Vinyl-propionate-E-2
O O
C C2H5
C5H10-R
1-Pentene-R
CH2 CH C3H7
C5H10NO-E
Valine-E-1
C5H10NOS-E
Methionine-E-1
O NH2 CH C C2H4 S CH3

O
C5H10NO2-E
Valine-E-2
NH CH C CH CH3 CH3
OH
O
C5H10NO2S-E Methionine-E-2
NH CH C OH C2H4 S CH3
S
O
C6H4S-R
Phenylene-sulfide-R
C6H5O-E
Phenol-E
C6H5S-E-1
Phenylene-sulfide-E-1
C6H5S-E-2
Phenylene-sulfide-E-2
SH
397
Alias
Segment Name
Molecular Structure
NH
C6H6N2-R-M m-Phenylene-diamine-R
NH
NH
C6H6N2-R-O o-Phenylene-diamine-R
NH
C6H6N2-R-P
p-Phenylene-diamine-R
NH
NH
NH
NH2
C6H7N2-E-M
m-Phenylene-diamine-E
NH
C6H7N2-E-O o-Phenylene-diamine-E
NH2
C6H7N2-E-P
p-Phenylene-diamine-E
NH
NH2
C6H7N3O-R
Histidine-R
C6H8NO-E
Vinylpyrrolidnone-E-1
CH CH O N C
C6H8N3O-E
Histidine-E-1
C6H8N3O2-E
Histidine-E-2
398
Alias
Segment Name
Molecular Structure
C6H8O2-R
Adipic-acid-R
O C (CH2)4
O C
CH2 CH
C6H9NO-R Vinylpyrrolidnone-R
CH C CH3
C6H9O2-E-1 Ethyl-methacrylate-E-3
O C2H5
CH CH
C6H9O2-E-2 n-Propyl-acrylate-E-1
O
C6H9O3-E Adipic-acid-E
O C3H7
O C OH
O C (CH2)4
CH2 CH CH2
C6H10-R
1,4-Hexadiene-R
CH CH CH3
CH2 CH2
C6H10NO-E Vinylpyrrolidnone-E-3
C6H10O2-R-1
Ethyl-methacrylate-R-1
CH3 CH2 C O C O C2H5
CH2 CH
C6H10O2-R-2 n-Propyl-acrylate-R
O C3H7
399
Alias
Segment Name
Molecular Structure
C6H10O3-R
Amylose-R
CH2OH O
C6H10O5-R-1
Cellulose-R
CH2OH O OH OH
C6H10O5-R-2
Dextran-R
O CH2 O HO OH OH
CH CH CH3 CH2 CH CH3
CH CH C4H9
C6H11-E-1
4-Methyl-1-pentene-E-1
C6H11-E-2
1-Hexane-E-1
C6H11NO-R-1
Caprolactam-R
NH (CH2)5 C
NH CH C
C6H11NO-R-2 Isoleucine-R
CH C2H5 CH3
O NH CH C CH2 CH CH3 CH3
C6H11NO-R-3
Leucine-R
C6H11O-E
Vinyl-isobutyl-ether-E-1
CH CH CH3 O CH2 CH CH3
400
Alias
Segment Name
Molecular Structure
C6H11O2-E-1
Ethyl-methacrylate-E-1
CH3 CH2 CH C O O C2H5 CH3
C6H11O2-E-2
Ethyl-methacrylate-E-2
CH3 C C O O C2H5
CH2 CH2
C6H11O2-E-3
n-Propyl-acrylate-E-2
C O
O C3H7
CH2OH
C6H11O3-E Amylose-E
HO
C6H11O5-E
Cellulose-E-1
HO
CH2OH O OH OH CH2OH O OH OH CH2 O O OH OH
C6H11O6-E-1
Cellulose-E-2
OH
C6H11O6-E-2
Dextran-E-2
HO
OH
C6H12-R-1
1-Hexane-R
CH2 CH C4H9
401
Alias
Segment Name
Molecular Structure
C6H12-R-2
4-Methyl-1-pentene-R
CH2 CH CH3 CH2 CH CH3

O (CH2)5 C
C6H12NO-E-1
Caprolactam-E-1
NH2
C6H12NO-E-2
Isoleucine-E-1
O NH2 CH C CH CH3 C2H5

NH2 CH C CH2 O CH3 CH3
C O OH
C6H12NO-E-3
Leucine-E-1
CH
C6H12NO2-E-1
Caprolactam-E-2
NH (CH2)5
C6H12NO2-E-2
Isoleucine-E-2
NH CH C
OH CH CH3 C2H5
O
NH CH C
C6H12NO2-E-3 Leucine-E-2
CH2
OH CH CH3 CH3
C6H12N2O-R
Lysine-R
NH CH C
C4H8 NH2
402
Alias
Segment Name
Molecular Structure
O NH CH C CH2 CH2 CH2 NH C NH NH2

CH2 CH CH3 O CH2 CH CH3
C6H12N4O-R
Arginine-R
C6H12O-R
Vinyl-isobutyl-ether-R
C6H12O2-R
Hexamethylene-diol-R
O (CH2)6 O
CH2 CH2 CH3 CH2 CH CH3
CH3 CH CH3 CH2 CH CH3
C6H13-E-1
C6H13-E-2
C6H13-E-3
1-Hexane-E-2
CH3 CH C4H9
C6H13N2O-E
Lysine-E-1
NH2 CH C
C4H8 NH2
C6H13N2O2-E Lysine-E-2
NH CH C
OH C4H8 NH2
403
Alias
Segment Name
Molecular Structure
O NH2 CH C CH2 CH2 CH2 NH C NH NH2 O NH CH C OH CH2 CH2 CH2 NH C NH NH2

CH2 CH2 CH3 O CH2 CH CH3
C6H13N4O-E
Arginine-E-1
C6H13N4O2-E
Arginine-E-2
C6H13O-E
Vinyl-isobutyl-ether-E-2
C6H13O2-E C6H14N2-R C6H15N2-E
Hexamethylene-diol-E Hexamethylene-diamine-R Hexamethylene-diamine-E
O (CH2)6 OH NH (CH2)6 NH NH (CH2)6 NH2

O C
C7H5O-E
Benzoic-acid-E
O
C7H5O2-E Phenylcarbonate-E
CH CH
C7H6N-E 4-Vinyl-pyridine-E-1
404
Alias
Segment Name
Molecular Structure
CH2 CH
C7H7N-R 4-Vinyl-pyridine-R
N CH2 CH2
C7H8N-E 4-Vinyl-pyridine-E-2
N
C7H10O2-R Pimelic-acid-R
C(CH2)5C
C7H11O2-E-1
n-Butyl-acrylate-E-1
CH CH C O O C4H9
C7H11O2-E-2
n-Propyl-methacrylate-E-1
CH3 CH C C O O C3H7
O O C(CH2)5COH
C7H11O3-E
Pimelic-acid-E
CH2 CH
C7H12O2-R-1 n-Butyl-acrylate-R
C O O C4H9
C7H12O2-R-2
n-Propyl-methacrylate-R
CH3 CH2 C C O O C3H7

CH CH C5H11
C7H13-E
1-Heptene-E-1
CH2 CH2
C7H13O2-E-1 n-Butyl-acrylate-E-2
C O O C4H9
405
Alias
Segment Name
Molecular Structure
C7H13O2-E-2
CH3 CH2 CH C O O C3H7 CH3 CH3 C C O O C3H7 CH2 CH C5H11 CH2 CH2 C5H11
C7H13O2-E-3
C7H14-R
1-Heptene-R
C7H15-E-1
1-Heptene-E-2
C7H15-E-2
1-Heptene-E-3
CH3 CH C5H11
C8H4O2-R
Terephthalate-R
O C
O C
O
C8H4O2-R-1 Phthalate-R
O C O C
O C OH
O C
C8H4O2-R-2 Isophthalate-R
C8H5O3-E
Terephthalic-acid-E
O C
O
C8H5O3-E-1 Phthalic-acid-E
O C OH
406
Alias
Segment Name
Molecular Structure
O C
C8H5O3-E-2 Isophthalic acid-E
O C OH
CH CH
C8H6Br-E p-Bromostyrene-E-1
Br
CH CH
C8H6Cl-E-1 o-Chlorostyrene-E-1
Cl
CH CH
C8H6Cl-E-2 p-Chlorostyrene-E-1
Cl
CH CH
C8H7-E Styrene-E-1
CH2 CH
C8H7Br-R p-Bromostyrene-R
Br
CH2 CH
C8H7Cl-R-1 o-Chlorostyrene-R
Cl
CH2 CH
C8H7Cl-R-2 p-Chlorostyrene-R
Cl
CH2 CH
C8H8-R Styrene-R
407
Alias
Segment Name
Molecular Structure
CH2 CH2
C8H8Br-E p-Bromostyrene-E-2
Br
CH2 CH2
C8H8Cl-E-1 o-Chlorostyrene-E-2
Cl
CH2 CH2
C8H8Cl-E-2 p-Chlorostyrene-E-2
Cl
CH CH
C8H8N-E 2-Methyl-5-vinylpyridine-E-1
CH3
CH3
C8H8O-R Phenylene-oxide-R
O CH3
CH2 CH2
C8H9-E
Styrene-E-2
CH2
C8H9N-R 2-Methyl-5-vinylpyridine-R
CH N
CH3
CH2 CH2
C8H10N-E 2-Methyl-5-vinylpyridine-E-2
CH3
408
Alias C8H12O2-R
Segment Name Suberic-acid-R
Molecular Structure
C(CH2)6C
C8H12O6-R
Cellulose-acetate-R
O CH2 O C CH3 O OH OH
C8H13O2-E-1
n-Butyl-methacrylate-E-1
CH C O
CH3 C O C4H9
CH3 C CH3 O CH2 CH CH3
C8H13O2-E-2
Isobutyl-methacrylate-E-1
CH C O
C8H13O2-E-3
sec-Butyl-methacrylate-E-1
CH C O
CH3 C
O
CH3 O CH C2H5
C8H13O3-E
Suberic-acid-E
C(CH2)6COH
C8H13O6-E
Cellulose-acetate-E
OH
O CH2 O C CH3 O OH OH
C8H14N2O2-R
Hexamethylene-diisocyanate-R
O O C NH (CH2)6 NH C
C8H14O2-R-1
n-Butyl-methacrylate-R
409
Alias
Segment Name
Molecular Structure
C8H14O2-R-2
Isobutyl-methacrylate-R
CH3 CH2 C CH3 C O O CH2 CH CH3
C8H14O2-R-3
sec-Butyl-methacrylate-R
CH3 CH2 C CH3 C O O CH C2H5

CH CH C6H13
C8H15-E
1-Octene-E-1
C8H15O2-E-1
CH3 CH2 CH C O O C4H9
C8H15O2-E-2

CH2 CH CH3 CH3 CH3
C8H15O2-E-3
O CH2 CH
C8H15O2-E-4
CH3 CH3 C CH3 C O O CH2 CH CH3
C8H15O2-E-5
CH3 CH2 CH O C
CH3 O CH C2H5
410
Alias
Segment Name
Molecular Structure
C8H15O2-E-6
CH3 CH3 C CH3 C O O CH C2H5

CH2 CH C 6H13 CH2 CH2 C 6H13
C8H16-R
1-Octene-R
C8H17-E-1
1-Octene-E-2
C8H17-E-2
1-Octene-E-3
CH3 CH C6H13
C9H7O3-E
Dimethyl-terephthalate-E
O C
CH3 CH C
O C O CH3
C9H9-E-1
Alpha-Methylstyrene-E-1
CH CH
C9H9-E-2 m-Methylstyrene-E-1
CH3
CH CH
C9H9-E-3 o-Methylstyrene-E-1
CH3
CH CH
C9H9-E-4 p-Methylstyrene-E-1
CH3
411
Alias
Segment Name
Molecular Structure
O
C9H9NO-R Phenylalanine-R
NH CH C CH2
O NH CH C CH2
C9H9NO2-R
Tyrosine-R
OH
CH CH
C9H9O-E p-Methoxystyrene-E-1
OCH3
C9H10-R-1
alpha-Methylstyrene-R
CH3 CH2 C
CH2 CH
C9H10-R-2 m-Methylstyrene-R
CH3
CH2 CH
C9H10-R-3 o-Methylstyrene-R
CH3
CH2 CH
C9H10-R-4 p-Methylstyrene-R
CH3
412
Alias
Segment Name
Molecular Structure
O
C9H10NO-E Phenylalanine-E-1
NH2 CH C CH2
C9H10NO2-E-1
Phenylalanine-E-2
O NH CH C CH2 OH
O
C9H10NO2-E-2 Tyrosine-E-1
NH2 CH C CH2
OH
O NH CH C CH2 OH
C9H10NO3-E
Tyrosine-E-2
OH
CH2
C9H10O-R p-Methoxystyrene-R
CH
OCH3 CH3 CH
C9H11-E-1
alpha-Methylstyrene-E-2
CH2
413
Alias
Segment Name
Molecular Structure
C9H11-E-2
alpha-Methylstyrene-E-3
CH3 CH3 C
CH2 CH2
C9H11-E-3 m-Methylstyrene-E-2
CH3 CH2 CH2

C9H11-E-4 o-Methylstyrene-E-2
CH3
CH2 CH2
C9H11-E-5 p-Methylstyrene-E-2
CH3 CH2 CH2

C9H11O-E p-Methoxystyrene-E-2
OCH3
CH
C9H12-R Ethylidene-norbornene-R
CH CH2 CH C O CH CH3
CH CH2
C9H14O2-R
Azelaic-acid-R
C(CH2)7C
C9H15O2-E-1
n-Hexyl-acrylate-E-1
CH CH C O O C6H13
414
Alias
Segment Name
Molecular Structure
C9H15O2-E-2
n-Pentyl-methacrylate-E-1
CH3 CH C C O O C5H11
O O C(CH2)7COH
C9H15O3-E
Azelaic-acid-E
C9H16O2-R-1
n-Hexyl-acrylate-R
CH2 CH C O O C6H13
C9H16O2-R-2
n-Pentyl-methacrylate-R
C9H17-E
1-Nonene-E-1
CH CH C7H15
CH2 CH2 C O O C6H13
CH3
C9H17O2-E-1
n-Hexyl-acrylate-E-2
C9H17O2-E-2
CH2 CH C O O C5H11
C9H17O2-E-3
C9H18-R
1-Nonene-R
CH2 CH C 7H15
C9H19-E-1
1-Nonene-E-2
CH2 CH2 C7H15

CH3 CH C 7H15
C9H19-E-2
1-Nonene-E-3
415
Alias
Segment Name
Molecular Structure
CH CH
C10H12-R Dicyclopentadiene-R
CH CH2 CH CH CH CH
CH CH2
C10H15O2-E
Cyclohexyl-methacrylate-E-1
CH3 CH C C O O CH3 CH2 C C O O

O O
C10H16O2-R
Cyclohexyl-methacrylate-R
C10H16O2-R-1
Sebacic-acid-R
C(CH2)8C
C10H17O2-E-1
CH3 CH2 CH C O O
CH3 CH3 C C O O
O O C(CH2)8COH
C10H17O2-E-2
C10H17O2-E-3
n-Hexyl-methacrylate-E-1
C10H17O3-E
Sebacic-acid-E
416
Alias
Segment Name
Molecular Structure
C10H18O2-R
n-Hexyl-methacrylate-R

CH CH C8H17
C10H19-E
1-Decene-E-1
C10H19O2-E-1
CH3 CH2 CH C O O C6H13 CH3 CH3 C O C O C6H13
C10H19O2-E-2
C10H20-R
1-Decene-R
CH2 CH C8H17 CH2 CH2 C8H17 CH3 CH C8H17
C10H21-E-1
1-Decene-E-2
C10H21-E-2
1-Decene-E-3
O NH CH C
C11H10N2O-R Tryptophan-R
CH2 N
O NH2 CH C
C11H11N2O-E
Tryptophan-E-1
CH2 N
417
Alias
Segment Name
Molecular Structure
O NH CH C
C11H11N2O2-E Tryptophan-E-2
CH2 N
OH
C11H21-E
1-Undecene-E-1
CH CH C9H19 CH2 CH C9H19 CH2 CH2 C9H19
C11H22-R
1-Undecene-R
C11H23-E-1
1-Undecene-E-2
C11H23-E-2
1-Undecene-E-3
CH3 CH C9H19
C12H6O2-R
2,6-Napthalene-diacid-R
C12H7O3-E
2,6-Napthalene-diacid-E
C12H16O8-R
Cellulose-triacetate-R
O O CH3 C O
CH2 O
O O C CH3
O O C CH3
C12H17O8-E
Cellulose-triacetate-E
HO O CH3 C O
O CH2 O C CH3 O O O C CH3
418
Alias
Segment Name
Molecular Structure
CH2OH O
C12H22N2O8-R Chitosan-R
OH NH2 O O CH2OH O
OH NH2
C12H23-E 1-Dodecene-E-1
CH CH C10H21
CH2OH O OH NH2 O O CH2OH OH
C12H23N2O8-E
Chitosan-E-1
OH NH2 CH2OH O OH NH2

C12H24-R 1-Dodecene-R
OH NH2 O O CH2OH O
C12H23N2O9-E
Chitosan-E-2
HO
CH2 CH C10H21 CH2 CH2 C10H21
C12H25-E-1
1-Dodecene-E-2
C12H25-E-2
1-Dodecene-E-3
CH3 CH C10H21
C13H9O3-E
2,6-Napthalene-dimethylester-E
C14H23NO10-R
Heparin-R
HO
CH2OH O O OH
CH2OH O O OH NH C CH3
419
Alias
Segment Name
Molecular Structure
C14H24NO10-E
Heparin-E-1
HO
CH2OH O OH OH
CH2OH O O OH NH C CH3
C14H24NO11-E
Heparin-E-2
HO
CH2OH O O OH
OH O OH NH C CH3
CH2OH O
C14H25O2-E
Decyl-methacrylate-E-1
C14H26O2-R
Decyl-methacrylate-R

CH3 CH2 CH C O O C10H21
C14H27O2-E-1
Decyl-methacrylate-E-2
CH3
C14H27O2-E-2 Decylmethacrylate-E-3
CH3 C C O O C10H21 CH3
C15H14O2-R
Bisphenol-A-R
C CH3 CH3
C15H15O2-E
Bisphenol-A-E
C CH3
OH
420
B Kinetic Rate Constant Parameters
This appendix provides decomposition rate parameters for commonly used initiators. Within each group the initiators are arranged by increasing total number of carbon atoms. The parameters are grouped as follows: Water Soluble Azo-nitriles Solvent Soluble Azo-Nitriles Diacyl Peroxides Peroxycarbonates Alkyl Peroxides Hydroperoxides Peroxyesters C-C Initiators Sulfonyl Peroxides
Initiator Decomposition Rate Parameters

The table at the end of this section shows the decomposition rate parameters for monofunctional free-radical initiators. These parameters assume firstorder decomposition kinetics. These data are all included in the INITIATOR database in Aspen Polymers (formerly known as Aspen Polymers Plus). Initiator decomposition rates depend on several factors including temperature, pressure, solvent type, and initiator concentration.
Solvent Dependency
Decomposition rates are lowest in solvents that act as radical scavengers, such as poly chlorinated organic compounds (e.g., TCE). Initiators used for bulk-phase vinyl chloride polymerizations are typically in these types of
421
compounds since they closely mimic the solvent environment during polymerization. Decomposition rates may be increased by a factor of 2-3 in polar solvents such as chlorobenzene compared to reactions in non-polar solvents such as benzene. Decomposition rates of water-soluble initiators are typically measured in water. The table that follows lists the solvents in which the rate parameters are measured. The user may wish to apply correction factors to the rate parameters when the polymerization solvent environment is different than the measurement basis.
Concentration Dependency
At high initiator concentrations there is an induced initiation effect. Primary radicals attack and split un-decomposed initiator molecules. This reduces the measured half-life time and efficiency of the initiator. All of the data reported in the following table are based on measurements at relatively low initiator concentrations (0.2 molar or less). Although the standard decomposition rate expressions do not account for induced initiator, the user may modify the rate expression using a gel effect term.
Temperature Dependency
Initiator decomposition rates are reported in several formats including rate constants, half-life times at specified temperatures, and half-life temperatures at specified times. These data are all related to each other through the following equations:
E k Tref = A exp RT ref kT = ln(0.5) T60 = t 1 ,T

2
E1 1 kT = kTref exp R T Tref
E ln(0.5) R ln 3600 A
Where: A = = = = = f = = = Pre-exponential factor (1/sec) Decomposition rate at reference temperature (1/sec) Decomposition rate at temperature T, K Activation energy (J/kmol-K) Universal gas constant Reference temperature, K Temperature, K Half life at temperature T, sec
kTref
kT
E R
Tref
t 1 ,T
2
These equations were applied to the published raw data to allow the rate constants to be published in a concise format here.
422
Pressure Dependency
Most sources do not publish activation volume, which describe the pressure dependency of the reaction rates. Initiator decomposition reactions are known to exhibit pressure dependence over very wide ranges of pressure. For example, the half-life of organic peroxides double with a 3000 bar pressure increase (Degussa, 2004), which implies an activation volume of 1.9x10-5 m 3 / kmol . This term can be ignored for processes that operate at reasonably low pressures. The following table shows the decomposition rate parameters for monofunctional free-radical initiators at a reference temperature of 60C (Tref(K)=333.15). These data are all included in the INITIATOR database in Aspen Polymers.
423
Decomposition Rate Parameters Formula / Molecular Structure MW CAS No kref (1/s) A (1/sec) kcal/mol GJ/kmol 1 min 1 hr
Decomposition Activation Energy
Half Life Temperature, C 10 hr Solvent Source
ID
Long Name
Trade Name(s)
Water Soluble Azo-Nitriles C8H20N6Cl2 271.19264 2997-92-4 3.3436E-05 6.44E+14 29.4 0.12300 110.5 73.7 55.9 Water DuPont
ABAH
2,2-azo-bis(2amidinopropane) dihydrochloride
Vazo 56 (DuPont) V-50 (Wako Chem)
HCl HN H 2N
C12H22N2O4 258.31776 2638-94-0 7.3642E-06 5.12E+12 27.2 0.11380 132.7
N N NH2
NH HCl
VAZO68
4,4-azo-bis (4-cyanovaleric acid)
Vazo 68 (DuPont)
88.7
68.0
Water
DuPont
HOOC N N COOH
250.34712 20858-12-2 1.3404E-03 1.00E+15 27.2 0.11400
VA61
2,2-azo-bis[2-(2imidazolin-2-yl)propane]
VA-061 (Wako Chem)
C12H22N6
N N N N HN
O N N HN CH2 CH2OH
78.4
45.0
28.9
Acidic water
Wako
N H
C12H24N4O4 O
HOH 2CH 2C NH
VA86
2,2-Azobis[2-methyl-N-(2- VA-086 hydroxyethyl)propionamide]
288.34712
61551-69-7
6.7869E-06 7.95E+14
30.6
0.12800
123.9
86.0
67.7
Water
Wako
VAZO44
Vazo 44 (DuPont) VA-44 (WakoChem)
C12H24Cl2N6
N N 2HCl HN
482.53664 20858-12-2
323.26840
27776-21-2
1.3564E-04 8.10E+12
25.6
0.10700
103.3
63.0
44.0
Water
DuPont
2,2-azo-bis(N,Ndimethylene isobutyramidine) dihydrochloride
N H
C12H30N6O10S2
N N
VA46B
VA-046B (Wako Chem)
2,2-azo-bis[2-(2imidazolin-2-yl)propane disulfate dihydrate
N N HN H2 SO4 H2 O
349.30628 n/a
1.4388E-03 1.18E+17
30.4
0.12700
75.9
46.0
31.4
Water
Wako
N H
C14H26Cl2N6
N N
VA41
VA-041 (WakoChem)
2,2-azo-bis[2-(5-methyl2-imidazolin-2-yl)propane] dihydrochloride
N N N N N H HCl
351.32216
2.7035E-04 2.53E+15
28.9
0.12100
91.3
57.4
41.0
Water
Wako
N H HCl
N 2HCl HN N N NH
C14H34N6O8
HOO C N N HN HN NH NH CO OH 4 H 2O
VA58
2,2-azobis[2-(3,4,5,6VA-058 (WakoChem) tetrahydropyrimidin-2yl)propane] dihydrochloride
C14H28Cl2N6
102834-39-0 2.5342E-05 1.44E+15
30.1
0.12600
111.8
75.5
58.0
Water
Wako
VA57
2,2-azobis[N-(2carboxyethyl)-2methylpropionamidine] tetrahydrate
VA-057 (WakoChem)
414.45960
n/a
2.8824E-05 5.56E+14
29.4
0.12300
112.0
74.9
57.0
Water
Wako
424
Decomposition Rate Parameters Formula / Molecular Structure C16H32N4O4 O MW 344.45464 n/a 7.8450E-07 6.41E+13 30.4 0.12700 148.2 105.4 85.0 Water CAS No kref (1/s) A (1/sec) kcal/mol GJ/kmol 1 min 1 hr 10 hr Solvent
Half Life Temperature, C Source Wako
ID
Long Name
Trade Name(s)
VA85
O N N HN CH2 OH
411.37472 11858-13-0 1.9254E-05 9.56E+15 31.5 0.13200 111.7 76.9 60.0
2,2-Azobis{2-methyl-N-[2- VA-085 (Wako Chem) (1-hydroxybuthyl)] propionamide}
H 3CH 2 C HOH2 C
C16H32Cl2N6O2
NH
CH2 CH3
VA60
N N 2HCl N CH 2 CH 2 OH
Water
Wako
2,2-azo-bis{2-[1-(2VA-060 (Wako Chem) hydroxyethyl)-2-imidazolin2-yl]propane} dihydrochloride
N N N CH 2 CH 2 OH
Solvent Soluble Azo-Nitriles C5H8N4O
V30
1-cyano-1-methylethylazofomamide
V-30 (Wako Chem)
CN N N CONH2
164.21024 78-67-1 1.0464E-05 2.74E+15 31.1
140.14488
10288-28-5
4.4161E-08 1.86E+15
34.5
0.14430
164.9
123.9 104.0 Toluene
Wako
AIBN
2,2'-azo-bis-isobutyronitrile Vazo 64 (DuPont) Perkadox AIBN (AkzoNobel)
C8H12N4
0.13023
118.3
82.0
64.4
Chlorobenzene AkzoNobel
NC
C10H16N4
N N
CN
AMBN
2,2'-azo-bis(2methylbutyronitrile)
CN N N C 2H 5
O N N
244.33976 230.26400 2589-57-3
CN
192.26400
13472-08-7
8.4357E-06 1.38E+15
30.8
0.12893
121.2
84.0
66.0
Vazo 67 (DuPont) Perkadox AMBN (AkzoNobel) V-59 (Wako Chem)
C 2H5
C10H18N2O4
V601
dimethyl 2,2'-azobis (2methylpropionate)
V-601 (Wako Chem)
O OCH3
2094-98-6
8.5556E-06 6.99E+14
30.4
0.12700
122.1
84.3
66.0
Toluene
Wako
H 3CO
C14H20N4
ACCN
1,1-azo-di-(hexa hydrobenzenenonitrile)
Vazo 88 (DuPont) Perkadox ACCN (AkzoNobel) V-40 (Wako Chem)
NC N N CN
248.37152
5.4449E-07 1.07E+16
34.0
0.14219
140.2
103.0 84.9
AMVN
2,2'-azo-bis(2,4-dimethyl valeronitrile)
Vazo 52 (DuPont) V-65 (Wako Chem)
C14H24N4
4419-11-8
1.0349E-04 1.78E+14
27.8
0.11630
102.1
65.0
47.2
Toluene
DuPont
VF096
2,2'-azo-bis[N-(2propenyl)-2methylpropionamide]
VF-096 (Wako Chem)
C14H24N4O2
O N N
O HN
280.37032
129136-92-1 1.5480E-07 4.67E+14
32.7
0.13700
157.8
116.1 96.0
Toluene
Wako
NH
425
Decomposition Rate Parameters Formula / Molecular Structure C16H28N4O2

CN N N CH 2 OCH3 CN H 3CO H 2C
Decomposition Activation Energy kcal/mol GJ/kmol 1 min 27.5 0.11500 79.4 46.1 30.0 1 hr 10 hr Solvent Toluene
Half Life Temperature, C Source Wako
ID 308.42408 15545-97-8 1.1718E-03 1.26E+15
Long Name
Trade Name(s)
MW
CAS No
kref (1/s)
A (1/sec)
AMOMVN
2,2'-azo-bis(4-methoxy2,4-dimethyl valeronitrile)
V-70 (Wako Chem)
VAM110
2,2'-azo-bis(N-butyl-2methylpropionamide)
Vam-100 (Wako Chem) C16H32N4O2
O N N HN C 4 H 9
364.53160 n/a 3.4427E-08 1.71E+13 31.5 0.13200 181.3
312.45584
n/a
2.3941E-08 4.40E+14
33.9
0.14200
174.2
130.9 110.0 Toluene
Wako
C 4 H9 NH
O N N HN NH O
VAM111
2,2'-azo-bis(N-cyclohexyl2-methylpropionamide)
Vam-110 (Wako Chem) C20H36N4O2
133.7 111.0 Toluene
Wako
Diacyl Peroxides C6H10O4
PP
dipropionyl peroxide
O O O
146.14300
3248-28-0
4.3006E-05 1.14E+15
30.5
0.12760
119.1
81.9
63.9
Benzene
Polymer Handbook
O
C8H10O8 234.16260 123-23-9
SAP
succinic acid peroxide
Luperox SAP (Atofina) SUCP-70-W (Degussa)
O O O OH O
142.19796 3437-84-1
8.7924E-06 4.89E+10
24.0
0.10043
142.3
91.0
67.4
Acetone
Atofina
HO O
C8H14O2
IBP
diisobutyryl peroxide
Trigonox 187-C30 (AkzoNobel)
O O O
242.23100
2.7220E-03 3.42E+14
26.1
0.10906
72.7
39.0
22.8
BP
dibenzoyl peroxide
Luperox AFR40 (Atofina) C14H10O4
O O O O
94-36-0
3.8607E-06 3.40E+14
30.4
0.12721
130.3
91.0
72.1
Benzene
Atofina
DCLBP
bis(2,4-dichlorobenzoyl) peroxide
DCLBP (Degussa)
C16H6Cl2O4
O O Cl O O Cl Cl
333.12664
133-14-2
4.2163E-05 3.95E+14
28.9
0.12100
109.1
72.0
54.1
Benzene
Degussa
Cl
426
Decomposition Rate Parameters Formula / Molecular Structure C16H14O4 MW 270.28476 3034-79-5 1.5072E-05 6.85E+13 28.4 0.11900 120.9 81.0 61.9 CAS No kref (1/s) A (1/sec) kcal/mol GJ/kmol 1 min 1 hr 10 hr Solvent Benzene
Half Life Temperature, C Source Degussa
ID
Long Name
Trade Name(s)
OMBP
bis(ortho-methylbenzoyl) peroxide
Perkadox 20 (Akzo Nobel) OMBP (Degussa)
O O O O
PMBP
bis(para-methylbenzoyl) peroxide
PMBP (Degussa)
C16H14O4
O O O O
270.28476
895-95-2
5.1895E-06 2.06E+14
29.9
0.12500
128.6
89.0
70.0
Benzene
Degussa
OP
dioctanoyl peroxide
Trigonox SE-8 (AkzoNobel)
C16H30O4
O O O
314.46556 3851-87-4 2.0300E-05 2.70E+15 30.7
286.41180
762-16-3
1.3761E-05 2.36E+15
30.8
0.12905
116.3
80.0
62.4
H 3C(CH2) 6
C18H34O4
(CH2) 6CH 3
INP
bis(3,5,5Trigonox 36 trimethylhexanoyl) peroxide (AkzoNobel) Luperox 219 (AtoFina)
O O O
0.12835
112.8
77.0
59.6
DP
didecanoyl peroxide
Luperox DEC (Atofina) Perkadox SE-10 (AkzoNobel)
C20H38O4
O O O O O O O C 11H23
398.62684 105-74-8
342.51932
762-12-9
1.4646E-05 8.34E+14
30.1
0.12600
117.2
80.0
62.0
Benzene
Degussa
C 9H 19
C24H46O4
C 9H19
1.7414E-05 3.84E+14 29.5 0.12337 116.9 79.0 60.8 Chlorobenzene AkzoNobel
LP
dilauroyl peroxide
Luperox LP (Atofina) Laurox (AkzoNobel)
C 11H 23
Peroxycarbonates C8H16O4
BPIC
tert-butylperoxy isopropyl carbonate
Trigonox BPIC
O O O
176.21264
2372-21-6
7.0005E-08 2.44E+16
35.9
0.15015
154.9
117.0 98.5
427
Decomposition Rate Parameters Formula / Molecular Structure C8H16O6 MW 208.21144 105-64-6 1.6931E-04 7.70E+14 28.4 0.11900 96.3 61.0 44.0 CAS No kref (1/s) A (1/sec) kcal/mol GJ/kmol 1 min 1 hr 10 hr Solvent Benzene
Half Life Temperature, C Source Degussa
ID
Long Name
Trade Name(s)
IPPC
diisopropyl peroxydicarbonate
IPPC (Degussa)
O O O
208.21144 16066-38-9 1.4752E-04 3.56E+15 29.5 0.12362 96.1 62.0
O
C8H16O6
NPPC
di-n-propyl peroxydicarbonate
Luperox 221 (AtoFina) Trigonox NPP-CK85 (AkzoNobel)
O O O O
232.23344 19910-65-7 1.2919E-04 3.38E+15 29.6 0.12385
45.5
SBPC
di-secbutyl peroxydicarbonate
Luperox 225 (AtoFina) Trigonox SBP (AkzoNobel)
C10H16O6
O O O
248.27620 2372-21-6 7.0005E-08 2.44E+16 35.9
97.2
63.0
46.4
TBPIC
tert-butylperoxyisopropylcarbonate
Trigonox BPIC (Akzo) C11H20O6 Luperox TBIC (AtoFina) O TBPIC (Degussa)
0.15015
154.9
117.0 98.5
O C 4H9 O C 2H 5
286.32508 1561-49-5 246.34704 12/4/3443
O O
6.4441E-08 3.95E+16 36.3 0.15172 154.4 117.0 98.7 Chlorobenzene AkzoNobel
TBPEHC
tert-butylperoxy 2ethylhexyl carbonate
Trigonox 117 C13H26O4 (AkzoNobel) Luperox TBEC (AtoFina)
O O
C14H22O6
CHPC
dicyclohexyl peroxydicarbonate
CHPC (Degussa)
O O O O O O
1.9626E-04 3.30E+16
30.8
0.12900
91.9
59.9
44.2
Chlorobenzene AkzoNobel (Polymer Handbook)
TAPEHC
tert-amylperoxy 2ethylhexyl carbonate
Trigonox 131 C14H28O4 (AkzoNobel) C 2H5 Luperox TAEC (AtoFina)
260.37392
70833-40-8
1.2326E-07 2.29E+16
35.5
0.14841
150.5
113.0 94.7
C 4H 9 O
C18H34O6
O O O O O O
O O
C 2H 5
EHPC
di(2-ethylhexyl) peroxydicarbonate
Luperox 223 (AtoFina) Trigonox EHP (AkzoNobel)
346.46436
16111-62-9
1.1396E-04 1.80E+15
29.3
0.12245
98.9
64.0
47.1
428
Decomposition Rate Parameters Formula / Molecular Structure C22H38O6 398.54012 15520-11-3 1.1205E-04 7.34E+15 30.2 0.12639 97.7 64.0 47.6 MW CAS No kref (1/s) A (1/sec) kcal/mol GJ/kmol 1 min 1 hr 10 hr Solvent
Half Life Temperature, C Source
ID
Long Name
Trade Name(s)
BCHPC
Di(4-tert-butylcyclohexyl) peroxydicarbonate
Perkadox 16 (AkzoNobel)
O O
C30H58O6
O O
514.78692 53220-22-7 9.9164E-05 3.06E+15 29.7 0.12430 99.5 65.0
O O
48.3 Chlorobenzene AkzoNobel
MYPC
Dimyristyl peroxydicarbonate
O O O
570.89444 26322-14-5 9.9270E-05 2.85E+15 29.7 0.12410
C 14H 29 O
C34H66O6
O C H 14 29
99.6 65.0 48.2 Chlorobenzene AkzoNobel
CEPC
dicetyl peroxydicarbonate
O O O
146.22972 110-05-4 3.7905E-09 4.36E+15 36.7
C 16H 33 O
O C H 16 33
Alkyl Peroxides 0.15346 182.9 141.0 120.7 Chlorobenzene AkzoNobel
DTBP
di-tert-butyl peroxide
Trigonox B (AkzoNobel) C8H18O2 Luperox DI (AtoFina)
O O
C10H22O2 174.28348 10508-09-5 2.1965E-08 3.99E+15 35.5 0.14835 168.7 128.0 108.3 Chlorobenzene AkzoNobel
DTAP
di-tert-amyl peroxide
Trigonox 201 (AkzoNobel) Luperox DTA (AtoFina)
O O
208.30060 3457-61-2 1.0091E-08 1.12E+15 35.1 0.14698 178.8 136.0 115.3 Chlorobenzene AkzoNobel
BCUP
tert-butylcumyl peroxide
Trigonox T (AkzoNobel) C13H20O2 BCUP (Degussa)
O O
C18H22O2 270.37148 80-43-3 1.0731E-08 9.28E+15 36.5 0.15267 172.2 132.0 112.4 Chlorobenzene AkzoNobel
DCUP
dicumyl peroxide
Perkadox BC (AkzoNobel) Luperox 500 (AtoFina)
O O
382.58652 3.6200E-09 3.05E+15 36.5 0.15260 184.4 142.0 121.4 Toluene Warson (1980)
DTBCP
di-tert-butyl cumyl peroxide C26H38O2
O O
Hydroperoxides
429
Decomposition Rate Parameters Formula / Molecular Structure 90.12220 75-91-2 2.1276E-12 3.09E+17 44.5 0.18600 226.9 MW CAS No kref (1/s) A (1/sec) kcal/mol GJ/kmol 1 min 1 hr 10 hr Solvent
ID
Long Name
Trade Name(s)
TBHP
tert-butyl hydroperoxide
Trigonox A (AkzoNobel) C4H10O2 Luperox TBH (AtoFina) TBHP (Degussa)
185.0 164.4 Chlorobenzene AkzoNobel
O OH
TAHP
tert-amyl hydroperoxide
Trigonox TAHP (Akzo) TAHP (AtoFina)
C5H12O2
C2 H 5
C8H18O2
O OH
TMBHP
1,1,3,3-tetramethylbutyl hydroperoxide
Trigonox TMBH (AkzoNobel)
O OH
146.22972
5809-08-5
9.0052E-11 9.13E+18
44.2
0.18500
172.7
CUHP
cumene hydroperoxide
Trigonox K (AkzoNobel) C9H12O2 Luperox CU (AtoFina) CUHP (Degussa)
152.19308
80-15-9
1.8527E-09 1.13E+12
31.7
0.13256
221.8
O OH
IPCHP
isopropylcumyl hydroperoxide
Trigonox M (AkzoNobel) C12H18O2
O OH
Peroxyesters
TBPA
tert-butyl peroxyacetate
Trigonox F (AkzoNobel) C6H12O3 Luperox 7 (AtoFina)
O O
132.15948
107-71-1
5.7708E-08 1.51E+16
35.7
0.14936
157.5
O
C7H14O3 146.18636
TAPA
tert-amyl peroxyacetate
Trigonox 133 (AkzoNobel) Luperox 555 (AtoFina)
O O O O O
690-83-5
2.5042E-07 1.53E+17
36.3
0.15171
141.3
106.0 88.7
C 2H 5
C8H16O3
TBPIB
tert-butyl peroxyisobutyrate Trigonox 41 (AkzoNobel)
160.21324
109-13-7
1.3027E-06 2.02E+15
32.3
0.13516
136.3
98.0
79.5
430
Decomposition Rate Parameters Formula / Molecular Structure C9H18O3 MW 174.24012 927-07-1 2.8161E-05 6.72E+14 29.5 0.12359 111.9 75.0 57.2 CAS No kref (1/s) A (1/sec) kcal/mol GJ/kmol 1 min 1 hr 10 hr Solvent
ID
Long Name
Trade Name(s)
TBPPI
tert-butyl peroxypivalate
Trigonox 25 (AkzoNobel) Luperox 11 (AtoFina) TBPPI (Degussa)
O O
C10H20O3
TBPEA
tert-butyl peroxydiethylacetate
Trigonox 27 (AkzoNobel)
O O O
188.26700
2550-33-6
2.4603E-06 2.52E+15
32.0
0.13400
130.6
93.0
74.8
TAPPI
tert-amyl peroxypivalate
Trigonox 125 (AkzoNobel) Luperox 554 (AtoFina) TAPPI (Degussa)
C10H20O3
O C 2 H5
194.23036 614-45-9 3.5920E-08 2.10E+16 36.2
188.26700
29240-17-3
3.8733E-05 4.16E+15
30.5
0.12776
107.0
72.0
55.0
O O
O O
202.29388 110-05-4 8.0391E-05 2.17E+14 28.1
TBPB
tert-butyl peroxybenzoate
Triganox C (AkzoNobel) C11H14O3 Luperox P (AtoFina) TBPB (Degussa)
0.15159
160.5
TBPN7
tert-butyl peroxyneoheptanoate
C11H22O3
O C 3 H7
O O O
216.32076 3006-82-4 208.25724 4511-39-1
0.11756
104.2
67.0
49.1
O O
C12H16O3
TAPB
tert-amyl peroxybenzoate
Trigonox 127 (AkzoNobel) Luperox TAP (AtoFina) TAPB (Degussa)
7.3536E-08 8.27E+15
35.1
0.14702
157.0
118.0 99.0
C 2 H5
C12H24O3
TBPEH
tert-butylperoxy-2ethylhexanoate
O O C 2H 5 C 4 H9
4.1442E-06 1.59E+14
29.8
0.12490
131.1
91.0
71.7
TMBPPI
1,1,3,3-tetramethylbutyl peroxypivalate
C13H26O3
O O
230.34764
22288-41-1
9.0908E-05 2.41E+14
28.1
0.11750
103.0
66.0
48.2
431
Decomposition Rate Parameters Formula / Molecular Structure C13H26O3 MW 230.34764 686-31-7 3.3205E-06 1.72E+15 31.6 0.13211 128.7 91.0 72.7 CAS No kref (1/s) A (1/sec) kcal/mol GJ/kmol 1 min 1 hr 10 hr Solvent
ID
Long Name
Trade Name(s)
TAPEH
tert-amyl peroxy-2ethylhexanoate
Trigonox 121(AkzoNobel) Luperox 575 (AtoFina) TAPEH (Degussa)
O O O C 2 H5
230.34764 13122-18-4 1.6062E-07 1.90E+15 33.6 0.14078 154.0 114.0 94.6
C4H 9
C 2H 5
C13H26O3
TBPIN
tert-butylperoxy-3,5,5trimethyl-hexanoate
Trigonox 42S (AkzoNobel)
O O
244.37452 26748-41-4 1.1742E-04 1.49E+14 27.6 0.11547
O
C14H28O3
TBPND
tert-butyl peroxyneodecanoate
Trigonox 23 (AkzoNobel) Luperox 10 (AtoFina) TBPND (Degussa)
O C 2 H5 O O C 4 H9 C 2 H5
260.37392 95732-35-7 1.0997E-05 3.49E+13 28.2
101.2
64.0
46.2
DMHBPEH 1,1-dimethyl-3hydroxybutyl peroxy-2ethylhexanoate
Luperox 665 (AtoFina)
C14H28O4
C2H 5 O O
258.40140 68299-16-1
0.11800
125.0
84.0
64.4
TCE
AtoFina
OH
C 4H 9 O
C15H30O3
TAPND
tert-amyl peroxyneodecanoate
1.7016E-04 1.46E+14
27.3
0.11438
97.9
61.0
43.3
C 2 H5 C 2H 5
C16H24O3 264.36476
O C 2H 5 O O C 4H 9
CUPN7
cumyl peroxyneoheptanoate Trigonox 197 (AkzoNobel) Luperox 288 (AtoFina)
O O O C C2 H 5 C 2H 5
272.42828
130097-36-8 2.4772E-04 3.27E+14
27.6
0.11557
93.8
58.0
40.8
TMBPEH
1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate
C16H32O3
O O O
22288-43-3
6.0205E-06 1.55E+14
29.6
0.12380
127.8
88.0
68.9
C 4H 9 C2 H 5
C16H32O4
DMHBPND 1,1-dimethyl-3hydroxybutyl peroxyneodecanoate
Luperox 610 (AtoFina)
288.42768
95718-78-8
4.0233E-04 1.14E+14
26.6
0.11131
90.4
54.0
36.6
C 4H 9 C 2H 5 O
C2 H 5 O
OH O
aAtoFina methylstyrene
432
Decomposition Rate Parameters Formula / Molecular Structure C18H36O3 300.48204 51240-95-0 2.8151E-04 4.02E+14 27.7 0.11579 92.5 57.0 39.9 MW CAS No kref (1/s) A (1/sec) kcal/mol GJ/kmol 1 min 1 hr 10 hr Solvent
ID
Long Name
Trade Name(s)
TMBPND
1,1,3,3,-tetramethylbutyl peroxyneodecanoate
Triganox 423 (AkzoNobel)
C 4H 9 C 2H 5 O
O C 2H 5 O O C4 H 9 C 2H 5
C18H22O2 270.37148 1889-67-4 6.1389E-18 7.57E+18 55.0 0.23019 304.5 306.44540 26748-47-0 3.1832E-04 2.95E+14 27.4 0.11459 91.7 56.0 38.8 C19H30O3
C2H 5 O O
CUPND
cumyl peroxyneodecanoate Trigonox 99 (AkzoNobel) Luperox 188 (AtoFina) CUPND (Degussa)
C-C Initiators 259.0 236.4 Chlorobenzene AkzoNobel
DMDPB
2,3-dimethyl-2,3diphenylbutane
Sulfonyl Peroxides
ACHSP
acetyl cyclohexanesulphonyl peroxide
Lupersol 228Z (AtoFina) C8H14O5S
O S O O O
222.26216
3179-56-4
7.3692E-04 7.27E+17
32.0
0.13390
80.1
51.0
36.6
Toluene
Warson (1980)
433
References
Note: Anonymous data sources from the internet are documented by the vendor name and the year in which the data were collected. AkzoNobel (2004). Initiators for Polymer Production, Product Catalog. AtoFina (2004). Organic Peroxides, General Catalog. AtoFina (2004). Organic Peroxides, Product Bulletin, Diacyl Peroxides. AtoFina (2004). Organic Peroxides, Product Bulletin, Dialkyl Peroxides. AtoFina (2004). Organic Peroxides, Product Bulletin, Peroxydicarbonates. AtoFina (2004). Organic Peroxides, Product Bulletin, Tertiary Alkyl Hydroperoxides. AtoFina (2004). Fine Chemicals Technical Data. Degussa (2004). Technical Information. Half-Life Times of Organic Peroxides. Dupont (2004). Vazo Free radical initiators. (http://www.dupont.com/vazo/grades.html) Masson, J.C. (1989). Decomposition Rates of Organic Free Radical Initiators. Polymer Handbook, 3rd Edition. New York. Wako Chemical (2004). Water Soluble Azo-Initiator. (http://www.wako-chem.co.jp/specialty/waterazo/main.htm) Wako Chemical (2004). Solvent Soluble Azo-Initiator. (http://www.wako-chem.co.jp/specialty/oilazo/main.htm) Warson, H. (1980). Per-Compounds and Per-Salts in Polymer Processes. England: Solihull Chemical Services, 5-17.
434
C Fortran Utilities
This appendix describes the input and output arguments for various Fortran utilities useful for writing user kinetic subroutines. For each utility a list of variables in the argument list is given along with their I/O status, their type, and a brief description. These utilities are available to you in addition to those documented in the Aspen Plus User Models reference manual. The utilities documented in this appendix are:
Component Attribute Handling Utilities CAELID CAID CAMIX CASPLT CASPSS CAUPDT COPYCA GETCRY GETDPN GETMWN GETMWW GETPDI GETSMF GETSWF LCAOFF LCATT NCAVAR
Component Handling Utilities CPACK IFCMNC ISCAT ISINI General Stream Handling Utilities IPTYPE LOCATS Other Utilities VOLL LPHASE NPHASE NSVAR SSCOPY ISOLIG ISPOLY ISSEG SCPACK XATOWT XATOXT
C Fortran Utilities
435
Component Attribute Handling Utilities

CAELID
Utility Description
This utility finds a component attribute element ID given the attribute ID and the element number.
Argument List
SUBROUTINE SHS_CAELID ( IDCAT, IELEM, IDCAEL )
Variable IDCAT IELEM IDCAEL I/O I I O Type INTEGER INTEGER INTEGER Dimension 2 --2 Description Comp attr. ID in two integer words Comp attr. element no. Comp attr. element ID in two integer words
Calling Sequence in User Routine

INTEGER IDCAT(2), IELEM, IDCAEL(2) DATA IDCAT / 'DPN ',' ' / IELEM=1 . . . CALL SHS_CAELID ( IDCAT, IELEM, IDCAEL )
CAID
Utility Description
This utility finds a component attribute ID given the component sequence number, the attribute type number, and the substream structure.
Argument List
SUBROUTINE SHS_CAID ( ISSCNC, NCSEQ, J, IDCAT )
Variable I/O Type Dimension Description
436
C Fortran Utilities
ISSCNC
INTEGER
---
Flag: 1 = conventional substream 2 = nonconventional substream
NCSEQ J IDCAT
I I O
INTEGER INTEGER INTEGER
----2
Attributed component sequence number Comp attr. type no. Comp attr. ID in two integer words

INTEGER ISSCNC, NCSEQ, J, IDCAT(2) ISSCNC=1 !'Conventional substream' J=1 . . . CALL SHS_CAID ( ISSCNC, NCSEQ, J, IDCAT )
CAMIX
Utility Description
This is the component attribute mixing utility. It mixes the attributes from two inlet streams into an outlet stream.
Argument List
SUBROUTINE SHS_CAMIX ( IP, SS1, SS2, SSO )
Variable IP I/O I Type I Dimension --Description Substream type 1 or 2 = conventional 3 = nonconventional SS1 SS2 SSO I I O R R R 1 1 1 1st input substream 2nd input substream Output substream

INTEGER IP REAL*8 SS1(1), SS2(1), SS0(1) IP=1 !'Conventional substream' .
C Fortran Utilities
437
. . CALL SHS_CAMIX ( IP, SS1, SS2, SSO )
CASPLT
Utility Description
This is the component attribute splitting utility. It calculates the attribute values in a product stream for a given feed stream.
Argument List
SUBROUTINE SHS_CASPLT ( FEED, PROD, NSUBS, IDXSUB, ITYPE )
Variable FEED PROD NSUBS ITYPE IDXSUB I/O I O I I I Type DBL DBL INT INT INT Dimensio n (1) (1) --NSUB NSUB Description Combined feed stream Given outlet stream Number of substreams Substream type vector Substream index vector

INTEGER NSUBS, ITYPE(1), IDXSUB(1) REAL*8 FEED(1), PROD(1) IDXSUB(1)=1 !'First substream' ITYPE(1)=1 !'Conventional' . . . CALL SHS_CASPLT ( FEED, PROD, NSUBS, IDXSUB, ITYPE )
CASPSS
Utility Description
This is the component attribute splitting utility for substreams. It calculates the attribute values in a product substream for a given feed substream.
Argument List
SUBROUTINE SHS_CASPSS ( FEED, PROD, ITYPE )
438
C Fortran Utilities
Variable FEED PROD ITYPE
I/O I O I
Type DBL DBL INT
Dimension (1) (1) NSUB
Description Feed substream Outlet substream Substream type

INTEGER ITYPE(1) REAL*8 FEED(1), PROD(1) ITYPE(1)=1 !'Conventional' . . . CALL SHS_CASPSS ( FEED, PROD, ITYPE )
CAUPDT
Utility Description
This utility calculates class zero component attribute values in a product stream based on class 2 component attributes.
Argument List
SUBROUTINE SHS_CAUPDT ( STREAM, NSUBS, IDXSUB, IPHASE )
Variable STREAM NSUBS IDXSUB IPHASE I/O R*8 I I I Type I I I I Dimension (1) --NSUBS NSUBS Description Stream vector Number of substreams Substream index vector Substream type vector 1= MIXED 2= CISOLID 3= NCSOLID

INTEGER NSUBS, IDXSUB(1), IPHASE(1) REAL*8 STREAM(1) IPHASE(1)=1 !'First phase' .
C Fortran Utilities
439
. . CALL SHS_CAUPDT ( STREAM, NSUBS, IDXSUB, IPHASE )
COPYCA
Utility Description
This utility copies all attribute values from one stream into another stream of the same type.
Argument List
SUBROUTINE SHS_COPYCA( LDIN, LD, LVRIN, LVR, IPHIN, IPH )
Variable LDIN LD LVRIN LVR IPHIN IPH I/O I I I I I I Type I I I I I I Dimension ------------Description Location of the descriptor bead for the input stream Location of the descriptor bead for the output stream Location of the real stream variable data for the input stream Location of the real stream variable Phase no. in the input stream Phase no. in the output stream data for the output stream

INTEGER IPHIN, IPH INTEGE LDIN, LD, LVRIN, LVR !'Use LOCATS utility model to obtain these values'
IPHIN=1 IPH=1 . . . CALL SHS_COPYCA( LDIN, LD, LVRIN, LVR, IPHIN, IPH )
GETCRY
Utility Description
This utility returns the crystallinity of a list of components.
440
C Fortran Utilities
Argument List
SUBROUTINE POLY_GETCRY ( NCNC, NCP, IDX, CRY )
Variable NCNC NCP IDX CRY I/O I I I O Type I I I I Dimension ----NCP NCP Description 1 = conventional substream 2 = non-conventional substream Number of components Component index vector Crystalline fraction

INTEGER NCNC, NCP, IDXP, CRY(1) NCNC=1 !'Conventional substream' NCP=1 IDXP=2 !'Polymer is 2nd component' . . . CALL POLY_GETCRY( NCNC, NCP, IDX, CRY )
GETDPN
Utility Description
This utility returns the number average degree of polymerization.
Argument List
SUBROUTINE POLY_GETDPN ( NCNC, NCP, IDX, DPN )
Variable NCNC NCP IDX DPN I/O I I I O Type I I I R Dimension ----NCP NCP Description 1 = conventional substream 2 = non-conventional substream Number of components Component index vector Degree of polymerization
C Fortran Utilities
441

INTEGER NCNC, NCP, IDXP REAL*8 DPN NCNC=1 !'Conventional substream' NCP=1 IDXP=2 !'Polymer is 2nd component' . . . CALL POLY_GETDPN( NCNC, NCP, IDX, DPN )
GETMWN
Utility Description
This utility calculates the true molecular weight of a polymer, from the degree of polymerization and the average segment molecular weight.
Argument List
SUBROUTINE POLY_GETMWN ( NCNC, NCP, IDX, XMWTRU )
Variable NCNC NCP IDX XMWTRU I/O I I I O Type INT INT INT DBL Dimension ----NCP NCP Description 1 = conventional substream 2 = non-conventional substream Number of components Component index vector True number average molecular weight

INTEGER NCNC, NCP, IDXP REAL*8 XMWTRU(1) NCNC=1 !'Conventional substream' NCP=1 IDXP=2 !'Polymer is 2nd component' . . . CALL POLY_GETMWN( NCNC, NCP, IDX, XMWTRU )
442
C Fortran Utilities
GETMWW
Utility Description
This utility returns the weight-average molecular weight vector for all of the polymer components present. For standard components, the component molecular weight is returned.
Argument List
SUBROUTINE POLY_GETMWW ( NCNC, NCP, IDX, MWW )
Variable NCNC NCP IDX MWW I/O I I I O Type INTEGER INTEGER INTEGER DBL Dimension ----NCP NCP Description 1 = conventional substream 2 = non-conventional substream Number of components present Component index vector Weight-average molecular weight

REAL*8 MWW INTEGER NCNC, NCP, IDXI NCNC=1 !'Conventional substream' NCP=1 !'Only one component (polymer)' IDXI=2 !'Polymer is 2nd component' . . . CALL POLY_GETMWW( NCNC, NCP, IDXI, MWW )
GETPDI
Utility Description
This utility returns the polydispersity index for all components listed in the IDX array. For standard components, the PDI is set equal to the value of the POLPDI parameter.
Argument List
SUBROUTINE POLY_GETPDI ( NCNC, NCP, IDX, MWW )
C Fortran Utilities
443
Variable NCNC NCP IDX PDI
I/O I I I O
Type INTEGER INTEGER INTEGER DBL
Dimension ----NCP NCP
Description 1 = conventional substream 2 = non-conventional substream Number of components present Component index vector Polydispersity index

INTEGER NCNC, NCP, IDXI REAL*8 PDI NCNC=1 !'Conventional substream' NCP=1 !'Only one component (polymer)' IDXI=2 !'Polymer is 2nd component' . . . CALL POLY_GETPDI( NCNC, NCP, IDXI, PDI )
GETSMF
Utility Description
This utility returns the segment mole fractions for the specified polymer or oligomer component.
Argument List
SUBROUTINE POLY_GETSMF ( NCNC, IDX, SMFRAC )
Variable NCNC IDX SMFRAC I/O I I O Type INTEGER INTEGER DBL Dimension ----NCOMP_NSEG Description 1 = conventional substream 2 = non-conventional substream Component index Segment mole fractions
The number of segments is retrieved from common NCOMP. The SMFRAC variable must be dimensioned to NCOMP_NSEG or larger.

INTEGER NCNC, NCP, IDXI
444
C Fortran Utilities
REAL*8 SMFRAC(10) ! dimension must be > Nseg NCNC=1 !'Conventional substream' IDXI=2 !'Polymer is 2nd component' . . . CALL POLY_GETSMF( NCNC, IDXI, SMFRAC)
GETSWF
Utility Description
This utility returns the segment weight (mass) fractions for the specified polymer or oligomer component.
Argument List
SUBROUTINE POLY_GETSWF ( NCNC, IDX, SMFRAC )
Variable NCNC IDX SWFRAC I/O I I O Type INTEGER INTEGER DBL Dimension ----NCOMP_NSEG Description 1 = conventional substream 2 = non-conventional substream Component index Segment mole fractions
The number of segments is retrieved from common NCOMP. The SWFRAC variable must be dimensioned to NCOMP_NSEG or larger.

INTEGER NCNC, NCP, IDXI REAL*8 SWFRAC(10) ! dimension must be > Nseg NCNC=1 !'Conventional substream' IDXI=2 !'Polymer is 2nd component' . . . CALL POLY_GETSWF( NCNC, IDXI, SWFRAC)
C Fortran Utilities
445
LCAOFF
Utility Description
This utility finds the offset of a component attribute from the beginning of the substream given the structure of the substream, the component sequence number and the attribute type number.
Argument List
FUNCTION SHS_LCAOFF (ISSCNC, NCSEQ, J)
Variable ISSCNC I/O I Type INTEGER Dimension --Description Flag: 1 = Conventional substream 2 = non conventional substream NCSEQ J LCAOFF I I O INTEGER INTEGER INTEGER ------Attributed component sequence number Comp. attribute type no. Attribute offset from substream

INTEGER ISSCNC, NCSEQ, J, SHS_LCAOFF ISSCNC=1 !'Conventional substream' NCSEQ=2 !'Second attributed component' J=1 !'First component attribute in the list for this component' . . . N = SHS_LCAOFF (ISSCNC, NCSEQ, J)
LCATT
Utility Description
This utility finds the offset of a component attribute from the substream given the structure of the substream, attributed component sequence number and the attribute ID.
Argument List
446
C Fortran Utilities
FUNCTION SHS_LCATT (ISSCNC, NCSEQ, IDCATT)

Variable ISSCNC I/O I Type INTEGER Dimension --Description Flag: 1 = conventional substream 2 = non conventional substream NCSEQ IDCATT LCATT I I O INTEGER INTEGER INTEGER --2 --Attributed component sequence number Component attribute ID in two integer words Attribute offset

INTEGER ISSCNC, NCSEQ, IAID(2), SHS_LCATT DATA IAD / 'DPN ', / ' ' / ISSCNC=1 NCSEQ=1 . . . N = SHS_LCATT (ISSCNC, NCSEQ, IAID)
NCAVAR
Utility Description
This utility finds the number of elements in a component attribute given the attribute type index, the component index, and the substream type.
Argument List
FUNCTION SHS_NCAVAR (ISSCNC, NCSEQ, J)
Variable ISSCNC I/O I Type INTEGER Dimension --Description Flag: 1 = conventional substream 2 = non conventional substream NCSEQ J NCAVAR I I O INTEGER INTEGER INTEGER ------Attributed component sequence number Comp attribute type no. Attribute length
C Fortran Utilities
447

INTEGER ISSCNC, NCSEQ, J, SHS_NCAVAR ISSCNC=1 !'Conventional substream' NCSEQ=1 J=1 . . . N = SHS_NCAVAR (ISSCNC, NCSEQ, J)
Component Handling Utilities

CPACK
Utility Description
This utility packs a list of conventional components into an output vector that contains components whose mole fraction is greater than a minimum value XMIN.
Argument List
SUBROUTINE SHS_CPACK (PHASE, NCP, IDX, X, FLOW)
Variable PHASE NCP IDX X FLOW I/O I O O O O Type REAL INTEGER INTEGER REAL REAL Dimension NVCP --NCC NCC --Description Vector of component flows Number of components actually present Index vector of components actually present Mole fraction vector of components actually present Total molar flow of the phase

INTEGER NCP, IDX(1) REAL*8 X(1), FLOW, PHASE(1) . . . CALL SHS_CPACK (PHASE, NCP, IDX, X, FLOW)
448
C Fortran Utilities
IFCMNC
Utility Description
This utility is used to retrieve parameter values from the plex.
Argument List
FUNCTION DMS_IFCMNC ( NAME )
Variable NAME I/O I Type CHARACTER*8 Dimension --Description Parameter name as a character string

C INTEGER TC, I . . . TC(I)=DMS_IFCMNC('TC')+I
ISCAT
Utility Description
This utility determines whether a component is a catalyst.
Argument List
FUNCTION PPUTL_ISCAT ( ICOMP )
Variable ICOMP ISCAT I/O I O Type I L Dimension ----Description Component index True for catalysts

INTEGER ICOMP LOGICAL PPUTL_ISCAT
C Fortran Utilities
449
ICOMP=2 ! . . . If ( PPUTL_ISCAT( ICOMP ) ) then...
ISINI
Utility Description
This utility determines whether a component is an ionic initiator.
Argument List
FUNCTION PPUTL_ISINI ( ICOMP )
Variable ICOMP ISINI I/O I O Type I L Dimension ----Description Component index True for initiators

INTEGER ICOMP LOGICAL PPUTL_ISINI ICOMP=2 ! . . . If ( PPUTL_ISINI( ICOMP ) ) then...
ISOLIG
Utility Description
This utility determines whether a component is an oligomer.
Argument List
FUNCTION SHS_ISOLIG ( ICOMP )
Variable ICOMP ISOLIG I/O I O Type I L Dimension ----Description Component index True for oligomers
450
C Fortran Utilities

INTEGER ICOMP LOGICAL SHS_ISOLIG ICOMP=3 ! . . . If ( SHS_ISOLIG( ICOMP ) ) then...
ISPOLY
Utility Description
This utility determines whether a component is a polymer.
Argument List
FUNCTION SHS_ISPOLY ( ICOMP )
Variable ICOMP ISPOLY I/O I O Type I L Dimension ----Description Component index True for polymers

INTEGER ICOMP LOGICAL SHS_ISPOLY ICOMP=2 ! . .. If ( ISPOLY( ICOMP ) ) then...
ISSEG
Utility Description
This utility determines whether a component is a segment.
Argument List
FUNCTION PPUTL_ISSEG ( ICOMP )
C Fortran Utilities
451
Variable ICOMP ISSEG
I/O I O
Type I L
Dimension -----
Description Component index True for segments

INTEGER ICOMP LOGICAL PPUTL_ISSEG ICOMP=5 ! . . . If ( PPUTL_ISSEG( ICOMP ) ) then...
SCPACK
Utility Description
This utility packs lists of conventional component flow rates from several phases into an output array which contains mole fractions of components that are present in at least one of the phases.
Argument List
SUBROUTINE SHS_SCPACK (NPHASE, LPHASE, NCP, IDX, X, FLOW)
Variable NPHASE LPHASE NCP IDX X FLOW I/O I I O O O O Type INTEGER INTEGER INTEGER INTEGER REAL REAL Dimension --NPHASE --NCC NCC, NPHASE NPHASE Description Number of phases to be packed Vector of phase plex addresses Number of components actually present Index vector of components actually present Mole fraction array of components actually present Vector of phase flow rates

INTEGER NPHASE, LPHASE(1), NCP, IDX(1) REAL*8 X(2), FLOW(2) . . .
452
C Fortran Utilities
CALL SHS_SCPACK (NPHASE, LPHASE, NCP, IDX, X, FLOW)
XATOWT
Utility Description
This utility returns the true weight fractions for all of the components present.
Argument List
SUBROUTINE POLY_XATOWT ( X, NCP, IDX, WT )
Variable X NCP IDX WT I/O I I I O Type DBL INTEGER INTEGER DBL Dimension NCP --NCP NCP Description Apparent mole fraction vector Number of components present Component index vector True weight fraction vector

C C C C C C Dimension of WT can be set high enough to avoid overwriting; Alternatively, the proper work space can be assigned to the array WT (preferred method) REAL*8 WT(10) . . . CALL POLY_XATOWT (X, NCP, IDX, WT)
XATOXT
Utility Description
This utility returns the true mole fractions for all of the components present.
Argument List
SUBROUTINE POLY_XATOXT ( NCP, IDX, XMW, X, XTRUE )
Variable I/O Type Dimension Description
C Fortran Utilities
453
NCP IDX XMW NCC X XTRUE
I I I I I O
INTEGER INTEGER DBL INTEGER IDNL DBL
--NCP NCC --NCP NCP
Number of components present Component index vector Molecular weight vector Number of components listed Apparent mole fraction vector True mole fraction vector

C C C C C C Dimension of XTRUE can be set high enough to avoid overwriting; Alternatively, the proper work space can be assigned to the array XTRUE (preferred method) REAL*8 XTRUE(10) . . . CALL POLY_XATOXT (NCP, IDX, XMW, X, XTRUE)
General Stream Handling Utilities

IPTYPE
Utility Description
This utility returns the substream type number from the stream class descriptor bead.
Argument List
FUNCTION SHS_IPTYPE (LD, I)
Variable LD I I/O I I Type INTEGER INTEGER Dimension ----Description Address of stream class descriptor bead Substream number
454
C Fortran Utilities

INTEGER I, SHS_IPTYPE INTEGR LD !'Use LOCATS utility model to obtain LD' I=1 !'Substream 1' . . . N = SHS_IPTYPE (LD, I)
LOCATS
Utility Description
This utility finds the integer and real plex addresses of a stream, the stream class bead location and bead number, given the stream bead number.
Argument List
SUBROUTINE SHS_LOCATS (NB, LVI, LVR, LD, NBD)
Variable NB LVI LVR LD NBD LOFFDB I/O I O O O O --Type INTEGER INTEGER INTEGER INTEGER INTEGER INTEGER Dimension ------------Description Stream bead number Integer plex location of the stream bead Real plex location of the real portion of the bead Integer plex location of the descriptor bead Descriptor bead number Offset to the descriptor bead number in the stream bead

INTEGER LVI, LVR, LD, NBD, LOFFDB INTEGER NB !'NB is obtained from the argument list' . . . CALL SHS_LOCATS (NB, LVI, LVR, LD, NBD)
C Fortran Utilities
455
LPHASE
Utility Description
This utility finds the offset of a substream from the beginning of a stream structure.
Argument List
FUNCTION SHS_LPHASE (LD, I)
Variable LD LPHASE I I/O I O I Type INTEGER INTEGER INTEGER Dimension ------Description Address of stream class descriptor bead Offset of substream I in the stream structure Substream number

INTEGER I, SHS_LPHASE INTEGER LD !'Use LOCATS utility to obtain LD' I=1 . . . N = SHS_LPHASE (LD, I)
NPHASE
Utility Description
This utility finds the number of substreams from the stream class descriptor bead.
Argument List
FUNCTION SHS_NPHASE (LD)
Variable LD NPHASE I/O I O Type INTEGER INTEGER Dimension ----Description Address of stream No. of substreams
456
C Fortran Utilities

INTEGER SHS_NPHASE INTEGER !'Use LOCATS utility model to obtain LD' . . . N = SHS_NPHASE (LD)
NSVAR
Utility Description
This utility returns the number of stream variables.
Argument List
FUNCTION SHS_NSVAR (LD)
Variable LD NSVAR I/O I O Type INTEGE R INTEGE R Dimension ----Description Address of stream class descriptor bead Length of stream variable

INTEGER SHS_NSVAR INTEGER LD !'Use LOCATS utility model to obtain LD' . . . N = SHS_NSVAR (LD)
SSCOPY
Utility Description
This utility copies substream information from one stream to another.
Argument List
SUBROUTINE SHS_SSCOPY( LD, S1, S2, IDX, I)
C Fortran Utilities
457
Variable LD S1 S2 IDX I
I/O I I O I I
Type I R R I I
Dimension --(1) (1) -----
Description Locator of descriptor bead Stream vector to copy from Stream vector to copy into Location of substream within stream vector Substream number

INTEGER LD !'Use LOCATS utility model to obtain LD' INTEGER IDX(1), I REAL*8 S(1), S2(1) I=1 !'Substream 1' . . . CALL SHS_SSCOPY( LD, S1, S2, IDX, I)
Other Utilities
VOLL
Utility Description
This utility calculates the mixture molar volume of liquid.
Argument List
SUBROUTINE DV, KER )
Variable T P N IDX X NBOPST KDIAG KKV V I/O I I I I I I I I O Type REAL*8 REAL*8 INTEGER INTEGER REAL*8 INTEGER INTEGER INTEGER REAL*8
PPMON_VOLL ( T, P, X, N, IDX, NBOPST, KDIAG, KKV, V,
Dimension ------N N 6 -------
Description Temperature (K) Pressure (N/m 2 ) Number of components present Component index vector Liquid mole fraction vector Physical property method vector Diagnostic level code Mole volume calculation code Mixture molar volume (m 3 /kgmole)
458
C Fortran Utilities
DV KER
O O
REAL*8 INTEGER
-----
Partial derivatives of mixture molar volume with respect to temperature (m 3 /kgmole - K) Error return code (=0 if an error or warning condition occurred in any physical property model; =0 otherwise)

INTEGER N, IDX(N), NBOPST(6) !'These variables are obtained from the argument list'
INTEGER KDIAG, KKV REAL*8 T, P, X(N) !'X is obtained from the argument list' KDIAG=4 KKV=1 . . . CALL PPMON_VOLL (T, P, X, N, IDX, NBOPST, KDIAG, KKV, V, DV, KER)
C Fortran Utilities
459
D Input Language Reference
This section describes the input language for: Specifying Components, 460 Specifying Component Attributes, 464 Specifying Attribute Scaling Factors, 466 Requesting Distribution Calculations, 467 Calculating End Use Properties, 468 Specifying Physical Property Inputs, 470 Specifying Step-Growth Polymerization Kinetics, 474 Specifying Free-Radical Polymerization Kinetics, 482 Specifying Emulsion Polymerization Kinetics, 493 Specifying Ziegler-Natta Polymerization Kinetics, 499 Specifying Ionic Polymerization Kinetics, 510 Specifying Segment-Based Polymer Modification Reactions, 517
Specifying Components
This section describes the input language for specifying components.
Naming Components
Following is the input language used to name components.
Input Language for Components
COMPONENTS
cid
[cname]
[outid]
...
Input Language Description for Components
COMPONENTS
cid
Component ID. Used to refer to the component in all subsequent input and is also used to identify the component in the simulation report. Aspen Plus input language conventions and naming guidelines apply to this keyword.
460
cname
The databank name or alias used for that component. Refer to the documentation for the desired databank to find out the correct databank name or alias for the desired component. Place an asterisk (*) in the cname position if you do not wish to retrieve the component from the databank. Note that in this case you are required to provide all necessary physical property parameters. Eight-character name used for the component in reports. (Default=cid)
outid
Input Language Example for Components
DATABANKS PURE13 / POLYMER / SEGMENT / INITIATOR COMPONENTS INI1 STY CAN LP STYRENE ACRYLONITRILE INIT STYRENE CAN XYLENE STY-SEG ACN-SEG SAN / / / / / / ; ; ; ; ; ; ; INITIATOR MONOMER MONOMER SOLVENT STYRENE SEGMENT ACN SEGMENT COPOLYMER
XYLENE P-XYLENE STYSEG STYRENE-R ACNSEG ACRYLONITRILE-R SAN SAN
Specifying Component Characterization Inputs

A POLYMERS paragraph is used to define polymers, their segments, oligomers, and heterogeneous catalysts, if any, involved in the polymerization. This paragraph is also used to define the polymer and catalyst component attributes desired in the simulation. Only the names of the attributes need to be specified in the POLYMERS paragraph. Initial values for the component attributes may be entered for the polymer and catalyst components in each stream via the STREAM paragraph. Following is the input language for the POLYMERS paragraph.
Input Language for Polymers, Oligomers, and Catalysts
461
POLYMERS PARAM SEGMENTS OLIGOMERS POLYMERS CATALYSTS INITIATORS ATTRIBUTES DISTRIBUTION
kwd=value seg-id seg-type / olig-id seg-id number / poly-id / cat-id mol-site / ini-id/ comp-id attr-list / polyid disttype NPOINTS=value FUNCLOG=YES/NO UPPER=value
Input Language Description for Polymers, Oligomers, and Catalysts
PARAM
Used to enter special parameters. Keywords are as follows. NSITE N-BIFUNINIT Number of catalyst site types Number of bifunctional initiators
SEGMENTS
Used to specify all the segments used in the simulation. The information entered through this keyword is used by the system to pass segment property information. seg-id seg-type Name of the segment (must be a valid component ID) Segment type. This information is used to differentiate segment types. The options are END, REPEAT, BRANCH3, or BRANCH4. The default value is REPEAT
POLYMERS
Used to identify all polymers present in the simulation. poly-id Name of the polymer (must be a valid component ID)
OLIGOMERS
Used to specify the structure of oligomers present in the simulation. olig-id seg-id Oligomer component ID ID for segment contained in that oligomer. All the segment names must be valid component IDs (Optional) Number of this segment in the oligomer (Default=1)
number POLYMERS
Used to identify all polymers present in the simulation. poly-id Name of the polymer (must be a valid component ID)
462
CATALYSTS
Used to identify all the heterogeneous polymerization catalysts present in the simulation and to specify the moles of catalytic sites per mole of catalyst. cat-id mol-site Catalyst component ID Moles of catalytic sites per unit mass of that catalyst
INITIATORS
Used to identify all the ionic polymerization initiators present in the simulation. ini-id Initiator component ID
ATTRIBUTES
Used to specify all the polymer/catalyst component attributes desired for each polymer/catalyst in the simulation. Only the attribute names need to be specified here. Values for the component attributes are entered in the COMP-ATTR sentence of the STREAM paragraph. comp-id attr-list Polymer or catalyst component ID List of component attributes. The component attributes specific to polymers are listed in Polymer Component Attributes in Chapter 2, while those for catalysts are listed in Site-Based Species Attributes in Chapter 2.
DISTRIBUTION Used to request polymer property distribution plots. polyid disttype NPOINTS Polymer ID Distribution type Number of points
FUNCLOG Calculate distribution as rW(r) vs. r on a log scale. Default is NO upper Upper limit
Since component attributes represent a significant feature in Aspen Polymers (formerly known as Aspen Polymers Plus), a complete subsection has been devoted to their use in the simulator. For more detailed information regarding component attributes, see the Polymer Structural Properties section of Chapter 2.
Input Language Example for Polymers, Oligomers and Catalysts
463
POLYMERS POLYMERS POLYSTYRENE SEGMENTS PRESENT SAN STYSEG REPEAT/ ACNSEG REPEAT ; DEFINE TYPE OF SEGMENTS ; DEFINE SEGMENTS IN
; DEFINE ATTRIBUTES FOR POLYMERS & ATTRIBUTES SAN DPN DPW PDI MWN MWW ZMOM FMOM SMOM SFLOW SFRAC LDPN LZMOM LFMOM LSFLOW LSFRAC LEFLOW LEFRAC PS CHAIN-SIZE NPOINTS=100 UPPER=9999
LPFRAC DISTRIBUTION
Specifying Component Attributes

This section describes the input language for specifying component attributes..
Specifying Characterization Attributes

See Specifying Component Characterization Inputs on page 461.
Specifying Conventional Component Attributes

To assign user component attributes to a conventional component use the ATTR-COMPS paragraph as follows:
Input Language for Catalyst Component Attributes
ATTR-COMPS
comp-id attr-list
CLASS=CV
...
Input Language Description for Catalyst Component Attributes
comp-id
Standard component ID.
464
attr-list
List of attributes. Valid attributes were given in User Attributes in Chapter 2.
Initializing Attributes in Streams

Following is the input language used to enter attribute values in streams.
Input Language for Material Streams
STREAM sid SUBSTREAM ssid basis-FLOW cid basis-FRAC cid COMP-ATTR cname Keywords: TEMP PRES
keyword=value flow / . . . frac / . . . cattrname (value-list) basis-FLOW
. . .
Optional Keywords: NPHASE
PHASE
Input Language Description for Material Streams
SUBSTREAM
Used to enter state and flash specifications for substreams. Ssid TEMP PRES basisFLOW NPHASE PHASE Substream ID Temperature Pressure Flow rate on a MOLE, MASS, or VOLUME basis Number of phases Used to specify the phase when NPHASE=1 PHASE=V (vapor), L (liquid), or S (solid)
basis-FLOW
Used to enter component flows. cid flow Component ID Component mole or mass flow
basis-FRAC
Used to enter component fractions. cid frac Component ID Component mole or mass fraction
COMP-ATTR
Used to enter component attribute values. Cname Component name
465
cattrname Component attribute name. For polymer attributes, values must be entered for at least SFRAC or SFLOW, and DPN or both ZMOM and FMOM value-list List of values for each element in the attribute. Use * to skip entries
Input Language Example for Material Streams
STREAM FEED SUBSTREAM MIXED TEMP=70 PRES=1 MASS-FLOW STY 13.5 /ACN 7.27 /XYLENE 79 /SAN 0.1E-5/INI1 0.23 COMP-ATTR SAN DPN (3000) DPW (6000) PDI (2) MWN (312450) MWW (624900) ZMOM (0.39E-10) FMOM (1.17E-7) SMOM (7.02E-4) SFLOW (0.55E-7 0.55E-7) SFRAC (0.5 0.5) LSFLOW (0. LEFLOW (0. 0.) 0.) / / / / / / / / / / /
Specifying Attribute Scaling Factors

This section describes the input language used to change the default scaling factors for component attributes.
Specifying Component Attribute Scale Factors

The ATTR-SCALING paragraph is used to override the default scaling factors and upper bounds for component attributes. The standard values for these
466
parameters are defined in the Aspen Plus system definition file through the TBS data table PPCMATTR.DAT. The component attribute scaling factors are used in flowsheet tear-stream convergence and in reactor model convergence as described in Component Attribute Scale Factors in Chapter 2. The model uses one set of scaling parameters for all elements of each component attribute. If one component attribute is used by more than one component, different scaling factors can be applied for each instance of the attribute.
Input Language for Attribute Scaling Factors
ATTR-SCALING SCALING COMP=comp-id ATTR=attr-id SCALE-FACTOR=scale UPPER-BOUND=upper
Input Language Description for Attribute Scaling Factors
SCALING
Used to enter special parameters. Keywords are as follows. comp-id attr-id scale upper Attributed component ID Attribute ID Number of catalyst site types Upper limit
Input Language Example for Component Attribute Scaling
ATTR-SCALING SCALING PP LSEFLOW SCALE=1E-008 UPPER=1.E35 SCALING PP LZMOM SCALE=1E-008 UPPER=1.E35 SCALING PP LSZMOM SCALE=1E-008 UPPER=1.E35 SCALING TICL4 CVSFLOW SCALE=1E-008 UPPER=1.E35 SCALING TICL4 CPSFLOW SCALE=1E-008 UPPER=1.E35
Requesting Distribution Calculations

See Specifying Component Characterization Inputs on page 461.
467
Calculating End Use Properties

This section describes the input language for calculating end use properties.
Input Language for Prop-Set
PROP-SET
propsetid
propname-list
keyword=value
Optional Keywords: COMPS PHASE UNITS TEMP PRES
Input Language Description for Prop-Set
Use the Prop-Set paragraph to define a property set. A property set is a collection of thermodynamic, transport, and other properties. Each property set you define is identified by an ID you supply. Propsetid Propname-list COMPS Property set ID. List of property names. (See Aspen Physical Property System Physical Property Data documentation.) List of component Ids (applies to all properties listed in Aspen Physical Property System Physical Property Data documentation). (Default=all components actually present when the property is calculated.) PHASE=V PHASE=L PHASE=L1 PHASE=L2 PHASE=T PHASE=S Vapor Total liquid First-liquid Second-liquid Total mixture Solid
PHASE
Phase compositions are determined at stream conditions. (Default=T, if listed as a valid phase for the property in Aspen Physical Property System Physical Property Data documentation; otherwise no default.) UNITS Units options selected for the units keywords that are listed for the property in Aspen Physical Property System Physical Property Data documentation. (Default=IN-UNITS if Prop-Set is specified for design specifications, Fortran blocks, optimization paragraphs and constraint paragraphs. Default=OUT-UNITS if Prop-Set is specified for reports. If a property has mole, mass, or flow units, the default will be mole units.)
468
TEMP PRES
Temperatures for property calculations. (Default=stream temperature. For VVSTD and VVSTDMX, Default=25C.) Pressures for property calculations. (Default=stream pressure. For VVSTD and VVSTDMX, Default=1 atm.)
Input Language for USER-PROPERTY
USER-PROPERTY
userpropid
propname-list
keyword=value
Keyword: SUBROUTINE Optional Keywords: FLASH UNIT-TYPE UNIT-LABEL COMP-DEP LVPCTDEP CURVE-PROP DEFAULT-PROP BLEND-METHOD BLEND-OPT EXTRAPOLATE
Input Language Description for USER-PROPERTY
Use the USER-PROPERTY paragraph to define the property. This property can be referenced in the Prop-Set paragraph in the same way as built-in properties. You must supply a Fortran subroutine to calculate the value of the user Prop-Set properties. userpropid User property set ID. This property must be different from built-in properties. (See Aspen Physical Property System Physical Property Data documentation.) Name of user-supplied subroutine for calculating the property. For details on writing the user-supplied subroutine, see Aspen Plus User Models reference manual. FLASH=NO Does not flash the stream before the user-supplied subroutine is called (Default) Does not flash the stream for total stream properties (When PHASE=T in the Prop-Set paragraph), but flashes for any other phase specification Always flashes stream before the usersupplied subroutine is called
SUBROUTINE
FLASH
FLASH= NOCOMPOSITE
FLASH=YES UNIT-TYPE
Units keyword for the property. If not entered, unit conversion is not performed on property values returned from the user-supplied subroutine.
469
UNIT-LABEL
Unit label for the property printed in the report. A unit label is used only when unit conversion is performed by the usersupplied subroutine (that is, when UNIT-TYPE is not given). COMP-DEP=YES COMP-DEP=NO Property is component property Property is a mixture property (Default)
COMP-DEP
Specifying Physical Property Inputs

This section describes the input language for specifying physical property inputs. More information on physical property methods and models is given in Volume 2 of this User Guide.
Specifying Property Methods

Following is the input language used to specify property methods.
Input Language for Property Methods
PROPERTIES opsetname keyword=value / opsetname [sectionid-list] keyword=value /... Optional keywords: FREE-WATER SOLU-WATER HENRY-COMPS henryid
HENRY-COMPS cid-list
Input Language Description for Property Methods
The PROPERTIES paragraph is used to specify the property method(s) to be used in your simulation. In this paragraph properties may be specified for the entire flowsheet, for a flowsheet section, or for an individual unit operation block. Depending on the component system used, additional information may be required such as Henry's law information, water solubility correlation, freewater phase properties. The input language for specifying property methods is as follows. opsetname sectionid-list FREE-WATER SOLU-WATER Primary property method name (See the Aspen Polymers User Guide, Volume 2). List of flowsheet section IDs. Free water phase property method name (Default=STEAMTA). Method for calculating the K-value of water in the organic phase.
470
SOLU-WATER=0
Water solubility correlation is used, vapor phase fugacity for water calculated by free water phase property method Water solubility correlation is used, vapor phase fugacity for water calculated by primary property method Water solubility correlation is used with a correction for unsaturated systems, vapor phase fugacity for water calculated by primary property method Primary property method is used. This method is not recommended for waterhydrocarbon systems unless waterhydrocarbon interaction parameters are available. (Default)
SOLU-WATER=1
SOLU-WATER=2
SOLU-WATER=3
HENRY-COMPS
Henry's constant component list ID.
The HENRY-COMPS paragraph identifies lists of components for which Henry's law and infinite dilution normalization are used. There may be any number of HENRY-COMPS paragraphs since different lists may apply to different blocks or sections of the flowsheet. henryid cid-list Henry's constant component list ID List of component IDs
Input Language Example for Property Methods
HENRY-COMPS PROPERTIES
HC
INI1 HENRY-COMPS=HC
POLYNRTL
Specifying Property Data

Following is the input language used to specify property data.
Input Language for Property Data
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PROP-DATA PROP-LIST paramname [setno] / . . . PVAL cid value-list / value-list / . . . PROP-LIST paramname [setno] / . . . BPVAL cid1 cid2 value-list / value-list / . . . COMP-LIST cid-list CVAL paramname setno 1 value-list COMP-LIST cid2-list BCVAL paramname setno 1 cid1 value-list / 1 cid1 value-list / . . . Physical property models require data in order to calculate property values. Once you have selected the property method(s) to be used in your simulation, you must determine the parameter requirements for the models contained in the property method(s), and ensure that they are available in the databanks. If the model parameters are not available from the databanks, you may estimate them using the Property Constant Estimation System, or enter them using the PROP-DATA or TAB-POLY paragraphs. The input language for the PROP-DATA paragraphs is as follows. Note that only the general structure is given, for information on the format for the input parameters required by polymer specific models see the relevant chapter in Volume 2 of this User Guide.
Input Language Description for Property Data
PROP-LIST PVAL BPVAL COMP-LIST CVAL BCVAL
Used to enter parameter names and data set numbers. Used to enter the PROP-LIST parameter values. Used to enter the PROP-LIST binary parameter values. Used to enter component IDs. Used to enter the COMP-LIST parameter values. Used to enter the COMP-LIST binary parameter values. paramname setno Parameter name Data set number. For CVAL and BCVAL the data set number must be entered. For setno > 1, the data set number must also be specified in a new property method defined using the PROP-REPLACE paragraph. (For PROP-LIST, Default=1) Component ID Component ID of first component of binary pair Component ID of second component of binary pair List of parameter values. For PROP-LIST, enter one value for each element of the property;
cid cid1 cid2 value-list
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for COMP-LIST, enter one value for each component in the cid-list. cid-list List of component ID
Input Language Example for Property Data
PROP-DATA IN-UNITS SI PROP-LIST PVAL HOPOLY PVAL COPOLY PROP-DATA IN-UNITS SI PROP-LIST PVAL HOPOLY PVAL COPOLY PVAL ABSEG PVAL ASEG PVAL BSEG PROP-DATA IN-UNITS SI PROP-LIST PVAL HOPOLY PVAL COPOLY PROP-DATA IN-UNITS SI PROP-LIST GMRENB BPVAL MCH ASEG -92.0 BPVAL ASEG MCH 430.0 / / / GMRENC 0.2 0.2 DHCONM -3.64261D4 -3.64261D4 / / / DHSUB 8.84633D4 8.84633D4 / / / TMVK 1.0 1.0 / TGVK / 0.0 / 0.0 MW 1.0 1.0 192.17 76.09 116.08 PLXANT -40.0 0 0 0 0 0 0 0 1D3 -40.0 0 0 0 0 0 0 0 1D3 / TB / 2000.0 / 2000.0
Estimating Property Parameters

Following is the input language used to estimate property parameters.
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Input Language for Property Parameter Estimation
ESTIMATE [option] STRUCTURES method SEG-id
groupno nooccur / groupno nooccur /...
Input Language Description for Property Parameter Estimation
The main keywords for specifying property parameter estimation inputs are the ESTIMATE and the STRUCTURES paragraphs. A brief description of the input language for these paragraphs follows. For more detailed information please refer to the Aspen Physical Property System Physical Property Data documentation. option method SEG-id groupno nooccur Option=ALL Estimate all missing parameters (default)
Polymer property estimation method name Segment ID defined in the component list Functional group number (group IDs listed in Appendix B of Volume 2 of this User Guide) Number of occurrences of the group
Input Language Example for Property Parameter Estimation
ESTIMATE ALL STRUCTURES VANKREV VANKREV COOVANKREV COOABSEG BSEG ABSEG 115 1 115 1 151 2 / 100 2 / 151 2 / 100 2 ;-(C6H4); -COO-CH2-CH2-
;-(C6H4)-COO-CH2-CH2-
Specifying Step-Growth Polymerization Kinetics

Following is the input language for the STEP-GROWTH REACTIONS paragraph.
Input Language for Step-Growth Polymerization
REACTIONS rxnid DESCRIPTION
STEP-GROWTH '...'
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REPORT REPORT=yes/no RXN-SUMMARY=yes/no RXN-DETAILS=yes/noI STOIC reactionno compid coeff / ... RATE-CON setno pre-exp act-energy [T-exp] [T-ref] [USER-RC=number] [CATALYST=compid] [CAT-ORDER=value] POWLAW-EXP reactionno compid exponent / [ASSIGN reactionno [ACTIVITY=value] RC-SETS=setno-list] SPECIES POLYMER=polymerid OLIGOMER=oligomer-list REAC-GRP groupid type / SPEC-GROUP compid groupid number / groupid ...
number
RXN-SET rxn-setno [A-NUCL-SPEC=compid] [A-ELEC-GRP=groupid] & [V-ELEC-SPEC=compid] [V-NUCL-GRP=groupid] & [V-NUCL-SPEC=compid] [V-ELEC-GRP=groupid] & RC-SETS=rc-setno-list SG-RATE-CON rc-setno [CAT-SPEC=compid] [CAT-GRP=groupid] & sgpre-exp [sgact-energy] [sgt-exp] [sgt-ref] [USERRC=number] SUBROUTINE KINETICS=kinname RATECON=rcname MASSTRANS=mtname USER-VECS NINTK=nintk NREALK=nrealk NINTRC=nintrc & NREALRC=nrealc NINTMT=nintmt NREALMT=nrealmt & NIWORK=niwork NWORK=nwork NURC=nurc INTK value-list REALK value-list INTRC value-list REALRC value-list INTMT value-list REALMT value-list INCL-COMPS compid-list REAC-TYPE FOR-CON=yes/no REV-CON=yes/no REARRANGE=yes/no EXCHANGE=yes/no CONVERGENCE
BULK=yes/no
SOLVE-ZMOM=yes/no OLIG-TOL=tolerance
SUPPRESS-WARN=yes/no USE-
OPTIONS
REAC-PHASE=phaseid CONC-BASIS=basis
The keywords for specifying rate constant parameters for the built-in reactions, and for specifying user reactions are described here.
Input Language Description for Step-Growth Polymerization
rxnid DESCRIPTION REPORT
Unique paragraph ID. Up to 64 characters between double quotes. Reaction report options- controls writing of reaction report in .REP file. REPORT=YES REPORT=NO RXNSUMMARY=YES Print reaction report Do not print reaction report Print stoichiometry for each modelgenerated and user-specified reaction. (Default).
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RXNSUMMARY=NO
Do not print this summary.
RXN-DETAILS=YES Print stoichiometry, rate constants, and probability factors for each modelgenerated and user-specified reaction. RXN-DETAILS=NO Do not print this detailed summary. STOIC Used to specify stoichiometry for user reactions. Reactionno compid coeff RATE-CON Reaction number Component ID Stoichiometric coefficient (positive for products, negative for reactants)
Used to specify rate constants for user reactions. SetNo pre-exp act-energy T-exp T-ref number CATALYST= compid Rate constant set number Pre-exponential factor in inverse-time units Activation energy in mole enthalpy units Temperature exponent Reference temperature User rate constant flag Optional catalyst component ID
CAT-ORDER=value Optional reaction order for catalyst (default=1) POWLAW-EXP Used to specify power-law exponents for user reactions. reactionno compid exponent ASSIGN Reaction number Component ID Power law exponent
Used to assign rate constant(s) to user reactions. reactionno ACTIVITY= value Reaction number Multiplying factor used to calculate net rate constant List of rate constants (from RATE-CON) which apply to this user reaction
RC-SETS = setno-list
SPECIES
Used to specify key components involved in the reactions. polymerid oligomer-list Component ID for polymer product List of oligomers to be tracked
REAC-GRP
Used to identify the names and types of reacting functional groups participating in the reaction network.
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groupid type EE-GRP NN-GRP EN-GRP E-GRP N-GRP EX-GRP NX-GRP SPEC-GROUP
Functional group ID Functional group type Electrophilic repeat unit Nucleophilic repeat unit Mixed electrophilic/nucleophilic repeat unit Electrophilic leaving group Nucleophilic leaving group Electrophilic modifier (end cap) Nucleophilic modifier (end cap)
Used to characterize the reacting functional group composition of the components (segments and monomers) participating in the step-growth reaction network. compid groupid number Component ID Reactive functional group ID Number of occurrences of group in species
SG-RATE-CON
Used to specify rate constants for model-generated stepgrowth reactions and to specify which catalyst they apply to (if any). setno CAT-SPEC= compid CAT-GRP= groupid USER-RC= number sgpre-exp sgact-energy sgt-exp sgt-ref Rate constant set number Component ID of catalyst species Group ID of catalyst group User rate expression flag Pre-exponential factor in inverse-time units Activation energy in mole-enthalpy units Temperature exponent Reference temperature in temperature units
RXN-SET
Used to assign sets of rate constants to model-generated reactions. A-NUCL-SPEC= compid A-ELEC-GRP= groupid V-ELEC-SPEC= compid Component ID of reactant which acts as the attacking nucleophile Group ID of electrophilic leaving group in attacking nucleophilic reactant Component ID of reactant which acts as the nucleophile. When reactions occur inside polymer molecules, this may be a segment.
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V-ELEC-GRP= groupid V-NUCL-SPEC= compid V-NUCL-GRP= groupid
Group ID of electrophilic group in victim species (attached to V-NUCL-GRP) Component ID of nucleophilic reactant attached to the victim electrophilic reactant at the reacting site Group ID of nucleophilic group in victim species (attached to V-ELEC-GRP) List of rate constants (from SG-RATECON) which apply to the set of reactions identified by the previous keywords
RC-SETS = rcsetno-list
SUBROUTINE
Used to provide the names of user-supplied Fortran subroutines. The subroutine argument lists are documented in the User Subroutines section of Chapter 3. KINETICS= kinname RATECON= rcname MASSTRAN= mtname User kinetic subroutine name User rate constant subroutine name User concentration basis / mass-transfer subroutine name
USER-VECS
Used to specify the size of vectors for user subroutines. NINTK=nintk NREALK=nrealk NINTRC=nintrc NREALRC= nrealrc NINTMT=nintmt NREALMT= nrealmt NIWORK= niwork NWORK=nwork NURC=nurc Length of integer array for kinetics Length of real array for kinetics Length of integer array for rate constants Length of real array for rate constants Length of integer array for user basis routine Length of real array for user basis routine Total length of integer workspace Total length of real workspace Number of rate constants calculated by user subroutine
INTK REALK INTRC REALRC INTMT REALMT
Used to enter integer parameter for kinetics. Used to enter real parameters for kinetics. Used to enter integer parameters for rate constants. Used to enter real parameters for rate constants. Used to enter integer parameters for mass transfer. Used to enter real parameters for mass transfer.
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INCL-COMPS
Used to list components which participate in reactions in the user kinetics model, but which do not appear in modelgenerated or user-specified reactions. Compid-list List of additional components to include in the mass-balance calculations
REAC-TYPE
Used to specify which classes of reactions will be generated by the step-growth model (default is YES for all types of reactions. FOR-CON= yes/no REV-CON= yes/no REARRANGE= yes/no EXCHANGE= yes/no Generate forward condensation reactions Generate reverse condensation reactions Generate re-arrangement reactions Generate end-group exchange reactions
CONVERGENCE
Used to specify convergence parameters. SOLVE-ZMOM= yes/no Explicitly solve zeroth moment (default = no) Specify tolerance for oligomer fractionation calculations (default is 1x10-4)
OLIG-TOL= tolerance
OPTIONS
Used to specify reaction model options. REAC-PHASE= phaseID CONC-BASIS= basis Specify the reacting phase as L, L1, L2, or V (default is L) Specify concentration units for rate constants as MOL/L (default), MMOL/L, MOL/KG, or MMOL/KG
SUPRESS-WARN= YES: do not print warnings when the yes/no specified phase is not present NO: always print warnings when the specified phase is not present (default) USE-BULK= yes/no YES: force the model to apply the specified reaction kinetics to the bulk phase when the specified phase is not present (default) NO: rates are set to zero when the specified phase is not present
Input Language Example for Step-Growth Polymerization
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REACTIONS NYLON STEP-GROWTH DESCRIPTION NYLON-6 KINETICS: REPORT RXN-DETAILS=YES SPECIES POLYMER=NYLON6 REAC-GROUP TNH2 E-GRP / TCOOH N-GRP / BCAP EN-GRP SPECIES-GRP T-NH2 TNH2 1 / T-NH2 BCAP 1 / T-COOH TCOOH 1 / T-COOH BCAP 1 / ACA TNH2 1 / ACA TCOOH 1 / SG-RATE-CON 1 ENERGY=23.271 SG-RATE-CON 2 CAT-SPEC=ACA ENERGY=20.670 & & SIMPLE MODEL WITHOUT CYCLICS
ACA BCAP 1 / B-ACA BCAP 1 / H2O TNH2 1 / H2O TCOOH 1 TREF=260 PRE-EXP= 5.461 ACTTREF=260 PRE-EXP=40.678 ACT-
SG-RATE-CON 3 CAT-SPEC=T-COOH TREF=260 PRE-EXP=40.678 ACTENERGY=20.670 SG-RATE-CON 4 ENERGY=29.217 SG-RATE-CON 5 CAT-SPEC=ACA ENERGY=26.616 TREF=260 PRE-EXP=0.0124 ACTTREF=260 PRE-EXP=0.0924 ACT-
SG-RATE-CON 6 CAT-SPEC=T-COOH TREF=260 PRE-EXP=0.0924 ACTENERGY=26.616 RXN-SET 1 ELECTRO-GRP=TNH2 NUCLEO-GRP=TCOOH RC-SETS= 1 2 3 RXN-SET 2 NUCLEOPHILE=H2O STOIC 1 CL -1.0 / H2O -1.0 / ACA 1.0 STOIC 2 CL -1.0 / H2O -1.0 / ACA 1.0 STOIC 3 CL -1.0 / H2O -1.0 / ACA 1.0 STOIC 4 ACA -1.0 / CL 1.0 / H2O 1.0 STOIC 5 ACA -1.0 / CL 1.0 / H2O 1.0 STOIC 6 ACA -1.0 / CL 1.0 / H2O 1.0 STOIC 7 CL -1.0 / B-ACA 1.0 STOIC 8 CL -1.0 / B-ACA 1.0 STOIC 9 CL -1.0 / B-ACA 1.0 STOIC 10 B-ACA -1.0 / CL 1.0 STOIC 11 B-ACA -1.0 / CL 1.0 STOIC 12 B-ACA -1.0 / CL 1.0 STOIC 13 CL -1.0 / ACA -1.0 / T-NH2 1.0 / T-COOH 1.0 STOIC 14 CL -1.0 / ACA -1.0 / T-NH2 1.0 / T-COOH 1.0 STOIC 15 CL -1.0 / ACA -1.0 / T-NH2 1.0 / T-COOH 1.0 STOIC 16 T-NH2 -1.0 / T-COOH -1.0 / ACA 1.0 / CL 1.0 RC-SETS= 4 5 6
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STOIC 17 T-NH2 -1.0 / T-COOH -1.0 / ACA 1.0 / CL 1.0 STOIC 18 T-NH2 -1.0 / T-COOH -1.0 / ACA 1.0 / CL 1.0 STOIC 19 CL -1.0 / B-ACA 1.0 STOIC 20 CL -1.0 / B-ACA 1.0 STOIC 21 CL -1.0 / B-ACA 1.0 RATE-CON 1 RATE-CON 2 RATE-CON 3 RATE-CON 4 RATE-CON 5 RATE-CON 6 RATE-CON 7 RATE-CON 8 RATE-CON 9 PRE-EXP=0.00424 ACT-ENERGY=19.880 TREF=260 TREF=260 TREF=260 TREF=260 TREF=260 TREF=260 TREF=260 TREF=260 TREF=260 TREF=260 TREF=260 TREF=260 TREF=260 TREF=260 TREF=260 TREF=260 TREF=260 TREF=260 TREF=260 TREF=260 TREF=260 PRE-EXP=0.840712 ACT-ENERGY=18.806 PRE-EXP=0.840712 ACT-ENERGY=18.806 PRE-EXP=1.370519 ACT-ENERGY=17.962 PRE-EXP=271.7817 ACT-ENERGY=16.888 PRE-EXP=271.7817 ACT-ENERGY=16.888 PRE-EXP=1.23117 ACT-ENERGY=22.845
PRE-EXP=93.61226 ACT-ENERGY=20.107 PRE-EXP=93.61226 ACT-ENERGY=20.107
RATE-CON 10 PRE-EXP=0.893159 ACT-ENERGY=26.888 RATE-CON 11 PRE-EXP=67.83767 ACT-ENERGY=24.151 RATE-CON 12 PRE-EXP=67.83767 ACT-ENERGY=24.151 RATE-CON 13 PRE-EXP=1.23117 ACT-ENERGY=22.845 RATE-CON 14 PRE-EXP=93.61226 ACT-ENERGY=20.107 RATE-CON 15 PRE-EXP=93.61226 ACT-ENERGY=20.107 RATE-CON 16 PRE-EXP=0.893159 ACT-ENERGY=26.888 RATE-CON 17 PRE-EXP=67.83767 ACT-ENERGY=24.151 RATE-CON 18 PRE-EXP=67.83767 ACT-ENERGY=24.151 RATE-CON 19 PRE-EXP=0.893159 ACT-ENERGY=26.888 RATE-CON 20 PRE-EXP=67.83767 ACT-ENERGY=24.151 RATE-CON 21 PRE-EXP=67.83767 ACT-ENERGY=24.151 POWLAW-EXP 1 CL 1.0 / H2O 1.0 POWLAW-EXP 2 CL 1.0 / H2O 1.0 / T-COOH 1.0 POWLAW-EXP 3 CL 1.0 / H2O 1.0 / ACA 1.0 POWLAW-EXP 4 ACA 1.0 POWLAW-EXP 5 ACA 1.0 / T-COOH 1.0 POWLAW-EXP 6 ACA 2.0 POWLAW-EXP 7 CL 1.0 / T-NH2 1.0 POWLAW-EXP 8 CL 1.0 / T-NH2 1.0 / T-COOH 1.0
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POWLAW-EXP 9 CL 1.0 / T-NH2 1.0 / ACA 1.0 POWLAW-EXP 10 T-NH2 1.0 POWLAW-EXP 11 T-NH2 1.0 / T-COOH 1.0 POWLAW-EXP 12 T-NH2 1.0 / ACA 1.0 POWLAW-EXP 13 CL 1.0 / ACA 1.0 POWLAW-EXP 14 CL 1.0 / ACA 1.0 / T-COOH 1.0 POWLAW-EXP 15 CL 1.0 / ACA 2.0 POWLAW-EXP 16 ACA 1.0 POWLAW-EXP 17 T-COOH 1.0 / ACA 1.0 POWLAW-EXP 18 ACA 2.0 POWLAW-EXP 19 ACA 1.0 POWLAW-EXP 20 ACA 1.0 / T-COOH 1.0 POWLAW-EXP 21 ACA 2.0 CONVERGENCE SOLVE-ZMOM=YES OPTIONS REAC-PHASE=L CONC-BASIS=MOL/KG
Specifying Free-Radical Polymerization Kinetics

Following is the input language for the FREE-RAD REACTIONS paragraph. The reaction keywords and rate coefficient parameters for free-radical polymerization are given. Users may select a subset of the built-in reactions for a given simulation.
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Input Language for Free-Radical Polymerization
REACTIONS PARAM SPECIES
reacid FREE-RAD QSSA=yes/no QSSAZ=yes/no QSSAF=yes/no RAD-INTENS=value POLYMER=cid INITIATOR=cid-list MONOMER=cid-list INHIBITOR=cid-list & SOLVENT=cid-list BI-INITIATOR=cid-list COINITIATOR=cid-list CHAINTAG=cid-list & CATALYST=cid-list INIT-DEC cid idpre-exp idact-energy idact-volume ideffic & idnrad ref-temp [GEL-EFFECT=gelid] [EFF-GEFF=gelid] [COEF1=value BYPROD1=cid] & [COEF2=value BYPROD2=cid] INIT-CAT cid1 cid2 icpre-exp icact-energy icact-volume iceffic icnrad ref-temp [GEL-EFFECT=gelid] [EFF-GEFF=gelid] & cid1 cid2 [COEF1=value BYPROD1=cid] [COEF2=value BYPROD2=cid] ispre-exp isact-energy isact-volume ref-temp &
INIT-SP INIT-SP-EFF BI-INIT-DEC
[GEL-EFFECT=gelid] [COEF1=value BYPROD1=cid] [COEF2=value BYPROD2=cid] cid coeffa coeffb coeffc cid bdpre-exp bdact-energy bdact-volume bdeffic ref-temp [GEL-EFFECT=gelid] [EFF-GEFF=gelid] & [COEF1=value BYPROD1=cid] [COEF2=value BYPROD2=cid] sdpre-exp sdact-energy sdact-volume sdeffic ref-temp [GEL-EFFECT=gelid] [EFF-GEFF=gelid] & cid cid2 cid2 cid2 cid2 cid2 cid cid2 cid2 cid2 cid2 cid2 cid2 cid2 cid2 cid2 [COEF1=value BYPROD1=cid] cipre-exp ciact-energy prpre-exp pract-energy cmpre-exp cmact-energy cppre-exp cpact-energy capre-exp caact-energy cspre-exp csact-energy bspre-exp bsact-energy tdpre-exp tdact-energy tcpre-exp tcact-energy inpre-exp inact-energy scpre-exp scact-energy hppre-exp hpact-energy pcpre-exp pcact-energy ptpre-exp tdpre-exp pbpre-exp ptact-energy tdact-energy pbact-energy [COEF2=value BYPROD2=cid] ciact-volume ref-temp [GEL-EFFECT=gelid] pract-volume ref-temp [GEL-EFFECT=gelid] cmact-volume ref-temp [GEL-EFFECT=gelid] cpact-volume ref-temp [GEL-EFFECT=gelid] caact-volume ref-temp [GEL-EFFECT=gelid] csact-volume ref-temp [GEL-EFFECT=gelid] bsact-volume ref-temp [GEL-EFFECT=gelid] tdact-volume ref-temp [GEL-EFFECT=gelid] tcact-volume ref-temp [GEL-EFFECT=gelid] inact-volume ref-temp [GEL-EFFECT=gelid] scact-volume ref-temp [GEL-EFFECT=gelid] hpact-volume ref-temp [GEL-EFFECT=gelid] pcact-volume ref-temp [GEL-EFFECT=gelid] pcact-volume tdact-volume pbact-volume ref-temp ref-temp ref-temp [GEL-EFFECT=gelid] [GEL-EFFECT=gelid] [GEL-EFFECT=gelid]
SEC-INIT-DEC cid
CHAIN-INI PROPAGATION CHAT-MON CHAT-POL CHAT-AGENT CHAT-SOL B-SCISSION TERM-DIS TERM-COMB INHIBITION SC-BRANCH HTH-PROP CIS-PROP TRANS-PROP TDB-POLY PDB-POLY
cid1 cid1 cid1 cid1 cid1 cid1 cid1 cid1 cid1 cid1 cid1 cid1 cid1 cid1
GEL-EFFECT gelid CORR-NO=corrno & MAX-PARAMS=maxparams GE-PARAMS=paramlist / ... SUBROUTINE GEL-EFFECT=subname OPTIONS REAC-PHASE=phaseid SUPRESS-WARN=yes/no USE-BULK=yes/no
Input Language Description for Free-Radical Polymerization
reacid PARAM
Paragraph ID. Used to specify polymerization mechanism, radiation intensity, and request the Quasi-Steady-State Approximation (QSSA). RAD-INTENS= Used to specify a value for the radiation value intensity to be used for the induced initiation reaction (default is 1.0)
QSSA= YES/NO
Used to request QSSA for all moments (default is NO)
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QSSAZ= YES/NO QSSAF= YES/NO QSSAS= YES/NO SPECIES
Used to request QSSA for the zeroth moment only (default is NO) Used to request QSSA for the first moment only (default is NO) Used to request QSSA for the second moment only (default is NO)
Reacting species identification. This sentence is used to associate components in the simulation with reactive species in the built-in free-radical kinetic scheme. The following species keywords are currently valid INITIATOR List of standard initiators
BI-INITIATOR List of bifunctional initiators CATALYST List of catalysts
COINITIATOR List of coinitiators MONOMER POLYMER CHAINTAG SOLVENT INHIBITOR MON-RSEG List of monomers Reacting polymer ID Chain transfer agends List of solvents which act as chain transfer agents List of inhibitors
Specifies the pairing between monomers and their corresponding repeat segments in a polymer. monomer r-seg Monomer ID Corresponding repeat segment ID
INIT-DEC
Identifier for initiator decomposition reaction. cid1 idpre-exp idact-energy idact-volume ideffic idnrad ref-temp Initiator ID Preexponential factor Activation energy Activation volume (default is 0.0) Initiator efficiency (default is 1.0) Number of radicals from one initiator molecule (default is 2.0) Reference temperature
GEL-EFF=gelid Gel effect sentence ID EFFGEFF=gelid Efficiency factor gel effect sentence ID
COEF1=value Stoichiometric coefficient of first by-product (default=1.0)
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BYPROD1=cid Byproduct 1 component ID COEF2=value Stoichiometric coefficient of 2nd by-product (default=1.0) BYPROD2=cid Byproduct 2 component ID INIT-CAT Identifier for catalyzed initiator decomposition reaction. cid1 cid2 icpre-exp icact-energy icact-volume iceffic icnrad ref-temp Initiator ID Catalyst ID Preexponential factor Activation energy Activation volume (default=0.0) Initiator efficiency (default=1.0) Number of radicals from one initiator molecule (default=2.0) Reference temperature
COEF1=value Stoichiometric coefficient of first by-product (default=1.0) BYPROD1=cid Byproduct 1 component ID COEF2=value Stoichiometric coefficient of 2nd by-product (default=1.0) BYPROD2=cid Byproduct 2 component ID INIT-SP Identifier for thermal and radiation induced initiation reaction. cid1 cid2 ispre-exp isact-energy isact-volume ref-temp INIT-SP-EFF Monomer ID Co-initiator ID Preexponential factor Activation energy Activation volume (default is 0.0) Reference temperature
Parameters for thermal and radiation induced initiation reaction. cid coeffa Monomer ID Exponent for coinitiator concentration (default is 0.0)
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coeffb coeffc ref-temp BI-INIT-DEC
Exponent for monomer concentration (default is 0.0) Exponent for radiation intensity (default is 0.0) Reference temperature
Bifunctional initiator primary decomposition cid1 bdpre-exp Bi-initiator ID Preexponential factor
bdact-energy Activation energy bdact-volume Activation volume (default is 0.0) bdeffic ref-temp Initiator efficiency (default is 1.0) Reference temperature
COEF1=value Stoichiometric coefficient of first by-product (default=1.0) BYPROD1=cid Byproduct 1 component ID COEF2=value Stoichiometric coefficient of 2nd by-product (default=1.0) BYPROD2=cid Byproduct 2 component ID SEC-INIT-DEC Bifunctional initiator secondary decomposition cid1 sdpre-exp sdact-energy Bi-initiator ID Preexponential factor Activation energy
sdact-volume Activation volume (default is 0.0) sdeffic ref-temp Initiator efficiency (default is 1.0) Reference temperature
COEF1=value Stoichiometric coefficient of first by-product (default=1.0) BYPROD1=cid Byproduct 1 component ID COEF2=value Stoichiometric coefficient of 2nd by-product (default=1.0) BYPROD2=cid Byproduct 2 component ID
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CHAIN-INI
Identifier for chain initiation reaction. cid1 cipre-exp ciact-energy ciact-volume ref-temp Monomer ID Preexponential factor Activation energy Activation volume (default is 0.0) Reference temperature
GEL-EFF=gelid Gel effect sentence ID PROPAGATION Identifier for chain propagation reaction. cid1 cid2 prpre-exp pract-energy pract-volume ref-temp Active segment ID Monomer ID Preexponential factor Activation energy Activation volume (default is 0.0) Reference temperature
GEL-EFF=gelid Gel effect sentence ID CHAT-MON Identifier for chain transfer to monomer reaction. cid1 cid2 cmpre-exp cmact-energy Monomer corresponding to polymer active segment ID Monomer ID Preexponential factor Activation energy
cmact-volume Activation volume (default is 0.0) ref-temp Reference temperature
GEL-EFF=gelid Gel effect sentence ID CHAT-POL Identifier for chain transfer to polymer reaction. cid1 cid2 cppre-exp cpact-energy cpact-volume ref-temp Active segment ID Segment ID on dead chain Preexponential factor Activation energy Activation volume (default is 0.0) Reference temperature
GEL-EFF=gelid Gel effect sentence ID CHAT-AGENT Identifier for chain transfer to transfer agent reaction. cid1 cid2 Active segment ID Transfer agent ID
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capre-exp caact-energy caact-volume ref-temp
Preexponential factor Activation energy Activation volume (default is 0.0) Reference temperature
GEL-EFF=gelid Gel effect sentence ID CHAT-SOL Identifier for chain transfer to solvent reaction. cid1 cid2 cspre-exp csact-energy csact-volume ref-temp Active segment ID Solvent ID Preexponential factor Activation energy Activation volume (default is 0.0) Reference temperature
GEL-EFF=gelid Gel effect sentence ID B-SCISSION Identifier for beta-scission reaction. cid1 bspre-exp bsact-energy bsact-volume ref-temp Active segment ID Preexponential factor Activation energy Activation volume (default is 0.0) Reference temperature
GEL-EFF=gelid Gel effect sentence ID TERM-DIS Identifier for chain termination by disproportionation reaction. cid1 cid2 tdpre-exp tdact-energy tdact-volume ref-temp First polymer active segment ID Second polymer active segment ID Preexponential factor Activation energy Activation volume (default is 0.0) Reference temperature
GEL-EFF=gelid Gel effect sentence ID TERM-COMB Identifier for chain termination by combination reaction. cid1 cid2 tcpre-exp Monomer corresponding to first polymer active segment ID Monomer corresponding to second polymer active segment ID Preexponential factor
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tcact-energy tcact-volume ref-temp
Activation energy Activation volume (default is 0.0) Reference temperature
GEL-EFF=gelid Gel effect sentence ID INHIBITION Identifier for chain inhibition reaction. cid1 cid2 inpre-exp inact-energy inact-volume ref-temp Polymer active segment ID Inhibitor ID Preexponential factor Activation energy Activation volume (default is 0.0) Reference temperature
GEL-EFF=gelid Gel effect sentence ID SC-BRANCH Identifier for short chain branching reaction. cid1 cid2 scpre-exp scact-energy scact-volume ref-temp Reactant polymer active segment ID Product active segment ID Preexponential factor Activation energy Activation volume (default is 0.0) Reference temperature
GEL-EFF=gelid Gel effect sentence ID HTH-PROP Head-to-head propagation reaction cid1 cid2 hppre-exp hpact-energy hpact-volume ref-temp Active segment ID Monomer ID Preexponential factor Activation energy Activation volume (default is 0.0) Reference temperature
GEL-EFF=gelid Gel effect sentence ID CIS-PROP Cis-propagation for diene monomers cid1 cid2 pcpre-exp pcact-energy pcact-volume Active segment ID Diene monomer ID Preexponential factor Activation energy Activation volume (default is 0.0)
489
ref-temp
Reference temperature
GEL-EFF=gelid Gel effect sentence ID TRANS-PROP Trans-propagation for diene monomers cid1 cid2 prpre-exp pract-energy pract-volume ref-temp Active segment ID Diene monomer ID Preexponential factor Activation energy Activation volume (default is 0.0) Reference temperature
GEL-EFF=gelid Gel effect sentence ID TDB-POLY Terminal double bond polymerization cid1 cid2 tbpre-exp tbact-energy tbact-volume ref-temp Reactant polymer active segment ID Terminal double bond segment ID Preexponential factor Activation energy Activation volume (default is 0.0) Reference temperature
GEL-EFF=gelid Gel effect sentence ID PDB-POLY Pendent double bond polymerization cid1 cid2 pbpre-exp pbact-energy pbact-volume ref-temp Reactant polymer active segment ID Pendent double bond segment ID Preexponential factor Activation energy Activation volume (default is 0.0) Reference temperature
GEL-EFF=gelid Gel effect sentence ID GEL-EFFECT Gel effect switch and correlation selection. This sentence is used to: Modify the reaction rate expression or initiator efficiency factor, typically to account for the gel effect at high conversion. Select a gel effect correlation from a list of built-in and user specified gel effect correlations Specify the maximum number of parameters Specify the parameter values for the selected correlation The default action is to not include a gel effect.
490
gelid
Gel effect sentence ID Used to identify the type of reaction to apply gel effect to. A list of valid reaction types follows Used to select a correlation number. If a correlation number greater than the number of built-in correlations (currently 2) is specified then the user should supply a Fortran subroutine containing the user gel effect correlation. Used to enter the maximum number of gel effect parameters for the correlation selected. Used to enter a list of parameters for the correlation selected.
GETYPE= reactiontype CORR-NO= corrno
MAX-PARAMS= maxparams
GE-PARAMS= paramlist
SUBROUTINE GEL-EFFECT= subname
User subroutines sentence. Used to specify the name of the subroutine containing user gel effect correlations. The user gel-effect subroutine argument list was shown in the Gel Effect section in Chapter 3. A Fortran template called USRGEL.F is available for your use.
OPTIONS
Used to specify reaction model options. REAC-PHASE= phaseID Specify the reacting phase as L, L1, L2, or V (default is L)
SUPRESS-WARN= YES: do not print warnings when the yes/no specified phase is not present NO: always print warnings when the specified phase is not present (default) USE-BULK= yes/no YES: force the model to apply the specified reaction kinetics to the bulk phase when the specified phase is not present (default) NO: rates are set to zero when the specified phase is not present
Input Language Example for Free-Radical Polymerization
REACTIONS SBD FREE-RAD DESCRIPTION "test file" PARAM QSSA=yes
491
SPECIES INITIATOR=APS MONOMER=STY BD
&
SOLVENT=EB POLYMER=SBD CHAINTAG=DDM COINITIATOR=CINI INIT-DEC APS 1.6220E+11 1.1530E+08 0.0 EFFIC=.80 NRADS=2 & BYPROD1=CO2 COEF1=0.1 BYPROD2=CO COEF2=0.2 INIT-SP STY CINI 438000.0 1.1480E+08 0.0 CHAIN-INI CHAIN-INI PROPAGATION PROPAGATION PROPAGATION PROPAGATION HTH-PROP HTH-PROP CIS-PROP CIS-PROP TRANS-PROP TRANS-PROP STY 2.2E7 3.2E7 BD 1.2E8 3.88E7 3.2E7 3.2E7 3.88E7 3.88E7 3.2E7 3.88E7 3.88E7 3.2E7 3.88E7 3.2E7 3.2E7 3.2E7 3.88E7 3.88E7 4.4E7 1.2E8 STY STY 2.2E7 STY BD BD BD BD BD BD BD
STY 8.5E7 BD BD BD 1.2E6 1.2E6 4.4E5 1.2E6 4.4E5
STY STY 2.2E5
STY BD STY BD
CHAT-MON STY STY CHAT-MON STY BD CHAT-MON BD CHAT-MON BD CHAT-AGENT CHAT-AGENT CHAT-SOL CHAT-SOL BD STY BD BD
2200. 4400. 12000. 8500. DDM EB
STY DDM 1051.0 2.9590E+07 0.0 900.0 2.9590E+07 0.0 1051.0 2.9590E+07 0.0 900.0 2.9590E+07 0.0 1.00E6 1.00E6 1.30E7 1.30E7 1.30E7 1.30E7 1.30E6 1.30E6 1.30E6 1.30E6 4.4E5 4.5E7 TDB-FRAC=1 4.5E7 TDB-FRAC=1 9.90E6 GEL-EFFECT=1 9.90E6 GEL-EFFECT=1 9.90E6 GEL-EFFECT=1 9.90E6 GEL-EFFECT=1 9.90E6 GEL-EFFECT=1 9.90E6 GEL-EFFECT=1 9.90E6 GEL-EFFECT=1 9.90E6 GEL-EFFECT=1 STY EB
B-SCISSION STY B-SCISSION BD TERM-COMB TERM-COMB TERM-COMB TERM-COMB TERM-DIS TERM-DIS TERM-DIS TERM-DIS TDB-POLY TDB-POLY STY STY STY BD BD BD BD STY STY STY STY BD BD BD BD STY STY BD
STY STY 2.2E5
3.2E7 3.2E7
492
TDB-POLY TDB-POLY PDB-POLY PDB-POLY GEL-EFFECT 0.0 2
BD BD BD
BD
1.2E6 4.4E3 1.2E2
3.88E7 3.88E7 3.2E7 3.88E7 &
STY 8.5E5 BD
STY BD
INIT-SP-EFF STY COEFFA=0.0 COEFFB=3.0 COEFFC=0.0 1 CORR-NO=2 MAX-PARAMS=10 GE-PARAMS=1 0 2.57 -5.05E-3 9.56 -1.76E-2 -3.03 7.85E-3
Specifying Emulsion Polymerization Kinetics

Following is the input language for the EMULSION REACTIONS paragraph. Users are able to select the phases in which the reactions are occurring and also define the kinetics of particle absorption, desorption, and termination.
Input Language for Emulsion Polymerization
REACTIONS PARAM SPLIT-PM SPECIES reacid EMULSION KBASIS=monomer/aqueous spm-cid kll INITIATOR=cid MONOMER=cid INHIBITOR=cid & DISPERSANT=cid . . . INIT-DEC phasid cid idpre-exp idact-energy [idact-volume] idnrad ref-temp INIT-CAT phased cid1 cid2 icpre-exp icact-energy [icact-volume] icnrad ref-temp INIT-ACT phasid cid1 cid2 iapre-exp iaact-energy [iaact-volume] ianrad ref-temp PROPAGATION phasid cid1 cid2 prpre-exp pract-energy [pract-volume] CHAT-MON phasid cid1 cid2 cmpre-exp cmact-energy [cmact-volume] CHAT-POL phasid cid1 cid2 cppre-exp cpact-energy [cpact-volume] CHAT-AGENT phasid cid1 cid2 capre-exp caact-energy [caact-volume] TERM-DIS phasid cid1 cid2 tdpre-exp tdact-energy [tdact-volume] TERM-COMB phasid cid1 cid2 tcpre-exp tcact-energy [tcact-volume] INHIBITION phasid cid1 cid2 inpre-exp inact-energy [inact-volume] REDUCTION phasid cid1 cid2 rdpre-exp rdact-energy [rdact-volume] rdnrad ref-temp OXIDATION phasid cid1 cid2 oxpre-exp oxact-energy [oxact-volume] GEL-EFFECT GETYPE=reactiontype CORR-NO=corrno & MAX-PARAMS=maxparams GE-PARAMS=paramlist / ... SUBROUTINE GEL-EFFECT=subname ABS-MIC ampre-exp amact-energy ABS-PART appre-exp apact-energy DES-PART dppre-exp dpact-energy EMUL-PARAMS emulid cmc-conc area
ideffic & iceffic & iaeffic ref-temp ref-temp ref-temp ref-temp ref-temp ref-temp ref-temp rdeffic & ref-temp &
Input Language Description for Emulsion Polymerization
reacid PARAM
Paragraph ID. Use to enter basis parameters.
493
KBASIS= monomer/ aqueous

SPLIT-PM
Basis for phase split ratios
Used to enter homosaturation solubility of species in the polymer phase. spm-cid kll Component ID of the species partitioning into the polymer phase Ratio of mass fraction of species in polymer phase to mass fraction in reference phase. KBASIS determines whether the reference phase is the monomer of aqueous phase
SPECIES
Reacting species identification. This sentence is used to associate components in the simulation with species in the built-in free-radical kinetic scheme. The following species keywords are currently valid INITIATOR CATALYST MONOMER CHAINTAG DISPERSANT INHIBITOR POLYMER EMULSIFIER ACTIVATOR REDOX-AGENT REDUCTANT
INIT-DEC
Identifier for initiator decomposition reaction. phasid cid idpre-exp idact-energy idact-volume ideffic idnrad ref-temp Reaction phase (DISPERSANT) Initiator ID Preexponential factor Activation energy Activation volume (optional) Initiator efficiency Number of radicals from one initiator molecule Reference temperature
INIT-CAT
Identifier for catalyzed initiator decomposition reaction. phasid cid1 cid2 icpre-exp icact-energy icact-volume iceffic icnrad Reaction phase (DISPERSANT) Initiator ID Catalyst ID Preexponential factor Activation energy Activation volume (optional) Initiator efficiency Number of radicals from one initiator molecule
494
ref-temp INIT-ACT
Identifier for initiation by activator and initiator. phasid cid1 cid2 iapre-exp iaact-energy iaact-volume iaeffic ianrad ref-temp Reaction phase (DISPERSANT) Initiator ID Activator ID Preexponential factor Activation energy Activation volume (optional) Initiator activation efficiency Initiator activation number of radicals Reference temperature
PROPAGATION
Identifier for chain propagation reaction. phasid cid1 cid2 prpre-exp pract-energy pract-volume ref-temp Reaction phase (POLYMER or DISPERSANT) Monomer corresponding to active polymer segment ID Monomer ID Preexponential factor Activation energy Activation volume (optional) Reference temperature
CHAT-MON
Identifier for chain transfer to monomer reaction. phasid cid1 cid2 cmpre-exp cmact-energy cmact-volume ref-temp Reaction phase (POLYMER) Monomer corresponding to active polymer segment ID Monomer ID Preexponential factor Activation energy Activation volume (optional) Reference temperature
CHAT-POL
Identifier for chain transfer to polymer reaction. phasid cid1 cid2 Reaction phase (POLYMER) Monomer corresponding to active polymer segment ID Monomer corresponding to reacting polymer segment ID or dead chain
495
cppre-exp cpact-energy cpact-volume ref-temp CHAT-AGENT
Preexponential factor Activation energy Activation volume (optional) Reference temperature
Identifier for chain transfer to transfer agent reaction. phasid cid1 cid2 capre-exp caact-energy caact-volume ref-temp Reaction phase (POLYMER) Monomer corresponding to active polymer segment ID Transfer agent ID Preexponential factor Activation energy Activation volume (optional) Reference temperature
TERM-DIS
Identifier for chain termination by disproportionation reaction. phasid cid1 cid2 tdpre-exp tdact-energy tdact-volume ref-temp Reaction phase (POLYMER or DISPERSANT) First active polymer segment ID Second active polymer segment ID Preexponential factor Activation energy Activation volume (optional) Reference temperature
TERM-COMB
Identifier for chain termination by combination reaction. phasid cid1 cid2 tcpre-exp tcact-energy tcact-volume ref-temp Reaction phase (POLYMER or DISPERSANT) First active polymer segment ID Second active polymer segment ID Preexponential factor Activation energy Activation volume (optional) Reference temperature
INHIBITION
Identifier for chain inhibition reaction. phasid cid1 cid2 Reaction phase (POLYMER) Active polymer segment ID Inhibitor ID
496
inpre-exp inact-energy inact-volume ref-temp REDUCTION
Preexponential factor Activation energy Activation volume (optional) Reference temperature
Identifier for reduction step of redox initiation. phasid cid1 cid2 rdpre-exp rdact-energy rdact-volume rdeffic rdnrad ref-temp Reaction phase (DISPERSANT) Reductant ID Redox agent (catalyst) ID Preexponential factor Activation energy Activation volume (optional) Reduction activation efficiency Reduction activation number of radicals Reference temperature
OXIDATION
Identifier for oxidation step of redox initiation. phasid cid1 cid2 oxpre-exp oxact-energy oxact-volume ref-temp Reaction phase (DISPERSANT) Initiator ID Redox agent (catalyst) ID Preexponential factor Activation energy Activation volume (optional) Reference temperature
GEL-EFFECT
Gel effect switch and correlation selection. This sentence is used to Include a gel effect for any reactions in the built-in kinetic scheme and for the initiator efficiency Select a gel effect correlation from a list of built-in and user specified gel effect correlations Specify the maximum number of parameters Specify the parameter values for the selected correlation The default action is to not include a gel effect.
GETYPE= reactiontype
INITIATION INIT-EFF
Used to identify the type of reaction to apply gel effect to. A list of valid reaction types follows Initiator decomposition Initiator efficiency
497
PROPAGATION CHAT-MON CHAT-POL CHAT-AGENT TERMINATION
Propagation, chain initiation and induced initiation reactions Chain transfer to monomer Chain transfer to polymer Chain transfer to agent Termination Used to select a correlation number. If a correlation number greater than the number of built-in correlations (currently 2) is specified then the user should supply a Fortran subroutine containing the user gel effect correlation. Used to enter the maximum number of gel effect parameters for the correlation selected. Used to enter a list of parameters for the correlation selected.
CORR-NO= corrno
MAX-PARAMS= maxparams
GE-PARAMS= paramlist
SUBROUTINE
User subroutines sentence.
GEL-EFFECT= subname
Used to specify the name of the subroutine containing user gel effect correlations. The user gel-effect subroutine argument list was shown in the Gel Effect section in Chapter 3. A Fortran template called USRGEL.F is available for your use.
ABS-MIC
Used to specify rate of radical absorption by micelles. ampre-exp amact-energy Preexponential factor Activation energy
ABS-PART
Used to specify rate of radical absorption by particles. appre-exp apact-energy Preexponential factor Activation energy
DES-PART
Identifier for radical desorption. dppre-exp dpact-energy Preexponential factor Activation energy
EMUL-PARAMS
Used to specify emulsion parameters for micellar nucleation. emulid cmc-conc area Emulsifier ID Critical micelle concentration Surface coverage or area per unit mole of emulsifier
498
Input Language Example for Emulsion Polymerization
REACTIONS EMLRXN EMULSION DESCRIPTION "EXAMPLE EMULSION INPUT" PARAM KBASIS=MONOMER SPECIES INITIATOR=APS MONOMER=STY NBA EMULSIFIER=EMUL & DISPERSANT=H2O POLYMER=POLYMER INIT-DEC DISPERSANT APS 1.0000E+16 1.4020E+08 & 0.0 EFFIC=.80 NRADS=2 PROPAGATION POLYMER STY STY 2341450.0 2.6000E+07 PROPAGATION POLYMER STY NBA 3265600.0 2.6000E+07 PROPAGATION POLYMER NBA NBA 1909530.0 2.2400E+07 PROPAGATION POLYMER NBA STY 1.4918E+07 2.2400E+07 CHAT-MON POLYMER STY STY 3310000.0 5.3020E+07 CHAT-MON POLYMER STY NBA 3310000.0 5.3020E+07 CHAT-MON POLYMER NBA NBA 438.90 2.7600E+07 CHAT-MON POLYMER NBA STY 438.90 2.7600E+07 TERM-COMB POLYMER STY STY 1.6125E+09 7000000.0 TERM-COMB POLYMER STY NBA 7.3204E+09 1.4600E+07 TERM-COMB POLYMER NBA NBA 3.3217E+10 2.2200E+07 TERM-COMB POLYMER NBA STY 7.3204E+09 1.4600E+07 ABS-MIC 1.0000E-07 0.0 ABS-PART 1.0000E-07 0.0 DES-PART 0.0 0.0 EMUL-PARAMS EMUL 0.0 5.0000E+08 SPLIT-PM STY .40 SPLIT-PM NBA .40
Specifying Ziegler-Natta Polymerization Kinetics

Following is the input language for the part of the polymerization REACTIONS paragraph specific to Ziegler-Natta kinetics. Ziegler-Natta inputs may be used to define the reaction kinetics for a wide variety of homo- and co-polymers produced by catalyzed polymerization, including HDPE. A subset of the built-in kinetics can be defined for a simulation by including the reaction keywords for the desired reactions and specifying the rate coefficient parameters for these
499
reactions. The reaction keywords and rate coefficient parameters for ZieglerNatta polymerization are also provided. Currently for two phase systems the polymerization reactions are applied to the liquid phase in the reactor. For gas phase polymerization systems the solid polymer, or the amorphous part of the polymer, is modeled as a liquid.
Input Language for Ziegler-Natta Polymerization
REACTIONS SPECIES reacid ZIEGLER-NAT PRECAT=cid CATALYST=cid COCATALYST=cid MONOMER=cid CHAINTAG=cid & SOLVENT=cid POISON=cid BYPRODUCT=cid HYDROGEN=cid POLYMER=cid & ELECDONOR=cid TDBSEGMENT=cid ACT-SPON site-id cid1 aspre-exp asact-energy asorder ref-temp ACT-COCAT site-id cid1 cid2 acpre-exp acact-energy acorder ref-temp ACT-EDONOR site-id cid1 cid2 aepre-exp aeact-energy aeorder ref-temp ACT-H2 site-id cid1 cid2 ahpre-exp ahact-energy ahorder ref-temp ACT-MON site-id cid1 cid2 ampre-exp amact-energy amorder ref-temp CHAIN-INI site-id cid1 cipre-exp ciact-energy ciorder ref-temp PROPAGATION site-id cid1 cid2 prpre-exp pract-energy prorder ref-temp CHAT-MON site-id cid1 cid2 cmpre-exp cmact-energy cmorder cmtdb-frac ref-temp CHAT-AGENT site-id cid1 cid2 capre-exp caact-energy caorder catdb-frac ref-temp CHAT-SOL site-id cid1 cid2 cspre-exp csact-energy csorder cstdb-frac ref-temp CHAT-COCAT site-id cid1 cid2 ccpre-exp ccact-energy ccorder cctdb-frac ref-temp CHAT-H2 site-id cid1 cid2 chpre-exp chact-energy chorder chtdb-frac ref-temp CHAT-EDONOR site-id cid1 cid2 cepre-exp ceact-energy ceorder cetdb-frac ref-temp CHAT-SPON site-id cid1 cid2 cnpre-exp cnact-energy cnorder cntdb-frac ref-temp DEACT-POISON site-id cid1 dppre-exp dpact-energy dporder ref-temp DEACT-COCAT site-id cid1 dcpre-exp dcact-energy dcorder ref-temp DEACT-MON site-id cid1 dmpre-exp dmact-energy dmorder ref-temp DEACT-EDONOR site-id cid1 depre-exp deact-energy deorder ref-temp DEACT-H2 site-id cid1 dhpre-exp dhact-energy dhorder ref-temp DEACT-SPON site-id dspre-exp dsact-energy dsorder ref-temp COCAT-POISON cid1 cid2 copre-exp coact-energy coorder ref-temp FSINH-H2 site-id cid1 fhpre-exp fhact-energy fhorder ref-temp RSINH-H2 site-id cid1 rhpre-exp rhact-energy rhorder ref-temp FSINH-POISON site-id cid1 fppre-exp fpact-energy fporder ref-temp RSINH-POISON site-id cid1 rppre-exp rpact-energy rporder ref-temp TDB-POLY site-id cid1 cid2 tdpre-exp tdact-energy tdorder ref-temp ATACT-PROP site-id cid1 cid2 atpre-exp atact-energy atorder ref-temp CAT-ACTIVATE cid1 cid2 avpre-exp avact-energy avorder ref-temp OPTIONS REAC-PHASE=phaseid SUPPRESS-WARN=yes/no USE-BULK=yes/no
Input Language Description for Ziegler-Natta Polymerization
reacid SPECIES
Reaction paragraph ID. Reacting species identification. This sentence is used to associate components in the simulation with the reactive species in the built-in kinetic scheme. The following species keywords are currently valid PRECAT MONOMER POISON HYDROGEN ELECDONOR CATALYST COCATALYST CHAINTAG SOLVENT BYPRODUCT POLYMER TDBSEGMENT
MON-RSEG
Specifies the pairing between monomers and their corresponding repeat segments in a polymer. monomer r-seg Monomer ID Corresponding repeat segment ID
500
ACT-SPON
Reaction identifier for spontaneous site activation of a catalyst potential site to a vacant active site of type k. site-id cid1 aspre-exp asact-energy asorder ref-temp Site type identifier for active site formed (k = 1, 2, ... , NSITE) Component ID of catalyst Preexponential factor (default is 0.0) Activation energy (default is 0.0) Reaction order for potential site concentration (default is 0.0) Reference temperature
ACT-COCAT
Reaction identifier for site activation by cocatalyst of a catalyst potential site to a vacant active site of type k. site-id cid1 cid2 acpre-exp acact-energy acorder ref-temp Site type identifier for active site (k = 1, 2, ... , NSITE) Component ID of catalyst Component ID of cocatalyst Preexponential factor (default is 0.0) Activation energy (default is 0.0) Reaction order for cocatalyst concentration (default is 0.0) Reference temperature
ACT-EDONOR
Reaction identifier for site activation by electron donor of a catalyst potential site to a vacant active site of type k. site-id cid1 cid2 aepre-exp aeact-energy aeorder ref-temp Site type identifier for active site formed (k = 1, 2, ... , NSITE) Component ID of catalyst Component ID of electron donor Preexponential factor (default is 0.0) Activation energy (default is 0.0) Reaction order for electron donor concentration (default is 0.0) Reference temperature
ACT-H2
Reaction identifier for site activation by hydrogen of a catalyst potential site to a vacant active site of type k. site-id cid1 Site type identifier for active site formed (k = 1, 2, ... , NSITE) Component ID of catalyst
501
cid2 ahpre-exp
Component ID of hydrogen Preexponential factor (default is 0.0)
ahact-energy Activation energy (default is 0.0) ahorder ref-temp ACT-MON Reaction order for hydrogen concentration (default is 0.0) Reference temperature
Reaction identifier for site activation by monomer of a catalyst potential site to a vacant active site of type k. site-id cid1 cid2 ampre-exp Site type identifier for active site formed (k = 1, 2, ... , NSITE) Component ID of catalyst Component ID of monomer Preexponential factor (default is 0.0)
amact-energy Activation energy (default is 0.0) amorder ref-temp CHAIN-INI Reaction order for monomer concentration (default is 0.0) Reference temperature
Reaction identifier for polymer chain initiation on a vacant active site of type k. The vacant site becomes a propagation site of type k. site-id cid1 cipre-exp ciact-energy ciorder ref-temp Site type identifier (k = 1, 2, ... , NSITE) Component ID of monomer Preexponential factor (default is 0.0) Activation energy (default is 0.0) Reaction order for monomer concentration (default is 0.0) Reference temperature
PROPAGATION
Reaction identifier for polymer chain propagation on an active site of type k. site-id cid1 cid2 prpre-exp pract-energy prorder Site type identifier (k = 1, 2, ... , NSITE) Component ID of active segment (specified in terms of the corresponding monomer ID) Component ID of monomer Preexponential factor (default is 0.0) Activation energy (default is 0.0) Reaction order for monomer concentration (default is 0.0)
502
ref-temp CHAT-MON
Reaction identifier for chain transfer to monomer on active site of type k. site-id cid1 cid2 cmpre-exp cmactenergy cmorder cmtdb-frac ref-temp Site type identifier (k = 1, 2, ... , NSITE) Component ID of active segment (specified in terms of the corresponding monomer ID) Component ID of monomer Preexponential factor (default is 0.0) Activation energy (default is 0.0) Reaction order for monomer concentration (default is 0.0) Fraction of generated dead polymer chains with terminal double bonds (default is 0.0) Reference temperature
CHAT-AGENT
Reaction identifier for chain transfer to agent on active site of type k. site-id cid1 cid2 capre-exp caact-energy caorder catdb-frac ref-temp Site type identifier (k = 1, 2, ... , NSITE) Component ID of active segment (specified in terms of the corresponding monomer ID) Component ID of chain transfer agent Preexponential factor (default is 0.0) Activation energy (default is 0.0) Reaction order for agent concentration (default is 0.0) Fraction of generated dead polymer chains with terminal double bonds (default is 0.0) Reference temperature
CHAT-SOL
Reaction identifier for chain transfer to solvent on active site of type k. site-id cid1 cid2 cspre-exp csact-energy csorder Site type identifier (k = 1, 2, ... , NSITE) Component ID of active segment (specified in terms of the corresponding monomer ID) Component ID of solvent Preexponential factor (default is 0.0) Activation energy (default is 0.0) Reaction order for solvent concentration (default is 0.0)
503
cstdb-frac ref-temp CHAT-COCAT
Fraction of generated dead polymer chains with terminal double bonds (default is 0.0) Reference temperature
Reaction identifier for chain transfer to cocatalyst on active site of type k. site-id cid1 cid2 ccpre-exp ccact-energy ccorder cctdb-frac ref-temp Site type identifier (k = 1, 2, ... , NSITE) Component ID of active segment (specified in terms of the corresponding monomer ID) Component ID of cocatalyst Preexponential factor (default is 0.0) Activation energy (default is 0.0) Reaction order for cocatalyst concentration (default is 0.0) Fraction of generated dead polymer chains with terminal double bonds (default is 0.0) Reference temperature
CHAT-H2
Reaction identifier for chain transfer to hydrogen on active site of type k. site-id cid1 cid2 chpre-exp chact-energy chorder chtdb-frac ref-temp Site type identifier (k = 1, 2, ... , NSITE) Component ID of active segment (specified in terms of the corresponding monomer ID) Component ID of hydrogen Preexponential factor (default is 0.0) Activation energy (default is 0.0) Reaction order for hydrogen concentration (default is 0.0) Fraction of generated dead polymer chains with terminal double bonds (default is 0.0) Reference temperature
CHAT-EDONOR
Reaction identifier for chain transfer to electron donor on active site of type k. site-id cid1 cid2 cepre-exp ceact-energy Site type identifier (k = 1, 2, ... , NSITE) Component ID of active segment (specified in terms of the corresponding monomer ID) Component ID of electron donor Preexponential factor (default is 0.0) Activation energy (default is 0.0)
504
ceorder cetdb-frac ref-temp CHAT-SPON
Reaction order for electron donor concentration (default is 0.0) Fraction of generated dead polymer chains with terminal double bonds (default is 0.0) Reference temperature
Reaction identifier for spontaneous chain transfer on active site of type k. site-id cid1 cnpre-exp cnact-energy cnorder cntdb-frac ref-temp Site type identifier (k = 1, 2, ... , NSITE) Component ID of active segment (specified in terms of the corresponding monomer ID) Preexponential factor (default is 0.0) Activation energy (default is 0.0) Reaction order (not used) Fraction of generated dead polymer chains with terminal double bonds (default is 0.0) Reference temperature
DEACT-POISON
Reaction identifier for site deactivation by poison of a catalyst active site of type k to a dead site. site-id cid1 dppre-exp Site type identifier (k = 1, 2, ... , NSITE) Component ID of poison Preexponential factor (default is 0.0)
dpact-energy Activation energy (default is 0.0) dporder ref-temp DEACT-COCAT Reaction order for poison concentration (default is 0.0) Reference temperature
Reaction identifier for site deactivation by cocatalyst of a catalyst active site of type k to a dead site. site-id cid1 dcpre-exp dcact-energy dcorder ref-temp Site type identifier (k = 1, 2, ... , NSITE) Component ID of cocatalyst Preexponential factor (default is 0.0) Activation energy (default is 0.0) Reaction order for cocatalyst concentration (default is 0.0) Reference temperature
DEACT-MON
Reaction identifier for site deactivation by monomer of a catalyst active site of type k to a dead site. site-id cid1 Site type identifier (k = 1, 2, ... , NSITE) Component ID of monomer
505
dmpre-exp
Preexponential factor (default is 0.0)
dmact-energy Activation energy (default is 0.0) dmorder ref-temp Reaction order for monomer concentration (default is 0.0) Reference temperature
DEACT- EDONOR Reaction identifier for site deactivation by electron donor of a catalyst active site of type k to a dead site. site-id cid1 depre-exp Site type identifier (k = 1, 2, ... , NSITE) Component ID of electron donor Preexponential factor (default is 0.0)
deact-energy Activation energy (default is 0.0) deorder ref-temp DEACT-H2 Reaction order for electron donor concentration (default is 0.0) Reference temperature
Reaction identifier for site deactivation by hydrogen of a catalyst active site of type k to a dead site. site-id cid1 dhpre-exp Site type identifier (k = 1, 2, ... , NSITE) Component ID of hydrogen Preexponential factor (default is 0.0)
dhact-energy Activation energy (default is 0.0) dhorder ref-temp DEACT-SPON Reaction order for hydrogen concentration (default is 0.0) Reference temperature
Reaction identifier for spontaneous site deactivation of a catalyst active site of type k to a dead site. site-id dspre-exp dsact-energy dsorder ref-temp Site type identifier (k = 1, 2, ... , NSITE) Preexponential factor (default is 0.0) Activation energy (default is 0.0) Reaction order (not used) Reference temperature
COCATPOISON
Reaction identifier for cocatalyst poisoning reaction. cid1 cid2 copre-exp coact-energy coorder Component ID of cocatalyst Component ID of poison Preexponential factor (default is 0.0) Activation energy (default is 0.0) Reaction order (not used)
506
ref-temp FSINH-H2
Reaction identifier for site inhibition by hydrogen-forward reaction. site-id cid1 fhpre-exp fhact-energy fhorder ref-temp Site type identifier (k = 1, 2, ... , NSITE) Component ID of hydrogen Preexponential factor (default is 0.0) Activation energy (default is 0.0) Reaction order for hydrogen concentration (default is 0.0) Reference temperature
RSINH-H2
Reaction identifier for site inhibition by hydrogen-reverse reaction. site-id cid1 rhpre-exp rhact-energy rhorder ref-temp Site type identifier (k = 1, 2, ... , NSITE) Component ID of hydrogen Preexponential factor (default is 0.0) Activation energy (default is 0.0) Reaction order for inhibited site concentration (default is 0.0) Reference temperature
FSINH-POISON
Reaction identifier for site inhibition by poison-forward reaction. site-id cid1 fppre-exp fpact-energy fporder ref-temp Site type identifier (k = 1, 2, ... , NSITE) Component ID of poison Preexponential factor (default is 0.0) Activation energy (default is 0.0) Reaction order for poison concentration (default is 0.0) Reference temperature
RSINH-POISON
Reaction identifier for site inhibition by poison-reverse reaction. site-id cid1 rppre-exp rpact-energy rporder ref-temp Site type identifier (k = 1, 2, ... , NSITE) Component ID of poison Preexponential factor (default is 0.0) Activation energy (default is 0.0) Reaction order for inhibited site concentration (default is 0.0) Reference temperature
507
TDB-POLY
Reaction identifier for terminal double bond propagation reaction. site-id cid1 cid2 tdpre-exp tdact-energy tdorder ref-temp Site type identifier (k = 1, 2, ... , NSITE) Component ID of active segment (specified in terms of the corresponding monomer) Component ID of TDB segment Preexponential factor (default is 0.0) Activation energy (default is 0.0) Reaction order (not used) Reference temperature
ATACT-PROP
Reaction identifier for atactic propagation reaction. site-id cid1 cid2 atpre-exp atact-energy atorder ref-temp Site type identifier (k = 1, 2, ... , NSITE) Component ID of active segment (specified in terms of the corresponding monomer) Component ID of monomer Preexponential factor (default is 0.0) Activation energy (default is 0.0) Reaction order for monomer concentration (default is 0.0) Reference temperature
CAT-ACTIVATE
Reaction identifier for catalyst activation reaction. cid1 cid2 avpre-exp avact-energy avorder ref-temp Component ID for pre-catalyst Component ID of catalyst Preexponential factor (default is 0.0) Activation energy (default is 0.0) Reaction order for catalyst Reference temperature
OPTIONS
Used to specify reaction model options. REAC-PHASE= Specify the reacting phase as L, L1, L2, or V (default is L) phaseID SUPRESSWARN= yes/no YES: do not print warnings when the specified phase is not present NO: always print warnings when the specified phase is not present (default)
508
USE-BULK= yes/no
YES: force the model to apply the specified reaction kinetics to the bulk phase when the specified phase is not present (default) NO: rates are set to zero when the specified phase is not present
Input Language Example for Zielger-Natta Polymerization
REACTIONS ZN-R2 ZIEGLER-NAT DESCRIPTION "ZIEGLER-NATTA KINETIC SCHEME" SPECIES CATALYST=CAT COCATALYST=CCAT MONOMER=E2 SOLVENT=HEXANE HYDROGEN=H2 POLYMER=HDPE ACT-SPON ACT-SPON ACT-SPON ACT-SPON ACT-COCAT ACT-COCAT ACT-COCAT ACT-COCAT CHAIN-INI CHAIN-INI CHAIN-INI CHAIN-INI 1 CAT 2 CAT 3 CAT 4 CAT .080 .080 .080 .080 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 &
1 CAT CCAT .150 2 CAT CCAT .150 3 CAT CCAT .150 4 CAT CCAT .150 1 E2 2 E2 3 E2 4 E2 90.0 90.0 255.0 90.0 255.0 90.0 .090 .240 .090 .240 5.550 18.50 5.550 18.50 .0040
255.0 0.0 255.0 0.0
PROPAGATION 1 E2 E2 PROPAGATION 2 E2 E2 PROPAGATION 3 E2 E2 PROPAGATION 4 E2 E2 CHAT-MON CHAT-MON CHAT-MON CHAT-MON CHAT-H2 CHAT-H2 CHAT-H2 CHAT-H2 CHAT-SPON 1 E2 E2 2 E2 E2 3 E2 E2 4 E2 E2 1 E2 H2 2 E2 H2 3 E2 H2 4 E2 H2 1 E2
509
CHAT-SPON CHAT-SPON CHAT-SPON DEACT-SPON DEACT-SPON DEACT-SPON
2 E2 3 E2 4 E2 1 2 3
.0120 .0040 .0120
0.0 0.0 0.0
1.0 1.0 1.0 1.0 1.0 1.0 1.0
.00010 0.0 .00060 0.0 .00010 0.0 .00060 0.0
DEACT-SPON 4 OPTIONS REAC-PHASE=L
Specifying Ionic Polymerization Kinetics

Following is the input language for the IONIC REACTIONS paragraph.
Input Language for Ionic Polymerization
REACTIONS SPECIES reacid IONIC ASSO-INI=cid INIT=cid CATALYST=cid & EX-AGENT=cid CT-AGENT=cid TM-AGENT=cid & POLYMERS MON-RSEG cid segid / cid segid / INIT-DISSOC cid1 cid2 idpre-exp-f idact-ener-f idpre-exp-r idact-ener-r idasso-no & idref-temp ACT-CATALYST site-id cid1 cid2 acpre-exp-f acact-ener-f acpre-exp-r acact-ener-r & accoefb accoefd acref-temp CHAIN-INI-1 site-id cid i1pre-exp-f i1act-ener-f i1ref-temp CHAIN-INI-2 site-id cid1 cid2 i2pre-exp-f i2act-ener-f i2coefd CHAIN-INI-T site-id cid itpre-exp-f itact-ener-f itref-temp PROPAGATION site-id cid1 cid2 prpre-exp-f pract-ener-f prref-temp ASSOCIATION site-id cid aspre-exp-f asact-ener-f aspre-exp-r asact-ener-r EXCH-GENERAL rxn id site-id1 cid1 site-id2 cid2 egpre-exp-f egact-ener-f egref-temp EXCH-AGENT rxn id site-id1 cid1 site-id2 cid2 eapre-exp-f eaact-ener-f & eapre-expr eaact-ener-r eacoefd earef-temp EQUILIB-CION site-id1 cid1 site-id2 eqpre-exp-f eqact-ener-f eqpre-exp-r & eqexp-ener-r eqcoefd eqref-temp CHAT-SPON site-id cid cspre-exp-f csact-ener-f csref-temp CHAT-MONOMER site-id cid1 cid2 cmpre-exp-f cmact-ener-f cmref-temp CHAT-DORM-P rxn id site-id1 cid1 site-id2 cid2 cdpre-exp-f cdact-ener-f cdref-temp CHAT-AGENT site-id cid1 cid2 capre-exp-f caact-ener-f caorder caref-temp TERM-C-ION site-id cid tcpre-exp tcact-energy tccoefb tcref-temp TERM-AGENT site-id cid1 cid2 tapre-exp-f taact-ener-f taorder taref-temp COUPLING site-id1 site-id2 site-id3 copre-exp-f coact-ener-f copre-exp-r & coact-eng-r coref-temp OPTIONS REAC-PHASE=phaseid SUPPRESS-WARN=yes/no USE-BULK=yes/no
Input Language Description for Ionic Polymerization
reacid
Reaction paragraph ID.
510
SPECIES
Reacting species identification. This sentence is used to associate components in the simulation with the reactive species in the built-in kinetic scheme. The following species keywords are currently valid: ASSOC-INIT INITIATOR CATALYST EXCH-AGENT CHAT-AGENT TERM-AGENT POLYMER
MON-RSEG
Identifying the reacting monomer and the corresponding repeat segment associated with it. cid1 cid2 Component ID of monomer Component ID of corresponding repeat segment
INIT-DISSOC
Reaction identifier for initiator dissociation reaction. Associated initiator of type m dissociates into type p initiator. cid1 cid2 idpre-exp-f idact-ener-f idpre-exp-r idact-ener-r idasso-no idref-temp Component ID of associated initiator Component ID of catalyst Preexponential factor for forward reaction Activation energy for forward reaction Preexponential factor for reverse reaction Activation energy for reverse reaction Initiator Association number Reference temperature
ACT-CATALYST
Reaction identifier for active species activation by catalyst of type n of an initiator of type m to form active species and/or counter-ion of type i. site-id cid1 cid2 acpre-exp-f acact-ener-f acpre-exp-r Site type identifier for active species formed (i = 1, 2, ..., NSITE) Component ID of initiator Component ID of catalyst Preexponential factor for forward reaction Activation energy for forward reaction Preexponential factor for reverse reaction
acact-ener-r Activation energy for reverse reaction accoefb accoefd acref-temp 0 if cid2 does not participate in the reaction. 1 if cid2 participates in the reaction 0 if counter-ion is absent. 1 if counter-ion is present Reference temperature
511
CHAIN-INI-1
Reaction identifier for chain initiation of active species of type i by monomer of type j. site-id cid i1pre-exp-f i1act-ener-f i1ref-temp Site type identifier for active species formed (i = 1, 2, ..., NSITE) Component ID of monomer Preexponential factor Activation energy Reference temperature
CHAIN-INI-2
Reaction identifier for chain initiation of active species of type i by monomer of type j reacting with initiator of type m. site-id cid1 cid2 i2pre-exp-f i2act-ener-f i2coefd tref Site type identifier for active species formed (i = 1, 2, ..., NSITE) Component ID of initiator Component ID of monomer Preexponential factor Activation energy 1 if counter-ion is formed. 0 otherwise Reference temperature
CHAIN-INI-T
Reaction identifier for chain initiation of transfer active species of type i by monomer of type j. site-id cid itpre-exp-f itact-ener-f itref-temp Site type identifier for active species formed (i = 1, 2, ..., NSITE) Component ID of monomer Preexponential factor Activation energy Reference temperature
PROPAGATION
Reaction identifier for polymer chain propagation on an active species of type i. site-id cid1 cid2 prpre-exp-f pract-ener-f prref-temp Site type identifier for active species formed (i = 1, 2, ..., NSITE) Component ID of active segment Component ID of monomer Preexponential factor Activation energy Reference temperature
512
ASSOCIATION
Reaction identifier for polymer association with active species of type i. site-id cid aspre-exp-f asact-ener-f aspre-exp-r Site type identifier for active species formed (i = 1, 2, ..., NSITE) Component ID of active segment Preexponential factor for forward reaction (forming aggregate polymer) Activation energy for forward reaction Preexponential factor for reverse reaction
asact-ener-r Activation energy for reverse reaction asasso-no asref-temp EXCH-GENERAL Polymer association Reference temperature
Reaction identifier for general exchange reaction between two growing polymer chains with unique active species and end segments attached to them. rxn id site-id1 cid1 site-id2 cid2 egpre-exp-f Reaction ID for a unique rate constant Site type identifier for first active species (i = 1, 2, ... , NSITE) Component ID of active segment on siteid1 Site type identifier for second active species (i = 1, 2, ... , NSITE) Component ID of active segment on siteid2 Preexponential factor
egact-ener-f Activation energy egref-temp EXCH-AGENT Reference temperature
Reaction identifier for exchange between growing i polymer species with k segment attached to it and an exchangeagent of type m. rxn id site-id1 cid1 site-id2 cid2 eapre-exp-f Reaction ID for a unique rate constant Site type identifier for first active species (i = 1, 2, ... , NSITE) Component ID of active segment on siteid1 Site type identifier for second active species (i = 1, 2, ... , NSITE) formed Component ID of exchange agent Preexponential factor for forward reaction
eaact-ener-f Activation energy for forward reaction
513
eapre-exp-r
Preexponential factor for reverse reaction
eaact-ener-r Activation energy for reverse reaction eacoefd earef-temp EQUILIB-CION 0 if Po is absent. 1 if Po is present Reference temperature
Reaction identifier for equilibrium with counter-ion between i and j active species with kth segment attached to it. site-id1 cid site-id2 eqpre-exp-f Site type identifier for first active species (i = 1, 2, ... , NSITE) Component ID of active segment Site type identifier for second active species (j = 1, 2, ... , NSITE) Preexponential factor for forward reaction
eqact-ener-f Activation energy for forward reaction eqpre-exp-r Preexponential factor for reverse reaction
eqact-ener-r Activation energy for reverse reaction eqcoefd eqref-temp CHAT-SPON 0 if counter-ion is absent. 1 if counter-ion is present Reference temperature
Reaction identifier for spontaneous chain transfer on active species of type i. site-id cid cspre-exp-f csact-ener-f csref-temp Site type identifier for active species (i=1, 2, ... , NSITE) Component ID of active segment Preexponential factor Activation energy Reference temperature
CHAT-MONOMER Reaction identifier for chain transfer to monomer of type j on active species of type i. site-id cid1 cid2 Site type identifier for active species (i=1, 2, ... , NSITE) Component ID of active segment Component ID of monomer
cmpre-exp-f Preexponential factor cmact-ener-f Activation energy cmref-temp Reference temperature
514
CHAT-DORM-P
Reaction identifier for chain transfer on active species of type i to form dormant polymer of type j. rxn id site-id1 cid1 site-id2 cid2 cdpre-exp-f cdact-ener-f cdref-temp Reaction ID for a unique rate constant Site type identifier for growing active species (i = 1, 2, ... , NSITE) Component ID of active segment on siteid1 Site type identifier for product active species (j = 1, 2, ... , NSITE) formed Component ID of monomer Preexponential factor Activation energy Reference temperature
CHAT-AGENT
Reaction identifier for chain transfer to chain transfer agent on active species of type i. site-id cid1 cid2 capre-exp-f caact-ener-f caorder caref-temp Site type identifier for active species (i=1, 2, ... , NSITE) Component ID of active segment Component ID of chain transfer agent Preexponential factor Activation energy Reaction order for chain transfer agent concentration Reference temperature
TERM-C-ION
Reaction identifier for chain termination with counter-ion. site-id cid tcpre-exp tcact-energy tcoefb tcref-temp Site type identifier for active species (i=1, 2, ... , NSITE) Component ID of active segment Preexponential factor Activation energy 0 if counter-ion does not participate in the reaction. 1 if it does Reference temperature
TERM-AGENT
Reaction identifier for termination with terminating agent. site-id cid1 cid2 Site type identifier (i = 1, 2, ... , NSITE) Component ID of active agent Component ID of terminating agent
515
tapre-exp-f taact-ener-f taorder taref-temp COUPLING
Preexponential factor Activation energy Reaction order for terminating agent concentration Reference temperature
Reaction identifier for coupling reaction between active species of type i and type j to form active species of type k. site-id1 site-id2 site-id3 copre-exp-f coact-ener-f copre-exp-r coact-ener-r coref-temp Site identifier for active species of type i participating in the reaction Site identifier for active species of type j participating in the reaction Site identifier for active species of type k formed by coupling reaction Preexponential factor Activation energy Preexponential factor Activation energy Reference temperature
OPTIONS
Specify reaction model options. REAC-PHASE= Specify the reacting phase as L, L1, L2, or V (default is L) phaseid SUPRESSWARN= yes/no USE-BULK= yes/no YES: do not print warnings when the specified phase is not present NO: always print warnings when the specified phase is not present (default) YES: force the model to apply the specified reaction kinetics to the bulk phase when the specified phase is not present (default) NO: rates are set to zero when the specified phase is not present
Input Language Example for Ionic Polymerization
516
REACTIONS rxnid SEGMENT-BAS DESCRIPTION '...' PARAM TREF=value PHASE=V/L/L1/L2 SOLVE-ZMOM=YES/NO & [SUPRESS-WARN=yes/no] [USE-BULK=yes/no] CBASIS=basis & [REAC-SITE=siteno S-BASIS=basis]
SPECIES POLYMER=polymerid STOIC reactionno compid coef / ... RATE-CON reactionno pre-exp act-energy [t-exp] [TREF=ref-temp] & [CATALYST=cid CAT-ORDER=value] [USER-RC=userid] / ... POWLAW-EXP reactionno compid exponent / [ASSIGN reactionno [ACTIVITY=value] RC-SETS=setno-list] MASSTRANS=mtname NREALRC=nrealc NINTMT=nintmt NWORKRC=nwork NIWORKMT=niwork NREALMT=nrealmt & NWORKMT=nwork &
SUBROUTINE USER-VECS
RATECON=rcname NINTRC=nintrc NIWORKRC=niwork
INTRC REALRC INTMT REALMT
NURC=nurc value-list value-list value-list value-list
Specifying Segment-Based Polymer Modification Reactions

The input language for the SEGMENT-BAS REACTIONS paragraph is described here.
Input Language for Segment-Based Polymer Modification Reactions
REACTIONS rxnid SEGMENT-BAS DESCRIPTION '...' PARAM T-REFERENCE=value PHASE=V/L/L1/L2 CBASIS=basis & SOLVE-ZMOM=YES/NO SPECIES POLYMER=polymerid STOIC reactionno compid coef / ... RATE-CON reactionno pre-exp act-energy [t-exp] / ... POWLAW-EXP reactionno compid exponent /
The keywords for specifying rate constant parameters, reaction stoichiometry, and reacting polymer are described here.
Input Language Description for Segment-Based Polymer Modification Reactions
reacid DESCRIPTION PARAM
Unique paragraph ID. Up to 64 characters between double quotes. Used to enter reaction specifications.
517
T-REF= value
Reference temperature. If no reference temperature is given, the term 1/Tref is dropped from the rate expression:
rate =
( C )k e
ij
j j oi
Eai 1 1 R T Tref
For more information, see the SegmentBased Reaction Model section in Chapter 3.
PHASE=V/L/L1 Reacting phase /L2

CBASIS Basis for power law rate expression. Choices are: MOLARITY MOLALITY MOLEFRAC MASSFRAC MASSCONC SUPRESSWARN= yes/no USE-BULK= yes/no YES: do not print warnings when the specified phase is not present NO: always print warnings when the specified phase is not present (default) YES: force the model to apply the specified reaction kinetics to the bulk phase when the specified phase is not present (default) NO: rates are set to zero when the specified phase is not present SOLVEZMOM= YES/NO REACSITE=siteno SBASIS=basis Option to explicitly solve for zeroth moment based on segment types (default=no) Site number associated with all reactions in this model For multi-site kinetics there are two options for calculating the segment concentrations used by the reactor model: COMPOSITE: use the composite segment concentrations (from SFLOW) SITE: use the site-based segment concentrations (from SSFLOW) SPECIES Used to specify reacting polymer.
POLYMER= polymerid
STOIC
Polymer component ID (for reacting polymer)
Used to specify stoichiometry for user reactions. Reactionno Reaction number
518
compid coef POWLAW-EXP
Component ID Stoichiometric coefficient (negative for reactants and positive for products)
Used to specify power-law exponents. Reactionno compid exponent Reaction number Component ID Power law exponent
ASSIGN
Used to assign rate constant(s) to user reactions. reactionno ACTIVITY= value Reaction number Multiplying factor used to calculate net rate constant List of rate constants (from RATE-CON) which apply to this user reaction
RC-SETS = setno-list
RATE-CON
Used to specify rate constant parameters. SetNo pre-exp act-energy t-exp T-ref USERRC=number CATALYST= compid Rate constant set number Pre-exponential factor in inverse time units Activation energy in mole enthalpy units Temperature exponent Reference temperature (default is global reference temperature in PARAM sentence) Used to specify an element number in the user rate constant array (default=do not apply user rate constant) Optional catalyst ID
CATOptional reaction order for catalyst ORDER=value (default=1) SUBROUTINE Used to provide the names of user-supplied Fortran subroutines. The subroutine argument lists are documented in the User Subroutines section of Chapter 3. RATECON= rcname BASIS= mtname USER-VECS User rate constant subroutine name User concentration basis / masstransfer subroutine name
Used to specify the size of vectors for user subroutines. NINTRC=nintrc NREALRC= nrealrc Length of integer array rate constant routine Length of real array for rate constant routine
519
NINTMT=nintmt NREALMT= nrealmt NIWORKRC= niwork NWORKRC=nwork NIWORKMT= niwork NWORKRC=nwork NURC INTRC REALRC INTMT REALMT
Length of integer array for basis subroutine Length of real array for basis subroutine Length of integer workspace for rate constant subroutine Length of real workspace for rate constant subroutine Length of integer workspace for basis routine Total length of real workspace for basis subroutine Number of rate constants returned by user rate constant routine
Used to enter integer parameters for user rate constant subroutine Used to enter real parameters for user rate constant subroutine Used to enter integer parameters for user basis subroutine Used to enter real parameters for user basis subroutine
Input Language Example for Segment-Based Polymer Modification Reactions
REACTIONS R-1 SEGMENT-BAS SPECIES POLYMER=PU STOIC 1 DEG -1. / MDI -1. / DEG-E 1. / MDI-E 1. / URETHANE 1. STOIC 2 DEG -1. / MDI-E -1. / DEG-E 1. / MDI-R 1. / URETHANE 1. STOIC 3 DEG-E -1. / MDI -1. / DEG-R 1. / MDI-E 1. / URETHANE 1. STOIC 4 DEG-E -1. / MDI-E -1. / DEG-R 1. / MDI-R 1. / URETHANE 1. STOIC 5 MDI-E -1. / H2O -1. / MDA-E 1. / CO2 1. STOIC 6 MDA-E -1. / MDI -1. / MDI-R 1. / MDI-E 1. / UREA-R 1. STOIC 7 MDA-E -1. / MDI-E -1. / MDI-R 2. / UREA-R 1. STOIC 8 MDI -1. / URETHANE -1. / MDI-E 1. / ALLOPHAN 1. & & & & &
520
STOIC 9 MDI-E -1. / URETHANE -1. / MDI-R 1. / ALLOPHAN 1. STOIC 10 MDI -1. / UREA-R -1. / MDI-E 1. / BIURET 1. STOIC 11 MDI-E -1. / UREA-R -1. / MDI-R 1. / BIURET 1 RATE-CON 1 2500. <1/sec> 10. RATE-CON 2 1000. <1/sec> 10. RATE-CON 3 5000. <1/sec> 10. RATE-CON 4 10. <1/sec> 10. RATE-CON 5 100. <1/sec> 10. ASSIGN-URC 1 ACTIVITY=4. RC-SETS=1 ASSIGN-URC 2 ACTIVITY=2. RC-SETS=1 ASSIGN-URC 3 ACTIVITY=2. RC-SETS=1 ASSIGN-URC 4 RC-SETS=1 ASSIGN-URC 5 RC-SETS=2 ASSIGN-URC 6 ACTIVITY=2. RC-SETS=3 ASSIGN-URC 7 RC-SETS=3 ASSIGN-URC 8 ACTIVITY=2. RC-SETS=4 ASSIGN-URC 9 RC-SETS=4 ASSIGN-URC 10 ACTIVITY=2. RC-SETS=5 ASSIGN-URC 11 RC-SETS=5 POWLAW-EXP 1 DEG 1. / MDI 1. POWLAW-EXP 2 DEG 1. / MDI-E 1. POWLAW-EXP 3 DEG-E 1. / MDI 1. POWLAW-EXP 4 DEG-E 1. / MDI-E 1. POWLAW-EXP 5 MDI-E 1. / H2O 1. POWLAW-EXP 6 MDA-E 1. / MDI 1. POWLAW-EXP 7 MDA-E 1. / MDI-E 1. POWLAW-EXP 8 MDI 1. / URETHANE 1. POWLAW-EXP 9 MDI-E 1. / URETHANE 1. POWLAW-EXP 10 MDI 1. / UREA-R 1. POWLAW-EXP 11 MDI-E 1. / UREA-R 1.
References
Aspen Physical Property System Physical Property Data. Cambridge, MA: Aspen Technology, Inc. Aspen Plus User Models. Cambridge, MA: Aspen Technology, Inc.
521
Index
A Absorption 209 Acrylic acid 195 Activated initiation 207 Activation energy fitting 348 Active species formation 246 Adding emulsion reactions 217 free-radical reactions 191 gel-effect 192, 218 ionic reactions 253 segment-based reactions 279 user basis subroutine 157, 281 user kinetic subroutine 157 user rate constant subroutine 157, 280 user step-growth reactions 155 Ziegler-Natta reactions 238 Addition polymerization about 78 ionic process differences 242 step-growth processes 257 Addition polymers 55 Addition reactions 99 Aggregate polymer 33, 34 Aggregation reactions 248 Aliphatic polycarbonates 85 Amorphous polymers 16 Analysis tools available 11, 36671 calculation procedure 367 case studies 368 optimization 369 sensitivity 368 Application tools 285 Applications data fitting 331 example uses 366 tools 36671 Architecture
Aspen Polymers 372 Aromatic polycarbonates 85 Aspen Plus distillation models 287, 293 Dupl 28890 equilibrium reactor models 296 Flash2 290 Flash3 290 fractionation models 287 FSplit 291 Heater 291 kinetic reactor models 296327 mass-balance reactor models 29496 Mixer 291 Mult 291 Pipe 292 Pump 292 RadFrac 293 RBatch 31927 RCSTR 296309 reaction models 83 reactor models 288, 294 REquil 296 RGibbs 296 RPlug 30919 RStoic 294 RYield 295 Sep 293 Sep2 293 stream manipulators 286 unit operation models 35157 Aspen Polymers application tools 285, 36671 architecture 372 built-in models 82 component attribute treatment in unit operations 32830 component databanks 378420 configuring 37273 data fitting 285, 33132 decomposition rate parameters 42123
522
Index
emulsion model 195219 end-use properties 72 features 5, 913 files 373 flowsheets 284 fortran utilities 43559 free-radical polymerization model 15994 input language 460520 installation 373 ionic model 24155 key parameters 334 kinetic rate constant parameters 42134 model definition 12 polyester technology package 91 property approach 56 reaction models 82 segment approach 27 segment-based reaction model 25681 steady-state features 285 steady-state modeling 28285 step-growth polymerization model 85158 templates 373 troubleshooting 37477 unit operation models 286330 unit operations 285 user models 83, 35165 user subroutines 13651, 265 76 Ziegler-Natta model 22040 Aspen PolyQuest 92 AspenTech support 3 AspenTech Support Center 3 Association reactions 248 Attributes See also Component attributes aggregate polymers 39, 48 bulk polymers 46 calculation methods 46 catalyst 44 fortran utilities 43648 handling in unit operations 328 initialization scheme 4650 initializing in streams 465 input language 43648 live polymers 38, 48 polymers 3536 required 43, 46 scale factors 50 scaling 466
site-based aggregate polymers 42, 49 site-based bulk polymers 48 site-based live polymers 41, 49 site-based polymers 39 specifying conventional component 464 user 45 variables for data regression 338 Ziegler-Natta 44 Average properties 5657 B Backbone modifications 260 Batch reactors 322 BatchFrac attribute handling 329 Beta-scission 179 Bifunctional initiator decomposition 167 Bifunctional initiators 170, 171 Bimodal distributions 54 Bivariate distributions 53 Block length 34 Branch formation 261 Branching degree of 32 free-radical polymerization 188 frequency 34 number of chains 34 reactions 235 Broyden solver 303 Bulk free-radical polymerization 159 94 polymer chain 165 polymer chain length moment equation 183 polymerization 160 Bulk polymerization 82 Butadiene 195 Butyl acrylate 195 Butyl methacrylate 195 C CAELID 436 CAID 436 Calculator block 367 CAMIX 437 Case study block 368 CASPLT 438
Index
523
CASPSS 438 Catalyst sites inhibited 226 propagation 226 types 226 vacant 226 Catalysts poisoning 235 preactivation 232 site activation 232 types 22124 Ziegler-Natta 24, 221 Ziegler-Natta reactions 225 Catalyzed initiation reaction 169 Categorizing polymers 19 CAUPDT 439 Chain initiation for ionic 247 initiation for Ziegler-Natta 232 scission 260 termination 249 Chain length average properties 57 distribution 20, 34, 5758, 62 first moment 46 instantaneous weight distribution 60 instanteous number-average 61 weight-average 61 zeroth moment 46 Chain size 53 Chain transfer dormant polymer formation 249 ionic reactions 249 spontaneous 234, 249 to agent 233, 249 to cocatalysts 234 to electron donor 234 to hydrogen 234 to monomer 175, 234, 249 to polymer 177 to small molecules 174, 233 to solvent 174, 233 to transfer agent 174 Chain-growth polymerization bulk 82 commercial polymers 81 comparison to step-growth 79 emulsion 82 overview 80
precipitation 82 solution 82 suspension 82 Characterizing approach 19 components 10, 12, 27 Chlorinated polyethylene 256 Chloroprene 195 Class 0 component attributes 33, 45, 328 Class 1 component attributes 33 Class 2 component attributes 33, 4546, 305, 328 CMC See Critical micelle concentration Cocatalysts poisoning 235 Combination reactions 100, 261 Component attributes about 19 aggregate polymer 33 available 3544 calculation methods 46 categories 34 class 0 33, 45 class 0 treatment in unit operations 328 class 1 33 class 2 33, 4546, 305 class 2 treatment in unit operations 328 classes 33 composite 34 copolymer composition 32 degree of branching 32 degree of cross-linking 32 degree of polymerization 23, 32 emulsion polymerization 214 for aggregate polymers 39, 48 for blocks 51 for bulk polymers 46 for catalysts 33, 44 for composite aggregate polymers 35 for composite live polymers 34 for composite polymers 34 for ionic initiators 32, 44 for live polymers 38, 48 for polymer properties 32 for polymers 3435, 3536
524
Index
for site-based aggregate polymers 35, 42, 49 for site-based bulk polymers 48 for site-based live polymers 35, 41, 49 for site-based polymers 35, 39 43 for site-based species 44 for streams 51 for structural properties 32 for Ziegler-Natta catalysts 32 free-radical polymerization 187 initialization 46, 51 initialization scheme 46 input language 43648 ionic polymerization 252 live polymer 33 molecular architecture 32 molecular weight 32 required 43, 46 scale factors 50 segment composition 32 segment-based reaction model 264 sequence length 32 specifying 5152 specifying conventional 51 specifying conventional attributes 464 specifying scale factors 52 specifying scaling factors 466 step-growth polymerization 120 structural properties tracked 23 types 34 unit operation model treatment 32830 user-specified 45 Ziegler-Natta 44 Ziegler-Natta polymerization 236 Component databanks about 25 for initiators 26 for PC-SAFT 26 for polymers 11, 26 for POLYPCSF 26 for pure components 25 for segments 11, 26 selecting 28 Components adding reacting 150 catalysts 24 categories 2125 characterizing 12
conventional 22 databanks 378420 defining 12 defining types 28 fortran utilities 352, 43648, 44854 input language 46064 ionic initiators 24 naming 28, 460 oligomers 23 POLYMER databank 37882, 37982 polymers 22 pure component databank 378 segment approach 27 SEGMENT databank 383420 segments 24 site-based 24 specifying 27 specifying catalysts 46164 specifying oligomers 46164 specifying polymers 46164 specifying step-growth 153 Composition 8 Condensation polymerization 78, 122 Condensation reactions 99 Configuring Aspen Polymers 37273 Consumption of radicals 5960 Continuous polymerization 88 Conventional components 22 Conventional species 259 Convergence for RCSTR 300 improving 50 initialization options (RCSTR) 306 parameter tuning 346 RBatch troubleshooting 32427 RCSTR troubleshooting 3079 RPlug troubleshooting 31519 scaling factors (RBatch) 324 scaling factors (RCSTR) 304 scaling factors (RPlug) 315 solver method (RBatch) 326 solver method (RPlug) 317 step size (RBatch) 326 step size (RPlug) 317 troubleshooting data regression 34547 Conversion energy balance 303
Index
525
Copolymer density 75 Copolymerization 61 free-radical 15994 ionic 24155 ionic propagation 248 user input for ionic model 246 user input for Ziegler-Natta model 231 Ziegler-Natta 22040 Copolymers 16 COPYCA 440 Coupling reactions 250 CPACK 448 CPE See Chlorinated polyethylene Critical micelle concentration 197 Cross linking 261 Cross-link formation 181 Cross-linking 32, 34 Crystalline polymers 16 Crystallinity 8 Custom prop-sets 73 Custom models See User models, See User models customer support 3 Cycle time 323 Cyclodepolymerization reactions 100 D DAMP-FAC 303 Damping factor 303 Data collection 333 defining regression cases 343 fitting 33132 interpreting regression results 344 literature search 332, 333 point 337 profile 337 regression 33132 review 332 sequencing regression cases 344 trend analysis 333, 335 verification 333 Data fitting See also Data regression
applications 331 data collection 333 data review 332 data verification 333 features 285 literature search 332, 333 model development 332, 335 model refinement 333, 336 parameters 33435 preliminary fit 332, 33435 procedure 33236 trend analysis 333, 335 Data regression See also Data fitting activation energy 348 base-case model 337 choosing parameters 347 convergence problems 34547 data sets 337 defining cases 337, 343 entering data 337 entering operating conditions 337 flowsheet variables 36971 fortran blocks 339 interpreting results 34445 manipulating variables 339 point data 341 procedure 33236, 33650, 33650 profile data 342 Prop-Sets 339 scaling fitted parameters 348 sensitivity studies 347 sequencing cases 344 standard deviation 343 troubleshooting 34547 tuning 346 Databanks component 25, 378420 functional group 11 INITIATOR 26 PC-SAFT 26 polymer 11 POLYMER 26, 37882 POLYPCSF 26 pure component 25, 378 segment 11 SEGMENT 26, 382420 selecting 28
526
Index
Dead polymer 34 Dead polymer chain 165 Dead sites 44 Dead zones 300, 313 Defining additional simulation options 13 components 12 feed streams 13 flowsheet options 12 global simulation options 12 polymerization kinetics 13 property models 13 regression cases 343 UOS model operating conditions 13 Degree of branching 32, 53 cross-linking 32 polymerization 32, 55 Density as polymer property 8 function 5657 of copolymer 75 Depolymerization 260 Design-spec block 368 Desorption 209 Developing models 12 Direct esterification 86 Displaying distribution data for reactors 67 distribution data for streams 67 distribution data tables 67 Disproportionation 176 Distillation models about 293 available 287 RadFrac 293 Distribution average properties and moments 5657 calcuations 467 chain length 62 copolymerization 61 displaying data table 67 displaying for reactors 67 displaying for streams 67 functions 54, 56 GPC 64, 65 in process models 56 kinetic reactors 62 method of instantaneous properties 5861
moment equation 18384 moments 5657 particle size 21214 plotting data 67, 68 plug flow reactors 63 polymer 62 procedure 65 specifying calculations 6668 specifying characteristics 66 streams 64 structural property 5369 tracking 62 verification 65 Distribution calculations specifying input language 467 Dupl about 28890 attribute handling 328 Duty in RBatch 319 in RCSTR 297 in RPlug 309 Dyads 34 free-radical rate equation 184 Dynamic models 10, 13 E EB-LOOP 303 e-bulletins 3 Editing emulsion reactions 217 free-radical reactions 191 ionic reactions 253 segment-based reactions 279 user step-growth reactions 155 Ziegler-Natta reactions 239 Elastomers 16 Electrophilic reactions 97 Emulsion polymerization absorption 209 accessing model 215 activated initiation 207 adding reactions 217 applications 195 aqueous phase 204 assigning rate constants 217 attributes 214 built-in reaction listing 216 chain growth 82 desorption 209 editing reactions 217
Index
527
homogeneous nucleation 200 202 industrial processes 196 input language 49399 kinetics 196211, 207 kinetics scheme (figure) 200 latex 198 latex reactions 203 micellar nucleation 197200 model 195219 model assumptions 211 model features 21114 monomer partitioning 21112 nomenclature 204 nucleation time 199 particle growth 197, 202 particle number 199 particle phase 206 particle size distribution 21214 population balance equation 213 products produced 196 properties calculated 214 radical balance 2037 rate constant 210 rate of particle formation 202 reactions 200 redox initiation 208 seed process 202 Smith-Ewart theory 207 specifying calculation options 218 specifying gel-effect 218 specifying model 215 specifying particle growth parameters 219 specifying phase partitioning 218 specifying reacting species 216 stage I (seed) 198 stage II (growth) 198, 202 stage III (finishing) 198 user profiles 214 End group reformation reactions 100 End-use properties about 7076 adding a Prop-Set 76 calculating 73, 76 density of copolymer 75 input language 46870 intrinsic viscosity 74
melt index 75 melt index ratio 76 relationship to structure 72 selecting 76 zero-shear viscosity 74 Energy balance conversion 303 Entering point data 341 profile data 342 standard deviations 343 Equilibrium for ionic polymerization 250 for Ziegler-Natta polymerization 235 phase 184 reactions with counter-ion 248 reactor models 296 Equilibrium models RGibbs 296 RYield 296 Esterification batch process 90 direct 86 operating conditions 89 results 88 secondary 87 Estimating property parameters 473 Ethylene process types 222 Ethylene-propylene 221, 224 Exchange reactions 248 F Features 5, 913 Feed streams defining 13 with polymers 23, 46 Files startup 373 Fitting activation energy 348 choosing parameters 347 Flash2 about 290 attribute handling 329 input variables 339 results variables 339 Flash3
528
Index
about 290 attribute handling 329 input variables 339 results variables 339 Flowsheeting options 11 Flowsheets basic unit operation models 286 calculation procedure 367 calculator block 367 case studies 368 design-spec block 368 distillation models 287, 293 Dupl block 28890 equilibrium reactor models 296 Flash2 block 290 Flash3 block 290 fractionation models 287 FSplit block 291 Heater block 291 incorporating spreadsheets 367 kinetic reactor models 296327 mass-balance reactor models 29496 Mixer block 291 model configuration tools 367 69 Mult block 291 optimization 369 Pipe block 292 polymer process 284 process studies 36769 Pump block 292 RadFrac block 293 RBatch block 31927 RCSTR block 296309 reactor models 288, 294 REquil block 296 RGibbs block 296 RPlug block 30919 RStoic block 294 RYield block 295 sensitivity study 368 Sep block 293 Sep2 block 293 setting fixed variables 368 steady-state 28285 stream manipulators 286 unit operation models 286330 variables 36971 variables for data regression 36971 Fortran arguments 43559
linking 374 monitors 352 templates 374 utilities 352, 43559 Fortran blocks in data regression 339 to enforce assumptions 339 to manipulate process variables 340 to scale paramters 349 Fortran utilities CAELID 436 CAID 436 CAMIX 437 CASPLT 438 CASPSS 438 CAUPDT 439 component handling 352 COPYCA 440 CPACK 448 for component attributes 43648 for components 44854 for mixture molar volume 458 for streams 45459 GETCRY 440 GETDPI 443 GETDPN 441 GETMWN 442 GETMWW 443 GETSMF 444 GETSWF 445 IFCMNC 449 IPTYPE 454 ISCAT 449 ISINI 450 ISOLIG 450 ISPOLY 451 ISSEG 451 LCAOFF 446 LCATT 446 LOCATS 455 LPHASE 456 NCAVAR 447 NPHASE 456 NSVAR 457 SCPACK 452 SSCOPY 457 stream handling 352 VOLL 458 XATOWT 453 XATOXT 453 Fractionation models 287 Free-radical iniators
Index
529
decomposition rate parameters 42123 Free-radical polymerization accessing model 189 adding reactions 191 applications 159 beta-scission reactions 179 bifunctonal initiator decomposition reaction 170, 171 branching 188 built-in reaction listing 190 bulk 160 bulk polymer chain length moment equation 183 calculation method 182 catalyzed initiation reaction 169 chain transfer reactions 174 dyads 184 editing reactions 191 gel effect 166 gel effect 18486 induced initiation reaction 169 industrial processes 160 initiation reactions 167 initiator decomposition reaction 168 input language 48293 kinetics 16179 kinetics nomenclature 162 kinetics scheme (figure) 161 live polymer chain length moment equation 183 model 15994 model assumptions 18287 model features 18287 modifying the rate expression 166 moment-property relationship equation 187 parameters 18789 pendent double bond polymerization 181 phase equilibrium 184 propagation reactions 172 properties calculated 18789 quasi-steady-state approximation 184 rate constant 166 reactions 161
solution 160 specifying calculation options 192 specifying gel-effect 192 specifying model 190 specifying reacting species 190 specifying reactions 191 specifying user profiles 193 structural properties 188 termination reactions 17475 user profile properties 188 Frequency function 5657 FSplit about 291 attribute handling 328 Functional group databank 11 G Gas-phase process 222 Gear integrator 315, 324 Gel effect built-in correlations 185 free-radical 166 free-radical polymerization 184 86 specifying 192, 218 user specified correlations 186 user subroutine arguments 186 Gel effect subroutine free-radical 166 Gel permeation chromatography 64 Generation of radicals 59 GETCRY 440 GETDPI 443 GETDPN 441 GETMWN 442 GETMWW 443 GETSMF 444 GETSWF 445 Glycol recovery 87 GPC 64 H HDPE See High density polyethylene Heat exchangers 299 Heater about 291 attribute handling 329
530
Index
help desk 3 Heterogeneous catalysts 221 High density polyethylene about 220 processes 222 High impact polypropylene 224 HIPP See High impact polypropylene Hold-up in RCSTR 297 Homogeneous catalysts 221 Homogeneous nucleation particle formation 197 process 200202 rate of particle formation 202 Homopolymers 15 I IFCMNC 449 INCL-COMPS 150 Induced initiation reaction 169 Industrial applications polymer production steps 282 84 polymer production steps (figure) 282 Industrial processes emulsion polymerization 196 free-radical polymerization 160 ionic polymerization 242 model uses 366 segment-based reaction model 257 step-growth polymerization 86 Ziegler-Natta polymerization 221 Inhibited sites 226 Inhibition catalyst sites 44, 234 Initators for ionic polymerization 246 Initialization hybrid option 307 integration option 306 options for RCSTR 306 solver option 306 Initiation activated 207 catalyzed 167 decomposition rate 167 free-radical 168, 170, 171 free-radical polymerization 167 induced 167
ionic 44, 243 reaction for catalyzed 169 reaction for decomposition 168 reaction for induced 169 redox 208 INITIATOR databank about 26 Initiators databank 26 free-radical 42123 ionic 24 Injection ports 314 Input language attribute scaling factors 466 catalysts 46164 component attributes 43648 components 46064 conventional component attributes 464 distribution calculations 467 emulsion 49399 end-use properties 46870 for Aspen Polymers 460520 free-radical 48293 ionic 51017 oligomers 46164 physical properties 47074 polymers 46164 property data 471 property methods 470 property parameter estimation 473 prop-set 46870 segment-based reactions 51721 step-growth 47482 streams 465 Ziegler-Natta 499509 Input variables Flash2 339 Flash3 339 MultiFrac 339 RadFrac 339 RBatch 338 RCSTR 338 RPlug 339 standard deviations 343 Installing Aspen Polymers 373 Instantaneous number-average 61 properties 56, 5861, 62 weight chain length 6061 Interfacial processes 82
Index
531
Intermolecular reactions 99 Intramolecular reactions 99 Intrinsic viscosity 74 Ionic initiator 24 Ionic initiators component attributes 32 properties tracked 44 Ionic polymerization accessing model 252 active species formation 246 adding reactions 253 aggregation 248 applications 241 assigning rate constants 254 association 248 built-in reaction listing 253 chain initiation 247 chain termination 249 chain transfer 249 comparison to other addition processes 242 copolymerization steps 246, 248 coupling 250 editing reactions 253 equilibrium with counter-ion 248 exchange 248 industrial processes 242 initiator attributes 243 initiator types 246 input language 51017 kinetics scheme 24250 kinetics scheme (figure) 244 model 24155 model assumptions 25051 model features 25051 nomenclature 245 phase equilibria 250 polymers tracked 243 propagation 247 properties calculated 25152 rate calculations 250 rate constants 246 reactions 244 specifying model 252 specifying reacting species 252 IPTYPE 454 ISCAT 449 ISINI 450 ISOLIG 450 ISPOLY 451
ISSEG 451 K Kinetic models RBatch 31927 RCSTR 296309 RPlug 30919 Kinetics data fitting 33132 decomposition rate parameters 42123 defining polymerization 13 emulsion (input language) 493 99 emulsion polymerization 196 211, 207 free-radical (input language) 48293 free-radical polymerization 161 79 ionic (input language) 51017 ionic polymerization 24250 mechanisms 10 melt polycarbonate 11820 multi-site 63 nylon reactions 10718 parameter influence on 334 polyester reactions 1017 polymerization 78 rate constant parameters 421 34 reactor models 296327 segment-based reaction model 261 single-site 63 specifying emulsion 21519 specifying free-radical 18993 specifying ionic 25254 specifying step-growth 5152 specifying step-growth (input language) 47482 specifying Ziegler-Natta 23739 step-growth polymerization 97 120 user fortran arguments 43559 user models 35761 user subroutine (example) 358 user subroutines 145
532
Index
Ziegler-Natta (input language) 499509 Ziegler-Natta polymerization 22535 L Latex definition 198 number of particles per liter 199 reactions 203 LCAOFF 446 LCATT 446 Linear condensation polymers 55 Linear low density polyethylene about 220 processes 222, 223 Linking fortran 374 Liquid enthalpy user subroutine (example) 363 Liquid process 223 Live polymer chain 165 polymer chain length moment equation 183 Live polymer 33, 34 LLDPE See Linear low density polyethylene Local work arrays 151, 275 LOCATS 455 Low density polyethylene 160 Low molecular weight polymer 55 LPHASE 456 M Mass balance 303 Mass-balance models RStoic 294 RYield 295 Material streams 46 MB-LOOP 303 Melt index 8, 75 Melt index ratio 76 Melt polycarbonate rate constants 119 reaction components 118 reaction kinetics 11820 step-growth reactions 119 Melt-phase nylon-6,6 processes 118 polymerization 96
processes 81 Metallocene catalysts 221 Method of instantaneous properties 56, 5861, 62 Method of moments 56, 182 Methylmethacrylate 195 Micellar nucleation 197200 MIXED substream variables 370 Mixer about 291 attribute handling 329 Mixing non-ideal in RCSTR 298 non-ideal in RPlug 312 Modeling applications 85, 159, 195, 220, 241, 256 data fitting 285, 33132 enforcing assumptions 339 features 285 nylon 9296 nylon-6,6 112 polycarbonates 9697 polyesters 8692 polymer phase change 295 polymer processes 284 steady-state 28285 tools 285 unit operations 285, 286330 Models accessing variables 36971 analysis tools 36769 application tools 36671 base case 337 calculations for user models 35257 defining 12 developing 332, 335 parameter fitting 33435 possible uses 366 process studies 36769 refining 333, 336 structure for user models 351 trend analysis 333, 335 unit operation 11 user 35165 USER2 routine 354 Molar volume fortran utilities 458 Molecular structure SEGMENT databank 383420 Molecular weight
Index
533
as component attribute 32 distribution 8, 56 number-average 75 weight-average 34, 75 Moment equations bulk polymer 183 general 182 live polymer 183 relationship to properties 187 Moments of chain length distribution first 38, 46 Monomers corresponding segment formulas 123 definition 15 functional groups 125 partitioning 21112 purification 283 synthesis 28384, 283 Most-probable distribution 55, 110, 116, 127 Mult about 291 attribute handling 329 MultiFrac attribute handling 329 input variables 339 results variables 339 Multimodal distributions 54 N NCAVAR 447 Newton solver 303 Nomenclature for emulsion model 204 for free-radical model 162 for ionic model 245 for segment-based reaction model 262 for step-growth model 99 for Ziegler-Natta model 229 POLYMER databank 37982 SEGMENT databank 382 NPHASE 456 NSVAR 457 Nucleation homogeneous 197, 200202 micellar 197200
period 198 time 198 time (equation) 199 Nucleophilic reactions about 97 nomenclature 99 Number average chain length distribution 61 degree of polymerization 55 Number-average degree of polymerization 34 Nylon aqueous salt solutions 94 melt-phase polymerization 96 production process 9296 salt preparation 94 Nylon-6 production process 92 rate constants 109 reaction components 108 reaction kinetics 107 step-growth reactions 108 user-specified reactions 109 Nylon-6,6 melt-phase polymerization 118 modeling approaches 112 production process 94 rate constants 114, 115 reaction components 112 reaction kinetics 111 step-growth reactions 113 user-specified reactions 116 O Occupied sites 44 Oligomers as components 23 definition 15 fractionation 126 segments 24 specifying 30 Optimization 369 Orienticity 34 P Packed vectors 151, 275 Parameters data fitting 33132 decomposition rate 42123
534
Index
estimating property 473 fitting 332, 33435 for free-radical polymerization 18789 influence of kinetics 334 integer 151, 275 kinetic rate constant 42134 POLYMER property 378 real 151, 275 scaling 348 SEGMENT property 382 to manipulate process variables 340 tuning for data regression 346 Particle growth in emulsion polymerization 202 specifying parameters 219 PBT See Polybutylene terephthalate PC-SAFT databank 26 PC-SAFT databank about 26 PEN See Polyethylene naphthalate Pendent double bond polymerization 181 PET See Polyethylene terephthalate Phase equilibria ionic polymerization 250 step-growth polymerization 122 Ziegler-Natta polymerization 235 Phase equilibrium free-radical polymerization 184 Phase partitioning specifying 218 Physical properties calculations in user models 356 fitting parameters 33435 input language 47074 user models 36165 user subroutine (example) 363 Pipe 292 Plant data fitting 33132 Plot distribution data 67, 68 PMMA See Polymethyl methacrylate Point data about 337 entering 341 Polyamides 86 Polybutadiene 241 Polybutene 241
Polybutylene terephthalate 91 Polycarbonates aliphatic 85 aromatic 85 production process 9697 reaction kinetics 11820 Polydispersity index 61 Polyesters assigning rate constants 104 polyester technology package 91 production process 85, 8692 reaction components 102 reaction kinetics 1017 side reactions 105 step-growth reactions 103 user-specified reactions 106 Polyethylene chlorinated 256 low density 160 Polyethylene naphthalate 91 Polyethylene terephthalate batch processes 8991 continuous step-growth polymerization 8689 solid-state models 92 Polyisobutylene 241, 256 Polymer chain bulk 165 dead 165 definition 165 live 165 POLYMER databank about 11, 26, 378 components 37982 nomenclature 37982 Polymerization addition 78 bulk 82 chain-growth 79, 80 condensation 78 condensation polymerization 122 continuous 88 degree of 32 emulsion 82, 195219 free-radical 15994 interfacial 82 ionic 24155 kinetics 10, 13, 78 manufacturing step 284 melt phase 81 precipitation 82 process overview 67
Index
535
process types 81 reaction types 78 reactions 78 solid-state 81 solution 82 step-growth 79, 80, 85158 suspension 82 Ziegler-Natta 22040 Polymers acrylic acid 195 addition 55 aggregate 33, 34 aliphatic polycarbonates 85 amorphous 16 aromatic polycarbonates 85 as components 23 average properties and moments 5657 branched 16 bulk polymer chain length moment equation 183 butadiene 195 butyl acrylate 195 butyl methacrylate 195 by chemical structure 18 by physical structure 16 by property 17 chain-growth 81 characterizing 19 chlorinated polyethylene 256 chloroprene 195 component attribute sets 3435 component attributes 32, 34 component characterization 10 crystalline 16 data fitting procedure 33236 data regression procedure 336 50 dead 34 definition 6 elastomers 16 emulsion properties calculated 214 end-use properties 7076 ethylene-propylene 221 free-radical properties calculated 18789 high density polyethylene 220 high-impact polystyrene 159
ionic properties calculated 251 52 ladder 16 linear 16 linear condensation 55 linear low density polyethylene 220 live 33, 34 live polymer chain length moment equation 183 low density polyethylene 160 low molecular weight 55 mass 120, 264 method of instantaneous properties 56, 58, 62 method of moments 56 methylmethacrylate 195 mole fraction 263 monomer purification 283 monomer synthesis 28384, 283 network 16 nomenclature 37982 phase change 295 polyamides 86 polybutadiene 241 polybutene 241 polyesters 85 polyisobutylene 241, 256 polymerization step 284 polymethyl methacrylate 160, 256 polyoxides 241 polypropylene 221 polystyrene 159, 160, 241 polyurethanes 86 polyvinyl acetate 159 polyvinyl alcohol 160, 256 polyvinyl chloride 159 processing 67 processing step 284 production rate 60 production steps 28284 properties 19 properties tracked 34 property distributions 5369 property parameters 378 prop-sets 71 purification 28384 reacting 257 recovery 9, 284
536
Index
segment-based properties calculated 264 segments 24, 382 separation 9, 284 specifying 29 star 16 step-growth 80 structural properties 23 structure 15 structure of 1519 styrene 195 synthesis 284 tetrafluroethylene 195 thermoplastics 16 thermosets 16 tracking structural properties 32 vinyl chloride 195 vinylacetate 195 Ziegler-Natta properties calculated 236 Polymethyl methacrylate 160, 256 Polyoxides 241 POLYPCSF databank 26 POLYPCSF databank about 26 Polypropylene about 221 process types 223 Polypropylene terephthalate 91 Polystyrene 159, 160, 241 Polyurethanes 86 Polyvinyl acetate 159 Polyvinyl alcohol 160, 256 Polyvinyl chloride 159 Population balance equation for emulsion polymerization 213 equation for free-radical polymerization 182 Potential sites 44 Power-law reaction model See Segment-based reaction model:about PPT See Polyproylene terephthalate Precipitation polymerization 82 Pressure drop 297, 310 in RBatch 320 in RCSTR 297 in RPlug 310 Process modeling data fitting 285
dynamic 10, 13 features 285 flowsheets for polymer processes 284 issues for polymers 79 steady-state 10, 13, 28285 tools 285 unit operations 285 Processing polymers 284 Profile data about 337 data sets 342 entering 342 RBatch 342 RPlug 342 Propagation depolymerization 260 free-radical polymerization 172 ionic polymerization 247 segment-based reaction model 261 sites 226 Ziegler-Natta polymerization 233 Properties average polymer 5657 branching 23 chain size 53 composition 8 copolymer composition 23, 53 copolymerization 61 crystallinity/density 8 degree of branching 53 degree of polymerization 23 density of copolymer 75 end-use 7076 estimating parameters 473 for polymers 56 input language 47074 intrinsic viscosity 74 melt index 8, 75 melt index ratio 76 method of instantaneous 58 molecular structure 23 molecular weight 23 molecular weight 8 moments of molecular weight distribution 23 particle size 53 polymer structural 32, 53 prop-set 71 segment composition 23 specifying data 471
Index
537
viscosity 8 zero-shear viscosity 74 Property distributions bimodal 54 bivariate 53 most-probable 55 multimodal 54 Schulz-Flory 54 Stockmayer bivariate 56 structural 5369 types 53 unimodal 54 Property methods input language 470 Property parameter databanks 11 Property set See also Prop-Sets Prop-Sets adding 76 custom 73 defining 71 for data regression 339 for polymers 71 properties 71 uses 71 Propylene processes 223, 224 Pseudocondensation reactions 99 Pump 292 Pure components databank 25, 378 Purification monomer 283 process step 28384 PVA See Polyvinyl alcohol Q QSSA See Quasi-steady-state approximation Quasi-steady-state approximation 184 R RadFrac about 293 attribute handling 329 input variables 339 results variables 339 Radiation initiation reaction 169 Radicals
absorption 206 balance 2037 consumption of 5960 depletion 204 desorption 206 generation 204 generation of 59 rate of production 204 termination 206 Random scission 100 Rate constant parameters data-fitting 285 Rate constants assigning to emulsion reactions 217 assigning to ionic reactions 254 assigning to step-growth reactions 154, 156 assigning to Ziegler-Natta reactions 239 data fitting 331 emulsion 210 for melt polycarbonate 119 for model generated reactions 131 for nylon-6 109 for nylon-6,6 114, 115 for polyesters 104 for user-specified reactions 135, 280 free-radical 166 ionic 246 kinetic parameters 42134 segment-based 261 specifying for segment-based power-law reactions 279 specifying for step-growth user reactions 155 step-growth 149 user subroutines 140, 270 Ziegler-Natta 231 Rate expression step-growth 129, 134 RBatch about 31927 attribute handling 330 batch reactors 322 common problems 327 cycle time 323 duty 319
538
Index
dynamic scaling 324 hybrid scaling options 325 input variables 338 pressure 320 profile data 342 residence time 321 results variables 338 scaling options 324 semi-batch reactors 322 solver method 326 specifying user profiles 193 static scaling options 324 step size 326 streams 322 temperature 319 troubleshooting convergence 32427 volume 321 RCSTR about 296309 algorithm 300 attribute handling 330 calculation loops 301 calculation table 301 common problems 308 component scaling 305 condensed phases 297 convergence 300 duty 297 effective hold-up 297 external heat exchanger 299 horizontal partition 298 hybrid initialization 307 initialization options 306 input variables 338 integration initialization 306 multiphase 297 non-ideal mixing 298 pressure 297 residence time 297 results variables 338 scaling options 304 single-phases 297 solver initialization 306 substream scaling 305 temperature 297 troubleshooting convergence 3079 vertical partition 299 with dead zone 300 Reacting phase specifying for segment-based power-law model 277
specifying for step-growth 156 Reacting polymers 257 Reaction models Aspen Plus 83, 35157 available 35157 basic unit operation 286 built-in 82 custom 83 distillation 287, 293 Dupl 28890 equilibrium 296 Flash2 290 Flash3 290 fractionation 287 FSplit 291 generic 83 Heater 291 kinetic 296327 mass-balance 29496 Mixer 291 Mult 291 Pipe 292 Pump 292 RadFrac 293 RBatch 31927 RCSTR 296309 reactor 288, 294 REquil 296 RGibbs 296 RPlug 30919 RStoic 294 RYield 295 Sep 293 Sep2 293 stream manipulators 286 treatment of component attributes 32830 Reactions active species 246 adding emulsion 217 adding free-radical 191 adding ionic 253 adding segment-based 279 adding user 155 adding Ziegler-Natta 238 addition 99 aggregation 248 assigning emulsion rate constants 217 assigning ionic rate constants 254 assigning step-growth rate constants 154
Index
539
assigning user rate constants 156 assigning Ziegler-Natta rate constants 239 association 248 backbone 260 beta-scission 179 bifunctional initiator decomposition 170, 171 branching (segment-based) 261 branching (Ziegler-Natta) 235 catalyst preactivation 232 catalyst site activation 232 catalyzed initiation 167, 169 chain initiation (free-radical 167 chain initiation (ionic) 247 chain initiation (Ziegler-Natta) 232 chain scission 260 chain termination (free-radical) 17475 chain termination (ionic) 249 chain transfer (free-radical) 174 chain transfer (ionic) 249 chain transfer (Ziegler-Natta) 233 chain-growth 80 classifying 78 cocatalyst poisoning 235 combination 100, 261 condensation 99 conventional species 259 coupling 250 cross linking 261 cyclodepolymerization 100 depolymerization 260 editing emulsion 217 editing free-radical 191 editing ionic 253 editing segment-based 279 editing user 155 editing Ziegler-Natta 239 electrophilic 97 emulsion polymerization 200 end group reformation 100 equilibrium with counter-ion 248 exchange 248 for step-growth polymerization 122 free-radical polymerization 161
homogeneous nucleation 200 including user 154 induced initiation 167, 169 Inhibition 177 initiator decomposition 167, 168 intermolecular 99 intramolecular 99 ionic polymerization 244 latex 203 melt polycarbonate kinetics 118 20 micellar nucleation 197 micellar nucleation (figure) 198 modification See Segment-based reaction model nucleophilic 97 nylon-6 kinetics 107 nylon-6,6 kinetics 111 particle growth 202 polyester kinetics 1017 polymerization 78 propagation (free-radical) 172 propagation (ionic) 247 propagation (segment-based) 261 propagation (Ziegler-Natta) 233 pseudocondensation 99 radiation initiation 169 radical balance 203 rearrangement 100 reverse condensation 99 ring addition 100 ring closing 100 ring opening 100 side group 260 site deactivation 234 site inhibition 234 specifying segment-based 276 80 specifying user rate constants 155 spontaneous initiation 169 step-growth 80 step-growth functional groups 124 step-growth polymerization 100 step-growth rate constants 154 supplied by emulsion model 211 14
540
Index
supplied by free-radical model 18287 supplied by ionic model 250 supplied by segment-based model 264 supplied by step-growth model 12934 supplied by Ziegler-Natta model 236 terminal double bond 235 termination (free-radical) 174 75 termination (ionic) 249 thermal initiation 169 types affecting catalyst states 225 user-specified step-growth 134 36 viewing emulsion 216 viewing free-radical 190 viewing ionic 253 viewing segment-based 278 viewing step-growth 153 viewing Ziegler-Natta 238 Ziegler-Natta polymerization 227 Reactor models about 294 available 288 data sets 342 equilibrium 296 input variables 338 kinetic 296327 mass-balance 29496 results variables 338 Reactors condensed phase RCSTR 297 convergence problems for RBatch 32427 convergence problems for RCSTR 3079 convergence problems for RPlug 31519 displaying distribution data 67 distribution 62 horizontal partition 298 multiphase RCSTR 297 multiphase RPlug 312 RCSTR algorithm 300 single-phase RCSTR 297 vertical partition 299 with dead zones 300, 313 with external heat exchanger 299
with injection ports 314 Rearrangement reactions 100 Recovery/separation 9, 284 Redox initiation 208 Regression See Data regression Reports for user models 357 step-growth options 156 REquil about 296 attribute handling 330 Residence time RBatch 321 RCSTR 297 RPlug 311 Results variables Flash2 339 Flash3 339 MultiFrac 339 RadFrac 339 RBatch 338 RCSTR 338 RPlug 339 standard deviations 343 Reverse condensation reactions 99 Rgibbs about 296 RGibbs attribute handling 330 Ring addition reactions 100 Ring closing reactions 100 Ring opening reactions 100 Routines USER2 354 RPlug about 30919 attribute handling 330 common problems 318 duty 309 dynamic scaling 315 hybrid scaling 317 input variables 339 multiphase 312 non-ideal mixing 312 pressure 310 profile data 342 residence time 311 results variables 339 scaling options 315 solver method 317 specifying user profiles 193 static scaling options 315 step size 317
Index
541
temperature 309 troubleshooting convergence 31519 with dead zone 313 with injection ports 314 Rstoic about 294 RStoic attribute handling 329 Ryield about 295 RYield attribute handling 329 S Salt aqueous solutions 94 preparation 94 Scale factors about 50 specifying 52 Scaling factors 466 Scaling factors component (RCSTR) 305 dynamic (RBatch) 324 dynamic (RPlug) 315 hybrid (RBatch) 325 hybrid (RPlug) 317 RBatch 324 RCSTR 304 RPlug 315 static (RBatch) 324 static (RPlug) 315 substream (RCSTR) 305 Schulz-Flory distribution 54 Scission 100, 260 SCPACK 452 Secondary esterification 87 Seed process 202 Segment approach 27 SEGMENT databank about 11, 26, 382 components 383420 nomenclature 382 Segment flow 34 Segment fraction 34 Segment-based model assigning rate constants 280
including user rate constant subroutine 280 Segment-based power-law model specifying reacting phase 277 user subroutines 26576 Segment-based reaction model about 25681 accessing 276 adding reaction schemes 278 adding reactions 279 applications 256 assumptions 263 backbone modifications 260 branch formation 261 chain scission 260 combination 261 conventional species 259 cross linking 261 depolymerization 260 editing reactions 279 features 263 including user basis subroutine 281 industrial processes 257 input language 51721 kinetics 261 mole fraction conversion 263 nomenclature 262 propagation 261 properties calculated 264 rate calculations 264 rate constants 261 reaction categories 25863 reactions allowed 25863 side group modifications 260 specifying model 276 specifying pre-exponential units 279 specifying rate constants 279 specifying reaction settings 277 Segments composition 15, 32 copolymers 16 definition 24 homopolymers 15 methodology in Aspen Polymers 27 mole fraction 263 molecular structure 383420 nomenclature 382
542
Index
property parameters 382 sequence 15 specifying 29 structure 15 types 24 Semi-batch reactors 322 Semi-crystalline copolymer density 75 Sensitivity blocks 368 Sep about 293 attribute handling 328 Sep2 about 293 attribute handling 328 Separation/recovery 9, 284 Side group modifications 260 Simulations dynamic 10 templates 373 Site activation 232 Site deactivation 234 Site inhibition 234 Site-based components about 24 attributes 44 specifying 30 Slurry process 222, 223 Smith-Ewart theory 207 Solid-state models 92 Solid-state processes 81 Solution polymerization 82, 160 Solution process 222 Solution processes 82 Solver methods RBatch 326 RPlug 317 Specifying additional simulation options 13 Aspen Polymers options 37273 attribute scaling factors (input language) 466 catalysts 46164 component attributes 5152 component attributes (input language) 43648 component attributes in blocks 51 component attributes in streams 51 component names 460 components 12, 27
components (input language) 46064 conventional component attributes 51, 464 data fit 33236 data regression 33650 databanks 28 distribution calculations 6668 distribution calculations (input language) 467 distribution characteristics 66 emulsion calculation options 218 emulsion kinetics 21519 emulsion kinetics (input language) 49399 emulsion model 215 emulsion rate constants 217 emulsion reacting species 216 end-use properties 76 end-use properties (input language) 46870 feed streams 13 fixed process variables 368 flowsheet options 12 free-radical calculation options 192 free-radical kinetics 18993 free-radical kinetics (input language) 48293 free-radical model 190 free-radical reacting species 190 gel-effect 192, 218 global simulation options 12 ionic kinetics 25254 ionic kinetics (input language) 51017 ionic model 252 ionic rate constants 254 ionic reacting species 252 oligomers 30, 46164 particle growth parameters 219 phase partitioning 218 physical properties (input language) 47074 point data 341 polymerization kinetics 13 polymers 29, 46164 pre-exponential units 157, 279 profile data 342 property data 471 property models 13 reacting phase 277 regression cases 343
Index
543
scale factors 52 segment-based reaction model 276 segment-based reaction rate constants 279 segment-based reaction scheme 278 segment-based reaction settings 277 segment-based reactions 27680 segment-based reactions (input language) 51721 segments 29 site-based components 30 standard deviations 343 step-growth components 153 step-growth kinetics 5152 step-growth kinetics (input language) 47482 step-growth model 152 step-growth rate constants 154, 155, 156 step-growth reacting phase 156 step-growth report options 156 stream attributes 465 UOS model operating conditions 13 user models 35165 user profiles 193 user step-growth reactions 154 Ziegler-Natta kinetics 23739 Ziegler-Natta kinetics (input language) 499509 Ziegler-Natta model 237 Ziegler-Natta rate constants 239 Ziegler-Natta reacting species 237 Spontaneous initiation reaction 169 Spreadsheets incorporating in flowsheets 367 SSCOPY 457 SSplit attribute handling 328 Standard deviations 343 Starting Aspen Polymers 37273 Startup files 373 Steady-state models data fitting 285 features 285
flowsheeting 28285 tools 285 unit operation 286330 unit operations 285 Step-growth polymerization accessing model 152 adding user reactions 155 addition processes 257 applications 85 Aspen PolyQuest 92 assigning rate constants 131, 135, 154, 156 batch PET 8991 built-in reaction listing 153 commercial polymers 80 comparison to chain-growth 79 continuous PET 8689 editing user reactions 155 electrophilic reactions 97 functional groups 124, 125 including user basis subroutine 157 including user kinetic subroutine 157 including user rate constant subroutine 157 including user reactions 154 industrial processes 86 input language 47482 interfacial 82 kinetics 97120 melt phase 81 melt polycarbonate reaction kinetics 11820 model 85158 model features 12023 model predictions 120 model structure 12351 model-generated reactions 129 34 nomenclature 99 nucleophilic reactions 97 nylon 9296 nylon-6 reaction kinetics 107 nylon-6,6 reaction kinetics 111 oligomer fractionation 126 overview 80 PBT 91 PEN 91 phase equilibria 122
544
Index
polycarbonates 9697 polyester reaction kinetics 1017 polyester technology package 91 polyesters 8692 PPT 91 rate constants 118, 129, 149 rate constants example 149 rate expression 129, 134 reacting groups 123 reacting species 123, 126 reaction mechanism 122 reaction stoichiometry 128 reactions 100 solid-state 81 solid-state models 92 solution 82 specifying components 153 specifying model 152 specifying pre-exponential units 157 specifying rate constants 154, 155 specifying reacting phase 156 specifying report options 156 specifying subroutines 157 user reactions 134 user subroutines 13651 Stockmayer bivariate distribution 56 Stoichiometry step-growth 128 Streams continuous batch charge 322 defining feed 13 displaying distribution data 67 distributions 64 fortran utilities 45459 initializing attributes 465 manipulating 286 MIXED variables 370 processing in user models 353 RBatch 322 time-averaged continuous reactor product 323 time-averaged continuous vent product 323 time-varying continuous feed 323 variables for data regression 338 Structure of components 22 of monomers 15 of oligomers 15, 23
of polymers 1519, 19, 23 of segments 15, 24 propertyend-use relationship 72 Styrene 195 Subroutines fortran arguments 43559 including user basis 157, 281 including user kinetic 157 including user rate constant 157, 280 local work arrays 151, 275 updating component list 150 user 13651, 26576 user basis 136, 263, 266 user forms 152 user gel effect 186 user kinetic (example) 358 user kinetics 145 user property (example) 363 user rate constant 140, 270 support, technical 3 Suspension polymerization 82 Synthesis monomer 283 polymer 284 T tacticity 34 TDB See Terminal double bond technical support 3 Temperature in RBatch 319 in RCSTR 297 in RPlug 309 Templates custom 373 fortran 374 simulation 373 Terminal double bond reactions 235 terminal double bonds 34 Terminal models free-radical 165 Ziegler-Natta 231 Terminal monomer loss 100 Termination between chain radicals 177 bimolecular 177 by combination 176 disproportionation 176 free-radical polymerization 174 75
Index
545
inhibition 177 Tetrafluroethylene 195 Thermal initiation reaction 169 Thermoplastics 16 Thermosets 16 Tips configuration 373 data regression 34547 Transesterification 88 Trommsdorff effect 185 Troubleshooting Aspen Polymers 37477 convergence (RBatch) 32427 convergence (RCSTR) 3079 convergence (RPlug) 31519 data regression convergence 34547 diagnostic messages 356 RBatch common problems 327 RCSTR common problems 308 RPlug common problems 318 simulation engine 376 user interface 374 U Unimodal distributions 54 Unit operation models 11 Unit operations Aspen Plus models 35157 available models 35157 basic models 286 calculations 356 diagnostics 356 distillation models 287, 293 Dupl 28890 equilibrium reactor models 296 features 285 Flash2 290 Flash3 290 fractionation models 287 FSplit 291 Heater 291 input variables 338 kinetic reactor models 296327 mass-balance reactor models 29496 Mixer 291 Mult 291 Pipe 292
property calculations 356 Pump 292 RadFrac 293 RBatch 31927 RCSTR 296309 reactor models 288, 294 reports 357 REquil 296 results variables 338 RGibbs 296 RPlug 30919 RStoic 294 RYield 295 Sep 293 Sep2 293 steady-state models 286330 stream processing 353 treatment of component attributes 32830 user model calculations 35257 user model structure 351 user models 35157 variables for data regression 338 USER 351, 357 User attributes properties tracked 45 User fortran arguments 43559 linking 374 templates 374 User models about 35165 calculations 35257 component list 150 diagnostics calculations 356 integer parameters 151, 275 kinetic 35761 packed vectors 151, 275 physical property 36165 property calculations 356 real parameters 151, 275 reports 357 stream processing 353 structure 351 unit operation 35157 unit operation calculations 356 USER block 351 USER2 block 351 User profiles for emulsion polymerization 214
546
Index
specifying 193 User prop-sets 73 User reactions adding step-growth 155 assigning rate constants for step-growth 156 editing step-growth 155 for polyesters 106 nylon-6 109 nylon-6,6 116 specifying rate constants for step-growth 155 specifying step-growth 154 step-growth polymerization 134 36 User routines fortran linking 374 User subroutines segment-based power-law model 26576 step-growth polymerization 136 51 USER2 about 351 model routine 354 V Vacant sites 44, 226 Variables accessing flowsheet 36971 indirect manipulation 339 input 338, 341, 342 results 338, 341, 342 standard deviations 343 Vectors packed 151, 275 Viewing emulsion reactions 216 flowsheet variables 36971 free-radical reactions 190 ionic reactions 253 segment-based reactions 278 step-growth reactions 153 Ziegler-Natta reactions 238 Vinyl chloride 195 Vinylacetate 195 Viscosity as polymer property 8 intrinsic 74 zero-shear 74 VOLL 458 Volume
in RBatch 321 W web site, technical support 3 Weight average chain length 61 degree of polymerization 55 X XATOWT 453 XATOXT 453 Z Z-average degree of polymerization 55 Z-average degree of polymerization 34 Zero-shear viscosity 74 Ziegler-Natta component attributes 44 Ziegler-Natta catalysts about 24 attributes 44 component attributes 32 dead sites 44 inhibited sites 44 occupied sites 44 potential sites 44 properties tracked 44 specifying 24 vacant sites 44 Ziegler-Natta polymerization accessing model 237 adding reactions 238 applications 220 assigning rate constants 239 built-in reaction listing 238 catalyst preactivation 232 catalyst reactions 225 catalyst site activation 232 catalyst states 225 catalyst types 221 chain initiation 232 chain transfer to small molecules 233 cocatalyst poisoning 235 copolymerization steps 231 editing reactions 239 ethylene processes 222 gas-phase process 222, 223 industrial processes 221
Index
547
input language 499509 kinetics scheme 22535 kinetics scheme (figure) 227 liquid process 223 model 22040 model assumptions 235 model features 235 nomenclature 229 phase equilibria 235 polyethylene processes 222 polypropylene process types 223 propagation 233 properties calculated 236 propylene processes 223, 224 rate calculations 236 rate constants 231 rate expressions 231 reactions 227 site deactivation 234 site inhibition 234 site types 226 slurry process 222, 223 solution process 222 specifying model 237 specifying reacting species 237 steps 230 terminal double bond 235
548
Index

Aspen Polymers+Vol1V7 1-Usr

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Aspen Polymers

User Guide Volume 1

Version Number: V7.1 January 2009

Introducing Aspen Polymers

About This Documentation Set

Introducing Aspen Polymers

Aspen Polymers Guides

Introducing Aspen Polymers

Aspen Plus Guides

Aspen Physical Property System Guides

Aspen Dynamics Guides

Introducing Aspen Polymers

Review lists of known deficiencies and defects

Introducing Aspen Polymers

1 Polymer Manufacturing Process Overview

About Aspen Polymers

1 Polymer Manufacturing Process Overview

Overview of Polymerization Processes

Polymer Molecular Bonds

Polymer Manufacturing Process Steps

1 Polymer Manufacturing Process Overview

Issues of Concern in Polymer Process Modeling

1 Polymer Manufacturing Process Overview

Step Monomer synthesis and purification

Modeling Issues/Concerns Feedstock purity Monomer degradation Emissions Waste disposal

Solvent removal Monomer recovery

Solvent removal Solids handling

Monomer Synthesis and Purification

1 Polymer Manufacturing Process Overview

Aspen Polymers Tools

1 Polymer Manufacturing Process Overview

Polymer Physical Properties

1 Polymer Manufacturing Process Overview

1 Polymer Manufacturing Process Overview

Defining a Model in Aspen Polymers

1 Polymer Manufacturing Process Overview

1 Polymer Manufacturing Process Overview

1 Polymer Manufacturing Process Overview

2 Polymer Structural Characterization

2 Polymer Structural Characterization

Polymer Types by Physical Structure

2 Polymer Structural Characterization

Polymer Types by Property

2 Polymer Structural Characterization

Thermal / Mechanical properties Fabrication

Polymer Categories by Chemical Structure

Polydienes Polyhalogen hydrocarbons Polyolefins Polyvinyls

2 Polymer Structural Characterization

Polymer Category Polyesters

Description Ester group on backbone

Examples Polycarbonate polyethylene therephthalate, polybutylene therephthalate polylactide

Polymer Structural Properties

2 Polymer Structural Characterization

2 Polymer Structural Characterization

Pure Component Databank

Property parameter databank selections IUPAC names

Segment structure Polymer properties to be tracked Additional characteristics

Defining Component Names and Types

To access the components specifications input sheet: 1 2 3

To specify component attributes for the polymers in your simulation:

Click specific attributes to add or remove them from the list.

Repeat these steps for each polymer.

You can define as many segments as needed for an oligomer.