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Polymer Chemistry 1I

Nazarbayev University
Polymer Syntheses
Eugene F Douglass, MS, PhD Polymer
Science - Professor
Presented by Click to enter name

Chapter 1
Polymerization of Hydrocarbons
Introduction
Free Radical Polymerization
Cationic Polymerization
Anionic Polymerization
Coordination Catalysts
Miscellaneous Methods

Introduction

Polymerization of ethylene with substituent groups

1 benzyl ethylene Styrene


Vinyl Chloride
Isoprene
Acrylic and Methacrylic acid
Methyl and Ethyl Acrylates

Most common method Free radical polymerization

Addition polymerization

Free radical polymerization

Initiation

Initiators Peroxides, AIBN, Oxidation/Reduction, Halogens

Propagation
Termination

Radical coupling
Disproportionation
Chain transfer

Techniques

Bulk
Solution
Suspension
Emulsion
Precipitation

Experimental Techniques

Bulk Polymerization Thermal polymerization of Styrene

Recipe
Dry and inhibitor free styrene 50 g in test tube
1.0 g Benzoyl Peroxide
1-2 Hours at 80C in water bath, until it become syrupy
Add toluene to dissolve and remove, ppt in Methanol to give
solid polystyrene
Calculate % yield.
Get IR for analysis

Emulsion Polymerization Polystyrene

Concept

Start

Monomer dispersed in water containing a soap forming an emulsion


Water soluble initiator is used
Relatively large droplets of monomer are present (about 1 m in
diameter), stabilized by soap molecules
Micelles of 50-100 soap molecules swollen with monomer of about 10
nm in diameter are present
Aqueous phase consisting of a few monomer molecules and the
initiator which form free radicals

Propagation

Emulsion Polymerization Polystyrene

Propagation

Termination

Monomer droplets and micelles compete for the free radicals, most
enter micelles
Polymerization occurs within micelles, new monomer dragged by
equilibrium forces from monomer droplets through aqueous phase
until monomer supply is exhausted.
Polymerization terminates upon entry of another free radical into
micelles unless replenished by more free radical and monomer.

Final product is a stable dispersion (latex)

Emulsion Polymerization Polystyrene

Used for coatings grade polystyrene


Large quantities of soap residue that impair clarity and
electrical properties.

Experimental Techniques

Emulsion Polymerization Styrene

Recipe
Dry and inhibitor free styrene 71.2 g
128.2 g of distilled water
31.4 ml of 0.680% Potassium Persulfate
100 ml of a 3.56% soap solution
Purge system with Nitrogen gas to remove dissolved air
(oxygen).
Raise temp to 80C using mantle, stir well for 2-3 hours
Describe results, put material to dry in evaporating dish

Emulsion Polymerization

Emulsion Polymerization

Explain thoroughly mechanism based on recipe.

Discussion of reaction conditions


Pilot plant and plant scale up, what features can be
used, techniques??
Read pages 57-66 Polymer Synthesis T & P

Acrylate Polymerization - Emulsion

Please read these informative pages from The Macrogalleria


Polystyrene
Poly(methylmethacrylate)
Free Radical Vinyl Polymerization
Emulsion Polymerization
Goal
The goal is to for you, the enthusiastic lab student, to synthesize a polymer by free-radical emulsion
polymerization. Procedure
Obtain a 10 or 20 mL Erlenmeyer flask
Place the following into the flask:

4 mL of deionized water

potassium persulfate free-radical initiator

sodium lauryl sulfate surfactant

2 mL of monomer
Purge with nitrogen gas for about 1 minute
Shake flask vigorously to form emulsion
Place in an 80oC oil bath for one hour, shaking periodically
Add DI water and NaCl to the flask to break emulsion
Remove polymer from flask and wash repeatedly with DI water
Dry polymer in oven

Different Acrylate monomers

Styrene
Methyl Methacrylate
Ethyl Acrylate
Butyl Acrylate
Hydroxyethyl Acrylate
Acrylic Acid
Methacrylic acid
Different comonomer blends make different copolymers
Some added all together at once, others added one at a time.

Some articles to read and look at, go to moodle

Acrylic Polymers Saunders Chapter 6

All based on Acrylic acid

Three routes to acrylic acid

Propylene

Acetylene

Ethylene

Methacrylic Acid

Esters of Acrylic acid

Various esters of acrylic acid are commercially available, but,


methyl, ethyl and butyl acrylates are most widely used.

Esters of Methacrylic acid

Various esters are commercially available but Methyl


Methacrylate is most important.

Acrylonitrile 3 routes, only one used most often.

Propylene route

Acrylamide
Cyanoacrylates

Polyacrylic Acid and Polymethacrylic acid

Next Weeks lab Polymerization of Ethyl Acrylate

Poly(Methyl Methacrylate)

Bulk Polymerization

Prepolymer formation, using benzoyl peroxide at 0.5%, then placed in a


casting cell and cured for 15 hours at 40C. 95C for 1 hour.

Suspension Polymerization batch amounts

Stirred reactor, for heating and pressure.

Heated to 80C to start, exotherm causes it to rise to 120C and


pressure to go up. Polymerization occurs in about an hour
Hard, rigid material results

Acrylic Copolymers

Thermoplastic acrylics

Acrylic Solutions

Methyl Methacrylate and an Alkyl Acrylate for flexibility

Aromatic hydrocarbon or ketone, such as MEK


Benzoyl Peroxide 0.2-1%
90-110C under slight pressure in a jacketed kettle

Acrylic latices - latex

Acrylic Copolymers

Thermosetting acrylics

Crosslinked films on heating

Acrylic Solutions

Acrylic Copolymers

Thermosetting acrylics

Thursdays lab

http://matse1.matse.illinois.edu/polymers/a.html
300 ml of 0.6 M (5%) ethyl acrylate, CH2 = CHCOOCH3 (To
prepare: mix 16 ml of ethyl acrylate with 284 ml of water.)
5 ml of 0.1 M potassium bromate, KBrO3, (To prepare:
dissolve 0.4 g KBrO3 in water and dilute to 25 ml. This will
be enough for 5 demonstrations.)
5 ml of 0.45 M sodium hydrogen sulfite, NaHSO3 (freshly
prepared) (To prepare: dissolve 0.47 g NaHSO3 in water and
dilute to 10 ml. This will be enough for 2 demonstrations.)

Thursdays lab - procedure

http://matse1.matse.illinois.edu/polymers/a.html

Procedure:

Perform this demonstration in a hood and wear gloves.

Place 300 ml of 5% methyl acrylate in a 1-Liter Erlenmeyer flask.

Add 5 ml of 0.1 M potassium bromate solution and 5 ml of 0.45 M


sodium hydrogen sulfite solution.

Swirl the flask to mix the contents thoroughly and allow the reaction to
proceed for about 15 minutes, shaking the flask occasionally during this
time. As the particles grow, the mixture quickly takes on a milky
appearance.

Pour the emulsion into 300 ml of 5 M sodium chloride solution to


coagulate the polymer.

Polyacrylonitrile - PAN

Textile Fibers end use

Solution Polymerization and Suspension Polymerization


primary methods, solution method is most convenient, as
when a solvent for the polymer is used, the fiber can be then
directly spun.

Polyacrylonitrile

Copolymers about 10% to make fibers easier to dye.


Examples include MMA, VA, 2-vinylpyridine
Heating of fibers leads to decomposition at higher
temperatures, heating at 1500-3000C results in a carbon fiber
with graphitic crystalline structure. The most important
source now for carbon fibers.

Nitrile resins
70:30 Acrylonitrile and MA formed in presence of butadieneacrylonitrile rubber (10-15%).

Polyacrylamide

Polyacrylamide is water soluble, so has only limited


commercial applications
Prepared by free radical polymerization

Different type of polymer results when initiated by a strong


base, a polyamide Nylon 3 is formed.

Polyacrylamide

Poly(2-cyanoacrylate)s

Methyl and ethyl 2-cyanoacrylate form the basis of the socalled super glues
Anionic polymerization easily occurs due to two electron
withdrawing groups on double bond. Weak bases such as
water bring about rapid polymerization

UV Curable polymers/coatings

Based primarily on acrylate monomers

Prepolymers made first with retention of crosslinking


functionality.

Very low VOC (volatile organic compounds)

Monomer often used as solvent

Prepolymer used as thickener

Combination of solution/bulk polymerization

UV Cured polyMMA bulk polymer

UV Cured coatings presentation


http://www.intermediates.basf.com/chemicals/coatings/uv-coatings

Suspension polymerization

Saunders pages 26, 79, 84, 94, 108,118,139, 144,152,155,


163,209,438
Recipe:

150 ml of a 1% solution of sodium poly(methacrylate) in water


50 ml of a 5% solution of sodium poly(methacrylate) in water (see
Note 1)
A buffer solution of 0.85 g of disodium phosphate and 0.05 g of
monosodium phosphate in 5 ml of water
0.5 g of dibenzoyl peroxide paste in water
50.0 g of methyl methacrylate (inhibitor free)
Deionized water (several liters)

Suspension polymerization

Procedure
1.

2.

3.

4.

5.

6.
7.
8.
9.

10.

In a laboratory hood, equip a 500-ml three-necked flask with a sealed stirrer and motor,
condenser, thermometer, and an addition funnel.
Add 150 ml of a 1% solution of sodium poly (methacrylate) in water and a buffer solution of
0.85 g of disodium phosphate and 0.05 g of monosodium phosphate in 5 ml of water
Add a dispersion of 0.5 g of dibenzoyl peroxide in 50 g of inhibitor-free methyl methacrylate to
the reaction flask.
Measure 25 ml of the 5% aqueous solution of sodium poly(methacrylate) into the addition
funnel.
Place the assembled reaction flask in the water bath, attach the stirring motor, and begin
stirring.
Adjust the stirrer speed so that droplets of monomer form that are 2-3 mm in diameter.
Heat the flask with the water bath at 80-82C for 45 to 60 min (see Notes 3 and 4).
Collect the solid particles on a funnel fitted with cheesecloth.
Bundle the particles in the cheesecloth, and place the bundle in 1 liter of boiling deionized
water. Remove the bundle and wash two more times in fresh boiling deionized water.
Open the bundle. Dry the product under reduced pressure at 60-70C.

Polyamides

Nylon 6-10 Interfacial technique


A.
B.
C.
D.

Sebacoyl chloride (reagent grade or freshly distilled)


Tetrachloroethylene (reagent grade or freshly distilled)
Hexamethylenediamine (reagent grade or freshly distilled)
50% aqueous ethanol

Procedure
1.

2.

3.

4.

Add a solution of 3.0 ml (0.014 mol) of sebacoyl chloride dissolved in 100 ml of


anhydrous tetrachloroethylene as received (see Note 1) to a tall-form beaker.
Carefully pour a solution of 4.4 g (0.038 mol) of hexamethylenediamine (see Note 2)
dissolved in 50 ml of water over this acid chloride solution.
Grasp the poly amide film that begins to form at the interface of these two solutions
with tweezers or a glass rod and slowly pull it out of the beaker in a continuous
fashion. Stop the process when one of the reactants becomes depleted.
Wash the resulting "rope"-like polymer with 50% aqueous ethanol or acetone, dry, and
weigh to afford 3.16-3.56 g (80-90%) yields of polyamide.

Polyamides

Linear aliphatic polyamides capable of fiber formation,


commonly called nylons. Fibers and engineered composites.
Fatty polyamides, derived from fatty acids.
Aromatic polyamides - aramids
Proteins
Polyimides

Linear Aliphatic Polyamides


Nylon 6,6 based on 6 carbon diamine and 6 carbon
dicarboxylic acid or di-acid chloride.
Nylon 6 based on ring opening of caprolactam

Condensation polymer

Raw Materials

Adipic acid

Hexamethylenediamine

Raw Materials

Azelaic acid
Sebacic acid
Dodecanedioic acid
-Aminoundecanoic acid
Caprolactam

Preparation

Neutralization of an aqueous solution of adipic acid by the


addition of hexamethylene diamine; exact end point
determined electrometrically. You must have exact
equivalence of the reactants. Why??

On heating, nylon salt dissociates and then polymerization


occurs

Preparation

Nylon 6,9; 6,10; & 6,12

All prepared by same methods above, except different diacids or diacid


chlorides

Nylon 11 is produced continuously by the heating of aminoundecanoic acid at 200-220C with the continuous removal of
water. Why continuous removal of water?
Nylon 6 is produced by the ring opening polymerization of
caprolactam. 5-10% water by weight, and 0.1% acetic acid is fed
into a reactor containing caprolactam (purged with nitrogen).
Mixture heated at about 250C for 12 Hours, at 15 atm pressure.
Low molecular weight material removed by leaching with water or
heating in a vacuum.
Nylon 12 heating dodecyl lactam at 300C in the prescence of
aqueous phosphoric acid

Polymerization mechanism

Polymerization mechanism - anionic

Physical Properties

Polyesters

Unsaturated polyesters
Alkyds
Poly(allyl ester)s
Poly(ethylene terephthalate)
Poly(butylene terephthalate)
Cyclohexylenedimethylene terephthalate polymers
Polyester thermoplastic elastomers
Polyarylates
Poly(p-hydroxybenzoate)s
Polyester plasticizer

Unsaturated Polyesters

Linear polyesters containing aliphatic unsaturation to crosslink


1946 Diethylene Glycol and Maleic Anhydride, cross linked
with styrene.

Glass fiber reinforced polyester laminates 1940s


Bulk Molding Compounds 1950s
Sheet Molding Compounds 1960s

Essentially mixtures of unsaturated polyesters, glass fiber and


filler, which are processed using standard techniques for
thermosetting materials

Raw Materials

Diols

Propylene glycol is the diol most widely used for the manufacture of
linear unsaturated polyesters. Preferred because it forms polyesters
that are compatible with styrene.
Diethylene glycol greater flexibility
Neopentylene glycol (2,2-dimethyl-1,3-propanediol) resistance to
thermal degradation
Diether of propylene glycol and bisphenol A

Ethylene Glycol helps crystallization and added with other diols.

Raw Materials

Unsaturated Acids and Anhydrides

Maleic Anhydride

Fumaric Acid and Chloromaleic acid

Phthalic Anhydride

Raw Materials

Unsaturated Acids and Anhydrides

Adipic Acid, Sebacic Acid, for flexibility, or Isophthalic acid toughness


with high heat distortion temperatures.
Flame resistance can be imparted with chlorinated acids and
anhydrides.

Crosslinking Monomers

Styrene, by far the most common


MMA
Diallyl Phthalate and Triallyl cyanurate

Preparation
Typical formulation
Propylene glycol
100 parts by weight
Maleic anhydride
72
Phthalic anhydride
54
The molar ratio of the ingredients shown above is 1.2: 0.67 : 0.33
Excess of glycol is to allow for loss during the reaction and limit the
molecular weight of the polymer.
150-200C for 6 -16 hours and water is continually distilled from the reactor.
Sometimes xylene is added o help remove water by azeotropic distillation,
and p-TSA added as a catalyst to lower reaction time.
It is then moved to a blending tank with about half the weight of polymer of
monomer is added, along with hydroquinone as inhibitor.
This blend is called the Polyester or Unsaturated Resin, which is then allowed
to cool to room temperature and then shipped to the customer

Preparation

Crosslinking

Use Styrene, or MMA most commonly


Types of initiators

Benzoyl Peroxide, 2,4 dichlorobenzoyl peroxide, di-tert-butyl


peroxide, and lauryl peroxide. Stable at RT, rapidly crosslink from 70
150C.
Cold curing use accelerators, and peroxides like methyl ethyl ketone
peroxide, and cyclohexanone peroxide.

Crosslinking

Cold curing use accelerators, and peroxides like methyl ethyl ketone
peroxide, and cyclohexanone peroxide. Metal salts of fatty acids used
as accelerators.

Alkyds Natural polyesters

Network polymers used in surface coatings


Many derived from phthalic anhydride and glycerol, then
modified with drying oils and fatty acids.

Raw materials
Polyhydric alcohols

Glycerol 3 OH groups on propane 1,2,3 propanetriol


Pentaerythritol, trimethylolpropane &n sorbitol
Sometimes ethylene and propylene glycols are added to
reduce crosslink intensity.

Dibasic acids and anhydrides

Phthalic anhydride, maleic anhydride, isophthalic acid, adipic


and sebacic acids.

Raw materials
Modifying oils and fatty acids

Oils and fatty acids derived from them are essentially


naturally occuring triglycerides, esters of glycerol and mixed
fatty acids (long carbon chains, zero to two or three double
bonds on chain)

Alkyd Resins
Short, medium and long oil resins
Drying oil resins most used in coatings
and alkyd paints
Semi-drying - some use in coatings and
alkyd paints for special purposes, like
high gloss finishes
Nondrying plasticizers

Preparation of Alkyd Polyesters

Fatty Acid process

Fusion method
Oil hydrolyzed to give free fatty acids
Heat to 240C with a mixture of polyol and dibasic acid.
Simultaneous transesterification of polyol, dibasic acid and fatty acids
occur, with all becoming part of the polymer structure.
Solvent or solution method
Xylene (5% by weight) added to the reaction, mixture heated with a
condenser/separation funnel apparatus, which collects an azeotrope
of xylene and water, which then separates, enabling return of the
xylene to the reaction flask.
Provides good temperature control

Preparation of Alkyd Polyesters

Alcoholysis process
Oil heated with the polyol to 240C with a
basic catalyst (Ca(OH)2)
molar ratio, resulting in principal
product of monoglyceride
Add dibasic acid, and then treated the
same as in the fatty acid process, fusion or
solvent method.

Structure of Alkyd Polyesters

Fatty acid residues incorporated into the structure enable usefulness of


material in surface coatings.

Structure of Alkyd Polyesters

Fatty acid residues incorporated into the structure enable usefulness of


material in surface coatings.

Alkyd Film Formation

Mechanism by which an alkyd resin is converted from a liquid


to a dry film is largely determined by the nature of the fatty
acid residues present (Saunders, page 245)

Drying process involves attack by oxygen in the unsaturated regions of


the unsaturated fatty acid residues.
Crosslinking initiated by the decomposition of the oxidation process.
Usually too slow under ambient conditions so resin requires driers,
which are usually naphthenate, linoleates or octoates of metals, like
Cobalt, Lead and Manganese

Modified alkyd resins

Blends with alkyd resins

Incorporated during manufacture

Cellulose nitrate
Chlorinated rubber
Silicone resins
Phenolic resins
Amino resins

Post manufacture

Styrene and other vinyl monomers, heated with initiators under reflux
until required viscosity is reached.

Epoxies

Bisphenol A and Epichlorohydrin

Bisphenol A

Epoxies

Bisphenol A and Epichlorohydrin

Epichlorohydrin

Liquid Resin Preparation

Bisphenol A and epichlorohydrin 1:4 molar ratio heated to 60C with


stirring. Add solid NaOH (2 moles / mole BPA) slowly so reaction
remains neutral.
Reaction is exothermic, cooling applied to keep at 60C.

Epoxies

Solid Resin Preparation

Bisphenol A and epichlorohydrin 1:4 molar ratio heated to 100C with


stirring. Add aqueous NaOH with vigorous stirring.
Results in 30% water in resin emulsion, coagulated washed with hot
water, water is then removed by heating to 150C under reduced
pressure.

Reactant Ratios yield different products

Crosslinking agents

Cannot be crosslinked at a reasonable rate by heat alone, so


we need a curing agent, so all systems are two part systems.

Resin
Curing agent

Curing agents

Tertiary amines

Crosslinking agents

Curing agents

Tertiary amines

Crosslinking agents

Curing agents

Polyfunctional amines

Crosslinking agents

Mechanism of amine link reaction with epoxy resin

Crosslinking agents

Mechanism of amine link reaction with epoxy resin

Crosslinking agents

Mechanism of amine link reaction with epoxy resin

Crosslinking agents

Curing agents

Acid Anhydrides

Crosslinking agents

Curing agents

Acid Anhydrides

Crosslinking agents

Curing agents

Acid Anhydrides

Modified BPA Epichlorohydrin epoxy

Resin Modified epoxies

Phenol Formaldehyde resins

Resin Modified epoxies

Amino resins

Lab Thursday

Bring things to glue together, perhaps use IR.


Reagents and Materials

Test glue curing time with a variety of materials

Tongue depressors, wood, paper, metal, etc.


IR of material between two glass slides.

Polyvinyl acetate - PVAc

Raw Materials

Ethylene route

Mixture of ethylene and acetic acid are oxidized over a palladium


catalyst at 5-10 atm, and 150-200C. Exit gases are quenched and vinyl
acetate is separated by distillation. 95% yield is typical
Acetylene route

Mixture of acetylene (in excess) and acetic acid vapor is passed


through a reaction tube at 190-220C. Tube contains a Zinc catalyst, and
about 50% of the acetic acid is converted per pass with other materials
recycled.

Polyvinyl acetate

Production - first commercial production of PVAc began in


Germany in 1920.

Readily polymerized by bulk, solution, suspension, and emulsion


techniques. Emulsion is the primary method. Resulting latexes used
mainly for water based paints and adhesives.
Emulsion polymerization

Polyvinyl acetate

Structure head to tail mostly

Properties

Too brittle, too much cold flow to be useful in bulk form for rigid
applications. PVAc mostly finds applications in film form in surface
coatings and adhesives. Tg is often lowered by using a plasticizer or
copolymers.

Polyvinyl acetate

Soluble in many solvents, swells in water and softens on


prolonged immersion in water. Readily hydrolyzed to
polyvinyl alcohol by acids and bases.
Decomposition occurs above 70C, accompanied by
elimination of acetic acid giving polyacetylene.
Copolymers

To help film formation and flexibility comonomers are often used in


emulsion polymerization, they include butyl acrylate, 2 ethylhexylacrylate, diethyl fumarate, diethyl maleate and vinyl esters of fatty
acids. Typically 15-20% comonomer

Polyvinyl alcohol very important hydrolysis product

Polyvinyl alcohol (PVA) cannot be prepared from its


monomer, as its monomer rapidly converts to acetaldehyde.
For commercial purposes all is obtained from polyvinyl
acetate by hydrolysis.

Acid and base hydrolysis often results in contamination, so most


common is alcoholysis using a small amount of base as catalyst:

Polyvinyl alcohol very important hydrolysis product

Preferred method to manufacture is solution polymerization


of vinyl acetate in methanol, followed by alcoholysis with base
catalyst.
A continuous process is mentioned in the book:

Polyvinyl alcohol very important hydrolysis product

Many grades of PVA are so-called partially hydrolyzed grades


in which 87-89% of the acetate groups have been replaced,
and completely hydrolyzed grades with 99-100% of the
acetate groups removed.
Water soluble for 87-89% hydrolyzed material, 99-100% no
Physical properties are somewhat dependent on the degree
of alcoholysis.

Glue Video wood glues, PVA etc

https://youtu.be/B9BHxscvE9g

Lab on Thursday

Seeded Emulsion Terpolymerization of Vinyl Acetate, Butyl


Acrylate, and Vinyl Neodecanoate with Gradual Monomer
and Initiator Additions

Lab on Thursday

Lab on Thursday

Making Polyvinyl alcohol from Polyvinyl acetate

Polyvinyl Chloride

Developed in 1872, but only a lab curiosity for over 50 years,


then in 1928 and years following Union Carbide, DuPont and
Farben (in Germany) started working with copolymers of
vinyl chloride with vinyl acetate. Then in 1930 BF Goodrich
developed an alternative approach that made the polymer
PVC usable in plasticized form, using high boiling organic
liquids to plasticize it.
First use mainly for electrical cable insulation, again all uses
were in the plasticized form.
One of the top four polymers in use today for all sorts of
applications. New car smell is plasticizer for the PVC
dashboard and other parts.

Polyvinyl Chloride

Raw materials from acetylene and ethylene

Polyvinyl Chloride

Raw materials from acetylene and ethylene

Polyvinyl Chloride

Preparation Mainly prepared by suspension polymerization,


bulk and emulsion lesser degrees

Bulk Polymerization, uses monomer as dispersent, done at high


pressure and 75C
Suspension polymerization

Polyvinyl Chloride

Preparation Mainly prepared by suspension polymerization,


bulk and emulsion lesser degrees

Bulk Polymerization, uses monomer as dispersent, done at high


pressure and 75C
Suspension polymerization

Polyvinyl Chloride

Preparation Mainly prepared by suspension polymerization,


bulk and emulsion lesser degrees

Emulsion polymerization high pressure, similar process to suspension

Polyvinyl Chloride

Structure primarily head to tail.

Polyvinyl Chloride

Structure primarily head to tail.

Some evidence that commercial PVC is branched

Polyvinyl Chloride

Physical properties colorless rigid material, relatively high


density and low softening point, high dielectric constant &
power factor, and flame retardant due to high chlorine content.
Very limited solubility, soluble at RT in oxygen containing, and
chlorinated solvents.
Most used with plasticizers: phthalates, aryl phosphates, aliphatic
acid estyers, epoxidized oils. 40-60 parts plasticizer to 100 parts
of polymer is typical for most common applications.
Degradation easy due to high temperatures and/or ultraviolet
light, so problem with some formulations in plastic car parts, like
dashboards.

Dehydrochlorination, elimination until almost all chlorine is gone,


unzipping.

Polyvinyl Chloride

Polyvinyl Chloride

Oxidation degrades more rapidly when heated in air.

Polyvinyl Chloride

Photodegradation - dehydrochlorination

Polyvinyl Chloride - modifications

Chlorinated PVC

Vinyl Chloride Vinyl acetate copolymers

Commercial 63-68% chlorine, copolymer of vinyl chloride and s-dichloroethylene

Made with suspension and solution polymerization (page 108)

Vinylidene chloride copolymers suspension and emulsion


processes. Page 110-11.

Polyurethanes

Types Flexible foams, rigid foams, integral foams,


elastomers, surface coatings, and adhesives

Development commercial development dates from 1937 when


Bayer (IG Farben, later Farbenfabriken Bayer, Germany) found
that the reactions of diisocyanates and glycols gave
polyurethanes with interesting physical properties as plastics and
fibers.
Raw materials urethane group results from the reaction
between an isocyanate and a hydroxyl compound

Polyurethanes

Raw materials diisocyanates, diols and polyols are the


principle raw materials
Diisocyanates

Made primarily by the reaction of phosgene and primary amines


Toluene diisocyanate (TDI) made from nitration and hydrogenation
then reaction with phosgene of toluene to get different types of TDI:
65:35 TDI
80:20 TDI
100% 2,4-TDI

Polyurethanes

Raw materials diisocyanates, diols and polyols are the


principle raw materials
Diisocyanates

Made primarily by the reaction of phosgene and primary amines

Diphenylmethane diisocyanate (MDI) derived from aniline

Polyurethanes

Raw materials diisocyanates, diols and polyols are the


principle raw materials
Diisocyanates

Made primarily by the reaction of phosgene and primary amines

Naphthylene diisocyanate (NDI) derived from naphthalene

Polyurethanes

Raw materials diisocyanates, diols and polyols are the


principle raw materials
Diisocyanates

Made primarily by the reaction of phosgene and primary amines

Hexamethylene diisocyanate (HDI) derived from


hexamethylene diamine:

Isophorone diisocyanate

Polyurethanes

Raw materials diisocyanates, diols and polyols are the


principle raw materials
90% Polyethers flexible and rigid foams, coatings,
elastomers Mw from 500 to 3000 is typical
10% Polyesters Mw from1000-2000 is typical, hydroxyl
terminated polyesters primarily. Polyesteramides originally
developed for elastomers, but now for leather adhesives and
flexible coatings for rubber goods.

Isocyanate reactions

Isocyanate reactions

Isocyanate reactions

Isocyanate reactions

Isocyanate reactions

Polyurethane products

Foams
Flexible foams
Diisocyanate, polyol and water two reactions proceed
simultaneously:

TDI is preferred diisocyanate


Polyether foams flexible foams produced by a one-shot process
Diisocyanate, polyol, water and catalysts and surfactant mixed
simultaneously
80% slab stock, 20% molded into parts

Polyurethane products

Polyether foam furniture applications, cushions

Polyester foam textile laminates, coat shoulder pads

Polyurethane products

Foams

Rigid foams
Polymeric MDI is preferred diisocyanate
Polyether and polyester foams, also one shot process, different
blowing agents are used, typically low boiling halogenated alkanes are
used. Trichlorofloromethane is most common.
Typical formulation:

Polyurethane products
Foams
Rigid are closed cell structures used for thermal insulation
products 97% of the volume of a typical foam is occupied by
gas.
Flexible foams furniture applications
Integral foams cellular core and a solid skin, molding
applications like automobile parts.
Elastomers
Cast elastomers

Polyurethane products
Foams
Rigid are closed cell structures used for thermal insulation
products 97% of the volume of a typical foam is occupied by
gas.
Flexible foams furniture applications
Integral foams cellular core and a solid skin, molding
applications like automobile parts.
Elastomers
Cast elastomers poured into a heated mold

Typical use printing rollers

Cast elastomers

Millable elastomers

Can be compounded in mills, and vulcanization is possible

Thermoplastic Elastomers

Typically prepared as fibers spandex

Use linear polyethers/polyesters and linear polyisocyanate


Typically prepolymer is prepared terminated with isocyanate,
then aliphatic diamine is added to effect chain extension.
Then material is spun into a coagulating bath or hot air to
produce a fiber.

Surface coatings
One component systems
Air curing systems
Urethane oils, drying due to atmospheric oxygen
Moisture curing
Cure with atmospheric water
Heat curing systems
Blocked isocyanates and polyester/polyether prepolymers mixed and
then cured using heat in an oven.
Two component systems
Isocyanate polyol mixed immediately prior to use
Prepolymer polyol systems
Adhesives same types, just between two substrates

Silicones Fluids, Resins and Elastomers

History early 20th century, polymer was considered a


problematic by-product.
Commercial interest developed in the 1930s by Corning
Glassworks and General Electric company, working on
electrically insulating materials

Nomenclature Silicone analogues to similar carbon compounds


are called silanes, or polyorganosiloxanes
Substituted silanes named after parent compound
Hydroxyl derivatives are silanols
Silanes with ether linkages are called siloxanes

Nomenclature

Raw materials

Silane production starts with chlorosilanes, which are


manufactured from silicon, or silicon dioxide and chlorine gas.

Production

Grignard process

Production

Direct process

Production

Olefin addition process

Polymerization

Hydrolysis of chlorosilanes to silanols, which then condense


spontaneously to siloxanes:

Polymerization

Hydrolysis of chlorosilanes to silanols, which then condense


spontaneously to siloxanes:

Mechanism

Silicone Products

Fluids Mw from 4000 to 25000

Silicone Products

Elastomers Mw from 300k 700k

Silicone Products

Elastomers Mw from 300k 700k

Silicone Products

Other elastomers (pgs 400-405):

Vinyl silicone elastomers


Phenyl silicone elastomers
Nitrile Silicone elastomers
Fluorosilicone elastomers
Room temperature vulcanizing elastomers
Liquid silicone elastomers
Borosilicones

Resins consist of branched polymers based on the


hydrolysis of trichlorosilanes and dichlorosilanes blended
together to avoid an unusable cross link density.

Silicone Products

Resins often have a mixture of methyl and phenyl groups as part of the
backbone.

Silicone Products

Types of resins:

Physical properties

Modified resins blending or copolymerization. Silicone alkyd resins


are one common example.
Thermal stability
Water repellant

Fluids

Silicone Products

Vulcanized Elastomers

Silicone Products

Vulcanized Elastomers

Crosslinked resins surface coatings and glass fiber laminates

Surface coatings heat resistance, water repellency, nonstick surfaces,


such as cake, candy, confection boxes often have silicone coatings.
Since they are crosslinked/cured, they serve well as nontoxic/nonstick
surface treatments for food handling equipment.

Glass fiber laminates best for electrical insulation quality


under high heat conditions (250C).

Fluoropolymers
History early 20th century, polymer
polychlorotrifluoroethylene was considered of limited value.
Commercial interest developed in 1938 when Plunkett
discovered polytetrafluoroethylene at the DuPont company
by accident
Important Homopolymers
Polytetrafluoroethylene
Polychlorotrifluoroethylene
Polyvinyl Fluoride
Polyvinylidene Fluoride

Development

80% of current output is PTFE (Teflon)


Pilot plant production started in 1943, and large scale
production in 1950 by DuPont (USA)
Many other polymers on this base have been investigated with
a few having commercial value.

Physical Properties
Outstanding Chemical Resistance
Outstanding Thermal Resistance extremes of temperature
Anti-stick characteristics, non-stick surfaces

Raw Materials

Tetrafluoroethylene

Chlorotrifluoroethylene

Vinyl Fluoride -

Raw Materials

Vinylidene Fluoride

Polytetrafluoroethylene

Suspension polymerization

Conventional techniques to produce granular product for molding


and extrusion
Specialized process to give finer particle size and lower molecular
weight, stabilized for latex form product suitable for film casting,
coatings and fiber treatment.
Coagulated from latex form for powder production used for extrusion
of thin sections

Physical Properties
White solid
Waxy appearance and feel
Tough flexible material with moderate tensile strength
Tendency to creep under certain conditions.

Physical properties

Physical properties

Polychlorotrifluoroethylene

Suspension polymerization

Conventional techniques to produce granular product for molding


and extrusion, temperature kept low

Physical Properties
White solid
Waxy appearance and feel
Greater tensile strength, hardness and resistance to creep
than PTFE
Lower softening point, less crystalline, can make thin
transparent films by quenching.
Others discussed in book pages 156-166.

Videos

Check You Tube and Google for any of interest to you.

https://youtu.be/vns5TVZ5xzw

https://youtu.be/rtPhlWi8t3I

The End
Presented by (click to enter name)

Polymer Chemistry 1
Nazarbayev University
Principles of Polymerization
Eugene F Douglass, MS, PhD Polymer
Science - Professor
Presented by Click to enter name

Chapter 4- Emulsion Polymerization


Topics to Cover
Process
Quantitative aspects
Other characteristics
Initiation
Surfactants
Chain Transfer
Other components
Energy Concerns
Molecular Weight
Particle size distribution
Surfactant free
Other Emulsion Polymerization systems
Living Radical Polymerization

Emulsion Polymerization - Process

Utility

First used during WW II for producing synthetic rubbers from 1,3


butadiene and styrene.
SBR and copolymers today
Vinyl acetate, chloroprene, acrylate copolymers.
Methacrylates, vinyl chloride, acrylamide, some fluorinated
ethylenes.
Qualitative picture
Components - recipe
Dispersing medium (mostly water)
Emulsifier and water-soluble initiator

Recipe

Grams lab scale


lbs/kg plant scale

Site of Polymerization

Monomer droplet polymer monomer mix droplet

Site of polymerization

Polymer particle swollen with monomer


Initiation occurs in aqueous phase with micelles forming
around growing polymer and dissolved monomer
Monomer droplet aqueous phase growing polymer
particle swollen with monomer
Two mechanisms for particle nucleation
Micellar particle nucleation
Homogeneous particle nucleation precipitated species
are stabilized with surfactant and absorb more monomer
and grow

Progress of Polymerization

Three intervals, separate monomer phase in intervals I and II.

Quantitative aspects

Rate of polymerization
rp = kp[M] like before

Other characteristics

Initiators
Water soluble K or NH4+ persulfate, hydrogen peroxide, 2,2azobis(2-amidinopropane)dihydrochloride
Partially soluble ones have also been used
Redox systems advantages include temps below 50C, persulfate with
ferrous, cumyl hydroperoxide or hydrogen peroxide with ferrous,
sulfite or bisulfite.
Surfactant
Anionic surfactants mostly used fatty acid soaps (sodium or
potassium stearate, laurate or palmitate), sulfates and sulfonates.
Nonionic surfactants often used to stabilize final polymer emulsion or
paint.
Other components antifreeze additives, inorganic electrolytes, buffers

Other emulsion polymerization systems

Surfactant free uses initiator that imparts surface active


properties to the polymer particles i.e. persulfate with
latexes
Inverse emulsion polymerization, water in oil emulsions.
Use nonionic surfactant to stabilize final emulsions
Mini and Micro-emulsion polymerization

Problems 4-1 to 4.3 assignment

Polymer Chemistry 1
Nazarbayev University
Principles of Polymerization
Eugene F Douglass, MS, PhD Polymer
Science - Professor
Presented by Click to enter name

Chapter 3
Topics to Cover
Nature of Radical Chain Polymerization
Structural Arrangement
Rate of Radical Chain Polymerization
Initiation
Molecular Weight
Chain Transfer
Inhibition and Retardation
Energy Concerns
Auto-acceleration
Molecular Weight Distribution
Pressure effects
Process Conditions
Specific Commercial Polymers
Living Radical Polymerization

Nature of Radical Chain Polymerization

Comparison of Chain and Step Polymerization

High Molecular Weight material is formed immediately


Radical, Anionic or Cationic reactive center adds many monomer
units very quickly in a chain reaction
Monomer concentration decreases quickly as polymer grows
Mixture consists of solvent, monomer, high polymer and growing
chains
Step very different
Any two molecular species can combine
Monomer disappears much faster as dimers, trimers etc form
Long reaction times necessary for both high conversion and high
molecular weights

Radical vs Ionic Chain Polymerizations

General Considerations

Thermodynamic
Polymerization will be impossible if reaction is not
thermodynamically feasible, G between monomer and polymer
must be negative
Kinetic feasibility will process proceed at a reasonable rate under a
proposed set of reaction conditions??
Radical, cationic, and anionic used under different conditions, as not all
processes can be used for all monomers or in proposed set of reaction
conditions,
Most monomers will react with free radical polymerization
Some monomers will not react with either cationic or anionic
parameters

Polymer Considerations

Carbon Carbon Double bond in monomers


Carbon Oxygen Bonds in Aldehydes and Ketones

Effect of Substituents

Free radical and Ionic

Electron donating vs Electron withdrawling groups affect each


type of initiating and propogating species.

Resonance Stabilization with free radicals

Structural Arrangement of Monomer units

Possible Modes of Propagation:

Carbon #1

Carbon #2

Structural Arrangement of Monomer units

Possible Modes of Propagation:

Head to Tail

Head to Head, tail to tail or random

Experimental Evidence

Head to Head:

The synthetic approach involves an appropriate choice of monomer for the particular HH
polymer. For example, HH poly(vinyl chloride) is obtained by chlorination of 1,4-poly-1,3butadiene,

Rate of Radical Chain Polymerization

Sequence of events

Initiation

Propagation

Rate of Radical Chain Polymerization

Sequence of events

Termination
Combination or disproportionation:

Addition of Cap or terminator


Resulting in dead polymer, one that no longer grows

Rate of Radical Chain Polymerization

Rate of monomer disappearance or rate of polymerization is


given by the term:

[]

= + ,

=
Steady State approximation leads to:

= = 2

Resulting in the rate of Polymerization being equal to:

1/2
[]( )
2

Initiation

Types of Initiators:
Thermal homolytic dissociation
Redox intiators
Photochemical
Ionizing Radiation Electron beam
Pure thermal
Electrolysis of monomer solutions

Thermal homolytic dissociation:


Acyl peroxides acetyl and benzoyl peroxides
Alkyl peroxides cumyl and t-butyl peroxides
Hydroperoxides t-butyl and cumyl hydroperoxies
Peresters
Acyl alkylsufonyl peroxides, dialkylperoxydicarbonates
, diperoxyketals, and ketone peroxides
Azo compounds AIBN

Thermolytic Initiators

Azo Compounds

Driving force production of highly stable


Nitrogen molecule ????
Other types:
Disulfides,

Redox Initiators
1. Peroxides and Reducing agents
Hydrogen peroxide with Fe+2
H2O2 + Fe+2 HO-1 + HO + Fe+3
Other peroxides and Fe+2
ROOR RO-1 + RO
ROOH OH-1 + RO
ROOCOR RCOO-1+ RO
Other reducing agents can also be used including Cr+2 , V+2 ,
Ti+3, Co+2, & Cu+1
You can also use amines as the reductant.

Redox Initiators
2. Inorganic reductants and inorganic oxidants

3. Organic inorganic redox pairs

4. Monomer itself, and thiosulfate or N,N-dimethylaniline

Photochemical Initiation

Photochemical or Photoinitiated polymerization

Reaction conditions UV, Visible, IR


Often uses a photosensitizer

Some compound in the system undergoes excitation by


energy absorption and subsequent decomposition into
radicals.
2. Some compound undergoes excitation and the excited
species interacts with a second compound (by either energy
transfer or redox reaction) to form radicals derived from the
latter and/or former compound(s).
UV Curable Coatings
1.

Bulk Monomer

Some monomers

M + h M*
M* R + R

Polymerization then continues as before. Conjugated double


bonds work the best.

Irradiation of Thermal and Redox initiators

Ionizing Radiation

C + C+1 A + B+1 B+1 + e-1 B


The radiolysis of olenic monomers results in the formation of cations, anions, and
free radicals as described above. It is then possible for these species to initiate
chain polymerizations. Whether a polymerization is initiated by the radicals,
cations, or anions depends on the monomer and reaction conditions. Most
radiation polymerizations are radical polymerizations, especially at higher
temperatures where ionic species are not stable and dissociate to yield radicals.
Radiolytic initiation can also be achieved using initiators, like those used in
thermally initiated and photoinitiated polymerizations, which undergo
decomposition on irradiation.

Pure Thermal Initiation

Thermal homolysis of impurities primarily


Some monomers are easier than others. And Styrene is the one monomer that
undergoes polymerization purely driven by heat.

Other methods

Electrolysis of monomer solutions


Plasma Polymerization placed in electrical discharge under
low pressure
Sonication

Initiator efficiency

Chain transfer to initiator


Side reactions of initiator species

Cage effect f (efficiency) < 1

Brackets indicate presence of solvent cage which traps the


free radicals for a short time until they defuse apart.

Termination

Disproportionation
Coupling

Molecular Weight ideally stop at desired molecular weight


Kinetic Chain length v - as the average number of monomer
molecules consumed (polymerized) per each radical, which
initiates a polymer chain. This quantity will obviously be given
by the ratio of the polymerization rate to the initiation rate
or to the termination rate, since the latter two rates are
equal.

Mode of Termination

Number average degree of polymerization Xn, average


number of monomer molecules contained in a polymer
molecule

For termination by coupling Xn = 2v


For termination by disproportionation Xn = v

Mn = M0Xn where M0 is the molecular weight of the


monomer.
Most polymer radicals appear to terminate by coupling,
except where chain transfer predominates.
Higher temperature gives more disproportionation.
Styrene, methyl acrylate and acrylonitrile mostly coupling

Methyl methacrylate both types are evident

Chain transfer
Mn + XA Mn-X + A

XA can be monomer, initiator, solvent or


other material

Purpose of chain transfer is to modify the molecular weight


by decreasing the size of the propagating chain.
Dependent on rate of reinitiation comparable to initial
propagating radical
It is a chain breaking reaction.

Molecular Weight Effects by chain transfer

Chain transfer to monomer and initiator

Monomer Chain Transfer constants

Monomer chain transfer constants are generally small for


most monomers (Table 3-4).

Cm generally low
because the reaction
involves the breaking of
the strong vinyl C-H
bond.

Note Vinyl chloride is


High!

Initiator Transfer Constants

Either monomer or initiator chain transfer constants

Agent Chain Transfer Constants

Some cases transfer to agent is likely, designed that way!

Chain transfer to polymer

Results branching of polymer chain


Sometimes crosslink, sometimes intramolecular - backbiting

Inhibition and Retardation

Inhibitors stop every radical


Retarders stop only a portion of the radicals
Use Stabilize monomers for storage, control specialty
polymerizations.

Energetic Characteristics

Activation energy and frequency factor

Particularly important for thermally initiated polymerization

Thermodynamics of Polymerization

Significance of G, H and S

Effects of Monomer structure


1. Differences in the resonance stabilization of monomer and
polymer due to differences in conjugation or hyperconjugation.
2. Steric strain differences in the monomer and polymer arising
from bond angle deformation, bond stretching, or interactions
between nonbonded atoms.
3. Differences in hydrogen bonding or dipole interactions in the
monomer and polymer.

Polymerization De-polymerization Equilibria

Ceiling Temperature
A temperature at which the propagation step becomes a reversible one.
The net rate of polymer production is zero
Floor temperature
A temperature that occurs in some cases where below this temperature
polymerization is impossible

Course of Polymerization

Auto-acceleration reaction rate increases with conversion


Diffusion controlled termination

Translational diffusion of two propagating radicals


Rearrangement of two chains which brings ends close
Chemical reaction of two radical ends.

Auto-acceleration of pMMA

Process conditions

Bulk Polymerization Monomer is used as solvent for growing polymer chains, until
you get precipitation or gel formation. Products: Polyethylene, Polystyrene, and
pMMA.

Problems highly exothermic nature of polymerization can lead to unzipping or


even charring/discoloration. Thermal control.

Broad distribution of molecular weight due to chain transfer to polymer

Run away effects

Necessary to react to low conversion and finish reaction later

Strong and elaborate stirring apparatus required


Solution polymerization Polymerization of monomer occurs in solution, solvent
effectively dissolves even completed polymer. Products: pVinyl Acetate, PAN, and
esters of Polyacrylic acids

Solvent as diluent aids in heat transfer away from exothermic reaction of


polymerization

Solvent aids in stirring, because viscosity is decreased.

Must design proper system to avoid solvent as chain transfer agent

Heterogeneous polymerization

Precipitation Polymerization begins as homogeneous polymerization (bulk or


solution) and then polymer falls out of solution, because the polymer is insoluble in the
reaction medium

Powdered or granular products often result

Initiators are soluble in reaction medium

Polymerization occurs upon absorption of monomer and initiator into growing


polymer particles.
Suspension polymerization Suspending monomer as droplets in water. The droplets
contain the reacting monomer and initiator, which are prevented from coalescing by
agitation and additives which stablize the suspension

Water acts as diluent aids in heat transfer away from exothermic reaction of
polymerization

Water aids in stirring, because viscosity is decreased, reaction is occurring inside


droplets. Each droplet is a bulk polymer system.

Must design proper system to avoid solvent as chain transfer agent


Emulsion or Dispersion Polymerization chapter 4

Specific Commercial Polymers

Polyethylene low density polyethylene is produced

Specific Commercial Polymers

Polystyrene continuous solution polymerization important


for industrial production, suspension and emulsion
polymerization is also used.

Specific Commercial Polymers

Polyvinyl chloride mostly suspension polymerization, some


bulk and emulsion polymerization also done.

Specific Commercial Polymers

Polyvinyl acetate, and polyvinylidene chloride, copolymers and


polymers derived from them are most often made with
suspension or emulsion polymerization processes

Acrylic Family

Acrylate and Methacrylate products, many of these are copolymers


with different esters of acrylic or methacrylic acid using as comonomers in the emulsion or suspension polymerization process.
pMMA made by solution, emulsion and suspension types. You want to
avoid overheating to avoid bubble formation as the bp of MMA is
100.5C
Polyacrylonitrile PAN mostly produced by solution and suspension
processes

Specific Commercial Polymers

Fluoropolymers polymers made from alkenes substituted


with one or more fluorine atoms

Polymerization of Dienes

Primarily suspension polymerization, with some emulsion


polymerization

Isoprene industrially produced


Butadiene, ABS rubber

Others brief discussion

Living Radical Polymerization

Free radical has to be stabilized somehow.

Block copolymer production

Monomers added mixed together in desired ratios


Monomers added one at a time to react.
First polymerization done to 90% conversion, then other
monomer(s) are added.
A-B, AAAA-BBBB etc
ABA
ABC
ABCB, CABAC many combinations

Functional Polymers

Usually copolymers with a small amount of functional group


added as a copolymer

Acrylic acid, Acrylonitrile, Alcohol end group

Acetylenic polymers

Reactions of acetylenes or diacetylenes to form conjugated polymers


of various kinds, even to add functionality.

Polymers are macromolecules built from smaller molecular subunits, called monomers. Synthetic polymers can be classified into two
main types according to the mechanism by which they synthetically grow from monomer to polymer: chain-growth polymers and stepgrowth polymers. In this lab, chain-growth polymerization of styrene monomer using benzoyl peroxide initiator will be performed. The
characteristics of chain-growth polymerizations are (A.,Ravve, 1995):

The repeating units are added one at a time to the chain,

Monomer concentration decreases steadily throughout the reaction,

High molecular weight polymers are formed quickly and the molecular weight of the polymers changes gradually throughout the
reaction,

Long reaction time produces high yields, but affects the molecular weight only slightly. While there are many types of specific chaingrowth polymerization mechanisms, four frequently used types are: free radical, anionic, cationic and coordination.

In our case we use free radical polymerization, which consists of three steps: Initiation, Propagation and Termination. At the
initiation stage of chain-growth free radical polymerization of styrene monomers, the initiator, I, forms free radicals species: , which
then couples with one electron of the carbon-carbon double bonds of the styrene monomer to form another radical. These bonds are
particularly susceptible to radical attack because of their relatively low stability and resonance stabilization of the resulting radical
throughout the phenyl group. In the next stage, propagation, the newly formed radical reacts with another monomer to form another
radical, resulting in a polymer that is one unit longer (Fred W, 1984). The process is then repeated to form a chain of monomers (a
polymer). The propagation step is terminated when two radicals combine together to form a neutral species, known as coupling or
combination or disproportionation, in which hydrogen transfer results in the formation of two molecules: one saturated and one
unsaturated end group (Hart H., 1999).

In this experiment free radical polymerization technique was used. In order to undergo initiation step, styrene was used with NaOH to
remove inhibitor and make it reactive, because styrene is stored with inhibitor to make it more stable for storing. Then, we placed
styrene inside a tube and flushed with nitrogen, this was done to avoid formation of explosive mixture of styrene and air. This is not
enough to make free radicals in initiation step; we need to add some benzoyl peroxide, which is used as initiator. Since, benzoyl
peroxide decomposes with hemolytic cleavage of oxygen-oxygen bond. We need to heat our sample to 80-90 degrees for 90 min. in
order to break down oxygen-oxygen bond and start initiation process. In case of low temperature, this reaction could take weeks. In
case of too high temperature, our product will be not syrupy, but solid like.
Initiation Step

Then during the reaction process we undergo propagation step, when new formed radical reacts with another monomer to form
another radical.
Propagation Step
Then this chain can be terminated by combining two radicals, known as coupling, so our polymer is growing and its chain continues.
Termination Step
Combination or Coupling

After 90 minutes of heating inside the water bath, we added toluene to dissolve the content in a tube. Actually, we might use any
non-polar solvent (like acetone), according to rule like dissolves like. Then all staff was placed inside the methanol (which is polar)
and it stops the reaction and finally solid polystyrene is precipitated.
Reaction conditions were discussed previously. Then what is important is a Pilot plant approach.
Pilot plant:
The technique seems quite similar to which we do in lab; instead amounts are much greater. What is interesting is that by pilot plant
approach they could produce super high molecular weight compounds (over MW: 320,000).

Initiation Step

2R

H
Then during the reaction process we undergo propagation step, when new formed radical reacts with another monomer to form another radical.
RCH2C
2R + CH2 CH
Propagation Step
X
X

H
H
Then this chain can be terminated by combining two radicals, known as coupling, so our polymer is growing and its chain continues.
R CH2CH n CH2C + CH2 CH
R CH2CH2 CH2C
Termination Step
n+1
Combination or Coupling

H
CH2C
X

CCH2
X

H
CH2C
X

H
CCH2
X

Initiation Step
Then during the reaction process we undergo
propagation step, when new formed radical reacts with
another monomer to form another radical.
Propagation Step
Then this chain can be terminated by combining two
radicals, known as coupling, so our polymer is growing
and its chain continues.
Termination Step
Combination or Coupling

If we want to understand experiment more deeply, we need to know the history of Polystyrene. First of Polystyrene is described as a strong plastic,
which is created from the monomer called styrene. Molecular formula is (C8H8) n and it has relatively low melting point ( 240 degree Celsius). Also,
it is one of the most used polymers in the world. According to article in Finanz Nachrichten, the worldwide market worth in 2012 accounted for
11.9 billion US dollars (Finanz Nachrichten, 2013). Moreover, it is predicted that in 2018 the data will be 19.1 billion dollars. For instance, it has
applications in production of cups, packaging peanuts, building materials and many household items.
Polystyrene has a long history of evolution behind it. In 1839, a German apothecary called Eduard Simon discovered polystyrene. Eduard Simon
isolated the substance from natural resin. However, he did not know what he had discovered. It took another German, organic chemist, Hermann
Staudinger, to realize that Simon's discovery comprised of long chains of styrene molecules, was a plastic polymer.
In 1922, Hermann Staudinger published his theories on polymers, stating that natural rubbers were made up of long repetitive chains of
monomers that gave rubber its elasticity. He went on to write that the materials manufactured by the thermal processing of styrene were similar to
rubber. They were the high polymers including polystyrene. In 1953, Hermann Staudinger won the Nobel Prize for Chemistry for his research (Bellis
M., 2015).
Thus, we understand how Polystyrene was invented and what is actual use is. Now, we will shift to the process by which it synthesized in our lab
experiment. The technique is Emulsion polymerization it refers to a unique process employed for some radical chain polymerizations. It involves the
polymerization of monomers in the form of emulsions (i.e., colloidal dispersions) (Sandler, 1998). Below is the simplified representation of Emulsion
Polymerization system.
From this (Fig. 4-1) we might clearly understand that polymer particle swollen with monomer. Then, initiation processes is held in aqueous phase
and at that time micelles forming around growing polymer and dissolved monomer. Also, there are two possibilities for particle nucleation. The first
one is Micellar particle nucleation and the second is Homogeneous particle nucleation. Where in second mechanism precipitated species are
stabilized with surfactant and absorb more monomer (Douglass E., 2015).
From the graph above (Fig. 4-2), we see three different intervals. Those intervals are different rate behaviors, which are observed during the
emulsion polymerization process. In interval I, the nucleation of the particle takes place. At this stage, the monomer convention is about 5-10%
(10171018 particles per liter are formed). Usually during the rest of the batch process, the number of particles is constant, only in case coagulation it
changes significantly.
In Interval II, the system is composed of monomer droplets and polymer particles. We might observe that monomer diffuses from the monomer
droplets through the aqueous phase. The transition occurs at about 7080% conversion. This step ends when the monomer droplets disappear.
The transition from Intervals II to III occurs at about 40% conversion for styrene. This represents that most of the monomer polymerizes during
Interval III. In this interval, the monomer concentration in the polymer particles decreases continuously (JKU, 2015).