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POLYMER HANDBOOK

FOURTH EDITION

Editors

J. BRANDRUP, E. H. IMMERGUT, and E. A. GRULKE


Associate Editors

A. ABE
D. R. BLOCH

A WILEY-INTERSCIENCE PUBLICATION

JOHNWlLEY & SONS, INC.


New York

Chichester

Weinheim

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Toronto

This book is printed on acid-free paper. @


Copyright 1999 by John Wiley & Sons, Inc. All rights reserved.
Published simultaneously in Canada.
No part of this publication may be reproduced, stored in a retrieval system
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Library of Congress Cataloging-in-Puhlication Data:
Polymer Handbook / Editors: J. Brandrup, E. H. Immergut, and
E. A. Grulke;
Associate Editors, A. Abe, D. R. Bloch. - 4th ed.
p.
cm.
"A Wiley-Interscience Publication."
Includes index.
ISBN 0-471-16628-6 (cloth : alk. paper)
1. PolymersTables. 2. PolymerizationTables. I. Brandrup, J.
II. Immergut, E. H. III. Grulke, Eric A.
QD388.P65 1999
547.7-dc21
98-37261
Printed in the United States of America.
10 9 8 7 6 5 4 3 2

Contributors
Abe, A.
Tokyo Institute of Polytechnics, Atsugi, Japan
Allegra, G.
Dipartimento di Chimica del Politecnico, Milano, Italy
Andreeva, L. N.
Institute of High Molecular Weight Compounds, Russian
Academy of Sciences, St. Petersburg, Russian Federation
Andrews, R, J.
Chemical and Materials Engineering Department, University of
Kentucky, Lexington, Kentucky, USA
Bai, F.
The Maurice Morton Institute of Polymer Science, Univeristy
of Akron, Akron, USA
Bareiss, R. E.
Editorial Office, Macromolecular Chemistry and Physics,
Mainz, FR Germany
Barrales-Rienda, J. M.
Instituto de Ciencia y Tecnologia de Polfmeros, Madrid, Spain
Bello, A.
Instituto de Ciencia y Tecnologia de Polfmeros, Madrid, Spain
Bello, P.
Instituto de Ciencia y Tecnologia de Polfmeros, Madrid, Spain
Bloch, D. R.
Lakeshore Research, Racine, Wisconsin, USA
Brandrup, J.
Wiesbaden, FR Germany
Calhoun, B. H.
The Maurice Morton Institute of Polymers Science, University
of Akron, Akron USA
Casassa, E. F.
Department of Chemistry, Carneagfe-Mellon University, Pittsburgh, Pennsylvania, USA
Cheng, S. Z. D.
The Maurice Morton Institute of Polymer Science, University
of Akron, Akron, Ohio, USA
Chiu, F.-C.
The Maurice Morton Institute of Polymer Science, University
of Akron, Akron, Ohio, USA
Cho, J.
Polymer Science and Engineering Department, Dankook
University, Seoul, South Korea
Collins, E. A.
Avon Lake, Ohio, USA
Daniels, C. A.
The Geon Company, Avon Lake, Ohio, USA
DeLassus, P. T.
The Dow Chemical Company, Freeport, Texas, USA
Dixon, K. W.
Akzo Nobel Chemicals, Inc., Dobbs Ferry, New York, USA

Elias, H.-G.
Michigan Molecular Institute, Midland, Michigan, USA
Fink, G.
Max-Planck-Institut fur Kohlenforschung, Miilheim an der
Ruhr, FR Germany
Fink, H.-P.
Fraunhofer Institut fiir angewandte Polymerforschung, TeltowSeehof, FR Germany
Fouassier, J. P.
Laboratoire de Photochimie Generate, Ecole Nationale
Superieure de Chimie, Mulhouse, France
Fu, Q.
The Maurice Morton Institute and Department of Polymer
Science, University of Akron, Akron, Ohio, USA
Furuta, I.
Japan Synthetic Rubber Company Ltd., Yokkaichi, Mie,
Japan
Ganster, J.
Fraunhofer Institute for Applied Polymer Research, TeltowSeehof, Germany
Greenley, R. Z.
Monsanto Corporation (retired), St. Louis, Missouri, USA
Grulke, E. A.
Chemical and Materials Engineering, University of Kentucky,
Lexington, Kentucky, USA
Goh, S. H.
Department of Chemistry, National University of Singapore,
Singapore
Guzman G. M.
Instituto de Ciencia y Tecnologfa de Polfmeros, Madrid,
Spain
Hill, D. J. T.
Department of Chemistry, University of Queensland, St. Lucia,
Australia
Hiltner, A.
Department of Macromolecular Science, School of Engineering
Case Western University, Cleveland, Ohio, USA
Inomata, K.
Department of Polymer Chemistry, Tokyo Institute of Technology, Ookayama, Meguro-ku, Tokyo, Japan
Iwama, M.
Japan Synthetic Rubber Company Ltd., Yokkaichi, Mie,
Japan
Jenkins, A. D.
School of Chemistry, Physics and Environmental Science,
University of Sussex, Brighton, Sussex, UK
Jenkins, J.
School of Chemistry, Physics and Environmental Science,
University of Sussex, Brighton, Sussex, UK

Johnson, M.
Chemistry/Physics Library, University of Kentucky, Lexington,
Kentucky, USA
Kamachi, M.
Department of Applied Physics and Chemistry, Fukui University of Technology, Gakuen, Fukui, Japan
Kerbow, D. L.
DuPont Fluoroproducts, Wilmington, Delaware, USA
Kimura, S.-L
Japan Synthetic Rubber Company Ltd., Yokkaichi, Mie,
Japan
Korte, S.
Zentrale Ferschung, Bayer AG, Leverkunsen, FR Germany
Krause, S.
Department of Chemistry, Rensselaer Polytechnic Institute,
Troy, New York, USA
Kurata, M.
Institute for Chemical Research, Kyoto University, Uji, Kyoto,
Japan
Lechner, M. D.
Physikalische Chemie, Universitat Osnabriick, Osnabriick, FR
Germany
Leonard, J.
Department de Chimie and CERSIM, Universite Laval,
Quebec, Canada
Li, F.
The Maurice Morton Institute of Polymer Science, University
of Akron, Akron, Ohio, USA

Muck, K.-F.
Ticona GmbH, Kelsterbach, FR Germany
Nagai, S.
Plastics Technical Association, Osaka, Japan
Nordmeier, E.
Physikalische Chemie, Universitat Osnabriick, Osnabriick
FR Germany
Ogo, Y.
Research Institute for Solvothermal Technology, Hayashi,
Takamatsu, Kagawa, Japan
Orwoll, R. A.
College of William and Mary, Williamsburg, Virginia, USA
Pauly, S.
Fachlaboratorium fur Permeationspriifung, Wiesbaden,
FR Germany
Peebles, L. H., Jr.
Chemistry Division, Naval Research Laboratory, Washington,
DC, USA
Perera, M. C. S.
Magnetic Resonance Facility, School of Science, Griffith
University, Nathan, Australia
Porzio, W.
Instituto di Chimica delle Macromolecole del C.N.R., Milano,
Italy
Pyda, M.
Department of Chemistry, University of Tennessee, Knoxville,
Tennessee, USA

Liggat, J.
Department of Pure and Applied Chemistry, University of
Strathclyde, Glasgow, Scotland

Quirk, R. P.
The Maurice Morton Institute of Polymer Science, University
of Akron, Akron, Ohio, USA

Lindemann, M.
Greenville, South Carolina, USA
Luft, G.
Institut fur Chemische Technologie, Technische Hochschule,
Darmstadt, FR Germany

Riande, E.
Instituto de Ciencia y Tecnologia de Polimeros, Madrid,
Spain

Magill, J. H.
School of Engineering, University of Pittsburgh, Pittsburgh,
Pennsylvania, USA
McKenna, T. F.
Centre Nationale de Ia Recherche Scientifique, Laboratoire de
Chimie et Procedes de Polymerisation/Departement Genie des
Procedes, Villeurbanne, France
Mehta, R. H.
Dupont Nylon, Chattanooga, Tennessee, USA
Mettle, S. V.
Dipartimento di Chimica del Politecnico, Milano, Italy
Metanomski, W. V.
Chemical Abstracts Service, Columbus, Ohio, USA
Michielsen, S.
School of Textile and Fiber Engineering, Georgia Institute of
Technology, Atlanta, Georgia, USA
Miller, R. L.
Michigan Molecular Institute, Midland, Michigan, USA
Morita, Y.
Japan Atomic Energy Research Institute, Takasaki,
Gunma-ken, Japan

Richter, W. J.
Max-Planck-Institut fur Kohlenforschung, Miilheim an der
Ruhr, FR Germany
Rothe, M.
University of UIm, UIm, FR Germany
Rule, M.
Coca Cola Company, Atlanta, Georgia, USA
Salort, J. F.
Madrid, Spain
Salom, C.
Escuela Tecnica Superior de Ingenieros Aeronauticos, Universidad Politecnica, Madrid, Spain
Sanchez, I. C.
Chemical Engineering Department, University of Texas at
Austin, Austin, Texas, USA
Santos, A. M.
Faculdade de Engenharia Quimica de Lorena - FAENQUIL,
Lorena, Sao Paulo, Brazil
Schoff, C. K.
PPG Industries, Allison Park, Pennsylvania, USA
Schuld, N.
Institut fur Physikalische Chemie, Universitat Mainz, Mainz,
FR Germany

Seferis, J. C.
Chemical Engineering Department, University of Washington,
Seattle, Washington, USA
Seguchi, T.
Japan Atomic Energy Research Institute, Takasaki, Gunma-ken,
Japan

Wagener, K. B.
Department of Chemistry and Center for Macromolecular
Science and Engineering, University of Florida, Gainesville,
Florida, USA
Whiteman, N. F.
The Dow Chemical Company, Freeport, Texas, USA

Schrader, D.
The Dow Chemical Company, Midland, Michigan, USA

Witenhafer, D. E.
Dublin, Ohio, USA

Sperati, C. A.
Chemical Engineering Department, Ohio University, Athens,
Ohio, USA

Wolf, B. A.
Institut fur Physikalische Chemie, Universitat Mainz, Mainz,
FR Germany

Steinmeier, D. G.
Physikalische Chemie, Universitat Osnabriick, Osnabruck,
FR Germany

Wu, S.
E. I. DuPont de Nemours, Central Research and Development
Department, Experimental Station, Wilmington, Delaware

Tsunashima, Y.
Institute for Chemical Research, Kyoto University, Uji, Kyoto,
Japan

Wunderlich, B.
Department of Chemistry, University of Tennessee, Knoxville,
Tennessee, USA

Tsvetkov, N. V.
Institute of High Molecular Weight Compounds, Russian
Academy of Science, St. Petersburg, Russian Federation

Wunderlich, W.
ROHM GmbH, Darmstadt, FR Germany

Tsvetkov, V. N.
Institute of High Molecular Weight Compounds, Russian
Academy of Science, St. Petersburg, Russian Federation

Yamada, B.
Department of Applied Chemistry, Faculty of Technology,
Osaka City University, Sumiyoshi, Osaka, Japan

Ueda, A.
Osaka Municipal Technical Research Institute, Morinomiya,
Joto-ku, Osaka, Japan

Zhu, L.
The Maurice Morton Institute of Polymer Science, University
of Akron, Akron, Ohio, USA

Preface
The purpose of the Polymer Handbook is to bring together
the data and constants needed in theoretical and experimental polymer research. All polymer researchers have
experienced the frustration of searching for data in the everexpanding polymer literature and know the difficulties
involved in trying to locate a particular constant that is
buried in a long journal article. The contributors to this
Handbook have taken on the arduous task of searching the
literature and compiling the data and constants that polymer
chemists, polymer physicists, and polymer engineers are
likely to need.
The 520 and odd tables in this Handbook are divided into
eight sections. The first lists the IUPAC nomenclature rules
for polymers and the International System of Units.
Although several naming conventions exist in the technical
literature, IUPAC names permit a consistent listing of all
polymers. Section II contains data and constants needed for
polymer synthesis, kinetic mechanisms, and thermodynamic studies of polymerization and depolymerization
reactions. Sections III and IV contain physical constants
of monomers, solvents, and oligomers. Section V lists the
physical constants of many important commercial polymers. Section VI and VII cover the solid state properties of
polymers and the properties of polymer solutions. Section
VIII of the Handbook lists the commonly used abbreviations or acronyms for polymers and Chemical Abstract
Registry Numbers, and gives suggestions for electronic data
searching for polymer information. This section should also
be consulted in the few cases where contributors have not
used IUPAC nomenclature.
As in the previous editions, the Polymer Handbook
concentrates on synthetic polymers, poly(saccharides) and
derivatives, and oligomers. Few data on biopolymers are
included. Spectroscopic data as well as data needed by
engineers and designers, such as mechanical and rheological data, are minimized, since many excellent compilations
exist elsewhere. Only fundamental constants and parameters that refer to the polymer molecule, that describe the
solid state of polymer molecules, or that describe polymer
solutions, were compiled. Constants that depend on
processing conditions or on sample history were not
emphasized, as they can be found in existing plastics
handbooks and encyclopedias.

A critical evaluation of the values published in the


literature was not attempted, since such a task would have
required an inordinate amount of time and a sizable staff.
Therefore, the users of this Handbook should consult the
original literature for details when in doubt about the
validity of any data. (The authors of the individual tables
were nevertheless requested to eliminate obviously erroneous data from otherwise complete compilations.)
The Fourth Edition revisions have focused on data
generated in the ten years since the publication of the Third
Edition. Therefore, a completely revised Polymer Handbook has been prepared. We have added new tables and
incorporated a large amount of new data into existing
tables. As a result, the Fourth Edition contains approximately twenty-five percent more data, and the number of
pages has increased from about 1850 in the Third Edition to
about 2250.
We hope that this new edition will be as useful to the
polymer research community as the three earlier editions
and that many of the Polymer Handbook's previous users
will also obtain the Fourth Edition for their laboratory and
library.
The publisher plans a CD-ROM for the Polymer
Handbook in the near future. We would be grateful if our
contributors and users send us any new data they
accumulate in the course of their research, and any errors,
misprints, omissions and other flaws. We will pass on such
data to the publisher, for the polymer database, and for
future editions of this Handbook.
We would like to thank all of the contributors to the
Polymer Handbook for their help and continued patience.
The staff at John Wiley, especially Carla Fjerstad, Shirley
Thomas, and Jacqueline Kroschwitz, have provided excellent help and support in getting all the work done. We hope
that the outstanding efforts of all these people will find due
appreciation among the users of this Handbook.
July, 1998

J. Brandrup
E. H. Immergut
E. A. Grulke
A. Abe
D. R. Bloch

Contents

Contributors .............................................................................................................................

Preface ....................................................................................................................................

ix

I.

Nomenclature Rules Units

Nomenclature ...............................................................................................................................................

I/1

A. Introduction ........................................................................................................................

I/1

B. IUPAC Recommendations ..................................................................................................


1.
Source-based Nomenclature ..................................................................................
1.1
Homopolymers ........................................................................................
1.2
Copolymers .............................................................................................
1.3
Nonlinear Macromolecules and Macromolecular Assemblies ................
2.
Structure-based Nomenclature ...............................................................................
2.1
Regular Single-strand Organic Polymers ...............................................
2.2
Regular Double-strand Organic Polymers ..............................................
2.3
Regular Single-strand Inorganic and Coordination Polymers .................
2.4
Regular Quasi-single-strand Coordination Polymers ..............................
2.5
Irregular Single-strand Organic Polymers ...............................................

I/1
I/2
I/2
I/2
I/3
I/3
I/3
I/6
I/6
I/7
I/7

C. Use of Common and Semisystematic Names .....................................................................

I/8

D. Chemical Abstracts (CA) Index Names ...............................................................................

I/8

E. Polymer Class Names ........................................................................................................

I/11

F. References .........................................................................................................................

I/12

Units .............................................................................................................................................................

I/13

A. Introduction ........................................................................................................................

I/13

B. International Units ..............................................................................................................

I/13

C. SI-prefixes ..........................................................................................................................

I/14

D. Conversion Factors ............................................................................................................

I/14

E. Conversion Table for SI vs. English-american Units ...........................................................

I/17

II.

Polymerization and Depolymerization

Decomposition Rates of Organic Free Radical Initiators ............................................................................

II/1

A. Introduction ........................................................................................................................

II/1

B. Tables of Decomposition Rates of Organic Free Radical Initiators .....................................


Table 1. Azonitriles ...............................................................................................................
Table 2. Miscellaneous Azo-derivatives ................................................................................

II/2
II/2
II/9

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xi

xii

Contents
Table 3.
Table 4.
Table 5.
Table 6.
Table 7.

Alkyl Peroxides .......................................................................................................


Acyl Peroxides ........................................................................................................
Hydroperoxides and Ketone Peroxides ..................................................................
Peresters and Peroxycarbonates ............................................................................
Miscellaneous Initiators ...........................................................................................

II/23
II/29
II/43
II/48
II/67

C. Notes ..................................................................................................................................

II/69

D. References .........................................................................................................................

II/70

Propagation and Termination Constants in Free Radical Polymerization ..................................................

II/77

A. Introduction ........................................................................................................................

II/77

B. Tables of
Table 1.
Table 2.
Table 3.
Table 4.
Table 5.
Table 6.
Table 7.
Table 8.
Table 9.
Table 10.
Table 11.
Table 12.
Table 13.

Propagation and Termination Constants .............................................................


Dienes .....................................................................................................................
Olefins .....................................................................................................................
Acrylic Derivatives ...................................................................................................
Methacrylic Derivatives ...........................................................................................
Itaconic Derivatives .................................................................................................
Fumaric Derivatives ................................................................................................
Vinyl Halides ...........................................................................................................
Vinyl Esters .............................................................................................................
Vinyl Ethers .............................................................................................................
Styrene Derivatives .................................................................................................
Vinyl Heteroaromatics .............................................................................................
Aldehydes ...............................................................................................................
Others .....................................................................................................................

II/79
II/79
II/79
II/80
II/82
II/85
II/87
II/87
II/87
II/88
II/88
II/90
II/90
II/90

C. References .........................................................................................................................

II/91

Transfer Constants to Monomers, Polymers, Catalysts and Initiators, Solvents and Additives, and
Sulfur Compounds in Free Radical Polymerization ...........................................................................

II/97

A. Introduction ........................................................................................................................

II/97

B. Tables of Transfer Constants .............................................................................................


Table 1. Transfer Constants to Monomers ...........................................................................
Table 2. Transfer Constants to Polymers .............................................................................
Table 3. Transfer Constants to Catalysts and Initiators ........................................................
Table 4. Transfer Constants to Solvents and Additives ........................................................
Table 5. Transfer Constants to Sulfur Compounds ...............................................................

II/98
II/98
II/103
II/106
II/110
II/150

C. Remarks .............................................................................................................................

II/157

D. References .........................................................................................................................

II/159

Photopolymerization Reactions ...................................................................................................................

II/169

A. Introduction ........................................................................................................................

II/169

B. Tables ................................................................................................................................
Table 1. Rate Constants of Cleavage, Electron Transfer and Monomer Quenching in
Radical Photoinitiators ............................................................................................
Annex to Table 1. Photoinitiator Compound Chemistries ......................................

II/170

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II/170
II/173

Contents
Table 2. Bimolecular Rate Constants for the Reaction of Phosphonyl Radicals with
Various Monomers in Cyclohexane at Room Temperature ....................................
Table 3. Bimolecular Rate Constants for the Reaction of Various Radicals with
Various Olefinic Monomers at Room Temperature .................................................
Table 4. Bimolecular Rate Constants for the Reaction of Ph2P = O and Ph2P = S with
Various Monomers ..................................................................................................
Table 5. Electron Transfer Reaction of Radicals with Diphenyliodonium Salts ....................
Table 6. Electron Transfer Rate Constants (ke) between Photosensitizers and
Cationic Photoinitiators and Quenching Rate Constants (kq) for Cyclohexene
Oxide in Methanol (M) and Acetonitrile (AN) ..........................................................
Table 7. Excitation Transfer Rate Constants (kT) for Thioxanthones and
Photoinitiators .........................................................................................................
Annex to Table 7. Compound Chemistries ............................................................
Table 8. Triplet State Lifetimes (T) of the Sensitizer (TXI) in Different Media, and
Rate Constant (kT) of the Interaction between TXI and TPMK ...............................
Table 9. Some Values of the Triplet State Energy Levels of Photoinitiators and
Monomers ...............................................................................................................
Table 10. Values of 0T, T, and kba in Solution ........................................................................
Table 11. Rate Constant of Interaction of Ketones and Light Stabilizers in Solution ..............
Annex to Table 11 ...................................................................................................

xiii
II/176
II/176
II/176
II/176

II/177
II/178
II/178
II/179
II/179
II/179
II/179
II/179

C. References .........................................................................................................................

II/180

Free Radical Copolymerization Reactivity Ratios .......................................................................................

II/181

A. Introduction ........................................................................................................................

II/181

B. Tables ................................................................................................................................
Table 1. Copolymer Reactivity Ratios ...................................................................................
Acenaphthalene to Fumarate, bis(3-chloro-2-butyl) ................................................
Fumarate, di-(2-chloroethyl) to N-N-divinylaniline ...................................................
N-vinylimidazole to Styrene, p-2-(2-hydroxypropyl)- ...............................................
Styrene, p-4-methoxyphenyl ketone to Vinylbenzoate, p-, sodium .........................
Vinylbenzoic acid, p- to Xanthate, S-methacryloyl O-ethyl .....................................
Table 2. Listing of Quick Basic (Microsoft) Program for Calculating Reactivity Ratios .........

II/182
II/182
II/182
II/212
II/241
II/268
II/285
II/288

C. References .........................................................................................................................

II/290

Q and e Values for Free Radical Copolymerizations of Vinyl Monomers and Telogens ...........................

II/309

A. Introduction ........................................................................................................................

II/309

B. Q and e
Table 1.
Table 2.
Table 3.
Table 4.

Values for Free Radical Copolymerizations ..........................................................


Monomers ...............................................................................................................
Telogens .................................................................................................................
Monomers Arranged by Q Values ...........................................................................
Monomers Arranged by e Values ...........................................................................

II/310
II/310
II/314
II/314
II/317

C. References .........................................................................................................................

II/319

Patterns of Reactivity (U,V) Parameters for the Prediction of Monomer Reactivity Ratios and
Transfer Constants in Radical Polymerization ...................................................................................

II/321

A. Introduction ........................................................................................................................

II/321

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xiv

Contents
B. Example .............................................................................................................................

II/322

C. Transfer Constants .............................................................................................................

II/322

D. Tables of Parameters .........................................................................................................


Table 1. Monomers ...............................................................................................................
Table 2. Transfer Agent ........................................................................................................

II/323
II/323
II/326

E. References .........................................................................................................................

II/327

Copolymerization Parameters of Metallocene-catalyzed Copolymerizations ............................................

II/329

A. Introduction ........................................................................................................................

II/329

B. A Brief Theoretical Outline of Copolymerization Reactions .................................................


1.
First-order Markov Model ........................................................................................
2.
Second-order Markov Model ...................................................................................

II/329
II/330
II/330

C. Calculation of the Copolymerization Parameters ................................................................


1.
First-order Markov Model ........................................................................................
1.1.
Copolymerization Parameters Deduced from the Mayo-lewis
Equation ..................................................................................................
1.2.
Determination of Copolymerization Parameters from the
Sequence Distribution (Triad Distribution) ..............................................
2.
Second-order Markov Model ...................................................................................
3.
Example ..................................................................................................................

II/331
II/331

D. Table of Copolymerization Parameters ...............................................................................

II/333

E. List of Catalysts/Cocatalysts Used .....................................................................................

II/336

F. References .........................................................................................................................

II/336

Rates of Polymerization and Depolymerization, Average Molecular Weights, and Molecular


Weight Distribution of Polymers .........................................................................................................

II/339

A. Introduction ........................................................................................................................

II/339

B. Reference Tables for the Calculation of Rates of Polymerization, Average Molecular


Weights, and Molecular Weight Distributions of Polymers for Various Types of
Polymerization ....................................................................................................................
Table 1. Addition Polymerization with Termination ...............................................................
Table 2. Addition Polymerization - "Living" Polymers with Partial Deactivation ....................
Table 3. Linear Condensation Polymerization without Ring Formation ................................
Table 4. Equilibrium Polymerization ......................................................................................
Table 5. Nonlinear Polymerization Systems .........................................................................
Table 6. Degradation of Polymers - May Be Accompanied by Crosslinking .........................
Table 7. Influence of Reactor Conditions and Design on the Molecular Weight
Distribution ..............................................................................................................

II/340
II/341
II/344
II/346
II/347
II/348
II/350

C. Some Distribution Functions and Their Properties ..............................................................


1.
Normal Distribution Function (Gaussian Distribution) .............................................
2.
Logarithmic Normal Distribution Function ...............................................................
3.
Generalized Exponential Distribution ......................................................................
4.
Poisson Distribution ................................................................................................

II/352
II/353
II/353
II/354
II/354

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II/331
II/331
II/332
II/332

II/352

Contents

xv

D. Molecular Weight Distribution in Condensation Polymers: the Stockmayer


Distribution Function ...........................................................................................................

II/354

E. References .........................................................................................................................

II/356

Heats and Entropies of Polymerization, Ceiling Temperatures, Equilibrium Monomer


Concentrations, and Polymerizability of Heterocyclic Compounds ...................................................

II/363

A. Heats of Polymerization ......................................................................................................


Table 1. Monomers Giving Polymers Containing Carbon Atoms Only in the Main
Chain .......................................................................................................................
1.1
With Acyclic Carbons Only in the Main Chain ........................................

II/365

1.1.1 Dienes ..............................................................................................

II/365

1.1.2 Monomers Giving Polymers with or without Aliphatic Side


Chains That Contain Only C, H ........................................................

II/365

1.1.3 Monomers Giving Polymers with Aliphatic Side Chains That


Contain Heteroatoms .......................................................................

II/368

1.1.4 Monomers Giving Polymers with Aromatic Side Chains That


Contain Only C, H ............................................................................

II/371

1.1.5 Monomers Giving Polymers with Aromatic Side Chains and


That Contain Heteroatoms ...............................................................
1.2
With Aromatic or Cyclic Carbons in the Main Chain ...............................
Table 2. Monomers Giving Polymers Containing Heteroatoms in the Main Chain ...............
2.1
Monomers Giving Polymers Containing O in the Main Chain,
Bonded to Carbon Only ..........................................................................

II/365
II/365

II/371
II/372
II/373
II/373

2.1.1 Ethers and Acetals ...........................................................................

II/373

2.1.2 Cyclic Esters .....................................................................................


2.2
Monomers Giving Polymers Containing O in the Main Chain,
Bonded to Other Heteroatoms (S, Si, P) ................................................
2.3
Monomers Giving Polymers Containing S in the Main Chain,
Bonded in the Chain to Carbon Only ......................................................
2.4
Monomers Giving Polymers Containing N in the Main Chain,
Bonded in the Chain to Carbon Only ......................................................
2.5
Monomers Giving Polymers Containing N in the Main Chain,
Bonded to Other Heteroatoms (P) ..........................................................
2.6
Other Monomers Giving Polymers Not Listed Above .............................
Table 3. Copolymers .............................................................................................................

II/376
II/377
II/378
II/378
II/379
II/379
II/380

B. Entropies of Polymerization ................................................................................................


Table 4. Monomers Giving Polymers Containing Main Chain Carbon Only .........................
4.1
Main Chain Acyclic Carbon Only ............................................................

II/381
II/382
II/382

4.1.1 Dienes ..............................................................................................

II/382

4.1.2 Monomers Giving Polymers without or with Aliphatic Side


Chains That Contain Only C, H ........................................................

II/382

4.1.3 Monomers Giving Polymers with Aliphatic Side Chains That


Contain Heteroatoms .......................................................................

II/384

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Contents
4.1.4 Monomers Giving Polymers with Aromatic Side Chains That
Contain Only C, H ............................................................................

II/385

4.1.5 Monomers Giving Polymers with Aromatic Side Chains That


Contain Heteroatoms .......................................................................

II/385

4.1.6 Other Monomers Giving Polymers Not Listed Above ......................


4.2
With Aromatic or Cyclic Carbons in the Main Chain ...............................
Table 5. Monomers Giving Polymers Containing Heteroatoms in the Main Chain ...............
5.1
Monomers Giving Polymers Containing O in the Main Chain,
Bonded to Carbon Only ..........................................................................

II/386
II/386
II/387

5.1.1 Ethers and Acetals ...........................................................................

II/387

5.1.2 Cyclic Esters .....................................................................................


5.2
Monomers Giving Polymers Containing O in the Main Chain,
Bonded to Other Heteroatoms (S, Si, P) ................................................
5.3
Monomers Giving Polymers Containing N in the Main Chain,
Bonded in the Chain to Carbon Only ......................................................
5.4
Other Monomers Giving Polymers Not Listed Above .............................
Table 6. Copolymers .............................................................................................................

II/390

C. Ceiling Temperatures and Equilibrium Monomer Concentrations .......................................


1.
Equilibria Involving Pure Liquid Monomers .............................................................
Table 7. Monomers Giving Polymers Containing Main Chain Acyclic
Carbon Only ............................................................................................
Table 8. Monomers Giving Polymers Containing Heteroatoms in the Main
Chain ......................................................................................................
8.1

II/391
II/391
II/392
II/392
II/393
II/394
II/394
II/395

Monomers Giving Polymers Containing O in the Main Chain,


Bonded to Carbon Only ....................................................................

II/395

Monomers Giving Polymers Containing O in the Main Chain,


Bonded to Other Heteroatoms (S, P, Si) .........................................

II/396

Monomers Giving Polymers Containing S in the Main Chain,


Bonded in the Chain to Carbon Only ...............................................

II/396

Monomers Giving Polymers Containing N in the Main Chain,


Bonded in the Chain to Carbon Only ...............................................

II/397

8.5 Other Monomers Giving Polymers Not Listed Above ......................


Equilibria Involving Gaseous Monomers .................................................................
Equilibria Involving Monomers in Solution ..............................................................
Table 9. Monomers Giving Polymers Containing Main Chain Carbon Only .........

II/397
II/397
II/398
II/398

8.2
8.3
8.4

2.
3.

II/387

9.1

Monomers Giving Polymers Containing Main Chain Acyclic


Carbon Only .....................................................................................

II/398

9.2

Monomers Giving Polymers Containing Main Chain Cyclic


Carbon ..............................................................................................
Table 10. Monomers Giving Polymers Containing Heteroatoms in the Main
Chain ......................................................................................................

II/399

10.1 Monomers Giving Polymers Containing O in the Main Chain,


Bonded to Carbon Only ....................................................................

II/399

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II/399

Contents

xvii

10.2 Monomers Giving Polymers Containing O in the Main Chain,


Bonded to Other Heteroatoms (Si, P) ..............................................

II/400

10.3 Monomers Giving Polymers Containing S in the Main Chain,


Bonded in the Chain to Carbon Only ...............................................

II/400

10.4 Monomers Giving Polymers Containing N in the Main Chain,


Bonded in the Chain to Carbon Only ...............................................
Table 11. Copolymers .............................................................................................

II/400
II/401

11.1 1:1 Copolymers ................................................................................

II/401

11.2 General Copolymers ........................................................................

II/401

D. Polymerizability of 5-, 6-, and 7-membered Heterocyclic Ring Compounds ........................


Table 12. 5-membered Ring Compounds ...............................................................................
Table 13. 6-membered Ring Compounds ...............................................................................
Table 14. 7-membered Ring Compounds ...............................................................................
Table 15. Comparison of Polymerizability (+ or -)of Unsubstituted 5-, 6- and
7-membered Ring Compounds ...............................................................................

II/401
II/402
II/403
II/404

E. Notes ..................................................................................................................................

II/406

F. References .........................................................................................................................

II/407

Activation Energies of Propagation and Termination in Free Radical Polymerization ...............................

II/415

A. Introduction ........................................................................................................................

II/415

B. Tables ................................................................................................................................
Table 1. Dienes .....................................................................................................................
Table 2. Olefins .....................................................................................................................
Table 3. Acrylic Derivatives ...................................................................................................
Table 4. Methacrylic Derivatives ...........................................................................................
Table 5. Vinyl Halogens ........................................................................................................
Table 6. Vinyl Ethers and Vinyl Esters ..................................................................................
Table 7. Styrene and Derivatives ..........................................................................................
Table 8. Vinyl Heteroaromatics .............................................................................................
Table 9. Miscellaneous Compounds .....................................................................................

II/416
II/416
II/416
II/417
II/418
II/420
II/421
II/421
II/422
II/423

C. References .........................................................................................................................

II/424

Activation Volumes of Polymerization Reactions ........................................................................................

II/429

A. Introduction ........................................................................................................................

II/429

II/405

B. Activation Volumes (sm /mol) of Some Polymerization Reactions ......................................

II/432

C. Activation Volumes of Initiator Decomposition ....................................................................

II/435

D. Activation Volumes of Chain Propagation ...........................................................................

II/435

E. Activation Volumes of Chain Termination ...........................................................................

II/436

F. Activation Volumes of Chain Transfer Reactions ................................................................

II/436

G. Influence of Pressure on Copolymerization ........................................................................


Table 1. Copolymerization Parameters .................................................................................
Table 2. Reactivity Ratios of Terpolymerization ....................................................................
Table 3. Activation Volumes .................................................................................................
Table 4. Q, e Values .............................................................................................................

II/437
II/437
II/438
II/439
II/440

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Contents
H. References .........................................................................................................................

II/440

Activation Enthalpies and Entropies of Stereocontrol in Free Radical Polymerizations .............................

II/445

A. Introduction ........................................................................................................................

II/445

B. Tables ................................................................................................................................
Table 1. Ratios of Some i-ADS for Different Mechanisms ....................................................
Table 2. Ratios of Rate Constants for Markov First Order Mechanisms ...............................
Table 3. H++s/i - H++i/s and S++s/i - S++i/s of Free Radical Polymerizations in
Different Solvents ....................................................................................................
Table 4. Activation Enthalpy Differences (H++A - H++B) Calculated from Various
Literature Data ........................................................................................................
Table 5. Activation Entropy Differences (S++A - S++B) Calculated from Various
Literature Data ........................................................................................................
Table 6. Calculated Compensation Temperatures T0 and Compensation Enthalpies
H++0 for Various Monomers and Modes of Addition, Assuming Markov
First Order Trials .....................................................................................................

II/446
II/446
II/446

C. References .........................................................................................................................

II/450

Products of Thermal Degradation of Polymers ...........................................................................................

II/451

A. Introduction ........................................................................................................................

II/451

B. Tables ................................................................................................................................
Table 1. Main-chain Acyclic Carbon Polymers .....................................................................
Table 2. Main-chain Carbocyclic Polymers ...........................................................................
Table 3. Main-chain Heteroatom Polymers ...........................................................................
Table 4. Main-chain Heterocyclic Polymers ..........................................................................
Table 5. Cellulose and Its Derivatives ...................................................................................

II/451
II/451
II/464
II/465
II/473
II/475

C. References .........................................................................................................................

II/475

Radiation Chemical Yields: G Values ..........................................................................................................

II/481

A. Introduction ........................................................................................................................

II/481

B. Tables of G Values .............................................................................................................


Table 1. Homopolymers ........................................................................................................
1.1
Polydienes ..............................................................................................
1.2
Polyolefins ..............................................................................................
1.3
Polyacrylates ..........................................................................................
1.4
Poly(methacrylates) ................................................................................
1.5
Poly(styrenes) .........................................................................................
1.6
Poly(vinyls) .............................................................................................

II/481
II/482
II/482
II/482
II/483
II/484
II/485
II/486

1.6.1 Acrylamides and Nitriles ...................................................................

II/486

1.6.2 Vinyl Monomers ................................................................................


Miscellaneous Polymers .........................................................................

II/486
II/487

1.7.1 Cellulose and Derivatives .................................................................

II/487

1.7.2 Poly(siloxanes) .................................................................................

II/487

1.7.3 Poly(amino Acids) ............................................................................

II/487

1.7.4 Polyesters .........................................................................................

II/488

1.7

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II/447
II/448
II/449

II/449

Contents

III.

xix

1.7.5 Polysulfones .....................................................................................

II/488

1.7.6 Polyketones ......................................................................................

II/488

1.7.7 Fluoropolymers .................................................................................

II/488

1.7.8 Others ...............................................................................................


Table 2. Copolymers .............................................................................................................
2.1
Copolymers with Ethylene ......................................................................
2.2
Copolymers with Methyl Methacrylate ....................................................
2.3
Copolymers with Styrene ........................................................................
2.4
Copolymers with Sulfur Dioxide ..............................................................
2.5
Other Copolymers ...................................................................................
Table 3. Polymers Blends .....................................................................................................
Table 4. Composites .............................................................................................................

II/489
II/490
II/490
II/490
II/491
II/491
II/492
II/493
II/493

C. References .........................................................................................................................

II/493

Physical Properties of Monomers and Solvents

Physical Properties of Monomers ................................................................................................................

III/1

A. Introduction ........................................................................................................................

III/1

B. Tables of
Table 1.
Table 2.
Table 3.
Table 4.

Table 5.

Table 6.

Table 7.
Table 8.
Table 9.

Table 10.

Table 11.

Physical Properties .............................................................................................


Acetylenes ..............................................................................................................
Acid Dichlorides ......................................................................................................
Acroleins .................................................................................................................
Acrylamides/Methacrylamides ................................................................................
4.1
Acrylamides ............................................................................................
4.2
Methacrylamide ......................................................................................
Acrylates/Methacrylates ..........................................................................................
5.1
Acrylate, Acids/Esters .............................................................................
5.2
Methacrylate, Acids/Esters .....................................................................
Alcohols ..................................................................................................................
6.1
Alkanediols .............................................................................................
6.2
Ether Diols ..............................................................................................
Allyl Functional ........................................................................................................
Amines, Difunctional ...............................................................................................
Anhydrides ..............................................................................................................
9.1
Monoanhydrides .....................................................................................
9.2
Dianhydrides ...........................................................................................
Butadienes ..............................................................................................................
10.1
1,2-butadienes ........................................................................................
10.2
1,3-butadienes ........................................................................................
Butenes ...................................................................................................................
11.1
1-butenes ................................................................................................
11.2
2-butenes ................................................................................................

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III/4
III/4
III/4
III/4
III/4
III/4
III/6
III/8
III/8
III/12
III/16
III/16
III/18
III/18
III/20
III/20
III/20
III/24
III/24
III/24
III/24
III/26
III/26
III/26

xx

Contents
Table 12. Epoxides .................................................................................................................
12.1
Monoepoxides ........................................................................................
12.2
Diepoxides ..............................................................................................
Table 13. Ethylene Halides .....................................................................................................
Table 14. Fumaric, Acids/Esters .............................................................................................
Table 15. lsocyanates .............................................................................................................
Table 16. Lactams ..................................................................................................................
Table 17. Lactones .................................................................................................................
Table 18. Maleate, Acids/Esters .............................................................................................
Table 19. Propenes .................................................................................................................
Table 20. Styrenes ..................................................................................................................
Table 21. Vinyl Functional .......................................................................................................
21.1
Aryl ..........................................................................................................
21.2
Esters ......................................................................................................
21.3
Ethers .....................................................................................................
21.4
N-substituted ...........................................................................................
21.5
Sulfonates ...............................................................................................

III/26
III/26
III/28
III/28
III/30
III/30
III/32
III/32
III/32
III/32
III/34
III/36
III/36
III/36
III/38
III/38
III/40

Isorefractive and Isopycnic Solvent Pairs ....................................................................................................

III/43

A. Introduction ........................................................................................................................

III/43

B. Table of Isorefractive and Isopycnic Solvent Pairs ..............................................................

III/43

Refractive Indices of Common Solvents .....................................................................................................

III/55

A. Introduction ........................................................................................................................

III/55

B. Table of Refractive Indices of Common Solvents ...............................................................

III/55

Physical Constants of the Most Common Solvents for Polymers ...............................................................

III/59

IV.

Physical Data of Oligomers

Physical Data of Oligomers .........................................................................................................................

IV/1

A. Introduction ........................................................................................................................

IV/2

B. Oligomers Containing Main Chain Acyclic Carbon Only .....................................................


Table 1. Oligo(olefins) ...........................................................................................................
1.1.
Oligo(methylenes) and Oligo(ethylenes) ................................................
1.2.
Oligo(perfluoromethylenes) and Oligo(perfluoroethylenes) ....................
1.3.
Oligo(isobutenes) ....................................................................................
1.4.
Oligo(1-alkenylenes) ...............................................................................
References ..............................................................................................................
Table 2. Oligo(dienes) ...........................................................................................................
2.1.
Oligomers of 1,3-butadiene ....................................................................
2.2.
Oligomers of lsoprene .............................................................................
2.3.
Oligomers of 1,3-butadiene Derivatives ..................................................
2.4.
1,4-oligo(alkadienes) ..............................................................................
2.5.
Oligomers of Cyclopentadiene and 1,3-cyclohexadiene .........................

IV/3
IV/3
IV/3
IV/6
IV/8
IV/9
IV/9
IV/14
IV/14
IV/15
IV/16
IV/16
IV/17

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xxi

2.6.
Oligomers of Allene ................................................................................
References ..............................................................................................................
Table 3. Oligo(acetylenes) ....................................................................................................
3.1.
Linear Oligomers of Acetylene ................................................................
3.2.
Polyenyne Oligomers ..............................................................................
3.3.
Oligomeric --diynes ............................................................................
3.4.
Oligo(alkynes) .........................................................................................
3.5.
Cyclic Oligo(alkynes) ..............................................................................
3.6.
Pericyclynes ............................................................................................
References ..............................................................................................................
Table 4. Oligomers with Aliphatic Side Chains Which in Addition Contain
Heteroatoms ...........................................................................................................
4.1.
Oligomeric Acrylic Derivatives ................................................................
4.2.
Oligomeric Methacrylic Derivatives .........................................................
4.3.
Oligomers of -alkyl Substituted Vinyl Derivatives .................................
4.4.
Oligo(vinyl) Derivatives ...........................................................................
References ..............................................................................................................
Table 5. Oligo(styrenes) ........................................................................................................
References ..............................................................................................................

IV/17
IV/18
IV/19
IV/19
IV/20
IV/20
IV/20
IV/20
IV/21
IV/21

C. Oligomers Contaning Heteroatoms in the Main Chain ........................................................


Table 6. Oligomers Containing O in the Main Chain .............................................................
6.1.
Oligo(ethers) and Oligo(acetals) .............................................................

IV/33
IV/33
IV/33

6.2.

References ..................................................................................................
Oligo(carbonates) ...................................................................................

IV/43
IV/47

6.3.

References ..................................................................................................
Oligo(esters) ...........................................................................................

IV/47
IV/48

6.4.

References ..................................................................................................
Oligo(urethanes) .....................................................................................

IV/56
IV/58

References ..................................................................................................
Table 7. Oligo(sulfides) and Oligo(selenides) .......................................................................
7.1.
Cyclic Oligo(thiomethylenes) and Oligo(Selenomethylenes) ..................
7.2.
Cyclic Oligo(thioalkylenes) ......................................................................
7.3.
Substituted Cyclic(thioethylenes) ............................................................
7.4.
Cyclic Co-oligomers of Formaldehyde and Thioformaldehyde ...............
7.5.
Cyclic Oligo(ether Sulfides) ....................................................................
7.6.
Thiacyclophanes .....................................................................................
References ..............................................................................................................
Table 8. Oligomers Containing N in the Main Chain .............................................................
8.1.
Oligo(amides) .........................................................................................

IV/61
IV/62
IV/62
IV/62
IV/62
IV/62
IV/63
IV/63
IV/63
IV/64
IV/64

References ..................................................................................................
Oligo(peptides) .......................................................................................

IV/70
IV/72

References ..................................................................................................

IV/84

8.2.

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IV/22
IV/22
IV/24
IV/26
IV/27
IV/28
IV/30
IV/32

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Contents
8.3.

Oligo(imines) ...........................................................................................

IV/88

8.4.

References ..................................................................................................
Oligo(ureas) ............................................................................................

IV/89
IV/89

References ..................................................................................................

IV/90

D. Carbon Chain Oligomers Containing Main Chain Cyclic Units ............................................


Table 9. Oligo(cyclopentylenes) ............................................................................................
Table 10. Oligo(spiranes) ........................................................................................................
Table 11. Oligo(xylylenes) ......................................................................................................
11.1.
Linear Oligo(xylenes) ..............................................................................
11.2.
Cyclic Oligo(xylylenes) ............................................................................
Table 12. Oligo(stilbenes) .......................................................................................................
Table 13. Oligo(benzyls) .........................................................................................................
Table 14. Oigo(2,5-dimethyl-benzyls) .....................................................................................
Table 15. Oligo(2,3,5,6-tetramethyl-benzyls) ..........................................................................
Table 16. Oligo(p-phenylene Oxides) .....................................................................................
Table 17. Oligo(p-phenylene Sulfides) ....................................................................................
Table 18. Oligo(p-phenoxyphenylmethanes) ..........................................................................
Table 19. Oligo(diphenylmethanes) ........................................................................................
References ..............................................................................................................
Table 20. Phenol-formaldehyde and Related Oligomers ........................................................
20.1.
Linear Phenol-formaldehyde Oligomers .................................................
20.2.
Oligomeric Phenol Alcohols ....................................................................
20.3.
Cyclic Phenol-formaldehyde Oligomers ..................................................
20.4.
Branched Phenol-formaldehyde Oligomers ............................................
20.5.
Hydroquinone Oligomers ........................................................................
References ..............................................................................................................
Table 21. Oligo(phenylenes) ...................................................................................................
21.1.
o-oligo(phenylenes) ................................................................................
21.2.
m-oligo(phenylenes) ...............................................................................
21.3.
p-oligo(phenylenes) ................................................................................
21.4.
Oligo(p-quinones) ...................................................................................
References ..............................................................................................................

IV/90
IV/90
IV/90
IV/90
IV/90
IV/90
IV/91
IV/91
IV/91
IV/91
IV/91
IV/91
IV/91
IV/91
IV/91
IV/92
IV/92
IV/93
IV/94
IV/94
IV/95
IV/95
IV/96
IV/96
IV/96
IV/97
IV/98
IV/98

E. Oligomers Containing Heterocyclic Rings in the Main Chain ..............................................


Table 22. Heterocyclic Oligomers ...........................................................................................
22.1
Oligo(furan) Derivatives ..........................................................................
22.2.
Oligo(thiophene) Derivatives ..................................................................
22.3.
Oligo(pyrrole) Derivatives .......................................................................
22.4.
Oligo(pyridine) Derivatives ......................................................................
22.5.
Cyclic Oligo(heterocyclics) ......................................................................
References ..............................................................................................................
Table 23. Oligo(saccharides) ..................................................................................................
23.1.
Oligomeric Pentoses ...............................................................................

IV/99
IV/99
IV/99
IV/100
IV/100
IV/100
IV/101
IV/101
IV/102
IV/102

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xxiii

23.2.
Oligomeric Hexoses ................................................................................ IV/102
23.3.
Oligomeric Amino Sugars ....................................................................... IV/103
References .............................................................................................................. IV/104

V.

Physical Constants of Some Important Polymers

Physical Constants of Rubbery Polymers ...................................................................................................

V/1

A. Introduction ........................................................................................................................

V/1

B. Tables ................................................................................................................................
Table 1. 1,4-cis(96-98%)Poly(butadiene) .............................................................................
Table 2. Poly(butadiene-co-acrylonitrile) ..............................................................................
Table 3. Poly(butadiene-co-styrene) .....................................................................................
Table 4. Poly(chloroprene)(CR Neoprene) ...........................................................................
Table 5. Poly(isobutene)-co-isoprene) Butyl Rubber (IIR) ....................................................
Table 6. Polyisoprene, Natural Rubber .................................................................................
Table 7. Ethylene-propylene-diene-terpolymer (EPDM) .......................................................

V/1
V/1
V/2
V/3
V/3
V/4
V/5
V/6

C. References .........................................................................................................................

V/6

Physical Constants of Poly(ethylene) ..........................................................................................................

V/9

A. Crystallographic Data and Crystallographic Modifications ..................................................

V/9

B. Molecular Parameters and Solution Properties ...................................................................

V/9

C. Crystallinity, Crystal Size and Crystallization Kinetics .........................................................

V/10

D. Equilibrium Thermodynamic Properties ..............................................................................

V/11

E. Other General Physical Properties .....................................................................................

V/12

F. Effect of Chain Branching (Short) on Physical Properties ...................................................

V/15

G. Properties of a Series of Selected Poly(ethylene) Samples ................................................

V/16

H. Properties of Typical Poly(ethylenes) .................................................................................

V/17

I.

References .........................................................................................................................

V/17

Physical Constants of Poly(propylene) ........................................................................................................

V/21

A. Crystallographic Data and Modifications of Isotactic Polypropylenes ..................................

V/21

B. Crystallographic Data and Modifications of Syndiotactic Polypropylenes ............................

V/21

C. Dimensions of Poly(propylene) Molecules ..........................................................................

V/22

D. Crystallinity and Crystallization Kinetics ..............................................................................

V/22

E. Equilibrium Thermodynamic Properties ..............................................................................

V/23

F. Other General Properties ...................................................................................................

V/24

G. Properties of Typical Mainly Isotactic Poly(propylenes) ......................................................

V/26

H. Properties of Some Commercial Poly(propylene) Grades ...................................................

V/26

I.

Mechanical Properties of Poly(propylene) Homopolymers ..................................................

V/27

J. Mechanical Properties of Poly(propylene) Random Copolymers ........................................

V/28

K. Mechanical Properties of Poly(propylene) Impact Copolymers ...........................................

V/28

L. References .........................................................................................................................

V/28

Physical Constants of Fluoropolymers ........................................................................................................

V/31

A. Introduction ........................................................................................................................

V/31

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Contents
B. Physical Constants of Poly(tetrafluoroethylene) .................................................................
Notes .......................................................................................................................................
Infrared Absorption Spectrum of Poly(tetrafluoroethylene) .....................................................
References ..............................................................................................................................

V/31
V/37
V/38
V/39

C. Physical Constants of Melt Processible Fluorocarbon Polymers PFA and FEP ..................
Notes .......................................................................................................................................
References ..............................................................................................................................

V/41
V/44
V/45

D. Physical Constants of Modified Poly(ethylene-co-tetrafluoroethylene) ................................


Notes .......................................................................................................................................
References ..............................................................................................................................

V/45
V/48
V/48

E. Physical Constants of Poly(vinylidene Fluoride) .................................................................


Notes .......................................................................................................................................
References ..............................................................................................................................

V/48
V/51
V/52

F. Physical Constants of Amorphous Fluoropolymers .............................................................


Notes .......................................................................................................................................
References ..............................................................................................................................

V/52
V/54
V/54

G. Physical Constants of Poly(chlorotrifluoroethylene) ............................................................


Notes .......................................................................................................................................
References ..............................................................................................................................

V/55
V/57
V/58

Physical Constants of Poly(acrylonitrile) .....................................................................................................

V/59

A. Tables of
Table 1.
Table 2.
Table 3.
Table 4.
Table 5.
Table 6.
Table 7.
Table 8.
Table 9.

Physical Constants .............................................................................................


Crystallinity/Crystallization Behavior .......................................................................
Electric and Electronic Properties ...........................................................................
Fiber Properties ......................................................................................................
Further Properties of Acrylic Fibers ........................................................................
Optical Properties ...................................................................................................
Polymerization: Kinetic and Thermodynamic Data .................................................
Solubility/Solution Properties ..................................................................................
Special Solid State Properties ................................................................................
Thermal and Thermodynamic Data ........................................................................

V/59
V/59
V/60
V/61
V/61
V/61
V/62
V/62
V/63
V/64

B. References .........................................................................................................................

V/64

Physical Constants of Poly(vinyl Chloride) ..................................................................................................

V/67

Physical Constants of Poly(vinyl Acetate) ...................................................................................................

V/77

Physical Constants of Poly(methyl Methacrylate) .......................................................................................

V/87

Physical Constants of Poly(styrene) ............................................................................................................

V/91

Physical Constants of Poly(oxymethylene) .................................................................................................

V/97

Physical Constants of Poly(oxyethylene-oxyterephthaloyl), (Poly(ethylene Terephthalate)) .....................

V/113

Physical Constants of Poly(oxytetramethylene-oxyterephthaloyl) and Copolymers with


Tetramethylene Oxide Thermoplastic Elastomers .............................................................................

V/119

Physical Constants of Various Polyamides: Poly[imino(1-oxohexamethylene)], (Polyamide 6)


Poly(iminoadipoyl-iminohexamethylene), (Polyamide 66), Poly(iminohexamethyleneiminosebacoyl), (Polyamide 610), Poly[imino(1-oxododecamethylene)], Poly(amide 12) ................

V/121

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Contents

xxv

Physical Constants of Cellulose ..................................................................................................................

V/135

A. Introduction ........................................................................................................................

V/135

B. Solid State Properties .........................................................................................................


Table 1. Unit Cell Dimensions ...............................................................................................
Table 2. Density ....................................................................................................................
Table 3. Average Ordered Fraction of Cotton and Linters Measured by Various
Techniques .............................................................................................................
Table 4. Average Ordered Fraction Measured by Various Techniques ................................
Table 5. Degree of Crystallinity .............................................................................................
Table 6. Crystallite Sizes ......................................................................................................
Table 7. X-ray Orientation of Cellulose Fibers ......................................................................
Table 8. Heat Capacity .........................................................................................................
Table 9. Thermal Expansion Coefficient ...............................................................................
Table 10. Other Thermal Properties .......................................................................................
Table 11. Refractive Index and Birefringence .........................................................................
Table 12. Resistivity ................................................................................................................
Table 13. Dielectric Constant and Loss Factor at 1 kHz .........................................................
Table 14. Other Electrical Properties ......................................................................................
Table 15. Crystal Elastic Modulus E1 in Chain Direction .........................................................
Table 16. Fiber Strength, Elongation and Modulus .................................................................

V/136
V/136
V/136

C. Solution Properties .............................................................................................................


Table 17. Typical Non-aqueous Cellulose Solvents ...............................................................
Table 18. Other Solvents ........................................................................................................
Table 19. Viscosity - Molecular Weight Relationships ............................................................
Table 20. Second Virial Coefficients .......................................................................................
Table 21. Sedimentation and Diffusion Coefficients ...............................................................
Table 22. Partial Specific Volumes, 2 ....................................................................................
Table 23. Geometrical Chain Characteristics .........................................................................
Table 24. Polymer-solvent Interaction Parameters .................................................................

V/147
V/147
V/148
V/148
V/150
V/150
V/151
V/151
V/152

D. References .........................................................................................................................

V/152

Physical and Mechanical Properties of Some Important Polymers ............................................................

V/159

A. Introduction ........................................................................................................................

V/159

B. Narrative Descriptions ........................................................................................................


1.
Multipurpose Polymers ...........................................................................................
2.
Polyolefins and Barrier Polymers ............................................................................
3.
Styrenics and Engineering Thermoplastics .............................................................
4.
Elastomers ..............................................................................................................

V/159
V/159
V/160
V/160
V/161

C. Properties of Commercial Polymers ...................................................................................


Table 1. Multipurpose Thermoplastics ..................................................................................
Table 2. Polyolefins and Barrier Polymers ............................................................................
Table 3. Styrenics and Engineering Thermoplastics .............................................................
Table 4. Elastomers ..............................................................................................................

V/162
V/162
V/164
V/166
V/168

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xxvi
VI.

Contents
Solid State Properties

Crystallographic Data and Melting Points for Various Polymers ................................................................

VI/1

A. Introduction ........................................................................................................................
1.
Nomenclature ..........................................................................................................
2.
Examples of Polymer Names ..................................................................................
2.1.
Polymer Names Based on Source ..........................................................
2.2.
Polymer Names Based on Structure ......................................................
References for Introduction .....................................................................................

VI/1
VI/1
VI/2
VI/2
VI/3
VI/5

B. Crystallographic Data for Various Polymers .......................................................................


Table 1. Poly(olefins) ............................................................................................................
Table 2. Poly(vinyls) and Poly(vinylidenes) ..........................................................................
Table 3. Poly(aromatics) and Poly(imides) ...........................................................................
Table 4. Poly(dienes) and Poly(diynes) ................................................................................
Table 5. Poly(peptides) .........................................................................................................
Table 6. Poly(amides) ...........................................................................................................
Table 7. Poly(esters) .............................................................................................................
Table 8. Poly(urethanes) and Poly(ureas) ............................................................................
Table 9. Poly(ethers) .............................................................................................................
Table 10. Poly(oxides) ............................................................................................................
Table 11. Poly(sulfides) and Poly(sulfones) ............................................................................
Table 12. Poly(saccharides) ...................................................................................................
Table 13. Other Polymers .......................................................................................................

VI/5
VI/6
VI/13
VI/15
VI/22
VI/26
VI/33
VI/40
VI/49
VI/51
VI/52
VI/57
VI/59
VI/64

C. Melting Points of Polymers .................................................................................................


Cellulose, see Poly (1,4--D-glucose) to Poly(4,4'-methylenediphenylene
isophthalamide) .......................................................................................................
Poly(4,4'-methylenediphenylene octadecamethylenediurea) to Poly(p-xylylene
undecanediamide) ..................................................................................................

VI/71
VI/71
VI/94

D. Appendix: Formula Index to the Tables .............................................................................. VI/113


0 to 4 ....................................................................................................................................... VI/114
5 to 30 ..................................................................................................................................... VI/133
E. References ......................................................................................................................... VI/159
1 to 839 ................................................................................................................................... VI/159
840 to 1946 ............................................................................................................................. VI/174
Glass Transition Temperatures of Polymers ............................................................................................... VI/193
A. Introduction ........................................................................................................................ VI/194
1.
Example of a Property Change at Tg ...................................................................... VI/194
2.
Tg: a "Non-Equilibrium" Transition ........................................................................... VI/195
B. Tg Measurement Methods .................................................................................................. VI/195
1.
Data Interpretation .................................................................................................. VI/195
2.
Oscillating Load Methods ........................................................................................ VI/196
C. Other Factors Affecting Tg .................................................................................................. VI/196
1.
Structure ................................................................................................................. VI/196

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2.
3.
4.
5.
6.

Contents

xxvii

Crystallinity/Crosslinking .........................................................................................
Diluents ...................................................................................................................
Molecular Weight ....................................................................................................
Thermal History .......................................................................................................
Pressure ..................................................................................................................

VI/196
VI/197
VI/197
VI/197
VI/197

D. Estimation Methods for the Glass Transition Temperature ................................................. VI/197


E. Classification, Nomenclature, and Abbreviations ................................................................ VI/197
1.
Naming Conventions ............................................................................................... VI/198
2.
Abbreviations .......................................................................................................... VI/198
F. Tables of Glass Transition Temperatures of Polymers ....................................................... VI/198
Table 1. Main-chain Acyclic Carbon Polymers ..................................................................... VI/198
1.1
Poly(acrylics) and Poly(methacrylics) ..................................................... VI/198
1.1.1 Poly(acrylic acid) and Poly(acrylic Acid Esters) ............................... VI/198
1.1.2 Poly(acrylamides) ............................................................................. VI/201
1.1.3 Poly(methacrylic Acid) and Poly(methacrylic Acid Esters) .............. VI/201
1.1.4 Poly(methacrylamides) ..................................................................... VI/205
1.1.5 Other - and -substituted Poly(acrylics) and
Poly(methacrylics) ............................................................................
1.2
Poly(alkenes) ..........................................................................................
1.3
Poly(dienes) ............................................................................................
1.4
Poly(styrenes) .........................................................................................
1.5
Poly(vinyl Alcohol) and Poly(vinyl Ketones) ............................................
1.6
PoIy(vinyl Esters) ....................................................................................
1.7
Poly(vinyl Ethers) and Poly(vinyl Thioethers) .........................................
1.8
Poly(vinyl Halides) and Poly(vinyl Nitriles) ..............................................
1.9
Others .....................................................................................................
Table 2. Main-chain Carbocyclic Polymers ...........................................................................
2.1
Poly(phenylenes) ....................................................................................
2.2
Others .....................................................................................................
Table 3. Main-chain Acyclic Heteroatom Polymers ..............................................................
3.1
Main-chain COC Polymers .............................................................

VI/205
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VI/207
VI/209
VI/212
VI/213
VI/214
VI/215
VI/216
VI/218
VI/218
VI/218
VI/219
VI/219

3.1.1 Poly(anhydrides) .............................................................................. VI/219


3.1.2 Poly(carbonates) .............................................................................. VI/219
3.1.3 Poly(esters) ...................................................................................... VI/221
3.1.4 Poly(ether Ketones) ......................................................................... VI/226
3.1.5 Poly(oxides) ...................................................................................... VI/226
3.2

3.1.6 Poly(urethanes) ................................................................................ VI/229


Main-chain O-heteroatom Polymers ....................................................... VI/231
3.2.1 Nitroso-polymers .............................................................................. VI/231
3.2.2 PoIy(siloxanes) ................................................................................. VI/231
3.2.3 Poly(sulfonates) ................................................................................ VI/233

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Contents
3.3

Main-chain C(S)nC- and CSN Polymers ................................... VI/233


3.3.1 Poly(sulfides) .................................................................................... VI/233
3.3.2 Poly(sulfones) and Poly(sulfonamides) ........................................... VI/234

3.4

3.3.3 Poly(thioesters) ................................................................................ VI/235


Main-chain CNC Polymers ............................................................... VI/235
3.4.1 Poly(amides) .................................................................................... VI/235
3.4.2 Poly(anilines) .................................................................................... VI/241
3.4.3 Poly(imides) ...................................................................................... VI/241
3.4.4 Poly(imines) ...................................................................................... VI/241

3.4.5 Poly(ureas) .......................................................................................


3.5
Poly(phosphazenes) ...............................................................................
3.6
Poly(silanes) and Poly(silazanes) ...........................................................
Table 4. Main-chain Heterocyclic Polymers ..........................................................................
4.1
Carbohydrates ........................................................................................
4.2
Liquid Crystals ........................................................................................
4.3
Natural Polymers ....................................................................................
4.4
Poly(acetals) ...........................................................................................
4.5
Poly(anhydrides) .....................................................................................
4.6
Poly(benzimidazoles) ..............................................................................
4.7
Poly(benzothiazinophenothiazines) ........................................................
4.8
Poly(benzothiazoles) ..............................................................................
4.9
Poly(benzoxazlnes) ................................................................................
4.10
Poly(benzoxazoles) ................................................................................
4.11
Poly(carboranes) ....................................................................................
4.12
Poly(dibenzofurans) ................................................................................
4.13
Poly(dioxoisoindolines) ...........................................................................
4.14
Poly(fluoresceins) ...................................................................................
4.15
Poly(furan Tetracarboxylic Acid Diimides) ..............................................
4.16
Poly(oxabicyclononanes) ........................................................................
4.17
Poly(oxadiazoles) ...................................................................................
4.18
Poly(oxindoles) .......................................................................................
4.19
Poly(oxoisoindolines) ..............................................................................
4.20
Poly(phthalazines) ..................................................................................
4.21
Poly(phthalides) ......................................................................................
4.22
Poly(piperazines) ....................................................................................
4.23
Poly(piperidines) .....................................................................................
4.24
Poly(pyrazinoquinoxalines) .....................................................................
4.25
Poly(pyrazoles) .......................................................................................
4.26
Poly(pyridazines) ....................................................................................
4.27
Poly(pyridines) ........................................................................................
4.28
Poly(pyromellitimides) .............................................................................
4.29
Poly(pyrrolidines) ....................................................................................

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Contents
4.30
Poly(quinones) ........................................................................................
4.31
Poly(quinoxalines) ..................................................................................
4.32
Poly(triazines) .........................................................................................
4.33
Poly(triazoles) .........................................................................................
Table 5. Copolymers .............................................................................................................

xxix
VI/250
VI/250
VI/252
VI/252
VI/252

G. References ......................................................................................................................... VI/253


1 to 953 ................................................................................................................................... VI/253
954 to 1560 ............................................................................................................................. VI/268
Rates of Crystallization of Polymers ............................................................................................................ VI/279
A. Introduction ........................................................................................................................
1.
Background .............................................................................................................
1.1
General Remarks ....................................................................................
1.2
Background .............................................................................................
1.3
Morphological Outline/Growth Features .................................................
2.
General Principles and Techniques Involved in Crystallization Rate Studies .........
2.1
Kinetics of Bulk Transformations ............................................................
2.2
Thermodynamic Crystallization Models ..................................................
2.3
Growth Kinetics of Lamellar Structures: Crystals and Spherulites .........
3.
Other Significant Aspects of Crystallization ............................................................
3.1
Nonisothermal Crystallization .................................................................
3.2
Crystallization of Blends .........................................................................
3.3
Solvent and Pressure-induced Crystallization ........................................
3.4
Crystallization of Mesophases ................................................................
3.5
Flow Induced Crystallization ...................................................................
3.6
Epitaxial Crystallization ...........................................................................
3.7
Orientational Crystallization ....................................................................
3.8
Crystallization of Copolymers .................................................................
3.9
Computer Simulations ............................................................................

VI/280
VI/280
VI/280
VI/280
VI/281
VI/282
VI/282
VI/284
VI/284
VI/286
VI/286
VI/287
VI/288
VI/288
VI/289
VI/289
VI/289
VI/290
VI/290

B. Tables of Rates of Crystallization of Various Polymers ....................................................... VI/291


1.
Rates of Crystal Growth .......................................................................................... VI/291
Table 1. Poly(alkenes), Poly(dienes), Poly(vinyls) ................................................ VI/291
1.1

2.

Homopolymer Melts ......................................................................... VI/291

1.2 Solutions ...........................................................................................


Table 2. Poly(oxides) ............................................................................................
Rates of Radial Spherulitic Growth .........................................................................
Table 3. Poly(dienes), Poly(alkenes), Poly(vinyls) ................................................
3.1

VI/296
VI/300
VI/304
VI/304

Homopolymer Melts ......................................................................... VI/304

3.2 Blends ............................................................................................... VI/312


Table 4. Poly(oxides) ............................................................................................ VI/315
4.1

Homopolymer Melts ......................................................................... VI/315

4.2

Complexes ....................................................................................... VI/318

4.3

Blends ............................................................................................... VI/319

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xxx

Contents
Table 5. Poly(carbonates) ..................................................................................... VI/326
Table 6. Poly(esters) ............................................................................................. VI/327
6.1

Homopolymer Melts ......................................................................... VI/327

6.2

Blends ............................................................................................... VI/329

6.3 Copolymers ...................................................................................... VI/331


Table 7. Poly(amides) ........................................................................................... VI/331
Table 8. Poly(siloxanes) ....................................................................................... VI/334
8.1

Homopolymer Melts ......................................................................... VI/334

8.2 Copolymers ...................................................................................... VI/334


Table 9. Others ..................................................................................................... VI/336
9.1
3.

Homopolymers Melts ....................................................................... VI/336

9.2 lonomers ........................................................................................... VI/340


Rates of Bulk Crystallization (Avrami Constants) ................................................... VI/341
Table 10. Poly(dienes), Poly(alkenes), Poly(vinyls) ................................................ VI/341
10.1 Melts and Solutions .......................................................................... VI/341
10.2 Blends and Copolymers ................................................................... VI/353
Table 11. Poly(oxides) ............................................................................................ VI/365
11.1 Homopolymer Melts ......................................................................... VI/365
11.2 Blends ............................................................................................... VI/371
Table 12. Poly(carbonates) ..................................................................................... VI/372
Table 13. Poly(esters) ............................................................................................. VI/373
13.1 Homopolymer melts ......................................................................... VI/373
13.2 Blends and Copolymers ................................................................... VI/377
Table 14. Poly(amides) ........................................................................................... VI/379
14.1 Blends of Poly(amides) .................................................................... VI/382
Table 15. Poly(urethanes) ...................................................................................... VI/383
Table 16.
Table 17.
Table 18.
Table 19.

15.1 Blends of Poly(urethanes) ................................................................


Poly(siloxanes) .......................................................................................
Poly(phosphazenes) ...............................................................................
Others .....................................................................................................
Composites .............................................................................................

VI/383
VI/384
VI/384
VI/385
VI/389

19.1 Composites of Blends ...................................................................... VI/390


C. References ......................................................................................................................... VI/391
Isomorphous Polymers Pairs ....................................................................................................................... VI/399
A. Introduction ........................................................................................................................ VI/399
B. Techniques ......................................................................................................................... VI/400
C. Tables of lsomorphous Pairs of Monomer Units .................................................................
Table 1. lsomorphous Units Within the Same Macromolecules (Copolymers) .....................
1.1
lsomorphous Units with Different Chemical Constitution ........................
1.2
lsomorphous Units with Different Configurations and/or with Headto-head, Head-to-tail Constitutional Disorder ..........................................

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VI/401
VI/401
VI/401
VI/405

Contents

xxxi

Table 2. Isomorphism of Macromolecules ............................................................................ VI/405


D. References ......................................................................................................................... VI/406
Miscible Polymers ........................................................................................................................................ VI/409
A. Definition of Miscibility ........................................................................................................ VI/409
B. Data Collection ................................................................................................................... VI/410
C. Arrangement of the Tables ................................................................................................. VI/410
D. Tables ................................................................................................................................
Table 1. Chemically Dissimilar Polymer Pairs Miscible in the Amorphous State at
Room Temperature .................................................................................................
Table 2. Polymer Pairs Containing One Monomer in Common, Miscible in the
Amorphous State at Room Temperature ................................................................
Table 3. Chemically Dissimilar Polymer Triads (and Tetrads) Miscible in the
Amorphous State at Room Temperature ................................................................
Table 4. Polymer Pairs Miscible in the Amorphous State at Room Temperature;
Molecular Weight Dependence Investigated ..........................................................
Table 5. Polymer Pairs That Appear to Have High Temperature Miscibility Although
Immiscible at or Below Room Temperature ............................................................
Table 6. Polymer Pairs Miscible at Room Temperature That Appear to Have a Lower
Critical Solution Temperature (LCST) Above Room Temperature .........................
Table 7. Polymer Pairs That Appear to Have Both a Lower Critical Solution
Temperature and a Upper Critical Solution Temperature .......................................
Table 8. Polymer Pairs That Cocrystallize ............................................................................

VI/411
VI/411
VI/444
VI/448
VI/450
VI/452
VI/454
VI/458
VI/459

E. References ......................................................................................................................... VI/461


Heat Capacities of High Polymers ............................................................................................................... VI/483
A. Introduction ........................................................................................................................ VI/483
B. Experimental Curves .......................................................................................................... VI/485
C. Data Tables for Solids and Liquids .....................................................................................
Table 1. cis-1,4-Poly(butadiene) (PBDc) ..............................................................................
Table 2. trans-1,4-Poly(butadiene) (PBDt) ............................................................................
Table 3. cis-1,4-Poly(2-methylbutadiene) (PMBD) ...............................................................
Table 4. Poly(ethylene) (PE) .................................................................................................
Table 5. Poly(propylene) (PP) ...............................................................................................
Table 6. PoIy(1-butene) (PB) ................................................................................................
Table 7. PoIy(1-pentene) (PPE) ............................................................................................
Table 8. PoIy(1-hexene) (PHE) .............................................................................................
Table 9. Poly(isobutene) (PIB) ..............................................................................................
Table 10. Poly(4-methyl-1-pentene) (P4MPE) ........................................................................
Table 11. Poly(tetrafluoroethylene) (PTFE) ............................................................................
Table 12. Poly(vinyl Fluoride) (PVF) .......................................................................................
Table 13. Poly(vinylidene Fluoride) (PVF2) ............................................................................
Table 14. Poly(trifluoroethylene) (P3FE) .................................................................................
Table 15. Poly(vinyl Chloride) (PVC) ......................................................................................

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VI/486
VI/486
VI/487
VI/488
VI/488
VI/489
VI/490
VI/490
VI/491
VI/492
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VI/493
VI/494
VI/494
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VI/496

xxxii

Contents
Table 16.
Table 17.
Table 18.
Table 19.
Table 20.
Table 21.
Table 22.
Table 23.
Table 24.
Table 25.
Table 26.
Table 27.
Table 28.
Table 29.
Table 30.
Table 31.
Table 32.
Table 33.
Table 34.
Table 35.
Table 36.
Table 37.
Table 38.
Table 39.
Table 40.
Table 41.
Table 42.
Table 43.
Table 44.
Table 45.
Table 46.
Table 47.
Table 48.
Table 49.
Table 50.

Poly(vinylidene Chloride) (PVC2) ...........................................................................


Poly(chlorotrifluoroethylene) (PC3FE) ....................................................................
Poly(vinyl Alcohol) (PVA) ........................................................................................
Poly(vinyl Acetate) (PVAc) ......................................................................................
Poly(styrene) (PS) ...................................................................................................
Poly(-methylstyrene) (PMS) ..................................................................................
Poly(vinyl Benzoate) (PVBZ) ..................................................................................
Poly(methyl Acrylate) (PMA) ...................................................................................
Poly(ethyl Acrylate) (PEA) ......................................................................................
Poly(n-butyl Acrylate) (PnBA) .................................................................................
Poly(iso-butyl Acrylate) (PIBA) ................................................................................
Poly(methacrylic Acid) (PMAA) ...............................................................................
Poly(methyl Methacrylate) (PMMA) ........................................................................
Poly(ethyl Methacrylate) (PEMA) ............................................................................
Poly(n-butyl Methacrylate) (PnBMA) .......................................................................
Poly(iso-butyl Methacrylate) (PIBMA) .....................................................................
Poly(hexyl Methacrylate) (PHMA) ...........................................................................
Poly(acrylonitrile) (PAN) ..........................................................................................
Poly(methacrylamide) (PMAM) ...............................................................................
Poly(oxy-1-oxoethylene) (PCL) ...............................................................................
Poly(oxy-1-oxohexamethylene) (PCL) ....................................................................
Poly(oxyethyleneoxyterephthaloyl) (PET) ...............................................................
Poly(imino-(1-oxohexamethylene)) (Nylon 6) .........................................................
Poly(iminoadipoyliminohexamethylene) (Nylon 66) ................................................
Poly(iminoadipoyliminododecamethylene) (Nylon 612) ..........................................
Poly(oxymethylene) (POM) .....................................................................................
Poly(oxyethylene) ...................................................................................................
Poly(oxytrimethylene) (PO3M) ................................................................................
Poly(oxytetramethylene) (PO4M) ............................................................................
Poly(oxypropylene) (POPr) .....................................................................................
Poly(oxy-1,4-phenylene) (POPh) ............................................................................
Poly(oxy-2,6-dimethyl-1,4-phenylene) (PPO) .........................................................
Poly(oxy-2,6-diphenyl-1,4-phenylene) (POPPO) ....................................................
Poly(oxycarbonyloxy-1,4-phenylene-isopropylidene- 1,4-phenylene) (PC) ............
Trigonal Selenium (SeT) .........................................................................................

VI/496
VI/497
VI/498
VI/498
VI/499
VI/500
VI/500
VI/501
VI/502
VI/502
VI/503
VI/504
VI/504
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VI/508
VI/509
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VI/510
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VI/512
VI/513
VI/514
VI/514
VI/515
VI/515
VI/516
VI/517
VI/517
VI/518
VI/519

D. References ......................................................................................................................... VI/519


Surface and Interfacial Tensions of Polymers, Oligomers, Plasticizers, and Organic Pigments ............... VI/521
A. Introduction ........................................................................................................................
1.
Definition .................................................................................................................
2.
Temperature Dependence ......................................................................................
3.
Macleod's Relation ..................................................................................................
4.
Molecular Weight Dependence ...............................................................................
5.
Effects of Glass and Crystal-melt Transitions .........................................................
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VI/521
VI/521
VI/522
VI/522
VI/522
VI/522

Contents
6.
7.

xxxiii

Effect of Surface Chemical Constitution ................................................................. VI/523


Dispersion (Nonpolar) and Polar Components ....................................................... VI/523

B. Tables ................................................................................................................................ VI/523


Table 1. Surface Chemical Constitution and Surface Tension ............................. VI/524
1.1

Hydrocarbon Surfaces ..................................................................... VI/524

1.2

Fluorocarbon Surfaces ..................................................................... VI/524

1.3

Chlorocarbon Surfaces .................................................................... VI/524

1.4 Silicane Surfaces .............................................................................. VI/524


Table 2. Surface Tension, Polarity, and Macleod's Exponent for
Amorphous Surfaces .............................................................................. VI/524
2.1

Hydrocarbon Polymers ..................................................................... VI/524

2.2

Styrene Polymers ............................................................................. VI/525

2.3

Halogenated Hydrocarbon Polymers ............................................... VI/525

2.4

Vinyl Polymers - Esters .................................................................... VI/526

2.5

Vinyl Polymers - Others ................................................................... VI/526

2.6

Acrylic Polymers - Nonfluorinated .................................................... VI/526

2.7

Acrylic Polymers - Fluorinated ......................................................... VI/527

2.8

Methacrylic Polymers - Nonfluorinated ............................................ VI/527

2.9

Methacrylic Polymers - Fluorinated ................................................. VI/527

2.10 Methacrylic Hydrogels ...................................................................... VI/527


2.11 Poly(ethers) ...................................................................................... VI/528
2.12 Poly(ether) Copolymers ................................................................... VI/529
2.13 Poly(esters) ...................................................................................... VI/529
2.14 Poly(carbonates) .............................................................................. VI/530
2.15 Poly(sulfones) ................................................................................... VI/530
2.16 Phenoxy Resins ............................................................................... VI/530
2.17 Epoxy Resins ................................................................................... VI/530
2.18 Poly(amides) .................................................................................... VI/530
2.19 Poly(imides) ...................................................................................... VI/531
2.20 Poly(imines) ...................................................................................... VI/531
2.21 Poly(urethanes) ................................................................................ VI/531
2.22 Poly(siloxanes) ................................................................................. VI/531
2.23 Organosilanes - Hydrolyzed and Condensed Films ........................ VI/532
2.24 Cellulosics ........................................................................................ VI/533
2.25 Poly(peptides) .................................................................................. VI/533
2.26 Miscellaneous ................................................................................... VI/533
Table 3. lnterfacial Tension for Amorphous Interfaces ......................................... VI/535
3.1

Hydrocarbon Polymers vs. Others ................................................... VI/535

3.2

Styrene Polymers vs. Others ........................................................... VI/537

3.3

Vinyl Polymers vs. Others ................................................................ VI/537

3.4

Acrylic Polymers vs. Others ............................................................. VI/538

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xxxiv

Contents
3.5

Methacrylic Polymers vs. Others ..................................................... VI/538

3.6

Poly(ethers) vs. Others .................................................................... VI/539

3.7

Poly(esters) vs. Others ..................................................................... VI/539

3.8

Poly(amides) vs. Others ................................................................... VI/539

3.9

Epoxy Resins vs. Others .................................................................. VI/539

3.10 Poly(Siloxanes) vs. Others ............................................................... VI/539


3.11 Miscellaneous ................................................................................... VI/540
C. References ......................................................................................................................... VI/540
Permeability and Diffusion Data .................................................................................................................. VI/543
A. Introduction ........................................................................................................................ VI/543
B. Conversion Factors for Various Units of the Permeability Coefficient ................................. VI/545
C. Tables ................................................................................................................................
Table 1. Permeability Coefficients, Diffusion Coefficients, and Solubility Coefficients
of Polymers .............................................................................................................
1.1
Poly(alkanes) ..........................................................................................
1.2
Poly(styrenes) .........................................................................................
1.3
Poly(methacrylates) ................................................................................
1.4
Poly(nitriles) ............................................................................................
1.5
Poly(vinyls) .............................................................................................
1.6
Fluorine Containing Polymers .................................................................
1.7
Poly(dienes) ............................................................................................
1.8
Poly(xylylenes) ........................................................................................
1.9
Poly(oxides) ............................................................................................
1.10
Poly(esters), Poly(carbonates) ...............................................................
1.11
PoIy(siloxanes) .......................................................................................
1.12
Poly(amides), Poly(imides) .....................................................................
1.13
Poly(urethanes) ......................................................................................
1.14
Poly(sulfones) .........................................................................................
1.15
Poly(aryl Ether Ether Ketone) .................................................................
1.16
Cellulose and Derivatives .......................................................................
Table 2. Permeability Coefficients of Six Different Fluorinated Hydrocarbons through
Polymers .................................................................................................................
Table 3. Permeability Coefficients of Various Organic Compounds through Lowdensity Poly(ethylene) .............................................................................................
Table 4. Permeability Coefficients and Diffusion Coefficients of an Equimolar Mixture
of Various Compounds (1.25 M Each) through High-density Poly(ethylene) ..........
Table 5. Permeability Coefficients of Various Organic Compounds through Highdensity Poly(ethylene) and Poly(propylene) ...........................................................
Table 6. Permeability Coefficients of Various Organic Compounds through Irradiation
Crosslinked Low-density Poly(ethylene) .................................................................
Table 7. Permeability Coefficients of Cases through Irradiation Crosslinked Lowdensity Poly(ethylene) .............................................................................................

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VI/545
VI/545
VI/545
VI/547
VI/548
VI/549
VI/549
VI/552
VI/553
VI/555
VI/555
VI/555
VI/558
VI/559
VI/560
VI/560
VI/561
VI/561
VI/562
VI/562
VI/564
VI/564
VI/564
VI/565

Contents

xxxv

Table 8. Permeability Coefficients of Chemically Crosslinked Poly(oxypropylene) ..............


Table 9. Permeability Coefficients of Gases through Various Elastomers ............................
Table 10. Permeability Coefficients of Gases through Various Commercial Elastomers
at 35C. ...................................................................................................................
Table 11. Permeability, Diffusion and Solubility Coefficients of Alkanes through
Santoprene (Blend of Ethylene-propylene Copolymer and lsotactic
Poly(propylene)) ......................................................................................................
Table 12. Permeability, Diffusion and Solubility Coefficients of Esters through
Poly(epichlorohydrin) (ECO) ...................................................................................

VI/565
VI/566
VI/566

VI/566
VI/567

D. References ......................................................................................................................... VI/568


Refractive Indices of Polymers .................................................................................................................... VI/571
A. Introduction ........................................................................................................................ VI/571
B. Molar Refraction ................................................................................................................. VI/571
C. Refractive Indices of Heterogeneous Polymers .................................................................. VI/572
D. Optical Anisotropy .............................................................................................................. VI/572
E. Applications ........................................................................................................................
Table 1. Intrinsic Optical Properties of Selected Polymers ...................................................
Table 2. Average Refractive Indices of Polymers (in Order of Increasing n) ........................
Table 3. Average Refractive Indices of Polymers (in Alphabetical Order) ............................

VI/573
VI/573
VI/574
VI/578

F. References ......................................................................................................................... VI/582


Radiation Resistance of Plastics and Elastomers ....................................................................................... VI/583
A. Introduction ........................................................................................................................
1.
General Comments .................................................................................................
2.
Criterion for Radiation Resistance ..........................................................................
3.
Factors of Influence and Their Consideration in Tables .........................................
3.1
Type of Polymer and Formulation ...........................................................
3.2
Type of Radiation and Dosimetry ...........................................................
3.3
Dose Rate and the Atmosphere .............................................................
3.4
Temperature ...........................................................................................
3.5
Other Stresses ........................................................................................

VI/583
VI/583
VI/583
VI/583
VI/583
VI/584
VI/584
VI/584
VI/584

B. List of Symbols Used .......................................................................................................... VI/584


C. Tables of
Table 1.
Table 2.
Table 3.
Table 4.

Radiation Resistance ..........................................................................................


Thermoplastics ........................................................................................................
Elastomers ..............................................................................................................
Aromatic Polymers ..................................................................................................
Organic Composite Materials ..................................................................................

VI/585
VI/585
VI/586
VI/587
VI/588

D. References ......................................................................................................................... VI/588


PVT Relationships and Equations of State of Polymers ............................................................................. VI/591
A. Introduction ........................................................................................................................ VI/591
B. Isothermal Compressibility Equations ................................................................................. VI/592
C. Empirical or Semiempirical 3-Parameter Equations of State ............................................... VI/593
D. Lattice or Quasi Lattice Models .......................................................................................... VI/593
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xxxvi

Contents
E. Continuum Models .............................................................................................................. VI/594
F. Tables ................................................................................................................................
Table 1. Zero Pressure Volume V0(T) and Bulk Modulus B0(T) ............................................
Table 2. Abbreviations of Polymer Names and the Experimental TemperaturePressure Range for Polymer Liquids ......................................................................
Table 3. PVT Properties of Other Polymers ..........................................................................
Table 4. Characteristic Parameters for the Sanchez-cho Equation of State .........................
Table 5. Characteristic Parameters for the Hartmann-haque Equation of State ...................
Table 6. Characteristic Parameters for the Simple Cell Model Equation of State .................
Table 7. Characteristic Parameters for the Flory, Orwoll and Vrij Equation of State ............
Table 8. Characteristic Parameters for the Simha-somcynsky Equation of State ................
Table 9. Characteristic Parameters for the Sanchez-lacombe Equation of State .................
Table 10. Characteristic Parameters for the AHS + vdW Equation of State ...........................

VI/595
VI/595
VI/596
VI/597
VI/597
VI/597
VI/598
VI/599
VI/599
VI/600
VI/600

G. References ......................................................................................................................... VI/601

VII. Solution Properties


Viscosity Molecular Weight Relationships and Unperturbed Dimensions of Linear Chain
Molecules ............................................................................................................................................

VII/1

A. Introduction ........................................................................................................................
1.
The Viscosity - Molecular Weight Relationship .......................................................
2.
Unperturbed Dimensions of Linear Chain Molecules ..............................................

VII/2
VII/2
VII/4

B. Effect of Molecular Weight Distribution on the Viscosity Constant K ...................................

VII/5

C. Tables of Viscosity - Molecular Weight Relationships, [] = KM ........................................


Table 1. Main-chain Acyclic Carbon Polymers .....................................................................
1.1
Poly(dienes) ............................................................................................
1.2
Poly(alkenes), Poly(acetylenes) .............................................................
1.3
Poly(acrylic Acid) and Derivatives ..........................................................
1.4
Poly(-substituted Acrylic Acid) and Derivatives ....................................
1.5
Poly(vinyl Ethers) ....................................................................................
1.6
Poly(vinyl Alcohol), Poly(vinyl Halides) ...................................................
1.7
Poly(vinyI Esters) ....................................................................................
1.8
Poly(styrene) and Derivatives .................................................................
1.9
Other Compounds ..................................................................................
1.10
Copolymers .............................................................................................
Table 2. Main-chain Carbocyclic Polymers ...........................................................................
Table 3. Main-chain Heteroatom Polymers ...........................................................................
3.1
Poly(oxides), Poly(ethers) .......................................................................
3.2
Poly(esters), Poly(carbonates) ...............................................................
3.3
Poly(amides) ...........................................................................................
3.4
Poly(amino Acids) ...................................................................................
3.5
Poly(ureas), Poly(urethanes), Poly(imines) ............................................
3.6
Poly(sulfides) ..........................................................................................
3.7
Poly(phosphates) ....................................................................................
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VII/5
VII/5
VII/5
VII/7
VII/10
VII/13
VII/17
VII/17
VII/18
VII/19
VII/24
VII/27
VII/31
VII/32
VII/32
VII/34
VII/36
VII/38
VII/39
VII/39
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Contents

xxxvii

3.8
Poly(siloxanes), Poly(silsesquioxanes) ...................................................
3.9
Poly(heterocyclics) ..................................................................................
3.10
Copolymers (Maleic Anhydride, Sulfones) ..............................................
3.11
Other Compounds ..................................................................................
Table 4. Cellulose and Derivatives, Poly(saccharides) .........................................................
Table 5. Miscellaneous .........................................................................................................

VII/40
VII/41
VII/42
VII/42
VII/43
VII/46

D. Calculated Unperturbed Dimensions of Freely Rotating Chains .........................................

VII/46

E. Unperturbed Dimensions of Linear Polymer Molecules ......................................................


Table 6. Main-chain Acyclic Carbon Polymers .....................................................................
6.1
Poly(dienes) ............................................................................................
6.2
Poly(alkenes), Poly(acetylenes) .............................................................
6.3
Poly(acrylic Acid) and Derivatives ..........................................................
6.4
Poly(-substituted Acrylic Acid) and Derivatives ....................................
6.5
Poly(vinyl Ethers), Poly(vinyl Alcohol), Poly(vinyl Esters),
Poly(vinyl Halides) ..................................................................................
6.6
Poly(styrene) and Derivatives .................................................................
6.7
Other Compounds ..................................................................................
6.8
Copolymers .............................................................................................
Table 7. Main-chain Carbocyclic Polymers ...........................................................................
Table 8. Main-chain Heteroatom Polymers ...........................................................................
8.1
Poly(oxides), Poly(ethers) .......................................................................
8.2
Poly(esters), Poly(carbonates) ...............................................................
8.3
Poly(amides) ...........................................................................................
8.4
Poly(amino Acids) ...................................................................................
8.5
Poly(urethanes) ......................................................................................
8.6
Poly(sulfides) ..........................................................................................
8.7
Poly(phosphates) ....................................................................................
8.8
Poly(siloxanes), Poly(silsesquioxanes), Poly(silmethylenes) .................
8.9
Poly(heterocyclics) ..................................................................................
8.10
Copolymers (Maleic Anhydride, Sulfones, Siloxanes) ............................
8.11
Other Compounds ..................................................................................
Table 9. Cellulose and Derivatives, Poly(saccharides) .........................................................

VII/47
VII/47
VII/47
VII/48
VII/49
VII/50

F. References .........................................................................................................................

VII/68

Sedimentation Coefficients, Diffusion Coefficients, Partial Specific Volumes, Frictional Ratios, and
Second Virial Coefficients of Polymers in Solution ............................................................................

VII/85

A. Sedimentation Coefficients, Diffusion Coefficients, Partial Specific Volumes, and


Frictional Ratios of Polymers in Solution ............................................................................
1.
Introduction .............................................................................................................
1.1.
Sedimentation Coefficient .......................................................................
1.2.
Diffusion Coefficient ................................................................................
1.3.
Molar Mass Averages Determined from Sedimentation and
Diffusion Coefficients ..............................................................................
1.4.
Partial Specific Volumes .........................................................................
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VII/58
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VII/60
VII/60
VII/61
VII/63
VII/63
VII/63
VII/63
VII/64
VII/64
VII/64
VII/65
VII/66
VII/66

VII/86
VII/86
VII/86
VII/87
VII/89
VII/89

xxxviii

Contents
1.5.
1.6.
1.7.

Frictional Ratios ......................................................................................


List of Symbols and Abbreviations ..........................................................
Miscellaneous .........................................................................................

B. Tables of Sedimentation Coefficients, Diffusion Coefficients, Partial Specific


Volumes, and Frictional Ratios of Polymers in Solution ......................................................
Table 1. Poly(alkenes) ..........................................................................................................
Table 2. Poly(dienes) ............................................................................................................
Table 3. Acrylic Polymers .....................................................................................................
Table 4. Vinyl Polymers ........................................................................................................
Table 5. Styrene Polymers ....................................................................................................
Table 6. (O, C)-Heterochain Polymers [Poly(ethers), Poly(esters), Poly(carbonates)] .........
Table 7. (N, C)- and (O, N, C)-Heterochain Polymers [Poly(amides), Poly(ureas),
Poly(urethanes)] ......................................................................................................
Table 8. Other Synthetic Polymers .......................................................................................
Table 9. Inorganic Polymers .................................................................................................
Table 10. Poly(saccharides) ...................................................................................................
Table 11. Other Biopolymers [Proteins, Poly(nucleotides)] ....................................................

VII/89
VII/90
VII/91
VII/92
VII/92
VII/94
VII/96
VII/105
VII/109
VII/134
VII/137
VII/140
VII/141
VII/144
VII/157

C. Second Virial Coefficients of Polymers in Solution ..............................................................


1.
Introduction .............................................................................................................
1.1.
Colligative Properties ..............................................................................
1.2.
Scattering Methods .................................................................................
1.3.
Sedimentation Velocity ...........................................................................
1.4.
Sedimentation Equilibrium ......................................................................
1.5.
pVT Measurements ............................................................................
1.6.
Averages of the Second Virial Coefficient ..............................................
1.7.
Second Virial Coefficient Molar Mass Relationship .............................
1.8.
Temperature Dependence, Pressure Dependence ................................
1.9.
Abbreviations ..........................................................................................
1.10.
Miscellaneous .........................................................................................

VII/163
VII/163
VII/163
VII/163
VII/163
VII/164
VII/164
VII/164
VII/164
VII/164
VII/164
VII/164

D. Tables of
Table 12.
Table 13.
Table 14.
Table 15.
Table 16.
Table 17.
Table 18.

VII/165
VII/165
VII/168
VII/170
VII/177
VII/179
VII/188

Table 19.
Table 20.
Table 21.
Table 22.

Second Virial Coefficients of Polymers in Solution ..............................................


Poly(alkenes), Poly(alkynes) ...................................................................................
Poly(dienes) ............................................................................................................
Poly(acrylics) ...........................................................................................................
Poly(vlnyls) ..............................................................................................................
Poly(styrenes) .........................................................................................................
(O, C)-heterochain Polymers [Poly(ethers), Poly(esters), Poly(carbonates)] .........
(N, C)- and (O, N, C)-heterochain Polymers [Poly(amides), Poly(ureas),
Poly(urethanes)] ......................................................................................................
Other Synthetic Polymers .......................................................................................
Inorganic Polymers .................................................................................................
Poly(saccharides) ...................................................................................................
Other Biopolymers [Proteins, Poly(nucleotides)] ....................................................

VII/191
VII/192
VII/192
VII/194
VII/196

E. References ......................................................................................................................... VII/198


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Contents

xxxix

Polymolecularity Correction Factors ............................................................................................................ VII/215


A. List of Symbols Used .......................................................................................................... VII/216
B. Introduction ........................................................................................................................ VII/217
Table 1 .................................................................................................................................... VII/223
C. Polymolecularity Correction Factors for Intrinsic Viscosity Versus Molecular Weight
Relationship .......................................................................................................................
Table 2 ....................................................................................................................................
Table 3 ....................................................................................................................................
Table 4 ....................................................................................................................................
Table 5 ....................................................................................................................................
Table 6 ....................................................................................................................................
Table 7 ....................................................................................................................................
Table 8 ....................................................................................................................................
Table 9 ....................................................................................................................................
Table 10 ..................................................................................................................................
Table 11 ..................................................................................................................................
Table 12 ..................................................................................................................................
Table 13 ..................................................................................................................................
Table 14 ..................................................................................................................................
Table 15 ..................................................................................................................................
Table 16 ..................................................................................................................................
Table 17 ..................................................................................................................................
Table 18 ..................................................................................................................................
Table 19 ..................................................................................................................................

VII/223
VII/223
VII/223
VII/223
VII/224
VII/224
VII/224
VII/224
VII/224
VII/225
VII/225
VII/225
VII/225
VII/225
VII/226
VII/226
VII/226
VII/226
VII/226

D. Polymolecularity Correction Factors for Sedimentation Coefficient Versus Molecular


Weight Relationship ...........................................................................................................
Table 20 ..................................................................................................................................
Table 21 ..................................................................................................................................
Table 22 ..................................................................................................................................
Table 23 ..................................................................................................................................
Table 24 ..................................................................................................................................
Table 25 ..................................................................................................................................
Table 26 ..................................................................................................................................
Table 27 ..................................................................................................................................

VII/227
VII/227
VII/227
VII/227
VII/227
VII/228
VII/228
VII/228
VII/229

E. Polymolecularity Correction Factors for Diffusion Coefficient Versus Molecular


Weight Relationship ...........................................................................................................
Table 28 ..................................................................................................................................
Table 29 ..................................................................................................................................
Table 30 ..................................................................................................................................
Table 31 ..................................................................................................................................
Table 32 ..................................................................................................................................
Table 33 ..................................................................................................................................
Table 34 ..................................................................................................................................

VII/229
VII/229
VII/229
VII/229
VII/230
VII/230
VII/230
VII/230

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Contents
Table 35
Table 36
Table 37
Table 38
Table 39
Table 40
Table 41

..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................

VII/230
VII/231
VII/231
VII/231
VII/231
VII/232
VII/232

F. Polymolecularity Correction Factors for Mean-Square Radius of Gyration versus


Molecular Weight Relationship ...........................................................................................
Table 42 ..................................................................................................................................
Table 43 ..................................................................................................................................
Table 44 ..................................................................................................................................
Table 45 ..................................................................................................................................
Table 46 ..................................................................................................................................
Table 47 ..................................................................................................................................

VII/232
VII/232
VII/233
VII/233
VII/233
VII/234
VII/234

G. Polymolecularity Correction Factors for Second Virial Coefficient Versus Molecular


Weight Relationship ...........................................................................................................
Table 48 ..................................................................................................................................
Table 49 ..................................................................................................................................
Table 50 ..................................................................................................................................
Table 51 ..................................................................................................................................

VII/234
VII/234
VII/235
VII/235
VII/235

H. Polymolecularity Correction Factors for the Determination of the Dimensions of


Macromolecules .................................................................................................................
1.
Fox-flory Relationship .............................................................................................
Table 52 ..................................................................................................................
Table 53 ..................................................................................................................
Table 54 ..................................................................................................................
Table 55 ..................................................................................................................
2.
Interconversion of Different Averages of the Mean-square Radius of
Gyration ..................................................................................................................
Table 56 ..................................................................................................................
Table 57 ..................................................................................................................
Table 58 ..................................................................................................................
Table 59 ..................................................................................................................
3.
Interconversion of Different Averages of the Mean-square End-to-end
Distance ..................................................................................................................
Table 60 ..................................................................................................................
Table 61 ..................................................................................................................
Table 62 ..................................................................................................................
Table 63 ..................................................................................................................
Table 64 ..................................................................................................................
Table 65 ..................................................................................................................

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VII/236
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VII/238
VII/238
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VII/239
VII/239
VII/239
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Contents
4.

I.

xli

The Effect of Polymolecularity on the Radius of Gyration of Stiff Polymer


Chains ..................................................................................................................... VII/240
Table 66 .................................................................................................................. VII/240
Table 67 .................................................................................................................. VII/240

Polymolecularity Correction Factors for the Determination of Unperturbed


Dimensions of Macromolecules ..........................................................................................
1.
Burchard-stockmayer-fixman Procedure ................................................................
Table 68 ..................................................................................................................
Table 69 ..................................................................................................................
Table 70 ..................................................................................................................
2.
Cowie-bywater Procedure .......................................................................................
Table 71 ..................................................................................................................
Table 72 ..................................................................................................................
Table 73 ..................................................................................................................
Table 74 ..................................................................................................................
3.
Baumann-stockmayer-fixman Procedure ................................................................
Table 75 ..................................................................................................................
Table 76 ..................................................................................................................
Table 77 ..................................................................................................................
Table 78 ..................................................................................................................
4.
Baumann-kurata-stockmayer Procedure ................................................................
Table 79 ..................................................................................................................
Table 80 ..................................................................................................................
Table 81 ..................................................................................................................
Table 82 ..................................................................................................................

VII/240
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VII/242
VII/242
VII/242
VII/242
VII/242
VII/243
VII/243
VII/243
VII/243
VII/244

J. References ......................................................................................................................... VII/244


Polymer-solvent Interaction Parameters ..................................................................................................... VII/247
A. Introduction ........................................................................................................................ VII/247
B. Concentration Variables ..................................................................................................... VII/247
C. Conversion of Concentration Variables .............................................................................. VII/247
D. Basic Equations .................................................................................................................. VII/247
E. Methods of Determination .................................................................................................. VII/248
F. Temperature Dependence .................................................................................................. VII/249
G. Concentration Dependence ................................................................................................ VII/249
H. Molecular Weight Dependence ........................................................................................... VII/250
I.

Polymer-solvent Interaction Parameters, ......................................................................... VII/250

J. References ......................................................................................................................... VII/262


Concentration Dependence of the Viscosity of Dilute Polymer Solutions: Huggins and Schulzblaschke Constants ............................................................................................................................ VII/265
A. Introduction ........................................................................................................................ VII/265
B. Tables ................................................................................................................................ VII/266

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xlii

Contents
Table 1. Huggins Constants .................................................................................................
1.1
Poly(dienes) and Poly(alkenes) ..............................................................
1.2
Poly(acrylic Acid) and Poly(methacrylic Acid) Derivatives ......................
1.3
Vinyl Polymers ........................................................................................
1.4
Poly(oxides) ............................................................................................
1.5
Poly(esters) .............................................................................................
1.6
Polyamides .............................................................................................
1.7
Other Compounds ..................................................................................
1.8
Cellulose, Cellulose Derivatives, and Polysaccharides ..........................
Table 2. Schulz-blaschke Constants .....................................................................................

VII/266
VII/266
VII/268
VII/272
VII/277
VII/278
VII/279
VII/280
VII/282
VII/284

C. References ......................................................................................................................... VII/285


Theta Solvents ............................................................................................................................................. VII/291
A. Introduction ........................................................................................................................
1.
Fundamentals .........................................................................................................
1.1
Thermodynamics ....................................................................................
1.2
Unperturbed Dimensions ........................................................................
2.
Methods to Determine Theta Solvents ....................................................................
2.1
Phase Equilibrium (PE) ...........................................................................
2.2
Second Virial Coefficient (A) ...................................................................
2.3
Cloud Point Titration (CP) .......................................................................
2.4
Cloud Temperature Titration (CT) ...........................................................
2.5
Unperturbed Dimensions (RGM, VM, DM, SM) ......................................
2.6
Other Methods ........................................................................................

VII/291
VII/291
VII/291
VII/292
VII/293
VII/293
VII/293
VII/294
VII/294
VII/294
VII/294

B. Tables of Theta Solvents for Polymers ...............................................................................


Table 1. Homochain Polymers ..............................................................................................
1.1
Poly(alkanes) ..........................................................................................
1.2
Poly(alkenes) ..........................................................................................
1.3
Poly(styrenes) .........................................................................................
1.4
Poly(vinyls) .............................................................................................
1.5
Poly(acrylics) and Related Compounds ..................................................
1.6
Poly(methacrylics) and Related Compounds ..........................................
1.7
Other Carbon Chains ..............................................................................
Table 2. Heterochain Polymers .............................................................................................
2.1
Poly(acetals) and Poly(ethers) ................................................................
2.2
Poly(esters) .............................................................................................
2.3
Poly(amides) ...........................................................................................
2.4
Polyureas and Polyurethanes .................................................................
2.5
Polysaccharides ......................................................................................
2.6
Carbon-sulfur Chains ..............................................................................
2.7
Silicon-oxygen Chains ............................................................................
2.8
Phosphorus-oxygen Chains ....................................................................

VII/295
VII/295
VII/295
VII/299
VII/300
VII/305
VII/307
VII/308
VII/312
VII/313
VII/313
VII/315
VII/316
VII/316
VII/316
VII/317
VII/317
VII/318

C. References ......................................................................................................................... VII/318

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Contents

xliii

Fractionation of Polymers ............................................................................................................................ VII/327


A. Principles of Polymer Fractionation .................................................................................... VII/327
B. Fractionation Methods ........................................................................................................
1.
Fractionation by Solubility .......................................................................................
2.
Fractionation by Chromatography ...........................................................................
3.
Cross Fractionation .................................................................................................
4.
Fractionation by Sedimentation ..............................................................................
5.
Fractionation by Diffusion .......................................................................................
6.
Fractionation by Ultrafiltration through Porous Membranes ....................................
7.
Fractionation by Zone Melting .................................................................................
8.
Electron Microscopic Counting Method ..................................................................

VII/328
VII/328
VII/330
VII/332
VII/333
VII/333
VII/333
VII/333
VII/333

C. Tables of Fractionation Systems for Different Polymers .....................................................


Table 1. Main-chain Acyclic Carbon Polymers .....................................................................
1.1
Poly(dienes) ............................................................................................
1.2
Poly(alkenes) ..........................................................................................
1.3
Poly(acrylic Acid) and Derivatives ..........................................................
1.4
Poly(methacrylic Acid) and Derivatives ..................................................
1.5
Other - and -Substituted Poly(acrylics) and Poly(methacrylics) .........
1.6
Poly(vinyl Ethers) ....................................................................................
1.7
Poly(vinyl Alcohol), Poly(vinyl Ketones), Poly(vinyl Halides),
Poly(vinyl Nitriles) ...................................................................................
1.8
Poly(vinyl Esters) ....................................................................................
1.9
Poly(styrenes) .........................................................................................
1.10
Other Compounds ..................................................................................
1.11
Random and Alternating Copolymers .....................................................
1.12
Block Copolymers ...................................................................................
1.13
Graft Copolymers ....................................................................................
1.14
Mixture of Polymers ................................................................................
Table 2. Main-chain Carbocyclic Polymers ...........................................................................
2.1
Poly(phenylenes) ....................................................................................
2.2
Formaldehyde Resins .............................................................................
Table 3. Main-chain Heteroatom Polymers ...........................................................................
3.1
Poly(oxides) ............................................................................................
3.2
Poly(carbonates) .....................................................................................
3.3
Poly(esters) .............................................................................................
3.4
Poly(urethanes) and Poly(ureas) ............................................................
3.5
Poly(amides) and Poly(imines) ...............................................................
3.6
Poly(amino Acids) ...................................................................................
3.7
Poly(sulfides), Poly(sulfones), Poly(sulfonamides) .................................
3.8
Poly(silanes) and Poly(siloxanes) ...........................................................
3.9
Poly(phosphazenes) and Related Polymers ...........................................
3.10
Other Compounds ..................................................................................
3.11
Random Copolymers ..............................................................................

VII/333
VII/333
VII/333
VII/336
VII/344
VII/346
VII/351
VII/353

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VII/353
VII/355
VII/356
VII/363
VII/366
VII/382
VII/389
VII/395
VII/397
VII/397
VII/397
VII/398
VII/398
VII/404
VII/405
VII/410
VII/411
VII/414
VII/416
VII/418
VII/422
VII/423
VII/425

xliv

Contents
3.12
Block Copolymers ...................................................................................
3.13
Graft Copolymers ....................................................................................
Table 4. Poly(saccharides) ...................................................................................................
4.1
Poly(saccharides) ...................................................................................
4.2
Graft Copolymers ....................................................................................
4.3
Mixtures of Polymers ..............................................................................

VII/427
VII/430
VII/431
VII/431
VII/436
VII/438

D. References .........................................................................................................................
1 to 1188 .................................................................................................................................
1189 to 2452 ...........................................................................................................................
2453 to 3608 ...........................................................................................................................

VII/438
VII/438
VII/458
VII/478

Solvents and Non Solvents for Polymers .................................................................................................... VII/497


A. Introduction ........................................................................................................................ VII/498
B. Abbreviations ..................................................................................................................... VII/498
C. Tables of Solvents and Nonsolvents ...................................................................................
Table 1. Main-chain Acyclic Carbon Polymers .....................................................................
1.1
Poly(dienes), Poly(acetylenes) ...............................................................
1.2
Poly(alkenes) ..........................................................................................
1.3
Poly(acrylics), Poly(methacrylics) ...........................................................

VII/499
VII/499
VII/499
VII/500
VII/501

1.3.1 Poly(acrylic Acids) ............................................................................ VII/501


1.3.2 Poly(acrylates) .................................................................................. VII/501
1.3.3 Poly(methacrylates) ......................................................................... VII/501
1.3.4 Poly(disubstituted Esters) ................................................................ VII/502
1.3.5 Poly(acrylamides), Poly(methacrylamides) .....................................
1.4
Poly(vinyl Ethers) ....................................................................................
1.5
Poly(vinyl Alcohols), Poly(acetals), Poly(vinyl Ketones) .........................
1.6
Poly(vinyl Halides) ..................................................................................
1.7
Poly(vinyl Nitrites) ...................................................................................
1.8
Poly(vinyl Esters) ....................................................................................
1.9
Poly(styrenes) .........................................................................................
1.10
Other Compounds ..................................................................................
Table 2. Main-chain Carbocyclic Polymers ...........................................................................
2.1
Poly(phenylenes) ....................................................................................
2.2
Other Compounds ..................................................................................
Table 3. Main-chain Carbonyl Polymers ...............................................................................
Table 4. Main-chain Acyclic Heteroatom Polymers ..............................................................
4.1
Main-chain COC Polymers .............................................................

VII/503
VII/503
VII/504
VII/505
VII/506
VII/506
VII/507
VII/508
VII/509
VII/509
VII/510
VII/510
VII/511
VII/511

4.1.1 Poly(oxides) ...................................................................................... VII/511


4.1.2 Poly(carbonates) .............................................................................. VII/513
4.1.3 Poly(esters) ...................................................................................... VII/513
4.1.4 Poly(anhydrides) .............................................................................. VII/515
4.1.5 Poly(urethanes) ................................................................................ VII/515

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Contents
4.2

xlv

Main-chain O Heteroatom Polymers ................................................... VII/515


4.2.1 Poly(sulfonates) ................................................................................ VII/515

4.3

4.2.2 Poly(siloxanes) ................................................................................. VII/516


Main-chain CSC and CSN Polymers ...................................... VII/516
4.3.1 Poly(sulfides) .................................................................................... VII/516
4.3.2 Poly(sulfones) ................................................................................... VII/517

4.4

4.3.3 Others ............................................................................................... VII/518


Main-chain CNC Polymers ............................................................. VII/518
4.4.1 Poly(amides) .................................................................................... VII/518
4.4.2 Poly(hydrazides) ............................................................................... VII/520
4.4.3 Poly(ureas) ....................................................................................... VII/521
4.4.4 Poly(carbodiimides) .......................................................................... VII/521

4.4.5 Other Compounds ............................................................................


4.5
Poly(phosphazenes) and Related Compounds ......................................
4.6
Poly(silanes), Poly(silazanes) .................................................................
Table 5. Main-chain Heterocyclic Polymers ..........................................................................
5.1
Poly(benzoxazoles), Poly(oxadiazoles), Poly(oxadiazolidines) ..............
5.2
Poly(dithiazoles), Poly(benzothiazoles) ..................................................
5.3
Poly(imides) ............................................................................................

VII/521
VII/522
VII/522
VII/523
VII/523
VII/524
VII/524

5.3.1 Poly(benzimides) .............................................................................. VII/524


5.3.2 Poly(pyromellitides) .......................................................................... VII/525
5.3.3 Others ...............................................................................................
5.4
Poly(quinoxalines) ..................................................................................
5.5
Poly(benzimidazoles) ..............................................................................
5.6
Poly(piperazines) ....................................................................................
5.7
Poly(anhydrides) .....................................................................................
5.8
Poly(thiophenes) .....................................................................................
5.9
Others .....................................................................................................
Table 6. Formaldehyde Resins .............................................................................................
Table 7. Natural Polymers and Modified Natural Polymers ..................................................
7.1
Natural Rubber and Derivatives ..............................................................
7.2
Cutta Percha ...........................................................................................
7.3
Cellulose and Derivatives .......................................................................

VII/525
VII/526
VII/526
VII/526
VII/527
VII/527
VII/527
VII/528
VII/528
VII/528
VII/529
VII/529

7.3.1 Cellulose ........................................................................................... VII/529


7.3.2 Cellulose Ethers ............................................................................... VII/529
7.3.3 Cellulose Esters ............................................................................... VII/530
7.3.4 Cellulose Nitrate and Sulfate ...........................................................
7.4
Starch and Derivatives ............................................................................
7.5
Other Poly(saccharides) .........................................................................
7.6
Natural Resins ........................................................................................
Table 8. Inorganic Polymers .................................................................................................
Table 9. Poly(electrolytes) ....................................................................................................
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VII/531
VII/531
VII/531
VII/532
VII/532
VII/533

xlvi

Contents
Table 10. Block Polymers ....................................................................................................... VII/533
Table 11. Dendrimers ............................................................................................................. VII/534
D. References ......................................................................................................................... VII/536

Specific Refractive Index Increments of Polymers in Dilute Solution ......................................................... VII/547


A. Introduction ........................................................................................................................ VII/547
B. Introduction from the Third Edition ...................................................................................... VII/547
C. Refractometric Calibration Data .......................................................................................... VII/550
D. Tables of Specific Refractive Index Increments of Polymer Solutions .................................
Table 1. Main-chain Acyclic Carbon Polymers .....................................................................
1.1
Poly(dienes) ............................................................................................
1.2
Poly(alkenes) ..........................................................................................
1.3
Poly(acrylic Acid) and Derivatives ..........................................................
1.4
Poly(methacrylic Acid) and Derivatives ..................................................
1.5
Other - or -Substituted Poly(acrylics) and Poly(methacrylics) ............
1.6
Poly(styrenes) .........................................................................................
1.7
Other Compounds ..................................................................................
Table 2. Main-chain Cyclic Carbon Polymers .......................................................................
Table 3. Main-chain Heteroatom Polymers ...........................................................................
3.1
COC Polymers (Poly(oxides), Poly(esters), and Others) ....................
3.2
CSC Polymers (Poly(sulfones) and Others) .......................................
3.3
CNC Polymers (Poly(amides), Poly(isocyanates),
Poly(urethanes), and Others) .................................................................
3.4
Poly(amino Acids) ...................................................................................
3.5
Poly(silanes) and Poly(silazanes) ...........................................................
3.6
Poly(heterocyclics) and Others ...............................................................
Table 4. Cellulose and Derivatives .......................................................................................
Table 5. Poly(saccharides) ...................................................................................................

VII/551
VII/551
VII/551
VII/553
VII/557
VII/561
VII/573
VII/574
VII/588
VII/594
VII/594
VII/594
VII/599
VII/599
VII/604
VII/606
VII/608
VII/609
VII/611

E. References ......................................................................................................................... VII/615


Particle Scattering Factors in Rayleigh Scattering ...................................................................................... VII/629
A. Introduction: General Relations for a Homogeneous Solute ............................................... VII/629
B. Scattering Factors for Various Molecular Models ................................................................ VII/630
C. Effects of Dispersion in Molecular Weight .......................................................................... VII/631
D. Determination of Molecular Weight and Radius of Gyration ................................................ VII/632
E. Calculation of Scattering Factors ........................................................................................ VII/633
F. Particle Scattering Factors and Dissymmetries .................................................................. VII/633
Table 1. Dissymmetries for Monodisperse Systems ............................................................. VII/634
Table 2. Dissymmetries for Monodisperse and Polydisperse Coils ...................................... VII/634
G. References ......................................................................................................................... VII/635
Dipole Moments of Polymers in Solution ..................................................................................................... VII/637
A. Introduction ........................................................................................................................ VII/637
B. Dipole Moments of Polymers In Solution ............................................................................ VII/638
Table 1. Polyoxides (Polyethers) .......................................................................................... VII/638
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Contents
Table 2.
Table 3.
Table 4.
Table 5.
Table 6.
Table 7.
Table 8.
Table 9.
Table 10.
Table 11.
Table 12.
Table 13.

Polysulfides (Polythioethers) ...................................................................................


Hydroxyl Terminated Oxide/Sulfide Copolymers ....................................................
Polyesters Derived from Aromatic Diacids ..............................................................
Aliphatic and Cycloaliphatic Polyesters ..................................................................
Polycarbonates .......................................................................................................
Vinyl Polymers ........................................................................................................
Acrylic Polymers .....................................................................................................
Methacrylic Polymers ..............................................................................................
Itaconate Polymers .................................................................................................
Polydienes ..............................................................................................................
Silicon Based Polymers ..........................................................................................
Styrene Copolymers ...............................................................................................

xlvii
VII/639
VII/640
VII/640
VII/641
VII/641
VII/642
VII/643
VII/644
VII/644
VII/644
VII/645
VII/645

C. References ......................................................................................................................... VII/646


Heat, Entropy and Volume Changes for Polymer-liquid Mixtures .............................................................. VII/649
A. Introduction ........................................................................................................................ VII/649
1.
Scope of the Table .................................................................................................. VII/649
2.
Experimental Methods ............................................................................................ VII/649
B. Key for the Tables .............................................................................................................. VII/650
C. Tables of Literature References for Heat, Entropy, and Volume Changes for
Polymer-solvent Mixtures ...................................................................................................
Table 1. Main-chain Carbon Polymers ..................................................................................
1.1
Poly(dienes) ............................................................................................
1.2
Poly(alkenes) ..........................................................................................
1.3
Poly(acrylics) ..........................................................................................
1.4
Vinyl Polymers ........................................................................................
1.5
Poly(styrenes) .........................................................................................
1.6
Other Compounds ..................................................................................
Table 2. Main-chain Carbon Heteroatom Polymers ..............................................................
2.1
Poly(oxides) and Poly(esters) .................................................................
2.2
Poly(amides) ...........................................................................................
2.3
Poly(siloxanes) .......................................................................................
2.4
Derivatives of Cellulose ..........................................................................
2.5
Other Compounds ..................................................................................

VII/650
VII/650
VII/650
VII/651
VII/654
VII/655
VII/657
VII/659
VII/659
VII/659
VII/661
VII/661
VII/662
VII/663

D. References ......................................................................................................................... VII/663


Heats of Solution of Some Common Polymers ........................................................................................... VII/671
A. Introduction ........................................................................................................................ VII/671
B. Table of Heats of Solution .................................................................................................. VII/671
C. References ......................................................................................................................... VII/673
Solubility Parameter Values ......................................................................................................................... VII/675
A. Introduction ........................................................................................................................ VII/675
B. Miscibility of Solvents and Polymers ................................................................................... VII/676
1.
Cohesive Energy Density and the Solubility (Hildebrand) Parameter ..................... VII/676
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xlviii

Contents
2.
3.

Cohesive Energy Parameters for Polar Systems .................................................... VII/677


Relationship Between Solubility Parameters and Other Thermodynamic
Parameters ............................................................................................................. VII/677

C. Solubility Parameter Measurements, Calculations, and Correlations ..................................


1.
Solvents ..................................................................................................................
2.
Polymers .................................................................................................................
2.1
Indirect Measurements ...........................................................................
2.2
Correlation Methods ...............................................................................
Table 1. Selected Solvents for Use in Polymer Solvency Testing ........................................
Table 2. Group Contribution to Cohesive Energy Density ....................................................
2.1
Carbon-containing Groups ......................................................................
2.2
Oxygen-containing Groups .....................................................................
2.3
Nitrogen-containing Groups ....................................................................
2.4
Other Groups ..........................................................................................
2.5
Structural Features .................................................................................
Table 3. Contribution to Ecoh and V .......................................................................................
Table 4. Solubility Parameter I: Component Group Contributions ........................................
Table 5. Solubility Parameter II: Component Group Contributions .......................................
Table 6. Equations to be Used for Hoy's System .................................................................

VII/679
VII/679
VII/680
VII/680
VII/682
VII/683
VII/684
VII/684
VII/684
VII/684
VII/684
VII/685
VII/685
VII/686
VII/686
VII/687

D. Solubility
Table 7.
Table 8.
Table 9.

VII/688
VII/688
VII/694
VII/698
VII/698
VII/698
VII/698
VII/699
VII/699
VII/699
VII/699
VII/700
VII/700
VII/700
VII/700
VII/701
VII/701
VII/701
VII/701
VII/702
VII/702
VII/708
VII/709
VII/710

Parameter Tables ................................................................................................


Solubility Parameters of Solvents in Alphabetical Order .........................................
Solubility Parameters of Solvents in Increasing Order of .....................................
Hansen Solubility Parameters of Liquids at 25C ...................................................
9.1
Paraffinic Hydrocarbons .........................................................................
9.2
Aromatic Hydrocarbons ..........................................................................
9.3
Halohydrocarbons ...................................................................................
9.4
Ethers .....................................................................................................
9.5
Ketones ...................................................................................................
9.6
Aldehydes ...............................................................................................
9.7
Esters ......................................................................................................
9.8
Nitrogen-containing Compounds ............................................................
9.9
Sulfur-containing Compounds ................................................................
9.10
Acid Halides and Anhydrides ..................................................................
9.11
Alcohols ..................................................................................................
9.12
Acids .......................................................................................................
9.13
Phenols ...................................................................................................
9.14
Water ......................................................................................................
9.15
Polyhydric Alcohols .................................................................................
Table 10. Solubility Parameters of Polymers ..........................................................................
10.1
Main Chain Carbon Polymers .................................................................
10.2
Main Chain CO Polymers .....................................................................
10.3
Main Chain CN Polymers .....................................................................
10.4
Other Polymers .......................................................................................
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Contents

xlix

E. References ......................................................................................................................... VII/711


Optically Active Polymers ............................................................................................................................ VII/715
A. Abbreviations Used ............................................................................................................ VII/715
B. Optically Active Polymers from Chiral Monomers ...............................................................
Table 1. Main-chain Acyclic Carbon Polymers .....................................................................
1.1
Poly(alkenes) ..........................................................................................
1.2
Poly(acrylics) and Related Polymers ......................................................
1.3
Poly(methacrylics) and Related Polymers ..............................................
1.4
Poly(vinyl Ethers), Poly(vinyl Ketones), and Poly(vinyl Esters) ..............
1.5
Poly(styrenes), Poly(carbazoles) ............................................................
1.6
Poly(dienes) ............................................................................................
1.7
Poly(isonitriles) .......................................................................................
1.8
Poly(alkynes) ..........................................................................................
1.9
Poly(maleimides) and Related Polymers ................................................
1.10
Other Compounds ..................................................................................
Table 2. Main-chain Acyclic Heteroatom Polymers ..............................................................
2.1
Poly(oxides) ............................................................................................
2.2
Poly(esters) .............................................................................................
2.3
Poly (sulfides), Poly(thioesters) ..............................................................
2.4
Poly(urethanes), Poly(ureas) ..................................................................
2.5
Poly(amides) ...........................................................................................
2.6
Poly(isocyanates) ...................................................................................
2.7
Poly(imines) ............................................................................................
2.8
Poly(amino Acids) ...................................................................................
Table 3. Poly(saccharides) ...................................................................................................

VII/716
VII/716
VII/716
VII/716
VII/717
VII/718
VII/719
VII/720
VII/720
VII/721
VII/722
VII/723
VII/723
VII/723
VII/724
VII/725
VII/725
VII/726
VII/728
VII/728
VII/729
VII/732

C. Optically Active Polymers from Achiral Monomers ..............................................................


Table 4. Main-chain Acyclic Carbon Polymers .....................................................................
4.1
Poly(acrylics) and Related Polymers ......................................................
4.2
Poly(methacrylics) and Related Polymers ..............................................
4.3
Poly(vinyl Ethers) ....................................................................................
4.4
Poly(styrenes) .........................................................................................
4.5
Poly(dienes) ............................................................................................
4.6
Poly(isonitriles) .......................................................................................
4.7
Poly(maleimides) ....................................................................................
4.8
Other Compounds ..................................................................................
Table 5. Main-chain Acyclic Heteroatom Polymers ..............................................................
5.1
Poly(oxides) and Poly(sulfides) ..............................................................
5.2
Poly(isocyanates) ...................................................................................

VII/733
VII/733
VII/733
VII/734
VII/735
VII/735
VII/735
VII/736
VII/736
VII/737
VII/737
VII/737
VII/738

D. References ......................................................................................................................... VII/739


Anisotropy of Segments and Monomer Units of Polymer Molecules ......................................................... VII/745
A. Introduction ........................................................................................................................ VII/745

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Contents
B. Tables of Anisotropy of Segments and Monomer Units of Polymer Molecules ...................
Table 1. Main-chain Acyclic Carbon Polymers .....................................................................
1.1
Poly(dienes) ............................................................................................
1.2
Poly(alkenes) ..........................................................................................
1.3
Poly(acrylic Acid) and Derivatives ..........................................................
1.4
Poly(methacrylic Acid) and Derivatives ..................................................
1.5
Poly(acrylic Acid) Derivatives with Mesogenic Side Groups ...................
1.6
Poly(methacrylic Acid) Derivatives with Mesogenic Side Groups ...........
1.7
Vinyl Polymers ........................................................................................
1.8
Poly(vinyl) Derivatives with Mesogenic Side Groups ..............................
1.9
Copolymers, Graft and Block Copolymers ..............................................
Table 2. Main-chain Carbocyclic Polymers ...........................................................................
Table 3. Main-chain Heteroatom Polymers ...........................................................................
3.1
Poly(oxides) ............................................................................................
3.2
Poly(esters) .............................................................................................
3.3
Poly(amides) ...........................................................................................
3.4
Poly(peptides) and Nucleic Acids ...........................................................
3.5
Poly(phosphazenes) ...............................................................................
3.6
Poly(siloxanes) .......................................................................................
Table 4. Main-chain Heterocyclic Polymers ..........................................................................
4.1
Poly(imides) ............................................................................................
4.2
Poly(pyrromellitimides) ...........................................................................
4.3
Poly(quinoxalines) ..................................................................................
4.4
Poly(benzimidazoles), Poly(benzoxazoles) ............................................
4.5
Poly(saccharides) ...................................................................................

VII/746
VII/746
VII/746
VII/747
VII/747
VII/748
VII/748
VII/749
VII/750
VII/751
VII/751
VII/752
VII/752
VII/752
VII/752
VII/755
VII/755
VII/755
VII/756
VII/756
VII/756
VII/756
VII/757
VII/757
VII/758

C. References ......................................................................................................................... VII/760


Gelation Properties of Polymer Solutions .................................................................................................... VII/765

VIII. Abbreviations of Polymer Names and Chemical Abstract Numbers


Abbreviations for Thermoplastics, Thermosets, Fibers, Elastomers and Additives ...................................

VIII/1

A. Introduction ........................................................................................................................

VIII/1

B. Abbreviations in Alphabetical Order ....................................................................................

VIII/2

C. Abbreviations and Acronyms Based on Poly(monomer) Names ......................................... VIII/15


D. Abbreviations for Polymers Named after a Characteristic Polymer Croup .......................... VIII/17
E. Abbreviations for Polymers Produced by Chemical Transformation of Other
Polymers ............................................................................................................................ VIII/18
F. Abbreviations for Blends, Reinforced Polymers, etc. .......................................................... VIII/19
G. ISO Codes for Thermoplastic Materials ..............................................................................
1.
Codes for ISO Data Blocks 1-5 ...............................................................................
1.1
ISO and DIN Codes for Data Block 1 .....................................................
1.2
ISO Codes for Items in Data Block 2 ......................................................
1.3
ISO Codes for Items in Data Block 3 ......................................................

This page has been reformatted by Knovel to provide easier navigation.

VIII/19
VIII/19
VIII/19
VIII/20
VIII/20

Contents
1.4
1.5

li

ISO Codes for Extending and Reinforcing Fillers (Data Block 4) ........... VIII/20
ISO Codes for Data Block 5 .................................................................... VIII/21

H. SPI Codes for the Recycling of Plastics .............................................................................. VIII/21


I.

Recommended Abbreviations and Acronyms for Names of Elastomers ............................. VIII/21

J. Abbreviations for Textile Fibers .......................................................................................... VIII/22


Chemical Abstract Registry Numbers and Online Database Searching for Polymer Literature ................ VIII/25
A. Nomenclature ..................................................................................................................... VIII/25
B. CAS Registry Numbers ...................................................................................................... VIII/25
C. Indexing and CAS Registry Number Assignment ................................................................ VIII/26
D. Example Searches .............................................................................................................
1.
Example of a Search Using the Polymer CAS Registry Number ............................
2.
Example of a Search Using the Monomer CAS Registry Number ..........................
3.
Example of a Combined Search .............................................................................
4.
Example of a Copolymer Search ............................................................................
5.
Example of an Engineering Database Search ........................................................
6.
Example of a Search with Punctuation in the Polymer Name .................................
7.
Example of an Engineering Materials Abstracts Search .........................................
8.
Example of a Polymer Trademark Search ..............................................................

VIII/26
VIII/26
VIII/26
VIII/26
VIII/28
VIII/29
VIII/29
VIII/29
VIII/29

E. List of CAS Regisry Numbers of Common Polymers .......................................................... VIII/32

Index .......................................................................................................................................

This page has been reformatted by Knovel to provide easier navigation.

IX/1

S E C T I O N

R U L E S

N o m e n c l a t u r e

W . V. Metanomski
Chemical Abstracts Service, Columbus, Ohio, USA

A. Introduction
B. IUPAC Recommendations
1. Source-Based Nomenclature
1.1. Homopolymers
1.2. Copolymers
1.3. Nonlinear Macromolecules &
Macromolecular Assemblies
2. Structure-Based Nomenclature
2.1. Regular Single-Strand Organic Polymers
2.2. Regular Double-Strand Organic Polymers
2.3. Regular Single-Strand Inorganic and
Coordination Polymers
2.4. Regular Quasi-Single-Strand Coordination
Polymers
2.5. Irregular Single-Strand Organic Polymers
C. Use of Common and Semisystematic Names
D. Chemical Abstracts (CA) Index Names
E. Polymer Class Names
F. References
A.

1-1
1-1
I-2
I-2
I-2
I-3
I-3
I-6
I-6
I-7
I-7
I-8
I-8
1-11
1-12

INTRODUCTION

Macromolecular (polymer) nomenclature has an almost


50-year history. As early as 1949 there existed a
Subcommission on Nomenclature within the International
Union of Pure and Applied Chemistry (IUPAC) under the
chairmanship of Maurice L. Huggins. The Subcommission
was part of the IUPAC Commission on Macromolecules,
chaired then by Herman F. Mark. Other notable pioneers in
polymer science, Jan Joseph Hermans, Otto Kratky, Harry
W. Melville, and George J. Smets, were members of the
Commission.
The Subcommission produced its first official report in
1952. It recognized then, what is just as true today, that the
practice in the field of small molecules of providing
rigorous definitions is impractical for polymers. The latter
consist of molecules not necessarily exactly of the same
size, chemical composition, or structure. The differences
result from the presence of end groups, branches, variation
in orientation of monomeric units, and irregularity in the
sequence of different types of units.
The American Chemical Society (ACS) Division of
Polymer Chemistry established its Nomenclature Commit-

tee in 1963 to try to unify earlier attempts to name polymers


in some coherent way. Their first major project resulted in a
structure-based nomenclature for regular linear polymers,
first published in ACS Polymer Preprints in 1967, adopted
by Chemical Abstracts in 1968, and incorporated in IUPAC
recommendations in 1975 [I].
When the IUPAC Commission on Macromolecules was
elevated to become the IUPAC Division of Macromolecular
Chemistry, the latter in turn established its Commission on
Macromolecular Nomenclature in 1968.
The Commission in the course of its nearly 30 years of
existence produced a series of major documents that have
shaped modern nomenclature and terminology of polymer
science. The recommendations are being published in the
IUPAC official journal, Pure and Applied Chemistry, and
occasionally are republished in the form of a "Compendium" which groups all the currently valid documents in a
single volume. The Commission published its "Compendium of Macromolecular Nomenclature" in 1991 [2]. The
book, which IUPAC has designated the "Purple Book", in
analogy to other IUPAC books ("Blue" - organic, "Red"
- inorganic, "Orange" - analytical, "Green"- physical,
and "Gold" - overall chemistry), has the two most basic
macromolecular nomenclature recommendations: "nomenclature of regular single-strand organic polymers" and
"source-based nomenclature for copolymers". In more
recent years, the Commission extended that basic nomenclature to double-strand (ladder and spiro) organic polymers, irregular and crosslinked polymers, and polymer
blends and interpenetrating networks.
In this article, the basic structure-based and source-based
nomenclature of polymers is explained and illustrated in
some detail. The continuing use of common and
semisystematic nomenclature with reference to specific
tables in this Handbook is highlighted. The current
Chemical Abstracts (CA) index names [3] are compared
and contrasted with the IUPAC practice and typical names
employed in the polymer journals and textbooks.
B.

IUPAC RECOMMENDATIONS

Since polymers, unlike low-molecular-weight compounds,


have no uniform structure and are mixtures of macromolecules of different length and different structural

arrangement, their graphical representation and their names


require a special approach.
Often enough, the structure of the polymer has not been
sufficiently characterized and the researcher cannot draw its
chemical structure. Consequently, no name of the polymer
reflecting its structure is possible.
A polymerization reaction for a polymer formed from
a monomer such as vinyl chloride can schematically be
represented by

polybutadiene
polyethylene
poly(methyl methacrylate)
poly(methyl vinyl ether)
polystyrene
poly(tetrafluoroethylene)
poly(vinyl alcohol)
poly(vinyl acetate)
poly(vinyl chloride)
poly(vinylidene dichloride)

That shows an idealized product. In fact, however, the


polymer consists of long-chains of various lengths. The
repeating units, - C H 2 - C H C l - , are not necessarily all
uniquely oriented and joined in a regular fashion as shown
in the idealized structure above. In addition to "head-totail" links

Parentheses are used when the name of the monomer


consists of two or more words, and when the monomer has
substituents.
These are all olefinic type reactants, from which two
carbon atoms originally linked by a double bond form a
bivalent group:

other links such as "head-to-head"

where R and R [ represent a hydrogen atom or a substituent


group. Many of these are joined, in turn, to each other but
their exact orientation or sequence is seldom known.
On the other hand, different polymers derived from a
single monomer and having identical constitutional units
can still be differentiated by additional information, such as
average molecular weight and other chemical and physical
characteristics.

and "tail-to-tail"

can occur, and the exact sequence of all these repeating


units usually is not known.
This becomes even more complicated when a copolymer
is derived from more than one monomer, such as styrene
and methyl acrylate, which contribute two constitutional or
monomeric units:

They can combine into a polymeric chain, resulting in


many types such as unspecified, statistical, random,
alternating, periodic, block, or graft copolymers.
Because the exact structure of the polymer is not always
known, two systems of naming polymers exist:
source-based nomenclature,
structure-based nomenclature.
1.

Source-Based Nomenclature

1.1. Homopolymers Homopolymers are derived from


only one species of monomer, which may be the actual
starting reactant (or source), or be a hypothetical monomer
if the homopolymer is formed by a modification of another
homopolymer.
The name of the polymer is formed by attaching the
prefix "poly" to the name of the actual or assumed
monomer, or the starting reactant (source), from which the
polymer is derived.
Examples: poly (acrylic acid)
polyacrylonitrile

1.2. Copolymers For copolymers, the names of monomers are cited after the prefix "poly". In addition, an
italicized connective (infix) is placed between the names of
monomers to denote the kind of sequential arrangement by
which the constitutional (monomeric) units, derived from
each monomer, are related in the structure [4].
Seven types of sequence arrangements are listed with
their corresponding connectives:

Type

Connective

unknown or unspecified
statistical (obeying known statistical laws)
random (obeying Bernoullian distribution)
alternating (for two monomeric units)
periodic (ordered sequence of more than two)
block (linear arrangement of blocks)
graft (side blocks chains connected to
main chain)

Examples:

-co-stat-raft-alt-per-block-graft-

poly[styrene-C(?-(methyl methacrylate)!
poly^tyrene-statf-acrylonitrile-statf-butadiene)
poly[ethylene-ran-(vinyl acetate)]
poly[(ethylene glycol)-tf/r-(terephthalic acid)]
poly[formaldehyde-/?er-(ethylene oxide)-per(ethylene oxide)]
polystyrene-&/oc&-polybutadiene
polybutadiene-gra/f-polystyrene

The names of the monomers are those common or


semisystematic names that are encountered most often in
the literature of polymer science. The order of citation of
monomers in copolymer names is arbitrary.
An equally acceptable alternative scheme for naming
copolymers utilizes the prefix "copoly", followed by
citation of the names of the monomers, separated by an
oblique stroke (a solidus). Parentheses are not needed to
enclose monomer names consisting of two or more words.
Examples:

the constituent macromolecules with an italicized connective between them.


Examples:

copoly(styrene/methyl methacrylate)
j"tatf-copoly(styrene/acrylonitrile/butadiene)
ran-copoly(ethylene/vinyl acetate)
a/f-copoly(ethylene glycol/terephthalic acid)
per-copoly(formaldehyde/ethyleneoxide/ethylene oxide)
Wtfc/:-copoly(styrene-butadiene)
gra/-copoly(butadiene-styrene)

1.3. Nonlinear Macromolecules and Macromolecular


Assemblies Most recently, the source-based nomenclature
has been extended for non-linear macromolecules and
macromolecular assemblies [5], The non-linear macromolecules comprise branched, graft, comb, star, cyclic, and
network macromolecules. The macromolecular assemblies
comprise polymer blends, interpenetrating polymer networks, and polymer-polymer complexes.
The following italicized qualifiers can be used as both
prefixes (e.g., blend-, net-) and infixes (connectives) (e.g.,
-blend-, -net-) to designate the skeletal structure of nonlinear macromolecules or macromolecular assemblies:

Type
cyclic
branched, unspecified
short-chain-branched
long-chain-branched
branched with branch point
of functionality /
comb
star
star with / arms
network
crosslink
polymer blend
interpenetrating polymer network
semi-interpenetrating polymer network
polymer-polymer complex

Connective
cyclo
branch
sh-branch
l-branch
f-branch
comb
star
f-star
net
t (Greek iota)
blend
ipn
sipn
compl

2.

poly styrene-com>-poly aery lonitrile


com&-poly(styrene~statf-acrylonitrile)
poly styrene-comZ?- [poly acrylonitrile;
poly(methyl methacrylate)]
4-sfar-polystyrene
star-(po\yA-block-polyB-block-polyC)
star-(polyA; polyB; polyC)
star-(polyacrylonitrile; polystyrene)
(M1 100000:20000)
fte-polystyrene--divinylbenzene
n^-poly[styrene-<3/Kmaleic anhydride)]^-(ethylene glycol)
polystyrene-Weftd-poly(2,6-dimethylphenol)
poly(methyl methacrylate)-We?i(i-poly(tt-butyl
acrylate)
(net-polystyrene)-sipn-poly(vinyl chloride)
[net-poly(styrenQ-stat-butSidiene]-ipn-[netpoly(ethyl acrylate)

Structure-Based Nomenclature

2.1. Regular Single-Strand Organic Polymers For


regular organic polymers which have only one species of
constitutional repeating unit (CRU) in a single sequential
arrangement and consist of single strands only, the name is
poly(constitutional repeating unit),
wherein the repeating group is named as a bivalent organic
group according to the IUPAC nomenclature rules for
organic compounds [I]. Each such repeating group can
consists of simple or substituted subunits such as:
methylene
ethylene
vinylene
hexane-l,6-diyl
1-chloroethylene
1 -oxopropane-1,3-diyl
adipoyl
1,4-phenylene
cyclohexane-1,4-diyl
oxy
thio
sulfonyl
imino
methylimino
hydrazo
piperidine-1,4-diyl

In naming non-linear homopolymer molecules, the


italicized prefix for the skeletal structure of the macromolecule is placed before the source-based name of the
constituent linear chain.
Assemblies of macromolecules held together by noncovalent bonds are named by a combination of the names of

silanediyl
dimethylsilanediyl
Before the total constitutional repeating unit (CRU) can
be given a unique name, a single preferred CRU must be
selected.
References page 1-12

For instance, in a polymer such as

it is immediately evident that a three-atom group (oxygen,


chlorine-substituted methylene group, and methylene
group) are being regularly repeated. Yet, the CRU can be
identified in at least three ways

d. for carbon-only acyclic chains, seniority is determined first by length, then by the number of
substituents, by the ascending order of locants,
and, finally, by the alphabetical order of the names of
the substituent groups.

c. carbocycles, e.g., 1,4-phenylene:

In all cases, the basic seniority rules apply only to those


atoms or groups of atoms that are in the main chain. The
kinds of substituents on the main chain (whether acyclic
carbon-only groups, or hetero-atom-containing groups, or
any ring systems) do not affect the selection of the CRU,
unless identical basic subunits in the chain have to be
further differentiated by the number of substituents and
their alphabetical order, but not by the type of the
substituent.
If completely identical subunits are separated by other
subunits, the direction of citation is determined by the
shorter part between them.
The preferred CRU is the one beginning with the subunit
of highest seniority. To establish direction, one proceeds
from this subunit to the neighboring subunit of the same
or next in seniority. In the example of a poly(chloroethylene oxide), shown above, where a regularly repeating
structure has been assumed, the subunit of the highest
seniority is the oxygen atom and the subunit next in
seniority is a substituted - C H 2 - C H 2 - . The substituted
subunit, - C H C l - C H 2 - , is oriented in such a way that the
substituent, chlorine atom, is assigned the lowest locant (1
rather than 2). The CRU is written to read from left to right.
Thus, the preferred CRU is

cyclobutane-1,3-diyl:
d. carbon-containing acyclic groups,
e.g., 1-chloroethylene: - C H C l - C H 2 propane-1,3-diyl: - C H 2 - C H 2 - C H 2 -

and the polymer

To obtain a unique name based on a preferred CRU, several


rules have to be applied. Rules have been developed to
specify both seniority among subunits, that is, the point at
which to begin writing the CRU, and also the direction in
which to move along the chain from left to right to reach
the end of the chain.
The order of seniority among the types of bivalent
groups that are parts of the chain of a single-strand polymer
is
a.

heterocycles, e.g., piperidine-l,4-diyl:


thiophene-2,5-diyl:

b. heteroatomic acyclic groups, e.g., oxy: - O - ,


sulfonyl: - S O 2 - , imino: - N H -

Within each structural type, the seniority is established by


further criteria:
a.

for heterocycles, a ring system containing nitrogen is


senior to a system containing a hetero atom other
than nitrogen, with further descending order of
seniority governed by the greatest number of rings in
the ring system, the largest individual ring in the ring
system, the largest number of hetero atoms, and the
greatest variety of hetero atoms;
b. for heteroatomic acyclic chains, oxygen is senior to
sulfur, sulfur to nitrogen, nitrogen to phosphorus,
phosphorus to silicon, silicon to germanium, etc.;
c. for carbocycles, a three-ring system is senior to a
two-ring system, a two-ring system containing two
6-membered rings is senior to one containing a 5and a 6-membered rings, a fused two-ring system
(two atoms common to both rings) is senior to a
spiro two-ring system (one atom in common), and an
unsaturated ring is senior to a saturated ring of the
same size;

is named
poly [oxy (1 -chloroethylene)]
The second example:

poly [(methylimino)methyleneimino-1,3-phenylene]
illustrates a polymer whose CRU starts with a substituted
nitrogen atom and proceeds through the shortest path to
the unsubstituted nitrogen atom and then through a
carbocycle.
The chemical structure of the CRU is enclosed in
parentheses or brackets. While dashes representing chemical bonds may be omitted within the formula unless
necessary for clarity, at the ends of the CRU, dashes must
be shown. They are drawn across the enclosing marks.

symbol a denoting the left-hand end group and the symbol


co denoting the other end group.

The third example:

Example:
poly(pyridine-3,5-diylcarbonyloxymethylene)
shows a polymer, whose CRU starts with a heterocycle and
then proceeds through a substituted carbon atom to a hetero
atom.
If the end groups of the chain are known, they may be
specified by adding prefixes to the polymer name, with the

Structure

a-(trichloromethyl)-co-chloropoly (1,4-phenylenemethylene)
The following table compares and contrasts structurebased and source-based names of some common polymers.

Structure-based name

Source-based or trivial name

Poly(methylene)
Poly(propylene)

Polyethylene
Polypropene

Poly (1,1 -dimethylethylene)


Poly (1 -methyl-1 -butenylene)

Polyisobutylene
Polyisoprene

Poly (1 -phenylethylene)

Polystyrene

PoIy(I -chloroethylene)

Poly(vinyl chloride)

Poly (1 -cyanoethylene)

Poly aery lonitrile

PoIy(I-acetoxyethylene)

Poly(vinyl acetate)

PoIy(1,1-difluoroethylene)
Poly(difluoromethylene)

Poly(vinylidene fluoride)
Polytetrafluoroethylene

Poly[(2-propyl-1,3-dioxane-4,6-diyl)methylene]

Poly(vinyl butyral)

Poly[ 1 -(methoxycarbonyl)-1 -methylethylene]

Poly(methyl methacrylate)

Poly(oxyethylene)

Poly(ethylene oxide)

Poly(oxy-1,4-phenylene)

Poly(phenylene oxide)

Poly[imino(l-oxohexane-1,6-diyl)]

Poly(e-caprolactam)

Poly(oxyethyleneoxyterephthaloyl)

Poly(ethylene terephthalate)

Poly(iminoadipoyliminohexamethylene)

Poly(hexamethylenediamine-a/?-adipic acid)
or poly(hexamethylene adipamide)
Poly(maleic anhydride-a/r-styrene)

Poly[(2,5-dioxotetrahydrofuran-3,4-diyl)( 1 -phenylethylene)]

References page 1-12

2.2. Regular Double-Strand Organic Polymers In a


double-strand polymer, the macromolecules consist of an
uninterrupted sequence of rings with adjacent rings having
two or more atoms in common (a ladder polymer) or one
atom in common (a spiro polymer).
As for a single-strand polymer, a single preferred
constitutional repeating unit (CRU) must be selected in
order to obtain a unique name [6]. The CRU is usually a
tetravalent group denoting attachment to four atoms and is
named according to the usual rules of organic nomenclature. Again, the name of the polymer is in the form of

common at each junction:

the name based on the preferred CRU is

poly(constitutional repeating unit)


Since the polymer has a sequence of rings, in order to
identify a preferred CRU, the rings must be broken by
observing the following criteria in decreasing order of
priority:
a. minimize the number of free valences in the CRU,
b. maximize the number of most preferred hetero atoms
in the ring system,
c. retain the most preferred ring system, and
d. choose the longest chain for acyclic CRU.
Further decisions are based on the seniority of ring
systems (indicated in the preceding section), on the
orientation of the CRU to give the lowest free valence
locant at the lower left of the structural diagram, and on
placing the acyclic subunits, if any, on the right side of the
ring system within the CRU.
For a polymer consisting of adjacent 6-membered
saturated carbon rings:

the name of the preferred CRU, which in this case is an


acyclic chain of four carbon atoms with four free valences
at each atom (the lowest at the lower left), is

poly (butane-1,4: 3,2-tetrayl)

poly(l,4-dithiin-2,3:5,6-tetrayl-5,6-dicarbonyl)
Here, by applying the seniority of the rings system, the
heterocycle was left intact, but the carbocycle was broken.
That left two bivalent acyclic subunits (carbonyl groups),
which according to the rule, have been placed on the right
side of the cyclic subunit, with attachments as in the
original polymer.
Another, still more complex ladder polymer, derived
from the polycondensation of 1,4,5,8-naphthalenetetracarboxylic dianhydride with 1,2,4,5-benzenetetramine:

poly[(7-oxo-7//,10//-benz[<ie]imidazo[4/,5/: 5,6]benzimidazo [2,l-a]isoquinoline-3,4:10,ll-tetrayl)-10-carbonyl]


illustrates a six-ring system with four free valences oriented
in such a way that the lowest free valence locant is at lower
left. It is followed within the total CRU by an acyclic group
at the upper right side of the diagram.
For a polymer consisting of regularly repeating adjacent
cyclohexane and 1,3-dioxane rings in a spiro sequence (one
atom in common at each junction):

the preferred CRU and the name are:

The free valence locants are always placed just in front of


the corresponding ending of the tetravalent unit and are
cited in the order
lower-left, upper-left: upper-right, lower-right
that is, in a clockwise direction, the left locants being
separated from the right locants by a colon.
For a more complex ladder polymer consisting of an
alternating sequence of 6-membered sulfur-containing rings
and keto-group containing carbocycles, with two atoms in

poly(2,4,8,10-tetraoxaspiro[5.5]undecane-3,3:9,9-tetrayl-9,9-diethylene)

2.3. Regular Single-Strand Inorganic and Coordination Polymers The names of inorganic and coordination
polymers are based on the fundamentals developed for
organic polymers [7]. As in the nomenclature of organic
polymers, these rules apply to structural representations

which may at times be idealized and do not take into


account irregularities, chain imperfections, or random
branching.
A constitutional repeating unit (CRU) is selected and
named. However, because of the basic difference between
the organic and inorganic nomenclature, the subunits of the
CRU are not named as bivalent groups, but as inorganic or
coordination groups indicating covalent and/or coordinate
bonding.
The name of the polymer is the name of the CRU
prefixed by the term "poly", "catena", or other structural
indicator. In order to arrive at the preferred CRU, seniorities
of the constitutent subunits are considered as well as the
preferred direction for the sequential citation.
The constituent subunit of the highest seniority must
contain one or more central atoms; bridging groups
between central atoms in the backbone of the polymer are
of lower seniority. This is consistent with the principle of
coordination nomenclature which puts the emphasis on the
coordination center.
Examples of homoatomic backbones are

catena-poly [dimethyltin]

caterca-poly[(difluorosilicon)
(dimethylsilicon)]

More common coordination polymers consist of a


mononuclear central atom with a bridging ligand. The
CRU of such a polymer cites the central atom first, which is
prefixed by its associated non-bridging ligands, followed in
turn by the name of the bridging ligand prefixed by the
Greek letter \i:

2.4. Regular
Quasi-Single-Strand
Coordination
Polymers In a regular quasi-single-strand coordination
polymer, the preferred CRU has one terminal constituent
subunit connected through a single atom to the next CRU
[7]. Such polymers are named as single-strand coordination
polymers:

catena-poly [palladiumdi-u-chloro]

catena-polyfsilicondi-u-thio]

catena-poly[platinum(ubromo-u-chloro)]

catena-poly [titaniumtri-u-chloro]

2.5. Irregular Single-Strand Organic Polymers Irregular polymers are named by placing the prefix "poly" before
the structure-based names of the constitutional units,
collectively enclosed in parentheses or brackets, with the
individual constitutional units separated by an oblique
stroke (a solidus) [8]. The stroke indicates the irregular or
unknown sequential arrangement of these units. The dashes
at each end of the formula are drawn fully inside the
enclosing marks to denote that these are not necessarily
terminal bonds of the macromolecule.
For instance, a partially hydrolyzed poly(vinyl acetate)
containing units:

is represented graphically and named:

catena-poly [(amminechlorozinc)-u-chloro]

catena-pory[(dihydroboron)-ju-(dimethylamido)]
poly( 1 -acetoxyethylene/1 -hydroxyethylene)

Multiple bridging ligands between the pair of central


atoms are cited in alphabetic order. Italicized element
symbols indicating the coordinating atoms in bridging
ligands are cited in the order of direction of the CRU and
are separated by a colon:

A copolymer of vinyl chloride and styrene joined head-totail is

poly (1 -chloroethy lene/1 -pheny lethylene)


A chlorinated polyethylene consisting of units

catena-poly [copper-[|i-chloro-bis-u-(diethyl
S')] -copper- u-chloro]

disulfide-S:
References page 1-12

is shown and named as

poly(chloromethylene/dichloromethylene/methylene)
C.

USE OF COMMON AND SEMISYSTEMATIC NAMES

The main purpose of chemical nomenclature is to identify a


chemical species by means of written or spoken words for a
useful communication among chemists. A systematic
nomenclature arose from the need to provide a relationship
between the structure and the name. In other words, the
reader should be able to deduce and identify the structure
from the name.
Traditional names, however, not necessarily based on
structures, have been widely used for many common
compounds. These are the so-called common, trivial, or
semisystematic names, which are satisfactory for communication within a given special chemical field.
It was earlier stated that in the macromolecular
nomenclature IUPAC is recommending the use of common
and semisystematic names for monomers in the sourcebased polymer names. The structure-based names, on the
other hand, are more related to the structural characteristic
of the polymers. But even there, IUPAC allows for a limited
number of common names for such substituent groups as
"allyl" and "vinyl", and for bivalent groups such as
"adipoyl" and "terephthaloyl".
The authors in this Handbook for the most part are using
the IUPAC-recommended names, or very close variants
thereof. On the other hand, in some compilations such as
"Crystallographic Data for Various Polymers" (in Section
VI), the author provides an excellent introduction and
explanation of the names used. For some structure-based
names, reflecting constitutional repeating units (CRU),
especially for those with a center of symmetry, the naming
of linking bivalent groups begins with the central subunit
and proceeds in both directions. The IUPAC method selects
the most senior bivalent group and proceeds naming from
left to right.

In no case, there is any misunderstanding in either case as


to which structure is associated with each name.
Abbreviations and acronyms are also extensively used in
the chemical literature for monomers, polymers, as well as
for additives, modifiers, and fillers. Their extensive list is
provided in Section VIII of this Handbook.
As is clearly stated there, the same abbreviation is often
used for different monomers and polymers, and the same
polymer may have different abbreviations or acronyms.
Examples:
1. DPP
2. PVA
3. trioctyl phosphate
4. polyacrylonitrile

diphenyl phthalate
dipropyl phthalate
poly(vinyl alcohol)
poly(vinyl acetate)
TOF
TOP
PAC
PAN

The IUPAC policy [9] on the use of abbreviations in the


chemical literature states that there are great advantages in
defining all abbreviations in a single conspicuous place in
each paper, preferably near the beginning of the paper in a
single list. An alternative is to define each abbreviation
fully the first time it appears in the text. No abbreviations
should be used in the titles of publications. A chapter of this
Handbook contains a set of abbreviations recognized by
international organizations.
D.

CHEMICAL ABSTRACTS (CA) INDEX NAMES

Chemical Abstracts Service (CAS), the publisher of printed


Chemical Abstracts (CA) and corresponding products and
services in microform, online databases, CD-ROM, and
World Wide Web also names the polymers, selected for
inclusion in the CAS Chemical Registry System and in the
CA Chemical Substance Indexes, in two ways:
a.

Examples:

Handbook name: poly(4,4'-sulfonyldiphenylene carbonate)


IUPAC name: poly(oxycarbonyloxy-l,4-phenylenesulfonyl-1,4-phenylene)
2.

Handbook name: poly (oxy die thy lene succinate)


IUPAC name: poly(oxyethyleneoxyethyleneoxysuccinyl)

in terms of the component monomer(s) from which


they are prepared
b. in terms of the final structure of the resulting
polymer.
There are definitive rules that govern when each type of
structure is recorded and named [3], The primary,
comprehensive representation of polymers by CAS is by
citation of the component monomer(s) because, in many
cases, the structure of the final polymer is either not known
or is not described in sufficient detail by the author.
When the polymer structure is well documented by the
author or can be confidently assumed, because one and only
one structure is chemically possible, then a supplementary
representation with a corresponding systematic name is
added to the CAS Registry System and included in the
printed indexes and online files.

The chemical nomenclature used by CAS has developed


in parallel, and generally in accordance, with the rules and
recommendations published by IUPAC. However, their
rules of systematic nomenclature do not necessarily lead to
a unique name for each compound, but do lead to an
unambiguous one. This causes no difficulty in normal
scientific communication, but is unacceptable in a formal,
rigidly controlled, alphabetic listing such as the CA
Chemical Substance Index.
The CA index names must not only be unambiguous,
unique, and totally reproducible, but also selected so as to
bring the names of structurally related substances into
juxtaposition in the alphabetic index. CAS has always
recognized that, while a unique name is needed for an index
and for substance identification, the use of such invariant
name in scientific papers is neither practicable nor
desirable.
In this section, it is intended to highlight the characteristics of the CA index names for polymers and compare
them with some of the typical names used in the scientific
community.
a.
b.

c.
d.

e.

IUPAC rules have been adapted to the specific needs


of a highly ordered alphabetical index.
Most common names were eliminated and exceptional treatment for various classes of substances
was discontinued.
A single preferred name is determined for each
identifiable substance.
A strict order of precedence of chemical functions
and compound classes is followed to determine the
preferred "index heading parent".
A total name is "inverted" by citing first the index
heading parent (usually, basic skeleton name with a
locant and suffix denoting the principal function),
followed by the comma of inversion, the substituents,
and the modification (derivative of the principal
function), e.g., 2-propenoic acid, 2-methyl-, methyl
ester

As mentioned above, most common names, including


those still sanctioned by IUPAC, have been replaced by
fully systematic names. The following is a short list of most
common monomers with both common names and CA
Index names:
Common
acrylamide
acrylic acid
acrylonitrile
adipic acid
8-caprolactam
8-caprolactone
ethylene glycol
ethylene oxide
fumaric acid

CA Index names (inverted form)


2-propenamide
2-propenoic acid
2-propenamide
hexanedioic acid
2//-azepin-2-one, hexahydro2-oxepanone
1,2-ethanediol
oxirane
2-butenedioic acid, (E)-

glycolic acid
hydroquinone
isophthalic acid
lactic acid
maleic acid
maleic anhydride
melamine
methacrylic acid
methyl acrylate
phthalic anhydride
propylene oxide
styrene
terephthalic acid
vinyl alcohol
vinyl chloride
vinylidene chloride

acetic acid, hydroxy1,4-benzenediol


1,3-benzenedicarboxylic acid
propanoic acid, 2-hydroxy2-butenedioic acid, (Z)2,5-furandione
1,3,5-triazine-2,4,6-triamine
2-propenoic acid, 2-methyl2-propenoic acid, methyl ester
1,3-isobenzofurandione
oxirane, methylbenzene, ethenyl1,4-benzenedicarboxylic acid
ethenol
ethene, chloroethene, 1,1-dichloro-

Similarly, commonly named substituent and multiplying


groups have their systematic equivalents in CA Indexes:
adipoyl
allyl
tert-butyl
ethylene
hexamethylene
isopropyl
succinyl
vinyl
vinylene

1,6-dioxo-1,6-hexanediyl
2-propenyl
1,1 -dimethylethyl
1,2-ethanediyl
1,6-hexanediyl
1-methylethyl
1,4-dioxo-1,4-butanediyl
ethenyl
1,2-ethenediyl

Homopolymers are described by the term "homopolymer" cited in the modification under the monomer name in
the index. In the structural diagram derived from the CAS
Registry System records, the structure of the monomer is
enclosed in parentheses followed by a subscript "x". The
corresponding empirical formula is also expressed in a
similar way.
Examples:
1. Poly (methacrylic acid):
(CH 2 =CH-COOH) x
CH3
(C 4 H 6 O 2 ),
CA name: 2-Propenoic acid, 2-methyl-, homopolymer
2. Polystyrene:
(CH2=CH)x
C6H5
(C 8 H 8 ),
CA name: Benzene, ethenyl-, homopolymer
3. PoIy(11-aminoundecanoic acid):
(H 2 N-(CH 2 )Io-COOH),
(C 11 H 23 NO 2 ),
CA name: Undecanoic acid, 11-amino-, homopolymer
References page 1-12

4. Poly (lac tic acid):


(CH3-CH-COOH)x
OH
(C3H6O3)*
CA name: Propanoic acid, 2-hydroxy-, homopolymer
Copolymers formed from two or more monomers are
described by the term "polymer with" (followed by the
other monomers in alphabetical order) cited in the
modification under each monomer name. In the structural
diagram derived from the CAS Registry System records, the
structures of monomers, separated by a period or periods,
are enclosed in parentheses followed by a subscript ' V .
The corresponding empirical formulas are similarly expressed. The descriptors alternating, block, and graft are
cited whenever applicable.
Examples:
1. Butadiene-vinyl ethyl ether copolymer:
(CH2=CH-CH=CH2CH2=CH-O-CH2CH3)X
(C4H8OC4H6)Jt (in Formula Index order)
CA names: 1,3-Butadiene, polymer with ethoxyethene
Ethene, ethoxy-, polymer with 1,3butadiene
2. Isophthalic acid-terephthalic acid-ethylene glycol
polyester:
(HOOC-m-C6H4-COOHHOOC-p-C6H4-COOHOH-(CH2)2-OH)X
(C 8 H 6 O 4 C 8 H 6 O 4 C 2 H 6 O 2 ),
CA names: 1,3-Benzenedicarboxylic acid, polymer
with 1,4-benzenedicarboxylic acid and
1,2-ethanediol
1,4-Benzenedicarboxylic acid, polymer
with 1,3-benzenedicarboxylic acid and
1,2-ethanediol
1,2-Ethanediol, polymer with 1,3-benzenedicarboxylic acid and 1,4-benzenedicarboxylic acid
Telomers are named as copolymers with the term
"telomer with" cited in the modification under both the
monomer (taxogen) and the chain-transfer agent (telogen).
In the structural representation, the monomer is enclosed in
parentheses with a subscript "*", followed by the telogen
structure. The corresponding empirical formula is
expressed in the same way.
Examples:
1. Vinylpyrrolidone homopolymer terminated with
mercaptopropionic acid:

CA names: 2-Pyrrolidinone, 1-ethenyl-, telomer


with 3-mercaptopropanoic acid
Propanoic acid, 3-mercapto-, telomer
with l-ethenyl-2-pyrrolidinone
2. Acrylic acid-vinyl choride copolymer terminated
with carbon tetrachloride:
(CH 2 =CH-COOH-CI-CH=CH 2 )X-CCI 4

(C3H4O2C2H3Cl)xCCl4
CA names: 2-Propenoic acid, telomer with chloroethene and tetrachloromethane
Ethene, chloro-, telomer with 2-propenoic acid and
tetrachloromethane
Methane, tetrachloro-, telomer with chloroethene
and 2-propenoic acid
Structural repeating units (SRU), equivalent to IUPAC
constitutional repeating units (CRU), are selected and
named for polymers that have well documented regular
structure, or can confidently be assumed. Assumptions are
made for
a. polyamides formed from a dibasic acid (ester or
halide) and a diamine; from an amino acid (ester or
halide); from a lactam;
b. polyesters formed from a dibasic acid (anhydride,
ester, or halide) and a dihydric alcohol (phenol);
from a hydroxy acid (ester, halide); from a lactone;
c. polycarbonates formed from carbonic acid (ester,
dihalide) and a dihydric alcohol (phenol);
d. polyurethanes formed from a diisocyanate and a
dihydric alcohol (phenol).
The structural repeating unit is named by citation of one
or more multivalent radicals of regular substitutive
nomenclature. The selection of the preferred SRU, its
orientation, and the construction of the name, proceeding
from left to right, follows the same rules as those in the
IUPAC recommendations for the CRU. In CA names,
however, the names of the radicals are fully systematic, as
explained and contrasted above. The empirical formula is
enclosed in parentheses followed by a subscript "n".
Examples:
1. Nylon 11:

CA name: Poly[imino(l-oxo-l,ll-undecanediyl)]
2. Poly(ethylene adipate):

CA name: Poly[oxy-1,2-ethanediyloxy(1,6-dioxo1,6-hexanediyl)]

3. Poly (ether ether ketone) (PEEK):

CA name: Poly(oxy-1,4-phenyleneoxy-1,4-phenylenecarbonyl-1,4-phenylene)
Poly(alkylene glycols) and their ethers and esters are
indexed in CA as structural repeating units with the
specified end groups, if aplicable.
Examples:
1. Poly(ethylene glycol):
HfO-CH 2 -CH 2 ^ n OH
CA name: Poly(oxy-l,2-ethanediyl), a-hydroco-hydroxy2. Poly(trimethylene glycol) dimethyl ether:
CH3 4 0 - C H 2 - C H 2 - C H 2 ^ O - C H 3
CA name: Poly(oxy-1, 3-propanediyl), a-methylco-methoxy3. Poly(tetramethylene glycol) diacrylate:
CH2=CH-C(O) 40-CH 2 -CH 2 -CH 2 -CH 2 ^ n
0-C(O)-CH=CH 2
CA name: Poly(oxy-1, 4-butanediyl), a-(l-oxo2-propenyl)-co- [(1 -oxo-2-propenyl)oxy ] E. POLYMER CLASS NAMES
In most textbooks, handbooks, encyclopedias, and indexes
to polymer nomenclature, information on polymer is
grouped under polymer class names. The following is a
list of such terms extracted from these sources.
Acrylic Polymers
Alkyd resins
Aminoplasts
Coumarone-indene-resins
Epoxy resins
Fluoropolymers
Phenolic resins
Polyacetals
Polyacetylenes
Polyacrylics
Polyalkylenes
Polyalkenylenes
Polyalkynylenes
Polyamic acids
Polyamides
Polyamines
Polyanhydrides
Polyarylenealkenylenes
Polyarylenealkylenes
Polyarylenes
Polyazomethines

Polybenzimidazoles
Polybenzothiazoles
Polybenzoxazinones
Polybenzoxazoles
Polybenzyls
Polycarbodiimides
Polycarbonates
Polycarboranes
Polycarbosilanes
Polycyanurates
Polydienes
Polyester-polyurethanes
Polyesters
Polyetheretherketones
Polyether-polyurethanes
Polyethers
Polyhydrazides
Polyimidazoles
Polyimides
Polyimines
Polyisocyanurates
Polyketones
Polyolefins
Polyoxadiazoles
Polyoxides
Polyoxyalkylenes
Polyoxyarylenes
Polyoxymethylenes
Polyoxyphenylenes
Polyphenyls
Polyphosphazenes
Polypyrroles
Polypyrrones
Polyquinolines
Polyquinoxalines
Polysilanes
Polysilazanes
Polysiloxanes
Polysilsesquioxanes
Polysulfides
Polysulfonamides
Polysulfones
Polythiazoles
Polythioalkylenes
Polythioarylenes
Polythioethers
Polythiomethylenes
Polythiophenylenes
Polyureas
Polyurethanes
Polyvinyl acetals
Polyvinyl butyrals
Polyvinyl formals
Vinyl polymers

These classes are not mutually exclusive, some are


relatively generic and some more specific. Some of them
References page 1-12

could be grouped and arranged in a hierarchy, e.g.,


Polyacetals
Polyvinyl acetals
polyvinyl butyrals
polyvinyl formals
Polyesters
polycarbonates

Polyethers
epoxy resins
polyetheretherketones
polyoxyalkylenes
polyoxymethylenes
polyoxyarylenes
polyoxyphenylenes

Some are synonymous or near synonymous, e.g.,


polyalkenylenes and polydienes, polyalkynylenes and
polyacetylenes, polyethers and polyoxides, polythioethers
and polysulfides.
F. REFERENCES
1. IUPAC, "Nomenclature of Regular Single-Strand Organic
Polymers (Recommendations 1975)", Pure Appl. Chem. 48,
373 (1976). Reprinted as Chapter 5 in Ref. 2.
2. IUPAC, "Compendium of Macromolecular Nomenclature".
W. V. Metanomski, (Ed.), Blackwell Scientific, Oxford,
1991.

3. Chemical Abstracts Service, "CA Index Guide 1997",


Appendix IV, "Chemical Substance Index Names",
Chemical Abstracts Service, Columbus, Ohio, 1997.
4. IUPAC, "Source-Based Nomenclature for Copolymers
(Recommendations 1985)", Pure Appl. Chem. 57, 1427
(1985). Reprinted as Chapter 7 in Ref. 2.
5. IUPAC, "Source-Based Nomenclature for Non-Linear
Macromolecules and Macromolecular Assemblies (Recommendations 1997)", Pure Appl. Chem. 69, 2511 (1997).
6. IUPAC, "Nomenclature of Regular Double-Strand (Ladder
and Spiro) Organic Polymers (Recommendations 1993)",
Pure Appl. Chem. 65, 1561 (1993).
7. IUPAC, "Nomenclature for Regular Single-Strand and
Quasi-Single-Strand Inorganic and Coordination Polymers
(Recommendations 1984)", Pure Appl. Chem. 57, 149
(1985). Reprinted as Chapter 6 in Ref. 2.
8. IUPAC, "Structure-Based Nomenclature for Irregular
Single-Strand Polymers (Recommendations 1994)", Pure
Appl. Chem. 66, 873 (1994).
9. IUPAC, "Use of Abbreviations in the Chemical Literature
(Recommendations 1979)", Pure Appl. Chem. 52, 2229
(1980).

U n i t s
J. Brandrup
Wiesbaden, FR Germany

A.
B.
C.
D.
E.

A.

Introduction
International Units
Si-Prefixes
Conversion Factors
Conversion Table for SI vs. English-American
Units

1-13
1-13
1-14
1-14
1-17

INTRODUCTION

The International System of Units (1) is used in this


Handbook as far as possible, since this system has become
obligatory in many European countries and since it is
supported by the National Bureau of Standards (2) and the
American Society for Testing and Materials (3). Only

cursory information is given here for units needed in this


Handbook. Detailed information may be found in the
following References:
1. "Si-units and recommendations for the use of their
multiples and of certain other units'', ISO 1000-1973.
2. "The International System of Units (SI)", Eds. C. H.
Page, P. Vigoreux, Natl. Bur. Std. Spec. Publ., 1981, 330.
3. "Standard Metric Practice Guide", ASTM E-380-85.
4. Manual of Symbols and Terminology for Physicochemical Quantities and Units; Pergamon Press, Oxford 1979
(Pure Appl. Chem., 51, 1 (1979).
5. F. S. Conant, using the SI units, Polym. Eng. ScL, 17,
222 (1977) (further references).

B. INTERNATIONAL UNITS
Selection of multiples
of the Si-unit

Quantity

Si-unit

Length
Area
Volume
Time
Frequency
Mass
Density
Force

m (metre)
m2
m3
s (second)
Hz (hertz)
kg (kilogram)
kg/m3
N (newton)

km, cm, mm, jum, nm


km2, dm2, cm2, mm2
dm3, cm3, mm3
ks, ms, us, ns
THz, GHz, MHz, kHz
Mg, g, mg, jag
mg/m3; kg/dm3; g/cm3
MN, kN, mN, uN

Pressure

Pa (pascal)
or N/m2

GPa, MPa, kPa,


mPa, uPa

Stress
Viscosity (dynamic)
Viscosity (kinematic)
Surface tension
Energy, work, heat

Pa or N/m2
Pas
m2/s
N/m
J (joule)

Power
Temperature
Thermal conductivity
Heat capacity
Specific heat
Entropy
Amount of substance
Electrical resistance
Electrical conductivity

W (watt)
K (kelvin), 0C
W/mK
J/K
J/(kgK)
J/K
mol (mole)
ft
S (I/ft)

GPa; MPa or N/mm2; kPa


mPas
mm2/s
mN/m
TJ, GJ, MJ,
kJ, mJ
GW, MW, kW, mW, uW

Accepted units
used with SI

Units accepted
temporarily
1A = 10 ~10 m

Non SI units
that should not be used
1 JJ. = 10 ~6 m

litre (1, L) (1 1= 1 dm3)


d, h, min
Iy= 10 ~9 kg

t
t/m3; kg/1
1 bar = 105 Pa
1 atm = 101325 Pa

Electronvolt (eV)
IeV1.602 x 10" 19 J

1 dyn = 10 ~5 N;
pond, kilopond
101325
1 Torr =
Pa
/OU
= 133.32Pa
poise; 1P = 0.1 Pas
stokes; 1 St= 1 cm2/s
dyn/cm
lerg=10~ 7 J
lcal = 4.1868J
I0K=IK
0.86kcal/(mhgrd)

kJ/K
kJ/(kgK)
kJ/K
Mole

1/13

SI-PREFIXES

Factor

Prefix

Symbol

Factor

Prefix

Symbol

10 18
10 15
10 12
10 9
10 6
10 3
10 2
10 l

exa
peta
tera
giga
mega
kilo
hecto
deca

E
P
T
G
M
k
h
da

10 ~l
10 ~2
10 ~3
10 " 6
10 ~9
10 " 1 2
10 ~15
10 ~18

deci
centi
milli
micro
nano
pico
femto
atto

d
c
m
\i
n
p
f
a

in

ft

yd

thou or mil

3.281
8.333 x 10~2
1
3
8.334 xlO~ 5

1.094
2.778 x 10~2
3.333XlO" 1
1
2.778 x 10" 5

3.937 x 104
1.0 x l O 3
1.2 x 104
3.6 x 104
1

D.

CONVERSION FACTORS

Length

Im
in
ft
yd
thou or mil

1
2.540 xlO~ 2
3.048XlO- 1
9.144X10" 1
2.540 xlO~ 5

Area

m2

Im2
sq. in
sq. ft
sq. yd
ar

1
6.452 x 10 ~4
9.29OxIO" 2
8.361 x KT 1
1.0 x l O 2

Volume

m3

1 m3
1 (lit)
cu. in
cu. ft
cu. yd
gal (US)
gal (UK)

Mass
lkg
lbm
ton (metric)
ton (UK)
cwt (UK)
ton (US)
ounce
grain
Density
lkg/m 3
Mg/m 3 =g/cm 3
lbm/cu. ft
lbm/cu. in
lbm/gal (UK)
lbm/gal (US)

3.937XlO 1
1
12
36
1.0 x l O " 3
sq. in
1.55OxIO3
1
1.44OxIO2
1.296 x 103
1.55OxIO5
1 (lit)

1
10~3
1.639 x 10 ~5
2.832 x 10~2
7.646XlO" 1
3.785 x 10~3
4.546 xlO~ 3

sq. ft

103
1
1.639 x 10 ~2
2.832 x 101
7.645 x 102
3.785
4.546

kg

lbm

1
4.536 x 10" 1
1 x 103
1.016 x l O 3
5.080 x 101
9.072 x 102
2.835 x 10~2
6.480 x 10 " 5

2.205
1
2.205 x 103
2.24OxIO 3
1.120 x 102
2.0 x 103
6.250 x 10~2
1.429 x 10 ~8

kg/m3
1
1.OxIO3
1.602 x 101
2.768 x 104
9.978XlO 1
1.198 x 102

1.076XlO1
6.994 x 10 ~3
1
9
1.076 x 103

sq. yd

ar

1.196
7.716 x 10 ~4
1.111 x 10" 1
1
1.196 x l O 2

l.OxlO" 2
6.452 x 10 ~6
9.29OxIO" 4
8.361 x 10" 3
1

cu. in

cu. ft

cu. yd

gal (US)

gal (UK)

6.102 x 104
6.102 x 101
1
1.728 x 103
4.666 x 104
2.31OxIO2
2.774 x 102

3.531 x 10l
3.531 x 10~2
5.787 x 10 ~4
1
2JxIO1
1.337 xlO" 1
1.605 x 10 - 1

1.308
1.308 x 10~3
2.143 x 10~5
3.703 x 10" 2
1
4.951 x 10~3
5.946 x 10~3

2.642 x 102
2.642 x 10" 1
4.329 x 10 ~3
7.481
2.02OxIO2
1
1.201

2.20 x 102
2.20 x 10" 1
3.605 x 10~3
6.229
1.682 xlO 2
8.327 x 10"1
1

ton (UK)
(long ton)
9.842xlO~ 4
4.464 x 10~4
9.842XlO" 1
1
5.0 x 10~2
8.929 x 10" 1
2.790 x 10~5
6.378 x 10 ~8

Mg/m3 = g/cm3
1.0 XlO" 3
1
1.602 x 10" 2
2.768 x 101
9.978 x 10~2
1.198 x 10" 1

cwt (UK)
(long cwt)

ton (US)
(short ton)

ounce

grain

1.968xlO~ 2
8.929 x 10~3
19.68
2.OxIO 1
1
1.786 x 101
5.580 x 10" 4
1.276 x 10 ~6

1.102xl0~ 3
5.0 x 10~4
1.102
1.120
5.600 x 10" 2
1
3.125 x 10~5
7.143 x 10 ~8

3.527XlO 1
1.6 x 101
3.527 x 104
3.584 x 104
1.792 x 103
3.2 x 104
1
2.286 x 10 " 3

1.543 x 104
7.0 x 103
1.543 x 107
1.568 x 107
7.840 x 105
1.4 x 107
4.375 x 102
1

lbm/cu.ft
6.243 XlO" 2
6.243XlO 1
1
1.728 x 103
6.229
7.480

lbm/cu.in

lbm/gal (UK)

lbm/gal (US)

3.613 x 10" 5
3.613xlO~ 2
5.789 x 10~4
1
3.605 x 10~3
4.329 x 10~3

1.002 x 10~2
1.002XlO1
1.605 x 10" 1
2.774 x 102
1
1.201

8.345 x 10" 3
8.345
1.337 x 10" 1
2.310 x 102
8.327XlO" 1
1

Force
IN
kp
lbf
dyn
tonf (UK)
tonf (US)

N (kg m/s2)

kgf, kp

lbf

dyn

tonf (UK) (long ton)

tonf (US) (short ton)

1
9.807
4.448
1.0 x IO"5
9.964 x 103
8.896 x 103

1.02OxIO-1
1
4.536 x 10~!
1.020 x 10~6
1.016 x 103
9.072 x 102

2.248 x HT 1
2.205
1
2.248 x 10~6
2.240 x 103
2.0 x 103

1.0 xlO 5
9.807 x 105
4.448 x 105
1
9.964 x 108
8.896 x 108

1.004 x 10~4
9.842 x 10~4
4.464 x 10~4
1.004 x 10~9
1
8.929 x 10"1

1.124 x 10" 4
1.102 x 10~3
5.0 x 10~4
1.124 x 10~9
1.120
1

Pressure
lPa(=lN/m2)
IkPa
1 MPa (=1 N/mm2
1 bar ( = 0.1 MPa)
lp/cm 2 t
lkp/m 2 t
lat^lkp/cm2)+
1 atm( = 760Torr)t
lTorr(= 1/760atm)f
Psi (lbf/sq. in)
f

Pa

MPa (N/mm 2 )

kPa

1
103
106
105
9.8IxIO 1
9.81
9.8IxIO 4
1.01325 x 105
1.33 x 102
6.895 x 103

10~3
1
103
102
9.8IxIO" 2
9.8IxIO" 3
9.8IxIO 1
1.01325 xlO 2
1.33XlO"1
6.895

10- 6
10" 3
1
10"1
9.8IxIO" 5
9.8IxIO" 6
9.81 x 10~2
1.01325XlO"1
1.33 x 10" 4
6.895 x 10" 3

bar

p/cm 2

kp/m 2

at+

atm*

Torrt

Psi (lbf/sq. in)t

10" 5
10" 2
10 !
1
9.81 x 10"4
9.8IxIO" 5
9.8IxIO" 1
1.013
1.33 x 10" 3
6.895 xlO" 2

1.02 x 10" 2
1.02x10'
1.02 xlO 4
1.02 xlO 3
1
10" !
103
1.033 x 103
1.36
7.03IxIO" 5

1.02XlO-1
1.02 xlO 2
1.02 x 105
1.02 xlO 4
10]
1
104
1.033 x 104
1.36XlO1
7.03IxIO" 6

1.02 x 10~5
1.02 xlO" 2
1.02x10"
1.02
10" 3
10~4
1
1.033
1.36 x 10" 3
7.031 x 10~2

9.87 x 10" 6
9.87 x 10" 3
9.87
9.87 xlO" 1
9.68 x 10 " 4
9.68 x 10" 5
9.68 xlO" 1
1
1.32 x 10" 3
6.805 xlO" 2

7.50xl0~ 6
7.50
7.5OxIO3
7.5OxIO2
7.36x10"'
7.36 x 10"2
7.36 xlO 2
7.6OxIO2
1
5.17IxIO" 1

1.450xl0~ 4
1.45OxIO-1
1.45OxIO2
1.45OxIO1
1.422 x 10 ~2
1.422 x 10~3
1.422XlO1
1.47OxIO1
1.934 x 10"2
1

Non SI units.

Stress
l P a ( = lN/m 2 )
lN/mm 2 (= IMPa)
lkp/cm2 ( = 1 at)t
lkp/mm 2 t
Psi lbf/sq. in

Pa

N/mm2

kp/cm 2t

kp/mm2t

Psi (lbf/sq. in)1

1
106
9.8IxIO 4
9.8IxIO 6
6.895 x 103

10" 6
1
9.8IxIO- 2
9.81
6.895 x 10~3

1.02 XlO" 5
1.02XlO1
1
102
7.031 x 10~2

1.02 xlO" 7
1.02XlO-1
10~2
1
7.031 x 10~4

1.45OxIO-4
1.45OxIO2
1.422XlO1
1.422 xlO 3
1

Non SI units.

Viscosity (dynamic)
lPas
mPas
cP
kps/m2
kph/m2
lbm/(fts)
lbm/(fth)
lbf s/sq. ft

Viscosity (kinematic)
Im2Zs
mm2/s
m2/h
cSt
sq. ft/s
sq. ft/h

Pas
(Ns/rcm2)
(kg/(sm))
1
1.0 x 10- 3
1.0 xlO" 3
9.807
3.530 x 104
1.488
4.134 x 10~4
4.788XlO 1

mPas
(mNs/m2)

cP

1.0 xlO 3
1.0 xlO 3
1
1
1
1
9.807 x 103
9.807 x 103
3.530 x 107
3.530 x 107
1.488 x 103
1.488 x 103
1
4.134 x 10" 4.134 x 10" 1
4.788 x 104 4.788 x 104

m2/s
1
1.0 x 10" 6
2.778 x 10~4
1.0 x IO' 6
9.290 x 10~2
2.581 x 10" 5

mm2/s
1.0 xlO 6
1
2.778 x 102
1.0
9.290 x 104
2.581 x 10" 1

kps/m 2

kph/m2

lbm/(fts)

1.02OxIO-1
1.020 x 10" 4
1.02OxIO-4
1
3.60 x 103
1.518 x 10"1
4.215 x 10~5
4.882

2.833 x 10 ~5
2.833 x 10~8
2.833 xlO~ 8
2.778 x 10" 4
1
4.215 x 10" 5
1.171 x IO"8
1.356 x l O " 3

6.720 x KT 1
6.720 x 10~4
6.72OxIO- 4
6.590
2.372 x 104
1
2.778 x 10" 4
3.2HxIO 1

m2/h
3.6OxIO3
3.60 x 10" 3
1
3.60 x 10- 3
3.345 x 102
9.290 x 10~2

cSt
1.0 x 106
1.0
2.778 x 102
1
9.290 x 104
2.581 x IO1

lbm/(fth)
2.419 x 103
2.419
2.419
2.372 x 104
8.540 x 107
3.60 x 103
1
1.158 x 105

sq. ft/s
1.076 x 10l
1.076 x 10~5
2.990 x 10"3
1.076 x 10~5
1
2.778 x 10~4

lbf s/sq. ft
2.089XlO" 2
2.089 x 10~5
2.089 x 10~5
2.048XlO- 1
7.373 x 102
3.103 x 10~2
8.634 x 10" 6
1

sq. ft/h
3.875 x 104
3.875 x 10~2
1.076 x 101
3.875 x 10" 2
3.60 x IO3
1

N/m (kg/s2)

Surface tension
lN/m
mN/m
kp/m
dyn/cm

Energy
IJ
kWh
kpm
PSh
lbfft
erg
HPh
kcal
BTU
a

J(Nm)
(kgm 2 /s 2 )
1
3.6OxIO6
9.807
2.648 x 106
1.356
1.0 x 10" 7
2.685 x 106
4.187 xlO 3
1.055 x 103

dyn/cm

1.02OxIO-1
1.020 xlO~ 4
1
1.020 x 10 ~4

1.0 xlO 3
1.0
9.807 x 103
1

kgfm
kpm

Psh

lbfft

erg

HPh

kcal

BTUa

1.02OxIO-1
3.67IxIO 5
1
2.70 x 105
1.363 x 10"1
1.020 x 10 " 8
2.737 x 105
4.269 X^ 102
1.076 x 102

3.777xlO~ 7
1.360
3.704 xlO~ 6
1
5.120 x 10"7
3.777 x 10~14
1.014
1.581 x 10" 3
3.985 x 10" 4

7.376X10" 1
2.655 x 106
7.233
1.953 x 106
1
7.375 x 10" 8
1.980 x 106
3.088 x 103
7.782 x 102

1.OxIO7
3.6OxIO13
9.807 x 107
2.648 x 1013
1.356 x 107
1
2.685 x 1013
4.187 xlO 1 0
1.055 x 1010

3.725xlO~ 7
1.341
3.653 x 10~6
9.863 x 10"1
5.051 x 10~7
3.725 x 10~14
1
1.560 xlO~ 3
3.930 x 10~4

2.388xlO~ 4
8.598 x 102
2.342 x 10~3
6.324 x 102
3.238 x 10~4
2.388 x IO' 11
6.412 x 102
1
2.520 x 10"1

9.478xlO~ 4
3.412 x 103
9.295 x 10~3
2.510 x 103
1.285 x 10~3
9.478 x 10"11
2.544 x 103
3.968
1

kWh
2.778xlO~ 7
1
2.724 xlO" 6
7.355 x 10"1
3.766 x 10~7
2.778 x 10"14
7.457 x 10"1
1.163 xlO~ 3
2.931 x 10" 4

kgf/m (kp/m)

1.0 xlO 3
1
9.807 x 103
1.0

1
1.0 xlO~ 3
9.807
1.0 x 10 ~3

British thennal unit.

J (Nm) (kgm 2 /s 2 )

Heat
1J
kcal
BTU
CHU
Wh
a

mN/m

kca!
2.388 x 10" 4
1
2.520 x 10" 1
4.539XlO" 1
8.598XlO" 1

1
4.187 xlO 3
1.055 x 103
1.90OxIO3
3.6OxIO3

BTU

CHU

9.478 x 10~A
3.968
1
1.80
3.412

5.262 x 10" 4
2.203
5.552 x 10" 1
1
1.894

Centigrade heat unit.

Power

W (J/s)
(kgm 2 /s 3 )

kgf m/s
kpm/s

1W
kpm/s
PS
HP
erg/s
ft lbf/s
kcal/h
BTU/h

1
1.020 x IO"1
9.807
1
7.355 x IO2
7.5 x IO1
7.457 x IO2 7.604 x 10l
1.0 x 10" 7 1.020 x 10~8
1.356
1.383 x 10" 1
1.163
1.186 x 10"1
2.931 x 10" 1 2.988 x 10~2

PS
HP (metr)
1.360 x 10" 3
1.333 x 10~2
1
1.014
1.360 x IO"10
1.843 x 10" 3
1.581 x 10" 3
3.985 x 10" 4

HP
1.341 x
1.315 x
9.863 x
1
1.341 x
1.818 x
1.560 x
3.930 x

erg/s
10~3
10" 2
10" 1
10" 10
10" 3
10" 3
10" 4

1.0 x 107
9.807 x 107
7.355 x 109
7.457 x IO9
1 x 10~8
1.356 x IO7
1.163 x IO7
2.931 x IO6

ft lbffs
7.376 x 10"1
7.233
5.425 x IO2
5.50 x IO2
7.375
1
8.578 x 10" 1
2.162 x 10" 1

kcal/h

BTU/h

8.598 x 10" 1
8.432
6.324 x 102
6.412 x IO2
8.598 x 10~8
1.166
1
2.520 x 10" 1

3.412
3.346XlO1
2.510 x IO3
2.544 x IO3
3.412 x 10" 7
4.626
3.968
1

Thermal conductivity

W/mK
(kgm/(s3K))

kcal/(mhC)

BTU/(fthF)

BTU/(inhF)

BTU in/
(sq.fthF)

1 W/(mK)
kcal/(mhC)
BTU/(fthF)
BTU/(inhF)
BTU in/(sq. fthF)

1
1.163
1.731
2.077 x IO1
1.442 x 10" 1

8.598 x 10~!
1
1.488
1.786 x IO1
1.24 x 10" 1

5.778 x 10~J
6.72OxIO" 1
1
1.2 x IO1
8.333 x 10~2

4.815 x 10~2
5.6OxIO" 2
8.333 x 10" 2
1
6.944 x 10~3

6.933
8.064
1.2XlO1
1.44 x IO2
1

Specific heat,
heat capacity

J/kgK
(m2Z(S2K))

kJ/(kgK)

kcal/(kgC)

BTU/(lbmF)

1 J/(kgK)
kJ/(kgK)
kcal/(kgC)
BTU/(lbmF)
Wh/(kgK)

1
1.0 x IO3
4.187 xlO 3
4.187 x IO3
3.6OxIO3

1.0 x 10 ~3
1
4.187
4.187
3.60

2.389 x 10 " 4
2.389 x 10" 1
1
1.0
8.598XlO" 1

2.389 x 10 ~4
2.389 x 10"1
1.0
1
0.8598

E.

C O N V E R S I O N TABLE FOR SI vs. E N G L I S H - A M E R I C A N U N I T S

SI to English-American unit

English-American unit to SI

Length
I m = 1.0936 yd = 3.28 ft
= 39.37 in
1 mm = 0.03937 in

lyd = 3 ft = 0.9144m
l f t = 12 in = 0.3048 m
Im = 25.4 mm

lkg = 2.20461b

lib = 0.45359 kg

1 N = l(kgm)/s 2 = 2.248 x 10" 1 lbf

I M = 4.448 N

1 Pa = 1 N/m 2 = 1.450 x 1O-4 lbf/in2

1 lbf /in 2 = 1 psi = 6.89475 x 103 Pa

Mass, weight

Force

Pressure
4

= 6.89475 x 10 ~2 bar

= 2.953 x 10 ~ in Hg
= 4.015 x 10~ 3 inH 2 O

HnHg = 3.38638 x 103Pa


= 3.38638 x 10"2 bar

1 bar = 105 Pa = 1.450 x 10l lbf /in 2


= 2.953 x 101UiHg

ImH 2 O = 2.49089 x 102Pa

= 4.015 x 10 HiH 2 O

= 2.49089 x 10 " 3 bar

Tension, stress
lN/mm 2 = 1.450 x 10 2 lbf/in 2

1 lbf/in2 = 6.89475 x 10 " 3 N/mm 2

Dynamic viscosity
IPas = (Ns)/m 2 = 2.089 x 10~2 (lbf s)/ft2
1

= lkg/(ms) = 6.72x 10" lbf/(ft s)

1 (lbf s)/ft2 = 4.78802 x 101 Pas


llb/(fts) = 1.488 Pa s

Kinematic viscosity
I m 2 / s = 1.076 x 101 ft 2 /s

Ift 2 /s = 9.29x 10~ 2 m 2 /s

U = I W s = INm = 7.376 x 10"1 ftlbf

1 ft lbf = 1.35582 J

Energy, quantity of heat

IkJ = 9.478 x 10- BTU

IBTU= 1.05506 kJ

Power, heat flow rate


I W = I Nm/s = 7.367 x 10 - 1 (ftlbf)/s
1

= 1 J/s = 4.425 x 10 (ftlbf)/min


= 3.412 BTU/h

l(ftlbf)/s= 1.35582 W
1 (ftlbf)/min = 2.25969 x 10~2 W
1 BTU/h = 2.93072 x 10" 1 W

Specific heat capacity


1 J/(kg K) = 2.388 x 10~ 4 BTU/(lb/ 0 F)
3

1 J/(m K) = 1.491 x 10~ BTU/(ft

3 0

F)

IBTU/(Ib 0F) =4.1868 x 10 3 J/(kgK)


IBTU/(ft 3 0F) =6.71 x 10 4 J/(m 3 K)

Thermal conductivity
1 W/(mK) = 6.933 (BTUin)/(ft 2 h F)
= 5.778 x 10~ 1 BTU/(fthF)
= 4.815 x 10 " 2 BTU/(inh 0F)

1 (BTUin)/(ft2h F) = 1.442 x 10^1 W/(mK)


lBTU/(fthF) = 1.7307 W/(m K)
1 BTU/(in h F) = 2.07689 x 101 W/(mK)

English-American unit to SI

SI to English-American unit
Heat flux density

lBTU/(ft 2 h) = 3.1546 W/m 2

l W / m 2 = 3.17x 10- 1 BTU/(ft 2 h)

1BTU/(in2 h) =4.54263 x 10 2 W/m 2

= 2.201 x Kr 3 BTU/(in 2 h)
Heat transfer coefficient
lW/(m 2 K) = 1.761 x 10- 1 BTU/(ft 2 hF)

1 BTU/(ft2 h F) = 5.678 W/(m 2 K)

1 (m2 K)/W = 5.678 (ft2 h F)/BTU

1 (ft2h F)/BTU = 1.761 x 10- 1 (m 2 /K)/W

I K = I 0 C = 1.8 0 F

1 0F = 5.555 x 10" 1 K = 5.555 x 10" 1 0C

Thermal resistance

Temperature

Conversion:
Tc= ^(rF-32)

r F = | r c + 32

7 K = ^ Tp+ 255.372

TF = I (TK- 255.372)

TQ - Temperature in Celsius ( 0 C); T? - Temperature in fahrenheit (0F); TK -

Temperature in kelvin (K).

S E C T I O N

Z
E

A
R

T
I

Il

I
Z

O
A

N
T

A
I

N
N

D e c o m p o s i t i o n
F r e e

R a t e s

R a d i c a l

o f

O r g a n i c

I n i t i a t o r s

K. W . D i x o n
Akzo Nobel Chemicals Inc., Dobbs Ferry, NY, USA
A. Introduction
11-1
B. Tables of Decomposition Rates of Organic
Free Radical Initiators
II-2
Table 1. Azonitriles
II-2
Table 2. Miscellaneous AzoDerivatives
M-9
Table 3. Alkyl Peroxides
II-23
Table 4. Acyl Peroxides
II-29
Table 5. Hydroperoxides and Ketone Peroxides II-43
Table 6. Peresters and Peroxy Carbonates
II-48
Table 7. Miscellaneous Initiators
II-68
C. Notes
II-69
D. References
II-70
A.

INTRODUCTION

The decomposition of most organic free radical initiators


follows first order kinetics. With certain peroxides, however, higher order decompositions are observed. Generally,
the higher order reaction is caused by a reaction of radicals
with the initiator (induced decomposition). The value of the
rate for unimolecular decomposition may be determined
either by extrapolation of the rate back to zero initiator
concentration or by use of a monomer or other radical
"trap". Some of the peroxides may also decompose by
non-radical routes. Acids, bases, and polar solvents favor
ionic intermediates. Koenig (296) presents an excellent
discussion of azo and peroxide decomposition pathways.
Decomposition rate (kd) data in these tables are reported
for first order kinetics:

where / is the initiator concentration (mol/1) and t is the


time (s). The decomposition rate constant k^ is related to
half-life (t ^ 2 ) by the following equation:

Fig. 1 relates kd in s" 1 to half-life for the range of k^ found


in the tables.
For some of the initiators listed, the enthalpy (AH *) is
given (Note h) rather than the Arrhenius activation energy

(E2). The two quantities are related by the equation


a = AH* +RT, where R is the gas constant (in kJ/moldeg.) and T is the absolute temperature (94). Assuming that
k& is linear with respect to \/T and that the activation
energy, a , and the decomposition rate constant, kd, for one
temperature are known, kd for any temperature can be
calculated from the following expression:

Where given by the author, the overall equation for kd in


terms of the frequency factor (A) and activation energy ( a )
has been included. Thus for any temperature (converted to
K) the kd may be calculated:

Although a wide range of initiators is reported in the tables,


the author admits that the compilation is far from complete.
There are several purposeful omissions: (a) azo compounds,
where the azo group is part of a ring structure - these
recombine almost exclusively; (b) compounds that decompose at appreciable rates only above 200 degrees. Neither
class would be expected to be useful initiators. The data
have been arranged into seven tables. Within each table the
individual initiators are listed according to the following
criteria:
1. Initiators:
(a) according to increasing number of carbon atoms;
(b) alphabetically (neglecting trivial prefixes), for
compounds containing equal number of carbons;
(c) miscellaneous initiators are listed alphabetically in
Table 7.
2. For each initiator, solvents are listed alphabetically.
3. For a given solvent, all measurements reported by one
investigator are listed in a series, with the activation
energy listed opposite the lowest temperature.
Abbreviations: DMSO - dimethyl sulfoxide; DMAC dimethylacetamide; DMF - dimethylformamide; THF tetrahydrofuran; DCB - 1,2-dichlorobenzene.

20hrs.
100 days

120 min.

12 min.

10 days

100 sec.
200 min.

10 sec.

1 sec.
0.12 sec.

20 min.

40hrs.
200 days
_200 sec.

60 min.

1 year
50 days

100 hrs.

10 hrs.

40 sec.

0.5 sec.

5 sec.

10 min.
Rate constant (*d)

Figure 1. Relationship of half life to rate constant (k^) (half lives are to the right of each vertical line)

B.

TABLES O F D E C O M P O S I T I O N RATES O F O R G A N I C FREE R A D I C A L I N I T I A T O R S

TABLE 1. AZONITRILES
Number of
C atoms
5

Initiator

Solvent

N-Acetyl N'-oc-cyanoethyl diimide

Toluene

2-Cyano-2-propyl-azo-formamide

Chlorobenzene
Toluene

Xylene

2-(Carbamoylazo)isobutyronitrile
N-Acetyl N'-ot-cyanocyclopentyldiimide

Toluene
Toluene

2,2/-Azo-bis-isobutyronitrile
(2,2'-azo-bis-2-methylpropionitrile)

Acetic acid

Acetonitrile
tert-Amyl alcohol
Aniline
Benzene

T( 0 C)
60.8
68.6
82.0
100
100
110
104
100
120
104
65.7
76.8
91.5
79.9
79.9
79.9
80
82
82
79.9
79.9
80.2
80.2
40.0
45.2
50.0
55.0
60.5
69.5

^d(S"1)
2.46 x 10 " 5
5.45 x l 0 ~ 5
2.49 xlO~ 4
1.5 x 10 " 5
2.1 x 10 ~5
6.8 x l O " 5
1.9 XlO" 5
2.IxIO-5
2.4xlO-4
1.93 x 10 ~5
1.82 x l O " 5
7.29 x 10 ~5
3.65 x l O " 4
1.43 x 10 ~4
1.48 x 10 ~4
1.62 XlO" 4
1.52 x l O - 4
1.50xl0" 4
1.49 XlO" 4
1.25 x 10 " 4
1.24 xlO~ 4
1.40 x 10~4
1.68 x l O " 4
5.44 x l O " 7
1.12 XlO" 6
2.64 XlO" 6
5.19 x l O " 6
1.16 x l O " 5
3.78 x l 0 ~ 5

Ea (kj/mol)

Notes

110.2

144.3
a
144.3
a
120.3

V2
V3
a
a
a
v2

128.4

a,t2
a,t2
a,t2
a,t2
a,t2
a,t2

Refs.
322
322
322
93
93
93
339
93
93
340
322
322
322
146
146
146
62
2
175
146
146
61
61
69
69
69
69
69
69

TABLE 1. cont'd
Number of
C atoms
S (cont'd)

Initiator
2,2'-Azo-bis-isobutyronitrile

Solvent
Benzene

Benzene or Toluene

H-Butanol
Isobutanol
Di-n-butyl phthalate

Carbon tetrachloride

Chlorobenzene

Cyclohexanone
Dichloroethane
Dichloroethane:
propionitrile (1:1)
Diethylene glycol
monobutylether
DMF
DMF
DMF/methyl
methacrylate (9/1)
(8/2)
(7/3)
(6/4)
(5/5)
(4/6)
(3/7)
(2/8)
(1/9)
N,iV-Dimethylaniline

Dioxane/Water (80/20)
pH7.0

Dioxane/Water (80/20)
pH 10.7
Dodecanethiol

T( 0 C)
40
50
60
70
78
37
43
50
60
100
T (K)
82
82
82
80.2
80
90
100
110
120
127
137
145
80
90
100
110
120
40
60
77
64
82
101
T (K)
82
70

^d(S"1)

Ea (kj/mol)

4.83 x 10~7
2.085 XlO" 6
8.45 xlO~ 6
3.166 XlO" 5
8.023 x l O " 5
2.83 x 10 ~7
7.35 x l O - 7
2.16 x l O " 6
9.15 x l O - 6
1.52 x l O - 3
1.58 x 1015
1.54 x 10~4
1.55 XlO" 4
1.66 x 10~4
(1.67-1.76) x 10~4
2.64 x 10 ~4
6.47 x l O - 4
1.78 XlO" 3
4.88 x l O - 3
1.43 XlO" 2
2.48 x l O " 2
5.43 XlO" 2
1.24XlO- 1
2.22 x l O " 4
4.23 XlO" 4
1.99 x l O - 3
5.3 x l O " 3
1.48 x l O - 2
2.15XlO" 7
4.0OxIO- 6
1.2IxIO- 4
1.93 x 10 ~5
1.93 x l O - 4
1.93 x l O - 3
2.89 x 1015
1.43 x 10 ~4
2.0IxIO- 5
1.64 x l O - 5

123.4

Notes

128.9

exp[- 128.9/#7]
a
a
a
122.2

y4
y4
y4
y4
y4
y 16
y 16
y 32

128.4

a,t2
a,t2
a

exp[- 130.23//?7]
a
m8

Refs.
66
66
66
66
66
39
39
39
19
39
39
175
2
2,175
61
236
236
236
236
236
236
236
236
375
375
375
375
375
69
69
62
344
344
344
344
2,175
293
293

1.94 x 10~5
2.442 x 10 ~5

293
26

6.2096 x l O - 5
6.45 x l O - 4

294
355

60
60
60
60
60
60
60
60
60
66.82
72.27
80
65.3
70.0
75.0
80.0

5.55 x 10~4
5.1OxIO- 4
5.1OxIO- 4
5.3OxIO- 4
5.65 x 10 ~A
5.35 x l O - 4
5.65 x l O - 4
6.25 x l O - 4
6.5OxIO- 4
3.483 x 10~5
6.914 XlO" 5
1.83 x l O - 4
2.53 x 10 " 5
3.20xl0~ 5
8.5 x l O - 5
1.62 x l O - 4

355
355
355
355
355
355
355
355
355
26
26
62
186
186
186
186

75.0
80

1.72 x l O " 4
1.46 x 10 ~4

70
66.82
71.2
60

a
141.0

186
62

Notes page 11-69; References page 11-70

TABLE 1. cont'd
Number of
C atoms
S (cont'd)

Initiator
2,2'-Azo-bis-isobutyronitrile

Solvent
Ethyl acetate
Ethyl acetate/
SnCl4 (1:1)
Glycerol/DMF 95/5, (v/v)
Maleimide (solid state)
Methyl methacrylate

Nitrobenzene
1-Nitrobutane
Propionitrile/SnCl4 (1:1)
Propylene carbonate
Styrene

Toluene

Toluene/SnCl4 (1:1)
Xylene

o-Xylene

3,6-Dicyano-3,6-dimethyl1,2-diazacyclohexene-l

Water
Dichloromethane

2,2/-Azo-bis[2-(hydroxymethyl)propionitrile

Methyl cellosolve

N-Acetyl W-a-cyanocyclohexyldiimide

Toluene

10

N-Acetyl N'-oc-cyanocycloheptyldiimide

Toluene

4,4/-Azo-bis-(4-cyanopentanol)
4,4/-Azo-bis-(4-cyanovaleric acid)
l,r-Azo-bis-l-cyclobutanenitrile

Acetone
Acetone
Mesitylene

2,2'-Azo-bis-2-methylbutyronitrile

Xylene
Toluene
Xylene

T( 0 C)
40
60
T (K)
71.2
65
72
50
50
60
70
70
80
100
82
T (K)
72.27
50
70
T (K)
68.4
60.00
60
65
70
80.4
90.0
100.0
105.0
69.8
80.2
80.3
60
50
77
82
80
80
82
85
95
105
T(K)
50
-6.06
0.03
2.52
77

82.0
92.8
100.6
59.4
66.1
79.6
70
70
130.4
141.6
120.4
69.8
80.2
80

kA (s^1)
4.7 x l O " 7
9.36 XlO- 6
8.56 x 1015
2.6054 x 10~5
4.97 x 10 ~5
2.07 x l O - 4
9.7 x 10 ~7
7.5 x l O - 6
7.2OxIO- 4
3.1 x 10" 5
1.27 x l O - 4
1.98 x l O " 4
2.24 x l O - 3
1.45 x l O " 4
9.10 x 1015
5.821 x 10 ~5
2.97 x 10~6
4.72 x l O - 5
1.29 x 1015
3.8 x l O - 5
9.03 x 10~6
9.8 x l O " 6
1.9 x l O - 5
4.OxIO- 5
1.55 x l O - 4
4.86 x 10- 4
1.6OxIO- 3
2.61 x 10 - 3
3.8 x l O - 5
(1.72-1.60) x 10- 4
1.3OxIO- 4
4.0 x 10" 5
2.OxIO- 6
9.46 x l O - 5
1.44 x l O - 4
1.53 xlO~ 4
1.5OxIO- 4
1.45 x l O " 5
2.75IxIO- 4
9.58IxIO- 4
2.782 x l O - 3
3.16xl0 1 5
1.56 x 10 ~6
4.6OxIO- 4
1.14 x l O " 3
1.64 x l O - 3
1.93 x 10 ~5

5.2IxIO- 5
1.7OxIO- 4
3.74 XlO" 4
4.44 x 10 ~5
9.82 x 10 ~5
4.51 x 10- 4
4.26 x 10~5
4.58 x 10 ~5
5.20xl0"5
1.6OxIO- 4
2.05 x 10 ~5
2.3 x IO"5
8.4-9.OxIO- 5
9.97 x 10~5

Ea (kj/mol)

Notes

128.5

a,t2
a,t2

exp[- 121 A/RT]

a
a
a
a,v20

132.2

V4
a
a
a

exp[- 121.0/RT]
127.6

a
a

exp[- 127.6/RT]
c,m3
a
121.3

142.3
m2

131.0

a
a
a
a
a,t4
a

131.8

exp[-131.8//?7]
88.8

114.8

112.0

m7
ni7
134.3

129.7
123.0

Refs.
69
69
290
294
185
185
289
289
355
216
216
226
226
2,175
290
26
132
132
132
234
291
290
339
47
47
47
47
47
61
61
234
290
175
175
175
62
62
2
332
332
332
332
285
252
252
252
339

322
322
322
322
322
322
305
305
101
101
101
61
61
62

TABLE 1. cont'd
Number of
C atoms

Initiator

10 (cont'd)

2,2'-Azo-bis-2-ethylpropionitrile

Nitrobenzene

2,2'-Azo-bis-2-methylbutyronitrile

Cyclohexanone

Solvent

Chlorobenzene

Ethanol

Ethylbenzene

N-benzoyl iV'-a-cyanoethyldiimide

4-Bromophenyl-azo-2-methyl2-propionitrile
4-Bromophenyl-azo-(methylpropanedinitrile)

DCB

4-Nitrophenyl-azo-2-methyl2-propionitrile
4-Nitrophenyl-azo-2-(methylpropanedinitrile)

DCB

Phenyl-azo-2-methyl-2propionitrile
Phenyl-azo-2-(methylpropanedinitrile)

11

Toluene
Toluene

DCB

DCB

DCB
DMF
1,2,4-Trimethylbenzene
DCB

Phenyl-azo-2-(methylpropanedinitrile)

DCB

4-Bromophenyl-azo-2-(ethylpropanedinitrile)

DCB

4-Methoxyphenylazo-2(methylpropanedinitrile)

Butanol
Chlorobenzene
DCB
Decane
DMSO
Heptane
Hexanol
Octane
Octanol
Propanol
Toluene
Chlorobenzene

4-Methoxyphenyl-azo2-(methylpropanedinitrile)

DCB

T( 0 C)
80
100
79.9
90.0
100.1
66
84
104
T (K)
80.0
90.0
100.0
80.0
90.0
100.0
67
69.2
83.2
90.0
160
80
85
90
T (K)
160
80
85
90
T(K)
160
160
160
80
85
90
T (K)
80
85
90
T (K)
80
85
90
T (K)
85
85
85
85
85
85
85
85
85
85
85
78.1
85.3
90.2
75.0
85.1
95.1
104.9

kd (s"1)
8.3 x 10~5
1.08 x l O - 3
1.06 x l O " 4
3.7IxIO-4
1.27xlO- 3
1.93 x 10 ~5
1.93 x l O - 4
1.93 XlO" 3
1.38 x 1015
1.05 x 10 " 4
3.23 x l O - 4
9.87 x l O - 4
8.22 x l O " 5
2.94 x l O - 4
1.02 x l 0 ~ 3
1.9 x l O " 5
1.31 x 10 ~5
7.96 x l O - 5
1.744 xlO~ 4
2.85 x 10 ~5
2.4xlO" 5
4.8xlO-5
9.4 x 10 ~5
7.23 xlO 1 6
2.3 x 10 " 5
3.1 x 10~5
6.0xl0"5
1.14 x l O - 4
1.35 xlO 1 6
5.65 x 10~5
6.9xlO" 5
5.35 x 10 ~5
4.45 x 10 ~5
8.0xl0"5
1.42 x l O - 4
8.48 x 1013
2.4xlO~ 5
4.8xlO" 5
9.4 x l O - 5
7.23 x 1016
1.85 x 10 " 5
3.65 x 10 ~5
7.05 x l O - 5
3.00 x 1016
2.9xlO" 4
9.5 x 10" 5
8.35 x l 0 ~ 5
3.8xl0"5
4.87 XlO" 4
5.15 x l 0 ~ 5
1.6 x l O " 4
4.4xlO~ 5
1.5xlO~ 4
3.1 x 10~4
6.75 x l 0 ~ 5
5.76 x 10 ~5
9.52 x 10 ~5
1.307 xlO~ 4
2.73 x l 0 ~ 5
8.35 x l 0 ~ 5
2.236 xlO~ 4
6.397 xlO~ 4

Ea (kj/mol)

Notes

143.1
131.6

a
a
h

exp[- 129.93//?7]
119.8

134.9

a
127.9

145.0

exp[-U5.0/RT]

139.1

exp[-139.1 /RT]

123.2

exp[- 123.2/RT]
145.0

exp[- 145.0/RT]
142.9

exp[- 142.9/RT]
110
71
115
142
114
136
102
140
112
103
137
71.5

116

Refs.
226
226
336
336
336
344
344
344
344
336
336
336
336
336
336
339
322
322
322
329
329
329
329
329
329
329
329
329
329
329
329
329
329
329
329
329
329
329
329
329
329
329
329
329
331
331
331
331
331
331
331
331
331
331
331
330
330
330
330
330
330
330

Notes page 11-69; References page 11-70

TABLE 1. confd
Number of
C atoms
11 {confd)

Initiator
4-Methoxyphenyl-azo2-(methylpropanedinitrile)

DCB

Phenyl-azo-2-(2-methylbutyronitrile)

DCB
DMF
1,2,4-Trimethylbenzene
DCB

4-Tolyl-azo-2-(methylpropanedinitrile)

12

13

14

Solvent

4,4/-Azo-bis-(l-bromo4-cyanopentane)
4,4/-Azo-bis-4-cyanopentanoic acid
4,4'-Azo-bis-(4-cyanopentanol)

Toluene

U'-Azo-bis-l-cyclopentanenitrile

Toluene

2,2'-Azo-bis-2-cyclopropylpropionitrile (mp 64-65)

Toluene

2,2'-Azo-bis-2-cyclopropylpropionitrile (mp 76-77)

Toluene

2,2'-Azo-bis-2,3dimethylbutyronitrile
2,2/-Azo-bis-2-methylvaleronitrile
4-Bromophenyl-azo-2(isopropylpropanedinitrile)

Toluene

T(K)
80
85
90
T (K)
160
160
160
80
85
90
T(K)
T(K)

kd (s"1)
5.67 x 1012
4.7xlO~ 5
8.1 x 10 " 5
1.38 x l O " 4
2.94 x 1012
5.OxIO" 5
5.2xl0~ 5
5.05 x 10 " 5
4.5xlO" 5
7.9xl0~5
1.365 XlO" 5
1.21 x 1013
1.OxIO11
1.9 x l O " 5
8.97 x 10 " 5
2.55 x 10 " 4
7.99 XlO" 4
2.81 x 10" 3
8.99 x l O " 3
2.6xlO-2
5.2 XlO" 2
7.45 x l O " 5
2.43 x 10 " 4
5.18 xlO~ 4
3.50 x 10~5
7.53 x 10 ~5
2.68 XlO" 4
3.90 x 10 ~5
8.17 x 10 " 5
2.46 XlO" 4
2.6 x l O " 5
1.02 x 10 " 4
4.2xlO~ 5
(1.65-1.74) x 10" 4
1.4xl0~ 5
2.80xl0"5
5.4 XlO" 5
1.73 xlO 1 6
3.06 x 10 " 5
1.177 x 10 ~A
4.594 XlO" 4
7.320xl0" 4
2.06 xlO 1 7
1.62 x l O " 5
3.17 x 10 " 5
2.252 XlO" 4
1.12 x l O " 4
2.21 x 10 " 4
4.26 XlO" 4
1.19 xlO 1 7
4.85 x 10 " 5

a (kj/mol)

Notes

exp[- U6/RT]
114.8

Refs.
330
329
329
329
329
329
329
329
329
329
329
329
307

exp[- 114.S/RT]

117.7

exp[- UlJ/RT]
exp[-104.7 /RT]

2,6-Dimethylphenyl-azo2-methylpropanedinitrile

DCB

N-Benzoyl W-a-cyanocyclopentyl diimide

Toluene

4-Bromophenyl-azoisobutylpropanedinitrile

DCB

4-Bromophenyl-azo-2(2-terf-butylpropionitrile)
4-Nitrophenyl-azo-2(2-terf-butylpropionitrile)
Phenyl-azo-2-(2-terf-butylpropionitrile)

DCB

69
80
80
90
100
110
120
130
80.3
89.2
95.1
44.2
49.5
59.2
44.2
49.5
59.3
69.8
80.2
69.8
80.2
80
85
90
T(K)
60.1
70.0
80.6
84.5
T(K)
76.7
82.0
98.4
80
85
90
T(K)
160

DCB

160

1.8 x l O " 5

329

DCB
1,2,4-Trimethylbenzene
Hexamethylphosphoramide
Toluene

160
160
160

9.35 x 10 " 5
9.65 x 10 ~5
9.5xl0~5

329
329
329

2,2'-Azo-bis-2-cyclobutylpropionitrile (mp 38-42)


2,2'-AzO-Ws^-CyClObUIyIpropionitrile (mp 81.5-82.5)

Water

T( 0 C)

Di-w-butyl phthalate

Toluene
DCB

Toluene

142.3

a
a

141.4

117.2

108.8

w
w
w
w
w
w

133.9
138.1
142.0

exp[- 142.0/RT]
130.5

exp[-130.5//?7]
131.9

141.6

exp[-141.6kJ//?7]

339
62
375
375
375
375
375
375
101
101
101
57
57
57
57
57
57
61
61
61
61
329
329
329
329
330
330
330
330
330
322
322
322
329
329
329
329
329

80.5

1.51 x 10 " 4

104

80.5

1.51 x 10 " 4

104

TABLE 1. cont'd
Number of
C atoms

Initiator

Solvent

14 {cont'd)

U'-Azo-bis-l-cyclohexanenitrile

Chlorobenzene
DMSO

Nitrobenzene
Toluene

2,2'-Azo-bis-2,4-dimethylvaleronitrile

Dimethyl-4,4'-azo-bis-cyanopentanoate (meso)

Xylene
Toluene

Xylene
DMAC

(no+)

(nD_)

4,4'-Azo-bis-4-cyano-l-methylpiperidine

DMSO

2,2'-Azo-bis-2-propylbutyronitrile

Nitrobenzene

2,2/-Azo-bis-2,3,3-trimethylbutyronitrile(mp 114-116)
2,2'-Azo-bis-2,3,3-trimethylbutyronitrile (mp 116-118)
2,2/-Azo-bis-2-methylhexylnitrile
2,2'-Azo-bis-2,4-dimethylvaleronitrile

Toluene

2,2/-Azo-bis-2,4-dimethylvaleronitrile
(mp 56-57)
2,2/-Azo-bis-2,4-dimethylvaleronitrile
(mp 74-76)
2,2/-Azo-bis-2-isopropylbutyronitrile
AH4-Chlorobenzoyl) N'-OLcyanocyclohexyl diimide
AHl-Cyanocyclohexyl)pentamethyleneketenimine

Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene

Chlorobenzene
Cumene
Toluene
terf-Butylbenzene

15

2-Phenyl-azo-2,4-dimethyl4-methoxyvaleronitrile
JV-Benzoyl N'-ot-cyanocycloheptyl diimide

Xylene
Toluene

T( 0 C)
79.97
100.12
80
85
90
95
100
80.3
95.2
102.4
88
77
51
68
T(K)
77
77.9
85.0
90.2
99.7
77.6
85.9
90.0
99.2
77.9
85.4
90.2
99.0
80
85
90
95
80
100
79.9
89.0
79.9
88.9
80.2
69.8
80.2
59.7
69.9
69.8
80.2
80.5
79.1
86.4
99.7
100
100
100
100
100
100
100
100
122
74.6
82.8
89.2

A^(S"1)
8.42 x l O " 6
1.107 XlO" 4
1.01 x l O " 5
2.01 x 10 " 5
3.89 x l O " 5
6.83 x l O " 5
1.14 x l O " 4
6.5 x 10" 6
5.44 x l O " 5
1.26 x l O " 4
1.9 XlO" 5
5.31 x 10 ~6
1.9 x l O " 5
1.9xlO" 4
6.98 xlO 1 4
5.77 x 10 ~4
1.43 x l O " 4
3.76 x 10 " 4
6.8OxIO" 4
2.05 XlO" 3
1.46 x l O " 4
4.03 x l O " 4
6.9OxIO" 4
2.04X10- 3
1.49 XlO" 4
3.90 x 10 ~4
6.95 x l O " 4
1.97xl0- 3
9.7xlO~ 6
1.75 x 10 " 5
3.64 x l O " 5
6.47 XlO" 5
2.55 x 10" 4
2.72 XlO" 5
7.42 x 10 " 5
2.59 x l O " 4
1.05 x 10 " 4
3.09 x 10" 4
1.58 x l O " 4
1.98 xlO~ 4
7.1 x 10 " 4
8.05 x 10 ~5
2.89 x 10 " 4
1.98 x l O " 4
7.IxIO"4
1.01 x 10" 4
8.6 x l O " 6
2.01 x 10 ~5
1.044 x l O - 4
3.85 x 10 " 5
2.07 x 10 " 5
3.93 x 10~5
1.42 x 10 " 5
3.10x 10" 5
1.83 x l O " 5
2.39 x 10 " 5
1.22 x 10- 5
1.9 x 10~5
6.43 x 10 " 5
1.781 x 10" 4
3.519 x l O " 4

E* (kj/mol)

Notes

140.2
135.6

121.3

121

a
a
a
a

exp[-121//?7]
133.9

133.5

133.5

136.4

128.9
146.4
125.5

a
a
a
a
a
a
a
a
a
a
a
a
a
h

a
a
w
w
w
w

121.3
121.3
121.3

w
w
w
w

132.7

p,z (1)
p,z (3950)
p,z (1)
p,z (3950)
p,z (1)
p,z(3950)
p,z (1)
p,z (3950)

122.8

Refs.
179
179
135
135
135
135
226
101
101
101
339
175
343
343
343
175
205
205
205
205
205
205
205
205
205
205
205
205
135
135
135
135
226
226
57
57
57
57
61
61
61
57
57
57
57
50
322
322
322
299
299
299
299
299
299
299
299
339
322
322
322

Notes page 11-69; References page II - 70

TABLE 1. cont'd
Number of
C atoms
15 (cont'd)

16

Initiator

Solvent

N-(4-Methoxybenzoyl) N'-OLcyanocyclohexyldiimide

Toluene

JV-(4-Methylbenzoyl) jy'-otcyanocyclohexyl diimide

Toluene

iV-Phenylacetyl W-a-cyanocyclohexyl diimide

Toluene

4-Cyano-l-methylpiperidine-4,4'-azo4'-cyano-l,l'-dimethylpiperidinium
nitrate

DMSO

4,4'-Azo-bis-4-cyano-1,1'-dimethylpiperidinium nitrate

DMSO

4,4/-Azo-bis(4-cyanopentanoyl)bis2-aminoethanol

DMF

Toluene

2,2/-Azo-bis-2-methylheptylonitrile

Toluene
Xylene
Toluene
Xylene

80

Toluene

80.5

Toluene

80.5

Toluene

40
1.175
50
4.45
40
6.95
50
2.89
80.5 (1.3250.35)

l,l'-Azo-bis-l-(2-methylcyclohexane)nitrile
l,l'-Azo-bis-l-cyclohexanecarbonitrile
2,2/-Azo-bis-cyclopentylpropionitrile (mp 72.2-74.5)
2,2'-Azo-bis-2-cyclopentylpropionitrile (mp 96.3-97.6)
2,2/-Azo-bis-2,4,4-trimethylvaleronitrile (mp 67.5-69)
2,2'-Azo-bis-2,4,4-trimethylvaleronitrile (mp 94.5-95.5)
2,2'-Azo-bis-2-isopropyl-3-methylbutyronitrile
U'-Azo-bis-l-cyano-^' dimethyl cyclohexane

Acetic acid
Toluene

Toluene
Toluene

133.9

132.6

124.7

115.1

a
a
exp[- 115/RT]

62

1.31 x 1O -4

104

1.30 x 10 ~4

104

w
w
w
w

50
50
50
50
50

135
135
135
135
61
104
101
101
101
357
357
357
357

x
x
x
x
x

10~4
10~4
10~5
10~4
10~4

Toluene

69
74
80

2.83 x l O - 5
4.65 x l O - 5
1.16 x l O " 4

DMF

134.1

322
322
322
322
322
322
322
322
322
135
135
135
135
135
135
135
135
357
357
357
357
357
357
101
101
101
101
343
343
343
50
62
101

166.9

4.7 x l O " 6

DMAC

4,4'-Azo-bis(4-cyanopentanoyl)bis2-(2-aminoethoxy)ethanol

Toluene

142.8

Refs.

1.5IxIO- 5
2.79XlO" 5
5.4OxIO- 5
9.77 XlO" 5
8.3 x 10 ~6
2.27 x 10 ~4
5.35 x 10~5
1.45 x l O - 4
2.6OxIO- 4
1.77 x 10~5
2.9OxIO- 5
4.9OxIO- 5
1.74 x l 0 ~ 5

Toluene

Notes

126.4

80
85
90
95
80.3
80.5
36.6
45.4
49.7
65
69
74
65

DMSO

2,2'-AzO-Ms^-CyClOhCXyIpropionitrile
l,l'-Azo-bis-l-cyclooctanenitrile

2,2'-Azo-bis-2-benzylpropionitrile

a (kj/mol)

7.1 x 1(T6
1.71 x 10 ~5
9.73 XlO- 5
1.06 x l O " 5
2.20 x 10 ~5
1.255 xlO~ 4
3.08 x 10 ~5
9.76 x 10 - 5
2.77xlO- 4
1.76 x 10~5
3.31 x 10~5
6.23 x 10 ~5
1.156xlO- 4
2.84 x l 0 ~ 5
5.1IxIO-5
9.87 x l 0 ~ 5
1.626xlO- 4
1.76 x 10 ~5
2.85 x 10 ~5
4.66 x l 0 ~ 5
1.73 x l O " 5
2.73 x l O - 5
4.53 x l O - 5
3.28 x 10~4
2.69 x l O " 5
9.72 x l O - 5
2.69X10- 4
1.9xlO" 5
1.9 x l O " 4
1.03 x 1015
1.63 x 10 ~4
1.78 x 10~4
7.43 x 10~6

2,2'-Azo-bis-(4-methoxy-2,4dimethylvaleronitrile)

l,r-Azo-bis-l-cycloheptane-nitrile

20

A:d (s"1)

80.8
87.9
101.2
81.4
87.3
101.9
74.3
82.9
91.2
80
85
90
95
80
85
90
95
65
69
74
65
69
74
69.5
48.9
58.9
67.3
30
47
T(K)
80.0
80.0
80.2

DMAC

18

T( 0 C)

113.5
121.3

132.2

108.4

357
357
54

TABLE 1. cont'd
Number of
C atoms
20 (cont'd)

22

34

Initiator
/

2,2 -Azo-bis-2-isobutyl-4-methylvaleronitrile
2,2'-Azo-bis-2-(4-chlorobenzyl)propionitrile
/
2,2 -Azo-bis-2-(4-nitrobenzyl)propionitrile
l,l'-Azo-bis-l-cyclodecanenitrile

4,4'-Azo-bis-(4-cyanopentanyl)bis(heptadecafluorododecanoate)

Solvent
Toluene

T( C)

kd (s" )

E* (kj/mol)

Notes

Refs.

Toluene

60.1
80.5
80

3.78 xlO~
3
5.28 x 10 "
5
8.8xl0~

50
50
54

Toluene

80

1.00 x 10 ~

54

Toluene

50.8
60.2
69.5
90
100
110
120
130

5.4OxIO"
4
1.7OxIO4
5.69xlO4
9.86 x 10 "
3
2.11 x 10 ~
3
4.4 x l 0 ~
2
1.1 x 10~
2
1.42 XlO"

Di-n-butyl phthalate

101
101
101
375
375
375
375
375

TABLE 2. MISCELLANEOUS AZO-DERIVATIVES


Number of
C atoms
2

Initiator
l,l'-Azo-bis-formamide

Solvent
DMF

DMSO

Formamide

Methyl-azo-3-propene

Hexamethylphosphoramide
Vapor

2,3-Diazobicyclo[2,2,l]hept-2-ene

Isooctane

2,2'-AzO-Ws-PrOPaHe

Toluene
Vapor

3,3'-Azo-bis-l-propene

Vapor

2,2'-Dichloro-2,2'-azo-bis-propane

Diphenyl ether

Siliconeoil

Methyl-azo-l,l-dimethyl-2-propene
(cw)
(trans)

Perfluoroazo-2-propane

Acetone

p-DiisopropylBenzene
Vapor

T( 0 C)

*d (s" 1 )

86.0
100.3
115.3
86.0
100.3
115.3
86.0
115.3
115.3

1.56 x 10 " 5
5.73 XlO" 5
1.14x10-4
5.48 XlO" 6
2.72 x l O - 5
1.01 XlO" 4
9.25 x 10 ~5
-2.0 x l O " 3
3.83 x 10~5

163.3
169.8
182.8
T (K)
131.5
142.3
164.1
180.8
164.1
250
260
270
280
290
142.65
152.68
167.12
158.5
167.9
178.5
185
199
221
-13.89
-5.04
4.00
114.55
123.83
133.33
T(K)

5.88 x 10 ~4
1.110 x l 0 ~ 3
3.36 XlO" 3
3.2 x 10 1 4
5.44 x 10~6
1.82 XlO" 5
1.66xlO- 4
8.35 x l O " 4
1.64 x l O " 4
7.67 x 10 " 3
1.67xlO- 2
3.35X10- 2
6.52X10- 2
1.28XlO-1
3.88 x l O " 4
1.10 x l O - 3
4.45 x l O - 3
1.03 x 10~4
4.54 x l O - 4
8.08 X l O " 4
4.8xlO"4
2.1 x 10" 3
1.6xlO- 2
3.62 x 10~5
1.7OxIO- 4
6.82 x l O - 4
1.02 x l O " 4
2.68 x l O " 4
8.44 XlO" 4
5.0IxIO16

Ea (kj/mol)

148

Notes
C2
C2
C2
c
c
c

268
268
268
268
268
268
268
268
268

298
298
298
298
180
180
180
180
180
110
110
110
110
110
319
319
319
297
297
297
240
240
240
252
252
252
252
252
252
360

exp[- /RT]
157.7

171.1

a
a
a
a
a

151.3

138.3

h,u 4
U4
U4

96.8

147.9

exp[-189.0//?7]

Refs.

Notes page 11-69; References page 11-70

TABLE 2. cont'd
Number of
C atoms
6 (cont'd)

Initiator

Solvent

l-Propyl-azo-3'-propene

Vapor

Triazobenzene

Nitrobenzene

Tetralin

terf-Butyl-azo-3-propene

2,2/-Azo-isobutyramide
Azo-bis-isobutyramidine

Azo-bis-isobutyramidine
2HCl (AIBA)

Vapor

Water
Water
Chloroform
DMSO
Methanol
Water (pH 1.9)
Water (pH 5.8)
Water (pH 9.5)
Water

AIBA

Water

AIBA-kaolin adduct

Water

AIBA-bentonite adduct

Water

Azo-bis(2-amidinopropane) 2HCl
2,2'-Azo-bis(2-amidinopropane) 2HCl
Azo-bis-isobutyramidine 2HNO3

Methanol
Water
Water
DMSO-cumene

2,2'-Azo-bis-isobutane

Vapor

2,2'-Azo-bis-isobutane

Diphenyl ether/isoquinoline (90/10)

J( 0 C)
101.32
114.10
126.02
T (K)
105
115
130
145
105
115
130
145
80.88
90.90
106.81
T (K)
88
60
60
60
70
60
50
60
50
60
50
60
60.0
70.0
75.0
80.0
40.15
50.05
60.20
70.10
100.10
70
50.0
60.0
70.0
80.0
50.0
55.0
65.0
70.0
80.0
50
50
56
60
70
160
180
190
210
174.8
188.3
188.8
165
175
185
190

kd (s'1)
1.10 x 10~ 6
5.60 x l O ~ 6
2.11 x l O ~ 5
6.3 x 10 1 4
3.5 x 10~ 7
1.20 x l O ~ 6
6.25 x l O ~ 6
2.5OxIO-5
4.0xl0~7
1.34 x 10~6
6.01 x 10 ~6
2.47 x l 0 ~ 5
2.13 x l O ~ 6
7.27 x l O ~ 6
3.89 x l O ~ 5
5.4 x 10 12
1.9xl0~ 5
3.15 x 10~5
2.80xl0~ 5
7.1 x 10~6
3.68 xlO~ 6
1.45 x 10 ~6
8.3 x 10 ~6
3.42 x 10 ~5
8.0xl0~ 6
3.22 x l 0 ~ 5
4.7 x 10 ~6
2.53 x l 0 ~ 5
3.70 x 10 ~5
1.33 xlO~ 4
2.58 xlO~ 4
5.13 xlO~ 4
2.49 xlO~ 6
9.79 xlO~ 6
4.03 x l 0 ~ 5
1.52 xlO~ 4
4.96 x l 0 ~ 3
1.52 xlO~ 4
1.37 x l 0 ~ 5
6.16 xlO~ 5
2.28 xlO~ 4
9.53 xlO~ 4
1.8OxIO- 5
3.97 xlO~ 5
1.53 xlO~ 4
3.21 x 10~4
1.04 XlO- 3
1.45 x 10 ~5
8.1x 10 ~6
1.93 x 10 ~5
4.86 x l 0 ~ 5
1.53 xlO~ 4
1.9xlO~ 5
5.01 x l 0 ~ 5
1.53 xlO~ 4
1.05 x l 0 ~ 3
6.8 x l 0 ~ 5
1.75 xlO~ 4
1.14 xlO~ 4
2.782 x l 0 ~ 5
8.74 x l 0 ~ 5
2.513 x l O ~ 4
4.143 XlO" 4

Ea (kj/mol)

Notes

149.2

v2i
V2I
V2I

e x p [ - 149.2/RT]
140.2

136.0

124.9

exp[- 124.9/RT]

v2i
V21
V2I
v2i
a
q2
q3

126.5
124.4
151.7
128.9

122.6

133.9

126.4

a
m4
m4
m4

176.6

m4
h

Refs.
298
298
298
298
45
45
45
45
45
45
45
45
298
298
298
298
342
288
288
184
21
184
341
341
341
341
341
341
233
233
233
233
237
237
237
237
237
21
233
233
233
233
233
233
233
233
233
356
356
340
21
21
339
221
221
221
243
243
243
171
171
171
171

TABLE 2. cont'd
Number of
C atoms
8 (cont'd)

Initiator
2,2'-Azo-bis-isobutane
2,2'-Dimethoxy-2,2'-azopropane

10

Diphenyl ether/isoquinoline (90/10)


Diphenyl ether

2,2/-Dimethylmercapto-2,2/azopropane

Diphenyl ether

Isopropyl-azo-l,l-dimethyl-2propene (cis)

Acetone

(trans)

Solvent

Diisopropylbenzene

2,2/-Azo-bis(2-methylpropane)
2-(4-Bromophenyl-azo)-2nitropropane

Vapor
DCB

rm-Butyl-azo-U-dimethyl2-propene (trans)

Diisopropylbenzene

2-(4-Nitrophenylazo)-2-nitropropane

DCB

oc-Phenylethyl-azo-methane

Diphenyl ether

2,2'-Diacetylthio-2,2'-azopropane

Hexadecane
Diphenyl ether

2,2 '-Diacetoxy-2,2 '-azopropane

Diphenyl ether

Siliconeoil
Azo-bis( 1,1 -dimethyl-2-propene)
(trans)

Xylene

Azo-bis-(l,l-dimethyl)-2-propyne
(trans)

Xylene

2,2/-Azo-bis-2-methylbutane

Ethylbenzene

Isoamyl alcohol

2,2'-Azo-bis-2-methylbut-3-ene

n-Decane

2,2'-Azo-bis-2-(methylcarboxy)propane
2,2'-Azo-bis-methyl-2-methylpropionate

Water

2,2'-Azo-bis-methyl-2-methylpropionate

Collidine
1,2-Dichlorobenzene
Diethyl oxalate
Ethylene glycol
Nitrobenzene
Undecane
Xylene

T( 0 C)

A;d (s *)

195
200
150.1
159.9
174.6
125.0
135.0
145.0
-25.09
-16.65
-8.20
97.41
106.06
115.06
160
130
135
140
T(K)
73.72
80.31
87.08
130
140
145
T(K)
151
161
171
161
130.0
140.0
149.4
190.0
200.1
210.3
258

6.73IxIO- 4
1.093 x 10~3
4.02 x l O " 5
1.50xl0~ 4
6.67 XlO" 4
3.40xl0~ 4
7.10 xlO~ 4
1.15 x l 0 ~ 3
6.30x 10" 5
2.87 x 10 " 4
1.10 x l O - 3
1.15 x 10~4
3.19 x l O - 4
9.22 x l O - 4
1.93 x 10 " 5
1.62 x 10~4
2.59 x 10 ~4
4.3OxIO- 4
1.1 xlO 1 3
8.69 x 10 ~5
1.83 x 10~4
3.80xl0~ 4
LOOx 10~4
2.44 x 10 ~4
4.06 x l O - 4
1.1 x 1013
4.35 x 10 ~5
1.16 x l O - 4
3.48 XlO" 4
1.2OxIO- 4
1.33 x 10~4
4.4OxIO" 4
1.19 x l O - 5
8.23 x 10 ~5
2.6IxIO-4
6.38 x l O " 4
1.46 x 10 ~2

42.03
49.98
57.39
41.32
48.20
57.19
180.0
190.0
200.0
180.0
190.0
200.0
44.90
55.44
63.74
50

5.95 x 10~5
1.73 x l O - 4
4.54 x l O - 4
5.37 x l 0 ~ 5
1.3OxIO- 4
4.39 x l O - 4
1.36 x KT 4
3.89 x l O - 4
1.03 x l O - 3
1.14xlO- 4
3.5IxIO-4
9.26 xlO~ 4
6.73 x 10 ~5
2.631 x 10 ~4
7.045 x l O " 4
3.51 x 10~6

80
80
80
80
80
100
80
80

1.67 x 10 ~A
1.44 x 10 " 4
1.52 x 10 ~4
1.24 x 10 " 4
1.6IxIO- 4
1.73 x 10- 3
1.04 x 10 ~4
1.09 x 10 ~4

Ea (kj/mol)

Notes

171.8

84.6

91.3

h,u5
U5
U5
h

137.8

a
130

exp[- 130/RT]
112.3

134

exp[- 134/RT]
161.5

151.3

171.4

109.4

111.9

176.4

176.0

107.3

129.3

149.8

a
a
a
a
a
a
a
a

Refs.
171
171
297
297
297
297
297
297
252
252
252
252
252
252
340
325
325
325
325
252
252
252
325
325
325
325
149
149
149
149
297
297
297
297
297
297
240
252
252
252
252
252
252
336
336
336
336
336
336
278
278
278
285
226
226
226
226
226
226
226
62

Notes page 11-69; References page 11-70

TABLE 2. cont'd
Number of
C atoms
10 (cont'd)

Initiator

Solvent

N,Af'-Azo-piperidine

Silicone oil

2-(4-Methoxyphenylazo)2-nitropropane

DCB

Dimethyl 2,2'-azo-isobutyrate

Acetic acid

Acetonitrile

Benzene

Cyclohexane

Dimethyl-2,2'-azo-isobutyrate

Methanol

Methanol/SnCl4

Methanol/ZnCl2
Paraffin
Toluene

11

2,3,7,8-Tetraazahexacyclo[7.4.1.04'12.0611.01013]tetradeca2,7-diene
2-(2,6-Dimethylphenylazo)2-nitropropane

a-Phenylethyl-azo-2-propane

12

Toluene/SnCl4
Acetonitrile-d3

DCB

Diphenyl ether/
benzoquinone
Diphenyl ether

Azo-bis-isobutanoldiacetate

Cyclohexane

Azo-bis-(l-carbomethoxy-3-methylpropane)

Benzene

Carbon tetrachloride

4,4'-Azo-bis-(4-cyanopentanoic acid)
(meso)

DMAC

T( 0 C)

kA (s" 1 )

181
228
135
140
150
T(K)
40
50
60
70
40
50
60
70
50
60
70
40
50
60
80
40
50
60
40
50
60
60
99.2
60
60
66
70
80
60
215
230
250
135
140
150
T(K)
143.2

1.7 x l O " 3
4.3 XlO- 2
7.4xlO" 5
1.30 x 10 ~4
3.67 XlO" 4
2.5 XlO 15
8.61 x 10 ~7
3.16 xlO~ 6
1.56 XlO" 5
5.49 x l O " 5
5.44 x 10~7
2.68 XlO" 6
1.01 x 10 " 5
3.57 XlO- 5
2.22 x 10 " 6
8.85 XlO" 6
3.27 x l O " 5
2.89 x 10 " 7
1.38 x l O " 6
5.85 XlO" 6
2.22 x l O - 5
6.86 x 10 " 7
3.12 XlO" 6
1.44 XlO" 5
1.20 x 10 " 6
4.46 x l O " 6
1.98 XlO" 5
1.51 x 10 ~5
1.02 x 10 " 3
8.9xlO- 6
8.11xlO" 6
1.93 x l 0 ~ 5
3.17 x l O " 5
1.19xlO- 4
1.63 x 10 ~4
1.18 x l 0 ~ 5
6.65 x l O " 5
3.4OxIO" 4
9.OxIO" 5
1.44 x 10 ~4
3.86 x l O " 4
4.8 xlO 1 3
1.5OxIO"4

143.0
152.0
165.5
170.0
180.0
189.0
199.0
36
45
55
65
45
55
65
77.6
85.3
90.9
99.8

1.54 x 10 ~4
4.24 xlO~ 4
1.57Ox 10" 3
4.86 x 10 " 5
1.27 XlO" 4
3.47 x l O " 4
1.01 x 10" 3
3.05 x 10 ~7
1.31 x 10 " 6
4.54 x l O " 6
1.82 x l O - 5
7.18 x 10 " 7
3.79 xlO~ 6
1.02 x l O " 5
1.33 x 10 ~4
3.7OxIO" 4
7.17 XlO" 4
2.02 x l O " 3

a (kj/mol)

Notes

153

exp[-153//CT]
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a

131.6
a

188.7

Xi
X1
Xi

exp[- 13S/RT]

113
ti 3
ti3

133.5

a
a
a
a

Refs.
240
240
325
325
325
325
326
326
326
326
326
326
326
326
326
326
326
326
326
326
326
326
326
326
326
326
326
326
240
290
340
340
340
340
290
174
174
174
325
325
325
325
220
310
310
310
189
189
189
189
68
68
68
68
68
68
68
205
205
205
205

TABLE 2. cont'd
Number of
C atoms
12 (cont'd)

Initiator

Solvent

4,4'-Azo-bis-(4-cyanopentanoic acid)
(nD)

Azo-bis-(AyV'-dimethylene
isobutyramidine) 2HCl
Azo-bis-(W-dimethyleneisobutyramidine)

tert-Butyl(2,2,4-trimethyl2-pentyl)diazene

60
70
75
70
60
44

2.06 x 10 " 4
6.64 x 10~4
1.08 XlO" 3
6.97 x 10 ~4
2.13 x 10 ~4
1.9xlO" 5

80
75
80
85
60
61
155
165.7
180.0
120.0
135.0
143.0
145.0
150.0
155.0
160.0
165.0
170.0
60
70
80
60
70
80
60
70
80
58

1.79 x 10~4
8.04 x 10 ~5
1.39 x l O - 4
2.6 x l O " 4
1.09 x 10~5
1.9xl0~ 5
1.6IxIO- 4
4.75 x 10 " 4
1.98 x l O - 3
1.06 x 10 ~4
5.94 x l O - 4
1.42IxIO- 3
7.56 xlO~ 5
1.273 xlO~ 4
2.147 x l O " 4
3.771 x 10~4
6.07 x l O - 4
1.033 x l O - 3
1.6IxIO- 5
5.88 x 10 ~5
2.02 XlO" 4
1.53xl0- 5
5.62 x l O - 5
2.OxIO- 4
1.62 x l O " 5
5.83 x l O - 5
2.066 XlO" 4
1.93 x 10 " 5

Methanol
Water

50
50

4.83 x 10 ~5
4.02 x 10 ~5

Methanol
-Decane

50
39.21
50.71
58.95

Chlorobenzene
Nitrobenzene
Water
DMSO

DMSO-cumene
DMSO-tetralin
Water
DMSO
DMSO-cumene

DMSO-tetralin
Methanol
Diphenyl ether

oc-Cumyl-azo-isopropane

Diphenyl ether

2,2/-Dicyclopropyl-2,2/-azopropane

Diphenyl ether/ ^
isoquinoline (90/10)

Di-(2-hydroxyethyl)-2,2'-azobis-isobutyrate

Dioxane

DMF

Toluene

14

2,2/-Azo-bis[AK2-hydroxyethyl)2-methylpropionamidine] 2HCl
2,2'-Azo-bis[2-(imidazoline-2-yl)propane 2HCl
2,2'-Azo-bis[2-(irnidazoline-2-yl)propane
2,2'-Azo-bis-(2-cyclobut1-enylpropane)

(s" 1 )

1.53 x l O - 4
4.1IxIO-4
7.0OxIO- 4
2.09 x l O - 3
1.55 x l O - 4
4.05 x l O " 4
6.98 x l O - 4
2.0OxIO- 3
1.51 x 10" 4
4.34 x l O - 4
7.33 xlO~ 4
2.24 x l O - 3
4.13 x l O " 5
5.93 x 10 ~4
1.56 x 10~4
1.9xl0" 5

(nD_)

2,2-Azo-bis-[2-methyl-J/V(2-hydroxyethyl) propionamide]
Azo-bis-(AyV'-dimethyleneisobutyramidine) 2HNO3

fcd

77.9
85.8
90.1
99.1
78.0
85.4
90.0
99.0
77.7
86.0
90.5
99.7
70
92.6
80
86

(n D + )

2,2-Azo-bis-(ethyl-2-methylpropionate)

T( 0 C)

Water

4.7xlO~ 6
1.286 x l O " 4
5.678 x 10 ~4
1.762 XlO" 3

Ea (kj/mol)

Notes

134.3

a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a

205
205
205
205
205
205
205
205
205
205
205
205
139
139
226
342

21
21
21
21
21
339

134.3

134.3

123.0

159.6

a
h

158.2

125.7

129.9

129.9

Refs.

21
21
21
21
21
339
314
314
314
310
310
310
171
171
171
171
171
171
292
292
292
292
292
292
292
292
292
339
356
356

112.3

356
278
278
278

Notes page 11-69; References page II - 70

TABLE 2. cont'd
Number of
C atoms

Initiator

U (cont'd)

2,2'-Azo-bis-(2-methylhex-3-ene)

n-Decane

Di-(2-chloroethyl)-2,2'-azo-bisisobutyrate

Dioxane

Solvent

DMF
Di-(2-chloroethyl)-2,2'-azo-bisisobutyrate

Toluene

l,l'-bis-(4-Chlorophenyl)
azomethane

Diphenyl ether

Di-(2-hydroxypropyl)2,2/-azo-bis-isobutyrate

Dioxane
DMF
Toluene

15
16

2,2/,3,3,3',3/-Hexamethyl2,2'-azo-butane

Diphenyl ether

U'-Diphenyl-azo-methane

Diphenyl ether

2,2'-Azo-bis[2-methyl-N-(phenylWater
methyl)propionamidine] 2HCl
2,2'- Azo-bis[2-(4-methylimidazoline-2-yl)-propane
Methanol
2,2'-Azo-bis[2-(4-methylimidazolineMethanol
2-yl)-propane 2HCl
Water
2,2'-Azo-bis[2-(3,4,5-trihydroMethanol
pyrimidine-2-yl)propane
2,2'-Azo-bis[2-(3,4,5-trihydroMethanol
pyrimidine-2-yl)propane 2HCl
Water
1-Methylcyclopentyl-azoterf-Butyl
benzene
a-cumene
l,r-Azo-bis-l-chloro1-phenylethane

Acetophenone
Benzophenone
Paraffin

Toluene

!,r-Azo-bis-1-chloro-l(3-bromophenyl)ethane
l,r-Azo-bis-l-chloro-l(4-bromophenyl)ethane

Toluene
Toluene

J(0C)

* d (s" 1 )

39.25
49.52
58.95
60
70
80
60
70
80
60
70
80
145.56
155.56
165.56
175.56
60
70
80
60
70
80
60
70
80
170.0
180.0
190.0
145.0
155.0
165.0
175.0
53

5.33 xlO~ 5
2.256 xlO~ 4
7.584 XlO" 4
1.56 x 10~5
5.55 x 10 " 5
1.9672 x l O - 4
1.25 x l O " 5
4.902 x l O - 5
1.9125 x 10" 4
1.666 x 10 " 5
5.018 x l O - 5
1.99 x l O " 4
2.3OxIO- 4
7.6OxIO" 4
1.49 XlO" 3
4.4OxIO" 3
1.80 x 10 " 5
7.6xlO~ 5
2.22 XlO" 4
1.97 x l O - 5
6.55 x l O " 5
2.3OxIO- 4
1.9Ox 10" 5
7.72 x l O " 5
2.365 x l O - 4
2.37 xlO" 4
5.29 x l O " 4
1.00 x l 0 ~ 3
1.72 x l O " 4
4.93 x l O - 4
1.12 x l O " 3
2.34 x l O - 3
1.93 x 10 " 5

50
50
50
50
50
50
88.3
107.3
117.6
74.8
83
67.8
86.2
98.2
94.5
112.3
120.5
129.3
137
64
74
64
74
59
69
59
69

Ea (kj/mol)

Notes

115.2

129.9
134.1
129.9
146.6

121.5
121.5
121.5
156.7

119.0

Refs.
278
278
278
292
292
292
292
292
292
292
292
292
297
297
297
297
292
292
292
292
292
292
292
292
292
297
297
297
297
297
297
297
339

10 ~5
10 " 5
10 " 5
10 ~6

356
356
356
356

7.8xlO~ 6
5.9xlO~ 6
5.00xl0" 5
4.95 x 10 " 4
1.43 x l O " 3
8.6xlO~ 4
1.95 x 10 " 3
2.8xlO" 4
3.3 x l O " 3
1.40xl0" 2
2.4xlO" 3
5.2 x l O - 2
1.03XlO"1
1.6XlO" 1
5.OxIO" 1
1.8 x 10 " 4
7.2 x l O " 4
1.79 xlO" 4
7.2OxIO" 4
1.64 x 10~4
6.64 x 10 ~4
1.77 xlO" 4
6.75 x 10 ~4

356
356
327
327
327
240
240
240
240
240
240
240
240
240
240
240
240
239
239
239
239
239
239

1.23 x
7.48 x
6.73 x
1.1 x

132.0

135.1

a
a
a
a
a
a

131.8
127.2

TABLE 2. cont'd
Number of
C atoms
16 (cont'd)

Initiator
U'-Azo-bis-l-chloro-l(4-chlorophenyl)ethane
2,2/-Azo-bis-(2-cyclopent-lenylpropane)

Solvent
Toluene
n-Decane

l,l'-Azo-bis-l,l-dicyclopropylethane

Diphenyl ether/
isoquinoline (90/10)

2,2/-Azo-bis-{2-methyk/V-[U(bis-hydroxymethyl)-2-hydroxyethyl]
propionamide}
2,2/-Azo-bis-{2-methyl-iV-[l,l(bis-hydroxymethyl)ethyl]
propionamide}
2,2'-Azo-bis[2-(4,
4-dimethylimidazoline-2-yl)
propane
2,2'-Azo-bis[2-(4,4-dimethylimidazoline-2-yl)propane 2HCl
2,2 '-Azo-bis[2-(4,5-dimethylimidazoline-2-yl)propane 2HCl

Water

2,2'-Azo-bis[2-(4,5,6,7-tetrahydrolH-l,3-diazepine-2-yl)propane
2HCl
2,2/-Azo-bis-(2,2,4-trimethylpentane)
U'-Azo-bis-l-phenylethane
l,r-Azo-bis-l-phenylethane

l,l'-Di-(3-chlorophenyl)-l,razo-ethane
l,l'-Di-(4-chlorophenyl)-l,l'azo-ethane

1.97 x 10~4
6.93 x 10 " 4
9.98 x l O " 5
4.593 x 10 " 4
1.528 x l O - 3
6.33 x l O " 5
2.03 x 10 ~4
6.07 XlO" 4
1.695 x l O " 3
1.9 x 10~5

Ea (kj/mol)

Notes

118.8
116.9

a
a
h

149.0

Refs.

239
239
278
278
278
171
171
171
171
342

342

82

1.9 x l O " 5

Methanol

50

9.3xlO" 6

356

Methanol
Water

50
50

9.55 x 10 ~5
9.30xl0"5

356
356

Methanol
Water
Methanol
Water

50
50
50
50

9.21
8.94
1.23
1.04

x 10 " 5
x 10 " 5
x 10~5
xlO"5

356
356
356
356

1.9 x 10~5

Diphenyl ether

110

Dodecane
Ethylbenzene
Toluene
Ethylbenzene

97.3
3.175 x l 0 ~ 5
100.4 (5.45 0.05) x 10~5
110.3 (1.69 0.01) x 10 ~4
105.02
8.473 x 10 " 5
105.28
9.02 x l O - 5
105.28
7.62 x l O " 5
105.02
7.623 x l O " 5
97.3
4.135 x 10 ~5
97.3
3.688 x 10 " 5
97.3
3.995 x 10 " 5
97.3
3.294 x 10 ~5
140.0
1.93 x l O " 4
150.1
5.29 x 10~4
164.8
2.18 x l O " 3
95
4.13 x l O " 5
105
1.218 x l O " 4
85
1.45 x 10~5
95
4.82 x l O " 5
105
1.650xl0~ 4
120.05
7.8xlO-5
130.0
2.63 xlO~ 4
139.0
7.38 XlO" 4
147.0
1.906 x l O - 3
105
1.121 x 10~4

N-Methyl-N-benzyl aniline
N-Methyl propionamide
Diphenylmethane
Propylene carbonate
Diphenyl ether

p-Cymene
p-Cymene

a,oc-Diethylbenzyl-azo-3-pentane

Diphenyl ether

l,l'-Di-(3-fluorophenyl)1,1'-azo-ethane
l,r-Di-(4-fluorophenyl)1,1'-azo-ethane

p-Cymene

Di-(3-hydroxybutyl)-2,2'-azo-bisisobutyrate

59
69
39.21
49.52
58.95
120
130
140
150
80

^d(S" 1 )

Water

(l,l'-d 2 )
(l,l,U',r,l'-d6)

terr-Butyl-(2,2,4,6,6-pentamethyl-4-heptyl)-diazine

T( 0 C)

/?-Cymene

Dioxane

DMF

85
95
105
60
70
80
60
70
80

5.5 x l O " 6
2.35 x 10 " 5
7.85 x l O - 5
2.22 x 10" 5
7.84 x 10 ~5
2.413 x l O " 4
1.83 x l O " 5
7.69 x l O " 5
2.424 XlO" 4

136.4

141.6

122.3

134.1

147.0

117.3

121.5

339
26
107,98
107,98
152
183
183
152
26
26
26
26
314
314
314
266,313
266,313
266.313
266,313
266,313
310
310
310
310
266,313
266,313
266,313
266,313
292
292
292
292
292
292

Notes page 11-69; References page II - 70

TABLE 2. cont'd
Number of
C atoms
16 (cont'd)

Initiator

Solvent

Di-(3-hydroxybutyl)-2,2'-azo-bisisobutyrate

Toluene

Di-(4-hydroxybutyl)-azo-bisisobutyrate

Dioxane

DMF

Toluene

l,r-Bis-(4-methoxyphenyl)azo-methane

Diphenyl ether

2,2',4,4,4',4'-Hexamethyl2,2'-azo-pentane

Diphenyl ether

1-Methylcyclohexyl-azo-a-cumene

17

18

terf-Butylbenzene

1,1 '-Diphenyl-l,l'-azo-ethane

p-Cymene

2-(Phenylazo)-2-propyl perbenzoate

Chlorobenzene

(l-Phenylethyl)-azo-diphenylmethane
l,l'-Bis(p-tolyl)-azo-methane

Chloroform-d
Chlorotoluene
Ethylbenzene
Diphenyl ether

3,7-Diphenyl-l,2-diaza-l-cycloheptene

l,l'-Azo-bis-cumene

Xylene

Benzene
terr-Butylbenzene

Chlorobenzene

Cumene

Dodecane
-Octane

Toluene

T( 0 C)
60
70
80
60
70
80
60
70
80
60
70
80
145.0
155.0
165.0
175.0
130.2
140.0
150.0
102.2
113.1
122.0
95
105
10
35
10
10
58
145.0
155.0
165.0
175.0
61.0
70.0
80.0
89.3
100.2
80
100.2
58.91
60
60
60
55
55
55
55
55
55
60
60
60
60.23
60
60
60
40.04
49.52
59.42
69.23
41.0
44.8
58.5

fcd

(s" 1 )
2.43 x 10 ~5
8.18 x 10 ~5
2.461xlO~ 4
2.12 x 10 ~5
6.57 x 10 ~5
2.539 x l 0 ~ 4
1.97 x l 0 ~ 5
6.19xlO- 5
2.50xl0~ 4
2.59 x l 0 ~ 5
6.66 XlO- 5
2.628 xlO~ 4
2.23 x 10~A
5.67 x 10 ~4
1.61 x 10~3
3.79 x l 0 ~ 3
1.82 xlO~ 4
4.51 x 10 ~4
1.28 x l 0 ~ 3
2.58 x 10 ~4
9.81xlO~ 4
2.2OxIO- 3
2.74 x l 0 ~ 5
8.21xl0~ 5
4.5 x 10~4
1.9 x l 0 ~ 3
5.IxIO-. 4
6.4xlO~ 4
1.9XlO" 5
2.00 x 10~4
4.69 xlO~ 4
1.22 x l O - 3
3.45 x l 0 ~ 3
3.80xl0~ 5
1.34 xlO~ 4
4.27 XlO" 4
1.59 x l O - 3
4.04 x 10 ~3
4.26 xlO~ 4
3.94 XlO" 3
1.94 xlO~ 4
1.03 x 10 ~4
4.03 x l 0 ~ 5
4.44 x l O - 6
8.50 x 10 " 5
6.88 x l 0 ~ 5
4.42 x l O - 5
8.1OxIO- 5
6.75 x l O " 5
3.83 x l O - 5
1.16 x l O - 4
4.73 x l 0 ~ 5
7.23X10- 6
1.47 x 10~4
1.14 x 10~4
4.44 x l 0 ~ 5
8.32xl0-6
9.46 x 10 ~6
4.33 x l O - 5
1.62 xlO~ 4
5.80xl0~ 4
9.6x10-6
1.98 xlO~ 5
1.28OxIO-4

E* (kj/mol)

Notes

117.3

125.7

125.7

121.5

145.0

132.8

131.1

124.0

145.4

a
h

a
a
V5
z (1256)
z (3890)
z (1013)
z (4154)
z (1013)
z (4154)
z (1256)
z (3890)

z (1256)
z (3890)
h

122.8

Refs.
292
292
292
292
292
292
292
292
292
292
292
292
297
297
297
297
297
297
297
327
327
327
266,313
266,313
372
372
372
372
339
297
297
297
297
138
138
138
138
138
44
44
217
333
333
333
280
280
280
280
280
280
333
333
333
217
333
333
333
217
217
217
217
309
309
309

TABLE 2. cont'd
Number of
C atoms
IS (cont'd)

Initiator

Solvent

l,l'-Azo-bis-4-bromocumene

Toluene

lJ'-Azo-bis-S-chlorocumene

Toluene

1,1'- Azo-bis-4-chlorocumene

Toluene

l,r-Azo-bis-l-chloro-l-(4-tolyl)ethane

Acetophenone

Paraffin

Toluene

2,2'-Azo-bis[2-(4-ethyl-4-methylimidazoline-2-yl)propane 2HCl
2,2/-Azo-bis[2-(4-ethyl-5-methylimidazoline-2-yl)propane 2HCl
2,2'-Azo-bis[2-(5,5-dimethyl-3,4,5-trihydropyrimidine-2-yl)propane
2,2/-Azo-bis[2-(5,5-dimethyl-3,4,5-trihydropyrimidine-2-yl)propane2HCl
l,l'-Azo-bis-4-fluorocumene

Methanol
Water
Methanol
Water
Methanol

l,l'-Di-3-trifluoromethylphenyl)-l,l'-azo-ethane
l,l/-Azo-bis-(2-methoxyphenyl)ethane

p-Cymene

Methanol
Water
Toluene

p-Cymene

l,l'-Azo-bis-(2-methoxyphenyl)ethane

Ethylbenzene

l,l/-Azo-bis-(3-methoxyphenyl)ethane
l,r-Azo-bis-(4-methoxyphenyl)ethane
l,r-Azo-bis-l-(4-methoxyphenyl)ethane
l,r-Azo-bis-l-phenylpropane

p-Cymene

2,2/-Azo-bis-2-phenyl-hexafluoropropane

Toluene

p-Cymene
Ethylbenzene
Ethylbenzene

U'-Dimethyl-azo-cyclooctane

Benzene

!,l'-Diphenyl-azo-cyclopropane

Benzene

Ethylbenzene

T( 0 C)
42.8
48.6
58.0
36.0
42.8
48.2
61.1
36.0
42.8
48.2
74.8
79.5
86
105
109.5
126
135.5
59
69
59
69
50
50
50
50
50

kd ( s 1 )
2.72 xlO~ 5
6.28 x l O " 5
2.189 x l O - 4
8.8 x 10~6
2.46 XlO" 5
5.55 x l 0 ~ 5
2.796xlO- 4
1.11 x 10 ~~5
2.9OxIO- 5
6.52 x l 0 ~ 5
2.1 x 10~3
3.OxIO" 3
7.4 x l O - 3
1.66 x l O " 3
2.5 x l O - 2
6.4 x l O - 2
UxlO"1
1.03 x 10 ~4
4.OxIO" 4
1.03 x l O - 4
3.93 XlO" 4
6.8OxIO" 5
7.38 x 10 " 5
9.48 x 10 " 5
1.1 x 10 " 4
9xlO"7

50
8.OxIO- 6
50
7.9xlO" 6
36.0
5.7xlO-6
42.8
1.31 x 10 ~5
48.2
2.94 XlO" 5
61.1
1.880xl0~ 4
95
4.13 x IO" 5
105
1.357 x 10~4
84.6
1.69 x 10~5
95
6.1IxIO-5
105
1.975 x l O - 4
106.06
2.29 x l O " 5
113.81
5.52 x 10~5
133.66
4.87 XlO" 4
95
1.53 x IO" 5
105
6.91 x 10 ~5
95
3.56 x l O " 5
105
1.09OxIO- 4
100.4
(7.15 0.1) x 10~5
110.3 (2.48 0.02) x 10 ~4
100.4
(2.35 0.1) x 10~5
110.3
(7.2 0.2) x 10- 5
45.0
8.36 x l O " 6
50.0
2.16 x l O " 5
55.0
4.92 x l O - 5
60.0
8.81xl0"5
67.0
2.46 x l O - 4
43.8
6.3 x l O - 5
53.8
2.4 x l O - 4
130.0
1.09 x l O " 4
140.0
3.05 x l O - 4
150.0
8.96 x l O " 4
165.0
9.6xlO" 5
175.0
2.2IxIO" 4
185.0
5.09 x l O - 4
170.0
1.67 x 10 ~4
180.0
3.48 x l O " 4

Ea (kj/mol)

Notes

117.7

115.9

112.5

126.8

115.9

134.9

135.6

171.8

a
a
a
h

126.5

149.8
135.1
137.2

115.5
145.8

135.3

Refs.
309
309
309
200
200
200
200
200
200
200
240
240
240
240
240
240
240
240
240
239
239
356
356
356
356
356
356
356
200
200
200
200
266,313
266,313
266
266,313
266,313
300
300
300
266,313
266,313
266,313
266,313
98
98
98
98
173
173
173
173
173
42
42
327
327
327
323
323
323
323
323

Notes page 11-69; References page 11-70

TABLE 2. cont'd
Number of
C atoms
IS (cont'd)

19

20

Initiator

Solvent

3,8-Diphenyl-l,2-diaza-lcyclooctene

Tetralin

U'-Di-O-tolyO-U'-azo-ethane
l,l'-Di-(4-tolyl)-l,r-azo-ethane

/?-Cymene
p-Cymene

Phenyl-azo-diphenylmethane

Decalin

2-(2-Phenyl-4-methylpentyl)azo-2-(4-methylpentane)

Diphenyl ether

l,l'-Azo-bis-l-acetoxy1-phenylethane

Paraffin

U'-Azo-bis-U-dicyclopropylbutane

Diphenyl ether/
isoquinoline (90/10)

9-Azo-bis-decalin (cis)

Ethylbenzene

(trans)

oc,a'-Azo-bis(a-methylbenzyl) diacetate

Dichlorobenzene

Azo-bis-4-methylcumene

Cumene

Toluene

2,2'-Azo-bis[2-(4-ethyl-5-isopropylimidazoline-2-yl)propane 2HCl
2,2'-Azo-bis-2-(4-tolyl)-propane

Methanol
Water
Toluene

l,r-Azo-bis-l,l,l-tricyclopropylmethane

Diphenyl ether/
isoquinoline (90/10)

l,r~Di-(4-ethylphenyl)1,1-azo-ethane
l,l'-Diphenyl-azo-butane

l,l'-Diphenyl-azo-cyclobutane

Decalin/
isoquinoline (90/10)
Isoquinoline
Cumene/
isoquinoline (90/10)
p-Cymene
Ethylbenzene

Ethylbenzene

T( 0 C)

^d(S"1)

143
151
165
173
105
95
105
124.5
144.5
103.0
110.0
120.0
130.0
131
142
149.5
120.0
125.0
130.0
135.0
140.0
147.0
180.0
190.0
200.0
180.0
190.0
200.0
65
70
80
90
55
55
55
41.0
49.5
58.5
50
50
36.0
42.8
61.1
105.0
110.0
115.0
120.0
125.0
130.0
135.0

9.52 x 10~5
2.09 x l O " 4
8.77 XlO" 4
1.82 xlO~ 3
8.17 x l O " 5
3.06 x 10~5
9.35 x l O - 5
3.44 x 10 " 5
2.69 x l O - 4
1.17 x l O " 4
2.52 x 10 ~4
8.51 x 10- 4
2.611 x l O " 3
3.2 x l O " 2
4.3 x 10~2
8.OxIO- 2
4.26 x l O " 5
7.94 x l O " 5
1.49 x l O " 4
2.697 x l O - 4
4.774 x l O " 4
1.055 XlO" 3
1.41 x 10" 4
3.95 x l O " 4
1.05 XlO" 3
1.9Ox 10" 4
5.35 XlO" 4
1.41xlO" 3
1.86 x 10 ~5
4.0OxIO" 5
1.592 x l O " 4
5.525 x l O " 4
8.86 x 10 " 5
7.54 XlO" 5
4.47 x 10- 5
1.33 x 10~5
5.02 XlO" 5
1.690xl0" 4
7.72 x 10~5
1.01 x 10 ~4
8.4xlO~ 6
1.62 x l O - 5
2.08 x l O " 4
7.89 x l O " 5
1.374 x l O " 4
2.36 XlO" 4
4.58 x l O " 4
7.76 xlO~ 4
1.38 x l O " 3
2.39 x l O " 3

118.5
118.5

3.60 x 10 " 4
3.30 x l O " 4

118.5
95
105
93.88
105.68
119.55
63.2
73.8
79.1
87.7

445xlO" 4
3.02 x l O " 5
9.14 x l O " 5
1.67 x 10~5
6.96 XlO" 5
3.39 x l O " 4
8.2xlO~ 6
3.5 XlO" 5
6.9 x l O " 5
1.69 XlO" 4

Ea (kj/mol)

Notes

153.6

126.5

142.3

159.0

175.1

175.1

z (1013)
z (4154)
120.7

110.0

143.5

Refs.
137
137
137
137
266,313
266,313
266,313
46
46
310
310
310
310
240
240
240
171
171
171
171
171
171
335
335
335
335
335
335
366
366
366
366
280,333
280,333
280,333
309
309
309
356
356
200
200
200
171
171
171
171
171
171
171
171
171

h
125.3
a
a
a
h
122.3

b,h

171
266,313
266,313
300
300
300
323
323
323
323

TABLE 2. cont'd
Number of
C atoms
20 (cont'd)

22

24

25

Initiator
(-HJ)-I,l'-Diphenyl-lmethyl-azo-methane
2,2'-Azo-bis(2-methyl-A^-phenylpropionamidine) 2HCl
2,2/-Azo-bis[A^-(4-chlorophenyl)2-methylpropionamidine] 2HCl
2,2'-Azo-bis[Af-(4-hydroxyphenyl)2-methylpropionamidine] 2HCl
l,r-Azo-bis-l-phenyl-3methylbutane
1,1'-Azo-bis-4-ethylcumene

Solvent

T( 0 C)

^d(S1)

Water

106.0
127.9
45

8.26 x l O " 6
1.18 x l O " 4
1.93 x 10 ~5

Water

45.5

Water

Cumene

Ethylbenzene
Toluene

l,r-Azo-bis-4-isopropylcumene

Toluene

U'-Diisopropyl-U'diphenyl-azo-ethane
l,l'-Diphenyl-azocyclopentane

Ethylbenzene

2,2'-Azo-bis[2-methyl-N-(phenylmethyl)propionamidine] 2HCl
2,2'-Azo-bis[2-(4-methyl-4-isobutylimidazoline-2-yl)propane 2HCl
2,2'-Azo-bis[2-(4-methyl-5-isobutylimidazoline-2-yl)propane 2HCl
2,2/-Azo-bis[2-(4-ethyl-5-propylimidazoline-2-yl)propane 2HCl
U'-Azo-bis-4-terf-butylcumene

Water

oc,a'-Azo-bis(a-methylbenzyl)dimethacrylate

Dichlorobenzene

Bis(2,2,4,6,6-pentamethyl4-heptyl)diazine

Diphenyl ether

l,r-Diphenyl-azo-cyclohexane

Benzene

3-Bromophenyl-azo-triphenylmethane
4-Bromophenyl-azo-triphenylmethane
4-Hydroxyphenyl-azo-triphenylmethane

Toluene

Benzene

Methanol
Water
Methanol
Water
Methanol
Water
Toluene

Toluene
Acetic acid
Pyridine
Toluene

2-Nitrophenyl-azo-9-phenylfluorene

Toluene

4-Nitrophenyl-azo-9-phenylfluorene

Toluene

2,4-Dinitrophenyl-azo-9-phenylfluorene
2-Nitrophenyl-azo-triphenylmethane

Toluene
Toluene

3-Nitrophenyl-azo-triphenylmethane

Toluene
Benzene
terf-Butylbenzene

Ea (kj/mol)

Notes

149.2

Refs.

318
318
339

1.93 x 10 ~5

339

47.5

1.93 x 10~5

339

100.4
110.3
42.8
48.6
58.0
42.8
51.2
58.0
50

7.6xl0"5
2.42 x 10 " 4
1.29 x l O " 5
3.29 x l O " 5
1.24Ox 10~4
1.13 x l O " 5
4.26 x l 0 ~ 5
1.078 xlO~ 4
3.52 x l O ' 5

98
98
309
309
309
309
309
309
324

323
323
323
339

29.5
40.0
50.0
52
50
50
50
50
50
50
42.8
48.6
58.0
65
70
80
90
100.1
109.2
125.0
45.5
54.0
69.7
53.8
64.0
53.35
64.30
54.00
64.00
54.00
64.00
54.00
64.00
45.45
55.55
45.45
55.55
55.55
64.94
64.94
75.06
53.8
64.0
60
60

3.16
1.24
4.68
1.93

x 10~4
x 10 " 3
XlO" 3
x 10 ~5

5.54 x 10 " 5
7.08 x 10 ~5
7.72 x 10 ~5
9.78 x 10 ~5
1.06 x 10 " 4
1.41 x 10~4
1.16 x l 0 ~ 5
2.58 x l 0 ~ 5
1.080xl0" 4
3.65 x 10~5
7.98 x 10 ~5
2.313 xlO~ 4
1.344 XlO" 3
3.03 x 10 ~4
7.62 x l O " 4
3.90xl0~ 3
2.52 x 10~5
8.74 x l O - 5
7.12 xlO~ 4
1.14 x 10 " 4
4.58 x 10 " 4
1.05 x 10 " 4
4.28 x 10 " 4
1.42 x 10~4
6.2xlO~ 4
1.52 x l O " 4
6.7 XlO" 4
1.70 x 10~4
6.4 x l O " 4
1.01 x 10~4
3.71 x 10" 4
2.06 x 10 " 4
7.53 XlO" 4
2.06 x 10 " 4
6.92 x 10 ~4
1.46 x 10 ~4
5.26 XlO" 4
5.8 x 10 ~5
1.99 x l O " 4
9.92 x 10 ~5
9.18 x 10 ~5

139.3
108.9

124.4

113.6
103.1

123.6
h

125.7
h
125.7

125.1
117.2
133.9
133.9
121.3
119.7
111.7
119.2
123.8
110.9

356
356
356
356
356
356
309
309
309
366
366
366
366
314
314
314
323
323
323
42
42
52
52
52
52
52
52
52
52
75
75
75
75
75
75
75
75
42
42
263
263

Notes page 11-69; References page 11-70

TABLE 2. cont'd
Number of
C atoms
25 (cont'd)

Initiator

Solvent

3-Nitrophenyl-azo-triphenylmethane

Cumene
Ethylbenzene
Octane
Toluene

4-Nitrophenyl-azo-triphenylmethane

Benzene
tert-Butylbenzene

Chlorobenzene

Cumene

Decane

1-Decene
Dodecane

1-Eicosene
Heptane

Hexadecane

1-Hexadecene
Hexane
1-Hexene
Nonane

Octadecane
1-Octadecene
Octane

1-Octene
Pentane
Tetradecane

4-Nitrophenyl-azo-triphenylmethane

2,4-Dinitrophenyl-azo-triphenylmethane
Phenyl-azo-triphenylmethane

1-Tetradecene
Toluene

Toluene
Acetic acid
Anisole

T( 0 C)

A^(S"1)

60
60
60
45
60
60
60
60
60
55
55
55
55
55
55
60
60
60
50
60
70
77.5
60
50
60
70
60
50
60
70
50
60
70
77.5
60
50
60
60
50
60
70

1.04 x 10~4
1.10 x 10~ 4
1.01 x 10~4
1.25 x 10 " 5
1.22 x l O ~ 4
1.09 x 10 " 4
9.7xlO~ 5
4.03 x l O - 5
4.44 x 10 " 6
8.50xl0~ 5
6.88 x l O " 5
4.42 x l O - 5
8.1OxIO- 5
6.75 XlO" 5
2.62 x l O - 5
1.15 x l O " 4
4.73 x l O " 5
7.23 XlO" 6
2.017 x l O " 5
9.988 x l O " 4
3.35OxIO- 4
1.16 XlO" 3
1.038 x l O " 4
1.933 x 10 ~5
9.166 x l O " 5
3.25OxIO- 4
7.6OxIO- 5
2.716 x l O " 5
1.043 x l O - 4
3.900xl0"4
1.716 x l O " 5
8.133 x l O " 5
2.966 x l O - 4
1.09xl0-3
8.25 x 10 ~5
2.75OxIO- 5
1.195 x l O ~ 4
1.143 x 10 ~4
2.20OxIO- 5
9.900 x l O " 5
3.71OxIO- 4

60
70
60
60
70
77.5
60
50
60
50
60
70
60
64.94
75.06
53.35
64.30
75.06
84.98
43.30
64.00
25.0

7.78OxIO- 5
2.783 x l O - 4
7.58 x 10 ~5
1.015 x 10~4
3.65OxIO- 4
1.78 x l O - 3
1.123 x l O ~ 4
3.600xl0"5
1.28OxIO- 4
1.866 x l O " 5
8.80OxIO- 5
3.116 x l O ~ 4
9.02 x 10 " 5
2.58 x 10~4
9.19 x l O - 4
5.7 x l O - 5
2.25 XlO" 4
1.9OxIO- 4
6.13 x 10~4
5.7 x 10~5
8.4 x l O - 4
2.58 x l O " 6

Ea (kj/mol)

Notes

z (1256)
z (3890)
z (1013)
z (4154)
z (1013)
z (6180)
z (1256)
z (3890)

123.0
113.0
122.6
117.2
120.5

b,h

Refs.
263
263
263
263
263
263
263
263
263
333
333
333
333
333
333
263
263
263
168,263
168,263
168
168
168
168,263
168,263
168
168
168
168,263
168
168,263
168,263
168
168
168
168,263
168,263
168
168,263
168,263
168
168,263
168
168
168,263
168
168
168
168,263
168,263
168,263
168,263
168
168
75
75
52
52
75
75
52
52
103

TABLE 2.
Number of
C atoms
25 (cont'd)

cont'd

Initiator
Phenyl-azo-triphenylmethane

Solvent
Anisole

Benzene

Benzonitrile

/m-Butylbenzene

Chlorobenzene

Cumene

Cyclohexane

Decane
Dodecane
Diethyl malonate

Ethylbenzene
Heptane
Hexadecane
Hexane
Nitrobenzene

Octane

Pyridine
Tetradecane
Toluene

26

2,2/-Azo-bis[2-(4-ethyl-5-propylimidazoline-2-yl)propane 2HCl
Azo-bis-diphenylmethane

Methanol
Water
Toluene

1,1'-Bis-biphenyl-azo-methane

Diphenyl ether

l,l'-Azo-bis-l-(4-tolyl)-cyclohexane

Toluene

T( 0 C)
50.2
74.7
25.0
74.5
80.1
85.9
25.0
49.6
74.7
50
25.0
50.3
74.7
50
50
50
25.0
49.6
74.7
50
50
50
25.0
49.6
74.7
60
60
25.1
74.5
80.1
85.9
50
60
60
60
25.0
74.5
80.1
85.9
50
50
50
60
53.35
64.00
60
43.8
53.8
45
50
45.45
55.55
43.30
53.35
53.3
50
50
54.0
64.0
135.0
145.0
155.0
165.0
36.0

^d(S1)
1.31 x 10~4
3.03 x l O ~ 3
3.0xl0~6
2.9 x l O ~ 3
6.8 x l 0 ~ 3
1.1 x l O ~ 2
4.29 x l O ~ 6
1.24 x l O - 4
3.12 x l 0 ~ 3
1.37 x l O ~ 4
2.62 x l O ~ 6
1.56 x l O ~ 4
3.14 x l 0 ~ 3
1.33 x 10 ~4
3.83 x l 0 ~ 5
9.53 x l O ~ 6
3.77 x l O ~ 6
1.67 x l O ~ 4
3.93 x l 0 ~ 3
1.50 x 10 ~4
6.82 x l 0 ~ 5
7.65 x l O ~ 6
4.22 x l O ~ 6
9.90 x l 0 ~ 5
1.75 x l 0 ~ 3
5.72 x 10~4
5.35 x 10 ~4
3.1 x 10~6
2.8 x 10 ~3
5.9 x l O " 3
1.0 x l 0 ~ 2
1.58 x 10 ~4
6.60xl0~4
4.76 x 10 ~4
7.60xl0~4
2.6xlO~ 6
3.0xl0~3
5.8 x l 0 ~ 3
9.8 x l 0 ~ 3
1.59 x 10 ~4
7.53 x l O ~ 5
1.17 x l 0 ~ 5
6.41 x l O ~ 4
1.74 x l 0 ~ 4
8.OxIO" 4
4.99 x 10 ~4
6.3 x 10" 5
2.4 x l O - 4
9.23 x l 0 ~ 5
1.73 x l O - 4
8.48 x l 0 ~ 5
3.5IxIO-4
6.0xl0~5
2.25 XlO" 4
2.25 x l O - 4
9.75 x 10 ~5
1.33 x 10 ~4
1.01 x 10 ~4
3.4OxIO- 4
1.23 x 10~4
3.58 x l O " 4
7.76 XlO" 4
2.09 x l O - 3
8.7xlO~ 6

E a (kj/mol)

Notes

Refs.

b
b

118.3

112.1

121.3

118.4

102.5

116.6

118.7

129.7

115.5

122.6
113.0
113.0

111.3
134.1

107.1

103
103
114
114
114
114
b,h
103
103
b
103
263
b,h
103
b
103
103
263
z (1140)
263
z (4265)
263
b,h
103
b
103
b
103
263
z (1140)
263
z (4265)
263
h
103
b
103
b
103
263
263
114
114
114
114
263
263
263
263
114
114
114
114
263
z (1140)
263
z (4265)
263
263
52
52
263
42
42
263
263
75
75
52
52
46
356
356
107,312
46,107,312
h
297
297
297
297
200

Notes page 11-69; References page 11-70

TABLE 2. cont'd
Number of
C atoms
26 (cont'd)

Initiator
l,l'-Azo-bis-l-(4-tolyl)-cyclohexane

Toluene

l,r-Diisopropyl-2,2'-dimethyl1,1 '-Diphenyl-azo-propane

Ethylbenzene

4-Methoxyphenyl-azo-triphenylmethane
l,r-Diphenyl-azo-cycloheptane

Toluene

3-Tolyl-azo-triphenylmethane

Benzene
terf-Butylbenzene
Cumene
Ethylbenzene
Octane
Toluene

4-Tolyl-azo-triphenylmethane

27
28

Solvent

4-Acetaminophenyl-azo-triphenylmethane
U'-Azo-bis-l,2-diphenylethane (meso)

Benzene

Benzene
tert-Butylbenzene
Cumene
Ethylbenzene
Octane
Toluene

Toluene
Ethylbenzene

(D,L)

30

l,l'-Dibutyl-l,l'-diphenylazo-pentane

Ethylbenzene

34

l,r-Azo-bis-(l,3-diphenylpentane)
3,10,13,20-Tetraphenyl-l,2,ll,12-tetraaza-Ul-cycloeicosadiene

Bromobenzene
Xylene
Xylene

3,12,15,24-Tetraphenyl-l,2,13,14-tetraaza-l,13-cyclotetracosadiene

Ethylbenzene
Xylene

40

44

Poly[oxyethylenexoxy(l-oxo-2,2-dimethylethylene)azo-(2-oxo-1,1 -dimethylethylene)

o-Xylene

T( 0 C)
42.8
61.1
50.0
60.0
70.0
54.00
64.00
16.2
24.8
33.4
41.1
50
50
50
50
45
43.8
53.8
45
50
50
50
50
50
45
43.30
53.35
45
50
54.00
64.00
96.56
106.47
115.28
96.56
106.47
115.28
50.0
60.0
70.0
89.7
118.8
110
120
130
112.95
110.8
119.8
110
120
130
85
95
105
T(K)

* d (s" 1 )
2.0IxIO" 5
2.009 x l O " 4
6.24 x l O " 5
2.49 x 10 " 4
7.77 XlO" 4
2.13 x l O " 4
7.6xlO" 4
1.65 x 10 " 4
5.52 xlO~ 4
1.66 x l 0 ~ 3
4.52 XlO" 3
1.3OxIO"4
1.3OxIO"4
1.51 x 10 " 4
1.72 x 10 " 4
8.9xl0"5
7.4 x l O " 5
2.77 XlO" 4
9.74 XlO" 5
1.81 x 10" 4
1.26 x 10 ~4
1.35 x 10 ~4
1.4OxIO"4
1.62 x 10 ~4
8.6xl0"5
6.9xlO" 5
2.25 XlO" 4
9.3 x l O " 5
1.52 x l O " 4
1.46 x 10" 4
5.9xlO" 4
2.75 x l O " 5
9.03 x 10" 5
2.42 XlO" 4
3.22 x l O " 5
1.04 XlO" 4
2.84 XlO" 4
5.05 x l O " 5
2.03 x 10~4
6.24 x l O " 4
1.5 x 10" 5
5.6 x 10 " 4
7.2OxIO" 5
2.3OxIO" 4
6.9OxIO" 4
8.76IxIO" 5
8.9 x 10"5
2.2 XlO" 4
7.63 xlO" 5
2.46 x 10"4
7.12 xlO" 4
2.106 x 10"4
7.312 x 10~4
1.995 x 10"3
1.99 x 1014

Ea (kj/mol)

Notes

117.2

113.8

100.4

125.5
138.5

138.9

108.9

145.6

126.4
143.9

124.0

exp[-124.0//?7]

a,h
a
a
a,h
a
a
h

Refs.
200
200
324
324
324
52
52
323
323
323
323
263
263
263
263
263
42
42
263
263
263
263
263
263
263
52
52
263
263
52
52
162
162
162
162
162
162
324
324
324
311
311
38
38
38
158
48
48
38
38
38
332
332
332
332

TABLE 3. ALKYL PEROXIDES


Number of
C atoms

Initiator

Methyl peroxide

Ethyl peroxide

Solvent
Vapor
Methanol
Styrene
Vapor

Vapor (toluene)

2,4-Pentanedione peroxide

Triethyl phosphate

Propyl peroxide

Vapor

Isopropyl peroxide
Allyl
tert-butylperoxide

Styrene
Toluene

Dimethylaminomethyl
peroxide

ter/-butyl

tert-Butyl

peroxide

Acetic acid

Acetonitrile

Benzene

Benzhydrol
terf-Butanol

2-Butanol
n-Butyl mercaptan
Tri-n-butylamine

T( 0 C)
T(K)
T(K)
60
140.2
147.8
160.0
176.5
184.5
145.9
145.9
200
210
218
226
234
245
100
115
125
146.5
155.3
166.8
175.4
60
130
140
150
160
110
120
130
115
120
125
130
95
125
115
120
125
130
80
130
100
100
115
130
120
120
120
120
120
125
130
135
125
120
125
130
135
125
125
125
135

^a(S1)

Ea (kj/mol)

1.6xlO 15
4.IxIO15
1.2xlO" 9
1.75 x 10 ~4
3.6OxIO- 4
1.08 x l O " 3
3.78 x l 0 ~ 3
7.16 x l O " 3
6.69 x l O - 4
5.02 x l O " 4
3.58 x 10 ~2
6.76xlO- 2
1.47XlO- 1
2.23XlO- 1
3.86XlO" 1
6.43XlO- 1
1.9X10" 6
6.IxIO"6
1.4 x l O " 5
2.50xl0~ 4
6.0OxIO- 4
1.95 x l O " 3
4.1OxIO- 3
6. xlO" 1 0
5.76 x l O " 5
1.785 XlO" 4
4.800xl0~ 4
1.27OxIO-3
5.5xl0~ 5
1.9 x l O " 4
4.76 x l O " 4
1.2 x l O " 5
2.19 x l O " 5
2.98 x l O " 5
6.29 x l O - 5
9.53 x 10 " 7
3.89 x l O - 5
1.19 x l O " 5
2.21 x 10~5
3.47 x l O - 5
5.63 x l O " 5
7.81xl0"8
(2.48-3.04) x 10~5
8.8 x l O " 7
8.75 XlO" 7
5.66 x l O " 6
3.0OxIO- 5
1.39 x l O - 5
7.6 x l O - 6
7.5 x l O - 6
3.7 XlO" 6
1.10 x l O - 5
1.99 x l O - 5
3.22 XlO" 5
6.19 x l O " 5
8.7xl0"5
1.41 x 10 ~5
2.49 x l O " 5
4.3OxIO- 5
7.32 x l 0 ~ 5
4.8xlO-5
1.5 x 10 ~5
(1.70.3) x 10" 5
(4.2 0.4) x 10 " 5

exp[- Ul.l/RT]
exp[-153.9//?7]
147.3
131.8

Notes

a
a
a
a
a
t8

132.6

92

132.2

154.8
139.1

a
a
a
a
a
a
a
h,m6

134.5

139.7

129.7

d
h

142.3
146.9

m 2 ,u 2
m 2 ,u 2
a

147.7

a
a
z (0.98)
z (864)
z (1620)
z (3480)
h

143.5

Refs.
72
225
92
127
127
127
127
127
187
187
87
87
87
87
87
87
337
337
337
128
128
128
128
92
321
321
321
321
303
303
303
192
192
192
192
208
208
192
192
192
192
129
129
126,337
197
126,337
126,337
33
33
33
33
192
192
192
192
140
192
192
192
192
140
140
64
64

Notes page II - 69; References page II - 70

TABLE 3. cont'd
Number of
C atoms
8 (cont'd)

Initiator
terf-Butyl

peroxide

Solvent
Tri-n-butylamine
tert-Butylbenzene

Carbon tetrachloride

Chlorobenzene

Cumene

Cyclohexane

Cyclohexanol
Cyclohexene

Cyclohexylamine
Decane

Dodecane

Dimethylaniline

Ethyl benzoate

Af-Ethylcyclohexyl amine
Heptane
Hexadecane

Hexane

T( 0 C)
145
T (K)
125
135
145
T (K)
125
125
125
120
120
120
120
125
150
121
141
164
T (K)
125
135
145
T (K)
95
120
125
130
135
125
120
125
130
135
120
120
120
120
125
80
110
130
115
130
140
80
110
130
120
125
130
135
120
125
130
135
125
80
110
80
110
130
80
110

kd (s~l)
(1.600.21) x 10~4
2.8 x 1 0 u
(1.5 0.2) x 10~5
(5.00.3)xl0-5
(1.51 0.22) xlO~ 4
2.8 x 1014
2.1OxIO- 6
2.49 x l O - 6
2.03 xlO~ 6
9xlO"6
2.4 x l O - 6
2.3 x l O - 6
8.6 x l 0 ~ 7
1.4OxIO- 6
4.45 x 104
1.93 x l 0 ~ 5
1.93 x l O - 4
1.93 XlO" 3
4.20 x 1015
(1.60.1) x 10~5
(5.2 0.3) x 10- 5
(1.560.13)x 10~4
2.8 x 1014
2.48 x 10 ~7
6.3 x l O - 6
1.52 x l O - 5
2.59 XlO" 5
4.64 x l 0 ~ 5
2.4 x l O " 5
7.6 x 10~6
1.38 x l O - 5
2.81 x 10- 5
4.4IxIO-5
8.3 XlO" 6
6.2 XlO" 6
3.77 x l O " 6
2.65 XlO" 6
5.50xl0~ 5
1.39 x 10 ~8
2.0IxIO-6
2.48 XlO" 5
3.00xl0~ 6
2.16 xlO~ 5
6.66 x l 0 ~ 5
1.29 x 10 ~8
1.87 xlO~ 6
2.44 x l 0 ~ 5
9.6xlO~ 6
1.89 x l 0 ~ 5
3.41 x l 0 ~ 5
5.84 x l 0 ~ 5
1.07 x l 0 ~ 5
1.92 x l 0 ~ 5
3.39 x l 0 ~ 5
5.90xl0~ 5
4.01 x 10 ~5
1.44 x 10 ~8
2.19 xlO~ 6
1.07 x 10 ~8
1.82 xlO~ 6
2.33 xlO~ 5
1.64 x 10 ~8
2.17 xlO~ 6

EB (kj/mol)

Notes

exp[- U6A/RT\

exp[- 146A/RT]
U1
s
s,t6
z (0.98)
z (1930)
z (2890)
z (5525)
ui,t 6

exp[- 153.46/RT]

exp[- H6A/RT]
170.7

156.1

157.3

z (0.98)
z (1275)
z (2890)
z (5725)
h

163

a
a
a

148.5

Refs.
64
123
64
64
64
123
301
301
301
33
33
33
33
301
346
344
344
344
344
64
64
64
123
208
192
192
192
192
140
192
192
192
192
33
33
33
33
143
270
270
270
337
337
337
270
270
270
192
192
192
192
192
192
192
192
143
270
270
270
270
270
270
270

TABLE 3. cont'd
Number of
C atoms
S (cont'd)

Initiator
terf-Butyl

peroxide

Solvent
2-Methyl-2-butanol

Methyl methacrylate
AT-Methylpipendine
Mineral oil
Nonane

Norbornanol
Nujol
Octane
2-Octanol
Piperidine
1-Propanol
Styrene
Tetradecane

Tetrahydrofuran

Toluene

Triethylamine

Vapor (acetone)

Vapor (carbon
tetrachloride)
Vapor (chloroform)
Vapor (dichlorodifluoromethane)
Vapor (trichloro
ethylene)
Vapor (methylene
chloride)
Vapor (3-pentanone)
Vapor (silicon
tetrafluoride)
Vapor (toluene)
Vapor

T( 0 C)

^d(S"1)

Ea (kj/mol)

Notes

149.4

Refs.

120
125
130
135
T (K)
125
T (K)
80
110
130
125
125
80
110
125
125
125
T(K)
80
110
130
120
125
130
135
125
100
120
120
120
120
125
125
T(K)
120
125
130
135
127.5
131
146
151.5
162
167
145
T (K)
150

1.26 xlO" 5
2.34 XlO" 5
4.47 xlO" 5
6.8OxIO"5
2.8 x 10 14
1.54 xlO" 5
1.31 x 1015
1.36 x 10 ~8
2.0IxIO" 6
2.54 x 10 ~5
4.4xlO" 5
7.8 XlO" 7
1.48 x 10 "8
2.19 xlO" 6
5.5xl0"5
3.49 x 10 ~5
2.8xl0"5
2.8xlO 1 4
1.12 xlO" 8
1.82 xlO" 6
2.38 xlO" 5
9.7xlO" 6
1.84 XlO" 5
3.39 xlO" 5
5.76 xlO" 5
1.5 x l 0 ~ 5
6.82 x 10 ~7
1.34 XlO" 5
9.5 xlO" 6
8.OxIO- 6
5.7 xlO" 6
1.6 xlO" 5
1.62 xlO" 5
1.3OxIO16
7.9xlO~ 6
1.69 xlO" 5
3.15 xlO" 5
5.55 XlO" 5
7.4 xlO" 6
1.13 XlO" 5
6.OxIO" 5
1.03 xlO" 4
3.6 xlO~ 4
5.2 xlO" 4
1.3 xlO" 4
5.9 x 10 16
8.58 x 10 "4

150
150

1.167 xlO" 3
>(2.00 x 10 ~4)

130
130

150

2.35 x 10"3

130

150

1.017 x 10 ~3

130

145
T (K)
160
160
160
148
158
103.2
111.9

1.5 x 10~ 4
6.8 x 10 16
1.05 xlO" 3
1.25 x l 0 ~ 3
1.27 xlO" 3
9.OxIO- 5
2.5 xlO" 4
5.6xlO" 7
2.03 XlO" 6

exp[- U6A/RT]
exp[- 154.6/RT]

exp[-146.4//?7]

155.2

z (0.98)
z (2000)
z (2850)
z (5170)

exp[- 15S3/RT]
169.9

165.3
exp[- 1653/RT]
1

165.3
exp[- 1653/RT]
113.0

a,i(2.6)
a,i(33)
a,i(100)

192
192
192
192
123
143
376
270
270
270
140
301
270
270
140
143
140
123
270
270
270
192
192
192
192
140
197
33
33
33
33
140
143
376
192
192
192
192
238
238
238
238
238
238
125
125
130

125
125
117
117
117
88
88
227
227

Notes page 11-69; References page II - 70

TABLE 3. cont'd
Number of
C atoms
S (cont'd)

Initiator
tert-Butyl peroxide

Solvent
Vapor

Vapor (He)

KBr pellets

terf-Butyl 2-chloro-l,l-dimethylethylperoxide

Cumene

sec-Butyl peroxide

Toluene
Vapor
Decane
Dodecane
Heptane
Hexadecane
Octane
Styrene
Tetradecane
Chlorobenzene
Chlorobenzene
Chlorobenzene
Chlorobenzene

Butyl peroxide

Bromo-terf-butyl peroxide
Chloro-terf-butyl peroxide
Bis(chloro-tert-butyl) peroxide
2-terf-Butyl peroxy-2-methyl1-propanol

T( 0 C)
120.2
129.5
138.5
145.4
125
135
145
129.6
141.0
152.5
166.8
130
140
150
160
170
129
138
149
152
139.7
147.2
154.6
159.8
T (K)
145
T(K)
149.5
160
160
160
130
140
150
160
280
290
300
310
320
330
340
350
109
127
149
120
130
140
150
100
100
80
80
80
80
80
60
80
150
150
150
150

A^(S" 1 )
6.39 x 10 " 6
1.98 XlO- 5
6.0OxIO- 5
1.24 x l O ~ 4
1.1 x K r 5
3.6 XlO- 5
1.15 x l O - 4
1.64 x l 0 ~ 5
6.28 XlO" 5
2.25 x l O - 4
8.92 x l O - 4
1.82 x l O - 5
5.75 x l O " 5
1.75 x l O - 4
4.88 x l O " 4
1.35 x l O - 3
1.97 x l O - 5
4.3 x l O - 5
1.30 x l O ~ 4
1.62 XlO" 4
6.OxIO- 5
1.43 x l O - 4
3.22 x l O - 4
5.53 x l O - 4
3.2 x 10 16
1.3 x l O - 4
1.9xlO 1 6
1.79 XlO" 4
4.0OxIO- 4
4.53 XlO" 4
4.83 x l O - 4
1.91 x 10" 5
5.95 x l 0 ~ 5
1.78 x l O " 4
4.96 x l 0 ~ 4
7.7
1.5IxIO 1
2.77X10 1
4.87XlO 1
8.34XlO 1
1.38 x l O 2
2.13 x l O 2
3.22 x l O 2
3.8 x 10" 7
2.96 x l O - 5
4.4 x l O " 4
8.82 x 10~6
2.8OxIO- 5
9.26 x l 0 ~ 5
2.78 x l O - 4
2.7 x 10 ~6
1.5 x 10" 6
1.43 x 10 " 8
1.17 x l O " 8
2.04 x 10~8
8.8 x 10 ~9
1.58 x l O " 8
3.3 x 10 ~9
9.6xlO-9
3.63 x 10 " 4
4.15 x 10 ~A
3.11 x 10 ~4
1.16 x 10 " 3

Ea (kj/mol)

159.0

Notes

a
a
a
a
a

163.6

exp[- 163.6/RT]
161.5
exp[-161.5//?7]
156.5
i(37-132)
154.8
a,i(2.6)
a,i(33)
a,i(100)
156.7
U3
U3
U3
U3
154.8
i(10)
i(10)
i(10)
i(10)
i(10)
KlO)
i(lO)
i(lO)
159.0
h

t6
t6
t6
t6
t6
142.3
t6

Refs.
227
227
227
227
64
64
64
86
86
86
86
96
96
96
96
96
88
88
88
88
63
63
63
63
63
125
175,125
83
117
117
117
277
277
277
277
111
111
111
111
111
111
111
111
241
241
241
363
363
363
363
197
197
270
270
270
270
270
92
270
346
346
346
346

TABLE 3. cont'd
Number of
C atoms

J(0C)

Initiator

Solvent

2-tert-Buty\ peroxy-2-methyl1-propanol-di
l-Hydroxybutyl--butyi peroxide

Chlorobenzene

150

a-Methylstyrene

1-Hydroxyisobutyl-isobutyl peroxide

a-Methylstyrene

1-Hydroxyisobutyl-l-di-isobutyll,l-d 2 peroxide

a-Methylstyrene

Dimethylaminomethylterf-amyl peroxide

Styrene

Diethylaminomethylterf-butyl peroxide

Styrene

N-Piperidinomethyltert-buty\ peroxide

Styrene

tert-Butyl tert-amyl peroxide

Cumene

10

tert-Amyl peroxide

Bulk

79.4
99.4
109.9
79.4
99.4
109.9
99.5
109.8
122.0
110
120
130
110
120
130
110
120
130
110
120
130
140
125
132.2
108
128
150
T (K)
125
125
125
132.2
136.7
142.2
149.2
136.7
142.2
149.7
110
120
130
140
110
120
130
140
150
127.5
130
132.5
135
137.5
140
142.5
145
147.5
150
80
85
100
115

8 (cont'd)

Chlorobenzene

Decalin
Octane
Triethylamine
Vapor

11
12

tert-Butyl 1,1-dimethylbutyl
peroxide

Cumene

ter/-Butyl 1,1,2-trimethylpropyl
peroxide

Cumene

2-Methyl-2-tert-butyl-peroxyacetate
Ethyl 2-terf-butylperoxymethylpropenoate

Chlorobenzene
Triisopropylbenzene

Apocamphane-1-formyl peroxide
2,2-Bis(tert-butylperoxybutane)

Benzene
Benzene

A:d (s" 1 )

Ea (kj/mol)

Notes

1.23 x 10" 3
1.7 x 10~5
1.06 x l O - 4
2.9 x l O - 4
3.7 x 10" 5
2.OxIO" 4
4.8 x l O - 4
6.9xlO~ 5
1.8 x 10~4
4.2 x l O - 4
4.9xlO"5
1.19 x 10" 4
3.76 x l O " 4
4.IxIO-5
1.35 x 10~4
3.25 x l O - 4
5.5 x 10" 5
2.66 x 10 ~4
4.16 x l O - 4
3.86 x 10" 6
1.287 x l O - 5
4.3OxIO- 5
1.406 x l O - 4
5.7xlO- 5
1.15 XlO" 4
1.93 x 10 ~5
1.93 x l O " 4
1.93 x 10- 3
4.02 xlO 1 5
2.8xl0-5
3.0xl0"5
3.5 x 10 ~5
7.2 x 10~5
1.15 XlO" 4
2.16 xlO~ 4
4.8 x l O " 4
1.34 x l O - 4
2.4IxIO- 4
5.61 x 10" 4
4.38 x l O " 6
1.537 x l O " 5
4.99 x l 0 ~ 5
1.544 x l O - 4
7.07 x 10 " 6
2.374 x 10 ~5
7.62 x l 0 ~ 5
2.308 xlO~ 4
4.12 x 10 " 4
1.63 x 10~4
1.95 x l O " 4
2.16 x l O " 4
2.56 x l O - 4
3.47 XlO" 4
3.92 x l O - 4
4.68 x l O - 4
5.37 x l O - 4
6.3OxIO- 4
7.76 x l O ~ 4
2.3 x 10 ~4
3.OxIO- 6
1.9 x l 0 ~ 5
9.36 x l 0 ~ 5

Refs.
346

102.9

83.7

c
c
c

89.5

130.7

132.4

130.7

tn
tn
tn
tn
tn
tn
tn
tn
tn

exp[- US35/RT]

154.8-171.5

i(200-225)
i(200-225)
i(200-225)
i(100-200)
i(440-610)
i(440-610)
i(440-610)

C2
C2
C2
C2
C2
C2
C2
C2
C2
C2
151

a
a
a

32
32
32
32
32
32
25
25
25
303
303
303
303
303
303
303
303
303
363
363
363
363
202
202
344
344
344
344
202
202
202
63
63
63
63
63
63
63
363
363
363
363
363
363
363
363
346
353
353
353
353
353
353
353
353
353
353
244
337
337
337

Notes page 11-69; References page II - 70

TABLE 3. cont'd
Number of
C atoms
12 (cont'd)

13

Initiator

Solvent

tert-Butyl 1,1,3,3-tetramethylbutyl
peroxide

Cumene

1-Hydroxy-l-hydroperoxydicyclohexyl peroxide

Benzene

Di-(I -hydroxycyclohexyl)peroxide
Diisopropylaminomethyltert-amyl peroxide

Chlorobenzene

1-Phenylethyl terf-butyl peroxide


terf-Butyla-cumyl
peroxide

Chlorobenzene
terf-Butylbenzene

Styrene

Chlorobenzene

Cumene

Dodecane

14

15
16

terf-Butyl />-chlorocumyl peroxide


tert-Butyl p-nitrocumyl peroxide
tert-Butyl l,l-dimethyl-2-phenylethyl peroxide

Cumene
Cumene
Cumene

U-Di-(terf-butylperoxy)cyclohexane
Ethyl-3,3-di-tert-butylperoxy)-butyrate
l-[4-(Dimethylamino)phenyl]ethyl tert-butyl peroxide

Benzene
Benzene
Chlorobenzene

tert-Butyl /?-methoxycumyl peroxide


tert-Butyl p-methylcumyl peroxide
terf-Butyl m-methoxycumyl peroxide
Bis(l, 1,2,2-tetramethylpropyl) peroxide
2-[4-(Dimethylamino)phenyl]propyl tert-buty\ peroxide
l,l-Di-(terf-amylperoxy)cyclohexane
tert-Butyl 3-isopropenylcumyl peroxide

Cumene
Cumene
Cumene
Cumene
Chlorobenzene

2,5-Dimethyl-2,5-di(tert-butylperoxy)-hexane

Benzene

Benzene
Chlorobenzene

Chlorobenzene

2,5-Dimethyl-2,5-di(terr-butylperoxy)-3-hexyne

Benzene

T( 0 C)

kd (s" 1 )

110
120
130
140
85
100
115
130
105
120
110
120
130
129.2
138
158
115
136
159
T(K)
138
158
125
128
138
148
158
125
125
110
120
130
140
93

1.085 x 10~5
3.73 x 10 ~5
1.141 x 10~4
3.40xl0~ 4
9.6xlO~ 6
5.1 x 10 ~5
1.9 xlO~ 4
5.2 x l O - 4
~1.9xl0~5
~1.9xlO~4
3.9xl0"5
1.21 x 10~4
3.OxIO" 4
3.09 x 10~5
1.48 xlO~ 4
9.62 XlO" 4
1.93 x 10 ~5
1.93 xlO~ 4
1.93 x l 0 ~ 3
1.17 xlO 1 5
1.44 xlO~ 4
8.88 xlO~ 4
3.04 x l 0 ~ 5
4.44 x 10 ~5
1.39 xlO~ 4
3.21 x 10 ~4
8.88 xlO~ 4
2.42 x 10 ~5
2.20 x 10 ~5
4.35 x 10 ~6
1.458 x 10~5
4.70xl0~ 5
1.463 xlO~ 4
1.9xlO~ 5

111
100.4
110.8
120.9
129.2
129.2
125
125
125
125
129.2

1.9xl0" 5
1.82 xlO~ 6
6.97 x 10 ~6
2.18 x l 0 ~ 5
6.18 x l 0 ~ 5
5.22 x l 0 ~ 5
3.72 x 10 ~5
3.22 x 10 ~5
2.84 x 10 ~5
4.84 xlO~ 4
1.51 x 10~4

90
104
126
152
T(K)
115
130
145
115
134
156
T (K)
115
130
145
160

1.9xl0~ 5
1.93 x 10 ~5
1.93 x 10 ~4
1.93x10-3
1.161xl0 13
1.15 x l 0 ~ 5
6.86 x 10 ~5
4.75 xlO~ 4
1.93 x l 0 ~ 5
1.93 xlO~ 4
1.93 x l 0 ~ 3
1.68 x 1016
3.91 x 10 ~6
2.35 x 10 ~5
1.14 xlO~ 4
6.17 xlO~ 4

Ea (kj/mol)

Notes

a,c2
a,c2
a,c2
a,c2

132.4

tn
tn
tn
a
a

exp[-146.98//?7]
a
a
146.4

a
a
a
a

a
a
151.7

m2

m2

exp[-128.33/#7]
166.9

exp[- 155.49/RT]
156.9

a
a
a

a
a
a
a

Refs.
363
363
363
363
337
337
337
337
344
344
303
303
303
282
80
80
344
344
344
344
80
80
352
80
80
80
80
352
352
363
363
363
363
338
338
282
282
282
282
282
352
352
352
352
282

338
344
344
344
344
126,337
126,337
126,337
344
344
344
344
126,337
126,337
126,337
126,337

TABLE 3. cont'd
Number of
C atoms
16 (cont'd)

17

18

Initiator
2,5-Dimethyl-2,5-di(terf-butylperoxy)-3-hexyne

rc-Butyl-4,4-bis(terf-butylperoxy)valerate

Solvent
Chlorobenzene

Dodecane

1,1 -Bis-(terr-butylperoxy)3,3,5-trimethylcyclohexane

Benzene

Cumyl peroxide

Benzene

terr-Butylbenzene
Chlorobenzene

Cumene

Dodecane

Diisopropylcarbinol
Neat

Bicyclo[2.2.2]octane1-formyl peroxide

20

a,a'-Bis(tert-butyrperoxy)diisopropyl benzene

Carbon tetrachloride

Chlorobenzene
Cyclohexane
Isooctane
Toluene
Benzene

Chlorobenzene

Neat

24

TABLE 4.
Number of
C atoms
4

2,5-Dimethyl-2,5-di-(2-ethylhexanoylperoxy) hexane

Benzene

T( 0 C)

^d(S" 1 )

Ea (kj/mol)

Notes

Refs.

120

1.93 x 10~5

344

141
164
T (K)
100
115
130

1.93 xlO~ 4
1.93 x l O - 3
1.90 x 1015
5.83 x 10" 6
3.53 x 10 ~5
2.9IxIO-4

344
344
344
8
8
8

85
100
115
115
130
145
158
112
132
154
T (K)
T (K)
138
158
128
138
148
158
138
150
155
160
165
30

6.9xlO~ 6
138
5.05 x l O - 5
2.7IxIO-4
2.05 x 10 ~5
159
1.05 x l O - 4
6.86 x l O - 4
1.72 x 10 ~3
1.93 x IO" 5
1.93 xlO~ 4
1.93 x l O - 3
9.24 x 1015
exp[- 152.61/RT]
4.31 x 1014
exp[- 1443/RT]
2.57 x l O - 4
1.52 x l O - 3
8.75XlO" 5
2.31 x 10- 4
5.37 xlO~ 4
1.83 x l O - 3
3.16 x 10~4
3.98 x 10~3
4.81 x 10- 3
9.63 x l O - 3
1.16 x l O - 2
1.71 x 10 " 4
1.73 x 10 " 3
1.68 x l O - 4
6.2OxIO" 4
6.IxIO-5
5.OxIO- 5
3.66 x 10 " 4
1.9 x l O " 5
147
4.91 x 10 ~5
9.61 x 10- 5
1.93 x 10~5
1.93 x l O - 4
1.93 x l O - 3
7.65 xlO 1 5 exp[- 152.69 kJ/RT]
3.61 x 10~3
4.44 x l O " 3
4.62 x l O - 3
1.9xlO- 5

30
30
30
30
115
125
130
114
134
156
T(K)
155
160
165
68

exp[- 150.61/RT]
a
a
a
a
a
a
a
a
a
a

a
a
a
a
a
a
a
a
a
a
a
n
vi

a
a
a

a
a
a
a

337
337
337
337
126,337
126,337
80
344
344
344
344
67
80
80
80
80
80
80
80
371
371
371
371
244
244
244
244
244
244
244
337
337
337
344
344
344
344
371
371
371
338

ACYL PEROXIDES

Initiator
Acetyl peroxide

Solvent
Acetic acid

T( 0 C)
55.2
64.9
75.2
85.2
73.2

kd (s"1)
2.8 x 10~6
9.9xlO~ 6
3.75 x l O - 5
1.3OxIO- 4
2.62 x l O - 5

a (kj/mol)

Notes

126.4

d,e
d,e
d,e
d,e
a

Refs.
106,176
106,176
106,176
106,176
100

Notes page 11-69; References page II - 70

Table 4. cont'd
Number of
C atoms
4 (cont'd)

Initiator
Acetyl peroxide

Solvent
Benzene

H-Butanol
seoButanol
tert-Butanol
Carbon tetrachloride

Chloroform
Cyclohexane

Cyclohexene

Cyclopentene

Cumene
Decane
n-Dodecane
Ethanol
Heptane
Hexadecane
-Hexane
1-Hexene

2-Methyl-l-pentene

rc-Octadecane
n-Octane
Isooctane

1-Pentene

Propionic acid

J( 0 C)
35
55
65
50
70
85
70
60.3
80
55.2
64.9
75.2
85.2
60.3
60.3
60.3
80.3
26
46
65
80
80.3
55.2
64.9
75.2
85.2
60
70
80
90
100
70
80
90
100
80
80
60
80
60.3
80.3
80
80
60
70
80
90
100
80
90
100
60
60
80
60
55.2
64.9
75.2
85.2
70
80
90
64.9
85.2

A^(S"1)
9.5 x 10 ~7
3.14 XlO" 6
1.27 x l O - 5
1.1 x l O " 6
2.39X10" 5
1.73 x l O " 4
2.38 XlO" 5
5.OxIO" 6
8.7xl0-5
2.6 XlO" 6
1.07x10-5
4.65x10-5
1.62 XlO" 4
3.4xlO" 5
3xl0~5
3.1xl0"6
4.9x10-5
1.08 x 10 " 7
4.84 XlO" 7
2.11 x l O " 6
5.5x10-5
~5
2.1 x 10"6
8.3 XlO" 6
3.6OxIO- 5
1.27 XlO" 4
4.5xlO~ 6
1.77x10-5
7.0x10-5
2.28 xlO" 4
7.61X10" 4
1.6OxIO-5
7.0x10-5
2.55 XlO" 4
7.25 xlO" 4
7.6xl0-5
6.85 x l 0 ~ 5
2.3xlO" 6
6.15x10-5
1.01 x 10 " 4
1.4OxIO-3
7.72 x 10 " 5
5.39 x l O " 5
3.4xlO~ 6
2.35 x 10" 5
8.7x10-5
3.05 XlO" 4
9.83 x l O " 4
9.OxIO" 5
3.12 XlO" 4
9.81 x 10 " 4
1.9xlO" 6
2.9xlO" 6
7.34x10-5
2.9xlO~ 6
2.35 x l O " 6
9.4 XlO" 6
4.03x10-5
1.49 XlO" 4
2.45 x 10 " 5
9.4 x 10"5
3.22 XlO" 4
1.4 x l O " 5
1.66 XlO" 4

Ea (kj/mol)

Notes

134

a
a
a
a

135.1

c,e
c,e
c,e
c,e

133.9

131.4

c,e
c,e
c,e
c,e

133.5

137.2

129.7

132.6

126.8

134.7

c,e
c,e
c,e
c,e

d,e

Refs.
68
68
68
337
126,337
126,337
16
4
20
106,176
106,176
106,176
106,176
4
4
4
4
68
68
68
20
4
106,176
106,176
106,176
106,176
20
20
20
20
20
20
20
20
20
20
168
70
168
4
4
168
168
70
20
20
20
20
20
20
20
70
70
168
70
106,176
106,176
106,176
106,176
20
20
20
106,176
106,176

Table 4. cont'd
Number of
C atoms
4 (cont'd)

Initiator
Acetyl peroxide

Solvent
n-Tetradecane
Toluene

Vapor (toluene)

Propionyl peroxide

Acetic acid
Acetic anhydride
Benzene

Benzonitrile
Dioxane
n-Hexane
Isooctane
Nitrobenzene
Toluene
Vapor

2-Iodopropionyl peroxide

Perfluoropropionyl peroxide

2,2,3,3-Tetrafluoropropionyl
peroxide
tert-Butyl permaleic acid
Butyryl peroxide

Acetone
Benzene

H-Butyl vinyl ether


Cyclohexene
95%Ethanol
Freon 113

Isooctane
Freon 113
Acetone
Acetic acid
Acetic anhydride

J( 0 C)
60
80
60.3
55.2
64.9
75.2
85.2
73.2
85.5
90
88.0
134.7
150.7
161.7
170.7
184.2
65.0
85.0
65.0
85.0
65.0
85.0
50
70
85
65.0
85.0
65.0
85.0
65.0
85.0
65.0
86.5
65.0
85.0
65.0
85.0
65.0
85.0
99.4
134.4
152.2
176.4
190.9
T (K)
56
62.5
62.5
62.5
62.5
62.5
62.5
20
30
40
T (K)
T(K)
25
35
87
65.0
85.0
65.0
85.0

^d(S1)
2.OxIO" 6
5.9OxIO" 5
5xlO"6
2.7 xlO~ 6
1.14 x l O " 5
4.70xl0~ 5
1.59 xlO~ 4
3.06 XlO" 5
1.72 XlO" 4
7.33 x l O " 5
3.12 x l O " 4
3.1 x 10" 2
1.18XlO"1
2.77XlO" 1
6.10X10" 1
1.76
3.8xlO~ 5
4.3 XlO" 4
3.5 x l O " 5
4.5 x l O " 4
1.88 x KT 5
2.4OxIO" 4
2.72 x l O " 6
4.3OxIO" 5
2.89 XlO" 4
3.9xl0"5
5.IxIO"4
4.5 x 10~5
4.5 x l O " 4
1.50x 10" 5
1.72 x l O " 4
9.8 x l O " 6
1.44 x l O " 4
3.7xl0"5
4.1 x 10 " 4
1.87 x l O " 5
2.54 x l O " 4
1.0 x l O " 5
1.6 xlO~ 4
8 xlO"4
2.6 XlO" 2
1.22XlO- 1
8.OxIO" 1
2.33
2.5 x 10 " 4
2.19 x 10 ~4
(2.40-2.81) x 10 ~4
7.12 XlO" 4
(2.36 0.07) x 10 ~4
2.47 x 10" 4
2.7xlO" 4
4.OxIO" 4
2.19 x 10 " 5
8.5OxIO- 5
3.26 XlO" 4
1.8 x 109
1.5xlO 17
2.26 x 10 " 4
7.17 x 10 " 4
1.9xlO~ 5
4.7 x 10" 5
5.6 x l O " 4
4.3 x 10 " 5
5.5 x l O " 4

Ea (kj/mol)

129.7
133.9

138.1
129.7
123.4

123.0
128.9
129.3
127.6

130.5
116.7

Notes

c,e
c,e
c,e
c,e
a
a
a

c,e
c,e
d,e
c,e
c,e
c,e
a
a
a
d,e
d,e
c,e
c,e

123.8
130.5
120.9

c,e
c,e
c,e

130.1
125.5
125.5

exp[- 125.5/RT]

100.1

s
s
n,s
p
s
s
s
h

exp[- 83.8//?7]
exp[- 121.5/RT}
86.3

108.8

125.1

a
c,e
c,e
c,e

Refs.
70
168
4
106,176
106,176
106,176
106,176
100
100
113
105
105
105
105
105
105
51
51
51
51
51
51
126,337
126,337
126,337
51
51
51
51
51
51
51
51
51
51
51
51
51
51
85
85
85
85
85
85
77
77
77
77
77
77
77
283
283
283
304
304
283
283
338
51
51
51
51

Notes page II - 69; References page II - 70

Table 4. cont'd
Number of
C atoms
8 (cont'd)

Initiator
Butyryl peroxide

Solvent
Benzene
Benzonitrile
Dioxane
Hexane
Isooctane
Toluene
Vapor

Isobutyryl peroxide

Acetonitrile
Benzene

Benzonitrile
tert-Butanol
Carbon tetrachloride

Chlorobenzene

Chloroform
Cyclohexane
Fluorobenzene
Isooctane

Cyclopropane formyl peroxide

Isopropanol
Nitrobenzene
Nujol
Tetralin
Toluene
Vapor
p-Xylene
Carbon tetrachloride

Diacetyl succinoyl diperoxide

Styrene

Succinoyl peroxide

Acetone

T( 0 C)
65.0
85.0
65.0
85.0
65.0
85.0
65.0
85.0
65.0
85.0
65.0
85.0
65.0
85.0
96.7
127.4
158.9
178.9
T(K)
40
20
30
40
40
40
40
40
40
45
50
55
60
40
23
39
57
T (K)
40
40
40
40
25
35
45
55
T (K)
40
40
40
40
40
40
40
40
64.5
70.4
77.8
60
73.5
85
70
85
100

^a(S1)
2.24 x 10~5
3.02 x l O - 4
4.3 x 10~5
5.8 x l O - 4
4.6xlO~ 5
4.6 x l O - 4
1.14 x 10~5
1.53 x l O - 4
1.11 x 10~5
1.56 x l O " 4
2.14 x l O " 5
2.87 x l O - 4
1.6 x l O " 5
2.OxIO- 4
8.6 x l O " 4
1.5 XlO" 2
3.OxIO" 1
1.27
1.9 xlO~ 4
6.81 x 10 " 4
1.6 x l O " 5
6.75 x l O - 5
2.59 x l O - 4
2.38 XlO" 4
2.4OxIO- 4
4.2xlO~ 4
2.5IxIO" 4
7.8xl0"5
1.58 XlO" 4
3.05 x l O - 4
5.61 x 10~4
7.67 xlO~ 4
1.73 x 10 " 4
1.93 x l O - 5
1.93 x l O - 4
1.93 XlO" 3
3.37 xlO 1 4
7.5 x 10 ~5
4.5 x 10 ~5
4.7OxIO- 5
1.23 x 10 " 4
3.35 x 10 ~6
1.54 XlO" 5
6.14 x l O - 5
2.26 x l O - 4
2.8 x 1014
3.2 x l O " 5
3.05 x 10~4
5.8OxIO- 4
4.63 XlO" 5
1.75 x 10 ~4
1.43 x 10 ~4
-1 x 10 ~5
1.4OxIO- 4
4.4xlO" 6
9.3 x 10 ~6
2.31 x 10- 5
5.2xlO~~6
2.3 x l O - 5
9.3 x 10- 5
2.8OxIO- 5
1.21 x 10- 4
4.36 x l O - 4

Ea (kj/mol)

Notes

131.4

d,e
c,e
d,e

131.4
116.3
131.4
133.5
130.5

c,e
c,e
c,e
c,e
c,e
c,e
d,e
c,e

123.8
123.8

exp[-123.8//?7]
109

1113
a
a
a
In3

exp[- 109.06//?7]

114.2

exp[- 1H2/RT]

125.5

99.6

a
a
a

Refs.
51
51
51
51
51
51
51
51
51
51
51
51
51
51
85
85
85
85
85
167
337
337
337
167
148,244
148
148
148
148
148
148
148
148
344
344
344
344
148
148
167
148
84
84
84
84
84
148
148
148
167
148
148
167
148
34
34
34
215
215
215
126,337
126,337
126,337

Table 4. cont'd
Number of
C atoms
9

10

11

Initiator
Acetyl benzoyl peroxide

T( 0 C)

Chlorobenzene

70
96
96
75
75
75
41
41
65
70
75
14
25
44.5
56.5
44.5
60
73.5
85
50
60
70

5-Bromo-2-thenoyl peroxide
4-Bromo-2-thenoyl peroxide
5-Chloro-2-thenoyl peroxide
a-Chloropropionyl m-chlorobenzoylperoxide
Cyclobutane formyl peroxide

Carbon tetrachloride
Carbon tetrachloride
Carbon tetrachloride
Acetonitrile
Cyclohexane
Carbon tetrachloride

Cyclopropane acetyl peroxide

Carbon tetrachloride

Diacetyladipoyl diperoxide

Styrene

Difuroyl peroxide

styrene

2,2,3,3,4,4,5,5-Octafluoropentanoyl
peroxide

Freon 113

Perfluoro-2-(2-ethoxysulfinic
acid) propionyl peroxide
Pivaloyl peroxide
2-Thenoyl peroxide
3-Thenoyl peroxide
Benzoyl isobutyryl peroxide

m-Chlorobenzoyl isobutyryl peroxide

12

Solvent

Freon 113
Carbon tetrachloride
Carbon tetrachloride
Carbon tetrachloride
Acetonitrile
Cyclohexane

Acetonitrile
Cyclohexane

p-Chlorobenzoyl isobutyryl peroxide

Cyclohexane

p-Fluorobenzoyl isobutyryl peroxide

Cyclohexane

5-Methyl-bis-2-thenoyl peroxide
p-Nitrobenzoyl isobutyryl peroxide

Carbon tetrachloride
Cyclohexane

P-Allyloxypropionyl peroxide

Toluene

p-Xylene

m-Chlorobenzoyl 2-methylbutanoyl peroxide

Acetic acid
Acetonitrile

kd (s"1)
2xl0~5
5.12 x l O " 4
4.08 XlO" 4
1.53 x 10 " 5
1.14 x 10 ~5
1.58 x 10 ~5
3.05 x 10 ~5
1.51xl0~ 5
5.15 x 10 " 5
8.95,6.63 x l O " 5
1.41 x 10" 4
9.45 x 10 ~5
9.75,10.57 x 10" 4
5.01 x 10 " 5
2.64 XlO" 4
6.5-8.OxIO" 4
6.6xlO" 6
4.73 XlO" 5
1.84 x l O " 4
7.0xl0"7
2.9 xlO~ 6
1.03 XlO" 5

20
30
40
T(K)

3.29 x 10 " 5
1.27 XlO" 4
5.01 x 10 " 4
2.8xlO 1 4

10
75
75
41
41
70
40
50
60
70
41
40
50
41
50
55
60
65
55
60
65
70
75
40
45
50
55
60
70
80
90
70
80
90
40
40

1.9xlO~ 4
2.21 x 10 ~~5
2.14 x 10 " 5
4.06 x 10 " 4
1.63 x l O " 5
3.05 xlO~ 4
1.45 x l O - 5
5.398 XlO" 5
1.924 x l O " 4
6.872 x l O " 4
1.03 x 10 ~3
3.486 x 10 " 5
1.362 x l O " 4
4.4OxIO- 5
1.029 x 10 ~4
1.651 x 10- 4
3.21 x 10- 4
5.638 x l O - 4
1.117 x 10 " 4
2.038 XlO" 4
4.893 x l O - 4
9.603 x l O " 4
2.92 x 10 " 5
8.1xl0"5
1.336 x l O " 4
2.889 x l O - 4
4.725 X l O ' 4
8.921 x 10 ~4
2.0IxIO" 5
8.62 x l O " 5
2.53 x l O " 4
2.32 x l O " 5
8.88 x l O " 5
2.95 x l O " 4
1.60 x 10 ~3
1.72 x 10 " 3

Ea (kj/mol)

Notes

z(25),vi3
z(19),vi3
a,mi
a,mi
a,mi
ni3
ni3

101.7
n

125.7

100.6

exp[-95.1//?7]

a,mi
a,mi

112.5

h,j
j
j
j

111.3

h,j
j
j

a
a
a
a
a
a

Refs.
155
284
284
232
232
232
167
167
34
34
34
34
34
24
24
24
215
215
215
287
287
287
283
283
283
304
244
232
232
167
167
167
164
164
164
164
167
164
164
167
164
164
164
164
164
164
164
164
232
164
164
164
164
164
191
191
191
191
191
191
256
256

Notes page II - 69; References page II - 70

Table 4. cont'd
Number of
C atoms
12 (cont'd)

14

Initiator
m-Chlorobenzoyl 2-methylbutanoyl peroxide

Solvent

Cyclobutane acetyl peroxide

2-Butanol
Carbon tetrachloride
Cyclohexane
Carbon tetrachloride

Cyclopentane formyl peroxide

Carbon tetrachloride

Hexanoyl peroxide
5-Hexenoyl peroxide

Toluene
Toluene

4-Methoxybenzoyl isobutyrylperoxide

Cyclohexane

4-Methylbenzoyl isobutyrylperoxide

Cyclohexane

4-Methyl-2-thenoyl peroxide
5-Methyl-2-thenoyl peroxide
Perfluoro-2-furnanacetyl peroxide
Perfluoro-2-propoxypropionylperoxide
Perfluoro-2-n-propoxypropionylperoxide

Carbon tetrachloride
Carbon tetrachloride
Freon 113
Freon 113
perF-ether mix.
Freon 113

Perfluoro-2-iso-propoxypropionylperoxide

Freon 113

2-Azidobenzoyl peroxide

Benzene

Benzoyl peroxide

Acetic acid
Acetone

Acetonitrile
Acetophenone

Allyl alcohol
Anisole
Benzaldehyde
Benzene

T( 0 C)
40
40
40
65
70
75
40
45
50
55
77
60.1
70.4
76.4
85.0
55
60
65
70
40
50
60
70
75
75
T (K)
T(K)
T (K)
20
30
40
20
30
40
50
80
75
50
70
85
100
70
70
80
94.5
80
30
80
90
25
30
55
60
60
80
70
78
78
79.8
80
66
72.5
78
70

kd (s"1)
9.0xl0~4
1.32 x 10 ~4
6.OxIO" 5
1.37 x 10 ~5
2.13,3.08 x 10- 5
3.83 x l O - 5
1.50 x 10 ~5
2.55 XlO" 5
4.96 XlO" 5
8.17,7.85 x 10" 5
1.186 x 10 ~4
1.06 x 10 " 5
4.15 XlO" 5
8.59 x l O " 5
2.668 x l O - 4
5.465 x 10 ~5
1.024 x l O " 4
1.876 XlO" 4
3.208 XlO" 4
9.6IxIO" 6
3.619 x l 0 ~ 5
1.305 XlO" 4
4.772 x l O " 4
2.92 x 10 " 5
4.21 x 10 ~5
1.2 x 1011
4.4xlO 1 4
8.9 x 1016
4.81 x 10 ~5
1.96 x 10 ~4
7.16 XlO" 4
8.32 x 10 ~5
3.43 x 10 ~4
1.34 x l 0 ~ 3
2.5 x 10~5
9.4 XlO" 4
7.53 x 10 " 5
2.25 x 10 ~6
2.63X10- 5
1.34 xlO~ 4
5.83 xlO~ 4
1.76 x 10 ~5
1.15 x 10~5
4.32xlO- 5
2.30xl0~ 4
3.80 x 10 ~4
1.42 x 10 ~7
5.50xl0~ 5
1.71 x 10- 4
6.4xlO~ 5
4.80 xlO~ 8
1.14 xlO~ 6
2.76 xlO~ 6
2.0xl0~6
2.5xlO-5
1.38x10-5
2.3OxIO- 5
1.67x10-5
3.48x10-5
4.8x10-5
7.72 x 10 ~6
1.87x10-5
3.77x10-5
1.17x10-5

Ea (kj/mol)

129.3

Notes

c
c
c
c

j
j
j
j
a,mi
^m1
exp[- 11A/RT]
exp[- 9Z.5/RT]
exp[-110.2/RT]
100.1

102.7

111.3

126.4

116.3

124.3

129.7

133.9

d2
d2
a,r
a
a
a
a
tj
a
a
a
a,r
a
a,r
a,r
p2
a
a,r
a,r
m2
m2
a
c
X9

a
a
a
a

Refs.
256
256
256
34
34
34
34
34
34
34
209
209
209
209
209
164
164
164
164
164
164
164
164
232
232
304
304
304
283
283
283
283
283
283
161
161
74
126
126
126
126
124
5
5
5
74
109
74
74
279
109
74
74
14
14
213
230
230
170
20
131
131
131
73

Table 4. cont'd
Number of
C atoms
14 (cont'd)

Initiator
Benzoyl peroxide

Solvent
Benzene

Benzyl alcohol
Bromobenzene

Butanol
Butanone
Di-n-butyl phthalate

Carbon tetrachloride
Chlorobenzene

Chloroform
Cumene

Cyclohexane
Decane
Decalin
Dioxane

J( 0 C)
75
80
80
50.8
54.9
60.9
65.6
71.0
75.8
70
85
100
70
70
75
75
85
85
100
100
79
80
80
80.2

80
80
117
127
137
147
75
79
70
80
80.2
80.2
80.2
80.2
71
91
113
T (K)
30
80
85
90
30
45
60
80
T (K)
100
80
80
80
70
80
80
80

kd (s"1)
2.62 x 10 " 5
4.39 XlO" 5
3.27 XlO" 5
4.28 XlO" 7
8.53 x l O - 7
1.66 x l O - 6
3.22 XlO" 6
5.94 x l O - 6
1.19 XlO" 5
1.27 XlO" 5
8.94 x l O - 5
4.96 x l O - 4
1.03 x l O - 5
1.18 XlO" 5
1.48 x l O - 5
1.66 x l O - 5
4.7 x l O - 5
5.5 XlO" 5
2.28 x l O - 4
2.56 x l O " 4
2.58 x l O - 5
3.35 x l O " 5
4.44 x 10 " 4
8.15 x l O " 5
2.19 x l O " 5
3.84 x l O - 5
3.55 x l 0 ~ 5
4.34 x l O - 5
6.06 x 10 " 4
4.64 x 10 " 5
2.78 x 10 ~3
7.44 X l O " 3
1.72 x l O - 2
3.89 X l O " 2
1.07 x 10 " 5
1.69 X l O " 5
1.35 x 10 ~5
4.64 x l O - 5
2.85 x l O " 5
2.36 x l O - 5
3.52 x l 0 ~ 5
2.62 X l O " 5
1.93 x l O - 5
1.93 x l O " 4
1.93 XlO" 3
6.94 x l O 1 3
5.47 x 10 ~8
3.69 x 10 ~5
6.39 XlO" 5
1.19 x l O - 4
7.3OxIO- 8
1.85 x l O 7
1.45 x l O - 6
1.70 XlO" 5
1.20 x 10 13
2.5 XlO" 4
7.72 x 10 ~5
2.53 x 10 " 5
2.26 x 10 " 4
1.30 x 10 " 5
6.72 x l O - 4
4.2OxIO- 4
4.18 x l 0 ~ 5

Ea (kj/mol)

123.8

130

128.0
124.3

Notes
a
a
a,b 2
a,t2
a,t2
a,t2
a,t2
a,t2
a,t2
a
a
a
a,m2
t2
m3
m3
m3
a,t6
a
a,r
t9

Hi1
m3
m5

120.1

a,r
a,r
yi6

a,r
t 6 ,a
I1
a,r
t9
Cm 1
c,m 3

exp[- 12235/RT]
a
a,r
a,r
a,r
a
120.5

exp[- 120.5/RT]
a,t7
a,r
a,r
ti
a,r
a,r
a,m!

Refs.
73
73
347
69
69
69
69
69
69
337
126,337
126,337
16
124
12
12
12
12
12
12
120
7
74
231
231
231
231
231
74
74
236
236
236
236
74
121
124
74
231
231
231
231
344
344
344
344
109
74
74
74
109
67
67
67
67
122
74
270
74
74
74
6
232

Notes page 11-69; References page 11-70

Table 4. cont'd
Number of
C atoms
14 (cont'd)

Initiator
Benzoyl peroxide

Solvent
Ethanol

Ethylbenzene

90% Formic acid


H-Heptane

Hexadecane
Hexane
Isooctane
Isopropylbenzene
Methyl acetate
Methylcyclohexane
4-Methyl-2pentanone
a-Methylstyrene
Mineral oil
Neat
Nitrobenzene
PEG 400

90% aq. PEG 400

80% aq. PEG 400

70% aq. PEG 400

rt-Pentanol
Phenol
Propionic acid
Propylene glycol

Styrene

T( 0 C)
25
40
50
30
75
80
85
90
80
80
80
80
130
135
140
145
145
145
145
150
155
160
80
80
80
80
80
49.2
53.9
80
80
70
80
105
80
30
25
40
50
70
25
40
50
70
25
40
50
70
25
40
50
70
80
80
80
25
40
50
34.8
49.4
61.0
74.8
100.0

^d(S1)
3.02 x l O ~ 8
2.77 x l O " 7
4.72 x l O - 7
3.61 x 10 " 8
1.8IxIO- 5
3.33 XlO" 5
5.56 XlO" 5
1.01 x 10- 4
3.15 x l 0 ~ 5
6.94 x 10 " 4
3.11 x 10 ~5
2.7IxIO-5
5.73 XlO" 3
1.02 x l O " 2
1.54 x l O - 2
2.25 XlO" 2
2.22xlO-2
2.21 x 10~2
2.12 x l O - 2
3.47 x l O " 2
5.21 x 10- 2
7.87 x l O - 2
2.51 x 10 " 5
2.85 x 10 ~5
2.79 x 10 ~5
2.7OxIO" 5
3.34 x 10~5
6.28 x 10 ~7
1.0 XlO" 6
5.25 x 10 ~5
4.28 x 10 ~5
3.02 x 10 " 5
2.89 x 10~5
7.22 x 10 ~3
4.58 x 10 ~5
6.6IxIO-8
5.0IxIO-7
5.73 x l O - 6
1.15 x l 0 ~ 5
1.15 XlO" 4
3.65 x 10~7
5.35 x l O " 6
1.15 x l O - 5
1.15 x l O " 4
2.77 x 10 ~7
3.09 x l O " 6
7.29 x l O - 6
1.15 x l O - 4
1.71 x 10 ~7
2.1IxIO-6
5.01 x 10- 6
1.15 x l O " 4
1.48 x 10 ~4
6.25 x 10 " 4
3.19 x 10~5
3.25 x 10 ~8
1.51 x l O ~ 7
3.16 x l O - 7
3.89 x 10 ~8
5.28 XlO" 7
2.58 x l O - 6
1.83 x l 0 ~ 5
4.58 x l O " 4

a (kj/mol)

Notes
a
a
a
a
a,r
a,r
a,r
a,r
c
a,r
a,r
z (1500)
z (1500)
z (1500)
z (500)
z (1000)
z (1500)
z (2000)
z (1500)
z (1500)
z (1500)

123.8

117.6

m2
c
a,t2
a,t2
a,r
a,r
a
m2
a
a,r
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a,r
a,r
a,r
a
a
a
a
a
a
a
a

Refs.
351
351
351
109
74
74
74
74
239
74
74
270
377
377
377
377
377
377
377
377
377
377
270
270
270
308
229
69
69
74
74
213
308
371
74
109
351
351
351
351
351
351
351
351
351
351
351
352
351
351
351
351
74
74
74
351
351
351
10
10
10
10
10

Table 4. cont'd
Number of
C atoms
14 (cont'd)

Initiator
Benzoyl peroxide

Solvent
Poly(styrene)

Tetradecane
Tetralin
Toluene

Poly(vinylchloride)

Styrene

3-Bromobenzoyl peroxide

4-Bromobenzoyl peroxide
4-terr-Butylbenzoyl peroxide
2-Chlorobenzoyl peroxide
3-Chlorobenzoyl peroxide
4-Chlorobenzoyl peroxide

p-Xylene
Benzene

Dioxane
Dioxane
Dioxane
Acetophenone
Benzene
Acetophenone
Dioxane
Acetophenone
Benzene

Dioxane
Styrene

Cyclohexane formyl peroxide

Benzene

Carbon tetrachloride

Cyclopentane acetyl peroxide

Carbon tetrachloride

Diacetylsebacoyl diperoxide

Carbon tetrachloride

T( 0 C)
56.4
64.6
76.7
83.4
98.5
70.9
80.1
89.5
80
80
30
49.0
55.1
60.2
65.1
70.3
60.00
64.6
76.7
83.4
98.5
50
60
70
80
60
80
80
80
80
80
80
80
80
80
80
80
50
85
100
80
34.8
49.4
61.0
74.8
100.0
30
35
40
45
50
35
45
50
60
35
40
45
65
70
75
60
73.5
85

^d(S"1)
3.8 x 10~7
1.47 x l O - 6
9.27 x l O " 6
2.5OxIO- 5
1.41 x l O " 4
2.86 x l O - 6
1.11 x l O - 5
3.33 x l O - 5
2.64 x 10 ~5
3.72 x 10 " 5
4.94 x l O " 8
6.OxIO- 7
1.31 x 10- 6
2.83 x l O - 6
5.69 x l O - 6
1.10 x l O - 5
2.24 x l O " 6
6.3xlO" 7
5.11 XlO" 6
1.44 x l O - 5
9.33 x l O " 5
7 x IO" 7
7.7 x l O - 6
9.9 x l O " 6
3.1OxIO- 5
1.1 x 10 " 6
1.22 x l O - 5
2.6OxIO- 5
2.57 x 10 ~5
3.23 x 10 ~5
6.06 x 10 ~5
3.88 x 10 " 4
3.12 x 10 " 4
2.85 x 10 ~5
2.63 x 10 ~5
3.83 x 10 " 5
2.17 x 10 ~5
6.2 x l O " 7
6.64 x l O - 5
3.86 x l O - 4
3.62 x 10 " 5
8.3xl0-8
8.3 x l O " 7
3.33 x l O - 6
2.22 x l O - 5
4.17 x l O - 4
9.64 x 10 ~5
1.46 x l O " 4
3.1OxIO- 4
5.11xlO" 4
7.77 x l O - 4
6.6xlO~~5
2.1IxIO-4
4.45 xlO~ 4
1.3OxlO" 3
2.87 x l O - 5
5.22,5.29 x 10 " 5
9.67 x l O - 5
1.48 x 10" 5
3.2OxIO" 5
4.97 x l O - 5
1.04 x 10 ~5
5.20xl0~5
2.3OxIO- 4

E a (kj/mol)

120.5
123.8

Notes

Refs.

a
a
a
a
a
a
a
a

17
17
17
17
17
15
15
15
270
74
109
69
69
69
69
69
291
17
17
17
17
287
287
287
229
116
116
7
6,232
6,232
232
5
7
5
6
5
7
126
126
126
6
10
10
10
10
10
219
219
219
219
219
148
148
148
148
34
34
34
34
34
34
215
215
215

a,r
a
a,t2
a,t2
a,t2
a,t2
a,t2
e,m3
a
a
a
a

125.7

123.0
128.4
127.2
128.9

84.5

a
a,mi
a,mi
a,m
a
a
a
a,mi
a
a
a
a
a
^m1
a
a
a
a
a
a,h

Xi
X1
xi

Notes page 11-69; References page II - 70

Table 4. cont'd
Number of
C atoms
14 (cont'd)

Initiator
2,4-Dichlorobenzoyl peroxide

Solvent
Benzene

Styrene

2,2,3,3,4,4,5,5,6,6,7,7-Dodecafluoroheptanoyl peroxide
Heptanoyl peroxide
6-Heptenoyl peroxide

2-Iodobenzoyl peroxide
2-Iodobenzoyl 4-nitrobenzoyl
peroxide

3-Methylbenzoyl peroxide
4-Methylbenzoyl peroxide
2-Nitrobenzoyl peroxide

Freon 113
Toluene
Toluene

Chloroform
Acetone
Acetonitrile
Benzene
Carbon tetrachloride
Chloroform
Nitrobenzene
Dioxane
Dioxane
Acetophenone
Methyl iodide

15

16

3-Nitrobenzoyl peroxide
4-Nitrobenzoyl peroxide
3,5-Dinitrobenzoyl peroxide
Perfluoroheptanoyl peroxide

Acetophenone
Acetophenone
Acetophenone
Freon 113

Benzoyl phenylacetyl peroxide

Benzene

4-terf-Butylbenzoyl isobutyryl
peroxide

Cyclohexane

3-Cyanobenzoyl benzoyl peroxide


3-Methoxybenzoyl benzoyl peroxide
4-Methoxybenzoyl benzoyl peroxide
4-Methoxybenzoyl 3-bromobenzoyl
peroxide
4-Methoxybenzoyl-3,5-dinitrobenzoyl peroxide

Dioxane
Dioxane
Dioxane
Dioxane
Benzene
Nitrobenzene

J( 0 C)
70
70
50
70
85
34.8
49.4
61.0
74.8
100.0
30
40
77
70
70
77
85
22
25
25
25
25
25
25
80
80
59.3
80
24.95
45.05
80
80
80
20
30
40
20
25
25
25
30
35
55
60
65
70
80
80
80
80

^d(S" 1 )
9.7OxIO" 5
1.24 xlO~ 4
1.08 xlO~ 5
1.37 xlO~ 4
7.69 XlO" 4
3.88 x 10 " 6
2.39 x l 0 ~ 5
7.78 xlO~ 5
2.78 xlO~ 4
4.17 x l 0 ~ 3
1.14 x 10~4
4.06 x 10 ~4
1.24 x 10 ~4
5.33 x 10 ~5
5.01 x 10 ~5
1.07 xlO~ 4
2.88 xlO~ 4
1.86 x 10 ~3
3.0xl0~4
2.1x 10 ~4
5.7xl0~5
3.4xl0~5
2.8xlO~ 4
6.2xlO~ 4
4.38 x 10 ~5
6.11 x 10 ~5
5.80xl0~ 5
1.34 x l 0 ~ 3
1.78 xlO~ 5
1.50xl0~ 4
3.80xl0"5
4.33 x 10 " 5
1.87 x l 0 ~ 5
3.01 x 10 ~5
1.11 xlO~ 4
4.20xl0~4
1.10 x 10~4
2.05 xlO~ 4
3.15 xlO~ 4
6.38 xlO~ 4
3.88 xlO~ 4
6.67 xlO~ 4
6.543 x 10 ~5
1.171 x 10~4
2.663 xlO~ 4
5.016 xlO~ 4
2.73 x 10 ~2
4.82 x 10 ~2
7.57 x 10 ~5
4.43 x 10 ~2

a (kj/mol)

117.6

100.6

Notes
a,j
a,k
a
a
a
a
a
a
a
a
h
a
a,k
a,j
a,j
a,k

119.7
81.2
126.4
126.8
130.5
98.0

a,mi
a,mi
a
a
h
a
a
a

90.8
vi
n

ti 0
tio
t 10
tio
a,m\
a,mi
a,mi
a,mi

Refs.
16
16
126,337
126,337
126,337
10
10
10
10
10
283
283
19
19
19
19
19
82
78
78
78
78
78
78
232
232
5
5
82
82
5
5
5
283
283
283
222
222
222
222
222
222
164
164
164
164
6
6
6
6

51
51
51

1.02 x 10 ~5
9.61 x 10 ~4
1.67 XlO" 3

t5

108
108
108

a
a

89
89

a
a
a

95
116
116
126
126
126

4-Methoxybenzoyl 4-nitrobenzoyl
peroxide

Benzene

70
70

2.08 x 10 ~5
8.03 x l 0 ~ 5

3,5-Dibromo-4-methoxybenzoyl
peroxide

Benzene

Caprylyl peroxide

Benzene

60
60
80
50
70
85

9.5 x 10 ~7
6.1 xlO~ 7
9.4 x 10 ~6
3.44 x 10 ~6
5.78 x l 0 ~ 5
3.78 xlO~ 4

128.9

Table 4. cont'd
Number of
C atoms
16 (cont'd)

Initiator

Solvent

Caprylyl peroxide
/7-(Chloromethyl)benzoyl peroxide

Mineral oil
Acetone

3-Cyanobenzoyl peroxide
4-Cyanobenzoyl peroxide
Cycloheptane formyl peroxide

THF
Toluene
Dioxane
Acetophenone
Dioxane
Carbon tetrachloride

Cyclohexane acetyl peroxide

Carbon tetrachloride

2-Ethyl-4-methyl-2-pentenoyl
peroxide
2-Ethylhexanoyl peroxide
2-Ethyl-2-hexenoyl peroxide
2-Iodophenylacetyl peroxide

2-Methoxybenzoyl peroxide
3-Methoxybenzoyl peroxide
4-Methoxybenzoyl peroxide
2-Methylbenzoyl peroxide
3-Methylbenzoyl peroxide
4-Methylbenzoyl peroxide
Endo-norbornane-2-carbonylperoxide

Mineral oil
Mineral oil
Mineral oil
Acetone
Chloroform
Toluene
Acetophenone
Acetophenone
Dioxane
Acetophenone
Dioxane
Acetophenone
Acetophenone
Dioxane
Acetophenone
Dioxane
Carbon tetrachloride

Exo-norbornane-2-carbonylperoxide

Carbon tetrachloride

Endo-norbornene-5-carbonylperoxide

Carbon tetrachloride

Exo-norbornene-5-carbonylperoxide

Carbon tetrachloride

Dioctanoyl peroxide

w-Heptane

T( 0 C)
T (K)
70
70
70
70
80
80
80
35
40
45
65
70
75
54.4
64.3
71.8
T(K)
T(K)
T (K)
0
0
0
50
80
80
80
80
80
70
80
80
80
80

A^(S"1)

Ea (kj/mol)

9.8 x 1015
2.07 x 10 ~5
1.82 x l O " 5
1.15 XlO" 5
8.8xl0"6
1.70 x 10 ~2
2.43 x 10 ~5
2.03 x 10 " 5
7.85 x 10 ~5
1.63,1.34XlO"5
2.02 XlO" 4
1.27 x 10 " 5
2.76 XlO" 5
3.61 x 10 " 5
3.1 x 10 " 6
1.19 x l O " 5
2.95 XlO" 5

exp[- UOA/RT]

7.IxIO16
1.2xlO 14
1.6 x 1016
2.6OxIO" 5
3.98 x 10 ~5
1.3xlO" 5
6.0xl0"5
2.15 XlO" 3
6.42 x 10 " 5
5.75 x 10 ~5
1.56 x 10 " 4
1.18 x 10 ~A
9.02 x 10 " 5
4.7OxIO" 5
4.4OxIO" 5
5.92 x 10 " 5
6.13 x 10~5

exp[-138.4//?7]
exp[- 106A/RT]
exp[-136.3//?7]

Notes

m7

a,mi
a
a,mi

113.8
120.9
120.1
126.4
126.4
125.1

Refs.
1
307
307
307
307
6
5
6
34
34
34
34
34
34
24
24
24

c,e,q
q
a
a
a
a,mi
a
a,mi
a
a
a,mi
a
a,mi

1
1
1
79
79
79
5
5
5
6
5
6
5
5
6
5
6

44.5
53.9
65.9

6.IxIO"6
2.83 XlO" 5
1.25 XlO" 4

j
j
j

23
23
23

44.5
53.9
65.9
44.5
53.9
65.9
44.5
53.9
65.9
44.5
53.9
65.9
445
53.9
65.9
44.5
53.9
65.9
44.5
53.9
65.9
70
80
80

9.1 x 10" 6
4.33 x l O " 5
1.28 x l O " 4
4.68 x 10 " 5
2.05 x 10 " 4
8.18 xlO~ 4
7.2 XlO" 5
1.6OxIO"4
8.48 XlO" 4
6.30xl0~ 5
1.2IxIO" 4
7.18 x l O " 4
2.22 x l O " 5
4.52 XlO" 5
2.37 x l O " 4
6.58 x 10 " 5
1.2IxIO- 4
8.42 XlO" 4
2.58 xlO~ 5
1.2OxIO"4
7.1OxIO- 4
1.70xl0" 5
7.0IxIO-5
6.8OxIO- 5

j,m 2
j , m2
j,m 2
j
j
j
j , m2
j,m 2
j , m2
j
j
j
j,m 2
j,m 2
j,m 2
j
j
j
j,m 2
j,m 2
j,m 2
z (1500)
z (500)
z (1000)

23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
377
377
377

Notes page 11-69; References page 11-70

Table 4.
Number of
C atoms
16 (cont'd)

18

cont'd

Initiator

Solvent

T( 0 C)

^d(S1)

Ea (kj/mol)

Notes

Refs.

80
80
80
90
95
100
63
80
100
T (K)
20
20
20
20
0
0
18
80
80
80

6.27 x 10~5
6.01 x l 0 ~ 5
5.77xlO-5
2.13 x l O ~ 4
3.8OxIO- 4
6.79 x l O ~ 4
1.93 x 10 ~5
1.93 x l O - 4
1.93 x l O - 3
2.30 x 10 15
1.02 x 10 ~3
4.76 x 10 ~4
1.86 x 10 ~4
1.6OxIO- 4
7.8xl0~5
2.5OxIO- 5
3.34 XlO" 4
1.42 x 10 ~4
1.4 x l O ~ 4
2.3 x 10 ~4

Acetonitrile
2-Butanol
Carbon tetrachloride
Cyclohexane

40
40
40
40

5.9xl0~3
4.4xlO~ 3
6.7 x 10 ~4
4.4xlO~ 4

256
256
256
256

5-terf-Butylthenoyl peroxide
Cinnamoyl peroxide

Acetonitrile
2-Butanol
Carbon tetrachloride
Cyclohexane
Carbon tetrachloride
Styrene

Dibenzoyl succinoyl diperoxide

Unknown

Nonanoyl peroxide
Isononanoyl peroxide (3,5,5trimethylhexanoyl peroxide)

Mineral oil

40
40
40
40
75
50
70
70
75
85
T(K)

4.2xlO~ 3
2.8 x 10 ~3
6.5 x 10 ~4
3.9xlO~ 4
4.03 x 10 ~5
1.2OxIO- 5
1.67 x l O - 4
7.7 x 10 ~6
1.42 x l O - 5
5.4 x l O - 5
8.4xlO 1 4

256
256
256
256
232
316
316
214
214
214
1

50
70
85
60
59
77
96
T (K)
60
70
80
80
80
80
80
80
90
100
120
125
130
135
140
145
150
T (K)

6.IxIO-6
8.02 x l 0 ~ 5
5.3OxIO- 4
1.9 x l O - 5
1.93 x 10 ~5
1.93 XlO" 4
1.93 x l O - 3
2.84 x 1015
5.28 x 10 ~6
2.06 x l 0 ~ 5
9.53 x l O - 5
9.1OxIO- 5
8.62 x l O - 5
8.24 x l O - 5
7.86 x l O - 5
7.46 x l O - 5
2.52 x l O - 4
8.8IxIO-4
6.98 x l O - 3
1.27xl0- 2
2.15 XlO" 2
2.6OxIO- 2
5.7IxIO- 2
8.62xl0-2
1.17XlO- 1
1.6 x 1015

Dioctanoyl peroxide

^-Heptane

Dioctanoyl peroxydicarbonate

Chlorobenzene

Phenylacetyl peroxide

Acetonitrile
Benzene
Carbon tetrachloride
Cyclohexane
Styrene
Toluene

Triptoyl peroxide

Benzene

Apocamphoyl peroxide
ds-5-rm-Butylcyclohexylformylm-chlorobenzoyl peroxide

Benzene

fra5-4-^rf-Butylcyclohexylformylm-chlorobenzoyl peroxide

Benzene

Chlorobenzene

n-Heptane

2-Nonenoyl peroxide

Mineral oil

z
z
z
z
z
z

(1500)
(2000)
(2500)
(1500)
(1500)
(1500)

exp[- 129.05/RT]

96.2

f,u2
f,uj

a,mi

125.5

X1
xi
xi

exp[-121A/RT]
126

a
a
a
a

exp[- 128.34/^7]
z (1500)
z (1500)
z(l)
z (500)
z (1000)
z (1500)
z (2000)
z (2500)
z (1500)
z (1500)
z (1500)
z (1500)
z (1500)
z (1500)
z (1500)
z (1500)
z (1500)
exp[-128.8//?7]

377
377
377
377
377
377
344
344
344
344
167
167
167
167
316
59
59
102
244
102

337
337
337
338
344
344
344
344
377
377
377
377
377
377
377
377
377
377
377
377
377
377
377
377
377
1

Table 4. cont'd
Number of
C atoms

Initiator

18 (cont'd)

3-Nonenoyl peroxide
2-Phenylpropionyl peroxide

19

Dibenzoyl itaconyl diperoxide

Solvent
Mineral oil
Cyclohexane
On silica
Styrene
Unknown

J(0C)
T (K)
55.8
49.4
70
70
75
85

Dibenzoyl a-methylsuccinoyldiperoxide

Unknown

70
75
85

20

Decanoyl peroxide

Benzene

Chlorobenzene

Dioctanoyl a-bromosuccinoyldiperoxide

Mineral oil
Unknown

60
70
85
63
80
100
T (K)
T(K)
70
75
85

Dioctanoyl a-chlorosuccinoyldiperoxide

Unknown

70
75
85

21

Dioctanoyl a-chlorosuccinoyldiperoxide
4-Ethyl-2-octenoyl peroxide
Dioctanoyl itaconoyl diperoxide

Chlorobenzene

70

Chlorobenzene
THF
Chlorobenzene

70
70
70

1.18 x 10 " 4
6.2xl0"5
1.54 x 10 " 5

Chlorobenzene

35
70
35
50
55
65
T(K)
55

9.42 x 10 " 5
3.02 x 10" 3
9.77 x 10" 4
7.92 x l O " 5
1.45 x l O " 4
4.13 x l O " 4
1.07 x l O 1 2
1.38 x l O " 4

85
T (K)
70

85
Unknown

70
75
85

22

Benzoyl 2-[mms-2-(3-nitrophenyl)vinyljbenzoyl peroxide


Benzoyl 2- [frans-2-(4-nitrophenyI)vinyl]benzoyl peroxide
Benzoyl 2-[fras-2-(4-nitrophenyI)vinyl]-4-nitrobenzoyl peroxide
Benzoyl 2-[frans-2-(phenyl)vinyl]benzoyl peroxide
4-Benzylidenebutyryl peroxide

3.7 x 10 14
6.8xlO~ 6
7.5 x 10 " 5
5.5 x 10" 5
5.63 x 10~ 4
1.87 XlO" 5
8.63xlO- 4
3.62 xl0~ 5
1.69 X l O " 3
1.00 X l O - 4
2.74 x 10 " 4
1.26 x l O " 5
4.26 X l O " 4
2.40xl0~5
9.6OxIO"4
8.7 x l O " 5
1.53 x 10~5
5.67 XlO" 5
3.8OxIO- 4
1.93 x 10 " 5
1.93 x l O - 4
1.93 x l 0 ~ 3
3.64 x 10 15
2.7xl015
1.52 x 10 ~~4
1.82 x l O " 5
2.74 XlO" 4
3.83 xlO- 5
6.97 x l O " 4
1.15 X l O " 4
2.02 x 10 ~A
2.42 x l O " 5
3.23 x l O " 4
4.83 xlO~ 5
8.5OxIO-4
1.58 x 10~ 4
8.2 x 10 1 4
3.23 x 10 ~4
2.8OxIO-5
5.47 x l O " 4
5.6OxIO"5
1.28 x l O " 3
1.92 X l O " 4
5.48 x 10 ~4
5.88 x l 0 ~ 5
9.58 x l O " 4
1.06 x l O " 4
2.61xl0"3
3.84 x l O " 4
1.87 x 10~4

Unknown
Mineral oil
Unknown

75

Dioctanoyl a-methyl succinoyldiperoxide

* d (s" 1 )

Methanol
Acetophenone

E31 (kj/mol)

Notes

exp[- 10S.0/RT]

83.7
115.1

82.8
116.3

127.2

exp[- 130.48//?7]
exp[- 131.9/K7]
96.2
126.4

95.4
126.4

X2
X2
X2
X2
X2
X2
X2
X2
X2
X2
X2
x2
a
a
a

X2
X2
X2
X2
x2
X2
X2
X2
X2
X2
X2
X2

e x p [ - 121A/RT]
92.9
127.6

96.2
131.0

84.5

1
258
258
316
214
214
214
214
214
214
214
214
214
214
214
214
126,337
126,337
126,337
344
344
344
344
1
214
214
214
214
214
214
214
214
214
214
214

X2
X2
X2
X2
X2
X2
X2
x2
X2
x2
x2
x2
t9

214
1
214
214
214
214
214
214
214
214
214
214
214
214
175

t9
t9
t9

175
175
175

h,t 9
t9
t9

175
175
175
133
133
133
133
133

99.6

exp[-99.6//?7]
98.7

Refs.

m2

Notes page II - 69; References page II - 70

Table 4. cont'd
Number of
C atoms
22 (cont'd)

Initiator
4-Benzylidenebutyryl peroxide

Solvent
Acetophenone
Benzene

Carbon tetrachloride

Nitrobenzene
Propylene carbonate

4-ter/-Butylbenzoyl peroxide
cis-4-tert-Butylcyclohexane formylperoxide

Toluene
Dioxane
Butane
Carbon tetrachloride

frarcs-4-te7t-Butylcyclohexane formylperoxide

Carbon tetrachloride

fras-4-(4-Chlorobenzylidene)butyryl peroxide

Benzene

Propylene carbonate

frarcs-4-(4-Fluorobenzylidene)butyryl peroxide

Benzene

Propylene carbonate

1-Naphthoyl peroxide

Benzene

4-Nitrobenzoyl-2-[rra5-2-(4-nitrophenyl)vinyl] benzoyl peroxide


2-Phenylisovaleryl peroxide

Chlorobenzene

5-Phenylpenta-2,4-dienoyl-peroxide
5-Phenylpentanoyl peroxide

Acetonitrile
Cyclohexane
On silica
Styrene
Acetophenone
Benzene
Carbon tetrachloride

Propylene carbonate
24

Dibenzoyl 2-bromosebacoyldiperoxide

Unknown

J( 0 C)
65
T(K)
50
60
70
60
70
T(K)
60
40
50
T (K)
50
40
50
60
70
80
40
40
40.0
45.45
50.7
40.0
44.7
48.9
50
60
70
40
50
60
50
60
70
40
50
60
54.6
59.9
64.5
70
55.0
55.0
50
70
77
77
70
77
85
T(K)
60
60
70
75
85

Dioctanoyl 2-bromosebacoyldiperoxide

Unknown

70
75

A^(S"1)
4.02 x 10 " 4
7.14xlOn
2.40xl0~ 5
6.8OxIO- 5
1.845 x l O - 4
3.47 x 10~5
1.06 XlO" 4
1.42xlO 13
3.38 x 10~4
7.36 x 10~5
2.13 XlO- 4
5.93 x 1010
2.08 XlO" 4
7.23 x l O - 5
2.093 x l O " 4
5.117 x l O - 4
1.64 x 10~4
6.08 x 10 ~2
1.25 x 10 ~5
1.69 x l O " 5
(8.65 0.35) x 10 ~5
(1.32 0.04) x 10- 4
(2.35 0.05) x 10- 4
(4.25 0.23) x 10~5
(7.10 0.38) x 10 ~5
(1.140.04)x 10~4
2.10xl0"5
6.56 x 10 ~5
1.75 x l O " 4
5.33 x 10 ~5
1.448 x 10~4
2.791 x 10~4
2.67 x 10 " 5
8.44 x 10 ~5
2.119 x l O - 4
6.53 x 10 ~5
1.685 x l O - 4
4.54OxIO- 4
1.01 x 10~4
1.86 x l O - 4
3.OxIO" 4
6.06 x 10~5
2.27 x 10 " 5
6.4xlO-6
2.56 x 10 ~4
2.18 x l O " 4
2.37 x 10 ~4
1.054 x l O " 5
2.76 x l O " 5
7.19 x l O - 5
1.87 x l O - 4
1.76xlO 15
4.41 x 10 ~5
2.8Ox 10" 5
4.80xl0~4
3.87 x 10~5
7.64 x l O - 4
7.22 XlO" 5
2.0OxIO" 3
2.02 x l O - 4
6.46 x 10 ~4
5.23 x 10~5
1.17IxIO- 3

Ea (kj/mol)

Notes

exp[- 98.1/RT]
91.2

m2
m2
h

112.5
exp[-112.5 /RT]

m2
m2
m2

89.5
exp[- 89.5/RT]
82.0

m2
h

76.1

a,mi
z (0.98)
z (1010)
h

81.6

95.0

94.1

t9

n2

127.6
130.1

exp[-130.1/i?7]

87.9
110.8

99.6
129.7

h,m2
m2
m2
m2
m2
m2
X2
X2
x2
X2
x2
X2
X2
X2
x2

Refs.
133
133
194
194
194
133
133
133
133
133
133
133
133
194
194
194
133
6
145
145
35
35
35
35
35
35
194
194
194
194
194
194
194
194
194
194
194
194
170
170
170
175
258
258
258
316
133
194
133
133
133
133
133
133
214
214
214
214
214
214
214
214
214

Next Page

Table 4. cont'd
Number of
C atoms
24 (cont'd)

Initiator

Solvent

Dioctanoyl 2-bromosebacoyldiperoxide

Unknown

Lauroyl peroxide

Benzene

Chlorobenzene

Ethyl acetate

Ethyl ether
Mineral oil
Styrene

26
28
36
x

TABLE 5.
Number of
C atoms
4

2-Phenoxybenzoyl peroxide
Myristoyl peroxide
Menthylphthaloyl peroxide
Aliphatic polymeric
diacyl peroxide

kd(s'1)

Benzene
Benzene

Acetophenone
Benzene
Dioxane
Chlorobenzene

Ea (kj/mol)

30
40
50
60
70
60
70
85
70
40
50
60
70
61
79
99
T (K)
40
50
61
70
30
T (K)
34.8
49.4
61.0
74.8
100.0
50
60
65
70
50

1.08 x 10 " 4
3.0OxIO" 3
3.72 x l 0 ~ 4
2.56 x 10 " 7
4.91 x 10~7
2.19 x l O - 6
9.17 xlO~ 6
2.86 x l O - 5
1.51 x 10~5
5.58 x l 0 ~ 5
3.75 x l O - 4
4.33 x l O - 5
2.91 x 10 ~7
1.15 XlO" 6
4.75 x l O - 6
1.87 xlO~ 5
1.93 x 10 ~5
1.93 x l O - 4
1.93 XlO" 3
3.92 xlO 1 4
6.03 x 10 ~7
2.7OxIO- 6
1.05 x l 0 ~ 5
3.99 x l 0 ~ 5
1.97 x 10 " 6
2.2 x 1016
2.06 x 10 ~7
2.25 x l O " 6
1.42 x l 0 ~ 5
1.00 x l O - 4
2.39 x l O - 3
3.1 x 10" 6
1.2OxIO- 5
2.22 x l O - 5
4.32 x l O - 5
2.03 x 10 ~4

50
60
70
65
70
55
75
75
80

6.58 x 10 ~5
1.815 x 10 ~4
4.729 x l O " 4
8.18x10 ~5
3.38 x 10 ~5
1.15 x 10~4
9.04 x 10 ~5
9.00 x 10 " 5
1.720xl0" 4

85

Carbon tetrachloride

rraw5-4-(4-Methoxybenzylidene)butyryl peroxide
frarcs-4-(4-Methylbenzylidene)butyryl peroxide

T( 0 C)

Notes
X2
X2
X2
a

127.2

a
a
a
a,j

exp[- 12337/RT]

a
exp[- 137.9/RT]
a
a
a
a
a
121.1

90.4

121.3

c,h
c
c
a
a
Vu
Vi5
V 15

Refs.
214
214
214
99
68
68
68
68
126,337
126,337
126,337
16
68
68
68
68
344
344
344
344
68
68
68
68
99
1
10
10
10
10
10
287
287
287
287
194
194
194
194
5
16
65
302
302
302

HYDROPEROXIDES AND KETONE PEROXIDES

Initiator

Solvent

sec-Butyl hydroperoxide

Toluene

ter/-Butyl hydroperoxide

Benzene

T( 0 C)
172.0
182.3
130
145
160
154.5
161.7
169.3
174.6

fcd

(s"1)
2.65 x 10 ~5
4.9 XlO" 5
3 x 10 ~7
1.6 XlO" 6
6.6 x l O - 6
4.29 XlO" 6
9.27 x l O - 6
2.OxIO- 5
4.OxIO- 5

Ea (kj/mol)

138

170.7

Notes

a
a
a
h

Refs.
199
199
337
337
337
76
76
76
76

Notes page 11-69; References page II - 70

Previous Page

Table 4. cont'd
Number of
C atoms
24 (cont'd)

Initiator

Solvent

Dioctanoyl 2-bromosebacoyldiperoxide

Unknown

Lauroyl peroxide

Benzene

Chlorobenzene

Ethyl acetate

Ethyl ether
Mineral oil
Styrene

26
28
36
x

TABLE 5.
Number of
C atoms
4

2-Phenoxybenzoyl peroxide
Myristoyl peroxide
Menthylphthaloyl peroxide
Aliphatic polymeric
diacyl peroxide

kd(s'1)

Benzene
Benzene

Acetophenone
Benzene
Dioxane
Chlorobenzene

Ea (kj/mol)

30
40
50
60
70
60
70
85
70
40
50
60
70
61
79
99
T (K)
40
50
61
70
30
T (K)
34.8
49.4
61.0
74.8
100.0
50
60
65
70
50

1.08 x 10 " 4
3.0OxIO" 3
3.72 x l 0 ~ 4
2.56 x 10 " 7
4.91 x 10~7
2.19 x l O - 6
9.17 xlO~ 6
2.86 x l O - 5
1.51 x 10~5
5.58 x l 0 ~ 5
3.75 x l O - 4
4.33 x l O - 5
2.91 x 10 ~7
1.15 XlO" 6
4.75 x l O - 6
1.87 xlO~ 5
1.93 x 10 ~5
1.93 x l O - 4
1.93 XlO" 3
3.92 xlO 1 4
6.03 x 10 ~7
2.7OxIO- 6
1.05 x l 0 ~ 5
3.99 x l 0 ~ 5
1.97 x 10 " 6
2.2 x 1016
2.06 x 10 ~7
2.25 x l O " 6
1.42 x l 0 ~ 5
1.00 x l O - 4
2.39 x l O - 3
3.1 x 10" 6
1.2OxIO- 5
2.22 x l O - 5
4.32 x l O - 5
2.03 x 10 ~4

50
60
70
65
70
55
75
75
80

6.58 x 10 ~5
1.815 x 10 ~4
4.729 x l O " 4
8.18x10 ~5
3.38 x 10 ~5
1.15 x 10~4
9.04 x 10 ~5
9.00 x 10 " 5
1.720xl0" 4

85

Carbon tetrachloride

rraw5-4-(4-Methoxybenzylidene)butyryl peroxide
frarcs-4-(4-Methylbenzylidene)butyryl peroxide

T( 0 C)

Notes
X2
X2
X2
a

127.2

a
a
a
a,j

exp[- 12337/RT]

a
exp[- 137.9/RT]
a
a
a
a
a
121.1

90.4

121.3

c,h
c
c
a
a
Vu
Vi5
V 15

Refs.
214
214
214
99
68
68
68
68
126,337
126,337
126,337
16
68
68
68
68
344
344
344
344
68
68
68
68
99
1
10
10
10
10
10
287
287
287
287
194
194
194
194
5
16
65
302
302
302

HYDROPEROXIDES AND KETONE PEROXIDES

Initiator

Solvent

sec-Butyl hydroperoxide

Toluene

ter/-Butyl hydroperoxide

Benzene

T( 0 C)
172.0
182.3
130
145
160
154.5
161.7
169.3
174.6

fcd

(s"1)
2.65 x 10 ~5
4.9 XlO" 5
3 x 10 ~7
1.6 XlO" 6
6.6 x l O - 6
4.29 XlO" 6
9.27 x l O - 6
2.OxIO- 5
4.OxIO- 5

Ea (kj/mol)

138

170.7

Notes

a
a
a
h

Refs.
199
199
337
337
337
76
76
76
76

Notes page 11-69; References page II - 70

TABLE 5. cont'd
Number of
C atoms
4 (cont'd)

Initiator
tert-Butyl hydroperoxide

Solvent
Benzene
Chlorobenzene

Cumene
Cyclohexane
Dodecane
Heptane
w-Octane

Toluene

Vapor

tert-Butyl hydroperoxide/cobalt
2-Ethyl hexanoate

Chlorohenzene

tert-Butyl hydroperoxide/cobalt
stearate
Methyl ethyl ketone peroxides

Benzene

tert-Amyl hydroperoxide

Ethyl acetate
Chlorobenzene

Acetone cyclic diperoxide

Benzene

3,3,6,6-Tetramethyl-1,2,4,5tetroxane

Toluene
Benzene

Toluene
Vapor

Cyclohexyl hydroperoxide

Benzene
Benzene/styrene (50/50)
Cyclohexane

T( 0 C)
172.3
182.6
171
199
231
182.6
100
172
86.1
98.5
172
149.8
159.9
169.6
179.6
100
172.5
181.5
192.6
204.5
214.9
570
670
773
873
973
0
0
0
25
25
45
45
100
115
130
70
153
190
228
135.5
145.5
165.0
165.0
135.5
140.5
145.5
150.5
165.0
165.0
130.1
150.1
170.1
177.1
185.1
194.1
207.1
215.1
250.1
70
70
130
140
150

#d ( s 1 )
1.09 x l O " 5
3.1 x 10~5
1.93 x 10~5
1.93 x l O " 4
1.93 x l O " 3
8.1 x 10" 5
1.2xlO- ?
1.4IxIO- 4
1.32 xlO~ 6
5.55 x l O - 6
1.41 x 10" 4
8xlO"6
2.5 XlO" 5
6.9 x l 0 ~ 5
1.82 x l 0 ~ 5
5.7xl0"8
9.2 x l O " 6
2.69 XlO" 5
8.3 x l O " 5
1.52 XlO" 4
3.24 xlO~ 4
3.4XlO 1
4.95
8.4XlO 1
5.66 x 102
2.58 x 103
1.01 x 10" 3
8.29 x 10 ~5
5.4OxIO" 4
2.3 XlO" 3
1.1 x l O " 3
1.4xlO" 3
l.OxlO" 3
1.3 x 10 " 5
4.80xl0"5
1.60xl0" 4
1.28 x 10~6
1.93 x 10 " 5
1.93 x l O " 4
1.93 x l O " 3
6.25 x l O " 7
2.09xl0-6
1.41 x 10" 5
1.37 x l O " 5
6.25 x l O " 7
1.19 x 10~6
2.09 x l O " 6
2.83 XlO" 6
1.41 x 10" 5
1.37 x l O " 5
1.8 x l O " 6
3.4xlO- 6
3.5xl0-6
4.6x10-6
1.3 x l 0 ~ 5
2.4 x l O - 5
8.5 x l O " 5
1.66 x l O " 4
4.88 x l O - 4
0
1.27 x 10~3
2.38 x l 0 ~ 3
1.16 x l O - 2
3.20xl0" 2

Ea (kj/mol)

Notes

128.4

163.2

c
b
b
f
f
f

Vi0
V7
V1

101

147.1

Vi
a
a
a

a
a
a
a
a

Refs.
199
199
344
344
344
199
199
199
41
41
199
118
118
118
118
199
199
199
199
199
199
188
188
188
188
188
190
190
190
198
198
198
198
337
337
337
13
344
344
344
286
286
286
286
373
373
373
373
373
373
365
365
365
365
365
365
365
365
365
91
91
91
91
91

TABLE 5. cont'd
Number of
C atoms
6 (cont'd)

Initiator
Cyclohexyl hydroperoxide

Solvent
Benzene

80

Cyclohexane

80

Cyclohexene

80

Dimethylheptadiene

80

1-Octene

80

Benzyl hydroperoxide

Styrene

1,4-Dimethylcyclohexanehydroperoxide
1,1,3,3-Tetramethylbutylhydroperoxide

1,4-Dimethylcyclohexane

Benzene

Chlorobenzene

2,5-Dimethyl-2,5-di(hydroperoxy)hexane

(S)x

Benzene

n-Octyl hydroperoxide
2,4,4-Trimethylpentyl2-hydroperoxide
Poly(phenyleneethyl hydroperoxide)/manganese resinate

White oil
White oil

Cumene hydroperoxide

Benzene

Chlorobenzene

Chlorobenzene

Cumene

Mesitylene
Styrene
Toluene

Cumyl hydroperoxide

10

p-Cymene hydroperoxide

T( 0 C)

White oil
Acetone-d6

/?-Cymene

^d(S" 1 )

60
60
120

Reaction order
varies from
1.5 to 2.0
Reaction order
varies from
1.5 to 2.0
Reaction order
varies from
1.5 to 2.0
Reaction order
varies from
1.5 to 2.0
Reaction order
varies from
1.5 to 2.0
9xlO~6
1.8 x l O - 5
1.4xlO" 5

130
145
160
135
153
173

1.7xlO~ 5
7.41 x 10- 5
2.83 XlO" 4
1.93 x 10 ~5
1.93xlO- 4
1.93 x l O - 3

130
145
160
150
150

2.7xlO~ 6
1.0 x l O - 5
3.16 x l O - 5
9.29 x 10 ~5
9.29 x 10 " 5

26
30
35
115
130
145
159
193
253
110
120
132
T(K)

2.0OxIO- 4
2.75 x 10" 4
3.67 XlO" 4
4xlO"7
1.7 x l O - 6
6.6 x l O ~ 6
1.93 x 10 ~5
1.93 x l O " 4
1.93xl0-3
2.742 x 10 ~6
5.194 x l O - 6
9.305 x l O - 6
2.1OxIO 11

125
139
182.3
150
-33.0
-23.0
-12.0
-18.0
-8.0

9xlO~6
3 xlO-5
6.45 x l O " 5
1.34 x 10~4
7.0xl0~5
2.28 XlO" 4
1.2IxIO- 3
8.3 x l O - 5
4.23 x l O - 4

-3.0
110
120
132
T(K)

1.65xlO- 3
5.50OxIO" 6
1.20OxIO- 5
2.089 XlO" 5
1.23 x l O 1 2

Ea (kj/mol)

Notes

Refs.
119

119

119

119

119

C3
C4
c

276
276
224

134

a
a
a

337
337
337
344
344
344

113

a
a
a
a
a

337
337
337
177
177

t3
t3
t3
a
a
a

212
212
212
337
337
337
344
344
344
367
367
367
367
58
58
199
199
199
177
264
264
264
264
264

137.2

112.5
112.5
46.0

122

exp[- S0.0/RT]
98.7
101.3

121.3
62.0

110.2

tu
tM
tu

exp[-85.48//?71

264
367
367
367
367

Notes page 11-69; References page II - 70

TABLE 5. cont'd
Number of
C atoms
10 (cont'd)

Initiator
Decalin hydroperoxide

Solvent

Pinane hydroperoxide

Acetic acid
Chlorobenzene
Decalin
1,2-Dichlorobenzene
Ethylene glycol
Nitrobenzene
Pyridine
Benzene

2-Phenylbutyl 2-hydroperoxide

sec-Butylbenzene

l-Phenyl-2-methylpropylhydroperoxide

Benzene

l-Phenyl-2-methylpropyl-2hydroperoxide

Benzene

Tetralin hydroperoxide

Poly(butene)
n-Butyl stearate
2-Ethyl-l-hexene
1-Hexadecene
Mineral oil

/i-Octadecane
Isooctane
Octyl ether
Poly(propylene)
-Tetradecane
Tetralin
2,2,4-Trimethyl-l-pentene
white oil
Toluene

(1O)n

Poly(cumyleneethylhydroperoxide)
(MWIlOO)

11

2,2-Bis(terf-butyldioxy)propane

Cumene

l-Methoxy-l-(terf-butylperoxy)
cyclohexane

Cumene

sc-Butyltoluene hydroperoxide

^c-Butyl toluene

2,2-Di-(tert-butylperoxy)butane

Chlorobenzene

2,2-Bis(ter/-butyldioxy)butane
Diisopropylbenzene
monohydroperoxide

Cumene
Chlorobenzene

l-Methoxy-l-(terr-amylperoxy)
cyclohexane

Cumene

12

T( 0 C)
130
130
130
130
130
130
130
130
145
160
110
120
132
T(K)
133.8
143.9
153.9
163.7
174
144.2
154.5
165.6
176.0
170
170
130
170
170
135.6
150.6
170
170
170
170
170
170
T(K)
170
150
130
140
150
90
100
110
120
80
90
100
110
100
110
120
T(K)
98
116
136
T(K)
100
150
182
218
80
90

^d(S"1)
5.5xl0~4
10% in 3 h
1.4IxIO- 5
4.48 x l O " 5
1.65 x 10 ~4
4.73 x 10 ~5
(2.31-2.89) x 10 ~4
7.08 x 10 " 6
2.72 x l 0 ~ 5
9.17 x l O - 5
2.944 x 10 ~6
6.61IxIO- 6
1.089 XlO" 5
4.06 xlO 1 2
3.18 x l O " 6
8.95 x 10 " 6
2.OxIO" 5
4.03 XlO" 5
9.77 x l O " 5
5.04 x 10 " 6
1.21 x IO"5
2.92 x l O " 5
6.97 XlO" 5
2.17 x l O " 3
1.47 x l O " 4
1.08 x l O " 4
1.26 x l O " 3
7.92 x l O " 4
4.2 x l O " 5
1.00 XlO" 4
4.82 x l O - 4
2.54 x 10~4
1 31 x 10" 4
1.45 x l 0 ~ 3
2.5OxIO" 3
2.32 x 10~4
2.27 x 109
1.67 x 10~3
1.34 x 10~4
2.79 x 10" 5
4.OxIO- 5
5.78 XlO" 5
2.16 x 10~6
9.14 x l O " 6
2.97 XlO" 5
9.56 x l O " 5
4.79 x 10 ~6
1.898 x 10 ~5
6.57 x l 0 ~ 5
2.139 x l O - 4
4.11IxIO- 6
8.194 XlO" 6
1.9555 x l O - 5
1.02 xlO 1 6
1.93 x 10 ~5
1.93 x l O - 4
1.93 xlO" 3
9.3OxIO 16
1.84 x 10 ~5
1.93XlO" 5
1.93 x 10 ~4
1.93 x l O - 3
7.82 xlO~ 6
3.07 x 10 " 5

a (kj/mol)

Notes

124.3
176.4
117.2

123.8

a
a
a

exp[-87.15//?7]
122.2

125.5

78.2
125.5
82.8

t3
t3
e,t3
t3
t3
t3
e,t3
t3
t3
t3
t3
t3
t3

117.2
131.4

119.2
121.3

exp[-102.1 /RT]
t3
121.3

txp[-\W2/RT]

exp[-154.08/^7]

Refs.
228
228
228
228
228
228
228
18
18
18
367
367
367
367
76
76
76
76
76
76
76
76
76
71
71
71
71
71
71
71
71
71
71
71
71
71
112
71
177
210
210
210
361
361
361
361
348
348
348
348
367
367
367
367
344
344
344
344
361
344
344
344
348
348

TABLE 5. cont'd
Number of
C atoms
12 (cont'd)
13

14

Initiator

Solvent

l-Methoxy-l-(te/Y-amylperoxy)
cyclohexane
l-Methoxy-l-(terf-hexylperoxy)
cyclohexane

Cumene

U-Bis(tert-butylperoxy)cyclopentane

Cumene

2,2-Bis(terf-butyldioxy)-3-methylbutane

Diphenylmethane

U-Bis(terf-butylperoxy)cyclohexane

Cumene

Cumene
Cumene

Chlorobenzene

l,l-Bis(terr-butylperoxy)-2-methylcyclopentane

15

16

17

w-Dodecane
n-Hexadecane
H-Hexane
n-Nonane
Cumene

1,1-Diphenylethyl hydroperoxide

Chlorobenzene

l-Methoxy-l-(rm-octylperoxy)cyclohexane

Cumene

U-Bis(^-butylperoxy)-2-methylcyclohexane

Cumene

U-Bis(terf-amylperoxy)cyclohexane

Cumene

l,l-Bis(terf-butylperoxy)cyclooctane

Cumene

l,l-Bis(^rr-butylperoxy)-2-n-propylcyclohexane

Cumene

l,l-Bis(terf-butylperoxy)2-isopropylcyclohexane

Cumene

l,l-Bis(ferf-butylperoxy)3,3,5-trimethylcyclohexane

Cumene

T( 0 C)
100
110
80
90
100
110
80
90
100
110
90
100
110
120
100
80
90
100
110
94
113
134
T (K)
100
100
100
100
80
90
100
110
90
110
130
150
T (K)
70
80
90
100
80
90
100
110
80
90
100
110
90
100
110
120
80
90
100
70
80
90
100
80
90
100
110

A:d (s"1)
1.058 xlO~ 4
3.450 x 10 " 4
8.34 x 10~6
3.17 x l O " 5
1.12Ox 10" 4
3.653 x l O - 4
4.98 x l O " 6
1.80xl0~ 5
6.67 x l O " 5
2.17 XlO" 4
1.08 x 10 ~5
3.75 x 10 ~5
1.29 XlO" 4
4.1IxIO-4
3.17 x l O " 5
3.47 x 10~6
1.45 x 10 ~5
5.06 x l O " 5
1.62 XlO" 4
1.93 x 10 " 5
1.93 x l O " 4
1.93 x l 0 ~ 3
3.47 x 1015
3.51 x 10 ~5
3.15 x l O " 5
3.82 x 10 " 5
3.62 x 10 ~5
1.55 x 10~5
5.82 x 10~5
1.85 x l O " 4
6.0OxIO" 4
2.OxIO" 9
1.007 XlO" 6
1.034 XlO" 6
1.223 XlO" 6
1.38 x 108
5.9xlO~ 6
2.3OxIO" 5
8.18 x l O " 5
2.84OxIO" 4
1.29 x 10~5
4.51 x 10 " 5
1.43 XlO" 4
4.58 x l O " 4
5.34 x l O " 6
2.02 x 10 " 5
7.32 x l O " 5
2.44 XlO" 4
1.11 x 10 " 5
4.15 x 10~5
1.36 x l O - 4
4.24 xlO~ 4
1.2OxIO- 5
4.19 x 10 " 5
1.38 XlO" 4
2.59 x 10" 5
4.86 x 10 ~5
1.98 x l O " 4
7.46 XlO" 4
3.82 x 10~6
1.50 x 10 " 5
5.31 x 10 " 5
1.75 XlO" 4

Ea (kj/mol)

exp[- 142A/RT]

exp[- 105A/RT]

Notes

Refs.
348
348
348
348
348
348
349,364
349,364
349,364
349,364
358
358
358
358
361
349,350
349,350
349,350
348,349,350
344
344
344
344
364
364
364
364
349
349
349
349
374
374
374
374
374
348
348
348
348
349
349
349
349
348
348
348
348
364
364
364
364
349
349
349
349
349
349
349
349,364
349,364
349,364
349,364

Notes page 11-69; References page 11-70

TABLE 5. cont'd
Number of
C atoms
Il (cont'd)

Initiator

Solvent

U-Bis(tert-butylperoxy)3,3,5-trimethylcyclohexane

Chlorobenzene

rc-Butyl 4,4-di-(terf-butylperoxy)
valerate

Chlorobenzene

18

l,l-Bis(terr-hexylperoxy)cyclohexane

Cumene

20

U-Bis(tert-butylperoxy)cyclododecane

Cumene

22

U-Bis(tert-octylperoxy)cyclohexane

Cumene

31

2,2-Bis[4,4-di-(tert-butylperoxycyclohexyl)propane

Chlorobenzene

TABLE 6.
Number of
C atoms
4
5

85
105
128
T (K)
102
121
143
T(K)
80
90
100
110
90
100
110
80
90
100
110
87
106
128
T(K)

kd (s"1)
1.93 x ICT5
1.93 x 10 ~4
1.93 X l O - 3
7.59 x 10 13
1.93 x 10 " 5
1.93 x 10 ~4
1.93 XlO- 3
1.91 x 1015
5.38 x 10~6
2.06 x 10 ~5
7.48 XlO" 5
2.48 XlO- 4
8.14 x l O " 6
3.22 x 10~5
9.93 XlO" 5
1.513 x 10~5
5.62 x 10 ~5
1.983 X l O - 4
6.26 x l O - 4
1.93 x 10 ~5
1.93 x 10 ~4
1.93 x l O - 3
8.79 x l O 1 4

Ea (kj/mol)

Notes

Refs.
344
344
344
344
344
344
344
344
348
348
348
348
364
364
364
348
348
348
348
344
344
344
344

exp[- 127.52/RT]

exp[- 143.51/RT]

exp[-135.56//?7]

PERESTERS AND PEROXYCARBONATES

Initiator
Dimethyl peroxalate
tert-Butyl percarbamate
tert-Butyl performate

Solvent

J( 0 C)

Pentane
Chlorobenzene
Chlorobenzene

25
90
130.8
140.8
140.6
140
140
140.6
140
140.6
140
79.5
88.4
92.8
64
64
64
64
79.6
87.8
92.6
88.2
92.8
99.4
75
85
85
100
115
130
75

4-Chlorotoluene
Cumene
6

J( 0 C)

Isobutyl peracetate

a-Methylstyrene

tt-Butyl peracetate

a-Methylstyrene

sec-Butyl peracetate

terr-Butyl peracetate

a-Methylstyrene

terf-Amyl

alcohol
Benzene

n-Butanol

A^(S"1)
1.7xlO~ 5
6.6xlO" 6
5.43 x 10 ~5
1.7OxIO- 4
1.8OxIO- 4
2.12 XlO" 3
5.06 x l O - 4
1.61 x 10~4
1.62 x l O - 3
1.77 x 10~4
1.02 XlO" 3
1.36 x l O " 5
3.61xl0" 5
5.58 x l O - 5
~9.6xl0~3
8.2 x l O - 3
6.5 x l O - 4
1.2 x l O - 3
1.57 x l O - 5
3.27 x l O - 5
5.38 x l O - 5
1.79XlO"5
3.19 x l O - 5
5.37 x l O - 5
2.8 x 10 " 6
1.2xlO~ 6
2.18 x l O - 6
1.54 x 10- 5
1.02 XlO" 4
5.69 x l O - 4
2.65 x 10 ~5

Ea (kj/mol)

Notes

159.0

64.0

m2
V8
V1
v8
b
b,v6

115.2

g2,vi6
g2,vi7
g2,vi8
g2,vi9
101.0

104.3

151.9

a
a
a
a

Refs.
203
141
218
218
218
218
218
218
218
218
218
253
253
253
253
253
253
253
253
253
253
253
253
253
193
193
126,337
126,337
126,337
126,337
193

TABLE 6. cont'd
Number of
C atoms
6 (cont'd)

Initiator
rm-Butyl peracetate

Solvent
2-Butanol

Chlorobenzene

Decane

rm-Butyl trichloroperacetate

Diethyl peroxydicarbonate

Dodecane
Hexadecane
Hexane
Octane
Paraffin
Tetradecane
Chlorobenzene

terr-Butanol
2,2'-Oxydiethylene
bis(allyl carbonate)

Diethyl peroxalate
ten-Amyl peracetate

Pentane
Chlorobenzene

tert-Butyl methoxyperacetate

Ethylbenzene

terf-Butyl peracrylate

Benzene

terr-Butylperoxy isopropyl

Chlorobenzene

terr-Butyl perpropionate
carborate

Benzene
Decane
Dodecane
Hexadecane
a-Methylstyrene

rm-Butyl 2-acetoxyperacetate
tert-Buty\ cyclopropanepercarboxylate

Octane
Tetradecane
Ethylbenzene
-Dodecane
rc-Hexadecane
2,2,4-Trimethylpentane

ferf-Butyl ethoxyperacetate

Ethylbenzene

T (0C)

d (s" 1 )

75
75
75
60
100
119
139
T (K)
100
115
125
100
100
100
130.1
100
130.1
100
60
66.8
77.0
45
55
40
50
60
25
90
108
129
T(K)
40.0
39.6
50.2
60.1
90
100
110
98
117
137
T(K)
80
90
100
100
100
70
90
100
100
91.8

1.13 x 10" 4
5.3 XlO" 5
4 xlO-7
2.3IxIO"8
1.93 XlO" 5
1.93 XlO" 4
1.93 x l O " 3
1.57 x 10 16
1.5 x IO" 5
7.9IxIO-5
2.45 XlO" 4
1.95 x 10- 5
1.78 x 10 ~5
1.55 x 10 " 5
5.08 x 10~4
2.07 x 10 ~5
3.13 x 10~4
1.55 x 10 ~5
1.19 x 10 " 5
2.75 x l O - 5
1.00 XlO" 4
1.25 x 10 " 5
5.7 x l 0 ~ 5
6.94 x l O " 6
2.86 x 10 " 5
1.28 x l O - 4
2.6xlO"5
1.93 x 10 " 5
1.93 x l O " 4
1.93xl0- 3
4.13 x l O 1 5
2.2xlO"4
1.94 x l O - 4
8.24 x l O - 4
2.35 x l O - 3
1.12 x l O " 5
1.5IxIO- 5
4.85 x l O - 5
1.93 x 10 " 5
1.93 XlO" 4
1.93 x l O - 3
2.49 x l O 1 6
1.53 x 10~6
6.04 x 10 " 6
1.82 x 10 ~5
1.78 x IO" 5
1.58 x 10 ~5
3.02 x 10~7
4.85 x l O " 6
2.03 x 10 ~5
1.68 x 10 ~5
2.73 x 10 ~5

113.0
102.6
113.0
102.6
113.0
120.4
40.0
40.6
46.0
55.6

5.48 x 10 ~5
1.28XlO" 5
4.92 x l O - 5
1.7IxIO- 5
6.19 x 10~5
1.505 XlO" 4
2.96 x 10 ~4
2.89 x l O - 4
5.58 x l O - 4
1.94 XlO" 3

E31 (kj/mol)

Notes

159.0

c
t7
m3
a,h

exp[- 149.36/RT]
134

125.9
126.8

a,h
h

133.9-138.1

c
c
a
a
a

127.2

exp[-141.1/#n
104.7
103.9

86.2

a,h
h

a
a
a

exp[-150.15//?7]
a
a

a
a

153.8

146.2

105
102.7

a
m 2 ,h

Refs.
193
193
193
81
344
344
344
344
337
337
337
270
270
270
169
270
169
270
81
28
28
18
18
90
90
90
203
344
344
344
344
315
328
328
328
211
211
211
344
344
344
344
213
213
270
270
270
213
213
270
270
328
255
255
255
255
255
255
315
328
328
328

Notes page 11-69; References page 11-70

TABLE 6. cont'd
Number of
C atoms
8 (cont'd)

Initiator
tert-Butyl heptafluoroperoxybutyrate

Solvent
Benzene

Methanol

Methoxybenzene

Nitrobenzene

Octane

Pyridine

Toluene

terf-Butyl methoxyperpropionate
terr-Butyl perisobutyrate

Ethylbenzene
Benzene

Bulk
Chlorobenzene

Cumene

Decane

terf-Butyl percrotonate

Dodecane
Hexadecane
Iso-octane
Nujol
Octane
Tetradecane
Benzene

T( 0 C)
65.0
70.0
75.0
80.0
60.0
65.0
70.0
75.0
80.0
60.0
65.0
70.0
75.0
10.0
15.0
19.6
30.0
55.0
60.2
65.0
70.0
40.0
45.0
50.0
85.0
90.0
95.0
100.0
30.0
40.0
50.0
65.0
75.0
80.0
85.0
40.3
78
70
85
100
70
90.6
100.7
110.0
79
98
118
T(K)
90.6
100.7
110.0
70
85
100
100
100
100
103.4
103.4
100
100
100
115
130

^d(S"1)
1.56 x 10 " 5
3.09 x 10 ~5
5.27 XlO" 5
9.08 x l O " 5
9.5 x l O " 6
1.61 x 10~5
2.7OxIO- 5
5.23xl0-5
9.18 x l 0 ~ 5
9.6 XlO" 6
1.93 x l O - 5
3.57 XlO" 5
6.35 x l 0 ~ 5
7.19 x 10~5
9.37 x l 0 ~ 5
1.304 x l O - 4
2.604 x l O - 4
5.01 x 10 ~5
8.56 x l O " 5
1.378 x l O - 4
2.444 XlO" 4
3.26 x 10 ~5
6.36 x l O " 5
9.31 x 10 " 5
5.1 x 10 ~6
9.5 xlO~ 6
1.75 x l O - 5
3.41 x 10 " 5
2.74 x 10 " 5
7.66 x l O " 5
1.868 x l O " 4
1.88 x 10 " 5
4.66 XlO" 5
7.06 x l O " 5
1.203 x l O " 4
4.30xl0~ 3
3.77 x 10~5
6.69 x l O " 5
5.33 x l O - 5
3.5OxIO- 4
4.12 XlO" 5
8.13 x 10" 5
2.75 x l O " 4
8.92 x l O " 4
1.93 xlO~ 5
1.93 x l O - 4
1.93 x l O " 3
2.07 xlO 1 5
6.9 x l O " 5
2.35 x l O " 4
6.57 x l O " 4
4.7 x l O " 6
2.6 x l O - 5
1.55 x l O " 4
1.46 x l O " 4
1.56 x 10 " 4
1.47 x 10 " 4
2.16 xlO~ 4
2.23 x l O " 4
1.59 x 10 ~4
1.52 x 10 " 4
2.5xlO" 5
1.5OxIO- 4
7.39 x l O - 4

Ea (kj/mol)

Notes
v 24
V24
V24
V24
V25
V25
V25
V25
V25
V26
V26
V26
V26

140.6

a
a
a
a
a
h

exp[-135.16/,RrI
133.1

140.6

122

a
a
a

138

a
a
a

Refs.
370
370
370
370
370
370
370
370
370
370
370
370
370
369
369
369
369
370
370
370
370
370
370
370
370
370
370
370
370
370
370
369
369
369
369
328
37
126,337
126,337
126,337
37
136
136
136
344
344
344
344
136
136
136
337
337
337
270
270
270
251
251
270
270
337
337
337

TABLE 6. cont'd
Number of
C atoms
8 (cont'd)

Initiator

Solvent

tert-Butyl permaleic acid

Acetone

tert-Butyl permethacrylate

Benzene

tert-Butyl peroxyisopropyl carbonate

Benzene

Cyclohexyl peracetate

a-Methylstyrene

Diisopropyl peroxalate
Diisopropyl peroxydicarbonate

Pentane
Benzene
Di-rc-butyl phthalate

Decane

Ethylbenzene
Mineral spirits

2,2/-Oxydiethylenebis(allyl carbonate)

Ethyl tert-butyl peroxalate

Toluene
Benzene

tert-Butyl 2-acetoxyperpropionate
ter/-Butyl 5-bromo-2-perthenoate

Ethylbenzene
Carbon tetrachloride

tert-Butyl 5-chloro-2-perthenoate

Carbon tetrachloride

tert-Butyl cyclobutanepercarboxylate

n-Hexadecane
2,2,4-Trimethylpentane

T( 0 C)

^d(S"1)

70
85
101
90
100
110
90
100
110
88.6
93.0
99.3
25
54.0
77
87
97
107
117
35
45
60
54.3
54.3
30
45
60
75
40
50
60
50
45
55
65
91.4
99.2
112.0
124.5
99.2
112.0
124.5

2.7xlO~ 6
1.6 x l O " 5
6.77 x l O " 5
1.92 x l O ' 5
7.66 XlO- 5
1.92 x l O " 4
6.64 x 10 " 6
2.21 x 10~5
6.87xl0-5
1.63 x l O " 5
2.30xl0"5
4.75 XlO" 5
6.0xl0~ 5
5.0xl0"5
1.39 x 10 ~3
4.09 x l O " 3
1.25 x l O " 2
3.54xl0-2
7.98 x l O " 2
6.3 x l O " 6
2.7xlO-5
1.85 x l O " 4
4.5 x 10 " 5
5.2x10-5
2xlO"6
1.8xl0-5
1.28 XlO" 4
7.55 x l O " 4
6.39 x 10~6
2.28 x 10 " 5
9.44xlO- 5
3.03 x 10 " 5
4.48 x 10~5
1.63 x l O " 4
5.93 x l O " 4
3.6OxIO" 4
2.24 x 10 " 6
1.18x10-5
4.30x10-5
2.29 x 10 " 6
9.56 XlO" 6
4.42x10-5

102.6
92.9
102.6
113.0

4.33 x 10~5
1.2IxIO- 5
4.84 x 10 " 5
1.668 XlO" 4

E2, (kj/mol)

Notes

113

a
a
a
a
a
a
a
a
a

137.0

109.4

113

113

117.6

112.5

143.5

143.5

ni2
yi 6
yi 6
y 16
yi6
y!6
a
a
a
m2
a
a
a
a
a
a
a
a
c,h

a
a
a
a
a
a

150.4

Refs.
337
337
337
211
211
211
9
9
9
253
253
253
203
60
236
236
236
236
236
337
337
337
60
60
337
337
337
337
90
90
90
90
31
31
31
328
176
176
176
176
176
176
255
255
255
255

ter/-Butyl 2,2-dimethyl3-bromoperpropionate

Cyclohexane

55
65
75

9.50xl0~ 6
3.58xl0-5
1.23 x l O " 4

118.2

h,t6
t6
t6

320
320
320

tert-Butyl 2,2-dimethyl3-chloroperpropionate

Cyclohexane

55
65
75

3.55 x 10" 6
1.48x10-5
5.65x10-5

128.6

h,t6
t6
t6

320
320
320

tert-Butyl 2,2-dimethyl3-iodoperpropionate

Cyclohexane
Ethylbenzene

2.91 x 10" 5
3.76 x l O - 4
4.8 x 10~4
4.22 x l O - 4
1.39 x 10 " 3
2.68 x l O " 3

116.9

tert-Butyl isopropoxyperacetate

55
75
40.0
39.9
49.9
55.3

h,t6
t6
a,h
h,m2

320
320
315
328
328
328

100.6
98.9

Notes page 11-69; References page 11-70

TABLE 6. cont'd
Number of
C atoms
9 (cont'd)

Initiator
tert-Butyl 1-methylcyclopropylpercarboxylate
Di-(tert-butylperoxy)-carbonate

terf-Butylperoxy isopropyl
carbonate
terf-Butyl perpivalate

Solvent
2,2,4-Trimethylpentane
Chlorobenzene

1,2-Dichlorobenzene
Cumene
Isopropyl ether
Benzene

Benzene

Chlorobenzene

Cumene

Cyclohexane

Decane

Dioxane/water (90/10)
Dodecane
Hexadecane
Hexane

Heptane
Isooctane
Mineral spirits

tert-Buty\ perpivalate-d6

Octane
Tetradecane
Chlorobenzene

T(0C)
102.6
113.0
99.95
110.1
120.1
120.1
99.95
99.95
85
100
115
50
70
85
50
55
60
65
70
48.9
58.6
64.3
57
75
94
T(K)
74.8
60
60.6
74
45
55
60
65
64.6
75.6
84.6
70.3
55
65
75
50
70
80
60.6
80
80
55
60
65
70
80
60.6
73.9
55
60
65
70
75
T (K)
80
80
60.6
74.0

* d (s"1)
2.30 x 10 " 5
7.47 x l O " 5
6.72 x 10~5
2.13 xlO~ 4
6.05X10- 4
5.98 x 10 ~4
6.72 x 10 " 5
2.76 x 10 ~4
3.3xlO" 6
2.2xlO" 5
1.36xlO- 4
9.77 x 10 " 6
1.24X10- 4
7.64X10- 4
1.03 XlO" 5
1.94 XlO" 5
3.92 x l 0 ~ 5
7.31 x 10~5
1.30x10-4
8.4xlO" 6
3.35xlO- 5
7.0IxIO- 5
1.93 x l 0 ~ 5
1.93xlO- 4
1.93 x l O " 3
7.09 XlO 14
2.79xlO- 4
3.85 XlO" 5
4.0OxIO- 5
1.93X10- 4
3.53 x 10 ~6
1.73 x l O " 5
2.95 XlO" 5
4.53 x l O - 5
5.8IxIO- 5
2.1OxIO- 4
5.94 x l O " 4
1.11 x l O - 4
1.03 x 10 ~5
4.02 x l O - 5
1.45 x l O - 4
4.IxIO"6
5.52 XlO" 5
2.18 x l O - 4
6.26 x 10~5
2.38 x 10 ~4
2.39 x 10 " 4
8.42 x 10 '6
1.59 XlO" 5
3.39 x l O - 5
6.19 XlO" 5
2.33 x 10 ~4
1.97 x 10 ~5
8.82 x l O " 5
1.01 x 10 ~5
2.15 x l 0 ~ 5
4.14 x l O - 5
7.58 XlO" 5
1.47X10- 4
3.56 x 1014
2.34 x 10 ~4
2.27 x 10 ~A
3.24 x 10~5
1.57 xlO~ 4

a (kJ/mol)

Notes

Refs.

133.7

255
255
27
27
27
27
27
27
337
337
337
126,337
126,337
126,337
359
359
359
359
359
249
28
28
344
344
344
344
28
81
156
156
160
160
362
160
159
159
159
267
320
320
320
337
337
270
156
270
270
359
359
359
358
270
165
165
359
359
359
359
359
376
270
270
156
156

133.1

138

119.7

125.5

a
a
a
a
a
a

k
h

exp[- 123.59/RT]
128.0

106.7

a,h
t9
t9
h

115.5

122.8

117

a
a
t9

t9
t9

exp[- 123/RT]

t9
t9

TABLE 6. cont'd
Number of
C atoms
9 (cont'd)

Initiator
tert-Butyl

perpivalate-d6

tert-Butyl 2-perthenoate

tert-Butyl 1-pyrollidinepercarboxylate
tert-Butyl Af-succinimidopercarboxylate

10

tert-Amyl

perpivalate

Solvent

(s"1)
5.05 x 10" 5
1.62 x 10~5
8.82 x l O - 5
3.3 x 10 " 6
1.66 x l 0 ~ 5
6.87 x l O - 5

Chlorobenzene

90

7.59 x 10 ~5

Acetonitrile
Benzene
Chlorobenzene

100
100
90
100
90
100
100
100
90
100
51
55
72
91
T (K)
50
60
70
80
35
45
60
47
63
82
T(K)
30
40
60
49
65
83
T (K)
74.7
80.7
90.8
40.3
99.8
116.6
129.9

9.9xlO~ 4
3.79 x 10~5
1.32 x 10 ~5
4.9IxIO-5
3.3xl0-6
1.10 x 10~5
9.OxIO- 6
6.00xl0"3
9.24 x 10 ~5
3.4IxIO-4
1.9XlO" 5
1.93 x 10 ~5
1.93 x l O - 4
1.93 x l O - 3
4.12 x 1015
1.05 x 10 ~5
3.5IxIO-5
1.309 XlO" 4
4.239 XlO" 4
6.9xlO~ 6
2.6xlO" 5
1.8OxIO- 4
1.93 x 10 ~5
1.93 XlO" 4
1.93 XlO" 3
3.19 xlO 1 5
2xlO"6
1.0 x l O - 5
1.34 x l O - 4
1.93 x 10 " 5
1.93 x l O - 4
1.93 XlO" 3
7.00 x 1015
1.98 xlO~ 4
4.37 x 10 " 4
1.25 x l O - 3
2.91 x 10 " 4
1.65 x 10 ~5
1.38 x 10~4
6.83 x l O - 4

113.0
92.9
102.6
113.0
75
93
113
T (K)
42.42
50.30
57.95
44.85
50.10
60.20

3.02 x 10 ~4
2.47 x 10 ~5
8.87 x 10 " 5
2.89 x l O - 4
1.93 x 10 " 5
1.93 x l O - 4
1.93 x l 0 ~ 3
2.45 x 1015
9.04 x 10 ~5
2.349 x l 0 ~ 5
5.66OxIO- 5
1.874 x 10 ~5
3.609 x l O - 5
1.306 x l O - 4

Carbon tetrachloride

Cumene
Cyclohexane
Cyclohexene
Methanol
Methylene chloride
Nitrobenzene
Benzene
Chlorobenzene

Decane

Chlorobenzene

Mineral spirits

Di-w-butyl peroxydicarbonate

Chlorobenzene

tert-Butyl 2-acetoxy-2methyl perpropionate

Ethylbenzene

tert-Butyl
tert-butoxyperacetate
tert-Butyl 4-carbomethoxyperbutyrate

Ethylbenzene
Cumene

tert-Butyl cyclopentylpercarboxylate

fcd

60.6
60.6
73.9
99.2
112.0
124.5

Dioxane/water (90/10)
Isooctane

Cumene

Di-(sec-butyl)peroxydicarbonate

T( 0 C)

n-Hexadecane
2,2,4-Trimethylpentane

tert-Butyl peroxydiethyl acetate

Chlorobenzene

tert-Butyl 2,2-dimethylperbutenoate

Cumene

tert-Butyl 2,2-dimethylperbutyrate

Cumene

Ea (kj/mol)

147.3

Notes
t9
t9
t9
m2
m2
m2

Refs.
156
165
165
176
176
176
141

113.4

h,m2
m2
t9

m2
a

exp[- 121J6/RT]

113

exp[-123.85//?7]
113

a
a
a

a
a
a

exp[- 126.65/RT]
m2

151.3

140.8

exp[- 134.00/RT]
100.7

142
142
141
142
141
142
142
142
141
142
338
344
344
344
344
362
362
362
362
337
337
337
344
344
344
344
337
337
337
344
344
344
344
328
328
328
328
257
257
257
255
255
255
255
344
344
344
344
274
274
274
274
274
274

Notes page 11-69; References page II - 70

TABLE 6. cont'd
Number of
C atoms
10 (cont'd)

Initiator
Di(tert-butylperoxy)-oxalate

Solvent
Benzene

tert-Butanol
Decane
Dodecane
Octane
n-Pentane
Tetradecane
Styrene

11

tert-Butyl 5-methyl-7-perthenoate

Carbon tetrachloride

P-Methyl-P-phenyl-P-peroxypropiolactone

Carbon tetrachloride

Bis(2-nitro-2-methylpropyl)-peroxydicarbonate
1-Phenylethylperacetate
tert-Butyl
4-chloroperbenzoate

tert-Butyl-JV-(2-chlorophenylperoxy)carbamate

Toluene
Benzene
Phenyl ether

Carbon tetrachloride
Toluene

tert-Butyl-AK3-chlorophenylperoxy>
carbamate

Toluene

tert-Butyl-AH4-chlorophenylperoxy)carbamate

Toluene

tert-Butyl cyclohexylperoxycarboxylate

-Hexadecane
2,2,4-Trimethylpentane

tert-Butyl-iV-(2,5-dichlorophenylperoxy) carbamate

Toluene

tert-Butyl 2,2-dimethylperpentanoate

Cyclohexane

Cumene
tert-Butyl 5-ethyl-2-perthenoate

Carbon tetrachloride

tert-Butyl 2-iodoperbenzoate

Chlorobenzene

tert-butyl 4-nitroperbenzoate

Phenyl ether

tert-Butyl 3,5-dinitroperbenzoate

Carbon tetrachloride
Carbon tetrachloride

T( 0 C)

kd (s"1)

Ea (kj/mol)

Notes
c,h
c
c

35.0
45.0
55.0
25.0
41
41
41
37.8
41
35
45
55
99.2
112.0
124.5
106.8
126
134
50

6.77 x 10" 5
2.6IxIO" 4
9.3 XlO" 4
1.83 x l O " 5
1.75 x 10 " 4
1.81 x 10" 4
1.79 x 10 " 4
1.01 x 10" 4
1.71 x 10~4
5.5xl0"5
1.71 x 10" 4
6.0IxIO" 4
4.6xlO~ 6
1.94 x l 0 ~ 5
7.95 XlO" 5
5.65 x 10 " 6
4.59 x 10 " 5
9.71 x 10" 5
2.22 x 10 ~5

106.7

100
100.0
110.1
120.2
130.9
80
87.0
95.5
103.3
78.0
87.0
96.6
102.7
73.0
78.5
87.0
92.5
92.9
102.6
82.2
92.9
102.6
113.0
88.0
95.0
103.3
114.5
55
65
75
45
55
99.2
112.0
124.5
85.0
102.4
118.8
110.1
120.2
130.9
141.5
80
80

1.14 x l O " 4
3.89 x 10 ~6
1.85 x l 0 ~ 5
6.39 XlO" 5
2.42 xlO~ 4
4.2xlO~ 7
3.5xl0"5
1.48 x 10 ~4
3.3 XlO" 4
2.6 x l O " 5
7.8xl0"5
2.03 xlO~ 4
4.62 XlO" 4
5.57 x 10 ~5
1.42 x 10 ~4
2.75 xlO~ 4
5.37 x l O " 4
6.70xl0~ 5
2.046 x 10 ~4
1.57 x l O " 5
6.13 x l 0 ~ 5
2.046 xlO~ 4
6.58 x l O " 4
2.75 x 10 ~5
5.58 x 10 ~5
1.48 xlO~ 4
4.82 xlO~ 4
1.66 x 10 ~5
6.31 x 10~5
2.23 xlO~ 4
6.2xlO~ 6
2.15 x l 0 ~ 5
5.39 x 10 ~6
2.12 x l 0 ~ 5
7.91 x 10~5
4.02 x 10 ~5
2.58 xlO~ 4
1.32 xlO~ 3
7.56 x 10 " 6
3.19 x l 0 ~ 5
1.11 xlO~ 4
3.92 xlO~ 4
2.9xlO~ 7
1.1 x 10 ~7

138.7
164.4

h
a
a
a
a

157.3

115.5

119.7

136.6

135.8

128.9

120.7

105.4

75.3

137.7

131.8

a,m2
a,m2
a,m2
h,v 9
c,v9
a

130.5

172.8

Refs.
30
30
30
197
270
270
270
197
270
215
215
215
176
176
176
195
195
195
90
259
53
53
53
53
354
36
36
36
36
36
36
36
36
36
36
36
255
255
255
255
255
255
36
36
36
36
320
320
320
160
160
176
176
176
134
134
134
53
53
53
53
354
354

TABLE 6. cont'd
Number of
C atoms
W (cont'd)

Initiator

Solvent

/m-Butyl-AH3-nitrophenylperoxy)carbamate

Toluene

fm-Butyl-AK4-nitrophenylperoxy)carbamate

Toluene

terf-Butyl perbenzoate

Acetic acid
Benzene

Bromobenzene
rc-Butanol
-Butyl acetate

tert-Butylbenzene
w-Butyl ether
Carbon tetrachloride
Chlorobenzene

4-Chlorotoluene

Cumene

Decane

Dodecane
Ethylbenzene
Heptane
Hexadecane
Methyl benzoate
Octane
Phenyl ether

Tetradecane
Trimethylbenzene
Xylene

T( 0 C)
78.0
88.7
98.0
106.0
73.0
87.0
98.0
106.0
100.0
110.0
100
115
130
110.0
119.4
130.0
119.4
90.0
100.0
110.0
119.4
110.0
1194
119.4
100.0
110.0
80
110.0
119.4
120
135
150
103
122
142
T(K)
110.0
119.4
130.0
60
79.6
85.0
99.3
115.0
130.2
100
115
130
115
115
119.4
115
115
119.4
115
100.0
110.1
120.2
130.9
115
T (K)
119.4
130.0

A:d (s"1)
8.4 x l O " 6
2.43 x 10 " 5
1.01 x 10- 4
2.36 x l O " 4
6.4xlO~ 6
3.11 x 10~5
8.75 x l O " 5
2.38 xlO~ 4
3.83 x 10 ~5
1.14 x 10~4
1.07 x KT 5
6.22 x l 0 ~ 5
3.5OxIO- 4
3.50xl0" 5
1.04 XlO" 4
3.30xl0~ 4
1.37 x 10 ~4
9.27 x 10 " 5
2.7OxIO- 4
1.06 x 10~4
2.67 x l O " 4
3.6IxIO- 5
1.10 xlO~ 4
1.03 x 10 ~4
7.8OxIO- 5
1.80 XlO" 4
8.8xl0"7
3.83 x 10~5
1.11 x l O " 4
1.3IxIO- 4
6.74 x l O - 4
3.12 x l O - 3
1.93 XlO" 5
1.93 x l O - 4
1.93 x l O " 3
2.23 xlO 1 6
3.25 x 10 " 5
9.80xl0"5
3.06 x l O - 4
3.85 XlO" 7
7.21 x 10 ~5
1.320xl0" 6
9.37 x l O - 6
5.8IxIO- 5
3.24 x l O " 4
1.4xlO- 5
8.05 XlO" 5
3.56 x l O - 4
6.77 XlO" 5
6.44 x KT 5
1.07 x 10~4
7.21 x 10~5
5.97 x 10 ~5
7.8OxIO" 5
7.06 x 10 " 5
6.94 x 10 ~6
2.28 x l O " 5
9.0OxIO- 5
2.92 x l O " 4
6.03 x 10 ~5
2.62 x 1016
1.09 x 10~4
3.42 x l O - 4

E2, (kj/mol)

Notes

133.1

113.8

130.1

a
a
a
a
a
a
a
a
a
a
a
a
a
a,m2
a,m2
a
a
a

145.2

144.3

120.5
123.4
148.5

99.2

141.8

exp[- 151.59/RT\
144.3

140.2

134

a
a
m2
m2
m2

c
c
c
a,h

a
a
a

a
156.9

exp[-152.0/RT]
141.4

a
a
a
a

a
a

Refs.
36
36
36
36
36
36
36
36
56
56
126,337
126,337
126,337
56
56
56
56
56
56
56
56
56
56
56
56
56
354
56
56
22
22
22
344
344
344
344
55
55
55
81
272
345
345
345
345
337
337
337
270
270
56
270
270
56
270
53
53
53
53
270
376
56
56

Notes page 11-69; References page II - 70

TABLE 6. cont'd
Number of
C atoms
11 (cont'd)

Initiator

Solvent

terf-Butyl-AK4-bromophenylperoxy)carbamate

Toluene

tert-Butyl percarboxycyclohexane

Chlorobenzene

Cumene

12

tert-Butyl per-2-methylphenylacetate

Isooctane

tert-Butyl-N-(phenylperoxy)
carbamate

Toluene

tert-Hexyl peroxypivalate

Chlorobenzene
Cumene

1,1,2-Trimethylpropyl perpivalate

Cumene

Cumyl peracetate
tert-Amyl peroxybenzoate

Carbon tetrachloride
Toluene
Chlorobenzene

4-Bromocumyl perpropionate

Benzene

oc-Methylstyrene

tert-Butyl bicyclo[2.2.1]lheptane2-percarboxylate

terf-Butyl endo-bicyclo[2.2.1]heptane percarboxylate

Cumene

Chlorobenzene

Cumene

terf-Butylexo-bicyclo[2.2.11]heptane-2-percarboxylate

Chlorobenzene

T( 0 C)
70.8
79.8
84.0
96.0
100.1
111.4
120.0
79.6
79.6
79.6
60.6
73.9
51.2
67.7
77.7
90.7
T(K)
40
50
60
70
80
40
50
60
70
100
100
99
118
139
T (K)
70
80
90
70
80
90
85
100
110
110
120
130
94.0
101.9
109.6
120.5
94.5
101.9
111.9
100.1
111.4
120.0
94.0
101.9
109.6
120.3
94.5
101.9
111.9
94.5
101.9
112.1

A^(S"1)
3.32 x 10 " 5
1.04 x 10 ~4
1.75 x l O - 4
7.70xl0~ 4
2.75 x 10 ~4
9.65 XlO- 4
2.39 XlO- 3
1.86 x l O " 5
1.42 x l 0 ~ 5
1.15xl0- 5
6.60 x 10 ~5
3.233 x l O - 4
3.4xlO-6
2.31 x 10 " 5
1.15 x l O - 4
6.41 x 10 ~4
1.51 x 1016
2.39 x 10 ~6
8.83 x l O - 6
3.37xl0-5
1.226 x l O - 4
4.166 x l O - 4
3.6xlO" 6
1.59x10-5
5.14x10-5
1.921 x 10- 4
4.68 x 10 " 5
3.43 x 10 ~5
1.93 x 10 ~5
1.93 x 10~4
1.93 x l O - 3
8.38 x 1015
1.48 x 10 " 6
5.73 x l O - 6
1.8IxIO- 5
1.99 x 10~6
4.93 x l O - 6
1.55x10-5
1.16 x 10~6
1.02 x 10 ~5
3.76xlO- 5
4.6x10-5
1.56 XlO" 4
4.99 x l O " 4
1.75XlO" 5
6.20xl0"5
1.7 x l O - 4
5.72 x l O - 4
9.69x10-5
1.96xlO- 5
6.53x10-5
4.6IxIO-5
1.96 xlO~ 4
5.4OxIO- 4
1.87 x l O " 5
5.3OxIO- 5
1.10 x l O " 4
4.3 x l O - 4
5.27xl0-5
1.12 x l O - 4
3.57 x l O - 4
8.86 x 10 ~5
2.28 x 10 ~4
8.85 x l O - 4

Ea (kj/mol)

Notes

177.6

131.0

139.7

z (1)
z (2030)
z (4050)
ni2
m2
h

exp[- 136.0/RT]

c
p

exp[- 147.02/RTl
129.7

121.3

a
a
a
a
a

155.2
160

150.2

137.2

149.0

154.0

130.1

Refs.
36
36
36
36
181
181
181
163
163
163
165
165
36
36
36
36
40
362
362
362
362
362
362
362
362
362
271
271
344
344
344
344
213
213
213
213
213
213
160
160
223
223
223
147
147
147
147
147
182
182
181
181
181
147
147
147
147
182
182
182
182
182
182

TABLE 6.
Number of
C atoms

cont'd

Initiator

Solvent

12 (cont'd)

Cumene

tert-Butyl endo-bicyclo[2.2.1]-hept5-ene-2-percarboxylate

Cumene

tert-Butyl exo-bicyclo[2.2.1]-hept5-ene-2-percarboxylate

Chlorobenzene

Cumene

tert-Butyl 4-bromophenoxyperacetate
tert-Butyl 4-chlorophenoxyperacetate
tert-Butyl 3-chlorophenylperacetate

Ethylbenzene
Ethylbenzene
Chlorobenzene

Cumene
tert-Butyl 4-chlorophenyl peracetate

Chlorobenzene

Cumene
tert-Butylcycloheptyl percarboxylate

rc-Hexadecane
2,2,4-Trimethylpentane

tert-Butyl 2,4-dichlorophenoxyperacetate
tert-Butyl 2,2-diethyl perbutyrate

Ethylbenzene
Cumene

tert-Butyl per-2-ethylhexanoate

Benzene
Chlorobenzene

tert-Butyl 2-methoxy-2-methylperpropionate

Chlorobenzene

tert-Butyl 4-methoxyperbenzoate

Phenyl ether

tert-Butyl peroxy-2-methylbenzoate

Chlorobenzene

tert-Butyl 4-methoxyperbenzoate
tert-Butyl 4-methylperbenzoate

Carbon tetrachloride
Phenyl ether

T( 0 C)

d (s"1)

96.0
100.1
111.4
120.0
84.4
94.7
100.1
108.6
113.5
94.5
101.9
112.1
94.5
101.9
112.0
94.5
101.9
112.1
94.5
101.9
112.1
70.5
70.5
79.6
90.7
100.5
79.6
79.6
79.6
90.7
100.5
79.6
79.6
92.9
102.6
92.9
102.6
70.5

1.33 x 10"4
1.90xl0" 4
6.79 xlO" 4
1.64 xlO" 3
2.19 xlO" 5
7.29 x l 0 ~ 5
1.37 xlO~ 4
3.6 XlO" 4
6.19 XlO" 4
6.05 x l O " 5
1.53 x l O " 4
4.72 XlO" 4
3.11 x l O " 5
7.35 x 10 ~5
2.48 x l O " 4
5.59 x l O " 5
1 25 x 10" 4
5.0OxIO" 4
4.48 x l O " 5
1.18 x l O - 4
3.97 x l O " 4
2.6xlO~ 4
2.9xlO~ 4
4.05 x 10 ~5
1.44 x l O - 4
4.38 x l O " 4
2.98 x 10 " 5
1.99 x l O " 5
8.44 x 10 " 5
2.95 x l O - 4
8.19 x l O " 4
6.54 x 10 " 5
4.45 x 10 " 5
1.801 x 10 " 4
5.17 x l O " 4
1.703 x 10 " 4
5.07 x l O " 4
9.4xlO" 5

45
55
65
72
72
91
113
T(K)
-14.0
-7.0
-1.0
15.0
100.0
110.1
120.2
130.9
96
115
136
T (K)
80
100.0
110.1
120.2

1.23 x 10 " 5
4.92 x l O " 5
1.46 x l O - 4
1.9xlO" 5
1.93 x 10 ~5
1.93 x l O " 4
1.93xl0- 3
1.54 xlO 1 4
2.05 x 10 " 5
6.73 x 10" 5
1.67 XlO" 4
1.28 XlO" 3
1.07 x 10 " 5
4.17 x l O " 5
1.28 x l O - 4
4.28 x l O " 4
1.93 x 10 " 5
1.93 x 10 " 4
1.93 x l O " 3
8.56 x 1015
l.OxlO" 6
9.42 x 10 " 6
3.19 XlO" 5
1.06 XlO" 4

Ea (kj/mol)

Notes

129.3

129.3

131.4

136.4

138.1

123.0

a
a
h

117.2

z (0.98)
z (6090)
h

121.5

z (0.98)
z (6090)
h

125.7

h
a

100.3

exp[- 124.90/RT]
86.3

149.8

m2
m2
m2
m2
a
a
a
a

expr[- 145.97/RT]
151.0

a
a
a

Refs.
147
181
181
181
147
147
147
147
147
182
182
182
182
182
182
182
182
182
182
182
182
315
315
178
178
178
207
207
178
178
178
207
207
255
255
255
255
315
160
160
160
338
344
344
344
344
275
275
275
275
53
53
53
53
344
344
344
344
354
53
53
53

Notes page 11-69; References page II - 70

TABLE 6. cont'd
Number of
C atoms
12 {cont'd)

Initiator
terr-Butyl 4-methylperbenzoate
rm-Butyl 2-methyl-2-terfbutylperoxyperpropionate

Solvent
Phenyl ether
Benzene

terf-Butyl 2-methylsulfonyl
perbenzoate

Chlorobenzene

tert-Butyl 2-(methylthio)perbenzoate

Chlorobenzene

tert-Butyl 4-(methylthio)perbenzoate
terf-Butyl 4-nitrophenoxyperacetate
/m-Butyl 4-nitrophenylperacetate

Chlorobenzene
Ethylbenzene
Chlorobenzene

terf-Butyl 4-nitrophenylperacetate

Decane
Dodecane
Hexadecane
Octane

Di-terf-butyl per-2-chlorosuccinoate

Tetradecane
Unknown

T( 0 C)
130.9
9.0
19.0
30.0
42.0
105
120
135
150.6
60
39.4
50.1
50.2
69.8
120.4
70.5
79.6
90.7
100.5
80
77.5
77.5
100
77.5
77.5
100
77.5
105
115
125

tert-Butyl peroctoate

Benzene

Decane

Di-rm-butyl persuccinoate

Styrene

/m-Butyl phenoxyperacetate
rm-Butyl phenylperacetate

Ethylbenzene
Chlorobenzene

Cumene

Decane
Dodecane
Hexadecane
Isooctane

70
85
100
70
85
100
105
115
125
70.5
60
77.0
88.6
79.6
90.7
100.5
79.6
79.6
79.6
79.6
85.0
79.6
79.6
79.6
79.6
79.61
77.5
77.5
77.5
85.0
95.2

^d(S"1)
3.25 x 10~A
6.66 xlO~ 5
1.99 x 10 ~4
6.94 xlO~ 4
2.43 x l 0 ~ 3
6.68 x 10 ~6
5.57 x 10~5
2.76 xlO~ 4
2.05 x l 0 ~ 3
8.08 x 10~A
2.59 x l O - 5
2.42 XlO- 4
1.88 x l O - 4
1.96 XlO" 3
1.75 x 10 ~4
6.7xlO" 5
2.5xlO" 5
8.9 XlO" 5
2.83 xlO~ 4
3.77 XlO" 5
6.3OxIO- 6
5.8IxIO" 6
1.3IxIO- 4
5.11 x 10" 6
6.42 x 10 " 6
1.6OxIO- 4
5.56 x 10 " 6
2.74 x 10 " 4
1.22 x l O - 5
5.9OxIO" 4
3.83 x l O - 5
1.52 XlO" 3
1.00 x l O - 4
1.4xlO" 5
8.55 x l O - 5
4.55 x l O - 4
6.9xlO~ 6
4.39 x l O - 5
2.64 x l O - 4
1.93 x 10 " 5
6.7 x l O - 5
2.53 XlO" 4
4.4xlO" 4
6.79 x 10~6
6.85 x l O - 5
2.45 x l O - 4
1.05 x l O - 4
3.53 XlO" 4
1.003 XlO" 3
1.07 x l O - 4
9.1 x 10 " 5
1.02 XlO" 4
9.0 x 10- 4
1.945 XlO" 4
6.6xlO- 5
5.6 xlO~ 5
6.78 x l O - 5
4.73 x l O - 5
1.1 x l 0 ~ 5
3.0OxIO- 5
2.75 x l 0 ~ 5
2.6OxIO- 5
1.08 x l O " 4
3.527 x l O - 4

E2, (kj/mol)

Notes

78.8

a
m2

95.0

a,h
b
c
m2

129.9
124.7

a,h
h

102.9
143.5

X2
X2
X2
x2
X2
x2
a
a
a
a
a
a
Xi
X1
X1
a,h
a,h
h
m2
h

130

130

154.8

113.1
120.1
117.6
116.7

z (0.98)
z (4050)
z (0.98)
z (4050)
m2
z (0.98)
z (4050)
z (0.98)
z (6090)

Refs.
53
275
275
275
275
22
22
22
22
97
134
134
134
134
134
315
178
178
178
169
168
168
168
168
168
168
168
214
214
214
214
214
214
337
337
337
337
337
337
215
215
215
315
81
28
28
178
178
178
157
157
163
163
165
157
157
163,207
163,207
274
168
168
168
165
165

TABLE 6. cont'd
Number of
C atoms
12 (cont'd)

Initiator
tert-Butyl phenylperacetate

tert-Buty\ 2-propylperpenten-2-oate
(cw)

(trans)

Solvent
Octane
Paraffin oil
Tetradecane
Cumene

Cumene

tert-Butyl 2,2,3,3-tetramethylperpropionate

Cumene

tert-Butyl thiophenylperacetate
tert-Butyl per-o-toluate
ferf-Butyl per-paratoluate

Ethylbenzene
Benzene
Cumene

tert-Butyl-AH3-tolylperoxy)carbamate

Toluene

tert-Butyl 2,4,5-trichlorophenoxyperacetate
4-Chlorocumyl perpropionate

Ethylbenzene
Benzene

a-Methylstyrene

Cumyl perpropionate

Benzene

a-Methylstyrene

4-Iodocumyl perpropionate

Benzene

a-Methylstyrene

4-Nitrocumyl perpropionate

Benzene

a-Methylstyrene

13

1,1,3-Trimethylbutyl perpivalate

Cumene

tert-Amyl per-2-ethylhexanoate

Benzene
Chlorobenzene

Benzyl(ter?-butylperoxy)oxalate

Benzene

T( 0 C)
77.5
85.0
77.3
94.9
100.1
100.1
100.1
110.1
94.9
100.1
100.1
100.1
110.1
42.2
54.9
70.3
70.5
97
84.0
99.3
115.0
64.0
70.7
78.0
88.5
70.5
70
80
90
70
80
90
70
80
90
70
80
90
70
80
90
70
80
90
70
80
90
70
80
90
40
50
60
70
70
73
91
111
T(K)
45
55
65

A^(S"1)
3.1IxIO"5
1.150 x 10~4
2.66 x 10 ~5
2.78 x 10 ~5
5.4 XlO" 5
4.26 x l 0 ~ 5
2.31 x 10~5
1.72 x l O - 4
2.47 x 10 ~5
4.7 x l O - 5
3.13 x l O - 5
1.42 x-K) - 5
1.64 x l O - 4
8.76 x l O " 6
5.84 x 10 ~5
3.36 x l O - 4
3.8 x 10 ~4
1.9xl0"5
1.660 x 10 ~6
1.139 x l O - 5
6.77 XlO" 5
4.58 x 10 " 5
9.17 x l O " 5
2.03 x l O - 4
5.78 x l O - 4
5.8 x l O " 5
1.46 x 10 " 6
5.68 x l O - 6
1.79 x l O " 5
1.50x 10" 6
4.54 x l O - 6
1.47 x l O - 5
2.6OxIO- 6
6.15 x l O - 6
1.90 x l O " 5
6.31 x 10 ~6
1.7IxIO- 5
4.94 x l O " 5
1.37 x 10~6
5.76 x l O - 6
1.79 x l O - 5
1.54 x 10~6
4.96 x l O - 6
1.62 x l O - 5
1.36 x 10 " 6
5.32 x l O " 6
1.78 x l O - 5
1.35 x 10~6
4.07 x l O - 6
1.43 x l O - 5
4.8OxIO- 6
1.77 x l O - 5
6.18 x l O " 5
2.344 x l O - 4
1.9xl0-5
1.93 x 10 ~5
1.93 x l O - 4
1.93 x l O - 3
1.77 x l O 1 5
3.65 x 10 " 5
1.33 x l O - 4
4.69 x l O - 4

Ea (kj/mol)

Notes

137.2

h
z (0.98)
z (1100)
z (4000)

143.9

h
z (0.98)
z(llOO)
z (3830)

114

a
a

102.9

a
129.3

118.8

101.7

106.7

133.1

125.5

133.5

124.7

a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a

exp[- 132.1 l/RT]


111.3

c,h
c
c

Refs.
168
165
168
172
172
172
172
172
172
172
172
172
172
267
267
267
315
338
345
345
345
36
36
36
36
315
213
213
213
213
213
213
213
213
213
213
213
213
213
213
213
213
213
213
213
213
213
213
213
213
362
362
362
362
338
344
344
344
344
31
31
31

Notes page 11-69; References page 11-70

TABLE 6. cont'd
Number of
C atoms
13 (cont'd)

Initiator

Solvent

tert-Butyl benzyloxyperacetate

Ethylbenzene

tert-Butyl benzylthioperacetate

Ethylbenzene

tert-Butyl bicyclo[2.2.2]octane1-percarboxylate

Cumene

ter/-Butyl endo-bicyclo[2.2.1j-2methylheptane-2-percarboxylate

Cumene

tert-Butyl exo-bicyclo[2.2.1]2-methylheptane-2-percarboxylate

Cumene

tert-Butyl 1,4-dimethylcyclohexane1-percarboxylate (cis)

Cumene

(trans)

Cumene

tert-Butyl 3-methoxyphenylperacetate

Chlorobenzene

terf-Butyl 4- methoxyphenylperacetate

Chlorobenzene

Cumene

tert-Butyl 4-methylphenyl peracetate

Decane
Dodecane
Ethylbenzene
Isooctane
Octane
Paraffin oil
Tetradecane
Chlorobenzene

Cumene

Di-terr-butyl perglutarate

terf-Butylperoxy 2-ethylhexylcarbonate

Decane
Dodecane
Ethylbenzene
Hexadecane
Octane
Tetradecane
Styrene

Chlorobenzene

T( 0 C)
40.0
40.0
51.0
60.7
40.0
60.0
70.0
65
75
85
80
90
100
75
80
85
90
95
60
65
70
75
80
60.0
70.0
80.0
60.0
70.0
80.0
79.6
90.7
100.5
56.0
60.3
70.2
79.3
48.9
60
60
79.6
77.5
77.5
70.5
60.5
77.5
60.5
77.5
70.4
79.6
90.7
79.6
79.6
77.5
77.5
70.5
77.5
77.5
77.5
105
115
125
99
117
137

A:d (s"1)
1.3 x 10" 4
1.45 x l O - 4
5.03 XlO" 4
1.62 x l O - 3
2.60xl0~~5
3.31 x 10- 4
1.14 XlO" 3
7.5 x 10 ~6
2.82 x l O " 5
8.47 x l O " 5
5.IxIO"5
1.67 x l O - 4
4.86 XlO" 4
7.35 x 10 ~5
1.39 x 10 " 4
2.64 x l O - 4
4.81 x 10 " 4
8.41 x 10- 4
7.78 x 10 " 5
1.44 x 10 " 4
2.75 x l O " 4
4.89 XlO" 4
8.93 XlO" 4
7.52 x l O " 5
2.66 x 10 " 4
8.49 xlO~ 4
6.93 x 10 ~5
2.52 x l O " 4
7.79 x l 0 ~ 4
9.9xl0~5
3.45 x 10 ~4
1.051 x 10" 3
4.57 x 10 ~5
9.9xlO~ 5
3.06 x l O " 4
7.99 xlO~ 4
1.93 XlO" 5
6.85 x 10 ~5
5.31 x 10 ~5
5.942 x l O - 4
2.52 x 10 ~4
2.60xl0~ 4
1.4xlO~ 3
4.72 x 10 ~5
2.53 x 10 ~4
4.20 x l 0 ~ 5
2.68 x 10 ~4
8.67 x 10 ~5
2.37 xlO~ 4
7.95 xlO~ 4
1.649 x 10 ~4
1.180xl0~ 4
9.08 x 10 ~5
8.57 x l 0 ~ 5
7.2xlO~ 4
1.032 x 10 ~4
8.83 x 10 ~5
7.75 x 10 ~5
2.65 x 10 ~5
1.06 xlO~ 4
3.0OxIO- 4
1.93 x 10 ~5
1.93 x 10 ~4
1.93 x l 0 ~ 3

Ea (kj/mol)

Notes

100.6
101.8

a,h
h,m2

108.1

h,m2

119.2

120.1

126.8

116.7

115.2

c
h

116.3

c
c,h
c

122.2

105.4

k
z (0.98)
z (4050)

Refs.
315
328
328
328
328
328
328
160
160
160
223
223
223
206
206
206
206
206
206
206
206
206
206
206
206
206
206
206
206
178
178
178
178
178
178
178
249
207
207

207

104.8

a,h

110.9

z (0.98)
z (6080)

Xi
X1

168
168
315
169
168
169
168
178
178
178
207
207
168
168
315
168
168
168
215
215
215
344
344
344

TABLE 6.

cont'd

Number of
C atoms
13 (cont'd)

14

Initiator
terf-Butylperoxy 2-ethylhexylcarbonate
terr-Butyl 2-phenylperpropionate

Solvent

T(K)

4.07 xlO 1 6

Cumene

40.7
60.1
80.1
40.8
54.7
70.7
40.0
95
114
135
T(K)
45
55
65
95
113
134
T (K)
54.7
70.2
85.4
70.8
85.4
101.0
40.0

7.88 x 10 " 6
8.44 x l O - 5
8.1OxIO- 4
6.15 x 10~6
3.82 x 10 ~5
2.73xlO- 4
2.62 x 10 " 5
1.93 x 10 " 5
1.93XlO" 4
1.93 x l O - 3
1.94 xlO 1 5
1.3OxIO" 5
4.89 x 10 " 5
1.89 x l O - 4
1.93 x 10 ~5
1.93 x l O " 4
1.93 x l O " 3
2.22 x 1016
4.38 x 1O -6
3.56 x l O - 5
2.44 x l O - 4
1.48 x 10 " 5
8.07 x 10" 5
4.38 x l O " 4
7.2xlO-4

50.0
50.0
50.0
60.0
67.0
50.0
60.0
67.0
50.0
60.0
67.0
99.6
109.8
99.6
109.8
34.1
39.7
47
46
64
84
T (K)
50.0
50.0
50.0
60.0
67.0
67.0
84.0
99.3
115.0
113.0
120.0
130.0
140.0

2.55 x 10 " 4
2.03 x 10 " 4
7.98 x 10~5
2.68 x l O - 4
6.36 x l O - 4
8.0OxIO- 5
2.56 x l O " 4
5.96 x l O - 4
8.1OxIO- 5
2.65 x l O - 4
5.95 x l O " 4
1.23 x 10 " 4
3.7OxIO- 4
3.5 x 10~5
1.03 x l O - 4
3.26 x 10 ~5
5.63 x 10" 5
1.9xlO- 5
1.93 x 10 " 5
1.93 x l O " 4
1.93 x l O " 3
1.52 x 1014
7.5OxIO- 5
6.4OxIO" 5
2.63 x 10- 5
9.27 x l O - 5
2.03 x l O " 4
1.98 x 10 - 4
1.464 x 10 " 5
9.94 XlO" 5
6.7 x l O - 5
8.67 x l O " 5
2.49 x 10 ~4
7.49 x l O " 4
2.22 x l O - 3

Cumene

terf-Butylthiobenzylperacetate
tert-Butyl peroxy-3,5,5-trimethylhexanoate

Ethylbenzene
Chlorobenzene

4-Nitrobenzyl(terf-butylperoxy)oxalate

Benzene

2-ethylhexyl-

Chlorobenzene

tert-Butyl di-terf-butylperacetate

Cumene

terf-Butyl 2-carbomethoxyphenylperacetate

Cumene

terf-Butyl 2-(4-chlorophenoxy)2-methylperpropionate
tert-Butyl 2-(4-chlorophenyl)2-methylperpropionate

Ethylbenzene
Acetonitrile
Benzene
Dodecane

Hexadecane

Octane

tert-Butyl a-methylpercinnamate
(cis)
(trans)

kd (s'1)

Chlorobenzene

tert-Butyl 2,2,4,4-tetramethylperbutyrate

terf-Amylperoxy
carbonate

T(0C)

Cumene
Cumene

tert-Butyl 2-methyl-2-phenylperpropionate
tert-Butyl perneodecanoate

Chlorobenzene
Cumene
Benzene
Chlorobenzene

tert-Butyl 2-(4-nitrophenyl)2-methylperpropionate

Acetonitrile
Benzene
Dodecane

tert-Butyl permesitoate

Octane
Cumene

tert-Butyl 1-phenylcyclopropylpercarboxylate

rc-Dodecane
Ethylbenzene

Ea (kj/mol)

Notes

exp[-151.72/RT]

344

111

100.6

a,h

exp[- 140.78/K7]
116.7

c,h
c
c

exp[- 148.41/#7]
125.3

116.9

108.1

128.0

f,h
f
f,h
f

125.5

exp[- 115 A7/RT]


105.2

147.5

Refs.

h,t i
ti
ti

273
273
273
267
267
267
315
344
344
344
344
31
31
31
344
344
344
344
245
245
245
257
257
257
315
265
265
265
265
265
265
265
265
265
265
265
150
150
150
150
249
249
338
344
344
344
344
265
265
265
265
265
265
345
345
345
255
323
323
323

Notes page 11-69; References page 11-70

TABLE 6. cont'd
Number of
C atoms
14 (cont'd)

Initiator
tert-Butyl 1-phenylcyclopropylpercarboxylate

Solvent
2,2,4-Trimethyl pentane

tert-Butyl phenyldimethylperacetate

Chlorobenzene
Isooctane

tert-Butyl 2-phenyl-3-perbutenoate
tert-Butyl 4-phenyl-3-perbutenoate
tert-Butyl 2-phenyl-2-methylperpropionate

Chlorohenzene
Chlorobenzene
Acetonitrile
Benzene
Benzophenone
Benzyl benzoate
Butyl phthalate
Chlorobenzene
Cumene
Dodecane

tert-Butyl 4-vinylphenylperacetate

Hexadecane
Methyl benzoate
Octyl phthalate
Toluene
Cumene

Dibenzyl peroxalate
Di-tert-butyl adipate

Pentane
Styrene

Dicyclohexyl peroxydicarbonate

Benzene
Chlorobenzene

a-Methylstyrene
Mineral spirits

15

4-Methoxybenzyl (tert-butylperoxy)oxalate

Benzene

1-Methyl-1-phenylethyl 2,2-dimethylperoxyporpionate

Cumene

tert-Amy\ perneodecanoate

Benzene
Chlorobenzene

Dibenzoyl monopercarbonate
tert-Butyl 1-adamantylpercarboxylate

Benzene
Cumene

T( 0 C)
102.6
113.0
120.4
60
40.6
60.6
60.6
60
60
50.0
50.0
60
60
60
60
60
50.0
60.0
67.0
60
60
60
60
60
70.9
85.4
100.3
25
105
115
125
50
44
60
77
T (K)
50
45
50
60
45
55
65
40
50
60
70
45
43
61
81
T (K)
60.00
45
55
65
64.6
74.6
84.6
60
70
80

^d(S" 1 )
2.53 x 10 ~5
8.96 x 10 ~5
2.04 xlO~ 4
9.6xlO~ 4
2.95 x 10 ~5
3.059 xlO~ 4
4.064 xlO~ 4
2.9xlO~ 3
1.15 x 10 ~4
3.08 x 10 " 4
2.18 xlO~ 4
7.73 x 10 ~A
7.92 x 10 ~4
6.5 x 10 ~4
7.00xl0~ 4
5.25 x 10 ~4
8.77 x 10 ~5
3.00xl0~ 4
7.13 xlO~ 4
2.88 xlO~ 4
3.53 x 10 ~4
7.55 x 10 ~4
5.70xl0~ 4
5.66 x 10 ~4
5.54 x 10 " 5
3.00xl0~ 4
1.48 x l 0 ~ 3
6.7 x 10 ~5
3.50xl0~ 5
1.23 xlO~ 4
3.05 xlO~ 4
5.4xlO~ 5
1.93 x 10 ~5
1.93 x l 0 ~ 4
1.93 x l 0 ~ 3
3.3 x 1016
5.9xlO~ 5
2.78 x 10 ~5
5.58 xlO~ 4
2.07 xlO~ 4
6.69 x 10 ~5
2.48 x 10 ~A
8.27 xlO~ 4
6.91 x 10 ~6
2.80 x 10 ~5
1.032 xlO~ 4
3.57 x l O - 4
1.9xl0~ 5
1.93 x 10 ~5
1.93 xlO~ 4
1.93 x l O - 3
1.47 x 1014
8.05 x 10 ~5
5.15 x 10 ~5
2.05 x 10 ~5
7.4OxIO- 5
6.87xl0-5
2.44 xlO~ 4
7.78 x l O - 4
5.4 x l O - 5
2.12 x l O - 4
7.20xl0~ 4

Ea (kj/mol)

Notes

141.2

109.2

96.2
98.3

c,h
t9
t9
m2
c,h
c,h,g

109.3

t 12

116.5

h,k
k

151.0

X2
X1
X1
c

exp[- 129.0/RT]
117

109.6

a
a
a
c,h
c
c

exp[- 114.38/K7]
116.5
115.5

h
h

116.7

124.7

Refs.
255
255
255
81
165
165
165
81
81
265
265
334
334
334
334
334
265
265
265
334
334
334
334
334
254
254
254
203
215
215
215
201
344
344
344
344
201
337
337
337
31
31
31
368
368
368
368
338
344
344
344
344
280
160
160
160
159
159
159
223
223
223

TABLE 6.
Number of
C atoms
15 (cont'd)

cont'd

Initiator
tert-Butyl 4-(carboethoxy)phenoxyperacetate
tert-Butyl a,p-dimethylpercinnamate (cis)

Solvent
Ethylbenzene

(trans)

tert-Butyl 1-pernaphthoate
tert-Butyl 2,2-dimethyl3-phenylthio perpropionate

Chlorobenzene
Cyclohexane

tert-Butyl 2-(4-methoxyphenyl)2-methylperpropionate

Acetonitrile
Benzene
Dodecane

tert-Butyl 1-phenylcyclo-n-Dodecane
butylpercarboxylate

tert-Butyl 4-tert-butylperbenzoate

Chlorobenzene

Di-tert-butyl perpimelate

Styrene

tert-Butyl 2-(4-tolyl)2-methylperpropionate

Acetonitrile
Benzene
Dodecane

tert-Butyl triisopropylperacetate

16

Octane
52.3
Ethylbenzene
n-Hexadecane
2,2,4-trimethyl pentane

Octane
Cumene

l,l-Dimethyl-2-phenylethylperpivalate

Cumene

1-Phenylethyl 4-methoxyperacetate
1-Phenylethyl 3-nitroperbenzoate
1-Phenylethyl 4-nitroperbenzoate
1-Phenylethyl perbenzoate
Dibenzyl peroxydicarbonate

Benzene
Benzene
Benzene
Benzene
Benzene

Di-tert-butyl2-iodoperisophthalate

Chlorobenzene

Di-tert-butyl perphthalate

Benzene

Di-n-butyl phthalate

Chlorobenzene

T( 0 C)
70.5
95.0
103.2
110.1
85.1
95.0
103.7
110.0
110.0
110.1
55
65
75
50
50
40
50
57
50
7.89 x 10 ~5
60.0
52.3
52.3
61.6
100.1
119.8
135.9
105
115
125
50.0
50.0
50.0
60.0
67.0
60.0
24.8
41.6
55.2
40
50
60
70
99.7
100
100
100
40
50
60
68.4
85.4
101.6
100
115
130
100
115
130
107
125
146
T(K)

A^(S"1)

Ea (kj/mol)

1.6xlO~ 4
1.02 xlO~ 4
2.29 x 10 ~4
5.15xlO- 4
3.9xl0~5
1.17xlO- 4
2.84xlO~4
6.05xl0-4
7.9OxIO- 4
8.69 x l 0 ~ 5
1.63 x 10 ~5
1.61 x 10 ~5
1.98xlO- 4
1.675 x 10 ~3
9.96 x 10 ~A
1.49 x l O " 4
4.21 x IO- 4
1.028 XlO" 3
4.18 xlO~ 4
3.62 x 10 " 4
8.80xl0~ 5
7.69 x 10 ~5
2.46x10-4
3.81 x 10 ~5
4.5OxIO- 4
2.38 x l 0 ~ 3
4.45 x 10 ~5
1.05x10-4
5.06x10-4
6.0OxIO" 4
3.85 x 10 " 4
1.9OxIO- 4
5.58 xlO~ 4
1.32OxlO" 3
5.43 x 10 " 4
5.32 x 10~6
6.84 x l O - 5
3.78 XlO" 4
4.56 x 10~6
1.833 x 10~5
6.1 x 10 ~5
2.5IxIO-4
3.50xl0"4
5.97 x 10 ~4
4.10xl0~4
4.03 x 10 ~4
2.0xl0"5
6.25 x l O - 5
2.67 x l O - 4
8.24 x 10~5
4.45 x l O - 4
1.68 x l O " 3
1.1 x 10 ~5
7.8IxIO-5
4.8IxIO"4
1.08 x 10 " 5
7.8 x l O " 5
4.8 XlO" 4
1.93 x 10 ~5
1.93 x l O - 4
1.93 x l O - 3
9.39 xlO 1 6

118.8

122.6

116.9

Notes
a

315

a,h
a
a
a,h
a
a
a
a,v6

151
151
151
151
151
151
151
151
154
320
320
320
265
265
265
265
265
265

h,t6
t6

93.0

255
ti
110.6

150.6

Xi
X1
X1

100.6

111.5

134.1
136.2
146.2
123.6
117

h
h
h
h
a
a
a
h

93.9

159

155.0

exp[-157.85/^7]

Refs.

a
a
a
h

323
255
255
255
134
134
134
215
215
215
265
265
265
265
265
265
267
267
267
362
362
362
362
259
259
259
259
337
337
337
248
248
248
337
337
337
269
269
269
344
344
344
344

Notes page 11-69; References page 11-70

TABLE 6. cont'd
Number of
C atoms
16 (cont'd)

Initiator
Di-tert-butyl perphthalate

Cumene

terr-Butyl 1-phenyl-l-cyclopentane percarboxylate


terf-Butyl 2,3-dimethyl2-phenylperbutyrate
Cumyl 7V-phenylperoxy carbamate
Dibenzyl peroxydicarbonate
Di-terr-butyl perphthalate

Di-tert-bxxty\ persuberate

17

Solvent

^d(S1)
6

Ethylbenzene

99.9
115.0
130.1
60.0

8.34 x 10"
4.68 XlO- 5
2.6OxIO- 4
1.52 x 10 ~3

Ethylbenzene

50

4.3OxIO- 5

T(K)
50
100
115
130
115
125
43.5
52.3
60
70
80
10
35
10
10
100

1.26 x l O 1 4
2.92 x 10 " 5
1.08 x 10 " 5
7.83 x l O - 5
4.8OxIO- 4
7.86 x 10 ~5
2.8IxIO-4
1.184 x l O " 4
3.51 x 10 ~4
1.9xlO~ 5
5.3OxIO- 5
1.38 x l O " 4
4.5 x 10~4
1.9 x l O - 3
6.4X10" 4
5.IxIO"4
2.16 x l O " 3

79.6
70.6
80.3
100.5
60.0
43.5
52.3
61.6
25
40
25
40
25
40
39.3
53.8
53.8
70.0
25
40
25
40
25
40
25
40
25
40
25
40
105
119.4
135.1
105
115
125
98
116
137
T (K)

2.38 x 10 " 5
9.44 x 10 ~6
2.8OxIO- 5
3.09 x l O - 4
1.9OxIO- 3
1.27 x 10 ~4
3.91 x 10 ~4
1.218 x l O - 3
1.89 x 10 ~5
1.22 x l O - 4
1.01 x 10 ~4
5.44 XlO" 4
5.26 x 10~5
3.24 x l O - 4
4.98 x 10 ~5
5.23 x l O ~ 4
4.58 x l O - 4
2.62 x l O " 3
1.76 XlO" 5
1.03 x l O - 4
9.8X10" 7
6.9 x l O - 6
1.11 x l O ~ 4
6.02 x 10 " 4
2.31 x 10~4
1.65 x l O " 3
1.33 x 10" 4
7.25 XlO" 4
8.21 x 10~4
4.75 x l O " 3
2.79 x 10 ~5
1.29 x 10 " 4
6.07 x l O - 4
5.13 x 10~5
1.2OxIO- 4
5.1OxIO- 4
1.93 x 10 ~5
1.93 x l O - 4
1.93 x l O - 3
1.35 x 10 16

Xylene
Toluene
Benzene

Styrene

tert-Butyl 1-phenylcyclopentylpercarboxylate
1,1,3,3-Tetramethylbutylper-2-ethylhexanoate

2,2,4-Trimethylpentane
Benzene

2-Phenylazo-2-propylperbenzoate

Chlorobenzene

1-Phenylethyl 4-dimethylaminoperbenzoate
Di-terf-butylperhomoterephthalate

J( 0 C)

/7-Chlorotoluene
Chloroform-di
Benzene
Cumene
Toluene

tert-Butyl 1-phenylcyclohexanepercarboxylate

Ethylbenzene
2,2,4-Trimethylpentane

tert-Butyl 2-(phenylthio)perbenzoate

Acetone
Acetonitrile
terf-Butanol
Chlorobenzene

Cyclohexane
DMSO
Ethanol
Isopropanol
Methanol
terf-Butyldibenzothiophene-4-percarboxylate

Chlorobenzene

Di-tert-butyl perazelate

Styrene

Chlorobenzene

E* (kj/mol)

Notes

140.8

ti

Refs.
269
269
269
323
324

exp[- U1.6/RT]
157.7

159.0
103.5

a
a
a
a
Xi
Xi
h

101

a
a
a

111.5

122.3

107.7

m2
ITi2
m2
m2
m2
m2
b
m2

128.0

154.8

exp[- 141.95/RT]

m2
m2
m2
m2
m2
m2
m2
m2
m2
m2
m2
m2
h

40
90
126
126
126
215
215
255
255
337
337
337
260
260
260
260
259
272
272
272
272
323
255
255
255
22
22
22
22
22
22
134
134
134
134
22
22
22
22
22
22
22
22
22
22
22
22
22
22
22
215
215
215
344
344
344
344

TABLE 6. cont'd
Number of
C atoms
18

Initiator
tert-Butyl 4-benzoylperbenzoate
terf-Butyl diphenylperacetate

2,4,4-Trimethylpentyl2-perneodecanoate

a,co-Di-0,O-ter?-butyl-(bispersuccinyl)ethylene glycol

tert-Buty\ 1-phenyl-l-cycloheptanepercarboxylate
Di-tert-buty\ /?-phenylenediperacetate

tert-Buty\ 2-(phenylthiomethyl)perbenzoate
tert-Buty\ thioxanthone-4-percarboxylate
Di-tert-butyl persebacate

Di-(2-ethylhexyl)peroxydicarbonate

Solvent
Benzene
Chlorobenzene
Chlorobenzene
Cumene

Decane
Dodecane
Hexadecane
Octane
tetradecane
Chlorobenzene

Ethylbenzene

Ethylbenzene
Cumene

Chlorobenzene
Chlorobenzene
Styrene

Benzene
Chlorobenzene

Decane

Mineral spirits

19

Di--heptyl persuccinate

Styrene

tert-BxAy\ diphenylmethylperacetate
terr-Butyl diphenylperglycidate
(cis)

Chlorobenzene
Cumene

(trans)

tert-Buty\ 2,2-diphenylperpropionate
tert-Butyl 4-hydroxy-3,5-di(tert-butyl)perbenzoate
tert-Butyl 4-(4-methylbenzoyl)perbenzoate

Cumene

Chlorobenzene
Benzene
Carbon tetrachloride
Benzene
Chlorobenzene

T( 0 C)

kd (s"1)

Ea (kj/mol)

25
110
60
40.3
49.6
59.9
70.4
77.5
77.5
77.5
77.5
77.5
40
57
76
T (K)

1.84 x 10 ~4
2.88 x 10 ~5
4.44 x 10 ~4
2.75 x 10 " 5
9.81xl0"5
3.10xl0"4
1.04 XlO- 3
1.66 x l O " 3
1.688 x l O " 3
1.632 x 10~3
1.651 x 10" 3
1.627 x 10 ~3
1.93 x 10 ~5
1.93 x 10 " 4
1.93 XlO" 3
3.97 x 1014

95
105
115

2.68 x 10 " 6
9.10xl0"6
2.97 XlO" 5

60.0

2.75 x 10 ~3

70.9
85.4
100.3
98.7
120.1
120
135
105
115
125

3.69 x 10 ~5
2.08 XlO" 4
8.83 x l O " 4
4.64 x 10 " 5
4.2OxIO" 4
1.89 x 10 " 4
1.15 x l O " 3
5.10xl0~ 5
1.2Ox 10" 4
5.0OxIO" 4

40
47
64
83
T (K)
30
45
60
40
50
60
60
73.5
85

1.9xlO~ 5
1.93 x 10 " 5
1.93 XlO" 4
1.93 XlO" 3
1.83 x 1015
5.3xl0"6
3.31xl0~ 5
2.32 XlO- 4
1.3xl0" 5
6.14 xlO" 5
2.3IxIO- 4
6.IxIO"" 6
3.85xl0- 5
1.70 XlO" 4

60
60.0
70.0
80.0
60.0
70.0
80.0
34.1
100
100
25
110

1.9xl0" 3
2.8xl0"5
5.5 x l 0 ~ 5
1.68 x l O " 4
1.6 x l O " 5
3.9 XlO" 5
1.20 XlO" 4
7.76 x 10 ~5
3.18 x
3.60 x
1.45 x
3.03 x

10 ~5
10 ~5
10 " 4
10 ~5

Notes
p2

101.7
104.6

a,h
h

exp[- 115.19/RT\
147.5

Refs.
279
279
81
136
136
136
136
168
168
168
168
168
344
344
344
344
306
306
306
323

112.7

134.7
156.5
154.8

h,k
k
k
h
h,m2
m2
Xi
Xi
Xi
a

exp[- 122.45//?7]
105

126

131.0

a
a
a
a
a
a
Xi
X1
X1

103.3
112.1

a,h
h

117.2

c,e
c,e
p2

254
254
254
154
154
22
22
215
215
215
338
344
344
344
344
337
337
337
337
337
337
215
215
215
81
204
204
204
204
204
204
249
246
246
279
279

Notes page 11-69; References page 11-70

TABLE 6. cont'd
Number of
C atoms
19 (cont'd)

20

21

22

23

Initiator
ten-Butyl a-phenylpercinnamate
(cw)
(trans)

Cumene
Cumene

Cumyl perneodecanoate

Benzene
Chlorobenzene

Di-rc-heptyl peradipate

Styrene

tert-Butyl 2-carbobenzoxyphenylperacetate

Cumene

tert-Butyl 2-methyl-2-phenylperhexanoate
oc,co-Di-0,O-tert-butyl-(bispersuccinyl)diethylene glycol

Ethylbenzene
Ethylbenzene

tert-Butyl
8-(phenylthio)1-pernaphthoate

Chlorobenzene

tert-Butyl 4-(2,4,6-trimethylbenzoyl)perbenzoate
tert-Butyl
2,2-diphenyl3,3-dimethylperbutanoate

Benzene
Chlorobenzene
Toluene (?)

Di-tert-butyl 2-thiophenylperisophthalate

Chlorobenzene

2,5-Dimethylhexyl
2,5-di(peroxybenzoate)

Benzene

Di-(4-tert-butylcyclohexyl)peroxydicarbonate

Chlorobenzene

tert-Butyl 2,6-di(phenylthio)perbenzoate
tert-Butylperoxy stearyl carbonate

Chlorobenzene

tert-Butyl 2,4,6-tri-tert-butylperbenzoate

24

Solvent

tert-Butyl

triphenylperacetate

Chlorobenzene

Cumene

Chlorobenzene
Cumene

Di-tert-butyl 2,3-diphenylpersuccinate

Cumene

Di-rc-heptyl persebacate

Styrene

2,5-Dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane

Benzene

Chlorobenzene

T( 0 C)

A:d (s"1)

Ea (kj/mol)

Notes

136.8

133.9

99.6
109.8
99.6
109.8
39
39
56
75
T(K)
60
73.5
85
71.0
85.4
102.4
50

1.52 x 10~4
4.4IxIO"4
8.2 x 10~5
2.59 x 10 ~4
1.9xl0~ 5
1.93 x 10 " 5
1.93 xlO~ 4
1.93 x l 0 ~ 3
3.12 xlO 1 4
1.02 x 10 ~5
6.57 x l O " 5
2.98 x l O - 4
8.84 x 10" 6
5.46 x 10 ~5
4.23 x l O - 4
5.01 x 10 " 5

95
105
115
50
70
70
80
25
110
30
39.7
50
12.1
25.0
40.0
100
115
130
48
64
82
T (K)
40.1

2.34 x 10 ~6
155.0
8.88 x 10 ~6
3.27 x l O - 5
3.83 x 10 ~5
99.2
3.44 x 10~4
3.12 x l O " 4
9.82 x l O - 4
1.34 x 10 ~4
1.8OxIO- 5
2.76 x 10 ~5
114.8
1.15 x 10 ~4
5.45 x l O - 4
1.68 x l O " 4
73.7
6.45 x 10 ~4
3.09 x l O - 3
1.87 x l 0 ~ 5
154.0
1.25 x 10 ~4
7.14 xlO~ 4
1.93 x 10 ~5
1.93 x 10 ~4
1.93 XlO" 3
7.44 x 1015
exp[- 12639/RT]
7.07 x l O " 5

98
117
137
T (K)
70.4
84.0
99.3
115.0
34.9
25.7
34.9
45.5
70.1
79.9
90.0
60
73.5
85
60
70
80
68
86

1.93XlO" 5
1.93 x l O - 4
1.93 XlO" 3
3.94 x 1016
5.84 x 10 " 6
3.54 x 10 " 5
2.67 x l O - 4
1.656 x l O " 3
7.8xlO" 4
1.7 x l O " 4
5.8 XlO" 4
2.3 XlO" 3
9.83 x 10 ~5
3.29 x 10 " 4
1.20 x l O " 3
1.17xlO" 5
7.13 x l O - 5
3.03 xlO~ 5
6.7xlO~ 6
2.92 x 10 " 5
1.14 XlO" 4
1.93 x 10 " 5
1.93 x l O " 4

exp[-114.59//?7]
133.1

129.5

Xi
Xi
X1
h

h,m2
m2
m2
p2
J2
J2
k
h

a
a
a

exp[- 151.59/RT]

100.8

125.5

c,h
c
c
xi
Xi
X1
a
a
a

131.0

142

Refs.
150
150
150
150
338
344
344
344
344
215
215
215
257
257
257
324
306
306
306
154
154
154
154
279
279
250
250
250
248
248
248
126,337
126,337
126,337
344
344
344
344
154
344
344
344
344
345
345
345
345
153
153
153
153
196
196
196
215
215
215
337
337
337
344
344

TABLE 6. cont'd
Number of
C atoms
24 (cont'd)
25

Initiator

Solvent

2,5-Dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane
tert-Butyl 2-(2,2-diphenylvinyl)perbenzoate

Chlorobenzene
Chlorobenzene

Cyclohexane
Methanol
tert-Butyl 2-percarboxybenzalfluorene
26

30

oc,co-Di-0,0-caprylyl-(bis
succinyl)ethylene glycol

Chlorobenzene
Methanol
Ethylbenzene

oc,co-Di-0,O-caprylyl-(bispersuccinyl)triethylene glycol

Ethylbenzene

Dimyristyl peroxydicarbonate

Chlorobenzene

34

Dicetyl peroxydicarbonate

Chlorobenzene

36

oc,0)-Di-0,0-heptanoyl-(bisperphthaloyl)triethylene glycol

Ethylbenzene

42

oc,co-Di-0,0-caprylyl-(bispersuccinyl)nonaethylene glycol

Ethylbenzene

46

a,oo-Di-0,0-heptanoyl-(bisperphthaloyl)tridecaethylene
glycol
a,ca-Di-O,O-caprylyl-(bispersuccinyl)tridecaethylene glycol

Ethylbenzene

50

TABLE 7.

Ethylbenzene

T( 0 C)
106
T(K)
90.0
90.3
100.0
105.5
119.3
90.0
90.4

*d (s" 1 )
1.93
2.19
1.32
7.45
3.27
4.64
1.54
3.5
2.3

x 10 ~3
x 1015
x 10~4
x 10~5
xlO"4
XlO" 4
xlO-3
x 10 ~5
x 10~3

90
90

3.75 x 10 ~4
2.47 x 10 ~3

65
75
85
95
65
75
85
95
48
65
84
T (K)
48
65
84
T (K)
65
75
85
95
65
75
85
95
75
85
95
65
75
85

1.48 x 10~5
4.10xl0"5
2.19 x l O - 4
6.92 x l O - 4
2.74 x 10 ~5
8.47 x 10 " 5
2.95 x l O - 4
8.92 x l O - 4
1.93 x 10 " 5
1.93 x l O - 4
1.93 x l O " 3
2.82 x 10 15
1.93 x 10 ~5
1.93 x l O - 4
1.93 x l O - 3
3.02 x 1015
5.02 x IO ~5
1.420 x 10 ~4
5.19 x l O - 4
1.410 x l O " 3
1.66 x 1O~5
6.57 x 10 " 5
1.78 XlO" 4
9.72 x l O - 4
1.13OxIO- 4
3.5OxIO" 4
8.80xl0~ 4
1.28 x l 0 ~ 5
4.46 x 10 ~5
1.91 x l O ~ 4

Ea (kj/mol)

Notes

Refs.
344
344
175
175
175
175
175
175
175

exp[- 130.SS/RT]
t9
t9
t9
t9

175
175
120.7

306
306
306
306
306
306
306
306
344
344
344
344
344
344
344
344
306
306
306
306
306
306
306
306
306
306
306
306
306
306

116.9

exp[- 124.10/RT]

exp[- 124.30/RT]
124.4

116.9

122.3

128.2

MISCELLANEOUS INITIATORS

Initiator

Solvent

Acetyl cyclohexyl sulfonyl peroxide

Benzene

AH1-Cyanocyclohexyl)pentamethylene keteneimine

Chlorobenzene

Dibenzyl hyponitrite

Paraffin

T ( 0 C)
30
40
45
80.0
89.2
100.1
61.5
68.5
75.5
80.5
132

^d(S1)
1.4XlO" 5
9.42 x l 0 ~ 5
2.10xl0~4
3.25 x 10 ~6
1.007 x l 0 ~ 5
4.025 XlO" 5
6.5 x 10~4
3.7 x l 0 ~ 3
8.3 x l O - 3
1.45 x l O ~ 2
8.7XlO- 1

a (kj/mol)

Notes

147

a
a
a

Refs.
337
337
337
179
179
179
240
240
240
240
240

Notes page 11-69; References page 11-70

TABLE 7. cont'd
Initiator
Di-terf-butyl hyponitrite

Peroxybenzoylnitrate

Solvent
tert-Butanol
rc-Butyl ether
Ethanol(95%)
Isooctane

Nujol
Vapor

Vapor + NO

Vapor + NO

2,3-Dimethyl-2,3-diphenylbutane

Chlorobenzene

3,4-Dimethyl-3,4-diphenylhexane

Chlorobenzene

l,4-Dimethyl-l,4-diphenyl-tetrazene-2

Benzophenone
Cumene
Paraffin

Siliconeoil
Potassium persulfate

0.1 M NaOH

Water (pH 3)
Water

1-Pentanesulfonylazide
1,4-Butanedisulfonyl azide
1,6-Hexanedisulfonyl azide
1,9-Nonanedisulfonyl azide

Diphenyl ether
Diphenyl ether
Diphenyl ether
Diphenyl ether

1,10-Decanedisulfonyl azide
l,4-Dimethylcyclohexane-a,a'-disulfonyl azide

Diphenyl ether
Diphenyl ether

T( 0 C)
65
65
65
45
55
65
75
65
7.6
19.9
30.4
40.6
50.1
60.5
T(K)
18.1
30.4
40.6
T (K)
30.4
50.2
68.5
T(K)
237
259
284
T(K)
201
226
254
T(K)
121
149
120
130
140
164.2
174.3
186
194
126
139
50
60
70
80
90
50
80
80
40
50
60
50
60
70
50
166
163
163
150
160
170
163
163

kd (s" 1 )

Ea (kj/mol)

4.68 x 10 " 4
4.50 x 10 " 4
3.93 x 10 ~4
2.72 xlO~ 5
116.9
1.07 x l O - 4
4.0OxIO" 4
1.33OxIO-3
5.17 x 10~4
2.79 x 10 ~6
69.1
1.05 x l O - 5
2.02 XlO" 5
3.64 x l O - 5
1.21 x 10- 4
2.74 XlO" 4
1 x 107
exp[-69.1//?7]
8.18 xlO" 5
108.5
3.62 XlO" 4
1.42 x l O - 3
1.6 x 1015
exp[- 108.5/RT]
1.34 x l 0 ~ 5
79.2
7.22 x l O - 5
3.41 x 10" 4
6.3 x l O - 8
exp[-79.2/i?n
1.93 x 10 ~5
1.93 x l O " 4
1.93 x l O - 3
7.34 xlO 1 8
exp[-230.19//?n
1.93 x 10 ~5
1.93 x l O - 4
1.93 x l 0 ~ 3
1.45 xlO 1 5
exp[- IS032/RT]
3.3xl0"4
3.45 x l 0 ~ 3
2.3xlO" 4
6.5 x l O - 4
1.67 XlO" 3
2.6xlO- 2
5.6 x l O - 2
1.43XlO"1
2.5XlO- 1
3.7xlO" 4
1.92 x l O - 3
9.5 x 10 ~7
140.2
3.16 xlO~ 6
2.33 x l O - 5
9.16 XlO" 5
3.5 x l O - 4
1.66 x 10 ~6
6.89 x 10~5
5.78 x l O - 5
1.65 xlO" 2
83.4
4.02 x l O " 2
1.08XlO"1
3.78 XlO" 3
121.5
2.18 x l O - 2
5.01xl0~ 2
1.1 x 10- 6
4.46 x 10 " 4
5.02 x 10 " 4
5.02 x 10 ~4
8.84 x 10 " 5
2.25 xlO" 4
4.45 x l O - 4
4.45 x 10 ~4
4.82 x 10" 4

Notes

a
a
a
a
a
a
a,vn
a,v u
d 3 ,v 22
d 3 ,v 22
d 3 ,v 22
d 3 ,v 23
d 3 ,v 23
d 3 ,v 23

Refs.
317
317
317
317
317
317
317
317
261
261
261
261
261
261
261
261
261
261
261
261
261
261
261
344
344
344
344
344
344
344
344
240
240
240
240
240
240
240
240
240
240
240
242
242
242
242
242
242
115
115
262
262
262
262
262
262
262
166
166
166
166
166
166
166
166

ro-Xylene-a,a'-disulfonyl azide
p-Xylene-o^oc'-disulfonyl azide
Benzenesulfonyl azide

Diphenyl ether
Diphenyl ether
Naphthalene

/7-Bromobenzenesulfonyl azide
p-Chlorobenzenesulfonyl azide
p-Methoxybenzenesulfonylazide
p-Nitrobenzenesulfonyl azide
p-Toluenesulfonyl azide

Naphthalene
Naphthalene
Naphthalene
Naphthalene
1,4-Dichlorobutane
Dimethyl terephthalate
Diphenyl ether

p-Toluenesulfonyl-p-tolylsulfone

Hexanoic acid
Naphthalene
Nitrobenzene
1-Octanol
Tetradecane
Acetonitrile

Dioxane

163
163
110
120
125
130
175
120
120
120
120
145
155
130
145
155
155
120
155
155
155
29.3
39.1
49.3
29.3
39.5
49.3

6.09 x 10 ~4
5.78 x 10 ~4
3.6xlO" 6
1.07 x l O - 5
1.97xlO- 5
3.41xl0"5
6.08 x l O - 5
1.36 x 10 ~5
1.15 x 10 " 5
1.31 x 10 ~5
1.6OxIO" 5
1.7OxIO- 4
3.23 x 10 ~4
3.30 x 10~5
1.44 XlO" 4
3.43 x l O " 4
2.97 x 10 ~4
1.12 x l O " 5
3.97 x 10 ~4
3.63 x 10" 4
3.80 x 10 ~4
3.9xl0-5
1.45 x l O - 4
5.4 XlO" 4
2.IxIO-5
1.01 x l O - 4
3.9 x 10 ~4

152.3

103.8

115.5

166
166
235
235
235
235
235
235
235
235
235
166
166
166
166
166
166
235
166
166
166
144
144
144
144
144
144

C. NOTES
a
/cd converted to s" 1 from author's units
b
kd values for several concentrations averaged
t)2 analyzed from nonisothermal conditions
c
kd increases with increasing initiator concentration
c 2 rate non-linear
c3 hydroperoxide concentration 7.83 x 10~ 3 mol/1
C4 hydroperoxide concentration 2.50 x 10~ 3 mol/1
d
kd decreases with increasing initiator concentration
d2 after 1st half life; rate slower initially
d3 rate is second order: units are 1/mol sec.
e fcd listed is for lowest initiator concentration
f
&d is extrapolated value for zero initiator
concentration
g
kd ^ has been corrected for induced decomposition
g2 corrected for uncatalysed reaction (7 x 10 ~5 s" 1 )
h
AH (not E2)
i
pressure (number gives mbar)
j
iodometric analysis
j 2 manometer measurement
k
infrared analysis
1
kd is limiting value with respect to additive
concentration
mi 3,4-dichlorostyrene added to minimize induced
decomposition
m2 styrene added to minimize induced decomposition
ni3 methyl methacrylate added to minimize induced
decomposition
ni4 isobutene added to minimize induced decomposition
m5 acenaphthalene added to minimize induced
decomposition
m 6 1 mol/1 oc-methylstyrene added to minimize induced

decomposition
mj butadiene added to minimize induced decomposition
mg acrylonitrile added to minimize induced
decomposition
n
trichloroacetic acid added
n2 3.2wt.% or about 0.1 monolayer
o
addition of trichloroacetic acid did not affect kd
p
degassed
p 2 photochemical benzophenone added: 6.56 x 10 17
quants/min @ 366 nm
q
addition of trichloroacetic acid increased kd several
fold
q 2 pH 2.90
q 3 pH 7.05
r
not inhibited, but initiator concentration low enough
(0.01-0.09 M) so that higher order decomposition is
unimportant
s
solvent not degassed
11 2,6-di-terr-butylphenol added to inhibit induced
decomposition
t2 oc,a-diphenyl-P-picrylhydrazyl added to inhibit
induced decomposition
t3 phenyl-oc-naphthylamine added to inhibit induced
decomposition
t4 tetrachloroquinone added to inhibit induced
decomposition
t5
1,3,5-trinitrobenzene added to inhibit induced
decomposition
t6 12 added to inhibit induced decomposition
tj
O 2 added to inhibit induced decomposition
t8
5-20% NO 2 added to inhibit decomposition
References page II - 70

t9
tio

vi
V2
V3
V4
V5
v6
v7
Vg
v9

galvanoxyl added to inhibit induced decomposition


a,y-bisdiphenylene-p-phenylallyl added to inhibit
induced decomposition
oc-naphthylamine added to minimize induced
decomposition
2,3 / ,5 / ,6 / -tetra-te7t-butyl indophenoxy added
benzoquinone added
2,6-di-teJt-butyl-4-methylphenol added
in absence of oxygen
from initiation data
in multisurface reaction vessel
rate reduced when nujol layer used to exclude Hg
vapor
rate increased when nujol layer used to exclude Hg
vapor
acetic acid added
CuCl 2 added
CuCl added
0.1 mol AgClO 4 /mol AIBN added
3.9 mol thiophenol added
tert-bxxtyl mercaptan added
2.5 mol cyclohexane added
~ 4 x l O ~ 2 mol pyridine added
2 x 10~ 2 mol pyridine added

D.

REFERENCES

tn
ti2
ti3
114
ui
u2
u3
U4
U5

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v 10
Vn
v 12
v 13
v 14
v 15
v 16
v 17
v is
v 19
V 20
v2i
V 22
v23
v24
v25
v 26
w
x1
x2
y
z

2.5 mol cumene added


buffered with sodium pyrophosphate
saturated with ethyl acetate
3.11 mol CCl4 present
peroxide in P(MMA)
peroxide in P(sty.)
0.26 mol piperidine
0.24 mol triethylamine
0.21 mol AT,Af-diethylaniline
0.22 mol pyridine
0.9 mol Z n C l 2
in presence of 1 5 N O
0.12 mol 18 crown 6 added
0.24 mol diglyme added
0.02 M pyridine added
0.10 M pyridine added
0.10 M 2,6-lutidine added
stereoisomers
actual rate divided by 2 because of two identical
peroxide groups
each peroxide group has different k^
measured in differential scanning calorimeter:
subscript is heating rate in deg/min
pressure (in bar)

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P r o p a g a t i o n
i n

F r e e

a n d

T e r m i n a t i o n

R a d i c a l

C o n s t a n t s

P o l y m e r i z a t i o n

M. Kamachi
Department of Applied Physics and Chemistry, Fukui University of Technology, Gakuen, Fukui, Japan
B. Y a m a d a
Department of Applied Chemistry, Faculty of Technology Osaka City University, Sumiyoshi, Osaka, Japan
A. Introduction
B. Tables of Propagation and Termination
Constants
Table 1. Dienes
Table 2. Olefins
Table 3. Acrylic Derivatives
Table 4. Methacrylic Derivatives
Table 5. ltaconic Derivatives
Table 6. Fumaric Derivatives
Table 7. Vinyl Halides
Table 8. Vinyl Esters
Table 9. Vinyl Ethers
Table 10. Styrene Derivatives
Table 11. Vinyl Heteroaromatics
Table 12. Aldehydes
Table 13. Others
C. References

11-77
11-79
II-79
II-79
II-80
II-82
II-85
U-87
II-87
II-87
II-88
II-88
II-90
II-90
II-90
11-91

The rate constants kv and kt have usually been assumed to


be independent of chain length. In this chapter termination
constants depending on the length of the polymer radicals
are also reported. In American literature the right hand side
of (A4) is written as 2t[P#] . In this chapter the definition
given in Eq. (A4) has been used.
Simultaneous determination of absolute values of both
kv and kt from a single experiment has not been reported. In
practice, the ratio k^/kt is determined from measurements
of molecular weight as a function of rate of polymerization
for a low conversion polymerization or from measurements
of initiation rate and polymerization rate in a low conversion. The ratio kp/kt is determined from nonsteady-state
measurements of the average lifetime, r, of the growing
polymer chain in a photochemically initiated polymerization. This lifetime may be defined by noting that the
concentration of chains present must be related to their
average lifetime and rate of disappearance by
(A6)

A.

INTRODUCTION

In free radical polymerization the propagation and termination rate constants describe the reactions

which, from (A3) and (A4), yields


(A7)

(Al)
dead polymer

(A2)

where P^ is a propagating chain of any length n and M is


the monomer. The rate constants are defined by the
following equations:

By combining the separately determined ratios, k^/kt and


kp/kt, the individual propagation and termination rate
constants may be calculated. Alternatively, the rate of
initiation, R[, may be measured as the rate of initiator
disappearance and equated to R1. This gives (from (A6) and
(A3))

(A3)
(A4)
where
(A5)

(A8)
There is a large degree of imprecision inherent in
measuring r and in combining data from different
experiments, which helps to explain the scatter in the data
tabulated here.

/Ct(XiO"6)

kp

/C1(XiO-6)

Figure 1. Arrhenius plots of all bulk polymerization data for


styrene for kp () and /ct (+). Solid lines are least squares obtained
by assuming all points to be of equal value.

The two monomers styrene and methyl methacrylate


have been so extensively studied that their data are
presented as Arrhenius plots (Figs. 1 and 2). Because of
the influence of solvents on the rates, only data of bulk
polymerizations are shown. It remains a wide scatter, which
should serve as a warning against casual acceptance of any
single number. Solid lines are the least squares that have
been calculated assuming all points to be of equal value.
For the termination rate of methyl methacrylate the leastsquares line results in a positive slope and is not shown. In
this case a temperature-independent kt could be a better
representation of the experiments.
The pulse laser polymerization (PLP) method has been
developed as a new method of obtaining kp. In the PLP
method, the value of kp can be estimated from the degree of
polymerization of polymer formed, vp, a knowledge of the
monomer concentration, [M], and tf the time between
pulses:
(A9)
The reproducibility of the PLP method has been recognized
by an IUPAC Working Party on Modeling of Kinetic and
Process of Polymerization, which is establishing a critical
review of the literature values of kp.

K9

1000
T
Figure 2. Arrhenius plots of all bulk polymerization data for
methyl methacrylate for /cp () and /ct(+). Solid lines are least
squares obtained by assuming all points to be of equal value. The
line for kx is not shown since a horizontal line for a temperature
independent kt could be a better representation.
Classification of the methods for the determination
of rate constants
The tabulated data refer to seven different methods.
Method A uses the following four methods for the
measurement of the lifetime r:
Al -rotating sector or a "flashing" laser
A2 - flow through a tube with spatially separated light
and dark sections
A3 - spacial intermittent polymerization (SIP)
A4 - intermittent illumination method
Method B effectively measures only a single decrease
(increase), in the radical concentration by the following
methods:
B l - dilatometry
B 2 - dielectric constant
B 3 - interferomety
B4 - temperature change
B5 - viscosity
B6 - light scattering
B7 - monomer pressure

B 8 - cathetometer
B9-inhibitor
BlO-scavenger

Method F uses pulse laser photopolymerization (PLP)


method

Method C uses electron spin resonance (ESR) for the


determination of the radical concentration
Method D refers to values obtained in emulsion polymerization by application of the Smith-Ewart theory

Fl - PLP
F2 - PLP-GPC (MWD)
F3 - PLP-MALDI TOF (-GPC)
Method G refers to the method of measuring molecular
weight (MW) and molecular weight distribution (MWD) by
Gl - gel permeation chromatography (GPC)
G2 - high performance liquid chromatography (HPLC)

Method E refers to recalculated values

B. TABLES OF PROPAGATION AND TERMINATION CONSTANTS


TABLE 1. DIENES
Monomer
1-Acetoxybutadiene
Butadiene

k9 (1/mol/s)

M x I O " 6 ) (l/mol/s)

Temp. (0C)

Method

18.0
&p = 1 . 2 x l 0 8
x exp(- 39000/RT)
150 4 0

281

25
10

Al
D

152
23

kt = 1.13 x l O 4
xexp(-711/r)

5
45-60

C
Gl

223
202

50

Fl

221

50

Fl
F2

Solvent: chlorobenzene
Solvent: chlorobenzene

40

D
D

Quoted in Ref. 86

l n * p = l n (3.873 x 1010)
- 53400/RT
111.6
kp = 8.05 x 107
xexp(-35710//?7)
Chloroprene
220
fcp = 2 . 9 x l 0 9
x exp(-41000/^7)
*p = 1.95 x l O 7
x exp(- 26630/RT)
2,3-Dimethyl-l,3-butadiene
&p = 8 . 9 x l 0 7
x exp(- 38000//?7)
Ethyl 4-ethoxy-2,4-pentadienoate
9.9
Ethyl 4-methyl-2,4-pentadienoate
29.7
Ethyl pentadienoate
30.9
1,3-Hexadiene
20 1 0
2,4-Hexadiene
16 1 2
Isoprene
2.8

2-Methyl-l,3-pentadiene

Remarks

Refs.

221
187
59
84

Fl

198

71
152
152
152
223
223
24

9.3
23
19
-

25
25
25
5
5
5

Al
Al
Al
C
C
D

125 3 0
35 10

5
5

C
C

k p (1/mol/s)

M x I O 6 ) (1/mol/s)

Temp. ( C)

Method

1050 5 0
455 5 0
200

83
-20.01
130

Al
Al
Al

3.9 (7.8) x 102


1.99 x 102
-

130
190
230

Al
C
Fl

3.2 x 103

190

Fl

Calalyst system: diisopropylbenzene,


monohydroperoxidetetraethylenepentamine

223
223

TABLE 2. OLEFINS
Monomer
Ethylene

Propylene

470 3 0
18.6 2
5400
p = 4.8x 107
x exp[(- 4450 + 3.Ix 10~6p)/T]
1.2 x 104
1.09 x 104
3.08 x 104

&p = 2 x l 0 6
x exp(- 32000/RT)

50-150

Remarks
Solvent: benzene
Pressure 1.8 x 10 8 Pa
Pressure (5-17.5) x 10 7 Pa, using
results of Ref. 141
Pressure 1.9 x 108 Pa
Initial pressure 2.27 x 108 Pa
Pressure 2.55 x 108 Pa,
at low or moderate conversion
Pressure 2.50 x 108 Pa,
at conversion 0
Radical telomerization

Refs.
53
66
139
142
135
151
167
167
129

References page 11-15

TABLE 3. ACRYLIC DERIVATIVES


Monomer

kp (1/mol/s)

kt (xlO~ 6 ) (1/mol/s)

Acrylamide

6000 1000
18000 1500
8200
220
(7.9 0.5) x 10 4
(4.3 0.2) x 104
(3.3 0.2) x 104
(2.3 0.1) x 10 4
fcp=7xl06
x exp[(- 21000 2000)/RT]

3.3 0.6
14.5 2.0
5.5
1.0
660 4 0
350 2 0
230 2 0
160 1 0

650

2.6

3150

2.6

Temp. (0C)

25
19
26
30
30

Method
Al, Bl
Al
A
A
Al
Al
Al
Al
Fl

Remarks
Solvent: water, pH 5.5
Solvent: water
Solvent: water
Solvent: DMSO
Solvent: water 0.38M
H 2 O : DMSO (90:10)
H 2 O:dioxane (90:10)
H 2 O : THF (92:8)

Refs.
79
41
89
89
126
119
119
119
197

Acrylic acid

-,butyl ester

- , cyclohexyl ester
-,ethyl ester

6600
2.7
13
0.018
2100
330
1977
3.84
67966
6.40.6
log 10 fcp = 6.0123-748.4/7
ln[(*t[p]/(1.00 + OMp)]
= l n * t [I]-0.6Op
1360
1.28
963
1.18
1320
1.07
360
0.36
2722 248
3.2 0.3
800
1.76
12.39 x 10 3
139.2

- , 2-ethylhexyl ester
- , methyl ester

23

Al
Al

30
25-80
30

Al
Al
B4
Al
Al
Fl
B5

30

Al

30
50
50

Al
Al
Al

25
25

155
1300

0.233
75

50
15

Al
Al

880

260

15

Al

25
25

Al
Bl
Al

1580
580
fcp = 1 . 0 x l 0 8
x exp(- 30000/RT)
1000
11680
21300
(1.5 0.2) x 10 4
(3.7 0.6) x 104
6.3 x 104
(1.4 0.2) x 104

55
6.5
fct
= 2.8xl0n
x exp(- 22000/RT)
3.5550
194
-

60

Al
Al
Al
G2

60
60
60

G2
G2
G2

- , 2-(acetoacetoxy-methyl)-, ethyl ester


- , 2-cyano-, ethyl ester

300
1622
1610
1613
1607

1.0
411
404
411
404

60
30
30
30
30

C
Al
Al
Al
Al

- , 2-chloro-, ethyl ester

1660
1408
1120
978
350

333
244
4.8 x 102
435
2.1

30
30
30
30
60

Al
Al
Al
Al
C

- , 2-fluoro-, ethyl ester


- , 2-acetoxymethyl-, methyl ester

Solvent: Water, pH 7.9,


(with 1.2MNaOH)
Solvent: water,
pH 7.9 (with 1.5NNaCl)
Solvent: water, pH 11

Pressure 5.0 x 107 Pa


Solvent: benzene 1.76M
kt \p\; kt for pressure p (bar),
kt [l] = 3.5x 106
Solvent: anisole 2.00M
Solvent: benzene 2.00M
Solvent: chlorobenzene 2.00M
Solvent: benzonitrile 2.00 M
Solvent: benzene 1.76M
Solvent: toluene 1.84 M
Solvent: benzene x\ molar fractions
of monomer, x = 0.401,
kp and kt also given by other [M]
Solvent: toluene 1.94M
From unpublished results of Ross
and Melville
From unpublished results of
Matheson

99
99
99
10
57
107
137
201
122
138
138
138
138
137
108
171

108
22
22
19
48
21

Solvent: benzene 2.69 M


Primary propagating step (jfcpl),
Ph-MA*
PhCO 2 -MA'
tert-BuO-MAm
Secondary propagating step (kp2),
Ph-MA-MA*, PhCO 2 -MA-MA',
tert-BuO-MA-MA*
Solvent: benseme
AcOH 7 wt.%
1,3-propanesulfone 0.5 wt.%
Optimum value, solvent: AcOH
Optimum value
Solvent: propanesulfone
AIBN 4.88 x 10" 2 M
Optimum value
Optimum value
Solvent: benzene LOOM,
MAIB 0.050 M

50
144
144
190
190
190

170
143
143
123
123
140
123
146
123
225

TABLE 3. cont'd
Monomer

fep

(1/mol/s)

fct(x..l0-6)

(l/mol/s)

Temp. ( 0 C)

Method

- , 2-acetyloxy-, methyl ester

430

60

- , 2-benzoyloxy-, ethyl ester


- , 2-(benzyloxymethyl)-, methyl ester

990
182

2.9
1.6

60
60

C
C

- , 2-[2,2-bis(carbomethoxy) ethyl],
methyl ester

4.0

0.038

60

- , 2-butoxy-, methyl ester

298
184

8
-

60
60

C
C

- , 2-butyroxymethyl-, methyl ester

360

1.4

60

19

0.51

60

8.6
1.6
300

21
1.8
1.1

60
60
60

C
C
C

11

0.08

50

0.57

0.11

60

0.76

1.4

60

- , 3-methyl, dimethyladamantyl ester

0.41
0.71

0.081
1.1

60
60

C
C

- , 3-methyl, terf-butyl ester

0.90
LO

2.3
4.7

60
60

C
C

- , 2-naphthoyloxymethyl-, ethyl ester

320

0.37

60

- , 2-pivaroxymethyl-, methyl ester

230

0.59

60

- , trans-2-vinyl-, methyl ester

125

60

3000-5000
127
52
51
20000
24

12.2
5
1.8

OD
25
25
25
40
50

B4
B4
B4
D

1960
15400
28000
1910
382 230
3300 300
3200 400
3000 600
(6.5 1.3) x 103
28.2

782
2700
3700
290
47.6 2 2
1200 170
300 5 0
240 70
4700 1300
0.20

60
25
25
25
25
50
50
50
50
60

Al
Al
Al
Al
Al
Al
Al
Al
Al
C

273
273
8267

17.9
11.9
2200

30
30
30

Al
Al
Al

- , 2-(2-carbomethoxy)- ethyl-,
methyl ester
- , 2-ethyl-, methyl ester
- , 2-ethyl-, cyclohexyl ester
- , 2-isobutyroxymethyl-, methyl ester
-,-2-(methoxycarbonylmethyl)-,
phenetyl ester
- , 3-methyl, adamantyl ester

Acrylonitrile

Ar-Acryloyl-2,2-dimethyl5 (R)-phenyl-l,3-dioxazoline
7V-Acryloylpiperidine
N-Acryloylpyrrolidine

23

Remarks
Solvent: 1,1,2-trichloroethane 2.0M
2,2'-azobis (4-methoxy-2,4dimethylvaleronitrile) 0.030 M, kp
also given by other temp.
Solvent: benzene 1.56M
Solvent: benzene 2.0M,
AIBN 5 ^ x IQ^ 3 M
Bulk AVN 0.05 M,
Ic p and kt also given by
other temp.
Solvent: benzene 2 M
Solvent: 1,1,2-trichloroethane 2.0M
2,2'-azobis (4-methoxy-2,4dimethylvaleronitrile) 0.030 M, kp
also given by other temp.
Solvent: benzene LOOM, MAIB
0.050 M
Bulk MAIB 0.05 M, kp and kt
also given by other temp.
Bulk AIBN 0.10M
Bulk AIBN 0.10M
Solvent: benzene LOOM,
MAIB 0.050 M
Solvent: benzene 2.22 M, kp and kt
also given by other temp.
and [M]
Bulk 4.8 M
MAIB 0.05 M
Solvent: benzene 2.4 M,
MAIB 0.05 M, kp
also given by other [M]
Bulk 4.0 M, MAIB 0.05 M
Solvent: benzene 2.0M,
MAIB 0.05 M
Bulk 5.9 M, MAIB 0.05 M
Solvent: benzene 2.0M,
MAIB 0.05 M
Solvent: benzene LOOM,
MAIB 0.01 M
Solvent: benzene LOOM,
MAIB 0.005 M
Solvent: benzene LOM,
AIBN 0.25 M

Solvent: DMF

Refs.
224

172
206
228

176
224

225
229
230
230
225
157

232
232

232
232
232
232
226
225
227
42
49
63
75
42
35

Primary radical termination in a


precipitating medium
Solvent: DMF
43
Solvent: water
54
Solvent: water
55
Solvent: DMSO
70
Solvent: DMF
68
Solvent: DMF 3.8 M
88
Solvent: DMSO 3.8 M
88
Solvent: Ethylene carbonate 3.8 M
88
Solvent: Mg (C1O4)2 12H2O 3.04M 88
Solvent: benzene 1.08 M,
231
MAIB 0.05 M, kp and kt
also given by other temp.
145
Optimum value
123
Optimum value
123

References page 11-15

TABLE 3. cont'd
Monomer

kp (1/mol/s)

ifetCxlO"6) (1/mol/s)

Temp. (0C)

Method

JVW'-Dimethylacrylamide

11000
27200
29198
15 x 10 3
2330 230

38
3540
4080
0.540 0.053

50
30
30
25
30

Al
Al
Al
Fl
A4

2760 342

0.452 0.056

30

9.9 x 10 3

25

Fl

kp (1/mol/s)

kt (x 10 ~6) (1/mol/s)

Temp. (0C)

Method

79.6 5.6
1.1 x 10 3
~21
26

16.5 1 . 4
~27
21

25
25
30
25

Al
Fl
Al

670

2.1

23

Al

1950
1410
110
895
1250
510

2.25
41.9
80
40
41.9
2.87

30
32.5
32.5
30
20

Al
Al
C
C
Al
Al

- , bornyl ester

580

3.3

60

- , n-butyl ester

369
573
360
lnfcp = 6 . 1 3 + 6.33 x 10 ~9 p
lnfcp = 15.8-2751/7

10.2
18.0
10

30
30
30
30
12-93
70
30

Al
Al
Al
F2
F2
B5
B5

10-90

Fl
Fl
A3
Al

3-Dimethyl-(acryloyloxyethyl)ammonium propane sulfonate

N-Methylacrylamide

Remarks

Optimum value
Solvent: water, pH 1.4
Solvent: formamide: 1,4-dioxane
(3:1 (v/v))
Solvent: formamide: 1,4-dioxane
(3:1 (v/v)), NaCl 0.1 M
Solvent: water, pH 1.9

Refs.
74
121
123
197
192
192
197

TABLE 4. METHACRYLIC DERIVATIVES


Monomer
Methacrylamide
Methacrylonitrile
p

Remarks
Solvent: water
Solvent: water, pH 1

Refs.
69
197
26
39

106.430.26

xexp[(-297001500)//?n
Methacrylic acid

- , benzyl ester

- , terf-butyl ester

2.6
In [(kt\p]/(\M + 0.0lp)]
= InJt1[I] - 0.73/7
ln*p = (14.41 0.09) - (247229)/T
jfcp = 3.44 x 10 6 exp(- 23300/RT)
1576
9.74
350
14
p

1O7.4o.4

30
25
9

_66

Solvent: water, pH 8.0


(with 0.22MNaOH)
pH=13.6

kp and kt also given as a


function of viscosity
Solvent: benzene 1.0 M,
AIBN 0.05 M
Pressure: 5.0 x 10 7 Pa

Pressure 1.0 x 10 8 Pa
77=1.92cp
kt \p]\ kt for pressure p (bar),
kt[l] = 13.4 x 10 6

99
99
101
153
153
87
103
193
27
106
109
216
216
212
122
219
169
225
52
203

F 1

xexp[-(27.72.5)x IO3/RT]
- , trans-4-tert-buty\cyclohexyl ester

- , cetyl ester
- , p-Ip-(cetyloxy)benzoyloxy]phenyl ester
- , 2-chloroethyl ester
- , 2-cyclohexylethyl ester
- , cyclohexyl ester
- , 2-decahydronaphthyl ester

550

1.9

60

510
570 1 0
300 9 0
300

1.9
0.5-2.3
0.16 0.04
0.25

60
60
30
50

C
C
Al
Al

170
254
1190

0.30
6.71
32.8

50
30
30

Al
Al
Al

510

5.4

60

570

3.1

60

Solvent: benzene LOM,


AIBN 0.05 M, trans 100%
trans 28.9%
Solvent: benzene
Solvent: dioxane 0.2 M

Solvent: toluene 0.2M

Solvent: benzene LOM,


AIBN 0.05 M
Solvent: benzene LOM,
AIBN 0.05 M

194
194
210
109
97

97
87
87
193
193

TABLE 4. cont'd
Monomer
- , 2,6-dimethylphenyl ester
- , dodecyl ester
-,ethyl ester

- , hexadecyl ester
- , isobornyl ester
- , isobutyl ester
- , isopropyl ester
- , lauryl ester

- , 2-methoxyethyl ester
- , methyl ester

kp (1/mol/s)

M x l O " 6 ) (1/mol/s)

Temp. (0C)

Method

68

2.1

30

Al

72
126

2.4
0.6
7.35
10

30
70
30
70

Al
B5
Al
B5
Fl

0.16
3.5

10-90
70
60

Fl
B5
C

10-90
30
30

Fl
Al
Al
Fl

219
87
109
169

30
23.6

Al
Al
Al

87
9
7

32.5
40
50
-30
20

C
Bl
E
Bl
Al

* p = 1.50 XlO 6
x exp(- 20460/RT)
ln* p = (15.110.17)-(275355)/r
390

lnfcp = (14.720.13)-(259042)/7
121
4.52
460 140
0.6 0.2
kp = 2.93 x l O 5
x exp(- 16190/RT)
249
9.30
310 2 0
66 4
fcp = 5 . 1 3 x l 0 6
kt = 1.36 x l O 3
x exp(- 26400/RT)
x exp(- 11900/flT)
187
72.1
404
17.6
410
24
13.2
0.488
390
517
527
28
260
270
280
285
310
330
340
240
335
270
330
250
240
280
320
390 4 0
410 40
410 4 0
18050

37
23
4.4
21
21
19.5
17.5
17
17
17
11.5
9
22
16
29
25
14
28
42 4
29 3
26 3
20 6

10
10
10
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
20

Bl
Bl
Bl
Al
Al
Al
Al
Al
Al
B5
B5
B5
B5
B5
B5
B5
B5
B5
Al
Al
Al
E

500 250
41.6
62
200
128
364

63 3 2
2.69
8.44
41.8

20
0
5
20
22
22.5

B6
B5
D
B6
Bl
B4

512.6
410

46.6
42.7

25
25

Al
Al

248
141
106
140

22.7
11.6
5.7
-

30
30
32
40

Al
A
B4
D

Remarks

Refs.
120

Optimum value
r? = 3.96cp

123
212
87
212
169

7^ = 0.91 cp

rj = 7.52cp
Solvent: benzene 1.0 M, AIBN
0.05 M

Solvent: ethyl acetate


Using results of Ref. 7
Solvent: ethyl acetate
kp also given as a function of temp.
and of viscosity for other solvents
Solvent: methanol
Solvent: pyridine
Solvent: DMF
Solvent: benzene 4.69 M
Solvent: fluorobenzene 4.69 M
Solvent: chlorobenzene 4.69 M
Solvent: anisole 4.69 M
Solvent: bromobenzene 4.69M
Solvent: benzonitrile 4.69 M
Solvent: methyl benzoate 4.69 M
Solvent: methylphenyl acetate 4.69 M
Solvent: dimethyl phthalate 4.69 M
Solvent: dimethyl carbonate 4.69 M
Solvent: diethyl oxalate 4.69 M
Solvent: methyl formate 4.69 M
Solvent: methyl propionate 4.69 M
Solvent: diethyl succinate 4.69 M
Solvent: acetonitrile 4.69 M
Solvent: methanol 50% by vol.
Solvent: n-octane 5% by vol.
Solvent: -nonane 20% by vol.
DP = (2-8) x 10 3 using results of
Ref. 86
DP = ( 3 - 5 ) x l 0 4
Assuming biradical initiation
Jfcp found as a linear function of Mw
Rate of initiation; 1.20 x 10 " 8
(moles/1/s)
kp and kt also given as a function of
viscosity for other solvents

219
212
193

153
51
62
72
92
94
94
94
85
85
85
85
85
85
90
90
90
90
90
90
90
90
90
104
104
104
96
96
11
65
91
29
60
30
93
14
87
58
65

References page 11-15

TABLE 4. cont'd
Monomer

A:p (1/mol/s)

M x l O ~ 6 ) (1/mol/s)

Temp. (0C)

Method

0.224
573

2.0

45
60

D
E

573

11.9

60

995 83
506 48
450 3 3
45629
448 47
498 39
61443
427 38
290
1020
530
550

43.6 4.9
35.6 3.9
42.0 3.0
43.82.0
47.2 6.6
42.9 4.7
39.93.3
30.9 3.7
21
292
55
68

80
30

kp= 4.92 XlO 5


x exp(- U210/RT)
315

kt = 9S
x exp(- 2930/RT)
33.9

15-30

A2

25

A2

336 9 0
441
fcp = 2 . 5 x l 0 6
x exp[(- 23000 2500)/RT]
kp=k (0.33 < Wp < 0.84)
= exp[-29.8(Wp-0.84)]
(0.84 < w p < 0.99)

28 12
19.7
720

25
30
25-60

Al
Al
C

50

w p (weight fraction of polymer)

150

At high conversions ( ~ 65%)


Special evaluation from
steady-state and Mn
Solvent: toluene

148
134

30
60

Al
Al
Al
Al
Al
Al
Al
Al
Al
Al
Al

Remarks

Refs.

Termination by combinat. using


results of Refs. 7 and 31
Termination by disprop. using results
of Refs. 7 and 31
Solvent: benzene 4.7 M
Solvent: anisole 2.0M
Solvent: benzene 2.0M
Solvent: C 6 D 6 2.0M
Solvent: fluorobenzene 2.0M
Solvent: chlorobenzene 2.0 M
Solvent: benzonitrile 2.0M
Solvent: benzene 1.0 M
Addition of 1 x 10 " 3 mol pyridine
Addition of 1 x 10" 3 mol acetone
Addition of 1 x 10 " 3 mol
triethanolamine
P n = IO4
kp and kt also given as a
function of P n
Pressure 5.0 x 106 Pa
Pressure 5.0 x 10 7 Pa

67
33
33
111
133
133
133
133
133
133
133
118
118
118
118
114
110
127
105
45

(*J= 790 300)


130
705.6

20.7 1.0
25

0
60

Al

170
306
292

0.2
25
25

F3
Fl
Fl

60
20-90

C
Fl

30

B5

670 3 0
22
InATp = 14.69-2670/7+
0.201/7x(1.0x 1 0 " 5 P - I )
\nkt[p] = InA:t[l] -0.57/7
26.6

1.4

BlO

5.8

0.017

BlO

kt(m,n) = 1.22 x W2(n x m)~ 0075

25

A3

21

70

B5

0.034

50

0.16

50

- 1 to - 70
60

Fl
C

- 8
30

F3
Fl

fcp = 106 694 exp(- 23940/RT)


lnJfcp (VmoVmin) = ln*p,<>-(3.86 [AIBME]0
+ 0.8) x (l-(f>m)- 1.6 (l-cj)m)60

131
680- 820

690-810

Fl

222
196

Solvent: ethanol (50%) 4.67 M, kv


also given by other [M] and solvents
175
207
kt\p\\ kt for pressure/? (bar),
fct[l] = 15.4x 106
Scavenger DPPH, solvent: DMF,
blank polymn.
Scavenger DPPH, solvent: DMF,
template polymn., template;
it-MMA
n: n-mer; m: m-mer, coupling with
rt-mer and m-mer
77 = 0.53 cP
No addition of chain-transfer agent,
Time 7.5-20.5 min.
Addition of 2% CBr4,
Time 7.5-20.5 min.
AIBME (dimethyl 2,2'azodiisobutyrate) 0.0434M, </>m;
monomer volume fraction
pX) = 700(l/mol/min)
Benzoin 7 x 10 " 4 M
Solvent: toluene, pressure
1.0 x 108 Pa, k p also given by
other pressures
Solvent/2-butanone, pressure
1.OxIO 8 Pa

122
115
115

147
212
149
149
217
158

199
208

208

TABLE 4. cont'd
Monomer

kp (1/mol/s)

M x l O " 6 ) (1/mol/s)

Temp. (0C)

Method

3138.1
794.0
815.0
957.0

394
62.4
51.6
38.2
25(3)

25
60

Fl
B5

60

21 2
45
50

60
25
40

C
Al

191
160
160

25
50

Fl
Fl
C

198
220
184

510 100
299
431
)tp = 2.39 x 106
x exp(- 22000/#D
359
12

135
292
200
135 5 0
170

-, octyl ester

35
2960
*p = 1.9068 x 106
xexp(-21181.07//?D
kp = 1.2169 x 106
x exp(- 25203.59//?D
kp = 3.0598 x 107
x exp(-28008.18/RT)
35
1710
240 8 0

0
25
28
0
50

29.1

50
30

Al
Fl
Bl
Al
C

Values from Chem. Abstr.

159
164
83
165
155

30% MMA in benzyl alcohol

227

Fl

30% MMA in NMP

227

p.s. 500 nm
Pressure 5.0 x 10 7 Pa

155
113
109
122

30
30
30
60

Al
Al
Al
Al
Al
Al
Al
Al
Al
Al
C

26
1470 170

0.301
0.499 0.058

32.5
30

C
A4

2760 342

0.452 0.056

30

185

0.034

20

B8

230

0.053

20

B8

kp (1/mol/s)

t ( x l 0 ~ 6 ) (1/mol/s)

Temp. (0C)

Method

1.7
3.9

2.5 x 10" 3
3.4xl0~3

60
60

C
C

Polyhydroxytetramethylene-a,
co-methacrylate of MW = 700

particle size 260 nm, kp


also given by other particle sizes
kp; average value

Fl

411
230 1 5
1768
1809
223 11
235 8
273 8
228
149
467
590

30
30

Emulsion polymn.,

161
204
204
204
166

A3
Fl

50
30
30

Solvent: benzene 3 M
Solvent: chlorobenzene 3 M
Solvent: benzonitrile 3 M

Refs.

Emulsion polymn., n-butyl aery late:


MMA: methacrylic acid (8:91:1),
particle size (p.s.) 50 nm, kp also
given by other temp, and particle sizes
p.s. 500 nm
155
225
227

62.6
2.6 0.9
ln[(fct[p]/(1.00- 0.19)]
= \nkt[l]-l.01p
11.9
2.02 0.22
2.060.21
2.160.19
2.26 0.22
1.72 0.11
1.96 0.12
1.88
0.813
45.1
2.6

-, phenyl ester

- , 2-phenylethyl ester
- , 3-phenylpropyl ester
- , rc-propyl ester
- , 3-tetracyclo-[4.4.02'5.l7'10]dodecyl ester
-, triphenylmethyl ester
3-Dimethyl-(methacryloyloxy-ethyl)
ammonium propane sulfonate

25.6
-

Remarks

Al
Al
B5

kt[p]\ kt for pressure p (bar),


ikt[l] =40.0 x 106
Solvent:
Solvent:
Solvent:
Solvent:
Solvent:
Solvent:

anisole 2.00M
benzene 2.00M
fluorobenzene 2.00M
chlorobenzene 2.00M
bromobenzene 2.00M
benzonitrile 2.00M

Solvent: benzene 1.0M,


AIBN 0.05 M

87
116
116
116
116
116
116
87
87
28
193

153
Solvent: formamide:
192
1,4-dioxane (3 :1 (v/v))
Solvent: formamide:
192
1,4-dioxane (3 : 1 (v/v)), NaCl 0.1 M
Calcd. from nonstationary
125
state kinetics
Calcd. from stationary state kinetics 125

TABLE 5. ITACONIC DERIVATIVES


Monomer
Itaconic acid
- , bis (4-terf-butyl-cyclohexyl) ester
- , bis (cyclohexyl-methyl) ester

Remarks

Solvent: benzene 0.5M


Solvent: benzene 1.5M,
MAIB 0.02 M

Refs.

213
182

References page 11-15

TABLE 5. cont'd
kp (1/mol/s)

M x l O " 6 ) (1/mol/s)

Temp. (0C)

Method

- , bis (3,5-dimethyl-l-adamantyl) ester


- , bis (2-ethylhexyl) ester

0.92
6.8
3.4
2.0
2.1
2.2
2.1
2.1
1.4
3.0

0.32 x 10~3
0.001

60
50
50
50
50
50
50
50
50
50

C
C
C
C
C
C
C
C
C
C

- , diadamantyl ester

0.56

0.30 x 10~3

60

- , di-n-butyl ester

3.5

1.59 x l O " 2

60

13

0.11

50

11
6.8
9.4
6.7
3.4
3.2

0.13
0.07
0.11
0.083
0.068
0.13
1.0 x l O " 3

50
50
50
50
50
50
50

5.3

8.5 x l O " 2

50

5.9

0.053

50

- , di-sec-butyl ester

0.6

4.0 x 10 ~3

60

- , di-terf-butyl ester

0.2

5.6 x 10~3

60

- , dicyclohexyl ester

2.3

1.4xlO" 3

60

- , diethyl ester

7.7

0.24

50

3.7

6.41 x l 0 ~ 2

60

- , diisobutyl ester

2.7

1.56 x 10~2

60

- , diisopropyl ester

1.1

5.0xl0~~ 3

60

- , dimethyl ester

5.2

0.36

60

10

0.59

50

- , a-ethyl-P-hexarluoropropyl ester

5.0

0.28

60

- , a-methyl-P-isopropyl ester
- , a-methyl-P-tert-butyl ester
- , a-isopropyl-P-methyl ester
- , a-fm-butyl-P-methyl ester
AT(2,6-dimethylphenyl)itaconimide

3.4
4.2
1.9
0.91
26

0.06
0.051
0.07
0.056
0.082

60
60
60
60
50

C
C
C
C
C

15

0.29

60

Monomer

Methyl N-phenyl-itaconamate

Remarks
Solvent: benzene 1.5 M
Solvent: hexane 1.03 M
Solvent: cyclohexane 1.03 M
Solvent: toluene 1.03 M
Solvent: benzene 1.03 M
Solvent: chlorobenzene 1.03 M
Solvent: ethyl acetate 1.03 M
Solvent: THF 1.03 M
Solvent: acetone 1.03 M
Solvent: benzene 2.0M,
MAIB 0.05 M
Solvent: benzene 1.5 M, kp and kt
also given by other [M]
Solvent: benzene 1.5M,
MAIB 0.02 M
Solvent: cyclohexane 1.33 M,
MAIB 5.00 x 10~2 M, kp and kt
also given by other temp.
Solvent: n-hexane 1.33 M
Solvent: chlorobenzene 1.33 M
Solvent: methyl benzoate 1.33 M
Solvent: benzene 1.33 M
Solvent: acetone 1.33 M
Solvent: acetonitrile 1.33 M
Solvent: benzene 0.794M,
AIBN 0.05 M kt also given
by other [M]
Solvent: benzene 0.794M,
MAIB 0.05 M
Solvent: benzene 2.0M,
MAIB 0.05 M
Solvent: benzene 1.5 M,
MAIB 0.02 M
Solvent: benzene 1.5M,
MAIB 0.02 M
Solvent: benzene 1.5 M,
MAIB 0.02 M
Solvent: benzene 2.0M,
MAIB 0.05 M
Solvent: benzene 1.5M,
MAIB 0.02 M
Solvent: benzene 1.5M,
MAIB 0.02 M
Solvent: benzene 1.5M,
MAIB 0.02 M
Solvent: benzene 1.5 M,
MAIB 0.02 M
Solvent: benzene 2.0M,
MAIB 0.05 M
Solvent: benzene 2.0M,
MAIB 0.05 M, kp and kt
also given by other [M] and temp.

Solvent: THF 0.44 M,


AIBN 0.05 M, J^p andfct
also given by other [M]
Solvent: DMF 1.4 M,
AIBN 0.05 M, jfcp andfct
also given by other [M] and temp.

Refs.
213
185
185
185
185
185
185
185
185
177
213
182
162

162
162
162
162
162
162
154

154
177
182
182
182
177
182
182
182
195
177
233

195
195
195
195
234

235

TABLE 6. FUMARIC DERIVATIVES


Monomer
Fumaric acid
- , bis (2-methoxy-ethyl) ester
- , bis (2-chloro-ethyl) ester
- , tert-butyl methyl ester
- , tert-buty\ isopropyl ester

- , di-terf-butyl ester
- , dicyclohexyl ester
- , diethyl ester

- , diisopropyl ester

- , dimethyl ester
- , dineopentyl ester
Ethyl o-formylphenyl fumarate

TABLE 7.

M x l O " 6 ) (1/mol/s)

Temp. (0C)

Method

0.19
0.26
0.23
0.51
0.35
0.39
0.61
0.60
0.21
0.015

330 x 10~6
320 x 10~6
150xl0~6
26xlO"6

60
60
60
60
60

C
C
C
C
C

1.75 x l O - 5
30 x 10~6
40 x 10~6
(510-560) x 10" 6
1.64 x l O - 4

60
60
60
30

C
C
C
Al

0.029 0.003

8 xlO-6

30

BlO

0.46
0.31 0.07

(80-100) x 10~6
0.84 x l O - 6

60
30

C
BlO

0.058
0.028
4.0

430 x 10~6
44xlO~6
1.4

60
60
60

C
C
C

k p (1/mol/s)

M x I O " 6 ) (1/mol/s)

Temp. (0C)

Method

7400

7.4xlO"5

40

22.7
570
kp = 3.3 x 106
x exp(- 15000/RT)
11000
3130
8.6
kp = 10 9
x exp(- 4540/7)

92
385
kt = 1.3 x 106
x exp(- 4200/RT)
2100
2300
0.175
kt = 106
x exp(- 2670/7)

-30
20

kp (1/mol/s)
4600
795
556-586
670-770
700
559
1100
1000
895
kp = 2.43 x l O 8
x exp(- 30600/RT)
9500-19000
(15-26) x 102

Remarks

Solvent: benzene l.OM


Solvent: benzene l.OM
Solvent: benzene l.OM
Solvent: benzene l.OM
AIBN
MAIB
Solvent: benzene l.OM
Solvent: benzene l.OM
Solvent: benzene l.OM
AVN (2,2'-azobis-2,4dimethylvaleronitrile),
ACN (l.l'-azobiscyclo-hexane1 -carbonitrile)
ACN, scavenger TPV
(1,3,5-triphenylverdazyl),
sovent: benzene
Solvent: benzene l.OM
ACN, scavenger TPV,
solvent: benzene
Solvent: benzene l.OM
Solvent: benzene l.OM
Solvent: benzene 1.16 M,
MAIB 0.100 M, kp and ^ t
also given by other [M]

Refs.

211
211
211
211
181
181
211
211
211
173

179

211
180
211
211
236

VINYL HALIDES

Monomer
Tetrafluoroethylene

Vinyl bromide
Vinyl chloride

Vinylidene chloride

TABLE 8.

kp (1/mol/s)

Remarks
Large active chain end concentration
measured by addition of inhibitor
in aqueous solution polymn.

Al

Refs.
81

Al

80
44
32

25
25
25
22-75

Al
Al
Al
Al

56
77
18
117

M x I O " 6 ) (1/mol/s)

Temp. (0C)

Method

220
46
2860-3040
2500-3100
2600
51.8
80
59
24
kt =4.16 x 105
x exp(- 21900/RT)
380-760
25

25
15
15.9
15.9
15.9
20
25
25
25

B5
Bl
Al
Al
Al
B4
Al
Al
B4
Al

60
50

E
Al

Quoted in Ref. 80

Solvent: N-methylpyrrolidone 2.0M

VINYL ESTERS

Monomer
Vinyl acetate

Remarks

Solvent: -hexane

At 4% conversion

Using results of Refs. 8 and 15

Refs.
13
47
1
3
4
37
2
15
36
8
64
128

References page 11-15

TABLE 8. cont'd
Monomer

Vinyl benzoate

TABLE 9.

kv (1/mol/s)

t (xIO~ 6 ) (1/mol/s)

Temp. (0C)

Method

Remarks

117zb 12
11310
48 5
97 10
61 9
37 5
8 1
637 101
78
#

31961
35154
239 4 5
311 d= 59
266 7 5
412 104
258 76
94.2 23.7
-

30

Al
Al
Al
Al
Al
Al
Al
Al

32.5
32.5
32.5
32.5
30
15-60

Al
C
C
C
Al
C

Solvent: benzene 2.00M


Solvent: C 6 D 6 2.00M
Solvent: anisole 2.00M
Solvent: fluorobenzene 2.00M
Solvent: chlorobenzene 2.00M
Solvent: ethyl benzoate 2.00M
Solvent: benzonitrile 2.00M
Solvent: ethyl acetate 2.00M
Solvent: ethyl acetate: ethyl
benzoate (1:1 (v/v))
Solvent: benzene
Solvent: benzene 5.41 M
Solvent: ethyl acetate 5.43 M

120
310
530
630
1900
280
1400
4435
64.4
p = 2.0 XlO 6
27.5
x exp[(- 19000 2900)/RT]
Jcp = 2 . 1 x l O 8
x exp(- 27820//?7)
ln[(*t|>]/(1.00-0.07/?)]
= lnJfct[l]-0.50p
106 1 4
253 6 3
185 8
402 3 2
245 13
522 48
168 18
383 76
69 13
257 72
33 3
299 4 4
26733
451 6 5

Monovinyl ether of ethylene glycol


Monovinyl ether of diethylene glycol

Monomer
Styrene

Pressure 5.0 x 10 7 Pa

Fl
30

B5

30

Al
Al
Al
Al
Al
Al
Al

130
130
130
130
130
130
130
130
130
153
153
153
153
112
45
209

kt\p]; kt for pressure p (bar)


t [l] = 52.0x 106
Solvent: anisole 1.01 M
Solvent: benzene 1.01 M
Solvent: fluorobenzene 1.01 M
Solvent: chlorobenzene 1.01 M
Solvent: ethyl benzoate 1.01 M
Solvent: benzonitrile 1.01 M
Solvent: ethyl acetate 1.01 M

122
116
116
116
116
116
116
116

VINYL ETHERS

Monomer

TABLE 10.

Refs.

k p (1/mol/s)

kt (x 10 6 ) (1/mol/s)

5.0 1.0
3.0 0.8

1.5 0.3
1.4 0.3

Temp. ( C )

Method

50
50

Al
Al

Refs.
136
136

STYRENE DERIVATIVES
k p (1/mol/s)

kt (x 10 ~6) (1/mol/s)

Temp. (0C)

Method

40 20
24

80 40
14

15
20

Al
Al

51.9
108
106
102
390
209
18.7
39.5
p = 2 . 1 6 x l 0 7
x exp(- 32500/RT)
22

10.5
32.5
108
-

30
30
30
40
50
50
25
25

Al
Al
Al
D
D
E
B5
Bl
Al

40
50
50

D
D
D

139
223
206

115
2.79
5.96
2t = 2 . 5 9 x l 0 3
x exp(- 9920/RT)
-

Remarks
Dimension of kp and kt: kg/mol/s
From copolymn. data with sulfur
dioxide

Quoted in Ref. 86
Using results of Ref. 20

Catalyst: cumene hydroperoxidetriethylenetetramine


Catalyst: persulfate

Refs.
46
25
16
38
78
59
5
61
6
17
20
24
24
40
67

TABLE 10. cont'd


Monomer

kp (1/mol/s)

M x l O " 6 ) (l/mol/s)

Temp. (0C)

* p = 2.24 XlO 14
xexp(-73510//?r)
50
80
64
370
915
25 3
9 1.5
35 7
19 4
35 5
19 3
29 7
15 4
238
11 2
27 4
31 0.4
*p = 1.09 XlO 7
* t = 1.703 x l O 3
x exp(- 31380/K7)
x exp(- 9489/RT)
66.6
22.4
66.5
p = 2.4 XlO 8
x exp(- 38000 11OO)/RT
187.1
29.4

84

-,p-bromo-,/?-chloro-,/7-cyano-,p-fluoro-,/7-methoxy-

25
60

D
Al

25
25
25
25
25
25
15-30

Al
Al
Al
Al
Al
Al
A2

65
118
Addition of 1 x 10 " 3 mol pyridine
118
Solvent: dodecane 40% by vol
104
100
Solvent: bromobenzene 20% by vol
100
Solvent: diethyl malonate 20% by vol 100
Solvent: diethyl phthalate 20% by vol 100
Solvent: dinonyl phthalate 60% by vol 100
DP = 2500
114

30
25
50-90

Al
C

60
F2
Fl

25
25
40
70

Fl
Fl
Fl
C

16.6-17.0

100

190
-

50
25

C
Gl

kt (m,/i) = 1.97 x 102 (n x m) " 1 2

30

A3

5
30-90

C
Fl
F2

25
25
60

Fl
Fl
B5

91.2
25
30
25
25
28

Gl
Al
Fl
Fl
Fl
Bl
Fl

180 1 0
p = 1.99xl0 7 exp(-30780//?D
In kp = 17.14-1.873 x 10" 9 p
- 3748/r + 2.02 x 10 " 6 p/T
77 4.1
79 5.1
187.0
201.0
167.0
641 48
89
107
92
78
23
In kp = 16.09-28950//?r (overall)
= 16.47-3003/KT (chain length > 4)
* p = 107-10-5
xexp[-(293)xlO3/*r]
fcp = 1.8861 x 107
x exp(- 30737.52//?r)
kp = 4.2060 x l O 8
x exp(- 37468.93/RT)
kp = 4.2458 x 108
xexp(-39014.90//?7)
186
150
219
112
2.92
71

78 1 2
96 9
63.2
51.1
37.9
132
0.6

46
77
35
127
1.06
33

Refs.
73

256
107

Remarks

Bl

kp = 107-630 x exp(- 32510/RT) - 1 2 - 93


25

76
70
380 110
480 1 0

Method

30
30
30
30
0
30

Pressure 5.0 x 10 7 Pa

102
98
98

Special evaluation from steady-state


kinetics and Mn

134

215
kp also given by other [M] and
196
solvents
Solvent/ethanol(25%)6.52M
196
Solvent: methanol (25%) 6.52 M
196
Pressure 2.0 x 108 Pa
186
Over a range of degree of polymn.
188
of the polymer radical from 40 to 410
Conversion 0-20%
174
TBP (terf-butyl peroxide)
kp and kt also given by other temp.
189
Laser-flash-initiated polymn. by
156
benzoin
n: n-mer, m: m-mer,
147
coupling with n-mer and m-mer
223
169
Pressure 1 x 10 5 -2.8 x 108 Pa
214

Solvent:
Solvent:
Solvent:
Solvent:
Solvent:

toluene 50% (v/v)


benzene 3 M
chlorobenzene 3 M
benzonitrile 3 M
toluene

kp also given by other temp.

Solvent: benzene 4.33 M

161
161
204
204
204
178
160
198
220
164
83
200

Bl

131

Fl

227

Fl

30% styrene in benzylalcohol

227

Fl

30% styrene in NMP

227

Al
Al
Al
Al
B5
Al

Solvent: dimethylacetamide

78
78
78
78
12
78

References page 11-15

TABLE 10. cont'd


Monomer

kv (l/mol/s)
kp = 1.67 x 1 0 n
x exp(- 58240/RT)
84
kp = 2.27 XlO 7
x exp(- 32060/RT)
kp = 10 5 7 7
x exp(- 23.0/RT)
&p = 3 . 6 3 x l 0 7
x exp(- 31500/RT)

- , o-methyl- , p-methyl-

Styrene-d8

TABLE 11.

A: t (xl0~ 6 ) (l/mol/s)

66

Temp. (0C)

Method
Bl

73

30

Al
Bl

78
73

24-55

Fl

t = 2 . 5 5 x l 0 4
x exp(- 14200/7?7)

Solvent: toluene 2M

Al

kp (l/mol/s)

Ict (x 10~ 6 ) (l/mol/s)

Temp. (0C)

Method

6.0
186
96.6
12
47
122

0.306
33
8.9
3
3.5
66

10
25
25
25
25
20

Al
Al
B4
B5
B4
Bl

209
17.3
953
22000 4000

43
1.2
65
600 db 200

20
20
20
25

Bl
Bl
B4
Al

k p (l/mol/s)

M x 10 ~6) (l/mol/s)

Temp. (0C)

Method

(7-10) x 10 ~3

190

B4

kp (l/mol/s)

kt(x 10~ 6 ) (l/mol/s)

Temp. (0C)

Method

Maleimide
- , N-tert-amyl- , N-tert-butyl-

69
100

0.048a,0.017b
0.021 a ,0.023 b

60
60

C
C

-,
-,
-,
-,

120
23
120
49

0.20a
0.027 a ,0.015 b
0.15 a ,0.23 b
0.054

60
60
60
50

C
C
C
C

55

0.069

W-Vinylcarbazole
2-Vinylpyridine
4-Vinylpyridine
5-Vinylpyridine
- , 2-methyl-

Af-Vinylpyrrolidone

226
168

Remarks

Refs.
80
76
76
34
75
94

Solvent: methanol 1.95 M, kp


also given as a function of [M]
Solvent: 50% (molar) aqueous methanol 94
Solvent: acetic acid
94
82
Solvent: water
132

ALDEHYDES

Monomer
Formaldehyde

TABLE 13.

Refs.

VINYLHETEROAROMATICS

Monomer

TABLE 12.

Remarks

Remarks
Solid monomer, gamma irradiation

Refs.
95

OTHERS

Monomer

A^m-butyl-dimethylsilylN-tert-octylN-trimethylsilylN-cyclohexyl-

Remarks

Solvent: benzene 1M
(a) Determined from steady-state
equation kt = (2kdf[l])/[P']2,
AIBN 0.005 M;
(b) determined from second order
plot of the decay curve of the
radical concentration, ATMP
(2,2 '-azobis-(2,4,4-trimethylpentane)) 0.02 M, for tert-BMl,
ATMP 0.01 M

Solvent: benzene 0.559 M,


AIBN 1.39 x 10" 2 M
Solvent: benzene 0.698 M,
AIBN 1.00 x 10~2 M, kp and kt
also given by other [M] and [I]

Refs.

205
205

205
205
205
163
163

TABLE 13. cont'd


A: p (1/mol/s)

Jt t (xl0" 6 ) (1/mol/s)

Temp. (0C)

- , AH2,6-diethylphenyl-

2.0

0.0078

60

- , Af-(2,6-dimethylphenyl)-

14

0.034

60

- , AH4-ethylphenyl)-

1200

3.9

60

- , #-(2-methylphenyl)-

190

0.59

60

- , Af-(2-carboethoxyphenyl)- , N-dodecyl-

96
54
104
175
80
128
149

0.10
0.12
0.45
1.0
0.40
0.064
0.17

60
50
50
50
50
50
50

C
C
C
C
C
C
C

386
250
235
196

0.55
-

50
50
50
50

C
C
C
C

33

0.10

50

400

0.07

50

B9

Monomer

- , iV-octadecylOligotetramethylene glycol dimethacrylic


ester (MW 600)

Method

Remarks
Solvent: benzene 1M,
AIBN 5 x 10- 3 M
Solvent: benzene 1M,
AIBN 5 x 10- 3 M
Solvent: benzene 1M,
AIBN 5 x 10- 3 M
Solvent: benzene 1M,
AIBN 5 x 10- 3 M
Solvent: benzene MAIB 0.005 M
Solvent: benzene MAIB 0.01 M
Solvent: toluene MAIB 0.01 M
Solvent: anisole MAIB 0.01 M
Solvent: chlorobenzene MAIB 0.01 M
Solvent: bromobenzene MAIB 0.01 M
Solvent: methyl benzoate MAIB
0.01 M
Solvent: THF, MAIB 0.01 M
Solvent: dioxane, MAIB 0.01 M
Solvent: ethyl acetate MAIB 0.01 M
Solvent: methyl ethyl ketone MAIB
0.01 M
Solvent: benzene AIBN 0.20M, kp
and k[ also given by other [I]

Refs.
183
183
183
183
237
238
238
238
238
238
238
238
238
238
238
239
124

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T r a n s f e r

C o n s t a n t s

P o l y m e r s ,

C a t a l y s t s

S o l v e n t s
S u l f u r

a n d

t o
a n d

I n i t i a t o r s ,

A d d i t i v e s ,

C o m p o u n d s

R a d i c a l

M o n o m e r s ,

i n

a n d
F r e e

P o l y m e r i z a t i o n

A. Ueda
Osaka Municipal Technical Research Institute, Osaka, Japan
S. Nagai
Plastics Technical Association, Osaka, Japan

A. Introduction
B. Tables
Table 1. Transfer Constants
Table 2. Transfer Constants
Table 3. Transfer Constants
Initiators
Table 4. Transfer Constants
Additives
Table 5. Transfer Constants
Compounds
C. Remarks
D. References
A.

to Monomers
to Polymers
to Catalysts and

11-97
11-98
II-98
11-103
11-106

to Solvents and
11-110
to Sulfur
11-150
11-157
11-159

INTRODUCTION

The transfer reaction in radical polymerization describes a


process in which the polymer radical reacts with another
molecule (monomer, polymer, catalyst, solvent, modifier,
etc.) forming a dead polymer and new radical. This new
radical can continue the kinetic chain:

If it is assumed that
(a) all new radicals X# react only by formation of
growing polymer radicals;
(b) all polymer radicals have equal reactivities independent of their size;
(c) all rate constants are independent of solvent;
(d) the consumption of monomer by initiation and
transfer is negligible compared with propagation;
(e) a steady-state concentration of polymer radicals is
quickly established (d[P#]/dr = 0).
The application of these assumptions to the common
reaction scheme results in the following relationship of
ideal kinetics (Ref. 145):

P n , p n 0 = number-average degree of polymerization


obtained in the presence or absence, respectively, of transfer agent X.
[M], [X] = concentration of monomer or transfer agent,
respectively.

The dimensionless transfer constant is defined by the ratio

where kv is the rate constant of propagation.


Based on the tables in the third edition, by K. C. Berger and G. Brandrup.

The left-hand side of this equation is obtained by measuring


the number average molecular weight of polymer at
different concentrations of the transfer agent X, all other
variables being kept constant. In many cases the degree of
polymerization was determined by measurement of viscosity (Remark R). It should be noted that the ratio of

viscosimetric to number average molecular weight shows a


considerable dependence on the molecular weight distribution.
The first term P n 0 of the right-hand side of this equation
is the number average molecular weight measured in the
absence of transfer agent X. This is limited to cases where
the transfer agent is a modifier. In all other cases, Pno is
calculated by combination of several kinetic expressions
and used with its numerical value:

This decrease of the transfer agent concentration with


increasing monomer conversion is important in practice
because very reactive transfer agents are used up preferentially, giving a broad molecular weight distribution if they
cannot be replenished.
In analogy to quickly decomposing initiators with their
criterion of "half-life", one can define, in addition to the
transfer constant Cx, a "half-conversion" U\/2 as that
monomer conversion where the transfer agent is half
consumed:

Initiation
Termination
Propagation
Number-average
molecular weight
where ku fct,d, and k^c are the rate constants of termination,
termination by disproportionation, and termination by
combination, respectively.

The second term of the right-hand side of the above


equation is given by the following expression:

where Cp is the constant of chain transfer with added


polymer before starting polymerization.
The transfer constant of very reactive molecules can be
determined from the rate of disappearance of both transfer
agent and monomer:

The following table demonstrates (with some examples for


a calibration curve) that the "half-conversion" IZ1^2
decreases with increasing transfer constant Cx:
The "Half-Conversion" of Transfer Agents
Cx

U1/2(%)

Cx

Ul/2(%)

0.1
0.2
0.5
1
2

99.9
96.8
75.0
50.0
29.3

5
10
20
50
100

13.0
6.7
3.4
1.4
0.7

The transfer agent must be replenished at this monomer


conversion at the latest, if polymerization is to proceed, still
yielding a narrow molecular weight distribution.
Numerous examples are known of polymerization
systems that possibly do not satisfy basic assumptions:
retardation (Remark J), induced decomposition and primary
radical termination by peroxide or hydroperoxide initiation
(Remarks C and B), diffusion control of termination
(Remark X), electron donor/acceptor complexes (Remarks
JJ), etc. Corresponding data in this table have to be used
with caution.

B. TABLES OF TRANSFER CONSTANTS


TABLE 1. TRANSFER CONSTANTS TO MONOMERS
Monomer

T( 0 C)

Acetic acid, allyl ester

80

Acrylamide

25

Acrylamide, AT,iV-dimethylAcrylic acid, benzyl ester

50
60
60
50
55
60
60
60

- , butyl ester

C M (xlO 4 )
170
700
0.12
0.16
0.2
0.2
0.558
0.651
0.6
1.5
0.883
0.905
0.333
1.05

Remarks

D
E
C2, F13, LL
C2, F13, LL
E

Cl, H, KK
Cl, H, KK

Refs.
29
27
92
74
75
103
560
560
103
272
291
291
561
561

TABLE 1. cont'd
Monomer
Acetic acid, butyl ester (cont'd)
-,ethyl ester

T( 0 C)
60
65
50
60
65
70

- , - 2 ethylhexyl ester
- , methyl ester

70
80
50
55
60
65

70

75
-, tetrahydrofurfuryl ester
-, 2-chloro-, ethyl ester
- , thio-, methyl ester
Acrylonitrile

40
60
60
20
25
30
40
50
60

Allyl bromide
Ammonium chloride, A^-diallyl-MJV-diethyl- , Ar,Ar-diallyl-AW-dimethylAnisole, p-\iny\
Anthranilic acid, vinyl ester
Benzoic acid, vinyl ester

1,3-Butadiene, 2-chloro- , 1,1,2-trichloro1-Butene


2-Butene, cis- , trans3-Butene-2-one, 3-methyl-

60
60
60
60
60
60
0
60
70
60
80
95
50
25
40
50
60
40
50
60
40
50
60
80

C M (xlO 4 )

Remarks

1.25
0.955
0.193
0.90
0.41
0.579
0.332
0.351
0.789
6.28
3.79
0.80
0.275
0.036
0.325
0.10
0.11
0.11
0.37
0.01
0.072
0.16
0.18
0.405
0.224
0.25
0.25
4.0
3.0
560
0.18
0.105
1.5
0.17
0.050
0.27
8.2
0.26
0.3
0.333
0.57
1.02
30
18
7
0.198
0.74
80
6.0
7.0
2.0
4.0
2.32
16
3.1
5.1
7.3
3.2
4.9
11.2
3.0
5.2
10.8
4.00

Cl, H, KK

F7
C, F17, R
C, F17, R
C, F17, R
C, F17, R
C, F17, R
F7
C,AA
B, AA
C, AA
C,AA
CFlO
CAA
C, AA
CFlO
B, AA
CAA
C AA
C, AA
CAA
C, FlO
C AA
C, F2
E
F8
F18
F17
F16
Cl, H, KK
Cl, H, KK
Cl, H, KK
C, R, HH
Cl, F30
Cl, F30

F2
E

Refs.
561
291
306
510
512
512
306
306
512
512
512
510
221
221
221
221
123
221
221
322
221
221
221
221
221
123
221
319
342
140
299
284
196
284
410
376
362
95
23
561
561
561
505
538
538
13
53
139
321,393
26
321
213
153
230
334
334
334
334
334
334
334
334
334
84

Remarks page 11-157; References page 11-159

TABLE 1. cont '6


Monomer
Butyric acid, vinyl ester
Carbamic acid, vinyl-, ethyl ester
Carbazole, A^-vinyl-7H-benzo(2)Decanoic acid, vinyl ester
Ethylene

T( 0 C)
50
80
60
70
50
60

70

26.7
22.3
0.25
11
45.5
0.4
1.4
4.2
5.0
5.32
1.1
3.5
9.0
0.0
1.6
4.7
11.2
5
3.2
3.2
7.0
6.25
19.4
50
6.4
7.8
8.5
11
13.5
10.8
12.3
12.8
23.8

60

42

83
110

130

- , chloro-

50-70
20
25
30
40
50

60

Glutaramic acid, MA^-diisobutyl-,


vinyl ester
- , AW-diisopentyl-,
vinyl ester

Hexanoic acid, vinyl ester


5-Hexen-3-yn-2-ol, 2-methylIsobutyric acid, vinyl ester
Laurie acid, vinyl ester
Maleic anyhydride
Maleic anhydride/methyl methacrylate
Maleimide, A^-(3-dimethylamino-6-methyl-phenyl)
Methacrylamide
Methacrylic acid, bornyl ester
- , butyl ester

-,
-,
-,
-,
-,
-,

tert-butyl ester
o-r-butylphenyl ester
/?-?-butylphenyl ester
n-dodecyl ester
2,3-epoxypropyl ester
ethyl ester

-,
-,
-,
-,
-,

0-ethylphenyl ester
p-ethylphenyl ester
glycidyl ester
hexadecyl ester
isobornyl ester

C M (xlO 4 )

60
70
80
80
60
80
50
75
60
50
60
60
50
60
70
60
60
60
60
45
60
80
90
60
60
60
70
60

51
51
51
36
5.0
46
45.5
750
100
720
10 x 105
2.85
0.54
120 x 105
0.14
0.35
30.41
2.01
80xl05
0.59
0.248
0.259
0.456
0.442
3.63
1.36
45 x 105
0.14
1.85

Remarks

Refs.

F4
Y

71
200
117
522
71
102
102
102
204
205
102
102
102
259
102
102
102
218
94
315
425
58
463
246
379
379
379
392
58
379
379
379
58

C, FlO

106

C, FlO
C, FlO
CFlO

107
107
107
200
226
200
71
175
367
542
515
162
233
515
264
9
550
550
515
198
193
193
193
193
550
550
515
138
162

R, F2
W5
W4, W5
W4
D, W
D, W
W4, W5
W4, W5
W4
C, F21,W5
W4, W5
W4, W5
W4
W3

Y
F5
F3
F4
C, F26
Y
F3

C
F2
JJl

JJl

C
C
JJl
CC
CC
CC
CC
C
C
JJl

TABLE 1. cont'd
Monomer
Methacrylic acid, isobutyl ester

- , n-nonyl ester
- , phenyl ester
- , o-tolyl ester
- , p-tolyl ester
Methacrylonitrile

Methyl methacrylate

J( 0 C)
35
50
60
80
100
60
27
60
60
60
25
60
70
80
0
30

40
50

60

65
70

75

80

Naphthalene, 1-vinyl1,4-Pentadiene, 1,1,2,3,3,4,5,5-octafluoroPhernol, o-vinyl2-Picoline, 5-vinyl1-Propene, 2-chloro-, 2-methylPropionic acid, vinyl ester

90
100
120
50
60
70
110
70
70
80
40
50
60
50

C M (xlO 4 )
0.189
0.179
0.14
0.165
0.224
0.301
0.382
105 x 105
400
0.61
1.13
1.06
2.08
5.81
8.00
10.05
0.128
0.148
0.117
0.260
0.15
30 x 105
242 x 105
0.10
0.15
0.477
241 x 105
0.85
0.07
0.10
0.103
0.18
240 x 105
0.20
0.17
0.20
0.23
0.265
0.29
0.30
0.45
0.807
1.37
240 x 105
0.27
0.33
0.60
0.70
0.25
0.40
0.10
0.38
0.58
290
310
300
500
130
6.7
1600
2.5
4.4
6.9
3.6
48.9

Remarks
DD
DD
F2
DD
DD
DD
JJl
R
C
C
C
Z
Z
Z
Z

D
JJ2
JJl
F2
D
JJl

C
JJO
CFlO

C, F17
D
JJl
CFlO
C
CFIl
C, F2

WlO

Refs.
193
193
264
264
193
193
193
515
534
550
550
550
125
125
125
125
69
18
69
224
508
525
528
147,327
145
224
528
69
274
34,290,317
316
145
556
123
123
267
145
440
123
123
104
224
459
528
123
123
123
123
145
123
147
145
145
216
216
216
68
186
11
27
334
334
334
158
71

Remarks page II-157; References page II-159

TABLE 1. cont'd
Monomer
Pyridine, 2-vinyl- , 4-vinyl2-Pyrrolidinone, 1-vinylStearic acid, vinyl ester
Styrene

T( 0 C)
15-35
25
20
50
O
25
27
30
45
50

60

67.8
70

75

80
80.3
90

99
100

110
117
132

Styrene, p-boromo-, o-chloro-

50
30
50

C M (xlO 4 )
O
6.7
4.0
69.8
O

Remarks
D

BB
0.108
0.279
0.358
0.31
0.2
0.32
0.3
0.35
0.40
0.50
0.6
0.62
0.65
0.78
0.07
0.6
0.6
0.6
0.75
0.79
0.85
0.92
1.1
1.37
20 x 10 5
1.0
O
0.6
0.6
0.8
0.96
1.16
1.35
2.0
O
1.6
5.0
5.00
0.7
0.75
1.00
4.0
0.85
1.25
1.47
1.79
1.5
1.72
1.8
1.83
2.80
1.40
2.45
3.0
3.4
5.33
23
0.25
0.25
0.28

A
BB
BB
H
F2
C, H
C
A, K
B, C, H
A
C
C
BB
A
A, F

C
JJl
CFlO
BB
B, H
A
A
C, F2
C,F10
C
C, F2
CFIl
BB
BB
CF
A
A
A
A, F
A
A
A
A, F
A
A

C
C, H

Refs.
38
283
59
71
360
17,69
69,245
17
145
318,360
245
360
354,355
318,327
388
145
145
388
146
467
34,171,223
145,240
318,360
467
145
145
447
53
234
515
34
123
104
360
388
67
145
145
123
123
123
123
123
98
360
318
34
360
145
145
145
98
145
145
145
145
318
145
145
145
145
192
62
60
60

TABLE 1. cont'd
Monomer
Styrene, p-iodoSuccinimide, JV-vinylValeric acid, 4-methyl-, vinyl ester
Vinyl acetate

T( 0 C)
50
55
80
-60
-40
-20
-20
O
20
25

40
45
50

60

65
70
Vinylidene chloride

50
60

C M (xlO 4 )

Remarks

Refs.

1.9
0.55
24.8
1.9
0.40
0.60
0.70
0.30
0.50
0.90
0.96
0.94
0.90
1.3
1.45
2.4
10.7
1.29
1.32
2.0
0.25
0.41
0.54
0.61
1.29
2
4.55
20
1.75
1.8
1.9
1.91
1.93
2.0
2.1
2.4
2.5
2.5
2.6
2.8
2.1
2.4
2.9
22
38

Fl
C

113
R
R

56
93
200
158
464
464
464
241
241
86
464
328
241
86
86
202
69
12
328
51
466
265
265
265
12
552
71
225
12
466
124
328
348
231
145
294
86
167
167
80
466
403
86
541
541

C P (xlO 4 )

Remarks

Refs.

D
D
D
D
D
14
D
D
17
17
D

W14
W15
C

112
C

C
C

TABLE 2. TRANSFER CONSTANTS TO POLYMERS


Polymer
Acrylamide, N,N-dimethylPoIy(N, Af-dimethylacrylamide)
Acrylic acid, ethyl ester
Poly(methyl methacrylate)
- , methyl ester
Poly(isoprene)
- , chlorinated
Poly (methyl acrylate)
Poly (methyl methacrylate)
Acrylonitrile
Cellulose

T( 0 C)
50

0.61

272

60

12800

M6

120

75
60

12.6
0.5
1.0
18000

C, F2
L
L
M6

308
212
105
120

1.0
11
20

L, N
L, M4
L, M5

361
361
361

60
60

Remarks page 11-157; References page 11-159

TABLE 2. cont'd
Polymer
Acrylonitrile, (cont'd)
Poly(acrylonitrile)
Poly(methyl methacrylate)

Poly(sarcosine)
1,3-Butadiene
PoIy(1,3-butadiene)
Ethylene

-, chloro
Poly(vinyl chloride)
Hexanoic acid, vinyl ester
Poly(oxyethylene), dodecyl ether
Methacrylic acid, butyl ester
Poly(methyl methacrylate)
-, dodecyl ester
Poly (methyl methacrylate)
-, ethyl ester
Poly(isoprene), chlorinated
Poly (vinyl chloride)
Methyl methacrylate
Poly(ethylene)
Poly(isoprene), chlorinated
Poly(methyl methacrylate)

T(0C)

50
60
60

60

Poly(vinyl chloride)
Poly(vinyl urethane)
Rubber, natural
2-Pyrrolidinone, 1-vinyl-dextran
Dextran

376
135
25
25
25
25
23

C,
C,
C,
C,
C,
C,
C,
C,
C,
C,

50

60

780

60

7700

M6

120

60

12800

M6

120

C, F2
C, F28

308
308

70
70

18.3
21.0

50
80
40

0.6
23.4
1.5
360
0.22
1.5
1.5
360
360
1000
0.1
1.5
2.1
360
2.48
0.22
1000
0.04
1.0
0.42
0.75
2.20
2.95
2.0
2.8
11
10.0
17
10.9
11.0

80
90

Poly(vinyl acetate)

F14
L
N
M2
M3
M

Refs.

11
108.40
150.70
194.81
214.46
337.31
256.85
195.81
199.89
155.78
348.46

60

Poly(styrene)

4.7
3.5
0.2
240
900
1270
400

Remarks

50
174.8
201.6
215.0
231.2
230.3
229.2
230.3
230.4
230.5
256.0

50

Poly(propylene)

C P (xlO 4 )

50
130
50
60
80
60
80
70
50
50
50

5
5.87

W20, F32
W20, F32
W20, F32
W20, F32
W22, F32
W21, F32
W20, F32
W19, F32
W18, F32
W20, F32

142
540
540
540
540
540
540
540
540
540
540
211
278

C, F17
N
M
N
N
M
M
N
M
N
M
N
M
C

C, F28
C, F8
C

209
307
326
326
147
326
327
326
327
147
105
326
262
326
262
147
147
292
209
292
148
262
262
263
263
250
308
157
258
258
333
203

TABLE 2. cont'd
Polymer
Styrene
Poly(oxyadipoyloxy-2,2-dibromomethyl trimethylene)
Poly(oxyethylene)
- , dodecyl ether
Poly(oxythexamethyleneoxy sebacoyl)
Poly(methyl methacrylate)

T( 0 C)

60
70
70
60
80
50

60

Poly(propylene)

Poly(styrene)

80
100
60
66
130
50

55
60

73.5
85
90
100
110

Poly(vinyl acetate)
Poly(vinyl chloride)
Poly(2-vinylpyridine)
Vinyl acetate
Poly(oxyethylene)
- , dodecyl ether
Poly (methyl methacrylate)
Poly(styrene)
Poly(vinyl acetate)

130
154
100
130
50
60
60
60
75
40
60
75
-15
0
11
21
31
40
50

C P (xlO 4 )
4.05
19
14
20
13
0.4
<0.3
1110
1140
16.4
17.5
5.7 x 104
32 x 104
3.74
6.04
0.025
26
0.3
0.30
1.9
4.5
14.0
16.6
15
0.8
1.9
3.1
15.4
15.8
16.6
1.0
1.4
5.8
2.0
9.2
10.8
1.8
1.5
6.6
9.2
160
8-10
17
40
10
40
750
21
26
12
15
19
0.36
0.5
1.7
2
4
16
11.2
30.9
32.0
0.06

Remarks

L
MlO
MlO
C, N
N
M
N
M
Ml
Ml
M7
M6
C

Ml
Ml
C
C
N

N
M
M8
M9

O
O
O

W15

Refs.

325
562
562
278
394
327
326
326
327
64
64
120
120
262
262
292
486
292
207
144,148
327
327
176
177
105
73
105
64
64
176
8
8
327
276
177
176
43
43
263
263
250
279
277
277
277
277
271
263
263
263
263
263
97
97
350
145
145
145
12
43
263
265

Remarks page 11-157; References page 11-159

TABLE 2. cont'd
T( 0 C)

Polymer
Vinyl acetate {cont'd)
Poly (vinyl acetate) (cont 'd)

60

60-70
70
Poly(vinyl acetate-co-vinyl chloride)

TABLE 3.

60

C P (xlO 4 )

Remarks

0.11
0.15
3
10.2
1.2
1.4
1.8
1.9
2.5
3.0
4.0
6.8
8.0
47.0
3.5
2
4
0.21
3.0

W14

P
O
VCL-Part
VOAC-Part

Refs.

265
265
43
12
124
168,169
348
328
329
165
105
12
105
263
350
403
403
166
166

TRANSFER CONSTANTS TO CATALYSTS AND INITIATORS

Catalyst/Initiator
Acrylamide
Bisulfite ion
Hydrogen peroxide
Potassium persulfate
Acrylic acid, benzyl ester
Isobutyronitrile, 2,2'-azobis-

- , ethyl ester
Isobutyronitrile, 2,2'-azobis- , methyl ester
Benzoyl peroxide

2-Butanone, peroxide

T(0C)

tert-Butyl peroxide

Chloroform/CuCl2
Acrylonitrile
Isobutyronitrile, 2,2'-azobis-

Azodiphenylmethane, benzyl-

-, cyclohexyl-

Remarks

0.17
0.0005
0.0258
0.028

55
60
65

0
0
0

291
291
291

65

306

55
60
65
70
65

60
70
65
70
75
120

0.0143
0.0246
0.0375
0.01
0.05
0.05
0.05
0.077
0.113
0.113
0.01
0.0266
0.00047
0.00082
0.00111
600

F13
D
F13, LL
F13, LL

Refs.

75
25
50
60

70
75
tert-Butyl hydroperoxide

Ci

C, FlO
FlO

FlO

Q(5-19), Fl

352
92
560
560

221
221
221
322
221
123
221
221
123
221
221
221
221
221
221
551

50
60

0
0

F16

362
95

50
60
80
50
60
80

0.07
0.07
0.07
0.02
0.04
0.05

R
R
R
R
R
R

536
536
536
536
536
536

TABLE 3. cont'd
Catalyst/Initiator
Azodiphenylmethane (cont'd)
- , 1-phenylethyl-

- , 2-propyl-

Benzoic acid, vinyl ester


Benzoyl peroxide
Isobutyronitrile, 2,2'-azobis3-Buten-2-one, 3-methylBenzoyl peroxide
Ethylene
Azoethane, 1,1 '-dimethylEthylene, chloroValeronitrile, 2,2'-azobis[2,4,4-trimethylMaleic anhydride
Benzoyl peroxide
Methacrylonitrile
Isobutyronitrile, 2,2'-azobisMethyl methacrylate
Acetophenone, 2-diazo-2-phenyl/7-Anisoyl peroxide
Benzoyl peroxide

2-Butanone peroxide

T (0C)

Remarks

0.1
0.1
0.1
0.02
0.04
0.05

80
80

0.0527
0

26
26

80

0.0509

84

83

0.5
0.51

25

0.85

425

75

2.63

175

60

125

70
60
50
60

0.0
0.037
0.01
0
0.02
0.0025
0.00698

459
316
145
34
145
123
123

65

75

80
tert-Buty\ hydroperoxide
terf-Butyl peroxide
Butyronitrile, 2-ethyl-,2,2'-azobis- , 2-methyl-, 2,2'-azobis- , 2,3,3-trimethyl-, 2,2'-azobisCinnamoyl peroxide
Cobalt, [bis-[ja-[(2,3-butane-dionedioximato)(2-)-O,O;]]
tetrafluorodiborato(2-)-A^',vV",;V'']-

60
20
60
60
60
60

Cyclohexanecarbonitrile, l,l'-azodiCyclopropanecarboxylic acid, 1-methyl2-(9/-anthryl)-, methyl ester


Hydrogen peroxide
Hydroperoxide, a,oc-dimethylbenzyl
Isobutyronitrile, 2,2'-azobis-

60

Methane, diazodiphenylPalmitoyl peroxide

70
60
60
50
60
70
60

Peroxide, bis(ra-chlorobenzoyl)
- , bis(o-chlorobenzoyl)

60
60

60
60

0.0033
0.0033
0.0040
0.0092
0.00553
0.00667
0.0071
0.0089
0.0111
0.0128
1.27 x [cat]
< 0.0001
0
0
0
0.009
36000
2500
0
0.002
0.046
0.33
0
0
0.0
0
0.16
0.003
0.019
0.35
0.8
0.009
0.012

R
R
R
R
R
R

Refs.

50
60
80
50
60
80

70

- , bis(p-chlorobenzoyl)
- , bis(m-nitrobenzoyl)

C1

D, W
D, W

12
F2

F17
FlO
FIl
FIl
F2
FlO
F17

C, D

536
536
536
536
536
536

204
205

123
123
123
123
123
123
123
123
123
123
34
35
317
317

317
316
563
F17
317
440
FIl
F2
FlO

111

FlO
110

563

290
34
327
34,290,317
267
316
145
316
316
290
145
316
316

Remarks page 11-157; References page 11-159

TABLE 3.

cont'd

Catalyst/Initiator
Methyl methacrylate (cont'd)
- , bis(p-nitrobenzoyl)
- , bis(m-phenylazobenzoyl)
2-Tetrazene, 1,1,4,4-tetramethyl0-Toluoyl peroxide
Valeronitrile, 2-methyl, 2,2'-azobisStyrene
Acetyl peroxide
p-Anisoyl peroxide
Benzoyl peroxide

J(0C)

Ci

60
50
30
60

0.144
0.00001
0.038
0.046
0.06
0

60
70
70
22
50
60
70

80
Cobalt, [Bis-[^-[(2,3-butane-dionedioximato)(2-)-O,O/]]
tetrafluorodiborato(2-)-N,iV/,A^//,N//]Di-3-phenylazo benzoyl peroxide
2-Butanone, peroxide

50
70
90
50
70
75

tert-Butyl hydroperoxide

Butyl peroxide
sec-Butyl peroxide
tert-Buty\ peroxide

60
70

80
60
80
60
80
60

70
80
Butyryl peroxide
Cinnamoyl peroxide
Crotonyl peroxide
Cyclohexanone peroxide
Ethyl peroxide
Formamide, 2-cyano-2-propylazoFuroyl peroxide
Hexanoyl peroxide
Hydroperoxide, a,a-dimethylbenzyl

70
70
70
60
60
80
100
70
70
40

0
0.074
0.1
0.13
0.048
0.055
0.101
0
0.075
0.12
0.18
0.13
0.813
1500
6.7
5.5
4.8
0.46
0.0667
0.1250
0.1670
0.1250
0.1670
0.2000
0.243
0.035
0.051
0.060
0.063
0.064
0.066
0.003
0.00076
0.00092
0.0029
0.0004
0.0021
0.00023
0.0003
0.0006
0.00086
0.0013
0.039
0.0022
0.0033
0.018
1.10
0.146
0.062
0.00066
0.0024
0.17
0.23
0.166
0.052

Remarks

C
D
111

F17
R
R
R
H
F2
FlO
FIl
F2
FlO
FIl
H
F6
F2, F5
F9
F2
F9
F2
F2
F9
F2, F12
F2
F2

F2
F2

Refs.

316
282
483
316
145
317
87,217
87
65
58
171
240
234
217
87
67
58,65
58,65
530
563
527
527
527
388
123
123
123
123
123
123
123
171
388
399
400
400
400
385
302
302
302
301
301
303
303
303
300
304
400
303
385
87
87
87
33
301
301
47
87
87
388

TABLE 3. cont'd
T( 0 C)

Catalyst/Initiator
Styrene (cont'd)
Hydroperoxide, a,a-dimethylbenzyl (cont'd)

-, a,a-dimethylbenzyl,
/?-isopropylIsobutyronitrile,2,2'-azobis-

50
60
70
70
50
60

Isopropyl peroxide
Lauroyl peroxide

60
80
70

p-Menth-8-yl hydroperoxide
Myristoyl peroxide

84
50
70

2-Naphthoyl peroxide
Nickel peroxide
Octanoyl peroxide

70
60
70

Oleoyl peroxide
Palmitoyl peroxide
Peroxide, bis(p-acetoxybenzoyl)
-, bis(ra-bromobenzoyl)
-, bis(o-[bromobenzoyl)

70
70
70
70
50
70
70
70
70
22
70
70
70
60
70
50
70
70
70
50
70
70
70
70
70
90
70
50
70
70
70
80
90
80
90
80
90
80
90
70

-, bis(/?-bromobenzoyl)
- , bis(p-ter-butylbenzoyl)
-, bis(m-chlorobenzoyl)
Peroxide, bis(o-chlorobenzoyl)
- , bis(p-chlorobenzoyl)
- , bis(/7-cyanobenzoyl)
- , bis(2,4-dichlorobenzoyl)
-,
-,
-,
-,
-,
-,
-,
-,
-,
-,

bis(oc,a-dimethylbenzyl)
bis(m-fluorobenzoyl)
bisO-fluorobenzoyl)
bis(p-fluorobenzoyl)
bis(hydroxyheptyl)
bis(m-iodobenzoyl)
bis(/?-methoxycarbonyloxy-benzoyl)
bis(m-nitrobenzoyl)
bis(/?-nitrobenzoyl)
bis(m-phenylazobenzoyl)

- , bis(5-phenyl-2,4-pentadienoyl)
- , bis(2-thiophenecarbonyl)
-,
-,
-, butylidenebis[rm-butyl

tert-butoxymaleoyl
tert-butoxyphthaloyl

-, sec-butylidenebis[terf-butyl
-, isobutylidenebis[terr-butyl
- , isopropylidenebis[tert-butyl
Pinanyl hydroperoxide

Ci
0.069
0.063
0.082
0.10
0.033
0
0
0
0
0.012
0.16
0.0003
0.0015
0
0.024
0
0.048
0
0.116
0.178
0.00265
0
0.098
0.154
0.142
0.187
0.465
1.0
2.17
0.193
0
0.346
2.0
1.91
0.216
0.804
2.9
2.6
0.01
0.246
0.40
0.219
< 0.005
0.262
0.208
6.2
7.4
5.5
4.8
5.24
0.23
0.38
1.52
0.018
0.00077
0.00140
0.00072
0.00115
0.00083
0.00155
0.00040
0.00105
0.026

Remarks
H
H
H
F2
H

F2
F2

C, F2

C
C

C
C
C
C
C
C
C
C
H

Refs.
388
171
388
399
388
327
388
171
318
468
447
301
301
217
87
217
388
217
87
87
266
217
87
87
87
87
87
58,65
87
87
87
87
65
87
217
87
217
217
388
87
87
87
388
87
87
87
87
281
281
87
65
65
87
87
411
411
411
411
411
411
411
411
388

Remarks page II-157; References page II-159

TABLE 3. cont'd
Catalyst/Initiator
Styrene (cont'd)
Pivalonitrile
Propylene, oxidized
Propyl peroxide
Sorboyl peroxide
Stearoyl peroxide
Succinonitrile, tetramethyl2-Tetrazene, 1,1,4,4-tetramethylo-Toluoyl peroxide
/7-Toluoyl peroxide
9-Undecenoyl peroxide
Valeronitrile, 2,2/-azobis[2,44-trimethylVinyl acetate
Benzoyl peroxide

T( 0 C)

60
60
70
60
70
70
60
30
70
50
70
70
25
60

Lauroyl peroxide
Palmitoyl peroxide

65
50
60
60
60

Peroxide, bis(m-bromobenzoyl)

60

- , bis(o-bromobenzoyl)

60

- , bis(/?-bromobenzoyl)
- , bis(o-chlorobenzoyl)

60
60

Isobutyronitrile, 2,2/-azobis-

Ci

0.000038
1.01
1.14
0.00084
1.19
0.154
0.000037
0.038
0.175
0.17
0.003
0.19
0.065
0.59
0.032
0.09
0.15
0.040
0.025
0.055
0.10
0.10
0.17
0.24
0.6
0.25
3.5
0.17
0.17

Remarks

13
13
13
13

Refs.

468
396
396
305
87
87
468
483
87
65
87
65
87
426
465
231
80
466
466
466
80
80
145
80
145
80
145
80
145

TABLE 4. TRANSFER CONSTANTS TO SOLVENTS AND ADDITIVES


Solvent/Additive
Acetic acid, allyl ester
Benzene
/7-Benzoquinone
-, 2,3,5,6-tetrachloro- , 2,3,5,6-tetramethyl- , 2,3,5-trichloroCarbon tetrachloride
Phosphorus trichloride
Acrylamide
Acetonitrile
tris(2-Carbamoylethyl)amine
Iron(III) chloride
Isopropyl alcohol
Methanol
Propionamide

Water
Acrylic acid, butyl ester
Aniline, MN-dimethylEthanol
Methanol
Propanol
Iso-propanol

J( 0 C)

C s (xlO 4 )

Remarks

80
80
80
80
80
100
40

21.0
5.2 x 105
16 x 105
4.14 x l O 4
5.5 x 105
2.0 x 104
1.0 x 104

J
J
J
J
C
C, D

25
50
80
30
25
60

5.5
85
4.26 x 104
19
7.2
0.13
220
64

25
40
50
80
80
80
80

0.204
5.8
380
4.28
0.47
3.78
14.12

F13
Fl 3

Refs.

273
27
27
27
27
210
214

F13
F13, S
C, F13
E
E

564
564
75
353
353
130
103
103

C, F13
F13

437
444

A, R
F31, A, R
A, R
A, R

161
548
548
548
548

TABLE 4. cont'd
Solvent/Additive
Acrylic acid, ethyl ester
Acetic acid
Acetone

Acetonitrile

Aniline, A^-dimethylBenzene

-, bromo- , chloro- , ethyl-

2-Butanone

Butyl alcohol

sec-Butyl alcohol

terf-Butyl alcohol

Butyric acid
Carbon tetrachloride

Chloroform

Cumene

Cyclohexane

T( 0 C)

50
80
100
40
60
80
100
50
60
80
100
50
50
60
80
100
60
80
100
40
80
100
40
60
80
100
50
60
80
90
40
60
80
100
45
63
80
100
40
60
80
100
80
40
60
70
80
100
40
60
70
80
100
50
60
80
90
50
60

C 8 (xlO 4 )

0.176
0.537
1.05
0.207
0.27
1.10
2.30
0.158
0.245
0.55
1.43
2300
0.016
0.22
0.27
0.45
0.525
2.2
0.163
0.685
3.34
0.054
0.37
1.68
0.668
11.6
16.80
28.7
1.44
0.151
1.92
3.29
4.45
1.28
2.91
5.85
12.6
10.6
18.5
22.20
31.5
0.068
0.17
0.712
1.64
0.855
0.332
0.90
3.2
1.13
1.55
2.80
0.195
0.89
1.57
1.49
4.74
11.7
13.8
22.2
26.0
28.9
0.48
0.61

Remarks

A
A
C
A
A
A
A
F16
C
C
A
A
A
A
A
A
A
A
C
A
A
A
A
A
A
A
A
A

C
A
A
C
C
A
A
A
A
C

Refs.

472
471
472
472
134
471
472
472
472
471
472
228
472
472
133
134
471
472
472
471
472
472
471
472
472
472
471
472
472
134
472
471
472
472
472
471
472
472
472
471
472
472
472
471
472
471
472
472
416
134
471
472
472
134
134
471
472
472
472
471
472
472
472
134

Remarks page II-157; References page II-159

TABLE 4. cont'd
Solvent/Additive
Acrylic acid, ethyl ester (cont'd)
cyclohexane (cont'd)
Dimethylformamide
Ethanol
Ethyl acetate

T( 0 C)

C s (xlO 4 )

Remarks

80
100
50
80
50
60

1.22
3.08
0.1
4.38
0.298
0.448
0.69
0.89
1.82
0.046
0.524
0.593
0.97
1.46
2.1
3.31
4.65
8.06
21
28.70
0.32
1.70
0.36

A
A
F7
A, R

80
100
80
50
60
80
100
45
63
80
100

Formic acid
Heaxane

Isobutyl alcohol

Isopropyl alcohol
80
60

Methanol

80

Propanol
Toluene

80
40
50
60
70
80
100

- , 2-ethylhexylester
Toluene
- , methyl ester
Acetone

70
80

28.70
2.13

60
80

0.23
0.622
1.1
<2.5
480
<1.0
60
42.1
26.7
72.7
1000
0.326
0.45
0.52
0.986
0.71
309
6.056
46.4
2040
107
<1.0
600
1890
1000
3.92
400
1200
33.1
1600

Acetophenone
Aluminum, triethyl
Aniline
-,MTV-dimethyl- , m-nitro-,p-nitroAnisole, m-nitroAnthracene
Benzene

50
60
50
50
50
50
50
50
80

- , chloro-

80

- , 0-dichloro-,
-,ethyl- , nitro- , 1,3,5-trinitroBenzoic acid, /?-nitroBenzonitrile
Copper(II) chloride
Phosphine, tributylPhosphorus trichloride
Propanol
Silane, dimethyphenyl- , methyldichloro- , tetraethyl- , trichloro-

ra-dinitro-

4.73
0.88
0.611
0.929
1.37
1.84
2.60
6.80

80
50
80
50
50
50
50
120
60
40
80
60
60
60
60

C
A
A
A

A
A

A
A
C
A, R
C
4
A, R

A,R

Refs.

471
472
510
548
472
472
134
471
472
471
472
472
471
472
472
472
471
472
445
548
134
472
548

C, F17, R
C, F17, R
C, F17, R
C
A
A

548
472
512
512
512
134
471
471

C, F17, R
C, F17, R

512
512

470
332
111
15
156
15
228
15
15
15
15
332
111
111
332
111
15
332
15
15
15
15
565
156
214
548
539
539
156
539

C
F2, S
F16

C
C
C

F34
F2
C, D
A, R
A, R
A, R
F2
A, R

TABLE 4.

cont'd

Solvent/Additive
Acrylic acid, methyl ester(cont'd)
- , triethyl- , triphenylStearic acid, methyl ester
Toluene
- , m-nitro-,/7-nitroTriethylamine
Tripropylamine
- , tetrahydrofurfuryl ester
Carbon tetrachloride
Acrylonitrile
Acetaldehyde
Acetamide, AW-dimethylAcetic acid
Acetone
Acetonitrile
Acrolein, bis(2-ethoxyethyl)acetal
- , bis(2-butoxyethyl)acetal
Aluminum, hydrodiisobutyl
-,triethyl
- , triisobutyl
Aniline

- , N,N-diethy\-

T( 0 C)

Remarks

Refs.

A, R
A, R

50
50
60
60

300
800
0.751
2.7
1.775
2.7
41.2
48.6
400
470

539
539
441
21,24
332
111
15
15
24
156

40

1.0

C, F2

60
60
60
60
80

50
50
50
50
60
50
60
60
60
60
60
100
100
40
50
60
40
50
60

Aniline, AW-dimethyl-

40
50

60
Anthracene
Arabinose
Benzene
- , bromo- , tert-butyl- , chloro-,ethyl- , iodoBenzoic acid, vinyl ester
/7-Benzoquinone
Borane, tributyl
2-Butanone
- , 3-methyll-Buten-3-yne
Butyl alcohol
sec-Butyl alcohol
tert-Butyl alcohol

C s (xlO 4 )

50
60
60
60
60
60
60
60
65
50
60
60
60
50
60
60
60

14
47
4.945
5.05
0.81
1.7
1.13
0.7
2.0
120
90.5
3940
590
17.0 x 104
28.0 x 104
32.0
44.0
9600
1.22 xlO 4
215
5.8IxIO 4
359
9.38 x 104
547
14.3 x 104
605
1.19 xlO 4
708
1040
1.5 x 104
1.54 xlO 4
870
964
2.18 xlO 4
1.8 x 104
13.0
2.46
1.36
1.93
0.79
35.73
5.19
1400
1.3 x 104
6470
6.43
21.08
3800
15.42
97.55
0.44

F2

F
F7
F14
F14
F
F14
Fl 5
F7
F7
F7
F7
F7
F7
F2, G
F2, J
F16, G, J
F16, G, J
F2, J
F16, G, J
F2, J
F16, G, J
F2, J
F16, G, J
F2, J
F16, G, J
F2, J
F16, J
F16, G, J
J
F2, J
F16, G, J
F8
G
G, S
G
G, S
G
G, S
F7
G
G
F7
G
G
G

319
436
377
375
197
377
377
95
377
86
499
156
156
156
247
247
229
229
227,229
229
229
229
229
227,229
229
229
229
229
229
161
228
227,229
24
229
229
15
361
95
95
95
95
95
95
136
15
156
95
95
377
95
95
95

Remarks page 11-157; References page 11-159

TABLE 4. cont'd
Solvent/Additive
Acrylonitrile (cont'd)
Butyric acid, 4-hydroxy-y-lactone
Cadmium, dibutyl
Carbonic acid, cyclic ethylene ester

Carbon tetrabromide
Carbon tetrachloride

T( 0 C)
50
60
50

60
50
60

Copper(II) chloride

60
80
60
80
35

Copper(II) sulfate

60
35

Chloroform

Crotonaldehyde
Crotononitrile, transCumene
Cyclohexane
-,methylDimethylamine
m-Dioxane, 5,5-dimethyl-2-vinylm-Dioxane, 5,5-dimethyl-2-vinyl- , 4-methyl-2-vinyl- , 2-vinyl1,3,-Dioxolane, 2-vinyll,3-Dioxolane-4-methanol, 2-vinylDiphenylamine-T
Erythritol
Ethane, 1,2-dichloro- , 1,1,2,2-tetrachloro- , 1,1,1-trichloro- , 1,1,2-trichloroEthanol, 2,2MmInOdI- , 2,2',2"-nitrilotriEther, dodecyl vinyl
Ethyl acetate
Formamide, N,N-dimethyl-

50
50
60
60
60
50
60
60
60
60
60
60
60
60
60
60
60
30
30
50
60
20
25
40
50

60

C s (xlO 4 )
0.658
0.74
5.5 x 104
0.073
0.33
0.39
0.474
0.5
0.511
1.0
0.128
400
500
1900
0.85
1.13
5.64
5.90
1.8 x 105
1.9 xlO 5
3.2 xlO 5
10 x 105
1900
2800
3000
1.07 x 104
1.35 xlO 4
3.93 x 104
13.6 x 104
21.OxIO 4
47
19
41.41
2.06
2.31
175
2.20
4.40
2.71
16.60
2.40
700
12.8
1.47
3.11
1.25
1.68
10.1
76.0
4.95
2.54
1.4
4.97
3.24
1.0
2.70
2.78
2.8
2.83
10
2.412
4.494
5.0

Remarks

F7

F7, J
G
C
G
C
U(0.01)
U(0.1)
U(l.O)
F7
F13, J
J, V(0.0001)
J, U(0.01)
J, V(0.001)
J, U(0.1)
J, V(O.Ol)
J, U(LO)
J, V(0.1)
F7
F7
G
G
G
F7
F7
F7
F7
F7
F7
F7
F8
G
G
G
G
F13
F13
C
G
C, J, F7
D, J
E

F7

F15

Refs.
375
374
156
293
197
374
375
404
458
356
293
493
20
24
96
336
95
336
402
402
402
37
402
402
402
402
402
402
402
402
377
377
95
95
95
377
498
498
498
498
498
61
361
95
95
95
95
476
476
4
95
248
91
458
347
374
197
377
375
356
347
22
86

TABLE 4. cont'd
Solvent/Additive
Acrylonitrile (cont'd)
Formamide, A^N-dimethyl- (cont'd)
-, Af-methylFormic acid
Glucose
ot,D-Glucoside, methyl- , -, 6-deoxy-6-iodo- , - , 6-deoxy-6-mercapto- , - , 6-deoxy-6-phthalimido- , -, 2,3-di-O-benzyl- , -, 2,3,4,6-tetra-O-acetyl- , -, 6,-O-(/?-toluenesulfonyl)- , - , 6-O-triphenylmethylP,D-Glucoside, methyl- , - , 6-deoxy-6-dipropylaminoGlutaronitrile, 2,4-dimethylGlyceraldehyde
Glycerol
2,4,6-Heptanetricarbonitrile
1-Heptanol, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluorol,5-Hexadien-3-yne
Hydrocyanic acid

T( 0 C)

50
50
60
60
60
60
60
60
60
60
60
60
60
50
60
60
50
60
50
50

Indium, triethyl
Iron(III) chloride
Isobutyl alcohol
Isobutylene
Isobutyronitrile

60
60
60
60
50
60

Lactonitrile
Lead, tetraethyl
Magnesium perchlorate
Mercury, diethyl
Methane, dichloro- , nitroMethanol
Methylamine
2,6-Octadiene, 2,6-dimethylOxime, acrolein
-, crotonaldehyde-, ethylisopropenylketone-, methacrolein-, methylacrolein-, methylvinylketone-, methylisopropenylketone-, methylisobutenylketone1-Pentanol, 2,2,3,3,4,4,5,5-octa-fluoro1-Pentanol, 4-methylPiperidine, 1-ethyl- , 1-methyl1-Propanol, 2,2,3,3-tetrafluoroSilane, tetraethyl
Sorbitol
Stibine, tributyl
Succinonitrile
Sulfur dioxide
Tin, tetrabutyl
Toluene

50
60
50
60
60
60
50
50
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
50
60
50
60

o-Toluidine, MN-dimethyl-

40
50

C s (xlO 4 )

1.8
0.5
6.9
20
50
1300
60
90
30
10
80
20
1100
0.6
32.1
23.5
1.0
1.9
1.17 x 104
0.81
6.2
2220
3.33 x 104
24.06
70
1.3
1.8
3.5
4.0
1
243
< 0.05
72.2
3.06
6.0
0.5
175
450
6.26 x 105
2.05 x 104
1.03 x 104
9.41 x 104
5.35 x 104
1.2 x 104
1.71 x 104
2.65 x 104
1.9
11.79
3300
2300
1.5
21.0
6.1
11.1 x 104
0.6
0
80.8
1.153
2.632
3.2
5.83
272
334

Remarks

Refs.

F14
F14
F8
F7
F7
F7
F7
F7
F7
F7
F7
F7
F7
F14
F8
F8
F14
F2
F7
F14
F
F7
F7
G

377
377
361
220
220
220
220
220
220
220
220
220
220
376
361
361
376
442
377
377
436
156
19
95
553
376
376
135
86
377
156
376
156
95
86
377
377
6
555
555
555
555
555
555
555
555
442
95
24
24
442
156
361
156
86
362
156
347
347
21
24,95
229
229

F14
16
F15
F14
F7
F7
G
F15
F14
F7

F2
G
J
J
F2
F7
F8
F7
F7
G
G
G
F2, J
F2, J

Remarks page 11-157; References page II-159

TABLE 4. cont'd
Solvent/Additive

T( 0 C)

Acrylonitrile (cont'd)
0-Toluidine, ^//-dimethyl- (confd)
Tributylamine
Triethylamine

Trimethylamine
Tripropylamine
Zinc, diethyl
Zinc chloride
Acrylonitrile/styrene (38.5-61.5 mol%)
Methanol
Anisole, /?-vinylAnisole, /?-isopropylBenzonitrile,/7-isopropylCumene
-,/7-bromo-,/7-tert-butyl-,/?-chloroBenzoic acid, vinyl ester
Benzene
Benzoic acid, isopropyl ester
2-Butanone
Carbon tetrachloride
Chloroform
Cyclohexane
1,3-Butadiene, 2-chloro1-Butene, 3-chloro-3-methyl2-Butene, l-chloro-3-methyl2,6-Octadiene, 2,7-dichloro3-Buten-2-one, 3-methylBenzene
-,ethylCyclohexane, methylToluene
Butyraldehyde, divinyl acetal
Aniline, N,TV-dimethylBenzene
Butyl alcohol
tert-Butyl alcohol
1,3-Dioxolane, 2-propylButyric acid, vinyl ester
Benzene
Carbamic acid, vinyl-, ethyl ester
Acetone
Benzene
Chloroprene
3-Chloro-(methyl-14C)l-butene(4-14C)
3-Cfcloro-2-pentene-(2,4-14C)
/?-Dioxin, 2,3-dihydro-/maleic anhydride
Benzene
Carbon tetrabromide
Carbon tetrachloride
Chloroform
/7-Dioxane
Toluene
m-Xylene

60
60
60

50
60
60
60
50

C s (xlO 4 )

30200
463
6700
1700
1900
3800
5900
6600
175
790
4820
1.05 x l O 4
1.06 x l O 4
0.006

Remarks

Refs.

F16, G, J
F2, J
J
T

227,229
229
24
20
20
22
24
24
377
24
156
24
156
410

F7, J
J
F7
J
F7
J
F7
F13

65

1.4

116

60
60
60
60
60
60

3.40
40.9
4.28
11.8
3.64
8.52

407
407
407
407
407
407

60
80
60
80
80
80
80

1.5
0.4
1.0
29.0
730
105
2.3

393
26
393
26
26
26
26

50
50
50

5.47
4.57
5.24

Fl
F2
F2

80
80
80
80

2.489
6.934
0.500
3.282

C
C
C
C

50
50
50
50
50

1060
27.7
3500
37.2
708

152
152
152
84
84
84
84
430
430
430
430
430

80

3.28

201

60
60

8.5
1.25

117
117

50
50

5.37
3.94

60
60
60
60
60
60
60

11500
100 x 105
1.7 x 105
3.6 x 104
1.07 x 104
6.OxIO 4
9.9 x 104

F2
F2

509
509

R
R
R
R
R
R
R

169
169
169
169
169
169
169

TABLE 4. cont'd
Solvent/Additive
Ethylene
Acetamide, AW-diethyl- , AW-diisopropyl- , Ar,A7-dimethyl- , N-ethyl-,TV-methylAcetic acid, butyl ester
- , tert-buty\ ester
- , methyl ester
Acetic acid, chloro- , - , methyl ester

T( 0 C)

C s (xlO 4 )

Remarks

130
130
130
130
130
130
130
130

125
57
182
115
61
89
40
40

C, W5
C, W5
C, W5
C, W5
C, W5
C, W5
C, W5
C, W5

454
454
454
454
454
454
454
454

90

130

610
1210
2170
2150
2580
630
1160
1880
1990
2090
1120

C, Ql
C, Q2
C, Q3
C, Q4
C, Q5
CQl
C, Q2
C, Q3
C, Q4
C, Q5
C, W5

434
434
434
434
434
434
434
434
434
434
454

130

6700

C, W5

454

55

1800
7900
11100
13000
1900
6900
9400
10500
2000
5900
8100
11100

C, Ql
C, Q2
C, Q3
C
CQl
C, Q2
C, Q3
C
C, Ql
C, Q2
C Q3
C

435
435
435
435
435
435
435
435
435
435
435
435

700
16100
27500
38000
65700
1000
17000
27700
39000
65200
1200
15400
23600
33000
54100
130
160
165
168
282
100
1970
0.629
20
21
9.4
18

C, Ql
C, Q2
C, Q3
C, Q4
C
CQl
C, Q2
C, Q3
C, Q4
C
CQl
C, Q2
C, Q3
C Q4
C
C, W5
C, W17
C, F21, W5
C, W5
C,W5
C, F21, W5
C, W5
E, W
D
D, W
C,W5
W3

484
484
484
484
484
484
484
484
484
484
484
484
484
484
484
454
456
259
456
455
159
457
143
204
205
260
218

120

Acetic acid, cyano- , - , methyl ester


Acetic acid, dichloro- , -, methyl ester

90

120

Acetic acid, trichloro- , - , methyl ester

55

90

120

Acetic anhydride
Acetone

130
130

Acetonitrile
Benzaldehyde
Benzene

200
130
130
20
83
130
50-70

Refs.

Remarks page 11-157; References page 11-159

TABLE 4. cont'd
Solvent/Additive

T( 0 C)

Ethylene (cont'd)
-,ethyl-

130

Benzene-D6
Benzoic acid, butyl ester
-,ethyl ester
- , methyl ester
Butane

200
130
130
130
130
130

- , 1-iodo-

100

2-Butanone

130

- , 3-methyl1-Butene

200
130
130

- , 2-methyl-

189
200
130

-,3-methyl2-Butene

130
130

- , 1,4-dichloro-,2-methyl
tert-Buty\ alcohol

130
130
30
130
130
130
130
130
20
50
70

Butylamine
Butyraldehyde
Butyric acid, methyl ester
Butyronitrile
Carbon tetrachloride

90

95

130

140

C s (xlO 4 )

Remarks

Refs.

430
480
520
560
500
5.6
140
55
53
40
45
9.45 x 104
11.3 xlO 4
12.6 x 104
550
600
750
840
330
470
560
900
570
210
530
1200
250
380
4100
470
0
2
220
3250
220
520
215
772
974
7000
32000
740
1210
20200
32500
34000
1250 200
22000 1000
43000 4000
1130 700
2000 1000
37000 3000
9800

C, W17
C, W5
C, W5
C, W5
C, W5
C, W5
C, W5
C, W5
C, W5
C, F21, W5
C, W17
Ql, W14
Q2, W14
Q3, W14
C, W17
C, F21, W5
C, W5
C, F21, W5
C, W5
C, W5
C, F21, W5
B, W5
C, W5
C, F21, W5
C, F21, W5
C, F21, W5
C, F21, W5
C, W5
C, W5
C, F21, W5
E, W4
C, F21,W5
C-W5
C, W5
C, W5
C, F21, W5
E, W
CQl,
C, Ql
C, W4
C
Ql, W12
CQl
Q2, W12
Q3, W12
W12
W23, Q(I)
W23, Q(2)
W23, Q(3)
W20, Q(I)
W20, Q(2)
W20, Q(3)
C,F21,W5

456
52
454
52
455
260
454
454
454
259
456
187
187
187
456
259
455
259
52
52
259
443
455
259
259
259
259
454
454
259
482
259
454
457
454
259
143
391
391
215
210
453
391
453
453
453
518
518
518
518
518
518
259

1600
1700
1800
2200
22000
23000
30000
36000
38000
39000
60000

CQl
C, Ql, F19
C, Ql, W13
C, Ql, F20
C, Q2
C, Q2, F19
C, Ql, Wl
C Q3
C Q2, F20
C Q3, F19
C,Q2, W13

170
170
170
170
170
170
170
170
170
170
170

TABLE 4. cont'd
Solvent/Additive
Ethylene (cont'd)
Carbon tetrachloride (cont'd)

Chloroacetic acid, methyl ester


Chloroform

Cumene
Cyclohexane

-,methylCyclopentane
Cyclopropane
Decane
1-Decene
Dibutylamine
Dichloroacetic acid, methyl ester
Dimethylamine
p-Dioxane
Ethane
- , U-bis(dimethylamino)- , l-bromo-2-chloro- , chloro- , 1,2-dibromo- , 1,1-dichloro-

T( 0 C)

C s (xlO 4 )

60000
61000
70000
90000
100000
110000
130000
140000
180000
90 590, 550, 1200
1680, 2240, 2340
28
2100
13000
15000
70
8000
30000
80
2470
15500
24900
31200
43900
95
2000120
10000 500
16000 3000
115050
5000 300
8000 1000
101
1500
4500
5400
103
2890
15400
23800
29800
41100
130
2900
140
3210
15200
22200
28000
37600
130
500
130
80
90
91
200
190
130
110
130
109
127
200
22&
130
0
130
120
189
425
189
1090
130
1070
901900, 6900, 9400
130
1900
130
320
130
6
130
1070
130
390
70
120
130
1250
70
1500

Remarks
C, Q3
C, Q3, F20
C, Q4, F20
C, Q4, F20
C, Q2, Wl
C, Q3, Wl
C, Q3, W13
C, Q4, Wl
C
C, Q(I), Q(2), Q(3)
C, Q(4), Q(5), Q(6)
E, Ql, W
E, Q2, W
E, Q3, W
C, W4
C
C, Ql, W12
C, Q2, W12
C, Q3, W12
C, Q4, W12
C, W12
W23, Q(I)
W23, Q(2)
W23, Q(3)
W20, Q(I)
W20, Q(3)
W20, Q(3)
E, Ql, W
E, Q3, W
E, Q2, W
C, Q1,W12
C, Q2, W12
C, Q3, W12
C, Q4, W12
C, W12
C, F21,W5
C, Ql, W12
C, Q2, W12
C, Q3, W12
C, Q4, W12
C, W12
C, F21, W5
C, F21, W5
C, W17
C, F21, W5
C, W5
C, F21, W5
C, W17
C, F21, W5
C, W5
C, F21, W5
C, F21, W5
B, W5
B, W5
C, W5
C, Q(I), Q(2), Q(3)
C, F21, W5
C, F21, W5
C, F21, W5
C, W5
C, W5
C, W4
C, W5
C, W4

Refs.
170
170
170
170
170
170
170
170
170
557
557
244
244
244
215
210
101
101
101
101
101
518
518
518
518
518
518
224
244
244
101
101
101
101
101
259
101
101
101
101
101
259
259
456
259
455
259
456
259
455
259
259
443
443
454
558
259
259
259
457
454
215
454
215

Remarks page 11-157; References page 11-159

TABLE 4. cont'd
Solvent/Additive

T( 0 C)

Ethylene (cont'd)
Ethane, 1,2-dichloro- , iodo-

130
65
100

- , 1,1,1-trichloroEthanol

Ethyl acetate
Ethylene oxide
Formaldehyde
Fomamide, W,TV-dimethylFormic acid, methyl ester
Furan, tetrahydroHeptaldehyde
Heptane
Hexane
1-Hexene
- , 2-ethylHydrogen
Isobutyronitrile
Isocyanic acid, butyl ester
Isopropanol

Isothiocyanic acid, butyl ester


Methane
- , bromochloro-

70
20
30
60
100
125
130
125-135
150
180
200
130
200
130
130
130
130
130
200
130
200
50-70
130
130
189
189
130
130
200
130
130
30
60
100
125
130
125-135
150
180
200
130
130
100

130
140

C s (xlO 4 )

110
1.51 x 105
1.59 x l O 5
1.65 x 105
1.1 x 105
1.36 x l O 5
1.43 x l O 5
1.48 x l O 5
1.49 x 105
500
5.71
110,210, 270
76,240, 280
89,270, 340
100,310, 320
68
69
75
190
92,260
73,350
135
45
121
7
560
260
42
288
289
401
2600
3900
4800
90
80
68
225
900
3300
159
160
400
1070
212
96,410, 520
65,310, 380
65,300, 350
75,380, 380
130
140
144
570
98,470, 460
86,440, 500
234
0
0
1600
4500
7500
8000
10000
16.OxIO 5

Remarks

C, F21, W5
Ql
Q2
Q3
Ql
Q1,W14
Q2, W14
Q3, W14
Q3
C, W4
E, W
E, Q(I), Q(3), Q(5)
E, Q(I), Q(3), Q(5)
E, Q(I), Q(3), Q(5)
E, Q(I), Q(3), Q(5)
C, W17
C, F21, W5
C, W5
C, W2
E, Q(I), Q(3)
E, Q(I), Q(3)
C, W5
C, W5
C, W17
C, F21, W5
C, W5
C, F21, W5
C, W5
C, W5
C, F21, W5
C, W5
C, W17
C, W5
C, W5
W3
C, F21,W5
C, F21, W5
B, W5
B, W5
C, F21, W5
C, W5
C, F21, W5
C, W5
C, F21, W5
C, W5
E, Q(I), Q(3), Q(5)
E, Q(I), Q(3), Q(5)
E, Q(I), Q(3), Q(5)
E, Q(I), Q(3), Q(5)
C, W17
C, F21, W5
C, W5
C, Wl
E, Q(I), Q(3), Q(5)
E, Q(I), Q(3), Q(5)
C, W5
C, W5
C, W5
C, Ql, WIl
C, Q2, WIl
C, Q3, WIl
C, Q4, WIl
C, W5
Ql, WIl, II

Refs.

259
189
189
189
452
188
188
188
452
215
143
523
523
523
523
456
259
454
381
523
523
455
454
455
259
457
259
454
454
259
455
457
457
457
218
259
259
443
443
259
454
259
455
259
454
523
523
523
523
456
259
454
381
523
523
455
454
259
2
2
2
2
454
1

TABLE 4. cont'd
Solvent/additive
Ethylene (cont'd)
Methane, bromochloro- (cont'd)
- , chloro- , dichloro- , dimethoxy- , iodo-

T( 0 C)

70
70
130
130
65
100

Methanol

Methylamine
1-Octene

30
60
100
125
130
150
180
130
130

Pentane, 2,2,4-trimethylPentene
- , 4,4-dimethyl- , 4-methylPhosphine
- , dibutyl
- , tributyl
- , triphenyl
Phosphorous acid, dimethyl ester
Propane

130
189
130
130
130
130
130
130
130
130

- , 2-chloroPropane, 2-chloro-2-methyl-, 2,2-dimethyl- , 2-iodo-

200
70
70
130
65
100

- , 2-methyl-

130

- , 1,1,1,2,2,3,3,3-octafluoro1-Propene

200
130
130

Propionaldehyde

200
130

Propionic acid, methyl ester

200
90

120

C 8 (xlO 4 )
47.0 x 105
4
700
360
73
41000
45000
45000
41000
45000
45000
36, 84, 100
46, 100, 140
34, 90, 120
56, 100, 140
21
53, 120, 160
37, 120, 160
53
360
360
64
900
175
310
207000
36000
4500
50
5100
27
27.6
31
65.2
250
40
8
5.7 x 105
5.9 x 105
6.07 xlO 5
4.55 x 105
4.70 x 105
4.83 x 105
50
72
136
4
110
122
150
200
2300
3300
2830
63000
92000

1.08 xlO 5
630, 420, 780
890, 1030, 1230
78000
1.12 xlO 5
1.39 xlO 5
780, 430, 1060
1220, 1300, 1410

Remarks

Refs.

Q2, WIl, II
C, W4
C, W4
C, F21,W5
C, W5
Ql
Q2
Q3
Ql
Q2
Q3
E, Q(I), Q(2), Q(3)
E, Q(I), Q(2), Q(3)
E, Q(I), Q(2), Q(3)
E, Q(I), Q(2), Q(3)
C, F21, W5
E, Q(I), Q(2), Q(3)
E, Q(I), Q(2), Q(3)
C, W5
C, W5
C, F21, W5
C, F21, W5
B, W5
C, W5
C, W5
C, W5
C, W5
C, W5
C, W5
C, F21, W5
C, F21, W5
C, W17
C, F21, W5
C, W5
C, W4
C, W4
C, F21, W5
Ql
Q2
Q3
Ql
Q2
Q3
C, F21, W5
C, W5
C, W5
C, F21, W5
C, W5
C, W5
C, W5
C, W5
C, W17
C, W5
C, W5
C, Ql
C, Q3

1
215
215
259
454
189
189
189
189
189
189
523
523
523
523
259
523
523
454
52
259
259
443
454
454
457
454
454
454
259
259
456
259
455
215
215
259
189
189
189
189
189
189
259
454
455
259
52
454
52
455
457
457
457
485
485

C, Q5
C, Q(I), Q(2), Q(3)
C, Q(4), Q(5), Q(6)
CQl

485
516
516
485

C, Q3
C, Q5
C, Q(I), Q(2), Q(3)
C, Q(4), Q(5), Q(6)

485
485
516
516

Remarks page II-157; References page II-159

TABLE 4. cont'd
Solvent/Additive

T( 0 C)

Ethylene (cont'd)
-, 3-cyano-, methyl ester
Silane, tetramethyl
Tetradecane
1-Tetradecene
Toluene

130
130
189
189
130

Tributylamine
Trichloroacetic acid, methyl ester
Tridecane
Trimethylamine

200
130
90
130
130

Water
/?-Xylene

20
130
200

Ethylene, bromoCarbon tetrachloride


Ethylene, chloroAcetaldehyde
Aniline, A^-dimethylBenzene
Butyraldehyde

Carbon tetrabromide

60
50
50
35
50

50
60

Cyclohexane, 1,2-epoxy-4- vinylEthane, 1,2-dichloroEther, dodecyl vinyl


Furan, tetrahydroHeptane, 2,4,6-trichloroOxalic acid, diethyl ester
Pentane, 2,4-dichloroEthylene, 1,1 -dichloroPhosphorus trichloride
Ethylene, tetrafluoroEthanol

25
50
50
25
40
50
50
25
25
50

790
0
580
1760
130
154
180
220
820
1000, 1700, 2770
140
180
330
1.71
300
317
400
434

110
2700
1500
350
420
500
580
4.7 x 104
50.0 x 104
3300
1.85 xlO 4
7.45 x 104
12.15 xlO 4
264
4.0
4.5
156
16
30
24
5
1.4
9.0
5
14

100

800
820
860
880
1540
1660
1700
350
390

100

Methanol

100
80
140
125-135
30-35

Remarks

C, W5
C, F21, W5
B, W5
B, W5
C, W5
C, W5
C, W17
C, W5
C, W5
C, Q(I), Q(2), Q(3)
C, F21, W5
C, F21, W5
C, W5
E, W
C, F21, W5
C, W5
C, W17
C, W5

50

60

Isopropanol

Hexanoic acid, vinyl ester


Benzene
1-Hexene
Carbon tetrachloride
Cyclohexanol
Ethyl alcohol

C s (xlO 4 )

454
259
443
443
52
454
456
455
454
559
259
259
454
143
259
454
456
455
417

W8
W7
W15
F26
Ql
Q2
Q3
Q4
C, F26

G
D
C, Q5, W2
C, Q6, W2
C, Q4, W2
C, Q3, W2
C, Q3, W2
C, Q4, W2
C, Q5, W2
C, Q3, W2
C, Q4, W2

4.9
4.1 x 104
390
170

Refs.

164
161
219
500
500
500
500
492
66
418
418
418
418
428
425
392
4
425
246
164
211
315
315
211
214
3
3
3
3
3
3
3
3
3
201

C, Ql, F19
C
D

170
381
381

TABLE 4. cont'd
Solvent/Additive

T( 0 C)

Isobutene
Carbon tetrachloride

100

Isobutyric acid, vinyl ester


Benzene
Maleic acid, diethyl ester
Stearamide, iV-allylMaleic anhydride/methyl methacrylate
Acetone
Maleic anhydride/styrene
Aniline, A^-dimethylCarbon tetrachloride
Methacrylic acid
Bromotrichloromethane
- , butyl ester
Benzene
-, 2-(diethylamino)ethyl ester/styrene
Carbon tetrachloride
Toluene
-, ethyl ester
Acetic acid
Acetone
Acetophenone
Benzene
-, chloro- , ethyl2-Butanone
Butyl alcohol
sec-Butyl alcohol
tert-Butyl alcohol
Carbon tetrachloride

80

Remarks

E, Q(I)
E, Q(2)

4.49
22.4

60

Refs.

537
201

173

1.6

HH

367

60
70

930
1.04

HH

489
365

70

300

60
80
80
80
80
80
80
80
80
80
80
80
80
80

566

0.158

264

23.6
13.3

335
335

80
80
80
80
80
80
80
80

0.095
0.102
0.281
0.081
0.436
1.428
0.252
0.454
1.604
0.417
0.901
5.640
0.703
2.360
2.067
0.928
1.821
0.311
1.820
0.536
0.919
0.429
0.865
0.702
0.445
0.236
0.436

70
70

0.983
2.05

137
137

60
80
80
80
80

0.165
1.971
1.110
0.510
0.510

C
C
C
C

264
183
183
183
183

100
120
60
60
60

900
1000
30800
0.001
0.996

80

Cumene
Cyclohexane
Ethane, 1,2-dichloroEthane, 1,1,2,2-tetrachloro-

80
80
80
80

Iron(III) chloride
Isobutyraldehyde
Toluene
Methyl methacrylate
Acetaldehyde
Acetic acid

(7.1 0.2) x 104


(8.1 0.5) xlO 5

90

Chloroform

-, 1,1,1-trichloroEthyl acetate
Ethyl alcohol
Heptane
2-Heptanone
Isobutyl alcohol
2,4-Pentanedione
Toluene
- , hexadecyl ester
Carbon tetrachloride
Cumene
- , isobutyl ester
Benzene
Carbon tetrachloride
Chloroform
Ethane, 1,2-dichloro- , 1,1,2,2-tetrachloroMethacrylonitrile
Carbon tetrabromide

C s (xlO 4 )

60
80

6.5
0.24

C
C
C
C

A, F7
A, F7
F7

83
83
83
83
83
83
83
83
83
83
83
183
83
183
83
83
183
83
183
83
83
83
83
83
83
83
83

109
109
19
70
21
86
31

Remarks page II-157; References page 11-159

TABLE 4.

cont'd

Solvent/Additive

T ()

Methyl methacrylate (cont'd)


Acetic acid, monochloro- , dichloro- , l,l-dimethyl-2,2,2-trinitroethyl ester
- , trichloroAcetone

60
60
45
60
60
80

Acetonitrile, (m-bromophenyl)- , (p-bromophenyl)- , (m-chlorophenyl)- , (p-chlorophenyl)- , (p-methoxyphenyl)- , phenyl- , m-tolyl-,/?-tolylAcetylene,/7-bromophenyl-,/?-chlorophenyl- , /MiitrophenylAluminum, hydrodiisobutyl
- , triethyl

60
60
60
60
60
60
60
60
60
60
60
60
50
60
60
80
100
30
50

Aniline
- , MN-dimethyl-

60
70
80
100
60
60
80
100
60
25
60
60
60
50
50
60

- , AW-divinyl- , Af-methylp-Anisaldehyde
Anisole
- , />-ethynyl-,/j-isopropyl-,p-methylAnthracene
Azobenzene
Benzaldehyde
-,/j-bromo-, m-chloro-,p-chloro-,/?-cyanoBenzene

60
60
60
60
25
30
50
52
60
75
80

- , allyl- , bromo-,

tert-butyl-

90
60
25
80

C 8 (xlO 4 )
0.64
0.80
520
1.10
0.195
0.225
0.275
3.89
2.78
4.28
3.21
19.0
5.18
5.75
7.83
41.3
38.9
127.5
3600
1550
1240
4.2
6.3
9.0
2.45
18
30.4
430
11.3
10.8
17.0
20.0
340
7.0
10.0
13.3
1.11
0
40.3
3.46
0.57
0
100
2.5
0.86
1.43
0.96
1.03
2.06
0
0.01
0.036
0.027
0.040
0.83
0.33
0.075
0.080
0.24
0.036
400
0
0.260

Remarks
R
R
R
A

K
K
K
S
R, F2
F2
F2
F2
F16
H
A, F2
A, F2
A, F2
F2
F2
F2
D
K

C
C
A
Il
D
A

Refs.
529
529
110
529
81
31
81
462
461
462
461
461
461
462
461
151
151
151
156
547
156
424
424
424
508
228
409
161
424
270
424
424
82
424
424
424
495
16
151
406
496
15
282
86
495
495
495
495
495
16
508
147,327
81
81
181
123
31
81
145
147
502
16
31

TABLE 4. cont'd
J( 0 C)

Solvent/Additive
Methyl methacrylate (cont'd)
-, chloro-

-,/7-diisopropyl-,
- , ethyl-

25
60
80
ra-dinitro-

- , ethynyl-,
Benzene sulfonylchloride
-,/7-chloro-,/7-dimethylBenzonitrile
-,p-hydroxy- , p-isopropylp-Benzoquinone
- , 2,3,5,6-tetrachloroBenzothiazolethion, 3-allylBenzyl ether
Bibenzyl
Biphenyl, 2,2-methyleneBorane, tributylBromoform
Butane, 1-chloro-, 1,1,1-trinitro1,4-Butanediol
2-Butanone

1-Butene
- , 3,4-epoxy-2-methyl2-Butene, cis- , trans3-Buten-2-ol, l-chloro-3-methylButyl alcohol
sec-Butyl alcohol
tert-Butyl alcohol

60
50
52
60
80
60

fluoro-

25
60
60
60
25
60
50
60
44.1
50
60
44.1
60
25
60
50
60
60
60
77
80
45
60
80
60
70
75
80
40
50
80
40
50
40
50
80
60
80
60
80
60
80

Butylamine, N-nitroButyl ether


1-Butyne, 1-phenylButyraldehyde

45
60
60
50

Carbon tetrabromide

30

C s (xlO 4 )

0
0.074
0.200
0.207
5.72
52
0.501
0.766
1.311
1.350
2.1
21.9
22.3
0
5.16
8.56
4.06
0
0.162
6.0
4.99
5.5 x 104
5.7 x 104
4.5 x 104
2600
153
10.4
8.0
0.0
41.8
53.5
7.45
23
1.20
8300
0.61
1.07
0.45
0.56
0.83
0.70
3.1
5.1
29.6
3.2
4.9
3.0
5.2
18.8
0.394
0.25
0.259
0.85
0.085
0.100
0.152
0
0.8
10.8
1.47
2.25
3.40
2800 600
1000 100

Remarks

Refs.

16
81
31
81
406
15
81
81
81
31
145
151
150
16
543
543
543
16
150
479
406
194
15
42
194
502
368
368
354
567
567
156
506
31
110
421
421
290
123
123
31
287
287
269
287
287
287
287
269
479
31
479
31
81
31
81
110
86
150
500
500
500
521
521

A
Il
K
J
D
R
R
R
D

D
F2

D, C, R
A
F24
F24
C
C
C
A

A
A
A

W8
W7
D, R, JJ3a
D, R, JJ3b

Remarks page 11-157; References page 11-159

TABLE 4. cont'd
Solvent/Additive

T( 0 C)

Methyl methacrylate (cont'd)


Carbon tetrabromide (cont'd)

Carbon tetrachloride

60
60
60
80
100
20
30
50
60

70
80

Chloroform

60
80

Copper(II) chloride
Cumene

60
60
80

-,p-bromo-

60

-, p-tert-butyl-,/7-chloroCyclohexane

60
60
60
80
80
60
60
50
79.5
80
44.1
60
79.5
79.5
60
60
60
80
45
60
80

-,methyl- , trans-lA-, diacetate


- , cis/trans-1,4-, dicarboxylic acid dimethylester
Cyclotetrasiloxane, octamethylp-Dioxane
Diphenylamine
Diphenylamine-T
Disiloxane, l,l-dimethoxy-3,3,3-trimethyl-l-phenyl- , hexamethylEpibromohydrin
Epichlorohydrin
Ethane, 1,2-dichloro- , nitro- , 1,1,2,2-tetrachloro- , 1,1,1-trichloro- , 1,1,1-trinitroEthyl acetate

80
45
60

C s (xlO 4 )
1000 500
50Od= 200
2700
1500
1900
3300
4600
0.2
20
0.20
0.82
0.925
2.40
5
20.11
18.52
0.42
0.5
1.74
2.393
2.421
3.3
24.4
0.454
1.77
1.129
1.400
1.9
1.9
105 x 105
1.9
2.56
1.9
2.4

Remarks

Refs.

D, R, JJ3c
D, R, JJ3d
F2

521
521
109
568
568
109
109
35
451
514
514
81
181
86
529
529
568
568
514
31
81
145
427
81
181
81
31
145
427
36
7
406
31
145

F2
F2
C, D
D, F2

C
R
R, H
R
R, H
A
Il
D
C
A
Il
D
F7
A
Il

3.71

2.74
3.07
12
0.10
0.195
8.46
1.16
2.5
0.080
0.222
0
0.3
0.032
0.104
16.53
9.3
0.35
0.756
2.0
0.155
0.200
0.235
0.600
1400
0.100
0.13
0.132
0.134
0.155

406

A
A
C
C
C
A
F2
R
R

A
A
C
A
C

406
406
86
31
31
569
569
450
474
31
194
46
474
474
529
529
81
81
110
81
31
81
31
110
316
290,316
216
290
290

TABLE 4. cont'd
Solvent/Additive

T( 0 C)

Methyl methacrylate (cont'd)


Ethyl acetate (cont'd)

Ethyl alcohol
Ethylene glycol
Germane, diethylchloro- , ethyldichloro- , triethyl- , triphenylGlycerol
Heptane
1-Heptanol, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroHydrazyl, 2,2-diphenyl-l-picryl
Hydroquinone
Indium, triethylIsobutyl alcohol

70
75
80
60
80
100
60
80
60
60
60
60
60
50
60
44.1
45
131
60
60
80

Isobutyric acid
- , methyl ester
Isopropyl alcohol

80
60
60
80
100
130

Lead, tetraethyl
Malononitrile, furfurylideneMercury, diethyl
Methane, bromotrichloro- , bromotrinitroMethane, dichloro- , nitro- , trinitro- , triphenylMethanol
1-Naphthol
2,6-Octadiene, 2,6-dimethylOleic acid, methyl ester
Oxime, acrolein- , crotonaldehyde-, ethylisopropenylketone- , methacrolein- , methylacrolein-, methylisobutenylketone-, methylisopropenylketone- , methylvinylketoneOxolane, c/s-3,4-diacetoxyPentane, 2,2,4-trimethyl1-Pentanol, 2,2,3,3,4,4,5,5-octa-fluoro2-Pentanone, 4,4-dimethyl-5,5,5-trinitro-

60
44.1
60
30
45
60
80
60
45
60
60
80
100
45
60
60
60
60
60
60
60
60
60
60
60
50
60
45

C s (xlO 4 )

0.156
0.46
0.55
0.83
0.240
0.40
0.625
0.80
0.28
0.60
22000
39300
5800
18500
0.152
1.8
2.8
20OxIO 5
7.0
100
332
0.10
0.505
0.229
0.250
0.900
0.26
0.583
1.907
3.00
8
43
45
3.14
1.2 x 104
0.898
830
1.2 xlO 4
4.5 xlO 4
1.0 x 104
0.100
0.217
2.0
5400
4.0
0.2
0.33
0.45
<5.0
6.7
1.68
8.0
25500
500
3000
17000
5200
4700
2900
1300
1.39
1.2
2.36
400

Remarks

C
110
C
C
A
A, F2
A, F2
A
F24
F24
A, R
A, R
A, R
A, R
F2
A

A
A

A
C
C
C
S
D, Q3
D
D, Q4

A, F2
A, F2
A

C
F2

Refs.

290
146
123
123
31
423
423
49
421
421
539
539
539
539
479
206
442
194
30
398
156
81
479
81
31
31
275
81
81
49
337
337
480
156
194
156
311
311
311
110
81
81
86
110
44
423
423
49
30
324
441
7
555
555
555
555
555
555
555
555
569
206
442
110

Remarks page II-157; References page II-159

TABLE 4. cont'd
Solvent/Additive
Methyl methacrylate (cont'd)
- , 4-methyl3-Pentanone

Pentasiloxane, dodecamethylPhenol
- , 0-bromo-,/7-bromo- , o-chloro- , o-ethyl-,/?-ethyl- , 0-isopropyl- , /?-isopropyl-,/7-methoxy- , 2,3,4,6-tetramethylPhenyl ether
Phosphine, octyl-,phenyl- , tributylPhthalic acid, dimethylester
Piperidine, 1-nitrosoPropane, 1,2-dichloro- , 1,1-dinitro- , 2,2-dinitro- , 1-nitro1,2-Propanediol
1-Propanol, 2,2,3,3-tetrafluoroPropene, 1,3-diphenyl1-Propene, 2-methylPropionic acid, 2,2,2-trinitroethyl ester
Propionitrile, 3-phosphino- , 3,3/-phosphinylidenediPropyl alcohol

Pyridine
Pyrocatechol
- , p-tert-buty\Pyrogallol
Silane, (oc-bromotolyl)trimethoxy- , bromomethylphenyltrimethoxy- , chlorotrimethyl- , dichlorodimethyl- , dichloromethyl- , diethylchloro- , dimethoxymethylphenyl- , dimethylphenyl- , hexamethoxy-^^'-thiodipropyDbis- , methyldichloro- , (3-mercaptopropyl)trimethoxy- , tetraethyl- , tetramethyl- , trichloro
- , trichloromethyl-

J(0C)

80
60
80

79.5
50
50
50
50
50
50
50
50
45
45
25
60
60
60
60
30
45
80
45
45
45
60
80
60
60
40
50
45
60
60
60
80
100
70
45
45
45
79.5
79.5
30
50
30
50
79.5
60
79.5
60
79.5
79.5
60
79.5
60
30
50
60
30
50

C s (xlO 4 )

0.700
0.833
1.729
1.775
2.7
0.145
2.5
5.0
5.0
3.5
7.2
7.5
13.3
13.3
<5.0
11.0
6.42
9.13
2.3 x 104
16.IxIO4
30.6
0.2
8.2
0.675
68
15
5
0.48
0.86
1.86
15.6
2.5
4.4
3000
1.4 x l O 4
1.3 x 104
0.69
0.84
1.25
0.176
<5
9
26
29.8
29.8
144
2.2
175
2.45
15.2
1700
0.20
0.2
300
25.8
15.2
3100
6930
5.75
5.0
1.3
5000
185
2.7

Remarks

A
Il

F24
F24
F2

A, F2
A, F2
A

R
D, F2
D, F2

A, R
R
A, R
R
R
A, R
R
D, F2
A, R
D, F2

Refs.

31
81
81
31
145
474
479
479
479
479
479
479
479
479
30
30
368
368
295
295
156
508
110
31
110
110
110
421
421
442
567
287
287
110
295
295
423
423
49
514
30
30
30
474
554
451
249
451
249
474
539
474
554
539
554
554
539
554
156
451
249
539
451
249

TABLE 4. cont'd
T( 0 C)

Solvent/Additive
Methyl methacrylate (cont'd)
- , triethyl
- , triisopropoxymethyl-

60
79.5

- , trimethoxymethyl-

79.5

- , trimethoxyphenyl-

79.5

- , triphenylSilicon chloride

60
30
50
79.5
79.5
79.5
79.5
79.5
79.5
79.5
79.5
79.5
79.5

Siloxane, l,l-dimethoxy-trimethyl-l-phenyl-di-3,3,3- , dodecamethyl penta- , l,l,l,3,5,5,5-heptamethyl-3-phenyltri- , 1,1,1,3,5,5,5-heptamethyl-tri- , 1,1,1,3,5,5,5-heptamethyl-tri- , l,l,l,3,5,5,5-heptamethyl-3-(3,3,3,3-tri-fluoropropyl)-tri- , hexamethyl-di- , hexamethyl-phenyl-tri- , l,l,l,5,5,5-bexamethyl-3-(2-phenylpropyl)-tri- , 3-(3-mercaptopropyl)1,1,1,3,5,5,5-heptamethyl-tri- , octamethyl cyclotetra- , octamethyl triSorbit-2,5-diacetate, 1,4:3,
6-, dianhydroStearamide, JV-allylStearic acid, methyl ester
Stibine, tributyl
Tin, tetrabutyl
Toluene

79.5
79.5
60
90
60
60
60
20
52
60

70
80

-, p-bromo-,
-,p-chloro-, a-chloro
- , p-ethynyl-,p-nitro-, 2,4,6-trinitrom-Tolunitrile, a-cyanop-Tolunitrile
-, a-cyanoTributylamine
Triethylamine

ra-chloro-

Tripropylamine
Trisiloxane, 1,1,1,3,5,5,5-heptamethyl- , - , 3-(p-methylphenethyl)- , - , 3-phenyl- , - , 3-propyl- , - , 3-(3,3,3-trifluoropropyl)-

60
60
60
60
60
44.1
44.1
60
60
60
70
20
60
60
79.5
79.5
79.5
79.5
79.5

C s (xlO 4 )

200
0.697
0.697
0.331
0.331
0.053
0.053
1200
256
3.0
0.032
0.145
0.232
0.284
0.189
0.205
0.104
1.84
2.08
1284.5
0.08
0.0316
29
3.01
0.282
<1.0
1.32
0.04
0.084
0.170
0.190
0.202
0.250
0.26
0.400
0.45
0.567
0.292
0.303
0.52
0.525
0.91
0.58
0.48
0.49
4.17
64.4
0
500
4.55
0.73
1.74
25.7
1.5
8.3
1900
14.6
0.284
2.08
0.232
0.189
0.205

Remarks

A, R

Refs.

R
R
R
R
R
R
R
R
R
R

539
474
554
474
554
474
554
539
451
249
554
554
554
554
554
554
554
554
554
554

R
R
C

554
554
569

R
R
R
A, R
D, F2

C, J

C, D
C
C
C
C
C
C
Il
A
C

C
K

C, D
J

173
441
156
156
35
81
21,81
316
32,316,317
316
275
316
496
123
32
81
145
31
123
496
496
496
181
151
194
194
462
496
461
270
35
24
25
156
474
474
474
474
474

Remarks page 11-157; References page 11-159

TABLE 4. cont'd
Solvent/Additive
Methyl methacrylate {cont'd)
- , l,l,l,5,5,5-hexamethyl-3-phenyl- , octamethylUrea, thioWater

m-Xylene
p-Xylene
2,4-Xylenol
Naphthalene, 1-vinylNaphthalene
Nonanoic acid, vinyl ester
Toluene
1-Octene
Butyl alcohol
sec-Butyl alcohol
Ethyl alcohol
Isopropyl alcohol
Methanol
Phthalimide, N-vinylChloroform
Ethane, 1,2-dichloroMethane, dichloro2-Picoline, 5-vinylAllyl ether
1-Propene
Carbon tetrachloride
Chloroform
1-Propene, 3-chloroCarbon tetrachloride
Hydrochloric acid
1-Propene, 2-methylCarbon tetrachloride
- , 3,3,3-trifluoroCarbon tetrabromide
Propionic acid, vinyl ester
Toluene
Propylene
Bromoethane

J( 0 C)
79.5
79.5
42
60
80.5
60
60
50

30-50

50
60
70

11.1
13.9
15.2

117-118
117-118
115-118
30-35
120-125
116-120
55
55
55
70
100
100

Styrene
Acetaldehyde

270
520
230
630
520
110

Remarks

A, R
F7, F24

4800
1.8 x 104
5.4 xlO 4

100

17.0 x 104
640000

474
474
503
268
479
529
48
496
496
479

R
R
R

357
357
357

C
C
C
D
C
C

381
381
381
381
381
381
313
313
313

21.4
(5-10) x 104
1.03 x 104

Refs.

216

3.4
0.35
0.97

100
80

11
C
C

210
210

C
Ql
Q2

210
238
238

210

C, Q(I-3)

570

1.4

50
75

1200
1400
1500
1800
1700
1900
1800
2200
2100
2700
17200 1100
33000 15000
17000 800
299000 8000

Q(I-4)
Q(I)
Q(2)
Q(3-4)
Q(I)
Q(2)
Q(3-4)
Q(l-2)
Q(3-4)
Q(l-4)
W23, Q(I)
W23, Q(2)
W24, Q(I)
W24, Q(2)

517
517
517
517
517
517
517
517
517
517
518
518
518
518

13800 800
266000 10000

W20, Q(I)
W20, Q(2)

518
518

125

Stearic acid, vinyl ester


Toluene

1.84
0.032
1.21
0
0.002
0.03
0
0.43
0.50
6.5

60

100

Chloroform

C s (xlO 4 )

150
95

50
70

20.7
21.6

60

8.5

158

R
R

357
357
86

TABLE 4. cont'd
Solvent/Additive
Styrene (cont'd)
Acetamide, N,Af-dimethylAcetic acid
- , methyl ester
- , bromo- , chloro- , - , methyl ester
- , dibromo-, ethyl ester
- , monochloro- , dichloro-,
-,
-,
-,
-,

dichloro-, ethyl ester


iodophenyl- , ethyl ester
tribromo-

- , -, ethyl ester
- , trichloro-

-, - , ethyl ester

T( 0 C)

50
60
40
100
60
68
68
60
100
90
60
60
60
68
60
100
90
90
60

Acetic anhydride
Acetoacetic acid, ethyl ester
- , 2-acetyl, ethyl ester
Acetone

60
90
100
60
100
100
60

- , oxime
Acetonitrile
- , m-bromophenylAcetonitrile, p-bromophenyl-, m-chlorophenyl-,/7-chlorophenyl-,/?-methoxyphenyl-,phenyl-, m-tolyl-,/7-tolylAcetyl bromide
Acetyl chloride, chloroAcetylene, p-bromophenyl- , p-chlorophenyl-,/7-nitrophenylAdipic acid, diallyl ester
- , di-(3,3,5,5-tetramethyl-4-nitrosocyclohexyl) ester
Allyl alcohol
Aluminum, hydrodiisobutyl

60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
100

- , triethoxy- , triethyl

100
100

-, triisobutyoxy- , triisobutyl
Aniline

100
110
50
60
50

- , MN-dimethyl- , AW-divinyl-

60

C s (xlO 4 )

0.743
4.6
2.22
0.33
430
300
200
0.3
0.75
2700
28.6
0.76
35.0
1.0
1.3
8000
6.0
8.8
3.0 x 104
2.4 xlO 4
10.5 x 104
270
66.0
100
3.75
65.0
90.0
145.0
0.7
1.3
3.0
4.1
<0.5
0.32
2.2
0.44
66.7
68.5
65.2
66.0
51.0
45.1
48.5
49.2
8600
3300
188.5
161
3130
6.0
1.1 x 104
1.5
26.9 x 104
28.OxIO 4
<0.1
8.05 x 104
17.OxIO4
<1.0
28.5 x 104
20
2.0
12
53
130

Remarks

A
A
C
R
R, H
R
R, H
A
A
C
C
A
R
R, H
A
C
A
A
C
A
A
A
A

S
K
K
K
F9, J
A
A
A
A
A
A
F2
A
F2

Refs.

375
113
385
72
112
149
149
128
128
64
529
529
529
529
128
149
128
72
178
64
64
178
128
529
529
128
64
128
128
72
72
182
128
501
128
128
462
461
462
461
461
461
462
461
112
112
151
151
151
446
314
128
156
155
155,156
156
155
155
155
154
128
154
161
82

Remarks page 11-157; References page 11-159

TABLE 4. cont'd
Solvent/Additive

T ()

C s (xlO 4 )

Styrene (cont'd)
Aniline, N-methyl- , 2,4,6-trinitro/7-Anisaldehyde
Anisole,/7-ethynyl- , m-isopropyl- , p-isopropyl- , p-methyl-,2,4,6-trinitroAnthracene
- , dihydro2H-Azepin-2-one, hexahydroAzobenzene
Benzaldehyde

50
50
60
60
60
60
60
50
44.1
50
130
70
60

13
11.8 x 104
2.86
60.0
5.23
3.23
0.78
20.3 x 104
2.OxIO 4
610
0.61
750
4.54
5.5
2.6
12.2
13.7
8.63
5.6
76.7
3.9
5.8
0.01
0.018
0.023
0.028
0.04
1.92
5.50
6.67
0.061
0.121
0.156
0.184
0.23
0.31
0.42
0.81
0.89
1.5
36
1.78
3
6.22
0.04
0.06
0.193
0.55
0.133
1.50
0.235
0.874
0.54
0.6
58.5 x 104
1950
7.02
10.70

-,/7-bromo-, m-chloro-,/7-chloro-,p-cyanoBenzene

100
60
60
60
100
60
35
40
50
60

70
75
80

100

132

-, allyl-, bromo- , sec-butyl- , tert-bx\ly\-

100
60
155
60
60

- , chloro-

80
100
60
80

- , - , 2,4,6-trinitro- , 1,2-dibromoethyl-,/?-dibutyl
- , /?-di-seobutyl- , p-<\i-tert-bu\y\-

100
140
50
60
60
60
60

0.87

- , m-dichloro-

140

- , o-dichloro-,/7-dichloro-

60
60

0.2
1.4
3.4
2.6

Remarks
F2

Refs.

H
H

154
370,372
495
151
405
406
496
370,372
159
271
108
281
495
86
298
495
495
495
298
495
119
119
327
127
79
255
145
415
123
123
185
255
273
127
145
235
235
235
127
145
524
182
237
415
145
127
185
127
255
182
255
185
235
58
370,372
112
415
415

415

C
C

58
67
182
182

J
D
C, I
C
A

A
F2
F2
A
C
A, 15
H
C
C
15
C
A
A, 15
A
A
A
A
A, 15
A, R
C
A
H
A, 15
A
15
A
C
C
C
15
A

TABLE 4. cont'd
Solvent/Additive

T( 0 C)

C s (xlO 4 )

Remarks

Styrene (cont'd)
Benzene, diethyl-, (mixture)

100

A
A
A

-, ethynyl-

60

-,
-,
-,
-,

60
60
60
40
50
60
44.1

3.35
6.33
5.13
3.30
6.60
0.67
0.70
0.710
0.83
2.7
1.07
1.113
1.38
1.62
2.2
2.33
2.31
2.9
4.9
96.3
98.3
12.76
9.43
13.30
9.48 x 105
6.43 x 105
3.51 x 105
1.3 x 105

70
50
60
60
60
44.1
60
80
45
80
80
80
80
80
25
60
60
60
80
60
60
100
100
60
100
60
100
60
100
60
60
100
60
80
100

700
5.72 x 105
40
5.3
18.6
1.4 x 105
22.7 x 105
56.6 x l O 5
53.2 x 105
4.3 x 105
21.OxIO 5
95.0 x 105
6700
2.6 x 105
71.6
62.4
3020
1.12 x 104
1.2 x l O 4
142
97.9
<0.1
34.8
0.06
0.35
0.04
0.37
1.2
0.3
0.43
1.85
5.5
3.2
5.6
9.3

-,/?-diisopropyl-,ethyl-

132
60
60

80
100

132

sec-hexylsec-pentyltri-sec-butyl1,3,5-trinitro-

Benzo[B] chrysene
Benzoic acid
-, m-(phenylazo)-, methyl ester
- , 2,4,6-trinitro-, ethyl ester
Benzoin
Benzonitrile
-,/7-isopropyl
Benzo[A]pyrene
p-Benzoquinone
/7-Benzoquinone, 2-anilino- , 2,5-dimethyl- , 2-methyl- , 2,3,5,6-tetrachloro- , 2,3,5,6-tetramethyl- , 2,3,5-trimethylBenzyl ether
Bibenzyl, ococ'-dibromoBicyclohexyl, 3,3,3',3',5,5,5',5'-octamethyl-4,4'-dinitrosoBiphenyl, 2,2 '-methyleneBorane, tributoxy- , tributyl
Butane, 1-bromo- , 1-chloro-, 2-chloro- , 2,2-dimethyl- , 1-iodo1,4-Butanediol

A
C
A, 15
C
15
C
A
A
A, 15
A
A
A
A, 15
K
J
H
H
H

J
C
A
J
J
J
J
J
J
J
J
D
F9, J
F9, J

A
A
A
A
A, S
A
A
A
F24
F24
F24

Refs.
235
235
235
497
406
127
79
255
145
363
185
255
235
127
145
235
235
127
145
151
150
415
415
415
372
370,372,373
372
159
281
370,372
128
150
406
159
42
27
199
27
27
27
27
27
368
368
112
314
314
567
567
156
156
128
128
128
128
128
128
304
128
128
422
422
422

Remarks page II-157; References page 11-159

TABLE 4. cont'd
Solvent/Additive
Styrene (cont'd)
2-Butanone

T( 0 C)

1-Butene
- , 3,3-dimethyl-2-phenyl- , 2,4-diphenyl- , 3,4-epoxy-2-methyl- , 2-methyl- , 3-methyl-

60
70
75
100
110
110
80
100
100

2-Butene
- , 1,4-dichloro- , 2,3-dimethyl-

100
80
100

-,2-methyl3-Buten-2-ol, l-chloro-3-methylButyl alcohol

100
80
40
50
60

sec-Butyl alcohol
terf-Butyl alcohol

Butylamine
terf-Butyl ether
tert-Buty\ isocyanide
1-Butyne, 1-phenylButyraldehyde

60
50
60
80
100
130
60
60
80
100
60
50

- , diallyl acetal
Butyric acid, 4-hydroxy-, y-lactone
Cadmium, dibutyl
Carobonic acid, cyclic ethylene ester
- , diallyl ester
- , di-(3,3,5,5-tetramethyl-4-nitrosocyclohexyl) ester
Carbon tetrabromide

60
100
60
50
100
50
60
60
80
40
60

60
60
70
80
90
100

C s (xlO 4 )
4.98
8.60
12.00
2.6
10
70
17.4
3.1
6.9
6.1
2.0
51
5.4
5.1
2.9
8.2
11.2
6.5
0.06
1.6
0.562
6.6
0.22
6.65
0.345
0.55
1.0
0.5
2.6
1.0
33.0
34.3
2.7
14.3
2.7
3.7
4.0
4.7
8.0
8.0
11.7
14.3
5.7
11.0
20.2
0.409
1170
0.235
6.2
1.3 x 104
1.4 x l O 4
1.8 x 104
1.78 x l O 4

2.2 x 10 4
2.5 x 10 4
13.6 x 10 4
4.2 x 10 4
(5.09 0.18) xlO 5
88300
40600
1.8 x 10 4
2.3 xlO 4
2.51 x 10 4
2.35 x 10 4

Remarks
C
C
C
A
A
A
A
A
A, R
A
C
A
A, R
A
F24
A
A, C

A
A
A
A
C, F2
C, F2
W8
F29, W8
F29, W16
F2, W7
F29, W7
F2, W15
F29, W15
F2
F29
A
A

E
F27, J
F9, J
F2
C

F2
Fl
A
112

F2
C
A

Refs.
182
123
123
358
433
433
269
358
358
524
358
112
358
524
358
269
119
430
128
323,385
479
430
422
385
422
261
261
128
301
301
4,75
150
412
412
414
414
413
414
413
414
413
414
128
128
446
375
156
458
446
314
314
109
64

109
109
128
487
520
568
568
61
109
64
128

TABLE 4. cont'd
Solvent/Additive

F( 0 C)

C s (xlO 4 )

Remarks

80
100
17
248
69
84
87
90
92
98
100
109
110
120
122
144.1
130.9
148
92
110
18
117
133
34.1
148
186
185
304
300
0.41
0.5
0.566
3.40
4.0
0.50
0.916
3.3
11
33
43
22.1
39
<5
0.8
0.82
1.04
3.88
1.31
2.00
2.90
8.29
7.57
3.46
6.90
0.024
0.031
0.04
0.063
8.5
0.066
0.083
0.156
0.16
0.23

W8

Refs.

Styrene (cont'd)

Carbon tetrachloride

50
60

60
60
76
80
85
95

Chloroform

100
132
140
60

68
80
Chloroform/acetone
m-Cresol
0-Cresol
p-Cresol
- , a-phenylCumene

60
50
50
60
50
60
60
60

80
100
- , m-bromo-,/7-bromo- , p-tert-butyl-,p-chloroCyclohexane

60
60
60
60
60

80
100

Q36
C, W8
C
C, W7
A
C
Q142
A, X
R
R, H
X
C
A
15
Q38
Q142
A
A
A
A
C
C
15
C

A
A, 15
15
A
A, 15

A
A, 15
C
F23
15
C
A
A, 15

412
412
513
513
63
401
113,183
401
128,129,210
401
366
63
223
416
114
529
529
115
568
568
236
236
185
163
63
63
128,129
129
58
501
128,210
255
182
149
185
255
501
247,248
247,248
121
247,248
121
121
7
127
145
406
185
127
145
405
406
406
406
127
79
145
255
119
185
255
273
127
145

Remarks page 11-157; References page 11-159

TABLE 4.

cont'd

Solvent/Additive

T( 0 C)

Styrene (cont'd)
Cyclohexane (cont'd)
132
Cyclohexanone
-, trans-lA-, diacetate
- , cis/trans-1,4-, dicarboxylic acid dimethylester
Cyclopentanone
1-Cyclopentene- 1-carboxylic acid, 3,3,5,5-tetramethyl-4-nitroso-,
diester with pyrocatechol
Cyclotetrasiloxane, octamethyl1,2,3,4-Dibenzpyrene
1,2,7,8-Dibenztetracene
1,2,9,10-Dibenztetracene
p-Dioxane

Diphenylamine-T
Disiloxane, hexamethylEpibromohydrine
Epichlorohydrine
Ethane, 1,2-dibromo-,1,2-dichloro-

60
60
60
60
60
80
50
44.4
44.4
44.4
60
100
60
79.5
60
60
60
80
60
70
80

- , pentaphenyl- , 1,1,2,2-tetrachloro- , l,l,2,2-tetrachloro-l,2-difluoro- , l,l,2-trichloro-l,2,2-trifluoroEthanehexacarboxylic acid, hexaethyl ester


1,1,2-Ethanetricarboxyic acid
Ether, benzyl methyl
-, p-bromobenzyl methyl
- , p-chlorobenzyl methyl
-, /7-cyanobenzyl methyl
- , dodecyl vinyl
Ethyl acetate

Ethyl alcohol
Ethylene, 1,1-diphenylEthylene glycol
- , bis(m-phenylazobenzoate)
Ethyl ether
Fluorene
Formamide, N,AT-dimethyl-

100
60
100
90
90
50
100
68
68
68
68
60
60
70
75
100
60
80
110
60
80
100
70
60
60
100
40
50
60
100

C 8 (xlO 4 )

Remarks

0.31
12.3
0.81
0.87
1.5
7.90
16.9
4.2
3.30

A
A, R
A
A
A, 15
C
C
C
C

235
524
235
127
145
182
569
569
182

1.3 x 104
1.0 x l O 4
4.0
6.0 x 104
13.OxIO 4
13.OxIO 4
0
2.28
2.75
0.8
0.9
0.387
67.48
37.87
0.988
1.914
0.333
4.12
1.1
1.137
9.8
3.84
20000
10.8
1.13
0.84
<50
0.94
6.0
6.0
4.0
20.0
3.32
4.11
15.5
5.5
6.67
0.39
1.32
1.611
2.60
450
1.36
2.70
4.70
900
5.64
75.0
124.0
1.09
0.869
4.0
1.08

F27, J
F9, J
C
J
J
J
A, S
C
C

314
314
450
159
159
159
128
4
182
220
46
474
529
529
255
255
255
182
67
255
112
235
127
235
14
14
89
72
149
149
149
149
4
4
119
123
123
72
423
479
423
432
422
422
422
281
4
127
127
458
375
113
256

F2
R
R
C
C
C
C
C
C
A
A
A
A
A

C
C
FlO
C
C
F2
F2
A
F24
F24
F24
C
C
A
A
E

Refs.

TABLE 4. cont'd
Solvent/Additive

T( 0 C)

C s (xlO 4 )

Remarks

Refs.

Styrene (cont'd)

Furan, tetrahydroa, D-Glucoside, methyl- , - , 6-deoxy-6-mercapto- , - , 2,3-di-O-benzyl- , - , 2,3,4,6-tetra-O-acejyl- , -,6-0-(p-toluenesulfbnyl)- , - , 2,3,4-tri-0-acetyl-6-deoxy-6-iodo- , - , 6-0-triphenylmethylP, D-Glucoside, methyl- , - , 6-deoxy-6-dipropylaminoGermane, ethyldichloro- , diethylchloro- , triethyl- , dimethylchloro- , triphenylHeptane

50

0.50

100
100
100
100
100
100

55000
62
2.0
2.0
50
21

1-Heptanol, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro1-Heptene
2-Heptene
Hexane
1-Hexene

100
60
60
60
60
60
60
100
60
100
100
100
100

2-Hexene
Hydrochloric acid
Hydroquinone
Hydroxylamine, MW-dibenzyl- , N-benzyl-N-phenyl- , iV,AT-diethylene- , W-ethyl-W-phenylIndium triethyl
Iron(III) chloride
Isobutyl alcohol

100
100
60
60
60
60
60
100
60
60

Isobutyl alcohol-D

100
130

22
56900
31600
2400
33500
23000
0.42
0.95
13.33
2.7
3.2
0.9
2.5
2.5
3.6
0
3.6
5000
3.8 x 104
2.5 x 104
20.5 x 104
1.760OxIO4
536.0 x 104
0.17
0.497
2.9
7.8
8.2
21.0
2.5
4.6
2.7
3.5
3.5
3.05
4.00
1.7
6.0
2.7
1.6
0.78
1.24
5.2
0.47
0.46
0.42
1.2
700
1200
0.82
1.2 x 104
30.0
62.0
0.88
0.72

Isobutyraldehyde
Isobutyric acid

60

Isobutyronitrile

100
130
60
60
80
100

Isophthalic acid, diallyl ester


Isopropyl alcohol

Isopropyl alcohol-D
Isopropyl-1-D alcohol-D
Lead, tetraethyl
Malonic acid, diallyl ester
- , diethyl ester
- , dimethyl ester
- , acetyl-, diethyl ester
- , bromo-, diethyl ester
- , butyl-, diethyl ester
- , dibromo-, diethyl ester
- , dichloro-, diethyl ester
- , diethyl-, diethyl ester
- , ethyl-, diethyl ester

130
100
100
100
60
60
100
100
100
60
100
100
60
60
100
100
100

449
220
220
220
220
220
220

A, R
A, R
A, R
A, R
A, R
A
A
F2
A
A
A
A
A, R
A
A
R
R
R
R
A
A
A
W8
C
A
A
A
F2
F2
A
F2
A
A
A
A

A
A
A
A
A

220
539
539
539
539
539
127
127
442
358
358
358
358
524
358
238
128
533
533
533
533
156
19
385
479
261
261
412
412
385
385
261
261
446
423
423
261
423
261
261
261
156
446
128
72
72
72
128
128
72
128
128
128
72
72

Remarks page 11-157; References page 11-159

TABLE 4. cont'd
Solvent/Addition

J( 0 C)

Styrene (cont'd)
Malonic acid, phenyl-, diethyl ester
Mercury, diethyl
Methane, bis(2-chloroethoxy)- , bromotrichloro-

100
100
80
80

60-80
- , dibromo- , dichloro- , diiodo- , diphenyl- , nitro- , triphenyl-

80
60
60
80
100
60
60
100

Methanetricarboxylic acid
Methanol

60
60
80
100
100
60

- , (4-biphenylyl)phenyl(p-vinyl-phenyl)- , bis(4-biphenylyl)(/?-vinyl-phenyl)Naphthalene
- , decahydro- , 2-isopropenyl-

80
100
50
50
60
60
80
99

- , 2-methoxy- , 1,2,3,9-tetahydro-l-phenyl1-Naphthol
- , 2,4-dichloro1-Naphthol-D
2-Naphthol
Naphtho[2,3-a]pyrene
2,6-Octadiene, 2,6-dimethyl2-Octene
Oleic acid, methyl ester

60
60
60
60
60
60
44.4
60
100
60

Oxalic acid, diallyl ester


- , diethyl ester
Oxetane, 3,3-bis(chloromethyl)Oxime, acrolein
- , crotonaldehyde- , ethylisopropenylketone- , methacrolein- , methylacrolein- , methylisobutylketone-,methylisopropenylketone-, methylvinylketoneOxolane, ds-3,4-diacetoxyPentane, 1-chloro- , 2,2,4-trimethyl2,4-Pentanedione

70
90
60
60
50
60
60
60
60
60
60
60
60
60
60
100
100

C s (xlO 4 )

3.5
0.335
6.0
7.6 x 104
7.7 x 104
2.4 xlO 6
2.78 x 106
6.5 x 105
(6.5 0.4) xlO 5
9450
110
0.15
9.5
11.8
710
2.3
4.2
35
10
3.5
6.0
8.0
0.91
0.296
0.74
1.10
1.22
3.5
3.5
11
0.4
56
70
69
86
<5.0
10000
480
490
75
77
24.0 x 105
2.0
2.8
3.15
3.52
455
420
6.64
4.2
13.5
8.0
10800
1500
4300
13000
400
2300
1100
2700
1.89
0.49
< 10
2.0

Remarks

C
D, Q2
D, Q2
D, Q3
D, Q3
15
A
C
A
A
A
A, R
A
A
F2
F2
F2

C
J
J
J
C
A
C
C
A
F22
C

C
A
A

Refs.

72
156
112
312
195
312
195
439
504
185
112
128
112
128
112
127
127
524
86
127
44
127
72
479
423
423
423
57
57
216
127
98
98
98
98
121
467
50,121
121
50,121
122
159
324
358
441
441
239
141
441
446
119
449
555
555
555
555
555
555
555
555
569
128
155
72

TABLE 4. cont'd
Solvent/Additive
Styrene (cont'd)
1-Pentanol, 2,2,3,3,4,4,5,5-octa-fluoro3-Pentanone
Pentasiloxane, dodecamethyl1-Pentene
- , 4,4-dimethyl-2-phenyl- , 2,4-diphenyl- , 4-methyl-2,4-diphenyl- , 4-methyl-2-phenyl- , 2,4,4-triphenyl2-Pentene
- , 2-methyl- , 4-methylPhenol
-,/7-benzyloxy
- , p-tert-buty\- , 0-chloro-,p-chloro- , 2,6-di-terf-butyl- , 2,6-diisopropyl-,p-fluoro-, m-methoxy-, o-methoxy-,/7-methoxy- , 0-phenyl- , 2,3,4,6-tetramethyl- , 2,4,6-trinitroPhenol-D,/7-benzyloxy- , 2,3,4,6-tetramethylPhenyl ether
Phosphine, dibutyl
- , diethyl
- , octyl
Phosphine, phenyl
- , tributyl
Phosphoric acid, tributyl ester
Phosphorus, white (P4)
Phosphorus trichloride
o-Phthalic acid
- , bis(2-methylallyl) ester
- , diallyl ester
- , di-(3,3,5,5-tetramethyl-4-nitrosocyclohexyl) ester
Piperidine
Propane, l-chloro-2,3-epoxy- , l-chloro-2-methyl
- , l,l,l,3-tetrabromo-3-phenyl- , 1,1,1-tribromo1,2-Propanediol
1,3-Propanediol, 2,2-bis(bromomethyl)-, diacetate
1,3-Propanedione, 1,3-diphenyl1-Propene, 3-chloro-2-methyl- , 2-methyl-, 1,3-diphenylPropionaldehyde, diallyl acetal
Propionic acid

T( 0 C)

C s (xlO 4 )

60
60
79.5
100
110
110
110
110
110
100
100
100
50
60
60
60
60
60
60
60
60
60
60
60
60
60
50
60
60
25
60
100
100
60
60
100
100
25
57
75

11.36
2.6
0.285
2.3
10
170
2900
10
2600
4.2
6.3
6.9
8.1
14
290
26
6.0
-11
49
310
54
<5
43
260
<5
580
2.1IxIO 5
10
20
7.94
7.86
2.08 x 104
1.35 x 104
3.6 x 104
43.9 x 104
24.4
<0.1
400
250
800

60
60
80
60
50
60
100
90
90
60
80
100
60
60
60
100
60
60
60

6.3
6.3
1.2 x 104
1.32 xlO 4
1.0
7.5
1.4
3.0
3.65 x 104
2.41 x 104
2.08
3.90
6.80
4.05
7.0
24.0
1.7
87.3
12.3
0.05
4.3
4.5
4.65

Remarks
F2
A
A
A
A
A
A
A
A
A
A
J

J
J

A
A, S
E
C, D

F9, J
F27, J
A
C
A
A
C
C
F24
F24
F24
A
A
A
A
C
A

Refs.
442
385
474
358
433
433
433
433
433
358
358
358
247,248
122
50,121
121
122
121
121
121
121
121
122
121
121
50,121
371
50
50
368
368
296
296
295
295
156
156
99
214
494
446
446
314
314
128
449
128
128
64
64
422
422
422
325
128
128
358
567
446
128
385
323
385

Remarks page 11-157; References page 11-159

TABLE 4. cont'd
Solvent/Additive
Styrene (cont'd)
Propionitrile, 3-phosphino- , 3,3'-phophinylidenediPropyl alcohol
Propylene oxide
2-Propyn-l-ol
Pyridine
Pyrocatechol
- , p-tert-buty\Pyrocatechol-D
- , p-tert-butylPyrogallol
Pyrogallol-D
Sebacic acid, diallyl ester
Silane, chlorotrimethyl- , dichlorodimethyl- , diethylchloro- , dimethylphenyl- , hexamethoxy-(3,3'-thiodipropyl) bis- , methyldichloro- , 3-mercaptopropyl-trimethoxy- , trichloro- , tetraethyl- , tetramethyl- , trichloromethyl- , triethyl- , trimethoxymethyl- , triphenyl-

T( 0 C)

60
60
60
80
100
50
60
60
60
60
60
60
60
60
60
50
50
60
60
79.5
60
79.5
60
100
50
50
60
70
80
79.5

Silicon chloride
Siloxane, hexamethyl-di- , dodecamethyl-penta- , octamethyltriSorbit-2,5-diacetate, 1,4:3,6-, dianhydroStannane, triphenylStearamide, Af-allyl-

60
70
80
50
79.5
79.5
79.5
60
60
90

Stearic acid, methyl ester

60

Stibine, tributyl
Stibene, dibromoStyrene, oe-bromo- , p-bromo-,dibromo- , a-ethyl- , a-methyl-

70
90
100
60
70
70
60
110
60
74
80
99

Succinic acid, diallyl ester


Succinonitrile, tetraphenylSulfonyl chloride, benzene-,/7-chloro-benzene- , p-methyl-benzene-

110
60
50
60
60
60

C s (xlO 4 )

50000
50000
2.00
3.14
3.60
1.6
7.0
0.6
1340
3600
260
370
10400
1600
4.8
12.5
17.8
5700
2200
118
9800
5.9 x 104
1.4 x 104
8.12
3.1
19.2
1200
33.4
36.8
0.23
0.230
3700
2.44
1.3
20.0
0.387
0.285
0.069
77
3.3 x 104
5.82
8.30
1.06
526
15.6
0.676
58.0
3020
10000
2000
1950
10
0.86
95
3.2
4.9
5.6
8.5
1.67
5.4
28000
4330
7650
3180

Remarks

A
A
F2
F2
F2
C
A
A
J
J
J

A, R
A, R
R
A, R
R
A, R

A, R

R
A, R

R
R
R
C
A, R
A, J
C, J
C
A
A

R
R
R

Refs.

295
295
423
423
423
449
128
128
50,121
50,121
50
50
50,121
50
446
249
249
539
539
554
539
554
539
156
249
249
539
90
90
474
554
539
90
90
249
554
554
554
569
539
173
173
441
239
141
441
156
112
172
172
112
439
431
343
98
98
98
98
431
446
89
543
543
543

TABLE 4. cont'd
Solvent/Additive
Styrene (cont'd)
Sulfonyl chloride,/?-methoxy-benzene-,methane- , phenylmethane- , a-phenyl-P-(methanesulfonyl)-ethaneTerephthalamide, NX-dimethyl-MAr'-dinitrosoTerephthalic acid, diallyl ester
Tin, tetrabutyl
Toluene

T ()
60
60
60
60
40
60
60
100
60

80

100

-,p-bromo- , m-chloro-,p-chloro- , oc-chloro-, oc,a-dichloro-, p-ethynyl-,(X- 2 Hi, toluene


-, PP- 2 H 2 , toluene
- , app- 2 H 3 , toluene
- , aaa-trichloro- , 2,4,6-trinitro/?-Toluidine
- , AW-dimethyl- , Af-methylm-Tolunitrile, a-cyanop-Tolunitrile
-,a-cyanos-Triazine, trimethylTriethylamine

Tripropylamine
Trisiloxane, octamethylUrea, l,3-bis(3,3,5,5-tetramethyl-4-nitrosocyclohexyl)Water
m-Xylene
p-Xylene
- , ot,a'-dibromo2,6-Xylenol

132
60
60
70
140
60
60
60
60
80
80
80
60
50
50
50
50
60
60
60
60
60

100
79.5
60
80
60
60
60
60
60

C s (xlO 4 )
3110
1180
3190
27600
1400
2000
4.5
3.71
0.105
0.121
0.125
0.134
0.16
0.21
0.82
1.10
2.05
0.15
0.298
0.3
0.308
0.310
0.313
0.813
0.53
0.55
0.645
0.72
0.8
1.12
1.30
1.25
0.62
1.8
1.07
1.56
50.0
72.0
0.825
0.820
0.992
57.5
14.6 x 104
78
16
11
91.4
2.07
112
0.468
1.4
3.0
7.1
7.5
24.2
0.069
14500
15000
0.006
0.31
0.78
0.84
150
110

Remarks
R
R
R
R

C
A
A, 15
C
C
15
C
C
C, F17
A
C
A
A
A, 15
A

A
A
K
C, F17
C, F17
C, F17
A
F2
F2
F2

W9
W6

F9, J
F9, J
A, R

Refs.
543
543
543
543
160
160
446
156
255
21,24,79
127
78
145
318
496
363
363
385
185
385
255
76,77
78,273
530
235
385
127
235
145
235
496
496
67
67
496
128
128
151
530
530
530
128
370,372
154
154
154
462
496
461
88
364
364
24
363,364
156
474
314
314
479
529
496
496
112
121

Remarks page 11-157; References page 11-159

TABLE 4. cont'd
Solvent/Additive
Styrene {confd)
Zinc, diethyl
- , p-chloroAnisole, p-isopropylBenzaldehyde
-,p-chloroBenzene, p-diisopropyl-

T( 0 C)
100
60
100
100
60

Benzonitrile, p-isopropylCarbon tetrabromide


Carbon tetrachloride
Cumene
-,p-bromo- , p-terf-butyl--, p-chloro- , p-iodoBenzene
- , p-methyl
Anisole, p-isopropylBenzene, p-diisopropyl-

60
60
60
60
60
60
60

Benzonitrile, p-isopropylCumene
-,p-bromo- , p-terf-butyl-,p-chloro- , pentafluoroBenzene, bromo- , chloro-,ethyl- , fluoro2-Butanone, 3-methylCumene
Furan, tetrahydro-

60
60
60
60
60

2-Pentanone, 4-methylToluene
Styrene/Styrene, p-chloroCarbon tetrachloride

60
60

Succinimide, N-vinylAcetic acid


Ethane, 1,2-dichloroValeric acid, 4-methyl-, vinyl ester
Benzene
Vinyl acetate
Acetaldehyde

Acetamide, N-butylAcetic acid

C s (xlO 4 )

Remarks

3660
3.86
1.9
9.7
3.62
7.24
8.84
52000
45
3.44
5.71
3.52
4.97

Refs.
156

A
A

F2

406
298
298
497
406
406
109
366
406
406
406
406

50

0.2

56

60
60

3.27
3.67
7.34
26.0
4.12
9.23
3.59
7.67

408
408
406
408
408
408
408
408

60
60
60
60
60
60
60

60

0
0
5.35
0.117
1.09
6.76
1.53
1.61
0.033
1.20
15
115

55
55

0.077
0.127

80

6.2

30
45
50
60

400
530
390
0.72
200
220
500
570
660
610
700
40
0.180
0.166
0.200
1.0
1.13
10
0.170

70
75
60
50
60

65

EF
EE
C, F25
C, F26

469
469
469
469
469
469
469
469
469
469
366
366
93
93
201

J
18
F2
J
J
C
19
F2
C

346
86
460
257
145
232
460
86
86
460
86
86
466
465
466
145
289
86
466

TABLE 4. cont'd
Solvent/Additive
Vinyl acetate (cont'd)
Acetic acid, allyl ester
- , benzyl ester
- , butyl ester
- , sec-butyl ester
- , tert-butyl ester
- , isobutyl ester
- , isopropyl ester

- , methyl ester
- , propyl ester
- , 1,3,3,3-tetrachloropropyl ester
- , bromo- , chloro- , cyano-, methyl ester
- , dichloro-, ethyl ester
- , phenyl- , trichloro- , ethyl ester
- , trifluoro-, ethyl ester
Acetic anhydride
Acetoacetic acid, ethyl ester
Acetone

Acetonitrile
-,phenylAcetophenone
- , 3'-hydroxy- , 3'-hydroxy-DAniline
- , AW-dimethyl- , W-methyl-,p-nitrom-Anisaldehyde
o-Anisaldehyde
/7-Anisaldehyde
Anisole
Anthracene

- , 9-phenylBenzaldehyde

T( 0 C)

60
60
50
50
60
50
60
50
50
60
67.5
75
60
50
60
70
60
70
70
60
60
60
70
60
50
60
70
60
70
75
60
60
50
60
70
45
45
50
50
50
50
60
60
60
60
20
30
40
50
60
50
60
70
75

C s (xlO 4 )

85
94
80
13.2
4.4
8.0
1.5
6.2
9.1
3.5
3.1
8.0
9.0
10
1.56
1.6
2.5
6.2
3.4
423.2
489
4450
2550
5000
210
400
1445
4400
30
8.0
80.4
1.5
11.70
12.0
25.6
42
10
2100
91.5
100
62.0
1405
1290
149
210
260
360
48600
2500
420
370
10
6.68 x 105
6.03 x l O 5
4.55 x 105
2.057 x 105
3.64 x 105
2.78 x 105
2.73 x 105
230
460
540
421
600

Remarks

F2
J
F2, J

J
J

C
C, J
C
C
J
J
C
C
C

C
C
J
J
C
J
J
F2
F2
F2
J
J
J
F2, J
J
J
J
J
J
J
J
F2
J
C,J
J

Refs.

86
86
86
208
208
86
208
232
208
208
145,232
86
86
86
145,231
145,232
86
208
145,232
389
386
389
389
86
86
86
389
86
71
86
390
86
289
145
330
184
86
86
15
86
390
51
51
15
154
154
154
15
86
86
86
86
41
41
41
15
41
41
41
145,355
86
86
390
86

Remarks page 11-157; References page 11-159

TABLE 4. cont'd
T( 0 C)

Solvent/Additive
Vinyl acetate (cont'd)
Benzaldehyde, m-chloro- , o-chloro-,p-chloro-,
- , p-cyano-,/7-isopropylBenz[A]anthracene
Benzene

ra-cyano-

60
60
60
60
60
60
50
60

70
75
- , bromo-

- , tert-butyl- , chloro-

Benzene, o-dichloro-,/7-dichloro- , m-dinitro- , 0-dinitro


- , p-dinitro-,ethyl- , nitro- , 1,3,5-trinitroBenzo[B]chrysene
Benzoic acid
- , ethyl ester
-,p-nitroBenzoic anhydride
Benzoin
Benzonitrile
- , m-hydroxy- , m-hydroxy-DBenzo[GHI]perylene
Benzophenone
Benzo[A]pyrene
Benzo[E]pyrene
p-Benzoquinone, 2,3,5,6-tetramethylBenzoyl chloride
Benzyl alcohol
Biphenyl
Borane, tributyl

50
60
70
75
60
60

70
75
75
70
45
50
45
45
50
60
50
45
50
50
60
60
50
60
60
50
45
45
50
50
50
50
45
50
70
70
50
60
10

C s (xlO 4 )

860
390
340
1070
610
540
1.17 xlO 5
1.07
1.2
1.2
2.4
2.96
20
5.27
1.4
1.40
3.6
18.9
8.0
9.2
10.0
134.2
25.2
3.61
5.6
6.8
8.0
8.35
80
2.61
12.7
42
11.8
1.05 x 106
645700
9.6 x 105
26.7 x 105
662800
55.15
100
110300
8.9 x 106
434280
2.83 x 105
50
26
245700
130
800
40.6
820
805
1.82 xlO 4
286
3.06 x 105
8400
9.5 x 105
366
300
556
263
6.4
9000

Remarks

J
J
J
J
J
J
J
J
C
C
J
C
W7
W15
C
C
W7
W15
J
C
C
C
C
C, J
C, J
C, J
J
C, J
J
J
J
J
J
J
J
J
J
J
J
C
C

Refs.

86
86
86
86
86
86
41
263
86
294
80
289
294
390
86
263
184
15
265
265
265
389
184
289
265
265
265
289
86
389
184
184
389
28
15
28
28
15
289
86
15
28
15
41
86
86
15
86
86
15
51
51
370
15
41
370
27
15
389
390
15
132
191

TABLE 4. cont'd
Solvent/Additive
Vinyl acetate (cont'd)
Butane, 1-bromo- , 1-chloro- , 1-iodo2,3-Butanedione
2-Butanone
-, 3-methyl1-Butene, 3-chloro-3-methyl2-Butene, l-chloro-3-methyll-Buten-3-yne
Butyl alcohol
sec-Butyl alcohol
tert-Butyl alcohol

Butyl ether
3-Butyn-2-ol, 2-methylButyraldehyde

T( 0 C)

60
70
60
60
60
60
75
60
50
50
60
60
70
60
70
75
60
70
60
60
40

60
Butyric acid, ethyl ester
- , methyl ester

70
50
60

Carbon tetrabromide

60
70

Carbon tetrachloride

0
20
45
60

Chloral

Chloral hydrate
Chloroform

2-Chloro-3-(methyl-14C)-lbutene(4-14C)
3-Chloro-2-pentene-(2,4-14C)

70
75
60
70

70
30
60

70
50
50

C s (xlO 4 )

50
1100
10
800
670
73.80
165
118.16
28900
4300
0
20.0
20.39
29.1
31.74
6.21
95.0
0.46
0.5
1.3
12.1
76
400
440
510
590
670
650
1000
388
45
18
19
7.39 x 106
28740
1500
4700
7600
800
1300
4700
6700
7300
8000
9000
9600
10000
10500
10700
2023
10500
5000
4927

4312
100
140
125.18
130
150
160
170
554
3980
628

Remarks

C
F2, J
C
F2
F2
J
19
C
C
C
19
C,J
J
W8
W7
W15

C
C
F2
C
E
J
Ql
Q2
Q3
Q4
F2
Q5
Q6
J
Q7
Q8
C
J
C

19
J
F2
C
F2
F2

Refs.

86
389
86
86
86
289
184
289
152
152
232
145
289
390
289
390
184
289
145
86
390
86
86
500
500
500
500
232,355
86
390
71
145,232
86
109,145
389
346
309
86
10
10
10
10
86
10
10
86
210
10
10
389
86
86
389

389
345
346
289
145
86
210
86
389
509
509

Remarks page II-157; References page 11-159

TABLE 4. cont'd
Solvent/Additive
Vinyl acetate (cont'd)
Chrysene
w-Cresol
m-Cresol-D
p-Cresol
p-Cresol-D
Crotonaldehyde
Cumene

Cyclohexane

T( 0 C)

50
45
45
45
45
60
60
70
75
60

-,methyl-

60

1,3-Cyclohexanedione, 5,5-dimethylCyclohexanol
Cyclohexanone

70
70
60
75
60

Cyclohexene
Dibenz[a,h]anthracene
Dibenzo[def,mno]chrysene
1,2,3,4-Dibenzpyrene
Diethylene glycol
Diethylphosphonate

p-Dioxane
Diphenylamine
Diphenylamine-D
Diphenylamine-T
Ethane, 1,1-dibromo- , 1,2-dibromo- , 1,1-dichloro- , 1,2-dichloro-,
-,
-,
-,
-,

75
50
40
50
60
50
70
60
60
60
60
60
70
50
60
60
60
60
70
60
60

1,2-dichlorohexachloropentachloro1,1,2,2-tetrabromo1,1,2,2-tetrachloro-

70
70
70
60
60

- , 1,1,1-trichloro- , 1,1,2-trichloro1,1-Ethanediol, diacetate


Ether, benzyl methyl
- , bis(2-chloroethyl)
- , dodecyl vinyl

70
60
60
60
60
70
60

-,ethyl
Ethyl acetate

60
20
40
50
60

C s (xlO 4 )

3360
375
85
710
130
1800
89.9
100
139
356
6.59
7.0
100
11.75
24
5580
127
180
670
620
1600
770
8.7 x 104
156.5 x 104
129.2 xlO 4
105.4 xlO 4
73.6 x 104
85.3
350
910
830
730
20
49.1
138
240
170
230
1100
134
65
5
7
7.18
10.2
1210
1348
6000
107.03
160
67.72
71.11
35.98
40
280
245
57.2
73.5
45.3
1.52
2.11
2.9
12
1.07

Remarks

J
J
J
J
J
J
C
C
19
F2
C
C
F2
C
J
F2
J
J
J
J
J
J
C
Fl
F2
F2
F2
F2
C

C
19
C
C
C

F2, J
C
C
C
C

Refs.

370
51
61
51
51
355
289
7,86
390
184
289
145
86
289
86
390
390
86
184
86
86
86
370
41
41
41
41
390
571
571
571
571
86
390
15
46
46
46
86
389
86
86
145
289
389
389
389
86
289
86
389
289
289
86
86
389
4
4
4
328
328
208
71
289

TABLE 4. cont'd
Solvent/Additive

T( 0 C)

Vinyl acetate (cont'd)


Ethyl acetate (cont'd)

Ethyl alcohol
Ethylene, tetrabromo- , tetrachloro- , tribromo- , trichloroEthylene glycol
Fluorene
- , 9-phenylFormamide, N9N, -dimethylFormic acid, ethyl ester
- , methyl ester
2-Furaldehyde
Furfuryl alcohol
Germane, diethylchloro- , dimethylchloro- , triethyl-,triphenylGlycolic acid, methyl ester
Heptane
1-Heptanol, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluorol,5-Hexadien-3-yne
Hexanoic acid, 2-ethyl-, ethyl ester
Hydroquinone
- , 2,5-di-terf-butyl- , 2,6-dimethyl- , tetramethylIsobutyl alcohol
Isobutyric acid
Isobutyric acid, ethyl ester
-, methyl ester
Isobutyronitrile
Isopropyl alcohol
Lactic acid, ethyl ester
-, methyl ester
Laurie acid, ethyl ester
Malonic acid, dimethyl ester
/?-Mentha-l,8-dene
Mesitol
Methane, bromotrichloro-

- , dichloro- , iodo- , nitro-,tribromo- , triphenylMethanol

C s (xlO 4 )
1.25

70
60
70
70
70
70
70
70
60
70
70
60
50
60
60
70
60
60
60
60
60
50
60
60
50
50
50
50
50
60
70
60
50
60
60
70
60
60
50
60
60
50
25
60
70
60
70
60
75
70
60
10
60

2.6
2.96
3.3
3.4
7.8
25
26.3
2800
465
34720
3810
83.0
4700
3610
16240
50
22
3
15000
2520
7800
86600
4500
56000
300
17.0
33.3
0
65
7000
38000
29000
74000
21.75
32.4
5.02
160
58
71
86
100
44.6
700
640
105
17
1900
5000
> 104
6000
>4xlO5
6303
4
1230
2300
2600
34760
700
9.0
10.0
10.5
3.4
2.26

Remarks

C
F2
C
C
C
C
C
C, J
J
C,J
C
C
J
C, J
A, R
A, R
A, R
A, R
F2
C
J
J
J
J
C
C

C
C
J
J
D, S
C
C
C
C
F2, J
J
C

Refs.

80

145,232
328
86
420
390
86
390
389
389
389
389
390
86
390
390
86
71
86
86
390
539
539
539
539
86
208
442
232
71
338
338
338
338
289
390
289
71
145,232
420
86
86
390
86
86
71
86
86
338
39
39
39
389
86
389
86
86
389
45
5
5
5
190
145,231

Remarks page II-157; References page 11-159

TABLE 4. cont'd
Solvent/Additive

T (0C)

Vinyl acetate (cont'd)


Methanol (cont'd)
Naphthacene
Naphthalene

70
50
50

- , decahydroNaphtho[l,2,3,4-def]chrysene
Nonanoic acid, ethyl ester
2,6-Octadiene, 2,7-dichloro- , 2,6-dimethyl-

70
60
50
50
50
60

Octanoic acid, ethyl ester


Oleic acid, methyl ester

50
60

Oxalic acid, diethyl ester


- , dimethyl ester

90
30
60
60

Paraldehyde
Pentane, 2,2,4-trimethyl2,4-Pentanedione
1-Pentanol, n 2,2,3,3,4,4,5,5-octafluoro2-Pentanone, 4-methyl3-Pentanone

70
50
60
60
60
60

Pentyl acetate

70
75
75
50
50

Orthoformic acid, trimethyl ester

Pentyl alcohol
Perylene
Phenanthrene

Phenol

70
45
50
60

- , m-chloro-,p-chloro- , p-nitro- , 2,3,4,6-tetramethylPhenol-D


-,m-chloro-,p-chloro-,2,3,4,6-tetramethylPhosphorus trichloride
Propane, 2-bromo-2-methyl- , 2-chloro-2-methyl
1-Propanol, 2,2,3,3-tetrafluoro1-Propene, 3-chloro- , 3-chloro-2-methylPropionaldehyde

45
45
50
45
45
45
45
45
60
60
60
60
60
60
60

Propionic acid, ethyl ester


- , methyl ester

70
50
60

Pyrene
Pyrocatechol, 4-(l,l,3,3,-tetramethylbutyl)Pyrogallol
Salicylic acid
Silane, dimethylphenyl-

50
50
50
70
60

C s (xlO 4 )

4.3
6.0
5.5
8.62 x 106
1150
1457
1715
48
1.35 x 105
80
3200
430
700
70
217
1000
358
7.6
8.0
4.0
1.0
2.0
136
8.0
10
26.1
34.52
10.0
114.39
7.2
87.0
56
2.88 x 105
870
5600

3380
215
120
600
205
400
8.86 x 104
1.13 x 104
35
70
80
800
1.5 x 104
150
26
7.11
3100
400
950
1000
457
40
23
26
11500
11000
50000
296
2200

Remarks

J
J
C,J
J
C
F2
C
J

C
F2
19
C
C
C
J
J

C,J
J
J
J
J
J
J
J
J
J
C, D
F2
J
J
F2
C
C
J
J
J
C
A, R

Refs.

320
86
320
370
370
15
390
86
41
71
152
324
7
71
441
86
441
345
346
86
86
145,232
390
208
86
442
289
145
289
390
184
184
41
370
15

390
51
15
86
51
51
15
51
51
51
51
51
214
86
86
442
86
86
86
86
390
71
232
420
370
338
338
390
539

TABLE 4. cont'd
Solvent/Additive
Vinyl acetate (cont'd)
Silane, methyldichloro- , trichloro- , triethyl- , triphenylStearamide, N-allylStearic acid, ehtyl ester
- , methyl ester
Succinic acid, diethyl ester
- , dihexyl ester
- , dimethyl ester
m-Tolualdehyde
p-Tolualdehyde
Toluene

T( 0 C)

60
60
60
60
90
50
60
60
60
60
60
60

75
80
50
70
70
60
70
75
50
50
50
50
50
50
60
50
60
50
70
75
60
60
60

280
290
400000

Q(3)
Q(3)
Q(3)

511
511
511

50
60

20
20

R
R

541
541

60
60
60
60
60

5400
8600
12000
2000
4000

A, R
A, R
A, R
A, R
A, R

539
539
539
539
539

C, Q(I-2)

572

60
70

Triphenylene
Veratraldeyhyde
Xylene
Vinyl chloride
Carbon tetrachloride
Chloroform
Bromotrichloromethane
Vinylidene chloride
Af-Methylpyrolidone
2-Vinylpyridine
Silane, diethylchloro- , Methyldichloro-,trichloro-,triethyl-,triphenylVinyltrimethylsilane
Bromoform

Refs.

A, R
A, R
A, R
A, R
C, J
C

60

Toluene, p-nitrop-Toluidine
-, N,Ar-dimethyl-, AT-methylToluonitrile
Triethylamine

Remarks

5800
8800
1200
2700
620.1
140
38.2
41
40
31
570
440
3.3
12.0
14.9
100
123
17.8
20.75
20.89
21.6
34
35
49.0
69.0
21.1
21.8
29.2
66
91.6
20.6
92.86
195
450
584
118
106300
750
380
830
38.3
360
370
160
550
14.9
278
166

50

- , bromo- , o-chloro-,p-chloro- , a-chloro-

C s (xlO 4 )

1200000

J
J
R
C
R
C
J
F2
W15
R
C
C
C
C
J
C
C
F2
F2
F2
F2
J
J
J
C
C

539
539
539
539
173
71
441
420
420
420
86
86
158
15
357
71
71
357
80
21,59,289
357
86
86
265
265
357
390
357
184
273
15
389
389
86
389
184
15
154
154
154
15
154
24,145
370
86
15
390
184

Remarks page 11-157; References page 11-159

TABLE 5. TRANSFER CONSTANTS TO SULFUR COMPOUNDS


Modifier
Acrylamide, A/-octadecyl-/acrylonitrile (1:1 mol ratio)
1-Dodecanethiol
Acrylic acid
1-Dodecanethiol
- , methyl ester
1-Butanethiol

J( 0 C)

Cx

Remarks

Refs.

60

0.539

C, F24

174

45

1.9

C, F31

549

Ethanethiol

30
60
50

2-Propanethiol

60

1.53
1.69
0.78
0.94 0.07
1.65 0.12
1.57 0.09
1.57 0.18
1.79
5.00
0.544
0.668
0.700
0.656

A
A
Ql
Ql
Q2
Q3
Q4
Q2
Q3
Ql
Q2
Q3
Q4

Acrylonitrile
1-Dodecanethiol
Hydrogen sulfide
Methyl sulfoxide

Methyl tetrasulfide
p-Toluenethiol
Acrylonitrile/1,3-butadiene (10-90%)
1-Hexanethiol,
- , 1,1,3,3,5,5-hexamethyl1-Pentanethiol,
- , 1,1,3,3-tetramethylAcrylonitrile/1,3-butadiene (20-80%)
1-Hexanethiol
- , 1,1,3,3,5,5-hexamethyl1-Pentanethiol
- , 1,1,3,3-tetramethylAcrylonitrile/1,3-butadiene (30-70%)
1-Hexanethiol
- , 1,1,3,3,5,5-hexamethyl1-Pentanethiol
- , 1,1,3,3-tetramethylAcrylonitrile/styrene (38.5-61.5 mol%)
1-Pentanethiol
- , 1,1,3,3,4-pentamethylButadiene
Xanthogendisulfide, dibutyl- , diethyl- , di-2-ethylhexyl- , di-isopropyl1,3-Butadiene
1-Butanethiol, 1,1,3,3-tetramethyl1-Octanethiol
- , 1,1,3,3,5,5,7,7-octamethyl1-Tetradecanethiol
1,3-Butadiene/styrene
1-Dodecanethiol
Formic acid, thio-, dithiobis_, _, _, ao'-dibutyl ester

50
50
20
30
40
50
80
50
5

0.73
0.13
0.1
0.47
0.0000812
0.11
0.29
0.795
0.69
0.97

C, F8
E

397
69,397
330
478,507
478,507
508
330,509
330
330
477
477
477
477
378
378
248
196
458
404
197
375
85
378

1.5

C, H

380

53.3

C, H

380

1.2

C, H

380

2.1

C, H

380

1.1

C, H

380

1.8

C, H

380

50

1.02

C, H

380

60
60
60
60

6.9
8.1
7.5
8.3

J
J
J
J

532
532
532
532

5
50
5
50

5.3
3.7
21.8
16.0
19.0
3.0
19.5

H
H
H
H
H
H
H

242
242
242
242
243
242
242

50
50
5

0.66

B, H, J

384

2.42

B, H, J

383

TABLE 5. cont'd
Modifier

T( 0 C)

1,3-Butadiene/styrene {cont'd)

- , - , ao'-diisopentyl ester

-5
50
5
-5
5
50
5
-5
50
5
50
5
50
5
-5
50
5

- , - , - , 0,O'-diisopropyl ester

-5
50
5

- , - , - , O,O'-di-sec-butyl ester
- , - , - 0,O'-dicyclohexyl ester
_, _, _, 0,0'-diethyl ester
- , - , - , 0,O'-diheptyl ester
- , - , - , 0,6>'-dihexyl ester
- , - , - , 0,O'-diisobutyl ester

- , - , - , 0,O'-dimethyl ester
- , - , - , 0,O'-dineopentyl ester
- , - , - , 0,0'-dioctyl ester
- , - , - , 0,O'-dipentyl ester
- , - , - , 0,0'-dipropyl ester
1-Heptanethiol
- , 1,1,3,3,5,5,6-heptamethyl1-Hexanethiol
- , 1,1,3,3,5,5-hexamethyl1-Octanethiol
- , 1,1,3,5,5,7,7-octamethyl/7-Dioxin, 2,3-dihydro/maleic anhydride
1-Butanethil
Ethylene
1-Butanethiol
Ethyl sulflde
Methyl sulfoxide
2-Propanethiol, 2-methylSulfur hexafluoride
Methyl methacrylate
Acetic acid, dithiodi-, diethyl ester
- , mercapto-, methyl ester
Acetophenone, 3'-mercapto- , 4'-mercapto-

-5
50
5
-5
50
5
50
5
50
5
-5
50
5
-5
50

Cx
1.75
5.34
1.65
1.565
1.78
3.71
8.43
4.23
16.04
0.41
1.12
0.74
1.78
1.87
1.573
6.43
1.21
7.0
1.85
4.38
2.83
3.4
12.5
0.40-1.31
0.80-3.01
1.40-3.70
1.80-3.50
1.80-6.0
9.78
1.185
9.78
16.43
15.86
27.04
1.01
3.40
0.23
0.64
1.45
1.70
3.20
4.42
1.815
9.20

Remarks
H
C, H, J
B, H, J
H
B, H, J
C, H, J
B, H, J
H
C, H, J
B, H, J
C, H, J
B, H, J
C, H, J
B, H, J
H
C, H, J
B, H, J
B, H, J
H
C, H, J
B, H, J
B, H, J
B, H
B, H, J,
B, H, J,
B, H, J,
B, H, J,
B, H, J,

Refs.
180
382

H
C, H, J
B, H, J
H
C, H, J
B, H, J
C, H, J
B, H, J
C, H, J
B, H, J
H
C, H, J
B, H, J
H
C, H, J

180
383
383
383
180
382
383
382
383
382
383
180
382
383
341
180
382
383
341
100
100
100
100
100
100
179
180
382
383
180
382
383
382
383
382
383
180
382
383
180
382

GG4
GG3
GG2
GGl
GG5

0.64

B, H, J

384

1.22
4.1
2.7-4.7

B, H, J
H
H

384
54,55
54

0.34

B, H, J

384

169

C, W5
C, W5
C, F21, W5
C, W5
C, F21, W5

457
454
259
457
259

60
130
130
130
130
130
60
60
45
45

6300
5.8
0.027
12
15.0
0.0000
0.00065
0.63
4.2
2.6

86
274
30
30

Remarks page II-157; References page 11-159

TABLE 5. cont'd
Modifier
Methyl methacrylate {cont'd)
Anisole, 4,4'-dithiodip-Anisoyl disulfide
Benzenesulfonic acid
- , compound with pyridine
- , thio-, S-phenyl ester
Benzenethiol
- , m-bromo- , /7-bromo- , m-chloro-,p-chloroBenzoyl disulfide
Benzyl disulfide
Benzyl sulfide

J( 0 C)
50
60
60

0.0044
0.0052
14.6

60
60
45
60
70
45
45
45
45
60
25
50
60
25
50

0.00365
0.0196
4.7
2.7
15
3.8
5.6
3.5
4.6
10.0
0.134
0.016
0.00627
0.0183
0.0098
0.0098
0.00154
0.0040
0.0039
0.084
0.021
0.66
0.67
0.008
0.22
0.09
0.35
0.33
0.21
0.13
0.55
0.00007
0.00258
16.7
0.0046
0.0098
10.0
0.0072
0.0117
290
0.0115
694
0.0176
0.0508
0.0127
0.0193
0.7
0.55
0.42
0.33
0.17
0.15
0.43
0.62
0.40
0.00013

Benzyl sulfone
Benzyl sulfoxide
Benzyl tetrasulfide
Benzyl trisulfide
1-Butanethiol

60
50
50
50
50
60

Carbanilide, thio-

50

_, _, 4,4/-bis(dimethylamino)- , - , 4,4'-dichloro- , - , 3,3/-dimethoxy-, -, 3,3'-dimethyl- , -, 4,4'-dimethyl- , - , 3,3'-dinitroCarbon disulfide


2,13-Dioxa-7,8-dithia-3,12-disila-tetradecane, 3,3,12,12-tetrameth oxyDisulfide, bis(p-bromobenzoyl)- , bis (p-bromophenyl)-

50
50
50
50
50
50
60
79.5
60
50
60
60
50
60
60
70
60
50
60
50
60
60
70
80
90
50
70
50
60
70
60

- , bis(p-chlorobenzoyl)- , bis(p-chlorophenyl)-,
-,
-,
-,

bis(p-cyanobenzoyl)bis(dimethylthiocarbamoyl)bis(p-nitrobenzoyl)bis(onitrophenyl)-

- , bis(/?-nitrophenyl)1-Dodecanethiol

Ethanethiol, 2-amino-, hydrochloride


Ethanol, 2-mercaptoEthyl disulfide
Formamidine, A^Af'-diphenyl- , - , U'-dithiobisMethyl sufoxide

Cx

50
60

0.22
0.0000071

Remarks

Refs.
285
285
369

F2
D
F2

F2, J
F2, J
A
F2
C, F2
C, F2
C, F2
C, F2
C, F2
C, F2
C, F2
A

F7
F7
F2
F2
C, F2
A

490
491
30
274
566
30
30
30
30
369
368
354
368
368
252
354
368
252
252
354
354
274
69,397
251
251
251
251
251
251
251
251
288
474
369
285
285
369
285
285
369
104
369
285
285
285
285
573
573
573
573
473
473
473
274
473
310
251
438

TABLE 5. cont'd
Modifier
Methyl methacrylate (cont'd)
2-Naphthalenethiol
1-Penthanethiol
Phenyl disulfide

Phenyl disufone
Phenyl sulfide
Phenyl sulfone
Phenyl sulfoxide
1-Propanethiol, 3-[l,3,3,3-tetramethyl-l-(trimethylsiloxy)disiloxanyl]- , 3-(trimethoxy)2-Propanethiol
- , 2-methylPropionic acid, 3-mercaptoSulfide, benzoyl dimethylthiocarbamoyl
Sulfur
Thiosulfuric acid, S-butyl ester
- , - , sodium salt
- , S-isopropyl ester
- , - , sodium salt
- , S-phenyl ester
- , - , compound with pyridine
- , - , potassium salt
- , S-propyl ester
- , - , sodium salt
m-Toluenethiol
p-Toluenethiol
a-Toluenethiol
p-Toluoyl disulfide
p-Tolyl disulfide
Styrene
Acetic acid, dithiodi-,
-,
-,
-,
-,
-,

-,
-,
-,
-,
-,
-,

diethyl ester
dimethyl ester
mercaptobutyl ester
ethyl ester
methyl ester

- , phenyl- , - , /?,/?'-dithiodi- , thio


Aniline, 2,2' dithiodi-

-, 4,4'-dithiodi- , N-dodecyl-, 4,4'-dithiodiAnisole, 2,2'-dithiodi- , 4,4'-dithiodi- , p-methyl-, a,a'-dithiobis-

T( 0 C)
45
60
50
25
50
60

Cx

Remarks

Refs.

60
25
50
60
50
50
79.5
79.5
60
60
50
70
20
60
44.1
50

1.3
3.1
0.8
0.0174
0.0038
0.0007
0.00176
0.0085
0.0110
0.0003
0.00554
0.0064
0.00132
0.0006
0.0013
0.128
0.693
0.38
0.18
0.39
0.38
5.5
0.08
1.3
0.075
0.106

60

0.00226

490

60

0.00167

490

60
60

0.374
0.00537

490
490

60
45
45
50
60
50
60

0.00190
4.7
7.4
0.027
11.0
0.0031
0.0044

490
30
30
354
369
285
285

50
99
60
99
99
50
60
60
99

< 0.005
0.2
0.015
0.1
>14.0
26.0
58.0
0.63
27.6

50
99
25
50

0.24
>14.7
3.8
3.0
3.4
3.0
0.24
0.21
3.0
0.18
0.021

75
50
50
50
50
99

H
D

A
A
D

F2
F2
D
A
C
F2, J

F2, J

J, R
A
A

30
274
344
368
285
310
368
285
491
491
368
252
368
252
252
474
474
274
274
473
473
280
280
118
194
354

297
96
86
96
96
146
126
323
96
89
96
297
297
297
297
89
89
89
89
96

Remarks page 11-157; References page 11-159

TABLE 5. cont'd
Modifier
Styrene {cont'd)
/7-Anisoyl disulfide
Anthranilic acid, 4,4'-dithiobisArylbenzene thiolsulfonate
- , /?-chloro
- , p-methoxy- , p-methylBenzenesulfonic acid
- , compound with pyridine
- , thio-, S-phenyl ester
Benzenethiol
- , o-ethoxy-,p-ethoxyBenzene thiosulfonate
- , aryl-p-chloro- , aryl-p-methoxy- , aryl-p-methyl
2-Benzimidazolethiol
Benzoic acid, 2,2/-dithiodi- , - , diethyl ester
- , -,dimethyl ester
-, 4,4'-dithiodi- , - , diethyl ester
- , o-mercapto- , -, methyl ester
-,thioBenzothiazole, 2,2/-dithiobis-

- , 2,2'-thiobis2-Benzothiazolethiol
Benzo[B]thiophene, 4,5,6,7-tetrahydro-4(2-thienyl)Benzoyl disulfide

Benzyl alcohol, ^o'-dithiobis-,/vAdithiobisBenzyl diselenide


Benzyl disulfide

T( 0 C)
60
50
60
60
60
60

96.0
3.0
0.95
2.22
1.872
1.237

60
50
60
99
99
99

0.00617
1.60
1.67
0.08
25.1
0.13

60
60
60
99
50
50
99
50

2.597
1.475
1.099
0.21
0.01
< 0.005
0.2
0.11
0.17
0.11
>14.7
17.0
6.23
2.3
2.1
2.3
2.4
2.73
< 0.005
0.03
0.26
0.011
< 0.005
0.010
0.0107
36.0
0.11
0.58
0.09
2.0
0.02
0.03
0.00878
0.01
0.011
0.548
0.069
0.00335
0.052
0.051
5.4
13.2
21.0
22.0
25
15.0
17.0
15.4

50
99
99
99
25
50
75
99
50
50
99
60
50
60
99
50
50
60
50
60

Benzyl sulfide
Benzyl sulfone
Benzyl sulfoxide
1-Butanethiol

Cx

99
25
50
60
50
50
25
60

70
80
99

Remarks

R, F2
R, F2
R, F2
R, F2
A
A

R, F2
R, F2
R, F2

A
D

D, Ql
D
A
A
A
A

Refs.
369
89
544
544
544
544
490
491
491
96
96
96
544
544
544
96
89
89
96
297
89
89,297
96
96
96
297
297
297
297
96
297
297
96
419
89
545
304
369
96
89
297
128
89
297
368
128
96
368
252
368
252
252
340
340
395
69,397
131
395
395
96

TABLE 5. cont'd
Modifier
Styrene (cont'd)
1-Butanethiol, 1,1,3,3-tetramethyl-

1-Butanethiol-D

Butyl disulfide

sec-Butyl disulfide
tert-Butyl disulfide
Butyl sulfide
tert-Butyl sulfide
Carbanilic acid, /?,/?'-dithiodi-diethyl ester
Carbon disulfide
Carbonic acid, dithio- , - , S,S'-bis(carboxymethyl)ester
- , trithio- , - , S,S'-bis(carboxymethyl) ester
1-Decanethiol
2,13-Dioxa-7,8-dithia-3,12-disilatetradecane, 3,3,12,12-tetramethoxyDiphenyldisulfide
Disulfide, bis(/?-bromobenzoyl)
- , bis(a-bromo-o-tolyl)
- , bis(/?-chlorobenzoyl)
- , bis(chlorobenzyl)
- , bis(2-chloroethyl)
- , bis(a-chloro-o-tolyl)
- , bis(>-cyanobenzoyl)
- , bis(diethylthiocarbamoyl)
- , bis(dimethylthiocarbamoyl)

T( 0 C)

5
50
60
70
80
25
55
60
99
150
50
50
60
60
60
50
60
50
50
80
80
79.5
60
60
50
60
50
50
50
60
60
60
70
80
95
115
130

- , bis(2-ethylhexyl)
- , bis(A^ethyl-A^phenylthio-carbamoyl)
- , bis(l-methylheptyl)
- , bis(morpholinothiocarbonyl)
- , bis(l-naphthylmethyl)
- , bis(/?-nitrobenzoyl
- , bis(o-nitrophenyl)
- , bis(l-phenylethyl)
- , bis(P-(2-pyridyl)ethyl)
- , bis(2,3,5,6-tetramethylphenyl)
- , bis(2,4,6-triisopropylphenyl)
1-Dodecanethiol

50
60
99
60
99
60
50
50
50
50
50
60
70
70
90
100
110

Cx

5.5
6.4
4.3
5.2
4.0
7.0
0.00079
0.00154
0.0024
0.0068
0.022
< 0.005
< 0.005
0.00014
0.0022
0.025
0.24
0.00066

Remarks

H
H
H
A
A
A

0.36
0.21
4.3
4.2
0.0118
0.147
745
1.0
196
< 0.005
0.01
1.3
3190
0.724
1.11
0.0136
0.568
0.620
0.780
0.860
0.939
1.035
0.984
1.150
< 0.005
1.75
0.0104
6.1
0.033
6650
<0.005
0.03
0.73
0.12
14.8
19.0
19
0.69
1.3
13.0
26.0

Refs.

242
222
242
395
395
395
448
448
304
96
359
89
89
304
304
304
89
288
297

C3, H
C3, H

J
J
J

C3, H
C3, H

297
574
574
474
546
369
297
369
297
297
297
369
286
286
104
40
481
481
40
40
481
40
481
297
286
96
286
96
369
89
89
297
297
89
69,126
59
562
574
574
156
156

Remarks page II-157; References page 11-159

TABLE 5. cont'd
Modifier
Styrene (cont'd)
terf-Dodecanethiol
Ethanethiol
Ethanol, 2,2'-dithiodi- , - , di(chloroacetate)
Ether, ethyl 3-mercaptopropyl
Ethyl disulfide
Formamidine, AW-diphenyl-, l,l'-dithiobisFormic acid, thio-, dithiobis, 0,0'-diisopropyl ester
1-Heptanethiol
1-Hexanethiol
- , 1,1,3,3,5,5-hexamethylHexyl disulfide
Hydrogen sulflde
Isobutyl disulfide
Isopropyl disulfide
Lauryl disulfide
Lepidine, 2,2-dithiodiMesityl disulfide
Methyl disulfide