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POLYMER HANDBOOK
J . BRANDRUP, E. H. IMMERGUT, and E. A. GRULKE
Associate Editors
A. ABE
D. R. BLOCH
Abe, A.
Tokyo Institute of Polytechnics, Atsugi, Japan
Allegra, G.
Dipartimento di Chimica de1 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 Polimeros, Madrid, Spain
Bello, A.
Instituto de Ciencia y Tecnologia de Polimeros, Madrid, Spain
Bello, P.
Instituto de Ciencia y Tecnologia de Polimeros, 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, Cameagie-Mellon University, Pitts-
burgh, 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, Mtilheim an der
Ruhr, FR Germany
Fink, H.-P.
Fraunhofer Institut fur angewandte .Polymerforschung, Teltow-
Seehof, FR Germany
Fouassier, J. P.
Laboratoire de Photochimie G&&ale, 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,
Ganster, J.
Fraunhofer Institute for Applied Polymer Research, Teltow-
Seehof, 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
Guzmin G. M.
Instituto de Ciencia y Tecnologia de Polimeros, 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 Technol-
ogy, 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
V
vi CONTRIBUTORS
Johnson, M. Muck, K.-F.
Chemistry/Physics Library, University of Kentucky, Lexington,
Kentucky, USA
Ticona GmbH, Kelsterbach, FR Germany
Nagai, S.
Kamachi, M. Plastics Technical Association, Osaka, Japan
Department of Applied Physics and Chemistry, Fukui Uni-
versity of Technology, Gakuen, Fukui, Japan
Nordmeier, E.
Kerbow, D. L.
Physikalische Chemie, Universitat Osnabriick, Osnabrtick
FR Germany
DuPont Fluoroproducts, Wilmington, Delaware, USA
ogo, Y.
Kimura, S.-I.
Japan Synthetic Rubber Company Ltd., Yokkaichi, Mie,
Japan
Research Institute for Solvothermal Technology, Hayashi,
Takamatsu, Kagawa, Japan
Orwoll, R. A.
Korte, S. College of William and Mary, Williamsburg, Virginia, USA
Zentrale Ferschung, Bayer AG, Leverkunsen, FR Germany
Pauly, S.
Krause, S.
Department of Chemistry, Rensselaer Polytechnic Institute,
Troy, New York, USA
Fachlaboratorium fur Permeationspriifung, Wiesbaden,
FR Germany
Kurata, M.
Institute for Chemical Research, Kyoto University, Uji, Kyoto,
Japan
Peebles, L. H., Jr.
Chemistry Division, Naval Research Laboratory, Washington,
DC, USA
Perera, M. C. S.
Lechner, M. D.
Physikalische Chemie, Universitat Osnabriick, Osnabrtick, FR
Germany
Magnetic Resonance Facility, School of Science, Griffith
University, Nathan, Australia
Leonard, J.
Porzio, W.
Department de Chimie and CERSIM, Universite Laval,
Quebec, Canada
Instituto di Chimica delle Macromolecole de1 C.N.R., Milano,
Italy
Li, F.
Pyda, M.
The Maurice Morton Institute of Polymer Science, University
of Akron, Akron, Ohio, USA
Liggat, J.
Department of Chemistry, University of Tennessee, Knoxville,
Tennessee: USA
Quirk, R. P.
Department of Pure and Applied Chemistry, University of
Strathclyde, Glasgow, Scotland
The Maurice Morton Institute of Polymer Science, University
of Akron, Akron, Ohio, USA
Lindemann, M.
Riande, E.
Greenville, South Carolina, USA
Instituto de Ciencia y Tecnologia de Polimeros, Madrid,
Spain
Luft, G.
Institut fur Chemische Technologie, Technische Hochschule,
Darmstadt, FR Germany
Richter, W. J.
Max-Planck-Institut fur Kohlenforschung, Miilheim an der
Magill, J. H.
School of Engineering, University of Pittsburgh, Pittsburgh,
Pennsylvania, USA
Ruhr, FR Germany
Rothe, M.
McKenna, T. F.
University of Ulm, Ulm, FR Germany
Rule, M.
Centre Nationale de la Recherche Scientifique, Laboratoire de
Chimie et Pro&d& de Polymerisation/Departement Genie des
Pro&d&, Villeurbanne, France
Mehta, R. H.
DuPont Nylon, Chattanooga, Tennessee, USA
Coca Cola Company, Atlanta, Georgia,
Salort, J. F.
Madrid, Spain
Salom, C.
Meille, S. V.
Dipartimento di Chimica de1 Politecnico, Milano, Italy
Metanomski, W. V.
Chemical Abstracts Service, Columbus, Ohio, USA
Escuela TCcnica Superior de Ingenieros Aeronauticos, Uni-
versidad Politecnica, Madrid, Spain
Sanchez, I. C.
Chemical Engineering Department, University of Texas at
Austin, Austin, Texas, USA
Michielsen, S. Santos, A. M.
School of Textile and Fiber Engineering, Georgia Institute of
Technology, Atlanta, Georgia, USA
Faculdade de Engenharia Quimica de Lorena - FAENQUIL,
Lorena, Sao Paulo, Brazil
Miller, R. L. Schoff, C. K.
Michigan Molecular Institute, Midland, Michigan, USA PPG Industries, Allison Park, Pennsylvania, USA
Morita, Y. Schuld, N.
Japan Atomic Energy Research Institute, Takasaki,
Gunma-ken, Japan
Institut fur Physikalische Chemie, Universitat Mainz, Mainz,
FR Germany
USA
Seferis, J. C.
Chemical Engineering Department, University of Washington,
Seattle, Washington, USA
Seguchi, T.
Japan Atomic Energy Research Institute, Takasaki, Gunma-ken,
Japan
Schrader, D.
The Dow Chemical Company, Midland, Michigan, USA
Sperati, C. A.
Chemical Engineering Department, Ohio University, Athens,
Ohio, USA
Steinmeier, D. G.
Physikalische Chemie, UniversitHt Osnabtick, Osnabriick,
FR Germany
Tsunashima, Y.
Institute for Chemical Research, Kyoto University, Uji, Kyoto,
Japan
Tsvetkov, N. V.
Institute of High Molecular Weight Compounds, Russian
Academy of Science, St. Petersburg, Russian Federation
Tsvetkov, V. N.
Institute of High Molecular Weight Compounds, Russian
Academy of Science, St. Petersburg, Russian Federation
Ueda, A.
Osaka Municipal Technical Research Institute, Morinomiya,
Joto-ku, Osaka, Japan
Cont ri but ors vii
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
Witenhafer, D. E.
Dublin, Ohio, USA
Wolf, B. A.
Institut fiir Physikalische Chemie, UniversitPt Mainz, Mainz,
FR Germany
wu, s.
E. I. DuPont de Nemours, Central Research and Development
Department, Experimental Station, Wilmington, Delaware
Wunderlich, B.
Department of Chemistry, University of Tennessee, Knoxville,
Tennessee, USA
Wunderlich, W.
ROHM GmbH, Darmstadt, FR Germany
Yamada, B.
Department of Applied Chemistry, Faculty of Technology,
Osaka City University, Sumiyoshi, 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 experi-
mental polymer research. All polymer researchers have
experienced the frustration of searching for data in the ever-
expanding 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.
I
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 thermody-
namic studies of polymerization and depolymerization
reactions. Sections III and IV contain physical constants
of monomers, solvents, and oligomers. Section V lists the
I
physical constants of many important commercial poly-
mers. 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 abbrevia-
tions 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 rheologi-
cal data, are minimized, since many excellent compilations
exist elsewhere. Only fundamental constants and para-
meters that refer to the polymer molecule, that describe the
I solid state of polymer molecules, or that describe polymer
1
solutions, were compiled. Constants that depend on
processing conditions or on sample history were not
emphasized, as they can be found in existing plastics
I
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 erro-
neous 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 Hund-
book 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 approxi-
mately 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 Handbooks 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 excel-
lent 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
i x
Contents
I. NOMENCLATURE RULES - UNITS
Nomenclature, I/l
W K Metanomski
Units, I/13
J. Brandrup
II. POLYMERIZATION AND DEPOLYMERIZATION
Decomposition Rates of Organic Free Radical
Initiators, II/l
K. W! Dixon
Propagation and Termination Constants in Free
Radical Polymerization II/77
M. Kamachi and B. Yamada
Transfer Constants to Monomers, Polymers,
Catalysts and Initiators, Solvents and Additives,
and Sulfur Compounds in Free Radical
Polymerization, II/97
A. Uedu and S. Nagai
Photopolymerization Reactions, II/169
J. P Fouassier
Free Radical Copolymerization Reactivity Ratios,
II/181
R. Z. Greenley
Q and e Values for Free Radical Copolymerizations
of Vinyl Monomers and Telogens, II/309
R. Z. Greenley
Patterns of Reactivity (U,V) Parameters for the
Prediction of Monomer Reactivity Ratios and
Transfer Constants in Radical Polymerization,
II/321
A. D. Jenkins and J. Jenkins
Copolymerization Parameters of Metallocene-
Catalyzed Copolymerizations, II/329
G. Fink and W J. Richter
Rates of Polymerization and Depolymerization,
Average Molecular Weights, and Molecular Weight
Distribution of Polymers, II/339
L. H. Peebles, Jr:
Heats and Entropies of Polymerization, Ceiling
Temperatures, Equilibrium Monomer
Concentrations, and Polymerizability of
Heterocyclic Compounds, II/363
J. Leonard
Activation Energies of Propagation and Termination
in Free Radical Polymerization, II/415
T F McKenna and A. M. Santos
Activation Volumes of Polymerization Reactions,
II/429
G. Luft and Y Ogo
Activation Enthalpies and Entropies of Stereocontrol
in Free Radical Polymerizations, II/445
H. -G. Elias
Products of Thermal Degradation of Polymers,
II/451
J. J. Liggat
Radiation Chemical Yields: G Values, II/481
M. C. S. Perera and D. J. I? Hill
Ill. PHYSICAL PROPERTIES OF MONOMERS
AND SOLVENTS
Physical Properties of Monomers, III/l
D. R. Bloch
Isorefractive and Isopycnic Solvent Pairs, III/43
H. -G. Elias
Refractive Indices of Common Solvents, III/55
H. -G. Elias
Physical Constants of the Most Common Solvents
for Polymers, III/59
D. R. Bloch
IV. PHYSICAL DATA OF OLICOMERS
Physical Data of Oligomers, IV/l
M. Rothe
V. PHYSICAL CONSTANTS OF SOME IMPORTANT
POLYMERS
Physical Constants of Rubbery Polymers, V/l
I. Furuta, S.-I. Kimura, and M. Iwama
Physical Constants of Poly(ethylene), V/9
L. Zhu, F-C. Chiu, Q. Fu, R. P Quirk, and
S. Z. D. Cheng
Physical Constants of Poly(propylene), V/21
F Bai, R Li, B. H. Calhoun, R. l? Quirk, and
S. Z. D. Cheng
Physical Constants of Fluoropolymers, V/31
D. L. Kerbow and C. A. Sperati
Physical Constants of Poly(acrylonitrile), V/59
S. Korte
Physical Constants of Poly(vinyl chloride), V/67
E. A. Collins, C. A. Daniels, and D. E. Witenhafer
xi
xii CONTENTS
Physical Constants of Poly(vinyl acetate), V/77
M. K. Lindemann
Physical Constants of Poly(methy1 methacrylate),
V/S7
W Wunderlich
Physical Constants of Poly(styrene), V/91
D. Schrader
Physical Constants of Poly(oxymethylene), V/97
K.-F Muck
Physical Constants of Poly(oxyethylene-
oxyterephthaloyl), (Poly(ethylene terephthalate)),
V/l13
M. Rule
Physical Constants of Poly(oxytetramethylene-
oxyterephthaloyl) and Copolymers with
Tetramethylene Oxide Thermoplastic Elastomers,
V/l19
K. B. Wagener
Physical Constants of Various Polyamides:
Poly[imino(l-oxohexamethylene)], (Polyamide 6)
Poly(iminoadipoyl-iminohexamethylene),
(Polyamide 66), Poly(iminohexamethylene-
iminosebacoyl), (Polyamide 610),
Poly[imino(l-oxododecamethylene)],
Poly(amide 12), V/l21
R. H. Mehta
Physical Constants of Cellulose, V/l35
J . Ganster and H.-R Fink
Physical and Mechanical Properties of Some
Important Polymers, V/l59
R T DeLassus and N. E Whiteman
VI. SOLID STATE PROPERTIES
Crystallographic Data and Melting Points for
Various Polymers, VI/l
R. L. Miller
Glass Transition Temperatures of Polymers, VI/193
R. J . Andrews and E. A. Grulke
Rates of Crystallization of Polymers, VI/279
J . H. Magi11
Isomorphous Polymers Pairs, VI/399
G. Allegra, S. V Meille, and W? Porzio
Miscible Polymers, VI/409
S. Krause, S. H. Goh
Heat Capacities of High Polymers, VI/483
M. Pyda and B. Wunderlich
Surface and Interfacial Tensions of Polymers,
Oligomers, Plasticizers, and Organic Pigments, VI/521
s. wu
Permeability and Diffusion Data, VI/543
S. Paul y
Refractive Indices of Polymers, VI/571
J . C. Seferis
Radiation Resistance of Plastics and Elastomers,
VI/583
T Seguchi and Y Morita
PVT Relationships and Equations of State of
Polymers VI/591
J . Cho and I . C. Sanchez
VII. SOLUTION PROPERTIES
Viscosity - Molecular Weight Relationships and
Unperturbed Dimensions of Linear Chain
Molecules, VII/l
M. Kurata and X Tsunashima
Sedimentation Coefficients, Diffusion Coefficients,
Partial Specific Volumes, Frictional Ratios, and
Second Virial Coefficients of Polymers in Solution,
VII/85
M. D. Lechnei; L. Nordmeier and D. G. Steinmeier
Polymolecularity Correction Factors, VII/215
R. E. Bareiss
Polymer-Solvent Interaction Parameters, VII/247
N. Schuld and B. A. Wolf .
Concentration Dependence of the Viscosity of Dilute
Polymer Solutions: Huggins and Schulz-Blaschke
Constants, VII/265
C. K. Schoff
Theta Solvents, VII/291
H. -G. Elias
Fractionation of Polymers, VII/327
J . M. Barrales-Rienda, A. Bello, R Bello, and
G. M. Guzman
Solvents and NonSolvents for Polymers, VII/497
D. R. Bloch
Specific Refractive Index Increments of Polymers in
Dilute Solution, VII/547
S. Michielsen
Particle Scattering Factors in Rayleigh Scattering,
VII/629
E. F Casassa
Dipole Moments of Polymers in Solution, VII/637
J . E Salort, C. Salom, and E. Riande
Heat, Entropy and Volume Changes for Polymer-
Liquid Mixtures, VII/649
R. A. Orwol l
Heats of Solution of Some Common Polymers,
VII/671
R. A. Onvol l
Solubility Parameter Values, VII/675
E. A. Grulke
Optically Active Polymers, VII/715
K. I nomata and A. Abe
Anisotropy of Segments and Monomer Units of
Polymer Molecules, VII/745
V N. Tsvetkov, L. N. Andreeva, and N. I ? Tsvetkov
Contents ** Xl11
Gelation Properties of Polymer Solutions, VII/765
A. Hiltner
Chemical Abstract Registry Numbers and Online
Database Searching for Polymer Literature, VIII/25
M. Johnson and E. A. Grulke
VIII. ABBREVIATIONS OF POLYMER NAMES AND
CHEMICAL ABSTRACT NUMBERS IX. Index, IX/l
Abbreviations for Thermoplastics, Thermosets,
Fibers, Elastomers and Additives, VIII/l
H.-G. Elias
c
SECTION I
NOMENCLATURE RULES-UNITS
Nomenclature
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
Pol ymer s
2.5. Irregular Single-Strand Organic Polymers
C. Use of Commonand Semisystematic Names
D. Chemical Abstracts (CA) Index Names
E. Polymer Class Names
F. References
l-l
I - 1
I-2
I-2
I-2
I-3
I-3
I-6
I-6
I-7
I-7
I-8
I-8
l -l 1
I-1 2
A. 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
-rigdrous 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 [ 11.
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 Compen-
dium which groups all the currently valid documents in a
single volume. The Commission published its Compen-
dium 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: nomen-
clature of regular single-strand organic polymers and
source-based nomenclature for copolymers. In more
recent years, the Commission extended that basic nomen-
clature to double-strand (ladder and Spiro) organic poly-
mers, 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.
6. IUPAC RECOMMENDATIONS
Since polymers, unlike low-molecular-weight compounds,
have no uniform structure and are mixtures of macro-
molecules of different length and different structural
I/l
I/2
NOMENCLATURE
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
nCH2=CHCl + +CH2-CHCl j,,
That shows an idealized product. In fact, however, the
polymer consists of long-chains of various lengths. The
repeating units, -CHz-CHCl-, are not necessarily all
uniquely oriented and joined in a regular fashion as shown
in the idealized structure above. In addition to head-to-
tail links
-CH2-CHCl-CH2-CHCl-
other links such as head-to-head
-CHCl-CH2-CH2-CHCl-
and tail-to-tail
-CH2-CHCl-CHCl-CH2-
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:
- YH- CH2-
-YH-cH2-
$=o
b-CH,
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
1.7. Homopolymers Homopolymers are derived froin
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
polybutadiene
polyethylene
poly(methy1 methacrylate)
poly(methy1 vinyl ether)
polystyrene
poly(tetrafluoroethylene)
poly(viny1 alcohol)
poly(viny1 acetate)
poly(viny1 chloride)
poly(vinylidene dichloride)
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:
R-CH=CH-R1 + -CHR-CHR I-
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.
7.2. Copo/ymers For copolymers, the names of mono-
mers 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 -co-
statistical (obeying known statistical laws) -stat-
random (obeying Bernoullian distribution) -ran-
alternating (for two monomeric units) -ah-
periodic (ordered sequence of more than two) -per-
block (linear arrangement of blocks) -block-
graft (side blocks chains connected to -graft-
main chain)
Examples: poly[styrene-co-(methyl methacrylate)]
poly(styrene-stat-acrylonitrile-stat-butadiene)
poly[ethylene-ran-(vinyl acetate)]
poly[(ethylene glycol)-alt-(terephthalic acid)]
poly[formaldehyde-per-(ethylene oxide)-per-
(ethylene oxide)]
polystyrene-block-polybutadiene
polybutadiene-graft-polystyrene
Structure-Based Nomenclature
I/3
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: copoly(styrene/methyl methacrylate)
stat-copoly(styrene/acrylonitrile/butadiene)
run-copoly(ethylenelviny1 acetate)
alt-copoly(ethylene glycol/terephthalic acid)
per-copoly(formaldehyde/ethylene oxide/ethy-
lene oxide)
block-copoly(styrene-butadiene)
graft-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 macromo-
lecules comprise branched, graft, comb, star, cyclic, and
network macromolecules. The macromolecular assemblies
comprise polymer blends, interpenetrating polymer net-
works, 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 non-
linear macromolecules or macromolecular assemblies:
Type Connective
cyclic
branched, unspecified
short-chain-branched
long-chain-branched
branched with branch point
of functionality f
comb
star
star with f arms
network
crosslink
polymer blend
interpenetrating polymer network
semi-interpenetrating polymer network
polymer-polymer complex
cycle
branch
sh-branch
l -branch
f-branch
comb
star
f-star
net
L (Greek iota)
blend
ipn
si pn
compl
In naming non-linear homopolymer molecules, the
italicized prefix for the skeletal structure of the macro-
molecule is placed before the source-based name of the
constituent linear chain.
Assemblies of macromolecules held together by non-
covalent bonds are named by a combination of the names of
the constituent macromolecules with an italicized con-
nective between them.
Examples: polystyrene-comb-polyacrylonitrile
comb-poly(styrene-stat-acrylonitrile)
polystyrene-comb-[polyacrylonitrile;
poly(methy1 methacrylate)]
4-star-polystyrene
star-(polyA-block-polyB-block-polyC)
star-(polyA; polyB; polyC)
star-(polyacrylonitrile; polystyrene)
(Ad, 100000 : 20000)
net-polystyrene+divinylbenzene
net-poly[styrene-alt-(maleic anhydride)]-
L-(ethylene glycol)
polystyrene-blend-poly(2,6-dimethylphenol)
poly(methy1 methacrylate)-blend-poly(n-butyl
acrylate)
(net-polystyrene)-sipn-poly(viny1 chloride)
[net-poly(styrene-stat-butadiene]-ipn-[net-
poly(ethy1 acrylate)
2. 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 [l]. Each such repeating group can
consists of simple or substituted subunits such as:
-CH2-
-CH2CH2-
-CH=CH-
-CH2CH2CH2CH2CH2CH2-
-CHCl-CH2-
-COCH2-CH2-
-COCH2CH2CH2CH2CO-
/-\
--ilk
-o-
OXY
-s- thio
-so2- sulfonyl
-NH- i mi no
-N(CH3)- met hyl i mi no
-NHNH- hydrazo
- N
3
-SiH2-
-Si(CHa)a-
methylene
ethylene
vinylene
hexane- 1,6-diyl
-1 -chloroethylene
1 -oxopropane- 1,3-diyl
adipoyl
1,4-phenylene
cyclohexane- 1,6diyl
piperidine- 1 ,Cdiyl
silanediyl
di met hyl si l anedi yl
Before the total constitutional repeating unit (CRU) can
be given a unique name, a single preferred CRU must be
selected.
References page I - 12
I/4
NOMENCLATURE
For instance, in a polymer such as
-00CH-CHz-0-CH-CH2-OCH-CH2-O-
C l C l C l
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
-0-CH-CH2- -00CH2-CH- -CH2-O-CH-
I
C l
or
Cl Or C l
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- 1,6diyl: -N
3-
thiophene-2,5-diyl: e
b. heteroatomic acyclic groups, e.g., oxy: -0-,
sulfonyl: -SOz-, imino: -NH-
C. carbocycles, e.g., 1,4-phenylene:
a-
cyclobutane-1,3-diyl: u
d. carbon-containing acyclic groups,
e.g., I-chloroethylene: -CHCl-CHz-
propane-1,3-diyl: -CHz-CH2-CHz-
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 5-
and 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;
d. for carbon-only acyclic chains, seniority is deter-
mined 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.
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(chloro-
ethylene 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 -CHz-CH2-. The substituted
subunit, -CHCl-CH2-, 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
-00CH-CH2-
and the polymer
+O-TCH2f;;
C l
is named
poly[oxy( 1-chloroethylene)]
The second example:
fN-F-NH
C l
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 chemi-
cal 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.
St r uc t ur e-Based Nomenc l at ur e
115
The third example: symbol CY denoting the left-hand end group and the symbol
o denoting the other end group.
poly(pyridine-3,5diylcarbonyloxymethylene)
Example:
I--\
shows a polymer, whose CRU starts with a heterocycle and
then proceeds through a substituted carbon atom toa hetero
atom.
If the end groups of the chain are known, they may be
specified by adding prefixes to the polymer name, with the
a-(trichloromethyl)-o-chloropoly( 1 ,Cphenylene-
methylene)
The following table compares and contrasts structure-
based and source-based names of some common polymers.
Structure Structure-based name Source-based or trivial name
fCH2CH2fn
t$CH,-),
+C%Mbjn
+C=CHCH2CH2&
Poly(methylene)
Poly(propylene)
Poly(l,l-dimethylethylene)
Poly( l-methyl- 1-butenylene)
f ;zH21;; Poly( 1-phenyletbylene)
bN
ti:"""2j;;
OCOCH3
fCWH2fn
fCWFz+n
+9CH2+,
OY
C3H7
t CPWHdi
COOCH3
f0CHzCH2fn
0
I I
f NH- C- (CWs-2;;
0
Poly(l-chloroethylene)
Poly( 1-cyanoethylene)
Poly( 1 -acetoxyethylene)
Poly( 1,l -difluoroethylene)
Poly(difluoromethylene)
Poly[(2-propyl-1,3-dioxane-4,6-diyl)methylene]
Poly[l-(methoxycarbonyl)-1-methylethylene]
Poly(oxyethylene)
Poly(oxy-1,4-phenylene)
Poly [imino( 1-oxohexane-1,6-diyl)]
?
Poly(E-caprolactam)
+OCH2CH2&
-
-0
\ , k-);; Poly(oxyethyleneoxyterephtbaloy1) Poly(ethylene terephthalate)
0 0
--(NH- &CH2)&NH(CH2)& Poly(iminoadipoyliminohexamethylene) Poly(hexamethylenediamine-alt-adipic acid)
or poly(hexamethylene adipamide)
- CH- CH- CHCH,?
O=L\ , C = O &Hs
Poly[(2,5-dioxotetrahydrofuran-3,4-diyl)( 1-phenylethylene)] Poly(maleic anhydride-alt-styrene)
Polyethylene
Polypropene
Polyisobutylene
Polyisoprene
Polystyrene
Poly(viny1 chloride)
Polyacrylonitrile
Poly(viny1 acetate)
Poly(vinylidene fluoride)
Polytetrafluoroethylene
Poly(viny1 butyral)
Poly(methy1 metbacrylate)
Poly(ethylene oxi de)
Poly(phenylene oxide)
0
References page I - 12
116
NOMENCLATURE
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 nomen-
clature. Again, the name of the polymer is in the form of
poly(constitutiona1 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
\ /n
poly(butane-1,4 : 3,2-tetrayl)
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
common at each junction:
J+jpfJ~:-~
0
the name based on the preferred CRU is
b v
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 (car-bony1 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&naphthalenetetra-
carboxylic dianhydride with 1,2,4,5-benzenetetramine:
poly[(7-oxo-7H,lOKbenz[de]imidazo[4,5 : 5,6]benzimi-
dazo [2,1-alisoquinoline-3,4: lO,l l-tetrayl)-lo-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:
, 0 - CH2
c\
C/
/\
0-CH2
poly(2,4,8,lO-tetraoxaspiro[5.5]undecane-3,3:9,9-tetrayl-9,9-diethylene)
2.3. Regular Single-Strand Inorganic and Coordina-
tion 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
Structure-Based Nomenclature
I/7
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, cute&, 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
73
F CH3
fyj;;
--f Ai- AiJ,
C3
A &H
3
catena-poly[dimethyltin] catenu-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 p:
rH3
fzn-Cl-fii-
Cl
cutenu-poly[(ammine-
chlorozinc)-p-chloro]
7 7H3
e--N%
iI A
3
cutenu-poly[(dihydro-
boron)-p-(dimethylamido)]
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:
cutena-poly[copper-[CL-chloro-bis-p-(diethyl disulfide-S:
S)]-copper-p-chloro]
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:
catenu-poly[palladium-
di-p-chloro]
cutenu-poly[silicon-
di-p-thio]
i >
dBT
\
Cl n
catenu-poly[platinum(~-
bromo-p-chloro)]
cutenu-poly[titanium-
tri-y-chloro]
2.5. h-regular Sing/e-Strand Organic Polymers Irregu-
lar 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
containing units:
hydrolyzed poly(viny1 acetate)
- CH- CH2- - CH- CH2-
0-CO--H3
and
bH
is represented graphically and named:
t y- CH2- / - y- CH2+
0-CCPCH3 O H
poly( 1-acetoxyethylene/l-hydroxyethylene)
A copolymer of vinyl chloride and styrene joined head-to-
tail is
t CH- CH2- / - CH- CH2f,
Cl
C65
poly( 1 -chloroethylene/l -phenylethylene)
A chlorinated polyethylene consisting of units
- C H - - C - -CH2-
Cl Cl
References page I - 12
118
NOMENCLATURE
is shown and named as
+CHCl-/-CC12-/-CH2- j,
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 commu-
nication 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 source-
based 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.
Examples:
+0-c-0-p-c6~4-S02-p-c6~4*
6
Handbook name: poly(4,4-sulfonyldiphenylene car-
bonate)
IUPAC name: poly(oxycarbonyloxy- 1,4-phenylene-
sulfonyl- 1,4-phenylene)
Handbook name: poly(oxydiethylene succinate)
IUPAC name: poly(oxyethyleneoxyethyleneoxysuc-
cinyl)
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(viny1 alcohol)
poly(viny1 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 . 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 character-
istics 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 excep-
tional 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 mod@cation (derivative of the principal
function), e.g., 2-propenoic acid, a-methyl-, methyl
est er
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 CA Index names (inverted form)
acrylamide 2-propenamide
acrylic acid 2-propenoic acid
acrylonitrile 2-propenamide
adipic acid hexanedioic acid
c-caprolactam 2H-azepin-2-one, hexahydro-
s-caprolactone 2-oxepanone
ethylene glycol 1,2-ethanediol
ethylene oxide oxirane
fumaric acid 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
Chemi cal Abstracts I ndex Names
119
acetic acid, hydroxy-
1,4-benzenediol
1,3-benzenedicarboxylic acid
propanoic acid, 2-hydroxy-
2-butenedioic acid, (Z)-
2,5-furandione
1,3,5-triazine-2,4,6-triamine
2-propenoic acid, 2-methyl-
2-propenoic acid, methyl ester
1,3-isobenzofurandione
oxirane, methyl-
benzene, ethenyl-
1,4-benzenedicarboxylic acid
ethenql
ethene, chloro-
ethene, 1,l -dichloro-
Similarly, commonly named substituent and multiplying
groups have their systematic equivalents in CA Indexes:
adipoyl
ally1
tert-butyl
ethylene
hexamethylene
isopropyl
succinyl
vinyl
vinylene
1,6-dioxo- 1,6-hexanediyl
2-propenyl
1,l -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 homopoly-
mer cited in the modiJication 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):
(CH2= y- COOHX
GKj:::
CA name: 2-Propenoic acid, 2-methyl-, homopoly-
mer
2. Polystyrene:
(CH2= 7%
C6%
GHs>x
CA name: Benzene, ethenyl-, homopolymer
3 . Poly( 11 -aminoundecanoic acid):
(H2WCHdlo-COOHL
(CllH23NOdx
CA name: Undecanoic acid, 1 l-amino-, homopoly-
mer
References page I - 12
c
,
I/10 NOMENCLATURE
4. Poly(lactic acid):
(CH3- y- COOH),
KY-k~~~r
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
mod$cation 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 x.
The corresponding empirical formulas are similarly ex-
pressed. The descriptors alternating, block, and graft are
cited whenever applicable.
Examples:
1. Butadiene-vinyl ethyl ether copolymer:
(CH2=CH-CH=CH2CH2=CH-0-CH2CH3>,
(C4Hs0C4H6)x (in Formula Index order)
CA names: 1,3-Butadiene, polymer with ethoxy-
ethene
Ethene, ethoxy-, polymer with 1,3-
butadiene
2. Isophthalic acid-terephthalic acid-ethylene glycol
polyester:
(HOOC-m-CgHq-COOH.HOOC-p-CgHq--COOH.
OH-(CH2)2-OH),
(CgH604.C8H604.C2H602)x
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 ,Zethanediol
1,2-Ethanediol, polymer with 1,3-benze-
nedicarboxylic acid and 1,4-benzenedi-
carboxylic 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 x, followed by the telogen
structure. The corresponding empirical formula is
expressed in the same way.
Examples:
1. Vinylpyrrolidone homopolymer terminated with
mercaptopropionic acid:
CH= CH2
t i
A
c-l==
0
- SH-CH2- CH2- COOH
x
(C&NO)n.C3%02S
CA names: 2-Pyrrolidinone, 1-ethenyl-,
with 3-mercaptopropanoic acid
Propanoic acid, 3-mercapto-,
with 1-ethenyl-2-pyrrolidinone
telomer
telomer
2. Acrylic acid-vinyl choride copolymer terminated
with carbon tetrachloride:
(CH2=CH-COOHC1-CH=CH2)x.CC14
(C3H402C2H3C1),CC14
CA names: 2-Propenoic acid, telomer with chloro-
ethene 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:
0
fNH&W,,)-,
(CllfhNO)n
CA name: Poly [imino( 1 -oxo- 1,ll -undecanediyl)]
2. Poly(ethylene adipate):
0 0
fO-CH,-CH2-O-!-(CH2)4-&
(Cd1204)n
CA name: Poly[oxy-1,2-ethanediyloxy(l,6-dioxo-
1,6-hexanediyl)]
Pol ymer Cl ass Names I/11
I
3. Poly(ether ether ketone) (PEEK):
0
SO--p-C~H~-O-p-Cfj*&p-cfjH&
(C19H1203)n
CA name: Poly(oxy-1,4-phenyleneoxy- 1,6pheny-
lenecarbonyl- 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):
H +O-CH2-CH2 jnOH
CA name: Poly(oxy-l,Zethanediyl), a-hydro-
o-hydroxy-
2. Poly(trimethylene glycol) dimethyl ether:
CH3fO-CH2-CH2-CH&O-CH3
CA name: Poly(oxy-1, 3-propanediyl), a-methyl-
o-methoxy-
3. Poly(tetramethylene glycol) diacrylate:
CH2=CH-C(O) GO-CH2-CH2-CH2-CH2+,
0-C(O)-CH=CH2
CA name: Poly(oxy-1, 4-butanediyl), rx-( l-oxo-
2-propenyl)-o-[(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
Pluoropolymers
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 I - 12
I/ 12 NOMENCLATURE
could be grouped and arranged in a hierarchy, e.g., 3. Chemical Abstracts Service, CA Index Guide 1997,
I
Polyacetals Polyethers
Polyvinyl acetals epoxy resins
polyvinyl butyrals polyetheretherketones
polyvinyl formals polyoxyalkylenes
polyoxymethylenes
Polyesters polyoxyarylenes
polycarbonates polyoxyphenylenes
Some are synonymous or near synonymous, e.g.,
polyalkenylenes and polydienes, polyalkynylenes and
polyacetylenes, polyethers and polyoxides, polythioethers
and polysulfides.
Appendix IV, Chemical Substance Index Names,
Chemical Abstracts Service, Columbus, Ohio, 1997.
i
/
4. IUPAC, Source-Based Nomenclature for Copolymers
(Recommendations 1985), Pure Appl. Chem. 57, 1427
(1985). Reprinted as Chapter 7 in Ref. 2.
I
5. IUPAC, Source-Based Nomenclature for Non-Linear
Macromolecules and Macromolecular Assemblies (Recom-
i
mendations 1997), Pure Appl. Chem. 69, 2511 (1997).
6. IUPAC, Nomenclature of Regular Double-Strand (Ladder
and Spiro) Organic Polymers (Recommendations 1993),
I
Pure Appl. Chem. 65, 1561 (1993).
c
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).
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.
9. IUPAC, Use of Abbreviations in the Chemical Literature
(Recommendations 1979), Pure Appl. Chem. 52, 2229
(1980).
Units
J. Brandrup
Wiesbaden, FR Germany
A. Introduction
B. International Units
C. SI-Prefixes
D. Conversion Factors
E. Conversion Table for SI vs. English-American
Uni t s
l-l 3
l-l 3
l-l 4
I-1 4
l-l 7
A. 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
6. INTERNATIONAL UNITS
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, IS0 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 Physicochem-
ical Quantities and Units; Pergamon Press, Oxford 1979
(Pure Appl. Chem., 51, 1 (1979).
5. F. S. Conant, using the SI units, Polym. Eng. Sci., 17,
222 (1977) (further references).
Quantity H-unit
Selection of multiples
of the SI-unit
Accepted units
used with SI
Units accepted
temporarily
Non SI units
that should not be used
Length
Area
Volume
Time
Frequency
M a s s
De n s i t y
Force
Pr es s ur e
Stress Pa or N/m*
Viscosity (dynamic) Pas
Viscosity (kinematic) m2/s
Surface tension N/ m
Energy, work, heat J (joule)
Power
Temperature
Thermal conductivity
Heat capacity
Specific heat
Entropy
Amount of substance
Electrical resistance
Electrical conductivity
W (watt)
K (kelvin), C
WlmK
J/ K
J&g K)
J/ K
mol (mole)
R
s (l/R)
m (metre)
,:
s (second)
Hz (hertz)
kg (kilogram)
kg/m 3
N (newton)
Pa (Pascal)
or N/m*
km, cm, mm, pm, nm
km*, dm*, cm*, mm*
dm3, cm3, mm3
ks, ms, us, ns
THz, GHz, MHz, kHz
Mg, g9 mg, lg
mg/m3; kg/dm3; g/cm3
MN W mN PN
lA= lo-torn
litre (1, L) (1 1 = 1 dm3)
d, h, min
t
t/m3; kg/l
GPa, MPa, kPa,
mPa, pPa
lbar=105Pa
latm=101325Pa
GPa; MPa or N/mm2; kPa
mPas
mm*/s
mN/m
TJ, GJ, MJ,
kJ, mJ
GW, MW, kW, mW, uW
Electronvolt (eV)
1eV=1.602x10-19J
1p=10-6m
ly=10-9kg
1 dyn = 10m5 N;
pond, kilopond
1 Torr=-
101325 Pa
760
= 133.32 Pa
poise; lP=O.lPas
stokes; 1 St = 1 cm*/s
dynlcm
1erg=10m7J
lcal=4.1868J
lK= 1K
0.86 kcal/(m h grd)
kJ/K
Wkg K)
kJ/K
I/13
I/14 UNI TS
C. SI-PREFIXES
Factor Prefix Symbol Factor Prefix Symbol
108
105
102
109
106
103
IO2
10
exa
peta
tera
gka
mega
kilo
hecto
deca
E
P
T
G
M
k
h
d a
lo-
10-2
10-3
10-6
10-9
10-12
;;I::
deci
centi
milli
micro
nano
pica
f emt o
atto
D. CONVERSION FACTORS
Length m i n ft
Yd
thou or ml1
Im 1 3. 937xl O' 3. 281 1. 094 3. 937x 104
in 2. 540 x 1O-2 1 8. 333 xlO- 2. 778 x lo- 1. 0 x 103
ft 3. 048 x lo- 1 2 1 3. 333 x lo- 1. 2 x 104
yd 9.144 x lo- 36 3 1 3. 6 x lo4
thou or mil 2. 540~ lo- 1.0 x 10-3 8. 334 x 10-5 2. 778 x lO-5 1
Area mz sq. in sq. ft ar
lm2 1 1.550 x 103 1. 076 x 10 1.196 1. 0 x 10-2
sq. in 6. 452 x 1O-4 1 6. 994 x lO-3 7. 716 x lO-4 6. 452~ 1O- 6
sq. ft 9. 290 x lo- 1.440 x 102 1 1.111 x 10-1 9. 290 x lO-4
sq. yd 8. 361 x lo- 1.296 x lo3 9 1 8. 361 x lO-3
ar 1. 0 x 102 1.550 A 105 1. 076 x lo3 1.196 x 10 1
Volume m3 1 (lit) cu. in cu. ft cu. yd
gal (US) @(UK)
lm3 1 103 6. 102 x IO4 3.531 x 10 1. 308 2. 642 x 10 2. 20 x 102
1 (lit) 10-3 1 6. 102 x 10 3.531 x 10-2 1.308 x 1O-3 2. 642 x lo- 2. 20 x lo-
cu. in 1.639 x lO-s 1.639 x lo-* 1 5. 787 x lO-4 2.143 x lO-5 4. 329 x 1O-3 3. 605 x 1O-3
cu. ft 2. 832 x 1O-2 2. 832~ 10 1. 728 x lo3 1 3. 703 x 10-2 7.481 6. 229
cu. yd 7. 646 x lo- 7. 645 x lo2 4. 666 x lo4 2. 7 x 10 1 2. 02ox 102 1.682 x IO*
gal (US) 3. 785 x 1O-3 3. 785 2. 310~ lo2 1.337 x IO- 4.951 x 10-3 1 8. 327 x i O- '
gal ( UK) 4. 546 x lO-3 4. 546 2. 714 x lo2 1.605 x lo- 5. 946 x lO-3 1.201 1
Mass
kg
l bm
ton (UK)
(long ton)
cwt (UK)
(long cwt)
ton (US)
(short ton) ounce grain
1 kg 1 2. 205 9. 842 x 1O-4 1.968 x 1O-2 1.102 x 10-3 3. 527 x 10 1. 543 x 104
l bm 4. 536~ lo- 1 4. 464 x 10-4 8. 929 x lO-3 5. 0 x 10-4 1.6 x 10 7. 0 x 103
ton (metric) 1 x 103 2. 205 x lo3 9. 842 x lo- 19.68 1.102 3. 527 x104 1. 543 x 10
ton (UK) 1. 016 x lo3 2. 240 x 10 1 2. 0 x 10 1.120 3. 584~ lo4 1. 568 x 10
cwt (UK) 5. 080~ 10 1.120 x 102 5. 0 x 10-2 1 5. 600 x lo-* 1.792 x lo3 7. 840 x 10
ton (US) 9. 072~ 10 2. 0 x 103 8. 929 x lo- 1.786 x 10 1 3. 2 x lo4 1. 4 x 10
ounce 2. 835 x lO-z 6. 250 x lO-2 2. 190 x lO-s 5. 580 x 1O-4 3.125 x lo- 1 4. 375x 102
grain 6. 480 x 1O-5 1.429 x lo-* 6. 378 x 1O-8 1.276 x 1O-6 7.143 x 10-8 2. 286~ 1O-3 1
Densi ty
1 kg/m3
Mg/m3 =g/cm3
lbm/cu. ft
lbm/cu. in
lbm/gal (UK)
lbm/gal (US)
kg/m3
1
1. 0 x 103
1. 602 x 10
2. 768~ lo4
9. 978~ 10'
1. 198 x lo2
Mg/m3 = g/cm3 lbmfcu.ft lbm/cu.in lbndgal (UK) lbndgal (US)
1.0 x 10-3 6. 243 x lO-2 3.613 x 1O-5 1.002 x 10-2 8. 345 x 1O-3
1 6. 243 x 10 3.613 x lO-2 1.002 x 10 8. 345
1.602 x lO-2 1 5. 789 x lO-4 1.605 x lo- 1.337 x lo-
2. 768~ 10 1.728 x lo3 1 2. 774~ lo2 2.310 x lo2
9. 978 x lO-2 6. 229 3. 605 x lO-3 1 8. 327 x lo-
1.198 x lo- 7. 480 4. 329 x 1O-3 1.201 1
Conversion Factors I/15
Force N ( kg m/ s )
k& kp
Ibf tonf (UK) (long ton) tonf (US) (short ton)
1N 1 1.020 x 10-1 2.248 x lo- 1. 0 x 105 1.004 x 10-4 1.124 x 1O-4
kp 9.807 1 2.205 9.807 x lo5 9.842 x 1O-4 1.102 x 10-3
lbf 4.448 4.536 x 10 - 1 4.448 x IO5 4.464 x 10 -4 5.0 x 10-4
d
yn
1.0 x 10-5 1.020 x 10-6 2.248 x 1O-6 1 1.004 x 10-9 1.124 x 1O-9
tonf (UK) 9.964 x lo3 1.016 x lo3 2.240 x lo3 9.964 x 10 1 1.120
tonf (US) 8.896 x lo3 9.072 x IO* 2.0 x 103 8. 896 x 10 8.929 x 10 - 1
Pa kPa MPa (N/mm 2, b a r p/cm z kplm at+ stmt Tcwr + Psi (IbUsq. in) +
1Pa(=lN/m2)
lkpa
1 MPa(=l N/mm
1 bar ( = 0.1 MPa)
lphn
lkp/m2+
lat(=lkp/cm*)+
1 atm ( = 76OTotr) +
lTotr(=l/76Oatm)+
Psi (lbfhq. in)
1
10
106
105
9.81 x 10
9.81
9.81 x 104
1.01325 x lo5
1.33 x 102
6.895 x 10
10 -3
1
10
102
9.81 x lo-*
9.81 x lo-3
9.81 x 10
1.01325 x lo2
1.33 x 10-1
6.895
10-6
lo-
lo-
9.81 x 10-5
9.81 x lO-6
9.81 x lo-*
1.01325 x lo-
1.33 x 10-4
6.895 x lo-
10-5
10-2
10
9.81 x lO-4
9.81 x 10-5
9.81 x lo-
1.013
1.33 x lo-
6.895 x lo-*
1.02 x 10-2 1.02 x lo- 1.02 x 10-5
1.02x 10 1.02x 102 1.02 x 10-2
1.02 x 104 1.02 x 105 1.02 x 10
1.02 x 103 1.02 x 104 1.02
1 10 10-3
lo- 1 10-4
103 104 1
1.033 x 10 1.033 x 104 1.033
1.36 1.36 x 10 1.36 x lo-
7.031 x 10-5 7.031 x 10-6 7.031 x 10-2
9.87 x 10-6
9.87 x 10 -3
9.87
9.87 x lo-
9.68; lO-4
9.68 x 10 -
9.68 x lo-
1.32 x lO-3
6.805 x 10 -2
7.50 x 10-6
7.50
7.50 x 103
7.50 x 102
7.36 x 10 -I
7.36 x lo-
7.36 x 10
7.60 x lo*
5.171 x 10-1
1.450 x 10 -4
1.450 x 10-1
1.450 x 102
1.450 x 10
1.422 x 10 -*
1.422 x 10 -)
1.422 x 10
1.470 x 10
1.934 x 10-2
t Non SI units.
Stress Pa N/llUll* kp/cm 2 i kp/mm * i Psi (Ibf/sq. in)i
lPa(=lN/m*) 1 10-6 1.02 x 10-5 1.02 x 10-7 1.450 x 10-4
1 N/mm*( = 1 MPa) 106 1 1.02 x 10 1.02 x lo- 1.450 x 102
1 kp/cm* (= 1 at)+ lo4 9. 81 x 9.81 x lo-* 1 10-2 1.422 x 10
1 kp/mm* + 9. 81 x lo6 9.81 102 1 1.422 x lo3
Psi lbflsq. in 6.895 x IO3 6.895 x 1O-3 7.031 x 10-2 7.031 x 10-4 1
t Non SI units.
Viscosity (dynamic)
Pas
(N s/rem*)
WCs m))
mPa s
(mNs/m2) CP kps/m* kph/m* Ibm/(ft s) lbm/(ft h) Ibfs/sq. ft
1Pas
mPa s
gs/m2
kph/m*
lbd(ft s)
lbm/(ft h)
lbf slsq. ft
1 1.0 x 103 1.0 x 103 1.020 x lo- 2.833 x 1O-5 6.720 x lo- 2. 419 x lo3 2.089 x lo-*
1.0 x 10-3 1 1 1.020 x 10-4 2.833 x 1O-8 6.720 x 1O-4 2.419 2.089 x 1O-5
1.0 x 10-3 1 1 1.020 x 10-4 2.833 x 1O-8 6.720 x 1O-4 2.419 2.089 x 1O-5
9.807 9.807 x lo3 9.807 x lo3 1 2.778 x 1O-4 6.590 2. 372 x lo4 2.048 x lo-
3.530 x 104 3.530 x 107 3.530 x 107 3.60 x lo3 1 .2.372 x lo4 8. 540 x lo7 7.373 x lo*
1.488 1.488 x lo3 1.488 x lo3 1.518 x lo- 4.215 x 1O-5 1 3. 60 x lo3 3.103 x lo-*
4.134 x 10-4 4.134 x lo- 4.134 x lo- 4.215 x 1O-5 1.171 x 10-8 2.778 x 1O-4 1 8.634 x 10m6
4.788 x 10 4.788 x lo4 4.788 x lo4 4.882 1.356 x lo-j 3.217 x 10 1. 158 x 10 1
Viscosity (kinematic) m*/s mm*/s m*fh cst sq. ft/s sq. ft/h
1 m*/s 1 1.0 x 106 3.60 x lo3 1.0 x 106 1.076 x 10 3.875 x lo4
mm*/s 1.0 x 10-6 1 3.60 x 1O-3 1.0 1.076 x lo- 3.875 x 1O-2
mZih 2.778 x 1O-4 2.778 x lo* 1 2.778 x lo* 2.990 x 1O-3 1.076 x 10
cst 1.0 x 10-6 1.0 3.60 x 1O-3 1 1.076 x 1O-5 3.875 x lo-*
sq. ws 9.290 x 10 -* 9.290 x lo4 3.345 x 102 9.290 x lo4 1 3.60 x IO3
sq. fvh 2.581 x lo- 2.581 x lo- 9.290 x 10 -* 2.581 x 10 2.778 x 1O-4 1
I/16 UNI TS
Surface tension N/ m (kg/sz) mN/m
kgYm (kp/m) dyn/cm
1 N/m 1 1.0 x 103 1.020 x 10-1 1.0 x 103
mN/m 1.0 x 10-3 1 1.020 x 10-4 1.0
kp/m 9.807 9.807 x lo3 1 9.807 x lo3
dyn/cm 1.0 x 10-3 1.0 1.020 x 10-4 1
J (NM kgfm
Energy (kgm%*) kWh
kpm
Psh lbfft
erg
HPh kcai BTU
1J 1 2. 778 x lo- 1.020 x 10 -1 3. 777 x 10-7 7. 376 x l o- ' 1. 0 x 10' 3. 725 x I O- ' 2. 388 x 1O-4 9. 478 x 1O- 4
kWh 3. 6Ox 106 1 3.671 x lo5 1.360 2. 655 x I O6 3. 60 x lOI 1.341 8. 598 x lo2 3.412 x lo3
bm 9. 807 2. 724 x 1O-6 1 3. 704x 10-6 7. 233 9. 807~ 10 3. 653 x lO-6 2. 342 x 1O-3 9. 295 x lo-
PSh 2. 648~lo6 7. 355 x 10-1 2. 70 x lo5 1 1.953 x 106 2. 648 x 10 I3 9.863 x lo-1 6. 324 x lo2 2.510 x lo3
lbf ft 1.356 3. 766 x lo- 1.363 x lo- 5.120 x lo- 1.356 x 10 5.051 x 10-7 3: 238x lO-4 1.285 x lo-
erg
1.0 x 10-7 2. 778 x lo-l4 1.020 x IO- 3.777 x lo-l4 7.375 1, 1O-8 3. 725 x lo-l4 2.388 x lo- 9.478 x lo-
HPh 2. 685 x lo6 7. 457 x lo- 2. 737 x lo5 1.014 1.980 x lo6 2. 685 : lOI 6. 412 x lo2 2. 544x 103
kcal 4.187 x lo3 1.163 x 1O-3 4. 269 ti lo! 1.581 x 1O-3 3. 088~ lo3 4.187 x 1OO 1.560: lO-3 1 3. 968
BTU 1.055 x 103 2. 931 x lO-4 1.076 x lo2 3. 985 x 1O-4 7. 782 x lo2 1.055 x 100 3.930 x 10-4 2. 520 x lo- 1
a British thermal unit.
Heat J (Nm) (kgm2/s2) kcal BTU CHU
1J 1 2.388 x 1O-4 9.478 x 1O-4 5.262 x 10-4
kcal 4.187 x lo3 1 3.968 2.203
BTU 1.055 x 103 2.520 x 10 - 1 5.552 x lo-
CHU 1.900 x 103 4.539 x lo- 1.80 1
Wh 3.60 x IO3 8.598 x lo- 3.412 1.894
a Centigrade heat unit.
W (J/s) kgfm/s PS
Power (kgm2/s3) kp m/s HP (metr) H P erg/s ft lbf/s kcaUh BTU/ h
1w 1 1.020 x lo- 1.360 x 1O-3 1.341 x 10-3 1.0 x 107 7.376 x lo- 8.598 x lo- 3.412
kp m/s 9. 807 1 1.333 x 10-2 1.315 x 10-2 9.807 x 10 7.233 8.432 3.346 x 10
PS 7.355 x 102 7.5 x 10 1 9.863 x lo- 7.355 x 109 5.425 x lo2 6.324 x lo2 2.510 x lo3
H P 7.457 x to2 7.604 x 10 1.014 7.457 x 109 5.50 x 102 6.412 x lo* 2.544 x lo3
erg/s 1.0 x 10-7 1.020 x 10-8 1.360 x lo- 1.341 L 10-10 1 x lo-s 7.375 8.598 x lO-8 3.412 x lo-
ft Ibf/s 1.356 1.383 x lo- 1.843 x 1O-3 1.818 x 10-3 1.356 x lo7 1 1.166 4.626
kcallh 1.163 1.186 x 10-1 1.581 x lO-3 1.560 x 10-3 1.163 x lo7 8.578 x lo- 1 3.968
BTU/h 2.931 x lo- 2.988 x lO-2 3.985 x lO-4 3.930 x 10 -4 2.931 x lo6 2.162 x lo- 2.520 x lo- 1
W/ m K BTU in/
Thermal conductivity (kg Ws 3 K)) kcal/(m h C) BTU/(ft b F) BTU/(in h F) (sq. ft h F)
1 W/(m K) 1 8.598 x lo- 5.778 x lo- 4.815 x 1O-2 6.933
kcaY(m hC) 1.163 1 6.720 x lo- 5.60 x lO-2 8.064
BTU/(ft h F) 1.731 1.488 1 8.333 x lO-2 1.2 x 10
BTU/@ h F) 2.077 x 10 1.786 x 10 1.2 x 10 1 1.44 x 102
BTU in&. ft h F) 1.442 x lo- 1.24 x lo- 8.333 x lO-2 6.944 x lO-3 1
Specific heat, J/kg K
heat capacity (m2/(s2 K))
W&it K)
kcal/(kg C) BTU/(lbm F)
1 J/(kg K) 1 1.0 x 10-3 2.389 x lO-4 2.389 x 10 -4
kJ@g K)
1.0 x 103 1 2.389 x lo- 2.389 x 10 -
kcal/(kg C) 4.187 x 103 4.187 I 1.0
BTU/(lbm F) 4.187 x lo3 4.187 1.0 1
WWkg K) 3.60 x lo3 3.60 8.598 x lo- 0.8598
Conversion Table for SI vs. English-American units I/17
E. CONVERSION TABLE FOR SI vs. ENGLISH-AMERICAN UNITS
SI to English-American unit Engl i sh-Ameri can uni t to SI
Length
1 m = 1.0936yd = 3.28ft
= 39.37 in
1 mm = 0.03937 in
lyd=3ft=0,9144m
lft = 12in = 0.3048m
1 in = 25.4 mm
Mass, weight
Force
1 kg = 2.2046 lb 1 lb = 0.45359 kg
1 N = l(kgm)/s* = 2.248 x lo- lbf 1 lbf = 4.448 N
Pressure
1Pa=1N/m2=1.450x10~41bf/in2
= 2.953 x 10m4in Hg
= 4.015 x 1O-3 in Hz0
1 bar = lOsPa = 1.450 x 10 lbf/in*
= 2.953 x 10 in Hg
= 4.015 x lo* in Hz0
1 lbf/in* = 1 psi = 6.89475 x lo3 Pa
= 6.89475 x lo-* bar
1 inHg = 3.38638 x lo3 Pa
= 3.38638 x lo-* bar
1 inH20 = 2.49089 x lo* Pa
= 2.49089 x 10m3 bar
Tension, stress
1 N/mm* = 1.450 x lo* lbf/in* 1 lbf/in* = 6.89475 x 10e3 N/mm*
Dynamic viscosity
1Pas = (Ns)/m* = 2.089 x IO-* (Ibfs)/ft*
= 1 kg/(ms) = 6.72 x lO~lbf/(fts)
1 (lbfs)/ft* =4.78802 x 1OPas
1 lb/(ft s) = 1.488 Pas
Kinematic viscosity
1 m*/s = 1.076 x 10 ft*/s 1 ft*/s = 9.29 x lo-* m*/s
Energy, quantity of heat
1 J = 1 Ws = 1 Nm = 7.376 x lo- ftlbf
1 kJ = 9.478 x lo- BTU
1 ft lbf = 1.35582 J
1 BTU = 1.05506 kJ
Power, heat flow rate
1 W = 1 Nm/s = 7.367 x lo-* (ftlbf)/s
= 1 J/s = 4.425 x 10 (ftlbf)/min
= 3.412BTU/h
1 (ft lbf)/s = 1.35582 W
1 (ftlbf)/min = 2.25969 x lo-* W
1 BTU/ h = 2.93072 x lo- W
Specific heat capacity
1 J/(kg K) = 2.388 x 1O-4 BTU/(lb/ OF)
1 J/(m3 K) = 1.491 x 10m5BTU/(ft3 OF)
1 BTU/(lb OF) = 4.1868 x lo3 J/(kgK)
1 BTU/(ft3 OF) = 6.71 x lo4 J/(m3 K)
Thermal conductivity
1 W/(mK) = 6.933 (BTUin)/(ft* h OF)
= 5.778 x lo- BTU/(fth OF)
= 4.815 x lo-* BTU/(in h F)
1 (BTUin)/(ft*hF) = 1.442 x lo-W/(mK)
1 BTU/ (ft h OF) = 1.7307 W/(mK)
1 BTU/(in h OF) = 2.07689 x 10 W/(m K)
I/l8 UNITS
SI to English-American unit Engl i sh-Ameri can uni t to SI
Heat flux density
1 W/m* = 3.17 x lo- BTU/(ft* h)
= 2.201 x 10e3 BTU/(in* h)
1 BTU/(ft* h) = 3.1546W/m2
1 BTU/(in* h) = 4.54263 x lo* W/m*
Heat transfer coefficient
Thermal resistance
1 W/(m* K) = 1.761 x lo-BTU/(ft* h OF) 1 BTU/(ft* h OF) = 5.678 W/(m* K)
Temperature
1 (m* K)/W = 5.678 (ft* h F)/BTU
1 K = 1 C = 1.8 F
1 (ft* h F)/BTU = 1.761 x IO- (m*/K)/ W
1 F = 5.555 x lo- K = 5.553 x lo- C
Conversion:
Tc=+32) T~=;T~f32
TK =; T~+255.372 TF = g (TK - 255.372)
Tc - Temperature in celsius (C); Tr - Temperature in fahrenheit (F); TK - Temperature in kelvin (IQ.
SECTION II
POLYMERIZATION AND
DEPOLYMERIZATION
Decomposition Rates of Organic
Free Radical Initiators
K. W. Dixon
Akzo Nobel Chemicals Inc., Dobbs Ferry, NY, USA
A. Introduction
B. Tables of Decomposition Rates of Organic
Free Radical Initiators
Table 1. Azonitriles
Table 2. Miscellaneous Azo-Derivatives
Table 3. Alkyl Peroxides
Table 4. Acyl Peroxides
Table 5. Hydroperoxides and Ketone Peroxides
Table 6. Peresters and Peroxy Carbonates
Table 7. Miscellaneous Initiators
C. Notes
D. References
II-1
II-2
II-2
II-9
II-23
II-29
II-43
II-48
II-68
II-69
II-70
A. INTRODUCTION
The decomposition of most organic free radical initiators
follows first order kinetics. With certain peroxides, how-
ever, 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:
dL/dt = kdL
where I is the initiator concentration (mol/l) and t is the
time (s). The decomposition rate constant kd is related to
half-life (t i/z) by the following equation:
t 1/2 = 0.693/kd
Fig. 1 relates kd in s-l to half-life for the range of kd found
in the tables.
For some of the initiators listed, the enthalpy (AH*) is
given (Note h) rather than the Arrhenius activation energy
(E,). The two quantities are related by the equation
E, = AH* + RT, where R is the gas constant (in kJ/mol-
deg.) and Tis the absolute temperature (94). Assuming that
kd is linear with respect to l/T and that the activation
energy, Ea, and the decomposition rate constant, kd, for one
temperature are known, kd for any temperature can be
calculated from the following expression:
logk2 = logkt -
Ea(T2 - TI)
2.303R(T2T1)
Where given by the author, the overall equation for kd in
terms of the frequency factor (A) and activation energy (E,)
has been included. Thus for any temperature (converted to
K) the kd may be calculated:
kd = A exp(-E,/RT)
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 decom-
pose 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.
II / 1
II/2 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
50 days s-loo hrs.
- - l Ohrs. , , 4osf%.
, , 5sec. 0. 5 sec.
- - l o mi n.
l . E+oB l . E+07 1. tz+O6 l . E+OS l . E+04 l . E+03 l . E+OZ l . E+Ol l . E+OO
Rdcconstmtkj l
Figure 1. Relationship of half life to rate constant (kd) (half lives are to the right of each vertical line)
B. TABLES OF DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 1. AZONITRILES
Number of
C atoms Initiator Solvent TN3 ka (S-l) E. (kJ/mol) Notes Refs.
5 N-Acetyl N-wcyanoethyl diimide Toluene
2-Cyano-2-propyl-azo-formamide Chlorobenzene
Toluene
Xylene
2-(Carbamoylazo)isobutyronitrile
N-Acetyl N-a-cyanocyclopentyl-
diimide
Toluene
Toluene
2,2-Azo-bis-isobutyronitrile
(2,2-azo-bis-2-methylpropionitrile)
Acetic acid
Acetonitrile
kwAmy1 alcohol
Aniline
Benzene
60. 8 2. 46 x lo-
68. 6 5. 45 x 10-5
82. 0 2 . 4 9 x 10-4
1 0 0 1.5 x 10-5
1 0 0 2.1 x 10-5
1 1 0 6. 8 x 10-5
1 0 4 1.9 x 10-5
1 0 0 2.1 x 10-5
1 2 0 2. 4 x 1O-4
1 0 4 1.93 x 10-5
65. 7 1.82 x 1O-5
76. 8 7 . 2 9 x 10-5
9 1 . 5 3. 65 x 1O-4
7 9 . 9 1.43 x 10-4
7 9 . 9 1.48 x 1O-4
7 9 . 9 1.62 x 1O-4
80 1.52 x 1O-4
82 1.50 x 10-4
82 1.49 x 10-4
19. 9 1.25 x 1O-4
79. 9 1.24 x 1O-4
80. 2 1.40 x 10-4
80. 2 1.68 x 10-4
40. 0 5. 44 x 10-7
45. 2 1.12 x 10-6
50. 0 2. 64 x 10-6
55. 0 5 . 1 9 x 10-6
60. 5 1.16 x 1O-5
69. 5 3. 78 x 1O- 5
1 1 0 . 2
144.3
a
144.3
a
120.3
v2
3
a
a
a
v2
128. 4 a, tz
apt2
a, t 2
a,t 2
as2
a,tz
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. contd
Azonitriles II / 3
Number of
C atoms Initiator Solvent T (C) ka (S-l) E, Wmol) Notes Refs.
8 (conrd) 2,2-Azo-bis-isobutyronitrile Benzene
Benzene or Toluene
n-Butanol
Isobutanol
Di-n-butyl phthalate
Carbon tetrachloride
Chlorobenzene
Cyclohexanone
Dichloroethane
Dichloroethane:
propionitrile (1 : I)
Diethylene glycol
monobutylether
DMF
DMF
DMF/methyl
methacrylate (9/1)
@/3
(713)
(6/4)
(515)
(4/6)
(317)
CV)
(1/9)
NJV-Dimethylaniline
DioxanefWater (80/20)
pH 7.0
Dioxane/Water (80/20)
pH 10.7
4 0
5 0
6 0
7 0
7 8
3 7
4 3
5 0
6 0
1 0 0
T W
8 2
8 2
8 2
80.2
8 0
9 0
1 0 0
1 1 0
1 2 0
1 2 7
1 3 7
1 4 5
8 0
9 0
1 0 0
1 1 0
1 2 0
4 0
6 0
7 7
6 4
8 2
1 0 1
T (K)
8 2
7 0
4.83 x lo-
2.085 x 1O-6
8.45 x 10 -6
3.166 x 1O-5
8.023 x lo-
2.83 x lo-
7.35 x lo-
2.16 x 1O-6
9.15 x 10-6
1.52 x 1O-3
1.58 x lOI5
1.54 x 10-4
1.55 X 10-4
1.66 x 10-4
(1.67-1.76) x 1O-4
2.64 x 1O-4
6.47 x 1O-4
1.78 x 1O-3
4.88 x 1O-3
1.43 x 10-2
2.48 x 1O-2
5.43 x 10-2
1.24 x lo-
2.22 x 10-4
4.23 x 1O-4
1.99 x 10-3
5.3 x 10-3
1.48 x 10-2
2.15 x lo-
4.00 x 10-6
1.21 x 10-4
1.93 x 10-5
1.93 x 10-4
1.93 x 10-3
2.89 x lOI
1.43 x 10-4
2.01 x 10-5
1.64 x 10-5
123. 4
128.9
exp[- 128.9/RT]
a
a
a
122.2
Y4
Y4
Y4
Y4
Y4
Yl6
Y16
Y32
128.4 a,t 2
as2
a
exp[- 130.23/RT]
a
m8
6 6
6 6
6 6
6 6
6 6
3 9
3 9
3 9
1 9
3 9
3 9
1 7 5
2
2,175
6 1
236
236
236
236
236
236
236
236
3 7 5
3 7 5
3 7 5
3 7 5
375
6 9
6 9
6 2
344
344
344
344
2,175
293
293
7 0
66.82
1.94 x 10-5
2.442 x 10-5
293
2 6
71.2 6.2096 x 10 -5 294
6 0 6.45 x 1O-4 3 5 5
6 0 5.55 x 10-4
6 0 5.10 x 10-4
6 0 5.10 x 1o-4
6 0 5.30 x 10-4
6 0 5.65 x 1O-4
6 0 5.35 x 10-4
6 0 5.65 x 1O-4
6 0 6.25 x 1O-4
6 0 6.50 x 1O-4
66.82 3.483 x 1O-5
72.27 6.914 x 1O-5
8 0 1. 83 x 1O-4
65.3 2.53 x 1O-5
70.0 3.20 x 1O-5
75.0 8.5 x 1O-5
80.0 1. 62 x 1O-4
a
141.0
3 5 5
3 5 5
3 5 5
3 5 5
3 5 5
3 5 5
3 5 5
3 5 5
3 5 5
2 6
2 6
6 2
1 8 6
1 8 6
1 8 6
1 8 6
75.0 1.72 x 1O-4
8 0 1.46 x 1O-4 a
1 8 6
6 2
Notes page II - 69; References page II - 70
II / 4 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 1. contd
Number of
C atoms Initiator Solvent
T(C) kd (S-) E. Wmol) Notes Refs.
8 (contd) 2,2-Azo-bis-isobutyronitrile Ethyl acetate
Ethyl acetate/
SnC14 (1: 1)
GlycerolIDMF 95/5, (v/v)
Maleimide (solid state)
Methyl methacrylate
Nitrobenzene
I-Nitrobutane
Propionitrile/SnC14 (1 : 1)
Propylene carbonate
Styrene
Toluene
Toluene/SnCl 4 (1 : 1)
Xylene
o-Xylene
3,6-Dicyano-3,6-dimethyl-
1,2-diazacyclohexene- 1
Water
Dichloromethane
2,2-Azo-bis[2-(hydroxymethyl)
propionitrile
Methyl cellosolve
9 N-Acetyl N-u-cyanocyclohexyl-
diimide
Toluene
1 0 N-Acetyl N-a-cyanocycloheptyl-
diimide
Toluene
4,4-Azo-bis-(4-cyanopentanol) Acetone
4,4-Azo-bis-(4-cyanovaleric acid) Acetone
1,l -Azo-bis-1-cyclobutanenitrile Mesitylene
2,2-Azo-bis-2-methylbutyronitrile
Xylene
Toluene
Xylene
40 4.7 x 10-7
6 0 9.36 x 1O-6
T W)
8.56 x lOI
128.5
exp[- 127.4/RT]
7 1 . 2 2.6054 x 10 -s
6 5 4.97 x 10-5
72 2.07 x 1O-4
50 9.7 x 10-7
50 7.5 x 10-6
60 7.20 x 1O-4
70 3.1 x 10-5
70 1.27 x 1O-4
8 0 1.98 x 10-4
1 0 0 2.24 x 1O-3
8 2 1.45 x 10-4
T 6) 9.10 x 105
7 2 . 2 7 5.821 x lo-s
5 0 2.97 x 1Om6
7 0 4.72 x 1O-5
T 6) 1.29 x 10
6 8 . 4 3.8 x 10-5
60.00 9.03 x 1Om6
6 0 9.8 x 10-6
6 5 1.9 x 10-5
7 0 4.0 x 10-5
8 0 . 4 1.55 x 10-4
9 0 . 0 4.86 x 10m4
1 0 0 . 0 1.60 x 1O-3
105.0 2.61 x 1O-3
6 9 . 8 3.8 x 10-5
8 0 . 2 (1.72-1.60) x 1O-4
8 0 . 3 1.30 x 10-4
6 0 4.0 x 10-5
5 0 2.0 x 10-6
7 7 9.46 x 1O-5
8 2 1.44 x 10-4
8 0 1.53 x 10-4
8 0 1.50 x 1o-4
8 2 1.45 x 10-5
8 5 2.751 x 1O-4
9 5 9.581 x 1O-4
105 2.782 x 1O-3
T 6) 3.16 x lOI
5 0 1.56 x 1O-6
- 6.06 4.60 x 10m4
0 . 0 3 1.14 x 10-3
2 . 5 2 1.64 x 1O-3
7 7 1.93 x 10-5
8 2 . 0 5.21 x 1O-5
9 2 . 8 1.70 x 1om4
1 0 0 . 6 3 . 7 4 x 1om4
5 9 . 4 4.44 x lo-s
66.1 9 . 8 2 x 1O-5
7 9 . 6 4 . 5 1 x 10-4
7 0 4.26 x lo-
7 0 4 . 5 8 x lo-
1 3 0 . 4 5 . 2 0 x 1O-5
1 4 1 . 6 1.60 x 1O-4
1 2 0 . 4 2 . 0 5 x lo-
6 9 . 8 2 . 3 x lo-
8 0 . 2 8.4-9.0 x 10 -5
8 0 9 . 9 7 x 10-5
1 3 2 . 2
exp[- 127.O/RT]
1 2 7 . 6
exp[- 127.6/RT]
121.3
142.3
1 3 1 . 0
131.8
exp[- 131.8/RT]
8 8 . 8
114.8
1 1 2 . 0
134.3
1 2 9 . 7
1 2 3 . 0 a
as2
as2
a
a
a
a,v 20
v4
a
a
a
a
a
cm3
a
m2
a
a
a
a
as4
a
h
a
m7
m7
6 9
6 9
290
294
1 8 5
1 8 5
289
289
3 5 5
216
216
226
226
2 , 1 7 5
290
26
1 3 2
1 3 2
1 3 2
234
2 9 1
290
339
4 7
47
47
4 7
4 7
61
6 1
234
290
1 7 5
1 7 5
175
6 2
62
2
332
332
332
332
2 8 5
252
252
252
339
322
322
322
322
322
322
3 0 5
3 0 5
101
101
101
61
61
6 2
TABLE 1. conrd
Azoni t ri l es II/5
Number o f
C atoms Initiator Solvent T (C) kd (S-l) E. Wmol) Notes Refs.
10 (co&d) 2,2-Azo-bis-2-ethylpropionitrile
2,2-Azo-bis-2-methylbutyronitrile
N-benzoyl N-a-cyanoethyldiimide
4-Bromophenyl-azo-2-methyl-
2-propionitrile
4-Bromophenyl-azo-(methyl-
propanedinitrile)
4-Nitrophenyl-azo-2-methyl-
2-propionitrile
4-Nitrophenyl-azo-2-(methyl-
propanedinitrile)
Phenyl-azo-2-methyl-2-
propionitrile
Phenyl-azo-2-(methyl-
propanedinitrile)
Phenyl-azo-2-(methyl-
propanedinitrile)
1 1 4-Bromophenyl-azo-2-(ethyl-
propanedinitrile)
4-Methoxyphenylazo-2-
(methylpropanedinitrile)
4-Methoxyphenyl-azo-
2-(methylpropanedinitrile)
Ni t r o b e n z e n e
Cyclohexanone
Ch l o r o b e n z e n e
Ethanol
Ethylbenzene
To l u e n e
To l u e n e
DCB
DCB
DCB
DCB
DCB
DMF
1,2,4-Trimethylbenzene
DCB
DCB
DCB
Butanol
Ch l o r o b e n z e n e
DCB
Decane
DMSO
He p t a n e
Hexanol
Oc t a n e
Oc t a nol
Pr o p a n o l
To l u e n e
Ch l o r o b e n z e n e
DCB
8 0 8.3 x 1O-5
1 0 0 1.08 x 1O-3
79.9 1.06~ 1O-4
90.0 3.71 x 10-4
100.1 1.27 x 1O-3
66 1.93 x 10-5
8 4 1.93 x 1o-4
1 0 4 1.93 x 10-3
T (W 1.38 x 1015
80.0 1.05 x 1o-4
90.0 3.23 x 1O-4
100.0 9.87 x 1O-4
80.0 8.22 x 1O-5
90.0 2.94 x 1O-4
100.0 1.02 x 10-3
6 7 1.9 x 10-5
69.2 1.31 x 10-5
83.2 7.96 x 1O-5
90.0 1.744 x 10 -4
1 6 0 2.85 x 1O-5
8 0 2.4 x 10 -
8 5 4.8 x 1O-5
90 9.4 x 10-5
T 6) 7.23 x lOI
1 6 0 2.3 x lo-
8 0 3.1 x 10-5
8 5 6.0 x 1O-J
90 1.14 x 10-4
T (K)
1.35 x 106
1 6 0 5.65 x 1O-5
1 6 0 6.9 x 1O-5
1 6 0 5.35 x 1o-5
80 4.45 x 10-5
8 5 8.0 x 1O-5
90 1.42 x 1O-4
T W
8.48 x lOI
80 2.4 x 1O-5
8 5 4.8 x 1O-5
90 9.4 x 10 -5
T (K) 7.23 x 1016
8 0 1.85 x 1O-5
8 5 3.65 x 1O-5
90 7.05 x 10-5
T W) 3.00 x 106
8 5 2.9 x 1O-4
8 5 9.5 x 10 -5
8 5 8.35 x 1O-5
8 5 3.8 x 1O-5
8 5 4.87 x 1O-4
8 5 5.15 x 10-5
8 5 1.6 x 1O-4
8 5 4.4 x 10-5
8 5 1.5 x 10-4
8 5 3.1 x 1o-4
8 5 6.75 x lo-s
78.1 5.74 x 10-5
85.3 9.52 x lo-
90.2 1.307 x 1o-4
75.0 2.73 x lo-
85.1 8.35 x lo-
95.1 2.236 x 1O-4
104.9 6.397 x 1O-4
143.1
131.6
exp[- 129.93/RTj
119.8
134.9
127.9
145.0
exp[- 145.O/RTJ
139.1
exp[- 139.1/RT]
123.2
exp[- 123.2/RT]
145.0
exp[- 145.O/RTj
142.9
exp[- 142.9/RT]
1 1 0
71
1 1 5
1 4 2
1 1 4
1 3 6
1 0 2
1 4 0
1 1 2
1 0 3
1 3 7
71.5
1 1 6
a 226
a 226
h 336
336
336
344
344
344
344
h 336
336
336
h 336
336
336
a 339
322
322
322
329
329
329
329
329
329
329
329
329
329
329
329
329
329
329
329
329
329
329
3 2 9
329
329
329
329
329
3 3 1
3 3 1
3 3 1
3 3 1
3 3 1
3 3 1
3 3 1
3 3 1
3 3 1
3 3 1
331
330
330
330
330
330
330
330
Not es page I I - 69; References page II - 70
II/6 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 1. contd
Number of
C atoms Initiator Solvent
T W) kd (S-) E. Wmol) Notes Refs.
11 (cant d) 4-Methoxyphenyl-azo-
2-(methylpropanedinitrile)
Phenyl-azo-2-(2-methyl-
butyronitrile)
4-Tolyl-azo-2-(methyl-
propanedinitrile)
12 4,4-Azo-bis-(l-bromo-
4-cyanopentane)
4,4-Azo-bis-4-cyano-
pentanoic acid
4,4-Azo-bis-(4-cyanopentanol)
1,l -Azo-bis- 1 -cycle-
pe nt a ne ni t r i l e
2,2-Azo-bis-2-cyclopropyl-
propionitrile (mp 64-65)
2,2-Azo-bis-2-cyclopropyl-
propionitdle (mp 76-77)
2,2-Azo-bis-2,3-
dimethylbutyronitrile
2,2-Azo-bis-2-methyl-
valeronitrile
4-Bromophenyl-azo-2-
(isopropylpropanedinitrile)
2,6-Dimethylphenyl-azo-
2-methylpropanedinitrile
13 N-Benzoyl N-u-cyanocyclo-
pentyl diimide
4-Bromophenyl-azo-
isobutylpropanedinitrile
4-Bromophenyl-azo-Z
(2-reti-butylpropionitrile)
4-Nitrophenyl-azo-2-
(2-terr-butylpropionitrile)
Phenyl-azo-2-(2-rert-butyl-
propionitrile)
1 4 2,2-Azo-bis-2-cyclobutyl-
propionitrile (mp 38-42)
2,2-Azo-bis-2-cyclobutyl-
propionitrile (mp 81.5-82.5)
DCB
DCB
DMP
1,2,4-Trimethylbenzene
DCB
To l u e n e
Wat er
Di-n-butyl phthalate
To l u e n e
To l u e n e
To l u e n e
To l u e n e
To l u e n e
DCB
DCB
To l u e n e
DCB
DCB
DCB 1 6 0 1.8 x 1O-5 329
DCB
1,2,4-Trimethylbenzene
Hexamethyl-
phosphoramide
To l u e n e
To l u e n e 80.5 1.51 x 10-4 w 1 0 4
exp[-116/RTJ
114.8
exp[- 114.8/RT]
T 6) 5.67 x 10
8 0 4.7 x 10-5
85 8.1 x 1O-5
90 1.38 x 10-4
T (W 2.94 x 102
1 6 0 5.0 x 10-5
1 6 0 5.2 x 1O-5
1 6 0 5.05 x 10-5
80 4.5 x lo-s
8 5 7.9 x 10-5
90 1.365 x 10 -
T W 1.21 x 103
T (K)
1.0 x 10
117.7
exp[- 117.7yRT]
exp[- 104.7/RT]
330
329
329
329
329
329
329
329
329
329
329
329
307
69 1.9 x 10-5
80 8.97 x 1O-5
80 2.55 x 1O-4
90 7.99 x 1o-4
1 0 0 2.81 x 10-3
1 1 0 8.99 x 1o-3
1 2 0 2.6 x 1O-2
1 3 0 5.2 x 1O-2
80.3 7.45 x 10-5
89.2 2.43 x 1O-4
95.1 5.18 x 10-4
44.2 3.50 x 10-5
49.5 7.53 x 10-5
59.2 2.68 x lo-
44.2 3.90 x 10-5
49.5 8.17 x 1O-5
59.3 2.46 x 1O-4
69.8 2.6 x lo-
80.2 1.02 x 10-4
69.8 4.2 x 1O-5
80.2 (1.65-1.74) x 1O-4
8 0 1.4 x 10-5
8 5 2.80 x lo-
90 5.4 x 10 -s
T (K)
1.73 x 106
60.1 3.06 x 1O-5
70.0 1.177 x 10-4
80.6 4.594 x 10-4
84.5 7.320 x 10 -4
T (W
2.06 x 10
76.7 1.62 x 1O-5
82.0 3.17 x 10-5
98.4 2.252 x 10-4
80 1.12 x 10-4
8 5 2.21 x 10-4
90 4.26 x 1O-4
T W
1.19 x 107
1 6 0 4.85 x 10-5
142.3
141.4
117.2
108.8
133.9
138.1
142.0
exp[- 142.O/RT]
130.5
exp[- 130.5/Rfl
131.9
141.6
exp[- 141.6kJ/RT]
a 339
a 6 2
375
3 7 5
3 7 5
3 7 5
3 7 5
375
101
101
101
W 57
W 5 7
w 5 7
W 5 7
W 5 7
W 5 7
6 1
61
61
61
329
3 2 9
329
329
330
330
330
330
330
322
322
322
329
329
329
329
329
1 6 0 9.35 x 1o-5 329
1 6 0 9.65 x 1O-5 329
1 6 0 9.5 x 10-5 329
80.5 1.51 x 10-4 W 1 0 4
.
Azonitriles II / 7
TABLE 1. contd
Number of
c atoms Initiator Solvent T(C) kd (s-) E, Wmol) Notes Refs.
14 (contd) 1,l -Azo-bis- 1 -cyclohexane nitrile Chlorobenzene
DMSO
Nitrobenzene
Toluene
2,2-Azo-bis-2,4-dimethyl-
valemnitrile
Dimethyl-4,4-azo-bis-cyano-
pentanoate (meso)
(not)
bD-)
4,4-Azo-bis-4-cyano-l-methyl-
piperidine
2,2-Azo-bis-2-propylbutyronitrile Nitrobenzene
2,2-Azo-bis-2,3,3-trimethylbutyro-
nitrile (mp 114-116)
2,2-Azo-bis-2,3,3-trimethylbutyro-
nitrile (mp 116-118)
2,2-Azo-bis-2-methylhexylnitrile
2,2-Azo-bis-2,4-dimethylvaleronitrile
2,2-Azo-bis-2,4-dimethylvaleronitrile
(mp 56-57)
2,2-Azo-bis-2,4dimethylvaleronitrile
(mp 74-76)
2,2-Azo-bis-2-isopropylbutyronitrile
N-(4Chlorobenzoyl) W-u-
cyanocyclohexyl diimide
N-(l-Cyanocyclohexyl)-
pentamethyleneketenimine
15
2-Phenyl-azo-2,4-dimethyl-
4-methoxyvaleronittile
IV-Benzoyl N-a-cyanocyclo-
heptyl diimide
Xylene
Toluene
Xylene
DMAC
DMSO
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Chlombenzene
Cumene
Toluene
rerr-Butylbenzene
Xylene
79. 97 8. 42 x 1O-6
100. 12 1.107 x 10-4
80 1.01 x 10-5
85 2.01 x 10-5
9 0 3. 89 x 1O-5
95 6. 83 x 1O-5
1 0 0 1.14 x 1o-4
80. 3 6. 5 x 1O-6
95. 2 5. 44 x 10-5
102. 4 1.26 x 1O-4
88 1.9 x 10-5
77 5.31 x 10-6
51 1.9 x 10-5
68 1.9 x 10-4
T (K)
6. 98 x 1014
77 5. 77 x 10-4
17. 9 1.43 x 10-4
85. 0 3. 76 x 1O-4
90. 2 6. 80 x 1O-4
99. 1 2. 05 x lO-3
77. 6 1.46 x 1O-4
85. 9 4. 03 x 10 -4
90. 0 6. 90 x 1O-4
99. 2 2. 04 x 10-3
11. 9 1.49 x 10-4
85. 4 3. 90 x 10-4
90. 2 6. 95 x 1O-4
99. 0 1. 91 x 10-3
80 9. 7 x 10-6
85 1.75 x 10-5
90 3. 64 x 10-5
95 6. 47 x 1O-5
80 2. 55 x lO-4
1 0 0 2. 72 x 1O-5
79. 9 7. 42~ 1O-5
89. 0 2.59 x 10-4
79. 9 1.05 x 10-4
88. 9 3. 09 x 10-4
80. 2 1.58 x lO-4
69. 8 1.98 x 10-4
80. 2 7.1 x 10-4
59. 7 8. 05 x 1O-5
69. 9 2. 89 x 1O-4
69. 8 1.98 x 1O-4
80. 2 7.1 x 10-4
80. 5 1.01 x 10-4
79. 1 8. 6 x 1O-6
86. 4 2.01 x 10-5
99. 1 1.044 x 10-4
l o o 3. 85 x 10-5
1 0 0 2. 07 x 1O-5
1 0 0 3. 93 x 1o-5
1 0 0 1. 42 x 1O-5
1 0 0 3. 1ox 10-5
1 0 0 1.83 x 1O-5
1 0 0 2.39 x 10-5
1 0 0 1.22 x 10-5
1 2 2 1.9 x 10-5
14. 6 6. 49 x 1O-5
82. 8 1.781 x 1O-4
89. 2 3.519 x 1o-4
1 4 0 . 2
1 3 5 . 6
1 2 1 . 3
121
exp[- 121/RT]
1 3 3 . 9
1 3 6 . 4
1 2 8 . 9
1 4 6 . 4
125.5
121.3
121.3
121.3
1 3 2 . 7
122.8
h
a
a
a
a
a
a
a
a
a
a
a
a
L
W
W
W
w
PYz (1)
p,z ( 3950)
PJ (1)
p,z (3950)
p.= (1)
p,z ( 3950)
PJ (1)
p,z ( 3950)
1 7 9
119
135
135
135
135
226
101
101
101
339
1 1 5
343
343
343
115
205
205
205
205
205
205
205
205
205
205
205
205
135
135
135
135
226
226
57
51
57
57
61
61
61
51
57
51
57
50
322
322
322
299
299
299
299
299
299
299
299
339
322
322
322
Notes page II - 69; References page II - 70
II/8 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 1. contd
Number of
C atoms _ Ini ti ator Solvent
T (C) kd (S-l) E. Wmol) Notes Ref s.
15 (conrd) N-(4-Methoxybenzoyl) N/-a-
cyanocyclohexyldiimide
N-(4-Methylbenzoyl) N-a-
cyanocyclohexyl diimide
N-Phenylacetyl N-cl-cyano-
cyclohexyl diimide
4-Cyano-1-methylpiperidine-4,4-azo-
4.cyano-l,l-dimethylpiperidinium
nitrate
16 4,4-Azo-bis-4-cyano-1,l -dimethyl-
piperidinium nitrate
4,4-Azo-bis(4cyanopentanoyl)bis
2-aminoethanol
1,l -Azo-bis- 1 -cycloheptane-nitrile
2,2-Azo-bis-(4-methoxy-2,4-
di met hyl val eroni t ri l e)
2,2-Azo-bis-2-methylheptylonitrile
18
1.1 -Azo-bis-1-(2-methylcyclohexane)-
nitrile
1,l -Azo-bis- 1 -cyclohexane-
carbonitrile
2,2-Azo-bis-cyclopentylpropio-
nitrile (mp 72.2-74.5)
2,2-Azo-bis-2-cyclopentyl-
propionitrile (mp 96.3-97.6)
2,2-Azo-bis-2,4,4-trimethyl-
valeronitrile (mp 67.5-69)
2,2-Azo-bis-2,4,4-trimethylvalero-
nitrile (mp 94.5-95.5)
2,2-Azo-bis-2-isopropyl-3-methyl-
butyronitrile
1,l -Azo-bis- 1 -cyano-4,4 -
dimethyl cyclohexane
2,2-Azo-bis-2cyclohexylL
propionitrile
1,l -Azo-bis-1-cyclooctanenitrile
20 4,4-Azo-bis(4-cyanopentanoyl)bis-
2-(2-aminoethoxy)ethanol
2,2-Azo-bis-2-benzylpropionitrile Toluene
Toluene
Toluene
Toluene
DMSO
DMSO
DMF
DMAC
Acetic acid
Toluene
Toluene
Toluene
Xylene
Toluene
8 0 . 8
8 7 . 9
1 0 1 . 2
8 1 . 4
8 7 . 3
1 0 1 . 9
7 4 . 3
8 2 . 9
9 1 . 2
8 0
8 5
9 0
9 5
8 0
8 5
9 0
9 5
6 5
6 9
7 4
6 5
6 9
74
6 9 . 5
4 8 . 9
5 8 . 9
6 7 . 3
3 0
4 7
T 6)
8 0 . 0
8 0 . 0
8 0 . 2
Xylene
Toluene
8 0
7.1 x 10-6
1.71 x 10-5
9 . 7 3 x 10-5
1.06 x 1O-5
2 . 2 0 x 10-5
1.255 x 1O-4
3 . 0 8 x 1O-5
9 . 7 6 x 1O-5
2 . 7 7 x 1O-4
1.76 x 1O-5
3.31 x 10-5
6 . 2 3 x 1O-5
1 . 1 5 6 x 1O-4
2 . 8 4 x 1O-5
5.11 x 10-5
9 . 8 7 x lo-
1 . 6 2 6 x 1O-4
1.76 x 1O-5
2 . 8 5 x 1O-5
4 . 6 6 x 1O-5
1.73 x 10-5
2 . 7 3 x 1O-5
4 . 5 3 x 10-5
3 . 2 8 x 1O-4
2 . 6 9 x 1O-5
9 . 7 2 x 1O-5
2 . 6 9 x 1O-4
1.9 x 10-5
1.9 x 10-4
1.03 x 105
1.63 x 1O-4
1.78 x 1O-4
7 . 4 3 x 10-6
4 . 7 x 10-6
80.5
Toluene 80.5
Toluene
Toluene
40
50
40
5 0
1.31 x 1om4
1.30 x 10-4
1.175 x 10-4
4 . 4 5 x 1o-4
6 . 9 5 x lo-
2.89 x 1O-4
Toluene 80.5 (1.325i0.35) x 10m4
DMSO
Toluene
Toluene
DMF
DMAC
8 0 1.51 x 10-5
8 5 2 . 7 9 x lo-
90 5 . 4 0 x 10-5
9 5 9 . 7 7 x 10-5
80.3 8.3 x 1O-6
8 0 . 5 2 . 2 7 x 1O-4
3 6 . 6 5 . 3 5 x 10-5
4 5 . 4 1.45 x 1o-4
4 9 . 7 2 . 6 0 x 1O-4
6 5 1.77 x 1o-5
6 9 2 . 9 0 x 10m5
7 4 4.90 x 10-5
6 5 1.74 x 10-5
6 9 2 . 8 3 x 1O-5 3 5 7
7 4 4 . 6 5 x 1O-5 3 5 7
8 0 1 . 1 6 x 1O-4 5 4
1 4 2 . 8
134.1
1 3 3 . 9
1 3 2 . 6 h
124.7 h
115.1
a
a
exp[- 115/RT]
1 2 6 . 4 a
322
322
322
322
322
322
322
322
322
1 3 5
1 3 5
135
135
135
1 3 5
1 3 5
135
3 5 7
3 5 7
357
357
357
357
101
101
101
101
3 4 3
3 4 3
343
5 0
6 2
101
1 6 6 . 9 a 6 2
w 1 0 4
w 1 0 4
113.5
121.3
w
w
w
w
50
50
50
50
5 0
132.2 h
1 0 8 . 4
1 3 5
1 3 5
1 3 5
1 3 5
61
1 0 4
101
101
101
357
3 5 7
351
3 5 7
TABLE 1. contcf
Mi scel l aneous Azo- Deri vat i ves II/9
Number of
c atoms Initiator Solvent
TCC) kd (s-l)
E, (kJ/mol) Notes Refs.
2 0 (contd) 2,2-Azo-bis-2-isobutyl-4-methyl- Toluene 6 0 . 1 3 . 7 8 x 1O-4 50
valeronitrile 8 0 . 5 5 . 2 8 x 1O-3 50
2,2-Azo-bis-2-(4-chIorobenzyl)- Toluene 8 0 8 . 8 x 10-5 54
propionitrile
2,2-Azo-bis-2-(4-nitrohenzyI)- Toluene 8 0 1.00 x 10-4 54
propionitrile
2 2 I,1 -Azo-bis- 1 -cyclodecanenitriIe Toluene 5 0 . 8 5 . 4 0 x 10-5 101
6 0 . 2 1 . 7 0 x 10-4 101
6 9 . 5 5 . 6 9 x 10 -4 101
3 4 4,4-Azo-bis-(4-cyanopentanyl)- Di-n-butyl phthalate 90 9.86 x 1O-4 3 7 5
bis(heptadecatluorododecanoate) 1 0 0 2.11 x 10-3 3 7 5
1 1 0 4 . 4 x 10-3 3 7 5
1 2 0 1.1 x 10-2 375
1 3 0 1.42 x 1O-2 3 7 5
TABLE 2. MISCELLANEOUS AZO-DERIVATIVES
Number of
c atoms Initiator Sol vent T(C) kd (S-l) E, Wmol) Notes Refs.
2 1,l -Azo-bis-formamide DMF
DMSO
Formamide
4 Methyl-azo-3-propene
Hexamethyl-
phosphoramide
Vapor
5 2,3-Diazobicyclo[2,2,l]hept-Zene Isooctane
6 2,2-Azo-bis-propane
Toluene
Vapor
3,3-Azo-bis-1-propene Vapor
2,2-Dichloro-2,2-azo-bis-propane Diphenyl ether
Silicone oil
Methyl-azo- 1 ,I -dimethyl-2-propene
(cis)
Acetone
(tram) p-Diisopropyl-
Benzene
Pertluoroazo-2-propane Vapor
8 6 . 0
1 0 0 . 3
115.3
8 6 . 0
100.3
1 1 5 . 3
8 6 . 0
1 1 5 . 3
115.3
163.3 5.88 x 1O-4
1 6 9 . 8 1.110 x 10-3
1 8 2 . 8 3.36 x 1O-3
T 6)
3.2 x 10 I4
131.5 5.44 x 10-6
142.3 1.82 x 1O-5
164.1 1.66 x 10-4
1 8 0 . 8 8.35 x lO-4
164.1 1.64 x 10 -4
250 7.67 x 1O-3
260 1.67 x 10 -2
270 3.35 x 10 -2
280 6.52 x 1O-2
290 1.28 x lo-
1 4 2 . 6 5 3.88 x 1O-4
1 5 2 . 6 8 1.10 x 10-3
1 6 7 . 1 2 4.45 x 10-3
1 5 8 . 5 1.03 x 10-4
1 6 7 . 9 4.54 x 10-4
178.5 8.08 x 10-4
185 4.8 x 1O-4
1 9 9 2.1 x 10-3
2 2 1 1.6 x 1O-2
- 13.89 3.62 x lo-
- 5.04 1.70 x 10-4
4.00 6.82 x 10 -4
1 1 4 . 5 5 1.02 x 10-4
1 2 3 . 8 3 2.68 x 1O-4
1 3 3 . 3 3 8.44 x 1O-4
T (K) 5.01 x 106
1.56 x 1O-5
5.73 x 10-5
1.14 x 10-4
5.48 x 1O-6
2.72 x 1O-5
1.01 x 10-4
9.25 x 10-5
-2.0 x 10-3
3.83 x lo-
1 4 8
exp[- 148/RT]
1 5 7 . 7
171.1
1 5 1 . 3
1 3 8 . 3
9 6 . 8
1 4 7 . 9
exp[- 189.O/RT]
c2
c2
CZ
C
C
C
h
hru4
u4
u4
h
h
268
268
268
268
268
268
268
268
268
298
298
298
298
1 8 0
1 8 0
1 8 0
1 8 0
1 8 0
110
1 1 0
1 1 0
1 1 0
110
3 1 9
319
3 1 9
297
297
297
240
240
240
252
252
252
252
252
252
360
Notes page II - 69; References page II - 70
II/l0 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 2. contcf
Number of
C atoms Initiator Sol vent
T (C) kd (S-l) E, Wmol) Notes Refs.
6 (contd) I-Propyl-azo-3.propene
Triazobenzene
ferr-Butyl-azo-3-propene
2,2-Azo-isobutyramide
Azo-bis-isobutyramidine
Azo-bis-isobukyramidine
2HCl (AIBA)
AIBA
AIBA-kaolin adduct
AIBA-bentonite adduct
Azo-bis(2amidinopropane) 2HCl
2,2-Azo-bis(2-amidinopropane) 2HCl
Azo-bis-isobutyramidine 2HNOs
Methanol
Water
Water
DMSO-cumene
2.2-Azo-bis-isobutane Vapor
2,2-Azo-bis-isobutane
Vapor
Nitrobenzene
Tetralin
Water
Water
Chloroform
DMSO
Methanol
Water (pH 1.9)
Water (pH 5.8)
Water (pH 9.5)
Water
Water
Water
Water
Diphenyl ether/iso-
quinoline (90/ 10)
1 0 1 . 3 2 1.10 x 10-6
1 1 4 . 1 0 5 . 6 0 x 1O-6
1 2 6 . 0 2 2.11 x 10-5
T (K) 6 . 3 x 10 l4
1 0 5 3 . 5 x 10-7
115 1.20 x 10-6
1 3 0 6 . 2 5 x 1O-6
145 2.50 x 10m5
105 4 . 0 x 10-7
115 1.34 x 10-6
1 3 0 6.01 x 1O-6
1 4 5 2 . 4 7 x lo-
8 0 . 8 8 2 . 1 3 x 1O-6
90.90 7 . 2 7 x 1O-6
106.81 3 . 8 9 x 1O-5
T W
5 . 4 x 102
8 8 1.9 x lo-s
60 3 . 1 5 x lo-s
6 0 2 . 8 0 x 1O-5
6 0 7.1 x 10-6
70 3 . 6 8 x 1O-6
60 1.45 x 10-6
50 8 . 3 x lo+
6 0 3 . 4 2 x 1O-5
5 0 8 . 0 x 1O-6
60 3 . 2 2 x 1O-5
50 4 . 7 x 10-6
60 2 . 5 3 x 10 -5
6 0 . 0 3 . 7 0 x 10-5
7 0 . 0 1.33 x 10-4
7 5 . 0 2 . 5 8 x 1O-4
8 0 . 0 5 . 1 3 x 1o-4
40.15 2 . 4 9 x 10 -6
50.05 9 . 7 9 x 10-6
60.20 4 . 0 3 x 10-5
70.10 1.52 x 1O-4
1 0 0 . 1 0 4.96 x 1O-3
7 0 1.52 x 1O-4
5 0 . 0 1.37 x 10-5
6 0 . 0 6 . 1 6 x 10-5
7 0 . 0 2 . 2 8 x 1O-4
8 0 . 0 9 . 5 3 x 10-4
5 0 . 0 1.80 x 1O-5
5 5 . 0 3 . 9 7 x 10-5
6 5 . 0 1.53 x 1o-4
7 0 . 0 3.21 x 1O-4
8 0 . 0 1.04 x 10-3
50 1.45 x 10-5
50 8.1 x 1O-6
5 6 1.93 x 10-5
6 0 4.86 x 1O-5
70 1.53 x 10-4
1 6 0 1.9 x 10-5
1 8 0 5.01 x 10-5
1 9 0 1.53 x 10-4
210 1.05 x 10-3
1 7 4 . 8 6 . 8 x 10-5
188.3 1.75 x 10-4
188.8 1 . 1 4 x 10-4
165 2.782 x lo-
175 8 . 7 4 x 1O-5
1 8 5 2 . 5 1 3 x 1O-4
1 9 0 4.143 x 10-4
1 4 9 . 2
exp[- 149.2/RT]
1 4 0 . 2
1 3 6 . 0
1 2 4 . 9
exp[- 124.9/RT]
1 2 6 . 5
1 2 4 . 4
1 5 1 . 7
1 2 8 . 9
1 2 2 . 6
133.9
1 2 6 . 4
1 7 6 . 6
v21
v21
v21
v21
v21
v21
v21
a
q2
q3
h
h
h
h
a
a
m4
m4
m4
m4
h
2 9 8
2 9 8
2 9 8
298
4 5
4 5
4 5
4 5
4 5
4 5
4 5
4 5
298
2 9 8
2 9 8
298
/
342 :
288
288
1 8 4
21
1 8 4
3 4 1
3 4 1
3 4 1
341 )
3 4 1
3 4 1
2 3 3
2 3 3
2 3 3
2 3 3
237
237
237
237
2 3 7
2 1
233
233
233
233
233
2 3 3
2 3 3
2 3 3
2 3 3
356
356
340
21
21
339
2 2 1
2 2 1
221
2 4 3
?
243
243
171
171
171
171
TABLE 2. contd
Miscellaneous Azo-Derivatives II/11
Number of
C atoms Initiator Solvent
T ((3 kd (S-l)
-
E. Wmol) Notes Refs.
8 (contd) 2,2-Azo-bis-isobutane
2,2-Dimethoxy-2,2- azopropane
2,2-Dimethylmercapto-2,2-
azopropane
Isopropyl-azo-1, I-dimethyl-2-
propene (cis)
(trans)
9
2,2-Azo-bis(2-methylpropane)
2-(4-Bromophenyl-azo)-2-
nitropropane
tert-Butyl-azo-l,l-dimethyl-
2-propene (trans)
2-(4-Nitrophenylazo)-2-nitro-
propane
a-Phenylethyl-azo-methane Diphenyl ether
10 2,2-Diacetylthio-2,2-azopropane
2,2-Diacetoxy-2,2-azopropane Diphenyl ether
Azo-bis( 1.1 -dimethyl-2-propene)
(tram)
Azo-bis-( 1,l -dimethyl)-2-propyne
(tram)
Xylene
2,2-Azo-bis-2-methylbutane Ethylbenzene
2,2-Azo-bis-2-methylbut-3-ene n-Demure
2,2-Azo-bis-2-(methylcarboxy)-
propane
2,2-Azo-bis-methyl-2-methyl-
propionate
2,2-Azo-bis-methyl-2-methyl- Undecane
propionate Xylene
Diphenyl ether/iso-
quinoline (90/ 10)
Diphenyl ether
Diphenyl ether
Acetone
Diisopropylbenzene
Vapor
D C B
Diisopropylbenzene
D C B
Hexadecane
Diphenyl ether
Silicone oil
Xylene
Isoamyl alcohol
Water
Collidine
1,2-Dichlorobenzene
Diethyl oxalate
Ethylene glycol
Nitrobenzene
195 6 . 7 3 1 x lo-
200 1.093 x 10-3
150.1 4 . 0 2 x 1O-5
1 5 9 . 9 1.50 x 10-4
1 7 4 . 6 6 . 6 7 x 10 -4
1 2 5 . 0 3 . 4 0 x 10-4
1 3 5 . 0 7.10 x 10-4
1 4 5 . 0 1.15 x 10-3
- 25.09 6.30 x 1O-5
- 16.65 2 . 8 7 x 1O-4
- 8.20 1 . 1 0 x 1o-3
9 7 . 4 1 1.15 x 10-4
1 0 6 . 0 6 3 . 1 9 x 10-4
1 1 5 . 0 6 9 . 2 2 x 1o-4
1 6 0 1.93 x 10-5
1 3 0 1.62 x 10m4
135 2 . 5 9 x 1O-4
1 4 0 4.30 x 1o-4
T W 1.1 x 103
73.72 8 . 6 9 x 1O-5
8 0 . 3 1 1.83 x 1O-4
8 7 . 0 8 3 . 8 0 x 1O-4
1 3 0 1.00 x 10-4
1 4 0 2 . 4 4 x 1O-4
145 4.06 x 1O-4
T (K) 1.1 x 103
151 4 . 3 5 x 10 -5
161 1 . 1 6 x 1O-4
171 3 . 4 8 x 1O-4
161 1.20 x 1o-4
1 3 0 . 0 1.33 x 10-4
1 4 0 . 0 4.40 x 10-4
1 4 9 . 4 1.19 x 10-5
1 9 0 . 0 8 . 2 3 x 1O-5
2 0 0 . 1 2.61 x 1O-4
2 1 0 . 3 6 . 3 8 x 1O-4
258 1 . 4 6 x lo-
42.03 5 . 9 5 x 10-5
49.98 1.73 x 10-4
51.39 4 . 5 4 x 10-4
41.32 5 . 3 7 x 10-5
48.20 1.30 x 1o-4
57.19 4.39 x 10 -4
1 8 0 . 0 1.36 x 1O-4
1 9 0 . 0 3 . 8 9 x 1O-4
200.0 1.03 x 10-3
1 8 0 . 0 1.14 x 1o-4
1 9 0 . 0 3.51 x 1o-4
200.0 9 . 2 6 x 1O-4
44.90 6 . 7 3 x lo-
55.44 2 . 6 3 1 x 1O-4
63.74 7.045 x 10 -4
5 0 3.51 x 10-6
8 0 1.67 x 1O-4
8 0 1.44 x 1o-4
8 0 1.52 x 1O-4
8 0 1 . 2 4 x 1O-4
8 0 1.61 x 1O-4
1 0 0 1.73 x 10-3
80 1.04 x 10-4
8 0 1.09 x 10-4
1 7 1 . 8
8 4 . 6
9 1 . 3
137.8
1 3 0
exp[- 130/RT]
1 1 2 . 3
1 3 4
exp[- 134/RT]
1 6 1 . 5
1 5 1 . 3
1 7 1 . 4
1 0 9 . 4
1 1 1 . 9
1 7 6 . 4
1 7 6 . 0
107.3
129.3
149.8
b5
U5
U5
h
h
a
h
h
h
171
171
291
297
297
291
2 9 7
297
252
252
252
252
252
252
340
3 2 5
3 2 5
325
3 2 5
252
252
252
3 2 5
3 2 5
3 2 5
3 2 5
1 4 9
1 4 9
1 4 9
1 4 9
297
297
297
2 9 7
297
297
240
h
h
h
h
h
252
252
252
252
252
252
336
336
336
336
336
336
278
278
278
2 8 5
a 226
a 226
a 226
a 226
a 226
a 226
a 226
a 6 2
Notes page 11-69; References page II- 70
II/12 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 2. contd
Number of
C atoms Initiator Solvent
T(Cl ka (S-l) E. Wmol) Notes Refs.
IO (contd) N,N-Azo-piperidine
2-(4-Methoxyphenylazo)-
2-nitropropane
Silicone oil
D C B
Dimethyl 2,2-azo-isobutyrate Acetic acid
Dimethyl-2,2-azo-isobutyrate Methanol
11
2,3,7,8-Tetraazahexacyclo-
[7.4.1.04~2.06~1.00~3]tetradeca-
2,7-diene
2-(2,6-Dimethylphenylazo)-
2nitropropane
cc-Phenylethyl-azo-2-propane
12 Azo-bis-isobutanoldiacetate Cyclohexane
Azo-bis-(I-carbomethoxy-3-methyl-
prowe)
4,4-Azo-bis-(4-cyanopentanoic acid)
(meso)
Acetonitrile
Benzene
Cyclohexane
Methanol/SnCl4
Methanol/ZnCl 2
Paraffm
Toluene
Toluene/SnCl 4
Acetonitrile-d 3
D C B
Diphenyl ether/
benzoquinone
Diphenyl ether
Benzene
Carbon tetrachloride
DMAC
181 1.7 x 10-3
228 4.3 x 10-2
1 3 5 7.4 x 10-5
1 4 0 1.30 x 10-4
1 5 0 3.67 x 1O-4
T 6)
2.5 x lOIs
40 8.61 x 10-7
50 3.16 x 1O-6
60 1.56 x 1O-5
70 5.49 x 10-5
40 5.44 x 10-7
50 2.68 x 1O-6
60 1.01 x 10-5
70 3.57 x lo-s
50 2.22 x 10-6
60 8.85 x 1O-6
70 3.27 x 1O-s
40 2.89 x lo-
50 1.38 x 1O-6
60 5.85 x 1O-6
8 0 2.22 x 1o-s
40 6.86 x 10-7
50 3.12 x 1O-6
60 1.44 x 10-5
40 1.20 x 10-6
50 4.46 x 1O-6
60 1.98 x 1O-s
60 1.51 x 10-5
9 9 . 2 1.02 x 10-3
60 8.9 x 10-6
60 8.11 x 10-6
66 1.93 x 10-5
70 3.17 x 10-5
8 0 1.19 x 10-4
60 1.63 x 1O-4
2 1 5 1.18 x 1O-s
230 6.65 x 1O-s
250 3.40 x 10-4
1 3 5 9.0 x lo-s
1 4 0 1.44 x 10-4
1 5 0 3.86 x 1O-4
T 6) 4.8 x lOI3
1 4 3 . 2 1.50 x 10-4
1 4 3 . 0 1.54 x 10-4
1 5 2 . 0 4.24 x 1O-4
165.5 1.570 x 10-3
1 7 0 . 0 4.86 x 1O-s
1 8 0 . 0 1.27 x 1O-4
1 8 9 . 0 3.47 x 10-4
1 9 9 . 0 1.01 x 10-3
3 6 3.05 x 10-7
4 5 1.31 x 10-6
55 4.54 x lo-6
6 5 1.82 x 10-5
4 5 7.18 x lo-
5 5 3.79 x 10-6
6 5 1.02 x 10-5
7 7 . 6 1.33 x 10-4
8 5 . 3 3.70 x 10-4
90.9 7.17 x 10-4
99.8 2.02 x 10-3
1 5 3
exp[- 153/RT]
1 3 1 . 6
1 8 8 . 7
exp[- 138/RZj
133.5
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
Xl
Xl
Xl
t13
t13
t13
240
240
3 2 5
3 2 5
3 2 5
3 2 5
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
1 7 4
1 7 4
1 7 4
325
325
325
325
220
310
310
310
1 8 9
1 8 9
1 8 9
1 8 9
6 8
6 8
6 8
6 8
6 8
6 8
6 8
2 0 5
2 0 5
2 0 5
205
TABLE 2. contd
Miscellaneous Azo- Deri vat i ves II/13
Number of
C at oms Initiator Sol vent T (Cl kd (S-l) E. Wmol) Notes Refs.
12 (contd) 4,4-Azo-bis-(4-cyanopentanoic acid)
(Doi)
@D+)
(Do-)
2,2-Azo-bis-(ethyl-2methyl- Chlorobenzene
2,2-Azo-bis-[2-methyl+
(2-hydroxyethyl) propionamide]
Azo-bis-(PI&-dimethyleneisobutyr-
amidine) 2HNOs
Azo-bis-(N,N-dimethylene
isobutyramidine) 2HCl
Azo-bis-(N,N-dimethyleneisobutyr-
amidine)
terr-Butyl(2,2,4-trimethyl-
2-pentyl)diazene
DMSO-tetralin
Methanol
Diphenyl ether
wCumyl-azo-isopropane Diphenyl ether
2,2-Dicyclopropyl-2,2-azopropane
Di-(2-hydroxyethyl)-2,2-azo-
bis-isobutyrate
14
2,2-Azo-bis[N-(2-hydroxyethyl)-
2-methylpropionamidine] 2HCl
2,2-Azo-bis[2-(imidazoline-2-yl)-
propane 2HCl
2,2-Azo-bis[2-(imidazoline-2-yl)-
propane
2,2-Azo-bis-(2-cyclobut-
I-enylpropane)
Nitrobenzene
Water
DMSO
DMSO-cumene
DMSO-tetralin
Water
DMSO
DMSO-cumene
Diphenyl ether/
isoquinoline (90/ 10)
Dioxane
DMF
Toluene
Water
8 0 1.79 x 10-4
7 5 8.04 x 1O-5
8 0 1.39 x 1o-4
8 5 2.6 x 1O-4
60 1.09 x 10-5
61 1.9 x 10-5
1 5 5 1.61 x 1O-4
165.7 4.15 x 10-4
1 8 0 . 0 1.98 x 1O-3
1 2 0 . 0 1.06 x 1O-4
1 3 5 . 0 5.94 x 10-4
1 4 3 . 0 1.421 x 1O-3
1 4 5 . 0 7.56 x 1O-5
1 5 0 . 0 1.273 x 1O-4
1 5 5 . 0 2.147 x 1O-4
1 6 0 . 0 3.771 x 10-4
1 6 5 . 0 6.07 x 1O-4
1 7 0 . 0 1.033 x 1o-3
60 1.61 x 1O-5
70 5.88 x 1O-5
8 0 2.02 x 10-4
6 0 1.53 x 10-5
70 5.62 x 1O-5
8 0 2.0 x 1o-4
60 1.62 x 1O-5
70 5.83 x 1O-5
8 0 2.066 x 10 -4
5 8 1.93 x 10-5 a
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
Methanol 50 4.83 x 1o-5 356
Water 50 4.02 x 1O-5 356
Methanol
n-Decane
5 0 4.7 x 10-6
3 9 . 2 1 1.286 x 1O-4
50. 7 1 5.678 x 1O-4
5 8 . 9 5 1.762 x 1O-3
112.3 h
356
278
278
278
1 7 . 9 1.53 x 10-4
8 5 . 8 4.11 x 10-4
90.1 7.00 x 1o-4
9 9 . 1 2.09 x 1O-3
78.0 1.55 x 10-4
8 5 . 4 4.05 x 10-4
90.0 6.98 x 1O-4
99.0 2.00 x 10-3
7 7 . 7 1.51 x 10-4
8 6 . 0 4.34 x 1o-4
9 0 . 5 7.33 x 10-4
9 9 . 7 2.24 x 1O-3
70 4.13 x 10-5
9 2 . 6 5.93 x 1o-4
8 0 1.56 x 1O-4
8 6 1.9 x 1o-5
60 2.06 x 1O-4
70 6.64 x 1O-4
15 1.08 x 10-3
70 6.97 x 1O-4
6 0 2.13 x 1O-4
44 1.9 x 1o-5
1 2 3 . 0
1 5 9 . 6
1 5 8 . 2
1 2 5 . 7
1 2 9 . 9
1 2 9 . 9
a 2 0 5
a 2 0 5
a 2 0 5
a 2 0 5
a 2 0 5
a 2 0 5
a 205
a 205
a 2 0 5
a 205
a 205
a 2 0 5
a 1 3 9
a 1 3 9
a 226
a 342
a
21
2 1
21
21
21
339
a
h
h
Notes page II - 69; References page II - 70
II/14 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 2. contd
Number of
C atoms Initiator Sol vent
T (0 ka (S-l) E. Wmol) Notes Refs.
14 (cornd) 2,2-Azo-bis-(2-methylhex-3-ene) n-Decane
Di-(2-chloroethyl)-2,2-azo-bis-
isobutyrate
Di-(2-chloroethyl)-2,2-azo-bis-
isobutyrate
1 ,l -bis-(4-Chlorophenyl)
azomethane
Di-(2-hydroxypropyl)-
2,2-azo-bis-isobutyrate
2,2,3,3,3,3-Hexamethyl.
2,2-azo-butane
1,l -Diphenyl-azo-methane Diphenyl ether
15
2,2-Azo-bis[2-methyl-N-(phenyl-
methyl)propionamidine] 2HCl
2,2-Azo-bis[2-(4-methyl-
imidazoline-2-yl)-propane
2,2-Azo-bis[2-(4-methylimidazoline-
2-yl)-propane 2HC1
2,2-Azo-bis[2-(3,4,5trihydro-
pyrimidine-2-yl)propane
2,2-Azo-bis[2-(3,4,%rihydro-
pyrimidine-2-yl)propane 2HCl
1-Methylcyclopentyl-azo-
cc-cumene
16 1,l -Azo-bis-l-chloro-
I-phenylethane
1.1 -Azo-bis-l-chloro-l-
(3-bromophenyl)ethane
l,l-Azo-bis-l-chloro-l-
(4-bromophenyl)ethane
Dioxane
DMF
Toluene
Diphenyl ether
Dioxane
DMF
Diphenyl ether
Water
Methanol 50 1.23 x 1O-5 356
Methanol 50 7 . 4 8 x 1O-5 356
Water 50 6 . 7 3 x 1O-5 356
Methanol 50 1.1 x 10-6 356
Methanol
Water
rert-Butyl benzene
50 7 . 8 x 1O-6
50 5 . 9 x 10 -6
8 8 . 3 5 . 0 0 x 10-5
107.3 4 . 9 5 x 10-4
1 1 7 . 6 1.43 x 10-3
7 4 . 8 8 . 6 x 1o-4
8 3 1.95 x 10-3
6 7 . 8 2 . 8 x 1O-4
8 6 . 2 3 . 3 x 10-3
9 8 . 2 1 . 4 0 x 10-2
9 4 . 5 2 . 4 x 1O-3
112.3 5 . 2 x 1O-2
120.5 1.03 x lo-r
129.3 1.6 x lo-
1 3 7 5 . 0 x 10-1
64 1.8 x 1O-4
74 7 . 2 x 1O-4
64 1.79 x 10-4
74 7 . 2 0 x 1O-4
59 1 . 6 4 x 10-4
69 6.64 x 1O-4
59 1.77 x 10-4
6 9 6 . 7 5 x 1O-4
1 3 2 . 0
356
356
h 3 2 7
327
327
240
240
240
240
240
240
240
240
240
240
240
240
a 239
a 239
a 239
a 239
a 239
a 239
Acetophenone
Benzophenone
Pa&in
Toluene
Toluene
Toluene
3 9 . 2 5 5 . 3 3 x 10-5
49.52 2.256 x 10 -4
5 8 . 9 5 7.584 x 10 -4
6 0 1.56 x lo-s
7 0 5 . 5 5 x 10-5
8 0 1 . 9 6 7 2 x 10 -4
6 0 1.25 x 1O-5
70 4.902 x 1O-5
8 0 1.9125 x 1O-4
60 1 . 6 6 6 x 10-5
70 5.018 x 1O-5
8 0 1.99 x 1o-4
1 4 5 . 5 6 2.30 x 1O-4
155>56 7.60 x 1O-4
1 6 5 . 5 6 1.49 x 10-3
1 7 5 . 5 6 4.40 x 10-3
60 1.80 x 1O-5
70 7 . 6 x 1O-5
80 2 . 2 2 x 10-4
60 1.97 x 10-5
70 6 . 5 5 x 1O-5
80 2 . 3 0 x 1O-4
60 1.90 x 10-5
70 7 . 7 2 x 1O-5
8 0 2 . 3 6 5 x 1O-4
1 7 0 . 0 2 . 3 7 x 1O-4
1 8 0 . 0 5 . 2 9 x 1O-4
1 9 0 . 0 1.00 x 10-3
1 4 5 . 0 1.72 x 1O-4
1 5 5 . 0 4 . 9 3 x 10-4
1 6 5 . 0 1.12 x 10-3
1 7 5 . 0 2 . 3 4 x 1O-3
5 3 1.93 x 10-5
1 1 5 . 2
1 2 9 . 9
134.1
1 2 9 . 9
1 4 6 . 6
121.5
1 2 1 . 5
121.5
1 5 6 . 7
1 1 9 . 0
135.1
1 3 1 . 8
1 2 7 . 2
h 278
278
278
292
292
292
292
292
292
292
292
292
h 297
297
297
297
292
292
292
292
292
292
292
292
292
h 297
297
297
h 297
297
297
297
a 339
TABLE 2. contd
Miscellaneous Azo- Deri vat i ves II/W
Number of
C atoms Initiator Solvent
T 03 kd (S-l) E. Wmol) Notes Refs.
16 (conrd) 1,l -Azo-bis-l-chloro-l-
(4-chlorophenyl)ethane
2,2-Azo-bis-(2-cyclopent-l-
e n y l p r o p a n e )
To l u e n e
n-Decane
1,l -Azo-bis-l,l-dicyclo- Diphenyl ether/
p r o p y l e t h a n e isoquinoline (90/ 10)
2,2-Azo-bis-(2-methyl-N-[l,l-
(bis-hydroxymethyl)-2-hydroxyethyl]
propionamide)
2,2-Azo-bis-[2-methyl-N-[l,l-
(bis-hydroxymethyl)ethyll
pr opi ona mi de )
2,2-Azo-bis[2-(4,
4-dimethylimidazoline-2-yl)
ewme
2,2-Azo-bis[2-(4,4-dimethyl-
imidazoline-2-yl)propane 2HCl
2,2-Azo-bis[2-(4,5dimethyl-
imidazoline-2-yl)propane 2HCl
2,2-Azo-bis[2-(4,5,6,7-tetrahydro-
lH-1,3-diazepine-2-yl)propane
2HCl
2,2-Azo-bis-(2,2,4-trimetbyl-
pe nt a ne )
1,l -Azo-bis-1-phenylethane
1,l -Azo-bis-1-phenylethane
(l,l-dd
(l,l,l,l,l,l-de)
rert-Butyl-(2,2,4,6,6-penta-
methyl-4-heptyl)-diazine
1,l -Di-(3-chlorophenyl)-l,l-
a z o - e t h a n e
1,l -Di-(4-chlorophenyl)-l,l-
a z o - e t h a n e
u,cr-Diethylbenzyl-azo-3-pentane
l,l-Di-(3-fluorophenyl)-
1,l -azo-ethane
1.1 -Di-(4-fluorophenyl)-
1,l -azo-ethane
Di-(3-hydroxybutyl)-2,2-azo-bis-
i s o b u t y r a t e
59 1.97 x 1o-4
69 6.93 x 1O-4
39.21 9.98 x 1O-5
49.52 4.593 x 10-4
58.95 1.528 x 1O-3
1 2 0 6.33 x lo-*
1 3 0 2.03 x 1O-4
1 4 0 6.07 x 1O-4
1 5 0 1.695 x 1O-3
8 0 1.9 x 10-5
118.8
116.9
a
a
h
149.0 h
Wat er a
239
239
278
278
278
171
171
171
171
342
Water 8 2 1.9 x 10-5 a 342
Me t ha nol 50 9.3 x 10-6 356
Me t ha nol
Water
50
50
9.55 x 10-5
9.30 x 10-5
356
356
Me t ha nol 50 9.21 x 1O-5 356
Water 50 8.94 x lo- 356
Me t ha nol 5 0 1.23 x 1O-5 356
Water 50 1.04 x 10-5 356
Diphenyl ether
Do d e c a n e
Et h y l b e n z e n e
To l u e n e
Et h y l b e n z e n e
1 1 0 1.9 x 10-5 a 339
97.3
100.4
110.3
105.02
105.28
105.28
105.02
97.3
97.3
97.3
97.3
140.0
150.1
164.8
9 5
105
8 5
9 5
105
120.05
130.0
139.0
147.0
105
3.175 x 10-5
(5.45 f 0.05) x 1o-5
(1.6950.01) x 1O-4
8.473 x 10 -
9.02 x 1O-5
7.62 x 1O-5
7.623 x 1O-5
4.135 x 10-5
3.688 x lo-s
3.995 x 10-5
3.294 x 10 -5
1.93 x 1o-4
5.29 x 1O-4
2.18 x 1O-3
4.13 x 10-5
1.218 x 1O-4
1.45 x 10-5
4.82 x 1O-5
1.650 x 1O-4
7.8 x 1O-5
2.63 x 1O-4
7.38 x 1O-4
1.906 x 1O-3
1.121 x 10-4
5.5 x 10-6
2.35 x 1O-5
7.85 x 1O-5
2.22 x 10-5
7.84 x 1O-5
2.413 x 1O-4
1.83 x 1O-5
7.69 x 1O-5
2.424 x 10 -4
136.4
N-Methyl-N-benzyl aniline
N-Methyl propionamide
Diphenylmethane
Pr opyl e ne c a r bona t e
Diphenyl ether 141.6 h
p-Cymene
p-Cymene
122.3 h
h
Diphenyl ether
p-Cymene
p-Cymene
2 6
107,98
107,98
1 5 2
1 8 3
1 8 3
1 5 2
2 6
2 6
2 6
2 6
314
314
314
266,313
266,3 13
266.313
266,313
266,313
310
310
310
310
266,313
Dioxane
D M F
8 5
9 5
105
60
70
8 0
6 0
70
8 0
147.0 h
117.3
121.5
266,3 13
266,313
266,313
292
292
292
292
292
292
Notes page II - 69; References page II - 70
II/16 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 2. contd
Number of
C atoms Initiator Sol vent T (3 kd (s-l) E, Wmol) Notes Refs.
16 (contd) Di-(3-hydroxybutyl)-2,2-azo-bis-
isobutyrate
Di-(4-hydroxybutyl)-azo-bis-
isobutyrate
1 ,l -Bis-(4-methoxyphenyl)-
azo-methane
Diphenyl ether
2,2,4,4,4,4-Hexamethyl-
2,2-azo-pentane
Diphenyl ether
1 -Methylcyclohexyl-azo-a-cumene rerr-Butylbenzene
1 ,l -Diphenyl- 1,l -azo-ethane
2-(Phenylazo)-2-propyl perbenzoate
(I-Phenylethyl)-azo-diphenylmethane
1,l -Bis(p-tolyl)-azo-methane
1 7 3,7-Diphenyl-1,2-diaza-l-cyclo-
heptene
1 8 1,l -Azo-bis-cumene
Toluene
Dioxane
DMF
p-Cymene
Chlorobenzene
Chloroform-d
Chlorotoluene
Ethylbenzene
Diphenyl ether
Benzene
rerr-Butylbenzene
Chlorobenzene
Cumene
Dodecane
n-Octane
Toluene
6 0 2.43 x 10 -
IO 8.18 x 10-5
8 0 2.461 x 1O-4
6 0 2.12 x lo-s
7 0 6.57 x 1O-5
8 0 2.539 x 10 -4
6 0 1. 97 x 1om5
7 0 6.19 x 1O-5
8 0 2.50 x 1O-4
6 0 2.59 x 1O-5
7 0 6.66 x 10-5
8 0 2.628 x 1O-4
145.0 2.23 x 1O-4
155.0 5.67 x 1O-4
165.0 1. 61 x 1O-3
175.0 3.79 x 1o-3
130. 2 1. 82 x 1O-4
140.0 4. 51 x 10-4
150.0 1. 28 x 1O-3
102.2 2.58 x 1O-4
113. 1 9. 81 x 10-4
122.0 2.20 x 10-3
9 5 2.74 x lo-
1 0 5 8. 21 x lo-
1 0 4.5 x 10-4
3 5 1 . 9 x 10-3
1 0 5 . 1 x 10-4
1 0 6.4 x 1O-4
5 8 1 . 9 x 10-5
145.0 2.00 x 10-4
155.0 4.69 x 1O-4
165.0 1. 22 x 10-3
175.0 3.45 x 10-3
61.0 3.80 x 10-5
70.0 1. 34 x 1o-4
80.0 4.21 x 1O-4
89.3 1. 59 x 10-3
100.2 4.04 x 10-3
8 0 4.26 x 1O-4
100.2 3.94 x 1o-3
58.91 1. 94 x 1o-4
6 0 1. 03 x 1o-4
6 0 4.03 x 10-5
6 0 4.44 x 10-6
5 5 8.50 x 1O-5
5 5 6.88 x 1O-5
5 5 4.42 x 1O-5
5 5 8.10 x 10-5
5 5 6.75 x 1O-5
5 5 3.83 x 10 -5
6 0 1. 16 x 1O-4
6 0 4.73 x 1o-5
6 0 7.23 x 1O-6
60.23 1. 47 x 1o-4
6 0 1.14 x 10-4
6 0 4.44 x 10-5
6 0 8.32 x lO-j
40.04 9.46 x 1O-6
49.52 4.33 x 10-5
59.42 1. 62 x 1O-4
69.23 5.80 x 10-4
41.0 9.6 x 1O-6
44.8 1. 98 x 10-5
58.5 1.280 x 1O-4
117. 3
125.7
125.7
121. 5
145.0 h
132.8 h
131. 1 h
124.0 h
a
145.4 h
a
a
vs
z (1256)
z (3890)
z (1013)
z (4154)
z (1013)
z (4154)
z (1256)
z (3890)
z (1256)
z (3890)
h
122.8
292
292
292
292
292
292
292
292
292
292
292
292
291
297
297
297
297
297
297
327
327
327
266,313
266,313
372
3 7 2
372
3 7 2
339
291
297
297
297
1 3 8
1 3 8
1 3 8
1 3 8
1 3 8
4 4
4 4
217
3 3 3
3 3 3
333
280
280
280
280
280
280
3 3 3
3 3 3
3 3 3
217
3 3 3
3 3 3
3 3 3
217
217
217
217
309
309
309
TABLE 2. contd
Miscellaneous Azo- Deri vat i ves II/17
Number of
C atoms Initiator Solvent
T (0 kd (S-l) E. Wmol) Notes Refs.
18 (contd) 1,l -Azo-bis-4-bromocumene Toluene
1.1 -Azo-bis-3-chlorocumene Toluene
1,l -Azo-bis-4-chlorocumene Toluene
1,l -Azo-bis-l-chloro-l-(Ctolyl)-
ethane
Acetophenone
2,2-Azo-bis[2-(4-ethyl-4-methyl-
imidazoline-2-yl)propane 2HCl
2,2-Azo-bis[2-(4-ethyl-5-methyl-
imidazoline-2-yl)propane 2HCl
2,2-Azo-bis[2-(5,5-dimethyl-3,4,5-tri-
hydropyrimidine-2-yl)propane
2,2-Azo-bis[2-(5,5-dimethyl-3,4,5-tri-
hydropyrimidine-2-yl)propane 2HCl
1,l -Azo-bis-4-fluorocumene
1 ,l -Di-3-ttifluoromethyl-
phenyl)- 1 ,l -azo-ethane
1 ,l -Azo-bis-(2-methoxyphenyl).
ethane
1 ,l -Azo-bis-(2-methoxyphenyl)-
ethane
1,1 -Azo-bis-(3-methoxyphenyl)-
ethane
1 ,l -Azo-bis-(4-methoxyphenyl)-
ethane
1,l -Azo-bis- 1-(6methoxyphenyl)-
ethane
1,l -Azo-bis- 1 -phenylpropane
2,2-Azo-bis-2-phenyl-hexafluoro-
propane
1,l -Dimethyl-azo-cyclooctane
1.1 -Diphenyl-azo-cyclopropane
Paraffin
Toluene
Methanol
Water
Methanol
Water
Methanol
Methanol
Water
Toluene
p-Cymene
p-Cymene
Ethylbenzene
p-Cymene
p-Cymene
Ethylbenzene
Toluene
Benzene
Benzene
Ethylbenzene
4 2 . 8
48.6
5 8 . 0
3 6 . 0
4 2 . 8
48.2
61.1
36.0
4 2 . 8
4 8 . 2
7 4 . 8
7 9 . 5
8 6
1 0 5
109.5
1 2 6
135.5
5 9
6 9
59
6 9
50
50
50
50
50
5 0
50
3 6 . 0
4 2 . 8
48.2
61.1
9 5
105
8 4 . 6
9 5
1 0 5
1 0 6 . 0 6
113.81
1 3 3 . 6 6
9 5
105
9 5
105
1 0 0 . 4
110.3 (2.48 f 0.02) x 1O-4
1 0 0 . 4 (2.35 fO.l) x 1O-5
110.3 (7.2f0.2) x 1O-5
45.0 8 . 3 6 x lo+
5 0 . 0 2 . 1 6 x 1O-5
5 5 . 0 4.92 x 1O-5
6 0 . 0 8.81 x 10-5
6 7 . 0 2 . 4 6 x 1O-4
4 3 . 8 6 . 3 x 1O-5
5 3 . 8 2 . 4 x 1O-4
1 3 0 . 0 1.09 x 10-4
1 4 0 . 0 3 . 0 5 x 10-4
1 5 0 . 0 8 . 9 6 x 1O-4
1 6 5 . 0 9 . 6 x lo-
1 7 5 . 0 2.21 x 10-4
1 8 5 . 0 5 . 0 9 x 1o-4
1 7 0 . 0 1.67 x 1O-4
1 8 0 . 0 3 . 4 8 x 1O-4
2 . 7 2 x 1O-5
6 . 2 8 x 1O-5
2.189 x 1O-4
8 . 8 x 10-6
2 . 4 6 x 1O-5
5 . 5 5 x 10-5
2.796 x 10 -4
1.11 x 10-5
2 . 9 0 x 1O-5
6 . 5 2 x lo-
2.1 x 10-3
3 . 0 x 10-3
7 . 4 x 10-3
1.66 x 10-3
2 . 5 x lo-
6 . 4 x lo-
1.7 x lo-
1.03 x 10-4
4 . 0 x 10-4
1.03 x 1o-4
3 . 9 3 x 10-4
6.80 x 10-5
7 . 3 8 x 1O-5
9 . 4 8 x 1O-5
1.1 x 10-4
9 x 10-7
8 . 0 x 1O-6
7 . 9 x 10-6
5 . 7 x 10-6
1.31 x 10-5
2.94 x lo-
1 . 8 8 0 x 10-4
4 . 1 3 x 10-5
1.357 x 10-4
1.69 x 1O-5
6.11 x 1O-5
1.975 x 10-4
2 . 2 9 x 1O-5
5 . 5 2 x 1O-5
4 . 8 7 x 1O-4
1.53 x 10-5
6.91 x 1O-5
3.56 x 1O-5
1 . 0 9 0 x 1o-4
(7.15 *o.l) x 10-5
117.7
1 1 5 . 9
1 1 2 . 5
1 2 6 . 8 a
1 1 5 . 9
1 3 4 . 9 h
1 3 5 . 6 h
1 7 1 . 8
1 2 6 . 5 h
1 4 9 . 8
135.1
1 3 7 . 2 h
115.5
145.8 h
135.3 h
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
266,3 13
266,313
300
300
300
266,313
266,313
266,313
266,313
9 8
9 8
9 8
9 8
1 7 3
173
173
173
173
4 2
4 2
3 2 7
3 2 7
3 2 7
3 2 3
3 2 3
3 2 3
3 2 3
3 2 3
Notes page II - 69; References page II - 70
II/l8 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 2. cont d
Number of
C atoms Initiator Sol vent
T ((3 ka (S-l) E. Wmol) Notes Refs.
18 (contd) 3,8-Diphenyl-1,2-diaza-l-
cyclooctene
I,1 -Di-(3-tolyl)-1,l -azo-ethane p-Cymene
1.1 -Di-(Ctolyl)-1,l -azo-ethane pCymene
19 Phenyl-azo-diphenylmethane
2-(2-Phenyl-4-methylpentyl)-
azo-2-(4-methylpentane)
Decalin
Diphenyl ether
20 1,l -Azo-bis-l-acetoxy-
I-phenylethane
Paraffin
1,l -Azo-bis- 1, I-dicyclopropyl- Diphenyl ether/
butane isoquinoline (90/ 10)
9-Azo-bis-decalin (cis) Ethylbenzene
(rruns)
~,a-Azo-bis(a-methylbenzyl) diacetate Dichlorobenzene
Azo-bis-4-methylcumene Cumene
2,2-Azo-bis[2-(4-ethyl-5-isopropyl- Methanol
imidazoline-2-yl)propane 2HCl Water
2,2-Azo-bis-2-(4-tolyl)-propane Toluene
l,l-Azo-bis-l,l,l-tricyclopropyl- Diphenyl ether/
methane isoquinoline (90/ 10)
1 ,l -Di-(4-ethylphenyl)-
1, 1-azo-ethane
1,l -Diphenyl-azo-butane
1,l -Diphenyl-azo-cyclobutane Ethylbenzene
Tetralin
Toluene
Decalin/
isoquinoline (90/10)
Isoquinoline
Cumenel
isoquinoline (90/ 10)
pCymene
Ethylbenzene
1 4 3 9 . 5 2 x 1O-5
151 2 . 0 9 x 1O-4
1 6 5 8 . 7 7 x 1O-4
1 7 3 1.82 x 1O-3
1 0 5 8 . 1 7 x 1O-5
9 5 3 . 0 6 x lo-*
1 0 5 9 . 3 5 x 1o-5
124.5 3 . 4 4 x 10-5
144.5 2 . 6 9 x 1O-4
1 0 3 . 0 1.17 x 1o-4
1 1 0 . 0 2 . 5 2 x 1O-4
1 2 0 . 0 8.51 x 1O-4
1 3 0 . 0 2 . 6 1 1 x 1O-3
131 3 . 2 x lo-*
1 4 2 4 . 3 x 10-2
149.5 8 . 0 x IO-*
1 2 0 . 0 4.26 x 1O-5
1 2 5 . 0 7 . 9 4 x lo-s
1 3 0 . 0 1.49 x 10-4
1 3 5 . 0 2.697 x 1O-4
1 4 0 . 0 4.774 x 10 -4
1 4 7 . 0 1.055 x 10-3
1 8 0 . 0 1.41 x 10-4
1 9 0 . 0 3 . 9 5 x 10-4
200.0 1.05 x 10-3
1 8 0 . 0 1.90 x 1o-4
1 9 0 . 0 5 . 3 5 x 10-4
200.0 1.41 x 10-3
6 5 1.86 x 10-5
70 4.00 x 10-5
80 1 . 5 9 2 x 1O-4
90 5 . 5 2 5 x 1O-4
5 5 8 . 8 6 x lo-s
5 5 7 . 5 4 x 10-5
5 5 4 . 4 7 x lo-s
41.0 1.33 x lo-s
4 9 . 5 5 . 0 2 x 1O-5
5 8 . 5 1 . 6 9 0 x 1O-4
50 7 . 7 2 x 1O-5
50 1.01 x 1o-4
3 6 . 0 8 . 4 x 1O-6
4 2 . 8 1.62 x 1O-5
61.1 2 . 0 8 x 1O-4
1 0 5 . 0 7.89 x lo-s
1 1 0 . 0 1 . 3 7 4 x 1o-4
1 1 5 . 0 2.36 x 1O-4
1 2 0 . 0 4 . 5 8 x 1O-4
1 2 5 . 0 7.76 x 10-4
1 3 0 . 0 1.38 x 1O-3
1 3 5 . 0 2 . 3 9 x 1O-3
118.5
118.5
118.5
9 5
105
93.88
1 0 5 . 6 8
1 1 9 . 5 5
6 3 . 2
7 3 . 8
79.1
8 7 . 7
3 . 6 0 x 1O-4
3 . 3 0 x 10-4
445 x 10-4
3 . 0 2 x 1O-5
9.14 x 10-5
1.67 x 1O-5
6 . 9 6 x 1O-5
3 . 3 9 x 10-4
8 . 2 x 1O-6
3 . 5 x 10-5
6 . 9 x 1O-5
1.69 x 1O-4
1 5 3 . 6
126.5
1 4 2 . 3
1 5 9 . 0
175.1
175.1
1 2 0 . 7
1 1 0 . 0
1 4 3 . 5
125.3
122.3
1 3 7
1 3 7
1 3 7
1 3 7
266,313
h 266,313
266,313
46
46
310
310
310
310
240
240
240
h 171
171
171
171
171
171
h 3 3 5
335
3 3 5
h 335
3 3 5
3 3 5
366
366
366
366
280,333
z (1013) 280,333
z (4154) 280,333
309
309
309
356
356
200
200
200
h 171
171
171
171
171
171
171
171
171
h 171
266,313
a 266,313
a 300
;: 3 0 0 3 0 0
3 2 3
3 2 3
3 2 3
b,h 3 2 3
TABLE 2. contd
Miscellaneous Azo-Derivatives II/19
Number of
C atoms Initiator Solvent T (C) ka (S-l) E. Wmol) Notes Refs.
20 (mlfd)
2 2
(-)-(s)-l,l-Diphenyl-l-
methyl-azo-methane
2,2-Azo-bis(2-methyl-fV-phenyl-
propionamidine) 2HCl
2,2-Azo-bis[N-(4-chlorophenyl)-
2-methylpropionamidine] 2HCl
2,2-Azo-bis[N-(4-hydroxyphenyl)-
2-methylpropionamidine] 2HCl
1,l -Azo-bis-1-phenyl-3-
methylbutane
1,l -Azo-bis-4-ethylcumene
1,l -Azo-bis-4-isopropylcumene Toluene
1,l -Diisopropyl- l,l-
diphenyl-azo-ethane
1,l -Diphenyl-azo-
cyclopentane
2 4
2,2-Azo-bis[2-methyl-fV-(phenyl-
methyl)propionamidine] 2HCl
2,2-Azo-bis[2-(4-methyl-4-isobutyl-
imidazoline-2-yl)propane 2HCl
2,2-Azo-bis[2-(4-methyl-Sisobutyl-
imidazoline-2-yl)propane 2HCl
2,2-Azo-bis[2-(4-ethyl-S-propyl-
imidazoline-2-yl)propane 2HCl
1,l -Azo-bis-4-rerr-butylcumene
~,a-Azo-bis(a-methylbenzyl)-
dimethacrylate
Bis(2,2,4,6,6-pentamethyl-
4-heptyl)diazine
1,l -Diphenyl-azo-cyclohexane Benzene
2 5 3-Bromophenyl-azo-triphenyl-
methane
4-Bromophenyl-azo-triphenyl-
methane
4-Hydroxyphenyl-azo-triphenyl-
methane
2-Nitrophenyl-azo-9-phenylfluorene Toluene
4-Nitrophenyl-azo-9-phenylfluorene
2,4-Dinitrophenyl-azo-9-phenyl-
fluorene
2-Nitrophenyl-azo-triphenylmethane
3-Nitrophenyl-azo-triphenylmethane
Cumene
Water
Water
Water
Ethylbenzene
Toluene
Ethylbenzene
Benzene
Water
Methanol
Water
Methanol
Water
Methanol
Water
Toluene
Dichlorobenzene
Diphenyl ether
Toluene
Toluene
Acetic acid
Pyridine
Toluene
Toluene
Toluene
Toluene
Toluene
Benzene
ferr-Butylbenzene
1 0 6 . 0 8 . 2 6 x 1O-6
1 2 7 . 9 1.18 x 1O-4
4 5 1.93 x lo-s
4 5 . 5 1.93 x 10-5
4 7 . 5 1.93 x 1o-5
1 0 0 . 4 7 . 6 x 1O-5
110.3 2 . 4 2 x 1O-4
4 2 . 8 1.29 x IO-
4 8 . 6 3 . 2 9 x 1O-5
58.0 1 . 2 4 0 x 10-4
42.8 1.13 x lo-s
5 1 . 2 4.26 x 1O-5
5 8 . 0 1 . 0 7 8 x 1O-4
50 3 . 5 2 x 1O-5
2 9 . 5 3 . 1 6 x 1O-4
40.0 1.24 x 1O-3
5 0 . 0 4.68 x 1O-3
5 2 1.93 x 10-5
50 5 . 5 4 x 10-5
50 7 . 0 8 x 1O-5
50 7.72 x lo-
50 9 . 7 8 x lo-
50 1.06 x 1O-4
50 1.41 x 10-4
4 2 . 8 1.16 x 1O-5
48.6 2 . 5 8 x 1O-5
5 8 . 0 1 . 0 8 0 x 10 -4
6 5 3 . 6 5 x 1O-5
70 7 . 9 8 x 10 -5
80 2.313 x 1O-4
90 1 . 3 4 4 x 10-3
100.1 3 . 0 3 x 10 -4
1 0 9 . 2 7.62 x 10 -4
1 2 5 . 0 3 . 9 0 x 10-3
4 5 . 5 2 . 5 2 x 1O-5
54.0 8 . 7 4 x 1O-5
6 9 . 7 7 . 1 2 x 1O-4
5 3 . 8 1 . 1 4 x 10-4
64.0 4 . 5 8 x 1O-4
53.35 1.05 x 10-4
64.30 4 . 2 8 x 1O-4
54.00 1.42 x 1O-4
64.00 6 . 2 x 1O-4
54.00 1.52 x 1O-4
64.00 6 . 7 x 1O-4
54.00 1 . 7 0 x 1o-4
64.00 6 . 4 x lO-4
45.45 1.01 x 10-4
55.55 3.71 x 10-4
45.45 2.06 x 1O-4
55.55 7 . 5 3 x 10-4
55.55 2 . 0 6 x 1O-4
64.94 6 . 9 2 x 1O-4
64.94 1 . 4 6 x 1O-4
75.06 5 . 2 6 x 1O-4
5 3 . 8 5 . 8 x 1O-5
64.0 1.99 x 10-4
60 9 . 9 2 x 1O-5
60 9 . 1 8 x 1O-5
1 4 9 . 2
1 0 8 . 9
1 2 4 . 4
1 1 3 . 6
1 2 3 . 6
1 2 5 . 7
1 2 5 . 7
125.1
1 1 7 . 2
1 3 3 . 9
1 3 3 . 9
121.3
119.7
111.7
1 1 9 . 2
123.8
1 1 0 . 9
318
318
339
339
339
9 8
9 8
309
309
309
309
309
309
324
323
3 2 3
3 2 3
339
356
356
356
356
356
356
309
309
309
366
366
366
366
314
314
314
323
3 2 3
3 2 3
42
42
5 2
52
5 2
5 2
5 2
5 2
52
5 2
7 5
7 5
7 5
7 5
7 5
7 5
7 5
7 5
4 2
4 2
2 6 3
2 6 3
Notes page II - 69; References page II - 70
II/20 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 2. contd
Number of
C atoms Initiator Sol vent
T (Cl kd (S-l) E, Wmol) Notes Refs.
2 5 (co&d) 3-Nitrophenyl-azo-triphenylmethane Cumene
Ethylbenzene
Octane
Toluene
4-Nitrophenyl-azo-triphenylmethane Benzene
reti-Butylbenzene
Chlorobenzene
Cumene
1 -Decene
Dodecane
1-Eicosene
Heptane
Hexadecane
LHexadecene
Hexane
1-Hexene
Nonane
Octadecane
1-Octadecene
Octane
1-Octene
Pentane
Tetradecane
4-Nitrophenyl-azo-triphenylmethane 1-Tetradecene
Toluene
2,4-Dinitrophenyl-azo-triphenyl-
methane
Phenyl-azo-triphenylmethane
Toluene
Acetic acid
Anisole
6 0 1.04 x 1o-4
6 0 1. 10 x 10-4
6 0 1. 01 x 10-4
4 5 1. 25 x 1O-5
6 0 1. 22 x 10-4
6 0 1. 09 x 10-4
6 0 9.7 x 10-5
6 0 4.03 x 10-5
6 0 4.44 x 10-6
5 5 8.50 x lO-5
5 5 6.88 x 10-5
5 5 4.42 x 1O-5
5 5 8.10 x 10-5
5 5 6.75 x 1O-5
5 5 2.62 x 1O-5
6 0 1. 15 x 10-4
6 0 4.73 x 10-5
6 0 7.23 x 1O-6
5 0 2.017 x 10 -5
6 0 9.988 x 1O-4
7 0 3.350 x 10-4
77.5 1. 16 x 1O-3
6 0 1. 038 x 1o-4
5 0 1. 933 x 10-5
6 0 9.166 x 1O-5
7 0 3.250 x 1O-4
6 0 7.60 x 1O-5
5 0 2.716 x 1O-5
6 0 1. 043 x 10-4
7 0 3.900 x 10-4
5 0 1.716 x 1O-5
6 0 8.133 x 1O-5
7 0 2.966 x 10 -4
77.5 1. 09 x 10-3
6 0 8.25 x 10 -5
50 2.750 x 1O-5
6 0 1.195 x 1o-4
6 0 1.143 x 1o-4
5 0 2.200 x 1o-5
6 0 9.900 x 10-5
7 0 3.710 x 1o-4
6 0 7.780 x 10-5
7 0 2.783 x 1O-4
6 0 7.58 x 1O-5
6 0 1. 015 x 10-4
7 0 3.650 x 10 -4
77.5 1. 78 x 10-3
6 0 1.123 x 1O-4
5 0 3.600 x 1O-5
6 0 1.280 x 10 -4
5 0 1.866 x 10-5
6 0 8.800 x 10 -5
7 0 3.116 x 1O-4
6 0 9.02 x lo-
64.94 2.58 x 1O-4
75.06 9.19 x 1o-4
53.35 5.7 x 1o-5
64.30 2.25 x 1O-4
75.06 1. 90 x 1o-4
84.98 6.13 x 1O-4
43.30 5.7 x 10-5
64.00 8.4 x 10-4
25.0 2.58 x 1O-6
123.0
113.0
122.6
117.2
120. 5
z (1256)
z (3890)
z (1013)
z (4154)
z (1013)
z (6180)
z (1256)
z (3890)
b,h
263
2 6 3
2 6 3
2 6 3
263
2 6 3
263
2 6 3
263
333
333
3 3 3
3 3 3
3 3 3
333
263
263
263
168,263
168,263
1 6 8
1 6 8
1 6 8
168,263
168,263
1 6 8
1 6 8
1 6 8
168,263
1 6 8
168,263
168,263
1 6 8
1 6 8
1 6 8
168,263
168,263
1 6 8
168,263
168,263
1 6 8
168,263
1 6 8
1 6 8
168,263
1 6 8
1 6 8
1 6 8
168,263
168,263
168,263
168,263
1 6 8
1 6 8
7 5
7 5
5 2
5 2
7 5
7 5
5 2
5 2
1 0 3
TABLE 2. contd
Miscellaneous Azo- Deri vat i ves II/21
Number of
C atoms Initiator Sol vent
T (Cl ka (S-l) E, Wmol) Notes Refs.
25 (conrd) Phenyl-azo-triphenylmethane Anisole 50.2
74.7
25.0
74.5
8 0 . 1
85.9
Benzene 25.0
49.6
74.7
5 0
Benzonitrile 25.0
50.3
74.7
rut-Butylbenzene 5 0
5 0
5 0
Chlorobenzene 25.0
49.6
74.7
5 0
5 0
5 0
Cyclohexane 25.0
49.6
74.7
Decane 6 0
Dodecane 6 0
Diethyl malonate 2 5 . 1
74.5
8 0 . 1
85.9
Ethylbenzene 5 0
Heptane 6 0
Hexadecane 6 0
Hexane 6 0
Nitrobenzene 25.0
74.5
8 0 . 1
85.9
Octane 5 0
5 0
5 0
6 0
Pyridine 53.35
64.00
Tetradecane 6 0
Toluene 43.8
53.8
4 5
5 0
45.45
55.55
43.30
53.35
53.3
2 6 2,2-Azo-bis[2-(4-ethyl-5-propyl- Methanol 5 0
imidazoline-2-yl)propane 2HCl Water 5 0
Azo-bis-diphenylmethane Toluene 54.0
64.0
1,l -Bis-biphenyl-azo-methane Diphenyl ether 135.0
145.0
155.0
165.0
1,l -Azo-bis-1-(4-tolyl)-cyclohexae Toluene 36.0
1. 31 X 10-4
3.03 x 10-3
3.0 x 10-6
2.9 x 1O-3
6.8 x 10-3
1 . 1 x 10-2
4.29 x 1O-6
1. 24 x 1O-4
3.12 x 1O-3
1. 37 x 10-4
2.62 x 1O-6
1. 56 x 1O-4
3.14 x 10-3
1. 33 X 10-4
3.83 x 1O-5
9.53 x 10-6
3.77 x 10-6
1. 67 x 1O-4
3.93 x 10-3
1.50 x 10-4
6.82 x 1O-5
7.65 x 1O-6
4.22 x 1O-6
9.90 x 10-5
1. 75 x 1o-3
5.72 x 10m4
5.35 x 1o-4
3 . 1 x 10-6
2.8 x 1O-3
5.9 x 10-3
1 . 0 x 10-2
1. 58 x 1O-4
6.60 x 1o-4
4.76 x 1O-4
7.60 x 1O-4
2.6 x 1O-6
3.0 x 10-3
5.8 x 1O-3
9.8 x 1O-3
1. 59 x 10-4
7.53 x 10-5
1. 17 x 10-5
6. 41 x 1O-4
1. 74 x 10-4
8.0 x 1O-4
4.99 x 10-4
6.3 x 1O-5
2.4 x 1O-4
9.23 x lo-
1. 73 x 10-4
8.48 x 1O-5
3. 51 x 10-4
6.0 x 1O-5
2.25 x 1O-4
2.25 x 1O-4
9.75 x 10-5
1. 33 x 10-4
1. 01 x 10-4
3.40 x 1o-4
1. 23 x 1O-4
3.58 x 1O-4
7.76 x 1O-4
2.09 x 1O-3
8.7 x 1O-6
118.3
121. 3
118.4
102. 5
118.7
129. 7
122.6
z (1140)
z (4265)
bh
b
b
z (1140)
z (4265)
h
b
b
b 1 0 3
b 1 0 3
1 1 4
1 1 4
1 1 4
1 1 4
b,h 1 0 3
1 0 3
b 1 0 3
2 6 3
b,h 1 0 3
b 1 0 3
1 0 3
2 6 3
2 6 3
263
1 0 3
1 0 3
1 0 3
2 6 3
2 6 3
2 6 3
1 0 3
1 0 3
1 0 3
263
263
1 1 4
1 1 4
1 1 4
1 1 4
263
2 6 3
2 6 3
2 6 3
1 1 4
1 1 4
1 1 4
1 1 4
2 6 3
2 6 3
2 6 3
2 6 3
5 2
5 2
2 6 3
4 2
4 2
2 6 3
2 6 3
15
15
5 2
5 2
4 6
356
356
107,312
46,107,312
h 297
297
2 9 7
2 9 7
200
z (1140)
z (4265)
Notes page II - 69; References page II - 70
II/22 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 2. contd
Number of
C atoms Initiator Sol vent
T (0 kd (s-l) E, Wmol) Notes Refs.
26 (conrd) 1,l -Azo-bis-1-(4-tolyl)-cyclohexanne
I.1 -Diisopropyl-2,2-dimethyl-
1.1 -Diphenyl-azo-propane
4-Methoxyphenyl-azo-triphenyl-
methane
1.1 -Diphenyl-azo-cycloheptane
3-Tolyl-azo-triphenylmethane
4-Tolyl-azo-triphenylmethane
2 7
2 8
4-Acetaminophenyl-azo-triphenyl-
methane
1,l -Azo-bis-1,2-diphenyl-
ethane (meso)
(QL)
3 0 1,l -Dibutyl- 1, I -diphenyl-
azo-pentane
3 4
40
1, I -Azo-bis-( 1,3-diphenyl-
pentane)
3,10,13,20-Tetraphenyl-1,2,11,12-tetra-
aza-1,l 1-cycloeicosadiene
44 3,12,15,24-Tetraphenyl-1,2,13,14-tetra- Ethylbenzene
aza-1,13-cyclotetracosadiene Xylene
Poly[oxyethylenexoxy-
(1-oxo-2,2-dimethylethylene)
azo-(2-oxo- 1,l -dimethyl-
ethylene)
Toluene
Ethylbenzene
Toluene
Benzene
Benzene
terz-Butylbenzene
Cumene
Ethylbenzene
Octane
Toluene
Benzene
rerfButylbenzene
Cumene
Ethylbenzene
Octane
Toluene
Toluene
Ethylbenzene
Ethylbenzene
Bromobenzene
Xylene
Xylene
o-Xylene
4 2 . 8 2.01 x 10-5
61.1 2.009 x 10 -4
50.0 6 . 2 4 x 1O-5
60.0 2 . 4 9 x 1O-4
70.0 7 . 7 7 x 10-4
54.00 2 . 1 3 x 1O-4
64.00 7 . 6 x 1O-4
16.2 1.65 x 1O-4
2 4 . 8 5 . 5 2 x 1O-4
3 3 . 4 1.66 x 10-3
41.1 4 . 5 2 x 1O-3
5 0 1 . 3 0 x 10-4
5 0 1 . 3 0 x 10-4
50 I.51 x 10-4
50 1.72 x 1O-4
4 5 8 . 9 x lo-s
4 3 . 8 7 . 4 x 10-5
5 3 . 8 2 . 7 7 x 1O-4
4 5 9 . 7 4 x lo-s
50 1.81 x 1o-4
50 1 . 2 6 x 1O-4
5 0 1.35 x 1o-4
50 1 . 4 0 x 10-4
50 1.62 x 1O-4
4 5 8 . 6 x 10-5
43.30 6 . 9 x 1O-5
5 3 . 3 5 2 . 2 5 x 1O-4
4 5 9 . 3 x 10-5
5 0 1.52 x lO-4
54.00 1.46 x 1O-4
64.00 5 . 9 x 10-4
96.56 2 . 7 5 x 1O-5
1 0 6 . 4 7 9 . 0 3 x 10 -5
1 1 5 . 2 8 2 . 4 2 x 1O-4
96.56 3 . 2 2 x 1O-s
1 0 6 . 4 7 1.04 x 1o-4
1 1 5 . 2 8 2 . 8 4 x 1O-4
50.0 5 . 0 5 x 10-5
6 0 . 0 2 . 0 3 x 1O-4
7 0 . 0 6 . 2 4 x 1O-4
8 9 . 7 1.5 x lo-s
1 1 8 . 8 5 . 6 x 1O-4
1 1 0 7 . 2 0 x 1O-5
1 2 0 2 . 3 0 x 1O-4
1 3 0 6 . 9 0 x 1O-4
112.95 8 . 7 6 1 x 1O-5
1 1 0 . 8 8 . 9 x 1O-5
1 1 9 . 8 2 . 2 x 1o-4
1 1 0 7 . 6 3 x 1O-5
1 2 0 2 . 4 6 x 1O-4
1 3 0 7.12 x 1O-4
8 5 2.106 x 1O-4
9 5 7.312 x 1O-4
1 0 5 1.995 x 10-3
r (K) 1.99 x 104
1 1 7 . 2
1 1 3 . 8
1 0 0 . 4
125.5
138.5
1 3 8 . 9
1 0 8 . 9
145.6
1 2 6 . 4
1 4 3 . 9
1 2 4 . 0
exp[ - 124.O/RT]
200
200
324
324
324
52
52
3 2 3
3 2 3
323
3 2 3
2 6 3
2 6 3
2 6 3
263
263
42
42
263
2 6 3
2 6 3
263
263
263 (
263
52
5 2
263
263
52
5 2
ah 1 6 2
a 1 6 2
a 1 6 2
ah 1 6 2
a 1 6 2
a 1 6 2
h 324
324
324
3 1 1
3 1 1
3 8
3 8
3 8
1 5 8
48
48
3 8
3 8
3 8
332
332
332
332
TABLE 3. ALKVL PEROXIDES
Alkyl Peroxides II/23
Number of
C atoms Initiator Solvent
TO3 ka (S-l) E. (kJ/mol) Notes Ref s.
2 Methyl peroxide
4 Ethyl peroxide
Vapor
Methanol
Styrene
Vapor
Vapor (toluene)
5 2,CPentanedione peroxide Triethyl phosphate
6 Propyl peroxide Vapor
7
Isopropyl peroxide Styrene
Ally1 fert-butylperoxide Toluene
Dimethylaminomethyl terr-butyl
peroxide
8 rerf-Butyl peroxide Acetic acid
Acetonitrile
Benzene
Benzhydrol
tea-Butanol
2-Butanol
n-Butyl mercaptan
Tri-n-butylamine
T W 1.6 x 10 l5
T (K)
4.1 x 105
6 0 1.2 x 10-9
140.2 1.75 x 10-4
147.8 3.60 x 1O-4
160.0 1.08 x 1O-3
176. 5 3.78 x 1O-3
184. 5 7.16 x 1O-3
145.9 6.69 x 1O-4
145.9 5.02 x 1O-4
200 3.58 x lo-*
210 6.76 x 1O-2
218 1.47 x lo-
226 2.23 x lo-
234 3.86 x lo-
2 4 5 6.43 x lo-
1 0 0 1.9 x 10-6
1 1 5 6.1 x 1O-6
1 2 5 1.4 x 10-5
146. 5 2.50 x 1O-4
155. 3 6.00 x 1O-4
166.8 1.95 x 10-3
175.4 4.10 x 10-3
6 0 6. x lo-I0
1 3 0 5.76 x 1O-5
1 4 0 1.785 x 1O-4
1 5 0 4.800 x 1O-4
1 6 0 1.270 x 1O-3
1 1 0 5.5 x 10-5
1 2 0 1.9 x 1o-4
1 3 0 4.76 x 1O-4
1 1 5 1.2 x 10-5
1 2 0 2.19 x 1O-5
1 2 5 2.98 x 1O-5
1 3 0 6.29 x 1O-5
9.5 9.53 x lo-
1 2 5 3.89 x 1O-5
1 1 5 1.19 x 10-5
1 2 0 2.21 x 10-5
1 2 5 3.47 x 10-5
1 3 0 5.63 x 1O-5
8 0 7.81 x 1O-8
1 3 0 (2. 48-3. 04) x 10 -5
1 0 0 8.8 x 10-7
1 0 0 8.75 x lo-
1 1 5 5.66 x 1O-6
1 3 0 3.00 x 10-5
1 2 0 1.39 x 10-5
1 2 0 7.6 x 1O-6
1 2 0 7.5 x 10-6
1 2 0 3.7 x 10-6
1 2 0 1.10 x 10-5
1 2 5 1.99 x 10-5
1 3 0 3.22 x 1O-5
1 3 5 6.19 x 1O-5
1 2 5 8.7 x 10-5
1 2 0 1.41 x 10-5
1 2 5 2.49 x 1O-5
1 3 0 4.30 x 10-5
1 3 5 7.32 x 1O-5
1 2 5 4.8 x 1O-5
1 2 5 1.5 x 10-5
1 2 5 (1.7f0.3) x 10-5
1 3 5 (4.2 f 0.4) x 1O-5
exp[- 147.7/RT]
exp[- 153.9/Rfl
147. 3
131.8
t8
132.6
9 2
132.2
154.8
139. 1 h,ms
134. 5
139.7 h
129.7
d
h
142. 3
146.9
m2,u2
m242
a
147. 7
143. 5
a
a
z (0.98)
z (864)
z (1620)
~(3480)
h
h
7 2
225
92 .
1 2 7
1 2 7
1 2 7
1 2 7
1 2 7
1 8 7
1 8 7
8 7
8 7
8 7
8 7
8 7
8 7
337
337
337
1 2 8
1 2 8
1 2 8
1 2 8
9 2
3 2 1
3 2 1
3 2 1
3 2 1
3 0 3
3 0 3
3 0 3
1 9 2
1 9 2
1 9 2
1 9 2
208
208
1 9 2
1 9 2
1 9 2
1 9 2
1 2 9
1 2 9
126,337
1 9 7
126,337
126,337
3 3
3 3
3 3
3 3
1 9 2
1 9 2
1 9 2
1 9 2
1 4 0
1 9 2
1 9 2
1 9 2
1 9 2
1 4 0
1 4 0
6 4
6 4
Notes page II - 69; References page II - 70
II / 24 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 3. contd
Number of
C atoms Initiator Sol vent
T (C) kd (S-l) E, Wmol) Notes Refs.
8 (conrd) rerr-Butyl peroxide Tri-n-butylamine
tert-Butylbenzene
Carbon tetrachloride
Chlorobenzene
Cumene
Cyclohexane
Cyclohexanol
Cyclohexene
Cyclohexylamine
Decane
Dodecane
Dimethylaniline
Ethyl benzoate
N-Ethylcyclohexyl amine
Heptane
Hexadecane
1 4 . 5 (1.60f0.21) x 1O-4
T 09 2.8 x lOI
1 2 5 (1.5 kO.2) x 10-5
1 3 5 (5.0 f 0.3) x 10 -5
1 4 5 (1.51 iO.22) x 10-4
T W
2.8 x 10
1 2 5 2.10 x 10-6
1 2 5 2.49 x 1O-6
1 2 5 2.03 x 1O-6
1 2 0 9 x lo-6
1 2 0 2.4 x 1O-6
1 2 0 2.3 x 1O-6
1 2 0 8.6 x 10-7
1 2 5 1.40 x 10-6
1 5 0 4.45 x 104
1 2 1 1.93 x 10-5
1 4 1 1.93 x 10-4
1 6 4 1.93 x 10-3
T (K) 4.20 x 1015
1 2 5 (1.6kO.l) x 1O-5
1 3 5 (5210.3) x 10-5
1 4 5 (1.5650.13) x 1O-4
T 09 2.8 x 10 I4
9 5 2.48 x lo-
1 2 0 6.3 x 10m6
1 2 5 1.52 x 10m5
1 3 0 2.59 x 10m5
1 3 5 4.64 x 1O-5
1 2 5 2.4 x 1O-5
1 2 0 7.6 x 1O-6
1 2 5 1.38 x 1O-5
1 3 0 2.81 x 1O-5
1 3 5 4.41 x 10-5
1 2 0 8.3 x 1O-6
1 2 0 6.2 x 1O-6
1 2 0 3.77 x 10-6
1 2 0 2.65 x 1O-6
1 2 5 5.50 x 10-5
8 0 1.39 x 10-8
1 1 0 2.01 X 10-6
1 3 0 2.48 x 1O-5
1 1 5 3.00 x 10-6
1 3 0 2.16 x 1O-5
1 4 0 6.66 x 10-5
8 0 1.29 x lo-*
1 1 0 1.87 x 1O-6
1 3 0 2.44 x 1O-5
1 2 0 9.6 x 1O-6
1 2 5 1.89 x 1O-s
1 3 0 3.41 x 10-5
1 3 5 5.84 x 1O-5
1 2 0 1.07 x 10-5
1 2 5 1.92 x 1O-5
1 3 0 3.39 x 10-5
1 3 5 5.90 x 10-5
1 2 5 4.01 x 10-5
8 0 1.44 x 10-8
1 1 0 2.19 x 1O-6
8 0 1.07 x lo-8
1 1 0 1.82 x 1O-6
1 3 0 2.33 x 10m5
8 0 1.64 x 1O-8
1 1 0 2.17 x 1O-6
exp[- 146.4/RTj
exp[- 146.4/RT]
Ul
s
%t6
z (0.98)
z (1930)
z (2890)
z (5525)
Ul>t6
exp[- 153.46/R~]
exp[- 146.4/RT]
170. 7 h
156. 1 h
157. 3
z (0.98)
z (1275)
z (2890)
z (5725)
h
1 6 3 a
a
a
148. 5 h
6 4
1 2 3
6 4
6 4
6 4
1 2 3
3 0 1
3 0 1
3 0 1
3 3
3 3
3 3
3 3
3 0 1
346
344
344
344
344
6 4
6 4
6 4
1 2 3
208
1 9 2
1 9 2
1 9 2
1 9 2
1 4 0
1 9 2
1 9 2
1 9 2
1 9 2
3 3
3 3
3 3
3 3
1 4 3
270
270
270
337
3 3 7
3 3 7
270
270
270
1 9 2
1 9 2
1 9 2
1 9 2
1 9 2
1 9 2
1 9 2
1 9 2
1 4 3
270
270
270
270
270
270
270
TABLE 3. contd
Alkyl Peroxi des II/25
Number of
c at oms Initiator Sol vent
T(C) ka (S-l) E. Wmol) Notes Refs.
8 (contd) [err-Butyl peroxide 2-Methyl-2-butanol
Methyl methacrylate
N-Methylpipendine
Mineral oil
Nonane
Norbomanol
Nujol
Octane
2-Octanol
Piperidine
1 Propanol
Styrene
Tetradecane
Tetrahydrofuran
Triethylamine
Vapor (acetone)
Vapor (carbon
tetrachloride)
Vapor (chloroform)
Vapor (dichloro-
difluoromethane)
Vapor (trichloro
ethylene)
Vapor (methylene
chloride)
Vapor (3-pentanone)
Vapor (silicon
tetrafluoride)
Vapor (toluene)
1 2 0
1 2 5
1 3 0
1 3 5
T 6)
1 2 5
T 09
8 0
1 1 0
1 3 0
1 2 5
1 2 5
8 0
1 1 0
1 2 5
1 2 5
1 2 5
T (K)
8 0
1 1 0
1 3 0
1 2 0
1 2 5
1 3 0
1 3 5
1 2 5
1 0 0
1 2 0
1 2 0
1 2 0
1 2 0
1 2 5
1 2 5
T (K)
1 2 0
1 2 5
1 3 0
1 3 5
127. 5
1 3 1
1 4 6
151. 5
1 6 2
1 6 7
1 4 5
T 6)
1 5 0
1. 26 x 1O-5
2.34 x 1O-5
4.47 x 10-5
6.80 x lo-s
2.8 x lOI
1. 54 x 10-5
1. 31 x 105
1. 36 x lo-*
2. 01 x 10-6
2.54 x 1O-5
4.4 x lo-
7.8 x lo-
1. 48 x lo-*
2.19 x 1O-6
5.5 x 10-5
3.49 x 10-5
2.8 x 1O-5
2.8 x 1014
1. 12 x 10-8
1. 82 x 1O-6
2.38 x 1O-5
9.7 x 10-6
1. 84 x 1O-5
3.39 x 10-5
5.76 x 1O-5
1 . 5 x 10-5
6.82 x lo-
1. 34 x 10-5
9.5 x 10-6
8.0 x 1O-6
5.7 x 10-6
1 . 6 x 1O-5
1. 62 x 1O-5
1.30 x 106 exp[- 158.3/RT]
7.9 x 10-6 169.9
1. 69 x 1O-5
3.15 x 10-5
5.55 x 10-5
7.4 x 10-6
1. 13 x 10-5
6.0 x 1O-5
1. 03 x 10-4
3.6 x 1O-4
5.2 x 1O-4
1 . 3 x 10-4 165. 3
5.9 x 106 exp[- 165.3/RT]
8.58 x 1O-4
1 5 0 1.167 x 1O-3
1 5 0 >(2.00 x 10 -4)
1 5 0
1. 50
1 4 5
T WI
1 6 0
1 6 0
1 6 0
1 4 8
1 5 8
103.2
111.9
2.35 x 1O-3
1.017 x 10-3
1 . 5 x 10-4 165. 3
6.8 x 10 6 exp[- 165.3/RZJ
1. 05 x lo-
1.25 x 1O-3
1.27 x 1O-3
9.0 x 10-5
2.5 x 1O-4
5.6 x lo-
2.03 x 1O-6
149.4 h
exp[- 146.4/RT]
exp[- 154.6/RT]
U
exp[- 146.4/RT]
155.2 h
z (0.98)
z mw
z (2850)
z (5170)
113.0 a,i(2.6)
a,i(33)
a,i( 100)
1 9 2
1 9 2
1 9 2
1 9 2
1 2 3
1 4 3
376
270
270
270
1 4 0
3 0 1
270
270
1 4 0
1 4 3
1 4 0
1 2 3
270
270
270
1 9 2
1 9 2
1 9 2
1 9 2
1 4 0
1 9 7
3 3
3 3
3 3
3 3
1 4 0
1 4 3
376
1 9 2
1 9 2
1 9 2
1 9 2
238
238
238
238
238
238
1 2 5
1 2 5
1 3 0
1 3 0
1 3 0
1 3 0
1 3 0
125
1 2 5
1 1 7
1 1 7
1 1 7
8 8
8 8
227
227
Notes page II - 69; References page II - 70
II/26 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 3. co&c/
Number of
C atoms Initiator Solvent
T(C) kd (S-l) E, GJ/mol) Notes Refs.
8 (contd) tert-Butyl peroxide Vapor 120.2
129. 5
138. 5
145.4
1 2 5
1 3 5
1 4 5
129.6
141.0
152. 5
166.8
1 3 0
1 4 0
1 5 0
1 6 0
1 7 0
1 2 9
1 3 8
1 4 9
1 5 2
139. 7
147. 2
154.6
159. 8
T (K)
1 4 5
T (K)
149. 5
1 6 0
1 6 0
1 6 0
1 3 0
1 4 0
1 5 0
1 6 0
Vapor (He) 280
290
300
310
320
330
340
350
KBr pellets 1 0 9
1 2 7
1 4 9
rert-Butyl Z-chloro-l,l-dimethylethyl- Cumene 1 2 0
peroxide 1 3 0
1 4 0
1 5 0
1 0 0
1 0 0
8 0
8 0
8 0
8 0
8 0
6 0
8 0
1 5 0
1 5 0
1 5 0
1 5 0
set-Butyl peroxide
Butyl peroxide
Bromo-w-r-butyl peroxide
Chloro-tert-butyl peroxide
Bis(chloro-tert-butyl) peroxide
2-rert-Butyl peroxy-2-methyl-
I-propanol
Toluene
Vapor
Decane
Dodecane
Heptane
Hexadecane
Octane
Styrene
Tetradecane
Chlorobenzene
Chlorobenzene
Chlorobenzene
Chlorobenzene
6.39 x 1O-6
1.98 x 1O-5
6.00 x 1O-5
1.24 x 1O-4
1.1 x 10-5
3.6 x 1O-5
1.15 x 10-4
1.64 x 1O-5
6.28 x 1O-5
2.25 x 1O-4
8.92 x 10 -4
1.82 x 1O-5
5.75 x 10-5
1.75 x 10-4
4.88 x 1O-4
1.35 x 10-3
1.97 x 10-5
4.3 x 10-5
1.30 x 10-4
1.62 x 1O-4
6.0 x 1O-5
1.43 x 10-4
3.22 x 1O-4
5.53 x 10-4
3.2 x 1016
1.3 x 10-4
1.9 x 106
1.79 x 10-4
4.00 x 10-4
4.53 x 1o-4
4.83 x 1O-4
1.91 x 10-5
5.95 x 10-5
1.78 x 1O-4
4.96 x 1O-4
7.7
1.51 x 10
2.77 x 10
4.87 x 10
8.34 x 10
1.38 x lo*
2.13 x 10
3.22 x lo*
3.8 x lo-
2.96 x 1O-5
4.4 x 10-4
8.82 x 1O-6
2.80 x 1O-5
9.26 x 1O-5
2.78 x 1O-4
2.7 x 1O-6
1.5 X 10-6
1.43 x lo-s
1.17 x 10-8
2.04 x lo-
8.8 x 10-9
1.58 x lo-*
3.3 x 10-9
9.6 x 1O-9
3.63 x 1O-4
4.15 X 10-4
3.11 x 10-4
1.16 x 1O-3
159,0 a
a
a
a
a
163.6
exp[- 163.6/RT]
161. 5
exp[- 161S/RT] 1
156. 5 i(37-132)
154. 8 aj(2.6)
a,i(33)
a,i( 100)
156.7
u3
u3
u3
u3
154. 8 i(10)
i(10)
$10)
i(10)
$10)
$10)
i(10)
i(10)
159.0 h
t6
t6
t6
t6
t6
142. 3
t6
2 2 7
227
227
227
6 4
6 4
6 4
8 6
8 6
8 6
8 6
9 6
9 6
9 6
9 6
9 6
8 8
8 8
8 8
8 8
6 3
6 3
6 3
6 3
6 3
1 2 5
75,125
8 3
1 1 7
1 1 7
1 1 7
277
2 7 7
277
277
1 1 1
1 1 1
1 1 1
1 1 1
1 1 1
1 1 1
1 1 1
1 1 1
2 4 1
2 4 1
2 4 1
363
3 6 3
3 6 3
3 6 3
1 9 7
1 9 7
270
270
270
270
270
9 2
270
346
346
3 4 6
346
TABLE 3. contcl
Alkyl Peroxides II/27
Number of
C atoms Initiator Sol vent
T (Cl kd (S-l) E, Wmol) Notes Refs.
8 (contd) 2-tert-Butyl peroxy-2-methyl-
I-propanol-d t
1-Hydroxybutyl-n-butyl peroxide
Chlorobenzene
a-Methylstyrene
1-Hydroxyisobutyl-isobutyl peroxide cc-Methylstyrene
1-Hydroxyisobutyl-l-di-isobutyl-
1,l -dz peroxide
cc-Methylstyrene
Dimethylaminomethyl-
rerr-amyl peroxide
Styrene
Diethylaminomethyl-
rerf-butyl peroxide
Styrene
N-Biperidinomethyl-
rert-butyl peroxide
Styrene
9 rerr-Butyl rerr-amyl peroxide Cumene
10 tert-Amy1 peroxide Bulk
Chlorobenzene
Decalin
Octane
Triethylamine
Vapor
tert-Butyl 1, 1-dimethylbutyl
peroxide
Cumene
rert-Butyl 1,1,2-trimethylpropyl
peroxide
Cumene
2-Methyl-2-rerr-butyl-peroxyacetate
Ethyl 2-rert-butylperoxymethyl-
propenoate
Chlorobenzene
Triisopropylbenzene
11
12
Apocamphane- 1 - formyl peroxide
2,2-Bis(terr-butylperoxybutane)
Benzene
Benzene
1 5 0 1.23 x 1O-3 346
79.4 1.7 X 10-5
99.4 1.06 x 1O-4
1 0 9 . 9 2 . 9 x 10-4
7 9 . 4 3 . 7 x 10-5
99.4 2 . 0 x 10-4
1 0 9 . 9 4 . 8 x 10-4
9 9 . 5 6 . 9 x 1O-5
1 0 9 . 8 1.8 x 1o-4
1 2 2 . 0 4 . 2 x 1O-4
1 1 0 4 . 9 x 10-5
1 2 0 1.19 x 10-4
1 3 0 3 . 7 6 x 1O-4
1 1 0 4.1 x 10-5
1 2 0 1.35 x 1o-4
1 3 0 3 . 2 5 x 1O-4
1 1 0 5 . 5 x 10-5
1 2 0 2 . 6 6 x 1O-4
1 3 0 4.16 x 1O-4
1 1 0 3 . 8 6 x 1O-6
1 2 0 1 . 2 8 7 x 10 -5
1 3 0 4.30 x 10-5
1 4 0 1 . 4 0 6 x 10 -4
1 2 5 5 . 7 x 10-5
1 3 2 . 2 1.15 x 10-4
1 0 8 1.93 x 10-5
1 2 8 1.93 x 10-4
1 5 0 1.93 x 10-3
T W
4 . 0 2 x 10 l5
1 2 5 2 . 8 x 1O-5
1 2 5 3 . 0 x lo-s
1 2 5 3.5 x 10-5
1 3 2 . 2 7 . 2 x 1O-5
1 3 6 . 7 1.15 x 1o-4
1 4 2 . 2 2 . 1 6 x 1O-4
1 4 9 . 2 4 . 8 x 1O-4
136.7 1.34 x 10-4
1 4 2 . 2 2.41 x 1O-4
149.7 5.61 x 1O-4
1 1 0 4 . 3 8 x 1O-6
1 2 0 1.537 x 10-5
1 3 0 4.99 x 10-5
1 4 0 1 . 5 4 4 x 10-4
1 1 0 7 . 0 7 x 10-6
1 2 0 2.374 x 1O-5
1 3 0 7 . 6 2 x 1O-5
1 4 0 2.308 x 1O-4
1 5 0 4 . 1 2 x 1O-4
127.5 1.63 x 1O-4
1 3 0 1.95 x 10-4
132.5 2 . 1 6 x 1O-4
1 3 5 2 . 5 6 x 1O-4
137.5 3 . 4 7 x 10-4
1 4 0 3 . 9 2 x 10-4
142.5 4 . 6 8 x 1O-4
1 4 5 5 . 3 7 x 10-4
147.5 6 . 3 0 x 10 -4
1 5 0 7 . 7 6 x 1O-4
8 0 2 . 3 x 1O-4
8 5 3 . 0 x 10-6
1 0 0 1.9 x 10-5
115 9 . 3 6 x 1O-5
1 0 2 . 9
8 3 . 7 C
C
C
8 9 . 5
* 130.7
tll
tll
t11
1 3 2 . 4
t11
t11
tll
1 3 0 . 7
tll
tll
tll
exp[- 148.35/RT]
154.8-171.5 i(200-225)
i(200-225)
i(200-225)
i(lOO-200)
i(440-610)
i(440-610)
i(440-610)
c2
c2
c2
c2
c2
c2
c2
c2
c2
c2
151 a
a
a
3 2
3 2
3 2
3 2
3 2
3 2
2 5
2 5
2 5
3 0 3
3 0 3
3 0 3
3 0 3
3 0 3
303
3 0 3
3 0 3
303
3 6 3
3 6 3
3 6 3
3 6 3
202
202
344
344
344
344
202
202
202
6 3
6 3
6 3
6 3
6 3
6 3
6 3
3 6 3
3 6 3
3 6 3
363
3 6 3
3 6 3
3 6 3
3 6 3
346
3 5 3
3 5 3
3 5 3
3 5 3
3 5 3
3 5 3
3 5 3
3 5 3
3 5 3
3 5 3
244
3 3 7
3 3 7
3 3 7
Notes page II - 69; References page II - 70
II/28 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 3. contd
Number of
C atoms Initiator Sol vent
-
T(C) kd (S-l) E. WhoI) Notes Refs.
12 (cm&d) rerr-Butyl 1,1,3,3-tetramethylbutyl
peroxide
1-Hydroxy-l-hydroperoxy-
dicyclohexyl peroxide
Di -( l-hydroxycyclohexyl)-
peroxide
Diisopropylaminomethyl-
rerr-amyl peroxide
13
I-Phenylethyl ret?-butyl peroxide
rerr-Butylcc-cumyl peroxide
1 4
reti-Butyl p-chlorocumyl peroxide
terr-Butyl p-nitrocumyl peroxide
terr-Butyl l, l-dimethyl-2-phenyl-
ethyl peroxide
1,l -Di-(rert-butylperoxy)-
cyclohexane
Ethyl-3,3-di-terr-butylperoxy)-butyrate
I-[4-(Dimethylamino)phenyl]-
ethyl tert-butyl peroxide
15
16
tert-Butyl p-methoxycumyl peroxide
rerr-Butyl p-methylcumyl peroxide
reti-Butyl m-methoxycumyl peroxide
Bis( 1,1,2,2-ktramethylpropyl) peroxide
2-[4-(Dimethylamino)phenyl]-
propyl rerr-butyl peroxide
1 ,l-Di-(terr-amylperoxy)-
cyclohexane
reti-Butyl 3-isopropenyl-
cumyl peroxide
2,5-Dimethyl-2,5-di(rer?-butyl-
peroxy)-hexane
2,5-Dimethyl-2,5-di(rert-butyl-
peroxy)-3-hexyne
Cumene
Benzene
Chlorobenzene
Styrene
Chlombenzene
rer&Butylbenzene
Chlorobenzene
Cumene
Dodecane
Cumene
Cumene
Cumene
Benzene
Benzene
Chlorobenzene
Cumene
Cumene
Cumene
Cumene
Chlorobenzene
Benzene
Chlorobenzene
Benzene
Chlorobenzene
Benzene
1 1 0 1.085 x lo-*
1 2 0 3.13 x 10-5
1 3 0 1.141 x 10-4
140 3.40 x 10-4
8 5 9.6 x 1O-6
1 0 0 5.1 x 10-5
115 1.9 x 10-4
1 3 0 5.2 x 10 -4
1 0 5 N1.9X 10-5
1 2 0 -1.9x 10-4
1 1 0 3.9 x 10-5
120 1.21 x 10-4
1 3 0 3.0 x 10-4
1 2 9 . 2 3.09 x 10-5
1 3 8 1.48 x 1O-4
1 5 8 9.62 x 1O-4
1 1 5 1.93 x 10-5
1 3 6 1.93 x 10-4
1 5 9 1.93 x 10-3
T 6) 1.17 x 105
1 3 8 1.44 x 10-4
1 5 8 8.88 x 10-4
125 3.04 x 10-5
1 2 8 4.44 x 10-5
1 3 8 1.39 x 10-4
1 4 8 3.21 x 1O-4
1 5 8 8.88 x 10-4
1 2 5 2.42 x 1O-5
125 2.20 x 10-5
1 1 0 4.35 x 10-6
1 2 0 1.458 x 1O-5
1 3 0 4.70 x 10 -5
1 4 0 1.463 x 1O-4
9 3 1.9 x 10-5
111 1.9 x 10-5
1 0 0 . 4 1.82 x 1O-6
1 1 0 . 8 6.97 x 1O-6
1 2 0 . 9 2.18 x 1O-5
1 2 9 . 2 6.18 x 10-5
1 2 9 . 2 . 5.22 x 1O-5
1 2 5 3.72 x 1O-5
125 3.22 x 1O-5
1 2 5 2.84 x 1O-5
1 2 5 4.84 x 1O-4
1 2 9 . 2 1.51 x 1o-4
90
1 0 4
1 2 6
1 5 2
T 03
115
1 3 0
1 4 5
115
1 3 4
1 5 6
T (K)
1 1 5
1 3 0
1 4 5
1 6 0
1.9 x 10-5
1.93 x 10-5
1.93 x 10-4
1.93 x 10-3
1.161 x lOI
1.15 x 10-5
6.86 x 10 -5
4.75 x 1o-4
1.93 x 10-5
1.93 x 1o-4
1.93 x 10 -3
1.68 x 106
3.91 x 1o-6
2.35 x 1O-5
1.14 x 1o-4
6.17 x 1O-4 a
a,c 2
a,c 2
a,c 2
a,c 2
1 3 2 . 4 t11
t11
tll
a
a
exp[- 146.98/RT]
a
a
1 4 6 . 4 a
a
a
a
a
a
1 5 1 . 7
m2
m2
a
exp[- 128.33/RT]
1 6 6 . 9 a
a
a
exp[- 155.49/RT]
1 5 6 . 9 a
a
a
3 6 3
363
363
363
337
337
337
337
344
344
303
303
303
282
8 0
8 0
344
344
344
344
80
80
352
80
80
8 0
80
352
352
3 6 3
3 6 3
3 6 3
363
338
338
282
282
282
282
282
352
352
352
352
282
338
344
344
344
344
1 2 6 , 3 3 7
1 2 6 , 3 3 7
1 2 6 , 3 3 7
344
344
344
344
1 2 6 , 3 3 7
1 2 6 , 3 3 7
1 2 6 , 3 3 7
1 2 6 , 3 3 7
TABLE 3. cont d
Acyl Peroxides II/29
Number of
C atoms Initiator Solvent T (Cl kd (S-l) E, Wmol) Notes Refs.
16 (contd) 2,5-Dimethyl-2,5-di(ferr-butyl- Chlorobenzene
peroxy)-3-hexyne
17 n-Butyl-4,4-bis(rerbutylperoxy)-
valerate
Dodecane
l,l-Bis-(ren-butylperoxy)-
3,3,5&methylcyclohexane Benzene
18 Cumyl peroxide Benzene
terf-Butylbenzene
Chlorobenzene
Cumene
Dodecane
Diisopropylcarbinol
Neat
Bicyclo[2.2.2]octane-
1-formyl peroxide
Carbon tetrachloride
2 0 cc,cc-Bis(teti-butylperoxy)-
diisopropyl benzene
Chlorobenzene
Cyclohexane
Isooctane
Toluene
Benzene
Chlorobenzene
Neat
2 4 2,5-Dimethyl-2,5-di-(2-ethyl-
hexanoylperoxy) hexane
Benzene
1 2 0 1.93 x 10-5
141 1.93 x 10-4
1 6 4 1.93 x 1o-3
T (K) 1.90 x 10 l5
1 0 0 5 . 8 3 x 1O-6
115 3 . 5 3 x 10-5
1 3 0 2 . 9 1 x 1O-4
8 5
1 0 0
115
1 1 5
1 3 0
1 4 5
158
1 1 2
1 3 2
1 5 4
T 09
T (K)
1 3 8
1 5 8
1 2 8
1 3 8
1 4 8
1 5 8
138
1 5 0
155
1 6 0
165
30
3 0
3 0
3 0
3 0
1 1 5
125
1 3 0
1 1 4
1 3 4
1 5 6
T (K)
1 5 5
1 6 0
165
6 8
6.9 x 1O-6
5.05 x 10-5
2.71 x 1O-4
2.05 x lo-
1.05 x 10-4
6.86 x 10-4
1.72 x 1O-3
1.93 x 10-5
1.93 x 1o-4
1.93 x 10-3
9.24 x 10
4.31 x lOi
2.57 x 1O-4
1.52 x 1O-3
8.75 x 1O-5
2.31 x 1O-4
5.37 x 1o-4
1.83 x 1O-3
3.16 x 1O-4
3.98 x 1O-3
4.81 x 1O-3
9.63 x 1O-3
1.16 x lo-
1.71 x 10-4
1.73 x 10-3
1.68 X 10-4
6.20 x 1O-4
6.1 x 1O-5
5.0 x lo-5
3.66 x 1O-4
1.9 x 10-5
4.91 x 10-5
9.61 x 1O-5
1.93 x 10-5
1.93 x 10-4
1.93 x 10-3
7.65 x 10
3.61 x 1O-3
4.44 x 10-3
4.62 x 1O-3
1.9 x 10-5
exp]- 150.67/RT]
a
a
a
1 3 8 a
a
a
1 5 9 a
a
a
a
exp[- 152.67/RT]
exp[- 144.3/RT]
a
a
a
a
a
a
a
a
a
a
a
n
VI
1 4 7 a
a
a
exp[- 152.69 kJ/RT]
a
a
a
a
344
344
344
344
8
8
8
337
337
337
3 3 7
1 2 6 , 3 3 7
1 2 6 , 3 3 7
8 0
344
344
344
344
6 7
8 0
8 0
8 0
8 0
80
8 0
8 0
3 7 1
3 7 1
3 7 1
3 7 1
244
244
244
244
244
244
244
3 3 7
3 3 7
3 3 7
344
344
344
344
3 7 1
3 7 1
3 7 1
3 3 8
TABLE 4. ACYL PEROXI DES
Number of
C atoms Initiator Solvent
T(C) kd (S-l) E. Wmol) Notes Ref s.
4 Acetyl peroxide Acetic acid 5 5 . 2 2 . 8 x 1O-6 126.4 d,e 1 0 6 , 1 7 6
6 4 . 9 9 . 9 x 10-6 d,e 1 0 6 , 1 7 6
7 5 . 2 3 . 7 5 x 10-5 d,e 1 0 6 , 1 7 6
8 5 . 2 1 . 3 0 x 1o-4 d,e 1 0 6 , 1 7 6
7 3 . 2 2 . 6 2 x lo- a 1 0 0
Notes page II - 69; References page II - 70
I i / 30 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
Table 4. contd
Number of
C atoms Initiator Solvent
T ((3 kd (S-l) E, (kJhol) Notes Ref s.
4 (contd) Acetyl peroxide Benzene
n-Butanol
set-Butanol
terr-Butanol
Carbon tetrachloride
Chloroform
Cyclohexane
Cyclohexene
Cyclopentene
Cumene
Decane
n-Dodecane
Ethanol
Heptane
Hexadecane
n-Hexane
1 -Hexene
2-Methyl-I-pentene
n-Octadecane
n-Octane
Isooctane
1-Pentene
Propionic acid
3 5 9.5 x lo-
5 5 3.14 x 10-6
6 5 1.27 x 1O-5
5 0 1.1 x 10-6
7 0 2.39 x 1O-5
8 5 1.73 x 10 -4
7 0 2.38 x lo-
60.3 5.0 x 1o-6
8 0 8.7 x lo-
55.2 2.6 x 1O-6
64.9 1.07 x 10-5
75.2 4.65 x lo-
85.2 1.62 x 1O-4
60.3 3.4 x 10-5
60.3 3 x 10-5
60.3 3.1 x 10-6
80.3 4.9 x 10-5
2 6 1.08 x IO-
4 6 4.84 x lo-
6 5 2.11 x 10-6
8 0 5.5 x 10-5
80.3 - 5
55.2 2.1 x 10-6
64.9 8.3 x 1O-6
75.2 3.60 x 1O-5
85.2 1.27 x 1O-4
6 0 4.5 x 10-6
7 0 1.77 x 10-5
8 0 7.0 x lo-
9 0 2.28 x 10-4
1 0 0 7.61 x 1O-4
7 0 1.60 x 1O-5
8 0 7.0 x 10-5
9 0 2.55 x 1O-4
1 0 0 7.25 x 1O-4
8 0 7.6 x 1O-5
8 0 6.85 x 1O-5
6 0 2.3 x 1O-6
8 0 6.15 x 1O-5
60.3 1.01 x 1o-4
80.3 1.40 x 10-3
8 0 7.72 x 1O-5
8 0 5.39 x 10-5
6 0 3.4 x 10-6
7 0 2.35 x 1O-5
8 0 8.7 x 1O-5
9 0 3.05 x 10-4
1 0 0 9.83 x 1O-4
8 0 9.0 x 10-5
9 0 3.12 x 1O-4
1 0 0 9.81 x 1O-4
6 0 1.9 x 10-6
6 0 2.9 x 10 -
8 0 7.34 x 10-5
6 0 2.9 x 1O-6
55.2 2.35 x 1O-6
64.9 9.4 x 10-6
75.2 4.03 x 10-5
85.2 1.49 x 1o-4
7 0 2.45 x 1O-5
8 0 9.4 x 10-5
9 0 3.22 x 1O-4
64.9 1.4 x 10-5
85.2 1.66 x 1o-4
1 3 4
135. 1
133.9
131.4
133. 5
137.2
129.7
132.6
126.8
134.7
c,e
c,e
c,e
c,e
c,e
c,e
c,e
c,e
c,e
c,e
c,e
c,e
d,e
6 8
6 8
6 8
3 3 7
126,337
126,337
1 6
4
2 0
106,176
106,176
106,176
106,176
4
4
4
4
6 8
6 8
6 8
2 0
4
106,176
106,176
106,176
106,176
2 0
2 0
2 0
2 0
2 0
2 0
2 0
2 0
2 0
2 0
1 6 8
7 0
1 6 8
4
4
1 6 8
1 6 8
7 0
2 0
2 0
2 0
2 0
2 0
2 0
2 0
7 0
7 0
1 6 8
7 0
106,176
106,176
106,176
106,176
2 0
2 0
2 0
106,176
106,176
i
Table 4. contd
Acyl Peroxides II/31
Number of
C atoms IilitiZItor Solvent T (Cl ka (S-l) E. Wmol) Notes Refs.
4 (contd) Acetyl peroxide n- Te t r a de c a ne 60
8 0
To l u e n e 60. 3
55. 2
64. 9
15. 2
85. 2
13. 2
85. 5
90
Vapor (toluene) 88. 0
134. 7
150. 7
161. 7
170. 7
184. 2
6 Pr o p i o n y l p e r o x i d e Acetic acid 65. 0
85. 0
Acetic anhydride 65. 0
85. 0
Be n z e n e 65. 0
85. 0
50
70
85
65. 0
85. 0
Dioxane 65. 0
85. 0
n-Hexane 65. 0
85. 0
Isooctaue 65. 0
86. 5
Ni t r o b e n z e n e 65. 0
85. 0
To l u e n e 65. 0
85. 0
Va p o r 65. 0
85. 0
99. 4
134. 4
152. 2
176. 4
190. 9
T W
2-Iodopropionyl peroxide Ac e t o n e 56
Be n z e n e 62. 5
62. 5
62. 5
n-Butyl vinyl ether 62. 5
Cyclohexene 62. 5
95% Ethanol 62. 5
Perfluoropropionyl peroxide Freon 113 20
30
40
T (W
Isooctane
T W
2,2,3,3-Tetrafluoropropionyl Freon 113 25
peroxide 35
8 rert-Butyl perrnaleic acid Ac e t o n e 81
Butyryl peroxide Acetic acid 65. 0
85. 0
Acetic anhydride 65. 0
85. 0
2. 0 x 10-6
5. 90 x 10-5
5x10- 6
2. 7 x 10-6
1.14 x 10-5
4. 70 x 1o-5
1.59 x 10-4
3. 06 x lO-5
1. 72 x 1O-4
7. 33 x 10-5
3. 12 x 1O-4
3. 1 x 10-2
1.18 x lo-
2. 77 x lo-
6.10 x lo-
1. 76
3. 8 x 10 -5
4. 3 x 10 -4
3. 5 x 10-5
4. 5 x 1o-4
1. 88 x 10-5
2. 40 x 1O-4
2. 12 x 10-6
4. 30 x 10-5
2. 89 x 1O-4
3. 9 x 10-5
5. 1 x 1o-4
4. 5 x 10-5
4. 5 x 10-4
1. 50 x 10-5
1. 72 x 1O-4
9.8 x 1O-6
1.44 x 10-4
3. 7 x 10-5
4.1 x 1o-4
1. 87 x 1O-5
2. 54 x 1O-4
1.0 x 10-5
1.6 x 1O-4
8 x 1O-4
2. 6 x 1O-2
1.22 x 10-1
8. 0 x lo-
2. 33
2. 5 x 1O-4
2.19 x 10-4
( 2. 40- 2. 81) ~ 1O-4
7.12 x 1O-4
( 2. 36f 0. 07) x 1O-4
2. 47 x 1O-4
2. 1 x 1o-4
4. 0 x 10-4
2.19 x 10-5
8. 50 x 1O-s
3. 26 x 1O-4
1. 8 x log
1. 5 x 10
2. 26 x 1O-4
7. 17 x 10-4
1. 9 x 10-5
4. 7 x 10-5
5. 6 x 1O-4
4. 3 x 1o-s
5. 5 x 10-4
129.7
133. 9
138. 1
129. 7
123. 4
123. 0
128. 9
129.3
127.6
130.5
116.7
123.8
130.5
120.9
130.1
125. 5
125. 5
exp[- 125.5/RT]
108. 8
100.1
exp[- 83.8/RT]
exp[- 121.5/RT]
86. 3
125. 1
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
c,e
c,e
c,e
S
S
n,s
P
S
S
s,
h
a
c,e
c,e
c,e
70
168
4
106, 176
106, 176
106, 176
106, 176
1 0 0
100
1 1 3
1 0 5
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
71
17
17
17
17
77
71
283
283
283
304
304
283
283
338
51
5 1
5 1
51
Notes page II - 69; References page II - 70
II/32 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
Table 4. contd
Number of
C atoms Initiator Solvent
T (C) kd (S-l) E, Wmol) Notes Ref s.
8 (contd) Butyryl peroxide Benzene
Benzonitrile
Dioxane
Hexane
Isooctane
Toluene
Vapor
Isobutyryl peroxide Acetonitrile
Benzene
Benzonitrile
terr-Butanol
Carbon tetrachloride
Chlorobenzene
Chloroform
Cyclohexane
Fluorobenzene
Cyclopropane formyl peroxide
Isopropanol
Nitrobenzene
Nujol
Tetralin
Toluene
Vapor
p-Xylene
Carbon tetrachloride
Diacetyl succinoyl diperoxide Styrene
Succinoyl peroxide Acetone
65. 0 2. 24 x 1O-5
85. 0 3. 02 x 1O-4
65. 0 4. 3 x 10-5
85. 0 5. 8 x 1O-4
65. 0 4. 6 x 1O-5
85. 0 4. 6 x 1O-4
65. 0 1.14 x 10-5
85. 0 1.53 x 1o-4
65. 0 1.11 x 1o-5
85. 0 1.56 x 1O-4
65. 0 2.14 x 1O-5
85. 0 2. 87 x 1O-4
65. 0 1.6 x 1O-5
85. 0 2. 0 x 10-4
96. 1 8. 6 x 1o-4
127. 4 1.5 x 10-2
158. 9 3. 0 x lo-
178. 9 1.27
T WI
1.9 x 1o-4
40 6.81 x 1o-4
20 1.6 x 1O-5
30 6. 75 x 1O-5
40 2. 59 x 1O-4
40 2. 38 x 1O-4
40 2. 40 x 1O-4
40 4. 2 x 1O-4
40 2.51 x 1O-4
40 7. 8 x 10-5
45 1.58 x 1O-4
50 3. 05 x 1o-4
55 5.61 x 1O-4
60 7. 67 x 1O-4
40 1.73 x 1o-4
23 1.93 x 10-5
39 1.93 x 10-4
57 1.93 x 10-3
T W)
3. 37 x 104
40 7. 5 x 10-5
40 4. 5 x 1o-5
40 4. 70 x 10-5
40 1.23 x 1O-4
25 3. 35 x 10-6
35 1.54 x 10-5
45 6.14 x 1O-5
55 2. 26 x 10 -4
T W)
2. 8 x lOI
40 3. 2 x 1O-5
40 3. 05 x 1o-4
40 5. 80 x 1O-4
40 4. 63 x 1O-5
40 1.75 x 10 -4
40 1.43 x 10-4
40 -1 x 10-5
40 1.40 x 10-4
64. 5 4. 4 x 10-6
10. 4 9. 3 x 10-6
11. 8 2.31 x 1O-5
60 5. 2 x lO-j
13. 5 2. 3 x 1O-5
85 9. 3 x 10-5
70 2. 80 x 1O-5
85 1.21 x 1o-4
1 0 0 4. 36 x 1O-4
1 3 1 . 4
1 3 1 . 4
116.3
1 3 1 . 4
133.5
130.5
123.i
1 2 3 . 8
exp[- 123.8/RT]
1 0 9
exp[- 109.06/RT]
1 1 4 . 2
exp[- 114.2/RT]
125. 5
99. 6
d,e
c,e
d,e
c,e
c,e
v
c,e
c,e
c,e
d,e
c,e
m3
a
a
a
m3
a
a
a
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. contd
Acyl Peroxides II/33
Number of
C atoms Initiator Solvent T (0 ka (S-) E. WhoI) Notes Refs.
9 Acetyl benzoyl peroxide
10 5.Bromo-2-thenoyl peroxide Carbon tetrachloride
4-Bromo-2-thenoyl peroxide Carbon tetrachloride
5-Chloro-2-thenoyl peroxide Carbon tetrachloride
a-Chloropropionyl m-chlorobenzoyl- Acetonitrile
peroxide Cyclohexane
Cyclobutane formyl peroxide Carbon tetrachloride
Cyclopropane acetyl peroxide Carbon tetrachloride
Diacetyladipoyl diperoxide Styrene
Difuroyl peroxide styrene
2 2 3 3 4 4 5 ,1,,,7. 5-Octafluoropentanoyl
peroxide
1 1
Perfluoro-2-(2-ethoxysulfinic
acid) propionyl peroxide
Pivaloyl peroxide
2-Thenoyl peroxide
3-Thenoyl peroxide
Benzoyl isobutyryl peroxide
mChlorobenzoy1 isobutyryl peroxide
p-Chlorobenzoyl isobutyryl peroxide Cyclohexane
p-Fluorobenzoyl isobutyryl peroxide Cyclohexane
5-Methyl-bis-2-thenoyl peroxide Carbon tetrachlotide
p-Nitrobenzoyl isobutyryl peroxide Cyclohexane
12 P-Allyloxypropionyl peroxide
mChlorobenzoy1 2-methyl- Acetic acid
butanoyl peroxide Acetonitrile
Freon 113
Freon 113
Carbon tetrachloride
Carbon tetrachloride
Carbon tetrachloride
Acetonitrile
Cyclohexane
Acetonitrile
Cyclohexane
p-Xylene
70 2 x 10-5
96 5.12 x 1O-4
96 4.08 x 1O-4
7 5 1.53 x 10-5
7 5 1.14 x 10-5
15 1.58 x 1O-5
4 1 3.05 x 10-5
4 1 1.51 x 10-5
6 5 5.15 x 10-5
70 8.95,6.63 x 1O-5
7 5 1.41 x 10-4
1 4 9.45 x 1o-5
2 5 9.75.10.57 x 10-4
44.5 5.01 x 10-5
5 6 . 5 2.64 x 10-4
4 4 . 5 6.5-8.0 x 1O-4
60 6.6 x 10-6
7 3 . 5 4.73 x 10-5
8 5 1.84 x 1O-4
50 7.0 x 10-7
60 2.9 x 1O-6
70 1.03 x 10-5
20 3.29 x 1O-5
3 0 1.27 x 1O-4
40 5.01 x 10-4
T 6) 2.8 x lOI
1 0 1.9 x 10-4
15 2.21 x 10-5
7 5 2.14 x 1O-5
4 1 4.06 x 1O-4
4 1 1.63 x 1O-5
70 3.05 x 1o-4
40 1.45 x 10-5
50 5.398 x 1O-5
60 1.924 x 1O-4
70 6.872 x 1O-4
4 1 1.03 x 10-3
40 3.486 x 1O-5
50 1.362 x 1O-4
4 1 4.40 x 10-5
50 1.029 x 1O-4
5 5 1.651 x 1O-4
60 3.21 x 1O-4
6 5 5.638 x 1O-4
5 5 1.117 x 10-4
60 2.038 x 1O-4
6 5 4.893 x 1O-4
70 9.603 x 10 -4
7 5 2.92 x 1O-5
40 8.1 x 1O-5
4 5 1.336 x 1O-4
50 2.889 x 1O-4
5 5 4.725 x 10 -4
60 8.921 x 1O-4
70 2.01 x 10-5
8 0 8.62 x 1O-5
90 2.53 x 1O-4
70 2.32 x 1O-5
8 0 8.88 x 10 -5
90 2.95 x 1O-4
40 1.60 x lo-
40 1.72 x 1O-3
~(25)~~ l3
z(l9),v 13
a,m 1
a,m L
a,m L
m3
m3
1 0 1 . 7
n
1 2 5 . 7 h
1 0 0 . 6 h
exp[- 95.1/RT]
am I
a,m 1
1 1 2 . 5 hj
1 1 1 . 3
hj
j
a
155
284
284
232
232
232
1 6 7
1 6 7
3 4
3 4
3 4
3 4
3 4
24
2 4
2 4
215
2 1 5
2 1 5
287
287
287
283
283
283
304
244
232
232
1 6 7
1 6 7
1 6 7
1 6 4
1 6 4
1 6 4
1 6 4
1 6 7
1 6 4
1 6 4
1 6 7
1 6 4
1 6 4
1 6 4
1 6 4
1 6 4
1 6 4
1 6 4
1 6 4
232
1 6 4
1 6 4
1 6 4
1 6 4
1 6 4
191
191
191
191
191
191
256
256
Notes page II - 69; References page II - 70
II/34 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
Table 4. contd
Number o f
C atoms Initiator Solvent
TV3 kd (S-l) E. Wmol) Notes Refs.
12 (co&d) mXhlorobenzoy1 2-methyl-
butanoyl peroxide
Cyclobutane acetyl peroxide
Cyclopentane formyl peroxide
Hexanoyl peroxide
5-Hexenoyl peroxide
4-Methoxybenzoyl isobutyryl-
peroxide
4-Methylbenzoyl isobutyryl-
peroxide
4-Methyl-2-thenoyl peroxide
5-Methyl-Zthenoyl peroxide
Perlluoro-2-fumanacetyl peroxide
Perlluoro-2-propoxypropionyl-
peroxide
Perfluoro-2+propoxypropionyl-
peroxide
Perlluoro-2-iso-propoxypropionyl-
peroxide
1 4 2-Azidobenzoyl peroxide
Benzoyl peroxide
2-Butanol
Carbon tetrachloride
Cyclohexane
Carbon tetrachloride
Carbon tetrachloride
Toluene
Toluene
Cyclohexane
Cyclohexane
Carbon tetrachloride
Carbon tetrachloride
Freon 113
Freon 113
perF-ether mix.
Freon 113
Freon 113
Benzene
Acetic acid
Acetone
Acetonitrile
Acetophenone
Ally1 alcohol
Anisole
Benzaldehyde
Benzene
40 9.0 x 10-4
40 1.32 x 1O-4
40 6.0 x 1O-5
6 5 1.37 x 10-5
70 2.13,3.08 x 1O-5
7 5 3.83 x lo-
40 1.50 x 10-5
4 5 2.55 x 1O-s
50 4.96 x 1O-5
5 5 8.17,7.85 x 1O-5
7 7 1.186 x 10-4
60.1 1.06 x 1O-5
7 0 . 4 4.15 x 1o-5
7 6 . 4 8.59 x 1O-5
8 5 . 0 2.668 x 1O-4
5 5 5.465 x 1O-5
6 0 1.024 x 1O-4
6 5 1.876 x 1O-4
70 3.208 x 1O-4
40 9.61 x 1O-6
50 3.619 x 1O-5
60 1.305 x 10-4
7 0 4.772 x 10 -4
7 5 2.92 x lo-
7 5 4.21 x lo-5
T 6)
1.2 x 10
T W
4.4 x 104
T W) 8.9 x 1016
20 4.81 x 1O-5
30 1.96 x 1O-4
40 7.16 x 1O-4
2 0 8.32 x 10 -5
3 0 3.43 x 10-4
40 1.34 x 10-3
50 2.5 x 1O-5
8 0 9.4 x 1o-4
7 5 7.53 x 10-5
50 2.25 x 1O-6
70 2.63 x 1O-5
8 5 1.34 x 10-4
1 0 0 5.83 x 1O-4
7 0 1.76 x lo-
70 1.15 x 10-5
8 0 4.32 x 1O-5
9 4 . 5 2.30 x 1O-4
80 3.80 x 1O-4
3 0 1.42 x lo-
8 0 5.50 x 10-5
90 1.71 x 10-4
2 5 6.4 x 1O-5
3 0 4.80 x lo-*
5 5 1.14 x 10-6
6 0 2.76 x 1O-6
60 2.0 x 10-6
8 0 2.5 x 1O-5
70 1.38 x 1O-5
7 8 2.30 x 1O-5
7 8 1.67 x 1O-5
7 9 . 8 3.48 x 1O-5
8 0 4.8 x 1O-5
66 7.72 x 1O-6
7 2 . 5 1.87 x 1O-5
7 8 3.77 x 10-5
70 1.17 x 10-5
129.3
j
j
j
j
am 1
am I
exp[-77.1/RT]
exp[- 98.5/RT]
exp[- 110,2/RT]
100.1 h
1 0 2 . 7 h
1 1 1 . 3
1 2 6 . 4
116.3
1 2 4 . 3
dz
d2
a,r
a
a
a
a
t1
a
a
a
a,r
a
a,r
a,r
P2
a
a,r
a,r
m2
m2
a
C
t9
1 2 9 . 7
1 3 3 . 9
256
256
256
34
34
3 4
3 4
34
34
34
209
209
209
209
209
1 6 4
1 6 4
1 6 4
1 6 4
1 6 4
1 6 4
1 6 4
1 6 4
232
232
304
304
304
283
283
2 8 3
2 8 3
283
283
161
161
74
1 2 6
1 2 6
1 2 6
1 2 6
1 2 4
5
5
5
74
1 0 9
74
74
279
1 0 9
74
74
1 4
1 4
2 1 3
230
230
1 7 0
2 0
131
131
131
7 3
Table 4. contd
Acyl Peroxi des II/35
Number of
C atoms Initiator Solvent
T(C) kd (S-I) E. Wmol) Notes Ref s.
14 (contd) Benzoyl peroxide Benzene
Benzyl alcohol
Bromohenzene
Butanol
Butanone
Di-n-butyl phthalate
Carbon tetrachloride
Chlorohenzene
Chloroform
C u m e n e
Cyclohexane
Decane
Decalin
Dioxane
15
8 0
8 0
50.8
54.9
60.9
65.6
71.0
75.8
7 0
8 5
1 0 0
7 0
7 0
7 5
7 5
8 5
8 5
1 0 0
100
7 9
8 0
8 0
80.2
8 0
8 0
1 1 7
1 2 7
1 3 7
1 4 7
7 5
7 9
7 0
8 0
80.2
80.2
80.2
80.2
7 1
9 1
1 1 3
T (K)
3 0
8 0
8 5
9 0
3 0
4 5
6 0
8 0
T WI
1 0 0
8 0
8 0
8 0
7 0
8 0
8 0
8 0
2.62 x 1O-5
4.39 x 10-5
3.27 x 1O-5
4.28 x lo-
8.53 x lo-
1.66 x 10-6
3.22 x 1O-6
5.94 x 10-6
1.19 x 10-5
1.27 x lo-
8.94 x 10-5
4.96 x 10 -4
1.03 x 10-5
1.18 x 10-5
1.48 x 1O-5
1.66 x 10-5
4.7 x lo-J
5.5 x 10-5
2.28 x 10-4
2.56 x 1O-4
2.58 x 1O-5
3.35 x 10-5
4.44 x 10-4
8.15 x 1O-5
2.19 x 1O-5
3.84 x 1O-5
3.55 x 10-5
4.34 x 10-5
6.06 x 10-4
4.64 x 1O-5
2.78 x 1O-3
7.44 x 10-3
1.72 x lo-
3.89 x 1O-2
1.07 x 10-5
1.69 x 1O-5
1.35 x 10-5
4.64 x 1O-5
2.85 x 1O-5
2.36 x 1O-5
3.52 x 1O-5
2.62 x 1O-5
1.93 x 10-5
1.93 x 10-4
1.93 x 10 -3
6.94 x lOI
5.47 x 10-8
3.69 x 1O-5
6.39 x 1O-5
1.19 x 10-4
7.30 x 10-8
1.85 x 10
1.45 x 10-6
1.70 x 10-5
1.20 x 103
2.5 x 1O-4
1.12 x 10-5
2.53 x 1O-5
2.26 x 1O-4
1.30 x 10-5
6.72 x 1O-4
4.20 x 1O-4
4.18 x 10-5
123. 8
1 3 0
128.0
124. 3
ml
m3
m5
120. 1
exp[- 122.35/RT]
120.5
exp[- 120.5/RT]
a
a
a,b 2
as2
02
as 2
as2
a,t2
a,t 2
a
a
a
am2
tl
m3
m3
m3
apt 6
a
a,r
t9
a,r
a,r
Y 16
a,r
t6.a
t1
a,r
t9
cm 1
cm3
a
a,r
a,r
a,r
a
a,t 7
a,r
a,r
t1
a,r
a,r
am I
7 3
7 3
347
6 9
6 9
6 9
6 9
6 9
6 9
3 3 7
126,337
126,337
1 6
1 2 4
1 2
1 2
1 2
1 2
1 2
1 2
1 2 0
7
7 4
2 3 1
2 3 1
2 3 1
2 3 1
2 3 1
7 4
7 4
236
236
236
236
14
1 2 1
1 2 4
7 4
2 3 1
2 3 1
2 3 1
2 3 1
344
344
344
344
1 0 9
14
7 4
7 4
1 0 9
6 7
6 7
6 7
6 7
1 2 2
7 4
270
7 4
7 4
7 4
6
232
Notes page II - 69; References page II - 70
II/36 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
Table 4. contcf
Number of
C atoms Initiator Solvent
T((2 kd (S-l) E, Wmol) Notes Refs.
14 (contd) Benzoyl peroxide Ethanol
Et h y l b e n z e n e
90% Formic acid
n - He p t a n e
He x a d e c a n e
He x a n e
I s o o c t a n e
I s o p r o p y l b e n z e n e
Met hyl acet at e
Me t h y l c y c l o h e x a n e
4 - Me t h y l - 2 p e n t a n o n e
a - Me t hyl s t yr e ne
Mineral oil
N e a t
Ni t r o b e n z e n e
PEG 400
90% aq. PEG 400
80% aq. PEG 400
70% aq. PEG 400
n - Pe n t a n o l
Ph e n o l
Propionic acid
Pr o p y l e n e g l y c o l
St y r e n e
25 3. 02 x lo-*
40 2. 77 x lo-7
50 4. 72 x lo-
30 3.61 x lo-*
75 1.81 x 1O-5
80 3. 33 x 10-5
85 5. 56 x 1O-5
90 1.01 x 10-4
80 3.15 x 10-5
80 6. 94 x 1O-4
80 3.11 x 10-5
80 2.71 x 1O-5
130 5. 73 x 10-3
135 1.02 x 10-2
140 1.54 x 10-2
145 2. 25 x lo-*
145 2. 22 x 10-2
145 2.21 x 10-2
145 2.12 x 10-2
150 3. 47 x 10-2
155 5.21 x lo-*
160 7. 87 x 10-2
80 2.51 x 1O-5
80 2. 85 x 1O-5
80 2. 79 x 1O-5
80 2. 70 x 1O-5
80 3. 34 x 10-5
49. 2 6. 28 x lo-
53. 9 1.0 x 10-6
80 5. 25 x 1O-5
80 4. 28 x 1O-5
70 3. 02 x 1O-5
80 2. 89 x 1O-s
105 7. 22 x 1O-3
80 4. 58 x 10-5
30 6.61 x 10-8
25 5.01 x 10-7
40 5. 73 x 10-6
50 1.15 x 10-5
70 1.15 x 10-4
25 3. 65 x lo-
40 5. 35 x 10-6
50 1.15 x 10-5
70 1.15 x 10-4
25 2. 77 x lo-
40 3. 09 x 10-6
50 7. 29 x 1O-6
70 1.15 x 10-4
25 1.71 x 10-7
40 2.11 x 10-6
50 5.01 x 10-6
70 1.15 x 1o-4
80 1.48 x 1O-4
80 6. 25 x 1O-4
80 3.19 x 10-5
25 3. 25 x 1O-8
40 1.51 x 10-7
50 3.16 x lo-
34. 8 3. 89 x lo-
49. 4 5. 28 x lo-
61. 0 2. 58 x 1O-6
74. 8 1.83 x 1O-5
100.0 4. 58 x 10-4
a
a
a
a
a,r
a,r
a,r
a,r
C
a,r
a,r
2 ( 1500)
z( 1500)
z( 1500)
z ( 500)
z (1000)
z (1500)
z ( 2000)
z( 1500)
z ( 1500)
z ( 1500)
m2
C
123. 8 as2
as2
a, r
a, r
a
m2
a
a,r
117.6 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
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
1 0
1 0
1 0
1 0
1 0
T a
Nl
c?
Table 4. contd
Acyl Peroxi des II/37
Number of
C atoms Initiator Solvent
T (Cl kd (S-l) E, Wmol) Notes Refs.
14 (contd) Benzoyl peroxide Poly(styrene)
Tetradecane
Tetralin
Toluene
Poly(vinylchloride)
Styrene
3-Bromobenzoyl peroxide
p-Xylene
Benzene
4-Bromobenzoyl peroxide
4-fer&Butylbenzoyl peroxide
2Chlorobenzoyl peroxide
3-Chlorobenzoyl peroxide
4-Chlorobenzoyl peroxide
Dioxane
Dioxane
Dioxane
Acetophenone
Benzene
Acetophenone
Dioxane
Acetophenone
Benzene
Dioxane
Styrene
Cyclohexane formyl peroxide
Carbon tetrachloride
Cyclopentane acetyl peroxide Carbon tetrachloride
Diacetylsebacoyl diperoxide Carbon tetrachloride
56. 4 3. 8 x 1O-7
64. 6 1.47 x 10-6
16. 1 9. 27 x 1O-6
83. 4 2. 50 x 1O-5
98. 5 1.41 x 10-4
70. 9 2. 86 x 1O-6
80. 1 1.11 x 10-5
89. 5 3. 33 x 10-5
80 2. 64 x 1O-5
80 3. 72 x 1O-5
30 4. 94 x lo-s
49. 0 6. 0~ 1O-7
55. 1 1. 31 x 10-6
60. 2 2. 83 x 1O-6
65. 1 5.69 x 1O-6
70. 3 1.10 x 10-5
60. 00 2. 24 x 1O-6
64. 6 6. 3 x 1O-7
16. 1 5.11 x 10-6
83. 4 1.44 x 10-5
98. 5 9. 33 x 10-5
50 7 x 1o-7
60 7. 7 x 10-6
70 9.9 x 1o-6
80 3.10 x 10-5
60 1.1 x 10-6
80 1.22 x 10-5
80 2. 60 x 1O-5
80 2. 57 x 1O-5
80 3. 23 x 1O-5
80 6. 06 x 10-5
80 3. 88 x 1O-4
80 3.12 x 1O-4
80 2. 85 x 1O-5
80 2. 63 x 1O-5
80 3. 83 x 10m5
80 2.17 x 1O-5
50 6. 2 x 1O-7
85 6. 64 x 1O-5
1 0 0 3. 86 x 1O-4
80 3. 62 x 1O-5
34. 8 8. 3 x 1O-8
49. 4 8. 3 x 1O-7
61. 0 3. 33 x 1o-6
74. 8 2. 22 x 10-5
1 0 0 . 0 4.17 x 10-4
30 9. 64 x 1O-5
35 1.46 x 1O-4
40 3.10 x 10-4
45 5.11 x 1o-4
50 7.17 x 1o-4
35 6. 6 x 10-5
45 2.11 x 10-4
50 4. 45 x 10-4
60 1.30 x 10-3
35 2. 87 x 1O-5
40 5. 22, 5. 29 x 1O-5
45 9.67 x 1O-5
65 1.48 x 10-5
70 3. 20 x 1O-5
75 4. 91 x 10-5
60 1.04 x 10-5
73. 5 5. 20 x 1O-5
85 2. 30 x 1O-4
120. 5
123. 8
125. 7
123. 0
128. 4
127. 2
1 2 8 . 9
84. 5
a,r
a
a,t2
as2
as2
a,t 2
a,t2
em 3
a
a
a
a
C
a
am L
a,m 1
am
a
a
a
am 1
a
a
a
a
a
a,m 1
a
a
a
a
a
a,h
Xl
Xl
Xl
17
17
17
17
1 7
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
1 0
1 0
10
10
1 0
219
219
219
219
219
1 4 8
1 4 8
1 4 8
1 4 8
34
34
34
34
34
34
215
215
215
Not es page I I - 69; References page II - 70
I I / 38 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
Tabl e 4. contd
Number of
C atoms Initiator Solvent
T(C) kd (S-l) E. Wmol) Notes Refs.
14 (contd) 2,4-Dichlorobenzoyl peroxide Be n z e n e
223344556677Dodeca-
17719,,0,,
fluoroheptanoyl peroxide
Heptanoyl peroxide
6-Heptenoyl peroxide
2-Iodobenzoyl peroxide
2-Iodobenzoyl 4-nitrobenzoyl
peroxide
3-Methylbenzoyl peroxide
4-Methylbenzoyl peroxide
2-Nitrobenzoyl peroxide
3-Nitrobenzoyl peroxide Ac e t o p h e n o n e
4-Nitrobenzoyl peroxide Ac e t o p h e n o n e
3,SDinitrobenzoyl peroxide Ac e t o p h e n o n e
Perlluoroheptanoyl peroxide Freon 113
15 Benzoyl phenylacetyl peroxide Be n z e n e
4-rerr-Butylbenzoyl isobutyryl
peroxide
3-Cyanobenzoyl benzoyl peroxide
3-Methoxybenzoyl benzoyl peroxide
4-Methoxybenzoyl benzoyl peroxide
4-Methoxybenzoyl 3-bromobenzoyl
peroxide
4-Methoxybenzoyl-3,5-dinitro-
benzoyl peroxide
4-Methoxybenzoyl 4nitrobenzoyl
peroxide
16 3,5-Dibromo-4-methoxybenzoyl
peroxide
Caprylyl peroxide Be n z e n e
Freon 113
To l u e n e
To l u e n e
Chloroform
Ac e t o n e
Acetonittile
Be n z e n e
Carbon tetrachloride
Chloroform
Ni t r o b e n z e n e
Dioxane
Dioxane
Ac e t o p h e n o n e
Methyl iodide
Cyclohexane
Dioxane
Dioxane
Dioxane
Dioxane
Ni t r o b e n z e n e
Be n z e n e
Be n z e n e
70 9.70 x 10 -5
70 1.24 x 1O-4
50 1.08 x 1O-5
70 1.37 x 10-4
8 5 7.69 x 1O-4
34.8 3.88 x 1O-6
49.4 2.39 x 10-5
61.0 7.78 x 10-5
74.8 2.78 x 10 -4
100.0 4.17 x 10-3
30 1.14 x 10-4
40 4.06 x 1O-4
7 7 1.24 x 1O-4
70 5.33 x 1o-s
70 5.01 x 10-5
7 7 1.07 x 10-4
8 5 2.88 x 1O-4
2 2 1.86 x 1O-3
2 5 3.0 x 1o-4
2 5 2.1 x 10-4
2 5 5.7 x 10-5
2 5 3.4 x 10-5
2 5 2.8 x 1O-4
2 5 6.2 x 1O-4
80 4.38 x 1O-5
80 6.11 x 1O-5
59.3 5.80 x 1O-5
80 1.34 x 10-3
24.95 1.78 x 1O-5
45.05 1.50 x 10-4
80 3.80 x lo-s
80 4.33 x 10-5
80 1.87 x 10-5
2 0 3.01 x 10-5
3 0 1.11 x 10-4
40 4.20 x 10 -4
20 1.10 x 1o-4
2 5 2.05 x 1O-4
2 5 3.15 x 10-4
2 5 6.38 x 1O-4
3 0 3.88 x 1O-4
3 5 6.67 x 1O-4
5 5 6.543 x 1O-5
60 1.171 x 10-4
6 5 2.663 x 1O-4
70 5.016 x 1O-4
8 0 2.73 x lo-*
8 0 4.82 x lo-*
8 0 7.57 x 10-5
8 0 4.43 x 10-2
aj
a,k
117.6 a
a
a
a
a
a
a
a
100.6 h
a
a,k
aj
ai
a,k
119.7
81.2
am 1
am 1
a
a
h
126.4 a
126.8 a
130.5 a
98.0
90. 8
Vl
n
t10
110
t10
t10
am I
am I
am I
am 1
16
16
126,337
126,337
126,337
10
10
1 0
1 0
1 0
2 8 3
283
19
1 9
1 9
19
19
8 2
78
7 8
7 8
7 8
7 8
7 8
232
232
5
5
8 2
8 2
5
5
5
2 8 3
2 8 3
2 8 3
222
222
222
222
222
222
1 6 4
1 6 4
1 6 4
1 6 4
6
6
6
6
5 1 1.02 x 10-5
5 1 9.61 x 1O-4
51 1.67 x 1O-3
t5
1 0 8
1 0 8
1 0 8
70 2.08 x 1O-5 a 8 9
70 8.03 x 10-5 a 8 9
60 9.5 x lo-
60 6.1 x 1O-7
8 0 9.4 x 10-6
50 3.44 x 10-6
70 5.78 x 10-5
8 5 3.78 x 1O-4
128.9 a
a
a
9 5
1 1 6
1 1 6
1 2 6
1 2 6
1 2 6
Table 4. contd
Acyl Peroxides II/39
Number of
C atoms Initiator Solvent
T(C) kd (s-l) E. Wmol) Notes Refs.
16 (contd) Caprylyl peroxide Mineral oil
p-(Chloromethyl)benzoyl peroxide Ac e t o n e
3-Cyanobenzoyl peroxide
4-Cyanobenzoyl peroxide
Cycloheptane formyl peroxide
Cyclohexane acetyl peroxide Carbon tetrachloride
2-Ethyl-4-methyl-2-pentenoyl
p e r o x i d e
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-norbomane-2-carbonyl-
peroxide
Exo-norbomane-2-carbonyl-
peroxide
Endo-norbomene-Scarbonyl-
peroxide
Exo-norbomene-karbonyl-
peroxide
Dioctanoyl peroxide n - He p t a n e
T H F
To l u e n e
Dioxane
Ac e t o p h e n o n e
Dioxane
Carbon tetrachloride
Mineral oil
Mineral oil
Mineral oil
Ac e t o n e
Chloroform
To l u e n e
Ac e t o p h e n o n e
Ac e t o p h e n o n e
Dioxane
Ac e t o p h e n o n e
Dioxane
Ac e t o p h e n o n e
Ac e t o p h e n o n e
Dioxane
Ac e t o p h e n o n e
Dioxane
Carbon tetrachloride
Carbon tetrachloride
Carbon tetrachloride
Carbon tetrachloride
T (K)
9.8 x 1015
7 0 2.07 x 1O-5
7 0 1.82 x 10-5
7 0 1.15 x 10-5
7 0 8.8 x 1o-6
8 0 1.70 x 10-2
8 0 2.43 x 1O-5
8 0 2.03 x 1O-5
3 5 7.85 x 10 -5
4 0 1.63,1.34x 1O-5
4 5 2.02 x 10-4
6 5 1.27 x 1O-5
7 0 2.76 x 1O-5
7 5 3.61 x 1O-5
54.4 3.1 x 10-6
64.3 1.19 x 10-5
71.8 2.95 x 1O-5
exp[- 140.1/RT)
m7
am I
a
am L
1
307
3 0 7
3 0 7
307
6
5
6
3 4
3 4
3 4
3 4
3 4
3 4
2 4
2 4
2 4
T 6)
7.1 x 106
T 6) 1.2 x 104
T (K)
1.6 x 1016
0 2.60 x 1O-5
0 3.98 x 10 -5
0 1.3 x 1o-5
5 0 6.0 x 1O-5
8 0 2.15 x 1O-3
8 0 6.42 x lo-
8 0 5.75 x 10-5
8 0 1.56 x 1O-4
8 0 1.18 x 1O-4
7 0 9.02 x 1O-5
8 0 4.70 x 10-5
8 0 4.40 x 10 -5
8 0 5.92 x 1O-5
8 0 6.13 x 1O-5
exp[- 138.4/RT]
exp[- 106.4/RT]
exp[- 136.3/RT]
113.8
120.9
120.1
126.4
126.4
125.1
c ,e,q
4
a
a
a
a,m 1
a
a,m L
a
a
am 1
a
am I
1
1
1
7 9
7 9
7 9
5
5
5
6
5
6
5
5
6
5
6
44.5 6.1 x lo+
j
2 3
53.9 2.83 x 1O-5
j
2 3
65.9 1.25 x 1O-4
j
2 3
44.5 9.1 x 10-6 j m2 2 3
53.9 4.33 x 10-5 j, m2 2 3
65.9 1.28 x 10-4
j m2
2 3
44.5 4.68 x 1O-5
j
2 3
53.9 2.05 x 10 -4
j
2 3
65.9 8.18 x 10-4
j
2 3
44.5 7.2 x 1O-5 j. m2 2 3
53.9 1.60 x 1O-4 jm2 2 3
65.9 8.48 x 1O-4
i m2
2 3
44.5 6.30 x lo- j
2 3
53.9 1.21 x 10-4
j
2 3
65.9 7.18 x 10-4
j
2 3
445 2.22 x lo- j,m2 2 3
53.9 4.52 x 1O-5
i m2
2 3
65.9 2.37 x 1O-4 i m2 2 3
44.5 6.58 x 1O-5
j
2 3
53.9 1.21 x 10-4
j
2 3
65.9 8.42 x 1O-4
j
2 3
44.5 2.58 x 1O-5 km2 2 3
53.9 1.20 x 10-4
i m2
2 3
65.9 7.10 x 1o-4 j m2
2 3
7 0 1.70 x 10-5 z (1500) 377
8 0 7.01 x 10-5
z (500)
377
8 0 6.80 x 10-5
z (low
3 7 7
Notes page II - 69; References page II - 70
II/40 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
Table 4. contd
Number of
C atoms Initiator Solvent T ((-2 kd (S-l) E. Wmol) Notes Refs.
16 (contii) Dioctanoyl peroxide n-Heptane
Dioctanoyl peroxydicarbonate Chlorobenzene
Phenylacetyl peroxide
Triptoyl peroxide Benzene
18 Apocamphoyl peroxide
cis-5-fert-Butylcyclohexylformyl-
m-chlorobenzoyl peroxide
frans-4-ferr-Butylcyclohexylformyl-
m-chlorobenzoyl peroxide
5-terr-Butylthenoyl peroxide
Cinnamoyl peroxide
Acetonitrile
2-Butanol
Carbon tetrachloride
Cyclohexane
Carbon tetrachloride
Styrene
Dibenzoyl succinoyl diperoxide Unknown
Nonanoyl peroxide
Isononanoyl peroxide (3,5,5-
trimethylhexanoyl peroxide)
2-Nonenoyl peroxide
exp[- 129,05/RT]
Acetonitrile
Benzene
Carbon tetrachloride
Cyclohexane
Styrene
Toluene 9 6 . 2 f,u 1
f,u 1
Benzene
8 0 6 . 2 7 x 1O-5
8 0 6.01 x 1O-5
8 0 5 . 7 7 x 10-5
90 2 . 1 3 x 1O-4
9 5 3 . 8 0 x 1O-4
1 0 0 6 . 7 9 x 1O-4
6 3 1.93 x 10-5
8 0 1.93 x 10-4
1 0 0 1.93 x 10-3
T W
2 . 3 0 x lOI5
2 0 1.02 x 10-3
2 0 4 . 7 6 x 1O-4
2 0 1.86 x 10-4
2 0 1.60 x 1O-4
0 7 . 8 x 10m5
0 2 . 5 0 x lo-
18 3 . 3 4 x 10-4
8 0 1.42 x 1O-4
8 0 1.4 X 10-4
8 0 2 . 3 x 1O-4
3 7 7
3 7 7
3 7 7
377
377
3 7 7
344
344
344
344
1 6 7
1 6 7
1 6 7
1
I
1 6 7
316
5 9
5 9
1 0 2
244
102
Acetonitrile 40 5 . 9 x 10-3 256
2-Butanol 40 4 . 4 x 10-3 256
Carbon tetrachloride 40 6 . 7 x 1O-4 256
Cyclohexane 40 4 . 4 x 10-4 256
40 4 . 2 x 1O-3
40 2 . 8 x 1O-3
40 6 . 5 x 1O-4
40 3 . 9 x 1om4
75 4 . 0 3 x 10-5
5 0 1 . 2 0 x 10-5
7 0 1.67 x 1O-4
7 0 7 . 7 x 10-6
7 5 1.42 x 1O-5
8 5 5 . 4 x 10-5
T (K)
8 . 4 x lOI
am I
1 2 5 . 5 Xl
Xl
X l
exp[- 127.1/RT]
256
256
1
256
256
232
316
316
214
214
214
1 Mineral oil
Benzene
Chlorobenzene
n-Heptane
Mineral oil
5 0 6.1 x 1O-6
7 0 8 . 0 2 x 1O-5
8 5 5 . 3 0 x 1o-4
60 1.9 x 10-5
5 9 1.93 x 10-5
7 7 1.93 x 1o-4
9 6 1.93 x 10-3
T (K)
2 . 8 4 x lOI5
6 0 5 . 2 8 x 1O-6
7 0 2 . 0 6 x lo-s
8 0 9 . 5 3 x 10-5
8 0 9 . 1 0 x 10-5
8 0 8 . 6 2 x 10m5
8 0 8 . 2 4 x 1O-5
8 0 7 . 8 6 x 1O-5
8 0 7 . 4 6 x 1O-5
9 0 2 . 5 2 x 1O-4
1 0 0 8.81 x 1o-4
1 2 0 6 . 9 8 x 1O-3
125 1.27 x 10m2
1 3 0 2 . 1 5 x lo-*
135 2.60 x 1O-2
1 4 0 5.71 x 10-2
145 8 . 6 2 x 1O-2
1 5 0 1.17 x lo-
T 09
1.6 x lOI
z (1500)
z (2000)
z (2500)
z (1500)
z (1500)
z (1500)
1 2 6 a
a
a
exp[- 128.34/RT]
z (1500)
z (1500)
z (1)
z (500)
z (1000)
z (1500)
z (2000)
z (2500)
z (1500)
z (1500)
z (1500)
z (1500)
z (1500)
z (1500)
z (1500)
i (1500)
z (1500)
exp[- 128.8/RT]
337
337
3 3 7
3 3 8
344
344
3 4 4
344
3 7 7
3 7 7
3 7 7
3 7 7
3 7 7
3 7 7
3 7 7
3 7 7
377
377
377
377
377
377
377
3 7 7
3 7 7
1
Table 4. contd
Acyl Peroxides II/41
Number of
C atoms Initiator Solvent T (0 kd (S-I) E. Wmol) Notes Refs.
18 (conrd) 3-Nonenoyl peroxide
2-Phenylpropionyl peroxide
19 Dibenzoyl itaconyl diperoxide
Dibenzoyl a-methylsuccinoyl-
diperoxide
2 0 De c a n o y l p e r o x i d e Be n z e n e
Dioctanoyl a-bromosuccinoyl-
diperoxide
Dioctanoyl a-chlorosuccinoyl-
diperoxide
21
Dioctanoyl a-chlorosuccinoyl-
diperoxide
4-Ethyl-2-octenoyl peroxide
Dioctanoyl itaconoyl diperoxide
Dioctanoyl a-methyl succinoyl-
diperoxide
2 2 Benzoyl 2-[nuns-2-(3-nitrophenyl)-
vinyllbenzoyl peroxide
Benzoyl 2-[rrans-2-(4nitrophenyl)-
vinyllbenzoyl peroxide
Benzoyl 2-[truns-2-(4nitrophenyl)-
vinyl]-4-nitrobenzoyl peroxide
Benzoyl 2-[rrans-2-(phenyl)vinyl]-
benzoyl peroxide
4-Benzylidenebutyryl peroxide
Mineral oil T 6)
Cyclohexane 55.8
On silica 49.4
St y r e n e IO
Un k n o wn 70
exp[- lOS.O/RZJ
83.7
115.1
15
8 5
Un k n o wn 70 82.8
116.3
7 5
8 5
127.2
XZ
x2
x2
x2
x2
x2
x2
x2
x2
x2
x2
x2
a
a
a
Ch l o r o b e n z e n e
Mineral oil
Un k n o wn
60
IO
8 5
6 3
8 0
1 0 0
T 6)
T 6)
70
exp[- 130.48/RT]
exp[- 131.9/Rfl
96.2
126.4
15
8 5
Un k n o wn 70 95.4
126.4
15
8 5
3.1 x 104
6.8 x 10-6
7.5 x 10 -5
5.5 x 10-5
5.63 x 1O-4
1.87 x 10-5
8.63 x 1O-4
3.62 x lo--
1.69 x 1O-3
1.00 x 10-4
2.74 x 1O-4
1.26 x 1O-5
4.26 x 1O-4
2.40 x 1O-5
9.60 x 1O-4
8.7 x 1O-5
1.53 x 10-5
5.67 x 1O-5
3.80 x 1O-4
1.93 x 10-5
1.93 x 10-4
1.93 x 10-9
3.64 x lOI
2.7 x lOI
1.52 x 1O-4
1.82 x 1O-5
2.74 x 1O-4
3.83 x 1O-5
6.91 x 1O-4
1.15 x 10-4
2.02 x 1o-4
2.42 x 1O-5
3.23 x 1O-4
4.83 x 10-5
8.50 x 10-4
x2
x2
x2
x2
x2
x2
x2
x2
x2
x2
x2
Un k n o wn 8 5
Mineral oil
T 6)
Un k n o wn 70
x2
expI- 127.41~~~
92.9
127.6
15
8 5
Un k n o wn 70 96.2
131.0
75
8 5
Ch l o r o b e n z e n e 70
1.58 x 10-4
8.2 x 104
3.23 x 1O-4
2.80 x 10-5
5.47 x 1o-4
5.60 x 10 -5
1.28 x lo-
1.92 x 1O-4
5.48 x 10-4
5.88 x lO-5
9.58 x 1O-4
1.06 x 10 -4
2.61 x 1O-3
3.84 x 10-4
1.87 x 1O-4
x2
x2
x2
x2
x2
x2
x2
x2
x2
XZ
x2
x2
t9
Ch l o r o b e n z e n e 70 1.18 x 10-4 t9
T H F 70 6.2 x 10 -5 t9
Ch l o r o b e n z e n e IO 1.54 x 10-5
t9
Ch l o r o b e n z e n e 3 5 9.42 x 1O-5
IO 3.02 x 1O-3
3 5 9.77 x 10-4
50 7.92 x 10 -5
5 5 1.45 x 10-4
6 5 4.13 x 10-4
T 6)
1.07 x 102
5 5 1.38 x 10-4
84.5
Me t ha nol
Ac e t o p h e n o n e 99.6
h,b
t9
t9
exp[- 99.6/RT]
98.7 m2
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
214
1
214
214
214
214
214
214
214
214
214
214
214
214
1 7 5
1 7 5
1 7 5
175
1 7 5
175
175
133
133
1 3 3
1 3 3
133
Not es page I I - 69; References page II - 70
I I / 42 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
Table 4. contd
Number OP
Catoms Initiator Solvent T (C) kd (S-l) E, Wmol) Notes Ref s.
22 (conrd) 4-Benzylidenebutytyl peroxide Acetophenone
4-ferr-Butylbenzoyl peroxide
cis-4-rert-Butylcyclobexane formyl-
peroxide
mans-4-reti-Butylcyclobexane formyl-
peroxide
frans-4-(4-Chlorobenzylidene)-
butyryl peroxide
Benzene
Carbon tetrachloride
Nitrobenzene
Propylene carbonate
Toluene
Dioxane
Butane
Carbon tetrachloride
Carbon tetrachloride
Benzene
Propylene carbonate
rrans-4-(4-Fluorobenzylidene)-
butyryl peroxide
Propylene carbonate
I-Naphthoyl peroxide
4-Nitrobenzoyl-2-[trans-2-(4-nitro-
phenyl)vinyl] benzoyl peroxide
2-Phenylisovaleryl peroxide
5-Phenylpenta-2,4-dienoyl-peroxide
SPhenylpentanoyl peroxide
2 4 Dibenzoyl 2-bromosebacoyl-
diperoxide
Dioctanoyl 2-bromosebacoyl-
diperoxide
Chlorobenzene
Acetonitrile
Cyclohexane
On silica
Styrene
Acetophenone
Benzene
Carbon tetrachloride
Propylene carbonate
Unknown
Unknown
6 5 4.02 x 1O-4
T 6) 7.14 x 10
50 2.40 x 1O-5
6 0 6.80 x 10-5
70 1.845 x 1O-4
6 0 3.47 x 10 -5
70 1.06 x 1O-4
T 09 1.42 x lOI3
60 3.38 x 1O-4
40 7.36 x 1O-5
50 2.13 x 1O-4
T W 5.93 x loto
5 0 2.08 x 1O-4
40 7.23 x 1O-5
5 0 2.093 x 1O-4
60 5.117 x 1o-4
70 1.64 x 1O-4
8 0 6.08 x 10-2
40 1.25 x 10-5
40 1.69 x lo-s
4 0 . 0 (8.65 f0.35) x 1O-5
4 5 . 4 5 (1.32 hO.04) x 1O-4
5 0 . 7 (2.35 f 0.05) x 10 -4
4 0 . 0 (4.25 k 0.23) x 1O-5
4 4 . 7 (7.10i0.38) x 1O-5
4 8 . 9 (1.14ik0.04) x 10-4
50 2.10 x 10-5
6 0 6.56 x 1O-5
70 1.75 x 10-4
40 5.33 x 10-5
5 0 1.448 x 1O-4
60 2.791 x 1O-4
5 0 2.67 x 1O-5
60 8.44 x 1O-5
70 2.119 x 1O-4
40 6.53 x 1O-5
50 1.685 x 1O-4
60 4.540 x 10 -4
5 4 . 6 1.01 x 1o-4
5 9 . 9 1.86 x 10-4
6 4 . 5 3.0 x 1o-4
70 6.06 x 10-5
5 5 . 0
55.0
50
7 0
7 7
7 7
7 0
7 7
8 5
T 6)
60
60
7 0
7 5
8 5
7 0
7 5
2.27 x 10 -5
6.4 x lO-j
2.56 x 1O-4
2.18 x 1O-4
2.37 x 1O-4
1.054 x 10 -5
2.76 x 1O-5
7.19 x 10-5
1.87 x 1O-4
1.76 x 1015
4.41 x 10-5
2.80 x 1O-5
4.80 x 1O-4
3.87 x lo-
7.64 x 1O-4
7.22 x lo-
2.00 x 10-3
2.02 x 1o-4
6.46 x 1O-4
5.23 x 1O-5
1.171 x 10-5
7-2
m2
e x p [ - 98.7/RT] rn2
91.2 h
112.5
m2
m2
exp[- 112.5/RT] rn2
8 9 . 5
exp[- 89.5/R7J
8 2 . 0
mz
h
76.1
am 1
z (0.98)
z (1010)
h
8 1 . 6 h
95.0 h
94.1 h
t9
n2
1 2 7 . 6
130.1
hm
m2
m2
m2
e x p [ - 130.1/RT] mz
m2
8 7 . 9
x2
110.8
XZ
x2
x2
x2
x2
9 9 . 6 x2
1 2 9 . 7
x2
133
133
1 9 4
1 9 4
1 9 4
133
133
133
133
133
133
133
133
1 9 4
1 9 4
1 9 4
1 3 3
6
1 4 5
145
3 5
3 5
3 5
3 5
3 5
3 5
1 9 4
1 9 4
1 9 4
1 9 4
1 9 4
1 9 4
1 9 4
1 9 4
1 9 4
1 9 4
1 9 4
1 9 4
1 7 0
1 7 0
1 7 0
175
258
258
258
316
1 3 3
1 9 4
1 3 3
1 3 3
133
133
1 3 3
133
214
214
214
214
214
214
214
214
214
i
:
Table 4. contd
Hydroperoxides and Ketone Peroxides II/43
Number o f
C atoms Initiator Solvent TV3 kd (s-l) E, W/mol) Notes Ref s.
24 (conrd) Dioctanoyl 2-bromosebacoyl- Unknown
diperoxide 8 5
Lauroyl peroxide Benzene 3 0
40
5 0
60
70
60
70
8 5
70
Carbon tetrachloride 40
5 0
60
70
Chlorobenzene 6 1
79
9 9
T 6)
Ethyl acetate 40
50
61
70
Ethyl ether 3 0
Mineral oil
T 6)
3 4 . 8
49.4
6 1 . 0
7 4 . 8
1 0 0 . 0
5 0
60
6 5
70
trans-4-(4-Methoxybenzylidene)- Benzene 50
butyryl peroxide
rrans-4-(4-Methylbenzylidene)- Benzene 5 0
butyryl peroxide 60
70
26 2-Phenoxybenzoyl peroxide Acetophenone 6 5
28 Myristoyl peroxide Benzene 7 0
36 Menthylphthaloyl peroxide D i o x a n e 5 5
x Aliphatic polymeric Chlorobenzene 7 5
diacyl peroxide 7 5
8 0
1.08 x 1O-4
3 . 0 0 x 1o-3
3 . 7 2 x 1O-4
2 . 5 6 x 1O-7
4 . 9 1 x 10-7
2 . 1 9 x 10-6
9 . 1 7 x 10-6
2 . 8 6 x 1O-5
1.51 x 10-5
5 . 5 8 x 1O-5
3 . 7 5 x 10-4
4 . 3 3 x 10-5
2.91 x lo-
1.15 x 10-6
4 . 7 5 x 10-6
1.87 x lo-
1.93 x 10-5
1.93 x 10-4
1.93 x 10-3
3 . 9 2 x 1o14
6 . 0 3 x lo-
2.70 x lO-6
1.05 x 10-5
3 . 9 9 x 10-5
1.97 x 10-6
2 . 2 x 106
2 . 0 6 x lo-
2 . 2 5 x 1O-6
1.42 x lO-5
1.00 x 10-4
2 . 3 9 x 10-3
3.1 x 10-6
1.20 x 10-5
2 . 2 2 x 10-5
4 . 3 2 x 1O-5
2 . 0 3 x 1O-4
6 . 5 8 x 1O-5
1 . 8 1 5 x 1O-4
4.729 x 10 -4
8 . 1 8 X 10-5
3 . 3 8 x 1O-5
1.15 x 10-4
9 . 0 4 x 10-5
9.00 x 10-5
1 . 7 2 0 x 10 -4
x2
x2
x2
a
1 2 7 . 2 a
a
a
aj
exp[- 123.37/RT]
a
exp[- 137.9/RTj
a
a
a
a
a
121.1
90.4
c,h
C
C
121.3 a
a
v 14
v 15
VI5
214
214
214
9 9
6 8
6 8
6 8
6 8
1 2 6 , 3 3 7
1 2 6 , 3 3 7
1 2 6 , 3 3 7
16
6 8
6 8
6 8
6 8
344
344
344
344
6 8
6 8
6 8
6 8
9 9
1
10
10
1 0
1 0
1 0
287
2 8 7
2 8 7
287
1 9 4
1 9 4
1 9 4
1 9 4
5
16
6 5
3 0 2
302
302
TABLE 5. HYDROPEROXIDES AND KETONE PEROXIDES
Number of
C at oms Initiator Solvent
T ((3 kd (S-l) E. Wmol) Notes Ref s.
4 set-Butyl hydroperoxide Toluene
terr-Butyl hydroperoxide Benzene
1 7 2 . 0 2 . 6 5 x 1O-5
182.3 4 . 9 x 10-5
1 3 0 3 x 10-7
145 1.6 x 10-6
1 6 0 6 . 6 x 10-6
154.5 4.29 x 10-6
161.7 9 . 2 7 x 10-6
169.3 2 . 0 x 10 -5
1 7 4 . 6 4 . 0 x 10-5
1 3 8
1 7 0 . 7
1 9 9
1 9 9
3 3 7
3 3 7
337
7 6
7 6
7 6
7 6
Notes page II - 69; References page II - 70
II / 44 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 5. contd
1
Number of
c atoms Initiator Solvent
T (C) ka (S-1 E, Wmol) Notes Refs.
1
t
4 (contd) tert-Butyl hydroperoxide Be n z e n e
Ch l o r o b e n z e n e
C u m e n e
Cyclohexane
Do d e c a n e
He p t a n e
n- Oc t a ne
To l u e n e
Va p o r
tert-Butyl hydroperoxidelcobalt
Z-Ethyl hexanoate
rerr-Butyl hydroperoxide/cobalt
s t ear at e
Methyl ethyl ketone peroxides
rert-Amy1 hydroperoxide
Acetone cyclic diperoxide
3,3,6,6-Tetramethyl- 1,2,4,5-
t e t r o x a n e
Ch l o r o h e n z e n e
Be n z e n e
Ethyl acetate
Ch l o r o b e n z e n e
To l u e n e
Be n z e n e
To l u e n e
Va p o r
Cyclohexyl hydroperoxide Be n z e n e
Benzenelstyrene (50/50)
172.3 1. 09 x 10-5
182.6 3.1 x 10-5
171 1.93 x 10-5
1 9 9 1.93 x 10-4
2 3 1 1.93 x 10-3
182.6 8.1 x 1O-5
1 0 0 1.2 x 10-7
1 7 2 1.41 x 10-4
86.1 1.32 x 1O-6
98. 5 5. 55 x 10-6
172 1.41 x 10-4
149. 8 8 x 1O-6
159. 9 2. 5 x 1O-5
169. 6 6. 9 x 1O-5
179. 6 1.82 x 1O-5
1 0 0 5. 7 x lo-s
172.5 9. 2 x lo+
181.5 2. 69 x 1O-5
192.6 8. 3 x 1O-5
204. 5 1.52 x 1O-4
214. 9 3. 24 x 1O-4
570 3. 4 x 10
670 4. 95
773 8. 4 x 10
873 5. 66 x lo*
973 2. 58 x lo3
0 1.01 x 10-3
0 8. 29 x 1O-5
0 5. 40 x 10-4
25 2. 3 x 1O-3
25 1.1 x 10-3
45 1.4 x 10-3
45 1.0 x 10-3
1 0 0 1.3 x 10-5
115 4. 80 x 1O-5
1 3 0 1.60 x 10-4
70 1.28 x 1O-6
153 1.93 x 10-5
190 1.93 x 10-4
228 1.93 x 10-3
135. 5 6. 25 x lo-
145. 5 2. 09 x lo+
165. 0 1.41 x 10-5
165. 0 1.37 x 10-5
135. 5 6. 25 x lo-
140. 5 1.19 x 10-6
145. 5 2. 09 x 10-6
150. 5 2. 83 x 1O-6
165. 0 1.41 x 10-5
165. 0 1.37 x 10-5
130. 1 1.8 x 1O-6
150. 1 3. 4 x 10-6
170. 1 3. 5 x 10-6
177. 1 4. 6 x 1O-6
185. 1 1.3 x 10-5
194. 1 2. 4 x 1O-5
207. 1 8. 5 x 1O-s
215. 1 1.66 x 10-4
250. 1 4. 88 x 1O-4
70 0
70 1.27 x 1O-3
130 2. 38 x 1O-3
140 1.16 x 1O-2
150 3. 20 x lo-*
C
C
128.4 b
b
163. 2 f
C
VI0
Vl
VI
101
Vl
a
a
a
147. 1 b
1 9 9
1 9 9
t
i
54
344
344
344
199
199
199
41
41
199
118
118
118
118
199
199
I
71
1 9 9
1
1 9 9
81
199
I
199
,
188
188
188
188
188
190
190
190
198
198
198
198
337
337
(1
337
13
344
9
344
344
286
286
286
286
373
373
373
373
373
373
365
365
365
365
365
365
365
365
365
91
91
1
9 1
9 1
91
TABLE 5. contd
Hydroperoxides and Ketone Peroxides II/45
Number of
C atoms Initiator Solvent
T(C) kd (S-l) E, Wmol) Notes Ref s.
Benzyl hydroperoxide
1,4-Dimethylcyclohexane-
hydroperoxide
1,1,3,3-Tetramethylbutyl-
hydroperoxide
Cumyl hydroperoxide
6 (co&d) Cyclohexyl hydroperoxide Benzene
Cyclohexane
8 0
80
Cyclohexene 8 0
Dimethylheptadiene 8 0
1-Octene 8 0
Styrene
1,4-Dimethylcyclohexane
Benzene
Chlorobenzene
60
60
1 2 0
1 3 0 1.7 x 1o-s
145 7.41 x 10-5
1 6 0 2.83 x lO-4
135 1.93 x lo-s
1 5 3 1.93 x 10-4
1 7 3 1.93 x 10-3
@)x
9
2,5-Dimethyl-2,5-di(hydro-
peroxy)hexane
n-Octyl hydroperoxide
2,4,4-Trimethylpentyl-
2-hydroperoxide
Poly(phenyleneethy1 hydro-
peroxide)/manganese resinate
Cumene hydroperoxide
Benzene
White oil
White oil
Chlorobenzene
Benzene
Chlorobenzene
1 3 0 2.7 x 1O-6
1 4 5 1.0 x lo-s
1 6 0 3.16 x lO-5
1 5 0 9.29 x lo-
1 5 0 9.29 x lO-5
Cumene
2 6 2.00 x 10-4
30 2.75 x lO-4
3 5 3.67 x 1O-4
1 1 5 4 x 10-7
1 3 0 1.7 x 10-6
1 4 5 6.6 x 10-6
1 5 9 1.93 x 10-5
1 9 3 1.93 x 10-4
2 5 3 1.93 x 10-3
1 1 0 2.742 x 1O-6
1 2 0 5.194 x 10-6
1 3 2 9.305 x 10-6
T 6) 2.10 x 10
Mesitylene
Styrene
Toluene
White oil
Acetone-d6
125 9 x 10-6
1 3 9 3 x lo-5
1 8 2 . 3 6.45 x 1O-5
1.50 1.34 x 10-4
- 33.0 7.0 x 10 -s
- 23.0 2.28 x 1O-4
- 12.0 1.21 x 10-3
- 18.0 8.3 x 1O-5
- 8.0 4.23 x 1O-4
1 0 p-Cymene hydroperoxide p-Cymene
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
9 x 10-6
1.8 x 1O-5
1.4 x lo-s
- 3.0 1.65 x lO-3
1 1 0 5.500 x 10 -e
1 2 0 1.200 x 10-5
1 3 2 2.089 x 10 -
T W
1.23 x lo*
1 3 7 . 2
1 3 4
1 1 3
112.5
112.5
46.0
1 2 2
exp[- 80.O/RT]
9 8 . 7
101.3
1 2 1 . 3
6 2 . 0
110.2
exp[- 85.48/RT]
c3 276
c4
276
c 224
a
a
a
3 3 7
337
3 3 7
344
344
344
a
a
a
a
a
t3
t3
t3
a
a
a
337
337
3 3 7
1 7 7
1 7 7
a
t 14
t14
t14
212
212
212
3 3 7
337
3 3 7
344
344
344
3 6 7
3 6 7
3 6 7
3 6 7
5 8
5 8
1 9 9
1 9 9
1 9 9
177
264
264
264
264
264
264
367
367
367
3 6 7
1 1 9
1 1 9
1 1 9
1 1 9
1 1 9
Notes page II - 69; References page II - 70
II/46 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 5. contd
Number of
C atoms Initiator Solvent T (C) ka (S-l) E. Wmol) Notes Refs.
10 (contd) Decalin hydroperoxide
Pinane hydroperoxide
2-Phenylbutyl 2-hydroperoxide set-Butylbenzene
1-Phenyl-2-methylpropyl-
hydroperoxide
I-Phenyl-2-methylpropyl-2-
hydroperoxide
Tetralin hydroperoxide
(10) Poly(cumyleneethylhydroperoxide)
(Mw 1100)
11 2,2-Bis(fert-butyldioxy)propane
1-Methoxy-1-(rerr-butylperoxy)
cyclohexane
set-Butyltoluene hydroperoxide set-Butyl toluene
12 2,2-Di-(ferf-butylperoxy)butane Chlorobenzene
2,2-Bis(terf-butyldioxy)butane
Diisopropylbenzene
monohydroperoxide
I-Methoxy-1-(rerr-amylperoxy)
cyclohexane
Acetic acid
Chlorobenzene
Decalin
1,2-Dichlorobenzene
Ethylene glycol
Nitrobenzene
Pyr i di ne
Benzene
Benzene
Poly(butene)
n-Butyl stearate
2-Ethyl-1-hexene
1-Hexadecene
Mineral oil
n-Octadecane
Isooctane
Octyl ether
Poly(propylene)
n-Tetradecane
Tetralin
2,2,4-Trimethyl-l-pentene
white oil
Cumene
Chlorobenzene
Cumene
1 3 0 5 . 5 x 10-4
1 3 0 10% in 3 h
1 3 0 1.41 x 10-5
1 3 0 4 . 4 8 x 1O-5
1 3 0 1.65 x 1O-4
1 3 0 4 . 7 3 x 10-5
1 3 0 (2.31-2.89) x 1O-4
1 3 0 7 . 0 8 x 1O-6
1 4 5 2 . 7 2 x 1O-5
1 6 0 9 . 1 7 x 10-5
1 1 0 2.944 x 1O-6
1 2 0 6 . 6 1 1 x 10-6
1 3 2 1 . 0 8 9 x 1O-5
T (K)
4.06 x 10 I2
133.8 3 . 1 8 x 1O-6
143.9 8 . 9 5 x 1O-6
1 5 3 . 9 2 . 0 x 10-5
1 6 3 . 7 4 . 0 3 x 10-5
1 7 4 9 . 7 7 x 10-5
1 4 4 . 2 5 . 0 4 x 10-6
154.5 1.21 x 10-5
1 6 5 . 6 2 . 9 2 x 1O-5
1 7 6 . 0 6 . 9 7 x 1O-5
1 7 0 2 . 1 7 x 1O-3
1 7 0 1.47 x 10-4
1 3 0 1.08 x 1O-4
1 7 0 1.26 x 1O-3
1 7 0 7 . 9 2 x 1O-4
1 3 5 . 6 4 . 2 x 1O-5
1 5 0 . 6 1.00 x 10-4
1 7 0 4.82 x 1O-4
1 7 0 2 . 5 4 x 1O-4
1 7 0 131 x 10-4
1 7 0 1.45 x 10-3
1 7 0 2 . 5 0 x 1O-3
1 7 0 2 . 3 2 x 1O-4
T W
2.27 x lo9
1 7 0 1.67 x 1O-3
1 5 0 1.34 x 10-4
1 3 0 2 . 7 9 x 1O-5
1 4 0 4 . 0 x 10-5
1 5 0 5 . 7 8 x 1O-5
90 2 . 1 6 x 1O-6
1 0 0 9 . 1 4 x 10-6
1 1 0 2 . 9 7 x 1O-5
1 2 0 9 . 5 6 x 1O-5
8 0 4.79 x 10-6
90 1 . 8 9 8 x 1O-5
1 0 0 6 . 5 7 x 1O-5
1 1 0 2.139 x 1O-4
1 0 0 4 . 1 1 1 x 10-6
1 1 0 8.194 x 1O-6
1 2 0 1 . 9 5 5 5 x lo-
T 6)
1.02 x 106
9 8 1.93 x 10-5
1 1 6 1.93 x 10-4
1 3 6 1.93 x 10-3
T W
9 . 3 0 x 106
1 0 0 1 . 8 4 x 1O-5
1 5 0 1.93 x 10-5
1 8 2 1.93 x 10-4
218 1.93 x 10-3
8 0 7 . 8 2 x 1O-6
90 3 . 0 7 x 10-5
124.3
1 7 6 . 4
1 1 7 . 2
123.8
exp[- 87.15/RT]
1 2 2 . 2
125.5 h
7 8 . 2
125.5
8 2 . 8
1 1 7 . 2
1 3 1 . 4
1 1 9 . 2
1 2 1 . 3
exp[- 102.1/RT]
121.3
exp[- 110.2/RT]
exp[- 154.08/RT]
a
a
a
h
t3
t3
e,t 3
t3
t3
t3
e,t 3
t3
t3
t3
t3
t3
t3
t3
2 2 8
2 2 8
2 2 8
2 2 8
2 2 8
2 2 8
2 2 8
18
18
18
3 6 7
3 6 7
3 6 7
3 6 7
7 6
7 6
7 6
7 6
76
76
76
7 6
7 6
7 1
7 1
7 1
7 1
71
71
71
71
71
7 1
71
7 1
7 1
1 1 2
7 1
1 7 7
210
210
210
3 6 1
3 6 1
3 6 1
3 6 1
348
348
348
348
367
367
367
367
344
344
344
344
3 6 1
344
344
344
348
3 4 8
TABLE 5. contd
Hydroperoxides and Ketone Peroxides II/47
Number of
C atoms Initiator Solvent
TV3 kd (S-l) E, Wmol) Notes Refs.
12 (contcq
13
1 -Methoxy- 1 -@err-amylperoxy)
cyclohexane
1-Methoxy-1-(ten-hexylperoxy)
cyclohexane
l,l-Bis(terr-butylperoxy)-
c y c l o p e n t a n e
2,2-Bis(?ert-butyldioxy)-3-methyl-
b u t a n e
14 l,l-Bis(rert-butylperoxy)-
cyclohexane
C u m e n e
C u m e n e
C u m e n e
Diphenylmethane
C u m e n e
C u m e n e
Ch l o r o b e n z e n e
n - Do d e c a n e
n- He xa de c a ne
n-Hexane
n - No n a n e
C u m e n e
Ch l o r o b e n z e n e
Cumene
C u m e n e
C u m e n e
Cumene
C u m e n e
C u m e n e
C u m e n e
l,l-Bis(fert-butylperoxy)-2-methyl-
c y c l o p e n t a n e
1,l -Diphenylethyl hydroperoxide
1 5 I-Methoxy-l-(terr-octylperoxy)-
cyclohexane
1,1-Bis(rert-butylperoxy)-2-methyl-
cyclohexane
16 l,l-Bis(tert-amylperoxy)-
cyclohexane
l,l-Bis(tert-butylperoxy)-
c y c l o o c t a n e
17 l,l-Bis(rerr-butylperoxy)-2-n-propyl-
c y c l o h e x a n e
l,l-Bis(terr-butylperoxy)-
2 - i s o p r o p y l c y c l o h e x a n e
l,l-Bis(tert-butylperoxy)-
3,3,5-trimethylcyclohexane
1 0 0
1 1 0
8 0
90
1 0 0
1 1 0
8 0
90
1 0 0
1 1 0
90
1 0 0
1 1 0
1 2 0
1 0 0
8 0
90
1 0 0
1 1 0
94
113
1 3 4
T 6)
1 0 0
1 0 0
1 0 0
loo
8 0
90
1 0 0
1 1 0
90
1 1 0
1 3 0
1 5 0
T W)
70
8 0
90
1 0 0
80
90
1 0 0
1 1 0
8 0
90
1 0 0
1 1 0
90
1 0 0
1 1 0
1 2 0
8 0
90
1 0 0
70
8 0
90
1 0 0
8 0
90
1 0 0
1 1 0
1.058 x 1O-4
3.450 x 10-4
8.34 x lo-
3.17 x 10-5
1.120 x 10-4
3.653 x 1O-4
4.98 x 10 -6
1.80 x lo-
6.67 x 1O-5
2.17 x 1O-4
1.08 x 1O-5 ,
3.75 x 10-5
1.29 x 1O-4
4.11 x 10-4
3.17 x 10-5
3.47 x 10-6
1.45 x 10-5
5.06 x 1O-5
1.62 x 1O-4
1.93 x 10-5
1.93 x 10-4
1.93 x 10-3
3.47 x 10 I5 exp[- 142.4/RIJ
3.51 x 10-5
3.15 x 10-5
3.82 x 1O-5
3.62 x 1O-5
1.55 x 10-5
5.82 x 1O-5
1.85 x 1O-4
6.00 x 1O-4
2.0 x 10-9
1.007 x 10 -6
1.034 x 1o-6
1.223 x 1O-6
1.38 x lo8 exp[- 105.4/RT]
5.9 x 10-6
2.30 x lo-
8.18 x 10-5
2.840 x 1O-4
1.29 x 1O-5
4.51 x 10-5
1.43 x 10-4
4.58 x 10 -4
5.34 x 10-6
2.02 x 10-5
7.32 x 1O-5
2.44 x 1O-4
1.11 x 10-5
4.15 x 10-5
1.36 x 1O-4
4.24 x 1O-4
1.20 x 10-5
4.19 x 10-5
1.38 x 1O-4
2.59 x 1O-5
4.86 x 1O-s
1.98 x 1O-4
7.46 x lo4
3.82 x 1O-6
1.50 x 10-5
5.31 x 10-5
1.75 x 10-4
348
348
348
348
3 4 8
3 4 8
349,364
349,364
349,364
349,364
3 5 8
358
358
358
3 6 1
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
3 4 8
348
3 4 8
3 4 9
349
3 4 9
349
3 4 8
3 4 8
3 4 8
3 4 8
364
364
364
364
349
349
349
349
349
349
349
349,364
349,364
349,364
349,364
Notes page II - 69; References page II - 70
II/48 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 5. contd
Number of
C atoms Initiator Solvent
T (Cl kd (S-) E. (kJ /mol) Notes Ref s.
17 (conrd) l,l-Bis(terf-butylperoxy)- Chlorobenzene 8 5 1.93 x 10-5 3 4 4
3,3,5-trimethylcyclohexane 105 1.93 x 10-4 3 4 4
1 2 8 1.93 x 10-3 3 4 4
T WI 7 . 5 9 x 10 l3 exp[- 127.52/RT] 3 4 4
n-Butyl 4,4-di-(tert-butylperoxy) Chlorobenzene 1 0 2 1.93 X 10-5 344
valerate 121 1.93 x 10-4 3 4 4
1 4 3 1.93 x 10-3 3 4 4
T 6) 1.91 x 105 exp[- 143.51/R71 344
18 l,l-Bis(tert-hexylperoxy)- Cumene 8 0 5 . 3 8 x 1O-6 3 4 8
cyclohexane 9 0 2 . 0 6 x 1O-5 3 4 8
1 0 0 7 . 4 8 x 1O-5 3 4 8
1 1 0 2 . 4 8 x 1O-4 348
20 1,l -Bis(rert-butylperoxy)- Cumene 90 8 . 1 4 x 1O-6 364
cyclododecane 1 0 0 3 . 2 2 x 1O-5 364
1 1 0 9 . 9 3 x 10-5 364
2 2 l,l-Bis(rerr-octylperoxy)- Cumene 8 0 1.513 x 10-5 3 4 8
cyclohexane 9 0 5 . 6 2 x 1O-5 348
1 0 0 1.983 x 1O-4 348
1 1 0 6 . 2 6 x 1O-4 3 4 8
31 2,2-Bis[4,4-di-(terr-butyl- Chlorobenzene 8 7 1.93 x 10-5 344
peroxycyclohexyl)propane 1 0 6 1.93 x 10-4 344
1 2 8 1.93 x 10-3 344
T W) 8 . 7 9 x 1014 exp[- 135.56/RT] 344
TABLE 6. PERESTERS AND PEROXYCARBONATES
Number of
C atoms Initiator Solvent TV3 kd (S-) E. Wmol) Notes Ref s.
Dimethyl peroxalate
rert-Butyl percarbamate
rerr-Butyl performate
Isobutyl peracetate
n-Butyl peracetate
set-Butyl peracetate
fert-Butyl peracetate
4
5
Pentane
Chlorobenzene
Chlorobenzene
4-Chlorotoluene
Cumene
a-Methylstyrene
a-Methylstyrene
c+Methylstyrene
ferr-Amy1 alcohol
n-Butanol
2 5 1.7 x 10-5
9 0 6 . 6 x 10-6
1 3 0 . 8 5 . 4 3 x 10-5 1 5 9 . 0
1 4 0 . 8 1 . 7 0 x 10-4
1 4 0 . 6 1.80 x 1O-4
1 4 0 2 . 1 2 x 10-3 6 4 . 0
1 4 0 5 . 0 6 x 1O-4
1 4 0 . 6 1.61 x 1O-4
1 4 0 1.62 x 1O-3
1 4 0 . 6 1.77 x 10-4
1 4 0 1.02 x 10-3
7 9 . 5 1 . 3 6 x 1O-5 1 1 5 . 2
8 8 . 4 3.61 x 1O-5
9 2 . 8 5 . 5 8 x 1O-5
64 - 9.6 x 1O-3
64 8 . 2 x 1O-3
64 6 . 5 x 1O-4
6 4 1.2 x 10-3
7 9 . 6 1.57 x 10-5 1 0 1 . 0
8 7 . 8 3 . 2 7 x 1O-5
9 2 . 6 5 . 3 8 x 1O-5
8 8 . 2 1.79 x 10-5 104.3
9 2 . 8 3 . 1 9 x 10-5
9 9 . 4 5 . 3 7 x 10-5
7 5 2 . 8 x 1O-6
8 5 1.2 x 10-6
8 5 2 . 1 8 x lo+ 1 5 1 . 9
1 0 0 1.54 x 10-5
115 1.02 x 10-4
1 3 0 5 . 6 9 x 1O-4
7 5 2 . 6 5 x 1O-5
h
m2
v8
VI
v8
b
b,v 6
g2,f16
g2.v 17
g2.v18
g2.v 19
2 0 3
141
218
218
218
218
218
218
218
218
218
253
2 5 3
253
253
253
2 5 3
2 5 3
2 5 3
253
2 5 3
2 5 3
2 5 3
2 5 3
193
1 9 3
1 2 6 , 3 3 7
1 2 6 , 3 3 7
1 2 6 , 3 3 7
1 2 6 , 3 3 7
193
TABLE 6. contd
Peresters ad Peroxycarbonates II/49
Number of
C at oms Initiator Solvent
T ((3 kd (S-l) E. Wmol) Notes Refs.
6 (conrd) rerr-Butyl peracetate 2-Butanol 75 1.13 x 10-4
7 5 5 . 3 x 10-5
7 5 4 x lo-
60 2 . 3 1 x lo-*
1 0 0 1.93 x 10-5
1 1 9 1.93 x 10-4
1 3 9 1.93 x 10-3
T 6)
1.57 x 106
1 0 0 1.5 x 10-5
115 7.91 x 10-5
125 2 . 4 5 x 1O-4
1 0 0 1.95 x 10-5
1 0 0 1.78 x lo-
1 0 0 1.55 x 10-5
130.1 5 . 0 8 x 1O-4
1 0 0 2 . 0 7 x 1O-5
130.1 3 . 1 3 x 10-4
1 0 0 1.55 x 10-5
60 1.19 x 10-5
6 6 . 8 2 . 7 5 x 1O-5
71.0 1 . 0 0 x 1o-4
4 5 1.25 x 10-5
55 5 . 7 x 10-5
40 6.94 x 1O-6
50 2 . 8 6 x lo-
60 1.28 x 1O-4
2 5 2 . 6 x 1O-5
90 1.93 x 10-5
1 0 8 1.93 x 10-4
1 2 9 1.93 x 1o-3
T W) 4 . 1 3 x 101s
40.0 2 . 2 x 1o-4
3 9 . 6 1 . 9 4 x 1o-4
5 0 . 2 8 . 2 4 x 1O-4
60.1 2 . 3 5 x 1O-3
90 1 . 1 2 x 10-5
1 0 0 1.51 x 10-5
1 1 0 4 . 8 5 x 1O-5
9 8 1.93 x 10-5
1 1 7 1.93 x 10-4
1 3 7 1.93 x 10-3
T 6)
2 . 4 9 x 1Or6
8 0 1.53 x 10-6
90 6.04 x 1O-6
1 0 0 1.82 x 1O-5
1 0 0 1.78 x 1O-5
1 0 0 1.58 x 1O-5
70 3 . 0 2 x lo-
90 4 . 8 5 x 1O-6
1 0 0 2 . 0 3 x 1O-5
1 0 0 1.68 x 1O-5
9 1 . 8 2 . 7 3 x 1O-5
1 1 3 . 0 5 . 4 8 x 1O-5
1 0 2 . 6 1.28 x 1O-5
1 1 3 . 0 4 . 9 2 x 1O-5
1 0 2 . 6 1.71 x 10-5
1 1 3 . 0 6 . 1 9 x 1O-5
1 2 0 . 4 1.505 x 10-4
40.0 2.96 x 1O-4
40.6 2 . 8 9 x 1O-4
46.0 5 . 5 8 x 1O-4
5 5 . 6 1.94 x 10-3
C 1 9 3
1 9 3
193
81
344
344
344
344
331
337
337
270
270
270
1 6 9
270
1 6 9
270
81
2 8
2 8
18
18
90
90
90
203
344
344
344
344
3 1 5
3 2 8
328
3 2 8
2 1 1
2 1 1
2 1 1
344
344
344
344
213
213
270
270
270
213
2 1 3
270
270
328
2 5 5
2 5 5
2 5 5
2 5 5
2 5 5
2 5 5
315
3 2 8
3 2 8
3 2 8
1 5 9 . 0
t7
m3
a.h Chlorohenzene
exp[- 149.36/RT]
1 3 4 Decane
Dodecane
Hexadecane
Hexane
Octane
Paraffin
Tetradecane
Chlorobenzene rerr-Butyl trichloroperacetate
Diethyl peroxydicarbonate rerr-Butanol
1 2 5 . 9 ah
1 2 6 . 8 h
2,2-Oxydiethylene
bis(ally1 carbonate)
Diethyl peroxalate Pentane
terr-Amy1 peracetate Chlorobenzene
133.9-138.1 C
1 2 7 . 2 a
a
a
7
exp[- 141.1/RT]
104.7
ah
1 0 3 . 9 h
rerr-Butyl methoxyperacetate Ethylbenzene
rerr-Butyl peracrylate Benzene
rerr-Butylperoxy isopropyl Chlorobenzene
8 6 . 2 a
a
a
exp[- 150.15/RT]
a
a
rerr-Butyl perpropionate
carborate
Benzene
Decane
Dodecane
Hexadecane
a-Methylstyrene
ren-Butyl 2-acetoxyperacetate
rerr-Butyl cyclopropane-
percarboxylate
Octane
Tetradecane
Ethylbenzene
n-Dodecane
n-Hexadecane
2,2,4-Trimethyl-
pentane
rerr-Butyl ethoxyperacetate Ethylbenzene
a
a
8
b
1 5 3 . 8 h
1 4 6 . 2 h
1 0 5 a
102.7 mz,h
Not es page I I - 69; References page II - 70
I I / 5 0 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 6. contd
Number of
C atoms Initiator Solvent
T(C) kd (S-l) E. (kI/mol) Notes Ref s.
Benzene
Methanol
Methoxybenzene
Nitrobenzene
Octane
Fyridine
Toluene
Ethylbenzene
Benzene
Bulk
Chlorobenzene
Cumene
Decane
Dodecane
Hexadecane
Iso-octane
Nujol
Octane
Benzene
rerr-Butyl heptafluoroperoxy-
butyrate
rert-Butyl methoxypetpropionate
felt-Butyl perisobutyrate
[err-Butyl percrotonate
8 (contd) 65.0 1.56 x 1O-5
70.0 3.09 x 10-5
75.0 5.27 x 1O-5
80.0 9.08 x lo-
60.0 9.5 x 10-6
65.0 1. 61 x lo-
70.0 2.70 x 1O-5
75.0 5.23 x 1O-5
80.0 9.18 x 1O-5
60.0 9.6 x 1O-6
65.0 1. 93 x 1o-5
70.0 3.57 x 10-5
75.0 6.35 x 1O-J
1 0 . 0 7.19 x 10-5
1 5 . 0 9.37 x 10-5
1 9 . 6 1.304 x 1o-4
30.0 2.604 x 1O-4
55.0 5. 01 x 10-5
60.2 8.56 x 1O-5
65.0 1.378 x 1O-4
70.0 2.444 x 1O-4
40.0 3.26 x 1O-5
45.0 6.36 x 1O-5
50.0 9.31 x 10-5
85.0 5 . 1 x 10-6
90.0 9.5 x 10-6
95.0 1. 75 x 10-5
100.0 3. 41 x 10-5
30.0 2.74 x 1O-5
40.0 7.66 x 1O-5
50.0 1. 868 x 10-4
65.0 1. 88 x 10-5
75.0 4.66 x 1O-5
80.0 7.06 x 1O-5
85.0 1. 203 x 1O-4
40.3 4.30 x 10-3
7 8 3.77 x 10-5
7 0 6.69 x 1O-5
8 5 5.33 x 10-5
1 0 0 3.50 x 10-4
7 0 4.12 x 1O-5
90.6 8.13 x 1O-5
100. 7 2.75 x 1O-4
110.0 8.92 x 1O-4
7 9 1. 93 x 1o-5
9 8 1. 93 x 1o-4
1 1 8 1. 93 x 10-3
T (K)
2.07 x 1015
90.6 6.9 x 1O-5
100. 7 2.35 x 1O-4
110.0 6.57 x 1O-4
7 0 4.7 x 10-6
8 5 2.6 x 1O-5
1 0 0 1. 55 x 10-4
1 0 0 1. 46 x 1O-4
1 0 0 1. 56 x 1O-4
1 0 0 1. 47 x 10-4
103.4 2.16 x 1O-4
103.4 2.23 x 1O-4
1 0 0 1. 59 x 1o-4
1 0 0 1. 52 x 1O-4
1 0 0 2.5 x 10-5
1 1 5 1. 50 x 10-4
1 3 0 7.39 x 10-4
v24
v24
v24
v24
v25
v25
v25
v25
v25
v26
V26
v26
v26
a
140.6 a
a
a
a
140.6 h
exp[- 13516/RT]
133. 1 h
1 2 2 a
a
a
1 3 8 a
a
a
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
3 7
126,337
126,337
126,337
3 7
1 3 6
1 3 6
1 3 6
344
344
344
344
1 3 6
1 3 6
1 3 6
3 3 7
3 3 7
3 3 7
270
270
270
2 5 1
2 5 1
270
270
337
337
337
TABLE 6. contd
Peresters and Peroxycarbonates II/51
Number of
C atoms Initiator Solvent T (Cl kti (s-l) E, W/mol) Notes Ref s.
8 (conrd) tert-Butyl permaleic acid Acetone
rerf-Butyl permethacrylate
rerr-Butyl peroxyisopropyl carbonate Benzene
Cyclohexyl peracetate a-Methylstyrene
Diisopropyl peroxalate
Diisopropyl peroxydicarbonate
Ethyl rert-butyl peroxalate
9 reti-Butyl 2-acetoxyperpropionate Ethylbenzene
rerr-Butyl S-bromo-2-pertbenoate Carbon tetrachloride
tert-Butyl 5-chloro-2-perthenoate Carbon tetrachloride
rert-Butyl cyclohutane-
percarboxylate
ter?-Butyl 2,2-dimetbyl-
3-bromoperpropionate
terr-Butyl 2,2-dimethyl-
3-chloroperpropionate
rerr-Butyl 2,2-dimethyl-
3-iodoperpropionate Cyclohexane
tert-Butyl isopropoxyperacetate Ethylbenzene
Pentane
Benzene
Di-n-butyl phthalate
Decane
Ethylbenzene
Mineral spirits
2,2-Oxydiethylene-
bis(ally1 carbonate)
Toluene
Benzene
n-Hexadecane
2,2,4-Trimethyl-
pentane
Cyclohexane
Cyclohexane
70 2.7 x 1O-6
8 5 1.6 x 1O-5
101 6.77 x 1O-5
90 1.92 x 1O-5
1 0 0 7.66 x 1O-5
1 1 0 1.92 x 1O-4
90 6.64 x 1O-6
1 0 0 2.21 x 10-5
1 1 0 6.87 x 1O-5
8 8 . 6 1.63 x 1O-5
93.0 2.30 x 1O-5
9 9 . 3 4.75 x 1o-5
2 5 6.0 x 1O-5
5 4 . 0 5.0 x 10-5
7 7 1.39 x 10-3
8 7 4.09 x 10-3
9 7 1.25 x lo--
1 0 7 3.54 x 10-2
1 1 7 7.98 x lo-*
3 5 6.3 x 1O-6
4 5 2.7 x 10 -5
60 1.85 x 1O-4
5 4 . 3 4.5 x 10-5
5 4 . 3 5.2 x 1O-5
30 2 x 10-6
4 5 1.8 x 1O-5
60 1.28 x 1O-4
75 7.55 x 10-4
40 6.39 x 1O-6
5 0 2.28 x 1O-5
60 9.44 x 10-5
50 3.03 x 10-5
4 5 4.48 x 1O-5
5 5 1.63 x 1O-4
6 5 5.93 x 10-4
91.4 3.60 x 1O-4
9 9 . 2 2.24 x 1O-6
1 1 2 . 0 1.18 x 1O-5
1 2 4 . 5 4.30 x 1o-5
9 9 . 2 2.29 x 1O-6
1 1 2 . 0 9.56 x 1O-6
124.5 4.42 x 1O-5
1 0 2 . 6 4.33 x 10-5
9 2 . 9 1.21 x 10-5
1 0 2 . 6 4.84 x lo-
1 1 3 . 0 1.668 x 10 -4
5 5 9.50 x 10-6
6 5 3.58 x 1O-5
7 5 1.23 x 1O-4
5 5 3.55 x 1o-6
6 5 1.48 x 1O-5
7 5 5.65 x 1O-5
5 5 2.91 x 1O-5
7 5 3.76 x 1O-4
40.0 4.8 x 1O-4
3 9 . 9 4.22 x 1O-4
4 9 . 9 1.39 x 10 -3
5 5 . 3 2.68 x 1O-3
1 1 3
1 3 7 . 0
1 0 9 . 4
1 1 3
m2
Y 16
Y16
Y 16
Y16
Y16
a
a
a
1 1 3
1 1 7 . 6
112.5
143.5
143.5
m2
a
a
a
a
a
a
a
a
c,h
a
a
a
a
a
a
1 5 0 . 4 h
1 1 8 . 2 h,t6 320
t6 320
t6 320
1 2 8 . 6
h,t6 320
t6 320
t6 320
1 1 6 . 9
1 0 0 . 6
9 8 . 9
h,t6
t6
ah
hm
3 3 7
3 3 7
3 3 7
2 1 1
2 1 1
2 1 1
9
9
9
253
253
253
203
60
236
236
236
236
236
337
337
3 3 7
60
60
3 3 7
3 3 7
3 3 7
337
90
90
90
90
31
31
31
328
1 7 6
1 7 6
1 7 6
1 7 6
1 7 6
1 7 6
2 5 5
2 5 5
2 5 5
255
320
320
3 1 5
3 2 8
3 2 8
3 2 8
Notes page II - 69; References page II - 70
II/52 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 6. contd
Number of
C atoms Initiator Solvent
T (C) kd (S-l) E. Wmol) Notes Refs.
9 (cont'd) lerr-Butyl l-methylcyclopropyl- 2,2,4-Trimethylpentane
percarboxylate
Di-(ret?-butylperoxy)-carbonate Chlorobenzene
fert-Butylperoxy isopropyl
carbonate
1,2-Dichlorobenzene
Cumene
Isopropyl ether
Benzene
rerrButy1 perpivalate
Chlorobenzene
Cyclohexane
Decane
Dioxane/water (90/10)
Dodecane
Hexadecane
Hexane
Heptane
Isooctane
Mineral spirits
fert-Butyl perpivalate-ds
Octane
Tetradecane
Chlorobenzene
1 0 2 . 6 2.30 x 1O-s
1 1 3 . 0 7.47 x 10-5
99.95 6.72 x 1O-5
110.1 2 . 1 3 x 1O-4
120.1 6.05 x 1O-4
120.1 5.98 x 1O-4
99.95 6.72 x 1O-5
99.95 2.76 x 1O-4
85 3.3 x 10-6
1 0 0 2.2 x 10-5
1 1 5 1 . 3 6 x 1O-4
50 9.77 x 10-6
70 1 . 2 4 x 1O-4
85 7.64 x 10-4
50 1.03 x 10-5
55 1.94 x 10-5
60 3.92 x 1O-5
65 7 . 3 1 x 10-5
70 1 . 3 0 x 10-4
48.9 8.4 x 1O-6
58.6 3.35 x 10-5
64.3 7.01 x lo-s
57 1.93 x lo-s
75 1.93 x 10-4
94 1.93 x 10-3
T (K)
7.09 x lOi
74.8 2.79 x 1O-4
60 3.85 x 1O-5
60.6 4.00 x 10-5
74 1.93 x 10-4
45 3.53 x 10-6
55 1.73 x 1o-5
60 2.95 x 1O-5
65 4.53 x 10-5
64.6 5.81 x 1O-5
75.6 2.10 x 10-4
84.6 5.94 x 10-4
70.3 1.11 x 10-4
55 1.03 x 10-5
65 4.02 x 1O-5
75 1.45 x 10-4
50 4.1 x 10-6
70 5.52 x 1O-5
80 2 . 1 8 x 1O-4
60.6 6.26 x 1O-5
80 2.38 x 1O-4
80 2.39 x 1O-4
55 8.42 x 1O-6
60 1.59 x 10-5
65 3.39 x 10-5
70 6 . 1 9 x 1O-5
80 2.33 x 1O-4
60.6 1.97 x 10-5
73.9 8.82 x 1O-5
5.5 1.01 x 10-5
60 2 . 1 5 x 1O-5
65 4.14 x 10-5
70 7.58 x 1O-5
75 1.47 x 10-4
T W) 3.56 x 10 i4
80 2.34 x 1O-4
80 2.27 x 1O-4
60.6 3.24 x 1O-5
74.0 1.57 x 1o-4
133.7 h
133.1
1 3 8 a
a
a
1 1 9 . 7 a
a
a
k
125.5 h
exp[- 123.59fRlJ
1 2 8 . 0
106.7
ah
t9
t9
h
115.5
1 2 2 . 8 h
1 1 7 a
a
t9
exp[- 123/RT]
t9
t9
t9
t9
255
255
27
27
27
27
27
27
337
337
337
1 2 6 , 3 3 7
1 2 6 , 3 3 7
1 2 6 , 3 3 7
359
359
359
359
359
249
28
28
344
344
344
344
28
81
1 5 6
1 5 6
1 6 0
1 6 0
362
1 6 0
1 5 9
1 5 9
1 5 9
267
320
320
320
337
337
270
1 5 6
270
270
359
359
359
358
270
165
1 6 5
359
359
359
359
359
376
270
270
1 5 6
1 5 6
TABLE 6. contd
Peresters and Peroxycarbonates II/53
Number of
C atoms Initiator Solvent TV3 kd (s-) E, Wmol) Notes Refs.
9 (confd) k=rt-Butyl perpivalate-de Dioxane/water (90/ 10)
Isooctane
tert-Butyl 2-perthenoate Carbon tetrachloride
6 0 . 6 5 . 0 5 x 10-5
t9 1 5 6
60.6 1.62 x 1O-5 t9 165
73.9 8 . 8 2 x 1O-5
t9
165
9 9 . 2 3 . 3 x 10-6 147.3
m2 1 7 6
1 1 2 . 0 1 . 6 6 x 10-5 m2 1 7 6
124.5 6 . 8 7 x lo-5 m2 1 7 6
90 7.59 x 10-5 141
1 0 0 9 . 9 x 10-4
1 0 0 3 . 7 9 x 10-5
90 1.32 x 1O-5
1 0 0 4 . 9 1 x 10-5
90 3 . 3 x 10-6
1 0 0 1 . 1 0 x 10-5
1 0 0 9 . 0 x 10-6
1 0 0 6 . 0 0 x 1O-3
9 0 9 . 2 4 x 1O-5
1 0 0 3.41 x 10-4
5 1 1.9 x 10-5
5 5 1.93 x 10-5
72 1.93 x 1o-4
9 1 1.93 x 10-3
T 03
4.12 x 1015
5 0 1.05 x 10-5
6 0 3.51 x 10-5
70 1 . 3 0 9 x 10-4
8 0 4.239 x 10 -4
3 5 6 . 9 x 1O-6
4 5 2 . 6 x 1O-5
6 0 1.80 x 1O-4
47 1.93 x 10-5
6 3 1.93 x 10-4
8 2 1.93 x 10-3
T 09
3 . 1 9 x 105
3 0 2 x 10-6
40 1.0 x 10-5
6 0 1 . 3 4 x 10-4
49 1.93 x 10-5
6 5 1.93 x 10-4
8 3 1.93 x 10-3
T (K)
7 . 0 0 x 105
7 4 . 7 1.98 x 1O-4
8 0 . 7 4.37 x 10-4
9 0 . 8 1.25 x 1O-3
4 0 . 3 2.91 x 10 -4
9 9 . 8 1.65 x lo-5
1 1 6 . 6 1.38 x 1O-4
1 2 9 . 9 6 . 8 3 x 1O-4
1 1 3 . 4 km2
m2
t o
m2
a
exp[- 127.76/RT]
1 1 3 a
a
a
exp[- 123.85/RT]
113 a
a
a
exp[- 126.65/RTj
m2
151.3 h
1 4 2
1 4 2
141
14i
141
1 4 2
1 4 2
1 4 2
141
1 4 2
338
344
344
344
3 4 4
362
3 6 2
3 6 2
3 6 2
3 3 7
3 3 7
331
3 4 4
3 4 4
3 4 4
3 4 4
3 3 7
3 3 7
3 3 7
3 4 4
3 4 4
3 4 4
344
3 2 8
3 2 8
3 2 8
3 2 8
2 5 7
2 5 7
2 5 7
1 1 3 . 0 3 . 0 2 x 1O-4
9 2 . 9 2 . 4 7 x 1O-5
1 0 2 . 6 8 . 8 7 x 1O-5
1 1 3 . 0 2 . 8 9 x 1O-4
7 5 1.93 x 10-5
9 3 1.93 x 10-4
1 1 3 1.93 x 10-3
T 03
2 . 4 5 x 1tl15
42.42 9.04 x 10-5
50.30 2.349 x 1o-5
5 7 . 9 5 5.660 x 1O-5
4 4 . 8 5 1 . 8 7 4 x 10 -5
50.10 3.609 x 1O-5
60.20 1 . 3 0 6 x 1O-4
1 4 0 . 8 h
exp[- 134.00/RT]
1 0 0 . 7 h
2 5 5
2 5 5
2 5 5
2 5 5
344
344
344
344
274
274
214
274
274
274
ter&Butyl l-pyrollidine-
percarboxylate
rert-Butyl N-succinimido-
percarboxylate
Chlorobenzene
Acetonitrile
Benzene
Chlorobenzene
10 rerr-Amy1 perpivalate
Cumene
Cyclohexane
Cyclohexene
Methanol
Methylene chloride
Nitrobenzene
Benzene
Chlorobenzene
Cumene
Di-(sec-butyl)peroxy- Decane
Chlorobenzene
Mineral spirits
Di-n-butyl peroxydicarbonate Chlorobenzene
tert-Butyl 2-acetoxy-2-
methyl perpropionate
terr-Butyl [err-butoxyperacetate
tert-Butyl 4-carbomethoxy-
perbutyrate
rerr-Butyl cyclopentyl-
percarboxylate
Ethylbenzene
Ethylbenzene
Cumene
n-Hexadecane
2,2,4-Trimethyl-
pentane
tert-Butyl peroxydiethyl acetate Chlorobenzene
terr-Butyl 2,2-dimethylperbutenoate Cumene
tert-Butyl 2,2-dimethylperbutyrate Cumene
Notes page II - 69; References page II - 70
II/54 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 6. contd
Number of
C atoms Initiator Solvent
T ((3 ka (s-l) E, Wmol) Notes Refs.
10 (contd) Di(terr-butylperoxy)-oxalate Benzene
tert-Butyl Smethyl-7-perthenoate Carbon tetrachloride
P-Methyl-P-phenyl-p-peroxy-
propiolactone
11
Bis(2-nitro-2-methylpropyl)-peroxy-
dicarbonate
I-Phenylethylperacetate
tert-Butyl 4-chloroperbenzoate
rerr-Butyl-N-(2-chlorophenylperoxy)-
carbamate
rert-Butyl-N-(3-chlorophenylperoxy)-
carbamate
terr-Butyl-N-(4-chlorophenylperoxy)-
carbamate
reti-Butyl cyclohexylperoxy-
carboxylate
rerr-Butyl-N-(2,5-dichlorophenyl-
peroxy) carbamate
rert-Butyl 2,2-dimethylperpentanoate Cyclohexane
[err-Butyl kthyl-2-pertbenoate Carbon tetrachloride
rert-Butyl 2-iodoperbenzoate Chlorobenzene
terr-butyl 4-nitroperbenzoate Phenyl ether
terr-Butyl 3,5dinitroperbenzoate
rert-Butanol
Decane
Dodecane
Octane
n-Pentane
Tetradecane
Styrene
Carbon tetrachloride
Toluene
Benzene
Phenyl ether
Carbon tetrachloride
Toluene
Toluene
Toluene
n-Hexadecane
2,2,4-Trimethyl-
pentane
Toluene
Cumene
Carbon tetrachloride
Carbon tetrachloride
3 5 . 0 6.77 x 1O-5
45.0 2.61 x 1O-4
5 5 . 0 9.3 x 10 -4
2 5 . 0 1.83 x 1O-5
4 1 1.75 x 10-4
4 1 1.81 x 1O-4
4 1 1.79 x 10-4
3 7 . 8 1.01 x 10-4
4 1 1.71 x 1o-4
3 5 5.5 x 10-5
4 5 1.71 x 10-4
5 5 6.01 x 1O-4
9 9 . 2 4.6 x 1O-6
1 1 2 . 0 1.94 x 10-5
124.5 7.95 x 10-5
1 0 6 . 8 5.65 x 1O-6
1 2 6 4.59 x 10-5
1 3 4 9.71 x 10-5
5 0 2.22 x 10-5
1 0 0 1.14 x 1o-4
1 0 0 . 0 3.89 x 1O-6
110.1 1.85 x 1O-5
1 2 0 . 2 6.39 x 1O-5
1 3 0 . 9 2.42 x 1O-4
8 0 4.2 x lo-
8 7 . 0 3.5 x 10-5
9 5 . 5 1.48 x 1O-4
103.3 3.3 x 10-4
78.0 2.6 x 1O-5
8 7 . 0 7.8 x 1O-5
9 6 . 6 2.03 x 1O-4
1 0 2 . 7 4.62 x 10 -4
73.0 5.57 x 10-5
7 8 . 5 1.42 x 1O-4
8 7 . 0 2.75 x 1O-4
9 2 . 5 5.37 x 10-4
9 2 . 9 6.70 x 1O-5
1 0 2 . 6 2.046 x 10 -4
8 2 . 2 1.57 x 10-5
92.9 6.13 x 1O-5
1 0 2 . 6 2.046 x 1O-4
1 1 3 . 0 6.58 x 1O-4
8 8 . 0 2.75 x 1O-5
95.0 5.58 x 1O-5
1 0 3 . 3 1.48 x 1O-4
1 1 4 . 5 4.82 x 1O-4
5 5 1.66 x 10-5
6 5 6.31 x 1O-5
7 5 2.23 x 1O-4
4 5 6.2 x 1O-6
5 5 2.15 x 1O-5
9 9 . 2 5.39 x 10-6
1 1 2 . 0 2.12 x 10-5
124.5 7.91 x 10-5
8 5 . 0 4.02 x 1O-5
1 0 2 . 4 2.58 x 1O-4
1 1 8 . 8 1.32 x 1O-3
110.1 7.56 x 1O-6
1 2 0 . 2 3.19 x 10-5
1 3 0 . 9 1.11 x 1o-4
141.5 3.92 x 10-4
8 0 2.9 x 10-7
8 0 1.1 x 10-7
1 0 6 . 7 ch
C
C
7 5 . 3
1 3 7 . 7
1 3 1 . 8
am 2
am 2
am 2
h,v 9
c,v 9
a
138.7
1 6 4 . 4
157.3 h
115.5 h
1 1 9 . 7 h
1 3 6 . 6
1 3 5 . 8
h
h
1 2 8 . 9 h
120.7 h
1 0 5 . 4
130.5
h
172.8
30
30
30
1 9 7
270
270
270
1 9 7
270
2 1 5
215
2 1 5
1 7 6
1 7 6
1 7 6
195
195
195
90
259
5 3
5 3
5 3
5 3
354
3 6
3 6
3 6
3 6
36
36
3 6
3 6
3 6
36
3 6
2 5 5
2 5 5
2 5 5
255
255
255
36
3 6
3 6
3 6
320
320
320
1 6 0
1 6 0
1 7 6
1 7 6
1 7 6
1 3 4
1 3 4
1 3 4
5 3
5 3
5 3
5 3
354
354
TABLE 6. contd
Peresters and Peroxycarbonates II/ 55
Number of
C atoms Initiator Solvent
T (0 kd (S-l) E. Wmol) Notes Ref s.
11 (contd) fer?-Butyl-N-(3-nitrophenylperoxy)-
carbamate
Toluene
tert-Butyl-N-(4-nitrophenylperoxy)-
carbamate
Toluene
terr-Butyl perbenzoate Acetic acid
Benzene
Bromobenzene
n-Butanol
nSuty1 acetate
rerr-Butylbenzene
n-Butyl ether
Carbon tetrachloride
Chlorobenzene
4-Chlorotoluene
Cumene
Dodecane
Ethylbenzene
Heptane
Hexadecane
Methyl benzoate
Octane
Phenyl ether
Tetradecane
Trimethylbenzene
Xylene
78.0 8.4 x 1O-6
88.7 2.43 x 1O-5
98.0 1.01 x 10-4
106.0 2.36 x 1O-4
73.0 6.4 x 1O-6
87.0 3.11 x 10-5
98.0 8.75 x 1O-5
106.0 2.38 x 1O-4
100.0 3.83 x 1O-5
110.0 1.14 x 10-4
1 0 0 1.07 x 10-5
1 1 5 6.22 x 1O-5
1 3 0 3.50 x 10-4
110.0 3.50 x 10 -5
119.4 1.04 x 10-4
130.0 3.30 x 10-4
119.4 1.37 x 10-4
90.0 9.27 x 1O-5
100.0 2.70 x 1O-4
110.0 1.06 x 1O-4
119.4 2.67 x 1O-4
110.0 3.61 x 1O-5
1 1 9 4 1.1ox 10-4
119.4 1.03 x 10-4
100.0 7.80 x 1O-5
110.0 1.80 x 1O-4
8 0 8.8 x 10-7
110.0 3.83 x 10 -5
119.4 1.11 x 10-4
1 2 0 1.31 x 10-4
1 3 5 6.74 x 1O-4
1 5 0 3.12 x 1O-3
1 0 3 1.93 x 10-5
1 2 2 1.93 x 10-4
1 4 2 1.93 x 10-3
T 6)
2.23 x 1OL6
110.0 3.25 x lo-5
119.4 9.80 x 1O-5
130.0 3.06 x 1O-4
6 0 3.85 x lo-
79.6 7.21 x 10-5
85.0 1.320 x 1O-6
99.3 9.37 x 10 -6
115.0 5.81 x 1O-5
130.2 3.24 x 1O-4
1 0 0 1.4 x 10-5
1 1 5 8.05 x 1O-5
1 3 0 3.56 x 1O-4
1 1 5 6.77 x 1O-5
1 1 5 6.44 x 1O-5
119.4 1.07 x 10-4
1 1 5 7.21 x 1O-5
1 1 5 5.97 x 10-5
119.4 7.80 x 10 -5
1 1 5 7.06 x 1O-5
100.0 6.94 x 1O-6
110. 1 2.28 x 1O-5
120.2 9.00 x 10-5
130.9 2.92 x 1O-4
1 1 5 6.03 x 1O-5
T 6) 2.62 x 10 I6
119.4 1.09 x 10-4
130.0 3.42 x 1O-4
133. 1 h
113. 8 h
130. 1
145.2
144. 3
120. 5
123.4
148. 5
99.2
a
a
a
a
a
a
a
a
a
a
a
a
a
am 2
a,m 2
a
a
a
141.8 a
a
m2
m2
m2
exp[- 151.59/ZUJ
144. 3
140.2
C
C
C
ah
1 3 4 a
a
a
a
a
156.9
exp[- 152.O/RT]
141.4 a
a
3 6
3 6
3 6
3 6
3 6
3 6
3 6
3 6
5 6
5 6
126,337
126,337
126,337
5 6
5 6
5 6
5 6
5 6
5 6
5 6
5 6
5 6
5 6
5 6
5 6
5 6
354
5 6
5 6
2 2
2 2
2 2
344
344
344
344 I
5 5
5 5
5 5
8 1
272
3 4 5
3 4 5
3 4 5
345
337
3 3 7
3 3 7
270
270
5 6
270
270
5 6
270
5 3
5 3
5 3
5 3
270
376
5 6
5 6
Notes page II - 69; References page II - 70
II/56 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 6. contd
1
Number of
C atoms Initiator Solvent
TW) kd (S-l) E. Wmol) Notes Refs.
r
I
11 (cornd) ferr-Butyl-N-(4-bromophenylperoxy)-
carbamate
Toluene
rerf-Butyl percarboxycyclohexane Chlorobenzene
terr-Butyl per-2-methylphenylacetate
reti-Butyl-N-(phenylperoxy)
carbamate
rert-Hexyl peroxypivalate
1,1,2-Trimethylpropyl perpivalate Cumene
Cumyl peracetate
12 rerr-Amy1 peroxybenzoate
4-Bromocumyl perpropionate Benzene
rerr-Butyl bicyclo[2.2.l]lheptane-
2-percarboxylate
rerr-Butyl endo-bicyclo[2.2.1]-
heptane percarboxylate
Cumene
Isooctane
Toluene
Chlorobenzene
Cumene
Carbon tetrachloride
Toluene
Chlorobenzene
a-Methylstyrene
Cumene
Chlorobenzene
terr-Butyl exo-bicyclo[2.2.1 l]-
heptane-2-percarboxylate
Chlorobenzene
7 0 . 8 3.32 x 1O-5
7 9 . 8 1.04 x 10-4
8 4 . 0 1.75 X 10-4
96.0 7.70 x 10-4
100.1 2.75 x 1O-4
1 1 1 . 4 9.65 x 1O-4
1 2 0 . 0 2.39 x 1O-3
7 9 . 6 1.86 x 10-5
7 9 . 6 1.42 x 1O-5
7 9 . 6 1.15 x 10-5
6 0 . 6 6.60 x 10-5
7 3 . 9 3.233 x 1O-4
5 1 . 2 3.4 x 10-6
6 7 . 7 2.31 x 1O-5
7 7 . 7 1.15 x 10-4
9 0 . 7 6.41 x 1O-4
T W
1.51 x 106
40 2.39 x 1O-6
5 0 8.83 x 1O-6
6 0 3.37 x 10-5
7 0 1.226 x 1O-4
8 0 4.166 x 1O-4
40 3.6 x 1O-6
50 1.59 x 10-5
60 5.14 x 10-5
70 1.921 x 1O-4
1 0 0 4.68 x 1O-5
1 0 0 3.43 x 10-5
9 9 1.93 x 10-5
1 1 8 1.93 x 10-4
1 3 9 1.93 x 10-3
T W)
8.38 x 10 l5
70 1.48 x 10-6
8 0 5.73 x 1o-6
90 1.81 x 1O-5
70 1.99 x 1o-6
8 0 4.93 x 10-6
90 1.55 x 10-5
8 5 1.16 x 1O-6
1 0 0 1.02 x 10-5
1 1 0 3.76 x 1O-5
1 1 0 4.6 x 1O-5
1 2 0 1.56 x 1O-4
1 3 0 4.99 x 10-4
94.0 1.75 x 10-5
1 0 1 . 9 6.20 x 1O-5
1 0 9 . 6 1.7 x 10-4
120.5 5.72 x 1O-4
9 4 . 5 9.69 x 1O-5
1 0 1 . 9 1.96 x 1O-5
1 1 1 . 9 6.53 x 1O-5
100.1 4.61 x 1O-5
1 1 1 . 4 1.96 x 1O-4
1 2 0 . 0 5.40 x 10-4
9 4 . 0 1.87 x 1O-5
1 0 1 . 9 5.30 x 10-5
1 0 9 . 6 1.10 x 10-4
120.3 4.3 x 10-4
9 4 . 5 5.27 x 1O-5
1 0 1 . 9 1.12 x 10-4
1 1 1 . 9 3.57 x 1o-4
9 4 . 5 8.86 x 10-5
1 0 1 . 9 2.28 x 10-4
112.1 8.85 x 1O-4
1 7 7 . 6 h
1 3 1 . 0 h
139.7
z (1)
z (2030)
z (4050)
m2
m2
h
exp[- 136.O/RT]
C
P
exp[- 147.02/RT]
129.7 a
a
a
121.3 a
a
1 5 5 . 2 h
1 6 0
1 5 0 . 2 h
137.2 h
1 4 9 . 0 h
1 5 4 . 0 h
130.1 h
3 6
3 6
1
3 6
3 6
181
181
181
163
163
163
165
165
3 6
3 6
3 6
3 6
40
362
362
362
362
362
362
362
362
362
2 7 1
2 7 1
344
344
344
344
213
213
213
2 1 3
213
213
1 6 0
1 6 0
2 2 3
2 2 3
2 2 3
147
147
147
1 4 7
1 4 7
1 8 2
1 8 2
181
181
181
1 4 7
1 4 7
1 4 7
147
1 8 2
1 8 2
1 8 2
1 8 2
1 8 2
1 8 2
,
.
Peresters and Peroxycarbonates II/57
TABLE 6. contd
Number of
C atoms Initiator Solvent T (C) kd (S-1 E, Wmol) Notes Refs.
12 (cmdd)
C u m e n e
terr-Butyl endo-bicyclo[2.2.1]-hept-
Sene-2-percarboxylate
kv?-Butyl exo-bicyclo[2.2.1]-hept-
5-ene-2-percarboxylate
C u m e n e
Ch l o r o b e n z e n e
rerr-Butyl 4-bromophenoxyperacetate Ethylbenzene
rerr-Butyl 4-chlorophenoxyperacetate Ethylbenzene
tert-Butyl 3-chlomphenylperacetate Ch l o r o b e n z e n e
rert-Butyl 4-chlorophenyl peracetate Ch l o r o b e n z e n e
ter?-Butylcycloheptyl percarboxylate
rerr-Butyl 2,4-dichlomphenoxy-
per acet at e
tert-Butyl 2,2-diethyl perbutyrate
tert-Butyl per-2-ethylhexanoate
terf-Butyl 2-methoxy-2-methyl-
pe r pr opi ona t e
ten-Butyl 4-methoxyperbenzoate Phenyl ether
reti-Butyl peroxy-2-methyl-
be nz oa t e
reti-Butyl4-methoxyperbenzoate Carbon tetrachloride
rert-Butyl 4-methylperbenzoate Phenyl ether
C u m e n e
C u m e n e
n- He xa de c a ne
2,2,4-Trimethylpentane
Ethylbenzene
C u m e n e
Be n z e n e
Ch l o r o b e n z e n e
Ch l o r o b e n z e n e
Ch l o r o b e n z e n e
96.0 1.33 x 10-4
100.1 1.90 x 10-4
111.4 6.79 x lO-4
120.0 1.64 x 10-3
84.4 2.19 x lO-5
94.7 7.29 x lO-5
100.1 1.37 x 10-4
108.6 3.6 x lO-4
113.5 6.19 x lO-4
94.5 6.05 x 1O-5
101.9 1.53 x 10-4
112.1 4.72 x 1O-4
94.5 3.11 x 10-5
101.9 7.35 x 10-5
112.0 2.48 x lO-4
94.5 5.59 x 10-5
101.9 1 25 x lO-4
112.1 5.00 x 10-4
94.5 4.48 x lO-5
101.9 1.18 x lO-4
112.1 3.97 x 10-4
70.5 2.6 x 1O-4
70.5 2.9 x 10 -4
79.6 4.05 x 10-5
90.7 1.44 x 10-4
100.5 4.38 x 1O-4
79.6 2.98 x lO-5
79.6 1.99 x 10-5
79.6 8.44 x 1O-5
90.7 2.95 x 1O-4
100.5 8.19 x 1O-4
79.6 6.54 x lO-5
79.6 4.45 x lo-
92.9 1.801 x lO-4
102.6 5.17 x 10-4
92.9 1.703 x 10-4
102.6 5.07 x 10-4
70.5 9.4 x 10-5
4 5 1.23 x lO-5
5 5 4.92 x lO-5
6 5 1.46 x 1O-4
72 1.9 x 10-5
72 1.93 x 10-5
91 1.93 x lo-4
113 1.93 x 10-3
f W)
1.54 x 104
- 14.0 2.05 x 1O-5
- 7.0 6.73 x lo-
- 1.0 1.67 x lO-4
15.0 1.28 x lO-3
100.0 1.07 x 10-5
110.1 4.17 x 10-5
120.2 1.28 x 1O-4
130.9 4.28 x lO-4
96 1.93 x 10-5
115 1.93 x 10-4
1 3 6 1.93 x 10-3
T 6)
8.56 x 10 I5
80 1.0 x 10-6
100.0 9.42 x lO-6
110.1 3.19 x 10-5
120.2 1.06 x 1O-4
129.3 h
129.3 h
131.4 h
136.4 h
138.1 h
123.0
a
a
h
117.2
z (0.98)
z W9W
h
121.5
125.7
z (0.98)
z 6@w
h
h
100.3
a
h
a
exp[- 124.9O/RT]
86.3
m2
m2
m2
m2
149.8 a
a
a
a
expr[- 145.97fRTj
151.0 a
a
a
1 4 7
181
181
181
1 4 7
1 4 7
1 4 7
1 4 7
1 4 7
1 8 2
1 8 2
1 8 2
1 8 2
1 8 2
1 8 2
1 8 2
1 8 2
1 8 2
1 8 2
1 8 2
1 8 2
315
315
1 7 8
1 7 8
1 7 8
207
207
1 7 8
1 7 8
1 7 8
207
207
2 5 5
255
t
255
I
255
315
1 6 0
1 6 0
1 6 0
338
344
344
344
344
2 7 5
275
275
2 7 5
5 3
5 3
5 3
5 3
344
344
344
344
354
5 3
5 3
5 3
Notes page II - 69; References page II - 70
II/58 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 6. contd
Number of
C atoms Initiator Solvent
T ((2 kd (S-l) E, Wmol) Notes Refs.
12 (contd) rert-Butyl 4-methylperbenzoate
tert-Butyl 2-methyl-2-terr-
butylperoxyperpropionate
rert-Butyl 2-methylsulfonyl
perbenzoate
rert-Butyl 2-(methylthio)perbenzoate Chlorobenzene
rert-Butyl 4-(methylthio)perbenzoate Chlorobenzene
rerr-Butyl 4nitrophenoxyperacetate Ethylbenzene
fert-Butyl 4-nitrophenylperacetate Chlorobenzene
fert-Butyl 4-nitrophenylperacetate
Di-terr-butyl per-2-chlorosuccinoate
Phenyl ether
Benzene
Chlorobenzene
Decane
Dodecane
Hexadecane
Octane
Tetradecane
Unknown
rert-Butyl peroctoate
Decane
Di-rerf-butyl persuccinoate Styrene
terr-Butyl phenoxyperacetate Ethylbenzene
terr-Butyl phenylperacetate Chlorobenzene
Cumene
Decane
Dodecane
Hexadecane
Isooctane
1 3 0 . 9
9 . 0
19.0
30. 0
42. 0
105
120
135
150. 6
60
3 9 . 4
50.1
50. 2
6 9 . 8
120. 4
10. 5
19. 6
90. 7
100. 5
80
17. 5
77. 5
1 0 0
77. 5
77. 5
1 0 0
77. 5
105
115
125
70
85
1 0 0
70
85
1 0 0
1 0 5
1 1 5
1 2 5
70. 5
60
17. 0
88. 6
79. 6
90. 1
100. 5
19. 6
19. 6
19. 6
79. 6
85. 0
79. 6
79. 6
79. 6
79. 6
7 9 . 6 1
77. 5
77. 5
77. 5
85. 0
95. 2
3. 25 x 1O-4
6. 66 x 10-5
1.99 x 1o-4
6.94 x 1O-4
2. 43 x 1O-3
6. 68 x 10-6
5. 57 x 10-5
2. 76 x 10m4
2. 05 x 1O-3
8. 08 x 10-4
2.59 x 10-5
2. 42 x 1O-4
1.88 x 1O-4
1.96 x 1O-3
1.75 x 10-4
6. 7 x lo-
2. 5 x 1O-5
8.9 x 1o-5
2. 83 x 1O-4
3. 77 x 10-5
6. 30 x 1O-6
5.81 x 10-6
1.31 x 1o-4
5.11 x 10-6
6. 42 x 1O-6
1.60 x 1O-4
5. 56 x 1O-6
2. 74 x 1O-4
1.22 x 10-5
5.90 x 10-4
3. 83 x 1O-5
1.52 x 1O-3
1.00 x 10-4
1.4 x 10-5
8. 55 x 10-5
4. 55 x 1o-4
6.9 x 1O-6
4.39 x 10-5
2. 64 x 1O-4
1.93 x 10-5
6. 7 x 1O-5
2. 53 x 1O-4
4. 4 x 10-4
6.79 x lO-j
6. 85 x 1O-5
2. 45 x 1O-4
1.05 x 10-4
3. 53 x 10-4
1.003 x 10-3
1.07 x 10-4
9.1 x 10-5
1.02 x 10-4
9.0 x 10-4
1.945 x 1om4
6. 6 x 10-5
5. 6 x 1O-5
6. 78 x 10m5
4. 73 x 10-5
1.1 x 10-5
3. 00 x lo-s
2. 75 x 1O-5
2. 60 x 1O-5
1.08 x 1o-4
3. 527 x 1O-4
78. 8
a
m2
95.0 ah
b
C
m2
1 2 9 . 9 ah
1 2 4 . 7 h
1 0 2 . 9
143.5
1 3 0
x2
x2
x2
x2
x2
x2
a
1 3 0
1 5 4 . 8
113.1
120.1
1 1 7 . 6
116.7
a
Xl
Xl
Xl
ah
a,h
h
m2
h
z (0.98)
z (4050)
z (0.98)
z (4050)
m2
z (0.98)
z (4050)
z (0.98)
z (6090)
53
275
275
275
275
22
22
22
22
9 7
134
134
134
134
134
315
178
178
178
1 6 9
1 6 8
1 6 8
1 6 8
1 6 8
1 6 8
1 6 8
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. contd
Peresters and Peroxycarbonates II/59
Number of
C a t o ms Initiator Solvent
T (C) kd (S-l) E, Wmol) Notes Refs.
12 (contd) cert-Butyl pbenylperacetate
rert-Butyl 2-propylperpenten-2-oate
(cis)
(tram)
rerr-Butyl 2,2,3,3-tetramethyl-
perpropionate
Cumene
tert-Butyl thiophenylperacetate Ethylbenzene
[err-Butyl per-o-toluate Benzene
rert-Butyl per-paratoluate Cumene
rerf-Butyl-N-(3-tolylperoxy)-
carbamate
terr-Butyl 2,4,5-trichloro-
phenoxyperacetate
4-Chlorocumyl perpropionate
Cumyl perpropionate
4-Iodocumyl perpropionate Benzene
4-Nitrocumyl perpropionate Benzene
1,1,3-Trimethylbutyl perpivalate
13 k&Amy1 per-2-ethylhexanoate
Benzyl(rerr-butylperoxy)oxalate
Octane
Paraffin oil
Tetradecane
Cumene
Cumene
Toluene
Ethylbenzene
Benzene
a-Methylstyrene
Benzene
cc-Methylstyrene
whlethylstyrene
a-Methylstyrene
Cumene
Benzene
Chlorobenzene
Benzene
7 1 . 5 3.11 x 10-5
8 5 . 0 1 . 1 5 0 x 10-4
1 1 . 3 2 . 6 6 x 1O-5
9 4 . 9 2 . 7 8 x 1O-5
100.1 5 . 4 x 10-5
100.1 4.26 x 1O-5
100.1 2.31 x 1O-5
110.1 1.72 x 1O-4
9 4 . 9 2 . 4 7 x 1O-5
100.1 4 . 7 x 10-5
100.1 3 . 1 3 x 10-5
100.1 1.42 FH-~
110.1 1.64 x 1O-4
42.2 8 . 7 6 x 1O-6
5 4 . 9 5 . 8 4 x 1O-5
1 0 . 3 3 . 3 6 x 1O-4
7 0 . 5 3 . 8 x 1O-4
9 7 1.9 x 10-5
8 4 . 0 1 . 6 6 0 x 10-6
9 9 . 3 1 . 1 3 9 x 10-5
1 1 5 . 0 6 . 7 7 x 1O-5
6 4 . 0 4 . 5 8 x 10-5
7 0 . 7 9 . 1 7 x 10-5
78.0 2 . 0 3 x 1O-4
88.5 5 . 7 8 x 1O-4
7 0 . 5 5 . 8 x lo-
IO 1.46 x 1O-6
80 5 . 6 8 x 1O-6
90 1.79 X 10-5
70 1.50 x 10-6
8 0 4.54 x 1o-6
90 1.47 x 10-5
7 0 2 . 6 0 x 1O-6
8 0 6 . 1 5 x 1O-6
9 0 1.90 x 10-5
70 6 . 3 1 x 1O-6
8 0 1.71 x 10-5
90 4 . 9 4 x 10-5
70 1.37 x 10-6
8 0 5 . 7 6 x 1O-6
90 1.79 x 10-5
7 0 1.54 x 10-6
8 0 4.96 x 1O-6
90 1 . 6 2 x 1O-5
70 1.36 x 1O-6
8 0 5 . 3 2 x 1O-6
90 1.78 x 1O-5
70 1.35 x 10-6
8 0 4 . 0 7 x 10-6
90 1.43 x 1o-5
40 4.80 x 1O-6
50 1 . 7 7 x 10-5
6 0 6 . 1 8 x 10-5
70 2.344 x 1O-4
IO 1.9 x 10-5
13 1.93 x 10-5
9 1 1.93 x 10-4
111 1.93 x 10-3
T W
1.77 x 1oL5
45 3 . 6 5 x 1O-5
5 5 1.33 x 1o-4
6 5 4 . 6 9 x 1O-4
1 3 7 . 2
1 4 3 . 9
1 1 4
1 0 2 . 9
1 2 9 . 3
118.8
1 0 1 . 7
1 0 6 . 7
133.1
125.5
133.5
124.7
h
z (0.98)
z (1100)
z (4000)
h
z (0.98)
z (1100)
z (3830)
h
a
a
h
a
a
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[- 132.11/RT]
1 1 1 . 3 ch
C
1 6 8
165
168
1 7 2
1 7 2
1 7 2
1 7 2
1 7 2
1 7 2
1 7 2
1 7 2
1 7 2
112
2 6 7
267
261
3 1 5
338
3 4 5
3 4 5
345
3 6
3 6
3 6
3 6
3 1 5
2 1 3
213
2 1 3
2 1 3
2 1 3
2 1 3
2 1 3
2 1 3
2 1 3
213
2 1 3
2 1 3
2 1 3
213
2 1 3
2 1 3
2 1 3
213
2 1 3
2 1 3
2 1 3
2 1 3
2 1 3
2 1 3
362
362
362
362
3 3 8
344
344
344
344
31
31
31
Notes page II - 69; References page II - 70
II/60 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 6. contd
Number of
C atoms Initiator Solvent T ((3 ka (S-l) E, Wmol) Notes Refs.
13 (conrd) [err-Butyl benzyloxyperacetate Ethylbenzene
rerr-Butyl benzylthioperacetate Ethylbenzene
rerr-Butyl bicyclo[2.2.2]octane-
I-percarboxylate
rerrButy1 endo-bicyclo[2.2.1]-2-
methylheptane-2-percarboxylate
terr-Butyl exo-bicyclo[2.2.1]-
2-methylheptane-2-percarboxylate
rert-Butyl 1,4-dimethylcyclohexane-
1-percarboxylate (cis)
(tram)
rerr-Butyl 3-methoxyphenyl-
peracetate
fert-Butyl 4- methoxyphenyl-
peracetate
ferr-Butyl 4-methylphenyl peracetate
Di-rerr-butyl perglutarate
rerr-Butylperoxy 2-ethylhexyl-
carbonate
Cumene
Cumene
Cumene
Cumene
Cumene
Chlorobenzene
Chlorobenzene
Cumene
Decane
Dodecane
Ethylbenzene
lsooctane
Octane
Pa&in oil
Tetradecane
Chlorobenzene
Cumene
Decane
Dodecane
Ethylbenzene
Hexadecane
Octane
Tetradecane
Styrene
Chlorobenzene
40.0 1.3 x 10-4
40.0 1.45 x 10-4
5 1 . 0 5 . 0 3 x 10-4
6 0 . 7 1.62 x 1O-3
40.0 2.60 x 1O-5
6 0 . 0 3.31 x 1o-4
70.0 1.14 x 10-3
6 5 7 . 5 x 10-6
7 5 2 . 8 2 x 1O-5
8 5 8 . 4 7 x 1O-5
8 0 5.1 x 10-5
90 1.67 x 1O-4
1 0 0 4.86 x 1O-4
7 5 7 . 3 5 x 10-5
80 1.39 x 10-4
8 5 2 . 6 4 x 10 -4
90 4 . 8 1 x 1O-4
9 5 8.41 x 1O-4
60 7 . 7 8 x 1O-5
6 5 1.44 x 10-4
70 2 . 7 5 x 1O-4
7 5 4.89 x 1O-4
8 0 8 . 9 3 x 1O-4
60.0 7 . 5 2 x 1O-5
70.0 2 . 6 6 x 1O-4
8 0 . 0 8 . 4 9 x 1O-4
6 0 . 0 6 . 9 3 x 1O-5
70.0 2 . 5 2 x 1O-4
8 0 . 0 7 . 7 9 x 10-4
7 9 . 6 9 . 9 x 10-5
9 0 . 7 3 . 4 5 x 10-4
100.5 1.051 x 10-3
5 6 . 0 4 . 5 7 x 10-5
6 0 . 3 9 . 9 x 10-5
7 0 . 2 3 . 0 6 x 10 -4
7 9 . 3 7 . 9 9 x 10-4
48.9 1.93 x 10-5
60 6 . 8 5 x 10-5
60 5.31 x 10-5
7 9 . 6 5.942 x 10 -4
7 7 . 5 2 . 5 2 x 1O-4
7 7 . 5 2 . 6 0 x 1O-4
7 0 . 5 1.4 x 10-3
6 0 . 5 4.72 x 1O-5
7 7 . 5 2 . 5 3 x 1O-4
6 0 . 5 4.20 x 1O-5
7 7 . 5 2 . 6 8 x 1O-4
70.4 8 . 6 7 x 1O-5
79.6 2.37 x 10 -4
9 0 . 7 7 . 9 5 x 1o-4
7 9 . 6 1 . 6 4 9 x 10-4
7 9 . 6 1 . 1 8 0 x 1O-4
7 7 . 5 9 . 0 8 x 1O-5
7 7 . 5 8 . 5 7 x lO-5
7 0 . 5 7 . 2 x 1O-4
7 7 . 5 1 . 0 3 2 x 1O-4
7 7 . 5 8 . 8 3 x 1O-5
7 7 . 5 7 . 7 5 x 10-5
1 0 5 2 . 6 5 x 1O-5
115 1.06 x 1O-4
1 2 5 3 . 0 0 x 10-4
99 1.93 x 10-5
1 1 7 1.93 x 10-4
1 3 7 1.93 x 10-3
1 0 0 . 6 ah
101.8 hmz
108.1 hm
1 1 9 . 2 h
120.1 h
1 2 6 . 8 h
1 1 6 . 7 h
1 1 5 . 2
C
h
116.3
1 2 2 . 2
C
0
C
h
1 0 5 . 4 h
k
z (0.98)
z (4050)
207
1 0 4 . 8 ah
1 1 0 . 9 h
z (0.98)
z (6080)
a
Xl
XI
315
328
3 2 8
328
328
328
328
1 6 0
1 6 0
1 6 0
223
223
223
206
206
206
206
206
206
206
206
206
206
206
206
206
206
206
206
1 7 8
1 7 8
1 7 8
1 7 8
1 7 8
1 7 8
1 7 8
249
207
207
1 6 8
1 6 8
3 1 5
1 6 9
1 6 8
1 6 9
1 6 8
1 7 8
1 7 8
1 7 8
207
207
1 6 8
1 6 8
3 1 5
1 6 8
1 6 8
1 6 8
215
2 1 5
2 1 5
344
344
344
TABLE 6. contd
Peresters and Peroxycarbonates II/61
Number of
C atoms Initiator Solvent T (C) kd (s-l) E, WmoU Notes Ref s.
13 (contd) rert-Butylperoxy 2-ethylhexyl-
carbonate
rert-Butyl 2-phenylperpropionate
tert-Butyl 2,2,4,4-tetra-
methylperbutyrate
rerr-Butylthiobenzylperacetate
terr-Butyl peroxy-3,5,5-tri-
methylhexanoate
4-Nitrobenzyl(rerr-butylperoxy)-
oxalate
14 rert-Amylperoxy 2-ethylhexyl-
carbonate
rert-Butyl di-terr-butylperacetate Cumene
fert-Butyl 2-carbomethoxyphenyl-
peracetate
terr-Butyl 2-(4-chlorophenoxy)-
2-methylperpropionate
terr-Butyl 2-(4.chlorophenyl)-
2-methylperpropionate
ferr-Butyl a-methylpercinnamate
(ci s)
(trans)
rer&Butyl 2-methyl-2-phenylper-
propionate
tert-Butyl pemeodecanoate
tert-Butyl 2-(4.nitrophenyl).
2.methylperpropionate
terr-Butyl permesitoate
tert-Butyl l-phenylcyclo- n-Dodecane
propylpercarboxylate Ethylbenzene
Chlorobenzene T W 4.07 x lOI exp[- 151.72/RT] 344
Cumene
Cumene
Ethylbenzene
Chlorobenzene
4 0 . 7 7 . 8 8 x 10m6
60.1 8 . 4 4 x lo-
80.1 8 . 1 0 x 10m4
4 0 . 8 6 . 1 5 x 1O-6
5 4 . 7 3 . 8 2 x 10m5
7 0 . 7 2 . 7 3 x lO-4
40.0 2 . 6 2 x lo-
9 5 1.93 x 10-5
1 1 4 1.93 x 10-4
135 1.93 x 1o-3
T (K) 1 . 9 4 x 1oL5
4 5 1.30 x 10-5
5 5 4.89 x 1O-5
6 5 1.89 x 10m4
9 5 1.93 x 10-5
113 1.93 x 10-4
1 3 4 1.93 x 10-3
T 6) 2 . 2 2 x 10 l6
5 4 . 7 4 . 3 8 x 1O-6
7 0 . 2 3 . 5 6 x lO-5
8 5 . 4 2 . 4 4 x lO-4
7 0 . 8 1.48 x 10-5
8 5 . 4 8 . 0 7 x 10m5
1 0 1 . 0 4 . 3 8 x 1O-4
40.0 7 . 2 x 1O-4
111 h
1 0 0 . 6 a,h
Benzene
exi[- 140.78/RT]
116.7 c,h
Chlorobenzene
exp[- 148.41/RT]
1 2 5 . 3
Cumene 1 1 6 . 9
Ethylbenzene
Acetonitrile
Benzene
Dodecane
2 7 3
2 7 3
2 7 3
2 6 7
267
267
315
344
344
344
344
31
31
31
344
344
344
344
245
2 4 5
2 4 5
2 5 7
2 5 7
257
3 1 5
5 0 . 0 2 . 5 5 x 1O-4
5 0 . 0 2 . 0 3 x lO-4
5 0 . 0 7 . 9 8 x 1O-5
6 0 . 0 2 . 6 8 x 1O-4
67.0 6.36 x 1O-4
5 0 . 0 8 . 0 0 x 10m5
6 0 . 0 2 . 5 6 x 1O-4
6 7 . 0 5 . 9 6 x lO-4
5 0 . 0 8 . 1 0 x 1O-5
6 0 . 0 2 . 6 5 x 10m4
6 7 . 0 5 . 9 5 x 1o-4
9 9 . 6 1.23 x 10m4
109.8 3 . 7 0 x 10-4
9 9 . 6 3.5 x 10-5
109.8 1.03 x lo-4
34.1 3 . 2 6 x 1O-5
3 9 . 7 5 . 6 3 x 1O-5
4 7 1.9 x 10-5
46 1.93 x 10-5
6 4 1.93 x 1o-4
8 4 1.93 x 10-3
T 6) 1.52 x lOI
5 0 . 0 7 . 5 0 x 1o-5
5 0 . 0 6 . 4 0 x 1O-5
5 0 . 0 2 . 6 3 x 1O-5
6 0 . 0 9 . 2 7 x 1O-5
6 7 . 0 2 . 0 3 x 1O-4
6 7 . 0 1.98 x 10m4
8 4 . 0 1 . 4 6 4 x 1O-5
9 9 . 3 9 . 9 4 x 10-5
1 1 5 . 0 6 . 7 x 10m5
1 1 3 . 0 8 . 6 7 x lO-5
1 2 0 . 0 2 . 4 9 x 1O-4
1 3 0 . 0 7 . 4 9 x 10-4
1 4 0 . 0 2 . 2 2 x 10-3
108.1 h
Hexadecane
Octane
Cumene 1 2 8 . 0 fh
Cumene 125.5 f,h
f
Chlorobenzene
Cumene
Benzene
Chlorobenzene
Acetonitrile
Benzene
Dodecane
exp[- 115.47/RT]
1 0 5 . 2 h
Octane
Cumene
147.5 h,t 1
tl
2 6 5
2 6 5
2 6 5
2 6 5
265
2 6 5
2 6 5
2 6 5
2 6 5
2 6 5
2 6 5
1 5 0
1 5 0
1 5 0
1 5 0
249
249
3 3 8
344
344
344
344
2 6 5
2 6 5
2 6 5
2 6 5
2 6 5
2 6 5
3 4 5
3 4 5
3 4 5
2 5 5
3 2 3
3 2 3
3 2 3
Notes page II - 69; References page II - 70
II/62 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 6. contd
Number of
C atoms Initiator Solvent
T ((2 ka (S-l) E, Wmol) Notes Refs.
14 (contd) fert-Butyl l-phenylcyclo-
propylpercarboxylate
tert-Butyl phenyldimethylperacetate
terr-Butyl 2-phenyl-3perbutenoate
tert-Butyl4-phenyl-3-perbutenoate
tert-Butyl 2-phenyl-2-methyl-
perpropionate
tert-Butyl 4-vinylphenylperacetate
Hexadecane
Methyl benzoate
Octyl phthalate
Toluene
Cumene
Dibenzyl peroxalate Pentane
Di-tert-butyl adipate Styrene
Dicyclohexyl peroxydicarbonate Benzene
Chlorobenzene
4-Methoxybenzyl (tert-butylperoxy)-
oxalate
I-Methyl-1-phenylethyl 2,2-dimethyl-
peroxyporpionate
15 terr-Amy1 pemeodecanoate
Dibenzoyl monopercarbonate
tert-Butyl l-adamantyl-
percarboxylate
2,2,4-Trimethyl pentane
Chlorobenzene
Isooctane
Chlorohenzene
Chlorobenzene
Acetonitrile
Benzene
Benzophenone
Benzyl benzoate
Butyl phthalate
Chlorobenzene
Cumene
Dodecane
a-Methylstyrene
Mineral spirits
Benzene
Cumene
Benzene
Chlorobenzene
Benzene
Cumene
1 0 2 . 6 2.53 x 1O-5
1 1 3 . 0 8.96 x lo-*
1 2 0 . 4 2.04 x 10-4
60 9.6 x 1O-4
40.6 2.95 x 1O-5
6 0 . 6 3.059 x 10 -4
6 0 . 6 4.064 x 10-4
60 2.9 x 1O-3
60 1.15 x 10-4
5 0 . 0 3.08 x 1O-4
5 0 . 0 2.18 x 1O-4
60 7.73 x 1o-4
60 7.92 x 1O-4
60 6.5 x 1O-4
60 7.00 x 10-4
60 5.25 x 1O-4
5 0 . 0 8.77 x lo-
6 0 . 0 3.00 x 10-4
6 7 . 0 7.13 x 10-4
60 2.88 x 1O-4
60 3.53 x 1o-4
60 7.55 x 10-4
60 5.70 x 10-4
60 5.66 x 1O-4
7 0 . 9 5.54 x 10-5
8 5 . 4 3.00 x 10-4
100.3 1.48 x 1O-3
2 5 6.7 x 1O-5
1 0 . 5 3.50 x 10-5
1 1 5 1.23 x 1O-4
1 2 5 3.05 x 10-4
5 0 5.4 x 10-5
44 1.93 x 10-5
60 1.93 x 10-4
7 7 1.93 x 10-3
T W
3.3 x 106
50 5.9 x 10-5
4 5 2.78 x 1O-5
50 5.58 x 1O-4
60 2.07 x 1O-4
4 5 6.69 x 1O-5
5 5 2.48 x 1O-4
6 5 8.27 x 1O-4
40 6.91 x 1O-6
50 2.80 x 1O-5
60 1.032 x 10 -4
70 3.57 x 1o-4
4 5 1.9 x 1o-5
4 3 1.93 x 10-5
61 1.93 x 10-4
81 1.93 x 10-3
T W)
1.47 x 1o14
60.00 8.05 x 1O-5
4 5 5.15 x 10-5
5 5 2.05 x 1O-5
6 . 5 7.40 x 10-5
6 4 . 6 6.87 x 1O-5
74.6 2.44 x 10-4
8 4 . 6 7.78 x 1O-4
60 5.4 x 10-5
70 2.12 x 10-4
8 0 7.20 x 1O-4
1 4 1 . 2 h
1 0 9 . 2
9 6 . 2
9 8 . 3
ch
t9
t9
mz
c,h
c,h,g
109.3 h
t12
116.5
0
k
1 5 1 . 0
Xl
X l
Xl
C
exp[- 129.O/RT]
1 1 7
1 0 9 . 6
a
a
a
ch
C
C
a
exp[- 114.38/RT]
116.5
115.5
h
h
116.7 h
1 2 4 . 7 h
255
255
255
81
1 6 5
1 6 5
1 6 5
81
81
265
265
334
334
334
334
334
2 6 5
2 6 5
2 6 5
334
334
334
334
334
254
254
254
2 0 3
215
215
215
2 0 1
344
344
344
344
2 0 1
337
3 3 7
337
31
3 1
31
368
368
3 6 8
3 6 8
338
344
344
3 4 4
344
280
1 6 0
1 6 0
1 6 0
1 5 9
1 5 9
1 5 9
223
223
223
TABLE 6. contd
Peresters and Peroxycarbonates II/63
Number of
C atoms Initiator Solvent
T (3 kd (S-l) E, Wmol) Notes Refs.
15 (contd) fen-Butyl 4-(carboethoxy)-
phenoxyperacetate
rert-Butyl u$-dimethyl-
percinnamate @is)
(trans)
rerr-Butyl I-pemaphthoate
rerr-Butyl 2,2-dimethyl-
3-phenylthio perpropionate
teti-Butyl 2-(4-methoxyphenyl)-
2-methylperpropionate
terf-Butyl I-phenylcyclo-n-Dodecane
butylpercarboxylate
terr-Butyl 4-tert-butylperbenzoate Chlorobenzene
Di-rert-butyl perpimelate Styrene
ter&Butyl 2-(4-tolyl)-
2-methylperpropionate
rert-Butyl triisopropylperacetate
l,l-Dimethyl-2-phenylethyl-
perpivalate
16
I-Phenylethyl4-methoxyperacetate Benzene
I-Phenylethyl 3-nitroperbenzoate Benzene
1-Phenylethyl 4-nitroperbenzoate Benzene
1-Phenylethyl perbenzoate Benzene
Dibenzyl peroxydicarhonate Benzene
Di-rert-butyl 2-iodoperisophthalate Chlorobenzene
Di-rerr-hutyl perphthalate Benzene
Ethylbenzene 7 0 . 5 1.6 x 1O-4
Chlorobenzene
Cyclohexane
Acetonitrile
Benzene
Dodecane
Octane
5 2 . 3
Ethylbenzene
n-Hexadecane
2,2,4-trimethyl pentane
Acetonitrile
Benzene
Dodecane
Octane
Cumene
Cumene
Di-n-hutyl phthalate
Chlorobenzene
95.0
1 0 3 . 2
110.1
85.1
95.0
1 0 3 . 7
1 1 0 . 0
1 1 0 . 0
110.1
5 5
6 5
75
50
50
40
50
5 7
50
7.89 x 1O-5
60.0
5 2 . 3
5 2 . 3
6 1 . 6
100.1
1 1 9 . 8
1 3 5 . 9
1 0 5
1 1 5
1 2 5
5 0 . 0
5 0 . 0
50.0
60.0
67.0
6 0 . 0
2 4 . 8
41.6
5 5 . 2
40
50
60
70
9 9 . 7
1 0 0
1 0 0
1 0 0
40
50
60
68.4
8 5 . 4
1 0 1 . 6
1 0 0
1 1 5
1 3 0
1 0 0
115
1 3 0
1 0 7
1 2 5
1 4 6
T 6)
1 . 0 2 x 10-4
2 . 2 9 x 10-4
5 . 1 5 x 10-4
3 . 9 x 10-5
1.17 x 10-4
2 . 8 4 x 1O-4
6 . 0 5 x 1O-4
7.90 x 10-4
8 . 6 9 x 1O-5
1.63 x 1O-5
1.61 x 1O-5
1 . 9 8 x 1O-4
1 . 6 7 5 x 1O-3
9.96 x 1O-4
1.49 x 10-4
4 . 2 1 x 1O-4
1 . 0 2 8 x 1O-3
4 . 1 8 x 1O-4
3 . 6 2 x 1O-4
8.80 x 10 -5
7.69 x 1O-s
2 . 4 6 x 1O-4
3.81 x 1O-5
4.50 x 1o-4
2.38 x 1O-3
4 . 4 5 x 10-5
1.05 x 10-4
5 . 0 6 x 1O-4
6.00 x 1O-4
3 . 8 5 x lO-4
1 . 9 0 x 10-4
5 . 5 8 x 1O-4
1 . 3 2 0 x 1O-3
5 . 4 3 x 10-4
5.32 x 1O-6
6 . 8 4 x 1O-5
3 . 7 8 x 1O-4
4.56 x 1O-6
1 . 8 3 3 x 1O-5
6.1 x lo-
2.51 x 1O-4
3.50 x 10-4
5 . 9 7 x 10-4
4.10 x 10-4
4 . 0 3 x 10-4
2 . 0 x 10-5
6 . 2 5 x 1O-5
2 . 6 7 x 1O-4
8 . 2 4 x 1O-5
4 . 4 5 x 10-4
1.68 x 10 -3
1.1 x 10-5
7.81 x 1O-5
4 . 8 1 x 1O-4
1.08 x 1O-5
7 . 8 x 1O-5
4 . 8 x 1O-4
1.93 x 10-5
1.93 x 10-4
1.93 x 10-3
9.39 x 106
1 1 8 . 8
1 2 2 . 6
2 116.9
a
ah
a
a
ah
a
a
a
hv.5
hrt6
t6
93.0 h
1 1 0 . 6
2 5 5
tl
h
1 5 0 . 6
Xl
Xl
XI
1 0 0 . 6 h
1 1 1 . 5 h
134.1
1 3 6 . 2
1 4 6 . 2
1 2 3 . 6
1 1 7
93.9
1 5 9
1 5 5 . 0
exp[- 157.85/RT]
3 1 5
151
151
151
151
151
151
151
151
1 5 4
320
320
320
265
265
265
265
265
265
3 2 3
255
255
2 5 5
1 3 4
1 3 4
1 3 4
2 1 5
2 1 5
2 1 5
2 6 5
265
2 6 5
2 6 5
265
/
265
I
267
2 6 7
267
362
362
362
362
259
259
259
259
3 3 7
3 3 7
337
248
248
248
3 3 7
3 3 7
337
269
269
269
344
344
344
344
Notes page II - 69; References page II - 70
II/64 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 6. contd
Number of
C atoms Initiator Solvent
T (C) kd (S-l) E. Wmol) Notes Ref s.
16 (contd) Di-[err-butyl perphthalate Cumene
rert-Butyl l-phenyl-l-cyclo-
pentane percarboxylate
tert-Butyl 2,3-dimethyl-
2-phenylperbutyrate
Cumyl N-phenylperoxy carbamate
Dibenzyl peroxydicarbonate
Di-rerf-butyl perphthalate
Di-tert-butyl persuberate
ferr-Butyl l-phenylcyclopentyl-
percarboxylate
1,1,3,3-Tetramethylbutyl-
per-2-ethylhexanoate
Styrene
2,2,4-Trimethyl-
pentane
Benzene
2-Phenylazo-2-propylperbenzoate Chlorobenzene
17
1-Phenylethyl 4-dimethyl-
aminoperbenzoate
Di-terr-butylperhomoterephthalate
tert-Butyl l-phenylcyclo-
hexanepercarboxylate
terr-Butyl 2-(phenylthio)perbenzoate
terf-Butyl dibenzothiophene-4-per-
carboxylate
Di-tert-butyl perazelate Styrene
Ethylbenzene
Ethylbenzene
Xylene
Toluene
Benzene
p-Chlorotoluene
Chloroform-d,
Benzene
Cumene
Toluene
Ethylbenzene
2,2,4-Trimethyl-
pentane
Acetone
Acetonitrile
tert-Butanol
Chlorobenzene
Cyclohexane
DMSO
Ethanol
lsopropanol
Methanol
Chlorobenzene
Chlorobenzene
9 9 . 9 8 . 3 4 x lo-6
1 1 5 . 0 4 . 6 8 x 1O-5
130.1 2 . 6 0 x 1O-4
6 0 . 0 1.52 x 1O-3
140.8 h
t1
269
269
269
3 2 3
5 0 4.30 x 10-5 324
T W 1.26 x lOI
50 2 . 9 2 x 1O-5
1 0 0 1.08 x 10-5
115 7 . 8 3 x 10-5
1 3 0 4.80 x 10-4
1 1 5 7.86 x 10 -5
125 2.81 x 10-4
4 3 . 5 1 . 1 8 4 x 10-4
5 2 . 3 3.51 x 10-4
6 0 1.9 x 10-5
7 0 5.30 x lo-5
8 0 1.38 x 10 -4
10 4 . 5 x 10-4
3 5 1.9 x 10-3
1 0 6 . 4 x 1O-4
10 5.1 x 10-4
1 0 0 2 . 1 6 x 1O-3
exp[- 117.6/RT]
1 5 7 . 7
1 5 9 : o
103.5
a
a
a
a
Xl
Xl
h
101 a
a
a
111.5 h
40
90
1 2 6
1 2 6
1 2 6
2 1 5
2 1 5
2 5 5
2 5 5
337
3 3 7
337
260
260
260
260
259
7 9 . 6 2 . 3 8 x 10m5
1 0 . 6 9 . 4 4 x lo-6
8 0 . 3 2 . 8 0 x 1O-5
100.5 3 . 0 9 x lo-4
6 0 . 0 1.90 x 10-3
4 3 . 5 1.27 x 1O-4
5 2 . 3 3.91 x 10-4
6 1 . 6 1 . 2 1 8 x 1o-3
2 5 1.89 x 1O-5
40 1.22 x 10-4
2 5 1.01 x 10-4
40 5 . 4 4 x 10-4
2 5 5 . 2 6 x 1O-5
40 3 . 2 4 x lO-4
3 9 . 3 4 . 9 8 x 10-5
5 3 . 8 5 . 2 3 x 1O-4
5 3 . 8 4 . 5 8 x 10-4
70.0 2 . 6 2 x 1O-3
2 5 1.76 x 1O-5
40 1.03 x 10-4
2 5 9 . 8 x 10-7
40 6 . 9 x 1O-6
2 5 1.11 x 10-4
40 6 . 0 2 x 1O-4
2 5 2.31 x 1O-4
40 1.65 x 1O-3
2 5 1.33 x 10-4
40 7 . 2 5 x 1O-4
2 5 8.21 x 10-4
40 4 . 7 5 x 10-3
105 2 . 7 9 x lo-
1 1 9 . 4 1.29 x 1O-4
135.1 6 . 0 7 x 1O-4
105 5 . 1 3 x 10-5
115 1.20 x 1o-4
1 2 5 5 . 1 0 x 10-4
9 8 1.93 x 10-5
1 1 6 1.93 x 10-4
137 1.93 x 10-3
T 6)
1.35 x 106
1 2 2 . 3 h
1 0 7 . 7 h
m2
m2
m2
m2
m2
m2
b
m2
1 2 8 . 0
m2
m2
m2
m2
m2
m2
m2
m2
m2
m2
m2
m2
h
1 5 4 . 8
exp[- 147.95/RT]
272
212
272
212
3 2 3
2 5 5
255
2 5 5
2 2
22
2 2
2 2
2 2
2 2
1 3 4
1 3 4
1 3 4
1 3 4
2 2
22
2 2
2 2
2 2
2 2
2 2
22
2 2
2 2
2 2
2 2
2 2
2 2
2 2
2 1 5
2 1 5
2 1 5
344
344
344
344
TABLE 6. contd
Peresters and Peroxycarbonates II/65
Number of
C atoms Initiator Solvent
T ((2 kd (S-l) E, Wmol) Notes Refs.
Benzene
Chlorobenzene
Chlorobenzene
Cumene
2 5 1.84 x 1O-4
1 1 0 2 . 8 8 x 1O-5
60 4.44 x 10-4
4 0 . 3 2 . 7 5 x lo-
49.6 9 . 8 1 x 1O-5
5 9 . 9 3 . 1 0 x 10-4
7 0 . 4 1.04 x 10-3
7 7 . 5 1.66 x 1o-3
7 7 . 5 1 . 6 8 8 x 10-3
7 7 . 5 1 . 6 3 2 x 1O-3
7 7 . 5 1.651 x 1O-3
7 7 . 5 1 . 6 2 7 x 1O-3
40 1.93 x 10-5
5 7 1.93 x 10 -4
76 1.93 x 10-3
T W
3 . 9 7 x 104
P2
1 0 1 . 7 ah
1 0 4 . 6 h
Decane
Dodecane
Hexadecane
Octane
tetradecane
Chlorobenzene
exp[- 115.79/RT]
219
219
81
1 3 6
1 3 6
1 3 6
1 3 6
1 6 8
1 6 8
1 6 8
1 6 8
1 6 8
344
344
344
344
Ethylbenzene 9 5 2.68 x 1O-6
1 0 5 9.10 x 10-6
115 2.97 x lo--
147.5 306
306
306
Ethylbenzene 60.0 2.75 x 1O-3 3 2 3
Cumene
Chlorobenzene
Chlorohenzene
70.9
8 5 . 4
100.3
9 8 . 7
120.1
1 2 0
1 3 5
105
1 1 5
1 2 5
3 . 6 9 x 1O-5
2 . 0 8 x 1O-4
8 . 8 3 x 1O-4
4.64 x lo-s
4.20 x 1O-4
1 . 8 9 x 1O-4
1.15 x 10-3
5 . 1 0 x 10-5
1 . 2 0 x 10-4
5.00 x 1o-4
1.9 x 10-5
1.93 x 10-5
1.93 x 10-4
1.93 x 10-3
1.83 x lOI5
5 . 3 x 10-6
3.31 x 10-5
2 . 3 2 x 1O-4
1.3 x 10-5
6.14 x 1O-5
2.31 x 1O-4
6.1 x 1O-6
3 . 8 5 x 1O-5
1 . 7 0 x 1o-4
1 1 2 . 7 U
k
k
1 3 4 . 7 h
156.5 hm
Styrene
m2
1 5 4 . 8
Xl
Xl
Xl
254
254
254
1 5 4
1 5 4
2 2
2 2
2 1 5
2 1 5
2 1 5
Benzene
Chlorohenzene
40
47
64
8 3
T 6)
30
4 5
60
40
50
60
60
7 3 . 5
8 5
a
Decane
exp[- 122.45/RTJ
1 0 5 a
a
Mineral spirits
a
1 2 6 a
Di-n-heptyl persuccinate Styrene 1 3 1 . 0
a
a
XI
Xl
X l
338
344
344
344
344
3 3 7
3 3 7
3 3 7
337
337
337
215
2 1 5
2 1 5
Chlorobenzene
Cumene
103.3 ah
112.1 h
Cumene 1 1 7 . 2 h
Chlorobenzene
6 0 1.9 x 10-3
60.0 2 . 8 x 1O-5
70.0 5 . 5 x 10-5
8 0 . 0 1.68 x 10-4
6 0 . 0 1.6 x 1O-5
7 0 . 0 3 . 9 x 10 -5
8 0 . 0 1.20 x 10-4
34.1 7 . 7 6 x 1O-5
81
204
204
204
204
204
204
249
Benzene 1 0 0 3 . 1 8 x 1O-5
Carbon tetrachloride 1 0 0 3 . 6 0 x 10-5
Benzene 2 5 1.45 x 10-4
Chlorobenzene 1 1 0 3 . 0 3 x 10-5
c,e
c,e
P2
246
246
279
279
18 terr-Butyl 4-benzoylperbenzoate
rert-Butyl diphenylperacetate
2,4,4-Trimethylp-entyl-
cL,o-Di-O,O-tert-butyl-(bis-
persuccinyl)ethylene glycol
rerr-Butyl l-phenyl-l-cyclo-
heptanepercarboxylate
Di-rert-butyl p-phenylene-
reti-Butyl 2-(phenylthiomethyl)-
perbenzoate
rert-Butyl thioxanthone-4-per-
carboxylate
Di-w-r-butyl persebacate
Di-(2-ethylhexyl)peroxy-
dicarbonate
19 rert-Butyl diphenylmethyl-
peracetate
rert-Butyl diphenylperglycidate
(cis)
(Wmw)
ferr-Butyl 2,2-diphenylperpropionate
rert-Butyl 4-hydroxy-3,5-di-
(rert-butyl)perbenzoate
rert-Butyl 4-(4-methylbenzoyl)-
perbenzoate
Notes page II - 69; References page II - 70
II/66 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 6. contd
Number of
C atoms Initiator Solvent
T (C) ka (S-l) E, &I/mol) Notes Refs.
19 (cent d) rerf-Butyl a-phenylpercinnamate
(cis)
(tram)
Cumyl pemeodecanoate
20 Di-n-heptyl peradipate Styrene
terf-Butyl 2-carbobenzoxy-
phenylperacetate
fert-Butyl 2-methyl-2-phenyl-
perhexanoate
a,w-Di-O,O-rert-butyI-(bis-
persuccinyl)diethylene glycol
21 rert-Butyl S-(phenylthio)-
1 -pemaphthoate
2 2
[err-Butyl 4-(2,4,6-trimethyl-
benzoyl)perbenzoate
terr-Butyl 2,2-diphenyl-
3,3-dimethylperbutanoate
Di-rert-butyl 2-thiophenyl-
perisophthalate
2,5-Dimethylhexyl
2,5-di(peroxybenzoate)
Di-(4-rerf-butylcyclohexyl)-
peroxydicarbonate
2 3 terr-Butyl 2,6-di(phenylthio)-
perbenzoate
fert-Butylperoxy stearyl carbonate
terr-Butyl 2,4,6-tri-ferr-butyl-
perbenzoate
2 4 rerr-Butyl triphenylperacetate
Di-rert-butyl 2,3-diphenyl-
persuccinate
Cumene
Di-n-heptyl persebacate Styrene
2,5-Dimethyl-2,5-bis(2-ethyl.
hexanoylperoxy)hexane
Cumene
Cumene
Benzene
Chlorobenzene
Cumene
Ethylbenzene
Ethylbenzene
Chlorobenzene
Benzene
Chlorobenzene
Toluene (?)
Chlorobenzene
Benzene
Chlorobenzene
Chlorobenzene
Chlorobenzene
Cumene
Chlorobenzene
Cumene
Benzene
Chlorobenzene
9 9 . 6 1.52 x 10-4
109.8 4 . 4 1 x 10-4
9 9 . 6 8 . 2 x 1O-5
1 0 9 . 8 2 . 5 9 x 10 -4
3 9 1.9 x 10-5
3 9 1.93 x 10-5
56 1.93 x 10-4
7 5 1.93 x 10-3
T 09
3 . 1 2 x lOI4
60 1.02 x 10-5
7 3 . 5 6 . 5 7 x 10-5
8 5 2 . 9 8 x 1O-4
7 1 . 0 8 . 8 4 x 1O-6
8 5 . 4 5.46 x 10 -5
1 0 2 . 4 4 . 2 3 x 1O-4
5 0 5.01 x 10-5
9 5 2 . 3 4 x 1O-6
105 8 . 8 8 x 10-6
115 3 . 2 7 x 1O-5
5 0 3 . 8 3 x 1O-5
70 3 . 4 4 x 1o-4
70 3 . 1 2 x 1O-4
8 0 9 . 8 2 x 1O-4
2 5 1 . 3 4 x 10-4
1 1 0 1.80 x 1O-5
30 2 . 7 6 x 1O-5
3 9 . 7 1.15 x 10-4
50 5 . 4 5 x 10-4
12.1 1.68 x 10-4
2 5 . 0 6 . 4 5 x 1O-4
40.0 3 . 0 9 x 10-3
1 0 0 1.87 x 1O-5
1 1 5 1.25 x 1O-4
1 3 0 7.14 x 1o-4
48 1.93 x 10-5
64 1.93 x 1o-4
8 2 1.93 x 10-3
T (K) 7 . 4 4 x 105
4 0 . 1 7 . 0 7 x 10 -5
9 8 1.93 x 10-5
1 1 7 1.93 x 10-4
1 3 7 1.93 x 10-3
T 6)
3 . 9 4 x 106
7 0 . 4 5 . 8 4 x 1O-6
8 4 . 0 3 . 5 4 x 10-5
9 9 . 3 2 . 6 7 x 1O-4
1 1 5 . 0 1 . 6 5 6 x 10 -3
3 4 . 9 7 . 8 x 1O-4
2 5 . 7 1.7 x 10-4
3 4 . 9 5 . 8 x 1O-4
45.5 2 . 3 x 1O-3
7 0 . 1 9 . 8 3 x 10 -5
7 9 . 9 3 . 2 9 x 1O-4
9 0 . 0 1 . 2 0 x 10-3
60 1.17 x 10-5
7 3 . 5 7 . 1 3 x 10-5
8 5 3 . 0 3 x 10-5
6 0 6 . 7 x 1O-6
70 2 . 9 2 x 1O-5
8 0 1.14 x 10-4
6 8 1.93 x 10-5
8 6 1.93 x 10-4
1 3 6 . 8 h
1 3 3 . 9 h
a
exp[- 114.59/RlJ
133.1
129.5
Xl
Xl
Xl
h
1 5 5 . 0 h
9 9 . 2 km2
m2
1 1 4 . 8
7 3 . 7
m2
P2
j2
j2
k
h
1 5 4 . 0 a
a
a
exp[- 126.39/RT]
exp[- 151.59/RT]
1 0 0 . 8 h
125.5
1 3 1 . 0
1 4 2
c,h
C
C
Xl
Xl
Xl
a
a
a
1 5 0
1 5 0
1 5 0
1 5 0
3 3 8
344
344
344
344
2 1 5
215
2 1 5
257
257
257
324
306
306
306
1 5 4
1 5 4
1 5 4
1 5 4
279
279
250
250
250
248
248
248
1 2 6 , 3 3 7
1 2 6 , 3 3 7
1 2 6 , 3 3 7
344
344
344
344
1 5 4
344
344
344
344
3 4 5
345
3 4 5
3 4 5
1 5 3
153
153
1 5 3
1 9 6
1 9 6
1 9 6
2 1 5
2 1 5
2 1 5
3 3 7
3 3 7
3 3 7
344
344
TABLE 6. conrd
Peresters and Peroxycarbonates II/67
Number of
C atoms Initiator Solvent
T ((2 kd (S-l) E, Wmol) Notes Refs.
24 (cow d )
25
26
36
46
2,5-Dimethyl-2,5-bis(2-ethyl-
hexanoylperoxy)hexane
ten-Butyl 2-(2,2-diphenylvinyl)-
perbenzoate
tert-Butyl 2-percarboxybenzal-
fluorene
cc,w-Di-O,O-caprylyl-(bis
succinyl)ethylene glycol
a,w-Di-O,O-caprylyl-(bis-
persuccinyl)triethylene glycol
Dimyristyl peroxydicarbonate
Dicetyl peroxydicarbonate .
cc,w-Di-O,O-heptanoyl-(bis-
perphthaloyl)triethylene glycol
u,w-Di-O,O-caprylyl-(bis-
persuccinyl)nonaethylene glycol
cc,w-Di-O,O-heptanoyl-(bis-
perphthaloyl)tridecaethylene
glycol
a,w-Di-O,O-caprylyl-(bis-
persuccinyl)tridecaethylene glycol
Chlorobenzene
Chlorobenzene
Cyclohexane
Methanol
Chlorobenzene
Methanol
Ethylbenzene
Ethylbenzene
Chlorobenzene
Chlorobenzene
Ethylbenzene
Ethylbenzene
Ethylbenzene
Ethylbenzene
1 0 6
T 6)
90. 0
90. 3
1 0 0 . 0
105.5
119.3
90. 0
90. 4
90
90
65
75
85
95
6. 5
15
85
95
48
65
84
T (K)
48
65
84
T 6)
65
15
85
95
65
15
85
95
15
85
9. 5
65
15
85
1.93 x 10-3
2 . 1 9 x lOI5
1.32 x 10m4
7. 45 x 10-5
3. 27 x lO-4
4. 64 x lO-4
1.54 x 10-3
3. 5 x 10-5
2. 3 x lO-3
3. 75 x 10-4
2. 41 x lO-3
1.48 x 1O-5
4.10 x 10-5
2 . 1 9 x lO-4
6. 92 x lO-4
2. 74 x lo-
8. 47 x lO-5
2. 95 x 1O-4
8. 92 x lO-4
1.93 x lo-s
1.93 x 10-4
1.93 x 10-3
2. 82 x lOI
1.93 x lo-s
1.93 x lo-4
1.93 x 10-3
3. 02 x lOI5
5. 02 x lO-5
1 . 4 2 0 x lO-4
5 . 1 9 x 10-4
1 . 4 1 0 x 10-3
1.66 x 10-5
6. 57 x lO-5
1. 18 x lO-4
9. 72 x 1O-4
1. 130 x 10-4
3. 50 x 10-4
8. 80 x 10-4
1.28 x 1O-5
4. 46 x lO-5
1.91 x 10-4
exp[- 130.88/RT]
120. 7
1 1 6 . 9
exp[- 124.lO/RT]
exp[- 124.3O/RT]
1 2 4 . 4
1 1 6 . 9
122.3
128. 2
344
344
175
t9 175
175
t9 175
t9 175
115
t9 115
115
175
h 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
TABLE 7. MISCELLANEOUS INITIATORS
Initiator Sol vent
T CC) ka (s-l) E, Wmol) Notes Refs.
Acetyl cyclohexyl sulfonyl peroxide
N-(l-Cyanocyclohexyl)pentamethylene keteneimine
Dibenzyl hyponitrite
Benzene
Chlorobenzene
Parafhn
30
40
45
80. 0
89. 2
100.1
6 1 . 5
68. 5
15. 5
80. 5
132
1.4 x 10-5
9. 42 x lO-5
2.10 x 10-4
3. 25 x 1O-6
1 . 0 0 1 x lo-s
4. 025 x lO-5
6. 5 x lO-4
3. 7 x 10-3
8. 3 x lO-3
1.45 x 10-2
8. 7 x lo-
1 4 7 a 337
a 337
a 337
119
179
179
240
240
240
240
240
Notes page II - 69; References page II - 70
II/68 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
TABLE 7. contd
Initiator Sol vent
T (Cl kd (S-l) E, Wmol) Notes Refs.
Di-rerr-butyl hyponitrite
Peroxybenzoylnitrate
2,3-Dimethyl-2,3-diphenylbutane
3,4-Dimethyl-3,4-diphenylhexane
l,CDimethyl-1,4-diphenyl-tetrazene-2
Potassium persulfate
I-Pentanesulfonylazide
1,4-Butanedisulfonyl azide
1,6-Hexanedisulfonyl azide
1,9-Nonanedisulfonyl azide
1 ,lO-Decanedisulfonyl azide
1,4-Dimethylcyclohexane-cr,a-disulfonyl azide
rerr-Butanol
n-Butyl ether
Ethanol (95%)
Isooctane
Nujol
Vapor
Vapor + NO
Vapor + NO
Chlorobenzene
Chlorobenzene
Benzophenone
Cumene
Paraffin
Silicone oil
0. 1 M NaOH
Water (pH 3)
Water
Diphenyl ether
Diphenyl ether
Diphenyl ether
Diphenyl ether
Diphenyl ether
Dipheny 1 ether
6 5 4 . 6 8 x 1O-4
6 5 4.50 x 1o-4
6 5 3 . 9 3 x 10-4
45 2 . 7 2 x 1O-5
5 5 1.07 x 10-4
6 5 4.00 x 10-4
15 1 . 3 3 0 x 10-3
6 5 5 . 1 7 x 1o-4
7 . 6 2 . 7 9 x 1O-6
19.9 1.05 x 10-5
3 0 . 4 2 . 0 2 x lo-s
4 0 . 6 3 . 6 4 x 10-5
5 0 . 1 1.21 x 10-4
6 0 . 5 2 . 7 4 x 1O-4
T (K)
1 x 10
18.1 8 . 1 8 x 1O-5
3 0 . 4 3 . 6 2 x 1O-4
40.6 1.42 x 1O-3
T K) 1.6 x 10 l5
3 0 . 4 1.34 x 10-5
5 0 . 2 7 . 2 2 x 1O-5
6 8 . 5 3.41 x 10-4
T (K) 6 . 3 x 1O-8
237 1.93 x 10-5
259 1.93 x 10-4
284 1.93 x 10-3
T W) 7 . 3 4 x 108
2 0 1 1.93 x lo-s
226 1.93 x 10-4
254 1.93 x 10-3
T W
1.45 x 105
121 3 . 3 x 10-4
1 4 9 3 . 4 5 x 10-3
1 2 0 2 . 3 x 1O-4
1 3 0 6 . 5 x 10 -4
1 4 0 1.67 x 1O-3
1 6 4 . 2 2 . 6 x lo-*
174.3 5 . 6 x lo-*
1 8 6 1.43 x lo-
1 9 4 2 . 5 x lo-
1 2 6 3 . 7 x 10-4
1 3 9 1.92 x 1O-3
50 9 . 5 x 10 -7
60 3 . 1 6 x 1O-6
70 2 . 3 3 x 1O-5
8 0 9.16 x 1O-5
90 3.5 x 1o-4
50 1.66 x 10-6
8 0 6 . 8 9 x 1O-5
80 5 . 7 8 x 10-5
40 1.65 x lo-*
50 4 . 0 2 x lo-*
60 1.08 x 10-1
50 3 . 7 8 x 10 -3
60 2 . 1 8 x 10-2
70 5.01 x 10-2
50 1.1 x 10-6
1 6 6 4.46 x 1O-4
163 5 . 0 2 x 1O-4
1 6 3 5 . 0 2 x 1O-4
1 5 0 8 . 8 4 x 1O-5
1 6 0 2 . 2 5 x 1O-4
1 7 0 4 . 4 5 x 10-4
1 6 3 4 . 4 5 x 10-4
1 6 3 4 . 8 2 x 1O-4
1 1 6 . 9
69.1
exp[- 69.1/RT]
108.5
exp[- 108.5/RT]
79.2
exp[- 79.2/RlJ
exp[- 230.19/RTJ
exp[- 180.32/R7'J
1 4 0 . 2
8 3 . 4
121.5
3 1 7
3 1 7
3 1 7
h 3 1 7
3 1 7
3 1 7
3 1 7
3 1 7
h 261
261
2 6 1
261
261
2 6 1
261
h 2 6 1
2 6 1
2 6 1
2 6 1
h 2 6 1
2 6 1
2 6 1
2 6 1
344
344
344
344
344
344
344
344
240
240
240
240
240
240
240
240
240
240
240
a 242
a 242
a 242
a 242
a 242
a 242
a,vll 1 1 5
a,vll 1 1 5
d3rvn 262
d3rvz 262
ds,v22 262
d3rv23 262
d3,Vz 262
d3,vz3 262
262
1 6 6
1 6 6
1 6 6
1 6 6
1 6 6
1 6 6
1 6 6
1 6 6
m-Xylene-a,a-disulfonyl azide Diphenyl ether
p-Xylene-a,cc-disulfonyl tide Diphenyl ether
Benzenesulfonyl azide Naphthalene
pBromobenzenesulfony1 azide
pChlorobenzenesulfony1 azide
p-Methoxybenzenesulfonylazide
p-Nitrobenzenesulfonyl azide
p-Toluenesulfonyl azide
p-Toluenesulfonyl-p-tolylsulfone
Naphthalene
Naphthalene
Naphthalene
Naphthalene
1,4-Dichlorobutane
Dimethyl terephthalate
Diphenyl ether
Hexanoic acid
Naphthalene
Nitrobenzene
1-Octanol *
Tetradecane
Acetonitrile
Dioxane
1 6 3 6 . 0 9 x 1O-4
1 6 3 5 . 7 8 x 10-4
1 1 0 3 . 6 x 1O-6
1 2 0 1.07 x 1o-5
125 1.97 x 10-5
1 3 0 3.41 x 1o-5
1 7 5 6 . 0 8 x 1o-5
1 2 0 1.36 x 1O-5
1 2 0 1.15 x 10-5
1 2 0 1.31 x 1o-5
1 2 0 1.60 x 1O-5
1 4 . 5 1.70 x 10-4
155 3 . 2 3 x 1O-4
1 3 0 3 . 3 0 x 10-5
1 4 5 1.44 x 1o-4
1 5 5 3 . 4 3 x 1o-4
1 5 5 2 . 9 7 x 1O-4
1 2 0 1.12 x 1o-5
155 3 . 9 7 x 1o-4
1 5 5 3 . 6 3 x 1O-4
1 5 5 3.80 x 1o-4
2 9 . 3 3 . 9 x 1o-5
39.1 1.45 x 10-4
4 9 . 3 5 . 4 x 10-4
2 9 . 3 2.1 x 1o-5
3 9 . 5 1.01 x 1o-4
4 9 . 3 3 . 9 x 1o-4
Not es II/69
152.3
103.8
1 1 5 . 5
1 6 6
1 6 6
2 3 5
2 3 5
2 3 5
2 3 5
235
2 3 5
2 3 5
2 3 5
2 3 5
1 6 6
1 6 6
1 6 6
1 6 6
1 6 6
1 6 6
2 3 5
1 6 6
1 6 6
1 6 6
h 1 4 4
1 4 4
1 4 4
h 1 4 4
1 4 4
1 4 4
C. NOTES
:
bz
C
c2
c3
c4
d
dz
d3
;
kd converted to s-l from authors units
kd values for several concentrations averaged
analyzed from nonisothermal conditions
kd increases with increasing initiator concentration
rate non-linear
hydroperoxide concentration 7.83 x lop3 mol/l
hydroperoxide concentration 2.50 x 10e3 mol/l
kd decreases with increasing initiator concentration
after 1st half life; rate slower initially
rate is second order: units are l/mol sec.
kd listed is for lowest initiator concentration
kd is extrapolated value for zero initiator
concentration
g
it2
h
i
j
j2
k
1
kd # has been corrected for induced decomposition
corrected for uncatalysed reaction (7 x lop5 s-)
AH (not E,)
pressure (number gives mbar)
iodometric analysis
manometer measurement
infrared analysis
kd is limiting value with respect to additive
concentration
ml
3,4-dichlorostyrene added to minimize induced
decomposition
m2
m3
styrene added to minimize induced decomposition
methyl methacrylate added to minimize induced
decomposition
m4
m5
isobutene added to minimize induced decomposition
acenaphthalene added to minimize induced
decomposition
m6
1 mol/l a-methylstyrene added to minimize induced
m7
m8
n
n2
0
P
P2
9
q2
q3
r
S
t1
t2
t3
t4
t5
t6
t7
t8
decomposition
butadiene added to minimize induced decomposition
acrylonitrile added to minimize induced
decomposition
trichloroacetic acid added
3.2 wt.% or about 0.1 monolayer
addition of trichloroacetic acid did not affect kd
degassed
photochemical benzophenone added: 6.56 x 10 l7
quants/min @ 366nm
addition of trichloroacetic acid increased kd several
fol d
pH 2.90
pH 7.05
not inhibited, but initiator concentration low enough
(0.01-0.09 M) so that higher order decomposition is
unimportant
solvent not degassed
2,6-di-tert-butylphenol added to inhibit induced
decomposition
a,a-diphenyl+picrylhydrazyl added to inhibit
induced decomposition
phenyl-a-naphthylamine added to inhibit induced
decomposition
tetrachloroquinone added to inhibit induced
decomposition
1,3,5trinitrobenzene added to inhibit induced
decomposition
12 added to inhibit induced decomposition
O2 added to inhibit induced decomposition
5-20% NO2 added to inhibit decomposition
References page II - 70
II/ 70 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
tg galvanoxyl added to inhibit induced decomposition
t 10 a,y-bisdiphenylene-P-phenylallyl added to inhibit
induced decomposition
t 11 a-naphthylamine added to minimize induced
decomposition
t 12 2,3,5,6-tetra-terbutyl indophenoxy added
t 1s benzoquinone added
t 14 2,6-di-tert-butyl-4-methylphenol added
Ul
in absence of oxygen
u2 from initiation data
u3
in multisurface reaction vessel
u4 rate reduced when nujol layer used to exclude Hg
vapor
ug rate increased when nujol layer used to exclude Hg
vapor
vi acetic acid added
v:! CuC12 added
vg CuCl added
v4 0.1 mol AgC104/mol AIBN added
vg 3.9 mol thiophenol added
vg tert-butyl mercaptan added
v7 2.5 mol cyclohexane added
v8
N 4 x 10m2 mol pyridine added
vg 2 x 10 -2 mol pyridine added
D. REFERENCES
1. J. E. Guillet, T. R. Walker, M. F. Meyer, J. P. Hawk,
E. B. Towne, Ind. Eng. Chem., Prod. Res. Develop., 3,
257 (1964).
2. L. M. Arnett, J. Am. Chem. Sot., 74, 2027 (1952).
3. L. M. Amett, J. H. Peterson, J. Am. Chem. Sot., 74, 2031
(1952).
4. W. M. Thomas, M. T. OShaughnessy, J. Polym. Sci., 11,455
(1953).
5. A. T. Blomquist, A. J. Buselli, J. Am. Chem. Sot., 73, 3883
(1951).
6. C. G. Swain, J. T. Parke, W. H. Stockmeyer, J. Am. Chem.
Sot., 72, 5426 (1950).
7. D. J. Brown, J. Am. Chem. Sot., 70, 1208 (1948).
8. S. W. Butaka, L. L. Zabrocki, M. F. McLaughlin,
J. R. Kolcznski, 0. L. Mageli, Ind. Env. Chem. Prod. Res.
Develop., 3, 261 (1964).
9. W. A. Strong, Ind. Eng. Chem. Prod. Res. Develop., 3, 264
(1964).
10. L. E. Redington, J. Polym. Sci., 3, 503 (1948).
11. B. Baysal, A. V. Tobolsky, J. Polym. Sci., 8, 529 (1952).
12. A. Conix, G. Smets, J. Polym. Sci., 10, 525 (1953).
13. M. R. Gopalan, M. Santhappa, J. Polym. Sci., 25,333 (1957).
14. J. C. Bevington, J. Toole, J. Polym. Sci., 28, 413 (1958).
15. H. C. Haas, J. Polym. Sci., 39, 493 (1959).
16. A. I. Lowell, J. R. Price, J. Polym. Sci., 43, 1 (1960).
17. H. C. Haas, J. Polym. Sci., 55, 33 (1961).
18. D. F. Doehnert, 0. L. Mageli, Mod. Plastics., 36, (6), 142
(1959).
19. R. C. Lamb, P. W. Ayers, M. K. Toney, J. Am. Chem. Sot.,
85, 3483 (1963).
vtu 2.5 mol cumene added
v ii buffered with sodium pyrophosphate
vt2 saturated with ethyl acetate
~13 3.11 mol CC14 present
vi4 peroxide in P(MMA)
vt5 peroxide in P(sty.)
vr6 0.26 mol piperidine
vr7 0.24 mol triethylamine
v 1s 0.21 mol N,N-diethylaniline
vt9 0.22 mol pyridine
~20 0.9 mol ZnC12
vqt in presence of 15N0
~22 0.12 mol 18 crown 6 added
~23 0.24 mol diglyme added ,
~24 0.02 M pyridine added
v 25 0.10 M pyridine added
v26 0.10 M 2,6-lutidine added
W stereoisomers
Xl
actual rate divided by 2 because of two identical
peroxide groups
x2 each peroxide group has different kd
Y
measured in differential scanning calorimeter:
subscript is heating rate in deg/min
Z pressure (in bar)
20. H. J. Shine, J. A. Waters, D. M. Hoffman, J. Am. Chem. Sot.,
85, 3613 (1963).
21. G. S. Hammond, R. C. Neuman, Jr., J. Am. Chem. Sot., 85,
1501 (1963).
22. D. L. Tuleen, W. G. Bentrude, J. C. Martin, J. Am. Chem.
SOL, 85, 1938 (1963).
23. H. Hart, F. J. Chloupek, J. Am. Chem. Sot., 85,1155 (1963).
24. H. Hart, R. A. Cipriani, J. Am. Chem. Sot., 84,3697 (1962).
25. L. J. Durham, H. S. Mosher, J. Am. Chem. Sot., 84, 2811
(1962).
26. R. C. Petersen, J. H. Markgraf, S. D. Ross, J. Am. Chem.
Sot., 83, 3819 (1961).
27. M. M. Martin, J. Am. Chem. Sot., 83, 2869 (1961).
28. P. D. Bartlett, D. M. Simons, J. Am. Chem. Sot., 82, 1753
(1960).
30. P. D. Bartlett, E. P Benzing, R. E. Pincock, J. Am. Chem.
Sot., 82, 1762 (1960).
31. P. D. Bartlett, R. E. Pincock, J. Am. Chem. Sot., 82, 1769
(1960).
32. L. J. Durham, H. S. Mosher, J. Am. Chem. Sot., 82, 4537
(1960).
33. C. Walling, G. Metzger, J. Am. Chem. Sot., 81,5365 (1959).
34. H. Hart, D. P. Woman, J. Am. Chem. Sot., 81,489l (1959).
35. H. H. Lau, H. Hart, J. Am. Chem. Sot., 81, 4897 (1959).
36. E. L. OBrien, F. M. Bennger, R. B. Mesrobian, J. Am.
Chem. Sot., 81, 1506 (1959).
37. N. A. Milas, A. Golubovic, J. Am. Chem. Sot., 80, 5994
(1958).
38. C. G. Overberger, I. Tashlick, M. Vemstein, R. G. Hiskey,
J. Am. Chem. Sot., 80, 6556 (1958).
39.
40.
41.
42.
43.
44.
45.
46.
41.
48.
49.
50.
51.
52.
53.
54.
55.
56.
57.
58.
59.
60.
61.
62.
63.
64
J. P. Van Hook, A. V. Tobolsky, J. Am. Chem. Sot., 80,779
(1958).
E. L. OBrien, F. M. Beringer, R. B. Mesrobian, J. Am.
Chem. Sot., 79, 6238 (1957).
B. K. Morse, J. Am. Chem. Sot., 79, 3375 (1957).
S. Solomon, C. H. Wang, S. G. Cohen, J. Am. Chem. Sot.,
79, 4104 (1957).
C. Walling, J. Pellon, J. Am. Chem. Sot., 79, 4786 (1957).
C. G. Overberger, J. G. Lombardino, I. Tashlich, R. G. Hiskey,
J. Am. Chem. Sot., 79, 2662 (1957).
K. E. Russel, J. Am. Chem. Sot., 77, 3487 (1955).
S. G. Cohen, C. H. Wang, J. Am. Chem. Sot., 77, 3628
(1955).
M. Talat-Erben, S. Bywater, J. Am. Chem. Sot., 77, 3712
(1955).
C. G. Overberger, M. Lapkin, J. Am. Chem. Sot., 77,465l
(1955).
G. S. Hammond, J. N. Sen, C. E. Boozer, J. Am. Chem. Sot.,
77, 3244 (1955).
C. G. Overberger, W. F. Hale, M. B. Berenbaum,
A. B. Finestone, J. Am. Chem. Sot., 76, 6185 (1954).
J. Smid, A. Rembaum, M. Szwarc, J. Am. Chem. Sot., 78,
3315 (1956).
S. G. Cohen, C. H. Wang, J. Am. Chem. Sot., 75, 5504
(1953).
A. T. Blomquist, I. A. Berstein, J. Am. Chem. Sot., 73,5546
(1951).
C. G. Overberger, H. Biletch, J. Am. Chem. Sot., 73, 4880
(1951).
A. T. Blomquist, A. F. Ferris, J. Am. Chem. Sot., 73, 3408
(1951).
A. T. Blomquist, A. F. Ferris, J. Am. Chem. Sot., 73, 3412
(1951).
C. G. Overberger, M. B. Berenbaum, J. Am. Chem. Sot., 73,
2618 (1951).
V. Stannett, R. B. Mesrobian, J. Am. Chem. Sot., 72, 4125
(1950).
P. D. Bartlett, J. E. Leffler, J. Am. Chem. Sot., 72, 3030
(1950).
S. G. Cohen, D. B. Sparrow, J. Am. Chem. Sot., 72, 611
(1950).
C. G. Overberger, M. T. OShaughnessy, H. Shalit, J. Am.
Chem. Sot., 71, 2661 (1949).
F. M. Lewis, M. S. Matheson, J. Am. Chem. Sot., 71, 747
(1949).
J. H. Raley, F. F. Rust, W. E. Vaughan, J. Am. Chem. Sot.,
70, 88 (1948).
J. H. Raley, F. F. Rust, W. E. Vaughan, J. Am. Chem. Sot.,
70, 1336 (1948).
65. C. S. Marvel, R. L. Frank, E. Prill, J. Am. Chem. Sot., 65,
1647 (1943).
66. C. E. H. Bawn, D. Verdin, Trans. Faraday Sot., 56, 815
(1960).
67. H. C. Bailey, G. W. Godin, Trans. Faraday Sot., 52, 68
(1956).
68. C. E. H. Bawn, R. G. Halford, Trans. Faraday Sot., 51,780
(1955).
69.
70.
71.
72.
13.
74.
75.
76.
77.
78.
79.
80.
81.
82.
83.
84.
85.
86.
87.
88.
89.
90.
91.
92.
93.
94.
95.
96.
97.
98.
99.
100.
101.
102.
103.
References II/71
C. E. H. Bawn, S. F. Mellish, Trans. Faraday Sot., 47, 1216
(1951).
W. Braun, L. Rajbenbach, F. R. Eirich, J. Phys. Chem., 66,
1591 (1962).
J. R. Thomas, 0. L. Harle, J. Phys. Chem., 63, 1027 (1959).
P. L. Hanst, J. G. Calvert, J. Phys. Chem,. 63, 104 (1959).
B. Barnett, W. E. Vaughan, J. Phys. Chem., 51, 926
(1947).
B. Bamett, W. E. Vaughan, J. Phys. Chem., 51,942 (1947).
S. G. Cohen, F. Cohen, C. H. Wang, J. Org. Chem., 28,1479
(1963).
R. R. Hiatt, W. M. J. Strachan, J. Org. Chem., 28, 1893
(1963).
J. E. Leffler, J. S. West, J. Org. Chem., 27, 4191 (1962).
W. Honsberg, J. E. Leffler, J. Org. Chem., 26, 733 (1961).
J. E. Leffler, A. F. Wilson, J. Org. Chem., 25, 424 (1960).
M. S. Kharasch, A. Fono, W. Nudenberg, J. Org. Chem., 16,
105 (1951).
P D. Bartlett, R. R. Hiatt, J. Am. Chem. Sot., 80, 1398
(1958).
J. E. Leffler, R. D. Faulkner, C. C. Petropoulos, J. Am. Chem.
Sot., 80, 5435 (1958).
L. Batt, S. W. Benson, J. Chem. Phys., 36, 895 (1962).
J. Smid, M. Szwarc, J. Chem. Phys., 29, 432 (1958).
A. Rembaum, M. Szwarc, J. Chem. Phys., 23,909 (1955).
R. K. Brinton, D. H. Volman, J. Chem. Phys., 20, 25
(1952).
R. E. Rebbert, K. J. Laidler, J. Chem. Phys., 20,574 (1952).
J. Murawski, J. S. Roberts, M. Szwarc, J. Chem. Phys., 19,
698 (1951).
J. E. Leffler, J. Am. Chem. Sot., 72, 67 (1950).
F. Strain, W. E. Bissinger, W. R. Dial, H. Rudolf, B. J. Dewitt,
H. C. Stevens, J. H. Langston, J. Am. Chem. Sot., 72, 1254
(1950).
A. Farkas, E. Passaglia, J. Am. Chem. Sot., 72,3333 (1950).
W. A. Pryor, D. M. Huston, T. R. Fiske, T. L. Pickering,
E. Ciuffarin, J. Am. Chem. Sot., 86, 4237 (1964).
J. C. Bevington, A. Wahid, Polymer, 4, 129 (1963).
A. A. Frost, R. G. Pearson, Kinetics and Mechanism,
Wiley, New York, 1953, p. 97.
J. C. Bevington, T. D. Levis, Polymer, 1, 1 (1960).
F. W. Birss, C. J. Danby, C. Hinshelwood, Proc. Roy Sot.
(London). A, 239, 154 (1957).
J. C. Martin, W. G. Bentrude, Chem. Ind. (London), 192
(1959).
S. G. Cohen, S. J. Groszos, D. B. Sparrow, J. Am. Chem.
Sot., 72, 3947 (1950).
W. E. Cass, J. Am. Chem. Sot., 72, 4915 (1950).
S. D. Ross, M. A. Fineman, J. Am. Chem. Sot., 73, 2176
(1951).
C. G. Overberger, H. Biletch, A B. Finestone, J. Lilker,
J. Herbert, J. Am. Chem. Sot., 75, 2078 (1953).
P. D. Bartlett, F. D. Greene, J. Am. Chem. Sot., 76, 1088
(1954).
M. G. Alder, J. E. Leffler, J. Am. Chem. Sot., 76.,1425
(1954).
II/72 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
104. C. G. Overberger, A. Lebovits, J. Am. Chem. Sot., 76,2722
(1954).
105. A. Rembaum, M. Szwarc, J. Am. Chem. Sot., 76, 5975
(1954).
106. M. Levy, M. Steinberg, M. Szwarc, J. Am. Chem. Sot., 76,
5978 (1954).
137. C. G. Overberger, I. Tashlick, J. Am. Chem. Sot., 81, 217
(1959).
138. C. G. Overberger, J. G. Lambardino, J. Am. Chem. Sot., 80,
2317 (1958).
139. G. S. Hammond, J. R. Fox, J. Am. Chem. Sot., 86, 1918
(1964).
107. S. G. Cohen, C. H. Wang, J. Am. Chem. Sot., 77, 2457
(1955).
108. J. E. Leffler, C. C. Petropoulos, J. Am. Chem. Sot., 79,3068
(1957).
109. W. E. Cass, J. Am. Chem. Sot., 68, 1976 (1946).
110. H. C. Ramsperger, J. Am. Chem. Sot., 50, 714 (1928).
111. F. P Lossing, A. W. Tickner, J. Chem. Phys., 20,907 (1952).
112. A. Robertson, W. A. Waters, J. Chem. Sot., 1578 (1948).
113. 0. J. Walker, G. L. E. Wild, J. Chem. Sot., 1132 (1937).
114. J. E. Leffler, R. A. Hubbard, II, J. Org. Chem., 19, 1089
(1954).
140. E. S. Huyser, C. J. Bredeweg, J. Am. Chem. Sot., 84, 2401
(1964).
141. E. Hedaya, R. L. Hinman, L. M. Kibler, S. Theodoropulos, J.
Am. Chem. Sot., 86, 2727 (1964).
142. T. Koenig, W. Brewer, J. Am. Chem. Sot., 86,2728 (1964).
143. E. S. Huyser, C. J. Bredeweg, R. M. Van Scoy, J. Am. Chem.
Sot., 86, 4148 (1964).
115. P. D. Bartlett, K. Nozaki, J. Polym. Sci., 3, 216 (1948).
116. J. C. Bevington, J. Toole, L. Trossarelli, Makromol. Chem.,
32, 57 (1959).
144. J. L. Kite, N. E. Pawlowski, J. Am..Chem. Sot., 86, 4898
(1964).
145. C. Walling, H. N. Moulden, J. H. Waters, R. C. Newman, J.
Am. Chem. Sot., 87, 518 (1965).
146. J. K. Kochi, D. M. Mog, J. Am. Chem. Sot., 87,522 (1965).
147. P. D. Bartlett, M. McBride, J. Am. Chem. Sot., 87, 1727
(1965).
117. A. N. Bose, C. Hinshelwood, Proc. Roy. Sot., (London) A,
249, 173 (1959).
148. R. C. Lamb, J. G. Pacifici, P W. Avers, J. Am. Chem. Sot..
87, 3928 (1965).
118. E. R. Bell, J. H. Raley, F. F. Rust, F. H. Seubold,
W. E. Vaughan, Disc. Faraday Sot., 10, 242 (1951).
119. L. Bateman, H. Hughes, A. L. Morns, Disc. Faraday Sot.,
14, 190 (1953).
149. S. Seltzer, F. T. Dunne, J. Am. Chem. Sot., 87, 2628
(1965).
150. L. A. Singer, N. P. Kong, J. Am. Chem. Sot., 88, 52 13
(1966).
120. G. S. Hammond, J. Am. Chem. Sot., 72, 3737 (1950).
121. G. S. Hammond, L. M. Softer, J. Am. Chem. Sot., 72,47 11
(1950).
151. R. M. Fantazier, J. A. Kampmeier, J. Am. Chem. Sot., 88,
5219 (1966).
122. G. A. Russell, J. Am. Chem. Sot., 78, 1044 (1956).
123. J. A. Offenbach, A. V. Tobolsky, J. Am. Chem. Sot., 79,
278( 1957).
124. G. S. Hammond, U. S. Nandi, J. Am. Chem. Sot., 83, 1213
(1961).
152. S. Seltzer, E. J. Hamilton, Jr., J. Am. Chem. Sot., 88, 3775
(1966).
153. J. P. Lorand, P. D. Bartlett, J. Am. Chem. Sot., 88, 3294
(1966).
125. G. 0. Pritchard, H. 0. Pritchard, A. F. Trotman-Dickenson,
J. Chem. Sot., 1425 (1954).
126. 0. L. Mageli, S. D. Butaka, D. J. Bolton, Wallace and
Tiernan, Lucid01 Division, Bulletin 30.30, Evaluation of
Organic Peroxides from Half-Life Data.
127. E. J. Harris, A. C. Egenon, Proc. Roy. Sot., (London) A, 168,
1 (1938).
154. T. H. Fischer, J. C. Martin, J. Am. Chem. Sot., 88, 3382
(1966).
155. C. Walling, Z. Cekovic, J. Am. Chem. Sot., 89,668l (1967).
156. T. Koenig, R. Wolf, J. Am. Chem. Sot., 89, 2948 (1967).
157. R. C. Neuman, J. V. Behar, J. Am. Chem. Sot., 89, 4549
(1967).
158. S. G. Mylonakis, S. Seltzer, J. Am. Chem. Sot., 90, 5487
(1968).
128. E. J. Harry, Proc. Roy. Sot., (London) A, 173, 126 (1939).
129. J. K. Allen, J. C. Bevington, Proc. Roy. Sot., (London) A,
262, 271 (1961).
159. J. P. Lorand, S. D. Cnodroff, R. W. Wallace, J. Am. Chem.
Sot., 90, 5266 (1968).
130. G. Archer, C. Hinshelwood, Proc. Roy. Sot., (London) A,
261, 293 (1961).
160. R. C. Fort Jr., R. E. Franklin, J. Am. Chem. Sot., 90, 5267
(1968).
161. J. E. Leffler, H. H. Gibson. Jr., J. Am. Chem. Sot., 90,4117
(1968).
131. J. H. McClure, R. E. Robertson, A. C. Cuthbertson, Can. J.
162. S. E. Scheppelle, S. Seltzer, J. Am. Chem. Sot., 90, 358
Res. B, 20, 103 (1942).
(1968).
132. J. W. Breitenbach, A. Schindler, Monatsh. Chem., 83, 724
(1952).
163. R. C. Neuman, J. V. Behar, J. Am. Chem. Sot., 91, 6024
(1969).
133. R. C. Lamb, F. F. Rogers, G D. Dean, F. W Voight, J. Am.
Chem. Sot., 84, 2635 (1962).
134. W. G. Bentrude, J. C. Martin, J. Am. Chem,. 84,156l (1962).
135. R. C. Neuman, R. P. Pankratz, J. Org. Chem., 36, 4046
(1971).
164. R. C. Lamb, J. R. Sanderson, J. Am. Chem. Sot., 91,5034
(1969).
136. P. D. Bartlett, L. B. Gonler, J. Am. Chem. Sot., 85, 1864
(1963).
165. T. Koenig, R. Wolf, J. Am. Chem. Sot., 91, 2574 (1969).
166. D. S. Breslow, M. F. Sloan, N. R. Newburg, W. B. Renfrow,
J. Am. Chem. Sot., 91, 2273 (1969).
167. C. Walling, H. P. Warts, J. Milovanovic, C. G. Pappiaonnou,
J. Am. Chem. Sot., 92,4927 (1970).
I i
References II/73
168. W. A. Pryor, K. Smith, J. Am. Chem. Sot., 92,5403 (1970).
169. T. Koenig, J. Huntington, R. Cruthoff, J. Am. Chem. Sot.,
92, 5413 (1970).
170. J. E. Leffler, R. G. Zepp, J. Am. Chem. Sot., 92, 3713
(1970).
171. J. C. Martin, J. W. Timberlake, J. Am. Chem. Sot., 92,978
(1970).
172. R. C. Newman Jr., G. D. Holmes, J. Am. Chem. Sot., 93,
4242 (1971).
173. J. B. Levy, E. J. Lehmann, J. Am. Chem. Sot., 93, 5790
(1971).
174. K. Shen, J. Am. Chem. Sot., 93, 3064 (1971).
175. T. W. Koenig, J. C. Martin, J. Org. Chem., 29, 1520 (1964).
176. R. D. Schuetz, J. L. Shea, J. Org. Chem., 30, 844 (1965).
177. J. R. Thomas, J. Am. Chem. Sot., 77, 246 (1955).
178. P. D. Bartlett, C. Ruchardt, J. Am. Chem. Sot., 82, 1756
(1960).
179. C. S. Wu, G. S. Hammond, J. M. Wright, J. Am. Chem. Sot.,
82, 5386 (1960).
180. S. G. Cohen, R. Zand, C. Steel, J. Am. Chem. Sot., 83,2895
(1961).
181. P. D. Bartlett, R. E. Pincock, J. Am. Chem. Sot., 84, 2445
(1962).
182. M. M. Martin, D. C. De Jongh, J. Am. Chem. Sot., 84,3526
(1962).
183. S. Selzer, J. Am. Chem. Sot., 83, 2625 (1961).
184. S. N. Gupta, U. S. Nandi, J. Polym. Sci. A-l, 8,3019 (1970).
185. T. Kagiya, M. Izu, S. Kauai, K. Fukni, J. Polym. Sci. A-l, 6,
1719 (1968).
186. K-P S. Kwei, J. Polym. Sci. A, 3, 2387 (1965).
187. C. Leggett, J. C. J. Thynne, Trans. Faraday Sot., 63, 2504
(1967).
188. S. W. Benson, G. N. Spokes, J. Phys. Chem., 72, 1182
(1968).
189. G. A. Mortimer, J. Org. Chem., 30, 1632 (1965).
190. W. H. Richardson, J. Org. Chem., 30, 2804 (1965).
191. R. C. Lamb, J. G. Pacifici, P W. Ayers, J. Org. Chem., 30,
3099 (1965).
192. E. S. Huyser, R. M. Van Scoy, J. Org. Chem., 33, 3524
(1968).
193. C. Walling, J. C. Azar, J. Org. Chem., 33, 3888 (1968).
194. R. C. Lamb, L. P. Spadafino, R. G. Webb, E. B. Smith,
W. E. McNew, J. G. Pacifici, J Org. Chem., 31, 147 (1966).
195. E D. Greene, W. Adam, G. A. Knudsen Jr., J. Org. Chem.,
31,2087 (1966).
196. L. M. Bobroff, L. B. Gortler, D. J. Sahn, H. Wiland, J. Org.
Chem., 31, 2678 (1966).
197. R. Hiatt, T. Mill, K. C. Irwin, J. K. Castleman, J. Org. Chem.,
33, 1421 (1968).
198. R. Hiatt, K. C. Irwin, C. W. Gould, J. Org. Chem., 33, 1430
(1968).
199. R. Hiatt, K. C. Irwin, J. Org. Chem., 33, 1436 (1968).
200. P. Kovacic, R. R. Flynn, J. F. Gormish, A. H. Kappelman,
J. R. Shelton, J. Org. Chem., 34, 3312 (1969).
201. D. E. Van Sickle, J. Org. Chem., 34, 3446 (1969).
202. E. S. Huyser, K. J. Jankauskas, J. Org. Chem., 35, 3196
(1970).
203. R. A. Sheldon, J. K. Kochi, J. Org. Chem., 35, 1223 (1970).
204. A. Padwa, N. C. Das, J. Org. Chem., 34, 816 (1969).
205. C. G. Overberger, D. A. Labianca, J. Org. Chem., 35, 1762
(1970).
206. W. G. Schindel, R. E. Pincock, J. Org. Chem., 35, 1789
(1970).
207. R. C. Newman Jr., J. V. Behar, J. Org. Chem., 36,654 (1971).
208. C. Walling, D. Bristol, J. Org. Chem., 36, 733 (1971).
209. R. C. Lamb, W. E. McNew Jr., J. R. Sanderson, D. C. Lunney,
J. Org. Chem., 36, 174 (1971).
210. G. S. Kolesnikov, A. Y. Chuchin, Polym. Sci. USSR, 7, 1931
(1965).
211. G. A. Nosayev, 0. N. Romanlsova, Polym. Sci. USSR, 8,14
(1966).
212. Y. A. Chuchin, V. A. Lazarev, M. B. Fromberg, Polym. Sci.
USSR, 10, 2968 (1968).
213. L. M. Aparovich, T. I. Yurzhenko, Polym. Sci. USSR, 10,
1313 (1968).
214. A. I. Prisyazhnyuk, S. S. Ivanchev, Polym. Sci. USSR, 12,
514 (1970).
215. S. G. Yerigova, S. S. Ivanchev. Polym. Sci. USSR, 11,2377
(1969).
216. C. H. Bamford, R. Denyer, J. Hobbs, Polymer, 8, 493
(1967).
217. S. F. Nelsen, P. D. Bartlett, J. Am. Chem. Sot., 88, 137
(1966).
218. R. E. Pincock, J. Am. Chem. Sot., 86, 1820 (1964).
219. R. C. Lamb, J. G. Pacifici, J. Am. Chem. Sot., 86, 914
(1964).
220. S. Seltzer, J. Am. Chem. Sot., 85, 14 (1963).
221. J. B. Levy, B. K. W. Copeland, J. Am. Chem. Sot., 82,5314
(1960).
222. T. Suchiro, H. Tsuruta, S. Hibino, Bull. Chem. Sot. Japan,
40, 674 (1967).
223. L. B. Humphrey, B. Hodgson, R. E. Pincock, Can. J. Chem.,
46, 3099 (1968).
224. V. Stannett, R. B. Mesrobian, Disc. Faraday Sot., 14, 242
(1953).
225. Y. Takezaki, C. Takeuchi, J. Chem. Phys., 22, 1527
(1954).
226. K. Ziegler, W. Deparade, W. Meye, Annalen, 567, 141
(1950).
227. A. R. Blake, K. 0. Kutschke, Can. J. Chem., 37, 1462
(1959).
228. C. F. H. Tipper, J. Chem. Sot., 1675 (1953).
229. W. R. Foster, G. H. Williams, J. Chem. Sot., 2862 (1962).
230. G. B. Gill, G. H. Williams, J. Chem. Sot., 995 (1965).
23 1. G. B. Gill, G. H. Williams, J. Chem. Sot., 7127 (1965).
232. R. D. Schuetz, D. M. Teller, J. Org. Chem., 27, 110
(1962).
233. H. G. G. Dekking, J. Appl. Polym. Sci., 9, 1641 (1965).
234. C. G. Overberger, P Fram, T. Alfrey Jr., J. Polym. Sci., 6,539
(1951).
235. K. Takemoto, R. Fujita, M. Imoto, Makromol. Chem., 112,
116 (1968).
236. K. E. J. Barrett, J. Appl. Polym. Sci., 11, 1617 (1967).
237. T. J. Dougherty, J. Am. Chem. Sot., 83,4849 (1961).
II/74 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
238. M. T. Jaquiss, J. S. Roberts, M. Szwarc, J. Am. Chem. Sot.,
74, 6005 (1952).
239. S. Goldschmidt, B. Acksteiner, Annalen, 618, 173 (1958).
240. J. C. McGowen, T. Powell, Rec. Trav. Chim., 81, 1061
(1962).
241. H. A. Bent, B. Crawford Jr., J. Am. Chem. Sot., 79, 1793
(1957).
242. I. M. Kolthoff, I. K. Miller, J. Am. Chem. Sot., 73, 3055
(1951).
243. D. F. McMillen, D. M. Golden, S. W. Benson, J. Am. Chem.
Sot., 94, 4403 (1972).
244. J. E. Leffler, A. A. More, J. Am. Chem. Sot., 94, 2483
(1972).
245. G. J. Abruscato, T. T. Tidwell, J. Am. Chem. Sot., 94, 672
(1972).
246. A. M. Hucek, J. T. Barbas, J. E. Leffler, J. Am. Chem. Sot.,
95, 4698 (1973).
247. E. L. Allred, K. J. Voorhees, J. Am. Chem. Sot., 95, 620
(1973).
248. J. C. Martin, M. M. Chau, J. Am. Chem. Sot., 96, 3319
(1974).
249. J. P. Lorand, J. Am. Chem. Sot., 96, 2867 (1974).
250. J. P. Lorand, R. W. Wallace, J. Am. Chem. Sot., 96, 1402
(1974).
251. T. Koenig, J. G. Huntington, J. Am. Chem. Sot., 96, 592
(1974).
252. P. S. Engel, D. J. Bishop, J. Am. Chem. Sot., 97, 6754
(1975).
253. R. R. Hiatt, L. C. Glover, H. S. Mosher, J. Am. Chem. Sot.,
97, 1556 (1975).
254. L-F. Lai, T. T. Tidwell, J. Am. Chem. Sot., 99, 1465 (1977).
255. R. A. Wolf, M. J. Migliore, P. H. Fuery, P. R. Gagnier,
I. C. Saheta, R. J. Trocino, J. Am. Chem. Sot., 100, 7967
(1978).
256. C. Walling, J. P. Sloan, J. Am. Chem. Sot., 101,7679 (1979).
257. C. M. Rynard, C. Thankachan, T. T. Tidwell, J. Am. Chem.
Sot., 101, 1196 (1979).
258. J. E. Lefller, J. T. Barbas, J. Am. Chem. Sot., 103, 768
(1981).
259. B. G. Dixon, G. B. Schuster, J. Am. Chem. Sot., 103,3068
(1981).
260. A. S. Nazran, J. Warkentin, J. Am. Chem. Sot., 104, 6405
(1982).
261. R. A. Kenley, D. G. Hendry, J. Am. Chem. Sot., 104, 220
(1982).
262. J. K. Rasmussen, S. M. Heilmann, F? E. Toren, A. V. Pocius,
T. A. Kotnour, J. Am. Chem. Sot., 105, 6845 (1983).
263. R. C. Neuman, G. D. Lockyer, J. Am. Chem. Sot., 105,3982
(1983).
264. W. A. Pryor, N. Ohto, D. F. Church, J. Am. Chem. Sot., 105,
3614 (1983).
265. J. P Engstrom, J. C. DuBose, J. Org. Chem., 38,3817 (1973).
266. J. R. Shelton, C. K. Liang, J. Org. Chem., 38, 2301 (1973).
267. J. A. Ernst, C. Thankachan, T. T. Tidwell, J. Org. Chem., 39,
3614 (1974).
268. J. E. Herweh, R. M. Fantazier, J. Org. Chem., 39, 786
(1974).
269. D. A. Cable, J. A. Ernst, T. T. Tidwell, J. Org. Chem., 37,
3420 (1972).
270. W. A. Pryor, E. H. Morkved, H. T. Bickley, J. Org. Chem.,
37, 1999 (1972).
271. J. E. Leffler, F. E. Scrivener, J. Org. Chem., 37, 1794 (1972).
272. A. I. Dalton, T. T. Tidwell, J. Org. Chem., 37, 1504 (1972)
273. J. P. Engstrom, F. D. Greene, J. Org. Chem., 37,968 (1972).
274. I? S. Engel, A. I. Dalton, L. Shen, J. Org. Chem., 39, 384
(1974).
275. W. B. Richardson, W. C. Koskinen, J. Org. Chem., 41,3182
(1976).
276. W. A. Pryor, D. Graham, J. Org. Chem., 43, 770 (1978).
277. L. Batt, S. W. Benson, J. Chem. Phys., 36, 895 (1962).
278. P. S. Engel, R. L. Allgren, W. K. Chae, R. A. Leckonby,
N. A. Matron, J. Org. Chem., 44, 4233 (1979).
279. L. Thijs, S. N. Gupta, D. C. Neckers, J. Org. Chem., 44,4123
(1979).
280. R. C. Neuman, M. J. Amrich, J. Org. Chem., 45, 4629
(1980).
281. J. R. Hurst, G. B. Shuster, J. Org. Chem., 45, 1053 (1980).
282. W. H. Richardson, S. A. Thomson, J. Org. Chem., 47,4515
(1982).
283. Z. Chengxue, Z. Renmo, P Hegi, J. Xiangshan, Q. Yangling,
W. Chengjiu, J. Xikui, J. Org. Chem., 47, 2009 (1982).
284. E. M. Shulman, A. E. Merbach, W. J. le Noble, J. Org.
Chem., 47, 431 (1982).
285. A. Pohlman, T. Mill, J. Org. Chem., 48, 2133 (1983).
286. L. F. R. CaRerata, G. N. Eyler, M. V. Mirifico, J. Org. Chem.,
49, 2107 (1984).
287. S. Molnar, J. Polym. Sci. A-l, 10, 2245 (1972).
288. K. Ito, J. Polym. Sci., Polym. Chem. Ed., 11, 1673 (1973).
289. M. B. Lachinov, V P. Zubov, V. A. Kabanov, J. Polym. Sci.,
Polym. Chem. Ed., 15, 1777 (1977).
290. B. Yamada, H. Kamei, T. Otsu, J. Polym. Sci., Polym. Chem.
Ed., 18, 1917 (1980).
291. S. G. Ng, K. K. Che, J. Polym. Sci., Polym. Chem. Ed., 20,
409 (1982).
292. B. B. Idage, S. P. Vemckar, N. D. Ghatge, J. Polym. Sci.,
Polym. Chem. Ed., 21, 2145 (1983).
293. B. L. Funt, G. Pawel Chak, J. Polym. Sci., Lett. Ed., 13,451
(1975).
294. M. G. Kulkami, R. A. Mashelkar, L. K. Doraiswam, J.
Polym. Sci., Lett. Ed., 17, 713 (1979).
295. P. S. Engel, Chem. Rev., 80, 99 (1980).
296. T. Koenig, in: Free Radicals, Wiley, New York, 1973,
p. 113.
297. B. K. Bandlish, A. W. Garner, M. L. Hodges, J. W. Tim-
berlake, J. Am. Chem. Sot., 97, 5856 (1975).
298. R. J. Crawford, K. Takagi, J. Am. Chem. Sot., 94, 7406
(1972).
299. R. C. Neuman., J. J. Amrich, J. Am. Chem. Sot., 94,273O
(1972).
300. S. E. Scheppele, W. H. Rapp, D, W. Miller, D. Wright,
T. Marriott, J. Am. Chem. Sot., 94, 539 (1972).
301. C. Walling, H. P. Waits, J. Phys. Chem., 71, 2361 (1967).
302. Y. L. Zherebin, S. S. Ivanchev, N. M. Domareva, Polym. Sci.,
USSR, 16, 1033 (1974).
303. R. V. Kucher, A. A. Turovskii, N. V. Dzumedzei, V. A. Tan&o,
Polym. Sci., USSR, 16, 1216 (1974).
304. V. A. Novikov, V. P. Sass, S. L. Ivanova, L. F. Sokolov,
S. V. Sokolov, Polym. Sci., USSR, 17, 1414 (1975).
305. V. P. Kartavykh, V. A. Drach, Y. N. Barantsevich,
Y. L. Abramenko, Polym. Sci., USSR, 19, 1413 (1977).
306. V. I. Galibei. L. V. Dudnik, T. A. Tolpygina, A. B. Petrova,
V. I. Sokolova, Polym. Sci., USSR, 19, 1519 (1977).
307. B. N. Pronin, Y. N. Barantsevich, L. V. Shumnyi, S. S. Ivanchev,
Polym. Sci., USSR, 19, 1850 (1977).
308. J. C. Martin, J. H. Hargis, J. Am. Chem. Sot., 91, 5399
( 1969) .
309. J. R. Shelton, C. K. Liang, P. Kovacic, J. Am. Chem. Sot.,
90, 354 (1968).
310. C. G. Overberger. A. V. DiGiulio, J. Am. Chem. Sot., 81,
2154 (1959).
311. C. G. Overberger, A. B. Finestone, J. Am. Chem. Sot., 78,
1638 (1956).
312. S. G. Cohen, C. H. Wang, J. Am. Chem. Sot., 77, 2457
(1955).
313. J. R. Shelton, C. K. Liang. J. Org. Chem., 38, 2301
(1973).
314. J. W. Timberlake. A. W. Garner, J. Org. Chem., 41, 1666
(1976).
315. C. Ruchardt, H. Bock, I. Ruthardt, Angew. Chem. Int. Ed., 5,
253 (1966).
316. W. Cooper, J. Chem. Sot., 2408 (1952).
317. H. Kiefer, T. G. Traylor, Tetrahedron Lett., 6163 (1966).
318. K. R. Kopecky, T. Gillan, Can. J. Chem., 47, 2371 (1969).
319. B. H. Al-Sader, R. J. Crawford, Can. J. Chem., 48, 2745
( 1970) .
320. D. D. Tanner, H. Yabuuchi, H, Lutzer, Can. J. Chem., 55,612
(1977).
321. R. Hiatt, V. G. K. Nair, Can. J. Chem., 58, 450 (1980).
322. T. R. Lynch, F. N. MacLachlan, J. L. Suschitzky, Can. J.
Chem., 51, 1378 (1973).
323. J. Bonnekessel, C. Ruchardt, Chem. Ber., 106,289O (1973).
324. W. Duismann, C. Ruchardt, Chem. Ber., 106, 1083 (1973).
325. R. Kerber, 0. Nuyken, L, Weithmann, Chem. Ber., 108,1533
(1975).
326. T. Otsu, B. Yamada, J. Macromol. Sci.-Chem., A3, 187
( 1969) .
327. I. Hinz, C. Ruchardt, Ann. Chem., 765, 94 (1972).
328. C. Ruchardt, I. Mayer-Ruthardt, Chem. Ber., 104, 593
(1971).
329. R. Kerber, 0. Nuyken, Makromol. Chem., 164, 183 (1973).
330. R. Kerber, 0. Nuyken, V. Pasupathy, Makromol. Chem., 170,
155 (1973).
331. R. Kerber, 0. Nuyken, R. Steinhausen, Makromol. Chem.,
175, 3225 (1974).
332. R. Walz, B. Bomer, W. Heitz, Makromol. Chem., 178, 2527
(1977).
333. R. C. Neuman, G. D. Lockyer, M. J. Amrich, Tetrahedron
Lett., 1221 (1972).
334. F. E. Herkes, J. Friedman, P. D. Bartlett, Int. J. Chem. Kinet.,
1, 193 (1969).
335. N.-T.-Giac, C. Ruchardt, Chem. Ber., 110, 1095 (1977).
Ref erences I I / 75
336. W. Duismann, C. Ruchardt, Chem. Bet, 111, 596 (1978).
337. Anon., Evaluation of Organic Peroxides from Half-Life
Data, Technical Bulletin, Lucid01 Division, Pennwalt (no
date).
338. Anon., Product Guide US Peroxygen Division, Witco, 1984.
339. Anon., Azo Polymerization Initiators, Wako Chemicals,
USA, 1983.
340. Anon., Product Bulletin V-6Ol, Wako Chemicals, USA
(no date).
341. Anon., Product Bulletin V-50, Wako Chemicals, USA,
1985. r
342. Anon. , Azo Ami de Compounds, Wako Chemi cal s, USA
(no date).
343. Anon., Product Bulletin V-65: Wako Chemicals, USA, 1985.
344. Anon., Initiators for Polymer Production, Akzo Nobel
Chemicals Inc., pp. 94- 116.
345. S. Icli, K. A. Kandil, C. Thankachan, T. T. Tidwell, Can. J.
Chem., 53, 979 (1975).
346. W. H. Richardson, M. B. Yelvington, A. H. Andrist,
E. W. Ertley, R. S. Smith, T. D. Johnson, J. Org. Chem.,
38, 4219 (1973).
347. D. J. Robbins, A. J. Almquist, D. C. Timm, J. I. Brand,
R. E. Gilbert, Macromol., 28, 8729 (1995).
348. K. Matsuyama, T. Sugiura, Y. Minoshima, J. Org. Chem., 60,
5520 (1995).
349. S. Suyama, H. Ishigaki, T. Nakamura, Y. Sugihara,
H. Kumura, Y. Watanabe, Polym. J., 26, 273 (1994).
350. Y. Sugihara, Y. Watanabe, H. Kumura, T. Nakamura,
S. Suyama, Y. Sawaki, Bull. Chem. Sot. Japan, 65, 664
(1992).
351. E. M. Chellquist, W. G. Gorman, Pharmaceutical Research,
9, 1341 (1992).
352. W. H. Hendrickson, C. C. Nguyen, J. T. Nguyen, K. T. Simons,
Tetrahedron Lett., 36, 7217 (1995).
353. C. Navarro, B. Maillard, Thermochimica Acta, 220, 103
(1993).
354. W. A. Pryor, W. H. Hendrickson Jr., J. Am. Chem. Sot., 105,
7114 (1983).
355. J. Szalko, W. Feist, J. Polym. Sci., Polym. Chem., 33, 1637
(1995).
356. H. Fujie, K. Shiraki, T. Miyagawa, N. Minamii, J. Macro-
mol. Sci., Pure Appl. Chem. A, 29, 741 (1992).
357. S. Idage, B. Idage, S. Vernekar, J. Appl. Polym. Sci., 45,931
(1992).
358. T. Komai, S. Suyama, Bull. Chem. Sot. Japan, 58, 3045
(1985).
359. T. Komai, H. Ishigaki, K. Matsuyama, Bull. Chem. Sot.
Japan, 58, 243 1 (1985).
360. K. V. Scherer Jr., L. Batt, P. H. Stewart, Int. J. Chem. Kinet.,
26, 73 (1994).
361. S. Suyama, Y. Watanabe, Y. Sawaki, Bull. Chem. Sot. Japan,
63, 716 (1990).
362. T. Komai, K. Matsuyama, M. Matsushima, Bull. Chem. Sot.
Japan, 61, 1641 (1988).
363. K. Matsuyama, Y. Higuchi, Bull. Chem. Sot. Japan, 64,259
(1991).
364. K. Matsuyama, H. Kumura, J. Org. Chem., 58, 1766
( 1993) .
II/76 DECOMPOSITION RATES OF ORGANIC FREE RADICAL INITIATORS
365. L. F. R. Cafferata, J. D. Lombardo, Int. J. Chem. Kinet., 26,
503 (1994).
366. B. Yamada, T. Otsu, Makromol. Chem., 190, 915 (1989).
367. U. Shanker, G. N. Kulsrestha, J. S. Sharma, B. S. Pathania,
Indian J. Tech., 23, 318 (1985).
368. T. Komai, K. Kato, K. Matsuyama, Bull. Chem. Sot. Japan,
61, 2641 (1988).
369. H. Sawada, H. Hagii, K. Aoshima, T. Arai, Bull. Chem. Sot.
Japan, 57, 1161 (1984).
370. H. Sawada, H. Hagii, K. Aoshima, M. Yoshida, M. Kobaya-
shi, Bull. Chem. Sot. Japan., 58, 3448 (1985).
37 1. F. Severini, R. Gallo, J. Thermal Anal., 30, 841 (1985).
372. A. S. Nazran, J. Warkentin, J. Am. Chem. Sot., 104, 6405
(1982).
373. L. F. R. Cafferata, G. N. Eyler, M. V. Mirifico, J. Org. Chem.,
49, 2107 (1984).
374. A. F. Shushunova, L. Y. Prokhorova, J. Chrom., 283, 365
(1984).
375. J. M. Bessiere, B. Boutevin, 0. Loubet, Polym. Bull., 30,545
(1993).
376. J. C. M. Torfs, L. Deij, A. J. Dorrepaal, J. C. Heijens, Anal. i
Chem., 56, 2863 (1984).
1
377. M. Buback, C. Hinton, Zeit. Phys. Chem., 193, 61
(1996).
I
Propagation and Termination Constants
in Free Radical Polymerization
M. Kamachi
Department of Applied Physics and Chemistry, Fukui University of Technology, Gakuen, Fukui, Japan
B. Yamada
Department of Applied Chemistry, Faculty of Technology Osaka City University, Sumiyoshi, Osaka, Japan
A. Introduction
B. Tables of Propagation and Termination
Const ant s
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. Ref erences
II-77
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
II-91
A. INTRODUCTION
In free radical polymerization the propagation and termina-
tion rate constants describe the reactions
kP
P; +M-I,,, (Al)
2P; kt dead polymer
W)
where P; is a propagating chain of any length n and M is
the monomer. The rate constants are defined by the
following equations:
R, = -7= kr[P][M]
R, = -F = k,[p]2
where
PI = 2 RI1
n=l
(A41
The rate constants k, 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 2kt [P] 2. In this chapter the definition
given in Eq. (A4) has been used.
Simultaneous determination of absolute values of both
k, and k, from a single experiment has not been reported. In
practice, the ratio ki/k, 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 conver-
sion. The ratio k,/k, is determined from nonsteady-state
measurements of the average lifetime, r, of the growing
polymer chain in a photochemically initiated polymeriza-
tion. 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
[P-]/r = Rt
which, from (A3) and (A4), yields
(A61
By combining the separately determined ratios, ki/k, and
kp/kt, the individual propagation and termination rate
constants may be calculated. Alternatively, the rate of
initiation, Ri, may be measured as the rate of initiator
disappearance and equated to Rt. This gives (from (A6) and
(A311
RP
k, = ~
Rir[M]
(A81
There is a large degree of imprecision inherent in
measuring 7 and in combining data from different
experiments, which helps to explain the scatter in the data
tabulated here.
II/77
II/78 PROPAGATION AND TERMINATION CONSTANTS IN FREE RADICAL POLYMERIZATION
k&l O-
100
I O
I
too
3
IO
I
IOOl
kt ( xl 0"
100
18
4 +
l 4
- l i*,
l
: 4 4
+ 4
l *.+
+ +
4s
4 + +
s
l
+
I I I I
a.0 a. 2 a. c a. 0
1000
T
Figure 1. Arrhenius plots of all bulk polymerization data for
styrene for k, (0) and k, (+). 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 least-
squares 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 k,. In the PLP
method, the value of k, can be estimated from the degree of
polymerization of polymer formed, vr, a knowledge of the
monomer concentration, [Ml, and tf the time between
pulses:
vp = kp[Mltf ( fw
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 k,.
P
0
I I I I 1
a. S.k
IO00
a.0
T
Figure 2. Arrhenius plots of all bulk polymerization data for
methyl methacrylate for k, (0) and kr (+). Solid lines are least
squares obtained by assuming all points to be of equal value. The
line for kr is not shown since a horizontal line for a temperature
independent kr 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 T:
Al - rotating sector or a flashing laser
A2 - flow through a tube with spatially separated light
and dark sections
A3 - spatial 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 1 - dilatometry
B2 - dielectric constant
B3 - interferomety
B4 - temperature change
B5 - viscosity
B6 - light scattering
B7 - monomer pressure
Dienes and Olefins II/79
Method F uses pulse laser photopolymerization (PLP)
met hod
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)
B8 - cathetometer
B9 - inhibitor
B 10 - scavenger
Method C uses electron spin resonance (ESR) for the
determination of the radical concentration
Method D refers to values obtained in emulsion polymer-
ization by application of the Smith-Ewart theory
Method E refers to recalculated values
B. TABLES OF PROPAGATION AND TERMINATION CONSTANTS
TABLE 1. DIENES
Monomer k, (VmoVs) k , ( x 10 -6) (l/mol/s) Temp. (C) Method Remarks Refs.
2 8 1 2 5 Al 1 5 2
1 0 D 2 3
1-Acetoxybutadiene
But a di e ne
18.0
k, = 1.2 x lo8
xexp(- 390OO/RT)
150f40 C 2 2 3
Gl 202
5
kt = 1.13 x 104
x exp(-711/7)
45-60
5 0 Ink, = In (3.873 x 10 lo)
-534OO/RT
1 1 1 . 6
k, = 8.05 x 10
x exp(- 35710/RT)
Chl or opr e ne 220
k, = 2.9 x lo9
x exp(- 41OOO/RT)
k, = 1.95 x 10
xexp(- 26630/RlJ
2,3-Dimethyl-1,3-butadiene k, = 8.9 x 10
xexp(- 38000/RT)
Ethyl 4-ethoxy-2,4-pentadienoate 9 . 9
Et hyl 4-methyl-2,4-pentadienoate 2 9 . 7
Ethyl pentadienoate 3 0 . 9
1,3-Hexadiene 20flO
2,4-Hexadiene 16f 12
I s opr e ne 2 . 8
Fl 2 2 1
Fl Solvent: chlorobenzene 2 2 1
F 2 Solvent: chlorobenzene 1 8 7
50
40 D
D
Quoted in Ref. 86 5 9
84
Fl 1 9 8
D 71
9 . 3 2 5 Al
2 3 2 5 Al
1 9 2 5 Al
5 C
5 C
5 D
1 5 2
1 5 2
1 5 2
223
223
Calalyst system: diisopropylbenzene, 2 4
monohydroperoxide-
tetraethylenepentamine
2 2 3
2 2 3 2-Methyl-1,3-pentadiene
125 130 5 C
35 f 10 5 C
TABLE 2. OLEFINS
Monomer k, (Urnok) k, (x 10e6) (YmoVs) Temp. (C) Method Remarks Ref s.
8 3
- 20.01
1 3 0
1 3 0
1 9 0
230
3.2 x lo3 190
Al
Al
Al
Al
C
Fl
Fl
Solvent: benzene
Pressure 1.8 x lo8 Pa
Pressure (5-17.5) x 10 Pa, using
results of Ref. 141
Pressure 1.9 x lO*Pa
Initial pressure 2.27 x lo* Pa
Pressure 2.55 x lo* Pa,
at low or moderate conversion
Pressure 2.50 x lo* Pa,
at conversion 0
5 3
66
1 3 9
1 4 2
135
151
1 6 7
1 6 7
50-150 Radical telomerization 1 2 9
Et hyl e ne 470 f 30 1050f50
18.6f2 455 f 50
5400 200
k, =4.8 x 10
xexp[(-4450+3.1 x 10-6p)/Tj
1.2 x 104 3.9 (7.8) x 10
1.09 x lo4 1.99 x 102
3.08 x lo4 -
Propylene k,=2x106
xexd-320OO/RT)
References page II - 15
II/80 PROPAGATION AND TERMINATION CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 3. ACRYLIC DERIVATIVES i
Monomer k, (VmoUs) kt (x 10 -6) (l/moVs) Temp. (C) Method Remarks Ref s. Iv
6000 i 1000
18000 f 1500
8200
220
(7.9 &0.5) x lo4
(4.3 f 0.2) x 104
(3.3 iO.2) x 104
(2.3fO.l) x lo4
k, =7 x 106
x exp[(- 21000f 2000)/RT]
650
3.3 + 0.6
14.5 f 2.0
5 . 5
1.0
660 f 40
350 i 20
230 i 20
160 f 10
Al, Bl Solvent: water, pH 5.5
2 5
19
2 6
3 0
3 0
Al
A
A
Al
Al
Al
Al
Fl
2 . 6 2 3 Al
3150 2 . 6 Al
6600 2 . 7
13 0.018
2100 330
1 9 7 7 3 . 8 4
679 f 66 6.4 f 0.6
2 5
2 5
3 0
25-80
3 0
Al
Al
B 4
Al
Al
Fl
B 5
7 9
4 1
8 9
8 9
1 2 6
1 1 9
1 1 9
1 1 9
1 9 7
Acrylamide
Acrylic acid
-, butyl ester
log 1, ~ k, = 6.0123- 748.4/T
1 3 6 0
963
1 3 2 0
360
2722 f 248
800
12.39 x lo3
ln[(k,(p]/(l.OO + 0.06p)l
= In k, [l]- 0.60~
1.28
1.18
1.07
0.36
3.2 f 0.3
1.76
1 3 9 . 2
3 0 Al
-, cyclohexyl ester
-1
ethyl ester
3 0 Al
5 0 Al
50 Al
-, 2-ethylhexyl ester 155 0 . 2 3 3 5 0 Al
-9 methyl ester 1 3 0 0 7 5 15 Al
880 260 15 Al
1 5 8 0
580
k,= 1.0 x lo*
xexp(- 3OOOO/RT)
1 0 0 0
1 1 6 8 0
21300
(1.5 f0.2) x lo4
5 5
k,=2:, 10
xexp(- 220OO/RT)
3.5550
1 9 4
2 5
2 5
Al 19
Bl 4 8
Al 21
60
Al
Al
Al
G2
(3.7 f 0.6) x lo4 6 0 G2
6.3 x lo4 6 0 G2
(1.4+0.2)x lo4 60 G2
-, 2-(acetoacetoxy-&ethyl)-, ethyl ester 300 1.0 6 0 C
-, 2-cyano-, ethyl ester 1 6 2 2 4 1 1 3 0 Al
1 6 1 0 404 3 0 Al
1 6 1 3 4 1 1 3 0 Al
1 6 0 7 404 3 0 Al
-, 2-chloro-, ethyl ester 1 6 6 0 3 3 3 3 0 Al
1 4 0 8 244 3 0 Al
-, 2-fluoro-, ethyl ester 1 1 2 0 4.8 x 102 3 0 Al
978 435 3 0 Al
-9 2-acetoxymethyl-, methyl ester 350 2.1 6 0 C
Solvent: water
Solvent: water
Solvent: DMSO
Solvent: water 0.38 M
HzO:DMSO (90: 10)
HzO:dioxane (90: 10)
HZ0 : THF (92 : 8)
9 9 Solvent: Water, pH 7.9,
(with 1.2 M NaOH)
Solvent: water,
pH 7.9 (with 1.5 N NaCl)
Solvent: water, pH 11
9 9
9 9
10
5 7
1 0 7
1 3 7
2 0 1
1 2 2
Pressure 5.0 x 10 Pa
Solvent: benzene 1.76 M
k, b]; k, for pressure p (bar),
kt [l] =3.5 x lo6
Solvent: anisole 2.OOM
Solvent: benzene 2.00 M
Solvent: chlorobenzene 2.00M
Solvent: benzonitrile 2.00 M
Solvent: benzene 1.76 M
Solvent: toluene 1.84 M
Solvent: benzene n; molar fractions
of monomer, x = 0.401,
k, and k, also given by other [Ml
Solvent: toluene 1.94 M
From unpublished results of Ross
and Melville
From unpublished results of
Matheson
1 3 8
1 3 8
138
138
1 3 7
1 0 8
171
108
22 ;
2 2
50
1 4 4
1 4 4
1 9 0
Solvent: benzene 2.69 M
Primary propagating step (k,,),
Ph-MA
PhCOz-MA
rerr-BuO-MA
Secondary propagating step (k,~),
Ph-MA-MA, PhCOz-MA-MA,
terc-BuO-MA-MA
Solvent: benseme
AcOHwt.%
1,3-propanesulfone 0.5 wt.%
Optimum value, solvent: AcOH
Optimum value
Solvent: propanesulfone
AIBN 4.88 x 10 - M
Optimum value
1 9 0
1 9 0
1 7 0
1 4 3
1 4 3
123
123
1 4 0
123
1 4 6
123
2 2 5
Optimum value
Solvent: benzene 1 .OO M,
MAIB 0.050 M
TABLE 3. contd
Acrylic Derivatives II/81
Monomer k, (VmoUs) k t ( x 10 -6) (Urnok) Temp. (C) Method Remarks Refs.
-, 2-acetyloxy-, methyl ester 430 60 C
-, 2-benzoyloxy-, ethyl ester 990 2 . 9 60 C
-, 2-(benzyloxymethyl)-, methyl ester 1 8 2 1.6 60 C
-, 2-[2,2-bis(carbomethoxy) ethyl],
methyl ester
4.0 0.038 60 C
-, 2-butoxy-, methyl ester 298 8 60 C
1 8 4
-
60 C
-, 2-butyroxymethyl-, methyl ester 360 1.4 60 C
-, 2-(2-carbomethoxy)- ethyl-,
methyl ester
-, 2-ethyl-, methyl ester
-, 2-ethyl-, cyclohexyl ester
-, 2-isobutyroxymethyl-, methyl ester
19 0 . 5 1 60 C
8 . 6 21 60 C
1.6 1.8 60 C
300 1.1 60 C
-, -2-(methoxycarbonylmethyl)-,
phenetyl ester
11 0 . 0 8 5 0 C
-, 3-methyl, adamantyl ester 0 . 5 7
0 . 7 6
0.11
1.4
6 0 C
60 C
-, 3methy1, dimethyladamantyl ester 0.41 0. 08 1 6 0 C
0.71 1.1 6 0 C
-, 3-methyl, [err-butyl ester 0.90 2 . 3 6 0 C
1.0 4 . 7 6 0 C
-, 2-naphthoyloxymethyl-, ethyl ester
-, 2-pivaroxymethyl-, methyl ester
320 0 . 3 7 60 C
230 0.59 60 C
-9 nuns-2-vinyl-, methyl ester
Acr yl oni t r i l e
1 2 5 60 C
3000-5000
1 2 7
5 2
51
20000
24
12.2
5
1.8
D
B4
B4
B4
D
2 3
0
2 5
2 5
2 5
40
5 0
1 9 6 0 782
1 5 4 0 0 2700
28000 3700
1 9 1 0 290
382 f 230 47.6 + 22
3300 i 300 1200% 170
3200 k 400 300 f 50
3000 i 600 240 i 70
N-Acryloyl-2,2-dimethyl-
5 (R)-phenyl-1,3-dioxazoline
(6.5 f 1.3) x lo3 4700 f 1300
2 8 . 2 0.20
6 0 Al
2 5 Al
2 5 Al
2 5 Al
2 5 Al
50 Al
50 Al
50 Al
50 Al
6 0 C
N-Acryloylpiperidine 273 17.9 3 0 Al
273 11.9 30 Al
N-Acryloylpyrrolidine 8 2 6 7 2200 30 Al
Solvent: 1,1,2-trichloroethane 2.OM
2,2-azobis (4-methoxy-2,4-
dimethylvaleronitrile) O.O30M, k,
also given by other temp.
Solvent: benzene 1.56 M
Solvent: benzene 2.0 M,
AIBN 5.tilK3 M
Bulk AVN 0.05 M,
k, and kr also given by
other temp.
Solvent: benzene 2 M
Solvent: 1 ,1,2-trichloroethane 2.0 M
2,2-azobis (4-methoxy-2,4-
dimethylvaleronitrile) 0.030 M, k,
also given by other temp.
Solvent: benzene 1 .OO M, MAIB
0 . 0 5 0 M
Bulk MAIB 0.05 M, k, and k,
also given by other temp.
Bulk AIBN 0.10 M
Bulk AIBN 0.10 M
Solvent: benzene LOOM,
MAIB 0.050 M
Solvent: benzene 2.22M, k, and kt
also given by other temp.
and [Ml
Bulk 4.8 M
MAIB 0.05 M
Solvent: benzene 2.4 M,
MAIB 0.05 M, k,
also given by other [M]
Bulk 4.0 M, MAIB 0.05 M
Solvent: benzene 2.0 M,
MAIB 0.05 M
Bulk 5.9 M, MAIB 0.05 M
Solvent: benzene 2.0 M,
MAIB 0.05 M
Solvent: benzene 1 .OO M,
MAIB 0.01 M
Solvent: benzene 1 .OO M,
MAIB 0.005 M
Solvent: benzene 1.0 M,
AIBN 0.25 M
Solvent: DMF
Primary radical termination in a
precipitating medium
Solvent: DMF
Solvent: water
Solvent: water
Solvent: DMSO
Solvent: DMF
Solvent: DMF 3.8 M
Solvent: DMSO 3.8 M
Solvent: Ethylene carbonate 3.8 M
224
1 7 2
206
228
1 7 6
224
225
229
230
230
225
232
232
232
232
232
232
226
225
227
42
49
6 3
7 5
42
3 5
4 3
5 4
5 5
70
6 8
8 8
8 8
8 8
Solvent: Mg (Clod)* 12H20 3.04M 8 8
Solvent: benzene 1.08 M, 2 3 1
MAIB 0.05 M, k, and kt
also given by other temp.
145
Optimum value 1 2 3
Optimum value 1 2 3
References page II - 15
II/82 PROPAGATION AND TERMINATION CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 3. contd
Monomer k, (VmoVs) kt (x 10e6) (Vmok) Temp. (C) Method Remarks Refs.
WV-Dimethylacrylamide
3-Dimethyl-(acryloyloxyethyl)-
a mmo n i u m s u l f o n a t e
propane
N-Methylactylamide
1 1 0 0 0
27200
29198
15 x 10s
2330 i 230
2760 f 342
9.9 x 10s
3 8
3540
4080
0.540 f 0.053
0.452 f 0.056
5 0
3 0
3 0
2 5
3 0
30
2 5
Al
Al
Al
Fl
A4
Fl
Optimum value
Sol ve nt : water, pH 1.4
Solvent: formamide : 1,Cdioxane
(3 : 1 (v/v))
Sol ve nt : formamide: 1,Cdioxane
(3 : 1 (v/v)), NaCl 0.1 M
Solvent: water, 1.9 pH
74
121
123
1 9 7
1 9 2
1 9 2
1 9 7
TABLE 4. METHACRYLIC DERIVATIVES
Monomer k, (VmoVs) k t ( x 10 -6) (YmoYs) Temp. (C) Method Remarks Refs.
Methacrylamide
Methacrylonitrile
Methacrylic acid
-, benzyl ester
-, bomyl ester 580 3 . 3 6 0 C
-, n-butyl ester 369 10.2
573 18.0
360 1 0
lnk,=6.13+6.33 x 10-9p
lnkr = 15.8-2751/T
2 . 6
ln[(k,[p1/(1.00+0.01p)l
=lnkJl] - 0.73~
Ink, = (14.41 hO.09) - (2472 f 29)/T
3 0 Al
3 0 Al
3 0 Al
30 F 2
12-93 F 2
70 B 5
3 0 B 5
79.6 f 5.6
1.1 x 10s
- 2 1
2 6
k = 106.435026
x exp[(P 29700 f 15OO)/RT]
16.5 it 1.4
- 2 7
21
2 5
2 5
3 0
2 5
Al Solvent: water
Fl Solvent: water, pH 1
Al
6 9
1 9 7
2 6
3 9
670 2.1 2 3 Al Solvent: water, pH 8.0 9 9
1 9 5 0 2 . 2 5
1 4 1 0 41.9
1 1 0 8 0
8 9 5 40
1250 41.9
510 2 . 8 7
3 0
3 2 . 5
3 2 . 5
30
20
Al
Al
C
C
Al
Al
(with 0.22 M NaOH)
pH = 13.6
k, and k, also given as a
function of viscosity
Solvent: benzene l.OM,
AIBN 0.05 M
9 9
101
1 5 3
153
8 7
1 0 3
193
Pressure: 5.0 x lo7 Pa
Pressure 1.0 x lo* Pa
q= 1.92~~
k, [PI; k, for pressure p (bar),
k,[l] = 13.4 x lo6
2 7
1 0 6
1 0 9
216
216
212
1 2 2
10-90 Fl 219
Fl 1 6 9
A3 2 2 5
Al 52
Fl 2 0 3
-, tert-butyl ester
-1 trans-Ctert-butyl-
cyclohexyl ester
-3 cetyl ester
-, p-[p-(cetyloxy)-
benzoyloxyl-
phenyl ester
-, 2-chloroethyl ester
-, 2-cyclohexyl-
ethyl ester
-9 cyclohexyl ester
-, 2-decahydro-
naphthyl ester
k, = 3.44 x lo6 exp(- 233OO/RT)
1 5 7 6
350
9.74
1 4
k, = 107.4*o.4
x exp[- (27.7 f 2.5) x 103/RT]
550
3 0
2 5
9-66
1.9 60 C
510 1.9 60 C
570 f 10 0.5- 2.3 60 C
300 f 90 0. 16f0. 04 30 Al
300 0 . 2 5 50 Al
1 7 0 0 . 3 0 5 0 Al
254 6.71 3 0 Al
1 1 9 0 3 2 . 8 3 0 Al
510
570
5 . 4
3.1
60
60
C
C
Solvent: benzene 1 .O M,
AIBN 0.05 M, tram 100%
t r am 28.9%
Solvent: benzene
Solvent: dioxane 0.2 M
Solvent: toluene 0.2 M
Solvent: benzene 1.0 M,
AIBN 0.05 M
Solvent: benzene 1.0 M,
AIBN 0.05 M
1 9 4
1 9 4
210
1 0 9
97
9 7
8 7
8 7
1 9 3
1 9 3
TABLE 4. contd
Met hacryl i c Deri vat i ves II/83
Monomer k, (VmoUs) k t ( x 10 -6) (l/mol/s) Temp. (C) Method Remarks Refs.
-, 2,6dimethyl-
phenyl ester
-, dodecyl ester
-9
ethyl ester
-, hexadecyl ester
-, isobomyl ester
-9 isobutyl ester
-9 isopropyl ester
-, lauryl ester
-, 2-methoxyethyl ester
-3 methyl ester
6 8 2.1
12
-
1 2 6
-
k,= 1.50 x lo6
x exp(- 20460/RT)
lnk,=(15.11f0.17)-(2753&55)/T
390
2 . 4
0 . 6
1 . 3 5
10
0.16
3 . 5
lnkp=(14.72i0.13)-(2590f42)/T
121 4.52
460 f 140 0.6 f 0.2
k,=2.93 x lo5
x exp(- 16190/RT)
249 9.30
310520 66f4
k,= 5.13 x lo6 k, = 1.36 x lo3
x exp(- 26400/RT) x exp(- 119OO/RT)
1 8 7 7 2 . 1
404 17.6
410 24
13.2 0.488
390
517 3 7 10 Bl
527 2 3 10 Bl
2 8 4.4 10 Bl
260 21 2 5 Al
270 21 2 5 Al
280 19.5 2 5 Al
2 8 5 17.5 2 5 Al
310 17 2 5 Al
330 17 2 5 Al
340 17 2 5 B5
240 11.5 2 5 B5
3 3 5 9 2 5 B5
270 2 2 2 5 B5
330 16 2 5 B 5
250 2 9 2 5 B5
240 2 5 2 5 B 5
280 1 4 2 5 B5
320 2 8 2 5 B5
390 i 40 4 2 1 4 2 5 Al
410f40 29f3 2 5 Al
410f40 26f3 2 5 Al
180f50 20f6 2 0 E
500 f 250 63f32 2 0 B 6
41.6 2 . 6 9 0 B5
6 2 5 D
200 -
20 B 6
1 2 8 8 . 4 4 2 2 Bl
364 4 1 . 8 2 2 . 5 B4
512.6 46.6 2 5 Al
410 4 2 . 7 2 5 Al
248 2 2 . 7 3 0 Al
141 11.6 3 0 A
1 0 6 5 . 7 3 2 B4
1 4 0 40 D
30 Al 1 2 0
30
70
3 0
70
Al
B5
Al
B5
Fl
Optimum value
v = 3.96 cp
17=0.91 cp
123
212
8 7
212
1 6 9
10-90 Fl
70 B 5
60 C
10-90
3 0
3 0
Fl
Al
Al
Fl
v= 7.52 cp
Solvent: benzene l.OM, AIBN
0 . 0 5 M
219
212
193
219
8 7
1 0 9
1 6 9
3 0
2 3 . 6
Al 8 7
Al 9
Al I
3 2 . 5 C
40 Bl
50 E
- 3 0 Bl
20 Al
1 5 3
Solvent: ethyl acetate 51
Using results of Ref. 7 6 2
Solvent: ethyl acetate 7 2
k, also given as a function of temp. 9 2
and of viscosity for other solvents
Solvent: methanol 94
Solvent: pyridine 9 4
Solvent: DMF 94
Solvent: benzene 4.69M 8 5
Solvent: fluorobenzene 4.69 M 8 5
Solvent: chlorobenzene 4.69M 8 5
Solvent: anisole 4.69 M 8 5
Solvent: bromobenzene 4.69 M 85
Solvent: benzonitrile 4.69M 8 5
Solvent: methyl benzoate 4.69 M 9 0
Solvent: methylphenyl acetate 4.69 M 9 0
Solvent: dimethyl phthalate 4.69 M 9 0
Solvent: dimethyl carbonate 4.69M 90
Solvent: diethyl oxalate 4.69 M 90
Solvent: methyl formate 4.69 M 90
Solvent: methyl propionate 4.69 M 90
Solvent: diethyl succinate 4.69 M 90
Solvent: acetonitrile 4.69M 90
Solvent: methanol 50% by vol. 1 0 4
Solvent: n-octane 5% by vol. 1 0 4
Solvent: n-nonane 20% by vol. 1 0 4
m = (2-8) x lo3 using results of 96
Ref. 86
m= (3-5) x 104 96
Assuming biradical initiation 1 1
6 5
k, found as a linear function of M,
Rate of initiation; 1.20 x 10ms
(moles/l/s)
k, and kt also given as a function of
viscosity for other solvents
9 1
2 9
6 0
3 0
9 3
14
8 7
5 8
6 5
References page II - 15
II/84 PROPAGATION AND TERMINATION CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 4. contd
Monomer k, (l/mol/s) k t ( x 10 -6) (YmoUs) Temp. (C) Method Remarks Ref s.
0.224
-
45 D
573 2 . 0 60 E
513 11.9 60 E
995 f 83
506 zt 48
450 i 33
456 f 29
448547
498 f 39
614f43
427 i 38
290
1 0 2 0
530
550
43.6 f 4.9
35.6% 3.9
42.Oi3.0
43.8 f 2.0
41.2 f 6.6
42.9 f 4.7
39.9 f 3.3
30.9 i 3.1
21
292
5 5
6 8
80
30
30
60
Al
Al
Al
Al
Al
Al
Al
Al
Al
Al
Al
k,=4.92 x lo5
x exp(- 18210/RT)
315
k,=98
x exp(- 2930/RT)
3 3 . 9
15- 30 A2
25 A2
336 f 90
4 4 1
k,=2.5 x lo6
28f12 25 Al
19.7 30 Al
720 25- 60 C
x exp[(- 23000 f 25OO)/RZJ
k, =k;(0.33 5 wp 5 0.84)
= ki exp[- 29.8 (w,, - 0.84)]
(0.84 5 wp 5 0.99)
(k; =790 f 300)
1 3 0 20.7 f 1 .O
705.6 2 5
1 7 0
306
-
292
50 C wp (weight fraction of polymer) 150
0
60
0. 2 F 3
25 Fl
25 Fl
670 f 30 2 2
Ink, = 14.69-2670/T+
0.201/Tx (1.0 x lo-sp- 1)
lnkJp]=lnkr[l]-0.57~
26. 6 1. 4
5. 8 0. 017
k,(m,n) = 1.22 x lO*(n x m) -.075 2 5
60
20- 90
30
5
5
- 21 70
-
0. 034 50
0. 16 50
k,= 106.6 exp(- 23940/RT) - 1 t o - 7 0
Ink, (l/moYmin) = In k,,o- (3.86 [AIBME]o 60
+0. 8)x(l - qb )-1.6(1-I$ )6.0
m m
131 - 8
680- 820 30
690- 810
Termination by combinat. using
67
33
results of Refs. 7 and 31
Termination by disprop. using results 33
of Refs. 7 and 31
Solvent: benzene 4.7 M
Solvent: anisole 2.OM
Solvent: benzene 2.OM
Solvent: C6Ds 2.OM
Solvent: fluorobenzene 2.OM
Solvent: chlorobenzene 2.0 M
Solvent: benzonitrile 2.0 M
Sol ve nt : be nz e ne 1 . O M
Addition of 1 x 10e3 mol pyridine
Addition of 1 x lo- mol acetone
Addition of 1 x low3 mol
111
133
133
133
133
133
133
133
118
118
118
118
triethanolamine
Fn = 104 1 1 4
k, and kt also given as a
function of Pn
Pressure 5.0 x lo6 Pa
Pressure 5.0 x 10 Pa
1 1 0
127
105
45
Al At high conversions (N 65%) 148
Special evaluation from 134
steady-state and iii,
Solvent: toluene 222
196
Solvent: ethanol (50%) 4.67 M, k,
also given by other [M] and solvents
C 175
Fl 207
B 5
BlO
k&l; kt for pressure p (bar),
k,[l] = 15.4 x lo6
Scavenger DPPH, solvent: DMF,
blank polymn.
Scavenger DPPH, solvent: DMF,
template polymn., template;
it-MMA
122
115
BlO 115
A3
B 5
n: n-mer; m: m-mer, coupling with
n-mer and m-mer
1)=0. 53 CP
147
212
D 149
D
No addition of chain-transfer agent,
Time 7.5-20.5 min.
Addition of 2% CBr4,
Time 7.5-20.5 min.
149
Fl
C AIBME (dimethyl 2,2-
azodiisobutyrate) O.O434M, 4,;
monomer volume fraction
k,,o = 700 (l/moVmin)
Benzoin 7 x 10m4 M
Solvent: toluene, pressure
1.0 x lo* Pa, k,also given by
other pressures
Solvent/2-butanone, pressure
1.0 x 10s Pa
217
158
F 3
Fl
199
208
Fl 208
3.
R
-
T,
-
M
Iti
-,
-,
TABLE 4. contd
ltaconic Der i vat i ves II/85
Monomer k, (VmoVs) kt(x10m6) (Vmolh) Temp. (C) Method Remarks Refs.
-1
octyl ester
-, phenyl ester
-, 2-phenylethyl ester
-, 3-phenylpropyl ester
-1 n-propyl ester
-, 3-tetracyclo-[4.4.02.5.1 ,O]-
dodecyl ester
-1 triphenylmethyl ester
31318. 1
794.0
815.0
957.0
510f 100
299
4 3 1
k,=2.39 x lo6
x exp(- 220OO/RT)
359
12
135
292
200
135f50
1 7 0
3 5
2960
k,= 1.9068 x lo6
x exp(- 21181.07/RT)
k,= 1.2169 x lo6
x exp(- 25203.59/RT)
k,=3.0598 x 10
x exp(- 28008,18/RT)
3 5
1 7 1 0
240 f 80
4 1 1
230 f 15
17658
180*9
223+11
235f8
273f8
228
1 4 9
467
590
2 6 0 . 3 0 1
3 9 1 4
62.4
5 1 . 6
3 8 . 2
25( f 3)
21f2
4 5
50
-
-
2 5 . 6
29.1
6 2 . 6
2. 6f 0. 9
ln[(k,[p]/(l.OO-0.19)]
=lnk,[l]- 1.01~
11.9
2.02 f 0.22
2.06 f 0.21
2.1650.19
2.26 f 0.22
1.72f0.11
1.9610.12
1.88
0.813
4 5 . 1
2 . 6
3-Dimethyl-(methacryloyloxy-ethyl)
ammonium propane sulfonate
1470 f 170 0.499 i 0.058
2760 f 342 0.452 f 0.056
Polyhydroxytetramethylene-a,
w-methacrylate of MW = 700
185 0.034
230 0 . 0 5 3
2 5 Fl
6 0 B 5
60
60
2 5
40
C
C
Al
2 5
5 0
Fl
Fl
C
0 Al
2 5 Fl
2 8 Bl
0 Al
5 0 C
50
3 0 A3
Fl
Fl 30% MMA in benzyl alcohol 227
Fl 30% MMA in NMP 227
50
3 0
3 0
Al
Al
B 5
3 0
3 0
3 0
3 0
3 0
60
Al
Al
Al
Al
Al
Al
Al
Al
Al
Al
C
3 2 . 5 C
3 0 A4
3 0
20
2 0
B 8
B8
Solvent: benzene 3 M
Solvent: chlorobenzene 3 M
Solvent: benzonitrile 3 M
161
204
204
204
1 6 6
191
1 6 0
1 6 0
1 9 8
220
Emulsion polymn., 1 8 4
particle size 260nm, k,
also given by other particle sizes
k,; average value 1 5 9
1 6 4
Values from Chem. Abstr. 8 3
1 6 5
Emulsion polymn., n-butyl acrylate: 1 5 5
MMA: methacrylic acid (8 : 91: l),
particle size (p.s.) 50nm. k, also
given by other temp. and particle sizes
p.s. 500nm 1 5 5
2 2 5
227
p . s . 5 0 0 n m 155
Pressure 5.0 x 1OPa 113
1 0 9
k&l; k, for pressure p (bar), 1 2 2
k,[l] =40.0 x lo6
8 7
Solvent: anisole 2.00M 1 1 6
Solvent: benzene 2.00M 1 1 6
Solvent: fluorobenzene 2.00M 1 1 6
Solvent: chlorobenzene 2.00M 1 1 6
Solvent: bromobenzene 2.00 M 116
Solvent: benzonitrile 2.00 M 116
8 7
8 7
2 8
Solvent: benzene 1 .O M, 193
AIBN 0.05 M
153
Solvent: formamide: 192
1,4-dioxane (3 : 1 (v/v))
Solvent: formamide: 1 9 2
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 k, (I/moUs) k , ( x 10 -6) (VmoVs) Temp. (C) Method Remarks Refs.
Itaconic acid
-, bi s (4-rerr-butyl-cyclohexyl) ester
-, bi s (cyclohexyl-methyl) ester
1.7 2 . 5 x 1O-3 6 0 C Solvent: benzene 0 . 5 M 2 1 3
3 . 9 3 . 4 x 1o-3 60 C Solvent: benzene 1.5 M, 1 8 2
MAlB 0.02 M
References page II - 15
II/86 PROPAGATION AND TERMINATION CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 5. contd
Monomer k, (YmoVs) kt (x10m6) (YmoV.9) Temp. (C) Method Remarks Refs.
-, bis (3,5-dimethyl-1-adamantyl) ester
-, bis (2-ethylhexyl) ester
-, diadamantyl ester 0 . 5 6
-, di-n-butyl ester 3 . 5
-, di-set-butyl ester
-, di-reti-butyl ester
-, dicyclohexyl ester
-, diethyl ester
-, diisobutyl ester
-, diisopropyl ester
2 . 7
1.1
-, dimethyl ester 5 . 2
-, a-ethyl-P-hexafluoropropyl ester 5 . 0
-3 a-methyl+isopropyl ester 3 . 4 0 . 0 6 60
-> cc-methyl-S-rerr-butyl ester 4 . 2 0 . 0 5 1 60
-. a-isopropyl-P-methyl ester 1.9 0 . 0 7 6 0
-, a-tert-butyl-S-methyl ester 0 . 9 1 0.056 6 0
N(2,6-dimethylphenyl) itaconimide 26 0.082 50
Methyl N-phenyl-itaconamate 15 0 . 2 9 6 0
0 . 9 2
6 . 8
3 . 4
2 . 0
2.1
2 . 2
2.1
2.1
1.4
3 . 0
0.32 x 1O-3
0 . 0 0 1
0.30 x 10-3
1.59 x 10-2
13 0.11
11
6 . 8
9 . 4
6 . 1
3 . 4
3 . 2
0 . 1 3 50
0 . 0 7 5 0
0.11 50
0 . 0 8 3 50
0.068 50
0 . 1 3 50
1.0 x 10-3 50
5 . 3 8.5 x lo-*
5 . 9
0 . 6
0 . 2
2 . 3
0.053
4.0 x 10-3
5.6 x 1O-3
1.4 x 10-3
7.1
3 . 7
0.24
6.41 x lo-
1.56 x lo-*
5.0 x 10-3
1 0
0.36
0 . 5 9
0 . 2 8
60
5 0
5 0
50
5 0
50
50
50
5 0
50
6 0
60
50
50
5 0
60
60
6 0
50
60
6 0
60
60
50
60
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
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 2.0 M,
MAIB 0.05 M
Solvent: benzene 1.5 M, k, and k,
also given by other [M]
Solvent: benzene 1.5 M,
MAIB 0.02M
Solvent: cyclohexane 1.33 M,
MAIB 5.00 x lo-M, k, and k,
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: acetonittile 1.33 M
Solvent: benzene 0.794M,
AIBN 0.05 M k, also given
by other [M]
Solvent: benzene 0.794 M,
MAIB 0.05 M
Solvent: benzene 2.0 M,
MAIB 0.05 M
Solvent: benzene 1.5 M,
MAIB 0.02M
Solvent: benzene 1.5 M,
MAIB 0.02 M
Solvent: benzene 1.5 M,
MAIB 0.02M
Solvent: benzene 2.0 M,
MAIB 0.05 M
Solvent: benzene 1.5 M,
MAIB 0.02 M
Solvent: benzene 1.5 M,
MAIB 0.02M
Solvent: benzene 1.5 M,
MAIB 0.02M
Solvent: benzene 1.5 M,
MAIB 0.02 M
Solvent: benzene 2.0 M,
MAIB 0.05 M
Solvent: benzene 2.0 M,
MAIB 0.05 M, k, and kt
also given by other [M] and temp.
Sol vent : THF 0. 44 M,
AIBN 0.05 M, k, and k,
also given by other [M]
Solvent: DMF 1.4M,
AIBN 0.05 M, k, and kt
also given by other [M] and temp.
2 1 3
1 8 5
185
185
185
1 8 5
185
1 8 5
185
1 7 7
2 1 3
1 8 2
1 6 2
1 6 2
1 6 2
1 6 2
1 6 2
1 6 2
1 6 2
1 5 4
1 5 4
1 7 7
1 8 2
1 8 2
1 8 2
1 7 7
1 8 2
1 8 2
1 8 2
1 9 5
111
233
1 9 5
195
195
1 9 5
234
2 3 5
i
Fumaric Derivatives, Vinyl Halides, and Vinyl Esters II/87
TABLE 6. FUMARIC DERIVATIVES
Monomer k, (l/mol/s) k t ( x 10 -6) (Ymolk) Temp. (C) Method Remarks Refs.
Fumaric acid
-, bis (2-methoxy-ethyl) ester
-, bis (Zchloro-ethyl) ester
-1 tert-butyl methyl ester
-3
rerr-butyl isopropyl ester
0 . 1 9
0 . 2 6
0 . 2 3
0 . 5 1
0 . 3 5
0 . 3 9
0 . 6 1
0.60
0 . 2 1
0.015
330 x 10-6
320 x 1O-6
1 5 0 x 10-6
26 x 1O-6
60
60
60
60
60
Sol ve nt : be nz e ne 1 . O M
Solvent: benzene l.OM
Sol ve nt : be nz e ne 1 . O M
Solvent: benzene 1.OM
AIBN
MAIB
Solvent: benzene 1.0 M
Solvent: benzene 1.0 M
Solvent: benzene l.OM
AVN (2,2-azobis-2,4-
dimethylvaleronitrile),
ACN (1,l -azobiscyclo-hexane-
1-carbonitrile)
ACN, scavenger TPV
(1,3,5&iphenylverdazyl),
sovent: benzene
Sol ve nt : be nz e ne 1 . O M
ACN, scavenger TPV,
solvent: benzene
Solvent: benzene 1 .O M
Solvent: benzene 1 .O M
Solvent: benzene 1.16 M,
MAIB O.lOOM, k, and kt
also given by other [M]
2 1 1
2 1 1
2 1 1
2 1 1
181
181
2 1 1
2 1 1
2 1 1
1 7 3
1.75 x 10-5
30 x 10-6
40 x 10-6
(510- 560) x 1O-6
1.64 x 10-4
6 0 C
6 0 C
60 C
3 0 Al
-, di-reti-butyl ester
-, dicyclohexyl ester
-, diethyl ester
0.029 f 0.003 8 x 10-6 30 BlO 1 7 9
0.46 (80- 100) x 1O-6 60 C
0.31 f0.07 0.84 x 1O-6 3 0 BlO
2 1 1
1 8 0
-, diisopropyl ester
-, dimethyl ester 0.058 430 x 10-6
-, dineopentyl ester 0.028 44 x 10-6
Ethyl o-formylphenyl fumarate 4 . 0 1.4
C
C
C
2 1 1
2 1 1
236
TABLE 7. VINYL HALIDES
Monomer k, (l/mol/s) kt(x10m6) (Ymolk) Temp. (C) Method Remarks Refs.
Tetrafluoroethylene
Vinyl bromide
Vinyl chloride
Vinylidene chloride
7400
2
2 2 . 7
570
k, = 3.3 x 106
x exp(- 15000/R7)
1 1 0 0 0
3130
8 . 6
k,= log
x exp(- 4540/7)
7.4 x 10-5
9 2
3 8 5
k, = 1.3 x lo6
x exp(- 4200/RTj
2100
2300
0.175
k,=106
x exp(- 267017)
40
- 3 0
20
2 5
2 5
2 5
22-75
Al
Al
Al
Al
Al
Al
Large active chain end concentration 8 1
measured by addition of inhibitor
in aqueous solution polymn.
8 0
Quoted in Ref. 80 44
3 2
56
7 7
18
Solvent: N-methylpyrrolidone 2.0 M 1 1 7
TABLE 8. VINYL ESTERS
Monomer k, (Ymolh) k t ( x 10 -6) (YmoVs) Temp. (C) Method Remarks Refs.
4600 220
795 46
556- 586 2860- 3040
670- 770 2500- 3100
700 2600
559 5 1 . 8
1 1 0 0 8 0
1 0 0 0 5 9
8 9 5 24
k,=2.43 x 10 k, =4.16 x lo5
x exp(- 30600/RT) x exp(- 21900/RT)
9500- 19000 380-760
(15-26) x lo2 2 5
2 . 5
15
15.9
15.9
15.9
2 0
2 5
2 5
2 5
B5
Bl
Al
Al
Al
B 4
Al
Al
B 4
Al
Sol ve nt : n-hexane
At 4% conversion
13
4 7
1
3
4
3 7
2
15
3 6
8
Vi nyl acet at e
6 0 E
5 0 Al
Using results of Refs. 8 and 15 64
128
References page II - 15
II/88 PROPAGATION AND TERMINATION CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 8. contd
Monomer k, (VmoVs) k , (x 10 -6) (VmoVs) Temp. (C) Method Remarks Ref s.
117512 319f61
113flO 351 f54
481t5 239 f 45
97flO 311 f59
61&9 266 f 75
37&5 412 f 104
8&1 258 zt 76
637 i 101 94.2 i 23.7
7 8 -
1 2 0 310
530 630
1 9 0 0 280
1 4 0 0 -
4 4 3 5 6 4 . 4
k, = 2.0 x 106 2 7 . 5
x exp[(- 19000 f 2900)/RT]
k, =2.7 x lO*
x exp(- 27820/RT)
ln[(k&]/(l.OO-0.07p)l
=lnk,[l]-0.50p
Vi nyl benzoate 106514 253 zt 63
185f8 402 i 32
245 f 13 522 i 48
168 f 18 383 f 76
69f13 257 f 72
3 3 1 3 299 f 44
267 ic 33 451 f65
3 0 Al
Al
Al
Al
Al
Al
Al
Al
32.5 Al
32.5 C
32.5 C
32.5 C
3 0 Al
15-60 C
Fl 209
3 0
3 0
B5 ktb]; k, for pressure p (bar) 1 2 2
Al
Al
Al
Al
Al
Al
Al
Solvent: benzene 2.00M 1 3 0
Solvent: C gD 6 2.00 M 1 3 0
Solvent: anisole 2.00 M 1 3 0
Solvent: fluorobenzene 2.00 M 1 3 0
Solvent: chlorobenzene 2.00 M 1 3 0
Solvent: ethyl benzoate 2.00 M 1 3 0
Solvent: benzonitrile 2.00 M 1 3 0
Solvent: ethyl acetate 2.00M 1 3 0
Solvent: ethyl acetate: ethyl 1 3 0
benzoate (1 : 1 (v/v))
Solvent: benzene
Solvent: benzene 5.41 M
Solvent: ethyl acetate 5.43 M
Pressure 5.0 x 1OPa
153
1 5 3
1 5 3
1 5 3
1 1 2
4 5
.
k,[l] = 52.0 x IO6
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 .O 1 M
1 1 6
1 1 6
1 1 6
1 1 6
1 1 6
1 1 6
1 1 6
TABLE 9. VINYL ETHERS
Monomer k, (VmoVs) kt (~10~~) (VmoVs) Temp. (C) Method Ref s.
Monovinyl ether of ethylene glycol 5.0f 1.0 1. 5f 0. 3 5 0 Al 1 3 6
Monovinyl ether of diethylene glycol 3.01tO.8 1.4&0.3 5 0 Al 1 3 6
TABLE 10. STYRENE DERIVATIVES
Monomer k, (UmoVs) kt(x10m6) (VmoVs) Temp. (C) Method Remarks Refs.
Styrene 40f20 8O~t40 15 Al
2 4 14 2 0 Al
5 1 . 9
1 0 8
1 0 6
1 0 2
390
209
18.7
3 9 . 5
k,= 2. 16~10'
x exp(- 32500/RT)
2 2
10. 5
3 2 . 5
1 0 8
-
115
2 . 7 9
5 . 9 6
3 0
3 0
3 0
40
50
50
2 5
2 5
2k, = 2.59 x lo3
x exp(- 9920/R7)
Al
Al
Al
D
D
E
B 5
Bl
Al
5 D
1 3 9
2 2 3
206
40
5 0
5 0
D
D
D
Dimension of k, and kt: kg/mol/s
From copolymn. data with sulfur
dioxide
Quoted in Ref. 86
Using results of Ref. 20
Catalyst: cumene hydroperoxide-
triethylenetetramine
Catalyst: persulfate
46
2 5
16
3 8
7 8
5 9
5
61
6
17
20
2 4
2 4
4 0
6 7
TABLE 10. contcf
Styrene Derivatives II/89
Monomer k, (l/moU.s) k t ( x 10 +) (Vmolh) Temp. (C) Method Remarks Refs.
k, =2.24 x 1014
x exp(- 73510/RlJ
50
8 0
370
25f3
35f7
35f5
29f7
23f8
27f4
k,=1.09 x lo7
x exp(- 31380/RT)
66.6
66.5
k,=2.4 x lo*
x exp(- 38000 f 17OO)/RT
187.1
6 4
915
9f1. 5
19f4
19f3
15f4
l l f 2
31 f0.4
k, = 1.703 x lo3
x exp(- 9489/RT)
22.4
29.4 6 0
2 5 D 6 5
60 Al 1 1 8
2 5 Al
2 5 Al
2 5 Al
2 5 Al
2 5 Al
2 5 Al
15-30 A2
30
2 5
50- 90
8 4
k,=107.630 x exp(- 325lOIRT) - 12- 93 F 2
2 5 Fl
76 2 5 Fl
70 2 5 Fl
380f 110 40 Fl
480 f 10 70 C
16.6-17.0 1 0 0 C
256 1 9 0 50 C
1 0 7
-
2 5 Gl
kt (m,n) = 1.97 x lo* (n x m) -.I* 3 0 A3
-, p-bromo-
-, p-chloro-
-, p-cyano-
-, p-fluoro-
-, p-methoxy-
180f 10
k,=1.99 x lo7 exp(- 30780fRT)
In k, = 17.14-1.873 x 1O-9 p
- 3748/T+2.02 x 1O-6 p/T
77f4.1
79f5.1
187.0
201.0
167.0
641 f48
8 9
1 0 7
9 2
7 8
2 3
In k,= 16.09-2895O/RT (overall)
= 16.47-3003/RT (chain length 2 4)
k = 107.1*0.5
x exp[-729 f 3) x 103/RTJ
k,= 1.8861 x lo7
x exp(- 30737.52/RT)
k,=4.2060 x lOa
x exp(- 37468.93/RT)
k,=4.2458 x 10
x exp(- 39014.90/RT)
1 8 6
1 5 0
219
1 1 2
2.92
7 1
78fl2
96f9
63.2
51.1
37.9
1 3 2
0.6
46 30 Al
7 7 30 Al
3 5 3 0 Al
1 2 7 3 0 Al
1.06 0 B5
3 3 3 0 Al
5
30- 90
2 5 Fl
2 5 Fl
60 B5
91.2
2 5
3 0
2 5
2 5
2 8
Bl 7 3
Addition of 1 x 10m3 mol pyridine
Solvent: dodecane 40% by vol
1 1 8
1 0 4
1 0 0
Al
C
Solvent: bromobenzene 20% by vol 1 0 0
Solvent: diethyl malonate 20% by vol 1 0 0
Solvent: diethyl phthalate 20% by vol 1 0 0
Solvent: dinonyl phthalate 60% by vol 100
m=2500 1 1 4
Pressure 5.0 x lo7 Pa 1 0 2
9 8
9 8
Special evaluation from steady-state 1 3 4
kinetics and iii,
2 1 5
k,also given by other [M] and
s o l v e n t s
1 9 6
Solvent/ethanol (25%) 6.52 M 1 9 6
Solvent: methanol (25%) 6.52 M 1 9 6
Pressure 2.0 x lo8 Pa 1 8 6
Over a range of degree of polymn. 1 8 8
of the oolvmer radical from 40 to 410
Conversion i)-20%
TBP (rert-butyl peroxide)
k, and kt also given by other temp.
Laser-flash-initiated polymn. by
benzoin
1 7 4
1 8 9
1 5 6
n: n-mer, m: m-mer,
coupling with n-mer and m-mer
1 4 7
C
Fl
F2 Pressure 1 x 10s-2.8 x lo* Pa
223
1 6 9
214
Gl
Al
Fl
Fl
Fl
Bl
Fl
Solvent: toluene 50% (v/v)
Solvent: benzene 3 M
Solvent: chlorobenzene 3 M
Solvent: benzonitrile 3 M
Solvent: toluene
k, also given by other temp.
Solvent: benzene 4.33 M
161
161
204
204
204
1 7 8
1 6 0
1 9 8
220
1 6 4
8 3
200
Bl 131
Fl 227
Fl 30% styrene in benzylalcohol 227
Fl 30% styrene in NMP 227
Solvent: dimethylacetamide
7 8
7 8
7 8
7 8
12
7 8
References page II - 15
II/90 PROPAGATION AND TERMINATION CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 10. contd
Monomer k, (YmoYs) k t ( x 10 -6) (VmoUs) Temp. (C) Method Remarks Refs.
-,
o-methyl-
-, p-methyl-
Styrene-d s
k, = 1.67 x 10
xexp(- 58240/RT)
84
k,=2.27x 10'
xexp(- 32060/RlJ
k = 105.
x ex;(-23.O/RT)
k,=3.63x 10
x exp(- 31500/RT)
66
kt=2.55 x lo4
x exp(- 14200/R?J
30
24-55
Bl
Al
Bl
Fl
Al
Solvent: toluene 2M
73
78
73
226
1 6 8
TABLE 11. VINYL HETEROAROMATICS
Monomer k, (VmoVs) kt (x 10 -6) (YmoVs) Temp. (C) Method Remarks Refs.
N-Vinylcarbazole 6.0
2-Vinylpyridine 1 8 6
96.6
4-Vinylpyridine 12
5-Vinylpyridine 47
-, 2-methyl- 1 2 2
209
17.3
N-Vinylpyrrolidone 953
220OOf4000
0.306 1 0 Al
33 25 Al
8.9 25 B 4
3 25 B5
3.5 25 B 4
66 20 Bl
43 20 Bl
1.2 20 Bl
65 20 B4
600f200 25 Al
80
76
76
34
75
Sol ve nt : methanol 1.95 M, k, 94
also given as a function of [MI
Solvent: 50% (molar) aqueous methanol 94
Solvent: acetic acid 94
82
Sol ve nt : water 1 3 2
TABLE 12. ALDEHYDES
Monomer k, (VmoVs) k t (x 10 -6) (VmoVs) Temp. (C) Method Remarks Ref s.
Formaldehyde
-
(7-10) x 10-3 - 190 B 4 Solid monomer, gamma irradiation 9 5
TABLE 13. OTHERS
Monomer k, (VmoVs) k,(x10m6) (l/mob) Temp. (C) Method Remarks Refs.
Maleimide
-, N-rerr-amyl-
-1
N-terr-butyl-
-7
N-terr-butyl-dimethylsilyl-
-,
N-rert-octyl-
-, N-trimethylsilyl-
-, N-cyclohexyl-
69
1 0 0
0.048a,0.017b
0.021 a,0.023

b
60
60
1 2 0 0.20a 60
23 0.027a,0.015b 60
1 2 0 0.15,0.23b 60
49 0.054 50
55 0.069
C Solvent: benzene 1 M
C (a) Determined from steady-state
equation k, = (2kdf[I])/[P12,
AIBN 0.005 M;
(b) determined from second order
plot of the decay curve of the
radical concentration, ATMP
(22.azobis-(2,4$trimethyl-
pentane)) 0.02 M, for terr-BMI,
ATMP 0 . 0 1 M
C
C
C
C Solvent: benzene 0.559M,
AIBN 1.39 x IO-* M
Solvent: benzene 0.698 M,
AIBN 1.00 x lo-M, k, and k,
also given by other [Ml and [I]
205
205
205
205
205
163
163
Tic
-
M
-
-9
-3
-,
-,
-,
-,
-,
0 1
-
C,
1
1
1
1
1
1
1
t
i 1
i
i
I
TABLE 13. contd
References II/91
Monomer k, (VmoVs) k t (x 10 -6) (l/mol/s) Temp. (C) Method Remarks Ref s.
-, N-(2,6-diethylphenyl- 2 . 0 0.0078 60 C Solvent: benzene 1 M, 183
AIBN 5 x 1O-3 M
-, N-(2,6-dimethylphenyl)- 14 0.034 60 C Solvent: benzene 1 M, 1 8 3
AIBN 5 x 1O-3 M
-, N-(Cethylphenyl)- 1 2 0 0 3 . 9 60 C Solvent: benzene 1 M, 1 8 3
AIBN 5 x 10-3M
-, N-(2-methylphenyl)- 1 9 0 0 . 5 9 6 0 C Solvent: benzene 1 M, 183
AIBN~x~O-~M
-, N-(2.carboethoxyphenyl)- 9 6 0.10 60 C Solvent: benzene MAIB 0.005 M 237
-, N-dodecyl- 5 4 0.12 5 0 C Solvent: benzene MAIB 0.01 M 238
1 0 4 0 . 4 5 50 C Solvent: toluene MAIB 0.01 M 238
175 1.0 5 0 C Solvent: anisole MAIB 0.01 M 238
8 0 0 . 4 0 5 0 C Solvent: chlorobenzene MAIB 0.01 M 238
1 2 8 0.064 5 0 C Solvent: bromobenzene MAIB 0.01 M 238
1 4 9 0 . 1 7 5 0 C Solvent: methyl benzoate MAIB 238
0 . 0 1 M
386 - 5 0 C Solvent: THF, MAIB 0.01 M 238
250 5 0 C Solvent: dioxane, MAIB 0.01 M 238
235 0 . 5 5 5 0 C Solvent: ethyl acetate MAIB 0.01 M 2 3 8
1 9 6 - 5 0 C Solvent: methyl ethyl ketone MAIB 238
0 . 0 1 M
-, N-octadecyl- 3 3 0.10 5 0 C Solvent: benzene AIBN 0.20M, k, 239
and k, also given by other [I]
Oligotetramethylene glycol dimethacrylic 400 0 . 0 7 5 0 B 9 1 2 4
ester (MW 600)
C. REFERENCES
1. G. M. Burnett, H. W. Melville, Nature, 156, 661 (1945).
2. C. G. Swain, P. D. Bartlett, J. Am. Chem. Sot., 68, 2381
(1946).
3. G. M. Burnett, H. W. Melville, Proc. R. Sot. London, Ser. A,
189, 456 (1947).
4. G. M. Burnett, H. W. Melville, Proc. R. Sot. London, Ser. A,
189, 494(1947).
5. W. V. Smith, J. Am. Chem. Sot., 70, 3695 (1948).
6. C. H. Bamford, M. J. S. Dewar, Proc. R. Sot. London, Ser. A,
192, 308 (1948).
7. M. S. Matheson, E. E. Auer, E. B. Bevilacque, E. J. Hart, J.
Am. Chem. Sot., 71, 497 (1949).
8. M. S. Matheson, E. E. Auer, E. B. Bevilacque, E. J. Hart, J.
Am. Chem. Sot., 71, 2610 (1949).
9. M. H. Mackay, H. W. Melville, Tram Faraday Sot., 45, 323
(1949).
10. H. W. Melville, A. F. Bickel, Trans. Faraday Sot., 45, 1049
(1949).
11. C. H. Bamford, M. J. S. Dewar, Proc. R. Sot. London, Ser. A,
197, 356 (1949).
12. D. W. E. Axford, Proc. R. Sot. London, Ser. A, 197, 374
(1949).
13. G. Dixon-Lewis, Proc. R. Sot. London, Ser. A, 198, 510
(1949).
14. L. Valentine, Thesis, Aberdeen (1949).
15. H. Kwart, H. S. Broadbent, P. D. Bartlett, J. Am. Chem. Sot.,
72, 1060 (1950).
16. H. W. Melville, L. Valentine, Trans. Faraday Sot., 46, 210
(1950).
17. G. M. Burnett, Trans. Faraday Sot., 46, 772 (1950).
18. J. D. Burnett, H. W. Melville, Trans. Faraday Sot., 46, 976
(1950).
19. Ross, Thesis, Aberdeen (1950).
20. M. S. Matheson, E. E. Auer, E. B. Bevilacqua, E. J. Hart, J.
Am. Chem. Sot., 73, 1700 (1951).
21. M. S. Matheson, E. E. Auer, E. B. Bevilacqua, E. J. Hart, J.
Am. Chem. Sot., 73,5395 (1951).
22. T. G. Majury, H. W. Melville, Proc. R. Sot. London, Ser. A,
205, 496 (1951).
23. M. Morton, P. P. Salatiello, H. Landfield, J. Polym. Sci., 8,
215 (1952).
24. M. Morton, P. P. Salatiello, H. Landfield, J. Polym. Sci., 8,
279 (1952).
25. W. G. Barb, Proc. R. Sot. London, Ser. A., 212, 177 (1952).
26. P J. Flory, in: P J. Flory (Ed.), Principles of Polymer
Chemistry, Cornell University Press, New York, 1953,
p. 158.
27. G. M. Burnett, P. Evans, H. W. Melville, Trans. Faraday
Sot., 49, 1096 (1953).
28. G. M. Burnett, P. Evans, H. W. Melville, Trans. Faraday
sot., 49, 1105 (1953).
29. G. M. Burnett, in: G. M. Burnett (Ed.), Mechanism of
Polymer Reactions, Interscience, New York, 1954, p. 230,
p. 233.
30. B. R. Chinmayanandam, H. W. Melville, Trans. Faraday
sot., 50, 73 (1954).
31. J. C. Bevington, H. W. Melville, R. P. Taylor, J. Polym. Sci.,
14, 463 (1954).
II/92 PROPAGATION AND TERMINATION CONSTANTS IN FREE RADICAL POLYMERIZATION
32. G. M. Burnett, W. W. Wright, Proc. R. Sot. London, Ser. A,
211, 41 (1954).
33. J. L. OBrien, F. Gormick, J. Am. Chem. Sot., 77, 4757
(1955).
34. P. F. Onyon, Trans. Faraday Sot., 51, 400 (1955).
35. J. Durup, M. Magat, J. Polym. Sci., 18, 586 (1955).
36. W. J. Bengough, H. W. Melville, Proc. R. Sot. London, Ser.
A, 230, 429 (1955).
37. H. Miyama, Bull. Chem. Sot. Japan, 29, 720 (1956); ibid.
30, 10 (1957).
38. E. A. Nicholson, R. G. W. Norrish, Disc. Faraday Sot., 22,
104 (1956).
39. N. Grassie, E. Vance, Trans. Faraday Sot., 52, 727 (1956).
40. E. Bartholome, H. Gerrens, R. Herbeck, H. Weitz, Z.
Elektrochem., 60, 334 (1956).
41. F. S. Dainton, M. Tordoff, Trans. Faraday Sot., 53, 499
(1957).
42. W. M. Thomas, R. L. Webb, J. Polym. Sci., 25, 124 (1957).
43. C. H. Bamford, A. D. Jenkins, R. Johnston, Proc. R. Sot.
London, Ser. A, 241, 364 (1957).
44. M. Kryszewski, Roczniki Chemii, 31, 893 (1957).
45. S. E. Bresler, E. N. Kasbezov, V. N. Shandrin, Vysokomol.
Soedin., Ser. A, 17, 507 (1957).
46. K. Ueberreiter, G. Sorge, Z. Phys. Chem. (Frankfurt), 13,
158 (1957).
47. W. J. Bengough, Trans. Faraday Sot., 54, 868 (1958).
48. W. J. Bengough, A. C. K. Smith, Trans. Faraday Sot., 54,
1553 (1958).
49. W. J. Bengough, J. Polym. Sci., 28, 475 (1958).
50. Z. A. Sinitsyna, Kh. S. Bagdasaryan, Zh. Fiz. Khim., 32,
1319 (1958).
51. S. W. Benson, A. M. North, J. Am. Chem. Sot., 81, 1339
(1959).
52. D. H. Grant, N. Grassie, Trans. Faraday Sot., 55, 1042
(1959).
53. Z. Litia, Z. Machacek, J. Polym. Sci., 38, 459 (1959).
54. F. S. Dainton, D. G. L. James, J. Polym. Sci., 39, 299
(1959).
55. F. S. Dainton, R. S. Eaton, J. Polym. Sci., 39, 313 (1959).
56. W. J. Bengough, S. A. McIntosh, R. A. M. Thomson, Nature,
184, 266 (1959).
57. W. J. Bengough, H. W. Melville, Proc. R. Sot. London, Ser.
A, 249, 445 (1959).
58. W. J. Bengough, H. W. Melville, Proc. R. Sot. London, Ser.
A, 249, 455 (1959).
59. Z. Manisek, A. Rezabek, Int. Symp. Macromol. Chem.
(Moscow), Section 2 (Russian version) (1960).
60. P. Hayden, H. W. Melville, J. Polym. Sci., 43, 201 (1960).
61. G. Henrici-Olive, S. Olive, Makromol. Chem., 37, 71
(1960).
62. G. V. Shulz, G. Henrici-Olive, S. Olive, Z. Phys. Chem.
(Frankfurt), 27, 1 (1960).
63. W. J. Bengough, Proc. R. Sot. London, Ser. A, 260, 205
(1961).
64. G. V. Schulz, D. J. Stein, Makromol. Chem., 52, 1 (1962).
65. P. E. M. Allen, G. M. Burnett, J. M. Downer, J. R. Majer,
Makromol. Chem., 58, 169 (1962).
66. W. Rabel, K. Ueberreiter, Ber. Bunsenges. Phys. Chem., 67,
710 (1963).
67. H. Gerrens, Ber. Bunsenges. Phys. Chem., 67, 741 (1963).
68. N. Coleboume, E. Collinson, D. J. Currie, F. S. Dainton,
Trans. Faraday Sot., 59, 1357 (1963).
69. F. S. Dainton, W. D. Sisley, Trans. Faraday Sot., 59, 1369
(1963).
70. E. F. T. White, M. J. Zissell, J. Polym. Sci., Part A: Gen. Pap.,
1, 2189 (1963).
71. M. Morton, W. E. Gibbs, J. Polym. Sci., Part A: Gen. Pap., 1,
2679 (1963).
72. J. Hughes, A. M. North, Trans. Faraday Sot., 60, 960
(1964).
73. K. P. Paoletti, Jr. F. W. Billmeyer, J. Polym. Sci., Part A: Gen.
Pap., 2, 2049 (1964).
74. A. M. North, A. M. Scallan, Polymer, 5,447 (1964).
75. A. F. Revzin, Kh. S. Bagdasaryan, Zh. Fiz. Khim., 38, 1020
(1964).
76. W. I. Bengough, W. Henderson, Trans. Faraday Sot., 61,141
(1965).
77. W. I. Bengough, R. A. M. Thomson, Trans. Faraday Sot., 61,
1735 (1965).
78. M. Imoto, M. Kinoshita, M. Nishigaki, Makromol. Chem.,
86, 217 (1965).
79. D. J. Currie, F. S. Dainton, W. S. Watt, Polymer, 6, 451
(1965).
80. J. Hughes, A. M. North, Trans. Faraday Sot., 62, 1866
(1966).
81. A. N. Plyusnin, N. M. Chirkor, Teor. Eksp. Khimiya, 2,777
(1966).
82. V. A. Agasandyan, E. A. Trosman, Kh. S. Bagdasaryan,
A. D. Litmonovich, V. Ya. Shtem, Vysokomol. Soedin., 8,
1580 (1966).
83. K. M. Gibov, G. P Gladyshev, Izv. Akad. Nauk Kaz. SSR,
Ser. Khim., 17, 53 (1967).
84. F. Hrab& M. BezdBk, V. Hynkova, Z. Pelzbauer, J. Polym.
Sci., Part C: Polym. Symp., 16, 1345 (1967).
85. C. H. Bamford, S. Brumby, Makromol. Chem., 105, 122
(1967).
86. Kh. S., in: Kh. S. Bagdasaryan (Ed.), Bagdasaryan Theory
of Free Radical Polymerization, translated from the Rus-
sian Second Edition (1966) by J. Schmorak, Israel Program
for Scientific Translations, 1968.
87. K. Yokota, M. Kani, Y. Ishii, J. Polym. Sci., Part A-l: Polym.
Chem., 6, 1325 (1968).
88. J. Ulbricht, J. Polym. Sci., Part C: Polym. Symp., 16, 3747
(1968).
89. W. F. Gromov, P. M. Chomikovski, A. D. Abkin,
N. A. Rosanova, Vysokomol. Soedin., Ser. B, 10, 754
(1968).
90. C. H. Bamford, S. Brumby, Chem. Ind., 1020 (1969).
91. G. N. Komienko, A. Chervenka, I. M. Belugovskii,
N. S. Yenikolopyan, Vysokomol. Soedin., Ser. A, 11,
2703 (1969).
92. J. P. Fischer, G. V. Schulz, Ber. Bunsenges. Phys. Chem., 74,
1077 (1970).
93. G. M. Burnett, G. G. Cameron, M. M. Zafar, Eur. Polym. J.,
6, 823 (1970).
References II/93
94. A. V. Angelova, Yu. L. Spirin, R. Ye. Kovalchuk, Vysoko-
mol. Soedin., Ser. A, 12, 2703 (1970).
95. D. P. Kiryukin, A. M. Kaplan, I. M. Barkalov, V. I. Goldans-
kii, Dokl. Akad. Nauk SSSR, 199, 857 (1971).
96. S. V. Koslov, I. M. Bulugovskii, N. S. Enikolopyan, Vyso-
komol. Soedin., Ser. B, 13, 46 (1971).
97. A. A. Baturin, Yu. B. Amerik, B. A. Krentsel, V. N. Tsvetkov,
I. N. Shtennikova, E. I. Ryumtsev, Dokl. Akad. Nauk SSSR,
202, 586 (1972).
98. S. B. Bresler, E. N. Kasbekov, V. N. Formichev, V. N. Shadrin,
Makromol. Chem., 157, 167 (1972).
99. T. M. Karaputadse, A. I. Kurilova, D. A. Topchiev,
V. A. Kabanov, Vysokomol. Soedin., Ser. B, 14,323 (1972).
100. G. M. Burnett, G. G. Cameron, S. N. Joiner, J. Chem. Sot.,
Faraday Trans. I, 69, 322 (1973).
101. K. Yokota, A. Konda, Makromol. Chem., 171, 113 (1973).
102. Y. Ogo, M. Yokawa, T. Imoto, Makromol. Chem., 171, 123
(1973).
103. G. Mayer, G. V. Schulz, Makromol. Chem., 173,101(1973).
104. G. G. Cameron, J. Cameron, Polymer, 14, 107 (1973).
105. M. Yokawa, Y. Ogo, T. Imoto, Makromol. Chem., 175, 179
(1974).
106. M. Yokawa, Y. Ogo, T. Imoto, Makromol. Chem., 175,2903
(1974).
107. M. Yokawa, Y. Ogo, T. Imoto, Makromol. Chem., 1752913
(1974).
108. M. Ratzsch, J. Zschach, Plaste und Kautschuk, 21, 245
(1974).
109. N. A. Plate, A. G. Ponomarenko, Polym. Sci. USSR (Engl.
Transl.), 16, 3067 (1974).
110. K. F. ODriscoll, H. K. Mahabadi, J. Polym. Sci., Polym.
Chem. Ed., 14, 869 (1976).
111. P. Penchev, Makromol. Chem., 177, 413 (1976).
112. M. Yokawa, Y. Ogo, Makromol. Chem., 177, 429 (1976).
113. M. Yokawa, Y. Ogo, T. Imoto, Makromol. Chem., 178, 443
(1976).
114. H. K. Mahabadi, K. F. ODriscoll, J. Macromol. Sci. A:
Chem., 11, 967 (1977).
115. J. Gons, E. J. Vorenkamp, G. Challa, J. Polym. Sci., Polym.
Chem. Ed., 15, 3031 (1977).
116. M. Kamachi, J. Satoh, D. J. Liaw, S. Nozakura, Macromo-
lecules, 10, 501 (1977).
117. K. Matsuo, G. W. Nelb, W. H. Stockmayer, Macromolecules,
10, 654 (1977).
118. B. M. Soghomonyan, N. M. Beilerian, Armen. Chim. Zh.,
31, 567 (1978).
119. T. 0. Osmanov, V. F. Gromov, P. M. Khomikovskii,
A. D. Abkin, Dokl. Akad. Nauk SSSR, 240, 910 (1978).
120. T. Otsu, B. Yamada, S. Sugiyama, Kobunshi Ronbunsyu, 35,
705 (1978).
121. B. Yamada, M. Yoshioka, T. Otsu, Kobunshi Ronbunsyu, 35,
795 (1978).
122. Y. Ogo, T. Kyotani, Makromol. Chem., 179, 2407 (1978).
123. B. Yamada, H. Ohnishi, T. Otsu, Mem. Fat. Eng., Osaka City
Univ., 19, 189 (1978).
124. N. N. Tvorogov, A. G. Kondrateva, Vysokomol. Soedin.,
Ser. A, 20, 230 (1978).
125. N. N. Tvorogov, A. G. Kondrateva, Vysokomol. Soedin.,
Ser. A, 20, 1550 (1978).
126. P. M. Komikovskii, A. D. Abin, Vysokomol. Soedin., Ser. B,
20, 263 (1978).
127. N. N. Bashenova, B. A. Egorov, Yu. D. Semchikov, Dokl.
Akad. Nauk SSSR, 245, 621 (1979).
128. H. A. Bruk, S. A. Pavlov, A. D. Abkin, Dokl. Akad. Nauk
SSSR, 245, 626 (1979).
129. A. G. Shostenko, V. E. Myshkin, Kinet. Katal., 20, 781
(1979).
130. M. Kamachi, D. J. Liaw, S. Nozakura, Polym. J., 11, 921
(1979).
131. S. W. Lansdowne, R. G. Gilbert, D. H. Napper, J. Chem.
Sot., Faraday Trans. I, 76, 1344 (1980).
132. E. V. Shtamm, Yu. I. Skurlatav, I. M. Karaputadse, Yu. E.
Kirsh, A. I? Purmal, Vysokomol. Soedin., Ser. B, 22, 420
(1980).
133. M. Kamachi, D. J. Liaw, S. Nozakura, Polym. J., 13, 41
(1981).
134. K. Jen-Feng, C. Chu-Yung, Polym. J., 13, 453 (1981).
135. T. Takahashi, P. Ehrlich, Polym. Prepr., 22, 203 (198 1).
136. Z. S. Nurkeeva, E. M. Shaidutinov, A. S. Seitov, Izv. Akad.
Nauk Kaz. SSR, Ser. Khim., 1982, 47 (1982).
137. D. J. Liaw, K. C. Chung, J. Chinese Inst. Chem. Eng., 13,145
(1982).
138. M. Kamachi, M. Fujii, S. Nozakura, J. Polym. Sci., Polym.
Chem. Ed., 20, 1489 (1982).
139. T. Takahashi, P. Ehrlich, Macromolecules, 15, 714 (1982).
140. B. Yamada, T. Hayashi, T. Otsu, J. Macromol. Sci. A: Chem.,
19, 1023 (1983).
141. P. C. Lim, G. Luft, Makromol. Chem., 184, 207 (1983).
142. P. C. Lim, G. Luft, Makromol. Chem., 184, 849 (1983).
143. B. Yamada, M. Yoshioka, T. Otsu, Makromol. Chem., 184,
1025 (1983).
144. A. Nagy, T. Foldes-Beresznich, T. Tudos, Eur. Polym. J., 20,
25 (1984).
14.5. B. Yamada, M. Yoshioka, T. Otsu, J. Polym. Sci., Polym.
Chem. Ed., 22, 463 (1984).
146. B. Yamada, T. Kontani, M. Yoshioka, T. Otsu, J. Polym. Sci.,
Polym. Chem. Ed., 22, 2381 (1984).
147. H. K. Mahabadi, Macromolecules, 18, 1319 (1985).
148. G. Meyerhoff, R. Sack, M. Kouloumbris, Polym. Prepr.,
26 (l), 293 (1985).
149. M. J. Ballard, D. H. Napper, R. G. Gilbert, D. F. Sangster,
J. Polym. Sci., Part A: Polym. Chem., 24, 1027 (1986).
150. M. J. Ballard, R. G. Gilbert, D. H. Napper, P. J. Pomery,
P. W. OSullivan, J. H. ODonnell, Macromolecules, 19,
1303 (1986).
151. M. Buback, H. Hippler, J. Schweer, H. -P. Vogele, Makro-
mol. Chem., Rapid Commun., 7, 261 (1986).
152. M. Kamachi, H. Umetani, S. Nozakura, Polym. J., 18, 211
(1986).
153. M. Kamachi, Adv. Polym. Sci., 82, 209 (1987).
154. T. Sato, S. Inui, H. Tanaka, T. Ota, M. Kamachi, K. Tanaka,
J. Polym. Sci., Part A: Polym. Chem., 25, 637 (1987).
155. W. Lau, D. G. Westmoreland, R. W. Novak, Macromole-
cules, 20, 457 (1987).
II/94 PROPAGATION AND TERMINATION CONSTANTS IN FREE RADICAL POLYMERIZATION
156. 0. F. Olaj, I. Schnoll-Bitai, F. Hinkelmann, Makromol.
Chem., 188, 1689 (1987).
157. T. Sato, K. Morino, H. Tanaka, T. Ota, Makromol. Chem.,
188, 2951 (1987).
158. J. Shen, Y. Tian, Y. Zeng, Z. Qiu, Makromol. Chem., Rapid
Commun., 8, 615 (1987).
159. R. Sack, G. V. Schulz, G. Meyerhoff, Macromolecules, 21
3345 (1988).
160. 0. F. Olaj, P Kremminger, I. Schnoll-Bitai, Makromol.
Chem., Rapid Commun., 9, 771 (1988).
161. 0. F. Olaj, I. Schntill-Bitai, Eur. Polym. J., 25, 635
(1989).
162. T. Sato, N. Morita, H. Tanaka, T. Ota, J. Polym. Sci., Part A:
Polym. Chem., 27, 2497 (1989).
163. T. Sato, K. Arimoto, H. Tanaka, T. Ota, K. Kato, K. Doiuchi,
Macromolecules, 22, 2219 (1989).
164. T. P. Davis, K. F. ODriscoll, M. C. Piton, M. A. Winnik,
Macromolecules, 22, 2785 (1989).
165. R. Sack-Kouloumbris, G. Meyerhoff, Makromol. Chem.,
190, 1133 (1989).
166. R. W. Garrett, D. J. T. Hill, J. H. ODonnell, P. J. Pomery,
C. L. Winzor, Polym. Bull., 22, 611 (1989).
167. M. Buback, J. Schweer, Z. Phys. Chem. (Munich), 161,153
(1989).
168. G. Clouet, P. Chaffanjon, J. Macromol. Sci. A: Chem., 27,
193 (1990).
169. T. P. Davis, K. F. ODriscoll, M. C. Piton, M. A. Winnik,
Macromolecules, 23, 2113 (1990).
170. T. Sato, N. Morita, H. Tanaka, T. Ota, Makromol. Chem.,
191, 2559 (1990).
171. F. Tudos, A. Nagy, T. Foldes-Berezsnich, Angew. Makro-
mol. Chem., 185/186, 303 (1991).
172. T. Sato, I. Kamiya, H. Tanaka, T. Ota, Eur. Polym. J., 27,
1087 (1991).
173. T. Otsu, B. Yamada, T. Ishikawa, Macromolecules, 24, 415
(1991).
174. B. Yamada, M. Kageoka, T. Otsu, Macromolecules, 24,5234
(1991).
175. J. Shen, Y. Tian, G. Wang, M. Yang, Makromol. Chem., 192,
2669 (1991).
176. B. Yamada, M. Satake, T. Otsu, Makromol. Chem., 192,
2713 (1991).
177. T. Sato, Y. Takahashi, M. Seno, H. Nakamura, H. Tanaka,
T. Ota, Makromol. Chem., 192, 2909 (1991).
178. 0. F. Olaj, I. Schnoll-Bitai, Makromol. Chem., Rapid Com-
mun., 12, 373 (1991).
179. B. Yamada, E. Yoshikawa, H. Miura, T. Otsu, Polym. Bull.,
26, 543 (1991).
180. B. Yamada, E. Yoshikawa, K. Shin&hi, H. Miura, T. Otsu,
Polymer, 32, 1892 (1991).
181. M. Yoshioka, T. Otsu, Macromolecules, 25, 559 (1992).
182. T. Otsu, K. Yamagishi, M. Yoshioka, Macromolecules, 25,
2713 (1992).
183. A. Matsumoto, Y. Oki, T. Otsu, Eur. Polym. J., 29, 1225
(1993).
184. W Lau, D. G. Westmoreland, Macromolecules, 25, 4448
(1992).
185. T. Sato, T. Shimizu, M. Seno, H. Tanaka, T. Ota, Makromol.
Chem., 193, 1439 (1992).
186. M. Buback, B. Huckestein, B. Lugwig, Makromol. Chem.,
Rapid Commun., 13, 1 (1992).
187. S. Deibert, F. Bandermann, J. Schweer, J. Sarnecki, Makro-
mol. Chem., Rapid Commun., 13, 351 (1992).
188. B. Yamada, M. Kageoka, T. Otsu, Polym. Bull., 28, 75
(1992).
189. B. Yamada, M. Kageoka, T. Otsu, Polym. Bull., 29, 385
(1992).
190. G. Moad, E. Rizzardo, D. H. Solomon, A. L. J. Beckwith,
Polym. Bull., 29, 647 (1992).
191. T. G. Carswell, D. J. T. Hill, D. I. Londero, J. H. ODonnell,
P. J. Pomery, C. L. Winzor, Polymer, 33, 137 (1992).
192. D. J. Liaw, J. R. Lin, K. C. Chung, J. Macromol. Sci. A: Pure
Appl. Chem., 30, 51 (1993).
193. A. Matsumoto, K. Mizuta, T. Otsu, J. Polym. Sci., Part A:
Polym. Chem., 31, 2531 (1993).
194. A. Matsumoto, K. Mizuta, T. Otsu, Macromolecules, 26,
1659 (1993).
195. T. Otsu, K. Yamagishi, A. Matsumoto, M. Yoshioka,
H. Watanabe, Macromolecules, 26, 3026 (1993).
196. B. R. Morrison, M. C. Piton, M. A. Winnik, R. G. Gilbert,
D. H. Napper, Macromolecules, 26, 4368 (1993).
197. P. Pascal, M. A. Winnik, D. H. Napper, R. G. Gilbert,
Macromolecules, 26, 4572 (1993).
198. R. A. Hutchinson, M. T. Aronson, J. R. Richards, Macro-
molecules, 26, 6410 (1993).
199. l? 0. Danis, D. E. Karr, D. G. Westmoreland, M. C. Piton,
D. I. Christie, P A. Clay, S. H. Kable, R. G. Gilbert,
Macromolecules, 26, 6684 (1993).
200. M. Deady, A. W. H. Mau, G. Moad, T. H. Spurling, Makro-
mol. Chem., 194, 1691 (1993).
201. M. Buback, B. Degener, Makromol. Chem., 194, 2875
(1993).
202. S. Deibert, F. Bandermann, Makromol. Chem., 194, 3287
(1993).
203. P. Pascal, M. A. Winnik, D. H. Napper, R. G. Gilbert,
Makromol. Chem., Rapid Commun., 14, 213 (1993).
204. E. L. Madruga, Makromol. Chem., Rapid Commun., 14,581
(1993).
205. A. Matsumoto, Y. Oki, T. Otsu, Polym. J., 25, 237 (1993).
206. B. Yamada, S. Kobatake, S. Aoki, Macromol. Chem. Phys.,
195, 933 (1994).
207. S. Beuermann, M. Buback, G. T. Russell, Macromol. Rapid
Commun., 15, 351 (1994).
208. S. Beuermann, M. Buback, G. T. Russell, Macromol. Rapid
Commun., 15, 647 (1994).
209. R. A. Hutchinson, J. R. Richards, M. T. Aronson, Macro-
molecules, 27, 4530 (1994).
210. A. Matsumoto, K. Mizuta, Macromolecules, 27, 5863
(1994).
211. A. Matsumoto, T. Otsu, Proc. Jpn. Acad., Ser. B, 70, 43
(1994).
212. V. P. Budtov, B. V. Revnov, Vysokomol. Soedin., Ser. A Ser.
B, 36, 1061 (1994).
213. A. Matsumoto, K. Yamagishi, T. Otsu, Eur. Polym. J., 31,
121 (1995).
Ref er ences I I / 95
214. M. Buback, F. D. Kuchta, Macromol. Chem. Phys., 196,
1887 (1995).
215. M. Buback, R. G. Gilbert, R. A. Hutchison, B. Klumperman,
F. Kuchta, B. G. Manders, K. F. ODriscoll, G. T. Russell, J.
Schweer, Macromol. Chem. Phys., 196, 3267 (1995).
216. U. Bergert, M. Buback, Macromol. Rapid Commun., 16,275
(1995).
217. U. Bergert, S. Beuermann, M. Buback, C. H. Kurz,
G. T. Russell, C. Schmaltz, Macromol. Rapid Commun.,
16, 425 (1995).
218. D. A. Shipp, T. A. Smith, D. H. Solomon, H. David, G. Moad,
Macromol. Rapid Commun., 16, 837 (1995).
219. R. A. Hutchinson, D. A. Paquet, J. H. McMinn, R. E. Fuller,
Macromolecules, 28, 4023 (1995).
220. J. Same&i, J. Schweer, Macromolecules, 28, 4080 (1995).
221. F. Bandrmann, C. Guenther, J. Schweer, Macromol. Chem.
Phys., 197, 1055 (1996).
222. M. D. Zammit, T. P. Davis, D. M. Haddleton, Macromole-
cules, 29, 492 (1996).
223. M. Kamachi, A. Kajiwara, Macromolecules, 29, 2378
(1996).
224. H. Tanaka, S. Yoshida, Macromolecules, 28, 8117 (1995).
225. S. Kobatake, B. Yamada, S. Aoki, Polymer, 36,413 (1995).
226. T. Sato, I. Kamiya, M. Seno, H. Tanaka, J. Macromol. Sci. A:
Pure Appl. Chem., 32, 415 (1995).
227. M. Ueda, S. Shimada, T. Ogata, K. Ookawa, H. Ito,
B. Yamada, J. Polym. Sci., Part A: Polym. Chem., 33,
1059 (1995).
228. S. Kobatake, B. Yamada, Macromolecules, 28,4047 (1995).
229. S. Kobatake, B. Yamada, J. Polym. Sci., Part A: Polym.
Chem., 34, 95 (1996).
230. S. Kobatake, B. Yamada, Polym. J., 28, 535 (1996).
231. M. Seno, T. Takikawa, H. Tanaka, T. Sato, Macromolecules,
28, 4795 (1995).
232. A. Matsumoto, K. Shimizu, K. Mizuta, T. Otsu, J. Polym.
Sci., Part A: Polym. Chem., 32, 1957 (1994).
233. T. Sato, Y. Hirose, M. Seno, H. Tanaka, J. Polym. Sci., Part
A: Polym. Chem., 33, 797 (1995).
234. T. Sato, A. Takarada, H. Tanaka, T. Ota, Makromol. Chem.,
192, 2231 (1991).
235. T. Sato, M. Okazaki, M. Seno, H. Tanaka, Makromol.
Chem., 194, 637 (1993).
236. T. Sato, S. Shimooka, M. Seno, H. Tanaka, J. Polym. Sci.,
Part A: Polym. Chem., 33, 2865 (1995).
237. A. Matsumoto, T. Kimura, J. Macromol. Sci. A: Pure Appl.
Chem., 33, 1049 (1996).
238. T. Sato, K. Ma&i, M. Seno, H. Tanaka, Polym. Bull., 35,
345 (1995).
239. T. Sato, K. Masaki, M. Seno, H. Tanaka, Makromol Chem.,
194, 849 (1993).
Transfer Constants to Monomers,
Polymers, Catalysts and Initiators,
Solvents and Additives, and
Sulfur Compounds in Free
Radical Polymerization+
A. Ueda
Osaka Municipal Technical Research Institute, Osaka, Japan
S. Nagai
Plastics Technical Association, Osaka, Japan
A. Introduction
0. Tables
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
Co mp o u n d s
C. Remarks
D. References
II-97
II-98
II-98
II-1 03
II-1 06
II-1 10
II-1 50
II-1 57
II-1 59
A. I NTRODUCTI ON
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:
P;+RX%P,R+X
ki,X
X*+M+Pi
The dimensionless transfer constant is defined by the ratio
Cx = ktr,x/k,
where k, is the rate constant of propagation.
t Based on the tables in the third edition, by K. C. Berger and G. Brandrup.
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 indepen-
dent 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]/dt = 0).
The application of these assumptions to the common
reaction scheme results in the following relationship of
ideal kinetics (Ref. 145):
1
-i+cc,--
[Xl
P,-Pn0 PI
P,, P,,a = number-average degree of polymerization
obtained in the presence or absence, respec-
tively, of transfer agent X.
[Ml, [X] = concentration of monomer or transfer agent,
respectively.
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 viscos-
ity (Remark R). It should be noted that the ratio of
I I /97
II/98 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
viscosimetric to number average molecular weight shows a
considerable dependence on the molecular weight distribu-
tion.
The first term Pns 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:
Initiation Ri = 2fkd[I] or therm. Ri = Rt
Termination
Rt = kt[P] 2 = (kt,d + k,c)[P] 2
Propagation
R, = k, WI PI1
Number-average
molecular weight
p
II0
= 20 +fi> R,
-i-TzK
where kt, kt,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:
WI PI PI
cx=Ch4+c1-+cs-+cC,-+...
WI [Ml PI
where C, 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:
B. TABLES OF TRANSFER CONSTANTS
TABLE 1. TRANSFER CONSTANTS TO MONOMERS
This decrease of the transfer agent concentration with
increasing monomer conversion is important in practice
because very reactive transfer agents are used up preferen-
tially, 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 U1iZ as that
monomer conversion where the transfer agent is half
consumed:
u,p = lOO( 1 - 0.5 lcx)
The following table demonstrates (with some examples for
a calibration curve) that the half-conversion U112
decreases with increasing transfer constant Cx:
The Half-Conversion of Transfer Agents
cx U1/2(%) CX U1/2(%b)
0.1 99.9 5 13.0
0.2 96.8 1 0 6.7
0.5 75.0 20 3.4
1 50.0 50 1.4
2 29.3 100 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.
Monomer
T (C) CM (x104) Remarks Refs.
Acetic acid, a l l y 1 ester
80 170 29
700 27
Acrylamide 25 0.12 D 92
0.16 74
0.2 75
0.2 E 103
50 0.558 C2, F13, LL 560
60 0.651 C2, F13, LL 560
60 0.6 E 103
50 1.5 272
55 0.883 291
60 0.905 291
60 0.333 Cl, H, KK 561
60 1.05 Cl, H, KK 561
Acrylamide, N,N-dimethyl-
Acrylic acid, benzyl ester
-, butyl ester
TABLE 1. conrd
Transfer Constants to Monomers II/99
Monomer T (Cl CM (x104) Remarks Refs.
Acetic acid, butyl ester (conrd)
-,
ethyl ester
60
65
50
-, -2 ethylhexyl ester
-, methyl ester
-1 tetrahydrofurfmyl ester
-, 2-chloro-, ethyl ester
thio-, methyl ester
A&ylonitrile
Ally1 bromide
Ammonium chloride, N,N-diallyl-N,N-diethyl-
-, N,N-diallyl-N,N,-dimethyl-
Anisole, p-vinyl
Anthranilic acid, vinyl ester
Benzoic acid, vinyl ester
1,3-Butadiene, 2-chloro-
-, 1,1,2-trichloro-
1 - Bu t e n e
2-Butene, cis-
-, trans-
3-Butene-2-one, 3-methyl-
60
65
70
70
80
50
5 5
60
65
70
75
40
60
60
20
2 5
30
40
50
60
60
60
60
60
60
60
0
60
70
60
80
95
50
25
40
50
60
40
50
60
40
50
60
80
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
01072
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
1 8
7
0.198
0.74
80
6.0
7.0
2.0
4.0
2.32
1 6
3.1
5.1
7.3
3.2
4.9
11.2
3.0
5.2
10.8
4.00
Cl , H, KK
F 7
C, F17, R
C, F17, R
C, F17, R
C, F17, R
C, F17, R
F 7
,C, AA
B, k~
C, AA
C, AA
C, FlO
C, AA
c AA
C, FlO
B, AA
C, AA
C, AA
c, hi
C, AA
C, FlO
C, AA
C, F2
E
F 8
F18
F17
F16
Cl, H, KK
Cl , H, KK
Cl , H, KK
C, R, HH
Cl, F30
Cl, F30
F2
E
C
561
291
306
510
512
512
306
306
512
512
512
510
2 2 1
221
221
221
1 2 3
221
2 2 1
322
2 2 1
221
221
221
2 2 1
1 2 3
221
319
342
140
299
284
196
284
410
376
362
95
23
561
561
561
505
538
538
1 3
5 3
139
121,393
26
3 2 1
213
1 5 3
230
334
334
334
334
334
334
334
334
334
84
Remarks page II - 157; References page II - 159
II / 100 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 1. contd
Monomer
T (Cl CM (x104) Remarks Refs.
Butyric acid, vinyl ester
Carbamic acid, vinyl-, ethyl ester
Carbazole, N-vinyl-7H-benzo(2)-
Decanoic acid, vinyl ester
Ethylene
50
80
60
70
50
60
8 3
110
-, chloro-
Glutaramic acid, N,N-diisobutyl-,
vinyl ester
-, N,N-diisopentyl-,
vinyl ester
Hexanoic acid, vinyl ester
5-Hexen-3-yn-2-01, 2-methyl-
Isobutyric acid, vinyl ester
Laurie acid, vinyl ester
Maleic anyhydride
Maleic anhydride/methyl methacrylate
Maleimide, N-(3-dimethylamino-6-methyl-phenyl)
Methacrylamide
Methacrylic acid, bomyl ester
-, butyl ester
-,
tert-butyl ester
o-t-butylphenyl est er
1: p-t-butylphenyl ester
-,
n-dodecyl ester
-, 2,3-epoxypropyl est er
-, ethyl ester
-3 o-ethylphenyl ester
-, p-ethylphenyl ester
-, glycidyl ester
-, hexadecyl ester
-, isobomyl ester
130
50-70
20
2 5
30
40
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
F4
Y
7 1
200
1 1 7
522
7 1
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
60 42 C, FlO 106
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
5 1
5 1
5 1
36
5.0
46
45.5
750
100
720
10 x 10s
2.85
0.54
120 x 10s
0.14
0.35
30.41
2.01
80 x lo5
0.59
0.248
0.259
0.456
0.442
3.63
1.36
45 x 10s
0.14
1.85
C, FlO
C, FlO
C, FlO
C
F2
JJl
JJl
C
C
JJl
c c
c c
c c
c c
C
C
JJl
107
107
1 0 7
200
226
200
7 1
1 7 5
367
542
515
162
233
515
264
9
550
550
515
1 9 8
1 9 3
1 9 3
1 9 3
1 9 3
550
550
515
1 3 8
162
R, F2
W 5
w4, w5
w4
Q W
Q W
w4, w5
w4, w5
w4
C, F21, W5
w4, w5
w4, w5
w4
w3
Y
F 5
F 3
F4
C, F26
Y
F 3
TABLE 1. contd
Transfer Constants to Monomers II / 101
Monomer T (Cl
CM (x104) Remarks Refs.
Methacrylic acid, isobutyl ester
-, n-nonyl ester
-, phenyl ester
-,
o-tolyl ester
-, p-tolyl ester
Methacrylonitrile
Methyl methacrylate
Naphthalene, I-vinyl-
1,4-Pentadiene, 1,1,2,3,3,4,5,5-octafluoro-
Phemol, o-vinyl-
2-Picoline, 5-vinyl-
I-Propene, 2-chloro-
-, 2-methyl-
Propionic acid, vinyl ester
3 5
50
60
8 0
100
60
21
60
60
60
2 5
60
70
80
0
30
40
50
60
65
70
75
80
90
100
120
50
60
70
110
70
70
80
40
50
60
-
50
0.189
0.179
0.14
0.165
0.224
0.301
0.382
105 x 10s
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 lo5
0.10
0.15
0.477
241 x lo5
0.85
0.07
0.10
0.103
0.18
240 x lo5
0.20
0.17
0.20
0.23
0.265
0.29
0.30
0.45
0.807
1.37
240 x lo5
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
DD
DD
F2
DD
DD
DD
JJl
R
C
C
C
Z
Z
Z
Z
D
JJ2
JJl
F2
D
JJl
C
J J O
C, FlO
C, F17
D
JJl
C, FlO
C
C, Fll
C, F2
WlO
1 9 3
1 9 3
264
264
1 9 3
193
1 9 3
515
534
550
550
550
125
125
125
125
69
1 8
69
224
508
525
528
147,327
1 4 5
224
528
69
274
34,290,317
316
145
556
1 2 3
1 2 3
267
1 4 5
440
1 2 3
123
104
224
459
528
1 2 3
1 2 3
1 2 3
1 2 3
1 4 5
1 2 3
147
1 4 5
1 4 5
216
216
216
68
186
11
27
334
334
334
1 5 8
7 1
Remarks page II - 157; References page II - 159
II f 102 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 1. cont' d
Monomer T (2 CM (xlo4) Remarks Refs.
Pyridine, 2-vinyl-
-, 4-vinyl-
2-Pyrrolidinone, l-vinyl-
Stearic acid, vinyl ester
Styrene
15- 35
2 5
20
50
0
25
21
30
45
50
60
67. 8
70
15
80
80. 3
90
99
100
110
117
132
Styrene, p-boromo-
-, o-chloro-
50
30
50
0
6. 1
4. 0
69. 8
0
0. 108
0. 219
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 105
1.0
0
0.6
0. 6
0. 8
0. 96
1. 16
1. 35
2. 0
0
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
D
BB
A
BB
BB
H
F2
C, H
C
A, K
B, CH
A
C
C
BB
A
A, F
C
JJl
C, FlO
BB
B, H
A
A
C, F2
C, FlO
C
C, F2
C, Fll
BB
BB
C F
A
A
A
A F
A
A
A
A F
A
A
C
C H
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
Transfer Constants to Polymers II / 103
TABLE 1. contd
Monomer TV-3 CM (xlo4) Remarks Refs.
Styrene, p-iodo-
Succinimide, N-vinyl-
Valerie acid, 4-methyl-, vinyl ester
Vinyl acetate
50
55
80
- 60
- 4 0
- 20
- 20
0
20
25
40
4 5
50
60
65
70
Vinylidene chloride 50
60
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
D
I7
I7
D
w14
w15
C
1 1 2
C
C
C
1 1 3
R
R
56
93
200
158
464
464
464
241
241
86
464
328
241
86
86
202
69
1 2
328
5 1
466
265
265
265
1 2
552
7 1
225
1 2
466
124
328
348
231
145
294
86
1 6 7
167
80
466
403
86
541
541
TABLE 2. TRANSFER CONSTANTS TO POLYMERS
Polymer
T (C)
cp (x104) Remarks Refs.
Acrylamide, N,N-dimethyl-
Poly(N,N-dimethylacrylamide)
Acrylic acid, ethyl ester
Poly(methy1 methacrylate)
-, methyl ester
Poly(isoprene)
-, chlorinated
Poly(methy1 acrylate)
Poly(methy1 methacrylate)
Acrylonitrile
Cellulose
50 0.61 272
60 12800 M6 120
75 12.6 C, F2 308
60 0.5 L 212
1.0 L 105
60 18000 M6 120
60 1.0 L N 361
11 L, M4 361
20 L, M 5 361
Remarks page II - 157; References page II - 159
II / 104 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 2. contd
Polymer T (Cl cp (xlO4) Remarks Refs.
Acrylonitrile, (contd)
Poly(acrylonitrile)
Poly(methy1 methacrylate)
50
60
60
Poly(sarcosine)
1,3-Butadiene
Poly( 1,3-butadiene)
Ethylene
-, chloro-
Poly(viny1 chloride)
Hexanoic acid, vinyl ester
Poly(oxyethylene), dodecyl ether
Methacrylic acid, butyl ester
Poly(methy1 methacrylate)
-, dodecyl ester
Poly(methyl methacrylate)
-, ethyl ester
Poly(isoprene), chlorinated
Poly(viny1 chloride)
Methyl methacrylate
Poly(ethylene)
Poly(isoprene), chlorinated
Poly(methy1 methacrylate)
Poly(propylene)
Poly(styrene)
Poly(viny1 acetate)
Poly(viny1 chloride)
Poly(viny1 urethane)
Rubber, natural
2Pyrrolidinone, 1-vinyl-dextran
Dextran
60
4.7
3.5
0.2
240
900
1270
400
376
1 3 5
2 5
2 5
25
2 5
23
50 11
174.8 108.40
201.6 150.70
215.0 194.81
231.2 214.46
230.3 337.31
229.2 256.85
230.3 195.81
230.4 199.89
230.5 155.78
256.0 348.46
C, W20, F32
C, W20, F32
C, W20, F32
C, W20, F32
C, W22, F32
C, W21, F32
C, W20, F32
C, W19, F32
C, W18, F32
C, W20, F32
142
540
540
540
540
540
540
540
540
540
540
50 5 L 2 1 1
60 780 278
60 7700 120
60 12800
M6
M6
C, F2
C, F28
120
70 18.3
70 21.0
308
308
50
80
40
50
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
1 7
10.9
11.0
C, F17
N
M
N
N
M
M
N
M
N
209
307
326
326
1 4 7
326
321
326
327
1 4 7
1 0 5
326
262
326
262
1 4 7
147
292
209
292
148
262
262
263
263
250
308
1 5 7
258
258
60
80
90
50
130
50
60
80
60
80
-
70
50
50
50
F14
L
N
M2
M 3
M
M
N
M
C
C, F28
c, F8
C
5 333
5.87 203
TABLE 2. contd
Transfer Constants to Polymer5 II/105
Polymer T (C) cp (x104) Remarks Refs.
St y r e n e
Poly(oxyadipoyloxy-2,2-dibromomethyl trimethylene)
Poly(oxyethylene)
-, dodecyl ether
Poly(oxythexamethyleneoxy sebacoyl)
Poly(methy1 methacrylate)
Poly(propylene)
Poly(styrene)
Poly(viny1 acetate)
Poly(vinyl chloride)
Poly(2-vinylpyridine)
Vinyl acetate
Poly(onyethylene)
130
154
100
130
50
60
-, dodecyl ether 60
Poly(methyl methacrylate)
Poly(styrene)
Poly(viny1 acetate)
60
70
70
60
80
50
60
80
loo
60
66
130
50
55
60
73.5
85
90
100
110
60
75
40
60
75
- 15
0
11
2 1
3 1
40
50
4.05
1 9
1 4
20
1 3
0.4
< 0.3
1110
1140
16.4
17.5
5.7 x 104
32 x lo4
3.74
6.04
0.025
26
0.3
0.30
1.9
4.5
14.0
16.6
1 5
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
1 7
40
1 0
40
750
2 1
26
1 2
1 5
1 9
0.36
0.5
1.7
2
4
1 6
11.2
30.9
32.0
0.06
L
Ml0
Ml0
C, N
N
M
N
M
Ml
Ml
M?
M6
C
L
Ml
Ml
C
C
N
N
M
MS
M9
0
0
0
w15
325
562
562
278
394
327
326
326
327
64
64
120
120
262
262
292
486
292
207
44,148
327
327
176
177
105
73
1 0 5
64
64
176
8
8
327
276
1 7 7
176
43
43
263
263
250
279
277
277
277
277
271
263
263
263
263
263
97
97
350
1 4 5
145
145
1 2
43
263
265
Remarks page II - 157; References page II - 159
0.11 w14 265
0.15 265
3 43
10.2 1 2
60 1.2 124
1.4 168,169
1.8 348
1.9 328
2.5 329
3.0 1 6 5
4.0 1 0 5
6.8 1 2
8.0 105
47.0 263
60-70 3.5 P 350
70 2 0 403
4 403
60 0.21 VCL-Part 166
3.0 VOAC-Part 166
II / 106 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 2. contd
Polymer
T (Cl cp (x104) Remarks Refs.
Vinyl acetate (contd)
Poly(viny1 acetate) (cant d)
Poly(viny1 acetate-co-vinyl chloride)
TABLE 3. TRANSFER CONSTANTS TO CATALYSTS AND INITIATORS
Catalyst/Initiator
T (Cl CI Remarks Refs.
Acrylamide
Bisulfite ion
Hydrogen peroxide
Potassium persulfate
-
75 0.17 F13 352
2 5 0.0005 D 92
50 0.0258 F13, LL 560
60 0.028
F13, LL 560
Acrylic acid, benzyl ester
Isobutyronitrile, 2,2-azobis-
-, ethyl ester
Isobutyronitrile, 2,2-azobis-
-. methyl ester
Benzoyl peroxide
2-Butanone, peroxide 65
tert-Butyl hydroperoxide
tert-Butyl peroxi de
Chloroforn-KuCl~
Acrylonitrile
Isobutyronitrile, 2,2-azobis-
Azodiphenylmethane, benzyl-
-> cyclohexyl-
55 0 291
60 0 291
6 5 0 291
65 0 306
55
60
6 5
70
70
75
60
70
65
70
75
120
50 0
60 0
50 0.07
60 0.07
80 0.07
50 0.02
60 0.04
80 0.05
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
221
221
221
C, FlO 322
221
FlO 123
221
221
FlO 1 2 3
221
221
221
221
221
221
Q(5- 19), Fl 551
F16 362
95
R 536
R 536
R 536
R 536
R 536
R 536
TABLE 3. contd
Transfer Constants to Catalysts and Initiators II / 107
Catalyst/Initiator T (C) CI
Remarks Refs.
Azodiphenylmethane (contd)
-,
l-phenylethyl-
-,
2-propyl-
Benzoic acid, vinyl ester
Benzoyl peroxide
Isobutyronitrile, 2,2-azobis-
3-Buten-2-one, 3-methyl-
Benzoyl peroxide
Et h y l e n e
Azoethane, 1,l -dimethyl-
Ethylene, chloro-
Valeronitrile, 2,2-azobis[2,4,4-trimethyl-
Maleic anhydride
Benzoyl peroxide
Methactylonitrile
Isobutyronitrile, 2,2-azobis-
Methyl methacrylate
Acetophenone, 2-diazo-2-phenyl-
p-Anisoyl peroxide
Benzoyl peroxide
2.Butanone peroxide
tert-Butyl hydroperoxide
terf-Butyl peroxide
Butyronitrile, 2-ethyl-,2,2-azobis-
-, 2-methyl-, 2,2-azobis-
-, 2,3,3&methyl-, 2,2-azobis-
Cinnamoyl peroxide
Cobalt, [bis-[u-[(2,3-butane-dionedioximato)(2-)-0,0]]
tetrafluorodiborato(2-)-N,N,N,N]-
Cyclohexanecarbonitrile, 1,l -azodi-
Cyclopropanecarboxylic acid, l-methyl-
2-(9-anthryl)-, methyl ester
Hydrogen peroxide
Hydroperoxide, a,cc-dimethylbenzyl
Isobutyronitrile, 2,2-azobis-
60
Methane, diazodiphenyl-
Palmitoyl peroxide
70
60
60
50
60
70
60
Peroxide, bis(m-chlorobenzoyl) 60
- bis(o-chlorobenzoyl) 60
-, his@-chlorobenzoyl) 60
-, bis(m-nitrobenzoyl) 60
50 0.1
60 0.1
80 0.1
50 0.02
60 0.04
80 0.05
80
80
80
8 3
0.0527
0
0.0509
0.5
0. 5 1
25
75
60
70
60
50
60
65
70
0.85
2.63 1 7 5
0 1 2 5
75
0.0
0.037
0.01
0
0.02
0.0025
0.00698
0.0033
0.0033
0.0040
0.0092
0.00553
0.00667
0.007 1
0.0089
0.0111
0.0128
1.27 x [cat]
< 0.0001
0
0
0
0.009
36000
80
60
20
60
60
60
60
R 536
R 536
R 536
R 536
R 536
R 536
26
26
84
D;W 204
D. W 205
425
459
316
1 4 5
34
1 2 1 4 5
F2 1 2 3
F17
FlO 1 2 3
Fll 123
1 2 3
Fll 1 2 3
F2 1 2 3
FlO 123
1 2 3
F17 1 2 3
1 2 3
34
C, D 3 5
317
317
317
2500 F17
0 317
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
440
Fll
F2
FlO
Ill
FlO
110
1 2 3
1 2 3
316
563
563
290
34
327
34,290,3 17
267
316
1 4 5
316
316
290
1 4 5
316
316
Remarks page II - 157; References page II - 159
II / 108 TRANSFER CONSTANTS I N FREE RADI CAL POLYMERI ZATI ON
TABLE 3. contd
Catalyst/Initiator T (0 CI
Remarks Refs.
Methyl methacrylate (contd)
-, his@-nitrobenzoyl)
-, bis(m-phenylazobenzoyl)
2-Tetrazene, 1,1,4,4-tetramethyl-
o-Toluoyl peroxide
Valeronitrile, 2-methyl, 2,2-azobis-
Styrene
Acetyl peroxide
p-Anisoyl peroxide
Benzoyl peroxide
Cobalt, [Bis-[y[(2,3-butane-dionedioximato)(2-)-O,O]]
tetrafluorodiborato(2-)-N,N,iV,N]-
Di-3-phenylazo benzoyl peroxide
2-Butanone, peroxide
tert-Butyl hydroperoxide
Butyl peroxide
set-Butyl peroxide
tert-Butyl peroxide
Butyryl peroxide
Cinnamoyl peroxide
Crotonyl peroxide
Cyclohexanone peroxide
Ethyl peroxide
Formamide, 2-cyano-2-propylazo-
Furoyl peroxide
Hexanoyl peroxide
Hydroperoxide, cr,a-dimethylbenzyl
60
50
30
60
6 0
70
70
22
50
60
70
80
50
70
90
50
70
75
60
70
80
60
80
60
80
60
70
80
70
70
70
60
60
80
100
70
70
40
0.144 316
0.00001 C 282
0.038 D 483
0.046 316
0.06 Ill 1 4 5
0 317
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
D
C
87,217
a7
65
58
1 7 1
240
234
217
87
67
58,65
58,65
F17 530
563
6.7
5.5
4.8
0.46
0.0667
0.1250
0.1670
0.1250
0.1670
0.2000
0.243
0.035
0.05 1
0.060
0.063
0.064
0.066
0.003
0.00076
o.ooo92
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
R 527
R 527
R 527
H 388
F2 1 2 3
FlO 1 2 3
Fll 123
F2 123
FlO 123
Fll 123
123
1 7 1
H 388
399
F6 400
400
F2. F5 400
385
F9 302
F2 302
F9 302
F2 301
F2 301
F9 303
303
F2. F12 303
300
304
F 2 400
F 2 303
385
87
87
87
33
F 2 301
F2 301
47
87
87
388 H
TABLE 3. contd
Transfer Constants to Catalysts and Initiators II / 109
Catalyst/Initiator
T (Cl Cl
Remarks Refs.
Styrene (contd)
Hydroperoxide, a,a-dimethylbenzyl (conrd)
-,
cc,cc-dimethylbenzyl,
p-isopropyl-
Isobutyronitrile,2,2-azobis-
Isopropyl peroxide
Lauroyl peroxide
p-Menth-8-yl hydroperoxide
Myristoyl peroxide
84
5 0
70
2-Naphthoyl peroxide 70
Nickel peroxide 60
Octanoyl peroxide 70
Oleoyl peroxide
Palmitoyl peroxide
Peroxide, his@-acetoxybenzoyl)
-, bis(m-bromobenzoyl)
-, bis(o-[bromobenzoyl)
-, his@-bromobenzoyl)
-, his@-tert-butylbenzoyl)
-, bis(m-chlorobenzoyl)
Peroxide, bis(o-chlorobenzoyl)
-, bis(p-chlorobenzoyl)
-> bis(p-cyanobenzoyl)
-, bis(2,4-dichlorobenzoyl)
-, bis(a,cr-dimethylbenzyl)
-, bis(m-fluorobenzoyl)
-, bis(o-fluorobenzoyl)
-3 his@-fluorobenzoyl)
-, bis(hydroxyhepty1)
-, bis(m-iodobenzoyl)
-, his@-methoxycarbonyloxy-benzoyl)
-, bis(m-nitrobenzoyl)
-, bis(p-nitrobenzoyl)
-, bis(m-phenylazobenzoyl)
-, bis(5-phenyl-2,4-pentadienoyl)
-, bis(2-thiophenecarbonyl)
-I
tert-butoxymaleoyl
-, rert-butoxyphthaloyl
-, butylidenebis[tert-butyl
-1 set-butylidenebis[tert-butyl
-, isobutylidenebis[tert-butyl
-> isopropylidenebis[tert-butyl
Pinanyl hydroperoxide
50
60
70
70
50
60
60
80
70
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
9 0
70
50
70
70
70
80
9 0
80
9 0
8 0
9 0
80
9 0
70
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
H
H
H
F2
H
F2
F2
H
C. F2
D
H
H
C
C
388
171
388
3 9 9
388
327
388
1 7 1
318
468
447
301
301
217
8 7
217
388
217
8 7
87
266
217
8 7
8 7
8 7
87
87
58,65
87
87
8 7
8 7
65
87
217
87
217
217
388
87
87
87
388
8 7
8 7
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
II / 110 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 3. cont' d
Catalyst/Initiator
T (Cl CI Remarks Refs.
Styrene (co&d)
Pivalonitrile
Propylene, oxidized
Propyl peroxide
Sorboyl peroxide
Stearoyl peroxide
Succinonitrile, tetramethyl-
2-Tetrazene, 1,1,4,4-tetramethyl-
o-Toluoyl peroxide
p-Toluoyl peroxide
60
60
70
60
70
70
60
30
70
50
70
0. 000038 468
1.01 396
1.14 396
0. 00084 305
1. 19 87
0. 154 87
0. 000037 468
0. 038 D 483
0. 175 87
0. 17 65
0. 003 87
0. 19 65
0. 065 87
0. 59 426
i
9-Undecenoyl peroxide
Valeronitrile, 2,2-azobis[2,4&rimethyl-
Vinyl acetate
Benzoyl peroxide
70
25
60 0. 032 465
0. 09 231
0.15 80
0. 040 466
0. 025 466
0. 055 466
0.10 80
0.10 80
0.17 13 145
0. 24 80
0. 6 13 145
0. 25 80
3. 5 13 145
0. 17 80
0. 17 13 145
65
50
60
60
60
Isobutyronitrile, 2,2-azobis-
Lauroyl peroxide
Palmitoyl peroxide
Peroxide, bis(m-bromobenzoyl) 60
-, bis(o-bromobenzoyl) 60
-, bis(p-bromobenzoyl) 60
-1
bis(o-chlorobenzoyl) 60
TABLE 4. TRANSFER CONSTANTS TO SOLVENTS AND ADDITIVES
Solvent/Additive T (0 cs (XlOQ Remarks Refs.
Acetic acid, ally1 ester
Benzene
p-Benzoquinone
-, 2,3,5,6-tetrachloro-
-, 2,3,5,6-tetramethyl-
-, 2,3,5-trichloro-
Carbon tetrachloride
Phosphorus trichloride
Acrylamide
Acetonitrile
tris(2-Carbamoylethyl)amine
Iron(II1) chloride
Isopropyl alcohol
Methanol
Propionamide
80 21. 0
80 5. 2 x lo5
80 16 x lo5
80 4.14 x 104
80 5. 5 x 105
100 2. 0 x 104
40 1.0 x 104
273
27
27
27
27
210
214
J
J
J
J
C
C, D
5. 5
85
4. 26 x lo4
1 9
7. 2
0. 13
220
64
0. 204
5. 8
F13
F13
564
564
75
353
353
130
103
103
437
444
25
50
80
30
25
60
25
40
F13
F13, S
C, F13
E
E
C, F13
F13
Acrylic acid, butyl ester
Aniline, N,N-dimethyl-
Ethanol
Methanol
Propanol
Iso-propanol
50 380
80 4. 28
80 0. 47
80 3. 78
80 14. 12
161
548
548
548
548
A R
F31, A, R
A, R
A, R
TABLE 4. contd
Transfer Constants to Solvents and Additives II/111
Solvent/Additive
T ((3
cs (x104) Remarks Refs.
Acrylic acid, ethyl ester
Acetic acid
Acetone
Acetonitrile
Aniline, NJ-dimethyl-
Benzene
-, bromo-
-, chloro-
-, ethyl-
2-Butanone
Butyl alcohol
set-Butyl alcohol
rert-Butyl alcohol
Butyric acid
Carbon tetrachloride
Chloroform
Cumene
Cyclohexane
5 0
8 0
100
4 0
6 0
8 0
100
5 0
6 0
8 0
100
5 0
5 0
6 0
8 0
100
6 0
8 0
100
4 0
8 0
100
4 0
6 0
8 0
100
5 0
6 0
8 0
9 0
4 0
6 0
8 0
100
4 5
6 3
8 0
100
4 0
6 0
8 0
100
8 0
4 0
6 0
7 0
8 0
100
4 0
6 0
7 0
8 0
100
5 0
6 0
8 0
9 0
5 0
6 0
0.176
0.537
1.05
0.207
0.27
1.10
2.30
0.158
0.245
0.55
1.43
2 3 0 0
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
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
4 7 2
471
4 7 2
4 7 2
134
471
4 7 2
4 7 2
4 7 2
471
4 7 2
2 2 8
4 7 2
4 7 2
1 3 3
134
471
4 7 2
4 7 2
471
4 7 2
4 7 2
471
4 7 2
4 7 2
4 7 2
471
4 7 2
4 7 2
134
4 7 2
471
4 7 2
4 7 2
4 7 2
471
4 7 2
4 7 2
4 7 2
471
4 7 2
4 7 2
4 7 2
471
4 7 2
471
4 7 2
4 7 2
4 1 6
134
471
4 7 2
4 7 2
134
134
471
4 7 2
4 7 2
4 7 2
471
4 7 2
4 7 2
4 7 2
134
Remarks page II- 157; References page II- 159
II / 112 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 4. contd
Solvent/Additive T (Cl
cs (x104) Remarks Refs.
Acrylic acid, ethyl ester (contd)
cyclohexane (contd)
Dimethylformamide
Ethanol
Ethyl acetate
Formic acid
Heaxane
Isobutyl alcohol
Isopropyl alcohol
Methanol
Propanol
To l u e n e
-, 2-ethylhexylester
To l u e n e
-,
methyl ester
Acetone
Acetophenone
Aluminum, triethyl
Aniline
-,
N,N-dimethyl-
-, m-nitro-
-, p-nitro-
Anisole, m-nitro-
Anthracene
Benzene
-, chloro- 80
-, o-dichloro- 80
-, m-dinitro- 50
-9 ethyl- 80
-, nitro- 50
-, 1,3,5trinitro- 50
Benzoic acid, p-nitro- 50
Benzonitrile 50
Copper(I1) chloride 120
Phosphine, tributyl- 60
Phosphorus trichloride 40
Propanol 80
Silane, dimethyphenyl- 60
-, methyldichloro- 60
-, tetraethyl- 60
-, trichloro- 60
80
100
50
80
50
60
80
100
80
50
60
80
100
45
63
80
100
-
80
60
80
80
40
*z
70
80
100
70 28.70
80 2.13
60
80
50
60
50
50
50
50
50
50
80
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
2 1
28.70
0.32
1.70
0.36
4.73
0.88
0.611
0.929
1.37
1.84
2.60
6.80
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
A
A
F7
A R
C
A
A
A
A
A
A
A
C
A R
C
4
A, R
AR
C, F17, R
C, F17, R
C, F17, R
C
A
A
C, F17, R
C, F17, R
C
C
F2, S
F16
C
C
C
F34
F2
C, D
A R
A R
A, R
F2
A R
471
472
510
548
472
472
134
471
472
471
472
472
471
472
472
472
471
472
445
548
134
472
548
548
472
512
512
512
134
471
471
512
512
470
332
1 1 1
15
156
15
228
15
15
1 5
1 5
332
1 1 1
1 1 1
332
1 1 1
15
332
15
15
15
15
565
156
214
548
539
539
1 5 6
539
TABLE 4. contd
Transfer Constants to Solvents and Additives I I / 113
Solvent/Additive T (Cl cs (x104) Remarks Refs.
Acrylic acid, methyl ester(contd)
-, triethyl-
triphenyl-
i;earic acid, methyl ester
To l u e n e
-, m-nitro-
-, p-nitro-
Triethylamine
Tripropylamine
-1 tetrahydrofurfuryl ester
Carbon tetrachloride
Acrylonitrile
Ac e t a l d e h y d e
Acetamide, N,N-dimethyl-
Acetic acid
Ac e t o n e
Acetonitrile
Acrolein, bis(2-ethoxyethyl)acetal
bis(2-butoxyethyl)acetal
kminum, hydrodiisobutyl
-1 triethyl
triisobutyl
kiline
-, N,N-diethyl-
Aniline, N,N-dimethyl- 40
An t h r a c e n e
Ar a bi nos e
Be n z e n e
-, bromo-
-1 tert-butyl-
-, chloro-
-, ethyl-
-, iodo-
Benzoic acid, vinyl ester
p-Benzoquinone
Borane, tributyl
Z-Butanone
-, 3-methyl-
1-Buten-3-yne
Butyl alcohol
secButy1 alcohol
rerr-Butyl alcohol
60
60
60
60
80
50
50
60
60
40
-
50
50
50
50
60
50
60
60
60
60
60
100
100
40
50
60
40
50
60
50
60
50
60
60
60
60
60
60
60
65
50
60
60
60
50
60
60
60
300
800
0.751
2.7
1.775
2.7
41.2
48.6
400
470
1.0
1 4
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 lo4
32.0
44.0
9600
1.22 x 104
215
5.81 x lo4
359
9.38 x lo4
547
14.3 x 104
605
1.19 x 104
708
1040
1.5 x 104
1.54 x 104
870
964
2.18 x lo4
1.8 x lo4
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
A, R
A, R
C
F2
c, F2
F
F7
F14
F14
F
F14
F15
F7
F7
F7
F7
F7
F7
F2, G
R J
F16, G, J
F16, G, J
F2, J
F16, G, J
FZ 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
3, S
F7
G
G
F7
G
G
G
539
539
441
21,24
332
1 1 1
1 5
1 5
24
156
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
1 6 1
228
227,229
24
229
229
1 5
361
95
95
95
95
95
95
136
1 5
156
95
95
377
95
95
95
Remarks page II - 157; References page II - 159
II/ 114 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 4. contd
Solvent/Additive T (Cl cs (xlO4) Remarks Refs.
Acrylonitrile (contd)
Butyric acid, 4-hydroxy-y-lactone
Cadmium, dibutyl 60
Carbonic acid, cyclic ethylene ester 50
Carbon tetrabromide
Carbon tetrachloride
Chl oroform
Copper(I1) chloride
Copper(I1) sulfate
Crotonaldehyde
Crotononitrile, trans-
Cumene
Cyclohexane
metbyl-
gmethylamine
m-Dioxane, 5,5-dimethyl-2-vinyl-
m-Dioxane, 5,5-dimethyl-2-vinyl-
-, 4-methyl-2-vinyl-
- , 2-vinyl-
1,3,-Dioxolane, 2-vinyl-
1,3-Dioxolane-4-methanol, 2-vinyl-
Diphenylamine-T
Erytbritol
Et hane, 1,2-dichloro-
-, 1,1,2,2-tetrachloro-
-, l,l,l-trichloro-
-, 1,1,2-trichloro-
Ethanol, 2,2-iminodi-
-, 2,2,2-nitrilotri-
Ether, dodecyl vinyl
Ethyl acetate
Formamide, N,N-dimetbyl-
50
60
50
60
60
80
60
80
35
60
3 5
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
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 IO5
1.9 x 10s
3.2 x IO5
10 x 10s
1900
2800
3000
1.07 x 104
1.35 x 104
3.93 x 104
13.6 x IO4
21.0 x 104
47
1 9
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
1 0
2.412
4.494
5.0
F-l
E
F7, J
G
C
G
C
U(O.01)
U(O.1)
U(1.0)
F 7
F13, J
J, V(O.0001)
J, U(O.01)
J, V(O.001)
J, U(O.1)
J, V(O.01)
J, U(l.0)
J, W.1)
F7
F7
G
G
G
Iv
F7
F7
F7
F7
F 7
F7
F8
G
G
G
G
F13
F13
C
G
C J, fl
Q J
E
F15
375
374
156
293
1 9 7
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
371
377
95
95
95
371
498
498
498
498
498
6 1
361
95
95
95
95
416
476
4
9 5
248
9 1
458
347
374
1 9 7
377
375
356
347
22
8 6
TA
-
Sol
-
A C
1
1
t
(
TABLE 4. contd
Solvent/Additive
T ((3
Transfer Constants to Solvents and Additives II/ 115
cs (x104) Remarks Refs.
Acrylonitrile (contd)
Formamide, N,N-dimethyl- (contd)
-, N-methyl-
Formic acid
Gl uc os e
u,n-Glucoside, met hyl -
-, -1 6-deoxy-6-iodo-
-I -1 6-deoxy-6-mercapto-
-, -, 6-deoxy-6-phthalimido-
-1 -9 2,3-di-o-benzyl-
-1 -1 2,3,4,6-tetra-o-acetyl-
-9 -. 6,-O-(p-toluenesulfonyl)-
-1 -, 6-O-triphenylmethyl-
P,n-Glucoside, methyl-
-, 6-deoxy-6-dipropylamino-
Ghitaronitrile, 2,4-dimethyl-
Glyceraldehyde
Glycerol
2,4,6-Heptanetricarbonitrile
1-Heptanol, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-
1,5-Hexadien-3-yne
Hydrocyanic acid
Indium, triethyl
Iron(III) chloride
Isobutyl alcohol
I s o b u t y l e n e
Isobutyronitrile
Lactonitrile
Lead, tetraethyl
Magnesium perchlorate
Mercury, diethyl
Methane, dichloro-
-, nitro-
Me t ha nol
Methylamine
2,6-Octadiene, 2,6-dimethyl-
Oxime, acrolein
-9 crotonaldehyde-
-1 ethylisopropenylketone-
-, methacrolein-
-1 metbylacrolein-
-,
methylvinylketone-
-9 methylisopropenylketone-
-9 methylisobutenylketone-
l-Pentanol, 2,2,3,3,4,4,5,5-octa-fluoro-
1-Pentanol, 4-methyl-
Piperidine, l-ethyl-
-, l-methyl-
1-Propanol, 2,2,3,3-tetrafluoro-
Silane, tetraetbyl
So r b i t o l
Stibine, tributyl
Suc c i noni t r i l e
Sulfur dioxide
Ti n, t e t r a but yl
To l u e n e
o-Toluidine, N,N-dimethyl-
50
50
60
60
60
60
60
60
60
60
60
60
60
50
60
60
50
60
50
50
60
60
60
60
50
60
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
40
50
1.8
0.5
6.9
20
50
1300
60
90
30
1 0
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
1 7 5
450
6.26 x lo5
2.05 x lo4
1.03 x 104
9.41 x 104
5.35 x 104
1.2 x 104
1.71 x 104
2.65 x lo4
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
F14
F14
F8
F7
F7
F7
F7
F7
F7
F7
F 7
F7
F 7
F14
F8
F8
F14
F2
F7
F14
F
F7
F7
G
F14
I6
F15
F14
F7
F7
G
F15
F14
F7
F2
G
J
F2
F7
F8
F7
F7
G
G
G
F2, J
F2, J
377
377
361
220
220
220
220
220
220
220
220
220
220
376
361
361
376
442
377
377
436
156
1 9
95
553
376
376
1 3 5
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
2 1
24,95
229
229
Remarks page II - 157; References page II - 159
II/ 116 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 4. contd
Solvent/Additive
T CC) cs (x104) Remarks Refs.
Acrylonitrile (contd)
o-Toluidine, N,N-dimethyl- (contd)
Tributylamine
Triethylamine
Trimethylamine
Tripropylamine
Zinc, diethyl
Zinc chloride
Acrylonitrile/styrene (38. 5-61. 5 mol%)
Methanol
Anisole, p-vinyl-
Anisole, p-isopropyl-
Benzonitrile, p-isopropyl-
Cumene
-,p-bromo-
-, p-tert-butyl-
-, p-chloro-
Benzoic acid, vinyl ester
Benzene
Benzoic acid, isopropyl ester
2-Butanone
Carbon tetrachloride
Chl oroform
Cyclohexane
1,3-Butadiene, 2-chloro-
1-Butene, 3-chloro-S-methyl-
2-Butene, 1-chloro-3-methyl-
2,6-Octadiene, 2,7-dichloro-
3-Buten-2-one, 3-methyl-
Benzene
ethyl-
Cyclohexane, methyl-
To l u e n e
Butyraldehyde, divinyl acetal
Aniline, N,N-dimethyl-
Benzene
Butyl alcohol
reti-Butyl alcohol
1,3-Dioxolane, 2-propyl-
Butyric acid, vinyl ester
Benzene
Carbamic acid, vinyl-, ethyl ester
Acetone
Benzene
Chloroprene
3-Chloro-(methyl- 14C)-
1-butene(4- 14C)
3-Chloro-2-pentene-(2,4- 14C)
p-Dioxin, 2,3-dihydro-/maleic anhydride
Benzene
Carbon tetrabromide
Carbon tetrachloride
Chl oroform
p-Dioxane
To l u e n e
m-Xylene
60
60
60
50
60
60
60
50
65 1.4 116
60 3.40 407
60 40.9 407
60 4.28 407
60 11.8 407
60 3.64 407
60 8.52 407
60 1.5 393
80 0.4 26
60 1.0 393
80 29.0 26
80 730 26
80 105 26
80 2.3 26
50 5.47 Fl 152
50 4.57 F2 152
50 5.24 F2 152
80 2.489 C 84
80 6.934 C 84
80 0.500 C 84
80 3.282 C 84
50 1060 430
50 27.7 430
50 3500 430
50 37.2 430
50 708 430
80 3.28 201
60 8.5 1 1 7
60 1.25 1 1 7
50 5.37 F2 509
50 3.94 F2 509
60 11500
60 100 x 10s
60 1.7 x 10s
60 3.6 x lo4
60 1.07 x 104
60 6.0 x lo4
60 9.9 x 104
30200
463
6700
1700
1900
3800
5900
6600
1 7 5
790
4820
1.05 x 104
1.06 x lo4
0.006
F16, G, J
F2, J
J
T
m, J
J
F7
J
F7
J
F7
F13
227,229
229
24
20
20
22
24
24
377
24
156
24
156
410
169
169
169
169
169
169
169
TI
-
SC
-
El
i
TABLE 4. contd
Transfer Constants to Solvents and Additives II / 117
Solvent/Additive T (0 cs (x104) Remarks Refs.
Et h y l e n e
Acetamide, N,N-diethyl-
-I N,N-diisopropyl-
-, N,N-dimethyl-
-, N-ethyl-
-, N-methyl-
Acetic acid, butyl ester
-1 rerz-butyl est er
methyl ester
Letic acid, chloro-
-, -7
methyl ester
Acetic acid, cyano-
methyl ester
,&& aci d, dichloro-
-, -,
methyl ester
Acetic acid, trichloro-
-3 -1 methyl ester
Acetic anhydride 130
Ac e t o n e 130
Acetonitrile
Benzaldehyde
Benzene
130 1 2 5
130 57
130 182
130 1 1 5
130 6 1
130 89
130 40
130 40
90
120
130
130
55
90
120
55
90
120
200
130
130
20
8 3
130
50-70
610
1210
2170
2150
2580
630
1160
1880
1990
2090
1120
1800
7900
11100
13000
1900
6900
9400
10500
2000
5900
8100
11100
700
16100
27500
38000
65700
1000
17000
27700
39000
65200
1200
15400
23600
33000
54100
130
160
1 6 5
168
282
100
1970
0.629
20
2 1
9.4
1 8
c, w5 454
c, w5 454
c, w5 454
c, w5 454
c, w5 454
c, w5 454
c, w5 454
c, w5 454
C Ql 434
C Q2
434
C Q3 434
C Q4 434
C Q5 434
C Ql
434
C Q2 434
C Q3 434
C Q4
434
C Q5 434
c, w5 454
c, w5 454
C Ql 435
C, Q2 435
C Q3 435
C 435
C Ql
435
C, Q2 435
C Q3 435
C 435
C, Ql 435
C Q2 435
C, Q3
435
C 435
C Ql 484
C, Q2
484
C Q3 484
C Q4 484
C 484
C Ql 484
C Q2 484
C Q3
484
C Q4 484
C 484
C Ql 484
C Q2 484
C Q3 484
C Q4 484
C 484
c, w5 454
c, w17 456
C, F21, W5 259
c, w5 456
c, w5 455
C, F21, W5 159
c, w5 457
E, W 1 4 3
D 204
Q W 205
c, w5 260
w3 218
Remarks page II - 157; References page II - 159
II/ 118 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 4. contd
Solvent/Additive T(C) cs (x104) Remarks Refs.
Ethylene (contd)
-1
ethyl- 130
Benzene-D6
Benzoic acid, butyl ester
-,
ethyl ester
methyl ester
Ltane
-, l-iodo-
2-Butanone
-, 3-methyl-
1-Butene
-, 2-methyl-
-, 3-methyl-
2-Butene
-, l,Cdichloro-
-, 2-met hyl
terr-Butyl alcohol
Butylamine
Butyraldehyde
Butyric acid, methyl ester
Butyronitrile
Carbon tetrachloride
200
130
130
130
130
130
100
130
200
130
130
189
200
130
130
130
130
130
30
130
130
130
130
130
20
50
70
90
95
130
140
430
480
520
560
500
5.6
140
55
53
40
45
9.45 x 104
11.3 x 104
12.6 x lo4
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 xk 200
22000 f 1000
43000 f 4000
113oZk700
2000 f 1000
37000 * 3000
9800
1600
1700
1800
2200
22000
23000
30000
36000
38000
39000
60000
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
C QL
C, Ql
c, w4
g1, w12
C Ql
Q2, W12
Q3, W12
w12
W23, Q(l)
W23, QG2
W23, Q(3)
W20, Q(l)
W20, Q(Z)
W20, Q(3)
C, F21, W5
C Ql
C, Ql, F19
C, Ql, W13
C, Ql, F20
C, Q2
C, Q2, F19
C, QL ~1
C, 43
C, Q2, F20
C, Q3, F19
C, Q2, W13
456
52
454
52
455
260
454
454
454
259
456
187
1 8 7
187
456
259
455
259
52
52
259
443
455
259
259
259
259
454
454
259
482
259
454
457
454
259
1 4 3
391
391
215
210
453
391
453
453
453
518
518
518
518
518
518
259
170
170
170
170
170
170
170
170
170
170
170
TABLE 4. contd
Transfer Constants to Solvents and Additives II/ 119
Solvent/Additive T ((3 cs (x104) Remarks Refs.
Ethylene (contd)
Carbon tetrachloride (contd)
Chloroacetic acid, methyl ester
60000
61000
70000
90000
100000
110000
130000
140000
180000
90 590, 550, 1200
1680. 2240. 2340
Chloroform 2 8
Cumene 130
Cyclohexane 130
methyl-
Cyclopentane
Cyclopropane
Decane
1-Decene
Dibutylamine
Dichloroacetic acid, methyl ester
Dimethylamine
p-Dioxane
Ethane
-, l,l-bis(dimethylamino)-
-, 1-bromo-Zchloro-
-, chloro-
-, 1,2-dibromo-
-, l,l-dichloro-
7 0
8 0
9 5
1 0 1
103
130
140
2 0 0
130
130
2 0 0
130
130
189
189
130
2100
13000
15000
8000
30000
2470
15500
24900
31200
43900
2OOOf 120
10000*500
16000 & 3000
1150f50
5000 zt 300
8000 f 1000
1500
4 5 0 0
5400
2890
15400
23800
29800
41100
2 9 0 0
3210
15200
22200
28000
37600
5 0 0
8 0
9 0
9 1
190
110
109
127
228
0
120
4 2 5
1090
1070
90 1900, 6900, 9400
130 1900
130 3 2 0
130 6
130 1070
130 3 9 0
7 0 120
130 1250
7 0 1500
C Q3
C, Q3, F20
C, Q4, F20
C, Q4, F20
C, Q2, ~1
C Q3, Wl
C, 43, W13
C Q4, ~1
C
C, Q(l), QG9, Q(3)
C Q(4), Q(5)> Q(6)
E, Ql, W
E, Q2, W
E, Q3, W
c, w4
k, Ql, W12
C, Q2, W12
C, Q3, W12
C, Q4, W12
c, w12
W23, Q(l)
W23, 463
W23, Q(3)
W20, Q(l)
W20, Q(3)
W20, Q(3)
E, QL W
E, Q3, W
E, 42, W
C, Ql, 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(l), QC% Q(3)
C, F21, W5
C, F21, W5
C, F21, W5
c, w5
c, w5
c, w4
c, w5
c, w4
170
170
170
170
170
170
170
170
170
557
5 5 7
2 4 4
2 4 4
2 4 4
215
2 1 0
1 0 1
1 0 1
1 0 1
1 0 1
1 0 1
5 1 8
5 1 8
5 1 8
5 1 8
5 1 8
518
2 2 4
2 4 4
2 4 4
1 0 1
1 0 1
1 0 1
1 0 1
1 0 1
2 5 9
1 0 1
1 0 1
1 0 1
1 0 1
1 0 1
2 5 9
2 5 9
4 5 6
2 5 9
4 5 5
2 5 9
4 5 6
2 5 9
455
2 5 9
259
443
443
4 5 4
558
2 5 9
2 5 9
2 5 9
4 5 7
4 5 4
215
4 5 4
215
Remarks page II - 157; References page II - 159
II / 120 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 4. contd
SolventJAdditive
T (Cl cs (x104) Remarks Refs.
Ethylene (contd)
Ethane, 1,2-dichloro-
-, iodo-
-, l,l,l-trichloro-
Ethanol
Ethyl acetate
Ethylene oxide
Formaldehyde
Fomamide, NJ/-dimethyl-
Formic acid, methyl ester
Furan, tetrahydro-
Heptaldehyde
Heptane
Hexane
1-Hexene
-, 2-ethyl-
Hydrogen
Isobutyronitrile
Isocyanic acid, butyl ester
Isopropanol
Isothiocyanic acid, butyl ester
Methane
-, bromochloro-
130 110
65 1.51 x 105
1.59 x 105
1.65 x lo5
100 1.1 x 105
1.36 x lo5
1.43 x 105
1.48 x lo5
1.49 x 105
70 500
20 5 . 7 1
30 110,210, 270
60 76,240, 280
100 89,270, 340
1 2 5 100,310, 320
130 68
69
75
125-135 190
150 92,260
180 73,350
200 1 3 5
130 45
200 1 2 1
130 7
130 560
130 260
130 42
130 288
289
200 401
130 2600
3900
200 4800
50-70 90
130 80
130 68
189 225
189 900
130 3300
130 159
160
200 400
130 1070
130 212
30 96,410, 520
60 65,310, 380
100 65,300, 350
1 2 5 75,380, 380
130 130
140
144
125-135 570
150 98,470, 460
180 86,440, 500
200 234
130 0
130 0
100 1600
4500
7500
8000
130 10000
140 16.0 x lo5
C, F21, W5
::
;;
Ql, W14
Q2, W14
Q3, W14
Q3
c, w4
:: &,> Q(3L QW
6 Q(l)> Q(3L Q(5)
E> Q(l)> Q(3L Q(5)
6 Q(l), Q(3)> QG)
c, w17
C, F21, W5
c, w5
c, w2
5 Q(l), Q(3)
6 Q(l), 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
w 3
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
6 Q(l)> Q(3L Q(5)
E, Q(l). Q(3L Q(5)
5 Q(l), Q(3L Q(5)
6 Q(l), Q(3L Q(5)
c, w17
C, F21, W5
c, w5
c, Wl
6 Q(l), Q(3), Q(5)
E, Q(l)> Q(3k Q(5)
c, w5
c, w5
c, w5
C, Ql, Wll
C, 42, Wll
C, Q3, Wll
C, Q4, Wll
c, w5
Ql, Wll, II
259
189
189
189
452
1 8 8
1 8 8
1 8 8
452
215
1 4 3
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. contd
Solvent/additive
T ((2
Transfer Constants to Solvents and Additives II / 121
cs (XlOq Remarks Refs.
Ethylene (contd)
Methane, bromochloro- (cont&
-, chloro-
-, dichloro-
-, dimethoxy-
-, iodo-
7 0
7 0
130
130
6 5
100
Methanol
Methylamine
1-Octene
Pentane, 2,2,4-trimetbyl- 130
Pentene 189
-, 4,4-dimethyl- 130
-, 4-methyl- 130
Phosphine 130
-, dibutyl 130
-7
tributyl 130
-, triphenyl 130
Phosphorous acid, dimethyl ester 130
Propane 130
3 0
6 0
100
1 2 5
130
150
180
130
130
-, 2-chloro-
Propane, 2-chloro-2-methyl-
-, 2,2-dimetbyl-
-, 2-iodo-
-, 2-methyl-
-, 1 1 1 2 2,3,3,3-octafluoro- 1 1 1 9
1 Propene
Propionaldehyde
Propionic acid, methyl ester
2 0 0
7 0
7 0
130
6 5
100
130
2 0 0
130
130
2 0 0
130
2 0 0
9 0
120
47.0 x 10s
4
7 0 0
3 6 0
7 3
41000
45000
45000
41000
45000
45000
36, 84, 100
46, 100, 140
34, 90, 120
56, 100, 140
2 1
53, 120, 160
37, 120, 160
5 3
3 6 0
3 6 0
6 4
9 0 0
175
3 1 0
207000
36000
4 5 0 0
5 0
5 1 0 0
2 7
27.6
3 1
65.2
2 5 0
4 0
8
5.7 x 10s
5.9 x 10s
6.07 x 10
4.55 x 10s
4.70 x 10s
4.83 x lo5
5 0
7 2
136
4
110
122
150
2 0 0
2 3 0 0
3300
2 8 3 0
63000
92000
1.08 x lo5
630, 420, 780
890, 1030, 1230
78000
1.12 x 10s
1.39 x 10s
780, 430, 1060
1220, 1300, 1410
42, Wll, II
c, w4
c, w4
c, F21, w5
c, w5
::
:;
Q2
:>3Q(U> Q(2), Q(3)
E, Q(l), Q(2), Q(3)
E, Q(l), Q(2), Q(3)
E, Q(l), Q(2h Q(3)
c, F21, w5
E, Q(l), Q(2), Q(3)
E> Q(l), Q(2h 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
::
::
::
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
C, Q5
C, Q(l), Q(2)> Q(3)
C Q(4h Q(5h Q(6)
C, Ql
C, Q3
C Q5
C Q(l), Q(2h Q(3)
C Q(4h Q(5h Q(h)
1
215
2 1 5
2 5 9
4 5 4
189
1 8 9
189
189
189
189
523
523
523
5 2 3
2 5 9
5 2 3
5 2 3
4 5 4
5 2
2 5 9
2 5 9
4 4 3
4 5 4
4 5 4
4 5 7
4 5 4
4 5 4
4 5 4
2 5 9
2 5 9
4 5 6
2 5 9
4 5 5
215
215
2 5 9
189
189
189
189
189
189
2 5 9
4 5 4
4 5 5
2 5 9
5 2
4 5 4
5 2
4 5 5
4 5 7
4 5 7
4 5 7
4 8 5
4 8 5
4 8 5
5 1 6
5 1 6
4 8 5
4 8 5
4 8 5
5 1 6
5 1 6
Remarks page II - 157; References page II - 159
II / 122 TRANSFER-CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 4. contd
Solvent/Additive
T (C)
cs (x104) Remarks Refs.
Ethylene (conrd)
-, 3-cyano-, met hyl est er
Silane, tetramethyl
Tetradecane
1-Tetradecene
To l u e n e
Tributylamine
Trichloroacetic acid, methyl ester
Tridecane
Trimethylamine
Wa t e r
p-Xylene
Ethylene, bromo-
Carbon tetrachloride
Ethylene, chloro-
Acetaldehyde
Aniline, N,N-dimethyl-
Benzene
Butyraldehyde
Carbon tetrabromide 50
Cycl ohexane, 1,2-epoxy-4-vinyl-
Et hane, 1,2-dichloro-
Ether, dodecyl vinyl
Furan, tetrahydro-
Heptane, 2,4,6-trichloro-
Oxalic acid, diethyl ester
Pentane, 2,4-dichloro-
Ethylene, 1, l-dichloro-
Phosphorus trichloride
Ethylene, tetrafluoro-
Ethanol
Isopropanol
Methanol 100
Hexanoic acid, vinyl ester
Benzene
1-Hexene
Carbon tetrachloride
Cyclohexanol
Ethyl alcohol
130
130
189
189
130
200
130
90
130
130
20
130
200
60 50 417
50
50
3 5
50
60
-
2 5
50
50
2 5
40
50
50
2 5
2 5
50
60 1 4 D 214
100
100
80
140
125-135
30-35
790 c, w5 454
0 C, F21, W5 259
580 B, W.5 443
1760 B, W5 443
130 c, w5 52
154 c, w5 454
180 c, w17 456
220 c, w5 455
820 c, w5 454
1000, 1700, 2770 C Q(l), QC% Q(3) 559
140 C, F21, W5 259
180 C, F21, W5 259
330 c, w5 454
1.71 E W 1 4 3
300 C, F21, W5 259
317 c, w5 454
400 c, w17 456
434 c, w5 455
110
2700
1500
350
420
500
580
4.7 x 104
50.0 x 104
3300
1.85 x lo4
7.45 x 104
12.15 x lo4
264
4.0
4.5
156
1 6
30
24
5
1.4
9.0
5
W 8
w7
w15
F26
C. F26
G
164
1 6 1
219
500
500
500
500
492
66
418
418
418
418
428
425
392
4
425
246
164
211
315
315
211
800 C, Q5, W2 3
820 c, Q6, W2 3
860 C Q4, W2 3
880 C 43, W2 3
1540 C Q3, W2 3
1660 C Q4, W2 3
1700 C, Q5, W2 3
350 C Q3, W2 3
390 C, Q4, W2 3
4.9
4.1 x 104
390
170
201
C, Ql, F19 170
C 381
D 381
TABLE 4. contd
Transfer Constants to Solvents and Additives II / 123
Solvent/Additive T CC) cs (x104) Remarks Refs.
I s o b u t e n e
Carbon tetrachloride 100 (7.1 kOo.2) x lo4 E, Q(l) 537
(8.1*0.5) x lo5 E, Q(2)
Isobutyric acid, vinyl ester
Benzene
Maleic acid, diethyl ester
Stearamide, N-allyl-
Maleic anhydride/methyl methacrylate
A c e t o n e
Maleic anhydridelstyrene
Aniline, N,N-dimethyl-
Carbon tetrachloride
Methacrylic acid
Bromotrichloromethane
-, butyl ester
Benzene
-, 2-(diethylamino)ethyl ester/styrene
Carbon tetrachloride
To l u e n e
-3 ethyl ester
Acetic acid
Acetone
Acetophenone
Benzene
-, chloro-
ethyl-
i:Butanone
Butyl alcohol
set-Butyl alcohol
tert-Butyl alcohol
Carbon tetrachloride
80 4.49 201
90 22.4 J 1 7 3
60 1.6 HH 367
60 930
70 1.04 HH
489
365
70 300 566
60 0.158 264
80 23.6 335
80 13.3 335
8 0
80
80
80
80
80
80
80
80
80
80
S
Chl oroform 80
C
C
Cumene 8 0
Cyclohexane 8 0
Et hane, 1,2dichloro- 80
Et hane, 1,1,2,2-tetrachloro- 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
C
C
8 0
80
80
80
80
80
80
80
8 3
8 3
8 3
8 3
8 3
8 3
8 3
8 3
8 3
8 3
8 3
1 8 3
8 3
1 8 3
8 3
83
1 8 3
8 3
1 8 3
8 3
8 3
8 3
8 3
8 3
8 3
8 3
83
70 0.983
70 2.05
-
1 3 7
1 3 7
60 0.165
80 1.971
80 1.110
80 0.510
80 0.510
C
C
C
C
264
1 8 3
1 8 3
1 8 3
1 8 3
100 900
120 1000
60 30800
60 0.001
60 0.996
A, F7
A ~7
F7
109
1 0 9
1 9
70
2 1
60 6.5
80 0.24 A
86
3 1
-, l,l,l-trichloro-
Ethyl acetate
Ethyl alcohol
Heptane
2-Heptanone
Isobutyl alcohol
2,4-Pentanedione
To l u e n e
-, hexadecyl ester
Carbon tetrachloride
Cumene
-, isobutyl ester
Benzene
Carbon tetrachloride
Chl oroform
Et hane, 1,2-dichloro-
-, 1,1,2,2-tetrachloro-
Methacrylonitrile
Carbon tetrabromide
Iron(II1) chloride
Isobutyraldehyde
To l u e n e
Methyl methacrylate
Acetaldehyde
Acetic acid
Remarks page II - 157; References page II - 1. 59
II / 124 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 4. contd
Solvent/Additive T (I cs (xlO4) Remarks Refs.
Methyl methacrylate (contd)
Acetic acid, monochloro-
-, dichloro-
-, l,l-dimethyl-2,2,2-trinitro-
ethyl ester
-, trichloro-
A c e t o n e
Acetonitrile, (m-bromophenyl)-
-, @-bromophenyl)-
-, (m-chlorophenyl)-
-, @-chlorophenyl)-
-, (p-methoxyphenyl)-
-, phenyl-
-, m-tolyl-
-, p-tolyl-
Acetylene, p-bromophenyl-
-, p-chlorophenyl-
-, p-nitrophenyl-
Aluminum, hydrodiisobutyl
-, triethyl
Aniline
-, N, N-dimethyl-
-, N,N-divinyl-
-, N-methyl-
p-Anisaldehyde
Anisole
-, p-ethynyl-
-, p-isopropyl-
-, p-methyl-
Anthracene
Azobenzene
Benzaldehyde
-,p-bromo-
-, m-chloro-
-, p-chloro-
-, p-cyano-
Benzene
-, allyl-
-, bromo-
-9 rert-butyl-
60 0.64 R 529
60 0.80 R 529
45
60
60
80
60
60
60
60
60
60
60
60
60
60
60
60
50
60
60
80
100
30
50
60
70
80
100
60
60
80
100
60
2 5
60
60
60
50
50
60
60
60
60
60
25
30
50
52
60
75
80
90
60
25
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
1 8
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
K
K
K
S
R, F2
F2
F2
F2
F16
H
A, F2
A, F2
A, F2
110
R 529
8 1
A 3 1
8 1
462
461
462
461
461
461
462
461
1 5 1
1 5 1
1 5 1
156
547
156
424
424
424
508
228
409
1 6 1
424
270
424
424
82
424
424
424
495
1 6
1 5 1
406
496
1 5
282
86
495
495
495
495
495
1 6
508
147,327
8 1
8 1
1 8 1
1 2 3
3 1
8 1
1 4 5
147
502
1 6
3 1
F2
F2
F2
D
K
C
D
C
C
A
I1
D
A
TABLE 4. contd
Transfer Constants to Solvents and Additives II / 125
Solvent/Additive T (3 cs (x104) Remarks Refs.
Methyl methacrylate (contd)
-, chloro-
-, p-diisopropyl-
-, m-dinitro-
-1 ethyl-
-,
ethynyl- 60
-, fluoro-
Benzene sulfonylchloride
-, p-chloro-
-, p-dimethyl-
Benzonitrile
-, p-hydroxy-
-, p-isopropyl-
p-Benzoquinone
-, 2,3,5,6-tetrachloro-
Benzothiazolethion, 3-allyl-
Benzyl ether
Bibenzyl
Biphenyl, 2,2-methylene-
Borane, tributyl-
Bromoform
Butane, l-chloro-
-, l,l,l-trinitro-
1.4-Butanediol
2 - Bu t a n o n e
1 - Bu t e n e
-, 3,4-epoxy-2-methyl-
2-Butene. cis-
-, trans-
3-Buten-2-01, 1-chloro-3-methyl-
Butyl alcohol
set-Butyl alcohol
rertSuty1 alcohol
Butylamine, N-nitro- 45
Butyl ether 60
1-Butyne, l-phenyl- 60
Bu t y r a l d e h y d e 50
Carbon tetrabromide
2 5
60
80
60
50
52
60
80
2 5
60
60
60
2 5
60
50
60
44.1
50
60
44.1
60
2 5
60
50
60
60
60
77
80
45
60
80
60
70
7 5
80
40
50
80
40
50
40
50
80
60
80
60
80
60
80
30
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
1 5 3
10.4
8.0
0.0
41.8
53.5
7.45
2 3
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 . 3 9 4
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
D
A
A
1 1
K
J
D
R
R
R
D
D
F2
JA C R
A
F24
F24
C
C
C
A
A
A
A
W8
WI
D, R, JJ3a
D, R, JJ3b
1 6
8 1
3 1
8 1
406
1 5
8 1
8 1
8 1
3 1
1 4 5
1 5 1
150
1 6
543
543
543
1 6
150
479
406
194
15
42
194
502
368
368
354
567
567
156
506
3 1
110
421
421
290
1 2 3
1 2 3
3 1
287
287
269
287
287
287
287
269
479
3 1
479
3 1
8 1
3 1
81
110
86
150
500
500
500
521
521
Remarks page II - 157; References page II - 159
II / 126 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 4. contd
Solvent/Additive T (Cl cs (x104) Remarks Refs.
Methyl methacrylate (contd)
Carbon tetrabromide (co&d)
Carbon tetrachloride
Chl oroform 60
Copper(R) chloride
Cumene
-, p-bromo-
-, p-tert-butyl-
-, p-chloro-
Cyclohexane
-9 methyl-
-, truns-l,C, di acet at e
cidtruns-1,4-, dicarboxylic acid dimethylester
Cyclotetrasiloxane, octamethyl-
p-Di oxane
Diphenylamine
Diphenylamine-T
Disiloxane, l,l-dimethoxy-3,3,3-trimethyl-l-phenyl-
-, hexamethyl-
Epibromohydrin
Epichlorohydrin
Et hane, 1,2-dichloro-
-, nitro-
-, 1,1,2,2-tetrachloro-
-, l,l,l-trichloro- 80
-, l,l,l-trinitro- 45
Ethyl acetate 60
60
60
60
80
100
20
30
50
60
IO
80
80
-
60
60
80
60
60
60
60
80
80
60
60
50
79.5
80
44.1
60
19.5
19.5
60
60
60
80
45
60
80
1000 f 500
500 f 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 10s
1.9
2.56
1.9
2.4
3.71
2.74
3.07
1 2
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
D, R, JJ3c
D, R, JJ3d
F2
F2
F2
C D
D, F2
C
R
R H
R
R H
A
11
D
C
A
11
D
Fl
A
11
A
A
C
C
C
A
F2
R
R
A
A
C
A
C
521
521
109
568
568
109
109
3 5
451
514
514
8 1
1 8 1
86
529
529
568
568
514
3 1
8 1
1 4 5
427
8 1
1 8 1
8 1
3 1
1 4 5
427
36
7
406
3 1
1 4 5
406
406
406
86
3 1
3 1
569
569
450
474
3 1
194
46
474
474
529
529
8 1
8 1
110
8 1
3 1
8 1
3 1
110
316
290,316
216
290
290
TABLE 4. cont' d
Solvent/Additive T ((3
Transfer Constants to Solvents and Additives II / 127
cs (x104) Remarks Refs.
Methyl methacrylate (contd)
Ethyl acetate (contd)
Ethyl alcohol
Ethylene glycol
Germane, diethylchloro-
-, ethyldichloro-
-3 triethyl-
triphenyl-
Gycerol
Heptane
1-Heptanol, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-
Hydrazyl, 2,2-diphenyl-l-pi@
Hydroquinone
Indium, triethyl-
Isobutyl alcohol
Isobutyric acid
methyl ester
;sbpropyl alcohol
Lead, tetraethyl 60
Malononitrile, furfurylidene- 44.1
Mercury, diethyl 60
Methane. bromotrichloro- 30
-, bromotrinitro-
Methane, dichloro-
-, nitro-
-, trinitro-
-, triphenyl-
Me t ha nol
1 - Na p h t h o l
2,6-Octadiene, 2,6-dimethyl-
Oleic acid, methyl ester
Oxime, acrolein-
-9
crotonaldehyde-
-1 ethylisopropenylketone-
-, methacrolein-
-1
methylacrolein-
-1 methylisobutenylketone-
-9
methylisopropenylketone-
methylvinylketone-
zxolane, cis-3,4-diacetoxy-
Pentane, 2,2,4-trimethyl-
1-Pentanol, 2,2,3,3,4,4,5,5-octa-fluoro-
2-Pentanone, 4,4-dimethyl-5,5,5-trinitro-
70
75
80
60
80
100
60
80
60
60
60
60
60
50
60
44.1
45
131
60
60
8 0
80
60
60
80
100
130
45
60
80
60
45
60
60
80
100
45
60
60
60
60
60
60
60
60
60
60
60
50
60
45
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
200x 10s
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 x 104
4. 5 x 104
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
C
1 1 0
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
QQ3
D
D, Q4
A, F2
A, F2
A
C
F2
2 9 0
146
1 2 3
1 2 3
3 1
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
8 1
8 1
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
II / 128 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 4. contd
Solvent/Additive
T (Cl
cs (x104) Remarks Refs.
Methyl methactylate (conr 6)
-, 4-methyl-
3-Pentanone
Pentasiloxane, dodecamethyl-
Phenol
-, o-bromo-
-,p-bromo-
-, o-chloro-
-, o-ethyl-
-, p-ethyl-
-, o-isopropyl-
-, p-isopropyl-
-, p-methoxy-
2,3,4,6-tetramethyl-
Phenyl ether
Phosphine, octyl-
-, phenyl-
tributyl-
&thalic acid, dimethylester
Piperidine, l-nitroso-
Pr opane, 1,2-dichloro-
-, l,l-dinitro-
-, 2,2-dinitro-
-, l-nitro-
1,2Propanediol
1-Propanol, 2,2,3,3-tetrafluoro-
Pr opene, 1,3-diphenyl-
1-Propene, 2-methyl-
Propionic acid, 2,2,2-trinitroethyl ester
Propionitrile, 3-phosphino-
-, 3,3-phosphinylidenedi-
Propyl alcohol
Pyridine
Pyrocatechol
-, p-reti-butyl-
Pyrogallol
Silane, (wbromotolyl)trimethoxy-
-, bromomethylphenyltrimethoxy-
-,
chlorotrimethyl-
-, dichlorodimethyl-
-, dichloromethyl-
-, diethylchloro-
-, dimethoxymethylphenyl-
-, dimethylphenyl-
-, hexamethoxy-(3,3-thiodipropyl)bis-
-1 methyldichloro-
-, (3-mercaptopropylhrimethoxy-
-7 tetraethyl-
-, tetramethyl-
-, trichloro
-3 trichloromethyl-
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
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 lo4
16.1 x lo4
30.6
0.2
8.2
0.675
68
1 5
5
0.48
0.86
1.86
15.6
2.5
4.4
3000
1.4 x 104
1.3 x 104
0.69
0.84
1.25
0.176
<5
9
26
29.8
29.8
144
2.2
1 7 5
2.45
15.2
1700
0.20
0.2
300
25.8
15.2
3100
6930
5.75
5.0
1.3
5000
1 8 5
2.7
D
S
A
F24
F24
F2
A 3 1
8 1
8 1
A 3 1
11 1 4 5
474
479
479
479
479
479
479
479
479
30
30
368
368
295
295
156
508
110
3 1
110
110
110
421
421
442
567
287
287
110
295
295
423
423
49
514
30
30
30
474
R 554
D, F2 451
249
D, F2 451
249
474
A, R 539
474
R 554
A, R 539
R 554
R 554
A, R
539
R 554
156
D, F2 451
249
A R 539
D. F2 451
249
A, F2
A, F2
A
TABLE 4. contd
Solvent/Additive T(C)
Transfer Constants to Solvents and Additives II / 129
cs (x104) Remarks Refs.
Methyl methacrylate (co&d)
-, triethyl
-1 triisopropoxymethyl-
-, trimethoxymetbyl-
-3 trimethoxyphenyl-
triphenyl-
&icon chloride
Siloxane, 1,1-dimethoxy-trimethyl-1-phenyl-di-3,3,3-
-, dodecamet hyl penta-
-1
1,1,1,3,5,5,5-heptametbyl-3-phenyltri-
-,
1,1,1,3,5,5,5-heptamethyl-tri-
-, 1,1,1,3,5,5,5-heptamethyl-tri-
-, 1,1,1,3,5,5,5-heptamethyl-3-(3,3,3,3-tri-
-, hexamethyl-di-
-, hexamethyl-phenyl-tri-
-, 1,1,1,5,5,5-bexamethyl-3-(2-phenylpropyl)-tri-
-, 3-(3-mercaptopropyl)-
1,1,1,3,5,5,5-heptamethyl-tri-
-,
octametbyl cyclotetra-
octamethyl tri-
iorbit-2,5-diacetate, 1,4:3,
6-, dianhydro-
Stearamide, N-allyl-
Steak acid, methyl ester
Stibine, tributyl
Tin, tetrabutyl
To l u e n e
-, p-bromo-
-, m-chloro-
-, p-chloro-
-, a-chloro
-, p-ethynyl-
-, p-nitro-
-, 2,4,6-trinitro-
m-Tolunitrile, a-cyano-
p-Tolunitrile
-, a-cyano-
Tributylamine
Triethylamine
Tripropylamine 60
Trisiloxane, 1,1,1,3,5,5,5-heptamethyl- 79.5
-, -, 3-(S-methylphenethyl)- 79.5
-9 -1 3-phenyl- 79.5
-1 -7 3-propyl- 19.5
-1 -1 3-(3,3,3+ifluoropropyl)- 79.5
60
19.5
79. 5
79.5
60
30
50
79.5
19.5
19.5
79.5
79.5
79.5
79.5
79.5
19.5
19.5
79.5 0.08
79.5 0.0316
60 29
9 0
60
60
60
20
52
60
70
80
60
6 0
60
60
60
44.1
44.1
60
60
60
70
20
60
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
3.01
0.282
<l.O
1.32
0.04
0.084
0.170
0.190
0.202
0.250
0.26
0.400
0.45
0.561
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
25.1
1.5
8.3
1900
14.6
0.284
2.08
0.232
0.189
0.205
A, R
R
R
R
A, R
D, fl
R
R
R
R
R
R
R
R
R
R
R
R
C
C, J
C D
C
C
C
C
C
C
I1
A
C
C
K
C D
J
5 3 9
474
554
474
554
474
554
539
451
249
554
554
554
554
554
554
554
554
554
554
554
554
569
173
441
156
156
35
8 1
21.81
316
32,316,317
316
275
316
496
123
32
8 1
1 4 5
3 1
1 2 3
496
496
496
1 8 1
1 5 1
194
194
462
496
461
270
35
24
25
156
474
474
414
414
474
Remarks page I I - 157; References page I I - 159
II / 130 TRANSFER CONSTANTS 1N FREE RADICAL POLYMERIZATION
TABLE 4. contd
Solvent/Additive
T (0
cs (x104) Remarks Refs.
Methyl methacrylate (co&d)
-, 1,1,1,5,5,5-hexamethyl-3-phenyl-
octamethyl-
Gea, thio-
Wa t e r
79.5
79.5
42
60
80.5
60
60
50
1.84
0.032
1.21
0
0.002
0.03
0
0.43
0.50
6.5
A R
F7, F24
474
474
503
268
479
529
48
60 30-50 216
50 11.1 357
60 13.9 357
70 15.2 357
117- 118 270 381
117- 118 520 381
115- 118 230 381
30-35 630 381
120- 125 520 381
116- 120 110 381
55
55
55
3.4
0.35
0.97
313
313
313
70 21.4 11
100
100
(5 -10) x 104
1.03 x 104
C
C
210
210
100
8 0
4800
1.8 x lo4
5.4 x 104
100 17.0 x 104
C
;:
C
210
238
238
210
640000
C, Q(l-3)
570
1.4 1 5 8
50
7 5
100
1 2 5
150
95
1200 QU-4)
517
1400 Q(l) 517
1500
QC9
517
1800
Q(3-4)
517
1700 Q(l) 517
1900
Q(z)
517
1800
Q(3-4)
517
2200 QU-2) 517
2100
Q(3-4)
517
2700
QU-4)
517
17200 f 1100 W23, Q(l) 518
33000 f 15000 W23, Q(z) 518
17000 f 800 W24 Q(l) 518
299000 zt 8000 ~24, ~(2) 518
13800 z!z 800 W20, Q(l) 518
266000 + 10000 W20, QW 518
50 20.7 R 357
70 21.6 R 357
60 8.5 8 6
m-Xylene
p-Xylene
2,4-Xylenol
Naphthalene, l-vinyl-
Naphthalene
Nonanoic acid, vinyl ester
To l u e n e
I-Octene
Butyl alcohol
set-Butyl alcohol
Ethyl alcohol
Isopropyl alcohol
Methanol
Phthalimide, N-vinyl-
Chl oroform
Ethane, l,Zdichloro-
Met hane, dichloro-
2-Picoline, 5-vinyl-
Ally1 ether
1 Propene
Carbon tetrachloride
Chl oroform
1-Propene, 3-chloro-
Carbon tetrachloride
Hydrochloric acid
1-Propene, 2-methyl-
Carbon tetrachloride
-, 3,3,3-trifluoro-
Carbon tetrabromide
Propionic acid, vinyl ester
To l u e n e
Propylene
Bromoethane
Chl oroform
Steak acid, vinyl ester
To l u e n e
Styrene
Acetaldehyde
TABLE 4. contd
Transfer Constants to Solvents and Additives II / 131
Solvent/Additive T (Cl cs (x104) Remarks Refs.
Styrene (contd)
Acetamide, N,N-dimethyl-
Acetic acid
->
methyl ester
-, bromo-
-, chloro-
-, -.
methyl ester
-, dibromo-, ethyl ester
-, monochloro-
50
60
40
100
60
68
68
60
100
90
60
-, dichloro- 60
-, dichloro-, ethyl ester
-, iodo-
-, phenyl-
-, -,
ethyl ester
-, tribromo-
60
68
60
100
-9 -1
ethyl ester
-, trichloro-
-
90
90
-
60
-, -1 ethyl ester
Acetic anhydride
Acetoacetic acid, ethyl ester
-, 2-acetyl, ethyl ester
Ac e t o n e
60
90
100
60
100
100
60
-, oxime
Acetonitrile
m-bromophenyl-
zcetonitrile, p-bromophenyl-
-7 m-chlorophenyl-
-, p-chlorophenyl-
-, p-methoxyphenyl-
-, phenyl-
-1
m-tolyl-
-, p-tolyl-
Acetyl bromide
Acetyl chloride, chloro-
Acetylene, p-bromophenyl-
-, p-chlorophenyl-
-, p-nitrophenyl-
Adipic acid, diallyl ester
-, di-(3,3,5,5-tetramethyl-4-nitrosocyclohexyl) est er
Al l y 1 a l c o h o l
Aluminum, hydrodiisobutyl
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
100
-1 triethoxy-
-, methyl
100
100
-7 triisobutyoxy-
triisobutyl
&line
-, N,N-dimethyl-
- , N, N-divinyl-
100
110
50
60
50
60
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 x lo4
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
1 6 1
3130
6.0
1.1 x 104
1.5
26.9 x lo4
28.0 x lo4
<O.l
8.05 x lo4
17.0 x 104
<l.O
28.5 x lo4
20
2.0
1 2
53
130
C
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
375
1 1 3
385
72
112
149
149
128
1 2 8
64
529
529
529
529
1 2 8
149
1 2 8
72
178
64
64
1 7 8
1 2 8
529
529
128
64
1 2 8
1 2 8
72
72
182
128
501
1 2 8
1 2 8
462
461
462
461
461
461
462
461
112
112
1 5 1
1 5 1
1 5 1
446
314
128
156
1 5 5
155,156
156
1 5 5
1 5 5
1 5 5
154
1 2 8
154
1 6 1
82
Remarks page II - 157; References page II - 159
II / 132 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 4. contd
Solvent/Additive
T (I
cs (x104) Remarks Refs.
Styrene (conrd)
Aniline, N-methyl-
-, 2,4,6-trinitro-
p-Anisaldehyde
Anisole, p-ethynyl-
-, m-isopropyl-
-, p-isopropyl-
-, p-methyl-
-, 2,4,6-trinitro-
An t h r a c e n e
-, dihydro-
2H-Azepin-2-one, hexahydro-
Azohenzene
Benzaldehyde
-,p-bromo-
-, m-chloro-
-, p-chloro-
-, p-cyano-
Benzene
-9 allyl-
-. bromo-
-1 sec-butyl-
-, rert-butyl-
-, chloro-
-, -9 2,4,6-trinitro-
-, 1,2-dibromoethyl-
-, p-dibutyl
-, p-di-sec-butyl-
-, p-di-rerr-butyl-
-, m-dichloro-
-, o-dichloro- 60
-, p-dichloro- 60
50
50
60
60
60
60
60
50
44.1
50
130
70
60
100
60
60
60
100
60
3 5
40
50
60
70
75
80
100
132
100
60
1 5 5
60
60
80
100
60
80
100
140
50
60
60
60
60
140
1 3
11.8 x lo4
2.86
60.0
5.23
3.23
0.78
20.3 x lo4
2.0 x 104
610
0.61
750
4.54
5.5
2.6
12.2
13.7
8.63
5.6
16.7
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 lo4
1950
1.02
10.70
0.87
0.2
1.4
3.4
2.6
F2
K
J
D
c 1
C
A
A
F2
F2
A
C
A, 15
H
C
C
I5
C
A
A, 15
A
A
A
A
A, 15
A, R
C
A
H
A, I5
A
15
A
C
C
C
15
A
154
370,372
495
1 5 1
405
406
496
370,372
159
271
108
281
495
86
298
495
495
495
298
495
119
119
321
127
79
255
1 4 5
415
123
1 2 3
1 8 5
255
273
1 2 7
1 4 5
235
235
235
127
1 4 5
524
182
237
415
1 4 5
1 2 7
1 8 5
127
255
182
255
1 8 5
235
58
370,372
112
415
415
415
58
61
182
182
TABLE 4. contcl
Transfer Constants to Solvents and Additives II / 133
Solvent/Additive T ((2
cs (x104) Remarks Refs.
Styrene (contd)
Benzene, diethyl-, (mixture)
-, p-diisopropyl-
-,
ethyl- 60
-,
ethynyl- 60
-1 sec-hexyl-
-9
sec-pentyl-
-, tri-sec-butyl-
-, 1,3,5-trinitro-
Benzo[B] chrysene
Benzoic acid
-,
m-(phenylazo)-, methyl ester
-, 2,4,6-trinitro-, ethyl ester
Benzoin
Benzonitrile
-, p-isopropyl
Benzo[A]pyrene
p-Benzoquinone
pBenzoqui none, 2-anilino-
-, 2,5-dimethyl-
-, 2-methyl-
-, 2,3,5,6-tetrachloro-
-, 2,3,5,6-tetramethyl-
-, 2,3,5-trimethyl-
Benzyl ether
Bibenzyl, cc,cc-dibromo-
Bicyclohexyl, 3,3,3,3,5,5,5,5-octamethyl-4,4-dinitroso-
Biphenyl, 2,2-methylene-
Borane, tributoxy-
-, tributyl
Butane, l-bromo-
-, l-chloro-
-, 2-chloro-
-, 2,2-dimethyl-
-, l-iodo-
1,4-Butanediol
100
132
60
80
100
132
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 lo5
6.43 x lo5
3.51 x 105
1.3 x 10s
70 700
50 5.72 x 10
60 40
60 5.3
60 18.6
44.1 1.4 x 105
60 22.7 x lo5
80 56.6 x lo5
45 53.2 x 10
80 4.3 x 105
80 21.0 x 105
80 95.0 x 10s
80 6700
80 2.6 x lo5
2 5 71.6
60 62.4
60 3020
60 1.12 x 104
80 1.2 x 104
60 142
60 97.9
100 <O.l
100 34.8
60 0.06
100 0.35
60 0.04
100 0.37
60 1.2
100 0.3
60 0.43
60 1.85
100 5.5
60 3.2
80 5.6
100 9.3
A
A
A
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
F9, J
F9, J
A
A
A
A
A, S
A
A
A
F24
F24
F24
235
235
235
497
406
1 2 7
79
255
1 4 5
363
1 8 5
255
235
1 2 7
1 4 5
235
235
127
1 4 5
1 5 1
150
415
415
415
372
370,372,373
372
159
281
370,372
1 2 8
150
406
159
42
27
199
27
27
27
27
27
368
368
112
314
314
567
567
156
156
128
128
128
1 2 8
1 2 8
128
304
1 2 8
1 2 8
422
422
422
Remarks page II - 157; References page II - 159
II / 134 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 4. contd
Solvent/Additive
T (Cl
cs (xlO4) Remarks Refs.
Styrene (contd)
2-Butanone
1-Butene
-, 3,3-dimethyl-2-phenyl-
-, 2,4-diphenyl-
-, 3,4-epoxy-2-methyl-
-, 2-methyl-
-, 3-methyl-
2-Butene
-, l,Cdichloro-
-, 2,3-dimethyl-
-, 2-methyl-
3-Buten-2-01, 1-chloro-3-methyl-
Butyl alcohol
see-Butyl alcohol
rerr-Butyl alcohol
Butylamine
reti-Butyl et her
terf-Butyl isocyanide
1-Butyne, l-phenyl-
Butyraldehyde
-, diallyl acetal
Butyric acid, 4-hydroxy-, y-lactone
Cadmium, dibutyl
Carobonic acid, cyclic ethylene ester
-, diallyl ester
-, di-(3,3,5,5-tetramethyl-4nitrosocyclohexyl) est er
Carbon tetrabromide
60
70
75
100
110
110
80
100
100
100
80
100
100
80
40
50
60
60
50
60
80
100
130
60
60
80
100
60
-
50
60
100
60
50
100
50
60
60
80
40
60
4.98
8.60
12.00
2.6
1 0
70
17.4
3.1
6.9
6.1
2.0
5 1
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 104
1.8 x lo4
1.78 x lo4
2.2 x 104
2.5 x lo4
13.6 x lo4
4.2 x lo4
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
(5.09f0.18) x lo5 II2
60 88300
60 40600
70 1.8 x lo4
80 2.3 x lo4 F2
90 2.51 x lo4 C
100 2.35 x lo4 A
182
1 2 3
1 2 3
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
1 2 8
487
520
568
568
6 1
109
64
128
TABLE 4. contd
Transfer Constants to Solvents and Additives II / 135
Solvent/Additive
T (C)
cs (x104) Remarks Refs.
Styrene (conrd)
Carbon tetrachloride 8 0
-
100
5 0 1 7
2 4 8
6 0 6 9
8 4
8 7
9 0
9 2
9 8
100
109
110
120
122
144.1
130.9
148
6 0 9 2
6 0 110
7 6 1 8
117
8 0 133
8 5 34.1
9 5 148
186
1 8 5
3 0 4
3 0 0
100
132
140
6 0 0.41
0.5
0.566
3.40
4.0
0.50
0.916
3.3
1 1
3 3
4 3
22.1
3 9
<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
Chloroform/acetone
m-Cresol
o-Cresol
p-Cresol
-, u-phenyl-
-, m-bromo- 6 0
-, p-bromo- 6 0
-, p-tert-butyl- 6 0
-, p-chloro- 6 0
Cyclohexane 6 0
6 8
8 0
6 0
50
5 0
6 0
5 0
6 0
6 0
6 0
8 0
100
8 0
100
W8
436
C, W8
C
c, w7
A
C
Q1 4 2
A, X
R
R H
X
C
A
15
Q38
Q1 4 2
A
A
A
A
C
C
15
C
A
A, I5
I5
A
A, 15
A
A, 15
C
F23
15
C
A
A, 15
4 1 2
4 1 2
513
5 1 3
6 3
401
113,183
401
128,129,210
401
3 6 6
6 3
223
4 1 6
114
5 2 9
5 2 9
1 1 5
5 6 8
5 6 8
2 3 6
2 3 6
1 8 5
1 6 3
6 3
6 3
128,129
129
5 8
501
128,210
255
182
149
1 8 5
2 5 5
501
247,248
247,248
1 2 1
247,248
1 2 1
1 2 1
7
127
1 4 5
4 0 6
1 8 5
127
1 4 5
4 0 5
4 0 6
4 0 6
4 0 6
127
7 9
1 4 5
255
119
185
255
273
127
1 4 5
Remarks page II - 157; References page II - 159
II / 136 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 4. contd
Solvent/Additive T (C) cs (x104) Remarks Refs.
Styrene (contd)
Cycl ohexane (co&d)
Cyclohexanone
-, rruns- 1,4-, diacetate
cis/trans-1,4-, dicarboxylic acid dimethylester
C yclopentanone
1-Cyclopentene-1-carboxylic acid, 3,3,5,5-tetramethyl-4-nitroso-,
diester with pyrocatechol
Cyclotetrasiloxane, octamethyl-
1,2,3,4-Dibenzpyrene
1,2,7,&Dibenztetracene
1,2,9,10-Dibenztetracene
p-Dioxane
Diphenylamine-T
Disiloxane, hexamethyl-
Epibromohydrine
Epichlorohydrine
Et hane, 1,2-dibromo-
-,1,2-dichloro-
-, pentaphenyl-
-, 1,1,2,2-tetrachloro-
-, 1,1,2,2-tetrachloro-1,2-difluoro-
-, 1,1,2-trichloro-1,2,2-trifluoro-
Ethanehexacarboxylic acid, hexaethyl ester
1,1,2-Ethanetricarboxyic aci d
Ether, benzyl methyl
-, p-bromobenzyl methyl
-, p-chlorobenzyl methyl
-, p-cyanobenzyl methyl
-, dodecyl vinyl
Ethyl acetate
Ethyl alcohol
Ethylene, l,l-diphenyl-
Ethylene glycol
-, bis(m-phenylazobenzoate)
Ethyl ether
Fluorene
Formamide, N,N-dimethyl-
1 3 2
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
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
0.31 A 235
12.3
A, R
524
0.81 A 235
0.87 A 1 2 7
1.5 A, 15 1 4 5
7.90 C 182
16.9 C 569
4.2 C 569
3.30 C 182
1.3 x 104
1.0 x 104
4.0
6.0 x lo4
13.0 x 104
13.0 x 104
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
F2
C
C
FlO
C
C
F2
F2
A
F24
F24
F24
C
C
A
A
E
314
314
450
159
159
159
1 2 8
4
182
220
46
474
529
529
255
255
255
182
67
255
112
235
1 2 7
235
1 4
1 4
89
72
1 4 9
1 4 9
149
149
4
4
119
1 2 3
1 2 3
72
423
479
423
432
422
422
422
281
4
127
127
458
375
113
256
Transfer Constants to Solvents and Additives II / 137
TABLE 4. contd
Solvent/Additive T (0
cs (x104) Remarks Refs.
Styrene (conr d)
Furan, tetrahydro-
cc, o-Glucoside, met hyl -
-, -9 6-deoxy-6-mercapto-
-9 -1
2,3-di-o-henzyl-
-9 -, 2,3,4,6-tetra-o-acetyl-
-, -,6-O-@-toluenesulfonyl)-
-1 -9
2,3,4-tri-0-acetyl-6-deoxy-6-iodo-
-1 -, 6-O-triphenylmethyl-
0, D-Glucoside, metbyl-
-, 6-deoxy-6-dipropylamino-
&mane, ethyldichloro-
-, diethylchloro-
-, triethyl-
-, dimethylchloro-
triphenyl-
HLptane
1-Heptanol, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-
1-Heptene
2-Heptene
Hexane
1 -Hexene
2-Hexene
Hydrochloric acid
Hydroquinone
Hydroxylamine, N,N-dibenzyl-
-9
N-benzyl-N-phenyl-
- , N, N-diethylene-
N-ethyl-N-phenyl-
&mm triethyl
Iron@) chloride
Isobutyl alcohol
Isobutyl alcohol-D
Isobutyraldehyde
Isobutyric acid
Isobutyronitrile
Isophthalic acid, diallyl ester
Isopropyl alcohol
Isopropyl alcohol-D
Isopropyl-l-D alcohol-D
Lead, tetraethyl
Malonic acid, diallyl ester
-, diethyl ester
-, dimethyl ester
-1
acetyl-, diethyl ester
-, bromo-, diethyl ester
-, butyl-, diethyl ester
-, dibromo-, diethyl ester
-, dichloro-, diethyl ester
-, diethyl-, diethyl ester
-7
ethyl-, diethyl ester
50
100 55000 220
100 62 220
100 2.0 220
100 2.0 220
100 50 220
100 2 1 220
100
60
60
60
60
60
60
100
60
100
100
100
100
100
100
60
60
60
60
60
100
60
60
100
130
60
100
130
60
60
80
100
130
100
100
100
60
60
100
100
100
60
100
100
60
60
100
100
100
0.50
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 lo4
20.5 x lo4
1.7600 x lo4
536.0 x lo4
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
C
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
W 8
C
A
A
A
F2
F2
A
F2
A
A
A
A
A
A
A
A
A
449
220
539
539
539
539
539
1 2 7
127
442
358
358
358
358
524
358
238
128
533
533
533
533
156
1 9
385
479
261
261
412
412
385
385
261
261
446
423
423
261
423
261
261
261
156
446
1 2 8
72
72
72
1 2 8
1 2 8
72
1 2 8
128
128
72
72
Remarks page II - 157; References page II - 159
II / 138 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 4. contd
Solvent/Addition
T ((3 cs (x104) Remarks Refs.
-, dibromo-
-. dichloro-
-, diiodo-
-, diphenyl-
-, nitro-
-,
triphenyl-
Methanetricarboxylic acid
Methanol
-, (4-biphenylyl)phenyl@-vinyl-phenyl)-
-, bis(4-biphenylyl)(p-vinyl-phenyl)-
Naphthalene
-, decahydro-
-, 2-isopropenyl-
-, 2-methoxy- 60
-, 1,2,3,9-tetahydro-l-phenyl- 60
1-Naphthol 60
-, 2,4-dichloro- 60
1-Naphthol-D 60
2-Naphthol 60
Naphtho[2,3-alpyrene 44.4
2,6-Octadiene, 2,6-dimethyl- 60
2-Octene 100
Oleic acid, methyl ester 60
Oxalic acid, diallyl ester
-, diethyl ester
Oxetane, 3,3-bis(chloromethyl)-
Oxime, acrolein
-, crotonaldehyde-
-,
ethylisopropenylketone-
-, methacrolein-
-3 methylacrolein-
-3 methylisobutylketone-
-,methylisopropenylketone-
methylvinylketone-
Gxolane, cis-3,4-diacetoxy-
Pentane, l-chloro-
-, 2,2,4-trimethyl-
2,CPentanedione
Styrene (contd)
Malonic acid, phenyl-, diethyl ester
Mercury, diethyl
Met hane, bis(2-chloroethoxy)-
-, bromotrichloro-
100
100
80
80
60-80
80
60
60
80
100
60
60
100
60
60
80
100
100
60
80
100
50
50
60
60
80
99
70
90
60
60
50
60
60
60
60
60
60
60
60
60
60
100
100
3.5
0.335
6.0 C
7.6 x lo4
D, Q2
7.7 x 104 Q Q2
2.4 x lo6 D, Q3
2.78 x lo6 D, 43
6.5 x lo5
(6.5 f 0.4) x lo5
9 4 5 0
110
0.15
9.5
11.8
710
2.3
4.2
35
1 0
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 lo5
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
15
A
C
A
A
A
A R
A
A
F2
F2
F2
A
C
J
C
A
C
C
A
F22
C
72
156
112
312
1 9 5
312
1 9 5
439
504
1 8 5
112
128
112
128
112
1 2 7
1 2 7
524
86
1 2 7
44
127
72
479
423
423
423
57
57
216
1 2 7
98
98
98
98
1 2 1
467
50,121
1 2 1
50,121
122
159
324
358
441
441
239
1 4 1
441
446
119
449
555
555
555
555
555
555
555
555
569
1 2 8
1 5 5
72
TABLE 4. contd
Transfer Constants to Solvents and Additives II / 139
Solvent/Additive
T (Cl cs (x104) Remarks Refs.
Styrene (conrd)
1-Pentanol, 2,2,3,3,4,4,5,5-octa-fluoro-
3-Pentanone
Pentasiloxane, dodecamethyl-
1-Pentene
-, 4,4-dimethyl-2-phenyl-
-, 2,4-diphenyl-
-, 4-methyl-2,4-diphenyl-
-, 4-methyl-2-phenyl-
-, 2,4,4-triphenyl-
2-Pentene
-, 2-methyl-
4-methyl-
Phenol
-, p-benzyloxy
-, p-terr-butyl-
-, o-chloro-
-, p-chloro-
-, 2,6-di-tert-butyl-
-, 2,6-diisopropyl-
-, p-fluoro-
-1 m-methoxy-
-> o-methoxy-
-, p-methoxy-
-, o-phenyl-
-, 2,3,4,6-tetramethyl-
-, 2,4,6-trinitro-
Phenol-D, p-benzyloxy-
-, 2,3,4,6-tetramethyl-
Phenyl 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) est er
Piperidine
Propane, 1-chloro-2,3-epoxy-
-, 1-chloro-2-methyl
-, 1,1,1,3-tetrabromo-3-phenyl-
-, l,l,l-tribromo-
1,2Propanediol
1,3-Propanediol, 2,2-bis(bromomethyl)-, diacetate
1,3Propanedione, 1,3-diphenyl-
1-Propene, 3-chloro-2-methyl-
-, 2-methyl-
-, 1,3-diphenyl-
Propionaldehyde, diallyl acetal
Propionic acid
60 11.36
60 2.6
79.5 0.285
100 2.3
110 1 0
110 170
110 2900
110 1 0
110 2600
100 4.2
100 6.3
100 6.9
50 8.1
60 1 4
60 290
60 26
60 6.0
60 -11
60 49
60 310
60 54
60 <5
60 43
60 260
60 <5
60 580
50 2.11 x 10s
60 1 0
60 20
25 7.94
60 7.86
100 2.08 x lo4
100 1.35 x 104
60 3.6 x lo4
60 43.9 x 104
100 24.4
100 <O.l
25 400
57 250
75 800
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 x lo4
1.0
7.5
1.4
3.0
3.65 x lo4
2.41 x lo4
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
F2
A
D
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
442
385
474
358
433
433
433
433
433
358
358
358
247,248
122
50,121
1 2 1
122
1 2 1
1 2 1
1 2 1
121
1 2 1
122
1 2 1
1 2 1
50,121
371
50
50
368
368
296
296
295
295
156
156
99
214
494
446
446
314
314
1 2 8
449
128
128
64
64
422
422
422
325
1 2 8
1 2 8
358
567
446
1 2 8
385
323
385
Remarks page II - 157; References page II - 159
II/140 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 4. contd
Solvent/Additive
T (Cl
cs (x104) Remarks Refs.
Styrene (contd)
Propionitrile, 3-phosphino-
-, 3,3-phophinylidenedi-
Propyl alcohol
Propylene oxide
2-Propyn- 1-01
Pyridine
Pyrocatechol
-, p-teti-butyl-
Pyrocatechol-D
-, p-rerr-butyl-
Pyrogallol
Pyrogallol-D
Sebacic acid, diallyl ester
Silane, chlorotrimethyl-
-, dichlorodimethyl-
-, diethylchloro-
-, dimethylphenyl-
-, hexamethoxy-(3,3-thiodipropyl) bis-
-3 methyldichloro-
-, 3-mercaptopropyl-trimethoxy-
-, trichloro-
-9 tetraethyl-
-.
tetramethyl-
-, trichloromethyl-
-, triethyl-
-, trimethoxymethyl-
-, triphenyl-
Silicon chloride
Siloxane, hexamethyl-di-
-, dodecamethyl-penta-
octamethyltri-
Sorbit-2,5-diacetate, 1,4:3,6-, dianhydro-
Stamtane, triphenyl-
Stearamide, N-allyl-
60
70
80
50
79.5
79.5
79.5
60
60
90
Steak acid, methyl ester 60
Stibine, tributyl
Stibene, dibromo-
Styrene, u-bromo-
-, j3-bromo-
-, di bromo-
-, cr-ethyl-
-7 u-methyl-
Succinic acid, diallyl ester
Succinonitrile, tetraphenyl-
Sulfonyl chloride, benzene-
-, p-chloro-benzene-
-, p-methyl-benzene-
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
70
90
1 0 0
60
70
70
60
110
60
74
80
99
110
60
50
60
60
60
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
1 0
0.86
95
3.2
4.9
5.6
8.5
1.67
5.4
28000
4330
7650
3180
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
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
1 7 3
1 7 3
441
239
1 4 1
441
156
112
172
172
112
439
431
343
98
98
98
98
431
446
89
543
543
543
TABLE 4. contd
Solvent/Additive
T ()
Transfer Constants to Solvents and Additives II / 141
cs (xlO4) Remarks Refs.
Styrene (co&d)
Sulfonyl chloride, p-methoxy-benzene-
-, methane-
-, phenylmethane-
a-phenyl-P-(methanesulfonyl)-ethane-
ikephthalamide, N,N-dimethyl-N,N-dinitroroso-
Terephthalic acid, diallyl ester
Tin, tetrabutyl
To l u e n e
-, p-bromo-
-, m-chloro-
-, p-chloro-
-, a-chloro-
-, cc,cc-dichloro-
-, p-etbynyl-
-3 u- H 1, t ol uene
-, PO-* HZ, toluene
-3 c@fl-* H3, toluene
-, craa-trichloro-
-, 2,4,6-trinitro-
p-Toluidine
-, N,N-dimethyl-
-, N-metbyl-
m-Tolunitrile, a-cyano-
p-Tolunitrile
-, a-cyano-
s-Triazine, trimethyl-
Triethylamine
Tripropylamine
Trisiloxane, octamethyl-
Urea, 1,3-bis(3,3,5,5-tetramethyl-4-nitrosocyclohexyl)-
Wa t e r
m-Xylene 60
p-Xylene 60
-, ~,a-dibromo- 60
2,6-Xylenol 60
60
60
60
60
40
60
60
100
60
8 0
100
132
60
60
70
140
60
60
60
60
80
80
80
60
50
50
50
50
60
60
60
60
60
100
19.5
60
80
60
3110 R 543
1180 R 543
3190 R 543
27600 R 543
1400 160
2000 160
4.5 446
3.71 156
0.105 C 255
0.121 21,24,79
0.125 A 1 2 7
0.134 78
0.16 A, 15 1 4 5
0.21 318
0.82 496
1.10 C 363
2.05 363
0.15 C 385
0.298 I5 1 8 5
0.3 C 385
0.308 C 255
0.310 76,71
0.313 78,273
0.813 C, F17 530
0.53 A 235
0.55 C 385
0.645 A 1 2 7
0.72 A 235
0.8 A, I5 1 4 5
1.12 A 235
1.30 496
1.25 496
0.62 67
1.8 67
1.07 496
1.56 A 1 2 8
50.0 A 1 2 8
72.0 K 1 5 1
0.825 C, F17 530
0.820 C, F17 530
0.992 C, F17 530
57.5 A 128
14.6 x lo4 370,372
78 F2 154
1 6 F2 154
11 F2 154
91.4 462
2.07 496
112 461
0.468 88
1.4 w9 364
3.0 W6 364
7.1 24
7.5 363,364
24.2 156
0.069 474
14500 F9, J 314
15000 F9, J 314
0.006 479
0.31 A R 529
0.78 496
0.84 496
150 112
110 1 2 1
Remarks page II - 157; References page II - 159
II / 142 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 4. contd
Solvent/Additive
T ((3 cs (xlO4) Remarks Refs.
St yrene (contd)
Zinc, diethyl
-, p-chloro-
Anisole, p-isopropyl-
Benzaldehyde
-, p-chloro-
Benzene, p-diisopropyl-
100 3660 156
60
100
100
60
3.86
1.9
9.7
3.62
1.24
8.84
52000
45
3.44
5.71
3.52
4.91
A
A
60
60
60
60
60
60
60
F2
406
298
298
491
406
406
109
366
406
406
406
406
50 0.2 56
60
60
60
60
60
60
60
3.27 408
3.67 408
1.34 406
26.0 408
4.12 408
9.23 408
3.59 408
7.67 408
60
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
A
469
469
469
469
469
469
469
469
469
469
60 1 5 E F 366
1 1 5 EE 366
55 0.077 C, F25 93
55 0.127 C, F26 93
80 6.2 201
30
45
50
60
400
530
390
0.12
200
220
500
570
660
610
700
40
0.180
0.166
0.200
1.0
1.13
1 0
0.170
J
18
F2
J
70
15
60
50
60
J
C
19
65
F2
C
346
86
460
251
145
232
460
86
86
460
86
86
466
465
466
1 4 5
289
86
466
Benzonitrile, p-isopropyl-
Carbon tetrabromide
Carbon tetrachloride
Cumene
-, p-bromo-
-, p-tert-butyl-
-, p-chloro-
-, p-iodo-
Benzene
-, p-methyl
Anisole, p-isopropyl-
Benzene, p-diisopropyl-
Benzonitrile, p-isopropyl-
Cumene
-, p-bromo-
-, p-tert-butyl-
-, p-chloro-
-, pentafluoro-
Benzene, bromo-
-, chloro-
-, ethyl-
-, fluoro-
2-Butanone, 3-methyl-
Cumene
Furan, tetrahydro-
2-Pentanone, 4-methyl-
To l u e n e
StyreneNyrene, p-chloro-
Carbon tetrachloride
Succinimide, N-vinyl-
Acetic acid
Et hane, 1,2-dichloro-
Valerie acid, 4-methyl-, vinyl ester
Benzene
Vinyl acetate
Acetaldehyde
Acet ami de, N-butyl-
Acetic acid
TABLE 4. contd
Transfer Constants to Solvents and Additives II / 143
Solvent/Additive
T (C) cs (xlO4) Remarks Refs.
Vinyl acetate (conld)
Acetic acid, ally1 ester
-, benzyl ester
-, butyl ester
-1
set-butyl ester
-, tert-butyl est er
-, isobutyl ester
-1 isopropyl ester
-1 methyl ester
-, propyl ester
-, 1,3,3,3-tetrachloropropyl est er
-. bromo-
-, chloro-
-9
cyano-, methyl ester
-, dichloro-, ethyl ester
-, phenyl-
-, trichloro-
-1
ethyl ester
trifluoro-, ethyl ester
Acetic anhydride
Acetoacetic acid, ethyl ester
Ac e t o n e
-, phenyl-
Ac e t o p h e n o n e
-, 3-hydroxy-
-, 3-hydroxy-D-
An i l i n e
-, N,N-dimethyl-
-, N-methyl-
-, p-nitro-
m- An i s a l d e h y d e
o - An i s a l d e h y d e
p - An i s a l d e h y d e
An i s o l e
An t b r a c e n e
-, 9-phenyl-
Benzaldehyde
60
60
5 0
50
60
5 0
60
5 0
50
60
61. 5
75
6 0
50
60
70
6 0
70
70
60
6 0
60
70
6 0
50
60
70
6 0
70
75
6 0
60
50
60
70
45
45
50
50
50
50
60
60
6 0
60
20
30
40
50
60
50
60
70
15
85
94
8 0
13. 2
4. 4
8. 0
1. 5
6. 2
9. 1
3. 5
3. 1
8.0
9. 0
1 0
1.56
1.6
2. 5
6. 2
3. 4
423. 2
489
4450
2550
5000
210
400
1445
4 4 0 0
30
8. 0
80. 4
1. 5
11. 70
12. 0
25. 6
42
1 0
2100
91.5
100
62. 0
1405
1290
149
210
260
360
48600
2500
420
370
1 0
6. 68 x 10s
6. 03 x lo*
4. 55 x 10s
2. 057 x lo5
3. 64x 10s
2. 78 x lo5
2. 73 x lo5
230
460
540
421
600
F 2
J
F2, J
J
J
C
C J
C
C
J
C
C
C
C
C
J
J
C
J
F2
F2
F2
fl, J
J
F2
J
C, J
J
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 II - 157; References page II - 159
II / 144 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 4. contd
Solvent/Additive T (3 cs (xlO4) Remarks Refs.
Vinyl acetate (contd)
Benzaldehyde, m-chloro-
-, o-chloro-
-, p-chloro-
-, m-cyano-
-, p-cyano-
-, p-isopropyl-
Benz[A]anthracene
-, bromo-
-9
tert-butyl-
-. chloro-
Benzene, o-dichloro-
-, p-dichloro-
-, m-dinitro-
-, o-dinitro-
-, p-dinitro-
-1 ethyl-
-, nitro-
-, 1,3,5-trinitro-
Benzo[B]chrysene
Benzoic acid
-,
ethyl ester
-, p-nitro-
Benzoic anhydride
Benzoin
Benzonitrile
-1 m-hydroxy-
m-hydroxy-D-
Bknzo[GHl]perylene
Benzophenone
Benzo[A]pyrene
Benzo[E]pyrene
p-Benzoquinone, 2,3,5,6-tetramethyl-
Benzoyl chloride
Benzyl alcohol
Biphenyl
Borane, tributyl
60
60
60
60
60
60
50
60
70
7 5
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
1 0
860
390
340
1070
610
540
1.17 x 10s
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 10s
645700
9.6 x lo5
26.7 x 10
662800
55.15
100
110300
8.9 x lo6
434280
2.83 x lo5
50
26
245700
130
800
40.6
820
805
1.82 x lo4
286
3.06 x 10
8400
9.5 x 10s
366
300
556
263
6.4
9000
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
C
C
86
86
86
86
86
86
4 1
263
86
294
80
289
294
390
86
263
184
1 5
265
265
265
389
184
289
265
265
265
289
86
389
184
184
389
28
1 5
28
28
1 5
289
86
1 5
28
15
4 1
86
86
1 5
86
86
1 5
5 1
5 1
370
1 5
4 1
370
27
1 5
389
390
15
132
1 9 1
TABLE 4. contd
Transfer Constants to Solvents and Additives II / 145
Solvent/Additive
T (Cl
cs (xlO4) Remarks Refs.
Vinyl acetate (cent d)
But ane, l-bromo-
-, l-chloro-
-, l-iodo-
2,3-Butanedione
2-Butanone
-, 3-methyl-
1-Butene, 3-chloro-3-methyl-
2-Butene, 1-chloro-3-methyl-
1-Buten-3-yne
Butyl alcohol
set-Butyl alcohol
rerr-Butyl alcohol
Butyl ether
3-Butyn-2-01, 2-methyl-
Butyraldehyde
Butyric acid, ethyl ester
-,
methyl ester
Carbon tetrabromide
Carbon tetrachloride
Chloral hydrate
Chloroform
2-Chloro-3-(methyl-4C)-lbutene(4- 14C)
3-Chloro-2-pentene-(2,4- 14C)
60
70
60
60
60
60
75
60
50
50
60
60
70
60
70
75
60
70
60
60
40
6 0
70
50
60
60
70
0
20
45
60
70
75
60
70
70
-
30
60
70
50
50
50
1100
1 0
800
670
73.80
1 6 5
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
1 8
1 9
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
C
F2, J
C
F2
F2
J
19
C
C
C
19
C J
J
W8
w7
w15
C
C
F2
C
:;:
C
J
C
C
I9
J
F2
C
F2
F2
86
389
86
86
86
289
184
289
152
152
232
1 4 5
289
390
289
390
184
289
1 4 5
86
390
86
86
500
500
500
500
232,355
86
390
7 1
145,232
86
109,145
389
346
309
86
1 0
1 0
1 0
1 0
86
1 0
1 0
86
210
1 0
1 0
389
86
86
389
389
345
346
289
1 4 5
86
210
86
389
509
509
Remarks page II - 157; References page II - 159
II / 146 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 4. contcf
Solvent/Additive
T (Cl
cs (xlO4) Remarks Refs.
Vinyl acetate (contd)
Chrysene
m-Cresol
m-Cresol-D
p-Cresol
p-Cresol-D
Crotonaldehyde
Cumene
Cyclohexane
-,
methyl-
1,3Cyclohexanedione, 5,5-dimethyl-
Cyclohexanol
Cyclohexanone
Cyclohexene
Dibenz[a,h]anthracene
Dibenzo[def,mno]chrysene
1,2,3,4-Dibenzpyrene
Diethylene glycol
Diethylphosphonate
p-Di oxane
Diphenylamine
Diphenylamine-D
Diphenylamine-T
Et hane, l,l-dibromo-
-, 1 ,Zdibromo-
-, l,l-dichloro-
-, 1,2-dichloro-
-, 1,2-dichloro- 70
-, hexachloro- 70
-, pentachloro- 70
-, 1,1,2,2-tetrabromo- 60
-, 1,1,2,2-tetrachloro- 60
-, l,l,l-trichloro-
-, 1,1,2-trichloro-
1 , 1-Ethanediol, diacetate
Ether, benzyl methyl
-, bis(Zchloroethy1)
-, dodecyl vinyl
e t h y l
l&y1 acetate
50
45
45
45
45
60
60
70
75
60
60
70
70
60
75
60
75
50
40
50
60
50
70
60
60
60
60
60
70
50
60
60
60
60
70
60
60
70
60
60
60
60
70
60
60
20
40
50
60
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 lo4
156.5 x lo4
129.2 x lo4
105.4 x 104
73.6 x lo4
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
1 2
1.07
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
C
F2, J
C
C
C
C
C
370
5 1
6 1
5 1
5 1
355
289
7,86
390
184
289
145
86
289
86
390
390
86
184
86
86
86
370
4 1
4 1
4 1
4 1
390
571
571
571
571
86
390
1 5
46
46
46
86
389
86
86
1 4 5
289
389
389
389
86
289
86
389
289
289
86
86
389
4
4
4
328
328
208
7 1
289
TABLE 4. contd
Solvent/Additive T (C)
Transfer Constants to Solvents and Additives I I / 147
cs (x104) Remarks Refs.
Vinyl acetate (contd)
Ethyl acetate (contd)
Ethyl alcohol
Ethylene, tetrabromo-
-, tetrachloro-
-, tribromo-
-, trichloro-
Ethylene glycol
Fluorene
-, 9-phenyl-
Formamide, N,N,-dimethyl-
Formic acid, ethyl ester
methyl ester
i:Furaldehyde
Furfuryl alcohol
Germane, dietbylchloro-
-, dimethylchloro-
trietbyl-
I:triphenyl-
Glycolic acid, methyl ester
Heptane
1-Heptanol, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-
1,5-Hexadien-3-yne
Hexanoic acid, 2-ethyl-, ethyl ester
Hydroquinone
-, 2,5-di-terr-butyl-
-, 2,6-dimethyl-
tetramethyl-
;sbbutyl alcohol
Isobutyric acid
Isobutyric acid, ethyl ester
-3 methyl ester
Isobutyronitrile
Isopropyl alcohol
Lactic acid, ethyl ester
methyl ester
&ric acid, ethyl ester
Malonic acid, dimethyl ester
p-Mentha-1,8-dene
Me s i t ol
Methane, bromotrichloro-
-, dichloro-
-, iodo-
-, nitro-
-, tribromo-
-, triphenyl-
Me t ha nol
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
1.25
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
7 1
86
100
44.6
700
640
105
1 7
1900
5000
29 104
6000
>4 x 10s
6303
4
1230
2300
2600
34760
700
9.0
10.0
10.5
3.4
2.26
C
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
C
C
C
J
J
Q S
C
C
C
C
F2, J
J
C
80
145,232
328
86
420
390
86
390
389
389
389
389
390
86
390
390
86
7 1
86
86
390
539
539
539
539
86
208
442
232
7 1
338
338
338
338
289
390
289
7 1
145,232
420
86
86
390
86
86
7 1
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 II - 159
II / 148 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 4. contd
Solvent/Additive T (Cl cs (xlO4) Remarks Refs.
Vinyl acetate (contd)
Methanol (contd)
Naphtbacene
Naphthalene
- , decahydro-
Naphtho[l,2,3,4-deflcbrysene
Nonanoic acid, ethyl ester
2,6-Octadiene, 2,7-dichloro-
-, 2,6-dimethyl-
70
60
50
50
50
60
Octanoic acid, ethyl ester 50
Oleic acid, methyl ester 60
Orthofonnic acid, trimethyl ester
Oxalic acid, diethyl ester
-, dimethyl est er
90
-
30
60
60
Paraldehyde 70
Pentane, 2,2,4-trimethyl- 50
2,4-Pentanedione 60
1-Pentanol, n 2,2,3,3,4,4,5,5-octafluoro- 60
2-Pentanone, 4-methyl- 60
3-Pentanone 60
Pentyl acetate
Pentyl alcohol
Perylene
Phenantbrene
Phenol
-, m-chloro-
-, p-chloro-
-, p-nitro-
-, 2,3,4,6-tetramethyl-
Phenol-D
-, m-chloro-
-, p-chloro-
-, 2,3,4,6-tetrametbyl-
Phosphorus trichloride
Propane, 2-bromo-2-methyl-
-, 2-chloro-2-methyl
1-Propanol, 2,2,3,3-tetrafluoro-
1-Propene, 3-chloro-
-, 3-chloro-2-methyl-
Propionaldehyde
Propionic acid, ethyl ester
-1 methyl ester
Pyrene 50
Pyrocatechol, 4-(1,1,3,3,-tetramethylbutyl)- 50
Pyrogallol 50
Salicylic acid 70
Silane, dimethylphenyl- 60
70
50
50
70
75
75
50
50
70
45
50
60
45
45
50
45
45
45
45
45
60
60
60
60
60
60
60
70
50
60
4.3
6.0
5.5
8.62 x lo6
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
1 0
26.1
34.52
10.0
114.39
7.2
87.0
56
2.88 x lo5
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
J
J
C J
J
C
F2
C
J
C
F2
19
C J
J
J
J
J
J
J
C D
F2
J
J
F2
C
C
J
J
J
C
A. R
320
86
320
370
370
1 5
390
86
41
7 1
152
324
7
7 1
441
86
441
345
346
86
86
145,232
390
208
86
442
289
1 4 5
289
390
184
184
4 1
370
1 5
390
5 1
15
86
5 1
5 1
1 5
5 1
5 1
5 1
5 1
5 1
214
86
86
442
86
86
86
86
390
7 1
232
420
370
338
338
390
539
TABLE 4. contd
Transfer Constants to Solvents and Additives II / 149
Solvent/Additive T (Cl cs (xlO4) Remarks Refs.
Vinyl acetate (contd)
Silane, methyldichloro-
-, trichloro-
-, triethyl-
-, triphenyl-
Stearamide, N-allyl-
Steak aci d, ehtyl est er
methyl ester
&cinic acid, diethyl ester
-, dihexyl ester
-, dimethyl est er
m-Tolualdehyde
p-Tolualdehyde
To l u e n e
-, bromo-
-, o-chloro-
-, p-chloro-
-, a-chloro-
Toluene, p-nitro-
p-Toluidine
-, N,N-dimethyl-
-, N-methyl-
Toluonitrile
Triethylamine
Tr i p h e n y l e n e
Ve r a t r a l de yhyde
Xy l e n e
Vinyl chloride
Carbon tetrachloride
Chloroform
Bromotrichloromethane
Vinylidene chloride
N-Methylpyrolidone
2-Vinylpyridine
Silane, diethylchloro-
-, Methyldichloro-
-, trichloro-
-, triethyl-
-, triphenyl-
Vinyltrimethylsilane
Bromoform
60
60
60
60
90
50
60
60
60
60
60
60
50
60
60
70
75
80
50
70
70
60
70
75
50
50
50
50
50
50
60
50
60
50
70
75
60 280
Q(3)
60 290
Q(3)
60 400000
Q(3)
50
60
60
60
60
60
60
5800
8800
1200
2700
620.1
140
38.2
4 1
40
3 1
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
20
20
5400
8600
12000
2000
4000
1200000
A R
A R
A R
A, R
C J
C
J
J
R
C
R
C
J
F2
w15
R
C
C
F2
F2
F2
F2
J
J
J
C
C
R
R
A R
A, R
A R
A R
A R
539
539
539
539
1 7 3
7 1
441
420
420
420
86
86
158
15
357
7 1
7 1
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
1 5
390
184
511
511
511
541
5 4 1
539
539
539
539
539
C Q(l-2) 572
Remarks page II - 157; References page II - 159
II/l50 TRANSFER CONSTANTS I N FREE RADI CAL POLYMERI ZATI ON
TABLE 5. TRANSFER CONSTANTS TO SULFUR COMPOUNDS
Modifier T(C) cx
Remarks Refs.
Acrylamide, N-octadecyl-lacrylonitrile (1: 1 mol ratio)
1-Dodecanethiol
Acrylic acid
1-Dodecanethiol
-, methyl ester
I-Butanethiol
Ethanethiol
60
45
30
60
50
0.539 C. F24 174
1.9 C, F31 549
6 0
1.53
1.69
0.78
0.94 f 0.07
1.65f0.12
1.57 f 0.09
1.57 f0.18
1.79
5.00
0.544
0.668
0.700
0.656
397
69,397
330
478,507
478,507
508
330,509
330
330
477
477
477
477
50
50
20
30
40
50
80
50
0.73
0.13
0.1
0.47
0.00008 12
0.11
0.29
0.795
0.69
0.97
J
378
378
248
196
458
404
197
375
8 5
378
5 1.5 C. H 380
53.3 C, H
380
5 1.2 C. H 380
5 2.1 C H
380
5 1.1 C H 380
5 1.8 C, H 380
50 1.02 C. H 380
6 0 6.9
6 0 8.1
60 7.5
60 8.3
532
532
532
532
5
50
5
50
50
50
5.3
3.7
21.8
16.0
19.0
3.0
19.5
242
242
242
242
243
242
242
5 0.66 B, H, J 384
5 2.42 J% H, J
383
2Propanethiol
Acrylonitrile
1-Dodecanethiol
Hydrogen sulfide
Methyl sulfoxide
Methyl tetrasulfide
p-Toluenethiol
Acrylonitrile/l,3-butadiene (lo-90%)
1-Hexanethiol,
-, 1,1,3,3,5,5-hexamethyl-
1-Pentanethiol,
-, 1,1,3,3-tetramethyl-
Acrylonitrile/l,3-butadiene (20-80%)
1-Hexanethiol
-, 1,1,3,3,5,5-hexamethyl-
1-Pentanethiol
-, 1,1,3,3-tetramethyl-
Acrylonitrile/l,3-butadiene (30-70%)
1-Hexanethiol
-, 1,1,3,3,5,5-hexamethyl-
1-Pentanethiol
-, 1,1,3,3-tetramethyl-
Acrylonitrilelstyrene (38. 5-61. 5 mol%)
1-Pentanethiol
-, 1,1,3,3,4-pentamethyl-
Butadiene
Xanthogendisulfide, dibutyl-
-, diethyl-
-, di-2-ethylhexyl-
-, di-isopropyl-
1,3-Butadiene
I-Butanethiol, 1,1,3,3-tetramethyl-
1-Octanethiol
-, 1,1,3,3,5,5,7,7-octamethyl-
1-Tetradecanethiol
1,3-Butadienektyrene
1-Dodecanethiol
Formic acid, thio-, dithiobis-
-, -, -3
O,O-dibutyl ester
TABLE 5. contd
Transfer Constants to Sulfur Compounds II/151
Modi fi er T (0 cx
Remarks Refs.
1,3-Butadienelstyrene (contd)
-, -7 -7 0, 0-di-set-butyl ester
-1 -7 - 0, 0-dicyclohexyl ester
-, -7 -7 0, O-diethyl ester
-1 -7 -, O,O-diheptyl est er
-1 -1 -7 O,O-dihexyl est er
-1 -9 -9 O,O-diisobutyl ester
-3 -1 O,O-diisopentyl ester
-9 -1 -1 O,O-diisopropyl ester
-, -9 -9 O,O-dimethyl est er
-3 -1 -1 O,O-dineopentyl ester
-9 -, -9 O,O-dioctyl ester
-1 -3 -1
O,O-dipentyl ester
-1 -1 -1
O,O-dipropyl ester
1-Heptanethiol
-, 1,1,3,3,5,5,6-heptamethyl-
I-Hexanethiol
-, 1,1,3,3,5,Shexamethyl-
1- Oc t a ne t hi ol
-, 1,1,3,5,5,7,7-octamethyl-
p-Dioxin, 2,3-dihydro/maleic anhydride
I-Butanethil
Et h y l e n e
1-Butanethiol
Ethyl sulfide
Methyl sulfoxide
2-Propanethiol, 2-methyl-
Sulfur hexafluoride
Methyl methactylate
Acetic acid, dithiodi-, diethyl ester
mercapto-, methyl ester
Letophenone, 3-mercapto-
-, 4-mercapto-
- 5
50
5
- 5
5
50
5
- 5
50
5
50
5
50
5
- 5
50
5
- 5
50
5
-
- 5
50
5
- 5
50
5
50
5
50
5
- 5
50
5
- 5
50
5 0.64 B, H, J
384
5
5 0.34
B, K J
384
60 6300 R 169
130 5.8 c, w5 457
130 0.027 c, w5 454
130 1 2 C, F21, W5 259
130 15.0 c, w5 457
130 o.oooo C, F21, W5 259
60 0.00065 86
60 0.63 274
45 4.2 30
45 2.6 30
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
1.22
B, H, J
384
4.1 H 54,55
2.7-4.7 H 54
H
C, H, J
B, H, J
H
B, H, J
C, H, J
B, K J
H
C K J
B, H, J
C K J
B, H, J
C H, J
B, K J
H
C K J
B, K J
B, K J
H
C K J
B, K J
B, H, J
B, H
B, H, J, GG4
B, H, J, GG3
B, H, J, GG2
B, H, J, GGl
B, H, J, GG5
H
C, H, J
B, H, J
H
C, H, J
B, H, J
C, H, J
JA H, J
C, H, J
B, K J
H
C K J
B, K J
H
C H, J
180
382
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
Remarks page II - 157; References page II - 159
II / 152 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 5. contd
Modifier T (Cl CX
Remarks Refs.
Methyl methacrylate (contd)
Anisole, 4,4-dithiodi-
p-Anisoyl disulfide
Benzenesulfonic acid
-,
compound with pyridine
-, thio-, Sphenyl est er
Benzenethiol
50 0.0044 285
60 0.0052 285
60 14.6 369
-, m-bromo-
-,p-bromo-
-, m-chloro-
-, p-chloro-
Benzoyl disulfide
Benzyl disulfide
Benzyl sulfide
60
60
45
60
70
45
4.5
4.5
45
60
2 5
50
60
25
50
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-
-1 -1 3,3 -dimethoxy-
-1 -1 3,3-dimethyl-
-3 -, 4,4-dimethyl-
-, 3,3-dinitro-
&bon di sul f i de
2,13-Dioxa-7,8-dithia-3,12-disila-tetradecane, 3,3,12,12-tetrameth oxy-
Disulfide, bis(p-bromobenzoyl)-
-, bis (p-bromophenyl)-
-, bis(p-chlorobenzoyl)-
-, bis@-chlorophenyl)-
-, bis(p-cyanobenzoyl)-
-, bis(dimethylthiocarbamoyl)-
-, bis(p-nitrobenzoyl)-
-, bis(o-nitrophenyl)-
-, bis(p-nitrophenyl)-
1-Dodecanethiol
Ethanethiol, 2-amino-, hydrochloride
Ethanol, 2-mercapto-
Ethyl disulfide
Formamidine, N,N-diphenyl-
-, 1,l -dithiobis-
Methyl sufoxide
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
50 0.22 C, F2 251
60 0.0000071 A 438
0.00365
0.0196
4.7
2.7
1 5
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
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
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
TABLE 5. contcf
Transfer Constants to Sulfur Compounds I I / 153
Modifier
T (0 CX
Remarks Refs.
Methyl methacrylate (contd)
2-Naphthalenetbiol
I-Penthanethiol
Phenyl disulfide
Phenyl disufone
Phenyl sulfide
Phenyl sulfone
Phenyl sulfoxide
lPropanetbio1, 3-[1,3,3,3-tetramethyl-1-(trimethylsiloxy)disiloxanyl]-
-, 3-(trimethoxy)-
2Propanethiol
-, 2-methyl-
Propionic acid, 3-mercapto-
Sulfide, benzoyl dimethylthiocarbamoyl
Sulfur
Thiosulfuric acid, S-butyl ester
-, -, sodium salt
-, S-isopropyl ester
-3 -, sodium salt
-, S-phenyl ester
-1 -1 compound with pyridine
-1 -, potassium salt
-, S-propyl ester
-, -, sodium salt
m-Toluenethiol
p-Toluenethiol
a-Toluenethiol
p-Toluoyl disulfide
p-Tolyl disulfide
St y r e n e
Acetic acid, dithiodi-
-9 -9 diethyl ester
-, -1 dimethyl est er
-9 -, mercapto-
-, -9 butyl ester
-1 -1 ethyl ester
-, -1 methyl ester
-, phenyl-
-9 -, p,p-dithiodi-
-, t h i o
Aniline, 2,2 dithiodi-
-, 4,4-dithiodi-
-, N-dodecyl-, 4,4-dithiodi-
Anisole, 2,2-dithiodi-
-, 4,4-dithiodi-
-, p-methyl-, u,u-dithiobis-
45
60
50
25
50
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
H
D
60
25
50
60
50
50
19.5
79.5
60
60
50
70
20
60
A
A
D
F2
F2
D
A
C
F2, J
30
274
344
368
285
310
368
285
491
491
368
252
368
252
252
414
474
274
274
473
473
280
280
118
194
354
60 0.00226 490
60 0.00167 490
60
60
0.374
0.00537
490
490
60 0.00190
45 4.7
45 7.4
50 0.027
60 11.0
50 0.003 1
60 0.0044
R J
490
30
30
354
369
285
285
50 < 0.005
99 0.2
60 0.015
99 0.1
99 >14.0
50 26.0
60 58.0
60 0.63
99 21.6
J, R
A
A
297
96
86
96
96
146
126
323
96
50
99
25
50
J
15
50
50
50
50
99
0.24
>14.7
3.8
3.0
3.4
3.0
0.24
0.21
3.0
0.18
0.021
89
96
297
297
297
297
89
89
89
89
96
Remarks page II - 157; References page II - 159
II 1154 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 5. contd
Modifier T (Cl CX Remarks
-
Refs.
Styrene (co&d)
p-Anisoyl disulfide
Anthranilic acid, 4,4-dithiobis-
Arylbenzene thiolsulfonate
-, p-chloro-
-, p-methoxy-
-, p-methyl-
Benzenesulfonic acid
-, compound with pyridine
-1 thio-, S-phenyl ester
Benzenethiol
-, o-ethoxy-
-, p-ethoxy-
Benzene thiosulfonate
-, aryl-p-chloro-
-, aryl-p-methoxy-
aryl-p-methyl
i:Benzimidazolethiol
Benzoic acid, 2,2-dithiodi-
-, -1 diethyl ester
-, -,dimethyl ester
-, 4,4-dithiodi-
-1 -, diethyl ester
-, o-mercapto-
-3 -7 methyl ester
-, thio-
Benzothiazole, 2,2-dithiobis-
-, 2,2-thiobis-
2-Benzothiazolethiol
Benzo[B]thiophene, 4,5,6,7-tetrahydro-4(2-thienyl)-
Benzoyl disulfide
Benzyl alcohol, o,o-dithiobis-
-, p,p-dithiobis-
Benzyl diselenide
Benzyl disulfide
Benzyl sulfide
Benzyl sulfone
Benzyl sulfoxide
1-Butanethiol
60 96.0
50 3.0
60 0.95
60 2.22
60 1.872
60 1.237
60 0.00617
50 1.60
60 1.67
99 0.08
99 25.1
99 0.13
60
60
60
99
50
50
99
50
50
99
99
99
25
50
7 5
99
50
50
99
60
50
60
99
50
50
60
50
60
99
25
50
60
50
50
2 5
60
70
80
99
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. 05 1
5.4
13.2
21.0
22.0
25
15.0
17.0
15.4
R ~2
R, F2
R, F2
R. F2
A
A
R, F2
R, F2
R, F2
J
A
A
D
J A Ql
D
A
A
A
A
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
291
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
1 3 1
395
395
96
TABLE 5. contd
Transfer Constants to Sulfur Compounds II / 155
Modifier
T (C) CX
Remarks Refs.
Styrene (contd)
1-Butanethiol, 1,1,3,3-tetramethyl-
1-Butanethiol-D
Butyl disulfide
set-Butyl disulfide
rerr-Butyl disulfide
Butyl sulfide
tert-Butyl sulfide
Carbanilic acid, p,p-dithiodi-diethyl ester
Carbon disulfide
Carbonic acid, dithio-
-1 -3
S,S-bis(carboxymethyl)ester
-, trithio-
-, -I
S,S-bis(carboxymethy1) est er
1-Decanethiol
2,13-Dioxa-7,8-dithia-3,12-disilatetradecane, 3,3,12,12-tetramethoxy-
Diphenyldisulfide
Disulfide, bis(p-bromobenzoyl)
-, bis(cr-bromo-o-tolyl)
-, bis(p-chlorobenzoyl)
-, bis(chlorobenzy1)
-, bis(Zchloroethy1)
-, bis(cc-chloro-o-tolyl)
-, bis(p-cyanobenzoyl)
-, bis(diethylthiocarbamoy1)
-, bis(dimethylthiocarbamoy1)
-, bis(2-ethylhexyl) 50
-, bis(N-ethyl-N-phenylthio-carbamoyl) 60
-, bis(l-methylheptyl) 99
-, bis(morpholinothiocarbony1) 60
-, bis(l-naphthylmethyl) 99
-, bis(p-nitrobenzoyl 60
-, bis(o-nitrophenyl) 50
-, bis(l-phenylethyl) 50
-, bis(P-(2-pyridyl)ethyl) 50
-, bis(2,3,5,6-tetramethylphenyl) 50
-, bis(2,4,6-triisopropylphenyl) 50
1- Dode c a ne t hi ol 60
5
5 0
60
70
80
2 5
5 5
60
99
150
50
50
60
60
60
50
60
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
A
A
242
222
242
395
395
395
448
448
304
96
359
89
89
304
304
304
89
288
50 0.36 297
50
80
80
79.5
60
60
50
60
50
50
50
60
60
60
70
80
C3, H
C3, H
95
1 1 5
130
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
1 9
0.69
1.3
13.0
26.0
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
i9,126
59
562
574
574
156
156
A c
70
70
90
100
110
C3, H
C3, H
Remarks page II- 157; References page II- 159
II / 156 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
TABLE 5. contd
Modifier
T (0 CX
Remarks Refs.
St yrene (contd)
tert-Dodecanethiol
Ethanethiol
Ethanol, 2,2-dithiodi-
-, di(chloroacetate)
Eiher, ethyl 3-mercaptopropyl
Ethyl disulfide
Formamidine, NJdiphenyl-, 1,l -dithiobis-
Formic acid, thio-, dithiobis, O,O-diisopropyl ester
I-Heptanethiol
1 -Hexanethiol
-, 1,1,3,3,5,5hexamethyl-
Hexyl disulfide
Hydrogen sulfide
Isobutyl disulfide
Isopropyl disulfide
Lauryl disulfide
Lepidine, 2,2dithiodi-
Mesityl disulfide
Methyl disulfide
Methyl sulfoxide
Morpholine, 4,4-dithiodi-
1-Naphthalenemethanethiol
I-Naphthalenethiol
2-Naphthalenethiol
1-Naphthoyl disulfide
1-Naphthyl disulfide
2-Naphthyl disulfide
1-Octadecanethiol
Octadecyl disulfide
1-Octanethiol
-, 1,1,3,3,5,5,7,7-octamethyl-
2-Octanethiol
1,4,5-Oxadithiepane
I-Pentanethiol
Phenetole, 2,2-dithiodi-
-, 4,4-dithiodi-
Phenyl disulfide
Phenyl disulfone
Phenyl sulfide
70
90
90
50
50
50
60
100
99
50
50
99
99
99
25
50
7 5
99
70
60
60
60
50
50
60
40
50
60
50
2 5
50
75
99
99
99
50
99
25
50
75
99
99
99
5
50
50
99
150
50
99
99
50
60
50
60
25
50
60
1.5
1.5
1.6
17.1
< 0.005
< 0.005
14.1
21.0
13.7
0.0045
6.72
5.3
7.5
15.1
15.3
3.2
2.9
2.4
0.0104
5.0
0.0020
0.00066
0.00023
0.04
0.69
0.0094
0.0000693
0.548
0.0000242
0.000048
<0.005
12.7
18.3
15.7
24.6
0.15
0.18
0.34
1.57
0.17
0.19
0.29
0.36
14.7
0.024
19.3
23.0
19.0
4.7
3.2
0.057
20.0
0.075
0.33
0.06
0.102
0.0103
0.111
0.147
0.022
0.025
0.0325
0.056
0.00548
C3, H
C3, H
C3, H
A
C, F2
H
H
H
H
A
H
A
A
A
A
D
574
574
574
331
297
297
126
69
69
96
251
297
96
96
96
297
297
297
96
1 4 5
304
304
128
89
89
304
458
375
429
438
297
297
297
297
96
96
96
89
96
297
297
297
96
96
96
339
242
242
242
96
359
344
96
96
297
491
368
491
285
491
491
368
252
368
T A B L E 5 . contcf
Modifier
T (C) CX
Remarks II / 157
Remarks Refs.
Styrene (co&d)
Phenyl sulfone
Phenyl sulfoxide
1-Propanethiol, S-(trimethoxysilyl)-
2Propanethio1, 2-methyl-
50
50
79.5
50
60
60
100
Propionic acid, 3,3-dithiodi-
-, -9 dipropyl ester
-, 2-mercapto-
-, S-mercapto-
Propyl disulfide
Pyridine, 2,2-dithiodi-
Quinoline, 2.2.dithiodi-
Sulfide, ethyl 2,Cdiphenylbutyl
-, ethyl phenethyl
I-Tetradecanethiol
Thiosulfuric acid, S-butyl ester
-, -,
sodium salt
-, S-isopropyl ester, sodium salt
-, S-phenyl est er
-, - potassium salt
-, Spropyl ester, sodium salt
p-Toluenethiol
a-Toluenethiol
-, p-methoxy-
p-Toluoyl disulfide
o-Tolyl disulfide
p-Tolyl disulfide
2,6-Xylyl disulfide
Vinyl acetate
Acetic acid, dithiodi-
15
50
99
50
-, -, diethyl ester 60
Acetic acid, ithio-
-, S-(2-hydroxyethyl)ester, acet at e
2cetyl disulfide
1 - Bu t a n e t h i o l
Butyl disulfide
Butyl sulfide
1,4,5-Oxadithiepane
Su l f u r
u-Toluenethiol
Thiol acetate
50
-
-
50
60
50
50
50
50
50
60 0.173 490
60 0.407 490
60
60
99
99
99
60
25
50
60 0.0132
60 0.29
60 48.0
60 1.0
60 0.026
60 0.25-2.5
45 470.0
IO 0.885
60 0.186
0.021
0.024
5.90
4.0
3.1
3.7
4.6
1.8
2.3
252
252
414
344
261
69,126
59
261
69,126
< 0.005
7.7
9.4
6.0
0.00234
0.01
0.05
30.0
7.15
19.0 H
297
1 7 8
178
291
304
89
89
331
331
242
0.763 490
0.150 490
0.07 96
25.5 96
26.0 96
46.3 369
0.22 297
0.23 291
0.28 291
0.32 291
0.11 291
0.15 96
0.69 291
1.41
1.5
86
351
J
J
J
J
J
C
F20
140
86
140,397
86, 351
351
3 5 1
28
390
515
C. REMARKS
A. Thermal initiation E . y-Ray initiation
B. Hydroperoxide initiation F. Solution polymerization in:
C. Peroxide initiation Fl. Acetonitrile
Cl. Ammonium per-sulfate F2. Benzene
c2. Potassium persulfate F3. Butyl acetate
c3. Sodium persulfate F4. Butyl chloride
D. Photoinitiation F5. Chlorobenzene
References page II - 159
II / 158 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
F6. o-Dichlorobenzene
F7. Dimethylformamide
F8. Dimethyl sulfoxide
F9. p-Dioxane
FlO. Ethyl acetate
Fl 1. Ethyl methyl ketone
F12. Heptane
F13. Water
F14. Magnesium perchlorate
F1.5. Succinonitrile
F16. Sulfur dioxide
F17. Toluene
F18. Zinc chloride
F19. Octane
F20. Methanol
F21. Propane
F22. Diethyl oxalate
F23. Cyclohexane
F24. Butyl alcohol
F25. Acetic acid
F26. 1 ,ZDichloroethane
F27. Ethylbenzene
F28. Cylohexanone
F29. Parabutyr aldehyde
F30. Water-methanol mixture
F3 1. tert-Butyl alcohol
F32. Hexane
F33. 1 -Propanol
F34. Carbon tetrachloride
G. Heterogeneous polymerization
H. Emulsion polymerization
I . Recalculated from data of:
Il. Basu, Sen, and Palit (1950)
1 2 . Baysal and Tobolsky (1952)
13. Chadha and Misra (1958)
14. Dixon-Lewis (1949)
15. Gregg and Mayo (1953)
16. Ham (1956)
17. Kwart, Broadbent, and Bartlett (1950)
18. Matsumoto, et. al. (1959)
1 9 . Palit and Das (1954)
1 1 0 . Palit, Nandi, and Saha (1954)
Ill. Saha, Nandi, and Palit (1956)
1 1 2 . Stein and Schulz (1960)
113. Wheeler, Lavin, and Crozier (1952)
J . Apparent transfer constant; retardation occurred
K. Average value
L . Estimated from model compounds
M. For end groups:
Ml. Tribromomethyl
M2. Butylamino
M3. Diethylamino
M4. Hydroxymethyl
M5. Aldehyde
M6. Thioglycolate
M7. -CH(OH)CH2-SH
M8. Dodecyl
M9. 2-Hydroxyethyl
MlO. -(CH2)i1SH
N. For middle groups
0. For side chain
P. For main chain
Q. Telomerization (number of monomer units in
transferring chain)
R. Calculated from viscosity average molecular
weight
S . Value uncertain
T. In presence of 0.4moVl lithium nitrate
U. In presence of ( ) mol/l sodium chloride
V. In presence of ( ) mol/l sodium bromide
W. Under pressure of:
Wl. 200psi (13.8 bar)
W2. 250 psi (17.2 bar)
w3. 1470psi (101.4bar)
W4. 5000 psi (344.8 bar)
W5. 20000 psi (1379.0 bar)
W6. 26600 psi (1834.1 bar)
W7. 28400 psi (1958.2 bar)
W8. 56000psi (3861.2bar)
W9. 64600 psi (4454.2 bar)
WlO. 168000psi (11583.6bar)
Wll. 6OOpsi (41.4bar)
W12. 2500psi (172.4bar)
W13. 18psi (1.2bar)
W14. 735 psi (50.7 bar)
W15. 14200psi (979.1 bar)
W16. 42600 psi (2937.3 bar)
W17. 34500psi (2378.8 bar)
W18. 3000bar
W19. 2700 bar
W20. 2400 bar
W21. 2000bar
W22. 1800 bar
W23. 150bar
W24. 600 bar
X. Corrected for loss of low molecular weight
polymer
Y. CM = 125 x exp(-7300/RT)
Z. CM = 3.0 x exp(-5673/RT)
AA. CM = 0.4 x exp(-6219/RT)
BB. CM = 0.2 x exp(-5400/RT)
CC. CM = 6.4 x exp(-4120/RT)
DD. CM = 4.77 x exp(-3540/RT)
EE. Radical is styrene
FF. Radical is p-chlorostyrene
GG. l/C varies with polym. rate and emulsifier of:
GGl. K caprate
GG2. K laurate
GG3. K myristate
GG4. K palmitate
GG5. K rosinate
HH. C is combined constant for copolymerization,
= (CSI x RI x Mr + Cs2 x R2 x M2)/
(RI xMt xMrf2xMi xM2
+R2 x M2 x M2)
II. In presence of FeBr2
Re f e r e n c e s II / 159
111. In presence of FE(CO)s
112. In presence of methacrylic acid methyl ester
JJO. Catalyzed by Co(II)-tetramethylhematoporphyrine
JJl. Catalyzed by Co(II)-hematoporphyrine-
tetramethyl ether
JJ2. Catalyzed by Co(II)-tetra4-tert-
butylbenzoporphyrine
D. REFERENCES
1. I. B. Afanasev, T. N. Eremina, Zh. Org. Khim., 2, 1832
(1966).
2. I. B. Afanasev, T. N. Eremina, E. D. Safronenko, Zh. Org.
Khim., 1, 844 (1965); J. Org. Chem. USSR, 1, 849 (1965).
3. I. B. Afanasev, E. D. Safronenko, A. A. Beer, Vysokomol.
Soedin., Ser. B, 9, 802 (1967).
4. G. Akazome, S. Sakai, K. Maurai, Kogyo Kagaku Zasshi,
63, 592 (1960); from CA, 56, 4924F (1962).
5. L. Alexandru, M. Oprish, Polym. Sci. USSR, 3, 99 (1962).
6. P. W. Allen, G. P. Mcsweeney, Trans. Faraday Sot., 54,715
(1958).
7. P. W. Allen, F. M. Merrett, J. Scanlan, Trans. Faraday Sot.,
51, 95 (1955).
8. U. N. Anistmov, S. S. Ivanchev, A. I. Yurzhenko, Vysoko-
mol, Soedin., Ser. A, 9, 692 (1967).
9. I. A. Arbusova, L. I. Medvedeva, Izv. Akad. Nauk SSSR, Ser.
Khim., 1957, 1349.
10. T. Asahara, T. Makishima, Kogyo Kagaku Zasshi, 69, 2173
(1966).
11. C. Aso, M. Sugabe, Kogyo Kagaku Zasshi, 68, 1970
(1965).
12. R. Autrata, J. Muller, Collect. Czech. Chem. Commun., 24,
3442 (1959).
13. D. W. E. Axford, Proc. Roy. Sot., Ser. A, 197, 137
(1949).
14. T. M. Babchinitser, K. K. Mozgova, V. V. Korshak, Dokl.
Akad. Nauk SSSR, 173,575 (1967); from CA, 67,117314E
(1967).
15. Kh. S. Bagdasarian, Z. A. Sinitsina, J. Polym. Sci., 52, 31
(1961).
16. C. H. Bamford, S. Brumby, Makromol. Chem., 105, 122
(1967).
17. C. H. Bamford, M. J. S. Dewar, Proc. Roy. Sot., Ser. A, 192,
309 (1948).
18. C. H. Bamford, M. J. S. Dewar, Proc. Roy. Sot., Ser. A, 197,
356 (1949).
19. C. H. Bamford, A. D. Jenkins, R. Johnston, Proc. Roy. Sot.,
Ser. A, 239, 214 (1957).
20. C. H. Bamford, A. D. Jenkins, R. Johnston, Proc. Roy. Sot.,
Ser. A, 241, 364 (1957).
21. C. H. Bamford, A. D. Jenkins, R. Johnston, Trans. Faraday
Sot., 55, 418 (1959).
22. C. H. Bamford, A. D. Jenkins, R. Johnston, E. F. T. White,
Trans. Faraday Sot., 55, 168 (1959).
23. C. H. Bamford, A. D. Jenkins, E. F. T. White, J. Polym. Sci.,
34, 271 (1959).
24. C. H. Bamford, E. F. T. White, Trans. Faraday Sot., 52,716
(1956).
553. In presence of ZnC12; [ZnClz]/[MMA] =
(a> 0
(b) 0.1
(c) 0.23
(d) 0.40
KK. Copolymerization of acrylonitrile and butyl acrylate
LL. Controlled to pH 3-4 with acetic acid
25. C. H. Bamford, E. F. T. White, Trans. Faraday Sot., 54, 268
(1958).
26. S. Banerjee, M. S. Muthana, J. Polym. Sci., 37,469 (1959).
27. P. D. Bartlett, G. S. Hammond, H. Kwart, Dis. Faraday Sot.,
2, 342 (1947).
28. P. D. Bartlett, H. Kwart, J. Am. Chem. Sot., 74, 3969
(1952).
29. P. D. Bartlett, F. A. Tate, J. Am. Chem. Sot., 75, 91 (1953).
30. S. C. Barton, R. A. Bird, K. E. Russell, Can J. Chem., 41,
2737 (1963).
31. S. Basu, J. N. Sen, S. R. Palit, Proc. Roy. Sot., Ser. A, 202,
485 (1950).
32. S. Basu, J. N. Sen, S. R. Palit, Proc. Roy. Sot., Ser. A, 214,
247 (1952).
33. B. Baysal, J. Polym. Sci., 33, 381 (1958).
34. B. Baysal, A. V. Tobolsky, J. Polym. Sci., 8, 529 (1952).
35. I. M. Belgovskii, L. S. Sakhonenko, N. S. Yenikolopyan,
Vysokomol. Soedin., 8, 369 (1966).
36. W. I. Bengough, W. H. Fairservice, Trans. Faraday Sot., 61,
1206 (1965).
37. W. I. Bengough, W. H. Fairservice, Trans. Faraday Sot., 63,
382 (1967).
38. W. I. Bengough, W. Henderson, Trans. Faraday Sot., 61,141
(1965).
39. W. I. Bengough, R. A. M. Thomson, Trans. Faraday Sot., 56,
407 (1960).
40. J. Beniska, E. Staudner, J. Polym. Sci. C, 16, 1301 (1967).
41. T. Berezhnykb-Wldes, F. Tudos, Eur. Polym. J., 2, 219
(1996).
42. J. C. Bevington, N. A. Ghanem, H. W. Melville, J. Chem.
SOL, 1995, 2822.
43. J. C. Bevington, G. M. Guzman, H. W. Melville, Proc. Roy.
Sot. Ser. A, 221, 437 (1954).
44. J. C. Bevington, H. G. Troth, Trans. Faraday Sot., 58, 2005
(1962).
45. J. C. Bevington, H. G. Troth, Trans. Faraday Sot., 59, 127
(1963).
46. J. C. Bevington, H. G. Troth, Trans. Faraday Sot., 59, 1348
(1963).
47. J. C. Bevington, A. Wahid, Polymer, 3, 585 (1962).
48. B. R. Bhattacharyya, U. S. Nandi, J. Polym. Sci. A-l, 4,2675
(1966).
49. B. R. Bhattacharyya, U. S. Nandi, Makromol. Chem. 116,8
(1968).
50. R. A. Bird, G. A. Harpell, K. E. Russell, Can. J. Chem., 40,
701 (1962).
51. R. A. Bird, K. E. Russell, Can. J. Chem., 43, 2123 (1965).
II / 160 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
52. L. Bogetich, G. A. Mortimer, G. W. Daues, J. Polym. Sci.,
61, 3 (1962).
53. E. P. Bonsall, L. Valentine, H. W. Melville, J. Polym. Sci., 7,
39 (1951).
54. C. Booth, L. R. Beason, J. Polym. Sci., 42, 93 (1960).
55. C. Booth, L. R. Beason, J. T. Bailey, J. Appl. Polym. Sci., 5,
116 (1961).
56. D. Braun, T.-O. 0. Ahn., W. Kern, Makromol. Chem., 53,
154 (1962).
57. D. Braun, G. Arcache, R. J. Faust, W. Neumann, Makromol.
Chem., 114, 51 (1968).
58. J. W. Breitenbach, Makromol Chem., 8, 147 (1952).
59. J. W. Breitenbach, Z. Elektrochem., 60, 286 (1956).
60. J. W. Breitenbach, H. Edelhauser, R. Hochrainer, Monatsh.
Chem., 97, 217 (1966).
61. J. W. Breitenbach, H. Karlinger, Mona&h. Chem., 82, 245
(1951).
62. J. W. Breitenbach, 0. F. Olaj, Makromol. Chem., 96, 83
(1966).
63. J. W. Breitenbach, 0. F. Olaj, K. Kuchner, H. Horacek,
Makromol. Chem., 87, 295 (1965).
64. J. W. Breitenbach, 0. F. Olaj, A. Schindler, Monatsh. Chem.,
91, 205 (1960).
65. J. W. Breintenbach, A. Schindler, Monatsh. Chem., 83, 724
(1952).
66. J. W. Breintenbach, A. Schindler, Monatsh. Chem., 86, 437
(1955).
67. J. W. Breintenbach, A. Schindler, Monatsh. Chem., 88, 53
(1957).
68. D. W. Brown, J. E. Fearn, R. E. Lowry, J. Polym. Sci. A, 3,16
(1965).
69. G. M. Burnett, Quart. Rev. (London), 4, 292 (1950).
70. G. M. Burnett, F. L. Ross, J. N. Hay, Makromol. Chem., 105,
1 (1965).
71. A. J. Buselli, M. K. Lindemann, C. E. Blades, J. Polym. Sci.,
28, 485 (1958).
72. J. I. G. Cadogan, D. H. Hey, J. T. Sharp, J. Chem. Sot., B,
1966, 933.
73. M. Cantow, G. Meyerhoff, G. V. Schulz, Makromol. Chem.,
49, 1 (1961).
74. E. A. S. Cavell, Makromol. Chem., 54, 70 (1962).
75. E. A. S. Cavell, I. T. Gilson, J. Polym. Sci. A-l, 4, 541
(1966).
76. R. N. Chadha, G. S. Misra, Indian J. Phys., 28, 37 (1954).
77. R. N. Chadha, G. S. Misra, Current Sci. (India), 23, 186
(1954).
78. R. N. Chadha, G. S. Misra, Makromol. Chem., 14,97 (1954).
79. R. N. Chadha, G. S. Misra, Current Sci. (India), 24, 26
(1955).
80. R. N. Chadha, G. S. Misra, Trans. Faraday Sot., 54, 1227
(1958).
81. R. N. Chadha, J. S. Shukla, G. S. Misra, Trans. Faraday Sot.,
53, 240 (1957).
82. E. Y. C. Chang, C. C. Price, J. Am. Chem. Sot., 83, 4650
(1961).
83. S. R. Chatterjee, S. N. Khanna, S. R. Palit, J. Indian Chem.
Sot., 41, 622 (1964).
84. A. K. Chaudhuri, Makromol. Chem., 31, 214 (1959).
85. S. Chubachi, P. K. Chatterjee, A. V. Tobolsky, J. Org. Chem.,
32, 1511 (1967).
86. J. T. Clarke, R. 0. Howard, W. H. Stockmayer, Makromol.
Chem., 44-46, 427 (1961).
87. W. Cooper, J. Chem. Sot. 1952, 2408.
88. A. T. Coscia, R. L. Kugel, J. Pellon, J. Polym. Sci., 55, 303
(1961).
89. A. J. Costanza, R. J. Coleman, R. M. Pierson, C. S. Marvel,
C. King, J. Polym. Sci., 17, 319 (1955).
90. J. Curtice, H. Gilman, G. S. Hammond, J. Am. Chem. Sot.,
79, 4754 (1957).
91. F. S. Dainton, R. G. Jones, Trans. Faraday Sot., 63, 15 12
(1967).
92. F. S. Dainton, M. Tordoff, Trans. Faraday Sot., 53, 499
(1957).
93. N. V. Daniel, A. F. Nikolaev, Vysokomol. Soedin., 8, 465
(1966).
94. F. Danusso, D. Sianesi, Chim. Ind. (Milan), 37, 695 (1955).
95. S. K. Das, S. R. Chatterjee, S. R. Palit, Proc. Roy. Sot., Ser.
A, 227, 252 (1955).
96. V. A. Dinaburg, A. A. Vansheidt, Zh. Obshch. Khim., 24,840
(1954).
97. G. Dixon-Lewis, Proc. Roy. Sot., Ser. A, 198, 510 (1949).
98. K. W. Doak, M. A. Deahl, I. H. Christmas, 137th ACS
Meeting, Cleveland, Ohio, Abstr. Papers, Vol. 1, No. 1, 151
(April 1960).
99. H. Drawe, A. Henglein, Makromol. Chem., 84, 203 (1965).
100. E. Dvorak, F. Hrabak, J. Polym. Sci. C, 16, 1051 (1967).
101. B. A. Englin, R. Kh. Freidlina, Izv. Akas. Nauk SSSR, Ser.
Khim., 1965 (13) 425; from CA, 63, 4122E (1965).
102. B. Erussalimsky, N. Tumarkin, F. Duntoff, S. Lyubetzky,
A. Goldenberg, Makromol. Chem., 104, 288 (1967).
103. T. A. Fadner, H. Morawetz, J. Polym. Sci., 45, 475 (1960).
104. T. E. Ferington, A. V. Tobolsky, J. Am. Chem. Sot., 77,451O
(1955).
105. T. G. Fox, S. Gratch, Ann. N. Y. Acad. Sci., 57, 367 (1953).
106. G. N. Freidlin, K. A. Solop, Vysokomol. Soedin., 7, 1060
(1965).
107. G. N. Freidlin, K. A. Solop, Vysokomol. Soedin., 8, 115 1
(1966).
108. T. M. Frunze, V. V. Korshak, E. L. Baranov, B. V. Lokshin,
Vysokomol. Soedin, 8, 455 (1966).
109. N. Fuhrma, R. B. Mesrobian, J. Am. Chem. Sot., 76, 3281
(1954).
110. T. R. Fukuto, J. P. Kispersky, US Dept. Corn., Office Tech.
Serv., Pb Rept. 147, 271 (1953).
111. S. Gadkary, S. Kapur, Makromol. Chem., 17, 29 (1955).
112. J. A. Gannon, E. M. Fettes, A. V. Tobolsky, J. Am. Chem.
Sot., 74, 1854 (1952).
113. M. H. George, J. Polym. Sci. A, 2, 3169 (1964).
114. M. H. George, P. F. Onyon, Trans. Faraday Sot., 59, 134
(1963).
115. M. H. George, P. F. Onyon, Trans. Faraday Sot., 59, 1390
(1963).
116. H. Gerrens, H. Ohlinger, R. Fricker, Markromol. Chem., 87,
209 (1965).
117. L. Ghosez, G. Smets, J. Polym. Sci., 37, 445 (1959).
118. G. P. Gladyshev, G. V. Leplyanin, Vysokomol. Soedin., Ser.
A, 9, 2438 (1967).
119. J. E. Glass, N. L. Zutty, J. Polym. Sci. A-l, 4, 1223 (1966).
120. M. S. Gluckman, M. J. Kampf, J. L. OBrien, T. G. Fox,
R. K. Graham, J. Polym. Sci., 37, 411 (1959).
121. M. P. Godsay, G. A. Harpell, K. E. Russell, J. Polym. Sci.,
57, 641 (1962).
122. M. P. Godsay, D. H. Lohmann, K. E. Russell, Chem. Ind.
(London), 1959, 1603.
123. M. R. Gopalan, M. Santhappa, J. Polym. Sci., 25, 333
(1957).
124. W. W. Graessley, H. Mittelhauser, R. Maramba, Makromol.
Chem., 86, 129 (1965).
125. N. Grassie, E. Vance, Trans. Faraday Sot., 52 727 (1956).
126. R. A. Gregg, D. M. Alderman, F. R. Mayo, J. Am. Chem.
Sot., 70, 3740 (1948).
127. R. A. Gregg, F. R. Mayo, Disc. Faraday Sot., 2,328 (1947).
128. R. A. Gregg, F. R. Mayo, J. Am. Chem. Sot., 70, 2373
(1948).
129. R. A. Gregg, F. R. Mayo, J. Am. Chem. Sot., 75, 3530
(1953).
130. V. F. Gromov, A. V. Matveeva, P. M. Khomikovskii,
A. D. Abkin, Vysokomol. Soedin., Ser. A, 9, 1444 (1967).
131. J. Guillot, A. Guyot, Compt. Rend., Ser. C, 266,1209 (1968).
132. H. C. Haas, H. Husek, J. Polym. Sci. A, 2, 2297 (1964).
133. Y. Hachihama, H. Sumitomo, Technol. Repts. Osaka Univ.,
5, 491 (1955); from CA, 51, 8474B (1957).
134. Y. Hachihama, H. Sumitomo, Technol. Repts. Osaka Univ.,
5, 497 (1955); from CA, 51, 8474C (1957).
135. G. E. Ham, J. Polym. Sci., 21, 337 (1956).
136. G. E. Ham, E. L. Ringwald, J. Polym. Sci., 8, 91 (1952).
137. D. Hardy, K. Nytrai, N. Fedorova, G. Kovacs, Polym. Sci.
USSR, 4, 584 (1963).
138. D. Hardy, K. Nytrai, N. Fedorova, G. Kovacs, Vysokomol.
Soedin, 4, 1872 (1962).
139. D. Hardy, V. Spiegel, K. Nytrai, Polym. Sci. USSR, 2, 528
(1961).
140. G. Hardy, J. Varga, K. Nytrai, I. Tsajlik, L. Zubonyai,
Vysokomol. Soedin., 6, 758 (1964).
141. S. A. Harrison, W. E. Tolberg, J. Am. Oil Chem. Sot., 30,
114 (1953); talc. by F. R. Mayo and C. W. Gould (1964).
142. R. A. Hayes, J. Polym. Sci., 13, 583 (1954).
143. E. J. Henley, C. Chong, J. Polym. Sci., 36, 511 (1959).
144. G. Henrici-Olive, S. Olive, Makromol. Chem., 37, 71
(1960).
145. G. Henrici-Olive, S. Olive, Fortschr. Hochpolymer. Forsch.,
2, 496 (1961).
146. G. Hemici-Olive, S. Olive, Makromol. Chem., 53, 122
(1962).
147. G. Hen&i-Olive, S. Olive, G. V. Schulz, Makromol. Chem.,
23, 207 (1957).
148. G. Henrici-Olive, S. Olive, G. V. Schulz, Z. Phys. Chem.
(Frankfurt), 20, 176 (1959).
149. R. Hiddema, Proefschrift Rijks Universitat Groningen, 1953,
Ref. 16 in Breitenbach (1956).
150. K. Higashiura, Kogyo Kagaku Zasshi, 69, 349 (1966).
References II / 161
151. K. Higaashiura, M. Oiwa, J. Polym. Sci., A-l, 6, 1857
(1968).
152. F. Hrabak, M. Bezdek, Makromol. Chem., 115, 43 (1968).
153. F. Hrabak, M. Bezdek, Collect. Czech. Chem. Commun., 33,
278 (1968).
154. F. Hrabak, L. Jiresova, Collect. Czech. Chem. Commun., 26,
1283 (1961).
155. T. Huff, E. Perry, J. Am. Chem. Sot., 82, 4277 (1960).
156. T. Huff, E. Perry, J. Polym. Sci. A, 1, 1553 (1963).
157. F. Ide, K. Nakatsuka, H. Tamura, Kobunshi Kagaku, 23,45
(1965); from CA, 64, 17716G (1966).
158. F. Ide, K. Okano, S. Nakano, K. Nakstsuka, Shikizai Kyo-
kaishi, 40, 571 (1967); from CA, 69, 3162Q (1968).
159. J. L. Ihrig, S. P. Sood, J. Polym. Sci. A-3, 1573 (1965).
160. M. Imoto, K. Higashiura, Kobunshi Kagaku, 17,468 (1960);
from CA, 55, 229006 (1961).
161. M. Imoto, T. Otsu, T. Oda, H. Takatsugi, M. Matsuda, J.
Polym. Sci., 22, 137 (1956).
162. M. Imoto, T. Otsu, K. Tsuda, T. Ito, J. Polym. Sci. A-2,1407
(1964).
163. M. Imoto, K. Takemoto, H. Azuma, Makromol. Chem., 114,
210 (1968).
164. M. Imoto, K. Takemoto, Y. Nakai, Makromol. Chem., 48,80
(1961).
165. S. Imoto, T. Kominami, Kobunshi Kagaku, 15, 60 (1958);
from CA, 53, 86906 (1959).
166. S. Imoto, T. Kominami, Kobunshi Kagaku, 15, 279 (1958);
from CA, 54, 2803A (1960).
167. S. Imoto,,J. Ukida, T. Kominami, Kobunshi Kagaku, 14, 127
(1957); from CA, 52, 1670A (1958).
168. S. Imoto, J. Ukida, T. Kominami, Kobunshi Kagaku, 14,384
(1957); from CA, 52, 5024D (1958).
169. S. Iwatsuki, K. Nishio, Y. Yamashita, Kogyo Kagaku Zasshi,
70, 384 (1967).
170. V. Jaacks, F. R. Mayo, J. Am. Chem. Sot., 87,337l (1965).
171. D. H. Johnson, A. V. Tobolsky, J. Am. Chem. Sot., 74,938
(1952).
172. M. H. Jones, Can. J. Chem., 34, 108 (1956).
173. E. F. Jordan, Jr., B. Artymyshyn, A. N. Wrigley, J. Polym.
Sci. A-l, 6, 575 (1968).
174. E. F. Jordan, Jr., G. R. Riser, W. E. Parker, A. N. Wrigley, J.
Polym. Sci. A-2, 4, 975 (1966).
175. R. M. Joshi, Makromol. Chem., 53, 33 (1962).
176. H. Kaemmerer, F. Rocaboy, Compt. Rend. Ser. AB, 256,
4440 (1963).
177. H. Kaemmerer, F. Rocaboy, Makromol. Chem., 72, 76
(1964).
178. K. Kaeriyama, Nippon Kagaku Zasshi, 88,783 (1967); from
CA, 69, 196072 (1968).
179. M. Kalfus, J. Kopytowski, S. Lesniak, Z. Skupinska, Polim-
ery, 9, (2) 54 (1964); from CA, 62, 9325E (1965).
180. S. Kamenar, Chem. Zvesti, 14, 525 (1960); from Chem.
Zentr., 133, 493 (1961).
181. S. L. Kapur, J. Sci. Ind. Res., 108, 186 (1951).
182. S. L. Kapur, J. Polym. Sci., 11, 399 (1953).
183. S. L. Kapur, S. D. Gadkary, J. Sci. Ind. Res., 17B, 152
(1958).
II / 162 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
184. S. L. Kapur, R. M. Joshi, J. Polym. Sci., 14, 489 (1954).
185. K. Katagiri, K. Uno, S. Okamura, J. Polym. Sci., 17, 142
(1955).
186. M. Kato, H. Kamogawa, J. Polym. Sci. A-l, 4,277l (1966).
187. V. Ya. Katsobashvili, R. Ya. Chernaya, I. B. Afanasev,
Vysokomol. Soedin., Ser. B, 9, 342 (1967).
188. V. Ya. Katsobashvili, E. D. Safronenko, I. B. Afanasev,
Vysokomol. Soedin., 7, 823 (1965).
189. V. Ya. Katsobashvili, E. D. Safronenko, I. B. Afanasev,
Vysokomol. Soedin., 8, 282 (1966).
190. H. Kawakami, N. Mori, K. Kawashima, M. Sumi, Kogyo
Kagaku Zasshi, 66, 88 (1963); from CA, 59,4042B (1963).
191. H. Kawakami, N. Mori, M. Sumi, Kobunshi Kagaku, 20,408
(1963); from CA, 61, 13422D (1964).
192. W. Kern, D. Braun, Makromol. Chem., 27, 23 (1958).
193. S. N. Khanna, S. R. Chatterjee, U. S. Nandi, S. R. Palit,
Trans. Faraday Sot., 58, 1827 (1962).
194. J. L. Kite, J. Am. Chem. Sot., 76, 6274 (1954).
195. W. J. Kirkham, J. C. Robb, Trans. Faraday Sot., 57, 1757
(1961).
196. H. Kitagama, Kobunshi Kagaku, 20, 5 (1963); from Mak-
romol. Chem., 64, 229 (1963).
197. H. Kiuchi, M. Watanabe, Kobunshi Kagaku, 21, 37 (1964)
from CA, 61, 7107F (1964).
198. I. M. Kochnov, M. F. Sorokin, Polym. Sci. USSR, 6, 869
(1964).
199. M. Kubin, L. Zikmund, Collect. Czech. Chem. Commun.,
32, 535 (1967).
200. C. J. Kurian, M. S. Muthana, Makromol. Chem., 29, 1
(1959).
201. C. J. Kurian, M. S. Muthana, Makromol. Chem., 29, 19
(1959).
202. H. Kwart, H. S. Broadbent, P. D. Bartlett, J. Am. Chem. Sot.,
72, 1060 (1950).
203. K. S. Kwei, F. R. Eirich, J. Phys. Chem., 66, 828 (1962).
204. Z. Laita, J. Polym. Sci., 38, 247 (1959).
205. Z. Laita, Z. Machacek, J. Polym. Sci., 38, 459 (1959).
206. M. Lazar, J. Pavlinec, Chem. Zvesti, 15, 428 (1961); from
CA, 55, 22896C (1961).
207. M. Lazar, J. Pavlinec, J. Polym. Sci. A, 2, 3197 (1964).
208. M. Lazar, J. Pavlinec, Z. Manasek, Collect. Czech. Chem.
Commun., 26, 1380 (1961).
209. M. Lazar, R. Rado, J. Pavlinec, J. Polym. Sci., 53, 163
(1961).
210. F. M. Lewis, F. R. Mayo, J. Am. Chem. Sot., 76,457 (1954).
211. D. Lim, M. Kolinsky, J. Polym. Sci., 53, 173 (1961).
212. D. Lim, 0. Wichterle, J. Polym. Sci., 29, 579 (1958).
213. M. Litt, V. Stannett, Makromol. Chem., 37, 19 (1960).
214. J. R. Little, P. F. Hartman, J. Am. Chem. Sot., 88,96 (1966).
215. J. R. Little, L. W. Hartzel, F. 0. Guenther, F. R. Mayo,
private communication to C. Walling, Free radicals in
solution, Wiley, NY, 1957, p. 257.
216. S. Loshaek, E. Broderick, P. Bernstein, J. Polym. Sci., 39,
223 (1959).
217. A. I. Lowell, J. R. Price, J. Polym. Sci., 43, 1 (1960).
218. S. G. Lyubetskii, B. A. Dolgoplosk, B. L. Erusalimskii,
Polym. Sci. USSR, 3, 164 (1962).
219. Z. Machacek, F. Cermak, Chem, Prum., 16,604 (1966); from
CA, 66, 18907Y (1967).
220. G. Machell, G. N. Richards, J. Chem. Sot., 1961, 3308.
221. V. Mahadevan, M. Santhappa, Makromol. Chem., 16, 119
(1955).
222. K. L. Malik, Naturwissenschaften, 45, 385 (1958).
223. T. Manabe, T. Utsumi, S. Okamura, J. Polym. Sci., 58, 121
(1962).
224. M. S. Matheson, E. E. Auer, E. B. Bevilacqua, E. J. Hart, J.
Am. Chem. Sot., 71, 497 (1949).
225. M. S. Matheson, E. E. Auer, E. B. Bevilacqua, E. J. Hart, J.
Am. Chem. Sot., 71, 2610 (1949).
226. S. G. Matsoyan, N. N. Morlyan, F. S. Kinoyan, Vysokomol.
Soedin., 7, 1159 (1965).
227. M. Matsuda, S. Abe, N. Tokura, J. Polym. Sci. A, 2, 3877
(1964).
228. M. Matsuda, K. Matsumoto, N. Tokura, Kogyo Kagaku
Zasshi, 68, 1269 (1965).
229. M. Matsuda. N. Tokura, J. Polym. Sci. A, 2, 4281 (1964).
230. M. Matsuda, S. Fujii, J. Polym. Sci. A-l, 5, 2617 (1967).
231. M. Matsumoto, M. Maeda, J. Polym. Sci., 17, 438 (1955).
232. M. Matsumoto, J. Ukida, G. Takayama, T. Eguchi,
K. Mukumoto, K. Imai, Y. Kazusa, M. Maeda, Makromol.
Chem. 32, 13 (1959).
233. B. Matuska, J. Kossler, V. Srajer, Collect, Czech. Chem.
Commun., 23, 1456 (1958).
234. J. A. May, Jr., W. B. Smith, J. Phys. Chem., 72, 216 (1968).
235. F. R. Mayo, J. Am. Chem. Sot., 65, 2324 (1943).
236. F. R. Mayo, J. Am. Chem. Sot., 70, 3689 (1948).
237. F. R. Mayo, J. Am. Chem. Sot., 75, 6133 (1953).
238. F. R. Mayo. J. Am. Chem. Sot., 76, 5392 (1954).
239. F. R. Mayo, C. W. Gould, J. Am. Oil Chem. Sot., 41, 25
(1964).
240. F. R. Mayo, R. A. Gregg, M. S. Matheson, J. Am. Chem.
SOL, 73, 1691 (1951).
241. V. V. Mazurek, V. G. Gasan-Zade, G. T. Nesterchuk, Polym.
Sci. USSR, 6, 1587 (1964).
242. E. J. Meehan, I. M. Kolthoff, H. R. Sinha, J. Polym. Sci., 16,
471 (1955).
243. E. J. Meehan, I. M. Kolthoff, P. R. Sinha, J. Polym. Sci. A-2
4911 (1964).
244. F. W. Mellows, M. Burton, J. Phys. Chem., 66, 2164
(1962).
245. H. W. Melville, L. Valentine, Trans. Faraday Sot., 46, 210
(1950).
246. H. S. Mickley, A. S. Michaels, A. L. Moore, J. Polym. Sci.,
60, 121 (1962).
247. E. B. Milovskaya, T. G. Zhuravleva, Vysokomol. Soedin.,
Ser. A, 9, 1128 (1967).
248. E. B. Milovskaya, T. G. Zhuravleva, L. V. Zamoyskaya, J.
Polym. Sci., C, 16, 899 (1967).
249. Y. Minoura, Y. Enomoto, Kogyo Kagaku Zasshi, 70, 1021
(1967).
250. Y. Minoura, Y. Hayashi, M. Imoto, Kobunshi Kagaku, 15,
260 (1958); from CA, 54 2803F (1960).
251. Y. Minoura, T. Sugimura, J. Polym. Sci. A-l, 4, 2721
(1966).
252. Y. Minoura, T. Sugimura, T. Hirahara, Kogyo Kagaku
Zasshi, 70, 357 (1967).
253. Y. Minoura, N. Yasumoto, T. Ishii, Kogyo Kagaku Zasshi,
65, 1299 (1962); from CA, 58, 1538D (1963).
254. Y. Minoura, N. Yasumoto, T. Ishii, Makromol. Chem., 71,
159 (1964).
255. G. S. Misra, R. N. Chadha, Makromol. Chem., 23, 134
(1957).
256. G. S. Misra, R. C. Rastogi, V. P. Gupta, Makromol. Chem.,
50, 72 (1961).
257. T. Miyake, M. Matsumoto, Kogyo Kagaku Zasshi, 62, 1101
(1959); from CA, 57, 1534214 (1962).
258. Y. Mori, K. Sato, Y. Minoura, Kogyo Kagaku Zasshi, 61,462
(1958); from CA, 55, 4021F (1961).
259. G. A. Mortimer, J. Polym. Sci. A-l, 4,881 and 1895 (1966).
260. G. A. Mortimer, L. C. Arnold, J. Am. Chem. Sot., 84,4986
(1962).
261. M. Morton, J. A. Cala, I. Piirma, J. Am. Chem. Sot., 78,
5394 (1956).
262. M. Morton, I. Piirma, J. Am. Chem. Sot., 80, 5596 (1958).
263. M. Morton, I. Piirma, J. Polym. Sci. A, 1, 3043 (1963).
264. A. S. Nair, M. S. Muthana, Makromol. Chem., 47, 114, 128
(1961).
265. H. Nakamoto, Y. Ogo, T. Imoto, Makromol. Chem., 111, 93
(1968).
266. T. Nakata, T. Otsu, M. Imoto, J. Polym. Sci. A, 3, 3383
(1965).
267. T. Nakaya, K. Ohashi, M. Imoto, Makromol. Chem., 114,
201 (1968).
268. U. S. Nandi, I? Ghosh, S. R. Palit, Nature, 195, 1197 (1962).
269. A. F. Nikolaev, N. V. Meiya, G. A. Balaev, Vysokomol.
Soedin., 7, 2122 (1965).
270. K. Noma, Y. Tajima, M. Niwa, Sci. Eng. Rev. Doshisha
Univ., 3, 91 (1962); from CA, 59, 2955C (1963).
271. R. G. W. Norrish, J. l? Simons, Proc. Roy. Sot., Ser. A, 251,4
(1959).
272. A. M. North, A, M. Scallan, Polymer, 5, 447 (1964).
273. K. Nozaki, Disc. Faraday Sot., 2, 337 (1947).
274. 3. L. OBrien, F. Gornick, J. Am. Chem. Sot., 77, 4757
(1955).
275. J. L. OBrien, J. R. Panchak, T. G. Fox, Abstract of 124th
ACS Meeting, Chicago, 1953.
276. S. Okamura, K. Katagiri, Makromol. Chem., 28, 177
(1958).
277. S. Okamura, K. Katagiri, T. Motoyama, J. Polym. Sci., 43,
509 (1960).
278. S. Okamura, T. Motoyama, J. Polym. Sci., 58, 221 (1962).
279. S. Okamura, K. Takeya, Kobunshi Kagaku, 15,353 (1958);
from CA, 54, 8143 (1960).
280. M. Okawara, T. Nakai, E. Imoto, Kogyo Kagaku Zasshi, 69,
973 (1966).
281. 0. F. Olaj, J. W. Breitenbach, I. Hofreitere, Makromol.
Chem., 91, 264 (1966).
282. 0. F. Olaj, J. W. Breitenbach, I. Hofreitere, Makromol.
Chem., 110, 72 (1967).
283. P. F. Onyon, Trans. Faraday Sot., 51, 400 (1955).
284. P. F. Onyon, .I. Polym. Sci., 22, 19 (1956).
Re f e r e n c e s II / 163
285. T. Otsu, Y. Kinoshita, M. Imoto, Makromol. Chem., 73,225
(1964).
286. T. Otsu, K. Nayatani, Makromol. Chem., 27, 149 (1955).
287. T. Otsu, A. Shimizu, M. Imoto, J. Polym. Sci. B, 2, 973
(1964).
288. T. Otsu, K. Tsuda, N. Kita, Mem. Fat. Eng., Osaka City
Univ., 7, 95 (1965); from CA, 66, 95434U (1967).
289. S. R. Palit, S. K. Das, Proc. Roy. Sot., Ser. A, 226,82 (1954).
290. S. R. Palit, U. S. Nandi, N. G. Saha, J. Polym. Sci., 14, 295
(1954).
291. S. K. Patra, D. Mangaraj, Makromol. Chem., 111, 168
(1968).
292. J. Pavlinec, M. Lazar, J. Polym. Sci. C, 22, 297 (1968).
293. L. H. Peebles, J. Polym. Sci. A, 3, 341 (1965).
294. L. H. Peebles, J. T. Clarke, W. H. Stockmayer, J. Am. Chem.
Sot., 82, 4780 (1960).
295. J. J. Pellon, J. Polym. Sci., 43, 537 (1960).
296. E. Perry, J. Polym. Sci., 54, S-46 (1961).
297. R. Pierson, A. Costanza, A. Weinstein, J. Polym. Sci., 17,
221 (1955).
298. G. Platau, F. R. Eirich, R. B. Mesrobian, A. E. Woodward, J.
Polym. Sci., 39, 357 (1959).
299. A. Prevot-Bernas, J. Sebban-Danon, J. Chem. Phys., 53,418
(1956).
300. W. A. Pryor, J. Phys. Chem., 67, 519 (1963).
301. W. A. Pryor, D. M. Huston, T. R. Fiske, T. L. Pickering,
E. Ciuffarin, J. Am. Chem. Sot., 86, 4237 (1964).
302. W. A. Pryor, G. L. Kaplan, J. Am. Chem. Sot., 86, 4234
(1964).
303. W. A. Pryor, A. Lee, C. E. Witt, J. Am. Chem. Sot., 86,4229
(1964).
304. W. A. Pryor, T. L. Pickering, J. Am. Chem. Sot., 84, 2705
(1962).
305. W. A. Pryor, E. P. Pultinas, Jr., J. Am. Chem. Sot., 85, 133
(1963).
306. P. V. T. Raghuram, U. S. Nandi, J. Polym. Sci. A-l, 5,2005
(1967).
307. S. P. Rao, M. Santhappa, Curr. Sci. (India), 34, (6) 174
(1965).
308. S. I? Rao, M. Santhappa, J. Polym. Sci. A-l, 5, 2681 (1967).
309. A. I. Restaino, W. N. Reed, J. Polym. Sci., 36, 499 (1959).
310. E. H. Riddle, Monomeric Acrylic Ester, Reinhold, NY,
1954, Ref. 14, p. 64.
3 11. J. C. Robb, E. Senogles, Trans. Faraday Sot., 58,708 (1962).
312. J. C. Robb, D. Vofsi, Trans, Faraday Sot., 55, 558 (1959).
313. M. E. Rozenberg, A. F. Nikolaev, A. V. Pustovalova, Vyso-
komol. Soedin., 8, 1155 (1966).
314. L. V. Ruban, A. L. Buchachenko, M. B. Neiman,
Yu. V. Koknanov, Vysokomol. Soedin., 8, 1642 (1966).
315. M. Ryska, M. Kolinsky, D. Lim, J. Polym. Sci. C, 16, 621
(1967).
316. N. G. Saha, U. S. Nandi, S. R. Palit, J. Chem. Sot., 427
(1956).
317. N. G. Saha, U. S. Nandi, S. R. Palit, Chem. Sot., 7 (1958).
318. N. G. Saha, U. S. Nandi, S. R. Palit, Chem. Sot., 12 (1958).
319. I. Sakurada, K. Noma, Y. Ofuji, Kobunshi Kagaku, 20, 481
(1963); from CA, 63, 8487C (1965).
II / 164 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
320. I. Sakurada, Y. Sakaguchi, K. Hashimoto, Kobunshi Kagaku,
19, 593 (1962); from CA, 61, 16159D (1964).
321. G. F. Santee, R. H. Marchessault, H. G. Clark, J. J. Kearny,
V. Stannett, Makromol. Chem., 73, 177 (1964).
322. M. Santhappa, V. M. Iyer, Current Sci. (India), 24, 173
(1955).
323. M. Santhappa, V. S. Vaidhyanathan, Current Sci. (India) 23,
259 (1954).
324. J. Scanian, Trans. Faraday Sot., 50, 756 (1954).
325. E. Schonfeld, I. Waltcher, J. Polym. Sci., 35, 536 (1959).
326. G. V. Schulz, G. Henrici, S. Olive, J. Polym. Sci., 17, 45
(1955).
327. G. V Schulz, G. Henrici, S. Olive, Z. Elektrochem., 60,296
(1956).
328. G. V. Schulz, L. Roberts-Nowakowska, Makromol. Chem.,
80, 36 (1964).
329. G. V. Schulz, D. J. Stein, Makromol. Chem., 52, 1 (1962).
330. G. l? Scott, C. C. Soong, W.-S. Huang, J. L. Reynolds, J. Org.
Chem., 29, 83 (1964).
331. G. P. Scott, J. C. Wang, J. Org. Chem., 28, 1314 (1963).
332. J. N. Sen, U. S. Nandi, S. R. Palit, J. Indian Chem. Sot., 40,
729 (1963).
333. K. P Shen, F. R. Eirich, J. Polym. Sci., 53, 81 (1961).
334. A. Shimzu, T. Otsu, M. Imoto, Bull. Chem. Sot. Japan, 38,
1535 (1965).
335. T. Shimomura, Y. Kuwabara, E. Tsuchida, I. Shinohara,
Kogyo Kagaku Zasshi, 71, 283 (1968).
336. T. Shimomura, E. Tsuchida, I. Shinohara, Mem. School Sci.
Eng., Waseda Univ., 8, 37 (1964); from CA, 63, 1498514
(1965).
337. T. Shimomura, E. Tsuchida, I. Shinohara, Mem. School Sci.
Eng., Waseda Univ., 29, 1 (1965); from CA, 65, 10675A
(1966).
338. M. Simonyi, F. Tudos, J. Pospisil, Eur. Polym. J., 3, 101
(1967).
339. P. R. Sinha, K. L. Mallik, J. Indian Chem. Sot., 34, 424
(1957).
340. C. Sivertz, J. Phys. Chem., 63, 34 (1959).
341. B. Skrabal, L. Rosik, Chem. Prumysl, 8, 46 (1958).
342. G. Smets, L. Convent, X. van der Borght, Makromol. Chem.,
23, 162 (1957).
343. G. Smets, L. Dehaes, Bull. Sot. Chim. Belges, 59, 13
(1950).
344. W. V. Smith, J. Am. Chem. Sot., 68, 2059 (1964).
345. R. D. Spencer, M. B. Fulton, U.S. Dept. Corn., Office Tech.
Serv., PB Rept., 144, 990 (1961).
346. R. D. Spencer, M. B. Fulton, B. H. Beggs, Abstracts of 137th
ACS Meeting, Cleveland, 1960.
347. N. T. Srinivasan, M. Santhappa, Makromol. Chem., 26, 80
(1958).
348. D. J. Stein, Makromol. Chem., 76, 170 (1964).
349. D. J. Stein, G. V. Schulz, Makromol. Chem., 38,248 (1960).
350. D. J. Stein, G. V. Schulz Makromol. Chem., 52,249 (1962).
351. W. H. Stockmayer, R. 0. Howard, J. T. Clarke, J. Am. Chem.
Sot., 75, 1756 (1953).
352. T. J. Suen, Y. Jen, J. V. Lockwood, J. Polym. Sci., 31, 481
(1958).
353. T. J. Suen, A. M. Schiller, W. N. Russell, Adv. Chem. Series
No. 34, Polymerization and Polycondensation Processes,
ACS, Washington, DC, 1962, pp. 217-24.
354. T. Sugimura, Y. Ogata, Y. Minoura, J. Polym. Sci. A-l, 4,
2747 (1966).
355. G. Takayama, Kobunshi Kagaku, 15, 89 (1958); from CA,
53, 868D (1959).
356. W. M. Thomas, E. H. Gleason, J. J. Pellon, J. Polym. Sci., 17,
275 (1955).
357. C. F. Thompson, W. S. Port, L. P. Witnauer, J. Am. Chem.
SOL, 81, 2552 (1959).
358. A. P. Titov, I. A. Livshits, Zh. Obshch. Khim., 29, 1605
(1959).
359. A. V. Tobolsky, B. Baysal, J. Am. Chem. Sot., 75, 1757
(1953).
360. A. V. Tobolsky, J. Offenbach, J. Polym. Sci., 16,3 11 (1955).
361. T. Toda, J. Polym. Sci., 58, 411 (1962).
362. N. Tokura, M. Matsuda, F. Yazaki, Makromol. Chem., 42,
108 (1960).
363. A. C. Toohey, K. E. Weale, Trans. Faraday Sot., 58, 2439
(1962).
364. A. C. Toohey, K. E. Weale, Trans. Faraday Sot., 58, 2446
(1962).
365. E. Tsuchida, Y. Ohtani, H. Nakadai, I. Shinohara, Kogyo
Kagaku Zasshi, 70, 573 (1967).
366. E. Tsuchida, Y. Ohtani, H. Nakadai, I. Shinohara, Kogyo
Kagaku Zasshi, 69, 1230 (1966).
367. E. Tsuchida, T. Shimomura, K. Fujimori, Y. Ohtani,
I. Shinohara, Kogyo Kagaku Zasshi, 70, 566 (1967).
368. K. Tsuda, S. Kobayashi, T. Otsu, Bull, Chem. Sot. Japan, 38,
1517 (1965).
369. K. Tsuda, T. Otsu, Bull. Chem. Sot. Japan, 39, 2206
(1966).
370. F. TudSs, T. Berezhnykh-Foldes, Eur. Polym. J., 2, 229
(1966).
371. F. Tudos, I. Kende, M. Azori, J. Polym. Sci., 53, 17
(1961).
372. F. Tudos, I. Kende, M. Azori, J. Polym. Sci. A, 1, 1353
(1963).
373. F. Tudos, I. Kende, M. Azori, J. Polym. Sci. A, 1, 1369
(1963).
374. J. Ulbricht, Faserforsch. Textiltech., 10, 166 (1959)
375. J. Ulbricht, Faserforsch. Textiltech., 11, 62 (1960).
376. J. Ulbricht, Z. Phys. Chem. (Frankfurt), 221, 346 (1962).
377. J. Ulbricht, B. Sandner, Faserforsch. Textiltech., 17, 208
(1966).
378. J. Ulbricht, R. Sourisseau, Faserforsch. Textiltech., 16, 213
(1965).
379. T. Uno, K. Yoshida, Kobunshi Kagaku, 15,819 (1958); from
CA, 54, 20298D (1960).
380. C. A. Uraneck, J. E. Bulreigh, J. Appl. Polym. Sci., 12, 1075
(1968).
381. W. H. Urry, F. W. Stacey, E. S. Huyser, 0. 0. Juveland, J.
Am. Chem. Sot., 76, 450 (1954).
382. V. Vaclavek, Chem. Prumysl, 10, 103 (1960).
383. V. Vaclavek, J. Appl. Polym. Sci., 11, 1881 (1967).
384. V. Vaclavek, J. Appl. Polym. Sci., 11, 1903 (1967).
385. V. S. Vaidhyanathan, M. Santhappa, Makromol. Chem., 16,
140 (1955).
386. R. L. Vale, W. G. P. Robertson, J. Polym. Sci., 33, 518
(1958).
387. B. M. E. van der Hoff, J. Polym. Sci., 44, 241 (1960).
388. B. M. E. van der Hoff, J. Polym. Sci., 48, 175 (1960).
389. A. A. Vansheidt, G. Khardi, Acta Chim. Acad. Sci. Hung.,
20, 261 (1959); from CA, 54, 6180B (1960).
390. A. A. Vansheidt, G. Khardi, Acta Chim. Acad. Sci. Hung.,
20, 381 (1959); from CA, 54, 1152F (1960).
391. F. K. Velichko, I. P. Lavrentev, Yu. P. Chizhov, Izv. Akad.
Nauk SSSR, Ser, Khim., 1966, 172; from CA, 64, 12485C
(1966).
392. G. Vidotto, A. Crosato-Amaldi, G. Talmini, Makromol.
Chem., 114, 217 (1968).
393. M. Vrancken, G. Smets, Makromol. Chem., 30, 197 (1959).
394. J. Vuillemenot, B. Barbier, G. Riess, A. Banderet, J. Polym.
Sci. A, 3, 1969 (1965).
395. L. A. Wall, D. W. Brown, J. Polym. Sci., 14, 513 (1954).
396. R. A. Wallace, K. L. Hadley, J. Polym. Sci. A-l, 4,71 (1966).
397. C. Walling, J. Am. Chem. Sot., 70, 2561 (1948).
398. C. Walling, E. R. Briggs, J. Am. Chem. Sot., 68, 1141
(1946).
399. C. Walling, Y. Chang, J. Am. Chem. Sot., 76,4878 (1954).
400. C. Walling, L. Heaton, J. Am. Chem. Sot., 87, 38 (1965).
401. C. Walling, J. J. Pellon, J. Am. Chem. Sot., 79,4776 (1957).
402. M. Watanabe, H. Kiuchi, J. Polym. Sci., 58, 103 (1962).
403. 0. L. Wheeler, E. Lavin, R. N. Crozier, J. Polym. Sci., 9, 157
(1952).
404. E. F. T. White, M. J. Zissell, J. Polym. Sci. A, 1,2189 (1963).
405. T. Yamamoto, Bull. Chem. Sot. Japan, 40, 642 (1967).
406. T. Yamamoto, T. Otsu, J. Polym. Sci. B, 4, 1039 (1966); see
also Bull. Chem. Sot. Japan, 40, 2449 (1967).
407. T. Yamamoto, T. Otsu, Koguo Kagaku Zasshi, 70, 2403
(1967).
408. T. Yamamoto, T. Otsu, M. Imoto, Kogyo Kagaku Zasshi, 69,
990 (1966).
409. S. D. Yevstratova, M. F. Margaritova, S. S. Medvedev,
Polym. Sci. USSR, 5, 681 (1964).
410. M. Yoshida, K. Tanouchi, Kobunshi Kangaku, 20, 545
(1963); from Makromol. Chem., 71, 216 (1964).
411. V. V. Zaitseva, V. D. Enalev, A. I. Yurzhenko, Vysokomol.
Soedin., Ser. A, 9, 1958 (1967).
412. V. M. Zhulin, M. G. Gonikberg, V. N. Zagorbinina, Dokl.
Akad. Nauk SSSR, 163, 106 (1965); from CA, 63, 11706G
(1965).
413. V. M. Zhulin, M. G. Gonikberg, V. N. Zagorbinina, Izv.
Akad. Nauk SSSR, Ser. Khim., 827 (1966).
414. V. M. Zhulin, M. G. Bonikberg, V. N. Zagorbinina, Izv.
Akad. Nauk SSSR, Ser. Khim., 997 (1966).
415. M. G. Zimina, N. P. Apukhtina, Kolloid Zh., 21, 181 (1959).
416. J. Aoyagi, K. Kitamura, I. Shinohara, Kogyo Kagaku Zasshi,
73, 2045 (1970).
417. J. Aoyagi, I. Shinohara, Kogyo Kagaku Zasshi, 74, 1191
(1971).
418. T. Asahara, M. C. Chou, Bull. Chem. Sot. Japan, 42, 1373
(1969).
Re f e r e n c e s II / 165
419. C. Aso, T. Kunitake, M. Shinsenji, H. Miyazaki, J. Polym.
Sci. A-l, 7, 1497 (1969).
420. J. C. Bevington, M. Johnson, J. P. Sheen, Eur. Polym. J., 8,
209 (1972).
421. G. C. Bhaduri, U. S. Nandi, Makroml. Chem., 128, 176
(1969).
422. G. C. Bhaduri, U. S. Nandi, Makromol. Chem., 128, 183
(1969).
423. B. R. Bhattacharyya, U. S. Nandi, Makromol. Chem., 149,
231 (1971).
424. B. R. Bhattacharyya, U. S. Nandi, Makromol. Chem., 149,
243 (1971).
425. D. Braun, F. Weiss, Makromol. Chem., 138, 83 (1970).
426. D. Braun, F. Weiss, Angew. Makromol. Chem., 15, 127
(1971).
427. C-T. Chen, W-D. Huang, J. Chin. Chem. Sot., 16,46 (1969);
from CA, 71, 102247U (1969).
428. Y. Choshi, A. Tsuji, G. Akazome, K. Murai, Kogyo Kagaku
Zasshi, 71, 908 (1968); from CA, 69, 677454 (1968).
429. N. N. Dass, M. H. George, Eur. Polym. J., 6, 897 (1970).
430. H. J. Dietrich, M. A. Raymond, J. Macromol. Sci. Chem. A,
6, 191 (1972).
43 1. J. P. Fischer, Makromol. Chem., 155, 211 (1972).
432. J. P. Fischer, Makromol. Chem., 155, 227 (1972).
433. J. P. Fischer, W. Ltiders, Makromol. Chem. 155,239 (1972).
434. R. Kh. Freidlina, A. B. Terentev, N. S. Ikonnikov, Dokl.
Akad. Nauk SSSR, 193, 605 (1970).
435. R. Kh. Freidlina, A. V. Terentev, N. S. Ikonnikov, Izv. Akad.
Nauk SSSR, Ser. Khim., 1970, 554.
436. S. S. Frolov, T. M. Slivchenko, Izv. Vyssh. Ucheb. Zaved.,
Khim. Khim. Tekhnol., 14, 1264 (1971); from CA, 76,
25660X (1972).
437. I. Geczy, H. I. Nasr, Acta Chim. (Budapest), 70,319 (1971);
from CA, 76, 100150M (1972).
438. S. N. Gupta, U. S. Nandi, J. Polym. Sci. A-l, 8, 1493 (1970).
439. D. A. J. Harker, R. A. M. Thomson, I. R. Walters, Trans.
Faraday Sot., 67, 3057 (1971).
440. M. Imoto, K. Ohashi, Makromol. Chem., 117, 117 (1968).
441. E. F. Jordan, Jr., B. Artymyshyn, A. N. Wrigley, J. Polym.
Sci. A-l, 7, 2605 (1969).
442. I. Kar, B. M. Mandal, S. R. Palit, J. Polym. Sci. A-l, 7,2829
(1969).
443. S. Kobayashi, Kogyo Kagaku Zasshi, 72, 2511 (1969).
444. C. Kwang-Fu, Kobunshi Kagaku, 29, 233 (1972).
445. I. M. Likhterova, E. M. Lukina, Zh. Obshch. Khim., 42,194
(1972); from CA, 76, 1275043 (1972).
446. A. Matsumoto, M. Oiwa, J. Polym. Sci. A-l, 10, 103 (1972).
447. J. A. May, Jr., W. B. Smith, J. Phys. Chem., 72,2993 (1968).
448. L. A. Miller, V. Stannett, J. Polym. Sci. A-l, 7, 3159 (1969).
449. Y. Minoura, M. Mitoh, Kogyo Kagaku Zasshi, 74, 747
(1971).
450. Y. Minoura, A. Tabuse, Kogyo Kagaku Zasshi, 74, 990
(1971).
451. Y. Minoura, H. Toshima, J. Polym. Sci. A-l, 7, 2837
(1969).
452. M. Modena, l? Piccardi, Eur. Polym. J., 7, 1 (1971).
453. N. Mogi, M. Shindo, Kogyo Kagaku Zasshi, 73,786 (1970).
II / 166 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
454. G. A. Mortimer, J. Polym. Sci. A-l, 8, 1513 (1970).
455. G. A. Mortimer, J. Polym. Sci. A-l, 8, 1535 (1970).
456. G. A. Mortimer, J. Polym. Sci. A-l, 8, 1543 (1970).
457. G. A. Mortimer, J. Polym. Sci. A-l, 10, 163 (1972).
458. I. G. Murgulescu, I. Vlagiu, Rev. Roum. Chim., 14, 411
(1969); from CA, 71, 71773F (1969).
459. T. Nakaya, M. Tanaka, M. Imoto, Makromol. Chem., 149,
221 (1971).
460. J. H. Ok, S. B. Pak, Hwahak Kwa Hwahak Kongop, 1971,
239 (Korean); from CA, 77, 20147U (1972).
461. T. Ota, S. Masuda, Kogyo Kagaku Zasshi, 73, 2020 (1970).
462. T. Ota, S. Masuda, C. Aoyama, M. Ebisudani, Kogyo
Kagaku Zasshi, 74, 994 (1971).
463. G. S. Park, D. G. Smith, Trans. Faraday Sot., 65, 1854
(1969).
464. F. Patat, P. Mehnert, Monatsh. Chem., 98, 538 (1967).
465. S. P. Potnis, A. M. Deshpande, Makromol. Chem., 125, 48
(1969).
466. S. P. Potnis, A. M. Deshpande, Makromol. Chem., 153, 139
(1972).
467. W. A. Pryor, J. H. Coca, Macromolecules, 3, 500 (1970).
468. W. A. Pryor, T. R. Fiske, Macromolecules, 2, 62 (1969).
469. W. A. Pryor, T.-L. Huang, Macromolecules, 2, 70 (1969).
470. E. Pulat, C. B. Senvar, Commun. Fat. Sci. Univ. Ankara, Ser.
B, 15, (3) 25 (1968); from CA, 72, 559342 (1970).
471. P V. T. Raghuram, U. S. Nandi, J. Polym. Sci. A-l, 7, 2379
(1969).
472. P. V. T. Raghuram, U. S. Nandi, J. Polym. Sci. A-l, 8, 3079
(1970). .
473. K. K. Roy, D. Pramanick, S. R. Palit, Makromol. Chem.,
153, 71 (1972).
474. J. C. Saam, D. J. Gordon, J. Polym. Sci. A-l, 8, 2509
(1970).
475. T. Saegusa, Y. Ito, N. Yasuda, Polym. J., 1, 591 (1970).
476. S. K. Saha, A. K. Chaudhuri, J. Polym. Sci. A-l, 10, 797
(1972).
477. G. P. Scott, A. M. R. Elghoul, J. Polym. Sci. A-l, 8, 2255
(1970).
478. G. P. Scott, F. J. Foster, Macromolecules, 2, 428 (1969).
479. R. B. Seymour, J. M. Sosa, V. J. Patel, J. Paint Technol., 43,
(563), 45 (1971).
480. T. Shimomura, E. Tsuchida, I. Shinohara, Kogyo Kagaku
Zasshi, 71, 1074 (1968); from CA, 69, 97249Y (1968).
481. E. Staudner, J. Beniska, Eur. Polym. J. Suppl., 1969, 537.
482. F. Suganuma, H. Mitsui, S. Machi, M. Hagiwara, T. Kagiya,
J. Polym. Sci. A-l, 6, 3127 (1968).
483. K. Sugiyama, T. Nakaya, M. Imoto, J. Polym. Sci. A-l, 10,
205 (1972).
484. A. B. Terentev, N. S. Ikonnikov, R. Kh. Freidlina, Izv. Akad.
Nauk SSSR, Ser. Khim, 73 (1971).
485. A. B. Terentev, N. S. Ikonnikov, R. Kh. Freidlina, Dokl.
Akad. Nauk USSR, 196, 1373 (1971).
486. A. S. Tevlina, H. S. Kolesnikov, S. N. Sividova, V. V. Ryltsev,
Vysokomol. Soedin., Ser. A, 9, 2473 (1967); Polym. Sci.
USSR, 9, 2797 (1967).
487. R. A. M. Thomson, I. R. Walters, Trans. Faraday Sot., 67,
3046 (1971).
488. R. A. M. Thomson, I. R. Walters, J. R. King, J. Polym. Sci.,
B, 10, 63 (1972).
489. E. Tsuchida, T. Tomono, Kogyo Kagaku Zasshi, 73, 2040
(1970).
490. M. Tsunooka, M. Fujii, N. Ando, M. Tanaka, N. Murata,
Kogyo Kagaku Zasshi, 73, 805 (1970).
491. M. Tsunooka, T. Higuchi, M. Fujii, M. Tanaka, N. Murata,
Kogyo Kagaku Zasshi, 73, 596 (1970).
492. G. Vidotto, S. Brugnaro, G. Talamini, Makromol. Chem.,
140, 249 (1970).
493. G. Vidotto, S. Brugnaro, G. Talamini, Makromol. Chem.,
140, 263 (1970).
494. F. Yamada, M. Kanbe, I. Shinohara, Memo. Sch. Sci. Eng.
Waseda Univ. 1969, No. 33, 67: from CA, 73, 88255C
(1970).
495. T. Yamamoto, M. Hasegawa, T. Otsu, Bull. Chem. Sot.
Japan, 42, 1364 (1969).
496. T. Yamamoto, S. Nakamura, M. Hasegawa, T. Otsu, Kogyo
Kagaku Zasshi, 72, 727 (1969).
497. T. Yamamoto, T. Otsu, J. Polym. Sci. A-l, 7, 1279
(1969).
498. N. Yamashita, T. Seita, M. Yoshihara, T. Maeshima, Kogyo
Kagaku Zasshi, 74, 2157 (1971).
499. N. Yamashita, T. Seita, M. Yoshihara, T. Maeshima, J.
Polym. Sci. B, 9, 641 (1971).
500. V. M. Zhulin, M. G. Gonikberg, A. L. Goff, V. N. Zagorbi-
nina, Vysokomol. Soedin., Ser. A, 11, 777 (1969).
501. N. Ya. Kaloforov, E. Borsig, J. Polym. Sci., Polym. Chem.
Ed., 11, (10) 2665 (1973).
502. 0. A. Aminova, B. D. Saidov, Dokl. Akad. NaukUzb. SSSR,
4, 45 (1979).
503. D. Pramanick, A. K. Chaterjee, Eur. Polym. J., 16, (9) 895
(1980).
504. D. A. J. Harker, R. A. M. Thomson, I. R. Walters, Trans.
Faraday Sot., 67, (Pt. 10) 3057 (1971).
505. U. A. Safaev, Kh. Rakhmatullaev, A. T. Dzhalilov, Uzb.
Khim. Zh., 3, 42 (1983).
506. E. Abuin, E. A. Lissi, J. Macromol. Sci., Chem., 13 (8), 1147
(1979).
507. G. P. Scott, F. J. Foster, Macromolecules, 2 (4), 428 (1969).
508. K. Yokota, H. Tomioka, A. Tazumi, J. Macromol. Sci.,
Chem., 6 (7), 1337 (1972).
509. M. Bezdek, J. Exner, J. Kriz, F. Hrabak, Makromol. Chem.,
147, 1 (1971).
5 10. A. Fehervari, E. Boros Gyevi, T. Foldes-Bereznish, F. Tudiis,
J. Macromol. Sci. A: Chem., 18 (3), 431 (1982).
511. B. A. Englin, T. A. Onishchenko, R. Kh. Freidlina, Izv.
Akad. Nauk SSSR, Ser, Khim. 12, 2542 (1971).
512. M. Raetzsch, I. Zschach, Plaste Kaut., 21 (5), 345 (1974).
513. T. Foldes-Bereznich, M. Szesztay, F. Tudos, J. Macromol.
Sci. A: Chem., 16 (5), 977 (1981).
514. J. Pavlinec, E. Borsig, J. Polym. Sci., Polym. Chem. Ed., 19
(9), 2305 (1981).
5 15. N. S. Enikolopyan, B. R. Smirnov, G. V. Ponomarev,
I. M. Belgovskii, J. Polym. Sci., Polym. Chem. Ed., 19
(4), 879 (1981).
516. A. B. Terentev, N. S. Ikonnikov, R. Kh. Freidlina, Dokl.
Akad. Nauk SSSR, 196, (6) 1373 (1971).
517.
518.
519.
520.
521.
522.
523.
524.
525.
526.
527.
528.
529.
530.
531.
532.
533.
534.
535.
536.
537.
538.
539.
540.
541.
A. G. Shostenko, V. E. Myshkin, Vysokomol. Soedin., Ser.
B, 20, 163 (1978).
Sl. A. Karapetyan, G. P. Shakhovskoi, N. A. Grigorev,
V. M. Zhulin, B. A. Englin, Izv. Akad. Nauk SSSR, Ser.
Khim., 6, 1303 (1970).
B. A. Englin, B. N. Ospipov, Izv. Akad. Nauk SSSR, Ser.
Khim., 1, 65 (1971).
C. H. Bamford, J. Chem. Sot., Faraday Trans., 1, 72 (12),
2805 (1976).
M. R. Lachinov, T. R. Aslamazova, V. P. Zubov,
V. A. Kabanov, Vysokomol. Soedin., Ser. A, 17 (5), 1146
(1975).
V. P. Naidenov, V. G. Syromyatnikov, Ukr. Khim. Zh. (Russ.
Ed.), 45 (lo), 982 (1979).
P. A. Zagorets, A. G. Shostenko, A. M. Dodonov,
N. P. Tarsova, Zh. Org. Khim., 10 (lo), 2093 (1974).
A. P. Titov, V. V. Kotov, Vysokomol. Soedin., Ser. B, 10 (7),
495 (1968).
B. R. Smirnov, V. E. Mironychev, I. V. Golikov,
M. M. Mogilevich, I. V. Enikolopov, Depos. Dot., SPSTL
598 Khp-D82, 9 pp. Avail. SPSTL (1982).
M. Niwa, N. Higashi, Sci. Eng. Rev. Doshisha Univ., 24 (3),
129 (1983).
0. F. Olaj, J. W. Breitenbach, I. Hofreiter, Rec. Chem. Progr.,
30 (2), 87 (1969).
B. R. Smirnov, A. I? Marchenko, G. V. Korolev,
I. M. Belgovskii, N. S. Enikolopyan, Vysokomol. Soedin.,
Ser. A, 23 (5), 1042 (1981).
R. B. Seymour, V. Patel, J. Paint Technol., 44 (569), 53
(1972).
N. M. Kozyreva, A. I. Kirilin, V. V. Korshak, Plast. Massy, 2,
24 (1983).
N. G. Podosenova, E. G. Zotilov, V. P. Budtov, Vysokomol.
Soedin., Ser. A, 25 (l), 43 (1983).
S. K. Verma, K. Wendler, M. Fedtke, Acta Polym., 35 (l), 58
(1984).
A. Hrivik, J. Beniska, E. Hudecova, Chem. Zvesti, 37 (4),
503 (1983).
S. Raghunath, M. H. Rao, K. N. Rao, Radiat, Phys. Chem.,
22 (6), 1011 (1983).
K. Kodaira, K. Ito, Nagoya Kogyo Gijutsu Shikensho
Hokoku, 31 (1/2), 22 (1982).
K. Kodaira, T. Ito, M. Omi, Y. Onishi, K. Ito, Nagoya Kogyo
Gijutsu Shik, Hokoku, 31 (6/7), 186 (1982).
V. Kim, A. G. Shostenko, M. D. Gasparyan, React. Kinet.
Catal. Lett., 12 (4), 479 (1979).
V. A. Kabanov, D. A. Topchiev, G. T. Nazhmethdinova, Izv.
Akad. Nauk SSSR, Ser. Khim., 9, 2146 (1983).
L. A. Smimova, Yu. D. Semchikov, L. I. Kamyshenkova,
T. G. Sveshnikova, A. N. Egorochkin, G. S. Kalinina,
B. A. Egorov, Vysokomol. Soedin., Ser. A, 24 (5), 999 (1982).
K. Yamamoto, M. Sugimoto, J. Makromol. Sci. A: Chem.,
13 (8), 1067 (1979).
K. Matsuo, G. W. Nelb, R. G. Nelb, W. H. Stockmayer,
Macromolecules, 10 (3), 654 (1977).
542. J. Lokaj, F. Hrabak, Eur. Polym. J., 14 (12), 1039 (1978).
543. M. Iino, M. Igarashi, M. Matsuda, Macromolecules, 12 (4)
697 (1979).
544.
545.
546.
547.
548.
549.
550.
551.
552.
553.
554.
555.
556.
557.
558.
559.
560.
561.
562.
563.
564.
565.
566.
567.
568.
569.
570.
571.
References II / 167
M. Yoshihara, N. Miryamoto, M. Fukumura, T. Maeshima, J.
Polym. Sci., Polym. Lett. Ed., 14 (2), 97 (1976).
W. A. Pryor, Tetrahedron Lett., 1201 (1963).
T. Otsu, Radical Polymerization - I, Kapakudojin, Koyoto,
1971, p. 143.
I. Grotewold, M. M. Hirschler, J. Polym. Sci., Polym. Chem.
Ed., 15, 383 (1977).
U. S. Nandi, M. Singh, P. V. T. Raghuram, Makromol.
Chem., 183 (8), 1467 (1982).
B. Cellard, Ch. Pichot, A. Revillon, Makromol. Chem., 183
(8), 1935 (1982).
L. Vrhovac, J. Velickovic, D. Filipovic, Makromol. Chem.,
185 (8), 1637 (1984).
B. Boutevin, Y. Pietrasanta, Makromol. Chem., 186 (4), 831
(1985).
M. A. Bruk, S. A. Pavlov, A. D. Abkin, Dokl. Akad. Nauk
SSSR, 245, 626 (1979).
W. Berger, H. J. Schneider, H. Schmidt, Faserforsch. Tex-
tiltech., 27 (8), 437 (1976).
J. C. Saam, D. J. Gordon, J. Polym. Sci., Part. A-l, 8 (9),
2509 (1970).
T. Ota, Kenkyu Hokoku-Asyhi Garasu Kogyo Gijutsu
Shoreikai, 42, 65 (1983).
B. R. Smimov, I. M. BelGovskii, G. V. Ponomarev,
N. S. Enikolopyan, Dokl. Akad. Nauk SSSR, 254 (l), 127
(Chem.).
R. Kh. Freidlina, A. B. Terentjev, N. S. Ikonnikov, Dokl.
Akad. Nauk, 3, 193, 605 (1970).
R. Kh. Freidlina, A. B. Terentjev, N. S. Ikonnikov, Isv. Akad.
Nauk, Ser. Chem., 554 (1970). ,
A. B. Terentijev, N. S. Ikonnikov, R. Kh. Freidlina, Isv.
Akad. Nauk, Ser. Chem., 1, 73 (1971).
C. F. Jasso, E. Mendizabal, M. E. Hemandez, Rev.
Plast. Mod., 62, 823 (1991); from CA, 117, 131596f
(1992).
I. Capek, Collect. Czech. Chem. Commun., 51,2546 (1986).
F. Vidal, R. G. Gilbert, Macromol. Chem. Phys., 197, 1835
(1996).
K. G. Suddaaby, D. R. Maloney, D. M. Haddleton, Macro-
molecules, 30, 702 (1997).
L. I. Abramova, E. N. Zilberman, V. V. Leshin, Izv. Vyssh.
Uchebn. Zaved., Khim. Khim. Tekhnol., 30, 117 (1987);
from CA, 107, 237343e (1987).
B. Boutevin, Y. Pietrasanta, Makromol. Chem., 186, 831
(1985).
G. Bauduin, B. Boutevin, J. P. Mistral, L. Sarraf, Makromol.
Chem., 186, 1445 (1985).
C. A. Barson, J. C. Bevington, B. J. Hunt, J. Polym. Sci., Part
A, Polym. Chem., 34, 227 (1996).
C. A. Barson, J. C. Bevington, B. J. Hunt, J. Polym. Sci., Part
A, Polym. Chem., 33, 863 (1995).
D. Braun, P. Hempler, Polym. Bull. (Berlin), 30, 55
(1993).
T. T. Vasileva, V. A. Kochetkova, B. V. Nelyubin,
V. I. Dostovalova, R. K. Freidlina, Izv. Akad. Nauk SSSR,
Ser. Khim., 808b (1987); from CA, 108, 111753r (1988).
G. Bauduin, B. Boutevin, B. Pucci, J. P. Rigaud, Makromol.
Chem., 188, 2339 (1987).
II / 168 TRANSFER CONSTANTS IN FREE RADICAL POLYMERIZATION
572. T. T. Vasileva, V. A. Kochetkova, B. V. Nelyubin,
R. K. Freidlina, Izv. Akad. Nauk. SSSR, Ser. Khim., 1397
(1986); from CA, 106, 11993e (1987).
573. F. Jahanzad, M. Kazemi, S. Sajjadi, F. A. Taromi, Polymer,
34, 3542 (1993).
574. B. K. Dietrich, W. A. Pryor, S. J. Wu, J. Appl. Polym. Sci.,
36, 1129 (1988).
575. S. Y. Lee, Y. J. Shin, Pollimo, 20,233 (1966); from CA, 124,
318076~ (1996).
Photopolymerization Reactions
J . P. Fouassier
Laboratoire de Photochimie G&r&ale, Mulhouse, Cedex, France
A. Introduction II-1 69 A. INTRODUCTION
B. Tables
Table 1.
Table 2.
Table 3.
Table 4.
Table 5.
Table 6.
Table 7.
Table 8.
Table 9.
II-1 70
Rate Constants of Cleavage, Electron
Transfer and Monomer Quenching
in Radical Photoinitiators II-1 70
Annex to Table 1. Photoinitiator
Compound Chemi stri es II-1 73
Bimolecular Rate Constants for
the Reaction of Phosphonyl Radicals
with Various Monomers in
Cyclohexane at Room Temperature II-1 76
Bimolecular Rate Constants for
the Reaction of Various Radicals
with Various Olefinic Monomers
at Room Temperature II-I 76
Bimolecular Rate Constants for
the Reaction of PhzP=O and
PhzP = S with Various Monomers II-1 76
Electron Transfer Reaction of Radicals
with Diphenyliodonium Salts II-1 76
Electron Transfer Rate Constants (k,)
Between Photosensitizers and Cationic
Photoinitiators and Quenching Rate
Constants (k,) for Cyclohexene Oxide
in Methanol (M) and Acetonitrile
(AN)
II-1 77
Excitation Transfer Rate Constants
(kr) for Thioxanthones and
Photoinitiators II-1 78
Annex to Table 7. Compound
Chemi stri es II-1 78
Triplet State Lifetimes (7~) of the
Sensitizer (TXI) in Different Media,
and Rate Constant (kr) of the
Interaction between TXI and TPMK II-1 79
Some Values of the Triplet State
Energy Levels of Photoinitiators and
Monomers II-1 79
Table 10. Values of T:, Tr, and k,b
in Solution
Table 11. Rate Constant of Interaction of
Ketones and Light Stabilizers
in Solution
Annex to Table 11
C. References
II-1 79
II-1 79
II-I 79
II-1 80
UV curing technologies use light beams to start photo-
chemical and chemical reactions in organic materials
(monomers, oligomers, prepolymers, polymers), mostly
through a Photo-Induced Polymerization (PIP) reaction.
This leads to the formation of a new polymeric material
whose applications lie in various industrial sectors, such as
coatings, graphic arts, imaging, microelectronics, etc.
Specific advantages of these technologies over the usual
thermal operations are rapid through-cure, solvent-free
formulation, room temperature treatment and low energy
requirements.
This PIP process is concerned with the creation of a
polymer P through a chain radical or cationic reaction
initiated by light in the presence of a photoinitiator (PI) and
a coupled PI/photosensitizer (PS):
light .
P I - R
$-- RM---------P
light
PI -acid species:X
+XM+---P
ps light
-excited PS
hi-
excited PI -R or acid species
The reactivities of PI and PS govern, for a large part, the
practical efficiency of the PIP reaction. The present chapter
reports typical data obtained (through time-resolved laser
spectroscopy experiments) on the excited state processes in
PI and PS occurring after the absorption of the photon. Rate
constants reported in the following tables correspond to the
following processes:
1 .
light
PI - lPI* - 3PI*
(ground singlet first excited triplet state
st at e) singlet state
Ri + R;
cleavage
kc-
PIH t S
Habstraction
SH h
PI t M
!!m!i?+
monomer quenching
M, k,
PIH t A -[PI- AH+]
electron transfer
AK k
II / 169
II / 170 PHOTOPOLYMERIZATION REACTIONS
2. R (or A or S . . .) t M ---!!K- RM
3. 3PI* + light stabilizer
ka
-
(L%
4. 3Ps* t PI
k,
-excitation transfer
5. pi: Triplet state lifetime under the given conditions
(equal to the reciprocal value of the sum of the first-order
rate constants of the different processes)
7~: Triplet state lifetime in the presence of a given
additive
6. 3PS* t cationic photoinitiator Ct
k
-ps+ c
(a) Energy transfer can sometimes occur:
3ps* t c+ -pstc+*
B. TABLES
Ilj
Ilk
Ill
Ilm
Iln
IlP
IQ
Ilr
11s
Ilr
11s
Ilr
11s
Ilr
11s
Ilr
11s
I2a
12b
12c
12d
12e
12f
1%
12h
12i
Ila 1.3 6 6 Ml, AHI, SI 4
Ilb 2.0 150
Ilc 1.2 2.5
Ild 1.2 2
Ile 0.2 1
Ilf 0.07 1 3
m 1 . 5 180
Ilh 0.6 8
Ili 0.27 0.05
Ila 3200 Mz, 552 2 1
3 6 0 Ms. S2 2 1
5.4 M3, S2 2 1
3 4 M4> S2 2 1
Ila 0.003 e 2 2
O.OOlf
Ila 7 S2, AH3 2 6
2 sz. AH4
1.9 S2, AH2
2 S2, AH5
0.56 s2, A&
1 0 s3 2 3
0.5 1500 M7r AH2, S4 2 5
0.9 15. 50
0.0064 = s2 2 6
0.0025 e
0.0056e
0.0043 e
5 6 s6, Ml 2 6
110
5. 500 s6, M2 2 6
7400
5 1 0 0 s6, Ms 2 6
6 5 0 0
4 9 969 M3 2 6
140
9.4 s6, M4 2 6
5 0
2 5 0 MI, AHI, SI 5
2 0
4.5
8
2 2
1 0
2 9
2 0
2 1
7.14
0.87
0.003
0.00025
0.83
0.003
0.67
1.18
0.80
0.26
<O.OOl
0.08
0.20
0.08
0.17
0.15
0.05
(b) Energy and electron transfer can also occur in the
first excited singlet state PS*.
Detailed data are available, especially in several chapters
of two edited books (1) and in a recent monograph (2). Few
data are known on the photopolymerization itself and
largely depend on the practical formulation used as well as
the experimental conditions. Typically, one photon
absorbed can lead to N 10000 polymerized double bonds
(3). Rate constants of propagation k, and termination kt for
a polyurethane acrylate resin containing an acrylate
monomer (weight ratio, 1 : 1) as reactive diluent are
N lo4 l/mol/s and 3 x lo4 l/mol/s respectively (when half
of the double bonds have been polymerized) (3).
TABLE 1. RATE CONSTANTS OF CLEAVAGE, ELECTRON TRANSFER AND MONOMER QUENCHING IN RADICAL PHOTOINITIATORSa
1O-sk, 10m9k, 10-6k, Monomers b/amines /
Compound
(s -9
(VmoVs) (Vmolh) solvents d Refs.
TABLE 1. contd
Rate constants of cleavage, electron transfer and monomer quenching in radical photoinitiators II / 171
t
Compound
lo-sk, 10m9k, 10-6k, Monomers b/aminescl
(s-l) (Ymolh) (VmoVs) solventsd Refs.
1 3 a
1 3 b
13c
I3d
13e
13f
1%
13h
14a
14b
14~
14d
14e
14f
1%
14h
14i
14e
14f
I4g
14h
14i
14f
I@
14h
14i
14f
1%
14h
14i
ISa
16a
I7a
17b
18a
19a
IlOa
Illa
Illb
Illc
Illd
112a
112b
112c
112d
112e
112a
112b
112c
112d
112e
112b
112c
112d
112e
112b
112c
112d
112e
113a
114a
114b
114~
114d
115a
115b
115~
1 0
1
2 5
0.005
1 0
0.006
0.007
0.13
2 100
2 100
2 100
2 100
2 200 MI, AHI, SI 6
2
<lo-4
=10-4
<lo-4
<lo-4
Sl
8100
4 8 0 0
6 5 0 0
1500
190
4 8 0
8 0 0
1000
2 0 0
1 3
6 0
1 7
<l
5.7
1300
7 0 0
3 8 0
180
Mz. S2
MI, S2
7
M3r S2
7
M4r S2 7
2 10
7 x 10-3
8
9
9
9
9
1 0
1 0
0.7
0.05
4 4 0
0.35
1 1
MI, SI
MI, AHI, SI
MI, AHI, SI
MI, AHI, SI
MI, AHI, SI
0.7
6 x 1O-5
0.85
2.5
> 10
0.8
21
0.12
0.01
0.9
0.4
7 0 0
1200
4 8 0
8 0 0
1000
2 0 0
1 3
8100
4 8 0 0
6500
1500
190
6
1 7
<lO
5.7
1300
7 0 0
3 8 0
180
11000
2900
1 5
1200
MI, S2
1 1
M21.92 1 1
M3, S2 1 1
M4, S2 1 1
1.4 1.6 AH2, S2 1 2
MI, AHI, SI 1 3
6.5
6.0
3.5
>5
4
>5
s2
1 4
References page II - 180
II / 172 PHOTOPOLYMERIZATION REACTIONS
TABLE 1. contd
Compound
lo-sk, 10-9k, 10-6k, Monomers b/amines 1
(s-3
(UmoUs) (Vm0V.s) solvents d Refs.
I15d
I16a
I16b
I17a
118a
119a
12Oa
121a
122a
122b
122c
122d
123a
123b
123~
123d
123e
123f
123a
123b
123~
123d
123a
123b
123~
123d
123a
123b
123~
123d
123a
123b
123~
123d
123a
123b
123~
123d
123a
123b
123~
123d
123a
123a
123b
123b
123g
123h
1 2 4
1 2 5
1 2 6
1 2 7
1 2 8
1 2 9
3.3
1.5
0.7
180
300
100
AHl, SI
15
Sl 1 6
Sl
1 7
Sl 1 8
s2
1 8
s2
1 8
s3
1 9
>3
0.05
0.16
0.3
29
60
NlO
- 5
0.02
0.014
93
2.3
2.0
1 5
2
3
3
Ml, AH3, S2
20 6
5
4
4
0.01
0.017
2.5
4H2, s5
Mz, S2, AHz
24
20 3000
6000
6000
6OCG
0.2
0.02
0.03
0.04
4
0.4
1
1
40
30
5
6
1
1
0.3
0.3
M3r S2 20
M4, S2
20
MS> S2
20
M6, s2 20
8
0.85
<10-5
<lo-5
4.4f
0.3
0.015
S2, -4% 26
26
23
Sl, Ma 1 3
Sl, M9
13
S2, AH7
26
S2, AHs 26
M7. S4
25
S2, Ml 37
Szr Mlo
37
S2, MIO 37
s2 39
S7r AH9 4 1
65
37
0.016
0.006
0.007
Compound chemi s t r i es gi ven i n Annex t o Tabl e 1,
b~~Mono~er8: M 1- methyl methacrylate; Mz - styrene; MS - vinyl acetate; Mq - acrylonitrile; MS - vinyl pyrrolidone; Ms - butylvinylether; M, - acrylamide; Ms -
PET& Mg - TMPTA; M 10 - butylmethacrylate.
Amines: AH I - methyl diethanolamine; AHI - triethylamine; AH3 - ethyl-4-(dimethylamino)-benzoate; AH4 - bis-(2-hydroxy ethyl)-methylamine; AH5 - methyl-4-
amino knzoate; AH6 - 1,4-diazabicyclo [2.2.2] octane (DABCO); AH, - dimethylamine; AHs - 2-(dimethyl aminoethyl)-benzoate; AH9 - diethylaniline.
dSolvents: S 1- toluene; S 2 - benzene; S 3 - acetonitrile; S4 - water; S 5 - 2-propanol; S.5 - acetone; S.7 - ethanol.
%ate constant of H abstraction by THF.
Rate constant of H abstraction by isopropanol.
Photoinitiator Compound Chemistries II / 173
ANNEX TO TABLE 1. PHOTOINITIATOR COMPOUND CHEMISTRIES
Compound R
RI R2 R3 R4
4$p4
R3
I l a
Il b
I l c
Il d
Ile
I l f
Ik
Il h
I l i
H
H
H
H
H
NW-Id2
0-4
CH3
H
H
H
H
H
H
H
H
CH3
H
H
H
H
H
H
H
H
CH3
H
H
OCH3
SCH3
S-4
NCHd2
WHd2
0-4
H
4
COOOR I l j
Il k -CH2N(CH3);Cl
I l l -CHzSO;Na+
I l m
Il n
IlP
w
C l
OCH3
F
COOH
I l r COOCH 3
11s
RI
43
P&OR,
0
12a
12b
12c
12d
I2e
12f
1%
12h
12i
H
OCH3
WHd2
SCH3
WH2)2OH
WHd20H
O(CHd$W2H50)3
O(CH2)20COCH=CHz
O(CH2)20COCH=CH2
H
H
H
H
H
H
H
H
COCH-==CH 2
13a
I3b
13c
13d
H
SCH3
OCH3
WH3)2
F-R2
RI
-0
y-753
0 CH-CH,
13e H CsHs WHd2
/
0 N CsH5 NW-Id2
=:
0 N CH=CH2 NCH3)2
E
0
UN
CH=CH2 OEN
I3f
1%
13h
0 OCH,
14a
OCH3
OC4H9
OWCH 3) 2
OH
OCOCH 3
H
CH3
14b
14c
14d
14e
I4f
I+?
14h
14i
0 R
References page II - 180
II / 174 PHOTOPOLYMERIZATION REACTIONS
ANNEX TO TABLE 1. contd
Compound R
Rl RZ R3 R4
$-y-a3
OTR
0-C-OC&H,
Fluorenone
0
p2
FTH
o OR2
ckw43
0 R
ma-rR
0 0
&
R
0
-A-c-p:
OC2Hs
I A &OC2HS
OqH,OCOCH= CH,
0
15a
I6a
I7a
17b
18a
19a
I9b
IlOa
Illa
Illb
Illc
Il l d
I12a
112b
112c
112d
112e
I13a
114a
I14b
I14c
114d
IlSa
115b
1 1 %
115d
116a
H
CHzSOjNa+
OH
OCOCH 3
H
CH3
CH3
H
i-C3H7
OC2H5
z-C4H9
H
CH3
H
H
CH3
CH30
C2H5
H
CH3
H
H
ANNEX TO TABLE 1. contd
Photoinitiator Compound Chemistries II / 175
Compound R
Rl R2 R3 R4
R2
0
R
123a
123b
123~
123d
123e
123f
123g
123h
1 2 4
Ac r i d i n e 1 2 5
Ph e n a z i n e 126
1 2 7
1 2 8
1 2 9
B r
116b
117a
118a
I19a
120a
121a
122a
122b
122c
122d
H
NO2
H
Cl
CH3
CH3(CHdz
H
H
H
H
H
H
Br
Cl
-0CHzCOOH
+
OCHzCH2CHzN(CH3)3SO3Me-
CsHl7
H
0
-&a
Cd25
H
H
H
H
OC3H7
OC3H7
References page II - 180
II / 176 PHOTOPOLYMERIZATION REACTIONS
TABLE 2. BIMOLECULAR RATE CONSTANTSa FOR THE REACTION OF PHOSPHONYL RADICALS WITH VARIOUS MONOMERS IN
CYCLOHEXANE AT ROOM TEMPERATUREb
Radical
Monomer
0
f-o
0
II 943
0
II ,OCH3
0
F
II ,OC2H5
OCH(CH3)2
P,
OCH3
P,
OCH3
P,
OC2H5
Methacrylonitrile 5.0 4.6 4.5 9.2 11
Styrene 6.0 4 . 5 8.0 22 2 5
Methylmethacrylate 8.0 5.0 5.8 5.8 5 . 3
Acrylonitrile 2.0 2.0 0.18 0.58 0.26
Methyl acrylate 3 . 5 2 . 1 1.3 1 . 7 1 . 6
n-Butyl vinyl ether 0.4 0.3 0.23 2 . 1 1 . 4
Vinyl acetate 0.16 0.13 0.082 0.29 0.18
O~RM in 10 l/mol/s.
bRef. 26.
TABLE 3. BIMOLECULAR RATE CONSTANTS FOR THE REACTION OF VARIOUS RADICALS WITH VARIOUS OLEFINIC MONOMERS AT
ROOM TEMPERATURE
Radical
Monomer
Ph-&Ph
AH
Ph2k=0 Ph PhSb2 PhSb3
Styrene 3 . 5 x 10-2 7 x 10-4 1.2 x 10-2 6
Methylmethacrylate 9 x 10e4 5.4 x 10-2 4 x 10-5 0.9 x 10-2 6 18 lo-i lo-It
Acrylonitrile 4 x 10-4 1 . 6 x lo-* 2 x 10-3 2
Methyl acrylate 2
n-Butyl vinyl ether <lo-6 0.5
Vinyl acetate 6 x 1O-4 2 x 10-2 0.2
N-Vinylpyrrolidone 4 x 10-5
kRM in lOl/mol/s.
bRef. 26.
CFrom Ref. 40.
+From Ref. 16.
TABLE 4. BIMOLECULAR RATE CONSTANTSa FOR THE REAC-
TION OF Phzkd AND Ph,is WITH VARIOUS MONOMERSbJ
Radical
Monomer Ph&O Ph$=S
Methacrylonitrile 1 . 9 0.9
Styrene 4.6 0.4
Methylmethacrylate 4 . 1 0.19
Acrylonitrile 1 . 3 0.52
Methyl acrylate 1 . 7 0.62
n-Butyl vinyl ether 5.0 0.15
Vinyl acetate 1 . 4 0.042
akRM in IO7 l/mol/s
bRef. 21.
Experiments were carried out in CH& solution at room temperature.
TABLE 5. ELECTRON TRANSFER REACTION OF RADICALS WITH
DIPHENYLIODONIUM SALTS
Radicals 10 m9k, (l/mol/s)
Ph2Pb 5 10-3
Ph #OH 0.03
(CH3)2k0H 0.06
Refs.
42
43
Electron Rate Constants and Quenching Rate Constants II / 177
TABLE 6. ELECTRON TRANSFER RATE CONSTANTS (k,) BETWEEN PHOTOSENSITIZERS AND CATIONIC PHOTOINITIATORS AND
QUENCHING RATE CONSTANTS (k,) FOR CYCLOHEXENE OXIDE IN METHANOL (M) AND ACETONITRILE (AN)
Photosensitizer Cationic photoinitiator Anion Sol vent
lo-k,
(l/mol/s)
lo-k,
(l/mot/s) Refs.
Chlorothioxanthone
Benzophenone
Ketocoumarin
Chlorothioxanthone
(C6H5)3S+ PF,
off-
CH,- S
I-
@P(C6HS)3
0
0
(~,f4h--4-~~2%%
AH,
BF, 38
(C&5)3Se+AsF; 1 5
AsF,
cl-
PF,
BF,
AsF;
AsF;
AsF,
Cl-
BF,
BF,
PF,
PF,
SbF,
AsF,
BF;
BF;
PF,
AsFi
M 24 0.3 28
24
26
24
AN 290
M 400
36
M 15 0.33
1
47
M 6 . 4 0.04
M 1 4 29
3 5
28
4
8
570
110
1 4
100
References page II - 180
II 1178 PHOTOPOLYMERIZATION REACTIONS
TABLE 6. contd
Photosensitizer Cationlc photoinitiator Anion Solvent
lo-k,
(l/mol/s)
lo-k,
(l/mol/s) Refs.
Xanthone
Michlers ketone
Thioxanthone
lo-Methylacridone
Acridone
Anthracene
Chlorothioxanthone
Pyrene
Benzophenone
lsopropylthioxanthone
cl- M 140
0.7
200
350
740
M 1 3 1
Wzp)zI+ cl- 400 28
130
500
250
TABLE 7. EXCITATION TRANSFER RATE CONSTANTS (kT) FOR THIOXANTHONES AND PHOTOINITIATORS
Thioxanthone Initiator Solvent 10e6k~ (l/mol/s)
T X 1
ETX
I TX
HMK
OMK
TPMK
NMK
TPMK
TPMK
Toluene 100
Methanol 290
Toluene 75
Methanol 380
Toluene 240
Methanol 630
Toluene 4700
Methanol 7900
Toluene 1 2
Methanol 110
Toluene 60
Methanol 55
Ref. 32.
ANNEX TO TABLE 7. COMPOUND CHEMISTRIES
TXs
Triplet state
energy level
R Rl R2 R3 R4
Abbrev. (kcal/mol)
4
RIQI$&
R2
R3
Moks
H Cl H H CTX 62
H
CWCHdz
H H I TX 6 1
CH3 H COOET H ETX 58,5
H H H COOET TX1 6 3
7H3
H
C-y-N20
SCH3
0 CH,
OCH3
WHdz
HMK 65
TPMK 6 1
OMK 65
NMK 63
Triplet State lifetimes, Triplet State Energy levels and Rate Constants II / 179
TABLE 8. TRIPLET STATE LIFETIMES (rT) OF THE SENSITIZER
(TXI) IN DIFFERENT MEDIA, AND RATE CONSTANT (kT) OF THE
INTERACTION BETWEEN TXI AND TPMKb
TABLE 11. RATE CONSTANT OF INTERACTION OF KETONES
AND LIGHT STABILIZERS IN SOLUTION
Photoinitiator Light stabilizer
10 -6ka
(VmoVs) Refs.
Medium
TT
(ns)
9
10-6kT
(cp at 28C) (VmoVs)
Benzophenone
Acetone
LSl 6500 34
LS2 8550
LS3 10300
LS4 15000
LS5 7050
SL6 5900 35
LSl 500 36
LSI 700
TMPTA (100%)
Acrylate (66/33)
Toluene-Ep. acrylate
(50/50)
Toluene-TMPTA (25/75)
Toluene-TMPTA (50/50)
Toluene-TMPTA (75/25)
HDDAd (100%)
HDDA-Ep. acrylate
(50/50)
Toluene-HDDA (50/50)
Tol uene-HDDA-Ep.
acrylate (25150125)
Toluene-PETA (50/50)
Toluene-PETA-Ep.
acrylate (43143114)
Toluene
Methanol
650 40 80
2200 1 8 5 3 1
1500 9.5 3 5
270 5.8 1 3 5
200 1 . 7 <40
280 0.9 150
650 5.2 95
2500 58 22
1000 1 . 2 140
850 5.8 68
ANNEX TO TABLE 11.
Lsl: p#xgg
220 3 . 1 40
360 6.9 69
50 0.53 240
140 0.52 630
Viscosity: q.
*Ref. 33; for formula, see Annex to Table 7.
Trimetbylolpropane triacrylate.
dHexanedioldiacrylate.
ePentaerytbritol triacrylate.
TABLE 9. SOME VALUES OF THE TRIPLET STATE ENERGY
LEVELS OF PHOTOINITIATORS AND MONOMERS
Compound Triplet state energy (AE) (kcaUmo1)
I l a 69
14a 73
I7a 53
I8a 53
19b 59
M2 6 1
I14a 15
124 57
Cited in Ref. 1 3
Cited in Ref. 38
Ls4: -1
TABLE 10. VALUES OF t;, fT, AND kit IN SOLUTION
Photoinitiators
10-6kb
a
$ bs)
ZT ( n s ) (YmoVs)
Ls5:
LS6:
LS7:
4200 4000 0.85
cH$* fmC(Z02-Q- CH3 3300 2000 14
0 CH3
,CH3
$X,-OH
0 CH3
Cl
470 470 15
4000 1750 24
Determined in bulk epoxyacrylate-HDDA (60 :4Ow/w); a in solution b in the
presence of LSl (2%).; Ref. 34.
References page II - 180
II / 180 PHOTOPOLYMERIZATION REACTIONS
C. REFERENCES
1. (a) Lasers in Polymer Science and Technology: Applica-
tions, J. P. Fouassier, J. F. Rabek (Eds.), CRC Press, Boca
Raton, 1990.
(b) Radiation Curing in Polymer Science and Technology,
J. l? Fouassier, J. F. Rabek (Eds.), Chapman & Hall, London,
(1993).
2. J. I? Fouassier, Photoinitiation, Photopolymerization, Photo-
curing, Hanser, Munich, (1995).
3. (a) C. Decker, in: S. P. Pappas, (Ed.), Radiation Curing:
Science and Technology, Plenum Press, New York,
1992.
(b) C. Decker, B. Elzaouk in Laser Curing of Photopoly-
mers, Proc. Polymer Photochemistry Symposium, Genes,
112, (1993).
(c) C. Decker, B. Elzaouk, Eur. Polym. J., 31 (12), 1155
(1995).
4. D. Ruhlmann, J. P. Fouassier, Eur. Polym. J., 27 (9), 991
(1991).
5. D. Ruhlmann, J. P Fouassier, W. Schnabel, Eur. Polym. J., 28
(3), 287 (1992).
6. D. Ruhlmann, F. Wieder, J. P. Fouassier, Eur. Polym. J., 28 (6),
591 (1992).
7. R. Kuhlmann, W. Schnabel, Polymer, 18, 1163 (1977).
8. J. P Fouassier, in: J. P. Fouassier, J. F. Rabek (Eds.) Lasers in
Polymer Science and Technology: Applications, CRC Press,
Boca Raton, 1990.
9. J. P. Fouassier, D. J. Lougnot, Polymer Comm., 31, 418
(1990).
10. J. P. Fouassier, D. J. Lougnot, J. Chem. Sot., Faraday Trans., 1,
83 (9), 2935 (1987).
11. G. Amirzadeh, R. Kuhlmann, W. Schnabel, J. Photochem., 10,
133 (1979).
12. J. P. Fouassier, D. J. Lougnot, L. Avar, Polymer, 36 (26), 5005
(1995).
13. J. P. Fouassier, in: J. P. Fouassier, J. F. Rabek (Eds.) Radia-
tion Curing in Polymer Science and Technology, Chapman
& Hall, London, vol. II, 1993.
14. T. Sumiyoshi, W. Schnabel, A. Henne, J. Photochem., 32,191
(1986).
15. D. Ruhlmann, K. Zahouily, J. P. Fouassier, Eur. Polym. J., 28
(9), 1063 (1992).
16. J. P. Fouassier, D. Burr, Macromolecules, 23, 3615 (1990).
17. J. P. Fouassier, D. J. Lougnot, J. C. Scaiano, Chem. Phys. Lett.,
160, 335 (1989).
18. l? J. Wagner, M. J. Lindstrom, Jacs, 109, 3062 (1987).
19. F. Morlet-Savary, J. P. Fouassier, H. Tomioka, Polymer, 33,
4202 (1992).
20. G. Amirzadeh, W. Schnabel, Makromol. Chem., 182, 2821
(1981).
21. R. Kuhlmann, W. Schnabel, Angew. Makromol. Chem., 57,
195 (1977).
22. R. Kuhlmann, W. Schnabel, Polymer, 17, 419 (1976).
23. F. Morlet-Savary, J. P. Fouassier, T. Matsumoto, K. Inomata,
Polymers for Adv. Techn., 5, 56 (1994).
24. N. S. Allen, A. W. Timms, W. A. Green, F. Catalina,
T. Co&es, S. Navaratnam, B. J. Parsons, J. Chem. Sot.
Faraday, 90, 83 (1994).
25. D. J. Lougnot, C. Turck, J. P. Fouassier, Macromolecules, 22,
108 (1989).
26. W. Schnabel, in: J. P. Fouassier, J. F. Rabek (Eds.), Lasers in
Polymer Science and Technology: Applications, vol. II,
CRC Press, Boca Raton, 1990.
27. T. Sumiyoshi, W. Weber, W. Schnabel, Z. Naturforsch, 40a,
541 (1985).
28. J. P. Fouassier, D. Burr, J. V. Crivello, J. Photochem. Photo-
biol., A: Chem., 49, 318 (1989).
29. G. Mannivannan, J. P Fouassier, J. V. Crivello, J. Polym. Sci.
Part A: Polym. Chem., 30, 1999 (1992).
30. H. J. Timpe, K. l? Kronfeld, U. Lammel, J. l? Fouassier,
D. J. Lougnot, J. Photochem., 52, 111 (1990).
3 1. M. R. V. Sahyun, R. J. DeVoe, P M. Olofson, in: J. P Fouassier,
J. F. Rabek, (Eds.), Radiation Curing in Polymer Science and
Technology, vol. II, Chapman & Hall, London, 1993.
32. A. Bohrer, G. Rist, K. Dietliker, V. Desobry, J. P. Fouassier,
D. Ruhlmann, Macromolecules, 25, 4182 (1992).
33. J. P. Fouassier, D. Ruhlmann, Eur. Polym. J., 29 (4), 505
(1993).
34. J. P. Fouassier, D. Ruhlmann, A. Erddalane, Macromolecules,
26, 721 (1993).
35. J. I? Guillory, C. F. Cook, Jacs, 95, 4885 (1973).
36. l? Bortolus, in: J. P. Fouassier, J. F. Rabek (Eds.), Radiation
Curing in Polymer Science and Technology, vol. II,
Chapman & Hall, London, 1993.
37. H-J. Timpe, Topics in Current Chemistry, vol. 156, 167,
(1990).
38. H-J. Timpe, K-P Kronfeld, J. Photochem. & Photobiol., A:
Chem., 46, 253 (1989).
39. J. C. Netto-Ferreira, D. Weir, J. C. Scaiano, J. Photochem. &
Photobiol., A: Chem., 48, 345 (1989).
40. J. C. Scaiano, L. C. Stewart, J. Am. Chem. Sot., 105 (1 l),
3609 (1983).
41. E. Klimtchuk, M. A. J. Rodgers, D. C. Neckers, J. Phys.
Chem., 96 (24), 9817 (1992).
42. Y. Yagci, W. Schnabel, Makromol. Chem., Rapid Commun.,
8, 209 (1987).
43. Y. Yagci, S. P. Pappas, W. Schnabel, Z. Naturforsch, 42a, 1425
(1987).
Free Radical Copolymerization
Reactivity Ratios
Robert Z. Greenley*
Monsanto Co., 544 Oak Valley Drive, St. Louis, MO 63131, USA
A. Introduction
B. Tables
Table 1. Copolymer Reactivity Ratios
Table 2. Listing of Quick Basic (Microsoft)
Program for Calculating Reactivity
Rat i os
C. References
II-1 81
II-1 82
II-1 82
II-288
II-290
A. INTRODUCTION
When a vinyl monomer is copolymerized with a second
monomer, the relationship between the composition of the
initially formed copolymer and the initial monomer mixture
is given by
dml Ml (041 + a)
-=
dm2 M2(r2M2 + Ml)
where ml is the number of moles of monomer 1 entering
the copolymer, m2, the number of moles of monomer 2
entering the copolymer, MI, the number of moles of
monomer 1 in the monomeric mixture, M2, the number of
the moles of monomer 2 in the monomer mixture, and r1
and r2 are the monomer reactivity ratios.
The monomer reactivity ratios, rl and r2, for any
monomer pair are the ratios of the rate constants of the
different propagation reactions:
-M; fM1- -MlM;
kll
N M; + M2- N MlM;
kn
NM; + M2- N M2M;
kn
wM;+M1-wM2M;
k21
with r1 = kll/k
12, r2 = kdh.
N M represents a poly-
mer chain ending in a radical derived from monomer M.
The original compilations of reactivity ratios and their
references were published by L. J. Young in the first two
editions of this Handbook. In the third edition, the original
listings and those through 1986 were re-evaluated. This
fourth edition contains an additional 548 evaluated mono-
mer pairs giving a total of 3,265 such pairs. Only free
*Retired.
radical reactivity ratios are listed. When the original
references were available, they were read. If the experi-
mental data was published, the reactivity ratios were
recalculated according to the methods of Kelen and Tudiis
(803,804). The 95% confidence limits for the reactivity
ratios were also calculated (805). If the authors used this
method for r-value evaluation, including adjustment of the
monomer feeds for total conversion, then the reported
values were utilized. There are a number of reported
reactivity ratios that are not reported here. This is due to the
absence of these values in the abstracts of papers which
were published in journals unavailable to the author.
All of the monomer pairs in Table 1 are cross-referenced.
The full spelling of each monomer was included in its
Monomer 1 citation. Sometimes truncated but distinguish-
able names have been used in the Monomer 2 lists.
If only the reactivity ratios and reference are given, then,
either no experimental data was given or the journal was not
available and the Chemical Abstracts summary was the
source of the data. If a Y or N (yes or no) appears in the
conversion (Conv.) column then the reactivity ratios were
recalculated. If a recalculation was performed but the 95%
confidence columns (95%) are still left blank, it indicates
that only two feed/polymer data pairs were available. In
general, if there is a citation (Y or N) in the Conv. column
but no reactivity ratios are shown in the reactivity ratio
columns, the copolymerization did not follow the copoly-
merization equation (ionic or penultimate effects were
prevalent). In a few cases, the data were too scattered to
allow a reactivity ratio calculation.
Recalculations yield negative reactivity ratios in several
cases. We are aware that this is a physically unrealistic
artifact. When the 95% confidence limits are applied to
these negative numbers, a value of zero usually falls within
these limits. It may be noted that a single reference
sometimes contains a variety of reactivity ratios for one
monomer pair. The reader may assume that these result
from a change of polymerization conditions; e.g., different
polymerization temperatures or polymerization media of
varying polarity.
For those who are interested in using the Kelen-TudBs
calculations, a listing of a simplistic program written in
QuickBasic (Microsoft) is also given (Table 2).
II / 181
II / 182 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
B. TABLES
TABLE 1. COPOLYMER REACTIVITY RATIOS
Monomer 1 Monomer 2
rl
f95% r2 f95% Conv. Refs.
Acenaphtbalene
Acenaphthalene
Acenaphthalene
Acenaphthalene
Acenaphthalene
Acenaphthalene
Acenaphthalene
Acenaphthalene
Acenaphthalene
Acenaphthalene
Acenaphthalene
Acenaphthalene
Acenaphthalene
Acenaphthalene
Acenaphthalene
Acenaphthalene
Acetamide, N-(4-methacryloyloxyphenyl)-
2-(4-metboxy)
Acetamide, N-vinyl-
Acetamide, N-vinyl-
Acetamide, N-vinyl-
Acetamide, N-vinyl-
Acetamide, N-vinyl-
Acetamide, N-vinyl-
Acetanilide, 4-(2-methacryloyloxy)-
ethyloxy)
Acetanilide, 4-(2-methactyloyloxy)-
hexyloxy)
Acetanilide, 4-(methacryloyloxy)-
Acetate, 2-chloro-, vinyl
Acetate, ally1
Acetate, chloro-, ally1
Acetate, dichloro-, ally1
Acetate, isopropenyl
Acetate, trichloro-, ally1
Acetylene, phenyl-
Acetylene, phenyl-
Acetylene, phenyl-
Acetylene, phenyl-
Acetylene, phenyl-
Acetylene, phenyl-
Acetylene, phenyl-
Acetylene, phenyl-
Acetylene, phenyl-
Acetylene, phenyl-
Acetylene, phenyl-
Acetylene, phenyl-
Acetylene, phenyl-
Aconitate, trimethyl
Aconitate, trimethyl
Aconitate, trimethyl
Aconitate, trimethyl
Aconitate, trimethyl
Acrolein
Acrolein
Acrolein
Acrolein
Acrolein
Acrolein
Acrolein
Acrolein
Acrylate, (-)-menthyl
Acrylonitrile
Carbazole, N-vinyl-
Fumarate, diisopropyl
Maleic anhydride
Maleic anhydride
Mal ei mi de, N-cyclohexyl-
Metbacrylate, (-)-me&y1
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylonitrile
Pyrrolidone, N-vinyl-
Pyrrolidone, N-vinyl-
Stilbene
Styrene
Methacxylate, 2-hydroxyethyl
2.56
6.62
2.51
0.46
0.46
0.57
2.48
1.05
0.99
2.25
2.38
1.77
0.13
0.55
0.14
0.15
0.02
- 0.03
0.06
0.02
- 0.04
0.11
0.316
0.36
0.38
0.44
0.15
0.12
0.05
0.085
0.04
0.04
5.65
0.33
1.49
0.23 - 0.01
3.81
0.61
0.04
645
575
331
1039
1039
26
1039
645
326
326
575
515
326
326
725
525
1 0 5 1
Acrylamide 0.3 1.4 984
Methacrylate, methyl 0.19 2.65 984
Methacrylate, methyl 0.71 1.18 984
Methacrylate, methyl 0.01 2.1 984
Vinyl acetate 5.5 0.6 984
Vinyl acetate 2 1 0 984
Methacrylate, 2-hydroxyethyl 0.67 1.39 1096
Methacrylate, 2-hydroxyethyl 0.87 1.19 1096
Methacrylate, 2-hydroxyethyl
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Fumarate, diisopropyl
Vinyl acetate
Acrylate, methyl
Acrylate, methyl
Acrylonitrile
Isoprene
Maleic anhydride
Methacrylate, methyl
Methacrylate, butyl
Methacrylate, isobutyl
Methacrylate, methyl
Metbactylate, met hyl
Methacrylonitrile
Pyridine, 2-vinyl-
Styrene
Acrylonitrile
Butadiene
Styrene
Vinyl chloride
Vinylidene chloride
Acrylamide
Acrylamide
Acrylate, butyl
Acrylate, butyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, methyl
Acrylate, methyl
1.94
1.18
0.43
0.69
0.54
0.011
0.28
0.212
0.093
0.325
0.1
0.08
0.2
0.21
0.27
1.69
0.07
0.04
0.072
0.01
0.083
26.56
0.016
0.78
0.8
1.8
0.77
0.57
0.67
0.41
0.622
0.664
0.266
3.01
0.06
1.5
1.7
1.9
- 0.06
1.111
0.78
0.062
0.045
0.044
0.16
0.095
0.33
- 0.48
0
- 0.013
0.19
0.15
1.95
1.59
1.86
2.29
1.2
1.98
- 0.07
1.41
0.12
0.11
0.22
0.009
0.02
0.92
0.4
0.091
0.94
0.58
0.1
0.19
0.58
0.44
0.03
0.4
0.324
4.24
0.4
1.026
0.04
64.6
0.8
0.18
0.638
1.12
0.6
1.09
7.86
0.83
23.74
0.23
0.02
0.032
0.41
0.25
3.58
0.12
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
N
N
Y
N
N
N
Y
1096
892
1045
1045
1045
1038
1045
60
731
60
648
197
443
565
565
357
732
648
192
357
1 4 7
147
147
1 4 7
149
207
208
291
292
291
292
207
291
Copolymer Reactivity Ratios II / 183
TABLE 1. contd
Monomer 1 Monomer 2
rl f95% r2 f95% Conv. Refs.
Acrolein Acrylate, methyl
Acrolein Acrylic acid
Acrolein Acrylic acid
Acrolein Acrylonitrile
Acrolein Acrylonitrile
Acrolein Acrylonitrile
Acrolein Acrylonitrile
Acrolein Methacrylate, methyl
Acrolein Methacrylate, methyl
Acrolein Methacrylonitrile
Acrolein Methacrylonitrile
Acrolein Pyridine, 2-vinyl-
Acrolein Styrene
Acrolein Styrene
Acrolein Styrene
Acrolein Styrenesulfonate, p-, sodium
Acrolein Styrenesulfonate, p-, sodium
Acrolein Styrenesulfonate, p-, sodium
Acrolein Vinyl acetate
Acrolein Vinyl chloride
Acrolein diethylacetal Acrylonitrile
Acrolein diethylacetal Maleic anhydride
Acrolein, methyl- Acrylate, butyl
Acrolein, methyl- Acrylonitrile
Acrolein, methyl- Acrylonitrile
Acrolein, methyl- Acrylonitrile
Acrolein, methyl- Acrylonitrile
Acrolein, methyl- Methactylate, methyl
Acrolein, methyl- Methacrylonitrile
Acrolein, methyl- Methacrylonitrile
Acrolein, methyl- Methacrylonitrile
Acrolein, methyl- Styrene
Acrolein, methyl- Styrene
Acrolein, methyl- Vinyl acetate
Acrolein, 2-chloro- Styrene
Acryl-2-ethyl-4,5,7-trinitro- Acrylate, N-(Zhydroxyethyl)-
9-flurenone-2-carboxylate carbazolyl
Acryl-2-ethyl-4,5,7-trinitro-9-flurenone- Methacrylate, N-(2-hydroxyethyl)
2-carboxylate carbazolyl
Acrylamide Acet ami de, N-vinyl-
Acrylamide Acrolein
Ac r yl a mi de Acrolein
Ac r yl a mi de Acrylic acid
Ac r yl a mi de Acrylic acid
Ac r yl a mi de Acrylic acid
Ac r yl a mi de Acrylic acid
Ac r yl a mi de Acrylic acid
Acrylamide Acrylic acid
Acrylamide Acrylic acid, cis-3-bromo-
Acrylamide Acrylic acid, cis-3-ethyl-
Acrylamide Acrylic acid, truns-3-bromo-
Acrylamide Acrylic acid, trans-3-ethyl-
Acrylamide Acrylonitrile
Acrylamide Acrylonitrile
Acrylamide Acrylonitrile
Acrylamide Acrylonitrile
Acrylamide Acrylonitrile
Acrylamide Cinnamic acid, cis-
Acrylamide Cinnamic acid, trans-
Acrylamide Crotonic acid
Acrylamide Crotonic acid
Acrylamide Crotonic acid
Acrylamide Crotonic acid
Acrylamide Crotonic acid, cis-
Acrylamide Crotonic acid, truns-
2.54
2.48
0.5
1.16
1.07
1.52
1.28
0.76
0.59
0.68
0.72
2.64
0.216
0.02
0.32
0.395
0.26
0.113
3.04
5.22
0.02
0.18
2.5
1.7
3.8
3.8
1.72
0.4
1.78
1.25
1.25
0.833
0.3
0.98
0.15
0.585
0.93
1.24
0.38
0.28
0.13
0.08
0.07
0.06
0.03
0.01
0.12
0.3
0.12
0.05
0.4
0.05
0.14
0.036
0.01
0.002
0.092
0.16
0.018
0.43
0.13
0.03
0.017
0.02
0.006
0.033
0. 07 1
0.009
0.12
0.11
0.42 0.19
0.07 0.01
0.092
1.08
0.08
1.15
0.88
0.71
0.48
0.6
1.136
1.33
1.17
1.2
-0.12
0.257
0.22
0.205
0.327
0.047
0.01
- 0.02
0.03
11.19
0.07
0.02
0.15
0.15
0.15
0.03
0.1
0.41
0.45
0.45
0.173
0.41
0.15
0.02
0.912
0.017
0.07
0.028
0.05
0.079
0.102 0.022 0.773 0.096
1.4
0.8
0.18
1.08
0.445
1.346
0.598
0.58
1.06
7.64
6.32
4.13
8.19
0.81
1.08
0.5
1.36
1.3
3.84
3.4
3.76
4.23
4.72
5.32
0.23
0.02
0.17
0.075
0.044
0.047
1.67
0.68
0.76
1.09
0.11
0.51
0.26
0.3
1.95
1.59
0.288
1.644
0.341
1.38
3.8
0.29
- 0.2
-0.16
- 0.33
- 0.21
0.863
0.97
1.8
0.88
0.8
0.58
0.1
0.029
0.069
0.012
0.14
0.11
0.1
0.16
0.11
0.033
0.1
0.75
0.68
0.24
0.89
1.37
- 0.24
-0.18
-0.19
0.11
0.12
0.28
0.15
0.14
0.19
7.2 0.33 - 0.085 0.024
N
Y
N
N
N
Y
N
N
N
Y
N
Y
Y
Y
Y
N
N
Y
N
N
Y
Y
N
N
Y
Y
Y
N
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
Y
Y
Y
292
57
57
207
207
208
504
291
292
208
446
208
291
292
307
57
57
57
207
271
767
767
589
455
587
589
9 1
589
208
587
589
223
589
589
806
715
703
984
207
208
221
278
278
37
869
869
298
298
298
298
228
228
330
421
461
298
298
298
298
569
569
341
341
References page II - 290
II / 184 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
r1
zt95%
r2
zt95% Conv. Refs.
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acrylamide
Acryl ami de, 2-chloro-N,N-dimethyl-
Acryl ami de, 2-chloro-N,N-dimethyl-
Acrylamide, N,N-dibutyl-
Acrylamide, N,N-diethyl-
Acrylamide, N,N-diethyl-
Acrylamide, N,N-dietbyl-
Acrylamide, N,N-diethyl-
Acrylamide, N,N-diethyl-
Acrylamide, N,N-diethyl-
Acrylamide, N,N-dimetbyl-
Acrylamide, N,N-dimethyl-
Acrylamide, N,N-dimetbyl-
Acrylamide, N,N-dimethyl-
Acryl ami de, N,N-dimethyl-
Acrylamide, N,N-dimethyl-
Acrylamide, N,N-dimethyl-
Acrylamide, N,N-dimethyl-
Acrylamide, N-(2-(4-hydroxyphenyl)ethyl)-
Acrylamide, N-(2-(propionamide)-
Acrylamide, N-methyl-
Acrylamide, N-methyl01
Acrylamide, N-methyl01
Acrylamide, N-methyl01
Acryl ami de, N-methyl01
Acryl ami de, N-methyl01
Acryl ami de, N-methyl01
Acrylamide, N-methyl01
Acrylamide, N-methyl01
Acrylamide, N-methyl01
Acrylamide, N-methyl01
Acrylamide, N-methylol-
Acrylamide, N-octadecyl-
Acrylamide, N-octadecyl-
Dioxolane, 1,3,4-methvlene-2-trichloro- 8.6
0.56
0.05
0.14
0.04
Maleic anhydr i de -
Metbacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 3-methoxy-
2-hydroxypropyl
Methacrylate, dimethylaminoethyl
sulfate
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylic acid
Metbacrylic acid
Methacrylic acid
Methylenebutyrolactone
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Succinimide, N-vinyl-
Vinyl chloride
Vinyl methyl ketone
Vinyl methyl ketone
Vinylene carbonate
Vinylmethylphenylsulfonium
tetrafluoro
Vinylsulfonic acid
Methacrylate, methyl
Styrene
Styrene
Acrylic acid
Butanoate, 3-acrylamido-3-methyl-,
sodium
Methacrylate, methyl
Styrene
Styrene
Styrene
Metbacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Styrene
Styrene
Styrene
Sulfonate, 2-acrylamido-
2-methylpropane
Vinyl methyl ketone
Methacrylamide, N-(2-hydroxypropyl)-
Styrene
Methacrylate, methyl
Acrylate, butyl
Acrylate, ethyl
Acrylate, methyl
Acrylonitrile
Acrylonitrile
Acrylonitrile
Methacrylate, methyl
Methacrylate, methyl
Styrene
Vinyl chloride
Styrene
Acrylonitrile
Methacrylate, methyl
0.037 616
0 655
1.89 689
0.98 928
3.98 689
0.52
2.29
0.53
0.82
0.9
0.57
0.58
0.56
0.3
0.58
1.32
0.33
0.59
8.97
0.2
1.86
0.05
0.44
0.09
1.07
1.9
2.34
3
2.53
3
1.63
4.4
0.15
2.85
1.17
1.21
1.49
1.13
0.65
1.05
0.17
0.2
0.17
0.09
0.45
0.12
0.13
0.14
0.43
0.06
0.04
0.16
0.03
3.99
1.02
13.8
3.4
0.7
0.13
0.47
0.75
0.05
0.1
0.44
0.23
3.5 0.15 0.3 0.1
- 0.159 0.502 2.71 0.398
- 0.036 0.152 1.29 0.065
0.294 0.058 1.6 0.058
0.35 0.12 0.36 0.04
0.987 0.153 0.22 0.138
0.41
0.39
0.34
0.18
0.57
0.59
0.21
0.12
0.49
0.47
1.108
0.15
0.08
0.09
0.21
0.3
0.15
0.2
0.59
1.65
1.23
1.36
1.54
2.15
2.8
2.64
1.15
1.37
1.32
0.162
0.16
0.08
0.1
0.15
0.35
0.1
0.12
0.949
0.82
0.95
0.86
0.05
0.61
1.4
1.9
1.2
2.33
2.56
0.7
0.7
0.48
0.4
1.4
0.42
0.36
0.09
0.3
0.72
0.1
1.01
1.84
1.14
0.87
1.4
1.3
0.7
0.98
0.22
1.62
1.62
0.03
0.03
0.17
0.11
1.55
1.034
4.119
0.43
0.09
0.21
0.09
0.05
0.02
0.07
N
N
N
N
N
N
N
Y
Y
Y
Y
Y
N
Y
N
N
N
N
N
N
N
Y
Y
N
N
Y
Y
Y
1052
314
314
314
691
1028
852
852
746
295
314
314
314
343
555
600
156
609
609
387
793
1066
917
917
806
205
857
170
739
739
739
315
315
691
170
315
315
857
609
965
295
691
441
442
441
442
577
596
593
596
596
1 5 7
891
119
290
TABLE 1. contd
copol ymer React i vi t y Rat i os II / 185
Monomer 1 Monomer 2
f.1
f95%
r2
Zt95% Conv. Refs.
Acrylamide, N-octadecyl-
Acrylamide, N-octadecyl-
Acrylamide, N-octadecyl-
Acrylamide, N-octyl-
Acrylamide, N-propyl-
Acrylamide, N-propyl-
Acrylamide, N-tert-butyl-
Acrylamide, N-terf-butyl-
Acrylamide, wfluoro-
Acrylamido, l-,-l-deoxy-o-glucitol
Acrylamido, 1-,-1-deoxy-D-glucitol
Acrylamido, l-,-l-deoxy-o-glucitol
Acrylamido, 2-,2-methylpropanesulfonate,
sodium
Acrylamido, 2-,-2-methylpropanesulfonic
acid
Acrylamido, 2-,-2-methylpropanesulfonic
acid
Acrylamido-2-methylpropane sulfonate
sodium salt
Acrylamidomethylamino, p-, azobenzene
Acrylamidomethylamino, p-, azobenzene
Acrylate, (-)-mentbyl
Acrylate, (-)-menthyl
Acrylate, 1.1.5trihydroperlluoroamyl
Acrylate, 2,3-dibromopropyl
Acrylate, 2,4,5-trichlorophenyl
Acrylate, 2,4,5-trichlorophenyl
Acrylate, 2,4,6-tribromophenyl
Acrylate, 2,4dinitrophenyl
Acrylate, 2,4-dinitrophenyl
Acrylate, 2(0-ethyl methylphosphonoxy)-,
methyl
Acrylate, 2-chloroethyl
Acrylate, 2-chloroetbyl
Acrylate, 2-chloroethyl
Acrylate, 2-chloroethyl
Acrylate, 2-chloroethyl
Acrylate, 2-chloroethw.
Acrylate, 2-chloroethyl
Acrylate, 2-chloroethyl
Acrylate, 2-chloroethyl
Acrylate, 2-chloroethyl
Acrylate, 2-chloroethyl
Acrylate, 2-chloroethyl
Acrylate, 2-chloroethyl
Acrylate, 2-chloroethyl
Acrylate, 2-chloroethylglucitol
Acrylate, 2-cyano-, methyl
Acrylate, 2-cyano-, methyl
Acrylate, 2-cyanoethyl
Acrylate, 2-ethylhexyl
Acrylate, 2-ethylhexyl
Acrylate, 2-etbylhexyl
Acrylate, 2-ethylhexyl
Acrylate, 2-etbylhexyl
Acrylate, 2-ethylhexyl
Acrylate, 2-hydroxyethyl
Acrylate, 2-hydroxyethyl
Acrylate, 2-hydroxyetbyl
Acrylate, 2nitrobutyl
Acrylate, 2-nitrobutyl
Acrylate, 2nitrobutyl
Acrylate, 3,4-epoxyhexahydrobenzyl
Styrene 0.54
Vinyl acetate 8.25
Vinylidene chloride 1.4
Styrene 0.258
Acrylate, butyl 0.4
Acrylate, methyl 0.26
Acrylonitrile 1.14
Methactylate, methyl 2.83
Methacrylate, methyl 0.148
Methacrylate, methyl 0.05
Styrene 0.03
Vinyl acetate 0.98
Vinyl acetate 11.6
Methacrylate, 2-hydroxyethyl 0.9 0.86
Methacrylate, 2-hydroxypropyl 1.03 0.89
N-Vinylpyrrolidone
Styrene
Vinyl acetate
Acenaphthalene
Pyridine, .4-vinyl-
Methactylonitrile
Styrene
Pyrrolidone, N-vinyl-
Styrene
Styrene
Acrylate, N-(2-hydroxyethyl)-carbai
Methacrylate, N-(Zhydroxyethyl)-
carbazolyl
Methacrylate, methyl
Acrylate, ethyl
Acrylate, methyl
Acrylonitrile
Itaconate, bis(tri-n-butyltin)
Itaconic anhydride
Itaconic anhydride
Maleic anhydride
Methacrylate, methyl
Fyrrolidone, N-vinyl-
Styrene
Styrene
Styrene
Vinyl butyl ether
Vinyl isobutyl ether
Styrene
Styrene, u-methyl-
Vinyl acetate
Styrene
Acrylate, glycidyl
Methacrylate, glycidyl
Styrene
Styrene
Vinyl acetate
Vinyl chloride
Acrylate, butyl
Acrylate, ethyl
Acrylate, methyl
Acrylonitrile
Methacrylate, methyl
Styrene
Acrylonitrile
0.66
8.5 0.083
12.98 0.126
0.291
0.14
0.16
0.163
0.23
0.1
rolyl 0. 158
0.186
0.44
1.03
1.07
0.87
0.683
- 0.016
0.251
7.15
0.37
0.52
0.1
0.139
0.12
2.01
2.24
0.14
0.001
0.5
0.128
1.12
0.09
0.31
0.26
7.5
4.15
0.9
0.97
0.9
1.76
0.27
0.12
0.388
0.14
1.46
0.11
0.119
0. 08 1
0.09
0.02
0.87
0.017
0.02
0.021
0.015
0.009
0.25
0.022
0.021
0.31
0.17
0.083
0.09
0.074
0.07
0.13
0.6
0.23
0.24
0.13
0.69
0.04
0.01
0.074
2.08
0.004
0.432
2.715
0.8
1.2
0.2
0.25
2.13
3.75
2.42
0.03
0.05
0.13
2.32
1.03
0.42
0.012
0.277
0.2
0.109
0.243
0.73
0.9
0.9
1.03
0.391
2.46
2.61
0.027
2.15
0.03
0.55
0.494
0.54
0
0
0.49
0.05
0.005
0.399
1.18
2.41
0.96
0.94
0.04
0.16
0.3
0.5
0.94
0.67
1.19
0.35
0.25
0.12
0.011
0.008
0.244
0.136
0.24
0.08
0.17
0.45
0.008
0.048
0.026
0.034
0.04
0.38
0.32
0.004
0.47
0.097
0.2
0.032
0.06
0.46
0.3
0.06
0.03
0.04
0.25
0.12
0.03
0.13
Y
Y
Y
Y
N
N
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
Y
N
N
N
N
N
N
N
Y
290
119
119
806
730
730
709
709
823
258
258
258
700
618
618
939
858
858
645
667
809
643
840
622
643
716
716
882
726
726
790
940
365
365
117
790
790
140
178
790
790
790
806
452
452
1 7 8
126
674
126
463
570
510
868
868
868
234
234
234
680
References page II - 290
II / 186 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
rl
f95%
rz
It95% Conv. Refs.
Acrylate, 3,4-epoxyhexahydrobenzyl
Acrylate, 4-acetylphenyl
Acrylate, P-acetoxymethyl-, methyl
Acrylate, P-acetoxymethyl-, methyl
Acrylate, P-chloro-2-hydroxypropyl
Acrylate, P-ethoxy-, ethyl
Acrylate, P-ethoxy-, ethyl
Acrylate, N-(2-hydroxyethyl)-
3,6-dichlorocarbazolyl
Acrylate, N-(2-hydroxyethyl)carbazolyl
Acrylate, N-(2-hydroxyethyl)carbazolyl
Acrylate, N-(2-hydroxyethyl)carbazolyl
/
Acrylate, N-(2-hydroxyethyl)carbazolyl
Acrylate, N-(2-hydroxyethyl)carbazolyl
Acrylate, a-(4-chlorobenzyl)-, ethyl
Acrylate, a-(Ccyanobenzyl)-, ethyl
Acrylate, cc-(4-methoxybenzyl)-, ethyl
Acrylate, a-(O-ethyl methylphosphonoxy)-
methyl
Acrylate, a-(hydroxymethyl)-, methyl
Acrylate, a-[2,2-bis(carbomethoxy)ethyl]-,
methyl
Acrylate, cc-[2,2-bis(carbomethoxy)ethyl]-,
methyl
Acrylate, wacetoxy-, ethyl
Acrylate, cc-acetoxy-, ethyl
Acrylate, a-acetoxy-, ethyl
Acrylate, a-acetoxy-, ethyl
Acrylate, a-acetoxy-, ethyl
Acrylate, a-benzyl-, methyl
Acrylate, a-benzyl-, ethyl
Acrylate, a-benzyl-, methyl
Acrylate, a-benzyl-, methyl
Acrylate, a-bromo-, ethyl
Acrylate, a-butyl-, methyl
Acrylate, a-chloro-, methyl
Acrylate, cc-chloro-, ethyl
Acrylate, wchloro-, ethyl
Acrylate, u-chloro-, ethyl
Acrylate, a-chloro-, ethyl
Acrylate, a-chloro-, ethyl
Acrylate, a-chloro-, ethyl
Acrylate, a-chloro-, ethyl
Acrylate, wchloro-, ethyl
Acrylate, wchloro-, methyl
Acrylate, cr-chloro-, methyl
Acrylate, cl-chloro-, methyl
Acrylate, a-chloro-, methyl
Acrylate, a-chloro-, sodium
Acrylate, wcyano-, methyl
Acrylate, a-cyano-, methyl
Acrylate, a-cyano-, methyl
Acrylate, wcyano-, methyl
Acrylate, cc-cyano-, methyl
Acrylate, wcyano-, methyl
Acrylate, cl-cyclohexyl-, methyl
Acrylate, cl-ethyl-, methyl
Acrylate, a-ethyloxymethyl-, methyl
Acrylate, a-fluoro-, ethyl
Acrylate, a-fluoro-, methyl
Acrylate, cc-hexafluoropropyloxymethyl-,
methyl
Styrene 1.97
Methacrylate, glycidyl 0.292
Methacrylate, methyl 0.24
Styrene 0.19
Acrylonitrile 0.7
Acrylonitrile 0. 26
Styrene 0.21
Methacrylate, 2,4-dinitrophenyl 0.115
0.35
0.141
0.56
0.44
0.029
0.27
0.644
0.91
0.34
0.24
2.42
46.98
1.207
0.3
0.13
1.8
27.03
0.032
Acryl-2-ethyl-4,5,7-trinitro-9-fluorene
Acrylate, 2,4-dinitrophenyl
Acryloyl-P-hydroxyethyl-
3,5-dinitrobenzoate
Methacryloyl-P-hydroxyethyl-
3,5-dinitrobenzoate
Methacryloyl-P-hydroxyethyl-
3,5-dinitrobenzoate
Styrene
Styrene
Styrene
Methacrylate, methyl
0.912 0.079 0.585 0.028
0.109 0.026 0.158 0.015
0.62 0.044 0.361 0.016
N 680
Y 1012
1 0 9 1
1 0 9 1
654
N 194
Y 194
Y 736
Y 715
Y 716
Y 702
1.04 0.14 0.08 0.026 Y 702
0.334 0.022 1.364 0.018
1.03
0.65
0.71
0.44
0.13
0.09
0.24
0.04
0.06
0.33
0.73
0.09
0.05
0.3
Y 719
806
806
806
851
Styrene 0.34 0.36 932
Methacrylate, methyl 0.04 3.7 1092
Styrene 0.09 0.58 1092
Acrylate, a-chloro-, ethyl 0.3
Acrylate, ethyl 0.968
Methacrylate, methyl 0.608
Styrene 0.173
Vinyl acetate 5.621
Styrene 0.175
Styrene 0.9
Metbacrylate met hyl 0.173
Methacrylate methyl 0.09
Styrene 0.44
Styrene 0.205
Methacrylate, methyl 1.13
Acrylate, wmethoxy-, methyl 0.58
Acrylate, a-acetoxy-, ethyl 1.71
Acrylate, cr-fluoro-, ethyl 2.9
Acrylate, methyl 3.22
Acrylonitrile, cc-methoxy- 0.9
Metbacrylonitrile 2
Styrene 0.32
Vinyl acetate 30
Acrylonitrile 1.76
Methacrylate, methyl 1.92
Styrene 0.3
Vinylidene cyanide 0.313
Styrenesulfonate, p-. sodium 0.27
Acrylonitrile 0.68
Acrylate, methyl 0.34
Methacrylate, methyl 0.03
Methacrylate, methyl 0.135
Methacrylonitrile 0.15
Styrene 0.61
Styrene 0.001
Styrene 0.197
Styrene 0.24
Acrylate, a-chloro-, ethyl 0.21
Styrene 0.16
Styrene 0.07
0.033
0.02
0.01
0.094
0.053
0.2
0.022
0.01
0.08
0.053
0.19
0.075
0.12
0.031
0.021
0.028
0.17
0.23
0.19
0.04
0.043
0.24
0.11 0.07
0.18
0.08
0.081
0.09
0.021
0.06
0.09
0.07
0.01
0.016
0.01
0.05
0.034
0.014
0.07
0.31
0.02
0.04
0.02
0.014
0.01
0.01
0.048
0.014
0.11
1.71
0.943
1.65
0.557
0.08
0.57
0.14
2.36
3.9
0.02
0.812
0.31
0.11
0.3
0.21
0.09
0.3
0.45
0.08
0.03
0.122
0.11
0.25
0.066
1.44
0.01
0.02
0.21
0.068
0.18
0.05
1.615
0.758
0.37
2.9
0.66
0.23
0.17
638
Y 244
Y 244
Y 244
Y 244
Y 49
806
Y 610
N 610
806
Y 49
Y 6
638
638
638
638
638
638
806
638
Y 6
N 3 1
74
Y 82
Y 834
N 1 4 1
N 1 4 1
N 1 4 1
Y 182
N 1 4 3
N 1 4 1
Y 49
Y 49
1047
638
806
1047
TABLE 1. contd
copolymer Reactivity Ratios II / 187
Monomer 1 Monomer 2
r1 f95%
r2
Zt95% Conv. Refs.
Acrylate, a-hydroxymethyl-, ethyl
Acrylate, whydroxymethyl-, ethyl
Acrylate, a-hydroxymethyl-, ethyl
Acrylate, a-isobutyl-, methyl
Acrylate, a-isopropyl-, methyl
Acrylate, a-isopropyloxymethyl-, methyl
Acrylate, wmethoxy, methyl
Acrylate, a-methoxy-, methyl
Acrylate, cr-p-chlorobenzyl-, methyl
Acrylate, a-p-methoxybenzyl-, methyl
Acrylate, a-phenoxymethyl-, methyl
Acrylate, CL- phenoxymethyl-, methyl
Acrylate, a-phenyl-, methyl
Acrylate, a-phenyl-, methyl
Acrylate, cl-phenyl-, methyl
Acrylate, cc-phenyl-, methyl
Acrylate, a-phenyl-, methyl
Acrylate, wphenyl-, methyl
Acrylate, a-phenyl-, methyl
Acrylate, wphenyl-, methyl
Acrylate, a-phenyl-, methyl
Acrylate, a-phenyl-, butyl
Acrylate, a-phenyl-, chloroethyl
Acrylate, wphenyl-, propyl
Acrylate, a-propyl-, methyl
Acrylate, cl-propyloxymethyl-, methyl
Acrylate, cc-set-butyl-, methyl
Acrylate, c+tetrafluoropropyloxymethyl-,
methyl
Acrylate, wtetrafluoropropyloxymethyl-,
methyl
A&ate, a-trifluoroethyloxymethyl-,
methyl
Acrylate, a-trifluoromethyl-, methyl
Acrylate, a-trifluoromethyl-, methyl
Acrylate, a-trifluoromethyl-, methyl
Acrylate, a-trifluoromethyl-, methyl
Acrylate, cc-trimethylsiloxy-, methyl
Acrylate, benzyl
Acrylate, benzyl
Acrylate, benzyl
Acrylate, benzyl
Acrylate, benzyl
Acrylate, benzyl
Acrylate, butyl
Ac r yl a t e , but yl
Ac r yl a t e , but yl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Azlactone, 2-vinyl-4,4-dimethyl- 0.668
Methacrylate, methyl 1.34
Styrene 0.546
Styrene 0.202
Styrene 0.036
Styrene 0.26
Acrylate, a-chloro-, ethyl 0.11
Styrene 0.513
Methacrylate, methyl 0.255
Methacrylate, methyl 0.13
Methactylate, met hyl 0.755
Styrene 0.256
Acrylate, methyl 1
Acrylonitrile 6.7
Methacrylate, methyl 0
Methacrylate, methyl 0
Methacrylonitrile 0.25
Styrene 1
Styrene 0.4
Styrene 0.45
Styrene 1.275
Styrene 0.107
Styrene 0.201
Styrene 0.126
Styrene 0.208
Styrene 0.29
Styrene 0.004
Methacrylate, methyl 0.61
Styrene 0.17
Styrene 0.2 0.26
Methacrylate, methyl -0.17
Methacrylate, methyl 0
Methacrylate, methyl 0.1
Styrene, p-chloro- 0
Styrene 1.42
Acrylonitrile 0.72
Acrylonitrile 0.63
Ally1 chloride 9.9
Methacrylate, methyl 0.19
Styrene 0.2
Styrene 0.248
2-Oxazoline, 2-isopropenyl- 0.24
Acrolein 0.638
Acrolein 1.12
Acrolein, methyl- 0.02
Acrylamide, N-propyl- 0.8
Acrylamide, N-methylol- 0.87
Acrylate, 2-hydroxyethyl 0.3
Acrylic acid 1.08
Acrylic acid 0.91
Acrylic acid, a-bromo- 0.19
Acrylonitrile 1.06
Acrylonitrile 0.894
Acrylonitrile 0.82
Acrylonitrile 0.9
Acrylonitrile 1.2
Ally1 acetate 10.2
Ally1 chloride 5.83
Benzofuran, 2-vinyl- 0.041
Butadiene 0.074
Ethylene 13.94
Furan, 2-vinyl-5-methyl 0.118
0.12
0.062
0.127
0.042
0.034
0.058
0.034
0.008
0.061
0.102
0.008
0.055
0.09
0.063
0.07
0.024
0.18
0.1
0.1
0.03
0.16
0.2
0.12
0.041
0.01
0.032
0.41
0.06
0.18
0.13
0.15
0.019
0.13
42.2
0.043
0.03
0.38
0.019
0.389
1.26
0.468
0.974
1.872
0.41
0.58
1.131
1.87
1.71
1.13
0.176
0.06
0.08
0.21
0.3
0.19
0.06
0.03
0.06
1.176
0.04
0.025
0.03
0.821
0.47
2.29
1.43
0.37
1.8
3.2
2.3
0.24
0.46
0.28
1.49
0.06
2.23
0.494
0.534
1.4
1.86
2.29
2.5
0.4
0.61
0.9
0.59
1.31
0.09
1.679
0.781
1.08
1
1
0.039
0.1
7.8
1.04
0.01
0.392
0.229
0.17
0.03
0.022
0.052
0.078
0.222
0.109
0.038
0.05
0.015
0.022
0.015
0.015
0.029
0.068
0.23
0.5
0.2
0.02
0.19
0.14
0.05
0.028
0.08
0.19
0.58
0.23
0.27
0.3
0.058
0.083
0.08
0.066
1.36
0.11
0.003
0. 05 1
Y
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
N
N
N
Y
Y
Y
Y
N
N
N
N
Y
Y
N
N
N
Y
N
Y
1 0 1 1
1 0 2 7
982
49
49
1047
638
806
905
905
1048
1048
141
141
1 4 1
49
1 4 3
1 4 1
399
488
49
488
488
488
49
1047
49
1047
1047
1047
681
825
825
825
1 1 0 1
2 3
385
438
277
1 7 8
277
894
291
292
589
730
441
868
1 8 7
252
733
1 1 8
162
233
513
513
1053
438
1020
257
42
1 1 0 5
References page II - 290
II / 188 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. conrd
Monomer 1 Monomer 2 r1 f95% r2 f95% Conv. Refs.
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
A&ate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, butyl
Acrylate, cis-B-cyano-, methyl
Acrylate, cis-B-cyano-, methyl
Acrylate, cresyl
Acrylate, cyclododecyl
Acrylate, cyclododecyl
Acrylate, cyclododecyl
Acrylate, cyclohexyl
Acrylate, cyclohexyl
Acrylate, cyclohexyl
Acrylate, cyclohexyl
Acrylate, cyclohexyl
Acrylate, cyclohexyl
Acrylate, di-, copper
Acrylate, di-, copper
Acrylate, di-, copper
Itaconate, bis(tri-n-butyltin)
Itaconate, dimethyl
Mal ei mi de, N-(2,4-dimethylphenyl)-
Methactylate,
2-(N,N-dimethylcarbamoyloxy)ethyl
Methactylate, 2-chloro-
2,3,3,3-fluoropropyl
Methacxylate, 2-hydroxyethyl
Methacrylate, 2-hydroxypropyl
Methacxylate, 2-hydroxypropyl
Methactylate, butyl
Methacrylate, glycidyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylic acid
Oxazoline, 2,2-isopropenyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 4-vinyl-
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene, o-chloro-
Styrene, p-1-(2-hydroxybutyl)-
Styrene, p-octylamine sulfonate
Succinimide, N-vinyl-
Thiophene, J-vinyl
Vinyl acetate
Vinyl bromide
Vinyl bromide
Vinyl chloride
Vinyl fluoride
Vinyl fluoride
Vinyl methyl ketone
Vinyl, p-, benzylethylcarbinol
Vinylanthracene, 9-
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Acrylonitrile
Styrene
Acrylonitrile
Styrene
Styrene
Styrene
N-Vinylpyrrolidone
Styrene
Styrene
Styrene
Styrene
Styrene
Methacrylate, di-, dicyclopentadienyl-
titanium
Styrene
Styrene
0.91 0.422 940
0.4 0.94 398
0.62 0.2 788
0.47 1.89 600
0.079 0.304 0.221 0.636 N 927
0.09
0.171
0.24
0.3
0.083
0.13
0.11
0.43
0.31
0.24
0.1
0.11
0.23
0.25
0.34
0.38
-0.106
0.29
0.18
0.19
0.21
0.15
0.164
0.164
0.2
0.17
0.3
1.54
0.386
3.48
4.07
3.7
4.4
1 9
1 9
0.8
0.17
3.717
0.873
0.46
0.58
0.11
0.041
0.16
0.052
0.15
0.018
0.07
0.1
4.75
5.35
3.3
2.2
2.16
0.92
2.86
1.88
1.25
1.4
2.51
2.59
4.3
0.79
0.79
0.75
1.23
0.44
0.84
0.66
0.82
0.8
0.698
0.698
2.25
0.4
2.3
0.15
0.499
0.018
0.18
0.19
0.07
0.01
0.01
1.81
0.4
0.126
0.934
0.84
0.87
4.2
0.32
6.82
0.57
0.2
0.32
0.4
0.31
0.01
0.04
0.05
0.06
0.05
0.099
0.05
0.03
0.14
0.34
0.08
0.11
0.1
0.21
0.03
0.2
3.39
0.44
0.072
0.16
0.06 0.24
0.046
0.022
0.054
0.006
0.773
0.34
0.31
0.301
1.297
0.272
0.254
0.16
0.17
0.18
1.09
0.067
0.15
0.08
0.072
0.088
0.048
0.141
0.13
0.09
0.07
0.72
0.47
0.54
0.461
0.122
0.913
0.885
0.53
0.7
0.58
0.89
0.12 0.08 5.94
0.56 0.09 1.74
0.15
0.14
0.08
0.07
0.014
0.107
0.102
0.11
0.12
0.1
0.05
0.03
Y 358
Y 333
Y 662
187
Y 674
N 30
Y 639
N 87
N 187
862
236
N 78
N 78
1032
1032
1032
N 1 9
N 20
N 38
38
463
549
612
632
558
548
817
789
1000
Y 301
N 268
268
518
604
606
N 53
591
Y 1 2 3
Y 118
464
464
N 1034
N 1034
Y 363
806
806
806
1 0 6 1
1 0 6 1
806
806
806
806
876
N 829
N 829
TABiE 1 . contd
Copolymer Reactivity Ratios II / 189
Monomer 1 Monomer 2
rl
rt95%
12
*95% Conv. Refs.
Acrylate, di-, nickel
Acrylate, di-, nickel
Acrylate, di-, zinc
Acrylate, di-, zinc
Acrylate, dibutylchlorotin
Acrylate, diethylaluminum
Acrylate, diethylaluminum
Acrylate, dodecyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acjlate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Actylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ethyl
Acrylate, ferrocenylmethyl
Methacrylate, di-, dicyclo-
pentadienyltitanium
Styrene
Acrylonitrile
Styrene
Acrylate, methyl
Styrene
Styrene
Acrylonitrile
2-Oxazoline, 2-isopropenyl-
Acrolein
Acrolein
Acrylamide, N-methylol-
Acrylate, 2-chloroethyl
Acrylate, 2-hydroxyethyl
Acrylate, a-acetoxy-, ethyl
Acrylate, hydroxyethyl
Acrylic acid
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Ally1 chloride
Benzofuran, 2-vinyl-
Carbazole, N-vinyl-
Ethylene, 1, l-diphenyl-
Imidazolid-2-one, 1,3-divinyl-
Imidazolid-2-one, 1-ethyl-3-vinyl-
Isopropenylisocyanate
Mal ei mi de, 2,3-dimethyl-
N-(2-methacryloyloxy)ethyl
Methacrylate, 2-(sulfonic acid)ethyl
Methacrylate, 2-bromoethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxypropyl
Methacrylate, 2-hydroxypropyl
Methacrylate, butyl
Methactylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylic acid
Norbomadiene
Oxazoline, 2-, 2-isopropenyl-
Propanesulfonate, S-[diethyl-
2-(2-methacroyloxyethoxy)]ethyl
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 4-vinyl-
Pyrimid-2-one, 1,3-divinylhexahydro-
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene 3-tr-n-butylstannyl-
Tropone, 2-methacryloyloxy-
Vinyl 2chloroethyl ether
Vinyl 2-chloroethyl ether
Vinyl isobutyl sulfide
Vinyl isobutyl sulfide
Vinylanthracene, 9-
Vinylidene chloride
Acrylate, methyl
0.95 0.65 876
0.53
0.24
0.9
0.09
0.046
0.06
0.07
0.035
0.16
0.02
0.25
1.83
0.41
1.1
0.81
- 0.002
0.88
0.19
0.6
1.09
1.4
0.9
0.5
0.943
0.5
1.02
1.2
0.81
4
0.95
1.13
0.015
1.1
0.8
0.41
0.47
0.79
0.28
0.02
0.02
0.016
0.07
0.06
0.44
0.03
0.075
0.05
0.07
0.27
0.24
0.033
0.09
0.08
0.78
0.01 0.334
0.13
0.06
1.15
2.37
1.39
1.2
1.98
1.4
1.03
0.97
0.968
0.88
0.91
0.92
1.16
0.66
0.44
0.08
5.16
0.27
0.5
- 0.08
0.01
0.15
1.55
0.03
0.01
3.06
829
646
829
659
652
652
233
894
291
292
442
126
868
244
890
711
1023
1 9 8
389
542
438
1020
151
65
800
800
434
619
0.3
0.37
0.189
0.273
0.207
0.22
0.41
0.28
0.22
0.008
0.054
0.045
0.17
0.05
0.44
1.03
0.06
3.2
2.1
11.21
13.32
9.08
2.43
1.83
2
2.04
0.43
1.05
3.95
0.39
2.39
0.19
3.97
- 0.01
1.39
0.19
564
657
358
333
662
690
30
469
81
1065
267
862
962
0.21
0.21
0.29
0.59
0.139
0.16
0.19
0.2
0.48
0.152
0.152
10.4
0.387
5
4.65
0.36
0.32
3.498
0.72
0.14
0.28
0.03
0.02
0.1
0.13
0.085
0.03
0.072
0.027 0.528
0.02
0.02
0.041
0.39
0.28
2.25
2.58
- 0.05
0.699
1.01
0.79
0.8
0.8
0.787
0.781
0.01
3.13
0.15
0
0.05
0.05
0.295
0.58
4.46
0.04
0.05
0.056
0.15
N
N
Y
Y
N
N
N
Y
N
N
N
N
Y
Y
Y
Y
Y
N
N
N
Y
N
N
Y
Y
N
N
Y
Y
250
832
832
800
1 7 8
463
530
530
542
673
671
985
1104
439
726
285
336
1 2 3
6 5
293
References page II - 290
II / 190 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
rl Zt95%
r2
f95% Conv. Refs.
Acrylate, ferrocenylmethyl
Acrylate, ferrocenylmethyl
Acrylate, ferrocenylmethyl
Acrylate, ferrocenylmetbyl
Acrylate, ferrocenylmethyl
Acrylate, ferrocenylmethyl
Acrylate, furfuryl
Acrylate, glycidyl
Acrylate, glycidyl
Acrylate, glycidyl
Acrylate, glycidyl
Acrylate, glycidyl
Acrylate, heptafluorobutyl
Acrylate, heptafluorobutyl
Acrylate, heptafluorobutyl
Acrylate, heptyl
Acrylate, heptyl
Acrylate, hydroxyethyl
Acrylate, hydroxyethyl
Acrylate, hydroxyethyl
Acrylate, isobutyl
Acrylate, isobutyl
Acrylate, isobutyl
Acrylate, isopropyl
Acrylate, m-chlorophenyl
Acrylate, m-nitrophenyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Maleic anhydride
Methacrylate, methyl
Methacrylate, methyl
Styrene
Styrene
Styrene
Methacrylate, 2-hydroxyethyl
Acrylate, 2-ethylhexyl
Acrylonitrile
Styrene
Styrene
Vinyl acetate
Butadiene
Methacrylate, methyl
Styrene
Maleimide, N-(2,4-dimethylphenyl)-
Methacrylate, methyl
Acrylate, ethyl
Acrylate, methyl
Acrylate, methyl
Methacrylate, methyl
Methacrylate, glycidyl
Methacrylate, methyl
Styrene
Acrylonitrile
Methacrylate methyl
2-Oxazoline, 2-isopropenyl-
2-Oxazolinium BF4, 3-methyl-
2-isopropenyl-
2-Oxazolinium, 2-isopropenyl-
Acetylene, phenyl-
Acetylene, phenyl-
Acrolein
Acrolein
Acrolein
Acrylamide, N-methylol-
Acrylamide, N-propyl-
Acrylate, 2-chloroethyl
Acrylate, 2-hydroxyethyl
Acrylate, a-chloro-, ethyl
Acrylate, a-cyano-, methyl
Acrylate, a-phenyl-, methyl
Acrylate, dibutylchlorotin
Acrylate, ferrocenylmethyl
Acrylate, hydroxyethyl
Acrylate, hydroxyethyl
Acrylate, tributyltin
Acrylic acid, wbromo-
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acryloyl chloride
Ally1 acetate
Ally1 acrylate
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Allylbenzene
Benzophenone, p-vinyl-
Benzophenone, p-vinyl-
Butadiene
Butadiene, 2-chloro-
Carbamate, NJ-diethyl-, vinyl
- 0.3
0.024
0.08
- 0.016
0.02
0.02
0.88
1.18
1
0.17
0.24
7.6
0.073
0.177
0.049
0.14
0.46
0.88
1
0.94
0.135
0.282
0.29
0.195
0.85
1.04
0.16
0.096
0.191
0.622
0.664
7.86
0.83
1.08
1.3
1.2
0.9
0.94
0.09
0.02
0.06
0.81
4.46
1
0.23
0.82
0.24
0.51
0.844
0.85
0.34
5
0.52
8.45
5.45
6.46
9.1
11.35
0.09
1.1
0.07
0.06
4.78
2.96
0.064
0.06
0.19
0.06
0.031
0.013
0.02
0.09
0.1
0.1
0.02
0.026
0.04
0.027
0.036
0.135
0.04
0.057
0. 03 1
0.062
0.045
3.58
0.12
0.38
0.04
0.04
0.1
0.03
0.02
0.037
0.2
0.66
0.02
0.02
0.87
0.22
0.09
2.8
2.9
1.87
2.3
2.5
1.35
1.12
1.01
0.6
0.73
0.003
0.359
0.084
0.31
0.2
2.51
0.5
1
0.23
4.1
1.24
1.04
0.755
1.3
0.928
1.9
0.251
2.08
0.272
0.093
- 0.07
1.41
2.54
1.9
0.26
1.07
0.9
3.22
0.34
1
0.09
0.14
1
0.94
0.03
0.1
0.56
1.54
1.31
2.3
0
0.33
0.05
0.07
0.4
- 0.02
- 0.036
3.6
3.54
1.09
10.4
- 0.027
0.14
0.19
0.17
0.08
0.07
0.34
0.039
0.01
0.13
0.05
0.1
0.03
0.5
0.12
0.08
0.024
0.073
0.248
0.08
0.483
0.327
0.072
0.01
0.03
0.4
0.93
0.13
0.07
0.1
0.1
0.03
0.044
0.08
0.016
1.06
0.077
4.53
0.049
Y
Y
Y
N
N
Y
Y
Y
Y
Y
N
Y
Y
Y
Y
Y
Y
Y
N
Y
N
N
N
Y
N
Y
Y
Y
Y
Y
Y
Y
325
293
293
293
293
576
1063
126
114
114
126
553
206
206
206
788
980
890
890
890
639
674
30
178
363
1074
894
908
908
60
731
207
291
292
441
730
726
868
638
141
1 4 1
659
293
890
890
659
733
1024
1 5 1
233
508
470
578
204
437
437
437
437
351
866
911
257
6 1
92
TABLE 1. contd
Copolymer Reactivity Ratios II / 191
Monomer 1 Monomer 2
r1 f95% r2 &95% Conv. Refs.
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Carbazole, N-vinyl-
Carbazole, N-vinyl-
Carbazole, N-vinyl-
Cinnamate, dibutylchlorotin
Diallyl phthalate
Diallyl phthalate
Diallylcyanamide
Diallylcyanamide
Ethylene
Ethylene
Ethylene 1, l-diphenyl-
Ethylene, l,l-diphenyl-
Ethylene tetrachloro-
Ethylene, trichloro-
Fumarate, diisopropyl
Hexatriene, tetrachloro-
He x e n e - 1
Imidazole, 1-vinyl-Zmethyl-
Indene
Indene
Isoprene
Isoprene, 3-acetoxy-
Isopropenyl, S-1-cyclohexenyl, acetate
Isopropenylisocyanate
Isopropenylisocyanate
Maleic anhydride
Maleic anhydride
Mal ei mi de, N-(4-bromophenyl)-
Mal ei mi de, N-(Cchlorophenyl)-
Mal ei mi de, N-(ctolyl)-
Maleimide, N-phenyl-
Methacrylate, 2,3-epithiopropyl
Methacrylate, 2-(N,N-dimethyl
carbamoyloxy)ethyl
Methacrylate, 2-chloroethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-hydroxypropyl
Methacrylate, ferrocenylmethyl
Methacrylate, methyl
Methacrylate, r-butyl dimethylsilyl
Methacrylic anhydride
Oxazoline, 2-,2-isopropenyl-
Oxazoline, 2-,2-isopropenyl-
Oxazoline, 2-,2-isopropenyl-
4,4-dimethyl
Oxazoline, 2-,4-acryloxy-methyl-
2,Cdimethyl
Oxazoline, 2-P-methacryl-oxy-
2,4-dimethyl
Oxazolinium, 2-, tetrafluoro-borate,
3-methyl
Phthalimide, N-(4-vinylphenyl)-
Phthalimide, N-(methacryloyloxy)-
Propenyl, 2-chloro-, acetate
Pyridine, 2-methyl-5-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-
Pyridine, 2-vinyl-5-ethyl-
Pyridine, 4-vinyl-
Pyridine, 4-vinyl-
Pyrrolidone, 1-benzyl-3-methylene-
5-methyl
Styrene
Styrene
0.53
0.43
0.51
1.65
6.208
6.18
6.1
6.1
0.13
0.073
0.069
0.16
0.049
0.11
0.028
- 0.2
0.028
0.038
0.05
0.05
0.029
0:045
0.005
0.008
19.4
0.09
0.12
830
3 3
1.9
0.262
-0.13
1.28
0.63
0.62
0.12
0.27
0.37
0.6
0.799
2.188
2.5
0.429
0.684
0.64
0.554
0.34
0.22
0.01
0.01
0.02
- 0.24
0.21
0
0
0.091
3.19
- 0.67
0.05
0.1
0.12
0.75
5.71
0.57
0.11
0.079
0.012
0
0.39
0.155
0.14
0.103
2.81
1.32
0.15
0.05
0.087
0.6
1.36
0.03
0.049
0.051
0.099
0.052
0.16
0.048
0.047
0.013
0.17
0.052
0.16
0.052
0.29
- 0.005
0.013
1.4
0.4
0.288
0.16
0.16
0.328
0.46
0.036
0.007
0.35
0.12
0.057
8.28
0.083
0.085
0.04
0.21
0.032
2.19
8.67
7.335
0.042
2.15
1.07
4.75
1.9
2.07
1.3
0.191
0.29 0.11
0.4 0.56
0.552 0.043 0.344 0.105
1.14
0.193
0.7
0.18
0.37
0.17
0.2
0.18
0.2
0.15
0.125
0.028
1.56
1.23
0
1
2.13
1.72
2.12
1.32
1.78
2.14
1.58
0.168
0.05
0.4
0.03
0.03
0.004
0.03
0.3
0.54
0.26
0.1
0.03
0.32
0.025 0.24
0.24
0.8 0.21
0.82
0.192 0.057
Y
Y
Y
Y
N
N
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
Y
N
Y
N
N
N
N
Y
Y
1 3
551
98
659
291
297
603
604
4 1
168
334
334
402
470
1038
5
60
465
606
606
424
770
770
434
99
260
470
628
628
644
644
187
600
726
358
333
293
324
1069
215
862
877
596
596
596
871
636
979
445
232
2
231
749
231
231
424
633
1 3 9
1 4
References page II - 290
II / 192 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
r1 It95% r2 Zt95% collv. Refs.
Acrylate, methyl Styrene 0.168
Acrylate, methyl Styrene 0.18
Acrylate, methyl Styrene 0.18
Acrylate, methyl Styrene 0.14
Acrylate, methyl Styrene 0.07
Acrylate, methyl Styrene 0.3
Acrylate, methyl Styrene 0.16
Acrylate, methyl Styrene 0.148
Acrylate, methyl Styrene, 2,5-dichloro- 0.142
Acrylate, methyl Styrene, 2,5-dichloro- 0.288
Acrylate, methyl Styrene, wmethoxy- 0.17
Acrylate, methyl Styrene, m-methyl- 0.14
Acrylate, methyl Styrene, p-1-(2-hydroxybutyl)- 0.18
Acrylate, methyl Styrene, p-N,N-dimethylamino- 0.06
Acrylate, methyl Styrene, p-dimethylamino- 0.192
Acrylate, methyl Styrene, p-methoxy- 0.07
Acrylate, methyl Styrene, p-methyl- 0.17
Acrylate, methyl Succinimide, N-vinyl- 0.357
Acrylate, methyl Vinyl 2chloroethyl ether 3.27
Acrylate, methyl Vinyl acetate 7.28
Acrylate, methyl Vinyl acetate 6.38
Acrylate, methyl Vinyl acetate 2.58
Acrylate, methyl Vinyl acetate 6.7
Acrylate, methyl Vinyl acetate 6.3
Acrylate, methyl Vinyl butyl ether 3.65
Acrylate, methyl Vinyl butyl ether 3.6
Acrylate, methyl Vinyl butylsulfonate 4.14
Acrylate, methyl Vinyl chloride 4.4
Acrylate, methyl Vinyl chloride 7.66
Acrylate, methyl Vinyl chloride 5
Acrylate, methyl Vinyl chloride 4
Acrylate, methyl Vinyl cymantrene 0.46
Acrylate, methyl Vinyl ethyl ether 3.3
Acrylate, methyl Vinyl fluoride 43
Acrylate, methyl Vinyl fluoride 43
Acrylate, methyl Vinyl hendecanoate 3.615
Acrylate, methyl Vinyl isobutyl ether 3.63
Acrylate, methyl Vinyl isobutyl sulfide 0.3
Acrylate, methyl Vinyl isobutyl sulfide 0.29
Acrylate, methyl Vinyl methyl sulfide 0.209
Acrylate, methyl Vinyl phenyl sulfide 0.57
Acrylate, methyl Vinyl stearate 5.8
Acrylate, methyl Vinyl thiolacetate 0.8
Acrylate, methyl Vinyl, 2-bromo-, ethyl ether 16.83
Acrylate, methyl Vinyl, p-, benzylethylcarbinol 0.18
Acrylate, methyl Vinylanthracene, 9- 2.998
Acrylate, methyl Vinylhydroquinone dibenzoate 0.46
Acrylate, methyl Vinylidene chloride 0.95
Acrylate, methyl Vinylidene chloride 0.8
Acrylate, methyl Vinylidene chloride 1
Acrylate, methyl Vinylisocyanate 1.38
Acrylate, mono-, ethylene glycol Acrylonitrile 1.2
Acrylate, o-chlorophenyl Acrylonitrile 1.171
Acrylate, o-chlorophenyl Methacrylate, methyl 0.4
Acrylate, octadecyl Acrylonitrile 1.04
Acrylate, octadecyl Acrylonitrile 1.35
Acrylate, octadecyl Acrylonitrile 0.32
Acrylate, octadecyl Methacrylate, methyl 0.464
Acrylate, octadecyl Styrene 0.37
Acrylate, octadecyl Styrene 0.18
Acrylate, octadecyl Styrene 0.31
Acrylate, octadecyl Styrene 0.18
Acrylate, octadecyl Vinylidene chloride 1
Acrylate, octyl Acrylonitrile 0.84
Acrylate, octyl Styrene 0.01
0.067
0.026
0.054
0.069
0.02
0.01
0.01
0.063
0.37
0.3
0.07
0.58
0.22
0.5
0.14
0.012
0.04
0.01
0.01
0.034
0.1
2.34
0.067
0.21
0.023
0.38
0.4
0.35
0.07
0.12
0.14
0.74
0.53
0.722
0.75
0.75
0.68
0.9
0.65
0.4
0.871
3.93
4.47
0.003
1.65
0.48
0.38
0.372
2
1.54
0.9
0
0.04
0.03
0.405
0.03
0.03
0.01
0
0
0.093
0.002
0
0.06
0.211
0
0.01
0.01
0.033
0
0.05
0.06
0.084
0.02
0.03
0.23
0.79
0.48
0.08
0.75
0.9
0.7
1
0.14
0.8
1.123
1.25
1.91
4.39
1.76
2.477
0.777
0.44
0.79
0.44
0.9
1.98
0.39
0.056
0.022
1.38
0.15
0.01
0.16
0.055
0.17
0.01
0.043
0.01
0.4
0.002
0.01
0.067
0.008
0.002
0.02
0.02
0.086
0.22
0.32
0.092
0.11
0.037
0.1
0.64
0.2
0.024
0.018
0.037
0.3
0.11
Y
Y
Y
Y
N
Y
Y
Y
Y
Y
N
Y
Y
Y
Y
Y
N
N
N
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
Y
Y
1 5 1
393
397
463
495
496
496
865
136
2
142
558
548
866
911
558
558
80
726
1067
158
25
489
568
345
574
1 8 5
1 5 1
46
470
518
354
470
604
606
1 4 5
347
285
336
1 9 5
1 9 3
537
566
194
591
1 2 3
440
1 0 7
107
377
435
682
363
621
1 1 8
233
290
290
290
290
290
290
118
1 1 8
806
TABLE 1. conrd
Copolymer Reactivity Ratios II / 193
Monomer 1 Monomer 2
rl
*95%
r2
Zt95% Conv. Refs.
Acrylate, octyl Vinyl chloride
Acrylate, octyl Vinylidene chloride
Acrylate, p-(cinnamoylamino)phenyl Styrene
Acrylate, p-bromophenyl Acrylonitrile
Acrylate, p-bromophenyl Methacrylate, methyl
Acrylate, p-chlorophenyl Acrylonitrile
Acrylate, p-chlorophenyl Methacrylate, methyl
Acrylate, p-chlorophenyl Methacrylate, methyl
Acrylate, p-methylphenyl Methacrylate, methyl
Acrylate, pentabromophenyl Styrene
Acrylate, pentachlorophenyl Acrylic acid
Acrylate, pentachlorophenyl Styrene
Acrylate, phenyl Acrylonitrile
Acrylate, phenyl Fumarate, diisopropyl
Acrylate, phenyl Methacrylate, methyl
Acrylate, phenyl Methacrylate, methyl
Acrylate, sodium Vinyl acetate
Acrylate, rert-butyl Methacrylate, glycidyl
Acrylate, tetrahydrofurfuryl Styrene
Acrylate, thio- butyl Styrene
Acrylate, thio-, ethyl Styrene
Acrylate, thio-, rert-butyl Styrene
Acrylate, tributyltin Acrylate, methyl
Acrylate, trifluoro-, methyl Styrene
Acrylate, trifluoro-, methyl Styrene
Acrylate, trifluoro-, methyl Vinyl acetate
Acrylate, trifluoro-, methyl Vinyl acetate
Acrylate, trifluoro-, methyl Vinyl chloride
Acrylate, trifluoro-, methyl Vinyl chloride
Acrylic acid Acrolein
Acrylic acid Acrolein
Acrylic acid Acrylamide
Acrylic acid Acrylamide
Acrylic acid Acrylamide
Acrylic acid Acrylamide
Acrylic acid Acrylamide
Acrylic acid Acrylamide
Acrylic acid Acrylamide, N,N-dimethyl-
Acrylic acid Acrylate, pentachlorophenyl
Acrylic acid Acrylate, butyl
Acrylic acid Acrylate, butyl
Acrylic acid Acrylate, ethyl
Acrylic acid Acrylic acid, 2-benzamido-
Acrylic acid Acrylic acid, N-acetyl-a-amino-
Acrylic acid Carbamate, N,N-diethyl-, vinyl
Acrylic acid Carbamate, N-vinyl-, ethyl
Acrylic acid Imi dazol e, l-vinyl-
Acrylic acid Methacrylate, isopropyl
Acrylic acid Methacrylate, methyl
Acrylic acid Methacrylate, butyl
Acrylic acid N-Vinylimidazole
Acrylic acid Phosphonic acid, u-phenylvinyl-
Acrylic acid Propenyl, 2-chloro-, acetate
Acrylic acid Propylene
Acrylic acid Pyrrolidone, N-vinyl-
Acrylic acid Styrene
Acrylic acid Styrene
Acrylic acid Styrene
Acrylic acid Styrene
Acrylic acid Styrene
Acrylic acid Styrene
Acrylic acid Styrene
Acrylic acid Styrene
Acrylic acid Vinyl acetate
Acrylic acid Vinyl chloride
4.8
0.679
0.35
1.026
0.191
0. 95 1
0.235
0.3
0.223
0.1
1.12
0.9
0.327
3.4
0.45
0.416
0.463
0.489
0.421
0.291
0.368
0.03
0
0
0
0
0
0
0.08
1.15
0.288
1.644
0.341
1.38
3.8
0.29
0.36
0.82
0.59
1.31
0.91
0.48
1.41
5.58
4.69
0.0025
1.03
1.73
0.24
1.932
0.7
1
0.88
0.05
0.08
0.25
0.35
0.136
0.15
0.45
0.25
8.66
6.69
0.057
0.062
0.014
0.063
0.023
0.036
0.045
0.041
0.079
0.196
0.17
0.075
0.055
0.28
0.029
0.069
0.012
0.14
0.04
0.27
0.3
0.32
-
0.096
0.21
0.077
0.13
0.69
0.029
6.63
0.88
0.12
0.851
1.08
0.8
0.926
0.32
1.01
1.09
1.45
0.16
0.82
2.11
0.43
0.07
1.56
1.54
2.096
0.475
0.439
0.18
0.157
0.82
1.4
1.4
0.24
0.24
1.5
1.5
2.48
0.5
1.08
0.445
1.346
0.598
0.58
1.06
0.35
1.12
1.08
0.91
1.02
2.08
0.49
0.097
0.26
0.32
0.68
0.418
3.53
0.187
0.04
0
0.1
0.25
1.1
0.15
0.22
0.253
0.25
0.25
0.15
0.021
0.107
0.018
0.13
0.056
0.056
0.132
0.275
0.13
0.14
0.443
0.186
0.14
0.038
0.034
1.24
0.17
0.075
0.044
0.047
0.12
0.18
0.13
0.068
0.02
0.42
0.025
0.83
0.21
0.069
0.059
0.011
518
Y 1 1 8
685
Y 363
Y 1074
Y 63
Y 1074
621
Y 1074
643
900
900
Y 363
1038
621
Y 672
Y 37
Y 814
806
806
806
806
659
595
598
595
598
595
598
Y 57
57
Y 221
Y 278
Y 278
Y 37
869
869
N 205
900
N 1 8 7
N 252
711
1019
661
Y 92
Y 8 1
955
847
N 964
N 1 8 7
Y 879
Y 132
445
Y 183
N 250
312
312
397
414
Y 47
490
542
561
Y 37
Y 1 3 5
References page II - 290
II / 194 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
rl It95%
r2
f95% Conv. Refs.
Acrylic acid Vinyl chloride 9.28
Acrylic acid Vinyl chloride 7.04
Acrylic acid Vinyl chloride 6.8
Acrylic acid Vinylhydroquinone 0.29
Acrylic acid Vinylhydroquinone dibenzoate 0.44
Acrylic acid Vinylidene chloride 1.246
Acrylic acid Vinylidene cyanide 0.212
Acrylic acid, 2-benzamido- Acrylic acid 2.08
Acrylic acid, 2-benzamido- Styrene 0.78
Acrylic acid, 2-ethyl Methacrylic acid 0.194
Acrylic acid, 2-ethyl Methacrylic acid 0.069
Acrylic acid, 2-ethyl Methacrylic acid 0.23
Acrylic acid, N-acetyl-a-amino Acrylic acid 0.49
Acrylic acid, N-acetyl-cc-amino- Styrene 0.44
Acrylic acid, a-bromo Methacrylate, methyl 0.11
Acrylic acid, a-bromo Acrylate, butyl 0.09
Acrylic acid, cc-bromo Acrylate, methyl 0.1
Acrylic acid, a-bromo Methacrylate, butyl 0.13
Acrylic acid, a-bromo Pyrrolidone, N-vinyl 0.07
Acrylic acid, cis-3-bromo- Acrylamide - 0.2
Acrylic acid, cis-3-ethyl Acrylamide -0.16
Acrylic acid, truns-3-bromo- Acrylamide - 0.33
Acrylic acid, truns-3-ethyl- Acrylamide - 0.21
Acrylic anhydride Ally1 chloride 11.66
Acrylic anhydride Methacrylonitrile 1
Acrylic anhydride Styrene 0.1
Acrylonitrile 1,3-pentadiene, cis- 0.026
Acrylonitrile 1,3-pentadiene, cis- 0.06
Acrylonitrile 1,3-pentadiene, trans- 0.069
Acrylonitrile 1,3-pentadiene, trans- 0.068
Acrylonitrile 2-Oxazoline, 2-isopropenyl- 0.13
Acrylonitrile Acenaphthalene 0.02
Acrylonitrile Acetylene, phenyl- 0.266
Acrylonitrile Aconitate, trimethyl 4.24
Acrylonitrile Acrolein 0.88
Acrylonitrile Acrolein 0.71
Acrylonitrile Acrolein 0.48
Acrylonitrile Acrolein 0.6
Acrylonitrile Acrolein diethylacetal 11.19
Acrylonitrile Acrolein, methyl- 0.15
Acrylonitrile Acrolein, methyl- 0.15
Acrylonitrile Acrolein, methyl- 0.03
Acrylonitrile Acrylamide 0.863
Acrylonitrile Acrylamide 0.97
Acrylonitrile Acrylamide 1.8
Acrylonitrile Acrylamide 0.88
Acrylonitrile Acrylamide 0.8
Acrylonitrile Acrylamide, N-methylol- 0.7
Acrylonitrile Acrylamide, N-methylol- 0.98
Acrylonitrile Acrylamide, N-methylol- 0.22
Acrylonitrile Acrylamide, N-octadecyl- 1.034
Acrylonitrile Acryl ami de, N-tert-butyl- 0.2
Acrylonitrile Acrylate, 2-chloroethyl 1.03
Acrylonitrile Acrylate, 2-nitrobutyl 0.67
Acrylonitrile Acrylate, 3,4-epoxyhexahydrobenzyl 0.25
Acrylonitrile Acrylate, P-chloro-2-hydroxypropyl 0.24
Acrylonitrile Acrylate, P-ethoxy-, ethyl 2.42
Acrylonitrile Acrylate, a-chloro-, methyl 0.122
Acrylonitrile Acrylate, a-cyano-, methyl 0.01
Acrylonitrile Acrylate, wphenyl-, methyl 0.08
Acrylonitrile Acrylate, benzyl 0.28
Acrylonitrile Acrylate, benzyl 1.49
Acrylonitrile Acrylate, butyl 1.679
Acrylonitrile Acrylate, butyl 0.781
Acrylonitrile Acrylate, butyl 1.08
0.51
0.33
0.11
0.042
0.016
0.027
0.04
0.11
0.1
0.16
0.11
0.56
0.13
0.004
0.173
0.242
0.104
0.096
0.04
0.044
0.92
0.06
0.03
0.01
0.19
0.033
0.1
0.75
0.02
0.25
0.13
1.8
0.081
0.02
0.19
0.083
0.08
0.03
0.024
0.11
0.026
0.95
0.437
0.291
0.48
0.13
1.12
2.29
1.14
1.41
0.91
0.37
0.19
0.24
0.85
0.25
7.64
6.32
4.13
8.19
0.02
0.42
0.16
0.017
0.071
0.018
0.064
0.52
2.56
0.325
- 0.48
1.16
1.07
1.52
1.28
0.02
1.7
3.8
1.72
0.81
1.08
0.5
1.36
1.3
1.2
2.33
2.56
1.4
1.14
0.87
1.76
0.388
0.7
- 0.26
1.76
0.68
6.7
0.72
0.63
1.06
0.894
0.82
0.09
0.069
0.092
0.065
0.042
0.132
0.417
1.67
0.68
0.76
1.09
0.02
0.04
0.01
0.012
0.029
0.01
0.02
0.06
0.083
0.11
0.13
0.08
0.07
0.42
0.11
0.51
0.26
0.17
0.69
0.074
0.56
0.18
0.09
0.16
0.15
0.019
0.13
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
N
N
Y
Y
Y
Y
Y
Y
N
N
N
Y
Y
Y
N
Y
N
Y
N
Y
N
N
Y
Y
N
229
288
379
337
444
288
82
1019
1019
1004
1004
961
661
661
733
733
733
733
694
298
298
298
298
219
219
219
912
912
912
912
894
575
60
147
207
207
208
504
767
455
587
9 1
228
228
330
421
461
442
577
596
119
709
790
234
680
654
194
6
1 4 1
1 4 1
2 3
385
1 1 8
162
233
TABLE 1. contd
Copolymer Reactivity Ratios II / 195
Monomer 1 Monomer 2
r1
f95%
r2
lf95% Conv. Refs.
Acrylonitrile Acrylate, butyl
Acrylonitrile Acrylate, butyl
Acrylonitrile Acrylate, cis-P-cyano-, methyl
Acrylonitrile Acrylate, cresyl
Acrylonitrile Acrylate, di-, zinc
Acrylonitrile Acrylate, dodecyl
Acrylonitrile Acrylate, ethyl
Acrylonitrile Acrylate, ethyl
Acrylonitrile Acrylate, ethyl
Acrylonitrile Acrylate, ethyl
Acrylonitrile Acrylate, glycidyl
Acrylonitrile Acrylate, m-chlorophenyl
Acrylonitrile Acrylate, methyl
Acrylonitrile Acrylate, methyl
Acrylonitrile Acrylate, methyl
Acrylonitrile Acrylate, mono-, ethylene glycol
Acrylonitrile Acrylate, o-chlorophenyl
Acrylonitrile Acrylate, octadecyl
Acrylonitrile Acrylate, octadecyl
Acrylonitrile Acrylate, octadecyl
Acrylonitrile Acrylate, octyl
Acrylonitrile Acrylate, p-bromophenyl
Acrylonitrile Acrylate, p-chlorophenyl
Acrylonitrile Acrylate, phenyl
Acrylonitrile Acryloyl chloride
Acrylonitrile Acryloylpyrrolidone
Acrylonitrile Ally1 acetate
Acrylonitrile Ally1 alcohol
Acrylonitrile Ally1 alcohol
Acrylonitrile Ally1 alcohol
Acrylonitrile Ally1 alcohol
Acrylonitrile Ally1 chloride
Acrylonitrile Ally1 chloride
Acrylonitrile Allylbenzene
Acrylonitrile Allylbenzene
Acrylonitrile Allylcyclohexane
Acrylonitrile Allylstearamide, N-
Acrylonitrile Benzothiazole, vinylmercapto-
Acrylonitrile Butadiene
Acrylonitrile Butadiene
Acrylonitrile Butadiene
Acrylonitrile Butadiene
Acrylonitrile Butadiene
Acrylonitrile But adi ene, 1,4-dicarboxylate, diethyl
Acrylonitrile But adi ene, l-(diethylamino)-
Acrylonitrile But adi ene, l-(diethylamino)-
Acrylonitrile Butadiene, l-acetoxy-
Acrylonitrile Butadiene, 1-ethoxy
Acrylonitrile Butadiene, 1-ethoxy
Acrylonitrile Butadiene, 2-chloro-
Acrylonitrile Butadiene, 2-chloro-
Acrylonitrile Butadiene, 2-chloro-
Acrylonitrile Butadiene, 2-fluoro-
Acrylonitrile Butadiene, 2trimethylsilyloxy-
Acrylonitrile Butadiene-1-carboxylate, ethyl
Acrylonitrile Butadiene-1-carboxylic acid
Acrylonitrile Butadiene-1-carboxylic acid
Acrylonitrile Bu t e n e - 1
Acrylonitrile Butene- 1, 4-(p-chlorophenyl)-
Acrylonitrile Butene-1, 4-(p-methoxy-phenyl)-
Acrylonitrile Butene-1, 4-cyclohexyl-
Acrylonitrile Butene-1, 4-phenyl-
Acrylonitrile Butene-2, cis
Acrylonitrile Butene-2, tram
Acrylonitrile Carbazole, N-vinyl-
1
1
0.72
0.41
2.37
0.92
1.16
0.66
0.44
1.01
1.3
0.56
1.54
1.31
0.8
1.123
1.91
4.39
1.76
1.98
0.8
0.32
0.43
1.2
1.56
6.57
2.6
3.9
1.79
2.145
3.45
3.82
5.35
3.81
3.79
0.191
0.046
0.1
0.05
0.06
0.03
0.29
0.481
0.208
0.012
0.02
0.01
0.04
0.05
0.056
0.077
0.036
0.3
0.2
0.03
13.46
4.68
2.56
5.03
4.51
22.32
62.99
0.39
0.15
0.07
0.08
0.78
01073
0.03
0.044
0.08
0.037
0.1
0.64
0.2
0.3
0.13
0.056
0.13
2.11
1.06
0.11
0.049
0.65
1.7
0.3
11.42
0.28
0.014
0.006
0.059
0.02
0.12
0.049
0.049
0.043
0.008
0.008
0.023
0.021
3.61
0.63
1.11
0.76
0.86
10.67
0.04
0.9
1.2
0.773
0.24
0.88
1.2
0.81
4
0.95
1
0.85
0.51
0.844
0.85
1.2
1.171
1.04
1.35
0.32
0.84
1.026
0. 95 1
0.327
1
0.43
- 0.09
0.05
0.1
0.12
-0.152
0.08
- 0.05
- 0.026
-0.18
0.03
0.178
0.358
0.452
0.35
0.1
0.2
2.79
0.426
0.425
0.82
0.065
0.065
5.35
4.8
5.38
0.6
0.065
3.2
4
11
0.24
0.066
- 0.085
0.014
0.024
0.11
0.84
0.09
0.067
0.16
0.07
0.27
0.036
0.02
0.037
0.2
0.023
0.38
0.4
0.35
0.74
0.062
0.063
0.045
0.12
0.16
0.37
0.008
0.03
0.15
0.022
1.01
0.27
0. 08 1
0.046
0.023
0.01
0.9
0.208
0.48
0.68
0.009
0.02
0.45
0.18
0.81
0.044
0.088
0.055
0.069
0.6
0.04
N
Y
N
N
Y
Y
N
Y
Y
N
Y
Y
Y
Y
Y
Y
N
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
513
513
1034
363
646
233
1023
1 9 8
389
542
114
363
1024
1 5 1
233
682
363
118
233
290
118
363
363
363
580
666
1 0 8
1 0 8
1 0 8
176
300
108
47
24
3 5 1
24
119
763
2 1
255
418
5 0 1
66
327
864
889
9 1
864
889
402
504
6 1
174
993
791
7 9 1
799
211
24
24
24
24
211
2 1 1
269
References page II - 290
II / 196 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contcf
Monomer 1 Monomer 2
r1
f95%
r2
f95% Conv. Refs.
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonittile
Acrylonitrile
Acrylonittile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Actylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Cinnamate, a-cyano-, ethyl
Cinnamon&rile
Cinnamon&rile, a-cyano-
Citraconimide, N-methyl-
Crotonaldehyde
Crotonaldehyde
Crotonate, wchloro-, ethyl
Crotonate, cc-cyano-, ethyl
Crotonate, wmethoxy-, methyl
Crotonate, cc-methyl-, methyl
Crotonate, cc-acetyl-, methyl
Crotonate, wcarboethoxy-, ethyl
Crotonate, ethyl
Crotonic acid
Cyclopentene, 4-, - 1,3-dione
Cyclopropene, 3,3-dimethoxy-
Diallyl phthalate
Diallyl phthalate
Ethylene
Ethylene, 1, l-diphenyl-
Ethylene, tetrachloro-
Ethylene, tetrachloro-
Ethylene, trichloro-
Ethylene, trichloro-
Fumarate, diisopropyl
Fumarate, diethyl
Fumarate, diethyl
Hexatriene, tetrachloro-
He x e n e - 1
Indene
Indene
Isobutylene
Isobutylene
Isobutylene
Isoprene
Isopropenyl methyl ketone
Isopropenyl methyl ketone
Isopropenylisocyanate
Itaconic acid
Itaconic anhydride
Maleate, diethyl
Maleate, diethyl
Maleic anhydride
Mal ei mi de, N-(2-bromophenyl)-
Mal ei mi de, N-(2-chlorophenyl)-
Mal ei mi de, N-(Cchlorophenyl)-
Mal ei mi de, N-2-bromophenyl-
Mal ei mi de, N-2-chlorophenyl-
Mal ei mi de, N-Cchlorophenyl-
Maleimide, N-octadecyl-
Maleimide, N-octadecyl-
Metbacrylamide, N-(p-chlorophenyl)-
12.6 2.3 -0.18 0.15
8.46 0.37 0.36 0.1
0.53
8
25
9.53
11.4
1
2.97
8.68
18.7
25.2
2 1
3.02
1.424
4.23
2.78
7
0.05
456
470
67
62.1
1 6
8
1 0
0.234
2.07
0. 28 1
0.29
1.295
0.98
1.02
0.03
0.3
0.36
0.24
0.59
0.034
1 2
20
6
2.029
0.956
0.972
2.02
0.955
0.972
2.482
2.46
0.399
0.71
0.038
0.15
0.52
0.058
0.037
0.012
0.031
0.01 0.01
0.05
0.6
0
0.01
0
0.06
0
0
0
0
0
0
0.04
0.245
0.04
0.037
0
- 0.02
0
0
0
0
0.2
0
0.1
4.01
- 1.08
0.09
0.07
0
0.02
0
0.45
1.2
0.7
0.1
0.86
4.83
0
0
0
0.338
1.078
0.743
0.348
1.08
0.743
0.389
0.39
0.627
0.559
0.549
2.34
0.71
1 4
1.25
0.05
0.12
0.008
0.25
0.25
0.24
0.002
0.38
0.34
0.014
0.74
0.33
0.214
0.095
0.112
0.205
0.095
0.112
0.119
0.115
0.019
0.019
0.026
0.14
0.085
0.045
0.048
0.048
0.044
0.048
0.048
0.023
0.023
0.051
0.048
0.06
1.07
0.19
Methacrylamide, N-@-methoxyphenyl)-
Methactylamide, N-@-methylphenyl)-
Methacxylamide, N-(p-nitrophenyl)-
Methacrylamide, N-phenyl-
Methacrylate, 2,2,6,6-tetramethyl-
4-piperidinyl
Methacrylate,
2-(NJ+dimethylcarbamoyloxy)ethyl
Methacrylate, 2-bromoethyl
Methacrylate, 2-chloroethyl
Methacrylate, 2-hydroxyethyl
Methacrylate, 2-naphthyl
Metbacrylate, 2-naphthyl
0.337
0.336
0.37
0.381
0.02
0.38 1.89
0.31
0.14
0.2
0.15
0.094
0.2
0.099
2.38
1.3
1
1.17
1.02
0.2
0.19
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
310
310
310
460
429
504
785
785
785
785
785
785
785
402
95
838
1 5 3
1 5 3
415
1 4 3
571
59
470
572
1038
470
640
4
60
360
360
2 1
211
484
417
490
542
434
164
365
470
640
470
863
863
863
915
915
915
863
915
352
352
352
352
352
664
600
657
382
689
611
611
TABLE 1. contcf
Monomer 1 Monomer 2 r1
Copolymer Reactivity Ratios II / 197
+95%
r2
f95% Conv. Refs.
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Methacrylate, 2-naphthyl 0.06
Methacrylate, 2-naphthyl - 0.01
Methacrylate, 3,5-dimethyladamantyl 0.19
Methacrylate, benzyl 0.2
Methacrylate, butyl 0.291
Methacrylate, ferrocenylmethyl 0.15
Methacrylate, glycidyl 0.95
Methacrylate, glycidyl 0.14
Methacrylate, isobutyl 0.217
Methacrylate, methyl 0.138
Methacrylate, methyl - 0.016
Methacrylate, mono-, ethylene glycol 0.19
Methacrylate, phenyl 0.36
Methacrylate, potassium 0.226
Methacrylate, potassium 18-crown- 0.07
6-ether
Methacrylic acid 0.04
Methacrylic.acid 0.092
Methacrylonitrile 0.43
Methacryloyl chloride 0.35
Methaclyloyl acet one 0.01
Methylenebutyrolactone 0.09
N,N-Divinylaniline 0.246
N-Vinylimidazole 3.393
Naphthalene, l-vinyl- 0.107
Norbornadiene 0.48
Norbornadiene 0.66
Ott-1-ene, 6,6-dimethyl-4,8-dioxaspiro 0.985
Oxazoline, 2-,2-isopropenyl- 0.13
Oxazoline, 2-,2-isopropenyl-, 0.24
4-dimethyl
Oxazoline, 2-,4-methacryloxy- 0.11
2,4-dimethyl
Pentadiene, trans- 1,3- 0.06
Pentadiene, cis-1,3- 0.026
Pentadiene, cis-1,3- 0.056
Pentadiene, cis- 1,3- 0.033
Pentadiene, trans- 1,3- 0.07
Pentadiene, truns- 1,3- 0.085
Pentadiene, trans- 1,3- 0.079
Pentadiene, cis-1,3- 0.06
Pentadienoate, trans-4-ethoxy-2,4-, ethyl 0.01
Pentene-1, 5-cyclohexyl- 4.22
Pentene- 1, 5-phenyl- 3.84
Phosphate, diethyl isopropenyl 15.2
Phosphine oxide, diphenylvinyl- 3.8
Phosphonic acid, a-phenylvinyl- 0.34
Phosphonic acid, a-phenylvinyl- 2.36
Phthalide, 3-(4.vinylphenoxy)- 0.084
Phthalimide, N-vinyl- 0.43
Phthalimide, N-(methacryloyloxy)- 0.204
Pinene 0.07
Propene, 2-chloro- 1.164
Propene, 3,3,3-trichloro- 12.2
Pr opene, I-chloro-, cis- 23.37
Propene, 1-chloro-, trans- 19.61
Pyridazinone, 3-(2-vinyl)-6-methyl- 0.32
Pyridazinone, 3-(2-vinyl)-6-methyl-4,5- 0.74
Pyridine, 2-methyl-Svinyl- 0.16
Pyridine, 2-vinyl- 0.05
Pyridine, 2-vinyl- 0.1
Pyridine, 2-vinyl-5-ethyl- 0.02
Pyridine, 2-vinyl-5-ethyl- 0.06
Pyridine, 4-vinyl- 0.11
Pyridine, 4-vinyl- 0.09
0.1
0.16
0.01
0.1
0.039
0.04
0.06
0.037
0.037
0.048
0.04
0.006
0.13
0.06
0.04
0.004
0.014
0.008
0.028
0.27
0.01
0.675
0.064
0.018
0.017
0.017
0.018
0.071
0.45
0.48
0.12
0.053
0.01
0.016
0.01
0.053
2.99
1.72
0.02
0.02
0.01
0.03
0.07
0.04
0.76
0.64
1.3
0.96
0.98
0.82
0.85
1.32
1.05
1.322
1.11
1.5
0.46
0.203
0.175
0.2
2.38
1.67
2.8
3.74
1.1
- 0.006
0.832
0.451
0.05
0.44
1.484
0.52
1.83
0.89
0.095
0.172
0.198
0.188
0.104
0.132
0.114
0.241
5.4
- 0.043
- 0.026
0.03
0.16
- 0.45
0
0.43
0.24
1.45
13.5
- 0.023
0.1
- 0.12
0.01
0.19
0.02
0.31
21.9
0.44
0.43
0.43
0.41
0.34
0.18
0.24
0.23
0.1
0.2
0.42
0.05
0.22
0.05
0.12
0.086
0.018
0.26
0.29
0.12
0.22
0.07
0.044
0.088
0.23
0.05
1.078
0.021
0.012
0.011
0.01
0.009
0.029
0.044
0.046
0.41
0.19
0.02
0.072
0.1
0.062
0.19
0.17
0.04
0.02
0.02
0.08
0.18
0.13
Y
N
N
N
Y
Y
N
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
N
N
Y
Y
Y
N
Y
N
Y
N
Y
Y
Y
Y
Y
Y
Y
N
N
N
N
N
N
611
6 1 1
335
23
1 6 5
325
114
433
1 6 5
216
681
682
363
808
808
1 6
216
198
580
339
745
45
879
967
267
69
838
862
596
596
867
867
952
997
867
952
997
867
723
24
24
650
843
132
590
721
1046
979
936
1 8 1
402
1 8 1
1 8 1
340
340
232
456
50
1 1 5
50
1 1 5
50
References page II - 290
II / 198 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer< 2
rl f95% r2 zt95% Conv. Refs.
Acrylonitrile Pyrrolidone, N-vinyl-
Acrylonitrile Silane, y-methacryloxypropyltrimethoxy- 0.094
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene, 2,4,6-trimethyl-
Styrene, 2,5-dichloro-
Styrene, 2,5-dichloro-
Styrene, 2,5-dichloro-
Styrene, 3-tri-n-butylstannyl-
Styrene, 4-methyl-
Styrene, a-(trimethylsilyloxy)-
Styrene, a-methoxy-
Styrene, a-methyl-
Styrene, a-methyl-
Styrene, a-methyl-
Styrene, a-methyl-
Styrene, a-methyl-
Styrene, a-methyl-
Styrene, a-methyl-
Styrene, wmethyl-
Styrene, m-methyl-
Styrene, p-1-(2-hydroxy-butyl)-
Styrene, p-1-(2-hydroxy-propyl)-
Styrene, p-2-(2-hydroxy-propyl)-
Styrene, p-acetoxy-
Styrene, p-chloro-
Styrene, p-chloromethyl-
Styrene p-methyl-
Succinimide, N-vinyl-
Tetrazole, 2-methyl-5-(4~vinyl)phenyl-
Tetrazole, 5-phenyl-2-(4-vinyl)phenyl-
Tetrazole, l-vinyl-
Toluenesulfonamide, N,N-methyl-vinyl-
Triallyl citrate
Tricyclo[4.2.2.0{2,5}]dec-7-ene-
3,4,9,10-tetracarboxylic aci d
Vinyl 12-ketostearate
Vinyl 2-chloroethyl ether
Vinyl 2-ethylhexanoate
Vinyl 3,3-bis(ethoxycarbonyl)propyl
ether
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl benzoate
Vinyl bromide
Vinyl bromide
Vinyl butyl ether
0
0.02
0.05
0.03
0.06
0.05
0.07
0.04
0.17
0.17
0.15
0.17
0.07
0.06
0.03
0.06
0.01
0.874
0.22
0.25
0.26
4.88
0.079
0.05
0.06
0.07
0.04
0.04
0.04
0.063
0.34
0.03
-
0.02
0.07
0.04
0.1
0.05
0.07
- 0.09
0.067
0.05
0.116
0.42
0.32
0.54
0.42
1.76
2.75
3.3
1.09
9.24
1.02
4.05
5.51
5.29
9.2
5.03
2.79
2.25
0.034
0.06
0.594
0.04
0. 05 1
0.01
0.005
0.041
0.15
0.27
0.01
0.06
3.79
0.33
0.29
0.4
0.36
0.39
0.37
0.37
0.4
0.3
0.33
0.33
0.36
0.46
0.41
0.43
0.55
0.35
0.065
0.08
0.07
0.09
0.001
0.227
0
- 0.002
0.08
0.17
0.24
0.14
0.09
0.103
0.14
0.08
0.43
0. 3 1
0.53
0.41
0.4
0.92
0.56
0.33
0.516
1.1
1.4
0.314
0.04
- 0.08
0.25
0.048
0.03
0.005
0.01
0.04
0.021
0.01
0.03
0.03
0.024
0.036
0.07
0.03
0.06
0.024 0.081
0.032
0.12
0.082
0.066
1.04
0.1
0.5
1.96
-0.18
0
- 0.047
0.06
0.36
0.05
0.82 0.04 0.067
0.91
1.13
6.39
1.08
0.2
0.06
- 0.06
- 0.03
0.019
0.06
0.06
0.22
0.08
0.09
0.051
0.04
Y
Y
N
Y
N
Y
N
N
N
Y
Y
N
N
N
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
Y
N
N
213
977
140
1 9 8
269
396
403
417
543
60
727
727
727
727
727
727
727
727
812
58
84
84
84
985
929
970
142
1 7 1
265
265
65
75
75
835
94
378
548
380
547
47
825
1035
378
80
583
583
925
80
367
963
146
597
47
1015
1 5 8
235
6
75
75
47
268
268
345
TABLE 1. contd
Copolymer Reactivity Ratios II / 199
Monomer 1 Monomer 2
rt &95% r2 &95% Conv. Refs.
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Vinyl butyl ether
Vinyl butyl sulfide
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloride
Vinyl chloroacetate
Vinyl chloroacetate
Vinyl chloroethyl ether
Vinyl chloromethyl ketone
Vinyl cymantrene
Vinyl dichloroacetate
Vinyl dichloroacetate
Vinyl dodecyl ether
Vinyl ether
Vinyl ethyl ether
Vinyl ethyl oxalate
Vinyl ethyl sulfide
Vinyl ethyl sulfide
Vinyl ethyl sulfoxide
Vinyl fluoride
Vinyl fluoride
Vinyl formate
Vinyl hendecanoate
Vinyl isobutyl ether
Vinyl isobutyl ether
Vinyl isobutyl ether
Vinyl isobutyl ether
Vinyl isobutyl sulfide
Vinyl isobutyl sulfide
Vinyl isobutyl sulfide
Vinyl isothiocyanate
Vinyl laurate
Vinyl methyl ketone
Vinyl methyl ketone
Vinyl octadecyl ether
Vinyl octyl ether
Vinyl phenyl ether
Vinyl phenyl sulfide
Vinyl phenyl sulfide
Vinyl stearate
Vinyl tert-butyl sulfide
Vinyl trichloroacetate
Vinyl, a-chloro-, triethoxysilane
Vinyl, p-, benzylethylcarbinol
Vinyl, p-, benzylmethylcarbinol
Vinyl-tris(trimethoxysiloxy)-silane
Vinyl-tris(trimethoxysiloxy)-silane
Vinylbenzoate, p-, sodium
Vinylbenzoic acid, p-
Vinylene carbonate
Vinylethynyl-4-piperidinol,
1,2,Qrimethyl
Vinylferrocene
Vinylferrocene
Vinylhydroquinone
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
0.98
0.086
3.26
2.55
2.62
3.62
3.65
4
4.18
0.34
1.04
0.064
0.446
7.45
0.25
0.82
0.94
0.69
1.34
0.09
0.06
1.63
44
24
2.54
1.88
- 0.24
- 0.05
0.98
1.26
0.08
0.062
0.08
0.36
4
0.59
0.63
0.85
0.81
2.5
0.11
0.11
4.639
0.09
7.34
0.04
0.11
3.9
3.85
0.174
0.06
14.9
0.08
0.186
0.16
0.56
0.92
1.04
0.44
0.58
0.65
0.57
0.5
0.13
0.01
0.34
0.12
0.25
0.21
0.22
0.33
0.05
0.019
0.048
0.32
0.12
0.45
0.01
0.01
0.16
1.79
0.44
0.26
0.07
0.15
0.19
0.005
0.004
0.004
0.13
0.01
0.01
0.015
0.024
0.9
0.17
0.04
0.009
0.025
0.36
0.11
0.2
- 0.03
0.041
- 0.01
0.07
0.02
0.044
0.052
0.04
- 0.007
0.09
- 0.02
0.88
- 0.065
0.044
0.18
0
0.02
0.06
0.06
0.06
0.05
- 0.08
0.005
1
- 0.004
0.09
0.7
0.99
- 0.04
- 0.04
0.03
0.022
0.03
1.4
0.04
1.75
1.39
0
0
0.23
0.03
0.03
0.078
0
0.047
0.31
0.54
0.07
0.08
0.23
1.63
0.08
0.38
0.165
0.15
0.04
0.32
0.28
0.4
0.42
0.49
0.69
0.76
0.01
0.028
0.037
0.03
0.08
0.002
0.01
0.016
0.02
0.12
0.093
0.015
0.12
0.03
0.03
0.03
0.14
0.12
0.91
0.09
0.06
0.01
0.02
0.01
0.038
0.01
0.11
0.02
0.01
0.007
0.013
0.039
0.2
0.34
0.42
0.092
0.03
0.14
0.034
N
Y
Y
N
N
Y
Y
Y
N
Y
Y
N
N
N
N
N
Y
Y
Y
N
N
N
N
N
Y
N
Y
N
N
Y
Y
Y
Y
N
Y
Y
Y
N
Y
Y
347
303
140
202
22
238
46
529
362
542
116
356
354
362
542
373
386
194
285
285
336
286
528
590
47
1 4 5
322
322
347
347
285
303
336
542
381
140
504
373
373
556
285
336
1 4 5
303
362
591
48
209
573
1 7 5
1 7 5
579
783
294
294
338
138
238
404
404
404
404
404
References page II - 290
II / 200 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2 rl *95%
r2
Lk95% Conv. Refs.
Acrylonittile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile, 2-chloro-
Acrylonitrile, 2-fluoro-
Acrylonitrile, a-chloro-
Acrylonitrile, a-fluoro-
Acrylonitrile, cc-hydroxymethyl-
Acrylonitrile, cc-methoxy
Acrylonitrile, a-methoxy
Acrylonitrile, a-perfluoropropyl-
Acryloxymethylpentamethyldisiloxane
Acryloyl chloride
Acryloyl chloride
Acryloyl chloride
Acryloyl chloride
Acryloyl chloride
Acryloyl chloride
Acryloyl chloride
Acryloyl chloride
Acryloyl chloride
Acryloyl-P-hydroxyethyl-3,5-
dinitrobenzoate
Acryloyl-P-hydroxyethyl-3,5-
dinitrobenzoate
Acryloyloxy, 2-, benzoic acid
Acryloyloxy, 2-, benzoic acid
Acryloylpyrrolidone
Adipate, divinyl
Ally1 acetate
Ally1 acetate
Ally1 acetate
Ally1 acetate
Ally1 acetate
Ally1 acetate
Ally1 acetate
Ally1 acetate
Ally1 acetate
Ally1 acetate
Ally1 acetate
Ally1 acetate
Ally1 acetate
Ally1 acetate
Ally1 acetate
Ally1 acetate
Ally1 acrylate
Ally1 acrylate
Ally1 acrylate
Ally1 alcohol
Ally1 alcohol
Ally1 alcohol
Ally1 alcohol
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylidene chloride
Vinylisocyanate
Vinylmethyldiacetoxysilane
Vinylmethylphenylsulfonium
tetrafluoroborate
Vinyltriethoxysilane
Vinyltriethoxysilane
Vinyltrimethoxysilane
Vinyltrimethylsilane
Styrene
Styrene
Styrene
Styrene
Styrene
Acrylate, cc-chloro-, ethyl
Styrene
Methacrylate, methyl
Methacrylate, 2-hydroxyethyl
Acrylate, methyl
Acrylonitrile
Methacrylate, 2-hydroxypropyl
Methacrylate, methyl
Methacrylate, methyl
Pyrrolidone, N-vinyl
Styrene
Vinyl chloride
Vinylidene chloride
Acrylate, N-(2-hydroxyethyl))carbazolyl
0.48
0.65
0.65
0.66
0.63
0.63
0.58
0.19
2.246
2.2
6.59
26.83
9.09
4.08
0.087
0.03
0.03
0.528
0.3
0.312
0
0.52
2.3
0.29
1.51
0.05
0.15
0.02
3.03
1.12
0.361
Methacrylate, N-ethyl-
3-hydroxymethylcarbazolyl
Methacrylate, N-methyl-N-phenyl-
2-amino
Styrene
Acrylonitrile
Styrene
Acrylate, butyl
Acrylate, methyl
Acrylonitrile
Isobutylene, 3-chloro-
Maleic anhydride
Methacrylate, ethyl
Methacrylate, methyl
Methacrylate, methyl
Styrene
Styrene
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl chloride
Vinyl chloride
Vinylidene chloride
Acrylate, methyl
Ally1 chloride
Vinyl acetate
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
0.103
1.82
0.64
0.43
0.011
0.039
0
- 0.09
0.15
- 0.001
- 0.57
- 2.42
0
0.01
0
0.45
0.7
0.7
1.2
0
0
0.33
10.4
17.35
0.05
0.1
0.12
0.054
0.6
29.59
0.76
0.04
0.02
0.086
0.054
0.05
0.02
0.22
0.016
0.015
0.2
0.02
0.011
0.066
0.12
0.007
0.82
37.66
0.05
0.16
0.37
0.95
0.95
1.3
1.74
1.43
1.8
0.39
0.16
-0.11
0.1
0.41
2.69
0.45
0.1
0.014
0.13
0.44
0.205
0.9
0.534
1.9
0.86
0.34
1.2
1.79
0.48
0.42
0.04
0.1
0.02
0.5
0.62
1.425
0.22
0.06
1.56
20.36
10.2
5
6.57
4.5
0.028
81.27
99.24
2 3
62.8
90
0.6
1
1
1.16
6.6
0.52
0.08
0.11
2.6
3.9
1.79
0.23
0.38
2.5
0.27
0.004
0.04
0.029
0.069
0.3
0.05
0.029
0.044
0.09
0.03
0.02
0.26
42.2
2.11
0.019
1.93
24.6
82.7
1.06
0.11
Y
Y
Y
Y
Y
Y
Y
Y
N
Y
Y
Y
N
N
Y
N
Y
Y
N
N
N
N
N
Y
404
404
404
404
404
404
468
435
754
793
209
237
237
209
884
884
806
850
981
638
806
926
822
508
580
649
508
776
599
220
288
288
702
701
651
651
666
815
1053
470
108
412
27
210
210
470
1053
470
140
502
998
470
475
470
578
578
578
1 0 8
1 0 8
176
300
TABLE 1. contd
Copolymer Reactivity Ratios II / 201
Monomer 1 Monomer 2
rl
f95%
r2
f95% conv. Refs.
Ally1 alcohol
Ally1 alcohol
Ally1 butyrate
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloride
Ally1 chloroacetate
Ally1 chloroacetate
Ally1 glycidyl hexahydrophthalate
Ally1 glycidyl phthalate
Ally1 isobutyrate
Ally1 propionate
Ally1 trichloroacetate
Ally1 trimethylacetate
Ally1 valerate
Allylbenzene
Allylbenzene
Allylbenzene
Allylbenzene
Allylbenzene
Allylbenzene
Allylcyclohexane
Allylstearamide, N-
Allylstearamide, N-
Allylstearamide, N-
Allyltriethoxysilane
Allylurea
Azlactone, 2-vinyl-4,4-dimethyl-
Azlactone, 2-vinyl-4,4-dimethyl-
Azobenzene, 4-(acrylamidomethylamino)-
Azobenzene, 4-(acrylamidomethylamino)-
Benzenesulfamide, p-methacrylamide-
Benzimidazole, vinylmercapto-
Benzoate, p-(acryloylethoxy)-,
p-butoxy phenyl
Benzoate, p-(acryloylethoxy)-, phenyl
Benzoate, p-(acryloyloxy)-,
p-butoxy phenyl
Benzoate, p-(acryloyloxy)-,
p-butoxy phenyl
Benzoate, p-(acryloyloxy)-,
p-methoxy phenyl
Methacrylate, ethyl
Methacrylate, methyl
Vinyl acetate
Acrylate, benzyl
Acr yl at e, but yl
Acrylate, ethyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylate, methyl
Acrylic anhydride
Acrylonitrile
Acrylonitrile
Ally1 acrylate
Methacrylate, benzyl
Methacxylate, methyl
Styrene
Styrene
Styrene
Vinyl acetate
Vinyl acetate
Vinyl acetate
Vinyl benzoate
Vinyl butyrate
Vinyl formate
Vinyl propionate
Vinylidene chloride
Methacrylic anhydride
Styrene
Styrene
Styrene
Vinyl acetate
Vinyl acetate
Styrene
Vinyl acetate
Vinyl acetate
Acrylate, methyl
Acrylonitrile
Acrylonitrile
Maleic anhydride
Methacrylonitrile
Triallyl citrate
Acrylonitrile
Acrylonitrile
Vinyl acetate
Vinylidene chloride
Vinyl chloride
Methacrylic anhydride
Acrylate, whydroxymethyl-, ethyl
Styrene
Styrene
Vinyl acetate
Vinyl butyl ether
Styrene
Benzoate, p-(acryloyloxy)-,
p-butoxy phenyl
Benzoate, p-(acryloyloxy)-,
p-butoxy phenyl
Benzoate, p-(acryloyloxy)-, p-butoxy
phenyl
Benzoate, p-(acryloyloxy)-, phenyl
Benzoate, p-(acryloyloxy)-, phenyl
p-butoxyphenyl
- 0.02
- 1.62
0.64
0.06
0.1
0.08
1.92
2.9
107.4
78.79
0.97
9.9
5.83
7.73
5.3
6.5
0.05
0.07
0.4
- 0.02
0.02
-0.152
0.08
0.08
0.02
0.02
0.008
0.03
8.45
5.45
6.46
9.1
11.66
2.145
3.45
10.4
58.7
0.56
0.049
0.65
0.05 0.16 35.55 15.82
0.03
- 2.4
0.61
0.75
0.88
1.15
0.78
0.68
0.24
- 0.01
0.06
0.06
0.14
0.51
0.42
0.81
0.34
0.58
- 0.036
- 0.05
- 0.026
3.21
0.15
0.089
0.15
0.24
0.13
36.8
1.355
0.66
0.34
0.46
0.31
0.57
0.62
3.49
29.76
34.3
34.3
34.8
1.04
1.29
2.32
1.15
1.07
11.35
3.82
5.35
1.4
1 3
0.02 0.15
0.016
0.15
0.022
0.66
1.7
0.3
- 0.061
0.339
-0.18
0.03
0.68
- 0.24
- 0.94
- 0.06
0.389
0.237
8.5
12.98
3.4
0.56
0.36
0.03
0.039
1.01
0.27
0.26
0.19
0.48
0.17
0.229
0.129
1.36
0.5
11.42
0.28
0.092
0.15
0.38
18.48
0.12
0.054
0.1
0.41
16.24
2.01
3.81
3.79
0.923
5.22
1.68
29.01
0.668
0.175
0.083
0.126
0
6.51
0.91
0.51
N
N
Y
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
210
210
998
438
438
438
204
437
437
437
437
219
108
47
578
438
204
1 0
204
438
204
3
438
438
438
438
438
3
106
782
782
782
998
998
913
998
998
351
24
351
351
351
367
24
119
119
119
237
106
1 0 1 1
1 0 1 1
880
880
1005
764
881
0.61 0.32 8 8 1
0.91 0.36 881
0.32 0.61 881
0.49 1.5 881
References page II - 290
II / 202 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
rl It95% r2 It95% Conv. Refs.
Benzoate, p-(acryloyloxy-ethoxy)-,
p-butoxy phenyl
Benzoate, p-(acryloyloxy-ethoxy)-,
p-methoxy phenyl
Benzoate, p-(acryloyloxy-ethoxy)-,phenyl
Benzoate, p-(methacryloyloxy)-,
p-octyloxy phenyl
Benzoate, p-(methacryloyloxyethoxy)
p-octyloxy phenyl
Benzocyclobutane, a-methylene-
Benzocyclobutane, a-methylene-
Benzocyclobutene, 4-vinyl-
Benzofuran, 2-vinyl-
Benzofuran, 2-vinyl-
Benzofuran, 2-vinyl-
Benzophenone, 2-hydroxy-
4-(methaclyloxy)-
Benzophenone, p-vinyl-
Benzophenone, p-vinyl-
Benzophenone, p-vinyl-
Benzophenone, p-vinyl-
Benzophenone, p-vinyl-
Benzophenone, p-vinyl-
Benzothiazole, vinylmercapto-
Benzothiazole, vinylmercapto-
Benzothiazole, vinylmercapto-
Benzothiazole, vinylmercapto-
Benzothiazole, vinylmercapto-
Benzothiazole, vinylmercapto-
Benzothiazole, vinylmercapto-
Benzothiazole, vinylmercapto-
Benzoate, p-(acryloyloxy)-,
p-butoxy phenyl
Benzoate, p-(acryloyloxy)-, phenyl
butoxy phenyl
Benzoate, p-(acryloyloxy)-, phenyl
0.61 0.32 856
1.26 0.23 8 8 1
-1 1.26 0.23 856
Maleic anhydride 0.002
Methacrylate, methyl 0.46
Methacrylate, methyl 1.47
Acrylate, butyl 7.8
Acrylate, ethyl 5.76
Methacrylate, methyl 3.89
Methacrylate, methyl 1.65
Acrylate, methyl
Acrylate, methyl
Styrene, p-N,N-dimethyl-aminomethyl-
Styrene, p-N,N-dimethylamino-
Styrene, p-dimethylamino-
Styrene, p-dimethylaminomethyl-
Acrylonitrile
Fumaronitrile
Maleic anhydride
Methacrylate, methyl
Styrene
Styrene
Vinyl acetate
Vinyl phenyl sulfide
3.6 1.06 0.09 0.02
3.54 0.077 1.1 0.02
2.54 0.136 0.26 0.017
0.84 0.18 0.07 0.05
0.842 0.072 0.176 0.046
2.54 0.259 0.135 0.017
0.178 0.081 0.191 0.014
Benzothiazolone, N-[(methacroyloxy)- Styrene
methyl]
Benzoxazole, vinylmercapto- Styrene
Bicyclo[2,2,l]hept-2-ene-5,6-dicarboximide, Methacrylate, methyl
N-benzyl
Bicyclo[2,2,l]hept-2-ene-5,6-dicarboximide, Methacrylate, methyl
N-benzyl
Bicyclo[2,2,1]hept-2-ene-5,6-dicarboximide, St yrene
N-benzyl
Bicyclo[2,2,l]hept-2-ene-5,6-dicarboximide, St yrene
N-benzyl
Bicyclo[2,2,l]hept-2-ene-5,6-dicarboximide, Vinyl acetate
N-benzyl
Bicyclo[2,2,l]hept-2-ene-5,6-dicarboximide, Vinyl acetate
N-benzyl
Bicyclo[2,2,l]hept-2-ene-5,6-dicarboximide, Vinyl acetate
N-benzyl
Borazine, P-vinyl Styrene
Butadiene Aconitate, trimethyl
Butadiene Acrylate, butyl
Butadiene Acrylate, heptafluorobutyl
0.43 0.14 1.25 0.083
0.349 0.087 2.171 0.07
0.5 0.095 3.02 0.14
2.53 0.47 0.013 0.037
0.95 0.61 0.24 0.12
3.1 0.01 0.35 0.02
0.24
0
0
0
0
0.35
0.15
0.014
0.001
0.4
1.04
0.359
Benzoate, p-(acryloyloxy)-, phenyl
p-butoxy phenyl
Benzoate, p-(acryloyloxy)-, phenyl
p-butoxy phenyl
Benzoate, p-(acryloyloxy)-,
p-butoxy phenyl
Benzoate, p-(acryloyloxy)-,
p-butoxy phenyl
Benzoate, p-(acryloyloxy)-, phenyl
Benzoate, p-(acryloyloxy)-, phenyl
Benzoate, p-(acryloyloxy)-,
p-methoxyphenyl
Benzoate, p-(methacryloyloxy)-,
@-octyloxy)phenyl
Benzoate, p-(acryloyloxy-ethoxy)-,
p-butoxy phenyl
Benzoate, p-(acryloyloxy-ethoxy)-,
phenyl
Benzoate, p-(acryloyloxy-ethoxy)-,
p-methoxy phenyl
Benzoate, p-(methacryloyloxy-
ethoxy)-, p-methoxy phenyl
Benzoate, p-(acryloyloxy)-,
p-butoxy phenyl
Benzoate, p-(acryloyloxy)-, phenyl
1.5 0.49 8 8 1
0.23 1.26 881
0.91 0.36 856
0.32 0.61 856
1.5 0.49 856
0.23 1.26 856
0.36 0.91 856
0.49 1.5 856
1.36
0.334
0.617
0.114
0.025
0.32
0.6
0.041
0.015
0.006
0.315
0.043
0.01
0.02
0.036
N
N
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
1083
1083
1085
1020
1020
1020
934
866
911
86
866
911
911
763
763
763
763
764
764
763
763
960
0.12 2.87
30.5
0.19 764
994
108 994
18.2 994
89.2 994
1.26 994
1.46 994
1.99
4.53
0
0.074
0.073
994
0.016
0.4
0.11
0.039
0.62
0.22
0.03
0. 03 1
Y
Y
Y
1018
147
257
206
TABLE 1. contd
Copolymer Reactivity Ratios II / 203
Monomer 1 Monomer 2
rl f95% r2 zt95% Conv. Refs.
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene
Butadiene monoxide
Butadiene, 1,4-dicarboxylate-,diethyl
Butadiene, 1,4-dicarboxylate-, diethyl
Butadiene, 1,4-dicarboxylate-,diethyl
Butadiene, 1-(2-hydroxyethylthio)-
Butadiene, l-(diethylamino)-
Butadiene, l-(diethylamino)-
Butadiene, l-acetoxy-
Acrylate, methyl
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Acrylonitrile
Butadiene, 2,3-dimethyl-
Butadiene, 2,3-dimethyl-
Butadiene, 2-chloro-
Butadiene, 2-phthalidomethyl
Cyclobutane, 1,2-dimethylene-
Cyclobutane, 1,2-dimethylene-
Ethylene, trichloro-
Ferrocene, ethyl-a-cylopentadienylide
Fumarate, diethyl
Isoprene
Isoprene
Maleamic acid, N-3-dimethylamino-
6-methyl phenyl
Maleate, diethyl
Methacrylate, 2-(N,N-dimethyl-
carbamoyloxy)ethyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylate, methyl
Methacrylonitrile
Methyleneglutaronitrile, 2-
Pentadiene, cis- 1,3-
Pentadiene, tram-1,3-
Pyridine, 2-methyl-5-vinyl-
Pyridine, 2-methyl-5-vinyl-
Pyridine, 2-methyl-5-vinyl-
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene
Styrene, 2,5-dichloro-
Styrene, 2,5-dichloro-
Styrene, p-chloromethyl
Styrene, a-methyl-
Styrene, p-chloro-
Vinyl chloride
Vinyl chloride
Vinylhendecanoate
Vinyl pelargonate
Vinyl stearate
Vinylferrocene
Vinylidene chloride
Maleic anhydride
Acrylonitrile
Pyridine, 2-vinyl-
Styrene
Styrene, p-chloro-
Acrylonitrile
Acrylonitrile
Acrylonitrile
1.09
0.358
0.452
0.35
0.1
0.2
1.26
0.3
0.06
1.014
0.1
0.1
9.64
0.02
2.13
0.94
0.14
0.37
8.08
1.06
0.75
0.504
0.7
0.39
0.63
1.22
0.61
1.32
1.29
1.44
1.55
1.37
1.35
1.59
1.8
1.4
1.4
0.5
1.38
1.83
1.38
0.449
0.662
0.87
1.5
1.22
8.8
5.27
22.56
26.3
42.5
4.34
1.97
0.05
2.79
0.69
0.55
3.27
0.426
0.425
0.82
4.53
0.046
0.23
0.01
0.92
0.049
0.05
0.21
0.37
0.04
0.024
0.15
0.02
0.56
0.14
0.11
0.41
0.043
0.017
0.13
2.16
3.35
24.54
4.73
0.18
0.25
0.18
0.9
0.23
0.1
0.208
0.48
0.68
0.07
0.046
0.1
0.05
0.06
0.03
0.78
0.86
3.41
1.35
5.76
5.76
0.03
1.51
0.25
1.06
0.608
0.08
0.25
0.027
0.32
0.053
0.26
0.09
0.47
0.72
0.41
0.84
0.37
0.38
0.58
0.44
0.6
0.44
0.38
0.68
0.82
0.83
0.64
0.45
0.187
0.42
0.139
1.6
0.04
0.11
0.22
0.02
0.02
0.16
0.044
0.64
0.29
0.41
0.09
0.24
0. 48 1
0.208
0.012
0.87
0.006
0.059
0.02
0.24
0.45
0.36
0.07
0.062
0.03
0.004
0.016
0.02
0.4
0.25
0.13
0.21
0.17
0.049
0.087
5.7
0.31
1.26
0.27
0.15
0.038
0.06
0.12
0.07
0.014
0.049
0.049
0.043
Y
Y
Y
N
Y
Y
N
Y
N
Y
Y
N
N
Y
N
Y
N
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
N
Y
Y
Y
Y
257
2 1
255
418
501
66
1 7 3
8 3
418
735
854
885
89
699
466
1 7 3
8 3
679
466
600
140
257
467
257
196
743
743
462
520
56
140
1 5 9
1 7 3
2 1
418
428
473
486
486
491
56
83
8 3
255
8
1075
70
255
517
717
1 4 5
1 4 5
1 4 5
802
257
1064
327
327
327
810
864
889
9 1
References page II - 290
II / 204 FREE RADICAL COPOLYMERIZATION REACTIVITY RATIOS
TABLE 1. contd
Monomer 1 Monomer 2
r1 f95% r2 *95% Conv. Refs.
Butadiene, l-chloro-
Butadiene, l-ethoxy-
Butadiene, l-ethoxy-
Butadiene, 1 -phthalimido-
Butadiene, l-succinimido-
Butadiene, 2,3-bis(diethylphosphono)-
Butadiene, 2,3-bis(diethylphosphono)-
Butadiene, 2,3-bis(diethylphosphono)-
Butadiene, 2,3-bis(diethylphosphono)-
Butadiene, 2,3-bis(diethylphosphono)-
Butadiene, 2,3-bis(diethylphosphono)-
Butadiene, 2,3-dichloro-
Butadiene, 2,3-dichloro-
Butadiene, 2,3-dichloro-
Butadiene, 2,3-dichloro-
Butadiene, 2,3-dichloro-
Butadiene, 2,3-dichloro-
Butadiene, 2,3-dichloro-
Butadiene, 2,3-dimethyl-
Butadiene, 2,3-dimethyl-
Butadiene, 2,3-dimethyl-
Butadiene, 2,3-dimethyl-
Butadiene, 2,3-chloro-
Butadiene, 2,3-chloro-
Butadiene, 2,3-chloro-
Butadiene, 2,3-chloro-
Butadiene, 2,3-chloro-
Butadiene, 2,3-chloro-
Butadiene, 2,3-chloro-
Butadiene, 2,3-chloro-
Butadiene, 2,3-chloro-
Butadiene, 2,3-chloro-
Butadiene, 2,3-chloro-
Butadiene, 2,3-chloro-
Butadiene, 2,3-chloro-
Butadiene, 2,3-chloro-
Butadiene, 2,3-chloro-
Butadiene, 2,3-chloro-
Butadiene, 2,3-dichloro-
Butadiene, 2-chloro-
Butadiene, 2-chloro-
Butadiene, 2-chloro-
Butadiene, 2-chloro-
Butadiene, 2-chloro-
Butadiene, 2-chloro-
Butadiene, 2-chloro-
Butadiene, 2-chloro-
Butadiene, 2-chloro-
Butadiene, 2-chloro-
Butadiene, 2-chloro-
Butadiene, 2-chloro-
Butadiene, 2-chloro-
Butadiene, 2-chloro-
Butadiene, 2-chloro-
Butadiene, 2-chloro-
Butadiene, 2-fluoro-
Butadiene, 2-fluoro-
Butadiene, 2-fluoro-
Butadiene, 2-fluoro-
Butadiene, 2-fluoro-
Butadiene, 2-fluoro-
Butadiene, 2-fluoro-
Butadiene, 2-fluoro-
Butadiene, 2-phthalidomethyl-
Butadiene, 2-trimethylsilyloxy-
Butadiene, 2-trimethylsilyloxy-
Styrene
Acrylonitrile
Acrylonitrile
Styrene
Styrene
Mal ei mi de
Mal ei mi de, N-(2-hydroxyethyl)-
Mal ei mi de, N-(Cchlorophenyl)-
Mal ei mi de, N-(4-methoxy-phenyl)-
Mal ei mi de, N-chloromethyl-
Maleimide, N-phenyl-
Butadiene, 2-chloro-
Ethylene, 1, l-diphenyl-
Methacrylate, methyl
Phosphonic acid, cc-phenylvinyl-
Phosphonic acid, a-phenylvinyl-
Styrene
Styrene
Butadiene
Butadiene
Isoprene
Styrene
Acrylate, methyl
Acrylonitrile
Acrylonitrile
Acrylonitrile
Butadiene
Butadiene, 1-(2-hydroxyethyl-thio)-
Butadiene, 2,3-dichloro-
Butadiene, 2-fluoro-
Butadiene, hexafluoro-
Butadiene, hexafluoro-
Ethylene, 1, l-diphenyl-
Fumarate, diethyl
Hexatriene, tetrachloro-
Isoprene
Isopropenyl methyl ketone
Methacrylate, methyl
Maleic anhydride
Methacrylate, isobutyl
Methacrylate, methyl
Methacrylic acid
Phosphonate, vinyl-,dimethyl
Phosphonic acid, a-phenylvinyl-
Phosphonic acid, a-phenylvinyl-
Quinoline, 2-vinyl-
Styrene
Styrene
Vinyl acetate
Vinyl butyrate
Vinyl formate
Vinyl formate
Vinyl propionate
Vinylidene cyanide
Acrylonitrile
Butadiene, 2-chloro-
Butadiene, hexafluoro-
Isoprene
Methacrylate, methyl
Styrene
Styrene
Styrene, u-methyl-
Butadiene
Acrylonitrile
Styrene
1.44
0.065
0.065
1.56
1.68
0.14
0.12
0.03
0.04
0.05
0.05
1.98
3.58
11.04
1.15
7.15
8.65
10.6
0.78
0.86
0.84
1.048
5.19
10.4
5.35
4.8
5.38
3.41
1
0.31
3.7
5.47
5.52
3.4
6.51
3.6
2.82
4.035
11.04
0.026
1.8
6.33
2.52
1.5
7.5
1.5
2.1
7.84
5.98
33.52
1 5
11.91
0.6
0.22
2.93
2.63
1.23
2.1
1.24
2.22
1.35
0.065
1.2
3.1
0.009
0.02
0.63
0.16
0.25
0.24
0.066
0.45
0.12
0.087
0.08
0.03
0.06
0.2
0.5
8.98
3.89
0.18
0.96
1.77
0.12
0.61
0.7
0.45
0.27
0.02
0.01
0.299
0.286
0.43
0.49
0.41
0.47
0.3
0.42
0.31
- 0.08
0.08
0.07
0.07
0.25
0.05
1.26
0.3
1.18
0.534
0.06
0.06
0.04
0.05
0.056
0.06
0.2
1.98
0.22
0.1
0.1
0.03
0.02
0.2
0.06
0.14
0.329
0.9
0.08
- 0.035
0.1
0.1
0.1
0.38
0.05
0.025
- 0.02
- 0.04
- 0.05
0.077
3.7
0.24
0.25
0.76
0.214
0.22
0.72
1.014
0.036
0.64
0.27
0.008
0.008
0.049
0.018
0.12
0.92
0.035
0.023
0.25
0.01
0.107
0.088
0.058
0.047
0.09
0.01
0.021
0.12
0. 11
0.03
0.15
0.24
0.049
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
Y
N
N
Y
Y
Y
Y
N
N
N
N
Y
Y
Y
Y
Y
Y
Y
Y
695
864
889
1 6 3
1 6 3
759
759
759
159
759
759
122
6 1
6 1
588
597
587
6 1
1 7 3
83
1 7 3
173
451
6 1
402
504
6 1
418
810
122
493
1 2 7
453
6 1
6 1
459
418
259
6 1
1068
1057
6 1
259
594
546
597
456
6 1
8
247
247
127
247
241
82
174
493
453
174
174
174
174
174
135
993
993
TABLE 1. contd
Copolymer Reactivity Ratios II / 205
Monomer 1 Monomer 2 rl zk95% r2 z!?95% Conv. Refs.
Butadiene, hexafluoro-
Butadiene, hexafluoro-
Butadiene, hexafluoro-
Butadiene, hexafluoro-
Butadiene,l-(2-hydroxyethylthio)-
Butadiene- lcarboxylate, ethyl
Butadiene-lcarboxylate, S-(-)a-phene
ammonium
Butadiene-1-c