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Rate Equations of Polymerization Reactions

Reiji Mezaki
Mitsubishi Research Institute

Guang-Hui Ma
Tokyo University of Agriculture and Technology

ChemTec Publishing

Copyright 0 1997 by ChemTec Publishing ISBN 1-895198-16-X
All rights reserved. No part of this publication may be reproduced, stored or transmitted in any form or by any means without written permission of copyright owner. No responsibility is assumed by the Author and the Publisher for any injury or/and damage to persons or properties a s a matter of products liability, negligence, use, or operation of any methods, product ideas, or instructions published or suggested in this book.

Printed in Canada ChemTec Publishing 38 Earswick Drive Toronto-Scarborough Ontario M1E 1C6 Canada Canadian Cataloguing in Publication Data Mezaki, Reiji Rate equations of polymerization reactions Includes bibliographical references and index. ISBN 1-895198-16-X
1. Polymerization. I. Ma, Guang-Hui

11. Title
QD281.P6M49 1997 547’.28 C97-900732-1

CONTENTS
1 1.1 Acrylonitrile.................................................................................................... 1 1.2 Butadiene ...................................................................................................... 16 1.3 Ethylene ........................................................................................................ 20 1.4 Isoprene ........................................................................................................ 41 1 .5 Methyl methacrylate .................................................................................... 42 1.6 Propylene .................................................................................................... 11 0 1.7 Styrene ........................................................................................................ 103 1 .8 Vinyl acetate .............................................................................................. 173 1.9 Vinyl chloride ............................................................................................ 200 1.10 Vinylidene chloride ................................................................................. 209 2 Ionic polymerization ............................................................................... 211 2.1 Acrylonitrile................................................................................................ 211 2.2 Butadiene .................................................................................................... 213 ............................................................................................. 218 2.3 &-Caprolactam 226 2.4 Isobutylene.................................................................................................. 2.5 Isoprene ...................................................................................................... 227 2.6 a-Methylstyrene .......................................................................................... 234 2.7 Styrene ........................................................................................................ 235 3 . Ziegler-Natta polymerization .................................................................. 242 3.1 Butadiene .................................................................................................... 242 3.2 Ethylene ...................................................................................................... 255 3.3 Isoprene ...................................................................................................... 265 3.4 Propylene .................................................................................................... 266 4 . Polycondensation reactions ..................................................................... 275 4.1 Transesterification of dimethyl terephthalate with ethylene glycol.......275 4.2 Esterification of terephthalic acid with ethylene glycol ........................ 282 4.3 Polycondensation of bis(2-hydroxyethy1)terephthalate ............................. 291 305 4.4 Polycondensation of molten-state poly(ethy1ene terephthalate).............. 4.5 Polycondensation of solid state poly(ethy1ene terephthalate) ................319 4.6 Polycondensation of solid-state polybutylene terephthalate ...................321 4.7 Transesterification of diphenyl carbonate with bisphenol...................... 323

1. Free radical polymerization ........................................................................

. .

.

Preface
This book is a compilation of rate expressions for industrially important polymerization reactions, which have appeared in major technical journals in both chemistry and chemical engineering. In this text we have selected only homopolymer systems, with the exception of polycondensation systems, although copolymers are more widely used. It is our intention to compile and publish the rate expressions for copolymerization reactions in a subsequent volume. In the polymer industry rate expressions are vital for the analysis, optimal design, and optimal operation of polymerization reactors. In reacting systems other than polymerization reaction comprehensive summaries of kinetic data have been published on may occasions. For polymerization reactions, however, no extensive compilation of rate expressions has been attempted, even though many useful textbooks have been published for the study of polymerization kinetics. It is true that computer aided searches of pertinent databases assist chemists and chemical engineers in finding rate expressions needed for their studies. Yet computer surveys of data bases are sometimes time consuming and often costly. We hope that this book will be of service for those who wish to conduct an efficient survey of the rate expressions of interest to them. The contents of the book can be used in a variety of ways. For example, chemists and chemical engineers can estimate polymerization rates for desired polymerization conditions by using the rate expressions assembled here. A comparison of the rates thus estimated against rates determined for a newly developed initiator or catalyst furnishes a useful evaluation of the initiator or catalyst. For the development of polymerization rate models we recommend that investigators modifi models on

I

the basis of their own data. In the area of polymerization reactions it is generally recognized that rate expressions are totally different if the polymerization occurs in the region where diffusion process of reactants and/or products are ratedetermining. On some occasions, needless to say, rate expressions reported in the past can be used without modifying the form of the rate equations. However the rate parameters contained in the equations must be reevaluated by using the experimental data gathered by the investigators themselves. The use of uniform units might be convenient for users of this book. No attempts were made to have such uniformity in order to avoid errors that we might introduce during the process of converting the units. It should be noted that many important journals issued in Russia, in Eastern Europe and in the People’s Republic of China were excluded in our search for rate expressions. This is mainly because some difficulties were experienced in obtaining both the original and the English versions of these journals. However the authors sincerely hope that the publication of this book will encourage other interested persons to collect rate expressions published in the geographical regions mentioned above. Perhaps in this way some collaborative efforts will result in a substantially more complete collection of rate expressions for polymerization reactions. June, 1997 Reiji Mezaki Guang-Hui Ma Tokyo, Japan

I1

Acrylonitrile

1

1. Free radical polymerization
1.1 Acrylonitrile
Emulsion polymerization Emulsifier: sodium lauryl sulfate Initiator: potassium persulfate Temperature: 50°C Maximum conversion: higher than 90%
For ~ 5 % ~ rp=KAkd”2[I] 1/2M01/3N”6[Mpi] For x>x,, 113 1/6 N K A ~ , J ” ~ [ I ] ” ~ ( M ~ X ) Mo( I-X) rp= I +BMox) A(Mo~)2/3N’/3+m( rtr=cinrp r,=2tk(j[l]
‘ P

P=

( 1/2)r,+rtr

b=4.46 X 10” [ I/hr] m=5 x io7 [cm*/11 K=5.8 X 1O6 [cm/g-mo11’2*hr1’2] C,,=2.6 x 1 o - ~ A: (36~)”~(M,/p,)~”,[ ~ m ~ / g - m o l ~ / ~ ] B: M , / I o ~ ~ , ,[l/g-moI.cm3] r,: rate of initiation, [g-mol/l*hr] rtr: rate of chain transfer, [g-mol/l. hr] rp: rate of propagation, [g-mol/l*hr] C,: chain transfer coefficient to monomer, [-I kd: decomposition rate constant of initiator, [ Uhr] f: efficiency of initiation, [-I m: distribution coefficient, [cm2/1] kps: propagation rate constant at polymer surface, [cm2/g-mol * hr] kt,: termination rate constant at polymer surface, [cm2/g-mol hr]

W. A.35 for y=300/700 y: monomer to water ratio.. 205 (1961).12 for y=150/850 Xcr=0..1 ' -azobiscyclohexane Temperature: Conversion: 25°C less than 0. H. [I/mol' sec] kt: termination rate constant.. I.. Proc. London.: value of x. A260. CI-. [ -] [I]: concentration of initiator. [g-mol/l] [MpJ: =m[Mwi] [Mwi]: =saturated value of [Mw] with pp: density of polymer.0 X 106 [I/mol. Omi.22 for y=200/800 Xc.=0. [g/mol] N: number of polymer particles in reaction mixture. [1/I] x: monomer conversion Xc. sec] k.=5.2 Free radical polymerization Is Mw: molecular weight of acrylonitrile.=0. 5.. [g/l] Xc. sec] carbonitrile kp: propagation rate constant. Roy.(X-: OH-. Photo-induced solution polymerization Solvent: water Initiator: FeJ+X. Eng. S.1 % kp=52 [I/mol. [g-mol/l] Mo: initial concentration of monomer. [g/cm3] p: degree of polymerization. [I/mol' sec] Bengough. 44 (1972). and Kubota. Japan.. NJ-) Temperature: 25°C . Soc. [ -] monomer [g-mol/l] K.ps k f = 112 /k 112 Tazawa. Photo-induced bulk polymerization Sensitizer: 1. J: Chem. at which monomer droplets disappear.

[l/molo sec] separation rate constant of the primary product.p + -M q-X -X-M p-M q-X M: monomer.1/2 [(I/molo sec )1/2] Fe3+0H" Fe3+ClFe3~3- 4 X 103 6 X 103 5 X 102 0.156 ke: ~: ki: ks: ko: the fraction of the light absorbed by Fe3+X-.p + X -X-M p-X (b) by recombination of active endings X-M. Separation of the primary product Fe2+X -Fe2+ + X Secondary dark back reaction Fe2+ + X -Fe3+ + XFree radical initiation of polymerization X + M -X -MPropagation of polymerization X-(Mk+ M -:"" X-(M)n+lTermination of polymerization (a) by free radicals X-M. ks ko ki kp k'. [l/sec] rate constant of primary dark back reaction.absorption Fe3+X. kt Ion pair ko/kj kp!k. [l/sec] rate constant of secondary dark back reaction.~ Fe2+X Primary dark back reaction Fe2+X-Fe3+XInitiation of polymerization Fe2+X + M -Fe2+ by the primary + X -Mproduct Fe2+X Light ke ~ k'. [l/molo sec] . [l/sec] rate constant of initiation reaction by the primary product Fe2+X.

243 (1951). M.4 Free radical polymerization kj: free radical initiation rate constant. N.~p p + Fe(ll) Subcritical Very p+P~P slow.. sec] Evans. [I/mol.* + S. + Sj* ~ Sj+l* Rj kJ[mJ[S*] kt[s*f k2[S*][Fe(III)] rapid a[ml]f(RJ phase termination S. 15. 25°C ("-=2537 A).. 25t ("-=3130A). [I/mol. + OH Feaq3+ -Fe2+ + OH ("-=2537 A). 30.[P][P*] k"t[p*f very mobile Weak adsorption m) aa ~ ml . Reprinted by permission of John Wiley & Sons. 25.. 25t ("-=2537 A). J. Copyright <9 1951 John Wiley & Sons.* ~ J J p Sj* + Fe(l11) ~ particle coalescence p + p + . M. [I/mol. sec] kt: termination rate constant by recombination of active endings. [I/mol. stable particle p+p~p p + p* ~ coalescence p* p ads p* + p* ~ k"t[pf k". Inc. Photo-induced solution polymerization Solvent: water Initiator: Fenton's reagent (Fe2+ and H2O2) Photochemical reactions: Feaq2+ . Inc. sec] k't: termination rate constant by free radicals.Feaq3+ + H Feaq3+laq-I Feaq2+ + H. Santappa. Polym. and 50t Rate Reaction Initiation OH + ml ~SI * Aqueous Aqueous phase propagation m.. G... 7. sec] kp: propagation rate constant. Sci. and Uri.

3 x iot3 6. []/mol sec] k.=kl [ml][S*]+k'.: rate of initiation.[P*][ml ads] k.3 3. [mol/l] - . [I/mol.[S*][P*] slow Rp=R.sec] k4Ii:stable particle coalescence rate constant.Acrylonitrile Particle propagation P* Particle activation Particle termination sj* 5 + ml P ads --j 4 P* k'. [Vmol-sec] k. sec] k2: termination rate constant with ferric ion in aqueous phase.[S*][P] slow s. [mol/l*sec] R. [mol/l] [p]: concentration of dead polymer in aqueous phase.: propagation rate in particle. [mol/l] [Sj*]: concentration of polytner radical with j units in aqueous phase.) Termination by Fe(II1) (k2) E [kcal/mol] 4.: mutual termination rate constant in aqueous phase.+R.: particle activation rate constant. [mol/l*sec] kl: propagation rate constant in aqueous phase.7 X lo5 R.4 2. [I/mol*sec] kip: particle propagation rate constant.. [Vmol sec] [inI]: monomer concentration in aqueous phase. [I/mol. [mol/l-sec] Raq: propagation rate in aqueous phase. [mol/l] [ml ads]: monomer concentration adsorbed on particle.1 5. [mol/l] [S*]: total concentration of polymer radicals.0 X lo7 3.[ml ads][ P*] Arrhenius parameters A [I/mol*sec] Propagation (kl) Mutual termination (k.: particle termination rate constant.* + P* + P* + P k'. [I/mol*sec] k.

Copyright 0 1959 John Wiley & Sons. Inc. 25°C (h=2537i%). P. 1Photochemical reactions: Fe. S.=k'. Seaman.[P*][m.. G. 25°C (h=2537a). Reprinted Sci. and Eaton.+ - .. L. by permission of John Wiley & Sons..+ P a[mi]f(Ri) Slow stable particle coalescence P+P-+P k"t[P]2 P* P + P* k"t[Pl[P*l k"t[P*]2 P P* + P* Weak adsorption very mobile ml ads ml aq Particle propagation R.+ - . Photo-induced solution polymerization Solvent: water Initiator: Fe3+.6 Free radical polymerization [PI: concentration of dead particle. ads] P* P* + m l ads .+ - . F. 25°C (h=3130a). J. H.+ - Reaction + --j - + .+ Fe2+ + OH .+ - (h=2537a).+ - . Inc. R. James. D. [mol/l] [P*]: concentration of particle with radical.' + OH I. 25°C Initiation Rate Fe3'0K kv Fe2' + OH Ri= @ lIabs OH + ml -+SI* Aqueous phase propagation ml + Sj* Sjtl* Raq=kp[ml 1[S*l Aqueous phase termination 2s*+ p kt[S*12 S* + Fe(II1) p + Fe(I1) ktdS*l[Fe(III)I Transformation of subcritical particle p to stable particles P P+P+P rapid p + P ..? Feaq + H 3t Fe. 39.' Fe. Fe2+. S.. 209 (1959)... [mol/l] Dainton. Fe3+0K. I + H Fea. Polym.

F.[ml][S*]+k'.: particle propagation rate constant. [mol/l] [ml ads]: monomer concentration adsorbed on particle.[ml ads][P*] k.: stable particle coalescence rate constant. Inc. [mol/l] (S*]: total concentration of polymer radicals.]: monomer concentration in aqueous phase. Reprinted by permission of John Wiley & Sons.[S*I[Pl k'. [I/mol*sec] k'.=l.: propagation rate constant in aqueous phase.: particle activation rate constant. [mol/l*sec] R. Polym. Copyright 0 1959 John Wiley & Sons.. [mol/l] Dainton.[S*][P*] slow --+ Rp=Ra.45 X 1 04. and James. D. [I/mol*sec] Kl: particle termination rate constant.+R. []/mol* sec] [m. J.Acrvlonitrile Particle activation Particle termination 7 s* + s* + P P* ---f P* P k. [mol/l] [Sj*]: concentration of polymer radical with j units in aqueous phase. [I/mol*sec] k. [I/mol*sec] k.: mutual termination rate constant in aqueous phase. G. Sci. Inc.=k. [I/mol*sec] Ri: rate of initiation.: propagation rate in particle. [mol/l] [PI: concentration of dead particle. [I/mol-sec] k t F1.. [Vmol *set] kl=2 X 1 09. [mol/l] [p]: concentration of dead polymer in aqueous phase. 299 (1959). [I/mol*sec] k". [mol/l] [P*]: concentration of particle with radical. L. [I/mol*sec] kif: termination rate constant with ferric ion in aqueous phase. S. Photo-induced solution polymerization Solvent: water Initiator: Fe3'0K Temperature: 15-50°C . [mol/l*sec] Raq: propagation rate in aqueous phase. 39. [mol/l-sec] k.3 X 104.

7 x io9 4.=$IIabs Fe3'0HFe2+ + OH OH + ml + S I * Aqueous phase propagation ml + S.3 x io4 2. [I/mol * sec] ktr [I/mol*sec] kP [I/mol.* Raq=kp[ml 1[S*l Aqueous phase termination 2s*+ p kl[S*I2 S* + Fe(II1) -+ p + Fe(I1) ktdS*I[Fe(I1I)l Transformation of subcritical particle p to stable particles P P+P+P rapid p + P + P a[ln I lf(Ri) Slow stable particle coalescence P + P + P k".[S*I[P*l - ---f Rate constants Temperature ["CI 15 25 30 k.2 x io4 6.25 x io4 .sec] 2.5 2.4 x io9 x io4 6.* + Sj+. --+ p* k"t[PI[P*l krlt[P *I2 P* + P * + P Weak adsorption very mobile ml aq ml ads Particle propagation P* + ml ads P* Rs=ktp[ *][m ads] P Particle activation S* + P + P * kSS*I [PI Particle termination S* + P * + P k'.8 Reaction Initiation Free radical polymerization Rate R.4 x I o4 4.[P]* p + p*.8 x io9 3.8 x io4 3.

39. [I/mol*sec] k. Polym.: particle activation rate constant. R.Acrylonitrile Arrhenius parameters A [I/mol*sec] 9 [kcal/mol] 4.. [mol/l] [S*]: total concentration of polymer radicals. Reprinted by permission of John Wiley & Sons. F.. [mol/l.3 x 1 0 ' ~ 6. [mol/l] [p]: concentration of dead polymer in aqueous phase. 313 (1959). [mol/l*see] k. [mol/l] [P*]: concentration of particle with radical. [mol/l*sec] R. [I/mol*sec] k. Copyright 0 1959 John Wiley & Sons. and Eaton. Sci.4 2.f: termination rate constant with ferric ion in aqueous phase.1 5. [mol/l] [m. [I/mol*sec] k1lt: stable particle coalescence rate constant. Inc. J. [ I/mol*sec] kt: particle termination rate constant. [I/mol* sec] k'.) Mutual termination (k.) Termination by Fe3'OK (ktf) 3.: propagation rate in particle. [mol/l] [PI: concentration of dead particle. . ads]: monomer Concentration adsorbed on particle.: propagation rate constant in aqueous phase. S.7 x io5 Ri: rate of initiation.3 E Propagation (k. see] kt: mutual termination rate constant in aqueous phase.sec] Raq: propagation rate in aqueous phase.0 X 10' 3. [mol/l] Dainton. Inc. [I/mol.]: monomer concentration in aqueous phase.: particle propagation rate constant. [I/mol*sec] [m. [mol/l] [Sj*]: concentration of polymer radical with j units in aqueous phase. S.

Reprinted by permission of John Wiley & Sons. Harumiya. [mol/l] [Jab]: absorbed light intensity.4-45.(~/k. Inc. Solution polymerization Solvent: water Initiator: ammonium persulfate (APS) Temperature: 35-50°C Maximum conversion: 80% R.. 10. sec] Miyama.b”~[Mlfor 365 I-L m RP=4.10 Free radical polymerization Photo-induced solution polymerization Solvent: dimethyl sulfoxide Initiator: azobis(isobutyronitri1e) (AINB) or hydrogen peroxide (H202) AINB Temperature: 25.A-1. N.=k[APS]”2[M]2=k2[M]2=~kp(~~/kt)”2[APS]1~2[M]2 ~=M{k. [mol/l*sec] [MI: monomer concentration.15 k~al/RT})1. Sci.38 k~al/RT})I.~”~[M] 3 13 p m for R. A.= 140(exp{-4.. Inc.)”2}=mV.. H.’~2/[M]2 m=(P/Vp”2)[M]2 I / .Jki[M]2P2+term related to chain transfer .9”C RP=97{exp(-4. and Takeda. Polyrn. [E/I.45 kCaI/RT))Iab”2[M] H202 Temperature: 25-45°C R. 943 (1972). Copyright 0 1972 John Wiley & Sons. J.=(ktd+ktJ2)k2V..: propagation rate.20(exp{-2..

345 0.: termination rate constant.-E.04 1.]: total concentration of polymer radical.54 2.3. [I/mol*sec] k.1 1 3.708 5.: propagation rate. [Vmol * sec] ktd: termination rate constant by disproportionation.20 5.310 3.510 2.510 2./2+EB=13.66 1.62 4.77 1. [mol/l] [R.768 1.48 1.3 [kcal/mol] Ed=3 I .85 3./2+EB=-2.70 I 0.60 4000 4780 5300 6020 6260 6560 8080 2840 3120 3700 4350 4760 5460 5560 2060 2370 2780 3030 3950 5280 38 47 57 70 77 97 107 20 23 27 36 41 49 54 12 13 15 17 20 29 Activation energy for polymerization: E=Ed/2+E.670 I .708 1.87 2.326 0.4 [kcal/mol] R.768 1.91 5.768 1. [mol/l-sec] f: efficiency of initiation.177 3.45 2..442 0. [Vmol-sec] [APS]: concentration of initiator.876 0. [I/mol*sec] kt.310 3.: termination rate constant by combination.42 2.21 4.79 2. Ep-E. [mol/l] . ["c:1 35 35 35 35 35 35 35 40 40 40 40 40 40 40 50 50 50 50 50 50 Initial concentration k2 X 1O4 p II Induction time of APS X IO2 [mol/l] [I/mol*sec] (conversion 45%) [min] 5.884 0.Acrylonitrile - 11 Temp.45 1.326 0.670 1.69 3.88 1.55 2. [-I b: decomposition rate constant of initiator.884 0.

. 67. Kogyo Kuguku Zushi.OH H / c\ + V(OH)32t Fast . I<" complexll k2 Slow ' COOH CH2-CHOH + VOz + k3 H30' + C02 +Jc . M.. Solution polymerization Initiator: Vst-lactic acid Solvent: aqueous sulfuric acid Temperature: 20-35°C Primary radical production cq / ' .. ' C/OH \ + VO-OH" H Fast + KIII complexlll --. [mol/l] P . [kcal/mol] Ed: activation energy for decomposition of initiator. and Watanabe. S. .. Yaguchi.12 Free radical polymerization [MI: concentration of monomer. [kcal/inol] E. [kcal/mol] Kiuchi.: efficient volume in polymerization locus.OH C' \ I{ + vo2+ e Fast I complex1 H COOH Slow ki CH2-CHOH + VO2 + CO2 (R.: activation energy for termination..: activation energy for propagation. [I] m: concentration of monomer i n polymerization locus.1 .) cF .: number-average degree of polymerization E: activation energy for polymerization. 1479 ( 1964). Slow COOH CH2-CHOH + V02 + H' + C02 . [mol/l] V. [kcal/mol] E. H.

+ VO-OH" + polymer + v4+ R-M.l.4053 0..96 .V(OH)3HS04" Kz. + M + R-M.. + V02' + product + V4' R . R-M.OH c\ + V(OH)3HS04' COOH Fast complexlv Slow kr where V02' + H30' 2 V(OH)y V(OH)32+ + HSOk VO.05 11. + VO~' polymer + v4+ Linear termination R-M. + M + R-M.281 From l/Rp vs..!. ["CI 1/[Lac] 20 30 - ko/ki From l/Rp vs. W'I 0. R-M. R-M. + M R-M. l/[Lac] - From l/Rp vs. + H' I<3..+ V(OH)32++ product + V4+ Re + VO*OH2' + product + V4+ + k3 1 k2 1 ko I k02 k03 Rp=(kdkt)k'[ Lac] [MI2/([M]+ko/ki[ V"] ) Rate parameters for V5'-lactic acid-acrylonitrile system in aqueous sulfuric acid kdkt Temperature From l/Rp vs.17 0.. .277 10. WS'l 13.Acrylonitrile 13 cq H / . --j VO*OH2' Initiation Propagation R. + V(OH)32' + polymer + V4+ Reaction of primary radical with Vs+ R.

: propagation rate constant.[I])’’~/k~[M]+k. P: dead polymer.[S]/k~[M] h=2.59 for AIBN f=0. Solution polymerization Solvent: dimethyl formamide Temperature: 50°C Radical formation Initiation Propagation Transfer Re initiation Termination I R* R* + M P* + M P* + s s* + M P* + P* + kd + + P* P* P ki k W + s* + P* P + + k. A-1. 643 (1969). M. [I/mol*sec] h: rate constant for reaction of primary radical with V5+. Inc. [mol/l] Saccubai.: termination rate constant.144 for APS kw=3 X 1O3 [I/mol*sec] . Reprinted by permission of John Wiley & Sons. Sci. Copyright 0 1969 John Wiley & Sons. J. M] v=kW(2fkd/ka)’”[ [I] ‘I2 1/ .12X [l/sec] for APS ki=2fkd f=0. S*: active solvent.. Inc. [mol/l*sec] [Lac]: concentration of lactic acid.. 7. [I/mol*sec] k. . S: non-active solvent. [I/mol*sec] ki: initiation rate constant.: propagation rate. and Santappa. R*: radical.14 Free radical polymerization k. kr ka I: initiator. [mol/l] [MI: concentration of monomer. [mol/l] [V”]: concentration of vanadate (V”). P*: growing polymer radical..08 X [ I/sec] for AIBN b=2.=(2fl~k. S. Polym. [Vmol-sec?] R.28 kr=k.

[mol/l ssec] - 15 P . 143 (1989). [I/mol-sec] ku: transfer rate constant.sec] v: rate of polymerization.: termination rate constant.sec] [i]: concentration of species i. K..=0.: propagation rate constant.= 1.93 [Vmol * sec] k..: number-average degree of polymerization. [-3 .Acrylonitrile k. 40. Rafler. [I/mol*sec] k. [mol/l] f: efficiency of initiation. G.. [-3 kd: decomposition rate constant of initiator. and Tauer. [I/mol*sec] k.. Fritzsche. Acta Polymerica. . P. [I/mol*sec] k. [ I/sec] ki: initiation rate constant. [I/mol.: reinitiation rate constant.20 X 1 O9 [I/mol.

sec] k.[M]N/2 k. Polym. and Landfield. [mol/l] N: number of particles per ml of water. 60-80°C for acetone Phase: gas Photo decomposition of di-tert-butyl peroxide (formation of primary radical) 2(CH3)3CO kl (CH3)3COOC(CH3)3 + hv Deactivation of tert-butoxy radical (CH3)3CO. sec] Morton... Sci.= 1. M. Photo-induced bulk polymerization Initiator: di-tert-butyl peroxide and acetone Temperature: 75-95°C for di-tert-butyl peroxide. [I/ml] -dm/dt: rate of polymerization.. J. 8. Reprinted by permission of John Wiley & Sons. k2 Propagation of tert-butoxy radical (CH3)3CO. [molecules/ml of water. P..: propagation rate constant. + M+ (CH3)3COM* kl0 + + 180 parts 100 5 1 variable variable .2 Butadiene Free radical polymerization Emulsion polymerization Initiator: hydroperoxide-polyamine Temperature: 0-30°C Recipe: Water Butadiene Soap Potassium chloride Diisopropylbenzene monohydroperoxide Triethylenetetramine or tetraethylenepentamine -dm/dt=k. 215 (1952). Inc. P. H. Copyright 0 1952 John Wiley & Sons.2 X 108exp(-9300 cal/RT) [I/mol-sec] [MI: monomer concentration in particle. (CH3)2CO + CH3. Salatiello. [Vmol. Inc.16 1.

CH3CO.4 [kcal/mol] [MI: concentration of butadiene. [kcal/mol] E2: activation energy for kZ. + CH3. Chem. 0 1953 American Chemical Society... Am. [kcal/mol] Elo: activation energy for klo.8k1. 75. J. [kcal/mol] E8: activation energy for k8.0 Di-tert-butyl peroxide Acetone E2=l 1. El2=5. .COM]/dt d [CO]/d t - Rc RD - k12[Ml k8 Overall rate equation: -dP/dt = kg[M] Initiator Activation energy (E9) for kg [kcal/mol] 5. El0=5. Eg: activation energy for overall rate constant k9. 31 11 (1953). and Graven. EsZ13. Soc. [kcal/mol] EI2: activation energy for kI2. [mol/l]. D. M.+ - RB k12 M: monomer.0 5 . d[CH. . H. (CH3)2CO*: photo-activated state. Deactivation of acetyl radical CO + CH3.Butadiene M: monomer R A 17 k2 klO[MI d[(CH3)3COM]/dt Photo decomposition of acetone (CH3)2CO + hv + (CH3)2CO* (CH3)2CO* + CH3CO. Propagation of acetyl radical CHRCO. 0 k 1.5f2. W.4. + M + CH3COM.2k2.0. [kcal/mol] Volman.

. J.: activation energy for k.2 k [l'~21m01'/2*~e~] 0. [kcal/mol] E. [kcal/mol] - Volman.: activation energy for k.161.0289 0.. [Vmol * sec] E: activation energy for k. 19.0 151. [kcal/mol] E. sec] k. 668 (1951). + C H ~ M I ~ I ' (CH3)2Mti+to + + + ki M: monomer. [kcal/mol] E.0 161.18 Free radical polymerization Thermally-induced bulk polymerization Initiator: di-tert-butyl peroxide Temperature: 140. + C2H6 CH3..)'/2[ M][C]'/2 k=kp(ki/k.=39. [mmHg]. Chem.0548 0.: termination rate constant by combination. Phys. [ l/sec] k. [I/mol. + M Ck3MII+. CH3Mn. D.: activation energy for kt. [mol/l] k: overall rate constant. [mol/l] [C]: pressure of peroxide. . [mmHg].: propagation rate constant.. CH3M..: decomposition rate constant of initiator.. CHI. Et=O [kcal/mol] [MI: pressure of butadiene.1 12 E=Ei/2+Ep-Et/2=22. + CH3. Ep=2. [Vmol sec] k. d[M]/dt=-k (ki/k.1.2"C Phase: gas (CH3)3COOC(CH3)3 4 2(CH3)3CO3 * 2(CH3)3CO* 2(CH3)2CO + 2CH3. + M + CH3M.6.1 [kcal/mol] E.. H.)" Temperature ["C] 140.

2 k [l”2/mo11’2sec] 0. + M -+ CH3Mx+l* CH3Mx* + CH3My.6 X 1 O‘exp ( -3 8. + M CH3M. E. [I/mol.) Temperature [“C] 129.)”2MI [C] ‘I2 [ k=k. 79.( 2k.85 1. C. (CH3)2Mx+y CH3Mx. k. [I/mol.Butadiene Thermally-induced bulk polymerization (1. [kcal/mol] E. + CH3Mx* + (CH3)2Mx+x .0 166. CH3Mx./k.=38.. . [kcal/mol] E: activation energy for overall rate constant k.: activation energy for k.91 10. D..4 140. k./2 M: monomer. J. [I/mol-sec] Ei: activation energy for ki. Chem. E.5 151. 0 1957 American Chemical Society. SOC. Am. L.3-butadiene) Initiator: di-tert-butyl peroxide Temperature: 130-165°C Phase: gas (CH3)3COOC(CH3)3+ 2(CH3)COCH3 + 2CH3 CH3.4. k.4 kcal/RT) [ 1/sec] E.9.: activation energy for k.: termination rate constant..=4. [ 1/sec] k. and Volman. [mol/l] ki: initiation rate constant.=O.. sec] k.5 k. H.sec] k: overall rate constant.+ - 19 kl + k. -d[M]/dt=kp(2k.1 [kcal/mol] [MI: pressure (concentration) of butadiene. [mol/l] [C]: pressure (concentration) of peroxide. E=24.: propagation rate constant./k.= 1.93 3. [kcal/mol] E. 2996 (1957). [kcal/mol] Landers.

Faraday SOC.3 0.7-1.458~4.8-1.1-3.4-2. di-tert-butyl peroxide(DTBO). [mol/l] pressure of monomer..8 675-1375 100-200 0. K.hr] Experimental ranges P [am] T TCl C [movI] \ .n3 Exmnents and activation e e e : P or f C E [dmol] 4.G.3 1200-2000 200-264 1200-2000 180-210 380-1050 120-140 400-1200 1100-1800 51 - 26700-34500 0. [-3 Laird. 22.3 2.6-0.5 7800-18400 1.4-2.. [atm] temperature.3 1.3 Ethylene Bulk polymerization Initiator: y-rays.85-34. and Seed.2 2100-8800 0. azodi-isobutyronitrile (ADIB).4-1.0 0.8-2.6-3..20 Free radical polymerization 1.O-1.458~4.2 1.9-1.9-2.6 Curies 0.6 1.2 2. ["C] or [OK] activation energy. and oxygen Temperature: 20-260°C Pressure: 400-2000 atrn Initiator Overall polymerization rate [movI. .1 C: P: T: E: catalyst concentration. Discussions. acetoxime.6-1. A.2-61.6-5.8 10. L.5 1.1 230 473-1 185 20-125 0.0-1.5 28800-35000 1640041900 0.9 2.5 0.2 1.2 1. [cal/mol] f: ethylene fugacity.4-6.04-1.9 1.7 Curies 0. . Morrell.1-3. R.3-0. 126 (1 956).

4 38.1 Activation energies Rate constant k ki kP Activation energy [kcal/mol] 27.Ethvlene Bulk Polymerization Initiator: di-tert-butyl peroxide Temperature: 130-165°C 2CH3COCH3 + 2CH3’ (CH3)3COO(CH3) CH3.+ - + -d[ M]/dt=kp(2ki/kJ[M][C] k=k.86 6. CH3M.6 X 106exp(-38.)”2 Rate constants Temperature [“C 1 ‘I2 kX IO4 [1”2/mo1”2* sec] 1.2 0 k.2 146.19 18.4 cal/RT) [MI: concentration of monomer.(2ki/k. CHJM~. [mol/l] [C]: concentration of initiator. [mol/l] ki: initiation rate constant. k. + M (CH3)2Mx+y CH3Mx* + CH3My.0 160. [I/mol-sec] . (CH3)2Mx+x CH3Mx* + CH3Mx* .=1.4 8.+ - 21 -+ - .2 131. + M 4 CH3M.

Inc. L.9 ASlr-ASp=3 8. Am. M. Bulk polymerization Initiator: in first stage AIBN.4 10..7 P. Kise.. [I/mol * sec] ktr: transfer rate constant. S. Inc. SOC. 31 15 (1967). [Vmol-sec] kb: short-chain branching rate constant. .]: total concentration of polymer radicals. Hagiwara..=kdktr R. D.: number-average degree of polymerization. [mol/l] - Machi. [-3 fM: fugacity of ethylene. and Kagiya..: overall propagation rate constant.: propagation rate constant. A-1. 0 1957 American Chemical Society. Copyright 0 1967 John Wiley & Sons. S. 79.set] Rlr: rate of transfer reaction. Rtr=klr[R * ]fM2. C. []/mol sec] P. 5.[R* ]fM2. T. [I/mol*sec] kt: termination rate constant.. J. H. Chem. [mol/] sec] k. [-I [R.=l 9. Reprinted by permission of John Wiley & Sons. in second stage no initiator Temperature: 20-80°C Pressure: 160-400 kg/cm2 In second stage: R.2 ASb-AS. 2996 (1957). [mol/l-sec] Rb: rate of short-chain branching. Rb=kb[R * ]fM2 Activation energy [kcal/mol] Propagation (kp) Transfer (ktr) Short-chain branching (kb) Activation entropy difference [cal/mol sec] - 5. [I/mol*sec] Landers. Polym.7 23. Sci.=k.: overall propagation rate. and Volman.. [mol/l .22 Free radical polymerization k. J.

(x) -+ Pl(x) + Rl(0) P. J.(y) P. <D=Qoexp( -E. Rl(0): primary radical. and Ehrlich. Bulk polymerization Initiator: di-tert-butyl peroxide (DTBP) Temperature: 130..+Jx+y) + a P Y E .: activation energy. [cal/mol] Chen.Ethylene Bulk polymerization Initiator: di-tert-butyl peroxide Temperature: 100-300°C Initiation Propagat ion Termination by combination Termination by thermal degradation ( (3-scission) Chain transfer to polymer 23 I 4 2R1(0) R.. [I/sec] for a .(x): polymer of chain length x with i branches. ~ E. AIChE Journal.(x) + PJ(y) + yg I: initiator.(x) + Rj+l(y) R. Howell. Copyright 0 1976 AIChE.165°C Pressure: up to 3 kbar ri=klCurBP rp=kpCRadicalCElliyleiie rt=ktCRadical -dCm'Bddt=kd(P . All rights reserved. P. R.T) ' CDTBP 2 . G.(x): radical of chain length x with i branches..95 X lo7 3 8400 709 1 2.+ - R. Vermeychuk.0 X lo5 9000 E* 1.sec] for P. 463 (1976). J. A.(x) + M R./RT) a a 0 B Y 1.(x) + R.72 X IO" 20000 Qo: frequency factor.60 X lo9 2400 E E. Reproduced with permission of the American Institute of Chemical Engineers. 9. C.y.(x+l) R. H.c. [I/mol. P.6 X 1 0I6 2.. 22. M: monomer.

[Vmol-sec] CDTBp: concentration of initiator. [l/sec] sec] ko(P. sec] k.: volume change for propagation. M. [mol/l*sec] termination rate. AVp-AVt/2=-22. H. [1'12/mo1'/2* ro(P. ~~O(P-IOOO))/T}CE~I.k( 112ki 112 IRCEtliyleneCDTBP I12 kd(P. [kJ/mol] Eo: overall activation energy. [cm3/mol] AV.24 Free radical polymerization dCEtliylene/dt=rO=kpk('12ki rp=ro (approximation) ko=k. [mOl/l*SeC] k. ["K] E. [mol/l*sec] b: decomposition rate constant of DTBP.. 184.. [mol/l*sec] propagation rate. [mol/l] P: pressure.85X 1O"exp{(. [cm3/mol] AVO: overall volume change./ktlR=l 1. Chem.s ~ c " ~ ] Eo=EP-Et/2+Ei/2. 193 (1983).~~~~~CDTBP I12 . [I/mol.6+6 r.0.P)/T}. Ep-Et/2=31t-8 AVo=AVp-AVt/2+ i/2 AV AVo=-17.: activation energy for propagation. [bar] T: temperature.5.41 X 10'5exp{(-18226-0.: termination rate constant. [mol/l] CRadical: concentration of total polymer radicals. Eo=IO7.5 t5.121 .120(P-1000))/T}. [I/mol sec] ko: overall polymerization rate constant.: propagation rate constant.272(P-I000))/T}.[1'/2/mo11". Makromol. [mol/l] CEtllylelle: concentration of monomer..02 X 103exp((-3724+0.85x 10"eXp{(-12898+0. [kJ/mol] E.: rt: ro: initiation rate. . [ l/sec] k. [mol/l*sec] overall polymerization rate.: activation energy for termination. and Lendle.2*7.T)=1. [kJ/mol] AVt: volume change for termination.12898+0.T)=5.: r.T)=5. [cm3/mol] Buback. [l/sec] ki: initiation rate constant.

with j units.5 27. 8 io4 ~ 9. P.0 X 1OI2 4 .5 .0 3 . A: monomer. 7 io3 ~ 4.0 3. E [kJ/mol] 121.7x 10’ - 37.: dead polymer with j units.4 7.6 x io3 19. Kinetic constants Rate constant k0 R : growing polymer radical . Initiation Chain propagation R +A j R+ jl Chain termination by disproportionation R j Rk + Pj Pk Chain termination by combination R + Rk j Pj+k R + A ---* P + RI j j Chain transfer to monomer Rj + X + P + RI j Chain transfer to a modifier X Chain transfer to a polymer molecule P j R k P j Pk + Rj Intramolecular chain transfer R j R j + ---f + I: initiator.7x ios 9.Ethylene Bulk polymerization Initiator: tert-butyl perneodecanoate Temperature: 449-569°C Pressure: 1700 bar 25 I + 2R* Decomposition of initiator R* + A + R1. R*: primary radical.O - 1 .

. [Vmol-sec] kt2: chain termination rate constant by combination. [Vmol-sec] ktrl: chain transfer rate constant to monomer. [I/mol*sec] ktl: chain termination rate constant by disproportionation.. . 1935 (1985). R. G.. Sn: solvent.26 Free radical polymerization cD=a/b= 1200 b: decomposition rate constant of initiator.987+VaP/82. Eng. K=koexp(-(E.: radical of chain length i. Pi: polymer of chain length i./I . + Rj + R. P. Bulk polymerization Initiator: oxygen and peroxide Initiation Propagation Monomer transfer Solvent transfer Long chain branching termination combination disproportionation Short chain branching R. B. Chem.40. M: monomer. Sci. [l/mol*sec] klr2: chain transfer rate constant to a modifier. and Luft. [ I/sec] ks: initiation rate constant. b: constants to describe the dependency of rate constant on degree of polymerization Feucht. I'J Ri + Rj + Pi + Pj R-(CH?)S + R-CH-CdHg I. [Vsec] a.: initiator.. [I/mol*sec] ktr3(i): chain transfer rate constant to a polymer molecule with j units. [I/mol sec] ktr4: intramolecular chain transfer.06)/T) . Tilger.

: propagation rate constant. [I/mol*sec] K.: initiation rate constant. tert-butyl perneodecanoate.6 0 ko: frequency factor. and di-tert-butyl peroxide Temperature: 180-280°C Pressure: 1300. tert-butyl per 2-ethylhexanoate. P.1950 bar .sec] Kscn: short chain branching rate constant. Chem.: activation energy.3 X lo9 [l/sec] - 8942 9935 1.Ethylene Polymerization rate constants Frequency factor Activation energy [cal/mol] 7769 298 0 - 27 Activation volume [ml/mol] -2 1. Eng.. [cal/mol] V.5 X 10' [l/mol*sec] 1. [ l/sec] K.8 X lo7 [I/mol*sec] 2. tert-butyl perbenzoate. [ l/sec] Shirodkar. [-I E. G..: monomer transfer rate constant. 41. [OK] K.3 1 . tert-butyl perpivalate. [ml/mol] P: pressure. Bulk polymerization Initiator: di-(2-ethylhexyl)peroxidicarbonate. [I/mol.: activation volume. sec] [I/mol*sec] 7. [I/mol sec] Kfi. O. Sci. [I/mol*sec] Ktd: termination rate constant by disproportionation.3 x 1O* [I/moI. P.o 0 - Propagation Termination by combination Termination by disproportionation Chain transfer to monomer Chain transfer to polymer Short chain branching 5. [atm] T: temperature. and Tsien.c: termination rate constant by combination. [Vmol sec] Kfsn:solvent transfer rate constant.. 1031 (1986).8 X 1Ox [Vmol-sec] 1.

a vinylidene double bond (V2) or a trans-vinyl double bond (V. kt.) R .28 Free radical polymerization 2RI M + RI R 1 + M + RI Transfer to polymer R1 + SC P + R2 R'I + SC P + R2 Creation of a long branching point R2 + M -+ RI + LB Creation of a secondary short-branched radical by intramolecular transfer (back-biting) RI R'2 Creation of a primary short-branched radical and of a short branching point R'2 + M R'l + SB + Decomposition of initiator Linear propagation A RI + + + + + p2-scission of secondary radicals and creation of a vinyl double bond R2 RI + V I + P R'2 + Rl + VI + P p3-scission of a short-branched primary radical and creation of a vinylidene double bond R'1 RI + V2 + P Transfer to a tertiary site carried by initiator RI or Rtl + TA -+ R1 + P Transfer to solvent R1 or R'I + TS + R1 + P R1 or R'1 + TAT R1 + P Transfer to a transfer agent + + kP2 kP2 kD.E ~ ) V ~ I + + . kat + Termination by disproportionation of two radicals and creation of a terminal vinyl double bond (VI). kt. or Rfl + Ti R1 + P R ~ + R I + P + P + V I P + P + E ~ V + (I-EI)VT I RI + R2 R1 + R'2 -+ P + P + ~ 2 V l+ (I-E~)VT R I + RI + P + P + E ~ V + ( I .

J-L. A: initiator..40 5 . V.086 X 1O4 1. SC: secondary carbons. p108. Blavier L. J. LB: long branching points. World Congress I11 of Chem... M: monomer.0 .978 X 10' 1.OS3 64. V2: vinylidene double bonds..88 44. R: R=RI+R'l+R2+R'2 free radical of any size.2 179.44 49. ko [!/mol sec] or[ 1/sec] 1.74 -97. SB: short branching points.7 10. 1986.0 2. Pons.70 AV [ml/mol] 49.9 5.2 1 46.95 - k=kOexp -(E+PAV)/RT} { E: E.70 50. and Villermaux.539 X 10' 1. M. VI: vinyl double bonds.r: trans-vinyl double bonds.1 7.16 48. Greffe.719 X 10' 5.978 X 1 O6 E [kJ/mol] 3 1.Ethylene 29 P: dead macromolecules of any size. Tokyo.14.83 40.58 40. . a trans-vinyl double bond) by disproportionation.247 x io5 2.471 X lo5 7. Eng.453 x 10" 5.149X lo7 5. AV: activation parameters probability for the creation of a vinyl double bond (vs..

[1”2/mo1’’2.* 2r0* + rIlcl* * deactivated products or hydroperoxide P. [l/mol*sec] + * O2 TI. r.* + rll*: polymer radical with n units of monomer.30 Free radical polymerization Oxygen-initiated bulk polymerization Initiator: oxygen and di-tert-butyl peroxide Temperature: 60-250°C Pressure: up to 2220 kbar Initiation Propagation Retardation Termination + C2H4 r.299 X 109exp(-8000 cal/RT).23.=l 000 [cal/mol] AVt=O kd: initiation rate constant.sec] k.: dead polymer with n units of monomer.=3. ~ c ” ~ ] s f= 1 AE.395 X 10’0exp(-30000 cal/RT).: retardation rate constant by 02.’”=l. [Vmol-sec] k. h=3.. [Vmol-sec] k.+. + ---f kd kP kr kt ..* + C2H4 0 2 r. PI. [l/sec] kp: propagation rate constant.: 1termination rare constant by combination. [I/mol ssec] f1/2kdk.[I/mol..

ktd ~ k l p kIS M: monomer..sec] I . H. ktd 3.(x) + RI(0) ki kP kt.Ethylene [i]: concentration of species i.(x) +M +M + Rj(y) Pj(y) + S + + + + + + + Rd1) R.: activation energy for termination. 4 10' ~ [~/mo~*sec] 9443 9500 .7 x I o6 [I/g*sec] kts ktP 4 . Takahashi.. Mukmmol. T. [mol/l] AE..O X 1 O6 [Urn01 sec] 7. kP kt. Chem. S: solvent. Kinetic constants Kinetic constant Frequency factor Activation energy [cal/mol] 27941 5245 3950 11315 k. [I/mol] Tatsukami. [cal/mol] AVt: volume change for termination.(x) Ri(x) Ri(x) Ri(x) R.0X 10" [I' '/inoll. 181. Pi(x): dead polymer containing i branches and x total monomer units in its structure. Y.3 x 1o6 [ 1/set] I . 1107 (1980) Oxygen-initiated bulk polymerization Initiator: oxygen Temperature: 60-320°C Pressure: 1900-2500 kg/cm2 31 Oxygen initiation Propagation Combination termination Thermal degradation Transfer to polymer Transfer to solvent 0 2 R. Ri(x): radical containing i branches and x total monomer units in its structure. and Yoshioka.O x 1o6 []/mol sec] 3 .'.(x+l) Pi+j-l(X+y) Pi(x) + RI(O) Pi(x) + Rj+l(y) P..

.4 X lo3 k.. A. Res. and Ehrlich. 0 1988 American Chemical Society. J.: transfer rate constant to polymer.32 Free radical polymerization ki: oxygen initiation rate constant.1750 bar ... T. J. [I/mol*sec] Brandolin.. [I/g*sec] k. 714 (1982). Photo-induced bulk polymerization Initiator: diphenyl disulfide Temperature: 132°C Pressure: 500. Ind. 15. 784 (1988).. Farber. Photo-induced bulk polymerization Photo source: high-intensity mercury-xenon arc lamp Initiator: 1 -(tert-butylazo)-1-phenoxycyclohexane Temperature: 130°C Pressure: 1800 kg/cm2 kt=2. E.0X 10' k. N. [I/mol*sec] k.: termination rate constant.: propagation rate constant. G e m . N. Eng. [I/mol*sec] ktd: thermal degradation rate constant.: propagation rate constant. M.: transfer rate constant to solvent. 27.: combination termination rate constant. [I/sec] k. and Valles. [I/mol*sec] Takahashi. 0 1982 American Chemical Society. Capiati.. [ I '..=5. [I/mol*sec] k.' * sec] k.'/mol'. Macronrolecules.. P.

Chem.: termination rate constant.-C.: termination rate constant Av*: activation volume.4 k. G..-C. M. 184. 184.8 5. and Yokawa.3 8. [ml/mol sec] Luft. ..O 4.Ethylene Rate constant Pressure [bar1 500 750 1000 1250 1500 1750 33 kP [ml/mol.5 7 kP k.: propagation rate constant. Makromol. P.5 1.1750 bar Rate constant Rate constant Activation energy [kJ/mol] 37 9.8 4. 849 (1983). and Luft. Lim.9 kt [ml/mol.9 Av * [ml/mol] 25. [ml/mol] Lim... Chem. sec] 17. G. sec] 1.6 2.. Photo-induced bulk polymerization Initiator: diphenyl disulfide Temperature: 400-470°C Pressure: 500. [ml/mol* sec] k. 207 (1983).. Makromol.2 2. P.8 5.2 1. kp: propagation rate constant k.8 2.

-P. Rapid Commun. H. [I/mol*sec] k.: activation energy for propagation reaction. overall density=0... H. [kJ/mol] Brackemann. 1977 (1 986). (220"C. [I/mol*sec] Buback..-P.: termination rate constant. 187.34 Free radical polymerization Photo-induced polymerization Photo source: laser Temperature: 463°C kP=i.. and Vogele.. Makromol. M.: propagation rate constant. [I/mol-sec] E. . M. Chem. J. Photo-induced bulk polymerization Photo source: laser Temperature: 190-230°C Pressure: up to 3200 bar k.o9xio4 kt=l .: propagation rate constant.. Schweer... 7. Chem.54 g/cm3)=30000 EP=36k4 k. H.. 261 (1986). €1.99 X 10' Quantum yield for the production of primary radical species: QS=1 k. Hippler. Makromol. and Vogele.. Buback.

Polyrn. [mol/l] S: concentration of solvent. [mol/l] k2: propagation rate constant. 38. Reprinted by permission of John Wiley & Sons. Sci. . Inc.Ethylene Solution polymerization Solvent: benzene Initiator: azoisopropane Temperature: 83°C 35 Type of reaction Termination by disproportionation Termination by combination Monoradical termination Transfer with monomer Transfer with solvent Transfer with initiator Initiation Reaction rate k3dR2 k3cR2 kSXR k4MR ksSR kKKR (k3d+k3c)R2+kSXR Transfer constants: k4/k2 5 5 X 10-4.5 0. []/mol sec] h: transfer constant with monomer.. Inc. Sons. [I/mol-sec] Copyright 0 1959 John Wiley & Laita.1 * M: concentration of monomer. 247 (1959). A. [l/mol*sec] k3d: disproportionation termination rate constant. k~/k2=0. [I/mol-sec] k5: monoradical termination rate constant. []/mol* see] k3c: combination termination rate constant. [l/mol ssec] ks: transfer constant with solvent. [mol/l] X: concentration of retarder.. [mol/l] K: concentration of initiator. [l/mol*sec] kK: transfer constant with initiator. [mol/l] R: concentration of growing polymer radical. J. ks/kz 5 2 X 1O”.

My: dead polymer with x and y units.: growing polymer radical with x and y units.0.36 Solution polymerization Solvent: benzene Initiator: azoisopropane Temperature: 83°C Kinetic constants Reaction Free radical polymerization Value [I/mol*sec] (4. Reprinted by permission of John Wiley & Sons. A. + M + M I ..+I* M.. respectively. Inc. R.. Sei. M. Solution polymerization Solvent: tert-butylalcohol Initiator: diethyl peroxy dicarbonate (DEPC) Temperature: 45-60 "C I + 2R. + My .o Propagation k2 Mutual termination k3 Monoradical termination kS Transfer with monomer Transfer with benzene k.0. Inc. M. Laita.-+ M. and Machacek. R. Copyright 0 1959 John Wiley & Sons.25 1. + I: initiator..05 +. J. Z. M: monomer. M. + M y * + Mxty M + My. 459 (1959).. 38. Polym. My. -d[I]/dt=b[I] b=Aexp (-AEd/RT) . respectively.: primary radical.7 +.3) X 1O2 (1.85 X lo2 0.05) X lo2 1.* + M M.

[ l/sec] k.. [I/mol*sec] kt.000128 [l/sec] (for half life of 1. f=l k. [I/mol*sec] ktd: termination rate constant by disproportionation. 58. Inc.40./kt=0. Inc. Sci. [mol/l] [PI: concentration of polymer. []/mol sec] AEd: activation energy of decomposition rate constant of initiator. [I/mol*sec] k.6 A [ l/sec] AEd [kcal/mol] 5 X 1017 33 1 .2 13.25 2.1 2.5 hr at 60°C) B=1.47 6.: termination rate constant by combination.25 Temperature ["CI 45 55 60 45 55 60 kd X 1 Os [ l/sec] 1.: initiation rate constant.1 1. N.00033 [I/mol sec] [MI: concentration of monomer. J.. [mol/l] kd: decomposition rate constant of initiator.Ethylene 37 Concentration of DEPC [mol/l] 1. H. . Polym.1 1.25 5.0 1.25 2. [mol/l] [I]: concentration of initiator.: propagation rate constant. [kcal/mol] f: initiator efficiency. Copyright 0 1962 John Wiley & Sons. [mol/l] [I0]: concentration of initiator at time 0.7 13. 455 (1962). 2 ~ 1 0 ' ~ 32 kd=0. [mol/l] [Mol: concentration of monomer at time 0. Reprinted by permission of John Wiley & Sons. [-I - Friedlander.

1. M: monomer. p-scission of sec.. R=KB [R] R=Kp[R] I: initiator. R." + M k P1 + RI I Chain transfer with solvent KLrs R. PII1:dead polymer with m units of monomer. 2R Kx. + s P + RI n Backbiting (intramolecular transfer) R"\R Chain transfer with polymer (intermolecular transfer) R+Pn m k P + R I p-scission of tert. radical R % P+R. radical R a p +R. R: primary radical. and ketones Initiator: various initiators shown in table Temperature: 150-300°C Pressure: 1800-3000 kg/cm2 Initiation I * (R***R) Kd. alcohols..38 Free radical polymerization Solution polymerization Solvent: hydrocarbons. or Pm+n Ktnll Propagation R.: growing polymer radical with m units of monomer. . P: total dead polymer with any size.. + M ~ r + ~n n Termination Chain transfer with monomer R. noninitiating species Rln+i Pm+I + pi.

Chain transfer with solvent (n-hexane) Kt. [-] . 5. Termination K.63 X 10" 3.IRT-PAV 'IRT) Rate constants of elementary reactions Propagation K.09X 51100 61500 61900 68000 69000 TBPV: tert-butyl peroxypivalate.00X 10" 1.5 4.760 14.12X10" 2.0 -19.7 [R]: concentration of total growing radical with ant size [MI: concentration of monomer [SI: concentration of solvent [PI: concentration of total dead polymer of any size A: frequency factor.77X 10" 5. TBPC: tert-butylperisopropylcarbonate..000 12.5 -22. TBIB: tert-butyl perisobutylate.4 -23.530 ..23 X 10" 1.19.99X102' 1.. 28300 31500 33700 37300 40600 AV+ 2.820 14.29X1030 7.5 2. radical K'. DCP: dicumyl peroxide.030 15..5 A Ea AV+ 0 0 0 0 0 TBPV TBIB TBPC DTBP DCP 5.5 2.86X103* 7. K=Aexp( -E.36X lo3' 5.03 X lo2' 5.520 3.5 2.6 -19.51 X 10" 10.75 X 10" 5. Back biting (overall) Kb f3-Scission of tert. Chain transfer with polymer K.080 13.63 X lo'* 5.5 2.7 13. radical K. DTBP: di-tert-butyl peroxide.88X 1017 3.82 X 10" 8.39X lOI9 4.Ethylene Rate constants of initiation Kd 39 Kx A E. p-Scission of sec.

Inc. M. Appl. K. Polym.. Furui.: activation energy.. Inc.. S. Yamamoto. Reprinted by permission of John Wiley & Sons. S. Copyright 0 1981 John Wiley & Sons. J. [cal/mol] AV: activation volume. [cm3/mol] P: pressure. . 21 (1981). [kg/cm2] Goto.40 Free radical Dolvmerization E. Sei. Appl. Polym... Symp.. and Sugimoto. 36.

P. Sci. Inc. 8. Salatiello. Inc. Copyright 0 1952 John Wiley & Sons. potassium chloride Emulsifier: soap Initiator: tetraethylenepentamine (TEPA) and di-isopropylbenzene monohydroperoxide (DIBHP) ° 5C Temperature: 5 C and 1 ° Initiator Temperature k . [I/mol.Isoprene 41 1.2 X 1 08exp(-9800 cal/RT) k: propagation rate constant.4 Isoprene Emulsion polymerization Ingredients: water.. M. H. and Landfield. Temperature ["CI [I/mol*sec] ["CI Activation energy [kcal/mol] DIBHP-TEPA 5 2. J. Polym.3 10.8 5-15 5-15 9.3 k. P..=l.. Morton. . Reprinted by permission of John Wiley & Sons. 279 (1952). soap.sec] ..

00 X 8.828.27[cat] 0.O X 10-5 -1 Catalyst Bz202 Azo CHP t-BHP BI CI AB1 3.33 1.5 Methyl methacrylate Free radical polymerization Bulk polymerization Initiator: 2-azobisisobutyroniitrle (Azo).+c. [l/mol*sec] ktc: termination rate constant by combination.77 0. [I/mol*sec] ktd: termination rate constant by disproportionation.[ SI/[M]+AR./k. [I/mol*sec] . [mol/l] Ri: initiation rate.41 X -0 -0 0. [ l/sec] k.[cat]/[M]+cs[S]/[M]+AR.10X IO-' 1. [I/mol * sec] ktn..=c.96 X 3.93 4. tert-butyl hydroperoxide (t-BHP) and cumene hydroperoxide (CHP) Temperature: 60°C 1/P.: transfer rate constant to monomer.36X 9. [mol/l] [c*]: total polymer radical concentration. [mol/l ssec] b: decomposition rate constant of initiator.. A=(2ktd+ktC)/k: [MI2 R.59 X lo-' 2.[c*l [MI cm=ktnn/kp.[ MI2=2AR:/( 1+x) X=ktd/(ktd+ktc) A=0.=k.=BI [cat] 1/P. [mol/l] [cat]: initiator concentration.6 X [MI: monomer concentration.: propagation rate. cs=ktrs/kp R. Ri=2(ktc+ktd)R.+cIR~~/BI[ M]+c..91 0.: propagation rate constant. [mol/l] [SI: solvent concentration.15 X 10' 7. benzoyl peroxide ( B z ~ O ~ ) . [mol/l*sec] R.31 X l o 6 7.65 X lo-* kd f(l+x) 0.=c.42 1. CI=ktrdkp. cln= .37X loa7 4.

82 X lo-* 2.8 kcal/RT) h=1.2 kdf ' [ 1/sec] 8.: transfer rate constant to solvent.=2kdfII] R.00X 10-4exp(8.)/ki (1) AIBN. Inc. [-3 f: catalyst efficiency. A. Reprinted by permission of John Wiley & Sons.19X 2. V.. J. Sei. B.5 37. defined as the rate of initiation of polymer chains divided by twice the rate of spontaneous decomposition of catalyst.: number-average degree of polymerization. 8.0 45. 529 (1952).Methyl methacrylate ktrr: transfer rate constant to catalyst. Bulk polymerization Initiator: 2. [l/mol*sec] k. [l/mol.80 A' =3.19~ 1.33 x .. and Tobolsky.0 67.=kp[C*I [Ma"] Rt=2(ktc+ktd)[C*I2 f '=f (l+x) X=ktd/(ktd+ktc) A' =(2ktd+kt.26 X 1O''exp( -30. sec] P.58 X 10"exp(-30.0 55.2'-azobisisobutyronitrile (AIBN) and dicumyl peroxide (DCP) Temperature: 30. Copyright 0 1952 John Wiley & Sons.83 X 4.56 x 9. [-] 43 Baysal.5 50..100 "C R..8 kcal/RT) f'=0. Inc.18 kcal/RT) Temperature ["CI 30. Polym. temperature: 30-85 "C h f ' =1.

[mol/l] f I: initiator efficiency.: propagation rate constant. [mol/l*sec] propagation rate.. Polym. A.33.68 X IO-* 1. temperature: 60. Copyright 0 1958 John Wiley & Sons.: kt.100°C k.~ 84. polymer R + polymer + + .: R. [mol/l] [C*]: radical concentration.jf = I .. [mol/l*sec] termination rate constant by combination.0 kdf ' [ 1/sec] 1. Inc. [l/mol*sec] ktd: termination rate constant by disproportionation. Sci.44 Free radical polymerization (2) DCP.oo x I . J. J. [mol/l] [Ma"]: average monomer concentration. and Tobolsky.4 kcal/RT) Temperature ["CI 60. [-3 Van Hook. P.3 Ri: R. Inc. 429 (1958). [I/mol*sec] [I]: concentration of initiator. V. Bulk polymerization Initiator: azobis(isobutyronitri1e) Temperature: 60°C Initiation Propagation Termination R + Pr + Pr + Pr + -+R M +PI M Pr+I P.0 72. [mol/l*sec] termination rate.26 X 106exp(-36.27 x 1o .: initiation rate. Reprinted by permission of John Wiley & Sons. [I/moI* sec] k.

.68X lo7 ktp: rate constant for initiation by primary radical. X. + + + 2R..6 k2=5. sec] kp: propagation rate constant. E.: rate constant termination with primary radical..2.: growing polymer radical with x units. + P. product M: monomer. growing polymer radical with x units.4. 2R. P. and Patrick C. 48.: rate constant of reaction between primary radicals.. product k"3 I: initiator. + 45 k".4-tetraphenyl hexane (TPH) and 1. R. [l/mol*sec] k'. Chem. [Vmol. [I/mol. . R . [I/mol-sec] k. [Vmol-sec] Allen. Makromol. sec] k".: P.1. Bulk polymerization Initiator: 3.. or P.55 X lo2. k3=2. XI. + X. + R.2-tetraphenyl cyclopentane (TPCP) Temperature: 60°C I Re + M X.: termination rate constant.sec] 3.. k'P [Vrnol-sec] 280 kP [I/mol.Methyl methacrylate 2R R: primary radical.: dead polymer with x units. 89 (1961). P. X.sec] 700 2k. X [I/mol. Xr+l* kl k'2 k2 k3 k'3 + + 4 P..: primary radical.3. + M X. P.

.68 X IO' k.0 x 1o-~.. sec] k3: termination rate constant. Bulk polymerization Initiator: l-methyl-2-(9'-anthryl)-cyclopropyl-carboxylate (ACP) and diphenyldiazomethane (DDM) Temperature: 60-90°C Maximum conversion: about 6. [-I Nakaya. M.2 X lo8 2. [-I C.1 [kcal/mol] ci=o.: chain transfer constant to initiator. K. Makromol. [mol/l. [mol/l] C.6 X lo8 k1'3/( k'2)2 [mol. [ l/sec] k'2: initiation rate constant. [I'/2/moll/2sec] * [i]: concentration of i.55 X lo2. and Capla.. sec] P3: rate constant termination with primary radical. R. [I/mol. and Imoto..0% R.... k3=2. 105. [Vmol. 212 (1967)..5 X 10' 2. sec/l] 8.=2.=k[DDM]o. M. T.6 x I o9 2. sec] Borsig.sec] k: initial polymerization rate constant..0 x 10" 7. [I/mol. [I/mol*sec] k'I3: rate constant of reaction between primary radicals. E. [I/mol* sec] k2: propagation rate constant. M. Makromol. Lazar. Chem.: decomposition rate constant of initiator. Chem.SIMMA]l. 114.o cl.. Ohashi.: chain transfer constant to monomer. 201 (1968).oat 70°C Overall activation energy=l3. .0 x k2=5.46 Initiator TPH TPCP Free radical polymerization kl [ 1 /sec] k13/k12 1.: initial polymerization rate.

[M][C]1/2/R. M: monomer.. and Matsuda.: propagation rate constant. Copyright 0 1970 John Wiley & Sons. Reprinted by permission of John Wiley & Sons. [I/mol.: primary radical termination rate constant. J.sec] R.. Inc. [mol/l] kd: decomposition rate constant. [mol/l] [MI: concentration of monomer. Sci.i/k. (2fkd/kt)112 B=(k.41 x [C]: concentration of initiator.: rate constant between primary radicals. Ar: growing polymer radical with r monomer units. [I/mol*sec] k.: termination rate constant. Polym.57 X B=1. or Pr+.=l/A+B[C]1/2/A[M] A=k. .2'-azobisisobutyronitrile Temperature: 60°C C R + M Xr + M Xr + X. Y: chain transfer agent.: dead polymer with r monomer units. [mol/l-sec] Ito. [Vmol-sec] k.: propagation rate. [ l/sec] ki: initiation rate constant.. 3 1 1 (1970). Appl. T. [Vmol esec] k.)(2fl<d/kl)l/Z A=3. r P. K.14.Methyl methacrylate Bulk polymerization Initiator: 2. P. [Vmol-sec] kt. Xr + R 2R + 47 2R +XI Xr+l + + + + P + P. Inc. products C: initiator. R: primary radical.

0 x Initial rate constant k' [I/min] 1.13X 1. [MI: concentration of initiator and monomer.11 x 1. respectively.5 X 4.60 X 1O-* 1.0 X 5. [I/mol * min] .3 X 10.48 Free radical polymerization Bulk polymerization Initiator: a. respectively.49 X [IO].60X 2.4 [kcal/mol] Temperature: 80°C Initiator concentration [mol/l] 2. [mol/l] [I].a'-azobisisobutyronitrile Temperature: 70-90°C "2t In([Mo]/[M])=k't=kp(2fkd/kt) "2[1~] Initiator concentration: 5.2 X 6.2 X Temperature ["CI 70 75 80 85 90 [mol/l] Initial rate constant [ l/min] 0.: propagation rate constant.78 X 1.29 X 3. [mol/l] f: initiator efficiency.85 X 10-2 2. [-I k': overall rate constant.24 X 10-2 Overall activation energy=l8.43 X I . [Mol: initial concentration of initiator and monomer. [l/min] k.

175. + Pi.Methyl methacrylate 49 h: initiator dissociation rate constant. products kd ki kP kt(n. [mol/l] [R-1: concentration of macroradicals. Makromol. Vizovisek. I: initiator. Lapanje. [l/mol*min] Malavasic. + +M + + Pi. V...[M] [R ] kl=-d[M]/P[R. I. R * + P.l2dt kp=2. Bulk polymerization Initiator: dibenzoyl peroxide and cyclohexyloxycarbonyl peroxide Temperature: 45-85"C -d[ M]/dt=k. 175.. + M P. and Shadrin. []/mol * sec] [MI: concentration of monomer. and Moze. [I/mol*sec] k. [mol/l] P: degree of polymerization. Kazbekov. Pn*: growing polymer .5X 106exp(-5400~600 cal/RT) kl=7. [-3 Bresler. 2875 (1974)..: propagation rate constant.. R..: primary free radical. Dead polymer P. S.: termination rate constant. E. Makromol. M: monomer. R. P~. 873 (1974). N. Chem.+I. E.2'-azobisisobutyronitrile Chain transfer agent: 1-butanethiol Temperature: 50-70°C I R. N. Bulk polymerization Initiator: 2.2 X lo8 k. T....: propagation rate constant.. [l/min] k...m) ktpr kl. + Re + + + 2R. PI... S. Chem. A.

[Vmol-sec] kt(. [Plj: growing polymer radical containing j units of monomer.50 Free radical polymerization radical containing r units of monomer. [l/mol*sec] ktd: termination rate constant by disproportionation.: rate constant of reaction between primary free radicals. Chem.: dead polymer containing n units of monomer. [I/mol*sec] k. H. [I/mol*sec] Kuo. [A]: monomer. 13.. F. F.. K. Bulk polymerization Initiator: benzoyl peroxide Temperature: 60°C + + Initiation Propagation Termination [I1 [RI + [AI + [Plj + [AI [P]i + [PI... klpr/kpki=7.".+kld=2. Makromol. Y. [R]: primary radical. J. 453 (1981). [ l/sec] ki: initiation rate constant..5 X IO7 k.: dead polymer containing r units of monomer.: propagation rate constant.. J.52X 1O-3exp(779 1 cal/RT) kd: decomposition rate constant. C. [MI. [Pli + [Plj-+ + 2[RI [PI1 [Plj+~ [M]i+j [Mli + [Mlj kd ki kP ktc ktd [I]: initiator. P. 2629 (1977).):termination rate constant. [Vmol-sec] k. K. [I/mol*sec] kp: propagation rate constant. [I/mol*sec] ktpr:rate constant of termination reaction with primary free radical. [I/mol*sec] Mahabadi. [I/mol*sec] ktc: termination rate constant by combination. and Chen. 178.6 b: decomposition rate constant. . [ l/sec] ki: initiation rate constant. kt=kt. and 0 'Driscoll.=705. Polym.

2'-azobisisobutyronitrile Temperature: 25°C I R" + M Propagation Pi. 0 1985 American Chemical Society.Methyl methacrylate Bulk polymerization Initiator: 2. 13 19 (1 985).in) I: initiator." + M Chain transfer +Y Termination by disproportionation P." : growing polymer radical containing n units of monomer. kt(n. P.22 kd: decomposition rate constant. []/mol sec] kt.O P.." + PI.: dead polymer containing n units of monomer.in)+ktd(n.. P.O + + Termination by combination PI. R" : primary free radical. Y: chain transfer agent. K. .ln): termination rate constant." P.ln~= X 108(nm)0.. + PI..in)=ktc(ii.. [Vmol-sec] ktc(ll. ktd(n.: transfer rate constant to Y. [ l/sec] ki: initiation rate constant. [Vmol sec] Mahabadi.l.m) ktc(n. P.. + Y" kd ki kP ktW + P. 18.m) kt(. [I/mol*sec] k.+. Macromolecules. [I/mol*sec] kt(n. [I/mol* sec] ktc(ll.075 1. H.O 51 Initiation + + + + 2R" Pi'' Pnt i o PI.l~: termination rate constant by combination.: propagation rate constant. M: monomer.)=ktc~~l.): termination rate constant by disproportionation.l...

2 kcal/RT) for 34-60'C ..R.Re RI.a'-azobisisobutyronitrile Temperature: 50 and 77°C 50 77 1. [I/mol*min] Arnett. M: monomer.05 [MMA] b=5. J.min] k. Bulk and solution polymerization Solvent: benzene Initiator: 9-anthryldiazometliane (ADM) Temperature: 70°C Initiation Propagat ion Termination ADM + . Am. Rp=k[ ADM]0-0.R.52 Free radical polymerization Bulk and solution polymerization Solvent: benzene Initiator: a. R.(=P) kd ki kP1 kP. 2027 (1952). +M +M 'RM*(=Rl*) R2' Rr+l. 0 1952 American Chemical Society. Soc.: termination rate constant. [ l/min] kp: propagation rate constant. Chem. 74. [I/mol. + Re + -+ R. M. . + + .67 k l : decomposition rate constant of initiator.09 0. + M R. Rr. kl * R * :primary radical.: polymer radical containing r units. L.2~10-~ 1...50 X 10'*exp(-25.

[I/mol.86-0. 115 (1968). sec] Nakaya. Chem. sec] k.93.a-azobisisobutyronitrile (AIBN) Temperature: 70°C Maximum conversion: about 8.: termination rate constant. [I/mol. [I/mol*sec] kK: chain transfer rate constant to initiator. [I/mol*sec] kPr: propagation rate constant of polymer radical containing r units. Chem.": chain transfer rate constant to monomer.: initiation rate constant. sec] k.65 1 us. 111. M.: initial polymerization rate. 117..3 [kcal/mol] for bulk polymerization (60-90°C) R.0% For ACPC R. [I/mol*sec] k... 117 (1968). T.32/mol' sec] 32 k.. Makromol.=2../kP=2. K. K. [1'. Makromol. [l/sec] k: initial polymerization rate constant.: propagation rate constant. [I/mol*sec] - Imoto. [mol/l] k: initial polymerization rate constant.C~=k~/k. and Imoto. and Ohashi. .=k[ACPC]' 82[MMA]i for bulk and solution polymerization CM=k. Bulk and solution polymerization Solvent: benzene Initiator: 1 -methyl-2-(9'-anthryl)-cyclopropyl-carboxylate (ACPC) and a.Methyl methacrylate 53 R..: initial polymerization rate. [mol/l*sec] [i]: concentration of i. [(l/mol)0. [mol/l] kd: decomposition rate constant of ADM.. [mol/l* sec] [i]: concentration of i.010" for bulk polymerization X X Overall activation energy for initial rate=l8. Ohashi. M.

+Ci[DMDM]/[MMA] A=O. [mol/l] R. H. 1043 (1971).. Burnett.O at 70°C Overall activation energy=] 9. 169 (1962). Wada.S [I. [Vmol. 58.=k[DMDM]053[MMA]0. M.=Ak. [I/mol*sec] k.: number-average degree of polymerization k: initial rate constant of polymerization.: rate constant of propagation. Makrornol.sec/mol].: propagation rate constant.84 I/P. M./k.. sec] ki: chain transfer rate constant to initiator.. and Majer. T..p'-dimethoxydiphenyldiazomethane (DMDM) Temperature: 60-90 "C R. sec] P. CIn=k. [I/mol*sec] Allen.. polyvinylacetate (PVA). A5. [mol/l. .. Emulsion polymerization Ingredients: water. R. M. J.54 Free radical polymerization Bulk and solution polymerization Solvent: benzene Initiator: p. M. and methylmethacrylate Initiator: polyvinylacetate Temperature: 40°C k. [ l/sec] kin: chain transfer rate constant to monomer. Chern.3 X Ci=ki/k.. [I/mol*sec] Nakaya. and Imoto. Tanaka..= 140 k. Sci.. J.: initial rate of polymerization.OX 10'5exp(-29100 cal/RT) for 50-80°C [i]: concentration of species i. G.-Chem. J. Downer. Macrornol..=O. [mol/l*sec] h: decomposition rate constant of initiator.3 [kcal/mol] kd=l. E.=3. P. M...+C.

.........6-3500/T k..... [I/g-mol*sec] Soh. + 0. Appl.O: volume of a latex particle at zero conversion...25.....( 1-X)/~NAV( 1n(kp)=l6......... (*) Emulsifier: sodium laurylsulfate 46% solution.......... Emulsifier: sodium laurylsulfate....Methyl methacrylate Emulsion polymerization Emulsifier: sodium laurylsulfate or + 0.)N........ ~ :volume of a latex particle at complete conversion...... 540"' 340(2) 17 1(2) . Reprinted by permission of John Wiley & Sons..... [mol/l] v... J.......................... [cm3] k....=V.. [cm3] v.......... ..... [MI: concentration of monomer..3% of Dowfax 2A1..( 1 -EX)/( 1-E) [M]o( 1-x)/( 1-EX)=[M] 1-EX) V...... 46% solution Initiator: potassium persulfate Temperature: 40-60°C -d( [MI V.....O........ K.......: propagation rate constant........... 2993 (1980).... Inc.. [I/mol.sec] N A V : Avogadro's number.3% of Dowfax 2A1. [-I x: fractional conversion........ S..... Inc........ .. Polym......... [cm3] v . [number/mol] E: volume shrinkage factor E=(V.....: volume of a latex particle......O-V......... [YO] k..... Copyright 0 1980 John Wiley & Sons........)/dt=kp[ M]/~NAv V.............=156 at 50°C Temperature ["CI 60 50 40 . Sci....... (I) 55 [ I/g-mol.........: propagation rate constant.................... .sec] k....dx/( 1-E)dt=k...

M. B.33 5 cop5 0. + P + + + 2R-.56 Free radical polymerization Emulsion polymerization Initiator: peroxydisulfate anion Temperature: 50°C Initiation Aqueous phase Propagat ion Entry I= R-* + M -RM. and Gilbert. M: monomer. Polym. Polym. potassium peroxydisulfate. Emulsion polymerization Ingredient: methyl methacrylate. Chem. R. Reprinted by permission of John Wiley & Sons. S. R. Ed. XM. D. krl + I=: initiator. -RM.60. Inc. seed latex.. -RM. 19. [I/mol*sec] Hawkett. Sei. water. Polym. Chem.=3 X IO7 ki: decomposition rate constant of initiator. H. E: entry into particle.9-26. Reprinted Ed. Napper. G. 1-4. Polym. k...: propagation rate constant. Inc. H. Copyright 0 1981 John Wiley & Sons. J. J. ki=1.* E k...: termination rate constant. by permission of John Wiley & Sons.3 X k. . and surfactant Initiator: potassium peroxydisulfate Temperature: 50°C In(kt)=12.940. 3225 (1984).I. [ l/sec] k.. =28.. [Vmol.78 > k. J. : polymer radical with n units.78 oP 0. [-I . Sei.: entry rate constant of oligomeric free radicals into particles.. ki k'.=500.: termination rate constant.: primary radical. P: a latex particle. Inc. [I/mol*sec] k.. 3173 (1981). Inc. G. 22. sec] k. 0. Copyright 0 1984 John Wiley & Sons. D. and Gilbert. Napper. - Ballard. [dm3/mol sec] a : weight fraction of polymer. + M -RM. R-.

=l50. 0 1986 American Chemical Society. H. kt=l .: propagation rate constant. and Bamford.Methyl methacrylate Emulsion polymerization Ingredient: MMA. [dm3/mol * sec] kpo: propagation rate constant in the absence of diffusion." =790 -t 300 [dm3/mol sec] 0 :weight . 380 (1946)..sec] k.84 5 0 ~ 5 0 . J. W.=k.. Pomery. and water Initiator: DPPH (a&-diphenyl p-picryl hydrazyl) Temperature: 50°C 57 k.-0. M. and O'Donnell.' exp{-29. C. J. 9 9 ) fraction of polymer. P. J. G.33 S 0 ~ 5 0 . seed latex... H. [dm3/mol-sec] Ballard..84)) k. [Vmol-sec] Dewar. P. k. M.r=0. R.: transfer rate constant. (0. Napper. DPPH.=k..3 X 1O7 k." k.8(0. 1303 (1986). Aerosol MA 80. J.: termination rate constant. H. [I/mol. 158. Gilbert.+M+P2+R R + M + P . Nature. Macromolecules. Photo-induced bulk polymerization Temperature: 0°C Initiation Propagation 2M 2X or DZ M + hv -+ 2X or DZ X + M + X DZ+M-jDI+R D. D. S. O'Sullivan. 19. [I/mol*sec] k.: propagation rate constant..03.. [-I k. Photo-induced bulk polymerization Temperature: 25°C k. 8 4 ) (0. + R --j .

D2: initial polymer growing at both ends. 2. PI: dead transfer polymer. Q: dead center. H.69 X 10' kl: initiation rate constant. [Vmol-sec] k: termination rate constant. [Vmol. Qtr: an active "half-chain" of length r units..+Q 2x 24 --+ + 2k4 k4 k4 k4 M: monomer. sec] k3: transfer rate constant. 310 (1947).6-50. Photo-induced bulk polymerization Temperature: 23. P2: dead initial polymer. D1: polymer growing at one end. C. Qr: an inactive "half-chain" of length r units.sec] A: constant I: light intensity Bamford. and Dewar..58 Termination Free radical polymerization D2 + X DI + Q D. sec] k2: propagation rate constant. [I/mol. . Discussions. J. + X . X: active center.13 x [Vmol sec] - 41.6 2. Faraday SOC. sec] AI: rate of initiation.5"C M + hv Qr + M Q'r + Q n = Q I + Qo rate=f( I) kP = Q'r+l = Qr + Qn kt M: monomer. [mol/l.t P2 + Q R + X +P. S.83 X k2 [I/mol*sec] k3 k4 [I/mol. kl [I/mol*sec] 6. R: growing transfer polymer. M. [Vmol. sec] 6.

Photo-induced bulk polymerization Temperature: 0°C 2M + 2X or D2 X + M + X D2 + M + D1 + R DI + M . H. X 10-2 [I/mol..1 4. PI: dead transfer polymer. X 10-7 [I/mol*sec] 6.9 3.sec] 59 k.Methyl methacrylate Temperature ["CI 23.. Faraday SOC.6 35. + . R: growing transfer polymer. DI: polymer growing at one end. X: active center. Q: dead center.6 6.t P2 + R R + M + PI + R D2+X+DI+Q D I + X + P Z + Q R + X + P I + Q 2x 24 M: monomer. and Melville. Pz: dead initial polymer. Trans. M. Mackay. D2: initial polymer growing at both ends. 323 (1949).8 k.5 k. [I/mol*sec] 45. [mol/l*sec] k. H.= 1O8 f(1): rate of initiation.9 50.=5 X 1OSexp(-4400 cal/RT) k.: propagation rate constant. [l/mol*sec] k.: disproportionation termination rate constant. W.8 6.05 5.

[-I I: light intensity A: constant [MI: monomer concentration. + M M.: number-average degree of polymerization. + Ma polymer -+s + --j + + Rate 2qIa 2kSR. A=32. [I/mol. k2=41..: polymer radical containing r units of monomer. London. M..+ - 2R. Ma M. []/mol sec] k3: transfer rate constant.69X lo6. Bamford. M. M. A197.<=(1+AI/kl [M]2)112 kl=6. 356 ( 1949).l 2ka[R. k3=6. [mol/l] h=2. H. Proc. []/mol sec] k2: propagation rate constant.1 kl : initiation rate constant.82 X lo-”. M.13 X p=4. sec] P.[M * 1[MI ktr[Mr. Re: primary radical. I [MI k. C. . Soc. and Dewar.51. S. Roy.60 Free radical polymerization Pn=2k2(kIb)-1/2/(2p+r) p=k3(k1h)-I’~.: dead polymer containing r units of monomer.6.. ][MI 2k. J. Me: monomer radical. + M Me + Me .. + M M. []/mol sec] b: termination rate constant. M: monomer. Photo-induced bulk polymerization Sensitizer: biacetyl Temperature: 5-70 “C Initiation Propagation Transfer with monomer Termination S + hv 2R* R.[M l2 - S: sensitizer.

71. sec] Grassie. S. sec] kt..=5.: rate constant of inactive reaction of primary radical. Proc. [I/mol*sec] ktr [I/mol*sec] 3.Methyl methacrylate 61 Temperature [“CI 30 60 k. M.. and Meliville.75 X 1O‘6 k. [I/mol*sec] k. London. E. 0 1949 American Chemical Society. 497 (1949). Auer. H.36 X lO’exp( -2840 cal/RT) ktr=2.: termination rate constant. [I/mol. J.75X 106exp(-12280 cal/RT) hv: quantum of frequency v q: quantum yield of dissociation of S I.9 x 10” 143 367 1 .. Am.87X k.. sec] k. W. Roy. [I/mol. Bevilacqua. E. 2 2 io7 ~ io7 1. .: termination rate constant. 285 (1951). N.. Soc. Chem. Photo-induced bulk polymerization Temperature: 15°C kdkt=6.57 x 10” 22.: absorbed light intensity k.13 X 106exp(-63 1 0 cal/RT) 2kt=1. J. [I/mol.: transfer rate constant to monomer. [I/mol*sec] k. [limo1 sec] - Matheson. [I/mol*sec] k. E.: propagation rate constant.: initiation rate constant.. B.. and Hart. [Vmol-sec] k.: propagation rate constant. A207. Soc. E.

Japan.=3 X kt/k. and Taylor. [mol ..96 X 1O-* ka/kto(‘) [%I 0. k.62 Free radical polymerization Photo-induced bulk polymerization Temperature: 30-50°C Maximum conversion: about 72% Conversion Temperature [“C 1 30 40 30 30 kdk. Melville. H. S. R. 1 0 10” ~ 2. SOC. Photo-induced bulk and solution polymerization Solvent: benzene Initiator: 2. C.48 x 10” 9. J. [I/mol*sec] k.86 X l o 3 2. 27. Copyright 0 1954 John Wiley & Sons. P. .47 x 9. [I/mol*sec] Fujii. Sci. 238 (1954)..93 x 1 o 2.: termination rate constant. []/mol sec] Bevington. 1. [I/mol*sec] kf: transfer rate constant to monomer.2’-azobisisobutyronitrile Temperature: 25°C k$k.20 x 10” 9.: termination rate constant.. Reprinted by permission of John Wiley & Sons. 449 (1954). W.: propagation rate constant. Inc. Chem.52 x 1 0 ‘ ~ 40 72+3 50 30 ‘”The ratio of kt at x% conversion to its initial value was estimated at 30°C.07 x 10” 6.33 x 10” 9.. [I/mol*sec] k. Inc.sec/l] k. J.=260.1 47+2 52k2 ~ 1 2 .. 12. Polym. Bull.: propagation rate constant.

.66 x io7 Activation energy=3. H..6 [kcal/mol] k.London.61 k. W. M.: propagation rate constant. 330 ( 1 954). Roy. H. Proc. SOC. W.: termination rate constant.Methyl methacrylate Photo-induced bulk polymerization Sensitizer: azobis(cyclohexanecarbonitri1e) Temperature: 15°C kdkt=9. 73 ( 1 954). ..=4. W. [I/mol*sec] Chinmayanandam. Photo-induced bulk polymerization Sensitizer: benzoin Temperature: 25°C Decomposition Initiation Propagation Termination benzoin 2R R + M +Pi PI + M * Pz P + M n Pn+1 P + Pn * Mn + M n a m + + k.sec] k.. B. P. M: monomer. and Melville.: dead polymer containing n units of monomer.: growing radical containing n units of monomer. I. Trans. k. [l/mol*sec] 63 Bengough. A225.: propagation rate constant. Faraday Soc. and Melville. [Vmol sec] k. 50.8 X 1 0-6 k.. R. kt R: primary radical.: termination rate constant. [Vrnol.=512.

9 17 125 262 0. [I/mol*sec] Miyama. Photo-induced bulk polymerization Temperature: 20-50°C Transfer agent: n-butyl mercaptan Maximum conversion: 35% Conversion [%I 0-2 6 26 35 3-5 13 0-2 Temperature ["CI kdk. 715 (1956).26 0.47 0.22 0. H.. X 1O5 (a) n-butyl mercaptan: 0 mol% 30 50 30 30 30 (b) n-butyl mercaptan: 0.52 10 27 .: propagation rate constant.: termination rate constant.59 0.66 X lO"exp( -3540 cal/RT) k.64 Free radical polymerization Photo-induced bulk polymerization Sensitizer: a-azobisisobutyronitrile Temperature: 30-40°C kdk.=2. Japan.53 0. 29. [I/mol*sec] k.30 0.9 mol% 30 50 50 (c) n-butyl mercaptan: 2 mol% 20 40 20 40 20 40 1. Chem. SOC.47 0.4 1.36 0. Bull.

Methyl methacrylate k.. Inc. Reprinted by permission of John Wiley & Sons.: propagation rate constant. and Sutani. J. Inc. X 1Os ["/. S. 20.I 50 52 42 1. [I/mol*sec] kt: termination rate constant.. Sci. S. Polym.. Inc.: termination rate constant.4 k. Tanaka.. Copyright 0 1956 John Wiley & Sons. Tanaka. [I/mol*sec] 65 Fujii. 584 (1956). Inc.. Polym.: propagation rate constant.1'-azobiscyclohexanecarbonitrile Transfer agent: n-butyl mercaptan Temperature: 20°C Maximum conversion: 52% n-Butyl mercaptan Absence Presence Conversion kdk. [I/mol-sec] Fujii. Sci. Photo-induced bulk polymerization Sensitizer: 1. and Sutani. Reprinted by permission of John Wiley & Sons. 20. [Vmol sec] k. 409 (1956). S. S. .. S. J. S. Copyright 0 1956 John Wiley & Sons...

66 Free radical polymerization Photo-induced bulk polymerization Sensitizer: 1.2 1 12. [I/mol. sec] Miyama.3 16.1 k.1 32.7 4. H.1 1.: propagation rate constant.23 1.2 6.sec] k.6 1.12 1.0 [%I 0 0.6 19.0 2.4 10.8 3 .01 1.7 2. 459 (1957)..2 8. 30. Japan.3 2. SOC. Chem.80 2.04 5. [I/mol.2 9.22 7.54 1.5 121.4 5.1 18.30 1.99 1. Bull.40 1. .48 1.60 3.6 85.8 12.2 22.4 14.34 4.2 7. X 1O5 0.O 3.7 2.1'-azobiscyclohexane carbonitrile Temperature: 30°C Conversion kdk.38 1.: termination rate constant.22 2.0 53.

64x 1 ) 0 7.64 io7 x 4.3 0 0 4.72 io4 x 7. []/mol* sec] 0 1 0 20 30 40 50 60 70 80 357 234 272 286 364 197 57 1 6 14 .42x io7 2. [I/mol*sec] 0 1 0 20 30 40 50 60 70 80 384 234 267 30 3 368 258 74 1 6 1 4.Methyl methacrylate Photo-induced bulk polymerization Sensitizer: 2.86 1' X 0 1. 4.98 io4 5.83X 1 O-'.26X 1' 0 4.20 lo6 X 6. Conversion [%I [mol/l*sec] 67 kP [l/mol*sec] k.5"C Maximum conversion: 80% Rate of initiation: 2.03X 1' x 4.36X Conversion [%I kP [l/mol* sec] k.10~ io7 2.73x io7 7.2 8 9 X 1' .2'-azobisisobutyronitrile Temperature: 22.90X 1O3 1.6 X lo2 [mol/l*sec] Rate of initiation: 8.26X lo6 1 4 X lo6 .51 X lo2 .59XIO5 2.

4 34. H.0 11. 1 8 io7 ~ 3.3 6.8 29.5 1. [kcal/mol] 5.7 -3.0 8.0 6.: activation energy for termination reaction. [I/molssec] E.4 E.6 7.3 -0. 201 (1960).8 Eoverall [kcal/mol] 5.9 -4.8 10. Reprinted by permission of John Wiley & Sons.: propagation rate constant.3 1. P.. [kcal/mol] Hayden. Sci.93 x lo6 8. W. [mol/l*sec] Conversion [%I 0 10 20 30 kP [I/mol*sec] kt []/mol sec] 357 234 272 286 4 . [l/mol*sec] k.84 x io5 Conversion [%I 0 5 10 15 2 25 30 35 40 45 Et [kcal/mol] 0.2 32.1 -4.2 8.. . J.3 13.5 23.0 k. Polym.6 11.6 3.8 6. Copyright 0 1960 John Wiley & Sons. [kcal/mol] E.60 x io7 4.: overall activation energy..: activation energy for propagation reaction.8 6. and Melville.: termination rate constant.68 Free radical polymerization Rate of initiation: 1.43.2 4. Inc.8 17.20X 10-8.6 5. Inc. [kcal/mol] Eovera.4 3.6 -4.

003 0.004 BZ BME BL k. Polymer.059 k 0. : growing radical containing n monomer units. [I/mol*sec] Hutchison.Methyl methacrylate Photo-induced bulk polymerization Sensitizer: benzoin (BZ). rate r. and Ledwith.=241as Mn* + M M . + M. + Mine I. MI.0. and benzil (BL) Temperature: 30°C 69 Sensitizer kdkt’I2 [(I/mol s ~ c ) ” ~ ] 0.. Re: primary radical formed from its decomposition. + Pi. [I/mol. . 14. Po: polymer molecule containing n monomer units. P + Pin or P. . 405 (1973). S: sensitizer. + R. A.+1. + M M. + S ..063 t.. + Min * Mn.038-tO. + MI.: termination rate constant. J.002 0.. M: monomer. + kP ktc ktd ktnn kt. benzoin methyl ether (BME).i+in n Pii+in + P. Mil. Photo-induced bulk polymerization Sensitizer: benzoin and benzoin methyl ether Temperature: 293°C S Re +M + + 2R. M . sec] k.: propagation rate constant.

[I/mol*sec] ktm: rate constant of chain transfer to monomer. + R * PI.3 kt=ktc+ktd k. 2R.. Pn* + P.. + M P..1934/T) .dPn*][MI ktc[Pn. Pn+l../k. R. F. + PI. Felder. [I/mol*sec] 4: primary quantum yield Ias: rate of absorption of light by sensitizer Mendiratta.. sec] ktd: rate constant of termination by disproportionation.: rate constant of propagation.. 21. PI..70 Free radical polymerization Sensitizer Benzoin Benzoin methyl ether +112k."2 [(l/mol*S ~ C ) ' ~ * I 1. K.: rate constant of chain transfer to sensitizer. sec] ktc: rate constant of termination by combination. Engineers. [Vmol. ][I'm. PI... Photo-induced bulk polymerization Sensitizer: 2. [I/mol. AZChE Journal. PI.042 X loa2 k4k1"2=44 exp ( . S. B.. 1115 Reproduced with permission of the American Institute of Chemical (1975). +labs kd[CI ki[R ][MI k#'n 1[MI ktr.269 X IOq2 4. M.2'-azobisisobutyronitrile Temperature: 25°C Rate Initiation C + hv C R* + M P. 3 ktd[Pn * 1[pin * 1 e ... + Y P.sec] kt. + -+ + f Propagation Transfer Termination + --j + 2R. All rights reserved.... + P. and Hill. [I/mol. Copyright 0 1975 AIChE.

J. [I/mol*sec] 244. Sci.Methyl methacrylate 71 C: sensitizer.91 10.8 29. [l/mol*sec] . Photo-induced bulk polymerization Sensitizer: 2.. Polym. 14.=3 15.95 13. Inc.1 278.. P.92 X 105exp(-4353 cal/RT) kl=9. Re: primary free radical.6 k. [I/mol.5 315.04 0. [ l/sec] ki: initiation rate constant. and Mahabadi. [mol/l] b: decomposition rate constant.80X 1O7exp(-70I cal/RT) k. M: monomer. Inc.03 0.0 13.sec] k. permission of John Wiley & Sons.05 0..: propagation rate constant. Y: chain transfer agent.2'-azobisisobutyronitrile (AIBN) Temperature: 15-30°C Maximum conversion: less than 1% - Temperature ["CI 15 20 25 30 [AIBN] [mol/l] 0. F. Copyright 0 1976 John Wiley & Sons.: growing polymer radical containing n units of monomer.sec] ktc: termination rate constant by combination. [Vmol sec] klr.Y: transfer rate constant to Y. H. [I/mol.025 X. P. Ed.0 kt [I/mol sec] - 14. Polym. K.=4. [I/mol * sec] - ODriscoll. K.62 28. kl=30 X lo6 [AIBN]: concentration of AIBN. [l/mol*sec] ktd: termination rate constant by disproportionation.: propagation rate constant.0 356. Chem.: dead polymer containing n units of monomer.X 10" k. Reprinted by 869 (1976).4 30. 30. k.

H.75: kt=l 04-5 X 1O7 x: conversion.. A l l .: monomer concentration at conversion x. 9. [Vrnol-see] Olaj. J.sec] XI. K. Rapid Commun.sec] k.50 299 43 1 k. Kremminger. f: efficiency. [I/mol*see] kt: termination rate constant. and Schnoll-Bitai. Sei. [Vmol. see] . [I/mol. [mol/l] kp: propagation rate constant. [[MIo: monomer concentration at conversion 0. Mukromol. Mucromol. [-I Mahabadi.. P.. and O'Driscoll. 0. [mol/l] [MI. 771 (1988). Chem. K.45 0.: termination rate constant.72 - Free radical polymerization - k t: average rate constant of termination.=O-6: kdkt=l O-'-lO-* x=O-0.75: f=0. [I/mol. F.-Chem. u e kinetically effective fraction of initiator radicals formed.4-0 [M]o-[M].. I. Photo-induced bulk polymerization Initiator: azobis(cyclohexanenitri1e) Temperature: 0°C Maximum conversion: about 75% x=O-0. 967 (1977).. F. Photo-induced bulk polymerization Sensitizer: benzoin Temperature: 25-40°C Temperature ["CI 25 40 kP []/mol see] kt X [I/mol-see] 0.: number-average degree of polymerization.: propagation rate constant.

and Meyerhoff. Cl-. R.+ M 3 X-(M). NY) Temperature: 25°C Light absorption Fe3'Xhv > Fe2+X Primary dark back reaction Fe2'X-+Fe3'XInitiation of polymerization by the primary product Fe2'X Fe2'X + M + Fe2+ + X-MSeparation of the primary product Fe2'X + Fe2* + X Secondary dark back reaction Fe2+ + X + Fe3' + XFree radical initiation of polymerization X + M + X-MPropagation of polymerization X-(M).Methyl methacrylate 73 Sack. 3345 (1988). M. Schulz.+.-X + X-M.+ X --+ X-M.+ -M. Photo-induced solution polymerization Solvent: water Initiator: Fe3+X-(X-=OW. 21.: polymer containing p units.... . Macromolecules. G.-X M: monomer....Termination of polymerization (a) by free radicals X-M.-X (b) by recombination of active endings X-M. G.-M.. V.

74

Free radical polymerization

Fe3'ClFe3')Ni

-

0.98
-

46

h: the fraction of the light absorbed by Fe3'X-, b: rate constant of primary dark back reaction,

[l/sec] [l/sec] kIi: rate constant of initiation reaction by the primary product Fe2+X, [I/mol.sec] k,: separation rate constant of the primary product, [l/sec] ko: rate constant of secondary dark back reaction, [I/mol*sec] ki: free radical initiation rate constant, [I/mol*sec] kp: propagation rate constant, [Vmol- sec] k',: termination rate constant by free radical, [I/mol-sec] k,: termination rate constant by recombination of active ending, [I/mol*sec]

Evans, M. G., Santappa, M., and Uri, N., J. Polym. Sci., 7, 243 (1951). Copyright 0 1951 John Wiley & Sons, Inc. Reprinted by permission of John Wiley & Sons, Inc. Photo-induced solution polymerization Solvent: water Initiator: ferric-hydroxide complex Temperature: 25-35 "C Fe3'0H' + hv + Fe2+ + OH MI* OH + MI Mj* + MI + Mj+l* Mj* + MI + Pj + MI* Mj* Mk* + Pj Pk O P,+j r
+

h=365pm

Rate=&
kP kf

k* Mj*: radical polymer with j units,

MI: monomer, MI*: monomer radical, P,: dead polymer with j units.

Methyl methacrylate

75

Temperature [“CI

k,
[I/mol*sec] 75 about 100

k,
[I/mol- sec]

25 35

1.8X lo4 about 2 X lo4

RI: rate of polymerization, [mol/l.sec] I,: intensity of light absorbed hv: quantum of frequency v k,: propagation rate constant, [I/mol *set] k,: termination rate constant, [l/mol. sec] kf: transfer rate constant to monomer, [I/mol*sec] [MI]: monomer concentration, [mol/l] P,: number-average degree of polymerization, [-3
Atkinson, B. and Cotten, G. R., Trans. Faraday SOC., 877 (1958). 54,

Photo-induced solution polymerization Solvent: viscous or non-viscous media Sensitizer: a,a’-azobisisobutyronitrile Temperature: 40°C
Non-viscous media k,=404, kt=1.76 X lo7, k ~ 8 . 0 X 10” 8 Viscous media k,=360 k 100, k,=(7.7 k 2.8) X 104, k ~ ( 8 . 0 -2.6) X 10” t

k,: propagation rate constant, [I/mol*sec] k,: termination rate constant, [I/mol*sec] kf: rate constant of combined transfer to monomer and to solvent, [I/mol*sec]
Benson, S. W. and North, A. M., J, Am. Chem. SOC., 81, 1339 (1959). 0 1959 American Chemical Society.

76

Free radical polymerization

Photo-induced solution polymerization Solvent: ethylacetate Catalyst: a-azobisisobutyronitrile Temperature: -40--20°C Temperature ["C1 -20 -3 0 -40 (ktc+2k,d)x 1W3/k,2 ( I ) [mol sec/l] 1.6 2.8 5.8 kp(2) []/mol sec]

-

24 13.2 5.43-1 1.1

(')From stationary state. (2)From non-stationary state. termination rate constant by combination, [I/mol*sec] termination rate constant by disproportionation, [I/mol*sec] propagation rate constant, [I/mol. sec] Hughes, J. and North, A. M., Trans. Faraday Soc., 60, 960 (1964). Photo-induced solution polymerization Solvent: six different solvents (see table) Sensitizer: azobisisobutyronitrile (AIBN) Temperature: 25°C [MMA]: 4.69 [mol/l], Solvent Benzene Fluorobenzene Chlorobenzene Anisole Bromobenzene Benzonitrile [AIBN]: 6.10X 10" [mol/l]

k, X 10-2 [I/mol*sec] 2.6 2.7 2.8 2.85 3.1 3.3

k, X 10-7 [I/mol*sec]
2.1 2.1 1.95 1.75 1.7 1.7

Methyl methacrylate
[MMA]: concentration of MMA, [mol/l] [AIBN]: concentration of AIBN, [mol/l] kp: propagation rate constant, [l/mol*sec] k,: termination rate constants, [I/mol*sec] Bamford, C. H. and Brumby, S., Mukromol. Chem., 105, 122 (1967).
Photo-induced solution polymerization Solvent: benzene Sensitizer: benzoin (B), benzoinacetate (BA), and benzoinmethylether (BME) Temperature: room temperature

77

S* S*

+
+

M M

4

non-radical products radical products

k, k',

S*: excited sensitizer, M: monomer.

Sensitizer B BA BME

[I/mol] 0.4
15 0.02

kqk

k, [I/mol sec] 4.8 X 10' 8.0X lo8

k,: decomposition rate constant of sensitizer, [ I/sec] kq, k, rate constant for reaction of monomers with excited sensitizers ': which lead to non-radical products and radical products, respectively.
Kuhlmann, R. and Schnabel, W., Angew. Makromol. Chem., 70, 145 (1978).
Photo-induced solution polymerization Solvent: various solvents Initiator: m,d-azobiscyclohexane carbonitrile (ACN) Temperature: 0°C I R" + M + M
---f

- + -

2R0 Pi*
P~+I-

- + -

78
Pno + PI," Ro + PI,' R' + Ro

Free radical polymerization
-+

- + -

+

dead polymer dead polymer product

kt
ktpr

kw

I: initiator, R" : primary radical, M: monomer, P,,' : polymer radicals with n units.
X k,=l63, ktPd/kpki=3.45 1O5 ktPr/k,ki=3 X 105/q, kt=1.43 X 1 07/q .45

rate constant of initiator, [ l/sec] ki: initiation rate constant, [l/mol. sec] k,: propagation rate constant, [Vmol-sec] kt: termination rate constant, [I/mol*sec] ktpr:rate constant for termination by primary radical, [I/mol-sec] k,,fl: rate constant, for termination by primary radical at a viscosity of 1 cP, [l/mol*sec] q: viscosity of solution, [cP] Mahabadi, H. K. and Meyerhoff, G., Eur. Polym. J., 15, 607 (1979).
Photo-induced and thermally-induced solution polymerization Solvent: benzene Initiator: 2,2'-azo-bis-isobutyronitrile Temperature: 0-60°C Maximum conversion: 7%

b: decomposition

Temperature ["C]
ktdkc

O(')

25")
2.13

60'2'
5.75

1.50

'"Photo-induced polymerization. (2)Thermally-inducedsolution polymerization.
ktc: termination rate constant by combination, [I/mol*sec] ktd: termination rate constant by disproportionation, [I/mol* sec]

Methyl methacrylate

79

(1954).

Bevington, J. C., Melville, H. W., and Taylor, R. P., J. Polym. Sci., 14, 463 Copyright 0 1954 John Wiley & Sons, Inc. Reprinted by permission of John Wiley & Sons, Inc.
Photo-induced bulk, thermally-induced bulk, and solution polymerization Solvent: four different solvents (see table) Sensitizer: azobisisobutyronitrile (AZBN) and azobisicyclohexane carbonitrile (AZCN) Temperature: 25-60°C
(1)Photo-induced bulk and solution polymerization and thermally-induced bulk and solution polymerization Sensitizer: AZCN, [AZCN]=l .OO g/1 Temperature: 25°C

Solvent [volYo]

k, X 1O-* [Vmol- sec]
4.1

k, X 1O'6 [I/mol*sec]
42.7 41.1 48.2 30.4 26.9 30.5 26.1 38.9

1-Fluoronaphthalene
45 1-Chloronaphthalene 25 30 45 60 1-Bromonaphthalene 45 4.5 4.8 4.2 4.4 5 .O 4.6 3.7

Toluene
45

2 k.56 2. M.84 1.49 2. [Vmol sec] 6. [mol/l] [AZCN]: concentration of AZCN.0 7..74 1. [mol/l] k.0 8. Polym.X 10-7 [I/mol*sec] 2.: propagation rate constant. 6 .34 1.94 - AZBN AZCN AZBN AZCN AZBN AZBN AZBN AZCN AZBN AZCN AZBN AZBN AZBN AZCN AZBN 1-Fluoronaphthalene 40 40 60 1 -Chloronaphthalene 20 40 40 60 60 80 1-Bromonaphthalene 20 40 40 60 2..6 6.4 8.4 8.13 1. [I/mol*sec] k. [AZBN] or [AZCN]=l .70 1..3 6.2 7. M. Eur. G.80 Free radical polymerization (2) Thermally-induced bulk and solution polymerization Sensitizer: AZBN and AZCN.84 1.OO 8/1 Temperature: 60°C Solvent [vol%] Initiator k X 10-2 .1 7.1 6. G.34 0. G. J.4 6.4 6.9 7.28 [AZBN]: concentration of AZBN.70 1. Cameron.8 7.. M. 823 (1 970). .15 1.56 1. [I/mol*sec] Burnett.74 1.: termination rate constants.4 6. and Zafar.

4 4. and azobisisobutyronitrile (AZBN) used in thermallyinduced polymerization Temperature: 25 and 60°C Reaction medium (parts by vol./kt X 1O3 [I/mol. [I/mol*sec] Cameron.92 6.: propagation rate constant.1 k 0. G. and Cameron.2 k0.6 k 0.3 (')Thermally-induced polymerization (2)Photo-induced polymerization k. Polymer. G.3 20. .4 4. X 10-7 [limo1 sec] - - 3.9 -t 0.4 4.1 k0. n-octane.sec] 15. 14. [I/mol*sec] kt: termination rate constant.29 3.7 k.4 2.3 2.) MMA-toluene ( 5 0:5 0) MMA-toluene-MeOH (50:15:35) Bulk MMA MM A-MeOH ( S O : 50) MMNn-octaneh-nonane (75:5:20) Temperature ["CI 60'" 60'" 25'*' 25'2' 25'2' k. X 10-2 [I/mol*sec] - k. 107 (1973).9 f0. J. and n-nonane (see table) Initiator: azobiscyclohexane carbonitrile (AZCN) used in photo-induced polymerization.. methanol (MeOH).Methyl methacrylate 81 Photo-induced bulk and thermally-induced bulk and solution polymerization Solvent: toluene.50 5.

X lo5 f 60°C 0.2.56 0.a'-azobisisobutyronitrile (AIBN) and a.69 [mol/l].55 0.4-TrichIorobenzene 1 .O 1 Bromobenzene 0.2.68 0.55 0.55 kt/k.1.98 Benzonitrile 1.59 0.57 0.7 1 0.07 1.01 Anisole Benzyl alcohol I .55 0. [mol sec/l] 30°C 300 280 320 [ 1/sec] 60°C"' MMA 0.99 1.2-Dichloroethane 1.1 -Trichloroethane 1.a'-azobiscyclohexane carbonitrile (ACN) Temperature: 30-60°C (1) Thermally-induced bulk and solution polymerization [MMA]: 4.57 0.86 Toluene 0.84 Benzene 0.08 X lo" [mol/l]. [ACN]: 6.98 1.1.2-TetrachIoroethane 190 120 240 180 160 250 340 140 "'The mean value of kd in pure MMA monomer and that in pure solvent.97 o-Dichlorobenzene 0.98 Ethyl benzene 0.82 Free radical polymerization Photo-induced bulk and solution polymerization and thermally-induced bulk and solution polymerization Solvent: thirteen different solvents (see table) Sensitizer: a. solvent: 50 vol% Solvent k.09 Chlorobenzene 0. .

2-TetrachIoroethane 270 270 250 260 300 260 270 270 1. [-I kp: propagation rate constant.2.4 0. T.8 1. Yamamoto.3 1. [ACN]: 6.4 [I/mol*sec] MMA Benzene Toluene Anisole Benzyl alcohol Chlorobenzene o-Dichlorobenzene Benzonitrile 1.7 1 ... T. . [I/mol*sec] Yamamoto.1. sec] k.1-Trichloroethane 260 260 240 1. solvent: 50 vol% 2k. [Vmol.69 [mol/l]. [ l/sec] f: initiator efficiency. 618 (1980).1. T. X loe7 [I/mol*sec] 2.: termination rate constant.2-Dichloroethane 1.86 1.o 1. Yamamoto.o b: decomposition rate constant. M.0 1..9 1. and Hirota.08 X Solvent kP 83 [mol/l]..5 1.Methyl methacrylate (2) Photo-induced bulk and solution polymerization Temperature: 30°C [MMA]: 4. Nippon Kagaku Kaishi.

[I/mol. G. initiator: benzoyl peroxide 1OO"C. thermally-induced bulk polymerization. Hill. Reprinted by permission of John Wiley & Sons. 59 (1960). K. . G. Chem.84 Free radical polymerization Photo-induced bulk and solution polymerization and thermally-induced bulk and solution polymerization Temperature: 25°C k..sec] . solvent: ethyl acetate O'C. M. solvent: Sharples 3B mercaptan (a mixture of tertiary C12 mercaptans). Radiation-induced bulk and solution polymerization and thermally-induced bulk and solution polymerization Temperature: -78. Russell. Moad.. R. Polym. Reprinted by permission of John Wiley & Sons. M..: apparent overall propagation rate constant.1/R){exp( -6925 cal/RT)+exp( -6 150 cal/RT)} h: Plank's constant k: Boltzmann's constant k. G.: propagation rate constant. 851 (1992).. J..Q '-azobisisobutyro- Buback. Polym.. Ed. F. F. k. Copyright 0 1992 John Wiley & Sons. D.. T. A. J.=295"'-299'2) (l) [I/mol-sec] Q bulk or solution polymerization by using nitrile or benzoin as an initiator. Inc.56.100°C -78"C. thermally-induced solution polymerization. radiation-induced solution polymerization. J. T. O'Driscoll. Shen. Sei.=(kT/h)exp( -28. and Winnik. Inc. radiation-induced bulk polymerization 50"C... J.. 30. A. []/mol* sec] Copyright 0 1960 John Wiley Bovey. Inc.. (2) photo-induced bulk polymerization. Sci. Polym. Gilbert. Inc. & Sons. initiator: benzoyl peroxide k.

[mol/l. Eur. Polym.?-CHX).=l.3 X 1 06exp(-5450 cal/RT) k..Methyl methacrylate Radiation-induced bulk polymerization Radiation source: y-ray Temperature: -25-55°C Maximum conversion: 80% R.sec] [MI: monomer concentration. see] k.. L.0H HO(CH2-CHX). 6.=k. k. [Vmol. S. [mol/l] Palma.: propagation rate constant.. sulphuric acid Emulsifier: cetyl trimethyl ammonium bromide Initiator: ferrous ion + hydrogen peroxide Temperature: 25°C Fe3" + HO + OHFe++ + H202 HO + Fe++ + Fe3' + HOHO + CH2=CHX + HOCH2-CHXHOCH2-CHX.. k.+.+ -(CHX-CH2).. [mol/l*sec] R.+ OH + HO(CH2-CHX)"OH + + kl k2 ki k.+ CH2=CHX + HOCHz-CHX-CH2-CHXHO(CH. G. . and Lora.OH HO(CH2-CHX)". J.[ MI R.. Busulini. [I/mol*sec] R.: initiation rate.'"/k.=2.. 453 (1970). k'. 85 Solution polymerization Solution: FeS04 solution.: propagation rate.: termination rate constant. 1 X 109exp(-3 150 cal/RT) k.

22 kpml w2 0..0003 0.003 0.o 1 .53 0.175 0.O 3 .O 3 .: termination rate constant by recombination of active endings. and Kilham.O 0. [I/mol*sec] kZ: rate constant of HO. [I/mol.83 0.934 0.0 1.971 Mo=approx. H.: propagation rate constant.03 0.0 1. J.967 1. [mol/l] .72 3.98 1.67 1.180 0. Emulsifying agent [%I 0 0. 668 (1946). [I/mol*sec] k.70 1.67 1.22 1.2'-azobisisobutyronitrile (AIBN) Temperature: 60°C .86 Free radical polymerization Emulsifying agent concentration [%] M O [mol/l] io4 [mol/l] k&l ktY2 1. Evans.5 0. G. Baxendale.175 0. K.41 kl: rate constant of HO generation reaction.21 1 .957 0. [I/mol-sec] k. Trans.092 0.generation reaction. ao=l 0-4 [mol/l] .175 0.sec] Mo: initial monomer concentration.175 0.153 0..o 1 . 0 1 [mol/l]... [mol/l] a: initial initiator concentration. M. Solution polymerization Solvent: seven different thiols (see table) Initiator: 2.241 0. [I/mol esec] Kt: termination rate constant by free radical. [I/mol*sec] k.46 1.o 1 .22 1.o 3 .483 0. 42. J. Faraday SOC.478 0.: initiation rate constant.175 0.

4757 (1955).: radical.: propagation rate constant.18 k./k 3. k. Chem. J.. M: monomer. [l/mol.: transfer rate constant to thiol. ktd=l.: radical from solvent.: polymerization rate.20Xlo7. S: solvent. R. SOC. R* + M + RR. F. [mol/l. sec] k. k. P: polymer.. ktc=0.. R. 0 1955 American Chemical Society.1 2.Methyl methacrylate Initiation Propagation Monomer transfer Thiol transfer Termination by combination Termination by disproportionation I + 2fR. and Gornick.0X lo3 k.=573. sec] [AIBN]: concentration of AIBN.62 0. sec] ktc: termination rate constant by combination. [mol/l] O’Brien. L.63 0.+M -+P+M* R * + S + P + S * Re + R * + P R.38 0.7 0. [Vmol.04 X 10~5[AIBN]1’2 Solvent 2-Naphthalenethiol Benzenethiol 1-Butanethiol Ethyl mercaptoacetate 2-Mercaptoethanol 2-Propanethiol 2-Methyl-2-propanethiol Cs=k. [I/mol*sec] kill: transfer rate constant to monomer. [I/mol*sec] R. kS ktc ktd I: initiator. S .=4.66 0. [l/mol*sec] kd:termination rate constant by disproportionation. + R e -+ P + P 87 kd k.19X lo7. J. . 77. Am.=3.

7 k. sucrose acetate isobutyrate (SAIB). Shukla. S. 53.a'-azobisisobutyronitrile Temperature: 30°C R.66 0.&.40 1. S.=367 [I/mol-sec] Cs=k..: transfer rate constant to solvent. R. 1O5 X [I/mol. Trans. J.25 1.X io5 k.8 281 1.0 715..0 271.: propagation rate constant.8 623.51 .88 Free radical polymerization Solution polymerization Solvent: seven different solvents (see table) Initiator: 2.. []/mol sec] Chadha. N. 240 (1957)... and Misra. k. Faraday Soc.=K[ MI [1]0.95 146.74 4. and butyl phthalate Initiator: a..6 1666.70 7. G..54 9. Solution polymerization Solvent: ethylacetate.2'-azobisisobutyronitrile (AIBN) Temperature: 60°C Solvent C. [Vmol-sec] kl.sec] Benzene Toluene Ethyl benzene Chlorobenzene Chloroform Carbon tetrachloride Acetone 0.0 3384.

G.: propagation rate constant. [mol/l] [I]: initiator concentration. = k.O X 1025exp( -30450 cal/RT) Initiator efficiency=O. . G. polymer ki k'l M: monomer.60 X lo7 2.. [ I/sec] k. [I/mol sec] 1.M. 859 (1961).: growing polymer radical.6' sec] h: decomposition rate constant of initiator..sec] k. [I/mol-sec] Baldwin. 3.03. : primary radical.Methyl methacrylate Solvent mixture Monomer+ethylacetate (1 :4) Monomer+ethylacetate+SAIB (1 :1:2) Monomer+SAIB (1 :4) Monomer+butylphthalate (1 :4) k.. and Reed. Inc. [I/mol. M.: rate constant for chain initiation by a primary radical. A l .50 [MI: monomer concentration.16X lo6 89 k. + -+ M.2'-azobisisobutyronitrile Temperature: 60°C Monomer concentration: 0.. A. Faraday.A. Solution polymerization Solvent: benzene Initiator: 2. M.00 x io5 2.: propagation rate. Reprinted by permission of John Wiley & Sons. R. 3209 (1963). Copyright 0 1963 John Wiley & Sons. [(l/mo1)0. Sci. J.1 molA R* + M Re + M. Trans./k'. [I/mol.81 X 1O6 4. [I/mol*sec] 229 210 23 5 240 h=l. [I/mol*sec] North.. 57.: termination rate constant. [mol/l*sec] K: overall polymerization constant. [mol/l] R.0 X 10-7 k. Polym. sec] k. Inc. Soc.: rate constant for chain termination by a primary radical.

[I/mol*sec] k: overall polymerization rate’constant.90 Free radical polymerization Solution polymerization Solvent: benzene Initiator: a. Mj+l..: growing polymer I: initiator. Sci.a’-azobisisobutyronitrile Temperature: 30°C Rate I Ro* + M Mj. with j units./kt”2=0.63.. [ l/sec] k. MI. + + 4 + 2Ro. [1”2/mo1”2* sec] f: efficiency of initiator. Reprinted by permission of John Wiley & Sons. M: monomer. b=1. 2901 (1964). + M M.6X IO6 .. + M. k..=k[AIBN]o. f=0. I. f=0. Inc.. 2kt=1 1. k. Copyright 0 1964 John Wiley & Sons.: termination rate constant. (bf/k.[M *][M]=kp(kdf/kt)lR Rt=2kt[M*]* Mj. inactive polymer h a : Ri=2bfII] R. and Imoto. Inc.)’/2 k=3.5[MMA] k=k.103. Ito.A2..=141.15 X IO4. Solution polymerization Solvent: benzene Initiator: a. [mol/l*sec] [i]: concentration of i..=k. J Polym.: polymerization rate. [I/mol*sec] k.7 R.33 X lo-’.: propagation rate constant. M. h=1.a’-azobisisobutyronitrile Temperature: 60°C Maximum conversion: about 15% R. [-3 Otsu.31 X primary radical. [mol/l] b: decomposition rate constant of initiator. T.

K.: propagation rate. 1325 (1968). [mol/l*sec] b: decomposition rate constant of initiator. Kani.: termination rate. [mol/l* sec] R. Jnc. Copyright 0 1968 John Wiley & Sons. and Ishii. J..85 14.: termination rate constant.75 kti/kik.2 5.30 6.4-dimethylvaleronitrile) Temperature: 40-60°C Solvent EA DC DEP DOP EA DC DEP DOP EA DC DEP k.58 0. [mol/l] [MI: monomer concentration.Methyl methacrylate f: initiator efficiency.: initiation rate. [ l/sec] k.68 2.3 11. M.23 9. [I/mol esec] k.012 1..(2&/kt) X 1O 4 [mo1'/2/I'/2*sec] 4. [mol/l] R. [mol/l* sec] R. Polym.40 12.33 3.47 3.1 12.93 5. Reprinted by permission of John Wiley & Sons. 6. A-1.5 7.O 19..8 1.80 25 . Sci. [I/mol*sec] Yokota.: propagation rate constant.44 1. X 10" [mol sec/l] 13..3 Temperature ["CI 60 60 60 60 50 50 50 50 40 40 40 . Solution polymerization Solvent: four different solvents (see table) Initiator: 2. Inc.780 1. Y.T-azobis(2.25 5. 91 [-I [M -1: total polymer radical concentration.

: initial polymerization rate. Sci. [ l/sec] k. [mol/l].=k[MCD]0. [I/mol*sec] Copyright 0 1971 John Wiley Ito. [1°~S'/mo10~5' sec] [i]: concentration of i. DEP: diethyl phthalate. 529 (1971). T.. and Imoto. [I/mol*sec] kti: termination rate constant by to primary radical. & Sons.: propagation rate constant. [Vmol-sec] ki: initiation rate constant.. Macromol. A5..42 X 1012exp(-25. Polym. Sci. .. Inc. DC: dimethyl carbitol. Reprinted by permission of John Wiley & Sons.5 kcal/RT) for 60-90°C Overall activation energy=l8.95 b=7. [MI: monomer concentration. [mol/l] b: decomposition rate constant of initiator. Wada. DOP: di-n-octyl phthalate.56[MMA]o. K.3 [kcal/mol] for 40-70°C For polymerization with DDM b=1. A-1. 2541 (1971). [mol/l] f: initiator efficiency. []/mol ssec] kt: termination rate constant.7% (MCD) For polymerization with MCD R. J. J. [-1 b: decomposition rate constant of initiator.32 X 1013exp(-27. Solution polymerization Solvent: benzene Initiator: p-methoxy-p'-cyanodiphenyldiazomethane(MCD) or diphenyldiazomethane (DDM) Temperature: 50°C Maximum conversion: 2.-Chem. [mol/l*sec] k: initial polymerization rate constant. Inc. 9. [ l/sec] Nakaya. H.. [C]: initiator concentration.8 [kcal/mol] for 50-80°C R.7 kcal/RT) for 50-80°C Overall activation energy= 15.92 Free radical polymerization EA: ethyl acetate. M.

9 10.47 3. products R. M.2 25.3 8.47 4..96 3.p-Dichloro-diphenyl ether (DCDPE) Diethyl malonate (DEM) Phenyl salicylate (PSC) Diethyl phthalate (DEP) Dioctyl phthalate (DOP) Dimethyl glycol phthalate (DMCP) 93 k.36 5. 219 (1972). X. + P.2'-azobisisobutyronitrile Temperature: 60°C C -+ 2R. + M X.9 7.5 6.9 17.9 6.36 8. X 1 0-6 kp X 1 0-2 [MMAI [mol/l] [I/mol.. P. P. X. [I/mol*sec] kt: termination rate constants. M.3 1 6.6 18.0 k.Methyl methacrylate Solution or bulk polymerization Solvent: nine different solvents (see table) Initiator: azobisisobutyronitrile (AIBN) Temperature: 60°C Solvent Diethyl ether (DEE) MMA Methylbenzoate (MB) Phenyl ethyl bromide (PEB) p.94 5. Xi.57 2. 2R. Solution polymerization Solvent: benzene Initiator: 2.894 36.sec] [I/mol. Chem.4 6. [Vmol.0 14.4 6.36 4.. or P.sec] 5. + + + + + kd ki kP +M + X. 157.5 6. kt kti ktii .. Xr+l..4 7.0 6.64 5..68 1. + R.79 0.8 13. sec] Zafar. Makromol.: propagation rate constant.6 6.

kti/kik.94 Free radical polymerization C: initiator.. kli/kikp=5250 b: decomposition rate constant of initiator.. X. K. Bull. [mol/l sec] ktii: termination rate constant. : primary radical. SOC. M: monomer.2'-azobis(2. S: solvent. units.: termination rate constant by primary radical. [mol/l*sec] kp: propagation rate constant. [I/mol*sec] . M: monomer. [ I/sec] ki: initiation rate constant.. + S T + polymer T + M +Xi + + - C: initiator. R: primary radical. [mol/l*sec] Ito. polymer R + R + product X. + M &+I X.: growing polymer radical with r units. [I/mol-sec] k. Chem. T. X. [mol/l.: polymer radical with n kii=4 X lo9. 1758 (1973). T: solvent radical. R .: propagation rate constant. and Matsuda. Solution polymerization Solvent: diethyl phthalate Initiator: 2.=3. [ Usec] ki: initiation rate constant. + X. Japan. sec] kt. Pr: dead polymer with r units.09 X lo3 [mol. [mol/l. -+ polymer R + X.sec/l] b: decomposition rate constant.4-~aleronitrile) Temperature: 50°C Maximum conversion: 10% C + 2R R + M +XI X. 42. sec] kt: termination rate constant.

3 11. [moI. [Vmol.2’-azobis(2.: termination rate constant by primary radical. sec] b: decomposition rate constant of initiator.Methyl methacrylate k.: termination rate constant. sec] k. Reprinted by permission of John Wiley & Sons.: reinitiation rate constant by solvent radical.sec/~] Bz-MMA (3:l) Bz-iPA-MMA (1:2:1) Bz-iPA-MMA (2:13:5) iPA-MMA (3:1) Ea-MMA (3:l) DC-MMA (3:l) DEP-MMA (3:1) 2. J.O 2.93 15. Polym. [I/mol-sec] k. Inc.secl kJk. Copyright 0 1974 John Wiley & Sons. diethyl phthalate (DEP) Initiator: 2.0 8. [Vmol.68 2. [I/mol*sec] k.) I/’ AX io4 Solvent [1’/2/mo1”2. [I/mol*sec] ki: initiation rate constant. [I/mol-sec] 95 Ito.i: rate constant of reaction between primary radicals.12 2.sec] k.. [I/mol.9 5 .0 14. ethyl acetate (Ea). [-3 .: propagation rate constant.11 1. [I/mol.sec/~] 154 137 135 138 218 101 40 kli/103k.k. [moI. [I/mol.2 5. isopropyl alcohol (iPA) dimethyl carbitol (DC). sec] kti: rate constant for termination by primary radical.25 k. Ed.00 2.4-dimethylvaleronitrile)(ABVN) Temperature: 50°C A= kp(fkd/k. K. Inc.: termination rate constant.14 2. 12. Chem. Sei. Solution polymerization Solvent: benzene (Bz). 1263 (1974). [I/sec] f: initiator efficiency...47 3. Polym. sec] ktr: transfer rate constant to solvent.

.. [I/mol*sec] k.: activation energy for initiation. [-3 E.5. Et=Epd=2. .: propagation rate constant.=l. P. 8684k. Ei=19 IQ: decomposition rate constant of initiator.Rdk. Inc. [kcal/mol] E. Copyright 0 1974 John Wiley & Sons. [I/mol-sec] kt: termination rate constant. []/mol sec] k. [mol/l] [I]: concentration of initiator./[I] [M])=Iog(2f&k.=l/P.: termination rate constant by primary radical. Reprinted by permission of John Wiley & Sons.87. S. [I/mol*sec] R. Solution polymerization Solvent: benzene Initiator: azobisisobutyronitrile Temperature: 60°C log(R. [mol/l*sec] [MI: concentration of monomer.o-k~Rdk~[M]2)(kikp[M]2/kp~RJ k. Inc. K...O+( 1/P.: propagation rate. [-I ki: initiation rate constant. and Kapoor. 2f&ki/kt= 1 1. [ l/sec] initiator efficiency.. C. J . 477 (1979).: activation energy for propagation.-1/Pn.. 12.70.Jkik. [-I P..[ MI2 l/P. [mol/l] P. fk=0. Ed=3 1. 2581 (1974).45 X 104./kt)-O. [kcal/mol] Ep.96 Free radical polymerization Ito. 15. Sci.: number-average degree of polymerization.4 X 10-6.o: number-average degree of polymerization without primary radical termination. Eur.. Polym. [kcal/mol] Et: activation energy for termination. J Polym. [kcal/mol] fk: Deb. K. h=9.: activation energy for termination by primary radical.35 X 1O-'. Ep=4.k.

33 4.72f0.30 4.38 0.99f0.56f0.29f0. monomer concentration: 2 [mol/l] Solvent C~HS-OCH~ C6H6 C6Hs-F C~HS-CI C~HS-CN C6D6 kP k. X 1 Om7 3.Methyl methacrylate Solution polymerization Solvent: various aromatic solvents (see table) Initiator: 2.47 3.20 506 f48 450f33 448f47 498f39 614f43 456 k29 * . monomer concentration: 2 [mol/l] Solvent 97 (k./k.19 4.2'-azobisisobutyronitrile (AIBN) and 2.66 4.) X 1O3 71. at 30"C.82 4.. at 30°C.2'-azobiscyclohexanecarbonitrile (ACN) Temperature: 20-40°C Initiator: AIBN.78 9.26 5.39 4.20f 0.45 Initiator: ACN.

.8 [kcal/mol] Activation energy of k.=0. initiator: AIBN. Polym... M. S. sec] k. initiator: AIBN. D.38 k0.1 [kcal/mol] k. k..: propagation rate constant.0f 0.20k0. [I/mol*sec] Kamachi.0 3 .98 Free radical polymerization Effect of monomer concentration on rate constants (solvent: benzene.54 4.o 2.46 * Temperature dependence of rate constants (solvent: benzene.20 0. 41 (1981).05 k0.09k0. J.O k.37 4. Liaw. . 13. and Nozakura.20 IL 0. monomer concentration: 2 [mo1/1]) Temperature ["CI 20 30 40 kP [I/mol-sec] kt X 10-7 []/mol* sec] 4. X 10-7 427k38 450 k33 454 36 * 3.30 4. at 30°C) Monomer concentration [mol/l] 1. J.38 -t 0.72 301 k 3 6 450 k 33 596k71 Activation energy of kP=5. [I/mol.: termination rate constant.30 4.

0 1989 American Chemical Society. K..Methyl methacrylate Solution polymerization Solvent: see table Initiator: 2.88-9. for solution polymerization kp: propagation rate constant.+ + 2R* PI* Pn+l* P” + Y . dimethyl carbitol (DC). + M 4 PI.39 kP [I/mol. for bulk polymerization Average of kp=295k 12 [I/mol*sec]. C. F. + PI.. 22. P. + PI.39 1.39 9. and Winnik. + Y -+ PI. 5 x 10” 10” 5 x 10” 5x Additive Monomer concentration [mol/l] 9. P.. O’Driscoll.* + M + PI.m) . kd ki kP ktv ktd(n.. Piton. and DE Initiator: AVBN Temperature: 50°C Initiation Propagation Chain transfer Termination by disproportionation I R.. M. Macromolecules..sec].39 7.. T.5 1-9. MEOH: methanol Average of kp=294k9 [l/mol. 2785 (1989). Solution polymerization Solvent: good solvent benzene (BZ). [I/mol sec] Davis.2’-azobisisobutyronitrile (AIBN) and benzoin (BZ) Temperature: 25°C 99 Initiator Initiator concentration [mol/l] 5 x 10” io-*. A.sec] AIBN BZ AIBN AIBN AIBN EA MEOH Polystyrene 292 297 295 292-304 296 EA: ethyl acetate.39 9. benzene-isopropyl alcohol (BZ-IPA). M.

rn)=kt*(xn)-2a/q Rp=(2fdkt/kt*)q0. .in)+ktd(n. [Vmol sec] kt*: a constant.+. [I/mol-sec] q: solvent viscosity Mahabadi. Macromolecules..: number-average degree of polymerization. [I/mol*sec] kl(n.l. H.in)=ktc(n. [mol/l*sec] X. [I/mol-sec] k.in) 2fkdkt/kt*=1. M: monomer.in)=ktO(nm)-a kt(n.m) I: initiator.: propagation rate constant.ml:termination rate constant. 606 (1 99 1).: primary free radical. [Vmol-sec] ktc(n. Pn: dead polymer with n units. 0 1991 American Chemical Society.100 Free radical polymerization Termination by combination Piis + Pin* + Pi. Pn*:growing polymer radical with n units. [-I b: decomposition rate constant. [ I/sec] k.70 X a=0.ln): termination rate constant by disproportionation.: initiation rate constant.. kt(n. Y: chain transfer agent.0995 &: polymerization - rate. [I/mol sec] ktd(. R. 24.rn): termination rate constant by combination.5[M] [I]o.5(Xn)a kt(n. ktc(n. [I/mol*sec] ktV: transfer rate constant to species Y. K.

CH3M.73 1. CH3M.8 147.Propylene 1.2 Activation energies Rate constants k ki kP kt Activation energy [kcal/mol] 24.4 5. CH3Mx:dead -d[M]/dt=kp(2ki/kJ[M] [C] I/’ k=kp(2ki/kt) Rate constants Temperature [“CI 135.77 4.?MX+. : growing polymer radical with x units. polymer with x units. + M CH3M2.6 0 .6 Propylene Bulk polymerization Initiator: tert-butyl peroxide Temperature: 130.165°C Phase: gas (CH3)3COO(CH3) 2CH3COCH3 + 2CH3. + M CH3Mx*+CH3My*+(CH3).8 38. CH3. CH3Mx*+CH3MX* ( C H ~ ) Z M ~ + ~ + + + + 101 ki k P k P kt ktl2 M: monomer.9 k [I”2/moI”-2-sec] 0.07 160. CH3M.

and Volman. Chem.4/RT) [MI: concentration of monomer. [mol/l] k: polymerization rate constant. 79.: propagation rate constant. [1'/2/mo1'/2sec] * ki: decomposition rate constant of initiator. Soc. L.: termination rate constant.2996 (1957).6 X 106exp(-38. [Vmol. [mol/l] [C]: concentration of initiator. 0 1957 American Chemical Society. .102 Free radical polymerization ki=l . D. H. J. Am.. [I/mol*sec] k. [ l/sec] k.sec] Landers.. C.

[Vmol. [I/mol. +2 2R. ktr/k. [Vmol. : primary free radical.Styrene 1.: thermally-initiated initiation rate constant.. [l/mol*sec] ktc:termination rate constant by combination. M.Am.7 Styrene Bulk polymerization Initiator: benzoyl peroxide Temperature: 60°C 2M 2M. . [I/mol*sec] k. A.: propagation rate constant. Gregg. [I/mol*sec] k. and Matheson. sec] k. [ I/sec] k. + 2M + 2M.sec] k. 1691 (1951)..: initiation rate constant. M. - 0 1951 American Chemical Society. Chem. F.. R.=O. S. 73. sec] Mayo.: rate constant of reaction between primary radicals.+ 2 polymer M. R. Sci. (monoradical) Ma + M M * Me + M polymer + Me Me + M . 0 5 5 k. [I/mol*sec] ktd: termination rate constant by disproportionation.. + M 1 polymer (coupling) + Bz202 ---t polymer + R. J. --+non-radical products 2R. R. [I/mol*sec] kd: decomposition rate constant of initiator. + + + + 103 M: monomer.: transfer rate constant of monomer. M : growing polymer radical.. B z ~ O ~ R.: transfer rate constant of initiator.=6 X 10” kI/k.

2'-azobisisobutyronitrile(AIBN) and dicumyl peroxide (DCP) Temperature: 30.16.14 kp: propagation rate constant. 2-azobisisobutyronitrile(AZO).0 2 3 6 6 7.sec] ktd: termination rate constant by disproportionation. Bulk polymerization Initiator: 2..6-1 00.: transfer rate constant to monomer...104 Free radical polymerization Bulk polymerization Initiator: dimethylanilinebenzoyl peroxide (DMABP). J Polym. [Vmol-sec] E.=2(ktc+kdC*I2 .=13. Inc. and Offenbach.: termination rate constant by combination. . [kcal/mol] Tobolsky. Copyright 0 1955 John Wiley & Sons.in/kpx 1o5 0 30 45 60 70 80 90 DMABP AZO AZO BPO and AZO AZO DTBP DTBP 50320 5210 2190 86 1 494 286 183 ca.311 (1955).. Reprinted by permission of John Wiley & Sons. and di-tert-butyl peroxide (DTBP) Temperature: 0-90°C Temperature ["C1 Initiator (2ktd+ktc)/k.. 59.. Sci. V.3"C for AIBN.. Inc.0"C for DCP Ri=2&[I] Rp=kp[C*I[MavI R... [Vmol-sec] kt. [mol sec/l] - ktr. []/mol sec] kt.5 ktr. benzoyl peroxide (BPO)....5 8.6 kcal/RT) El.: activation energy for k.. J. 22exp(-5. [Vmol. A.5-85.in/kP=O.

89 x 7.80 X 10I4exp(-30.~ 1 O-' IO-' 10-4 b '=9.46 kcal/RT) .2 76.08 x 1.+ combination and disproportionation products Temperature LOCI 30. 5 8 X 10'5exp(-30.44 X 1.5 50.28 x 1.3 bf' [ 1/sec] 6.68 X 10-4exp(12.5 37.0 55.0 67.62 A' =5.Stvrene 105 (1) AIBN Temperature: 30-85 "C Azo I + [2(CH3)2CCN] + N2 [2(CH3)2 CCN] + (CH3)2CCNCCN(CH3)2 + disproportionation products [2(CH3)2CCN] + 2(CH3)2CCN 2(CH3)2 CCN + (CH&CCNCCN(CH3)2 + disproportionation products (CH3)2 CCN + P.84 X 1.2 85.8kcal/RT) f=0.44 x 2.29 X IO-* 1o .84 X 5.0 45.8 kcal/RT) f b = l .

0 72.0 x io-' 1.27X - 4. J PoZym.70 X 1.0 68.6 60.4kcal/RT) R. [mol/l*sec] kd: specific decomposition rate constant of initiator.0 1. [l/mol-sec] ktd: specific termination rate constant by disproportionation. [ l/sec] k. V. and Tobolsky.7X lo-' 3.. [I/mol*sec] ktc: specific termination rate constant by combination. J. Reprinted by permission of John Wiley & Sons. A.100 "C Temperature ["CI 59. [I/mol*sec] [I]: concentration of initiator.5 x h f ' = 1 . [mol/l] f: initiator efficiency.3 85. Inc. [mol/l esec] R. Sci.0 76.3 94. .429 (1958). [mol/l sec] Rt: termination rate..04X - kt& 5.106 (2) DCP Free radical polymerization Temperature: 60.35 X 106 3. Inc.~ 7. [mol/l] [Ma"]:average monomer concentration.86 x 1o .5 kdf ' [ 1/sec] 1. [-I Van Hook. [I/mol* sec] ktr: transfer rate constant.5 84.62 X 1 0 6 100.: propagation rate constant.OO X 106exp(-36. Copyright 0 1958 John Wiley & Sons.: propagation rate.: initiation rate. P.33. [mol/l] [C*]: radical concentration.

R*: primary free radical. 80.. [I/mol*sec] k.60 kd/kt”2=0. Chem. [mol/l] [Catlo: initial concentration of initiator.* + M+ P. sec] f: initiator efficiency. [mol/l] h:decomposition rate constant of initiator. M: monomer.: propagation rate constant. V.*: growing polymer radical containing n monomer units. A.5927 (1958). SOC.+I* Pn* + Pin*+ Pn+m --f Rate 2kSl kSdR*I[Ml vab[R*1[p* 1 k‘lSR*I[PI kdR*l2 kw[P*I[Ml kab[P*]* I: initiator. [MI : initial concentration of monomer and concentration of monomer when time reaches infinity. J.f”~[Cat]0”~/k~~’~h’’~ kd= 1.60 x 10” f=0.Styrene Bulk polymerization Initiator: 2-azobisisobutyronitrile ‘Temperature: 100°C -In ([M]~/[M]0)=2k.2’-azobisisobutyronitrile Temperature: 40-70°C I + 2R* R* + M + RM* RP R* + P* R* + P + RH + P* R* + R* + non-active product P. P. P*: growing polymer radical of any size. Bulk polymerization Initiator: 2. [ l/sec] k.. [-I Tobolsky. .: termination constant. P. respectively. [I/mol. 0 1958 American Chemical Society. Am..0915 107 [MIo.: dead polymer containing n monomer units.

76 0. [I/mol* sec] T: temperature.0739 0.. S. [mol/l] .71 0. and Olive.0093 kJktlR h x io4 [11’2/mo11/2 ~ c ~ ’ ~ [l/sec] s ] - f 0.71 0.0592 0.0337 0.02 12 0.: decomposition rate constant. [Vmol-sec] kab: termination rate constant.kd”2f’/2 [Cat]112[M]/kt1/2 ~ Temperature [“CI 60 70 80 90 100 100 [Catlo(’) [mol/l] 0.08 18.09 15 0. [ l/sec] kSt: initiation rate constant.341295/T IOg(kab)=8.02 14 0. G. [I/mol*sec] kK: inactive reaction rate constant between primary radicals.26-2475/T 1og(kw)=6. [Vrnol-sec] k.09 15 0. Chem. [I/mol*sec] klab: rate constant of termination by primary radical.2’-azobisisobutyronitrile Temperature: 60.0 0..108 Free radical polymerization log(k.12 0. [OK] Henrici-Olive.02 10 0.60 5.1YO d[M]/dt=k. [I/mol* sec] Ptr: transfer rate constant of primary radical to polymer.42-1 15/T k.71 0. Bulk polymerization Initiator: 2.02 16 0. [mol/l] [Cat]: concentration of initiator.0 18.045 1 0./kab)=4.100°C Maximum conversion: 97. 7 1 ( I 960).6 1 “’Initial concentration of initiator [MI: concentration of monomer.0341 0. 37.71 0. [mol/l] [Catlo: initial concentration of initiator.: propagation rate constant.45 1. Makromol.

X lo-' [I/mol*sec] 7. D. Chem.. C. polymer P. P. k. A. [I/mol*sec] 109 Tobolsky... R. [l/mol. [I/mol. J. R.89 (1961).: initiation rate constant. [-I b:decomposition rate constant of initiator. SOC. [ l/sec] k.. Pr: growing polymer radical containing r monomer units.. sec] k. M. Rogers. and Brickman. Am. sec] k.: termination rate constant.: propagation rate constant. M: monomer. and Patrick. C. [Vmol sec] k. + R polymer 2R + product + + ---f k'. kt k't krrt R: primary radical.: termination rate constant. [I/mol. kP [I/mol sec] k'P [I/mol*sec] 2k. 1277 (1 960).Styrene f: initiator efficiency. sec] krtt: constant for reaction between primary radicals. [I/mol*sec] rate Allen.: propagation rate constant.0 176 1100 k'. 0 1960 American Chemical Society. + P. [I/mol*sec] k'. Bulk polymerization Initiator: azobisisobutyronitrile Temperature: 60°C Initiation Propagation Termination +R R+M+P1 Pr + M Prtl P. E. E. V.: rate constant for termination by primary radical. Mukromol. Chem. 48.82. ..

1 X X kPi:initiation rate constant.2/(k. + R5' MI.. + % * M.57 X (3) Radiation-induced solution polymerization Sensitizer: azobisisobutyronitrile Solvent: carbon tetrachloride Temperature: 60°C k.+ - Termination + I: initiator. Pn+m M.~/k..= 1 .+kId)=5. Mn.=6X klrl/k.klr~/k.. + M + Mn+l* M.s/k.52 X 1 0-4. k=l..=O.. + Mi. + R .: propagation rate constant. + M + P . Ri. + S P.. + P.. (1) Bulk polymerization Initiator: azobisisobutyronitrile Temperature: 60°C kp2/(klc+ktd)=5.2/(klc+kld)=5 . solution.s/k.. : primary radical.sec] k. + M + P. + R i * + P.. k. .. MI.=l. + I P.: growing polymer radical containing n monomer units. 1 X 10-2 k. P.=6 X lo". + M + M * * Mn.. S: solvent.: dead polymer containing n monomer units.52 X los4.52 X k. and radiation-induced solution polymerization Formation of primary radicals Initiation of polymerization Propagation Chain transfer I + R1 Ri.=6 1O'5. M. [I/mol.110 Free radical polymerization Bulk.+ . [Vmol-sec] .=O.~/k..k.57 X l o 5 (2) Solution polymerization Initiator: azobisisobutyronitrile Solvent: carbon tetrachloride Temperature: 60°C k.. . k=l.. kt.l/k. M: monomer.

58.=4.. 121 (1962).sec] ktr. 123 (1962).73 X lo4 at 50°C 2kikr'4/k'. 2kik1'4/k'.: polymer radical containing r monomer units. [I/mol*sec] ktrs:transfer rate constant to solvent.. [I/mol. [ l/sec] k'2: initiation rate constant. [Vmol. [I/mol.+. Bulk polymerization Initiator: phenylazotriphenylmethane Temperature: 50-60°C C 2R. [I/mol*sec] Misra. [ l/sec] 111 Manabe. P. Hafeez. 51. Sci.Styrene k. [Vmol.. Inc. + Re + P.sec] ktrM:transfer rate constant to monomer. Utsumi. + M + X l . Copyright 0 1962 John Wiley & Sons. [I/mol. + product --f ki k'2 k2 k4 k'4=ak4 k"4 =a2 k4 C: initiator. + P. A. J.: polymer molecules containing r monomer units.: primary radical. + X. G.. and Sharma. + P.. R. 2R. sec] k: decomposition rate constant of initiator. Chem. [I/mol.=6... or P. S. X.: termination rate constant by combination. Inc.. S. sec] k'4: rate constant for termination by primary radical.8 X lo5 at 60°C ki: decomposition rate constant. [l/mol*sec] ktd: termination rate constant by disproportionation. sec] k"4: rate constant for reaction between primary radicals. XI* + M + Xr+l X. and Okamura. T. . []/mol * sec] k4: termination rate constant. Reprinted by permission of John Wiley & Sons. Makromol.. T. Polym..: transfer rate constant to initiator. R. [I/mol*sec] kZ:propagation rate constant... S. XI.sec] kIti: termination rate constant by primary radical. K.

+ M . 1758 ( 1 969). K.sec] k. 0 1968 American Chemical Society. Bull.: dead polymer containing r monomer units. Phys. [l/mol.216 (1968). kti/kik.. Bulk polymerization Initiator: 2.. J. [I/mol. . A. P.. B. W.Japan..+ P. 42.: growing polymer radical containing r monomer units. sec] Ito. and Matsuda. Xr*+ Re P.. 2 R * + product --+ kd ki k. [I/mol*sec] k.: termination rate constant. M: monomer. [I/mol.: propagation rate constant.: propagation rate constant. + P.t X l * X. and Smith.+. [I/mol..2'-azobisisabutyronitrile(AIBN) and benzoyl peroxide (BPO) Temperature: 60°C C -+ 2R. SOC. Re : primary radical..36 X 1 O4 for AIBN kti/kik. 72. T. R. Chem. [Vrnol. + X.23 X 1 O3 for BPO kd: decomposition rate constant.= 1.=l . + M + Xr+l. sec] ktii: rate constant for reaction between primary radicals . Chem. kti ktii C: initiator. X.sec] k. [I/mol-sec] kti:rate constant for termination by primary radical . or P.=710-t kt: termination rate constant. X. J.112 Bulk polymerization Initiator: benzoyl peroxide Temperature: 60°C Free radical polymerization kt/k. [ l/sec] ki: initiation rate constant. sec] 115 May. k.

+ polymer-P R.=kt"2(k&I] +kMiH [AH] [MI) '12/kp[ M]+k. + Ph. + M + R.2 X 1O4 [I/mol*sec] pi= 1 x 1 o5 [!/mol sec] kp=l..= x 1o .~/k. + C02 BzO.H[ M ] + k t r ~Rith+Ri)'I2/(2kt)'12} MI2/ ~( kmA=l x [I/moI. Ph*+M-+R* R.[I/mol*sec] 1 ~ ~ h f = 2 x 1 o .+ ktr~~[AH]/kp[M]+ktr~[ II/kp[MI+ktrt[I I/kp[MI [A H ] = ~ ~ D A [ { krDA+kM.[ 1/set] 1~c02=4. + polymer-T + (=2R. + M + R. BzO.) Propagation Chain transfer Termination Primary radical termination R~II.45 X lo2 [I/mol.sec] krDA= 1.sec] . + AH + Re + polymer-T R.= 1.=~~MIH[AH] [MI=2kit1i[MI~ Ri=2k&l] Rp=d[ M]/dt=kp( Ri+Ritll)'l2[MI/( 2kt)'12 1/Ti .8 io3 [ l/sec] x k. + M + Re + polymer-T R * + Bz202 --+ Bz202 * + polymer-T polymer-T Re + Re Re + BzO.3 x 1 w4 [ 1/SeC] kMl1.Styrene Bulk polymerization Initiator: benzoyl peroxide Temperature: 60°C 113 Initiation 2M + (=AH) H HPh AH + 2M AH+M+ H Ph -+ B ~ 2 0 2 2Bz0.

sec] kt=1. [g-moM sec] R. [g-mol/l] [I 1: concentration of primary radical. and Coco.5 ktrM=l x 10” [I/mOl* SeC] ktrl=8[I/mol...:number-average degrees of polymerization.. J.+ AH + R .500 (1970).7X IO7 [I/mol-sec] k p ~ ~ X 6O9 [I/mol*sec] =1 R. + polymer-P R . Macromolecules.114 Free radical polymerization ktrAH= X 1O2 [I/mol*sec] 1. [g-mol/l] Pryor. [g-mol/l] [I]: concentration of initiator. + R. [g-mol/l * sec] PI. [-I [MI: monomer concentration. 3.4 (=2R*) kMIH Propagation Chain transfer AIBN + 2IBN IBN. H.: rate of thermal initiation. A. W. [g-mol/l] [AH]: concentration of AH. 0 1970 American Chemical Society.+ polymer-T R.+ polymer-T Re + AIBN + R .: rate of polymerization including both thermal initiation and initiator-initiation. R * + M + R. Bulk polymerization Initiator: azobisisobutyronitrile Temperature: 60°C Initiation 2M+ AH ---f qph (=AH) 2M ktDA AH+M-+ a H Ph krD. [g-mol/l*sec] Ri rate of initiation by initiator.+ polymer-T .. + M + R .

~ A ( R ~ ~ ~ + R ~ ) ” ~ / ( ~ ~ I ) ” kmA= 1 x 1o .: rate of polymerization including both thermal initiation and initiator-initiation.+ k~r~~[AH]/kp[M]+ktr~[II/kp[MI+ktrr[r ’ I/kp[MI {~ ~ D } [AH]=~~DA[M]~/ A + ~ M I I ~ [ M I + ~ . [g-mol/l*sec] PI.:number-average degrees of polymerization. [g-mol/l] [I]: concentration of initiator.3 x 1o‘4[ l/SeC] kMIH=l IO-* [I/moI*sec] x kdf=6 X 1 0*6[ I/sec] k.5 x 1 o2 [I/mOl’ SeC] 1 klrM= x I 0” [I/moI sec] kIrl=5[I/mol*sec] kl= 1. [g-mol/l*sec] R.45 X 1O2 [I/mol*sec] ktrAH=l . J.sec] kp= 1. [-I [MI: monomer concentration. 3. W. [g-mol/l*sec] Ri: rate of initiation by initiator. and Coco.[I/moI sec] ~ krDA=l. [g-mol/l] Pryor.=k1”2(k&I]+kMlH[AH] [M])’/2/k.[M]+klr~/k. A. + Re + polymer-T Re + I B N .=3 X lo3 [I/mol. H. [g-mol/l] [I -1: concentration of primary radical. 500 (1970). [g-mol/l] [AH]: concentration of AH. 0 1970 American Chemical Society. 4 polymer-T 115 kt ~PRT R ~ I ~ ~ = ~ ~ M I H [ A HMI3 [M]=2ki11i[ ] Ri=2kdflI] Rp=d [M]/dt=kp( Ri+Rilh)lR[MI/(2kt)’l2 1/Pl.7 X 1O7 [I/mol*sec] k p ~ ~ X 8 O9 [Vmol sec] =1 - - RiIh: rate of thermal initiation.. . Macromolecules.Styrene Termination Primary radical termination R.

E. X 10-4 [mol.3 - R. 167 (1972).3 0 0.45 0. E.116 Bulk polymerization Initiator: benzoyl peroxide Temperature: 50-90°C Free radical polymerization d [M]/dt=-kp[MI [R*] k.2'-azobisisobutyronitrile Temperature: 45°C Maximum conversion: close to 100% [MI[C]'12/Rp=(kt/&kl)'I2+k1i[C]'"/kik.: polymerization rate.3 0..9 f kli/kik.5 0.18 1. N. [I/mol. sec] [MI: concentration of monomer.[ MI X kt/fk: [mol * sec/l] 3. Mukrornol.. V.sec/l] 0 5 30 31 26 10 4 0. 157.39 0. S. [mol/l*sec] [MI: monomer concentration.: propagation rate constant..7 0.45 0.9 0.270 1.5 0.4 X 1 08exp((-9000k400 cal)/RT} k.45 0. Chem.8 0.=2.2 0. [mol/l] Bresler..8 5.6 0. Bulk polymerization Initiator: 2.180 567 167 26.730 2. [mol/l] . [mol/l] [R*]: concentration of free radicals.N.4 0.. Kazbekov. N. V. and Shadrin.9 0. Fomichev.

J. R2. [I/mol. Reprinted by permission of John Wiley & Sons. or P. Chem. [-I f: initiator efficiency. Polym.+ P. Sci.. Inc. 13. Bulk polymerization Initiator: benzoyl peroxide Temperature: 30-80°C Decomposition primary decomposition secondary decomposition induced decomposition Initiation primary initiation secondary initiation third initiation Transfer to initiator Termination polymer radical termination primary radical 1 termination primary radical 2 termination kid P. Copyright 0 1975 John Wiley & Sons.. + P. sec] k..Polym.. sec] kp: propagation rate constant.i: rate constant of primary radical termination. Ed.: initiation rate constant. [mol/l] x: conversion. [I/mol. * R2-P + . + P.Styrene [C]: initiator concentration. [ l/sec] k..+ P . K.. [l/mol*sec] 117 Ito... [-I b:decomposition rate constant of initiator.401 (1975). RI-P R I . [I/mol*sec] kt: termination rate constant.+ P. Inc. -.

~+I* P. Bulk polymerization Initiator: 2.l)=-l3. K.3: third initiation rate constant./kpk..6 (k J/mol)/RT In(kid/kp)=4. R.. and Meyerhoff.I kp)=-31.30+38.1 07. C. M: monomer. sec] Berger.: polymer radical termination rate constant.8.2:secondary initiation rate constant. R.118 Free radical polymerization In( 2&. P. + P. P. [I/mol. sec] k. [Vmol.0 (kJ/mol)/RT 1 In(ki. Re + M + P I * PI.2'-azobisisobutyronitrile Transfer agent: 1-butanethiol Temperature: 50-70°C I 2R. [I/mol*sec] ktr. Deb. [I/mol. ktp.2: secondary decomposition rate constant. + P. : growing polymer radical containing n monomer units.39+37.58+88. 10.78 (kJ/mol)/RT kd.65 (kJ/mol)/RT In(h. [I/mol*sec] kPd.l)=.l: primary initiation rate constant.=5 X 1O-'exp( 12915 cal/RT) ..2: primary radical 2 termination rate constant. -+ dead polymer R. Macromolecules.[:transfer rate constant to initiator. [I/mol sec] kprt...11-19.. + R. [I/mol*sec] ki.. 1075 (1977)..408 . Pn:dead polymer containing n monomer units. 0 1977 American Chemical Society. -+ product + + I: initiator...27 (kJ/mol)/RT In(kp. 1)=26. [I/mol sec] ki. C. : primary free radical. + M P.. G.sec] ki.?/ki. [Vsec] h.l: primary decomposition rate constant. [Vsec] kid:induced decomposition rate constant.3/ki.I/ki..]: primary radical 1 termination rate constant.39. + P.

Y. [I/mol-sec] k. F.94 1 O7 X k. [I/mol. sec] ktd: rate constant for termination by disproportionation. J. H. ktc ktd [I]: initiator.: propagation rate constant. Polym. 178. [I/mol. [R]: primary free radical.1 k. [PI.=187. [MI. kt=kt. k. [ l/sec] k. sec] kl~ll.+ [MI. [I/mol*sec] ktm:rate constant of reaction between primary radicals..453 (1981). + [A]+ [PI. F.. K.2629 (1977).. []/mol sec] Mahabadi. .: dead polymer with j units. []/mol* sec] Kuo. and Chen. Chem.: propagation rate constant. J.: initiation rate constant. [PI. []/mol sec] ktc: rate constant for termination by combination..sec] k.+ktd=2. Makromol. [Pli + [Plj--t [M]i + [MIj + kd k. [ 1/set] k. K.lll~: termination rate constant..: initiation rate constant.~:decomposition rate constant.. sec] ktpr:rate constant of termination reaction with primary radical. Bulk polymerization Initiator: benzoyl peroxide Temperature: 60°C Initiation Propagation Termination [I1 --3 2[RI [RI + [AI [PI1 [PI. [I/mol. and O'Driscoll. 13.. [A]: monomer.: growing polymer radical with j units. [I/mol. C.Styrene 119 h:decomposition rate constant. + [PI..

[l/mol-sec] * 10 Yamada. kt. sec] [I/mol* Mahabadi. P. [I/mol-sec] rate ktd(n. [I/mol.O Pn+lo kd k i kP + + + P.ln)+kt~(n. M.in) + Pn+in I: initiator.m) ktc(n. Macromolecules. Kageoka.. R" : primary free radical. [I/mol.: propagation rate constant." Pn" + Pino P.ln): rate constant for termination by disproportionation. M: monomer. and Otsu. [ l/sec] ki: initiation rate constant.=480 k. 28. 0 1985 American Chemical Society.2'-azobisisobutyronitrile Temperature: 30°C Initiation Propagation Chain transfer Termination by disproportionation Termination by combination I R" + M Pn" + M +Y Pn0 + PI. H.: transfer rate constant to Y. 1319 (1985). K. Pno : growing polymer radical containing n monomer units.. ktd(n.O ---f ---f 2R" P.sec] ktc(n..97X 108(nm)-'.ln): constant for termination by combination.: propagation rate constant. Polym. kt(n.. . [I/mol*sec] k.120 Free radical polymerization Bulk polymerization Initiator: 2. 18. + Yo + P.. P. sec] k. Y: chain transfer agent such as monomer or initiator. Bulk polymerization Initiator: dimethyl 2.2'-azobisisobutyrate Temperature: 70°C k..ln)). B. [I/mol* sec] kt(n.: dead polymer containing n monomer units..ln): termination rate constant (=ktc(.75 (1992). T. Bull.p)=l...12 b:decomposition rate constant.

4-dimethylvaleronitrile (AVN). methyl 2.05 0.92 (')Photo-induced polymerization Temperature Conversion range ["CI [%I 0 50 70 100 k.sec] 130 0-6 0-35 0-85 0-40 0-50 k.2 0.5 0.20 108 2. [I/mol.Styrene 121 Bulk and photo-induced bulk polymerization Initiator: 1.3 256 48 1 1620 3350 108exp(-39.2'-azobisisobutyrate (MAIB).=5.05 3.1 I-azobis.5 kdX IOs [ 1/sec] 0 50 70 100 130 ACN/UV"' AVN MAIB MAIB TBP 4.1-cyanocyclohexane (ACN). or t-butyl peroxide (TBP) Temperature: 0-1 30°C Temperature 1°C 1 Initiator E1 1 [mol/l] 0.7 kJ/RT) .2'-azobis-2.00 2. 2.1 0.50 X 12.

M..90 1. and styrene Emulsifier: stearic acid Initiator: potassium persulfate Temperature: 40-60°C -d[CsHs]/dt=k[cat]”* Activation energy for k=18500+ 500 [cal/mol] [CgHs]: concentration of monomer. Bull.43 6. T. Chem. and Adams. [mol/l] Price. C. stearic acid. . 29. [ I/sec] k. [mol/l] Yamada. [l/mol*sec] E. Kageoka. B.: termination rate constant. [mol/l] [cat]: concentration of initiator.. potassium persulfate.: activation energy of termination reaction. SOC. 0 1945 American Chemical Society.: propagation rate constant.90 Et=15.1674 (1945). Polym. and Otsu.67.32 4. C.704 I . E. [Vmol sec] k. J.122 Free radical polymerization Temperature [“CI 0 50 70 100 130 kt X 1 0-8 [l/mol*sec] 0.6 b:decomposition rate constant of initiator.. [kJ/mol] [I]: concentration of initiator.. Emulsion polymerization Ingredients: water..385 (1992).. Am. C.

[I/mol-sec] kt: termination rate constant.: concentration of monomer in the polymer..3 X I O‘6 at 60°C P: degree of polymerization. soap. potassium persulfate.. Soc. M. + M Mn+l’ k.. [-3 m: number of monomer. Emulsion polymerization Ingredients: water.. J.2. PoZym.. Reprinted by permission of John Wiley & Sons. sodium oleate. 0 1948 American Chemical Society. M: monomer. [-3 k.Styrene 123 Emulsion polymerization Ingredients: water. Sci. dodecyl mercaptan. Inc.257 (1947).3695 (1948).=3. Inc. + k. L. Chem. V.192 0. . and styrene Emulsifier: sodium oleate and dodecyl mercaptan Initiator: potassium persulfate Temperature: 35-50°C -dC. Am. W.: propagation rate constant. Copyright 0 1947 John Wiley & Sons..5 X 10”exp (-1 1700 cal/RT) kdkt=Pr/m=l...0 42. and styrene Emulsifier: soap Initiator: potassium persulfate Temperature: 30-60°C M. M..907 Activation energy of k=22500 [cal/mol] C. [I/mol*sec] Smith. [-I r: number of free radicals present. J./dt=kC2/* Temperature [“C] 35. : growing polymer radical containing n monomer units. 70.304 0. potassium persulfate.0 k [ l/sec] 0.5 50. [g/g] Corrin.

Inc.5 8... M.7 7. versene. potassium persulfate. P.279 (1 952). Emulsion polymerization Ingredients: water. sodium sulfate.1 Potassium persulfate HP-TETA With potassium persulfate: k. Salatiello. Inc. 1 X 107exp(-7400 cal/RT) With CHP-TETA: k. and styrene (2) water. soap. J. Sci.=4. sodium hydrogen phosphate.124 Free radical polymerization Emulsion polymerization Ingredients: (1) water. [I/mol*sec] Morton.=3 .9"C -d M/dt=kpM(N/2) .5-70.3 X 107exp(-8400 cal/RT) k. P. and styrene Emulsifier: sodium lauryl sulfate Buffer: sodium hydrogen phosphate Initiator: potassium persulfate Temperature: 30. Copyright 0 1952 John Wiley & Sons. and styrene Emulsifier: soap Initiator: cumene hydroperoxide-triethylenetetramine(CHP-TETA) and potassium persulfate Temperature: 5°C and 40°C Maximum conversion: 60% Initiator Temperature k. Reprinted by permission of John Wiley & Sons. triethylenetetramine. soap.8.. potassium persulfate.. [I/mol*sec] ["C 1 40 5 139 22 Temperature ["CI 40-50 5-15 5-15 Activation energy [kcal/mol] 6. and Landfield. cumene hydroperoxide. H. sodium lauryl sulfate.: propagation rate constant. potassium chloride. Polym.

=k. Copyright 0 1964 John Wiley & Sons.2 50.5 311. J. K. Sci.2049 (1964).=282 k.O 357. Emulsion polymerization Ingredient: potassium persulfate. Inc.. [number/ml] k. Reprinted by permission of John Wiley & Sons. Inc.5 40. [mol/l] N: number of latex particles/ml of aqueous phase in the emulsion. nonionic octyl phenoxyethyl surfactant.24 X kP [I/mol-sec] 51..1 300.=2.9 10'4exp(-l7570 cal/RT) M: monomer concentration in polymerization particle.3 291 .: propagation rate constant. [gA] . [I/mol*sec] n: number of free radicals per particles. sec] Paoletti. P. [I/mol.0 120. W.5 51. Polym. [mol/particle] [MI: monomer concentration within the particles. KOH.Styrene 125 Temperature ["CI 30.0 50.2 70.n[Ml n=1/(2 X 6.02 X [M]=905 k. F. and Billmeyer. sodium lauryl sulfate Initiator: potassium persulfate Temperature: 60°C Maximum conversion: 9 1.9 k..: propagation rate constant. A2.O% R.

6-3500/T kp=156 at 50°C . and Hamielec. A2r-33. A. and styrene Emulsifier: octylphenoxyethyl surfactant and sodium lauryl sulfate Initiator: potassium persulfate Temperature: 60°C Maximum conversion: 70% kt=(kt)oA~exp(-(A~X+AzX2+A3X3+A4X4)) Ao=l. sodium laurylsulfate. potassium persulfate.39.=4. A. Emulsion polymerization Ingredients: water.30. Inc. Chem. Copyright 0 1973 John Wiley & Sons.dx/( I -E)dt=kp(1. and styrene Emulsifier: sodium laurylsulfate Initiator: potassium persulfate Temperature: 40-60°C -d( [M]V.sec] Grancio. Sci.3321 (1973). [l/mol*sec) X: conversion of monomer.A-1.126 Free radical polymerization Rpp:rate of polymerization per particle.681.Polym. Ed. (kt)o=5X . Inc. D. [g/particle. M. Emulsion polymerization Ingredients: water. 11. Sci. Polym. J Polym. Reprinted by permission of John Wiley & Sons.8. and Williams. Reprinted by permission of John Wiley & Sons. potassium persulfate.)/dt=kp[ M]/~NAV Vp=Vp. E..X ) / ~ N A-EX) 1 ~( In(kp)=16. Copyright 0 1970 John Wiley & Sons. J. A ~ 9 6 .. N. lo7 k. 5 6A4=56. octylphenoxyethyl surfactant. [-I Friis.2617 (1970). [I/mol sec] (kJo: termination rate constant in pure styrene.203. Inc.: termination rate constant. J . R. sodium lauryl sulfate. Inc. .( 1-EX)/( 1-E) [M]o( 1-x)/( 1-EX)=[M] Vp.

k. 19..O: volume of a latex particle at zero conversion. -RM. S. [dm3/mol sec] k. Emulsion polymerization Initiator: peroxydisulfate anion Temperature: 50°C Initiation Aqueous phase Propagation Entry I= + 2R. - Hawkett. R. Inc.: termination rate constant. Inc.O x: fractional conversion. [-] 127 Soh. 3173 (1981).. Chem.R * -+ M + -RM. [dm3/mol sec] k.. [mol/l] [Mlo: initial concentration of monomer. k. Copyright 0 1980 John Wiley & Sons. Reprinted by permission of John Wiley & Sons. ~ :volume o f a latex particle at complete conversion.: polymer radical with n units. -RM.-l* + M + -Rh4. Polym.: propagation rate constant. -+E -RM.=250. Polym. D. and Gilbert. Inc.. Inc. G. Napper.. K. k. Copyright 0 1981 John Wiley & Sons. Sci.: volume of a latex particle.. I=: initiator. sec] k.. [dm3/mol. Polym. R*-: primary radical. [cm3] v . J. E: entry into particle. Reprinted by permission of John Wiley & Sons. J. [ l/sec] k'.)/V.Styrene [MI: concentration of monomer. kt=7 X 1O7 ki: decomposition rate constant of initiator. H. P: a latex particle. S.: propagation rate constant. Appl.: rate constant for entry of an oligomeric radical ion with n monomer units into a particle. . [dm3/mol sec].. M: monomer..: initiation rate constant.*+P ki k'.O-V. [cm3] k.2993 (1980). [l/mol*sec] NAV: Avogadro's number E: volume shrinkage factor E=(V. Ed. [cm3] v. Sci. [mol/l] v. B. 25.

14X los 0. A.. [ l/sec] kI: initiation rate constant. Napper.024)"' p (')For H202/Fe2+.: the number of particles per unit volume. 1257 (1983). 2. [ I/sec] kt: bimolecular termination rate constant. [mol/l] PI: Penboss. Chem.128 Free radical polymerization Emulsion polymerization Surfactant: Aerosol MA 80 (sodium dioctyl sulphosuccinate) Initiator: potassium persulphate (K&08). H.23 4 x 10" (0. I. [I/mol* sec] h:entry rate constant of oligomeric free radicals into the particles. rate of free radicals captured by latex particles.1OX lo5 0. G. pl=ke[R*1 PI=')' (wc2mA2+4p[ I])"2-N~m~} P=ktk1/k2. -+ inert products kt R. and thus subject to some uncertainty.013 2. Soc.21 X lo-'')(') 0..2'-azobis(2-amidino-propane)hydrochloride and Temperature: 50°C I R.. [Vmol-sec] kdkd 1x 0. Faraday Trans.. kl 2R. D. P. R.20X lo-'' 0. value obtained assuming [I]=[Fe2']. [I/mol.64 X lo-'' 0.y=k2/2kt kd. : radical. 79. [ml/sec] kd: decomposition rate constant per free radical.4X 0. J. [I/moll y. . [number/l] NA: Avogadro's constant [I]: initiator concentration. and Gilbert. hydrogen peroxide and iron (11) sulphate (V-50) (H202/Fe2+). R.23 X IO5 (0. + (latex particle) (entry into particle) ke -+ I: initiator.sec] N. I.

and styrene Initiator: sodium persulfate Temperature: 70-90°C Persulfate decomposition Aqueous-phase initiation ani. [mol/sec] p: rate of free radicals captured by latex particles.583X 1016exp(-16708.=ktoexp(-2( BX+CX2+DX3) k.: polymer-phase termination rate constant. [mol/sec] kI: initiator decomposition rate constant. D=-O. [I/mol*sec] kto: polymer-phase termination rate constant at low conversion. : primary free radical.CND JCRVaq i Rt=kwtCR Vaq p1=p+2Rt CN=N/O\IAV~J f=P/Pl k1=4.539 X 105exp(-4235cal/RT) k. Aerosol MA.295 X 109exp(-2370cal/RT) J=2 k.Styrene Emulsion polymerization Ingredients: water.: polymer radical.457. 2R+ + Rate PI P Rt 12: initiator. 1.73. I* + 1 + R * PRe + L + Pa. L: latex. VERSENEX 80.o=l. [I/mol sec] k. x 1015 19 B=0.=2.l576 at 90°C R. [ I/sec] k.4kWI/*=2. Paq:aqueous phase. propagation Capture of free radicals by latex particles Aqueous phase termination I2 129 21.: aqueous-phase free radical termination rate. PI=2kICIVaq p=k. M: styrene dissolved in aqueous phase. [mol/sec] PI: rate of free radical generation. P.: monomer propagation rate constant.6 cal/T) k. [I/mol*sec] . C=3. sodium persulfate.

P2: dead initial polymer. [mol/l] CN:latex particle concentration in aqueous-phase. DI: polymer growing at one end. D.: latex diameter. D2: initial polymer growing at both ends. I. Gundlach. [-I. 6.023 X 1023. 22. R: growing transfer polymer. Q: dead center. . Photo-induced bulk and solution polymerization (1) Photo-induced bulk polymerization Temperature: 0-25°C Initiation Propagation 2M M + hv X +M D? + M D1 + M R+M D2 + X D1 + X R+X 2x + + Termination 2X or D2 2X or D2 +X +Dl+R +P2+R +PI+R +Di+Q -tP2+Q -tPi+Q 24 X: active center. and Nelsen.sec] k. P.. [dm] J: constant represents the dependence of p on D.. J=1 for diffusion. [I] N: total number of latex particle inside reactor.[number/mol] Kao. J=2 for collision f: free radical capture efficiency.130 Free radical polymerization k:free radical capture rate constant. [mol/l] Vaq:volume of aqueous phase. Polym. R. C. Polym. [mol/l] CR:free radical concentration in aqueous-phase..: aqueous-phase termination rate constant. Inc. Ed. Chem. [-I CI: initiator concentration in aqueous-phase. [-3 NA:Avogadro's number. Copyright 0 1984 John Wiley & Sons. Reprinted by permission of John Wiley & Sons. 3499 (1984). Inc. [13J/mol.. J. T. []/mol* sec] D.. Sci. PI: dead transfer polymer.

7 3.3 X 10I2exp(-37. n-heptane.99 X 10’ 4.904X 80°C 1. CH2CICH2C1.60 X lo6 c2w3r2 80°C v 3 Toluene 80°C 100°C 120°C 5.Styrene 131 Temperature kl k2 [“CI [I/mol*sec] [I/mol*sec] 0 25 k3 k4 [I/mol*sec] 1.47 x 10” 6.120°C c1 c4 60°C k’3 CBr4 100°C 60°C 80°C 159 282 6.l ~ 6.0+-2kcal/RT) k2=1. ethylbenzene. CBr4.8 1 kcal/RT) +_ (2) Photo-induced solution polymerization Solvent: CC14.7 7.2 6.94 4.02 X 1 06exp(-6.50X 107exp(-14.1 112 16.5 1 X 1.68 X lo8 .7 kl=l 2.79 X IO6 [I/mol-sec] 7.5 1 kcal/RT) k3=1.68 X 4.15X low3 1.07 X 108exp(-2.83 x io6 2.804 E A 1. benzene.32 x 1 0 .54 10.70X 18.89X lo-* 100°C 5X E A 0.9 1 18.163 X 21.2 2.92 X lo6 CH2ClCH2CI 60°C 1.2+-1 kcal/RT) 1b=3. and tetrachloroethane Temperature: 60. C2H4Br2.2 1.26X 10” 80°C 0. toluene.

132

Free radical polymerization
Ethylbenzene
80°C 100°C 4.06X 18.2 1.60X IO9 120°C 1.41 X 10" 80°C 1.57X 10"

Benzene
100°C

kt3 1.43X E
A

6.67X 10" 19.1 8.79 X lo*

n-Heptane
100°C
k'3

Tetrachloroethane
I00"C 0.300

3.89 X 1O-*

kl: initiation rate constant, [I/mol-sec] k2: propagation rate constant, [Vmol. sec] k3: transfer rate constant, [I/mol*sec] b:termination rate constant, [I/mol*sec] k'3: chain transfer rate constant to solvent, []/mol sec] E: activation energy for k'3, [kcal/mol] A: frequency factor for k'3, [I/mol*sec]
Discussions, 2,3 10 (1947). Bamford, C. H. and Dewar, M. J. S., Faraday SOC.
Photo-induced bulk polymerization Sensitizer: benzoyl peroxide Temperature: 25-30°C Pressure: vacuum Maximum conversion: about 32%

M =PI Pr + M = Pr+, P,+M =Mr+P1 Pr+P, =Mr+M,

Styrene

133

M: monomer, Mi: dead polymer containing i units of monomer, PI: polymer radical containing i units of monomer. -d[ M]/dt=R=k,[ MI f(I)1'2/kt1'2 1/P=kdk,+kl/(k:[M]2) Temperature ["CI 25 30 k,
[l/mol- sec]

kt [I/mol*sec]

kf []/mol sec]

39.5 f5 51.9

(7.9k2.O)X lo6 1.05 x io7

(1.1 kO.5)X 10" 1.66 X IO"

f(1): rate of initiation, [mol/l sec] k,: propagation rate constant, [I/mol*sec] kf: transfer rate constant to monomer, [Vmol-sec] k,: disproportionation termination rate constant, [Vmol sec] [MI: concentration of monomer, [mol/l] R: overall rate of polymerization, [mol/l*sec] P : mean degrees of polymerization, [-I

-

Melville, H. W. and Valentine, L., Trans. Furuduy SOC., 46,210 (1950).
Photo-induced bulk polymerization Temperature: 0-55°C Maximum conversion: lower than 1 %

Initiation Propagation Termination Transfer

M
P1 I

= PI

+M

= P,+I = M + Mrn i = M,

P + Prn n P,, + M

+ PI

Rate I k,[Pl[Ml kt[PI2 kdP1[MI

M: monomer, P,,: polymer radical containing n units of monomer, Mn: dead polymer containing,n units of monomer. 1/P =k$k,+ktW(k,2[M]2)

134

Free radical polymerization

Temperature ki ["CI [I/mol*sec] 15 25

kP [I/mol*sec]

kt []/mol* sec]

kf

[I/mol*sec]

I .48 X I 3 4x 10-l~

29.2 39.5

5.55 x io6 5.96X IO6

5.70~ 1.26X 10"

ki=4.15 X lO"exp(-36400 cal/RT) kp=l.44 X 1 06exp(-6300cal/RT) kt= 1.43 X 1O*exp(-1900 cal/RT) kr4.08 X 107exp(-14400 cal/RT) R: rate of monomer conversion, [mol/l * sec] [MI: concentration of monomer, [mol/l] P : average degree of polymerization, [-I I: rate of initiation, [mol/l sec] k,: initiation rate constant, [I/mol*sec] kp: propagation rate constant, [Vmol sec] kf: transfer rate constant to monomer, [I/mol*sec] k,: disproportionation termination rate constant, [I/mol*sec] Burnett, G. M., Trans. Faraday Suc., 47,772 (1950). Photo-induced bulk polymerization Sensitizer: a-azobisisobutyronitrileand 2-azobispropane Temperature: 10-60°C M. + M =Ma Ma + Me = polymer M: monomer, Ma: growing polymer radical. -d[M]/dt=2k, [M ]* k,=2.16 X 107exp(-7700cal/RT) 2k,=2.59 X 1 09exp(-2370cal/RT) Rate kP[M 1[MI 2k,[M*]*

-

Styrene
k,: propagation rate constant, [Vmol-sec] k,: termination rate constant, [I/mol*sec] [MI: concentration of monomer, [mol/l] total concentration of growing radicals, [mol/l]
[ M e ] :

135

Matheson, M. S., Auer, E. E., Bevilacqua, E. B., and Hart, E. J., J. Am. Chem. Soc., 73, 0 195 1 American Chemical Society. 1700 (1 95 I).
Photo-induced bulk polymerization Sensitizer: 2,2'-azobisisobutyronitrile Temperature: 15°C

kdkt=6.8 X
k,: propagation rate constant, [Vmol ssec] k,: termination rate constant, [Vmol-sec]

Majury, T. G. and Melville, H. W., Proc. Roy. Soc., London, A205,496 (1951).
Photo-induced bulk polymerization Sensitizer: benzoyl peroxide Temperature: 15°C

kdkt=2.0X
k,: propagation rate constant, [I/mol. sec] k,: termination rate constant, [I/mol .set]

Grassie, N. and Melville, H. W., Proc. Roy. Soc., London, A207,285 (1951).

136

Free radical polymerization

Photo-induced bulk polymerization Sensitizer: a-azobisisobutyronitrile(A), cumene hydroperoxide (C), tert-butylhydroperoxide (TB), and benzoyl peroxide (B) Temperature: 60°C

R;=Bl[Cat] 1/P,=C,,+CIICat]/[M]+aR, Cm=ktr/kp, C1=kl/kp,a=(2ktd+kt,)/k;[M]2 Sensitizer A B C TB CI=kI/k, Bl [moI/l.sec2]
5.19X 1.21 x 1 0 ' ~ 2.49 X 4.06 x

0
0.048 0.063

0.035

kl: specific rate constant for disappearance of radical pairs by transfer to catalyst, [I/mol*sec] k,: specific rate constant for propagation, [I/mol sec] kt,: specific rate constant for disappearance of radical pairs by combination, [I/mol- sec] ktT:specific rate constant for disappearance of radical pairs by transfer to monomer, []/mol sec] ktd: specific rate constant for disappearance of radical pairs by disproportionation, [I/mol*sec] R,: propagation rate, [mol/l. sec] [Cat]: sensitizer concentration, [mol/l] P,: number-average degree of polymerization, [-I

-

74,938 (1952). Johnson, D. H. and Tobolsky, A. V., J. Am. Chem. SOC., 0 1952 American Chemical Society.

Styrene
Photo-induced bulk polymerization Sensitizer: 2,2'-azobisisobutyronitrile Temperature: 25°C

137

kf/k,=3 X 10-5 kl/k;=5000 k,d=O kt=ktc+ktd k,: propagation rate constant, [I/mol. sec] kf: transfer rate constant to monomer, [l/mol*sec] kt,: rate constant of termination by combination, [l/mol * sec] ktd: rate constant of termination by disproportionation, []/mol * sec]
Bevington, J. C., Melville, H. W., and Taylor, R. P., J. Polym. Sci.,12,449 (1954). Copyright 0 1954 John Wiley & Sons, Inc. Reprinted by permission of John Wiley & Sons, Inc.

Photo-induced bulk polymerization Sensitizer: with or without 2,2'-azobisisobutyronitrile (AIBN) Temperature: 20-30°C Conversion: 0-70%
d[M]/dt=k,[R] [MI

d[R]/dt=qIabs+ki[M]2-kt[R]"
_____~

Conversion[%] Temperature["C]

n 1.9-2.1 1.9-2.1
1.7-1.8

kdk,
0.55 x 2.36X 6.36X 2.56 x 1 o - ~ 1.30X IO-* 1.37X

ktx/k,J2)

0

38* 1 43 k 2
6022

20 30 30 30
30

1
3.75 X 9.22 x
1.81 X

70+2
(I)

30

1.4-1.6

1.71 X

AIBN was used as a photo-sensitizer in this experiment. No sensitizer was used in the others. (2) The ratio of k,, at x% conversion to ktoat nearly 0% conversion.

2'-azobispropane Temperature: 30°C kdk. Photo-induced bulk polymerization Sensitizer: benzoylperoxide Temperature: 30°C Pressure: 1-3000 [kg/cm2] Initiation Propagation Termination Transfer hv+C + R R + M +PI P +M n €'..: rate constant of propagation.: rate constant of termination.02 X k. Fujii. Mn: dead polymer chain containing n units of monomer. C: sensitizer. Pn: growing polymer chain containing n units of monomer.[ MI2) .+Pl + + klf(1) k2 k3 k4 M: monomer. 196 (1956). Bull.: propagation rate constant.. 27. SOC.+M -+ M. sec] k.. [I/mol*sec] k. [I/mol. Chem.216 (1954). S. sec] k. []/mol sec] Mikami.138 Free radical polymerization ki: rate constant of thermal initiation. 1 /P =k/k*+k3R/(2k. [mol/l] Japan. sec] Iabs: absorbed light intensity [MI: concentration of monomer.: termination rate constant. Nippon Kagaku Kaishi. [mol/l] [R]: concentration of total radical polymers. H.+I P + Pn n I Mn+ln P. R: free radical. 77. Photo-induced bulk polymerization Sensitizer: 2. [Vmol. [I/mol. = 2.

G. [l/mol*sec] k2: propagation rate constant.sec] kt: termination rate constant. E. sec] Japan. A.. [mol/l.Discussions.5 108 206 400 6..Stvrene Pressure [kg/cm23 1 1000 2000 3000 k2 139 klf(I) []/mol* sec] 19. Photo-induced bulk polymerization Sensitizer: 2.2 X 9. [-I - Nicholson. R.25 x 3. sec] P : number-average degree of polymerization.5 x 10-7 k3 [I/mol*sec] [I/mol.2'-azobispropane Temperature: 30°C kJk. Chem.54 x io7 io7 io7 io7 klf(I): rate constant of initiation. []/mol sec] [MI: monomer concentration. SOC.05 x 2.711 (1956). [l/mol. 29.8 x 10. [mol/l] R: rate of polymerization. H. [I/mol*sec] k3: termination rate constant of combination. . [I/mol.65 x 3. Faraday SOC.9 x 1 0 ' ~ 9. 104 (1956). and Norrish. Bull. W.=2. 22.: propagation rate constant. [I/mol*sec] h:transfer rate constant to monomer.sec] 72.02 X 10-6 k. Miyama.

Chem.2 0.: termination rate constant..31 f0.715 (1956).5f0.Japan. [I/mol. Bull.3 1. SOC. [I/mol-sec] 35*7 35t5 29f8 29f7 23k8 20f5 27k4 kt X 1 0-7 [I/mol-sec] 1.: propagation rate constant.. 322 (1973). [I/mol. G.2'-azobisisobutyronitrile Solvent: bromobenzene. diethyl phthalate. S.8f0. Trans. and dinonyl phthalate Temperature: 25°C Solvent vol% k. G. Photo-induced solution and bulk polymerization Sensitizer: 2. [I/mol*sec] Miyama.: propagation rate constant.6f0.I. diethyl malonate..2'-azobisisobutyronitrile Temperature: 30-40°C kdk.4 1. 1.0.2 0. M.9f0. sec] k. Cameron. sec] Burnett.O9 10-3exp(-3710 X cal/RT) k.. G.04 None Bromobenzene Diethyl malonate Diethyl phthalate Dinonyl phthalate 20 50 20 20 50 60 k.: termination rate constant.140 Free radical polymerization Photo-induced bulk polymerization Sensitizer: 2.4 1 9t.=l. .1 k0. N. [I/mol. 69. sec] k. H. and Joiner.3 . 29. Faraday SOC.

F. + M.sec] k.: =ktc+ktd. R. S.. 21. M. M. [I/mol sec] k..~ 4..: dead polymer molecules containing n monomer units.. M. Felder. K.: rate constant of chain transfer to sensitizer.. []/mol sec] ktn. R ..Jkl”2= 143exp(-2774/T) kp: rate constant of propagation. and Hill. [I/mol*sec] +: primary quantum yield Ias: rate of absorption of light by sensitizer Mendiratta. ..Styrene Photo-induced bulk polymerization Sensitizer: benzoin and benzoin methyl ether Temperature: 293°C S + 2R. M.”2[(l/mol*s ~ c ) ” ~ ] I . + S + P.605 x 1 0 .. P. + 141 S: sensitizer. [I/mol.. M: monomer.: rate constant of chain transfer to monomer. Reproduced with permission of the American Institute of Chemical Engineers.+M +MI. [I/mol.sec] kid: rate constant of termination by disproportionation. + M -+ Mn+l’ Mn*+ Mi. Sensitizer Benzoin Benzoin methyl ether @112kdk. AZChE Journal.: primary radicals formed from its decomposition. M.* + P. [I/mol 'set] klc: rate constant of termination by combination. 1 1 15 (1 975). Copyright 0 1975 AIChE.* + M + P n + M ’ l . Pn+in M. R. B.. + P.. All rights reserved.042 X lo” k. : growing radicals containing n monomer units.. + R’.

ktd[Pn * 1[pin * 1 C: sensitizer.. ktr.: primary free radical.=74 5 kt=(37+0. Y: chain transfer agent.2'-azobisisobutyronitrile Temperature: 25°C Conversion: 0.. Polym.3)X lo6 $I& rate of photo-induced initiation. [I/mol*sec] [i]: concentration of species i. [i/moi sec] b:decomposition rate constant. + @abs kd[Cl R. J. Inc. H.: propagation rate constant. 14. : growing polymer radical containing n monomer units.: rate constant of termination by combination. + M + P I * ki[R. Ed. [I/mol-sec] kt.Polym. ktc[Pn. P. K.. [I/mol. [I/mol*sec] k... 1[MI Transfer P.869 (1976).01-1.* 4 P. 2R... Copyright 0 1976 John Wiley & Sons. K. F.. + M 4 Pn+l* kp[Pn. Inc. and Mahabadi.dPn * I [Y] Termination P. Sci. k. + Y + P .. --+P. + Pi. + PI. Reprinted by permission of John Wiley & Sons.d: rate constant of termination by disproportionation. P. sec] k.142 Free radical polymerization Photo-induced bulk polymerization Sensitizer: 2. I [Pm ] P...: dead polymer containing n monomer units.05% Rate Initiator C C 2 2R. R. [I/mol*sec] ktr. * .Y: transfer rate constant to Y. + R . ][MI Propagation Pn. [mol/l] O'Driscoll. M: monomer. + PI. Chem. [ I/sec] ki: initiation rate constant.

6 89.7 60.8 89.075 0. [I/mol.6 89. 73.sec] XI.03 0.02 0.4 89. Macromol.Styrene Photo-induced bulk polymerization Sensitizer: 2. - kP [l/mol * sec] k .: average rate constant of termination.4 44. A l l ..: propagation rate constant.-Chem..7 90.075 0.045 0.. Sci.4 34. [Vrnol-sec] - k. 967 (1977).6 37 39 39.03 0.0 15 0. .095 X .:number-average degree of polymerization.6 89.=1 . K. [mol/l] k.045 0. kp= 1.703 X 109exp(-2268 cal/RT) [AIBN]: concentration of AIBN. F. J.2'-azobisisobutyronitrile (AIBN) Temperature: 15-30°C - 143 Temperature ["CI 15 20 25 30 30 30 30 30 30 [AIBN] [mol/l] 0. H. K. [-] Mahabadi. x io-6 32. and O'Driscoll.09 X 1 07exp(-7051 cal/RT) k.2 47 50 53 [l/mol*sec] 2705 2686 2600 2770 2400 1650 1300 950 780 48.

sec] Olaj. [ l/sec] k.8 kdk. 177 (1987).sec] [MI: concentration of monomer.: propagation rate. Makromol.=80 k.7 10.lk. G. F.”*)[ MI Sensitizer [I1 [mmol/l] 0...: termination rate constant. and Gleixner. F. [mol/l.. 155. [I/mol*sec] k. 0. 186. [mol/l] f: sensitizer efficiency. [Vmol-sec] k. [-3 b:decomposition rate constant.: termination rate constant. Photo-induced bulk polymerization Sensitizer: benzoin Temperature: 25°C kp2/kt=8. X 10-7 10. Chem. I.. 0..9x 1oV5 k.2’-azobisisobutyronitrile (AIBN) Temperature: 25°C Maximum conversion: less than 1. .: propagation rate constant. Chem.: propagation rate constant.23 2. Angew.4 11.144 Free radical polymerization Photo-induced bulk polymerization Sensitizer: benzoin and 2. [mol/l] [I]: concentration of initiator.88 1.O% Rp=(291]k#2( k. Makromol. [I/mol. [Vmol.sec] Olaj..2569 (1985).. and Bitai. Bitai.0 Benzoin Benzoin AIBN R. I.

66 8.=78 f6 for bulk polymerization =84 +. [I/mol.73-8.771 (1988).Styrene Photo-induced bulk polymerization Sensitizer: benzoin Temperature: 25-40°C 145 Temperature kP [“C 1 [I/mol*sec] k. 9...32 1S O k.2’-azobisisobutyronitrile Solvent: as shown in table Temperature: 25°C Initiator concentration [mol/l] lo”.. Chem.66 6. X 1O-* [I/mol. Rapid Commun. Photo-induced bulk and solution polymerization Photo source: laser Sensitizer: 2. [I/mol*sec] Olaj. 0. Kremminger.: propagation rate constant.73-8. Makromol.sec] 25 40 89 161 1.sec] 8.: termination rate constant. I..1 1 for solution polymerization .66 78 85 80-90 84-9 1 84 IO-^ EB EB MEOH Polystyrene EB: ethyl benzene.93-8.~ Additive Monomer concentration kp [mol/l] [l/mol. Average k. P.sec] k. and Schnoll-Bitai.66 1. F. MEOH: methanol. 5 x 1o-2 10” 5 x 10” 5 x 10.66 1.

314T) kt=ktc+ktd b:decomposition rate constant... M.63 X 107exp(-31500 caV8. k. [ l/sec] ki: initiation rate constant. 22.. R.. A. + MI. [Vmol * sec] ktd:rate constant for termination by disproportionation. 0 1989 American Chemical Society.. Sci. []/mol sec] - Clouet. [I/mol*sec] k. Termination by combination M. M: monomer. A27..n I Termination by disproportionation MI.: propagation rate constant.: propagation rate constant. Macromol. K. BPO: 70-90°C) I -+ 2R. M. Piton.-Chem.146 Free radical polymerization k. T. P.: rate constant for termination by combination.=3..55 X 10'0exp(-14200 ca1/8. J. M.. M. P.. G. + M. . 193 (1990). + M + RMn+I* M1 + M.3 14T) kt=2. [Vmol sec] k. Photo-induced bulk polymerization Sensitizer: 2. : growing polymer radical containing n monomer units. [Vmol-sec] Davis... R -: primary radical. Initiation + kd ki k* ktd ktc I: initiator. and Winnik. 2785 (1989). and Chaffanjon.. -+ M"+. C. Macromolecules.: dead polymer containing n monomer units. F.+M +RM* Propagation RM..2'-azobisisobutyronitrile(AIBN) and benzoyl peroxide (BPO) Temperature: 30-90°C (AIBN: 3O-5O0C. O'Driscoll.

15)X lo7 k. Re : radical.9+0.8 x io9 1. G.6 x 10' kl: decomposition rate constant.03) X lo2 kt=(0. [l/mol ssec] kt: termination rate constant. [l/mol*sec] 147 Cameron. Photo-induced solution polymerization Solvent: benzene Sensitizer: benzoin (B).+M S*:excited sensitizer. 107 (1 973).=(0. G. Sensitizer b/kl 6.17 k4 [I/mol] k ~ . and Cameron..8 90.25 t0. ~R. 14.C-Ph I I ki H non-radical products + radical products + R-Ma (or other products) + k. J. +M [I/mol*sec] B BA BME 8. II 4- .: propagation rate constant. k'. M: monomer. and benzoinmethylether (BME) Temperature: room temperature * 0 OR Ph-C-C-Ph S* + M S* + M R. benzoinacetate (BA).+ M Ph-C. [ Usec] .0 0.1 x io9 4.Styrene Photo-induced solution polymerization Solvent: dodecane Sensitizer: azobisisobutyronitrile Temperature: 25°C k. Polymer.

B.. Angew. and Otsu. [dm3/mol* sec] k. []/mol sec] kR. M.+M: constant for reaction of radicals with monomers. Mukromol.5234 (1991). Kageoka. and Schnabel. [dm3/mol sec] Yamada.145 (1978). Chem.: termination rate constant.94 x io3 k. R.. 24.7OX IO7 0-20 93.. [I/mol.=350-480 Conversion [%I k. Macromolecules.: propagation rate constant. .66X lo7-1.. 70. T. [dm3/mol sec] 1.148 Free radical polymerization b.klq: rate constant for reaction of monomers with excited sensitizers which lead to non-radical products and radical products..8 7.2'-azobis(isobutyrate) (MAIB) and t-butyl peroxide (TBP) Temperature: 70°C k. Photo-induced and thermally-induced bulk polymerization Initiator: dimethyl-2. W.sec] rate Kuhlmann. respectively.

7 -1. Inc. W. water and Aerosol MA (100% active dihexyl ester of sodium sulfosuccinate) Emulsifier: Aerosol MA Initiator: potassium persulfate or benzoyl peroxide Temperature: 30-70°C Conversion range: 97-90% Temperature k..Styrene 149 Radiation-induced emulsion polymerization Radiation source: y-ray Ingredients: seed latexes.10 0.9 0. [-I k. J.3 1 5.: propagation rate constant.140 120-220 Temperature ["CI 30 50 Monomer k. E.28-3.3 faq:efficiency of radical in the aqueous phase.265 (1961). [l/mol*sec] k. [I/mol. Bradford. B. J. [I/mol*sec] fas=1 0.1-10 0..77-3 . Copyright 0 1961 John Wiley & Sons. [I/mol*sec] Vanderhoff. potassium persulfate. Reprinted by permission of John Wiley & Sons.37-0. H.2-6.0 0.. Sci.79 [%I 20 40 20 40 20 40 faq=/3 1 - 70 10-170 2. sodium bicarbonate. and Tarkowski.sec] faq= I 30 50 70 88-160 200-380 340-6 10 faq=1/3 30-57 67.1.O 1. L.: termination rate constant.75 0.3 1. Polym. . Inc..

Radiation-induced bulk polymerization Radiation source: y-ray Temperature: 0-50°C Maximum conversion: below 12% k. M... Downer. [Vmol . and Sharma.. A-I. and styrene Initiator: polyvinylacetate Temperature: 25-40°C Initiator k.Jkl=4.57 X 10-”exp(9490cal/RT) k.985 X 104exp(-1 1830 cal/RT) kt. 1729 IF. Reprinted by permission of John Wiley & Sons. and styrene . Temperature [“CI [I/mol-sec] 40 25 PVA latex PVA latex 75 50 k. [Vmol. Makromol. P. and Majer. R... C.: propagation rate constant. S. Y.. Radiation-induced emulsion polymerization Radiation source: y-ray Ingredients: water. G. Inc. polyvinylacetate (PVA). Chem. . Copyright 0 1969 John Wiley & Sons. Sei. J. E.sec] k. [l/mol*sec] Huang.. Polym. J. M.150 Free radical polymerization Radiation induced emulsion polymerization Radiation source: y-ray Ingredients: water.sec] k.. 169 (1 962).: rate constant of propagation. M.. 58. R. 7. Inc. sodium dodecylsulfate.. (1969). sec] Allen. [I/mol. Westlake. M.: transfer rate constant to monomer.: termination rate constant../kt=1 .. Burnett. J.

Inc. D. J. [mol/l-sec] k apparent termination rate constant in emulsion polymerization. [mol/l] [R]: radical concentration at the reaction locus.: termination rate constant by combination. O. Inc. [mol/l] $./2k~[M]*)+(kt. and Hummel.. sec] k.85 X 104exp(-12027cal/RT) ktnIl=O R. G../kp) 54-74"C: m=1/2 74-109°C: m=1/2-0 above 109°C: m=O k.: propagation rate constant.. [I/mol. M. C. sec] k..[MI: rate of production of free radicals per unit radiation dose . Reprinted by permission of John Wiley & Sons.Styrene Emulsifier: sodium dodecylsulfate Temperature: 25°C Maximum conversion: 67% -d[M]/dt=kp[M] [R] -d[R]/dt=k.sec] k. Radiation-induced bulk polymerization Radiation source: y-ray Temperature: 50.. Schneider..: transfer rate constant to monomer. [Vmol. [mol/l."[R]* k:=1 X 151 lo3 [MI: monomer concentration at the reaction locus..109°C Maximum conversion: 100% R..: propagation rate constant. [Vmol sec] [MI: concentration of monomer....=-d[ M]/dt=( kJkt $m[ M]I)"[ MI 1/P"=(ktR. [I/mol*sec] : C27. Polym./kt=2.: rate of polymerization. Sci. Copyright 0 1969 John Wiley & Sons. [mol/l] k. Ley.119 (1969). J..

and Hodgins.=l 07. J. Solution polymerization Solvent: carbon tetrachloride Initiator: 2.3383 (197 1).303RT) f k. k* I. [-3 Sood. Gilbert. J. [I/mol-sec] Lansdowne. H.5exp(-(29 3 kJ/RT)} k: rate constant for the first-order loss of free radicals from the particles. sodium dodecyl sulphate. Sci. S. 76.. polystyrene seed latex. and Sangster. T: radical derived from I. Aerosol MA80.4f 1. Chem.5)-(42 f10 kJ/2. Inc.1'o. ki kP kf . [ 1/sec] kp: propagation rate constant. F. R. Napper.303RT) lOg(po)=(10.8f0. R: primary radical. Polym. SOC. D.2'-azobisisobutyronitrile Temperature: 60°C k ... M: monomer. [ l/sec] PO:rate constant for entry of thermally generated free radicals into the particles.: initiator. D. 2R (2R) + S + inert products R+M + X X+M + X X+S +T+P T+M -X 2x +P - kd k. S: solvent. W.9. and styrene Temperature: 30-65°C Iog(k)=(3. W.152 - Free radical polymerization P ": average degree of polymerization.. J. I. 1344 (1980).0)-(87* 10 kJ/2. P.A-1. G... Radiation-induced emulsion polymerization Radiation source: y-ray Ingredients: water.. Copyright 0 1971 John Wiley & Sons. Reprinted by permission of John Wiley & Sons. S. Faraday Trans.. Inc.

M. [I/mol*sec] k. and Onyon. P: dead polymer.: propagation rate constant. F.. [ l/sec] ki: initiation rate constant. [l/mol*sec] k. [Vmol sec] k..: propagation rate constant.: decomposition rate constant.=765 kg/ki=0.: reinitiation rate constant.64 kf/k. ~ ~ l ~ ~ l + ~ R l kt/2k.: rate constant of reaction between primary radicals.: termination rate constant. [I/mol*sec] k.Styrene solvent.: termination rate constant. [I/mol*sec] kf: transfer rate constant to solvent. 153 ~ p = ~ p ~ ~ l ~ ~ 1 + 1 6 ~ ~ l ~ ~ [XI = ~ . George. X: growing polymer radical. [I/mol*sec] . Trans. H. [I/mol*sec] k./k. Furuduy SOC..a'-azobisisobutyronitrile Temperature: 30-60°C k. Solution and bulk polymerization Solvent: five different hydrocarbons (see table) Initiator: a. 1390 (1963). P. [I/mol*sec] 59. [mol s e d ] Solvent 60°C Benzene 2-Butanone Acetone Diethyl oxalate Cyclohexane Bulk styrene - 50°C - 40°C 7063 - 35°C 7112 - 30°C 1737 - 44 17 - 12258 - 1585 1434 1 162 816 665 1144 - - 8260 3044 - k.=O.O 135 k.

Reprinted by permission of John Wiley & Sons. Solution polymerization Solvent: benzene Initiator: 2.55X 10gOexp(-l cal/T) The value of kt. Inc. L. J. Copyright 0 1966 John Wiley & Sons." : polymer radical containing r monomer units.O4 styrene in benzene for h:decomposition rate constant of initiator.+.051X 107exp(-3557cal/T) ktc=l.. was corrected in the following way: I12 1/(ktc)s1'2=$d(ktc)b"lk $p=[M]bulk/{[S](Ts/Tin)+[M]} Ts/Tln=1. E.2'-azobisisobutyronitrile Temperature: 50-75°C Maximum conversion: 42.+M" Termination Rr0 + Rso P.: dead polymer containing r monomer units. P. R.255 X 109exp(-844 cal/T) kld=O k ~ 2 . Rro + Rso -+ Pr + Ps --+ kfs kf ktc kid &" : primary radical. N. So : solvent free radical. S: solvent. Polym.154 Free radical polymerization Glass. J..4. Sci. 1 X 106exp(-6377cal/T) 3 1000 kfs=9. Inc.' + S + Pr+ So + M --+P.5% Reactor: batch Initiation Initiator +M + 2%" kd rate of formation of RIo=I kP +Rlo Propagation RI' + M + R2" R2" + M -+ RO 3 Rro + M + R. 1223 (1966).A-1. M: monomer. [ l/sec] . and Zutty.+lo Transfer R.58 X 101Sexp(-15500 cal/T) kp=l. b=l.

6 0. [ Ug-mol.k. 1087 (1967). [g-mol/l] [MI: monomer concentration in solution polymerization. [ l/g-mol-sec] (ktc) rate constant for termination by combination in bulk polymerization.2 1.00 5.4-dimethylvaleronitrile) Temperature: 50 and 70°C ~~ ~ Solvent kp(2fkd/k1)l’* 1O4 X [1”2/mo1”2 sec] * 0..3 2.725 1. [g-mol/l] [SI: solvent concentration. DEP: diethyl phthalate.3 3. and Tebbens.. [ l/g-mol * sec] ktc: rate constant for termination by combination. [g-mol/l] T: temperature. Copyright 0 1967 AIChE.27 4.70 1. Hodgins. [ l/g-mol sec] (ktJ s: rate constant for termination by combination in solvent.30 1. [“K] 155 - Hamielec.26 7. 13.26 5. A. sec] kf. J . bulk: [ 1 /g-mol*sec] ktd: rate constant for termination by disproportionation.X 10-4 [mol sec/l] - Temperature [“CI DC DEP DOP DC DEP DOP DC DEP DOP 3.6 3. sec] kf: transfer rate constant to monomer..: transfer rate constant to solvent.: propagation rate constant.43 k.3 50 50 50 60 60 60 70 70 70 DC: dimethyl carbitol.72 2. W.3 3. Solution polymerization Solvent: three kinds of solvents as shown in table Initiator: 2. AIChE Journal.Styrene k. [ l/g-mol. K. DOP: di-n-octyl phthalate./k.2 2. [ l/g-mol * sec] [M]bulk:monomer concentration in bulk polymerization. Reproduced with permission of the American Institute of Chemical Engineers..2’-azobis(2.46 9. All rights reserved. E. .

8 3.4 5.A-l.2'-azobisisobutyronitrile was used.2'-azobisisobutyronitrileand benzoyl peroxide Temperature: 60°C Solvent None None'') Bromobenzene vol% kP [I/mol*sec] k.8 Diethyl malonate Diethyl phthalate Benzonitrile 20 20"' 40 50 50"' 20 50 20 40 50 20 40 50 186 187 184 182 167 167 163 178 133 174 163 162 186 158 134 ("Benzoyl peroxide initiator was used.2 6.0 6. sec] kti: termination rate constant by initiator.2 6. 2. . K. [I/mol.2 7. 93 1 (1972).7 6. Reprinted by permission of John Wiley & Sons. Solution and bulk polymerization Solvent: bromobenzene. diethyl phthalate. [I/mol-sec] b:decomposition rate constant.7 6.. Inc.0 6. [Vmol. In other runs. sec] k.1 3. Copyright 0 1972 John Wiley & Sons.1 5. [ I/sec] Ito.0 6.: propagation rate constant. Sci. Polym.: termination rate constant. diethyl malonate. and benzonitrile Initiator: 2.6 6. J. X 10-7 [I/mol*sec] 7.: initiation rate constant. [Vmol sec] k. [-I k. Inc.2 5.156 Free radical polymerization f: initiator efficiency.lO.

P. and dimethyl formamide (DMF) Initiator: benzoyl peroxide (BPO) Temperature: 50-60°C Rate Production of primary radicals Initiation Propagation Termination of growing radicals by mutual deactivation Primary radical termination Primary radical deactivation M + 2R..rt[P I[R. 1 krr[R.80 0.5X10.' 9. or PI. 69. PI.35 0.322. G.l[Ml k. Solution polymerization Solvent: benzene. 1 (1973).72 Styrene-benzene-BPO Styrene-toluene-BPO Styrene-DMF-BPO 50 60 .:dead polymer containing m units of monomer. [Ilmol.: termination rate constant.. and Joiner.Styrene k: propagation rate constant. : primary radical... In(R. Faraday SOC.[P. Cameron.12 - I: initiator.[P*12 k. ["C] [mol*sec/l] 60 0... R .6X 5.. -+ inactive products + 2fkkd[I] ki[R../[I] [M]2)=ln(2fkkdk. M. + M +PI. : polymer radical conta'ining m units of monomer. k. M: monomer.03X1OS 2.75 X [ 1/sec] 2. S . R. + M -jP2' Pi. + polymer R .. G.9X10-' 6. P. + P. Trans.97X lo5 1. + M + Piti. ][MI k.+ R . P I . PI.4 X 0.04 X IO4 fkkd MI2 kd fk [I/sec] 2. toluene. [l/mol*sec] 157 Burnett.1 X 1. G. N./kt)-2kp&Jkikp[ System Temperature kprt/kIk. P.+ R . sec] .. + P.

4-dimethylvaleronitrile) Temperature: 50°C A=k. [-I b:decomposition rate constant of initiator.4 2.. [mol/l] k. [I/mol.746 0.: termination rate constant.: propagation rate constant.: propagation rate constant.4 8. [moI.158 Free radical polymerization R. Eur.oo 1. and Meyerhoff. Solution polymerization Solvent: benzene (Bz). ethyl alcohol (EA). . Polyrn. [mol/l*sec] fk: catalyst efficiency.10./[C] ”*[MI A X lo4 kt/k. [I/mol*sec] k. [I/mol-sec] . and cumene (Cm) Initiator: 2. 1: total concentration of polymer radical.0 2. [ l/sec] ki: initiation rate constant..: rate constant of primary radical deactivation.9 4. [mol/l] [I]: concentration of initiator. [I/mol*sec] kprt:rate constant of primary radical termination.i/ 1 04kik.746 1 . [mol/l*sec] [C]: initiator concentration.2’-azobis(2. [mol/l] [MI: monomer concentration.: polymerization rate.709(1974). [I”2/moI”2-sec] [mol.840 0. P.01 0.(fl<d/kt)1/2sR.2 St St-Bz (1: 1) St-Bz-EA (3:1 :2) St-Bz-EA (6: 115) St-EA (1: 1) St-Cm (1 :1) 1 .2 12. [mol/l] Deb.set] k. I .: propagation rate. [I/mol*sec] [MI: concentration of monomer.sec/~] 9. [mol/l] [P.oo 833 850 1204 1530 1530 850 R. sec] k. G. sec/11 Solvent k. C. [Vmol .

2'-azobisisobutyronitrile Temperature: 75-95°C Initiation Propagation Transfer to monomer Transfer to solvent Termination by combination Termination by disproportionation I Aj + M Aj+M Aj+S Aj Ak A. Polym.=l." kls ktC ktd I: initiator. [I/mol*sec] b:decomposition rate constant of initiator.: initiation rate constant.: termination rate constant. Reprinted by permission of John Wiley & Sons. Inc. [l/mol-sec] . [I/mol-sec] klm:rate constant of transfer reaction to monomer..= 1. [-I Ito. [Vmol sec] kti:rate constant for termination by primary radical. [l/mol. + A k + .10 X lO-'exp( 13200 cal/RT) f: initiator efficiency. [I/mol*sec] ktd: rate constant of termination by disproportionation. [I/mol*sec] k.: propagation rate constant. Sci. S: solvent. P.2581 (1974).58 X 10'5exp(-30800cal/RT) ktJk.: rate constant of transfer reaction to solvent. K. Solution polymerization Solvent: toluene initiator: 2. Ao: primary free radical. [ l/sec] f initiator efficiency. f=0. M: monomer..4 k.: dead polymer containing j monomer units.: growing polymer radical containing j monomer units. 12. sec] ktc:rate constant of termination by combination.Styrene 159 k.sec] k. [-3 k.+ - 2Ao Aj+l +Pj+Ao +Pj+Ao + Pj+k + Pj + P k ki kP kl. Inc. J. [l/mol*sec] kt. A.: initiation rate constant. Copyright 0 1974 John Wiley & Sons. [Vmol.

S: solvent. Reprinted by permission of John Wiley & Sons. Reproduced with permission of the American Institute of Chemical Engineers. [-I ki: initiation rate constant. Solution polymerization Solvent: benzene Initiator: benzoyl peroxide Temperature: 60°C Process Production of primary radical Initiation by R Propagat ion I -+ 2R. M :monomer. F.43 (1976).. 13.. Sei.4 k. Copyright 0 1976 AIChE. F.sec] kp: propagation rate constant. J. A. Ao: primary free radical. Ser. Inc. C. .160 Free radical polymerization Scamehorn. 72. D.. D.58 X 10'5exp(-30800 cal/RT) ktJk. Chem. All rights reserved. C. [I/mol. + Ak 2Ao + Aj+l -+ P. AIChE Symp.: growing polymer radical containing j monomer units. 1241 (1975). J. f=0. [Vmol-sec] Timm. PoZym.. J. R*+M +MI* M I . Pj: dead polymer containing j monomer units. Solution polymerization Solvent: toluene Initiator: 2.2'-azobisisobutyronitrile Temperature: 75-95°C Initiation Propagat ion Termination by combination I Aj + M A.10 X 1O"exp( 13200 cal/RT) f: initiator efficiency. Copyright 0 1975 John Wiley & Sons. and Scamehorn.=1. and Timm. [I/mol*sec] ktc:rate constant of termination by combination. Inc. Polym.= 1. Ed. + M +M2.+k + ki kP ktc I: initiator.

: termination rate constant between polymer radicals.rt[RI .8 x 2.: initiation rate constant by R.+ P * + polymer R1* + P + polymer k'd[R*1 k'i[R1* ][MI kt[P l2 kp.sec] k. MI2} log(R. M2*: polymer radical with two monomer units.8684 { kpd/kikp( 1+k'd/ki[M])} { Rp/[ 2.58 3. I: initiator.t[P I[R. [I/mol.9 x 1 0 ' ~ 2.: propagation rate. [I/mol*sec] . : primary radical. MI * : polymer radical with one monomer unit.: initiation rate constant by R1 [I/mol.I 161 - . Epd=10. sec] fk: initiator efficiency.0 x 2.89 7.50X IO5 1.: propagation rate constant. R1*: radical obtained from decomposition of primary radical.6. [ l/sec] k. 1 k'.73 Ei+Ep+Ep.Styrene Decomposition of primary radical Initiation by RI Termination Termination with R Termination with R1 Re +R1* + X RI. R. Ei=74 R. [ l/sec] k'. o ~ 2.2/[1] [M])=l0g(2fkhkt/kl)-O..9 x io-' 3 .86 5. + M +MI* P I *+ Pz* -+ polymer R . [I/mol*sec] kprt:rate constant for termination by R. Ep=32. [I/mol..75 3.I[P. [l/mol*sec] * rate constant for termination by RI .03 6.. M: monomer. [mol/l.5 x l. .sec] k. [-3 h:decomposition rate constant of initiator. Pa : polymer radical with any monomer units.=96..5.17 6.sec] k'd: decomposition rate constant of R.

8684 (kpfi/kikp(l+k'&[M])} {Rd[MI2} . [mol/l] [MI: concentration of monomer. M2-:polymer radical with two monomer units. M: monomer. [mol/l] Ei: activation energy for initiation reaction.: activation energy for propagation reaction. R * + M -+MI* MI.2'-azobisisobutyronitrile(AIBN) Temperature: 60°C Process Production of primary radical Initiation by R. : primary radical. MI * : polymer radical with one monomer unit. Makromol. I. R. Termination Termination with R. [kJ/mol] E. + M + M I . [kJ/mol] Deb. 179. log(Rp2/[1][M])=log(2fkkdkp2/kt)-O. P. -+ polymer Re + P * polymer RI + Pa + polymer + + I: initiator..162 Free radical polymerization [I]: concentration of initiator. 1549 (1978). [kJ/mol] Epfi:activation energy for termination reaction by R. Solution polymerization Solvent: benzene Initiator: 2. R1*: radical obtained from decomposition of primary radical. D.*+X RI. C. Propagation Decomposition of primary radical Initiation by R. Chem. PI + P2. + M M2* R. -tR. P..: polymer radical with any monomer units. Termination with RI * I + 2R.. and Gaba.

00 X 1 0-9 4. I.~ 6. 179.. Ei=66 R.: propagation rate constant.75 4.03 6. [I/mol*sec] k. [I/mol*sec] Pp.5..42 x io4 3 . [I/mol. 3 0 io4 ~ 3. and Gaba.89 7.Styrene 163 1.80 x 3. [kJ/mol] Epd:activation energy for termination reaction by R.17 6.00 x 5.: termination rate constant between polymer radicals. [kJ/mol] e .58 3.: activation energy for propagation reaction. [ l/sec] ki: initiation rate constant by R. Chem.. 5 0 io4 ~ 2. 1559 (1978). [kJ/mol] E.: activation energy for initiation reaction. [-I b:decomposition rate constant of initiator. D. C. e . [mol/l] E.: initiation rate constant by R1 [I/mol. 4 0 io4 ~ 3.00 X 10-9 6.=32.+E. [I/mol*sec] k'd: decomposition rate constant of R .40~ S .E. Mukromol. .90 x 1o ..: rate constant for termination by R [I/mol*sec] 1 [I]: concentration of initiator. [ l/sec] k'..80 x io4 Ei+E.35 x io4 3 . sec] k. [mol/l] [MI: concentration of monomer. P.72 2...=88.6.: propagation rate.44 5. Epd=10. [mol/l-sec] fk: initiator efficiency.26~10~ 3 .sec] k.: rate constant for termination by R e . Deb.72 x 5.

164

Free radical Polvmerization

Solution polymerization Solvent: benzene (BZ), benzene-isopropyl alcohol (BZ-IPA), dimethyl carbitol (DC), DE, ethyl acetate (EA) Initiator: 2,2'-azobis(2,4-dimethylvaleronitrile) Temperature: 50°C

I 2R" R" + M + Pio Propagation P1 1 1+O PnO + M PnO + Y 4 P,+Y" Chain transfer Termination by disproportionation Pno + Pin' P, + P, Termination by combination Pno + Pino Pn+m I: initiator, M: monomer, R" : primary free radical, P,' : grow,,ig polymer rad.;al containing n monomer units, Pn: dead polymer containing n monomer units, Y: chain transfer agent.
Initiation
+
+

-+

+

kt(n,~~)=ktc(n,in)+kta(n,tn)=kt~(~~)~~

kt(n,m)=kt* (Xn)-2a/q RP=(2fkdkp2/k,*)~O.'[MI [I]O.'( X,,)" kto=1 O-2CT/rNoq

a=O. 1306 2kk;/kt*=8.27

X

1 0-'

kd: decomposition rate constant, [ l/sec]
ki: initiation rate constant, [l/mol*sec] k,: propagation rate constant, [I/mol sec] kt,: transfer rate constant, [I/mol*sec] k,(",,,,):termination rate constant between two rac icals of size n and m, 'mol sec] ktc(,,m):rate constant of termination by combination between two radic 5 of size n and m, [I/mol. sec] ktd(,,,"):rate constant of termination by disproportionation between two radicals of size n and m, [I/mol.sec] R,: polymerization rate, [mol/l esec] X,: number-average degree of polymerization, [-I kt*: a constant a: a constant q: viscosity of medium

Styrene
[MI: monomer concentration, [mol/l] [I]: initiator concentration, [mol/l] f: initiator efficiency, [-I C: constant T: temperature r: hydrodynamic radius of a monomer unit in a segment No: the number of monomer units in a segment Mahabadi, H. K., Macromolecules, 24,606 (1991). 0 1991 American Chemical Society.

165

Thermally-induced solution polymerization Solvent: thirteen different hydrocarbons (see table) Temperature: 60- 132°C
Solvent 60°C kl/k, X 1Os 100°C E,-E:l) [kcal/mol] 14.8 13.7 10.1 5.5 5.5 3.7 5.1 3.1
-

ln(Al/Ap)(') 9.06 8.67 4.03 - 1.27 -1.09 -2.76 0.24 0.19 7.2 1 -2.44
-

132°C

1.84 8.9 0.18 Benzene 5.5 0.6 tert-ButyI benzene 6.45 1.25 Toluene 16.2 Ethylbenzene 29 6.7 iso-PropyI benzene 20.0 8.2 42 Diphenylmethane 23 80 35 Triphenylmethane 750 Fluorene 1240 Pentaphenylethane 200000 0.24 8.7 Cyclohexane 1.6 n-Heptane 4.2 9.5 4 Decalin 900 Carbon tetrachloride 1810 3250

13.4 5.0 4.8

2.53

(')Calculated from the Arrhenius equation, k,/k,=(A,/A,)exp(-E/RT), where E=E,-E,.

k,: propagation rate constant, [I/mol-sec]
k,: termination rate constant, [I/mol*sec] E,: activation energy for k,, [kcal/mol]

166

Free radical polymerization

E,: activation energy for k,, [kcal/mol]
Gregg, R. A. and Mayo, F. R., Faraday Soc. Discussions, 2,328 (1947).
Thermally-induced bulk polymerization Temperature: 0-25°C

Initiation Propagation Transfer

Termination

2M +2XorD2 X + M +X D2 + M + D1 + R DI + M + P2 + R R + M -+Pl+R DI + Q D2 + X D l + X +P:!+Q R+X +Pl+Q 2X +2Q
+

X: active center, Q: dead center, M: monomer, D2: initial polymer growing at both ends, D,: polymer growing at one end, R: growing transfer polymer, PI: dead transfer polymer, P2: dead initial polymer. [xl=(kl/k4)1/2[Ml I [D21=k1w1/4 { k3+(klk4)-1/2 [D I 1=2[D21 [Rl=4 [Ddkdki k4)-Il2 -I=kl/{k3+(klk4)1/2} P P2=2F1 [ d [P Jdt=k3( k I /b)1’2MI2 d[Pz]/dt=kl [MI2/2 P,=2k2(k1k4)-”~/(2P+ 1) P=k3(klk$l2

Styrene
-

167

Temperature kl ["C] [I/mol*sec]
0 25

k2 [I/mol*sec] 6.9 1 18.7

k3

k4
[I/mol*sec]

P"

P

[I/mol * sec]

4.5 1 X 1.32 X lo-''

7.47X10'5 6.68 X

1.83X106 2.79 X IO6

9.08X104 26 2.67 X lo4 1 1

kl=l.23 X 1O''exp(-37.0 2 kcal/RT), k = 1.02 X 1O'exp (-6.5 f 1 kcal/RT), 2 k3=1.50X 107exp(-14.2f 1 kcal/RT), k4 = 3.07X 10'exp (-2.82 1 kcal/RT) kl: initiation rate constant, [I/mol-sec] kl: propagation rate constant, [I/mol*sec] k3: transfer rate constant, [I/mol*sec] b:termination rate constant, [I/mol. sec] P 1 and P2:number-average degrees of polymerization of the transfer and dead initial polymers, respectively, [-I P ,,: number-average degree of polymerization, [-I Bamford, C. H. and Dewar, M. J. S., Proc. Roy. Soc., London, A192,309 (1948).
Thermally-induced bulk polymerization Temperature: 25 and 125°C

*

25 ["C1 Initiation Propagation Transfer Termination ki k, kf k,
1.3 x
10-l~

125 ["CI 2.9 x 170.0 0.15 5.2 X lo6

Activation energy [kcal/mol] 35.0 5.5 13.2 1.8

18.7 6.7 x 2.8 X 10'

k,: initiation rate constant, [I/mol*sec] k,: propagation rate constant, [I/mol- sec] kf: transfer rate constant to monomer, [l/mol*sec]

168

Free radical polymerization

k,: termination rate constant, [Vmol sec] Vaughan, M. F., Trans. Faraday SOC., 48,576 (1952).
Thermally-induced bulk polymerization Temperature: 60°C

Thermal initiation M + M AH AH+M Propagation Chain transfer Termination R. Re R. R.

+

qph
(=AH) (=R*)+MeCHPh(=R.)
H Ph

kfDA

+

2M

krDA
~MIH

+

+M + AH +M + Re

+ polymer-P -+ R. + polymer-T + Re + polymer-T
+ R.
+

polymer-T

Rill,:rate of thermal initiation, [g-moVl* sec] Rpttl: thermal polymerization rate, [g-mol/l*sec] P ,,: number-average degree of polymerization, [-I [MI: monomer concentration, [g-molll]

Styrene
[AH]: concentration of AH, [g-mol/l] Pryor, W. A. and Coco. J. H., Macromolecules, 3, 500 (1970). 0 1970 American Chemical Society.
Thermally-induced bulk polymerization Temperature: 100-200°C Maximum conversion: 100%

169

initiation

M +M

kl_ Q kI

(=AH)

M +M

2
k-2

k

H HPh . .

PhCHCH2CH2CHPh
+

1,2-diphenyIcyclobutanes Ph CHCH2CH2CHPh AH + S + non-radical products
M + AH M + AH
+

b Y C

ks ki

P h C HCH3 (=

M

e

)

+

(=A*)
H Ph

+

trimer

k ,
aromatization, very fast k A k B

Propagation Termination by combination Chain transfer

Rr*+ M ; R; + R R; + M R,. + A H

+

+

Rr+l. P,+,

kP

kt
kfnl
kfAH

-+
+

R i a + P,
R1*+Pr

M: monomer, R : polymer radical containing r monomer units, P,: dead polymer ; containing r monomer units.

(Ik,2/kt)1’2=Aoexp(A, X+A2X2+A3X3) ks,/k,=(ksn)o/(k,)o+BIX I=2kik1[MI3/{k-~+(ki+k,)[M]+kf~~(I/kt)”~} ~2 kikl[ MI3/k-l=2ki[ MI3

/k.)o=2. [mol/l] V: volume of system. sec] k.03+7.255 X 109exp(-844/T) Ao= 1. [MI2 dV/(V*dt)= -{E/([M]o+E[M]))* d[M]/dt E=(Vx=. [l/mol.=kfi.=C *[Pr.05 1 X 107exp(-3557/T) (kfi.( Cm+ P/2)-(M P)odV/Vdt d(MP)l/dt=Rp-(MP).=2. []/mol* sec] kh. [-I I: rate of initiation.964 X 1OSexp(-10040/T) A.56-1.12-T)/202. [mol/l-sec] Rp: rate of propagation. (MP).l.dVNdt M 00 00 00 (MP)o=C [Pro].5} ki=2. [l/mol*sec] I 9 2 r=2 .: propagation rate constant.: termination rate constant.] R.=d[M]/dt-( [MI .85 X 10”T B1=-1.19 X 105exp(.sec] [MI: monomer concentration.: transfer rate constant to monomer. P=ktRdk.170 Free radical polymerization d(M P)o/d t=R.3 1 X 106exp(-6377/T) (kt)o=l.13 8 1O/T) r: number of monomer units.+P) C.dV)/(V * dt) +=1/( 1+C.J0: propagation rate constant for initial state. [I/mol*sec] (kfiJO: transfer rate constant to monomer for initial state. [I] X: conversion of monomer.05 X lO-’T A2=9.dV)/(V * dt) d[Prl/dt=Rp(Cii. [mol/l.. [-I k. [mol/l] [Mlo: initial concentration of monomer. ( M P ) I = Cr[Pr.76 X 10-2T A3=-3.57-5.dVNdt d(MP)Jdt=Rp(2Cm+3 P)/( Cm+p)2-( P).(Ciii+(3)+P(Cin+P)2 r/2)cbr-([Prl. [I/mol*sec] (k.013 X 1O”logl0((473.-Vx=O)Nx=O (kp)O=l.

Sci.. [I/g-mol*sec] k.. + P.: nth moment of dead polymer. Thermally-induced bulk polymerization Temperature: 200-230°C Maximum conversion: 98% Initiation M + M e K-2 k I Propagat ion Termination by combination Chain transfer AH + M + PhCHCH3 (= Me) + AH + M --+trimer A. W. Appl. kfAH km M: monomer. + M + Rr+I. J. A. E.: termination rate constant by combination.)o: termination rate constant for initial state. MI)/[MI0 } d [M]/dt=-k. Reprinted by permission of John Wiley & Sons.. [Vg-mol * sec] k h : transfer rate constant to monomer. : polymer radical containing r monomer units.16. a a H HPh (=AH) (= A * ) H Ph Rr*+ AH + RI * R. Inc. [M]( I/kt)”2{ ([M]o+E[ E= ~(v~x=l-(v~o~~(v~o (kp)O=l . [mol/l] 171 Hui... Polym. Copyright 0 1972 John Wiley & Sons.: dead polymer containing r monomer units. R. [I/g-mol. P.sec] k. R. and Hamielec.05 1 X lo7exp(-3557/T). Inc.255 X 109exp(-844/T) k. R. [Vmol.* + P.: rate constant of initiation..Styrene (k.749 (1 972).. + P. A.. (kfin)o=2. + R. + M + R I * M * + M +RI.sec] .3 X 106exp(-6377/T) 1 (kl)o=l .: propagation rate constant. [I/mol*sec] (MP). + M + Ri.

[I] Husain. Copyright 0 1978 John Wiley & Sons. [MI: monomer concentrations at initial state and time t. J.172 Free radical polymerization k. (V). [I/g-mol*sec] I: rate of initiation. Sci. respectively. Polynz. Appl. and Hamielec. E. Reprinted by permission of John Wiley & Sons.. Inc. A. 1207 (1978). [I/g-mol* sec] (k&: transfer rate constant to monomer at the zero conversion. [-I (V)o. [Vg-mol sec] (k& termination rate constant at the zero conversion.22. [g-mol/l] X: conversion. A. [g-mol/l*sec] [M]o. . Inc.: volumes of system when conversion is 0 and 1.=..: propagation rate constant.

45 4. 0 1946 American Chemical Society. (1) . .3 0..007 0) x. R: primary radical. Nozaki.0 2. P. [I/mol*sec] [MI: initial monomer concentration. Am. and Bartlett.0 485 5x io4 5 X lo6 5X lo8 l/(r+l))1'2r. [mol/l] [M]=10.99993 0. [P]=8.8 Vinyl acetate Bulk polymerization Initiator: benzoyl peroxide Temperature: 45°C P 2R R+M +R R + R + R-R or disproportionation products --j kl k2 k3 P: initiator. K. (')r=kJk2 kl: decomposition rate constant of initiator..O9 X % reaction at point [l/sec] k2 k3 x.27 X -d[M]/dt=2. SOC.86 [mol/l]. M: monomer.05 0.34 0. [mol/l] 68. [mol/l] [PI: initiator concentration..9966 0.88 0.sec]..-( 0. Chem.: the value of x (=[M]/[Mo]) at the inflection point.9995 0. [ l/sec] k2: propagation rate constant. x. D.977 0.m 9 99 999 9999 99999 of maximum rate 12.9 49.2377 (1 946)..Vinyl acetate 173 1. kl=l. R-R: dead polymer. [I/mol-sec] k3: termination rate constant.3 X [mol/l.5 496 4960 4. J...

D.. H. [ I/min] k2: propagation rate constant. and Kwart. [I/mol*min] b:termination rate constant with terminator or retarder. X: stable product. [I/mol*min] k3: termination rate constant.[ R] [MI [R]=(2k I [P]/h [Z]")"" [Z]= { 2kl kq"[P]/h( -dln [M]/dt)"}I"" Terminator kl [ l/min] w 2 n m 2. J Am. d [R]/dt=2 k I [PI -h[R]"[ Z]'" +0 d [M]/dt=k.174 Bulk polymerization Initiator: benzoyl peroxide Temperature: 45°C Free radical polymerization Initiation Propagation Termination Termination or retardation with terminator or retarder + 2R P R+M +R R+R +X nR + mZ + X kl k2 k3 h P: initiator.38-1. min] Bartlett.2-Diphenylpicryl hydrazyl Duroquinone Iodine (1. Z: terminator or retarder. P. 0 1950 American Chemical Society. Soc..34~ - 1 90 6 X lo4 1 1 1 1 3/2 kl: decomposition rate constant of initiator. . R: primary radical.46) X 10" 1. 72. 1051 (1950). M: monomer. Chem. [I/mol.

.71 X 0.90 X 1 OU2 Overall activation energy: 2 1..0 X 6. Chem. 1507 (1 974). Malavasic. and Lapanje. T.2'-azobisisobutyronitrile Temperature: 55-70°C Conversion: 90% 175 Temperature ["C] 55 60 65 70 Initial rate constant [ l/min] 0. 175.0 X 0. Vizovisek.90X 1 0-2 1.58X 2.. S.48x 1.30X 4..6 [kcal/mol] Temperature: 60°C Initiator concentration [mol/l] Initial rate constant [ l/min] 1.Vinyl acetate Bulk polymerization Initiator: 2.0x 3.97X 1. Makromol. I.0 X 1 0-2 1. A. F. ...58X 1.0X 5.77x 1 o-2 Moze.48X 3. Cernec.ox 2.

=Ri=2kiqI] Stage 1: monomer/polymer ratio within particles remains constant. volume of the particles increase with time QO dVdVp*dt=(kfin[Mp]-kp* Qo)Yo QI* dvflp. P. N. Pr + P. 175.+Pl* P. Chem. P. P.: termination rate constant.+I* +P..+ P. [I/mol*sec] Bresler..zO ktdd Rfin=kfimnN[MpIm~ R.2875 (1974).. PI : primary radical. + P. S. V. Kazbekov. Mukromol.0 X 106exp{(-4700* 700) cal/RT} kp: propagation rate constant... dt=(kpMp+kfin[MpI)Y~ .. Emulsion polymerization Emulsifier: potassium peroxide Temperature: 50-60°C Propagation Monomer transfer Polymer transfer Terminal double-bond polymerization Termination by disproportionation Termination by combination P. N... P. +M +M + P... P. Pr. and Shadrin. + Pr+.. + P. kt.. : growing polymer radical containing r units of monomer.176 Free radical polymerization Bulk polymerization Initiator: dibenzoyl peroxide and cyclohexyl oxycarbonyl peroxide Temperature: 43-80°C Maximum conversion: 20% kt=2.. + + kP + + kfi" kp F kP* ktd kt. M: monomer. + P. E. K. P. [ h o l sec] k..: dead polymer containing r units of monomer.75 X 10' (constant for the temperature range as shown above) kp=2. P.. P.

[mol/l*sec] R..55 Ao=l .dt=(kfpQl+kp* Qo)Yo m m m m Qo=C[Prl.gO. [l/mol*sec] k. []/mol*sec] kfi.: termination rate constant by combination.d: termination rate constant by disproportionation.Q I=l r=l F r2[Pr1.: initiation rate. [mol/l. [b o 1 * sec] kp*: rate constant of terminal double-bond polymerization.=moQdQ~=mo {2(kp[Mpl+kp*Q1 )*+kp EMpl(kfm[Mpl+kfpQi)) /(kp[Mpl(kfin[Mpl+kfpQ~ )-2kfpQI (kp[Mpl+kp* QI )1 Bn=(kfpQl2/Q0+kp* QI)/ [Mp](kp+kfin) Stage 2: composition of particles varies with the overall monomer conversion dQo/dx=CInMo-KQoMo/[MP] dQl/dx=Mo ~ Q ~ / ~ ~ = M o + ~ ( M o + K Q I M o / [[Mpl+cpQ2+KQ1) M~I)(( /(CdMpI+C. A2=-419. [-I .Vinyl acetate Q2..jgO kp=1.sec] N: total number of polymer particles. [particles/l] n: average number of radicals per particles.1014.=kfin/kp.92. Q ~ = C r [ p r l .Q I )1 d(QoBJdx=(CPQ1+KQo)Mo/[Mpl CI. [mol/l-sec] R.: transfer rate constant to monomer.= 1. K=kp*/kp k. [l/mol.: termination rate. Cp=kfdkp.89 X 107exp(-5650 cal/RT). Y o = ClPr.: transfer rate constant to polymer. [ 1/sec] kp: propagation rate constant.43 X 106exp(-9020 cal/RT) kfi. dVdVp..l+kfin[Mpl+kp* )/kfin[Mpl QI M. k.59. [I/mol*sec] k..1 ~ 1 r=l Mn=moQ~/Q~=mo(kp[M...3 ki: initiator decomposition rate constant.=3 X 106exp(-9950 cal/RT). 177 dVdVp.07 X 107exp(-5650 cal/RT). [Vmol-sec] Rfi.sec] k.dt=2Yo(kp[MpI +kp* Ql)(kp[MpI+kfm[Mpl+kfpQ2 +kp* Ql)/(kfin[Mpl+kfpQ~) kp[Mp]Yo + QoBn.: transfer rate to monomer. k p * = A o + A I ~ + A 2 ~ 2 + A ~ ~ 3 . AI=-169. A3=. k.

of John Wiley & Sons.178 Free radical polymerization [P. Inc. [g/mol] mo: molecular weight of monomer. Goosney. Polym. [mol/l] Mo: initial monomer concentration. Sci. [I] NA:Avogadro’s number. Copyright 0 1974 John Wiley & Sons. D.+1. + P. Emulsion polymerization Emulsifier: potassium peroxide Temperature: 50°C Propagation Rr.. Termination by combination kP kfm k..: nth moment of polymer radical.. [-] M. 0 . E. [mol/l] V. [g/mol] M.. Fris.: average number of branch points per molecule.. [-3 18. [mol/l] [P.: total volume of monomer-swollen polymer particles. [mol/l] [M. R. 1: concentration of growing radical polymer with r monomer units. J. +Pr + P. Terminal double-bond polymerization Rr. + M + P r + R 1 * Monomer transfer Polymer transfer R. and Hamielec. J.. R... -Pr + R. + M + R.]: concentration of dead polymer with r monomer units. -jRr+s* Termination by disproportionation Rr* + R. Wright. kP* ktd kk M: monomer. : growing polymer radical containing r units of monomer. P.* +P.+.:nth moment of dead polymer.. [mol/l] B.. [number/mol] f: initiator efficiency.. N.. Reprinted by permission 1247 (1974).[ g/mol] x: degree of conversion. + P.: weight-average molecular weight.: number-average molecular weight. A. D.]: monomer concentration within the polymer particles. R.. [mol/l] Y. + R. Inc. [-3 Q.: dead polymer containing r units of monomer. RI : primary radical. Appl.

75. Cp=kdkp. d(VpRr.4407.)/(V.=mQI/Qo=mo{ 1+Kx. [Vmol.=~~xP(A+A~x+A~x~+A~x~) A=l7. ]/dt+p[Mp] [Rr...: propagation rate constant.Vinyl acetate Stage 1: x i x .6620./( ( ~ ~ p ~ c ~ ( ~ ~ c ~ ~ ~ ~ + ~ ~ c BlI=CpMnxc/( 1-x. [I/mol*sec] k%: transfer rate constant to polymer.+Cpx.. dt)=kp[Mp]rRr. k'd=4. [Vmol * sec] .)}2/{Cl. [ 1/sec] k. d[Rr. d./( l-x. K=kp*/kp Stage 2: X ~ X . A1=-0. I ']-(kp[Mp]+kfin[Mp]+kfpQ~ +kp* Qo)[Rr * I r-2 +kfpr[Pr]Yo+kp*C [pr-sl[Rs.55 X 10 9 (( 1-x)/( 1-0.=0.=930.)mo+Kx./( 1-G)}/Cin l-&)MW=moQ2/Q~=2mo( I+Kx.3 S I d[ Pr]/dt=( kfm[ Mp]+kfpQ I)[Rr * ]-(kfpr[Prl+kp* [PrI)Yo dQo/dx=CInMo-KQoMo/[ Mp] dQl/dx=Mo dQddx=M0+2(Mo+KQ1Mo/[M~])([M~]+C. kfi.l* -(kp[Mp]+kml[Mp]+kfpQ~+kp* Qo)Rr * r-2 179 +kfprPrY o+kp* S I Pr-& =O P.19~))+ 0.Q~+KQI)/(C~~[M~]+C~QI d(QoBn)/dx=(CQ~ +KQo)Mo/[MpI 2fii=1 O-'. kp=3000.25. A2=-6.7530. A3=-0.00 1~ x ] / N A ~~./( 1-x.sec] kh: transfer rate constant to monomer.3495 kFp=l.=kfin/kp.) C. dp=l 150 ki: initiator decomposition rate constant. * dVd(Vp dt)=(kfm[Mp]+k~pQ~)RrkfprPr+kp* * -( Pr)Yo r-I I=l r=l M..

AppZ.]: concentration of dead polymer with r units.: density of polymer. [!/mol sec] ktc: termination rate constant by combination. J.]: concentration of radical polymer with r units. [g/mol] M. f: initiator efficiency. [-3 [Mp]:monomer concentration within the polymer particles. Copyright 0 1975 John Wiley & Sons.mol * dm/sec] dill: density of monomer. [mol/l sec] R. [mol/l*sec] N: total number of polymer particles. [-I q:conversion at which the separate monomer phase disappears. Sci. [I] NA:Avogadro's number.. [-I Fris. [mol/l] Mo: initial monomer concentration. A. and Hamielec. [mol/l] [R. [g/mol] mo: molecular weight of monomer.: nth moment of dead polymer.: weight-average molecular weight.: termination rate. [g/l] d. [-3 Q. [I/mol-sec] ktd: termination rate constant by disproportionation. Inc. [mol/l] [P.: average number of branch points per molecule.97 (1975).180 Free radical polymerization k.: number-average molecular weight. [particles/l] n: average number of radicals per particles.. . [g/mol] x: degree of conversion. [I.. [I/mol*sec] kw: termination rate constant. Inc. [mol/l sec] Ri: initiation rate.: transfer rate to monomer.: nth moment of polymer radical. [gA] R.. [mol/l] V. E. [-I M. Reprinted by permission of John Wiley & Sons.: total volume of monomer-swollen polymer particles.*: rate constant of terminal double-bond polymerization.-. N.. [I/mol*sec] b:desorption rate constant kld: specific desorption rate constant.19. [mol/l] B. PoZym. [mol/l] Y.

[I/mol.: primary radical. 3 173 (1981). B..~1-o . G.: decomposition rate constant of initiator.. E: entry into particle.. D. [ l/sec] k’i: initiation rate constant.: termination rate constant. 19. [I/mol*sec] k. Inc. Reprinted by permission of John Wiley & Sons. Inc. M: monomer..Vinyl acetate Emulsion polymerization Initiator: peroxydisulfate Temperature: 50°C 181 I=: initiator.35 1 o . : growing polymer radical containing n units of monomer. S. [I/mol. H.: entry rate constant of oligomeric free radicals into the particles.~ k. sec] kp: propagation rate constant. P: latex particle. J. [mol/l] Hawkett. [-I [MI: monomer concentration. R. [mol/l] [I]: initiator concentration. Sci. Emulsion polymerization Initiator: potassium persulfate Emulsifier: sodium lauryl sulfate Temperature: 43-45°C Maximum conversion: 50% . Chem. Ed. Copyright 0 198 I John Wiley & Sons. Polym.Polym.3X 3 X lo3 1X lo8 0. 2R-. Napper. [I/mol*sec] z: critical value of the degree of aqueous phase polymerization. -RM.sec] k. and Gilbert. 50 1.

C. [-I V. Inc. P.: polymerization rate.: termination rate constant. Trivedi. [mol/l] [I]. M: monomer. N. Photo-induced.: concentration of monomer in the polymer phase.: concentration of initiator in aqueous phase.. J. [mol/l*sec] k. [I/mol *set] b:decomposition rate constant of initiator. 21. Photo-induced bulk polymerization Sensitizer: benzoyl peroxide Temperature: 25°C via M or sensitizer 2R light R+M +R 2R -+ R-R or disproportionation products rate of initiation fl k2 k3 R: free radical. and Swain. Rajagopal. Copyright 0 1983 John Wiley & Sons.=l X lo3 kt=8X lo7 k. [I/mol*sec] 67. Am.: volume fraction of the aqueous phase. Inc. Chem. 20 1 1 (1 983). D. Sci. [I/mol*sec] k.: termination rate constant.: propagation rate constant. Ed.: volume fraction of the polymer phase that contains polymer particles and the monomer.95 X IO7 [I/mol*sec] in polymer phase kt=1. and Joshi. G. thermally-induced. [mol/l] V. R-R: dead polymer. [I/mol*sec] [MI.182 Free radical polymerization x [~/sec] 4 3 " ~ at 1~=1. Polym. K.Polym.2273 (1945). . Reprinted by permission of John Wiley & Sons. SOC... [ l/sec] k. J. S. K. R.375 R. and peroxide induced bulk polymerization Temperature: 25°C k... M.. Bartett. 0 1945 American Chemical Society. Chem.: propagation rate constant.

.=7. 4 M. J..2381 (1946).7 X lo2 k. PI P. and Bartlett.London. sec] I: intensity of light Burnett.Vinvl acetate kl = 3 X 183 IO-* kZ= 1. sec] k3: termination rate constant.: termination rate constant. 68. P..456 (1947).9-3 1.1 X IO9 k. A189. [I/mol.4"C Initiation Propagation Termination M P.: propagation rate constant.. + M P.1 X IO3 k 3 = 8 X l OI kl: decomposition rate constant of initiator. Chem. M. Proc. W. [ I/sec] k2: propagation rate constant. [Vmol.. H.: active polymer molecule of r units. + P. M: monomer. G.. and Melville. 0 1946 American Chemical Society. Photo-induced bulk polymerization Sensitizer: benzoquinone Temperature: 15. + f(I) k P + k.. at 15°C kt=3. .: deactivated polymer of r units. G. SOC. SOC. [I/mol*sec] k. D. Roy. + M. [I/mol. C... M.. Am..sec] I: intensity of light Swain. P.

D1: polymer growing at one end only.3~10-~ 2 .9 x 10' 2.0~10~ 7. [I/mol. 2 ~ 1 0 ~ Activation energies and frequency factors Rate constant E [kcal/mol] 3.8X IO3 1.1 0 k2: propagation rate constant. P2: initial polymer. R: growing transfer polymer. D2: initial polymer growing at both ends.2X IO8 2.4X IO-' 2. X: active center. Q: dead center.2 x lo8 .184 Free radical polymerization Photo-induced bulk polymerization Temperature: -1 5-0°C Initiation Propagation Transfer 2M X+M D2 + M Di+M R+M D2 + X Dl+X R+X 2x rate=aI[ MI2 k2 k3 k3 k3 Termination 2k4 k4 k4 k4 M: monomer. Temperature ["CI 0 -15 k2 [l/mol*sec] k3 []/mol sec] - k4 [l/mol*sec] 2. PI:dead transfer polymer. sec] A [l/mol*sec] 9.2 6.8 x io5 9.

: termination rate constant. Soc. [I/mol*sec] .7 2640 3700 11.16 X 10"exp(-5240 cal/RT) R. M..: rate of initiation. [I/mol. Temperature ["C] k P 2k.[M12 k. polymer Ma + M + polymer + radical from monomer + +M + Me + M: monomer. [l/mol. London.[M.. A195.: growing polymer radical. Proc. 510 (1949). Photo-induced bulk polymerization Sensitizer: a -azobis(isobutyronitrile) Temperature: 0-60°C Initiation Propagation Termination Transfer with monomer Rate Ri kP[M * I[Ml 2k.Vinyl acetate k3: transfer rate constant to monomer. [mol/l] Dixon-Lewis.68 14. [kcal/mol] A: frequency fator. Roy. G.5 25 1012 5. [I/mol*sec] b:termination rate constant. M .][M] 185 Ma M.9 690 4. sec] E: activation energy. [I/mol*sec] k.002 kp=2.8 0. X 1O-' ktr 0 15. sec] 1: intensity of light a:constant [MI: monomer concentration.43 X lo8 exp(-7320 cal/RT) 2kt=4..88 50 60 325 2. [mol/l*sec] kp: propagation rate constant.

Roy. Bevilacqua.. E. Photo-induced bulk polymerization Sensitizer: a-azobis(isobutyronitri1e) Temperature: 15°C k. T.. J.: propagation rate constant.. 0 1949 American Chemical Society. Soc.12 k2 X 10”=0. J. G. and Hart. 71.. sec] Matheson. and Melville. 0 1950 American Chemical Society. []/mol . and Bartlett. [I/mol*sec] London. Soc.186 Free radical polymerization ktr: transfer rate constant with monomer. Broadbnet. Am. [ I/mol*sec] Kwart. SOC... London. 1060 (1950). A207. [Vmol-sec] k3: termination rate constant.2’-azobisisobutyronitrile Temperature: 15°C k. N.0X I 0-5 k. Roy.496 (1951). E. 26 10 (1949). [I/mol. H. J./kt=3. Photo-induced bulk polymerization Sensitizer: di-tert-butylperoxide Temperature: 25°C 2k3 X 10-’=5..=2.. D. E./k.: termination rate constant. A205. 72... Auer. P.. . Chem. S. S.944-1 . 285 (195 1).. Am.66-6. Grassie.. Chem. E. H. [I/mol. H. sec] k.O 1 k2: propagation rate constant.set] Majury.: termination rate constant. [I/mol*sec] k. W. B. Proc.. Photo-induced polymerization Sensitizer: 2.: propagation rate constant. and Melville. H. Proc. M.5X 10-6 k. W. Soc.

: termination rate constant.5 1o . [Vmol * sec] Bengough. W. 895 1290 1980 555 87 k. Soc. Proc. and Melville. I.15 .1 .7 1.=2. Roy. A225. H.Vinyl acetate Photo-induced bulk polymerization Sensitizer: ceazobis(cyc1ohexane)carbonitrile Temperature: 15°C 187 x k. [l/mol*sec] k. W. Photo-induced bulk polymerization Sensitizer: 1.l'-azobis(cyc1ohexane)carbonitrile Temperature: 16-62°C Maximum conversion: 65% Temperature: 25°C Conversion [YO] 4 23 46 57 65 k.~k. London.~ k.330 (1954). X 1 0-5 240 126 90 6..: propagation rate constant..

k.0 4.4 X lo7 Conversion [%I 4 6 20 23 46 54 57 65 73 E. 2 4.=574. and Melville.=2.8 11. [I/mol*sec] k. [I/mol*sec] Miyama. .: energy of activation for termination. I.2 24.6 > 11.: energy of activation for propagation.4 > 14. [l/mol*sec] E..4 10.: propagation rate constant.4 k. Photo-induced bulk polymerization Sensitizer: azobisisobutyronitrile Temperature: 30 and 40°C kdk.429 (1955). W.: termination rate constant. 29. Soc.=2.2 2 4. H. Chem. A230. Bull. Roy. [l/mol ssec] k.4 E. Proc. Soc. [kcal/mol] Bengough.: propagation rate constant.4 8.8 > 13.: termination rate constant.6 7.. H.2 3. <1 <I - 1.715 (1956). Japan. W.0 > 15.72 X 10'3exp(3250 cal/RT) k.. [kcal/mol] E.4 3.188 Free radical polymerization Temperature: 15°C (early stage of polymerization) k. London.

X lo5 1.00 49. sec] Miyama.52 2.5 0 28.30 66.40 71..80 59.: propagation rate constant.: termination rate constant.40 71.15 39.15 39.10 k. 29.os 2.8 15.3 18.05 .10% Conversion 189 kdk.6 0. [I/mol.30 66.Vinyl acetate Photo-induced bulk polymerization Sensitizer: 1.72 4.l '-azobis(cyc1ohexane)carbonitrile Temperature: 20°C Maximum conversion: 7 1. H.Japan.93 518 172 85. Photo-induced bulk polymerization Sensitizer: 1.80 59.90 0.1 16.0 9. Bull.l '-azobis(cyc1ohexane)carbonitrile Temperature: 20°C Maximum conversion: 7 1. Chem.720 (1956).10% Conversion 0 28.00 49.10 k.20 0.02 2. X lo-' 559 484 354 149 29.78 13. SOC. [l/mol*sec] k.

64 1.6 16. .7 13. Photo-induced bulk polymerization Sensitizer: I .2 7.72 1.0 68.3 45. X 1O5 1.: termination rate constant. [Vmol.43 1.63 3. H.5 8.: propagation rate constant. 1'-azobis(cyc1ohexane)carbonitrile Temperature: 30°C Maximum conversion: 68.53 1. 30. Chem.20 1.6 4.: termination rate constant.26 1.8 0 1.2 35.37 1. 10 (1957). Bull.3 10.1 20.1 14. Bull. SOC.0 18.: propagation rate constant.459 (1957).89 6.9 10.8 28. sec] k.88 2.2 60. I k.15 11.190 Free radical polymerization k.50 4. SOC. Chem. [I/mol.Japan.4 3.31 1.1% Conversion kdk.9 6.. [Vmol sec] Miyama. H.5 53..2 2. 30.56 1. sec] k.Japan.8 37.22 1.49 1. [I/mol*sec] Miyama.10 2.

5)X lo3 [l/mol*sec] at [MI = 0. and Schnabel. [l/mol*sec] Bengough. W. M: monomer.419 (1976). W. + R* 3BP* + M 'BP + M* R.Vinyl acetate Photo-induced bulk polymerization Sensitizer: 1. Polymer. b=(5. 17. + M -+' B P + M . . products + ---f + + ---f + ---f + BP: benzophenone. sec] k... + M RM. .: termination rate constant. [I/mol. Trans. RM. 54.5)X lo8 [I/mol*sec] b=(5.+Kproducts R. 6 k.=795 kt=4.4+0. + R. 3BP*: triplet excited benzophenone molecules.: propagation rate constant.4 [mol/l] Kuhlmann.( o r K M * ) K. K.products + K.868 (1958). Faraday Soc.5+ 1. : growing polymer radical.l '-azo-bis-(cyc1ohexane)carbonitrile Temperature: 15°C k. + R. 191 Photo-induced bulk polymerization Sensitizer: benzophenone 'BP* 3BP* BP +hv 'BP 3BP* 3BP* + 3BP*+ 'BP + 'BP 3BP* + RH K. I.. R.6 x io7 [kcal/mol] Overall energy of a c t i v a t i o ~ 4 .

W. [I/mol*see] Kuhlmann. and benzoinisopropylether (BIPE) Solvent: benzene 0 OR II I 0 II OR [Ph-C-C-Ph]* . [l/sec] non-radical products. Chem. R. 70.1 decomposition rate constant.192 Free radical polymerization Photo-induced solution polymerization Sensitizer: benzoin (B).. and Schnabel. [I/mol see] kq: rate constant for reaction of monomers with excited sensitizers which lead to k:rate constant for reaction of monomers with excited sensitizers which lead to radical products. Sensitizer kl B BA BME k&l [Vmol] [ 1/see] 1 . 2 io9 ~ kl: k&I [l/sec] [I/mol] kl k. Benzoinmethylether (BME). 3 io7 ~ 1. M: monomer. Makromol.+ - I Ph-C. 145 ( 1 978). 6 X lo7 kqk [I/mol] [Vmol] <io-2 5 . Angew. . benzoinacetate (BA). + I SC-Ph I kl H S* + M + non-radical products S* + M radical product --+ H k4 kqr S*: excited sensitizer..

50 0.6 2. and Hirota. 3. Mito.: termination rate constant.8 2. [VAc]=5.1 1. [VAc]=10.2. [I/mol.O 2.9 3. [sec] [VAc]: concentration of vinyl acetate.40 0. .72 [mol/l] and [ACN]=l. [I/mol*sec] T: radical life time. Yamamoto.42 0.2-DichIoroethane 1.sec] 3550 290 250 80 110 170 2350 2730 1130 2k.: propagation rate constant. Nippon Kagaku Kuishi.3 3 . 408 (1979).1. T.1 3.39 0.48 0. M.Vinvl acetate Photo-induced solution polymerization Sensitizer: azobiscyclohexane carbonitrile (ACN) Solvent: see table (50 ~01%) Temperature: 30°C Solvent z kP 193 [=I None(') Benzene Toluene Ethyl benzene Chlorobenzene o-Dichlorobenzene Cyclohexane 1.2 [mol/l] (')Nosolvent case..49 0. X [l/mol..2-TetrachIoroethane 0.50 X In the other cases. sec] k. T.4 3.sec] 2.42 [l/mol. [mol/l] Yamamoto.36 [mol/l] k. A.43 0..50 0.. [mol/l] [ACN]: concentration of ACN.

42 -1. J.OX1O2 2.0 X 10' k.: propagation rate constant. 58. M. 169 (1962). J. M.5 X io9 . and Majer. Downer.8 X lo2 5. Makromol.. and vinylacetate Initiator: polyvinylacetate Temperature: 14-28°C Initiator Temperature ["CI 15 14 28 25 kP [I/mol-sec] Y -ray PVA latex and y-ray 23 0 23 0 220 3 10-470 k..30 Bulk Normal solution 7. Burnett. Chem. polyvinylacetate. M. kt 6.6~ io9 Abnormal (after 5% polymerization) 6. Solution and bulk polymerization Solvent: ethylacetate and n-hexane Temperature: 3 1-63°C Solvent Ethylacetate n-Hexane Activation energy [kcal/mol] 4. G. [I/mol*sec] Allen. P.194 Free radical polymerization Radiation-induced emulsion polymerization Radiation source: y-ray Ingredients: water.... R.7X102 2. E.

Roy. Soc.: propagation rate constant.5 772.80 - ktr.50 83. sec] Chadha. J.9 4633. H.0 308..60 208.240(1957). 53.s/kp ktr. W. S..=3700 Cs=ktr. M. Solution polymerization Solvent: see table Initiator: 2.: termination rate constant.. [I/mol-sec] Burnett. Faraday SOC. [Vmol. Trans. Proc.: propagation rate constant. N. [I/mol*sec] k..50 125 1.Vinyl acetate k.S x 1' 0 [l/mol*sec] Benzene Toluene Ethyl benzene Chlorobenzene Chloroform Carbon tetrachloride Acetone 109. and Misra. sec] k..00 432. . G. R. [Vmol.s:transfer rate constant to solvent.2'-azobisisobutyronitrile Temperature: 60°C 195 Solvent cSxio5 29.90 55 1..7 2040. Shukla. S.9 k. A189.O - I 17. London.494 (1947). and Melville. G.

P.: rate constant for termination by primary radical. Mukromol.X 6. Solution polymerization Solvent: ethyl acetate (EA) and dimethyl carbitol (DC) Initiator: 2.4-dimethylvaleronitrile) Temperature: 50°C C R+M + 2R +XI kd ki . [I/mol*sec] k'. 48.: growing radical with r units of monomer. P. C. M: monomer. sec] Allen.sec] kp: propagation rate constant. [I/mol. E.: termination rate constant.196 Free radical polymerization Solution polymerization Solvent: benzene Initiator: 2..+I + polymer --t polymer products + + I k'P[Rl[Ml kJP1[MI kt[PI2 k't[Rl [PI 2k". [I/mol*sec] k". M. R. P.sec] kip: initiation rate constant. + P. 9 2k. [I/mol. Chem.0 I: decomposition rate of initiator..[R]* R: primary radical. k P 2300 k'.2'-azobis( isobutyronitrile) Temperature: 60°C Rate Initiation Propagation Chain termination R+M Pr + M P. and Patrick.2'-azobis(2. 89 (1961). + R 2R --tR +PI P.: rate constant for reaction between primary radicals. [mol/l. [I/mol*sec] k.

Ito.8 5. M: monomer. X..0 18. [I/mol*sec] A-1.: rate constant for termination by primary radical.k. Reprinted by permission of John Wiley & Sons. X 10-4 6. 29. Copyright 0 1972 John Wiley & Sons.0 EA DC DC h:decomposition rate constant of initiator. [I/mol*sec] ki. + P. Inc.: termination rate constant... sec] k.: initiation rate constant. [I/mol*sec] k. P. Thermally-induced and photo-induced solution polymerization Initiator: 2. + X. Sci.2'-azobis(isobutyronitrile)(AZBN) Sensitizer: 2. X.4 16.2 kt.+R + P .: rate constant for reaction between primary radicals. Inc. Polyrn. J. -+P. or P.: propagation rate constant.4 7. 2R + products 197 kP kt kti kii C: initiator../k. [ l/sec] k. 1481 (1972). 10. R: primary radical.Vinyl acetate X n + M +Xn+l X. [Vmol.: growing radical with n units of monomer.2'-azobis(cyclohexane-1-carbonitrile) Solvent: shown in table Temperature: 30°C . [I/mol*sec] k.: dead polymer with n units of monomer.. Solvent Solvent/monomer [volume/volume] 1 3 7 kt/k. K.

05 1.00 [mol/l] .334 0.10 k.97 k 0.02 1.00 [mol/l]. Inhibitor=p-benzoquinone Photo-induced polymerization Solvent k.04 2.I 7 f0.76 0. 10 [mol/l] [monomer]=2.45 3.0235 430.13f0.66f0.39 0.37k 1.48 f0.37 0.1 1 +OS9 2.10 6.75 4.2'-azobis(isobutyronitrile)]=O.8 3.61 3.08 f0.09 0. X 1O'2 Tl/mol*secl 0.58 + 0.942 + 0. X 1O-* Tl/mol*secl 2. [monomer]=2.-carbonitrile)]= 1 3.64 Initiator [2.30 3.00 X IO" [mol/l].39f0.198 Free radical Dolymerization Thermally-induced polymerization Solvent 0.5 1 f0.01 1.05 0.61 f0.10 0.19 f 0.54 * Sensitizer [2.12 0.12+ 1.974 4.237 3.2'-azobis(cyclohexane.

M. D. and Nozakura.88 4.. EtBz: ethyl benzoate k. . J.76 0:5.921 (1979).: termination rate constant. J .82 2.1 1 :2..0 [mol/l] 199 EtAc:EtBz Volume ratio 1 :o k.48:1. [I/mol*sec] Kamachi. [I/mol. Liaw.: propagation rate constant. .22:O 5..74:3. Polym.64 [Monomer]=2.sec] k. S. X I 0-2 [I/mol*sec] 2: 1 1:l I :2 0: 1 63 7 104 78 48 37 EtAc: ethyl acetate.Vinyl acetate Photo-induced polymerization Solvent EtAc:EtBz Molar ratio 8. 11.

=5 . Sci..5/T) b=3.61 kl [ l/hr* 0. H. [mol%] R: overall rate of polymerization. [ l/hr] k: overall rate constant of polymerization.9 Vinyl chloride Free radical Polymerization Bulk polymerization Initiator: 2. and Hamielec.89 2.2 1 CM=kfm/k. Reprinted by permission of John Wiley & Sons.: propagation rate constant.) X 10-2 [ l/hr.79 X 1 018exp(-15460/T) [I]: initiator concentration. 50. [-3 Abdel-Alim. [ l/hr-mol%] k. Appl.54 X 101’exp(-8505..: termination rate constant.4 1 3.16. Copyright 0 1972 John Wiley & Sons. [ l/hr] kl: initiation rate constant.25 6. [I/hr*mol%] f initiator efficiency. .23 1. E. [ l/hr* ken:transfer rate constant to monomer. A.1 /T) kl=3. [ l/hr* RI: initiation rate.78exp(-2768. Inc. J. and 70°C Temperature [“C1 30 50 70 (k:/k.200 1. Inc.2’-azobisisobutyronitrile Temperature: 30. 783 (1 972). A.mol%] 1. Polym. [ l/hr] k. [ l/hr*mol%] b:initiator decomposition rate constant.

ki=1.l: growing polymer radical with n units of monomer.=1.15X10-6 C: conversion. k. []/mol* sec] ktm: chain transfer rate constant to monomer..+ M I Pn + Pin P n + Pin . k.: propagation rate constant. Chem.l X lo4.=1. Bulk polymerization Initiator: lauroyl peroxide Temperature: 50°C Initiation Propagation Chain transfer to monomer Termination I + R+MI+ PI. P.. Mukromol..: initiation rate constant. []/mol sec] k. k.: propagation rate constant. and Sund. T. b=1.. MI:monomer. Fl$gstad.013 X lo4.=l.f + + I: initiator. H.3X10S.. Hertzberg. [I/mol. [!/mol sec] ki: rate constant for the decomposition of initiator. [I/mol*sec] . 164. sec] klc: termination rate constant by combination.02. [I/mol. R: primary radical. + MI + PI. [-I ktp: termination rate constant in the polymer phase.15 X 10-6 k. [mol/l] - Ugelstad. [ l/sec] [1]0: initial concentration of initiator. J. M.8702X IO9 klm=10. sec] k. 171 (1 973).)~'20.45kpC~'2 kl.: dead polymer with n units of monomer.Vinyl chloride Bulk polymerization Initiator: lauroyl peroxide Temperature: 50°C 20 1 dC/dt=(k~[I]o/kl. E.=1..

W.32 X lO"exp(-l5460/T) kpo=3X 1O9 exp(-3320/T) { kp=kpoexp 0.: dead polymer with n units of monomer.+I -+ P.)} ktm=5 .=O. [ I/sec] Ray. [ l/min] + - I*+M Rx+M R. Jain..+Py R. + R.19.4 159 1 p=0. R. Inc.. 1297 (1975). and Salovey. Reprinted by permission of John Wiley & Sons. Polym. R..202 Free radical polymerization ktd: termination rate constant by disproportionation. H. R. [I/mol*sec] h:decomposition rate constant. S.O11 5ktm b=6. [ l/min] h:rate constant for decomposition of initiator. 32kt. ktl=7.+Ry Rx+ R y 21* RI R.: growing polymer radical with n units of monomer.42642 kb: rate constant for short-chain branching. kb=O. + P. I*: primary radical.+Ry R x P... J. P. Inc.2( 1/Vf 1Nf. Bulk and suspension polymerization Temperature: 50 "C Initiation Propagation Transfer to monomer Transfer to polymer Intramolecular transfer Termination I M: monomer.+Py Px+y -+ + + + ---f . Copyright 0 1975 John Wiley & Sons. K. I: initiator. + M R..78kpexp(-2768/T) k.8 X 10I3exp(-2190/T) vo=5 [I] Vfcr=Vfat xf vf=ax+p a=-0. Sci. Appl.

C.6 X 1O7 [l/mol*hr] n=10-5-5 X r.Vinyl chloride 203 k... [number/mol] n: average number of radicals per latex particle. hr]. Copyright 0 1969 John Wiley & Sons.. Mucromol.: rate constant for chain propagation.49 (1969). C27..: propagation rate constant. [Vmol. J. Sci. min] kt..=3 . Mork. [I/mol* min] Vf: free volume fraction of reacting mixture in polymer-rich phase Vfcr:critical value of Vf beyond the propagation rate becomes diffusion-controlled Sidiropoulou. Dahl. . and Kiparissides. [I/mol*min] ktp:rate constant for chain transfer to polymer. [I/mol*hr] CM': monomer concentration in latex particles [mol/l] NA: Avogadro's number. P. Reprinted by permission of John Wiley & Sons. Emulsion polymerization Initiator: K2S208 Emulsifier: Empicol-8043 (sodium laurylsulfate) and Aeroso I DBM (d i-n-buty 1su I fosuccinate) Temperature: 50°C rp=k.: rate constant for chain transfer to monomer. P.: rate constant for chain initiation. J. [I/mol*min] ktc: rate constant for termination by combination. Polym. VC: vinyl chloride. P. A27. and Rangnes.257 (1990). [I/mol*min] kt: =ktc+ktd ktl:termination rate constant in monomer rich phase... [mol VC/I H20.-Chem. [I/mol*min] ktd:rate constant for termination by disproportionation. [ l/mol*min] k. J. k.: polymerization rate. Inc.CMpnN"/NA c ~ ' = 6[mOl/l] k. Sei.. [-I N": number of latex particles per liter H20.. C. [1/1] Ugelstad. Inc. E.

l -azo.3 X 106exp(-3700cal/RT) Ri=2. M: monomer. A221. [l/mol sec] kt: mutual termination rate constant.2'-diphenyl.1-cyclohexanenitrile Solvent: tetrahydrofuran (THF) Retarder: 2.1-picryl hydrazy I Temperature: 2555°C Rate Initiation Propagation Monomer termination Mutual termination A+hv+ R+M P + M -+ P+M 4 P +P 4 ---f R P P inactive products inactive products Ri kJP1[MI kx[Pl[Ml kt[PI2 A: photosensitizer. R: primary radical from sensitizer. and Wright. P: growing polymer radical.9X 105exp(-7800 cal/RT) kt=l. W.= 1.204 Free radical Dolymerization Photo-induced solution polymerization Sensitizer: 1.07 X 10-8[mol/l*sec] at 25°C [mol/l.sec] at 55°C R3p3..41 (1954). Roy.=3. M.: monomer termination rate constant. . Burnett. k. SOC. [I/mol*sec] Ri: initiation rate. [I/mol*sec] k.39 X Activation energy of initiation=3200 [cal/mol] k..3 X 10'2exp(-4200 cal/RT) k. Proc. G. [mol/l*sec] London.: propagation rate constant. W.

1 X 10-2 k. Copyright 0 1967 John Wiley & Sons. Solution polymerization Solvent: diethyl oxalate and 2. and Moore.. [mol/l*hr] f: initiator efficiency. [Vrnol-hr] kts: solvent transfer rate constant.. M..75 kd=2X CM=k$k. Reprinted by permission of John Wiley & Sons. Inc. J. M. and Lim. []/mol * hr] [C]: initiator concentration.2’-azobisisobutyronitrile Temperature: 40°C 1=2&[C] f=0. D. Reprinted by permission of John Wiley & Sons.Vinvl chloride Solution polymerization Solvent: tetrahydrofuran Initiator: 2. [mol/l] 205 - Mickley.. Kolinsky. L. Ryska. [Vmol hr] k. H. Inc. S. [-3 b:initiator decomposition rate constant..4-dichloropentane valeronitrile Initiator: 2.. Inc. .=5 X IO” Cs=kts/kp=3X IO” I: initiation rate. Polym. Sci. Michaels.: propagation rate constant kt: transfer rate constant C16.: propagation rate constant. A.. Copyright 0 1962 John Wiley & Sons. S. J. [ l/hr] kf: monomer transfer rate constant.4-dimethyl-4-methoxy) Transfer agent: tetrabromomethane Temperature: 25°C kp2/kt=4.621 (1967). A.. 121 (1962).2’-azobis(2. Polym.60. Sci. Inc.

)o+C. Crosato-Arnaldi.206 Free radical polymerization Solution polymerization Solvent: 1. [-I (PJ0: number-average polymerization degree in absence of solvent.[M] CM=kt.2-dichIoroethane Initiator: lauroyl peroxide Temperature: 50°C 1/P. Mukromol.: number-average polymerization degree.)o=C~ul+(fk~k../k.217 (1968)../k. [mol/l] b:decomposition rate constant of initiator.[S]/[M] (I/P.5 X k. 1 x 10” Cs=k. [-I Vidotto. [I/mol*min] k. [mol/l] [I]: concentration of initiator. [I/mol-min] ktrs: transfer rate constant to solvent.)”~[I]”~/k. .69 [min’”.. [mol/l] [MI: concentration of monomer.=l . [I/mol-min] f: initiator efficiency. [ l/min] k. [I/mol. [-3 [SI: concentration of solvent. and Talamini.=4. 114.. Chem.”*/k.: termination rate constant. G. m01’/~/1’/~] P...: transfer rate constant to monomer. A...: propagation rate constant..=( I/P.min] k.. G.=l..

G.40 [s/cm3] g2=(1-os)( 1-x) [I]: concentration of initiator.1}/os b=3. and 2.: transfer rate constant LPO 1.2’-azo-bis-isobutyronitrile (AIBN) Temperature: 50°C Maximum conversion: 90% 207 Rate constant kt’l2/k.85[g/cm3] pp=1. k..6/RT) I/P= (x/pP)+((1-x)/pln) [s/cm31 pIll=0. 117.45 AIBN 1.79 X 10’3exp(-19806/RT) [l/m01%”~*hr] p=5... x >0. A. Chem. Gasparini.79 X 10’8exp(-15460/T) [l/hr] k=2. benzoyl peroxide (BPO). x 5 os R=p( 1-x)g. and Talamini. [-I .85 Crosato-Arnaldi. Suspension polymerization dx/dt=r(T(t). t) d[I]/dt=-kd[ I]+( [I]/p)(ddp)(dddt) r=k[ I]’. Makromol. 140 (1968).98 X 1O”exp(4828.: propagation rate constant k. [mol%] x: monomer conversion.. P.4 .. q= {P( 1 .Vinyl chloride Suspension polymerization Medium: water Suspending agent: vinylacetate/maleic anhydride copolymer Initiator: lauroyl peroxide (LPO).’R R=( 1+qx).

[ I/hr] k: overall polymerization rate constant. [-3 ‘r:reaction temperature.. . [g/cm3] pp:density of polymer. Polym. [-I p: kinetic constant defined as above. [mol%/hr] R: rate defined as above equation. [-I g: gel effect correlation defined as above.30. [-I 0. C.925 (1990).208 Free radical polymerization r: overall polymerization rate. [g/cm’] pm:density of monomer.: critical conversion defined as above. J. Sci. [-3 p: density of system. [ I/mol%”**hr] q: kinetic constant defined as above. Eng.. [g/cm3] Pinto. [” K] kd: initiator decomposition rate constant.

+ M p.10 Vinylidene chloride Photo-induced bulk polymerization Temperature: 15-35°C Maximum conversion: 5. [I/mol. + PI.. [I/mol*sec] Burnett...:dead polymer containing n units of monomer. Trans.0X 105 . PI: primary radical.=the order of 1030 [MI: monomer concentration.=40 [kcal/mol] Frequency factor of k. k. J. [mol radical/l. PI.. D.:growing radical containing n units of monomer.6 36. Faraday Soc. + - Pi + M PI. 46. sec] kp: propagation rate constant. ' I 2 Temperature kP [I/mol*sec] l"C1 15 25 35 Activation energy of kp=25 [kcal/mol] Activation energy of k.976 (1950).Vinylidene chloride 1.8 0.3 8.=Ap=the order of 10l6 Frequency factor of kt=A. and Melville. MI. kt [I/mol*sec] 2.sec] kt: mutual termination rate constant.26% Initiation Propagat ion Termination M + hu + 209 2P1 P2 Pn+I 21 kP M: monomer. W. H.23 x io5 1.75 x io5 18. + + kP M"+ MI. [mol/l] I: light density. d [M]/dt=[ MI(21)'12kd k.

:transfer rate constant to monomer.210 Free radical polymerization Thermally-induced and photo-induced solution polymerization Solvent: N-methylpyrrolidone Temperature: 25-75°C Initiation Propagation Monomer transfer Solvent transfer Regeneration Termination I: initiator. Ma : growing radical.5.: termination rate constant.. log(kt)=12. K. 10. .. W.0-1160/T E. [ l/sec] k.0-l 970/T.: frequency factor for termination reaction. 654 (1977). [I/mol*sec] k.: activation energy for propagation reaction. R. Re : primary radical. Nelb. G.: activation energy for termination reaction. [kcal/mol] A. Nelb.: propagation rate constant. H.: regeneration rate constant.=10l2 decomposition rate constant of initiator.4. and Stockmayer. A.. [l/mol*sec] ktn. [Vrnol-sec] A. 0 1977 American Chemical Society. [I/mol*sec] kd: Matsuo. [I/mol-sec] E. [kcal/mol] E. S: solvent.. P: polymer. A.: frequency factor for propagation reaction.=109. [I/mol*sec] ktrs:transfer rate constant to solvent. log(kP)=9. [I/mol*sec] k. Macromolecules. W.. M: monomer. Et=5t2.=9* 1. G.

+ AN -+ AN' AN.8 [kcal/mol] [i]: R.[X]=kt[AN'] Rp=(kfkPK/kt)[ANl2 [TEP] At the high temperature such as about room temperature: k. [AN-][AN] .Acrylonitrile 21 1 2.< ki k.: concentration of species i polymerization rate propagation rate constant termination rate constant .+ CH&H-CN (X) X Z + (C~HS)~P+-CH~-CH-CN (Z) ..-+poly-AN AN: acrylonitrile.P'-CH~-CH(CN)-CH~-CH(CN)(Z-AN') (3) Z-AN.* . >ki ki[Z] [AN]=kt[ AN-] Rp=(kikpK/kt)[ANl3[TEP] Overall activation energy for the polymerization=6.: k.+ - + AN (C~HSO).: k. R = k.1 Acrylonitrile Anionic solution polymerization Solvent: benzene and acetonitrile Catalyst: triethyl phosphite (TEP) Temperature: . Ionic polymerization 2. Z: zwitterion. At the low temperature such as below 0°C: k.10-50°C TEP + AN & (C2H5)3P .

212 Ionic polymerization k.. 13. J. P. Copyright 0 1975 John Wiley & Sons. and Quintana. . Sei. 2517 (1975). Inc. Polym. Chem.: initiation rate constant for reaction (3) K: equilibrium constant for reaction (1) Ogawa. Polym.: rate constant for reaction (2) k. Inc. Ed.. T. Reprinted by permission of John Wiley & Sons.

Inc.0 1 14(” Hexane 50°C 0.010 [mol/l]... Livigni. Copyright 0 1963 John Wiley & Sons. ‘2’[n-BuLi]>0.5 k 0 .00 12“’ Cyclohexane 5°C 0.1 +.004 [mol/l].. 1735 (1963).Butadiene 2. J. L. and Fetters. Sci. n-hexane.: propagation rate constant.3 X 1 04exp(-6100 cal/RT) for THF k.05 213 k. A l . J.. and toluene Catalyst: n-butyllithium (n-BuLi) Temperature: 5-50°C Maximum conversion: 100% R=K[M]* Polymerization rate constant K [I/mol. Reprinted by permission of John Wiley & Sons. Polym. Anionic solution polymerization Solvent: cyclohexane. E. Inc. [I/mol*sec] Morton. E.2 Butadiene Anionic solution polymerization Solvent: n-hexane and tetrahydrofuran (THF) Catalyst: butyllithium Temperature: 0-50°C Maximum conversion: 90% Solvent n-hexane THF Activation energy of propagation [kcal/mol] 21..0443‘2’ “’[n-BuLi] >0. min] Cyclohexane 30°C 0. A.0. .=4. M.0076“’ Toluene 50°C 0. 3 6. R. Bostick.

90 tert-BuLi 0.. and toluene Catalyst: n-butyllithium(n-BuLi).51 k0.=k. PoZym. H. Inc. L.=k. A3.. Reprinted by permission of John Wiley & Sons. Copyright 0 1965 John Wiley & Sons.03 ki (Cyclohexane) n-BuLi 0. [mol/l] [MI: concentration of monomer.214 Ionic polymerization R: polymerization rate.002 n-Hexane 0. Inc.min] [BuLi]: concentration of butyllithium.[BuLi]’”[M] for [BuLi] > [mol/l] for [BuLi] < [mol/l] . J.=k‘. Sci. and i-BuLi Temperature: 50°C R. sec-BuLi. [Umol. Copyright 0 1965 John Wiiey & Sons. H.. [mol/l] Hsieh. Reprinted by permission of John Wiley & Sons. [mol/l*min] ki: initiation rate constant. n-hexane. 163 (1965).[BuLi]’”[M] R.min] K: polymerization rate constant. Inc. Anionic solution polymerization Solvent: cyclohexane and toluene Catalyst: sec-butyllithium (sec-BuLi) Temperature: 5-30°C R. Anionic solution polymerization Solvent: cyclohexane.015 sec-BuLi 0. Inc. [mol/l] Hsieh. PoZym. L. tert-BuLi. [mol/l..015f0. 153 (1965). J.024+0.[BuLi] [MI Initiation rate constant ki [i/mol smin] ki (n-BuLi) Cyclohexane 0. A3.003 Toluene 0. [I/mol.min] [MI: monomer concentration. Sci.16 Ri: initiation rate.

N'.Butadiene Propagation rate constant k. Inc.N.033 0.: propagation rate.: propagation rate constant. 173 (1965). J.. A3.. [mol/l] [MI: concentration of monomer. Inc. H. Polym.: propagation rate constant.020 k. [ ~ " ~ / m o minl ~'/~ R.N'-tetramethyl ethylene diamine (TMEDA) Catalyst: n-butyllithium (n-BuLi) Solvent: n-hexane Maximum conversion: 30% Temperature: -4-7°C BuLVTMEDA TMEDA BU-L~*(TMEDA)~ =CH-CH =CH2 CH2 + Bu-Li+(TMEDA)Z Bu-CH2-CH-Lii(TMEDA)2 CH=CH2 + JL I BuLi/TMEDA +CH2 =CH-CH =CH2 JL Bu-CH2-CH-Li CH=CH2 TMEDA I (TMEDA) 1 BU-CH~-CH-L~'(TMEDA)~ CH=CH2 I . Anionic solution polymerization Modifier: N. Reprinted by permission of John Wiley & Sons. L. [~'/~/rno~'/~. [l'/2/mo1''2 min] P. Sci.min] 30 0. [mol/l] Hsieh. Copyright 0 1965 John Wiley & Sons. and k'. Solvent Cyclohexane Temperature ["CI k P [I'/2/mo1''2* minl 215 k'. [mol/l-min] [BuLi]: concentration of sec-butyllithium.

SOC. sec] k.12 * ki: initiation rate constant. PI: growing polymer with one unit of monomer. F. C.. J. I.5 k 1 .+~ Li'(TMEDA)2 CHzCH2 Initial polymerization rate=k. P.5 4.ki[ B] [A] Activation energy [kJ/mol] Initiation Propagation 15. N. 90% for 50°C Initiation: Propagation: I + M P.: growing polymer with x units of monomer.. Anionic solution polymerization Solvent: hexane Catalyst: n-butyllithium (n-BuLi) Modifier: tetramethyl ethylene diamine (TMEDA) Temperature: 50-70°C Maximum conversion: 100% for 60 and 70"C. and Robb. 1 (1972). Li'(TMEDA)2 +CH2 =CH-CH =CHz CH=CH2 I AL BU(CH~-CH)-. Chem. J.+I Kl KP I: initiator..: propagation rate constant. J. Trans. 68. J. Furaduy.216 Ionic rtolvmerization Bu(CH2-CH)-.0 14. M: monomer.. [dm3/mol sec] [A]: ratio of BuLi/TMEDA [B]: concentration of butadiene. [mol/dm3] Hay. . + M -+ + PI P.O I Pre-exponential factor logA 9.8 Rate constant X 1O3 at 240°K 397. McCabe..8 2.0 0. [dm3/mol.

W.3338e~p(-19306 217 K.. J.. Polym. Miller. G. Sci.Butadiene For fully modified (excess TMEDA at TMEDA/Li=2. permission of John Wiley & Sons.994 X 10'2[I]~.[I]o=l . Appl.: initiation rate constant [IlO: effective initiator concentration Chang. Inc. Inc. C. R.. J.024 X 108[l]oexp(-10332 cal/RT) For unmodified polymerization (no TMEDA) cal/RT) K.. 39.5) K. and Schorr.[I]o=7. Copyright 0 1990 John Wiley & Sons. . Reprinted by 2395 (1990). Jr. C.: propagation rate constant K.

[mol/l] Wittmer. [mol/kg] [C-1: concentration of sodium caprolactam added. Makromol. [mol/kg] [I]: concentration of imide groups in the form of acyllactam and. H. [C-]=(0.5 [kcal/mol] [CHI: concentration of caprolactam.77) X 10-2 [mol/kg]. sec] [i]: concentration of species i.88) X 10-2 [mol/kg] kK0. Chem.. and Gerrens.44-0. [mol/l.79 [kg”2/mol”2.44-1.62-1. vBr: polymerization rate.6-bis(carbamidocaprolactam) Initial temperature: 122-156°C vB. V. 27 (1965) Anionic polymerization Catalyst: a mixture of sodium caprolactam and tetraacetylhexamethylene diamine Temperature: 140.sec] Overall activation energy E= 17.218 2. 89.’[I][C-]o. in the form of diacylamino groups in the polymeric chain.170°C Maximum conversion: 9. [mol/kg] . [mol/kg] K: dissociation constant.6kcal/RT)[catalyst][cocatalyst][monomer] .2 mol% 2 -CO-N-CO-CHz- I [I1 + -N--CO e [C-I -CO-N-CO-C‘-CO[KU + 2 -NH-CO- At 150°C -d[CH]/dt=k K0. = 2 5 X 10’8exp(-36.5 - [I]=(O. P.3 &-Caprolactam Ionic polymerization Anionic polymerization Catalyst: sodium caprolactam Cocatalyst (accelerator): hexamethylene. at more advanced stages of the reaction..5=1.1.

E.014 0. J .5 61.014 - Catalyst [moll 0.4 223 804 0. and Sebenda.002 . Chem. 2.002 0. 0 .&-Caprolactam k: polymerization rate constant. Z .C R Activator K. Anionic polymerization Catalyst: sodium caprolactam Activator: N-carbanilinocaprolactam Temperature: 85-135°C Maximum conversion: 30% 219 Catalyst Temperature ["CI 85 100 115 135 150 Kp: propagation rate constant. Collection Czechoslov.'o C -N 0 C(CH2)SN -CR 0 H O 'I > /H II C-N-C(CH& II 0 0 II hCR .. + ( i 0 0 II 0 II 0 II 0 II - M O .9 15. 0 1969 American Chemical Society.014 0. 270 (1968). J.. C. Commun.II 0 M+N-c + 0 Activator [equiv] 0. 33. [ 13'2/mo13/2min] * Greenley. J.009 - KP [13/2/mo~3/2*min] 2.. [kg/mol*sec] Sittler.009 0.. R. Macromolecules.009 0. and Kurz. E. 561 (1969). . Stauffer.II + O .

. .H . 1 f y p 0 II (9:: kZ+ -N k2.-N u (J(J+(j = I II H O t N-C ? C-N-C 9 9 (-) ? kl+ kl.C N I1G I I U uuu+o C-N C-N-C .

G.4-TCCI: 2. [I/mol*min] [MIo: initial monomer concentration..77 2.70 0.0 AcCI: n-acetylcaprolactam.033 AcC 1 PhCCl 2. HMCCI: hexamethylene-bis-carbamoyl caprolactam. [mol/l] .36 0. 469 (1975). and Talamini.70 10. Inc. A. [moI2/l2/sec] Rigo.70 6.&-Caprolactam kl+. Anionic polymerization Catalyst: sodium metal or sodium caprolactam Activator: shown in table Initial temperature: 160 and 190°C dp/dt=(k[AI2/[M]o)( I+)( l+mP/[A])exp( -U/RT) Activator k X IO-" [I/mol*min] m [mol/l] 0.93 0. [mol/l] m: describes the intensity of self-acceleration effect during chain growth. [kcal/mol] p: degree of conversion.. Polym.. PhCCI: phenylcarbamoyl caprolactam. k: polymerization rate constant. [-I [A]: concentration of activator =[C]/N. 2. [mol/l] U: activation energy for polymerization.22 2. G.16 0. k2+.4-TCC1 DPhMCCl HMCCI 0. Copyright 0 1975 John Wiley & Sons..4-toluylene-bis-carbamoylcaprolactam. Ed. Lett. DPhMCCI: 4. kl-. 13.4-diphenyImethane-bis-carbamoylcaprolactam. Reprinted by permission of John Wiley & Sons. Inc. k2-: 22 1 rate constants defined in reaction schemes. Fabbri.

[ l/sec] Bo: autocatalystic parameter. Y. [-I E.42 X 1 O'* n 1. Eng.0 Ea [kcal/mol] 2494 X: monomer conversion. 1791 (1982). Sei. D. A. [-I [C]: concentration of catalyst. Ivanova. [sec] [-I Lin. G.. L. Frolov. A. N. E. Ottino. J... 23. Polymer.222 Ionic polymerization N: the functionality of the activator... V. . and Andrianova. [kcal/mol] n: the order of dependence on monomer concentration. Ivanova. [-I Ao: pre-exponential constant./RT) A0 [ 1/sec] 2. J. Anionic polymerization Catalyst: sodium metal Initiator: phenyl isocyanate Temperature: 140. t: reaction time.145°C Autocatalystic type rate equation dX/dt=Ao( 1-X)"(1+BoX)exp(-E. 25.. L. S. M. and Thomas...: apparent activation energy. [mol/l] Malkin.2 B O 6. S.. 1155 (1985). Z. Polym.

P.160°C Maximum conversion: 100% Reaction System Pre-exponential factor sec] [~~’~/mo~~’* 223 - Activation energy [kcal/mol] 16.. et al. PA(Nov. Eng.83 X lo7 1..8 % Initial reaction temperature: 153. 1982)./RT) . and Sundberg. R. C.&-Caprolactam Anionic polymerization Catalyst: sodium metal Initiator: phenyl isocyanate (PhNCO) and hexamethylene diisocyanate (HDI) Initial temperature: 130.00“’ 15.50X lo7 Published values of reference: Sibal. D. Sci. Polym.83 x io7 i s o x io7 1. 26.36“’ 20.42 19.00 Polymerization Degradation Polymerization Degradation (l) NdPhNCO NdPhNCO NdHDI NdHDI 1. “Designing Nylon-6 polymerization systems for RIM”. 560 (1986). A. Cimini. Pittsburgh. Anionic polymerization Catalyst: sodium hydride Activator: bis-&-caprolactam bis-diphenyl methane diisocyanate polypropylene glycol 1000 Maximum conversion: 95. Presented at the Second International Conference on Reactive Polymer Processing. W.157°C Temperature rise during the reaction: 32-37°C dX/dt=Ao(1-X)( l+BX)exp( -E.

01 2.20f0.43f0. t: reaction time.0 93. [sec] A: A=Ao([M]o/[A]02) [-I .50f0.50f0.04 26. [ 1/sec] By B': autocatalystic parameter.01 2.20 t0.38k0.758 0.9 95. To=155 ["C].87 dX/dt=AIo(1-X)"(l+B'X)exp( -E'.77 k0.60f0.04 0.8 AoX IO-'' [I/sec] 2.05 25.224 Ionic polymerization Kinetic Parameters of Malkin's Equation [A10 [mol%] 1.15 f 0.00 f 0.50f0.05 1.758 0.42k0.88k0. AIo: pre-exponential constant.89 k0.03 26.05 25. Ea=25.UTo)} 1-X)( 1+BX)exp K1=13 [I/mol]. K2=962 [I/mol].03 0.02 1.40*0.376 A'o X lo-'' [ 1/sec] 2.59k0.20 1. 0 5 B Ea [kcal/mol] A X lo-'' 0.5 [kcal/mol] [AIo: initial activator concentration.05 4.36-10.1 5 -10.08 2.01f0.140 0.140 0./RT) Kinetic Parameters [A10 [mol%] 1.376 X.568 0.02 25.05 1. [-3 Ao.568 0.20 31 0.14 3. [%I 94./R( UT.16k0.01 t 0 .08 * 25. [kcal/mol] n: the order of dependence on monomer concentration.33 k0.60 7.02 1.: apparent activation energy. [-3 E.04 1.05 dX/dt=( K1[A]~/[M]o-K~[A]~~/[M]~~)({ -E.30 -10. [mol/l] X: monomer conversion.08 25.46-10.15 25.02 2.10 4.20-10.04 2.03 n B' Ea [kcal/mol] 1.04 1.02 0.0 95.4320.58 15. [mol/l] [MIo: initial monomer concentration.03 2.

. KZ:constant.E-Caprolactam X. L. J. J. and Chen. Reprinted by permission of John Wiley & Sons. ['YO] K. Appl. 1671 (1993). J. Sci. [I/mol] To: initial temperature.. Kuo. Inc. Copyright 0 1993 John Wiley & Sons. Y. 50. ["C] 225 Yeh. ...: equilibrium conversion. F. C. Inc.. Polym.

M. . Artigiani.: propagation rate constant.226 2. G. Dimaina. and Giusti. kl=100. 29. Inc. Polym. chain. F..+ + MI + Pn+lt P.+ + AIM M. Reprinted by 1215 (1984). : AIM: Et2AICI. MI: monomer.+ + Cl2 + M.. Copyright 0 1984 John Wiley & Sons. kt2: transfer rate constants.. > PI' kP kt 1 kt2 P. Appl. + PIt P. kt2=SOO kl: initiation tare constant. k2=O. M. [ I/sec] k.OS. propagating species. [I/mol*sec] ktl. [I/mol*sec] k2: initiation tare constant. P. Temperature: -45°C Initiation Propagation Transfer AIM + CI2 +AIMCl2 kl ---f k.CI+CI. Inc.. []/mol * sec] Maschio.4 Isobutylene Ionic polymerization Cationic solution polymerization Solvent: CH3CI Initiator: AIEt. permission of John Wiley & Sons. J..: dead polymer kp=7500. ktl=100... Sci.. + PIt P .

640. Copyright 0 1963 John Wiley & Sons.. J. E. and Fetters. [I/mol. Bostick.. 70% for 50°C .8 4 0. sec] Morton. L.3 6. M.=l . Inc.. J. Livigni. Sci.. Inc. A.Isomene 2. Reprinted by 1735 (1963). permissionof John Wiley & Sons. Al.: propagation rate constant.. R. PoZynz.O X 104exp(-6800 cal/RT) Solvent effect on apparent activation energy for propagation Solvent Activation energy [kcal/mol] 22. 53% for 29°C For THF k.5 Isoprene Anionic solution polymerization Solvent: n-hexane or tetrahydrofuran (THF) Initiator: butyllithium Temperature: 0-29°C Maximum conversion: about 50% for O°C. E. Anionic solution polymerization Solvent: n-hexane or tetrahydrofuran (THF) Initiator: polyisoprenyl lithium Temperature: 30-60°C Maximum conversion: about 90% for O"C.1 227 n-Hexane THF k.

[l/mol-min] [MI: monomer concentration.0022"' '"[n-BuLi] Cyclohexane 5 0°C 0.4X lo3 8. at 30"C.04 [mol/l].. at 60°C. J. [I/mol*sec] k. and Fetters.9 k. and toluene Initiator: n-butyllithium (n-BuLi) Temperature: 5-50°C Maximum conversion: 100% R=K[M]' Polymerization rate constant K. Reprinted by permission of John Wiley & Sons.: propagation rate constant. R: polymerization rate.5X lo4 0.40 4.1 18(*) >0..0148") Toluene 50°C 0. [I/mol.8 1. L. [I/mol. Polym. Anionic solution polymerization Solvent: cyclohexane. [kcal/mol] A. 33 11 (1964). [mol/l] .: activation energy for propagation.sec] E.001 [mol/l].002-0.1 3. Copyright 0 1964 John Wiley & Sons.0189'" [I/mol*min] Hexane 50°C 0. Inc. '2'[n-BuLi]=0. A2.228 Ionic Polymerization Rate constant Solvent THF Hexane k. M. sec] E. Inc. n-hexane. [mol/l*min] K: polymerization rate constant. J. Sci.7 4. [I/mol*sec] Morton. [I/moI*sec] 0. Cyclohexane 30°C 0. [kcal/mol] A: frequency factor.14 6..

J. 153 (1965)..43 -10.27 0. J. n-hexane. and toluene Initiator: sec-butyllithium (sec-BuLi) Temperature: 5-30°C [mol/l] R. L. Reprinted by permission of John Wiley & Sons.035 R. A3.. Inc. [mol/l] [MI: concentration of monomer. H.012+-0.44 tert-BuLi i-BuLi 0.03 n-BuLi 0.=~‘. Inc.: initiation rate. Reprinted by permission of John Wiley & Sons.[BuLi] [MI Initiation rate constant k. [mol/l *min] ki: initiation rate constant. Copyright 0 1965 John Wiley & Sons. H. [mol/l] Hsieh. and i-BuLi Temperature: 50°C Ri=k.=~.. Polym. Anionic solution polymerization Solvent: cyclohexane. [l/mol min] [BuLi]: concentration of butyllithium. A3.018-10...012 sec-BuLi 0.002 n-Hexane 0. Polym.[BUL~]”~[M] [BuLi] > for [mol/l] R. sec-BuLi. Inc. Copyright 0 1965 John Wiley & Sons. (n-BuLi) ki (Cyclohexane) Cyclohexane 0. 163 (1965).003 Toluene 0. Sci.Isoprene 229 Hsieh. and toluene Initiator: n-butyllithium (n-BuLi). Sci. L. tert-BuLi. Anionic solution polymerization Solvent: cyclohexane. Inc.[BUL~]’’~[M]for IO-4< [BuLi]< . [I/mol*min] k.

[mol/l-min] [BuLi]: concentration of sec-butyllithium. and k’. 0.0212 0. 173 (1965). rate controlling .39 X 107exp(-6930/T) 0.: propagation rate constant...58X 105exp(-1340/T) 7920 0.096 0. [l’/3/mol’”.04 10400 9130 Propagation reaction Cj+l Cj + M --j k. Polym. Inc. Inc.[l/mol*min] Solvent Cyclohexane Toluene Temperature[”C] 30 5 k. [l”2/mo1”2 min] * k’.: propagation rate. H. Sci.155 0.230 Ionic polymerization Propagation rate constant k. 0. A3. kb KI 4.: propagation rate constant.012 k’. Anionic Solution polymerization Solvent: hexane Catalyst: n-butyllithium Temperature: 30-50°C Initiation rate constants and equilibrium constants Value Constant Definition 30°C 40°C 50°C I/mol*min * I2/rnoI2min I2/mol2 Unit k.133 6.00514 1. L.0067 k. [mol/l] [MI: concentration of monomer.0107 0. Reprinted by permission of John Wiley & Sons. [mol/l] Hsieh. Copyright 0 1965 John Wiley & Sons.min] R.14X 1023exp(-16700/T) 0. J.775 4.

1 1. : initiation rate constant. Inc.: equilibrium constant for association of active polymers. R. Sei. [mol/l*min] k.: active polymer of length j. Copyright 0 1974 John Wiley & Sons.66X lo6 Vmol smin ~~/~/moP’~ 13/mo13 k.47 148 5. Ahmad.. Inc.. [mol/l] [I]: initiator concentration. =CC. K2 K3 2. [cT]’[pT]( 1 +K2[IIa+K3[PT]b. [~ ~ / ~ / m o ~ ~ ‘ ~ ] K3: equilibrium constant related with K.Isomene 23 1 Association of active polymer 4CT + AT Kp=[A~]/[c~]4at equilibrium Association of active polymer with initiator c + I e (CjI) j k2 C. 1805 (1974).. [Vmol amin] K2: equilibrium constant for association of active polymer with initiator..8 56. associated polymer. A.1 22. CT: total active polymer. [I/mol*min] k b : initiation rate constant. G. 18. Polym. J. b=3 Propagation rate constants and equilibrium constants Value Constant Definition 30°C 40°C 11. [mol/l] RI: initiation rate.28X lo6 [PT]: total polymer concentration (= C [Pj]). Appl. [mol/l] [MI: monomer concentration.: propagation rate constant. [I3/mol3] Porter. a=3/4. and Anthony.08X lO-’exp(5660/T) 8.91 X IO6 AT: total Unit 50°C 16.2 2. E..min] K1.03 X 1 O’”exp(9 180/T) 4. Reprinted by permission of John Wiley & Sons. equilibrium constant of initiation reaction. [I3/mol3] K. [I2/mol2. .68 X 105exp(-3140/T) 1. [I2/mol2] k. R.

86X1 0 4. associated polymer.62XIO3 1 6 X lo2 .89X1' 0 3 7 X IO4 .62X1 0 6. I: initiator.1 KI e p .6 0 Cj + M + Cj+l 4CT + AT c + I + (CjI) j Cj: active polymer of length j. 0 ) x ( 2 0 T x(526ep32/) 30 C ° 40°C 6. e p 1 8 4 e p .97Xlo9 x(4.7 0 / ) x(2.0 4° 0C 3.2 Unit l/mol*min 13/m013 l2/moI2 ep2.17Xlo-' 3.1 lmlmn /o. M: monomer.24 lo2 X 3.i l2/moI2 lml /o 14 X . =CC.8ep-30T x(37)x(62/) K. ) x ( 4 0 / ) 2 0 X IO5 . AT: total Definition 2° 0C 3° 0C 1.98 lo3 X 91 ..14X 2. e p . CT: total active polymer.8 3 e p 1 8 0 T x ( 2 .98X 10 2 2 X 1' .87Xlo7 7. Rp=kp[Py]M]/ { 1+( 1+~.54X 1.3 4..8ep160T .1 3 ) x ( 8 0 / ) 3.232 Ionic polymerization Anionic solution polymerization Solvent: benzene Catalyst: n-butyllithium Temperature: 20-40°C RI=kI[I]/( 1+Kl [II2+K2[pT]) Initiation rate constants and equilibrium constants Value Cntn osat Definition Unit 2° 0C kl e p l S ) x ( 6 6 / ) x(9lep-90T K.[PT]~)''~+KI [ [I]2] KqpC2=(+KpPT3)1'4 1 Propagation rate constants and equilibrium constants Value Constant k.)x(395T K2 e p .

A. 19. J Appl. G. [I/mol*min] K.. [12/mo~2] 233 Magott.Isoprene [PT]: total polymer concentration. = [P. Ahmad.. . and Anthony...: propagation rate constant. Reprinted by permission (1975). [I/mol] k. [I2/mol2] K2 equilibrium constant of initiation reaction. Polym. Inc.. Inc. J. R. R. [mol/l*min] KI: equilibrium constant of initiation reaction.]. [mol/l] [MI: monomer concentration. [mol/l] [I]: initiator concentration. Sci. of John Wiley & Sons. [I3/mol3] KI: equilibrium constant for association of active polymer with initiator. 165 Copyright 0 1975 John Wiley & Sons.: equilibrium constant for association of active polymers. [mol/l-min] kI: initiation rate constant. [mol/l] Rl: initiation rate.

J.1 k: polymerization rate constant.6 16.. Worsfold.2 k [I/mol * min] 84. [mol/l]. J. 1141 (1958).2 13.234 2.10°C -d[monomer]/dt = k[ initiator] { [monomer]-[monomer]. [monomer]: concentration of monomer. and Bywater.) Temperature ["CI -10 -10 -10 -10 -10 -10 -77 -77 -77 -77 -77 Catalyst concentration x io4 [mo1/11 11.4 11..6 a-Methylstyrene Ionic Polymerization Anionic solution polymerization Solvent: tetrahydrofuran (THF) Catalyst: sodium naphthalene Temperature: -77. Can.2 50. . [Vmol min] [initiator]: concentration of initiator.9 16..7 14.1 20.6 24. [mol/l]. 36. [monomer].8 12.3 82. [mol/l].5 96.2 74.2 31. S.8 16.3 85. D. Chem.2 12.1 69.5 28.4 26.8 23.: equilibrium concentration of monomer.

Am.. [mol/l] R. [mol/l] [BuLi]: concentration of n-butyllithium...020 [mol/l] Activation energy for propagation= 17 [kcal/mol] [MI: concentration of monomer.Li * Bu(M).Styrene 23 5 2 7 Styrene .=k[M] for [BuLi] >0. [mol/l. for [BuLi] < 0. J. Chem.=k. 81. M: styrene monomer. BuLi + M + Bu(M)Li Bu(M). SOC. [I/mol. sec] Welch. F. [I/mol.: propagation rate. 0 1959 American Chemical Society. sec] k.020 [mol/l] R.[M][BuLi] R. . [ l/sec] k. Anionic solution polymerization Solvent: benzene Catalyst: butyllithium Temperature: 10-30°C d [C]/dt=-k 1 [C] [MI d[ M]/dt=-k. ILi ki k. [C] 'I2[ MI C: butyllithium. J.: propagation rate constant. Anionic solution polymerization Solvent: benzene and toluene Catalyst: n-butyllithium (BuLi) Temperature: 20-50°C Initiation: Propagation: M: monomer. 1345 (1959). sec] k: propagation rate constant.: initiation rate constant.

563 0. 1891 (1960).sec] [MI: monomer concentration. Can. [I/mol*sec] k2: propagation rate constant.236 Ionic polymerization Temperature ["CI 30. [mol/l] [C]: catalyst concentration.0 kl X lo4 [~"~/mol'/~. Chem. and Bywater S.45 Apparent activation for initiation=l8000 [cal/mol] Apparent activation for propagation=l4300 [cal/mol] kl : initiation rate constant. J.387 0.0 10.265 0.0 20. D. [Vmol.0 4. [mol/l] I Worsfold.68 1. .155 14. 38.. .0 15.3 25.929 0.min] k2 [11~2/mo11'2*min] 0.

[Vrnol. Anionic solution polymerization Initiator: n-butyllithium (BuLi).015 0..0 0.028t0.061 0. Reprinted by permission of John Wiley & Sons. [mol/l*min] K: polymerization rate constant.0131"' 237 Cyclohexane "'[n-BuLi] >0.042t0.min] [MI: monomer concentration.03 . and toluene Temperature: 50°C R. tert-BuLi. Wiley & Sons.007 R: polymerization rate. Polym.002 0. Inc. A3.85 50.Styrene Anionic solution polymerization Solvent: cyclohexane Initiator: n-butyllithium (n-BuLi) Temperature: 5-50°C Maximum conversion: 100% R=K [MI Solvent Temperature ["CI 30 [mol/l] Polymerization rate constant K []/mol*min] 0.. Inc. n-hexane. sec-BuLi. L.008 0. [mol/l] Copyright 0 1965 John Hsieh. 153 (1965). J. Sci. H.=ki[BuLi][M] Initiation rate constant k.028 ki (cyclohexane) sec-BuLi tert-BuLi tert-BuLi 2. [Vrnol-min] kj (n-BuLi) Cyclohexane n-Hexane Toluene n-BuLi 0. and i-BuLi Solvent: cyclohexane.

J. Copyright 0 1965 John Wiley & Sons. Inc. [mol/l] Hsieh. 163 (1965). [mol/l] [MI: concentration of monomer. J.. Reprinted by permission of John Wiley & Sons. [mol/l.min] ki: initiation rate constant.: propagation rate constant. Inc. Inc..min] [BuLi]: concentration of sec-butyllithium. L. [mol/l] Hsieh. Anionic solution polymerization Initiator: sec-butyllithium (sec-BuLi) Solvent: cyclohexane and toluene Temperature: 5-30°C R. [I/mol. Inc.080 k.. [mol/l] [MI: concentration of monomer.238 Ionic polymerization Ri: initiation rate.[BUL~]”~[M] [BuLi] > for [mol/l] Propagation rate constant k. H. [1”2/mo1”2* min] Solvent Cyclohexane Toluene Temperature [“C] 30 5 kP 0. A3. L. Sci. - . Polym. Reprinted by permission of John Wiley & Sons. min] [BuLi]: concentration of butyllithium.. [1”2/mo1’/2min] R.: propagation rate. H. Sci. [mol/l. Polym. Copyright 0 1965 John Wiley & Sons.494 0.=~. A3. 173 (1965).

612 (1965). + Ak A.. 69. 624 (1965). 62. Polym. 701 (1966).] YI I + M +A. Prep. 5 .Styrene Anionic solution polymerization Solvent: benzene. polystyrylrubidium. S. Chem. J.. and tetrahydrofuran Catalyst: polystyryllithium.8 21. for propagation via ion-pairs Counter-ion Li Na K Rb Benzene 17(3). (4)at 30°C. Faraday Soc. A.=kdkr I: unassociated n-BuLi. polystyrylpotassium. 66 (1965). J. A. 1092 (1964). polystyrylsodium.94 3. and Bywater. Aj+M+Aj+l A. dioxane. Chem.. S.: activated intermediate BuMjLi' an activator. E. (3)Morton. Fortschr. Phys. (2)Bhattacharyya et al.... and polystyrylcaesium Temperature: 25°C 239 Absolute values of k. M: monomer.4 19. [Vmol sec] Roovers. 4.5 24. Aj * Ak: activated polystyryl anion complex. [Iy]: associated n-BuLi..*& + Ka Ki KP Ke. Polymer Chem.: propagation rate constant. C.. k. L.5 Tetrahydrofuran(*) 160 80 60-80 50-80 22 cs 47 24 18 (')Bhattacharyya et al. Anionic solution polymerization Solvent: benzene Initiator: n-butyllithium (n-BuLi) Temperature: 10-25°C + Initiator association Initiation Propagation Polystyryl anion association [I. . Hochpo1ym.. >3 0(4) - Dioxane(') 0. 69. Div. Bywater.-Forsch. J. Phys. Trans.

[I/mol. F. L.[ Complex] [MI =ko. [I/mol] k.29. 0 io5 ~ Ki: initiation rate constant. [mol/l] .240 Ionic polymerization Activation energy [cal/mol] Initiation Propagat ion Association 10500 2000 -3 12001 Frequency factor 1. K=4 X IO5 [I/mol] k0. Chem. Sci. [I/mol*sec] kop: rate constant for polymerization by uncomplexed living ends. [I/mol. Eng..[ LE] [M]+k'. Anionic solution polymerization Solvent: tetrahydrofuran in the presence of pyridine Initiator: a-methylstyrene tetramer disodium PSt-Na' + CsHsN + complex Equilibrium constant=K K=[Complex]/[LE] [Py]=[LE]o/[LE] { [Pylo-[LE]o} -d[ M]/dt=k. 2145 (1974).[ LE] [M]+k'. [I/mol*sec] Keq: polystyryl anion association equilibrium constant Timm.[ LE]o[ MI =ko. D.1 X IO2 1 . [mol/l] [LE]: total living ends concentration. sec] [MI: concentration of monomer. [mol/l] [LE]o: initial concentration of total living ends. [I/mol*min] K. and Kubicek. C.: propagation rate constant.: apparent rate constant of polymerization..: rate constant for polymerization by complex. sec] k'.=2900 [I/mol*sec] K: equilibrium constant of complex formation.[ LE]o[ MI kp=kOdK([Pylo-[LElo)+k'.1 x io5 3.

kl=0.0 [12/mo12-min] k3=0.5 - kl. P. [mol/l] 24 1 Yagi. respectively.. k2. 12: iodine. M + P. MI2: styrene diiodide. K. HI. + . [mol/l] [Pyla: initial concentration of pyridine.. [l/mol.. P.**212. 1097 (1976). k5: propagation rate constant.min].: dead polymer chain. min].6 [l2/moI2 min] ks=lO. Pseudocationic solution polymerization Solvent: ethylene dichloride Initiator: iodine Initiation I2 + M K + MI2 MI2 HI + 212 Propagat ion Chain breaking M + HI2' + P. 14. units are [l/min].. and [l2/moI2* min].* *212 13- k. [ l/min] 1 K=0. Chem. Bull. 8. Reprinted by permission of John Wiley & Sons. Inc. Toda. MI: unsaturated side product. k..1 [l/mol.Styrene [Py]: concentration of pyridine..*: growing polymer chain. Copyright 0 1976 John Wiley & Sons. Sci. G. P. k3.. M. Tsuyama.. . F. J.O [l/mol. Y. [l/min] K: equilibrium constant h: initiation Maschio. Polym.+1*. [Vmol. Ed. 147 (1982). rate constants. Cerrai. Inc. Polym. Polym.+ - + MI + HI kl + P1**212 P. and Iwakura.. S.7 [ l/min] k2=4.212 M. + 1 . and Giusti..min] b: chain breaking rate constant. [I2/mol2. + HI k4 k5 + 212 ks M: styrene.min] b=0.min] b=O..

l Two kinds of deactivation/reactivation processes: inac act)^ 2cinact concentration of active sites. 3. The initiation is instantaneous. [mol/l] case I: kl=- 2At W~+A-C~C( CO-C)-' W2+A cth(Aklt) log K/ZA-COC(CO-C)-' . 2. the stationary rate conforming to the established equilibrium. A reversible bimolecular deactivation of active sites occurs in the course of polymerization.242 Ziegler-Natta polymerization 3.c(t) 2cact 2cact k .5 mol/l (constant) co=Q(t)/Mn(t) wo=kP[TiI&l2][MI co=a[Ti12Cl2][MI w0=klpco Assumption: 1. I cinact: concentration of inactive sites. At time t case I: case 11: Cact: w(t)=k'. [mol/l]. all the macromolecules are growing. At the beginning of polymerization.1 Butadiene Homogeneous polymerization Catalyst: TiI2Clz/Al(iso-C4H9)3 Temperature: 20-30°C Monomer concentration: 0. Ziegler-Natta polymerization 3.

72 13.57 1.75 24.15 0. c(t): concentration of active sites at time t.5 -t 0.5 co: initial concentration of active sites. [mol/l] Q(t): polymer yield at time t. [mol/l-sec] .5f0.92 2.4 65.2 52. [l/sec] kl [I/mol.86 3. [g/l] [MI: molar concentration of monomer.8 31.63 0. [mol/l] [TiI2C12]: molar concentration of titanium halide.Butadiene 243 c=co case I Temperature ["CI case I1 k2X102 K X 1 0 3 [I/mol.sec] k'.6 9.5 4.5 5.3 1 15.80 1.52 1.73 2.59 3.sec] 10 20 30 40 1.75 0.8 k 0.98 8.1 9.96 17.4 [kcal/mol] -11.8-tO.32 E.1 23. 12.0t0.sec] k2X lo5 K X 1 0 7 kl [ I/sec] [mol/l] [I/mol. [mol/l] Mn(t): number-average molecular weight at time t.6 4.60 6. [mol/l] c. [mol/l] est: concentration of active sites at stationary state.82 -6..89 2.2 39.35 0..7 9. [g/mol] wo: initial propagation rate.

[mol/l-sec] kp: propagation rate constant. [mol/l] or [-I Eact: activation energy..244 Ziegler-Natta polymerization w(t): propagation rate at time t.1-ene C*Pr + B + C*B + Qr Regeneration of active sites C*B + M + C*P. [I/sec] kl: rate constant of deactivation. . [kcal/mol] Bresler. + QI Transfer to but. [I/mol*sec] ktp: rate constant defined in above equation. S. Grechanovsky. [I/mol* sec] K: equilibrium constant. L.... 1 11 (1970) Homogeneous polymerization Catalyst: cobalt octoate/diethylaluminium chloride/water Temperature: 15°C Initiation (formation of active sites) CO + AI + H20 + C* Formation of byproducts CO + AI + H20 + Eb Propagation C* + M -+ C*P. Makromol. + Qr + C ki kP kP k. Chem. Muzsay. A. C*Pr + M + C*Pr+l Transfer to monomer C*Pr + M + C*P. 133. Ya. V. + B Cobalt deactivation C*P. sec] k2: rate constant of reactivation. and Poddubnyi. I.. [l/mol. A.

C: (leactivated catalyst site. [ 1/min][mol/l]'"".: rate constant of formation of byproduct. C*B: short-lived but-1-ene/ catalyst complex. [mo1/11 [i]: concentration of species i. Eb: catalyst byproduct.: rate constant of propagation. C*PI: growing chain of unit length. [I/mol. [I/mol.82X 106exp(-5117.min] (at 15°C) kl=0. [I/mol.O X 109.95 X 109exp(-4570.=1.[C*][M] d [Co]Nd t=-ki[ Co]"-ks[ CO] d[C*P]Ndt=ki[Co]"'-k~[C*P] dYo/dt=kp[C * ][M]-k.: rate constant of regeneration of active sites.= 1 . d[M]/Vdt=-k..: growing chain of chain length r. [I/mol. C*P. C*: active catalyst site.: rate constant of initiation.)/ki k. [I/mol. [mol/l] k.=ki( 1-f) k.002 [ I/min] (at 15°C) m=l.min] dXo/dt=kp[C*][M]+k.Y I dYz/dt=kp[MI (Y0-2Y ~)+kp[ * ] [M]-k[ MI (Yo-Yz)+kb[B](Yo-Y2)-kiY2 C dX I/dt=dXo/dt+k.Butadiene 245 Co: cobalt octoate. [ I/min] k.[M]Yo+kb[B]Yo-k[M][C*P~]-kb[B][C*P~]-kt[C*P~] . M: butadiene monomer. in: constant k.4 V: volume of reaction mixture. AI: diethylaluminium chloride.X1/Xo Mw=MInX2/X1 f=( k. [ 1/min] [mol/l]'-In k.min] kb: rate constant of transfer to but-1-ene.OX [I/mol. [I] [C*PI: total moles of growing chains. B: but-1-ene.[ M]Yo dX2/dt=dXo/dt+kp[M](Y o+2Y 1) MN=M.1 cal/T) [l/mol*min] kb=l.-k.6 cal/T) [I/mol. min] k: rate constant of transfer to cobalt. Qr: dead polymer chain of chain length r.min] k=2. min] k.min] kl: rate constant of catalyst deactivation.Y 0 dY l/dt=kp[M]Yo+kp[C *][M]+kJ M](Yo-Y I)+kb[ B]( YO-Y l)+k.

E.. [mol/l] MN: number average molecular weight. K] fi catalyst formation efficiency. Sci. Reprinted by permission of John Wiley & Sons. [g/mol] Mw: weight average molecular weight. + B + C2*B + Qr Regeneration of active sites Cl*B + M CI*PI + B + k 1 kc2 + kbl kb2 + . J. [g/mol] T: temperature. Polym. Inc. MacGregor. A. Appl.+I C2*Pr + M + C2*Prt-1 Transfer to monomer + C I * P ~ M -+ CI*PI + Qr + CZ*Pr + M + C ~ * P I Qr Transfer to 1-butene CI*B + Qr Cl*Pr + B C2*P.246 Ziegler-Natta polymerization Yi: i-th moment of the growing chain distribution. A. F. and Hamielec. E.: molecular weight of monomer... [-I Honig. Copyright 0 1987 John Wiley & Sons. Homogeneous polymerization Catalyst: cobalt octoate/diethyl aluminium chloride/water Temperature: 15°C Maximum conversion: 80% Initiation (formation of active site) CO + AI + H20 Cl* CO + AI + H20 + C2* Initiation CI* + M + CI*PI Cz* + M -+ C ~ * P I Formation of byproducts CO + AI + H20 + Eb Propagation CI*Pr + M + C~*P. J. 829 (1987). Inc.. Gloor. J. 34.. [mol/l] Xi: i-th moment of the total chain distribution. J. [glrnol] M. P.

[I/mol.. S. M: butadiene monomer. Sci. CI: deactivated catalyst site with active site 1.1 cal/T) [I/mol*min] kb=i0-4 [~/rno~-min] 1 5 " ~ ) (at kl=0. Inc. [l/min] constant of regeneration of active sites with site i.6 cal/T) [I/mol. E b : catalyst byproduct. Kp=( 1.: growing chain of length r with site 2. and Miller. Qr: dead polymer chain of chain length r. C2*B: short-lived 1-butene/catalyst complex with active site 2.min] constant of transfer to l-butene with site i.: rate constant of initiation with site i.: rate k.. C2*: active catalyst site 2. [I/mol*min] constant of catalyst deactivation with site i.. C1*: active catalyst site 1. [l/rnin][m~l/l]~~"'.min] constant of formation of byproduct. . Ct*Pr: growing chain of length r with site 1. Polym. 44. [I/mol. 837 (1992). Inc.m: constant constant of propagation with site i.Butadiene C2*B + M + C2*P1 Catalyst deactivation C~*pr--+ Qr + CI Qr + C2 C2*Pr + 247 +B kz2 k. Jr. C2*P. J. Nitirahardjo. Appl. r: constant. CI*B: short-lived I-butenejcatalyst complex with active site 1. [I/mol.002 [ l/min] (at 15°C) kll: rate kp.: rate kbi: rate k.min] constant of transfer to cobalt with site i. [ I/min][mol/l]". B: 1-butene.. W.95 X 109)exp(-4570. Lee. AI: diethylaluminium chloride. Copyright 0 1992 John Wiley & Sons.82 X 1 06)exp(-5 1 17. S. C2: deactivated catalyst site with active site 2..min] k=(2.: rate kzi: rate k. Reprinted by permission of John Wiley & Sons. J. 1 kt2 Co: cobalt octoate.

9 6. Solution polymerization Solvent: benzene Catalyst: nickel carboxylate/boron trifluoride etherate/triethylaluminium Monomer concentration: 1.=k. triethylaluminium: 16. E.lk.6 5.8 1.4 1.=l 1.o .6 X IO” [mol/l]. [Vmol.248 Ziegler-Natta polymerization Solution polymerization Solvent: toIuene/water (water: 2 x 10” mol/]) Catajyst: cobalt acetonyl acetonate and aluminium diethyl chloride Temperature: -2-40°C R.: activation energy of polymerization. X 1O4 [I/mol*sec] 8 5 4 2 40 30 40 40 1. [mol/l. boron trifluoride etherate: 18.[ C]..’[ Butad iene] [Co(acac).. Rubber and Plastic Age.. nickel carboxylate: 2.] E.7 2.6 X lo” [mol/l] Temperature: 20-40°C Maximum conversion: 100% -d[ M]/d t=ak.56 X 10” [mol/l]. [MI 1/ =ki. C.7 1. [kcal/mol] [Butadiene]: concentration of butadiene.3 1.: polymerization rate. k X 1O4 [ l/sec] 2.: polymerization rate constant.sec] E..2 1.86 [kcal/mol] R.5 k.8 1. [mol/l] Bawn. sec] k’. X 104/k. H. 510 (1965). [I/mol-sec] 6 3 3 2 k.8 5.18 [mol/l].+a[C]o/~[M]o Temperature [“CI 01 1O2 k. [mol/l] [Co(acac)3]: concentration of cobalt acetonyl acetonate...

R.[H20]/[ All’” kl=(3. [Co]=0.: transfer rate constant to monomer. [-I cc: constant. I [mmol/l] Temperature: 25°C d[M]/dt=k. Komatsu. 61 (1970)..[ MI [PI [Co]=[Co]iexp(-kct) [Mol kpkc[Co]i In ~.. T. [mol/l] [CIO: catalyst concentration at initial time. [-I P : number-average degree of polymerization.0-24. [Vmol sec] k... [Vmol sec] kt: termination rate constant.: propagation rate constant..Butadiene kt=O [MI: monomer concentration. [l/sec] 249 - - - Yoshimoto.94)X [l/sec] .. [mol/l] x: conversion.8 1) X 1O”. Solution polymerization Solvent: benzene Catalyst: CoC12-4C5H5N-(C2H5)2AlCl-Et2AlCl* H20 [A1]=5. A.. K.4-4.29k0. Chem. 139.0 [mmol/l]. and Ueda.. [mol/l] [Mlo: monomer concentration at initial time.t) k C 1 k. [H20]=1. Onishi.=( 8. Y. [-] kt. Mukromol. []/mol sec] k: first-order rate constant. Takeuchi.029-10. Sakata. Yamamoto.[MI kc-kt I-exp(-k. K.7 [mmol/l]. [ l/sec] k.88 k3. K...t) kl I-exp(-k.

All rights reserved. 66 (1976).r + M Pi. [mol/l] [MI: concentration of monomer at any reaction time.: rate constant of propagation. [mol/l] [Coli: initial concentration of CoC12 4Py. [I/mol* sec] kt: rate constant of termination.. + CI* P2. PIJ: the living polymer of chain length one of type I species. [ l/sec] - Hsu. + C2* + + CI* kr kpi kfm 1 kfi"2 M: monomer. AZChE Journal. Copyright 0 1976 AIChE. [mol/l] [Mol: initial monomer concentration.: rate constant of initiation. Reproduced with permission of the American Institute of Chemical Engineers..+] PI.250 Zienler-Natta polymerization [Co]: concentration of free CoC12 4Py. C. Solution polymerization Solvent: toluene Catalyst: nickel(I1) stearate-diethyl aluminium chloride Temperature: 20°C Ni(Stearate)2 + M + DEAC C1* + M + PI. and Ng. L. DEAC: diethyl aluminium chloride. [l/sec] k. Pi. [mol/l] k.: the living polymer of chain length r of type i. 22. [mol/l] [PT]: concentration of total active polymer.^ + M + P. CI*: Complex of type I... Pr: dead polymer with chain length r. . c1* + c2* Pi.. + M -+ P. C2*: Complex of type 11. C.

* + P. the sum of [Cl*] and [C2*]. S A . [I/mol*sec] kfi. . Appl.* -+ + + + Pi* Pr+l* P.: rate constant of type I converted to type 11. 653 (1981).sec] kp2: propagation rate constant of type I1 complex.l: transfer rate constant of chain to monomer with respect to active species I. [l/sec] kpi: propagation rate constant of type i complex. 26. J.. Reprinted by permission of John Wiley & Sons. Copyright 0 1981 John Wiley & Sons. [mol/l] [MI: monomer concentration at any time t. [mol/l] [C*]: total concentration of active species. [l/mol. and Hsu.. Polym. [I/mol*sec] Lee. [I/mol.8 17 -2. C.. [I/mol*sec] kpl: propagation rate constant of type I complex.Butadiene 25 1 Parameter Activation energy [kJ/mol] 21 6. [mol/l] k.6 [Mol: initial monomer concentration.sec] kp: overall propagation rate constant. Inc.. D-H. [I/mol. + C* P. Solution polymerization Solvent: toluene Catalyst: Co(acac)3-(i-Bu)3Al-H20 Temperature: 20°C Initiation Propagation Chain transfer Termination C* + M Pr* + M Pr* + T P. C. sec] kfin2: transfer rate constant of chain to monomer with respect to active species 11. Inc.

C. W. [i/mol. [mol/l] [MI: monomer concentration. and Hsu.2 26.42 1.min] k.024 0.42 14. P. [mol/l] [Mlo: initial monomer concentration. Inc. [Vmol. Inc.94 1.2 0.4 13.5 16.*: living polymers with chain length of r. [mol/l] Yang.025 0.024 0.06 0.94 1.97 0. L. [mol/l] [C*]O: initial concentration of active complex. T: transfer agent.Appl.0 0.kP[C*l In In( l+k. [I/mol. . Polym.26 0.min] kp: rate constant of propagation.4 0. -d[P*]/dt=k[P*]* -d[M]/dt=kp[P*] [MI [P*]=-[C *]O/(kJC *lot+ 1) [Mol .: inactive polymers with chain length of r. 145 (1983).86 2. C. [mol/l] [C*]: concentration of active complex. Reprinted by permission of John Wiley & Sons.047 0. I Copyright 0 1983 John Wiley & Sons.252 Ziegler-Natta polymerization C*: active complex formed from the reduction of Co(III) + Co( D) with (i-BuhAl and water. P.[C*]ot) [MI kc[C*Io 1.3 0. Sei. 28.. min] k: rate constant of termination by combination. [Vmol smin] [P*]: total concentration of living polymers..4 0.: rate constant of transfer.01 1 112 19.. .41 4760 770 976 0.027 ki: rate constant of initiation. [mol/l] [i]: concentration of species i.

42 X 7. In[M]i/[M]=(kp[C~*]i/ktc[C~*]i)ln( 1+ktc[Co*]it) k.* + M + Pr* + T Pr* + P..46 X 10-4+B IT+B~[H~~]+B~[H~O]~+B~T[H~O]+B~[H~ [DEAC] ktC[Co*].62X -8..=.: inactive polymers with chain length of r.Butadiene Solution Polymerization Solvent: toluene Catalyst: CoC12 * 4Py/Et2 * AICVH20 Temperature: 1 1.6-25°C Initiation Propagation Chain transfer Termination CO* + M P.46 x los6 -8.* + 253 - Pi* Pr+l * Pr + C* P.64X l o 6 .71 X -1. M: monomer.=5.55X 1. Co*: active complex.[C0*].X 1O”+B3[DEAC]+B4T2 +B7T[H20]+BsT[DEAC]+B9[H20][DEAC] 1.78 X -5.44 Rate constant Parameter estimate kp[Co*]i BI B2 Bs B7 B9 4.50X loM5 -2. Pr*: living polymers with chain length of r.97X Rate constant ktc[Co*li Parameter estimate B3 B 4 B7 B8 B9 1.67X 4. T: transfer agent. P.

34X104 4. sec] kt. [g/mol] M../M.33X IO3 -1.16X105 6 . [mol/l] [Co*]. [mol/l] [MI: concentration of monomer.: number-average molecular weight.: weight-average molecular weight. W.89X102 -1. [mol/l] [H20]: concentration of water. D.76 1.. Parameter estimate PD B2 B3 B5 Bg BI B2 B3 B4 B5 Bg 6. [mol/l] [Mli: initial concentration of monomer. W. HSU.254 Parameter estimate M. 32. 3 0 X lo4 -1.39X103 -9. F..30X lo-* ki: rate constant of initiation.: initial concentration of active complex. Sei. PD=M.: rate constant of chain transfer.09X lo3 1. [Vmol. K. Ziealer-Natta polymerization Parameter estimate M. [I/mol. Inc.: rate constant of termination by combination. min] [Co*]: concentration of active complex. 5287 (1986). . [mol/l] T: temperature.22X l o 3 -1.34 -1.58X IO3 -1. [sec] M. [I/mol-sec] kp: rate constant of propagation.18X104 1. Reprinted by permission of John Wiley & Sons.28X IO-' -3. Appl.58X IO3 B1 B2 B3 B4 B5 Bb 8. Copyright 0 1986 John Wiley & Sons. Inc.. J. and Bacon.01 X 1 0 2 1. C. Polyrn. ["C] t: polymerization time. [l/mol*sec] kt. Ho. [mol/l] [DEAC]: concentration of diethylaluminium chloride. [g/mol] PD: polydispersity. C..

H. and Symcox.213 [mol/l] [Ti(OC4H9)4]=0. E. C. Inc. 255 Bawn.[C][m] Activation energy=l2. Solution polymerization Solvent: toluene Catalyst: bis-(cyclopentadieny1)-titanium dichloride/dimethylaluminium chloride Temperature: 0-60°C (C5H5)2TiC12 + (CH3)2AICI -+ (C5H5)2TiC12.Ethylene 3.34. R..4 [kcal/mol] . Sci. Reprinted by permission of John Wiley & Sons.[Cl2 Activation energy= 16.(CH3) polymer - fast ki kP + k. Polym.2 Ethylene Solution polymerization Solvent: hexane Catalyst: Ti(OC4H9)4-AI(C2H5)5 Temperature: 25-50°C Ethylene pressure: 25-95 mmHg Activation energy=l3 [kcal/mol] for [AIEt3]=0. Chain propagation d[P]/dt=k.2 [kcal/mol] Chain termination -d[C]/dt=k. Inc. 139 (1959).. (CH3)2AICI (C5Hs)lTiCh (CH3)2AICI + [AT](CH3) [ATI(CHd + nC2H4 ---t [ATI(C2H4)n(CW 2[ATI(C2H4).07 [mol/l] C2H4 pressure=56 mmHg and 90 mmHg. Copyright 0 1959 John Wiley & Sons. J..

4 39.19+ 0. J. 0 1959 American Chemical Society.07 k0. Solution polymerization Solvent: hexane and heptane Catalyst: TiCI4-alkylaluminium Temperature: 39-67°C Ethylene pressure: 760mmHg R.12310. Am.0'2' N X IO5 [mol/l] k. [mol/l] ki: initiation rate constant.43 9.9 2.256 Temperature ["CI Zienler-Natta Polymerization kiX IO3 kP [I/mol sec] [ 1/sec] kt [I/mol*sec] 0 15 30 40 0. 86 (1959).0 '2)[Ti]=16.15 5.282 zk0.13 4. [I/mol*sec] 90% confidence limits 10. J. [I/mol-sec] Chien. 81.7 1 1 SOk0.: propagation rate constant. AI/Ti=2.14 [mmol/l]. [ l/sec] k.30 50. SOC.99 zk 0..05 2..19310.MN Propagation rate constant as a function of temperature Temperature ["C] 39. [mol/l] [C]: concentration of propagating metal alkyl complex.4'" 54.57 13. Chem.=k. C.0 52 k 2.26 1. [l/mol* sec] kt: termination rate constant.49 k0. AI/Ti=0. W.0 0.5 .6k 1.7 [mmol/l].5'" 67.58 [AT]: propagating metal alkyl complex [PI: concentration of polymer formed. [mol/l] [m]: concentration of monomer.7 127+ 16 175535 '"[Ti]=2.

[Vmol. Copyright 0 1960 John Wiley & Sons. Japan. and Perry. and Grieveson. Kagiya.. [mol/l.. S. Bull..: propagation rate constant. 56. Chem.. C. Polym. 80 (1965). h] k: polymerization rate constant. Chem. 217 (1960). F. T. S. [mol/l] [CZH~]: concentration of ethylene. [mol/l] [All: concentration of AI(C2H5)CI.: polymerization rate. E. [mol/l] 257 Feldman. Sci. . and Yuasa. Inc.7 [kcal/mol] Fukui. Machi. K. 303 (1962). 83. [mol/l.. N. [mol/l] N: active center concentration.. Solution polymerization Solvent: cyclohexane Catalyst: AI(C~HS)CI/~-T~CI~ Temperature: 30-60°C Rate=k[TiCh]’ [C2H4] [AI]’ k=6.Ethylene R.. B..1 X 1 O”exp( -1 7300 cal/RT) Rate: polymerization rate. T. Solution polymerization Solvent: n-heptane Catalyst: AI(C2H5)5-TiC14 Pressure: 43 kg/cm2 Activation energy of polymerization in the liquid phase=2. [mol/l] Berger. Shimidzu.. sec] M: solubility of ethylene in solvent. M. Inc. J. [I/mol.. 35. Soc. sec] k. Makromol. Reprinted by permission of John Wiley & Sons. M. h] [TiC13]: concentration of y-TiCI3.

sec] K"2/Kp=3.. Makromol. [mol/l] [C*]: concentration of active polymerization sites.sec] KM: monomer transfer rate constant..-+ Cat . [Vmol sec] : Grieveson.. 84. [Vmol. B.7 X [MI: monomer concentration.CH2-CH2Cat .sec] KH~-3 [I/mol..CH2-CH2 Chain transfer with monomer Cata.. .4X 106.258 Ziegler-Natta polymerization Solution polymerization Solvent: cyclohexane Catalyst: Al(C2H~)Cl/y-TiC13 Temperature: 30-60°C Spontaneous termination (hydride transfer) Cat .8 X KM-~O-~ [I/mol.. [I/mol*sec] K H ~hydrogen transfer rate constant.-CH2-CH3 + CH2=CH - + KS + - K M JH2 =CH2 Chain transfer with added terminating agent (for example with hydrogen) Cat. 93 (1965). M. [mol/l] [H2]: concentration of hydrogen.. [mol/l] K..[M] [C*] Termination ~~~~=Ks[C*]+KM[M][C*]+KH~[H~][C*] K.=3 ...-H + CH3-CH2 K2 H d - Propagation rate=K.CH2-CH2. [I/mol.Ks-3 X 1O'4 [I/mol*sec] KM/K. .-8O.. 1 [Vmol-sec] Ks/K. Chem.=1..: propagation rate constant.H + CH2=CHCat . sec] Ks: solvent transfer rate constant.

6 [g-C2H4/g./( 1+k'2P:) B'kBPE k=kl P~+k2 Temperature ["C] k'l k'2 0 - 20 2.35 = 10.. Kojima. [hr] PE: ethylene pressure. 71..64X 8.04X 8.3 - 1.Ethylene 259 Solution polymerization Solvent: toluene Catalyst: Al(C2H5)3/TiCh Temperature: 0-60°C r=Aexp( -kz)+B A=k'lP.8X lo-* 1 1. A. T.. [kcal/mol] 4.CzH4/g*TiC13h(cmHg)'] kl [l/h.cmHg] 0. Kogyo Kuguku Zashi. 1124 (1968). kl.TiCI3.63 X 0. Keii. k2: constants r: polymerization rate. [cmHg] Matsuda. C2Hdg-TiC13.3 6 X 10-2 1.5 X 0. .01 3. h ( ~ m H g ) ~ ] T: reaction time.5 40 4. T.h(~ml-Ig)~] ke [I/cmHg] [g.67 X 10-2 0. T.75 1. and Ishida.6 [kcal/mol] 6-7 [kcal/mol] k'2.59 30 3.5 = = k2 [I/hI Activation energy of kl Activation energy of k2 Activation energy of k B k'l.9 X 10-2 0.. [g.2 X 0.

[mol/l sec] C.: number of active centers. Bukatov..... K. G. G.. D. sec] polymerization rate. B.=8. Zakharov.260 Ziegler-Natta polymerization Solution polymerization Solvent: hexane Catalyst: 6-TiC13. 177.3AIC13+AI(C2H5)3 Temperature: 75°C V=K.C. and Yermakov Y. I.3AIC13+AI(C2H5)3 Temperature: 20-80°C V=K. .3) X 1 O4 K. 177. Makromol. Makromol. 763 (1976).C. Chumaevskii.: V: C.. D. [I/mol.2 ?c 0. sec] V: polymerization rate.. Kp=(1. Chem. A. [mol/l] C.0 X 105exp(-13 kJ/RT) K. N.. Kuznetzova.. [mol/l. V. G. [I/mol.sec] number of active centers. [mol/l] monomer concentration.C..: propagation rate constant. 747 (1976). B..: C. I. [mol/l] Zakharov. I.: monomer concentration. [mol/l] Chumaevskii. N... Solution polymerization Solvent: hexane Catalyst: 6-TiC13. Chem.: propagation rate constant.C. 0. A. Bukatov.. V. and Yermakov Y. 0.

dealkylation and reduction of Ti(II1) to Ti(I1) may occur in the same way. P..E h kz P.l. E: ethylene de(-TiC12R)/dt=kalkVC(AIR~)~(-T~C~~)-~~~~~~~C(AIR~C~) I -kredlIcI Ve(-TiCI2R)’ .E P.l: polymer chain. I I i-o-Ti \ c 1 \c1 - .Ethylene Solution polymerization Solvent: cyclohexane Catalyst: TiClJAl/Al(CH2CH(CH3)& Temperature: 68°C 26 1 Polymerization scheme: Alkylation and dealkylation of supported Ti(1V): \ c 1 k&!i ~ \ c 1 Reduction of Ti(1V) to Ti(II1): ‘R k k + RH + olefin AI -0-Ti The alkylation.+1 -cat cat: catalyst.cat + E Insertion of ethylene: P. .-cat.-Cat. Coordination of ethylene: P.

': dealkylation rate constants of supported titanium(IV). [mol/l] k. -TiR.: propagation rate constant of active center (i).'..sec] Rp(i): propagation rate of active center (i). respectively. kaI:". [l/mol*sec]. healkl". [mol/l] Active center: -TiC12R. K. [l/sec] or [l/mol-sec] . [l/sec] eactive(i): degree of coverage of active sites (i) on the surface. Schnaup. ..(-TiCIR)=3. heal.41 X 10-1 [l/sec] kp(-TiR)=7. heal.(-TiR)=l. c(AlR2Cl): concentration of AIR3 and AIR2C1.262 Ziegler-Natta polymerization de(-TiCLR)/dt=ka~k111~(A")~(-TiClz)-kdea~~'1~(AlR2Cl)e( -TiCIR) -kreduoll'e( 1R)2 -Tic de(-TiR)/dt=ka~k"c(AIR3)B(-TiCl)-kdea~kl1c(A1R2C1)8( -TiR)-kredu. kreduc . respectively. kaliV. [mol/l] the c(AlR3)."$(-TiR)2 d~(-T~C1~)/dt=kdea~~1vc(AlR~Cl)~(-TiC1~R)-ka~~vc(AlR~)~( 111 de(-TiCI2)/dt=kdea1k C(AIR~CI)~(-T~C~R)-~~I$~~C(AIR~)~(-T~ de(-TiCl)/dt=kaeal~1~(A1R2Cl)e(-TiR)-ka~k'1~(AlR3)e(-TiC~) kp(-TiC12R)=1. kreduc : reduction rate constants of Ti(1V) to Ti(III). [mol/l-sec] c: concentration of ethylene. X 10-4 [ 1/sec] 18 If concentration are used instead of surface coverages: kP(-TiCl2R)=l7 [I/mol*sec] kp(-TiC1R)=5 [I/mol*sec] k. (111) and (11).50 X [ l/sec] kalklV'kalkll"kalkll= 10 [h O l * SeC] kdeaiklv=kdeaiklll=kdeal$l= 1 [I/mOl' SeC] kreduolv=5 X 10-l [ 1/sec] . 11. Makromol."'=2. and Reichert. -TiClR. [I/mol*sec] IV 111 I1 kreduc .-H. k.46 kredu.52X 10-2 [ l/sec] kreduol1=8.l$': alkylation rate constants of supported titanium(IV). 315 (1990).1 6 [ 1/sec] k. A. Rapid Commun. Ti(II1) to Ti(I1) and Ti(I1) to Ti(I). respectively. respectively. Chem. (111) and (11).l [l/mol.

~.: dead polymer chain.+I c*-PI. + A12/2 + C* + P.[C*-PI [H2] d[Al2]/dt=-( 1/2)( ki[ SI [AI.Ethylene Solution polymerization Solvent: tetrahydrofuran(THF) Catalyst: silica-supported TiCIJMgCI2/THF activated by Al(C2H5)3 Temperature: SO-80°C Ethylene concentration: 128-428 [mmol/l] 263 Initiation (formation of active sites) S + A12/2 + C* Propagation C* + M . PI.: living polymer with n units. Deactivation C*-P CI .[SI [A 121 d[C *-P]/dt=ki[ SI [AI21I/'-kd[C *-PI d [Cl]/dt=-kd[C *-PI d[Hz]/dt=-( 1/2)k. C*-PI.?] 1'2+ktal[ C*-PI [AI21 . C*-PI. C*: active center..[ C*-P] [H2] "2+klln[C *-PI [M]+kt. Termination C*-P. Al2: aluminium alkyl dimer. + H2/2 -+ C* + PI. CI: deactivated site.+ - S: surface site. M: monomer. + M + C* + Pn+l C*-PI.l. ( 1/V)(d[M]/dt)=k.l[ C *-PI [A121II2+kte[ C*-PI d[ S]/dt=-k..[C*-P] [MI d[ P]/dt=k. + c * + PI.+ C*-PI C*-P..l + M + C*-P.

[mol/l] [SI: concentration of surface site. [1”2/mo11/2*sec] k. [ 1/sec] kd: rate constant of deactivation.: hydrogen transfer reaction constant. Chem. [mol/l] [CJ: concentration of deactivated site. Znd. [I/mol*sec] ktl..: total concentration of dead polymer.]: total concentration of living polymer. []/mol sec] ktal: alkylaluminium transfer reaction constant. H. 2074 (1991). I. [I] ki: rate constant of active site formation. [mol/l] [HI: concentration of hydrogen. J.01 x Unit [I/mol-sec] kd [l’”/mo1’’2 sec] [I/mol*sec] [11/2/mo1”2*sec] [1’/2/moI”2*sec] [ 1/sec] [C*-PI= C [C*-P.8 175 0.103 12. [mol/l] V: volume of reactor. Kim. [mol/l] [PI= CP. [mol/l] [AI]: concentration of aluminium alkyl dimer. [l’/2/mol’’2 sec] ktB: spontaneous transfer reaction constant. I. S. and Woo. [mol/l] [MI: monomer concentration. .... [ Usec] - Kim.989 1. 30.: rate constant of propagation. Res. Eng. [11/2/mol’” sec] ktm: monomer transfer reaction constant. 0 1991 American Chemical Society.264 Zienler-Natta Polvmerization k kP ki ktm ktli ktal Value at 80°C 16680 0.

Gibbs W. [mol/l] [AI alkyl]: concentration of aluminium triisobutyl. 0 1958 American Chemical Society.. 5615 (1958). J. Am. and Lal.20 Temperature: 0-20°C Polymerization rate=0. AI/Ti molar ratio= 1.... J. Chem.760[M][Al alkyl][TiC14] Activation energy=l4400 [cal/mol] [MI: monomer concentration of monomer. 80.3 Isoprene Solution polymerization Solvent: heptane and pentane Catalyst: aluminium triisobutykTiC14. E. Soc. [mol/l] [Ti]: concentration of TiC14. M. [mol/l] at 10 "C 265 Saltman. W. .Isoprene 3.

07-0.5 kcal/RT) .0 Temperature: 30-70°C Pressure: 100-700 [mmHg] Stage I: initial polymerization stage (polymerization rate R increases rapidly) ( I ) Propylene is introduced afier the addition of AI(C2H5)3 R=k. sec] 0.17 0. Ziegler-Natta polymerization Gas phase polymerization Catalyst: TiCkAI(C2H5)3 [TiC13]=2 [g/l].=k:exp( __ . Ro-R.4-3.P2K[A]t/(l+K[A]) Temperature ["CI 57 44 32 Initial rate [mol/l*sec] 0.10 kcal/RT) R. [AI]/[Ti]=0.22 (2) Propylene is introduced before the addition of AI(C2H5)3 R=k*P[A]t Stage 11: kinetic behaviors are almost independent of the addition of propylene and AI(C*H5)3.06 0.12 0.266 3 4 Propylene . R-R. k3=k'3+kff3P k3=k:Pexp( -6.08 0. .28 Stationary rate [mol/l. =exp{-(k'3+kf'3P)t} _ .

. [cmHg] [A]: concentration at AI(C2H5)3. [sec] R: polymerization rate at time t. [Vatrn. [g-CsHdg-TiCh* hr] Keii. Reprinted by permission of John Wiley & Sons.. [g-C3Hdg-TiC13* hr] Ro: initial polymerization rate. [mmol/l] t: polymerization time. T. [I/mol. Inc. Polym. [Vsec] P3: rate constant. [I/mol. N. [I/sec] k rate constant..O 15 17 2-3 12 10 K: constant. K.. and Saiki. [I/mol] kl: rate constant.Propylene Values of activation energies Rate constant ki k2 k 3 267 Activation energy [kcal/mol] k"3 k.: polymerization rate at stationary state.C16. Inc. Sci.. [g-C3Hdg-TiCh hr] R. Copyright 0 1967 John Wiley & Sons. J.sec] k2: rate constant.sec] k3: rate constant. sec] : P: propylene pressure. [I/sec] k"3: rate constant. Soga. 1507 (1967).

[I/mol] kld: constant. 0 1982 American Chemical Society. Prod. .02% Doi. 21.sec] &: initial polymerization rate.. [mol/l*sec] k. [mol/l. Chem.1/AI(C2H5)3 38 38 38 ~ . K. B-1: Ti content 1.T ~ C I ~ / A I ( C ~ H S ) ~ C41 I 40 6-Tic 13/AI(C2H5)3 [MI: monomer concentration. Murata.. Y. Ind. Eng. [mol/l] Rl: polymerization rate at time t.. M. and Keii. Dev./dt=k'd [C * 12 1 h=k'd/kP[M] l/R.=l/Ro+ht 1/[ c*]I=1/[ c*]~+k'df Catalyst-system Temperature ["C1 Time [min] 10 60 10 30 60 80 60 kP [l/mol*sec] 41 41 B. [mol/l] [C*I1: catalyst concentration at time t..: mean propagation rate constant. [l/mol*sec] A-l/AI(C2H5)3 300f 15 320 t-25 320 k40 320f30 360+60 32+3 31 10 + A-1: Ti content 0. 580 (1982). [I/mol*sec] h: constant.268 Ziegler-Natta polymerization Gas phase polymerization Catalyst: MgCl2-supported TiC1~/C~HSCOOC2Hs/A1(C2Hs)3 Temperature: 38-4 1"C Ri=kp[Ml[C*]t -d [C*].48%. T. Res.. [mol/l] [C*]o: initial concentration of catalyst. Yano.

. [g C&/hr] pcp6: partial pressure of propylene..T ~ C I ~ Temperature: 2. Kagiya. Shimidzu. . [g] Natta.. I. Copyright 0 1960 John Wiley & Sons.. [atm] GTI: weight of a-TiCl3 in the catalyst system. and Fukui.3. Yuasa. Polym. and Pasquon.7-37. G..7 [kcal/mol] for 2-40°C Kodama. Advances in Catalysis. N2: inactive complex.149°C Pressure: 3. N3: exchanged active complex.0 [kg/cm2] Maximum conversion: 100% Apparent activation energy=5.36-6.80 [atm] Initiation Propagation Transfer Tic13 + AI(C2H5)2CI + M N + M .. S. T. XI.. S. K. Inc. N: active site. T. S.Propylene Solution polymerization Solvent: n-heptane Catalyst: AI(C2HS)3/a-TiC13 269 r=Aexp( . Solution polymerization Solvent: hexane Catalyst: AI(C2H5)2CI-TiC13 Temperature: 50-90°C Pressure: 1. 1 (1959). 20 (1960). Reprinted by permission of John Wiley & Sons. J. Appl.10000 cal/RT)GTip C ~ H ~ r: polymerization rate under steady-state conditions. Machi. NO: initiated active complex. Solution polymerization Solvent: n-heptane Catalyst: A I ( C ~ H S ) ~ . Sci. Inc..N N -+ N2 N -+ N3 + NO kl k2 k3 M: monomer.

...6 7.0 31 110 kl: propagation rate constant. [f exp ( -kz+ 1 )] k=koexp( -6. K. Y.270 Rate constants Temperature ["CI 50 70 90 Ziegler-Natta polymerization kl [ l/min.. Inc. [ l/min. J. 243 (1963).. J. ko: constant k: constant f: constant Keii. M. Reprinted by permission of John Wiley & Sons..: polymerization rate at steady state. Taira.5 kcal/RT) r..5 [ 1/min] 109 124 126 9. Sci. Polym. r. Inc. Takagi... H. E.: polymerization rate at z hours after the polymerization starts.=r. V. Saiki. and Cavender. - . and Murayama. 681 (1962). Solution polymerization Solvent: n-heptane Catalyst: AI(C2H5)3/TiC13 Temperature: 1657°C r. T. Copyright 0 1962 John Wiley & Sons. 58.atm] k2.1 11. N. Schuurmans.. [l/min] Kohn. k3: transfer rate constant.atm] k2X lo3 k3X lo3 [l/min] 3. T. Shokubai. L. Soga. J. 5.

. klr2: rate constant of chain transfer reaction. J.Propylene Solution polymerization Solvent: heptane Catalyst: a-TiCl3-(C2H5)2AlCI Temperature: 30-90°C 27 1 30 50 70 90 0.6 -[kcal/mol] 8. Elr2=7.: polymerization rate. EIrI=l [kcal/mol]..90 x 1o . Elr2: activation energy for ktrl. [mol/l] k. [I/mol*sec] R. Copyright 0 1963 John Wiley & Sons. [mol/l*sec] [C]: concentration of catalyst. Inc.426 f0.54 x I . J. Inc. [I/mol*sec]. W. Polym.50 k0. [kcal/mol] Elrl. klr2.6 R.0 [kcal/mol]. E.: rate of increase of cI4activity.20 0. Sci.58X 9.15 k0. .sec] ktrl: rate constant of chain transfer reaction. Reprinted by permission of John Wiley & Sons.. C. [mo~/~. 425 (1963).20 3.: polymerization rate constant. [kcal/mol] Chien.100 t0.018 1.60X IO" E.: activation energy for k. [l"2/mo1'/2 sec]. A l .=13. [mol/l] [m]: concentration of monomer.50 x 1.~ 3.54 x io-' 3.12 - - 6.

atm] hr.5 ["C] 80 40 28 16 8 4 200 - BO [g(C2H~)/g(TiC13).. T.5 ["C] 300 - - 133 110 37 157 118 43 171 - r: polymerization rate. Polym. Inc.exp( -kt)] B=Boexp( -2. Copyright 0 1966 John Wiley & Sons. 2429 (1966). f constant.. [g(C2H5)/g(TiCI3).5 ["C] 286 26 1 214 142 118 53 37.272 Solution polymerization Solvent: n-heptane Catalyst: Zn(C2H5)2/TiC13 Temperature: 2536°C Ziegler-Natta polymerization r=BP[ l+f. Sci. Inc. [atm] B: constant. [g(C2H~)/g(TiC13)* hr] P: propylene pressure. and Keii.5 ["C] 298 - 30.7 kcal/RT) k=koexp( -3. [l/hr] k: constant. [-I Soga. atm] hr. K. . Reprinted by permission of John Wiley & Sons. 43. A l . J.8 kcal/RT) Zn(C2H5)2 [mmol/l] 48. 4.

: propagation rate constant. Solution polymerization Solvent: hexane Catalyst: 6-TiC13. K. N. G..=90 20 273 * K. 747 (1976).3AlCI3 + AI(CzHs)2AI Temperature: 30-70°C V=K. G.. sec] number of active centers.C.Propylene Solution polymerization Solvent: hexane Catalyst: 6-TiC13. [mol/l]. D.. A. V. [mol/l. Kuznetzova. Bukatov.. [mol/l. monomer concentration..: monomer concentration. 0. 177.: V: C.. I. [mol/l] C. B. 763 (1976). V. [I/mol*sec] V: polymerization rate. and Yermakov Y.. Makromol.=3. N.3AIC13+AI(C2H5)2CI Temperature: 70°C V=KpCpCin K. 0.C. I.. A. Bukatov. Chem. Zakharov.. . [mol/l] Zakharov. Chumaevskii. 177.0 X 1OSexp( -23 kJ/RT) K. and Yermakov Y. B. [Vmol-sec] polymerization rate..: number of active centers.: C... I.sec] C.. Chem. G. Makromol. D. [mol/l] Chumaevskii.: propagation rate constant..

sec] k.... and Yermakov. V. 183.(Mg) Temperature: 70°C V=k. G. [mol/mol of Ti] CM: monomer concentrations. T.274 Ziegler-Natta polymerization Solution polymerization Solvent: heptane Catalyst: T ~ C ~ ~ / M ~ C ~ ~ / C ~ H S C O O C ~ H S / A ~ ( C ~ H S ) ~ Temperature: 4 1"C Pressure: 660 Torr P. Chem..=kp[ MI t With 0. 2657 (1982). Chem. [mol/l] Bukatov. [mol/dm3] P. E. Doi.. Zakharov.: number-average degree of polymerization. [sec] Suzuki. A. Makromol.: propagation rate constant..sec] v: polymerization rate. Makromol. D.. Sergeev. [dm3/mol sec] [MI: monomer concentration in the solvent. H. I..cpcM kp=500-1000 [I/mol. 2235 ( 1 979). .. Y.: overall polymerization rate constant. Tamura.. Shepelev. [mol/(mol of Ti).45 mol/dm3 and 5 seconds k p > 4 .. M. 180. A. [I/mol. sec] C.: number of active centers. Solution polymerization Solvent: hexane Catalyst: TiCI. S. 4 X lo2 [dm3/mol. S. and Keii.. Y. [units/mol] t: polymerization time. sec] k..

EG: ethylene glycol.. . r . * .Transesterification of dimethyl terephthalate with ethylene glycol 275 4.* A l . .o x 1o . CT: the end methanol ester group(CH30-). singly substituted mixed ester.min] kE=3.~ at 1SO"C'~' k. * * * A T CF + kr/K kr I .* * A . Second-order rate constants from the literature Reaction Catalyst Rate constant [I/mol. . . * * .2x 1o . * AF + kdKr AF: free ethylene glycol species (HOCH2CH20H). . Polycondensation reactions 4... monomer. . AT: end-group ethylene glycol ester unit (HOCH2CH20-). AI: an internal ethylene glycol ester unit (-OCH2CH20-).1 Transesterification of dimethyl terephthalate with ethylene glycol Zero functional species: dimethyl terephthalate and its oligomer Monofunctional species: methanol.r/kE=O. . e . and its higher oligomer Bifunctional species: ethylene glycol.+ A . BHET: bis(2-hydroxyethy1)terephthalate . A I . kr k. / K ..5 kp=3. . CF: free methanol (CH30H).~ at 262°C kp=2. A T + CT. and its high oligomer Temperature: 180-262°C Ester interchange Transesterification Polymerization AF + CT.5 X 1 0-3 at 23 1" C Energy [kcal/mol] 15 Reference Ester interchange DMT") with EG") Polymerization BHET") BHET zinc acetate ( 31 no catalyst antimony trioxide 23 (4) (5) 29 "'DMT: dimethyl terephthalate. + CF kr .

276

Polycondensation reactions
(2)Fontana's orig'mal rate constants were based on a third order rate expression (one order with respect to catalyst concentration). Here the catalyst concentration was included in kE. (3)Fontana, C. M., J. Polym. Sci., A-1, 6, 2343 (1968). (4)Challa, G., Makromol. Chem., 38, 125 (1960). (')Stevenson, R. W. and Nettleton, H. R., J. Polym. Sci., A-1, 6, 889 (1968). At 220°C KP=KE=KT= 1 k~/kp=4 kT/kp=8, k~/kp=4 ,

KE: ester interchange reaction equilibrium constant, [-I Kp: polymerization reaction equilibrium constant, [-I KT: transesterification reaction equilibrium constant, [-I kE: second- or third-order forward ester interchange rate constant, [I/mol*min] kp: second-order forward polymerization rate constant, [I/mol. min] kT: second- or third-order forward transesterification rate constant, []/mol * min] Ault, J. W. and Mellichamp, D. A., Chem. Eng. Sci., 27, 2219 (1972). Catalyst: zinc acetate Temperature: 180- 197°C Molecular species model: C H 3 O O C a COOCH3 + HOCH2CH20H CH300C

a

ki

COOCH2CH20H
kz

+ CH3OH

C H 3 0 0 C e COOCH2CH20H + HOCH2CH20H

HOCH2CH200C e C O O C H z C H 2 0 H

+ CH30H

Transesterification of dimethyl terephthalate with ethylene glycol Rate constants for the molecular species model Catalyst Apparent Compound Mass, Reaction rate [mol] temperature constant x io4 ["c] k', X 1O3 180 197 197 197 180 175 2.5535 2.0370 1.4187 0.98768 1.4372 3.1787

277

Data

True rate constant
kl

[l2/moI2* min]

Fontana(" zinc acetate 1.81 Tomita and Ida(2' zinc acetate 1.00 Tomita and Ida'2' zinc acetate 0.70 Tomita and Ida(2' zinc acetate 0.50 Tomita and Ida(*' zinc acetate 1.00 Peebles and Wagner(3) zinc acetyl- 5.51 acetonate

3.527 5.093 5.067 4.938 3.593 1.442

lnkl=433 5S/T+ 10.840 Methyl ester group model: CH3OOC-@ COOCH3 + HOCH2CH20H
ki

HOCH2CH200C G C O O C H 2 C H 2 O H Rate constants for the methyl ester group model Catalyst Apparent Compound Mass Reaction rate x lo4 temperature constant [moll ["CI k',X lo3 zinc acetate 1.81 Ida(2' zinc acetate 1.00 Ida(2' zinc acetate 0.70 Ida(2' zinc acetate 0.50 Ida(2' zinc acetate 1.00 Wagner(3)zinc acetyl- 5.5 1 acetonate
180 197 197 197 180 175

+ CH30H

Data

True rate constant kl [I2/mol2*min] 3.527 5.092 5.027 4.943 3.593 1.350

Fontana(') Tomita and Tomita and Tomita and Tomita and Peebles and

7.7373 6.0264 4.1646 2.9248 4.3551 3.5508

278

Polycondensation reactions

(')Fontana, C. M., J. Polym. Sci.,A-1, 6, 2343 (1968). (2)Tomita, K. and Ida, H., Polymer, 14, 55 (1973). ("Peebles, L. H. and Wagner, W. S., J. Phys. Chem., 63, 1206 (1959). lnkI=-4306.8/T+10.777 kIa: apparent rate constant, [-I k,: true rate constant, [I2/mol2.min] Nx: the number of moles of species X A: DMT, B: ethylene glycol, C: catalyst, E: methyl ester, m: methanol, R: methyl 2-hydroxyethyl terephthalate (MHET), V: reaction volume. Yamanis, J. and Adelman, M., J. Polym. Sci. Polym. Chem. Ed, 14, 1961 (1976). Copyright 0 1976 John Wiley & Sons, Inc. Reprinted by permission of John Wiley & Sons, Inc. Catalyst: zinc acetate Temperature: the first stage: prepolymer (monomer for polycondensation stage) containing mainly bis(2-hydroxyethyl) terephthalate (and its linear oligomers) is prepared by dimethyl terephthalate and ethylene glycol. 140-220°C the second stage: polycondensation stage, prepolymer produced in the first stage is polycondensed. 260-290°C. The first stage: Ester interchange reaction CH300C

a

COOCH3

+ HOCH2CH2OH

&
kilKi

ki

HOCH2CH200C - @ 2 O O C H 2 C H 2 0 H + CH30H Transesterification reaction CH300C

CH300C

a a

COOCH3

+ HOCH2CH200C

9 COOCH2CH20H

kz
kilKz

(1)

COOCH2CH200C--@

COOCH2CH20H

+ CH30H

(2)

Transesterification of dimethyl terephthalate with ethylene glycol
The second stage: Polycondensation 2 eCOOCH2CHzOH

279

k3
k3/1<3

e
Side reactions

COOCH2CH200C-@--

+ HOCH2CH20H

(3)

-@ COOCH2CH20H+ e

C O O H + [CH2CH201+

CH3CHO

(4) (5)

+HOCH2CH20H -++ [CH2CH20]

HOCH2CH20CH2CH20H

-QCOOCH2CH20H +
-@COOH

[CH2CH20]

+

HOCH2CH20H

k7

F==+K r kd

e C O O C H 2 C H 2 0 H + H20 -0COOH

(7)

+ H O C H 2 C H * O O C - @ - F====+ - ks

a
-Q COOCH2CH200C -@+ P

kdKa

C O O C H 2 C H 2 0 0 C ~ -+ H20

(8)

a C O O H

+ CH2=CHOOCe
+
CH;? CH2 CH2 1 CH2 I ‘ 0 ’

(9)

/o\

~ C O O C H 2 C H 2 0 C H 2 C H 2 0+ e C O O H H

(10)

280
2 HOCH2CH20H
--@COOCH2CH20H

Polycondensation reactions
HOCH2CH20CH2CH20H + H20
0

-@COOH

+/ \

-0 COOCHzCH20H
0

CH2-CH2

-

CH2CH20

+ HOCH2CH20H
GCOOCH2CH20CH2CH20H

*

/

+ H20

e C O O H + HOCH2CH20CH2CH20H

CHz-CH2
0

/ \

+ HOCH2CH20H + HOCH2CH20CH2CH20H + a C O O C H 2 C H 2 0 H +-@OOCH2CH20CH2CH2OH

*

CHz-CH2

/ \

COOCH2CH20H

+ GCOOCH2CH20H
COOH +

ko

e

COOCH2CH20CH2CH20H

Transesterification of dimethyl terephthalate with ethylene glycol
Kinetic parameters used in the present work Activation energy [kcal/mol] 15.0 Frequency factor [I/mol*min] 6.0 x io4 4.0 x io4 2 . 0 io4 ~ 3 . o io4 ~ 2.0 x 1 o4 1.0~10~ 6.8X IOs 2.17 x 109(l) 2 . 1 7 io9 ~ 2 . 1 7 io9 ~ 1.ox lo6 1.ox lo6 Equilibrium constant

28 1

Reaction

Ester interchange eq.( 1 )

0.3

Transesterification eq.(2)

15.0

0.15

Polycondensation eq.(3) Acetaldehyde formation eq.(4) Free DEG‘*) formation eq.( 14) Incorporated DEG formation eq.( 17) Esterification reaction eq.(7) Esterification reaction eq.(8)

18.5 29.8 29.8 29.8 17.6 17.6

0.5
-

-

2.5
1.25

(‘)Units are 1/min. (2’DEG: diethylene glycol (HOCH2CH20CH&H20H) kl-k3, kS-k8: second-order rate constants, [l/mol*min] b: first-order rate constant, [ l/min] KI-KS: equilibrium constants, [-I Ravindranath, K. and Mashelkar, R. A., J. Appl. Polym. Sci., 26, 3179 (1981). Copyright 0 1981 John Wiley & Sons, Inc. Reprinted by permission of John Wiley & Sons, lnc.

42 Estimates of rate constants at 1967°C k21=7.25 3. D: bis(2-hydroethyl)terephthalate.67 6.196. ~ [ ~ / m i n ] k32=(2.0427 0.7"C A+Bk"'C+D C + B + D + E (1) (2) A: terephthalic acid.183 EI CO [mol/kg] - [Dl0 [mol/kg] - k l l X lo2 [kg/mol smin] 5.282 Polycondensation reactions 4. [A'l=[A']d(~ I [A'lot) +kl d[C]/dt=k21[C]+k22[CI2 d[C]/dt=k2[C]o d[D]/dt=k.1952 0.53)X 1 0 .38 t0.70 0. C: 2-( hydroxyethyl)terephthalate. [C] k3=k31+k32[A'l Effect of initial concentration of 2-hydroxyethyl terephthalate [C] and bis(2-hydroxyethy1)terephthalate [D] on the rate of esterification of terephthalic acid [A'] at 1967°C [A'lo [mol/kg] 0.5 x [l/minl X k22=4.25 5.210 0.1* 1. B: ethylene glycol.1886 0.1046 0.2 Esterification of terephthalic acid with ethylene glycol Catalyst: no catalyst Temperature: 180. E: water.1913 0.1913 - - 0.74 5.84 6.153 0.OS I ) X I 0-2 [kg/mol*min] .0 10-3 [kg/mol * min] k31=(7.

k31. k22.. F. Bazant. k32.Esterification of terephthalic acid with ethylene glycol 283 [A']: instantaneous concentration of terephthalic acid. 34.: instantaneous concentration of terephthalic acid at time zero. [mol/kg] [C]. manganese acetate. or no catalyst Temperature: 240°C (at the boiling point of the reaction mixture) A1 + A2 A3 + A14 A4 + A14 A3 + A2 A8 + A14 A1 + A4 2A3 * A8 + A14 AS + A14 A3 + A4 A8 + A2 + AS + A14 AS + A3 A6 + A14 Bs As + A2 @ 2A4 + + + + --f ICBS A6 + A3 f A7 + A14 Chemical formula HOOCC6HdCOOH HOC2H40H HOC2H400CC6~COOH HOC2H4OOCC6H4COOC2H4OH HO(C2H4OOCC6H4COO)2C2H4OH HO(C2H4OOCC6H4COO)3C2H4OH HO(C2H4OOCC6H4COO)4C2H4OH HO(C2H4OOCC.. k2.. [mol/kg] [A']..: instantaneous concentration of 2-(hydroxyethy1)terephthalate at time 0. Chem. Commun. k21. k3: defined in equations (3)-(7) MareS. V. Catalyst: cobalt acetate. and Krupicka.jH4COO)2H HOC2H40C2H40H H20 List of symbol and chemical formulas of compounds Symbol Compound Terephthalic acid Ethylene glycol 2-Hydroxyethyl hydrogen terephthalate Bis(2-hydroxyethyl) terephthalate Dimer Trimer Tetramer Acidic dimer Diethylene glycol Water . Collection Czechoslov. [mol/kg] kll. 2208 (1969). J.

Chem..26 0.26 0.762 - 0. potassium chloride concentration 0.389 0. [I/mol*hr] - Effect of reaction mixture composition on parameter Catalyst [%I KCl [%] B8 [I/mol*hr] 0.193 2.19 0.12 2.764 0. M.134 2. V.52 1.35 0. [-I Rod.96 1. hr] 1-9.28 3.670 0. Collection Czechosolv. 41..3 0.48 Catalyst concentration 0 3% based on the total batch weight: ..39 0. Commun. . no potassium chloride was present. defined in equations ( ) ( ) [I/mol. 2339 (1976).63 (I) 0. ( 2 ) No catalyst.3 0.3 1.3YO based on the total batch weight. and kir.524 0. Milarik.03 1.71 0.57 1. Eldiwani. Z.19 BI-B8: reaction rate constant. K: equilibrium constant of equation (a).3 0.284 Polycondensation reactions Parameter Values Parameter []/mol hr] Series I(') Series II(*) 1.52 0.03 0. G.

Esterification reactions HOOCeCOOH ki 285 + HOCH2CH20H k d1Cz HOCH2CH200C H O O C G COOH e COOCH2CH20H + H20 F====+ kz + HOCH2CH200C-@COOCH2CH20H kdKz H O O C G COOCH2CH200C -@COOCH2CH2OH + H20 Polycondensation reaction 2 aCOOCH2CH20H @ k3 kdK3 e Side reactions eCOOCH2CH20H -0COOCH2CH20H COOCH2CH200Ce + HOCH2CH20H e C O O H + CH3CHO + HOCH2CH20H 3 COOH + HOCH2CH20CH2CH20H 2 aCOOCHzCH2OH -0 iCOOH .Esterification of terephthalic acid with ethylene glycol Catalyst: no catalyst Temperature: 240-260°C Pressure: 3-6 atm.

OK] [cal/mol] 2.+kciec i=l.038X 10" 3.min] k".min] ko2 [kg/mol*min] kC2 [kg2/moI2-min] ko3 [kg/mol*min] kc3 [kg2/moI2 min] [l/min] k5.OK] AHi: enthalpy change of i-th reaction.80 -19.286 Polycondensation reactions Rate equations: RI=kl (2eCg-e. [cal/mol] A&: entropy change of i-th reaction. [cal/mol . 3 E X 10'~ AS AH [cal/mol] [cal/mol .80 29.31 49. 2.672 X lo5 8. [kg2/moI2.16 21.462 X lo8 7.04 X 10' 0.80 -10.=ko. [mol/kg] w: concentration of water in the liquid phase.564 X 10 5.g 2 R6=k6eg k. [cal/mol] . e.w/K1) R2=k2(eceg-2zw/K2) R3=k3(e.325 X IO6 1.-4zg/K3) %=Le.~ 8.86 29.21 -5666 -9 122 K3 e.04 X 1O8 1.55 x 1 0 .: concentration of acid end groups and hydroxyl end groups in the liquid phase.63 29.00 20.71 10. [mol/kg] Ei: activation energy of i-th reaction. R5=2k5e. [mol/kg] z: concentration of diester group in the liquid phase. k6 [kg/mol*min] K2 i=2.. [equidkg] g: concentration of ethylene glycol in the liquid phase./RT) KI=K2/K3 Kinetic and thermodynamic parameters A ko1 [kglmol. 3 ki=Aiexp ( -Ei/RT) Ki=exp( ASi/R-A H.

[kg/mol-min] b: first order rate constant. COOCH2CH20H a + H20 k3 + HOCH2CH200C a C O O C H 2 C H 2 0 H ' . Catalyst: not specified Temperature: 240-265°C Pressure: atmospheric . 610 (1982). %: reaction rates. [l/min] K1. %. R5..Esterification of terephthalic acid with ethylene glycol kl. Polym. and Mashelkar. 22. R3.min] 287 Ravindranath. A. k + H20 HOCH2CH200C eCOOCH2CH200C-&OOCH2CH20H Polycondensation reaction 2 -DCOOCH2CH20H F==== ka k. Eng.. k2. k3. eCOOCH2CH2OOC Side reactions 2 -@COOCHzCH20H e + HOCH2CH20H e COOCHZCH~OCHZCH~OOC e + H20 . [mol/kg.1. Sei. R2.. K2. b: second order rate constant. ks. K. K3: equilibrium constants.O kg/cm2 Esterifications H O O C e C O O H + HOCHzCH20H HOCH2CH200C HOOCeCOOH ki 'k. R. [-I R1.

so06 x 10’ 1. O.5716X 7. k H20 ki -@COOCH2CH20CH2CH20H + Kinetic constants: ki=Aiexp( -Ei/RT) A kl k2 k3 E [cal/mol] 1 O8 lo’ IO7 19640 18140 223 I O 18380 2810 14960 42520 I .8463 X 4.8229 X 2.. Imamura.. T.hr] Yamada.288 Polycondensation reactions e C O O C H 2 C H 2 O H + HOCH2CH20H % = --@ COOCH2CH20CH2CH20H + H20 2 HOCH2CH20H ---+ k9 HOCH2CH20CH2CH20H + H20 -@COOH 4. Sci. Y.4905 X k4 k5 ks k7 lo6 1OI5 kl-k7: rate constants. and Makimura... [cal/mol] A: frequency factor.HOCH2CH20CH2CH20H ’ . . 708 (1986).9816X 9. [kg/mol. Eng. Polym. 26. [kg/mol* hr] E: activation energy.094 1 6.

a Polycondensation reaction 2 C O O C H 2 C H 2 0 0 C e + H20 e COOCH2CH20H ' . k COOCH2CH200C ka e e + HOCH2CH20H Side reactions 2 --@200CH2CH20H -%+ -@ C O O C H 2 C H 2 0 C H 2 C H 2 O O C ~ + HO2 a C O O C H 2 C H 2 0 H + HOCH2CH20H e COOCH2CH20CH2CH20H 4.Esterification of terephthalic acid with ethylene glycol Catalyst: potassium titanium oxyoxalate Temperature: 250°C Pressure: atmospheric Esterification reactions HOOCeCOOH ks 289 + HOCH2CH2OH HOCH2CH200C -@COOCH2CH20H + H20 k3 H O O C e COOH + HOCH2CH200C -@2OOCH2CHzOH 'k.H20 2 HOCH2CH20H % HOCH2CH20CH2CH20H + H20 .

385 (1988). Y. [kglrnol-hr] Yamada.1667X lO"Ti+l)X 1.5165 X 109exp(-22310 cal/RT) b'(1.7640X 107exp(-18380 cal/RT) kS=(0.01916Ti+l)X3. kl-k7: rate constants. Sci.6667 X lO"T.+l)X 7.3333 X 10-3Ti+l)X6. Eng.+l)X 2..5515 X 108exp(-18140 cal/RT) k3=(0.5657 X 109exp(-19640 cal/RT) k2=(9.O15Ti+l)x 1.7069exp(-2810 cal/RT) b=(3. T.. and Imamura.015833T. .0583 X lO''exp( -42520 cal/RT) k8=2k7 k9=4 k7 Ti: mole number of potassium titanium oxyoxalate supplied for lo6 moles of TPA.+l)X6.2595 X 106exp(-14960 cal/RT) k7=(0.290 Polycondensation reactions e C 0 O H + HOCH2CH20CH2CH20H ' . Polym. 28. k ki eCOOCH2CH20CH2CH20H + H20 Rate constants kl=(O.0125T.

7 10.S2 Ea [kcal/mol] 22 23 23.3 Polycondensation of bis(2-hydroxyethy1)terephthalate Catalyst: no catalyst Temperature: 195. E'.6 -37.2 15.0 k X lo2 []/mol * hr] a COOCH2CH20H G: HOCH2CH20H k'x IO2 []/mol hr] 0.: -@ C O O C H 2 C H 2 0 0 C a COOCH2CH20H dg/dt=ke*-4k'zg Rate constants k and k' of reversible polycondensation Temperature ["CI 195.0 X 1 0-' b=5.2 17.7 11.O 254.4 -38.0"C 29 1 UI + U1 U2 + G UI + Uj Uj+l + G Ui + Uj --+ Ui.8 0.0"C Rate constant [I/mol*h] kl=3.~ k'=4.23 1.5 AS' [cal/mol-OK] -41.1 8. j > l kl ko U I : HOCH2CH200C U.0 223 .O 254.4 2.0 2.=23 [kcal/mol] Energies and entropy changes of activation at 262.0 223 .8 .0 262.4 Ea=24 [kcal/mol] .9 11.54 2.0-282. + G + + k11 j>l i.0 282.S/l .0 30.Polycondensation of bis(2-hydroxyethy1)terephthalate 4.3 x I o .4 x 1 o-' kll/kl/ko=l/l.4 4.

. Mukromol. 38.hr] kl : rate constant of polycondensation reaction between monomer and polymer molecules. Chem..: activation energy for k'. [mol/l] e: concentration of 2-hydroxyethyl ester end-groups (-COOCH2CH20H). [kcal/mol] E'. Catalyst: no catalyst Temperature: 223-254°C Redistribution reaction: Ester interchange between the alcoholic hydroxyl group of a 2-hydroxyethyl ester end-group and an ester linkage of an ethylene diester group: R -COCH2CH20 + -C f7 I +I OCCH2CH2OC l? ^_Y -YHZCH2O H - . [I/mol. [mol/l] z: concentration of ethylene diester groups ( <00CH2CH200C -). [cal/mol * O K ] E. [Vmol-hr] k': rate constant for glycolysis of PET. [I/mol.: activation energy for k. [I/mol*hr] AS': entropy of activation. [mol/l] k: rate constant for polycondensation to PET.292 Polycondensation reactions g: concentration of free ethylene glycol (HOCH2CH20H). [kcal/mol] Challa. [I/mol*hr] ko: rate constant of polycondensation reaction between polymer molecules. 123 (1960). hr] kl 1 : rate constant of polycondensation reaction between monomer molecules. G.

OOC- + -_OC I at 23 1"C k. A-1.. 6. Polym.Polycondensation of bis(2-hydroxyethy1)terephthalate Temperature ["CI 223 254 kr [l/mol*h] 1. Catalyst: Sb203 Stabilizer: (C6H50)3PO (0. and Nettleton. [I/mol*sec] E. k'=0. R.9X 1.hr]. ER=24 [kcal/mol] kR=O. [kcal/mol] ER:activation energy for redistribution reaction. Sci. W. Inc.l1 [I/mol*hr] k. Temperature: 22 1-25 1"C Catalyst: antimony trioxide (Sb203) 2 -COOCH2CH20H e k -COOCH2C__.2 x 293 Activation energy: E. [Vmol-hr] kR: redistribution rate constant.: activation energy for polymerization reaction.=0. G. [kcal/mol] Challa.: activation energy for redistribution reaction.6 Torr . 889 (1968). Mukromol.33 [l/mol. Copyright 0 1968 John Wiley & Sons. rate constant of redistribution reaction. R. Reprinted by permission of John Wiley & Sons.06% w/w BHET) Temperature: 27 5 -2 85 "C Pressure: 0. 38.151 [I/mol*hr].. []/mol* hr] E. H. 138 (1960). k': rate constants defined in reaction scheme. Inc. Chem..=3 1 [kcal/mol] kr.=29 [kcal/mol]. [kcal/mol] Stevenson. J. E.

k. k ki PET + EG + e C O O H e PET + H2O k3 a PET Side reactions COOCH2CH20H * kG -@ O H " CO ' + CH3CHO a C O O H + --@2OOCH=CH2 aCOOCH=CH2 + -0 COOCH2CH20H k9 PET + CH3CHO -dCoH/dt=klC ~ H ~ .~ .. ~ ~ E kl=84. J. k5=l80k7 OH: hydroxyethyl-ester end-group. Japan Petrol. [ 0 /mol. T. k3.@ -+ HOCH2CH20H ki . Inst. 58 (1978).1 8500 cal/RT) kl=k2. k5>> k6. [ m o I / a ] kl.25k3. H.~ ~ C E G C D E S ..=0.. Chijiiwa.. k ~ C O O C H 2 C H 2 0 0 C . 21.: weight percent of catalyst in BHET (%) ci: concentration of i component in reaction mixture.. k2. DES: diester radical in polymer. ..0h.exp( . R. EG: ethylene glycol C. k3=4. COOH: carboxyl end-group. hr] Yokoyama. k7>> k8. and Kajira.~ C C O O H / ~ ~ + ~ ~ C O H .k9.5 X 108C. T.294 Main reactions Polycondensation reactions 2 aCOOCH2CH20H aCOOCH2CHzOH ' .. Catalyst: Sb203 Stabilizer: (C6H50)3P0 Temperature: 275-285°C 2 ~ C O O C H I C H ~ O'H . Sano. klo: polycondensation reaction rate constant.

J. /mol * hr] [o Yokoyama.09 C.: weight percent of catalyst in monomer. and Kajira..)<0...))C.Polycondensation of bis(2-hydroxyethy1)terephthalate 295 kl={2. Catalyst: Sb2O3 Stabilizer: (C6H50)3P0 Temperature: 27 5-2 8 5 "C Main reactions 2 aCOOCH2CH20H ' . R. 21.01 K(C. Japan Petrol. C..0 X 1016exp(-40000 cal/RT) 0.exp(-l8500 cal/RT)+4.: weight percent of stabilizer in monomer [-3 kl: polycondensation reaction rate constant. k ki e C O O C H 2 C H 2 0 0 C e + HOCH2CH20H e C O O C H 2 C H 2 0 H+ . H. 208 (1978).29 X 1010exp(-16. T. Sano..8C. Inst.Q C O O H * kz C O O C H 2 C H 2 0 0 C e + H20 Side reactions COOCH2CH200Ce + k3 e C O O C H = C H 2 + -@COOH -&OOCH2CH20H _k4_ *COOH + CH3CHO . Chijiiwa.. [-3 C. T.

+ eCOOCH2CH20H ' . Chijiiwa. Kugaku kogaku Ronbunshu. k'l.. EG: ethylene glycol. T. Sano.. H. Sano.. 236 (1979).. k5. [mol/Q ] kl... Inst.~1) 3 ~ D B S . . H.: weight percent of catalyst in polymer [%] Ci: concentration of component i in a reaction mixture. 21.3C.~ ~ C D E S + ~ ~ C O H ) / ~ ~ ~ H 2 0 ~ ~ ~ = . Yokoyama. and Kajira. Japan Petrol.. X 10'3Cxexp( -29800 cal/RT) h=5. k2. k3. J... 271 (1978). X 10'°C. R.~ ~ ~ C 0 0 ~ 1 .0 X 10I6exp(-40000 cal/RT) -1 k2=1.1 X 1010exp(-24200cal/RT) -37800 cal/RT) k3=4. DES: diester radical in polymer. T.296 Polycondensation reactions eCOOCH=CH.hr] [a Yokoyama.k 4 ~ 0 I kl=8.. kIs: reaction rate constants. /mol. T.exp(-17400 cal/RT)+8.~ C C O O H / ~ ~ .2CXX 10'2Cxexp( OH: hydroxyethyl-ester end-group. Chijiiwa./dt=-( ~ C ~ H / ~ ~ . R. H20: water C. k k5 e COOCH2CH200C-@- + CH3CH0 (5) -dCo~/dt'k~Co~~-k'~C~~~~~~-d~~~~~/df+k4 -dC~OOH/dt=k2COHCCOOH-k'2CH2O~DES-h~OH-k3~~~S dC. and Kajira.. 5.5C. COOH: carboxyl end-group.5CxX 109Cxexp( 8500 cal/RT)+4. h. k'2. T.

. DEG. + A E. +E. + DEG E. Z + A - *COOCH3 Methyl ester end group -0 COOC2H40H -@COOC2H400C e C O O H e Hydroxyethyl ester end group Diester group Acid end group DEG ester end group Vinyl ester end group e COOC2H40C2H40H aCOOCH=CH2 . and acid end groups E. h 22 ~ 2 + M k / Z Polycondensation reaction k3 (3 ) E. + EG E. + W ---f ks + E. E. + EG E. E.Polycondensation of bis(2-hydroxyethy1)terephthalate Catalyst: Sb203 Temperature: 240-290°C Ester interchange reaction E. + E./I<.. 297 +M (1) (2) Transesterification reaction + E. + EDEG E. E. + EG h. + + E. w Z kdKs +W Degradation reactions of diester groups Z E. + E. i3/KJ z + EG Side reactions forming acetaldehyde. + E. Esterification reactions k7 E.

and Mashelkar.0 18. Polym.15 0.6 17. K..8 X IO5 4.04 X IO6 1. + G MF. Temperature: 254-300°C Polycondensation Pin + Pi.8 17.5 k4 k5. k9: first-rate constants. Polym. Appl.04X 10' 3. Reprinted by permission of John Wiley & Sons.0 15.0 x io4 2. Copyright 0 1982 John Wiley & Sons. Eng.. A.. [ l/min] KI-K5: equilibrium constants Ravindranath.. R. Reaction with monofunctional compounds Pin + k.25 (')Units are [ ~ m i n ] kl-k3. J. and Mashelkar. K. A.6 37. % +G .5 29. 22 619 (1982). Sci. 2625 (1982).6 x io9(') Equilibrium constant 0.16~ io7(') 4. k5-kg : the second rate constants. [I/mol.. Inc. MFn J .8 29.5 1. 27.8 Frequency factor [Vmol-min] 4. Sci. k7 k8 k9 2.3 0.298 EG M W DEG A Polycondensation reactions HOC2H40H CH30H H20 HOC2H40C2H40H CH3CHO Ethylene glycol Methanol Water Diethylene glycol Acetaldehyde Kinetic parameters Activation energy [kcal/mol] kl k2 k3 15.. R.0 x104 6. Inc. Ravindranath.16X lo7 1.. Pin+.min] b.

Carbonyl end reaction z'. -&. + CH3CHO Z'.. 1122 z. Z. Z. d Pn+. + CH3CHO Z.: X: X': a e COOCH =CH2 COOH a C O C H 3 0 . PI" E%.40H MF... 7 C.% w x + c02 X' + c 2 0 PI. + P.: CH3(CH2)-14 Of ~OCH~CHIOY Z.Polycondensation of bis(2-hydroxyethy1)terephthalate Redistribution Cyclization Degradation reactions Thermal chain scission Vinyl end reactions Pin + P" P n kc 299 w + Pin+ii-r+ Pr G.: Z'. + H20 d + CH3CHO z.. + G d P. + ZIn-.: OHCH2CH2O-E-!a MFI: CH3(CH2).

85 [I/mol*hr] X ln(k'. S.00/1..17 (exptl) 4. [mol/l] Kumar. 01 . Inc.26 0.397 [l/mol. Gupta.21 0. Catalyst: Sb203 Temperature: 280°C Polycondensation reactions 2 a C O O C 2 h O H ks e + HOCzH40H -@COOC*H400Ce . 314 (1 982).75 "'exptl: experimental data.. 4421 (1982). 27. and Kunzru. J. []/mol * hr] RI R2 R3 R4 R5 R6 254 260 282 300 0.987T 103+19. N.. and Somu.00 2.. Inc.13 2. Reprinted by permission of John Wiley & Sons..55 (exptl) 3.37 2. Copyright 0 1982 John Wiley & Sons. Gupta.00/1.300 Polycondensation reactions Various rate parameters Temperature ["CI k .71 1. A. Appl. 0.)=-23.054 (exptl) 0..00 1. hr] X [Pl]0: initial concentration of BHET.88/1..71 01 . 0.114 (exptl) 0.. Eng. Kumar.1 01 .78 (exptl) 5.13 (exptl) 2. A. K. K. Sei.27 1.24 0.63 (exptl) 2.63 2.987T 1 03+1 X 7.00 2. Gupta..987T 103+27. Sei.724 [I/mol-hr] ln(kr)=-30.. Polym.22. D. B.37 (exptl) 2.229 2. B. Gupta. S.047 (exptI)(') 0. Polym. ln(kP)=-22.00 1..

Polycondensation of bis(2-hydroxyethy1)terephthalate Polymer chain and hydroxyl end group degradations 30 1 e COOC2H4OOCe + e C O O H + CH2=CHOOC-@-@COOC2H40H + kz (2) (3) -@COOH + CH3CH0 keg Esterification reactions a C O O H + HOC2H40H e k *c e C O O C 2 H 4 0 H + H20 -@COOH (4) + HOC2H400C ec k. e C O O C 2 H 4 0 0 C e + H20 (5) e Polycondensation involving vinyl end group COOC2H40H + C H 2 = C H O O C e '-@ O O C z H 4 0 0 C e C Cyclic oligomer formations HOC2H4f-OOC + CH3CHO k" (6) -@COOC2H4 j$H + +OOC+@ + H O C * H & O O C e COOC2H4 + H & COOC2H4+ + (7) --@ COOCH=CH2 + vinyl polymer -@COOH + polyene (8) .

Intermolecular acidolysis + a C O O H ~COOC&L-O-CO-@ (1 1) e k"r -@)-c00r2H4 -Qcoo + HOOC e Transesteri fication: -@)-cooc2H400c~ + ~ 0 0 c 2 H 4 0 0 c ~ - (12) e *y c + COOC2H40 oc -@ PC2H400c* (13) .302 Polycondensation reactions Diethylene glycol formations e C O O C 2 H 4 0 H + HOC2h0H * + COOH + HOC2H40C2H40H ---f (9) 2 eCOOC2H40H e COOH + +COOCzH40C2H40H + GCOOC2H40H O C e (10) -~COOC2&-O-CO-@ -@-COOC2H40H c k'r +-43COObH.

5 0. + E. keg. 24. k'.08 X lo6 2.8 17. E.5 - 2. + G \krli<r E. k. + E. Temperature: 2 17-277°C Main reaction Important side reactions Acetaldehyde formation Diethylene glycol formations Water formations E.36 X lo6 8..5 1. (12).8 18. Eng. Vinyl group formations &Z + W Z + E.. + E.'. + E.32 x io7(') 2. + ED E. + D E. K.36~ 10' Equilibrium constant 303 1) Eq(3) Eq(4) Eq(5) Eq(11) Eq( 12) 18. Polym.: forward and reverse rate constants of reactions (1)-(6). ( l l ) .. E. 30 (1984).5 29.25 - - (')Units are [ ~ m i n ] . kgc. k7 E. Ravindranath. k. E.. k. + E. and Mashelkar. + G E. C.5 18. kgr. + W + -- f=l kdK3 k3 Z + G E. A..Polycondensation of bis(2-hydroxyethy1)terephthalate Kinetic parameters Activation energy [kcal/mol] Frequency factor [I/mol*min] 1.6 37. kC. Sei.. + A E. k'. Z + A - k9 k3 A: CH3CHO D: HOCH2CH20CH2CH20H . k.2 x io9 1..08 X lo6 7.6 17.. R.36X lo5 1.

. and Gupta.25 - (')Units are [~/min] k3. min] b: first-order rate constants. 1045 Copyright 0 1984 John Wiley 8z Sons.04X lo6 3..16 x 107(') 4 . k5-k9: the second rate constants.5 29. J. [l/mol.: e C O O C H 3 E. Reprinted by permission (1984). S.. A. K.5 - &=2..04 X IO6 1.: a C O O C 2 H 4 0 H E.5 KS=1. Inc. Inc. of John Wiley & Sons...6 37. N. Sharma. 29. Appl.8 29.8 X lo5 4.3 04 E.8 17. S.: a C O O C H . . 1 6 io7 ~ 4.6 x io9 Equilibrium constant k4 k5 k k7 k8 k9 18. [-I Kumar. Polym. [ l/min] K3-KS: equilibrium constants.8 K3=0.: a C O O H Polycondensation reactions ED: e C O O C 2 H 4 0 C 2 H d O H E. Sci.6 17.C H 2 W: H20 z: ~ c o o c 2 H 4 0 0 c ~ Temperature dependence of various rate and equilibrium constants Activation energy [kcal/mol] k3 Frequency factor [I/mol*min] 6.16~ io7 1.8 29.

Polycondensation of molten-state poly(ethy1ene terephthalate) 305 4.OH + H20 kc (4) a COOH + HOC2H400C ee + HI0 --oCOOC2H400C4@ Polycondensation involving vinyl end group e C O O C 2 H 4 0 H+ C H 2 = C H O O C a - (5) a COOC2H400Ce + CH3CHO kv (6) .4 Polycondensation of molten-state poly(ethy1ene terephthalate) Catalyst: Sb203 Temperature: 280°C Polycondensation reaction 2 e COOC2H40H e ks +COOCzH400C-@ + HOC2H40H (1) Polymer chain and hydroxyl end group degradations ~cooc2€€400c~+ -OCOOH + CH2=CHOOCe kz (2) a C O O C 2 H 4 0 H+ e C O O H Esterification reactions .0 C O O H + HOC2H40H + CH3CH0 keg (3 1 s k 'e -@COOC2H.

OH 3 COOC2H4 HOC2H&OOC-@ zOH x (7) + fO O C G C O O C 2 H 4 z aCOOCH=CH2 + vinyl polymer -+ e C O O H + polyene (8) Diethylene glycol formations -@OOC2&0H + + HOC2H40H --f COOH + HOC2H40C2hOH + (9) 2 -@OOC2H40H e COOH + -@COOC2H40CzH40H O e + -@COOC2H40H O COo(i2H4 C e (10) -@COOCzH4 -0-C -(@COOC2H40H -k.C O e -43COOC2H4 (1 1 ) + -@COOH HOOC c k'r * + e (12) cod .O ...306 Polycondensation reactions Cyclic oligomer formation HOC2H4f-OOC e COOC2H4 -3. kgr +a Intermolecular acidolysis a C O O C 2 H 4 .

5 - 2..32 x io7(') 2.5 1. kgc. Sei.08 x lo6 2. kgr.. k.6 37. keg. (12).25 - (')Units are [ ~ / m i n ] k. R.. Ravindranath.. A. kg'c. k'g.Polycondensation of molten-state poly(ethy1ene terephthalate) Transesterification 307 -QC O O C 2 H ..36X IO6 8. Pc. kC.5 29. k. Eng. (1 I). K.: forward and reverse rate constants of reactions (l)-(6).8 17. 0 0 C e + -@OOCzH400C a- e e Eq( 1 ) Eq(3) W4) Eq(5) Eq(2) Eq(l1) Eq( 12) -0CT + PCIHe(N)c43oc COOC2H40 e (13) Kinetic parameters Activation energy [kcal/mol] 18. and Mashelkar. Polym.08 X IO6 7.6 17.36X 10' I 3 6 x io5 Equilibrium constants 0. 30 (1984). 24.8 18.2 x io9 1.5 Frequency factor [l/mol*min] 1.5 18. k. .

+ pp pn A A k.01/0. R5=klc/kp. R3=k'.88 X 103/1 .0 R2 1.747 1..0 2.: PI. + G Polycondensation PI.397 .368 0.02/0./kp.0 1.001 R5 0.001 0.0 2.002 0.002 0.0 2./kP.531 0. R2=k.0 1.002 R 3 0.01/0.4298 ln(k.002 0. &=kJkp.01/0.0 2.001 0. %=k.5X I 03/1.987T+13.0 2...248 0.02/0.0 R4 0. Pln+p-r + p.02/0.0 R3 2.01/0.0 2.303 0. + PI.0110.0 2.001 0.001 0. k.01/0.308 Temperature: 280-360°C Polycondensation reactions PI.03 In(kp)=-18.987T+27.002 0.0210.0 2.0 1. + n12 MI: M I : C.0 1.02/0.: RI=k'dk.0 2.002 0. 2.02/0./kp Rate parameters R1 to & at various temperatures Temperature["C] 280 290 300 320 340 360 R.001 0. \nk. Mn+m + G A C.0 1.0 2.)=-30.+. G. Reaction with monofunctional compounds Pin + Mn Redistribution Cyclization P.

. Eng. Madan.. S. Shah. Polym.: polycondensation rate constant. S.Polycondensation of molten-state poly(ethy1ene terephthalate) k. and Gupta. A. 194 (1984). G. []/mol min] k. 309 .. K. [I/mol*hr] Kumar. N.: redistribution rate constant. Sci.. 24..

Y. + W Sn + EG + Vin + Qm 3 ---$ + - 2ki 4ki 2ki 2ki + U. + EG Wn + EG k'eg Zk. Qn + W Ti. + W SI. + M Esterifications (for n 2 1) Pn * Si1 + A Qn Un + A S. + M n T + Vni n Zii+in + M Ester interchange reactions (for n l 1 ) Q. Tii. + M Rn + EG + Q. + Rin 3 Vn+in + M T + Uin 3 Writ. W Qn+m + W Zk. + Yn + A T.310 Qn Polvcondensation reactions Vntm + M Si Sntm + M Sn + Rin 3 Untin + M Wntin + M Sn + U m Sn + Vin * Yn+in + M Ti. + EG Zk. + EG + PI.. + Wn + A Acid end group formations (for n 2 1 ) P. +W + P n P n Pn + Sin + + ePiitin Uin e Win e Zk. + Qin * Tn+m + M Ti.. + M Un + EG Sn + M Vn + EG -+ TI..+in + W .

Polycondensation of molten-state poly(ethy1ene terephthalate) 3 11 .

312 Qn Qn Polycondensation reactions + Sin + + -+ + - + + - Sin Qn + Tin Qn + Tin SI1 + Sin Sn + Tin Sn + T i n T i 1 + Ti n + + + Un + Win Vi1 + Yin Uii + Zin Vi. + Win Wn + Yin Wn + W m Yn + Ziii W + Zin n .

Polycondensation of molten-state poly(ethy1ene terephthalate) 3 13 .

3320 X 1 07exp(-1 5000/RT) 4.1714 X 109exp(-1 8500/RT) 2.2126 X 109exp(.9286 X 108exp(.8505 X 10'oexp(-29800/RT) 7. Sei.3 14 Polycondensation reactions Rate constant 7.9286 X 108exp(-1 8500/RT) 3. and Choi.6640 X 107exp(-15000/RT) 4..8504 X 10Sexp(-l7600/RT) 1. . 2987 (1990). G.1 7600/RT) 9.18500/RT) 1. Reprinted by permission of John Wiley & Sons. Polym.8505 X 10'oexp(-29800/RT) 4. J.5857X 109exp(-18500/RT) 4. min i2/mo12min * * 12/mo12min i2/mo12min i2/mo12min 12/mo12min * 12/mo12min i2/mo12min * 12/moi2 min 12/mo12min 12/mo12min 12/mo12min * * 12/mo12min I/mol*min * l2/moI2 min Lei.8505 X 1Oi0exp(-29800/RT) 1. 41. Y.. Inc.1975 X 1012exp(-37800/RT) 7.7008 X 108exp(-1 7600/RT) 4.2126 X 109exp(. D.17600/RT) 4. Appl. Inc. Copyright 0 1990 John Wiley & Sons. K.9286 X 1 08exp(-1 8500/RT) Unit 12/mo12.

~ C O O C 2 & O O C+~H20 (6) .Polycondensation of molten-state poly(ethy1ene terephthalate) Temperature: 280°C Polycondensation reactions through ester interchange 2 a C O O C 2 & O H F====+ ki k ilK I 3 15 *COOC2H4OOCe Acetaldehyde formation -@200C2&OH + + HOC2H40H (1) e C O O H + CH3CH0 k2 (2) Diethyleneglycol (DEG) formations -(=&COOC2H40H + HOC2H40H + e 2 -@COOC2H40H Water formations e C O O H COOH + + HOC2H40C2H40H k3 (3) e C O O H + --()-COOC2H40C2H40H ka F==== 2 kdK h (4) + HOC2H40H eCOOC2H40I-I e C O O H + H20 kolK3 (5) + H O C 2 H 4 0 0 C .ko ..@w ..

5 1. R.5 29..5 - 2. K. k3-k. 415 (1984). Copyright 0 1984 AIChE. AIChE Journal. [-I Ravindranath.6 37.8 17. k7: first-order rate constants.6 17.08 X lo6 2.36X lo6 8.3 16 Polycondensation reactions Degradation of diester end group ~cooc2H400c~ + a C O O H + CH2=CHOOCe Polycondensation reaction of vinyl end group ~ C O O C H = C H 2 HOC2&00C + k7 (7) e + CH3CHO k8 -@ C O O C 2 H 4 0 0 C a Kinetic parameters Activation energy [kcal/mol] Eq( 1) Eq(2) W 3 ) .8 29.08 X lo6 7. and Mashelkar.36 X lo6 0. A. 30.8 18.5 (8) Frequency factor []/mol min] - Equilibrium constant 1. [l/min] KI-K3 : equilibrium constants.32 x io7 2. .5. [Vmol-min] k2. Reproduced with permission of the American Institute of Chemical Engineers.25 - (')Units are [ ~/min] k.2 x io9") 1. k g : second order rate constants.32 x io7(') 8. (4) E45) Eq(6) Eq(7) Eq(8) 18.. All rights reserved.

Polycondensation of molten-state poly(ethy1ene terephthalate) Temperature: 26 5-2 75 "C Depolymerization reactions . 0 0 C 2 H 4 0 0 C e + HOC2H40H Acetaldehyde formation reactions -@COOC2H40H --+ 3 17 + 2-OOC2H40H -e e C O O H + CH3CH0 + CH3CHO k2 COOCH=CH2 + HOC2H400C-@- -@ COOC2H400C a- k3 GCOOC2HdOH + HOC2H40H Water formation reactions e COOC2hOC2H40H k5 a C O O H + HOC2H40H ka/I<n + H2O G C O O C 2 H 4 0 H + H20 e C O O H + HOC2H400C-@- & kclK3 + H20 -@COOC2H4OOC-@Diethyleneglycol (DEG) formation reaction e C O O C 2 H 4 0 H + HOC2H40H + -0 + HOC2H40C2H40H COOH k7 .& .

30.2 7.8 37. Y. Park.5 29. 0. k8: first order rate constants.5 29. K. 707 (1 992).08 2. and Kang.58 X Activation energy for D. k3-k7: second order rate constants.4 [kal/g.8 18.6 29. Inc... Inc..2'" (')Unit is [l/min] [cm2/s] at 265°C De=2. Y.6 83. [cm2/s] k.. S.8 17. D.584 390'" 13. Polym. J.6 17.=38..2 2... B Polym.318 Polycondensation reactions Diester group degradation reaction C O O C 2 H 4 0 0 C+ ~ COOH Kinetic parameters Reaction + CH~=CHOOC-@- k8 Activation energy [kcal/mol] 18. [ml/mol*min] Lee. J. Reprinted by permission of John Wiley & Sons.min] k2. Moon. Phys. Sci. Copyright 0 1992 John Wiley & Sons.mol] De: diffusion coefficient of ethylene glycol in poly(ethy1ene terephthalate) melts.08 83. O.8 Frequency factor X 10-9 [ml/mol*m in] 0. . [ml/mol.

Polycondensation of solid state poly(ethy1ene terephthalate) 319 4.5 Polycondensation of solid state poly(ethy1ene terephthalate) Temperature: 230-245°C Depolymerization reaction --@200C2H400C-@ + HOC2H40H 7 k 1/1< I 2 GCOOC2H40H Acetaldehyde formation reactions aCOOC2H40H aCOOCH=CH2 e C O O H - + CH3CH0 k 2 e + + HOC2H400C-@C O O C 2 H 4 0 0 C e + CH3CHO k3 a Water formation reactions COOC2H40H + HOC2H40H GCOOC2hOC2H40H + H20 -@COOH HOC2&0H c====+ ka/I<n G C O O C 2 H 4 0 H + H20 e C O O H ka + HOC2H400C G& kdK3 G C O O C 2 H 4 0 0 C e + H20 .

mol] D. Kwon.. H.5 1.5 29..8 Frequency factor [ml/mol*min] 1.08 x io9 7. M. k 5 k 5 k8 (I) 2.6 37. Polym.320 Polycondensation reactions Diethyleneglycol (DEG) formation reaction e C O O C 2 H 4 0 H + HOC2H40H + COOH + HOC2H40C2HdOH Diester group degradation reaction e k7 e C O O C 2 H 4 0 0 C e+ -@COOH + CH2=CHOOC -@ k8 Kinetic parameters Reaction Activation energy [kcal/mol] 18. M.5 29. 0. H.=28 [kal/g.. J . H.32 X 10" 2.=5.8 k7 18. O. and Park.: diffusion coefficient of ethylene glycol in solid states poly(ethy1ene terephthalate).5 - - k4. k3-k7: second order rate constants. 25.. k8: first order rate constants. K.2 x io9(') Equilibrium constant kl k2 k3 0. Jeon.8 17.6 17. [ml/mol-min] k2.56X 10" 8.08 X IO9 2. [ml/mol-min] Yoon.25 - Unit: is [~/min] D.36 X lo9 8. 219 ( 1993) . [cm3/sec] kl.32 x 1 0 ~ ' ~ ) 3.67 X 1O-8 [cm2/sec] at 230°C Activation energy for D.

Polycondensation of solid-state polybutylene terephthalate 321 4. ~ C O O ( C H ~ ) ~ 0 0 C ~ H2O + Pln Degradation reaction k3 Pn~COO(CH~)~00C~Pln + Pl... .-COO(CH2)400C -P. e l P.P.~COO(CH~)~OOC~Pr + HO(CH2)400Ch... e + Pn-COO(CH2)~00C~P..-COO(CH2)400C ks + HOOC-P. - + HO(CH2)400C “Pr e Pl.Pln + HO(CH2)40H Esterification reaction kz Pl. HOOC-PI.-COOH + P. P1 1.COO(CH2)40H A P. Alcoholysis Pi. Esterolysis P n ~ C O O ( C H 2 ) 4 0 0 C ~ P+l lPs-COO(CH2)400C~P. + P1.-COOH + CH2=CH-CH=CH2 Side reaction Pnh.6 Polycondensation of solid-state polybutylene terephthalate Temperature: 2 14°C Transesterification reaction PIl-COO( CH2)4 -OH + HO-(CH2)400C -Pin e ki Pn-COO(CH2)400Ch.. e P l .-COO(CH2)400C - P.-COO(CH2)4-OH + HOOC-PI.&COOH + THF Acidolysis Pn-COO(CH2)400C-P.

p393. Sarti. Inc. Copyright 0 1984 John Wiley & Sons. Pisa. 2873 (1984).. Polymer. et al.. Gostoli. 22. Reprinted by permission of John Wiley & Sons.322 Polycondensation reactions Kinetic and equilibrium data for relevant chemical reactions Reaction Equilibrium constant Kinetic constant Reference "'Pilati. Eng.. J. . (3)Passalacqua. 22. 17.. Appl. 1479 (1983).V. G. AIM. (')Devaux. Polym. F. F. 1566 (1981). Short communication and posters. Inc.. Pilati. et al... and Giacomo. F. Polym.. Polymer. 29. et al. B. 10-14 October 1983. DI. (4'Pilati. Sci. Sci. '"Pilati. Polymer... 6" Convegno Italian0 di Scienza e Technologia delle Macromolecole. 229 (1982).. J. C. C. F. 1044 (1976). 24. et al.

Copyright 0 1990 John Wiley & Sons.180 X 10'5exp(-16884/RT) [mI2/mol2*min] k: forward reaction rate constant. S. [mI2/mol2 min] * k backward reaction rate constant.. [ml2/moI2* min] Hersh. J. Inc.min] kl=8. H20 Temperature: 150-1 80°C A + B c ' C + P k. Sei. Appl.7 Transesterification of diphenyl carbonate with bisphenol Catalyst: LiOH. and Choi. Y. P: H O G k=4..1 k CH. Reprinted by permission of John Wiley & Sons.Transesterification of diphenyl carbonate with bisphenol 323 4. .41. Inc. K. 1033 (1990). Polym.890 X 10'7exp(-21048/RT) [m12/mo12. N.

H. Borsig. P.119. W.115. S.239 B Bacon.176 109 186 77 24.233 45. H. Bywater. I95 146 292. Bresler. 149 32 244 49. 254 89 56. D. F. J. S. Y.227 84 34 80. M. E. B. M.293 217 23 50. Ault.140. Bresler. G. P.134.147 32 46 270 175 24 I 88.186 62. Bitai.204 209 85 234. G. C.196 222 23 1. C. Bazant. Bukatov. Z. J. L. Cameron. C. Cavender.274 54. R. H. G. Berger. 257 61. E.150. H.273. S.84 260. Atkinson. Bevilacqua.150.135. G. Cerrai.79. M. A. Chinmayanandam.157 81. S.137 125 144 29 46 213. Bostick. E. K. W. Chien.19 1 75 118 C Cameron. S. H. E.324 260. B.194. G. Capiati. Broadbnet. N.54. M. E. Brumby. E. J. I.77. E.l82. C.58. M. Bartlett. Billmeyer. Ahmad. H. Clouet. E. C. B. BlavierL.188. 140. Bawn.109.57 57.8 I.324 Author Index Author Index A Abdel-Alim. Burnett. Adams. H. 1.34.295.296 63 3 14. J. G. E. W. W. J. Choi.169 . K. Bamford.186 276 Bradford.187. V. A. H.174. R. Challa. F. 157. D. Andrianova. C. Cimini. D. Coco. G. F. L. Benson. Allen. Cernec. Brandolin. W. V. Arnett. C. Ballard. E.225 256. Baxendale. Burnett. Brackemann. A. Chaffanjon. R. P.63. C. Baldwin. N. J.116.135.147. Chen. T. Adelman. S.233 52 226 75 61. Auer. Chen. M. P. J. N. B. E. Capla.194.195. Baysal.132. A. S. Artigiani. 200 122 278 23 1. C. D. M. M. F. Berger.27 1 294. Anthony. B. C. N. J. L. J. Bovey. Bevington. Chang. G. Buback. I67 l73. R.273 223 I46 I 14. Y. Chumaevskii. Brickman. R.183. D. B. Chadha.80. Chijiiwa. A.60.183. J.255 86 43 283 2.236. Busulini. Bengough. W.186 248.

Hamielec. R. Z. V. J. C. J. llart. C. T. DI. Gupta. P. S. F. Hodgins.254 . D. Honig.238 250. N. J-L. Greenley. N. G.171. N. Davis. Henrici-Olive. Harumiya. Gilbert. E. F. R. Fritzsche. A.304.163 57. J. N. S. M. Gregg. A. Ho. K. 162. P. S. V. M.227. s. George.57. A.252.309 H Corrin.163 207 153 218 323 265 56. Dimaina.60.158. P. S. Goto. B. L. P.186 17 244 219 29 103. F. R. T. 1.180. N. Hili. Gornick. Dewar. H. P. A. A. Hsu. M. Grassie. Hippler. H. P.162. Hayden.25 1. Gerrens. C. Fujii. Friedlander. M. A. G. Doi. Fris.118.258 130 300 300. Giacomo. P. Eldiwani. Feldman. S. R. Fabbri. Fetters. Farber.141 257 2 13.146 96. B.9 99. C. J. Graven. FIQgstad.32 284 4. M.132. S. F. V. E. Hafeez.193 254 152. Cotton. W. 1-1. T.127. H. G. N. D. D. 22 1 32 70. Feucht.200. 178. Dainton. Crosato-Arnaldi. Gleixner. M. Giusti. G.207 D Dahl.180 15 222 62.228. K. P. M. E 203 6. Downer. 123 75 206.65.152. D. Hill. H. P. Gloor.84. W. J. Hsieh. Evans. A. B. P. E.7. Hay. M. R.186 10 56. Gasparini. G. N.86 F Eaton.172. M.194 69 23.230. Hagiwara. W. F.135. Dixon-Lewis. J. C. Fukui. J.74. Hertzberg. Frolov. K.274 54.58.237. Grancio. H. B. Felder. G. Greffe.167 226 185 268. N. L. J. J.135. Grechanovsky. R. G.127. M. S. S.228 26 20 1 116 37 126.178. L. Glass.141 34 83. E.215.269 40 G Gaba. Hirota.150. R. Howell. Hawkett. J.155. Goosney. Furui. I8 1 111 22 126. E. GibbsW. Deb.166 257. Grieveson.18 1 216 68 108 324 20 1 84 70. G. Ehrlich. P. Gundlach. Gupta. G. M. J. B. J.155 246 23 214. Y. Fomichev.138 257.241 154 144 246 178 87 323 40 126 61.Author Index ~ 325 226. Hersh. Gostoli.128.246 61. M.

14. Kwon. S. K.94. Krupgka. J. J.119. G. D. T. H. F. K. Lansdowne. Jeon. R. K Keii.290 46.175 46 69 25 1 318 247 314 24 151 98. Ivanova. Y. K. C.117. Kiuchi. M. Kremminger. M. M. S. Ishii.268. M. I99 205 33 222 2 13. Landers. Ledwith. J. 120. Kapoor. D. 288. Ito. R. Y. Ilui. Lee. Lendle. Kurz. A.102 16. M. P. S. S. Ito.309 300 50. Kuhlmann. H. D.148. N. A. J. Kwart. G. 0 Husain. Kumar. M. I. 112. Kagiya. Kuo. I. Lazar. D. W.53.54. Lim. J. Hummel. 202 67 320 136 140. Kubota.36 265 19. I.191. L. A. N. Kubicek. G. Kamachi.92.225 219 260.304. J. Komatsu. Kise. K. 246 K Kageoka. L.273 174. -C. R. A. P. D. C. Landfield. 269 270 259 205 249 72.95. Kim. Kolinsky. S. A.122. H. Author Index I50 76 171 151 172 69 Kodama. James. M. Kohn. E.326 Huang. K. C. E. Kilham.148 22.186 320 I Imamura.227 85 26.33 M MacGregor. Liaw. Lal.272. D.295. Livigni. Kao.267. Lee. F. J. Kiparissides. Hughes. N.145 283 240 2 i‘7.159. Lora. Imoto. Lee.270. M.199 318 91 130 96 49. S. Johnson. J. Kazbekov. N. L. W. S. H. J. S. I. L.96. Kajira. Lei. D-H.274 86 264 264 203 22 12 . A.22. J. N.156. J. K. J. Laita. Joshi.197 222 222 24 1 J Jain. Lin. Y. Kani. T. G. Lufi. A. J. F. T.116 176 259. Kuznetzova. L 20 35.269 294. Y. Ishida. K. G . R. R. Y. Lapanje. H. Hutchison.192 300. Ivanova.41. H. S. Ley.157 182 Laird. Iwakura.257. D.90. M. Kunzru. Joiner. H. Kazbekov. Kojima. Lim. S. D. Kim. S. M. S. H.296 98.92 259 91 90 47. Kang. A. E.124 152 49.

89 173 98.94.141 73. L. Mashelkar. T. F. T.144. P. Onyon.137.187. A. Machi.24 1 28 1. 14. Makimura. Miller.199 283 226. Otsu.195 193 10. Norrish. Nelb. Paoletti.62. M. O’Sullivan. K. K Majer. W. Matsuo. T. S.64. S.307. Matsuda. A. Ng. Manabe.54.100. Olive.5 1.122. M. G . A.320 269 . Michaels. J. S.57. H. T.71.152. Mare. Mackay. J. K. 133. H. Mendiratta. A. G. Morrell. Mellichamp.194 135. 188. Matheson. F. Y. 87 57 50.227. Pasquon. G. P. Meyerhoff. D. S. North.2 13. A. R. 0. D. L.7 1.145 108 2 249 153 90. G.142.I43. K.Author Index Machacek.175 268 270 244 Morton. S.79. I.146 57 104 212 46.72.53. W. H. A. J. S.303. F. Murayama.316 6 I . S. Y. Miyama. 124. Okamura.76. 0. R. W. T.165 54. A. Omi. Nitirahardjo. Moad. H.99.66.183. Muzsay.103. O’Driscoll. O’Donnell. G. Natta. Ottino.78.120. A. 186. T. G.186 288 49. 1 19. 1 . Y .128. P. Nozaki.298. Mito.53 111 72. Murata. T. 119. G. S.186 47. Ogawa.127. F. Olaj. Ohashi. H. P. J. M.209 70.228 49. G. G.287. T. Malkin. Magott. Moon. : Maschio.78.143.142. J. Napper. Moze.92 56. Mickley. Onishi.19S.247 284 88. Nozakura.148 222 P Palma.190 84 318 20s 203 20 0 O’Brien.120. H. G. Mayo. McCabe. A. Z. Offenbach.84. 46. R. M.118.135. 36 22.72. M. Nicholson. C. Nelb. J. W.269 59 309 233 50. N Nakaya. F. E. 85 125 3 18. 0. M.111. Nelsen. K.112.68. J. Mahabadi. Malavasic. A. 0. Moore. May.189. S. Jr Minarik.175 222 111 327 16. K.257.135.181 269 210 210 130 293 250 139 247 139 75. R. R. Mork. R. H.61. S. Madan. H.150. J. K. W.63. R.166 216 276 59.259 210 112 103. G. M. Misra. Melville.139. L. A.140.4I . Nettleton.. S. Park. Majury.158 205 205 138 2 17. D. R. A. A. J. S. Mikami.188.

Schneider.298. Shukla. Ryska. M.183 255 . E. 1-1. Ray. R. P. L. Sack. Seed. Sood. M. J. L. S. Author Index 45. Soga. Rigo. Porter. Roovers. P. D. C. N. I. Sutani. P. Sund. R. -H. Saltman. Saccubai. Rod. J. W. G. Sergeev. C. A. S.303. P. E. G. I. S. S. K. C. Shah. H. Penboss. Perry.14$. R. K. Schuurmans. M. H. Pinto. Saiki. R.115. R. Shepelev. J. G. C. N. Rangnes. T. Pilati.295. F. Seaman. N. W. Stockmayer. Santappa. Suzuki. P. Reed. P. S. Pomery.14. J. F. C.195 203 284 219 112 123 267. D. G. 212 R Rafler. G. Poddubnyi. 77.307. Schulz. Id.269 27 88. Sebenda. Salovey. R. S. Z.169 Schnabel. S. W.196 128 257 323 208 99. G. J. Reichert. C. Sugimoto. Schnaup. Symcox. H.287. V. A. K. S. R. C.109. E. Schorr. A. Sangster. W. Shimidzu. J.272 55. J. W. Shirodkar. Sir. Pons. Sakata.316 202 89 262 22 1 216 284 I09 239 84 205 S 14 73 267. P.I91.176 309 111 Q Quintana.328 Patrick. A. R. M. Schnoll-Bitai. K. Somu. Sidiropoulou.146 244 57 29 23 I I22 114. Rajagopal. 124 202 265 152 294. N. Ya. V. C. C. Smith. 15 I82 203 28 1. E.145 217 73 270 34 6 219 20 274 49. C. T. G.127 300 I52 219 293 210 40 20 1 223 65 274 182. H. Russell. K. E Swain. A. J. T. N. S. W. 1. Scamehorn. K. Smith.296 4. A. Rogers. P. R. Salatiello.192 262 151 72. J.270. Sundberg. Stauffer. G. Robb. Shadrin. Ravindranath. E.270 249 l6. Pryor. J. Piton. C.116. Sharma. E Price. Schweer.74 323 160 150 304 84 274 257. Sharma. P. Stevenson. C. M. Shen. M. V. Sarti. E.4l. W. Sittler. C. S. J. Soh. Sharma. F. V. Sano. B. W.

295. F. A. Vizovisek. Tarkowski.249 83. L. Westlake. V. K.74 111 v 133 32 44.274 33 91 294. K.102 .274 I54 62. Winnik.Author Index T Taira. Wright.106.240 43. L.146 218 264 234.136 24 1 182 27 24 1 U 249 20 1. J. Zafar. Volrnan. Yuasa. F. W. M. S.193 278 252 268 225 260. Yamamoto. W. VanHook. W. Takeda. Tebbens. J.236 178 204 24 1 12 120. Zutty.44. Takeuchi. K.109. Tatsukami.269 Z 80. Worsfold. C. K. M. L.107.22 1 274 54 65 149 31 15 329 W 54. K. A. P. T. Tobolsky. 'Timm. Valles. A. Utsumi. 1. Ueda. Welch. Yokota. Williams. N. s. J.18. R. Yeh. Vidotto. S. K. Yarnamoto. Tanaka. G. Yaguchi. Vaughan. D. Tamura.99.203 4.273. B. Zakharov. 270 270 31. Yano. Vermeychuk. Valentine. D. T. E. M. F.106 149 I68 23 Yagi. I75 34 17.92 12 235 150 Wada. M. Taylor. Toda. D. M. Yoshimoto. P.79. K. M. Vogele. H. 206 29 49. I. Villennaux. I. 1-1. S. B. Yokoyama. Yamada. T. T. D. I48 288. D. J.273.296 320 249 31 257. Y. Yoshioka.207. J. M. J. L.93 260. G . S. Yoon. Wittmer. J. Tsien. Yokawa. 14. Tsuyama. M. H. Uri.32 IO 249 206. G. M. L.137 2 155 222 26 160. J. T. 0. Yang. Tilger. M. A. 'l'auer. L. Thomas. Ugelstad. T. Tazawa. Takagi. V.104.19. V. Takahashi. J. Yamada. K. H.122. A. M. G. Yamanis. H. Y.290 40. F. Talamini. Wright. J. Y I26 84. J. J. K. YermakovY. P. 1-1. Watanabe. N. -P. Vanderhoff. W. 'l'anaka. woo.22. E. 'Trivedi.