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**Extra info for Rate equations of polymerization reactions**

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6 b: decomposition rate constant, [ l/sec] ki: initiation rate constant, [Vmol-sec] k,: propagation rate constant, [I/mol*sec] ktc: termination rate constant by combination, [l/mol*sec] ktd: termination rate constant by disproportionation, [I/mol*sec] Kuo, J. F. and Chen, C. Y. Polym. J, 13, 453 (1981). 51 Methyl methacrylate Bulk polymerization Initiator: 2,2'-azobisisobutyronitrile Temperature: 25°C Initiation I R" + M Propagation Pi," + M Chain transfer +Y Termination by disproportionation P,O + PI," + PI," P,,O Termination by combination P,,O + + + + + + 2R" Pi'' Pnt i o PI, + Y" P, + PI, P,+,, kd ki kP ktW ktd(n,m) ktc(n,in) I: initiator, M: monomer, R" : primary free radical, P," : growing polymer radical containing n units of monomer, P,: dead polymer containing n units of monomer, Y: chain transfer agent.

6 0 ko: frequency factor, [-I E,: activation energy, [cal/mol] V,: activation volume, [ml/mol] P: pressure, [atm] T: temperature, [OK] K,: initiation rate constant, [ l/sec] K,: propagation rate constant, [I/mol sec] Kfi,,: monomer transfer rate constant, [Vmol sec] Kfsn:solvent transfer rate constant, [I/mol*sec] K,c: termination rate constant by combination, [I/mol*sec] Ktd: termination rate constant by disproportionation, [I/mol- sec] Kscn: short chain branching rate constant, [ l/sec] Shirodkar, P.

105, 212 (1967). , Makromol. , 114, 201 (1968). Methyl methacrylate 47 Bulk polymerization Initiator: 2,2'-azobisisobutyronitrile Temperature: 60°C C R + M Xr + M Xr + X, Xr + R 2R 2R +XI + + + + + Xr+l Pr + P, or Pr+, P, products C: initiator, R: primary radical, M: monomer, Ar: growing polymer radical with r monomer units, P,: dead polymer with r monomer units, Y: chain transfer agent. 41 x [C]: concentration of initiator, [mol/l] [MI: concentration of monomer, [mol/l] kd: decomposition rate constant, [ l/sec] ki: initiation rate constant, [Vmol esec] k,: propagation rate constant, [I/mol*sec] k,: termination rate constant, [Vmol-sec] kt,: primary radical termination rate constant, [Vmol-sec] k,,: rate constant between primary radicals, [I/mol- sec] R,: propagation rate, [mol/l-sec] Ito, K.