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A trans-vinyl double bond) by disproportionation. , World Congress I11 of Chem. , Tokyo, p108, 1986. 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 r,* r, Termination r,* 0 2 * + C2H4 + C2H4 + O2 + TI,* 2r0* rIlcl* * deactivated products or hydroperoxide P,,+,,, -+ + ---f kd kP kr kt rll*: polymer radical with n units of monomer, PI,: dead polymer with n units of monomer.

S -+ --j + + M. l 2ka[R. I [MI k,[M * 1[MI ktr[Mr. : polymer radical containing r units of monomer, M,: dead polymer containing r units of monomer.

Bulk polymerization Initiator: benzoyl peroxide Temperature: 60°C Initiation Propagation Termination [I1 [RI + [AI + [Plj + [AI [P]i + [PI, [Pli + [Plj-+ + + -+ 2[RI [PI1 [Plj+~ [M]i+j [Mli + [Mlj kd ki kP ktc ktd [I]: initiator, [R]: primary radical, [A]: monomer, [Plj: growing polymer radical containing j units of monomer, [MI,: dead polymer containing r units of monomer. 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.

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