Radiation-induced seeded copolymerization of tetrafluoroethylene with propylene. II. Kinetic analysis

The radiation-induced seeded copolymerization of tetrafluoroethylene with propylene was kinetically analyzed by assuming that growing radical in polymer particle is deactivated by degradative chain transfer to propylene and/or by recombination with newly entered radical which grows for a while before recombination. Apparent rate constant of initiation is 2.6 × 10^?9 mole/liter rad independent of the monomer composition in polymer particles. Apparent rate constant of propagation lies in the range of 10⁵ hr^?1 increasing with tetrafluoroethylene fraction. Change in apparent rate constant of chain transfer with propylene fraction suggests that first-order termination by radical occlusion or radical escape to aqueous phase may occur simultaneously with the degradative chain transfer. Average number of radical in a particle is found to increase with dose rate and levelled off at the value of 0.9. The higher value above 0.5 is explained by Trommsdorff effect. The dose rate exponent of average number of radical changes from 1 to 0 with increasing dose rate. This change is consistent with the dose rate effect on the polymerization rate under the constant number of polymer particles.