Abstract
The rate of chemical-initiated bulk polymerization is studied theoretically and experimentally over the complete course of reaction. Taking into consideration the effects of the decrease of jump frequency of a polymer segment during polymerization on the rate of each elementary reaction, a new kinetic model is proposed. This model is applied to the bulk polymerization of methyl methacrylate and styrene for several initiator concentrations and temperatures. Though the polymerization of these monomers shows very different auto-acceleration effects, experimental data of conversion and number-average and weight-average chain length can be successfully correlated to limiting conversion by this model.
