Kinetics of the emulsion polymerization of vinyl acetate

Abstract

AbstractRecent investigations of the emulsion polymerization of vinyl acetate report a variable behavior. The reaction has been reported to exhibit a half‐order rate dependence and no particle number dependence on the initiator level, or a first‐order dependence for both the reaction rate and particle number on the initiator concentration, or some behavior between these two extremes. While two recent models have attempted to account for the changes in the reaction rate dependence by postulating either an aqueous phase or a polymer phase termination, no adequate explanation of the particle number behavior has been given, nor has a single model been suggested that agrees with all of the experimental data. This investigation confirms the results of previous investigators and develops an empirical model for the particle number, taking into account the effects of the initiator level, emulsifier level and alkyl chain length, temperature, and ionic strength on the particle number. This particle number model, used with a polymer phase termination reaction model, yields a polymerization rate expression which agrees with all previous data.