Kinetics of long-chain branching in emulsion polymerization: 2. Vinyl acetate polymerization

Abstract The loci of polymerization in emulsion polymerization are the polymer particles, with diameters usually in the submicrometre range. The effect of such compartmentalization of the reaction system on the molecular weight distribution development in non-linear polymerization is investigated by application of newly developed simulation models for emulsion polymerizations that include chain transfer to polymer and terminal double bond polymerization. Kinetic parameters and experimental data for vinyl acetate polymerization reported by Friis et al. (1974, 1975) are used. It was found that the effect of compartmentalization must be accounted for in vinyl acetate emulsion polymerizations, and that the kinetics of long-chain branching in this reaction system needs careful reinvestigation using an appropriate reaction model and analytical techniques with higher precision.