Emulsion polymerization of vinyl acetate using a polymerizable surfactant. III. Mathematical model

A mathematical model was developed to aid in the further understanding of the growth of latex particles in the emulsion polymerization of vinyl acctate using a polymerizable surfactant, sodium dodecyl allyl sulfosuccinate (TREM LF-40). The model incorporates the main features of the system observed experimentally: copolymerization in the aqueous phase, at the particle surface, and chain transfer to TREM LF-40. The reactions at the particle/water interface and, more specifically, the chain transfer to TREM LF-40 leading to a decrease in the average number of radicals per particle, was found to be the most significant mechanism for explaining the difference in kinetic results found for TREM LF-40 and its nonpolymerizable counterpart. The copolymerization of vinyl acetate with TREM LF-40 was also shown to slow the overall polymerization rate. However, the copolymerization alone was not sufficient to account for the decreased polymerization rates observed experimentally. A combination of copolymerization and chain transfer to TREM LF-40 was found to provide a good fit of the experimental results. © 1993 John Wiley & Sons, Inc.