Control of network structure in emulsion crosslinking copolymerization

Abstract

A kinetic model for network structure development during crosslinking copolymerization of vinyl and divinyl monomer is proposed. The model calculations suggest that polymer networks synthesized by free-radical copolymerization are, in general, inhomogeneous at least on a microscopic scale. By application of the same kinetic parameters as those for bulk polymerizations, it was found that the crosslinking density of the polymers formed in the earlier stages of polymerization is very high in emulsion polymerizations and polymer networks tend to be highly heterogeneous. Homogeneous networks cannot be formed even under Flory's simplifying assumptions for vinyl/divinyl copolymerization in emulsion polymerizations. The present kinetic model can be used to find semi-batch policies to control the network structure, and semi-batch policies were used to illustrate the synthesis of homogeneous polymer networks.