Phase separation in free-radical crosslinking copolymerization: formation of heterogeneous polymer networks

Abstract

A model combining both the thermodynamic and kinetic aspects of free-radical crosslinking copolymerization (FCC) is presented to predict the formation conditions and the properties of heterogeneous (porous) networks. The model involves thermodynamic equations describing the phase equilibria between the network and separated phases during FCC of vinyl/divinyl monomers and kinetic equations giving the concentration of reacting species and the polymer properties as a function of the monomer conversion. Calculation results are presented for styrene/ m-divinylbenzene (S/ m-DVB) copolymerization system in the presence of inert diluents. S/ m-DVB copolymerization system at a high m-DVB concentration, or, at a low monomer concentration phase separates at the gel point and results in the formation of a microgel solution. The calculation results also show that the heterogeneity in S/ m-DVB copolymer networks increases on increasing DVB or diluent concentration, or, on decreasing the solvating power of the diluent, in accord with the experimental data published previously. The model also predicts correctly the equilibrium volume swelling ratio of heterogeneous networks in solvents.