Modeling of the Free-Radical Copolymerization Kinetics with Cross Linking of Vinyl/Divinyl Monomers in Supercritical Carbon Dioxide

A mathematical model for free-radical copolymerization kinetics with cross linking of vinyl/ divinyl monomers in carbon dioxide at supercritical conditions was developed. The copolymerization of styrene and divinylbenzene is analyzed as a case study. The effects of the kinetic and physical parameters on monomer conversion, molecular-weight development, copolymer composition, appearance of the gelation point, gel fraction, and average cross-link density are studied. Model predictions show the expected trends, although the system is quite sensitive to pressure, which provides an interesting and promising way to tailor some of the polymer properties.