Modeling of the Nitroxide-Mediated Radical Copolymerization of Styrene and Divinylbenzene

A mathematical model for the copolymerization kinetics with crosslinking of vinyl/divinyl monomers in the presence of nitroxide controllers has been developed and validated using experimental data of TEMPO-mediated copolymerization of styrene (STY) and divinylbenzene (DVB). Polymerization rate, molecular weight development, gelation point, evolution of sol and gel weight fractions, crosslink density, and copolymer composition, as well as concentrations of the species participating in the reaction mechanism can be calculated with the model. Diffusion-controlled effects were assessed and found unimportant. The presence of nitroxide controllers seems to favor the production of more homogeneous polymer networks, but this effect decreases as the initial fraction of crosslinker is increased.