Modeling of Branching and Gelation in RAFT Copolymerization of Vinyl/Divinyl Systems

The reversible addition−fragmentation chain transfer radical polymerization (RAFT) with branching/cross-linking is theoretically investigated on the basis of the method of moments. The system considered consists of the copolymerization of vinyl monomer in the presence of a small amount of divinyl comonomer. It is found that the gel point is significantly postponed by increasing the RAFT agent concentration. Flory’s criterion, ρr w,0 = 1, is found to be satisfied at the gel point in the RAFT cross-linking process regardless of the unequal reactivities of vinyl/divinyl monomers in the absence of cyclization. The gel conversion can be analytically expressed and is determined by the polymerization recipe and the relative reactivities of various double bonds. The gel point is postponed by the presence of intramolecular cyclization, and its effect becomes significant in a dilute polymerization system. Branching distribution is found to be very broad with a large fraction of linear primary and slightly branched chains. By the introduction of the dependence of the reactivity of the pendant double bond on the local heterogeneity, the branching distribution becomes narrower and can be fine-tuned.