Kinetic gelation modeling of controlled radical polymerizations

A kinetic gelation model has been developed that incorporates the kinetics of a living/controlled radical polymerization. Specifically, the kinetics of an iniferter polymerization were implemented in the model to determine the effect of the kinetics on the polymer structure. In particular, the replacement of the termination step with a reversible termination was examined. The model predicts the formation of more monodisperse linear polymers in the presence of an iniferter and a reversible termination reaction. When termination by combination is allowed to occur, the polydispersity increases. For cross-linking reactions, it was concluded that the iniferter only had an effect on reactions with small amounts of crosslinking agent, resulting in a delay in the gel point and a more heterogeneous structure. When the amount of cross-linking agent is increased, there is no difference in the network structure obtained by a crosslinking reaction with an iniferter versus a cross-linking reaction with the classical free-radical initiator.