Microstructure evolution and simulation of copolymerization reaction using a percolation kinetic gelation model

Abstract

A new kinetic gelation model that incorporates the kinetics of non-linear free radical copolymerization is presented. Copolymerization of bi- and tetrafunctional monomer mixtures is simulated to characterize kinetic effects on polymerization statistics and microstructures. An algorithm for random next step selection in a self-avoiding random walk and efficient mechanisms of component's mobility are introduced to improve the universality of the predictions by removing commonly occurring simulation deficiencies due to early trapping of radicals. The model has the capability to predict the onset of the sol–gel transition, and the effect of chemical composition on the transition point. It is shown that a better understanding of microstructure evolution during polymerization and chemical gelation is attained. Lastly, one important benefit of the simulation method is the ability to simulate very highly packed random chains or microgels within a polymer network.