Reaction Diffusion Enhanced Termination in Polymerizations of Multifunctional Monomers

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Abstract
A model was developed to predict the reaction behavior of multifunctional monomers during photopolymerization. The model incorporates transition regions from reaction to diffusion controlled propagation and termination, a reaction diffusion termination mechanism and volume relaxation, and is able to predict reaction rates, radical concentrations, and kinetic constants for termination and propagation. For reactions leading to highly crosslinked polymers, the reaction diffusion termination mechanism was significant even at low conversions and dominated as the polymerization proceeded. Reaction diffusion was evidenced by plateau regions in the termination kinetic constant, which were found to be most dependent on two model parameters, monomer size and a mass transfer ratio.