Monte Carlo simulation of controlled/living radical polymerization in emulsified systems

摘要

A new MC simulation method is proposed for the controlled/living radical polymerization in a dispersed medium, assuming an ideal miniemulsion system. This tool is used to consider the effects of particle size on the polymerization rates and the molecular weight distributions. For NMP, the polymerization kinetics are basically governed by two conflicting factors, (i) the confined space effect that promotes the coupling reaction between a radical and a trapping agent and (ii) the isolation effect of radicals into different particles that suppresses the overall frequency of bimolecular termination. For RAFT polymerization, a significant rate enhancement by reducing the particle size could be observed only for the systems with fast fragmentation of adduct radicals.