Effects of initiator homolysis rate constant on kinetics and chain length distribution in living free-radical polymerization

Abstract

The kinetics, chain length and distribution of living free-radical polymerization with initiators of different homolytic rate constant, kd, were simulated by a Monte Carlo algorithm. The results show that, for the system with a lower kd (10-5-10-4 s-1), the polymerization rate is much faster and chain length increases linearly with monomer conversion. However, for the system with higher kd, nonlinear increase in average chain length, and lower reaction rate are found in the simulation results. Low polydispersity indices were obtained for higher and lower kd.