Radical Lifetimes in Atom Transfer Radical Polymerization: A Monte Carlo and Deterministic Investigation

Abstract

Mean radical lifetimes and fluctuations in lifetime are shown to decrease with conversion and polydispersity index for atom transfer radical polymerization (ATRP) of both methyl methacrylate and styrene. In the first study of its kind, a comprehensive investigation of radical lifetimes in both ATRP and conventional free-radical polymerizations is reported using a kinetic Monte Carlo model. Quantile–quantile plots show the radical lifetimes to be exponentially distributed with equal mean and standard deviation. Radical lifetimes are shown to be thousands of times longer in conventional free-radical polymerization compared with ATRP. Reduced mean radical lifetimes and fluctuations offer a new perspective on the ATRP mechanism. Reduction in radical lifetime fluctuations ensures less variability in the number of monomer units added during the propagation steps and keeps the polydispersity index low. Deterministic models are used along with the kinetic Monte Carlo model to investigate several facets of these polymerization systems and are validated against experimental data.