A Simulation of Kinetics and Chain Length Distribution of Styrene FRP and ATRP: Chain-Length-Dependent Termination

A high-performance Monte Carlo simulation, which takes diffusion-controlled and chain-length-dependent termination into account, is developed to thoroughly simulate the kinetics of free radical and atom transfer radical polymerization (ATRP) of styrene. The average termination rate constant greatly decreases during ATRP; nonetheless, it is almost independent of conversion and smaller in free radical polymerization (FRP). Polymer chains are entirely initiated at the beginning of the ATRP, whereas initiation of chains continues over the course of the FRP. The dead polymers are much lower in the concentration in ATRP too. In addition, unlike FRP, the rate of initiation decreases quickly at the beginning of the ATRP and amounts to zero. Besides, molecular weight linearly increases with conversion in the ATRP. Moreover, molecular weight distribution shifts toward higher molecular weight in the ATRP system, whereas that of free-radically generated polymers remains intact throughout the reaction. Finally, the simulation results correspond closely to the experimental data. (C) 2011 Wiley Periodicals, Inc. Adv Polym Techn 30: 257-268, 2011; View this article online at wileyonlinelibrary.com. DOI 10.1002/adv.20221