Simulation of Styrene Polymerization by Monomolecular and Bimolecular Nitroxide-Mediated Radical Processes over a Range of Reaction Conditions

Abstract

Simulations of polymerization rate, molecular weight development and evolution of the concentrations of species participating in the reaction mechanism over a range of operating conditions, and a parameter sensitivity analysis showing the effects of temperature, activation/deactivation equilibrium constant and initial concentrations of controller and initiator (if present) on these variables are presented for the nitroxide-mediated radical polymerization of styrene. The simulations were performed with a computer program based on a detailed reaction mechanism. The simulated profiles of conversion, number average molecular weight (M n ), and polydispersity agree well with experimental data. Previously unknown activation energies for reactions involved in the mechanism are estimated. The temperature dependence of the kinetic rate constants obtained in this study will be useful for future modeling and optimization studies.