Stochastic Simulation of Imperfect Mixing in Free Radical Polymerization

• Published in: Macromolecular symposia. Vol. 271; no. 1; pp. 64 - 74
• Main Authors: Hernandez, Hugo F, Tauer, Klaus
• Format: Journal Article Conference Proceeding
• Language: English
• Published: Weinheim Wiley-VCH Verlag 01.09.2008; WILEY-VCH Verlag; WILEY‐VCH Verlag; WILEY
• Subjects: Algorithms; Applied sciences; Chemical reactions; Computer simulation; Conversion; Diffusion coefficient; Exact sciences and technology; hybrid stochastic simulation; imperfect mixing; kinetic monte carlo simulation; Mass transfer; Organic polymers; Physicochemistry of polymers; Polymerization; Polymethyl methacrylates; Preparation, kinetics, thermodynamics, mechanism and catalysts; radical polymerization; stochastic simulation algorithm; Stochasticity; trommsdorff effect; Monte Carlo method; Free radical polymerization; Bulk polymerization; Theoretical study; Methyl methacrylate polymer; Stochastic simulation; Chemical reaction kinetics
• ISSN: 1022-1360; 1521-3900
• DOI: 10.1002/masy.200851107

A modified algorithm for the stochastic simulation of chemical reactions subject to mass transfer limitation (imperfect mixing) is presented. This algorithm takes into account the mixing by diffusion of the reacting species between two consecutive reactions. The method is used to simulate the effect of mass transfer limitation in free-radical polymerization. Since this is a stiff reaction network, a hybrid stochastic-deterministic approach is considered. The hybrid stochastic algorithm under imperfect mixing (HSSA-IM) is applied to the bulk polymerization of methyl methacrylate up to high conversions. The accuracy of the algorithm relies on the precise determination of diffusion coefficients during the reaction.