A COMPARATIVE-STUDY OF THE MASTER EQUATION APPROACH AND THE DISCRETE GALERKIN METHOD FOR THE SIMULATION OF FREE-RADICAL POLYMERIZATION

The present article deals with the mathematical treatment of free radi cal polymerization reactions. As a typical example the synthesis of po ly(methyl methacrylate) under realistic experimental conditions is inv estigated. Since the mathematical treatment of the kinetic rate equati ons raises severe numerical problems, alternative approaches are requi red. In this paper two of these methods, i.e. the discrete Galerkin me thod and the master equation approach, are compared. The discrete Gale rkin method circumvents difficulties encountered by the direct integra tion of the kinetic rate equations but requires much a priori knowledg e of the chemical reaction system. Within the framework of the master equation approach the polymerization reaction is regarded as a stochas tic process. For the simulation of this stochastic process a modified algorithm is presented. The example of the polymerization of methyl me thacrylate shows that the master equation approach is an efficient too l in the simulation of free radical polymerization reactions.