MODELING OF FREE-RADICAL POLYMERIZATION UP TO HIGH CONVERSION .2. DEVELOPMENT OF A MATHEMATICAL-MODEL

In free radical polymerization diffusion-controlled processes take pla ce simultaneously to the normal chemical reactions. Despite extensive efforts to model such processes a consistent model for the design of a polymerization reactor has not yet been established. In this article a semiempirical model describing the conversion, polymerization degree , and molecular weight distribution (MWD) for the free radical polymer ization is developed for the entire course of the reaction. The model includes the change of termination, propagation, transfer, and initiat ion rate. By simultaneous parameter estimation from the conversion and degrees of polymerization data the model parameters have been determi ned for isothermal polymerizations of methyl methacrylate (MMA) and st yrene (ST). The simulation results for the conversion, degrees of poly merization, and MWD are in good accordance with experimental data for suspension and bulk polymerization of MMA and ST up to very high conve rsions. The influence of diffusion on the propagation rate in case of polymerization of MMA is negligible compared to the influence of the c age effect on the radical efficiency; in case of ST polymerization bot h effects must be included in the kinetic model. The model presented i s also tested for polymerizations conducted in the presence of solvent and/or chain transfer agents. (C) 1997 John Wiley & Sons, Inc.