Abstract
There are gel, glass, and cage effects in the methyl methacrylate (MMA) bulk polymerization. These effects will cause the propagation and termination rate constants and initiator efficiency change during the polymerization process, and make the kinetics and molecular weight more complex. A violent increase of conversion will bring a large amount of reaction heat evolved in a short time, and will promote temperature increase if the heat cannot be removed in time. Molecular weight of polymer will raise ten times at the same time. So, the temperature of polymerization system, kinetics of polymerization, and molecular weight and its distribution of polymer cannot be controlled. To control and unify them, the semibatch polymerization method is preferably selected. Furthermore, the kinetic and molecular weight models for MMA semibatch polymerization with the participation of chain transfer agent and new materials addition flow rate are presented. Using the presented models, the effects of temperature, initiator concentration and type, monomer or solvent concentration, and chain transfer agent concentration and type on the kinetics, and molecular weight and its distribution are simulated in this article. Experimental data of kinetics and molecular weight obtained from the published literature are compared with the simulation results to examine the presented models. ยฉ 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2838โ2846, 2006