Thermal Polymerization of Methyl Methacrylate at High Temperature

Kinetic studies of the bulk polymerization of methyl methacrylate at high temperature have been carried out first without any additives and then in the presence of 1-Butanethiol as a chain transfer agent. A pressurised dilatometric reactor operating at high temperature is used to determine the time-conversion curves at temperatures between 150 and 180°C. A two-stage polymerization is observed. The high polymerization rate obtained initially is attributed to traces of an initiating impurity, while the second, slower polymerization stage could be considered as the actual thermal polymerization. The chain transfer agent or an impurity it may contain also initiates the reaction. Therefore, the rates of both the initial polymerization and of the second stage are increased when the thiol is added. Experimental data on the degree of conversion versus time and on the final average molecular weight are used to determine the chain transfer constants to the monomer and to the mercaptan as well as the initiation rate constants. These constants are used to model the thermal polymerization of MMA at high temperatures where these initiation reactions can no longer be neglected, especially when an industrial polymerization process has to be optimized and controlled.