Comparison of the kinetics of conventional and microwave methyl methacrylate polymerization

A comparative investigation of the conventional and microwaves kinetics of methyl methacrylate (MMA) polymerization was performed. A method for determining the increase of the reaction rate in the microwave field (β) was presented. It was found that at all of the investigated temperatures and powers the polymerization rates increased in the presence of microwave energy by up to 8.9 times compared with conventional polymerization. Isothermal kinetics of the conventional MMA polymerization was investigated and its parameters were determined using isoconversion method. It was found that the calculated kinetics parameters changes complexly with degree of MMA conversion (α) and are in the mutual linear functional relationship, which is so called “compensation effect.” The complex changes of the kinetics parameters with α are explained with the postulated model for the mechanism of the MMA polymerization. The kinetics of the MMA polymerization under the microwave field (MWF) with different input power was investigated and its parameters were determined on the basis of the conversion‐temperature curves and Arrhenius equation. The values of the kinetics parameters for MMA polymerization in the MWF are dependent on α and are from 1.2 to 12 times lower than that for conventional MMA polymerization. A new method for the determination of activation energy (E_a) of the investigated process in the MWF was described. Decreased E_a value of the polymerization process in the MWF compared with the conventional polymerization is explained with the formation of the nonequilibrium energetic distribution of the reactants due to the rapid transfer of energy in the reaction system. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1775–1782, 2007