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Abstract
The free-radical bulk polymerization of many monomers is characterized by a sudden rise in the rate of polymerization, a phenomenon called autoacceleration. Many mathematical models have been developed to describe this phenomenon. In this paper, the development of a new kinetic model is described. The model very successfully describes experimental data obtained by differential scanning calorimetry of the bulk free-radical polymerization of methyl methacrylate. The proposed model is composed of two contributions to the conversion of the monomer, one originating from polymerization according to the classical theory of radical polymerization and the other originating from polymerization during the autoacceleration. The rate constant of the autoacceleration (second contribution) is about eightfold higher than the rate constant of the first-order reaction (first contribution).