Copolymerization characteristics of methyl acrylate and methyl methacrylate. I. Study of copolymerization kinetics by a deuterium tracer method

The kinetics of copolymerization for the methyl acrylate–methyl methacrylate system was studied by using monomers which contain deuterium as a tracer. The experiments were made on two series of copolymerizations: methyl acrylate–deuteromethyl methacrylate, (CH2C(CH3)COOCH2D), and deuteromethyl acrylate (CH2CHCOOCH2D)–methyl methacrylate copolymerization systems. Mass spectrometric analysis was employed for determining the composition of copolymers. The agreement of the experimental results of the two series was reasonable. The monomer reactivity ratios for the methyl acrylate (M1)–methyl methacrylate (M2) system were determined as r1 = 0.47 ± 0.09 and r2 = 2.3 ± 0.5 at 130°C. These values were compared with those calculated from the Price-Alfrey Q-e scheme.