Abstract
Abstract The AIBN-initiated polymerization of methyl methacrylate in pyridine at 50° C proceeds to higher conversion than that carried out in bulk. The increased values of the overall rate constant are due to the increased values of the initiation rate constant. The overall activation energy (13.1 kcal/mole monomer) and the activation energy for initiator decomposition (12.6 kcal/ mole) are lower than those given in the literature. In addition to anomalies of the kinetic and energetic parameters, an increase in the frequencies of the y-skeletal modes (5–20 cm−1) of methyl methacrylate on its mixing with pyridine (molar ratio 1:1.33) is also observed. At this ratio, an increase in the band strength of the methyl methacrylate v(C=0) vibrations is also observed. The most plausible explanation of the obtained anomalies in the polymerization of methyl methacrylate in pyridine (6.215–7.991 mole/liter) is the formation of a weak complex which affects the initiation step. The values of k /kt l/2 = 0.24, E = 1/2 E...
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