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The Thermal Dimerization and Polymerization of 1,3-Cyclohexadiene

1967; Marcel Dekker; Volume: 1; Issue: 8 Linguagem: Inglês

10.1080/10601326708053783

2332-4082

Tadashi Nakata, Nobuo Choumei,

Thermal and Kinetic Analysis

Abstract The thermal polymerization of 1,3-cyclohexadiene to produce dimer and low molecular weight polymer is reported. The reaction initiated thermally and/or by benzoyl peroxide is kinetically of the second order, and the activation energy is 13.1 kcal/mole. The activation energy for the reaction is in quantitative agreement with that of the homopolymerization of 1,3-cyclohexadiene estimated from the kinetic study on the copolymerization with acrylonitrile. Evidently the dimerization process to give dimer as a product of typical Diels-Alder condensation is a competing type of reaction with radical polymerization to give a low molecular weight polymer. The ratio of the rate constant for two competing types of reaction at 200°C is found to be 1.21. The thermal polymerization in the presence of oxygen produces dimer in greater yield as a result of inhibition of the radical polymerization process.