Radiation Induced Polymerization of Cyclic Dienes

概要

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1, 3-Cyclohexadiene (1, 3-CHD) and 1, 2-dimethylenecyclohexane (1, 2-DMCH) were polymerized under the action of γ-ray irradiation, and they were compared with the results of the polymerizations by radical and cationic catalysts. 1, 2-DMCH was easily polymerized with a radical catalyst, but the polymerizability by cationic catalyst was lower than 1, 3-CHD. Polymer was obtained in a high yield at the temperature range between 30 and 50°C by radiation, but almost no polymer was obtained at -78°C, even in CH2Cl2 solution. Theradical mechanism is supposed for the former and the cationic one for the latter. The polymer obtained had the high crystalline structure of all cis-1, 4-addition configuration. The rate of radiation induced polymerization of 1, 3-CHD at room temperature was very small. On the contrary, considerably large rate of polymerization was observed at lower temperature in CH2Cl2. This monomer had the lower polymerizability with a radical catalyst, but was easily polymerized with a cationic catalyst. It is supposed that the reason for lower polymerizability of 1, 3-CHD by a radical catalyst is a hydrogen abstraction from ring -CH2- to make a degradative chain transfer reaction, and also the reason for lower polymerizability of 1, 2-DMCH by an ionic catalyst is the termimation reaction accompanying positive charge transfer and H (+) derivation.
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