Abstract
AbstractThe γ‐radiation‐induced polymerization of ethylene with the use of liquid carbon dioxide as a solvent, was studied from the viewpoint of kinetics. The polymerization was carried out at conversions less than 10% under the pressure ranging from 100 to 400 kg./cm.2, dose rates 1.3 × 104−1.6 × 105 rad/hr., and temperatures of 20–90°C. The concentration of carbon dioxide varied up to 84.1 mole‐%. The polymerization rate and the polymer molecular weight were observed to increase with reaction time. This observation, however, becomes less pronounced with increasing concentration of carbon dioxide and with rising temperature. The exponents of the pressure and the dose rate were determined to be 2.3 and 0.85 for the rate, and 2.0 and −0.20 for the molecular weight, respectively. From the kinetic considerations for these results, the effect of carbon dioxide on the initiation and termination reaction in the polymerization was evaluated.
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