Effect of acetylene on the γ‐radiation‐induced polymerization of ethylene

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Abstract
The effects of acetylene on the γ‐radiation‐induced polymerization of ethylene were studied from the viewpoint of the gaseous products and polymer structure. The experiments were carried out under a pressure of 400 kg/cm2; the temperature was 30°C; the does rate was 1.1 × 105 rad/hr; and the acetylene content was 0–20%. The solid polymer was obtained in the polymerization of ethylene containing 2.2% acetylene, while the monomer containing 19.7% acetylene gave a yellowish viscous oil. The polymer yield and molecular weight decreased remarkably with acetylene content. The main gaseous product was hydrogen, and trace amounts of butane, butene‐1, butadiene‐1,3, and benzene and its derivatives were also observed. The rate of formation of hydrogen was almost independent of acetylene content and there was no difference in acetylene contents before and after the irradiation was found. The infrared spectra of the polymers showed the presence of vinylidene, trans‐vinylene, and terminal vinyl unsaturations, 1,4‐disubstituted benzene, and carbonyl groups. The contents of trans‐vinylene, terminal vinyl, and methyl groups increased with acetylene content, and that of vinylidene was independent of acetylene content. The monomer reactivity ratios of ethylene and acetylene were evaluated as 45.5 and 66.0, respectively. On the basis of the results, the effects of acetylene on the γ‐radiation‐induced polymerization of ethylene were discussed.