γ-Ray Initiated Polymerization of Crystalline Monomers1
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Abstract
Acrylamide, methacrylamide, methylene-bis-acrylamide, vinyl carbazole, vinyl stearate, acrylic acid, methacrylic acid and potassium, calcium and barium acrylates have been polymerized in the solid state by irradiation with γ-rays. Further, the molecular weight of polyacrylamide obtained at low conversion was constant over a 270-fold variation of radiation intensity and in the temperature range 20 to 65°, but increased slightly with the energy of the radiation. The polymerization rate, however, was linear with field intensity, independent of the energy of radiation and had an over-all activation energy of 4.7kcal./mole. Irradiation of acrylamide at —179° produced “frozen-in” radicals in concentrations of the order of 10-4 molal. In the polymerization of vinyl stearate the temperature dependences of rate and molecular weight exhibit a discontinuity on passing through the melting point of the monomer. With barium acrylate there is no significant variation in polymerization rate between 10 and 65°. Crystalline maleic anhydride, allylamine hydrochloride and picrate, and stilbene did not polymerize on exposure to γ-rays.
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