The γ-ray-induced solution polymerization of bis(β-chloroethyl) vinylphosphonate (CEVP) in several kinds of organic solvents was carried out, and the reaction mechanism was studied. Polymerization in a temperature range from 40° to -78°C is considered to be carried out by a free radical mechanism. The dependence on the dose rate (I) of the rate of solution polymerization (Rp) in both dioxane and chloroform shows that the indexes of I increase with the concentration of the monomer, but that they do not differ much from 0.5 in a wide range of concentration. The chain transfer constants for these two solvents from the monomer are smaller than that for the monomer in the bulk polymerization of CEVP, though they are much larger than the values found in solution polymerization of ordinary vinyl monomers. A kinetic equation has been derived from these results, and the reaction mechanisms were considered by applying the experimental data to the equation. The rates of solution polymerization were generally smaller than those of bulk polymerization, owing to the energy transfer reactions from the monomer to the solvents.

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