Abstract
Abstract In order to assertain the polymerization mechanism in the solid state, a solid mixture of propargyl alcohol (monomer), hydrogen peroxide and water was irradiated at −196°C by an ultraviolet light. The structure of the free radicals so formed in the solid medium was then studied by the electron-spin-resonance method. The trapped free radical was a monomer radical, CH≡C–CHOH. This shows that the HO·radicals produced by the photolysis of hydrogen peroxide abstracted the methylenic hydrogen atoms from the alcohol. An examination of the kinetic behavior of free radicals revealed that HO· radicals migrated freely and reacted with monomers at −196°C. The reaction between the monomer radical and HO· radicals is more important than the recombination between monomer radicals.
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