Abstract
AbstractPolymerization of acrylonitrile initiated by a potassium superoxide (KO2)‐nitrobenzene system was carried out in anhydrous dimethylsulfoxide (DMSO) at 25°C. The initial rate of polymerization was rapid and a high‐molecular‐weight polymer was obtained. The molecular weight was proportional to monomer concentration and inversely to concentration of initiator within 5 min. The overall activation energy was estimated as −2.6kcal/mol deg in the temperature range of 20–50°C. In addition to nitrobenzene anion radical, other anion radicals generated by one‐electron transfer from KO2 to charge transfer agents such as m‐dinitrobenzene benzoquinone, benzophenone, and naphthalene were effective in the polymerization of acrylonitrile. It is proposed that polymerization proceeds via an anionic mechanism that involves one‐electron transfer from anion radicals to monomer.
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