Reactivity of organometallic compounds in olefin polymerization. V. The co‐catalytic action of oxygen on the vinyl polymerization induced by organometallic compounds

Abstract

AbstractAs we reported, oxygen has a significant co‐catalytic effect on the vinyl polymerization induced by some organometallic compounds. The present paper is concerned with a study to elucidate the mechanism of the co‐catalytic action. It was found that the oxidation of organometallics such as dialkylzinc and trialkylboron afforded the metal salts of the corresponding hydroperoxides and the latter compounds exhibited a remarkable catalytic action on the polymerization of methyl methacrylate and vinyl acetate even at room temperature. Alkyllithium was also found to act as a radical initiator when it was oxidized by molecular oxygen prior to use. This result is in a sharp contrast to the „ionic behaviour”︁ of the usual lithium compounds in the vinyl polymerization. It was also found that a limited amount of active hydrogen compounds such as water, alcohol or amine played the role of a co‐catalyst in the vinyl polymerization.