The role of CT monomer complexes in radical copolymerization

Abstract

The mechanism of the copolymerization of monomers forming a charge‐transfer complex in the reaction mixture was investigated. A condition for establishing a certain mechanism consists in the determination of the elementary rate constants of the copolymerization; the results are in good agreement with well‐known elementary rate constants for radical polymerization. We could prove the mechanism by the method of Giese producing radicals in high concentrations. The radicals react either with monomers or monomer pairs, and the initiating radicals obtained are subsequently transferred into the hydrogenated form. The initial reaction products were identified by gas chromatography. Only addition to the radicals of either maleic anhydride or styrene and not of the CT‐complex was established by the reaction products in the mixture of styrene with maleic anhydride.