The reaction of benzoyl peroxide with cyclohexane and cyclohexene. Contribution to the mechanism of the catalyzing action of peroxides in the polymerization of vinyl derivatives

Abstract

AbstractThe course of the reactions of benzoyl peroxide with cyclohexane and cyclohexene may be accounted for by a mechanism involving free radicals and radical chain reactions. With cyclohexane, the average length of the chain hardly exceeds one step and one mole of hydrocarbon reacts with one mole of peroxide. With cyclohexene, chains of two and three steps also occur and about two and one‐half moles of hydrocarbon per mole of peroxide take part in the reaction. It is shown that this is due to the one‐sided addition of the primary radicals (originating from the peroxide) to the double bond, yielding a new radical without a double bond which can in turn react in the same way with another unsaturated molecule, thus giving rise to polycyclic compounds (chain formation). This polymerization reaction is, however, soon halted by a competitive side reaction involving substitution of the α‐ (or β)‐methylene group, which leaves the double bond intact. In polymerizable vinyl derivatives in which no reactive α‐methylene group is present, the competitive reaction cannot occur and the radical chain reaction continues to form a growing chain of interlinked monomeric molecules with annihilation of the double bonds. The two terminal groups of the macromolecules of the final polymerizate are radicals originating from the peroxide used as a catalyst. If a solvent is used, radicals of the latter may also appear occasionally as terminal groups of the polymer. The mechanism of the catalytic action of diacyl peroxides in the polymerization of vinyl derivatives is thus clarified. The molecule linking reaction induced by free radicals in unsaturated compounds also provides an explanation of the action of benzoyl peroxide as a rubber vulcanizer; the peroxide radicals are found as substituents in the rubber molecule.