Kinetics of the benzoyl peroxide and azobis-isobutyronitrile initiated thermal polymerizations of N-vinylcarbazole in solution

Whereas the azobis-isobutyronitrile thermally initiated polymerization of N-vinylcarbazole in solution obeys the usual rate law for a free-radical polymerization, the rate law for the benzoyl peroxide initiated polymerization is found to have a monomer exponent of two and an initiator exponent of one; a partial charge-transfer mechanism of the polymerization is proposed.