Complex-Radical Copolymerization of Vinylcyclohexyl Ketones with Maleic Anhydride and N-p-tolylmaleimide

Abstract

Some features of the formation and photochemical reactions of cyclohexylketone containing macromolecules including copolymers of vinylcyclohexyl ketone (VCHK) and its derivatives (V-a-Cl-CHK and V-d-C1-CHK) with maleic anhydride (MA) and N-p-tolylmaleimide (TMI) have been revealed. It has been established that keto-enol tautomerism is the only reaction realized in the vinylcyclohexylketone molecules having mobile hydrogen atom at a -position in the cyclohexane ring, enol form of which is formed by charge-transfer complexes with anhydride or imide of maleic acid as acceptor monomers. The kinetic parameters of these reactions, including complex-formation and copolymerization constants, as well as the ratios of chain growth rates for the participation of monomeric charge-transfer complexes and free monomers,В are all determined. It is shown that an alternative copolymerization is realized with the monomer systems containing VCHK and V-d-C1-CHK, which are carried out through a complex-mechanism due to the ketoenol tautomerism; while random copolymer enriched with vinyl ketone units is formed with the system containing oc-substituted VCHK. It is found that characteristics of photochemical reactions ofВ alternating copolymer synthesized depend on the type of substitutation in the vinyl ketone molecule; unlink VCHK-MA(TMI) and V-d-C1-CHK-MA(TMI) copolymers case which easily crosslink upon UVirradiation, and the N-substituted derivatives of these copolymers which decompose under similar condition.