Complex-radical copolymerization of vinylcyclohexyl ketones with
maleic anhydride and N-p-tolylmaleimide
Zakir M.O. Rzaev1a,Güneri Akovali1, E.Yu. Kuliyeva2 and N.Yu. Lezgiev2
1 Departments of Chemistry & Polymer Science and Technology, Middle East Technical University, 06531Ankara, Türkiye
1aVisiting Professor from Institute of Polymer Materials, Azerbaijan Academy of Sciences, 370001 Baku, Azerbaijan
2Department of Chemistry, Azerbaijan Institute of Technology, Gendje-Azerbaijan
Some features of the formation and photochemical reactions of cyclohexylketone containing macromole-culesincluding 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, 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 keto-enol tautomerism; while random copolymer enriched with vinyl ketone units is formed with the system containing oc-ubstituted VCHK. It is found that characteristics of photochemical reactions of alternating copolymer synthesized depend on the type of substitution in the vinyl ketone molecule; unlink VCHK-MA(TMI) and V-d -Cl-CHK-MA(TMI) copolymers case which easily crosslink upon UV-irradiation, and the N-substituted derivatives of these copolymers which decompose under similar condition.