Hyperbranched macromolecules through donor-acceptor type copolymerization of allyl-vinylene bifunctional monomers

摘要

Present review is an attempt to generalize and systematize the results accumulated in synthesis of cyclolinear and hyperbranched reactive macromolecules via radical alternating copoly-merization of various bifunctional monomers containing donor and acceptor type double bonds. Synthesis of hyperbranched reactive macromolecules was carried out using complex-radical cycloco-polymerization of donor-acceptor type bifunctional monomers such as monoallyl ester of maleic acid (MAM), allyl acrylate (AA), allyl methadrylate (AM), allyl trans-cinnamate (AC), methylallylmaleate (MeAM), methylallylfumarate (MAF) and allyl-alpha-(N-maleimido) acetate (AMI), and maleic anhydride (MA) and styrene (St) as typical acceptor and donor comonomers, respectively. The kinetic parameters of these reactions, constants of cyclization, complex-formation and copolymerization, as well as the ratios of chain growth rates for the participation of monomeric charge transfer complexes and free monomers, were all determined. It was demonstrated that in the studied systems, copoly-merizations predominantly proceed according to alternating mechanism with formation of macro-molecules having cyclolinear structure in the steady-state and hyperbranched structure in the high conversion conditions. It was shown that formation of linear and hyperbranched macromolecules containing allyl or vinylene groups in the side chain occurs selectively carry out and depends on the nature of used comonomer. General schemes and proposed mechanism of hyperbranching and crosslinking reactions were also described. Some useful properties of synthesized reactive copolymers were discussed.