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

Abstract

Present review is an attempt to generalize and systematize the results accumulated in synthesis of cyclolinear and hyperbranched reactive macromolecules via radical alternating copolymerization of various bifunctional monomers containing donor and acceptor type double bonds. Synthesis of hyperbranched reactive macromolecules was carried out using complex‐radical cyclocopolymerization of donor‐acceptor type bifunctional monomers such as monoallyl ester of maleic acid (MAM), allyl acrylate (AA), allyl methacrylate (AM), allyl trans‐cinnamate (AC), methylallylmaleate (MeAM), methylallylfumarate (MAF) and allyl‐α‐(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, copolymerizations predominantly proceed according to alternating mechanism with formation of macromolecules 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. © 2002 Society of Chemical Industry.

Formation of a Supramolecular Hyperbranched Polymer from Self-Organization of an AB2 Monomer Containing a Crown Ether and Two Paraquat Moieties

“…In the past decade, chemists elegantly fabricated a large variety of supramolecular polymers . However, almost all of these polymers are only one-dimensional. , Hyperbranched polymers, three-dimensional polymers prepared from polycondensations of AB m ( m ≥ 2) monomers, have potential applications as processing modifiers, toughening additives, drug delivery vehicles, synthesis supporting materials, advanced coatings, polymeric electrolytes, and optical waveguide materials . Here, we report the formation of a supramolecular hyperbranched polymer from self-organization of an AB 2 monomer 1 containing complementary recognition sites, a bis( m -phenylene)-32-crown-10, and two paraquat moieties…”

Synthesis of poly(ethyl acrylate-co-allyl acrylates) from acrylate mixtures prepared by a continuous solvent-free enzymatic process

“…5 Allyl acrylate is used for preparing copolymeric materials. [6][7][8][9][10][11] It is also common in dentistry. 5 Acrylates are highly sensitive to the conditions used in traditional chemical esterification.…”

Compared Reactivity of Allyl Ribosides in UV-Initiated Free Radical Copolymerization with Acceptor Monomers

“…The cyclopolymerization of allyl−vinylene bifunctional monomers bearing both types of double bonds, as in methyl allyl fumarate or maleate, has been investigated . Tailored multifunctional allyl ether maleates and allyl esters of unsaturated acids lead to hyperbranched polymers − exhibiting specific rheologic and mechanical properties in relation with their particular structure. Styrene polymerization conducted in the presence of various allyl ethers however take place with little or no copolymerization and with no evidence of transfer reaction, emphasizing the importance of the individual nature of each monomer on the reactivity of the blend …”