Copolymerization of ω-Unsaturated Oligo(Methyl Methacrylate): New Macromonomers

Abstract

The free-radical copolymerization of ω-unsaturated oligo(methyl methacrylate) (1) with each of ethyl acrylate, styrene, methyl methacrylate, acrylonitrile, and vinyl acetate have been investigated. Incorporation of (1) into the polymer was observed in all cases although the molecular weights of the copolymers were substantially lower than those of the homopolymers obtained in the absence of (1) but under otherwise identical conditions. These experiments, together with a product study of the reactions of (1) with cyanoisopropyl radicals, have shown that the addition of free radicals to the double bond of (1) occurs readily. The sterically hindered radical so formed, however, undergoes facile β-scission, resulting in the termination of chains (chain transfer) in competition with chain propagation. The implications of these findings to the usefulness of (1) in the synthesis of graft copolymers and their relevance to the chemistry of free-radical polymerizations when methyl methacrylate is employed as a monomer or comonomer are discussed.