Synthesis of functionalized polymers by means of living anionic polymerization, 2 - Synthesis of well-defined chain-end and in-chain functionalized polymers with 1,3-butadienyl groups

The synthesis of well-defined functionalized polystyrenes and poly(methyl m ethacrylate)s with 1,3-butadienyl groups has been described by the methodol ogy based on the functionalization reactions of living anionic polymers of a new substituted 1,1-diphenylaethylene with a 1,3-butadienyl group, 1-[4-( 4-methylene-5-hexenyl)-phenyl]-1-phenylethylene (1). Both chain-end and in- chain functionalized polystyrenes with one or two 1,3-butadienyl groups wer e synthesized by utilizing the addition reactions of living polystyrenes to 1 followed by methanol termination or treatment with appropriate electroph iles. On the other hand, chain-end and in-chain functionalized poly(methyl methacrylate)s with one or two 1,3-butadienyl groups were obtained by the l iving anionic polymerization of methyl methacrylate with the adduct prepare d from 1 and either s-BuLi or lithium naphthalenide. The 1,3-buadienyl grou ps thus introduced were quantitatively transformed into anhydride or epoxy functions without any side reactions by the (C2H5)(2)AlCl-catalyzed Diels-A lder reaction or by treatment with 3-chloro-peroxybenzoic acid.