Successive Synthesis of Multiarmed and Multicomponent Star-Branched Polymers by New Iterative Methodology Based on Linking Reaction between Block Copolymer In-Chain Anion and α-Phenylacrylate-Functionalized Polymer

A series of multiarmed and multicomponent miktoarm (mu-) star polymers have been successfully synthesized by developing a new iterative methodology based on a specially designed linking reaction of the block copolymer in-chain anions, whose anions are positioned between the blocks, with alpha-phenylacrylate (PA)-functionalized polymers. The iterative methodology involves the following two reaction steps: a) introduction of two different polymer segments by the linking reaction of a block copolymer in-chain anion with a PA-functionalized polymer and b) regeneration of the PA reaction site. By repeating this reaction sequence, two different polymer segments are advantageously and successively introduced into the mu- star polymer. In practice, repetition of the reaction sequence affords well-defined 3-arm ABC, 5-arm ABCDE, 7-arm ABCDEFG, and even 9-arm ABCDEFGHI mu-star polymers, composed of polystyrene, polystyrenes substituted with functional groups, polyisoprene, and poly(alkyl methacrylate) arms, respectively.