Synthesis of heteroarm star‐branched polymers by means of anionic living polymerization

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Abstract
The synthesis of well‐defined three‐ and five‐arm star polymers, with varying arm lengths, was described by the method based on anionic living polymerization. A three‐arm AB2 star polymer was synthesized by the linking reaction of a specially designed two chloromethylphenyl‐end‐functionalized polystyrene prepolymer with the anionic living polymer of t‐butyl methacrylate initiated with diphenylmethylpotassium. A five‐arm AA′2B2 star polymer was synthesized by the linking reaction of the same functionalized polystyrene having two chloromethylphenyl termini with the block copolymeric anion prepared from the coupling reaction of polystyryllithium with 1,1‐diphenylethylene‐end‐functionalized poly(α‐methylstyrene). Both star polymers were obtained in more than 95% yields and were found to possess well‐defined structures in terms of molecular weight, molecular weight distribution, arm number, and composition. Copyright © 2001 John Wiley & Sons, Ltd.