Abstract
To synthesize star-branched polymers, we have developed a new methodology of using polymer anions (Mw = ca. 10 kg/mol) consisting of the same or different two polymer chains in the coupling reaction of chain-end-multifunctionalized polystyrenes with 4, 8, and 16 benzyl bromide moieties. The coupling reactions efficiently proceeded to afford 9-, 17-, and 33-arm regular star-branched polystyrenes as well as A5B4, A9B8, and A17B16 asymmetric stars consisting of polystyrene (A) and poly(4-trimethylsilylstyrene) (B) segments in greater than 85% isolated yields. However, the yields of the coupling reactions were high but not quantitative when either chain-end-functionalized polystyrene with 32 benzyl bromide moieties or a high molecular weight polymer anion (Mw = 20.0 kg/mol) was used.
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