The synthesis of specially designed chain-functionalized polystyrenes with a definite number of benzyl bromide moieties by an iterative divergent methodology is described. Such functionalized polystyrenes involve α,ω-chain-end-functionalized polystyrenes with benzyl bromide moieties, in-chain-functionalized polystyrenes with benzyl bromide moieties, and in-chain-functionalized polystyrenes with benzyl bromide moieties that are placed at two sites in a chain. The number of benzyl bromide moieties varied from 2 to 16 at each place. Three series of well-defined star−linear block polystyrenes of the types star- block -linear- block -star, linear- block -star- block -linear, and linear- block -star- block -linear- block -star- block -linear have been successfully synthesized by coupling these benzyl bromide-chain-functionalized polystyrenes with polystyryllithiums end-capped with 1,1-diphenylethylene.
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Haraguchi et al. (2003) studied this question.