Star-shaped polymers have unique physical properties and they are sought after materials in industry. However, the ease of synthesis is essential for translation of these materials into large-scale applications. Herein, a highly efficient synthetic method to prepare star-shaped polymers by combination of Cu-mediated reversible deactivation radical polymerization (Cu-RDRP) and thiol-bromo click reaction is described. Well-defined linear and block polymers with a very high bromine chain end fidelity are obtained via Cu-RDRP and subsequently react with multi-functional thiol compounds. High coupling efficiencies of larger than 90% are obtained owing to the quick and efficient reaction between thiols and alkyl bromides. Moreover, the arms of the obtained star-shaped polymers are linked via thioether bonds to the core, making them susceptible for oxidative degradation.
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