A General Strategy To Access Alternating Styrene/Substituted Styrene Copolymers by Using a Traceless Controlling Group

Abstract We herein report a synthetic strategy for alternating copolymers of styrene and substituted styrenes by utilizing α‐styryl boronate pinacol ester ( StBpin ) as the co‐monomer through radical alternating copolymerization followed by protodeboronation. The excellent alternating polymerization behavior of the StBpin co‐monomer in such a radical polymerization system is considered to be attributed to the steric hindrance and radical stabilization exerted by the Bpin group. This strategy is effective with a wide range of substituted styrene co‐monomers regardless of the electronic nature of the substituents, and the protodeboronation of the alternating Bpin‐containing polymers is highly efficient without polymer backbone alternation. RAFT living polymerization was also compatible with this approach. Thus, this strategy provides a way to build‐up alternating copolymers consisting of similar styrene‐type co‐monomers, which has been inaccessible by conventional synthetic methods.