Site-Specifically Initiated Controlled/Living Branching Radical Polymerization: A Synthetic Route toward Hierarchically Branched Architectures.

Controlled/living radical polymerization was developed to synthesize branched polyacrylates and polystyrene with tunable degrees of branching and low dispersities. This method is based on a polymerization-induced branching process that occurs when n-butyl α-bromoacrylate is copolymerized under atom transfer radical polymerization conditions. This novel branching polymerization demonstrates excellent synthetic versatility, enabling the preparation of complex macromolecular architectures constructed from branched-polymer building blocks.