Recent developments in the one-step synthesis of structurally controlled hyperbranched polymers by radical polymerization in terms of molecular weight, dispersity, number of branching points, branching density, and number of chain-end groups are reported. The structural character of HB-polyacrylates and HB-polystyrenes synthesized by organotellurium-mediated radical polymerization (TERP) resembles that of dendrimers and dendrons, which, although enabling complete control over branched structures, requires tedious stepwise synthesis. Successful control is realized by a new molecular design for the monomer inducing the branching structure, in which the reactivity of the dormant group changes from inactive to active upon the reaction and incorporation of the monomer into the polymer backbone. The principle of the monomer design and the scope and limitation of the polymerization method are described here.
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The author deeply appreciates the intellectual and physical contributions of collaborators and coworkers, especially Drs. Atanu Kotal (now at JIS University, India), Shenyong Ren (now at the China University of Petroleum), and Yangtian Lu (Kyoto University). Drs. Atanu Kotal and Shenyong Ren pioneered this work, and Dr. Yangtian Lu realized the idea and helped prepare the paper. Financial support from the Japan Society for the Promotion of Science KAKENHI (16H06352) is also acknowledged.
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Yamago, S. Practical synthesis of dendritic hyperbranched polymers by reversible deactivation radical polymerization. Polym J 53, 847–864 (2021). https://doi.org/10.1038/s41428-021-00487-x