High‐Yield Synthesis of Molecular Bottlebrushes With Block Copolymer Side Chains by the Copper Superoxido Complex Enabled ATRP via a Grafting‐From Approach

The combination of controlled radical polymerization technique and grafting-from strategy has been widely employed for synthesizing molecular bottlebrushes (MBBs); however, this approach always meets challenges at the high monomer conversion stage due to the intra- and inter-molecular cross-linking caused by inevitable radical-radical coupling. Herein, we report the utilization of copper superoxido complex-enabled atom transfer radical polymerization (ATRP) for the grafting-from synthesis of MBBs with well-defined architectures in high yield. Owing to the use of a low concentration of copper catalyst, the intra- and inter-molecular cross-linking is greatly minimized, leading to the precise synthesis of MBBs with narrow distribution, near-quantitative monomer conversion, and worm-like architecture. Under this premise, we further evaluate the feasibility of this approach for the one-pot preparation of MBBs with block copolymer (BCP) side chains as well as dye-loaded functional MBBs. Overall, this work proposes an efficient grafting-from approach for MBBs with precise architectures and unprecedentedly high yield, which can be utilized for multicomponent MBBs with diverse functions.