High-Yield Synthesis of Molecular Bottlebrushes via PISA-Assisted Grafting-from Strategy.

To prepare molecular bottlebrushes with high yield via a grafting-from strategy using a reversible deactivation radical polymerization (RDRP) technique has always been a big challenge due to the intra- and intermolecular radical-radical coupling. Herein, a polymerization-induced self-assembly (PISA)-assisted grafting-from strategy based on reversible addition-fragmentation chain transfer (RAFT) dispersion polymerization was developed to synthesize the Janus molecular bottlebrushes with a well-defined structure and high yield using polynorbornene-g-(poly(ethylene glycols)-branch-RAFT agent) (PNB-g-(PEG-branch-CTA)) as a solvophilic multifunctional macro-CTA. The results indicated the biradical coupling terminations of propagating side chains could be significantly suppressed due to the nanoconfinement effect in the PISA of the generated Janus molecular bottlebrushes. Janus molecular bottlebrushes with a narrow molecular weight distribution (Mw/Mn < 1.25) and negligible intermolecular cross-linking at monomer conversion as high as 84% were prepared, demonstrating the efficiency and versatility of the PISA-assisted grafting-from approach.