Heterogeneous Photocatalyst Enables Large-Scale Broadband Light-Driven Atom Transfer Radical Polymerization with High Oxygen and Inhibitor Tolerance

Reversible-deactivation radical polymerization (RDRP) is a cornerstone of polymer industry. Normally, RDRPs are highly sensitive to oxygen and inhibitors, which hamper their industrial applications. Present methods cannot achieve facile polymerization in presence of both oxygen and inhibitors, particularly for large-scale production. Herein, we report development of phenanthroline-based conjugated hypercrosslinked polymer (Phen-CHCP) as a photocatalyst for photoinduced copper-catalyzed atom transfer radical polymerization (Cu-ATRP) with both high oxygen and inhibitors tolerance. Investigation of a new catalytic mechanism indicated that heterogeneous properties accelerate the diffusion of oxygen and inhibitors towards the Phen-CHCP interface. The ATRP initiator dominates the photoreduction process, not only accelerates the Cu-catalyzed redox cycle but also stabilizes the phenol inhibitor. As a result, various monomers achieved > 95% conversions under broadband lights irradiation. This development strongly encourages the large-scale polymerizations, and we typically synthesized block copolymer of poly((2-methoxyethyl) acrylate-block-n-butyl acrylate) in situ at 20 L scale (conversion 96%, Đ = 1.26), which highlight the strong potential for industrial applications.