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 present phenanthroline-based conjugated hypercrosslinked polymer (Phen-CHCP) that serves as an efficient photocatalyst for photoinduced copper-catalyzed atom transfer radical polymerization (Cu-ATRP), exhibiting high tolerance toward oxygen and common polymerization inhibitors. Investigation indicated that heterogeneous nature enables the fast and direct initiator activation in the presence of photoexcited Phen-CHCP, not only accelerating the Cu-catalyzed redox cycle but also stabilizing the phenol inhibitor. As a result, various monomers achieved >95% conversions under broadband lights irradiation. This development strongly encourages large-scale in situ copolymerization and synthesized poly((2-methoxyethyl) acrylate-block-n-butyl acrylate) at 20 L scale (conversion 96%, Đ = 1.26), which highlights the strong potential for industrial applications. Reversible-deactivation radical polymerisations are highly sensitive to oxygen and inhibitors, hindering their industrial application. Here, the authors report a heterogeneous phenanthroline-based conjugated hypercrosslinked polymer photocatalyst for photoinduced copper-catalysed atom transfer radical polymerisations, achieving high oxygen and inhibitor tolerance.