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<p>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 &gt;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%, <i>Đ</i> = 1.26), which highlights the strong potential for industrial applications.</p>

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Heterogeneous photocatalyst enables large-scale broadband light-driven atom transfer radical polymerization with high oxygen and inhibitor tolerance

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年5月14日

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  • Wei-Wei Fang,
  • Zi-Hui Fan,
  • Bin Xia,
  • Yi-Xing Liu,
  • Fan Zhang,
  • Ning Chen,
  • Tian-Ci Sun,
  • Xun-Liang Hu,
  • Hui Gao,
  • Bing Hu,
  • Xiao-Guo Zhou,
  • Bi-En Tan,
  • Lei Xia,
  • Tao He

摘要

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.