Conjugated cross-linked phosphine as broadband light or sunlight-driven photocatalyst for large-scale atom transfer radical polymerization

Wei-Wei Fang; Gui-Yu Yang; Zi-Hui Fan; Zi-Chao Chen; Xun-Liang Hu; Zhen Zhan; Irshad Hussain; Yang Lu; Tao He; Bi-En Tan

doi:10.1038/s41467-023-38402-y

Conjugated cross-linked phosphine as broadband light or sunlight-driven photocatalyst for large-scale atom transfer radical polymerization

Nat Commun. 2023 May 20;14(1):2891. doi: 10.1038/s41467-023-38402-y.

Authors

Wei-Wei Fang^#¹, Gui-Yu Yang^#¹, Zi-Hui Fan¹, Zi-Chao Chen¹, Xun-Liang Hu², Zhen Zhan², Irshad Hussain³, Yang Lu¹, Tao He⁴, Bi-En Tan⁵

Affiliations

¹ School of Chemistry and Chemical Engineering, Anhui Province Key Laboratory of Advanced Catalytic Materials and Reaction Engineering, Hefei University of Technology, Hefei, Anhui, 230009, PR China.
² School of Chemistry and Chemical Engineering, Key Laboratory of Material Chemistry for Energy Conversion and Storage Ministry of Education, Hubei Key Laboratory of Material Chemistry and Service Failure, Huazhong University of Science and Technology, Wuhan, Hubei, 430074, PR China.
³ Department of Chemistry & Chemical Engineering, SBA School of Science & Engineering, Lahore University of Management Sciences (LUMS), Lahore Cantt, Lahore, 54792, Pakistan.
⁴ School of Chemistry and Chemical Engineering, Anhui Province Key Laboratory of Advanced Catalytic Materials and Reaction Engineering, Hefei University of Technology, Hefei, Anhui, 230009, PR China. taohe@hfut.edu.cn.
⁵ School of Chemistry and Chemical Engineering, Key Laboratory of Material Chemistry for Energy Conversion and Storage Ministry of Education, Hubei Key Laboratory of Material Chemistry and Service Failure, Huazhong University of Science and Technology, Wuhan, Hubei, 430074, PR China. bien.tan@mail.hust.edu.cn.

^# Contributed equally.

Abstract

The use of light to regulate photocatalyzed reversible deactivation radical polymerization (RDRP) under mild conditions, especially driven by broadband light or sunlight directly, is highly desired. But the development of a suitable photocatalyzed polymerization system for large-scale production of polymers, especially block copolymers, has remained a big challenge. Herein, we report the development of a phosphine-based conjugated hypercrosslinked polymer (PPh₃-CHCP) photocatalyst for an efficient large-scale photoinduced copper-catalyzed atom transfer radical polymerization (Cu-ATRP). Monomers including acrylates and methyl acrylates can achieve near-quantitative conversions under a wide range (450-940 nm) of radiations or sunlight directly. The photocatalyst could be easily recycled and reused. The sunlight-driven Cu-ATRP allowed the synthesis of homopolymers at 200 mL from various monomers, and monomer conversions approached 99% in clouds intermittency with good control over polydispersity. In addition, block copolymers at 400 mL scale can also be obtained, which demonstrates its great potential for industrial applications.