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Photocontrolled radical polymerization for the synthesis of ultrahigh-molecular-weight polymers

Nature Synthesis volume 4, pages 15–30 (2025)Cite this article

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Abstract

Compared with conventional thermally initiated radical polymerization, photocontrolled radical polymerization offers mild, environmentally friendly reaction conditions, fast polymerization rates, high end-group fidelity and spatiotemporal control. Access to ultrahigh-molecular-weight (UHMW) polymers with precisely defined molecular weights, structures and topologies requires a high degree of living character with minimal side reactions and has been a longstanding challenge in polymer synthesis. The recent development of photocontrolled radical polymerization has enabled facile synthesis of UHMW polymers. Here we discuss methods for producing various UHMW polymers via photocontrolled radical polymerization, including photoiniferter reversible addition–fragmentation chain transfer (RAFT) polymerization, photoinduced electron/energy transfer–RAFT polymerization, photoenzymatic RAFT polymerization, photocontrolled atom transfer radical polymerization and photocontrolled organotellurium-mediated radical polymerization, followed by an overview of the applications of UHMW polymers as high-performance materials. Finally, we provide our future perspective for developments in this emerging field.

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Fig. 1: Photoiniferter RAFT polymerization.
Fig. 2: Mechanism of PET–RAFT polymerization.
Fig. 3: Synthesis of UHMW polymers via PET–RAFT polymerization using various photocatalysts.
Fig. 4: Photoenzymatic RAFT polymerization.
Fig. 5: Photo-ATRP.
Fig. 6: Photo-TERP.
Fig. 7: Synthesis of star polymers.

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Acknowledgements

We thank the National Natural Science Foundation of China (22193020, 22193024 and 22371089) for financial support.

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Authors and Affiliations

  1. State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun, China

    Shilong Zhu, Weina Kong, Shuangqi Lian, Ao Shen & Zesheng An

  2. Dainton Building, Department of Chemistry, University of Sheffield, Sheffield, UK

    Steven P. Armes

  3. Key Laboratory for Molecular Enzymology and Engineering of Ministry of Education, School of Life Sciences, Jilin University, Changchun, China

    Zesheng An

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  1. Shilong Zhu
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S.Z., W.K., S.L., A.S. and Z.A. wrote the manuscript. S.P.A. and Z.A. revised the manuscript.

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Zhu, S., Kong, W., Lian, S. et al. Photocontrolled radical polymerization for the synthesis of ultrahigh-molecular-weight polymers. Nat. Synth 4, 15–30 (2025). https://doi.org/10.1038/s44160-024-00710-6

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