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Controlled radical copolymerization of fluoroalkenes by using light-driven redox-relay catalysis

Nature Synthesis volume 2, pages 653–662 (2023)Cite this article

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Abstract

Fluoroalkenes are feedstocks in the manufacture of high-performance fluoropolymers with various applications. However, the synthesis of well-defined fluoropolymers typically requires harsh conditions and high-pressure techniques to handle gaseous fluoroalkenes. Here, we report the combination of a redox-relay pathway and thermally activated delayed fluorescence (TADF) catalysis to enable controlled copolymerizations of various fluoroalkenes, under ambient conditions. Using this method, a broad scope of main-chain fluoropolymers is prepared with excellent selectivity at low organocatalyst dosages (loadings down to 5 ppm). In addition, polymers with various sequences (for example, diblock and triblock) and topologies (either brush or branched) are synthesized by integration with different agents and synthetic protocols. Mechanistic studies reveal that the rationally designed organic TADF catalyst displays the unique characteristics of redox-relay-based electron transfer, a long lifetime of delayed fluorescence and fine-tuned electronic properties. This work provides an informative concept for precise polymer synthesis and may inspire advanced applications in fluoropolymer engineering.

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Fig. 1: Main-chain fluoropolymers synthesized via different methods.
Fig. 2: Optimization of reaction conditions for the HFP-iBVE copolymerization.
Fig. 3: Copolymerization results with different amines and CTAs.
Fig. 4: Investigation of the reaction mechanism and photocatalyst properties.
Fig. 5: Kinetic investigations for the HFP copolymerizations.
Fig. 6: Investigations on the synthetic scope of copolymerizations.
Fig. 7: Synthesis of fluoropolymers of different topologies.

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Data availability

The authors declare that all data supporting the findings of this study are available within the article and its supplementary information. Details about materials, analytic methods, experimental procedures, mechanistic studies, characterization data and NMR spectra are available in the Supplementary Information.

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Acknowledgements

This research was financially supported by National Natural Science Foundation of China (NSFC, no. 21971044, M.C.), Shanghai Pilot Program for Basic Research—Fudan University 21TQ1400100 (no. 21TQ007, M.C.), Science and Technology Commission of Shanghai Municipality and State Key Laboratory of Molecular Engineering of Polymers.

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Authors and Affiliations

  1. Department of Macromolecular Science, State Key Laboratory of Molecular Engineering of Polymers, Fudan University, Shanghai, China

    Yucheng Zhao, Yufei Chen, Huyan Zhou, Yang Zhou, Kaixuan Chen, Yu Gu & Mao Chen

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Contributions

Y. Zhao and M.C. conceived and designed the research. Y. Zhao, Y.C. and K.C. performed synthesis. Y. Zhao, Y.C., H.Z. and Y. Zhou performed characterization. Y. Zhao, Y.C., H.Z., Y. Zhou, K.C., Y.G. and M.C. analysed data. Y. Zhao, Y.G. and M.C. wrote the manuscript and the supplemental information. All authors approved the final version.

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Correspondence to Mao Chen.

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Zhao, Y., Chen, Y., Zhou, H. et al. Controlled radical copolymerization of fluoroalkenes by using light-driven redox-relay catalysis. Nat. Synth 2, 653–662 (2023). https://doi.org/10.1038/s44160-023-00284-9

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