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Photoorganocatalyzed Reversible-Deactivation Alternating Copolymerization of Chlorotrifluoroethylene and Vinyl Ethers under Ambient Conditions: Facile Access to Main-Chain Fluorinated Copolymers

  • Kunming Jiang
    Kunming Jiang
    State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai, China, 200433
    More by Kunming Jiang
  • , 
  • Shantao Han
    Shantao Han
    State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai, China, 200433
    More by Shantao Han
  • , 
  • Mingyu Ma
    Mingyu Ma
    State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai, China, 200433
    More by Mingyu Ma
  • , 
  • Lu Zhang
    Lu Zhang
    State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai, China, 200433
    More by Lu Zhang
  • , 
  • Yucheng Zhao
    Yucheng Zhao
    State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai, China, 200433
    More by Yucheng Zhao
  • , and 
  • Mao Chen*
    Mao Chen
    State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai, China, 200433
    *[email protected]
    More by Mao Chen
    Orcidhttp://orcid.org/0000-0002-5504-3775
Cite this: J. Am. Chem. Soc. 2020, 142, 15, 7108–7115
Publication Date (Web):March 30, 2020
https://doi.org/10.1021/jacs.0c01016
Copyright © 2020 American Chemical Society
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    Abstract

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    Fluoropolymers have found broad applications for many decades. Considerable efforts have focused on expanding access toward main-chain fluorinated polymers. In contrast to previous polymerizations of gaseous fluoroethylenes conducted at elevated temperatures and with high-pressure metallic vessels, we here report the development of a photoorganocatalyzed reversible-deactivation radical alternating copolymerization of chlorotrifluoroethylene (CTFE) and vinyl ethers (VEs) at room temperature and ambient pressure by exposing to LED light irradiation. This method enables the synthesis of various fluorinated alternating copolymers with low Đ and high chain-end fidelity, allowing an iterative switch of the copolymerization between “ON” and “OFF” states, the preparation of fluorinated block alternating copolymers, as well as postsynthetic modifications.

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