Organocatalyzed Photocontrolled Radical Polymerization of Semifluorinated (Meth)acrylates Driven by Visible Light

• Published in: Angewandte Chemie International Edition 2018-01, Vol.57 (1), p.333-337
• Main Authors: Gong, Honghong, Zhao, Yucheng, Shen, Xianwang, Lin, Jun, Chen, Mao
• Format: Article
• Language: English
• Subjects: Acrylates; flow chemistry; Fluorination; fluorine; Iodides; metal-free processes; Photopolymerization; Polymerization; Polymers; synthetic methods
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201711053

Fluorinated polymers are important materials that are widely used in many areas. Herein, we report the development of a metal‐free photocontrolled radical polymerization of semifluorinated (meth)acrylates with a new visible‐light‐absorbing organocatalyst. This method enabled the production of a variety of semifluorinated polymers with narrow molar‐weight distributions from semifluorinated trithiocarbonates or perfluoroalkyl iodides. The high performance of “ON/OFF” control and chain‐extension experiments further demonstrate the utility and reliability of this method. Furthermore, to streamline the preparation of semifluorinated polymers, a scalable continuous‐flow approach has been developed. Given the broad interest in fluorinated materials and photopolymerization, we expect that this method will facilitate the development of advanced materials with unique properties. Flowing with fluorine: A new photoredox catalyst enabled the metal‐free photocontrolled radical polymerization of semifluorinated (meth)acrylates to provide semifluorinated polymers with narrow molecular‐weight distributions and high chain‐end‐group fidelity at high monomer conversions. Furthermore, a continuous‐flow approach was established to promote the scalable synthesis of semifluorinated block copolymers.