State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai, China, 200433.
J Am Chem Soc. 2020 Apr 15;142(15):7108-7115. doi: 10.1021/jacs.0c01016. Epub 2020 Apr 7.
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 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.
几十年来，氟聚合物已经得到了广泛的应用。人们已经投入了相当大的精力来拓展含氟聚合物的主链。与之前在高温和高压金属容器中进行气态氟乙烯聚合的方法不同，我们在这里报告了在室温常压下通过 LED 光照射进行氯三氟乙烯（CTFE）和乙烯基醚（VEs）的光有机催化可逆失活自由基交替共聚的发展。这种方法能够合成具有低和高链端保真度的各种氟化交替共聚物，允许在“开”和“关”状态之间进行共聚反应的迭代切换，制备氟化嵌段交替共聚物，以及进行后合成修饰。
