Fluoropolymers of well-defined structures exhibit significant potential in a broad range of high-tech applications. However, the controlled synthesis of fluoropolymers from easily available monomers remains difficult. In this work, we report the development of an organocatalyzed controlled radical copolymerization of (perfluoroalkyl)ethylenes (PFAEs) and unconjugated vinyl monomers (UCMs) under light irradiation, which has enabled on-demand access toward side-chain fluorinated polymers under metal-free conditions. This method furnishes a large variety of polymers with diverse fluoroalkyl and ester/amide as pendent groups, tunable molar masses, and low dispersities (ca. Đ = 1.1–1.3), and adjustable fractions of PFAE and UCM units. Obtained fluoropolymers exhibit good chain-end fidelity and activity, allowing chain-extension polymerizations to prepare block copolymers of complicated compositions. Furthermore, the PFAE copolymers exhibit outstanding light transmission and low refractive index.

中文翻译：

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（全氟烷基）乙烯和乙烯基酯/酰胺的光驱动有机催化受控自由基共聚


具有明确结构的含氟聚合物在广泛的高科技应用中表现出巨大的潜力。然而，从容易获得的单体中受控合成含氟聚合物仍然很困难。在这项工作中，我们报道了在光照射下（全氟烷基）乙烯 （PFAE） 和未共轭乙烯基单体 （UCM） 的有机催化受控自由基共聚的开发，这使得在无金属条件下按需获得侧链氟化聚合物成为可能。该方法为各种聚合物提供了不同的氟烷基和酯/酰胺作为下垂基团、可调摩尔质量和低分散度 （约 Đ = 1.1–1.3） 以及 PFAE 和 UCM 单元的可调馏分。获得的含氟聚合物具有良好的链端保真度和活性，允许链延伸聚合制备复杂成分的嵌段共聚物。此外，PFAE 共聚物具有出色的透光率和低折射率。