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Updated: Jun 7, 2025

Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
Published on: April 22, 2016
Light-Driven Organocatalyzed Controlled Radical Copolymerization of (Perfluoroalkyl)ethylenes and Vinyl Esters/Amides
Qianhao Ye1, Kaixuan Chen1, Chengda Zhou1
1Department of Macromolecular Science, State Key Laboratory of Molecular Engineering of Polymers, Fudan Univesity, Shanghai 200433, China.
Abstract:
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.
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