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Precise Synthesis of Ultra‐High‐Molecular‐Weight Fluoropolymers Enabled by Chain‐Transfer‐Agent Differentiation under Visible‐Light Irradiation
Author(s) -
Gong Honghong,
Gu Yu,
Zhao Yucheng,
Quan Qinzhi,
Han Shantao,
Chen Mao
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201912698
Subject(s) - copolymer , polymer , chain transfer , irradiation , polymerization , chemistry , photochemistry , side chain , radical polymerization , polymer chemistry , chemical engineering , materials science , organic chemistry , physics , nuclear physics , engineering
Ultra‐high‐molecular‐weight (UHMW) polymers display outstanding properties and hold potential for wide applications. However, their precise synthesis remains challenging. Herein, we developed a novel reversible‐deactivation radical polymerization based on the strong and selective fluorine–fluorine interaction, allowing chain‐transfer agents to spontaneously differentiate into two groups that take charge of the chain growth and reversible deactivation of the growing chains, respectively. This method enables dramatically improved livingness of propagation, providing UHMW polymers with a surprisingly narrow molecular weight distribution ( Đ ≈1.1) from a variety of fluorinated (meth)acrylates and acrylamide at quantitative conversions under visible‐light irradiation. In situ chain‐end extensions from UHMW polymers facilitated the synthesis of well‐defined block copolymers, revealing the excellent chain‐end fidelity achieved by this method.