期刊
ACS CATALYSIS
卷 12, 期 12, 页码 7269-7277出版社
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.2c01640
关键词
photoredox catalysis; PET-RAFT; organocatalysis; reversible-deactivation radical polymerization; fluoropolymer; copolymer
资金
- NSFC [21971044]
- Science and Technology Commission of Shanghai Municipality
- Shanghai Pilot Program for Basic Research-FuDan University [21TQ1400100, 21TQ007]
- State Key Laboratory of Molecular Engineering of Polymers
By developing an organic photoredox catalyst, controlled photo-controlled radical copolymerization of multiple PFVEs and unconjugated comonomers is achieved. This method has high reaction efficiency and can produce a variety of complex fluoropolymers.
Perfluorinated vinyl ethers (PFVEs) are an important category of monomers for producing fluoropolymers that have found broad applications. In this work, by developing a dibenzo[a,c]phenothiazine-based organic photoredox catalyst, we realize photo-controlled radical copolymerization of various PFVEs and unconjugated comonomers (e.g., vinyl esters, vinyl amides, and vinyl ethers) with a high reaction efficiency when exposed to visible-light irradiation, affording a large series of main- and side-chain fluorinated copolymers of low dispersities (D = 1.06-1.24) and good chain-end fidelity at excellent conversions of unconjugated comonomers. Furthermore, this method not only facilitates the ON/OFF temporal switch of the chain growth with tunable kinetics for the ON states upon altering the wavelengths of light sources but also allows photo-controlled chain extensions with copolymers and homopolymers as additional blocks, presenting a facile and versatile platform to customize complex fluoropolymers for material engineering.
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