Photocontrolled cationic degenerate chain transfer polymerizations via thioacetal initiators

被引:23
作者
Sifri, Renee J. [1 ]
Kennedy, Audrey J. [1 ]
Fors, Brett P. [1 ]
机构
[1] Cornell Univ, Dept Chem & Chem Biol, Ithaca, NY 14853 USA
关键词
LIVING RADICAL POLYMERIZATION; VISIBLE-LIGHT; VINYL ETHERS; ACTIVATION; PPM;
D O I
10.1039/d0py01100b
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
Recent developments in photocontrolled polymerizations have facilitated the development of previously inaccessible materials. While photocontrolled radical polymerizations have been extensively studied, related processes involving cationic polymerizations are underexplored and limited to RAFT processes. In this study, we disclose a visible light, temporally controlled cationic polymerization of vinyl ethers utilizing thioacetals and a photoredox catalyst. We demonstrate a broad scope of thioacetal initiators that achieve a well-controlled polymerization by recapping propagating chains via photocatalyst turnover in combination with a degenerate chain transfer process through sulfonium intermediates. Furthermore, we show that a photocatalyst with a more reducing ground state reduction potential allows for enhanced control and excellent temporal regulation of polymerization.
引用
收藏
页码:6499 / 6504
页数:6
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