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Issue 40, 2020
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Photocontrolled cationic degenerate chain transfer polymerizations via thioacetal initiators

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Abstract

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.

Graphical abstract: Photocontrolled cationic degenerate chain transfer polymerizations via thioacetal initiators

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Supplementary files

Article information


Submitted
31 Jul 2020
Accepted
11 Sep 2020
First published
11 Sep 2020

Polym. Chem., 2020,11, 6499-6504
Article type
Paper

Photocontrolled cationic degenerate chain transfer polymerizations via thioacetal initiators

R. J. Sifri, A. J. Kennedy and B. P. Fors, Polym. Chem., 2020, 11, 6499
DOI: 10.1039/D0PY01100B

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