Issue 45, 2022

Ring size-reactivity relationship in radical ring-opening copolymerisation of thionolactones with vinyl pivalate

Abstract

The radical ring-opening copolymerisation (rROcoP) of unsubstituted thionolactones of different ring sizes, namely γ-thionobutyrolactone (TBL), δ-thionovalerolactone (TVL), ε-thionocaprolactone (TCL) and ω-thionopentadecalactone (TPDL), with vinyl pivalate has been mechanistically investigated. The crucial effect of the ring-size on the ability of thionolactone to copolymerise and ring-open is depicted, with the fraction of ring-opened thionolactone units following the order 7 > 16 > 5 > 6 membered thionolactone. DFT calculations in combination with experimental results show the importance of the stabilization of the intermediate ring-retained radical for the thionolactone reactivity. A chain-terminating effect was revealed for TBL, TVL and TPDL. The incorporation of thionolactone units in the copolymers was evidenced by substantial decrease in Mw after chemical degradation.

Graphical abstract: Ring size-reactivity relationship in radical ring-opening copolymerisation of thionolactones with vinyl pivalate

Supplementary files

Article information

Article type
Paper
Submitted
06 Sep 2022
Accepted
21 Oct 2022
First published
21 Oct 2022

Polym. Chem., 2022,13, 6284-6292

Ring size-reactivity relationship in radical ring-opening copolymerisation of thionolactones with vinyl pivalate

O. Ivanchenko, S. Mazières, R. Poli, S. Harrisson and M. Destarac, Polym. Chem., 2022, 13, 6284 DOI: 10.1039/D2PY01153K

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