Issue 77, 2024

Productive chemistry induced by mechanochemically generated macroradicals

Abstract

Large or repeated mechanical loads degrade polymeric materials by accelerating chain fragmentation. This mechanochemical backbone fracture usually occurs by homolysis of otherwise inert C–C, C–O and C–S bonds, generating highly reactive macroradicals. Because backbone fracture is detrimental on its own and the resulting macroradicals can initiate damaging reaction cascades, a major thrust in contemporary polymer mechanochemistry is to suppress it, usually by mechanochemical release of “hidden length” that dissipates local molecular strain. Here we summarize an emerging complementary strategy of channelling mechanochemically generated macroradicals in reaction cascades to form new load-bearing chemical bonds, which enables local self-healing or self-strengthening, and/or to generate mechanofluorescence, which could yield detailed quantitative molecular understanding of how material-failure-inducing macroscopic mechanical loads distribute across the network. We aim to identify generalizable lessons derivable from the reported implementations of this strategy and outline the key challenges in adapting it to diverse polymeric materials and loading scenarios.

Graphical abstract: Productive chemistry induced by mechanochemically generated macroradicals

Article information

Article type
Feature Article
Submitted
29 jun 2024
Accepted
15 aug 2024
First published
16 aug 2024
This article is Open Access
Creative Commons BY license

Chem. Commun., 2024,60, 10629-10641

Productive chemistry induced by mechanochemically generated macroradicals

C. Wang, C. Sun and R. Boulatov, Chem. Commun., 2024, 60, 10629 DOI: 10.1039/D4CC03206C

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