Productive Chemistry Induced by Mechanochemically Generated Macroradicals

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.