Enhanced polymer mechanical degradation through mechanochemically unveiled lactonization

The mechanical degradation of polymers is typically limited to a single chain scission per triggering chain stretching event, and the loss of stress transfer that results from the scission limits the extent of degradation that can be achieved. Here, we report that the mechanically triggered ring-opening of a [4.2.0]bicyclooctene (BCOE) mechanophore sets up a delayed, force-free cascade lactonization that results in chain scission. Delayed chain scission allows many eventual scission events to be initiated within a single polymer chain. Ultrasonication of a 120 kDa BCOE copolymer mechanically remodels the polymer backbone, and subsequent lactonization slowly (~days) degrades the molecular weight to 4.4 kDa, > 10× smaller than control polymers in which lactonization is blocked. The force-coupled kinetics of ring-opening are probed by single molecule force spectroscopy, and mechanical degradation in the bulk is demonstrated. Delayed scission offers a strategy to enhanced mechanical degradation and programmed obsolescence in structural polymeric materials.