Force-reversible chemical reaction at ambient temperature for designing toughened dynamic covalent polymer networks

Force-reversible C-N bonds, resulting from the click chemistry reaction between triazolinedione (TAD) and indole derivatives, offer exciting opportunities for molecular-level engineering to design materials that respond to mechanical loads. Here, we displayed that TAD-indole adducts, acting as crosslink points in dry-state covalently crosslinked polymers, enable materials to display reversible stress-responsiveness in real time already at ambient temperature. Whereas the exergonic TAD-indole reaction results in the formation of bench-stable adducts, they were shown to dissociate at ambient temperature when embedded in a polymer network and subjected to a stretching force to recover the original products. Moreover, the nascent TAD moiety can spontaneously and immediately be recombined after dissociation with an indole reaction partners at ambient temperature, thus allowing for the adjustment of the polymer segment conformation and the maintenance of the network integrity by force-reversible behaviors. Overall, our strategy represents a general method to create toughened covalently crosslinked polymer materials with simultaneous enhancement of mechanical strength and ductility, which is quite challenging to achieve by conventional chemical methods. Weak force-activated covalent bonds as crosslink points can increase mechanical strength and ductility in polymers but the bonds, once broken, cannot be reformed in real time under ambient conditions leading to irreversible damage. Here, the authors demonstrate that triazolinedione (TAD)-indole adducts acting as crosslink points enable materials to display already at ambient temperature reversible stress-responsiveness in real time.

Automated summary

The click chemistry reaction between triazolinedione (TAD) and indole derivatives was used to create force-reversible C-N bonds, which enable materials to display reversible stress-responsiveness in real time. This method provides a general strategy to enhance mechanical strength and ductility in covalently crosslinked polymer materials.