Photoresponsive chain collapse in a flexo-rigid functional copolymer to modulate the self-healing behaviour.

Synthetic systems mimicking the natural self-folding process are attractive to impart multiple structural control over polymer crosslinking and the subsequent alteration of their macroscopic self-healing properties. In that regard, polymers P1-P5 containing pendant photo-crosslinkable moieties were designed and underwent intra- or interchain collapse to form diverse nanostructures. The shape and dimension of the nanostructures could be efficiently controlled by the concentration, solvent compatibility and characteristics of the polymers. Photodimerization of the coumarin moieties transformed the extended coiled chain of the polymer to uniform sized nanoparticles in a dilute condition, while in the crowded macromolecular concentration regime, the polymer folded into nanostructures with polydisperse topologies that were far from a condensed globule or partially swollen globule conformation. Scaling law exponents for polymer chain compaction suggested an interchain collapse with rigid compact segments connected by flexible polymer chains that draws an analogy with elastomers. Such a hardening of the rigid segment as a consequence of photodimerization rendered a significant increase in the glass transition temperature (Tg), which could be reversibly controlled upon decrosslinking. Lastly, the structural variation of this class of polymers over self-healing was explored and the crosslinked polymers showed phototriggered non-autonomic and intrinsic self-healing behaviour under ambient conditions. This is an interesting approach to access a photomodulated self-healing system with low Tg polymers that shows the coexistence of autonomic and nonautonomic self-healing pathways and that may find application in designing smart coatings for photovoltaic devices.