Mechanistic Insights on Spontaneous Moisture-Driven Healing of Urea-Based Polyurethanes

Self-healing polymeric materials that can spontaneously repair in a perpetual manner are highly appealing to address safety and restoration issues in different key applications. Usually built from reversible moieties that require to be activated using, for example, temperature, light, or pH changes, most of these self-healing materials rely on energy-demanding processes and/or external interventions to promote self-healing. In this work, we propose to exploit rapid dynamic exchanges between urea-based moieties and moisture as an alternative to promote local and spontaneous healing responses to damage using atmospheric moisture as an external stimulus. Non-hygroscopic urea-based polyurethanes with repetitive moisture-induced healing abilities at different degrees of humidity were thus designed through coupling reactions with non-hygroscopic polypropylene glycol and urea moieties. As supported by density functional theory (DFT) calculations coupled to local FTIR experimental studies, we furthermore established that the healing mechanism is ultimately related to the formation of water-urea clusters. Obviously, this work represents a platform for designing more advanced spontaneous self-healing materials beyond the present study, which hold promise for use in a wide range of technological applications.