Autonomous self-healing and superior tough polyurethane elastomers enabled by strong and highly dynamic hard domains.

Self-healing materials show exceptional application potential for their high stability and longevity. However, a great challenge of the application of self-healing materials is the tradeoff between mechanical robustness and room temperature self-healing. In order to address this tradeoff, inspired by the characteristic that small molecules of living organisms self-assemble into large protein molecules by non-covalent interactions, we constructed polyurethane with highly dynamic and strong hard domains composed of dense hydrogen bonds and π-π interactions between the phenylurea groups at the end of the side chain. The prepared elastomer (PU-HU₂-60) exhibits exceptional tensile performance (tensile strength is 18.27 MPa and ultimate elongation is 904.6%) and crack tolerance (fracture energy is 57.78 kJ m^-2), surpassing those of most room temperature self-healing materials. After being damaged, the dynamic change process of hydrogen bonds and π-π interactions enables the elastomer to show a high self-healing efficiency of 92.15% at room temperature. Using molecular dynamics (MD) simulations and experiments, we verified that hydrogen bonds and π-π interactions promote the formation of hard domains and the autonomous self-healing of elastomers. The prepared elastomers can also be recycled and they showed ultra-high and restorable adhesion between metals. This work demonstrates a new strategy to balance the mechanical and self-healing properties of elastomers to expand their practical applications such as metal adhesives.