An unparalleled H-bonding and ion-bonding crosslinked waterborne polyurethane with super toughness and unprecedented fracture energy.

Self-healing polyurethane elastomers have been extensively studied; however, developing an eco-friendly self-healable waterborne polyurethane (WPU) with exceptional mechanical properties remains a great challenge. Herein, we report healable, and highly tough WPU elastomers with unprecedented crack tolerance by introducing the concerted interactions of strong multiple H-bonds and ionic bonds in the network. The WPU elastomer demonstrated that the microphase separation structure contributes to an ultrahigh tensile strength (≈58 MPa), super toughness (≈456 MJ m), and unprecedented record fracture energy (≈320 kJ m). Due to the dynamic reconstruction of reversible H-bonds and ionic bonds, the WPU elastomer demonstrates a robust self-healability at 50 °C, allowing complete recovery of mechanical properties. Importantly, the thermoplasticity and reprocessability of WPUs enable direct 3D printing of different objects and electrospinning of tubes, showing great potential for expanding their application scope in soft robots and artificial stents.