Healable, Recyclable, and Mechanically Tough Polyurethane Elastomers with Exceptional Damage Tolerance

There is a huge requirement of elastomers for use in tires, seals, and shock absorbers every year worldwide. In view of a sustainable society, the next generation of elastomers is expected to combine outstanding healing, recycling, and damage‐tolerant capacities with high strength, elasticity, and toughness. However, it remains challenging to fabricate such elastomers because the mechanisms for the properties mentioned above are mutually exclusive. Herein, the fabrication of healable, recyclable, and mechanically tough polyurethane (PU) elastomers with outstanding damage tolerance by coordination of multiblock polymers of poly(dimethylsiloxane) (PDMS)/polycaprolactone (PCL) containing hydrogen and coordination bonding motifs with Zn2+ ions is reported. The organization of bipyridine groups coordinated with Zn2+ ions, carbamate groups cross‐linked with hydrogen bonds, and crystallized PCL segments generates phase‐separated dynamic hierarchical domains. Serving as rigid nanofillers capable of deformation and disintegration under an external force, the dynamic hierarchical domains can strengthen the elastomers and significantly enhance their toughness and fracture energy. As a result, the elastomers exhibit a tensile strength of ≈52.4 MPa, a toughness of ≈363.8 MJ m−3, and an exceptional fracture energy of ≈192.9 kJ m−2. Furthermore, the elastomers can be conveniently healed and recycled to regain their original mechanical properties and integrity under heating. Healable, recyclable, and mechanically tough elastomers with exceptional fracture energy of ≈192.9 kJ m−2 are fabricated by crosslinking polyurethanes with in‐situ‐formed dynamic hierarchical domains capable of deformation and disintegration under external force. Elastomers can be healed and recycled in a highly efficient way to restore their original mechanical properties.