High‐Performance Thermoplastic Polyurethane Elastomers with Simultaneously Enhanced Strength, Toughness, and Resilience Enabled by Synergistic Hierarchical Hydrogen Bonds and Strain‐Induced Crystallization

Developing thermoplastic polyurethane elastomers (TPUs) with high strength while retaining inherent toughness and elasticity remains a fundamental challenge. However, most high‐performance TPUs rely on high‐density dynamic noncovalent interactions, raising the risk of deterioration in certain mechanical and processing properties. Herein, a novel TPU material is synthesized by utilizing poly(δ‐valerolactone) (PVL) as the soft segment, coupled with isophorone diisocyanate and oxalyl dihydrazide as the hard segment components. The incorporation of PVL endows the TPU with pronounced strain‐induced crystallization (SIC) triggered by chain alignment during deformation. The resulting stress‐hardening effect provides additional, reversible load‐bearing capacity that synergistically complements the dynamic physical cross‐linking of the hydrogen‐bond networks, enabling high mechanical strength without compromising elastic recovery. Consequently, a high‐performance TPU is achieved with a tensile strength of 88.4 MPa and a toughness of 445.4 MJ m −3 . Meanwhile, the internal energy of crystals formed during stretching is as low as 6.1 cal g −1 , indicating their instability and susceptibility to melting upon force removal. Concurrently, accompanied by rapid restructuring of the hydrogen‐bond networks, the elastic recovery of the high‐performance TPUs exceeds 90%. This cooperative reinforcement mechanism establishes an effective design principle for constructing next‐generation TPUs that simultaneously exhibit high strength, toughness, and resilience.