Most tough hydrogels are reinforced by introducing energy dissipation mechanisms, but simultaneously realizing a high toughness and low hysteresis is challenging because the energy dissipation structure cannot recover rapidly. In this work, high mechanical performance highly entangled double network hydrogels without energy dissipation structure are fabricated, in which physical entanglements act as the primary effective crosslinking in the first network. This sliding entanglement structure allows the hydrogel network to form a highly uniform oriented structure during stretching, resulting in a high tensile strength of ~3 MPa, a fracture energy of 8340 J m⁻² and a strain-stiffening capability of 47.5 in 90% water content. Moreover, almost 100% reversibility is obtained in this hydrogel via energy storage based on entropy loss. The highly entangled double network structure not only overcomes the typical trade-off between the high toughness and low hysteresis of hydrogels, but more importantly, it provides an insight into the application of entanglement structures in high-performance hydrogels.

New linear polyurethane was synthesized via a Diels–Alder (DA) reaction between a polyurethane prepolymer end-capped with furan groups (MPF) and bismaleimide (BMI). The structure of the linear polyurethane with DA bonds was characterized by ¹H NMR, ATI-FTIR, TGA and AFM. The introduction of DA bonds enables the polyurethane thermal reversibility, which was studied thoroughly by ¹H NMR, DSC and GPC. Besides, the new linear polyurethane with DA bonds also exhibits self-healing properties under heat treatment, which was observed by polarized optical microscope. The self-healing efficiency determined by the recovery of breaking tensile strength after being damaged and healed can reach up to 80%.