Ligament Inspired Ultra‐Strong and Tough Bio‐Based Polyurethane Elastomers via Dynamic Hydrogen Bonding Induced Confinement Effect

Abstract Thermoplastic polyurethane elastomer (TPU) is extensively utilized in biomedical engineering, flexible electronics, and intelligent drives due to their excellent mechanical adjustability and biocompatibility. However, traditional TPU still faces significant challenges in balancing raw material renewability and mechanical property enhancement. Herein, inspired by the “fiber‐matrix” hierarchical structure of ligaments, an innovative molecular engineering strategy of dynamic hydrogen bonding‐induced confinement effect (DHBCE) is proposed. Bio‐based polytrimethylether diol (PO3G) serves as the soft phase, providing the elastomer with super‐ductility, while 2,5‐furan diformylhydrazide (FDHA) is designed as the building unit of the hard phase dynamic network. A reversible dynamic hydrogen bond network is constructed at the molecular level to drive the gradient continuous distribution of soft and hard phases. This bionic “soft‐hard” gradient bi‐continuous microstructure achieves a substantial increase in the elastomer's strength and toughness (breaking strength: 76.54 MPa, toughness: 589.75 MJ m −3 ). Notably, the elastomer also exhibits excellent biocompatibility. Biomimetic artificial ligaments with mechanical response characteristics similar to natural ligaments can be precisely fabricated using melting deposition 3D printing technology. This research advances the sustainable development of biomedical elastomers through innovative molecular design and the application of bio‐based raw materials.