Stretchable Self‐Healing Plastic Polyurethane with Super‐High Modulus by Local Phase‐Lock Strategy

Abstract In this work, a multiblock polyurethane (PU‐Im) consisting of polyether and polyurethane segments with imidazole dangling groups is demonstrated, which can further coordinate with Ni 2+ . By controlling the ligand content and metal–ligand stoichiometry ratio, PU‐Im‐Ni complex with vastly different mechanical behavior can be obtained. The elastomer PU‐2Im‐Ni has extraordinary mechanical strength (61MPa) and excellent toughness (420 MJ m −3 ), but the plastic PU‐4Im‐Ni exhibits super‐high modulus (515 MPa), strength (63 MPa), and good stretchability (≈800%). The metal–ligand interaction between polyurethane segments and Ni 2+ is proved by Raman spectra, dynamic mechanical analysis (DMA), and transmission electron microscopy (TEM). The polyurethane segments domain formed by microphase separation is dynamically “locked” by Ni 2+ coordinated with imidazole, revealing a local phase‐lock effect. The phase‐locking hard domains reinforce the PU‐Im‐Ni complex and maintain stimuli‐responsive self‐healing ability, while the free polyether segments provide stretchability. Primarily, the water environment with plasticization effect serves as an effective and eco‐friendly self‐healing approach for PU‐Im‐Ni plastic. With the excellent mechanical performance, thermal/aquatic self‐healing ability, and unique damping properties, the PU‐Im‐Ni complexes show potential applications in self‐healing engineering plastic and cushion protection fields.