Recyclable and Ultra‐Strong Adhesives Spanning Ambient to Cryogenic Temperatures

ABSTRACT Adhesives that combine high strength, recyclability and reliability across a broad temperature range are vital for advanced manufacturing. However, simultaneously achieving strong interfacial adhesion, closed‐loop recyclability, and robustness with low‐temperature tolerance remains challenging due to intrinsic architectural and interactional constraints of polymers. Herein, a series of poly(disulfide)‐based adhesives bearing side‐chain B21C7 crown ether and ammonium units was prepared via random copolymerization. The crown ether‐ammonium host–guest coupling forms dynamic interfacial networks that could significantly enhance the energy dissipation and adhesion strength. Meanwhile, the synergistic effects of the flexible polymer backbone and bound water effectively suppress thermal stress contraction and ice crystallization at low temperatures, broadening the operational temperature window. The adhesive achieves an interfacial strength of 14.39 MPa at room temperature and maintains 10.53 MPa even at −196°C, exhibiting exceptional wide‐temperature adhesion. Notably, this cryogenic adhesion strength ranks among the highest reported for closed‐loop recyclable adhesives. Moreover, it demonstrated closed‐loop recyclability and functions as both a structural and conductive adhesive with robust stability under harsh environments. This work provides new opportunities for creating high‐performance recyclable adhesives capable of reliable operation under extreme conditions.