Facilely Accessible and Reusable High‐Performance Poly(Thioester Amide) Adhesives with Exceptional Versatility and Environmental Stability

Abstract Despite significant advancements in adhesive technology, developing adhesives that combine strong adhesion with reusability remains a formidable challenge. Current commercial adhesives often fail under cold or humid conditions, highlighting the need for next‐generation systems with enhanced environmental resilience and reusability. In this study, a facile and robust polymer adhesive is developed and synthesized via the spontaneous, catalyst‐free ring‐opening copolymerization (ROCOP) of N ‐alkyl aziridine and glutaric thioanhydride (GTA). The resulting cyclic alternating poly(thioester amide)s (PTEAs), particularly P(Az Bn ‐GTA) derived from N ‐benzylaziridine (Az Bn ) and GTA, exhibit versatile adhesion across various substrates, including dissimilar materials, with a maximum adhesion strength of 17.8 MPa on steel. By introducing multiple interaction sites and tailoring side groups, a well‐balanced combination of cohesive and interfacial adhesion energies is achieved, conferring the polymers with exceptional elasticity and toughness. Moreover, the incorporation of flexible backbones and hydrophobic moieties imparts remarkable resistance to ultralow temperature and water. Reversible adhesion is demonstrated through simple heating and cooling cycles, with stable performance maintained over 10 reprocessing cycles. Overall, the high performance and reusability of P(Az Bn ‐GTA) surpass those of previously reported adhesives, positioning it as an advanced and sustainable alternative aligned with circular economy principles.