Mismatched Supramolecular Interactions Facilitate the Reprocessing of Super‐Strong and Ultratough Thermoset Elastomers

Thermoset elastomers have been extensively applied in many fields because of their excellent mechanical strengths and durable characteristics, such as an excellent chemical resistance. However, in the context of environmental issues, the nonrecyclability of thermosets has become a major barrier to the further development of these materials. Here, a well‐tailored strategy is reported to solve this problem by introducing mismatched supramolecular interactions (MMSIs) into a covalently cross‐linked poly(urethane‐urea) network with dynamic acylsemicarbazide moieties. The MMSIs significantly strengthen and toughen the thermoset elastomer by effectively dissipating energy and resisting external stress. In addition, the elastomer recycling efficiency is improved 2.7‐fold due to the superior reversibility of the MMSIs. The optimized thermoset elastomer features outstanding characteristics, including an ultrahigh tensile strength (110.8 MPa), an unprecedented tensile toughness (1245.2 MJ m−3), as well as remarkable resistance to chemical media, creep, and damage. Most importantly, it exhibits an extraordinary multirecyclability, and the 4th recycling efficiency remains close to 100%. This scalable method promotes the development of thermosets with both high performance and excellent recyclability, thereby providing valuable guidance for addressing the issue of nonrecyclability from a molecular design standpoint. A bioinspired strategy for improving the recyclability of mechanically strong and tough thermoset elastomers is developed using mismatched supramolecular interactions to molecularly engineer the covalently cross‐linked polymer network. This work produces a robust elastomer with an extraordinary multirecyclability comparable to thermoplastic materials. This work presents a novel pathway for enabling the sustainable recycling of extremely durable thermosets.