Ultrastable, Superrobust, and Recyclable Supramolecular Polymer Networks

Abstract Supramolecular polymer networks (SPNs), crosslinked by noncovalent bonds, have emerged as reorganizable and recyclable polymeric materials with unique functionality. However, poor stability is an imperative challenge faced by SPNs, because SPNs are susceptible to heat, water, and/or solvents due to the dynamic and reversible nature of noncovalent bonds. Herein, the design of a noncovalent cooperative network (NCoN) to simultaneously stabilize and reinforce SPNs is reported, resulting in an ultrastable, superrobust, and recyclable SPN. The NCoN is constructed by multiplying the H‐bonding sites and tuning the conformation/geometry of the H‐bonding segment to optimize the multivalence cooperativity of H‐bonds. The rationally designed H‐bonding segment with high conformational compliance favors the formation of tightly packed H‐bond arrays comprising higher‐density and stronger H‐bonds. Consequently, the H‐bonded crosslinks in the NCoN display a covalent crosslinking effect but retain on‐demand dynamics and reversibility. The resultant ultrastable SPN not only displays remarkable resistance to heat up to 120 °C, water soaking, and a broad spectrum of solvents, but also possesses a superhigh true stress at break (1.1 GPa) and an ultrahigh toughness (406 MJ m −3 ). Despite the covalent‐network‐like stability, the SPN is recyclable through activating its reversibility in a high‐polarity solvent heated to a threshold temperature.