Robust Supramolecular Adhesives Based on Natural Small Molecules Through Hydrogen Bonding

Abstract The environmental persistence and widespread application of conventional polymer adhesives raise critical concerns regarding network design complexity and long‐term residue accumulation. Herein, we present a water‐soluble supramolecular adhesive synthesized from natural small molecules. Unlike traditional polymer networks relying on weak intermolecular forces, this system establishes a robust ordered architecture through dynamic disulfide bond ring‐opening polymerization and carboxylate ion electrostatic interactions. Water‐soluble hexamethylenetetramine (HMTA) strategically increases hydrogen‐bonding site density while stabilizing the network topology, efficiently reducing chain entanglement. These synergistic effects endow the material with strong adhesion capability even at minimal usage (∼0.4 mg/cm 2 ), achieving a maximum adhesion strength capable of supporting up to 10 7 times its weight while maintaining considerable resistance to various environmental factors, including thermal extremes (−80°C to 120°C) and exposure to organic solvents. This supramolecular design paradigm offers an eco‐friendly alternative to conventional polymeric adhesives.