Molecular Design of Underwater Adhesive Copolymers: Synergy Between Long-Chain Alkyl Crystallization–Melting Switching and Carboxyl Group Interfacial Interactions

Achieving strong adhesion in underwater or humid environments remains challenging because the interfacial hydration layer prevents direct contact between the adhesive and the substrate. Conventional adhesives typically fail under these conditions, so new strategies are needed to actively displace the water layer and create stable interfacial interactions. In this study, we prepared a series of copolymers with different monomer ratios via photocuring, using methacrylic acid (MAA) and stearyl methacrylate (SMA) as monomers. We focused on their thermal transition behavior and adhesion performance under both dry and underwater conditions. The results show that at an SMA molar fraction of 85%, the copolymer exhibits crystalline melting between 30 and 40 °C, where the storage modulus drops from approximately 107 Pa to 104 Pa, indicating a stiff-to-soft transition. Under dry conditions, this composition shows an adhesion strength of 1.67 MPa to glass, which remains 1.2 MPa underwater, and it can support a hanging load of 5 kg. The copolymer adheres well to glass and aluminum but shows weak adhesion to PTFE. After surface abrasion, the adhesion strength to glass increases to 1.6–1.8 MPa. In summary, the copolymer achieves effective underwater adhesion through the synergy of hydrophobic water displacement, thermally induced stiff-to-soft switching, and hydrogen bonding.