Self-healing of coating damage is highly desirable for long-term corrosion protection. However, achieving intrinsic autonomous self-healing often involves a trade-off, as increased molecular mobility can compromise coating stability and corrosion resistance, particularly in harsh, water-rich environments. Herein, a robust anti-corrosion coating with remarkable autonomous self-healing ability is presented. By integrating a hydrophobic deep eutectic solvent (HDES) into a disulfide bond-crosslinked siloxane-modified epoxy resin (SiEP-SS), the SiEP-SS/HDES40 (40 wt.% HDES) coating achieves rapid self-healing within 1 h in both atmospheric and underwater environments. This remarkable performance arises from the synergy between the SiEP-SS matrix elasticity (elastic recovery ratio We = 71.4%) and the confined flow of HDES, which together promote crack closure and damage-interface reconnection. The coating demonstrates outstanding corrosion resistance and long-term durability, withstanding 1000 h of salt spray testing, enabled by hydrophobic interactions within the SiEP-SS/HDES network. Molecular dynamics simulations reveal the critical roles of HDES mobility and hydrophobic interactions in promoting interfacial healing. The SiEP-SS/HDES coating exhibits significant scalability without performance degradation, providing a robust solution for corrosion protection and laying the foundation for designing DES-based advanced protective coatings with autonomous self-healing ability.
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