Covalent Adaptable Ionic Networks for Robust, On‐Demand Dismantlable and Fully Recyclable Adhesives

On-demand debonding is a critical yet challenging requirement for advanced adhesives. Herein, we report a rational design strategy for robust, on-demand debondable, and fully recyclable adhesives via constructing covalent adaptable ionic networks (CAINs). Integrating the advantages of poly(ionic liquid)s (PILs) and covalent adaptable networks (CANs), the CAINs exhibit exceptional adhesion strength (>15 MPa on stainless steel), significantly outperforming most reported adhesives based solely on PILs or CANs. The material also maintains a shear strength of 11.0 MPa after immersion in liquid nitrogen, demonstrating excellent low‑temperature tolerance. Bis(trifluoromethanesulfonyl)imide anions endow the adhesives with remarkable hydrophobicity and excellent waterproof performance. Importantly, facile on-demand debonding is achieved via ethanol treatment under mild conditions, enabling complete substrate separation and efficient material recovery with minimal performance degradation over multiple cycles. Mechanistic studies indicate that the covalent crosslinked network is the primary contributor to high adhesion, while hydrogen bonding plays a secondary supportive role. This work establishes a versatile platform for designing high-performance dismantlable adhesives with superior recyclability, advancing sustainable adhesive technologies in advanced manufacturing and materials engineering.