Ternary Synergistic Catalysis Enables Mild Solvent‐Free Closed‐Loop Upcycling of Polyurethane Foam

Efficient recycling of polyurethane foam (PUF) under mild conditions remains a critical challenge. Herein, we report a ternary 1,1,3,3‐tetramethylguanidine (TMG)/cadmium (Cd)/1‐methyl‐2‐hydroxymethylimidazole (HMMI) catalyst with Cd as the metal center, integrating Brønsted base, Lewis acid, and binuclear metal. Combined with a multistage degradation strategy, it achieves complete cleavage of carbamate/urea bonds in PUF under solvent‐free mild conditions (180–200°C, 4 h, degradant dosage: 10 wt% relative to PUF mass), enabling spontaneous phase separation into high‐purity recycled polyols (RP) and isocyanate‐derived hard segments (HS). RP exhibits properties similar to virgin polyols (VP) (hydroxyl value: 66 mgKOH g −1 ; viscosity: 950 mPa s) and can replace 40 wt% of VP without compromising foam performance, while HS serves as a reinforcing additive for rigid foams. This closed‐loop strategy minimizes waste, aligns with circular economy principles, and provides a scalable pathway for PUF upcycling.