Intrinsic Catalytic Self‐Scission‐Reconstruction Enables Direct Upcycling of Flame‐Retardant Polyurethane Foams

ABSTRACT Flexible polyurethane foams (FPUFs) are indispensable in industrial and consumer products, yet their end‐of‐life management remains an enduring environmental challenge. The addition of flame retardants, though essential for fire safety, typically compromises recyclability and limits value recovery. Here, we introduce an intrinsic catalytic self‐scission‐reconstruction strategy mediated by spiroborate potassium, a dynamic linkage that autonomously responds to temperature and molecular environment by self‐cleaving into catalytic and degradative units. This adaptive system integrates durable flame retardancy with direct chemical upcycling of FPUFs through catalytic urethane bond rearrangement. The resulting foam exhibits a high limiting oxygen index and effectively suppresses heat and smoke release while preserving long‐term structural stability. Upon gentle thermal activation, without external catalysts, it undergoes self‐controlled fragmentation into borate‐crosslinked oligomers rich in reactive moieties, which can be directly reconstructed without purification, into robust adhesives via self‐catalytic dynamics. The regenerated adhesives display outstanding bonding strength (up to 12.58 MPa) across diverse substrates and maintain integrity under harsh chemical (HCl, NaOH, NaCl) and extreme thermal conditions (−196 °C). This work establishes a general self‐scission‐reconstruction approach for up‐recycling of flame‐retardant materials, transforming fire‐safe polymers from end‐of‐life liabilities into high‐value functional materials.