Microcage flame retardants with complete recyclability and durability via reversible interfacial locking engineering†

Flame retardants are effective in protecting materials from fire but pose environmental challenges due to limited recyclability. Urgently needed for circular material economy are new flame retardants that are chemically recyclable and durable. Here, we report a new facile and scalable strategy for engineering reversible microcages with infinite chemical recyclability to starting monomers, exceptional durability, and versatile flame retardancy. This is achieved through a highly synergistic hierarchical assembly of easily obtainable phosphoric acid and Cu²⁺ monomers. By leveraging dynamic reversible assembly networks, microcages can be circularly and infinitely dissociated into starting monomers via eco-friendly pH adjustment. Remarkable recovery rates of 92% for phosphoric acid and 96.2% for Cu²⁺ monomers are achieved, while the separated virgin matrix undergoes conventional chemical recycling, facilitating reformulation and seamless reintroduction into new supply chains as needed. Notably, when integrated with matrix-like surfaces, microcage clasp matrices tightly engage through in situ formed interfacial locking structures, showcasing outstanding flame-retardant efficiency, prolonged durability in hydrothermal aging, and extensive applicability across diverse polymeric materials such as polyurethane, epoxy resin, and polycarbonate. This study emphasizes a novel, straightforward, and scalable chemical platform, utilizing reversible interfacial locking engineering, for the development of flame retardants that are not only infinitely recyclable but also durable and broadly applicable.