Covalent Adaptable Networks through Dynamic N,S-Acetal Chemistry: Toward Recyclable CO₂-Based Thermosets

Finding new chemistry platforms for easily recyclable polymers has become a key challenge to face environmental concerns and the growing plastics demand. Here, we report a dynamic chemistry between CO₂-sourced alkylidene oxazolidones and thiols, delivering circular non-isocyanate polyurethane networks embedding N,S-acetal bonds. The production of oxazolidone monomers from CO₂ is facile and scalable starting from cheap reagents. Their copolymerization with a polythiol occurs under mild conditions in the presence of a catalytic amount of acid to furnish polymer networks. The polymer structure is easily tuned by virtue of monomer design, translating into a wide panel of mechanical properties similar to commodity plastics, ranging from PDMS-like elastomers [with Young's modulus (E) of 2.9 MPa and elongation at break (ε_break) of 159%] to polystyrene-like rigid plastics (with E = 2400 MPa, ε_break = 3%). The highly dissociative nature of the N,S-acetal bonds is demonstrated and exploited to offer three different recycling scenarios to the thermosets: (1) mechanical recycling by compression molding, extrusion, or injection molding─with multiple recycling (at least 10 times) without any material property deterioration, (2) chemical recycling through depolymerization, followed by repolymerization, also applicable to composites, and (3) upcycling of two different oxazolidone-based thermosets into a single one with distinct properties. This work highlights a new facile and scalable chemical platform for designing highly dynamic polymer networks containing elusive oxazolidone motifs. The versatility of this chemistry shows great potential for the preparation of materials (including composites) of tuneable structures and properties, with multiple end-of-life scenarios.