Mechanically Robust and Chemically Recyclable Polyhydroxyurethanes from CO₂-Derived Six-Membered Cyclic Carbonates

In the current context of sustainable chemistry development and new regulations, aminolysis of cyclic carbonate is one of the most promising routes to nonisocyanate polyurethanes, also called polyhydroxyurethanes (PHU). In this study, a new kind of shape memory PHU vitrimers with outstanding mechanical properties and chemical recyclability is prepared. The monomer employed for aminolysis to form the PHUs is bis(six-membered cyclic carbonate) of 4,4'-biphenol (BCC-BP), which is synthesized by bi(1,3-diol) precursors and CO₂. The synthetic strategy, isocyanate-free and employing CO₂ as a building block, is environmentally friendly and suits the concept of carbon neutrality. The thermal properties, mechanical properties, and dynamic behaviors of the PHUs are explored. The maximum breaking strength and elongation at break of the resultant PHUs reach 65 MPa and 452%, respectively, exceeding other reported PHU-based materials in combined performance. Such a PHU material can also lift up a load 4700 times heavier than its own weight by a shape recovery process. Finally, the bi(1,3-diol) can be regenerated through the alcoholysis of PHUs to realize chemical recycling. This work provides a feasibility study for a green synthetic approach and for designing a novel PHU material with outstanding properties.