Facile Solid-State Mechanochemical Synthesis of Eco-Friendly Thermoplastic Polyurethanes and Copolymers Using a Biomass-Derived Furan Diol

Herein, we report a facile, one-pot, green, and solvent-less (solid-state) mechanochemical approach toward the synthesis of eco-friendly polyurethanes (PUs) at room temperature using biomass-derived 2,5-bis­(hydroxymethyl)­furan (BHMF) combined with vibration milling. This approach is simple, straightforward, and very fast even at room temperature because of the instantaneous energy generated during grinding. BHMF, a biomass-derived monomer, was successfully used to synthesize PUs via ball milling; the resulting PUs have a maximal M_w of 163k and are flexible (T_g = 96 °C) and thermally stable (T_d = 197 °C). In addition, ball milling enabled the synthesis of PU copolymers with various diols and diamines, resulting in variation of the polymer properties, such as the glass transition temperature (T_g).