Biobased Polyethers via Acyclic Diene Metathesis Polymerization of α,ω-Diene Furanics

A new class of furanic α,ω-dienes was synthesized by using cellulose-derived 2,5-bis(hydroxymethyl)furan as a renewable starting material. The ability of these monomers to undergo acyclic diene metathesis polymerization was investigated under various reaction conditions, including type of metathesis catalyst and catalyst loading. The resulting biobased polyethers were characterized through high-performance size exclusion chromatography, differential scanning calorimetry, and thermal gravimetric analysis. The novel polymers showed molecular weights up to 43 kDa and exhibited good thermal stability (Td5% up to 301 °C) and low glass-transition temperatures (−67 °C < Tg < −24 °C). Polymerization reactions were also conducted employing selected green solvents (Cyrene, dimethyl isosorbide, and γ-valerolactone), and the results were compared to those of the solventfree procedure. Finally, in order to increase the Tg values of the polyethers, copolymerization experiments were performed employing the best performing furanic α,ω-diene as well as a biobased aromatic monomer derived from syringaresinol.