Biobased High- T g Aliphatic Polyethers via the Ring-Opening Polymerization of Dihydrolevoglucosenone-Derived Spiro-Epoxides

We present a concise and efficient strategy for synthesizing a novel aliphatic polyether with a high glass-transition temperature ( T g ) from dihydrolevoglucosenone (Cyrene), a cellulose-derived green solvent and platform molecule. Using a one-step Corey–Chaykovsky reaction, Cyrene was converted into a spiro-epoxide, DBOO. The anionic ring-opening polymerization (AROP) of DBOO afforded the corresponding polyether, PDBOO. To the best of our knowledge, this is the first example of a polyether synthesized via the AROP of a spiro-epoxide. PDBOO exhibits an exceptionally high T g (140 °C), which is uncommon for aliphatic polyethers. The diastereomeric ratio of DBOO strongly influences the properties of the resulting material, including its crystallinity and solvent resistance. Moreover, these intriguing characteristics are rationalized through molecular mechanics calculations, which revealed the rigid and compact molecular conformation of the polymer. Overall, this study not only demonstrates the effective use of abundant biomass resources to produce high-performance polymeric materials but also demonstrates the polymerization potential of a new class of epoxide monomers, structurally unique spiro-epoxides, thus paving the way for the development of novel polymer materials with distinctive properties.