Polymers from Cellulosic Waste: Direct Polymerization of Levoglucosenone using DBU as a Catalyst

The bio-based platform molecule levoglucosenone (LGO) is now produced at multi-ton scale by the pyrolysis of cellulosic waste. As such it has become an industrially viable, non-petroleum-derived chemical feedstock. Herein we report the direct (one-step) and operationally simple polymerization of LGO that provides a highly sustainable method for polymer synthesis. Specifically, the ability of LGO to act as an electrophile has been harnessed so as to deliver high molecular weight polymers (Mn=236,000 g/mol, D=2.4) possessing excellent thermal stabilities (TD5 %=249 degrees C). Furthermore, there is a significant capacity for the effective chemical manipulation of these polymers as exemplified by treatment of them under Baeyer-Villiger conditions and so creating a simple and green route to hydrophilic materials. These one- and two-step transformations provide the most direct route to new, LGO-derived polymer scaffolds yet reported. E-factors of ca. 0.012 and atom economies of up to 99 % have been realized.From bio-waste to polymers! Treatment of cellulose-derived LGO with 8 mole % DBU effects its polymerization to give poly-Cyrene (7) that is itself converted into the water soluble poly-2H-HBO (11) on reaction with aqueous hydrogen peroxide.image