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

Abstract

AbstractThe 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, Đ=2.4) possessing excellent thermal stabilities (TD5 %=249 °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.