Polymers from Sugars and Cyclic Anhydrides: Ring-Opening Copolymerization of a <scp>d</scp>-Xylose Anhydrosugar Oxetane

A d-xylose 3,5-anhydrosugar derivative has been used as an oxetane co-monomer in the ring-opening copolymerization (ROCOP) with cyclic anhydrides, to form a family of seven novel sugar-derived polyesters, up 100% renewable content. ROCOP proceeds high alternating selectivity AB-type copolymers that are thermally robust (Td,onset > 212 °C) and exhibit broad range glass-transition temperatures (Tg 60–145 °C). These polyesters amenable further postpolymerization functionalization. The hydroxy group sugar moiety can be unveiled, then functionalized further, e.g., phosphorylated. internal alkene some anhydride moieties also subject thiol-ene reactions. Combining those orthogonal strategies affords AB copolyesters functional substituents. By exploiting living character process, block have synthesized through sequential addition experiments.