In this work, the organocatalytic strategy for the ring-opening copolymerization (ROCOP) of 3,5-anhydro-D-xylose oxetane 1 and various anhydrides has been demonstrated by use of phosphazene base (P1) and triethyl borane (TEB).The ROCOP proceeds efficiently to generate sugar-derived polyesters with perfectly alternating sequence distribution, controlled molar masses, and moderate dispersity. These polyesters show good thermal stability (T max > 320 C) and adjustable glass transition temperatures (T g 70 $ 110 C) with the variation of anhydrides. This work provides efficient organocatalyst for the selective copolymerization for biomass-derived degradable polyesters.

Ring-opening alternating copolymerization (ROAC) has been an attractive strategy for polyester synthesis recently. To date, the ROAC catalysts are restricted to organometallics and organic super-bases. In this work, we report...