• biopolymers;
  • catalysis;
  • cationic polymerization;
  • ring-opening polymerization;
  • polyesters


Binaphthyl-diyl hydrogen phosphate has been assessed for the first time as a catalyst for the ring-opening polymerization of ε-caprolactone (CL) and δ-valerolactone (VL). In the presence of benzyl alcohol as coinitiator at 40–60 °C, the polymerization is quantitative and controlled both in terms of dispersity and of number-average molecular weight corresponding to the monomer/initiator ratio. The use of a selectively protected D-glucose derivative bearing the primary C6 hydroxyl group as initiator leads to the quantitative end-functionalization of the polyesters in rather short reaction times (ca. 10 min at 60 °C for δ-VL) with dispersities around 1.08–1.10. Methyl-α-D-glucopyranoside has been used as a carbohydrate polyol initiator in bulk. The initiation efficiency is partial, leading to hydrophilic carbohydrates functionalized polylactones in a one-step procedure. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013