A Versatile Step-Growth Polymerization Route to Functional Polyesters from an Activated Diester Monomer.

This work describes a versatile and efficient condensation polymerization route to aliphatic polyesters by organo-catalyzed (4-dimethylaminopyridine) transesterification reactions between an activated pentafluorophenyl-diester of adipic acid and structurally different diols. By introducing "monofunctional impurity" or "stoichiometric imbalance," this methodology can afford well-defined end-functionalized polyesters with predictable molecular weights and narrow dispersity under mild conditions without any necessity for the removal of the byproducts to accelerate the polymerization reaction, which remains a major challenge in conventional polyester synthesis with non-activated diesters. Wide substrate scope with structurally different monomers and the synthesis of block copolymers by chain extension following either ring-opening polymerization or controlled radical polymerization have been successfully demonstrated. Some of the polyesters synthesized by this newly introduced approach show high thermal stability, crystallinity, and enzymatic degradation in aqueous environments.