Synthesis of tadpole-shaped copolyesters based on living macrocyclic poly(ɛ-caprolactone)

Synthesis of an asymmetric tadpole-shaped aliphatic copolyester consisting of a poly(ɛ-caprolactone) ring and two poly(l-lactide) tails was reported for the first time. First, a high molecular weight cyclic PCL macroinitiator (Mn = 31,000) was prepared by intramolecular photocross-linking of “living” chains. Polymerization of l-lactide was resumed by the tin dialkoxide containing macrocycles, thus making the targeted tadpole-shaped copolyester available. A preliminary investigation of the crystallization of these copolyesters was carried out by differential scanning calorimetry and polarized optical microscopy.