Block–Stereoblock Copolymers of Poly(ϵ‐Caprolactone) and Poly(Lactic Acid)

Abstract

Abstract A magnesium complex of the type {ONNN}Mg‐HMDS wherein {ONNN} is a sequential tetradentate monoanionic ligand is introduced. In the presence of an alcohol initiator this complex catalyzes the living and immortal homopolymerization of the lactide enantiomers and ϵ‐caprolactone at room‐temperature with exceptionally high activities, as well as the precise block copolymerization of these monomers in a one‐pot synthesis by sequential monomer addition. Copolymers of unprecedented microstructures such as the PCL‐b‐PLLA‐b‐PDLA and PDLA‐b‐PLLA‐b‐PCL‐b‐PLLA‐b‐PDLA block–stereoblock microstructures that feature unique thermal properties are readily accessed.