A magnesium complex of the type ONNNMg-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.
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