Poly(lactic acid) (PLA) is a biodegradable polymer prepared by the catalyzed ring opening polymerization of lactide. An ideal catalyst should enable a sequential polymerization of the lactide enantiomers to afford stereoblock copolymers with predetermined number and lengths of blocks. We describe a magnesium based catalyst that combines very high activity with a true-living nature, which gives access to PLA materials of unprecedented microstructures. Full consumption of thousands of equivalents of L-LA within minutes gave PLLA of expected molecular weights and narrow molecular weight distributions. Precise PLLA-b-PDLA diblock copolymers having block lengths of up to 500 repeat units were readily prepared within 30 min, and their thermal characterization revealed a stereocomplex phase only with very high melting transitions and melting enthalpies. The one pot sequential polymerization was extended up to precise hexablocks having "dialed-in" block lengths.

Zinc complexes of {ONNN}-type sequential tetradentate monoanionic ligands reacted with diethylzinc to give the mononuclear ethylzinc complexes. The benzyloxy complexes were formed readily and were found to be highly active as well as living/immortal catalysts for ring-opening polymerization of rac-lactic acid with a clear isospecific inclination. Chiral gas chromatography analysis revealed a mild preference for a given lactide enantiomer by the chiral catalysts.

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.

The longest PLA stereo-diblock copolymer by one-pot synthesis.

Phenylene-salalens-sequential tetradentate dianionic {ONNO}-type ligands that include an ortho-phenylene group bridging between an imine and amine internal donors bound to phenol arms with a broad variety of substitution patterns are described. Zirconium and hafnium complexes of the type [{ONNO}M(O-tBu) ] were formed as single diastereomers, which, according to crystallographic structures, featured the fac(around the amine)-mer(around the imine) wrapping mode. The reactivity and stereoselectivity in rac-lactide (rac-LA) polymerizations were found to depend on the substitution pattern: complexes featuring small groups on the imine-side phenol and bulky groups on the amine-side phenol exhibited the favorable combination of high activity and high isoselectivity (P ≤0.91). Isotactic stereoblock copolymers of high molecular weights were prepared. The polymers crystallized in the stereocomplex phase according to thermal (differential scanning calorimetry) and crystallographic analysis.