Stereogradient Poly(Lactic Acid) from meso-Lactide/L-Lactide Mixtures

The production of L-lactide from L-lactic acid involves a substantial formation of meso-lactide as an impurity, and, upon polymerization with the industrial catalyst tin octanoate, results in poly(L-lactic acid) of reduced crystallinity due to stereoerrors randomly distributed along the polymer chains. We describe a new approach wherein, instead of avoiding stereoerrors by removing the meso-lactide prior to polymerization, the stereoerrors in the polymer are tolerated, by crowding them in a stereogradient copolymer. A zirconium complex of an amine tris(phenolate) ligand is found to exhibit very high syndioselectivity in the ring opening polymerization catalysis of meso-lactide at room temperature, and gives rise to stereogradient copolymers in the polymerization of mixtures of meso-lactide/L-lactide in the melt at 180 °C. Relative to the stereo-random copolymers obtained with tin octanoate, the stereogradient copolymers exhibit enhanced crystallinities manifested in lower solubilities and higher melting temperatures and enthalpies.