Highly Isoselective Ring-Opening Polymerization of rac-Lactide Using Chiral Binuclear Aluminum Catalyst.

The microstructure can significantly affect the physical and mechanical properties of polymers. Five chiral binuclear aluminum methyl complexes (rac1 to rac5) are synthesized by using chiral binaphthalene diamine ligand and characterized by both 1 H and 13 C NMR spectroscopy. The crystal structures of rac3 and rac5 are also identified by single crystal X-ray diffraction. In the presence of i PrOH initiator, these aluminum complexes catalyze the ring-opening polymerization (ROP) of rac-lactide (rac-LA) in a controlled manner and produce polymers with high to excellent isoselectivity (Pm up to 0.93). Even with a catalyst loading as low as 0.1%, polylactide with a Pm of 0.83 can still be obtained. Kinetic studies reveal the first-order dependence on monomer concentration whereas kinetic resolution polymerization provides the evidence to support that these binuclear aluminum catalysts catalyzed ROP of rac-LA adopts enantiomorphic site control mechanism. Furthermore, this strategy can also be applied to the ROP of both ε-caprolactone and δ-valeroactone.