Tetradentate iminophenolate copper complexes in rac-lactide polymerization

Abstract

Copper(II) nitrate complexes of 2-(((2-((2-aminoethyl)amino)ethyl)imino)methyl)phenol, 2-(((2-((2-aminoethyl)amino)ethyl)imino)methyl)-4,6-dichlorophenol, 2-(((2-(piperazin-1-yl)ethyl)imino)methyl)phenol and (2,4-di-tert-butyl-6-(((2-(piperazin-1-yl)ethyl)imino)methyl)phenol, as well as a copper(II) acetate complex of 2-(((2-(piperidin-1-yl)ethyl)imino)methyl)phenol, have been prepared and characterized by X-ray diffraction studies. In combination with benzyl alcohol, all complexes are active in rac-lactide polymerization at 140 °C in molten monomer to provide moderately heterotactic polylactic acid. Most complexes showed complicated reaction kinetics, indicative of two interconverting active species. Molecular weight control was poor and a strong tendency toward intramolecular transesterification led to oligomeric products. There was no indication that the basic site of the ligand is participating in the polymerization reaction by deprotonation of the alcohol nucleophile.