Use of pyrazoles as ligands greatly enhances the catalytic activity of titanium iso-propoxide for the ring-opening polymerization of l-lactide: a cooperation effect

Abstract

Using TiOⁱPr₄ with a pyrazole ligand for one-pot LA polymerization improved catalytic activity compared with using TiOⁱPr₄ only. At 60 °C, TiOⁱPr₄ with ^furPz exhibited a higher catalytic activity (approximately 3-fold) than TiOⁱPr₄. At room temperature, TiOⁱPr₄ with ^BuPz exhibited a higher catalytic activity (approximately 17-fold) than TiOⁱPr₄. High molecular mass PLA (M_nGPC = 51 100, and Đ = 1.10) could be produced by using TiOⁱPr₄ with ^furPz in melt polymerization ([TiOⁱPr₄] : [^furPz] = 1000 : 1 : 1 at 100 °C, 240 min). The crystal structure of ^MePz₂Ti₂OⁱPr₇ revealed the cooperative activation between two Ti atoms during LA polymerization.