Journal of the American Chemical Society vol. 125, no. 37, pp. 11350 - 11359
Indexed
SCI; SCIE; SCOPUS
Document Type
Article
Abstract
We report the preparation, structural characterization, and detailed lactide polymerization behavior of a new ZN(II) alkoxide complex, (L 1ZnOEt) 2 (L 1 = 2,4-di-tert-butyl-6-{[(2′ -dimethylaminoethyl)methylamino]-methyl}phenolate). While an X-ray crystal structure revealed the complex to be dimeric in the solid state, nuclear magnetic resonance and mass spectrometric analyses showed that the monomeric form L 1ZnOEt predominates in solution. The polymerization of lactide using this complex proceeded with good molecular weight control and gave relatively narrow molecular weight distribution polylactide, even at catalyst loadings of <0.1% that yielded M n as high as 130 kg mol -1. The effect of impurities on the molecular weight of the product polymers was accounted for using a simple model. Detailed kinetic studies of the polymerization reaction enabled integral and nonintegral orders in L 1ZnOEt to be distinguished and the empirical rate law to be elucidated, -d[LA]/dt = K p[L 1ZnOEt][LA]. These studies also showed that L 1ZnOEt polymerizes lactide at a rate faster than any other Zn-containing system reported previously. This work provides important mechanistic information pertaining to the polymerization of lactide and other cyclic esters by discrete metal alkoxide complexes.