A Highly Active Zinc Catalyst for the Controlled Polymerization of Lactide

We report the preparation, structural characterization, and detailed lactide polymerization behavior
of a new Zn(II) alkoxide complex, (L1ZnOEt)2 (L1 = 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 L1ZnOEt
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 Mn 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 L1ZnOEt to be distinguished and the empirical rate law
to be elucidated, −d[LA]/dt = kp[L1ZnOEt][LA]. These studies also showed that L1ZnOEt 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.