Kinetic and Mechanistic Studies of <scp>l</scp>-Lactide Polymerization in Supercritical Chlorodifluoromethane

Abstract

The ring-opening polymerization of l-lactide (l-LA) initiated by 1-dodecanol/tin(II) octoate was carried out in supercritical chlorodifluoromethane at 110 °C under a pressure of 200 bar. MALDI-TOF mass spectroscopy and 1H NMR studies suggested that polymerization proceeded via a traditional coordination−insertion mechanism involving a tin alkoxide bond and the cleavage of the acyl−oxygen bond of the monomer. The polymerization was controlled using the linear relation between ln([LA]0/[LA]) on the polymerization time and the molecular weight on conversion. The relative polymerization rate constants increased with increasing tin(II) octoate and 1-dodecanol concentrations. Gel permeation chromatography analysis indicated that the molecular weight distribution was bimodal, at least for certain monomer conversion. The bimodal distribution may be a result of specific intermolecular interactions between chlorodifluoromethane and hydroxyl groups on 1-dodecanol or on dormant macromolecules. The mechanisms of the initiation and chain transfer steps of l-lactide polymerization in supercritical chlorodifluoromethane are proposed.