Macromolecular engineering of polylactones and polylactides. X. Selective end‐functionalization of poly(D,L)‐lactide

Functional aluminum alkoxides, such as Et3–pAl(OCH2X)p, where p = 1,3 and X = a functional group, are very effective initiators for the (D, L)‐lactide polymerization in toluene at 70°C. The coordination‐insertion type of polymerization is living. Linear polyesters of a predictable molecular weight and a narrow molecular weight distribution are obtained within the period of time required for the total monomer conversion. The functional group (X) associated with the active alkoxy group of the initiator is selectively and quantitatively attached to one chain end, whereas the second end group is systematically a hydroxyl function resulting from the hydrolysis of the living growing site. Asymmetric telechelic polylactides are thus obtained in a perfectly controlled way. A kinetic study has shown that the polymerization is first order in both the monomer and initiator. © 1993 John Wiley & Sons, Inc. Copyright © 1993 John Wiley & Sons, Inc.