Macromolecular engineering of polylactones and polylactides - I. End-functionalization of poly e{open}- caprolactone

Aluminum alkoxides carrying functional alkoxy groups are effective initiators for the e{open}-caprolactone polymerization in toluene and tetrahydrofuran. The coordination-insertion type of polymerization is living and yields exclusively linear polyesters of a predictable molecular weight with a narrow molecular weight distribution within the period of time required for the total monomer conversion. The functional group associated to the active alkoxy group of the initiator is selectively attached to one chain-end, and the second end-group is systematically a hydroxyl function resulting from the hydrolysis of the living growing site. Asymmetric telechelic polyesters are thus obtained in a perfectly controlled way, including macromonomers. Beside (meth)acrylic double bond, the functional end-group derived from the initiator can be, for instance, an unsaturation, a halogen and a tert-amine. Coupling the asymmetric telechelic polymer via the OH end-group (or the precursor Al alkoxide end-group) is a direct way to the related symmetric telechelic of a twofold increased molecular weight. © 1989 Springer-Verlag.