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Polylactides and related materials have been widely used in many applications due to their unique biodegradability and biocompatibility. Ring-opening polymerization initiated by aluminum complexes constitute the most effective and versatile synthetic strategy for preparing polylactides with a wide range of physical, mechanical, and degradation properties. Over the past decade, several aluminum species with N,O-donor ligands have been found to be particularly efficient as ring-opening polymerization catalysts. In the course of this work a series of pyridine-containing tridentate ligands have been synthesized. Reaction of these ligands with AlMe3 yields the aluminum complexes (1−3). The crystal structure of the compound 1 was studied by X-ray analysis. The compounds obtained are under investigation of their catalytic activity in ring-opening polymerization of cyclic esters (D,L-lactide, ε-caprolactone).