Sittichoke TabthongTanin NanokPattarawut SumritPalangpon KongsaereeSamran PrabpaiPitak ChuawongPimpa HormnirunKasetsart UniversityMahidol University2018-11-232018-11-232015-09-30Macromolecules. Vol.48, No.19 (2015), 6846-686115205835002492972-s2.0-84944077652https://repository.li.mahidol.ac.th/handle/20.500.14594/35734© 2015 American Chemical Society. A series of bis(pyrrolidene) Schiff base aluminum complexes (1-7) were synthesized and characterized by NMR spectroscopy and elemental analysis. All complexes were efficient initiators for the ring-opening polymerizations of l-LA and rac-LA in toluene at 70 °C. Kinetic studies revealed first-order kinetics in monomer and the rates of l-LA and rac-LA polymerizations decreased in the order of 1,2-benzylene (4) 蠑 1,3-propylene (2) > 2,2-dimethyl-1,3-propylene (3) > 1,4-butylene (5) > rac-1,2-cyclohexylene (7) > 1,2-ethylene (1) 蠐 1,2-phenylene (6). Microstructure analyses of the resulting polylactides by homonuclear decoupled1H NMR spectroscopy disclosed the isotactic-biased stereocontrol of all synthesized complexes, except 5. Isotactic stereoblock polylactide with a high Pmvalue of 0.80 was produced by 3. A systematic DFT study on the rac-lactide ring-opening mechanism initiated by the initiators synthesized in this study revealed the correlation between the structure of backbone linker and the polymerization activity and stereoselectivity.Mahidol UniversityChemistryMaterials ScienceArticleSCOPUS10.1021/acs.macromol.5b01381