Department of Chemistry, University of Bath, Claverton Down, Bath, UKBA2 7AY.
Dalton Trans. 2011 Nov 21;40(43):11469-73. doi: 10.1039/c1dt11438g. Epub 2011 Sep 20.
In this paper we report the first use of Al(III) salalen complexes for the ring opening polymerisation of rac-lactide. Polylactides with narrow polydispersities (PDIs range from 1.04-1.65) and moderate degrees of stereoselectivity were formed. Eight salalen Al(III) complexes have been prepared and fully characterised by solution-state NMR spectroscopy and, where appropriate, single crystal X-ray diffraction. With ligand 3H(2) either a monomeric or dimeric Al(III) species was formed, the dimeric species was favoured at low concentrations. The complexes were tested for the ring opening polymerisation of rac-lactide in toluene at 80 or 100 °C. Interestingly, various tacticities of polymer were formed, which were dependent upon the nature of the group bound to the amine nitrogen centre.
在本文中,我们报告了首例使用 Al(III) salalen 配合物开环聚合 rac-丙交酯的情况。聚合产物的相对分子质量分布较窄(PDI 范围为 1.04-1.65),且具有中等程度的立构选择性。我们共制备了 8 种 salalen Al(III)配合物,并通过溶液态 NMR 光谱对其进行了全面表征,对于适当的配合物还进行了单晶 X 射线衍射分析。在配体 3H(2)存在时,形成了单体或二聚体的 Al(III)物种,而在低浓度下更有利于形成二聚体。我们还在 80 或 100°C 的甲苯中测试了这些配合物对 rac-丙交酯的开环聚合反应。有趣的是,形成了各种不同立构规整性的聚合物,这取决于与胺氮中心键合的基团的性质。