单（双）核铝络合物的合成及催化性能研究

发布时间：2018-01-15 02:05

  本文关键词：单（双）核铝络合物的合成及催化性能研究　出处：《大连理工大学》2014年硕士论文　论文类型：学位论文

  更多相关文章： β-酮亚胺 β-二酮亚胺 铝络合物 双核 ε-己内酯

【摘要】：聚己内酯(PCL)是性能优良的脂肪族聚酯,目前主要通过使用金属化合物催化己内酯的开环聚合制备。由于其具有良好的生物相容性,细胞可以在其基架上正常生长,并且具有可渗透性以及可降解性,因此在生物医学和制药工业中有着重要而广泛的应用前景。近年来,研究工作者不断开发出各种金属有机络合物,通过选择合适的金属和配体以实现己内酯高效、可控的聚合。尽管目前可用于催化ε-己内酯开环聚合反应的金属络合物种类繁多,但能实现高效、可控的催化体系还很少,并且多数催化剂并不稳定,部分催化体系不仅价格昂贵而且毒性较大,限制了其应用。因此研究开发低毒并且高效的催化体系,对促进聚己内酯的发展应用具有非常重要的意义。 本论文选用低毒性并且含量丰富的铝金属作为催化金属中心原子,合成了11个新N-烷基-β-酮亚胺和二酮亚胺铝络合物催化剂,并考察了其催化ε-己内酯开环聚合性能。具体实验结果如下：制备了一系列的β-酮亚胺铝络合物NacacR alEtCl(R=tBu,2a;iPr,2b;CH3,2c),β-二酮亚胺铝络合物NacnacR AlEtCl (R=tBu,3c;iPr,3d; Bn,3e), NacnacRAl(CH2SiMe3)Cl (R=tBu,4a;iPr,4b),和氧桥联双核铝络合物[NacnacR AlEt]2(μ-O)(R=tBu,5a;iPr,5b),[NacnaciPr AlCl]2(μ-O)(5c),这些络合物通过1H NMR,13C NMR, EI-MS进行了表征,其中络合物5a的分子结构通过X-单晶衍射进行了确定。实验结果证明这些铝络合物均可以催化ε-己内酯的开环聚合反应,其中络合物4a表现出最高的催化活性,在单体与催化剂摩尔浓度比例为100：1时,以甲苯为溶剂,在80℃条件下反应10分钟即可获得数均分子量为4.12×104,分子量分布(PDD为1.06的聚己内酯,单体转化率达到98%。
[Abstract]:Polycaprolactone (PCL) is a kind of aliphatic polyester with excellent properties. At present, it is mainly prepared by using metal compounds to catalyze the ring-opening polymerization of caprolactone, because of its good biocompatibility. Cells can grow normally on its base, and have permeability and degradability, so it has important and extensive application prospect in biomedicine and pharmaceutical industry in recent years. Researchers have been developing various organometallic complexes to achieve high efficiency of caprolactone by selecting suitable metal and ligand. Controlled polymerization. Although there are many kinds of metal complexes which can be used to catalyze the ring-opening polymerization of 蔚 -caprolactone, there are few catalytic systems which can achieve high efficiency and controllable, and most of the catalysts are unstable. Part of the catalytic system is expensive and toxic, which limits its application. Therefore, the research and development of low toxicity and high efficiency catalytic system is of great significance to promote the development and application of polycaprolactone. In this thesis, 11 new N- alkyl-尾-keto-imide and diketo-imine aluminum complex catalysts were synthesized by using low toxicity and abundant aluminum metal as the central atoms of the catalyst. The catalytic properties of 蔚 -caprolactone ring-opening polymerization were also investigated. The experimental results were as follows: a series of 尾 -keto-imide aluminum complexes, NacacR alEtCl-rtButBu2a, were prepared. IPRA 2b; Ch _ 3N _ 2c, 尾 -diketo-imine aluminum complex NacnacR AlEtCl ~ (3) C; IPrn 3 d; BNP 3e, NacnacRAl(CH2SiMe3)Cl TBU 4a; IPRA 4bN, and oxygen bridged binuclear aluminum complex [NacnacR AlEt. [The complexes were characterized by 1H NMR-13C NMRs, EI-MS. The molecular structure of the complex 5a was determined by X-ray diffraction. The experimental results show that these aluminum complexes can catalyze the ring-opening polymerization of 蔚 -caprolactone. The complex 4a showed the highest catalytic activity. Toluene was used as solvent when the molar ratio of monomer to catalyst was 100: 1. Poly (caprolactone) with a number average molecular weight of 4.12 脳 10 ~ 4 and a molecular weight distribution of 1.06 was obtained at 80 鈩，

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