探究烯醇及胺基配合物的制备方法及其催化性能

发布时间：2018-06-28 02:54

本文选题：镁配合物 + 开环聚合　；参考：《山西大学》2017年硕士论文

【摘要】：近年来,白色污染等环境问题日益困扰着人们的生活,为了解决这一问题,具有可降解性的、生物相容性的以及无毒的这种新型的聚酯高分子材料成为科研工作者关注研究的热点,这些高分子材料取代传统的不可降解材料而具有很大的经济效益以及社会效益。随之产生的运用金属配合物作为催化剂进行开环聚酯的研究也取得了较高的成就,能够较好的控制聚合物的分子量,分子量分布也较窄。镁是人体必须的元素,无毒性。同时镁金属配合物催化活性好,对于己内酯或是丙交酯的开环聚合具有较好的可控性,所以我们尝试合成含有N,O配位点这种结构的对有机体无害金属配合物进行开环聚合,并通过改变配体的取代基实现结构不同来合成具有不同催化性能的催化剂。本课题组长期主要研究的是以各种吡啶为母体的N,O和N,N双齿金属络合物的合成以及这些金属络合物对环酯的开环聚合的研究。本论文主要分为三部分:第一章:序论部分。主要概括叙述了可降解的聚酯材料如PCL和PLA的研究发展现状以及N,O配位的配体的锌镁铝金属配合物对环酯的开环聚合的应用。第二章:以2-甲基和乙基吡啶为原料,经过锂化,与几种无α-H的腈发生加成消除反应,经过酸性水解、中和、萃取、蒸馏收集到配体化合物,继续和正丁基镁发生反应,合成相应的金属镁配合物,并利用核磁、元素分析和X单晶衍射仪对配合物进行结构表征,同时研究了这些金属镁配合物对ε-CL的开环聚合的催化性能。此外研究了金属锆化合物对乙烯的催化聚合。第三章:以2-甲基吡啶为原料,经锂化,后与苯腈反应,经硫酸水解,氢氧化钠中和,萃取提纯后得到一种二聚体的配体。然后与对苯二甲腈反应,得到桥联的[N,O,N,O]的四齿配体。8-甲基喹啉与丁基锂的反应,带有负电荷的丁基首先进攻缺电子的吡啶环,发生亲核加成反应。并对这些化合物进行核磁、以及X-ray单晶衍射的分析。
[Abstract]:In recent years, environmental problems such as white pollution have increasingly troubled people's lives. In order to solve this problem, it has biodegradability. Biocompatible and nontoxic polyester polymer materials have become the focus of scientific research. They have great economic and social benefits instead of traditional non-degradable materials. The study of ring opening polyester using metal complexes as catalyst has made great achievements, which can better control the molecular weight of polymer and narrow the molecular weight distribution. Magnesium is an essential element in the body and is non-toxic. At the same time, magnesium metal complexes have good catalytic activity and can be controlled for the ring-opening polymerization of caprolactone or lactide. The catalysts with different catalytic properties were synthesized by changing the substituents of ligands. For a long time, our group mainly studied the synthesis of Nino and N didentate metal complexes with pyridine as parent and the ring opening polymerization of cyclic esters by these metal complexes. This paper is divided into three parts: the first chapter: the preface part. The research and development of degradable polyester materials, such as PCL and PLA, and the application of zinc, magnesium, aluminum and metal complexes of Nano O ligands to ring opening polymerization of cycloesters are reviewed. In chapter 2, ligand compounds were collected from 2-methylpyridine and ethylpyridine by lithiation, and then reacted with 伪 -H free nitriles. The ligands were collected by acid hydrolysis, neutralization, extraction and distillation. The corresponding metal magnesium complexes were synthesized and characterized by NMR, elemental analysis and X-ray diffraction. The catalytic properties of these complexes for ring-opening polymerization of 蔚 -CL were also studied. In addition, the catalytic polymerization of ethylene with zirconium compounds was studied. In chapter 3, a ligand of dimer was obtained by lithiation of 2-methylpyridine, reaction with benzonitrile, hydrolysis with sulfuric acid, neutralization with sodium hydroxide, extraction and purification. The bridged tetradentate ligand. 8-methylquinoline reacted with lithium Ding Ji. The negatively charged Ding Ji first attacked the electron-deficient pyridine ring and the nucleophilic addition reaction took place. These compounds were analyzed by nuclear magnetic field and X-ray single crystal diffraction.
【学位授予单位】：山西大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4

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