碳链桥联的脒基—胺基金属化合物的合成、表征及应用研究

发布时间：2018-12-11 23:19

【摘要】：本论文涉及的工作是基于新型的限制几何构型(CGC)的含氮多齿配体化合物展开的,主要有:含苯基和SiMe3取代基的二胺、乙撑桥联的混合脒基-胺基化合物和丙撑桥联的混合脒基-胺基化合物。主要研究内容是:配体的合成,配体与无水过渡金属氯化盐或后过渡金属氯化盐的反应;对得到的一系列金属有机化合物进行结构表征;将所得IVB族金属有机化合物进行催化乙烯聚合性能研究;还研究了铁(钴)金属有机化合物的顺磁性。具体内容如下:第一章:导论——概述了与本论文研究内容有关的研究背景,包括:(1)几种重要的金属有机化合物的发展以及它们在有机合成和催化中的应用及发展研究;(2)限定几何构型(CGC)催化剂及其在烯烃聚合中的催化研究。第二章:合成了三种含SiMe3和Ph取代基的二胺配体(2a,2b,L1),以及三种碳链桥联的混合脒基-胺基配体化合物(L2,L3和L4),并通过X-ray、NMR和元素分析等对其结构进行了表征。第三章:以配体L1,L2为起始原料,分别与无水ZrCl4反应,合成了锆化合物3a-3d(Scheme 2,Scheme 3),并通过X-ray、NMR和元素分析等对其结构进行表征。在助催化剂MAO作用下,所得锆金属化合物3b对乙烯聚合的催化活性最高,为4.86×105 g PE mol-1(Zr)h-1。以配体化合物2a为起始原料,分别与ZrCl4和TiCl4(THF)2反应,合成了锆化合物3e和钛化合物3f(Scheme 4),也通过X-ray、NMR和元素分析等对其结构进行了表征。第四章:以配体L3为起始原料,分别与IVB族金属氯化物以及无水FeCl2反应,合成了IVB族金属化合物4a-4c以及亚铁化合物4d(Scheme 5)。还以配体2b为起始原料,与无水FeCl2反应合成了铁化合物4e,并通过X-ray、NMR和元素分析等对所得金属化合物结构进行了表征。在助催化剂MAO作用下,所得钛金属化合物4a对乙烯聚合的催化活性最高,为1.784×105 g PE mol-1(Ti)h-1,并且所得聚合物为具有超高分子量的高晶态、高线性聚乙烯。在室温下,顺磁性铁化合物4d(FeII)和4e(FeIII)的磁化率随磁场强度的变化呈“S”曲线,这表明二者都是超顺磁性物质。第五章:以配体2a为起始原料,与无水MCl2(M=Fe,Co,Ni)反应合成了后过渡金属化合物5a,5c,5d(Scheme 7);以配体L2为起始原料,与无水Fe Cl2反应,合成了亚铁化合物5b(Scheme 8),并通过元素分析对所得金属化合物结构进行表征。在室温下,顺磁性后过渡金属化合物5a-5c的磁化率随磁场强度的变化呈“S”曲线,这表明5a-5c都是超顺磁性物质。在氯化合物5d中,氯化镍催化了碳碳偶联,并形成两个五元杂环桥联的新结构,镍化合物中生成了为桥联杂环化合物的合成提供新方法及新思路。
[Abstract]:The work involved in this thesis is based on a new type of nitrogen-containing polydentate ligand with restricted geometric configuration (CGC), which mainly consists of diamines containing phenyl and SiMe3 substituents. Ethylene-bridged mixed amidine-amino compounds and propyl-bridged miramidine-amino compounds. The main research contents are as follows: synthesis of ligand, reaction of ligand with anhydrous transition metal chloride or post-transition metal chloride, structure characterization of a series of organometallic compounds. The catalytic properties of IVB group organometallic compounds for ethylene polymerization were studied, and the paramagnetic properties of Fe (Co) organometallic compounds were also studied. The main contents are as follows: chapter 1: introduction: the research background related to this thesis is summarized, including: (1) the development of several important organometallic compounds and their application and research in organic synthesis and catalysis; (2) (CGC) catalysts with limited geometry and their catalytic properties in olefin polymerization. In chapter 2, three diamine ligands containing SiMe3 and Ph substituents (2aan2bhl 1) and three carbon-chain bridged mixed amidinyl ligands (L _ 2o _ L _ 3 and L _ 4) were synthesized and synthesized by X-ray. The structure was characterized by NMR and elemental analysis. Chapter 3: the zirconium compound 3a-3d (Scheme _ 2 Scheme _ 3) was synthesized from ligand L _ 1C _ L _ 2 as starting material and reacted with anhydrous ZrCl4 respectively. The structure of the compound was characterized by X-rayne NMR and elemental analysis. The obtained zirconium metal compound 3b has the highest catalytic activity for ethylene polymerization under the co-catalyst MAO, which is 4.86 脳 105g PE mol-1 (Zr) h-1. Zirconium 3e and titanium 3f (Scheme _ 4) were synthesized from ligand 2a and reacted with ZrCl4 and TiCl4 (THF) _ 2, respectively. Their structures were characterized by X-ray NMR and elemental analysis. Chapter 4: using ligand L3 as starting material, IVB group metal compounds 4a-4c and ferrous compounds (Scheme 5) were synthesized by reaction with IVB group metal chloride and anhydrous FeCl2, respectively. Iron compounds 4e were synthesized from ligand 2b and reacted with anhydrous FeCl2. The structure of the metal compounds was characterized by X-ray NMR and elemental analysis. Under the action of co-catalyst MAO, the titanium metal compound 4a has the highest catalytic activity for ethylene polymerization, which is 1.784 脳 105g PE mol-1 (Ti) h-1, and the obtained polymer is high-crystalline, high-linear polyethylene with ultra-high molecular weight. At room temperature, the magnetic susceptibility of the paramagnetic iron compounds 4d (FeII) and 4e (FeIII) show a "S" curve with the magnetic field intensity, which indicates that both of them are superparamagnetic materials. Chapter 5: the post-transition metal compound (Scheme 7) was synthesized by the reaction of ligand 2a with anhydrous MCl2. Ferrous compound 5b (Scheme 8) was synthesized from ligand L2 and reacted with anhydrous Fe Cl2. The structure of the obtained metal compound was characterized by elemental analysis. At room temperature, the magnetic susceptibility of the transition metal compound 5a-5c after paramagnetism shows a "S" curve with the change of the magnetic field intensity, which indicates that 5a-5c is a superparamagnetic material. Nickel chloride catalyzes carbon-carbon coupling in chloride compounds for 5 days and forms a new structure of two quaternary heterocyclic bridges. The formation of nickel compounds provides a new method and new ideas for the synthesis of bridged heterocyclic compounds.
【学位授予单位】：山西大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O641.4

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