五元含N,O,S杂环亚胺基过渡金属聚烯烃催化剂的合成及表征
发布时间：2019-03-07 09:48
【摘要】：自从Brookhart合成出经典的吡啶双亚胺后过渡金属烯烃聚合催化剂并将其应用在烯烃聚合方面以来,由于其高效的催化活性,逐渐地受到越来越多的关注。这种类型的后过渡金属催化剂中,配体的共扼结构和侧链取代基的大位阻成为烯烃聚合高活性的关键。因此,该领域的研究大多数主要集中在其配体结构的调整和改变方面。本论文主要以Brookhart型后过渡金属双亚胺吡啶配体为模型,从电子效应和位阻效应等方面对其配体进行修饰和改变,从而开发新型的五元杂环类烯烃聚合催化体系,并将合成的催化剂应用于乙烯聚合实验中检测其催化性能。其主要工作如下:1.分别以2-乙酰基吡咯、2-乙酰基噻吩和2-乙酰基呋喃作为前驱体与一系列苯胺及其衍生物在微波辐射下进行席夫碱缩合反应,得到新型的吡咯单亚胺配体、噻吩单亚胺配体以及呋喃单亚胺配体。然后,对所合成的部分配体进行核磁,红外以及元素分析等表征,并通过X-射线单晶衍射确定配体的晶体结构。利用结构表征的数据对三大系列配体的分子空间结构进行分析,同时对这类席夫碱缩合反应的反应机理进行探讨。2.利用合成的吡咯,噻吩及呋喃单亚胺配体分别与过渡金属盐Ni(II)的氯化物发生反应,使之形成相应的后过渡金属配合物。通过实验结果发现,吡咯单亚胺能与NiCl_2反应生成新型的镍配合物,配合物的晶体结构经X-射线单晶衍射表征证实为预期化合物。利用结构表征的数据对吡咯单亚胺镍配合物的分子空间结构进行深入探讨。同时,在液相反应和水热反应的条件下分别探索噻吩单亚胺、呋喃单亚胺配体与过渡金属盐Ni(II)氯化物的反应,但是反应均未发生。我们认为当呋喃单亚胺或噻吩单亚胺配体单独存在时,五元环中的氧原子和硫原子是很差的氢键供体。因此,在液相反应和水热合成中其与金属Ni(II)氯化物很难发生配位得到相应的配合物。3.在温度为20℃,压强为0.5MPa下,对合成的吡咯亚胺类后过渡金属配合物(1d,2d,4d,5d,10d)进行烯烃聚合实验。反应结束后,溶液为淡黄色澄清溶液。然后,对其进行GC-MS表征检测发现,这类配合物对乙烯具有齐聚作用,同时其催化活性在1.83~4.23kg·mol~(-1)(Ni)·h~(-1)之间。其中1d,2d都对C_6有较高的选择性;4d,5d都对C_8有较高的选择性;而10d则对C_4具有较高的选择性。
[Abstract]:Since Brookhart synthesized the classical transition metal olefin polymerization catalyst after pyridine diimine and applied it to olefin polymerization, more and more attention has been paid to it because of its high catalytic activity. In this type of post-transition metal catalysts, the conjugation structure of ligands and the large resistance of side chain substituents are the keys to the high activity of olefin polymerization. Therefore, most of the research in this field focuses on the adjustment and change of its ligand structure. In this thesis, the Brookhart type post-transition metal diimine pyridine ligand was used as a model to modify and change its ligand from the aspects of electron effect and steric resistance effect, so as to develop a novel catalytic system for the polymerization of five-membered heterocyclic olefins. The synthesized catalyst was applied to the ethylene polymerization experiment to test its catalytic performance. Its main work is as follows: 1. Using 2-acetylpyrrole, 2-acetyl thiophene and 2-acetyl furan as precursors, a series of aniline and its derivatives were synthesized by Schiff base condensation reaction under microwave irradiation, and a novel pyrrolidine ligand was obtained by the condensation of 2-acetylpyrrolidine, 2-acetyl thiophene and 2-acetyl furan under microwave irradiation. Thiophene monoimine ligand and furan monoimine ligand. Then, the synthesized ligands were characterized by NMR, IR and elemental analysis. The crystal structure of the ligands was determined by X-ray single crystal diffraction. The molecular spatial structure of three series of ligands was analyzed by using the data of structural characterization, and the reaction mechanism of the Schiff base condensation reaction was also discussed. 2. The synthesized pyrrole thiophene and furanmonimine ligands reacted with the chloride of the transition metal salt Ni (II) respectively to form the corresponding post-transition metal complexes. The results show that pyrrolidine can react with NiCl_2 to form a new nickel complex. The crystal structure of the complex is confirmed to be expected by X-ray single crystal diffraction. The molecular spatial structure of pyrrolidine monoimine nickel complexes was studied by using the data of structure characterization. At the same time, the reaction of thiophene monoimine, furan monoimine ligand and transition metal salt Ni (II) chloride under the conditions of liquid phase reaction and hydrothermal reaction were studied respectively, but none of the reactions took place. We consider that the oxygen and sulfur atoms in the five-membered ring are poor hydrogen-bonded donors when the furan monoimine or thiophene monoimine ligand exists alone. Therefore, it is difficult to coordinate with metal Ni (II) chloride in liquid phase reaction and hydrothermal synthesis to obtain corresponding complexes. The olefin polymerization of pyrrolidine post-transition metal complexes (1 d, 2 d, 4 d, 5 d, 10 d) was carried out at 20 鈩，
本文编号：2436006
[Abstract]:Since Brookhart synthesized the classical transition metal olefin polymerization catalyst after pyridine diimine and applied it to olefin polymerization, more and more attention has been paid to it because of its high catalytic activity. In this type of post-transition metal catalysts, the conjugation structure of ligands and the large resistance of side chain substituents are the keys to the high activity of olefin polymerization. Therefore, most of the research in this field focuses on the adjustment and change of its ligand structure. In this thesis, the Brookhart type post-transition metal diimine pyridine ligand was used as a model to modify and change its ligand from the aspects of electron effect and steric resistance effect, so as to develop a novel catalytic system for the polymerization of five-membered heterocyclic olefins. The synthesized catalyst was applied to the ethylene polymerization experiment to test its catalytic performance. Its main work is as follows: 1. Using 2-acetylpyrrole, 2-acetyl thiophene and 2-acetyl furan as precursors, a series of aniline and its derivatives were synthesized by Schiff base condensation reaction under microwave irradiation, and a novel pyrrolidine ligand was obtained by the condensation of 2-acetylpyrrolidine, 2-acetyl thiophene and 2-acetyl furan under microwave irradiation. Thiophene monoimine ligand and furan monoimine ligand. Then, the synthesized ligands were characterized by NMR, IR and elemental analysis. The crystal structure of the ligands was determined by X-ray single crystal diffraction. The molecular spatial structure of three series of ligands was analyzed by using the data of structural characterization, and the reaction mechanism of the Schiff base condensation reaction was also discussed. 2. The synthesized pyrrole thiophene and furanmonimine ligands reacted with the chloride of the transition metal salt Ni (II) respectively to form the corresponding post-transition metal complexes. The results show that pyrrolidine can react with NiCl_2 to form a new nickel complex. The crystal structure of the complex is confirmed to be expected by X-ray single crystal diffraction. The molecular spatial structure of pyrrolidine monoimine nickel complexes was studied by using the data of structure characterization. At the same time, the reaction of thiophene monoimine, furan monoimine ligand and transition metal salt Ni (II) chloride under the conditions of liquid phase reaction and hydrothermal reaction were studied respectively, but none of the reactions took place. We consider that the oxygen and sulfur atoms in the five-membered ring are poor hydrogen-bonded donors when the furan monoimine or thiophene monoimine ligand exists alone. Therefore, it is difficult to coordinate with metal Ni (II) chloride in liquid phase reaction and hydrothermal synthesis to obtain corresponding complexes. The olefin polymerization of pyrrolidine post-transition metal complexes (1 d, 2 d, 4 d, 5 d, 10 d) was carried out at 20 鈩，
本文编号：2436006
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