五元含N,O,S雜環(huán)亞胺基過渡金屬聚烯烴催化劑的合成及表征
發(fā)布時(shí)間：2019-03-07 09:48
【摘要】：自從Brookhart合成出經(jīng)典的吡啶雙亞胺后過渡金屬烯烴聚合催化劑并將其應(yīng)用在烯烴聚合方面以來(lái),由于其高效的催化活性,逐漸地受到越來(lái)越多的關(guān)注。這種類型的后過渡金屬催化劑中,配體的共扼結(jié)構(gòu)和側(cè)鏈取代基的大位阻成為烯烴聚合高活性的關(guān)鍵。因此,該領(lǐng)域的研究大多數(shù)主要集中在其配體結(jié)構(gòu)的調(diào)整和改變方面。本論文主要以Brookhart型后過渡金屬雙亞胺吡啶配體為模型,從電子效應(yīng)和位阻效應(yīng)等方面對(duì)其配體進(jìn)行修飾和改變,從而開發(fā)新型的五元雜環(huán)類烯烴聚合催化體系,并將合成的催化劑應(yīng)用于乙烯聚合實(shí)驗(yàn)中檢測(cè)其催化性能。其主要工作如下:1.分別以2-乙�；量�、2-乙�；绶院�2-乙�；秽鳛榍膀�(qū)體與一系列苯胺及其衍生物在微波輻射下進(jìn)行席夫堿縮合反應(yīng),得到新型的吡咯單亞胺配體、噻吩單亞胺配體以及呋喃單亞胺配體。然后,對(duì)所合成的部分配體進(jìn)行核磁,紅外以及元素分析等表征,并通過X-射線單晶衍射確定配體的晶體結(jié)構(gòu)。利用結(jié)構(gòu)表征的數(shù)據(jù)對(duì)三大系列配體的分子空間結(jié)構(gòu)進(jìn)行分析,同時(shí)對(duì)這類席夫堿縮合反應(yīng)的反應(yīng)機(jī)理進(jìn)行探討。2.利用合成的吡咯,噻吩及呋喃單亞胺配體分別與過渡金屬鹽Ni(II)的氯化物發(fā)生反應(yīng),使之形成相應(yīng)的后過渡金屬配合物。通過實(shí)驗(yàn)結(jié)果發(fā)現(xiàn),吡咯單亞胺能與NiCl_2反應(yīng)生成新型的鎳配合物,配合物的晶體結(jié)構(gòu)經(jīng)X-射線單晶衍射表征證實(shí)為預(yù)期化合物。利用結(jié)構(gòu)表征的數(shù)據(jù)對(duì)吡咯單亞胺鎳配合物的分子空間結(jié)構(gòu)進(jìn)行深入探討。同時(shí),在液相反應(yīng)和水熱反應(yīng)的條件下分別探索噻吩單亞胺、呋喃單亞胺配體與過渡金屬鹽Ni(II)氯化物的反應(yīng),但是反應(yīng)均未發(fā)生。我們認(rèn)為當(dāng)呋喃單亞胺或噻吩單亞胺配體單獨(dú)存在時(shí),五元環(huán)中的氧原子和硫原子是很差的氫鍵供體。因此,在液相反應(yīng)和水熱合成中其與金屬Ni(II)氯化物很難發(fā)生配位得到相應(yīng)的配合物。3.在溫度為20℃,壓強(qiáng)為0.5MPa下,對(duì)合成的吡咯亞胺類后過渡金屬配合物(1d,2d,4d,5d,10d)進(jìn)行烯烴聚合實(shí)驗(yàn)。反應(yīng)結(jié)束后,溶液為淡黃色澄清溶液。然后,對(duì)其進(jìn)行GC-MS表征檢測(cè)發(fā)現(xiàn),這類配合物對(duì)乙烯具有齊聚作用,同時(shí)其催化活性在1.83~4.23kg·mol~(-1)(Ni)·h~(-1)之間。其中1d,2d都對(duì)C_6有較高的選擇性;4d,5d都對(duì)C_8有較高的選擇性;而10d則對(duì)C_4具有較高的選擇性。
[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，
本文編號(hào)：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，
本文編號(hào)：2436006
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