Asymmetric diimine pyridine iron or cobalt complex catalyst, and preparation method and application thereof

A technology of iron diimide pyridine and complexes, applied in the direction of iron organic compounds, cobalt organic compounds, etc., can solve problems such as limiting metal catalysts, and achieve the effects of high catalytic activity, high molecular weight, and strong tolerance

Active Publication Date: 2012-05-23
INST OF CHEM CHINESE ACAD OF SCI
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  • Abstract
  • Description
  • Claims
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  • Asymmetric diimine pyridine iron or cobalt complex catalyst, and preparation method and application thereof
  • Asymmetric diimine pyridine iron or cobalt complex catalyst, and preparation method and application thereof
  • Asymmetric diimine pyridine iron or cobalt complex catalyst, and preparation method and application thereof

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Experimental program
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Effect test

Embodiment 1

[0057] Embodiment 1, preparation complex Fe3 (in formula I, R1=i-Pr; R2=H; M=Fe)

[0058] 1. Preparation of 2-acetyl-6-(1-(2,6-benzhydryl-4-methylaniline) ethyl)pyridine: in 2,6-benzhydryl-4-methyl Toluene (60mL) solution of phenylaniline (3.48g, 8mmol) and 2,6-diacetylpyridine (1.30g, 4mmol) was added with catalyst equivalent (0.15g) of p-toluenesulfonic acid, and the reaction was refluxed for 6h. The solvent was removed, and the residue was subjected to alumina column chromatography with a mixed solvent of petroleum ether and ethyl acetate at a volume ratio of 20:1. Mixed solvent of ether and ethyl acetate, the fraction with Rf value of 1 / 2-1 / 3 (ie the second fraction) was collected, and the solvent was removed to obtain a yellow solid. Yield: 44%. Melting point: 134-136°C.

[0059] The structure confirmation data are as follows: FT-IR (KBr, cm -1 ): 3024, 2919, 2160, 2030, 1977, 1702, 1642 (C=N), 1493, 1466, 1365, 1235, 1118, 1076, 1031, 819, 765, 739, 698. 1 H NMR (400...

Embodiment 2

[0099] Embodiment 2, preparation complex Fe1 (in formula I, R1=Me; R2=H; M=Fe)

[0100] 1. The preparation of 2-acetyl-6-(1-(2,6-benzhydryl-4-methylaniline)ethyl)pyridine is the same as in Example 1.

[0101] 2. Preparation of ligand: 2-(1-(2,6-dimethylaniline) ethyl)-6-(1-(2,6-dibenzhydryl-4-methylaniline) ethyl ) pyridine (L1): 2-acetyl-6-(1-(2,6-dibenzhydryl-4-methylaniline) ethyl)pyridine (1.14g, 2.0mmol) and 2,6-bis A catalyst equivalent (300 mg) of p-toluenesulfonic acid was added to a solution of methylaniline (0.21 g, 2.0 mmol) in toluene (50 mL). Heated to reflux for 8h. The solvent toluene was removed, and the residue was subjected to alumina column chromatography with a solvent of petroleum ether and ethyl acetate at a volume ratio of 50:1. The elution fraction was detected by a thin-layer silica gel plate, and the developing solvent was a mixed solvent of petroleum ether and ethyl acetate with a volume ratio of 100:1, and the fraction with an Rf value of 2 / 3-1 / 3...

Embodiment 3

[0108] Embodiment 3, preparation complex Fe2 (in formula I, R1=Et; R2=H; M=Fe)

[0109] 1. The preparation of 2-acetyl-6-(1-(2,6-benzhydryl-4-methylaniline)ethyl)pyridine is as in Example 1.

[0110] 2. Preparation of ligand: 2-(1-(2,6-diethylaniline) ethyl)-6-(1-(2,6-dibenzhydryl-4-methylaniline) ethyl ) pyridine (L2): 2-acetyl-6-(1-(2,6-dibenzhydryl-4-methylaniline) ethyl)pyridine (1.14g, 2.0mmol) and 2,6-bis A catalytic equivalent of p-toluenesulfonic acid was added to a solution of ethylaniline (0.22, 2.0 mmol) in toluene (50 mL). Heated to reflux for 8h. The solvent toluene was removed, and the residue was subjected to alumina column chromatography with a solvent of petroleum ether and ethyl acetate at a volume ratio of 50:1. The elution fraction was detected by a thin-layer silica gel plate, and the developing solvent was a mixed solvent of petroleum ether and ethyl acetate with a volume ratio of 100:1, and the fraction with an Rf value of 2 / 3-1 / 3 (ie the third fracti...

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Abstract

The invention discloses a tridentate nitrogen ligand 2,6-diimine pyridine contained iron or cobalt complex and a preparation method thereof. The structural formula of the complex is shown in a formula I, wherein M is iron or cobalt, and R1 and R2 are selected from any one of hydrogen and alkyl. The preparation method is as follows: under anaerobic conditions, a ligand shown in a formula IV is reacted with FeCl2 4H2O or CoCl2 to obtain the complex shown in the formula I. The N ^ N ^ N ligand containing asymmetric 2,6-diimine pyridine ligand and iron metal complex is synthesized, and the metal complex is used for catalyzing an ethylene polymerization reaction, and shows high catalytic activity. The obtained polymer has a high molecular weight, the catalyst has strong tolerance to high temperature, for example, at a higher temperature (80 DEG C), the iron (II) complex shows high polymerization activity on ethylene, and the polymerization activity can reach 2.2*107g mol<-1> (Fe) h<-1>; and the metal complex has wide industrial application prospects. (Formula I) (Formula IV).

Description

technical field [0001] The invention relates to a kind of unsymmetrical pyridinediimine iron or cobalt complex catalyst and its preparation method and application. Background technique [0002] Polymer materials are the pillars of modern science and technology and social development, and have become indispensable and important materials in various fields of cutting-edge technology, national defense construction and national economy. Among them, polyethylene is the synthetic resin with the fastest development, the largest output and a wide range of uses. Industrialized polyethylene catalysts have Ziegler-Natta type catalysts (DE Pat 889229 (1953); IT Pat 545332 (1956) and IT Pat 536899 (1955); Chem.Rev., 2000, 100, 1169 and related documents of this special series), Phillips type catalyst (Belg.Pat.530617 (1955); Chem.Rev.1996,96,3327) and metallocene type catalyst (W.Kaminsky, Metalorganic Catalysts for Synthesis and Polymerization, Berlin: Springer, 1999), and in recent ye...

Claims

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Application Information

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IPC IPC(8): C07F15/02C07F15/06C08F10/02C08F4/70
Inventor 孙文华于建刚张文娟刘浩
Owner INST OF CHEM CHINESE ACAD OF SCI
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