Ethane oligomerization and polymeric chromium catalyst and preparation method thereof

A catalyst, the technology of ethoxycarbonylpyridine chromium halide, is applied in the field of N-N-O tridentate ligand chromium complex catalyst, which can solve the problem of no model compound, limited ethylene oligomerization and polymerization industrial development, active center and mechanism are not confirmed, etc. problem, to achieve the effect of low price

Active Publication Date: 2011-06-15
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Characterized by analytical means such as NMR, but until now there is still no real model compound
The active center and mechanism of the catalytic reaction have not yet been confirmed, and the active chromium accounts for less than 1%
[0004] However, most of the above-mentioned catalysts ar

Method used

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  • Ethane oligomerization and polymeric chromium catalyst and preparation method thereof
  • Ethane oligomerization and polymeric chromium catalyst and preparation method thereof
  • Ethane oligomerization and polymeric chromium catalyst and preparation method thereof

Examples

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Example Embodiment

[0045] Example 1

[0046] 1. Preparation of catalyst C1: add tetrahydrofuran chromium chloride (0.372g, 1mmol) and the corresponding 6-ester-2-iminopyridine L1 (0.296g, 1mmol) into a Schlenk bottle, vacuum and pass N 2 After three replacements, add treated dichloromethane (10ml), stir at room temperature for 24 hours, add anhydrous ether after concentration, a green precipitate precipitates, after filtration, vacuum drying to obtain the complex (0.390g, 0.86mmol), C1 yield: 86%. Elemental analysis theoretical value C 18 H 20 Cl 3 CrN 2 O 2 : C, 47.54; H, 4.43; N, 6.16. Found: C, 47.44; H, 4.60; N, 6.33%. IR(KBr: cm -1 ): 1642; 1587; 1467; 1407; 1381; 1341; 1291; 1217; 1097; 992; 851; 768cm -1 .

[0047] 2. Ethylene polymerization: Dry a 250ml polymerization flask equipped with a magnetic stirrer at 130°C for 6 hours continuously, apply vacuum while hot and use N 2 Gas replacement 3 times. Add catalyst C1 (2.3mg, 5μmol), then vacuum and replace with ethylene twice. Use a syringe ...

Example Embodiment

[0048] Example 2

[0049] 1. The preparation of catalyst C1 is the same as in Example 1.

[0050] 2. Ethylene polymerization: vacuum a 250 ml stainless steel kettle equipped with mechanical stirring and thermocouple and replace it with nitrogen 3 times, and then replace it with ethylene 2 times. After cooling to 25°C, add a toluene solution of catalyst C1 (2.3mg, 5μmol) and a certain amount of toluene in sequence, and finally add a certain amount of ethyl aluminum dichloride (1mol / L, 5ml) to make Al / Cr=1000, The total volume of toluene is 100 mL. The pressure of ethylene was immediately increased to 10 atmospheres, and stirred vigorously at 25°C for 30 minutes. After cooling, take out a small amount of the reaction solution, neutralize the MAO in it with dilute hydrochloric acid at 0°C, take a small amount of toluene layer, dry with anhydrous sodium sulfate, and determine the content and distribution of oligomers by gas chromatography. As a result, no oligomer was formed. The r...

Example Embodiment

[0051] Example 3

[0052] 1. The preparation of catalyst C1 is the same as in Example 1.

[0053] 2. Ethylene polymerization: Dry a 250ml polymerization flask equipped with a magnetic stirrer at 130°C for 6 hours continuously, apply vacuum while hot and use N 2 Gas replacement 3 times. Add catalyst C1 (2.3mg, 5μmol), then vacuum and replace with ethylene twice. A certain amount of toluene (29.6ml) was injected with a syringe, and then a hexane solution (0.375ml) of diethyl aluminum chloride was added. Make Al / Cr=150, keep 1 atm ethylene pressure at 25°C, and stir vigorously for 30 minutes. A 5% hydrochloric acid ethanol solution was added to the reaction solution for neutralization, and a white solid was precipitated. But the amount is so small that it cannot be filtered out.

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Abstract

The present invention discloses a series of complex containing 6-ethyl-2-iminobis-phenazopyridine-chromium halide with the formula below, in which R<1>-R<5> can individually select hydrogen, alkyl containing 1-20 carbon atoms, alkaryl, arylalkyl, and halogen, which is represented by X. The present invention also discloses the preparation method for the novel complex, as well as the catalytic compound containing the novel complex and the application thereof to oligomer and polymer of ethane. The preparation of the complex provided by the present invention steps from raw materials with simple structure and low cost, each procedure is easily accomplishable with high yield, the modifiable space of the ligand is relatively large, high polymerization activity is observed in the corresponding catalyst combination, the obtained polymer has lower molecular weight, and the distribution of molecular weight is narrow (compared with the cases reported by previous researches), however, the Tm( DEG C) is above 130, and the obtained polymer is high-linear polyethylene.

Description

Technical field: [0001] The invention relates to a chromium catalyst for ethylene oligomerization and polymerization, in particular to a novel N-N-O tridentate ligand chromium complex catalyst, and its preparation method is used to catalyze ethylene oligomerization and polymerization. Background technique: [0002] As we all know, there are currently two industrialized ethylene polymerization catalyst systems, one is the Ziegler-Natta catalyst, which is a binary system composed of transition metal salts and alkyl metal compounds, and the other is the chromium-based ethylene polymerization catalyst developed by Philips. . According to statistics, 1 / 3 of the world's total ethylene products are produced using chromium-based ethylene polymerization catalysts developed by Philips. Chromium-based catalysts have become the main catalyst system for the preparation of HDPE and LLDPE. Chromium-based catalysts have attracted more and more attention because of their high activity, sim...

Claims

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Application Information

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IPC IPC(8): C07F11/00B01J31/18B01J31/34C08F4/622C07C2/22C08F10/02
Inventor 王文清张文娟于永玲张树李留忠孙文华
Owner CHINA PETROLEUM & CHEM CORP
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