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Ethylene trimerization/tetramerization catalyst composition and application thereof

A technology of ethylene trimerization and composition, which is applied in the direction of catalysts, hydrocarbons, hydrocarbons, etc., can solve the problems of restricting industrial scale-up, generating more polymers, and only importing them, and achieves ultra-high polymerization reactivity, Response triggers fast, smooth-running effects

Active Publication Date: 2017-10-24
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

CN1606539A discloses a multi-dentate ligand phosphine, arsenic and / or antimony coordination compound containing aluminoxane and chromium salt, which is used in the process of ethylene oligomerization; WO2003053890 reports a sulfur, Nitrogen heteroatom ligands are used for olefin oligomerization. The catalytic system has high activity, but the disadvantage is that more polymers will be generated during the oligomerization process.
[0005] Jun Zhang, et al also reported that vinyl-bridged bisphosphine ligands have high catalytic activity for ethylene tetramerization, and the total yield of the products 1-hexene and 1-octene can reach 80%, The disadvantage is that this technology uses methylcyclohexane as a solvent and modified MMAO as a cocatalyst. The modified MMAO is expensive and can only be imported, which limits the industrial scale-up of MMAO as a cocatalyst.
[0006] Moreover, in the above-mentioned prior art, it is generally believed that the existence of water and oxygen is very unfavorable to the ethylene oligomerization process, so it is necessary to strictly control the reaction in an anhydrous and oxygen-free environment during the production process, such as the above-mentioned All are carried out under anhydrous and anaerobic conditions in the prior art mentioned
This makes all currently known ethylene trimerization and oligomerization reactions very demanding on the process, resulting in very poor reaction initiation and repeatability of the polymerization process

Method used

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  • Ethylene trimerization/tetramerization catalyst composition and application thereof
  • Ethylene trimerization/tetramerization catalyst composition and application thereof
  • Ethylene trimerization/tetramerization catalyst composition and application thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0035] A 500ml stainless steel polymerization kettle was used for the polymerization reaction. First, the pressure-holding test was carried out on the reaction kettle. Under the condition that the sealing of the reaction kettle was confirmed, vacuum drying was carried out at 120°C for 4 hours, and then the temperature was lowered to 80°C and replaced with ethylene gas three times. Add solvent n-heptane, trimethylaluminum, tert-butyl hydroperoxide to the reaction kettle in turn, start stirring and premix for 3 minutes, then add a chromium complex solution containing 1 μmol of chromium to the reaction kettle, and the bisphosphine compound R in the body 1 -R 4 All are o-methoxyphenyl, R' is methyl, R" is tert-butyl; the chromium compound used is chromium acetylacetonate. The total volume of the resulting composition is 100ml, based on the weight of the organic solvent, the tert-butyl The content of hydrogen oxide is 40mg / Kg.Al / Cr ratio is 500.Control reaction pressure 5.0MPa, f...

Embodiment 2

[0039] The specific steps are the same as in Example 1, except that the cocatalyst is an equimolar mixed solution of trimethylaluminum and diethylaluminum chloride, the Al / Cr ratio is 600, and the tert-butyl hydroperoxide content is 150mg / Kg , the reaction time is 1 hour. The results of ethylene oligomerization are shown in Table 1.

Embodiment 3

[0041] The concrete steps are the same as in Example 1, except that the cocatalyst is triethylaluminum, and the Al / Cr ratio is 500. In the bisphosphine ligand, R' is a tert-butyl group, and R" is a cyclopropyl group, and the reaction temperature is 50 ℃. ℃, the pressure is 4.0MPa, the content of tert-butyl hydroperoxide is 250mg / Kg, and the reaction time is 20 minutes. The ethylene oligomerization reaction results are shown in attached table 1.

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Abstract

The invention discloses an ethylene trimerization catalyst composition which comprises diphosphine ligand shown in formula I, a transition metal compound, an aluminum-containing promoter and peroxide, and in formula I shown in the specification, R1 and R4 are identical or different and are independently selected from alkyl, a naphthenic base and an aromatic group; R' and R'' are hydrogen or are independently selected from alkyl, cycloalkane and aromatic groups. Meanwhile, the invention further provides a method for ethylene trimerization reaction with the catalyst composition. The ethylene trimerization catalyst composition is high in catalysis activity on the contrary and good in catalysis activity and selectivity of 1-octylene.

Description

technical field [0001] The present invention relates to a method for oligomerization of ethylene, in particular to a novel catalyst composition and its application in ethylene trimerization and tetramerization. Background technique [0002] The oligomerization of olefins, mainly alpha-olefins, using chromium-based catalysts has been extensively studied. More precisely, many chromium-based catalysts have been developed and used for the oligomerization of olefins to produce alpha-olefins. Among them, the trimerization of ethylene to make 1-hexene and the tetramerization of ethylene to make 1-octene have special significance. As important organic raw materials and chemical intermediates, 1-hexene and 1-octene are mainly used to produce high-quality polyethylene (PE). Linear low density polyethylene (LLDPE) produced by copolymerizing 1-hexene or 1-octene with ethylene can significantly improve the properties of PE, especially the mechanical properties, optical properties, tear...

Claims

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Application Information

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IPC IPC(8): B01J31/24C07C2/36C07C11/107C07C11/02
CPCC07C2/36B01J31/143B01J31/24C07C2531/24B01J2540/10B01J2531/90B01J2531/62B01J2531/0241B01J35/19C07C11/107C07C11/02
Inventor 祁彦平吴红飞栗同林隋军龙刘珺徐珂韩春卉
Owner CHINA PETROLEUM & CHEM CORP
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