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Ethylene oligomerization catalyst composition and applications thereof

A technology for ethylene oligomerization and composition, applied to a novel catalyst composition and its application field in ethylene oligomerization, can solve the problem of polymerization reaction process reaction initiation and poor repeatability, unfavorable ethylene oligomerization reaction process, and modified MMAO price. Expensive and other problems, to achieve the effect of ultra-high polymerization activity, rapid reaction initiation and low price

Active Publication Date: 2016-05-11
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, etal also reported that vinyl-bridged bisphosphine ligands have high catalytic activity for ethylene tetramerization, and the total yield of products 1-hexene and 1-octene can reach 80%, which is not enough. The disadvantage is that this technology uses methylcyclohexane as a solvent and modified MMAO as a co-catalyst. The modified MMAO is expensive and can only be imported, which limits the industrial scale-up of the co-catalyst system with MMAO
[0006] Moreover, in the prior art, it is generally believed that water 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
This makes all known ethylene oligomerization or 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 oligomerization catalyst composition and applications thereof
  • Ethylene oligomerization catalyst composition and applications thereof
  • Ethylene oligomerization catalyst composition and applications thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] The polymerization reaction adopts a 500ml stainless steel polymerization kettle. First, the pressure-holding test was carried out on the reactor. Under the condition that the seal of the reactor was confirmed, it was vacuum-dried 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, 500 equivalents of trimethylaluminum and water to the reaction kettle, start stirring and premixing for 3 minutes, then add a chromium complex solution containing 1 μmol of chromium to the reaction kettle until the reaction volume is 100ml, and the water content It is 40mg / Kg. Start stirring, open the ethylene feed valve, maintain the reaction pressure at 5.0 MPa, initiate the reaction, and stop the reaction after 30 minutes. After the test, the pressure was released to normal pressure, and the kettle was opened. After weighing the reaction solution, 1.5 mL of internal standard nonane was added, and the reacti...

Embodiment 2

[0037] The specific steps are the same as in Example 1, except that the cocatalyst is a mixed solution of 300 equivalents of trimethylaluminum and 300 equivalents of diethylaluminum chloride, the Al / Cr ratio is 600, and the water content is 80 mg / Kg. for 1 hour. The results of ethylene oligomerization are shown in Table 1.

Embodiment 3

[0039] The specific steps are the same as in Example 1, the cocatalyst is triethylaluminum, the Al / Cr ratio is 500, the reaction temperature is 50° C., the pressure is 4.0 MPa, the water content is 50 mg / Kg, and the reaction time is 20 minutes. The results of ethylene oligomerization are shown in Table 1.

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Abstract

The present invention discloses an ethylene tetrapolymerization catalyst composition, which comprises a diphosphine ligand represented by a formula I, a transition metal compound, an aluminum-containing co-catalyst, water and an organic solvent, wherein R' and R" are different and are independently selected from hydrogen and tert-butyl, and the existing 4 R can be the same or different and are respectively and independently selected from alkyl, cycloalkyl and aryl. The invention further discloses a method for carrying out an ethylene oligomerization reaction by using the catalyst composition. The formula I is defined in the specification.

Description

technical field [0001] The invention relates to a method for ethylene oligomerization, in particular the invention relates to a novel catalyst composition and its application in ethylene oligomerization. Background technique [0002] The oligomerization of olefins, mainly α-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 α-olefins. Among them, the trimerization of ethylene into 1-hexene and the tetramerization of ethylene into 1-octene are of special significance. As important organic raw materials and chemical intermediates, 1-hexene and 1-octene are mainly used to produce high-quality polyethylene (PE). The linear low-density polyethylene (LLDPE) produced by the copolymerization of 1-hexene or 1-octene and ethylene can significantly improve the properties of PE, especially the mechanical properties, optical properties, tear streng...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/24C07C11/107C07C11/02C07C2/36
Inventor 祁彦平栗同林吴红飞郑明芳王霄青韩春卉刘珺隋军龙徐珂
Owner CHINA PETROLEUM & CHEM CORP
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