A kind of method of ethylene oligomerization

A technology of ethylene oligomerization and ethylene, which is applied in the direction of chemical instruments and methods, hydrocarbons, organic compounds/hydrides/coordination complex catalysts, etc., can solve the problem of polymerization process reaction initiation and poor repeatability, and the price of modified MMAO Expensive, unfavorable ethylene oligomerization process and other problems, to achieve the effect of rapid reaction initiation, low price and low requirements

Active Publication Date: 2018-05-11
CHINA PETROLEUM & CHEM CORP +1
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  • 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 this method uses expensive alkyl aluminoxane as a cocatalyst, and 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 the solvent and modified MMAO as the cocatalyst. The modified MMAO is expensive and can only be imported, which limits the industrial scale-up of the MMAO as the cocatalyst system.
[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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  • A kind of method of ethylene oligomerization
  • A kind of method of ethylene oligomerization
  • A kind of method of ethylene oligomerization

Examples

Experimental program
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Effect test

Embodiment 1

[0033] The ethylene oligomerization reaction specifically comprises the steps:

[0034] (1) In a continuous reaction device, water-containing ethylene, solvent n-heptane, metal procatalyst solution (concentration is 2.5 μ mol / mL, such as formula I, wherein 4 Rs are all phenyl groups, M is chromium, and X is chlorine , n=3), cocatalyst trimethylaluminum solution (concentration is 1mmol / mL) enters reactor respectively, and its flow rate is 80g / h, 160g / h, 3.5g / h, 2.6g / h, keeps in the reaction system Al / Cr mol ratio is 500, and the residence time that keeps reaction material in reactor is 30 minutes;

[0035] (2) The reaction pressure is 5MPa and the reaction temperature is 80°C, wherein, based on ethylene, the mass content of water is 400 mg / Kg (ppm);

[0036] (3) Carry out gas chromatography (GC) analysis to the reaction outlet material. See attached table 1 for the data.

Embodiment 2

[0038] 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 ethylene water content is 300 mg / Kg. The results of ethylene oligomerization are shown in Table 1.

Embodiment 3

[0040] 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 ethylene water content is 500 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 relates to a method for ethylene oligomerization, comprising carrying out ethylene oligomerization reaction in the presence of a main catalyst represented by formula (I), a cocatalyst, an organic solvent and water; wherein, the 4 Rs present may be the same or different, Each is independently selected from alkyl, cycloalkyl and aromatic groups, preferably phenyl or substituted phenyl; R' and R" are different, and each independently selects hydrogen and tert-butyl, M is a transition metal, X selected from halogen, and n is an integer of 1-3.

Description

technical field [0001] The invention relates to a method for ethylene oligomerization, in particular to a method for continuous reaction of ethylene trimerization and tetramerization. Background technique [0002] The oligomerization of olefins, mainly α-olefins, using chromium-based catalysts has been extensively studied. Among them, the trimerization of ethylene into 1-hexene and the tetramerization of ethylene into 1-octene have special significance. 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 strength and impact resistance of polyethylene. The strength has been significantly improved, and it is very suitable for packaging films and agricultural covering films such as greenhouses and greenhouses. At the same time, 1-hexene and 1-octene are also used as plasticizers, fatty acids, alcohols for d...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C11/02C07C11/107C07C2/22B01J31/24
CPCY02P20/52
Inventor 祁彦平吴红飞郑明芳栗同林隋军龙徐珂刘珺王霄青韩春卉
Owner CHINA PETROLEUM & CHEM CORP
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