Ethylene oligomerization catalyst composition containing 1, 10-phenanthroline amino-iron (II) complex substituted by formyl or isobutyryl

A technology for phenanthroline amide and ethylene oligomerization, which is applied in the directions of organic compound/hydride/coordination complex catalyst, physical/chemical process catalyst, hydrocarbon compound, etc. big problem

Active Publication Date: 2013-04-03
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] From the teaching of this patent, it can be seen that when triethylaluminum is a cocatalyst, even at a higher cocatalyst dosage, 2-imino-1,10-phenanthroline coordinates Fe 2+ Chloride-catalyzed ethylene oligomerization activity is still relatively low, and the practicability is poor, so the high-cost methyl aluminoxane is mainly used as a cocatalyst in its patent
However, the cost of methylaluminoxane is too high and the amount used is too large. When it is used as a cocatalyst for ethylene oligomerization on a large scale, it will inevitably lead to high production costs.

Method used

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  • Ethylene oligomerization catalyst composition containing 1, 10-phenanthroline amino-iron (II) complex substituted by formyl or isobutyryl
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  • Ethylene oligomerization catalyst composition containing 1, 10-phenanthroline amino-iron (II) complex substituted by formyl or isobutyryl

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0040] 1. Synthesis of Catalyst Chloride 2-Formyl-1,10-Phenanthroline Condensed 2,6-Diethylanilinate Iron (II) Complex

[0041] a. Synthesis of 2-formyl-1,10-phenanthroline

[0042]Put 5.1 g (28.3 mmol) of 1,10-phenanthroline into a 250 ml three-necked flask, and dissolve it with 100 ml of toluene under nitrogen protection and magnetic stirring. Slowly add 3ml of trimethylaluminum (d=0.75g / ml, 31.3mmol) dropwise to the three-necked flask under stirring at -60°C, the dropwise addition is completed in about 15 minutes, continue stirring at this temperature for 18h, and then raise the temperature To about 30 ℃, continue to stir for 10h. Then the reaction mixture was cooled to about -30°C, 50ml of distilled water was slowly added thereto, and then heated to 30°C and stirred for 10h. Then separate the liquids, take out the organic phase, and extract the inorganic phase three times with dichloromethane, each time the consumption of dichloromethane is 20ml, and combine the organic ...

Embodiment 2

[0056] Using the main catalyst prepared in Example 1, the cocatalyst is triethylaluminum to carry out ethylene oligomerization, the difference from Example 1 is: the consumption of triethylaluminum toluene solution is 1.07ml (concentration is 0.74mol / l ), so that Al / Fe=396. At 30°C, the ethylene pressure was maintained at 1 MPa, and the reaction was stirred for 30 minutes. A small amount of reaction mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was 3.78×10 6 g·mol -1 (Fe)·h -1 , the oligomer contents are C 4 16.1%, C 6 ~C 10 59.9%, C 6 ~C 18 80.6% (including 91.7% linear α-olefins), C 20 ~C 28 3.3%. The remaining reaction mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained. The analysis results are shown in Table 1.

Embodiment 3

[0058] Adopt the procatalyst prepared in embodiment 1, cocatalyst is triethylaluminum to carry out ethylene oligomerization reaction, and the difference with embodiment 1 is: the consumption of triethylaluminum toluene solution is 0.8ml (concentration is 0.74mol / l ), so that Al / Fe=296. At 30°C, the ethylene pressure was maintained at 1 MPa, and the reaction was stirred for 30 minutes. Take out a small amount of reaction mixture with a syringe and carry out GC analysis after neutralizing with 5% dilute hydrochloric acid: oligomerization activity is 4.03×10 6 g·mol -1 (Fe)·h -1 , the oligomer contents are C 4 21.9%, C 6 ~C 10 60.8%, C 6 ~C 18 75.7% (including 91.8% linear α-olefins), C 20 ~C 28 2.4%. The remaining reaction mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained. The analysis results are shown in Table 1.

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Abstract

The invention provides an ethylene oligomerization catalyst composition. The ethylene oligomerization catalyst composition comprises a main catalyst of a 1, 10-phenanthroline amino-iron (II) complex which is substituted by formyl in a formula (I) or a 1, 10-phenanthroline amino-iron (II) complex which is substituted by isobutyryl in a formula (II) and a catalyst promoter of triethyl aluminum, wherein the molar ratio of the metallic aluminium of the catalyst promoter to the central metallic aluminium of the main catalyst (I) is between 30 and 500, and the molar ratio of the metallic aluminium of the catalyst promoter to the central metallic aluminium of the main catalyst (II) is between 30 and 900. According to the ethylene oligomerization catalyst composition, the triethyl aluminum which is used as the catalyst promoter is low in price, and the usage of the catalyst promoter is greatly reduced, the catalyst has good catalytic activity of catalyzing ethylene oligomerization, so that the ethylene oligomerization reaction cost is greatly lowered; the selectivity of linear alpha-olefin in an oligomerization product is high; the oligomerization product is distributed reasonably; polyvinyl cannot be generated; and thus, the ethylene oligomerization catalyst composition has a wide industrial prospect.

Description

technical field [0001] The invention relates to the field of ethylene oligomerization, in particular to a catalyst composition containing formyl or isobutyryl substituted 1,10-phenanthroline amidoiron (II) complex and triethylaluminum. The present invention also relates to a process for the oligomerization of ethylene using the composition described above. Background technique [0002] Linear α-olefins are widely used in the fields of ethylene comonomers, surfactant synthesis intermediates, plasticizer alcohols, synthetic lubricating oils and oil additives. In recent years, with the continuous development of the polyolefin industry, the worldwide demand for α-olefins has grown rapidly. At present, the vast majority of α-olefins are prepared by ethylene oligomerization. The used catalyst of ethylene oligomerization mainly contains nickel series, chromium series, zirconium series and aluminum series etc., in recent years, Brookhart group (Brookhart, the people such as M, J.A...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/22C07C11/02C07C2/22
CPCY02P20/52
Inventor 刘珺李维真郑明芳张海英王怀杰周钰赵岚栗同林吴红飞贾志光
Owner CHINA PETROLEUM & CHEM CORP
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