Ethylene oligomerization method

A technology of ethylene oligomerization and ethyl, which is applied in the direction of chemical instruments and methods, hydrocarbons, hydrocarbons, etc., can solve the problems of expensive aluminoxane and high production cost

Inactive Publication Date: 2011-10-05
CHINA PETROLEUM & CHEM CORP
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] As we all know, aluminoxane is relatively expensive. If aluminoxane is used as a cocatalyst in large-scale application of ethylene oligomerization, it will inevitably lead to high production costs.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0082] 1. Preparation of the main catalyst

[0083] 2-Acetyl-1,10-phenanthroline (0.4445g, 2mmol) and 2,6-diethylaniline (0.4175g, 2.8mmol) were added 40mg p-toluenesulfonic acid as catalyst and 2g was added Molecular sieve was used as dehydrating agent, refluxed in 30ml of ethanol for 1 day, filtered to remove solvent toluene, the residue was dissolved and supported with dichloromethane, overbased alumina column, rinsed with petroleum ether / ethyl acetate (4:1) , the second fraction is the product, and the solvent is removed to obtain a yellow solid, which is a ligand of 2-acetyl-1,10-phenanthroline (2,6-diethylaniline), and the yield is 0.6 g and the yield is 84%. . NMR analysis: 1 H NMR (300MHz, CDCl 3 ): δ9.25 (dd, J=3.0Hz, 1H); 8.80 (d, J=8.3Hz, 1H); 8.35 (d, J=8.3Hz, 1H); 8.27 (dd, J=7.8Hz, 1H) ); 7.86(s, 2H); 7.66(m, 1H); 7.15(d, J=7.6Hz, 2H); 6.96(t, J=7.5Hz, 1H); 2.58(s, 3H, CH) 3 ); 2.43 (m, 4H, CH 2 CH 3 ); 1.16(t, J=7.5Hz, 6H, CH 2 CH 3 ). Elemental Analy...

Embodiment 2

[0088] Adopt the main catalyst prepared in Example 1, the cocatalyst is triethylaluminum to carry out ethylene oligomerization, and the difference from Example 1 is: the consumption of triethylaluminum toluene solution is 0.54ml (concentration is 0.74mol / l) , so that Al / Fe=199.8. At 40 °C, the ethylene pressure of 1 MPa was maintained, and the reaction was stirred for 30 min. Take out a small amount of the mixture with a syringe and neutralize it with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity is 2.02 × 10 6 g·mol -1 ·h -1 , the oligomer content is C 4 12.1%, C 6 ~C 10 64.5%, C 6 ~C 18 86.8% (including 97.5% of linear alpha-olefins), C 20 ~C 28 1.1%, K value 0.57. The remaining mixture was neutralized with 5% hydrochloric acid in acidified ethanol, and no polymer was obtained. The analysis results are shown in Table 1.

Embodiment 3

[0090] Adopt the main catalyst prepared in Example 1, the cocatalyst is triethylaluminum to carry out ethylene oligomerization, and the difference from Example 1 is: the consumption of triethylaluminum toluene solution is 0.4ml (concentration is 0.74mol / l) , so that Al / Fe=148. At 40 °C, the ethylene pressure of 1 MPa was maintained, and the reaction was stirred for 30 min. Take out a small amount of the mixture with a syringe and neutralize it with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity is 1.21 × 10 6 g·mol -1 ·h -1 , the oligomer content is C 4 24.7%, C 6 ~C 10 57.4%, C 6 ~C 18 72.7% (including 92.9% of linear alpha-olefins), C 20 ~C 28 2.6%, K value 0.52. The remaining mixture was neutralized with 5% hydrochloric acid in acidified 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 method. Chloride of Fe<2+>, Co<2+> and Ni<2+> with 2-imino-1, 10-phenanthroline coordinated is taken as a main catalyst, Triethylaluminium is taken as a cocatalyst for replacing a high-price methylaluminoxane and the like, and the mol ratio of aluminum in the cocatalyst of triethylaluminium to central metal in the main catalyst is more than 30 and less than 200 or more than 200 and less than 500, The amount of the cocatalyst is greatly reduced, therefore the cost of the ethene oligomerization reaction is greatly reduced, the invention has a broad industrialization prospect.

Description

technical field [0001] The invention relates to an ethylene oligomerization method, in particular to a method using 2-imino-1,10-phenanthroline chloride iron(II), cobalt(II) or nickel(II) complexes as main catalysts, Ethylene oligomerization process with triethylaluminum as cocatalyst. Background technique [0002] Linear α-olefins are widely used in 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 alpha-olefins are prepared by oligomerization of ethylene. The catalysts used in the ethylene oligomerization method mainly include nickel series, chromium series, zirconium series and aluminum series. ; WO99 / 02472, 1999), the Gibson group (Gibson, V.C. et al., Chem. Commun., 1998, 849-850; Chem. Eur. J., 2000, 2221-2231) found some Fe(II) an...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C2/30
Inventor 郑明芳王怀杰刘珺李维真张海英王吉龙吴红飞栗同林赵岚张凌燕贾志光
Owner CHINA PETROLEUM & CHEM CORP
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