A kind of coordination type catalyst and the method for using the ethylene oligomerization of the catalyst to co-produce 1-hexene and 1-octene

An ethylene oligomerization and catalyst technology, applied in the direction of organic compound/hydride/coordination complex catalyst, chemical instrument and method, physical/chemical process catalyst, etc., to achieve the effect of stabilizing the catalytic system and improving catalytic activity

Active Publication Date: 2017-09-29
CHINA PETROLEUM & CHEM CORP +2
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In 2004, Sasol's Bollmann et al. (J.Am. Chem. Soc. 2004, 126, 14712) successfully developed the first real catalytic system for the selective tetramerization of ethylene to produce 1-octene (R 2 ) 2 PN(R 1 )P(R 2 ) 2 (R 2 =phenyl, ethyl, naphthyl, R 1 =methyl, alkyl, phenyl), the selectivity of 1-octene exceeds 70% (wt), the selectivity of terminal olefins can reach more than 90%, the reactivity exceeds 26000 g / (mmol Cr.h), but a small amount of C 6 component, where C 6 The selectivity of terminal olefins is only about 70%
Gambarotta et al. (Angew. Chem. Int. Ed. 2010, 49, 9225) synthesized a series of N-bridged bispyridine ligands (2-C 5 h 4 N) 2 NR and its chromium-based catalysts, which can catalyze the selective oligomerization of ethylene to generate 1-octene, but the system will generate a large amount of polyethylene

Method used

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  • A kind of coordination type catalyst and the method for using the ethylene oligomerization of the catalyst to co-produce 1-hexene and 1-octene
  • A kind of coordination type catalyst and the method for using the ethylene oligomerization of the catalyst to co-produce 1-hexene and 1-octene
  • A kind of coordination type catalyst and the method for using the ethylene oligomerization of the catalyst to co-produce 1-hexene and 1-octene

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0021] The method for co-producing 1-hexene and 1-octene by ethylene oligomerization is shown in the following formula, and the catalyst is used to catalyze ethylene oligomerization.

[0022]

[0023] The catalyst toluene solution of 1 mmol / L was freshly prepared in the glove box, and 10 mL of the catalyst solution was measured for use. Install the reaction kettle, preheat to 100°C, dry in vacuum and cool to room temperature, replace with ethylene atmosphere, add 50 mL of toluene solution, 10 mL of catalyst toluene solution, 1 mL of methylaluminoxane toluene solution (1.5 mol / L ), rapidly heated to 60 °C, while raising the ethylene pressure to 3 MPa, stirring at 800 rpm, and maintaining it for 60 min. Rapidly cool the reaction system to 0 °C, release the pressure, collect the gas with a gas trap, collect the solid polymer by filtration and weigh it dry, calculate the mass percentage separately, add 10 mL absolute ethanol and 1 mL 10% hydrochloric acid to the liquid Quenchi...

Embodiment 2

[0026] Change 60 DEG C of reaction temperature into 50 DEG C in embodiment 1, other operation conditions are constant, calculate and obtain catalyst activity by gas chromatography analysis and be 8.5 * 10 6 g / mol Cr h, the product composition is shown in Table 1, and the high polymer content is 0.82%.

Embodiment 3

[0028] Change 60 ℃ of reaction temperature into 40 ℃ among the embodiment 1, other operating conditions are constant, calculate and obtain catalyst activity by gas chromatographic analysis and be 7.8 * 10 6 g / mol Cr h, the product composition is shown in Table 1, and the high polymer content is 0.62%.

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Abstract

The invention discloses a coordination catalyst and a method for co-producing 1-hexene and 1-octene through ethylene oligomerization using the catalyst. The coordination catalyst provided by the invention contains a structural system capable of transmitting group electron induction or conjugation effects, which can better realize the electron transfer between atoms coordinated with the metal, stabilize the catalytic system, improve catalytic activity, and simultaneously increase the Selectively prepare 1-hexene and 1-octene, the selectivity of terminal olefins is >95%, the highest can exceed 99%, successfully realize the co-production of 1-hexene and 1-octene under the condition of high-end olefin selectivity.

Description

technical field [0001] The invention relates to a coordination catalyst, and also relates to a method for coproducing 1-hexene and 1-octene through ethylene oligomerization using the catalyst. Background technique [0002] Linear α-olefin refers to the number of carbon atoms is C 4 and C 4 The above linear olefins contain carbon-carbon double bonds. It is an important intermediate in industrial production and is widely used as a comonomer for the production of linear low-density polyethylene, as well as a precursor for detergents, synthetic lubricants and plasticizers. In the field of linear α-olefin applications, C 4 -C 8 The short-chain olefins occupy about 40% of the linear alpha-olefins market and are the most in demand. Polyolefin products with 1-hexene and 1-octene as comonomers have good mechanical properties and excellent processing properties, so they are widely used in industrial production and have a large demand (J. Organomet. Chem.2004 , 689, 3641). [00...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J31/24C07C11/107C07C11/02C07C2/36
CPCY02P20/52
Inventor 钟东文曹育才朱红平肖树萌钟向宏沈安倪晨叶晓峰梁胜彪刘振宇
Owner CHINA PETROLEUM & CHEM CORP
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