High-selectivity catalyst system used in trimerization and tetramerization of ethylene and use method thereof

An ethylene trimerization, high-selectivity technology, applied in chemical instruments and methods, physical/chemical process catalysts, organic compound/hydride/coordination complex catalysts, etc. impact, etc.

Active Publication Date: 2015-04-15
EAST CHINA UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In these studies, a large part of the work is to modify the substituents on the N atom in PNP. It is found that by changing the substituents, the co-selectivity of 1-hexene/1-octene will be significantly affected.
The high-selectivity oli

Method used

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  • High-selectivity catalyst system used in trimerization and tetramerization of ethylene and use method thereof
  • High-selectivity catalyst system used in trimerization and tetramerization of ethylene and use method thereof
  • High-selectivity catalyst system used in trimerization and tetramerization of ethylene and use method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0076] 1 Preparation of Ligand 5

[0077] At 0°C, diphenylphosphine chloride and the corresponding (isopropylcyclohexyl)methylamine were added into the dichloromethane solution at a molar ratio of 2:1 and stirred. After stirring for 40 minutes, continue to stir overnight at room temperature. Amine hydrochloride produced in the reaction was removed by filtration. The product was obtained after recrystallization with a yield of 81%.

[0078] 2 ethylene oligomerization reaction

[0079] Ethylene oligomerization was carried out in a 300mL autoclave. Before oligomerization started, the reactor was replaced with nitrogen three times and with ethylene twice. Then add solvent toluene into the autoclave, stir under ethylene atmosphere, and heat to set temperature. The predetermined amount of MAO, ligand and CrCl 3 (THF) 3 Add to the autoclave and stir for 1 min. Feed ethylene into the reactor and adjust the pressure in the reactor to reach the set value, and the reaction starts....

Embodiment 2

[0081] 1 Preparation of Ligand 7

[0082] At 0°C, diphenylphosphine chloride and the corresponding (isobutylcyclohexyl)methylamine were added to the dichloromethane solution at a molar ratio of 2:1 and stirred. After stirring for 40 minutes, continue to stir overnight at room temperature. Amine hydrochloride produced in the reaction was removed by filtration. The product was obtained after recrystallization with a yield of 76%.

[0083] 2 ethylene oligomerization reaction

[0084] Ethylene oligomerization was carried out in a 300mL autoclave. Before the oligomerization starts, the reactor is replaced with nitrogen and ethylene to keep the oxygen value of the water in the reactor low. Then add solvent toluene into the autoclave, stir under ethylene atmosphere, and heat to set temperature. A predetermined amount of MAO, ligand and Cr(acac) 3 Add to the autoclave and stir for 1 min. Feed ethylene into the reactor and adjust the pressure in the reactor to reach the set value...

Embodiment 3

[0086] 1 Preparation of Ligands 17

[0087] At 0°C, add chlorinated diphenylphosphine and the corresponding (1,2,5-trimethyl)cyclohexylamine into the dichloromethane solution at a molar ratio of 2:1 and stir. After stirring for 40 minutes, continue to Stir overnight. Amine hydrochloride produced in the reaction was removed by filtration. The product was obtained after recrystallization with a yield of 70%.

[0088] 2 ethylene oligomerization reaction

[0089] Ethylene oligomerization was carried out in a 300mL autoclave. Before the oligomerization starts, the reactor is replaced with nitrogen and ethylene to keep the oxygen value of the water in the reactor low. Then add solvent toluene into the autoclave, stir under ethylene atmosphere, and heat to set temperature. Add predetermined amount of MAO, ligand and chromium(III) 2-ethylhexanoate into the autoclave and stir for 1 min. Feed ethylene into the reactor and adjust the pressure in the reactor to reach the set value, ...

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Abstract

The invention provides a high-selectivity catalyst system used in trimerization and tetramerization of ethylene and a use method thereof. The catalyst system includes three components: (1) a chromium compound, (2) a ligand, of which a general structure formula is (Ph2)P-N(R1)-P(Ph2), wherein R1 is a synthetic phenyl group, alkyl group or cycloalkyl group; and (3) an activating agent or a co-catalyst. According to the catalyst system, a conventional PNP chromium-series catalyst is improved so that a co-selectivity of 1-hexane and 1-octylene is increased, wax-like products are reduced and a high activity is maintained.

Description

technical field [0001] The invention relates to a PNP type chromium series catalyst for ethylene high-selectivity trimerization and tetramerization and a method for preparing and catalyzing ethylene trimerization and tetramerization. Background technique [0002] Linear α-olefins (linearα-olefins, LAOs) refer to C 4 and C 4 The above linear olefins, and their series products are important basic organic chemical raw materials, and are widely used in the preparation of high-performance polyolefins, high-grade detergents, high-grade alcohols, high-grade lubricating oils, surfactants and oil additives. where C 6 -C 8 The α-olefins are mainly used as comonomers to produce high-performance polyolefins, with the largest consumption and the greatest value-added potential, and are currently the most urgently needed products in China. [0003] Polyethylene is a class of polymer materials widely used in industry and daily life. Due to abundant raw materials, low price, easy proces...

Claims

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Application Information

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IPC IPC(8): B01J31/24C07C11/02C07C11/107C07C2/34
Inventor 刘振唐思扬李宁占兴稳程瑞华何雪莲刘柏平
Owner EAST CHINA UNIV OF SCI & TECH
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