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Catalyst composition of ethylene oligomerization and the application

An ethylene oligomerization and catalyst technology, applied in the direction of catalyst, catalytic reaction, hydrocarbon, etc., to achieve the effect of good selectivity, less polyethylene and high activity

Active Publication Date: 2007-09-12
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] Although 1-octene has important applications in the chemical industry, there is currently no technology for the highly selective synthesis of 1-octene by ethylene oligomerization

Method used

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  • Catalyst composition of ethylene oligomerization and the application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0019] 1. Preparation of (diphenyl) phosphorus nitrogen (cyclopropyl) phosphorus (diphenyl) ligand

[0020] in the N 2 Add dehydrated dichloromethane (20mL), triethylamine (3.75mL), and diphenylphosphine chloride (1.326mL, 7.2mmol) into a fully replaced stirred 100mL reactor, cool to 0°C, and slowly Cyclopropylamine (3.6 mmol) was added, the reaction was stirred for 30 min and then raised to room temperature to continue the reaction for 12 hours, filtered and dried to obtain the product (0.87 g, 56.6%).

[0021] 2. Preparation of catalyst

[0022] in the N 2 Add dehydrated toluene (10mL) into a fully replaced stirred 100mL reactor, and add 1.4mol / L methylalumoxane in sequence according to the ratio of a:b:c:d=1:0.5:300:1 Toluene solution c, (diphenyl) phosphorus nitrogen (cyclopropyl) phosphorus (diphenyl) b, chromium isooctanoate a, 1,1,2,2-tetrachloroethane d, react at room temperature for 10 minutes and set aside.

[0023] 3. Ethylene oligomerization

[0024] A 500mL a...

Embodiment 2

[0026] 1. Preparation of (diphenyl) phosphorus nitrogen (cyclopentyl) phosphorus (diphenyl) ligand

[0027] in the N 2 Add dehydrated dichloromethane (20mL), triethylamine (3.75mL), and diphenylphosphine chloride (1.326mL, 7.2mol) into a fully replaced stirred 100mL reactor, cool to 0°C, and slowly Add cyclopentylamine (0.415 mL, 3.5 mmol). After stirring for 30 minutes, the reaction was continued at room temperature for 12 hours. Filtration and drying gave the product (0.55 g, 32.68%).

[0028] 2. Preparation of catalyst

[0029] in the N 2 Add dehydrated cyclohexane (10 mL) into a fully replaced stirred 100 mL reactor, and add 1.4 mol / L of methyl aluminum in the ratio of a: b: c: d = 1: 0.5: 50: 0.5 Oxylkane toluene solution c, (diphenyl) phosphorus nitrogen (cyclopentyl) phosphorus (diphenyl) b, tetrahydrofuran chromium chloride a, 1,1,2,2-tetrabromoethane d react at room temperature for 5 minutes and set aside .

[0030] 3. Ethylene oligomerization

[0031] A 500mL...

Embodiment 3

[0033] 1. Preparation of (diphenyl) phosphorus nitrogen (fluorenyl) phosphorus (diphenyl) ligand

[0034] in the N 2 Add dehydrated dichloromethane (20mL), triethylamine (3.75mL), and diphenylphosphine chloride (1.326mL, 7.2mol) into a fully replaced stirred 100mL reactor, cool to 0°C, and slowly Fluorenamine (0.652 g, 3.6 mmol) was added. After stirring for 30 minutes, the reaction was continued at room temperature for 12 hours. Filtration and drying gave the product (0.48g, 24.3%).

[0035] 2. Preparation of catalyst

[0036] in the N 2 Add dehydrated cyclohexane (10mL) into a fully replaced stirred 100mL reactor, and add propylaluminoxane c in sequence according to the ratio of a:b:c:d=1:1:200:3, ( Diphenyl) phosphorus nitrogen (fluorenyl) phosphorus (diphenyl) b, chromium acetylacetonate a, 1,2-dimethoxyethane d, react at room temperature for 5 minutes and set aside.

[0037] 3. Ethylene oligomerization

[0038] A 500mL autoclave was heated to vacuum for 2 hours, fi...

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Abstract

The present invention relates to catalyst composition for oligomerizing ethylene and its application. The catalyst composition includes complex of acetylacetone chromium, tetrahydrofuran chromium chloride and / or chromium isooctanate; ligand containing P and N; activator of methyl aluminoxane, ethyl aluminoxane, propyl aluminoxane and / or butyl aluminoxane; and promoter of X1R6X2, where, each of X1 and X2 is F, Cl, Br, I or alkoxyl, and R6 is alkyl or aryl group; with the molar ratio of the complex, the ligand, the activator and the promoter being 1 to 0.5-10 to 50-3000 to 0.5-10. The catalyst composition is used in oligomerizing reaction of ethylene to prepare 1-octene, and has high catalytic activity and high 1-octene selectivity.

Description

technical field [0001] The present invention relates to a catalyst system composed of a chromium compound a, a ligand b containing P and / or N, an aluminum alkyl c and a promoter d, a catalyst composition for ethylene oligomerization and ethylene oligomerization its application. technical background [0002] As we all know, linear α-olefins such as 1-octene and 1-hexene are important chemical products and intermediates, and are widely used in polyethylene comonomers, plasticizer alcohols, flavors and fragrances, synthetic lubricants and oil additives, etc. field. The use of 1-octene and 1-hexene as comonomers can significantly improve the density of polyethylene and improve its mechanical properties such as tear resistance and tensile strength. When used as a plasticizer alcohol, it can improve the low-temperature flexibility, processability and outdoor weather resistance of polyethylene products, especially for the manufacture of cables and wires, auto parts or decorative ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/02C07C2/08C07C11/02
CPCB01J2231/20C08F110/02B01J2531/62B01J31/0204B01J31/188C07C2531/14B01J31/0231C07C2/32B01J31/0201C07C2531/22Y02P20/52C08F2500/02
Inventor 张宝军姜涛李建忠邢立华宁英男孙淑坤匡洞庭孙永成韩云光陈谦陈洪侠张德顺李玉龙张永军苑慧敏王斯晗王桂芝张婧元
Owner PETROCHINA CO LTD
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