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Ethylene oligomerization catalyst composition and application thereof

An ethylene oligomerization and catalyst technology, applied in the direction of hydrocarbons, hydrocarbons, physical/chemical process catalysts, etc., to achieve the effect of less polyethylene and high activity

Inactive Publication Date: 2013-09-11
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

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

Method used

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  • Ethylene oligomerization catalyst composition and application thereof

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. After stirring for 30 minutes, the reaction was continued at room temperature for 12 hours. Filtration and drying gave the product (0.87g, 56.6%).

[0021] 2. Preparation of 1,4-bis(N(P(phenyl) 2 ) 2 )-benzene ligand

[0022] 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 Add 1,4 phenylenediamine (0.19 g, 1.8 mmol). After stirring for 30 minutes, the reaction was continued at room temperature for 12 hours. Filtration and drying gave the product (0.8 g, 52.3%).

[0023] 3. Preparation of cat...

Embodiment 2

[0028] 1. Preparation of (diphenyl) phosphorus nitrogen (cyclopentyl) phosphorus (diphenyl) ligand

[0029] 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%).

[0030] 2. Preparation of catalyst

[0031] in the N 2 Add dehydrated cyclohexane (10 mL) into a fully replaced stirred 100 mL reactor, and add 1.4 mol / L in sequence according to the ratio of a: b: c: d: e = 1: 0.5: 50: 0.5: 0.5 Methylalumoxane toluene solution c, (diphenyl)phosphorus nitrogen (cyclopentyl)phosphorus (diphenyl) b, tetrahydrofuran chromium chloride a, 1,1,2,2-tetrabromoethane d, 1,4-bis(N(P(phenyl) 2 ) 2 )-benzene ligand e, after reacting at room temperature for 5 minut...

Embodiment 3

[0035] 1. Preparation of (diphenyl) phosphorus nitrogen (fluorenyl) phosphorus (diphenyl) ligand

[0036] 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%).

[0037] 2. Preparation of catalyst

[0038] in the N 2 Add dehydrated cyclohexane (10mL) into a fully replaced stirred 100mL reactor, and add propylaluminum oxide in the ratio of a:b:c:d:e=1:1:200:3:1 Alkane c, (diphenyl) phosphorus nitrogen (fluorenyl) phosphorus (diphenyl) b, chromium acetylacetonate a, 1,2-dimethoxyethane d, 1,4-bis(N(P(benzene base) 2 ) 2 )-benzene ligand e, after reacting at room temperature for 5 minutes, it is ready for use.

[0039] 3. Ethylene oligomerization

[...

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Abstract

The invention relates to an ethylene oligomerization catalyst composition and an application thereof. The composition comprises the following components: a component a contains chromium acetylacetonate, tetrahydrofuran chromium chloride and / or chromium 2-ethylhexanoate; in the formula of a component b, R1, R2, R3 and R4 are phenyl, benzyl or naphthyl; and R5 is isopropyl, butyl, cyclopropyl, cyclopentyl, cyclohexyl or fluorenyl; a component c contains methyl aluminoxane, ethyl aluminoxane, propyl aluminoxane and / or butyl aluminoxane; a component d has a formula X1R6X2, wherein X1 and X2 are F, Cl, Br, I or alkoxy, and R6 is alkyl or aryl; in the formula of a component e, R is a linking group and selected from alkyl and derivatives thereof as well as aryl and derivatives thereof; and the molar ratio is 1: (0.5-10): (50-3000): (0.5-10): (0.5-10). The catalyst has the catalytic activity being more than 5.0*10<6>g mol<-1>Cr.h<-1>, and the mass of 1-hexene and 1-octylene is more than 93%.

Description

technical field [0001] The invention relates to a catalyst system composed of chromium compound a, ligand b, activator c, accelerator d and second ligand e, a catalyst composition for ethylene oligomerization and its application. Background technique [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 parts. [0003] Although 1-hexene and 1-octene ha...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/24C07C2/36C07C11/107C07C11/02
Inventor 李建忠王斯晗王桂芝杨玉和贺德福徐显明徐可忠于杨张宝军陈谦于部伟王力搏黄付玲王亚丽王秀绘刘玉香徐艳孙玲王东军王淑兰苑慧敏王凤荣曾群英白玉洁杜海孙淑坤李文鹏
Owner PETROCHINA CO LTD
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