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Ethylene polymerization catalyst, preparation and application thereof

A technology of ethylene polymerization and catalyst, which is applied in the field of ethylene polymerization catalyst and its preparation and application, and can solve the problems of low copolymerization ability of comonomers

Active Publication Date: 2010-11-17
PETROCHINA CO LTD +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

We (application number: 200910083230.8) found that after the traditional high-efficiency Ziegler-Natta catalyst is modified with alcohol, the catalyst can effectively catalyze the copolymerization of ethylene and higher Alpha-olefins, but the use of this modified high-efficiency Ziegler-Natta catalyst catalyzes ethylene / When olefins with large steric hindrance are copolymerized, the copolymerization ability of the comonomer is low

Method used

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  • Ethylene polymerization catalyst, preparation and application thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0037] 1) Prepare the main catalyst: In the reactor fully replaced by nitrogen, add 4g of magnesium dichloride, 3.5ml of epichlorohydrin, 5.5ml of tributyl phosphate, 75ml of toluene, 10ml of hexane, and 3.2ml of ethanol in sequence, and stir Raise the temperature to 70°C, after the solid is completely dissolved to form a homogeneous solution, keep the temperature for 1 hour; then cool down to -25°C, add 58ml of titanium tetrachloride dropwise, after the dropwise addition, add 4mL of trimethylsilyl mercaptan, 3.5ml of triethyl Oxyisopropoxysilane, after reacting for 1h, keep the temperature at -10°C for 1h, 0°C for 1h, 20°C for 1h, add 5ml of hexane, heat up to 60°C, add 10ml of hexane, react for 2h, stop Stir, leave the suspension, separate layers, extract the supernatant, wash twice with toluene, wash twice with hexane, and blow dry with nitrogen to obtain a main catalyst component with good fluidity and narrow particle size distribution;

[0038] 2) Copolymerization of ethy...

Embodiment 2

[0040] 1) Preparation of the main catalyst: In the reactor fully replaced by nitrogen, 4g of magnesium dichloride, 7.5ml of epichlorohydrin, 10.5ml of tributyl phosphate, 75ml of toluene, 8ml of hexane, and 6.2ml of isooctyl alcohol were added successively. Heat up to 60°C under stirring, after the solid is completely dissolved to form a uniform solution, keep the temperature for 1 hour; then cool down to -25°C, add 40ml of titanium tetrachloride dropwise, add 2.5g of triethylsilyl mercaptan after the dropwise addition, 2g Tetraethoxysilane, after reacting for 1 hour, heat up to 60°C, 3ml of hexane, react for 2 hours, stop stirring, let the suspension stand, separate layers, extract the supernatant, wash twice with toluene, and wash twice with hexane , blown dry with nitrogen to obtain a main catalyst component with good fluidity and narrow particle size distribution;

[0041] 2) Copolymerization of ethylene: After a 0.5-liter stainless steel autoclave was fully replaced with ...

Embodiment 3

[0043] 1) Prepare the main catalyst: in the reactor fully replaced by nitrogen, add 3g of magnesium dichloride, 5ml of epichlorohydrin, 10.5ml of tributyl phosphate, 75ml of toluene, 5.2ml of tert-butanol, and 3ml of hexane in sequence, and stir After the solid is completely dissolved to form a uniform solution, keep the temperature for 1 hour; then cool down to -25°C, add 50ml of titanium tetrachloride dropwise, add 3.5g of trinonylsilyl mercaptan, 3g of di Ethoxyisopropoxy tert-butylsilane, after reacting for 1h, keep the temperature at -10°C for 1h, 0°C for 1h, 20°C for 1h, heat up to 60°C for 2h, stop stirring, and let the suspension stand. Layering, extracting the supernatant, washing with toluene twice, washing with hexane twice, and blowing dry with nitrogen to obtain a main catalyst component with good fluidity and narrow particle size distribution;

[0044] 2) Copolymerization of ethylene: After a 0.5-liter stainless steel autoclave was fully replaced with nitrogen, 2...

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Abstract

The invention relates to an ethylene polymerization catalyst, preparation and application thereof. The catalyst consists of a carrier, transition metal halides, organic alcohol compounds, organic silicone compounds and an organic thiols in a molar ratio of 1:(0.01-20):(0.1-6):(0.01-5):(0.001-5). The organic thiols is one or a mixture of two or more of the compounds with a general formula of HS-R1, wherein the R1 is an alkyl group of which the carbon atom number is 1 to 20, a cycloalkyl group of which the carbon atom number is 3 to 20, an aryl group of which the carbon atom number is 6 to 30, an organic silyl group of which the carbon atom number is 1 to 30, an organic cycloalkyl group of which the carbon atom number is 3 to 30, an organic aryl group of which the carbon atom number is 6 to40 or an organic siloxy group of which the carbon atom number is 1 to 30. The catalyst has high activity; a polymer has high molecular weight and wide molecular weight distribution; and the preparation method has the characteristics of simple method, low requirement on equipment and low pollution to environment.

Description

technical field [0001] The invention relates to an ethylene polymerization catalyst as well as its preparation method and application. Background technique [0002] Olefin polymerization catalysts are the core of polyolefin polymerization technology. From the perspective of the development of olefin polymerization catalysts, there are two main aspects: (1) the development of polyolefin resin catalysts that can prepare special or better performance, such as metallocene catalysts (2) For the production of general-purpose polyolefin resins, on the basis of further improving catalyst performance, simplify the catalyst preparation process, reduce catalyst costs, and develop environmentally friendly technologies to improve efficiency ,Increase competitiveness. Before the 1980s, the focus of polyethylene catalyst research was on the pursuit of catalyst efficiency. After nearly 30 years of hard work, the catalytic efficiency of polyethylene catalysts has increased by orders of magn...

Claims

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Application Information

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IPC IPC(8): C08F110/02C08F210/02C08F210/16C08F4/646C08F4/02C08F4/52C08F4/6592C08F4/68
Inventor 义建军黄启谷刘宏吉汪威张明革袁苑孔媛郑宏涛曹晶磊池亮于现建王莉
Owner PETROCHINA CO LTD
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