Supported metallocene catalyst system and preparation method thereof

A technology of metallocene catalysts and metallocene compounds, which is applied in the field of metallocene catalyst systems supported by organic polymer carriers and its preparation, can solve the problems of complex preparation methods and unfavorable release of active centers of metallocene catalysts, and achieve the goal of preparation methods Simple, good shape of catalyst and polymer, uniform particle size

Active Publication Date: 2015-04-29
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the above carrier is only a solid carrier, which is not conducive to the loading of metallocene catalysts and the release of active centers.
CN101440137A improved on this basis, adopting polystyrene, divinylbenzene and acrylonitrile copolymer to support metallocene, but the preparation method of this method is more complicated

Method used

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  • Supported metallocene catalyst system and preparation method thereof
  • Supported metallocene catalyst system and preparation method thereof
  • Supported metallocene catalyst system and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] Comonomer treatment: use 10% NaOH solution to remove the polymerization inhibitor before use of styrene and divinylbenzene, and then use it after washing with deionized water for 3 times; use neutral alumina chromatography for hydroxyethyl methacrylate The column was used after removing the polymerization inhibitor. The following examples do not specifically illustrate that the comonomers are used after treatment.

[0029] Preparation of organic porous support: In a 250ml glass reactor, add 150ml ethanol and 15ml deionized water, then add 6ml (about 5.6g) styrene, 8ml55% (about 7.5g) divinylbenzene and 5ml methacrylic acid Hydroxyethyl ester (about 5.0g), styrene and divinylbenzene are used to remove the polymerization inhibitor with 10% NaOH solution before use, and then washed with deionized water for 3 times before use, and hydroxyethyl methacrylate is used in neutral The alumina chromatographic column was used after removing the polymerization inhibitor. Stir at r...

Embodiment 2

[0032] Preparation of organic porous support: In a 250ml glass reactor, add 108ml ethanol and 12ml deionized water, then add 3ml (about 2.7g) styrene, 4ml55% (about 3.7g) divinylbenzene and 2ml methacrylic acid Hydroxyethyl ester (about 2.0g), styrene and divinylbenzene use 10% NaOH solution to remove the polymerization inhibitor before use, and then use it after washing 3 times with deionized water. Use neutral hydroxyethyl methacrylate The alumina chromatographic column was used after removing the polymerization inhibitor. Stir at room temperature for 5 minutes, then add 2% polyvinyl alcohol (polymerization degree: 1750) of monomer mass, stir for 1 hour at 45°C, dissolve the polyvinyl alcohol stabilizer, then add 4ml DNBP, and 1.5% monomer mass of AIBN, heated up to 70°C, reacted for 3 hours, then raised the temperature to 80°C, reacted for 5 hours, stirred at 600 rpm, washed 3 times with ethanol, dried to obtain porous organic carrier a-2.

[0033] Loading of the metalloce...

Embodiment 3

[0035] Preparation of organic porous carrier: The preparation of organic porous carrier in Example 3 is different from Example 2 except that the amount of porogen used is different, the preparation steps are the same as the amount of other reagents, and 7mlDNBP is added in Example 3 instead of adding 4mlDNBP to prepare The obtained organic vehicle is designated as a-3.

[0036] Loading of the metallocene catalyst: 4.5 g of the organic porous carrier a-3 prepared by the method of the present invention was vacuum filtered in a vacuum dryer at 120° C. for 24 hours. Add the treated carrier into a 250ml nitrogen-substituted reactor, add 25ml of 10% (mass percent) MAO (produced by CNPC Lanzhou Chemical Research Center) toluene solution, and stir at 20°C for 1 hour. Then add 0.18 g of Cp 2 ZrCl 2 (Dicyclopentadienyl zirconium dichloride) metallocene compound, 10ml of toluene was stirred for 0.5 hours, then reacted at -20°C for 3 hours, the solvent was removed after the reaction, an...

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Abstract

The invention relates to a metallocene catalyst system for olefin polymerization and a preparation method thereof. The catalyst is mainly prepared from an organic high-molecular polymer carrier, a co-catalyst and a metallocene compound, wherein the carrier is styrene-divinyl benzene-hydroxyethyl methylacrylate terpolymer; a molar ratio of aluminum Al in the co-catalyst to metal atom M in the metallocene compound is 50-300; and based on the molar percentage of aluminum Al, each gram of organic high-molecular polymer carrier contains 1-12mmol of co-catalyst. The preparation method mainly comprises the steps of synthesizing the organic high-molecular polymer carrier, and loading the metallocene catalyst. The preparation method is simple and environment-friendly, the prepared catalyst and polymer have good shape since a novel organic porous carrier is adopted, and the catalyst has relatively high activity.

Description

technical field [0001] The invention relates to a metallocene catalyst system, in particular to a metallocene catalyst system supported by an organic polymer carrier and a preparation method thereof. Background technique [0002] In order to make the metallocene catalyst suitable for industrial slurry polymerization or gas phase polymerization, it is necessary to support the metallocene catalyst, first, to reduce the amount of expensive methyl aluminoxane (MAO), and second, to control the morphology of the polymer And avoid polymer sticking to the kettle, etc. The supports currently used to support metallocene catalysts generally include inorganic supports and organic supports. There are many reports on inorganic material carrier as metallocene catalyst carrier, U.S. Patent US4,808,561, US5,026,797, US5,763,543, US5,661,098, US6,455,647, Chinese patent CN1174549, CN1356343 report using inorganic substances such as silicon dioxide, magnesium chloride , alumina, etc. are use...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F4/02C08F4/6592C08F212/36C08F212/08C08F220/28C08J9/28C08F10/02
Inventor 王雄徐人威朱博超韩晓昱刘义任峰姚培洪贾军纪郝萍吴江王丹丹许云波巨娟侠白虹姜健
Owner PETROCHINA CO LTD
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