Metallocene catalyst system and preparation method thereof

A technology of metallocene catalysts and metallocene compounds, applied in the field of metallocene catalyst systems and their preparation, can solve the problems of unfavorable metallocene catalyst active center release and complex preparation methods, and achieve catalysts and polymers with good morphology and simple preparation methods , the effect of narrow dispersion

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

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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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  • Metallocene catalyst system and preparation method thereof
  • Metallocene catalyst system and preparation method thereof
  • Metallocene catalyst system and preparation method thereof

Examples

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Effect test

Embodiment 1

[0029] Comonomer treatment: use 10% NaOH solution to remove the polymerization inhibitor before use of styrene and divinylbenzene, and then use it after washing 3 times with deionized water; use neutral oxidation for ethylene glycol dimethacrylate The aluminum chromatographic column was used after removing the polymerization inhibitor. The following examples do not specifically illustrate that the comonomers are used after treatment.

[0030] Preparation of organic porous support: In a 250ml glass reactor, add 150ml ethanol and 15ml deionized water, then add 8ml (about 7.4g) styrene, 8ml 55% (about 7.5g) divinylbenzene and 5ml dimethyl Ethylene glycol acrylate (about 4.8g), stirred at room temperature for 5 minutes, then added 2% polyvinyl alcohol (polymerization degree: 1750) of monomer mass at 45°C, stirred for 1 hour to dissolve the polyvinyl alcohol stabilizer, Then add 10ml DNBP and 1.5% AIBN of monomer mass, raise the temperature to 70°C, react for 3 hours, then raise t...

Embodiment 2

[0033] Preparation of organic porous support: In a 250ml glass reactor, add 108ml ethanol and 12ml deionized water, then add 4ml (about 3.9g) styrene, 4ml 55% (about 3.7g) divinylbenzene and 2ml dimethyl Ethylene glycol acrylate (about 2.0g), stirred at room temperature for 5 minutes, then added 2% polyvinyl alcohol (polymerization degree: 1750) of monomer mass at 45°C, stirred for 1 hour to dissolve the polyvinyl alcohol stabilizer, Then add 4ml DNBP and 1.5% AIBN of monomer mass, raise the temperature to 70°C, react for 3 hours, then raise the temperature to 80°C, react for 5 hours, stir at 600 rpm, wash with ethanol 3 times, and dry Finally, the porous organic carrier a-2 is obtained.

[0034] Loading of the metallocene catalyst: 3.2 g of the organic porous carrier a-2 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 21ml of 10% (mass percent...

Embodiment 3

[0036] 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.

[0037] 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 an olefin polymerized metallocene catalyst system 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 monodisperse porous styrene-divinyl benzene-ethylene glycol dimethacrylate terpolymer; the co-catalyst (based on the molar percentage of aluminum Al) and the metallocene compound (based on the molar percentage of metal atom M in the compound) are in a molar ratio Al:M being 75-300; 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 and a preparation method thereof, in particular to a metallocene catalyst 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 chlorid...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F4/6592C08F4/02C08F212/08C08F212/36C08F222/14C08J9/26C08F10/00
Inventor 王雄朱博超徐人威韩晓昱任峰刘义姚培洪贾军纪许云波吴江郝萍王丹丹姜立刚白虹姜健
Owner PETROCHINA CO LTD
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