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Supported metallocene catalyst and olefin polymer, and preparation methods thereof

A metallocene catalyst and metallocene compound technology are applied in the field of supported metallocene catalysts and olefin polymers and their preparation, which can solve the problems of high price and low polyolefin bulk density, and achieve the effect of reducing the preparation cost.

Active Publication Date: 2012-05-16
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The supported catalyst is used for ethylene polymerization and has good polymerization activity, but the mono-titanocene catalyst needs to be added with expensive alkyl aluminoxane at the same time
[0003] CN101182364A discloses the catalyst of modified magnesium chloride supported metallocene compound, when the supported monolocene catalyst does not add alkyl aluminoxane in the polymerization system to carry out olefin polymerization, obtains better reactivity, but experiment proves, this method prepares The resulting polyolefin has a lower bulk density

Method used

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  • Supported metallocene catalyst and olefin polymer, and preparation methods thereof
  • Supported metallocene catalyst and olefin polymer, and preparation methods thereof
  • Supported metallocene catalyst and olefin polymer, and preparation methods thereof

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preparation example Construction

[0033] The present invention also provides a preparation method of the above-mentioned supported metallocene catalyst, the method comprising: under the protection of an inert gas, sequentially supporting the alkylaluminoxane and the metallocene compound on the carrier.

[0034] The method for preparing a supported metallocene catalyst according to the present invention, wherein the method further includes heating the carrier at a temperature of 300-900° C. for 7 hours under the protection of an inert gas before loading the alkylaluminoxane -30 hours.

[0035]According to the preparation method of the supported metallocene catalyst of the present invention, the supported method can be determined according to the well-known content in the field of olefin polymerization catalyst preparation, the present invention is not particularly limited, for example, a preferred supported method includes the following step:

[0036] The first step is to prepare an activated support: under th...

preparation Embodiment 1

[0054] This preparation example is used for preparing R in formula 1 1 , R 2 , R 3 , R 4 and R 5 is methyl and R 1 ’ and R 2 ' is the metallocene compound of isopropyl group.

[0055] Two well-dried 250 ml three-neck flasks were placed in an ice bath and fully replaced with nitrogen three times. Add 1.78 grams of 2,6-diisopropylphenol and 50 milliliters of dry toluene to one of the three-necked flasks, stir until fully dissolved, then slowly add 4.2 milliliters of 2.5 mol / L concentration of butyllithium in hexane within 10 minutes solution. After the dropwise addition was completed, the ice bath was removed, and the reaction was stirred at room temperature for 4 hours to obtain a reaction liquid after the reaction of 2,6-diisopropylphenol and butyllithium. Add 2.89 grams of pentamethylcyclopentadienyl titanium trichloride (purchased from Strem Company) to another three-necked bottle, add 50 ml of dry tetrahydrofuran, start stirring, after fully dissolving, slowly add t...

preparation Embodiment 2

[0057] This preparation example is used for preparing R in formula 1 1 , R 2 , R 3 , R 4 and R 5 is methyl and R 1 ’ and R 2 ' is a metallocene compound of phenyl group.

[0058] Two well-dried 250 ml three-neck flasks were placed in an ice bath and fully replaced with nitrogen three times. Add 2.48 grams of 2,6-diphenylphenol and 50 milliliters of dry toluene to one of the three-necked flasks, stir until fully dissolved, then slowly add 4.2 milliliters of 2.5 mol / L hexane solution of butyllithium in 10 minutes . After the dropwise addition was completed, the ice bath was removed, and the reaction was stirred at room temperature for 4 hours to obtain a reaction liquid after the reaction of 2,6-diisopropylphenol and butyllithium. Add 2.89 g of pentamethylcyclopentadienyl titanium trichloride to another three-necked flask, add 50 ml of dry tetrahydrofuran, start stirring, and after fully dissolving, slowly add 2,6-diphenylphenol and butyl The reaction solution after lit...

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Abstract

The invention provides a supported metallocene catalyst, which comprises a carrier, and alkyl aluminoxane and a metallocene compound which are supported on the carrier, wherein the metallocene compound has a structure shown as a formula 1. The invention also provides a method for preparing the supported metallocene catalyst, a method for preparing an olefin polymer by using the catalyst, and the olefin polymer prepared by the method for preparing the olefin polymer. In the olefin polymerization process, the supported metallocene catalyst can reduce the using amount of the alkyl aluminoxane so as to reduce the preparation cost of the olefin polymer; the high molecular weight polyethylene prepared by using the catalyst has a good shape and high bulk density; and the catalyst can be applied to gas-phase polymerization and slurry polymerization processes. The formula 1 is shown as the specifications.

Description

technical field [0001] The invention relates to a supported metallocene catalyst, an olefin polymer and a preparation method thereof. Background technique [0002] In recent years, in the field of olefin polymerization, monometallocene compounds have attracted more and more attention, especially aryl (alk)oxy titanocene metal compounds not only exhibit the properties of ethylene, styrene, non-conjugated di Olefin polymerization is highly active, and it has high activity and excellent copolymerization ability for the copolymerization of α-olefins, cycloolefins, etc. Metallocene catalysts are catalysts with a single active center, which have excellent performance and can control the molecular weight and molecular weight distribution, molecular chain branching structure, comonomer content and distribution on the main chain of polyethylene. In the existing reports, many single titanocene compounds have been synthesized and applied to ethylene polymerization. In order to be wid...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F4/6592C08F4/02C08F10/00
Inventor 邓晓音王伟郑刚刘长城王红英
Owner CHINA PETROLEUM & CHEM CORP
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