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Loaded non-metallocene catalyst, its preparation method and application

A non-metallocene, supported technology, applied in the field of non-metallocene catalysts, can solve the problems of low catalytic activity, difficult to control the carrier forming process and particle shape, and difficult to control the polymer shape, and achieve the effect of a simple preparation method.

Active Publication Date: 2013-09-18
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, this type of catalyst adopts vacuum drying or solvent precipitation during the carrier forming process, and it is difficult to control the carrier forming process and particle shape, so the shape of the polymer is difficult to control
[0009] Catalysts supported on anhydrous magnesium chloride show high catalytic activity in olefin polymerization, but such catalysts are very brittle and break easily in the polymerization reactor, resulting in poor polymer morphology
Silica-supported catalysts have good fluidity and can be used in gas-phase fluidized bed polymerization, but silica-supported metallocene and non-metallocene catalysts show low catalytic activity

Method used

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  • Loaded non-metallocene catalyst, its preparation method and application
  • Loaded non-metallocene catalyst, its preparation method and application
  • Loaded non-metallocene catalyst, its preparation method and application

Examples

Experimental program
Comparison scheme
Effect test

no. 1 approach

[0179] In the context of the present invention, unless otherwise clearly defined, or the meaning is beyond the scope of understanding of those skilled in the art, hydrocarbon or hydrocarbon derivative groups with more than 3 carbon atoms (such as propyl, propoxy, butyl , butane, butene, butenyl, hexane, etc.) all have the same meaning as when the prefix "positive" is not prefixed. For example, propyl is generally understood as n-propyl and butyl is generally understood as n-butyl.

[0180] The invention relates to a preparation method of a supported non-metallocene catalyst, comprising the following steps: reacting a porous carrier optionally subjected to thermal activation treatment, a Grignard reagent and a halogenating reagent to obtain a composite carrier; The chemical treatment agent of the metal compound reacts with the composite carrier to obtain a modified composite carrier; the step of contacting the non-metallocene complex with the modified composite carrier in the p...

Embodiment 1

[0399] The Grignard reagent adopts methylmagnesium chloride (MeMgCl), the solvent for dissolving the Grignard reagent adopts tetrahydrofuran, the halogenated reagent adopts chlorobutane, and the porous carrier adopts silica, that is, silica gel, and the model is ES757 of Ineos Company, which is non-metallocene The complex adopts the structure The compound, the chemical treatment agent adopts titanium tetrachloride, and the second solvent adopts dichloromethane.

[0400] Firstly, the silica gel was continuously fired at 600° C. under nitrogen atmosphere for 4 hours to thermally activate it.

[0401] Weigh the activated silica gel, add it into the Grignard reagent solution (containing 0.1mol Grignard reagent) at normal temperature to form a homogeneous slurry, add the halogenated reagent dropwise to the homogeneous slurry under stirring at normal temperature, and the dropping time is 30 minutes . After the dropwise addition was completed, the mixture was stirred at room tempe...

Embodiment 2

[0407] Basically the same as Example 1, but with the following changes:

[0408] The Grignard reagent uses ethylmagnesium chloride (EtMgCl), the solvent used to dissolve the Grignard reagent is ether, the halogenated reagent uses ethyl chloride, and the non-metallocene complex uses The porous carrier was changed to 955 type silica gel of Grace Company, which was continuously calcined at 400° C. under nitrogen atmosphere for 8 hours to be thermally activated. The chemical treatment agent was titanium tetrachloride, and the second solvent was chloroform.

[0409] Wherein the proportioning is that the proportioning of the Grignard reagent in terms of Mg element and the solvent for dissolving the Grignard reagent is 1mol: 500mL, and the molar ratio of the Grignard reagent to the halogenated reagent is 1: 2; The molar ratio of the metal complex is 1: 0.1; the molar ratio of the Grignard reagent to the chemical treatment agent is 1: 0.20; the ratio of the Grignard reagent to the po...

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Abstract

The invention relates to a loaded non-metallocene catalyst and its preparation method. The loaded non-metallocene catalyst has the characteristics of simple and feasible process, controllable non-metallocene component content, and substantial copolymerization effect, etc. The invention also relates to application of the loaded non-metallocene catalyst in olefin homopolymerization / copolymerization. Compared with the prior art, during application, the loaded non-metallocene catalyst has high olefin polymerization catalytic activity, small particle size and uniform distribution, and the obtained polymer has a high bulk density.

Description

[0001] This application is based on the ongoing research project of "National Eleventh Five-Year Support Program Topics". The project has been highly valued and strongly supported by the Ministry of Science and Technology of the People's Republic of China. Its goal is to form a new generation of polyolefin catalyst technology with independent intellectual property rights, improve the homogeneity of domestic related products, improve the grade of polyolefin varieties in my country, and promote its development. Development in the direction of diversification, serialization, specialization and high performance. technical field [0002] The present invention relates to a non-metallocene catalyst. Specifically, the present invention relates to a supported non-metallocene catalyst, its preparation method and its application in olefin homopolymerization / copolymerization. Background technique [0003] The non-metallocene catalysts that appeared in the mid-to-late 1990s are also call...

Claims

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Application Information

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IPC IPC(8): C08F10/00C08F4/658C08F4/656C08F4/654C08F4/653C08F4/655C08F4/02
Inventor 李传峰任鸿平郭峰阚林柏基业马忠林陈韶辉王亚明杨爱武
Owner CHINA PETROLEUM & CHEM CORP
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