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Supported non-metallocene catalyst as well as preparation method and application thereof

A non-metallocene, supported technology, applied in the direction of catalyst activation/preparation, chemical instruments and methods, physical/chemical process catalysts, etc., can solve problems such as difficult to adjust, low catalytic activity, fragile, etc.

Active Publication Date: 2011-05-04
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0008] 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
[0012] Nevertheless, the ubiquitous problems of the supported non-metallocene catalysts in the prior art are that the loading process is complicated, and generally requires multi-step treatment of the support before loading the non-metallocene complexes, and the olefin polymerization activity is low and difficult to adjust. , and in order to improve its polymerization activity, a higher amount of co-catalyst must be assisted in the polymerization of olefins

Method used

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  • Supported non-metallocene catalyst as well as preparation method and application thereof
  • Supported non-metallocene catalyst as well as preparation method and application thereof
  • Supported non-metallocene catalyst as well as preparation method and application thereof

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preparation example Construction

[0088] According to the present invention, it relates to a preparation method of a supported non-metallocene catalyst, comprising the following steps: dissolving a magnesium compound and a non-metallocene complex in a solvent to obtain a magnesium compound solution; The step of mixing the porous carrier with the magnesium compound solution to obtain a mixed slurry; drying the mixed slurry to obtain a composite carrier; and treating the composite carrier with a chemical treatment agent selected from group IVB metal compounds to obtain the Steps for a supported non-metallocene catalyst.

[0089] The steps for obtaining the magnesium compound solution are specifically described below.

[0090] Specifically, the magnesium compound (solid) and the non-metallocene complex are dissolved in an appropriate solvent (hereinafter sometimes referred to as "a solvent for dissolving the magnesium compound"), thereby obtaining the magnesium compound solution.

[0091] As the solvent, for ex...

Embodiment 1

[0299] The magnesium compound adopts anhydrous magnesium chloride, the solvent for dissolving the magnesium compound and the non-metallocene complex adopts tetrahydrofuran, and the chemical treatment agent adopts titanium tetrachloride. The porous carrier adopts silica, that is, silica gel, the model is ES757 of Ineos Company, and the non-metallocene complex adopts the structure of compound of.

[0300] Firstly, the silica gel was continuously fired at 600° C. under nitrogen atmosphere for 4 hours to thermally activate it.

[0301] Weigh 5g of anhydrous magnesium chloride and non-metallocene complexes, add tetrahydrofuran solvent and dissolve completely at room temperature, then add heat-activated silica gel, stir for 2 hours, heat evenly to 90°C and directly vacuum-dry to obtain a composite carrier.

[0302] Then add 60ml of hexane to the composite carrier, add titanium tetrachloride dropwise for 30 minutes under stirring conditions, stir and react at 60°C for 4 hours, filt...

Embodiment 1-1

[0306] Basically the same as Example 1, but with the following changes:

[0307] The porous carrier was changed to Grace's 955, and it was continuously calcined at 400° C. for 8 hours under a nitrogen atmosphere to be thermally activated.

[0308] Non-metallocene complexes using The solvent for dissolving magnesium compounds and non-metallocene complexes was changed to toluene, and the chemical treatment agent was changed to zirconium tetrachloride (ZrCl 4 ).

[0309] Wherein the ratio is as follows: the ratio of magnesium compound to toluene is 1mol:150ml; the molar ratio of magnesium compound to non-metallocene complex is 1:0.15; the mass ratio of magnesium compound to porous carrier is 1:4; the magnesium compound and chemical treatment agent The molar ratio is 1:0.20.

[0310] Supported non-metallocene catalysts are designated CAT-1-1.

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Abstract

The invention relates to a supported non-metallocene catalyst and a preparation method thereof. The catalyst has the characteristics of simple and practical preparation method, flexible and adjustable polymerization activity and the like, and the non-metallocene compound in the catalyst and the chemical treatment agent have synergy beneficial to giving play to activity. The invention also relatesto an application of the supported non-metallocene catalyst in olefin homopolymerization / copolymerization. Compared with the prior art, the catalyst is characterized in that the dosage of the promoter is less in the application.

Description

technical field [0001] 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 [0002] The non-metallocene catalysts that appeared in the middle and late 1990s, also known as post-metallocene catalysts, the central atoms of the main catalysts include almost all transition metal elements, which have reached or even surpassed metallocene catalysts in some performance aspects, becoming The fourth generation of olefin polymerization catalysts after Ziegler, Ziegler-Natta and metallocene catalysts. The polyolefin product produced by this type of catalyst has excellent performance and low production cost. The coordination atoms of non-metallocene catalysts are oxygen, nitrogen, sulfur and phosphorus, and do not contain cyclopentadiene groups or their derivative groups, such as ind...

Claims

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Application Information

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IPC IPC(8): B01J31/26B01J31/22B01J31/24B01J37/00C08F10/00C08F4/645C08F4/654
Inventor 李传峰任鸿平姚小利马忠林郭峰汪开秀刘经伟王亚明杨立娟
Owner CHINA PETROLEUM & CHEM CORP
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