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Loaded non-metallocene catalyst and preparation method and application thereof

A non-metallocene and non-metallocene ligand technology, applied in the field of non-metallocene catalysts, can solve the problems of difficult to control the content of catalyst components, low catalytic activity, high vacuum and the like

Active Publication Date: 2013-09-04
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The problem with this catalyst is that the loading process requires high temperature and high vacuum, so it is difficult to apply to industrial production
[0012] 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
[0016] Even so, the ubiquitous problem of supported non-metallocene catalysts in the prior art is that multi-step treatment of the support is required, and includes the treatment of compounds containing catalytically active metals before loading the non-metallocene ligands, or first loading Non-metallocene ligands, after being treated with compounds containing catalytically active metals, the loading process is complicated
Moreover, since the non-metallocene ligands are formed step by step and immobilized on the treated carrier, the catalyst components and their content are difficult to control, and there are batch product quality problems

Method used

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  • Loaded non-metallocene catalyst and preparation method and application thereof
  • Loaded non-metallocene catalyst and preparation method and application thereof
  • Loaded non-metallocene catalyst and preparation method and application thereof

Examples

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preparation example Construction

[0082] 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 ligand 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.

[0083] The steps for obtaining the magnesium compound solution are specifically described below.

[0084] Specifically, the magnesium compound (solid) and the non-metallocene ligand are dissolved in an appropriate solvent (ie, a solvent for dissolving the magnesium compound), thereby obtaining the magnesium compound solution.

[0085] As the solvent, for example, C 6-12 Aromatic hydrocarbons, ...

Embodiment 1

[0291] The magnesium compound adopts anhydrous magnesium chloride, the solvent for dissolving the magnesium compound and the non-metallocene ligand adopts tetrahydrofuran, and the chemical treatment agent adopts titanium tetrachloride. The porous carrier adopts silicon dioxide, that is, silica gel, the model is ES757 of Ineos Company, and the non-metallocene ligand adopts the structure of compound of.

[0292] Firstly, the silica gel was continuously fired at 600° C. under nitrogen atmosphere for 4 hours to thermally activate it.

[0293] Weigh 5g of anhydrous magnesium chloride and non-metallocene ligands, 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.

[0294] 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,...

Embodiment 1-1

[0298] Basically the same as Example 1, but with the following changes:

[0299] 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.

[0300] Non-metallocene ligands use , the solvent for dissolving magnesium compounds and non-metallocene ligands was changed to toluene, and the chemical treatment agent was changed to zirconium tetrachloride (ZrCl 4 ).

[0301] The proportioning ratio is as follows: the ratio of magnesium compound to toluene is 1mol: 150ml; the molar ratio of magnesium compound to non-metallocene ligand 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.

[0302] Supported non-metallocene catalysts are designated CAT-1-1.

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Abstract

The invention relates to a loaded non-metallocene catalyst and a preparation method and application thereof. The loaded non-metallocene catalyst has the characteristics of simple and practicable preparation method, flexible and adjustable polymerization activity and the like. The invention also relates to the application of the loaded non-metallocene catalyst to the homopolymerisation / copolymerization of olefin. Compared with the prior art, the application has the characteristic of small using amount of a cocatalyst.

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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Patent Type & Authority Patents(China)
IPC IPC(8): C08F10/00B01J31/38B01J31/24B01J31/22B01J37/00C08F4/654C08F4/658C08F4/02C08F110/02C08F210/02
Inventor 姚小利李传峰任鸿平马忠林郭峰汪开秀刘经伟王亚明
Owner CHINA PETROLEUM & CHEM CORP
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