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Supported non-metallocene catalyst and its preparation method and use

A non-metallocene, supported technology, applied in the field of non-metallocene catalysts, can solve problems that affect the stable operation of polymerization production equipment, low mechanical strength of catalysts, and complicated loading process

Active Publication Date: 2012-04-04
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, these patents all involve loading non-metallocene organic compounds containing transition metals on the treated carrier, and the catalyst preparation process is relatively complicated.
[0007] Catalysts supported by anhydrous magnesium chloride show high catalytic activity in olefin polymerization, but such catalysts are weak and easily broken in the polymerization reactor, resulting in poor polymer morphology
Silica-supported catalysts have good fluidity and can be used in slurry polymerization and gas-phase fluidized-bed polymerization, but pure silica-supported metallocene and non-metallocene catalysts show lower catalytic activity
Since the magnesium compound is used as a single carrier, the mechanical strength of the catalyst is low, and polymer fine powder is easily formed during the polymerization process, which affects the stable operation of the polymerization production device
[0016] Even so, the ubiquitous problem of the supported non-metallocene catalysts existing in the prior art is that the loading process is complicated
For the composite support formed by porous carrier and magnesium compound, such as Chinese patent 200410066068.6, and the patent PCT / CN2005 / 001737 based on its application discloses a loading method of a highly active non-metallocene catalyst and a Supported non-metallocene olefin polymerization catalyst, its preparation method and its application, due to the existence of alcohol in the system, it will have an adverse effect on the performance of the non-metallocene complex supported on it, limiting the intrinsic performance of the non-metallocene complex full play

Method used

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  • Supported non-metallocene catalyst and its preparation method and use
  • Supported non-metallocene catalyst and its preparation method and use
  • Supported non-metallocene catalyst and its preparation method and use

Examples

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preparation example Construction

[0084] The invention relates to a preparation method of a supported non-metallocene catalyst, comprising the following steps: reacting a chemical treatment agent selected from group IVB metal compounds with a porous carrier optionally subjected to thermal activation treatment to obtain a modified carrier; making magnesium Dissolving the compound in a solvent to obtain a magnesium compound solution; contacting the modified carrier and the magnesium compound solution with a non-metallocene ligand to obtain a mixed slurry; adding a precipitant to the mixed slurry to obtain a composite The step of supporting; and the step of reacting the chemical treatment agent selected from the group IVB metal compound with the composite carrier to obtain the supported non-metallocene catalyst.

[0085] The porous carrier will be specifically described below.

[0086] According to the present invention, as the porous support, for example, those organic or inorganic porous solids conventionally u...

Embodiment 1

[0283] The porous carrier is silicon dioxide, that is, silica gel, model ES757 of Ineos Company. First, the silica gel is thermally activated by continuously calcining at 600° C. for 4 hours under a nitrogen atmosphere.

[0284] The chemical treatment agent is titanium tetrachloride (TiCl 4 ). Weigh 5g of thermally activated silica gel, add 60ml of hexane, add titanium tetrachloride under normal temperature stirring conditions, react at 60°C for 2h, filter, wash with hexane 3 times, 60ml each time, and finally vacuum dry to obtain modified carrier.

[0285] The magnesium compound adopts anhydrous magnesium chloride, and the solvent for dissolving the magnesium compound and the non-metallocene ligand adopts tetrahydrofuran. The non-metallocene ligand adopts the structure compound of.

[0286] Weigh anhydrous magnesium chloride and non-metallocene ligands, add tetrahydrofuran solvent and dissolve completely at room temperature to obtain magnesium compound solution, then add...

Embodiment 2

[0291] Basically the same as Example 1, but with the following changes:

[0292] 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. The chemical treatment agent was changed to zirconium tetrachloride (ZrCl 4 ), hexane was changed to toluene. Non-metallocene ligands use The solvent for dissolving magnesium compounds and non-metallocene ligands was changed to toluene, and the precipitating agent was changed to cyclohexane.

[0293] Then add 60ml of toluene to the composite carrier, add zirconium tetrachloride dropwise for 30 minutes under stirring conditions, stir and react at 80°C for 4 hours, filter, wash with toluene twice, use 60ml of toluene each time, vacuum at 60°C Dry to obtain a supported non-metallocene catalyst.

[0294] Wherein the ratio is that the mass ratio of the magnesium compound to the porous carrier is 1:1; in terms of Mg element, the molar ratio of...

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Abstract

The invention relates to a supported non-metallocene catalyst and its preparation method. The preparation method of the supported non-metallocene catalyst is an in-situ preparation method, is simple, is easy for operation, realizes control on non-metallocene content and has an obvious copolymerization effect. The invention also relates to a use of the supported non-metallocene catalyst in alkene homopolymerization / copolymerization. Compared with the prior art, the use of supported non-metallocene catalyst has the characteristics of high alkene catalysis activity, high polymer bulk density andcontrollable molecular weight distribution.

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): C08F4/654C08F4/651C08F4/02C08F10/00
Inventor 任鸿平李传峰郭峰阚林柏基业马忠林陈韶辉汪开秀王亚明陈海滨杨爱武
Owner CHINA PETROLEUM & CHEM CORP
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