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A catalytic system for olefin polymerization

A catalytic system, a technology for olefin polymerization, applied in the field of olefin polymerization catalytic systems, and can solve problems such as catalyst difficulties

Active Publication Date: 2017-03-22
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

From the overall situation of commercialized catalysts in the current market, it is better to effectively adjust the overall performance of the catalyst through external electron donors or composite external electron donor compounds, that is, to obtain catalysts with superior orientation ability and hydrogen tuning sensitivity. difficult

Method used

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  • A catalytic system for olefin polymerization
  • A catalytic system for olefin polymerization
  • A catalytic system for olefin polymerization

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0055] Preparation of solid catalyst component A (main catalyst) (prepared according to Example 1 of Chinese patent CN201010548601.8)

[0056] In the reactor fully replaced by high-purity nitrogen, 4.8g of magnesium chloride, 70ml of toluene, 4ml of epichlorohydrin, 12.5ml of tributyl phosphate (TBP), and 1.0ml of tetraethoxysilane were added in sequence, and the temperature was raised to 60 °C, and maintained for 1.0 hour, the solid was completely dissolved. 1.4 g of phthalic anhydride and 30 ml of toluene were added and maintained for an additional hour. Cool the solution below -28°C, add 456ml of TiCl (5ml / min) dropwise within 1 hour, slowly raise the temperature to 85°C (5°C / min), and gradually precipitate solids during the heating process, add di-n-butyl phthalate 1.1 ml of ester was maintained at 85°C for 1 hour, filtered, and washed twice with toluene to obtain a solid precipitate. Then add toluene 72ml, TiCl4 48ml, be heated up to 110 ℃, process 0.5 hour, after drain...

Embodiment 2

[0065] Preparation of composite external electron donor compound solution

[0066] Method 1: In the early stage of polymerization, the hexane solution of triethylaluminum, the hexane solution of the external electron donor alkene-based trihydrocarbyloxysilane, the hexane solution of the external electron donor dihydrocarbyl dihydrocarbyloxysilane, and the solid Catalysts are added to the hopper in sequence, and after a brief pre-complexation, they are added to the polymerization kettle.

[0067] Method 2: First mix the hexane solution of the external electron donor olefin-based trihydrocarbyloxysilane and the external electron donor dihydrocarbyl dihydrocarbyloxysilane in proportion, and then follow the hexane solution of triethylaluminum , the external electron donor mixed solution, and the solid catalyst are sequentially added to the hopper, and after a short pre-complexation, they are added to the polymerization kettle.

[0068] Method 3: Same as method 2, except that the ...

Embodiment 3

[0070] Propylene polymerization

[0071] In a 5-liter autoclave, use a nitrogen stream to purge at 70°C for 1 hour, then replace the polymerization vessel 3 times with gas-phase propylene, and introduce 5 ml of a hexane solution of triethylaluminum (triethylaluminum) under nitrogen protection. concentration of 0.5mmol / ml), 1ml of hexane solution of compound external electron donor compound (concentration of external electron donor is 0.1mmol / ml), 10ml of anhydrous hexane and 8-12mg of granular solid catalyst (main catalyst ). Close the autoclave, introduce an appropriate amount of hydrogen and 1.0-1.2Kg of liquid propylene; rapidly raise the internal temperature to 70°C under stirring. After polymerization at 70°C for 1 hour, the stirring was stopped to remove unpolymerized propylene monomer, the polymer was collected, dried in vacuum at 70°C for 2 hours, and the activity (AC) was calculated by weighing.

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Abstract

The present invention relates to a catalysis system for an olefin polymerization reaction. According to the present invention, a titanium-containing solid granular catalyst component adopting a carboxylic ester compound as an internal electron donor is added with an alkenyl trialkoxy silane compound and a dialkyl dialkoxy silane compound during olefin polymerization, wherein the alkenyl trialkoxy silane compound and the dialkyl dialkoxy silane compound are adopted as the composite external electron donor, such that the high activity and the high directional capability of the catalyst can be maintained, the hydrogen response of the catalyst is substantially improved, especially in the case of requirement of direct polymerization to obtain the high melt index polymer, and the polymerization method is simple.

Description

technical field [0001] The present invention relates to a catalyst system for olefin polymerization, more specifically, to a titanium-containing solid catalyst component containing a titanium compound, an internal electron donor of a carboxylate, a cocatalyst, and an olefin-based trihydrocarbon Oxysilane and dihydrocarbyldihydrocarbyloxysilane are catalyst systems for olefin polymerization with complex external electron donors. [0002] technical background [0003] As we all know, the catalyst system used in the polymerization of α-olefins and their mixtures generally consists of three parts, which are: (1) main catalyst (solid catalyst), (2) co-catalyst (usually alkyl aluminum compounds) and (3) an external electron donor compound added during polymerization. [0004] The use of one or several external electron donor compounds to control the stereoregularity and morphology of polymers during polymerization is well known to those skilled in the art. In addition to affectin...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08F10/00C08F4/649C08F4/646
Inventor 夏先知张天一郭正阳万真
Owner CHINA PETROLEUM & CHEM CORP