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Olefin polymerization catalyst system and application thereof

A technology of olefin polymerization and catalyst, which is applied in the field of olefin polymerization, can solve problems such as difficulties, and achieve the effects of simple polymerization method, high polymerization activity, and improved hydrogen adjustment sensitivity

Active Publication Date: 2017-03-29
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, from the general situation, it is difficult to effectively adjust the overall performance of the catalyst through the external electron donor or the composition of the external electron donor compound in the prior art, that is, to obtain a catalyst with superior polymerization activity and hydrogen modulation sensitivity.

Method used

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  • Olefin polymerization catalyst system and application thereof
  • Olefin polymerization catalyst system and application thereof
  • Olefin polymerization catalyst system and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment approach

[0100] According to a specific embodiment of the present invention, the specific preparation method of the magnesium halide alcoholate carrier includes: mixing anhydrous magnesium halide and lower carbon alcohol, and heating up to react to form a magnesium halide alcoholate melt, and the reaction temperature is 90-140°C, after high-shearing in the dispersion medium, put it into the cooled inert medium to form spherical magnesium halide alcoholate particles, and obtain spherical carriers after washing and drying. High shear can be obtained by conventional methods, such as high-speed stirring method (such as CN1330086), spray method (such as US6020279), and high-gravity rotating bed (such as CN1580136A) and emulsifier method (CN1463990A). The dispersant system uses hydrocarbon inert solvents, such as kerosene, white oil, silicone oil, paraffin oil, vaseline oil, etc. The cooling medium is selected from pentane, hexane, heptane, petroleum ether, raffinate and the like.

[0101] ...

preparation example

[0113] (1) In a 300ml stirred glass reaction bottle fully replaced by high-purity nitrogen, add 90ml of titanium tetrachloride and 10ml of hexane, cool to -20°C, add 8g of spherical magnesium chloride alcoholate carrier (preparation method See Chinese patent CN1330086A),

[0114] (2) Under stirring, when slowly heating up to 40°C, add 1.5ml of diol ester compound and 1.5ml of diether compound,

[0115] (3) Continue to heat up to 110°C, and after reaching the temperature, keep the temperature for 0.5h, remove the liquid by suction filtration,

[0116] (4) Add 100ml of titanium tetrachloride, raise the temperature to 110°C, keep the temperature for 1h after reaching the temperature, and remove the liquid by suction filtration. A total of three titanium treatments were added,

[0117] (5) Then wash five times with hexane, and obtain spherical catalyst A after vacuum drying.

Embodiment

[0119] According to the ingredients in Examples 1-15 and Comparative Examples 1-4 in Table 1, and referring to the following conditions, the polymerization of propylene was carried out.

[0120] In a 5-liter autoclave, nitrogen flow was used to purging at 70°C for 1 hour, then the polymerization vessel was replaced 3 times with gas-phase propylene, and 5ml of alkylaluminum compound (the concentration of triethylaluminum was 0.5 mmol / ml), 1ml of the hexane solution of the external electron donor (the concentration of the external electron donor is 0.1mmol / ml), 10ml of anhydrous hexane and 4-6mg of titanium-containing solid catalyst component A. Close the autoclave, introduce a certain volume of hydrogen (at 25°C, atmospheric pressure) (L) and 1.0-1.2Kg of liquid propylene; quickly raise the internal temperature to 70°C while stirring. After the polymerization reaction at 70°C for 1 hour, the stirring was stopped to remove unpolymerized propylene monomer, and the polymer was col...

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Abstract

The invention relates to the field of olefin polymerization, and discloses a catalyst system. The catalyst system comprises a titaniferous solid catalyst component, an aluminum alkyl compound and an external electron donor compound, wherein the titaniferous solid catalyst component contains at least two internal electron donor compounds of a polytrimethylene terephthalate type compound and a diether type compound, and the external electron donor compound is an ether base ester compound or a combination of the ether base ester compound and hydroxyl silane dialkyl oxygen radicals. The invention further provides application of the catalyst in olefin polymerization reaction. According to the catalyst system and the application of the catalyst in the olefin polymerization reaction, by adding the ether base ester compound or the combination of the ether base ester compound and the hydroxyl silane dialkyl oxygen radicals as the external electron donors to be used in the olefin polymerization reaction when the solid catalyst component with the polytrimethylene terephthalate type compound and the diether type compound being the internal electron donors is subjected to the olefin polymerization reaction, not only can the catalyst maintain high activity, but also sensibility of hydrogen regulation of the catalyst can be improved.

Description

technical field [0001] The invention relates to the field of olefin polymerization, in particular, the invention relates to a catalyst system and its application in olefin polymerization. Background technique [0002] As we all know, the catalyst system used in the homopolymerization or copolymerization of α-olefins generally consists of three parts, which are: (1) main catalyst (solid catalyst), (2) cocatalyst (usually alkyl aluminum compounds) and (3) an external electron donor compound added during polymerization. [0003] 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 affecting the stereoregularity of the polymer, the external electron donor often affects other aspects of the performance of the catalyst to varying degrees. Although many compounds are known to act as external electron donors, the use of different externa...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F10/00C08F4/649C08F4/646
Inventor 张天一夏先知赵瑾刘月祥
Owner CHINA PETROLEUM & CHEM CORP
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