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A kind of propylene polymerization catalyst system and its application

A technology of propylene polymerization and catalyst, which is applied in the application field of preparing high-rigidity heat-resistant polypropylene, and can solve the problems of low-standard polypropylene

Active Publication Date: 2022-07-05
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

For example, composite external electron donors are commonly used in the industry for the production of high-flow polypropylene, such as composite external electron donors composed of methylcyclohexyldimethoxysilane (CHMMS) and dicyclopentyldimethoxysilane (DCPDMS) , usually commercially used catalysts have high hydrogen modulation sensitivity to CHMMS external electron donors, but the isotacticity of the prepared polypropylene is low, adding DCPDMS external electron donors will increase the polymer isotacticity, so that the product has a high Higher isotacticity at melt index

Method used

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  • A kind of propylene polymerization catalyst system and its application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] The solid component (A) is the preparation of the main catalyst:

[0027] Under nitrogen protection, in a 500ml four-hole glass reactor, at 0 ℃, first add 250ml of titanium tetrachloride, and under stirring, add 10g of magnesium chloride alcoholate (MgCl 2 *2.8C 2 H 5 OH) was added dropwise to the cooled titanium tetrachloride, and after the dropwise addition was completed, the temperature was raised to 120° C. for a predetermined time of reaction, allowed to stand, and filtered with suction. After dropping to room temperature, add 250 ml of titanium tetrachloride, then heat up to 100 ° C and add 2.05 g (about 7.4 mmol) of diisobutyl phthalate (DIBP) internal electron donor, and react at this temperature for 1 h, The temperature was raised to 120° C. to react for a period of time, left standing, washed several times with toluene and n-hexane, and vacuum-dried to obtain free-flowing catalyst particles cat-1. Solid catalyst component titanium content: 3.2%, ester conte...

Embodiment 2

[0029] The solid component (A) is the preparation of the main catalyst:

[0030] Under nitrogen protection, in a 500ml four-hole glass reactor, at 0 ℃, first add 250ml of titanium tetrachloride, and under stirring, add 10g of magnesium chloride alcoholate carrier (MgCl 2 *2.8C 2 H 5 OH) was added dropwise to the cooled titanium tetrachloride, and after the dropwise addition was completed, the temperature was raised to 120° C. for a predetermined time of reaction, allowed to stand, and filtered with suction. After cooling to room temperature, add 250ml of titanium tetrachloride, then heat up to 100°C and add 2.10g of di-n-butyl phthalate (DNBP) as an electron donor, react at this temperature for 1h, then heat up to 120°C for a period of reaction time, left to stand, washed several times with toluene and n-hexane, and dried under vacuum to obtain free-flowing catalyst particles cat-2. Solid catalyst component titanium content: 2.8%, ester content 11.7%.

Embodiment 3

[0032] Preparation of di-n-butyl 2-cyano-2,3-dimethylsuccinate:

[0033] using S N 2 is prepared by coupling, and the preparation method can refer to the method used in CN1240729C.

[0034] At 0°C, 157 mmol of 2-cyanopropionic acid was added to a freshly prepared solution of lithium diisopropylamide (41 mL, 314 mmol of diisopropylamine and 126 mL of BuLi (2.5 M in hexane; 314 mmol) and 1 L of tetrahydrofuran THF). The mixture was stirred at 0°C for 15 minutes and then at 45°C for 4 hours while in a separate reactor 14.1 ml (157 mmol) 2-bromopropionic acid and 28 g (157 mmol) hexamethylphosphoryl were added at 0°C The mixture of triamine HMPA was added to a suspension of 3.8 g (157 mmol) NaH in 500 mL THF while controlling gas formation. After the addition, the mixture was stirred at 0°C for 15 minutes, then the mixture was added to the above mixture of lithium 2-cyanopropionate at 0°C, and the mixture was stirred at 35°C for 2 hours at 0°C. The mixture was rapidly cooled w...

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Abstract

A propylene polymerization catalyst system, comprising a solid catalytic component (A), an aluminum alkyl (B) and a multi-component external electron donor (C), wherein the component (A) is a magnesium chloride-supported Ti solid component, and contains adjacent Phthalic acid diester internal electron donor; component (B) is trialkyl aluminum; component (C) includes the first type of external electron donor and the second type of external electron donor, the first type of external electron donor The molar ratio with the second type of external electron donor is 1-70:30-99; wherein the first type of external electron donor is selected from dicyclopentyldimethoxysilane, diisopropyldimethoxysilane Silane; the second type of external electron donor is selected from di-n-butyl 2-cyano-2,3-dimethylsuccinate. The heat-resistant polypropylene obtained by using the catalyst system has high regularity and wide molecular weight distribution, so that the material has a good balance of rigidity and toughness. The technology does not need to modify the original device, is suitable for existing industrial production devices with different processes, and has good economic promotion value.

Description

technical field [0001] The present invention relates to an olefin polymerization catalyst system and its application, in particular to an olefin polymerization catalyst system containing an external electron donor and its application in preparing high-rigidity heat-resistant polypropylene. Background technique [0002] Polypropylene is a polymer polymerized from propylene monomer. It has the advantages of wide modulation range, excellent processing performance, strong chemical corrosion resistance and high cost performance due to its mechanical properties, thermal properties and crystallization properties. It is widely used in various fields such as automobiles, household appliances, and biomedicine, and has become one of the most widely used general-purpose plastics in global demand. [0003] Due to the gradual improvement of living standards, household appliances, especially various small appliances, have also become a huge potential market for the polypropylene production...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08F10/06C08F110/06C08F4/649C08F4/646
CPCC08F10/06C08F110/06C08F4/6495C08F4/6465
Inventor 王雄徐人威高玉林剡军巨娟侠曹振祥刘晨李忠闫功臣魏瑶韩晓昱张卫华张翠玲樊洁李艳芹郭义
Owner PETROCHINA CO LTD
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