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Propylene polymerization catalyst system and application thereof

A propylene polymerization and catalyst technology, which is applied in the application field of preparing high-rigidity heat-resistant polypropylene, can solve the problem of low-standard polypropylene, and achieve good rigidity-toughness balance, good economic promotion value, and good rigidity-toughness balance Effect

Active Publication Date: 2020-12-11
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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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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  • Propylene polymerization catalyst system and application thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

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

[0027] Under the protection of nitrogen, in a 500ml four-port glass reactor, at 0°C, first add 250ml of titanium tetrachloride, and then 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. to react for a predetermined time, left to stand, and suction filtered. After cooling down to room temperature, add 250ml of titanium tetrachloride, then raise the temperature to 100°C and add 2.05g (about 7.4 mmol) of diisobutyl phthalate (DIBP) as an internal electron donor, and react at this temperature for 1h. Raise the temperature to 120°C to react for a period of time, let stand, wash with toluene and n-hexane several times, and dry in vacuum to obtain free-flowing catalyst particles cat-1. Titanium content of solid catalyst component: 3.2%, ester content 12.7%.

Embodiment 2

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

[0030] Under the protection of nitrogen, in a 500ml four-port glass reactor, at 0 ° C, first add 250ml of titanium tetrachloride, and in the case of 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. to react for a predetermined time, left to stand, and suction filtered. After cooling down to room temperature, add 250ml of titanium tetrachloride, then raise the temperature to 100°C and add 2.10g of di-n-butyl phthalate (DNBP) internal electron donor, react at this temperature for 1 hour, then raise the temperature to 120°C for a period of reaction time, let it stand, washed several times with toluene and n-hexane, and vacuum dried to obtain free-flowing catalyst particles cat-2. Titanium content of solid catalyst component: 2.8%, ester co...

Embodiment 3

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

[0033] Use S N 2 coupling for preparation, the preparation method can refer to the method used in CN1240729C.

[0034] Add 157 mmol 2-cyanopropionic acid to freshly prepared lithium diisopropylamide solution (41 mL, 314 mmol diisopropylamine and 126 mL of BuLi (2.5M in hexane; 314 mmol) and 1 L of tetrahydrofuran at 0 °C THF). The mixture was stirred at 0°C for 15 minutes and then stirred at 45°C for 4 hours, while in another reactor, 14.1ml (157mmol) of 2-bromopropionic acid and 28g (157mmol) of hexamethylphosphoryl A mixture of triamine HMPA was added to a suspension of 3.8 g (157 mmol) NaH in 500 mL THF while controlling gas evolution. After the addition, the mixture was stirred at 0°C for 15 minutes, then added to the above mixture of 2-cyanopropionate lithium salt at 0°C, and then stirred at 35°C for 2 hours. The mixture was rapidly cooled with 150 mL of NaCl-saturated 1 N HCl solution. The mixture was...

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Abstract

The invention provides a propylene polymerization catalyst system, which comprises a solid catalytic component (A), aluminum alkyl (B) and a multi-element external electron donor (C), wherein the component (A) is a magnesium chloride-loaded Ti solid component and contains a phthalic acid diester internal electron donor, the component (B) is trialkylaluminum, the component (C) comprises a first-class external electron donor and a second-class external electron donor, the molar ratio of the first-class external electron donor to the second-class external electron donor is 1-70:30-99, the first-class external electron donor is selected from dicyclopentyl dimethoxy silane and diisopropyl dimethoxy silane, and the second-class external electron donor is selected from 2-cyano-2,3-dimethyl succinic acid di-n-butyl ester. According to the invention, the heat-resistant polypropylene obtained by using the catalyst system has high isotacticity and wide molecular weight distribution, so that the material has good rigidity and toughness balance; and according to the technology, an original device does not need to be changed, and the technology is suitable for existing different process industrial production devices and has good economic popularization value.

Description

technical field [0001] The 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 the preparation of high-rigidity heat-resistant polypropylene. Background technique [0002] Polypropylene (polypropylene) is a polymer polymerized from propylene monomer. Because of its mechanical properties, thermal properties and crystallization properties, it has a wide modulation range, excellent processing performance, strong chemical corrosion resistance and high cost performance. 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 with the largest global demand. [0003] Due to the gradual improvement of living standards, household appliances, especially various small household appliances, have also become a huge potential market fo...

Claims

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Application Information

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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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