Olefin polymerization catalyst composition and preparing method thereof

A technology for olefin polymerization and catalyst, which is applied in the field of catalyst active components and catalyst compositions containing the catalyst active components, and can solve the problem of unsatisfactory catalyst catalytic efficiency and orientation ability, increase of dealcoholization process and consumption of raw materials and energy. , the complex preparation process, etc.

Inactive Publication Date: 2008-07-09
中国石油天然气股份有限公司大庆化工研究中心 +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The preparation of early carrier catalysts usually adopts the co-grinding method of magnesium halide and titanium halide. The shape of the catalyst particles obtained in this way is not good, and the particle size distribution is very wide, which brings many difficulties to the industrial production of polypropylene; Many patents have adopted various chemical reaction methods to prepare high-efficiency catalysts, which can change the particle shape of the polymer to a certain extent, and the efficiency and orientation of the catalyst
[0004] Patents USP4111835 and USP4399054 in the seventies of the 20th century announced the carrier of magnesium chloride alcoholate prepared by spraying method and high-pressure extrusion method, but in the form of the carrier, the catalytic efficiency and orientation ability of the catalyst are all unsatisfactory
Proposed in CN1047302A is the preparation method of the spherical catalyst carrier of the spherical polymer with particle diameter between 1~5mm, the catalytic efficiency and orientation ability of the catalyst have been greatly improved compared with previous patent reports, but the preparation process of this method is more complicated, and the The alcohol content in the obtained magnesium chloride alcoholate carrier is relatively high, and the magnesium alcohol molar ratio is as high as 3.0, and dealcoholization treatment is required, which increases the consumption of dealcoholization process and raw materials and energy
This is unfavorable for some developments that require high melt index products

Method used

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  • Olefin polymerization catalyst composition and preparing method thereof
  • Olefin polymerization catalyst composition and preparing method thereof
  • Olefin polymerization catalyst composition and preparing method thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0056] (1) Preparation of spherical alcoholate carrier

[0057] Under the protection of nitrogen, 0.29 moles of anhydrous magnesium chloride, 0.78 moles of absolute ethanol, 7 moles of methyl silicone oil and 7 moles of liquid paraffin were sequentially added into a special reaction kettle, and the temperature of the reaction system was raised to 120°C, and the reaction system was maintained at this temperature for 3 Hour, the rotating speed of stirrer is controlled at 500 rev / min. Add 0.16 moles of 2,2-dibutanedioic acid ethyl acyl-9,9-bis(methoxymethyl)fluorene, and stir and disperse at a speed of 2000rpm for 15 minutes, then pressurize the reaction vessel, and inject the mixed hydraulic pressure into A certain amount of hexane has been added and the temperature is lowered to -30°C in a cooling kettle, and stirred at a low speed for 15 minutes. Use normal hexane to wash the solid particles 3 to 6 times, the amount of hexane is 1000 to 1500 ml / time, filter and then vacuum dr...

Embodiment 2

[0064] In addition to the low-carbon alcohol is anhydrous butanol, the addition is 1.1 moles, and the internal electron donor is 1,1-dibutanedioic acid ethyl acyl-9,9-bis(methoxymethyl)fluorene, the addition is 2.8 mol, the temperature of the spherical alcoholate carrier system is raised to 80°C, the amount of liquid paraffin added is 6 mol, and 3 mol of AlEt is used in the bulk polymerization of propylene 3 , all the other preparation conditions and the consumption of substance are identical with embodiment 1, the alcohol / Mg (mol / mol)=2.14 in the obtained carrier, the titanium content in the catalyst active component is 2.10%, record spherical catalyst activity with BET method The specific surface area of ​​the component is 290m 2 / g, the porosity is 0.31ml / g, and the pore size distribution is at least 65% of which the pore radius is less than 100 Ȧ. The activity of catalyst is 38.3Kg polypropylene / g catalyst, and the isotacticity of polypropylene is 97.3% (boiling n-heptane...

Embodiment 3

[0066] In addition to the low-carbon alcohol is anhydrous isopropanol, the addition is 0.29 moles, the inert solvent is methyl silicone oil, the addition is 14 moles, and the electron donor 4,4-dibutanedioic acid ethyl acyl-9,9 - 0.05 moles of bis(methoxymethyl)fluorene, the spherical alcoholate carrier system is heated up to 130°C, the addition of titanium tetrabromide is 5.8 moles, and the alkyl aluminum used in the bulk polymerization of propylene is 6 moles of alkyl aluminum chloride Except, all the other preparation conditions and the consumption of substance are identical with embodiment 1, and the alcohol / Mg (mol / mol)=2.53 in the obtained carrier, the titanium content in the catalyst active component is 2.06%, records spherical catalyst by BET method The active component has a specific surface area of ​​290m2 / g, a porosity of 0.31ml / g, and a pore size distribution of at least 65% of which have a pore radius smaller than 100 Å. No external electron donor is added during ...

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Abstract

The invention relates to an olefin polymerization catalyst for the polymerization of alkene, in particular to the polymerization of propylene, or copolymerization, and a process for preparation, the invention relates to a catalytic activity component which is prepared by novel ester ether compound, and catalyst composition which contains the catalytic activity component, and a process for preparation. The catalytic activity component takes magnesium chloride to be carrier, a noevl binary ether ester compound which is showed as the general formula I is added in the process for preparation, the catalyst composition which contains catalytic activity component not only has higher catalytic activity and hydrogen sensitivity, meanwhile can guarantee polyacrylic resin to have higher stereoregularity when the composition is used for propylene polymerization. And the integrity of the polymerisate is better.

Description

technical field [0001] The present invention relates to an active component of a catalyst for olefin polymerization, especially propylene polymerization or copolymerization, and a catalyst composition containing the catalyst active component, more specifically, to a catalyst prepared by using a novel ether ester compound An active component and a catalyst composition containing the catalyst active component. technical background [0002] In the synthesis technology of polypropylene, the titanium / magnesium catalyst system is widely used in the synthesis process of isotactic polypropylene due to its high efficiency and high stereospecificity (isotacticity). In the industrial production of polypropylene, there are two main requirements for catalysts: one is to have higher activity in the polymerization reaction, and the other is to have relatively good comprehensive performance of the obtained polymer. The main properties of polypropylene include the isotacticity of the polyme...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F10/00C08F4/654
Inventor 付义郎笑梅赵成才吴林美邹恩广张铭辉赵增辉高宇新李欣王立娟何书艳王淑英张丽洋杨国兴丁伟于涛曲广淼栾和鑫
Owner 中国石油天然气股份有限公司大庆化工研究中心
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