A kind of supported metallocene catalyst for ethylene polymerization, preparation method and application

A metallocene catalyst and ethylene polymerization technology, which is applied in the field of preparation and modified magnesium chloride-supported metallocene catalyst, can solve the problems of limited industrial application, high production cost, and poor shape of carrier particles, and achieve high ethylene polymerization catalytic activity and particle shape The effect of good, good particle morphology

Active Publication Date: 2016-12-28
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Because the homogeneous metallocene catalyst requires a large amount of MAO to achieve high activity, the production cost is high, and the obtained polymer is amorphous, which cannot be used in the widely used slurry method or gas phase polymerization process. An effective way is to support the soluble metallocene catalyst
[0003] At present, there are many research reports on metallocene loading, among which SiO 2 CN1174848; CN1174849; CN1356343; US4,808,561; US5,026,797; US5,763,543; Appl.99 / 21898; US6,455,647; J.Mol.Catal.A2002,188,123; PCTInt.APP1.2004 / 078804; CN101817892; CN101172988; Uncontrollable; although the use of spherical magnesium chloride (containing alcohol) can ensure that the metallocene-loaded catalyst has a good particle shape, the carrier still contains alcohol, water, alkoxy and other components, and the preparation of the carrier is complicated. The above shortcomings limit Industrial Application of Magnesium Chloride Supported Metallocene Catalyst
[0004] There are also literatures that use carriers containing magnesium chloride, silica gel, etc. to load metallocenes (Polymer International, 200251: 417-423; US5962360), but the activity is very low, and a large amount of MAO needs to be added during polymerization

Method used

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  • A kind of supported metallocene catalyst for ethylene polymerization, preparation method and application
  • A kind of supported metallocene catalyst for ethylene polymerization, preparation method and application

Examples

Experimental program
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Effect test

Embodiment 1

[0045] (1) Preparation of chlorinated hydrocarbyl silicon / magnesium chloride support

[0046] Under the protection of nitrogen, take 5.62 grams of magnesium chloride carrier and add 100 ml of dried hexane to disperse into a suspension, add 1 ml of SiCl 2 (n-Bu) 2 , start stirring, heat up to 30° C., react for 4 hours, and dry in vacuum to obtain a solid powder with good fluidity.

[0047] (2) Preparation of alkyl aluminoxane / chlorinated hydrocarbyl silicon / magnesium chloride support

[0048] Under nitrogen protection, take 5.0 grams of the modified magnesium chloride carrier obtained above and add it to a glass reactor, add 60 milliliters of dried toluene, disperse into a suspension, and add 18 milliliters of 10 wt% MAO (methylaluminoxane) toluene solution , heated to 50 ° C, stirred for 4 hours, then washed three times with 50 ml × 3 toluene, then washed with hexane, and dried in vacuum to obtain a solid powder with good fluidity, that is, a magnesium chloride carrier conta...

Embodiment 2

[0057] (1) Preparation of chlorinated hydrocarbyl silicon / magnesium chloride support

[0058] With embodiment 1 step (1), only SiCl in embodiment 1 2 (n-Bu) 2 Change to SiCl 4 .

[0059] (2) Preparation of alkyl aluminoxane / chlorinated hydrocarbyl silicon / magnesium chloride support

[0060] Same as step (2) of Example 1.

[0061] (3) Preparation of supported metallocene catalyst B

[0062] Same as step (3) of Example 1 to obtain supported metallocene catalyst B. Characterized by ICP, in catalyst B, the weight content of Zr is 0.44%, and the weight content of Al is 11.31%.

Embodiment 3

[0064] (1) Preparation of chlorinated hydrocarbyl silicon / magnesium chloride support

[0065] With embodiment 1 step (1), only SiCl in embodiment 1 2 (n-Bu) 2 Change to CH 3 SiCl 3 .

[0066] (2) Preparation of alkyl aluminoxane / chlorinated hydrocarbyl silicon / magnesium chloride support

[0067] Same as step (2) of Example 1.

[0068] (3) Preparation of supported metallocene catalyst C

[0069] Same as step (3) of Example 1 to obtain supported metallocene catalyst C. Characterized by ICP, in catalyst C, the weight content of Zr is 0.48%, and the weight content of Al is 11.31%.

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Abstract

The invention relates to a supported metallocene catalyst for ethylene polymerization and a preparation method thereof. The catalyst includes (a) a metallocene compound; (b) a chlorinated hydrocarbyl silicon modifier; (c) an alkyl aluminoxane; (d) a reaction product of a magnesium chloride carrier; its preparation method includes: (1) a chlorinated hydrocarbyl Preparation of silicon-modified magnesium chloride carrier, (2) preparation of alkylaluminoxane-modified magnesium chloride carrier, (3) preparation of magnesium chloride-supported metallocene catalyst, the obtained metallocene catalyst catalyzes ethylene homopolymerization or copolymerization with high polymerization activity. The preparation method of the magnesium chloride carrier used is simple, and the obtained loaded catalyst particle has good shape and adjustable size. The obtained supported metallocene catalyst catalyzes the copolymerization reaction of ethylene and α-olefin, has high copolymerization activity and the obtained resin powder has good particle shape and high bulk density, and can be applied to slurry method and gas phase method polymerization technology.

Description

technical field [0001] The invention relates to a modified magnesium chloride supported metallocene catalyst, a preparation method and the application of the obtained catalyst in olefin polymerization. technical background [0002] The development and application of metallocene catalysts is another major breakthrough in the field of olefin polymerization catalysts after the traditional Ziegler-Natta catalysts, especially in the 1980s, Kaminsky and Sinn et al. (Angew.Chem., 1980, 19, 390; Adv. Organoment.Chem., 1980, 18, 99) developed a high-efficiency cocatalyst methylaluminoxane (MAO), making the research on metallocene catalysts enter a stage of rapid development. Because the homogeneous metallocene catalyst requires a large amount of MAO to achieve high activity, the production cost is high, and the obtained polymer is amorphous, which cannot be used in the widely used slurry method or gas phase polymerization process. An effective way is to support the soluble metalloce...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08F10/02C08F4/6592
Inventor 高榕李岩廖浩瀚刘东兵周俊领徐世媛
Owner CHINA PETROLEUM & CHEM CORP
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