A Supported Monometallocene Catalyst for Ethylene Polymerization

A single metallocene and ethylene polymerization technology, which is applied in the field of preparation of modified silica gel-supported single metallocene catalysts, can solve the problems of large amount of MAO, low activity, and inability to use, and achieve high catalytic activity for ethylene polymerization. The preparation method is simple and resizable effect

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

AI Technical Summary

Problems solved by technology

Because the homogeneous single 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 to overcome the above problems The most effective way is to support the soluble mono-metallocene catalyst
[0003] At present, there are a lot of research reports on the loading of single metallocenes, among which the catalysts using spherical magnesium chloride (containing alcohol) to support single metallocenes have good particle morphology, such as PCT Int.Appl.99 / 21898; US6,455,647; J.Mol .Catal.A2002,188,123; PCT Int.APP1.2004 / 078804, but the carrier contains alcohol, water, alkoxy and other components, and the preparation of the carrier is complicated; while Si0 2 CN1174849; CN1356343; US4,808,561; US5,026,797; US5,763,543; , a large amount of methylalumoxane must still be introduced during the polymerization process, the above shortcomings limit the industrial application of silica gel-supported single metallocene catalysts
There are also reports in the literature that use carriers containing magnesium chloride, silica gel, etc. to support mono-metallocenes (Polymer International, 51: 417-423, 2002; US5962360; CN102336855A), but the activity is very low, and a large amount of MAO needs to be added during polymerization.
The above disadvantages limit the industrial application of silica-supported monometallocene catalysts

Method used

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  • A Supported Monometallocene Catalyst for Ethylene Polymerization
  • A Supported Monometallocene Catalyst for Ethylene Polymerization
  • A Supported Monometallocene Catalyst for Ethylene Polymerization

Examples

Experimental program
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Effect test

Embodiment 1

[0056] (1) Preparation of chlorinated hydrocarbyl silicon / silica gel support

[0057] Under the protection of nitrogen, take 10.0 grams of dry silica gel carrier and put it into a glass reactor, add 100 ml of dried hexane, 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.

[0058] (2) Preparation of alkylmagnesium halide / hydrocarbyl silicon chloride / magnesium chloride carrier

[0059] Under the protection of nitrogen, take 10.0 grams of the above-mentioned modified silica gel carrier and add it to a glass reactor, add 100 ml of dried toluene, disperse it into a suspension, add 5 ml of 2M ethylmagnesium chloride, start stirring, heat up to 30 ° C, and react After 4 hours, it was vacuum dried to obtain a solid powder with good fluidity.

[0060] (3) Preparation of alkyl aluminoxane / hydrocarbyl magnesium halide / hydrocarbyl silicon chloride / magnesium chlo...

Embodiment 2

[0072] (1) Preparation of chlorinated hydrocarbyl silicon / silica gel support

[0073] With embodiment 1 step (1), only SiCl in embodiment 1 2 (n-Bu) 2 Change to SiCl 4 .

[0074] (2), (3), (4) are the same as the preparation methods of (2), (3), and (4) in Example 1.

[0075] The supported metallocene catalyst B was obtained. Characterized by ICP, in catalyst B, the weight content of Ti is 0.31%, the weight content of Al is 11.21%, and the weight content of magnesium is 2.67%.

Embodiment 3

[0077] (1) Preparation of chlorinated hydrocarbyl silicon / silica gel support

[0078] Same as step (1) of Example 1.

[0079] (2) Preparation of halogenated hydrocarbyl magnesium / chlorinated hydrocarbyl silicon / silica gel carrier

[0080] Same as step (2) of embodiment 1, only ethylmagnesium chloride in embodiment 1 is replaced by ethylmagnesium bromide.

[0081] (3), (4) are the same as in embodiment 1 (3), (4) preparation method

[0082] The supported metallocene catalyst C is obtained. Characterized by ICP, in catalyst C, the weight content of Ti is 0.29%, the weight content of Al is 10.87%, and the weight content of magnesium is 2.48%.

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Abstract

The invention relates to a supported monometallocene catalyst for ethylene polymerization and a preparation method thereof, the catalyst comprising (a) a monometallocene compound; (b) a chlorinated hydrocarbyl silicon modifier; (c) a modified hydrocarbyl magnesium halide (d) alkyl aluminoxane; (e) reaction product of silica gel carrier; its preparation method includes: (1) preparation of chlorinated hydrocarbyl silicon modified silica gel carrier, (2) halogenated hydrocarbyl magnesium modified silica gel carrier (3) preparation of modified silica gel carrier of alkyl aluminoxane, (4) preparation of silica gel-supported single metallocene catalyst, the obtained single metallocene catalyst catalyzes ethylene polymerization or copolymerization with high polymerization activity . The preparation method of the silica gel carrier used in the method is simple, and the obtained loaded catalyst particle has good shape and adjustable size.

Description

technical field [0001] The invention relates to a preparation method of a modified silica gel supported mono-metallocene catalyst and the application of the obtained catalyst in olefin polymerization. technical background [0002] The development and application of a single metallocene catalyst is another major breakthrough in the field of olefin polymerization catalysts after the traditional Ziegler-Natta catalyst, 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 single metallocene catalysts enter a stage of rapid development. Because the homogeneous single 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 to overcome the above problems The mo...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08F10/02C08F4/6592
Inventor 高榕廖浩瀚李岩刘东兵周俊领黄廷杰
Owner CHINA PETROLEUM & CHEM CORP
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