A kind of modified silica gel supported metallocene catalyst, and preparation method

A technology of metallocene catalysts and metallocene compounds, which is applied in the field of preparation of modified silica gel-supported metallocene catalysts, can solve the problems of limiting the industrial application of silica gel-supported metallocene catalysts, low catalyst loading efficiency, and large amount of MAO. Adjustable size, high ethylene polymerization catalytic activity, high bulk density effect

Active Publication Date: 2016-08-17
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 reports on metallocene loading research, among which the catalyst using spherical magnesium chloride (containing alcohol) to support metallocene has good particle morphology, such as PCT Int.Appl.99 / 21898; US6,455,647; J.Mol.Catal .A 2002,188,123; PCT Int.APP1.2004 / 078804; CN 101817892; CN 101172988, but the carrier contains alcohol, water, alkoxy and other components, and the preparation of the carrier is complicated; 2 CN 102286114; CN 1174848; CN 1174849; CN 1356343; US 4,808,561; US ​​5,026,797; US 5,763,543; The loading efficiency of the catalyst is low, and a large amount of methylalumoxane is still introduced during the polymerization process. The above shortcomings limit the industrial application of silica gel-loaded metallocene catalysts.
[0004] There are also literatures that use carriers containing magnesium chloride, silica gel, etc. to load metallocenes (Polymer International, 2002, 51, 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 modified silica gel supported metallocene catalyst, and preparation method
  • A kind of modified silica gel supported metallocene catalyst, and preparation method
  • A kind of modified silica gel supported metallocene catalyst, and preparation method

Examples

Experimental program
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Effect test

Embodiment 1

[0046] (1) Preparation of chlorinated hydrocarbyl silicon / silica gel support

[0047] Under the protection of nitrogen, take 2.5 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.

[0048] (2) Preparation of alkyl aluminoxane / chlorinated hydrocarbyl silicon / silica gel support

[0049] Under the protection of nitrogen, take 5.0 grams of the modified silica gel 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 silica gel carrier containi...

Embodiment 2

[0058] (1) Preparation of chlorinated hydrocarbyl silicon / silica gel support

[0059] With embodiment 1 step (1), only SiCl in embodiment 1 2 (n-Bu) 2 Change to SiCl 4 .

[0060] (2) Preparation of alkyl aluminoxane / chlorinated hydrocarbyl silicon / silica gel support

[0061] Same as step (2) of Example 1.

[0062] (3) Preparation of supported metallocene catalyst B

[0063] 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 0.46%, and the weight content of Al is 11.12%.

Embodiment 3

[0065] (1) Preparation of chlorinated hydrocarbyl silicon / silica gel support

[0066] With embodiment 1 step (1), only SiCl in embodiment 1 2 (n-Bu) 2 Change to CH 3 SiCl 3 .

[0067] (2) Preparation of alkyl aluminoxane / chlorinated hydrocarbyl silicon / silica gel support

[0068] Same as step (2) of Example 1.

[0069] (3) Preparation of supported metallocene catalyst C

[0070] 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 0.52%, and the weight content of Al is 11.28%.

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Abstract

The present invention relates to a supported metallocene catalyst for ethylene polymerization and a preparation method, the catalyst comprising (a) a metallocene compound; (b) a chlorinated hydrocarbyl silicon modifier; (c) an alkyl aluminoxane; (d) Reaction product of silica gel carrier; its preparation method includes: (1) chlorinated hydrocarbyl silicon modified silica gel carrier, (2) alkyl aluminoxane modified silica gel carrier, (3) modified silica gel carrier supported metallocene catalyst The obtained metallocene catalyst catalyzes ethylene homopolymerization or copolymerization and has high polymerization activity. The preparation method of the silica gel carrier used 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 metallocene catalyst 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 metallocene cat...

Claims

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Application Information

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