Supported metallocene catalyst for ethylene polymerization and its preparation method and application

A metallocene catalyst and ethylene polymerization technology, applied in the field of olefin polymerization catalysts, can solve the problems of limiting the industrial application of silica gel-loaded metallocene catalysts, low catalyst loading efficiency, and complicated carrier preparation, and achieve high ethylene polymerization catalytic activity, good shape, The effect of high bulk density

Active Publication Date: 2017-03-29
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 a lot of research reports on metallocene loading, 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 .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 metallocene catalysts
There are also reports in the literature that metallocenes are loaded on carriers containing magnesium chloride and silica gel (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 metallocene catalysts

Method used

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  • Supported metallocene catalyst for ethylene polymerization and its preparation method and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035] (1) Preparation of chlorinated hydrocarbyl silicon / silica gel support

[0036] Under the protection of nitrogen, take 5.5 grams of silica gel 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.

[0037] (2) Preparation of halogenated hydrocarbyl magnesium modified silica gel carrier

[0038] Under the protection of nitrogen, take 5.0 g of the modified silica gel carrier obtained in (1) and add it to a glass reactor, add 50 ml of dried toluene, disperse it into a suspension, add 5 ml of 1M ethylmagnesium chloride, start stirring, and heat up to React at 30°C for 4 hours and dry in vacuum to obtain a solid powder with good fluidity.

[0039] (3) Preparation of alkylaluminum / borate modified silica gel support

[0040] Under the protection of nitrogen, take 5.0 grams of the modified silica gel carrier obtain...

Embodiment 2

[0044] (1) Preparation of chlorinated hydrocarbyl silicon / silica gel support

[0045] Same as step (1) of Example 1.

[0046] (2) Preparation of halogenated hydrocarbyl magnesium modified silica gel carrier

[0047] Same as embodiment 1 step (2)

[0048] (3) Preparation of alkylaluminum / borate modified silica gel support

[0049] Same as embodiment 1 step (3)

[0050] (4) Preparation of supported metallocene catalyst B

[0051] With embodiment 1 step (4), only 0.129 gram (1,3-BuMeCp) in embodiment 1 2 ZrCl 2 Replaced with 0.156 g (1,3-BuMeCp) 2 HfCl 2 [Bis(1,3-butylmethylcyclopentadienyl) hafnium dichloride] to obtain supported metallocene catalyst B. Characterized by ICP, in catalyst B, the weight content of Hf is 0.91%, the weight content of Al is 7.84%, and the weight content of Mg is 2.33%.

Embodiment 3

[0053] (1), (2), (3) are the same as the preparation methods of (1), (2), and (3) in Example 1.

[0054] (4) Preparation of supported metallocene catalyst C

[0055] Same as step (4) of Example 1, only 0.129 grams of (1,3-BuMeCp) in Example 1 2 ZrCl 2 Replaced with 0.121 g of bis-(n-butylcyclopentadienyl)zirconium dichloride (nBuCp) 2 ZrCl 2 , to obtain the supported metallocene catalyst C. Characterized by ICP, in catalyst C, the weight content of Zr is 0.51%, the weight content of Al is 7.10%, and the weight content of Mg is 2.47%.

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Abstract

The present invention discloses a supported metallocene catalyst for ethylene polymerization, wherein the catalyst comprises the reaction product of the following components: (1) a metallocene compound, (2) chlorinated hydrocarbonyl silicon, (3) halogenated hydrocarbonyl magnesium, (4) alkyl aluminum, (5) a borate compound, and (6) a silica gel carrier. According to the present invention, the catalyst presents the high activity when the catalyst is used for the ethylene polymerization; and the bulk density of the polymer powder material is high.

Description

technical field [0001] The invention belongs to the field of olefin polymerization catalysts, in particular to a modified silica gel supported metallocene catalyst, its preparation method and its application in olefin polymerization. Background technique [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 ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08F10/02C08F210/16C08F4/6592
Inventor 李岩廖浩瀚高榕刘东兵周俊领
Owner CHINA PETROLEUM & CHEM CORP
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