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

A metallocene catalyst, a technology for ethylene polymerization, applied in the field of olefin polymerization catalysts, can solve the problems of limited industrial application, large amount of MAO, poor shape of carrier particles, etc., and achieve high ethylene polymerization catalytic activity, lower production costs, and good particle shape. Effect

Active Publication Date: 2017-02-15
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 silica gel 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 the silica gel. Industrial Applications of Supported Metallocene Catalysts
[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 and its preparation method and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0032] (1) Preparation of chlorinated hydrocarbyl silicon / silica gel support

[0033] 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.

[0034] (2) Preparation of alkylaluminum / chlorinated hydrocarbyl silicon / borate / silica gel support

[0035] Under the protection of nitrogen, take 5.0 grams of the modified silica gel carrier obtained above and put it into a glass reactor, add 60 ml of dried toluene, disperse into a suspension, add 8 ml of 5 mmol / ml triisobutyl aluminum toluene solution, and heat up to 50° C., stirred and reacted for 4 hours, then washed three times with 60 ml×3 toluene, then washed with hexane, and dried in vacuum to obtain a solid powder with good fluidity. Take 3 grams of the above powder and add it to a glass reaction vessel u...

Embodiment 2

[0039] (1) Preparation of chlorinated hydrocarbyl silicon / silica gel support

[0040] Same as step (1) of Example 1.

[0041] (2) Preparation of alkylaluminum / chlorinated hydrocarbyl silicon / borate / silica gel support

[0042] Same as embodiment 1 step (2)

[0043] (3) Preparation of supported metallocene catalyst B

[0044] With embodiment 1 step (3), 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 0.96%, and the weight content of Al is 7.91%.

Embodiment 3

[0046] (1) and (2) are the same as (1) and (2) preparation methods in Example 1.

[0047] (3) Preparation of supported metallocene catalyst C

[0048] Same as step (3) 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 0.53%, and the weight content of Al is 7.22%.

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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) alkyl aluminum, (4) a borate compound, and (5) 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): C08F10/02C08F4/6592C08F4/02
Inventor 李岩廖浩瀚高榕刘东兵周俊领
Owner CHINA PETROLEUM & CHEM CORP
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