A kind of supported metallocene catalyst and its preparation method and application

A metallocene catalyst and metallocene compound technology, 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., achieve high catalytic activity of ethylene polymerization, reduce production cost, 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 CN 102286114; CN 1174848; CN 1174849; CN 1356343; US 4,808,561; US ​​5,026,797; US 5,763,543; Appl.99 / 21898; US 6,455,647; J.Mol.Catal.A 2002,188,123; PCTInt.APP1.2004 / 078804; CN 101817892; CN 101172988; Poor and 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 The Industrial Application of MgCl-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 and its preparation method and application
  • A kind of supported metallocene catalyst and its preparation method and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035] (1) Preparation of chlorinated hydrocarbyl silicon / magnesium chloride support

[0036] Under the protection of nitrogen, take 5.5 grams of magnesium chloride carrier and add 100 milliliters of dried hexane to disperse into a suspension, add 1 milliliter 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 alkylaluminum / hydrocarbyl chloride / borate / magnesium chloride support

[0038] 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, add 8 milliliters of 5 mmol / ml triisobutylaluminum 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 ...

Embodiment 2

[0042] (1) Preparation of chlorinated hydrocarbyl silicon / magnesium chloride support

[0043] Same as step (1) of Example 1.

[0044] (2) Preparation of alkylaluminum / hydrocarbyl chloride / borate / magnesium chloride support

[0045] Same as embodiment 1 step (2)

[0046] (3) Preparation of supported metallocene catalyst B

[0047] 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 0.92%, and the weight content of Al is 7.6%.

Embodiment 3

[0049] (1) and (2) are the same as (1) and (2) preparation methods in Example 1.

[0050] (3) Preparation of supported metallocene catalyst C

[0051] 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 0.51%, and the weight content of Al is 7%.

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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 magnesium chloride 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, and in particular relates to a modified 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 to suppor...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08F10/02C08F10/00C08F4/6592C08F4/02
Inventor 李岩高榕廖浩瀚刘东兵周俊领
Owner CHINA PETROLEUM & CHEM CORP
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