A kind of method of magnesium chloride supported metallocene catalyst

A metallocene catalyst and magnesium chloride technology are applied in the field of preparation of magnesium chloride supported metallocene catalysts, which can solve the problems of complicated carrier preparation, limited industrial application, poor carrier particle shape and the like, and achieve high bulk density, adjustable particle size and good shape. Effect

Active Publication Date: 2011-11-30
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although there are many research reports on magnesium chloride compound supported metallocene catalysts, such as PCT Iht.Appl.99 / 21898; US6,455,647; J.Mol.Catal.A 2002,188,123; , but the cost of carrier preparation and catalyst loading is high, and the particle shape of the carrier is poor and uncontrollable; although the use of spherical magnesium chloride (containing alcohol) can ensure that the catalyst after the metallocene is loaded has a good particle shape, the carrier still contains alcohol, Water, alkoxy and other components, the preparation of the carrier is complicated, the above shortcomings limit the industrial application of magnesium chloride-supported metallocene catalysts
[0004] There are also literatures that use carriers containing magnesium chloride, silica gel, etc. to load metallocenes (Polymer International, 51: 417-423, 2002; 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 method of magnesium chloride supported metallocene catalyst
  • A kind of method of magnesium chloride supported metallocene catalyst
  • A kind of method of magnesium chloride supported metallocene catalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0041] Under nitrogen protection, in a glass reactor, add 24.54 grams of anhydrous magnesium chloride at room temperature, then add 700 milliliters of dried tetrahydrofuran, start stirring, raise the temperature to 65 ° C, stir and dissolve for 5 hours to ensure that the magnesium chloride is completely dissolved, and then pass through Buchi B -290 spray dryer prepares spherical magnesium chloride / tetrahydrofuran particles, the content of tetrahydrofuran is 25wt%, and the particle size is D 50 18 microns.

[0042] Spherical magnesium chloride / tetrahydrofuran particles were vacuum-dried at 100°C for 2 hours, and then vacuum-dried at 300°C for 10 hours to obtain a magnesium chloride carrier with good fluidity. No tetrahydrofuran was detected by gas chromatography analysis.

[0043] Under the protection of nitrogen, take 4.51 grams of the magnesium chloride carrier obtained above and add it to a glass reactor, add 60 milliliters of dried toluene, disperse into a suspension, add 2...

Embodiment 2

[0046] Use (nBuCp) 2 ZrCl 2 Instead of (1,3-BuMeCp) 2 ZrCl 2 , all the other are with embodiment 1.

[0047] Under the protection of nitrogen, take 4.25 grams of the magnesium chloride carrier obtained in Example 1 and add it to a glass reactor, add 60 milliliters of dried toluene, disperse into a suspension, add 26 milliliters of 10 wt% MAO (methylaluminoxane) toluene The solution was heated to 50° C., stirred and reacted 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 magnesium chloride carrier containing methylaluminoxane.

[0048] Under nitrogen protection, 3.32 grams of magnesium chloride carriers containing methylaluminoxane obtained were added to a glass reactor, 35 milliliters of dried toluene was added to make a slurry, and 0.131 grams of (nBuCp) dissolved in 20 milliliters of toluene 2 ZrCl 2 The solution of (bis-n-butylcyclopentadienyl zirconium dic...

Embodiment 3

[0050] Spherical MgCl / THF particles were prepared on a pilot plant.

[0051] Under the protection of nitrogen, in the reactor, add 7.2 kg of anhydrous magnesium chloride at room temperature, then add 200 liters of dried tetrahydrofuran, start stirring, raise the temperature to 65 ° C, stir and dissolve for 7 hours to ensure that the magnesium chloride is completely dissolved, and then spray through the pilot test Dryer (3 kg carrier capacity per hour) prepared spherical magnesium chloride / tetrahydrofuran particles, tetrahydrofuran content 31wt%, particle size D 50 is 26 microns.

[0052] 200 grams of spherical magnesium chloride / tetrahydrofuran particles were vacuum-dried at 100° C. for 2 hours, and then vacuum-dried at 300° C. for 10 hours to obtain a magnesium chloride carrier with good fluidity. Through gas chromatography analysis, no tetrahydrofuran was detected.

[0053] Under nitrogen protection, take 4.39 grams of the magnesium chloride carrier obtained above and add i...

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Abstract

The invention discloses a method for preparing a supported metallocene catalyst using magnesium chloride as a carrier. The method comprises: (1) preparation of a magnesium chloride carrier, (2) preparation of a magnesium chloride carrier of an alkyl aluminoxane, (3) magnesium chloride loading The preparation of the metallocene catalyst; wherein the preparation of the magnesium chloride carrier adopts the spraying method using tetrahydrofuran as a solvent. The preparation of the magnesium chloride carrier used in the method is simple, and the obtained supported catalyst particle has good shape and adjustable size. The supported metallocene catalyst obtained by the method catalyzes the copolymerization reaction of ethylene and higher α-olefins, has high copolymerization activity and the obtained resin powder has good particle shape and high packing density, and can be applied to slurry method and gas phase polymerization process .

Description

technical field [0001] The invention relates to a preparation method of a magnesium chloride supported metallocene catalyst and the application of the catalyst prepared according to the invention 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 support th...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08F4/76C08F4/02C08F10/00
Inventor 刘东兵王洪涛廖浩瀚傅捷徐世媛刘克杜宗友
Owner CHINA PETROLEUM & CHEM CORP
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