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Load-type metallocene catalyst, preparation method thereof and application thereof

A technology of metallocene catalyst and metallocene compound, which is applied in the field of supported metallocene catalyst and its preparation and application, and can solve the problems of low catalytic activity, low polymerization temperature, easy polymer sticking and energy consumption, etc.

Active Publication Date: 2013-03-06
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0016] The object of the present invention is to overcome the problem that the catalytic activity of the supported metallocene catalyst in the prior art is low, and the polymer obtained when used for olefin polymerization is easy to stick to the kettle and has high energy consumption, and provides a catalyst with high catalytic activity for olefin polymerization. A metallocene catalyst that does not stick to the kettle during polymerization and has a low polymerization temperature and realizes secondary loading of magnesium chloride

Method used

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  • Load-type metallocene catalyst, preparation method thereof and application thereof
  • Load-type metallocene catalyst, preparation method thereof and application thereof
  • Load-type metallocene catalyst, preparation method thereof and application thereof

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preparation example Construction

[0053] The present invention also provides a method for preparing the above-mentioned supported metallocene catalyst, the preparation method comprising: under the protection of an inert gas, ball milling anhydrous magnesium chloride and alkylaluminoxane at a temperature of 15-100°C for 0.1- 100 hours, then under the protection of an inert gas, the carrier is first contacted with the first solution to obtain the carrier after the first contact, and the first solution contains the product obtained by ball milling and the first solvent; remove the first contact after the first solution The first solvent on the carrier; the second contact is carried out between the carrier removed from the first solvent and the second solution to obtain the second contacted carrier, the second solution contains the metallocene compound and the second solvent, wherein, The carrier is hollow spherical mesoporous silica, the average particle diameter of the carrier is 3-20 microns, the specific surfac...

Embodiment 1

[0092] This example is used to illustrate the supported metallocene catalyst and its preparation method according to the present invention.

[0093] Add 1.0 gram of triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene (Aldrich Company, P123) and 1.69 gram of ethanol into the buffer solution (pH=4.4) of acetic acid and sodium acetate of 28ml, at 15 ℃ Stir until the polyoxyethylene-polyoxypropylene-polyoxyethylene is completely dissolved, then add 6g of trimethylpentane to the above solution, stir at 15°C for 8 hours, then add 2.13 grams of tetramethoxysilane to the In the above solution, after stirring for 20 hours at 15°C, the solution was transferred to a polytetrafluoroethylene-lined reactor, and crystallized in an oven at 60°C for 24 hours, then filtered, washed with distilled water, and dried to obtain mesoporous hollow spheres. Silicon oxide raw powder.

[0094] The hollow spherical mesoporous silica raw powder obtained in the previous step was calcined in...

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Abstract

The invention provides a load-type metallocene catalyst which comprises a carrier and an alkyl aluminoxane / magnesium chloride complex and a metallocene compound loaded on the carrier. The hollow ball mesoporous silica carrier has an average particle diameter of 3 to 20 micrometers, a specific surface area of 200 to 300 square meter per gram, a pore volume of 0.5 to 1.5 milliliter per gram, a most probable pore size of 3 to 20 nanometers and an average pore wall thickness of 1 to 2.9 micrometers. The metallocene compound has a structure as shown in formula 1. The load-type metallocene catalyst provided by the invention has a catalytic efficiency up to 3.8 * 10<8> gPE / (mol Zr * h) while homopolymerization and a catalytic efficiency up to 3.7 * 10<8> gPE / (mol Zr * h) while copolymerization under 70 DEG C, overcomes defects of sticking to kettles, is low in a polymerization temperature, and reduces energy consumption to some extent.

Description

technical field [0001] The invention relates to a supported metallocene catalyst and its preparation method and application. Background technique [0002] Olefin polymerization catalysts are the core of the development of polyolefin technology, and the carrier is a very critical factor in the innovation of catalysts. The carrier not only plays the role of supporting and dispersing the active center, but also may act as a special ligand and active center, thereby improving the activity and selectivity of the catalyst. At present, most olefin polymerization processes (such as gas phase polymerization, slurry polymerization, etc.) need to use supported catalysts to improve the activity of the catalysts. Meet the process requirements, avoid the phenomenon of polymer sticking to the kettle, and improve the shape of the polymer. [0003] Among the various supports used in supported olefin polymerization catalysts, MgCl 2 Carrier is the most widely used and most effective carrie...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F4/6592C08F4/02C08F10/02
Inventor 亢宇张明森黄文氢王洪涛郭顺刘长城邱波姜健准
Owner CHINA PETROLEUM & CHEM CORP
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