Supported metallocene catalyst and preparation method and application thereof

A technology of metallocene catalysts and metallocene compounds, applied in the field of supported metallocene catalysts and their preparation and application, which can solve the problems of easy sticking of polymers, energy consumption, low catalytic activity, low polymerization temperature, etc.

Active Publication Date: 2014-08-27
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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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 it is used for olefin polymerization is easy to stick to the kettle and has high energy consumption, and provides a catalyst with high catalytic activity, which is used for olefin A supported metallocene catalyst that does not stick to the kettle during polymerization and has a low polymerization temperature

Method used

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  • Supported metallocene catalyst and preparation method and application thereof
  • Supported metallocene catalyst and preparation method and application thereof
  • Supported metallocene catalyst and preparation method and application thereof

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preparation example Construction

[0061] The present invention also provides a method for preparing the above-mentioned supported metallocene catalyst. The preparation method includes: ball milling anhydrous magnesium chloride and alkylaluminoxane at a temperature of 15-100°C under the protection of inert gas. After 100 hours, under the protection of inert gas, the carrier is contacted with the first solution for a third time to obtain the carrier after the third contact. The first solution contains the product obtained by ball milling and the first solvent; The first solvent on the carrier; the carrier from which the first solvent has been removed is subjected to a fourth contact with the second solution to obtain the carrier after the fourth contact, the second solution contains the metallocene compound and the second solvent, wherein, The average particle diameter of the carrier is 20-80 microns, the specific surface area is 550-650 square meters / g, the pore volume is 0.4-1.2 ml / g, and the most probable pore ...

Embodiment 1

[0099] This example is used to illustrate the supported metallocene catalyst and its preparation method according to the present invention.

[0100] 2.0 grams of triblock copolymer polyethylene oxide-polypropylene oxide-polyethylene oxide (Aldrich, P123) and 15 grams of N,N-dimethylformamide (DMF) were added to 11.2 grams of 37% by weight In a solution of hydrochloric acid and 64ml of water (pH=4.4), stir at 40°C until the polyoxyethylene-polyoxypropylene-polyoxyethylene is completely dissolved, and then 4.45g of ethyl orthosilicate is added to the above solution, 40 After stirring for 1 hour at ℃, add 1 gram of industrial 955 silica gel. After stirring for 0.3 hours at 40℃, transfer the solution to a reactor lined with polytetrafluoroethylene, crystallize in an oven at 150℃ for 24 hours and then filter. , Washed with distilled water and dried to obtain spherical mesoporous silica raw powder.

[0101] The raw spherical mesoporous silica powder obtained in the previous step is calc...

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Abstract

The invention provides a supported metallocene catalyst which comprises a carrier, and an alkylaluminoxane / magnesium chloride complex and a metallocene compound which are supported on the carrier; the carrier is spherical mesoporous silica, wherein the carrier has an average particle diameter of 20-80 microns, a specific surface area of 550-650 square meter / g, a pore volume of 0.4-1.2 ml / g, and a most probable pore size of 1-7 nanometers; the metallocene compound has a structure as shown in formula 1. When the supported metallocene catalyst of the invention is used for catalyzing olefin polymerization, the catalytic efficiency for homopolymerization at 70 DEG C is up to 2.3*10<8> gPE / (mol Zr.h), and the catalytic efficiency for copolymerization at 70 DEG C is up to 2.2*10<8> gPE / (mol Zr.h); the supported metallocene catalyst overcomes the defect of kettle adhesion, has a low polymerization temperature, and thus reduces the 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 catalyst is the core of polyolefin technology development, 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.) require the use of supported catalysts to increase the activity of the catalyst. Meet the process requirements, avoid the phenomenon of polymer sticking, and improve the shape of the polymer. [0003] Among the various supports used in supported olefin polymerization catalysts, MgCl 2 The carrier is by far the most used and most effective carrier in industry. Howe...

Claims

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Application Information

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