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Supported polyolefin catalyst, preparation and application

A polyolefin catalyst and a supported technology, which is applied to the supported polyolefin catalyst and the fields of preparation and application, can solve the problems of reduced activity and great influence of homogeneous catalyst loading, etc.

Active Publication Date: 2009-11-18
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Studies have shown that the carrier has a great influence on the loading of homogeneous catalysts, and the activity of homogeneous catalysts often decreases after loading

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0032] Bis-(n-butyl-cyclopentadienyl)zirconium dichloride supported catalyst

[0033] 1. Preparation of spherical amorphous zirconium phenylphosphate: 23gZrOCl2 8H 2O was dissolved in 240ml deionized water to prepare a 0.3mol / l solution; 33g phenylphosphoric acid was dissolved in 210ml deionized water to prepare a 1.0mol / l phenylphosphoric acid solution; under stirring conditions, ZrOCl 2 The solution is slowly added dropwise to the phenylphosphoric acid solution to obtain a zirconium phenylphosphate gel; the mixed system is sealed in a reaction kettle, crystallized at 70° C. for 20 hours, centrifuged, and washed with deionized water to obtain a zirconium phenylphosphate wet gel. Take a small amount of zirconium phenylphosphate wet gel and measure the solid content to be 20%. The zirconium phenylphosphate wet gel was dissolved in a certain amount of deionized water to obtain 400 ml of zirconium phenylphosphate slurry with a solid content of 7%, and the obtained slurry was mol...

Embodiment 2

[0038] Bis-(n-butyl-cyclopentadienyl)titanium dichloride supported catalyst

[0039] 1. Preparation of spherical amorphous zirconium phenylphosphate: 5gZrOCl2 8H 2 O is dissolved in 47ml of deionized water, and 7g of phenylphosphoric acid is dissolved in 42 milliliters of deionized water to prepare a phenylphosphoric acid solution; under stirring conditions, the ZrOCl solution is slowly added dropwise to the phenylphosphoric acid solution to obtain a zirconium phenylphosphate gel; the mixed system is reacted The kettle was sealed, crystallized at 70° C. for 20 hours, centrifuged, washed with deionized water to obtain a zirconium phenylphosphate wet gel. The zirconium phenylphosphate wet gel was dissolved in a certain amount of deionized water to obtain 150 ml of zirconium phenylphosphate slurry with a solid content of 5%, and the obtained slurry was molded by a rotary spray dryer. Control the feeding rate of the peristaltic pump to 30ml / min, the speed of the nozzle to 25000 r...

Embodiment 3

[0043] Cyclopentadienyl indenyl zirconium dichloride supported catalyst

[0044] 1. Preparation of spherical amorphous zirconium phenylphosphate: 5gZrOCl2 8H2O was dissolved in 47ml deionized water, 7g phenylphosphoric acid was dissolved in 42ml deionized water to prepare phenylphosphoric acid solution; under stirring condition, ZrOCl 2 The solution is slowly added dropwise to the phenylphosphoric acid solution to obtain a zirconium phenylphosphate gel; the mixture is sealed in a reaction kettle, crystallized at 70° C. for 20 hours, centrifuged, and washed with deionized water to obtain a zirconium phenylphosphate wet gel. The zirconium phenylphosphate wet gel was dissolved in a certain amount of deionized water to obtain 150 ml of α-zirconium phenylphosphate slurry with a solid content of 4%, and the obtained slurry was molded by a rotary spray dryer. Control the feeding rate of the peristaltic pump to 20ml / min, the speed of the nozzle to 25000 rpm, and the temperature of the...

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Abstract

The invention relates to a supported polyolefin catalyst, preparation method and application; a carrier is spherical organic benzene zirconium phosphate; the main catalyst for olefin polymerization is a metallocene compound, the central atom Ti, Zr or Hf of the metallocene compound accounts for 0.01-50% of the carrier content; organic ligands are cyclopentadienyl and the derivative thereof, or indenyl and the derivative thereof, or flourenyl and the derivative thereof, or the bridging cyclopentadienyl and the derivative thereof, or the bridging indenyl and the derivative thereof, or the bridging flourenyl and the derivative thereof; the catalyst is used for homopolymerization or copolymerization of any one of or the mixture of any two or more of ethene, and alpha-olefin, cycloolefin and dialkene of C3-C20; the cocatalyst is alkyl aluminium, alkylaluminium halide or alkylaluminoxane; the ratio of Al and the central atom zirconium of the metallocene compound is 10-3000; the polymerization temperature is minus 78 DEG C to 200 DEG C, the pressure is 0.1 to 10MPa, and the catalytic activity is high.

Description

technical field [0001] The invention relates to a preparation method of a polyolefin catalyst with organophenyl zirconium phosphate as a carrier and a method for catalyzing olefin polymerization thereof, wherein organic benzene in organophenyl zirconium phosphate refers to benzene or benzene derivatives, and the main catalyst for catalyzing olefin polymerization is metallocene catalysts. Background technique [0002] Metallocene catalysts for polymerization are mainly divided into two categories: homogeneous and supported. The homogeneous metallocene catalyst system has problems such as poor product morphology and high dosage of cocatalyst methylaluminoxane in the polymerization process. The preparation of supported metallocene catalysts by loading technology can reduce the amount of co-catalyst; at the same time, increase the molecular weight of the polymer, improve the shape of the polymer, and increase the bulk density of the polymer, so that the metallocene catalyst can...

Claims

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Application Information

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IPC IPC(8): C08F10/00C08F4/6592
Inventor 义建军祖凤华张法智徐庆红袁苑贾军纪卢晓英朱博超
Owner PETROCHINA CO LTD
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