Catalyst precursor and its preparation method, catalyst and its application, and ethylene polymerization method

A technology of catalysts and bimetallic catalysts, applied in chemical instruments and methods, titanium organic compounds, compounds of group 4/14 elements of the periodic table, etc., can solve problems such as complex catalyst preparation processes, and achieve simple structure and high catalytic efficiency , Improve the effect of polymerization activity

Active Publication Date: 2014-05-21
CHINA PETROLEUM & CHEM CORP +1
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the preparation process of this catalyst is r

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  • Catalyst precursor and its preparation method, catalyst and its application, and ethylene polymerization method

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preparation example Construction

[0035] The present invention also provides a method for preparing the catalyst precursor, wherein the method includes under the conditions of the complexation reaction, the method includes: the method includes under the conditions of the complexation reaction, will have the structure shown in formula IV The general formula of compound and molecular structure is MCl 4 (THF) 2 The compound is contacted in an organic solvent to obtain the above-mentioned bimetallic catalyst precursor with an open structure shown in formula I based on a salicylaldimine ligand.

[0036] Formula IV,

[0037] Among them, R 1 , R 2 , R 3 , R 4 , R 1 ’, R 2’, R 3 ’ and R 4 ' each independently hydrogen, phenyl or C1-C20 alkyl, R 5 and R 5 ' each independently hydrogen or C1-C20 alkyl;

[0038] M is one of titanium, zirconium and hafnium, preferably titanium.

[0039] The preparation process of the above-mentioned bimetallic catalyst precursor with the open structure shown in formula I ba...

preparation example 1

[0066] This preparation example is used to illustrate the preparation of the bis salicylaldimine-titanium metal catalyst precursor with the structure shown in formula II.

[0067] 6,6'-(1E,1'E)-(4,4'-methylenebis(4,1-phenylene)bis(imine-1-substituted-1-ylidene))bis(form Base-1-substituted-1-ylidene)bis(2-tert-butylphenol) (prepared according to the preparation method recorded in Eur.Polym.J.2012,48,191-199, the same below) (1.77g, 3.41mmol ) was dissolved in dichloromethane solvent (the amount of dichloromethane used was 30mL), and the solution was added to the dichloromethane solution containing tetrachlorobis(tetrahydrofuran)titanium (2.28g, 6.82mmol) at -78°C (the amount of dichloromethane used is 30 mL), react at low temperature for 1 hour, return to room temperature 25°C, and continue to react for 16 hours. After the reaction was finished, the solvent was removed with a vacuum line, the residue was washed with dichloromethane and filtered through diatomaceous earth, the ...

preparation example 2

[0070] This preparation example is used to illustrate the preparation of the bis salicylaldimine-titanium metal catalyst precursor with the structure shown in formula II.

[0071]6,6'-(1E,1'E)-(4,4'-methylenebis(4,1-phenylene)bis(imine-1-substituted-1-ylidene))bis(form Base-1-substituted-1-ylidene)bis(2-tert-butylphenol)(0.24g, 0.46mmol) was dissolved in dichloromethane solvent (the amount of dichloromethane used was 30mL), and the Add this solution to a dichloromethane solution (the amount of dichloromethane is 30mL) containing tetrachlorobis(tetrahydrofuran)titanium (0.32g, 0.96mmol), react at low temperature for 1 hour, return to room temperature and heat to 40 °C, the reaction was continued for 12 hours. After the reaction was finished, the solvent was removed with a vacuum line, the residue was washed with dichloromethane and filtered through diatomaceous earth, the filtrate was sucked dry, and the crude product was recrystallized with dichloromethane / n-hexane to obtain ...

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Abstract

The invention discloses a catalyst precursor and its preparation method, a catalyst and its application, and an ethylene polymerization method. The catalyst precursor is a bimetallic catalyst precursor which has an open structure shown as a formula I and is based on a salicylaldehyde imine ligand, the preparation method of the catalyst precursor is as follows: under complexation reaction conditions, contacting a compound having a structure shown as a formula IV with a compound with a molecular structure general formula of MCl4 (THF) 2 in an organic solvent; the catalyst provided by the invention comprises the catalyst precursor and alkyl aluminoxane; the invention also provides the application of the catalyst in olefin polymerization, the invention also provides the ethylene polymerization method which is as follows: under olefin polymerization conditions, in the presence of an organic solvent, contacting ethylene with the catalyst precursor and the alkyl aluminoxane for polymerization. The preparation method of the catalyst precursor is simple, and the catalyst is high in catalytic efficiency. The formula I and the formula IV are shown in the specification.

Description

technical field [0001] The invention relates to the field of olefin coordination polymerization, in particular to a catalyst precursor and a preparation method thereof, a catalyst containing the catalyst precursor, an application of the catalyst in olefin polymerization, and an ethylene polymerization method. Background technique [0002] Polyolefin materials are widely used in various fields of the national economy due to their relatively small density, good chemical resistance, water resistance, good mechanical strength, and electrical insulation. [0003] Coordination polymerization represented by Ziegler-Natta catalysts and metallocene catalysts has promoted the rapid development of the polyolefin industry and gradually matured. Nowadays, non-metallocene catalysts have become a hotspot in the field of coordination polymerization, and salicylaldimine ligand transition metal catalysts are one of them. This type of catalyst has good olefin catalytic activity, for example: ...

Claims

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Application Information

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IPC IPC(8): C08F10/00C08F4/642C08F110/02C07F7/28C07F7/00
Inventor 韩书亮于国柱贺小进邵明波李传清徐林解希铭
Owner CHINA PETROLEUM & CHEM CORP
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