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Asymmetric constrained-geometry dinuclear metallocene compound and preparation method and application thereof

A metallocene compound, asymmetric technology, applied in the direction of titanium organic compounds, chemical instruments and methods, compounds of Group 4/14 elements of the periodic table, etc. problem, to achieve the effect of stable steric configuration, good catalytic activity and copolymerization ability

Active Publication Date: 2016-01-27
PETROCHINA CO LTD +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the above-mentioned bridging method uses carbon bridges to connect two CpNSi-type CGCs, which will undoubtedly increase the steric hindrance of α-olefin insertion; while bridging through N atoms, the steps are long and the raw materials are expensive.

Method used

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  • Asymmetric constrained-geometry dinuclear metallocene compound and preparation method and application thereof
  • Asymmetric constrained-geometry dinuclear metallocene compound and preparation method and application thereof
  • Asymmetric constrained-geometry dinuclear metallocene compound and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0079] The present embodiment provides a kind of asymmetric restricted configuration dinuclear metallocene compound, the molecular formula of this compound (complex 1) is: [(tBuNTiCl 2 )(η 5 -C 5 h 4 )C(H)(CH 2 ) 2 C(CH 3 )(η 5 -C 5 h 4 )(tBuNTiCl 2 )].

[0080] The synthetic route of complex 1 is as follows:

[0081]

[0082] The specific preparation process of complex 1 is:

[0083] (1) Under the protection of argon, use methanol as a solvent, mix 4-oxopentaldehyde (100g, 1.0mol) and tetrahydropyrrolidine (7.0g, 0.10mol), cool the reaction bottle to 0°C, and slowly drop Add the newly cracked cyclopentadiene (132g, 2.0mol), continue to stir the reaction for 4 hours after the completion of the dropwise addition, add the saturated aqueous common salt solution of dilute acetic acid after the completion of the reaction to adjust the pH to weak acidity, remove the solvent methanol on the rotary evaporator, The aqueous phase was extracted with ether, and the combined...

Embodiment 2

[0089] This example provides the application of the complex 1 prepared in Example 1 as a catalyst in homogeneously catalyzed ethylene polymerization.

[0090] Homogeneously catalyzed ethylene polymerization comprises the following steps:

[0091] Replace the 100mL autoclave equipped with a magnetic stirrer and air duct with ethylene gas for 3 times, under the protection of nitrogen, add toluene, cocatalyst MAO2.5mL (1.60M)[Al / M=1000], 2.0μmol complexation Material 1, control the total volume to 100mL, feed ethylene gas, start the polymerization reaction at 50°C, maintain the ethylene pressure at 1.2MPa, stir the reaction for 30min, close the cylinder, release the pressure, and then terminate the reaction with 10% hydrochloric acid ethanol. Transfer the polymer to a beaker, let it stand overnight, filter and wash the polymer fully with ethanol, dry it in vacuum at 50°C to constant weight, weigh the polymer mass, and calculate that the polymerization activity of the catalyst is ...

Embodiment 3

[0093] This example provides the application of the complex 1 prepared in Example 1 as a catalyst in the homogeneously catalyzed copolymerization of ethylene and 1-hexene.

[0094] Homogeneously catalyzed ethylene and 1-hexene copolymerization comprises the following steps:

[0095] Replace the 100mL autoclave equipped with a magnetic stirrer and gas tube with ethylene gas for 3 times, and add toluene, 1-hexene 10mL, cocatalyst MAO2.5mL (1.60M) [Al / M=1000 ], 2.0μmol complex 1, control the total volume to 100mL, feed ethylene gas, start the polymerization reaction at 50°C, maintain the ethylene pressure at 0.3MPa, stir the reaction for 30min, close the cylinder, and terminate the reaction with 10% hydrochloric acid ethanol . Transfer the polymer to a beaker, let it stand overnight, filter and wash the polymer fully with ethanol, dry it in vacuum at 50°C to constant weight, weigh the polymer, and calculate the catalyst polymerization activity to be 1.14×10 6 gpolymer / molM h, M...

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Abstract

The invention provides an asymmetric constrained-geometry dinuclear metallocene compound, a preparation method of the asymmetric constrained-geometry dinuclear metallocene compound and application of the asymmetric constrained-geometry dinuclear metallocene compound. The dinuclear metallocene compound has an asymmetric double-site CGC (constrained geometry complex), which has the advantages that not only is the activity of a single-site catalyst obtained, but also the electronic environment and spatial environment of two metal centers are controlled conveniently through the modification of a substituent group on a bridge base C and the adjustment of the length of a carbon bridge, therefore the molecular weight distribution of a polymer is regulated, and widely-distributed polyolefin is produced. The technical scheme provided by the invention has the advantages of short synthetic route, simple synthesis technology and low industrial cost.

Description

technical field [0001] The invention belongs to the technical field of metallocene catalysts, and in particular relates to an asymmetric restricted configuration dinuclear metallocene compound and its preparation method and application. Background technique [0002] The first [η 5 , η 1 -C 5 Me 4 SiMe 2 N-t-Bu]ScH.PMe 3 Constrained configuration metallocene (CGC) compound catalyst, its unique copolymerization ability has aroused great interest in the academic circle, so CGC chemistry ushered in great development, DOW company [ShapiroPJ, eta1.[J]1990, 9: 867-869.] development A series of [C 5 R 4 (SiMe 2 )nNR]MCl 2 / MAO polyolefin catalysts, especially classical CGC catalysts using tetramethylcyclopentadiene ligands [η 5 , η 1 --C 5 Me 4 SiMe 2 N-t-Bu]TiCl 2 The high activity and excellent copolymerization ability exhibited by / MAO have been highly valued by the polyolefin industry. EXXON has also developed a CGC catalytic system, which is widely used in the fi...

Claims

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Application Information

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IPC IPC(8): C07F7/28C07F7/00C08F10/00C08F4/6592
Inventor 张瑀健王建伟米普科许胜高宇新宋磊赵成才王斯晗姜进宪何书艳王立娟王炎鹏李洪兴赵增辉任合刚王登飞付义谢彬王淑英张瑞任鹤
Owner PETROCHINA CO LTD
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