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Constrained-configuration dinuclear metallocene, and preparation method and application thereof

A metallocene compound and configuration technology, which is applied in the field of configuration-limited dinuclear metallocene compounds and their preparation, can solve the problems of increasing alpha-olefin steric hindrance, long steps, expensive raw materials, etc., and achieves stable steric configuration and good regulation. , the effect of 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 Si atoms, the steps are long and the raw materials are expensive.

Method used

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  • Constrained-configuration dinuclear metallocene, and preparation method and application thereof
  • Constrained-configuration dinuclear metallocene, and preparation method and application thereof
  • Constrained-configuration dinuclear metallocene, and preparation method and application thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0077] The present embodiment provides a kind of restricted configuration binuclear metallocene compound, and the molecular formula of this compound (complex 1) is: [(tBuNTiCl 2 )(η 5 -C 5 h 4 )C(H)] 2 [(CH 2 ) 3 ].

[0078] The synthetic route of complex 1 is as follows:

[0079]

[0080] The specific preparation process of complex 1 is:

[0081] (1) Under the protection of argon, use methanol as a solvent, mix glutaraldehyde (100g, 1.0mol) and tetrahydropyrrolidine (3.5g, 0.05mol), cool the reaction bottle to 0°C, and slowly add new cracking Cyclopentadiene (132g, 2.0mol), after the dropwise addition, continue to stir for 4 hours. After the reaction, add a saturated saline solution of dilute acetic acid to adjust the pH to weak acidity. Remove the solvent methanol on a rotary evaporator. Extract with ether, combine the organic phases, wash with saturated NaCl, anhydrous MgSO 4 Drying; filtering, removing the residual solvent under reduced pressure to obtain a tot...

Embodiment 2

[0087] This example provides the application of the complex 1 prepared in Example 1 as a catalyst in homogeneously catalyzed ethylene polymerization.

[0088] Homogeneously catalyzed ethylene polymerization comprises the following steps:

[0089] 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 gas 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 60°C to constant weight, weigh the polymer mass, and calculate that the polymerization activity of the catalyst...

Embodiment 3

[0091] 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.

[0092] Homogeneously catalyzed ethylene and 1-hexene copolymerization comprises the following steps:

[0093] 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 60°C to constant weight, weigh the polymer, and calculate the catalyst polymerization activity to be 1.1×10 6 gpolymer / molM h, Mw...

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Abstract

The invention provides a constrained-configuration dinuclear metallocene, and a preparation method and application thereof. The metallocene has a two-center CGC (Critical Grid Current), so that not only is the activity of a single-site catalyst realized, but also electronic environments and space environments of the two metal centers are conveniently controlled through adjusting the length of a carbon bridge, the molecular weight distribution of a polymer is further regulated and controlled, and wide-distribution polyolefin is produced. The technical scheme provided by the invention has the advantages of short synthetic route, simple synthetic process and low industrial cost.

Description

technical field [0001] The invention belongs to the technical field of metallocene catalysts, and in particular relates to a restricted configuration binuclear metallocene compound and its preparation method and application. Background technique [0002] In 1994, the synthesis and application research of CGC catalyst opened a new era of olefin copolymerization. DOW company applied for a large number of CGC patents, which are characterized in that the side chain of the alkene ring contains a coordinating nitrogen atom. This type of compound (such as formula III) is suitable for Homogeneous and supported catalytic copolymerization of ethylene α-olefins under high pressure with an activity of 10 6 gPolymer / mol·Metal·h, α-olefin insertion rate is 5-8% mol. [0003] [0004] In 2001, JerzyKlosin et al [JerzyKlosin.PreparationofNewOlefinPolymerizationPrecatalystsbyFacileDerivatizationofImino–EnamidoZrMe3andHfMe3Complexes[J]2013,32(21),pp6488–6499.] studied in detail the influe...

Claims

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Application Information

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IPC IPC(8): C07F17/00C08F10/00C08F4/6592
Inventor 张瑀健米普科高针针许胜高宇新宋磊赵成才赵增辉曹婷婷何书艳王立娟王炎鹏谢彬李洪兴任合刚王登飞付义马丽张楠
Owner PETROCHINA CO LTD
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