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Bridged indene fluorene zirconium, hafnium compound and its preparation method and application in propylene oligomerization

A hafnium compound, the technology of catalyzing propylene, applied in chemical instruments and methods, organic chemistry, metallocene, etc., can solve the problems of limited molecular weight range of propylene oligomers, limited activity and selectivity, and limited practical value catalyst structure, etc., to achieve high catalytic performance active effect

Active Publication Date: 2017-07-25
EAST CHINA UNIV OF SCI & TECH
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  • Abstract
  • Description
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AI Technical Summary

Problems solved by technology

However, the molecular weight range of propylene oligomers prepared by this catalyst is very limited, and changing the polymerization conditions to control the molecular weight often sacrifices the β-methyl elimination selectivity
[0006] In summary, although metallocene catalysts are considered to be potential good catalysts for the preparation of allyl-terminated propylene oligomers, they have practical value in terms of activity and selectivity. The catalyst structure is very limited and can maintain high activity. and selectivity, and the catalyst structure that can control the molecular weight of the polymer has not been reported so far

Method used

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  • Bridged indene fluorene zirconium, hafnium compound and its preparation method and application in propylene oligomerization
  • Bridged indene fluorene zirconium, hafnium compound and its preparation method and application in propylene oligomerization
  • Bridged indene fluorene zirconium, hafnium compound and its preparation method and application in propylene oligomerization

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0044] Synthesis of zirconium complex C1

[0045] (1) Synthesis of substituted indene In1

[0046]

[0047] Put 0.67g of magnesium bars in a three-necked flask, add 30mL of anhydrous ether, and dropwise add 4.10g of bromobenzene in 30mL of ether solution. At room temperature, 3.20 g of 2-methyl-2,3-dihydro-1-indanone in 40 mL of diethyl ether solution was added dropwise, and the reaction was stirred at room temperature for 3 h. In an ice-water bath, use 30 mL of saturated NH 4 Cl aqueous solution was used to terminate the reaction, the aqueous phase was extracted with 120 mL ether, and the organic phase was extracted with anhydrous MgSO 4 Dry, spin dry, dissolve with 70mL toluene, add 0.50g p-toluenesulfonic acid monohydrate, reflux for 4h, add 30mL saturated NaHCO 3 , the aqueous phase was extracted with 100mL petroleum ether, and the organic phase was extracted with anhydrous MgSO 4 Dry, spin off the solvent, and separate by column to obtain 3.83 g of light yellow liq...

Embodiment 2

[0057] Synthesis of zirconium complex C3

[0058] (1) Synthesis of substituted indene In2

[0059]

[0060] 2.90g of 2-methylindene was placed in a Schlenk bottle, dissolved in 60mL of ether, and 10.1mL (2.2mol / L) of n-butyllithium in n-hexane was added dropwise in a liquid nitrogen-ethanol bath, and the reaction was stirred overnight. Add 3.81g benzyl bromide in 20mL diethyl ether solution under ice-cooling, stir at room temperature for 4d, add 30mL saturated NH 4 Cl aqueous solution was used to terminate the reaction, the aqueous phase was extracted with 45 mL ether, and the organic phase was extracted with anhydrous MgSO 4 After drying, the solvent was removed and separated by column to obtain 3.58 g of light yellow liquid with a yield of about 73.3%.

[0061] 1 H NMR (400MHz, 298K, CDCl 3 ):δ7.21-7.14(m,3H,Ar-H),7.14-7.05(m,4H,Ar-H),6.89(td,J=7.4,1.8Hz,1H,Ar-H),6.76( d,J=7.4Hz,1H,Ar-H),6.35(s,1H,3-Ind-CH),3.47(dd,J=8.6,5.6Hz,1H,1-Ind-CH),3.23(dd ,J=13.8,5.6Hz,1H,C...

Embodiment 3

[0070] Synthesis of zirconium complex C9

[0071] (1) Synthesis of substituted indene In5

[0072]

[0073] Put 3.40g of 4,7-dimethylindene in a Schlenk bottle, dissolve it with 60mL of ether, add 10.7mL (2.2mol / L) of n-butyl lithium in n-hexane dropwise in a liquid nitrogen-ethanol bath, and stir the reaction overnight. Add 4.04g of benzyl bromide in 20mL ether solution under ice-cooling, stir at room temperature for 4d, and dissolve with 30mL saturated NH 4 Cl aqueous solution was used to terminate the reaction, the aqueous phase was extracted with 45 mL ether, and the organic phase was extracted with anhydrous MgSO 4 After drying and removing the solvent, it was separated by column to obtain 3.66 g of light yellow liquid with a yield of about 66.2%.

[0074] 1 H NMR (400MHz, 298K, CDCl 3 ):δ7.38-7.19(m,5H,Ar-H),7.04-6.90(m,2H,Ar-H),6.85(d,J=5.6Hz,1H,3-Ind-CH),6.37( d,J=5.6Hz,1H,2-Ind-CH),3.82-3.72(m,1H,1-Ind-CH),3.64(dd,J=13.2,4.4Hz,1H,CH 2 ),2.54(s,3H,CH 3 ),2.39...

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Abstract

The invention discloses an ethylene-bridged indenyl-fluorenyl zirconium (hafnium) compound as well as a preparation method and application thereof in oligomerization of propylene. The ethylene-bridged indenyl-fluorenyl zirconium (hafnium) compound can be obtained by virtue of firstly reacting an ethylene-bridged indenyl-fluorenyl ligand compound with an alkyl alkali metal in an organic medium and then adding ZrCl4 or HfCl4. The ethylene-bridged indenyl-fluorenyl zirconium (hafnium) compound disclosed by the invention is an efficient catalyst and has high catalytic activity when used for catalyzing oligomerization of propylene under relatively mild conditions and thus the propylene oligomer containing allyl end groups can be highly selectively obtained in the presence of an untreated alkyl aluminoxane co-catalyst; and meanwhile, the control of the molecular weight of the oligomer can be achieved by virtue of controlling polymerization conditions and the ethylene-bridged indenyl-fluorenyl zirconium (hafnium) compound has very high industrial application values and has the structure represented by the formula as shown in the specification.

Description

technical field [0001] The invention relates to a class of improved ethylene bridging substituted indene-fluorene zirconium and hafnium compounds and a preparation method thereof, and relates to the application of this type of catalyst in the preparation of propylene oligomers with high allyl end group content. Background technique [0002] Long-chain α-olefin is a kind of olefin compound with important application value. It is not only an important raw material for the manufacture of detergents and greases, but also an important intermediate for various other industrial products. Among them, long-chain alpha-olefins containing allyl end groups are more valuable because they are also important comonomers for the production of modified polyolefin materials. Polyolefin materials are currently the most widely used plastic species, with an annual output of more than 100 million tons worldwide. Using long-chain α-olefins as comonomers to modify polyolefin materials for the produ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F17/00C08F4/6592C08F10/06
Inventor 马海燕张雷张滨
Owner EAST CHINA UNIV OF SCI & TECH
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