Imidazole bridged metallocene, catalyst and preparation and application thereof

A metallocene catalyst, metallocene technology, applied in the direction of metallocene, physical/chemical process catalyst, organic compound/hydride/coordination complex catalyst, etc., can solve the problem that high-value solvent oil cannot be produced, cannot be obtained, reduce Special solvent oil value and other issues, to achieve the effect of reducing catalyst cost, improving selectivity, and low sensitivity

Pending Publication Date: 2022-07-05
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0015] Existing catalyst formulations and technologies cannot obtain a high proportion of C 16 and C 20 High-carbon olefins cannot produce high-value solvent oils, which reduces the value of special solvent oils

Method used

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  • Imidazole bridged metallocene, catalyst and preparation and application thereof
  • Imidazole bridged metallocene, catalyst and preparation and application thereof
  • Imidazole bridged metallocene, catalyst and preparation and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0053] (1) Add 66g cyclopentadiene (66g / mol) to tetrahydrofuran, cool to -40°C, then dropwise add 64g butyllithium (64g / mol), stir for 6h, then add 127g 1,4-dichloro Butane (127 g / mol). Stirring was continued for 10 h.

[0054] (2) 34g of imidazole (68g / mol), 156g of chlorobutylcyclopentadiene (156g / mol) and 106g of sodium carbonate (106g / mol) were added to 680g of acetonitrile, heated and stirred at a temperature of 70°C and reacted for 24h, The solid was removed by filtration, and the liquid was separated by rotary distillation to obtain N,N-dicyclopentadienylbutylimidazole.

[0055] (3) Dissolve 86 g of N,N-dicyclopentadienylbutylimidazole (345 g / mol) in 3450 g of tetrahydrofuran, and cool to -40°C. After stirring, 48 g of n-butyllithium (64 g / mol) was added dropwise, and the reaction was stirred for 5 h. Then, 58 g of zirconium tetrachloride (233 g / mol) was added thereto, followed by stirring for 24 hours.

[0056] (4) Drain the tetrahydrofuran in the solution, add 603...

Embodiment 2

[0062] (1) Add 66g cyclopentadiene (66g / mol) to tetrahydrofuran, cool to -40°C, then dropwise add 76.8g butyllithium (64g / mol), stir for 3h, then add 127g 1,4-dichloro butane (127 g / mol). Stirring was continued for 10 h. Distillation separation to obtain chlorobutylcyclopentadiene.

[0063] (2) 34g of imidazole (68g / mol), 187g of chlorobutylcyclopentadiene (156g / mol) and 159g of sodium carbonate (106g / mol) were added to 1700g of acetonitrile, heated and stirred at a temperature of 50°C for 24h, The solid was removed by filtration, and the liquid was separated by rotary distillation to obtain N,N-dicyclopentadienylbutylimidazole.

[0064] (3) 86 g of N,N-dicyclopentadienylbutylimidazole (309 g / mol) was dissolved in 4299 g of tetrahydrofuran, and cooled to -40°C. After stirring, 56 g of n-butyllithium (64 g / mol) was added dropwise, and the reaction was stirred for 5 h. Then, 70 g of zirconium tetrachloride (233 g / mol) was added thereto, followed by stirring for 24 hours.

...

Embodiment 3

[0071] (1) Add 66g of cyclopentadiene (66g / mol) to tetrahydrofuran, cool to -40°C, then dropwise add 51.2g of butyllithium (64g / mol), stir for 3h, then add 101.6g of 1,4-di Chlorobutane (127 g / mol). Stirring was continued for 10 h.

[0072] (2) 34g of imidazole (68g / mol), 140g of chlorobutylcyclopentadiene (156g / mol) and 53g of sodium carbonate (106g / mol) were added to 340g of acetonitrile, heated and stirred at a temperature of 80°C for 24h, The solid was removed by filtration, and the liquid was separated by rotary distillation to obtain N,N-dicyclopentadienylbutylimidazole.

[0073] (3) Dissolve 86 g of N,N-dicyclopentadienylbutylimidazole (309 g / mol) in 860 g of tetrahydrofuran, and cool to -40°C. After stirring, 44.8 g of n-butyllithium (64 g / mol) was added dropwise, and the reaction was stirred for 5 h. Then, 46.6 g of zirconium tetrachloride (233 g / mol) was added thereto, followed by stirring for 24 hours.

[0074] (4) Drain the tetrahydrofuran in the solution, add ...

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Abstract

The invention discloses a metallocene catalyst. The catalyst comprises imidazole bridged metallocene, alkyl metal and a solvent, imidazole bridged metallocene is used as a main catalyst, and alkyl metal is used as a cocatalyst; wherein the molar ratio of the imidazole bridged metallocene to the alkyl metal is 1: (5-500), and the solvent accounts for 40-90 wt% of the catalyst. The main catalyst provided by the invention adopts a novel metallocene structure, so that the electron and space effects of metallocene are effectively regulated and controlled, and the catalytic activity of metallocene is greatly improved. The catalyst composition provided by the invention improves the selectivity and yield of C16 and C20 isoalkanes in butylene oligomerization products.

Description

technical field [0001] The invention relates to a metallocene, a catalyst and its preparation and application, in particular to a metallocene catalyst for preparing high-boiling solvent oil by oligomerizing butene. Background technique [0002] Mixed butenes are oligomerized to generate C8-C20 iso-olefins, which can be hydrogenated to produce isoparaffin solvent oil. Synthetic isoparaffin solvent oil is a special oil that does not contain sulfur, aromatic hydrocarbons and other harmful substances and has no peculiar smell. It can be used as a solvent for the production of coatings, pesticides, inks and other products. At the same time, it can also be used as the base oil of low melting point lubricating oil. where C 16 and C 20 It is a high-value solvent oil that is used in ink solvents and other uses such as high-carbon hydrocarbons. A large amount of butene can be obtained from the ethylene cracking process of petroleum refining and the olefin-to-olefin process of coal...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F17/00B01J31/22C07C2/32C07C11/02C10M105/04
CPCC07F17/00B01J31/2265B01J31/181C07C2/32C10M105/04B01J2531/48B01J2231/20C10M2203/024C07C11/02
Inventor 张志智王陶孙潇磊刘全杰张喜文
Owner CHINA PETROLEUM & CHEM CORP
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