N-heterocyclic carbene functionalized porous organic polymer supported copper catalyst, preparation method thereof and application of catalyst

A nitrogen-heterocyclic carbene and porous polymer technology, applied in the field of catalyst preparation, can solve the problems of corrosion of reaction equipment, poor recycling performance, and easy loss of active components, etc., and achieve good application prospects and excellent recycling performance , the effect of strong coordination ability

Active Publication Date: 2019-05-14
南京宇源新能碳中和科技有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the solubility of CuCl in methanol is poor, the reaction efficiency is low, and chloride ions are highly corrosive to stainless steel reactors.
Chinese patent CN1197792A adds MgCl in the reaction solution 2 and other additives, which increase the solubility of cuprous chloride in methanol, thereby improving the catalytic performance, but still do not solve the problems such as the corrosion of reaction equipment
However, the supported catalyst prepared by surface covalent bond modification often leads to the easy loss of active components and poor recycling performance due to the uneven distribution of active components and the distribution of active components on the surface of the carrier.

Method used

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  • N-heterocyclic carbene functionalized porous organic polymer supported copper catalyst, preparation method thereof and application of catalyst
  • N-heterocyclic carbene functionalized porous organic polymer supported copper catalyst, preparation method thereof and application of catalyst
  • N-heterocyclic carbene functionalized porous organic polymer supported copper catalyst, preparation method thereof and application of catalyst

Examples

Experimental program
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Effect test

Embodiment 1

[0047] Example 1 The application of a nitrogen-heterocyclic carbene functionalized porous organic polymer-supported copper catalyst in the oxidative carbonylation of liquid alcohols, the steps are as follows:

[0048] (1) Preparation of carrier (PNHC-1)

[0049] Mix 10 g of 1-butyl-3-methylimidazolium chloride salt and 2.5 g of deionized water at room temperature to obtain a 1-butyl-3-methylimidazolium chloride salt solution, and then add 0.461g of bis(1-imidazolyl)methane and 0.739g of 1,3,5-tri(bromomethyl)benzene were stirred and reacted at room temperature (25°C, the same below) for 2 hours for prepolymerization, and then the reaction The temperature of the solution was raised to 100°C, and the mixture was stirred and reacted at 100°C for 36 hours to carry out polymerization; after the reaction was completed, a massive solid was obtained, which was washed with water for 6 times, then washed with absolute ethanol for 3 times, and then filtered to obtain a solid The porous ...

Embodiment 2

[0056] Example 2 The application of a nitrogen-heterocyclic carbene functionalized porous organic polymer-supported copper catalyst in the oxidative carbonylation of liquid alcohols, the steps are as follows:

[0057] (1) Preparation of carrier (PNHC-2)

[0058] 15g of 1-propyl-3-methylimidazolium bromide and 3.0g of deionized water were fully stirred at room temperature to obtain a 1-propyl-3-methylimidazolium bromide solution, and then 0.953 g of bis(1-imidazolyl)methane and 1.447g of 1,2,4,5-tetrakis(bromomethyl)benzene were stirred and reacted at room temperature for 1 hour for pre-polymerization, and then the temperature of the reaction solution was raised to 90°C, Stir the reaction at 90°C for 48 hours to carry out polymerization; after the reaction is completed, blocky solids are obtained. The blocky solids are washed with water for 6 times, and then washed with ethanol for 3 times. After filtering, the obtained solids are vacuum-dried overnight at 60°C to obtain The p...

Embodiment 3

[0064] Example 3 The application of a nitrogen-heterocyclic carbene functionalized porous organic polymer-supported copper catalyst in the oxidative carbonylation of liquid alcohols, the steps are as follows:

[0065] (1) Preparation of carrier (PNHC-3)

[0066] 20g of 1-hexyl-3-methylimidazole nitrate and 2.8g of deionized water were fully stirred at room temperature to obtain a 1-hexyl-3-methylimidazole nitrate solution, and then 0.960g of Bis(1-imidazolyl)methane and 1.540g of 1,3,5-tri(bromomethyl)benzene were stirred and reacted at room temperature for 1 hour for pre-polymerization, and then the temperature of the reaction solution was raised to 115°C. Under stirring reaction 24 hours carry out polymerization; Obtain block solid after reaction is finished, block solid is washed 6 times with water earlier, then cleans with ethanol 3 times, filters, and gained solid obtains porous polymer carrier after 60 ℃ of vacuum drying overnight ( PNHC-3), the mass of PNHC-3 is 2.52g,...

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Abstract

The invention relates to the technical field of catalyst preparation, in particular to an n-heterocyclic carbene functionalized porous organic polymer supported copper catalyst, a preparation method thereof and an application of the catalyst. Imidazolium ionic liquid serves as a solvent, water serves as a co-solvent, bis(1-imidazolyl) methane and polybrominated methyl aromatic hydrocarbon serve asco-monomers, pre-polymerization is performed for 0.5-3 hours at room temperature, polymerization reaction is performed for 12-48 hours at the temperature of 80-140 DEG C to obtain a porous polymer containing imidazolium salt, and then cuprous salt is supported on the porous polymer under alkaline conditions to obtain the n-heterocyclic carbene functionalized porous organic polymer supported copper catalyst. The porous catalyst has the advantages of large specific surface area and wide pore diameter distribution, and methanol and ethanol oxidative carbonylation can be efficiently catalyzed tosynthesize dialkyl carbonate. Compared with a traditional supported catalyst, the catalyst is high in activity, not easily lost, long in recycling life and expected to be used for practical industrialproduction.

Description

technical field [0001] The invention relates to the technical field of catalyst preparation, in particular to a nitrogen-heterocyclic carbene functionalized porous organic polymer-supported copper catalyst, a preparation method thereof, and an application in liquid alcohol oxidative carbonylation. Background technique [0002] Organic carbonate is a kind of "green" chemical product with high added value, which can replace highly toxic and carcinogenic phosgene, dimethyl sulfate as methylating reagent, carbonylation reagent, etc. to manufacture many high value-added chemical products, There are many uses in organic synthesis, medicine, pesticides, solvents, fuel additives, etc. The industrial preparation methods of dimethyl carbonate include phosgene method, transesterification method and oxidative carbonylation method (including liquid phase method and gas phase method). Among them, the oxidative carbonylation method is a reaction using alcohol, oxygen, and carbon monoxide ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/22B01J35/10C07C69/96C07C68/00
CPCY02P20/54
Inventor 雷以柱李志王毅红陈定梅万亚荔田茂军兰国松
Owner 南京宇源新能碳中和科技有限公司
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