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A kind of polymer supported copper catalyst and its preparation and application

A technology of copper catalyst and polymer, which is applied in the field of polymer-supported copper catalyst and its preparation and application, can solve the problems of difficult separation of products, high price of ionic liquid, high price of metal ruthenium, etc., achieve high activity and selectivity, easy Recycling and reuse, the effect of simple preparation method

Active Publication Date: 2021-12-28
NANJING TECH UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] At present, there are many methods for preparing TMBQ by oxidizing TMP, among which there is a method for oxidizing TMP with molecular oxygen in the presence of copper chloride (Appl.Catal., A.2005,280,55-73), but this method will form Cl-containing by-products and requires the use of corrosion-resistant equipment; then in order to reduce CuCl 2 The dosage, try to use ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate (Catal.Commun., 2009, 10 (5): 725-727), the yield can reach 97%, but ionic liquid The price is more expensive, and the purity of the product is difficult to guarantee; for example, Ti(Ⅳ) / SiO 2 Catalyst (Catal.Today, 2009, 141:330-336), the yield reaches 98%. The author uses a small amount of acetonitrile as a coordination solvent to help TMP realize the adsorption on the Ti site. The catalyst has high catalytic activity and high selectivity sex
But using H 2 o 2 As an oxidant, no oxygen is cheap and safe; there is also a ruthenium catalyst (Adv.Synth.Catal.2010,352,1615-1620) that has been developed, which uses H 2 o 2 Oxidation, but the yield can only reach 83%, and the price of metal ruthenium is relatively expensive, which is not conducive to industrial production; for the catalyst doped with vanadium (ACS Catal.2018,8,1297-1307), the catalyst has a higher conversion rate and selectivity and reusability, but vanadium is easily deactivated during the reaction, and considering environmental protection, it cannot be put into industrial production
[0004] Although there are many reports on Cu-containing catalysts so far, most of them are faced with the problem of high dosage or difficult separation of products.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment example 1

[0017] Take 901.0mg o-phenanthroline (5mmol), 390.5mg benzene (5mmol), 1141.4mg dimethoxymethane (15mmol), then add 10ml 1,2-dichloroethane, stir well and add 3333.5mg anhydrous AlCl 3 , then stirred at 25°C for 4h, then placed at 150°C for aging, washed with methanol, dried, and finally washed with sodium hydroxide solution to remove anhydrous aluminum trichloride, and washed with deionized water to medium after suction filtration sexual, dry. A cross-linked polymer of o-phenanthroline and aryl compound is obtained. Take 500.0mg carrier, add to 16.9mg Cu(CH 3 OO) 2 .H 2 O in 20ml of ethanol solution, stirred for 5h, then rotary evaporated and dried to obtain the catalyst A1 (4.0% Cu) required for the reaction.

Embodiment example 2

[0019] Take 450.5mg of o-phenanthroline (2.5mmol), 390.5mg of benzene (5mmol), 1141.4mg of dimethoxymethane (15mmol), then add 10ml of 1,2-dichloroethane, stir well and then add 3333.5mg of Water AlCl 3 , then stirred at 25°C for 4h, then placed at 150°C for aging, washed with methanol, dried, and finally washed with sodium hydroxide solution to remove anhydrous aluminum trichloride, and washed with deionized water to medium after suction filtration sexual, dry. A cross-linked polymer of o-phenanthroline and aryl compound is obtained. Take 500.0mg carrier, add to 16.9mg Cu(CH 3 OO) 2 .H 2 O in 20ml of ethanol solution, stirred for 5h, then rotary evaporated and dried to obtain the catalyst A2 (4.0% Cu) required for the reaction.

Embodiment example 3

[0021] Take 901.0mg of phenanthroline (5mmol), 195.25mg of benzene (2.5mmol), 1141.4mg of dimethoxymethane (15mmol), then add 10ml of 1,2-dichloroethane, stir evenly and add 3333.5mg of Water AlCl 3 , then stirred at 25°C for 4h, then placed at 150°C for aging, washed with methanol, dried, and finally washed with sodium hydroxide solution to remove anhydrous aluminum trichloride, and washed with deionized water to medium after suction filtration sexual, dry. A cross-linked polymer of o-phenanthroline and aryl compound is obtained. Take 500.0mg carrier, add to 16.9mg Cu(CH 3 OO) 2 .H 2 O in 20ml ethanol solution, stirred for 5h, then rotary evaporated and dried to obtain the catalyst A3 (4.0% Cu) required for the reaction.

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PUM

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Abstract

The invention describes a polymer-supported copper catalyst and its preparation and application, which is characterized in that the carrier is a cross-linked polymer of o-phenanthroline and an aryl compound, the active component is metallic copper, and the copper is loaded on o-phenanthroline On cross-linked polymers with aryl compounds, where the mass loading of copper is 1%-10%. The preparation method is to synthesize cross-linked polymer with o-phenanthroline, aryl compound and dimethoxymethane under strong acid catalysis, and further load copper compound copper on the polymer to obtain the polymer-supported copper catalyst . The supported metal copper catalyst can be used to catalyze oxygen oxidation of 2,3,6-trimethylphenol to prepare 2,3,5-trimethyl-1,4-benzoquinone. The preparation method of the catalyst is simple, has high activity and selectivity, good stability, and the catalyst can be repeatedly used, and has good industrial prospects.

Description

technical field [0001] The invention relates to a polymer-loaded copper catalyst and its preparation and application, which are used to catalyze oxygen oxidation of 2,3,6-trimethylphenol to prepare 2,3,5-trimethyl-1,4-benzoquinone. Background technique [0002] Functionalized benzoquinone (BQ) is a structural moiety in a variety of bioactive compounds, and the selective catalytic oxidation of alkylphenols with oxidants is the most economical and ecological route to produce important BQs, especially trimethyl-p-benzoquinone (TMBQ, Vitamin E key intermediate). Its preparation is mainly obtained by oxidizing 2,3,6-trimethylphenol (hereinafter referred to as TMP), and after its hydrogenation, 2,3,5-trimethylhydroquinone, the main raw material for preparing vitamin E, is obtained. [0003] At present, there are many methods for preparing TMBQ by oxidizing TMP, among which there is a method for oxidizing TMP with molecular oxygen in the presence of copper chloride (Appl.Catal., A...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J31/06C07C46/08C07C50/02
CPCC07C46/08B01J31/06C07C2601/16B01J2231/70C07C50/02
Inventor 黄军李如月郭婉婉
Owner NANJING TECH UNIV