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Non-covalent polymer catalyst suitable for oxidization of 2,3,6-trimethylphenol and preparation method of non-covalent polymer catalyst

A technology of trimethylphenol and catalyst, which is applied in the field of non-covalent polymer catalysts and its preparation for the oxidation of 2,3,6-trimethylphenol, which can solve the problems of separation of products and catalysts, environmental pollution, and stability of small molecules Poor performance and other problems, to achieve the effect of good industrial application prospects, simple preparation method, and product selectivity

Active Publication Date: 2019-04-26
CENT SOUTH UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] At present, the industrial production of 2,3,5-trimethyl-p-benzoquinone is mainly prepared by the catalytic oxidation of 2,3,6-trimethylphenol, and the catalysts are mostly small molecules, such as CuCl 2 and Co (Salen), O 2 As an oxidant, although this type of catalyst has good conversion rate and selectivity, due to the poor stability of small molecules, the dissolution of small molecule catalysts in the reaction process makes it difficult to separate the product from the catalyst, making it difficult to recycle the catalyst and pollute the catalyst wastewater. The environment greatly restricts the industrial production of 2,3,5-trimethyl-p-benzoquinone. Therefore, finding a catalyst with good cycle performance and good catalytic performance is an urgent problem to be solved at present.
[0004] Compared with covalent polymers, non-covalent polymers have the advantages of simple synthesis and clear structure, but their poor stability limits the application of non-covalent polymers in heterogeneous catalysis.

Method used

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  • Non-covalent polymer catalyst suitable for oxidization of 2,3,6-trimethylphenol and preparation method of non-covalent polymer catalyst
  • Non-covalent polymer catalyst suitable for oxidization of 2,3,6-trimethylphenol and preparation method of non-covalent polymer catalyst
  • Non-covalent polymer catalyst suitable for oxidization of 2,3,6-trimethylphenol and preparation method of non-covalent polymer catalyst

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Embodiment 1

[0041] The invention provides a method for preparing a non-covalent polymer catalyst suitable for oxidation of 2,3,6-trimethylphenol, comprising the following steps:

[0042] (1) Synthesis of Salphen: In a 500ml three-necked flask, add 3,3-diaminobenzidine (1g, 4.67mmol) and 150ml of methanol, under nitrogen protection, dissolve salicylaldehyde (2.74g, 22.4mmol) in 100ml of methanol dropwise Added to the reaction solution, stirred at room temperature for 24h, filtered, washed with methanol to obtain the crude product, recrystallized from THF to obtain the desired Salphen compound, wherein the bisalphen structure is as follows:

[0043]

[0044] (2) Synthesis of cobalt (Salphen): In a 250ml three-necked flask, add Salphen (251mg, 0.4mmol) and 100ml THF, ultrasonically dissolve, under nitrogen protection, methanol (30ml) of cobalt acetate tetrahydrate (238mg, 0.95mmol) The solution was added dropwise to the THF solution of bi-Salphen, stirred at room temperature for 24 h, fil...

Embodiment 2

[0049] The invention provides a method for preparing a non-covalent polymer catalyst suitable for oxidation of 2,3,6-trimethylphenol, comprising the following steps:

[0050] (1) Synthesis of Salphen: In a 500ml three-necked flask, add 3,3-diaminobenzidine (1g, 4.67mmol) and 150ml of methanol, under nitrogen protection, dissolve salicylaldehyde (2.74g, 22.4mmol) in 100ml of methanol dropwise Added to the reaction solution, stirred at room temperature for 24h, filtered and washed with methanol to obtain the crude product, THF recrystallized to obtain the desired Salphen compound;

[0051] (2) Synthesis of cobalt (Salphen): In a 250ml three-necked flask, add Salphen (251mg, 0.4mmol) and 100ml THF, ultrasonically dissolve, under nitrogen protection, methanol (30ml) of cobalt acetate tetrahydrate (238mg, 0.95mmol) The solution was added dropwise to the THF solution of Salphen, stirred at room temperature for 24h, filtered, washed with methanol and water to obtain the desired Co(Sa...

Embodiment 3

[0055] The invention provides a method for preparing a non-covalent polymer catalyst suitable for oxidation of 2,3,6-trimethylphenol, comprising the following steps:

[0056] (1) Synthesis of Salphen: In a 500ml three-necked flask, add 3,3-diaminobenzidine (1g, 4.67mmol) and 150ml of methanol, under nitrogen protection, dissolve salicylaldehyde (2.74g, 22.4mmol) in 100ml of methanol dropwise Added to the reaction solution, stirred at room temperature for 24h, filtered and washed with methanol to obtain the crude product, THF recrystallized to obtain the desired Salphen compound;

[0057] (2) Synthesis of cobalt (Salphen): In a 250ml three-necked flask, add Salphen (251mg, 0.4mmol) and 100ml THF, ultrasonically dissolve, under nitrogen protection, methanol (30ml) of cobalt acetate tetrahydrate (238mg, 0.95mmol) The solution was added dropwise to the THF solution of Salphen, stirred at room temperature for 24h, filtered, washed with methanol and water to obtain the desired Co(Sa...

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Abstract

The invention discloses a catalyst suitable for catalytic oxidation of 2,3,6-trimethylphenol for preparing 2,3,5-trimethyl p-benzoquinone, and belongs to the technical field of preparation of catalysts. The catalyst is prepared from Co(Salphen) and a bipyridine compound; the bipyridine compound comprises two contrapuntal pyridyls, and a Co atom in the Co(Salphen) and a nitrogen atom in the bipyridine compound are connected with each other by a coordination bond, so as to form a non-covalent polymer catalyst. The catalyst is simple in preparation method, the 2,3,5-trimethyl p-benzoquinone can be generated through catalytic oxidation of the 2,3,6-trimethylphenol by taking O2 as an oxidizing agent at room temperature and normal pressure, the limit that most of the type of heterogeneous reactions need hydrogen peroxide and high temperature before is overcome, and the conversion rate of a substrate and the selectivity of a product in a recycling process of the catalyst can be well maintained.

Description

technical field [0001] The invention belongs to the technical field of catalyst preparation, and relates to a catalyst suitable for the catalytic oxidation of 2,3,6-trimethylphenol to prepare 2,3,5-trimethyl-p-benzoquinone, in particular to a catalyst suitable for 2,3 , A non-covalent polymer catalyst for the oxidation of 6-trimethylphenol and a preparation method thereof. Background technique [0002] 2,3,5-trimethyl-p-benzoquinone is an important intermediate for the synthesis of vitamin E. There are two main ways to synthesize 2,3,5-trimethyl-p-benzoquinone, one is sulfonation-oxidation method, The other is a one-step catalytic oxidation method. The sulfonation-oxidation method has serious environmental pollution and has been gradually eliminated; the one-step catalytic oxidation method has mild conditions, is friendly to the environment, and has broad development prospects. [0003] At present, the industrial production of 2,3,5-trimethyl-p-benzoquinone is mainly prepa...

Claims

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Application Information

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IPC IPC(8): B01J31/22C07C46/08C07C50/02C08G79/14
CPCB01J31/1691B01J31/2217B01J2531/0252B01J2531/845C07C46/08C07C2601/16C08G79/14C07C50/02Y02P20/584
Inventor 潘春跃张合喻桂朋
Owner CENT SOUTH UNIV
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