KR20200043648A - Method for producing 2,5-furandicarboxylic acid using ionic liquid and carbon dioxide - Google Patents

Abstract

The present invention relates to a method for manufacturing 2,5-furandicarboxylic acid, comprising the following steps: generating an ionic liquid by an acid-base reaction of an organic base and 2-Furoic acid; and conducting a reaction of the ionic liquid, a catalyst, and carbon dioxide to manufacture 2,5-furandicarboxylic acid. By the same, it is possible to manufacture 2,5-furandicarboxylic acid in a high yield by directly conduct reaction in a simple process in a single container. In addition, it is possible to eco-friendly manufacture 2,5-furandicarboxylic acid in large quantities, and have an effect of easy storage and input of raw materials.

Description

Manufacturing method of 2,5-furandicarboxylic acid using ionic liquid and carbon dioxide {METHOD FOR PRODUCING 2,5-FURANDICARBOXYLIC ACID USING IONIC LIQUID AND CARBON DIOXIDE}

The present invention relates to a method for producing 2,5-furandicarboxylic acid using a fluoroic acid-based ionic liquid, and more specifically, an ionic liquid and carbon dioxide produced by an acid-base reaction of an organic base and 2-furic acid. It relates to a method for producing 2,5-furandicarboxylic acid by reacting in a solventless condition using a catalyst.

With the establishment of an industrial production system starting from World War II, plastics based on various resins began to be mass-produced as consumer goods. In particular, from the late 1970s, more than 300 million tons of plastic has been produced and consumed worldwide, exceeding steel production. However, since plastic is produced using naphtha from the oil refining process, depletion of petroleum resources and carbon dioxide emissions are a problem, and as it is used as the main material for disposable products, it is discarded immediately after using the product. When it is difficult to incinerate because it does not rot, incineration substances such as dioxin are released into the atmosphere, causing environmental problems, and research on alternative materials has been continuously conducted.

As a substitute for plastics, scientists are working hard to develop bioplastic materials using starch or cellulose in plants. In particular, one of the materials in the spotlight among bioplastic materials is a plastic manufactured based on 2,5-furandicarboxylic acid (FDCA).

In the case of 2,5-furandicarboxylic acid, 5-hydroxymethylfurfural (HMF), which has limitations in securing raw materials, is used in the presence of a precious metal catalyst to perform an oxidation reaction using an explosive oxidizing agent such as air or pure oxygen. It is generally manufactured through. However, 5-hydroxymethylfurfural, a hexahedral sugar, is difficult to mass-produce due to difficulty in supplying raw materials, and when it undergoes an oxidation reaction, there is a safety risk in that an oxidizing agent having high explosiveness must be used. There is a problem in that it is difficult to prepare furandicarboxylic acid.

Therefore, it is possible to prepare 2,5-furandicarboxylic acid in a single reaction by avoiding the oxidation process of 5-hydroxymethylfurfural, a hexose sugar, and using inexpensive and abundant carbon dioxide and a pentasaccharide material, which is a material having high industrial utility. Process is required.

An object of the present invention is to provide a method for preparing 2,5-furandicarboxylic acid by reacting an ionic liquid and carbon dioxide generated by an acid-base reaction of an organic base with 2-furic acid under a solventless condition using a catalyst. , It is to provide a method for preparing 2,5-furandicarboxylic acid that can escape the oxidation process of 5-hydroxymethylfurfural, a hexose sugar, and can prepare 2,5-furandicarboxylic acid in large quantities.

Another object of the present invention is to provide a pentagonal substance in the form of an ionic liquid that is not affected by moisture when synthesizing 2,5-furandicarboxylic acid from a pentose substance and carbon dioxide.

Another object of the present invention is to provide a catalyst for the production of 2,5-furandicarboxylic acid that can be used in synthesizing 2,5-furandicarboxylic acid from pentose substance and carbon dioxide.

Another object of the present invention is to provide 2,5-furandicarboxylic acid or a salt thereof prepared according to the 2,5-furandicarboxylic acid production method.

According to an aspect of the present invention, according to Reaction Scheme 1, (a) 2-Furoic acid represented by Chemical Formula 1 (2-Furoic acid) and an organic base (Base) by an acid-base reaction to the ionic represented by Chemical Formula 2 Preparing a liquid; And (b) reacting an ionic liquid represented by Chemical Formula 2, a catalyst, and carbon dioxide to prepare 2,5-furandicarboxylic acid represented by Chemical Formula 3 or a salt thereof; 2,5-furandicarboxylic acid containing or Methods of preparing the salts thereof are provided.

[Scheme 1]

In Reaction Scheme 1, M is a proton or alkali metal ion.

In addition, the catalyst of step (b) may be a compound represented by Formula 4 or a compound represented by Formula 5.

[Formula 4]

[Formula 5]

In Chemical Formulas 4 and 5, M ¹ and M ² are the same as or different from each other, and each independently an alkali metal, and Y is pyrazolide ([Pyr] ^- ), imidazolide ([Im] ^- ), 1, 2,4-triazolide ([4-Triaz] ^- ), 1,2,3-triazolide ([3-Triaz] ^- ), tetrazolide ([Tet] ^- ), indolide ([Ind] ^- ), Benzotriazole ([Bentri] ^- ) and 3-amino-1,2,4-triazolide ([3-AT] ^- ).

In addition, in Chemical Formula 5, Y is 1,2,4-triazolide ([4-Triaz] ^- ), benzotriazolide ([Bentri] ^- ) and 3-amino-1,2,4-triazolide It may be any one selected from ([3-AT] ^- ).

In addition, the step (b) may be performed under a solvent-free condition.

In addition, the catalyst may be 1.0 to 2.0 mmol based on 1 mmol of the ionic liquid.

In addition, in the step (a), the organic base is 1-alkylimidazole, choline, 1,8-diazabicyclo (5,4,0) undec-7-ene (1 , 8-Diazabicyclo (5.4.0) undec-7-ene), trialkylpyridine, trialkylphosphine, triazoles and tetrazoles May be

In addition, the alkali metal may be any one selected from lithium, sodium, potassium, rubidium and cesium.

In addition, the reaction of step (b) may be carried out at a temperature of 100 to 300 ℃.

In addition, the reaction of the step (b) (b-1) performing the injection and discharge of carbon dioxide into the reactor 1 to 10 times to discharge the air inside the reactor; And (b-2) 2,5- represented by Chemical Formula 3 by reacting the carbon dioxide and the ionic liquid by supplying the carbon dioxide inside the reactor from which the air is discharged and stirring the ionic liquid represented by Chemical Formula 2 The step of preparing a furandicarboxylic acid or a salt thereof; may be to include.

In addition, carbon dioxide in step (b-2) may be supplied at a pressure of 50 to 1,000 psi.

In addition, the stirring speed in step (b-2) may be 300 to 1,000 rpm.

According to another aspect of the present invention, a compound represented by Chemical Formula 4 or Chemical Formula 5 is provided.

[Formula 4]

[Formula 5]

In the above Chemical Formulas 1 and 2, M ¹ and M ² are the same or different from each other, and each independently an alkali metal, and Y is pyrazolide ([Pyr] ^- ), imidazolide ([Im] ^- ), 1, 2,4-triazolide ([4-Triaz] ^- ), 1,2,3-triazolide ([3-Triaz] ^- ), tetrazolide ([Tet] ^- ), indolide ([Ind] ^- ), Benzotriazole ([Bentri] ^- ) and 3-amino-1,2,4-triazolide ([3-AT] ^- ).

In addition, in Chemical Formula 5, Y is 1,2,4-triazolide ([4-Triaz] ^- ), benzotriazolide ([Bentri] ^- ) and 3-amino-1,2,4-triazolide It may be any one selected from ([3-AT] ^- ).

Further, the compound represented by Chemical Formula 4 or Chemical Formula 5 may be a catalyst for use in preparing 2,5-furandicarboxylic acid or a salt thereof using organic or inorganic 2-Furoate and carbon dioxide. .

In addition, the alkali metal may be any one selected from lithium, sodium, potassium, rubidium and cesium.

According to another aspect of the present invention, 2,5-furandicarboxylic acid prepared according to the 2,5-furandicarboxylic acid production method or a salt thereof is provided.

The method for producing 2,5-furandicarboxylic acid of the present invention directly reacts ionic liquid and carbon dioxide generated by an acid-base reaction of an organic base and 2-furic acid in a single container in a simple process, resulting in a high yield of 2,5 -Can produce furandicarboxylic acid.

In addition, 2,5-furan is used as a reactant using ionic liquid and cheap and abundant carbon dioxide produced by reacting with an organic base using a material such as 2-furic acid obtained by oxidizing perfural in mass production in China. Since dicarboxylic acid is produced, it is eco-friendly and has an effect capable of being manufactured in large quantities.

In addition, by replacing the previously used substrate with a high hygroscopicity with an ionic liquid, there is an effect of easy storage and input of raw materials.

Since these drawings are for reference to explain exemplary embodiments of the present invention, the technical spirit of the present invention should not be construed as being limited to the accompanying drawings.
1 is a flow chart showing a method for producing 2,5-furandicarboxylic acid.
2A is an LC-MS spectrum of the reactant produced according to Example 3, FIG. 2B is an LC-MS spectrum of sample cesium 2-furoate, and FIG. 2C is an LC-MS spectrum of sample cesium 2,5-furandicarboxylic acid to be.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art to which the present invention pertains may easily practice.

However, the following description is not intended to limit the present invention to specific embodiments, and when it is determined that a detailed description of known technologies related to the present invention may obscure the subject matter of the present invention, the detailed description will be omitted. .

The terms used herein are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, terms such as “include” or “have” are intended to indicate that a feature, number, step, operation, component, or combination thereof described in the specification exists, or that one or more other features or It should be understood that numbers, steps, operations, elements, or combinations thereof do not preclude the presence or addition possibilities of those in combination.

Further, terms including ordinal numbers such as first and second to be used below may be used to describe various components, but the components are not limited by the terms. The terms are used only for the purpose of distinguishing one component from other components. For example, the first component may be referred to as a second component without departing from the scope of the present invention, and similarly, the second component may be referred to as a first component.

Also, when a component is said to be "formed" or "stacked" on another component, it may be formed or stacked directly attached to the front or one side of the surface of the other component, but may be intermediate. It should be understood that other components may exist in the.

Hereinafter, a method for producing 2,5-furandicarboxylic acid using the ionic liquid and carbon dioxide of the present invention will be described in detail. However, this is presented as an example, and the present invention is not limited thereby, and the present invention is only defined by the scope of claims to be described later.

The method for producing 2,5-furandicarboxylic acid of the present invention is to react ionic liquid with carbon dioxide.

In detail, according to Reaction Scheme 1, (a) an acid-base reaction of 2-Furoic acid represented by Chemical Formula 1 and an organic base to prepare an ionic liquid represented by Chemical Formula 2 step; And (b) reacting an ionic liquid represented by Chemical Formula 2, a catalyst, and carbon dioxide to prepare 2,5-furandicarboxylic acid represented by Chemical Formula 3 or a salt thereof; 2,5-furandicarboxylic acid containing or It is a method for preparing the salt.

[Scheme 1]

In Reaction Scheme 1, M is preferably a proton or alkali metal ion.

In addition, it is preferable that the catalyst of step (b) is a compound represented by Formula 4 or a compound represented by Formula 5.

[Formula 4]

[Formula 5]

In Chemical Formulas 4 and 5, M ¹ and M ² are the same as or different from each other, and each independently an alkali metal, and Y is pyrazolide ([Pyr] ^- ), imidazolide ([Im] ^- ), 1, 2,4-triazolide ([4-Triaz] ^- ), 1,2,3-triazolide ([3-Triaz] ^- ), tetrazolide ([Tet] ^- ), indolide ([Ind] ^- ), Benzotriazide ([Bentri] ^- ) and 3-amino-1,2,4-triazolide ([3-AT] ^- ) is preferably one selected from.

In addition, in Chemical Formula 5, Y is 1,2,4-triazolide ([4-Triaz] ^- ), benzotriazolide ([Bentri] ^- ), and 3-amino-1,2,4-triazoli De ([3-AT] ^- ) is preferably any one selected from.

In addition, it is preferable that step (b) is performed under solvent-free conditions.

In addition, the catalyst may be 1.0 to 2.0 mmol on the basis of 1 mmol of the ionic liquid, preferably 1.3 to 1.8 mmol, more preferably 1.5 to 1.6 mmol.

In addition, in the step (a), the organic base is 1-alkylimidazole, choline, 1,8-diazabicyclo (5,4,0) undec-7-ene (1 , 8-Diazabicyclo (5.4.0) undec-7-ene), trialkylpyridine, trialkylphosphine, triazoles and tetrazoles. And preferably 1-alkylimidazole, more preferably 1-methylimidazole, 1-propylimidazole, 1-butylimidazole, more preferably 1-methylimidazole can do.

In addition, the alkali metal may be any one selected from lithium, sodium, potassium, rubidium and cesium, and preferably cesium.

In addition, the reaction of step (b) may be carried out at a temperature of 100 to 300 ° C, preferably 150 to 250 ° C, more preferably 180 to 230 ° C. When the reaction temperature in step (b) is less than 100 ° C, the reaction time between the ionic liquid and carbon dioxide is long, which is undesirable, and when it exceeds 300 ° C, side reactions increase, making it difficult to prepare 2,5-furandicarboxylic acid. Do not.

In addition, the step (b) of the reaction (b-1) to perform the injection and discharge of carbon dioxide to the reactor 1 to 10 times to discharge the air inside the reactor; And (b-2) 2,5- represented by Chemical Formula 3 by reacting the carbon dioxide and the ionic liquid by supplying the carbon dioxide inside the reactor from which the air is discharged and stirring the ionic liquid represented by Chemical Formula 2 Preparing a furandicarboxylic acid or a salt thereof.

In addition, carbon dioxide of step (b-2) may be supplied at a pressure of 50 to 1,000 psi, preferably 150 to 500 psi, more preferably 250 to 350 psi. When the carbon dioxide of step (b-2) is supplied at a pressure of less than 50 psi, the yield of 2,5-furandicarboxylic acid decreases, which is not preferable, and when it exceeds 1,000 psi, it is unnecessary because yield improvement cannot be expected any more. .

In addition, the stirring speed of step (b-2) may be 100 to 1,000 rpm, preferably 300 to 800 rpm, more preferably 400 to 600 rpm. When the stirring speed of step (b-2) is less than 100 rpm, the ionic liquid, carbon dioxide, and catalyst are not sufficiently mixed and thus the yield of 2,5-furandicarboxylic acid decreases, which is undesirable, and when it exceeds 1,000 rpm, it is no longer This is unnecessary since yield improvement cannot be expected.

Hereinafter, the catalyst for producing 2,5-furandicarboxylic acid of the present invention will be described.

The catalyst for the production of 2,5-furandicarboxylic acid of the present invention is a compound represented by Formula 4 or Formula 5.

[Formula 4]

[Formula 5]

In Formula 1 and Formula 2,

M ¹ and M ² are the same or different from each other, and each independently an alkali metal,

Y is pyrazolide ([Pyr] ^- ), imidazolide ([Im] ^- ), 1,2,4-triazolide ([4-Triaz] ^- ), 1,2,3-triazolide ([3-Triaz] ^- ), tetrazolide ([Tet] ^- ), indolide ([Ind] ^- ), benzotriazolide ([Bentri] ^- ) and 3-amino-1,2,4-tria Zolid ([3-AT] ^- ).

In addition, in Chemical Formula 5, Y is 1,2,4-triazolide ([4-Triaz] ^- ), benzotriazolide ([Bentri] ^- ) and 3-amino-1,2,4-triazolide It may be any one selected from ([3-AT] ^- ).

Further, the compound represented by Chemical Formula 4 or Chemical Formula 5 may be a catalyst for use in preparing 2,5-furandicarboxylic acid or a salt thereof using organic or inorganic 2-Furoate and carbon dioxide.

In addition, the alkali metal may be any one selected from lithium, sodium, potassium, rubidium and cesium, and preferably cesium.

When 2,5-furandicarboxylic acid or a salt thereof is prepared using the compound, a process that saves energy, cost, and time without using a toxic reactant may be provided.

Therefore, the 2-Furoic acid-based ionic liquid and carbon dioxide react with the compound to easily prepare 2,5-furandicarboxylic acid or a salt thereof in a single container.

The method for preparing 2,5-furandicarboxylic acid or a salt thereof of the present invention is limited in securing raw materials in the conventional method, and the hexahedral sugar 5-hydroxylfurfural (HMF: 5-hydroxylfurfural) in the presence of a precious metal catalyst is air or pure oxygen. 2-Furoic acid (FA) obtained by oxidizing perfural, a representative material of pentose, which is highly industrially applicable, by avoiding the oxidation process in a method that has been produced through an oxidation reaction using an explosive oxidizing agent such as ) To react with an organic base to react the ionic liquid produced with carbon dioxide to provide a technique for preparing 2,5-furandicarboxylic acid or a salt thereof.

In addition, 2-puroic acid (FA) obtained by oxidizing perfural, a pentose sugar, is reacted with an organic base to form an ionic liquid and used as a reactant. The salt was changed to a liquid ionic liquid-based reactant to increase the ease of process operation and the efficiency of the reaction.

Therefore, it is possible to provide a large amount of 2,5-furandicarboxylic acid or a salt thereof as a process in a more efficient process than a conventional method using a solid as a reactant.

[Example]

Hereinafter, a preferred embodiment of the present invention will be described. However, this is for illustrative purposes, and the scope of the present invention is not limited thereby.

Manufacturing example 1: 1 - Methylimidazolium  2- Furoate (One- methylimidazolium  2-furoate)

Dissolve 100 mmol (8.21 g) of 1-methylimidazole in 10 mL of ethyl acetate (EA), and 50 mL of 99 mmol (11.10 g) of 2-Furoic acid (FA) in ethyl acetate After dissolving in the 2-furic acid solution in an ice bath, the 1-methylimidazole solution is dropped dropwise, and the two solutions are acid-base reacted.

After dropping all the 1-methylimidazole solution, after reacting at room temperature for 1 hour or more, ethyl acetate is removed by an evaporator, and the remaining ionic liquid is washed three times or more with diethylether.

After diethyl ether was removed by an evaporator, the mixture was dried in a reduced pressure oven at a temperature of 70 ° C. for 24 hours to prepare 1-methylimidazolium 2-furate represented by Chemical Formula 6.

[Formula 6]

Manufacturing example 2: 1 - Profile Imidazolium  2- Furoate (One- propylimidazolium  2-furoate)

1-propylimidazole 2-puroate was prepared in the same manner as in Preparation Example 1, except that 100 mmol (11.01 g) of 1-propylimidazole was used instead of 1-methylimidazole. .

Manufacturing example 3: 1 - Butyl imidazolium  2- Furoate (One- butylimidazolium  2- furoate )

1-butylimidazole 2-puroate was prepared in the same manner as in Preparation Example 1, except that 100 mmol (12.42 g) of 1-butylimidazole was used instead of 1-methylimidazole. .

Manufacturing example  4: Choline 2- Furoate ( choline  2- furoate )

Choline hydroxide was used in the same manner as in Production Example 1, except that 100 mmol (20 g) of choline hydroxide methanol solution (45 mass%) was used instead of 1-methylimidazole, and methanol was used instead of ethyl acetate. 2-Furoate was prepared.

Manufacturing example 5: 1 ,8- Diazabicyclo (5,4,0) undec -7- Yen (1,8-Diazabicyclo (5.4.0) undec-7-ene) series Furoate

1,8-Diazabicyclo (5,4,0) undec-7-ene (1,8-Diazabicyclo (5.4.0) undec-7-ene) 100mmol (15.224g) instead of 1-methylimidazole A 1,8-diazabicyclo (5,4,0) undec-7-ene-based furoate was prepared in the same manner as in Production Example 1, except that it was used.

Manufacturing example  6: Tributylpyridinium  2- Furoate

Tributylpyridinium 2-furoate was prepared in the same manner as in Preparation Example 1, except that 100 mmol of tributylpyridine was used instead of 1-methylimidazole.

Manufacturing example  7: Tributylphosphonium  2- Furoate

Tributylbutylphosphonium 2-furoate was prepared in the same manner as in Preparation Example 1, except that 100 mmol of tributylphosphine was used instead of 1-methylimidazole.

Manufacturing example  8: Cesium triazole (Cs [1,2,4- triazolide ])

50 mmol (16.3 g) of cesium carbonate (Cs ₂ CO ₃ ) and 100 mmol (6.91 g) of 1,2,4-triazole (1,2,4-triazole) are dissolved in 25 mL of methanol and reacted by refluxing for one day.

After the reaction, methanol, a solvent, was removed by an evaporator, and the resulting salt in the form of particles was dried in a vacuum oven at 100 ° C. for 24 hours to prepare cesium triazole.

Manufacturing example  9: Cesium benzotriazole (Cs [ Benzotriazolide ])

Cesium benzotriazole was prepared in the same manner as in Preparation Example 8, except that 100 mmol (11.91 g) of benzotriazole was used instead of 1,2,4-triazole.

Manufacturing example  10: cesium 2- Furoate (Cesium 2- Furoate )

Cesium in the same manner as in Preparation Example 8, except that 25 mmol (2.80 g) of 2-Furoic acid (FA) was used instead of 1,2,4-triazole and 100 mL of water was used instead of methanol. 2-Furoate was prepared.

Example  One

High-pressure stainless steel reactor 100 m equipped with a magnetic stirrer and an electric heater, respectively, so that the molar ratio of 1-methylimidazolium 2-furoate and cesium carbonate (Cs ₂ CO ₃ ) prepared according to Preparation Example 1 was 1: 1.6, respectively. A mixture was prepared by mixing 5 mmol and 8 mmol without solvent.

After purging carbon dioxide into the reactor at 80 psi pressure, the atmosphere was evacuated three times.

While stirring at 500 rpm, heated to 220 ° C., the carbon dioxide pressure was raised to 300 psi, and then the reaction was maintained for 12 hours while maintaining the pressure at 300 psi to prepare a 2,5-furandicarboxylic acid salt of Chemical Formula 7 below.

[Formula 7]

 M of the above structure is an alkali metal proton ion of the catalyst and can be converted to 2,5-furandicarboxylic acid by reacting with an aqueous hydrochloric acid solution later.

Example  2

A 2,5-furandicarboxylic acid salt was prepared in the same manner as in Example 1, except that 1-methylimidazolium 2-furoate prepared according to Preparation Example 1 was exposed to air for one day and then used.

Example  3

2 in the same manner as in Example 1, except that 1-propylimidazolium 2-furoate prepared according to Preparation Example 2 was used instead of 1-methylimidazolium 2-purate prepared according to Preparation Example 1 , 5-furandicarboxylic acid salt was prepared.

Example  4

2 in the same manner as in Example 1, except that 1-butylimidazolium 2-furoate prepared according to Preparation Example 3 was used instead of 1-methylimidazolium 2-purate prepared according to Preparation Example 1 , 5-furandicarboxylic acid salt was prepared.

Example  5

2,5-furandi in the same manner as in Example 1, except that choline 2-furoate prepared according to Preparation Example 4 was used instead of 1-methylimidazolium 2-purate prepared according to Preparation Example 1 A carboxylic acid salt was prepared.

Example  6

The 1,8-diazabicyclo (5,4,0) undec-7-ene-based furoate prepared according to Preparation Example 5 was used instead of the 1-methylimidazolium 2-puroate prepared according to Preparation Example 1 A 2,5-furandicarboxylic acid salt was prepared in the same manner as in Example 1 except for the above.

Example  7

2,5 in the same manner as in Example 1, except that tributylpyridinium 2-furoate prepared according to Preparation Example 6 was used instead of 1-methylimidazolium 2-purate prepared according to Preparation Example 1 -Furandicarboxylic acid salt was prepared.

Example  8

2,5 in the same manner as in Example 1, except that tributylphosphonium 2-furoate prepared according to Preparation Example 7 was used instead of 1-methylimidazolium 2-purate prepared according to Preparation Example 1 -Furandicarboxylic acid salt was prepared.

Example  9

A 2,5-furandicarboxylic acid salt was prepared in the same manner as in Example 1, except that cesium triazide prepared according to Preparation Example 6 was used instead of cesium carbonate.

Example  10

A 2,5-furandicarboxylic acid salt was prepared in the same manner as in Example 1 except that cesium carbonate was used instead of cesium benzotriazole prepared according to Preparation Example 7.

Example  11

A 2,5-furandicarboxylic acid salt was prepared in the same manner as in Example 1, except that the reaction temperature was heated to 210 ° C instead of heating to 220 ° C.

Example  12

A 2,5-furandicarboxylic acid salt was prepared in the same manner as in Example 1, except that the reaction temperature was heated to 200 ° C instead of heating to 220 ° C.

Example  13

A 2,5-furandicarboxylic acid salt was prepared in the same manner as in Example 1, except that the reaction temperature was heated to 190 ° C instead of heating to 220 ° C.

Example  14

A 2,5-furandicarboxylic acid salt was prepared in the same manner as in Example 1, except that the reaction temperature was heated to 180 ° C instead of heating to 220 ° C.

Example  15

2,5-furandicarboxylic acid salt in the same manner as in Example 1, except that the reaction temperature was heated to 200 ° C. instead of heating to 220 ° C., and the reaction pressure was maintained at 800 psi instead of maintaining at 300 psi. Was prepared.

Example  16

2,5-furandicarboxylic acid salt in the same manner as in Example 1 except that the reaction temperature was heated to 200 ° C instead of heating to 220 ° C, and the reaction pressure was maintained at 1040psi instead of maintaining at 300psi. Was prepared.

Example  17

The reaction temperature was heated to 200 ° C. instead of heating to 220 ° C., and the same as in Example 1, except that the molar ratio of 2-furoate and cesium was 1: 1 instead of 1: 1.6. 2,5-furandicarboxylic acid salt was prepared by the method.

Example  18

The reaction temperature was heated to 200 ° C. instead of heating to 220 ° C., and the same as in Example 1 except that the molar ratio of 2-furoate and cesium was 1: 0.5 instead of 1: 1.6. 2,5-furandicarboxylic acid salt was prepared by the method.

Comparative example  One

2,5-furandi in the same manner as in Example 1, except that cesium 2-furoate prepared according to Preparation Example 10 was used instead of 1-methylimidazolium 2-furoate prepared according to Preparation Example 1 A carboxylic acid salt was prepared.

Comparative example  2

Instead of 1-methylimidazolium 2-furoate prepared according to Preparation Example 1, cesium 2-furoate prepared according to Preparation Example 10 was exposed to air for one day and then used in the same manner as in Example 1 2,5-furandicarboxylic acid salt was prepared.

Comparative example  3

A 2,5-furandicarboxylic acid salt was prepared in the same manner as in Example 1, except that 5 mmol of 2-furic acid was used instead of 1-methylimidazolium 2-furoate prepared according to Preparation Example 1.

Comparative example  4

Example 1, except that 1-methylimidazole 2- furoate prepared in accordance with Preparation Example 1 was used instead of 1-methylimidazole 100mmol (8.21g) and 2-furoic acid 99mmol (11.10g) In the same manner as 1, 2,5-furandicarboxylic acid salt was prepared.

Comparative example  5

Instead of 1-methylimidazolium 2-furoate prepared according to Preparation Example 1, 100-mmol (8.21g) and 2-mmol-puric acid 99mmol (11.10g) were added, and then reacted after stirring for 3 hours. A 2,5-furandicarboxylic acid salt was prepared in the same manner as in Example 1, except that.

Table 1 below summarizes the reaction conditions for the production of 2,5-furandicarboxylic acid according to Examples 1 to 10.

division materials Substrate air exposure Substrate agitation catalyst 2-Furoate: cesium
Mole ratio Reaction pressure
(psi) Reaction temperature
(℃) Example 1 1-methylimidazolium
2-Puroate - - Cesium carbonate 1: 1.6 300 220 Example 2 1-methylimidazolium 2-furoate ○ - Cesium carbonate 1: 1.6 300 220 Example 3 1-propylimidazolium 2-furoate - - Cesium carbonate 1: 1.6 300 220 Example 4 1-butylimidazolium 2-furoate - - Cesium carbonate 1: 1.6 300 220 Example 5 Choline 2-Furoate - - Cesium carbonate 1: 1.6 300 220 Example 6 DBU-based furoate - - Cesium carbonate 1: 1.6 300 220 Example 7 Tributylpyridinium 2-furoate - - Cesium carbonate 1: 1.6 300 220 Example 8 Tributylphosphonium
2-Puroate - - Cesium carbonate 1: 1.6 300 220 Example 9 1-methylimidazolium
2-Puroate - - Cesium triazole 1: 1.6 300 220 Example 10 1-methylimidazolium
2-Puroate - - Cesium benzotriazole 1: 1.6 300 220 Example 11 1-methylimidazolium 2-furoate - - Cesium carbonate 1: 1.6 300 210 Example 12 1-methylimidazolium 2-furoate - - Cesium carbonate 1: 1.6 300 200 Example 13 1-methylimidazolium 2-furoate - - Cesium carbonate 1: 1.6 300 190 Example 14 1-methylimidazolium 2-furoate - - Cesium carbonate 1: 1.6 300 180 Example 15 1-methylimidazolium 2-furoate - - Cesium carbonate 1: 1.6 800 200 Example 16 1-methylimidazolium
2-Puroate - - Cesium carbonate 1: 1.6 1040 200 Example 17 1-methylimidazolium
2-Puroate - - Cesium carbonate 1: 1 300 200 Example 18 1-methylimidazolium
2-Puroate - - Cesium carbonate 1: 0.5 300 200 Comparative Example 1 Cesium 2-Furoate - - Cesium carbonate 1: 1.6 300 220 Comparative Example 2 Cesium 2-Furoate ○ - Cesium carbonate 1: 1.6 300 220 Comparative Example 3 2-furic acid - - Cesium carbonate 1: 1.6 300 220 Comparative Example 4 1-methylimidazole and 2-furic acid - - Cesium carbonate 1: 1.6 300 220 Comparative Example 5 1-methylimidazole and 2-furic acid - ○
(3h) Cesium carbonate 1: 1.6 300 220

[Test Example]

2,5- Furandicarboxylic acid  Structure confirmation of salt: LC-MS analysis

Figure 2a is the LC-MS spectrum of the reactant produced according to Example 3, Figure 2b is the LC-MS spectrum of the sample cesium 2-furate, Figure 2c is the LC-MS spectrum of the sample cesium 2,5-furandicarboxylic acid It is shown.

According to Figures 2a to 2c, it can be confirmed that the reactant produced according to Example 3 is a 2,5-furandicarboxylic acid salt.

Conversion rate, yield and Selectivity  analysis: HPLC

After the reactions of Examples 1 to 2 were terminated, wait until the temperature reached room temperature, and the resulting mixture was transferred to a vial and quantitatively analyzed using high performance liquid chromatography (HPLC). Analysis was performed using a high performance liquid chromatography (HPLC) instrument (Agilent Technologies 1200 series, Bio-Rad Aminex HPX-87 H pre-packed column, and UV-detector), and H ₂ SO ₄ (0.0005M) in water was mobile phase. It was used as. In addition, the conversion method of the ionic liquid and the yield calculation method of furandicarboxylic acid (FDCA: 2,5-furandicarboxylic acid) may be those using the following Equations 1 and 2.

[Equation 1]

[Equation 2]

C _FA of Tables 2 to 6 below represents the conversion of 2-furoate in the substrate, and Y _FDCA represents the yield of 2,5- _{furandicarboxylic} acid salt.

Effect of temperament state

The effects of substrate types and conditions on the production of 2,5-furandicarboxylic acid from 2-furoate and carbon dioxide were studied and the results are shown in Table 2.

division Type of temperament Whether air is exposed C _FA
(%) Y _FDCA
(%) Example 1 1-methylimidazolium 2-furoate - 93.2 90.6 Example 2 1-methylimidazolium 2-furoate ○ 91.5 85.9 Comparative Example 1 Cesium 2-Furoate - 91.0 85.6 Comparative Example 2 Cesium 2-Furoate ○ 83.1 72.2

According to Table 2 above, when 2,5-furandicarboxylic acid was prepared under the same conditions of 5 mmol of substrate, 2-furoate and cesium molar ratio of 1: 1.6, reaction temperature of 220 ° C, reaction pressure of 300 psi, reaction time of 12 hours, When the substrate used was exposed to air for one day and reacted, it was confirmed that the reactivity was poor. In the case of cesium 2-furoate having high hygroscopicity, the yield of 2,5-furandicarboxylic acid salt was significantly decreased from 85.6% to 72.2%. Can be confirmed. On the other hand, the ionic liquid showed a slight reactivity of 2,5-furandicarboxylic acid salt from 90.6% to 85.9%, but still showed high reactivity.

Effect of substrate input method

The effect of the substrate input method on the production of 2,5-furandicarboxylic acid from the substrate and carbon dioxide was studied and the results are shown in Table 3.

division Type of temperament Whether the substrate is stirred
(Stirring time) C _FA
(%) Y _FDCA
(%) Example 1 1-methylimidazolium 2-furoate - 93.2 90.6 Comparative Example 3 2-furic acid - 76.4 75.5 Comparative Example 4 1-methylimidazole and 2-furic acid - 80.1 72.4 Comparative Example 5 1-methylimidazole and 2-furic acid ○ (3h) 83.5 80.1

According to Table 3, when the substrate 5mmol, 2-furoate and cesium molar ratio of 1: 1.6, the reaction temperature 220 ℃, the reaction pressure 300psi, the reaction time of 12 hours under the same conditions to prepare 2,5-furandicarboxylic acid, Example 1 used as a substrate after synthesizing an ionic liquid showed the highest activity. In addition, in case of Comparative Example 4 in which the reaction was performed with 1-methylimidazole and 2-furic acid respectively, the activity was similar to that of Comparative Example 3 with only 2-furic acid, and the activity was higher than that in the case of using an ionic liquid. In the case of Comparative Example 5, which reacted after stirring for 3 hours after remarkably dropping, it can be confirmed that the ionic liquid is an important substrate form in the reaction because the reactivity is increased again.

Effects of ionic liquids

The effect of the ionic liquid on the production of 2,5-furandicarboxylic acid from ionic liquid and carbon dioxide was studied and the results are shown in Table 4.

division Ionic liquid C _FA
(%) Y _FDCA
(%) Example 1 1-methylimidazolium 2-furoate 93.2 90.6 Example 3 1-propylimidazolium 2-furoate 86.8 82.7 Example 4 1-butylimidazolium 2-furoate 83.8 81.4 Example 5 Choline 2-Furoate 82.4 11.9 Example 6 DBU-based furoate 72.4 20.1 Example 7 Tributylpyridinium 2-furoate 79.8 50.7 Example 8 Tributylphosphonium 2-furoate 82.1 61.3

According to Table 4 above, the molar ratio of 5 mmol of the substrate, 2-furoate and cesium is 1: 1.6, the reaction temperature is 220 ° C, 2,5-furandi of Example 1 using 1-methylimidazolium 2-furoate as an ionic liquid when 2,5-furandicarboxylic acid was prepared under the same conditions of reaction pressure of 300 psi and reaction time of 12 hours. It can be seen that the yield of carboxylic acid was the highest at 90.6%. In Examples 5 and 6, when choline 2-furoate and DBU-based furoate were used as reactants, it is thought that cation exchange between the ionic liquid and cesium catalyst is not easy, and thus it is thought to interfere with the conversion to FDCA.

Effect of catalyst

The effect of the catalyst on the production of 2,5-furandicarboxylic acid from ionic liquids and carbon dioxide was studied and the results are shown in Table 5.

division catalyst C _FA
(%) Y _FDCA
(%) Example 1 Cesium carbonate 93.2 90.6 Example 9 Cesium triazole 19.7 15.4 Example 10 Cesium benzotriazole 23.34 1.1

According to Table 5 above, the molar ratio of 5 mmol of the substrate, 2-furoate and cesium is 1: 1.6, the reaction temperature is 220 ° C, When 2,5-furandicarboxylic acid was prepared under the same conditions of reaction pressure of 300 psi and reaction time of 12 hours, the yield of 2,5-furandicarboxylic acid of Example 1 using cesium carbonate as a catalyst was the highest at 90.6%. Can be confirmed.

Reaction temperature effect

The effect of temperature on the production of 2,5-furandicarboxylic acid from ionic liquids and carbon dioxide was studied and the results are shown in Table 6.

division Reaction temperature
(℃) C _FA
(%) Y _FDCA
(%) Example 1 220 93.2 90.6 Example 11 210 90.4 88.2 Example 12 200 88.8 84.9 Example 13 190 46.2 15.6 Example 14 180 30.1 7.6

According to Table 6 above, when 2,5-furandicarboxylic acid was prepared under the same conditions of a molar ratio of 5 mmol, 2-furoate and cesium of the substrate 1: 1.6, a reaction pressure of 300 psi, and a reaction time of 12 hours, the reaction temperature was 220 ° C. Phosphorus Example 1 showed the highest activity with an ionic liquid conversion rate of 93.2% and a 2,5-furandicarboxylic acid yield of 90.6%, and it was confirmed that the lower the reaction temperature, the significantly lower the activity.

Reaction pressure effect

The effect of pressure on the production of 2,5-furandicarboxylic acid from ionic liquids and carbon dioxide was studied and the results are shown in Table 7.

division Reaction pressure
(psi) C _FA
(%) Y _FDCA
(%) Example 12 300 88.8 84.9 Example 15 800 92.2 89.1 Example 16 1040 89.4 83.2

According to Table 7, when 2,5-furandicarboxylic acid was prepared under the same conditions of 5 mmol of substrate, 2-furoate and cesium molar ratio of 1: 1.6, reaction temperature of 200 ° C, reaction time of 12 hours, at a reaction pressure of 300 psi. The ionic liquid conversion rate was 88.8%, 2,5-furandicarboxylic acid yield was 84.9%, and there was no significant change in activity when the reaction pressure was 300 psi or more.

Therefore, it can be seen that when the 2,5-furandicarboxylic acid was prepared under the same conditions other than the reaction pressure, even if the reaction pressure increased, the yield of 2,5-furandicarboxylic acid was not significantly affected.

Of ionic liquids and catalysts Mole ratio  effect

The effect of the molar ratio of cesium on 2-furoate and catalyst in the ionic liquid on the preparation of 2,5-furandicarboxylic acid from ionic liquid and carbon dioxide was studied and the results are shown in Table 8.

division 2-Furoate: cesium
Mole ratio C _FA
(%) Y _FDCA
(%) Example 12 1: 1.6 88.8 84.9 Example 17 1: 1 86.2 82.4 Example 18 1: 0.5 31.2 16.5

According to Table 8 above, the substrate 5mmol, the reaction temperature 200 ℃, Ionic liquid in Example 17 in which the molar ratio of 2-furoate in the ionic liquid and cesium in the catalyst is 1: 1, when 2,5-furandicarboxylic acid is prepared under the same conditions of 300 psi reaction pressure and 12 hours reaction time Conversion rate of 86.2%, 2,5-furandicarboxylic acid yield of 82.4%, there was no significant change until the molar ratio 1: 1, but the molar ratio of 1: 0.5 indicates that the catalyst has a lower number of moles than the molar number of the ionic liquid.

The scope of the present invention is indicated by the following claims rather than the above detailed description, and it should be interpreted that all changes or modified forms derived from the meaning and scope of the claims and equivalent concepts thereof are included in the scope of the present invention. do.

Claims (16)

According to Scheme 1,
(a) preparing an ionic liquid represented by Chemical Formula 2 by acid-base reaction of 2-Furoic acid represented by Chemical Formula 1 with an organic base; And
(b) preparing a 2,5-furandicarboxylic acid represented by Chemical Formula 3 or a salt thereof by reacting an ionic liquid represented by Chemical Formula 2, a catalyst, and carbon dioxide in a reactor;
Method for preparing 2,5-furandicarboxylic acid or a salt thereof comprising:
[Scheme 1]

In Reaction Scheme 1,
M is a proton or alkali metal ion. According to claim 1,
Method for producing 2,5-furandicarboxylic acid or a salt thereof, wherein the catalyst of step (b) is a compound represented by formula (4) or a compound represented by formula (5):
[Formula 4]

[Formula 5]

In Chemical Formulas 4 and 5,
M ¹ and M ² are the same or different from each other, and each independently an alkali metal,
Y is pyrazolide ([Pyr] ^- ), imidazolide ([Im] ^- ), 1,2,4-triazolide ([4-Triaz] ^- ), 1,2,3-triazolide ([3-Triaz] ^- ), tetrazolide ([Tet] ^- ), indolide ([Ind] ^- ), benzotriazolide ([Bentri] ^- ) and 3-amino-1,2,4-tria Zolid ([3-AT] ^- ). According to claim 2,
In Chemical Formula 5, Y is 1,2,4-triazolide ([4-Triaz] ^- ), benzotriazolide ([Bentri] ^- ) and 3-amino-1,2,4-triazolide ([ 3-AT] ^- ) 2,5-furandicarboxylic acid, or a method for producing a salt thereof, characterized in that any one selected from. According to claim 1,
Method of producing 2,5-furandicarboxylic acid or a salt thereof, wherein step (b) is performed under solvent-free conditions. According to claim 1,
Method for producing 2,5-furandicarboxylic acid or a salt thereof, wherein the catalyst is 1.0 to 2.0 mmol based on 1 mmol of the ionic liquid. According to claim 1,
In step (a), the organic base is 1-alkylimidazole (1-alkylimidazole), choline (choline), 1,8-diazabicyclo (5,4,0) undec-7-ene (1,8 -Diazabicyclo (5.4.0) undec-7-ene), trialkylpyridine, trialkylphosphine, triazoles and tetrazoles. Preparation method of 2,5-furandicarboxylic acid or its salt. According to claim 2,
Method for producing 2,5-furandicarboxylic acid or a salt thereof, wherein the alkali metal is any one selected from lithium, sodium, potassium, rubidium and cesium. According to claim 1,
Method of producing 2,5-furandicarboxylic acid or a salt thereof, wherein the reaction of step (b) is performed at a temperature of 100 to 300 ° C. According to claim 1,
The reaction of step (b)
(b-1) performing the injection and discharge of carbon dioxide into the reactor 1 to 10 times to discharge air inside the reactor; And
(b-2) 2,5-furan represented by Chemical Formula 3 by reacting the carbon dioxide and the ionic liquid by supplying the carbon dioxide into the reactor from which the air is discharged, and stirring the ionic liquid represented by Chemical Formula 2 Preparing a dicarboxylic acid or a salt thereof;
Method of producing 2,5-furandicarboxylic acid or a salt thereof, characterized in that it comprises. The method of claim 9,
Method for producing 2,5-furandicarboxylic acid or a salt thereof, characterized in that the carbon dioxide of step (b-2) is supplied at a pressure of 50 to 1,000 psi. The method of claim 9,
Method for producing 2,5-furandicarboxylic acid or a salt thereof, characterized in that the stirring speed of step (b-2) is 300 to 1,000 rpm. A compound represented by Formula 4 or Formula 5.
[Formula 4]

[Formula 5]

In Formula 1 and Formula 2,
M ¹ and M ² are the same or different from each other, and each independently an alkali metal,
Y is pyrazolide ([Pyr] ^- ), imidazolide ([Im] ^- ), 1,2,4-triazolide ([4-Triaz] ^- ), 1,2,3-triazolide ([3-Triaz] ^- ), tetrazolide ([Tet] ^- ), indolide ([Ind] ^- ), benzotriazolide ([Bentri] ^- ) and 3-amino-1,2,4-tria Zolid ([3-AT] ^- ). The method of claim 12,
In Chemical Formula 5, Y is 1,2,4-triazolide ([4-Triaz] ^- ), benzotriazolide ([Bentri] ^- ), and 3-amino-1,2,4-triazolide ( [3-AT] ^-A compound characterized in that any one selected from. The method of claim 12,
A compound characterized by that the compound represented by Formula 4 or Formula 5 is a catalyst for use in preparing 2,5-furandicarboxylic acid or a salt thereof using organic or inorganic 2-Furoate and carbon dioxide . The method of claim 12,
The alkali metal is a compound, characterized in that any one selected from lithium, sodium, potassium, rubidium, and cesium. A 2,5-furandicarboxylic acid prepared according to the method of claim 1 or a salt thereof.

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