CN112047912A

CN112047912A - Preparation method of furan dicarboxylic acid

Info

Publication number: CN112047912A
Application number: CN202011108401.0A
Authority: CN
Inventors: 傅尧; 李兴龙; 徐冬冬; 沈鸿波
Original assignee: University of Science and Technology of China USTC
Current assignee: University of Science and Technology of China USTC
Priority date: 2020-10-16
Filing date: 2020-10-16
Publication date: 2020-12-08
Anticipated expiration: 2040-10-16
Also published as: CN112047912B

Abstract

The invention discloses a preparation method of furan dicarboxylic acid, which comprises the following steps: the method comprises the following steps of reacting hydroxymethyl furfural, a light stabilizer, a cocatalyst and a solvent in the presence of an oxygen source to obtain furandicarboxylic acid. The method has the advantages of high selectivity, few byproducts, mild reaction conditions and certain industrial application prospect.

Description

Preparation method of furan dicarboxylic acid

Technical Field

The invention relates to the technical field of chemical substance preparation, in particular to a preparation method of furan dicarboxylic acid.

Background

With the rapid growth of the world's economy, the increasing exhaustion of fossil fuels (particularly petroleum) and the resulting environmental pollution have brought a series of social and environmental problems to the human society. Therefore, research related to the synthesis of fuels and fine chemicals starting from biomass, which is one of renewable energy sources, and derivatives thereof has become one of the hot spots of concern to domestic and foreign scientists.

2, 5-furan dicarboxylic acid (FDCA) is used as a novel polymeric structural monomer, has stable performance per se, and can be used for preparing polyester, polyamide, polyurethane and the like. Polyethylene furandicarboxylate (PEF) prepared by FDCA is considered as an important polyester material for replacing polyethylene terephthalate (PET), and has the advantages of biodegradability, environmental protection and the like. Derivatives of FDCA formed by oxidation, reduction, amination, and the like, including furan dicarboxaldehyde, 2, 5-dimethylolfuran, 2, 5-dimethyloltetrahydrofuran, and the like, are also good polymer monomers. Adipic acid, succinic acid and the like obtained by ring opening of FDCA are also industrial raw materials having a wide range of industrial applications.

The traditional method for preparing FDCA mainly comprises the oxidation conversion of 5-hydroxymethylfurfural (5-HMF), but the yield of the process for preparing 5-HMF from sugar is low, the product is unstable in nature and is easy to generate various side reactions with intermediates under the catalysis of acid, so that the difficulty of purification and separation of the product is increased, and the development and utilization of the downstream FDCA product are limited.

Disclosure of Invention

Based on the technical problems in the background art, the invention provides a preparation method of furandicarboxylic acid. The method has the advantages of high selectivity, few byproducts, mild reaction conditions and the like.

The present invention provides a process for producing furandicarboxylic acid, comprising:

the method comprises the following steps of reacting hydroxymethyl furfural, a light stabilizer, a cocatalyst and a solvent in the presence of an oxygen source to obtain furandicarboxylic acid.

In some embodiments, the light stabilizer is a hindered amine light stabilizer, including but not limited to Chimassorb 944, light stabilizer HS-508.

In some embodiments, the promoter is at least one of vanadyl acetylacetonate, vanadyl sulfate, and vanadium pentoxide.

In some embodiments, the solvent is at least one of ethyl acetate, acetone, methyl isobutyl ketone, and dimethyl sulfoxide.

In some embodiments, the oxygen source is hydrogen peroxide.

In some embodiments, the reaction temperature is from 10 to 40 ℃. Preferably, the reaction temperature is 10-30 ℃.

In some embodiments, the reaction time is from 0.5 to 72 hours. Preferably, the reaction temperature is 10-24 hours.

In some embodiments, the molar ratio of light stabilizer to hydroxymethylfurfural is from 0.05:1 to 10: 1. Preferably, the molar ratio of light stabilizer to hydroxymethylfurfural is from 0.05:1 to 0.3: 1.

In some embodiments, the molar ratio of co-catalyst to hydroxymethylfurfural is from 0.1:1 to 10: 1. Preferably, the molar ratio of co-catalyst to hydroxymethylfurfural is from 0.1:1 to 0.5: 1.

In some embodiments, the molar ratio of the oxygen source to hydroxymethylfurfural is from 3:1 to 20: 1. Preferably, the molar ratio of the oxygen source to hydroxymethylfurfural is 4:1 to 8: 1.

In some embodiments, the molar volume ratio of hydroxymethylfurfural to solvent is from 1:5 to 1:20 mol/L.

The invention increases the selectivity of the reaction by selecting proper light stabilizer, cocatalyst and oxygen source, improves the yield of the furan dicarboxylic acid, has mild reaction conditions and is suitable for industrial production.

Drawings

FIG. 1 shows the nuclear magnetic hydrogen spectrum (d-DMSO dissolution) of the product furandicarboxylic acid of example 1.

Detailed Description

In order to better explain the present invention and to facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. The following examples are, however, merely a brief listing of the invention and do not represent or limit the scope of the invention. The protection scope of the invention is subject to the claims. Except for special emphasis, the light stabilizer and 5-hydroxymethylfurfural used are purchased from Aladdin, and the other reagents are purchased from the national pharmaceutical group

Example 1

1mmol of hydroxymethylfurfural, 10mL of ethyl acetate, 0.5mL of hydrogen peroxide, 10 mol% of Chimassorb 944 and 10 mol% of vanadyl sulfate are added into a 35mL pressure-resistant tube, and the mixture reacts for 12 hours at 30 ℃ under magnetic stirring. After the reaction is finished, cooling to room temperature, diluting with methanol to a constant volume of 100mL, sampling, filtering and testing. Detecting the purity of the FDCA by using high performance liquid chromatography, wherein the liquid phase conditions are as follows: hitachi L2000 HPLC system, Alltech C18 column, mobile phase: and (B) pump A: pure methanol, pump B: 0.5% trifluoroacetic acid in water, mobile phase composition ratio of pump a to pump B being 20:80, flow rate: 1.0mL/min, column temperature: 30 ℃, detector: DAD, detection wavelength: 264 nm. Furandicarboxylic acid yield was 94% by HPLC. The nuclear magnetic hydrogen spectrum of the prepared furan dicarboxylic acid is shown in figure 1.

Example 2

The specific reaction process and detection method were the same as in example 1 except that vanadyl sulfate was changed to vanadyl acetylacetonate, and the yield of furandicarboxylic acid as a product was 89%.

Example 3

The specific reaction process and detection method are the same as those in example 1, except that vanadyl sulfate is changed to vanadium pentoxide, wherein the yield of the product furandicarboxylic acid is 92%.

Example 4

The specific reaction process and detection method were the same as in example 1 except that ethyl acetate was changed to acetone, wherein the yield of the product furandicarboxylic acid was 81%.

Example 5

The specific reaction process and detection method were the same as in example 1 except that ethyl acetate was changed to dimethyl sulfoxide, wherein the yield of furandicarboxylic acid product was 89%.

Example 6

The specific reaction process and detection method are the same as those in example 1, except that the amount of hydrogen peroxide is changed to 0.2ml, and the yield of the product furandicarboxylic acid is 81%.

Example 7

The specific reaction process and detection method were the same as in example 1 except that the reaction temperature was changed to 40 c, wherein the yield of the product furandicarboxylic acid was 86%.

Example 8

The specific reaction process and detection method were the same as in example 1 except that the reaction temperature was changed to 20 deg.c, wherein the yield of the product furandicarboxylic acid was 93%.

Example 9

The specific reaction process and detection method were the same as in example 1 except that the reaction time was changed to 36 hours, wherein the yield of the product furandicarboxylic acid was 94%.

Example 10

The specific reaction process and detection method were the same as in example 1 except that the reaction time was changed to 6 hours, wherein the yield of the product furandicarboxylic acid was 80%.

Example 11

The specific reaction process and detection method are the same as those of example 1, except that the light stabilizer Chimassorb 944 is changed into the light stabilizer HS-508, and the yield of the product furandicarboxylic acid is 88%.

Example 12

The specific reaction process and detection method were the same as in example 1 except that the amount of the light stabilizer was changed to 20 mol%, wherein the yield of the product furandicarboxylic acid was 93%.

Example 13

The specific reaction process and detection method were the same as in example 1 except that the amount of vanadyl sulfate as a co-catalyst was changed to 50 mol%, wherein the yield of furandicarboxylic acid as a product was 85%.

Example 14

The specific reaction process and detection method were the same as in example 1 except that the amount of ethyl acetate as a solvent was changed to 5ml, wherein the yield of the product furandicarboxylic acid was 87%.

The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims

1. A method of making furandicarboxylic acid, comprising:

2. The method of claim 1, wherein the light stabilizer is a hindered amine light stabilizer,

preferably the hindered amine light stabilizer is Chimassorb 944 or a light stabilizer HS-508.

3. The process of claim 1 or 2, wherein the promoter is at least one of vanadyl acetylacetonate, vanadyl sulfate, and vanadium pentoxide.

4. The method of claim 1 or 2, wherein the solvent is at least one of ethyl acetate, acetone, methyl isobutyl ketone, and dimethyl sulfoxide.

5. The method of claim 1 or 2, wherein the oxygen source is hydrogen peroxide.

6. The process according to claim 1 or 2, wherein the reaction temperature is 10-40 ℃; preferably, the reaction temperature is 10-30 ℃;

wherein the reaction time is 0.5-72 hours; preferably, the reaction time is 10 to 24 hours.

7. The process of claim 1 or 2, wherein the molar ratio of the light stabilizer to hydroxymethylfurfural is from 0.05:1 to 10: 1; preferably, the molar ratio of the light stabilizer to hydroxymethylfurfural is from 0.05:1 to 0.3: 1.

8. The process of claim 1 or 2, wherein the molar ratio of the co-catalyst to hydroxymethylfurfural is from 0.1:1 to 10: 1; preferably, the molar ratio of the cocatalyst to hydroxymethylfurfural is 0.1:1 to 0.5: 1.

9. The process of claim 1 or 2, wherein the molar ratio of the oxygen source to hydroxymethylfurfural is from 3:1 to 20: 1; preferably, the molar ratio of the oxygen source to hydroxymethylfurfural is 4:1 to 8: 1.

10. The process of claim 1 or 2, wherein the molar volume ratio of hydroxymethylfurfural to the solvent is from 1:5 to 1:20 mol/L.