A process for the preparation of 2,5-furandicarboxylic acid

Abstract

The application provides a preparation method of 2,5-furan dicarboxylic acid, wherein 5-hydroxymethylfurfural is reacted under the action of an oxidant and an ether solvent to obtain 2,5-furan dicarboxylic acid in an oxygen atmosphere. The application uses 5-hydroxymethylfurfural as a raw material, and 2,5-furan dicarboxylic acid is prepared through one-step oxidation under the action of an oxidant and an ether solvent. The introduction of an initiator reduces the reaction temperature, avoids the self-polymerization of monomers, and improves the reaction yield and selectivity. The reaction system of the application also shortens the reaction time, avoids the use of metals in the reaction, has a mild reaction condition, does not need high temperature and high pressure, increases the reaction safety, simplifies the reaction condition, and is more suitable for industrial production.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of organic synthesis, and particularly relates to a preparation method of 2,5-furan dicarboxylic acid. BACKGROUND

[0002] With the increasing shortage of fossil energy and the expansion of energy demand, the use of renewable biomass energy has attracted more and more attention. Phthalate esters are plasticizers commonly used in the plastic processing process and are widely used in plastic containers, packaging materials, medical devices, children's toys and many other products. Such substances are environmental endocrine disruptors and also have varying degrees of liver and kidney toxicity and reproductive toxicity, and even the risk of carcinogenesis and teratogenesis. The European Union and many countries are limiting the use of plasticizers in plastics. Research has found that 2,5-furan dicarboxylic acid dialkyl ester can be added as a plasticizer to plastics and can be applied to the fields of fibers, films, packaging materials and engineering plastics, etc., and has excellent properties of low carbon, environmental protection and biodegradability, is one of the best substitutes for petroleum-based raw materials terephthalate polyesters in the future, and has important application potential value. Furan dicarboxylic acid is an important intermediate for synthesizing 2,5-furan dicarboxylic acid dialkyl ester, and the research on its preparation method is of great significance.

[0003] At present, there are many studies on the synthesis of 2,5-furan dicarboxylic acid, but most of the research schemes have the defects of complex catalyst or harsh reaction conditions, the need for high temperature or high pressure, low safety, high cost, the use of noble metal catalysts with high cost, metal residue in the product obtained by metal system catalysis, which is difficult to remove, and is not conducive to subsequent bio-based application.

[0004] Publication No. CN116265448A provides a method for preparing furan dicarboxylic acid from furfuroic acid and a method for preparing furan dicarboxylic acid dimethyl ester. The method for preparing furan dicarboxylic acid from furfuroic acid includes that furfural and CO2 are reacted under the condition of a catalyst to generate furan dicarboxylic acid; wherein the catalyst is a porous organic polymer loaded solid base; and the furan dicarboxylic acid is attached to the solid base. The catalyst of the method needs to be prepared by oneself, which is relatively complex and is not conducive to industrial production; in addition, the reaction also needs high temperature of 260 DEG C, and the reaction condition is harsh.

[0005] Publication No. DE102016118154B3 provides a production method of 2,5-FDCA, a method for producing 2,5-FDCA (2,5-furan dicarboxylic acid) from 5-HMF (5-(hydroxymethyl)furfural), wherein an enzyme catalyst having HMF / furfural oxidoreductase activity is brought into contact with process water originating from a hydrothermal carbonization process, the process water used is pretreated to reduce the content of HMF dimers contained in the process water, and the content of HMF dimers is reduced by filtering the process water at 100 DEG C.

[0006] CN107848997B discloses a method for preparing 2,5-furan dicarboxylic acid and its ester from 5-hydroxymethylfurfural and humin, comprising: a) oxidizing raw materials containing hydroxymethylfurfural and humin to produce a mixture containing crude humin-containing 2,5-furan dicarboxylic acid; b) separating the mixture to obtain a solid 2,5-furan dicarboxylic acid / humin composition. The method requires high pressure of 450 psig and high temperature of 200 DEG C, and has high requirements for the reactor and harsh reaction conditions.

[0007] Therefore, it is urgent to develop a method for preparing 2,5-furan dicarboxylic acid with high conversion rate, convenient industrial production and safe reaction. SUMMARY

[0008] In view of the deficiencies of the prior art, the purpose of the present application is to provide a method for preparing 2,5-furan dicarboxylic acid. The method provided by the present application avoids the use of metal in the reaction, has mild reaction conditions, does not require high temperature and high pressure, increases the safety of the reaction, simplifies the reaction conditions, and is more suitable for industrial production.

[0009] To achieve the purpose of the present application, the following technical solutions are adopted:

[0010] A method for preparing 2,5-furan dicarboxylic acid, wherein 5-hydroxymethylfurfural is reacted under an oxygen atmosphere in the presence of an oxidizing agent and an ether solvent to obtain 2,5-furan dicarboxylic acid.

[0011] The oxygen atmosphere in the present application can be a common oxygen bag or oxygen balloon, and the oxygen pressure is close to standard atmospheric pressure, without the need for intentional pressurization.

[0012] Specifically, the ether solvent is at least one selected from ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, 1,4-dioxane, diisopropyl ether, ethyl ether and anisole.

[0013] Specifically, the oxidizing agent is hydrogen peroxide.

[0014] Specifically, the mass ratio of 5-hydroxymethylfurfural, oxidizing agent and ether solvent is 1:(2-5):(7-10).

[0015] Specifically, an initiator is also needed in the reaction, and the initiator is at least one selected from azobisisobutyronitrile, BPO, potassium persulfate and tert-butyl hydroperoxide.

[0016] Preferably, the mass ratio of 5-hydroxymethylfurfural and initiator is 1:(0.1-0.3).

[0017] Specifically, the reaction temperature is 40-80℃; preferably, the reaction temperature can be 40℃, 50℃, 60℃, 70℃ or 80℃, etc., but is not limited to the above listed values, and other values not listed in the above value range are also applicable.

[0018] Preferably, the reaction temperature is 60-70℃; more preferably, the reaction temperature can be 60℃, 61℃, 62℃, 63℃, 64℃, 65℃, 66℃, 67℃, 68℃, 69℃ or 70℃, etc., but is not limited to the above listed values, and other values not listed in the above value range are also applicable.

[0019] Specifically, the reaction time is 0.5-2h; preferably, the reaction time can be 0.5h, 0.7h, 0.9h, 1h, 1.2h, 1.4h, 1.6h, 1.8h or 2h, etc., but is not limited to the above listed values, and other values not listed in the above value range are also applicable.

[0020] Specifically, the reaction needs to be carried out under natural light irradiation. The light irradiation can be natural light irradiation or lamp light irradiation condition, and any light irradiation condition that can realize the reaction is applicable.

[0021] Specifically, the reaction also needs post-treatment, including the following steps: after the reaction is completed, water is added for extraction, the aqueous phase is taken for reduced pressure distillation to obtain brown solid, the white solid is obtained through refining, and the 2,5-furan dicarboxylic acid is obtained through filtration.

[0022] Preferably, the refining is that the brown solid obtained by the reaction is added into about 5 times weight ratio of methanol and about 0.5 times weight ratio of activated carbon, the temperature is increased to 55-65℃, stirring is carried out for 1-3h, then filtration is carried out to obtain colorless solution, the solvent is removed through reduced pressure distillation to obtain white solid, about 4 times weight ratio of ethanol is added, the temperature is increased to 60-80℃, stirring is carried out until the solution is clear, then the temperature is decreased to about 5℃, and the white solid, i.e. 2,5-furan dicarboxylic acid, is precipitated after incubation for 5-7h.

[0023] Compared with the prior art, the present application provides a preparation method of 2,5-furan dicarboxylic acid, which has the following advantages

[0024] Beneficial effects:

[0025] (1) The present application uses 5-hydroxymethyl furfural as raw material, and one-step oxidation is carried out under the action of oxidizing agent and ether solvent to prepare furan dicarboxylic acid, and the introduction of initiator reduces the reaction temperature, avoids the self-polymerization of monomer, and improves the reaction yield and selectivity.

[0026] (2) The reaction system of the present application also shortens the reaction time, avoids the use of metal in the reaction, and has mild reaction conditions without high temperature and high pressure, thereby increasing the reaction safety, simplifying the reaction conditions, and being more suitable for industrial production. Detailed Implementation

[0027] To further illustrate the technical means and effects of the present invention, the following describes the technical solution of the present invention in conjunction with preferred embodiments of the present invention. However, the present invention is not limited to the scope of the embodiments.

[0028] Example 1

[0029] This embodiment provides a method for preparing 2,5-furandicarboxylic acid, comprising the following steps: In a reaction flask, dipropylene glycol dimethyl ether (113.5 g, 0.7 mol, 162.13 g / mol), 5-hydroxymethylfurfural (12.6 g, 0.1 mol, 126.11 g / mol), hydrogen peroxide (37 g, 0.3 mol), and azobisisobutyronitrile (0.32 g, 0.02 mol) are added sequentially. After mixing evenly, the air is replaced with an oxygen atmosphere, and the mixture is stirred and heated to 60°C under natural light for 1 hour. The reaction is monitored by TLC until the conversion of the raw materials is completed. After the reaction was completed, 100 ml of water was added for extraction three times. After separating the aqueous layer, the water was removed by vacuum distillation to obtain 16.8 g of brown solid. The brown solid obtained from the reaction was added to methanol at a weight ratio of 5 and activated carbon at a weight ratio of 0.5. The mixture was heated to 60 °C and stirred for 2 h. After filtration, a colorless solution was obtained. After removing the solvent by vacuum distillation, a white solid was obtained. Ethanol at a weight ratio of 4 was added, and the mixture was heated to 70 °C and stirred until dissolved. The mixture was then cooled to 5 °C and kept at that temperature for 6 h, precipitating a large amount of white solid. After filtration, 15.3 g of 2,5-furandicarboxylic acid product was obtained. The reaction yield was 98% and the purity was 99.9%.

[0030] Example 2

[0031] This embodiment provides a method for preparing 2,5-furandicarboxylic acid, which is basically the same as that in Example 1, except that ethylene glycol dimethyl ether (63.1 g, 0.7 mol, 90.121 g / mol) is added to the reaction flask, and 14.7 g of 2,5-furandicarboxylic acid product is finally obtained, with a reaction yield of 94% and a purity of 99.8%.

[0032] Example 3

[0033] This embodiment provides a method for preparing 2,5-furandicarboxylic acid, which is basically the same as that in Example 1, except that diethylene glycol dimethyl ether (93.9 g, 0.7 mol, 134.17 g / mol) is added to the reaction flask, and 15.1 g of 2,5-furandicarboxylic acid product is finally obtained, with a reaction yield of 97% and a purity of 99.9%.

[0034] Example 4

[0035] The present example provides a method for preparing 2,5-furan dicarboxylic acid, which is basically the same as example 1, except that 1,4-dioxane (61.7 g, 0.7 mol, 88.105 g / mol) is added in the reaction bottle, and finally 13.3 g of 2,5-furan dicarboxylic acid product is obtained, with a reaction yield of 85% and a purity of 99.9%.

[0036] Example 5

[0037] The present example provides a method for preparing 2,5-furan dicarboxylic acid, which is basically the same as example 1, except that hydrogen peroxide (24.5 g, 0.2 mol) is added, and finally 13.3 g of 2,5-furan dicarboxylic acid product is obtained, with a reaction yield of 85% and a purity of 99.9%.

[0038] Example 6

[0039] The present example provides a method for preparing 2,5-furan dicarboxylic acid, which is basically the same as example 1, except that hydrogen peroxide (61.5 g, 0.5 mol) is added, and finally 14.2 g of 2,5-furan dicarboxylic acid product is obtained, with a reaction yield of 91% and a purity of 99.8%.

[0040] Example 7

[0041] The present example provides a method for preparing 2,5-furan dicarboxylic acid, which is basically the same as example 1, except that dipropylene glycol dimethyl ether (129.7 g, 0.8 mol, 162.13 g / mol) is added, and finally 15.8 g of 2,5-furan dicarboxylic acid product is obtained, with a reaction yield of 95% and a purity of 99.8%.

[0042] Example 8

[0043] The present example provides a method for preparing 2,5-furan dicarboxylic acid, which is basically the same as example 1, except that dipropylene glycol dimethyl ether (162.1 g, 1.0 mol, 162.13 g / mol) is added, and finally 14.2 g of 2,5-furan dicarboxylic acid product is obtained, with a reaction yield of 91% and a purity of 99.9%.

[0044] Example 9

[0045] The present example provides a method for preparing 2,5-furan dicarboxylic acid, which is basically the same as example 1, except that azobisisobutyronitrile (0.16 g, 0.01 mol) is added, and finally 14.1 g of 2,5-furan dicarboxylic acid product is obtained, with a reaction yield of 90% and a purity of 99.9%.

[0046] Example 10

[0047] The present example provides a method for preparing 2,5-furan dicarboxylic acid, which is basically the same as example 1, except that azobisisobutyronitrile (0.48 g, 0.03 mol) is added, and finally 14.8 g of 2,5-furan dicarboxylic acid product is obtained, with a reaction yield of 95% and a purity of 99.9%.

[0048] Example 11

[0049] The present example provides a method for preparing 2,5-furan dicarboxylic acid, which is basically the same as example 1, except that the reaction is stirred under natural light and heated to 40°C for 2 hours, and finally 11.4 g of 2,5-furan dicarboxylic acid product is obtained, with a reaction yield of 73% and a purity of 99.9%.

[0050] Example 12

[0051] The present example provides a method for preparing 2,5-furan dicarboxylic acid, which is basically the same as example 1, except that the reaction is stirred under natural light and heated to 70°C for 1 hour, and finally 15.1 g of 2,5-furan dicarboxylic acid product is obtained, with a reaction yield of 97% and a purity of 99.9%.

[0052] Example 13

[0053] The present example provides a method for preparing 2,5-furan dicarboxylic acid, which is basically the same as example 1, except that the reaction is stirred under natural light and heated to 80°C for 1 hour, and finally 14.2 g of 2,5-furan dicarboxylic acid product is obtained, with a reaction yield of 91% and a purity of 99.8%.

[0054] Example 14

[0055] The present example provides a method for preparing 2,5-furan dicarboxylic acid, which is basically the same as example 1, except that the initiator potassium persulfate (5.4 g, 0.02 mol, 270.322 g / mol) is added, and finally 13.6 g of 2,5-furan dicarboxylic acid product is obtained, with a reaction yield of 87% and a purity of 99.9%.

[0056] Comparative Example 1

[0057] The present comparative example provides a method for preparing 2,5-furan dicarboxylic acid, which is basically the same as example 1, except that diisopropyl ether (71.5 g, 0.7 mol, 102.175 g / mol) is added in the reaction bottle, and finally 4.2 g of 2,5-furan dicarboxylic acid product is obtained, with a reaction yield of 27%.

[0058] Comparative Example 2

[0059] This comparative example provides a method for preparing 2,5-furan dicarboxylic acid, which is substantially the same as Example 1, except that in the reaction bottle, anisole (75.6 g, 0.7 mol, 108.138 g / mol) is added, and finally 0.8 g of 2,5-furan dicarboxylic acid product is obtained, with a reaction yield of 5%.

[0060] Comparative Example 3

[0061] This comparative example provides a method for preparing 2,5-furan dicarboxylic acid, which is substantially the same as Example 1, except that in the reaction bottle, anisole (75.6 g, 0.7 mol, 108.138 g / mol) is added, and finally 0.8 g of 2,5-furan dicarboxylic acid product is obtained, with a reaction yield of 5%.

[0062] Comparative Example 4

[0063] This comparative example provides a method for preparing 2,5-furan dicarboxylic acid, which is substantially the same as Example 1, except that in the reaction bottle, anisole (75.6 g, 0.7 mol, 108.138 g / mol) is added, and finally 0.8 g of 2,5-furan dicarboxylic acid product is obtained, with a reaction yield of 5%.

[0064] Comparative Example 5

[0065] This comparative example provides a method for preparing 2,5-furan dicarboxylic acid, which is substantially the same as Example 1, except that in the reaction bottle, anisole (75.6 g, 0.7 mol, 108.138 g / mol) is added, and finally 0.8 g of 2,5-furan dicarboxylic acid product is obtained, with a reaction yield of 5%.

[0066] Comparative Example 6

[0067] This comparative example provides a method for preparing 2,5-furan dicarboxylic acid, which is substantially the same as Example 1, except that in the reaction bottle, anisole (75.6 g, 0.7 mol, 108.138 g / mol) is added, and finally 0.8 g of 2,5-furan dicarboxylic acid product is obtained, with a reaction yield of 5%.

[0068] Comparative Example 7

[0069] This comparative example provides a method for preparing 2,5-furan dicarboxylic acid, which is substantially the same as Example 1, except that in the reaction bottle, anisole (75.6 g, 0.7 mol, 108.138 g / mol) is added, and finally 0.8 g of 2,5-furan dicarboxylic acid product is obtained, with a reaction yield of 5%.

[0070] Comparative Example 8

[0071] This comparative example provides a method for preparing 2,5-furan dicarboxylic acid, which is substantially the same as Example 1, except that in the reaction bottle, anisole (75.6 g, 0.7 mol, 108.138 g / mol) is added, and finally 0.8 g of 2,5-furan dicarboxylic acid product is obtained, with a reaction yield of 5%.

[0072] Comparative Example 9

[0073] This comparative example provides a method for preparing 2,5-furan dicarboxylic acid, which is substantially the same as Example 1, except that the reaction temperature is 30°C, and no reaction occurs ultimately, and no target product is generated.

[0074] Comparative Example 10

[0075] This comparative example provides a method for preparing 2,5-furan dicarboxylic acid, which is substantially the same as Example 1, except that the reaction time is 10 h, and 13.9 g of 2,5-furan dicarboxylic acid product is ultimately obtained, with a reaction yield of 89%.

[0076] Comparative Example 11

[0077] This comparative example provides a method for preparing 2,5-furan dicarboxylic acid, which is substantially the same as Example 1, except that dipropylene glycol dimethyl ether (64.9 g, 0.4 mol, 162.13 g / mol) is added, and 2.34 g of 2,5-furan dicarboxylic acid product is ultimately obtained, with a reaction yield of 15%.

[0078] Comparative Example 12

[0079] This comparative example provides a method for preparing 2,5-furan dicarboxylic acid, which is substantially the same as Example 1, except that hydrogen peroxide (12.3 g, 0.1 mol) is added, and 4.7 g of 2,5-furan dicarboxylic acid product is ultimately obtained, with a reaction yield of 30%.

[0080] Comparative Example 13

[0081] This comparative example provides a method for preparing 2,5-furan dicarboxylic acid, which is substantially the same as Example 1, except that hydrogen peroxide (74 g, 0.6 mol) is added, and 15.1 g of 2,5-furan dicarboxylic acid product is ultimately obtained, with a reaction yield of 96.7% and a purity of 93%. Although the yield is substantially the same as Example 1, there is too much hydrogen peroxide remaining, and the risk of post-processing is high.

[0082] Comparative Example 14

[0083] This comparative example provides a method for preparing 2,5-furan dicarboxylic acid, which is substantially the same as Example 1, except that azobisisobutyronitrile (0.08 g, 0.005 mol) is added, and 2.5 g of 2,5-furan dicarboxylic acid product is ultimately obtained, with a reaction yield of 16%.

[0084] Comparative Example 15

[0085] The comparative example 2 provides a preparation method of 2,5-furan dicarboxylic acid, which is basically the same as the example 1, except that azobisisobutyronitrile (0.64g, 0.04mol) is added, and finally 15.2g of 2,5-furan dicarboxylic acid product is obtained, with a reaction yield of 97.4% and a purity of 99.7%. Although the yield is basically the same as that of the example 1, it will cause waste of raw materials.

[0086] The applicant declares that the present application illustrates a preparation method of 2,5-furan dicarboxylic acid by the above examples, but the present application is not limited to the above examples, i.e. it does not mean that the present application must rely on the above examples to be implemented. It should be understood by those skilled in the art that any improvement of the present application, equivalent replacement of each raw material of the product of the present application, addition of auxiliary ingredients, selection of specific modes, etc. all fall within the protection scope and disclosure scope of the present application.

[0087] The above describes the preferred embodiments of the present application, but the present application is not limited to the specific details in the above embodiments, and within the technical concept scope of the present application, various simple modifications can be made to the technical solutions of the present application, and these simple modifications all belong to the protection scope of the present application.

[0088] In addition, it should be noted that each specific technical feature described in the above specific embodiments can be combined in any appropriate manner without contradiction, and in order to avoid unnecessary repetition, the present application will not further describe various possible combination manners.

Claims

1. A method for producing 2,5-furan dicarboxylic acid, characterized by, 5-hydroxymethylfurfural is reacted in an oxygen atmosphere in the presence of an oxidizing agent and an ether solvent to obtain 2,5-furan dicarboxylic acid; the ether solvent is at least one selected from ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether and 1,4-dioxane; the oxidizing agent is hydrogen peroxide; an initiator is also added in the reaction, the initiator is azobisisobutyronitrile or potassium persulfate; the reaction temperature is 40-80 DEG C; the reaction needs to be carried out under natural light irradiation.

2. The preparation method according to claim 1, characterized in that, The mass ratio of 5-hydroxymethylfurfural, oxidizing agent and ether solvent is 1:(2-5):(7-10).

3. The preparation method according to claim 1, characterized in that, The mass ratio of 5-hydroxymethylfurfural and initiator is 1:(0.1-0.3).

4. The preparation method according to claim 1, characterized in that, The reaction temperature is 60-70 DEG C.

5. The method of claim 1, wherein the step of forming the first and second layers is performed by a process selected from the group consisting of: sputtering, evaporation, and chemical vapor deposition. The reaction time is 0.5-2 h.

6. The method of claim 1, wherein the step of forming the first and second layers is performed by a process selected from the group consisting of: sputtering, evaporation, and chemical vapor deposition. The reaction also needs post-treatment, including the following steps, after the reaction is completed, water is added for extraction, the aqueous phase is taken for vacuum distillation to obtain brown solid, which is refined to obtain white solid, and the 2,5-furan dicarboxylic acid is obtained by filtration.