Method for preparing 2, 5-furandimethylamine from 2, 5-furandicarboxylic acid

Abstract

The invention relates to a method for preparing 2, 5-furandimethylamine from 2, 5-furandicarboxylic acid, which comprises the following steps: contacting a reaction substrate, a catalyst and a solvent in a closed container, and reacting in a mixed atmosphere of ammonia gas and hydrogen, the catalyst is raney nickel and / or raney cobalt, and the reaction substrate is 2, 5-furandicarboxylic acid. The method disclosed by the invention is short in process flow, free of highly toxic intermediate products, low in production cost, high in production efficiency, high in product selectivity and easy to industrialize.

Description

Technical Field

[0001] The present disclosure relates to the fields of green chemistry and catalysis, and in particular, to a method for preparing 2,5-furandiamine from 2,5-furandicarboxylic acid. Background Art

[0002] The bicyclic primary diamine - 2,5-furandiamine with a heterocyclic structure is an important organic raw material, which can replace m-phenylenediamine and m-xylenediamine and has wide applications in the production of high molecular materials, liquid crystal materials, pharmaceuticals, pesticides, etc. For example, when 2,5-furandiamine is used as a curing agent for resin components made of epoxy resin and reactive diluent, it is more conducive to the hardening process.

[0003] Currently reported methods for preparing 2,5-furandiamine mainly include the reduction amination method of 2,5-furandialdehyde, the hydrogenation method of 2,5-furandialdehyde oxime, and the hydrogenation method of 2,5-furandicarbonitrile. These three methods all start from 2,5-furandialdehyde as the raw material, but 2,5-furandialdehyde has active reaction properties and is not easy to store. Reduction amination is commonly used for the conversion of aldehydes or alcohols to prepare primary amine compounds. At present, there are few research reports on the reaction process of directly reducing amination of diacids to prepare diamines. Coeck et al. first reported the reaction of one-pot reduction amination of carboxylic acids to prepare primary amines. The main reaction substrates are monocarboxylic acids, and the yield of primary amines is high; however, when three dicarboxylic acid substrates are subjected to reduction amination, cyclic products such as lactams or cyclic secondary amines are mainly formed. The highest yield of the bicyclic primary diamine is sebac diamine, only 30%, and the yield of hexamethylenediamine is 0. Moreover, the catalyst is an expensive Ru-based catalyst, and the preparation cost is high.

[0004] 2,5-Furandicarboxylic acid has better stability than 2,5-furandialdehyde and is defined as one of the twelve bio-based platform compounds. After consultation, there is currently no research report on preparing 2,5-furandiamine using 2,5-furandicarboxylic acid as the substrate. Summary of the Invention

[0005] The purpose of the present disclosure is to provide a method for preparing 2,5-furandiamine from 2,5-furandicarboxylic acid. This method uses a non-noble metal catalyst, which is inexpensive, non-toxic, has a simple reaction process, simple product post-treatment, no highly toxic intermediate products, low production cost, high production efficiency, and high product selectivity, and is easy to industrialize.

[0006] To achieve the above purpose, the present disclosure provides a method for preparing 2,5-furandiamine from 2,5-furandicarboxylic acid, and the method includes:

[0007] Contacting the reaction substrate, the catalyst and the solvent in a closed container, and carrying out the reaction under a mixed atmosphere of ammonia gas and hydrogen gas; the catalyst is Raney nickel and / or Raney cobalt, and the reaction substrate is 2,5-furandicarboxylic acid.

[0008] Optionally, the catalyst is Raney nickel.

[0009] Optionally, the method includes mixing the reaction substrate with the solvent to form a binary carboxylic acid solution, and then contacting the solution with the catalyst to carry out the reaction; the mass concentration of the binary carboxylic acid solution is 20-40%, preferably 24-30%.

[0010] Optionally, the pressure of the ammonia gas is 0.1-2 MPa, preferably 0.25-0.75 MPa.

[0011] Optionally, the pressure of the hydrogen gas is 0.1-2 Mpa, preferably 0.7-1.2 Mpa.

[0012] Optionally, the mass ratio of the reaction substrate to the catalyst is 100:2-15, preferably 100:8-15.

[0013] Optionally, the reaction conditions include a reaction temperature of 120-190 °C, preferably 150-180 °C; the reaction time is 5-20 h, preferably 10-15 h.

[0014] Optionally, before starting the reaction, the method further includes heating the reaction system to the reaction temperature at a rate of 3-10 °C / min; the rate is preferably 4-7 °C / min.

[0015] Optionally, the solvent includes one or more of ether solvents and alcohol ether solvents.

[0016] Optionally, the solvent is selected from one or more of propylene glycol methyl ether, propylene glycol ethyl ether, cyclopentyl methyl ether, and isopropyl ether.

[0017] Through the above technical solutions, the present disclosure uses a non-noble metal Raney nickel / cobalt catalyst, and under a mixed atmosphere containing ammonia and hydrogen, 2,5-furandicarboxylic acid is directly reduced and aminated to obtain 2,5-furandiamine, and the product selectivity is high. The method of the present disclosure has a short process flow, no highly toxic intermediate products, low production costs, high production efficiency, and is easy to industrialize.

[0018] Other features and advantages of the present disclosure will be described in detail in the subsequent specific implementation section. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] The drawings are used to provide a further understanding of the present disclosure, and constitute a part of the specification, and are used to explain the present disclosure together with the following specific implementation, but do not constitute a limitation to the present disclosure. In the drawings:

[0020] Figure 1It is the mass spectrum of 2,5-furandicarboxylic diamine in Embodiment 1 of the present disclosure. Detailed Embodiments

[0021] The following further elaborates on the detailed embodiments of the present disclosure with reference to the accompanying drawings. It should be understood that the detailed embodiments described herein are only for the purpose of illustrating and explaining the present disclosure, and are not intended to limit the present disclosure.

[0022] The present disclosure provides a method for preparing 2,5-furandicarboxylic diamine from 2,5-furandicarboxylic acid, the method comprising:

[0023] bringing a reaction substrate, a catalyst, and a solvent into contact in a closed container, and carrying out a reaction in a mixed atmosphere of ammonia and hydrogen; the catalyst is Raney nickel and / or Raney cobalt, and the reaction substrate is 2,5-furandicarboxylic acid.

[0024] The present disclosure uses a non-noble metal Raney nickel / cobalt catalyst and, in a mixed atmosphere containing ammonia and hydrogen, directly reduces and amines bio-based 2,5-furandicarboxylic acid to obtain 2,5-furandicarboxylic diamine, and the product has high selectivity. The method of the present disclosure has a short process flow, simple post-treatment of the product, no highly toxic intermediate products, low production costs, high production efficiency, is easy to industrialize, and has good environmental and economic benefits.

[0025] According to the present disclosure, the reaction can proceed according to the following reaction formula:

[0026]

[0027] According to an embodiment of the present disclosure, the catalyst is Raney nickel. The above embodiment is conducive to the product having higher selectivity and a higher conversion rate of 2,5-furandicarboxylic acid.

[0028] According to an embodiment of the present disclosure, the method includes mixing the reaction substrate and the solvent to form a dicarboxylic acid solution, and contacting the dicarboxylic acid solution with the catalyst to carry out the reaction; the mass concentration of the dicarboxylic acid solution is 20-40%, preferably 24-30%. The above embodiment is conducive to the product having higher selectivity.

[0029] According to an embodiment of the present disclosure, the pressure of the ammonia is 0.1-2 MPa, preferably 0.25-0.75 MPa. The pressure of the hydrogen is 0.1-2.0 MPa, preferably 0.7-1.2 MPa. The above embodiment is conducive to the product having higher selectivity and a higher conversion rate of 2,5-furandicarboxylic acid.

[0030] According to an embodiment of the present disclosure, the mass ratio of the reaction substrate to the catalyst is 100:2 - 15, preferably 100:8 - 15. The above embodiment is conducive to the product having higher selectivity and a higher conversion rate of 2,5-furandicarboxylic acid.

[0031] According to an embodiment of the present disclosure, the conditions of the reaction include a reaction temperature of 120 - 190°C, preferably 150 - 180°C; and a reaction time of 5 - 20 h, preferably 10 - 15 h. The above embodiment is conducive to the product having higher selectivity.

[0032] According to an embodiment of the present disclosure, before starting the reaction, the method may include heating the reaction system from temperature T1 to the reaction temperature at a rate of 3 - 10°C / min; T1 is 60 - 80°C; the rate is preferably 4 - 7°C / min. The above embodiment is conducive to the product having higher selectivity.

[0033] According to an embodiment of the present disclosure, the solvent includes one or more of ether solvents and alcohol ether solvents; the ether solvent may be selected from ethers having 3 - 8 carbon atoms; the alcohol ether solvent may be selected from alcohol ethers having 3 - 8 carbon atoms; in a further embodiment, the solvent is selected from one or two of propylene glycol methyl ether, propylene glycol ethyl ether, cyclopentyl methyl ether, and isopropyl ether. The above embodiment is conducive to the product having higher selectivity.

[0034] According to the present disclosure, the product is qualitatively analyzed by gas chromatography - mass spectrometry; and quantitatively analyzed by high - performance liquid chromatography.

[0035] The present disclosure will be further illustrated by the following examples, but the present disclosure is not limited thereby.

[0036] In the examples, the Raney nickel used was purchased from MACKLIN, product number R817297, 50 μm; the Raney cobalt used was purchased from MACKLIN, product number R817300, 50 μm; the Ru / C catalyst used was purchased from Shanghai Aladdin, product number A58343.

[0037] In the examples of the present disclosure, the high - performance liquid chromatography analysis was carried out on an instrument of model Agilent 1260LC; the gas chromatography - mass spectrometry analysis was carried out on an instrument of model Thermo Scientific ISQ 7000.

[0038] Unless otherwise specified, the remaining chemical reagents used in the examples are all commercially available products.

[0039] Example 1

[0040] Take 20.00 g of 2,5-furandicarboxylic acid and dissolve it in 60.00 g of propylene glycol methyl ether (the mass fraction of 2,5-furandicarboxylic acid in the solution is 25%). After mixing evenly, add it to a high-pressure reactor, and add 2.60 g of Raney nickel catalyst to the reactor. After repeatedly displacing the gas in the high-pressure reactor with nitrogen 3 times, introduce 0.55 MPa of ammonia and 1.00 MPa of hydrogen. Within 0.3 hours, the temperature of the reactor is raised from 60 °C to 170 °C, and the heating rate is 6.1 °C / min. React at 170 °C for 13 hours. In this reaction, the mass ratio of 2,5-furandicarboxylic acid to Raney nickel is 100:13. After the reaction is completed, take out the reaction solution for testing. The conversion rate of 2,5-furandicarboxylic acid is analyzed to be 99.9%, and the selectivity of 2,5-furandimethylamine is 51.1%.

[0041] Example 2

[0042] Take 20.00 g of 2,5-furandicarboxylic acid and dissolve it in 60.00 g of cyclopentyl methyl ether (the mass fraction of 2,5-furandicarboxylic acid in the solution is 25%). After mixing evenly, add it to a high-pressure reactor, and add 1.60 g of Raney nickel catalyst to the reactor. After repeatedly displacing the gas in the high-pressure reactor with nitrogen 3 times, introduce 0.35 MPa of ammonia and 0.80 MPa of hydrogen. Within 0.35 hours, the temperature of the reactor is raised from 65 °C to 180 °C, and the heating rate is 5.5 °C / min. React at 180 °C for 20 hours. In this reaction, the mass ratio of 2,5-furandicarboxylic acid to Raney cobalt is 100:8. After the reaction is completed, take out the reaction solution for testing. The conversion rate of 2,5-furandicarboxylic acid is analyzed to be 99.9%, and the selectivity of 2,5-furandimethylamine is 47.5%.

[0043] Example 3

[0044] Take 20.00 g of 2,5-furandicarboxylic acid and dissolve it in 46.67 g of cyclopentyl methyl ether (the mass fraction of 2,5-furandicarboxylic acid in the solution is 30%). After mixing evenly, add it to a high-pressure reactor, and add 2.40 g of Raney nickel catalyst to the reactor. After repeatedly displacing the gas in the high-pressure reactor with nitrogen 3 times, introduce 0.60 MPa of ammonia and 1.00 MPa of hydrogen. Within 0.4 hours, the temperature of the reactor is raised from 60 °C to 175 °C, and the heating rate is 4.8 °C / min. React at 175 °C for 10 hours. In this reaction, the mass ratio of 2,5-furandicarboxylic acid to Raney nickel is 100:12. After the reaction is completed, take out the reaction solution for testing. The conversion rate of 2,5-furandicarboxylic acid is analyzed to be 99.9%, and the selectivity of 2,5-furandimethylamine is 37.8%.

[0045] Example 4

[0046] The method of this example is the same as that of Example 1, except that the catalyst in this example is Raney cobalt. After the reaction, the reaction solution was taken out for testing. The conversion rate of 2,5-furandicarboxylic acid was analyzed to be 87.9%, and the selectivity of 2,5-furandimethylamine was 21.3%.

[0047] Example 5

[0048] The method of this example is the same as that of Example 1, except that the pressure of ammonia in this example is 1.0 MPa. After the reaction, the reaction solution was taken out for testing. The conversion rate of 2,5-furandicarboxylic acid was analyzed to be 89.6%, and the selectivity of 2,5-furandimethylamine was 16.1%.

[0049] Example 6

[0050] The method of this example is the same as that of Example 1, except that the pressure of hydrogen in this example is 0.4 MPa. After the reaction, the reaction solution was taken out for testing. The conversion rate of 2,5-furandicarboxylic acid was analyzed to be 99.9%, and the selectivity of 2,5-furandimethylamine was 25.4%.

[0051] Example 7

[0052] The method of this example is the same as that of Example 1, except that the amount of Raney nickel used in this example is 1.4 g, and the mass ratio of 2,5-furandicarboxylic acid to Raney nickel is 100:7. After the reaction, the reaction solution was taken out for testing. The conversion rate of 2,5-furandicarboxylic acid was analyzed to be 78.6%, and the selectivity of 2,5-furandimethylamine was 12.4%.

[0053] Example 8

[0054] 20.00 g of 2,5-furandicarboxylic acid was dissolved in 60.00 g of propylene glycol methyl ether (the mass fraction of 2,5-furandicarboxylic acid in the solution was 25%). After mixing evenly, it was added to a high-pressure reactor, and 2.60 g of Raney nickel catalyst was added to the reactor. After the gas in the high-pressure reactor was repeatedly replaced with nitrogen 3 times, 0.55 MPa of ammonia and 1.00 MPa of hydrogen were introduced. Within 25 minutes, the temperature of the reactor was raised from 60 °C to 210 °C at a heating rate of 6 °C / min, and the reaction was carried out at 210 °C for 13 hours. In this reaction, the mass ratio of 2,5-furandicarboxylic acid to Raney nickel was 100:13. After the reaction, the reaction solution was taken out for testing. The conversion rate of 2,5-furandicarboxylic acid was analyzed to be 99.9%, and the selectivity of 2,5-furandimethylamine was 9.4%.

[0055] Comparative Example 1

[0056] Take 20.00 g of 2,5-furandicarboxylic acid and dissolve it in 60.00 g of propylene glycol methyl ether. After mixing evenly, add it to a high-pressure reactor, and add 2.60 g of Ru / C catalyst to the reactor. After repeatedly displacing the gas in the high-pressure reactor with nitrogen 3 times, introduce 0.55 MPa of ammonia and 1.00 MPa of hydrogen. Within 0.3 hours, the temperature of the reactor is raised from 60 °C to 170 °C, and the reaction is carried out at 170 °C for 13 hours. In this reaction, the mass fraction of 2,5-furandicarboxylic acid in the solution is 25%, and the mass ratio of 2,5-furandicarboxylic acid to Ru / C catalyst is 100:13. After the reaction is completed, take out the reaction solution for testing. The conversion rate of 2,5-furandicarboxylic acid is 99.9%, and the selectivity of 2,5-furandimethylamine is 0.

[0057] Table 1

[0058] Conversion rate of 2,5-furandicarboxylic acid / % Selectivity of 2,5-furandimethylamine / % Example 1 99.9 51.1 Example 2 99.9 47.5 Example 3 99.9 37.8 Example 4 87.9 21.3 Example 5 89.6 16.1 Example 6 99.9 25.4 Example 7 78.6 12.4 Example 8 99.9 9.4 Comparative Example 1 99.9 0

[0059] According to the data in Table 1, the method of the present disclosure realizes the one-step preparation of 2,5-furandimethylamine from 2,5-furandicarboxylic acid. The catalyst uses non-noble metals, has low cost and is non-toxic. The reaction process is simple, there is no highly toxic intermediate product, the production cost is low, the production efficiency is high and the product selectivity is high, which is easy to industrialize and has good environmental and economic benefits. By comparing Example 1 with Example 4, it can be seen that the preferred catalyst of the present disclosure makes the reaction product have higher selectivity and the conversion rate of 2,5-furandicarboxylic acid is higher. By comparing Example 1 with Example 5, it can be seen that within the preferred ammonia pressure range of the present disclosure, the reaction product has higher selectivity and the conversion rate of 2,5-furandicarboxylic acid is higher. By comparing Example 1 with Example 6, it can be seen that within the preferred hydrogen pressure range of the present disclosure, the reaction product has higher selectivity. By comparing Example 1 with Example 7, it can be seen that within the preferred mass ratio range of the reaction substrate to the catalyst of the present disclosure, the reaction product has higher selectivity and the conversion rate of 2,5-furandicarboxylic acid is higher. By comparing Example 1 with Example 8, it can be seen that within the reaction condition range of the present disclosure, the reaction product has higher selectivity.

[0060] The preferred embodiments of the present disclosure have been described in detail above in conjunction with the accompanying drawings. However, the present disclosure is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present disclosure, various simple modifications can be made to the technical solutions of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.

[0061] In addition, it should be noted that, within the scope of no conflict, the various specific technical features described in the above specific embodiments can be combined in any appropriate manner. To avoid unnecessary repetition, the present disclosure will not separately describe various possible combination methods.

[0062] In addition, any combination can be made among various different embodiments of the present disclosure, as long as it does not violate the idea of the present disclosure, and it should also be regarded as the content disclosed by the present disclosure.

Claims

1. A method for preparing 2,5-furandiamine from 2,5-furandicarboxylic acid, characterized in that, The method includes: Contacting a reaction substrate, a catalyst and a solvent in a closed container and carrying out a reaction under a mixed atmosphere of ammonia and hydrogen; the catalyst is Raney nickel and / or Raney cobalt, and the reaction substrate is 2,5-furandicarboxylic acid.

2. The method according to claim 1, wherein, The catalyst is Raney nickel.

3. The method according to claim 1, wherein, The method includes mixing the reaction substrate and the solvent to form a dicarboxylic acid solution, and then contacting the solution with the catalyst to carry out the reaction; the mass concentration of the dicarboxylic acid solution is 20-40%, preferably 24-30%.

4. The method according to claim 1, wherein, The pressure of the ammonia is 0.1-2 MPa, preferably 0.25-0.75 MPa.

5. The method according to claim 1, wherein, The pressure of the hydrogen is 0.1-2 Mpa, preferably 0.7-1.2 Mpa.

6. The method according to claim 1, wherein, The mass ratio of the reaction substrate to the catalyst is 100:2-15, preferably 100:8-15.

7. The method according to claim 1, wherein The conditions of the reaction include a reaction temperature of 120-190 °C, preferably 150-180 °C; and a reaction time of 5-20 h, preferably 10-15 h.

8. The method according to claim 7, wherein Before starting the reaction, the method further includes heating the reaction system to the reaction temperature at a rate of 3-10 °C / min; the rate is preferably 4-7 °C / min.

9. The method according to claim 1, wherein The solvent includes one or more of ether solvents and alcohol ether solvents.

10. The method according to claim 9, wherein The solvent is selected from one or more of propylene glycol methyl ether, propylene glycol ethyl ether, cyclopentyl methyl ether and isopropyl ether.

Images