Method for preparing primary diamine from dicarboxylic acid
By reacting the dicarboxylic acid with the ammonia source under a hydrogen atmosphere by reacting the dicarboxylic acid with the ammonia source in the prior art, the problems of high energy consumption and high cost of diamine preparation by hydrogenating dinitrile in the prior art are solved, and efficient and low-cost preparation of binary primary amines is achieved, which is suitable for industrial production.
Patent Information
- Application Number
- CN202410132781.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-01-30
- Publication Date
- 2025-08-01
AI Technical Summary
In the prior art, the diamine preparation process for dinitrile hydrogenation has high energy consumption, high raw materials, low product selectivity, complex process flow, and high cost of precious metal catalysts. The method of dicarboxylic acid to directly prepare diamine in one step is low, mainly producing cyclization products.
Using Rainie nickel and/or Rainie cobalt catalysts, the dicarboxylic acid, ammonia source and solvent are contacted under a hydrogen atmosphere, and the reaction conditions such as temperature, time and pressure are controlled to achieve one-step conversion of the dicarboxylic acid into a binary primary amine.
It realizes a binary primary amine preparation method with simple process, no toxic intermediate products, low production cost, high production efficiency and high product selectivity, and is easy to industrialize.
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Figure CN120398694A_ABST
Abstract
Description
Technical Field
[0001] The present disclosure relates to the fields of green chemistry and catalysis, and in particular, to a method for preparing a secondary diamine from a dicarboxylic acid. Background Art
[0002] Secondary diamines are important organic raw materials and have wide applications in the production of polymer materials, liquid crystal materials, pharmaceuticals, pesticides, etc. For example, hexamethylenediamine, m-xylylenediamine, p-xylylenediamine, etc. are important monomers for the production of polyamides. m-Xylylenediamine and p-xylylenediamine are also good epoxy resin curing agents. The preparation of diamines such as hexamethylenediamine, m-xylylenediamine, and p-xylylenediamine is mainly carried out by hydrogenation of the corresponding dinitriles. The preparation process of dinitriles has problems such as high energy consumption, highly toxic raw materials, low product selectivity, and complex process flow.
[0003] Currently, there are few research reports on the reaction process for directly preparing diamines from diacids in one step. Coeck et al. first reported the reaction of one-pot reductive amination of carboxylic acids to prepare primary amines. The main reaction substrate is monocarboxylic acid, and the yield of primary amines is high; however, when three dicarboxylic acid substrates are subjected to reductive amination, cyclic products such as lactams or cyclic secondary amines are mainly formed, and the yields of secondary diamines are relatively low. Moreover, the catalyst is an expensive Ru-based catalyst, and the preparation cost is high. Summary of the Invention
[0004] The purpose of the present disclosure is to provide a method for preparing a secondary diamine from a dicarboxylic acid. The method has a simple process, no highly toxic intermediate products, low production cost, high production efficiency, high product selectivity, and is easy to industrialize.
[0005] To achieve the above purpose, the present disclosure provides a method for preparing a secondary diamine from a dicarboxylic acid, the method comprising:
[0006] Contacting a dicarboxylic acid, an ammonia source, a catalyst, and a solvent in a closed container and reacting under a hydrogen atmosphere; wherein, the dicarboxylic acid is represented by formula (1),
[0007]
[0008] R1 is selected from one of an alkylene group having 2-12 carbon atoms and a five-membered heterocyclic group; the ammonia source is ammonia water or an ammonium salt; the catalyst is Raney nickel and / or Raney cobalt.
[0009] Optionally, the alkylene group is selected from one or more of ethylene, butylene, hexylene, octylene, and phenylene; the five-membered heterocyclic group is selected from one or more of furanylene, tetrahydrofuranylene, and thiophenylene.
[0010] Optionally, the dicarboxylic acid is selected from one or more of succinic acid, adipic acid, suberic acid, sebacic acid, 2,5-furandicarboxylic acid, 2,5-tetrahydrofurandicarboxylic acid, 2,5-thiophenedicarboxylic acid, isophthalic acid, and terephthalic acid.
[0011] Optionally, the method includes mixing the dicarboxylic acid with the solvent to form a dicarboxylic acid solution, and then contacting the dicarboxylic acid solution with the ammonia source and the catalyst to carry out the reaction; the mass fraction of the dicarboxylic acid solution is 20-40%, preferably 20-30%.
[0012] Optionally, the ammonium salt is selected from one or more of ammonium chloride, ammonium sulfate, ammonium bromide, ammonium carbonate, ammonium bicarbonate, ammonium oxalate, and ammonium acetate, preferably one or more of ammonium chloride, ammonium sulfate, ammonium bromide, and ammonium oxalate;
[0013] The mass fraction of the ammonia water is 22%-30%.
[0014] Optionally, the molar ratio of the dicarboxylic acid to the ammonia source is 1:2-7, preferably 1:3-5; the mass ratio of the dicarboxylic acid to the catalyst is 100:2-15, preferably 100:6-13.
[0015] Optionally, the reaction conditions include a reaction temperature of 120-250 °C, preferably 160-200 °C; a reaction time of 5-50 h, preferably 5-25 h; and the pressure of hydrogen is 0.1-2 Mpa, preferably 0.5-1 Mpa.
[0016] Optionally, before starting the reaction, the method further includes heating the reaction system to the reaction temperature at a rate of 0-5 °C / min; the rate is preferably 0.5-2 °C / min.
[0017] Optionally, the solvent includes one or more of ether solvents and alcohol ether solvents.
[0018] Optionally, the solvent is selected from one or more of propylene glycol methyl ether, propylene glycol ethyl ether, cyclopentyl methyl ether, and isopropyl ether.
[0019] Through the above technical solutions, the present disclosure uses a Raney cobalt / nickel catalyst to directly synthesize a dibasic primary amine in one step with a dicarboxylic acid. The method of the present disclosure has a simple process flow, no highly toxic intermediate products, low production costs, high production efficiency, high product selectivity, and is easy to industrialize.
[0020] Other features and advantages of the present disclosure will be described in detail in the subsequent specific implementation section. Description of the Drawings
[0021] The accompanying drawings are used to provide a further understanding of the present disclosure and form a part of the specification. Together with the following specific embodiments, they are used to explain the present disclosure, but do not constitute a limitation to the present disclosure. In the accompanying drawings:
[0022] Figure 1 is the mass spectrum of hexamethylenediamine in Example 1. Specific Embodiments
[0023] The following further elaborates on the specific embodiments of the present disclosure with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are only for explaining and understanding the present disclosure, and are not used to limit the present disclosure.
[0024] The present disclosure provides a method for preparing a primary diamine using a dicarboxylic acid, the method comprising:
[0025] contacting a dicarboxylic acid, an ammonia source, a catalyst, and a solvent in a closed container and reacting under a hydrogen atmosphere; wherein, the dicarboxylic acid is represented by formula (1),
[0026]
[0027] R1 is selected from one of an alkylene group having 2 to 12 carbon atoms and a five-membered heterocyclic group; the ammonia source is aqueous ammonia or an ammonium salt; the catalyst is Raney nickel and / or Raney cobalt.
[0028] The present disclosure uses a Raney cobalt / nickel catalyst to directly prepare a primary diamine from a dicarboxylic acid in one step. The method of the present disclosure has a simple process flow, no highly toxic intermediate products, low production costs, high production efficiency, high product selectivity, and is easy to industrialize.
[0029] According to one embodiment of the present disclosure, the reaction can proceed according to the following reaction formula:
[0030]
[0031] According to one embodiment of the present disclosure, the alkylene group is selected from one or more of ethylene, butylene, hexylene, octylene, and phenylene; the five-membered heterocyclic group is selected from one or more of furanylene, tetrahydrofuranylene, and thiophenylene.
[0032] According to one embodiment of the present disclosure, the dicarboxylic acid is selected from one or more of succinic acid, adipic acid, suberic acid, sebacic acid, 2,5-furandicarboxylic acid, 2,5-tetrahydrofurandicarboxylic acid, 2,5-thiophenedicarboxylic acid, isophthalic acid, and terephthalic acid.
[0033] According to an embodiment of the present disclosure, the method includes mixing the dicarboxylic acid with the solvent to form a dicarboxylic acid solution, and then contacting the solution with the ammonia source and the catalyst to carry out the reaction; the mass concentration of the dicarboxylic acid solution is 20-40%, preferably 20-30%. The above embodiment is beneficial to higher selectivity of the product.
[0034] According to an embodiment of the present disclosure, the ammonium salt is selected from one or more of ammonium chloride, ammonium sulfate, ammonium bromide, ammonium carbonate, ammonium bicarbonate, ammonium oxalate, and ammonium acetate, preferably one or more of ammonium chloride, ammonium sulfate, ammonium bromide, and ammonium oxalate; the mass fraction of the ammonia water is 22%-30%. The above embodiment is beneficial to higher selectivity of the product.
[0035] According to an embodiment of the present disclosure, the molar ratio of the dicarboxylic acid to the ammonia source is 1:2-7, preferably 1:3-5; the mass ratio of the dicarboxylic acid to the catalyst is 100:2-15, preferably 100:6-13. The above embodiment is beneficial to high conversion rate of the dicarboxylic acid and higher selectivity of the product.
[0036] According to an embodiment of the present disclosure, the reaction conditions include a reaction temperature of 120-250°C, preferably 160-200°C; a reaction time of 5-50 h, preferably 5-25 h; and the pressure of hydrogen is 0.1-2 Mpa, preferably 0.5-1 Mpa. The above embodiment is beneficial to higher selectivity of the product.
[0037] 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 0-5°C / min; T1 is 20-60°C; the rate is preferably 0.5-2°C / min. The above embodiment is beneficial to higher selectivity of the product.
[0038] 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 with 3-8 carbon atoms; the alcohol ether solvent may be selected from alcohol ethers with 3-8 carbon atoms; in a further embodiment, the solvent is selected from one or more of propylene glycol methyl ether, propylene glycol ethyl ether, cyclopentyl methyl ether, and isopropyl ether. The above embodiment is beneficial to higher selectivity of the product.
[0039] According to the present disclosure, the product is qualitatively analyzed by high performance gas chromatography; the quantitative analysis is carried out by the external standard method.
[0040] The present disclosure will be further illustrated by the following examples, but the present disclosure is not limited thereby.
[0041] In the examples, the Raney nickel used was purchased from MACKLIN, with the product number R817297 and a particle size of 50 μm; the Raney cobalt used was purchased from MACKLIN, with the product number R817300 and a particle size of 50 μm; the Ru / C catalyst used was purchased from Shanghai Aladdin, with the product number A58343. Unless otherwise specified, the remaining chemical reagents used in the examples were all commercially available products.
[0042] In the examples of the present disclosure, the high-performance gas chromatography analysis was carried out on an instrument of model Thermo Scientific Trace1300; the mass spectrometry analysis was carried out on an instrument of model Thermo Scientific ISQ 7000.
[0043] Example 1
[0044] Take 20.00 g of adipic acid and dissolve it in 46.67 g of cyclopentyl methyl ether (the mass fraction of adipic acid is 30%), add 37.22 g of ammonia water (the mass fraction of ammonia water is 25%), mix evenly and then add it to a high-pressure reactor. Add 2.6 g of Raney nickel catalyst to the reactor. After repeatedly displacing the gas in the high-pressure reactor with nitrogen 3 times, introduce hydrogen gas. After repeatedly displacing 3 times, increase the pressure to 1 Mpa with hydrogen gas; within 1.2 hours, raise the temperature of the reactor from 35 °C to 170 °C, with a heating rate of 1.9 °C / min, and then react at 170 °C for 13 hours. In this reaction, the molar ratio of adipic acid to ammonia water is 1:4, and the mass ratio of adipic acid to the Raney nickel catalyst is 100:13. After the reaction is completed, take out the reaction solution for testing. The conversion rate of adipic acid is analyzed to be 99.9%, and the selectivity of hexamethylenediamine is 36.1%.
[0045] Example 2
[0046] Take 20.00 g of adipic acid and dissolve it in 80.00 g of propylene glycol methyl ether (the mass fraction of adipic acid in the solution is 20%), add 50.95 g of ammonium oxalate, mix evenly and then add it to a high-pressure reactor. Add 1.6 g of Raney cobalt catalyst to the reactor. After repeatedly displacing the gas in the high-pressure reactor with nitrogen 3 times, introduce hydrogen gas. After repeatedly displacing 3 times, increase the pressure to 0.8 Mpa with hydrogen gas; within 1.4 hours, raise the temperature of the reactor from 35 °C to 180 °C, with a heating rate of 1.7 °C / min, and then react at 180 °C for 20 hours. In this reaction, the mass fraction of adipic acid in the solution is 20%, the molar ratio of adipic acid to ammonium oxalate is 1:3, and the mass ratio of adipic acid to the Raney cobalt catalyst is 100:8. After the reaction is completed, take out the reaction solution for testing. The conversion rate of adipic acid is analyzed to be 99.9%, and the selectivity of hexamethylenediamine is 27.3%.
[0047] Example 3
[0048] Dissolve 20.00 g of isophthalic acid in 46.67 g of cyclopentyl methyl ether (the mass fraction of isophthalic acid in the solution is 30%), add 40.93 g of ammonia water (the mass fraction of ammonia water is 25%), mix evenly and then add it to a high-pressure reactor. Add 2.4 g of Raney nickel catalyst to the reactor. After repeatedly displacing the gas in the high-pressure reactor with nitrogen 3 times, introduce hydrogen, and after repeatedly displacing 3 times, increase the pressure to 1 Mpa with hydrogen; within 1.2 hours, raise the temperature of the reactor from 35 °C to 170 °C, with a heating rate of 1.9 °C / min, and then react at 170 °C for 10 hours. In this reaction, the molar ratio of isophthalic acid to ammonia water is 1:5, and the mass ratio of isophthalic acid to the catalyst Raney nickel is 100:12. After the reaction is completed, take out the reaction solution for testing. The conversion rate of isophthalic acid is analyzed to be 99.9%, and the selectivity of m-xylenediamine is 25.6%.
[0049] Example 4
[0050] Dissolve 20.00 g of adipic acid in 46.67 g of cyclopentyl methyl ether (the mass fraction of adipic acid in the solution is 30%), add 60.49 g of ammonia water (the mass fraction of ammonia water is 25%), mix evenly and then add it to a high-pressure reactor. Add 2.6 g of Raney nickel catalyst to the reactor. After repeatedly displacing the gas in the high-pressure reactor with nitrogen 3 times, introduce hydrogen, and after repeatedly displacing 3 times, increase the pressure to 1 Mpa with hydrogen; within 1.2 hours, raise the temperature of the reactor from 35 °C to 170 °C, with a heating rate of 1.9 °C / min, and then react at 170 °C for 13 hours. In this reaction, the molar ratio of adipic acid to ammonia water is 1:6.5, and the mass ratio of adipic acid to the catalyst Raney nickel is 100:13. After the reaction is completed, take out the reaction solution for testing. The conversion rate of adipic acid is analyzed to be 99.9%, and the selectivity of hexamethylenediamine is 17.2%.
[0051] Example 5
[0052] Dissolve 20.00 g of adipic acid in 46.67 g of cyclopentyl methyl ether (the mass fraction of adipic acid in the solution is 30%), add 37.22 g of ammonia water (the mass fraction of ammonia water is 25%), mix evenly and then add it to a high-pressure reactor. Add 0.8 g of Raney nickel catalyst to the reactor. After repeatedly displacing the gas in the high-pressure reactor with nitrogen 3 times, introduce hydrogen, and after repeatedly displacing 3 times, increase the pressure to 1 Mpa with hydrogen; within 1.2 hours, raise the temperature of the reactor from 35 °C to 170 °C, with a heating rate of 1.9 °C / min, and then react at 170 °C for 13 hours. In this reaction, the molar ratio of adipic acid to ammonia water is 1:4, and the mass ratio of adipic acid to the catalyst Raney nickel is 100:4. After the reaction is completed, take out the reaction solution for testing. The conversion rate of adipic acid is analyzed to be 73.6%, and the selectivity of hexamethylenediamine is 13.4%.
[0053] Example 6
[0054] Dissolve 20.00 g of adipic acid in 46.67 g of cyclopentyl methyl ether (the mass fraction of adipic acid is 30%), add 37.22 g of ammonia water (the mass fraction of ammonia water is 25%), mix evenly and then add it to a high-pressure reactor. Add 2.6 g of Raney nickel catalyst to the reactor. After repeatedly displacing the gas in the high-pressure reactor with nitrogen 3 times, introduce hydrogen gas. After repeatedly displacing 3 times, increase the pressure to 1 Mpa with hydrogen gas; within 1.7 hours, raise the temperature of the reactor from 35 °C to 230 °C, with a heating rate of 1.9 °C / min, and then react at 230 °C for 13 hours. In this reaction, the molar ratio of adipic acid to ammonia water is 1:4, and the mass ratio of adipic acid to the Raney nickel catalyst is 100:13. After the reaction is completed, take out the reaction solution for testing. The conversion rate of adipic acid is analyzed to be 99.9%, and the selectivity of hexamethylenediamine is 10.1%.
[0055] Comparative Example 1
[0056] Dissolve 20.00 g of adipic acid in 46.67 g of cyclopentyl methyl ether (the mass fraction of adipic acid in the solution is 30%), add 37.22 g of ammonia water (the mass fraction of ammonia water is 25%), mix evenly and then add it to a high-pressure reactor. Add 2.6 g of Ru / C catalyst to the reactor. After repeatedly displacing the gas in the high-pressure reactor with nitrogen 3 times, introduce hydrogen gas. After repeatedly displacing 3 times, increase the pressure to 1 Mpa with hydrogen gas. Within 1.2 hours, raise the temperature of the reactor from 35 °C to 170 °C, with a heating rate of 1.9 °C / min, and then react at 170 °C for 13 hours. In this reaction, the molar ratio of adipic acid to ammonia water is 1:4, and the mass ratio of adipic acid to the Ru / C catalyst is 100:13. After the reaction is completed, take out the reaction solution for testing. The conversion rate of adipic acid is analyzed to be 99.9%, and the selectivity of hexamethylenediamine is 0.
[0057] Table 1
[0058]
[0059]
[0060] According to the data in Table 1, the method of the present disclosure has a simple process flow, no highly toxic intermediate products, low production costs, high production efficiency, high product selectivity, and is easy to industrialize. By comparing Example 1 and Example 4, it can be seen that within the preferred molar ratio range of the dicarboxylic acid to the ammonia source in the present disclosure, the selectivity of the product is higher. By comparing Example 1 and Example 5, it can be seen that within the preferred mass ratio range of the dicarboxylic acid to the catalyst in the present disclosure, the conversion rate of the dicarboxylic acid is higher and the selectivity of the product is higher. By comparing Example 1 and Example 6, it can be seen that within the preferred reaction temperature T range in the present disclosure, the selectivity of the product is higher.
[0061] 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 fall within the protection scope of the present disclosure.
[0062] In addition, it should be noted that, among the various specific technical features described in the above specific embodiments, they can be combined in any suitable manner without conflict. To avoid unnecessary repetition, the present disclosure will not separately describe various possible combination manners.
[0063] Furthermore, 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 a dibasic primary amine from a dibasic carboxylic acid, characterized in that, The method includes: Bringing a dicarboxylic acid, an ammonia source, a catalyst and a solvent into contact in a closed container and carrying out a reaction under a hydrogen atmosphere; wherein, the dicarboxylic acid is as shown in formula (1), R1 is selected from one of an alkylene group having 2 to 12 carbon atoms and a five-membered heterocyclic group; the ammonia source is ammonia water or an ammonium salt; the catalyst is Raney nickel and / or Raney cobalt.
2. The method according to claim 1, wherein The alkylene group is selected from one or more of ethylene, butylene, hexylene, octylene and phenylene; the five-membered heterocyclic group is selected from one or more of furanylene, tetrahydrofuranylene and thiophenylene.
3. The method according to claim 1, wherein, The dicarboxylic acid is selected from one or more of succinic acid, adipic acid, suberic acid, sebacic acid, 2,5-furandicarboxylic acid, 2,5-tetrahydrofurandicarboxylic acid, 2,5-thiophenedicarboxylic acid, isophthalic acid and terephthalic acid.
4. The method according to claim 1, wherein The method includes mixing the dicarboxylic acid with the solvent to form a dicarboxylic acid solution, and then bringing it into contact with the ammonia source and the catalyst to carry out the reaction; the mass fraction of the dicarboxylic acid solution is 20-40%, preferably 20-30%.
5. The method according to claim 1, wherein The ammonium salt is selected from one or more of ammonium chloride, ammonium sulfate, ammonium bromide, ammonium carbonate, ammonium bicarbonate, ammonium oxalate and ammonium acetate, preferably one or more of ammonium chloride, ammonium sulfate, ammonium bromide or ammonium oxalate; The mass fraction of the ammonia water is 22%-30%.
6. The method according to claim 1, wherein The molar ratio of the dicarboxylic acid to the ammonia source is 1:2-7, preferably 1:3-5; the mass ratio of the dicarboxylic acid to the catalyst is 100:2-15, preferably 100:6-13.
7. The method according to claim 1, wherein The conditions of the reaction include a reaction temperature of 120-250°C, preferably 160-200°C; a reaction time of 5-50 h, preferably 5-25 h; the pressure of the hydrogen is 0.1-2 Mpa, preferably 0.5-1 Mpa.
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 0-5°C / min; the rate is preferably 0.5-2°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.