Method for preparing 1, 4-butanediamine from butanedinitrile

Abstract

The invention relates to a method for preparing 1, 4-butanediamine from succinonitrile, which comprises the following steps: S1, adding succinonitrile, Raney nickel, alkali and an alcohol solvent into a system under a nitrogen condition, and heating to 30-100 DEG C; s2, adding sodium borohydride into the system, and carrying out gas phase detection on the reaction process; after the reaction is completed, stopping the reaction, filtering and rectifying; and when the GC purity of the distillate reaches 99% or above, receiving the product. The invention provides a scheme for preparing the 1, 4-butanediamine, which is mild in reaction condition, easy to operate and relatively low in cost, and has a great industrial application prospect.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of butanediamine synthesis, in particular to a method for preparing 1,4-butanediamine from butanedinitrile. BACKGROUND

[0002] 1,4-butanediamine, also known as putrescine, has a molecular formula of H2N(CH2)4NH2(1,4-diaminobutane), and is a white crystal at room temperature, with strong irritating odor and corrosive property. As an important organic synthesis intermediate and biochemical precursor, 1,4-butanediamine is widely used in the fields of engineering plastics, surfactants, medicines and agricultural chemicals, etc. Among them, the most important industrial use of 1,4-butanediamine is to produce polyamide materials, i.e. aliphatic nylon fiber PA46. PA46 is well-known for its high melting point, high crystallinity, high heat resistance and high mechanical strength, and is widely used in the fields of textiles, mechanical chemical industry, electronics and electrical appliances, automobile manufacturing, etc. The development of high-efficiency and high-selectivity preparation method of 1,4-butanediamine has great value due to its wide market demand and increasing potential demand year by year.

[0003] Currently, the industrial production of 1,4-butanediamine mainly relies on the hydrogenation reduction of succinonitrile, but this method has many problems: such as harsh reaction conditions, serious environmental pollution, high energy consumption, etc. US2006 / 0122433A1 reports the catalytic hydrogenation of succinonitrile, the catalyst is Cr / Fe doped Raney nickel or Raney cobalt catalyst, continuous kettle reaction is adopted, the reaction temperature is 60-100℃, the reaction pressure is 8-90MPa, and the qualified 1,4-butanediamine can be prepared with a selectivity of more than 90%. With PtO2 as the catalyst and acetic acid as the solvent, the hydrogen reduction of succinonitrile can also be realized at room temperature and normal pressure, and 1,4-butanediamine can be obtained in high yield (Journal of the Chemical Society. Perkin transactions I, 1986, 983-988), but the catalyst PtO2 used in this reaction is expensive and the reaction time is long (72 hours). Ni-MgO supported catalyst system can also realize the hydrogenation reduction of succinonitrile to 1,4-butanediamine (Journal of Catalysis, 2001, 197, 210-219), but the selectivity of 1,4-butanediamine in the obtained product is very low (not more than 25%), which does not have the basis for industrialization. As an important reducing agent, borane can be widely used in the reduction reaction of carboxylic acid, amide, ketone and other functional groups in organic synthesis, and its reduction has the characteristics of high selectivity and mild conditions. With trifluoroacetic acid as the promoter and tetrahydrofuran as the solvent, sodium borohydride (NaBH4) or borane can catalyze the reduction of succinonitrile, and the target product 1,4-butanediamine can be obtained after neutralization operation (Journal of Organic Chemistry, 1991, 56, 3467-3468; Chemical and Pharmaceutical Bulletin, 1995, 43, 2001-2004). However, this method has many operation steps and low yield (the highest is 57%), which has great limitations for industrialization. It should be noted that 1,4-butanediamine is also a kind of biological amine, which can be generated in the metabolic process of basic amino acids (lysine, ornithine or arginine), therefore, theoretically, the preparation of the target product can be realized by biotechnological modification of microorganisms and construction of cell factories, which can meet the realistic requirements of environmental protection and sustainable development. However, so far, the academic and industrial circles have not found suitable strains to realize the efficient production of 1,4-butanediamine, and the currently reliable highest report is 24.2g / L (Biotechnology & Bioengineering, 2010, 104, 651-662), which does not have the possibility of industrialization. In view of the rapid development of biological synthesis method, it has certain potential in the industrial production of 1,4-butanediamine. SUMMARY

[0004] The present application is to solve the existing problems, aims at providing a method for preparing 1,4-butanediamine from succinonitrile. In order to achieve the above-mentioned purpose, the technical scheme adopted by the present application comprises:

[0005] S1, under the condition of nitrogen, adding succinonitrile, Raney nickel, base and alcohol solvent into a flask, and heating to 30-100℃;

[0006] S2, adding sodium borohydride into the above system in batches, and detecting the progress of the reaction by gas phase; when the reaction is completed, stopping the reaction, filtering with diatomite, and rectifying; when the purity of the distillate reaches more than 99% by GC, receiving the product. The reaction equation of the foregoing scheme is as follows:

[0007]

[0008] Preferably, in S1, the target temperature is 50-70℃.

[0009] Preferably, in S1, the mass ratio of Raney nickel to succinonitrile is 1%-20%, or 1%-10%, or 5%-10%. The Raney nickel used in the reaction is a ternary and quaternary catalyst containing Fe and Mo and other impurity elements.

[0010] Preferably, in S1, the base is sodium hydroxide or potassium hydroxide.

[0011] Preferably, in S1, the mass ratio of base to Raney nickel is 5%-30%, or 5%-20%, or 8%-15%. Preferably, in S1, the alcohol solvent is methanol, ethanol, isopropanol, n-butanol or isobutanol.

[0012] Preferably, in S1, the mass ratio of alcohol solvent to succinonitrile is 1:1-20:1, or 4:1-10:1.

[0013] Preferably, in S2, the molar ratio of sodium borohydride to succinonitrile is 1:1-10:1, or 2:1-3:1. Preferably, in S2, the reduction reaction time is 0.5-10 hours, or 1-5 hours, or 2-4 hours. Preferably, in S2, borane and its complex are added into the system for reaction instead of sodium borohydride. Preferably, the complex is borane-ether, borane-tetrahydrofuran, borane-dimethyl sulfide, borane-pyridine, borane-diisopropylamine or borane-N,N-diethyl aniline, etc. Under the optimal conditions, almost all reactions can obtain similar reduction results (85%-95%).

[0014] Compared with the prior art, the application uses butanedinitrile as raw material, uses cheap Raney nickel as catalyst, and selects sodium borohydride as hydrogen source, and develops a 1,4-butanediamine synthesis method with mild conditions, extremely high yield and industrial application prospect. 1,4-butanediamine can be obtained under relatively mild conditions with high yield. The scheme of the application requires shorter time and has high total yield (75-95%), and can solve the problems of large reaction pressure, many by-products and high cost in the prior art, and has high industrial production prospect.

[0015] It needs to be emphasized that the existing literature discloses that the amorphous nickel (different from the common Raney nickel) and sodium borohydride system can reduce part of nitrile compounds (Organic & Biomolecular Chemistry, 2012, 10, 663-670). Through a large amount of screening of catalysts, it is found that the ternary and quaternary Raney nickel containing Fe and Mo and other impurity elements can promote the reduction of butanedinitrile by sodium borohydride with relatively higher activity, and the target product 1,4-butanediamine is obtained with high yield.

[0016] Compared with the scheme in the prior art using trifluoroacetic acid as a promoter, the Raney nickel used in the application is more efficient and has less dosage, and can be reused; the final product is easier to purify (reducing the neutralization process), and has lower cost. DETAILED DESCRIPTION

[0017] The above scheme is further described below in combination with specific examples, and the preferred embodiment of the application is described in detail as follows:

[0018] Example 1:

[0019] Butanedinitrile (800 g), Raney nickel (40 g) and sodium hydroxide (4 g) were added to a 10 L glass reactor containing 4 kg of anhydrous methanol, a vacuum pump and a nitrogen system were connected, and oxygen in the reaction system was removed. When the system was heated to 50 DEG C, 0.8 kg of sodium borohydride was added to the above system in batches, and the duration was about 2 hours. The feeding speed was controlled to ensure that the excess gas released could be stably discharged through the nitrogen system.

[0020] After the feeding was completed, the system was kept at 50 DEG C for 2 hours (GC showed that there was no raw material). The reaction was stopped, diatomite was filtered, and the filtrate was collected and rotary dried to obtain the crude product. 1,4-butanediamine with a GC purity of greater than 99% was obtained by rectification, and the yield was 91%.

[0021] The Raney nickel can be reused, and it still maintains the initial activity after 5 recycling verification.

[0022] Example 2:

[0023] Butanedinitrile (1590 g), Raney nickel (50 g) and sodium hydroxide (8 g) were added to a 20 L glass reactor containing 9 kg of anhydrous ethanol. A vacuum pump and nitrogen system were connected to remove oxygen from the reaction system. When the system was heated to 70 °C, 3.1 kg of sodium borohydride was added to the system in batches, and the duration was about 2 hours.

[0024] After the feeding was completed, the system was kept at 70 °C for 1.5 hours to continue the reaction (GC showed that there was no raw material). The reaction was stopped after cooling, and the filtrate was collected by diatomite filtration and rotary evaporation of the solvent to obtain the crude product. By rectification, 1,4-butanediamine with a GC purity of more than 99% was obtained, and the yield was 92%.

[0025] Example 3:

[0026] Butanedinitrile (800 g), Raney nickel (20 g) and potassium hydroxide (2 g) were added to a 10 L glass reactor containing 4 kg of anhydrous methanol. A vacuum pump and nitrogen system were connected to remove oxygen from the reaction system. When the system was heated to 60 °C, 1.5 kg of sodium borohydride was added to the system in batches, and the duration was about 2 hours.

[0027] After the feeding was completed, the system was kept at 60 °C for 3.5 hours to continue the reaction (GC showed that there was no raw material). The reaction was stopped after cooling, and the filtrate was collected by diatomite filtration and rotary evaporation of the solvent to obtain the crude product. By rectification, 1,4-butanediamine with a GC purity of more than 99% was obtained, and the yield was 84%.

[0028] Example 4:

[0029] Butanedinitrile (400 g), Raney nickel (20 g) and sodium hydroxide (2 g) were added to a 20 L glass reactor containing 2.5 kg of anhydrous methanol. A vacuum pump and nitrogen system were connected to remove oxygen from the reaction system. When the system was heated to 50 °C, 10 liters of 1 mol / L borane tetrahydrofuran solution was slowly added to the system by a peristaltic pump, and the duration was about 2 hours. Attention should be paid to the dropping speed to ensure that the borane precipitated and the excess gas released could be stably discharged through the nitrogen system.

[0030] After the feeding was completed, the system was kept at 50 °C for 2 hours to continue the reaction (GC showed that there was no raw material). The reaction was stopped after cooling, and the filtrate was collected by diatomite filtration and rotary evaporation of the solvent to obtain the crude product. By rectification, 1,4-butanediamine with a GC purity of more than 99% was obtained, and the yield was 90%.

[0031] The application provides a method for preparing 1,4-butanediamine from butanedinitrile, wherein butanedinitrile can be subjected to hydrogenation reaction at normal temperature and pressure under the action of a Raney nickel / sodium borohydride system, and 1,4-butanediamine is obtained at a high yield (75-95%). The application provides a mild reaction condition, easy operation and a low-cost solution for preparing 1,4-butanediamine, and has great industrial application prospect.

Claims

1. A method for preparing 1,4-butanediamine from succinate, characterized in that... include: S1, Under nitrogen atmosphere, succinic acid, Raney nickel, alkali and alcohol solvent are added to the system and heated to 30℃~100℃; S2, sodium borohydride is added to the above system, and the reaction progress is monitored in the gas phase; when the reaction is complete, the reaction is stopped, filtered, and distilled; when the GC purity of the distillate reaches 99% or more, the product is collected.

2. The method according to claim 1, characterized in that: In S1, the target temperature is 50-70℃.

3. The method according to claim 1, characterized in that: In S1, the mass ratio of Raney nickel to succinic anion is 1%–20%, or 1%–10%, or 5%–10%.

4. The method according to claim 1, characterized in that: In S1, the base is sodium hydroxide or potassium hydroxide.

5. The method according to claim 1 or 4, characterized in that: In S1, the mass ratio of alkali to Raney nickel is 5%-30%, or 5%-20%, or 8%-15%.

6. The method according to claim 1, characterized in that: In S1, the alcohol solvent is methanol, ethanol, isopropanol, n-butanol, or isobutanol.

7. The method according to claim 1 or 6, characterized in that: In S1, the mass ratio of alcohol solvent to succinic acid is 1:1-20:1, or 4:1-10:

1.

8. The method according to claim 1, characterized in that: In S2, the molar ratio of sodium borohydride to succinic acid is 1:1-10:1, or 2:1-3:

1.

9. The method according to claim 1, characterized in that: In S2, the reduction reaction time is 0.5-10 hours, or 1-5 hours, or 2-4 hours.

10. The method according to claim 1, characterized in that: In S2, borane and its complexes are added to the system to carry out the reaction; and / or, the complexes are borane-diethyl ether, borane-tetrahydrofuran, borane-dimethyl sulfide, borane-pyridine, borane-diisopropylamine, or borane-N,N-diethylaniline, etc.

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