A process for the preparation of dihydroxypropylhydroxylamine

Abstract

The application discloses a method for preparing dihydroxypropyl hydroxylamine, which comprises the following steps: S1, mixing a hydrogen peroxide solution and an anhydride to obtain an oxidizing solution; S2, mixing dihydroxypropyl amine with a solvent, and adding the oxidizing solution in S1 to perform an oxidation reaction; and S3, contacting the obtained oxidation product with an extraction solvent to perform solvent extraction, obtaining an extraction liquid which is the anhydride and the organic solvent, and obtaining a raffinate which is the hydrophilic solvent and the dihydroxypropyl hydroxylamine, wherein the raffinate is subjected to vacuum distillation to remove the hydrophilic solvent, and then dihydroxypropyl hydroxylamine product is obtained. The method uses the anhydride and the hydrogen peroxide as oxidants, and uses dihydroxypropyl amine as raw material, and only one step is needed to prepare the dihydroxypropyl hydroxylamine compound, the raw material is cheap and easy to obtain, the reaction yield is high, the product is easy to purify, and the dihydroxypropyl hydroxylamine product obtained is high in purity.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic synthesis. Specifically, it relates to a preparation method of dihydroxypropyl hydroxylamine compound. BACKGROUND

[0002] Dihydroxypropyl hydroxylamine is an important fine chemical, usually referred to as HPHA, which is widely used in styrene polymerization inhibition field due to its very good polymerization inhibition effect on olefins. In addition, due to its strong reducing property, it can be used to produce antioxidants and as a boiler descaling agent, etc.

[0003] At present, there are few reports on the synthesis method of dihydroxypropyl hydroxylamine. CN106957240A discloses a method for preparing hydroxypropyl hydroxylamine. First, free alkyl hydroxylamine is generated by reacting substituted hydroxylamine with lye, and then propylene oxide is added to the above solution to generate dihydroxypropyl hydroxylamine. Since the free hydroxylamine generated in the first step is unstable, it needs to be carried out in an ice water bath. However, the reaction between hydroxylamine salt and lye will release a large amount of heat, which may cause the decomposition of hydroxylamine and reduce the yield. The reaction temperature of propylene oxide is about 20℃, which needs to be heated, and may also cause certain loss of hydroxylamine. US6028225A discloses a method for directly synthesizing dihydroxypropyl hydroxylamine by using free hydroxylamine and propylene oxide. The raw materials used in this method are not stable enough and are prone to decomposition, which is not convenient for storage. CN112159333A discloses an improved method, i.e. mixing propylene oxide and hydroxylamine salt in a solvent in advance, then adding lye dropwise, which can complete the two-step reaction at one time, avoid the generation and decomposition of free hydroxylamine, and improve the safety of production and the yield of product. However, the neutralization process of hydroxylamine hydrochloride and lye will inevitably produce hydrochloride, which is not only difficult to separate from the raw materials, but also causes the discharge of salt-containing wastewater. The raw materials used in the above methods are hydroxylamine salt or hydroxylamine, which have high cost and may cause the residual of metal salt.

[0004] Therefore, how to provide a dihydroxypropyl hydroxylamine preparation method with low cost, high yield and easy product separation has become a problem to be solved in the field. SUMMARY

[0005] The technical problem to be solved by the present application is to provide a method for preparing dihydroxypropyl hydroxylamine.

[0006] The method for preparing dihydroxypropyl hydroxylamine provided by the present application comprises the following steps:

[0007] S1, mixing hydrogen peroxide solution and acid anhydride to obtain an oxidation solution;

[0008] S2, mixing dihydroxypropyl amine with a solvent, and adding the oxidation solution of S1 to perform an oxidation reaction to obtain an oxidation product;

[0009] S3, the obtained oxidation product is contacted with an extraction solvent to perform solvent extraction, the obtained extraction liquid is anhydride and organic solvent, the obtained raffinate is hydrophilic solvent and dihydroxypropyl hydroxylamine, and the raffinate is subjected to vacuum distillation to remove the hydrophilic solvent to obtain the dihydroxypropyl hydroxylamine product.

[0010] The method for preparing dihydroxypropyl hydroxylamine provided by the application has the following advantages:

[0011] The application uses anhydride and hydrogen peroxide as an oxidant, and dihydroxypropyl amine as a raw material, and only one step is needed to prepare dihydroxypropyl hydroxylamine compound. The raw material is cheap and easy to obtain, the reaction yield is high, the product is easy to purify, and the obtained dihydroxypropyl hydroxylamine product has high purity. As can be seen from the examples, the purity of the prepared dihydroxypropyl hydroxylamine product can reach 95 wt%. DETAILED DESCRIPTION

[0012] The technical solutions of the application are described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the application, and are not used to limit the application.

[0013] In a first aspect, the application provides a method for preparing dihydroxypropyl hydroxylamine, comprising the following steps:

[0014] S1, mixing hydrogen peroxide solution and anhydride to obtain an oxidation liquid;

[0015] S2, mixing dihydroxypropyl amine and a solvent, and adding the oxidation liquid of S1 to perform oxidation reaction to obtain an oxidation product;

[0016] S3, contacting the oxidation product with an extraction solvent to perform solvent extraction, the obtained extraction liquid is anhydride and organic solvent, the obtained raffinate is hydrophilic solvent and dihydroxypropyl hydroxylamine, and the raffinate is subjected to vacuum distillation to remove the hydrophilic solvent to obtain the dihydroxypropyl hydroxylamine product.

[0017] The chemical structural formula of the dihydroxypropyl hydroxylamine compound is:

[0018]

[0019] In the method provided by the application, in S1, the anhydride is an organic carboxylic anhydride, which is selected from one or more of chain carboxylic anhydride and ring-forming carboxylic anhydride. Preferably, the anhydride is selected from one or more of chain carboxylic anhydride containing 2-6 carbon atoms and ring-forming carboxylic anhydride containing 4-8 carbon atoms. More preferably, the anhydride is selected from one or more of acetic anhydride, propionic anhydride, butyric anhydride, succinic anhydride, glutaric anhydride and phthalic anhydride.

[0020] In the method, in S1, the hydrogen peroxide solution is a 1-70% by mass hydrogen peroxide solution; preferably, the hydrogen peroxide solution is a 25-50% by mass hydrogen peroxide solution.

[0021] In S1, the molar ratio of the hydrogen peroxide to the acid anhydride is 1-10:1; preferably, the molar ratio of the hydrogen peroxide to the acid anhydride is 2-4:1.

[0022] In the method, in S1, the hydrogen peroxide solution and the acid anhydride are mixed uniformly at 50-140°C; preferably, the hydrogen peroxide solution and the acid anhydride are mixed uniformly at 70-115°C.

[0023] In the method, the amount of the hydrogen peroxide solution added is such that the molar ratio of the hydrogen peroxide to the dihydroxypropylamine is 1-10:1; preferably, the molar ratio of the hydrogen peroxide to the dihydroxypropylamine is 2-5:1.

[0024] In the method, in S2, the solvent is selected from one or more of water, alcohols, alkanes and aromatic hydrocarbons; preferably, the solvent is selected from one or more of water, aliphatic alcohols or cycloalkyl alcohols containing 1-6 carbon atoms, and alkanes or aromatic hydrocarbons containing 5-9 carbon atoms; more preferably, the solvent is selected from one or more of water, methanol, ethanol, propanol, n-butanol, isobutanol, tert-butanol, tert-amyl alcohol and cyclohexanol.

[0025] In the method, in S2, the mass ratio of the solvent to the dihydroxypropylamine is 0.5-25:1, preferably 1-3:1.

[0026] In the method, in S2, the dihydroxypropylamine and the solvent are slowly added to the oxidation solution obtained in S1 within 1-60 min; preferably, the dihydroxypropylamine and the solvent are added within 20-40 min.

[0027] In S2, the reaction time is 1-10 h; preferably, the reaction time is 1.5-5 h.

[0028] In the method, after S2, the main components of the oxidation product obtained are dihydroxypropylhydroxylamine, dihydroxypropylamine, acid anhydride, water and solvent, and the target product needs to be further separated; the oxidation product obtained in S2 is contacted with an extraction solvent to perform solvent extraction, the obtained extraction liquid is acid anhydride and organic solvent, and the obtained raffinate is dihydroxypropylhydroxylamine, hydrophilic solvent and unreacted dihydroxypropylamine; the raffinate is subjected to vacuum distillation to remove water to obtain dihydroxypropylhydroxylamine product.

[0029] In S3, the extraction solvent is selected from one or more of alcohols, nitriles, alkanes, ethers and aromatic hydrocarbons; preferably, the extraction solvent is selected from one or more of alkanes or aromatic hydrocarbons containing 5-9 carbon atoms, and aliphatic or ether containing 2-6 carbon atoms, and halogenated alkanes containing 1-3 carbon atoms; more preferably, the extraction solvent is selected from one or more of benzene, toluene, chloroform and carbon tetrachloride.

[0030] In S3, the mass ratio of the extraction solvent to the dihydroxypropylamine is 1-50:1; preferably, the mass ratio of the extraction solvent to the dihydroxypropylamine is 5-20:1.

[0031] In the method provided by the present application, in S3, the obtained oxidation product is subjected to solvent extraction to obtain a raffinate containing dihydroxypropyl hydroxylamine, a hydrophilic solvent and unreacted dihydroxypropylamine, wherein the hydrophilic solvent refers to water and water-miscible organic solvents, and the hydrophilic solvent is removed by vacuum distillation to obtain dihydroxypropyl hydroxylamine product.

[0032] In S3, the vacuum distillation is carried out at a pressure of 10-100 kPa and a temperature of 70-180℃.

[0033] In the method provided by the present application, preferably, the reaction kettle used is an isothermal reactor with stirring equipment.

[0034] The present application uses anhydride and hydrogen peroxide as oxidant, and dihydroxypropylamine as raw material, and only one step reaction is needed to prepare dihydroxypropyl hydroxylamine compound, and the subsequent separation is easy, and high purity product can be obtained.

[0035] The method of the present application is further illustrated by examples below, but the present application is not limited in any way by the examples.

[0036] In the examples and comparative examples:

[0037] The reagents used are commercially available chemical reagents.

[0038] The yield is the mass of the dihydroxypropyl hydroxylamine product actually obtained / the mass of the dihydroxypropyl hydroxylamine product that can be obtained theoretically x 100%;

[0039] The purity of the product is the mass of dihydroxypropyl hydroxylamine in the actual product / the total mass of the product x 100%.

[0040] Example 1

[0041] In the reactor was added phthalic anhydride 17.77 g, 30 wt% hydrogen peroxide 34.02 g, heated to 95 °C and stirred. The dihydroxypropylamine 13.32 g was mixed with water 13.32 g and slowly added to the reactor, controlling the addition time in 20 min, the reaction time was 1.5 h.

[0042] After the reaction was completed, it was cooled to room temperature, and the crude product was extracted with benzene 120 g as the extraction solvent, and the raffinate phase was distilled under reduced pressure to remove water to obtain dihydroxypropyl hydroxylamine product 13.43 g, the yield was 88.1 wt%, the amount of dihydroxypropyl hydroxylamine in the product was analyzed, and the purity of the product was calculated to be 97.9 wt%.

[0043] Example 2

[0044] In the reactor was added acetic anhydride 10.21 g, 35 wt% hydrogen peroxide 19.44 g, heated to 75 °C and stirred. The dihydroxypropylamine 13.32 g was mixed with ethanol 23.97 g and slowly added to the reactor, controlling the addition time in 30 min, the reaction time was 4 h.

[0045] After the reaction was completed, it was cooled to room temperature, and the crude product was extracted with benzene 150 g as the extraction solvent, and the raffinate phase was distilled under reduced pressure to remove water and ethanol to obtain dihydroxypropyl hydroxylamine compound 12.82 g, the yield was 83.1 wt%, the amount of dihydroxypropyl hydroxylamine in the product was analyzed, and the purity of the product was calculated to be 96.7 wt%.

[0046] Example 3

[0047] In the reactor was added succinic anhydride 23.02 g, 40 wt% hydrogen peroxide 38.27 g, heated to 80 °C and stirred. The dihydroxypropylamine 13.32 g was mixed with tert-butyl alcohol 19.98 g and slowly added to the reactor, controlling the addition time in 25 min, the reaction time was 2 h.

[0048] After the reaction was completed, it was cooled to room temperature, and the crude product was extracted with benzene 150 g as the extraction solvent, and the raffinate phase was distilled under reduced pressure to remove water and ethanol to obtain dihydroxypropyl hydroxylamine compound 12.82 g, the yield was 83.1 wt%, the amount of dihydroxypropyl hydroxylamine in the product was analyzed, and the purity of the product was calculated to be 96.7 wt%.

[0049] Example 4

[0050] In the reactor was added glutaric anhydride 22.82 g, 45 wt% hydrogen peroxide 30.24 g, heated to 100 °C and stirred. The dihydroxypropylamine 13.32 g was mixed with isobutyl alcohol 39.96 g and slowly added to the reactor, controlling the addition time in 40 min, the reaction time was 5 h.

[0051] After the reaction is completed, the temperature is lowered to room temperature, and the crude product is extracted with 200 g of chloroform as the extraction solvent. The raffinate is distilled under reduced pressure to remove water and a small amount of isobutyl alcohol, and 12.71 g of dihydroxypropyl hydroxylamine compound is obtained at a yield of 80.7 wt%. The amount of dihydroxypropyl hydroxylamine in the product is analyzed, and the purity of the product is calculated to be 94.8 wt%.

[0052] Example 5

[0053] In a reactor, 22.22 g of phthalic anhydride is added, 47.62 g of 30 wt% hydrogen peroxide is added, and the temperature is raised to 105°C while stirring. 13.32 g of dihydroxypropyl amine is mixed with 17.31 g of n-butanol, and the mixture is slowly added to the reactor, with the addition time controlled to be 25 min, and the reaction time is 2.5 h.

[0054] After the reaction is completed, the temperature is lowered to room temperature, and the crude product is extracted with 150 g of toluene. The raffinate is distilled under reduced pressure to remove water and a small amount of n-butanol, and 13.59 g of dihydroxypropyl hydroxylamine compound is obtained at a yield of 88.7 wt%. The amount of dihydroxypropyl hydroxylamine in the product is analyzed, and the purity of the product is calculated to be 97.3 wt%.

[0055] Example 6

[0056] In a reactor, 17.01 g of succinic anhydride is added, 42.52 g of 40 wt% hydrogen peroxide is added, and the temperature is raised to 90°C while stirring. 13.32 g of dihydroxypropyl amine is mixed with 15.98 g of water, and the mixture is slowly added to the reactor, with the addition time controlled to be 20 min, and the reaction time is 3 h.

[0057] After the reaction is completed, the temperature is lowered to room temperature, and the crude product is extracted with 150 g of carbon tetrachloride. The raffinate is distilled under reduced pressure to remove water, and 12.96 g of dihydroxypropyl hydroxylamine compound is obtained at a yield of 83.6 wt%. The amount of dihydroxypropyl hydroxylamine in the product is analyzed, and the purity of the product is calculated to be 96.3 wt%.

[0058] Comparative Example 1

[0059] In the reactor was added 6.95 g of hydroxylamine hydrochloride, 10 g of deionized water, and after complete mixing and dissolution, 17.4 g of propylene oxide was added; the reaction temperature was controlled at 0°C, and stirring was maintained; a 31 wt% aqueous NaOH solution was prepared, and 12.89 g was added dropwise to the reactor, of which 4.0 g was NaOH. The dropwise addition time was 2 h, and after the dropwise addition was complete, the temperature and stirring were maintained for 10 h. 0.05 mass% of the reaction product methyltrioctylammonium chloride was added, in an amount of 0.02 g, and two extractions were performed using dichloromethane, each in an amount of 20 mL. The extracted phases were combined, and the dichloromethane solvent was removed by distillation under reduced pressure to obtain 13.16 g of hydroxypropylhydroxylamine solid, with a yield of 84.0 wt%. The amount of dihydroxypropylhydroxylamine in the product was analyzed, and the product purity was calculated to be 95.1 wt%.

Claims

1. A process for the preparation of dihydroxypropylhydroxylamine, characterized in that, The method comprises the following steps: S1, mixing hydrogen peroxide solution and acid anhydride at 50-140℃ to obtain an oxidation solution; S2, mixing dihydroxypropylamine with a solvent, and adding the oxidation solution in S1 to perform oxidation reaction to obtain an oxidation product; S3, contacting the obtained oxidation product with an extraction solvent to perform solvent extraction, obtaining an extraction liquid of acid anhydride and organic solvent, and an extraction residue of hydrophilic solvent and dihydroxypropylhydroxylamine, and distilling the extraction residue under reduced pressure to remove the hydrophilic solvent and obtain dihydroxypropylhydroxylamine product.

2. The process for the preparation of dihydroxypropylhydroxylamine according to claim 1, characterized in that, The acid anhydride in S1 is organic carboxylic anhydride, which is selected from one or more of chain carboxylic anhydride and ring carboxylic anhydride.

3. The process for the preparation of dihydroxypropylhydroxylamine according to claim 2, characterized in that, The acid anhydride is selected from one or more of chain carboxylic anhydride with 2-6 carbon atoms and ring carboxylic anhydride with 4-8 carbon atoms.

4. The process for the preparation of dihydroxypropylhydroxylamine according to claim 3, characterized in that, The acid anhydride is selected from one or more of acetic anhydride, propionic anhydride, butyric anhydride, succinic anhydride, glutaric anhydride and phthalic anhydride.

5. Process for the preparation of dihydroxypropylhydroxylamine according to any one of claims 1 to 4, characterized in that, In S1, the molar ratio of hydrogen peroxide to acid anhydride is 1-10:

1.

6. The process for the preparation of dihydroxypropylhydroxylamine according to claim 5, characterized in that, The molar ratio of hydrogen peroxide to acid anhydride is 2-4:

1.

7. The process for the preparation of dihydroxypropylhydroxylamine according to claim 5, characterized in that, In S1, the mass concentration of hydrogen peroxide solution is 1%-70%.

8. The process for the preparation of dihydroxypropylhydroxylamine according to claim 7, characterized in that, The mass concentration of hydrogen peroxide solution is 25%-50%.

9. The process for the preparation of dihydroxypropylhydroxylamine according to any one of claims 1 to 4, characterized in that, In S1, the hydrogen peroxide solution and acid anhydride are mixed uniformly at 70-115℃.

10. The process for the preparation of dihydroxypropylhydroxylamine according to any one of claims 1 to 4, characterized in that, The molar ratio of hydrogen peroxide to dihydroxypropylamine is 1-10:

1.

11. The process for the preparation of dihydroxypropylhydroxylamine according to claim 10, characterized in that, The molar ratio of hydrogen peroxide to dihydroxypropylamine is 2-5:

1.

12. The process for the preparation of dihydroxypropylhydroxylamine according to any one of claims 1 to 4, characterized in that, The solvent in S2 is selected from one or more of water, alcohol, alkane and aromatic hydrocarbon solvent.

13. The process for the preparation of dihydroxypropylhydroxylamine according to claim 12, characterized in that, The solvent is selected from one or more of water, aliphatic alcohol with 1-6 carbon atoms or cycloalkyl alcohol, and alkane or aromatic hydrocarbon with 5-9 carbon atoms.

14. The process for the preparation of dihydroxypropylhydroxylamine according to claim 13, characterized in that, The solvent is selected from one or more of water, methanol, ethanol, propanol, n-butanol, isobutanol, tert-butanol, tert-amyl alcohol and cyclohexanol.

15. The method for preparing dihydroxypropyl hydroxylamine compound according to claim 12, characterized in that, In S2, the mass ratio of the solvent to dihydroxypropylamine is 0.5-25:

1.

16. The method for preparing dihydroxypropyl hydroxylamine compound according to claim 15, characterized in that, In S2, the mass ratio of the solvent to dihydroxypropylamine is 1-3:

1.

17. The process for the preparation of dihydroxypropylhydroxylamine according to any one of claims 1 to 4, characterized in that, In S2, the dihydroxypropylamine and solvent are slowly added to the oxidation solution within 1-60 min, and the reaction time is 1-10 h.

18. The process for the preparation of dihydroxypropylhydroxylamine according to claim 17, characterized in that, The dihydroxypropylamine and solvent are slowly added to the oxidation solution within 20-40 min.

19. The process for the preparation of dihydroxypropylhydroxylamine according to claim 17, characterized in that, The reaction time is 1.5-5 h.

20. The process for the preparation of dihydroxypropylhydroxylamine according to any one of claims 1 to 4, characterized in that, The extraction solvent in S3 is selected from one or more of alcohol, nitrile, alkane, ether and aromatic hydrocarbon organic solvent.

21. The process for the preparation of dihydroxypropylhydroxylamine according to claim 20, characterized in that, The extraction solvent in S3 is selected from one or more of alkane or aromatic hydrocarbon with 5-9 carbon atoms, aliphatic or ether with 2-6 carbon atoms, and halogenated alkane with 1-3 carbon atoms.

22. The process for the preparation of dihydroxypropylhydroxylamine according to claim 21, characterized in that, The extraction solvent in S3 is selected from one or more of benzene, toluene, chloroform and carbon tetrachloride.

23. The process for preparing dihydroxypropylhydroxylamine according to claim 20, characterized in that, In S3, the mass ratio of the extraction solvent to dihydroxypropylamine is 1-50:

1.

24. The process for preparing dihydroxypropylhydroxylamine according to claim 23, characterized in that, In S3, the mass ratio of the extraction solvent to dihydroxypropylamine is 5-20:

1.

25. The process for preparing dihydroxypropylhydroxylamine according to claim 20, characterized in that, In S3, the operation conditions of the reduced pressure distillation are as follows: pressure is 10-100 kPa, and temperature is 70-180℃.

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