CN113429299A - Method for purifying phenylenediamine - Google Patents
Method for purifying phenylenediamine Download PDFInfo
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- CN113429299A CN113429299A CN202110852526.2A CN202110852526A CN113429299A CN 113429299 A CN113429299 A CN 113429299A CN 202110852526 A CN202110852526 A CN 202110852526A CN 113429299 A CN113429299 A CN 113429299A
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- phenylenediamine
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/84—Purification
Abstract
The invention relates to the technical field of phenylenediamine purification, in particular to a method for purifying phenylenediamine, which comprises the steps of firstly dissolving phenylenediamine in a good solvent to form a solution, then mixing the solution of phenylenediamine with an antisolvent of phenylenediamine to generate crystals, carrying out a plurality of dissolving-crystallizing processes, and finally drying the obtained crystals to obtain a high-purity phenylenediamine product, wherein the method comprises the steps of mixing a phenylenediamine saturated solution and an antisolvent, selecting the solvent and controlling process conditions to obtain the phenylenediamine product with the purity of more than 99.80 percent with the yield of more than 83 percent, compared with other purification processes in the prior art, the method does not need special customized equipment, the purified phenylenediamine product is a high-white product, the whole process is rapid and simple, the energy consumption is low, the high-purity product can be obtained at normal temperature, and the used solvent can be recovered, the method has the advantages of low requirement on the purity of the crude product, wider application range and convenient operation, and can meet the requirement of industrialized production and manufacturing.
Description
Technical Field
The invention relates to the technical field of phenylenediamine purification, in particular to a method for purifying phenylenediamine.
Background
Phenylenediamine is an organic chemical intermediate with wide application, and is widely applied to dyes, pigments, high molecular polymers, rubber antioxidants, photo developers, antioxidants and the like. In general, the phenylenediamine product with lower purity has the characteristic of easy oxidative discoloration, so that the phenylenediamine product needs to be purified and refined.
The domestic traditional process adopts a casting body cooling method, but the product has the defects of poor quality, poor operating environment, low economic benefit and the like, the rectification process is another traditional process which is used more at present, and in the conventional rectification process used at present, for phenylenediamine systems with approximate boiling points, the product requirement of certain purity can be met only by needing higher theoretical plate number and reflux ratio, so the energy consumption of the rectification process of high-purity products is higher; in addition, the phenylenediamine purification method in the prior art also includes a solvent crystallization method, a melt crystallization method and a sublimation and desublimation crystallization method, for example, a solvent crystallization method adopting special customized equipment is disclosed in the Chinese patent CN 100358860C; chinese patent CN101250113B discloses a method of combining rectification with a molten crystalline phase; cao academic Congress et al describe a sublimation and desublimation crystallization method (research on p-phenylenediamine production process, applied chemical, 2002,31(3), 34).
In the method, the p-phenylenediamine crude product is applicable when the relative purity is high, and is not applicable to the crude product with low purity or has undesirable effect, and in addition, the method has the defects of high purification temperature and high energy consumption.
Disclosure of Invention
In order to solve the problems, the invention provides a method for purifying phenylenediamine, which has the advantages of simple process, easy operation and low energy consumption, and meets the requirements of industrial production and manufacturing.
The technical scheme adopted by the invention is as follows:
a method for purifying phenylenediamine comprises the following steps:
s1, under the protection of inert gas, dissolving crude phenylenediamine in a good solvent, stirring, and carrying out suction filtration to remove insoluble substances, wherein the obtained filtrate is a crude phenylenediamine solution;
s2, adding the crude phenylenediamine solution into an anti-solvent, or adding the anti-solvent into the crude phenylenediamine solution, mixing the two solutions, standing, and crystallizing to obtain a phenylenediamine crystal;
and S3, repeating the dissolving and crystallizing processes in S1 and S2 for a plurality of times, and drying the phenylenediamine crystals obtained by the crystallization for a plurality of times in vacuum to obtain the high-purity phenylenediamine product.
Further, in S1, the purity of the crude phenylenediamine is 90-99.5%; in S3, the purity of the high-purity phenylenediamine is 99.80% or more.
Further, in S1, the crude phenylenediamine includes p-phenylenediamine, m-phenylenediamine, and o-phenylenediamine.
Further, in S1, the inert gas is any one of nitrogen, argon and helium.
Further, in S1, the temperature at the time of dissolution was room temperature to 100 ℃.
Further, in S1, the temperature at the time of dissolution was room temperature to 80 ℃.
Further, in S1, the good solvent is any one of water, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, dichloromethane, and chloroform.
Further, in S2, the anti-solvent is any one of n-hexane, isopropanol, isobutanol, n-butanol, n-pentanol, isopentanol, benzene, and ethyl acetate.
Further, in S2, the temperature of crystallization is set to-10 to 30 ℃.
Further, in S3, the dissolving and crystallizing process is repeated 1-5 times.
The invention has the following beneficial effects:
the invention relates to a phenylenediamine purification method, which comprises the steps of dissolving phenylenediamine in a good solvent to form a solution, mixing the phenylenediamine solution with an antisolvent of the phenylenediamine, generating crystallization (precipitation) from the phenylenediamine, and drying the obtained crystallization through multiple dissolving-crystallization (precipitation) processes to obtain a high-purity phenylenediamine product, wherein the method comprises the steps of mixing the phenylenediamine saturated solution with the antisolvent, selecting the solvent and controlling process conditions to obtain the phenylenediamine product with the purity of more than 99.80 percent with the yield of more than 83 percent, compared with other phenylenediamine purification processes in the prior art, the method does not need special customized equipment, the purified phenylenediamine product is a high-white product, the whole process is rapid and simple, the energy consumption is low, the product with higher purity can be obtained at normal temperature, the used solvent can be recovered, and the requirement on the purity crude product is lower, the application range is wider, the operation is convenient, and the industrial production and manufacturing requirements can be met.
Drawings
FIG. 1 is a gas chromatogram of the product obtained in example 1 of the present invention;
FIG. 2 is a gas chromatogram of the product obtained in example 2 of the present invention;
FIG. 3 is a gas chromatogram of the product obtained in example 3 of the present invention;
FIG. 4 is a gas chromatogram of the product obtained in example 4 of the present invention;
FIG. 5 is a gas chromatogram of the product obtained in example 5 of the present invention;
FIG. 6 is a gas chromatogram of the product obtained in example 6 of the present invention;
Detailed Description
The invention will be further described with reference to the accompanying drawings.
Example 1
Under the protection of nitrogen at room temperature, 10g of crude p-phenylenediamine with the purity of 95 percent is added into a flask containing 30ml of N, N-Dimethylformamide (DMF), after magnetic stirring is carried out for 30min, insoluble substances are removed by suction filtration, filtrate is collected into the flask, the filtrate is DMF saturated solution of the p-phenylenediamine, then 40ml of isopropanol is added into the DMF saturated solution of the p-phenylenediamine, white crystals appear at the bottom of the flask, after standing for 10 min, suction filtration is carried out, the obtained filtrate is recovered, the white crystals are dried at room temperature in vacuum and then collected, the purity of the obtained purified p-phenylenediamine is 99.82 percent, and the yield is 85 percent.
Example 2
Under the protection of nitrogen at room temperature, 10g of crude p-phenylenediamine with the purity of 97 percent is added into a flask containing 30ml of N, N-Dimethylformamide (DMF), after magnetic stirring is carried out for 30min, insoluble substances are removed through suction filtration, filtrate is collected into the flask, then 40ml of ethanol/N-hexane mixed solvent (the volume ratio is 2:1) is added into the filtrate, white crystals appear at the bottom of the flask, after standing for 10 min, suction filtration is carried out, the obtained filtrate is recovered, the white crystals are dried at room temperature in vacuum and then collected, the purity of the obtained purified p-phenylenediamine is 99.91 percent, and the product yield is 87 percent.
Example 3
20g of p-phenylenediamine with a purity of 93 percent are added into a flask containing 30ml of dimethylacetamide (DMAc) under the protection of nitrogen at room temperature, magnetically stirring for 30min, vacuum filtering to remove insoluble substances, collecting filtrate, adding 40ml of toluene into the filtrate, white crystals appeared at the bottom of the flask, and after standing for 10 minutes, suction filtration was carried out, and the obtained filtrate was recovered to test the purity of p-phenylenediamine to be 98.73% and the yield to be about 92% (test results here, not shown in the drawing), and the white crystals were again dissolved in 30ml of DMAc, magnetically stirring for 30min, adding 35ml of toluene into p-phenylenediamine solution, white crystals appeared at the bottom of the flask, and after standing for 10 minutes, suction filtration was performed, the obtained filtrate was recovered, and the white crystals were collected after vacuum drying at room temperature, and the purity of the purified p-phenylenediamine obtained in this example was 99.88%, and the final yield was 84%.
Example 4
Under the protection of nitrogen at room temperature, 13g of p-phenylenediamine with the purity of 97 percent is added into a flask containing 30ml of water, after stirring for 30min at the temperature of 80 ℃, insoluble impurities are removed by suction filtration while the mixture is hot, the mixture is cooled to room temperature, white crystals are separated out, after standing for 30min, the mixture is heated to 60 ℃ again, after stirring for 30min, the mixture is cooled to-10 ℃, the white crystals are separated out, 40ml of chloroform is added into an aqueous solution of the p-phenylenediamine, the white crystals appear at the bottom of the flask, after standing for 10 min, suction filtration is carried out, the obtained filtrate is recovered, the white crystals are dried at the room temperature in vacuum and then collected, the purity of the purified p-phenylenediamine is 99.97 percent, and the yield is 89 percent in the embodiment.
Example 5
Under the protection of nitrogen at room temperature, 10g of p-phenylenediamine with the purity of 93 percent is added into a flask containing 30ml of ethanol, after magnetic stirring is carried out for 30min, insoluble substances are removed by suction filtration, filtrate is collected into the flask, 40ml of cyclohexane is added into the ethanol and the solution of the p-phenylenediamine, white crystals appear at the bottom of the flask, after standing for 10 min, suction filtration is carried out, the obtained filtrate is recovered, the white crystals are dried at room temperature in vacuum and then collected, and the purity of the purified p-phenylenediamine is 99.88 percent, and the yield is 88 percent.
Example 6
Under the protection of nitrogen at room temperature, 25g of m-phenylenediamine with the purity of 96% is added into a flask containing 30ml of water, after magnetic stirring is carried out for 30min, insoluble substances are removed through suction filtration, a filtrate is collected into the flask, the filtrate is an aqueous solution of the m-phenylenediamine, 40ml of butyl acetate/cyclohexane is added into the aqueous solution of the m-phenylenediamine, white crystals appear at the bottom of the flask, after standing for 10 min, suction filtration is carried out, the obtained filtrate is recovered, the white crystals are dried in vacuum at room temperature and collected, and the purity of the purified m-phenylenediamine obtained in the embodiment is over 99.87%, and the yield is 86%.
The products collected in examples 1-6 were analyzed by gas chromatography, and the samples were separated by capillary chromatography, detected by a hydrogen flame ionization detector, and quantified by area normalization. The analysis results are shown in fig. 1-6, and it can be known from fig. 1-6 that the phenylenediamine product purified by the method of the present invention has high purity of 99.85-99.99%, and the method has the advantages of simple process, easy operation, good purification effect, and good application prospect, and can meet the requirement of industrial production.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A method for purifying phenylenediamine is characterized by comprising the following steps:
s1, under the protection of inert gas, dissolving crude phenylenediamine in a good solvent, stirring, and carrying out suction filtration to remove insoluble substances, wherein the obtained filtrate is a crude phenylenediamine solution;
s2, adding the crude phenylenediamine solution into an anti-solvent, or adding the anti-solvent into the crude phenylenediamine solution, mixing the two solutions, standing, and crystallizing to obtain a phenylenediamine crystal;
and S3, repeating the dissolving and crystallizing processes in S1 and S2 for a plurality of times, and drying the phenylenediamine crystals obtained by the crystallization for a plurality of times in vacuum to obtain the high-purity phenylenediamine product.
2. The method for purifying phenylenediamine according to claim 1, wherein in S1, the purity of said crude phenylenediamine is 90% to 99.5%; in S3, the purity of the high-purity phenylenediamine is 99.80% or more.
3. The method for purifying phenylenediamine according to claim 1, wherein in S1, said crude phenylenediamine comprises p-phenylenediamine, m-phenylenediamine and o-phenylenediamine.
4. The method for purifying phenylenediamine according to claim 1, wherein said inert gas is any one of nitrogen, argon and helium in S1.
5. The method for purifying phenylenediamine according to claim 1, wherein the temperature at the time of dissolution in S1 is from room temperature to 100 ℃.
6. The method for purifying phenylenediamine according to claim 5, wherein the temperature at the time of dissolution in S1 is from room temperature to 80 ℃.
7. The method according to claim 1, wherein the good solvent in S1 is any one of water, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, dichloromethane, and chloroform.
8. The method of claim 1, wherein the anti-solvent of S2 is any one of n-hexane, isopropanol, isobutanol, n-butanol, n-pentanol, isopentanol, benzene, and ethyl acetate.
9. The method for purifying phenylenediamine according to claim 1, wherein the crystallization temperature in S2 is set to-10 to 30 ℃.
10. The method for purifying phenylenediamine according to claim 1, wherein the dissolving and crystallizing steps are repeated 1 to 5 times in S3.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113754546A (en) * | 2021-10-25 | 2021-12-07 | 沈阳感光化工研究院有限公司 | Method for purifying m-phenylenediamine |
| CN114249658A (en) * | 2021-12-23 | 2022-03-29 | 四川北方红光特种化工有限公司 | Method for preparing polymerization-grade m-phenylenediamine through melt crystallization and recycling mother liquor |
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| US4191708A (en) * | 1977-01-28 | 1980-03-04 | Sumitomo Chemical Company, Limited | Process for preparing and purifying p-phenylenediamine |
| CN101250113A (en) * | 2008-03-28 | 2008-08-27 | 上海安诺芳胺化学品有限公司 | Method for refining p-phenylene diamine |
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| CN111170872A (en) * | 2020-01-13 | 2020-05-19 | 中北大学 | Method for purifying p-phenylenediamine |
| CN111848408A (en) * | 2020-06-30 | 2020-10-30 | 杨美玲 | Novel continuous production method of phenylenediamine |
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2021
- 2021-07-27 CN CN202110852526.2A patent/CN113429299A/en active Pending
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113754546A (en) * | 2021-10-25 | 2021-12-07 | 沈阳感光化工研究院有限公司 | Method for purifying m-phenylenediamine |
| CN113754546B (en) * | 2021-10-25 | 2023-10-03 | 沈阳感光化工研究院有限公司 | Method for purifying m-phenylenediamine |
| CN114249658A (en) * | 2021-12-23 | 2022-03-29 | 四川北方红光特种化工有限公司 | Method for preparing polymerization-grade m-phenylenediamine through melt crystallization and recycling mother liquor |
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