CN116874399B - Preparation method of mercaptosuccinic acid - Google Patents
Preparation method of mercaptosuccinic acidInfo
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- CN116874399B CN116874399B CN202310863571.7A CN202310863571A CN116874399B CN 116874399 B CN116874399 B CN 116874399B CN 202310863571 A CN202310863571 A CN 202310863571A CN 116874399 B CN116874399 B CN 116874399B
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- mercaptosuccinic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/26—Separation; Purification; Stabilisation; Use of additives
- C07C319/28—Separation; Purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/64—Sulfur atoms
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Abstract
本申请提供一种巯基丁二酸的制备方法，属于精细化工技术领域。巯基丁二酸的制备方法包括以下步骤：将马来酸酐和组合催化剂溶于水并混合，再向混合后的水溶液中加入硫代乙酸，得到前驱体溶液，组合催化剂包括酸性吡啶和碱性胺；对前驱体溶液进行第一次加热处理，以使马来酸酐和硫代乙酸进行加成反应，得到中间体反应液，以及对中间体反应液进行第二次加热处理，以使中间体反应液中的中间体进行水解反应，再对中间体反应液水解后的体系进行第一次降温结晶，以使巯基丁二酸结晶析出，该制备方法能够改善制备得到的巯基丁二酸的纯度较低的问题，同时，还能降低巯基丁二酸的制备成本且兼顾解决环境污染的问题。
The present application provides a method for preparing mercaptosuccinic acid, belonging to the field of fine chemical technology. The method for preparing mercaptosuccinic acid comprises the following steps: dissolving maleic anhydride and a combined catalyst in water and mixing them, then adding thioacetic acid to the mixed aqueous solution to obtain a precursor solution, wherein the combined catalyst comprises an acidic pyridine and a basic amine; performing a first heating treatment on the precursor solution to cause an addition reaction between the maleic anhydride and the thioacetic acid to obtain an intermediate reaction liquid; performing a second heating treatment on the intermediate reaction liquid to cause a hydrolysis reaction of the intermediate in the intermediate reaction liquid; and then performing a first cooling and crystallization on the hydrolyzed intermediate reaction liquid to crystallize mercaptosuccinic acid. This preparation method can improve the problem of low purity of the prepared mercaptosuccinic acid, and at the same time, can reduce the preparation cost of mercaptosuccinic acid while also addressing environmental pollution issues.
Description
Technical Field
The application relates to the technical field of fine chemical engineering, in particular to a preparation method of mercaptosuccinic acid.
Background
In the prior art, the existing preparation method of the mercaptosuccinic acid is usually carried out under alkaline conditions, the hydrolysis mode can lead to lower purity of the finally prepared mercaptosuccinic acid, and meanwhile, the existing preparation mode usually uses an organic solvent as a solvent, so that the problems of higher cost and environmental pollution in the preparation of the mercaptosuccinic acid can be caused.
Disclosure of Invention
The application aims to provide a preparation method of mercaptosuccinic acid, which can improve the problem of lower purity of the prepared mercaptosuccinic acid, reduce the preparation cost of mercaptosuccinic acid and solve the problem of environmental pollution.
Embodiments of the present application are implemented as follows:
the embodiment of the application provides a preparation method of mercaptosuccinic acid, which comprises the following steps:
Dissolving maleic anhydride and a combined catalyst in water, mixing, adding thioacetic acid into the mixed aqueous solution to obtain a precursor solution, heating the precursor solution for the first time to enable the maleic anhydride and the thioacetic acid to perform an addition reaction to obtain an intermediate reaction solution, heating the intermediate reaction solution for the second time, wherein the lower temperature limit of the second heating is not lower than the upper temperature limit of the first heating, so that the intermediate in the intermediate reaction solution is subjected to hydrolysis reaction, and then cooling and crystallizing the hydrolyzed system of the intermediate reaction solution for the first time to enable mercaptosuccinic acid to be crystallized out.
According to the preparation method, on one hand, alkaline conditions are not required to be created in the hydrolysis process, namely alkaline substances are not required to be added, so that inorganic salts are not generated in the hydrolysis process, compared with the existing preparation process, the purity of the mercaptosuccinic acid is not reduced by the inorganic salts, and correspondingly, toxic acetone is not required to be adopted for refining the mercaptosuccinic acid, so that the purity of the prepared mercaptosuccinic acid can be improved, meanwhile, the preparation method has the advantage of better safety, on the other hand, water is directly adopted as a solvent, compared with the existing preparation process, the preparation cost of the mercaptosuccinic acid can be effectively reduced, and the problem of environmental pollution is solved.
In some alternative embodiments, after the first cooling crystallization, the method further comprises concentrating the mother solution obtained after the first cooling crystallization and crystallizing the mother solution for the second time in order to separate out the mercaptosuccinic acid crystals in the mother solution.
According to the technical scheme, the mother liquor after the first cooling crystallization is subjected to the second cooling crystallization, so that the residual mercaptosuccinic acid in the mother liquor can be effectively collected, and correspondingly, the yield of the mercaptosuccinic acid is equal to the sum of the yields obtained after the two cooling crystallization, so that the yield of the mercaptosuccinic acid is effectively improved, wherein the mother liquor is concentrated before the second crystallization, so that the concentration of the mercaptosuccinic acid in the mother liquor can be improved, and the efficiency of the second cooling crystallization is improved.
In some alternative embodiments, the acidic pyridine comprises at least one of pyridine 2-carboxylate, pyridine 3-carboxylate, and pyridine 4-carboxylate, and/or the basic amine comprises at least one of pyridine, piperidine, piperazine, 2-methylpyridine, 1-methylpiperidine, and N-methylpiperazine.
In the technical scheme, the types of the acid pyridine and the alkaline amine which can be suitable for the technical scheme provided by the embodiment of the application are rich, and more implementable schemes can be provided, so that the technical scheme of the application is convenient to popularize and apply.
In some alternative embodiments, the mass ratio of acidic pyridine to basic amine is 1 (0.8-1.2).
In the technical scheme, the mass ratio of the acidic pyridine to the basic amine is limited within a specific range, so that the combined catalyst has good catalytic performance, and the addition reaction of the maleic anhydride and the thioacetic acid has high reaction efficiency.
In some alternative embodiments, at least one of the following conditions A-C is satisfied:
The ratio of the mass of the A maleic anhydride to the mass of the water is 1 (1-3).
The ratio of the mass of the B maleic anhydride to the mass of the combined catalyst is 1 (0.01-0.04).
The ratio of the mass of the C maleic anhydride to the mass of the thioacetic acid is 1 (1-2).
In the technical scheme, the mass ratio of the maleic anhydride to the water to the maleic anhydride to the combined catalyst to the maleic anhydride to the thioacetic acid is respectively limited in a specific range, so that the concentration of the reaction raw materials in the reaction system and the mass ratio of the combined catalyst are both in a better range, and the reaction is more thorough.
In some alternative embodiments, the treatment temperature is 40-80 ℃ during the first heat treatment.
In the technical scheme, the addition reaction in the first stage is an exothermic reaction, the treatment temperature in the first heating treatment process is controlled within a specific range, on one hand, the setting of the upper temperature limit can effectively avoid the excessive reaction, so that the risk of generating byproducts is effectively reduced, the purity and the yield of mercaptosuccinic acid are further improved, and on the other hand, the setting of the lower temperature limit is used for providing more proper reaction conditions, so that the reaction raw materials can fully react.
In some alternative embodiments, the process temperature is 80-100 ℃ during the second heat treatment.
In the technical scheme, the second stage is hydrolysis reaction, the treatment temperature in the hydrolysis process is limited in a specific range, and the reaction intermediate can be fully converted into mercaptosuccinic acid.
In some alternative embodiments, the step of adding thioacetic acid to the mixed aqueous solution includes dropwise adding thioacetic acid to the mixed aqueous solution over a period of 5-8 hours.
According to the technical scheme, the dripping time of the thioacetic acid is controlled under a proper condition, so that the mass ratio of the thioacetic acid in the reaction system is lower, and the maleic anhydride and the thioacetic acid can be fully reacted under a milder condition.
In some alternative embodiments, the treatment temperature is 5-30 ℃ during the first cooling crystallization.
In the technical scheme, the treatment temperature in the first cooling crystallization process is limited in a specific range, so that the mercaptosuccinic acid in the solution can be crystallized more thoroughly.
In some alternative embodiments, the step of dissolving and mixing the maleic anhydride and the combination catalyst in water includes dissolving and mixing the maleic anhydride and the combination catalyst in water under heating conditions, and the upper temperature limit of the treatment is no higher than the lower temperature limit of the first heat treatment.
Optionally, the treatment temperature is 25-35 ℃.
In the technical scheme, the maleic anhydride is heated in the process of dissolving the maleic anhydride in water, so that the dissolution efficiency of the maleic anhydride can be improved.
Further, the temperature of the heating treatment is limited to a specific range, and the dissolution efficiency of maleic anhydride can be improved more.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a process flow diagram of a preparation method of mercaptosuccinic acid provided by the embodiment of the application;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of mercaptosuccinic acid provided in example 1 of the present application;
FIG. 3 is a nuclear magnetic resonance carbon spectrum of mercaptosuccinic acid provided in example 1 of the present application;
fig. 4 is a graph showing the infrared test results of mercaptosuccinic acid provided in example 1 of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In the present application, "and/or" such as "feature 1 and/or feature 2" means that "feature 1" alone, and "feature 2" alone, and "feature 1" plus "feature 2" alone, are all possible.
In the description of the present application, unless otherwise indicated, "plural" in "one or more" means two or more, and the range of "numerical value a to numerical value b" includes both the end values "a" and "b", and "measurement unit" in "numerical value a to numerical value b+ measurement unit" represents "measurement unit" of both "numerical value a" and "numerical value b".
In the prior art, the existing preparation process of mercaptosuccinic acid mostly adopts an organic solvent as a solvent in the initial stage of the reaction, and the subsequent hydrolysis process is usually carried out under alkaline conditions. The traditional preparation process has two major problems that on one hand, a large amount of inorganic salt is usually generated by hydrolysis under alkaline conditions, the purity of the mercaptosuccinic acid is influenced by the existence of the inorganic salt, and in order to remove the inorganic salt, acetone with toxicity is usually adopted for refining, and the acetone has toxicity, high management cost and high raw material cost, so that the preparation of the mercaptosuccinic acid is difficult to ensure and has high cost, and on the other hand, the organic solvent is adopted as a solvent, so that the raw material cost is high, and the environment pollution is easy to cause because the production waste liquid contains a large amount of organic solvent.
Based on the above, the inventor provides a novel preparation process of mercaptosuccinic acid through creative research, which can directly use water as a solvent, and subsequent hydrolysis is not needed to be carried out under alkaline conditions, so that the problem of lower purity of the prepared mercaptosuccinic acid can be solved, and meanwhile, the preparation cost of the mercaptosuccinic acid can be reduced, and the problem of environmental pollution can be solved.
The following specifically describes a preparation method of mercaptosuccinic acid in the embodiment of the present application.
The embodiment of the application provides a preparation method of mercaptosuccinic acid, which comprises the following steps:
Dissolving maleic anhydride and a combined catalyst in water, mixing, adding thioacetic acid into the mixed aqueous solution to obtain a precursor solution, heating the precursor solution for the first time to enable the maleic anhydride and the thioacetic acid to perform an addition reaction to obtain an intermediate reaction solution, heating the intermediate reaction solution for the second time, wherein the lower temperature limit of the second heating is not lower than the upper temperature limit of the first heating, so that the intermediate in the intermediate reaction solution is subjected to hydrolysis reaction, and then cooling and crystallizing the hydrolyzed system of the intermediate reaction solution for the first time to enable mercaptosuccinic acid to be crystallized out.
According to the preparation method provided by the embodiment of the application, the preparation of the mercaptosuccinic acid is carried out, on one hand, alkaline conditions are not required to be created in the hydrolysis process, namely alkaline substances are not required to be added, so that inorganic salts are not generated in the hydrolysis process, compared with the existing preparation process, the purity of the mercaptosuccinic acid is not reduced by the inorganic salts, and correspondingly, toxic acetone is not required to be adopted for refining the mercaptosuccinic acid, so that the purity of the prepared mercaptosuccinic acid can be improved, meanwhile, the method has the advantage of better safety, on the other hand, water is directly adopted as a solvent, and compared with the existing preparation process, the preparation cost of the mercaptosuccinic acid can be effectively reduced, and the problem of environmental pollution is solved.
It will be appreciated that in order to better control the progress of the reaction, it is desirable to monitor the change in the contents of the reaction starting materials and reaction intermediates during the addition reaction and hydrolysis reaction, respectively.
The monitoring method is not limited, and for example, high performance liquid chromatography or gas chromatography may be used.
For a better understanding of the technical solution, an additional description is given here by means of the reaction equation.
The reaction equation in the addition stage is as follows:
the reaction equation for the hydrolysis stage is as follows:
It can be understood that in the process of the first cooling crystallization, due to the large volume of the mixed system, it is difficult to completely crystallize out all the mercaptosuccinic acid, so that the second cooling crystallization can be performed in consideration of the yield of the mercaptosuccinic acid.
As an example, after the first cooling crystallization, the method further comprises concentrating the mother solution obtained after the first cooling crystallization and crystallizing the mother solution for the second cooling crystallization in order to separate out the mercaptosuccinic acid crystals in the mother solution.
In the embodiment, the mother liquor after the first cooling crystallization is subjected to the second cooling crystallization, so that the residual mercaptosuccinic acid in the mother liquor can be effectively collected, and correspondingly, the yield of the mercaptosuccinic acid is equal to the sum of the yields obtained after the two cooling crystallization, so that the yield of the mercaptosuccinic acid is effectively improved, wherein the mother liquor is concentrated before the second crystallization, so that the concentration of the mercaptosuccinic acid in the mother liquor can be improved, and the efficiency of the second cooling crystallization is improved.
It will be appreciated that the types of acidic pyridine and basic amine in the combination catalyst are not limited and may be set according to conventional choices in the art.
As one example, the acidic pyridine includes at least one of pyridine 2-carboxylate, pyridine 3-carboxylate, and pyridine 4-carboxylate, and/or the basic amine includes at least one of pyridine, piperidine, piperazine, 2-methylpyridine, 1-methylpiperidine, and N-methylpiperazine.
In the embodiment, the technical scheme provided by the embodiment of the application has rich applicable types of acidic pyridine and alkaline amine, and can provide more implementable schemes, thereby being convenient for popularization and application of the technical scheme of the application.
It will be appreciated that the mass ratio of the two monomer catalysts may be adjusted in view of the catalytic performance of the combined catalyst.
As an example, the mass ratio of acidic pyridine to basic amine is 1 (0.8-1.2), such as, but not limited to, a mass ratio of any one point value or a range value between any two of 1:0.8, 1:0.9, 1:1.0, 1:1.1 and 1:1.2.
In this embodiment, the mass ratio of the acidic pyridine to the basic amine is limited to a specific range, so that the combined catalyst has good catalytic performance, and the addition reaction of the maleic anhydride and the thioacetic acid has high reaction efficiency.
It is understood that the efficiency of the addition reaction and the availability of the reaction materials can be effectively improved under suitable reaction conditions (such as the concentration of the reaction materials, the amount of the catalyst combination, the treatment temperature of the first heat treatment, etc.).
As an example, at least one of the following conditions a to C is satisfied:
the ratio of the mass of the A maleic anhydride to the mass of the water is 1 (1-3), such as, but not limited to, a mass ratio of any one point value or a range value between any two of 1:1, 1:1.5, 1:2, 1:2.5 and 1:3.
The ratio of the mass of the B maleic anhydride to the mass of the combined catalyst is 1 (0.01-0.04), such as, but not limited to, any one point value or a range value between any two point values of 1:0.01, 1:0.02, 1:0.03 and 1:0.04.
The ratio of the mass of the C maleic anhydride to the mass of the thioacetic acid is 1 (1-2), such as, but not limited to, a mass ratio of any one point value or a range value between any two of 1:1, 1:1.2, 1:1.4, 1:1.6, 1:1.8 and 1:2.0.
In this embodiment, the mass ratio of maleic anhydride to water, maleic anhydride to the combination catalyst, and maleic anhydride to thioacetic acid are respectively limited to a specific range, so that the concentration of the reaction raw materials in the reaction system and the mass ratio of the combination catalyst can be within a preferable range, thereby enabling the reaction to be more complete.
As an example, during the first heat treatment, the treatment temperature is 40-80 ℃, such as, but not limited to, a treatment temperature of any one point value or a range value between any two of 40 ℃, 50 ℃, 60 ℃, 70 ℃ and 80 ℃.
In the embodiment, the addition reaction in the first stage is an exothermic reaction, and the treatment temperature in the first heating treatment process is controlled within a specific range, so that on one hand, the setting of the upper temperature limit can effectively avoid the excessive reaction, thereby effectively reducing the risk of generating byproducts and further contributing to the improvement of the purity and yield of mercaptosuccinic acid, and on the other hand, the setting of the lower temperature limit is used for providing more appropriate reaction conditions so that the reaction raw materials can fully react.
It will be appreciated that under suitable reaction conditions (e.g., the treatment temperature of the second heat treatment), the intermediate is able to be more thoroughly converted to mercaptosuccinic acid during the hydrolysis reaction stage.
As an example, during the second heat treatment, the treatment temperature is 80-100 ℃, such as, but not limited to, a treatment temperature of any one point value or a range value between any two of 80 ℃, 85 ℃, 90 ℃, 95 ℃ and 100 ℃.
In this embodiment, the second stage is a hydrolysis reaction, and the treatment temperature in the hydrolysis process is limited to a specific range, so that the reaction intermediate can be sufficiently converted into mercaptosuccinic acid.
In addition reaction, if the reaction is too severe, a byproduct is generated after the raw material reaction, and the target product cannot be obtained, so that the dripping time of thioacetic acid can be adjusted to create a milder reaction condition.
As an example, the step of adding thioacetic acid to the mixed aqueous solution includes dropwise adding thioacetic acid to the mixed aqueous solution within 5-8 hours.
In this embodiment, the time period of the addition of the thioacetic acid is controlled to be suitable, so that the mass ratio of the thioacetic acid in the reaction system can be made to be low, so that the maleic anhydride and the thioacetic acid can be sufficiently reacted under relatively mild conditions.
It is understood that the treatment temperature of the reduced temperature crystallization is related to the crystallization effect.
As an example, during the first cooling crystallization, the processing temperature is 5 to 30 ℃, such as, but not limited to, a processing temperature of any one point value or a range value between any two of 5 ℃,10 ℃, 20 ℃ and 30 ℃.
In the embodiment, the treatment temperature in the first cooling crystallization process is limited in a specific range, so that the mercaptosuccinic acid in the solution can be crystallized more thoroughly.
The dissolution rate of maleic anhydride in water is limited by the physical and chemical properties of the reaction raw materials, and the process in the dissolution stage may be adjusted in consideration of the dissolution efficiency.
As an example, the step of dissolving and mixing the maleic anhydride and the combination catalyst in water includes dissolving and mixing the maleic anhydride and the combination catalyst in water under heating conditions, and the upper limit of the treatment temperature is not higher than the lower limit of the temperature of the first heat treatment.
In this embodiment, the dissolution efficiency of maleic anhydride can be improved by heating the maleic anhydride in the process of dissolving the maleic anhydride in water.
As an example, the process temperature is 25-35 ℃, such as, but not limited to, a process temperature of any one point value or range value between any two of 25 ℃,30 ℃, and 35 ℃.
In this embodiment, the temperature of the heating treatment is limited to a specific range, and the dissolution efficiency of maleic anhydride can be improved more.
It should be noted that, the processes or steps not specifically described or defined in the preparation method of mercaptosuccinic acid may be set according to conventional choices in the art.
As an example, the method further comprises filtering and drying sequentially after the cooling crystallization.
As an example, a process flow diagram of a method for preparing mercaptosuccinic acid is schematically shown in fig. 1.
The features and capabilities of the present application are described in further detail below in connection with the examples.
Example 1
The embodiment of the application provides a preparation method of mercaptosuccinic acid, which comprises the following steps:
Dissolving maleic anhydride and a combined catalyst in water, stirring and mixing at 30 ℃ to completely dissolve the maleic anhydride, and then dropwise adding thioacetic acid into the mixed aqueous solution to obtain a precursor solution, wherein the mass of the maleic anhydride is 20g (namely 1 time equivalent), the mass of the combined catalyst is 0.02 time equivalent (the mass ratio of pyridine-2-formate to pyridine is 1:1), the mass of the thioacetic acid is 1.2 time equivalent, and the dropwise adding time is 6 hours.
The precursor solution is heated to 60 ℃ and is subjected to heat preservation reaction, and the residual quantity of the maleic anhydride is tracked by adopting HPLC until the maleic anhydride is completely reacted, so as to obtain an intermediate reaction solution.
Heating the intermediate reaction liquid to 90 ℃ and preserving heat for reaction, adopting HPLC to track the residual quantity of the intermediate until the intermediate is completely reacted, then cooling to 20 ℃, filtering and drying to obtain the mercaptosuccinic acid monohydrate.
Concentrating and crystallizing the mother solution after the first cooling to separate out mercaptosuccinic acid crystals, and filtering and drying to obtain mercaptosuccinic acid secondary precipitate.
The following examples and comparative examples were carried out according to the procedure of example 1, unless otherwise specified.
For a better understanding of the differences between the various examples and comparative examples, a summary is provided herein in the form of a table.
Table 1 process conditions for each of the examples and comparative examples
In order to better illustrate the differences between the technical solutions provided by the embodiments of the present application and the prior art, the present application also provides comparative example 4.
Comparative example 4
The comparison example of the application provides a preparation method of mercaptosuccinic acid, which is different from the example 1 only in that sodium hydroxide is added into an intermediate reaction liquid and heated to 90 ℃ for heat preservation reaction, HPLC is adopted to track the residual quantity of the intermediate until the intermediate is completely reacted, acid is added after the reaction is finished to adjust the pH value of a mixed system to 2, and then the temperature is reduced to 20 ℃, and the mixture is filtered and dried to obtain a mercaptosuccinic acid monohydrate.
Concentrating and crystallizing the mother solution after the first cooling to separate out mercaptosuccinic acid crystals, and filtering and drying to obtain mercaptosuccinic acid secondary precipitate.
Test example 1
Purity test of mercaptosuccinic acid
The testing method comprises the following steps:
Preparation of mercaptosuccinic acid was carried out according to the preparation methods of examples 1 to 17 and comparative examples 1 to 4, respectively, and then mercaptosuccinic acid monoanalytes in each of examples and comparative examples were prepared as test samples for HPLC, and the purity of the products was tested by HPLC equipment.
TABLE 2 purity of mercaptosuccinic acid monoanalyte in examples and comparative examples
| Numbering device | Purity (%) | Number of impurities | Maximum mono-hetero (%) | Sodium ion content |
| Example 1 | 99.5 | 3 | 0.3 | 0.6ppm |
| Example 2 | 99.3 | 3 | 0.4 | 0.6ppm |
| Example 3 | 99.6 | 3 | 0.2 | 0.8ppm |
| Example 4 | 96.0 | 3 | 2.5 | 0.6ppm |
| Example 5 | 99.0 | 3 | 0.4 | 0.5ppm |
| Example 6 | 99.5 | 3 | 0.3 | 0.6ppm |
| Example 7 | 99.6 | 3 | 0.3 | 0.6ppm |
| Example 8 | 99.5 | 3 | 0.4 | 0.6ppm |
| Example 9 | 99.0 | 4 | 0.8 | 0.6ppm |
| Example 10 | 98.5 | 4 | 1.5 | 0.7ppm |
| Example 11 | 99.2 | 3 | 0.4 | 0.8ppm |
| Example 12 | 99.8 | 2 | 0.2 | 0.7ppm |
| Example 13 | 99.7 | 3 | 0.2 | 0.6ppm |
| Example 14 | 98.3 | 3 | 0.5 | 0.8ppm |
| Example 15 | 90.3 | 6 | 4.8 | 0.7ppm |
| Example 16 | 99.5 | 3 | 0.2 | 0.6ppm |
| Example 17 | 98.5 | 4 | 0.9 | 0.7ppm |
| Comparative example 1 | 97.6 | 4 | 1.8 | 0.7ppm |
| Comparative example 2 | 98.5 | 3 | 0.9 | 0.6ppm |
| Comparative example 3 | 95.9 | 5 | 1.0 | 0.6ppm |
| Comparative example 4 | 93.6 | 6 | 2.5 | 1.5% |
Referring to Table 2, it is understood from the test results of examples 1 to 3, examples 5 to 8, examples 11 to 14, and examples 16 to 17 and comparative example 4 that the preparation process according to the present application provides preparation with higher purity compared with the mercaptosuccinic acid corresponding to the former hydrolysis under alkaline conditions.
As can be seen from the test results of examples 4, 9-10 and 15 and example 1, the parameters are controlled within the specific range provided in the present embodiment according to the single variable principle, and the mercaptosuccinic acid corresponding to the former has higher purity than the mercaptosuccinic acid not within the specific range.
As can be seen from the test results of comparative examples 1 to 3 and example 1, the combined catalyst provided by the examples of the present application has higher purity than the mercaptosuccinic acid corresponding to the former catalyst, which is obtained by using only one component as the catalyst and not providing the catalyst.
Test example 2
Yield test of mercaptosuccinic acid
The testing method comprises the following steps:
The preparation of mercaptosuccinic acid was carried out according to the preparation methods of examples 1 to 17 and comparative examples 1 to 4, respectively, and then the yields of mercaptosuccinic acid monoanalyte and mercaptosuccinic acid dibasic in each of examples and comparative examples were calculated according to the theoretical yield (30.60 g) and the actual yield of the product, respectively.
TABLE 3 yield of mercaptosuccinic acid mono-and di-analytes in examples and comparative examples
Referring to Table 3, it is understood from the test results of examples 1 to 3, examples 5 to 8, examples 11 to 14, and examples 16 to 17 and comparative example 4 that the preparation process according to the present application provides a higher total yield of mercaptosuccinic acid than hydrolysis under alkaline conditions.
As can be seen from the test results of examples 4, 9-10 and 15 and example 1, according to the principle of single variable, the parameters corresponding to the parameters are controlled within the specific range provided in the present embodiment, and the yield of mercaptosuccinic acid corresponding to the parameters is higher than that of mercaptosuccinic acid not within the specific range.
From the test results of comparative examples 1 to 3 and example 1, it is understood that the combined catalyst provided by the example of the present application has a higher total yield of mercaptosuccinic acid than the catalyst prepared by using only one component and not providing the catalyst.
Test example 3
Qualitative characterization of mercaptosuccinic acid
The testing method comprises the following steps:
The preparation of mercaptosuccinic acid was performed according to the preparation process of example 1, and then the mercaptosuccinic acid monohydrate in the preparation process was subjected to sample preparation according to the nuclear magnetic resonance test requirement and the infrared test requirement, respectively, wherein the solvent in the nuclear magnetic resonance test sample was D 2 O, and the reference salt in the infrared test sample was potassium bromide.
Referring to fig. 2, the nmr hydrogen spectrum result shows two groups of peaks, namely delta 3.81-3.70 (m, 1H) and 3.04-2.80 (m, 2H), the signal belongings are shown in the following chart, the integral ratio of the two groups of peaks is about 1:2 (two kinds of hydrogen corresponding to different positions, and the number ratio is 1:2), and the theoretical result is consistent, so that the prepared product is proved to be mercaptosuccinic acid.
Referring to fig. 3, the nmr carbon spectrum results show four groups of peaks, namely delta 177.12, 175.27, 67.19, 39.93 and 36.42, and the signal attribution is shown in the following chart, which is consistent with the theoretical result, and the prepared product is proved to be mercaptosuccinic acid.
Referring to FIG. 4, it is clear that the region 3300-2405cm -1 has an extremely wide band, which is a characteristic absorption peak of-COOH, and the overlapping 2560cm -1 absorption band is a characteristic absorption peak of-SH, 2962cm -1 and 2910cm -1 are characteristic absorption peaks of saturated C-H, and 1703cm -1 is a characteristic absorption peak of carbonyl in-COOH, which is consistent with the theoretical result, and the prepared product is proved to be mercaptosuccinic acid.
The embodiments described above are some, but not all embodiments of the application. The detailed description of the embodiments of the application is not intended to limit the scope of the application, as claimed, but is merely representative of selected embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Claims (9)
1. The preparation method of the mercaptosuccinic acid is characterized by comprising the following steps of;
dissolving maleic anhydride and a combined catalyst in water, mixing, and adding thioacetic acid into the mixed water solution to obtain a precursor solution, wherein the combined catalyst comprises acidic pyridine and alkaline amine;
performing a first heating treatment on the precursor solution to perform an addition reaction between the maleic anhydride and the thioacetic acid to obtain an intermediate reaction solution, and
Performing a second heating treatment on the intermediate reaction liquid, wherein the lower temperature limit of the second heating treatment is not lower than the upper temperature limit of the first heating treatment, so that the intermediate in the intermediate reaction liquid is subjected to hydrolysis reaction, and then performing a first cooling crystallization on a system obtained after the hydrolysis of the intermediate reaction liquid, so that the mercaptosuccinic acid is crystallized and separated out;
The acidic pyridine comprises at least one of pyridine-2-carboxylate, pyridine-3-carboxylate and pyridine-4-carboxylate, and/or the basic amine comprises at least one of pyridine, piperidine, piperazine, 2-methylpyridine, 1-methylpiperidine and N-methylpiperazine;
the mass ratio of the acidic pyridine to the alkaline amine is 1 (0.8-1.2).
2. The method for producing mercaptosuccinic acid according to claim 1, further comprising concentrating the mother liquor obtained after the first cooling crystallization and crystallizing the mother liquor at a second cooling in order after the first cooling crystallization, so as to crystallize mercaptosuccinic acid out of the mother liquor.
3. The method for producing mercaptosuccinic acid according to claim 1 or 2, wherein at least one of the following conditions a to C is satisfied:
the ratio of the mass of the maleic anhydride to the mass of the water is 1 (1-3);
The ratio of the mass of the maleic anhydride to the mass of the combined catalyst is1 (0.01-0.04);
and C, the ratio of the mass of the maleic anhydride to the mass of the thioacetic acid is 1 (1-2).
4. The method for preparing mercaptosuccinic acid according to claim 1 or 2, wherein the treatment temperature is 40-80 ℃ in the first heating treatment process.
5. The preparation method of mercaptosuccinic acid according to claim 1 or 2, wherein the treatment temperature is 80-100 ℃ in the second heating treatment process.
6. The preparation method of mercaptosuccinic acid according to claim 1 or 2, wherein the step of adding thioacetic acid to the mixed aqueous solution comprises dropwise adding thioacetic acid to the mixed aqueous solution within 5-8 hours.
7. The preparation method of mercaptosuccinic acid according to claim 1 or 2, wherein the treatment temperature is 5-30 ℃ in the first cooling crystallization process.
8. The method for producing mercaptosuccinic acid according to claim 1 or 2, wherein the step of dissolving and mixing maleic anhydride and the combination catalyst in water comprises dissolving and mixing maleic anhydride and the combination catalyst in water under heating conditions, and the upper limit of the treatment temperature is not higher than the lower limit of the temperature of the first heat treatment.
9. The method for preparing mercaptosuccinic acid according to claim 8, wherein the treatment temperature is 25-35 ℃.
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| CN1189818A (en) * | 1995-06-07 | 1998-08-05 | 诺沃斯国际公司 | Method for the preparation of 3-(methylthio)propionaldehyde and 2-hydroxyl-4-(methylthio)butyronitrile |
| CN112479951A (en) * | 2020-11-25 | 2021-03-12 | 山东益丰生化环保股份有限公司 | Continuous synthesis method of carboxyethyl sulfosuccinate |
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| GB1002328A (en) * | 1961-10-16 | 1965-08-25 | Monsanto Co | Sulphur-containing anhydrides |
| US4172207A (en) * | 1977-02-22 | 1979-10-23 | Mack Gerry P | Process for mercaptoalkanedicarboxylic acid esters |
| JP2855871B2 (en) * | 1991-03-27 | 1999-02-10 | 堺化学工業株式会社 | Method for producing thiomalic acid |
| JPH08311055A (en) * | 1995-05-19 | 1996-11-26 | Nippon Oil & Fats Co Ltd | Production of carboxyalkylthiosuccinic anhydride |
| US20110004017A1 (en) * | 2007-09-20 | 2011-01-06 | Showa Denko K.K. | Method for producing b-mercaptocarboxylic acids |
| CN107628974B (en) * | 2017-10-11 | 2019-06-25 | 合肥立方制药股份有限公司 | A kind of dimercaptosuccinic acid and its salt and preparation method |
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| CN1189818A (en) * | 1995-06-07 | 1998-08-05 | 诺沃斯国际公司 | Method for the preparation of 3-(methylthio)propionaldehyde and 2-hydroxyl-4-(methylthio)butyronitrile |
| CN112479951A (en) * | 2020-11-25 | 2021-03-12 | 山东益丰生化环保股份有限公司 | Continuous synthesis method of carboxyethyl sulfosuccinate |
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