Preparation method of sodium polydipropane disulfide sulfonate

Abstract

The invention provides a preparation method of sodium polydipropane disulfide sulfonate, firstly mixing a thioamide compound, 1,3-propane sultone and a solvent, reacting to obtain 3-sulfimido propane sulfonic acid, then controlling pH>10 with an organic base, adding an oxidant to the 3-sulfimido propane sulfonic acid for reaction, and finally obtaining sodium polydipropane disulfide sulfonate after reduced pressure concentration, soaking, washing, suction filtration and drying. The present invention directly performs sulfonation oxidation with thioamide compounds and 1,3-propane sultone as raw materials to obtain sodium polydipropane disulfide sulfonate, provides a new synthesis idea of ​​sodium polydipropane disulfide sulfonate, avoids the problem of using inorganic substances such as hydrogen sulfide or sulfide salt as raw materials in the prior art, reduces the synthesis steps of sodium polydipropane disulfide sulfonate, has the characteristics of simple process, low energy consumption, less waste water, high yield of product and high effective content, and is conducive to the industrial production of sodium polydipropane disulfide sulfonate.

Description

Technical Field

[0001] The invention relates to the technical field of organic synthesis, in particular to a method for preparing sodium polydipropane disulfide sulfonate. Background Art

[0002] As an important chemical raw material, sodium polydipropane disulfide sulfonate (SPS) is a white or light yellow powder that is easy to absorb moisture, highly water-soluble, slightly soluble in alcohols, and can be stored in a cool and dry place. In practical applications, sodium polydipropane disulfide sulfonate is widely used as an acid copper plating brightener to obtain decorative and functional coatings (such as printed circuit boards); sodium polydipropane disulfide sulfonate can be used in combination with typical copper plating formulas such as non-ionic surfactants, polyamines and other thiol compounds, and can also be used in combination with dyes.

[0003] In the prior art, the synthesis method of polysodium disulfide propane sulfonate mainly adopts sulfonation of inorganic substances such as hydrogen sulfide or sulfide salt with organic substances, and combines it with alkalization or oxidation processes to prepare it. Among them, the alkalization sulfonation method directly uses hydrogen sulfide as a raw material, which has great safety hazards because hydrogen sulfide is a highly toxic gas, and also has technical defects such as high energy consumption, high production cost, and difficulty in obtaining high-purity products.

[0004] At present, the synthesis method of sodium polydipropane disulfide sulfonate using sulfide salt is as follows: the invention patent (application number is CN201710092055.3) discloses a method of using 1,3-propane sultone as a raw material, reacting with sodium thiosulfate in a mixed solvent of alcohol and water to prepare pente salt, and then alkalizing and oxidizing the prepared pente salt to obtain sodium polydipropane disulfide sulfonate; the temperature of the oxidation reaction in this process is relatively high, and the control requirements of the process conditions are strict, and it is easy to have limited side reactions during alkaline hydrolysis to generate sodium sulfate, and the sodium sulfate crystals are in the form of a colloid, which is difficult to remove, and it is easy to cause a sharp drop in the yield and purity of SPS, which is not conducive to industrial production.

[0005] The invention patent (application number CN202211370844.6) discloses a method for preparing sodium polydipropylene disulfide sulfonate, which uses 1,3-propane sultone and thiourea as starting materials, adopts a resin exchange method, and obtains sodium polydipropylene disulfide sulfonate through oxidation reaction and alkali neutralization reaction; this process uses ammonia water as an alkali regulator, and the amount of ammonia water used is large. In addition, ammonium ions are introduced into the reaction, and cationic resins need to be used to remove the ammonium ions, which increases the water consumption of the reaction system. Subsequent crystallization requires distillation of a large amount of water, resulting in excessive energy consumption. At the same time, a large amount of wastewater is also generated, resulting in problems of resource waste and environmental pollution.

[0006] In view of this, it is necessary to design an improved method for preparing sodium polydisulfide dipropane sulfonate to solve the above problems. Summary of the invention

[0007] The object of the present invention is to provide a method for preparing sodium polydipropane disulfide sulfonate, which directly carries out sulfonation oxidation with thioamide compounds and 1,3-propane sultone as raw materials to prepare sodium polydipropane disulfide sulfonate, so as to solve the technical problems of high preparation temperature, low yield and effective content and high energy consumption of sodium polydipropane disulfide sulfonate in the prior art.

[0008] To achieve the above-mentioned object of the invention, the present invention provides a method for preparing sodium polydipropane disulfide sulfonate, comprising the following steps:

[0009] S1, mixing a thioamide compound, 1,3-propane sultone and a solvent and stirring them uniformly to obtain a 3-sulfimidopropane sulfonic acid solution; the molar ratio of the thioamide compound to the 1,3-propane sultone is 1:(1.01-1.10);

[0010] S2, adding a regulator to the 3-sulfimidopropane sulfonic acid solution of step S1, controlling the pH of the solution to be greater than 10, continuing to add an oxidant to the 3-sulfimidopropane sulfonic acid solution for oxidation reaction, and then concentrating under reduced pressure, washing, filtering, and drying to obtain sodium polydisulfide dipropane sulfonate.

[0011] As a further improvement of the present invention, in step S1, the thioamide compound includes one of thioacetamide and sodium methyldithiocarbamate.

[0012] As a further improvement of the present invention, in step S2, the regulator is an alkali metal salt of an alcohol.

[0013] As a further improvement of the present invention, the regulator is one of sodium methoxide, sodium ethoxide and sodium tert-butoxide.

[0014] As a further improvement of the present invention, in step S2, the molar ratio of 3-sulfimidopropane sulfonic acid in the 3-sulfimidopropane sulfonic acid solution to the added oxidant is 1:(0.05-0.1).

[0015] As a further improvement of the present invention, in step S1, in the reaction system of the thioamide compound, 1,3-propane sultone and the solvent, the reaction temperature is 20 to 60° C. and the reaction time is 0.5 to 3.0 h.

[0016] As a further improvement of the present invention, in step S2, the temperature of the oxidation reaction is 30-70°C and the time is 3-9 hours.

[0017] As a further improvement of the present invention, in step S1, the mixing process of the thioamide compound, 1,3-propane sultone and the solvent is: firstly mix the thioamide compound with the solvent, then slowly dropwise add 1,3-propane sultone, and control the dropping temperature to be less than 30°C.

[0018] As a further improvement of the present invention, in step S1, the solvent includes a mixture of one or more of water, methanol, ethanol, isopropanol, acetone, and acetonitrile in any proportion.

[0019] As a further improvement of the present invention, in step S2, the oxidant is one or more of sodium hypochlorite, hydrogen peroxide, oxygen, and copper oxide.

[0020] The beneficial effects of the present invention are:

[0021] 1. The preparation method of the polydipropane disulfide sodium sulfonate of the present invention comprises the following steps: firstly mixing a thioamide compound, 1,3-propane sultone and a solvent to obtain 3-sulfimido propane sulfonic acid by reaction, then controlling the pH value to be greater than 10, continuously adding an oxidant to the 3-sulfimido propane sulfonic acid to react, and finally obtaining the polydipropane disulfide sodium sulfonate by vacuum concentration, soaking, washing, suction filtration and drying. The preparation method of the present invention directly performs sulfonation oxidation with thioamide compound and 1,3-propane sultone as raw materials to obtain the polydipropane disulfide sodium sulfonate, reduces the synthesis steps of the polydipropane disulfide sodium sulfonate, has the characteristics of simple process, low energy consumption, less waste water, high yield of the product and high effective content, and is conducive to the industrial production of the polydipropane disulfide sodium sulfonate.

[0022] 2. The present invention adopts thioamide organic compounds as raw materials for sulfonation reaction, replacing inorganic substances such as hydrogen sulfide or sulfide salt in the prior art, and provides a new synthesis idea for polydipropane disulfide sodium sulfonate, avoiding the safety hazards caused by the existing hydrogen sulfide as raw material and the problem that sulfide salt is easy to produce by-products as raw materials. When adjusting the pH of the solution, the present invention adopts an organic base, that is, an alkali metal salt of an alcohol, as a regulator. The regulator will not bring in new ionic impurities, and there is no need to use a cationic resin for impurity removal later, which reduces the production cost, does not generate a large amount of wastewater, and reduces resource waste and post-processing steps; in addition, the organic base as a regulator is relatively mild, has low corrosiveness, has the advantages of green environmental protection, and can also be connected to organic molecules, has the effect of directional catalytic oxidation, and improves the purity and yield of polydipropane disulfide sodium sulfonate. DETAILED DESCRIPTION

[0023] In order to make the purpose, technical solutions and advantages of the present invention more clear, the present invention is described in detail below in conjunction with specific embodiments.

[0024] In addition, it should be noted that the terms "comprises", "includes" or any other variations thereof are intended to cover non-exclusive inclusion, so that a process, method, article or apparatus that includes a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or apparatus.

[0025] A method for preparing sodium polydipropane disulfide sulfonate comprises the following steps:

[0026] S1, mixing a thioamide compound, 1,3-propane sultone and a solvent and stirring them uniformly to obtain a 3-sulfimidopropane sulfonic acid solution; the molar ratio of the thioamide compound to 1,3-propane sultone is 1:(1.01-1.10);

[0027] S2, adding a regulator to the 3-sulfimidopropane sulfonic acid solution of step S1, controlling the pH of the solution to be greater than 10, continuing to add an oxidant to the 3-sulfimidopropane sulfonic acid solution for oxidation reaction, and then concentrating under reduced pressure, washing, filtering, and drying to obtain sodium polydisulfide dipropane sulfonate.

[0028] Specifically, in step S1, the thioamide compound includes one of thioacetamide and sodium methyldithiocarbamate. The thioamide organic compound is used as the raw material for the sulfonation reaction, replacing inorganic substances such as hydrogen sulfide or sulfide salt in the prior art, providing a new synthesis idea for sodium polydisulfide propane sulfonate, avoiding the safety hazards caused by the existing hydrogen sulfide as a raw material, the sulfide salt as a raw material is easy to produce by-products, and the process conditions control requirements are strict.

[0029] It should be noted that in step S1, 3-sulfiliminepropane sulfonic acid is the reaction product of a thioamide compound and 1,3-propane sultone, and is a newly named chemical formula, and its specific chemical structure varies depending on the different thioamide compounds as reactants.

[0030] In step S2, the regulator is an alkali metal salt of an alcohol. The regulator is specifically one of sodium methoxide, sodium ethoxide, and sodium tert-butoxide. An organic base, i.e., an alkali metal salt of an alcohol, is used as the pH regulator of the solution. The regulator will not introduce new ionic impurities, and there is no need to use a cationic resin or other methods for impurity removal in the future, which reduces production costs, does not generate a large amount of waste water, reduces resource waste and post-processing steps; in addition, the organic base is used as a regulator, which is relatively mild, has low corrosiveness, has the advantages of being green and environmentally friendly, and can also be connected to organic molecules, has the effect of directional catalytic oxidation, and improves the purity and yield of polydisulfide sodium propane sulfonate.

[0031] Preferably, in step S2, the molar ratio of 3-sulfimidopropane sulfonic acid in the 3-sulfimidopropane sulfonic acid solution to the added oxidant is 1:(0.05-0.1). The oxidation reaction temperature is 30-70°C and the time is 3-9h.

[0032] In step S1, in the reaction system of thioamide compound, 1,3-propane sultone and solvent, the reaction temperature is 20-60°C and the reaction time is 0.5-3.0h. The mixing process of thioamide compound, 1,3-propane sultone and solvent is: firstly mix the thioamide compound with the solvent, then slowly drop 1,3-propane sultone, and control the dropping temperature to be less than 30°C.

[0033] More specifically, in step S1, the solvent includes a mixture of one or more of water, methanol, ethanol, isopropanol, acetone, and acetonitrile in any proportion. In step S2, the oxidant is one or more of sodium hypochlorite, hydrogen peroxide, oxygen, and copper oxide.

[0034] The method for preparing sodium polydipropane disulfide sulfonate adopts thioamide compounds and 1,3-propane sultone as raw materials to directly carry out sulfonation oxidation to prepare sodium polydipropane disulfide sulfonate, thereby reducing the synthesis steps of sodium polydipropane disulfide sulfonate, having the characteristics of simple process, low energy consumption, less waste water, high product yield (more than 91%) and high effective content (more than 98%), and being conducive to the industrial production of sodium polydipropane disulfide sulfonate.

[0035] Example 1

[0036] This embodiment provides a method for preparing sodium polydipropane disulfide sulfonate, comprising the following steps:

[0037] S1. Add 300 mL of methanol and 75.13 g (1 mol) of thioacetamide to a 500 mL four-necked bottle and stir evenly. Cool to 20° C. and slowly drop 129.46 g (1.06 mol) of 1,3-propane sultone. Control the dropping temperature to <30° C. After the dropwise addition, continue the reaction at 30° C. for 2 hours to obtain a 3-sulfimidopropanesulfonic acid solution. The specific reaction process is as follows:

[0038]

[0039] S2, adding sodium methoxide to the 3-sulfimidopropane sulfonic acid solution of step S1, controlling the pH of the solution to be greater than 10, continuing to add 3.97 g (0.05 mol) of copper oxide to the 3-sulfimidopropane sulfonic acid solution, heating to 50° C. for oxidation reaction for 6 h, then removing the solvent by vacuum concentration, washing with ethanol, filtering and drying to obtain sodium polydisulfide dipropane sulfonate; the specific reaction process is as follows:

[0040]

[0041] Example 2

[0042] This embodiment provides a method for preparing sodium polydipropane disulfide sulfonate. Compared with Example 1, the difference is that in step S1, 131.19 g (1 mol) of sodium methyl dithiocarbamate is used instead of thioacetamide, and the rest is roughly the same as Example 1 and will not be repeated here.

[0043] Comparative Example 1

[0044] Comparative Example 1 provides a method for preparing sodium polydisulfide propane sulfonate. Compared with Example 1, the difference is that 158.1 g (1 mol) of sodium thiosulfate is used instead of thioacetamide. The rest is roughly the same as Example 1 and will not be repeated here.

[0045] Comparative Example 2

[0046] Comparative Example 2 provides a method for preparing sodium polydipropane disulfide sulfonate. Compared with Example 1, the difference is that 56.06 g (1 mol) of sodium hydrosulfide is used instead of thioacetamide, and the rest is roughly the same as Example 1, which will not be repeated here.

[0047] Comparative Example 3

[0048] Comparative Example 3 provides a method for preparing sodium polydipropane disulfide sulfonate. Compared with Example 1, the difference is that ammonia water is used instead of sodium methoxide to adjust the pH. The rest is roughly the same as Example 1 and will not be repeated here.

[0049] Comparative Example 4

[0050] Comparative Example 4 provides a method for preparing sodium polydipropane disulfide sulfonate. Compared with Example 1, the difference is that sodium hydroxide solution is used instead of sodium methoxide to adjust the pH. The rest is roughly the same as Example 1 and will not be repeated here.

[0051] The yield and content of sodium polydipropane disulfide sulfonate of Examples 1 to 2 and Comparative Examples 1 to 4 were tested, and the results are shown in the following table.

[0052] Table 1 Test results of Examples 1 to 2 and Comparative Examples 1 to 4

[0053] Yield (%) content(%) Example 1 93 98.53 Example 2 92 98.23 Comparative Example 1 80 90.27 Comparative Example 2 81 91.32 Comparative Example 3 80 94.42 Comparative Example 4 78 95.02

[0054] As can be seen from Table 1, Examples 1 and 2 use thioamide compounds for sulfonation reaction, and organic bases are used to adjust the pH, so the yield and content of sodium polydisulfide propane sulfonate are relatively high; Comparative Examples 1 and 2 use sulfide salts for sulfonation reaction, and Comparative Examples 3 and 4 use inorganic bases to adjust the pH, so that the yield and content of the product are relatively low.

[0055] Example 3

[0056] This embodiment provides a method for preparing sodium polydipropane disulfide sulfonate. Compared with Example 1, the difference is that in step S1, the amount of 1,3-propane sultone added is 134.35 g (1.1 mol), in step S2, sodium ethoxide is added to adjust the pH>10, and the amount of copper oxide added is 6.36 g (0.08 mol); the rest is roughly the same as Example 1 and will not be repeated here.

[0057] Example 4

[0058] This embodiment provides a method for preparing sodium polydipropane disulfide sulfonate. Compared with Example 1, the difference is that in step S1, the amount of 1,3-propane sultone added is 128.24 g (1.05 mol), in step S2, sodium tert-butoxide is added to adjust the pH>10, and the amount of copper oxide added is 7.95 g (0.1 mol); the rest is roughly the same as Example 1 and will not be repeated here.

[0059] Example 5

[0060] This embodiment provides a method for preparing sodium polydipropane disulfide sulfonate. Compared with Example 1, the difference is that in step S1, the amount of 1,3-propane sultone added is 131.9 g (1.08 mol), and in step S2, the amount of copper oxide added is 5.56 g (0.07 mol); the rest is roughly the same as Example 1 and will not be repeated here.

[0061] Example 6

[0062] This embodiment provides an industrial preparation method of sodium polydipropane disulfide sulfonate, comprising the following steps:

[0063] S1. Add 300L methanol and 75.13kg (1kmol) thioacetamide to a 100L reactor and stir evenly. Cool to 20°C and slowly drop 129.46kg (1.06kmol) 1,3-propane sultone. Control the dropwise addition temperature to <30°C. After the dropwise addition is completed, continue the reaction at 30°C for 2 hours to obtain a 3-sulfimidopropanesulfonic acid solution.

[0064] S2. Add sodium methoxide to the 3-sulfimidopropane sulfonic acid solution of step S1, control the pH of the solution to be greater than 10, continue to add 3.97 kg (50 mol) of copper oxide to the 3-sulfimidopropane sulfonic acid solution, heat to 50° C. for oxidation reaction for 6 hours, then remove the solvent by vacuum concentration, wash with isopropanol, filter, and dry to obtain sodium polydisulfide dipropane sulfonate.

[0065] The yield and content of sodium polydipropane disulfide sulfonate in Examples 3 to 6 were tested, and the results are shown in the following table.

[0066] Table 2 Test results of Examples 3 to 6

[0067]

[0068]

[0069] As can be seen from Table 2, the preparation methods of sodium polydipropane disulfide sulfonate of Examples 2 to 5 have the advantages of high yield and high effective content; Example 6 is an industrial scale-up experiment of Example 1. By comparing the two, it can be seen that the present invention does not require too fine process control conditions in the scale-up experiment, and the yield and content are still high, indicating that the method is suitable for industrial production.

[0070] In summary, the present invention provides a method for preparing sodium polydisulfide propane sulfonate, wherein thioamide compounds, 1,3-propane sultone and a solvent are first mixed to react to obtain 3-sulfimido propane sulfonic acid, and then pH is controlled to be greater than 10, and an oxidant is continuously added to the 3-sulfimido propane sulfonic acid to react, and finally sodium polydisulfide propane sulfonate is obtained after reduced pressure concentration, soaking, washing, suction filtration and drying. The present invention adopts thioamide organic compounds as raw materials for sulfonation reaction, replacing inorganic substances such as hydrogen sulfide or sulfide salts in the prior art, avoiding the safety hazards caused by the existing hydrogen sulfide as raw materials and the problem that sulfide salts are easy to produce by-products as raw materials; when adjusting the pH of the solution, an organic base is used as a regulator, and no new ionic impurities are introduced, and no subsequent impurity removal is required, which reduces the production cost, and does not generate a large amount of waste water, thereby reducing resource waste and post-processing steps. The preparation method of the present invention has the characteristics of simple process, low energy consumption, less waste water, high yield of products and high effective content, which is conducive to the industrial production of sodium polydisulfide propane sulfonate.

[0071] The above embodiments are only used to illustrate the technical solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention may be modified or replaced by equivalents without departing from the spirit and scope of the technical solution of the present invention.

Claims

1. A method for preparing sodium polydipropane disulfide sulfonate, characterized in that: The following steps are involved: S1. Mix a thioamide compound, 1,3-propane sultone and a solvent and stir them evenly to obtain a 3-sulfimidopropane sulfonic acid solution; the molar ratio of the thioamide compound to the 1,3-propane sultone is 1:(1.01-1.10); the thioamide compound is one of thioacetamide and sodium methyldithiocarbamate; S2. Add a regulator to the 3-sulfimidopropane sulfonic acid solution of step S1, control the pH of the solution to be greater than 10, continue to add an oxidant to the 3-sulfimidopropane sulfonic acid solution for oxidation reaction, and then obtain sodium polydisulfide propane sulfonate after reduced pressure concentration, soaking, washing, suction filtration and drying; the regulator is one of sodium methoxide, sodium ethoxide and sodium tert-butoxide.

2. The method for preparing sodium polydipropane disulfide sulfonate according to claim 1, characterized in that: In step S2, the molar ratio of 3-sulfimidopropane sulfonic acid to the added oxidant in the 3-sulfimidopropane sulfonic acid solution is 1:(0.05-0.1).

3. The method for preparing sodium polydipropane disulfide sulfonate according to claim 1, characterized in that: In step S1, in the reaction system of the thioamide compound, 1,3-propane sultone and solvent, the reaction temperature is 20-60° C. and the reaction time is 0.5-3.0 h.

4. The method for preparing sodium polydipropane disulfide sulfonate according to claim 1, characterized in that: In step S2, the oxidation reaction temperature is 30-70°C and the time is 3-9 hours.

5. The method for preparing sodium polydipropane disulfide sulfonate according to claim 1, characterized in that: In step S1, the mixing process of the thioamide compound, 1,3-propane sultone and the solvent is: firstly, the thioamide compound and the solvent are mixed, and then 1,3-propane sultone is slowly added dropwise, and the dropping temperature is controlled to be less than 30°C.

6. The method for preparing sodium polydipropane disulfide sulfonate according to claim 1, characterized in that: In step S1, the solvent is a mixture of one or more of water, methanol, ethanol, isopropanol, acetone, and acetonitrile in any proportion.

7. The method for preparing sodium polydipropane disulfide sulfonate according to claim 1, characterized in that: In step S2, the oxidant is one or more of sodium hypochlorite, hydrogen peroxide, oxygen, and copper oxide.

Images