Preparation method of 3-mercaptopropane sodium sulfonate

Abstract

The invention provides a preparation method of 3-mercaptopropanesulfonic acid sodium salt, which comprises the following steps: S1, dissolving sulfurized cyclopropane, an addition sulfonating agent and an antioxidant in a solvent to form a mixed solution, heating, slowly adding inorganic acid to control the pH value to be 1-3, and continuously reacting the mixed solution at the temperature to obtain a reactant solution containing 3-mercaptopropanesulfonic acid; s2, adjusting the reactant solution containing 3-mercaptopropanesulfonic acid to be alkaline by adopting a pH regulator to obtain a 3-mercaptopropanesulfonic acid sodium crude product, and purifying and drying to obtain a 3-mercaptopropanesulfonic acid sodium refined product; the preparation method provided by the invention has the advantages of simple process, no side reaction, no use of toxic reagents in the reaction process, lower raw material cost and suitability for industrial production, and the 3-mercaptopropane sodium sulfonate with the yield of 96% or more and the purity of 98% or more is finally prepared.

Description

Technical Field

[0001] The present invention relates to the technical field of organic synthesis, in particular to a method for preparing sodium 3-mercaptopropane sulfonate. Background Art

[0002] Sodium 3-mercaptopropane sulfonate (MPS) is primarily used as an electroplating additive intermediate for the preparation of copper plating brighteners, making it particularly suitable for electroplating of printed circuit boards. Currently, the most common synthesis method for preparing sodium 3-mercaptopropane sulfonate (MPS) is based on 1,3-propane sultone (1,3-PS) and sodium hydrosulfide as starting materials.

[0003] Patent CN101624361A discloses a method for synthesizing high-purity sodium 3-mercaptopropane sulfonate. The method involves synthesizing sodium hydrosulfide from sodium methoxide and hydrogen sulfide, which is then reacted with 1,3-propane sultone (1,3-PS) to produce sodium 3-mercaptopropane sulfonate. However, the highly toxic hydrogen sulfide gas used in the reaction poses significant risks in industrial production, and there is also the risk of oxidation by air during the reaction.

[0004] Patent CN116375619A discloses a synthesis process for sodium 3-mercaptopropane sulfonate. The patent specifically involves using silicon tetrachloride and methanol to generate hydrochloric acid, which then reacts with sodium sulfide to produce sodium hydrosulfide, which then reacts with 1,3-propane sultone (1,3-PS) to produce sodium 3-mercaptopropane sulfonate. However, the reaction uses silicon tetrachloride liquid as a fuming liquid, and introduces a new silicon element, resulting in low atomic utilization.

[0005] Patent CN117800882A discloses a process for synthesizing sodium 3-mercaptopropane sulfonate. The specific process involves reacting hydrogen sulfide gas with alkali solution under a protective atmosphere to produce liquid sodium hydrosulfide, which then reacts with 1,3-propane sultone (1,3-PS) to produce sodium 3-mercaptopropane sulfonate. However, the reaction between alkali solution and sodium hydrosulfide is prone to side reactions, producing the impurity sodium sulfide, and the use of highly toxic hydrogen sulfide gas places high demands on production conditions.

[0006] Therefore, developing a non-toxic preparation method for producing sodium 3-mercaptopropane sulfonate with high yield and high purity has important industrial application value. Summary of the Invention

[0007] In view of the above-mentioned shortcomings of the prior art, the object of the present invention is to provide a method for preparing sodium 3-mercaptopropane sulfonate, which is used to solve the problems of the prior art in the production process of sodium 3-mercaptopropane sulfonate, such as the use of toxic hydrogen sulfide gas, low content and purity, and high cost.

[0008] To achieve the above-mentioned object and other related objects, the present invention provides a method for preparing sodium 3-mercaptopropane sulfonate, comprising the following steps:

[0009] S1, dissolving cyclopropane sulfide, an addition sulfonating agent, and an antioxidant in a solvent to form a mixed solution, slowly adding an inorganic acid to control the pH to 1-3 after heating, and then maintaining the mixed solution at this temperature to continue reacting to obtain a reactant solution containing 3-mercaptopropanesulfonic acid;

[0010] S2. The pH of the reaction solution containing 3-mercaptopropanesulfonic acid is adjusted to alkaline using a pH regulator to obtain a crude product of sodium 3-mercaptopropanesulfonate, which is then purified and dried to obtain a refined product of sodium 3-mercaptopropanesulfonate.

[0011] Preferably, in step S1, the molar ratio of the cyclopropane sulfide, the added sulfonating agent, and the inorganic acid is 1:(0.55-1.4):(1.4-1.6).

[0012] Preferably, in step S1, the molar ratio of the cyclopropane sulfide to the antioxidant is 1:(0.005-0.01).

[0013] Preferably, in step S1, the addition sulfonating agent is selected from one or more of sodium sulfite, sodium bisulfite, potassium bisulfite, sodium metabisulfite, and sodium metabisulfate.

[0014] Preferably, in step S1, the inorganic acid is selected from one or more of hydrochloric acid and sulfuric acid.

[0015] Preferably, in step S1, the antioxidant is selected from one or more of L-ascorbic acid, butylated hydroxytoluene (BHT), and butylated hydroxyanisole (BHA).

[0016] Preferably, in step S1, the solvent is a mixture of an organic solvent and water, and the organic solvent is selected from one or more of acetonitrile, acetone, and tetrahydrofuran.

[0017] Preferably, in step S1, the total concentration of the mixed solution is 10-21 wt%.

[0018] Preferably, in step S1, the temperature is raised to 50-60°C.

[0019] Preferably, in step S1, the continued reaction is for 3 to 5 hours.

[0020] Preferably, in step S2, the pH adjuster is selected from one or more of sodium hydroxide, sodium carbonate, and sodium bicarbonate.

[0021] Preferably, in step S2, adjusting to alkalinity is adjusting to a pH of 9-11.

[0022] Preferably, in step S2, the purification is performed by nanofiltration using a nanofiltration membrane.

[0023] Preferably, in step S2, the drying is spray drying.

[0024] As described above, the preparation method of sodium 3-mercaptopropane sulfonate of the present invention has the following beneficial effects:

[0025] The preparation method of sodium 3-mercaptopropane sulfonate of the present invention comprises the following steps: using cyclopropane sulfide and an added sulfonating agent as starting materials, reacting under the action of an inorganic acid, adjusting the pH with a pH regulator, and purifying to obtain the product sodium 3-mercaptopropane sulfonate. The prepared sodium 3-mercaptopropane sulfonate has a high yield and purity, wherein the yield can reach above 96%, and the purity can reach above 98%.

[0026] The preparation method of sodium 3-mercaptopropane sulfonate of the present invention has a simple process, no side reaction, no toxic reagents are used in the reaction process, and the raw material cost is low, so the method is suitable for industrial production. DETAILED DESCRIPTION

[0027] The following describes the embodiments of the present invention through specific examples. Those skilled in the art will readily understand the other advantages and benefits of the present invention from the disclosure herein. The present invention may also be implemented or applied through various other specific embodiments, and the details in this specification may be modified or altered based on different viewpoints and applications without departing from the spirit of the present invention.

[0028] When a numerical range is disclosed herein, the above range is deemed to be continuous and includes the minimum and maximum values of the range, as well as every value between such minimum and maximum values. Further, when a range refers to an integer, every integer between the minimum and maximum values of the range is included. In addition, when multiple ranges are provided to describe features or characteristics, the ranges can be merged. In other words, unless otherwise indicated, all ranges disclosed herein should be understood to include any and all subranges included therein. For example, a specified range from "1 to 10" should be deemed to include any and all subranges between a minimum of 1 and a maximum of 10. Exemplary subranges of the range 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8, 5.5 to 10, and the like.

[0029] In addition, it should be understood that one or more method steps mentioned in the present invention do not exclude the existence of other method steps before or after the combination step or the insertion of other method steps between these explicitly mentioned steps, unless otherwise specified; and, unless otherwise specified, the numbering of each method step is merely a convenient tool for identifying each method step, and is not intended to limit the order of arrangement of each method step or to define the scope of implementation of the present invention. Changes or adjustments in their relative relationships, without substantially changing the technical content, should also be regarded as the scope of implementation of the present invention.

[0030] The present invention provides a method for preparing sodium 3-mercaptopropane sulfonate, comprising the following steps:

[0031] S1, dissolving cyclopropane sulfide, an addition sulfonating agent, and an antioxidant in a solvent to form a mixed solution, slowly adding an inorganic acid to control the pH to 1-3 after heating, and then maintaining the mixed solution at this temperature to continue reacting to obtain a reactant solution containing 3-mercaptopropanesulfonic acid;

[0032] S2. The pH of the reaction solution containing 3-mercaptopropanesulfonic acid is adjusted to alkaline using a pH regulator to obtain a crude product of sodium 3-mercaptopropanesulfonate, which is then purified and dried to obtain a refined product of sodium 3-mercaptopropanesulfonate.

[0033] The present invention uses cyclopropane sulfide and an added sulfonating agent as starting materials. The added sulfonating agent, under acidic conditions, generates sulfurous acid, which reacts with the cyclopropane sulfide to form the intermediate 3-mercaptopropanesulfonic acid. This intermediate is then alkalized to produce sodium 3-mercaptopropane sulfonate. Compared to the prior art method of using 1,3-propane sultone as the starting material to prepare the intermediate, the present preparation method has no side reactions and no harmful materials during the reaction process, ultimately producing sodium 3-mercaptopropane sulfonate in high yield and purity.

[0034] In the preparation method of the present invention, in step S1, the molar ratio of the cyclopropane sulfide, the addition sulfonating agent, and the inorganic acid is 1:(0.55-1.4):(1.4-1.6). For example, 1:(0.55-1.3):(1.4-1.6), 1:(0.55-0.6):(1.4-1.6), 1:(0.6-0.7):(1.4-1.6), 1:(0.7-0.8):(1.4-1.6), 1:(0.8-0.9):(1.4-1.6), 1:(0.9-1.0):(1.4-1.6 ), 1:(1.0~1.1):(1.4~1.6), 1:(1.1~1.2):(1.4~1.6), 1:(1.2~1.3):(1.4~1.6), 1:(1.3~1.4):(1.4~1.6), 1:(0.55~1.4):(1.4~1.5) or 1:(0.55~1.4):(1.5~1.6).

[0035] In the preparation method of the present invention, in step S1, the molar ratio of the cyclopropane sulfide to the antioxidant is 1:(0.005-0.01), for example, 1:(0.005-0.006), 1:(0.006-0.007), 1:(0.007-0.008), 1:(0.008-0.009), or 1:(0.009-0.01).

[0036] In the preparation method of the present invention, in step S1, the addition sulfonating agent is selected from one or more of sodium sulfite, sodium bisulfite, potassium bisulfite, sodium metabisulfite, and sodium metabisulfate.

[0037] In the preparation method of the present invention, in step S1, the inorganic acid is selected from one or more of hydrochloric acid and sulfuric acid. If an organic acid is used, it will undergo an esterification reaction with the mercaptan to produce impurities.

[0038] In the preparation method of the present invention, in step S1, the antioxidant is selected from one or more of L-ascorbic acid, butylated hydroxytoluene, and butylated hydroxyanisole.

[0039] In the preparation method of the present invention, in step S1, the solvent is a mixture of an organic solvent and water, and the organic solvent is selected from one or more of acetonitrile, acetone, and tetrahydrofuran. In a preferred embodiment of the present invention, the mass ratio of the organic solvent to water is 1:(1-3). For example, it is 1:(1-2) or 1:(2-3). Cyclopropane sulfide is an organic substance, and the added sulfonating agent is an inorganic substance. The solubility of the two is different. Mixing an organic solvent with water as a solvent is more conducive to forming a homogeneous phase. Alcoholic organic solvents will react with cyclopropane sulfide and cannot be used.

[0040] In the preparation method of the present invention, in step S1, the total concentration of the mixed solution is 10-21 wt%, for example, 10-12 wt%, 12-14 wt%, 14-16 wt%, 16-18 wt%, 18-20 wt% or 20-21 wt%.

[0041] In the preparation method of the present invention, in step S1, the temperature is raised to 50-60°C, for example, 50-52°C, 52-54°C, 54-56°C, 56-58°C or 58-60°C.

[0042] In the preparation method of the present invention, in step S1, the continued reaction is for 3 to 5 hours, for example, 3 to 3.5 hours, 3.5 to 4 hours, 4 to 4.5 hours, or 4.5 to 5 hours.

[0043] In the preparation method of the present invention, in step S2, the pH regulator is selected from one or more of sodium hydroxide, sodium carbonate, and sodium bicarbonate.

[0044] In the preparation method of the present invention, in step S2, the adjustment to alkalinity is to adjust the pH to 9 to 11, for example, 9 to 10 or 10 to 11.

[0045] In the preparation method of the present invention, in step S2, the purification is performed by nanofiltration using a nanofiltration membrane. In a preferred embodiment of the present invention, the pore size of the nanofiltration membrane is 100 to 200 Daltons, for example, 100 to 120 Daltons, 120 to 140 Daltons, 140 to 160 Daltons, 160 to 180 Daltons, or 180 to 200 Daltons.

[0046] In the preparation method of the present invention, in step S2, the drying is spray drying.

[0047] Example 1

[0048] Preparation of sodium 3-mercaptopropane sulfonate:

[0049] S1, 74.1g (1mol) cyclopropane sulfide, 124.9g (1.2mol) sodium bisulfite, 1.76g (0.01mol) L-ascorbic acid, co-dissolved in 1000g of acetonitrile-water mixture (wherein 300g acetonitrile, 700g water) to form a mixed solution, the temperature was raised to 50-60°C, 148.0g (1.5mol) 37wt% aqueous hydrochloric acid solution was slowly added dropwise to adjust the pH thereof to 1-3, and after completion of the addition, the mixture was stirred at 50-60°C to obtain a reactant solution containing 3-mercaptopropanesulfonic acid;

[0050]

[0051] S2. The pH of the reactant solution was adjusted to 10 with a 30 wt % aqueous sodium hydroxide solution to obtain a crude product of sodium 3-mercaptopropane sulfonate; the crude product solution was purified by nanofiltration through a nanofiltration membrane with a cutoff of 100 to 200 Daltons, and the retentate was spray-dried (setting the feed rate to 10 to 25 g / s, the nozzle temperature to 130 to 150° C., and the atomizing disk speed to 16,000 to 18,000 rpm) to obtain sodium 3-mercaptopropane sulfonate;

[0052]

[0053] Example 2

[0054] Compared with Example 1, the difference is that in step S1, the amounts of raw materials used are: 74.1 g (1 mol) of cyclopropane sulfide, 135.3 g (1.3 mol) of sodium bisulfite, 1.76 g (0.01 mol) of L-ascorbic acid, and 148.0 g (1.5 mol) of 37 wt% aqueous hydrochloric acid solution. The rest is the same as in Example 1.

[0055] Example 3

[0056] Compared with Example 1, the difference is that in step S1, the amounts of raw materials used are: 74.1 g (1 mol) of cyclopropane sulfide, 145.7 g (1.4 mol) of sodium bisulfite, 1.76 g (0.01 mol) of L-ascorbic acid, and 148.0 g (1.5 mol) of 37 wt% aqueous hydrochloric acid solution. The rest is the same as in Example 1.

[0057] Example 4

[0058] Compared with Example 2, the difference is that in step S1, 157.8 g (1.6 mol) of 37 wt% hydrochloric acid aqueous solution is used.

[0059] The rest of Example 4 is the same as Example 2.

[0060] Example 5

[0061] Compared with Example 2, the difference is that in step S1, 0.65 mol of sodium sulfite is used instead of 1.3 mol of sodium bisulfite.

[0062] Example 6

[0063] Compared with Example 2, the difference is that in step S1, butylated hydroxytoluene (BHT) is used instead of L-ascorbic acid.

[0064] Comparative Example 1

[0065] Compared with Example 1, the difference is that in step S1, the amounts of raw materials used are: 74.1 g (1 mol) of cyclopropane sulfide, 104.1 g (1 mol) of sodium bisulfite, 1.76 g (0.01 mol) of L-ascorbic acid, and 148.0 g (1.5 mol) of 37 wt% aqueous hydrochloric acid solution. The rest is the same as in Example 1.

[0066] Comparative Example 2

[0067] Compared with Example 1, the difference is that in step S1, the amounts of raw materials used are: 74.1 g (1 mol) of cyclopropane sulfide, 166.6 g (1.6 mol) of sodium bisulfite, 1.76 g (0.01 mol) of L-ascorbic acid, and 148.0 g (1.5 mol) of 37 wt% aqueous hydrochloric acid solution. The rest is the same as in Example 1.

[0068] Comparative Example 3

[0069] Compared with Example 1, the difference is that in step S1, the amount of raw material used is: 197.3 g (2.0 mol) of 37 wt% hydrochloric acid aqueous solution. The rest is the same as Example 1.

[0070] Comparative Example 4

[0071] Compared with Example 1, the difference is that in step S1, the amount of L-ascorbic acid used is 0.2 g (0.001 mol). The rest is the same as Example 1.

[0072] Results and Analysis:

[0073] The purity of the sodium 3-mercaptopropane sulfonate prepared in the above examples and comparative examples was detected by HPLC external standard method, and the yield was calculated. The results are shown in Table 1.

[0074] Table 1

[0075]

[0076]

[0077] Combining the examples, comparative examples and Table 1 above, it can be seen that the sodium 3-mercaptopropane sulfonate prepared by the preparation method of the present invention has a high yield and purity, the yield can reach more than 96%, and the purity can reach more than 98%.

[0078] In Comparative Example 1, the molar ratio of cyclopropane sulfide: sodium bisulfite is 1:1, and the yield of sodium 3-mercaptopropane sulfonate is lower than that of Example 1. The main reason is that the cyclopropane sulfide is not completely reacted and there is a large amount of residue, resulting in a low final yield and purity.

[0079] In Comparative Example 2, the molar ratio of cyclopropane sulfide to sodium bisulfite is 1:1.6, and the purity of sodium 3-mercaptopropane sulfonate is low. The main reason is that there is a large amount of sodium hydrosulfite remaining, which produces sulfur dioxide as a side reaction, causing the cyclopropane sulfide to undergo a ring-opening reaction, resulting in a decrease in product purity. Therefore, it can be seen that when the molar ratio of cyclopropane sulfide to sodium bisulfite is low, the reaction of cyclopropane sulfide is incomplete; when the molar ratio of cyclopropane sulfide to sodium bisulfite is high, more sodium bisulfite remains, and more sodium bisulfite is prone to produce sulfur dioxide gas, which reduces the purity and yield of sodium 3-mercaptopropane sulfonate; therefore, the molar ratio of cyclopropane sulfide to sodium bisulfite needs to be controlled within a limited range.

[0080] In Comparative Example 3, a large amount of hydrochloric acid was used, and the yield and purity of sodium 3-mercaptopropane sulfonate were significantly lower than those in Example 1. This may be because hydrochloric acid itself reacted with cyclopropane sulfide to produce impurity chloromercaptopropane liquid, resulting in a decrease in purity and yield.

[0081] In Comparative Example 4, the proportion of L-ascorbic acid is low, and the purity of sodium 3-mercaptopropane sulfonate is significantly lower than that in Example 4. This may be because the proportion of L-ascorbic acid is low, which cannot effectively prevent the oxidation of sodium 3-mercaptopropane sulfonate by oxygen in the air.

[0082] In summary, the preparation method of sodium 3-mercaptopropane sulfonate of the present invention uses cyclopropane sulfide and an added sulfonating agent as starting materials, has no side reactions, and does not contain harmful solvents during the reaction process. The finally prepared sodium 3-mercaptopropane sulfonate has a high yield and purity.

[0083] Therefore, the present invention effectively overcomes various shortcomings of the prior art and has high industrial utilization value.

[0084] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the present invention. Anyone skilled in the art may modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by one of ordinary skill in the art without departing from the spirit and technical principles disclosed herein are intended to be covered by the claims of the present invention.

Claims

1. A method for preparing sodium 3-mercaptopropane sulfonate, characterized in that: The following steps are involved: S1, dissolving cyclopropane sulfide, an addition sulfonating agent, and an antioxidant in a solvent to form a mixed solution, slowly adding an inorganic acid to control the pH to 1-3 after heating, and then maintaining the mixed solution at this temperature to continue reacting to obtain a reactant solution containing 3-mercaptopropanesulfonic acid; S2. The pH of the reaction solution containing 3-mercaptopropanesulfonic acid is adjusted to alkaline using a pH regulator to obtain a crude product of sodium 3-mercaptopropanesulfonate, which is then purified and dried to obtain a refined product of sodium 3-mercaptopropanesulfonate.

2. The preparation method of sodium 3-mercaptopropane sulfonate according to claim 1, wherein In step S1, the molar ratio of the cyclopropane sulfide, the added sulfonating agent, and the inorganic acid is 1:(0.55-1.4):(1.4-1.6).

3. The preparation method of sodium 3-mercaptopropane sulfonate according to claim 1, wherein In step S1, the molar ratio of the cyclopropane sulfide to the antioxidant is 1:(0.005-0.01).

4. The preparation method of sodium 3-mercaptopropane sulfonate according to claim 1, wherein In step S1, the addition sulfonating agent is selected from one or more of sodium sulfite, sodium bisulfite, potassium bisulfite, sodium metabisulfite, and sodium metabisulfate; And / or, in step S1, the inorganic acid is selected from one or more of hydrochloric acid and sulfuric acid.

5. The preparation method of sodium 3-mercaptopropane sulfonate according to claim 1, wherein In step S1, the antioxidant is selected from one or more of L-ascorbic acid, butylated hydroxytoluene, and butylated hydroxyanisole.

6. The method for preparing sodium 3-mercaptopropane sulfonate according to claim 1, wherein In step S1, the solvent is a mixture of an organic solvent and water, and the organic solvent is selected from one or more of acetonitrile, acetone, and tetrahydrofuran.

7. The method for preparing sodium 3-mercaptopropane sulfonate according to claim 6, wherein The mass ratio of the organic solvent to water is 1:(1-3).

8. The method for preparing sodium 3-mercaptopropane sulfonate according to claim 1, wherein In step S1, the total concentration of the mixed solution is 10-21 wt%; And / or, in step S1, the heating is to 50-60°C; And / or, in step S1, the continued reaction is for 3 to 5 hours.

9. The method for preparing sodium 3-mercaptopropane sulfonate according to claim 1, wherein In step S2, the pH regulator is selected from one or more of sodium hydroxide, sodium carbonate, and sodium bicarbonate; And / or, in step S2, the adjusting to alkalinity is adjusting to a pH of 9-11.

10. The method for preparing sodium 3-mercaptopropane sulfonate according to claim 1, wherein In step S2, the purification is performed by nanofiltration using a nanofiltration membrane; And / or, in step S2, the drying is spray drying.

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