Preparation method of sodium thiazolinyl dithiopropane sulfonate and application thereof

Abstract

The application discloses a preparation method and application of sodium thiazolinyl dithiopropane sulfonate, and comprises the following steps: adding 1,3-propane sulfolane solution and an oxidizing agent into a mixed solution containing 2-mercaptothiazoline, sodium hydrosulfide and a solvent at 5-25 DEG C, and then reacting at 20-35 DEG C, and then recrystallizing to obtain sodium thiazolinyl dithiopropane sulfonate; the one-pot method is used to synthesize sodium thiazolinyl dithiopropane sulfonate by using 2-mercaptothiazoline, sodium hydrosulfide and 1,3-propane sulfolane as raw materials, a series of problems such as low yield and low effective content caused by multi-step reaction and repeated purification are avoided, the yield (more than 80%) and the purity (more than 95%) of the product are greatly improved, and the product is beneficial to large-scale production.

Description

Technical Field

[0001] The present invention relates to the technical field of chemical synthesis, and in particular to a preparation method of sodium thiazoline disulfide propane sulfonate and application thereof. Background Art

[0002] Sodium thiazolinyl dithiopropane sulfonate (SH-110), molecular formula: C6H11NO3S4, molecular weight: 273, CAS number: 8106-00-1, is a white to yellow solid powder. It is primarily used as a brightener in acid copper plating and is an essential additive in copper plating, producing decorative and functional coatings. Unlike SPS, SH-110 combines a grain refiner and a leveler, making it particularly suitable for circuit board electroplating.

[0003] In the related technology, SH-110 is obtained by reacting 1,3-propane sultone, sulfur, etc. as raw materials, but the preparation temperature is high, the reaction conditions are demanding, and the product yield and purity are low.

[0004] Therefore, a method for preparing sodium thiazolyldithiopropane sulfonate with low reaction temperature, high yield and high purity is needed. Summary of the Invention

[0005] In view of this, the present application provides a preparation method of sodium thiazolinyl dithiopropane sulfonate and its application, which are used to solve the problem of how to improve the yield and purity of sodium thiazolinyl dithiopropane sulfonate and reduce the reaction temperature.

[0006] In order to achieve the above technical objectives, this application adopts the following technical solutions:

[0007] In a first aspect, the present application provides a method for preparing sodium thiazolinyl dithiopropane sulfonate, comprising the following steps: adding a 1,3-propane sultone solution and an oxidant dropwise in sequence to a mixture comprising 2-mercaptothiazoline, sodium hydrosulfide, and a solvent at 5-25° C., reacting the mixture at 20-35° C., and then recrystallizing the mixture to obtain sodium thiazolinyl dithiopropane sulfonate.

[0008] Preferably, the molar ratio of sodium hydrosulfide to 2-mercaptothiazoline is 1:2-5.

[0009] Preferably, the molar ratio of sodium hydrosulfide to 1,3-propane sultone is 1:1.05-3.

[0010] Preferably, the oxidant is hydrogen peroxide.

[0011] Preferably, the molar ratio of sodium hydrosulfide to the oxidant is 1:1.05-2.5.

[0012] Preferably, the solvent includes one or more of methanol, ethanol, n-butanol, isopropanol.

[0013] Preferably, the solvent used for recrystallization is one or more of water, methanol, ethanol, n-butanol, isopropanol.

[0014] Preferably, the temperature for recrystallization is 25-30℃.

[0015] Preferably, the reaction time is 3-4h.

[0016] In a second aspect, the application provides a use of the preparation method in the preparation of a copper plating additive.

[0017] The application has the following advantages: the application uses 2-mercaptothiazoline, sodium hydrosulfide and 1,3-propane sulfolane as raw materials to synthesize thiazoline-based sodium dithiopropane sulfonate by one-pot method, avoids low yield and low effective content caused by multi-step reaction and repeated purification, greatly improves the yield (more than 80%) and purity (more than 95%) of the product, and is beneficial to large-scale production.

[0018] The application provides a preparation method of thiazoline-based sodium dithiopropane sulfonate, which is simple in process, high in yield and effective content, and beneficial to industrialized production. DETAILED DESCRIPTION

[0019] In order to make the purpose, technical scheme and advantages of the application clearer, the application will be further described in detail below with reference to examples. It should be understood that the specific examples described herein are only used to explain the application, and are not used to limit the application.

[0020] The application provides a preparation method of thiazoline-based sodium dithiopropane sulfonate, which includes the following steps: 1,3-propane sulfolane solution and an oxidizing agent are sequentially added dropwise into a mixed solution containing 2-mercaptothiazoline, sodium hydrosulfide and a solvent at 5-25℃, then reaction is carried out at 20-35℃, and then recrystallization is carried out, so that thiazoline-based sodium dithiopropane sulfonate is obtained.

[0021] Specifically, the preparation method of thiazoline-based sodium dithiopropane sulfonate is as follows: 1,3-propane sulfolane is added dropwise into a mixed solution containing 2-mercaptothiazoline, a solvent and sodium hydrosulfide by using a peristaltic pump to control the drop rate, the drop temperature is maintained at 5-25℃, then hydrogen peroxide is added dropwise by using a peristaltic pump to control the drop rate, the drop temperature is kept unchanged, reaction is completed at 20-35℃, then the solvent is removed, water is added to remove 2-mercaptothiazoline, and finally thiazoline-based sodium dithiopropane sulfonate is obtained by recrystallization purification; the reaction is as follows:

[0022]

[0023] Among them, 2-mercaptothiazoline, sodium hydrosulfide, and 1,3-propane sultone solution are used as raw materials, and hydrogen peroxide is used as a catalyst. Sodium thiazoline disulfide propane sulfonate is prepared by a one-pot method. The reaction temperature is low, the purity and yield are high, and the process is simple.

[0024] Preferably, the dropping temperature is maintained at 20-25°C, the reaction temperature is 30-35°C, and the reaction time is 3-4h. A low dropping temperature is not conducive to the formation of sodium 3-mercaptopropane sulfonate, and a high dropping temperature will cause 3-mercaptopropane sulfonic acid to self-oxidize. A low reaction temperature leads to side reactions and a decrease in the content of the main product. A high reaction temperature also causes 3-mercaptopropane sulfonic acid to self-oxidize. The process of generating sodium 3-mercaptopropane sulfonate is as follows:

[0025]

[0026] In this embodiment, the molar ratio of sodium hydrosulfide to 2-mercaptothiazoline is 1:2-5. Preferably, the molar ratio of sodium hydrosulfide to 2-mercaptothiazoline is 1:2-3. Too little 2-mercaptothiazoline will lead to a decrease in the yield and purity of SH-110.

[0027] In this embodiment, the molar ratio of sodium hydrosulfide to 1,3-propane sultone is 1:1.05-3; preferably, the molar ratio of sodium hydrosulfide to 1,3-propane sultone is 1:1.09-2; if the amount of 1,3-propane sultone is too small, the yield of SH-110 will be reduced.

[0028] In this embodiment, the oxidant is hydrogen peroxide. The molar ratio of sodium hydrosulfide to the oxidant is 1:1.05-2.5; preferably, the molar ratio of sodium hydrosulfide to the oxidant is 1.09-2. Too little hydrogen peroxide will result in a reduced yield of SH-110.

[0029] In this embodiment, the solvent includes one or more of methanol, ethanol, n-butanol, and isopropanol; preferably, the solvent is methanol.

[0030] In this embodiment, the solvent used for recrystallization is one or more of water, methanol, ethanol, n-butanol, and isopropanol; preferably, the solvent used for recrystallization is one or more of methanol and water. The recrystallization temperature is 60-65°C.

[0031] The present application provides an application of a preparation method in the preparation of a copper plating additive; the sodium thiazolyl disulfide propane sulfonate prepared by the preparation method of this scheme is used as one of the components of the copper plating additive.

[0032] The present invention is further described below through specific examples.

[0033] Example 1

[0034] A method for preparing sodium thiazolinyl dithiopropane sulfonate comprises the following steps:

[0035] To a 1000mL four-necked flask, add 225ml of methanol, 57.5g (0.73%, 0.75mol) of sodium hydrosulfide and 178.5g (1.5mol) of 2-mercaptothiazoline and stir evenly. Cool to 20°C and slowly add 100.6g (0.82mol) of 1,3-propane sultone dropwise. Use a peristaltic pump to control the dripping rate and the dripping temperature at 20-25°C. After 1,3-propane sultone is added to 1 / 3 of the total mass, 103.9g (27%, 0.82mol) of hydrogen peroxide is added dropwise using a peristaltic pump to control the dripping rate. The dripping rate of hydrogen peroxide and 1,3-propane sultone is 1:1, and the dripping temperature is controlled at 20-25°C. After the dropwise addition of hydrogen peroxide and 1,3-propane sultone is completed, the temperature is raised to 30-35°C and kept warm for 3 hours. After the reaction is completed, the reaction solution is poured into a 1000 ml single-necked bottle and rapidly dehydrated using a rotary evaporator to obtain a white solid. 200 g of water is added to the solid, and the water-insoluble 2-mercaptothiazoline is filtered out. The water in the filtrate is dehydrated until it becomes white. The temperature is controlled at 60-64°C, 300 g of methanol is added, and the mixture is naturally cooled to 20°C. The mixture is centrifuged and dried to obtain 174.29 g (yield 85.1%, purity 98.3%) of sodium thiazolinyl dithiopropane sulfonate.

[0036] Example 2

[0037] A method for preparing sodium thiazolinyl dithiopropane sulfonate comprises the following steps:

[0038] To a 1000mL four-necked flask, add 225ml of methanol, 57.5g (0.73%, 0.75mol) of sodium hydrosulfide and 178.5g (1.5mol) of 2-mercaptothiazoline and stir evenly. Cool to 20°C and slowly add 183.0g (1.5mol) of 1,3-propane sultone dropwise. Use a peristaltic pump to control the dripping rate and the dripping temperature at 20-25°C. After 1,3-propane sultone is added to 1 / 3 of the total mass, 103.9g (27%, 0.82mol) of hydrogen peroxide is added dropwise using a peristaltic pump to control the dripping rate. The dripping rate of hydrogen peroxide and 1,3-propane sultone is 1:1, and the dripping temperature is controlled at 20-25°C. After the hydrogen peroxide and 1,3-propane sultone were added dropwise, the temperature was raised to 30-35°C and kept warm for 3 hours to terminate the reaction. The reaction solution was poured into a 1000 ml single-necked bottle and rapidly dehydrated using a rotary evaporator to obtain a white solid. 200 g of water was added to the solid, and the water-insoluble 2-mercaptothiazoline was filtered out. The water in the filtrate was dehydrated until it turned white. The temperature was controlled at 60-64°C, 300 g of methanol was added, and the mixture was naturally cooled to 20°C. The mixture was centrifuged and dried to obtain 164.25 g (yield 80.2%, purity 98.1%) of sodium thiazolinyl dithiopropane sulfonate.

[0039] Example 3

[0040] A method for preparing sodium thiazolinyl dithiopropane sulfonate comprises the following steps:

[0041] To a 1000mL four-necked flask, add 225ml of methanol, 57.5g (0.73%, 0.75mol) of sodium hydrosulfide and 267.7g (2.25mol) of 2-mercaptothiazoline, stir evenly, cool to 20°C, slowly add 100.6g (0.82mol) of 1,3-propane sultone dropwise, control the dripping rate with a peristaltic pump, and control the dripping temperature at 20-25°C. After 1,3-propane sultone is added to 1 / 3 of the total mass, add 103.9g (27%, 0.82mol) of hydrogen peroxide dropwise using a peristaltic pump to control the dripping rate. The dripping rate of hydrogen peroxide and 1,3-propane sultone is 1:1, and the dripping temperature is controlled at 20-25°C. After the dropwise addition of hydrogen peroxide and 1,3-propane sultone is completed, the temperature is raised to 30-35°C and maintained for 3 hours to terminate the reaction; the reaction solution is poured into a 1000 ml single-necked bottle and rapidly dehydrated using a rotary evaporator to obtain a white solid, to which 200 g of water is added, and the water-insoluble 2-mercaptothiazoline is filtered out. The water in the filtrate is dehydrated until it becomes whitish, the temperature is controlled at 60-64°C, 300 g of methanol is added, and the mixture is naturally cooled to 20°C, centrifuged, and dried to obtain 179.20 g (yield 87.5%, purity 98.5%) of sodium thiazolinyl dithiopropane sulfonate.

[0042] Example 4

[0043] A method for preparing sodium thiazolinyl dithiopropane sulfonate comprises the following steps:

[0044] To a 1000mL four-necked flask, add 225ml of methanol, 57.5g (0.73%, 0.75mol) of sodium hydrosulfide and 178.5g (1.5mol) of 2-mercaptothiazoline and stir evenly. Cool to 20°C and slowly add 100.6g (0.82mol) of 1,3-propane sultone dropwise. Use a peristaltic pump to control the dripping rate and the dripping temperature at 20-25°C. After 1,3-propane sultone is added to 1 / 3 of the total mass, 188.9g (27%, 1.5mol) of hydrogen peroxide is added dropwise using a peristaltic pump to control the dripping rate. The dripping rate of hydrogen peroxide and 1,3-propane sultone is 1:1, and the dripping temperature is controlled at 20-25°C. After the dropwise addition of hydrogen peroxide and 1,3-propane sultone is completed, the temperature is raised to 30-35°C and kept warm for 3 hours to terminate the reaction; the reaction solution is poured into a 1000 ml single-necked bottle and rapidly dehydrated using a rotary evaporator to obtain a white solid, to which 200 g of water is added, and the water-insoluble 2-mercaptothiazoline is filtered out. The water in the filtrate is dehydrated until it becomes white, the temperature is controlled at 60-64°C, 300 g of methanol is added, and the mixture is naturally cooled to 20°C, centrifuged, and dried to obtain 176.54 g (yield 86.2%, purity 98.5%) of sodium thiazolinyl dithiopropane sulfonate.

[0045] Example 5

[0046] A method for preparing sodium thiazolinyl dithiopropane sulfonate comprises the following steps:

[0047] To a 1000L reactor, 225L of methanol, 57.5kg (0.73%, 0.75kmol) of sodium hydrosulfide and 178.5kg (1.5kmol) of 2-mercaptothiazoline were added and stirred evenly. The temperature was lowered to 20°C, and 100.6kg (0.82kmol) of 1,3-propane sultone was slowly added dropwise. The dripping rate was controlled by a peristaltic pump, and the dripping temperature was controlled at 20-25°C. After 1,3-propane sultone was added to 1 / 3 of the total mass, 103.9kg (27%, 0.82kmol) of hydrogen peroxide was added dropwise using a peristaltic pump. The dripping rate of hydrogen peroxide and 1,3-propane sultone was 1:1, and the dripping temperature was controlled at 20-25°C. After the hydrogen peroxide and 1,3-propane sultone were added dropwise, the temperature was raised to 30-35°C and kept warm for 3 hours to terminate the reaction; the solvent was dehydrated in the reactor to obtain a white solid, to which 200 kg of water was added, the mixture was centrifuged, and the filtrate was collected. The water in the filtrate was further dehydrated until it turned white. The temperature was controlled at 60-64°C, 300 kg of methanol was added, and the mixture was naturally cooled to 20°C. The mixture was centrifuged and dried to obtain 177.1 kg (yield 86.5%, purity 98.4%) of sodium thiazolinyl dithiopropane sulfonate.

[0048] Example 6

[0049] A method for preparing sodium thiazolinyl dithiopropane sulfonate is the same as Example 5 except that the amount of sodium hydrosulfide is adjusted to 115 kg (1.5 kmol). The yield of the obtained product is similar to that of Example 5, which also shows that the present invention is suitable for scale-up production.

[0050] Comparative Example 1

[0051] A method for preparing sodium thiazolinyl dithiopropane sulfonate, the other contents of which are the same as those of Example 1, except that the amount of sodium hydrosulfide is adjusted to 0.675 mol, that is, the molar ratio of sodium hydrosulfide to 1,3-propane sultone is 1:0.9.

[0052] Comparative Example 2

[0053] A method for preparing sodium thiazolinyl dithiopropane sulfonate is the same as Example 1 except that the amount of 2-mercaptothiazoline is adjusted to 0.75 mol, that is, the molar ratio of sodium hydrosulfide to 2-mercaptothiazoline is 1:1.

[0054] Comparative Example 3

[0055] A method for preparing sodium thiazolinyl disulfide propane sulfonate is the same as Example 1 except that the amount of hydrogen peroxide is adjusted to 85 g (27%, 0.675 mol), that is, the molar ratio of sodium hydrosulfide to hydrogen peroxide is 1:0.9.

[0056] Comparative Example 4

[0057] A method for preparing sodium thiazoline disulfide propane sulfonate, the other contents of which are the same as those in Example 1, except that the dropping temperature is adjusted to 40°C.

[0058] Evaluation Test

[0059] The yield and purity of sodium thiazolyldithiopropanesulfonate (SH-110) obtained in Example 1 and Comparative Example 1 were tested, and the results are shown in Table 1.

[0060] Table 1 Test results

[0061]

[0062] As shown in Table 1, when the molar ratio of sodium hydrosulfide to 1,3-propane sultone is 1:0.9, the amount of sodium 3-mercaptopropane sulfonate decreases, which in turn affects the oxidation yield of SH-110, but has no effect on the purity of SPS.

[0063] When the molar ratio of sodium hydrosulfide to 2-mercaptothiazoline is 1:1, the yield and purity of SH-110 decrease greatly, mainly because the decrease of 2-mercaptothiazoline leads to the oxidation of part of 3-mercapto propane sulfonate sodium into polydisulfide propane sulfonate sodium, which in turn leads to the decrease of the yield and purity of SH-110.

[0064] When the molar ratio of sodium hydrosulfide to hydrogen peroxide is 1:0.9, the yield of SH-110 decreases, and the purity changes little, mainly because the decrease of the oxidant leads to the decrease of the generated SH-110, and the yield decreases after crystallization and purification.

[0065] When the dropping temperature increases, two competitive reactions occur, i.e. the reaction of 2-mercaptothiazoline with 3-mercapto propane sulfonate sodium and the reaction of 3-mercapto propane sulfonate sodium itself. Because the temperature increases, the reaction of 3-mercapto propane sulfonate sodium itself is the main reaction, which inhibits the reaction of 2-mercaptothiazoline with 3-mercapto propane sulfonate sodium, thus leading to the sharp decrease of the yield and purity of SH-110.

[0066] The yield of the product obtained in Examples 1-6 is between 85% and 87%, and the purity of the product is 98.3-98.5%.

[0067] The above is only the preferred specific embodiment of the present application, but the protection scope of the present application is not limited to this. Any change or replacement that can be easily thought of by those skilled in the art within the technical range disclosed by the present application should be covered in the protection scope of the present application.

Claims

1. A method for preparing sodium thiazolinyl dithiopropane sulfonate, characterized in that: The method comprises the following steps: adding 1,3-propane sultone solution and an oxidant dropwise in sequence to a mixed solution containing 2-mercaptothiazoline, sodium hydrosulfide and a solvent at 5-25° C., reacting at 20-35° C., and then recrystallizing to obtain the sodium thiazoline dithiopropane sulfonate.

2. The method for preparing sodium thiazolinyl dithiopropane sulfonate according to claim 1, wherein The molar ratio of the sodium hydrosulfide to 2-mercaptothiazoline is 1:2-5.

3. The preparation method of sodium thiazolinyl dithiopropane sulfonate according to claim 1, wherein The molar ratio of the sodium hydrosulfide to 1,3-propane sultone is 1:1.05-3.

4. The method for preparing sodium thiazolinyl dithiopropane sulfonate according to claim 1, wherein The oxidant is hydrogen peroxide.

5. The method for preparing sodium thiazolinyl dithiopropane sulfonate according to claim 1, wherein The molar ratio of the sodium hydrosulfide to the oxidant is 1:1.05-2.

5.

6. The method for preparing sodium thiazolinyl dithiopropane sulfonate according to claim 1, wherein The solvent includes one or more of methanol, ethanol, n-butanol, and isopropanol.

7. The method for preparing sodium thiazolinyl dithiopropane sulfonate according to claim 1, wherein The solvent used for the recrystallization is one or more of water, methanol, ethanol, n-butanol and isopropanol.

8. The method for preparing sodium thiazolinyl dithiopropane sulfonate according to claim 1, wherein The recrystallization temperature is 60-65°C.

9. The method for preparing sodium thiazolinyl dithiopropane sulfonate according to claim 1, wherein The reaction time is 3-4 hours.

10. Use of the preparation method according to any one of claims 1 to 9 in preparing a copper plating additive.

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