Method for rapidly preparing stannous methanesulfonate
By using microwave heating and infrared temperature control, combined with a SiC material reactor and antioxidants, the problems of long preparation time and unstable yield of stannous methanesulfonate were solved, and a rapid and stable preparation process was achieved with a yield of 84.1% to 92.4%.
Patent Information
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- LIUZHOU HUAXI COLORED DESIGN & RESEARCH INSTITUTE CO LTD
- Filing Date
- 2025-08-14
- Publication Date
- 2026-07-23
Smart Images
Figure CN2025114534_23072026_PF_FP_ABST
Abstract
Description
A method for rapid preparation of stannous methanesulfonate Technical Field
[0001] This invention belongs to the field of stannous methanesulfonate preparation, and specifically relates to a method for rapidly preparing stannous methanesulfonate. Background Technology
[0002] With the rapid development of the electroplating and electronics industries, people have increasingly higher requirements for electroplating solutions, and there are more and more aspects to pay attention to, such as the safety, stability, and environmental friendliness of the electroplating solution. Electroplating solutions with stannous methanesulfonate as the main salt have advantages such as solution stability, low toxicity, low corrosion, low foaming, and high coating quality, and are mainly used in the tin plating process of electronic components.
[0003] Currently, the preparation process of stannous methanesulfonate mainly involves a displacement reaction between tin and methanesulfonic acid. CN1657520A discloses a method for preparing stannous methanesulfonate from tin powder. The method involves a displacement reaction between tin powder and methanesulfonic acid, followed by filtration, crystallization, and washing of the reaction solution to obtain stannous methanesulfonate crystals. Different concentrations of the crystals are then prepared. The yield of stannous methanesulfonate in this invention is approximately 90%.
[0004] Li Liqing disclosed a research study on the synthesis process of stannous methanesulfonate. He investigated the effect of experimental conditions on the yield of stannous methanesulfonate. Methanesulfonic acid and tin granules were heated to 140℃ in an oil bath and reacted for approximately 5.5 hours. The reaction was considered complete when the tin granules in the three-necked flask were completely dissolved. The reaction was stirred with an electric stirrer during the process. The reaction solution was then cooled to crystallize, filtered, and the filtrate was recovered. The filter cake was washed with anhydrous diethyl ether (the washing liquid could be separated from the diethyl ether and methanesulfonic acid by distillation at 40℃ and recovered for reuse). The product was then vacuum dried to obtain a white solid product. The results showed that the synthetic route was simple, the product was a white solid, the yield was high, and the product purity was high. The optimal process was a temperature of 140℃ and a reaction time of 5.5 hours, with tin granules having a diameter of 3 mm being the best choice. Under these experimental conditions, the yield of stannous methanesulfonate reached 97.08%. However, in actual operation, this yield is not stable, and the preparation time is long. Summary of the Invention
[0005] The purpose of this invention is to solve the above-mentioned technical problems and provide a simple, easy-to-control, rapid and stable method for preparing stannous methanesulfonate.
[0006] To achieve the above objectives, the technical solution of the present invention is as follows:
[0007] A rapid method for preparing stannous methanesulfonate involves reacting tin with a methanesulfonic acid solution under microwave heating for a period of time, followed by cooling and crystallization, filtration, washing, and drying to obtain the stannous methanesulfonate product. The molar ratio of tin to methanesulfonic acid is 1:(2-8), the microwave power is 500W-1500W, the reaction temperature is 120℃-150℃, and the reaction time is 1-2 hours. The filtrate obtained after filtration is a methanesulfonic acid solution, which can be recycled back to the microwave reactor for continued use.
[0008] The reaction principle of this invention is as follows:
[0009]
[0010] As a further technical solution, the tin mentioned above is tin flower or tin powder.
[0011] As a further technical solution, the mass concentration of the methanesulfonic acid solution mentioned above is 70% to 98%.
[0012] As a further technical solution, the molar ratio of tin to methanesulfonic acid is 1:4, the microwave power is 1500W, the reaction temperature is 140℃, the reaction time is 2 hours, and the mass concentration of the methanesulfonic acid solution is 70%.
[0013] As a further technical solution, the cooling crystallization described above involves naturally cooling the reaction product to 40°C to 50°C.
[0014] As a further technical solution, the washing described above is performed using anhydrous ethanol.
[0015] As a further technical solution, the microwave reactor for the tin and methanesulfonic acid solution described above is made of SiC material and is equipped with an infrared temperature measurement system.
[0016] As a further technical solution, the stannous methanesulfonate crystals are prepared into a stannous methanesulfonate solution, and an antioxidant is added to the stannous methanesulfonate solution to obtain an antioxidant stannous methanesulfonate liquid product.
[0017] As a further technical solution, the antioxidant mentioned above is hydroquinone, calculated at 0.2-0.6g per 100mL of stannous methanesulfonate solution.
[0018] Compared with the prior art, the beneficial effects of the present invention are as follows:
[0019] Compared to the problems of high-temperature decomposition and unstable yield caused by the temperature difference between the inside and outside of the reactor in traditional oil bath heating, this invention uses a combination of infrared and microwave. Infrared temperature control can precisely control the reaction temperature and avoid decomposition of stannous methanesulfonate due to excessive temperature. Microwaves directly intensify the molecular motion of reactant molecules, which significantly accelerates the reaction. Combined with the limited preparation parameters of this invention, rapid preparation of stannous methanesulfonate can be achieved within 1 to 2 hours, and the yield can be stabilized at 84.1% to 92.4%.
[0020] The microwave reactor of this invention uses SiC material, which utilizes SiC's strong microwave absorption properties to achieve rapid heating, shorten reaction time, and is also more energy-efficient. Attached Figure Description
[0021] Figure 1 is a schematic diagram of the stannous methanesulfonate product of Example 4 of the present invention;
[0022] Figure 2 shows the relationship between the yield of stannous methanesulfonate product of the present invention and microwave power (see red line).
[0023] Figure 3 shows the relationship between the yield of stannous methanesulfonate product of the present invention and the reaction temperature (see red line).
[0024] Figure 4 shows the relationship between the yield of stannous methanesulfonate product of the present invention and the molar ratio of tin to methanesulfonic acid raw materials (see red line).
[0025] Figure 5 shows the relationship between the yield of stannous methanesulfonate product and the mass concentration of methanesulfonic acid in this invention (see red line). Detailed Implementation
[0026] The present invention will be further described in detail below with reference to the embodiments, but the implementation of the present invention is not limited to the scope shown in the embodiments.
[0027] The methanesulfonic acid solution used in this embodiment is an industrial standard solution with a mass concentration of 70% and 98%. The density of the 70% methanesulfonic acid solution is 1.33 g / cm³. 3 The density of a 98% methanesulfonic acid solution is 1.481 g / cm³. 3 .
[0028] Example 1
[0029] Weigh 14.5 g of tin flowers and simultaneously measure 50.5 ml of 70% methanesulfonic acid solution into a SiC reaction vessel, then place it in a microwave oven. Heat to 140°C with 1000 W and react for 2 hours. Pour the reacted solution from the reaction vessel into a beaker. Measure the temperature of the solution in the beaker using an electronic thermometer. Allow it to cool naturally until crystals precipitate. When the temperature drops to 50°C, filter to separate the crystals and unreacted methanesulfonic acid. Wash the stannous methanesulfonate crystals with anhydrous ethanol. Recycle the filtrate, dry, and weigh to obtain 34.30 g of stannous methanesulfonate product, with a yield of 90.9%. Add pure water, methanesulfonic acid, and 0.4 g of hydroquinone to the stannous methanesulfonate product to prepare a stannous methanesulfonate solution of the desired concentration.
[0030] Example 2
[0031] 14.5 g of tin flowers were weighed, and 50.5 ml of 70% methanesulfonic acid solution was measured and placed in a SiC reaction vessel, which was then placed in a microwave oven. The mixture was heated to 140°C at 500 W and reacted for 2 hours. The resulting solution was then poured from the reaction vessel into a beaker. The temperature of the solution in the beaker was measured using an electronic thermometer. The mixture was allowed to cool naturally until crystals precipitated. When the temperature dropped to 50°C, the crystals and unreacted methanesulfonic acid were separated by filtration. The stannous methanesulfonate crystals were washed with anhydrous ethanol, and the filtrate was recycled. After drying and weighing, 31.92 g of stannous methanesulfonate was obtained, with a yield of 84.6%. Pure water, methanesulfonic acid, and 0.4 g of hydroquinone were added to the stannous methanesulfonate crystals to prepare a stannous methanesulfonate solution of the desired concentration.
[0032] Example 3
[0033] 14.5 g of tin flowers were weighed, and 50.5 ml of 70% methanesulfonic acid solution was measured and placed in a SiC reaction vessel, which was then placed in a microwave oven. The mixture was heated to 130°C at 1000 W and reacted for 2 hours. The resulting solution was then poured from the reaction vessel into a beaker. The temperature of the solution in the beaker was measured using an electronic thermometer. The mixture was allowed to cool naturally until crystals precipitated. When the temperature dropped to 50°C, the crystals and unreacted methanesulfonic acid were separated by filtration. The stannous methanesulfonate crystals were washed with anhydrous ethanol, and the filtrate was recycled. After drying and weighing, 31.72 g of stannous methanesulfonate was obtained, with a yield of 84.06%. Pure water, methanesulfonic acid, and 0.2 g of hydroquinone were added to the stannous methanesulfonate crystals to prepare a stannous methanesulfonate solution of the desired concentration.
[0034] Example 4
[0035] 14.5 g of tin flowers were weighed, and 50.5 ml of 70% methanesulfonic acid solution was measured and placed in a SiC reaction vessel, which was then placed in a microwave oven. The mixture was heated to 140°C at 1500 W and reacted for 2 hours. The resulting solution was then poured from the reaction vessel into a beaker. The temperature of the solution in the beaker was measured using an electronic thermometer. The mixture was allowed to cool naturally until crystals precipitated. When the temperature dropped to 50°C, the crystals and unreacted methanesulfonic acid were separated by filtration. The stannous methanesulfonate crystals were washed with anhydrous ethanol, and the filtrate was recycled. After drying and weighing, 34.87 g of stannous methanesulfonate was obtained, with a yield of 92.4%. The product appearance is shown in Figure 1. Pure water, methanesulfonic acid, and 0.2 g of hydroquinone were added to the stannous methanesulfonate crystals to prepare a stannous methanesulfonate solution of the desired concentration.
[0036] Effect of experimental conditions on the yield of stannous methanesulfonate
[0037] (1) Effect of microwave power on the yield of stannous methanesulfonate
[0038] 14.5 g of tin flowers were weighed, and 50.5 ml of a 70% methanesulfonic acid solution was measured and placed in a SiC reaction vessel, which was then placed in a microwave oven. The mixture was heated to 140°C at different microwave powers (500 W, 1000 W, 1500 W) and reacted for 2 hours. The resulting solution was then poured from the reaction vessel into a beaker. The temperature of the solution in the beaker was measured using an electronic thermometer. The mixture was allowed to cool naturally until crystals precipitated. When the temperature dropped to 50°C, the crystals and unreacted methanesulfonic acid were separated by filtration. The stannous methanesulfonate crystals were washed with anhydrous ethanol, and the filtrate was recycled. After drying and weighing, stannous methanesulfonate was obtained. The results are shown in Figure 2.
[0039] As shown in Figure 2, microwave power has a significant impact on the yield of stannous methanesulfonate. As the microwave power increases, the yield of stannous methanesulfonate increases. When the microwave power reaches 1500W, the yield of stannous methanesulfonate reaches 92.4%.
[0040] (2) Effect of temperature on the yield of stannous methanesulfonate
[0041] 14.5 grams of tin flowers were weighed, and 50.5 ml of a 70% methanesulfonic acid solution was measured and placed in a SiC reaction vessel, which was then placed in a microwave oven. The vessel was heated to different reaction temperatures (120℃, 130℃, 140℃, and 150℃) at 1500W for 2 hours. The resulting solution was then poured from the reaction vessel into a beaker, and the temperature of the solution in the beaker was measured using an electronic thermometer. The solution was allowed to cool naturally until crystals precipitated. When the temperature dropped to 50℃, the crystals and unreacted methanesulfonic acid were separated by filtration. The stannous methanesulfonate crystals were washed with anhydrous ethanol, and the filtrate was recycled. After drying and weighing, stannous methanesulfonate was obtained. The results are shown in Figure 3.
[0042] As shown in Figure 3, the yield of stannous methanesulfonate increases with increasing reaction temperature. The yield of stannous methanesulfonate reaches a maximum of 91.8% when the reaction temperature is 140℃. When the reaction temperature exceeds 140℃, methanesulfonic acid undergoes a side reaction and decomposes, which reduces the yield of stannous methanesulfonate.
[0043] (3) Effect of material ratio on the yield of stannous methanesulfonate
[0044] Different weights of tin flowers (29g, 14.5g, and 9.7g) were weighed, and 50.5ml of 70% methanesulfonic acid solution was measured and placed in a SiC reaction vessel, which was then placed in a microwave oven. The mixture was heated to a reaction temperature of 140℃ at 1500W and reacted for 2 hours. The resulting solution was then poured from the reaction vessel into a beaker, and the temperature of the solution in the beaker was measured using an electronic thermometer. The mixture was allowed to cool naturally until crystals precipitated. When the temperature dropped to 50℃, the crystals and unreacted methanesulfonic acid were separated by filtration. The stannous methanesulfonate crystals were washed with anhydrous ethanol, and the filtrate was recycled. After drying and weighing, stannous methanesulfonate was obtained. The results are shown in Figure 4.
[0045] As shown in Figure 4, when the molar ratio of tin flaves to methanesulfonic acid is 1:2, the tin flaves reaction is incomplete, and the yield of stannous methanesulfonate is only 81.42%. The highest yield of stannous methanesulfonate is obtained when the molar ratio of tin flaves to methanesulfonic acid is 1:4, reaching 92%. The yield of stannous methanesulfonate decreases when the molar ratio of tin flaves to methanesulfonic acid is 1:6. This may be because when the amount of methanesulfonic acid is too large, some stannous methanesulfonate will dissolve in the methanesulfonic acid, resulting in a decrease in yield.
[0046] (4) Effect of methanesulfonic acid concentration on the yield of stannous methanesulfonate
[0047] 14.5 grams of tin flowers were weighed, and 50.5 ml of methanesulfonic acid solutions of different mass concentrations (70%, 85%, and 98%) were placed in a SiC reaction vessel, which was then placed in a microwave oven. The mixture was heated to a reaction temperature of 140°C at 1500 W and reacted for 2 hours. The resulting solution was then poured from the reaction vessel into a beaker, and the temperature of the solution in the beaker was measured using an electronic thermometer. The solution was allowed to cool naturally until crystals precipitated. When the temperature dropped to 50°C, the crystals and unreacted methanesulfonic acid were separated by filtration. The stannous methanesulfonate crystals were washed with anhydrous ethanol, and the filtrate was recycled. After drying and weighing, stannous methanesulfonate was obtained. The results are shown in Figure 5.
[0048] As shown in Figure 5, the yield of stannous methanesulfonate is highest when the concentration of methanesulfonic acid is 70%. As the concentration increases, the yield decreases. This may be because when the concentration is too high, the reaction rate is fast, which may lead to product accumulation and the occurrence of side reactions, both of which may affect the yield.
[0049] The above embodiments are merely specific examples to further illustrate the purpose, technical solution, and beneficial effects of the present invention, and the present invention is not limited thereto. Any modifications, equivalent substitutions, improvements, etc., made within the scope of the disclosure of the present invention are included within the protection scope of the present invention.
Claims
1. A process for the rapid preparation of stannous methanesulfonate, characterized in that: The methyl sulfinate stannous product is obtained by reacting tin with a methyl sulfonic acid solution in microwave heating for a period of time, then cooling and crystallizing, filtering, washing and drying; the molar ratio of the tin to the methyl sulfonic acid is 1: (2-6), the microwave power is 500-1500 W, the reaction temperature is 120-150 DEG C, and the reaction time is 1-2 hours.
2. A process for the rapid preparation of stannous methanesulfonate according to claim 1, characterized in that: The tin is tin flower or tin powder.
3. A process for the quick preparation of stannous methanesulfonate according to claim 1, characterized in that: The mass concentration of the methyl sulfonic acid solution is 70-98%.
4. The method for rapidly preparing stannous methanesulfonate according to claim 3, characterized by: The molar ratio of the tin to the methyl sulfonic acid is 1:4, the microwave power is 1500 W, the reaction temperature is 140 DEG C, the reaction time is 2 hours, and the mass concentration of the methyl sulfonic acid solution is 70%.
5. The process for the quick preparation of stannous methanesulfonate according to claim 1, characterized by the fact that: The cooling and crystallization is natural cooling of the reaction product to 40-50 DEG C.
6. A process for the quick preparation of stannous methanesulfonate according to claim 1, characterized by: The washing is carried out with anhydrous ethanol.
7. The process for the quick preparation of stannous methanesulfonate according to claim 1, characterized by the fact that: The microwave reactor for the reaction of the tin with the methyl sulfonic acid solution is made of SiC and is provided with an infrared temperature measuring system.
8. The process for the quick preparation of stannous methanesulfonate according to claim 1, characterized by the fact that: The methyl sulfinate stannous product is prepared into a methyl sulfinate stannous solution, an antioxidant is added to the methyl sulfinate stannous solution, and an antioxidant methyl sulfinate stannous liquid product is obtained.
9. The method for rapidly preparing stannous methanesulfonate according to claim 8, characterized by: The antioxidant is hydroquinone, and 0.2-0.6 g of the antioxidant is added per 100 mL of the methyl sulfinate stannous solution.