Preparation method of propargyl alcohol ether sodium propane sulfonate

Abstract

The invention discloses a preparation method of propargyl alcohol ether sodium propanesulfonate, which comprises the following steps: mixing propargyl alcohol, solid sodium hydroxide and methyl tert-butyl ether in a reaction container connected with a water segregator, carrying out primary heating reaction under a vacuum condition to obtain a sodium propargyl alcohol crude product, continuously dropwise adding 1, 3-propanediol into the reaction container under a normal pressure condition, and carrying out secondary heating reaction under a vacuum condition to obtain a sodium propargyl alcohol ether sodium propanesulfonate product. Adding 1, 3-propane sultone, and carrying out secondary heating reaction to obtain a propargyl alcohol ether sodium propanesulfonate crude product; and adding water to dissolve the propargyl alcohol ether sodium propanesulfonate crude product, layering, dehydrating the obtained water phase, and recrystallizing to obtain the propargyl alcohol ether sodium propanesulfonate. The methyl tert-butyl ether is utilized to carry water in vacuum, the reaction is promoted to proceed forward, the conversion rate of the sodium propargyl alcohol is improved, the reaction temperature is reduced, the yield and quality of the product sodium propargyl alcohol ether propane sulfonate are improved, amplified production is facilitated, the production cost is reduced, and the risk of the reaction process is reduced.

Description

Technical Field

[0001] The invention relates to the technical field of chemical synthesis, and in particular to a method for preparing sodium propargyl alcohol ether propane sulfonate. Background Art

[0002] Sodium propargyl alcohol ether propane sulfonate (3-(1-sulfohex-5-yn-3-yloxy)hex-5-yne-1-sulfonate), molecular formula: C6H5NaO4S, molecular weight: 200.18, CAS number: 30290-53-0, is a light yellow solid. Sodium propargyl alcohol ether propane sulfonate is mainly used in electroplating nickel. As a nickel plating intermediate, it is the main component of nickel plating additives, which can enhance the brightness and fill the low area. In the entire nickel plating brightener market, this product has a large demand and excellent application effect. In the nickel plating additive formula, the amount of sodium propargyl alcohol ether propane sulfonate added is related to the application effect of the formula, such as brightness, fill, and stability, so the yield and purity of sodium propargyl alcohol ether propane sulfonate are important indicators for product quality control.

[0003] In the related art, the main method for synthesizing sodium propargyl alcohol ether propane sulfonate is to react a strong base such as sodium methoxide, sodium tert-butoxide and other strong alkaline substances with propargyl alcohol to remove the proton on the alcohol hydroxyl group to generate sodium propargyl alcohol, which is then reacted with 1,3-propane sultone to obtain sodium propargyl alcohol ether propane sulfonate. However, this method has the following disadvantages: (1) high temperature proton removal is required during use, which has a high risk factor; (2) the price is high, resulting in increased production costs; (3) the conversion rate of propargyl alcohol is low, resulting in low yield and purity of sodium propargyl alcohol ether propane sulfonate.

[0004] Therefore, it is necessary to provide a new method for preparing sodium propargyl alcohol ether propane sulfonate. Summary of the invention

[0005] In view of this, the present application provides a method for preparing sodium propargyl alcohol ether propane sulfonate, which is used to solve the problem of how to improve the yield and purity of sodium propargyl alcohol ether propane sulfonate under low temperature conditions.

[0006] In order to achieve the above technical objectives, this application adopts the following technical solutions: In a first aspect, the present application provides a method for preparing sodium propargyl alcohol ether propane sulfonate, comprising the following steps: S1. Propynol, solid sodium hydroxide and methyl tert-butyl ether are mixed in a reaction vessel connected to a water separator, and a heating reaction is carried out under vacuum conditions to obtain a crude product of sodium propynol, and 1,3-propane sultone is continuously added dropwise to the reaction vessel under normal pressure, and a secondary heating reaction is carried out to obtain a crude product of sodium propynol ether propane sulfonate; S2. Add water to dissolve the crude sodium propargyl alcohol ether propane sulfonate and separate the layers, then dehydrate the obtained aqueous phase and recrystallize it to obtain sodium propargyl alcohol ether propane sulfonate.

[0007] Preferably, the temperature of the primary heating reaction is 25-55°C.

[0008] Preferably, the temperature of the secondary heating reaction is 25-65° C., and the reaction time is 1-2 h.

[0009] Preferably, the temperature for dropwise addition of 1,3-propane sultone is 25-65° C., and the dropwise addition time is 3-5 hours.

[0010] Preferably, in step S1, after no more water appears in the water separator, 1,3-propane sultone is continuously added dropwise to the reaction container.

[0011] Preferably, the molar ratio of propargyl alcohol to solid sodium hydroxide is 1:1-10.

[0012] Preferably, the mass ratio of propargyl alcohol to methyl tert-butyl ether is 1:1-10.

[0013] Preferably, the molar ratio of propargyl alcohol to 1,3-propane sultone is 1:1-10.

[0014] Preferably, the solvent used for recrystallization includes one or more of methanol, ethanol, n-butanol and isopropanol.

[0015] Preferably, step S2 further comprises recycling the organic phase after stratification. The beneficial effects of the present application are as follows: the present invention uses propargyl alcohol and solid sodium hydroxide as starting raw materials, utilizes methyl tert-butyl ether to vacuum carry water, brings out the water generated by the reaction, promotes the reaction to proceed in the forward direction, that is, promotes the generation of sodium propargyl alcohol, and then sodium propargyl alcohol reacts with 1,3-propane sultone to obtain high-purity sodium propargyl alcohol ether propane sulfonate through crystallization. The present application improves the conversion rate of sodium propargyl alcohol, reduces the reaction temperature, improves the yield and quality of the product sodium propargyl alcohol ether propane sulfonate, is conducive to scale-up production, reduces production costs, and reduces the risk of the reaction process; the present application overcomes the problems of high reaction temperature, high risk, high catalyst price, and low conversion rate of propargyl alcohol in the production process of sodium propargyl alcohol ether propane sulfonate in the prior art. The process of the present application is simple, the yield and purity of the product are high, and it is conducive to industrial production. DETAILED DESCRIPTION

[0016] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0017] The present application provides a method for preparing sodium propargyl alcohol ether propane sulfonate, comprising the following steps: S1. Propynol, solid sodium hydroxide and methyl tert-butyl ether are mixed in a reaction vessel connected to a water separator, and a heating reaction is carried out under vacuum conditions to obtain a crude product of sodium propynol, and 1,3-propane sultone is continuously added dropwise to the reaction vessel under normal pressure, and a secondary heating reaction is carried out to obtain a crude product of sodium propynol ether propane sulfonate; S2. Add water to dissolve the crude sodium propargyl alcohol ether propane sulfonate and separate the layers, then dehydrate the obtained aqueous phase and recrystallize it to obtain sodium propargyl alcohol ether propane sulfonate.

[0018] In step S1, the water separation principle of the water separator is used in combination with the vacuum water removal of methyl tert-butyl ether to remove the water generated by the reaction, thereby promoting the reaction to proceed in the forward direction, improving the conversion rate of sodium propargyl alcohol, lowering the reaction temperature, and then continuing to drop 1,3-propane sultone to react, thereby obtaining a crude product of sodium propargyl alcohol ether propane sulfonate. The reaction process involved is as follows:

[0019] Among them, the molecular formula of sodium propargyl alcohol is .

[0020] As a reaction device commonly used by technical personnel in this field, the reaction container of the present application includes a round-bottom flask, the round-bottom flask is connected to a water separator, the water separator is connected to a condenser, and the round-bottom flask of the present application is connected to a vacuum pump for controlling the vacuum degree.

[0021] In the present application, the temperature of a single heating reaction is 25-55°C, for example, 25°C, 30°C, 35°C, 45°C, 50°C, 55°C or any value of 25-55°C, that is, in the present application, a single heating reaction can be completed at a minimum of 25°C.

[0022] In the present application, the temperature for dropping 1,3-propane sultone is 25-65°C, such as 25°C, 30°C, 35°C, 45°C, 50°C, 55°C, 65°C or any value of 25-65°C, the dropping time is 3-5 hours, the temperature for the secondary heating reaction is 25-65°C, such as 25°C, 30°C, 35°C, 45°C, 50°C, 55°C, 65°C or any value of 25-65°C, and the reaction time is 1-2h. In step S1, after no more water appears in the water separator, it means that the reaction of generating crude sodium propargyl alcohol is completed. At this time, continue to drop 1,3-propane sultone into the reaction vessel, which is beneficial to improve the yield and purity of the product.

[0023] The specific operation is: after no more water appears in the water separator, 1,3-propane sultone is added dropwise to the reactor at a temperature of 25-65°C for 3-5 hours. After the addition is completed, the temperature is kept at 25-65°C for 1 hour.

[0024] In some embodiments, the molar ratio of propargyl alcohol to solid sodium hydroxide is 1:1-10, such as 1:1-10, 1:1, 1:2, 1:4, 1:6, 1:8, 1:10, or any ratio of 1:1-10.

[0025] In some embodiments, the mass ratio of propargyl alcohol to methyl tert-butyl ether is 1:1-10, such as 1:1-10, 1:1, 1:2, 1:4, 1:6, 1:8, 1:10 or any ratio of 1:1-10.

[0026] In some embodiments, the molar ratio of propargyl alcohol to 1,3-propane sultone is 1:1-10, such as 1:1-10, 1:1, 1:2, 1:4, 1:6, 1:8, 1:10, or any ratio of 1:1-10.

[0027] In some embodiments, the solvent used for recrystallization includes one or more of methanol, ethanol, n-butanol, and isopropanol.

[0028] In step S2, water is added to dissolve the crude sodium propargyl ether propane sulfonate and the crude product is separated into layers to obtain an aqueous phase containing sodium propargyl ether propane sulfonate and an organic phase of methyl tert-butyl ether. In some embodiments, the organic phase after separation is recycled to save raw materials. The present solution is further described below through specific embodiments.

[0029] Example 1 A method for preparing sodium propargyl alcohol ether propane sulfonate comprises the following steps: S1. Add 40g (1.0mol) of sodium hydroxide, 56g (1.0mol) of propargyl alcohol and 168g of methyl tert-butyl ether to a 500mL four-necked flask connected to a water separator, stir, control the system temperature at 25°C, evacuate the entire system, and wait until no water is discharged from the water separator, that is, the reaction is completed to obtain a crude product of sodium propargyl alcohol; turn off the vacuum, add 170.8g (1.4mol) of 1,3-propane sultone dropwise at normal pressure and 25°C for 3 hours, and after the addition of 1,3-propane sultone is completed, keep warm at 25°C for 1 hour to obtain a crude product of sodium propargyl alcohol ether propane sulfonate; S2. Add water to dissolve the crude sodium propargyl alcohol ether propane sulfonate and separate the layers. Heat and dehydrate the obtained aqueous phase until a white solid precipitates. Recrystallize it with methanol and centrifuge it to dry it to obtain 90.9 g of sodium propargyl alcohol ether propane sulfonate (yield 78.1%, purity 95.21%).

[0030] Example 2 A method for preparing sodium propargyl alcohol ether propane sulfonate comprises the following steps: S1. Add 96g (2.4mol) of sodium hydroxide, 112g (2.0mol) of propargyl alcohol and 336g of methyl tert-butyl ether to a 1L four-necked flask connected to a water separator, stir, control the system temperature at 25°C, evacuate the entire system, and wait until no water is discharged from the water separator, that is, the reaction is completed to obtain a crude product of sodium propargyl alcohol; turn off the vacuum, add 341.6g (2.8mol) of 1,3-propane sultone dropwise at normal pressure and 25°C for 3 hours, and after the addition of 1,3-propane sultone is completed, keep warm at 25°C for 1 hour to obtain a crude product of sodium propargyl alcohol ether propane sulfonate; S2. Add water to dissolve the crude sodium propargyl alcohol ether propane sulfonate and separate the layers. The organic phase is reused in step S1. The obtained aqueous phase is heated and dehydrated until a white solid precipitates. The solid is recrystallized with methanol and centrifuged to dry to obtain 374.2 g of sodium propargyl alcohol ether propane sulfonate (yield 93.5%, purity 98.36%).

[0031] Example 3 A method for preparing sodium propargyl alcohol ether propane sulfonate comprises the following steps: S1. Add 96g (2.4mol) of sodium hydroxide, 112g (2.0mol) of propargyl alcohol and 336g of methyl tert-butyl ether to a 1L four-necked flask connected to a water separator, stir, control the system temperature at 25°C, evacuate the entire system, and wait until no water is discharged from the water separator, that is, the reaction is completed to obtain a crude product of sodium propargyl alcohol; turn off the vacuum, add 292.8g (2.4mol) of 1,3-propane sultone dropwise at normal pressure and 25°C for 3 hours, and after the addition of 1,3-propane sultone is completed, keep warm at 25°C for 1 hour to obtain a crude product of sodium propargyl alcohol ether propane sulfonate; S2. Add water to dissolve the crude sodium propargyl alcohol ether propane sulfonate and separate the layers. The organic phase is reused in step S1. The obtained aqueous phase is heated and dehydrated until a white solid precipitates. The solid is recrystallized with methanol and centrifuged to dry to obtain 342.4 g of sodium propargyl alcohol ether propane sulfonate (yield 85.6%, purity 97.67%).

[0032] Example 4 A method for preparing sodium propargyl alcohol ether propane sulfonate comprises the following steps: S1. Add 96g (2.4mol) of sodium hydroxide, 112g (2.0mol) of propargyl alcohol and 336g of methyl tert-butyl ether to a 1L four-necked flask connected to a water separator, stir, control the system temperature at 50°C, evacuate the entire system, and wait until no water is discharged from the water separator, that is, the reaction is completed to obtain a crude product of sodium propargyl alcohol; turn off the vacuum, add 341.6g (2.8mol) of 1,3-propane sultone dropwise at normal pressure and 50°C for 3 hours, and after the addition of 1,3-propane sultone is completed, keep warm at 50°C for 1 hour to obtain a crude product of sodium propargyl alcohol ether propane sulfonate; S2. Add water to dissolve the crude sodium propargyl alcohol ether propane sulfonate and separate the layers. The organic phase is reused in step S1. The obtained aqueous phase is heated and dehydrated until a white solid precipitates. The solid is recrystallized with methanol and centrifuged to dry to obtain 306 g of sodium propargyl alcohol ether propane sulfonate (yield 76.5%, purity 94.38%).

[0033] Example 5 A method for preparing sodium propargyl alcohol ether propane sulfonate comprises the following steps: S1. Add 96kg (2.4kmol) of sodium hydroxide, 112kg (2.0kmol) of propargyl alcohol and 336kg of methyl tert-butyl ether to a 1000L four-necked flask connected to a water separator, stir, control the system temperature at 25°C, evacuate the entire system, and wait until no water is discharged from the water separator, that is, the reaction is completed to obtain a crude product of sodium propargyl alcohol; turn off the vacuum, add 341.6kg (2.8kmol) of 1,3-propane sultone dropwise at normal pressure and 25°C for 3 hours, and after the addition of 1,3-propane sultone is completed, keep warm at 25°C for 1 hour to obtain a crude product of sodium propargyl alcohol ether propane sulfonate; S2. Add water to dissolve the crude sodium propargyl alcohol ether propane sulfonate and separate the layers. The organic phase is recycled to step S1. The obtained aqueous phase is heated and dehydrated until a white solid precipitates. The solid is then recrystallized with methanol and centrifuged to dry to obtain 377.2 kg of sodium propargyl alcohol ether propane sulfonate (yield 94.3%, purity 98.61%).

[0034] Comparative Example 1 A method for preparing sodium propargyl alcohol ether propane sulfonate, the other contents are the same as those in Example 2, except that the amount of propargyl alcohol is adjusted to 1.44 mol, and the yield of the obtained sodium propargyl alcohol ether propane sulfonate is 92.9% and the purity is 98.24%.

[0035] Comparative Example 2 A method for preparing sodium propargyl alcohol ether propane sulfonate, the other contents of which are the same as those of Example 2, except that when synthesizing sodium propargyl alcohol, there is no vacuuming step, and the yield of the obtained sodium propargyl alcohol ether propane sulfonate is 76.3%, and the purity is 88.25%.

[0036] Comparative Example 3 A method for preparing sodium propargyl alcohol ether propane sulfonate, the other contents of which are the same as those of Example 2, except that methanol is not added, and the yield of the obtained sodium propargyl alcohol ether propane sulfonate is 65.3% and the purity is 99.62%.

[0037] Comparative Example 4 A method for preparing sodium propargyl alcohol ether propane sulfonate, the other contents are the same as those of Example 2, except that the amount of 1,3-propane sultone is adjusted to 146.4 g (1.2 mol), and the yield of the obtained sodium propargyl alcohol ether propane sulfonate is 85.2% and the purity is 97.46%.

[0038] It can be seen from the purity and yield results of the sodium propargyl alcohol ether propane sulfonate obtained in each embodiment and comparative example that embodiment 5 is equivalent to the amplification experiment of embodiment 2. It can be seen from the comparison between the two that the present invention can further improve the yield in the amplification experiment and is suitable for industrial production. In comparative example 1, propargyl alcohol is excessive, and the yield of sodium propargyl alcohol ether propane sulfonate is not much different from the excess recovery rate of sodium hydroxide, but the price of propargyl alcohol is 15 times that of sodium hydroxide, and propargyl alcohol is a highly toxic substance, and the recovery process is risky, so sodium hydroxide is selected to be excessive. In comparative example 2, the process of synthesizing sodium propargyl alcohol, there is no vacuuming step, and the product yield decreases, indicating that at low temperature and normal pressure, methyl tert-butyl ether cannot reflux with water, and cannot promote the reaction to generate sodium propargyl alcohol. In comparative example 3, methanol is not added in the crystallization process, and the product yield decreases sharply, but the purity is indeed increasing, indicating that water is used as a benign solvent in the purification process, and a large amount of products are not proposed in the mother liquor, which is unfavorable for realizing industrialization. In Comparative Example 4, the amount of 1,3-propane sultone was adjusted to 146.4 g, and the product yield decreased. The possible reasons were that the amount of 1,3-propane sultone decreased, the reaction was not sufficient, and the amount of sodium propargyl alcohol ether propane sulfonate generated decreased.

[0039] The above results show that in the system of the present invention, the molar ratio of propargyl alcohol to sodium hydroxide is 1:1.2, the mass ratio of propargyl alcohol to methyl tert-butyl ether is 1:3, the molar ratio of propargyl alcohol to 1,3-propane sultone is 1:1.4, and the reaction temperature is 25-30°C, which can greatly improve the yield of the product to 91%-94% and the effective content of the product to 98.36%.

[0040] The invention uses propargyl alcohol and solid sodium hydroxide as starting raw materials, utilizes methyl tert-butyl ether to carry water in vacuum, carries out water generated by the reaction, promotes the reaction to proceed in the forward direction, namely promotes the generation of sodium propargyl alcohol, and the sodium propargyl alcohol reacts with 1,3-propane sultone to obtain high-purity sodium propargyl alcohol ether propane sulfonate through crystallization. The application improves the conversion rate of sodium propargyl alcohol, reduces the reaction temperature, improves the yield and quality of the product sodium propargyl alcohol ether propane sulfonate, is conducive to scale-up production, reduces production costs, and reduces the risk of the reaction process. The application overcomes the problems of high reaction temperature, high risk, high catalyst price, and low conversion rate of propargyl alcohol in the production process of sodium propargyl alcohol ether propane sulfonate in the prior art. The process of the application is simple, the yield and purity of the product are high, and it is conducive to industrial production.

[0041] The above are only preferred specific implementations of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by any technician familiar with the technical field within the technical scope disclosed by the present invention should be covered within the protection scope of the present invention.

Claims

1. A method for preparing sodium propargyl alcohol ether propane sulfonate, characterized in that: The following steps are involved: S1. Propynol, solid sodium hydroxide and methyl tert-butyl ether are mixed in a reaction vessel connected to a water separator, and a heating reaction is carried out under vacuum conditions to obtain a crude product of sodium propynol, and 1,3-propane sultone is continuously added dropwise to the reaction vessel under normal pressure, and a secondary heating reaction is carried out to obtain a crude product of sodium propynol ether propane sulfonate; S2. Add water to dissolve the crude sodium propargyl alcohol ether propane sulfonate and separate the layers, then dehydrate the obtained aqueous phase and recrystallize it to obtain the sodium propargyl alcohol ether propane sulfonate.

2. The method for preparing sodium propargyl alcohol ether propane sulfonate according to claim 1, characterized in that: The temperature of the primary heating reaction is 25-55°C.

3. The method for preparing sodium propargyl alcohol ether propane sulfonate according to claim 1, characterized in that: The temperature of the secondary heating reaction is 25-65° C., and the reaction time is 1-2 hours.

4. The method for preparing sodium propargyl alcohol ether propane sulfonate according to claim 1, characterized in that: The temperature for dropwise adding 1,3-propane sultone is 25-65° C., and the dropwise adding time is 3-5 hours.

5. The method for preparing sodium propargyl alcohol ether propane sulfonate according to claim 1, characterized in that: In step S1, after no more water appears in the water separator, 1,3-propane sultone is continuously added dropwise to the reaction container.

6. The method for preparing sodium propargyl alcohol ether propane sulfonate according to claim 1, characterized in that: The molar ratio of the propargyl alcohol to the solid sodium hydroxide is 1:1-10.

7. The method for preparing sodium propargyl alcohol ether propane sulfonate according to claim 1, characterized in that: The mass ratio of the propargyl alcohol to methyl tert-butyl ether is 1:1-10.

8. The method for preparing sodium propargyl ether propane sulfonate according to claim 1, characterized in that: The molar ratio of the propargyl alcohol to 1,3-propane sultone is 1:1-10.

9. The method for preparing sodium propargyl alcohol ether propane sulfonate according to claim 1, characterized in that: The solvent used for the recrystallization includes one or more of methanol, ethanol, n-butanol and isopropanol.

10. The method for preparing sodium propargyl alcohol ether propane sulfonate according to claim 1, characterized in that: Step S2 also includes recycling the organic phase after stratification.

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