A method for preparing sodium n,n-dimethyl dithio carbonyl propane sulfonate

Abstract

The application discloses a preparation method of sodium N,N-dimethyl dithiocarbonyl propane sulfonate. Dimethylamine, carbon disulfide and sodium hydroxide are mixed and then enter a first-stage micro-channel reactor to react to obtain a reactant; the reactant is mixed with 1,3-propane sulfonic acid lactone and then enters a second-stage micro-channel reactor to react, and after the reaction is completed, a crude product is prepared; after the crude product is purified and dried, the sodium N,N-dimethyl dithiocarbonyl propane sulfonate is prepared. The preparation method is stable and controllable, the product is high in purity and yield, safe and reliable, green and environment-friendly, and is worthy of industrial promotion.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis, and particularly relates to a method for preparing sodium N,N-dimethyldithiocarbonylpropane sulfonate. Background Technology

[0002] Sodium N,N-dimethyldithiocarbonylpropane sulfonate is a high-performance copper plating brightener. When used in combination with surfactants such as polyethers and wetting agents, it can produce a bright and flexible coating. High-quality sodium N,N-dimethyldithiocarbonylpropane sulfonate can be used in the production of electrolytic copper foil and also as an ink additive, especially in thermal printing inks.

[0003] Currently, no literature or patent reports have been found regarding the synthesis of sodium N,N-dimethyldithiocarbonylpropane sulfonate. A similar synthesis process is reported in CN201110314813.4, which describes a production process for potassium N-methyldithiocarbamate. First, a 40% wt aqueous solution of monomethylamine containing 0.99 mol of monomethylamine is gradually added dropwise to 1.2 mol of carbon disulfide and reacted at 15-45°C for 2-3 hours to obtain N-methyldithiocarbamate. Since this reaction is exothermic, the cooling rate needs to be increased to control the dropping rate and ensure the reaction temperature does not exceed 45°C. Then, a solution containing 1.05 mol of potassium hydroxide is added... A 0% potassium hydroxide aqueous solution was neutralized at 35-45℃ for 2 hours to obtain an N-methyldithiocarbamate solution with a mass percentage concentration of 60% and a yield of 98.9%. The reaction solution was then placed in a conical intermediate tank for settling and separation. Excess carbon disulfide in the lower layer was recovered, and the N-methyldithiocarbamate solution was placed in a mixing tank. Wastewater from cleaning the condenser and the reaction vessel was treated by decolorization, adsorption, precipitation, and filtration. The treated water was used to adjust the concentration of the N-methyldithiocarbamate solution. This method uses a conventional batch reactor with excess carbon disulfide. Carbon disulfide is a widely used enzyme inhibitor with cytotoxic effects, which can disrupt normal cell metabolism, interfere with lipoprotein metabolism, and cause vascular lesions, neuropathy, and damage to major organs. Furthermore, its boiling point is only 46.2℃, making it highly volatile, flammable, and explosive. Therefore, this method poses significant safety hazards and is environmentally unfriendly. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a method for preparing sodium N,N-dimethyldithiocarbonylpropane sulfonate. The reaction process of this invention is stable and controllable, yields high-purity and high-yield products, and is safe, reliable, and environmentally friendly.

[0005] The objective of this invention is achieved through the following technical solution: A method for preparing sodium N,N-dimethyldithiocarbonylpropane sulfonate includes the following steps: (1) Dimethylamine, carbon disulfide and sodium hydroxide are mixed and then reacted in a primary microchannel reactor to obtain reactants; the reactants are mixed with 1,3-propanesulfonate lactone and reacted in a secondary microchannel reactor. After the reaction is completed, crude product is obtained. (2) After purifying the crude product described in step (1), dry it to obtain sodium N,N-dimethyldithiocarbonylpropanesulfonate.

[0006] Preferably, the molar ratio of dimethylamine, carbon disulfide, sodium hydroxide and 1,3-propanesulfonate lactone in step (1) is 1:0.95~1:1~1.05:0.95~1.

[0007] Preferably, the dimethylamine, carbon disulfide and sodium hydroxide in step (1) are mixed by a static mixer.

[0008] Preferably, the parameters of the primary microchannel reactor reaction in step (1) are: pressure of 0.2~2MPa, reaction temperature of 5~25℃, and reaction time of 10~40s. The reaction is exothermic, and the temperature is lowered by a refrigerant.

[0009] Preferably, the reactants in step (1) are mixed with 1,3-propanesulfonate lactone using a static mixer.

[0010] Preferably, the parameters of the secondary microchannel reactor reaction in step (1) are: pressure of 0.2~2MPa, reaction temperature of 20~60℃, and reaction time of 5~30s. The reaction is exothermic, and the temperature is lowered by a refrigerant.

[0011] Preferably, the dimethylamine in step (1) is a commercially available 40% dimethylamine solution.

[0012] Preferably, the carbon disulfide described in step (1) is used with a water seal.

[0013] Preferably, the sodium hydroxide in step (1) is prepared as a 50wt% sodium hydroxide solution when used.

[0014] Preferably, the purification method in step (2) is: decolorization and purification using pharmaceutical needle-shaped 767 activated carbon.

[0015] Preferably, the drying method in step (2) is spray drying.

[0016] The chemical reaction formula of this invention is as follows:

[0017] Compared with the prior art, the beneficial effects of the present invention include: (1) The preparation method of the present invention is stable and controllable, with high product purity, high yield, safety and reliability, and is green and environmentally friendly.

[0018] (2) The product prepared by the present invention can be used in the production of electrolytic copper foil. At present, my country is vigorously developing green new energy, and the lithium battery industry is experiencing explosive growth. The demand for electrolytic copper foil is also increasing. The use of high-quality copper plating additives can make the electrolytic copper foil thinner, with higher tensile strength and peel resistance, further improving the energy storage efficiency and safety of lithium batteries. Therefore, the product of the present invention has broad market prospects and good economic and social benefits. Attached Figure Description

[0019] Figure 1 This is a flowchart of the preparation method of sodium N,N-dimethyldithiocarbonylpropanesulfonate according to the present invention.

[0020] Figure 2 The liquid chromatogram of the product prepared in Example 1.

[0021] Figure 3 H of the product prepared in Example 1 1 -NMR spectrum. Detailed Implementation

[0022] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0023] The primary and secondary microchannel reactors used in the examples are both Corning G1 microchannel reactors. The primary microchannel reactor has two microchannel plates, while the secondary microchannel reactor has only one plate.

[0024] The dimethylamine mentioned in the examples is a commercially available 40wt% dimethylamine solution; the carbon disulfide is water-sealed; and the sodium hydroxide is prepared as a 50wt% sodium hydroxide solution.

[0025] The purity of the products in the examples was determined by HPLC external standard method.

[0026] Example 1 A method for preparing sodium N,N-dimethyldithiocarbonylpropane sulfonate, comprising the following steps: (1) The molar ratio of dimethylamine: carbon disulfide: sodium hydroxide: 1,3-propanesulfonate lactone is 1:0.9919:1.0078:0.9817; Dimethylamine solution, carbon disulfide solution, and sodium hydroxide solution were pumped together into a static mixer at a rate of 130 g / min, 88 g / min, and 93 g / min, respectively, and then introduced into a primary microchannel reactor. The back pressure valve of the primary microchannel reactor was adjusted to control the pressure at 0.5 MPa, the temperature at 20 °C, and the reaction time at 20 s to obtain the reactants. The 1,3-propanesulfonate lactone feed pump was then turned on, allowing 1,3-propanesulfonate lactone to enter the secondary microchannel reactor along with the reactants at a flow rate of 142 g / min. The back pressure valve of the secondary microchannel reactor was adjusted to control the pressure at 0.4 MPa, the temperature at 30 °C, and the reaction time at 10 s. (2) After the reaction in step (1) is completed, the reaction solution is received, and 3% of its total mass of activated carbon is added for decolorization and purification; the carbon powder is removed by filtration, and the mother liquor is centrifuged and sprayed to obtain 18 kg of product with a purity of 99.28%, with a yield of 97.31%.

[0027] Example 2 A method for preparing sodium N,N-dimethyldithiocarbonylpropane sulfonate, comprising the following steps: (1) The molar ratio of dimethylamine: carbon disulfide: sodium hydroxide: 1,3-propanesulfonate lactone is 1: 0.9581: 1.0620: 0.9817; Dimethylamine solution, carbon disulfide solution, and sodium hydroxide solution were pumped together into a static mixer at a rate of 130 g / min, 85 g / min, and 98 g / min, respectively, and then introduced into a primary microchannel reactor. The back pressure valve of the primary microchannel reactor was adjusted to control the pressure at 0.8 MPa, the temperature at 10 °C, and the reaction time at 10 s to obtain the reactants. The 1,3-propanesulfonate lactone feed pump was then turned on, allowing the 1,3-propanesulfonate lactone to enter the secondary microchannel reactor along with the reactants at a flow rate of 142 g / min. The back pressure valve of the secondary microchannel reactor was adjusted to control the pressure at 0.6 MPa, the temperature at 25 °C, and the reaction time at 5 s. (2) After the reaction in step (1) is completed, the reaction solution is received, and 3% of its total mass of activated carbon is added for decolorization and purification; the carbon powder is removed by filtration, and the mother liquor is centrifuged and sprayed to obtain 17.4 kg of product with a purity of 98.56%, with a yield of 93.38%.

[0028] Comparative Example 1 A method for preparing sodium N,N-dimethyldithiocarbonylpropane sulfonate, comprising the following steps: (1) The molar ratio of dimethylamine: carbon disulfide: sodium hydroxide: 1,3-propanesulfonate lactone is 1: 0.9018: 1.0078: 0.9817; Dimethylamine solution, carbon disulfide solution, and sodium hydroxide solution were pumped together into a static mixer at a rate of 130 g / min, 80 g / min, and 93 g / min, respectively, and then introduced into a primary microchannel reactor. The back pressure valve of the primary microchannel reactor was adjusted to control the pressure at 0.5 MPa, the temperature at 20 °C, and the reaction time at 15 s to obtain the reactants. The 1,3-propanesulfonate lactone feed pump was then turned on, allowing the 1,3-propanesulfonate lactone to enter the secondary microchannel reactor along with the reactants at a flow rate of 142 g / min. The back pressure valve of the secondary microchannel reactor was adjusted to control the pressure at 0.4 MPa, the temperature at 30 °C, and the reaction time at 10 s. (2) After the reaction in step (1) is completed, the reaction solution is received, and 3% of its total mass of activated carbon is added for decolorization and purification; the carbon powder is removed by filtration, and the mother liquor is centrifuged and sprayed to obtain 16.8 kg of product with a purity of 97.41%, with a yield of 89.11%.

[0029] Comparative Example 2 A method for preparing sodium N,N-dimethyldithiocarbonylpropane sulfonate, comprising the following steps: (1) The molar ratio of dimethylamine: carbon disulfide: sodium hydroxide: 1,3-propanesulfonate lactone is 1: 0.9919: 1.0078: 1.0509; Dimethylamine solution, carbon disulfide solution, and sodium hydroxide solution were pumped together into a static mixer at a rate of 130 g / min, 88 g / min, and 93 g / min, respectively, and then introduced into a primary microchannel reactor. The back pressure valve of the primary microchannel reactor was adjusted to control the pressure at 0.5 MPa, the temperature at 20 °C, and the reaction time at 20 s to obtain the reactants. The 1,3-propanesulfonate lactone feed pump was then turned on, allowing 1,3-propanesulfonate lactone to enter the secondary microchannel reactor along with the reactants at a flow rate of 152 g / min. The back pressure valve of the secondary microchannel reactor was adjusted to control the pressure at 0.4 MPa, the temperature at 30 °C, and the reaction time at 10 s. (2) After the reaction in step (1) is completed, the reaction solution is received, and 3% of its total mass of activated carbon is added for decolorization and purification; the carbon powder is removed by filtration, and the mother liquor is centrifuged and sprayed to obtain 14.88 kg of product with a purity of 96.19%, with a yield of 77.94%.

[0030] The purity and yield of the products prepared in Comparative Examples 1-2 and Examples 1-2 were statistically compared, and the statistical results are shown in Table 1.

[0031] Table 1. Summary of Purity and Yield Statistics

[0032] Referring to Table 1, we can see that reducing the amount of carbon disulfide will affect the quality and yield. At the same time, excessive 1,3-propanesulfonyl lactone will also affect the quality and yield, while increasing production costs.

[0033] The specific embodiments of the present invention described above do not constitute a limitation on the scope of protection of the present invention. Any other corresponding changes and modifications made in accordance with the technical concept of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. A method for preparing sodium N,N-dimethyldithiocarbonylpropane sulfonate, characterized in that, Includes the following steps: (1) Dimethylamine, carbon disulfide and sodium hydroxide are mixed and then reacted in a primary microchannel reactor to obtain reactants; the reactants are mixed with 1,3-propanesulfonate lactone and reacted in a secondary microchannel reactor. After the reaction is completed, crude product is obtained. The molar ratio of dimethylamine, carbon disulfide, sodium hydroxide and 1,3-propanesulfonate lactone in step (1) is 1:0.95~1:1~1.05:0.95~1; (2) After purifying the crude product described in step (1), dry it to obtain sodium N,N-dimethyldithiocarbonylpropanesulfonate.

2. The method for preparing sodium N,N-dimethyldithiocarbonylpropane sulfonate according to claim 1, characterized in that, The parameters of the primary microchannel reactor reaction in step (1) are: pressure of 0.2~2MPa, reaction temperature of 5~25℃, and reaction time of 10~40s.

3. The method for preparing sodium N,N-dimethyldithiocarbonylpropane sulfonate according to claim 2, characterized in that, The parameters of the secondary microchannel reactor reaction in step (1) are: pressure of 0.2~2MPa, reaction temperature of 20~60℃, and reaction time of 5~30s.

4. The method for preparing sodium N,N-dimethyldithiocarbonylpropane sulfonate according to claim 1, characterized in that, In step (1), the dimethylamine, carbon disulfide and sodium hydroxide are mixed using a static mixer.

5. The method for preparing sodium N,N-dimethyldithiocarbonylpropane sulfonate according to claim 4, characterized in that, The reactants in step (1) are mixed with 1,3-propanesulfonate lactone using a static mixer.

6. The method for preparing sodium N,N-dimethyldithiocarbonylpropane sulfonate according to claim 1, characterized in that, When using the dimethylamine in step (1), a commercially available 40wt% dimethylamine solution is purchased; when using the carbon disulfide in step (1), a water seal is used.

7. The method for preparing sodium N,N-dimethyldithiocarbonylpropane sulfonate according to claim 6, characterized in that, The sodium hydroxide in step (1) is prepared as a 50wt% sodium hydroxide solution when used.

8. The method for preparing sodium N,N-dimethyldithiocarbonylpropane sulfonate according to claim 1, characterized in that, The purification method described in step (2) is as follows: decolorization and purification using pharmaceutical needle-shaped 767 activated carbon.

9. The method for preparing sodium N,N-dimethyldithiocarbonylpropane sulfonate according to claim 8, characterized in that, The drying method described in step (2) is spray drying.

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