CN111925352A - Method for synthesizing vinyl sulfate - Google Patents
Method for synthesizing vinyl sulfate Download PDFInfo
- Publication number
- CN111925352A CN111925352A CN202010657303.6A CN202010657303A CN111925352A CN 111925352 A CN111925352 A CN 111925352A CN 202010657303 A CN202010657303 A CN 202010657303A CN 111925352 A CN111925352 A CN 111925352A
- Authority
- CN
- China
- Prior art keywords
- kettle
- sulfate
- vinyl sulfate
- temperature
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
- C07D327/10—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms two oxygen atoms and one sulfur atom, e.g. cyclic sulfates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing vinyl sulfate, which comprises the steps of adding ethylene glycol into a reaction kettle, and reducing the temperature of the reaction kettle to below 35 ℃; adding thionyl chloride into the reaction kettle; then raising the temperature of the kettle to 45-60 ℃, and continuously preserving the heat for 1-3 hours; when the temperature of the kettle is 30-60 ℃, vacuumizing to-0.05 to-0.1 MPa; returning the kettle pressure to normal pressure, dropwise adding alkali liquor into the reaction kettle when the kettle temperature is 10-40 ℃, and adjusting the pH value of the kettle liquor to 7.5-8; separating the lower layer solution to obtain a finished product of the ethylene sulfite; adding a sodium hypochlorite solution into the reaction kettle; dissolving a vinyl sulfate crude product in an organic solvent, and adding ice water into the solution; adding a dehydrating agent into the vinyl sulfate organic solution; concentrating and crystallizing the obtained vinyl sulfate organic solution, and drying the obtained solid; the primary crystals were redissolved in an organic solvent and filtered to give a white filter cake. The invention has the advantages of high product yield and high purity.
Description
Technical Field
The invention relates to a synthetic method of an organic compound, in particular to a synthetic method of vinyl sulfate.
Background
The ethylene sulfate is an important lithium ion battery electrolyte additive, can inhibit the reduction of the initial capacity of the battery, increase the initial discharge capacity, reduce the battery expansion after high-temperature placement, and improve the charge-discharge performance and cycle number of the battery. With the rapid development of the lithium ion battery industry, the demand of the lithium ion battery electrolyte rapidly increases, and as an important additive in the lithium ion battery electrolyte, the demand of high-purity ethylene sulfate rapidly increases.
The existing vinyl sulfate synthesis methods mainly comprise the following steps:
1) the method uses flammable and explosive ethylene, has serious safety problems in large-scale production and has higher requirements on equipment and personnel operation;
2) ethylene glycol and sulfuric acid ester are synthesized into the ethylene sulfite, and the method has more byproducts, lower product yield and strong equipment corrosivity;
3) 1, 2-dibromoethane and silver sulfate are refluxed in toluene to prepare ethylene sulfate, and the method has low product yield and high raw material price;
4) ethylene oxide and sulfur trioxide react in dioxane to synthesize ethylene sulfate, and the ethylene oxide is a high-toxicity substance and is gas at normal temperature, so that the requirement on equipment is high.
Disclosure of Invention
The invention provides a vinyl sulfate synthesis method with high product yield and high purity.
A method for synthesizing vinyl sulfate comprises the following steps:
s1, adding ethylene glycol into the reaction kettle, and cooling the kettle to below 35 ℃;
s2, adding thionyl chloride into the reaction kettle;
s3, raising the temperature of the reaction kettle to 30-45 ℃, and preserving the heat for 1-3 hours; then raising the temperature of the kettle to 45-60 ℃, and continuously preserving the heat for 1-3 hours;
s4, after the heat preservation is finished, when the temperature of the kettle is 30-60 ℃, vacuumizing to-0.05-0.1 MPa, maintaining the vacuum for 1-3 hours, and degassing the reaction liquid;
s5, after degassing, restoring the kettle pressure to normal pressure, dropwise adding alkali liquor into the reaction kettle when the kettle temperature is 10-40 ℃, and adjusting the pH value of the kettle liquor to 7.5-8; after the kettle liquid is layered, separating a lower layer solution to obtain a finished product of the ethylene sulfite;
s6, adding the ethylene sulfite into a reaction kettle, reducing the temperature of kettle liquid to 0-10 ℃, and adding a buffering agent and a catalyst;
s7, adding a sodium hypochlorite solution into the reaction kettle, and maintaining the temperature of the reaction kettle at 0-10 ℃;
s8, filtering the reaction mixed liquid to obtain a solid, namely a vinyl sulfate crude product;
s9, dissolving the vinyl sulfate crude product in an organic solvent, adding ice water into the solution, stirring for 5-10 min, standing for layering, separating out a water phase, and repeatedly washing for 4-10 times to obtain a vinyl sulfate organic solution;
s10, adding a dehydrating agent into the vinyl sulfate organic solution, and filtering to obtain an anhydrous vinyl sulfate organic solution;
s11, concentrating and crystallizing the obtained vinyl sulfate organic solution, and drying the obtained solid to obtain a primary crystal of the vinyl sulfate; re-dissolving the primary crystal in an organic solvent, distilling out part of the solvent under reduced pressure, cooling for crystallization, and filtering to obtain a white filter cake;
and S12, putting the filter cake obtained in the step S11 into an oven for drying to obtain a white solid, namely a finished product of the vinyl sulfate.
Further, the molar ratio of the amount of the thionyl chloride in the step S2 to the amount of the ethylene glycol in the step S1 is 1: 1.92 to 2.1.
Further, the preferable molar ratio of the amount of thionyl chloride used in step S2 to the amount of ethylene glycol used in step S1 is 1: 1.95 to 2.05.
Preferably, in step S2, the thionyl chloride is added in the following manner: adding thionyl chloride into a dropping funnel, opening a valve between the reaction kettle and a tail gas absorption groove firstly when the temperature in the reaction kettle reaches the reaction temperature, and then opening the valve of the dropping funnel. The reaction temperature is 5-35 ℃, and the preferable reaction temperature is 15-30 ℃.
Further, the alkali solution in step S5 is an aqueous solution of one or more of sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium hydroxide, and potassium hydroxide.
Preferably, in step S5, after degassing, the vacuum is turned off, and the kettle pressure is returned to normal pressure; and after the pH value of the kettle liquid is adjusted to 7.5-8, closing the reaction kettle, stirring, standing for a period of time, and layering the kettle liquid.
Further, the buffer in step S6 is selected from one or two of sodium dihydrogen phosphate and potassium dihydrogen phosphate; the mol ratio of the buffering agent to the ethylene sulfite is 0.1-1: 1.
The mol ratio of the buffering agent to the ethylene sulfite is preferably 0.3-0.6: 1.
Preferably, in step S6, after the ethylene sulfite is added to the reaction kettle, the reaction kettle is opened and stirred, and the circulating cooling liquid is introduced into the jacket of the reaction kettle.
Further, the catalyst in the step S6 is one or more selected from ruthenium trichloride, rhodium trichloride, palladium dichloride, osmium trichloride, iridium trichloride and platinum chloride, and the molar ratio of the catalyst to the ethylene sulfite is 1: 100-10000. The mol ratio of the catalyst to the ethylene sulfite is preferably 1: 1000-5000.
Further, the molar ratio of the total amount of sodium hypochlorite in the sodium hypochlorite solution in the step S7 to the vinyl sulfite in the step S6 is 1-1.5: 1.
Preferably, in step S7, adding the sodium hypochlorite solution and ice or ice water into the reaction kettle, controlling the dropping rate of the sodium hypochlorite solution and the adding rate of the ice or ice water, maintaining the temperature of the reaction kettle at 0-10 ℃, and completing the addition of the sodium hypochlorite within 30-60 min.
In step S7, the sodium hypochlorite solution has a concentration of 5% to 25%. The concentration of the sodium hypochlorite solution is preferably 8-15%.
In step S7, the molar ratio of the total amount of sodium hypochlorite in the sodium hypochlorite solution to the vinyl sulfite in step S6 is preferably 1-1.2: 1.
Further, the organic solvent in step S9 is one or more of chloroform, carbon tetrachloride, dichloroethane, trichloroethane, dichloropropane, trichloropropane, chlorobenzene, and dichlorobenzene; the mass ratio of the organic solvent to the vinyl sulfate crude product is 3-30: 1.
In the step S9, the mass ratio of the organic solvent to the crude vinyl sulfate is preferably 5-15: 1.
Further, the mass ratio of the amount of the ice water used in the step S9 to the crude product of the vinyl sulfate is 0.2-1: 1.
The mass ratio of the amount of the ice water used in the step S9 to the crude product of the vinyl sulfate is preferably 0.4-0.6: 1.
Further, the dehydrating agent in step S10 is one or more of sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate, aluminum sulfate, ferric sulfate, sodium chloride, potassium chloride, calcium chloride, magnesium chloride, and aluminum chloride; the molar ratio of the consumption of the dehydrating agent in the step S10 to the crude vinyl sulfate product in the step S9 is 0.1-1: 1.
The molar ratio of the consumption of the dehydrating agent in the step S10 to the crude vinyl sulfate product in the step S9 is 0.3-0.6: 1.
Further, the organic solvent in step S11 is one or more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propylene carbonate, and ethylene carbonate; the amount of the organic solvent used in step S11 is equivalent to the weight of the organic solvent used in step S9.
The weight of the organic solvent distilled under reduced pressure in step S11 is 50-80%, preferably 60-70% of the total weight of the solvent.
In step S11, the temperature of the cooling crystallization is-5 to 10 ℃, preferably 0 to 5 ℃.
In the step S11 and the step S12, the drying temperature is 30-80 ℃, and preferably 40-60 ℃.
Compared with the prior art, the method has the advantages of high product yield, low product impurity content, less three-waste discharge and low process cost. The method is characterized in that a stage of synthesizing the ethylene sulfite is particularly important for degassing after heat preservation, most of the removed gas is strong acid gas, if the degassing is incomplete, a large amount of alkali liquor is used in the later neutralization, the ethylene sulfite has certain solubility in water, the yield is lower when the alkali liquor is more used, and the amount of wastewater after the acid-base neutralization is correspondingly increased at the same time, so that the alkali liquor amount can be controlled at a lower level, the final molar yield is more than 95% (calculated by ethylene glycol), and the chromatographic content is more than 99%; the invention discloses a process for preparing vinyl sulfate, which comprises the steps of adding vinyl sulfate into a battery, wherein the vinyl sulfate is very high in requirements on purity, water content, acid value and the like, and directly synthesizing the vinyl sulfate, so that the product purification is a key point, the prior process basically uses a haloalkane solvent for refinement, the total yield is low, a large amount of waste residues are generated, and halogenated alkane is usually remained in the product during drying operation and does not reach the standard, and the invention discovers that a crude product of the vinyl sulfite is dissolved by using an organic solvent in the step S9, water-soluble impurities are removed by washing, then the crude product is dissolved by using an organic solvent in the step S11, the solvent has very good solubility on main impurities in the product, finally a qualified product can be obtained by only leaving a small amount of the solvent for cooling and separating out, the yield is high, the waste residues are few, the organic solvent in the step S11 is a solvent commonly used in the, further decomposition of the product under high temperature is avoided, the final molar yield can reach more than 90 percent, the purity can reach more than 99.5 percent, the water content is less than or equal to 60ppm, and the acid value is less than or equal to 60 ppm.
Detailed Description
The present invention is described in detail below by way of examples, it being understood that these examples are for illustrative purposes only and in no way limit the scope of the present invention. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention, and that such changes and modifications may be within the scope of the invention.
Example 1
And (3) synthesizing ethylene sulfite: adding 100g of ethylene glycol into a reaction kettle, opening and stirring, introducing a circulating cooling liquid into a jacket of the reaction kettle, and slowly dropwise adding 202g of thionyl chloride into the reaction kettle, wherein the adding mode of the thionyl chloride is as follows: adding thionyl chloride into a dropping funnel, opening a valve between the reaction kettle and a tail gas absorption tank when the temperature in the reaction kettle reaches the reaction temperature, and then opening the valve of the dropping funnel to finish adding thionyl chloride within about 2 hours. Controlling the reaction temperature at 10-20 ℃, and absorbing the tail gas by using 20% sodium hydroxide solution. After the dropwise addition, raising the temperature of the kettle liquid to 35 ℃, preserving the heat for 1 hour, continuously raising the temperature of the kettle liquid to 45 ℃, and continuously preserving the heat for 3 hours; after the heat preservation, the reaction solution was degassed after the vacuum pumping was carried out to-0.08 MPa and the maintenance was carried out for 2 hours. And (3) recovering the kettle pressure to normal pressure, cooling the kettle liquid to room temperature, adding a 10% sodium carbonate solution to adjust the pH value to 7.5-8, standing for a period of time, and separating a lower layer solution after the kettle liquid is layered to obtain 165.5g of ethylene sulfite. The ethylene sulfite synthesized by the method has a molar yield of 95% or more (calculated by ethylene glycol) and a chromatographic content of 99% or more.
Synthesizing vinyl sulfate: adding 165.5g of ethylene sulfite into a reaction kettle, opening and stirring, introducing a circulating cooling liquid into a jacket of the reaction kettle, controlling the initial temperature to be 0-10 ℃, adding 55g of potassium dihydrogen phosphate and 0.2g of ruthenium trichloride, and uniformly stirring; and (3) dropwise adding 1340g of 10% sodium hypochlorite solution into the reaction kettle under stirring, controlling the dropwise adding speed, simultaneously adding a proper amount of ice blocks, controlling the temperature to be 0-10 ℃, and stirring for 30min after dropwise adding. The reaction solution was filtered to obtain 180g of a crude vinyl sulfate product. Dissolving the obtained vinyl sulfate crude product in 1083g of dichloroethane, adding 90g of ice water into the solution, stirring for 5 minutes, standing for layering, separating out a water phase, and repeatedly washing with water for 6 times to obtain a vinyl sulfate-dichloroethane solution; adding 72g of anhydrous magnesium sulfate into the vinyl sulfate-dichloroethane solution, stirring for 30min, and filtering; and (3) heating the obtained filtrate to 50 ℃ under reduced pressure, distilling off the dichloroethane solvent to obtain a solid, putting the solid into an oven, and drying at 50 ℃ to obtain a white solid. 1083g of dimethyl carbonate is added into the obtained solid, stirred and dissolved, the temperature is increased to 60 ℃ under reduced pressure, 760g of dimethyl carbonate is distilled out, the temperature is immediately reduced to 10 ℃ for crystallization, white solid is obtained by filtration, and the white solid is put into an oven and dried under the condition of 50 ℃ to obtain 172g of finished product of the ethylene sulfate.
Example 2
And (3) synthesizing ethylene sulfite: adding 350g of ethylene glycol into a reaction kettle, opening and stirring, introducing a circulating cooling liquid into a jacket of the reaction kettle, and slowly dropwise adding 698g of thionyl chloride into the reaction kettle, wherein the adding mode of the thionyl chloride is as follows: adding thionyl chloride into a dropping funnel, opening a valve between the reaction kettle and a tail gas absorption tank when the temperature in the reaction kettle reaches a reaction temperature, then opening the valve of the dropping funnel, finishing adding the thionyl chloride within about 2 hours, controlling the reaction temperature to be 5-15 ℃, and absorbing the tail gas by using 20% sodium hydroxide solution. After the dropwise addition, raising the temperature of the kettle liquid to 30 ℃, preserving the heat for 2 hours, continuously raising the temperature of the kettle liquid to 40 ℃, and continuously preserving the heat for 3 hours; after the heat preservation, the reaction solution was degassed after the vacuum was evacuated to-0.09 MPa and maintained for 1.5 hours. And (3) recovering the kettle pressure to normal pressure, cooling the kettle liquid to room temperature, adding a 10% sodium bicarbonate solution to adjust the pH value to 7.5-8, standing for a period of time, and separating a lower layer solution after the kettle liquid is layered to obtain 585g of ethylene sulfite. The ethylene sulfite synthesized by the method has a molar yield of 95% or more (calculated by ethylene glycol) and a chromatographic content of 99% or more.
Synthesizing vinyl sulfate: adding 585g of ethylene sulfite into a reaction kettle, opening and stirring, introducing a circulating cooling liquid into a jacket of the reaction kettle, controlling the initial temperature to be 0-10 ℃, adding 193g of sodium dihydrogen phosphate and 1.1g of rhodium trichloride, and uniformly stirring; dropwise adding 2321g of sodium hypochlorite solution with the concentration of 20% into the reaction kettle under stirring, controlling the dropwise adding speed, simultaneously adding a proper amount of ice blocks, controlling the temperature to be 0-10 ℃, and stirring for 30min after dropwise adding. The reaction solution was filtered to obtain 638g of a crude vinyl sulfate product. Dissolving the obtained vinyl sulfate crude product in 2553g of dichloropropane, adding 255g of ice water into the solution, stirring for 5 minutes, standing for layering, separating out a water phase, and repeatedly washing with water for 8 times to obtain a vinyl sulfate-dichloropropane solution; adding 319g of anhydrous calcium sulfate into the vinyl sulfate-dichloropropane solution, stirring for 30min, and filtering; and (3) heating the obtained filtrate to 50 ℃ under reduced pressure, distilling off the dichloroethane solvent to obtain a solid, putting the solid into an oven, and drying at 50 ℃ to obtain a white solid. 1083g of diethyl carbonate is added into the obtained solid, stirred and dissolved, the temperature is reduced to 60 ℃, 650g of diethyl carbonate is distilled out, the temperature is reduced to 5 ℃ for crystallization, white solid is obtained by filtration, and the white solid is placed into an oven and dried at 45 ℃ to obtain 612g of finished product of the ethylene sulfate.
Example 3
And (3) synthesizing ethylene sulfite: adding 200g of ethylene glycol into a reaction kettle, opening and stirring, introducing a circulating cooling liquid into a jacket of the reaction kettle, and slowly dropwise adding 407g of thionyl chloride into the reaction kettle, wherein the adding mode of the thionyl chloride is as follows: adding thionyl chloride into a dropping funnel, opening a valve between the reaction kettle and a tail gas absorption tank when the temperature in the reaction kettle reaches a reaction temperature, then opening the valve of the dropping funnel, finishing adding the thionyl chloride within about 2 hours, controlling the reaction temperature to be 15-20 ℃, and absorbing the tail gas by using 20% sodium hydroxide solution. After the dropwise addition, raising the temperature of the kettle liquid to 35 ℃, preserving the heat for 1 hour, continuously raising the temperature of the kettle liquid to 50 ℃, and continuously preserving the heat for 2 hours; after the heat preservation is finished, vacuumizing to-0.06 MPa, maintaining for 3 hours, and degassing the reaction liquid. And (3) recovering the kettle pressure to normal pressure, cooling the kettle liquid to room temperature, adding a 15% potassium carbonate solution to adjust the pH value to 7.5-8, standing for a period of time, and separating a lower layer solution after the kettle liquid is layered to obtain 331g of ethylene sulfite. The ethylene sulfite synthesized by the method has a molar yield of 95% or more (calculated by ethylene glycol) and a chromatographic content of 99% or more.
Synthesizing vinyl sulfate: adding 331g of ethylene sulfite into a reaction kettle, opening and stirring, introducing a circulating cooling liquid into a jacket of the reaction kettle, controlling the initial temperature to be 0-10 ℃, adding 146g of sodium dihydrogen phosphate and 0.3g of ruthenium trichloride, and uniformly stirring; and (3) under stirring, adding 2510g of sodium hypochlorite solution with the concentration of 10% into the reaction kettle dropwise, controlling the dropwise adding speed, adding a proper amount of ice blocks simultaneously, controlling the temperature to be 0-10 ℃, and stirring for 30min after dropwise adding. The reaction solution was filtered to obtain 364g of a crude vinyl sulfate product. Dissolving the obtained crude product of the vinyl sulfate in 2912g of carbon tetrachloride, adding 110g of ice water into the solution, stirring for 5 minutes, standing for layering, separating out a water phase, and repeatedly washing for 5 times to obtain a vinyl sulfate-carbon tetrachloride solution; adding 218g of anhydrous aluminum sulfate into the vinyl sulfate-carbon tetrachloride solution, stirring for 30min, and filtering; and (3) heating the obtained filtrate to 50 ℃ under reduced pressure, distilling off the dichloroethane solvent to obtain a solid, putting the solid into an oven, and drying at 50 ℃ to obtain a white solid. 1083g of methyl ethyl carbonate is added into the obtained solid, stirred and dissolved, the temperature is reduced to 70 ℃, 760g of methyl ethyl carbonate is distilled out, the temperature is reduced to 5 ℃ for crystallization, white solid is obtained by filtration, and the white solid is placed into an oven and dried at the temperature of 60 ℃, thus obtaining 346g of finished product of the ethylene sulfate.
Example 4
And (3) synthesizing ethylene sulfite: adding 280g of ethylene glycol into a reaction kettle, opening and stirring, introducing a circulating cooling liquid into a jacket of the reaction kettle, and slowly dropwise adding 580g of thionyl chloride into the reaction kettle, wherein the adding mode of the thionyl chloride is as follows: adding thionyl chloride into a dropping funnel, opening a valve between the reaction kettle and a tail gas absorption tank when the temperature in the reaction kettle reaches a reaction temperature, then opening the valve of the dropping funnel, finishing adding the thionyl chloride within about 2 hours, controlling the reaction temperature to be 10-20 ℃, and absorbing the tail gas by using 20% sodium hydroxide solution. After the dropwise addition, raising the temperature of the kettle liquid to 10 ℃, preserving the heat for 1 hour, continuously raising the temperature of the kettle liquid to 60 ℃, and continuously preserving the heat for 1.5 hours; after the heat preservation, the reaction solution was degassed after the vacuum was evacuated to-0.07 MPa and maintained for 2.5 hours. And (3) recovering the kettle pressure to normal pressure, cooling the kettle liquid to room temperature, adding a 2% sodium hydroxide solution to adjust the pH value to 7.5-8, standing for a period of time, and separating a lower layer solution after the kettle liquid is layered to obtain 473g of ethylene sulfite. The ethylene sulfite synthesized by the method has a molar yield of 95% or more (calculated by ethylene glycol) and a chromatographic content of 99% or more.
Synthesizing vinyl sulfate: adding 473g of ethylene sulfite into a reaction kettle, opening and stirring, introducing a circulating cooling liquid into a jacket of the reaction kettle, controlling the initial temperature to be 0-10 ℃, adding 156g of potassium dihydrogen phosphate and 0.3g of iridium trichloride, and uniformly stirring; under stirring, 2720g of a 15% sodium hypochlorite solution is added into the reaction kettle dropwise, the dropwise adding speed is controlled, an appropriate amount of ice blocks are added at the same time, the temperature is controlled to be 0-10 ℃, and stirring is carried out for 30min after dropwise adding is finished. The reaction solution was filtered to obtain 522g of a crude vinyl sulfate product. Dissolving the obtained vinyl sulfate crude product in 3135g of chlorobenzene, adding 261g of ice water into the solution, stirring for 5 minutes, standing for layering, separating out a water phase, and repeatedly washing for 6 times to obtain a vinyl sulfate-chlorobenzene solution; adding 157g of anhydrous calcium chloride into the vinyl sulfate-chlorobenzene solution, stirring for 30min, and filtering; and (3) heating the obtained filtrate to 50 ℃ under reduced pressure, distilling off the dichloroethane solvent to obtain a solid, putting the solid into an oven, and drying at 50 ℃ to obtain a white solid. 1083g of dimethyl carbonate is added into the obtained solid, stirred and dissolved, the temperature is increased to 60 ℃ under reduced pressure, 760g of dimethyl carbonate is distilled out, the temperature is immediately reduced to-5 ℃ for crystallization, white solid is obtained by filtration, and the white solid is put into an oven and dried at 50 ℃ to obtain 512g of finished product of the ethylene sulfate.
Example 5
And (3) synthesizing ethylene sulfite: adding 160g of ethylene glycol into a reaction kettle, opening and stirring, introducing a circulating cooling liquid into a jacket of the reaction kettle, and slowly dropwise adding 322g of thionyl chloride into the reaction kettle, wherein the adding mode of the thionyl chloride is as follows: adding thionyl chloride into a dropping funnel, opening a valve between the reaction kettle and a tail gas absorption tank when the temperature in the reaction kettle reaches a reaction temperature, then opening the valve of the dropping funnel, finishing adding the thionyl chloride within about 2 hours, controlling the reaction temperature to be 10-20 ℃, and absorbing the tail gas by using 20% sodium hydroxide solution. After the dropwise addition, raising the temperature of the kettle liquid to 40 ℃, preserving the heat for 1 hour, continuously raising the temperature of the kettle liquid to 55 ℃, and continuously preserving the heat for 2 hours; after the heat preservation, the reaction solution was degassed after the vacuum was evacuated to-0.075 MPa and maintained for 3 hours. And (3) recovering the kettle pressure to normal pressure, cooling the kettle liquid to room temperature, adding a 10% sodium carbonate solution to adjust the pH value to 7.5-8, standing for a period of time, and separating a lower layer solution after the kettle liquid is layered to obtain 266g of ethylene sulfite. The ethylene sulfite synthesized by the method has a molar yield of 95% or more (calculated by ethylene glycol) and a chromatographic content of 99% or more.
Synthesizing vinyl sulfate: adding 266g of ethylene sulfite into a reaction kettle, opening and stirring, introducing a circulating cooling liquid into a jacket of the reaction kettle, controlling the initial temperature to be 0-10 ℃, adding 176g of sodium dihydrogen phosphate and 0.1g of ruthenium trichloride, and uniformly stirring; and (3) dropwise adding 2200g of sodium hypochlorite solution with the concentration of 10% into the reaction kettle under stirring, controlling the dropwise adding speed, simultaneously adding a proper amount of ice blocks, controlling the temperature to be 0-10 ℃, and stirring for 30min after dropwise adding. The reaction solution was filtered to obtain 290g of a crude vinyl sulfate product. Dissolving the obtained vinyl sulfate crude product in 2322g of dichloroethane, adding 174g of ice water into the solution, stirring for 5 minutes, standing for layering, separating out a water phase, and repeatedly washing with water for 6 times to obtain a vinyl sulfate-dichloroethane solution; adding 116g of anhydrous magnesium chloride into the vinyl sulfate-dichloroethane solution, stirring for 30min, and filtering; and (3) heating the obtained filtrate to 50 ℃ under reduced pressure, distilling off the dichloroethane solvent to obtain a solid, putting the solid into an oven, and drying at 50 ℃ to obtain a white solid. 1083g of ethylene carbonate is added into the obtained solid, stirred and dissolved, the temperature is reduced to 80 ℃, 650g of ethylene carbonate is distilled out, the temperature is reduced to 0 ℃ for crystallization, white solid is obtained by filtration, and the white solid is placed into an oven and dried at the temperature of 55 ℃, thus obtaining 276g of finished product of ethylene sulfate.
Claims (10)
1. A method for synthesizing vinyl sulfate is characterized by comprising the following steps:
s1, adding ethylene glycol into the reaction kettle, and cooling the kettle to below 35 ℃;
s2, adding thionyl chloride into the reaction kettle;
s3, raising the temperature of the reaction kettle to 30-45 ℃, and preserving the heat for 1-3 hours; then raising the temperature of the kettle to 45-60 ℃, and continuously preserving the heat for 1-3 hours;
s4, after the heat preservation is finished, when the temperature of the kettle is 30-60 ℃, vacuumizing to-0.05-0.1 MPa, maintaining the vacuum for 1-3 hours, and degassing the reaction liquid;
s5, after degassing, restoring the kettle pressure to normal pressure, dropwise adding alkali liquor into the reaction kettle when the kettle temperature is 10-40 ℃, and adjusting the pH value of the kettle liquor to 7.5-8; after the kettle liquid is layered, separating a lower layer solution to obtain a finished product of the ethylene sulfite;
s6, adding the ethylene sulfite into a reaction kettle, reducing the temperature of kettle liquid to 0-10 ℃, and adding a buffering agent and a catalyst;
s7, adding a sodium hypochlorite solution into the reaction kettle, and maintaining the temperature of the reaction kettle at 0-10 ℃;
s8, filtering the reaction mixed liquid to obtain a solid, namely a vinyl sulfate crude product;
s9, dissolving the vinyl sulfate crude product in an organic solvent, adding ice water into the solution, stirring for 5-10 min, standing for layering, separating out a water phase, and repeatedly washing for 4-10 times to obtain a vinyl sulfate organic solution;
s10, adding a dehydrating agent into the vinyl sulfate organic solution, and filtering to obtain an anhydrous vinyl sulfate organic solution;
s11, concentrating and crystallizing the obtained vinyl sulfate organic solution, and drying the obtained solid to obtain a primary crystal of the vinyl sulfate; re-dissolving the primary crystal in an organic solvent, distilling out part of the solvent under reduced pressure, cooling for crystallization, and filtering to obtain a white filter cake;
and S12, putting the filter cake obtained in the step S11 into an oven for drying to obtain a white solid, namely a finished product of the vinyl sulfate.
2. The method for synthesizing vinyl sulfate as claimed in claim 1, wherein the molar ratio of the amount of thionyl chloride used in step S2 to the amount of ethylene glycol used in step S1 is 1: 1.92 to 2.1.
3. The method for synthesizing vinyl sulfate according to claim 1, wherein the alkali solution in step S5 is an aqueous solution of one or more of sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium hydroxide, and potassium hydroxide.
4. The vinyl sulfate synthesis method according to claim 1, wherein the buffer in step S6 is selected from one or two of sodium dihydrogen phosphate and potassium dihydrogen phosphate; the mol ratio of the buffering agent to the ethylene sulfite is 0.1-1: 1.
5. The vinyl sulfate synthesis method according to claim 1, wherein the catalyst in step S6 is one or more selected from ruthenium trichloride, rhodium trichloride, palladium dichloride, osmium trichloride, iridium trichloride and platinum chloride, and the molar ratio of the catalyst to vinyl sulfite is 1: 100-10000.
6. The method for synthesizing vinyl sulfate according to claim 1, wherein the molar ratio of the total amount of sodium hypochlorite in the sodium hypochlorite solution in step S7 to the vinyl sulfite in step S6 is 1-1.5: 1.
7. The vinyl sulfate synthesis method 1 according to claim 1, wherein the organic solvent in step S9 is one or more of chloroform, carbon tetrachloride, dichloroethane, trichloroethane, dichloropropane, trichloropropane, chlorobenzene, and dichlorobenzene; the mass ratio of the organic solvent to the vinyl sulfate crude product is 3-30: 1.
8. The vinyl sulfate synthesis method according to claim 1, wherein the mass ratio of the amount of ice water used in step S9 to the crude vinyl sulfate product is 0.2-1: 1.
9. The vinyl sulfate synthesis method according to claim 1, wherein the dehydrating agent in step S10 is one or more of sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate, aluminum sulfate, ferric sulfate, sodium chloride, potassium chloride, calcium chloride, magnesium chloride, and aluminum chloride; the molar ratio of the consumption of the dehydrating agent in the step S10 to the crude vinyl sulfate product in the step S9 is 0.1-1: 1.
10. The method for synthesizing ethylene sulfate according to claim 1, wherein the organic solvent in step S11 is one or more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propylene carbonate, and ethylene carbonate; the amount of the organic solvent used in step S11 is equivalent to the weight of the organic solvent used in step S9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010657303.6A CN111925352A (en) | 2020-07-09 | 2020-07-09 | Method for synthesizing vinyl sulfate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010657303.6A CN111925352A (en) | 2020-07-09 | 2020-07-09 | Method for synthesizing vinyl sulfate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111925352A true CN111925352A (en) | 2020-11-13 |
Family
ID=73313829
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010657303.6A Pending CN111925352A (en) | 2020-07-09 | 2020-07-09 | Method for synthesizing vinyl sulfate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111925352A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112679466A (en) * | 2020-12-27 | 2021-04-20 | 江苏瀚康新材料有限公司 | Method for synthesizing vinyl sulfate |
| CN113683592A (en) * | 2021-08-27 | 2021-11-23 | 江苏瀚康新材料有限公司 | Preparation method of ethyl methyl carbonate solution containing ethylene sulfate |
| CN114195757A (en) * | 2022-01-05 | 2022-03-18 | 香河昆仑新能源材料股份有限公司 | Method for synthesizing vinyl sulfate |
| CN114225855A (en) * | 2021-11-29 | 2022-03-25 | 山东石大胜华化工集团股份有限公司 | Vinyl sulfate synthesis device and method |
| CN115557927A (en) * | 2022-09-13 | 2023-01-03 | 珠海正杏新材料科技有限公司 | Preparation method of vinyl sulfate |
| CN115677652A (en) * | 2022-11-14 | 2023-02-03 | 陕西煤业化工技术研究院有限责任公司 | Method for continuously preparing vinyl sulfate |
| CN115806540A (en) * | 2022-11-18 | 2023-03-17 | 山东兴文工业技术研究院有限公司 | Preparation method of ethylene sulfite |
| CN115974831A (en) * | 2022-09-14 | 2023-04-18 | 多氟多新材料股份有限公司 | Preparation method of cyclic sulfate |
| CN116239564A (en) * | 2023-01-09 | 2023-06-09 | 曹文兵 | Preparation method of cyclic sulfite, tri (trimethylsilane) phosphate and cyclic sulfate carbonate solution continuous co-production |
| CN116535385A (en) * | 2022-08-29 | 2023-08-04 | 苏州华一新能源科技股份有限公司 | Method for preparing vinyl sulfate |
| CN118084857A (en) * | 2024-01-31 | 2024-05-28 | 福建省德旭新材料有限公司 | Preparation method of vinyl sulfate |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106187989A (en) * | 2016-07-26 | 2016-12-07 | 张家港瀚康化工有限公司 | The preparation method of sulfuric acid vinyl ester |
| CN109369609A (en) * | 2018-11-02 | 2019-02-22 | 珠海市赛纬电子材料股份有限公司 | A kind of preparation method of sulfuric acid vinyl ester |
| CN109485633A (en) * | 2018-12-06 | 2019-03-19 | 东营石大胜华新能源有限公司 | A kind of preparation method of sulfuric acid vinyl ester |
| CN109776361A (en) * | 2017-11-14 | 2019-05-21 | 石家庄圣泰化工有限公司 | The synthetic method of sulfuric acid vinyl ester |
| CN109988145A (en) * | 2019-05-13 | 2019-07-09 | 福建博鸿新能源科技有限公司 | A kind of preparation method of sulfuric acid vinyl ester |
-
2020
- 2020-07-09 CN CN202010657303.6A patent/CN111925352A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106187989A (en) * | 2016-07-26 | 2016-12-07 | 张家港瀚康化工有限公司 | The preparation method of sulfuric acid vinyl ester |
| CN109776361A (en) * | 2017-11-14 | 2019-05-21 | 石家庄圣泰化工有限公司 | The synthetic method of sulfuric acid vinyl ester |
| CN109369609A (en) * | 2018-11-02 | 2019-02-22 | 珠海市赛纬电子材料股份有限公司 | A kind of preparation method of sulfuric acid vinyl ester |
| CN109485633A (en) * | 2018-12-06 | 2019-03-19 | 东营石大胜华新能源有限公司 | A kind of preparation method of sulfuric acid vinyl ester |
| CN109988145A (en) * | 2019-05-13 | 2019-07-09 | 福建博鸿新能源科技有限公司 | A kind of preparation method of sulfuric acid vinyl ester |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112679466A (en) * | 2020-12-27 | 2021-04-20 | 江苏瀚康新材料有限公司 | Method for synthesizing vinyl sulfate |
| CN113683592A (en) * | 2021-08-27 | 2021-11-23 | 江苏瀚康新材料有限公司 | Preparation method of ethyl methyl carbonate solution containing ethylene sulfate |
| CN114225855A (en) * | 2021-11-29 | 2022-03-25 | 山东石大胜华化工集团股份有限公司 | Vinyl sulfate synthesis device and method |
| CN114195757A (en) * | 2022-01-05 | 2022-03-18 | 香河昆仑新能源材料股份有限公司 | Method for synthesizing vinyl sulfate |
| CN116535385A (en) * | 2022-08-29 | 2023-08-04 | 苏州华一新能源科技股份有限公司 | Method for preparing vinyl sulfate |
| CN115557927A (en) * | 2022-09-13 | 2023-01-03 | 珠海正杏新材料科技有限公司 | Preparation method of vinyl sulfate |
| CN115974831A (en) * | 2022-09-14 | 2023-04-18 | 多氟多新材料股份有限公司 | Preparation method of cyclic sulfate |
| CN115677652A (en) * | 2022-11-14 | 2023-02-03 | 陕西煤业化工技术研究院有限责任公司 | Method for continuously preparing vinyl sulfate |
| CN115806540A (en) * | 2022-11-18 | 2023-03-17 | 山东兴文工业技术研究院有限公司 | Preparation method of ethylene sulfite |
| CN116239564A (en) * | 2023-01-09 | 2023-06-09 | 曹文兵 | Preparation method of cyclic sulfite, tri (trimethylsilane) phosphate and cyclic sulfate carbonate solution continuous co-production |
| CN118084857A (en) * | 2024-01-31 | 2024-05-28 | 福建省德旭新材料有限公司 | Preparation method of vinyl sulfate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111925352A (en) | Method for synthesizing vinyl sulfate | |
| CN112679466A (en) | Method for synthesizing vinyl sulfate | |
| CN109485633A (en) | A kind of preparation method of sulfuric acid vinyl ester | |
| CN108840854B (en) | Method for synthesizing 5-chlorothiophene-2-carboxylic acid by one-pot method | |
| CN107556286A (en) | A kind of synthetic method of 1,3 propene sultone | |
| CN116496159A (en) | Preparation method of ethyl 6,8-dichloro octoate | |
| CN115557927A (en) | Preparation method of vinyl sulfate | |
| CN103314004B (en) | New preparation method of 5,7-pregnadiene-3,20-dione-diethyl ketal | |
| CN110143922B (en) | Synthetic method of 1, 1' -dithio-di-caprolactam | |
| CN102617335B (en) | Process for synthesizing p-tert-butylbenzoic acid | |
| CN101899020A (en) | DZ synthesized by mixing mother solution | |
| CN110128258B (en) | Synthetic method of sitagliptin intermediate 2,4, 5-trifluorophenylacetic acid | |
| CN103539745B (en) | A kind of preparation method of secnidazole | |
| CN1685818A (en) | Simplified production technology of bisultap | |
| CN116425729A (en) | Litaset morpholine salt and preparation method and application thereof | |
| CN113292467B (en) | Method for purifying vitamin A oil mother liquor by using alcohol-containing alkali liquor | |
| CN111548295B (en) | Preparation method of di (2-ethylhexyl) peroxydicarbonate | |
| CN110407871B (en) | Glyphosate crystallization device and crystallization method | |
| CN210765083U (en) | Glyphosate crystal cleaning device | |
| CN112159388A (en) | Preparation method of vinyl sulfate derivative | |
| CN109912651B (en) | Preparation method of benzyltriphenylphosphonium chloride | |
| CN111592556A (en) | Bromoacetyl-7-ACA production process | |
| EP0068248B1 (en) | Process for the production of dithionites | |
| CN112745246A (en) | Purification method of shakubiqu intermediate | |
| CN1706792A (en) | Purifying process of 3,4,5-trimethoxyl benzoic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201113 |