CN107353277B - Preparation method of cyclic sulfates - Google Patents
Preparation method of cyclic sulfates Download PDFInfo
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- CN107353277B CN107353277B CN201710560064.0A CN201710560064A CN107353277B CN 107353277 B CN107353277 B CN 107353277B CN 201710560064 A CN201710560064 A CN 201710560064A CN 107353277 B CN107353277 B CN 107353277B
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- 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
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Abstract
The invention provides a preparation method of cyclic sulfates, which comprises the steps of A) reacting reaction gas with dioxane under the protection of inert gas to obtain oily matter, wherein the reaction gas is sulfur trioxide or sulfur dioxide, and B) sublimating or distilling the oily matter to obtain the cyclic sulfates.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of cyclic sulfates.
Background
The cyclic sulfate and cyclic carbonate are used as kinds of organic chemical products, mainly used as additives of lithium ion battery electrolyte, such as ethylene sulfite, ethylene sulfate, ethylene carbonate, etc. the ethylene sulfite can be used as organic solvent of lithium ion battery electrolyte and also as additive of lithium ion battery electrolyte, the ethylene sulfate is used as novel additive of lithium ion battery electrolyte, and has the functions of inhibiting the reduction of initial capacity of battery, increasing initial discharge capacity, reducing battery expansion after high temperature placement, improving charge and discharge performance and cycle number of battery, and the high-purity ethylene carbonate is mainly used as additive of lithium ion battery electrolyte.
The preparation process of the ethylene sulfite disclosed in the prior art comprises the step of preparing the ethylene sulfite by the reaction of ethylene oxide and sulfur dioxide under the conditions of high temperature (220-300 ℃) and high pressure (more than 10MPa) through metal catalysis. The processes for preparing vinyl sulfate disclosed in the prior art include preparing vinyl sulfate by the catalytic oxidation of vinyl sulfite with ruthenium metal. The preparation process of ethylene carbonate disclosed in the prior art comprises preparing ethylene carbonate by catalyzing carbon dioxide and ethylene oxide to react under the conditions of high temperature (more than 140 ℃) and high pressure (more than 2MPa) by using a divinylbenzene polymer. The preparation process has the disadvantages of high cost, much wastewater generated in the preparation process and low yield.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a method for preparing cyclic sulfates, which has high purity and yield and low cost.
The invention provides a preparation method of cyclic sulfates, which comprises the following steps:
A) reacting the reaction gas with dioxane under the protection of inert gas to obtain oily matter; the reaction gas is sulfur trioxide or sulfur dioxide;
B) sublimating or distilling the oily matter to obtain cyclic sulfate.
Preferably, the inert gas is or more selected from nitrogen, helium, argon and xenon.
Preferably, the dioxane is heated to 90-140 ℃ before being mixed with the reaction gas.
Preferably, the mass ratio of the reaction gas to dioxane is 1: (1-10).
Preferably, the reaction temperature is 30-150 ℃.
Preferably, the method also comprises mixing the reaction gas with inert gas and then reacting with dioxane; the volume ratio of the reaction gas to the inert gas is 0.2-5: 1.
Preferably, the reaction gas is mixed and reacted with dioxane at the speed of , and the mixing speed is 3-8 mL/min.
Preferably, the step a) after the reaction is specifically: dioxane was concentrated under reduced pressure to give an oil.
Preferably, the sublimation temperature is 50-85 ℃.
Preferably, the distillation temperature is 45-100 ℃.
Compared with the prior art, the invention provides a preparation method of cyclic sulfates, which comprises the steps of A) reacting reaction gas with dioxane under the protection of inert gas to obtain oily matter, wherein the reaction gas is sulfur trioxide or sulfur dioxide, and B) sublimating or distilling the oily matter to obtain the cyclic sulfates.
Drawings
FIG. 1 is a gas chromatogram of vinyl sulfate prepared in example 1 of the present invention;
FIG. 2 is a gas chromatogram of the vinyl sulfite prepared in example 2 of the present invention.
Detailed Description
The invention provides a preparation method of cyclic sulfates, which comprises the following steps:
A) reacting the reaction gas with dioxane under the protection of inert gas to obtain oily matter; the reaction gas is sulfur trioxide or sulfur dioxide;
B) sublimating or distilling the oily matter to obtain cyclic sulfate.
The invention provides a preparation method of cyclic sulfate.
The cyclic sulfate ester is ethylene sulfite and ethylene sulfate. Vinyl sulfite and vinyl sulfate, which are well known to those skilled in the art.
The preparation method of the cyclic sulfate provided by the invention comprises the following step of reacting a reaction gas with dioxane under the protection of an inert gas to obtain an oily substance.
Preferably, the dioxane is heated under the protection of inert gas, and the reaction gas is mixed with the dioxane at speed for reaction, wherein the mixing is preferably carried out by introducing the reaction gas into the dioxane for reaction.
In the present invention, the inert gas is preferably or more selected from nitrogen, helium, argon and xenon, more preferably or more selected from nitrogen, helium and argon, and most preferably nitrogen.
In the present invention, since the reaction is carried out in the presence of an inert gas, the atmosphere in the reaction vessel needs to be replaced with the inert gas before the reaction, thereby ensuring an inert gas atmosphere.
The dioxane is not limited, but is preferably anhydrous dioxane; the source is not limited, and may be commercially available.
In the invention, the heating of dioxane specifically comprises: heating the dioxane to 90-140 ℃ before mixing with the reaction gas; more preferably, the temperature is increased to 95 to 135 ℃. The heating is preferably oil bath heating.
After heating, the reaction gas was mixed with dioxane at to react.
Wherein the mass ratio of the reaction gas to dioxane is preferably 1: (1-10); more preferably 1: (2-8); most preferably 1: (3-7).
The reaction gas is mixed and reacted with dioxane at constant speed, and the mixing speed is preferably 3-8 mL/min, more preferably 3.5-8 mL/min.
The reaction temperature is preferably 30-150 ℃; more preferably 60 to 140 ℃; the most preferable is 90-100 ℃; most preferably 95-100 ℃; the reaction time is preferably 15-40 min; more preferably 20 to 35 min.
According to the invention, the method also comprises the steps of mixing the reaction gas with the inert gas and then reacting with dioxane; the volume ratio of the reaction gas to the inert gas is preferably 0.2-5: 1; more preferably 0.5-4.5: 1; most preferably 1-4: 1; most preferably 1: 1.
At the moment, the flow rate of the mixed gas of the reaction gas and the inert gas is preferably 3-8 mL/min; more preferably 3.5 to 8 mL/min.
Among them, the mode of mixing the reaction gas and the inert gas is preferably that the reaction gas and the inert gas are mixed through the glass filler.
The reaction temperature is preferably 30-150 ℃; more preferably 60 to 140 ℃; the most preferable is 90-100 ℃; most preferably 95-100 ℃; the reaction time is preferably 15-40 min; more preferably 20 to 35 min.
The inert gas is preferably or more selected from nitrogen, helium, argon and xenon, more preferably or more selected from nitrogen, helium and argon, and most preferably nitrogen.
The reaction vessel of the present invention is not limited, and may be any reaction vessel known to those skilled in the art; preferably a three-mouth bottle; more preferably a three-necked flask with magnetic stirring and a thermometer.
After the reaction is finished, preferably stirring naturally, and cooling to room temperature. The stirring speed and the cooling mode are not limited in the invention, and the stirring speed and the cooling mode are well known to those skilled in the art; preferably, the temperature is reduced to 25-35 ℃.
After cooling, the dioxane was concentrated under reduced pressure to give an oil.
The present invention is not limited to the specific parameters for the concentration of dioxane under reduced pressure, and those skilled in the art will be familiar with the present invention. Because the dioxane of the invention is a reactant and also acts as a reaction solvent, the product can be separated and the solvent can be recovered by decompression and concentration, thereby avoiding waste.
Wherein, when the reaction gas comprises sulfur dioxide, the oily matter is the ethylene sulfite, and at the moment, the oily matter is distilled to obtain the cyclic sulfate. Namely the ethylene sulfite.
The distillation is preferably carried out by firstly heating to 40-45 ℃ and collecting front fraction; then heating to 45-100 ℃; more preferably, heating to 40-45 ℃ first, and collecting front fraction; then heating to 50-90 ℃; most preferably, heating to 40-45 ℃ first, and collecting front fraction; and then heating to 60-70 ℃.
The heating is preferably oil bath heating; the vacuum degree is preferably 3-7 mbar.
The container for the distillation is not limited in the present invention, and is preferably a three-necked bottle.
Wherein, when the reaction gas comprises sulfur trioxide, the oily matter is vinyl sulfate, and at the moment, the oily matter is sublimated to obtain the cyclic sulfate. Namely the vinyl sulfate.
The sublimation is preferably carried out by transferring the oily substance into a sublimator, maintaining constant vacuum degree, and heating for sublimation to obtain vinyl sulfate.
The heating is preferably oil bath heating; the sublimation temperature is preferably 50-85 ℃; more preferably 60-80 ℃; the most preferable range is 68-72 ℃. The vacuum degree is preferably 3-7 mbar.
The invention provides a preparation method of cyclic sulfates, which comprises the steps of A) reacting reaction gas with dioxane under the protection of inert gas to obtain oily matter, wherein the reaction gas is sulfur trioxide or sulfur dioxide, and B) sublimating or distilling the oily matter to obtain the cyclic sulfates.
The purity and yield of the prepared vinyl sulfate or vinyl sulfite are preferably identified by the following method:
the analysis method comprises the following steps:
shimadzu gas chromatograph 2014C
FID detector
GC chromatography column RTx-560 m 0.32mm 3 μm
A sample inlet of 220 DEG C
Detector 250 deg.c
The temperature of the column box is 80 ℃ for 1min 80 ℃ → 250 ℃ for 15 ℃/min 250 ℃ for 15 min.
In order to further illustrate the present invention at , the following examples are provided to describe the preparation of cyclic sulfates in detail.
Example 1
Building a magnetic stirring and thermometer in a 1000ml three-mouth bottle, replacing air in the bottle with nitrogen, adding 650.0g of anhydrous dioxane under the protection of nitrogen, and heating to 95 ℃ in an oil bath;
fully mixing dry nitrogen and sulfur trioxide gas by using a glass filler, adjusting the flow rate to ensure that the volume ratio of the dry nitrogen to the sulfur trioxide gas is 1:1, the total flow rate is 3.7ml/min, gradually changing the solution from colorless to pale yellow, completely introducing the solution for about 30min, consuming 99.5g of sulfur trioxide, and continuously reacting for 5 min;
naturally stirring, cooling to room temperature, concentrating under reduced pressure, and recovering 532.4g dioxane to obtain 198.0g pale yellow oil;
198.0g of pale yellow oil are transferred into a sublimator, the vacuum degree is maintained at 3mbar, the oil bath is gradually heated to 70 ℃ and sublimation is carried out to obtain 117.5g of white acicular solid vinyl sulfate with the purity of 99.64 percent and the yield of 76.17 percent.
GC identification was performed according to the method of the present invention, and as shown in FIG. 1, FIG. 1 is a gas chromatogram of vinyl sulfate prepared in example 1 of the present invention, wherein 15.399min is vinyl sulfate.
Example 2
Building a magnetic stirring and thermometer in a 1000ml three-mouth bottle, replacing air in the bottle with nitrogen, adding 610.0g of anhydrous dioxane under the protection of nitrogen, and heating to 95 ℃ in an oil bath;
fully mixing dry nitrogen and sulfur dioxide gas by using a glass filler, adjusting the flow rate to ensure that the volume ratio of the dry nitrogen and the sulfur dioxide gas is 1:0.8, the total flow rate is 4.5ml/min, gradually changing the solution into light yellow after the solution is colorless, completely introducing the solution for about 30min, consuming 86.0g of sulfur dioxide, and continuously reacting for 5 min;
naturally stirring, cooling to room temperature, concentrating under reduced pressure, and recovering 496.0g dioxane to obtain 182.1g pale yellow oily substance;
182.1g of pale yellow oil are transferred into a three-necked flask, the vacuum degree is kept at 7mbar, the temperature of an oil bath is raised to 45 ℃, 10.3g of front cut fraction is collected, the temperature of the oil bath is raised to 65 ℃, and distillation is carried out to obtain 105.8g of colorless transparent liquid ethylene sulfite with the purity of 99.58 percent and the yield of 72.89 percent.
GC identification was performed according to the method of the present invention, and as shown in FIG. 2, FIG. 2 is a gas chromatogram of the vinyl sulfite prepared in example 2 of the present invention, wherein 11.360min is vinyl sulfite.
Example 3
Building a magnetic stirring and thermometer in a 1000ml three-mouth bottle, replacing air in the bottle with nitrogen, adding 510.0g of anhydrous dioxane under the protection of nitrogen, and heating to 120 ℃ in an oil bath;
fully mixing dry nitrogen and sulfur trioxide gas through a glass filler, adjusting the flow rate to ensure that the volume ratio of the dry nitrogen to the sulfur trioxide gas is 1:2, the total flow rate is 5.7ml/min, gradually changing the solution from colorless to light yellow, completely introducing for about 15min, consuming 102.2g of sulfur trioxide, and continuously reacting for 5 min;
naturally stirring, cooling to room temperature, concentrating under reduced pressure, and recovering 417.8g dioxane to obtain 183.2g pale yellow oily substance;
183.2g of the pale yellow oil were transferred into a sublimator, the vacuum was maintained at 3mbar and the oil bath was gradually warmed to 75 ℃ and sublimed to give 118.7g of vinyl sulfate as a white needle-like solid with a purity of 99.68% and a yield of 74.92%.
Example 4
Building a magnetic stirring and thermometer in a 2000ml three-necked flask, replacing air in the flask with nitrogen, adding 1370.0g of anhydrous dioxane under the protection of nitrogen, and heating to 110 ℃ in an oil bath;
fully mixing dry nitrogen and sulfur dioxide gas by using a glass filler, adjusting the flow rate to ensure that the volume ratio of the dry nitrogen to the sulfur dioxide gas is 1:3, the total flow rate is 8.0ml/min, gradually changing the solution into light yellow after colorless, consuming 344.1g of sulfur dioxide after about 40min of introduction is finished, and continuously reacting for 5 min;
naturally stirring, cooling to room temperature, concentrating under reduced pressure, and recovering 973.0g dioxane to obtain 697.2g pale yellow oily substance;
697.2g of pale yellow oil are transferred into a three-necked flask, the vacuum degree is kept at 7mbar, the temperature of an oil bath is raised to 45 ℃, 35.5g of front cut fraction is collected, the temperature of the oil bath is raised to 70 ℃, and 441.3g of colorless transparent liquid ethylene sulfite with the purity of 99.53 percent and the yield of 75.99 percent are obtained by distillation.
Example 5
Building a magnetic stirring and thermometer in a 2000ml three-mouth bottle, replacing air in the bottle with nitrogen, adding 1300.0g of anhydrous dioxane under the protection of nitrogen, and heating to 130 ℃ in an oil bath;
fully mixing dry nitrogen and sulfur trioxide gas by using a glass filler, adjusting the flow rate to ensure that the volume ratio of the dry nitrogen to the sulfur trioxide gas is 1:1, the total flow rate is 7.4ml/min, gradually changing the solution from colorless to pale yellow, consuming 199.1g of sulfur trioxide after about 30min of introduction is finished, and continuously reacting for 5 min;
naturally stirring, cooling to room temperature, concentrating under reduced pressure, and recovering 1061.1g dioxane to obtain 409.4g pale yellow oily substance;
409.4g of pale yellow oil are transferred into a sublimator, the vacuum degree is kept at 3mbar, the oil bath is gradually heated to 72 ℃ and sublimation is carried out to obtain 240.7g of white acicular solid vinyl sulfate with the purity of 99.64 percent and the yield of 77.98 percent
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
- The preparation method of cyclic sulfates is characterized by comprising the following steps:A) reacting the reaction gas with dioxane under the protection of inert gas to obtain oily matter; the reaction gas is sulfur trioxide or sulfur dioxide; heating to 90-140 ℃ before mixing the dioxane and the reaction gas;B) sublimating or distilling the oily matter to obtain cyclic sulfate.
- 2. The method according to claim 1, wherein the inert gas is or more selected from nitrogen, helium, argon and xenon.
- 3. The production method according to claim 1, wherein the mass ratio of the reaction gas to dioxane is 1: (1-10).
- 4. The method of claim 1, further comprising mixing a reactive gas with an inert gas and reacting with dioxane; the volume ratio of the reaction gas to the inert gas is 0.2-5: 1.
- 5. The preparation method according to claim 1, wherein the reaction gas is mixed with dioxane at , and the mixing speed is 3-8 mL/min.
- 6. The preparation method according to claim 1, wherein the step A) is specifically as follows: dioxane was concentrated under reduced pressure to give an oil.
- 7. The method according to claim 1, wherein the sublimation temperature is 50 to 85 ℃.
- 8. The method according to claim 1, wherein the distillation temperature is 45 to 100 ℃.
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| CN111662268B (en) * | 2020-06-12 | 2023-01-10 | 上海如鲲新材料股份有限公司 | Preparation method and application of cyclic sulfate compound |
| CN114920725B (en) * | 2022-05-25 | 2024-03-19 | 重庆敏恒科技有限公司 | Method for preparing high-purity vinyl sulfate by sublimation crystallization and purification |
| CN115724822A (en) * | 2022-11-23 | 2023-03-03 | 武汉奥克特种化学有限公司 | Production process of electronic-grade vinyl sulfate |
| CN115894433A (en) * | 2022-11-23 | 2023-04-04 | 武汉奥克特种化学有限公司 | Process for continuously synthesizing vinyl sulfate crude product |
| CN116836147B (en) * | 2023-06-28 | 2024-04-19 | 辽宁奥克化学股份有限公司 | Preparation method and application of cyclic sulfate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1037708A (en) * | 1988-05-16 | 1989-12-06 | 罗纳-布朗克制药公司 | The method for making of cyclic sulfates |
| CN1058592A (en) * | 1990-07-09 | 1992-02-12 | 罗纳-布朗克罗莱尔股份有限公司 | Process for preparation of cyclic sulfates |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1037708A (en) * | 1988-05-16 | 1989-12-06 | 罗纳-布朗克制药公司 | The method for making of cyclic sulfates |
| CN1058592A (en) * | 1990-07-09 | 1992-02-12 | 罗纳-布朗克罗莱尔股份有限公司 | Process for preparation of cyclic sulfates |
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