CN107353277A - A kind of preparation method of cyclic sulfates - Google Patents
A kind of preparation method of cyclic sulfates Download PDFInfo
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- CN107353277A CN107353277A CN201710560064.0A CN201710560064A CN107353277A CN 107353277 A CN107353277 A CN 107353277A CN 201710560064 A CN201710560064 A CN 201710560064A CN 107353277 A CN107353277 A CN 107353277A
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- preparation
- dioxane
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- cyclic sulfates
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- 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
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Abstract
The invention provides a kind of preparation method of cyclic sulfates, including：A) under conditions of inert gas shielding, reacting gas and dioxane is reacted, obtain grease；The reacting gas is sulfur trioxide or sulfur dioxide；B the grease) is obtained into cyclic sulfates through distilling or distilling.It is provided by the invention that cracking annulation is occurred with dioxane using sulfur trioxide or sulfur dioxide, the purity and high income of cyclic sulfates are obtained, while the technology path technique of the present invention is simple, raw material is easy to get, and cost is low, mild condition, and it is few to produce waste water.
Description
Technical field
The present invention relates to technical field of organic synthesis, more particularly, to a kind of preparation method of cyclic sulfates.
Background technology
Cyclic sulfates and cyclic carbonate are mainly used as lithium-ion battery electrolytes as a kind of Organic chemical products
Additive, such as ethylene sulfite, sulfuric acid vinyl ester, ethylene carbonate.Ethylene sulfite can be used as lithium ion battery battery
The organic solvent of matter is solved, but also as the additive of lithium-ion battery electrolytes.Sulfuric acid vinyl ester is as new type lithium ion battery
Electrolysis additive, its role is to suppress the decline of battery initial capacity, increase initial discharge capacity, after reducing high temperature placement
Cell expansion, improve the charge-discharge performance and cycle-index of battery.High purity carbon vinyl acetate is mainly used as lithium ion battery
The additive of electrolyte.
The preparation technology of ethylene sulfite disclosed in prior art includes, and passes through metal catalytic oxirane and titanium dioxide
Sulphur reaction under the conditions of high temperature (220 DEG C~300 DEG C), high pressure (being more than 10MPa) prepares ethylene sulfite.Prior art discloses
The preparation technology of sulfuric acid vinyl ester include, sulfuric acid vinyl ester is prepared by metal Ru catalysis oxidation ethylene sulfite.It is existing
The preparation technology of ethylene carbonate disclosed in technology includes, and carbon dioxide and oxirane are catalyzed by divinyl benzene polymers
Reaction prepares ethylene carbonate under the conditions of high temperature (being more than 140 DEG C), high pressure (being more than 2MPa).And above-mentioned preparation technology cost mistake
Height, waste water produces more in preparation process, while yield is low.
The content of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of preparation method of cyclic sulfates, this hair
The preparation method purity and high income of the cyclic sulfates of bright offer, while cost is low.
The invention provides a kind of preparation method of cyclic sulfates, including：
A) under conditions of inert gas shielding, reacting gas and dioxane is reacted, obtain grease；The reaction
Gas is sulfur trioxide or sulfur dioxide；
B the grease) is obtained into cyclic sulfates through distilling or distilling.
Preferably, one or more of the inert gas in nitrogen, helium, argon gas and xenon.
Preferably, before the dioxane mixes with reacting gas, 90~140 DEG C are first heated to.
Preferably, the mass ratio of the reacting gas and dioxane is 1：(1~10).
Preferably, the reaction temperature is 30~150 DEG C.
Preferably, in addition to by reacting gas with inert gas mix and reacted again with dioxane；The reacting gas with
The volume ratio of inert gas is 0.2~5:1.
Preferably, the reacting gas is with certain speed and dioxane hybrid reaction, and the mixing velocity is 3~
8mL/min。
Preferably, the step A) reaction after be specially：Be concentrated under reduced pressure dioxane, obtains grease.
Preferably, the temperature of the distillation is 50~85 DEG C.
Preferably, the temperature of the distillation is 45~100 DEG C.
Compared with prior art, the invention provides a kind of preparation method of cyclic sulfates, including：A) in inert gas
Under conditions of protection, reacting gas and dioxane are reacted, obtain grease；The reacting gas is sulfur trioxide or dioxy
Change sulphur；B the grease) is obtained into cyclic sulfates through distilling or distilling.It is provided by the invention to use sulfur trioxide or dioxy
Change sulphur and cracking annulation occurs with dioxane, obtain the purity and high income of cyclic sulfates, while the technology of the present invention
Route technique is simple, and raw material is easy to get, and cost is low, mild condition, and it is few to produce waste water.
Brief description of the drawings
Fig. 1 is the gas chromatogram for the sulfuric acid vinyl ester that the embodiment of the present invention 1 is prepared；
Fig. 2 is the gas chromatogram for the ethylene sulfite that the embodiment of the present invention 2 is prepared.
Embodiment
The invention provides a kind of preparation method of cyclic sulfates, including：
A) under conditions of inert gas shielding, reacting gas and dioxane is reacted, obtain grease；The reaction
Gas is sulfur trioxide or sulfur dioxide；
B the grease) is obtained into cyclic sulfates through distilling or distilling.
The present invention is to provide the preparation method of cyclic sulfates.
Cyclic sulfates of the present invention are ethylene sulfite and sulfuric acid vinyl ester.For known to those skilled in the art
Ethylene sulfite and sulfuric acid vinyl ester.
The preparation method of cyclic sulfates provided by the invention is first under conditions of inert gas shielding, by reacting gas
Reacted with dioxane, obtain grease.
It is preferred that it is specially：Under conditions of inert gas shielding, dioxane is heated, by reacting gas with certain speed
Mix, react with dioxane.The mixing is preferably that reacting gas is passed through in dioxane to react.
In the present invention, the inert gas is preferably selected from the one or more in nitrogen, helium, argon gas and xenon；Institute
State the one or more that inert gas is more preferably in nitrogen, helium and argon gas；Most preferably nitrogen.
The present invention reacts in the presence of inert gas, so needing in inert gas replacement reaction vessel before the reaction
Air, it is ensured that inert gas environment.
The present invention is for the dioxane without restriction, preferably anhydrous dioxane；To its source also without
Limit, can be commercially available.
In the present invention, it is described to be specially by dioxane heating：Before dioxane mixes with reacting gas, preferably first add
Heat is to 90~140 DEG C；More preferably it is heated to 95~135 DEG C.The heating is preferably oil bath heating.
After heating, reacting gas is mixed with certain speed with dioxane, reacted.
Wherein, the mass ratio of the reacting gas and dioxane is preferably 1：(1~10)；More preferably 1：(2~8)；
Most preferably 1：(3~7).
The reacting gas is preferably 3~8mL/ with certain speed and dioxane hybrid reaction, the mixing velocity
min；More preferably 3.5~8mL/min.
The reaction temperature is preferably 30~150 DEG C；More preferably 60~140 DEG C；Most preferably 90~100 DEG C；The most
Preferably 95~100 DEG C；The reaction time is preferably 15~40min；More preferably 20~35min.
According to the present invention, in addition to reacting gas is mixed with inert gas and reacted again with dioxane；The reaction gas
The volume ratio of body and inert gas is preferably 0.2~5:1；More preferably 0.5~4.5:1；Most preferably 1~4:1；It is the most preferred
For 1:1.
Now, the flow of the mixed gas of reacting gas and inert gas is preferably 3~8mL/min；More preferably 3.5~
8mL/min。
Wherein, the mode that reacting gas mixes with inert gas is preferably through glass filler by reacting gas and inert gas
Mixing.
The reaction temperature is preferably 30~150 DEG C；More preferably 60~140 DEG C；Most preferably 90~100 DEG C；The most
Preferably 95~100 DEG C；The reaction time is preferably 15~40min；More preferably 20~35min.
The inert gas preferably is selected from the one or more in nitrogen, helium, argon gas and xenon；The inert gas is more excellent
Elect the one or more in nitrogen, helium and argon gas as；Most preferably nitrogen.
The present invention is for the reaction vessel without restriction, reaction vessel well known to those skilled in the art；It is excellent
Elect there-necked flask as；There-necked flask more preferably with magnetic agitation and thermometer.
Reaction finishes, and preferably stirs naturally, is cooled to room temperature.The present invention is for the speed of the stirring and the mode of cooling
Without limiting, those skilled in the art are known；It is preferred that it is cooled to 25~35 DEG C.
After cooling, be concentrated under reduced pressure dioxane, obtains grease.
The present invention is known without restriction, those skilled in the art for the design parameter of the dioxane that is concentrated under reduced pressure
.Because dioxane of the present invention is reactant, while also it is the effect of reaction dissolvent, therefore production can be separated by being concentrated under reduced pressure
Thing and recycling design, avoid wasting.
Wherein, when reacting gas includes sulfur dioxide, grease is ethylene sulfite, now, by the oily
Thing obtains cyclic sulfates through distillation.As ethylene sulfite.
It is described to distill preferred specifically, being first to heat to 40~45 DEG C, collect front-end volatiles；Then it is heated to 45~100 DEG C；More
It is preferred that being first to heat to 40~45 DEG C, front-end volatiles are collected；Then it is heated to 50~90 DEG C；40~45 DEG C are most preferably first to heat to,
Collect front-end volatiles；Then it is heated to 60~70 DEG C.
The heating is preferably oil bath heating；The vacuum is preferably 3~7mbar.
Container of the invention for the distillation is without restriction, preferably there-necked flask.
Wherein, when reacting gas includes sulfur trioxide, grease is sulfuric acid vinyl ester, now, by the grease
Cyclic sulfates are obtained through distillation.As sulfuric acid vinyl ester.
The distillation is preferably specially that grease is transferred in sublimator, keeps certain vacuum degree, heating sublimation obtains
Sulfuric acid vinyl ester.
The heating is preferably oil bath heating；The temperature of the distillation is preferably 50~85 DEG C；More preferably 60~80 DEG C；
Most preferably 68~72 DEG C.The vacuum is preferably 3~7mbar.
The invention provides a kind of preparation method of cyclic sulfates, including：A, will) under conditions of inert gas shielding
Reacting gas reacts with dioxane, obtains grease；The reacting gas is sulfur trioxide or sulfur dioxide；B) by the oil
Shape thing obtains cyclic sulfates through distilling or distilling.It is provided by the invention to be sent out using sulfur trioxide or sulfur dioxide with dioxane
Raw cracking annulation, obtains the purity and high income of cyclic sulfates, while the technology path technique of the present invention is simple, raw material
It is easy to get, cost is low, mild condition, and it is few to produce waste water.
Present invention preferably employs following manner to the sulfuric acid vinyl ester or the purity of ethylene sulfite and receipts that are prepared
Rate is identified：
Analysis method：
Shimadzu gas chromatograph 2014C
Fid detector
GC chromatographic column RTx-5 60m*0.32mm*3 μm
220 DEG C of injection port
250 DEG C of detector
80 DEG C of post case temperature, 80 DEG C of 1min → 250 DEG C, 15 DEG C/min, 250 DEG C of 15min.
In order to further illustrate the present invention, with reference to embodiments to a kind of preparation of cyclic sulfates provided by the invention
Method is described in detail.
Embodiment 1
To 1000ml there-necked flasks, magnetic agitation and thermometer are built, air in nitrogen displacement bottle, nitrogen protection is lower to be put into
650.0g anhydrous dioxanes, oil bath heating is to 95 DEG C；
Drying nitrogen is sufficiently mixed with sulfur trioxide gas through glass filler, regulation flow makes its volume ratio be 1:1, always
Flow is 3.7ml/min, and solution gradually becomes light yellow by colourless, and about 30min, which is passed through, to be finished, consumption of sulfur trioxide 99.5g, after
Continuous reaction 5min；
Naturally stirring is cooled to room temperature, and be concentrated under reduced pressure recovery 532.4g dioxane, obtains light yellow oil 198.0g；
198.0g light yellow oils are transferred in sublimator, keep 3mbar vacuums, oil bath is gradually heating to 70
DEG C, distillation obtains 117.5g white needles sulfuric acid vinyl esters, purity 99.64%, yield 76.17%.
GC identifications are carried out according to the method described in the present invention, as shown in figure 1, Fig. 1 is what the embodiment of the present invention 1 was prepared
The gas chromatogram of sulfuric acid vinyl ester, wherein 15.399min are sulfuric acid vinyl ester.
Embodiment 2
To 1000ml there-necked flasks, magnetic agitation and thermometer are built, air in nitrogen displacement bottle, nitrogen protection is lower to be put into
610.0g anhydrous dioxanes, oil bath heating is to 95 DEG C；
Drying nitrogen is sufficiently mixed with sulfur dioxide gas through glass filler, regulation flow makes its volume ratio be 1:0.8,
Total flow is 4.5ml/min, and solution gradually whether there is discoloration into light yellow, and about 30min, which is passed through, to be finished, and consumes sulfur dioxide 86.0g,
Continue to react 5min；
Naturally stirring is cooled to room temperature, and be concentrated under reduced pressure recovery 496.0g dioxane, obtains light yellow oil 182.1g；
182.1g light yellow oils are transferred in there-necked flask, keep 7mbar vacuums, oil bath is warming up to 45 DEG C, receives
Collect 10.3g front-end volatiles, oil bath is warming up to 65 DEG C, and distillation obtains 105.8g colourless transparent liquid ethylene sulfites, purity
99.58%, yield 72.89%.
GC identifications are carried out according to the method described in the present invention, as shown in Fig. 2 Fig. 2 is what the embodiment of the present invention 2 was prepared
The gas chromatogram of ethylene sulfite, wherein 11.360min are ethylene sulfite.
Embodiment 3
To 1000ml there-necked flasks, magnetic agitation and thermometer are built, air in nitrogen displacement bottle, nitrogen protection is lower to be put into
510.0g anhydrous dioxanes, oil bath heating is to 120 DEG C；
Drying nitrogen is sufficiently mixed with sulfur trioxide gas through glass filler, regulation flow makes its volume ratio be 1:2, always
Flow is 5.7ml/min, and solution gradually becomes light yellow by colourless, and about 15min, which is passed through, to be finished, consumption of sulfur trioxide 102.2g,
Continue to react 5min；
Naturally stirring is cooled to room temperature, and be concentrated under reduced pressure recovery 417.8g dioxane, obtains light yellow oil 183.2g；
183.2g light yellow oils are transferred in sublimator, keep 3mbar vacuums, oil bath is gradually heating to 75
DEG C, distillation obtains 118.7g white needles sulfuric acid vinyl esters, purity 99.68%, yield 74.92%.
Embodiment 4
To 2000ml there-necked flasks, magnetic agitation and thermometer are built, air in nitrogen displacement bottle, nitrogen protection is lower to be put into
1370.0g anhydrous dioxanes, oil bath heating is to 110 DEG C；
Drying nitrogen is sufficiently mixed with sulfur dioxide gas through glass filler, regulation flow makes its volume ratio be 1:3, always
Flow is 8.0ml/min, and solution gradually whether there is discoloration into light yellow, and about 40min, which is passed through, to be finished, and consumes sulfur dioxide 344.1g,
Continue to react 5min；
Naturally stirring is cooled to room temperature, and be concentrated under reduced pressure recovery 973.0g dioxane, obtains light yellow oil 697.2g；
697.2g light yellow oils are transferred in there-necked flask, keep 7mbar vacuums, oil bath is warming up to 45 DEG C, receives
Collect 35.5g front-end volatiles, oil bath is warming up to 70 DEG C, and distillation obtains 441.3g colourless transparent liquid ethylene sulfites, purity
99.53%, yield 75.99%.
Embodiment 5
To 2000ml there-necked flasks, magnetic agitation and thermometer are built, air in nitrogen displacement bottle, nitrogen protection is lower to be put into
1300.0g anhydrous dioxanes, oil bath heating is to 130 DEG C；
Drying nitrogen is sufficiently mixed with sulfur trioxide gas through glass filler, regulation flow makes its volume ratio be 1:1, always
Flow is 7.4ml/min, and solution gradually becomes light yellow by colourless, and about 30min, which is passed through, to be finished, consumption of sulfur trioxide 199.1g,
Continue to react 5min；
Naturally stirring is cooled to room temperature, and be concentrated under reduced pressure recovery 1061.1g dioxane, obtains light yellow oil
409.4g；
409.4g light yellow oils are transferred in sublimator, keep 3mbar vacuums, oil bath is gradually heating to 72
DEG C, distillation obtains 240.7g white needles sulfuric acid vinyl esters, purity 99.64%, yield 77.98%
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
- A kind of 1. preparation method of cyclic sulfates, it is characterised in that including：A) under conditions of inert gas shielding, reacting gas and dioxane is reacted, obtain grease；The reacting gas For sulfur trioxide or sulfur dioxide；B the grease) is obtained into cyclic sulfates through distilling or distilling.
- 2. preparation method according to claim 1, it is characterised in that the inert gas be selected from nitrogen, helium, argon gas and One or more in xenon.
- 3. preparation method according to claim 1, it is characterised in that before the dioxane mixes with reacting gas, first It is heated to 90~140 DEG C.
- 4. preparation method according to claim 1, it is characterised in that the mass ratio of the reacting gas and dioxane is 1：(1~10).
- 5. preparation method according to claim 1, it is characterised in that the reaction temperature is 30~150 DEG C.
- 6. preparation method according to claim 1, it is characterised in that also include with inert gas mixing reacting gas again Reacted with dioxane；The volume ratio of the reacting gas and inert gas is 0.2~5:1.
- 7. preparation method according to claim 1, it is characterised in that the reacting gas is with certain speed and dioxy six Ring hybrid reaction, the mixing velocity are 3~8mL/min.
- 8. preparation method according to claim 1, it is characterised in that the step A) reaction after be specially：It is concentrated under reduced pressure Dioxane, obtain grease.
- 9. preparation method according to claim 1, it is characterised in that the temperature of the distillation is 50~85 DEG C.
- 10. preparation method according to claim 1, it is characterised in that the temperature of the distillation is 45~100 DEG C.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111662268A (en) * | 2020-06-12 | 2020-09-15 | 上海如鲲新材料有限公司 | Preparation method and application of cyclic sulfate compound |
| CN114920725A (en) * | 2022-05-25 | 2022-08-19 | 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 |
| CN116836147A (en) * | 2023-06-28 | 2023-10-03 | 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 |
-
2017
- 2017-07-11 CN CN201710560064.0A patent/CN107353277B/en active Active
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 |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111662268A (en) * | 2020-06-12 | 2020-09-15 | 上海如鲲新材料有限公司 | Preparation method and application of cyclic sulfate compound |
| 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 |
| CN114920725A (en) * | 2022-05-25 | 2022-08-19 | 重庆敏恒科技有限公司 | Method for preparing high-purity vinyl sulfate by sublimation, crystallization and purification |
| 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 |
| CN116836147A (en) * | 2023-06-28 | 2023-10-03 | 辽宁奥克化学股份有限公司 | Preparation method and application of cyclic sulfate |
| 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 |
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