CN108658928A - The synthetic method of sulfuric acid vinyl ester - Google Patents
The synthetic method of sulfuric acid vinyl ester Download PDFInfo
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- CN108658928A CN108658928A CN201710204714.8A CN201710204714A CN108658928A CN 108658928 A CN108658928 A CN 108658928A CN 201710204714 A CN201710204714 A CN 201710204714A CN 108658928 A CN108658928 A CN 108658928A
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- sulfuric acid
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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 synthetic method of sulfuric acid vinyl ester belongs to the technical field of electrochmical power source, includes the following steps：A, haptoreaction is carried out under the conditions of by sulfur dioxide and ethylene oxide existing for composite catalyst, controlling reaction temperature is 120 160 DEG C, and being passed through sulfur dioxide gas makes the pressure of reaction system be 5 12MPa, and the reaction time is 1 2.5h, ethylene sulfite is obtained, it is spare；B, it to step A obtains that sodium bicarbonate aqueous solution is added in ethylene sulfite, it is cooled to 5~5 DEG C, the mixed liquor of sodium metaperiodate and ruthenium trichloride is added dropwise thereto under the conditions of 5~5 DEG C, 1 1.5h is kept the temperature after being added dropwise, obtain the reaction solution that water phase and organic phase coexist, stratification goes out aqueous phase separation, and obtained organic phase is sulfuric acid vinyl ester crude product；C, the sulfuric acid vinyl ester crude product that step B is obtained under the conditions of 70 80 DEG C is subjected to molecular distillation, obtains sulfuric acid vinyl ester.Sulfuric acid vinyl ester purity prepared by the present invention is high, high income, is added in battery, the performance of battery is more preferable.
Description
Technical field
The invention belongs to the technical fields of electrochmical power source, and in particular to a kind of synthetic method of sulfuric acid vinyl ester.
Background technology
It is increasing for the demand of electrochmical power source with the development of the electronics and information industry in China, its performance is wanted
Ask higher and higher.Due to lithium ion battery have it is small, have a safety feature, light-weight, higher than energy, voltage is high, long lifespan,
The incomparable advantage of other electrochmical power sources such as pollution-free, at present it have become mobile phone, palm PC, laptop,
The main power source of the portable electronic devices such as microcam digital camera.In recent years, the basic research of lithium ion battery and
Application and development becomes one of hot spot.Lithium battery includes anode, cathode, electrolyte and diaphragm, and still, battery is in charge and discharge process
In, heat can be discharged, battery performance is caused to reduce.A kind of electrolysis additive is provided in the prior art, for improving high temperature
In the case of battery performance, preparation method is：The first step carries out addition reaction, and second step carries out oxidation reaction, specially exists
Carbon tetrachloride is added in the addition reaction of dihydric alcohol and thionyl chloride, is used as solvent, for providing polarity, but in addition reaction
Hydrogen chloride can be generated during progress, the presence of carbon tetrachloride can be such that hydrogen chloride is dissolved in carbon tetrachloride, to reaction into
Journey has an impact, and is bothered to the processing of later stage solvent, not easy-clear, and carbon tetrachloride is toxic product, harmful,
Not use.And battery can discharge heat in charge and discharge process, and battery performance is caused to reduce, the sulfuric acid ethylene produced
The poor performance of battery when ester encounters high-temperature condition in use, impaired serious, the battery high-temperature for being not added with additive recycles 50 weeks
Afterwards, will produce serious capacity reduces, and in order to overcome disadvantage mentioned above, we are dedicated to studying a kind of electrolysis additive, can have
The performance for improving battery under high-temperature condition of effect.
Invention content
The present invention is the defect of the poor performance of battery when solving high-temperature condition in the prior art, provides sulfuric acid vinyl ester
Synthetic method, easy to operate, sulfuric acid vinyl ester high income, the purity of synthesis are high.
The present invention be realize its purpose the technical solution adopted is that：
The synthetic method of sulfuric acid vinyl ester, includes the following steps：
A, haptoreaction, control reaction temperature are carried out under the conditions of by sulfur dioxide and ethylene oxide existing for composite catalyst
Degree is 120-160 DEG C, and being passed through sulfur dioxide gas makes the pressure of reaction system be 5-12MPa, and reaction time 1-2.5h is obtained
Ethylene sulfite, it is spare；
B, it to step A obtains that sodium bicarbonate aqueous solution is added in ethylene sulfite, is cooled to -5~5 DEG C, in -5~5 DEG C
Under the conditions of the mixed liquor of sodium metaperiodate and ruthenium trichloride is added dropwise thereto, keep the temperature 1-1.5h after being added dropwise, obtain water phase and have
The reaction solution that machine mutually coexists, stratification go out aqueous phase separation, and obtained organic phase is sulfuric acid vinyl ester crude product；
C, the sulfuric acid vinyl ester crude product that step B is obtained under the conditions of 70-80 DEG C is subjected to molecular distillation, obtains sulfuric acid second
Enester.
Composite catalyst is (2-4) by molar ratio：(1-2)：Ferric trichloride, ruthenium trichloride and the ruthenic oxide group of (1-2)
At.
The dosage of composite catalyst is 0.01-0.1 times of ethylene oxide weight.
Before carrying out haptoreaction, the air that is passed through in inert gas replacement reaction system.
Sodium bicarbonate aqueous solution is added in step B and adjusts pH value to 8-9.
The molar ratio of the mixed liquor meso-periodic acid sodium and ruthenium trichloride of sodium metaperiodate and catalyst is 1：(0.000001-
0.00006)。
The molar ratio of sodium metaperiodate and ethylene sulfite is 1：(2-6).
The time for adding of the mixed liquor of sodium metaperiodate and ruthenium trichloride is 1.5-2.5h.
The beneficial effects of the invention are as follows：
Sulfuric acid vinyl ester purity prepared by the present invention is up to 99.5% or more, moisture≤100PPM, and acid value≤
80PPM, battery also have acid value requirement very high moisture, and moisture is high, and battery performance declines, and acid value is high, and battery life is low, this hair
SEI films are formed in cathode after the bright electrolysis additive for battery, cathode is effectively protected, not only prevents capacity under high temperature
Reduction, can also effectively improve the performance of battery under high-temperature condition.
The pH value that the reaction process of step B of the present invention must be strictly controlled reaction is alkaline state 8-9, to the shadow of yield
It is also vital to ring, and super go beyond the scope of pH value can make sulfuric acid vinyl ester yield substantially reduce, this is inventor into mistake
What long-term creative research was summarized.And in the reaction process ruthenium trichloride for shortening the reaction time, ruthenium trichloride with
The ratio of sodium metaperiodate will be controlled, and will not then shorten beyond this ratio reaction time, sodium metaperiodate amount is excessive, be easy to cause
It is low to measure very little yield for product oxygenolysis.
The present invention must could improve the purity of sulfuric acid vinyl ester, and make final products by the method for molecular distillation
Moisture is low, and conventional rectification can not achieve this effect, and otherwise sulfuric acid vinyl ester can change colour, decompose, and be added in battery
Battery performance at high temperature cannot be not only improved afterwards but also there can be application risk.
Composite catalyst of the present invention can improve the purity and yield of ethylene sulfite, and catalyst is easy to get, for follow-up system
Standby high-purity, the sulfuric acid vinyl ester offer basic guarantee of high yield.The control of the composite catalyst ratio is that stable reaction carries out
Guarantee, by long-term creative research, using the catalyst of the ratio, excellent catalytic effect can reduce the progress of side reaction.
Specific implementation mode
The present invention is further explained in the light of specific embodiments.
Embodiment 1
(1), in the autoclave of the provided with electromagnetic valve of 200ml stirring, 5.0g composite catalysts are added, and (composite catalyst is by rubbing
You are than being 2：1：1 ferric trichloride, ruthenium trichloride and ruthenic oxide composition), after nitrogen displaced air, 100g epoxy second is added
Alkane, then, heat temperature raising reaction solution, but when reaction temperature is raised to 120 DEG C, sulfur dioxide gas is passed through to 8MPa, and protecting
It holds and reacts 1.5h under the temperature and pressure, cooling water is led in autoclave, be cooled to 40-50 DEG C, release product in kettle, obtain Asia
The crude product of gained is carried out vacuum decompression distillation, obtains refined ethylene sulfite by sulfuric acid vinyl ester crude product
241.03g, through chromatography, purity 99.2%, yield is 98.2% (opposite ethylene oxide).
(2), it to step (1) obtains that sodium bicarbonate aqueous solution is added in ethylene sulfite, adjusting pH value is 8-9, cooling
To -5~3 DEG C, mixed liquor (the wherein sodium metaperiodate of sodium metaperiodate and ruthenium trichloride is added dropwise thereto under the conditions of -5~3 DEG C
It is 149.7g to measure, and the molar ratio of sodium metaperiodate and ruthenium trichloride is 1:0.000007), a length of 2h when dropwise addition, is protected after being added dropwise
Warm 1.5h obtains the reaction solution that water phase and organic phase coexist, and stratification goes out aqueous phase separation, and obtained organic phase is
Sulfuric acid vinyl ester crude product；
(3), the sulfuric acid vinyl ester crude product that step (2) obtains under the conditions of 70-80 DEG C is subjected to molecular distillation, obtains sulphur
Vinyl acetate 266.84g, through chromatography, purity 98.9%, yield is 96.5% (opposite ethylene sulfite).
Embodiment 2
(1), in the autoclave of the provided with electromagnetic valve of 200ml stirring, 8.0g composite catalysts are added, and (composite catalyst is by rubbing
You are than being 3：2：1 ferric trichloride, ruthenium trichloride and ruthenic oxide composition), after nitrogen displaced air, 100g epoxy second is added
Alkane, then, heat temperature raising reaction solution, but when reaction temperature is raised to 140 DEG C, sulfur dioxide gas is passed through to 6MPa, and protecting
It holds and reacts 2h under the temperature and pressure, cooling water is led in autoclave, be cooled to 40-50 DEG C, release product in kettle, obtain sulfurous
The crude product of gained is carried out vacuum decompression distillation, obtains refined ethylene sulfite 242.5g, passed through by vinyl acetate crude product
Chromatography, purity 99.4%, yield are 98.8% (opposite ethylene oxide).
(2), it to step (1) obtains that sodium bicarbonate aqueous solution is added in ethylene sulfite, adjusting pH value is 8-9, cooling
To -3~5 DEG C, mixed liquor (the wherein sodium metaperiodate of sodium metaperiodate and ruthenium trichloride is added dropwise thereto under the conditions of -3~5 DEG C
It is 106.9g to measure, and the molar ratio of sodium metaperiodate and ruthenium trichloride is 1:0.000005), a length of 2.5h when dropwise addition, after being added dropwise
1h is kept the temperature, obtains the reaction solution that water phase and organic phase coexist, stratification goes out aqueous phase separation, and obtained organic phase is
Sulfuric acid vinyl ester crude product；
(3), the sulfuric acid vinyl ester crude product that step (2) obtains under the conditions of 70-80 DEG C is subjected to molecular distillation, obtains sulphur
Vinyl acetate 242.54g, through chromatography, purity 99.1%, yield is 97.8% (opposite sodium metaperiodate).
Embodiment 3
(1), in the autoclave of the provided with electromagnetic valve of 200ml stirring, be added 10.0g composite catalysts (composite catalyst by
Molar ratio is 4：1：2 ferric trichloride, ruthenium trichloride and ruthenic oxide composition), after nitrogen displaced air, 100g epoxies are added
Ethane, then, heat temperature raising reaction solution, but when reaction temperature is raised to 160 DEG C, sulfur dioxide gas is passed through to 10MPa, and
It keeps reacting 2.5h under the temperature and pressure, cooling water is led in autoclave, be cooled to 40-50 DEG C, release product in kettle, obtain
The crude product of gained is carried out vacuum decompression distillation, obtains refined ethylene sulfite by ethylene sulfite crude product
241.77g, through chromatography, purity 99.5%, yield is 98.5% (opposite ethylene oxide).
(2), it to step (1) obtains that sodium bicarbonate aqueous solution is added in ethylene sulfite, adjusting pH value is 8-9, cooling
To -4~1 DEG C, mixed liquor (the wherein sodium metaperiodate of sodium metaperiodate and ruthenium trichloride is added dropwise thereto under the conditions of -1~1 DEG C
It is 218.2g to measure, and the molar ratio of sodium metaperiodate and ruthenium trichloride is 1:0.00001), a length of 1.5h when dropwise addition, is protected after being added dropwise
Warm 1.3h obtains the reaction solution that water phase and organic phase coexist, and stratification goes out aqueous phase separation, and obtained organic phase is
Sulfuric acid vinyl ester crude product；
(3), the sulfuric acid vinyl ester crude product that step (2) obtains under the conditions of 70-80 DEG C is subjected to molecular distillation, obtains sulphur
Vinyl acetate 266.2g, through chromatography, purity 98.7%, yield is 95.9% (opposite ethylene sulfite).
The sulfuric acid vinyl ester for detecting above-mentioned gained is light yellow crystal, density 1.601-1.605g/cm3, fusing point 95-
97 DEG C, it is 231-231.5 DEG C that boiling point is detected at 760mmHg.
Additive of the sulfuric acid vinyl ester as lithium-ion battery electrolytes, effect, which also resides in, inhibits battery initial capacity
Decline, increases initial discharge capacity and reduce the cell expansion after high temperature is placed, improve the charge-discharge performance and cycle-index of battery.
The purity of sulfuric acid vinyl ester is higher, and after being added to battery, the cycle performance of battery is better, and heat-resisting quantity is more preferable.The addition present invention
The battery of sulfuric acid vinyl ester recycles 300 times, capacity retention ratio 95% at 45 DEG C, recycles 400 times, capacity retention ratio 88%,
Cycle 500 times, capacity retention ratio 80%.After the battery is placed 7 days at 60 DEG C, measurement capacity conservation rate is 90%, capacity
Recovery rate is 92%.
Claims (8)
1. the synthetic method of sulfuric acid vinyl ester, which is characterized in that include the following steps：
A, haptoreaction is carried out under the conditions of by sulfur dioxide and ethylene oxide existing for composite catalyst, controlling reaction temperature is
120-160 DEG C, being passed through sulfur dioxide gas makes the pressure of reaction system be 5-12MPa, and reaction time 1-2.5h obtains sulfurous
Vinyl acetate, it is spare；
B, it to step A obtains that sodium bicarbonate aqueous solution is added in ethylene sulfite, is cooled to -5~5 DEG C, in -5~5 DEG C of conditions
Under the mixed liquor of sodium metaperiodate and ruthenium trichloride is added dropwise thereto, keep the temperature 1-1.5h after being added dropwise, obtain water phase and organic phase
The reaction solution coexisted, stratification go out aqueous phase separation, and obtained organic phase is sulfuric acid vinyl ester crude product；
C, the sulfuric acid vinyl ester crude product that step B is obtained under the conditions of 70-80 DEG C is subjected to molecular distillation, obtains sulfuric acid ethylene
Ester.
2. the synthetic method of sulfuric acid vinyl ester according to claim 1, which is characterized in that composite catalyst is by molar ratio
(2-4)：(1-2)：Ferric trichloride, ruthenium trichloride and the ruthenic oxide composition of (1-2).
3. the synthetic method of sulfuric acid vinyl ester according to claim 1, which is characterized in that the dosage of composite catalyst is ring
0.01-0.1 times of oxidative ethane weight.
4. the synthetic method of sulfuric acid vinyl ester according to claim 1, which is characterized in that before carrying out haptoreaction,
The air being passed through in inert gas replacement reaction system.
5. the synthetic method of sulfuric acid vinyl ester according to claim 1, which is characterized in that sodium bicarbonate is added in step B
Aqueous solution adjusts pH value to 8-9.
6. the synthetic method of sulfuric acid vinyl ester according to claim 1, which is characterized in that sodium metaperiodate and catalyst it is mixed
The molar ratio for closing liquid meso-periodic acid sodium and ruthenium trichloride is 1：(0.000001-0.00006).
7. the synthetic method of sulfuric acid vinyl ester according to claim 1, which is characterized in that sodium metaperiodate and sulfurous acid ethylene
The molar ratio of ester is 1：(2-6).
8. the synthetic method of sulfuric acid vinyl ester according to claim 1, which is characterized in that sodium metaperiodate and ruthenium trichloride
The time for adding of mixed liquor is 1.5-2.5h.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112159388A (en) * | 2020-09-30 | 2021-01-01 | 湖南阿斯达新材料有限公司 | Preparation method of vinyl sulfate derivative |
| CN112375064A (en) * | 2020-11-10 | 2021-02-19 | 湖北吉和昌化工科技有限公司 | Vinyl sulfate synthesis process |
| JP2021195362A (en) * | 2020-06-12 | 2021-12-27 | 上海如鯤新材料有限公司 | Preparation method of cyclic sulfuric ester-based compound, and use thereof |
| CN115504959A (en) * | 2022-10-22 | 2022-12-23 | 山东师范大学 | Safe and clean synthesis method of vinyl sulfate |
| CN115745952A (en) * | 2022-11-29 | 2023-03-07 | 香河昆仑新能源材料股份有限公司 | Preparation method of ethylene sulfite |
| CN115745952B (en) * | 2022-11-29 | 2024-05-31 | 香河昆仑新能源材料股份有限公司 | Preparation method of ethylene sulfite |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021195362A (en) * | 2020-06-12 | 2021-12-27 | 上海如鯤新材料有限公司 | Preparation method of cyclic sulfuric ester-based compound, and use thereof |
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| CN112375064B (en) * | 2020-11-10 | 2022-07-05 | 湖北吉和昌化工科技有限公司 | Vinyl sulfate synthesis process |
| CN115504959A (en) * | 2022-10-22 | 2022-12-23 | 山东师范大学 | Safe and clean synthesis method of vinyl sulfate |
| CN115504959B (en) * | 2022-10-22 | 2023-06-27 | 山东师范大学 | Synthesis method of vinyl sulfate |
| CN115745952A (en) * | 2022-11-29 | 2023-03-07 | 香河昆仑新能源材料股份有限公司 | Preparation method of ethylene sulfite |
| CN115745952B (en) * | 2022-11-29 | 2024-05-31 | 香河昆仑新能源材料股份有限公司 | Preparation method of ethylene sulfite |
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Application publication date: 20181016 |