CN114685424A - Preparation method of vinyl dithionate - Google Patents
Preparation method of vinyl dithionate Download PDFInfo
- Publication number
- CN114685424A CN114685424A CN202011554811.8A CN202011554811A CN114685424A CN 114685424 A CN114685424 A CN 114685424A CN 202011554811 A CN202011554811 A CN 202011554811A CN 114685424 A CN114685424 A CN 114685424A
- Authority
- CN
- China
- Prior art keywords
- dithionate
- vinyl
- ozone
- divinyl
- solvent
- 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.)
- Granted
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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of vinyl dithionate, which comprises the following steps: A1. a closed loop step: reacting erythritol with thionyl chloride to obtain ethylene bisulphite; A2. an oxidation step: the method comprises the step of oxidizing the ethylene bisulphite to obtain ethylene bisulphate under the oxidation action of ozone-containing gas, wherein the ozone content in the ozone-containing gas is 0.1-50%. The invention has the advantages of high reaction yield and high product purity.
Description
Technical Field
The invention relates to synthesis of an electrolyte additive of a lithium ion battery, in particular to a preparation method of vinyl dithionate with high purity and low moisture content.
Background
The lithium ion battery has the advantages of small volume, good safety performance, light weight, high specific performance, high voltage, long service life, no pollution and the like, so that the lithium ion battery is widely applied. In recent years, with the rapid development of new energy automobile market in China, the demand of power lithium batteries is greatly increased, and with the continuous improvement of the energy performance requirements of the market on the lithium batteries, the research and development of lithium ion battery electrolytes and functional additives are concerned.
The cyclic vinyl sulfate compound is used as the electrolyte additive of the lithium ion battery, can inhibit the reduction of the initial capacity of the battery, increase the initial discharge capacity, reduce the expansion of the battery after high-temperature placement, and improve the charge and discharge performance and cycle number of the battery. The divinyl bisulphate is one of cyclic vinyl sulphates, and has wide market demand and development prospect. The preparation method of the vinyl bichromate reported at present comprises the following two methods:
acylation method
The acylation process produces cyclic sulfates primarily by the reaction of sulfuryl fluoride with vicinal diols.
Patent CN107629032A discloses a method for preparing vinyl dithionate from sulfuryl fluoride and erythritol as raw materials under the action of an acid-binding agent and a catalyst. Although the method has cheap raw materials, the method has low reaction yield, strong corrosiveness and great environmental pollution, and is not suitable for industrial production.
Two, oxidation process
The oxidation method uses erythritol and thionyl chloride as raw materials to generate an intermediate vinyl dithionite firstly, and then generates vinyl dithionite through oxidation.
Patent CN106905291A discloses a method for obtaining vinyl dithionate by oxidizing sodium hypochlorite as an oxidant under the catalysis of ruthenium trichloride aqueous solution. However, in the method, the sodium hypochlorite has strong oxidizability and is extremely unstable, the process cost is high, the control is not easy, and the generated wastewater amount is large; meanwhile, the product has more chlorinated impurities, more water and low purity, and the application of the product as an electrolyte additive is influenced.
KR102080198A discloses a method for preparing vinyl dithionate under the catalysis of ruthenium trichloride aqueous solution by using calcium perchlorate as an oxidant. However, the calcium perchlorate in the method is extremely expensive and too high in cost, and can only be used for preparation of reagents in a laboratory, so that industrialization cannot be realized; on the other hand, the product has more chlorinated impurities and high water acidity, and the requirement of the product as an electrolyte additive cannot be met.
Patent CN110386916A discloses a method for obtaining vinyl dithionate by oxidizing peroxysulfuric acid prepared from hydrogen peroxide and concentrated sulfuric acid, in the method, the peroxysulfuric acid is an explosive chemical, the safety risk is high, and the overproof sulfate ions in the product also affect the later application.
In conclusion, the existing preparation process of the vinyl dithionate generally has the problems of low product purity and overproof moisture and acidity, so that the development of the preparation process of the vinyl dithionate, which is simple in process, low in moisture content and acidity, high in product purity and high in yield, has important significance.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of the divinyl ester bi-sulfate, which has high product purity, low moisture content and low acidity and is suitable for industrial production.
The purpose of the invention is realized by the following technical scheme:
a method of preparing vinyl dithioate, the method comprising:
A1. a closed loop step: reacting erythritol with thionyl chloride to obtain ethylene bisulphite;
A2. an oxidation step: the vinyl dithionite is oxidized by ozone-containing gas to obtain vinyl dithionite.
The molar ratio of the thionyl chloride to the erythritol is (2-4): 1, preferably, the molar ratio is (2.1-2.2): 1.
ozone is used as an oxidizing gas, and has the advantages of rapid reaction, simple flow, no secondary pollution and the like, so that the preparation process of the divinyl bisulphate has convenient post-treatment, less three wastes and environmental protection.
The ozone-containing gas of the present invention may be a pure ozone gas or a mixture of ozone and other gases, which may be air, oxygen or inert gases. Preferably, the ozone-containing gas is an ozone-containing mixed gas, and the ozone content is 0.1 to 50%, and within this range, the oxidizing property is controllable and the ozone-containing gas can be easily produced. More preferably, the ozone-containing gas has an ozone content of 1 to 10%.
In a specific embodiment, the ozone-containing gas is prepared by an ozone generator, and the ozone content is 3-5%.
According to the above preparation method of vinyl dithionate, preferably, the reactant obtained by reacting erythritol and thionyl chloride is washed to neutrality with deionized water.
According to the preparation method of the vinyl dithionate, the thionyl chloride is added into the erythritol in a dropwise adding mode, the reaction temperature is controlled to be 0-80 ℃ in the dropwise adding process, and after dropwise adding is finished, the temperature is kept at 20-80 ℃ for reaction for 1-8 hours. Preferably, the reaction temperature is controlled to be 15-20 ℃ in the dripping process, and the reaction is carried out for 3-4 hours at the temperature of 40-50 ℃.
After the reaction is finished, a large amount of pasty solid divinyl dithionite is separated out from the reaction liquid, deionized water is added to quickly break up the reaction system, and the filtered and separated divinyl dithionite is added to the deionized water to be washed to be neutral.
In order to avoid the influence of the moisture in the divinyl bisulphite on the purity of the product, the divinyl bisulphite solid washed to be neutral is preferably dried under reduced pressure.
According to the above preparation method of vinyl dithionate, preferably, the step a2 further includes:
dissolving the divinyl bisulphite in a first solvent, introducing ozone-containing gas under a stirring state until the reaction is finished, and removing the first solvent by reduced pressure distillation to obtain a crude product of the divinyl bisulphite;
and recrystallizing and purifying the crude product of the divinyl bisulphate by adopting a second solvent to obtain a divinyl bisulphate product with the purity of more than 99.5 percent, wherein the acidity of the divinyl bisulphate product is less than or equal to 50ppm, and the moisture content of the divinyl bisulphate product is less than or equal to 50 ppm. More preferably, the acidity of the vinyl bisulphate product is less than or equal to 40ppm and the moisture content is less than or equal to 30 ppm.
The mass ratio of the first solvent to the ethylene bisulphite is (4-30): 1, preferably selecting the mass ratio of (7-10): 1.
the reaction temperature in the oxidation step is-20 to 60 ℃, and the preferable reaction temperature is 0 to 5 ℃.
Further, the first solvent is at least one selected from the group consisting of toluene, xylene, ethyl acetate, isopropyl acetate, dimethyl carbonate, diethyl carbonate, dichloromethane, 1, 2-dichloroethane, n-hexane, t-butyl methyl ether, dioxane, and acetonitrile. Preferably, the first solvent is selected from acetonitrile and dichloromethane.
The second solvent is at least one selected from toluene, xylene, ethyl acetate, butyl acetate, isopropyl acetate, dimethyl carbonate, diethyl carbonate, dichloromethane, 1, 2-dichloroethane, n-hexane, tert-butyl methyl ether, dioxane, acetonitrile, methanol and ethanol. Preferably, the second solvent is selected from acetonitrile.
Compared with the prior art, the invention has the beneficial effects that:
1. the method adopts ozone-containing gas for oxidation to obtain the vinyl dithionate, can obtain products with high yield without a catalyst, has simple process and convenient post-treatment, is an anhydrous system for reaction, is green and environment-friendly, and is suitable for industrial production;
2. the product purity obtained by the preparation process is more than 99.5 percent, the water content is controlled below 50ppm, and the acidity is controlled below 50 ppm.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention to these embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
Example 1
The embodiment provides a preparation method of vinyl dithionate, which specifically comprises the following steps:
s1, a closed loop step: adding 244.2g (2mol) of solid erythritol into a 2L three-necked bottle, starting stirring, dropwise adding 523.1g (4.4mol) of thionyl chloride into the three-necked bottle, controlling the temperature to be between 15 and 20 ℃ in the dropwise adding process, keeping the temperature at 45 ℃ after the dropwise adding is finished, reacting for 4 hours, precipitating a large amount of pasty solid from a reaction liquid, slowly dropwise adding 800g of deionized water after cooling, quickly stirring and scattering a reaction system, pulping and washing the filtered solid for multiple times by using the deionized water until the pH is neutral, and drying a filter cake at 60 ℃ under reduced pressure to obtain 397.8g of white solid with the purity of 97.9 percent and the crude yield of 93 percent;
A2. an oxidation step: adding 171.2g (0.8mol) of ethylene dithionite into a 2L three-neck flask, adding 1284g of acetonitrile, stirring until the solid is completely dissolved, cooling a reaction system to 0-5 ℃, introducing ozone-containing gas (the ozone content is 3 percent, the rest is oxygen, the gas flow rate is 0.10L/min) prepared by an ozone generator into the three-neck flask under the condition of slow stirring, stopping introducing the gas after GC tracking detection reaction, distilling under reduced pressure to remove the acetonitrile, filtering and drying to obtain 187g of white solid with the purity of 97 percent. Recrystallizing the crude product of the vinyl dithionate with acetonitrile to obtain 169.2g of pure vinyl dithionate, wherein the yield is 86%, the purity is 99.5%, the water content is tested to be 20ppm, and the acidity is tested to be 46 ppm.
Example 2
The operation of this example is the same as example 1 except that:
in the ring closure step, the amount of thionyl chloride was reduced to 499.4g (4.2mol) to give 389g of a white solid with 98.1% purity and 90.8% crude yield.
In the oxidation step, the reaction temperature is controlled to be 5-10 ℃, 166g of pure vinyl dithionate is obtained, the yield is 84.3%, the purity is 99.3%, the moisture content is tested to be 22ppm, and the acidity is tested to be 50 ppm.
Example 3
The operation of this example is the same as example 1 except that:
in the ring closure step, the amount of erythritol was reduced to 122.1g (1mol), the amount of thionyl chloride was reduced to 285.4g (2.4mol), a 1L three-necked flask was used as a reaction vessel, and the amount of deionized water was reduced to 400 g. 192g of a white solid was obtained with a purity of 98.3% and a crude yield of 89.7%.
In the oxidation step, the reaction temperature was controlled at-5 ℃, acetonitrile was removed by distillation under reduced pressure, and dried to obtain 184.3g of a white solid with a purity of 96.5%. After recrystallization with acetonitrile, 165.2g of pure vinyl dithionate is obtained, the yield is 83.9%, the purity is 99.5%, the moisture content is 25ppm, and the acidity is 40 ppm.
Example 4
The operation of this example is the same as example 1 except that:
in the ring-closing step, the temperature is controlled to be 35-40 ℃ in the dripping process, and 383.5g of white solid is obtained, the purity is 98.1%, and the crude yield is 89.6%.
In the oxidation step, the amount of vinyl dithionite was reduced to 85.6g (0.4mol), dissolved in 1712g of dichloromethane, distilled under reduced pressure to remove acetonitrile and dried to give 94.2g of a white solid with a purity of 96%. Recrystallization is carried out by acetonitrile to obtain 81.7g of pure product of the vinyl dithionate, the yield is 83 percent, the purity is 99.5 percent, the water content is tested to be 30ppm, and the acidity is tested to be 42 ppm.
Example 5
The operation of this example is the same as example 1 except that:
in the oxidation step, the flow rate of the gas containing ozone gas is reduced to 0.05L/min, and 188g of crude pure product of vinyl dithionate with the purity of 96.3 percent is finally obtained. Recrystallizing with acetonitrile to obtain 168.7g pure product of vinyl dithionate, with yield of 85.7%, purity of 99.5%, moisture content of 22ppm, and acidity of 40 ppm.
Example 6
The operation of this example is the same as example 1 except that:
in the oxidation step, the ozone content in the ozone-containing gas is increased to 6 percent, and 178g of crude and pure product of the vinyl dithionate with the purity of 94.3 percent is finally obtained. Recrystallizing with acetonitrile to obtain pure product of vinyl dithionate 150.5g, yield 76.4%, purity 99.5%, moisture content 25ppm, and acidity 58 ppm.
Comparative example 1
The procedure of the present comparative example was the same as example 1, the oxidation step was as follows:
adding 85.6g (0.4mol) of ethylene dithionite into a 3L three-neck flask, adding 1712g of solvent dichloromethane, stirring until the solid is completely dissolved, adding 13g of catalyst 10% ruthenium trichloride aqueous solution, cooling a reaction system to-5-0 ℃, then dropwise adding 1030 g of 12% sodium hypochlorite solution into the three-neck flask under rapid stirring, changing the reaction solution from brown to milky, separating out the solid, filtering, washing a large amount of filter cakes with water, layering the filtrate, concentrating an organic layer to separate out the solid, combining the crude products, and drying 68.2 g; the purity of the crude product is 96.3%. And (3) purification: the ethylene bisulphate is recrystallized by dimethyl carbonate to obtain 60g of high-purity product ethylene bisulphate, the yield is 61%, the purity is 98.9%, the moisture content is 200ppm, and the acidity is 168 ppm.
Comparative example 2
The procedure of the present comparative example was the same as example 1, the oxidation step was as follows:
preparing peroxysulfuric acid: cooling 146 g of 70% hydrogen peroxide to 0 ℃, slowly dripping 690 g of 85% concentrated sulfuric acid, controlling the temperature to be 0-5 ℃, stirring after dripping, keeping the temperature and reacting for 6 hours to obtain a peroxysulfuric acid solution for later use.
An oxidation step: adding 85.6g (0.4mol) of ethylene dithionite into a 3L three-necked bottle, adding 800g of dimethyl carbonate as a solvent, stirring until the solid is completely dissolved, adding 13g of a 10% ruthenium trichloride aqueous solution as a catalyst, cooling a reaction system to 0-5 ℃ by using 580g of disodium hydrogen phosphate as a pH buffering agent, then dropwise adding 370g of a prepared peroxysulfuric acid solution into the three-necked bottle under rapid stirring, changing the reaction solution from brown to milky white, separating out solids, filtering, washing a filter cake with a large amount of water, layering the filtrate, concentrating an organic layer to separate out the solids, combining the crude products, and drying 79.5 g; the purity of the crude product is 97.8%. And (3) purification: the ethylene bisulphate is recrystallized by dimethyl carbonate to obtain 69g of high-purity product ethylene bisulphate, the yield is 70%, the purity is 99.1%, the moisture content is tested to be 150ppm, and the acidity is tested to be 140 ppm.
Claims (10)
1. A method for preparing vinyl dithionate is characterized in that: the preparation method comprises the following steps:
A1. a closed loop step: reacting erythritol with thionyl chloride to obtain ethylene bisulphite;
A2. an oxidation step: the divinyl bissulfite obtains the divinyl bissulfite under the oxidation action of the ozone-containing gas.
2. The method for producing vinyl dithionate according to claim 1, characterized in that: the ozone-containing gas contains 0.1 to 50% of ozone.
3. The method of producing vinyl dithionate according to claim 1, wherein: the step A1 further comprises: and washing a reactant obtained by reacting erythritol and thionyl chloride to be neutral by using deionized water.
4. The method of producing vinyl dithionate according to claim 3, wherein: the step A2 further comprises:
dissolving the divinyl dithionite in a first solvent, and introducing ozone-containing gas under a stirring state until the reaction is finished to obtain a crude product of the divinyl dithionite;
and recrystallizing and purifying the crude product of the divinyl ester bi-sulfate by using a second solvent to obtain a divinyl ester bi-sulfate product with the purity of more than 99.5 percent.
5. The method for producing vinyl dithionate according to claim 4, characterized in that: the first solvent is at least one selected from toluene, xylene, ethyl acetate, isopropyl acetate, dimethyl carbonate, diethyl carbonate, dichloromethane, 1, 2-dichloroethane, n-hexane, tert-butyl methyl ether, dioxane and acetonitrile.
6. The method of preparing vinyl dithionate according to claim 4, wherein: the second solvent is at least one selected from toluene, xylene, ethyl acetate, butyl acetate, isopropyl acetate, dimethyl carbonate, diethyl carbonate, dichloromethane, 1, 2-dichloroethane, n-hexane, tert-butyl methyl ether, dioxane, acetonitrile, methanol and ethanol.
7. The method for producing vinyl dithionate according to any of claims 1-6, wherein: the molar ratio of the thionyl chloride to the erythritol is (2-4): 1.
8. the method for producing vinyl dithionate according to any of claims 1-7, wherein: and adding the thionyl chloride into the erythritol in a dropwise adding mode, controlling the reaction temperature to be 0-80 ℃ in the dropwise adding process, and after dropwise adding is finished, keeping the temperature of 20-80 ℃ for reaction for 1-8 hours.
9. The method for producing vinyl dithionate according to any of claims 1-6, wherein: the mass ratio of the first solvent to the ethylene bisulphite is (4-30): 1.
10. the method of producing vinyl dithionate according to claim 9, wherein: the reaction temperature in the oxidation step is-20-60 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011554811.8A CN114685424B (en) | 2020-12-25 | 2020-12-25 | Preparation method of vinyl dithionate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011554811.8A CN114685424B (en) | 2020-12-25 | 2020-12-25 | Preparation method of vinyl dithionate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114685424A true CN114685424A (en) | 2022-07-01 |
| CN114685424B CN114685424B (en) | 2023-09-05 |
Family
ID=82130345
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011554811.8A Active CN114685424B (en) | 2020-12-25 | 2020-12-25 | Preparation method of vinyl dithionate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114685424B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115215834A (en) * | 2022-08-29 | 2022-10-21 | 长沙创新药物工业技术研究院有限公司 | Preparation method of vinyl sulfate |
| CN115322170A (en) * | 2022-08-29 | 2022-11-11 | 苏州华一新能源科技股份有限公司 | Preparation method of vinyl sulfate |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103098290A (en) * | 2010-10-22 | 2013-05-08 | 三井化学株式会社 | Cyclic sulfate compound, non-aqueous electrolyte solution containing same, and lithium secondary battery |
| CN106905291A (en) * | 2015-12-22 | 2017-06-30 | 天津鑫源广泰新材料科技有限公司 | A kind of 3, the production method of 3-di- sulfuric acid vinyl ester |
| CN108822073A (en) * | 2018-06-19 | 2018-11-16 | 辽宁科隆精细化工股份有限公司 | A kind of preparation method and applications of sulfuric acid vinyl ester |
| CN110117297A (en) * | 2019-04-10 | 2019-08-13 | 珠海市赛纬电子材料股份有限公司 | A kind of preparation method of 2- phosphate base sulfuric acid acrylic ester |
| CN110386916A (en) * | 2019-07-23 | 2019-10-29 | 常熟市常吉化工有限公司 | A kind of synthetic method of cyclic sulfates |
| CN111909129A (en) * | 2020-09-03 | 2020-11-10 | 常熟市常吉化工有限公司 | Method for preparing cyclic sulfate by direct oxidation of hydrogen peroxide |
-
2020
- 2020-12-25 CN CN202011554811.8A patent/CN114685424B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103098290A (en) * | 2010-10-22 | 2013-05-08 | 三井化学株式会社 | Cyclic sulfate compound, non-aqueous electrolyte solution containing same, and lithium secondary battery |
| CN106905291A (en) * | 2015-12-22 | 2017-06-30 | 天津鑫源广泰新材料科技有限公司 | A kind of 3, the production method of 3-di- sulfuric acid vinyl ester |
| CN108822073A (en) * | 2018-06-19 | 2018-11-16 | 辽宁科隆精细化工股份有限公司 | A kind of preparation method and applications of sulfuric acid vinyl ester |
| CN110117297A (en) * | 2019-04-10 | 2019-08-13 | 珠海市赛纬电子材料股份有限公司 | A kind of preparation method of 2- phosphate base sulfuric acid acrylic ester |
| CN110386916A (en) * | 2019-07-23 | 2019-10-29 | 常熟市常吉化工有限公司 | A kind of synthetic method of cyclic sulfates |
| CN111909129A (en) * | 2020-09-03 | 2020-11-10 | 常熟市常吉化工有限公司 | Method for preparing cyclic sulfate by direct oxidation of hydrogen peroxide |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115215834A (en) * | 2022-08-29 | 2022-10-21 | 长沙创新药物工业技术研究院有限公司 | Preparation method of vinyl sulfate |
| CN115322170A (en) * | 2022-08-29 | 2022-11-11 | 苏州华一新能源科技股份有限公司 | Preparation method of vinyl sulfate |
| CN115215834B (en) * | 2022-08-29 | 2023-12-12 | 长沙创新药物工业技术研究院有限公司 | Preparation method of vinyl sulfate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114685424B (en) | 2023-09-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109776487B (en) | Preparation method of vinyl sulfate | |
| CN109988145B (en) | Preparation method of vinyl sulfate | |
| CN114685424A (en) | Preparation method of vinyl dithionate | |
| CN111755753B (en) | Cyclic carbonic acid vinyl sulfate ester as lithium ion battery electrolyte additive and preparation method thereof | |
| CN111909129A (en) | Method for preparing cyclic sulfate by direct oxidation of hydrogen peroxide | |
| RU2591703C2 (en) | Method for preparation of 3,3-dimethylbutyraldehyde | |
| CN111825652A (en) | Method for preparing vinyl sulfate | |
| CN113800485B (en) | Preparation method of lithium bis (fluorosulfonyl) imide | |
| CN111116429B (en) | Method for synthesizing alkali metal trifluoromethanesulfonate or alkali metal methanesulfonate | |
| CN111978341B (en) | Preparation method of lithium difluoroborate | |
| CN115141175B (en) | Method for preparing cyclic sulfate | |
| CN114195757A (en) | Method for synthesizing vinyl sulfate | |
| CN101717348B (en) | Synthesis method of diisopropyl azodiformate | |
| CN109369609A (en) | A kind of preparation method of sulfuric acid vinyl ester | |
| CN113444066A (en) | Preparation method of vinyl sulfate | |
| CN113979454A (en) | Preparation method of fluorosulfonic acid alkali metal salt | |
| CN108586296B (en) | Continuous synthesis method of p-nitrotoluene-o-sulfonic acid | |
| CN114805395B (en) | Preparation method of oxacephem parent nucleus intermediate | |
| CN114275757B (en) | Preparation method of lithium difluorophosphate | |
| CN116217539A (en) | Method for preparing vinyl sulfate by catalyzing hydrogen peroxide oxidation | |
| CN110256318B (en) | Clean production method of tetrabenzylthiuram disulfide | |
| KR20230010091A (en) | Method for producing high purity lithium bis(fluorosulfonyl)imide | |
| CN115368377B (en) | Preparation method of cyclic sulfate | |
| CN114805290A (en) | Preparation method of vinyl sulfate | |
| CN115124051A (en) | Preparation method and application of fluorosulfonate |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |