CN114133375B - Synthetic method and application of vinyl sulfate - Google Patents
Synthetic method and application of vinyl sulfate Download PDFInfo
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- CN114133375B CN114133375B CN202111540651.6A CN202111540651A CN114133375B CN 114133375 B CN114133375 B CN 114133375B CN 202111540651 A CN202111540651 A CN 202111540651A CN 114133375 B CN114133375 B CN 114133375B
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- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000010189 synthetic method Methods 0.000 title claims description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 71
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 44
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 22
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 22
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 13
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 7
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 3
- 230000015572 biosynthetic process Effects 0.000 claims abstract 2
- 238000003786 synthesis reaction Methods 0.000 claims abstract 2
- 238000003756 stirring Methods 0.000 claims description 16
- 239000002841 Lewis acid Substances 0.000 claims description 10
- 150000007517 lewis acids Chemical class 0.000 claims description 10
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 10
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 8
- 229940102001 zinc bromide Drugs 0.000 claims description 5
- WWFKDEYBOOGHKL-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;bromide Chemical group Br.CCN1CN(C)C=C1 WWFKDEYBOOGHKL-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000001308 synthesis method Methods 0.000 claims description 4
- XXZFCJVFXKCILB-UHFFFAOYSA-N 1-methylpyrrolidine;hydrobromide Chemical compound [Br-].C[NH+]1CCCC1 XXZFCJVFXKCILB-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000004064 recycling Methods 0.000 description 7
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 6
- 239000002000 Electrolyte additive Substances 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 description 3
- -1 aluminum halides Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ONQBOTKLCMXPOF-UHFFFAOYSA-N 1-ethylpyrrolidine Chemical group CCN1CCCC1 ONQBOTKLCMXPOF-UHFFFAOYSA-N 0.000 description 1
- CCHMCSUMELBOLK-UHFFFAOYSA-N 1-methylpyrrolidin-2-one;hydrobromide Chemical compound Br.CN1CCCC1=O CCHMCSUMELBOLK-UHFFFAOYSA-N 0.000 description 1
- YSTQDJNWDMBAOZ-UHFFFAOYSA-N [Br].C(C)N1CN(C=C1)C Chemical compound [Br].C(C)N1CN(C=C1)C YSTQDJNWDMBAOZ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing vinyl sulfate, which comprises the following steps: under the combined action of a catalyst and a cocatalyst, the synthesis of the vinyl sulfate is realized by taking supercritical carbon dioxide as a solvent by a one-pot method, the raw materials of the catalyst comprise ethylene oxide, carbon dioxide and sulfur trioxide, the reaction process can be subjected to transitional state ethylene carbonate, and then the transitional state ethylene carbonate and the sulfur trioxide are subjected to transesterification so as to generate the target product ethylene sulfate.
Description
Technical Field
The invention relates to the field of lithium ion battery electrolyte additives, in particular to a method for synthesizing vinyl sulfate serving as a lithium ion battery electrolyte additive.
Background
The ethylene sulfate is a lithium ion battery electrolyte additive, can inhibit the reduction of the initial capacity of the battery, increases the initial discharge capacity, reduces the expansion of the battery after being placed at high temperature, improves the cycle times and the charge-discharge performance of the battery, prolongs the cycle life of the battery, has compatible high-low temperature performance and is an excellent lithium ion battery electrolyte additive.
The current industrial preparation of vinyl sulfate is mainly a synthesis method of ethylene glycol and thionyl chloride and a direct addition method of sulfur trioxide and ethylene oxide. The synthesis method of ethylene glycol and thionyl chloride refers to the reaction of ethylene glycol and thionyl chloride to obtain ethylene sulfite as an intermediate, wherein the ethylene sulfite is oxidized by an oxidant to generate ethylene sulfate, and the oxidant mainly comprises sodium hypochlorite, sodium periodate, potassium permanganate and potassium persulfate. When sodium hypochlorite is used as an oxidant, the oxidation reaction is often incomplete, so that the intermediate ethylene sulfite has higher residue, and the product is difficult to purify and separate; when sodium periodate is used as an oxidant, ruthenium trichloride is used as a catalyst, so that the cost is high and the recycling is difficult; when potassium persulfate is used as an oxidant, the reaction selectivity is poor, side reactions are more, the product yield is low, and more three wastes are generated. The method for preparing the vinyl sulfate by directly adding the sulfur trioxide and the ethylene oxide is characterized in that sulfuric anhydride and the ethylene oxide are simultaneously added into dioxane for reaction, and the raw materials used by the method are high in toxicity and volatility, high in pressure in the production process and high in production facilities and safety countermeasures.
Therefore, a synthetic method of vinyl sulfate with complete reaction, convenient purification and separation, low cost, low toxicity of raw materials and less generation of three wastes is urgently needed.
Disclosure of Invention
Aiming at the technical problems of preparing vinyl sulfate in the prior art, the invention provides a method for synthesizing vinyl sulfate, which has the advantages of simple process, convenient separation, high yield, low cost and less three-waste emission.
The invention aims at realizing the following technical scheme:
a method for synthesizing vinyl sulfate comprises the following steps:
1) Reacting ethylene oxide with supercritical carbon dioxide under the combined catalysis of Lewis acid and quaternary ammonium salt at 40-45 ℃, wherein the molar ratio of the Lewis acid to the ethylene oxide is 0.4-0.8:1, and the molar ratio of the quaternary ammonium salt to the ethylene oxide is 0.01-0.05:1, so as to obtain a ethylene carbonate intermediate;
2) Carrying out transesterification reaction on the ethylene carbonate and sulfur trioxide at the temperature of 40-45 ℃ to generate ethylene sulfate; the reaction route is as follows:
the Lewis acid is a catalyst, preferably, the Lewis acid is one or a combination of a plurality of transition metal halides; more preferably, the lewis acid is one or a combination of aluminum halides or zinc halides, most preferably, the lewis acid is one or a combination of aluminum trichloride or zinc bromide;
preferably, the lewis acid is used in a molar ratio to ethylene oxide of 0.8:1.
The quaternary ammonium salt is a cocatalyst, preferably an imidazole type quaternary ammonium salt; most preferably, the compound is one or two of 1-ethyl-3-methylimidazole bromine salt, N-ethyl and methylpyrrolidine bromine salt.
Preferably, stirring is accompanied during the reaction in step 1) and step 2).
Further, the stirring reaction time in the step 1) is 15-60min, preferably 30min; step 2) stirring reaction time is 1-2h.
Preferably, the molar ratio of sulfur trioxide to ethylene oxide is 1:1; the molar ratio of the carbon dioxide to the ethylene oxide is 5.3:1-10.6:1.
The beneficial effects of the invention are as follows:
1) The invention makes ethylene oxide react with carbon dioxide in a supercritical state (the pressure is more than or equal to the critical pressure of 7.38Mpa of the carbon dioxide), and uses Lewis acid catalyst and quaternary ammonium salt cocatalyst to catalyze together, so that the raw materials are cheap and easy to obtain, and expensive catalyst is avoided;
2) The excessive carbon dioxide is released in a gas form after the reaction is finished, the intermediate ethylene carbonate and sulfur trioxide completely react, only the reaction product in a solid state is remained, the separation process is extremely convenient, the purity of the product is high, the production flow is simplified, and good economic benefits are realized;
3) In addition, carbon dioxide is used as a reaction raw material and a solvent in the reaction, and can be recovered and reused, so that three wastes are hardly generated, the environment is friendly, and great social benefits are achieved.
The invention also claims the application of the vinyl sulfate prepared by the synthesis method in the field of lithium ion battery electrolyte additives.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below by means of specific embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Firstly, adding 20g of ethylene oxide, 48g of aluminum trichloride and 4.3g of 1-ethyl-3-methylimidazole bromide into a reaction kettle, then controlling the temperature of the reaction kettle to be 40 ℃, gradually introducing carbon dioxide into the reaction kettle, boosting the pressure of the reaction kettle, stopping introducing the carbon dioxide when the pressure of the reaction kettle reaches 10Mpa, stirring the reaction kettle in the state for 15min, gradually adding 36g of sulfur trioxide into the reaction kettle through a pump, ensuring the pressure and the temperature of the reaction kettle to be unchanged in the whole process, adding the sulfur trioxide for 30min, stirring the reaction kettle in the state for 1h, cooling the reaction kettle after the reaction is finished, releasing the pressure of the reaction kettle, changing the carbon dioxide into gas at the moment, recovering the catalyst by virtue of simple filtration after the recovery, and obtaining 45g of white high-purity solid vinyl sulfate from the remainder of the reaction kettle by virtue of reduced pressure distillation, wherein the content is 99.9%, the yield is 80%, and the yield is basically maintained after the third circulation.
Example 2
Adding 20g of ethylene oxide, 61g of zinc bromide and 3.07g N-ethyl, methyl pyrrolidone bromide into a reaction kettle, controlling the temperature of the reaction kettle to be 45 ℃, gradually introducing carbon dioxide into the reaction kettle, gradually pressurizing the reaction kettle to 10Mpa, stirring the reaction kettle for 20min under the state, gradually introducing 36g of sulfur trioxide into the reaction kettle through a pump, finishing the addition within 30min, stirring the reaction kettle under the state for 1h, cooling the reaction kettle after the reaction is finished, simultaneously decompressing the reaction kettle, changing the carbon dioxide into gas, escaping, dissolving the residual solid in the reaction kettle by using dichloromethane, and then carrying out simple filtration, wherein the residual can obtain 40g of white high-purity solid vinyl sulfate with the content of 99.99 percent, the yield is 75 percent, recycling the recovered catalyst, and the yield can be maintained at 75 percent after four times of recycling.
Example 3
Adding 20g of ethylene oxide, 61g of zinc bromide and 0.87g of 1-ethyl-3-methylimidazole bromide into a reaction kettle, controlling the temperature of the reaction kettle to be 45 ℃, gradually introducing carbon dioxide into the reaction kettle, gradually increasing the pressure in the reaction kettle to 10Mpa, keeping the state and stirring for 45min, gradually adding 36g of sulfur trioxide into the reaction kettle through a pump, ensuring that the pressure and the temperature of the reaction kettle are unchanged in the whole process, adding the sulfur trioxide for 30min, keeping the state and stirring for 2h, cooling the reaction kettle after the reaction is finished, decompressing the reaction kettle, allowing the carbon dioxide to escape, dissolving the residual solid in dichloromethane, and then performing simple filtration to recover the catalyst, wherein 43g of white high-purity solid vinyl sulfate can be obtained from the remainder through reduced pressure distillation, the content is 99%, the yield is 71%, the recovered catalyst is recycled, and after four times of circulation, the yield is 70% and basically kept unchanged.
Example 4
Adding 20g of ethylene oxide, 24.24g of aluminum trichloride and 4.3g of 1-ethyl-3-methylimidazole bromide into a reaction kettle, controlling the temperature of the reaction kettle to be 40 ℃, gradually introducing carbon dioxide into the reaction kettle, pressurizing the reaction kettle, stopping introducing the carbon dioxide when the pressure of the reaction kettle reaches 10Mpa, stirring the reaction kettle in the state for 30min, gradually adding 36g of sulfur trioxide into the reaction kettle through a pump, ensuring the pressure and the temperature of the reaction kettle to be unchanged in the whole process, adding the sulfur trioxide for 30min, stirring the reaction kettle in the state for 2h, cooling the reaction kettle while decompressing the reaction kettle, changing the carbon dioxide into gas, overflowing the gas, recycling the gas, introducing the recovered solid into the next circulation reaction, dissolving the residual solid in the reaction kettle by using methylene dichloride, simply filtering the dissolved solid to recover the catalyst, and carrying out reduced pressure distillation on the residue to obtain 40g of white high-purity solid ethylene sulfate, wherein the content is 99.99%, the yield is 69%, recycling the recovered catalyst, and the yield is basically maintained unchanged after three times of circulation.
Example 5
Adding 20g of ethylene oxide, 82g of zinc bromide and 4.4g N-ethyl, methyl pyrrolidine bromide into a reaction kettle, controlling the temperature of the reaction kettle to be 45 ℃, gradually introducing carbon dioxide into the reaction kettle, gradually pressurizing the reaction kettle to 10Mpa, stirring the reaction kettle for 30min under the state, gradually introducing 36g of sulfur trioxide into the reaction kettle through a pump, finishing the addition within 30min, stirring the reaction kettle under the state for 2h, cooling the reaction kettle after the reaction is finished, simultaneously decompressing the reaction kettle, changing the carbon dioxide into gas, escaping, dissolving the residual solid in the reaction kettle by using dichloromethane, and then carrying out simple filtration, wherein the residue can obtain 50.8g of white high-purity solid vinyl sulfate with the content of 99.99%, the yield is 90%, recycling the recovered catalyst, and the yield can be maintained at 90% after four times of recycling.
The above-described embodiments are merely preferred embodiments for fully explaining the present invention, and the scope of the present invention is not limited thereto. Equivalent substitutions and modifications will occur to those skilled in the art based on the present invention, and are intended to be within the scope of the present invention. The protection scope of the invention is subject to the claims.
Claims (4)
1. The synthesis method of the vinyl sulfate is characterized by comprising the following steps of:
1) Reacting ethylene oxide with supercritical carbon dioxide in a reaction kettle under the combined catalysis of Lewis acid and quaternary ammonium salt at the temperature of 40-45 ℃, wherein the molar ratio of the Lewis acid to the ethylene oxide is 0.4-0.8:1; the molar ratio of the quaternary ammonium salt to the ethylene oxide is 0.01-0.05:1, so as to obtain a ethylene carbonate intermediate;
2) Introducing sulfur trioxide into the reaction kettle in the step 1), and enabling ethylene carbonate and sulfur trioxide to undergo transesterification reaction at 40-45 ℃ to generate ethylene sulfate; the reaction route is as follows:
the Lewis acid is zinc bromide or aluminum trichloride, and the quaternary ammonium salt is 1-ethyl-3-methylimidazole bromide or N-ethyl, methylpyrrolidine bromide.
2. The synthetic method according to claim 1, wherein the reaction of step 1) and step 2) is accompanied by stirring.
3. The synthetic method according to claim 2, wherein the stirring reaction time of the step 1) is 15-60min, and the stirring reaction time of the step 2) is 1-2h.
4. A method of synthesis according to claim 3, wherein the molar ratio of sulfur trioxide to ethylene oxide is 1:1 and the molar ratio of carbon dioxide to ethylene oxide is from 5.3:1 to 10.6:1.
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| CN112159388B (en) * | 2020-09-30 | 2022-10-11 | 湖南阿斯达新材料有限公司 | Preparation method of vinyl sulfate derivative |
| CN116742124B (en) * | 2023-06-14 | 2024-02-09 | 广州天赐高新材料股份有限公司 | Novel use of nitrogen-containing compound, electrolyte additive composition and battery electrolyte |
| 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 (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105214731A (en) * | 2014-07-03 | 2016-01-06 | 中国石油化工股份有限公司 | Catalyst and the method thereof of ethylene carbonate is prepared for oxirane and carbon dioxide |
| CN106831701A (en) * | 2016-12-08 | 2017-06-13 | 盐城利庞新型材料科技有限公司 | The preparation method and its catalyst of sulfuric acid vinyl ester |
| 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 |
| CN111995615A (en) * | 2020-09-27 | 2020-11-27 | 中节能万润股份有限公司 | Preparation method of cyclic sulfate |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105214731A (en) * | 2014-07-03 | 2016-01-06 | 中国石油化工股份有限公司 | Catalyst and the method thereof of ethylene carbonate is prepared for oxirane and carbon dioxide |
| CN106831701A (en) * | 2016-12-08 | 2017-06-13 | 盐城利庞新型材料科技有限公司 | The preparation method and its catalyst of sulfuric acid vinyl ester |
| 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 |
| CN111995615A (en) * | 2020-09-27 | 2020-11-27 | 中节能万润股份有限公司 | Preparation method of cyclic sulfate |
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