CN116836147A - Preparation method and application of cyclic sulfate - Google Patents
Preparation method and application of cyclic sulfate Download PDFInfo
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- CN116836147A CN116836147A CN202310777253.9A CN202310777253A CN116836147A CN 116836147 A CN116836147 A CN 116836147A CN 202310777253 A CN202310777253 A CN 202310777253A CN 116836147 A CN116836147 A CN 116836147A
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- carbonate
- sulfur trioxide
- cyclic sulfate
- epoxy compound
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- 125000004122 cyclic group Chemical group 0.000 title claims abstract description 43
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims abstract description 78
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 239000000725 suspension Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000004593 Epoxy Substances 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 18
- 150000002148 esters Chemical class 0.000 claims abstract description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000012452 mother liquor Substances 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 20
- 125000002947 alkylene group Chemical group 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 11
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 8
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 52
- -1 hydroxyethyl functional groups Chemical group 0.000 description 21
- 238000004817 gas chromatography Methods 0.000 description 11
- 239000011521 glass Substances 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 8
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 description 7
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- MGAFPXGQLWFEPK-UHFFFAOYSA-N 1,3,2-dioxathiepane 2,2-dioxide Chemical compound O=S1(=O)OCCCCO1 MGAFPXGQLWFEPK-UHFFFAOYSA-N 0.000 description 1
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 description 1
- OQXNUCOGMMHHNA-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2,2-dioxide Chemical compound CC1COS(=O)(=O)O1 OQXNUCOGMMHHNA-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ZHOJVVFLZNWEFB-UHFFFAOYSA-N dimethyl carbonate;oxolane Chemical compound C1CCOC1.COC(=O)OC ZHOJVVFLZNWEFB-UHFFFAOYSA-N 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002351 wastewater 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
- H01M10/056—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
-
- 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)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Epoxy Compounds (AREA)
Abstract
The application discloses a preparation method and application of cyclic sulfate, wherein the method comprises the following steps: (1) Sulfur trioxide is dispersed in carbonic ester to form suspension solution A; (2) an epoxy compound is dissolved in a carbonate to form a solution B; (3) the solution A and the solution B are contacted and reacted to generate the cyclic sulfate. The preparation method disclosed by the application is mild in reaction condition, free of catalyst addition, environment-friendly, high in target product conversion rate and high in product purity, and is suitable for large-scale industrial production.
Description
Technical Field
The application relates to the technical field of organic synthesis, in particular to a method for synthesizing cyclic sulfate through the reaction of an epoxy compound and sulfur trioxide and application thereof.
Background
Cyclic sulfate is an important organic chemical raw material and functional chemicals, such as vinyl sulfate (DTD) can be used for synthesizing organic products containing hydroxyethyl functional groups, and simultaneously, the vinyl sulfate can be used as an electrolyte additive of a lithium ion battery to remarkably improve various performances of the battery. With the vigorous development of new energy industry and lithium ion battery industry, the performance requirement on lithium ion batteries is higher and higher, so that the requirement on high-quality vinyl sulfate is correspondingly increased.
Currently, the process for preparing cyclic sulfate is to react an o-diol with thionyl chloride to form an intermediate cyclic sulfite, which is then oxidized to form the cyclic sulfate. For example, ethylene glycol reacts with thionyl chloride to generate ethylene sulfite, and then sodium hypochlorite is used as an oxidant to obtain ethylene sulfate (DTD) under the catalysis of ruthenium trichloride aqueous solution. However, this method suffers from various process drawbacks such as: the toxicity of thionyl chloride is high; the noble metal catalyst ruthenium trichloride is expensive and difficult to recycle; sodium and chloride ion indexes in the product are easy to exceed standard, and the application performance of the product is affected; the excessive sodium hypochlorite strong oxidant is used for generating a large amount of salt-containing wastewater, and the method is not friendly to the environment.
In theory, the one-step method of directly preparing cyclic sulfate by reacting sulfur trioxide with alkylene oxide is an atom economic reaction, but how to obtain high-quality products with high yield is the subject of deep research. In 1962, DOW (Dow) published patent US3045027A, it was proposed to synthesize DTD by low-temperature complexation of sulfur trioxide with dioxane and further reaction with ethylene oxide, but the isolation yield was only about 10%. CN91104594.5 reports that sulfur trioxide and epoxy compounds (ethylene oxide, propylene oxide, epichlorohydrin) are added to dioxane at the same time, the addition speed and the molar ratio are strictly controlled, and the cyclic sulfate product can be obtained by reacting at 30-60 ℃, the yield is >80%, and the product purity is >97%.
In order to solve the heat transfer problem of large heat release during the reaction of sulfur trioxide and alkylene oxide, a novel microchannel reactor is used for researching the reaction, CN109456303A, CN115894433A and the like report a process for preparing vinyl sulfate by respectively dissolving sulfur trioxide and ethylene oxide in chlorinated alkane and then separately and simultaneously adding the dissolved sulfur trioxide and ethylene oxide into the microchannel reactor for reaction, and the process can effectively solve the safety problem of the reaction process.
Along with the expansion of the application field of the cyclic sulfate, the development of a process for preparing the cyclic sulfate by using the sulfur trioxide-alkylene oxide method, which has high conversion rate and high product purity and is suitable for large-scale industrial production, is still an urgent technical requirement of the fine chemical industry.
Disclosure of Invention
Aiming at the defects of the prior art, the application provides a preparation method and application of cyclic sulfate.
The application provides a preparation method of cyclic sulfate, which comprises the following steps:
(1) Sulfur trioxide is dispersed in carbonic ester to form suspension solution A;
(2) The epoxy compound is dissolved in the carbonic ester to form a solution B;
(3) The solution A and the solution B are contacted and reacted to generate the cyclic sulfate.
The process for producing a cyclic sulfate according to the present application, wherein the carbonate used in step (1) and step (2) is the same;
preferably, the carbonate is a dialkyl carbonate;
more preferably, the alkyl group of the dialkyl carbonate is a short carbon chain alkyl group, and the short carbon chain alkyl group is a C1-C3 linear or branched alkyl group;
further preferably, the carbonate is selected from one or more of the following: dimethyl carbonate, methylethyl carbonate, diethyl carbonate.
The preparation method of the cyclic sulfate, wherein in the step (2), the epoxy compound is alkylene oxide and/or halogenated alkylene oxide;
preferably, the epoxy compound is an alkylene oxide and/or a halogenated alkylene oxide having 2 to 8 carbon atoms;
more preferably, the epoxy compound is selected from one or more of the following: ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin.
The preparation method of the cyclic sulfate comprises the following steps of (1), wherein the mass fraction of sulfur trioxide in the suspension solution A is 10-40%; and/or
In the step (2), the mass fraction of the epoxy compound in the solution B is 20-40%.
The preparation method of the cyclic sulfate comprises the following steps of (1) and (2) wherein the temperature condition of the step (1) is 10-25 ℃, preferably 20 ℃; and/or
In the step (1), the sulfur trioxide is liquid.
According to the preparation method of the cyclic sulfate, in the step (3), the molar ratio of the sulfur trioxide in the suspension solution A to the epoxy compound in the solution B is 1:1.01-1.05; and/or
In the step (3), the reaction temperature is-20-45 ℃.
The preparation method of the cyclic sulfate, according to the application, further comprises an extraction and purification step;
preferably, the extraction and purification step comprises:
(4) Concentrating the reaction mother liquor obtained by the contact reaction of the solution A and the solution B in the step (3) to obtain a concentrated mother liquor, and then dissolving, washing, concentrating and drying the concentrated mother liquor by chloralkane to obtain cyclic sulfate;
more preferably, the concentration method is reduced pressure distillation concentration.
Wherein the chlorinated alkane is selected from one or more of the following: dichloromethane, dichloroethane, chloroform, preferably dichloromethane, more preferably, the mass ratio of the chlorinated alkane to the concentrated mother liquor is 5-10:1; and/or
The mass ratio of the total mass of water used in the water washing step to the concentrated mother liquor is 5-10:1, and the water washing step is preferably carried out 2 times.
Wherein the temperature in the concentrating step is controlled to be lower than 50 ℃; and/or
The drying temperature is 40 to 50 ℃, preferably 50 ℃.
The application also provides an application of the preparation method of the cyclic sulfate in preparing lithium ion battery electrolyte.
The preparation method of the application can have the following beneficial effects but is not limited to:
according to the method for synthesizing the cyclic sulfate through the reaction of the sulfur trioxide-carbonate complex and the carbonate solution of the epoxy compound, the low-toxicity carbonate is used for replacing toxic chloralkane to serve as a solvent, the danger of the application process of the sulfur trioxide is reduced through the participation of the sulfur trioxide-carbonate complex in the reaction, the separation yield in the reaction process is more than 80%, and the GC analysis purity of the product is more than 99%. The preparation method disclosed by the application is mild in reaction condition, free of catalyst addition, environment-friendly, high in target product conversion rate and high in product purity, and is suitable for large-scale industrial production.
Drawings
FIG. 1 shows a flow chart of a cyclic sulfate preparation process in one embodiment of the present application.
FIG. 2 shows a suspension of the sulfur trioxide-carbonate complex produced by the present application.
FIG. 3 shows the analytical spectrum of the Gas Chromatography (GC) test of the product of example 1 of the application.
Detailed Description
The application is further described in detail below by means of the figures and examples. The features and advantages of the present application will become more apparent from the description.
The word "exemplary" is used herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments. Although various aspects of the embodiments are illustrated in the accompanying drawings, the drawings are not necessarily drawn to scale unless specifically indicated.
In addition, the technical features described below in the different embodiments of the present application may be combined with each other as long as they do not collide with each other.
The application discloses a preparation method of cyclic sulfate, which comprises the following steps:
(1) Dissolving sulfur trioxide in carbonic ester to form suspension solution A;
(2) The epoxy compound is dissolved in the carbonic ester to form a solution B;
(3) The solution A and the solution B are contacted and reacted to generate the cyclic sulfate.
In the prior art, the yield and the product purity of the cyclic sulfate prepared by the reaction of sulfur trioxide and an epoxy compound are low, and meanwhile, due to the problem of massive heat release during the reaction of the sulfur trioxide and the epoxy compound, chlorinated alkane is introduced as a solvent to respectively dilute the sulfur trioxide and the ethylene oxide for reaction in a novel micro-channel reactor in the prior art, but the chlorinated alkane is used as the solvent to have certain toxicity in a large amount, so that the method does not meet the requirements of green chemistry. FIG. 1 shows a flow chart of a cyclic sulfate preparation process in one embodiment of the present application. The technical scheme of the application uses low-toxicity carbonic ester, and a certain amount of liquid sulfur trioxide is stirred and added into the carbonic ester at normal temperature to form white milk-like suspension, as shown in figure 2. After adding water to the suspension, the layers were separated, the aqueous layer was sulfuric acid solution, and the oil layer was still pure carbonate, whereby it was confirmed that a sulfur trioxide-carbonate complex could be formed in the white milk-like suspension. In the reaction process of sulfur trioxide and epoxy compounds, the sulfur trioxide-carbonic ester complex is introduced to reduce the danger of the application process of sulfur trioxide, avoid a large amount of acid smog generation caused by heat release during the reaction of the sulfur trioxide and the epoxy compounds, and simultaneously provide a proper reaction solvent for the synthesis of cyclic sulfate.
According to one embodiment of the application, the carbonates used in step (1) and step (2) are the same;
preferably, the carbonate is a dialkyl carbonate;
more preferably, the alkyl group of the dialkyl carbonate is a short carbon chain alkyl group, and the short carbon chain alkyl group is a C1-C3 linear or branched alkyl group;
further preferably, the carbonate is selected from one or more of the following: dimethyl carbonate, methylethyl carbonate, diethyl carbonate.
According to an embodiment of the present application, in step (2), the epoxy compound is an alkylene oxide and/or a halogenated alkylene oxide;
preferably, the epoxy compound is an alkylene oxide and/or a halogenated alkylene oxide having 2 to 8 carbon atoms;
more preferably, the epoxy compound is selected from one or more of the following: ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin.
According to one embodiment of the present application, in step (1), the mass fraction of sulfur trioxide in the suspension solution a of the sulfur trioxide-carbonate complex is 10-40%; and/or
In the step (2), the mass fraction of the epoxy compound in the solution B is 20-40%.
According to one embodiment of the application, the temperature conditions of step (1) are 10 to 25 ℃, preferably 20 ℃; and/or
In the step (1), the sulfur trioxide is liquid.
When the concentration of sulfur trioxide is too high, the fluidity of the suspension solution a of the generated sulfur trioxide-carbonate complex becomes poor, which is unfavorable for the progress of the subsequent reaction.
According to one embodiment of the application, in step (3), the molar ratio of sulfur trioxide in solution A to epoxy compound in solution B is 1:1.01-1.05; and/or
In the step (3), the reaction temperature is-20-45 ℃.
According to one embodiment of the application, the method further comprises an extraction purification step;
preferably, the extraction and purification step comprises:
(4) Concentrating the reaction mother liquor obtained by the contact reaction of the solution A and the solution B in the step (3) to obtain a concentrated mother liquor, then dissolving with chloralkane, washing with water, concentrating by reduced pressure distillation, and drying to obtain cyclic sulfate;
more preferably, the concentration method is reduced pressure distillation concentration.
According to one embodiment of the application, in step (4), the chlorinated alkane is selected from one or more of the following: dichloromethane, dichloroethane, chloroform, preferably dichloromethane;
more preferably, the mass ratio of the chlorinated alkane to the concentrated mother liquor is 5-10:1.
In the step (4), the mass ratio of the total mass of water used in the water washing step to the reaction concentrated mother liquor is 5-10:1, and the water washing step is preferably carried out 2 times.
According to one embodiment of the application, in step (4), the temperature in the concentration step is controlled to be below 50 ℃.
In the step (4), the drying temperature is 40 to 50 ℃, preferably 50 ℃.
According to one embodiment of the application, in step (4), the temperature of reduced pressure distillation is controlled to be less than 50 ℃, the reaction mother liquor is concentrated until the carbonic ester solvent cannot be distilled out, and then the reaction mother liquor is dissolved by chloralkane, and the mass ratio of chloralkane to the reaction concentrated mother liquor is 5-10:1. In the process of washing the chlorinated alkane solution with water, the quality of the water is consistent with that of the chlorinated alkane, the water washing process needs to be fully stirred, and the number of times of water washing is preferably 2. The washed chloralkane layer is distilled and concentrated under reduced pressure, the temperature is controlled to be less than 50 ℃, and the cyclic sulfate product is obtained by drying at 50 ℃, the separation yield is more than 80%, and the purity of the product is more than 99%.
The reaction system can be carried out on a conventional stirred tank or a novel microchannel reactor.
The application also provides an application of the preparation method of the cyclic sulfate in preparing lithium ion battery electrolyte.
The following examples will further illustrate the application but should not be construed as limiting the application. The reagents used in these examples, unless specifically indicated, are all chemically pure reagents and are commercially available.
Example 1
This example is a description of the preparation method of the cyclic sulfate of the present application.
(1) Preparation of sulfur trioxide-dimethyl carbonate suspension a: at 20 ℃, 40 g of liquid sulfur trioxide is stirred and added dropwise to 60 g of dimethyl carbonate to form a white milk-like suspension, namely a sulfur trioxide-carbonate complex is formed, and the mass content of the sulfur trioxide in the suspension solution is 40%.
(2) Preparation of ethylene oxide-dimethyl carbonate solution B: 22.22 g of ethylene oxide was added to 55.075 g of dimethyl carbonate at 20℃to form a 40% solution.
(3) A500 ml glass reactor with stirring and temperature control means was equipped, and solution A and solution B were simultaneously added dropwise to the glass reactor over 60 minutes, the temperature being strictly controlled to 10℃during the entire addition, and the reaction mixture was stirred for 30 minutes at 10℃after the addition.
(4) The resulting reaction mixture was then distilled at 45℃under reduced pressure to give dimethyl carbonate until no fraction was obtained, to give 64 g of a reaction concentrated mother liquor. Then adding 620 g of methylene dichloride at normal temperature for dissolution, washing with 620 g of deionized water for 2 times, fully stirring in the water washing process, concentrating the methylene dichloride phase obtained by layering by distillation at 40 ℃ under reduced pressure and drying at 50 ℃ to obtain 52.7 g of a vinyl sulfate (DTD) product, wherein the yield is 84%, and the purity of GC analysis is 99.7%.
The vinyl sulfate (DTD) product prepared in this example was subjected to Gas Chromatography (GC) detection, and the results are shown in table 1. Fig. 3 shows an analysis chart of the gas chromatography detection, wherein the No. 3 peak is a vinyl sulfate peak.
Table 1 example 1 product gas phase detection data sheet
Example 2
This example is a description of the preparation method of the cyclic sulfate of the present application.
(1) Preparation of sulfur trioxide-diethyl carbonate suspension solution a: at 20 ℃, 40 g of liquid sulfur trioxide is stirred and added dropwise into 360 g of diethyl carbonate to form a white milk-like suspension, namely a sulfur trioxide-carbonate complex is formed, and the mass content of the sulfur trioxide in the suspension solution is 10%.
(2) Preparation of ethylene oxide-diethyl carbonate solution B: 23.1 grams of ethylene oxide was added to 92.4 grams of diethyl carbonate at 20 c to form a 20% solution.
(3) A1000 ml glass reactor with stirring and temperature control means was equipped, and solution A and solution B were simultaneously added dropwise to the glass reactor over 60 minutes, the temperature being strictly controlled at-20℃throughout the addition period, and the reaction mixture was stirred for 30 minutes at-20℃after the addition.
(4) The resulting reaction mixture was then distilled off diethyl carbonate under reduced pressure at 45℃until no fraction was obtained, giving 68.5 g of a reaction concentrated mother liquor. Then 343 g of methylene chloride is added at normal temperature for dissolution, and the mixture is washed with water of which the total mass is 343 g for 2 times, the mixture is fully stirred in the water washing process, the methylene chloride phase obtained by layering is distilled and concentrated at 40 ℃ under reduced pressure and dried at 50 ℃ to obtain 55.8 g of a product of ethylene sulfate (DTD), the yield is 90%, and the GC analysis purity is 99.2%.
Example 3
This example is a description of the preparation method of the cyclic sulfate of the present application.
(1) Preparation of sulfur trioxide-methyl ethyl carbonate suspension solution a: at 20 ℃, 40 g of liquid sulfur trioxide is stirred and added dropwise into 160 g of ethyl methyl carbonate to form a white milk-like suspension, namely a sulfur trioxide-carbonate complex is formed, and the mass content of the sulfur trioxide in the suspension solution is 20%.
(2) Preparation of propylene oxide-methyl ethyl carbonate solution B: 29.58 g of propylene oxide were added to 69 g of ethyl methyl carbonate at 20℃to form a 30% solution.
(3) A500 ml glass reactor with stirring and temperature control means was equipped, and solution A and solution B were simultaneously added dropwise to the glass reactor over 60 minutes, the temperature being strictly controlled to 45℃throughout the addition period, and the reaction mixture was stirred for a further 30 minutes at 45℃after the addition.
(4) The resulting reaction mixture was then distilled off under reduced pressure at 45℃until no fraction was obtained, to give 66.4 g of a reaction concentrated mother liquor. Then adding 556 g of methylene dichloride at normal temperature for dissolution, washing with 556 g of deionized water for 2 times, stirring thoroughly during the washing, concentrating the methylene dichloride phase obtained by layering by distillation under reduced pressure at 40 ℃ and drying at 50 ℃ to obtain 56.58 g of propylene sulfate product, wherein the yield is 82%, and the GC analysis purity is 99.4%.
Example 4
This example is a description of the preparation method of the cyclic sulfate of the present application.
(1) Preparation of sulfur trioxide-dimethyl carbonate suspension a: at 20 ℃, 40 g of liquid sulfur trioxide is stirred and added dropwise to 93 g of dimethyl carbonate to form a white milk-like suspension, namely a sulfur trioxide-carbonate complex is formed, and the mass content of sulfur trioxide in the suspension solution is 30%.
(2) Preparation of butylene oxide-dimethyl carbonate solution B: 37.5 grams of butylene oxide was added to 88 grams of dimethyl carbonate at 20 c to form a 30% solution.
(3) A500 ml glass reactor with stirring and temperature control means was equipped, and solution A and solution B were simultaneously added dropwise to the glass reactor over 60 minutes, the temperature being strictly controlled to 25℃during the entire addition, and the reaction mixture was stirred for 30 minutes at 25℃after the addition.
(4) The resulting reaction mixture was then distilled at 45℃under reduced pressure to give dimethyl carbonate until no fraction was obtained, yielding 78.5 g of a reaction concentrated mother liquor. Then, 465 g of methylene dichloride is added at normal temperature for dissolution, and the mixture is washed with 465 g of deionized water for 2 times, and the mixture is fully stirred in the water washing process, and the methylene dichloride phase obtained by layering is distilled and concentrated at 40 ℃ under reduced pressure and dried at 50 ℃ to obtain 66.12 g of butylene sulfate product, the yield is 87%, and the GC analysis purity is 99.1%.
Example 5
This example is a description of the preparation method of the cyclic sulfate of the present application.
(1) Preparation of sulfur trioxide-methyl ethyl carbonate suspension solution a: at 20 ℃, 40 g of liquid sulfur trioxide is stirred and added dropwise into 160 g of ethyl methyl carbonate to form a white milk-like suspension, namely a sulfur trioxide-carbonate complex is formed, and the mass content of the sulfur trioxide in the suspension solution is 20%.
(2) Preparation of epichlorohydrin-methyl ethyl carbonate solution B: 47.2 g of epichlorohydrin was added to 190 g of ethyl methyl carbonate at 20℃to form a 20% solution.
(3) A1000 ml glass reactor with stirring and temperature control means was equipped, and solution A and solution B were simultaneously added dropwise to the glass reactor over 60 minutes, the temperature being strictly controlled at 35℃during the entire addition, and the reaction mixture was stirred for 30 minutes at 35℃after the addition.
(4) The resulting reaction mixture was then distilled off under reduced pressure at 45℃until no fraction was obtained, to give 89.5 g of a reaction concentrated mother liquor. Then adding 785 g of methylene dichloride at normal temperature for dissolution, washing with 785 g of deionized water for 2 times, stirring thoroughly during the washing, concentrating the methylene dichloride phase obtained by layering by distillation under reduced pressure at 40 ℃ and drying at 50 ℃ to obtain 75 g of chloropropene sulfate product, wherein the yield is 86%, and the GC analysis purity is 99.4%.
The application has been described above in connection with preferred embodiments, which are, however, exemplary only and for illustrative purposes. On this basis, the application can be subjected to various substitutions and improvements, and all fall within the protection scope of the application.
Claims (10)
1. A process for the preparation of a cyclic sulfate, the process comprising the steps of:
(1) Sulfur trioxide is dispersed in carbonic ester to form suspension solution A;
(2) The epoxy compound is dissolved in the carbonic ester to form a solution B;
(3) The solution A and the solution B are contacted and reacted to generate the cyclic sulfate.
2. The process according to claim 1, wherein the carbonate used in step (1) and step (2) is the same;
preferably, the carbonate is a dialkyl carbonate;
more preferably, the alkyl group of the dialkyl carbonate is a short carbon chain alkyl group, and the short carbon chain alkyl group is a C1-C3 linear or branched alkyl group;
further preferably, the carbonate is selected from one or more of the following: dimethyl carbonate, methylethyl carbonate, diethyl carbonate.
3. The production method according to claim 1 or 2, wherein in the step (2), the epoxy compound is an alkylene oxide and/or a halogenated alkylene oxide;
preferably, the epoxy compound is an alkylene oxide and/or a halogenated alkylene oxide having 2 to 8 carbon atoms;
more preferably, the epoxy compound is selected from one or more of the following: ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin.
4. A production method according to any one of claims 1 to 3, wherein in step (1), the mass fraction of sulfur trioxide in the suspension solution a is 10-40%; and/or
In the step (2), the mass fraction of the epoxy compound in the solution B is 20-40%.
5. The process according to any one of claims 1 to 4, wherein the temperature conditions of step (1) are 10 to 25 ℃, preferably 20 ℃; and/or
In the step (1), the sulfur trioxide is liquid.
6. The process according to any one of claims 1 to 5, wherein in step (3), the molar ratio of sulfur trioxide in suspension solution a to epoxy compound in solution B is 1:1.01-1.05; and/or
In the step (3), the reaction temperature is-20-45 ℃.
7. The production method according to any one of claims 1 to 6, characterized in that the method further comprises an extraction purification step;
preferably, the extraction and purification step comprises:
(4) Concentrating the reaction mother liquor obtained by the contact reaction of the solution A and the solution B in the step (3) to obtain a concentrated mother liquor, and then dissolving, washing, concentrating and drying the concentrated mother liquor by chloralkane to obtain cyclic sulfate;
more preferably, the concentration method is reduced pressure distillation concentration.
8. The method of claim 7, wherein the chlorinated alkane is selected from one or more of the following: dichloromethane, dichloroethane, chloroform, preferably dichloromethane, more preferably, the mass ratio of the chlorinated alkane to the concentrated mother liquor is 5-10:1; and/or
The mass ratio of the total mass of water used in the water washing step to the concentrated mother liquor is 5-10:1, and the water washing step is preferably carried out 2 times.
9. The method of claim 7 or 8, wherein the temperature in the concentrating step is controlled to be lower than 50 ℃; and/or
The drying temperature is 40 to 50 ℃, preferably 50 ℃.
10. Use of the method for preparing cyclic sulfate according to any one of claims 1 to 9 for preparing lithium ion battery electrolyte.
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