CN114805290A - Preparation method of vinyl sulfate - Google Patents
Preparation method of vinyl sulfate Download PDFInfo
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- CN114805290A CN114805290A CN202210512674.4A CN202210512674A CN114805290A CN 114805290 A CN114805290 A CN 114805290A CN 202210512674 A CN202210512674 A CN 202210512674A CN 114805290 A CN114805290 A CN 114805290A
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- Prior art keywords
- vinyl sulfate
- fluoride
- reaction
- potassium fluoride
- product
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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 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims abstract description 86
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000011698 potassium fluoride Substances 0.000 claims abstract description 43
- 235000003270 potassium fluoride Nutrition 0.000 claims abstract description 43
- 239000000047 product Substances 0.000 claims abstract description 35
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims abstract description 34
- JGWFUSVYECJQDT-UHFFFAOYSA-N trimethyl(2-trimethylsilyloxyethoxy)silane Chemical compound C[Si](C)(C)OCCO[Si](C)(C)C JGWFUSVYECJQDT-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000006227 byproduct Substances 0.000 claims abstract description 16
- 239000005935 Sulfuryl fluoride Substances 0.000 claims abstract description 13
- 239000012043 crude product Substances 0.000 claims abstract description 13
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000005051 trimethylchlorosilane Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims abstract description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 10
- CTIKAHQFRQTTAY-UHFFFAOYSA-N fluoro(trimethyl)silane Chemical compound C[Si](C)(C)F CTIKAHQFRQTTAY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 239000003495 polar organic solvent Substances 0.000 claims abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 8
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 8
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 8
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 4
- 229940090181 propyl acetate Drugs 0.000 claims description 4
- 239000011775 sodium fluoride Substances 0.000 claims description 4
- 235000013024 sodium fluoride Nutrition 0.000 claims description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 4
- ODNBVEIAQAZNNM-UHFFFAOYSA-N 1-(6-chloroimidazo[1,2-b]pyridazin-3-yl)ethanone Chemical compound C1=CC(Cl)=NN2C(C(=O)C)=CN=C21 ODNBVEIAQAZNNM-UHFFFAOYSA-N 0.000 claims description 3
- GUNJVIDCYZYFGV-UHFFFAOYSA-K Antimony trifluoride Inorganic materials F[Sb](F)F GUNJVIDCYZYFGV-UHFFFAOYSA-K 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 2
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 2
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 10
- 239000002699 waste material Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000012025 fluorinating agent Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 21
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 239000002904 solvent Substances 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 230000006872 improvement Effects 0.000 description 10
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 9
- 239000012535 impurity Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 229960001701 chloroform Drugs 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 description 4
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 description 3
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012286 potassium permanganate 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
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction 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
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000002000 Electrolyte additive Substances 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- XFKVHUONJVDEIW-UHFFFAOYSA-N [Cl].S(O)(O)(=O)=O Chemical compound [Cl].S(O)(O)(=O)=O XFKVHUONJVDEIW-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention belongs to the technical field of compound preparation, and particularly relates to a preparation method of vinyl sulfate, which comprises the following steps: adding ethylene glycol and trimethylchlorosilane into an organic solvent for reaction to prepare 1, 2-bis (trimethylsiloxy) ethane; sulfuric acid chloride and a fluorinating agent act in a polar organic solvent to prepare sulfuryl fluoride; introducing sulfuryl fluoride into 1, 2-bis (trimethylsiloxy) ethane, stirring for reaction to obtain a vinyl sulfate crude product, and absorbing a trimethylfluorosilane byproduct generated in the reaction process by using a potassium hydroxide solution to generate trimethylsiloxane and potassium fluoride; and fourthly, adding deionized water into the crude product of the vinyl sulfate, fully washing, concentrating, crystallizing, filtering, and drying under reduced pressure to obtain a finished product of the vinyl sulfate. Compared with the prior art, the preparation method provided by the invention has the advantages of simple process and low cost, can be used for preparing a high-purity vinyl sulfate target product, and can be used for completely recovering byproducts, thereby greatly reducing the discharge of three wastes.
Description
Technical Field
The invention belongs to the technical field of compound preparation, and particularly relates to a preparation method of vinyl sulfate.
Background
The ethylene sulfate is used as a novel lithium ion battery electrolyte additive, and the structural components of an interface film are improved by forming a stable passivation film, so that the reduction of the internal resistance of the battery and the improvement of the service life of the battery are facilitated.
At present, the preparation process of the vinyl sulfate mainly adopts a two-step method: 1) ethylene glycol and thionyl chloride react to synthesize ethylene sulfite; 2) oxidizing the ethylene sulfite into ethylene sulfate by using an oxidant. The differences of the synthesis methods disclosed in the first step of preparing the ethylene sulfite are not great, and the second oxidation procedure mainly comprises the following scheme: 1) ruthenium trichloride is used as a catalyst, and sodium periodate, sodium hypochlorite or potassium persulfate is used as an oxidant; 2) potassium permanganate or a hydrogen peroxide/sulfuric acid system is used as oxidizing agent. However, ruthenium trichloride is expensive as a catalyst, and sodium periodate, sodium hypochlorite or potassium persulfate are used as oxidizing agents to generate a large amount of wastewater and solid waste. Potassium permanganate then causes heavy metal pollution and also has the problems of a large amount of waste water and solid waste, the hydrogen peroxide reduction product is water, the process is relatively green, but the process still needs to use a catalyst and the overall yield is low.
In view of the above, the present invention aims to provide a method for preparing vinyl sulfate, which has the advantages of simple preparation process and low cost, can prepare a high-purity target product of vinyl sulfate, and can completely recover byproducts, thereby greatly reducing the discharge of three wastes.
Disclosure of Invention
The invention aims to: aiming at the defects of the prior art, the preparation method of the vinyl sulfate is provided, the preparation process is simple, the cost is low, the high-purity target product of the vinyl sulfate can be prepared, in addition, the byproducts can be completely recovered, and the discharge of three wastes is greatly reduced.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of vinyl sulfate comprises the following steps:
firstly, adding ethylene glycol and trimethylchlorosilane into an organic solvent for reaction to prepare 1, 2-bis (trimethylsiloxy) ethane;
secondly, sulfuric acid chlorine and a fluorinating reagent act in a polar organic solvent to prepare sulfuryl fluoride;
thirdly, introducing the sulfuryl fluoride obtained in the second step into the 1, 2-bis (trimethylsiloxy) ethane obtained in the first step, stirring and reacting to obtain a vinyl sulfate crude product, and absorbing a trimethylfluorosilane byproduct generated in the reaction process by using a potassium hydroxide solution to generate trimethylsiloxane and potassium fluoride;
and step four, adding deionized water into the vinyl sulfate crude product obtained in the step three, fully washing, concentrating, crystallizing, filtering, and drying under reduced pressure to obtain a finished product of the vinyl sulfate.
The preparation method of the vinyl sulfate is an improvement, the mixed system of the trimethyl siloxane and the potassium fluoride generated in the third step is layered, the trimethyl siloxane on the upper layer is separated out, the pure product is obtained by distillation and purification, and the potassium fluoride water solution on the lower layer is crystallized after concentration to obtain the potassium fluoride product.
As an improvement of the preparation method of the ethylene sulfate, the organic solvent in the first step is at least one of dichloromethane, chloroform, n-hexane, cyclohexane, acetonitrile, acetone, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethyl acetate, propyl acetate, butyl acetate, diethyl ether and methyl tert-butyl ether.
As an improvement of the preparation method of the vinyl sulfate, the stoichiometric molar ratio of the ethylene glycol to the trimethylchlorosilane is 1: 2-1: 3.
as an improvement of the preparation method of the vinyl sulfate, the stoichiometric molar ratio of the ethylene glycol to the trimethylchlorosilane is 1: 2-1: 2.2.
as an improvement of the preparation method of the vinyl sulfate, the reaction temperature of the first step is 25-80 DEG o C。
As an improvement of the process for preparing vinyl sulfate of the present invention, the polar organic solvent in the second step includes at least one of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethyl acetate, propyl acetate, butyl acetate, propyl propionate, acetonitrile, propionitrile, acetone, tetrahydrofuran, diethyl ether, methyl tert-butyl ether, propyl ether, butyl ether and ethylene glycol dimethyl ether.
As sulfuric acid of the inventionAn improvement of the preparation method of the vinyl ester, the reaction temperature of the second step is 25-80 DEG o C。
As an improvement of the preparation method of the vinyl sulfate, the fluorinating agent in the second step comprises at least one of sodium fluoride, potassium fluoride, zinc fluoride, antimony trifluoride and hydrogen fluoride. The stoichiometric molar ratio of sulfuryl chloride to fluorinating reagent is 1: 2-1: 5, preferably 1: 2-1: 2.5, the reaction temperature of the second step is 40-60 DEG o C。
As an improvement of the preparation method of the vinyl sulfate, the reaction temperature of the third step is 40-80 DEG o C; fourthly, the temperature of the reduced pressure drying is 40-80 DEG C o C。
Compared with the prior art, the preparation method provided by the invention has the advantages of simple process and low cost, can be used for preparing a high-purity vinyl sulfate target product, and can be used for completely recovering byproducts, thereby greatly reducing the discharge of three wastes.
That is, the raw materials used in the invention are easy to obtain, the cost is low, the production process is simple, the yield is high, the product is easy to separate and purify, and the amount of three wastes is small and simple. The hexamethyldisiloxane and potassium fluoride byproduct produced is also of high value.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The mere fact that one or more method steps are recited in the present invention does not exclude the presence of other method steps before or after the combination step or the interposition of other method steps between these explicitly recited steps, unless otherwise indicated.
Example 1
A500 mL reaction flask was charged with 31g (0.5 mol) of ethylene glycol, 100mL of methylene chloride as a solvent, and 109g (1 mol) of trimethylchlorosilane and 30 g of chlorotrimethylsilane were added in portions o Stirring and reacting for 8 hours under C to obtain a 1, 2-bis (trimethylsiloxy) ethane/dichloromethane solution, and absorbing the generated hydrogen chloride gas by water.
A1000 mL reaction flask was charged with 69.6g (1.2 mol) of potassium fluoride, 200mL of anhydrous acetonitrile was added as a solvent, and 67g (0.5 mol) of sulfuryl chloride and 60 g of acetonitrile were added in portions o Stirring and reacting under C, introducing generated sulfuryl fluoride gas into the 1, 2-bis (trimethylsiloxy) ethane/dichloromethane solution after the reaction in the previous step, and controlling the temperature to be 60 DEG o C reaction was stopped after 8 hours. Absorbing trimethyl fluorosilane gas generated in the reaction process by using a potassium hydroxide solution to obtain byproducts hexamethyldisiloxane and potassium fluoride. Adding deionized water into the reaction system, washing thoroughly, removing ionic impurities, concentrating under reduced pressure to remove a large amount of dichloromethane, recrystallizing, filtering to obtain crude product of vinyl sulfate, 60% o Drying under reduced pressure at C gave 55.8 g of product in 90% yield.
The reaction principle of this example is:
layering the generated trimethyl siloxane and potassium fluoride mixed system, separating the upper layer trimethyl siloxane, distilling and purifying to obtain a pure product, and concentrating and crystallizing the lower layer potassium fluoride aqueous solution to obtain a potassium fluoride product.
The technical scheme of the invention has the advantages of easily obtained raw materials, low cost, simple production process, high yield, easy separation and purification of products, small amount of three wastes and simplicity. The hexamethyldisiloxane and potassium fluoride byproduct produced is also of high value.
Example 2
A500 mL reaction flask was charged with 31g (0.5 mol) of ethylene glycol, 100mL of chloroform as a solvent, and 109g (1 mol) of trimethylchlorosilane and 40 g of chlorotrimethylsilane were added in portions o Stirring and reacting for 10 hours under C to obtain a 1, 2-bis (trimethylsiloxy) ethane/trichloromethane solution, and absorbing the generated hydrogen chloride gas by water.
A1000 mL reaction flask was charged with 69.6g (1.2 mol) of potassium fluoride and 200mL of dimethyl carbonate as a solvent, and 67g (0.5 mol) of sulfuryl chloride and 70 g of sulfuric acid were added in portions o Stirring and reacting under C, introducing generated sulfuryl fluoride gas into the 1, 2-bis (trimethylsiloxy) ethane/trichloromethane solution obtained in the previous step, and controlling the temperature to be 50 DEG o C reaction was stopped after 10 hours. Reaction processAbsorbing the generated trimethyl fluorosilane gas by using a potassium hydroxide solution to obtain byproducts hexamethyldisiloxane and potassium fluoride. Adding deionized water into the reaction system, washing thoroughly, removing ionic impurities, concentrating under reduced pressure to remove a large amount of dichloromethane, recrystallizing, filtering to obtain crude product of vinyl sulfate, 70 o And C, drying under reduced pressure to obtain the product.
Layering the generated trimethyl siloxane and potassium fluoride mixed system, separating the upper layer trimethyl siloxane, distilling and purifying to obtain a pure product, and concentrating and crystallizing the lower layer potassium fluoride aqueous solution to obtain a potassium fluoride product.
Example 3
A500 mL reaction flask was charged with 31g (0.5 mol) of ethylene glycol, 100mL of n-hexane as a solvent, and 119.9g (1.1 mol) of trimethylchlorosilane and 50 g of chlorotrimethylsilane were added in portions o Stirring and reacting for 12 hours under C to obtain a 1, 2-bis (trimethylsiloxy) ethane/n-hexane solution, and absorbing the generated hydrogen chloride gas by water.
A1000 mL reaction flask was charged with 50.4g (1.2 mol) of sodium fluoride and 200mL of diethyl carbonate as a solvent, and 67g (0.5 mol) of sulfuryl chloride and 65 g of the mixture were added in portions o Stirring for reaction under C, introducing generated sulfuryl fluoride gas into the 1, 2-bis (trimethylsiloxy) ethane/n-hexane solution obtained in the previous step, and controlling the temperature to be 70 DEG o C reaction was stopped after 7 hours. Absorbing trimethyl fluorosilane gas generated in the reaction process by using a potassium hydroxide solution to obtain byproducts hexamethyldisiloxane and potassium fluoride. Adding deionized water into the reaction system, fully washing, removing ionic impurities, then carrying out reduced pressure concentration to remove a large amount of dichloromethane, carrying out recrystallization operation, filtering to obtain a crude product of vinyl sulfate, 65% o And C, drying under reduced pressure to obtain the product.
Layering the generated trimethyl siloxane and potassium fluoride mixed system, separating the upper layer trimethyl siloxane, distilling and purifying to obtain a pure product, and concentrating and crystallizing the lower layer potassium fluoride aqueous solution to obtain a potassium fluoride product.
Example 4
A500 mL reaction flask was charged with 31g (0.5 mol) of ethylene glycol and 100mL of cyclohexane as a solvent, and the mixture was divided into portions109g (1 mol) of trimethylchlorosilane, 30 g o And C, stirring and reacting for 20 hours to obtain a 1, 2-bis (trimethylsiloxy) ethane/cyclohexane solution, and absorbing the generated hydrogen chloride gas by water.
A1000 mL reaction flask was charged with 155.1g (1.5 mol) of zinc fluoride, 200mL of ethyl acetate was added as a solvent, and 67g (0.5 mol) of sulfuryl chloride and 65 g of sulfuric acid were added in portions o Stirring and reacting at the temperature of C, introducing generated sulfuryl fluoride gas into the 1, 2-bis (trimethylsiloxy) ethane/cyclohexane solution after the reaction in the previous step, and controlling the temperature to be 70 DEG o C reaction was stopped after 7 hours. Absorbing trimethyl fluorosilane gas generated in the reaction process by using a potassium hydroxide solution to obtain byproducts hexamethyldisiloxane and potassium fluoride. Adding deionized water into the reaction system, fully washing, removing ionic impurities, then carrying out reduced pressure concentration to remove a large amount of dichloromethane, carrying out recrystallization operation, filtering to obtain a crude product of vinyl sulfate, 55 o And C, drying under reduced pressure to obtain the product.
Layering the generated trimethyl siloxane and potassium fluoride mixed system, separating the upper layer trimethyl siloxane, distilling and purifying to obtain a pure product, and concentrating and crystallizing the lower layer potassium fluoride aqueous solution to obtain a potassium fluoride product.
Example 5
A500 mL reaction flask was charged with 31g (0.5 mol) of ethylene glycol, 100mL of acetonitrile as a solvent, 163.5g (1.5 mol) of trimethylchlorosilane, 50 g o Stirring and reacting for 16 hours under C to obtain a 1, 2-bis (trimethylsiloxy) ethane/acetonitrile solution, and absorbing the generated hydrogen chloride gas by water.
A1000 mL reaction flask was charged with 357.52g (2 mol) of antimony trifluoride, 200mL of tetrahydrofuran as a solvent, and 67g (0.5 mol) of sulfuryl chloride and 45 g of sulfuryl chloride were added in portions o Stirring and reacting at the temperature of C, introducing generated sulfuryl fluoride gas into the 1, 2-bis (trimethylsiloxy) ethane/acetonitrile solution obtained in the previous step, and controlling the temperature to be 55 DEG o C reaction was stopped after 6 hours. Absorbing trimethyl fluorosilane gas generated in the reaction process by using a potassium hydroxide solution to obtain byproducts hexamethyldisiloxane and potassium fluoride. Adding deionized water into the reaction system for full washing, and removingConcentrating under reduced pressure to remove a large amount of dichloromethane after sub-impurities, recrystallizing, and filtering to obtain crude product of vinyl sulfate, 68 o And C, drying under reduced pressure to obtain the product.
Layering the generated trimethyl siloxane and potassium fluoride mixed system, separating the upper layer trimethyl siloxane, distilling and purifying to obtain a pure product, and concentrating and crystallizing the lower layer potassium fluoride aqueous solution to obtain a potassium fluoride product.
Example 6
A500 mL reaction flask was charged with 31g (0.5 mol) of ethylene glycol, 100mL of dimethyl carbonate as a solvent, 163.5g (1.5 mol) of trimethylchlorosilane, 56 g in portions o Stirring and reacting for 11 hours under C to obtain a 1, 2-bis (trimethylsiloxy) ethane/dimethyl carbonate solution, and absorbing the generated hydrogen chloride gas with water.
A1000 mL reaction flask was charged with 84 g (2 mol) of sodium fluoride and 200mL of diethyl ether as a solvent, and 67g (0.5 mol) of sulfuryl chloride and 55 g of sulfuric acid were added in portions o Stirring for reaction under C, introducing generated sulfuryl fluoride gas into the 1, 2-bis (trimethylsiloxy) ethane/dimethyl carbonate solution after the reaction in the previous step, and controlling the temperature to 65 DEG o C reaction was stopped after 3 hours. Absorbing trimethyl fluorosilane gas generated in the reaction process by using a potassium hydroxide solution to obtain byproducts hexamethyldisiloxane and potassium fluoride. Adding deionized water into the reaction system, fully washing, removing ionic impurities, then carrying out reduced pressure concentration to remove a large amount of dichloromethane, carrying out recrystallization operation, filtering to obtain a crude product of vinyl sulfate, 63 o And C, drying under reduced pressure to obtain the product.
Layering the generated trimethyl siloxane and potassium fluoride mixed system, separating the upper layer trimethyl siloxane, distilling and purifying to obtain a pure product, and concentrating and crystallizing the lower layer potassium fluoride aqueous solution to obtain a potassium fluoride product.
Example 7
A500 mL reaction flask was charged with 31g (0.5 mol) of ethylene glycol, 100mL of acetone as a solvent, and 141.7g (1.3 mol) of chlorotrimethylsilane, 62 o Stirring and reacting for 13 hours under C to obtain 1, 2-bis (trimethylsiloxy) ethane/acetone solution, and generating hydrogen chlorideThe gas is absorbed by water.
134.42g (1.3 mol) of zinc fluoride was added to a 1000 mL reaction flask, 200mL of ethylene glycol dimethyl ether was added as a solvent, and 67g (0.5 mol) of sulfuryl chloride and 45 g of ethylene glycol dimethyl ether were added in portions o Stirring and reacting under C, introducing generated sulfuryl fluoride gas into the 1, 2-bis (trimethylsiloxy) ethane/acetone solution after the reaction in the previous step, and controlling the temperature to be 66 DEG o C reaction was stopped after 5 hours. Absorbing trimethyl fluorosilane gas generated in the reaction process by using a potassium hydroxide solution to obtain byproducts hexamethyldisiloxane and potassium fluoride. Adding deionized water into the reaction system, fully washing, removing ionic impurities, then carrying out reduced pressure concentration to remove a large amount of dichloromethane, carrying out recrystallization operation, filtering to obtain a crude product of vinyl sulfate, 59 o And C, drying under reduced pressure to obtain the product.
Layering the generated trimethyl siloxane and potassium fluoride mixed system, separating the upper layer trimethyl siloxane, distilling and purifying to obtain a pure product, and concentrating and crystallizing the lower layer potassium fluoride aqueous solution to obtain a potassium fluoride product.
Variations and modifications to the above-described embodiments may occur to those skilled in the art, which fall within the scope and spirit of the above description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (10)
1. The preparation method of the vinyl sulfate is characterized by comprising the following steps:
firstly, adding ethylene glycol and trimethylchlorosilane into an organic solvent for reaction to prepare 1, 2-bis (trimethylsiloxy) ethane;
secondly, sulfuric acid chloride and a fluorinating reagent act in a polar organic solvent to prepare sulfuryl fluoride;
thirdly, introducing the sulfuryl fluoride obtained in the second step into the 1, 2-bis (trimethylsiloxy) ethane obtained in the first step, stirring and reacting to obtain a vinyl sulfate crude product, and absorbing a trimethylfluorosilane byproduct generated in the reaction process by using a potassium hydroxide solution to generate trimethylsiloxane and potassium fluoride;
and step four, adding deionized water into the vinyl sulfate crude product obtained in the step three, fully washing, concentrating, crystallizing, filtering, and drying under reduced pressure to obtain a finished product of the vinyl sulfate.
2. The method for producing vinyl sulfate according to claim 1, characterized in that: and (3) layering the mixed system of the trimethylsiloxane and the potassium fluoride generated in the third step to separate the upper layer of the trimethylsiloxane, distilling and purifying to obtain a pure product, and crystallizing the lower layer of the potassium fluoride aqueous solution to obtain a potassium fluoride product.
3. The method for producing vinyl sulfate according to claim 1, characterized in that: the organic solvent in the first step is at least one of dichloromethane, chloroform, n-hexane, cyclohexane, acetonitrile, acetone, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethyl acetate, propyl acetate, butyl acetate, diethyl ether and methyl tert-butyl ether.
4. The method for producing vinyl sulfate according to claim 1, characterized in that: the stoichiometric molar ratio of ethylene glycol and trimethylchlorosilane is 1: 2-1: 3.
5. the method for producing vinyl sulfate according to claim 1, characterized in that: the stoichiometric molar ratio of ethylene glycol and trimethylchlorosilane is 1: 2-1: 2.2.
6. the method for producing vinyl sulfate according to claim 1, characterized in that: the reaction temperature of the first step is 25-80 DEG C o C。
7. The method for producing vinyl sulfate according to claim 1, characterized in that: the polar organic solvent in the second step includes at least one of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethyl acetate, propyl acetate, butyl acetate, propyl propionate, acetonitrile, propionitrile, acetone, tetrahydrofuran, diethyl ether, methyl tert-butyl ether, propyl ether, butyl ether, and ethylene glycol dimethyl ether.
8. The method for producing vinyl sulfate according to claim 1, characterized in that: the reaction temperature of the second step is 25-80 DEG C o C。
9. The method for producing vinyl sulfate according to claim 1, characterized in that: and the fluorinating reagent in the second step comprises at least one of sodium fluoride, potassium fluoride, zinc fluoride, antimony trifluoride and hydrogen fluoride, and the stoichiometric molar ratio of sulfuryl chloride to the fluorinating reagent is 1: 2-1: 5, the reaction temperature of the second step is 40-60 DEG o C。
10. The method for producing vinyl sulfate according to claim 1, characterized in that: the reaction temperature of the third step is 40-80 DEG C o C; fourthly, the temperature of the reduced pressure drying is 40-80 DEG C o C。
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