CN111825652A - Method for preparing vinyl sulfate - Google Patents
Method for preparing vinyl sulfate Download PDFInfo
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- CN111825652A CN111825652A CN201910309704.XA CN201910309704A CN111825652A CN 111825652 A CN111825652 A CN 111825652A CN 201910309704 A CN201910309704 A CN 201910309704A CN 111825652 A CN111825652 A CN 111825652A
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- Prior art keywords
- vinyl
- hours
- sulfite
- reaction
- vinyl sulfate
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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 53
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- RBBXSUBZFUWCAV-UHFFFAOYSA-N ethenyl hydrogen sulfite Chemical compound OS(=O)OC=C RBBXSUBZFUWCAV-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000007800 oxidant agent Substances 0.000 claims abstract description 26
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 70
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 46
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 claims description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 238000006482 condensation reaction Methods 0.000 claims description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000007844 bleaching agent Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 11
- 239000000460 chlorine Substances 0.000 claims description 11
- 229910052801 chlorine Inorganic materials 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 150000002825 nitriles Chemical class 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 7
- 150000002576 ketones Chemical class 0.000 claims description 7
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 7
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 5
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 5
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 5
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 4
- 229940090181 propyl acetate Drugs 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- -1 vinyl sulfate ester Chemical class 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 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
- 238000001816 cooling Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000011356 non-aqueous organic solvent Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 235000011483 Ribes Nutrition 0.000 description 1
- 241000220483 Ribes Species 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 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
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 210000000614 rib Anatomy 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method for preparing vinyl sulfate, which comprises the following steps: (1) providing a mixture of an oxidizing agent and an organic solvent, wherein the oxidizing agent comprises calcium hypochlorite; and (2) adding vinyl sulfite to the mixture to form vinyl sulfate. In the invention, the method for preparing the vinyl sulfate avoids a water system heterogeneous oxidation reaction mode adopted in the prior art. The method directly reacts in the organic solvent, solves the practical problem that the vinyl sulfate ester is decomposed in water from the source, and obviously reduces the water residue and the free acid residue in the product, thereby improving the reaction yield of the vinyl sulfate ester and improving the purity of the product.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a method for preparing vinyl sulfate. The ethylene sulfate can be used as an additive of the lithium ion battery electrolyte.
Technical Field
The ethylene sulfate is a novel organic film forming additive with excellent effect for the electrolyte of the secondary lithium ion battery. Because the central sulfur atom of the vinyl sulfate is more electronegative, the reduction at the graphite cathode interface is stronger than that of the corresponding carbonate, and therefore, a more stable solid electrolyte phase interface film is formed in preference to the electrode interface. The vinyl sulfate added into the lithium battery electrolyte can inhibit the reduction of the initial capacity of the battery, increase the initial discharge capacity, reduce the expansion of the battery after being placed at high temperature, improve the charge and discharge performance of the battery and increase the cycle number.
The published data show that the current method for preparing the vinyl sulfate is mainly carried out at low temperature by adopting an aqueous oxidant such as the vinyl sulfite and sodium hypochlorite and a catalyst, and an organic solvent which is immiscible with water such as dichloromethane and the like is usually added to carry out extraction protection on the vinyl sulfate so as to form a heterogeneous reaction system. Because the ethylene sulfate is easy to hydrolyze to form a strong acid substance, sodium bicarbonate is also needed to be added for neutralization in the oxidation process, and the pH value range needs to be strictly controlled. The disadvantages of this method are:
1. the reaction system is heterogeneous, so that the reaction is difficult to fully proceed and the yield is low;
2. the low temperature is strictly controlled in the reaction, a large amount of heat is released due to the oxidation reaction, and the reaction heat needs to be continuously and circularly removed by a low-temperature refrigerator in the industrial production, so that the energy consumption is high;
3. produce a large amount of high COD waste water, increase the environmental burden and increase the waste water treatment cost.
Therefore, there is a need for a novel method for preparing vinyl sulfate, which overcomes the above-mentioned disadvantages and problems of the prior art, and is suitable for industrial production with low cost and low energy consumption.
Disclosure of Invention
Aiming at the defects and problems in the prior art, the inventor of the invention finds a preparation method of vinyl sulfate, which is mild in reaction, simple in process, low in cost and energy consumption and more suitable for industrial production, through intensive research.
To this end, the present invention provides a process for preparing vinyl sulfate, the process comprising:
(1) providing a mixture of an oxidizing agent and an organic solvent, wherein the oxidizing agent comprises calcium hypochlorite; and
(2) vinyl sulfite is added to the mixture to form vinyl sulfate.
In one embodiment of the invention, the oxidizing agent is selected from calcium hypochlorite or bleaching powder. In one embodiment of the invention, the oxidizing agent is dry or substantially free of water.
In one embodiment of the present invention, the organic solvent is selected from the group consisting of esters, ethers, alcohols, nitriles, ketones, halogenated alkanes and combinations of one or more of aromatic hydrocarbons;
preferably, the adding amount of the organic solvent is 300-1000% of the mass of the ethylene sulfite.
In one embodiment of the invention, the ester is selected from the group consisting of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl acetate, ethyl acetate and propyl acetate;
the ether is selected from one or more of diethyl ether, 1, 4-dioxane, tetrahydrofuran and glycol dimethyl ether;
the alcohol is selected from one or more of methanol, ethanol, butanol, propanol, butanol and isopropanol;
the nitrile is selected from acetonitrile, propionitrile, or a combination thereof;
the ketone is selected from acetone, methyl ethyl ketone, cyclohexanone or any combination thereof;
the halogenated alkane is selected from dichloromethane, dichloroethane or any combination thereof; and
the aromatic hydrocarbon is selected from benzene, toluene, xylene, chlorobenzene or any combination thereof.
In one embodiment of the present invention, the molar ratio of the oxidizing agent to the vinyl sulfite is (1 to 1.3):1 in terms of available chlorine.
In one embodiment of the present invention, in step (1), the mixture further comprises a catalyst;
preferably, the catalyst is selected from ruthenium trichloride, ruthenium oxide or a combination thereof;
preferably, the addition amount of the catalyst is 0.01-0.2% by mass of the oxidant.
In one embodiment of the invention, in the step (2), under the stirring condition, at the temperature of 0-60 ℃, dripping the vinyl sulfite into the mixture, and carrying out heat preservation reaction for 1-12 hours to form a reaction solution containing the vinyl sulfate;
preferably, the method further comprises: and filtering the reaction liquid containing the vinyl sulfate, and concentrating and recrystallizing to form the vinyl sulfate.
In one embodiment of the present invention, in the step (2), the vinyl sulfite is prepared by a condensation reaction of ethylene glycol and thionyl chloride;
preferably, ethylene glycol is added into thionyl chloride and reacted at a temperature of 50-80 ℃ for 1-3 hours to form a reaction solution containing ethylene sulfite;
preferably, the glycol is dripped into thionyl chloride within 1-3 hours;
preferably, the reaction solution containing the vinyl sulfite is distilled to form neutral vinyl sulfite.
In one embodiment of the present invention, in the condensation reaction, the molar ratio of the thionyl chloride to ethylene glycol is (1 to 3): 1.
In one embodiment of the present invention, the vinyl sulfite is added dropwise to the mixture over 1 to 3 hours.
In the invention, the method for preparing the vinyl sulfate avoids a water system heterogeneous oxidation reaction mode adopted in the prior art. The method directly reacts in the organic solvent, solves the practical problem that the vinyl sulfate ester is decomposed in water from the source, and obviously reduces the water residue and the free acid residue in the product, thereby improving the reaction yield of the vinyl sulfate ester and improving the purity of the product.
In the non-aqueous reaction system, the vinyl sulfate product has a stable structure, does not need to strictly limit the oxidation reaction temperature, avoids the traditional low-temperature reaction mode, does not need to carry out an additional low-temperature freezing means, can meet the requirement by adopting a normal-temperature circulating water mode to cool timely, and greatly reduces the reaction energy consumption and the equipment investment.
More remarkably, compared with the traditional technical means, the whole reaction process of the invention does not involve the generation of wastewater, is environment-friendly, belongs to an environment-friendly process, and has more advantages under the situation that the requirement on the environment is increasingly strict.
Other features and aspects will become apparent from the following detailed description, and from the claims.
Detailed Description
Unless otherwise defined, technical or scientific terms used in the claims and the specification should have the ordinary meaning as understood by those of ordinary skill in the art to which the invention belongs. Unless otherwise indicated, all parts are parts by weight and all percentages are percentages by weight.
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the specific embodiments described below.
In the present invention, the term "available chlorine" is defined as the chlorine of hypochlorite in the oxidizing agent of the present invention.
In the present invention, the method for preparing vinyl sulfate comprises: (1) providing a mixture of an oxidizing agent and an organic solvent, wherein the oxidizing agent comprises calcium hypochlorite; and (2) adding vinyl sulfite to the mixture to form vinyl sulfate. In particular embodiments, the oxidizing agent is selected from calcium hypochlorite or bleaching powder. In the present invention, the bleaching powder is usually a mixture of calcium hydroxide, calcium chloride and calcium hypochlorite, the main component of which is calcium hypochlorite [ Ca (ClO) ]2]The content of available chlorine is 30-38%. The bleaching powder may be a commercially available product, for example, from Chanxagming Ribes chemical Co. In the present invention, the oxidizing agent of the present invention may optionally be dry or substantially free of water in order to be compatible with the non-aqueous reaction system of the present invention.
In the present invention, the organic solvent is selected from one or more of ester solvents, ether solvents, alcohol solvents, nitrile solvents, ketone solvents, halogenated alkane solvents, and aromatic hydrocarbon solvents.
In a specific embodiment, the ester is selected from the group consisting of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl acetate, ethyl acetate and propyl acetate.
In a specific embodiment, the ether is selected from the group consisting of diethyl ether, 1, 4-dioxane, tetrahydrofuran, and combinations of one or more of ethylene glycol dimethyl ether.
In particular embodiments, the alcohol is selected from the group consisting of methanol, ethanol, butanol, propanol, butanol, and isopropanol.
In a particular embodiment, the nitrile is selected from acetonitrile, propionitrile, or a combination thereof.
In a specific embodiment, the ketone is selected from acetone, methyl ethyl ketone, cyclohexanone, or any combination thereof.
In a particular embodiment, the haloalkane is selected from dichloromethane, dichloroethane, or any combination thereof.
In a particular embodiment, the aromatic hydrocarbon is selected from benzene, toluene, xylene, chlorobenzene or any combination thereof.
In the present invention, the amount of the organic solvent to be added may be appropriately adjusted depending on the solubility of vinyl sulfate in various solvents, as long as the amount of the organic solvent to be added is sufficient to dissolve the product vinyl sulfate. In a specific embodiment, the adding amount of the organic solvent is 300-1000%, 300-900%, 300-800%, 300-700%, 300-600%, 300-500%, 300-400%, 400-1000%, 400-900%, 400-800%, 400-700%, 400-600%, 400-500%, 500-1000% of the weight of the ethylene sulfite, 500% -900%, 500% -800%, 500% -700%, 500% -600%, 600% -1000%, 600% -900%, 600% -800%, 600% -700%, 700% -1000%, 700% -900%, 700% -800%, 800% -1000%, 800% -900% or 900% -1000%.
In the present invention, the amount of the oxidizing agent added is adjusted according to the amount of the added vinyl sulfite. Typically, the oxidizing agent is added in a slight excess over the amount of vinyl sulfite added to allow for sufficient conversion of the vinyl sulfite to vinyl sulfate. In a specific embodiment, the molar ratio of the oxidizing agent to the vinyl sulfite is (1-1.3): 1, (1-1.2): 1, (1-1.1): 1, (1-1.05): 1, (1.05-1.3): 1, (1.05-1.2): 1, (1.05-1.1): 1, (1.1-1.3): 1, (1.1-1.2): 1 or (1.2-1.3): 1 in terms of available chlorine.
In order to accelerate the reaction, a catalyst may be further added in step (1) of the process of the present invention. To accommodate the non-aqueous reaction system of the present invention, the catalyst of the present invention may optionally be dry or substantially free of water. In a specific embodiment, the catalyst is selected from ruthenium trichloride, ruthenium oxide, or a combination thereof.
In the present invention, the amount of the catalyst to be added is adjusted according to the amount of the oxidizing agent to be added. Generally, the catalyst is added in an amount of 0.01 to 0.2%, 0.01 to 0.15%, 0.01 to 0.1%, 0.01 to 0.05%, 0.05 to 0.2%, 0.05 to 0.15%, 0.05 to 0.1%, 0.1 to 0.2%, 0.1 to 0.15%, or 0.15 to 0.2% by mass of the oxidizing agent.
In a specific embodiment, the step (2) comprises adding (or dropping) vinyl sulfite into the mixture under stirring at room temperature or at a temperature of 0-60 ℃, 0-50 ℃, 0-40 ℃, 0-30 ℃, 0-20 ℃, 0-10 ℃, 10-60 ℃, 10-50 ℃, 10-40 ℃, 10-30 ℃, 10-20 ℃, 20-60 ℃, 20-50 ℃, 20-40 ℃, 20-30 ℃, 30-60 ℃, 30-50 ℃, 30-40 ℃, 40-60 ℃, 40-50 ℃ or 50-60 ℃, and reacting for 1-12 hours, 1-10 hours, 1-8 hours, 1-6 hours, 1-4 hours, 1-2 hours, 2-12 hours, 2-10 hours, 2-8 hours, 2-6 hours, 2-4 hours, 4-12 hours, 4-10 hours, 4-8 hours, 4-6 hours, 6-12 hours, 6-10 hours, 6-8 hours, 8-12 hours, 8-10 hours or 10-12 hours, and forming the reaction solution containing the vinyl sulfate.
After the reaction liquid containing the vinyl sulfate is formed, in order to obtain pure vinyl sulfate, the method of the invention further comprises the following steps: filtering the reaction solution containing the vinyl sulfate. The filtration process can be carried out in a manner known to those skilled in the art, provided that the loss of vinyl sulfate is minimized and the yield of vinyl sulfate is increased. The resulting filtrate is filtered, concentrated and recrystallized (e.g., with dichloromethane) to provide pure vinyl sulfate.
In the present invention, the ethylene sulfite may be commercially available or homemade. The vinyl sulfite is readily available to those skilled in the art. In a particular embodiment of the invention, the vinyl sulfite may be prepared by a condensation reaction of ethylene glycol and thionyl chloride. Adding ethylene glycol into thionyl chloride, and reacting at 50-80 ℃, 50-70 ℃, 50-60 ℃, 60-80 ℃, 60-70 ℃ or 70-80 ℃ for 1-3 hours, 1-2.5 hours, 1-2 hours, 1-1.5 hours, 1.5-3 hours, 1.5-2.5 hours, 1.5-2 hours, 2-3 hours, 2-2.5 hours or 2.5-3 hours to form a reaction solution containing vinyl sulfite.
For economic reasons, the ethylene glycol is dripped into the thionyl chloride within 1-3 hours, 1-2.5 hours, 1-2 hours, 1-1.5 hours, 1.5-3 hours, 1.5-2.5 hours, 1.5-2 hours, 2-3 hours, 2-2.5 hours or 2.5-3 hours.
To obtain a relatively pure vinyl sulfite, the reaction solution comprising vinyl sulfite may be subjected to distillation to provide neutral vinyl sulfite. In a specific embodiment of the present invention, the molar ratio of the thionyl chloride and ethylene glycol to be subjected to the condensation reaction is (1 to 3):1, (1 to 2.5):1, (1 to 2):1, (1 to 1.5):1, (1.5 to 3):1, (1.5 to 2.5):1, (1.5 to 2):1, (2 to 3):1, (2 to 2.5):1 or (2.5 to 3): 1.
For economic reasons, vinyl sulfite is added dropwise to the mixture over 1 to 3 hours, 1 to 2.5 hours, 1 to 2 hours, 1 to 1.5 hours, 1.5 to 3 hours, 1.5 to 2.5 hours, 1.5 to 2 hours, 2 to 3 hours, 2 to 2.5 hours, or 2.5 to 3 hours.
In a more specific embodiment of the present invention, the present invention is a process for preparing vinyl sulfate by:
(1) condensation reaction
Taking ethylene glycol and thionyl chloride as reaction raw materials, and dropwise adding ethylene glycol into a thionyl chloride-containing reactor with a tail gas absorption device at normal temperature and normal pressure; after the dropwise adding is finished, heating to 50-80 ℃, and continuing to perform heat preservation reaction for 1-3 hours to obtain a reaction solution of the ethylene sulfite;
distilling the reaction liquid to obtain neutral ethylene sulfite for later use.
(2) Oxidation reaction
Adding a non-aqueous organic solvent, an oxidant bleaching powder and a catalyst into an oxidation reaction kettle. Dropwise adding ethylene sulfite at 0-60 ℃ while stirring; after the dropwise addition is finished, the reaction is continued for 1-12 hours under heat preservation, then the filtration is carried out, and the filtrate is concentrated to obtain a vinyl sulfate crude product;
and recrystallizing and purifying to obtain the high-purity vinyl sulfate product.
In the present invention, the molar ratio of thionyl chloride to ethylene glycol in the condensation reaction is (1-3): 1, preferably (1-2): 1, and more preferably (1.1-1.5): 1.
In the oxidation reaction, the non-aqueous organic solvent is selected from one or a mixture of esters, ethers, alcohols, nitriles, ketones, halogenated alkanes and aromatic hydrocarbons. Wherein the ester solvent is selected from dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl acetate, ethyl acetate or propyl acetate; the ether solvent is selected from diethyl ether, 1, 4-dioxane, tetrahydrofuran or ethylene glycol dimethyl ether; the alcohol solvent is selected from methanol, ethanol, butanol, propanol, butanol or isopropanol; the nitrile solvent is selected from acetonitrile or propionitrile; the ketone solvent is selected from acetone, methyl ethyl ketone or cyclohexanone; the halogenated alkane solvent is selected from dichloromethane or dichloroethane; the aromatic hydrocarbon solvent is selected from benzene, toluene, xylene or chlorobenzene.
In the invention, the addition amount of the non-aqueous organic solvent is 3-10 times of the mass of the ethylene sulfite. This may be adjusted as appropriate depending on the solubility of the vinyl sulfate in the different solvents, as long as the product vinyl sulfate is sufficiently dissolved.
In the oxidation reaction, the molar ratio of the bleaching powder (calculated by available chlorine) as an oxidant to the ethylene sulfite is (1-1.3): 1.
The oxidation reaction catalyst is ruthenium trichloride or ruthenium oxide. The dosage of the catalyst is 0.01-0.2% of the mass of the bleaching powder.
In the condensation reaction, the dripping time of the ethylene glycol is 1-3 hours. In the oxidation reaction, the dripping time of the ethylene sulfite is 1-3 hours.
The present invention will be described in further detail with reference to specific examples, so that the advantages of the present invention will be more apparent. It should be understood that the description is intended for purposes of illustration only and is not intended to limit the scope of the present disclosure. The experimental procedures, in which specific conditions are not specified, in the following examples are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
Example 1
1. Condensation reaction:
ethylene glycol and thionyl chloride are used as raw materials. 357g (3mol) of thionyl chloride was added to a reaction flask equipped with a stirring device and a tail gas absorption device. 124g (2mol) of ethylene glycol was added dropwise at normal temperature and pressure over 3 hours. After the dropwise addition, the temperature is raised to 80 ℃ for continuous heat preservation reaction for 1 hour, and the generated hydrogen chloride tail gas is absorbed into hydrochloric acid by water.
After the reaction, the reaction solution of the ethylene sulfite was distilled under reduced pressure to obtain 202g of neutral ethylene sulfite. The purity of the obtained vinyl sulfite by Gas Chromatography (GC) was 99.1%, and the yield was 97.1%.
2. And (3) oxidation reaction:
288g of bleaching powder with 30 percent of available chlorine, 1400g of dichloromethane and 0.57g of ruthenium trichloride as a catalyst are added into an oxidation reaction bottle, and 202g of the ethylene sulfite in the step 1 starts to be dripped into the oxidation reaction bottle under stirring at 10 ℃, wherein the dripping time is 3 hours. The temperature was slowly raised to 36 ℃ during the dropwise addition. After the dropwise addition, the reaction was continued at this temperature for 10 hours. The temperature is reduced to room temperature and filtered, and the filtrate is decompressed and concentrated to obtain 218g of crude solid vinyl sulfate.
And recrystallizing and purifying 218g of the crude vinyl sulfate product by using dichloromethane to obtain 200g of high-purity vinyl sulfate. The GC purity was 99.89%.
Example 2
1. Condensation reaction:
ethylene glycol and thionyl chloride are used as raw materials. 131g (1.1mol) of thionyl chloride were added to a reaction flask equipped with a stirring device and a tail gas absorption device. 62g (1mol) of ethylene glycol was added dropwise at normal temperature and pressure over 1 hour. After the dropwise addition, the temperature is raised to 50 ℃, the reaction is continued for 3 hours, and the generated hydrogen chloride tail gas is absorbed into hydrochloric acid by adopting water.
After the reaction, the reaction solution of the ethylene sulfite was distilled under reduced pressure to obtain 104g of neutral ethylene sulfite. The GC purity of the resulting vinyl sulfite was 98.56% and the yield was 6.3%.
2. Oxidation reaction
114g of bleaching powder with 30 percent of available chlorine, 312g of dimethyl carbonate and 0.012g of ruthenium trichloride serving as a catalyst are added into an oxidation reaction bottle. 104g of the vinyl sulfite obtained in step 1 was added dropwise with stirring at 5 ℃. The dripping time is 1 hour, the temperature is slowly increased to 35 ℃ in the dripping process, and the temperature is increased to 55-60 ℃ after the dripping is finished, and the heat preservation reaction is continued for 1 hour. Cooling to room temperature, filtering, and concentrating the filtrate under reduced pressure to obtain 100g of crude solid vinyl sulfate.
Then, 100g of the crude product of the vinyl sulfate is subjected to recrystallization purification treatment by using dichloromethane, so that 88g of high-purity vinyl sulfate is obtained. The GC purity was 99.92%.
Example 3
1. Condensation reaction
Ethylene glycol and thionyl chloride are used as raw materials. 140g (1.18mol) of thionyl chloride are introduced into a reaction flask with a stirring device and a tail gas absorption device. 62g (1mol) of ethylene glycol was added dropwise at normal temperature and pressure over 1.5 hours. After the dropwise addition, the temperature is raised to 65 ℃, the reaction is continued for 2 hours under the condition of heat preservation, and the generated hydrogen chloride tail gas is absorbed into hydrochloric acid by adopting water.
After the reaction, the reaction solution of the ethylene sulfite was distilled under reduced pressure to obtain 105g of neutral ethylene sulfite. The GC purity of the resulting vinyl sulfite was 99.23% and the yield was 97.2%.
2. Oxidation reaction
120g of bleaching powder with available chlorine of 32%, 100g of acetonitrile, 300g of isopropanol and 0.05g of ruthenium oxide serving as a catalyst are added into an oxidation reaction bottle. 105g of the vinyl sulfite obtained in step 1 was added dropwise with stirring at room temperature of 20 ℃. The dripping time is 1 hour, the temperature is slowly raised to 43 ℃ in the dripping process, and the temperature is kept at 40-45 ℃ after the dripping is finished for reaction for 5 hours. Cooling to room temperature, filtering, and concentrating the filtrate under reduced pressure to obtain 108g of a crude solid vinyl sulfate product.
And recrystallizing and purifying 108g of the crude vinyl sulfate product by using dichloromethane to obtain 98g of high-purity vinyl sulfate. The GC purity was 99.89%.
Example 4
1. Condensation reaction
Ethylene glycol and thionyl chloride are used as raw materials. 178g (1.5mol) of thionyl chloride were added to a reaction flask with a stirring device and a tail gas absorption device. 80g (1.3mol) of ethylene glycol was added dropwise at normal temperature and pressure over 1 hour. After the dropwise addition, the temperature is raised to 65 ℃, the reaction is continued for 2 hours under the condition of heat preservation, and the generated hydrogen chloride tail gas is absorbed into hydrochloric acid by adopting water.
After the reaction, the reaction solution of the ethylene sulfite was distilled under reduced pressure to obtain 132g of neutral ethylene sulfite. The GC purity of the resulting vinyl sulfite was 98.91% and the yield was 94.3%.
2. Oxidation reaction
180g of bleaching powder with the available chlorine of 28 percent, 500g of 1, 4-dioxane and 0.03g of catalyst ruthenium trichloride are added into an oxidation reaction bottle. 132g of the above-mentioned vinyl sulfite was started to be added dropwise with stirring at 25 ℃ at room temperature. The dripping time is 2 hours, the temperature is slowly increased to 36 ℃ in the dripping process, and the temperature is kept at 30-36 ℃ after the dripping is finished and the reaction is kept for 8 hours. Cooling to room temperature, filtering, and concentrating the filtrate under reduced pressure to obtain crude 136g of solid vinyl sulfate.
And recrystallizing and purifying 136g of the crude vinyl sulfate product by using dichloromethane to obtain 121g of high-purity vinyl sulfate. The GC purity was 99.88%.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.
Claims (10)
1. A method of making vinyl sulfate, the method comprising:
(1) providing a mixture of an oxidizing agent and an organic solvent, wherein the oxidizing agent comprises calcium hypochlorite; and
(2) vinyl sulfite is added to the mixture to form vinyl sulfate.
2. The method of claim 1, wherein the oxidizing agent is selected from calcium hypochlorite or bleaching powder.
3. The method of claim 1, wherein the organic solvent is selected from the group consisting of esters, ethers, alcohols, nitriles, ketones, halogenated alkanes, and combinations of one or more of aromatic hydrocarbons;
preferably, the adding amount of the organic solvent is 300-1000% of the mass of the ethylene sulfite.
4. The method of claim 3, wherein the ester is selected from the group consisting of one or more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl acetate, ethyl acetate, and propyl acetate;
the ether is selected from one or more of diethyl ether, 1, 4-dioxane, tetrahydrofuran and glycol dimethyl ether;
the alcohol is selected from one or more of methanol, ethanol, butanol, propanol, butanol and isopropanol;
the nitrile is selected from acetonitrile, propionitrile, or a combination thereof;
the ketone is selected from acetone, methyl ethyl ketone, cyclohexanone or any combination thereof;
the halogenated alkane is selected from dichloromethane, dichloroethane or any combination thereof; and
the aromatic hydrocarbon is selected from benzene, toluene, xylene, chlorobenzene or any combination thereof.
5. The method of claim 1, wherein the molar ratio of the oxidant to the vinyl sulfite is (1-1.3): 1, in terms of available chlorine.
6. The method of claim 1, wherein in step (1), the mixture further comprises a catalyst;
preferably, the catalyst is selected from ruthenium trichloride, ruthenium oxide or a combination thereof;
preferably, the addition amount of the catalyst is 0.01-0.2% by mass of the oxidant.
7. The method according to claim 1, wherein in the step (2), under stirring conditions, at a temperature of 0-60 ℃, vinyl sulfite is dropwise added into the mixture, and the mixture is subjected to heat preservation reaction for 1-12 hours to form a reaction solution containing vinyl sulfate;
preferably, the method further comprises: and filtering the reaction liquid containing the vinyl sulfate, and concentrating and recrystallizing to form the vinyl sulfate.
8. The method of claim 1, wherein in step (2), the vinyl sulfite is prepared by a condensation reaction of ethylene glycol and thionyl chloride;
preferably, ethylene glycol is added into thionyl chloride and reacted at a temperature of 50-80 ℃ for 1-3 hours to form a reaction solution containing ethylene sulfite;
preferably, the glycol is dripped into thionyl chloride within 1-3 hours;
preferably, the reaction solution containing the vinyl sulfite is distilled to form neutral vinyl sulfite.
9. The method according to claim 8, wherein the molar ratio of thionyl chloride to ethylene glycol in the condensation reaction is (1-3): 1.
10. The method of claim 7, wherein vinyl sulfite is added dropwise to the mixture over 1 to 3 hours.
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| CN112679466A (en) * | 2020-12-27 | 2021-04-20 | 江苏瀚康新材料有限公司 | Method for synthesizing vinyl sulfate |
| CN113416178A (en) * | 2021-05-18 | 2021-09-21 | 杭州师范大学 | Lithium battery additive amido vinyl sulfate, and preparation method and application thereof |
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