CN114181190A - 2, 4-butane sultone and preparation method and application thereof - Google Patents
2, 4-butane sultone and preparation method and application thereof Download PDFInfo
- Publication number
- CN114181190A CN114181190A CN202111576672.3A CN202111576672A CN114181190A CN 114181190 A CN114181190 A CN 114181190A CN 202111576672 A CN202111576672 A CN 202111576672A CN 114181190 A CN114181190 A CN 114181190A
- Authority
- CN
- China
- Prior art keywords
- butane sultone
- preparation
- butanol
- chloro
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- VWEYDBUEGDKEHC-UHFFFAOYSA-N 3-methyloxathiolane 2,2-dioxide Chemical compound CC1CCOS1(=O)=O VWEYDBUEGDKEHC-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims abstract description 60
- UTBUFLARLRSVFF-UHFFFAOYSA-N 3-chlorobutan-1-ol Chemical compound CC(Cl)CCO UTBUFLARLRSVFF-UHFFFAOYSA-N 0.000 claims abstract description 40
- 235000019437 butane-1,3-diol Nutrition 0.000 claims abstract description 30
- 239000012320 chlorinating reagent Substances 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 7
- 239000003792 electrolyte Substances 0.000 claims abstract description 6
- 230000000996 additive effect Effects 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 21
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- 238000006277 sulfonation reaction Methods 0.000 claims description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 14
- 238000004821 distillation Methods 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 230000020477 pH reduction Effects 0.000 claims description 12
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 12
- 235000010265 sodium sulphite Nutrition 0.000 claims description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- 230000018044 dehydration Effects 0.000 claims description 9
- 238000006297 dehydration reaction Methods 0.000 claims description 9
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 7
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 4
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 4
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 4
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 3
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 3
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims description 3
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 3
- 239000005049 silicon tetrachloride Substances 0.000 claims description 3
- 239000001119 stannous chloride Substances 0.000 claims description 3
- 235000011150 stannous chloride Nutrition 0.000 claims description 3
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 claims description 3
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 2
- 229910015900 BF3 Inorganic materials 0.000 claims description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 claims description 2
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 claims description 2
- 229940099427 potassium bisulfite Drugs 0.000 claims description 2
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 claims description 2
- RWPGFSMJFRPDDP-UHFFFAOYSA-L potassium metabisulfite Chemical compound [K+].[K+].[O-]S(=O)S([O-])(=O)=O RWPGFSMJFRPDDP-UHFFFAOYSA-L 0.000 claims description 2
- 229940043349 potassium metabisulfite Drugs 0.000 claims description 2
- 235000010263 potassium metabisulphite Nutrition 0.000 claims description 2
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 2
- 235000019252 potassium sulphite Nutrition 0.000 claims description 2
- 229940001607 sodium bisulfite Drugs 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 11
- 231100000419 toxicity Toxicity 0.000 abstract description 3
- 230000001988 toxicity Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 238000005660 chlorination reaction Methods 0.000 description 15
- 239000000706 filtrate Substances 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 12
- 238000005406 washing Methods 0.000 description 10
- 238000001914 filtration Methods 0.000 description 9
- 229940001482 sodium sulfite Drugs 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 description 6
- 238000004537 pulping Methods 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- KMBRJVMBQNMRDM-UHFFFAOYSA-N 1-hydroxybutane-1-sulfonic acid Chemical compound CCCC(O)S(O)(=O)=O KMBRJVMBQNMRDM-UHFFFAOYSA-N 0.000 description 5
- -1 alkyl sultone compounds Chemical class 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000007363 ring formation reaction Methods 0.000 description 4
- 150000003333 secondary alcohols Chemical class 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- AKMIPCJUTXDZKR-UHFFFAOYSA-N 4-chlorobutan-2-ol Chemical compound CC(O)CCCl AKMIPCJUTXDZKR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 2
- WCASXYBKJHWFMY-NSCUHMNNSA-N 2-Buten-1-ol Chemical compound C\C=C\CO WCASXYBKJHWFMY-NSCUHMNNSA-N 0.000 description 2
- YEGPVWSPNYPPIK-UHFFFAOYSA-N 4-hydroxybutane-1-sulfonic acid Chemical compound OCCCCS(O)(=O)=O YEGPVWSPNYPPIK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- SIIVGPQREKVCOP-UHFFFAOYSA-N but-1-en-1-ol Chemical compound CCC=CO SIIVGPQREKVCOP-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 2
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- WCASXYBKJHWFMY-UHFFFAOYSA-N gamma-methylallyl alcohol Natural products CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000003138 primary alcohols Chemical class 0.000 description 2
- KHZCHGONTXFPLX-UHFFFAOYSA-M sodium;1-hydroxybutane-1-sulfonate Chemical compound [Na+].CCCC(O)S([O-])(=O)=O KHZCHGONTXFPLX-UHFFFAOYSA-M 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HXHGULXINZUGJX-UHFFFAOYSA-N 4-chlorobutanol Chemical compound OCCCCCl HXHGULXINZUGJX-UHFFFAOYSA-N 0.000 description 1
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 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
- 239000002841 Lewis acid Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229940101006 anhydrous sodium sulfite Drugs 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000006210 cyclodehydration reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012022 methylating agents Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
- C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
- C07D327/04—Five-membered rings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides 2, 4-butane sultone and a preparation method and application thereof, wherein the preparation method comprises the steps of firstly reacting 1, 3-butanediol, a chlorinating reagent and a catalyst to obtain 3-chloro-1-butanol; sequentially sulfonating, acidifying and cyclizing the obtained 3-chloro-1-butanol to obtain the 2, 4-butane sultone; the preparation raw materials adopted by the preparation method are low in price, easy to obtain and low in toxicity; the preparation method is simple in preparation process, and the prepared 2, 4-butane sultone is high in yield and purity and can be used as an additive to be added into electrolyte for a lithium ion battery.
Description
Technical Field
The invention belongs to the technical field of material synthesis, and particularly relates to 2, 4-butane sultone and a preparation method and application thereof.
Background
Sulfur-containing lithium ion battery electrolyte additives, particularly alkyl sultone compounds such as 1, 3-propane sultone and 1, 4-butane sultone, can form films on the surfaces of a positive electrode and a negative electrode of a lithium ion battery, and further contribute to improving the high-temperature cycle performance and the storage performance of the lithium ion battery under a high-voltage and high-nickel system; wherein, a methyl group is introduced into the molecular structure of the 2, 4-butane sultone, so that the 2, 4-butane sultone has a lower freezing point, and the use effect of the 2, 4-butane sultone is better than that of other alkyl sultone additives in a low-temperature environment. The excellent performance makes 2, 4-butane sultone one of the most common additives of lithium ion battery electrolyte.
In the synthesis method of 2, 4-butane sultone, crotonaldehyde is most commonly used as a starting material, 1, 4-Michael addition is carried out on crotonaldehyde and sulfite to obtain 3-sulfo-1-butyraldehyde, palladium-carbon catalytic hydrogenation is carried out to obtain a hydroxybutyric acid intermediate, and ring closure is carried out to obtain a final product; application publication No. CN109293625A discloses a method for synthesizing high-purity 1, 4-butane sultone, which comprises the following steps: firstly, adding 4-chlorobutanol and sodium sulfite solution into an alcohol solvent, heating and refluxing for 4-8 hours, obtaining a mixed solution A after refluxing is finished, concentrating the mixed solution A to recover the alcohol solvent, adding hydrochloric acid for acidification, concentrating until the material becomes viscous, adding the alcohol solvent, separating out sodium chloride crystals, filtering, concentrating the filtrate to recover the alcohol solvent, and obtaining 4-hydroxybutanesulfonic acid; then, continuously carrying out flash evaporation dehydration on the 4-hydroxybutanesulfonic acid at the vacuum degree of 1-8 mmHg and the temperature of 130-165 ℃ to obtain industrial grade 1, 4-butanesultone; and finally, adding an azeotrope into the industrial grade 1, 4-butane sultone, fractionating at normal pressure to recover the azeotrope, performing reduced pressure fractionation under the vacuum degree of 2-4 mmHg, and collecting fractions at the temperature of 120-121 ℃ to obtain the high-purity 1, 4-butane sultone. The method is simple and environment-friendly, greatly improves the sulfonation yield, and greatly improves the purity and yield of the 1, 4-butane sultone. Application publication No. CN102807552A discloses a method for synthesizing 2, 4-butane sultone by using butenol (crotyl alcohol) as a raw material, sulfonating the crotyl alcohol into hydroxybutane sulfonate by using bisulfite, acidifying the hydroxybutane sulfonate into hydroxybutane sulfonic acid, and finally performing high-temperature vacuum dehydration and cyclization to obtain the 2, 4-butane sultone. Application publication No. CN112961139A discloses a method for synthesizing 2, 4-butane sultone, which comprises the following steps: firstly, dissolving 1, 3-propane sultone in a first organic solvent under the protection of inert gas in the whole process, then adding sodium hydrogen in batches, and heating to 40-50 ℃ after the addition is finished; then, dropwise adding a methylating agent, and carrying out heat preservation reaction after dropwise adding; and finally, cooling to room temperature, adding ice water, extracting by using a second organic solvent, and rectifying the second organic solvent layer under negative pressure to obtain the final product 2, 4-butane sultone.
However, the synthesis method of 2, 4-butane sultone provided in the above prior art has the problems of toxic raw materials and unsafe process.
Therefore, in order to solve the technical problems, the invention provides a preparation method of 2, 4-butane sultone, which has nontoxic and easily obtained raw materials and safe process.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide 2, 4-butane sultone and a preparation method and application thereof, wherein the preparation method comprises the following steps: firstly, 1, 3-butanediol, a chlorinating agent and a catalyst are reacted to obtain 3-chloro-1-butanol; sequentially sulfonating, acidifying and dehydrating the obtained 3-chloro-1-butanol to obtain the 2, 4-butane sultone; the preparation method is safe in process, and the adopted raw materials are safe and easy to obtain, so that a novel preparation method is provided for preparing the 2, 4-butane sultone.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing 2, 4-butane sultone, comprising the steps of:
(1) reacting 1, 3-butanediol, a chlorinating agent and a catalyst to obtain 3-chloro-1-butanol;
(2) sulfonating, acidifying and dehydrating the 3-chloro-1-butanol to obtain the 2, 4-butane sultone.
The preparation method of the 2, 4-butane sultone provided by the invention comprises two steps: firstly, carrying out chlorination reaction on 1, 3-butanediol and a chlorinating agent in the presence of a catalyst to obtain 3-chloro-1-butanol; then, sulfonating, acidifying and cyclizing the obtained 3-chloro-1-butanol to obtain the 2, 4-butane sultone, wherein the whole reaction flow is shown as a formula I:
one of the raw materials adopted in the preparation method of the 2, 4-butane sultone provided by the invention is 1, 3-butanediol, and the 1, 3-butanediol is a bulk chemical raw material in common daily chemical and rubber and plastic industries, is low in price and is simple to synthesize. 1, 3-butanediol has two hydroxyl functional groups, namely primary alcohol and secondary alcohol respectively, and the secondary alcohol is easier to perform chlorination reaction due to different reactivity and reaction rate of the two hydroxyl groups when performing chlorination reaction, and the secondary alcohol can generate secondary alcohol chloride, namely 3-chloro-1-butanol, with high selectivity under the mediation of Lewis acid or a strong protonic acid auxiliary agent; while the chlorinated or dichloride of the primary alcohol is generated less or cannot be generated; according to the invention, 1, 3-butanediol and a chlorinating agent are prepared into 3-chloro-1-butanol under the condition of the existence of a catalyst by utilizing the principle, the 3-chloro-1-butanol can be directly subjected to sulfonation reaction with the sulfonating agent without separation to generate hydroxybutanesulfonic acid, and the 2, 4-butanesultone can be obtained through acidification and cyclodehydration.
In conclusion, the raw materials adopted by the preparation method of the 2, 4-butane sultone provided by the invention are low in price, easy to obtain and low in toxicity, the preparation method is simple in process, and the prepared 2, 4-butane sultone is high in yield and purity, and completely meets the requirements of lithium ion battery electrolyte on additives.
In the present invention, the acidification and cyclization step can be achieved by conventional selection and conventional implementation of the step of preparing the alkylsulfonic acid lactone, and the acidification and cyclization step is not particularly limited.
Preferably, the chlorinating agent in step (1) comprises any one of hydrogen chloride, thionyl chloride, silicon tetrachloride, trimethylchlorosilane, sodium chloride or potassium chloride or a combination of at least two of the above.
As a preferable technical scheme of the invention, the selected chlorinating agent comprises any one or a combination of at least two of hydrogen chloride, thionyl chloride, silicon tetrachloride, trimethylchlorosilane, sodium chloride or potassium chloride, so that the secondary alcohol in the 1, 3-butanediol can be more selectively generated into the 3-chloro-1-butanol, and the yield of the finally obtained 2, 4-butane sultone is higher.
Preferably, the molar ratio of the 1, 3-butanediol and the chlorinating agent in the step (1) is 1 (1-3), such as 1:1.2, 1:1.4, 1:1.6, 1:1.8, 1:2, 1:2.2, 1:2.4, 1:2.6 or 1: 2.8.
According to the preferable technical scheme, when the molar ratio of the 1, 3-butanediol to the chlorinating reagent is 1 (1-3), the yield of the 3-chloro-1-butanol is improved, and the yield of the 2, 4-butane sultone is improved, on one hand, if the dosage of the 1, 3-butanediol is higher, the chlorination reaction is incomplete, the yield of the 3-chloro-1-butanol is reduced, and the total yield of the 2, 4-butane sultone is reduced; on the other hand, if the amount of 1, 3-butanediol is too low, the selectivity of the chlorination reaction is deteriorated, the content of 4-chloro-2-butanol as a by-product is increased, and more 5-methyl-1, 2-oxathiapentane-2, 2-dioxide as a by-product is finally produced, thereby reducing the yield of 2, 4-butanesultone as a product.
Preferably, the catalyst in step (1) comprises any one or a combination of at least two of aluminum chloride, ferric trichloride, boron trifluoride, titanium tetrachloride, zinc chloride, zinc acetylacetonate or stannous chloride.
Preferably, the molar ratio of the 1, 3-butanediol and the catalyst in the step (1) is 1 (0.05-1), such as 1:0.1, 1:0.15, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8 or 1: 0.9.
Preferably, the temperature of the reaction in step (1) is 0to 100 ℃, for example, 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ or 90 ℃.
Preferably, the reaction time in step (1) is 0.5-8 h, such as 1h, 2h, 3h, 4h, 5h, 6h or 7 h.
Preferably, the reaction of step (1) is carried out in a solvent.
Preferably, the sulfonation of step (2) is carried out in the solvent.
Preferably, the solvent comprises water and/or a linear ether.
Preferably, the solvent comprises any one of deionized water, diethyl ether, methyl tert-butyl ether, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol diethyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether, polyethylene glycol dimethyl ether or polyethylene glycol diethyl ether, or a combination of at least two thereof.
Preferably, the sulfonating agent used for sulfonating in step (2) comprises one or a combination of at least two of sulfur dioxide, thionyl chloride, sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metabisulfite and potassium metabisulfite.
Preferably, the molar ratio of the 1, 3-butanediol and the sulfonating agent in the step (1) is 1 (1-3), such as 1:1.2, 1:1.4, 1:1.6, 1:1.8, 1:2, 1:2.2, 1:2.4, 1:2.6 or 1: 2.8.
Preferably, the temperature of sulfonation in step (2) is 60-100 ℃, such as 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃ or 95 ℃.
Preferably, the sulfonation time in the step (2) is 0.5-8 h, such as 1h, 2h, 3h, 4h, 5h, 6h or 7 h.
Preferably, the step (2) further comprises a step of removing the solvent before acidification.
Preferably, the acidification in the step (2) further comprises the steps of dehydration and distillation.
In the present invention, the dehydration and distillation steps can be carried out by conventional selection and conventional purification means for the step of producing an alkylsulfonic acid lactone, and the dehydration and distillation steps are not particularly limited.
As a preferred technical scheme, the preparation method comprises the following steps:
(1) reacting 1, 3-butanediol, a chlorinating agent and a catalyst in a molar ratio of 1 (1-3) to 0.05-1 in a solvent at 0-100 ℃ for 0.5-8 h to obtain 3-chloro-1-butanol;
(2) and sulfonating the 3-chloro-1-butanol by using a sulfonating reagent, removing a solvent, acidifying, dehydrating and distilling to obtain the 2, 4-butane sultone.
In a second aspect, the invention provides 2, 4-butane sultone, wherein the 2, 4-butane sultone is prepared by the preparation method of the first aspect.
In a third aspect, the invention provides a use of the 2, 4-butane sultone as described in the second aspect as an additive in an electrolyte of a lithium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method of 2, 4-butane sultone provided by the invention comprises the steps of firstly reacting 1, 3-butanediol, a chlorinating reagent and a catalyst to obtain 3-chloro-1-butanol; then, sulfonating, acidifying and cyclizing the obtained 3-chloro-1-butanol to obtain the 2, 4-butane sultone; the preparation raw materials adopted by the preparation method are low in price and easy to obtain, the toxicity is low, the preparation process of the preparation method is simple, the yield of the prepared 2, 4-butane sultone is high, the purity is high, and the requirements of the electrolyte in the lithium ion battery on additives are completely met.
Detailed Description
In the present specification, unless otherwise specified, the following meanings are given to the symbols, units, abbreviations and terms. For example, when numerical ranges are expressed using "or", they include both endpoints, and the units are common. For example, 5 to 25% includes 5% to 25%.
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
A method for preparing 2, 4-butane sultone, comprising the steps of:
(1) putting 0.15mol of anhydrous zinc chloride and 60g of concentrated hydrochloric acid with the mass percentage of 38% into a reaction kettle, adding 0.3mol of 1, 3-butanediol after a stirring solution is clarified, heating to 60 ℃ and reacting for 4 hours to obtain 3-chloro-1-butanol;
(2) dissolving 0.3mol of sodium sulfite and 0.36mol of sodium bisulfite in 325g of deionized water to prepare a solution, slowly dripping into a reaction kettle for obtaining 3-chloro-1-butanol in the step (1), heating to 100 ℃ after finishing dripping, carrying out sulfonation reaction for 6h, distilling under normal pressure to remove the solvent, adding 50g of absolute ethyl alcohol, pulping, washing, carrying out suction filtration, repeating for three times, collecting all filtrate, adding 60g of concentrated hydrochloric acid for acidification for 2h, filtering, carrying out high-temperature dehydration and ring closing at 180 ℃ (5-10 Torr) and carrying out reduced pressure distillation to obtain the 2, 4-butane sultone.
Example 2
A method for preparing 2, 4-butane sultone, comprising the steps of:
(1) putting 0.3mol of 1, 3-butanediol, 270.37g of ethylene glycol dimethyl ether, 0.6mol of deionized water and 0.015mol of zinc acetylacetonate into a reaction kettle, heating to 60 ℃, adding 0.3mol of trimethylchlorosilane into the reaction kettle after a stirring solution is clarified, and carrying out heat preservation reaction for 4 hours to obtain 3-chloro-1-butanol;
(2) dissolving 0.15mol of sodium sulfite and 0.15mol of sodium metabisulfite in 216g of deionized water to prepare a solution, slowly dripping the solution into a reaction kettle for obtaining the 3-chloro-1-butanol in the step (1), heating to 100 ℃ after finishing dripping, carrying out sulfonation reaction for 6 hours, carrying out normal pressure distillation on a lower-layer water phase after liquid separation to remove a solvent to obtain a white solid, adding 50g of absolute ethyl alcohol into the white solid, pulping, washing, carrying out suction filtration for three times, collecting all filtrate, adding 60g of concentrated hydrochloric acid to acidify for 2 hours, filtering, and carrying out high temperature dehydration and ring closing at 180 ℃ (5-10 Torr) and reduced pressure distillation on the filtrate to obtain the 2, 4-butane sultone.
Example 3
A method for preparing 2, 4-butane sultone, comprising the steps of:
(1) putting 0.9mol of trimethylchlorosilane, 487g of diethylene glycol diethyl ether and 0.3mol of anhydrous aluminum chloride into a reaction kettle, heating to 60 ℃, adding 0.3mol of 1, 3-butanediol, and reacting for 4 hours to obtain 3-chloro-1-butanol;
(2) dissolving 0.39mol of sodium sulfite and 0.51mol of sodium bisulfite in 378g of deionized water to prepare a solution, slowly dripping the solution into the reaction kettle of the 3-chloro-1-butanol obtained in the step (1), heating to 100 ℃ after finishing dripping, carrying out sulfonation reaction for 4 hours, stopping the reaction, and carrying out normal pressure distillation on the lower-layer water phase after liquid separation to remove the solvent to obtain a white solid; and adding 50g of absolute ethyl alcohol into the white solid, pulping, washing, performing suction filtration, repeating for three times, collecting all filtrate, adding 60g of concentrated hydrochloric acid for acidification for 2 hours, filtering, dehydrating the filtrate at a high temperature of 180 ℃ (5-10 Torr), closing rings, and performing reduced pressure distillation to obtain the 2, 4-butane sultone.
Example 4
A method for preparing 2, 4-butane sultone, comprising the steps of:
(1) in an ice-water bath, 0.015mol of zinc chloride, 0.6mol of deionized water, 0.3mol of 1, 3-butanediol and 201g of diethylene glycol dimethyl ether are put into a reaction kettle, 0.36mol of thionyl chloride is slowly dripped, the ice-water bath is removed after the dripping is finished, the temperature is raised to 60 ℃ for reaction for 6 hours, and 3-chloro-1-butanol is obtained;
(2) dissolving 0.3mol of sodium sulfite and 0.36mol of sodium bisulfite in 325g of deionized water to prepare a solution, slowly dripping into a reaction kettle for obtaining 3-chloro-1-butanol in the step (1), heating to 100 ℃ after finishing dripping, carrying out sulfonation reaction for 6h, distilling under normal pressure to remove the solvent, adding 50g of absolute ethyl alcohol, pulping, washing, carrying out suction filtration, repeating for three times, collecting all filtrate, adding 60g of concentrated hydrochloric acid for acidification for 2h, filtering, carrying out high-temperature dehydration and ring closing at 180 ℃ (5-10 Torr) and carrying out reduced pressure distillation to obtain the 2, 4-butane sultone.
Example 5
A method for preparing 2, 4-butane sultone, comprising the steps of:
(1) putting 0.6mol of potassium chloride, 0.3mol of zinc chloride, 6mol of deionized water, 0.9mol of phosphoric acid and 0.3mol of 1, 3-butanediol into a reaction kettle, heating to 60 ℃, carrying out reflux water diversion, and carrying out heat preservation reaction for 8 hours to obtain 29.64g of 3-chloro-1-butanol;
(2) dissolving 0.39mol of sodium sulfite and 0.51mol of sodium metabisulfite in 594.5g of deionized water to prepare a solution, slowly dripping the solution into the reaction kettle of the 3-chloro-1-butanol obtained in the step (1), heating to 100 ℃ after finishing dripping, carrying out sulfonation reaction for 8 hours, stopping the reaction, and carrying out normal pressure distillation on the lower-layer water phase after liquid separation to remove the solvent to obtain a white solid; and adding 50g of absolute ethyl alcohol into the white solid, pulping, washing, performing suction filtration, repeating for three times, collecting all filtrate, adding 60g of concentrated hydrochloric acid, acidifying for 6 hours at 60 ℃, filtering, dehydrating and closing the ring at a high temperature of 180 ℃ (5-10 Torr), and performing reduced pressure distillation on the filtrate to obtain the 2, 4-butane sultone.
Example 6
A method for preparing 2, 4-butane sultone, comprising the steps of:
(1) 0.6mol of sodium chloride, 0.3mol of stannous chloride, 6mol of deionized water, 0.9mol of sulfuric acid and 0.3mol of 1, 3-butanediol are put into a reaction kettle, 135g of ethylene glycol diethyl ether is added slowly, the temperature is raised to 60 ℃ for reflux water diversion, and the reaction is carried out for 8 hours under heat preservation to obtain 3-chloro-1-butanol;
(2) dissolving 0.39mol of sodium sulfite and 0.51mol of sodium bisulfite in 432g of deionized water to prepare a solution, slowly dripping into the reaction kettle of the 3-chloro-1-butanol obtained in the step (1), heating to 100 ℃ after dripping, keeping the temperature for reaction for 6 hours, sulfonating, stopping reaction, separating liquid, and distilling the lower-layer water phase at normal pressure to remove the solvent to obtain a white solid; adding 50g of absolute ethyl alcohol into the white solid, pulping, washing, performing suction filtration, repeating for three times, collecting all filtrate, adding 60g of concentrated hydrochloric acid, acidifying for 2 hours at 60 ℃, filtering, dehydrating the filtrate at 180 ℃ (5-10 Torr), closing the ring, and performing reduced pressure distillation to obtain the 2, 4-butane sultone.
Example 7
A method for preparing 2, 4-butane sultone, which is different from the method in the embodiment 1 only in that the reaction temperature in the step (1) is 0 ℃, the reaction time is 8h, and other conditions, parameters and steps are the same as the embodiment 1.
Example 8
A method for preparing 2, 4-butane sultone, which is different from the method in the embodiment 1 only in that the reaction temperature in the step (1) is 100 ℃, the reaction time is 0.5h, and other conditions, parameters and steps are the same as the embodiment 1.
Example 9
A method for preparing 2, 4-butane sultone, which is different from the method in the embodiment 1 only in that the temperature of sulfonation reaction in the step (2) is 60 ℃, the reaction time is 8h, and other conditions, parameters and steps are the same as the embodiment 1.
Example 10
A process for the preparation of 2, 4-butanesultone which differs from example 2 only in that the amount of chlorotrimethylsilane used is 0.2mol, and the other conditions, parameters and procedures are the same as in example 1.
Example 11
A process for preparing 2, 4-butane sultone which differs from example 2 only in that the amount of chlorotrimethylsilane used is 1mol and the other conditions, parameters and steps are the same as in example 1.
Example 12
A method for preparing 2, 4-butane sultone, which is different from the method in the embodiment 2 only in that the reaction temperature in the step (1) is 120 ℃, the reaction time is 0.5h, and other conditions, parameters and steps are the same as the embodiment 1.
Comparative example 1
A preparation method of 2, 4-butane sultone specifically comprises the following steps (refer to example 1 in CN 102807552A):
(1) respectively adding 2mol of anhydrous sodium sulfite and 500mL of water into a 1000mL three-neck flask with a stirrer and a thermometer, stirring until the mixture is uniformly mixed, controlling the reaction temperature to be not more than 50 ℃ and the pH value to be 6.5, dropwise adding a mixed solution of 1mol of butenol and 20mL of sulfuric acid within 2h under the condition that the sodium sulfite and the sodium bisulfite exist in the system, continuously stirring for 30min after dropwise adding, concentrating, cooling and filtering the reaction solution to remove crystalline sodium sulfate, washing for a plurality of times by using absolute ethyl alcohol, and mixing the filtrate and the washing solution to form a sodium hydroxybutanesulfonate aqueous solution;
(2) adding 90mL of concentrated hydrochloric acid and 200mL of absolute ethanol into the sodium hydroxybutanesulfonate aqueous solution, stirring for 15min, placing in a refrigerator, freezing to 0 ℃, filtering to remove precipitated sodium chloride, and washing sodium chloride crystals with ethanol for several times. And mixing the filtrate with the washing solution, distilling under reduced pressure to remove the solvent and water to obtain reddish brown oily hydroxybutanesulfonic acid liquid, dehydrating under a certain negative pressure, then increasing the negative pressure, replacing a receiving bottle, reacting for 6 hours after the temperature reaches 180 ℃ and the vacuum degree is 5-10 Torr, and obtaining the 2, 4-butanesultone.
And (3) performance testing:
(1) selectivity of chlorination reaction: performing High Performance Liquid Chromatography (HPLC) analysis on the solution obtained after the chlorination reaction in the step (1) of the embodiment 1-12, and quantifying the obtained 3-chloro-1-butanol and 4-chloro-2-butanol by an external standard method, wherein the mass percentage of the 3-chloro-1-butanol in the total amount of the 3-chloro-1-butanol and the 4-chloro-2-butanol is calculated;
(2) the total yield is as follows: obtaining 0.3mol of 1, 3-butanediol according to theoretical calculation to finally obtain 40.8g (0.3mol) of 2, 4-butane sultone, and calculating to obtain the total yield by utilizing the actual division of the mass of the obtained 2, 4-butane sultone and the theoretical mass;
(3) purity: and (3) dissolving the finally obtained sample in a dimethyl carbonate solvent, analyzing by using a gas chromatograph, and calculating the ratio of the peak area of the 2, 4-butane sultone dissolved in the dimethyl carbonate to the peak area before dissolution, namely the purity of the 2, 4-butane sultone.
Examples 1-12 and comparative example 1 were tested according to the test methods described above, with the test results shown in table 1:
TABLE 1
As can be seen from the data in table 1:
firstly, the preparation method provided by the invention adopts 1, 3-butanediol to carry out chlorination reaction, the chlorination reaction has high reaction selectivity for preparing 3-chloro-1-butanol, the product 2, 4-butane sultone can be obtained by further carrying out sulfonation, acidification and cyclization by using the 3-chloro-1-butanol as a raw material, the yield is high, the purity also meets the basic requirements of lithium batteries, and the raw materials adopted by the preparation method are simple and easy to obtain, so that the preparation method has great industrial mass production potential.
Secondly, the choice of different chlorinating agents and catalysts has different effects on the selectivity of chlorination. At present, ZnCl is used2The chlorination is carried out under the acidic condition, and the selectivity of the chlorination reaction can reach about 97 percent.
Specifically, comparing example 1 with examples 7, 8 and 9, and comparing example 2 with example 12, it can be seen that the chlorination reaction selectivity is reduced due to the over-high temperature of the chlorination reaction; still further, as can be seen from the comparison between example 2 and examples 10 and 11, the amount of the chlorinating agent also has an influence on the selectivity, and too much amount of the chlorinating agent also causes the selectivity to be reduced; in the case of insufficient amount of the chloride, the selectivity is not reduced, but the chlorination is incomplete, so that the 3-chloro-1-butanol is reduced, and the total yield is influenced finally.
Comparing example 1 with comparative example 1, it can be seen that the preparation method provided in example 1 has an improvement in both the overall yield and purity of 2, 4-butane sultone over the method provided in the prior art (CN 102807552A).
The applicant states that the invention is illustrated by the above examples to be a 2, 4-butane sultone and its preparation and use, but the invention is not limited to the above examples, i.e. it is not meant to imply that the invention must be practiced by means of the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A preparation method of 2, 4-butane sultone is characterized by comprising the following steps:
(1) reacting 1, 3-butanediol, a chlorinating agent and a catalyst to obtain 3-chloro-1-butanol;
(2) sulfonating, acidifying and cyclizing the 3-chloro-1-butanol to obtain the 2, 4-butane sultone.
2. The preparation method according to claim 1, wherein the chlorinating agent in step (1) comprises any one or a combination of at least two of hydrogen chloride, thionyl chloride, silicon tetrachloride, trimethylchlorosilane, sodium chloride or potassium chloride;
preferably, the molar ratio of the 1, 3-butanediol to the chlorinating agent in the step (1) is 1 (1-3).
3. The production method according to claim 1 or 2, wherein the catalyst of step (1) comprises any one of aluminum chloride, ferric trichloride, boron trifluoride, titanium tetrachloride, zinc chloride, zinc acetylacetonate or stannous chloride or a combination of at least two thereof;
preferably, the molar ratio of the 1, 3-butanediol to the catalyst in the step (1) is 1 (0.05-1).
4. The method according to any one of claims 1 to 3, wherein the temperature of the reaction in step (1) is 0to 100 ℃;
preferably, the reaction time in the step (1) is 0.5-8 h.
5. The production method according to any one of claims 1 to 4, wherein the reaction in step (1) is carried out in a solvent;
preferably, the sulfonation of step (2) is carried out in the solvent;
preferably, the solvent comprises water and/or a linear ether;
preferably, the solvent comprises any one of deionized water, diethyl ether, methyl tert-butyl ether, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol diethyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether, polyethylene glycol dimethyl ether or polyethylene glycol diethyl ether, or a combination of at least two thereof.
6. The preparation method according to any one of claims 1 to 5, wherein the sulfonation reagent used in the step (2) comprises any one or a combination of at least two of sulfur dioxide, thionyl chloride, sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metabisulfite or potassium metabisulfite;
preferably, the molar ratio of the 1, 3-butanediol and the sulfonating reagent in the step (1) is 1 (1-3);
preferably, the temperature of sulfonation in the step (2) is 60-100 ℃;
preferably, the sulfonation time in the step (2) is 0.5-8 h.
7. The method according to any one of claims 1 to 6, wherein the step (2) further comprises a step of removing the solvent before the acidification;
preferably, the acidification in the step (2) further comprises the steps of dehydration and distillation.
8. The production method according to any one of claims 1 to 7, characterized by comprising the steps of:
(1) reacting 1, 3-butanediol, a chlorinating agent and a catalyst in a molar ratio of 1 (1-3) to 0.05-1 in a solvent at 0-100 ℃ for 0.5-8 h to obtain 3-chloro-1-butanol;
(2) and sequentially sulfonating the 3-chloro-1-butanol, removing a solvent, acidifying, dehydrating and distilling to obtain the 2, 4-butane sultone.
9. 2, 4-butane sultone, wherein the 2, 4-butane sultone is prepared by the preparation method of any one of claims 1 to 8.
10. Use of the 2, 4-butane sultone of claim 9 as an additive in lithium ion battery electrolytes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111576672.3A CN114181190B (en) | 2021-12-22 | 2021-12-22 | 2, 4-butane sultone and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111576672.3A CN114181190B (en) | 2021-12-22 | 2021-12-22 | 2, 4-butane sultone and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114181190A true CN114181190A (en) | 2022-03-15 |
| CN114181190B CN114181190B (en) | 2023-04-25 |
Family
ID=80544695
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111576672.3A Active CN114181190B (en) | 2021-12-22 | 2021-12-22 | 2, 4-butane sultone and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114181190B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102807552A (en) * | 2012-07-31 | 2012-12-05 | 福建创鑫科技开发有限公司 | Method for synthetizing 2, 4-butane sulfonic acid lactone |
| CN114805288A (en) * | 2021-01-20 | 2022-07-29 | 武汉松石科技股份有限公司 | Method for preparing 2, 4-butane sultone |
-
2021
- 2021-12-22 CN CN202111576672.3A patent/CN114181190B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102807552A (en) * | 2012-07-31 | 2012-12-05 | 福建创鑫科技开发有限公司 | Method for synthetizing 2, 4-butane sulfonic acid lactone |
| CN114805288A (en) * | 2021-01-20 | 2022-07-29 | 武汉松石科技股份有限公司 | Method for preparing 2, 4-butane sultone |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114181190B (en) | 2023-04-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104495767B (en) | A kind of preparation method of imidodisulfuryl fluoride lithium salt | |
| CN107698611B (en) | A kind of synthetic method of electrolyte lithium salt difluorine oxalic acid boracic acid lithium | |
| CN111116429B (en) | Method for synthesizing alkali metal trifluoromethanesulfonate or alkali metal methanesulfonate | |
| CN112250662B (en) | Preparation method of cyclic sulfate | |
| CN110156811A (en) | A kind of synthesis preparation method of the bicyclic sulfuric ester of pentaerythrite | |
| CN105503812A (en) | Continuous production method for high-purity vinylene carbonate | |
| CN112142574B (en) | Synthesis method of 9, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene | |
| CN109293625A (en) | A kind of synthetic method of high-purity 1,4- butane sultones | |
| CN114873571B (en) | Preparation method of difluoro sulfonyl imide salt | |
| CN113880057A (en) | Clean production process of bis (fluorosulfonyl) imide | |
| CN103360410B (en) | Ofloxacine USP 23 preparation method | |
| JP6740424B1 (en) | Preparation method of high-purity lithium salt by mixing in a predetermined ratio and its application | |
| CN114805288B (en) | Method for preparing 2, 4-butane sultone | |
| CN114181190B (en) | 2, 4-butane sultone and preparation method and application thereof | |
| CN111018757B (en) | Method for synthesizing 3-mercaptopropionic acid from acidic waste gas | |
| CN101659653B (en) | Preparation method of propenyl-1, 3-sulfonic acid lactone | |
| CN107722048A (en) | Ring-type sulfonic acid silicon substrate lactone and preparation method thereof | |
| WO2023020319A1 (en) | Method for preparing imidazole carboxylate and use thereof | |
| JP2005179254A (en) | Cold molten salt and method for producing the same | |
| CN109369474B (en) | Preparation method of lithium bis (trifluoromethylsulfonyl) imide | |
| CN101948461B (en) | Method for synthesizing 1,4-dioxane | |
| CN102008978B (en) | Chiral catalyst and preparation method and application thereof | |
| CN111892557B (en) | Synthetic method of piperazine film-forming ionic liquid | |
| CN114085170A (en) | Preparation method of lithium alkyl sulfate | |
| CN100432082C (en) | Synthesis method of chloro diisopropyl phosphine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |