CN114436908A - High-elongation lithium ion membrane compound of tertiary aryl ether diene difluoromethyl sulfonic acid - Google Patents
High-elongation lithium ion membrane compound of tertiary aryl ether diene difluoromethyl sulfonic acid Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 206
- 239000012528 membrane Substances 0.000 title claims abstract description 92
- 150000001993 dienes Chemical class 0.000 title claims abstract description 26
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 14
- CGDXUTMWWHKMOE-UHFFFAOYSA-N difluoromethanesulfonic acid Chemical compound OS(=O)(=O)C(F)F CGDXUTMWWHKMOE-UHFFFAOYSA-N 0.000 title claims description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 6
- 125000005013 aryl ether group Chemical group 0.000 title 1
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 54
- -1 aryl ether diene Chemical group 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 29
- 238000006266 etherification reaction Methods 0.000 claims abstract description 25
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 19
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 claims abstract description 14
- 238000001308 synthesis method Methods 0.000 claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 4
- 230000000903 blocking effect Effects 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 78
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 63
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 50
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 38
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 30
- 230000003647 oxidation Effects 0.000 claims description 23
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 20
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 20
- 238000000926 separation method Methods 0.000 claims description 19
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 14
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 14
- 229910052794 bromium Chemical group 0.000 claims description 14
- 239000007858 starting material Substances 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 11
- 230000002194 synthesizing effect Effects 0.000 claims description 11
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical group OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims description 11
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 10
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 10
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 10
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 10
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 10
- 238000007670 refining Methods 0.000 claims description 10
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 10
- 150000005215 alkyl ethers Chemical class 0.000 claims description 9
- 238000005868 electrolysis reaction Methods 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000003377 acid catalyst Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 238000005336 cracking Methods 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 2
- 125000000468 ketone group Chemical group 0.000 claims description 2
- SIRFJGFXOSGPRT-UHFFFAOYSA-N difluoromethyl benzenesulfonate Chemical compound FC(F)OS(=O)(=O)C1=CC=CC=C1 SIRFJGFXOSGPRT-UHFFFAOYSA-N 0.000 claims 2
- 150000001346 alkyl aryl ethers Chemical class 0.000 claims 1
- 125000003710 aryl alkyl group Chemical group 0.000 claims 1
- 239000007784 solid electrolyte Substances 0.000 abstract description 27
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- 230000035515 penetration Effects 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 58
- 239000000243 solution Substances 0.000 description 45
- 238000000967 suction filtration Methods 0.000 description 39
- 239000007864 aqueous solution Substances 0.000 description 36
- 238000004128 high performance liquid chromatography Methods 0.000 description 36
- 238000005406 washing Methods 0.000 description 32
- 239000007788 liquid Substances 0.000 description 29
- 238000003756 stirring Methods 0.000 description 26
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 24
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 20
- 239000013078 crystal Substances 0.000 description 18
- 235000019441 ethanol Nutrition 0.000 description 17
- 239000000706 filtrate Substances 0.000 description 16
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 16
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 16
- 239000012295 chemical reaction liquid Substances 0.000 description 15
- 150000003839 salts Chemical class 0.000 description 15
- 238000004817 gas chromatography Methods 0.000 description 13
- 238000003860 storage Methods 0.000 description 13
- 230000008034 disappearance Effects 0.000 description 12
- 238000004821 distillation Methods 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 11
- 229920000557 Nafion® Polymers 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- XPKMFHPRXPJWRJ-UHFFFAOYSA-N 2-(difluoromethylsulfonyl)ethanol Chemical compound OCCS(=O)(=O)C(F)F XPKMFHPRXPJWRJ-UHFFFAOYSA-N 0.000 description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000012065 filter cake Substances 0.000 description 8
- 235000019253 formic acid Nutrition 0.000 description 8
- 239000003112 inhibitor Substances 0.000 description 8
- 230000001590 oxidative effect Effects 0.000 description 8
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 8
- 235000010265 sodium sulphite Nutrition 0.000 description 8
- 238000005070 sampling Methods 0.000 description 7
- 239000012043 crude product Substances 0.000 description 6
- 230000033001 locomotion Effects 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000002227 LISICON Substances 0.000 description 4
- 241000183024 Populus tremula Species 0.000 description 4
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 108091006146 Channels Proteins 0.000 description 3
- 108090000862 Ion Channels Proteins 0.000 description 3
- 102000004310 Ion Channels Human genes 0.000 description 3
- 229910021525 ceramic electrolyte Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005562 fading Methods 0.000 description 3
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000005518 polymer electrolyte Substances 0.000 description 3
- 229920001021 polysulfide Polymers 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910010615 Li6.75La3 Inorganic materials 0.000 description 1
- FVXHSJCDRRWIRE-UHFFFAOYSA-H P(=O)([O-])([O-])[O-].[Ge+2].[Al+3].[Li+].P(=O)([O-])([O-])[O-] Chemical compound P(=O)([O-])([O-])[O-].[Ge+2].[Al+3].[Li+].P(=O)([O-])([O-])[O-] FVXHSJCDRRWIRE-UHFFFAOYSA-H 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- CVJYOKLQNGVTIS-UHFFFAOYSA-K aluminum;lithium;titanium(4+);phosphate Chemical compound [Li+].[Al+3].[Ti+4].[O-]P([O-])([O-])=O CVJYOKLQNGVTIS-UHFFFAOYSA-K 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000008378 aryl ethers Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- KAYYMSTXKCZITA-UHFFFAOYSA-N ethenoxyethene;sulfuryl difluoride Chemical compound C=COC=C.FS(F)(=O)=O KAYYMSTXKCZITA-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 229920005570 flexible polymer Polymers 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- FHUGMWWUMCDXBC-UHFFFAOYSA-N gold platinum titanium Chemical compound [Ti][Pt][Au] FHUGMWWUMCDXBC-UHFFFAOYSA-N 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229940087748 lithium sulfate Drugs 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- QWGCQZJUWQYRGZ-UHFFFAOYSA-M lithium;difluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)F QWGCQZJUWQYRGZ-UHFFFAOYSA-M 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/20—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic unsaturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/11—Halogen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/13—Organo-metallic compounds
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/23—Oxidation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to an ionic membrane compound of lithium difluoro methyl sulfonate of tertiary aryl ether diene and a synthesis method thereof, which need four-step synthesis reaction of etherification reaction, difluoromethyl reaction, membrane electrolytic oxidation reaction and dehydrated diene. The polymerized ionic membrane solid electrolyte has high Li + conductivity, low contact resistance for clinging to the surface of a metal lithium sheet to deform, selective penetration of Li + only, shuttle blocking effect and other excellent performances.
Description
Technical Field
The invention relates to a new compound of an ionic membrane solid electrolyte and a synthesis method thereof, which are applied to the field of new materials of ionic membrane solid electrolytes for lithium battery metal lithium sheet negative electrode protection.
Background art at present, many solid electrolytes are reported at home and abroad, and can be divided into organic ionic membrane solid electrolytes, inorganic ceramic solid electrolytes (LISICON) and PEG ether polymer solid electrolytes (ASPE) rich in electron-rich oxyalkane bonds. The chemical evolution 2020, 32 (4) 481-496 full solid polymer electrolyte for lithium batteries introduces various solid electrolyte performances except the ionic membrane solid electrolyte in detail, wherein the Li SiC ceramic solid electrolyte (including LLZTO, LAGP, LATP and other ceramic electrolytes) and the ASPE solid electrolyte hardly reach Li more than or equal to 0.001S/cm at room temperature+Ion conductivity, difficult to charge and discharge with large current; the ceramic solid electrolyte needs to be sintered at a high temperature of more than or equal to 1000 ℃, is brittle and hard, cannot be deformed, is difficult to process and cannot completely and tightly coat the metal lithium sheet; particularly, the surface expansion and contraction are severe when the metal lithium sheet negative electrode is charged and discharged, the ceramic solid electrolyte cannot be tightly attached to the metal lithium sheet, and the contact resistance is particularly large.
The organic ionic membrane solid electrolyte has very high ionic conductivity and is very suitable for large-current charge and discharge; chemical research and application 2008, 20 (2) 212-215 research and application of ionic membrane cell current density introduce that Nafion ionic membrane can reach 5000A/M in large-scale electrolytic production in chlor-alkali industry2The calculated ionic conductivity of the current density is more than or equal to 0.05S/cm.
US3282875 describes a Nafion perfluorosulfonic acid ionic membrane, a well-known by dupont, which is a flexible polymer prepared by copolymerizing tetrafluoroethylene and a monovinyl ether sulfonyl fluoride having a chemical structure of formula H; because no crosslinking exists, the Nafion ionic membrane can be dissolved in alcohols, aromatic hydrocarbon solvents, high-boiling-point ester solvents or DMF, and the Nafion ionic membrane solid electrolyte cannot be stably used for a long time in an environment containing an organic electrolyte solvent;
zhang Qiang "Energy and Environmental Science" 2014 (7) 347-353 "electronic shield for polymeric filters facing high-stable lithium-sulfate batteries" describes a method for preventing the shuttle effect of polysulphide in a lithium-sulphur battery by coating a metallic lithium sheet with a Nafion ion membrane, wherein CF is hydrolyzed by the Nafion ion membrane2SO3 —The shuttle effect of the group and electrostatic repulsion preventing the movement of the polysulphide anion is better than that of a Celgard 2400 lithium battery diaphragm, but the Nafion ionic membrane is not crosslinked, can be swelled and damaged by an electrolyte solvent and is only subjected to charge and discharge cycles for 500 times.
CN201711491825 introduces a polypropylene microporous membrane, which is impregnated with mono-olefinic bond water-soluble 4-allyloxy benzene sulfonate pyridinium with a chemical structure of J, wherein the distribution and the size of polypropylene membrane pores cannot be controlled, and the polypropylene has poor temperature resistance, so that the distribution of sulfonic acid groups of a polymeric ionic membrane is uneven, the distribution and the size of membrane pores are unstable, ionic channels of the ionic membrane are randomly distributed from 2nm to 50nm, and a compact cross-linked ionic membrane capable of blocking the permeation of an organic solvent cannot be prepared;
CN201910908916 reports that three monoethylenically polymerized monomers, namely acrylic acid, vinyltriethoxysilane and triacrylateylaminobenzoic acid, are subjected to radical polymerization to obtain an ionic membrane, and the ionic membrane is crosslinked by using triethoxysilane, but a silicon-oxygen bond is broken by strong acid and strong base, so that the performance of the ionic membrane is very unstable; and acrylic acid has the strength pKa of 4.75, is weak in acidity and is firmly chelated with Li < + > ions, and Li+The movement migration resistance is particularly large, and if the lithium battery is used, only micro current can be charged and discharged; the stronger the acid strength, the smaller the complexation resistance of cation movement, and the Li of the ionic membrane+The higher the ionic conductivity can be.
The existing ionic membrane is a high polymer material copolymerized by a plurality of mono-olefinic bond monomer compounds, and due to different polymerization rates of various mono-olefinic bond polymerization monomers, pore channels of the polymerized ionic membrane are distributed unevenly, the degree of crosslinking is low and uneven, the degree of crosslinking is high in some regions, and the crosslinking is not carried out in some regions, so that the quality of the ionic membrane is uneven, the permeation of an organic solvent cannot be blocked, the service life is short, and the ionic membrane is difficult to be used in products containing the organic solvent, such as the coating protection of a lithium-sulfur battery metal lithium sheet.
Aiming at the problems, the invention designs and provides a novel ionic membrane compound, various functions of the ionic membrane solid electrolyte are designed on one molecule in a centralized manner, and the ionic membrane compound has a definite molecular structure, and each ionic membrane monomer molecule has 2 olefinic bonds, so that uniform compact crosslinking can be ensured, the problem that a Nafion ionic membrane is not crosslinked and is quickly swelled, damaged and invalid by an organic solvent is solved, the membrane pore channel distribution, the pore channel size and the like can be highly uniform, the quality performance of each production batch of the ionic membrane solid electrolyte can be ensured, the high repeatability is consistent, and the ionic membrane solid electrolyte compound has higher application value in the solid electrolyte protection of metal lithium sheet cathodes such as lithium-sulfur batteries and the like.
Disclosure of Invention
The invention relates to an ionic membrane new compound of lithium aryl tert-alkyl ether diene difluoromethylsulfonate and a synthesis method thereof, wherein the ionic membrane new compound is the lithium aryl tert-alkyl ethoxy alkyl ether diene difluoromethylsulfonate with a chemical structure shown as a formula A:
wherein: m =1~3, n =0~ 1.
According to the lithium aryl tertiary alkyl ethoxy alkyl ether diene difluoromethyl sulfonate with the chemical structure shown in the formula A, various performance requirements of the solid electrolyte are designed into one compound molecule in a centralized manner, and the polymerized and coated ionic membrane solid electrolyte integrates various excellent performances; the surface of the metal lithium sheet negative electrode can expand and contract greatly during charging and discharging, and the polyether bond flexible alkyl chain of the compound in the formula A can extend flexibly and is tightly attached to the surface of the metal lithium sheet to change, so that the very low contact resistance is kept, and the growth of lithium dendritic crystals is also prevented.
Li+Is a cation with strong electron-rich oxygen chelating ability once Li is added+The movement resistance of separation and migration is very large due to chelation with electron-rich oxygen, and only small current charging and discharging can be realized on the battery material; since the LISICON ceramic solid electrolyte or the ASPE solid electrolyte is rich in electron-rich ether-bonded oxygen, Li is chelated+Too strong, Li+The resistance to motion is too large and therefore Li cannot be increased+The ionic conductivity is more than or equal to 0.001S/cm; however, in the compound of formula A, lithium difluoromethylsulfonate is a lithium salt of a super strong acid having pKa = -11.30 due to the strong electron-withdrawing group of difluoromethyl group, and a difluoromethylsulfonic acid group having a super strong acid strength similar to that of the compound of formula K, the more acidic the oxygen-containing group, the more Li+The weaker the chelating ability of the oxygen-containing group, Li+The smaller the migration motion resistance; CF of the Compound of formula A2SO3 —Radical and Li+Extremely weak chelating ability, Li+Can be rapidly transferred to realize large-current charge and discharge.
The compound of the formula A has 2 olefinic bonds in the molecule, and each compound of the formula A is a polymerization cross-linking agent, so that the polymerized ionic membrane solid electrolyte can be subjected to compact cross-linking; the spacing between dienes of the compound in the formula A is 2.2-3.0 nm, and an ion channel with the thickness less than 0.5nm is formed after compact crosslinking; after the compound of the formula A is polymerized and coated on a lithium metal sheet, only Li is allowed+The solution permeates through the solid electrolyte layer of the compact crosslinked ionic membrane, but prevents organic solvent from permeating to the surface of the lithium metal sheet, and after compact crosslinking, continuous distribution CF is formed2SO3 —Very small ion channels of radicals, superimposed CF2SO3 —The shuttle effect of the lithium-sulfur battery can be completely blocked by the strong electrostatic repulsion of the groups to the polysulphide anions.
Compound of formula A CF2SO3 —The ionic capacity of the group is more than or equal to 2.0mmol/g and is far higher than that of a Nafion ionic membrane, so that Li of the ionic membrane solid electrolyte after the compound of the formula A is polymerized is ensured+The ionic conductivity is more than or equal to 0.05S/cm. The power battery is charged and discharged in large current and has high Li content+The conductivity and the high electron conductivity can obviously reduce the heating loss and avoid the thermal runaway risk caused by heatingThe energy density is greatly reduced, and the ionic membrane solid electrolyte polymerized by the compound of the formula A has excellent Li+The ionic conductivity can greatly improve the heating performance of the power battery.
The synthesis method of the lithium aryl tert-alkyl ethoxy alkyl ether diene difluoromethylsulfonate with the chemical structure of the formula A needs to adopt 3- (4-alpha-methoxyethylphenyl) -3-methyl-1-halobutane with the chemical structure of the formula B as a starting material:
wherein: x is chlorine or bromine.
The synthesis method of the compound of the formula A needs to adopt a hydroxyethyl ether alkyl-2-ketone compound with a chemical structure of a formula C as a starting material:
wherein: m =1~3, n =0~ 1.
The synthesis of the compound of the formula A needs four-step synthesis reaction of etherification reaction, difluoromethyl reaction, membrane electrolysis oxidation reaction and dehydrated diene, and finally synthesizes the lithium aryl tert-alkyl ethoxy alkyl ether diene difluoromethyl sulfonate ionic membrane compound with the chemical structure of the formula A:
(1) and (3) etherification reaction: in dioxane, a compound shown in a formula B, a slightly excessive compound shown in a formula C and a small amount of tetrabutylammonium bromide are mixed and dissolved, potassium carbonate and a small amount of potassium iodide are added, the etherification reaction of the compound shown in the formula B and the compound shown in the formula C is completed at 60-90 ℃, acetic acid is added for neutralization after the reaction is finished, and an aromatic tertiary alkyl ether ketone compound with a chemical structure shown in a formula D is obtained by separation:
wherein: m = 1-3, n = 0-1;
(2) and (3) difluoromethyl reaction: dissolving the compound of the formula E in methanol, adding a small amount of LiOH for alkaline catalysis, and adding the compound of the formula E and the ketone group of the compound of the formula D at the temperature of 10-40 ℃ to obtain a methanol solution of the compound of the formula F; the molar ratio of the compound of the formula E to the compound of the formula D is 1.1-1.4: 1;
wherein: m = 1-3, n = 0-1;
(3) film electrolytic oxidation reaction: adding excessive LiOH into a methanol solution of a compound in the formula F, keeping the strong alkaline pH of the solution to be more than or equal to 12, continuously performing membrane electrolysis oxidation in a bromine membrane electrolysis device, adding a proper amount of hydrobromic acid after the pH of the material is reduced to be pH = 9-10, neutralizing to be pH = 6.0-7.5, distilling to recover hydrous methanol, refining with absolute ethyl alcohol, and separating to obtain an aromatic tert-alkyl ethoxy alkyl ether-2-hydroxy-2-difluoromethyl sulfonic acid lithium compound in a chemical structure in the formula G;
wherein: m = 1-3, n = 0-1;
(4) and (3) dehydrating diene reaction: adding an acid catalyst and cyclohexane into the compound of the formula H, heating to 80-90 ℃, refluxing, acid cracking, adding a small amount of lithium carbonate for neutralization after complete cracking, distilling and recovering the cyclohexane, adding absolute ethyl alcohol for dissolving, and separating to obtain the lithium aryl tert-alkyl ethoxy alkyl ether diene difluoromethylsulfonate with the chemical structure of the formula A;
wherein: m =1~3, n =0~ 1.
In the etherification reaction, the molar ratio of the compound shown in the formula B to the compound shown in the formula C is 1: 1.2-1.5; the molar ratio of the potassium iodide to the compound of the formula B is 0.1-0.3: 1.
in the membrane electrolytic oxidation reaction, the molar ratio of the LiOH to the compound of the formula F to be added is 2-4: 1.
in the membrane electrolytic oxidation reaction, a dense cross-linked anion membrane which can block methanol permeation but can open the membrane electrolytic oxidation device is required to be adopted by the membrane electrolytic oxidation deviceOver Br—An anion.
In the dehydrodiene reaction, trichloroacetic acid is selected as an acid catalyst, and the addition amount of the trichloroacetic acid is 10-30 wt% of the mass of the compound shown in the formula G.
Description of the drawings:
FIG. 1: the group and function of the lithium ion membrane compound of aryl tertiary alkyl ethoxy alkyl ether diene difluoromethyl sulfonate;
FIG. 2: a membrane electrolytic oxidation unit system;
1: stainless steel cathode: length 138mm and width 74 mm;
2: a cathode chamber;
3: a dense cross-linked anionic membrane;
4: an oxidation chamber;
5: an anode chamber;
6: plating a platinum-gold titanium mesh anode; length 138mm and width 74mm
7: an anode storage tank; 5000ml polypropylene barrel B
8: an anode chamber circulating pump;
9: an oxidation chamber circulating pump;
10: a material storage tank of the oxidation chamber; 5000ml polypropylene bucket C.
Explanation of abbreviated terms:
LISICON: lithium super-ionic conductor glass film, a Lithium ion conducting ceramic electrolyte;
ASPE: all-solid-state polymer electrolyte (All-solid-state polymer electrolyte);
LAGP: lithium aluminum germanium phosphate;
LATP: lithium aluminum titanium phosphate;
LLZTO： Li6.75La3Zr1.75Ta0.25O12a solid ceramic electrolyte;
HPLC: high pressure liquid chromatography analysis;
GC: and (4) analyzing by gas chromatography.
The specific implementation mode is as follows:
in order to better understand the present invention, the following examples are presented to describe the synthetic process, but the present invention is not limited to the following examples.
Example 1:
synthesizing a compound with a formula K of m =1 and n =0, and taking 3- (4-alpha-methoxyethylphenyl) -3-methyl-1-bromobutane as a starting material;
1: and (3) etherification reaction:
adding 3500g of dioxane, 1363g (4.8 mol) of 3- (4-alpha-methoxyethylphenyl) -3-methyl-1-bromobutane, 585g (4.0 mol) of 5-hydroxyethyl ether-2-pentanone, 132g (0.8 mol) of potassium iodide, 40g of tetrabutylammonium bromide and 560g of anhydrous potassium carbonate (2.0 mol) into a 10000ml three-necked bottle, uniformly stirring at room temperature, heating in a water bath to keep at 60-70 ℃ for etherification reaction, reacting for 12.5h, and analyzing the disappearance of 5-hydroxyethyl ether-2-pentanone in a reaction solution by GC (gas chromatography), and finishing the reaction; cooling to room temperature, adding 85% formic acid to neutralize until the pH is = 6-7, performing suction filtration to remove solids, washing a filter cake with dioxane, recovering a dioxane washing solution, combining the dioxane washing solution with a crude suction filtration solution of a compound (m =1, n = 0) shown in the formula D, maintaining the temperature at the top temperature of less than or equal to 80 ℃, performing reduced pressure distillation to desolventize, and recovering dioxane.
Separation and refining: pouring the desolvated crude compound of the formula D into room-temperature water, wherein the unreacted 3- (4-alpha-methoxyethylphenyl) -3-methyl-1-bromobutane and the compound of the formula D are insoluble in water, separating out the crude solid compound of the formula D (m =1, n = 0) which is insoluble in water, and washing away the residual dioxane and inorganic salt; preparing 6240g of a 10% aqueous solution of 624g of sodium bisulfite (6 mol), keeping the temperature at 30-40 ℃, pouring a crude solid of a water-insoluble compound shown in the formula D into an aqueous solution of sodium bisulfite at 30-40 ℃, stirring for 2.5-3 h, dissolving the compound shown in the formula D (m =1, n = 0) in water, performing suction filtration to recover a solid of 3- (4-alpha-methoxyethylphenyl) -3-methyl-1-bromobutane which is insoluble in the aqueous solution of sodium bisulfite, adjusting the pH of the separated aqueous solution of sodium sulfite to be more than or equal to 10 by using 20% NaOH, separating out a solid of the water-insoluble compound shown in the formula D (m =1, n = 0), performing suction filtration to collect the compound shown in the formula D (m =1, n = 0), and drying to obtain 1192g (3.4 mol) of white crystals of the refined compound shown in the formula D (m =1, n = 0), wherein the HPLC purity is 99.2%.
2: and (3) difluoromethyl reaction:
adding 2500g of anhydrous methanol, 390g (2.4 mol) of hydroxyethyl difluoromethyl sulfone and 53g (2.2 mol) of LiOH into a 5000ml three-necked flask, stirring at room temperature to dissolve, adding 702g (2 mol) of a compound (m =1, n = 0) of a formula D, reacting at 20-30 ℃ for 10-11 h, and analyzing the disappearance of the compound of the formula D by HPLC sampling, wherein the obtained reaction liquid (m =1, n = 0) of the compound of the formula F is directly used for the next membrane electrolytic oxidation reaction without separation.
3: film electrolytic oxidation reaction:
adding 3000g of 3% LiOH aqueous solution into a 5000ml cathode storage vat A by using a membrane electrolytic oxidation device provided with a compact cross-linked anion membrane, and switching on a circulating pump and a cathode chamber for continuous circulation; adding 3500g of 50% LiBr aqueous solution into a 5000ml anode storage vat B, heating and keeping the temperature at 55-60 ℃, and switching on a circulating pump and an anode chamber for continuous circulation; adding the reaction solution of the compound (m =1, n = 0) shown in the formula F into a 5000ml oxidation solution storage barrel C, adding 96g of LiOH (4 mol), stirring for dissolving, keeping strong alkalinity with pH being more than or equal to 12, and starting a circulating pump and an oxidation chamber for continuous circulation; connecting 8V electrolytic power supply, electrolyzing the anode chamber to generate bromine, and maintaining the temperature of the feed liquid B in the anode barrel at 60 ℃ or higher to generate bromine Br2Volatilizing to enter an oxidizing liquid storage barrel C for absorption; the oxidizing liquid storage barrel C releases heat, Br2Rapidly oxidizing the carbanion of compound of formula F (m =1, n = 0), rapidly fading bromine, maintaining oxidizing fluid reservoir C without reflux; the membrane electrolysis continuously operates at 8V/25-30A, the fading of bromine in the oxidation liquid starts to slow after 2.5-3 h, the pH of the oxidation liquid starts to drop to pH = 9-10, the HPLC analysis formula F compound disappears, the membrane electrolysis oxidation reaction is finished, a proper amount of hydrazine hydrate is dripped to digest the red and oxidizing properties of the bromine, and the starch-KI test paper does not change color and is cooled to room temperature.
Pouring the oxidation solution into a 5000ml three-necked flask, adding a proper amount of hydrobromic acid to neutralize the oxidation solution to pH = 6.0-7.0, heating the solution in a water bath, completely recovering aqueous methanol by distillation, adding 2500G of absolute ethanol to dissolve the remained solid, performing suction filtration to remove insoluble solid salts such as LiBr and the like, and performing reduced pressure distillation on the filtrate to recover ethanol to obtain 854G (1.75 mol) of light yellow crystals of the compound of the formula G (m =1, n = 0) with the HPLC purity of 98.6%.
4: and (3) dehydrating diene reaction:
adding 489G (1 mol) of a compound (m =1, n = 0) of a formula G, 96G of trichloroacetic acid, 3G of p-methoxyphenol serving as a polymerization inhibitor and 500G of cyclohexane into a 3000ml three-necked bottle, heating, refluxing, azeotropically dehydrating for 2-3 h, distilling and recovering the cyclohexane at the top temperature of less than or equal to 85 ℃ after water discharge is stopped, adding 1200G of absolute ethyl alcohol and a proper amount of lithium carbonate into the remained solid to neutralize the pH to be 6.0-7.0, performing suction filtration to remove the solid, and distilling and removing the ethyl alcohol from the clear filtrate under reduced pressure to obtain 403G (0.92 mol) of a compound (m =1, n = 0) of a formula A with the HPLC purity of 97.4%.
Example 2:
synthesizing a compound with a formula M of M =2 and n =0, and taking 3- (4-alpha-methoxyethylphenyl) -3-methyl-1-bromobutane as a starting material;
1: and (3) etherification reaction:
adding 3600g of dioxane, 1361g (4.8 mol) of 3- (4-alpha-methoxyethylphenyl) -3-methyl-1-bromobutane, 642g (4.0 mol) of 6-hydroxyethyl ether-2-hexanone, 132g (0.8 mol) of potassium iodide, 40g of tetrabutylammonium bromide and 560g of anhydrous potassium carbonate (2.0 mol) into a 10000ml three-necked bottle, uniformly stirring at room temperature, heating in a water bath to keep at 60-70 ℃ for etherification reaction, and after 14h of reaction, analyzing the disappearance of 6-hydroxyethyl ether-2-hexanone in a reaction solution by GC, and finishing the reaction; cooling to room temperature, adding 85% formic acid to neutralize until the pH is = 6-7, performing suction filtration to remove solids, washing a filter cake with dioxane, recovering a dioxane washing solution, mixing the dioxane washing solution with a crude product suction filtration solution of the compound shown in the formula D, maintaining the top temperature to be less than or equal to 80 ℃, performing reduced pressure distillation to remove the solvent, and recovering the dioxane.
Separation and refining: pouring the desolventized crude compound of the formula D into water at room temperature, wherein the unreacted 3- (4-alpha-methoxyethylphenyl) -3-methyl-1-bromobutane and the compound of the formula D are insoluble in water, separating out a crude solid compound of the formula D (m =2, n = 0) insoluble in water, and washing away residual dioxane and inorganic salts; preparing 6240g of a 10% aqueous solution of 624g of sodium bisulfite (6 mol), keeping the temperature at 30-40 ℃, dissolving a crude solid of a water-insoluble compound shown in the formula D (m =2, n = 0), pouring the crude solid into an aqueous solution of sodium bisulfite at 30-40 ℃, stirring for 2.5-3 h, dissolving the compound shown in the formula D in water, recovering 3- (4-alpha-methoxyethylphenyl) -3-methyl-1-bromobutane which is insoluble in the aqueous solution of sodium bisulfite, adjusting the pH of the separated aqueous solution of sodium sulfite to be more than or equal to 10 by using 20% NaOH, separating out a solid of the water-insoluble compound shown in the formula D (m =2, n = 0), performing suction filtration to collect the compound shown in the formula D, and drying to obtain 1275g (3.5 mol) of a white crystal of the refined compound shown in the formula D (m =2, n = 0), wherein the HPLC purity is 99.4%.
2: and (3) difluoromethyl reaction:
after adding 2500g of anhydrous methanol, 391g (2.4 mol) of hydroxyethyl difluoromethyl sulfone and 53g (2.2 mol) of LiOH into a 5000ml three-necked flask and stirring at room temperature to dissolve, 728g (2 mol) of a compound (m =2, n = 0) of formula D is added, the mixture is kept at 20-30 ℃ for reaction for 10-11 h, HPLC sampling analysis shows that the compound (m =2, n = 0) of formula D disappears, and the obtained reaction liquid of the compound (m =2, n = 0) of formula F is directly used for the next membrane electrolytic oxidation reaction without separation.
3: film electrolytic oxidation reaction:
the synthetic feeding, synthetic operation and condition control are the same as the membrane electrolytic oxidation reaction of the example 1;
pouring the oxidized liquid into a 5000ml three-necked bottle, adding a proper amount of hydrobromic acid to neutralize the oxidized liquid to pH = 6.0-7.0, heating the mixture in a water bath, completely distilling and recovering aqueous methanol, adding 2500G of absolute ethyl alcohol to dissolve the remained solid, performing suction filtration to remove insoluble solid salts such as LiBr and the like, and distilling the filtrate under reduced pressure to recover ethanol to obtain 852G (1.7 mol) of light yellow crystals of the compound of the formula G (m =2, n = 0) with the HPLC purity of 98.2%.
4: and (3) dehydrating diene reaction:
adding a compound of a formula G (m =2, n = 0) 503G (1 mol), 96G trichloroacetic acid, a polymerization inhibitor p-methoxyphenol 3G and 500G cyclohexane into a 3000ml three-neck flask, heating, refluxing, azeotropically dehydrating for 2-3 h, distilling and recovering the cyclohexane at the top temperature of less than or equal to 85 ℃ after water outlet is stopped, adding anhydrous ethanol 1200G and a proper amount of lithium carbonate into the remained solid to neutralize the pH to be 6.0-7.0, filtering to remove the solid by suction, and distilling and removing the ethanol from the clear filtrate under reduced pressure to obtain the compound of the formula A (m =2, n = 0) 412G (0.91 mol) with the HPLC purity of 97.6%.
Example 3:
synthesizing a compound with a formula N of m =3 and N =0, and taking 3- (4-alpha-methoxyethylphenyl) -3-methyl-1-bromobutane as a starting material;
1: and (3) etherification reaction:
adding 3800g of dioxane, 1363g (4.8 mol) of 3- (4-alpha-methoxyethylphenyl) -3-methyl-1-bromobutane, 696g (4.0 mol) of 7-hydroxyethyl ether-2-heptanone, 132g (0.8 mol) of potassium iodide, 40g of tetrabutylammonium bromide and 560g of anhydrous potassium carbonate (2.0 mol) into a 10000ml three-necked bottle, uniformly stirring at room temperature, heating in a water bath, keeping at 60-70 ℃ for etherification reaction, and after 16h of reaction, analyzing the disappearance of the reaction liquid 7-hydroxyethyl ether-2-heptanone by GC, and finishing the reaction; cooling to room temperature, adding 85% formic acid to neutralize until the pH is = 6-7, performing suction filtration to remove solids, washing a filter cake with dioxane, recovering a dioxane washing solution, mixing the dioxane washing solution with a crude suction filtration solution of a compound (m =3, n = 0) shown in the formula D, maintaining the temperature at the top temperature of less than or equal to 80 ℃, performing reduced pressure distillation to desolventize, and recovering dioxane.
Separation and refining: pouring the crude product of the desolvated compound (m =3, n = 0) of the formula D into water at room temperature, wherein the unreacted 3- (4-alpha-methoxyethylphenyl) -3-methyl-1-bromobutane and the compound (m =3, n = 0) of the formula D are insoluble in water, separating out a crude solid product of the compound (m =3, n = 0) of the formula D which is insoluble in water, and washing away residual dioxane and inorganic salts; preparing 6245g of a 10% aqueous solution of 624g of sodium bisulfite (6 mol), keeping the temperature at 30-40 ℃, dissolving a crude solid of a water-insoluble compound shown in the formula D in water, pouring the crude solid into an aqueous solution of sodium bisulfite at 30-40 ℃, stirring for 3-4 h, dissolving a compound shown in the formula D (m =3, n = 0) in water, recovering 3- (4-alpha-methoxyethylphenyl) -3-methyl-1-bromobutane which is insoluble in the aqueous solution of sodium bisulfite, adjusting the pH of the separated aqueous solution of sodium sulfite to be more than or equal to 10 by using 20% NaOH, separating out a solid of the water-insoluble compound shown in the formula D (m =3, n = 0), performing suction filtration to collect the compound shown in the formula D (m =3, n = 0), and drying to obtain 1356g (3.6 mol) of a white crystal of the compound shown in the formula D (m =3, n = 0) with the HPLC purity of 99.5%.
2: and (3) difluoromethyl reaction:
after adding 2500g of anhydrous methanol, 390g (2.4 mol) of hydroxyethyl difluoromethyl sulfone and 53g (2.2 mol) of LiOH into a 5000ml three-necked flask, stirring and dissolving at room temperature, adding 756g (2 mol) of the compound of formula D (m =3, n = 0), reacting at 20-30 ℃ for 11-12 h, and analyzing disappearance of the compound of formula D (m =3, n = 0) by HPLC sampling, wherein the obtained reaction solution of the compound of formula F (m =3, n = 0) is directly used for the next membrane electrolytic oxidation reaction without separation.
3: film electrolytic oxidation reaction:
the synthetic feeding, synthetic operation and condition control are the same as the membrane electrolytic oxidation reaction of the example 1;
pouring the oxidized liquid into a 5000ml three-necked flask, adding a proper amount of hydrobromic acid to neutralize the oxidized liquid to pH = 6.0-7.0, heating the mixture in a water bath, completely distilling and recovering aqueous methanol, adding 2800G of anhydrous ethanol to dissolve the remained solid, performing suction filtration to remove insoluble solid salts such as LiBr, and performing reduced pressure distillation on the filtrate to recover ethanol to obtain 871G (1.69 mol) of light yellow crystals of a compound of a formula G (m =3, n = 0), wherein the HPLC purity is 98.1%.
4: and (3) dehydrating diene reaction:
adding 517G (1 mol) of a compound of formula G (m =3, n = 0), 96G of trichloroacetic acid, 3G of p-methoxyphenol serving as a polymerization inhibitor and 500G of cyclohexane into a 3000ml three-necked bottle, heating, refluxing, azeotropically dehydrating for 3-3.5 h, distilling and recovering the cyclohexane at the top temperature of less than or equal to 85 ℃ after water outlet is stopped, adding 1200G of absolute ethyl alcohol and a proper amount of lithium carbonate into the remained solid to neutralize the pH to be 6.0-7.0, performing suction filtration to remove the solid, and distilling and removing the ethyl alcohol from the clear filtrate under reduced pressure to obtain 427G (0.92 mol) of the compound of formula A (m =3, n = 0), wherein the HPLC purity is 96.8%.
Example 4:
synthesizing a compound P with m =1 and n =1, wherein 3- (4-alpha-methoxyethylphenyl) -3-methyl-1-bromobutane is used as a starting material;
1: and (3) etherification reaction:
adding 4000g of dioxane, 1362g (4.8 mol) of 3- (4-alpha-methoxyethylphenyl) -3-methyl-1-bromobutane, 760g (4.0 mol) of 5- (hydroxyethyl ether ethoxy) -2-pentanone, 132g (0.8 mol) of potassium iodide, 40g of tetrabutylammonium bromide and 560g of anhydrous potassium carbonate (2.0 mol) into a 10000ml three-necked bottle, uniformly stirring at room temperature, heating in a water bath to keep at 60-70 ℃ for etherification reaction, and after reacting for 16.5h, analyzing the disappearance of 5- (hydroxyethyl ether ethoxy) -2-pentanone in a reaction solution by GC (gas chromatography), and finishing the reaction; cooling the obtained reaction liquid of the compound (m =1, n = 1) in the formula D to room temperature, adding 85% formic acid to neutralize the reaction liquid until the pH is = 6-7, performing suction filtration to remove solids, washing a filter cake with dioxane, recovering a dioxane washing solution, combining the dioxane washing solution with a crude suction filtration liquid of the compound (m =1, n = 1) in the formula D, maintaining the temperature at the top temperature of less than or equal to 80 ℃, performing reduced pressure distillation and desolventizing, and recovering dioxane.
Separation and refining: pouring the desolventized crude compound of the formula D (m =1, n = 1) into water at room temperature, wherein the unreacted 3- (4-alpha-methoxyethylphenyl) -3-methyl-1-bromobutane and the compound of the formula D are insoluble in water, separating out crude solid compounds of the compound of the formula D which are insoluble in water, and washing away residual dioxane and inorganic salts; preparing 6240g of a 10% aqueous solution of 624g of sodium bisulfite (6 mol), keeping the solution at 30-40 ℃, dissolving a crude solid of a water-insoluble compound of formula D (m =1, n = 1) in water, pouring the crude solid into an aqueous solution of sodium bisulfite at 30-40 ℃, stirring for 2.5-3 h, dissolving the compound of formula D (m =1, n = 1) in water, recovering 3- (4-alpha-methoxyethylphenyl) -3-methyl-1-bromobutane which is insoluble in the aqueous solution of sodium bisulfite, adjusting the pH of the separated aqueous solution of sodium sulfite to be more than or equal to 10 by using 20% NaOH, separating out a solid of the water-insoluble compound of formula D (m =1, n = 1), performing suction filtration to collect the compound of formula D (m =1, n = 1), and drying to obtain a refined compound of formula D (m =1, n = 1) with a purity of 1308g (3.3 mol) of white crystals and an HPLC purity of 99.5%.
2: and (3) difluoromethyl reaction:
after 2500g of anhydrous methanol, 390g (2.4 mol) of hydroxyethyl difluoromethyl sulfone and 53g (2.2 mol) of LiOH were added to a 5000ml three-necked flask and dissolved with stirring at room temperature, 788g (2 mol) of the compound of formula D (m =1, n = 1) was added, the mixture was reacted at 20 to 30 ℃ for 10 to 11 hours, and the compound of formula D (m =1, n = 1) was analyzed by HPLC for disappearance, and the reaction solution of the compound of formula F (m =1, n = 1) was used in the next step of membrane electrolytic oxidation without separation.
3: film electrolytic oxidation reaction:
the synthetic feeding, synthetic operation and condition control are the same as the membrane electrolytic oxidation reaction of the example 1;
pouring the oxidized liquid into a 5000ml three-necked bottle, adding a proper amount of hydrobromic acid to neutralize the oxidized liquid to pH = 6.0-7.0, heating the mixture in a water bath, completely distilling and recovering aqueous methanol, adding 2500G of absolute ethyl alcohol to dissolve the remained solid, performing suction filtration to remove insoluble solid salts such as LiBr and the like, and distilling the filtrate under reduced pressure to recover ethanol to obtain 904G (1.7 mol) of light yellow crystals of a compound of a formula G (m =1, n = 1) with the HPLC purity of 98.7%.
4: and (3) dehydrating diene reaction:
adding 533G (1 mol) of a compound (m =1, n = 1) of a formula G, 96G of trichloroacetic acid, 3G of p-methoxyphenol serving as a polymerization inhibitor and 500G of cyclohexane into a 3000ml three-necked bottle, heating, refluxing, azeotropically dehydrating for 2-3 h, distilling and recovering the cyclohexane at the top temperature of less than or equal to 85 ℃ after water outlet is stopped, adding 1300G of absolute ethanol and a proper amount of lithium carbonate into the remained solid to neutralize the pH to be 6.0-7.0, performing suction filtration to remove the solid, and distilling and removing ethanol from the clear filtrate under reduced pressure to obtain 447G (0.93 mol) of the compound (m =1, n = 1) of the formula A with the HPLC purity of 96.8%.
Example 5:
synthesizing a compound of a formula Q with m =2 and n =1, wherein 3- (4-alpha-methoxyethylphenyl) -3-methyl-1-bromobutane is used as a starting material;
1: and (3) etherification reaction:
adding 4200g of dioxane, 1363g (4.8 mol) of 3- (4-alpha-methoxyethylphenyl) -3-methyl-1-bromobutane, 816g (4.0 mol) of 6- (hydroxyethyl ether ethoxy) -2-hexanone, 132g (0.8 mol) of potassium iodide, 40g of tetrabutylammonium bromide and 560g of anhydrous potassium carbonate (2.0 mol) into a 10000ml three-necked flask, uniformly stirring at room temperature, heating in a water bath to keep at 60-70 ℃ for etherification reaction, and after 16h of reaction, analyzing the disappearance of 6- (hydroxyethyl ether ethoxy) -2-hexanone in a reaction solution by GC, and finishing the reaction; cooling the obtained reaction liquid of the compound (m =2, n = 1) in the formula D to room temperature, adding 85% formic acid to neutralize the reaction liquid until the pH is = 6-7, performing suction filtration to remove solids, washing a filter cake with dioxane, recovering a dioxane washing solution, combining the dioxane washing solution with a crude suction filtration liquid of the compound (m =2, n = 1) in the formula D, maintaining the temperature at the top temperature of less than or equal to 80 ℃, performing reduced pressure distillation and desolventizing, and recovering dioxane.
Separation and refining: pouring the crude product of the desolvated compound (m =2, n = 1) of the formula D into water at room temperature, wherein the unreacted 3- (4-alpha-methoxyethylphenyl) -3-methyl-1-bromobutane and the compound of the formula D are insoluble in water, separating out a solid crude product of the compound (m =2, n = 1) of the formula D which is insoluble in water, and washing away residual dioxane and inorganic salts; preparing 6240g of a 10% aqueous solution of 624g of sodium bisulfite (6 mol), keeping the solution at 30-40 ℃, dissolving a crude solid of a water-insoluble compound (m =2, n = 1) in formula D, pouring the crude solid into an aqueous solution of sodium bisulfite at 30-40 ℃, stirring for 3-4 h, dissolving the compound (m =2, n = 1) in water, recovering 3- (4-alpha-methoxyethylphenyl) -3-methyl-1-bromobutane which is insoluble in the aqueous solution of sodium bisulfite, adjusting the pH of the separated aqueous solution of sodium sulfite to be more than or equal to 10 by using 20% NaOH, separating out a solid of the water-insoluble compound (m =2, n = 1) in formula D, performing suction filtration to collect the compound (m =2, n = 1), and drying to obtain a refined compound (m =2, n = 1) in the form of 1315g of white crystals (3.2 mol) with the purity of HPLC of 99.1.
2: and (3) difluoromethyl reaction:
after adding 2500g of anhydrous methanol, 390g (2.4 mol) of hydroxyethyl difluoromethyl sulfone and 53g (2.2 mol) of LiOH into a 5000ml three-necked flask, stirring and dissolving at room temperature, adding 816g (2 mol) of the compound of formula D (m =2, n = 1), reacting at 20-30 ℃ for 10-11 h, and analyzing the disappearance of the compound of formula D (m =2, n = 1) by HPLC sampling, wherein the obtained reaction solution of the compound of formula F (m =2, n = 1) is directly used for the next membrane electrolytic oxidation reaction without separation.
3: film electrolytic oxidation reaction:
the synthetic feeding, synthetic operation and condition control are the same as the membrane electrolytic oxidation reaction of the example 1;
pouring the oxidized liquid into a 5000ml three-necked bottle, adding a proper amount of hydrobromic acid to neutralize the oxidized liquid to pH = 6.0-7.0, heating the mixture in a water bath, completely distilling and recovering aqueous methanol, adding 2500G of absolute ethyl alcohol to dissolve the remained solid, performing suction filtration to remove insoluble solid salts such as LiBr and the like, and distilling the filtrate under reduced pressure to recover ethanol to obtain 924G (1.69 mol) of a compound (m =2, n = 1) in the form of pale yellow crystals with the HPLC purity of 98.3%.
4: and (3) dehydrating diene reaction:
adding a compound of a formula G (m =2, n = 1) 547G (1 mol), 96G trichloroacetic acid, a polymerization inhibitor p-methoxyphenol 3G and 500G cyclohexane into a 3000ml three-neck flask, heating, refluxing, azeotropically dehydrating for 2-3 h, distilling and recovering the cyclohexane at the top temperature of less than or equal to 85 ℃ after water outlet is stopped, adding 1400G absolute ethyl alcohol and a proper amount of lithium carbonate into the remained solid to neutralize the pH to be 6.0-7.0, performing suction filtration to remove the solid, and distilling and removing the ethyl alcohol from the clear filtrate under reduced pressure to obtain 445G (0.9 mol) of a compound of a formula A (m =2, n = 1) with the HPLC purity of 96.4%.
Example 6:
synthesizing a compound with a formula R of m =3 and n =1, wherein 3- (4-alpha-methoxyethylphenyl) -3-methyl-1-bromobutane is used as a starting material;
1: etherification reaction:
adding 4500g of dioxane, 1362g (4.8 mol) of 3- (4-alpha-methoxyethylphenyl) -3-methyl-1-bromobutane, 872g (4.0 mol) of 7- (hydroxyethyl ether ethoxy) -2-heptanone, 132g (0.8 mol) of potassium iodide, 40g of tetrabutylammonium bromide and 560g of anhydrous potassium carbonate (2.0 mol) into a 10000ml three-necked bottle, uniformly stirring at room temperature, heating in a water bath to keep at 60-70 ℃ for etherification reaction, and after reacting for 16.5h, analyzing the reaction solution by GC (gas chromatography) to eliminate 7- (hydroxyethyl ether ethoxy) -2-heptanone, and finishing the reaction; and cooling the obtained reaction liquid (m =3, n = 1) of the compound shown in the formula D to room temperature, adding 85% formic acid to neutralize the reaction liquid until the pH is = 6-7, performing suction filtration to remove solids, washing a filter cake by dioxane, recovering a dioxane washing solution, combining the dioxane washing solution and a crude suction filtration liquid of the compound shown in the formula D (m =3, n = 1), maintaining the temperature at the top temperature of less than or equal to 80 ℃, performing reduced pressure distillation and desolventizing, and recovering dioxane.
Separation and refining: pouring the crude product of the desolvated compound (m =3, n = 1) of the formula D into water at room temperature, wherein the unreacted 3- (4-alpha-methoxyethylphenyl) -3-methyl-1-bromobutane and the compound (m =3, n = 1) of the formula D are insoluble in water, separating out a crude solid product of the compound (m =3, n = 1) of the formula D which is insoluble in water, and washing away residual dioxane and inorganic salts; preparing 6240g of a 10% aqueous solution of 624g of sodium bisulfite (6 mol), keeping the solution at 30-40 ℃, dissolving a crude solid of a water-insoluble compound (m =3, n = 1) shown in the formula D, pouring the crude solid into an aqueous solution of sodium bisulfite at 30-40 ℃, stirring for 1-2 h, dissolving the compound (m =3, n = 1) shown in the formula D in water, recovering 3- (4-alpha-methoxyethylphenyl) -3-methyl-1-bromobutane which is insoluble in the aqueous solution of sodium bisulfite, adjusting the pH of the separated aqueous solution of sodium sulfite to be more than or equal to 10 by using 20% NaOH, separating out a solid of the water-insoluble compound (m =3, n = 1) shown in the formula D, performing suction filtration to collect the compound (m =3, n = 1) shown in the formula D, and drying to obtain 1355g (3.2 mol) of a white crystal of the refined compound (m =3, n = 1) shown in the formula D, wherein the purity is 99.2% by HPLC.
2: and (3) difluoromethyl reaction:
adding 2500g of anhydrous methanol, 390g (2.4 mol) of hydroxyethyl difluoromethyl sulfone and 53g (2.2 mol) of LiOH into a 5000ml three-necked flask, stirring at room temperature to dissolve, adding 845g (2 mol) of the compound shown in the formula D, reacting at 20-30 ℃ for 10-11 h, analyzing the disappearance of the compound shown in the formula D (m =3, n = 1) by HPLC sampling, and directly using the obtained reaction liquid of the compound shown in the formula F (m =3, n = 1) in the next step of membrane electrolytic oxidation reaction without separation.
3: film electrolytic oxidation reaction:
the synthetic feeding, synthetic operation and condition control are the same as the membrane electrolytic oxidation reaction of the example 1;
pouring the oxidized liquid into a 5000ml three-necked bottle, adding a proper amount of hydrobromic acid to neutralize the oxidized liquid to pH = 6.0-7.0, heating the mixture in a water bath, completely distilling and recovering aqueous methanol, adding 2500G of absolute ethyl alcohol to dissolve the remained solid, performing suction filtration to remove insoluble solid salts such as LiBr and the like, and distilling the filtrate under reduced pressure to recover ethanol to obtain 958G (1.71 mol) of pale yellow crystals of the compound of the formula G (m =3, n = 1) with the HPLC purity of 98.2%.
4: and (3) dehydrating diene reaction:
adding a compound of a formula G (m =3, n = 1) 561G (1 mol), 96G trichloroacetic acid, a polymerization inhibitor p-methoxyphenol 3G and 500G cyclohexane into a 3000ml three-neck flask, heating, refluxing, azeotropically dehydrating for 2-3 h, distilling and recovering the cyclohexane at the top temperature of less than or equal to 85 ℃ after water outlet is stopped, adding 1300G of absolute ethanol and a proper amount of lithium carbonate into the remained solid to neutralize the pH to be 6.0-7.0, performing suction filtration to remove the solid, and distilling and removing the ethanol from the clear filtrate under reduced pressure to obtain a compound of a formula A (m =3, n = 1) 465G (0.91 mol) with the HPLC purity of 96.2%.
Example 7:
synthesizing a compound with a formula K of m =1 and n =0, and taking 3- (4-alpha-methoxyethylphenyl) -3-methyl-1-chlorobutane as a starting material;
1: and (3) etherification reaction:
adding 3200g of dioxane, 1200g (5 mol) of 3- (4-alpha-methoxyethylphenyl) -3-methyl-1-chlorobutane, 586g (4.0 mol) of 5-hydroxyethyl ether-2-pentanone, 150g (0.9 mol) of potassium iodide, 40g of tetrabutylammonium bromide and 560g of anhydrous potassium carbonate (2.0 mol) into a 10000ml three-neck flask, uniformly stirring at room temperature, heating in a water bath to keep at 80-90 ℃ for etherification reaction, reacting for 18h, and analyzing by GC that 5-hydroxyethyl ether-2-pentanone does not disappear in the reaction liquid, and finishing the reaction; cooling the obtained reaction liquid of the compound (m =1, n = 0) in the formula D to room temperature, adding 85% formic acid to neutralize the reaction liquid until the pH is = 6-7, performing suction filtration to remove solids, washing a filter cake with dioxane, recovering a dioxane washing solution, mixing the dioxane washing solution with a crude suction filtration liquid of the compound (m =1, n = 0) in the formula D, maintaining the temperature at the top temperature of less than or equal to 80 ℃, performing reduced pressure distillation and desolventizing, and recovering dioxane.
Separation and refining: pouring the crude product of the compound of formula D after desolventization into water at room temperature, wherein the unreacted 3- (4-alpha-methoxyethylphenyl) -3-methyl-1-chlorobutane and the compound of formula D (m =1, n = 0) are insoluble in water, separating out a crude solid product of the compound of formula D (m =1, n = 0) which is insoluble in water, and washing away residual dioxane and inorganic salts; preparing 624g of sodium bisulfite (6 mol) 10% aqueous solution 6240g, keeping the temperature at 30-40 ℃, dissolving a water-insoluble crude solid of a compound of formula D (m =1, n = 0) in water, pouring the crude solid into a sodium bisulfite aqueous solution at 30-40 ℃, stirring for 2.5-3 h, dissolving the compound of formula D (m =1, n = 0) in water, recovering 3- (4-alpha-methoxyethylphenyl) -3-methyl-1-chlorobutane which is insoluble in the sodium bisulfite aqueous solution, adjusting the pH of the separated sodium sulfite aqueous solution to be more than or equal to 10 by using 20% NaOH, precipitating the water-insoluble solid of the compound of formula D (m =1, n = 0), carrying out suction filtration to collect the compound of formula D (m =1, n = 0), and drying to obtain a refined compound of formula D (m = 915 1, n = 0) with white crystal purity g (2.6 mol) and HPLC 99.4%.
2: and (3) difluoromethyl reaction:
after adding 2500g of anhydrous methanol, 390g (2.4 mol) of hydroxyethyl difluoromethyl sulfone and 53g (2.2 mol) of LiOH into a 5000ml three-necked flask, stirring and dissolving at room temperature, adding 701g (2 mol) of a compound of formula D (m =1, n = 0), reacting at 20-30 ℃ for 10-11 h, and analyzing disappearance of the compound of formula D (m =1, n = 0) by HPLC sampling, wherein the obtained reaction solution of the compound of formula F (m =1, n = 0) is directly used for the next membrane electrolytic oxidation reaction without separation.
3: film electrolytic oxidation reaction:
adding 3000g of 3% LiOH aqueous solution into a 5000ml cathode storage vat A by using a membrane electrolytic oxidation device provided with a compact cross-linked anion membrane, and switching on a circulating pump and a cathode chamber for continuous circulation; adding 3500g of 50% LiBr aqueous solution into a 5000ml anode storage vat B, heating and keeping the temperature at 55-60 ℃, and switching on a circulating pump and an anode chamber for continuous circulation; adding the reaction solution of the compound (m =1, n = 0) shown in the formula F into a 5000ml oxidation solution storage barrel C, adding 120g of LiOH (5 mol), stirring for dissolving, keeping strong alkalinity with pH being more than or equal to 12, and starting a circulating pump and an oxidation chamber for continuous circulation; connecting 8V electrolytic power supply, electrolyzing the anode chamber to generate bromine, and maintaining the temperature of the feed liquid B in the anode barrel at 60 ℃ or higher to generate bromine Br2Volatilizing and absorbing in an oxidizing solution storage barrel C; the oxidizing liquid storage barrel C releases heat, the carbanion of the compound of the formula F (m =1, n = 0) is rapidly oxidized, bromine rapidly fades, and the oxidizing liquid storage barrel C is kept not to flow back; the membrane electrolysis continuously operates at 8V/25-30A, the bromine fading of the oxidation liquid begins to slow down after 3 hours, the pH of the oxidation liquid begins to drop to pH = 10-11, a compound (m =1, n = 0) of a formula F analyzed by HPLC disappears, the membrane electrolysis oxidation reaction is finished, a proper amount of hydrazine hydrate is dripped to digest the bromine red and the oxidability, the starch-KI test paper does not change color, and the temperature is reduced to room temperature.
Pouring the oxidized liquid into a 5000ml three-necked bottle, adding a proper amount of hydrobromic acid to neutralize the oxidized liquid to pH = 6.0-7.0, heating the mixture in a water bath, completely distilling and recovering aqueous methanol, adding 2500G of absolute ethanol to dissolve the remained solid, performing suction filtration to remove insoluble solid salts such as LiBr and the like, and distilling the filtrate under reduced pressure to recover ethanol to obtain 862G (1.76 mol) of light yellow crystals of the compound of the formula G (m =1, n = 0) with the HPLC purity of 98.6%.
4: and (3) dehydrating diene reaction:
adding 489G (1 mol) of a compound (m =1, n = 0) of a formula G, 140G of trichloroacetic acid, 3G of p-methoxyphenol serving as a polymerization inhibitor and 500G of cyclohexane into a 3000ml three-neck flask, carrying out heating reflux azeotropic dehydration for 2.5-3 h, distilling and recovering the cyclohexane at the top temperature of less than or equal to 85 ℃ after water discharge is stopped, adding 1400G of absolute ethyl alcohol and a proper amount of lithium carbonate into the remaining solid to neutralize the solid to the pH of = 6.0-7.0, carrying out suction filtration to remove the solid, and carrying out reduced pressure distillation on the clear filtrate to remove the ethyl alcohol, thereby obtaining 402G (0.92 mol) of the compound (m =1, n = 0) of the formula A and having the HPLC purity of 97.5%.
Example 8:
synthesizing a compound with a formula P, wherein m =1 and n =1, and taking 3- (4-alpha-methoxyethylphenyl) -3-methyl-1-chlorobutane as a starting material;
1: and (3) etherification reaction:
adding 3500g of dioxane, 1320g (5.5 mol) of 3- (4-alpha-methoxyethylphenyl) -3-methyl-1-chlorobutane, 761g (4.0 mol) of 5- (hydroxyethyl ether ethoxy) -2-pentanone, 150g (0.9 mol) of potassium iodide, 40g of tetrabutylammonium bromide and 560g of anhydrous potassium carbonate (2.0 mol) into a 10000ml three-necked bottle, uniformly stirring at room temperature, heating in a water bath to keep at 80-90 ℃ for etherification reaction, and after reacting for 18.5h, GC analysis is carried out on the reaction solution to ensure that 5- (hydroxyethyl ether ethoxy) -2-pentanone does not disappear, thus finishing the reaction; cooling the obtained reaction liquid of the compound (m =1, n = 1) in the formula D to room temperature, adding 85% formic acid to neutralize the reaction liquid until the pH is = 6-7, performing suction filtration to remove solids, washing a filter cake with dioxane, recovering a dioxane washing solution, combining the dioxane washing solution with a crude suction filtration liquid of the compound (m =1, n = 1) in the formula D, maintaining the temperature at the top temperature of less than or equal to 80 ℃, performing reduced pressure distillation and desolventizing, and recovering dioxane.
Separation and refining: pouring the crude desolvated compound of formula D (m =1, n = 1) into water at room temperature, wherein the unreacted 3- (4- α -methoxyethylphenyl) -3-methyl-1-chlorobutane and the compound of formula D (m =1, n = 1) are insoluble in water, separating out the crude solid water-insoluble compound of formula D (m =1, n = 1), and washing away the residual dioxane and inorganic salts; preparing 6240g of a 10% aqueous solution of 624g of sodium bisulfite (6 mol), keeping the temperature at 30-40 ℃, dissolving a crude solid of a water-insoluble compound shown in the formula D (m =1, n = 1), pouring the crude solid into an aqueous solution of sodium bisulfite at 30-40 ℃, stirring for 2.5-3 h, dissolving the compound shown in the formula D in water, recovering 3- (4-alpha-methoxyethylphenyl) -3-methyl-1-chlorobutane which is insoluble in the aqueous solution of sodium bisulfite, adjusting the pH of the separated aqueous solution of sodium sulfite to be more than or equal to 10 by using 20% NaOH, separating out a solid of the water-insoluble compound shown in the formula D (m =1, n = 1), performing suction filtration to collect the compound shown in the formula D (m =1, n = 1), and drying to obtain 995g (2.5 mol) of a white crystal of the compound shown in the formula D (the refined formula D), wherein the purity of the white crystal is 99.4% by HPLC.
2: and (3) difluoromethyl reaction:
adding 2500g of anhydrous methanol, 390g (2.4 mol) of hydroxyethyl difluoromethyl sulfone and 53g (2.2 mol) of LiOH into a 5000ml three-necked flask, stirring at room temperature to dissolve, adding 789g (2 mol) of the compound shown in the formula D, reacting at 20-30 ℃ for 10-11 h, analyzing the disappearance of the compound shown in the formula D by HPLC sampling, and directly using the obtained reaction solution of the compound shown in the formula F (m =1, n = 1) in the next step of membrane electrolytic oxidation reaction without separation.
3: film electrolytic oxidation reaction:
the synthetic feeding, synthetic operation and condition control are the same as the membrane electrolytic oxidation reaction of the example 7;
pouring the oxidized liquid into a 5000ml three-necked bottle, adding a proper amount of hydrobromic acid to neutralize the oxidized liquid to pH = 6.0-7.0, heating the mixture in a water bath, completely distilling and recovering aqueous methanol, adding 2500G of absolute ethyl alcohol to dissolve the remained solid, performing suction filtration to remove insoluble solid salts such as LiBr and the like, and distilling the filtrate under reduced pressure to recover ethanol to obtain 938G (1.76 mol) of a light yellow crystal of a compound of a formula G (m =1, n = 1) with the HPLC purity of 98.4%.
4: and (3) dehydrating diene reaction:
adding 533G (1 mol) of compound shown in formula G, 150G of trichloroacetic acid, 3G of polymerization inhibitor p-methoxyphenol and 500G of cyclohexane into a 3000ml three-neck flask, heating, refluxing, azeotropically dehydrating for 2.5-3 h, distilling and recovering the cyclohexane at the top temperature of less than or equal to 85 ℃ after water discharge is stopped, adding 1500G of absolute ethyl alcohol and a proper amount of lithium carbonate into the remained solid to neutralize the pH to be 6.0-7.0, filtering to remove the solid by suction, and distilling and removing the ethyl alcohol from the clear filtrate under reduced pressure to obtain 448G (0.93 mol) of compound shown in formula A (m =1, n = 1) with the HPLC purity of 97.1%.
Claims (8)
1. A high-elongation lithium ion membrane compound of tert-alkyl aryl ether diene difluoromethylsulfonate and its synthesis method, lithium tert-alkyl ethoxy alkyl aryl ether diene difluoromethylsulfonate with chemical structure of formula A:
wherein: m =1~3, n =0~ 1.
2. The method for synthesizing the lithium ion membrane compound of aryl tertiary alkyl ethoxy alkyl ether diene difluoromethyl sulfonate as claimed in claim 1, is mainly characterized in that 3- (4-alpha-methoxyethyl phenyl) -3-methyl-1-halogenated butane compound with chemical structure of formula B is used as starting material;
wherein: x is chlorine or bromine.
3. The method for synthesizing lithium aralkyl ethoxy alkyl ether diene difluoromethyl sulfonate ionic membrane compound according to claim 1, which is characterized in that hydroxyethyl ether alkyl-2-one compound with chemical structure of formula C is used as starting material;
wherein: m =1~3, n =0~ 1.
4. The method for synthesizing lithium bis (difluoromethyl) benzenesulfonate ionic membrane compounds of aryl tert-alkyl ethoxy alkyl ethers according to claim 1, characterized in that four-step synthesis reaction of etherification, difluoromethyl reaction, membrane electrolytic oxidation and dehydrated diene is required, and finally lithium bis (difluoromethyl) benzenesulfonate ionic membrane compounds of aryl tert-alkyl ethoxy alkyl ethers with chemical structure of formula a are synthesized:
(1) and (3) etherification reaction: in dioxane, a compound shown in a formula B, a slightly excessive compound shown in a formula C and a small amount of tetrabutylammonium bromide are mixed and dissolved, potassium carbonate and a small amount of potassium iodide are added, the etherification reaction of the compound shown in the formula B and the compound shown in the formula C is completed at 60-90 ℃, acetic acid is added for neutralization after the reaction is finished, and an aromatic tertiary alkyl ether ketone compound with a chemical structure shown in a formula D is obtained by separation:
wherein: m = 1-3, n = 0-1;
(2) and (3) difluoromethyl reaction: dissolving the compound of the formula E in methanol, adding a small amount of LiOH for alkaline catalysis, and adding the compound of the formula E and the ketone group of the compound of the formula D at the temperature of 10-40 ℃ to obtain a methanol solution of the compound of the formula F; the molar ratio of the compound of the formula E to the compound of the formula D is 1.1-1.4: 1;
wherein: m = 1-3, n = 0-1;
(3) film electrolytic oxidation reaction: adding excessive LiOH into a methanol solution of a compound in the formula F, keeping the strong alkaline pH of the solution to be more than or equal to 12, continuously performing membrane electrolysis oxidation in a bromine membrane electrolysis device, reducing the pH of the material to be 9-10, adding a proper amount of hydrobromic acid, keeping the pH of a neutralization oxidation solution to be 6.0-7.5, distilling and recovering aqueous methanol, refining with absolute ethyl alcohol, and separating to obtain an aromatic tert-alkyl ethoxy alkyl ether-2-hydroxy-2-difluoromethyl sulfonic acid lithium compound in a chemical structure of a formula G;
wherein: m = 1-3, n = 0-1;
(4) and (3) dehydrating diene reaction: adding an acid catalyst and cyclohexane into the compound of the formula G, heating to 80-90 ℃, refluxing and acid cracking, adding a small amount of lithium carbonate for neutralization after complete cracking, distilling and recovering the cyclohexane, adding absolute ethyl alcohol for dissolving, and separating to obtain the lithium aryl tertiary alkyl ethoxy alkyl ether diene difluoromethyl sulfonate with the chemical structure of the formula A;
wherein: m =1~3, n =0~ 1.
5. The membrane etherification reaction according to claim 4, wherein the molar ratio of the compound of formula B to the compound of formula C is 1:1.2 to 1.5; the molar ratio of the potassium iodide to the compound of the formula B is 0.1-0.3: 1.
6. the electromembrane oxidation reaction of claim 4, wherein the molar ratio of the added LiOH to the compound of formula F is 2-4: 1.
7. membrane electrolytic oxidation reaction according to claim 4, characterized essentially by the necessity of using dense cross-linked anionic membranes capable of blocking methanol permeation but capable of passing Br—An anion.
8. The dehydrodiene reaction of claim 4, wherein the acid catalyst is trichloroacetic acid, and the amount of the acid catalyst is 10-30 wt% of the compound of formula G.
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| 唐小红等: "离子膜电槽电流密度的研究及应用", 《化学研究与应用》 * |
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