CN108912155A - A kind of preparation method of difluoro oxalate borate - Google Patents
A kind of preparation method of difluoro oxalate borate Download PDFInfo
- Publication number
- CN108912155A CN108912155A CN201810992866.3A CN201810992866A CN108912155A CN 108912155 A CN108912155 A CN 108912155A CN 201810992866 A CN201810992866 A CN 201810992866A CN 108912155 A CN108912155 A CN 108912155A
- Authority
- CN
- China
- Prior art keywords
- boron trifluoride
- oxalate borate
- difluoro oxalate
- ether
- preparation
- 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.)
- Pending
Links
- KWWDVIIKMNQADG-UHFFFAOYSA-N boric acid;difluoro oxalate Chemical compound OB(O)O.FOC(=O)C(=O)OF KWWDVIIKMNQADG-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 229910015900 BF3 Inorganic materials 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 238000002425 crystallisation Methods 0.000 claims abstract description 7
- 230000008025 crystallization Effects 0.000 claims abstract description 6
- 239000000010 aprotic solvent Substances 0.000 claims abstract description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 57
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 52
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- 235000006408 oxalic acid Nutrition 0.000 claims description 19
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 11
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 10
- -1 alchlor Chemical compound 0.000 claims description 10
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 10
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 9
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 9
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 7
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 239000005049 silicon tetrachloride Substances 0.000 claims description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 5
- 239000012320 chlorinating reagent Substances 0.000 claims description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims description 5
- 150000002825 nitriles Chemical class 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 4
- 150000004292 cyclic ethers Chemical class 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- PVKVBDZRILNPJY-UHFFFAOYSA-N 1-butoxybutane;trifluoroborane Chemical compound FB(F)F.CCCCOCCCC PVKVBDZRILNPJY-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-L Oxalate Chemical compound [O-]C(=O)C([O-])=O MUBZPKHOEPUJKR-UHFFFAOYSA-L 0.000 claims description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- CHNLPLHJUPMEOI-UHFFFAOYSA-N oxolane;trifluoroborane Chemical compound FB(F)F.C1CCOC1 CHNLPLHJUPMEOI-UHFFFAOYSA-N 0.000 claims description 3
- 229910001415 sodium ion Inorganic materials 0.000 claims description 3
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 2
- LVZGQWKTUCVPBQ-UHFFFAOYSA-N acetic acid;trifluoroborane Chemical compound CC(O)=O.FB(F)F LVZGQWKTUCVPBQ-UHFFFAOYSA-N 0.000 claims description 2
- MEMUCXUKCBNISQ-UHFFFAOYSA-N acetonitrile;trifluoroborane Chemical group CC#N.FB(F)F MEMUCXUKCBNISQ-UHFFFAOYSA-N 0.000 claims description 2
- VWCIBMAHWVHJJM-UHFFFAOYSA-N butyl acetate trifluoroborane Chemical compound C(C)(=O)OCCCC.B(F)(F)F VWCIBMAHWVHJJM-UHFFFAOYSA-N 0.000 claims description 2
- FZUIUHFZKOQKHQ-UHFFFAOYSA-N diethyl carbonate;trifluoroborane Chemical compound FB(F)F.CCOC(=O)OCC FZUIUHFZKOQKHQ-UHFFFAOYSA-N 0.000 claims description 2
- UNWSCLFRWCYCHG-UHFFFAOYSA-N ethyl acetate;trifluoroborane Chemical compound FB(F)F.CCOC(C)=O UNWSCLFRWCYCHG-UHFFFAOYSA-N 0.000 claims description 2
- OYTBOLVDKAGZLT-UHFFFAOYSA-N methyl hydrogen carbonate trifluoroborane Chemical compound COC(O)=O.B(F)(F)F OYTBOLVDKAGZLT-UHFFFAOYSA-N 0.000 claims description 2
- DBIWHDFLQHGOCS-UHFFFAOYSA-N piperidine;trifluoroborane Chemical class FB(F)F.C1CCNCC1 DBIWHDFLQHGOCS-UHFFFAOYSA-N 0.000 claims description 2
- 229910001414 potassium ion Inorganic materials 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- UYAGPULHTNCMOT-UHFFFAOYSA-N [B].FB(F)F Chemical compound [B].FB(F)F UYAGPULHTNCMOT-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 150000003457 sulfones Chemical class 0.000 claims 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 31
- 238000000034 method Methods 0.000 abstract description 12
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 125000000129 anionic group Chemical group 0.000 abstract 1
- 239000012535 impurity Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 45
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 39
- 238000003756 stirring Methods 0.000 description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 30
- 239000007787 solid Substances 0.000 description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 21
- 229910052786 argon Inorganic materials 0.000 description 21
- 239000013078 crystal Substances 0.000 description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- 229910017604 nitric acid Inorganic materials 0.000 description 20
- 229910001868 water Inorganic materials 0.000 description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 17
- 229910052744 lithium Inorganic materials 0.000 description 17
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 13
- 101710134784 Agnoprotein Proteins 0.000 description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 238000004062 sedimentation Methods 0.000 description 10
- 238000004879 turbidimetry Methods 0.000 description 10
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 9
- 150000002431 hydrogen Chemical class 0.000 description 9
- 235000010338 boric acid Nutrition 0.000 description 8
- 229960002645 boric acid Drugs 0.000 description 8
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 description 8
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 7
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000000643 oven drying Methods 0.000 description 5
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 5
- 238000004607 11B NMR spectroscopy Methods 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- IJMWOMHMDSDKGK-UHFFFAOYSA-N Isopropyl propionate Chemical compound CCC(=O)OC(C)C IJMWOMHMDSDKGK-UHFFFAOYSA-N 0.000 description 4
- 229910003910 SiCl4 Inorganic materials 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 4
- 239000011255 nonaqueous electrolyte Substances 0.000 description 4
- 229940090181 propyl acetate Drugs 0.000 description 4
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 4
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 3
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 3
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 description 3
- 230000005311 nuclear magnetism Effects 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 2
- GQQFGLUEAGQQJA-UHFFFAOYSA-N 1,3-dioxecan-2-one Chemical compound O=C1OCCCCCCCO1 GQQFGLUEAGQQJA-UHFFFAOYSA-N 0.000 description 2
- 238000004293 19F NMR spectroscopy Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229910006124 SOCl2 Inorganic materials 0.000 description 2
- 229910003074 TiCl4 Inorganic materials 0.000 description 2
- 229940043232 butyl acetate Drugs 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- BYKSDPYYTJQZOA-UHFFFAOYSA-N difluoro oxalate Chemical compound FOC(=O)C(=O)OF BYKSDPYYTJQZOA-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229940093499 ethyl acetate Drugs 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 2
- 229940011051 isopropyl acetate Drugs 0.000 description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- ZFCQDZKQFPEDJE-UHFFFAOYSA-N thiolane 1,1-dioxide trifluoroborane Chemical compound S1(=O)(=O)CCCC1.B(F)(F)F ZFCQDZKQFPEDJE-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- KFNNIILCVOLYIR-UHFFFAOYSA-N Propyl formate Chemical compound CCCOC=O KFNNIILCVOLYIR-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000001897 boron-11 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- SLCLABDXYGNNOO-UHFFFAOYSA-N dimethyl carbonate;trifluoroborane Chemical compound FB(F)F.COC(=O)OC SLCLABDXYGNNOO-UHFFFAOYSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000000806 fluorine-19 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Secondary Cells (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of preparation methods of difluoro oxalate borate, which is characterized in that includes the following steps：（1）Boron trifluoride complex is dissolved in aprotic solvent, binoxalate and chloride is added, reaction obtains difluoro oxalate borate solution；（2）Solution is deaerated and is concentrated, poor solvent, which is added, is precipitated the crystallization of difluoro oxalate borate, is then filtered, washed, dries to get difluoro oxalate borate.Method and process of the invention is simple, and the reaction time is short, high income, and product purity is high, can be effectively controlled metal ion and anionic impurity content, can prepare high-purity difluoro oxalate borate target product.
Description
Technical field
The present invention relates to a kind of preparation sides of difluoro oxalate borate that can be used in battery with nonaqueous electrolyte additive
Method.
Background technique
Difluoro oxalate borate may be used as the additive of battery with nonaqueous electrolyte.For example, difluorine oxalic acid boracic acid lithium is available
Make the battery with nonaqueous electrolyte additive such as lithium ion battery, lithium-ion capacitor, difluoro oxalate Boratex can be used as sodium ion
The additive of battery.As the preparation method of one such i.e. difluorine oxalic acid boracic acid lithium, such as patent document one（Chinese patent：
A kind of synthesis technology obtaining difluorine oxalic acid boracic acid lithium and di-oxalate lithium borate；The patent No.：CN200910144760.9）, side
Method be by fluorine-containing compound, the compound of boracic, the compound containing lithium and the compound containing oxalate in reaction medium
Reaction, obtains the solution containing difluorine oxalic acid boracic acid lithium and di-oxalate lithium borate, in the patent, needs by filtering and organic solvent
The method of extraction separates difluorine oxalic acid boracic acid lithium with two kinds of substances of di-oxalate lithium borate, and passes through crystallisation by cooling and recrystallization etc.
For method by purification of products, step is more, and process is extremely complex, is not easy to industrialized production.Patent document two（European patent：
Process for synthesizing ionic metal complex；The patent No.：EP1308449A2）Using oxalic acid, tetrafluoro
Lithium borate, lithium fluoride and boron chloride or trimethoxy-boron react in dimethyl carbonate, obtain difluorine oxalic acid boracic acid lithium, still
Raw material LiBF4 itself is the additive of lithium ion battery, it is difficult to which high-volume obtains, and at high cost, economically infeasible.
Summary of the invention：
It is an object of the invention to overcome the deficiencies of existing technologies, providing one kind can be used in battery with nonaqueous electrolyte additive
Difluoro oxalate borate preparation method.
The present invention uses following technical scheme:
A kind of preparation method of difluoro oxalate borate, which is characterized in that include the following steps：
（1）Binoxalate, boron trifluoride complex and aprotic solvent are fitted into reaction vessel and mixed, chlorinating agent, which is added, makes it
Reaction, obtains the solution containing difluoro oxalate borate of clear；
（2）Solution is deaerated and is concentrated, poor solvent, which is added, is precipitated the crystallization of difluoro oxalate borate, is then filtered, washed, dries
Obtain the difluoro oxalate borate that purity is higher than 99.8%.
Preferably, the boron trifluoride complex is boron trifluoride acetonitrile, boron trifluoride diethyl carbonate, boron trifluoride
Dimethyl carbonate, boron trifluoride tetrahydrofuran, boron trifluoride gamma-butyrolacton, boron trifluoride ethyl acetate, boron trifluoride ether,
Boron trifluoride methyl ether, boron trifluoride glycol dimethyl ether, boron trifluoride butyl ether, boron trifluoride acetic acid, boron trifluoride piperidines, trifluoro
Change one of boron butyl acetate, boron trifluoride sulfolane or multiple combinations.
Preferably, the binoxalate oxalate ion and the molar ratio of boron trifluoride in boron trifluoride complex are
1：（0.9~2）.It is furthermore preferred that mole of the binoxalate oxalate ion and boron trifluoride in boron trifluoride complex
Than being 1：（1~1.2）.Boron trifluoride is preferably appropriate excessive, and otherwise binoxalate unreacted is complete to remain in reaction solution, it is difficult to remove
It goes.Boron trifluoride also should be excessive too many, in order to avoid waste raw material or cause other unnecessary reactions.
Preferably, the chlorinating agent is phosphorus trichloride, phosphorus pentachloride, silicon tetrachloride, titanium tetrachloride, alchlor, two
At least one of chlorine sulfoxide.
Preferably, the range that the temperature of the reaction is 0 ~ 50 DEG C.It is furthermore preferred that the temperature of the reaction be 20 ~
45 DEG C of range.Reaction temperature is too high, and chloride-sublimation is very fast, cannot react completely；Reaction temperature is too low and is unfavorable for reacting
It carries out.
Preferably, the aprotic solvent be linear carbonate, cyclic carbonate, cyclic ester, chain ester, cyclic ether,
One of chain ether, nitrile or multiple combinations.Include but are not limited to ethylene carbonate, butylene carbonate, pentylene,
Dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, ethylene carbonate, propene carbonate, gamma-butyrolacton,
Methyl formate, Ethyl formate, propyl formate, butyl formate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, second
Sour isobutyl ester, propyl propionate, isopropyl propionate, dimethyl ether, diethyl ether, dipropyl ether, t-butyl methyl ether, 1,1- dimethyl ethane,
1,2- dimethoxy-ethane, ethylene oxide, tetrahydrofuran, propylene oxide, acetonitrile, propionitrile.It is preferred that dimethyl carbonate, carbonic acid diethyl
Ester, dipropyl carbonate, methyl ethyl carbonate, ethylene carbonate, propene carbonate, gamma-butyrolacton, methyl formate, Ethyl formate, first
Propyl propionate, butyl formate, ethyl acetate, propyl acetate, butyl acetate, propyl propionate, isopropyl propionate, dimethyl ether, diethyl ether,
One of dipropyl ether, 1,1- dimethyl ethane, 1,2- dimethoxy-ethane, tetrahydrofuran, propylene oxide, acetonitrile or a variety of groups
It closes.
Preferably, the poor solvent is cyclic carbonate, linear carbonate, cyclic ester, chain ester, cyclic ether, chain
One of shape ether, nitrile, petroleum ether, n-hexane, hexamethylene, toluene, ethylbenzene, methylene chloride, chloroform, dichloroethanes or
It is a variety of to be mixed with arbitrary proportion.Include but are not limited to ethylene carbonate, butylene carbonate, pentylene, dimethyl carbonate,
Diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, ethylene carbonate, propene carbonate, gamma-butyrolacton, methyl formate, first
Acetoacetic ester, propyl formate, butyl formate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, third
Propyl propionate, isopropyl propionate, dimethyl ether, diethyl ether, dipropyl ether, t-butyl methyl ether, 1,1- dimethyl ethane, 1,2- dimethoxy
Ethane, ethylene oxide, tetrahydrofuran, propylene oxide, acetonitrile, propionitrile, petroleum ether, n-hexane, hexamethylene, toluene, ethylbenzene, dichloro
Methane, chloroform, dichloroethanes.It is preferred that tetrahydrofuran, propylene oxide, acetonitrile.It is preferred that ethylene carbonate, dimethyl carbonate,
Diethyl carbonate, Ethyl formate, propyl formate, propyl propionate, dimethyl ether, diethyl ether, ethylene oxide, tetrahydrofuran, acetonitrile, second
One of nitrile, propionitrile, petroleum ether, n-hexane, hexamethylene, toluene, ethylbenzene, methylene chloride, dichloroethanes or multiple combinations.
In the present invention, when binoxalate encounters boron trifluoride, difluoro oxalate borate and hydrofluoric acid are generated, due to hydrofluoric acid
There is certain solubility in organic solvent, which is a balanced reaction, and chlorinating agent is added by hydrofluoric acid into chlorination
Hydrogen evolution, so that the reaction for generating difluoro oxalate borate constantly carries out.Binoxalate is constantly dissolved to reaction solution simultaneously
Become clear.
Preferably, the crystallization temperature is -25 DEG C ~ 50 DEG C；The drying is vacuum drying, and vacuum degree is -0.01
~ -0.1MPa, drying temperature are 40 DEG C ~ 120 DEG C.
In addition, the counter cation of the binoxalate is selected from by lithium ion, sodium ion, potassium ion and tetraalkyl
At least one counter cation in ammonium ion composition.
In the present invention, the reaction carries out preferably in closed container, and air or moisture is avoided to enter.Reactant grass
Sour hydrogen salt should be dried sufficiently, and be free of the crystallization water.Reaction preferably carries out in the environment of inert gas shielding, the indifferent gas
Body is selected from one of nitrogen, helium, argon gas and neon.
It is of the present invention reaction preferably be stirred to react, the present invention for stirring concrete mode without limit, ability
Known to field technique personnel.
Beneficial effects of the present invention：
1, the present invention provides a kind of methods for preparing difluoro oxalate borate powder.
2, method and process of the invention is simple, and the reaction time is short, high income, can be effectively controlled metal ion and anion is miscellaneous
Matter content can prepare high-purity difluoro oxalate borate target product.
Detailed description of the invention
The B of the difluorine oxalic acid boracic acid lithium prepared in Fig. 1 embodiment 1 composes nuclear-magnetism figure（11B-NMR）.
Specific embodiment
The present invention will be further described in detail below with reference to specific embodiments.
Embodiment 1：
In the glove box full of dry argon gas, dried oxalic acid hydrogen lithium is added into three-neck flask（LiHC2O4）48.0g
（0.5mol）And phosphorus pentachloride（PCl5）20.8g（0.1mol）, then the tetrahydrofuran dry to three-neck flask addition（THF）
108g, flask are connected with valvular gas conduit, another two mouthfuls of caps flatly.Flask is taken out from glove box, is placed in
35 DEG C of stirred in water bath, boron trifluoride tetrahydrofuran is added into flask using constant pressure funnel（BF3·THF）73.5g
（0.525mol）, react and start to carry out, the gas of generation is flowed through equipped with being absorbed in sodium hydroxide solution device, and time-consuming 2 is added dropwise
Hour.Solid is slowly dissolved, solution went clear, and keeps the temperature one hour at 35 DEG C, and reaction is released without gas indicates that reaction terminates.?
Under the protection of argon gas stream, dichloroethanes is added into flask（CH2Cl2）800mL is slowly stirred at 25 DEG C and is precipitated to crystal, stops
It only stirs, after crystal sedimentation, dichloroethanes is used in filtering（CH2Cl2）Washing, gained crystal are transferred to vacuum oven drying, vacuum
Degree is -0.098MPa, and drying temperature is 90 DEG C, obtains white solid 57.5g, yield 80%.
The present invention uses obtained product11B-NMR and19F-NMR is analyzed and identified, and NMR is with deuterated DMSO
For solvent, carried out on the basis of TMS.Fig. 1 is that difluoro oxalate borate is made in the present embodiment11B-NMR composes nuclear-magnetism figure, and display produces
Product purity is greater than 99.8%.Being displaced between 10ppm ~ 0ppm as seen from the figure has the unimodal of difluoro oxalate borate, is identified as
Difluorine oxalic acid boracic acid lithium salt.
The content of chloride ion is analyzed using turbidimetry, specially：0.5g solid sample is taken, 8mL deionized water is dissolved in,
1mL AgNO is added3/HNO3Solution（AgNO3：HNO3：H2O=1:65:34, mass ratio）, then that acquired solution distilled water is dilute
It releases to 25mL, compares determining chloride ion range with standard sample turbidity.Chloride ion content is lower than 5ppm.
Embodiment 2：
In the glove box full of dry argon gas, dry dimethyl carbonate is added into three-neck flask（DMC）67.5g, while stirring
It mixes side and boron trifluoride methylcarbonate is added（BF3·DMC）41.0g is dissolved, and dried oxalic acid hydrogen lithium is then added
（LiHC2O4）24.0g（0.25mol）.Flask is taken out from glove box, is impregnated in 35 DEG C of water-baths, and be stirred continuously.It uses
Constant pressure funnel is slowly added into phosphorus trichloride（PCl3）13.7g（0.1mol）, reaction takes place.The gas of generation flows into dress
Have in sodium hydroxide solution device and absorbs.Add phosphorus trichloride（PCl3）It is 1.5 hours time-consuming, one hour then is kept the temperature at 35 DEG C,
Reaction solution becomes clarification, and no gas, which is released, indicates that reaction terminates.Reaction solution is vacuumized, while being warming up to 50 DEG C, concentration and evaporation.?
Under the protection of argon gas stream, hexamethylene 800mL is added into flask, slowly stirs and is precipitated to crystal.Bath temperature is reduced to -10
DEG C, stopping stirring, after crystal sedimentation, filtering is washed with hexamethylene, and it is dry to be transferred to vacuum oven, and vacuum degree is-
0.097MPa, drying temperature are 80 DEG C, obtain white solid 31.6g, yield 88%.
The content of chloride ion is analyzed using turbidimetry, specially：0.5g solid sample is taken, 8mL deionized water is dissolved in,
1mL AgNO is added3/HNO3Solution（AgNO3：HNO3：H2O=1:65:34, mass ratio）, then that acquired solution distilled water is dilute
It releases to 25mL, compares determining chloride ion range with standard sample turbidity.Chloride ion content is lower than 5ppm.
Embodiment 3：
In dry argon gas glove box, dry ether is added into three-neck flask（Ether）55.6g, then into flask
The sufficiently dry oxalic acid hydrogen lithium 24.0g of investment（0.25mol）With boron trifluoride ether 36.9g, flask is connected with valve flatly
Gas conduit, another two mouthfuls of caps.Flask is taken out into glove box, is impregnated in 40 DEG C of water-baths, and constantly stirs mixture.
Silicon tetrachloride is slowly added dropwise using constant pressure funnel（SiCl4）11.9g（0.07mol）, reaction takes place.The gas of generation
It flows into be equipped in sodium hydroxide solution device and absorb.Silicon tetrachloride is added dropwise（SiCl4）It is 1 hour time-consuming, then one is kept the temperature at 40 DEG C
Hour, reaction solution becomes clarification, and no gas, which is released, indicates that reaction terminates.40 DEG C are warming up to, solvent is evaporated.In the protection of argon gas stream
Under, methylene chloride is added into flask（CH2Cl2）800mL is slowly stirred and is precipitated to crystal.Bath temperature is reduced to 0 DEG C, is stopped
Stirring, after crystal sedimentation, methylene chloride is used in filtering（CH2Cl2）Washing, it is dry to be transferred to vacuum oven, and vacuum degree is-
0.097MPa, drying temperature are 100 DEG C, obtain white solid 25.8g, yield 72%.
The content of chloride ion is analyzed using turbidimetry, specially：0.5g solid sample is taken, 8mL deionized water is dissolved in,
1mL AgNO is added3/HNO3Solution（AgNO3：HNO3：H2O=1:65:34, mass ratio）, then that acquired solution distilled water is dilute
It releases to 25mL, compares determining chloride ion range with standard sample turbidity.Chloride ion content is lower than 5ppm.
Embodiment 4：
In dry argon gas glove box, dry ethyl acetate is added into three-neck flask（EA）66.0g, then into flask
The sufficiently dry sodium bioxalate of investment（NaHC2O4）28g（0.25mol）With boron trifluoride ethyl acetate（BF3·EA）40.5g burning
Bottle is connected with valvular gas conduit, another two mouthfuls of caps flatly.Flask is taken out into glove box, is impregnated in 40 DEG C of water-baths
In, and constantly stir mixture.Titanium tetrachloride is slowly added dropwise using constant pressure funnel（TiCl4）13.3g（0.07mol）, instead
It should take place.The gas of generation, which flows into be equipped in sodium hydroxide solution device, to be absorbed.Titanium tetrachloride is added dropwise（TiCl4）Time-consuming 1
Hour, one hour then is kept the temperature at 40 DEG C, reaction is released without gas indicates that reaction terminates.Reaction solution is filtered, filtrate is taken out true
Sky, while 50 DEG C are warming up to, concentration and evaporation.Under the protection of argon gas stream, methylene chloride is added into flask（CH2Cl2）800mL,
It slowly stirs and is precipitated to crystal.Bath temperature is reduced to 0 DEG C, stops stirring, after crystal sedimentation, methylene chloride is used in filtering
（CH2Cl2）Washing is transferred to vacuum oven drying, and vacuum degree is -0.097MPa, and drying temperature is 100 DEG C, obtains white solid
28.8g, yield 72%.
To obtained product, use11B-NMR and19F-NMR is analyzed and identified, NMR be using deuterated DMSO as solvent,
It is carried out on the basis of TMS.11B-NMR and19F-NMR spectrum nuclear-magnetism figure shows that product is difluoro oxalate Boratex.
The content of chloride ion is analyzed using turbidimetry, specially：0.5g solid sample is taken, 8mL deionized water is dissolved in,
1mL AgNO is added3/HNO3Solution（AgNO3：HNO3：H2O=1:65:34, mass ratio）, then that acquired solution distilled water is dilute
It releases to 25mL, compares determining chloride ion range with standard sample turbidity.Chloride ion content is lower than 5ppm.
Embodiment 5：
In dry argon gas glove box, dry methyl formate is added into three-neck flask（MF）, Ethyl formate（EF）, formic acid
Propyl ester（PM）, butyl formate（BF）, ethyl acetate（EA）, propyl acetate（PA）, butyl acetate（BA）, propyl propionate（PP）Altogether
99.2g（Each component quality is average）, boron trifluoride butyl acetate is added while stirring（BF3·BA）47.8g is dissolved, so
Dried oxalic acid hydrogen lithium is put into backward flask（LiHC2O4）24.0g（0.25mol）, flask is taken out into glove box, is impregnated in
15 DEG C of stirred in water bath, and constantly stir mixture.Alchlor is slowly added to using feeder for solid materials（AlCl3）12.0g
（0.09mol）, reaction takes place.The gas of generation, which flows into be equipped in sodium hydroxide solution device, to be absorbed.Add alchlor
（AlCl3）It is 1.5 hours time-consuming, one hour then is kept the temperature at 15 DEG C, reaction is released without gas indicates that reaction terminates.In argon gas stream
Under protection, hexamethylene 1800mL is added into flask, slowly stirs and is precipitated to crystal.Bath temperature is reduced to -10 DEG C, stops stirring
It mixes, after crystal sedimentation, filtering is washed with hexamethylene, and being transferred to the dry vacuum degree of vacuum oven is -0.09MPa, and drying temperature is
100 DEG C, obtain white solid 24.8g, yield 69%.
The content of chloride ion is analyzed using turbidimetry, specially：0.5g solid sample is taken, 8mL deionized water is dissolved in,
1mL AgNO is added3/HNO3Solution（AgNO3：HNO3：H2O=1:65:34, mass ratio）, then that acquired solution distilled water is dilute
It releases to 25mL, compares determining chloride ion range with standard sample turbidity.Chloride ion content is lower than 5ppm.
Embodiment 6：
In dry argon gas glove box, dry isopropyl propionate, dimethyl ether are added into three-neck flask（DME）, diethyl ether
（DEE）, dipropyl ether（DPE）, 1,2- dimethoxy-ethane（DME）Total 69.1g（Each component quality is average）, three are added while stirring
Boron fluoride gamma-butyrolacton（BF3·GBL）40.0g is dissolved, and dried oxalic acid hydrogen lithium is then put into flask
（LiHC2O4）24.0g（0.25mol）, flask is taken out into glove box, is impregnated in 40 DEG C of stirred in water bath, and be constantly stirred
Object.Thionyl chloride is slowly added dropwise using constant pressure funnel（SOCl2）16.1g（0.135mol）, reaction takes place.It generates
Gas, which flows into be equipped in sodium hydroxide solution device, to be absorbed.Thionyl chloride is added dropwise（SOCl2）It is 1 hour time-consuming, then protected at 40 DEG C
Temperature one hour, reaction is released without gas indicates that reaction terminates.Under the protection of argon gas stream, n-hexane is added into flask（n-
hexane）, hexamethylene（CYH）, toluene（MB）, ethylbenzene（EB）Total 800mL（Ratio is any）, slowly stir and be precipitated to crystal.Drop
Low bath temperature stops stirring to 0 DEG C, and after crystal sedimentation, filtering is washed with poor mixing solvent, and it is dry to be transferred to vacuum oven
It is dry, obtain white solid 29.5g, yield 82%.
The content of chloride ion is analyzed using turbidimetry, specially：0.5g solid sample is taken, 8mL deionized water is dissolved in,
1mL AgNO is added3/HNO3Solution（AgNO3：HNO3：H2O=1:65:34, mass ratio）, then that acquired solution distilled water is dilute
It releases to 25mL, compares determining chloride ion range with standard sample turbidity.Chloride ion content is lower than 5ppm.
Embodiment 7：
In dry argon gas glove box, dry diethyl carbonate is added into three-neck flask（DEC）57.2g while stirring
Boron trifluoride butyl ether 55.5g is added, is dissolved, dried oxalic acid hydrogen lithium is then put into flask（LiHC2O4）24.0g
（0.25mol）, flask is taken out into glove box, is impregnated in 50 DEG C of stirred in water bath, and constantly stir mixture.Use constant pressure addition
Silicon tetrachloride is slowly added dropwise in funnel（SiCl4）11.9g（0.07mol）, reaction starts.The gas of generation, which flows into, is equipped with sodium hydroxide
It is absorbed in solution containment.Silicon tetrachloride is added dropwise（SiCl4）It is 1 hour time-consuming, one hour then is kept the temperature at 50 DEG C, reaction is put without gas
Indicate that reaction terminates out.Under the protection of argon gas stream, acetonitrile is added into flask（AN）, propionitrile（C2H5CN）, petroleum ether（PE）Altogether
800mL（Ratio is any）, slowly stir and be precipitated to crystal.Stop stirring, after crystal sedimentation, filtering is washed with poor mixing solvent
It washs, is transferred to vacuum oven drying, obtains white solid 25.5g, yield 71%.
The content of chloride ion is analyzed using turbidimetry, specially：0.5g solid sample is taken, 8mL deionized water is dissolved in,
1mL AgNO is added3/HNO3Solution（AgNO3：HNO3：H2O=1:65:34, mass ratio）, then that acquired solution distilled water is dilute
It releases to 25mL, compares determining chloride ion range with standard sample turbidity.Chloride ion content is lower than 5ppm.
Embodiment 8：
In dry argon gas glove box, dry dimethyl carbonate is added into three-neck flask（DMC）81.0g while stirring
Add boron trifluoride glycol dimethyl ether 37.4g, dissolved, dried oxalic acid hydrogen lithium is then put into flask（LiHC2O4）
24.0g（0.25mol）, flask is taken out into glove box, is impregnated in 30 DEG C of stirred in water bath, and constantly stir mixture.Using solid
Body feeder is slowly added into phosphorus pentachloride（PCl5）10.4g（0.05mol）, reaction takes place.The gas inflow of generation is equipped with
It is absorbed in sodium hydroxide solution device.Add phosphorus pentachloride（PCl5）It is 1.5 hours time-consuming, one hour then is kept the temperature at 30 DEG C, instead
Should release without gas indicates that reaction terminates.Under the protection of argon gas stream, dimethyl ether is added into flask（DME）, diethyl ether
（DEE）, ethylene oxide（EOT）, tetrahydrofuran（THF）Total 1800mL（Ratio is any）, slowly stir and be precipitated to crystal.Reduce water
Extremely -25 DEG C of bath temperature, stopping stirring, after crystal sedimentation, filtering is washed with poor mixing solvent, it is transferred to vacuum oven drying,
Vacuum degree is -0.097MPa, and drying temperature is 120 DEG C, obtains white solid 24.8g, yield 69%.
The content of chloride ion is analyzed using turbidimetry, specially：0.5g solid sample is taken, 8mL deionized water is dissolved in,
1mL AgNO is added3/HNO3Solution（AgNO3：HNO3：H2O=1:65:34, mass ratio）, then that acquired solution distilled water is dilute
It releases to 25mL, compares determining chloride ion range with standard sample turbidity.Chloride ion content is lower than 5ppm.
Embodiment 9：
In dry argon gas glove box, dry propylene oxide is added into three-neck flask（PO）58.0g is added while stirring
Boron trifluoride sulfolane 51.7g, is dissolved, and dried oxalic acid hydrogen lithium is then put into flask（LiHC2O4）24.0g
（0.25mol）, flask is taken out into glove box, is impregnated in 25 DEG C of stirred in water bath, and constantly stir mixture.It is fed using solid
Device is slowly added to phosphorus pentachloride（PCl5）Solid 12.3g（0.06mol）, reaction takes place.The gas of generation, which flows into, is equipped with hydrogen
It is absorbed in sodium hydroxide solution device.Add phosphorus pentachloride（PCl5）It is 1.5 hours time-consuming, one hour then is kept the temperature at 15 DEG C, reaction
No gas, which is released, indicates that reaction terminates.Under the protection of argon gas stream, Ethyl formate is added into flask（EF）, propyl formate
（PM）, propyl propionate（PP）Total 1800mL（Ratio is any）, slowly stir and be precipitated to crystal.Bath temperature is reduced to -10 DEG C, is stopped
Only stir, after crystal sedimentation, filtering wash with poor mixing solvent, be transferred to the dry vacuum degree of vacuum oven for-
0.097MPa, drying temperature are 40 DEG C, obtain white solid 28.0g, yield 78%.
The content of chloride ion is analyzed using turbidimetry, specially：0.5g solid sample is taken, 8mL deionized water is dissolved in,
1mL AgNO is added3/HNO3Solution（AgNO3：HNO3：H2O=1:65:34, mass ratio）, then that acquired solution distilled water is dilute
It releases to 25mL, compares determining chloride ion range with standard sample turbidity.Chloride ion content is lower than 5ppm.
Embodiment 10：
In dry argon gas glove box, dry acetonitrile is added into three-neck flask（AN）60.0g adds trifluoro while stirring
Change boron methyl ether 37.0g, is dissolved, dried oxalic acid hydrogen lithium is then put into flask（LiHC2O4）24.0g, by flask
Glove box is taken out, is impregnated in 40 DEG C of stirred in water bath, and constantly stir mixture.Trichlorine is slowly added dropwise using constant pressure funnel
Change phosphorus（PCl3）Liquid 13.7g, reaction take place.The gas of generation, which flows into be equipped in sodium hydroxide solution device, to be absorbed.Drop
Add phosphorus trichloride（PCl3）It is 1 hour time-consuming, one hour then is kept the temperature at 40 DEG C, reaction is released without gas indicates that reaction terminates.?
Under the protection of argon gas stream, ethylene carbonate is added into flask（EC）, dimethyl carbonate（DMC）, diethyl carbonate（DEC）Altogether
800mL（Ratio is any）, slowly stir and be precipitated to crystal.Bath temperature is reduced to 0 DEG C, stops stirring, after crystal sedimentation, mistake
Filter, is washed with poor mixing solvent, is transferred to vacuum oven drying, is obtained white solid 30.6g, yield 85%.
The content of chloride ion is analyzed using turbidimetry, specially：0.5g solid sample is taken, 8mL deionized water is dissolved in,
1mL AgNO is added3/HNO3Solution（AgNO3：HNO3：H2O=1:65:34, mass ratio）, then that acquired solution distilled water is dilute
It releases to 25mL, compares determining chloride ion range with standard sample turbidity.Chloride ion content is lower than 5ppm.
Above-described embodiment is merely illustrative of the technical solution of the present invention and is not intended to limit it, all without departing from the present invention
Any modification of spirit and scope or equivalent replacement should all cover the range in technical solution of the present invention.
Claims (9)
1. a kind of preparation method of difluoro oxalate borate, which is characterized in that include the following steps：
（1）Binoxalate, boron trifluoride complex and aprotic solvent are fitted into reaction vessel and mixed, chlorinating agent, which is added, makes it
Reaction, obtains the solution containing difluoro oxalate borate of clear；
（2）Solution is deaerated and is concentrated, poor solvent, which is added, is precipitated the crystallization of difluoro oxalate borate, is then filtered, washed, dries
Obtain the difluoro oxalate borate that purity is higher than 99.8%.
2. a kind of preparation method of difluoro oxalate borate according to claim 1, which is characterized in that described is borontrifluoride
Boron complex is boron trifluoride acetonitrile, boron trifluoride diethyl carbonate, boron trifluoride methylcarbonate, boron trifluoride tetrahydro furan
It mutters, boron trifluoride gamma-butyrolacton, boron trifluoride ethyl acetate, boron trifluoride ether, boron trifluoride methyl ether, boron trifluoride second two
Diethylene glycol dimethyl ether, boron trifluoride butyl ether, boron trifluoride acetic acid, boron trifluoride piperidines, boron trifluoride butyl acetate, boron trifluoride ring fourth
One of sulfone or multiple combinations.
3. a kind of preparation method of difluoro oxalate borate according to claim 1, which is characterized in that the oxalic acid hydrogen
The molar ratio of boron trifluoride is 1 in salt oxalate ion and boron trifluoride complex：（0.9~2）.
4. a kind of preparation method of difluoro oxalate borate according to claim 1, which is characterized in that the chlorinating agent
It is at least one of phosphorus trichloride, phosphorus pentachloride, silicon tetrachloride, titanium tetrachloride, alchlor, thionyl chloride.
5. a kind of preparation method of difluoro oxalate borate according to claim 1, which is characterized in that the reaction
The range that temperature is 0 ~ 50 DEG C.
6. a kind of preparation method of difluoro oxalate borate according to claim 1, which is characterized in that described is non-proton
Solvent is one of linear carbonate, cyclic carbonate, cyclic ester, chain ester, cyclic ether, chain ether, nitrile or a variety of groups
It closes.
7. a kind of preparation method of difluoro oxalate borate according to claim 1, which is characterized in that described is bad molten
Agent is cyclic carbonate, linear carbonate, cyclic ester, chain ester, cyclic ether, chain ether, nitrile, petroleum ether, n-hexane, hexamethylene
One of alkane, toluene, ethylbenzene, methylene chloride, chloroform, dichloroethanes a variety of are mixed with arbitrary proportion.
8. a kind of preparation method of difluoro oxalate borate according to claim 1, which is characterized in that the crystallization temperature
Degree is -25 DEG C ~ 50 DEG C；The drying is vacuum drying, and vacuum degree is -0.01 ~ -0.1MPa, and drying temperature is 40 DEG C ~ 120
℃。
9. a kind of preparation method of difluoro oxalate borate according to claim 1, which is characterized in that binoxalate resists
Counter cation be selected from least one of be made of lithium ion, sodium ion, potassium ion and tetraalkyl ammonium ion contend with sun from
Son.
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