JP2007277020A - Method for purifying tetrafluoroborate - Google Patents
Method for purifying tetrafluoroborate Download PDFInfo
- Publication number
- JP2007277020A JP2007277020A JP2006102124A JP2006102124A JP2007277020A JP 2007277020 A JP2007277020 A JP 2007277020A JP 2006102124 A JP2006102124 A JP 2006102124A JP 2006102124 A JP2006102124 A JP 2006102124A JP 2007277020 A JP2007277020 A JP 2007277020A
- Authority
- JP
- Japan
- Prior art keywords
- tetrafluoroborate
- acid
- hydrofluoric acid
- group
- boric acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 tetrafluoroborate Chemical compound 0.000 title claims abstract description 100
- 238000000034 method Methods 0.000 title claims abstract description 31
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 85
- 239000004327 boric acid Substances 0.000 claims abstract description 31
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 26
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 15
- 125000005496 phosphonium group Chemical group 0.000 claims abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 4
- 230000007062 hydrolysis Effects 0.000 claims description 25
- 238000006460 hydrolysis reaction Methods 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 22
- 238000000746 purification Methods 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 2
- 238000003682 fluorination reaction Methods 0.000 claims 1
- 239000000413 hydrolysate Substances 0.000 abstract 3
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 abstract 2
- VFLDPWHFBUODDF-FCXRPNKRSA-N curcumin Chemical compound C1=C(O)C(OC)=CC(\C=C\C(=O)CC(=O)\C=C\C=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-FCXRPNKRSA-N 0.000 description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 14
- 229940109262 curcumin Drugs 0.000 description 14
- 235000012754 curcumin Nutrition 0.000 description 14
- 239000004148 curcumin Substances 0.000 description 14
- VFLDPWHFBUODDF-UHFFFAOYSA-N diferuloylmethane Natural products C1=C(O)C(OC)=CC(C=CC(=O)CC(=O)C=CC=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000003990 capacitor Substances 0.000 description 9
- 239000012535 impurity Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000003109 Karl Fischer titration Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 4
- 239000011255 nonaqueous electrolyte Substances 0.000 description 4
- 241000407170 Curcuma Species 0.000 description 3
- 235000014375 Curcuma Nutrition 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- ZJACZNZOAGQFTP-UHFFFAOYSA-N 1-(ethoxymethyl)-1-methylpyrrolidin-1-ium Chemical compound CCOC[N+]1(C)CCCC1 ZJACZNZOAGQFTP-UHFFFAOYSA-N 0.000 description 2
- SGPKVBVUPTYUET-UHFFFAOYSA-N 1-(methoxymethyl)-1-propylpyrrolidin-1-ium Chemical compound CCC[N+]1(COC)CCCC1 SGPKVBVUPTYUET-UHFFFAOYSA-N 0.000 description 2
- JFLBXOUJTNALFC-UHFFFAOYSA-N 1-ethyl-1-(methoxymethyl)pyrrolidin-1-ium Chemical compound COC[N+]1(CC)CCCC1 JFLBXOUJTNALFC-UHFFFAOYSA-N 0.000 description 2
- QWTKWUKAOVCYBM-UHFFFAOYSA-N 1-methyl-1-(propoxymethyl)pyrrolidin-1-ium Chemical compound CCCOC[N+]1(C)CCCC1 QWTKWUKAOVCYBM-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 2
- SZWHXXNVLACKBV-UHFFFAOYSA-N tetraethylphosphanium Chemical compound CC[P+](CC)(CC)CC SZWHXXNVLACKBV-UHFFFAOYSA-N 0.000 description 2
- XOGCTUKDUDAZKA-UHFFFAOYSA-N tetrapropylphosphanium Chemical compound CCC[P+](CCC)(CCC)CCC XOGCTUKDUDAZKA-UHFFFAOYSA-N 0.000 description 2
- GARJMFRQLMUUDD-UHFFFAOYSA-N 1,1-dimethylpyrrolidin-1-ium Chemical compound C[N+]1(C)CCCC1 GARJMFRQLMUUDD-UHFFFAOYSA-N 0.000 description 1
- PSIOIZDELPYQPO-UHFFFAOYSA-N 1,2-dimethylpyrazol-1-ium Chemical compound CN1C=CC=[N+]1C PSIOIZDELPYQPO-UHFFFAOYSA-N 0.000 description 1
- GMUSNOZEJRLWKH-UHFFFAOYSA-N 1,2-dimethylpyrimidin-1-ium Chemical compound CC1=NC=CC=[N+]1C GMUSNOZEJRLWKH-UHFFFAOYSA-N 0.000 description 1
- XLJSMWDFUFADIA-UHFFFAOYSA-N 1,3-diethylimidazol-1-ium Chemical compound CCN1C=C[N+](CC)=C1 XLJSMWDFUFADIA-UHFFFAOYSA-N 0.000 description 1
- HVVRUQBMAZRKPJ-UHFFFAOYSA-N 1,3-dimethylimidazolium Chemical compound CN1C=C[N+](C)=C1 HVVRUQBMAZRKPJ-UHFFFAOYSA-N 0.000 description 1
- KLHAPWPQFHROAB-UHFFFAOYSA-N 1-(butoxymethyl)-1-methylpyrrolidin-1-ium Chemical compound CCCCOC[N+]1(C)CCCC1 KLHAPWPQFHROAB-UHFFFAOYSA-N 0.000 description 1
- XAKVXORGVYVQFC-UHFFFAOYSA-N 1-(methoxymethyl)-1-methylpiperidin-1-ium Chemical compound COC[N+]1(C)CCCCC1 XAKVXORGVYVQFC-UHFFFAOYSA-N 0.000 description 1
- KOCWJEWXPJKXHS-UHFFFAOYSA-N 1-(methoxymethyl)-1-methylpyrrolidin-1-ium Chemical compound COC[N+]1(C)CCCC1 KOCWJEWXPJKXHS-UHFFFAOYSA-N 0.000 description 1
- RMTSCWSMELBQFT-UHFFFAOYSA-N 1-butyl-1-(methoxymethyl)pyrrolidin-1-ium Chemical compound CCCC[N+]1(COC)CCCC1 RMTSCWSMELBQFT-UHFFFAOYSA-N 0.000 description 1
- WVKQECDSKDGQDQ-UHFFFAOYSA-O 1-butyl-1H-triazol-1-ium Chemical compound CCCC[NH+]1C=CN=N1 WVKQECDSKDGQDQ-UHFFFAOYSA-O 0.000 description 1
- MIZPCNCPEWLKOV-UHFFFAOYSA-N 1-butyl-2-methylpyrazol-2-ium Chemical compound CCCCN1C=CC=[N+]1C MIZPCNCPEWLKOV-UHFFFAOYSA-N 0.000 description 1
- XLOSBJZGLWEIFL-UHFFFAOYSA-N 1-butylpyrazin-1-ium Chemical compound CCCC[N+]1=CC=NC=C1 XLOSBJZGLWEIFL-UHFFFAOYSA-N 0.000 description 1
- MGASSKTWAZLFTD-UHFFFAOYSA-N 1-butylpyridazin-1-ium Chemical compound CCCC[N+]1=CC=CC=N1 MGASSKTWAZLFTD-UHFFFAOYSA-N 0.000 description 1
- WACRAFUNNYGNEQ-UHFFFAOYSA-N 1-ethyl-1-methylpiperidin-1-ium Chemical compound CC[N+]1(C)CCCCC1 WACRAFUNNYGNEQ-UHFFFAOYSA-N 0.000 description 1
- NIHOUJYFWMURBG-UHFFFAOYSA-N 1-ethyl-1-methylpyrrolidin-1-ium Chemical compound CC[N+]1(C)CCCC1 NIHOUJYFWMURBG-UHFFFAOYSA-N 0.000 description 1
- QNXMTMCQDZQADU-UHFFFAOYSA-N 1-ethyl-1-propylpyrrolidin-1-ium Chemical compound CCC[N+]1(CC)CCCC1 QNXMTMCQDZQADU-UHFFFAOYSA-N 0.000 description 1
- IRGDPGYNHSIIJJ-UHFFFAOYSA-N 1-ethyl-2,3-dimethylimidazol-3-ium Chemical compound CCN1C=C[N+](C)=C1C IRGDPGYNHSIIJJ-UHFFFAOYSA-N 0.000 description 1
- MLYBVSISIUUHHY-UHFFFAOYSA-N 1-ethyl-2-methylpyrazin-1-ium Chemical compound CC[N+]1=CC=NC=C1C MLYBVSISIUUHHY-UHFFFAOYSA-N 0.000 description 1
- BOFPDEISADDIGX-UHFFFAOYSA-N 1-ethyl-2-methylpyrazol-2-ium Chemical compound CCN1C=CC=[N+]1C BOFPDEISADDIGX-UHFFFAOYSA-N 0.000 description 1
- ALNWCYLRUYXLCD-UHFFFAOYSA-O 1-ethyl-2H-triazol-1-ium Chemical compound CC[NH+]1C=CN=N1 ALNWCYLRUYXLCD-UHFFFAOYSA-O 0.000 description 1
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 1
- OEIMXYNKWKCFOE-UHFFFAOYSA-N 1-ethylpyridazin-1-ium Chemical compound CC[N+]1=CC=CC=N1 OEIMXYNKWKCFOE-UHFFFAOYSA-N 0.000 description 1
- OIDIRWZVUWCCCO-UHFFFAOYSA-N 1-ethylpyridin-1-ium Chemical compound CC[N+]1=CC=CC=C1 OIDIRWZVUWCCCO-UHFFFAOYSA-N 0.000 description 1
- OGLIVJFAKNJZRE-UHFFFAOYSA-N 1-methyl-1-propylpiperidin-1-ium Chemical compound CCC[N+]1(C)CCCCC1 OGLIVJFAKNJZRE-UHFFFAOYSA-N 0.000 description 1
- YQFWGCSKGJMGHE-UHFFFAOYSA-N 1-methyl-1-propylpyrrolidin-1-ium Chemical compound CCC[N+]1(C)CCCC1 YQFWGCSKGJMGHE-UHFFFAOYSA-N 0.000 description 1
- RGPPCBVEBOWHLY-UHFFFAOYSA-N 1-methyl-2-propylpyrazol-1-ium Chemical compound CCCN1C=CC=[N+]1C RGPPCBVEBOWHLY-UHFFFAOYSA-N 0.000 description 1
- JWAWEQBUZOGIBZ-UHFFFAOYSA-O 1-methyl-2h-triazol-1-ium Chemical compound C[N+]1=CC=NN1 JWAWEQBUZOGIBZ-UHFFFAOYSA-O 0.000 description 1
- MTGKCDNVVMKVRH-UHFFFAOYSA-N 1-methyl-3-propyl-2h-pyrimidin-1-ium Chemical compound CCCN1C[N+](C)=CC=C1 MTGKCDNVVMKVRH-UHFFFAOYSA-N 0.000 description 1
- XLKPEAFVZSNDOE-UHFFFAOYSA-N 1-methylpyridazin-1-ium Chemical compound C[N+]1=CC=CC=N1 XLKPEAFVZSNDOE-UHFFFAOYSA-N 0.000 description 1
- VAUFFDKLUVJZTG-UHFFFAOYSA-O 1-propyl-2h-triazol-1-ium Chemical compound CCC[N+]1=CC=NN1 VAUFFDKLUVJZTG-UHFFFAOYSA-O 0.000 description 1
- IYVYLVCVXXCYRI-UHFFFAOYSA-N 1-propylimidazole Chemical compound CCCN1C=CN=C1 IYVYLVCVXXCYRI-UHFFFAOYSA-N 0.000 description 1
- ZZUBADFFZKAPJC-UHFFFAOYSA-N 1-propylpyridazin-1-ium Chemical compound CCC[N+]1=CC=CC=N1 ZZUBADFFZKAPJC-UHFFFAOYSA-N 0.000 description 1
- CRTKBIFIDSNKCN-UHFFFAOYSA-N 1-propylpyridin-1-ium Chemical compound CCC[N+]1=CC=CC=C1 CRTKBIFIDSNKCN-UHFFFAOYSA-N 0.000 description 1
- VAJZCFLYJRMBFN-UHFFFAOYSA-N 4,4-dimethylmorpholin-4-ium Chemical compound C[N+]1(C)CCOCC1 VAJZCFLYJRMBFN-UHFFFAOYSA-N 0.000 description 1
- NWORVTSPNLVHSH-UHFFFAOYSA-N 4-ethyl-4-methylmorpholin-4-ium Chemical compound CC[N+]1(C)CCOCC1 NWORVTSPNLVHSH-UHFFFAOYSA-N 0.000 description 1
- VRQUKNXRQCZCOW-UHFFFAOYSA-N 4-ethyl-4-propylmorpholin-4-ium Chemical compound CCC[N+]1(CC)CCOCC1 VRQUKNXRQCZCOW-UHFFFAOYSA-N 0.000 description 1
- RZWDVVAASLNVBS-UHFFFAOYSA-N 4-methyl-4-propylmorpholin-4-ium Chemical compound CCC[N+]1(C)CCOCC1 RZWDVVAASLNVBS-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- RGSSJDPUQVEJIL-UHFFFAOYSA-N CCC[N+]1=C(C)[S+](C)C=C1 Chemical compound CCC[N+]1=C(C)[S+](C)C=C1 RGSSJDPUQVEJIL-UHFFFAOYSA-N 0.000 description 1
- AEGJIDJYXSUSMM-UHFFFAOYSA-N C[S+]1C=CN=C1C Chemical compound C[S+]1C=CN=C1C AEGJIDJYXSUSMM-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PQBAWAQIRZIWIV-UHFFFAOYSA-N N-methylpyridinium Chemical compound C[N+]1=CC=CC=C1 PQBAWAQIRZIWIV-UHFFFAOYSA-N 0.000 description 1
- GSBKRFGXEJLVMI-UHFFFAOYSA-N Nervonyl carnitine Chemical compound CCC[N+](C)(C)C GSBKRFGXEJLVMI-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- XHIHMDHAPXMAQK-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-butylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC=C1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F XHIHMDHAPXMAQK-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 125000005619 boric acid group Chemical group 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- IUNCEDRRUNZACO-UHFFFAOYSA-N butyl(trimethyl)azanium Chemical compound CCCC[N+](C)(C)C IUNCEDRRUNZACO-UHFFFAOYSA-N 0.000 description 1
- YQPAAVMEUPILEE-UHFFFAOYSA-N butyl(trimethyl)phosphanium Chemical compound CCCC[P+](C)(C)C YQPAAVMEUPILEE-UHFFFAOYSA-N 0.000 description 1
- JTSLKOMZLHUIMT-UHFFFAOYSA-N butyl-(ethoxymethyl)-diethylazanium Chemical compound CCCC[N+](CC)(CC)COCC JTSLKOMZLHUIMT-UHFFFAOYSA-N 0.000 description 1
- FZYZWGCASHMHDP-UHFFFAOYSA-N butyl-(ethoxymethyl)-dimethylazanium Chemical compound CCCC[N+](C)(C)COCC FZYZWGCASHMHDP-UHFFFAOYSA-N 0.000 description 1
- VJGAQZSQPXJMQG-UHFFFAOYSA-N butyl-(methoxymethyl)-dimethylazanium Chemical compound CCCC[N+](C)(C)COC VJGAQZSQPXJMQG-UHFFFAOYSA-N 0.000 description 1
- XDVUELLFFZMZPX-UHFFFAOYSA-N butyl-diethyl-(methoxymethyl)azanium Chemical compound CCCC[N+](CC)(CC)COC XDVUELLFFZMZPX-UHFFFAOYSA-N 0.000 description 1
- OZHYULYUYJVOPW-UHFFFAOYSA-N butyl-ethyl-methyl-propylazanium Chemical compound CCCC[N+](C)(CC)CCC OZHYULYUYJVOPW-UHFFFAOYSA-N 0.000 description 1
- DLIJPAHLBJIQHE-UHFFFAOYSA-N butylphosphane Chemical compound CCCCP DLIJPAHLBJIQHE-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical group 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
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- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ZJHQDSMOYNLVLX-UHFFFAOYSA-N diethyl(dimethyl)azanium Chemical compound CC[N+](C)(C)CC ZJHQDSMOYNLVLX-UHFFFAOYSA-N 0.000 description 1
- RBECNRCKEQGFRU-UHFFFAOYSA-N diethyl(dimethyl)phosphanium Chemical compound CC[P+](C)(C)CC RBECNRCKEQGFRU-UHFFFAOYSA-N 0.000 description 1
- DUWSQQWAYMDIDY-UHFFFAOYSA-N diethyl-(methoxymethyl)-methylazanium Chemical compound CC[N+](C)(CC)COC DUWSQQWAYMDIDY-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- IKXAGLHOBMLMFG-UHFFFAOYSA-N ethoxymethyl(triethyl)azanium Chemical compound CCOC[N+](CC)(CC)CC IKXAGLHOBMLMFG-UHFFFAOYSA-N 0.000 description 1
- UGYNCNQTQKRZKR-UHFFFAOYSA-N ethoxymethyl(trimethyl)azanium Chemical compound CCOC[N+](C)(C)C UGYNCNQTQKRZKR-UHFFFAOYSA-N 0.000 description 1
- URDYKTRHJTYNMQ-UHFFFAOYSA-N ethoxymethyl(tripropyl)azanium Chemical compound CCC[N+](CCC)(CCC)COCC URDYKTRHJTYNMQ-UHFFFAOYSA-N 0.000 description 1
- VRTBTDVPBFYRMM-UHFFFAOYSA-N ethoxymethyl-diethyl-methylazanium Chemical compound CCOC[N+](C)(CC)CC VRTBTDVPBFYRMM-UHFFFAOYSA-N 0.000 description 1
- QDIDVEQNGJDCLN-UHFFFAOYSA-N ethoxymethyl-diethyl-propylazanium Chemical compound CCC[N+](CC)(CC)COCC QDIDVEQNGJDCLN-UHFFFAOYSA-N 0.000 description 1
- RWNNJGPZFYSWLD-UHFFFAOYSA-N ethoxymethyl-dimethyl-propylazanium Chemical compound CCC[N+](C)(C)COCC RWNNJGPZFYSWLD-UHFFFAOYSA-N 0.000 description 1
- DAOSJUPOGKHGLD-UHFFFAOYSA-N ethoxymethyl-ethyl-dimethylazanium Chemical compound CCOC[N+](C)(C)CC DAOSJUPOGKHGLD-UHFFFAOYSA-N 0.000 description 1
- ZPUQFHINROWWCC-UHFFFAOYSA-N ethoxymethyl-ethyl-dipropylazanium Chemical compound CCC[N+](CC)(CCC)COCC ZPUQFHINROWWCC-UHFFFAOYSA-N 0.000 description 1
- NMTZFVFRGJNYRW-UHFFFAOYSA-N ethoxymethyl-methyl-dipropylazanium Chemical compound CCC[N+](C)(CCC)COCC NMTZFVFRGJNYRW-UHFFFAOYSA-N 0.000 description 1
- IQLVJVXTKNBZRC-UHFFFAOYSA-N ethyl(trimethyl)phosphanium Chemical compound CC[P+](C)(C)C IQLVJVXTKNBZRC-UHFFFAOYSA-N 0.000 description 1
- OQULBFLJJHJSOL-UHFFFAOYSA-N ethyl-(methoxymethyl)-dipropylazanium Chemical compound CCC[N+](CC)(CCC)COC OQULBFLJJHJSOL-UHFFFAOYSA-N 0.000 description 1
- BPJRIMYDFCYEAA-UHFFFAOYSA-N ethyl-(methoxymethyl)-methyl-propylazanium Chemical compound CCC[N+](C)(CC)COC BPJRIMYDFCYEAA-UHFFFAOYSA-N 0.000 description 1
- ZOZZQPFBMNNPPO-UHFFFAOYSA-N ethyl-dimethyl-propylazanium Chemical compound CCC[N+](C)(C)CC ZOZZQPFBMNNPPO-UHFFFAOYSA-N 0.000 description 1
- XRUDAGYWANYZNW-UHFFFAOYSA-N ethyl-dimethyl-propylphosphanium Chemical compound CCC[P+](C)(C)CC XRUDAGYWANYZNW-UHFFFAOYSA-N 0.000 description 1
- YOMFVLRTMZWACQ-UHFFFAOYSA-N ethyltrimethylammonium Chemical compound CC[N+](C)(C)C YOMFVLRTMZWACQ-UHFFFAOYSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- NNCAWEWCFVZOGF-UHFFFAOYSA-N mepiquat Chemical compound C[N+]1(C)CCCCC1 NNCAWEWCFVZOGF-UHFFFAOYSA-N 0.000 description 1
- SUQNNSTVKPMHRZ-UHFFFAOYSA-N methoxymethyl(trimethyl)azanium Chemical compound COC[N+](C)(C)C SUQNNSTVKPMHRZ-UHFFFAOYSA-N 0.000 description 1
- MEVCELUSWHCAFS-UHFFFAOYSA-N methoxymethyl(tripropyl)azanium Chemical compound CCC[N+](CCC)(CCC)COC MEVCELUSWHCAFS-UHFFFAOYSA-N 0.000 description 1
- CYMZPHRZTDBXCR-UHFFFAOYSA-N methoxymethyl-dimethyl-propylazanium Chemical compound CCC[N+](C)(C)COC CYMZPHRZTDBXCR-UHFFFAOYSA-N 0.000 description 1
- DPLISQLAZUOVEE-UHFFFAOYSA-N methoxymethyl-methyl-dipropylazanium Chemical compound CCC[N+](C)(CCC)COC DPLISQLAZUOVEE-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JZDAZYYKZYRVOR-UHFFFAOYSA-N n-ethyl-n-(methoxymethyl)propan-1-amine Chemical compound CCCN(CC)COC JZDAZYYKZYRVOR-UHFFFAOYSA-N 0.000 description 1
- GLAGQEORJDLVPM-UHFFFAOYSA-N n-ethyl-n-methoxypropan-2-amine Chemical compound CCN(OC)C(C)C GLAGQEORJDLVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- BXYHVFRRNNWPMB-UHFFFAOYSA-N tetramethylphosphanium Chemical compound C[P+](C)(C)C BXYHVFRRNNWPMB-UHFFFAOYSA-N 0.000 description 1
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 1
- KDYHSGOHECNGNG-UHFFFAOYSA-N triethyl(methoxymethyl)azanium Chemical compound CC[N+](CC)(CC)COC KDYHSGOHECNGNG-UHFFFAOYSA-N 0.000 description 1
- SEACXNRNJAXIBM-UHFFFAOYSA-N triethyl(methyl)azanium Chemical compound CC[N+](C)(CC)CC SEACXNRNJAXIBM-UHFFFAOYSA-N 0.000 description 1
- TZWFFXFQARPFJN-UHFFFAOYSA-N triethyl(methyl)phosphanium Chemical compound CC[P+](C)(CC)CC TZWFFXFQARPFJN-UHFFFAOYSA-N 0.000 description 1
- YGDBTMJEJNVHPZ-UHFFFAOYSA-N trimethyl(propyl)phosphanium Chemical compound CCC[P+](C)(C)C YGDBTMJEJNVHPZ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本発明は、テトラフルオロホウ酸塩の精製方法に関し、より詳細には、電気二重層キャパシタ等の非水電解液電池の電解質として使用されるテトラフルオロホウ酸塩中に含まれる不純物としてのホウ酸又はテトラフルオロホウ酸アニオンの加水分解生成物を除去することが可能なテトラフルオロホウ酸塩の精製方法に関する。 The present invention relates to a method for purifying tetrafluoroborate, and more specifically, boric acid as an impurity contained in tetrafluoroborate used as an electrolyte of a non-aqueous electrolyte battery such as an electric double layer capacitor. Alternatively, the present invention relates to a method for purifying tetrafluoroborate capable of removing a hydrolysis product of a tetrafluoroborate anion.
近年、バッテリーや電気二重層キャパシタをはじめとする電気化学デバイスの出力密度、エネルギー密度向上の要求が高まっており、それと同時に、長期的に使用した際の性能劣化を如何に低く抑えられるかということも重要な課題となっている。なかでも電気二重層キャパシタはバッテリーと比較して化学反応を伴わない為、性能劣化が起こりにくいことが長所の一つである。その信頼性を高く維持するには使用する電解質に含まれる不純物の含有量の制御が必要不可欠である。電気二重層キャパシタの電解質としては４級アンモニウムテトラフルオロボレートがしばしば使用される。テトラフルオロボレートアニオンは電気化学的な耐酸化性に優れており、分子容がコンパクトでありながらマイナス電荷が分散しており、電気伝導性に優れるためである。 In recent years, there has been an increasing demand for improving the power density and energy density of electrochemical devices such as batteries and electric double layer capacitors, and at the same time, how low performance degradation can be suppressed when used over the long term. Is also an important issue. Among them, the electric double layer capacitor is not accompanied by a chemical reaction as compared with the battery, and one of the advantages is that the performance deterioration is less likely to occur. In order to maintain the reliability high, it is essential to control the content of impurities contained in the electrolyte used. Quaternary ammonium tetrafluoroborate is often used as the electrolyte of the electric double layer capacitor. This is because the tetrafluoroborate anion is excellent in electrochemical oxidation resistance, has a small molecular volume, disperses negative charges, and is excellent in electrical conductivity.
テトラフルオロホウ酸ナトリウムやテトラフルオロホウ酸リチウム、４級アンモニウムテトラフルオロホウ酸等のテトラフルオロホウ酸塩は、水との共存下に於いて、下記の反応式のように加水分解を起こすことが知られている（下記、非文献特許１参照）。 Tetrafluoroborate salts such as sodium tetrafluoroborate, lithium tetrafluoroborate, and quaternary ammonium tetrafluoroborate can cause hydrolysis as shown in the following reaction formula in the presence of water. It is known (see Non-Patent Document 1 below).
非水電解液電池の電解質にホウ酸をはじめとするテトラフルオロホウ酸塩の加水分解生成物が含まれていると、例えば、下記特許文献１に開示されている通り、電気二重層キャパシタやリチウムイオン電池、電解コンデンサー等の非水電解液電池にとって耐電圧の低下、長期的なサイクル特性の低下の原因となる。このためテトラフルオロホウ酸塩を製造する際、前記反応に示される加水分解生成物（［ＢＦｎ（ＯＨ）４−ｎ］−（ｎは１〜３の自然数））及びホウ酸の混入量を極力小さくすることが望まれる。 When the hydrolysis product of tetrafluoroborate such as boric acid is contained in the electrolyte of the nonaqueous electrolyte battery, for example, as disclosed in Patent Document 1 below, an electric double layer capacitor or lithium For non-aqueous electrolyte batteries such as ion batteries and electrolytic capacitors, this causes a decrease in withstand voltage and long-term cycle characteristics. Therefore making the tetrafluoroborate salt, the hydrolysis product shown in the reaction - the ([BF n (OH) 4 -n] (n is a natural number of 1 to 3)) and mixed amount of boric acid It is desirable to make it as small as possible.
電気二重層キャパシタの電解質として多用されている４級アンモニウムテトラフルオロホウ酸は、従来、４級アンモニウムハライド等とホウフッ化水素酸水溶液とを反応させアニオン部分を塩交換させることによって得られていた。例えば、下記特許文献２には、４級アンモニウムハライド（ハライドはクロライド、ブロマイド）とホウフッ化水素酸水溶液とを反応させて４級アンモニウムテトラフルオロホウ酸を得る製造方法が開示されている。また、下記特許文献３には、４級アンモニウムヒドロキシドとホウフッ化水素酸水溶液とを反応させる製造方法が開示されている。更に、下記特許文献４及び５には、４級アンモニウム重炭酸塩とホウフッ化水素酸水溶液とを反応させる製造方法が開示されている。 Quaternary ammonium tetrafluoroboric acid, which is frequently used as an electrolyte for electric double layer capacitors, has been conventionally obtained by reacting a quaternary ammonium halide or the like with an aqueous borohydrofluoric acid solution to salt-exchange the anion portion. For example, Patent Document 2 below discloses a production method for obtaining quaternary ammonium tetrafluoroboric acid by reacting a quaternary ammonium halide (halide is chloride or bromide) with a borohydrofluoric acid aqueous solution. Patent Document 3 below discloses a production method in which a quaternary ammonium hydroxide and a borohydrofluoric acid aqueous solution are reacted. Further, Patent Documents 4 and 5 below disclose a production method in which a quaternary ammonium bicarbonate and a borohydrofluoric acid aqueous solution are reacted.
前述の通り、テトラフルオロホウ酸塩の製造にはホウフッ化水素酸水溶液が使用されることが多いが、テトラフルオロホウ酸アニオンは水溶液中に於いて加水分解しており、［ＢＦｎ（ＯＨ）４−ｎ］−（ｎは１〜３の自然数）及びホウ酸等の不純物が含まれる。また、通常使用されるホウフッ化水素酸水溶液の濃度は４０重量％程度なので、余分な水を大量に除去する必要がある。工業的には加熱操作によって水分除去を行うことが有利だが、加熱によりテトラフルオロホウ酸アニオンの加水分解は加速され、得られるテトラフルオロホウ酸塩にはホウ酸を始めとした種々の加水分解生成物が不純物として混入してしまう。この様に、従来よりテトラフルオロホウ酸塩の製造に於いては、前記不純物の混入という問題がつきまとう。従って、テトラフルオロホウ酸塩中から不純物をいかに簡便に除去し、高純度のテトラフルオロホウ酸塩が得られるか否かが課題となっている。 As described above, a borohydrofluoric acid aqueous solution is often used for the production of tetrafluoroborate, but the tetrafluoroborate anion is hydrolyzed in the aqueous solution, and [BF n (OH) 4-n ] - (n is a natural number of 1 to 3) and impurities such as boric acid are included. Moreover, since the concentration of the borohydrofluoric acid aqueous solution usually used is about 40% by weight, it is necessary to remove a large amount of excess water. Industrially, it is advantageous to remove water by heating operation, but the hydrolysis of tetrafluoroborate anion is accelerated by heating, and the resulting tetrafluoroborate has various hydrolysis products including boric acid. Things are mixed as impurities. As described above, in the production of tetrafluoroborate, there is a problem of contamination of the impurities. Therefore, how to easily remove impurities from tetrafluoroborate and obtain high-purity tetrafluoroborate is a problem.
こうした課題を背景に、非水電解液用テトラフルオロホウ酸塩のホウ酸を低減するための精製方法として、下記特許文献１には、得られたテトラフルオロホウ酸塩をアルコール中に於いて再結晶する方法が開示されている。また、下記特許文献６には、テトラフルオロホウ酸塩中に含まれるホウ酸をアルコール類によりエステル化し、続いて蒸留操作により留去する方法が開示されている。 Against this background, as a purification method for reducing boric acid in tetrafluoroborate for non-aqueous electrolytes, Patent Document 1 below discloses that the obtained tetrafluoroborate is reconstituted in alcohol. A method of crystallization is disclosed. Patent Document 6 below discloses a method in which boric acid contained in tetrafluoroborate is esterified with alcohols and subsequently distilled off by distillation.
しかしながら、アルコール類等の有機溶媒中で再結晶させ、ホウ酸の含有量を低減させる精製方法に於いては、有機溶媒に対する溶解度が高いテトラフルオロホウ酸塩の場合には、その精製工程を繰り返す必要があり、収率が低下するという問題がある。更に、テトラフルオロホウ酸塩の中には常温溶融塩も存在し、こうした場合、再結晶できないといった問題点が生じる。また、ホウ酸をアルコール類によりエステル化して除去をする方法に於いては、ホウ酸の含有量が高い場合には有機溶媒を大量に使用する必要があり、工業的に大量生産をする方法として適切ではないといった問題もある。
本発明は前記問題点に鑑みなされたものであり、その目的は、ホウ酸やテトラフルオロホウ酸アニオンの加水分解生成物の含有量が極めて少ない高純度のテトラフルオロホウ酸塩に簡便に、かつ収率良く精製することが可能な方法を提供することにある。 The present invention has been made in view of the above problems, and its purpose is simply to produce a highly pure tetrafluoroborate having a very low content of hydrolysis products of boric acid and tetrafluoroborate anions, and An object of the present invention is to provide a method that can be purified with good yield.
本願発明者等は、前記従来の問題点を解決すべく、テトラフルオロホウ酸塩の精製方法について検討した。その結果、下記構成を採用することにより前記目的を達成できることを見出して、本発明を完成させるに至った。 The inventors of the present application have studied a method for purifying tetrafluoroborate in order to solve the conventional problems. As a result, the inventors have found that the object can be achieved by adopting the following configuration, and have completed the present invention.
即ち、本発明に係るテトラフルオロホウ酸塩の精製方法は、前記の課題を解決する為に、一般式Ｘ（ＢＦ４）ｍ（ここで、前記Ｘは、４級アンモニウム、４級ホスホニウム、アンモニウム、ＩＡ族元素、IIＡ族元素及びIIIＢ族元素からなる群より選択される少なくとも何れか１つを示し、ｍは自然数であり、Ｘの価数に等しい。）で表されるテトラフルオロホウ酸塩に含まれるホウ酸又はテトラフルオロホウ酸アニオンの加水分解生成物に対し過剰となる量のフッ化水素酸を、該テトラフルオロホウ酸塩に添加することにより、該加水分解生成物の少なくとも何れかと反応させてホウフッ化水素酸を生成させ、前記フッ化水素酸の留去に伴い、前記ホウフッ化水素酸を除去することを特徴とする。 That is, the tetrafluoroborate purification method according to the present invention has the general formula X (BF 4 ) m (where X is a quaternary ammonium, a quaternary phosphonium, an ammonium, And at least one selected from the group consisting of Group IA elements, Group IIA elements, and Group IIIB elements, and m is a natural number and is equal to the valence of X. By adding an excess amount of hydrofluoric acid to the hydrolysis product of boric acid or tetrafluoroborate anion contained in the tetrafluoroborate, at least one of the hydrolysis products It reacts to produce borohydrofluoric acid, and the borohydrofluoric acid is removed as the hydrofluoric acid is distilled off.
前記方法によれば、テトラフルオロホウ酸塩にフッ化水素酸を添加することにより、不純物として含まれるホウ酸及びテトラフルオロホウ酸アニオン（［ＢＦｎ（ＯＨ）４−ｎ］−（ｎは１〜３の自然数））等の加水分解生成物とフッ化水素酸とを反応させる。この反応により、前記加水分解生成物よりも沸点又は分解温度の低いホウフッ化水素酸が生成する。更に、未反応の残存しているフッ化水素酸を留去することにより、従来よりも容易に加水分解生成物を除去することができる。即ち、前記方法によれば、従来繰り返し行われていた精製工程が不要となり、収率の低下を抑制することができる。また、ホウ酸をアルコール類によりエステル化して除去をする方法に於いては、有機溶媒を大量に使用する必要があったが、本発明に於いてはその有機溶媒も不要である。その結果、防爆設備を導入する必要もなく、製造コストを低減し工業的な実施を可能にする。 According to the above-described method, by adding hydrofluoric acid to tetrafluoroborate, boric acid and tetrafluoroborate anions ([BF n (OH) 4 -n ] − (n is 1) contained as impurities. A hydrolyzed product such as a natural number of ~ 3) is reacted with hydrofluoric acid. By this reaction, borohydrofluoric acid having a boiling point or a decomposition temperature lower than that of the hydrolysis product is generated. Furthermore, the hydrolysis product can be removed more easily than in the past by distilling off the unreacted remaining hydrofluoric acid. That is, according to the said method, the refinement | purification process performed conventionally conventionally becomes unnecessary, and the fall of a yield can be suppressed. In the method of removing boric acid by esterification with alcohols, it is necessary to use a large amount of an organic solvent. However, in the present invention, the organic solvent is not necessary. As a result, it is not necessary to introduce explosion-proof equipment, and manufacturing costs can be reduced and industrial implementation is possible.
前記Ｘ（ＢＦ４）ｍで表されるテトラフルオロホウ酸塩が、常温溶融塩としての４級アンモニウムテトラフルオロホウ酸塩であってもよい。 The tetrafluoroborate represented by X (BF 4 ) m may be a quaternary ammonium tetrafluoroborate as a room temperature molten salt.
本発明に於いては、前記テトラフルオロホウ酸塩が常温溶融塩としての４級アンモニウムテトラフルオロホウ酸塩であっても、好適に加水分解生成物の除去が可能になり、高純度のテトラフルオロホウ酸塩が得られる。 In the present invention, even if the tetrafluoroborate is a quaternary ammonium tetrafluoroborate as a room temperature molten salt, it is possible to suitably remove the hydrolysis product, and high purity tetrafluoroborate. A borate is obtained.
本発明のテトラフルオロホウ酸塩の精製方法について、以下に説明する。本発明の精製方法は、一般式Ｘ（ＢＦ４）ｍで表されるテトラフルオロホウ酸塩中に含まれるホウ酸又はテトラフルオロホウ酸アニオンの加水分解生成物の少なくとも何れかを除去するものであり、過剰のフッ化水素酸を添加することによりホウフッ化水素酸を生成させた後、フッ化水素酸の留去に伴い、ホウフッ化水素酸を除去するものである。 The method for purifying tetrafluoroborate according to the present invention will be described below. The purification method of the present invention removes at least one of boric acid or a hydrolysis product of a tetrafluoroborate anion contained in a tetrafluoroborate represented by the general formula X (BF 4 ) m. In addition, after adding borohydrofluoric acid by adding excess hydrofluoric acid, borohydrofluoric acid is removed along with the distillation of hydrofluoric acid.
前記Ｘは、４級アンモニウム、４級ホスホニウム、アンモニウム、ＩＡ族元素、IIＡ族元素、及びIIIＢ族元素からなる群より選択される少なくとも何れか１つを表す。また、ｍは自然数であり、Ｘの価数に等しい。 X represents at least one selected from the group consisting of quaternary ammonium, quaternary phosphonium, ammonium, a group IA element, a group IIA element, and a group IIIB element. M is a natural number and is equal to the valence of X.
前記４級アンモニウムとしては、テトラアルキルアンモニウムカチオン、イミダゾリウムカチオン、ピラゾリウムカチオン、ピリジニウムカチオン、トリアゾリウムカチオン、ピリダジニウムカチオン、チアゾリウムカチオン、オキサゾリウムカチオン、ピリミジニウムカチオン、ピラジニウムカチオン等が挙げられるがこの限りではない。主な例として以下の化合物が挙げられる。 Examples of the quaternary ammonium include tetraalkyl ammonium cation, imidazolium cation, pyrazolium cation, pyridinium cation, triazolium cation, pyridazinium cation, thiazolium cation, oxazolium cation, pyrimidinium cation, A pyrazinium cation and the like can be mentioned, but not limited thereto. The following compounds are mentioned as main examples.
テトラアルキルアンモニウムカチオンとしては、テトラエチルアンモニウム、テトラメチルアンモニウム、テトラプロピルアンモニウム、テトラブチルアンモニウム、トリエチルメチルアンモニウム、トリメチルエチルアンモニウム、ジメチルジエチルアンモニウム、トリメチルプロピルアンモニウム、トリメチルブチルアンモニウム、ジメチルエチルプロピルアンモニウム、メチルエチルプロピルブチルアンモニウム、Ｎ，Ｎ−ジメチルピロリジニウム、Ｎ−エチル−Ｎ−メチルピロリジニウム、Ｎ−メチル−Ｎ−プロピルピロリジニウム、Ｎ−エチル−Ｎ−プロピルピロリジニウム、Ｎ，Ｎ−ジメチルピペリジニウム、Ｎ−メチル−Ｎ−エチルピペリジニウム、Ｎ−メチル−Ｎ−プロピルピペリジニウム、Ｎ−エチル−Ｎ−プロピルピペリジニウム、スピロ−Ｎ，Ｎ’−ビピリジニウム、スピロ−Ｎ，Ｎ’−ビピペリジニウム、スピロ−Ｎ−ピペリジニウム−Ｎ−ピリジニウム、スピロ−Ｎ−アジリジニウム−Ｎ−ピリジニウム、スピロ−Ｎ−アジリジニウム−Ｎ−ピペリジニウム、Ｎ，Ｎ−ジメチルモルホリニウム、Ｎ−メチル−Ｎ−エチルモルホリニウム、Ｎ−メチル−Ｎ−プロピルモルホリニウム、Ｎ−エチル−Ｎ−プロピルモルホリニウム、トリメチルメトキシメチルアンモニウム、ジメチルエチルメトキシメチルアンモニウム、ジメチルプロピルメトキシメチルアンモニウム、ジメチルブチルメトキシメチルアンモニウム、ジエチルメチルメトキシメチルアンモニウム、メチルエチルプロピルメトキシメチルアンモニウム、トリエチルメトキシメチルアンモニウム、ジエチルプロピルメトキシメチルアンモニウム、ジエチルブチルメトキシメチルアンモニウム、ジプロピルメチルメトキシメチルアンモニウム、ジプロピルエチルメトキシメチルアンモニウム、トリプロピルメトキシメチルアンモニウム、トリブチルメトキシメチルアンモニウム、トリメチルエトキシメチルアンモニウム、ジメチルエチルエトキシメチルアンモニウム、ジメチルプロピルエトキシメチルアンモニウム、ジメチルブチルエトキシメチルアンモニウム、ジエチルメチルエトキシメチルアンモニウム、トリエチルエトキシメチルアンモニウム、ジエチルプロピルエトキシメチルアンモニウム、ジエチルブチルエトキシメチルアンモニウム、ジプロピルメチルエトキシメチルアンモニウム、ジプロピルエチルエトキシメチルアンモニウム、トリプロピルエトキシメチルアンモニウム、トリブチルエトキシメチルアンモニウム、Ｎ−メチル−Ｎ−メトキシメチルピロリジニウム、Ｎ−エチル−Ｎ−メトキシメチルピロリジニウム、Ｎ−プロピル−Ｎ−メトキシメチルピロリジニウム、Ｎ−ブチル−Ｎ−メトキシメチルピロリジニウム、Ｎ−メチル−Ｎ−エトキシメチルピロリジニウム、Ｎ−メチル−Ｎ−プロポキシメチルピロリジニウム、Ｎ−メチル−Ｎ−ブトキシメチルピロリジニウム、Ｎ−メチル−Ｎ−メトキシメチルピペリジニウム、Ｎ−エチル−Ｎ−メトキシメチルピロリジニウム、Ｎ−メチル−Ｎ−エトキシメチルピロリジニウム、Ｎ−プロピル−Ｎ−メトキシメチルピロリジニウム、Ｎ−メチル−Ｎ−プロポキシメチルピロリジニウム等が挙げられるがこれらの限りではない。 Tetraalkylammonium cations include tetraethylammonium, tetramethylammonium, tetrapropylammonium, tetrabutylammonium, triethylmethylammonium, trimethylethylammonium, dimethyldiethylammonium, trimethylpropylammonium, trimethylbutylammonium, dimethylethylpropylammonium, methylethylpropyl Butylammonium, N, N-dimethylpyrrolidinium, N-ethyl-N-methylpyrrolidinium, N-methyl-N-propylpyrrolidinium, N-ethyl-N-propylpyrrolidinium, N, N-dimethyl Piperidinium, N-methyl-N-ethylpiperidinium, N-methyl-N-propylpiperidinium, N-ethyl-N-propylpipe Dinium, spiro-N, N′-bipyridinium, spiro-N, N′-bipiperidinium, spiro-N-piperidinium-N-pyridinium, spiro-N-aziridinium-N-pyridinium, spiro-N-aziridinium-N-piperidinium, N, N-dimethylmorpholinium, N-methyl-N-ethylmorpholinium, N-methyl-N-propylmorpholinium, N-ethyl-N-propylmorpholinium, trimethylmethoxymethylammonium, dimethylethylmethoxy Methylammonium, dimethylpropylmethoxymethylammonium, dimethylbutylmethoxymethylammonium, diethylmethylmethoxymethylammonium, methylethylpropylmethoxymethylammonium, triethylmethoxymethylammonium, Ethylpropylmethoxymethylammonium, diethylbutylmethoxymethylammonium, dipropylmethylmethoxymethylammonium, dipropylethylmethoxymethylammonium, tripropylmethoxymethylammonium, tributylmethoxymethylammonium, trimethylethoxymethylammonium, dimethylethylethoxymethylammonium, dimethylpropyl Ethoxymethylammonium, dimethylbutylethoxymethylammonium, diethylmethylethoxymethylammonium, triethylethoxymethylammonium, diethylpropylethoxymethylammonium, diethylbutylethoxymethylammonium, dipropylmethylethoxymethylammonium, dipropylethylethoxymethylammonium , Tripropylethoxymethylammonium, tributylethoxymethylammonium, N-methyl-N-methoxymethylpyrrolidinium, N-ethyl-N-methoxymethylpyrrolidinium, N-propyl-N-methoxymethylpyrrolidinium, N -Butyl-N-methoxymethylpyrrolidinium, N-methyl-N-ethoxymethylpyrrolidinium, N-methyl-N-propoxymethylpyrrolidinium, N-methyl-N-butoxymethylpyrrolidinium, N-methyl -N-methoxymethylpiperidinium, N-ethyl-N-methoxymethylpyrrolidinium, N-methyl-N-ethoxymethylpyrrolidinium, N-propyl-N-methoxymethylpyrrolidinium, N-methyl-N -Propoxymethylpyrrolidinium, etc. Not.
テトラアルキルホスホニウムカチオンとしては、テトラエチルホスホニウム、テトラメチルホスホニウム、テトラプロピルホスホニウム、テトラブチルホスホニウム、トリエチルメチルホスホニウム、トリメチルエチルホスホニウム、ジメチルジエチルホスホニウム、トリメチルプロピルホスホニウム、トリメチルブチルホスホニウム、ジメチルエチルプロピルホスホニウム、メチルエチルプロピルブチルホスホニウム等が挙げられる。 Tetraalkylphosphonium cations include tetraethylphosphonium, tetramethylphosphonium, tetrapropylphosphonium, tetrabutylphosphonium, triethylmethylphosphonium, trimethylethylphosphonium, dimethyldiethylphosphonium, trimethylpropylphosphonium, trimethylbutylphosphonium, dimethylethylpropylphosphonium, methylethylpropyl And butylphosphonium.
イミダゾリウムカチオンとしては、１，３−ジメチルイミダゾリウム、１−エチル−３−メチルイミダゾリウム、１，３−ジエチルイミダゾリウム、１，２−ジメチル−３−エチルイミダゾリウム、１，２−ジメチル−３−プロピルイミダゾリウム等が挙げられるがこれらの限りではない。ピラゾリウムカチオンとしては１，２−ジメチルピラゾリウム、１−メチル−２−エチルピラゾリウム、１−プロピル−２−メチルピラゾリウム、１−メチル−２−ブチルピラゾリウム等が挙げられるがこれらの限りではない。ピリジニウムカチオンとしてはＮ−メチルピリジニウム、Ｎ−エチルピリジニウム、Ｎ−プロピルピリジニウム、Ｎ−ブチルピリジニウム等が挙げられるがこれらの限りではない。トリアゾリウムカチオンとしては、１−メチルトリアゾリウム、１−エチルトリアゾリウム、１−プロピルトリアゾリウム、１−ブチルトリアゾリウム等が挙げられるがこれらの限りではない。 Examples of the imidazolium cation include 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1,3-diethylimidazolium, 1,2-dimethyl-3-ethylimidazolium, 1,2-dimethyl- Although 3-propyl imidazolium etc. are mentioned, it is not restricted to these. Examples of the pyrazolium cation include 1,2-dimethylpyrazolium, 1-methyl-2-ethylpyrazolium, 1-propyl-2-methylpyrazolium, 1-methyl-2-butylpyrazolium, and the like. This is not the case. Examples of the pyridinium cation include, but are not limited to, N-methylpyridinium, N-ethylpyridinium, N-propylpyridinium, N-butylpyridinium, and the like. Examples of the triazolium cation include, but are not limited to, 1-methyltriazolium, 1-ethyltriazolium, 1-propyltriazolium, 1-butyltriazolium, and the like.
ピリダジニウムカチオンとしては１−メチルピリダジニウム、１−エチルピリダジニウム、１−プロピルピリダジニウム、１−ブチルピリダジニウム等が挙げられるがこれらの限りではない。チアゾリウムカチオンとしては、１，２−ジメチルチアゾリウム、１，２−ジメチル−３−プロピルチアゾリウム等が挙げられるがこれらの限りではない。オキサゾリウムカチオンとしては、１−エチル−２−メチルオキサゾリウム、１，３−ジメチルオキサゾリウム等が挙げられるがこれらの限りではない。ピリミジニウムカチオンとしては、１，２−ジメチルピリミジニウム、１−メチル−３−プロピルピリミジニウム等が挙げられるがこれらの限りではない。ピラジニウムカチオンとしては、１−エチル−２−メチルピラジニウム、１−ブチルピラジニウム等が挙げられるがこれらに限定されるものではない。 Examples of the pyridazinium cation include, but are not limited to, 1-methylpyridazinium, 1-ethylpyridazinium, 1-propylpyridazinium, 1-butylpyridazinium and the like. Examples of thiazolium cations include, but are not limited to, 1,2-dimethylthiazolium, 1,2-dimethyl-3-propylthiazolium, and the like. Examples of the oxazolium cation include, but are not limited to, 1-ethyl-2-methyloxazolium, 1,3-dimethyloxazolium, and the like. Examples of the pyrimidinium cation include 1,2-dimethylpyrimidinium and 1-methyl-3-propylpyrimidinium, but are not limited thereto. Examples of the pyrazinium cation include, but are not limited to, 1-ethyl-2-methylpyrazinium, 1-butylpyrazinium and the like.
前記４級ホスホニウムとしては、テトラエチルホスホニウム、テトラプロピルホスホニウム、テトラブチルホスホニウム等のテトラアルキルホスホニウムカチオン等が挙げられる。 Examples of the quaternary phosphonium include tetraalkylphosphonium cations such as tetraethylphosphonium, tetrapropylphosphonium, and tetrabutylphosphonium.
前記ＩＡ族元素としては特に限定されないが、リチウム、ナトリウム、カリウム、ルビジウム、セシウム等が好ましい。 The group IA element is not particularly limited, but lithium, sodium, potassium, rubidium, cesium and the like are preferable.
前記IIＡ族元素としては特に限定されないが、ベリリウム、カルシウム、マグネシウム、ストロンチウム、バリウム等が好ましい。 The IIA group element is not particularly limited, but beryllium, calcium, magnesium, strontium, barium and the like are preferable.
前記IIIＢ族元素としては特に限定されないが、アルミニウム、ガリウム等が好ましい。 The IIIB group element is not particularly limited, but aluminum, gallium and the like are preferable.
尚、テトラフルオロホウ酸塩が４級アンモニウムテトラフルオロホウ酸塩（常温溶融塩）である場合、従来行われていた再結晶による精製方法では精製が不可能であった。しかし、本発明の精製方法では前記の様な常温溶融塩の場合にも簡便に精製を行うことができる。 In addition, when the tetrafluoroborate is quaternary ammonium tetrafluoroborate (room temperature molten salt), it was impossible to purify by a conventional recrystallization method. However, in the purification method of the present invention, purification can be carried out easily even in the case of the room temperature molten salt as described above.
フッ化水素酸の添加量はテトラフルオロホウ酸塩中の加水分解生成物に対し化学量論比に於いて過剰量となる程度であれば効果が得られ、例えばテトラフルオロホウ酸塩が固体の場合はこれを完溶させるだけのフッ化水素酸を添加すれば足りる。より具体的には、工業的な実用性の観点からテトラフルオロホウ酸塩の重量に対して０．０１重量倍〜１０重量倍、より好ましくは０．２重量倍〜２重量倍である。添加量が０．０１重量倍未満であると、フッ化水素酸に対し未反応の加水分解生成物が多く含まれる結果、これらの不純物の除去を十分に行うことができない場合がある。その一方、添加量が１０重量倍を超えると、添加したフッ化水素酸の留去工程が長時間必要であるという不都合な場合がある。尚、テトラフルオロホウ酸塩中の加水分解生成物の含有量は、カールフィッシャー水分測定により間接的に検出することができる。例えば、加水分解生成物がホウ酸の場合、検出量は水とほぼ同じ重量で検出される（厳密には水に対し０．８７倍）。従って、フッ化水素酸の添加量の設定は、カールフィッシャー水分測定値を目安に、ホウ酸をホウフッ化水素酸にするのに必要な化学量論比以上となる様にすれば足りる。 An effect can be obtained if the amount of hydrofluoric acid added is an excess in the stoichiometric ratio with respect to the hydrolysis product in tetrafluoroborate. For example, tetrafluoroborate is a solid solution. In such a case, it is sufficient to add hydrofluoric acid to dissolve it completely. More specifically, it is 0.01 to 10 times by weight, more preferably 0.2 to 2 times by weight with respect to the weight of tetrafluoroborate from the viewpoint of industrial practicality. When the addition amount is less than 0.01 times by weight, there are cases where these impurities cannot be sufficiently removed as a result of containing a large amount of unreacted hydrolysis products with respect to hydrofluoric acid. On the other hand, when the addition amount exceeds 10 times by weight, there may be an inconvenience that the step of distilling off the added hydrofluoric acid is necessary for a long time. The content of the hydrolysis product in tetrafluoroborate can be indirectly detected by Karl Fischer moisture measurement. For example, when the hydrolysis product is boric acid, the detected amount is detected at almost the same weight as water (strictly, 0.87 times that of water). Therefore, the amount of hydrofluoric acid to be added may be set so that the stoichiometric ratio or more necessary for making boric acid into borohydrofluoric acid with reference to the measured value of Karl Fischer moisture.
また、前記フッ化水素酸としては特に限定されず、例えば無水フッ化水素酸が使用できる。フッ化水素酸の濃度としては、２０〜１００重量％が好ましく、より好ましくは５０〜１００重量％、更に好ましくは７５〜１００重量％である。 Moreover, it does not specifically limit as said hydrofluoric acid, For example, anhydrous hydrofluoric acid can be used. As a density | concentration of hydrofluoric acid, 20-100 weight% is preferable, More preferably, it is 50-100 weight%, More preferably, it is 75-100 weight%.
前記テトラフルオロホウ酸塩にフッ化水素酸を添加する際、フッ化水素酸は液状で添加してもガス状で添加してもよく、その投入方法は特に限定されるものではない。また、前記テトラフルオロホウ酸塩にフッ化水素酸を添加する際の添加速度は適宜必要に応じて設定すればよく、特に限定されるものではない。但し、フッ化水素酸の添加の際は、該フッ化水素酸の沸点を考慮して約２０℃以下となる様に冷却しながら行うのが好ましい。 When hydrofluoric acid is added to the tetrafluoroborate, hydrofluoric acid may be added in a liquid state or a gaseous state, and the charging method is not particularly limited. Moreover, what is necessary is just to set the addition rate at the time of adding hydrofluoric acid to the said tetrafluoro borate suitably as needed, and is not specifically limited. However, the addition of hydrofluoric acid is preferably performed while cooling so that the boiling point of hydrofluoric acid is about 20 ° C. or less.
前記フッ化水素酸を前記テトラフルオロホウ酸塩に添加した後、テトラフルオロホウ酸塩中に含まれるホウ酸や加水分解生成物をホウフッ化水素酸に変換させる際の温度としては、−２０℃〜２００℃が好ましく、０℃〜５０℃がより好ましく、０℃〜３０℃が更に好ましい。前記温度範囲内で、必要に応じて沸騰しない程度に加熱することもできる。 After adding the hydrofluoric acid to the tetrafluoroborate, the temperature when converting boric acid and hydrolysis products contained in the tetrafluoroborate to borohydrofluoric acid is −20 ° C. -200 degreeC is preferable, 0 degreeC-50 degreeC is more preferable, and 0 degreeC-30 degreeC is still more preferable. Within the said temperature range, it can also heat to the extent which does not boil as needed.
前記テトラフルオロホウ酸塩とフッ化水素酸との反応は、常温でも速やかに進行する。よって、反応時間を長くとる必要はなく、テトラフルオロホウ酸塩にフッ化水素酸を添加後、直ちにフッ化水素酸の除去を行ってもよい。フッ化水素酸の除去方法としては特に限定するものではなく、定法により蒸留でき、減圧又は加熱してもよく、これらを組み合わせてもよい。また、加熱を行いながら、窒素、アルゴン又は空気等、テトラフルオロホウ酸塩と反応しないガスを吹き込んで除去を行うこともできる。前記フッ化水素酸塩を除去する際の温度は、フッ化水素酸の沸点１９．９℃以上であれば特に限定されるものではない。また、上限温度としてはテトラフルオロホウ酸塩の分解温度以下であればよい。より具体的には、１９．９〜２００℃が好ましく、５０〜２００℃がより好ましく、１１０〜２００℃が更に好ましく、１３０〜２００℃が特に好ましい。 The reaction between the tetrafluoroborate and hydrofluoric acid proceeds rapidly even at room temperature. Therefore, it is not necessary to take a long reaction time, and hydrofluoric acid may be removed immediately after adding hydrofluoric acid to tetrafluoroborate. The method for removing hydrofluoric acid is not particularly limited, and the hydrofluoric acid can be distilled by a conventional method, and may be reduced in pressure or heated, or a combination thereof. Moreover, it can remove by blowing in gas which does not react with tetrafluoroborate, such as nitrogen, argon, or air, while heating. The temperature at which the hydrofluoric acid salt is removed is not particularly limited as long as the boiling point of hydrofluoric acid is 19.9 ° C. or higher. Further, the upper limit temperature may be equal to or lower than the decomposition temperature of tetrafluoroborate. More specifically, 19.9-200 degreeC is preferable, 50-200 degreeC is more preferable, 110-200 degreeC is further more preferable, and 130-200 degreeC is especially preferable.
本発明の精製方法によって、前記テトラフルオロホウ酸塩に含まれる〔ＢＦｎ（ＯＨ）４−ｎ〕−（ｎは１〜３の自然数）又はホウ酸等の加水分解生成物の含有量が１回の操作で所望の数値に達しない場合には、本発明の精製方法を繰り返し行うことができる。これにより、前記加水分解生成物の含有量を一層低減することができる。 Purification method of the present invention, the contained in tetrafluoroborate [BF n (OH) 4-n] - the content of the (n is a natural number of 1 to 3) or hydrolysis products such as boric acid 1 If the desired value is not reached by a single operation, the purification method of the present invention can be repeated. Thereby, content of the said hydrolysis product can be reduced further.
本発明の精製方法により得られるテトラフルオロホウ酸塩を含む電解液は、不純物である前記加水分解生成物の総含有量が微量である。この為、耐電圧及び長期信頼性に優れている。その結果、前記電解液を電気二重層キャパシタ、電解コンデンサー又は電池等に好適に使用することができる。 The electrolytic solution containing tetrafluoroborate obtained by the purification method of the present invention has a very small total content of the hydrolysis products as impurities. For this reason, it is excellent in withstand voltage and long-term reliability. As a result, the electrolytic solution can be suitably used for an electric double layer capacitor, an electrolytic capacitor, a battery, or the like.
以下に、この発明の好適な実施例を例示的に詳しく説明する。但し、この実施例に記載されている材料や配合量等は、特に限定的な記載がない限りは、この発明の範囲をそれらのみに限定する趣旨のものではなく、単なる説明例に過ぎない。 Hereinafter, preferred embodiments of the present invention will be described in detail by way of example. However, the materials, blending amounts, and the like described in the examples are not intended to limit the scope of the present invention only to them, but are merely illustrative examples, unless otherwise specified.
（ホウ酸及びテトラフルオロホウ酸アニオンの加水分解生成物の分析）
ホウ酸及びテトラフルオロホウ酸アニオンの加水分解生成物は、カールフィッシャー滴定法により間接的に検出した。カールフィッシャー滴定法は、下記化学反応式（１）に示すヨウ素と水が定量的、かつ、選択的に反応することを利用した水分の分析方法である。
(Analysis of hydrolysis products of boric acid and tetrafluoroborate anions)
The hydrolysis products of boric acid and tetrafluoroborate anions were detected indirectly by Karl Fischer titration. The Karl Fischer titration method is a moisture analysis method utilizing the quantitative and selective reaction of iodine and water shown in the following chemical reaction formula (1).
ホウ酸化合物は、下記化学反応式（２）に示す様に、カールフィッシャー試薬と反応することが知られている（例えば、三菱化学のカールフィッシャー試薬、マニュアル、Ｐ４１参照） Boric acid compounds are known to react with Karl Fischer reagent as shown in the chemical reaction formula (2) below (see, for example, Karl Fischer reagent of Mitsubishi Chemical, manual, P41).
よって、式（２）の反応を利用してホウ酸化合物の含有量を測定することができる。カールフィッシャー滴定分析の検出値からは、それがホウ酸化合物の含有量であるか、水の含有量であるかは判別し難い。従って、下記の実施例及び比較例に於いては、クルクマ反応により、ホウ酸化合物が含有するか否かの定性試験を行った。クルクマ反応とは、黄色のクルクミン指示薬がホウ酸の作用によって異性化して赤褐色を呈する反応である（例えば、定性分析化学、中巻、イオン反応編、Ｐ．３１５参照）。 Therefore, content of a boric acid compound can be measured using reaction of Formula (2). From the detection value of Karl Fischer titration analysis, it is difficult to determine whether it is a boric acid compound content or water content. Therefore, in the following Examples and Comparative Examples, a qualitative test was conducted as to whether or not a boric acid compound contained by the Curcuma reaction. The Curcuma reaction is a reaction in which a yellow curcumin indicator is isomerized by the action of boric acid to give a reddish brown color (for example, see Qualitative Analytical Chemistry, Volume 1, Ion Reaction, P.315).
クルクマ反応によるクルクミン呈色とカールフィッシャー滴定法とにより、ホウ酸化合物を簡便に、間接的に定量できる。クルクミン呈色が起こらない場合、カールフィッシャー滴定法の検出値は水を検出していることを示す。その一方、クルクミン呈色が起きる場合、カールフィッシャー滴定法の検出値にはホウ酸及びホウ酸化合物を含むことを示す。 The boric acid compound can be easily and indirectly quantified by curcumin coloration by the Curcuma reaction and the Karl Fischer titration method. When no curcumin coloration occurs, the detection value of the Karl Fischer titration method indicates that water is detected. On the other hand, when curcumin coloration occurs, it indicates that the detection value of the Karl Fischer titration method includes boric acid and a boric acid compound.
（実施例１）
水分値３０００ｐｐｍ、クルクミン呈色が赤褐色のトリエチルメチルアンモニウムテトラフルオロボレート５０．０ｇに対し、無水フッ化水素酸８．５ｇを添加し均一混合した。その後、１３０℃の条件下で、窒素５Ｌ／ｍｉｎにて３時間フローしながら、フッ化水素酸、ホウフッ化水素酸及び水を留去した。精製後のトリエチルメチルアンモニウムテトラフルオロボレート４９.８ｇについて、水分量を測定したところ２９０ｐｐｍであった。また、クルクミン呈色は赤褐色であった。
Example 1
8.5 g of anhydrous hydrofluoric acid was added to and mixed uniformly with 50.0 g of triethylmethylammonium tetrafluoroborate having a moisture value of 3000 ppm and a curcumin color of reddish brown. Then, hydrofluoric acid, borohydrofluoric acid, and water were distilled off while flowing at 130 ° C. with nitrogen at 5 L / min for 3 hours. About 49.8 g of triethylmethylammonium tetrafluoroborate after purification, the water content was measured and found to be 290 ppm. The color of curcumin was reddish brown.
更に、得られたトリエチルメチルアンモニウムテトラフルオロボレートに再度無水フッ化水素酸７．５ｇを添加し、均一混合した後、前記と同様の条件でフッ化水素酸、ホウフッ化水素酸及び水を留去した。精製後のトリエチルメチルアンモニウムテトラフルオロボレート４９．７ｇについて、水分量を測定したところ１９ｐｐｍであった。また、クルクミン呈色は黄色であった。 Further, 7.5 g of anhydrous hydrofluoric acid was again added to the obtained triethylmethylammonium tetrafluoroborate and mixed uniformly, and then hydrofluoric acid, borohydrofluoric acid and water were distilled off under the same conditions as described above. did. About 49.7 g of triethylmethylammonium tetrafluoroborate after purification, the water content was measured and found to be 19 ppm. The color of curcumin was yellow.
（実施例２）
水分値２２００ｐｐｍ、クルクミン呈色が赤褐色の１−エチル−３−メチルイミダソリウムテトラフルオロボレート５０．０ｇに対し、無水フッ化水素酸５．０ｇを添加し均一混合した。その後、１３０℃の条件下で、窒素５Ｌ／ｍｉｎにて２時間バブリングしながら、フッ化水素酸、ホウフッ化水素酸及び水を留去した。精製後の１−エチル−３−メチルイミダソリウムテトラフルオロボレート４９．７ｇについて、水分量を測定したところ３１０ｐｐｍであった。また、クルクミン呈色は赤褐色であった。
(Example 2)
To 50.0 g of 1-ethyl-3-methylimidazolium tetrafluoroborate having a moisture value of 2200 ppm and curcumin coloration of reddish brown, 5.0 g of anhydrous hydrofluoric acid was added and mixed uniformly. Then, hydrofluoric acid, borohydrofluoric acid, and water were distilled off while bubbling under nitrogen at 5 L / min for 2 hours under conditions of 130 ° C. About 49.7 g of 1-ethyl-3-methylimidazolium tetrafluoroborate after purification, the water content was measured and found to be 310 ppm. The color of curcumin was reddish brown.
更に、得られた１−エチル−３−メチルイミダソリウムテトラフルオロボレートに再度無水フッ化水素酸５．０ｇを添加し、均一混合した後、前記と同様の条件でフッ化水素酸、ホウフッ化水素酸及び水を留去した。精製後の１−エチル−３−メチルイミダソリウムテトラフルオロボレート４９．６ｇについて、水分量を測定したところ２３ｐｐｍであった。また、クルクミン呈色は黄色であった。 Further, 5.0 g of anhydrous hydrofluoric acid was again added to the obtained 1-ethyl-3-methylimidazolium tetrafluoroborate and mixed uniformly, and then hydrofluoric acid and borofluoride were used under the same conditions as described above. Hydrogen acid and water were distilled off. A water content of 49.6 g of 1-ethyl-3-methylimidazolium tetrafluoroborate after purification was 23 ppm. The color of curcumin was yellow.
（実施例３）
水分値２５００ｐｐｍ、クルクミン呈色が赤褐色のリチウムテトラフルオロボレート１００１．６ｇに対し、無水フッ化水素酸１３０．０ｇを添加し撹拌して均一混合した。その後、−３０℃に冷却して白色固体をろ別した。得られた白色固体を、１００℃の湯浴にてフッ化水素酸を留去した。更に、１０５℃の条件下で、窒素５Ｌ／ｍｉｎにて５時間フローしながら、フッ化水素酸、ホウフッ化水素酸及び水を完全に留去した。精製後のリチウムテトラフルオロボレート６０５．０ｇについて、水分量を測定したところ４１ｐｐｍであった。また、クルクミン呈色は黄色であった。
(Example 3)
130.0 g of anhydrous hydrofluoric acid was added to 1001.6 g of lithium tetrafluoroborate having a moisture value of 2500 ppm and reddish brown curcumin, and the mixture was stirred and mixed uniformly. Then, it cooled to -30 degreeC and filtered white solid. Hydrofluoric acid was distilled off from the obtained white solid in a hot water bath at 100 ° C. Furthermore, hydrofluoric acid, borohydrofluoric acid, and water were completely distilled off while flowing at 105 ° C. with 5 L / min of nitrogen for 5 hours. The water content of the purified lithium tetrafluoroborate 605.0 g was 41 ppm. The color of curcumin was yellow.
（比較例１）
水分値４０００ｐｐｍ、クルクミン呈色が赤褐色のテトラエチルアンモニウムテトラフルオロボレート１００ｇに対し、エタノール５００ｇを添加し、９０℃に加熱してエタノールに完全に溶解させた。得られた溶液を室温まで自然放冷した後、更に１５℃になるまで冷却した。冷却により析出した結晶をろ別し、１０℃のエタノールで洗浄した。その後、１２０℃の条件下で、窒素５Ｌ／ｍｉｎにてフローしながら、５時間で乾燥を行った。精製後のテトラエチルアンモニウムテトラフルオロボレート７５ｇについて水分量を測定したところ、２００ｐｐｍであった。また、クルクミン呈色は赤褐色であった。
(Comparative Example 1)
500 g of ethanol was added to 100 g of tetraethylammonium tetrafluoroborate having a water content of 4000 ppm and a curcumin color of reddish brown, and heated to 90 ° C. to completely dissolve in ethanol. The resulting solution was allowed to cool to room temperature and then cooled to 15 ° C. Crystals precipitated by cooling were filtered off and washed with ethanol at 10 ° C. Then, it dried in 5 hours, flowing under nitrogen 5 L / min on 120 degreeC conditions. It was 200 ppm when the moisture content was measured about 75 g of tetraethylammonium tetrafluoroborate after refinement | purification. The color of curcumin was reddish brown.
Claims (2)
前記フッ化水素酸の留去に伴い、前記ホウフッ化水素酸を除去することを特徴とするテトラフルオロホウ酸塩の精製方法。 General formula X (BF 4 ) m (wherein X represents at least one selected from the group consisting of quaternary ammonium, quaternary phosphonium, ammonium, group IA element, group IIA element and group IIIB element) M is a natural number and is equal to the valence of X.) Excess amount of fluorination with respect to the hydrolysis product of boric acid or tetrafluoroborate anion contained in the tetrafluoroborate represented by Hydrochloric acid is added to the tetrafluoroborate to react with at least one of the hydrolysis products to produce borohydrofluoric acid,
A method for purifying tetrafluoroborate, wherein the borohydrofluoric acid is removed as the hydrofluoric acid is distilled off.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007277111A (en) * | 2006-04-03 | 2007-10-25 | Stella Chemifa Corp | Method for producing tetrafluoroborate |
| JP2007281014A (en) * | 2006-04-03 | 2007-10-25 | Stella Chemifa Corp | Method of refining quaternary ammonium tetrafluoroborate salt |
| JP2012026981A (en) * | 2010-07-27 | 2012-02-09 | Maezawa Ind Inc | Tetrafluoroborate ion detection agent, tetrafluoroborate ion detection kit, and tetrafluoroborate ion detection method |
| JP2012131658A (en) * | 2010-12-21 | 2012-07-12 | Morita Kagaku Kogyo Kk | Method for producing lithium borofluoride |
| CN109438511A (en) * | 2018-12-11 | 2019-03-08 | 河南省科学院化学研究所有限公司 | A method of synthesis tetrafluoro boric acid di-tert-butyl-phenyl phosphonium salt |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007277111A (en) * | 2006-04-03 | 2007-10-25 | Stella Chemifa Corp | Method for producing tetrafluoroborate |
| JP2007281014A (en) * | 2006-04-03 | 2007-10-25 | Stella Chemifa Corp | Method of refining quaternary ammonium tetrafluoroborate salt |
| JP2012026981A (en) * | 2010-07-27 | 2012-02-09 | Maezawa Ind Inc | Tetrafluoroborate ion detection agent, tetrafluoroborate ion detection kit, and tetrafluoroborate ion detection method |
| JP2012131658A (en) * | 2010-12-21 | 2012-07-12 | Morita Kagaku Kogyo Kk | Method for producing lithium borofluoride |
| CN109438511A (en) * | 2018-12-11 | 2019-03-08 | 河南省科学院化学研究所有限公司 | A method of synthesis tetrafluoro boric acid di-tert-butyl-phenyl phosphonium salt |
| CN109438511B (en) * | 2018-12-11 | 2020-11-06 | 河南省科学院化学研究所有限公司 | A kind of method for synthesizing di-tert-butylphenylphosphonium tetrafluoroborate |
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