JP6692033B2 - Silicon-containing sulfonate - Google Patents
Silicon-containing sulfonate Download PDFInfo
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- JP6692033B2 JP6692033B2 JP2015230596A JP2015230596A JP6692033B2 JP 6692033 B2 JP6692033 B2 JP 6692033B2 JP 2015230596 A JP2015230596 A JP 2015230596A JP 2015230596 A JP2015230596 A JP 2015230596A JP 6692033 B2 JP6692033 B2 JP 6692033B2
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- Prior art keywords
- silicon
- formula
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- group
- ion
- Prior art date
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims description 148
- 239000010703 silicon Substances 0.000 title claims description 148
- 229910052710 silicon Inorganic materials 0.000 title claims description 148
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 title claims description 129
- -1 phosphonium ion Chemical class 0.000 claims description 48
- 125000000217 alkyl group Chemical group 0.000 claims description 43
- 150000003839 salts Chemical class 0.000 claims description 43
- 125000004432 carbon atom Chemical group C* 0.000 claims description 42
- 239000003792 electrolyte Substances 0.000 claims description 30
- 239000002608 ionic liquid Substances 0.000 claims description 27
- 238000003860 storage Methods 0.000 claims description 26
- 230000005611 electricity Effects 0.000 claims description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 14
- 150000001768 cations Chemical class 0.000 claims description 14
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 12
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims description 5
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 5
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 5
- 229910001414 potassium ion Inorganic materials 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 claims description 5
- 229910001415 sodium ion Inorganic materials 0.000 claims description 5
- 125000003003 spiro group Chemical group 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 51
- 238000005160 1H NMR spectroscopy Methods 0.000 description 29
- 229910052708 sodium Inorganic materials 0.000 description 24
- 239000011734 sodium Substances 0.000 description 24
- 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 23
- 239000000243 solution Substances 0.000 description 22
- 239000002904 solvent Substances 0.000 description 22
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 17
- 238000003786 synthesis reaction Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 9
- 239000011777 magnesium Substances 0.000 description 9
- 229910052749 magnesium Inorganic materials 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- ZOSPVHQYAGHQPI-UHFFFAOYSA-M 1-(2-methoxyethyl)-1-methylpyrrolidin-1-ium chloride Chemical compound [Cl-].COCC[N+]1(CCCC1)C ZOSPVHQYAGHQPI-UHFFFAOYSA-M 0.000 description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000003456 ion exchange resin Substances 0.000 description 8
- 229920003303 ion-exchange polymer Polymers 0.000 description 8
- 238000006386 neutralization reaction Methods 0.000 description 8
- 150000003871 sulfonates Chemical class 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000003729 cation exchange resin Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- JLFVMLUGHPBHAQ-UHFFFAOYSA-M diethyl-(2-methoxyethyl)-methylazanium;iodide Chemical group [I-].CC[N+](C)(CC)CCOC JLFVMLUGHPBHAQ-UHFFFAOYSA-M 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000003747 Grignard reaction Methods 0.000 description 3
- WRYCSMQKUKOKBP-UHFFFAOYSA-N Imidazolidine Chemical group C1CNCN1 WRYCSMQKUKOKBP-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical group C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 229920001429 chelating resin Polymers 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 159000000003 magnesium salts Chemical class 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000006277 sulfonation reaction Methods 0.000 description 3
- ABJGUZZWSKMTEI-UHFFFAOYSA-M tributyl(dodecyl)phosphanium;bromide Chemical group [Br-].CCCCCCCCCCCC[P+](CCCC)(CCCC)CCCC ABJGUZZWSKMTEI-UHFFFAOYSA-M 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000005055 methyl trichlorosilane Substances 0.000 description 2
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 125000003386 piperidinyl group Chemical group 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 125000000168 pyrrolyl group Chemical group 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 description 1
- IBODDUNKEPPBKW-UHFFFAOYSA-N 1,5-dibromopentane Chemical compound BrCCCCCBr IBODDUNKEPPBKW-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical group C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 description 1
- 125000002393 azetidinyl group Chemical group 0.000 description 1
- 125000004069 aziridinyl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- IJMWREDHKRHWQI-UHFFFAOYSA-M magnesium;ethene;chloride Chemical compound [Mg+2].[Cl-].[CH-]=C IJMWREDHKRHWQI-UHFFFAOYSA-M 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/62—Quaternary ammonium compounds
- C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D207/06—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with radicals, containing only hydrogen and carbon atoms, attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
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Description
本発明は、ケイ素含有スルホン酸塩に関し、詳しくは、シラシクロアルカン構造を含む新規なケイ素含有スルホン酸塩に関する。 The present invention relates to silicon-containing sulfonates, and more particularly to novel silicon-containing sulfonates containing a silacycloalkane structure.
近年、デジタルカメラ、スマートフォン、タブレット機器等の携帯電子機器の普及がめざましく、これに伴って、それらの機器の電源として用いられる、充電により繰り返し使用できる二次電池等の蓄電デバイスの需要が大きく伸びるとともに、その高容量化、高エネルギー密度化の要望がますます高まりつつある。 In recent years, the spread of portable electronic devices such as digital cameras, smartphones, and tablet devices has been remarkable, and along with this, the demand for power storage devices such as secondary batteries that can be repeatedly used by charging and that are used as power sources for those devices has greatly increased. At the same time, there is an increasing demand for higher capacity and higher energy density.
これらの蓄電デバイスでは、一般に、非プロトン性の有機溶媒に電解質塩を溶解させた溶液が電解液として使用されている。これら電解質塩及び非プロトン性の有機溶媒の組み合わせについては、現在まで種々検討されてきている。電解質塩としては、４級アンモニウム塩（特許文献１〜３）や４級ホスホニウム塩（特許文献４）等が、有機溶媒への溶解性及び解離度、並びに電気化学的安定域が広いことから汎用されている。 In these power storage devices, a solution in which an electrolyte salt is dissolved in an aprotic organic solvent is generally used as the electrolytic solution. Various combinations of these electrolyte salts and aprotic organic solvents have been studied so far. As the electrolyte salt, a quaternary ammonium salt (Patent Documents 1 to 3), a quaternary phosphonium salt (Patent Document 4), or the like is widely used because it has a wide solubility and dissociation degree in an organic solvent and an electrochemically stable region. Has been done.
しかし、前記電解質塩はアニオンにフッ素原子等のハロゲン原子を含んでいることから、環境負荷という点で依然として問題があり、改善が望まれている。また、前述した用途に用いられる電解質塩には、高イオン導電性、広い電位窓等の電気化学的特性が要求される。 However, since the electrolyte salt contains a halogen atom such as a fluorine atom in the anion, there is still a problem in terms of environmental load, and improvement is desired. Further, the electrolyte salt used for the above-mentioned applications is required to have high ionic conductivity and electrochemical characteristics such as a wide potential window.
本発明は、前記事情に鑑みてなされたものであり、ハロゲン原子を含まず、蓄電デバイスの電解質、電解液等として好適に用いられる新規なスルホン酸塩を提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a novel sulfonate that does not contain a halogen atom and can be suitably used as an electrolyte of an electricity storage device, an electrolytic solution, or the like.
本発明者らは、前記目的を達成するために鋭意検討を重ねた結果、シラシクロアルカン構造を含むスルホン酸アニオンと、１価のカチオンとからなるケイ素含有スルホン酸塩が、電気化学的特性に優れることを見出し、本発明を完成させた。 The present inventors have conducted extensive studies to achieve the above-mentioned object, and as a result, a silicon-containing sulfonate composed of a sulfonate anion containing a silacycloalkane structure and a monovalent cation has an electrochemical characteristic. They have found that they are excellent and have completed the present invention.
すなわち、本発明は、下記蓄電デバイス用電解質塩及びイオン液体を提供する。
１．下記式（１）で表されるケイ素含有スルホン酸塩からなる蓄電デバイス用電解質塩。
２．Ｒ1が、メチル基又はエチル基である１の蓄電デバイス用電解質塩。
３．ｎが、２又は３である１又は２の蓄電デバイス用電解質塩。
４．Ａ+が、ナトリウムイオン、カリウムイオン及びリチウムイオンから選ばれる１価の金属イオンである１〜３のいずれかの蓄電デバイス用電解質塩。
５．Ａ+が、式（２）で表される４級アンモニウムイオンである１〜３のいずれかの蓄電デバイス用電解質塩。
６．前記４級アンモニウムイオンが、下記式（２−１）〜（２−４）で表されるものから選ばれる５の蓄電デバイス用電解質塩。
７．Ａ+が、式（３）で表される４級ホスホニウムイオンである１〜３のいずれかの蓄電デバイス用電解質塩。
８．Ａ+が、式（４）で表されるイミダゾリウムイオンである１〜３のいずれかの蓄電デバイス用電解質塩。
９．Ａ+が、式（５）で表されるピリジニウムイオンである１〜３のいずれかの蓄電デバイス用電解質塩。
１０．前記ケイ素含有スルホン酸塩が、イオン液体である１〜１０のいずれかの蓄電デバイス用電解質塩。
１１．下記式（１''）で表されるケイ素含有スルホン酸塩からなるイオン液体。
That is, the present invention provides the following electrolyte salt and ionic liquid for an electricity storage device .
1. An electrolyte salt for an electricity storage device comprising a silicon-containing sulfonate represented by the following formula (1).
2. 1. An electrolyte salt for an electricity storage device, wherein R 1 is a methyl group or an ethyl group.
3. The electrolyte salt for an electricity storage device according to 1 or 2, wherein n is 2 or 3.
4. The electrolyte salt for an electricity storage device according to any one of 1 to 3, wherein A + is a monovalent metal ion selected from sodium ion, potassium ion and lithium ion.
5 . The electrolyte salt for an electricity storage device according to any one of 1 to 3 , wherein A + is a quaternary ammonium ion represented by the formula (2).
6 . The electrolyte salt for an electricity storage device of 5 , wherein the quaternary ammonium ion is selected from those represented by the following formulas (2-1) to (2-4).
7 . The electrolyte salt for an electricity storage device according to any one of 1 to 3 , wherein A + is a quaternary phosphonium ion represented by the formula (3).
8 . The electrolyte salt for an electricity storage device according to any one of 1 to 3 , wherein A + is an imidazolium ion represented by the formula (4).
9 . The electrolyte salt for an electricity storage device according to any one of 1 to 3 , wherein A + is a pyridinium ion represented by the formula (5).
1 0 . The electrolyte salt for an electricity storage device according to any one of 1 to 10 , wherein the silicon-containing sulfonate is an ionic liquid.
11. An ionic liquid comprising a silicon-containing sulfonate represented by the following formula (1 ″).
本発明のケイ素含有スルホン酸塩は、ハロゲンフリーであるため環境負荷が小さい。また、本発明のケイ素含有スルホン酸塩は、従来のハロゲンフリーの塩に比べて広い電位窓を有し、電気化学的に安定である。 Since the silicon-containing sulfonate of the present invention is halogen-free, its environmental load is small. Further, the silicon-containing sulfonate of the present invention has a wider potential window than the conventional halogen-free salt and is electrochemically stable.
［ケイ素含有スルホン酸塩］
本発明のケイ素含有スルホン酸塩は、下記式（１）で表されるものである。
The silicon-containing sulfonate of the present invention is represented by the following formula (1).
式（１）中、Ｒ1は、炭素数１〜４のアルキル基を表す。前記アルキル基としては、直鎖状、分岐状、環状のいずれでもよく、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、シクロプロピル基、ｎ−ブチル基、ｓ−ブチル基、イソブチル基、ｔ−ブチル基、シクロブチル基等が挙げられる。これらのうち、Ｒ1としては、炭素数１〜３のアルキル基が好ましく、炭素数１〜３の直鎖アルキル基がより好ましく、メチル基又はエチル基が更に好ましい。 In formula (1), R 1 represents an alkyl group having 1 to 4 carbon atoms. The alkyl group may be linear, branched, or cyclic, and may be methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, s-butyl, isobutyl, Examples thereof include t-butyl group and cyclobutyl group. Of these, R 1 is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and further preferably a methyl group or an ethyl group.
式（１）中、ｍは、１又は２を表す。ｎは、２〜４の整数を表すが、２又は３が好ましい。 In formula (1), m represents 1 or 2. n represents an integer of 2 to 4, but 2 or 3 is preferable.
式（１）中、Ａ+は、１価のカチオンを表す。前記１価のカチオンとしては、特に限定されないが、１価の金属イオン、４級アンモニウムイオン、４級ホスホニウムイオン、イミダゾリウムイオン、ピリジニウムイオン等が好ましい。 In formula (1), A + represents a monovalent cation. The monovalent cation is not particularly limited, but monovalent metal ions, quaternary ammonium ions, quaternary phosphonium ions, imidazolium ions, pyridinium ions and the like are preferable.
前記１価の金属イオンとしては、ナトリウムイオン、カリウムイオン、リチウムイオン等のアルカリ金属イオン、銀イオン等が挙げられるが、コスト面から、アルカリ金属イオンが好ましい。 Examples of the monovalent metal ion include alkali metal ions such as sodium ion, potassium ion, and lithium ion, and silver ion. From the viewpoint of cost, the alkali metal ion is preferable.
前記４級アンモニウムイオンとしては、下記式（２）で表されるもの等が挙げられる。
式（２）中、Ｒ2〜Ｒ5は、それぞれ独立に、炭素数１〜４のアルキル基、又は−(ＣＨ2)k−ＯＲで表されるアルコキシアルキル基を表す。ｋは、１又は２を表す。Ｒは、メチル基又はエチル基を表す。 In formula (2), R 2 to R 5 each independently represent an alkyl group having 1 to 4 carbon atoms or an alkoxyalkyl group represented by — (CH 2 ) k —OR. k represents 1 or 2. R represents a methyl group or an ethyl group.
前記炭素数１〜４のアルキル基としては、Ｒ1として例示したものと同様のものが挙げられる。前記アルコキシアルキル基としては、メトキシメチル基、エトキシメチル基、メトキシエチル基及びエトキシエチル基が挙げられる。前記アルコキシアルキル基のうち、好ましくはメトキシエチル基又はエトキシエチル基である。 Examples of the alkyl group having 1 to 4 carbon atoms are the same as those exemplified as R 1 . Examples of the alkoxyalkyl group include a methoxymethyl group, an ethoxymethyl group, a methoxyethyl group and an ethoxyethyl group. Of the above alkoxyalkyl groups, a methoxyethyl group or an ethoxyethyl group is preferable.
また、Ｒ2〜Ｒ5のいずれか２つが、互いに結合してこれらが結合する窒素原子とともに環を形成してもよく、更に、残りの２つも互いに結合して窒素原子をスピロ原子とするスピロ環を形成してもよい。この場合、前記環としては、アジリジン環、アゼチジン環、ピロリジン環、ピペリジン環、アゼパン環、イミダゾリジン環、ピリジン環、ピロール環、イミダゾール環、キノール環等が挙げられるが、ピロリジン環、ピペリジン環、イミダゾリジン環、ピリジン環、ピロール環、イミダゾール環、キノール環等が好ましく、ピロリジン環、イミダゾリジン環等がより好ましい。また、前記スピロ環としては、１,１'−スピロビピロリジン環が特に好ましい。 Further, any two of R 2 to R 5 may be bonded to each other to form a ring with the nitrogen atom to which they are bonded, and the remaining two are also bonded to each other to form a spiro atom having a nitrogen atom as a spiro atom. You may form a ring. In this case, examples of the ring include an aziridine ring, an azetidine ring, a pyrrolidine ring, a piperidine ring, an azepan ring, an imidazolidine ring, a pyridine ring, a pyrrole ring, an imidazole ring, and a quinol ring, but a pyrrolidine ring, a piperidine ring, An imidazolidine ring, a pyridine ring, a pyrrole ring, an imidazole ring, a quinol ring and the like are preferable, and a pyrrolidine ring and an imidazolidine ring are more preferable. As the spiro ring, a 1,1′-spirobipyrrolidine ring is particularly preferable.
式（２）で表される４級アンモニウムイオンとして具体的には、下記式（２−１）〜（２−４）で表されるもの等が挙げられる。
式（２−１）〜（２−４）中、Ｒ及びｋは、前記と同じ。Ｒ11〜Ｒ14は、それぞれ独立に、炭素数１〜４のアルキル基を表す。Ｒ15及びＲ16は、それぞれ独立に、炭素数１〜４のアルキル基を表す。また、Ｒ15及びＲ16は、互いに結合してこれらが結合する窒素原子とともに環を形成してもよい。 In formulas (2-1) to (2-4), R and k are the same as above. R 11 to R 14 each independently represent an alkyl group having 1 to 4 carbon atoms. R 15 and R 16 each independently represent an alkyl group having 1 to 4 carbon atoms. R 15 and R 16 may be bonded to each other to form a ring with the nitrogen atom to which they are bonded.
前記４級ホスホニウムイオンとしては、下記式（３）で表されるもの等が挙げられる。
式（３）中、Ｒ6は、炭素数１〜１２のアルキル基を表す。前記炭素数１〜１２のアルキル基は、直鎖状、分岐状、環状のいずれでもよく、前述した炭素数１〜４のアルキル基のほか、ｎ−ペンチル基、シクロペンチル基、ｎ−ヘキシル基、シクロヘキシル基、ｎ−ヘプチル基、ｎ−オクチル基、ｎ−ノニル基、ｎ−デシル基、ｎ−ウンデシル基、ｎ−ドデシル基等が挙げられる。 In formula (3), R 6 represents an alkyl group having 1 to 12 carbon atoms. The alkyl group having 1 to 12 carbon atoms may be linear, branched or cyclic. In addition to the alkyl group having 1 to 4 carbon atoms described above, an n-pentyl group, a cyclopentyl group, an n-hexyl group, Examples thereof include cyclohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group and n-dodecyl group.
式（３）中、Ｒ7は、炭素数１〜２０のアルキル基を表す。前記炭素数１〜２０のアルキル基は、直鎖状、分岐状、環状のいずれでもよく、前述した炭素数１〜１２のアルキル基のほか、ｎ−トリデシル基、ｎ−テトラデシル基、ｎ−ペンタデシル基、ｎ−ヘキサデシル基、ｎ−ヘプタデシル基、ｎ−オクタデシル基、ｎ−ノナデシル基、ｎ−エイコシル基等が挙げられる。 In formula (3), R 7 represents an alkyl group having 1 to 20 carbon atoms. The alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic. In addition to the alkyl group having 1 to 12 carbon atoms described above, n-tridecyl group, n-tetradecyl group, n-pentadecyl group. Group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group and the like.
式（３）で表される４級ホスホニウムイオンのうち、Ｒ6とＲ7とが異なる構造のものはイオン液体を形成しやすい。この場合、Ｒ6としては、炭素数２〜８のアルキル基が好ましく、炭素数３〜８のアルキル基がより好ましく、炭素数４〜８のアルキル基が更に好ましい。Ｒ6として具体的には、例えば、ｎ−ブチル基、ｎ−ヘキシル基等が好ましい。Ｒ7としては、炭素数１０〜２０のアルキル基が好ましく、炭素数１２〜２０のアルキル基がより好ましい。 Among the quaternary phosphonium ions represented by the formula (3), those having a structure in which R 6 and R 7 are different from each other easily form an ionic liquid. In this case, R 6 is preferably an alkyl group having 2 to 8 carbon atoms, more preferably an alkyl group having 3 to 8 carbon atoms, and further preferably an alkyl group having 4 to 8 carbon atoms. Specific examples of R 6 include an n-butyl group and an n-hexyl group. As R 7 , an alkyl group having 10 to 20 carbon atoms is preferable, and an alkyl group having 12 to 20 carbon atoms is more preferable.
式（３）で表される４級ホスホニウムイオンの例を以下に示すが、これらに限定されない。
前記イミダゾリウムイオンとしては、下記式（４）で表されるもの等が挙げられる。
式（４）中、Ｒ8及びＲ9は、それぞれ独立に、炭素数１〜４のアルキル基、又は−(ＣＨ2)k−ＯＲで表されるアルコキシアルキル基を表す。Ｒ及びｋは、前記と同じである。前記炭素数１〜４のアルキル基及びアルコキシアルキル基としては、Ｒ2〜Ｒ5として例示したものと同様のものが挙げられる。 In formula (4), R 8 and R 9 each independently represent an alkyl group having 1 to 4 carbon atoms or an alkoxyalkyl group represented by — (CH 2 ) k —OR. R and k are the same as above. Examples of the alkyl group having 1 to 4 carbon atoms and the alkoxyalkyl group include the same groups as those exemplified as R 2 to R 5 .
前記ピリジニウムイオンとしては、下記式（５）で表されるもの等が挙げられる。
式（５）中、Ｒ10は、炭素数１〜８のアルキル基、又は−(ＣＨ2)k−ＯＲで表されるアルコキシアルキル基を表す。Ｒ及びｋは、前記と同じである。 In formula (5), R 10 represents an alkyl group having 1 to 8 carbon atoms or an alkoxyalkyl group represented by — (CH 2 ) k —OR. R and k are the same as above.
前記炭素数１〜８のアルキル基としては、直鎖状、分岐状、環状のいずれでもよく、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、シクロプロピル基、ｎ−ブチル基、ｓ−ブチル基、イソブチル基、ｔ−ブチル基、シクロブチル基、ｎ−ペンチル基、ｎ−ヘキシル基、ｎ−ヘプチル基、ｎ−オクチル基、シクロペンチル基、シクロヘキシル基等が挙げられる。前記アルコキシアルキル基としては、Ｒ2〜Ｒ5として例示したものと同様のものが挙げられる。 The alkyl group having 1 to 8 carbon atoms may be linear, branched, or cyclic, and may be methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, s- Examples thereof include a butyl group, an isobutyl group, a t-butyl group, a cyclobutyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a cyclopentyl group and a cyclohexyl group. Examples of the alkoxyalkyl group are the same as those exemplified as R 2 to R 5 .
本発明のケイ素含有スルホン酸塩は、カチオンの種類によってはイオン液体となる。例えば、カチオンが式（２−４）で表されるものはイオン液体となるし、式（３）で表されるもののうち、Ｒ6とＲ7とが異なる構造のものはイオン液体になりやすい。イオン液体とはイオンのみから構成される塩であって、一般に融点が１００℃以下のものをいう。本発明のケイ素含有スルホン酸塩からなるイオン液体は、ハロゲンフリーであるため環境負荷が小さく、また、従来のハロゲンフリーのイオン液体よりも耐熱性に優れる。本発明のケイ素含有スルホン酸塩からなるイオン液体の分解点は、好ましくは２５０℃以上、より好ましくは２８０℃以上、更に好ましくは３００℃以上である。 The silicon-containing sulfonate of the present invention becomes an ionic liquid depending on the type of cation. For example, a cation represented by the formula (2-4) is an ionic liquid, and a cation represented by the formula (3) having a structure in which R 6 and R 7 are different is likely to be an ionic liquid. .. The ionic liquid is a salt composed only of ions and generally has a melting point of 100 ° C. or lower. The ionic liquid comprising the silicon-containing sulfonate of the present invention is halogen-free and therefore has a small environmental load, and is superior in heat resistance to conventional halogen-free ionic liquids. The decomposition point of the ionic liquid comprising the silicon-containing sulfonate of the present invention is preferably 250 ° C or higher, more preferably 280 ° C or higher, and further preferably 300 ° C or higher.
［ケイ素含有スルホン酸塩の製造方法］
カチオンが１価の金属イオンである本発明のケイ素含有スルホン酸塩（下記式（６）で表されるもの）は、例えば、下記スキームＡに従って合成することができる。
The silicon-containing sulfonate of the present invention in which the cation is a monovalent metal ion (represented by the following formula (6)) can be synthesized according to the following scheme A, for example.
式中、Ｒ1、ｍ及びｎは、前記と同じ。ｎ'は、０〜２の整数を表す。Ｍ+は、１価の金属イオンを表す。前記１価の金属イオンとしては、前述したものと同様のものが挙げられる。Ｘは、ハロゲン原子を表す。前記ハロゲン原子としては、フッ素、塩素、臭素及びヨウ素原子が挙げられるが、塩素、臭素及びヨウ素原子が好ましい。 In the formula, R 1 , m and n are the same as above. n'represents an integer of 0-2. M + represents a monovalent metal ion. Examples of the monovalent metal ion include the same as those described above. X represents a halogen atom. Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms, and chlorine, bromine and iodine atoms are preferable.
出発原料である式（６''）で表される化合物は、従来公知の方法（J. Am. Chem. Soc., 1954, 76, pp. 6012-14等）に従って合成することができる。 The compound represented by the formula (6 ″), which is a starting material, can be synthesized according to a conventionally known method (J. Am. Chem. Soc., 1954, 76, pp. 6012-14 etc.).
スキームＡ中、第１段階の工程は、式（６''）で表される化合物と有機ハロゲン化物とをカップリング反応させて式（６'）で表される化合物とする工程である。式（６''）で表される化合物と、カップリングさせる有機ハロゲン化物との使用比率は、モル比で１：１〜１：１.５程度とすることができる。通常は１：１に近い比率で行うことが好ましい。なお、前記カップリング反応としては、グリニャール反応等を利用し得る。 In Scheme A, the step of the first step is a step of coupling the compound represented by the formula (6 ″) with an organic halide to give a compound represented by the formula (6 ′). The use ratio of the compound represented by the formula (6 ″) and the organic halide to be coupled can be about 1: 1 to 1: 1.5 in molar ratio. Usually, it is preferable to carry out at a ratio close to 1: 1. The coupling reaction may be a Grignard reaction or the like.
第１段階の工程においてグリニャール反応を利用する場合、式（６''）で表される化合物とマグネシウムとを反応させてグリニャール試薬にしてもよく、前記有機ハロゲン化物をグリニャール試薬にしてもよい。グリニャール反応において使用する溶媒としては、ジエチルエーテル、テトラヒドロフラン等のエーテル系溶媒が挙げられる。また、反応温度は、通常２５〜５０℃程度であり、好ましくは３６℃程度である。反応時間は、通常２〜６時間程度であり、好ましくは４時間程度である。 When the Grignard reaction is used in the first step, the compound represented by formula (6 ″) may be reacted with magnesium to form a Grignard reagent, or the organic halide may be a Grignard reagent. Examples of the solvent used in the Grignard reaction include ether solvents such as diethyl ether and tetrahydrofuran. The reaction temperature is usually about 25 to 50 ° C, preferably about 36 ° C. The reaction time is usually about 2 to 6 hours, preferably about 4 hours.
スキームＡ中、第２段階の工程は、式（６'）で表される化合物をスルホン化する工程である。スルホン化剤としては、亜硫酸水素ナトリウム等が挙げられる。なお、スルホン化は、J. Org. Chem., 1961, 26 (6), pp. 2097-2098を参考にして行うことができる。 In Scheme A, the second step is a step of sulfonating the compound represented by the formula (6 ′). Examples of the sulfonating agent include sodium hydrogen sulfite. The sulfonation can be carried out with reference to J. Org. Chem., 1961, 26 (6), pp. 2097-2098.
第２段階の工程において使用する溶媒としては、水のみ、又は水に補助溶媒としてメタノール、エタノール等のアルコール類、アセトン、アセトニトリル等の親水性溶媒等を加えた混合溶媒が挙げられる。また、反応温度は、通常２５〜１００℃程度であり、好ましくは３５〜７０℃程度である。反応時間は、通常２〜７２時間程度であり、好ましくは５〜２４時間程度である。 Examples of the solvent used in the step of the second step include water alone, or a mixed solvent obtained by adding alcohols such as methanol and ethanol as a cosolvent, and a hydrophilic solvent such as acetone and acetonitrile to water. The reaction temperature is usually about 25 to 100 ° C, preferably about 35 to 70 ° C. The reaction time is usually about 2 to 72 hours, preferably about 5 to 24 hours.
カチオンが４級アンモニウムイオン、４級ホスホニウムイオン、イミダゾリウムイオン、ピリジニウムイオン等である本発明のケイ素含有スルホン酸塩は、例えば、下記式（６）で表されるケイ素含有スルホン酸塩と下記式（７）で表される塩とを用いた、イオン交換樹脂を用いた中和法によって製造することができる。 The silicon-containing sulfonate of the present invention in which the cation is a quaternary ammonium ion, a quaternary phosphonium ion, an imidazolium ion, a pyridinium ion or the like is, for example, a silicon-containing sulfonate represented by the following formula (6) and the following formula. It can be produced by a neutralization method using an ion exchange resin with the salt represented by (7).
式（６）で表されるケイ素含有スルホン酸塩は、前述した方法に従って合成できる。式（７）で表される塩は、従来公知の方法に従って合成することができ、又は市販品を使用することができる。 The silicon-containing sulfonate represented by the formula (6) can be synthesized according to the method described above. The salt represented by the formula (7) can be synthesized according to a conventionally known method, or a commercially available product can be used.
この中和法の場合、まず式（６）で表されるケイ素含有スルホン酸塩及び式（７）で表される塩を、それぞれ陽イオン交換樹脂及び陰イオン交換樹脂を用いて下記式（１'）で表されるケイ素含有スルホン酸及び水酸化物に変換した後、両者を混合することによって得ることができる。
本発明においてこの中和法を適用する場合、式（６）で表されるケイ素含有スルホン酸塩、式（７）で表される塩共にイオン交換するものならば、対イオンの制限は特にない。しかし、コスト面から、式（６）で表されるケイ素含有スルホン酸塩としてはナトリウム塩、カリウム塩等が好ましい。式（７）で表される塩の対イオンとしてはハロゲンイオンが好ましく、コスト面から、塩素イオン、臭素イオンが特に好ましい。 When the neutralization method is applied in the present invention, there is no particular limitation on the counter ion as long as the silicon-containing sulfonate represented by the formula (6) and the salt represented by the formula (7) are ion-exchanged. .. However, from the viewpoint of cost, sodium salts, potassium salts and the like are preferable as the silicon-containing sulfonate represented by the formula (6). As the counter ion of the salt represented by the formula (7), a halogen ion is preferable, and a chlorine ion and a bromine ion are particularly preferable in terms of cost.
前記中和反応におけるケイ素含有スルホン酸及び水酸化物のモル比は特に制限がなく、５：１〜１：５程度とすることができる。コスト面を考慮すると、１：１に近い比率で行うことが好ましく、特に水層の中和点を反応終結点とするのが好ましい。
反応終了後は、通常の後処理を行って目的物を得ることができる。
The molar ratio of the silicon-containing sulfonic acid and the hydroxide in the neutralization reaction is not particularly limited and can be about 5: 1 to 1: 5. Considering the cost, it is preferable to carry out at a ratio close to 1: 1, and it is particularly preferable to use the neutralization point of the aqueous layer as the reaction end point.
After completion of the reaction, usual post-treatment can be carried out to obtain the desired product.
前記ケイ素含有スルホン酸塩のその他の製造方法として、例えば、式（６）で表されるケイ素含有スルホン酸塩と、式（７）で表される塩とを用いて、イオン交換樹脂を用いてイオン交換させる方法が挙げられる。 As another method for producing the silicon-containing sulfonate, for example, a silicon-containing sulfonate represented by formula (6) and a salt represented by formula (7) are used, and an ion exchange resin is used. A method of exchanging ions can be mentioned.
イオン交換方法として具体的には、まず、式（７）で表される塩の水溶液を陽イオン交換樹脂を充填したカラムに通し、前記塩のカチオンを陽イオン交換樹脂に担持させ、水を通して洗浄する。次に、式（６）で表されるケイ素含有スルホン酸塩を前記カラムに通し、溶出液を回収し、精製することで、目的のケイ素含有スルホン酸塩を得ることができる。 Specifically, as an ion exchange method, first, an aqueous solution of the salt represented by the formula (7) is passed through a column packed with a cation exchange resin, the cation of the salt is supported on the cation exchange resin, and washed with water. To do. Next, the silicon-containing sulfonate represented by formula (6) is passed through the column, and the eluate is collected and purified to obtain the desired silicon-containing sulfonate.
前記陽イオン交換樹脂としては、一般的に使用されている陽イオン交換樹脂を用いることができるが、強酸性陽イオン交換樹脂を用いることが好ましい。これらは、市販品として入手可能である。 As the cation exchange resin, a commonly used cation exchange resin can be used, but it is preferable to use a strongly acidic cation exchange resin. These are available as commercial products.
また、本発明のケイ素含有スルホン酸塩のうちケイ素含有スルホン酸有機塩は、前記の合成法以外でも成書（「イオン性液体−開発の最前線と未来−」、シーエムシー出版、２００３年、「イオン液体ＩＩ−驚異的な進歩と多彩な近未来−」、シーエムシー出版、２００６年等）記載の一般的なイオン液体合成方法で合成することが可能である。例えば、式（７）で表される塩と式（６）で表されるケイ素含有スルホン酸塩とを溶媒中で反応させて製造することもできる。この場合、溶媒は水、有機溶媒どちらでも構わない。 Further, among the silicon-containing sulfonates of the present invention, the silicon-containing sulfonic acid organic salt is not limited to the above-mentioned synthetic method, and can be used in the publications (“ionic liquids—the forefront and future of development”, CMC Publishing Co., 2003, It can be synthesized by a general ionic liquid synthesis method described in "Ionic Liquid II-Amazing Progress and Various Near Futures", CMC Publishing Co., Ltd., 2006). For example, it can be produced by reacting the salt represented by the formula (7) with the silicon-containing sulfonate represented by the formula (6) in a solvent. In this case, the solvent may be either water or an organic solvent.
［ケイ素含有スルホン酸塩の用途］
本発明のケイ素含有スルホン酸塩は、電気二重層キャパシタ、リチウムイオンキャパシタ、レドックスキャパシタ、リチウム二次電池、リチウムイオン二次電池、リチウム空気電池、プロトンポリマー電池等の蓄電デバイスの電解質や電解質用添加剤として使用し得る。更に、本発明のケイ素含有スルホン酸塩は、ゴム、プラスチック等の高分子材料に添加する帯電防止剤や可塑剤等としても使用し得る。
[Use of silicon-containing sulfonate]
The silicon-containing sulfonate of the present invention is an electrolyte for an electric storage device such as an electric double layer capacitor, a lithium ion capacitor, a redox capacitor, a lithium secondary battery, a lithium ion secondary battery, a lithium air battery, a proton polymer battery, or an additive for an electrolyte. It can be used as an agent. Further, the silicon-containing sulfonate of the present invention can be used as an antistatic agent or a plasticizer added to a polymer material such as rubber or plastic.
また、本発明のケイ素含有スルホン酸塩からなるイオン液体は、ハロゲンフリーのイオン液体であるため、環境負荷の少ないグリーン溶媒として有用である。特に、本発明のケイ素含有スルホン酸塩からなるイオン液体は、従来のイオン液体のみならず、従来の固体の電解質塩と比べても広い電位窓を有し、電気化学的に安定であるため、特に蓄電デバイスの電解質、電解液等として好適に用いることができる。 Further, the ionic liquid comprising the silicon-containing sulfonate of the present invention is a halogen-free ionic liquid, and thus is useful as a green solvent having a low environmental load. In particular, the ionic liquid comprising the silicon-containing sulfonate of the present invention has not only a conventional ionic liquid but also a wider potential window than the conventional solid electrolyte salt, and is electrochemically stable, In particular, it can be suitably used as an electrolyte, an electrolytic solution, etc. of an electricity storage device.
以下、実施例及び比較例を挙げて本発明をより具体的に説明するが、本発明は下記実施例に限定されない。なお、実施例等で使用した試薬、分析装置及び条件は以下のとおりである。 Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. The reagents, analyzers and conditions used in the examples and so on are as follows.
［１］核磁気共鳴（1Ｈ−ＮＭＲ）スペクトル
装置：日本電子(株)製 ＡＬ−４００
溶媒：重水、重ジメチルスルホキシド又は重クロロホルム
［２］融点
装置：セイコーインスツルメンツ(株)製 ＤＳＣ ６２００
測定条件：２０〜６０℃まで毎分１０℃昇温、６０℃で１分間保持後、６０〜−９０℃まで毎分１℃降温、−９０℃で１分間保持後、−９０〜６０℃まで毎分１℃昇温の条件で測定した。
［３］分解点
装置：セイコーインスツルメンツ(株)製 ＴＧ−ＤＴＡ ６２００
測定条件：空気雰囲気下、３０〜５００℃まで毎分１０℃昇温の条件で測定し、１０％重量減少した温度を分解点とした。
［４］サイクリックボルタンメトリー測定
装置：電気化学測定装置ＨＳＶ−１００（北斗電工(株)製）
測定条件：作用極にグラッシーカーボン電極、対極に白金電極、参照極にＡｇ／Ａｇ+型参照電極を用いて、掃引速度５ｍＶ／ｓｅｃで測定を行った。
[1] Nuclear magnetic resonance ( 1 H-NMR) spectrum device: AL-400 manufactured by JEOL Ltd.
Solvent: heavy water, heavy dimethyl sulfoxide or heavy chloroform [2] Melting point apparatus: Seiko Instruments Inc. DSC 6200
Measurement conditions: 10 ° C./minute heating to 20 to 60 ° C., holding at 60 ° C. for 1 minute, 1 ° C./minute cooling to 60 to −90 ° C., holding at −90 ° C. for 1 minute, then to −90 to 60 ° C. The measurement was performed under the condition that the temperature was raised by 1 ° C. per minute.
[3] Decomposition point device: TG-DTA 6200 manufactured by Seiko Instruments Inc.
Measurement conditions: Under an air atmosphere, the temperature was increased from 30 to 500 ° C. at 10 ° C./min, and the temperature at which the weight was reduced by 10% was taken as the decomposition point.
[4] Cyclic voltammetry measuring device: electrochemical measuring device HSV-100 (manufactured by Hokuto Denko Co., Ltd.)
Measurement conditions: A glassy carbon electrode was used as the working electrode, a platinum electrode was used as the counter electrode, and an Ag / Ag + type reference electrode was used as the reference electrode, and the measurement was performed at a sweep rate of 5 mV / sec.
［１］ケイ素含有スルホン酸ナトリウム塩の合成
［実施例１］ケイ素含有スルホン酸ナトリウム塩１の合成
滴下漏斗、還流冷却管及び磁気攪拌子を備えた三口フラスコに、マグネシウム２２.２５ｇ（９１５ｍｍｏｌ）を加えて脱気乾燥、窒素置換し、マグネシウムの表面を削るために窒素気流下で一晩攪拌した。三口フラスコに、メチルトリクロロシラン６７.３２ｇ（４５０ｍｍｏｌ）及びジエチルエーテル（４００ｍＬ）を入れ、滴下漏斗に１,４−ジブロモブタン９６.２６ｇ（４４６ｍｍｏｌ）のジエチルエーテル（３００ｍＬ）溶液を入れ、室温でゆっくりと滴下した。滴下開始後すぐに白濁し、滴下終了時には茶色懸濁液になった。滴下終了後、更に４時間加熱還流した。放冷後、吸引濾過でマグネシウム塩を濾別し、常圧蒸留でジエチルエーテルを留去した。残渣を常圧で蒸留し、沸点１３４℃留分を分取し、無色油状物のＳｉ−クロロ−Ｓｉ−メチルシラシクロペンタンを得た（収量２７.８７ｇ、収率４６.０％）。 To a three-necked flask equipped with a dropping funnel, a reflux condenser and a magnetic stirrer, 22.25 g (915 mmol) of magnesium was added, degassed and dried, and the atmosphere was replaced with nitrogen, and the mixture was stirred overnight under a nitrogen stream to scrape the surface of magnesium. .. 67.32 g (450 mmol) of methyltrichlorosilane and diethyl ether (400 mL) were placed in a three-necked flask, and a solution of 96.26 g (446 mmol) of 1,4-dibromobutane in diethyl ether (300 mL) was placed in the dropping funnel, and slowly added at room temperature. And dripped. Immediately after the start of the dropwise addition, it became cloudy, and at the end of the dropwise addition, it became a brown suspension. After completion of the dropping, the mixture was heated and refluxed for 4 hours. After allowing to cool, magnesium salts were filtered off by suction filtration, and diethyl ether was distilled off by atmospheric distillation. The residue was distilled under normal pressure, and the fraction with a boiling point of 134 ° C. was collected to obtain a colorless oily product of Si-chloro-Si-methylsilacyclopentane (yield 27.87 g, yield 46.0%).
滴下漏斗、還流冷却管及び磁気攪拌子を備えた三口フラスコに、窒素気流下でＳｉ−クロロ−Ｓｉ−メチルシラシクロペンタン１９.２２ｇ（１４３ｍｍｏｌ）及びＴＨＦ（８０ｍＬ）を入れて室温で攪拌し、そこに塩化ビニルマグネシウムのテトラヒドロフラン溶液１００ｍＬ（１４６ｍｍｏｌ）を室温でゆっくりと滴下した。滴下終了後、４時間加熱還流した。氷浴でフラスコを冷却しながら１ｍｏｌ／Ｌ塩酸を加えて加水分解し、有機層を抽出分離した。得られた淡黄色透明の有機層を無水硫酸マグネシウムで乾燥した。ジエチルエーテルを常圧蒸留で留去し、残渣を常圧で蒸留して１０６℃留分を分取し、無色液体としてＳｉ−メチル−Ｓｉ−ビニルシラシクロペンタンを得た（収量８.５２８ｇ、収率４７.２％）。 A three-necked flask equipped with a dropping funnel, a reflux condenser and a magnetic stirrer was charged with 19.22 g (143 mmol) of Si-chloro-Si-methylsilacyclopentane and THF (80 mL) under a nitrogen stream and stirred at room temperature. 100 mL (146 mmol) of a solution of vinylmagnesium chloride in tetrahydrofuran was slowly added dropwise thereto at room temperature. After completion of dropping, the mixture was heated under reflux for 4 hours. While cooling the flask in an ice bath, 1 mol / L hydrochloric acid was added for hydrolysis, and the organic layer was extracted and separated. The obtained pale yellow transparent organic layer was dried over anhydrous magnesium sulfate. Diethyl ether was distilled off under atmospheric pressure, the residue was distilled under atmospheric pressure, and the 106 ° C. fraction was collected to obtain Si-methyl-Si-vinylsilacyclopentane as a colorless liquid (yield 8.528 g, Yield 47.2%).
得られたＳｉ−メチル−Ｓｉ−ビニルシラシクロペンタン、これの２倍の物質量のＮａＨＳＯ3及び０.１７倍の物質量のＮａＮＯ2、並びにＮａＮＯ2と同重量のＮａＮＯ3をオートクレーブに投入した。続いてＳｉ−メチル−Ｓｉ−ビニルシラシクロペンタンの６０倍容量のイオン交換水とメタノールとの混合液（比率２：１）を投入し、オートクレーブを閉じ密閉系にし、激しく攪拌を行い終夜反応させた。充分に長時間反応させた後、オートクレーブを開放し、析出した固体分を桐山ロートを用いた減圧濾過で濾別した。得られた濾液をエバポレータで濃縮した。この時、メタノールが留去した程度で止め、イオン交換水を残した溶液とし、そのまま冷蔵庫に入れた。結晶が析出した後、桐山ロートを用い、減圧濾過により濾別した。この時、洗浄液は冷蔵庫で冷やしておいたイオン交換水を用いた。得られた結晶を同様の方法でイオン交換水のみを溶媒として再結晶を数度繰り返し行い、目的物であるケイ素含有スルホン酸ナトリウム塩１を得た（収率３０％）。ケイ素含有スルホン酸ナトリウム塩１の1Ｈ−ＮＭＲチャート（溶媒：重水）を図１に示す。 The resulting Si- methyl -Si- vinyl silacyclopentane, twice the amount of substance of NaHSO 3 and 0.17 times the substance amount of NaNO 2 in which, as well as NaNO 2 the same weight of NaNO 3 were added to the autoclave .. Then, a mixed solution of Si-methyl-Si-vinylsilacyclopentane with 60 times the volume of ion-exchanged water and methanol (ratio 2: 1) was added, the autoclave was closed to make a closed system, and the mixture was vigorously stirred and reacted overnight. It was After reacting for a sufficiently long time, the autoclave was opened, and the precipitated solid was filtered by vacuum filtration using a Kiriyama funnel. The obtained filtrate was concentrated with an evaporator. At this time, the solution was stopped when methanol was distilled off, and a solution was left with ion-exchanged water, and the solution was placed in the refrigerator as it was. After the crystals were deposited, they were filtered by vacuum filtration using a Kiriyama funnel. At this time, the cleaning liquid used was ion-exchanged water that had been cooled in a refrigerator. The obtained crystals were recrystallized several times by the same method using only ion-exchanged water as a solvent to obtain a silicon-containing sodium sulfonate salt 1 as a target product (yield 30%). 1 H-NMR chart (solvent: heavy water) of silicon-containing sodium sulfonate 1 is shown in FIG.
［実施例２］ケイ素含有スルホン酸ナトリウム塩２の合成
滴下漏斗、還流冷却管及び磁気攪拌子を備えた三口フラスコに、マグネシウム５.６５ｇ（２３２ｍｍｏｌ）を加えて脱気乾燥、窒素置換し、マグネシウムの表面を削るために窒素気流下で一晩攪拌した。三口フラスコに、実施例１に記載の方法で得た中間体Ｓｉ−クロロ−Ｓｉ−メチルシラシクロペンタン２１.５９ｇ（１６１ｍｍｏｌ）とジエチルエーテル（８０ｍＬ）とを入れ、滴下漏斗に３−クロロ−１−プロペン（塩化アリル）１２.７６ｇ（１６７ｍｍｏｌ）のジエチルエーテル（２０ｍＬ）溶液を入れ、室温でゆっくりと滴下した。滴下途中で黒色懸濁液になり、後に灰色懸濁液に変化した。滴下終了後、更に４時間加熱還流した。氷浴でフラスコを冷却しながら１ｍｏｌ／Ｌ塩酸を加えて加水分解し、有機層を抽出分離した。得られた淡黄色透明の有機層を無水硫酸マグネシウムで乾燥させた。ジエチルエーテルを常圧蒸留で留去し、残渣を減圧蒸留して５８−６３℃／４.２ｋＰａ留分を分取し、無色液体としてＳｉ−アリル−Ｓｉ−メチルシラシクロペンタンを得た（収量１６.６６ｇ、収率７３.８%）。 To a three-necked flask equipped with a dropping funnel, a reflux condenser and a magnetic stirrer, 5.65 g (232 mmol) of magnesium was added, degassed and dried, and the atmosphere was replaced with nitrogen, and the mixture was stirred overnight under a nitrogen stream to scrape the surface of magnesium. .. 21.59 g (161 mmol) of the intermediate Si-chloro-Si-methylsilacyclopentane obtained by the method described in Example 1 and diethyl ether (80 mL) were placed in a three-necked flask, and 3-chloro-1 was placed in a dropping funnel. A solution of 12.76 g (167 mmol) of propene (allyl chloride) in diethyl ether (20 mL) was added, and the mixture was slowly added dropwise at room temperature. During the dropping, it became a black suspension and later changed to a gray suspension. After completion of the dropping, the mixture was heated and refluxed for 4 hours. While cooling the flask in an ice bath, 1 mol / L hydrochloric acid was added for hydrolysis, and the organic layer was extracted and separated. The obtained pale yellow transparent organic layer was dried over anhydrous magnesium sulfate. Diethyl ether was distilled off by atmospheric distillation, the residue was distilled under reduced pressure and the 58-63 ° C./4.2 kPa fraction was collected to obtain Si-allyl-Si-methylsilacyclopentane as a colorless liquid (yield. 16.66 g, yield 73.8%).
Ｓｉ−メチル−Ｓｉ−ビニルシラシクロペンタンをＳｉ−アリル−Ｓｉ−メチルシラシクロペンタンに変更した以外は、実施例１に記載の方法と同様にしてスルホン化反応及び精製を行い、ケイ素含有スルホン酸ナトリウム塩２を得た（収率１０％）。ケイ素含有スルホン酸ナトリウム塩２の1Ｈ−ＮＭＲチャート（溶媒：重水）を図２に示す。 The sulfonation reaction and purification were performed in the same manner as in the method described in Example 1 except that Si-methyl-Si-vinylsilacyclopentane was changed to Si-allyl-Si-methylsilacyclopentane, and the silicon-containing sulfonic acid was used. Sodium salt 2 was obtained (yield 10%). The 1 H-NMR chart (solvent: heavy water) of silicon-containing sodium sulfonate 2 is shown in FIG.
［実施例３］ケイ素含有スルホン酸ナトリウム塩３の合成
滴下漏斗、還流冷却管及び磁気攪拌子を備えた三口フラスコに、マグネシウム４.０２ｇ（１６５ｍｍｏｌ）を加えて脱気乾燥、窒素置換し、マグネシウムの表面を削るために窒素気流下で一晩攪拌した。三口フラスコに、実施例１に記載の方法で得た中間体Ｓｉ−クロロ−Ｓｉ−メチルシラシクロペンタン２０.６５ｇ（１５４ｍｍｏｌ）、ジエチルエーテル（４０ｍＬ）及びＴＨＦ（３ｍＬ）を入れ、滴下漏斗に１−ブロモ−４−ブテン２０.００ｇ（１４８ｍｍｏｌ）のジエチルエーテル（３０ｍＬ）溶液を入れ、室温でゆっくりと滴下した。滴下開始後すぐに黒ずみ、灰色懸濁液になった後に黒色溶液となった。これを二日加熱還流させると灰色懸濁液へ変化した。氷浴でフラスコを冷却しながら１ｍｏｌ／Ｌ塩酸を加えて加水分解し、有機層を抽出分離した。得られた淡黄色透明の有機層を無水硫酸マグネシウムで乾燥させた。ジエチルエーテルを常圧蒸留で留去し、残渣を減圧蒸留して５８−６５℃／２.０ｋＰａ留分を分取し、Ｓｉ−ホモアリル−Ｓｉ−メチルシラシクロペンタンを無色液体として得た（収量１４.７２ｇ、収率６４.５％）。 To a three-necked flask equipped with a dropping funnel, a reflux condenser and a magnetic stirrer, 4.02 g (165 mmol) of magnesium was added, deaerated and dried, and the atmosphere was replaced with nitrogen, and the mixture was stirred overnight under a nitrogen stream to scrape the surface of magnesium. .. A three-necked flask was charged with 20.65 g (154 mmol) of the intermediate Si-chloro-Si-methylsilacyclopentane obtained by the method described in Example 1, diethyl ether (40 mL) and THF (3 mL), and the dropping funnel was charged with 1 A solution of 20.00 g (148 mmol) of -bromo-4-butene in diethyl ether (30 mL) was added, and the mixture was slowly added dropwise at room temperature. Immediately after the start of dropping, the solution became dark and became a gray suspension, which then became a black solution. When this was heated under reflux for 2 days, it turned into a gray suspension. While cooling the flask in an ice bath, 1 mol / L hydrochloric acid was added for hydrolysis, and the organic layer was extracted and separated. The obtained pale yellow transparent organic layer was dried over anhydrous magnesium sulfate. Diethyl ether was distilled off under atmospheric pressure, the residue was distilled under reduced pressure, and a 58-65 ° C / 2.0 kPa fraction was collected to obtain Si-homoallyl-Si-methylsilacyclopentane as a colorless liquid (yield. 14.72 g, yield 64.5%).
Ｓｉ−メチル−Ｓｉ−ビニルシラシクロペンタンをＳｉ−ホモアリル−Ｓｉ−メチルシラシクロペンタンに変更した以外は、実施例１に記載の方法と同様にしてスルホン化反応及び精製を行い、目的物であるケイ素含有スルホン酸ナトリウム塩３を得た（収率２８％）。ケイ素含有スルホン酸ナトリウム塩３の1Ｈ−ＮＭＲチャート（溶媒：重ジメチルスルホキシド）を図３に示す。 Except that Si-methyl-Si-vinylsilacyclopentane was changed to Si-homoallyl-Si-methylsilacyclopentane, the sulfonation reaction and purification were carried out in the same manner as in the method described in Example 1 to obtain the desired product. Silicon-containing sulfonic acid sodium salt 3 was obtained (yield 28%). FIG. 3 shows the 1 H-NMR chart (solvent: heavy dimethyl sulfoxide) of silicon-containing sodium sulfonate 3.
［実施例４］ケイ素含有スルホン酸ナトリウム塩４の合成
窒素気流下で、還流冷却管、滴下漏斗及び磁気攪拌子を備えた三口フラスコに、マグネシウム９.７２ｇ（０.４００ｍｏｌ）を入れ活性化させ、ここにメチルトリクロロシラン３０.２２ｇ（０.２０２ｍｏｌ）とジエチルエーテル２００ｍＬとを入れ、滴下漏斗から１,５−ジブロモペンタン５１.４８ｇ（０.２２４ｍｏｌ）のジエチルエーテル（１００ｍＬ）溶液を攪拌しながらゆっくり滴下し、滴下終了後一晩攪拌した。析出したマグネシウム塩を吸引濾過で取り除き、ジエチルエーテルを常圧蒸留で留去した。残渣を減圧蒸留で蒸留して６３−７９℃／４.２ｋＰａ留分を分取し、目的物であるＳｉ−クロロ−Ｓｉ−メチルシラシクロヘキサンを無色透明液体として得た（収量２２.００ｇ、収率７４％）（ただし、生成物は塩素置換体と臭素置換体の混合物として得られた。）。 Under a nitrogen stream, 9.72 g (0.400 mol) of magnesium was placed in a three-necked flask equipped with a reflux condenser, a dropping funnel and a magnetic stirrer for activation, and 30.22 g (0.202 mol) of methyltrichlorosilane was activated. And diethyl ether (200 mL) were added, and a solution of 1,5-dibromopentane (51.48 g, 0.224 mol) in diethyl ether (100 mL) was slowly added dropwise with stirring through a dropping funnel, and the mixture was stirred overnight after completion of the addition. The precipitated magnesium salt was removed by suction filtration, and diethyl ether was distilled off under atmospheric pressure. The residue was distilled by vacuum distillation to collect a fraction of 63-79 ° C./4.2 kPa to obtain the desired product, Si-chloro-Si-methylsilacyclohexane, as a colorless transparent liquid (yield 22.00 g, yield). 74%) (however, the product was obtained as a mixture of a chlorine-substituted product and a bromine-substituted product).
次に、窒素気流下で、還流冷却管、滴下漏斗及び磁気攪拌子を備えた三口フラスコに、マグネシウム４.８６ｇ（０.２０ｍｏｌ）を入れ活性化させ、ここに前記Ｓｉ−クロロ−Ｓｉ−メチルシラシクロヘキサン７.８７ｇ（０.１９ｍｏｌ）とジエチルエーテル１５０ｍＬとを入れ、滴下漏斗からアリルクロリド７.９６ｇ（０.２１ｍｏｌ）のジエチルエーテル（５０ｍＬ）溶液を攪拌しながらゆっくり滴下し、滴下終了後一晩攪拌した。析出したマグネシウム塩を吸引濾過で取り除き、ジエチルエーテルを常圧蒸留で留去した。残渣を減圧蒸留で蒸留して７５−７８℃／３.７ｋＰａ留分を分取し、目的物であるＳｉ−アリル−Ｓｉ−メチルシラシクロヘキサンを無色透明液体として得た（収量２１.７７ｇ、収率７４％）。 Then, under a nitrogen stream, 4.86 g (0.20 mol) of magnesium was placed in a three-necked flask equipped with a reflux condenser, a dropping funnel and a magnetic stirrer for activation, and the Si-chloro-Si-methyl was introduced thereinto. 7.87 g (0.19 mol) of silacyclohexane and 150 mL of diethyl ether were added, and a solution of 7.96 g (0.21 mol) of allyl chloride in diethyl ether (50 mL) was slowly added dropwise with stirring through a dropping funnel. Stir overnight. The precipitated magnesium salt was removed by suction filtration, and diethyl ether was distilled off under atmospheric pressure. The residue was distilled under reduced pressure to fractionate a 75-78 ° C./3.7 kPa fraction to obtain the desired product, Si-allyl-Si-methylsilacyclohexane, as a colorless transparent liquid (yield 21.77 g, yield). 74%).
還流冷却管及び磁気攪拌子を備えた三口フラスコに、ＮａＨＳＯ3 １２.６１ｇ（１２１ｍｍｏｌ）、ＮａＮＯ2 ０.７１ｇ（１０ｍｍｏｌ）、ＮａＮＯ3 ０.７２ｇ（８ｍｍｏｌ）、水１００ｍＬ、メタノール２５０ｍＬ及びＳｉ−アリル−Ｓｉ−メチルシラシクロヘキサン９.２１ｇ（６０ｍｍｏｌ）を入れ、３日間攪拌した。析出した白色固体を吸引濾過で取り除き、濾液中のメタノールを常圧蒸留で留去し室温まで冷却すると無色結晶が析出した。この結晶を一旦濾別し、得られた結晶をエタノールを用いて再結晶させ、目的物であるケイ素含有スルホン酸ナトリウム塩４を無色結晶として得た（収量７.３０ｇ、収率４７％）。ケイ素含有スルホン酸ナトリウム塩４の1Ｈ−ＮＭＲチャート（溶媒：重ジメチルスルホキシド）を図４に示す。 In a three-necked flask equipped with a reflux condenser and a magnetic stirrer, NaHSO 3 12.61 g (121 mmol), NaNO 2 0.71 g (10 mmol), NaNO 3 0.72 g (8 mmol), water 100 mL, methanol 250 mL and Si-allyl. 9.21 g (60 mmol) of -Si-methylsilacyclohexane was added and stirred for 3 days. The precipitated white solid was removed by suction filtration, methanol in the filtrate was distilled off under atmospheric pressure, and cooled to room temperature to precipitate colorless crystals. The crystals were once filtered off, and the obtained crystals were recrystallized using ethanol to obtain the desired product, silicon-containing sodium sulfonate 4 as colorless crystals (yield 7.30 g, yield 47%). FIG. 4 shows the 1 H-NMR chart (solvent: heavy dimethyl sulfoxide) of silicon-containing sodium sulfonate 4.
［２］ケイ素含有スルホン酸有機塩の合成
ケイ素含有スルホン酸塩の合成はいずれもカチオン原料のハライド塩を対応する水酸化物に変換したものとアニオン原料のケイ素含有スルホン酸ナトリウム塩（ケイ素含有スルホン酸ナトリウム塩１〜４）を対応するスルホン酸へ変換した後、中和反応により合成した。詳細を以下に示す。
[2] Synthesis of Silicon-Containing Sulfonic Acid Organic Salt In the synthesis of silicon-containing sulfonates, the cation raw material halide salt is converted to the corresponding hydroxide and the anion raw material silicon-containing sulfonic acid sodium salt (silicon containing sulfone is used). The acid sodium salt 1 to 4) was converted to the corresponding sulfonic acid and then synthesized by a neutralization reaction. Details are shown below.
［実施例５］ケイ素含有スルホン酸塩１の合成
特開２０１４−０８２３１５号公報に記載の方法で、Ｎ−２−メトキシエチル−Ｎ−メチルピロリジニウムクロライドを合成した。Ｎ−２−メトキシエチル−Ｎ−メチルピロリジニウムクロライドをイオン交換水に溶解した溶液（５倍希釈）を調整した。この溶液に、洗浄液が中性を示すまで良く洗浄した強塩基性イオン交換樹脂ORLITE DS-2（オルガノ(株)、交換容量１.４ｍｅｑ／ｍＬ、ＯＨ型）をＮ−２−メトキシエチル−Ｎ−メチルピロリジニウムクロライドの２.５倍モル相当量投入した。６〜７時間後、桐山ロートで濾過をしてイオン交換樹脂を濾別した。濾液に新たに洗浄済みのORLITE DS-2を原料の２.５倍モル相当量を投入し、一晩放置後、桐山ロートで濾過をしてイオン交換樹脂を濾別し、塩の大部分がクロライド塩から水酸化物に変換した溶液を得た。更に、濾液をORLITE DS-2（原料の１０倍モル相当）を充填したカラムに空間速度ＳＶ＝１で流し処理し、中和反応用の水酸化物水溶液を得た。 N-2-methoxyethyl-N-methylpyrrolidinium chloride was synthesized by the method described in JP-A-2014-082315. A solution (5-fold dilution) of N-2-methoxyethyl-N-methylpyrrolidinium chloride dissolved in ion-exchanged water was prepared. Strongly basic ion exchange resin ORLITE DS-2 (Organo Corporation, exchange capacity 1.4 meq / mL, OH type), which had been thoroughly washed until the washing solution showed neutrality, was added to this solution in N-2-methoxyethyl-N. -Methylpyrrolidinium chloride was added in an amount equivalent to 2.5 times the molar amount. After 6 to 7 hours, the ion exchange resin was separated by filtration with a Kiriyama funnel. The newly washed ORLITE DS-2 was added to the filtrate in an amount equivalent to 2.5 times the molar amount of the raw material, left overnight, and then filtered with a Kiriyama funnel to filter out the ion exchange resin. A solution of chloride salt converted to hydroxide was obtained. Further, the filtrate was flown through a column packed with ORLITE DS-2 (corresponding to 10 times mol of the raw material) at a space velocity SV = 1 to obtain a hydroxide aqueous solution for neutralization reaction.
ケイ素含有スルホン酸ナトリウム塩１をイオン交換水に溶解した溶液（１０倍希釈）を調整した。この溶液に、洗浄液が中性を示すまでよく洗浄した強酸性イオン交換樹脂AMBERLYST 15JS-HG・DRY（オルガノ(株)、交換容量４.７ｍｅｑ／ｇ、Ｈ型）をケイ素含有スルホン酸ナトリウム塩１の２.５倍モル相当量投入した。６〜７時間後、桐山ロートで濾過をしてイオン交換樹脂を濾別した。濾液に新たに洗浄済みのAMBERLYST 15JS-HG・DRYを原料の２.５倍モル相当量を投入し、一晩放置後、桐山ロートで濾過をしてイオン交換樹脂を濾別し、塩の大部分がスルホン酸ナトリウム塩からスルホン酸に変換した溶液を得た。更に濾液をAMBERLYST 15JS-HG・DRY（原料の１０倍モル相当）を充填したカラムに空間速度ＳＶ＝１で流し処理し、中和反応用のスルホン酸水溶液を得た。 A solution (10-fold diluted) in which silicon-containing sodium sulfonate 1 was dissolved in ion-exchanged water was prepared. A strongly acidic ion exchange resin AMBERLYST 15JS-HG DRY (Organo Corporation, exchange capacity 4.7 meq / g, H type) that had been thoroughly washed until the washing liquid became neutral was added to this solution. 2.5 times the molar equivalent amount of was added. After 6 to 7 hours, the ion exchange resin was separated by filtration with a Kiriyama funnel. The newly washed AMBERLYST 15JS-HG / DRY was added to the filtrate in an amount equivalent to 2.5 times the amount of the raw material, left overnight and then filtered with a Kiriyama funnel to filter out the ion exchange resin to remove salt. A solution was obtained in which a portion was converted from sulfonic acid sodium salt to sulfonic acid. Further, the filtrate was flown through a column packed with AMBERLYST 15JS-HG.DRY (corresponding to 10 times mol of the raw material) at a space velocity SV = 1 to obtain a sulfonic acid aqueous solution for neutralization reaction.
前記水酸化物水溶液とスルホン酸ナトリウム水溶液とをｐＨ試験紙でｐＨを確認しつつ混合し、ｐＨ試験紙がｐＨ７を示した時点で混合を終了し、ケイ素含有スルホン酸塩１の水溶液を調製した。この水溶液からエバポレータで大部分の水を留去した後、更に１１０℃（オイルバス使用）で真空ポンプを用いて１時間以上真空引きを行い、目的物であるケイ素含有スルホン酸塩１を得た。ケイ素含有スルホン酸塩１の1Ｈ−ＮＭＲチャート（溶媒：重クロロホルム）を図５に、ＤＳＣチャートを図６に、ＴＧ−ＤＴＡチャートを図７に示す。なお、ケイ素含有スルホン酸塩１は、イオン液体であった。 The hydroxide aqueous solution and the sodium sulfonate aqueous solution were mixed while confirming the pH with a pH test paper, and when the pH test paper showed pH 7, the mixing was terminated to prepare an aqueous solution of silicon-containing sulfonate 1. .. After most of the water was distilled off from this aqueous solution with an evaporator, the solution was further evacuated at 110 ° C. (using an oil bath) for 1 hour or more using a vacuum pump to obtain the target silicon-containing sulfonate 1. .. A 1 H-NMR chart (solvent: deuterated chloroform) of silicon-containing sulfonate 1 is shown in FIG. 5, a DSC chart is shown in FIG. 6, and a TG-DTA chart is shown in FIG. 7. The silicon-containing sulfonate 1 was an ionic liquid.
［実施例６］ケイ素含有スルホン酸塩２の合成
ケイ素含有スルホン酸ナトリウム塩１をケイ素含有スルホン酸ナトリウム塩２に変えた以外は、実施例５と同様の方法によりケイ素含有スルホン酸塩２を得た。ケイ素含有スルホン酸塩２の1Ｈ−ＮＭＲチャート（溶媒：重クロロホルム）を図８に、ＤＳＣチャートを図９に、ＴＧ−ＤＴＡチャートを図１０に示す。なお、ケイ素含有スルホン酸塩２は、イオン液体であった。 A silicon-containing sulfonate 2 was obtained by the same method as in Example 5, except that the silicon-containing sodium sulfonate 1 was changed to the silicon-containing sodium sulfonate 2. The 1 H-NMR chart (solvent: deuterated chloroform) of the silicon-containing sulfonate 2 is shown in FIG. 8, the DSC chart is shown in FIG. 9, and the TG-DTA chart is shown in FIG. The silicon-containing sulfonate 2 was an ionic liquid.
［実施例７］ケイ素含有スルホン酸塩３の合成
ケイ素含有スルホン酸ナトリウム塩１をケイ素含有スルホン酸ナトリウム塩３に変えた以外は、実施例５と同様の方法によりケイ素含有スルホン酸塩３を得た。ケイ素含有スルホン酸塩３の1Ｈ−ＮＭＲチャート（溶媒：重クロロホルム）を図１１に、ＤＳＣチャートを図１２に、ＴＧ−ＤＴＡチャートを図１３に示す。なお、ケイ素含有スルホン酸塩３は、イオン液体であった。 A silicon-containing sulfonate 3 was obtained in the same manner as in Example 5 except that the silicon-containing sodium sulfonate 1 was replaced with the silicon-containing sodium sulfonate 3. A 1 H-NMR chart (solvent: deuterated chloroform) of silicon-containing sulfonate 3 is shown in FIG. 11, a DSC chart is shown in FIG. 12, and a TG-DTA chart is shown in FIG. The silicon-containing sulfonate 3 was an ionic liquid.
［実施例８］ケイ素含有スルホン酸塩４の合成
Ｎ−２−メトキシエチル−Ｎ−メチルピロリジニウムクロライドをトリブチルドデシルホスホニウム臭化物塩（東京化成工業(株)）に変えた以外は、実施例５と同様の方法によりケイ素含有スルホン酸塩４を得た。ケイ素含有スルホン酸塩４の1Ｈ−ＮＭＲチャート（溶媒：重クロロホルム）を図１４に、ＤＳＣチャートを図１５に、ＴＧ−ＤＴＡチャートを図１６に示す。なお、ケイ素含有スルホン酸塩４は、イオン液体であった。 Silicon-containing sulfonate 4 was obtained in the same manner as in Example 5, except that N-2-methoxyethyl-N-methylpyrrolidinium chloride was replaced with tributyldodecylphosphonium bromide salt (Tokyo Kasei Kogyo Co., Ltd.). It was The 1 H-NMR chart (solvent: deuterated chloroform) of the silicon-containing sulfonate 4 is shown in FIG. 14, the DSC chart is shown in FIG. 15, and the TG-DTA chart is shown in FIG. 16. The silicon-containing sulfonate 4 was an ionic liquid.
［実施例９］ケイ素含有スルホン酸塩５の合成
Ｎ−２−メトキシエチル−Ｎ−メチルピロリジニウムクロライドをトリブチルドデシルホスホニウム臭化物塩（東京化成工業(株)）に、ケイ素含有スルホン酸ナトリウム塩１をケイ素含有スルホン酸ナトリウム塩３に変えた以外は、実施例５と同様の方法によりケイ素含有スルホン酸塩５を得た。ケイ素含有スルホン酸塩５の1Ｈ−ＮＭＲチャート（溶媒：重クロロホルム）を図１７に、ＤＳＣチャートを図１８に、ＴＧ−ＤＴＡチャートを図１９に示す。なお、ケイ素含有スルホン酸塩５は、イオン液体であった。 N-2-methoxyethyl-N-methylpyrrolidinium chloride was changed to tributyldodecylphosphonium bromide salt (Tokyo Chemical Industry Co., Ltd.), and silicon-containing sulfonic acid sodium salt 1 was changed to silicon-containing sulfonic acid sodium salt 3. A silicon-containing sulfonate 5 was obtained in the same manner as in Example 5. A 1 H-NMR chart (solvent: deuterated chloroform) of silicon-containing sulfonate 5 is shown in FIG. 17, a DSC chart is shown in FIG. 18, and a TG-DTA chart is shown in FIG. The silicon-containing sulfonate 5 was an ionic liquid.
［実施例１０］ケイ素含有スルホン酸塩６の合成
ケイ素含有スルホン酸ナトリウム塩１をケイ素含有スルホン酸ナトリウム塩４に変えた以外は、実施例５と同様の方法によりケイ素含有スルホン酸塩６を得た。ケイ素含有スルホン酸塩６の1Ｈ−ＮＭＲチャート（溶媒：重クロロホルム）を図２０に、ＤＳＣチャートを図２１に、ＴＧ−ＤＴＡチャートを図２２に示す。なお、ケイ素含有スルホン酸塩６は、イオン液体であった。 A silicon-containing sulfonate 6 was obtained in the same manner as in Example 5, except that the silicon-containing sodium sulfonate 1 was replaced with the silicon-containing sodium sulfonate 4. A 1 H-NMR chart (solvent: deuterated chloroform) of silicon-containing sulfonate 6 is shown in FIG. 20, a DSC chart is shown in FIG. 21, and a TG-DTA chart is shown in FIG. The silicon-containing sulfonate 6 was an ionic liquid.
［実施例１１］ケイ素含有スルホン酸塩７の合成
Ｎ−２−メトキシエチル−Ｎ−メチルピロリジニウムクロライドをトリブチルドデシルホスホニウム臭化物塩（東京化成工業(株)）に、ケイ素含有スルホン酸ナトリウム塩１をケイ素含有スルホン酸ナトリウム塩４に変えた以外は、実施例５と同様の方法によりケイ素含有スルホン酸塩７を得た。ケイ素含有スルホン酸塩７の1Ｈ−ＮＭＲチャート（溶媒：重クロロホルム）を図２３に、ＤＳＣチャートを図２４に、ＴＧ−ＤＴＡチャートを図２５に示す。なお、ケイ素含有スルホン酸塩７は、イオン液体であった。 N-2-methoxyethyl-N-methylpyrrolidinium chloride was changed to tributyldodecylphosphonium bromide salt (Tokyo Kasei Kogyo Co., Ltd.), and silicon-containing sodium sulfonate 1 was replaced with silicon-containing sodium sulfonate 4. A silicon-containing sulfonate 7 was obtained in the same manner as in Example 5. The 1 H-NMR chart (solvent: deuterated chloroform) of the silicon-containing sulfonate 7 is shown in FIG. 23, the DSC chart is shown in FIG. 24, and the TG-DTA chart is shown in FIG. 25. The silicon-containing sulfonate 7 was an ionic liquid.
［実施例１２］ケイ素含有スルホン酸塩８の合成
Ｎ−２−メトキシエチル−Ｎ−メチルピロリジニウムクロライドをＮ,Ｎ−ジエチル−Ｎ−メチル−Ｎ−(２−メトキシエチル)アンモニウムアイオダイドに変えた以外は、実施例５と同様の方法によりケイ素含有スルホン酸塩８を得た。なお、Ｎ,Ｎ−ジエチル−Ｎ−メチル−Ｎ−(２−メトキシエチル)アンモニウムアイオダイドは、Electrochimica Acta, 49 (2004) pp. 3603-3611記載の合成法に準じ合成した。ケイ素含有スルホン酸塩８の1Ｈ−ＮＭＲチャート（溶媒：重クロロホルム）を図２６に、ＤＳＣチャートを図２７に、ＴＧ−ＤＴＡチャートを図２８に示す。 By a method similar to that in Example 5, except that N-2-methoxyethyl-N-methylpyrrolidinium chloride was replaced with N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium iodide. A silicon-containing sulfonate 8 was obtained. The N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium iodide was synthesized according to the synthesis method described in Electrochimica Acta, 49 (2004) pp. 3603-3611. The 1 H-NMR chart (solvent: deuterated chloroform) of silicon-containing sulfonate 8 is shown in FIG. 26, the DSC chart is shown in FIG. 27, and the TG-DTA chart is shown in FIG. 28.
［実施例１３］ケイ素含有スルホン酸塩９の合成
Ｎ−２−メトキシエチル−Ｎ−メチルピロリジニウムクロライドをＮ,Ｎ−ジエチル−Ｎ−メチル−Ｎ−(２−メトキシエチル)アンモニウムアイオダイドに、ケイ素含有スルホン酸塩１をケイ素含有スルホン酸ナトリウム塩２に変えた以外は、実施例５と同様の方法によりケイ素含有スルホン酸塩９を得た。ケイ素含有スルホン酸塩９の1Ｈ−ＮＭＲチャート（溶媒：重クロロホルム）を図２９に、ＤＳＣチャートを図３０に、ＴＧ−ＤＴＡチャートを図３１に示す。 N-2-methoxyethyl-N-methylpyrrolidinium chloride in N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium iodide and silicon-containing sulfonate 1 in silicon-containing sodium sulfonate A silicon-containing sulfonate 9 was obtained in the same manner as in Example 5, except that the salt 2 was used. The 1 H-NMR chart (solvent: deuterated chloroform) of silicon-containing sulfonate 9 is shown in FIG. 29, the DSC chart is shown in FIG. 30, and the TG-DTA chart is shown in FIG. 31.
［実施例１４］ケイ素含有スルホン酸塩１０の合成
Ｎ−２−メトキシエチル−Ｎ−メチルピロリジニウムクロライドをＮ,Ｎ−ジエチル−Ｎ−メチル−Ｎ−(２−メトキシエチル)アンモニウムアイオダイドに、ケイ素含有スルホン酸塩１をケイ素含有スルホン酸ナトリウム塩３に変えた以外は、実施例５と同様の方法によりケイ素含有スルホン酸塩１０を得た。ケイ素含有スルホン酸塩１０の1Ｈ−ＮＭＲチャート（溶媒：重クロロホルム）を図３２に、ＤＳＣチャートを図３３に、ＴＧ−ＤＴＡチャートを図３４に示す。 N-2-methoxyethyl-N-methylpyrrolidinium chloride in N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium iodide and silicon-containing sulfonate 1 in silicon-containing sodium sulfonate A silicon-containing sulfonate 10 was obtained in the same manner as in Example 5, except that the salt 3 was used. A 1 H-NMR chart (solvent: deuterated chloroform) of the silicon-containing sulfonate 10 is shown in FIG. 32, a DSC chart is shown in FIG. 33, and a TG-DTA chart is shown in FIG. 34.
ＤＳＣ及びＴＧ−ＤＴＡ測定より求めたケイ素含有スルホン酸塩１〜１０の融点及び分解点（１０％重量減少、大気下）を表１に示す。 Table 1 shows the melting points and decomposition points (10% weight loss, under air) of the silicon-containing sulfonates 1 to 10 determined by DSC and TG-DTA measurements.
［３］電位窓の測定
［実施例１５〜１７、比較例１］
ケイ素含有スルホン酸塩１（実施例１５）、８（実施例１６）、９（実施例１７）、及び１−エチル−３−メチルイミダゾリウムテトラフルオロボレート(EMIBF4)（比較例１）について、サイクリックボルタンメトリー測定を行った。ケイ素含有スルホン酸塩１、８、及びEMIBF4については、各々１Ｍの炭酸プロピレン溶液を調整し、ケイ素含有スルホン酸塩９については、０.１Ｍのプロピレンカーボネート溶液を調整し、測定を行った。
結果を図３５に示す。図３５から明らかなように、既存のイオン液体であるEMIBF4に比し、本発明のケイ素含有スルホン酸塩の電位窓はいずれも広く、電気化学的安定性に優れることがわかった。
[3] Measurement of potential window [Examples 15 to 17, Comparative Example 1]
Silicon-containing sulfonate 1 (Example 15), 8 (Example 16), about 9 (Example 17), and 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF 4) (Comparative Example 1), Cyclic voltammetry measurement was performed. For the silicon-containing sulfonates 1 and 8 and EMIBF 4 , a 1M propylene carbonate solution was prepared, and for the silicon-containing sulfonate 9, a 0.1M propylene carbonate solution was prepared and measured.
Results are shown in FIG. As is clear from FIG. 35, it was found that the potential windows of the silicon-containing sulfonates of the present invention are wider than those of the existing ionic liquid, EMIBF 4, and that they have excellent electrochemical stability.
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