JP6182113B2 - Method for producing amino-substituted phosphazene compound, method for producing electrolyte for non-aqueous secondary battery, and method for producing non-aqueous secondary battery - Google Patents
Method for producing amino-substituted phosphazene compound, method for producing electrolyte for non-aqueous secondary battery, and method for producing non-aqueous secondary battery Download PDFInfo
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- JP6182113B2 JP6182113B2 JP2014125369A JP2014125369A JP6182113B2 JP 6182113 B2 JP6182113 B2 JP 6182113B2 JP 2014125369 A JP2014125369 A JP 2014125369A JP 2014125369 A JP2014125369 A JP 2014125369A JP 6182113 B2 JP6182113 B2 JP 6182113B2
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- secondary battery
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- lewis acid
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- -1 amino-substituted phosphazene compound Chemical class 0.000 title claims description 126
- 238000004519 manufacturing process Methods 0.000 title claims description 45
- 239000003792 electrolyte Substances 0.000 title description 15
- 150000001875 compounds Chemical class 0.000 claims description 69
- 125000004432 carbon atom Chemical group C* 0.000 claims description 46
- 229910052744 lithium Inorganic materials 0.000 claims description 34
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 33
- 125000001424 substituent group Chemical group 0.000 claims description 29
- 239000011968 lewis acid catalyst Substances 0.000 claims description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 22
- 239000008151 electrolyte solution Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 18
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 11
- 229910052731 fluorine Inorganic materials 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 125000005843 halogen group Chemical group 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 125000004429 atom Chemical group 0.000 claims description 9
- 229910052796 boron Inorganic materials 0.000 claims description 9
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 9
- 125000001153 fluoro group Chemical group F* 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 229910007926 ZrCl Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 7
- 229910052718 tin Inorganic materials 0.000 claims description 7
- 239000011135 tin Substances 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 229910003902 SiCl 4 Inorganic materials 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 150000002738 metalloids Chemical group 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 4
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 239000011244 liquid electrolyte Substances 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 description 65
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 60
- 239000000047 product Substances 0.000 description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000000126 substance Substances 0.000 description 21
- 229910052757 nitrogen Inorganic materials 0.000 description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- 238000006467 substitution reaction Methods 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 208000012839 conversion disease Diseases 0.000 description 16
- 238000000746 purification Methods 0.000 description 16
- 238000000926 separation method Methods 0.000 description 16
- 238000004293 19F NMR spectroscopy Methods 0.000 description 15
- 150000001555 benzenes Chemical class 0.000 description 15
- 238000004817 gas chromatography Methods 0.000 description 15
- 239000007788 liquid Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 235000002639 sodium chloride Nutrition 0.000 description 15
- 229910000314 transition metal oxide Inorganic materials 0.000 description 15
- 238000005292 vacuum distillation Methods 0.000 description 15
- 150000003839 salts Chemical class 0.000 description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 13
- 239000007789 gas Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 125000000217 alkyl group Chemical group 0.000 description 11
- 125000003277 amino group Chemical group 0.000 description 11
- 239000007774 positive electrode material Substances 0.000 description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 125000005647 linker group Chemical group 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- 239000007773 negative electrode material Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- 229910003002 lithium salt Inorganic materials 0.000 description 8
- 159000000002 lithium salts Chemical class 0.000 description 8
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical class CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 8
- 229920000049 Carbon (fiber) Polymers 0.000 description 7
- 125000003342 alkenyl group Chemical group 0.000 description 7
- 239000004917 carbon fiber Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000000806 fluorine-19 nuclear magnetic resonance spectrum Methods 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000004020 conductor Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 5
- 239000003125 aqueous solvent Substances 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 5
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 5
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 239000002841 Lewis acid Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 125000000304 alkynyl group Chemical group 0.000 description 4
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000007810 chemical reaction solvent Substances 0.000 description 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- 150000007517 lewis acids Chemical class 0.000 description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- 239000011255 nonaqueous electrolyte Substances 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 3
- 229910013063 LiBF 4 Inorganic materials 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 3
- 125000004423 acyloxy group Chemical group 0.000 description 3
- 125000004450 alkenylene group Chemical group 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
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- 239000007858 starting material Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
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- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical group CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 2
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 description 2
- 229910013825 LiNi0.33Co0.33Mn0.33O2 Inorganic materials 0.000 description 2
- 229910012752 LiNi0.5Mn0.5O2 Inorganic materials 0.000 description 2
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
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- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 229910001504 inorganic chloride Inorganic materials 0.000 description 1
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- 229910052740 iodine Inorganic materials 0.000 description 1
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical class [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- WDAXFOBOLVPGLV-UHFFFAOYSA-N isobutyric acid ethyl ester Natural products CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
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- 239000000314 lubricant Substances 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
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- 230000007246 mechanism Effects 0.000 description 1
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- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- NCKZHFSVCRZQGH-UHFFFAOYSA-N methylsulfinylmethane;phosphoric acid Chemical compound CS(C)=O.OP(O)(O)=O NCKZHFSVCRZQGH-UHFFFAOYSA-N 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
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- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 1
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- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
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- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
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- 238000005191 phase separation Methods 0.000 description 1
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- RKEWSXXUOLRFBX-UHFFFAOYSA-N pimavanserin Chemical compound C1=CC(OCC(C)C)=CC=C1CNC(=O)N(C1CCN(C)CC1)CC1=CC=C(F)C=C1 RKEWSXXUOLRFBX-UHFFFAOYSA-N 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
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- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
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- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003860 storage Methods 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
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
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- 239000000057 synthetic resin Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
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-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
- C07F9/65814—Cyclic phosphazenes [P=N-]n, n>=3 n = 3 or 4
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
- C07F9/65815—Cyclic phosphazenes [P=N-]n, n>=3 n = 3
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
- C07F9/65817—Cyclic phosphazenes [P=N-]n, n>=3 n = 4
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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Description
本発明は、アミノ置換ホスファゼン化合物の製造方法、これを利用した非水二次電池用電解液の製造方法および非水二次電池の製造方法に関する。 The present invention relates to a method for producing an amino-substituted phosphazene compound, a method for producing an electrolyte for a non-aqueous secondary battery using the same, and a method for producing a non-aqueous secondary battery.
ホスファゼン化合物は、様々な用途に適用されている。特に最近では、各種材料に優れた難燃性を付与することができる化合物として注目されている。例えば、リチウムイオン二次電池において、難燃性を付与する化合物として利用され、その電解液の添加剤とすることが提案されている(特許文献1参照)。そこでは、ハロゲン化環状ホスファゼンをアルコール化合物で置換した誘導体が難燃剤として利用されている。 Phosphazene compounds are applied in various applications. In recent years, it has attracted attention as a compound that can impart excellent flame retardancy to various materials. For example, in a lithium ion secondary battery, it has been proposed to be used as a compound imparting flame retardancy and to be used as an additive for the electrolytic solution (see Patent Document 1). Therein, a derivative in which a halogenated cyclic phosphazene is substituted with an alcohol compound is used as a flame retardant.
従来、ホスファゼン化合物に特定の置換基を導入した誘導体の合成方法が知られている。例えば上記のアルコキシ置換されたフッ化ホスファゼンは、(PNF2)nで表される化合物と、R−OM(式中、Rはアルキル基、Mはアルカリ金属を示す。)で表されるアルコラート、あるいはR−OH(式中、Rは上記と同義。)で表されるアルコールを、無触媒、炭酸ナトリウム、炭酸カリウム等の塩基性触媒の存在下に反応させる方法等が提案されている(特許文献2〜6参照)。
また、アミノ基が置換されたフッ素化ホスファゼンの合成については、(PNF2)nで表される化合物と、2当量のアミンを反応させる方法(非特許文献1参照)が知られている。そこではジメチルアミノトリメチルシランを用いてアミノ置換反応を行うことを提案している。
一方、多置換型のホスファゼン化合物の合成法としては、(PNCl2)nで表される化合物と、ヒドロキシ化合物を、酸化亜鉛や塩化亜鉛等の触媒の存在下で反応させることで、短時間に高置換率で導入することが提案されている(特許文献7、8参照)。
Conventionally, a method for synthesizing a derivative in which a specific substituent is introduced into a phosphazene compound is known. For example, the above alkoxy-substituted fluorinated phosphazene includes a compound represented by (PNF 2 ) n and an alcoholate represented by R—OM (wherein R represents an alkyl group, M represents an alkali metal), Alternatively, a method of reacting an alcohol represented by R—OH (wherein R is as defined above) in the presence of a non-catalyst, a basic catalyst such as sodium carbonate, potassium carbonate, etc. has been proposed (patent). Reference 2-6).
As for the synthesis of a fluorinated phosphazene substituted with an amino group, a method of reacting a compound represented by (PNF 2 ) n with 2 equivalents of an amine (see Non-Patent Document 1) is known. It proposes to carry out amino substitution reaction using dimethylaminotrimethylsilane.
On the other hand, as a method for synthesizing a polysubstituted phosphazene compound, a compound represented by (PNCl 2 ) n and a hydroxy compound are reacted in the presence of a catalyst such as zinc oxide or zinc chloride in a short time. It has been proposed to introduce at a high substitution rate (see
上述のようにホスファゼン化合物の合成方法については、これまでいくつかのものが提案されている。しかしながら、その検討はまだ十分になされているとは言えない。昨今、電池や電子材料等に適用される難燃剤としての利用が広がるなか、合成方法の多様化は欠かせない課題である。特に、アミノ置換体の優れた難燃性が注目されており(国際公開第2013/047342号パンフレット)、その製造技術の開発が求められる。 As described above, several methods for synthesizing phosphazene compounds have been proposed so far. However, it has not been fully studied. In recent years, diversification of synthesis methods is an indispensable issue as the use as a flame retardant applied to batteries, electronic materials and the like has expanded. In particular, the excellent flame retardancy of amino-substituted products has attracted attention (International Publication No. 2013/047342 pamphlet), and the development of a production technique thereof is required.
本発明は、かかる実情に鑑みてなされたものであり、アミノ置換ホスファゼン化合物の新たな合成方法の提供を目的とする。さらに、必要により、高収率、高選択率、高純度で、かつ安価にて、アミノ置換ホスファゼン化合物を製造する製造方法、さらにこれを利用した非水二次電池用電解液および非水二次電池の製造方法の提供を目的とする。 The present invention has been made in view of such circumstances, and an object thereof is to provide a new synthesis method of an amino-substituted phosphazene compound. Furthermore, if necessary, a production method for producing an amino-substituted phosphazene compound at high yield, high selectivity, high purity, and low cost, and an electrolyte for non-aqueous secondary battery and non-aqueous secondary using the same It aims at providing the manufacturing method of a battery.
上記の課題は以下の手段により解決された。
〔1〕下記式(2)で表されるフッ素化ホスファゼン化合物とアミン化合物とをルイス酸触媒の存在下で反応させて、上記フッ素化ホスファゼン化合物に上記アミン化合物を置換した化合物を合成する、下記式(1)で表されるアミノ置換ホスファゼン化合物の製造方法。
〔2〕上記ルイス酸触媒が、アルミニウム、マグネシウム、リチウム、マンガン、鉄、銅、亜鉛、スズ、ホウ素、ケイ素、チタン、ジルコニウム、クロム、コバルト、ニッケル、モリブデン、およびバナジウムからなる群から選ばれる元素を含む化合物からなる〔1〕に記載の製造方法。
〔3〕上記アミン化合物の炭素数が1〜12である〔1〕または〔2〕に記載の製造方法。
〔4〕上記ルイス酸触媒を上記フッ素化ホスファゼン化合物に対して0.2〜3当量で加える〔1〕〜〔3〕のいずれか1つに記載の製造方法。
〔5〕上記ルイス酸触媒が、M−Z結合を少なくとも1つ有する化合物からなる〔1〕〜〔4〕のいずれか1つに記載の製造方法。
式中、Mは金属原子、半金属原子であり、Zはハロゲン原子である。
〔6〕上記ルイス酸触媒が、アルミニウム、マグネシウム、リチウム、鉄、銅(II)、ホウ素、ケイ素からなる群から選ばれる元素を含む化合物からなる〔1〕〜〔5〕のいずれか1つに記載の製造方法。
〔7〕上記ルイス酸触媒が塩素または臭素を有する化合物からなる〔1〕〜〔6〕のいずれか1つに記載の製造方法。
〔8〕上記ルイス酸触媒を上記フッ素化ホスファゼン化合物に対して0.25〜1当量で加える〔1〕〜〔7〕のいずれか1つに記載の製造方法。
〔9〕上記ルイス酸触媒が、AlCl3、MgCl2、LiCl、LiBr、CuCl2、FeCl3、ZrCl4、ZrOCl2、SiCl4、Me2SiCl2、TMS−Cl、およびBCl3からなる群から選ばれる少なくとも一種である〔1〕〜〔8〕のいずれか1つに記載の製造方法。
Meはメチル基を表す。TMSはトリメチルシリル基を表す。
〔10〕 〔1〕〜〔9〕のいずれか1つに記載の製造方法を介して、上記アミノ置換ホスファゼン化合物を含有する非水二次電池用電解液を調製する非水二次電池用電解液の製造方法。
〔11〕 〔10〕に記載の製造方法を介して、正極と負極と上記非水二次電池用電解液とを具備する非水二次電池を作製する非水二次電池の製造方法。
The above problem has been solved by the following means.
[1] A fluorinated phosphazene compound represented by the following formula (2) is reacted with an amine compound in the presence of a Lewis acid catalyst to synthesize a compound in which the amine compound is substituted for the fluorinated phosphazene compound. The manufacturing method of the amino substituted phosphazene compound represented by Formula (1).
[ 2 ] The Lewis acid catalyst is an element selected from the group consisting of aluminum, magnesium, lithium, manganese, iron, copper, zinc, tin, boron, silicon, titanium, zirconium, chromium, cobalt, nickel, molybdenum, and vanadium. [1 ] The production method according to [1 ] .
[ 3 ] The production method according to [1] or [ 2], wherein the amine compound has 1 to 12 carbon atoms.
[ 4 ] The production method according to any one of [1] to [ 3 ], wherein the Lewis acid catalyst is added in an amount of 0.2 to 3 equivalents with respect to the fluorinated phosphazene compound.
[ 5 ] The production method according to any one of [1] to [ 4 ], wherein the Lewis acid catalyst comprises a compound having at least one MZ bond.
In the formula, M is a metal atom or a metalloid atom, and Z is a halogen atom.
[ 6 ] In any one of [1] to [ 5 ], the Lewis acid catalyst is composed of a compound containing an element selected from the group consisting of aluminum, magnesium, lithium, iron, copper (II), boron, and silicon. The manufacturing method as described.
[ 7 ] The production method according to any one of [1] to [ 6 ], wherein the Lewis acid catalyst comprises a compound having chlorine or bromine.
[ 8 ] The production method according to any one of [1] to [ 7 ], wherein the Lewis acid catalyst is added in an amount of 0.25 to 1 equivalent to the fluorinated phosphazene compound.
[ 9 ] The Lewis acid catalyst is selected from the group consisting of AlCl 3 , MgCl 2 , LiCl, LiBr, CuCl 2 , FeCl 3 , ZrCl 4 , ZrOCl 2 , SiCl 4 , Me 2 SiCl 2 , TMS-Cl, and BCl 3. The production method according to any one of [1] to [ 8 ], which is at least one selected.
Me represents a methyl group. TMS represents a trimethylsilyl group.
[ 10 ] Production of non-aqueous secondary battery electrolyte containing the amino-substituted phosphazene compound via the production method according to any one of [1] to [ 9 ] Method.
[ 11 ] The manufacturing method of the non-aqueous secondary battery which produces the non-aqueous secondary battery which comprises a positive electrode, a negative electrode, and the said electrolyte solution for non-aqueous secondary batteries through the manufacturing method as described in [ 10 ].
本発明によれば、アミノ置換ホスファゼン化合物の新たな合成方法を提供することができる。さらに、必要により、高収率、高選択率、高純度で、かつ安価にて、アミノ置換ホスファゼン化合物を製造することができる。さらに上記アミノ置換ホスファゼン化合物を利用した非水二次電池用電解液および非水二次電池の製造方法を提供することができる。 According to the present invention, a new method for synthesizing amino-substituted phosphazene compounds can be provided. Furthermore, if necessary, an amino-substituted phosphazene compound can be produced with high yield, high selectivity, high purity and low cost. Furthermore, the manufacturing method of the electrolyte solution for non-aqueous secondary batteries using the said amino substituted phosphazene compound and a non-aqueous secondary battery can be provided.
以下において、本発明について詳細に説明する。以下に記載する構成要件の説明は、代表的な実施形態や具体例に基づいてなされることがあるが、本発明はそのような実施形態に限定されるものではない。
本発明の製造方法では、フッ素化ホスファゼン化合物と、アミン化合物とを、ルイス酸触媒の存在下で反応させて、アミノ置換ホスファゼン化合物を合成する。以下、本発明の好ましい実施形態を中心に本発明について詳細に説明する。
Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be made based on representative embodiments and specific examples, but the present invention is not limited to such embodiments.
In the production method of the present invention, an amino-substituted phosphazene compound is synthesized by reacting a fluorinated phosphazene compound with an amine compound in the presence of a Lewis acid catalyst. Hereinafter, the present invention will be described in detail focusing on preferred embodiments of the present invention.
<アミノ置換ホスファゼン化合物>
本発明において合成されるアミノ置換ホスファゼン化合物において、置換されたアミノ基の数は、1〜2個である。なお、本発明において、アミノ基は置換アミノ基(例えばアルキルアミノ基やアリールアミノ基)を含む意味であり、後記置換基Y1のなかで定義されるアミノ基(NR1R2)である。
ホスファゼン化合物は環状ホスファゼン化合物であり、6員環または8員環の環状ホスファゼン化合物である。
<Amino-substituted phosphazene compound>
At the amino-substituted phosphazene compounds synthesized in the present invention, the number of substituted amino groups, Ru 1-2 Kodea. In the present invention, the amino group makes sense der containing substituted amino groups (e.g., an alkylamino group or an arylamino group), an amino group, as defined within the below substituents Y 1 (NR 1 R 2) der The
Phosphazene compounds Ri cyclic phosphazene compound der, Ru cyclic phosphazene compound der of 6-membered ring or 8-membered ring.
上記アミノ置換ホスファゼン化合物は下記式(1)で表される化合物である。
The amino-substituted phosphazene compound Ru compound der represented by the following formula (1).
Y1及びY2以外の基がハロゲン原子の中でもフッ素原子であると、例えば、リチウムイオン電池の電解液の添加剤(難燃剤)として適用した際に、特に高い難燃性の付与、あるいは電池性能の維持に資するため好ましい。 When the group other than Y 1 and Y 2 is a fluorine atom among halogen atoms, for example, when applied as an additive (flame retardant) for an electrolyte solution of a lithium ion battery, imparting particularly high flame resistance, or a battery This is preferable because it contributes to maintenance of performance.
Y1は、−NR1R2を表す。R1、R2はそれぞれ一価の置換基又は水素原子を表し、一価の置換基であることが好ましい。R1とR2は置換基同士が環を形成していてもよく、任意の置換基Tを有していてもよい。置換基Tとしては特に限定されないが、下記に例示のものが好ましく、具体的には、ハロゲン原子(例えばフッ素原子)、カルボニル基含有基(例えば炭素数2〜6)、アルコキシ基(例えば炭素数1〜6)、シリル基(例えば炭素数1〜6)などが挙げられる。例えば、カルボニル基含有基としては、アシル基(炭素数2〜12が好ましく、2〜6がより好ましい。アセチル基、プロピオニル基など)、アリーロイル基(炭素数7〜23が好ましく、7〜15がより好ましく、7〜11が特に好ましい。ベンゾイル基など)、アシルオキシ基(炭素数2〜12が好ましく、2〜6がより好ましい。アセチルオキシ基、プロピオニルオキシ基など)、アリーロイルオキシ基(炭素数7〜23が好ましく、7〜15がより好ましく、7〜11が特に好ましい。ベンゾイルオキシ基など)、(メタ)アクリロイル基、(メタ)アクリロイルオキシ基、カルバモイル基(炭素数1〜12が好ましく、1〜6がより好ましく、1〜3が特に好ましい。カルバモイル基、N−メチルカルバモイル基、N,N−ジメチルカルバモイル、N−フェニルカルバモイル等)が挙げられる。 Y 1 represents —NR 1 R 2 . R 1 and R 2 each represents a monovalent substituent or a hydrogen atom, and is preferably a monovalent substituent. R 1 and R 2 may form a ring with each other, or may have an arbitrary substituent T. Although it does not specifically limit as substituent T, The thing illustrated below is preferable, and, specifically, a halogen atom (for example, fluorine atom), a carbonyl group containing group (for example, C2-C6), an alkoxy group (for example, carbon number). 1-6) and silyl groups (for example, having 1 to 6 carbon atoms). For example, as the carbonyl group-containing group, an acyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6. acetyl group, propionyl group, etc.) or aryloyl group (preferably having 7 to 23 carbon atoms, preferably having 7 to 15 carbon atoms). More preferably, it is particularly preferably 7 to 11. Benzoyl group or the like, acyloxy group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6, acetyloxy group, propionyloxy group or the like), aryloyloxy group (carbon number). 7 to 23 are preferable, 7 to 15 are more preferable, and 7 to 11 are particularly preferable, such as a benzoyloxy group, (meth) acryloyl group, (meth) acryloyloxy group, carbamoyl group (1 to 12 carbon atoms are preferable, 1 to 6 is more preferable, and 1 to 3 is particularly preferable, carbamoyl group, N-methylcarbamoyl group, N, N-dimethyl. Carbamoyl, N- phenylcarbamoyl, etc.).
R1、R2はそれぞれ、水素原子、アルキル基、アルケニル基が好ましい。その中でも、炭素数1〜6のアルキル基が好ましく、炭素数1〜4のアルキル基がより好ましく、炭素数1〜3のアルキル基が特に好ましい。R1、R2は互いに結合してまたは縮合して環を形成していてもよい。このとき、窒素原子、酸素原子、硫黄原子などのヘテロ原子を取り込んでいてもよい。具体的に、以下のヘテロ連結基を介して環を形成していてもよい。形成される環として好ましくは、5員環または6員環が好ましい。5員環としては含窒素の5員環が好ましく、その環をなす化合物として例示すれば、ピロール、イミダゾール、ピラゾール、インダゾール、インドール、ベンゾイミダゾール、ピロリジン、イミダゾリジン、ピラゾリジン、インドリン、カルバゾール、またはこれらの誘導体など(いずれもN置換)が挙げられる。6員環としては、ピペリジン、モルホリン、ピペラジン、またはこれらの誘導体など(いずれもN置換)が挙げられる。 R 1 and R 2 are each preferably a hydrogen atom, an alkyl group, or an alkenyl group. Among these, a C1-C6 alkyl group is preferable, a C1-C4 alkyl group is more preferable, and a C1-C3 alkyl group is especially preferable. R 1 and R 2 may be bonded to each other or condensed to form a ring. At this time, a hetero atom such as a nitrogen atom, an oxygen atom, or a sulfur atom may be incorporated. Specifically, a ring may be formed through the following hetero-linking group. The ring to be formed is preferably a 5-membered ring or a 6-membered ring. As the five-membered ring, a nitrogen-containing five-membered ring is preferable, and examples of the compound forming the ring include pyrrole, imidazole, pyrazole, indazole, indole, benzimidazole, pyrrolidine, imidazolidine, pyrazolidine, indoline, carbazole, or these And the like (both are N-substituted). Examples of the 6-membered ring include piperidine, morpholine, piperazine, and derivatives thereof (all are N-substituted).
Y2は、フッ素原子または−NR3R4を表し、フッ素原子であることが特に好ましい。R3、R4は、R1、R2と同義であり、好ましいものも同じである。R3とR4は置換基同士が環を形成していてもよい。ハロゲン原子の中でもフッ素原子が好ましい理由は上記で述べたことと同じである。R3、R4は任意の置換基Tを有していてもよい。置換基Tの好ましいものは、上記と同義である。 Y 2 represents a fluorine atom or —NR 3 R 4, and is particularly preferably a fluorine atom. R 3 and R 4 have the same meanings as R 1 and R 2 , and preferred ones are also the same. In R 3 and R 4, the substituents may form a ring. The reason why a fluorine atom is preferable among the halogen atoms is the same as described above. R 3 and R 4 may have an arbitrary substituent T. Preferable substituents T have the same meaning as described above.
nは1を表す。
n represents 1 .
なお、式(1)では、シス体およびトランス体の区別なく両者を含みうる意味で記載している。この点は、以下の例示化合物の構造式および式(2)の化合物の解釈において同じである。 In the formula (1), the cis form and the trans form are described in a meaning that they can be included without distinction. This point is the same in the following structural formulas of exemplary compounds and interpretation of the compound of formula (2).
上記アミノ置換ホスファゼン化合物の好ましい具体例を以下に示す。ただし、以下の化合物により本発明はなんら制限を受けるものではない。
<フッ素化ホスファゼン化合物>
次に、本発明の環状ホスファゼン誘導体の製造方法に使用する出発物質化合物として好適に利用される式(2)で表される化合物およびアミン化合物について説明する。
<Fluorinated phosphazene compounds>
Next, the compound represented by formula (2) and the amine compound that are suitably used as the starting material compound used in the method for producing the cyclic phosphazene derivative of the present invention will be described.
上記フッ素化ホスファゼン化合物は、下記式(2)で表される化合物である。
nは1を表す。
本発明においては、反応原料として、ハロゲン化ホスファゼン化合物の中でもフッ素化ホスファゼン化合物を選定した。この理由として、上記のとおりアプリケーション上の利点が挙げられるが、本発明で採用されるルイス酸触媒との関係で反応上の利点が挙げられる。ハロゲン化ホスファゼンはその置換反応の際にハロゲン原子を系内に放出する。中でもフッ素アニオンは塩素アニオン等と比べ反応性が高い(例えば、Chem. Ber. 116, 367-374 (1983) “Darstellung und Strukturbestimmung von Ammoniak-Phosphorpentafluorid (1/1)”参照)。そのため、フッ素アニオンが未反応の基質と反応し、副生成物を生じさせてしまうことがある。そうすると、目的化合物の収率ないし選択率を低下させてしまうこととなる。これに対して、本発明において好適に適用されるルイス酸触媒は、そのような副反応を抑制し、収率・選択率を高める働きを奏する。すなわち、フッ素アニオンを系内でトラップする作用があるものと解される。このような効果が顕著に現れる観点から、上記のとおり、本発明においては、ハロゲン原子としてフッ素原子を有する基質とルイス酸触媒とを組み合わせて用いる。
n represents 1 .
In the present invention, among the halogenated phosphazene compounds, fluorinated phosphazene compounds were selected as reaction raw materials. The reasons for this include application advantages as described above, but reaction advantages in relation to the Lewis acid catalyst employed in the present invention. Halogenated phosphazenes release halogen atoms into the system during the substitution reaction. Among them, the fluorine anion is more reactive than the chlorine anion (see, for example, Chem. Ber. 116, 367-374 (1983) “Darstellung und Strukturbestimmung von Ammoniak-Phosphorpentafluorid (1/1)”). Therefore, the fluorine anion may react with an unreacted substrate to produce a by-product. If it does so, the yield thru | or selectivity of a target compound will be reduced. On the other hand, the Lewis acid catalyst suitably applied in the present invention functions to suppress such side reactions and increase the yield and selectivity. That is, it is understood that the fluorine anion is trapped in the system. From the viewpoint that such an effect appears remarkably, as described above, in the present invention, a substrate having a fluorine atom as a halogen atom and a Lewis acid catalyst are used in combination.
また、本発明の好ましい実施形態によれば、アミノ基の一置換体及び二置換体(特に一置換体)を選択的に合成することができる。その理由は不明の点を含むが、ルイス酸触媒が、置換数(逐次反応の各段階)による反応障壁に適合し、上記置換数の化合物を選択的に生成させるものと解される。上記特許文献7、8は反応の選択性ではなく高置換率とすることを目的としている。なお、フッ素化ホスファゼンのアミノ基の一置換体または二置換体(特に一置換体)は難燃剤として特に有用である(国際公開第2013/047342号パンフレット)。
In addition, according to a preferred embodiment of the present invention, mono- and di-substituted amino groups (particularly mono-substituted) can be selectively synthesized. Although the reason includes an unknown point, it is understood that the Lewis acid catalyst is adapted to the reaction barrier depending on the number of substitutions (each step of the sequential reaction) and selectively generates the compound having the number of substitutions. The above-mentioned
<アミン化合物>
アミン化合物は化学構造中にアミノ基を有する化合物を意味し、上記アミノ基は上記NR1R2(NR3R4と言っても同じである)であることが好ましい。アミン化合物は炭素数1〜12であることが好ましく、1〜8がより好ましく、1〜6であることが特に好ましい。炭素数が少ないもののときには、1〜3であることが好ましい。アミン化合物は具体的に、H−NR1R2で表される化合物であることが好ましく、メチルアミン、エチルアミン、ジメチルアミン、ジエチルアミン、エチルメチルアミンなどが挙げられる。中でも、ジメチルアミン、ジエチルアミンであることが特に好ましい。R1およびR2は上記式(1)で定義したものと同義である。アミン化合物において、R1およびR2が環を形成してもよいことは、上記と同義であり、その好ましいものもアミノ置換ホスファゼンのR1およびR2が形成する環として例示したものと同じである。
<Amine compound>
The amine compound means a compound having an amino group in the chemical structure, and the amino group is preferably the NR 1 R 2 (same as NR 3 R 4 ). The amine compound preferably has 1 to 12 carbon atoms, more preferably 1 to 8, and particularly preferably 1 to 6. When the number of carbon atoms is small, it is preferably 1 to 3. Specifically, the amine compound is preferably a compound represented by H—NR 1 R 2 , and examples thereof include methylamine, ethylamine, dimethylamine, diethylamine, and ethylmethylamine. Of these, dimethylamine and diethylamine are particularly preferable. R 1 and R 2 have the same meaning as defined in the above formula (1). In the amine compound, R 1 and R 2 may form a ring as defined above, and preferred examples thereof are the same as those exemplified as the ring formed by R 1 and R 2 of the amino-substituted phosphazene. is there.
本反応では、置換後に当量のフッ化水素が発生する。生成するフッ化水素を中和するために、塩基性化合物を添加してもよい。添加する塩基性化合物としては、有機、無機化合物があるが、有機塩基が特に好ましい。有機塩基としては、トリエチルアミン、ジイソプロピルエチルアミンなどが挙げられる。アミン置換反応の場合は、置換に使用するアミンを中和に用いてもよい。あるいは、上記のようにフッ素アニオンのトラップ性のよい触媒を用いて、触媒中にこれを取り込んだ形で反応を終了させてもよい。 In this reaction, an equivalent amount of hydrogen fluoride is generated after substitution. In order to neutralize the generated hydrogen fluoride, a basic compound may be added. The basic compound to be added includes organic and inorganic compounds, and an organic base is particularly preferable. Examples of the organic base include triethylamine and diisopropylethylamine. In the case of an amine substitution reaction, the amine used for substitution may be used for neutralization. Alternatively, as described above, a catalyst having a good trapping property of fluorine anion may be used, and the reaction may be terminated in a form in which the catalyst is incorporated into the catalyst.
<ルイス酸触媒>
本発明に係るアミノ置換ホスファゼン化合物の製造方法においては、その合成反応にルイス酸触媒を適用する。ここで「ルイス酸」とは、電子対を受け取ることができる物質を示す。本発明においては中でもフッ素アニオンのトラップ作用の高いルイス酸触媒を用いることが好ましい。
ルイス酸触媒を構成する化合物に含まれる金属または半金属(M)としては、アルミニウム、マグネシウム、リチウム、マンガン、鉄、銅、亜鉛、スズ、ホウ素、ケイ素、チタン、ジルコニウム、クロム、コバルト、ニッケル、モリブデン、バナジウム、タングステン、ストロンチウム、アンチモン、ゲルマニウム、ガリウム、インジウム、ハフニウム、スカンジウム、イットリウム、ランタノイド金属などが挙げられる。なかでも、収率の観点から、上記金属または半金属は、アルミニウム、マグネシウム、リチウム、マンガン、鉄、銅、亜鉛、スズ、ホウ素、ケイ素、チタン、ジルコニウム、クロム、コバルト、ニッケル、モリブデン、バナジウムが好ましく、アルミニウム、マグネシウム、リチウム、鉄、銅(II)、亜鉛、ホウ素、ケイ素がより好ましく、アルミニウム、マグネシウム、リチウム、鉄、銅(II)、ホウ素、ケイ素が更に好ましく、アルミニウム、マグネシウム、リチウム、鉄、銅が特に好ましい。
<Lewis acid catalyst>
In the method for producing an amino-substituted phosphazene compound according to the present invention, a Lewis acid catalyst is applied to the synthesis reaction. Here, “Lewis acid” refers to a substance that can accept an electron pair. In the present invention, it is particularly preferable to use a Lewis acid catalyst having a high fluorine anion trapping action.
As the metal or metalloid (M) contained in the compound constituting the Lewis acid catalyst, aluminum, magnesium, lithium, manganese, iron, copper, zinc, tin, boron, silicon, titanium, zirconium, chromium, cobalt, nickel, Examples include molybdenum, vanadium, tungsten, strontium, antimony, germanium, gallium, indium, hafnium, scandium, yttrium, and lanthanoid metals. Among these, from the viewpoint of yield, the above metals or metalloids are aluminum, magnesium, lithium, manganese, iron, copper, zinc, tin, boron, silicon, titanium, zirconium, chromium, cobalt, nickel, molybdenum, vanadium. Preferably, aluminum, magnesium, lithium, iron, copper (II), zinc, boron, silicon are more preferable, aluminum, magnesium, lithium, iron, copper (II), boron, silicon are more preferable, aluminum, magnesium, lithium, Iron and copper are particularly preferable.
上記ルイス酸触媒は、M−Z結合を少なくとも1つ有する化合物からなることが好ましい。式中、Mは金属または半金属原子であり、その好ましいものは上記と同義である。Zはハロゲン原子、スルホネート部位(トリフルオロメタンスルホネート部位等)、アシレート部位(アセテート部位)、硫酸部位、硝酸部位である。Zは、なかでもハロゲン原子が好ましく、ヨウ素、臭素、塩素、フッ素がより好ましく、ヨウ素、臭素、塩素がさらに好ましく、臭素、塩素がさらに好ましく、塩素が特に好ましい。 The Lewis acid catalyst is preferably composed of a compound having at least one MZ bond. In the formula, M is a metal or metalloid atom, and preferred ones are as defined above. Z is a halogen atom, a sulfonate moiety (such as a trifluoromethanesulfonate moiety), an acylate moiety (acetate moiety), a sulfuric acid moiety, or a nitric acid moiety. Among them, Z is preferably a halogen atom, more preferably iodine, bromine, chlorine or fluorine, further preferably iodine, bromine or chlorine, further preferably bromine or chlorine, particularly preferably chlorine.
ルイス酸として、例えばBF3OEt2、AlBr3、AlCl3、AlCl2F、ZnI2、MgCl2、LiCl、LiBr、SnCl4、CuCl2、FeCl 2 、FeCl3、ZnCl2、シリルクロリド化合物、MnCl2、CoCl2、NiCl2、ZrOCl2、ZrCl4、SrCl2、InCl3、HfOCl2、GaCl3、EtAlCl2、BiCl3、TiCl4、GeCl4、SbCl3、FeBr3、VCl3、MoCl5、BCl3、BBr3、Cu(OTf)2、Ln(OTf)3、Fe2(SO4)3、ZrCl4、Zr(SO4)2、ZnSO4、Fe(NO3)3、Ni(NO3)2、Mg(OAc)2、Fe(OAc)3、Co(OAc)2等が使用できる。なかでも、収率の観点から、AlBr3、AlCl3、AlCl2F、ZnI2、MgCl2、LiCl、LiBr、SnCl4、CuCl2、FeCl3、ZnCl2、シリルクロリド化合物、MnCl2、CoCl2、NiCl2、ZrOCl2、ZrCl4、EtAlCl2、TiCl4、FeBr3、VCl3、MoCl5、BCl3、BBr3が好ましく、AlBr3、AlCl3、MgCl2、LiCl、LiBr、CuCl2、FeCl3、ZnCl2、シリルクロリド化合物、ZrCl4、ZrOCl2、EtAlCl2、FeBr3、BCl3がより好ましく、AlCl3、MgCl2、LiCl、LiBr、CuCl2、FeCl3、ZrCl4、ZrOCl2、シリルクロリド化合物、BCl3が更に好ましく、AlCl3、MgCl2、LiCl、LiBr、CuCl2、FeCl3が特に好ましい。
シリルクロリド化合物は、Si−Cl結合を有する化合物の総称であり、(RS)nsSi(Cl)4−nsであることが好ましい。ここで、RSは、アルキル基(炭素数1〜12が好ましく、1〜6がより好ましく、1〜3が特に好ましい)、アルケニル基(炭素数2〜12が好ましく、2〜6がより好ましい)、アリール基(炭素数6〜22が好ましく、6〜14がより好ましく、6〜10が特に好ましい)であり、なかでもアルキル基が好ましい。複数あるRSは同じであっても異なってもよい。
nsは0〜3の整数であり、2または3が好ましい。
シリルクロリド化合物としては、SiCl4、Me2SiCl2、TMS−Cl、TES−Cl、PhSiCl3、ジビニルジクロロシラン、メチルビニルジクロロシランが好ましく、なかでも、SiCl4、Me2SiCl2、TMS−Clが好ましい。
OTfはトリフルオロメタンスルホネート部位、OAcはアセテート部位を表す。Meはメチル基を表す。Etはエチル基を表す。Phはフェニル基を表す。Acはアセチル基を表す。TMSはトリメチルシリル基を表す。TESはトリエチルシリル基を表す。
Examples of Lewis acids include BF 3 OEt 2 , AlBr 3 , AlCl 3 , AlCl 2 F, ZnI 2 , MgCl 2 , LiCl, LiBr, SnCl 4 , CuCl 2 , FeCl 2 , FeCl 3 , ZnCl 2 , silyl chloride compound, MnCl 2, CoCl 2, NiCl 2, ZrOCl 2,
The silyl chloride compound is a general term for compounds having a Si—Cl bond, and is preferably (R S ) ns Si (Cl) 4-ns . Here, R S is an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms) or an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms). ), An aryl group (having 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, and particularly preferably 6 to 10 carbon atoms), and an alkyl group is particularly preferable. A plurality of R S may be the same or different.
ns is an integer of 0 to 3, and 2 or 3 is preferable.
As the silyl chloride compound, SiCl 4 , Me 2 SiCl 2 , TMS-Cl, TES-Cl, PhSiCl 3 , divinyldichlorosilane, and methylvinyldichlorosilane are preferable, and SiCl 4 , Me 2 SiCl 2 , TMS-Cl are preferable. Is preferred.
OTf represents a trifluoromethanesulfonate site, and OAc represents an acetate site. Me represents a methyl group. Et represents an ethyl group. Ph represents a phenyl group. Ac represents an acetyl group. TMS represents a trimethylsilyl group. TES represents a triethylsilyl group.
本発明において、ルイス酸は、1種のみを用いてもよく、2種以上を用いてもよい。 In the present invention, only one Lewis acid may be used, or two or more Lewis acids may be used.
ルイス酸触媒の使用量は、コストの観点から、出発原料であるフッ素化ホスファゼン化合物に対して0.01当量以上であることが好ましく、0.05当量以上がより好ましく、0.2当量以上が更に好ましく、0.25当量以上が特に好ましい。上限としては、5当量以下であることが好ましく、3当量以下がより好ましく、2当量以下が更に好ましく、1当量以下が特に好ましい。ルイス酸触媒の使用量は、上下限の範囲として言えば、出発原料であるフッ素化ホスファゼン化合物に対して0.01当量〜5当量であることが好ましく、0.05〜3当量であることがより好ましく、0.2当量〜3当量であることが更に好ましく、0.2当量〜2当量であることが更に好ましく、0.25当量〜1当量であることが特に好ましい。 The use amount of the Lewis acid catalyst is preferably 0.01 equivalents or more, more preferably 0.05 equivalents or more, and more preferably 0.2 equivalents or more with respect to the fluorinated phosphazene compound as a starting material from the viewpoint of cost. More preferred is 0.25 equivalent or more. The upper limit is preferably 5 equivalents or less, more preferably 3 equivalents or less, still more preferably 2 equivalents or less, and particularly preferably 1 equivalent or less. The amount of the Lewis acid catalyst used is preferably 0.01 equivalents to 5 equivalents and 0.05 to 3 equivalents with respect to the fluorinated phosphazene compound that is the starting material, in terms of the upper and lower limits. More preferably, it is more preferably 0.2 equivalents to 3 equivalents, still more preferably 0.2 equivalents to 2 equivalents, and particularly preferably 0.25 equivalents to 1 equivalent.
本反応の温度としては、製造効率等の点からは、−20℃以上が好ましく、−15℃以上がより好ましく、−10℃以上が特に好ましい。上限は、100℃以下が好ましく、60℃以下がより好ましく、50℃以下が特に好ましい。本反応の時間としては、24時間以内が好ましく、10時間以内がより好ましく、5時間以内が更に好ましく、3時間以内が特に好ましい。反応終了後、必要により分液や蒸留等の精製を行う。 The temperature of this reaction is preferably −20 ° C. or higher, more preferably −15 ° C. or higher, and particularly preferably −10 ° C. or higher from the viewpoint of production efficiency. The upper limit is preferably 100 ° C. or lower, more preferably 60 ° C. or lower, and particularly preferably 50 ° C. or lower. The reaction time is preferably within 24 hours, more preferably within 10 hours, further preferably within 5 hours, and particularly preferably within 3 hours. After completion of the reaction, purification such as separation or distillation is performed as necessary.
<反応溶媒>
本発明の製造方法においては、反応溶媒を用いても用いなくてもよいが、これを用いて行うことが好ましい。有機溶媒としては、脂肪族炭化水素化合物、ハロゲン化炭化水素化合物、エーテル化合物、エステル化合物、ケトン化合物、ニトリル化合物、アミド化合物、スルホキシド化合物、カルボン酸化合物、芳香族炭化水素化合物、尿素化合物等が挙げられる。
脂肪族炭化水素化合物としては、ペンタン、ヘキサンまたはシクロヘキサンなどが挙げられる。
ハロゲン化炭化水素化合物としては、塩化メチレン、クロロホルムまたは1,2−ジクロロエタンなどが挙げられる。
エーテル化合物としては、ジエチルエーテル、ジイソプロピルエーテル、ジオキサン、テトラヒドロフラン、アニソール、エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテルまたはジエチレングリコールジエチルエーテルなどが挙げられる。
エステル化合物としては、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸イソプロピルまたは酢酸ブチルなどが挙げられる。
ケトン化合物としては、アセトン、2−ブタノンまたは4−メチル−2−ペンタノンなどが挙げられる。
ニトリル化合物としては、アセトニトリルなどが挙げられる。
アミド化合物としては、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミドまたはN−メチルピロリドンなどが挙げられる。
スルホキシド化合物としては、ジメチルスルホキシド、スルホランなどが挙げられる。
カルボン酸としては、酢酸などが挙げられる。
芳香族炭化水素化合物としては、ベンゼン、クロロベンゼン、ジクロロベンゼン、ニトロベンゼン、トルエンまたはキシレンなどが挙げられる。
尿素化合物としては、1,3−ジメチル−2−イミダゾリジノンなどが挙げられる。
反応溶媒としては、無極性溶媒、極性溶媒を用いることができる。無極性溶媒としては、溶媒を構成する分子の双極子モーメントが0又は低い値の溶媒であれば特に制限はないが、例えば、ヘキサン、ペンタン、シクロヘキサン及びトルエン等が挙げられる。これらの中でも、取り扱い易く、安価である点で、ヘキサンが特に好ましい。
上記極性溶媒としては、溶媒を構成する分子が双極子モーメントを有する溶媒であれば特に制限はないが、例えば、アセトニトリル、テトラヒドロフラン、ジエチルエーテル、ターシャリーブチルメチルエーテル、酢酸エチル、アセトン、ニトロベンゼン、ジメチルアセトアミド、N−メチルピロリドン等が挙げられる。これらの中でも、取り扱い易い点で、アセトニトリル、ターシャリーブチルメチルエーテル、テトラヒドロフラン等が好ましく、アセトニトリルが特に好ましい。反応溶媒は1種のみを用いてもよく、2種以上を用いてもよく、また2相系で反応してもよい。
<Reaction solvent>
In the production method of the present invention, a reaction solvent may or may not be used, but it is preferable to use this. Examples of the organic solvent include aliphatic hydrocarbon compounds, halogenated hydrocarbon compounds, ether compounds, ester compounds, ketone compounds, nitrile compounds, amide compounds, sulfoxide compounds, carboxylic acid compounds, aromatic hydrocarbon compounds, urea compounds, and the like. It is done.
Examples of the aliphatic hydrocarbon compound include pentane, hexane, and cyclohexane.
Examples of the halogenated hydrocarbon compound include methylene chloride, chloroform, and 1,2-dichloroethane.
Examples of the ether compound include diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, anisole, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether.
Examples of the ester compound include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, and butyl acetate.
Examples of the ketone compound include acetone, 2-butanone, and 4-methyl-2-pentanone.
Examples of the nitrile compound include acetonitrile.
Examples of the amide compound include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.
Examples of the sulfoxide compound include dimethyl sulfoxide and sulfolane.
Examples of the carboxylic acid include acetic acid.
Examples of the aromatic hydrocarbon compound include benzene, chlorobenzene, dichlorobenzene, nitrobenzene, toluene, and xylene.
Examples of the urea compound include 1,3-dimethyl-2-imidazolidinone.
As the reaction solvent, a nonpolar solvent or a polar solvent can be used. The nonpolar solvent is not particularly limited as long as the dipole moment of the molecules constituting the solvent is 0 or a low value, and examples thereof include hexane, pentane, cyclohexane, and toluene. Among these, hexane is particularly preferable because it is easy to handle and inexpensive.
The polar solvent is not particularly limited as long as the molecule constituting the solvent has a dipole moment. For example, acetonitrile, tetrahydrofuran, diethyl ether, tertiary butyl methyl ether, ethyl acetate, acetone, nitrobenzene, dimethyl Examples include acetamide and N-methylpyrrolidone. Among these, acetonitrile, tertiary butyl methyl ether, tetrahydrofuran, and the like are preferable from the viewpoint of easy handling, and acetonitrile is particularly preferable. As the reaction solvent, only one kind may be used, two or more kinds may be used, and the reaction may be performed in a two-phase system.
本発明の製造方法で得られるアミノ置換ホスファゼン化合物は様々な用途に用いることができる。例えば、各種電気機器や工業製品に適用される樹脂、電解液、潤滑剤、塗料等の難燃剤として適用することができる。あるいは、殺虫剤として利用することもできる(独国公開特許公報第2139691号明細書等参照)。昨今そのニーズが高いものとして非水二次電池への利用が挙げられる。以下では、非水二次電池に適用する際の好ましい実施形態にについてその概略を説明する。 The amino-substituted phosphazene compound obtained by the production method of the present invention can be used for various applications. For example, it can be applied as a flame retardant for resins, electrolytes, lubricants, paints and the like applied to various electrical equipment and industrial products. Alternatively, it can also be used as an insecticide (see German Offenlegungsschrift 213991). Recently, the use of non-aqueous secondary batteries is one of the high needs. Below, the outline is demonstrated about preferable embodiment at the time of applying to a non-aqueous secondary battery.
本明細書において化合物の表示(例えば、化合物と末尾に付して呼ぶとき)については、当該化合物そのもののほか、その塩、そのイオンを含む意味に用いる。また、所望の効果を奏する範囲で、置換基を導入するなど一部を変化させた誘導体を含む意味である。
本明細書において置換・無置換を明記していない置換基(連結基についても同様)については、その基に任意の置換基を有していてもよい意味である。これは置換・無置換を明記していない化合物についても同義である。好ましい置換基としては、下記置換基Tが挙げられる。
置換基Tとしては、下記のものが挙げられる。
アルキル基(好ましくは炭素原子数1〜20のアルキル基、例えばメチル、エチル、イソプロピル、t−ブチル、ペンチル、ヘプチル、1−エチルペンチル、ベンジル、2−エトキシエチル、1−カルボキシメチル等)、アルケニル基(好ましくは炭素原子数2〜20のアルケニル基、例えば、ビニル、アリル、オレイル等)、アルキニル基(好ましくは炭素原子数2〜20のアルキニル基、例えば、エチニル、ブタジイニル、フェニルエチニル等)、シクロアルキル基(好ましくは炭素原子数3〜20のシクロアルキル基、例えば、シクロプロピル、シクロペンチル、シクロヘキシル、4−メチルシクロヘキシル等)、アリール基(好ましくは炭素原子数6〜26のアリール基、例えば、フェニル、1−ナフチル、4−メトキシフェニル、2−クロロフェニル、3−メチルフェニル等)、ヘテロ環基(好ましくは炭素原子数2〜20のヘテロ環基、好ましくは、少なくとも1つの酸素原子、硫黄原子、窒素原子を有する5または6員環のヘテロ環基が好ましく、例えば、2−ピリジル、4−ピリジル、2−イミダゾリル、2−ベンゾイミダゾリル、2−チアゾリル、2−オキサゾリル等)、アルコキシ基(好ましくは炭素原子数1〜20のアルコキシ基、例えば、メトキシ、エトキシ、イソプロピルオキシ、ベンジルオキシ等)、アリールオキシ基(好ましくは炭素原子数6〜26のアリールオキシ基、例えば、フェノキシ、1−ナフチルオキシ、3−メチルフェノキシ、4−メトキシフェノキシ等)、アルコキシカルボニル基(好ましくは炭素原子数2〜20のアルコキシカルボニル基、例えば、エトキシカルボニル、2−エチルヘキシルオキシカルボニル等)、アミノ基(好ましくは炭素原子数0〜20のアミノ基、アルキルアミノ基、アリールアミノ基を含み、例えば、アミノ、N,N−ジメチルアミノ、N,N−ジエチルアミノ、N−エチルアミノ、アニリノ等)、スルファモイル基(好ましくは炭素原子数0〜20のスルファモイル基、例えば、N,N−ジメチルスルファモイル、N−フェニルスルファモイル等)、アシル基(好ましくは炭素原子数1〜20のアシル基、例えば、アセチル、プロピオニル、ブチリル、ベンゾイル等)、アシルオキシ基(好ましくは炭素原子数1〜20のアシルオキシ基、例えば、アセチルオキシ、ベンゾイルオキシ等)、カルバモイル基(好ましくは炭素原子数1〜20のカルバモイル基、例えば、N,N−ジメチルカルバモイル、N−フェニルカルバモイル等)、アシルアミノ基(好ましくは炭素原子数1〜20のアシルアミノ基、例えば、アセチルアミノ、ベンゾイルアミノ等)、アルキルチオ基(好ましくは炭素原子数1〜20のアルキルチオ基、例えば、メチルチオ、エチルチオ、イソプロピルチオ、ベンジルチオ等)、アリールチオ基(好ましくは炭素原子数6〜26のアリールチオ基、例えば、フェニルチオ、1−ナフチルチオ、3−メチルフェニルチオ、4−メトキシフェニルチオ等)、アルキルもしくはアリールスルホニル基(好ましくは炭素原子数1〜20のアルキルもしくはアリールスルホニル基、例えば、メチルスルホニル、エチルスルホニル、ベンゼンスルホニル等)、ヒドロキシル基、シアノ基、ハロゲン原子(例えばフッ素原子、塩素原子、臭素原子、ヨウ素原子等)が挙げられる。
また、これらの置換基Tで挙げた各基は、上記の置換基Tがさらに置換していてもよい。
化合物ないし置換基・連結基等がアルキル基・アルキレン基、アルケニル基・アルケニレン基、アルキニル基・アルキニレン基等を含むとき、これらは環状でも鎖状でもよく、また直鎖でも分岐していてもよく、上記のように置換されていても無置換でもよい。またアリール基、ヘテロ環基等を含むとき、それらは単環でも縮環でもよく、同様に置換されていても無置換でもよい。
In the present specification, the indication of a compound (for example, when referring to a compound with a suffix) is used in the meaning of including the compound itself, its salt, and its ion. In addition, it is meant to include derivatives in which a part thereof is changed, such as introduction of a substituent, within a range where a desired effect is exhibited.
In the present specification, a substituent that does not specify substitution / non-substitution (the same applies to a linking group) means that the group may have an arbitrary substituent. This is also synonymous for compounds that do not specify substitution / non-substitution. Preferred substituents include the following substituent T.
Examples of the substituent T include the following.
An alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.), alkenyl A group (preferably an alkenyl group having 2 to 20 carbon atoms, such as vinyl, allyl, oleyl, etc.), an alkynyl group (preferably an alkynyl group having 2 to 20 carbon atoms, such as ethynyl, butadiynyl, phenylethynyl, etc.), A cycloalkyl group (preferably a cycloalkyl group having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.), an aryl group (preferably an aryl group having 6 to 26 carbon atoms, for example, Phenyl, 1-naphthyl, 4-methoxyphenyl, -Chlorophenyl, 3-methylphenyl, etc.), a heterocyclic group (preferably a heterocyclic group having 2 to 20 carbon atoms, preferably a 5- or 6-membered heterocycle having at least one oxygen atom, sulfur atom, nitrogen atom) A cyclic group is preferable, for example, 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-thiazolyl, 2-oxazolyl, etc., an alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, for example, Methoxy, ethoxy, isopropyloxy, benzyloxy, etc.), aryloxy groups (preferably aryloxy groups having 6 to 26 carbon atoms, such as phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy, etc.), An alkoxycarbonyl group (preferably an alkoxycarbonyl having 2 to 20 carbon atoms) Nyl groups such as ethoxycarbonyl, 2-ethylhexyloxycarbonyl, etc., amino groups (preferably including amino groups having 0 to 20 carbon atoms, alkylamino groups, arylamino groups, such as amino, N, N-dimethyl Amino, N, N-diethylamino, N-ethylamino, anilino, etc.), sulfamoyl groups (preferably sulfamoyl groups having 0 to 20 carbon atoms, such as N, N-dimethylsulfamoyl, N-phenylsulfamoyl, etc.) ), An acyl group (preferably an acyl group having 1 to 20 carbon atoms, such as acetyl, propionyl, butyryl, benzoyl, etc.), an acyloxy group (preferably an acyloxy group having 1 to 20 carbon atoms, such as acetyloxy, benzoyl) Oxy, etc.), a carbamoyl group (preferably a C 1-20 carbon atom) Rubamoyl group such as N, N-dimethylcarbamoyl, N-phenylcarbamoyl, etc., acylamino group (preferably acylamino group having 1 to 20 carbon atoms such as acetylamino, benzoylamino, etc.), alkylthio group (preferably carbon An alkylthio group having 1 to 20 atoms such as methylthio, ethylthio, isopropylthio, benzylthio, etc., an arylthio group (preferably an arylthio group having 6 to 26 carbon atoms such as phenylthio, 1-naphthylthio, 3-methylphenylthio) 4-methoxyphenylthio, etc.), an alkyl or arylsulfonyl group (preferably an alkyl or arylsulfonyl group having 1 to 20 carbon atoms, such as methylsulfonyl, ethylsulfonyl, benzenesulfonyl, etc.), a hydroxyl group, Anomoto, halogen atom (e.g. fluorine atom, a chlorine atom, a bromine atom, an iodine atom) and the like.
In addition, each of the groups listed as the substituent T may be further substituted with the substituent T described above.
When a compound or a substituent / linking group includes an alkyl group / alkylene group, an alkenyl group / alkenylene group, an alkynyl group / alkynylene group, etc., these may be cyclic or linear, and may be linear or branched These may be substituted as described above or may be unsubstituted. Moreover, when an aryl group, a heterocyclic group, etc. are included, they may be monocyclic or condensed and may be similarly substituted or unsubstituted.
本明細書で規定される各置換基は、本発明の効果を奏する範囲で下記の連結基Lを介在して置換されていてもよい。たとえば、アルキル基・アルキレン基、アルケニル基・アルケニレン基等はさらに構造中に下記のヘテロ連結基を介在していてもよい。
連結基Lとしては、炭化水素連結基〔炭素数1〜10のアルキレン基(より好ましくは炭素数1〜6、さらに好ましくは1〜3)、炭素数2〜10のアルケニレン基(より好ましくは炭素数2〜6、さらに好ましくは2〜4)、炭素数6〜22のアリーレン基(より好ましくは炭素数6〜10)〕、ヘテロ連結基〔カルボニル基(−CO−)、エーテル基(−O−)、チオエーテル基(−S−)、イミノ基(−NRN−)、イミン連結基(RN−N=C<、−N=C(RN)−)〕、またはこれらを組み合せた連結基が好ましい。なお、縮合して環を形成する場合には、上記炭化水素連結基が、二重結合や三重結合を適宜形成していてもよい。
RNは水素原子または置換基である。置換基としては、アルキル基(炭素数1〜24が好ましく、1〜12がより好ましい)、アルケニル基(炭素数2〜24が好ましく、2〜12がより好ましい)、アルキニル基(炭素数2〜24が好ましく、2〜12がより好ましい)、炭素数6〜10のアリール基、炭素数7〜11のアラルキル基が好ましい。)である。
本明細書において、連結基を構成する原子の数は、1〜36であることが好ましく、1〜24であることがより好ましく、1〜12であることがさらに好ましく、1〜6であることが特に好ましい。連結基の連結原子数は10以下であることが好ましく、8以下であることがより好ましい。下限としては、1以上である。上記連結原子数とは所定の構造部間を結ぶ経路に位置し連結に関与する最少の原子数を言う。たとえば、−CH2−C(=O)−O−の場合、連結基を構成する原子の数は6となるが、連結原子数は3となる。
Each substituent defined in the present specification may be substituted via the following linking group L within a range that exhibits the effects of the present invention. For example, the alkyl group / alkylene group, alkenyl group / alkenylene group and the like may further have the following hetero-linking group interposed in the structure.
Examples of the linking group L include a hydrocarbon linking group [an alkylene group having 1 to 10 carbon atoms (more preferably 1 to 6 carbon atoms, still more preferably 1 to 3), an alkenylene group having 2 to 10 carbon atoms (more preferably carbon atoms). 2-6, more preferably 2-4), an arylene group having 6-22 carbon atoms (more preferably 6-10 carbon atoms)], a hetero linking group [carbonyl group (—CO—), ether group (—O -), thioether group (-S-), an imino group (-NR N -), imine linking group (R N -N = C <, - N = C (R N) -) ], or connecting a combination thereof Groups are preferred. In addition, when condensing and forming a ring, the said hydrocarbon coupling group may form the double bond and the triple bond suitably.
RN is a hydrogen atom or a substituent. Examples of the substituent include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 12), and an alkynyl group (having 2 to 2 carbon atoms). 24 is preferable, and 2 to 12 are more preferable), an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 11 carbon atoms are preferable. ).
In the present specification, the number of atoms constituting the linking group is preferably 1 to 36, more preferably 1 to 24, still more preferably 1 to 12, and 1 to 6. Is particularly preferred. The number of linking atoms in the linking group is preferably 10 or less, and more preferably 8 or less. The lower limit is 1 or more. The number of connected atoms refers to the minimum number of atoms that are located in a path connecting predetermined structural portions and are involved in the connection. For example, in the case of —CH 2 —C (═O) —O—, the number of atoms constituting the linking group is 6, but the number of linking atoms is 3.
本明細書において、特定の符号で表示された置換基や連結基等が複数あるとき、あるいは複数の置換基等(置換基数の規定も同様)を同時もしくは択一的に規定するときには、それぞれの置換基等は互いに同一でも異なっていてもよい。また、複数の置換基や連結基が隣接するときにはそれらが互いに結合したり縮合したりして環を形成していてもよい。 In this specification, when there are a plurality of substituents or linking groups indicated by a specific symbol, or when a plurality of substituents etc. (same definition of the number of substituents) are specified simultaneously or alternatively, The substituents and the like may be the same as or different from each other. When a plurality of substituents or linking groups are adjacent to each other, they may be bonded to each other or condensed to form a ring.
<非水二次電池用電解液>
(電解質)
本実施形態の非水二次電池には、非水二次電池用の電解液が適用される。電解液に用いる電解質は周期律表第一族又は第二族に属する金属イオンの塩であることが好ましい。その材料は電解液の使用目的により適宜選択される。例えば、リチウム塩、カリウム塩、ナトリウム塩、カルシウム塩、マグネシウム塩などが挙げられ、二次電池などに使用される場合には、出力の観点からリチウム塩が好ましい。本発明の製造方法で製造したアミノ置換ホスファゼン化合物をリチウム二次電池用非水系電解液として用いる場合には、金属イオンの塩としてリチウム塩を選択することが好ましい。リチウム塩としては、リチウム二次電池用非水系電解液の電解質に通常用いられるリチウム塩が好ましく、特に制限はないが、例えば、以下に述べるものが好ましい。
<Electrolyte for non-aqueous secondary battery>
(Electrolytes)
An electrolyte solution for a non-aqueous secondary battery is applied to the non-aqueous secondary battery of this embodiment. The electrolyte used in the electrolytic solution is preferably a salt of a metal ion belonging to
(L−1)無機リチウム塩:LiPF6、LiBF4、LiAsF6、LiSbF6等の無機フッ化物塩;LiClO4、LiBrO4、LiIO4等の過ハロゲン酸塩;LiAlCl4等の無機塩化物塩等。 (L-1) Inorganic lithium salts: inorganic fluoride salts such as LiPF 6 , LiBF 4 , LiAsF 6 , LiSbF 6 ; perhalogenates such as LiClO 4 , LiBrO 4 , LiIO 4 ; inorganic chloride salts such as LiAlCl 4 etc.
(L−2)含フッ素有機リチウム塩:LiCF3SO3等のパーフルオロアルカンスルホン酸塩;LiN(CF3SO2)2、LiN(CF3CF2SO2)2、LiN(FSO2)2、LiN(CF3SO2)(C4F9SO2)等のパーフルオロアルカンスルホニルイミド塩;LiC(CF3SO2)3等のパーフルオロアルカンスルホニルメチド塩;Li[PF5(CF2CF2CF3)]、Li[PF4(CF2CF2CF3)2]、Li[PF3(CF2CF2CF3)3]、Li[PF5(CF2CF2CF2CF3)]、Li[PF4(CF2CF2CF2CF3)2]、Li[PF3(CF2CF2CF2CF3)3]等のフルオロアルキルフッ化リン酸塩等。 (L-2) Fluorine-containing organic lithium salt: Perfluoroalkane sulfonate such as LiCF 3 SO 3 ; LiN (CF 3 SO 2 ) 2 , LiN (CF 3 CF 2 SO 2 ) 2 , LiN (FSO 2 ) 2 , Perfluoroalkanesulfonylimide salts such as LiN (CF 3 SO 2 ) (C 4 F 9 SO 2 ); perfluoroalkanesulfonylmethide salts such as LiC (CF 3 SO 2 ) 3 ; Li [PF 5 (CF 2 CF 2 CF 3 )], Li [PF 4 (CF 2 CF 2 CF 3 ) 2 ], Li [PF 3 (CF 2 CF 2 CF 3 ) 3 ], Li [PF 5 (CF 2 CF 2 CF 2 CF 3 )], Li [PF 4 ( CF 2 CF 2 CF 2 CF 3) 2], Li [PF 3 (CF 2 CF 2 CF 2 CF 3) 3] fluoroalkyl fluoride such as potash Acid salts, and the like.
(L−3)オキサラトボレート塩:リチウムビス(オキサラト)ボレート、リチウムジフルオロオキサラトボレート等。
これらのなかで、LiPF6、LiBF4、LiAsF6、LiSbF6、LiClO4、Li(Rf1SO3)、LiN(Rf1SO2)2、LiN(FSO2)2、及びLiN(Rf1SO2)(Rf2SO2)が好ましく、LiPF6、LiBF4、LiN(Rf1SO2)2、LiN(FSO2)2、及びLiN(Rf1SO2)(Rf2SO2)などのリチウム塩がさらに好ましい。ここで、Rf1、Rf2はそれぞれパーフルオロアルキル基を示す。
なお、電解液に用いる電解質は、1種を単独で使用しても、2種以上を任意に組み合わせてもよい。
電解液における電解質(好ましくは周期律表第一族又は第二族に属する金属のイオンもしくはその金属塩)は、以下に電解液の調製法で述べる好ましい塩濃度となるような量で添加されることが好ましい。塩濃度は電解液の使用目的により適宜選択されるが、一般的には電解液全質量中10質量%〜50質量%であり、さらに好ましくは15質量%〜30質量%である。モル濃度としては0.5M〜1.5Mが好ましい。なお、イオンの濃度として評価するときには、その好適に適用される金属との塩換算で算定されればよい。
(L-3) Oxalatoborate salt: lithium bis (oxalato) borate, lithium difluorooxalatoborate and the like.
Among these, LiPF 6 , LiBF 4 , LiAsF 6 , LiSbF 6 , LiClO 4 , Li (Rf 1 SO 3 ), LiN (Rf 1 SO 2 ) 2 , LiN (FSO 2 ) 2 , and LiN (Rf 1 SO 2 ) (Rf 2 SO 2 ), preferably LiPF 6 , LiBF 4 , LiN (Rf 1 SO 2 ) 2 , LiN (FSO 2 ) 2 , and LiN (Rf 1 SO 2 ) (Rf 2 SO 2 ) More preferred are salts. Here, Rf 1 and Rf 2 each represent a perfluoroalkyl group.
In addition, the electrolyte used for electrolyte solution may be used individually by 1 type, or may combine 2 or more types arbitrarily.
The electrolyte in the electrolytic solution (preferably a metal ion belonging to
(非水溶剤)
本実施形態の電解液に用いられる非水溶剤としては、非プロトン性有機溶媒であることが好ましく、なかでも炭素数2〜10の非プロトン性有機溶媒であることが好ましい。上記非水溶剤は、エーテル基、カルボニル基、エステル基、またはカーボネート基を有する化合物であることが好ましい。上記化合物は置換基を有していてもよい。
(Non-aqueous solvent)
The non-aqueous solvent used in the electrolyte solution of the present embodiment is preferably an aprotic organic solvent, and more preferably an aprotic organic solvent having 2 to 10 carbon atoms. The non-aqueous solvent is preferably a compound having an ether group, a carbonyl group, an ester group, or a carbonate group. The above compound may have a substituent.
非水溶剤としては、例えば、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、エチルメチルカーボネート、メチルプロピルカーボネート、γ−ブチロラクトン、γ−バレロラクトン、1,2−ジメトキシエタン、テトラヒドロフラン、2−メチルテトラヒドロフラン、テトラヒドロピラン、1,3−ジオキソラン、4−メチル−1,3−ジオキソラン、1,3−ジオキサン、1,4−ジオキサン、酢酸メチル、酢酸エチル、プロピオン酸メチル、プロピオン酸エチル、酪酸メチル、イソ酪酸メチル、トリメチル酢酸メチル、トリメチル酢酸エチル、アセトニトリル、グルタロニトリル、アジポニトリル、メトキシアセトニトリル、3−メトキシプロピオニトリル、N,N−ジメチルホルムアミド、N−メチルピロリジノン、N−メチルオキサゾリジノン、N,N’−ジメチルイミダゾリジノン、ニトロメタン、ニトロエタン、スルホラン、燐酸トリメチル、ジメチルスルホキシドあるいはジメチルスルホキシド燐酸などが挙げられる。これらは、一種単独で用いても2種以上を併用してもよい。中でも、エチレンカーボネート、プロピレンカーボネート、ジメチルカーボネート、ジエチルカーボネートおよびエチルメチルカーボネート、γ−ブチロラクトンからなる群のうちの少なくとも1種が好ましく、特に、エチレンカーボネートあるいはプロピレンカーボネートなどの高粘度(高誘電率)溶媒(例えば、比誘電率ε≧30)とジメチルカーボネート、エチルメチルカーボネートあるいはジエチルカーボネートなどの低粘度溶媒(例えば、粘度≦1mPa・s)との組み合わせがより好ましい。電解質塩の解離性およびイオンの移動度が向上するからである。
しかしながら、本発明に用いられる非水溶剤は、上記例示によって限定されるものではない。
Examples of the non-aqueous solvent include ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, γ-butyrolactone, γ-valerolactone, 1,2-dimethoxyethane, tetrahydrofuran, 2 -Methyltetrahydrofuran, tetrahydropyran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,3-dioxane, 1,4-dioxane, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, butyric acid Methyl, methyl isobutyrate, methyl trimethylacetate, ethyl trimethylacetate, acetonitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, 3-methoxypropionitrile, N, Examples thereof include N-dimethylformamide, N-methylpyrrolidinone, N-methyloxazolidinone, N, N′-dimethylimidazolidinone, nitromethane, nitroethane, sulfolane, trimethyl phosphate, dimethyl sulfoxide, and dimethyl sulfoxide phosphoric acid. These may be used alone or in combination of two or more. Among these, at least one member selected from the group consisting of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate, and γ-butyrolactone is preferable. Particularly, a high viscosity (high dielectric constant) solvent such as ethylene carbonate or propylene carbonate. A combination of (for example, relative dielectric constant ε ≧ 30) and a low viscosity solvent (for example, viscosity ≦ 1 mPa · s) such as dimethyl carbonate, ethyl methyl carbonate, or diethyl carbonate is more preferable. This is because the dissociation property of the electrolyte salt and the ion mobility are improved.
However, the non-aqueous solvent used in the present invention is not limited by the above examples.
(電解液の調製方法等)
本発明の非水二次電池用電解液の製造方法は、上記アミノ置換ホスファゼン化合物の製造方法を介して、これを含有する非水二次電池用電解液を調製することにより実施することができる。具体的には、例えば、金属イオンの塩としてリチウム塩を用いた例を含め、上記各成分を上記非水電解液溶媒に溶解して、常法により調製される。
(Electrolyte preparation method etc.)
The manufacturing method of the electrolyte solution for non-aqueous secondary batteries of this invention can be implemented by preparing the electrolyte solution for non-aqueous secondary batteries containing this through the manufacturing method of the said amino substituted phosphazene compound. . Specifically, for example, each component is prepared by a conventional method by dissolving the above components in the non-aqueous electrolyte solvent, including an example in which a lithium salt is used as a metal ion salt.
<非水二次電池>
本発明の非水二次電池の製造方法は、上記非水二次電池用電解液の製造方法を介して、正極と負極と上記非水二次電池用電解液とを具備する電池を作製することで実施することができる。
本発明に係る好ましい実施形態のリチウムイオン二次電池は、上記本発明の非水二次電池用電解液と、リチウムイオンの挿入放出が可能な正極(正極集電体,正極活物質層)と、リチウムイオンの挿入放出又は溶解析出が可能な負極(負極集電体,負極活物質層)とを備える。これら必須の部材に加え、電池が使用される目的、電位の形状などを考慮し、正極と負極の間に配設されるセパレータ、集電端子、及び外装ケース等を含んで構成されてもよい。必要に応じて、電池の内部及び電池の外部の少なくともいずれかに保護素子を装着してもよい。このような構造とすることにより、電解液内でリチウムイオンの授受が生じ、充電、放電を行うことができ、回路配線を介して動作機構を介して運転あるいは蓄電を行うことができる。以下、これらの各部材について述べる。
(電極合材)
電極合材は、集電体(電極基材)上に活物質と導電剤、結着剤、フィラーなどの分散物を塗布したものであり、リチウム電池においては、活物質が正極活物質である正極合材と活物質が負極活物質である負極合材が使用されることが好ましい。次に、電極合材を構成する分散物(電極用組成物)中の各成分等について説明する。
<Non-aqueous secondary battery>
The non-aqueous secondary battery manufacturing method of the present invention produces a battery comprising a positive electrode, a negative electrode, and the non-aqueous secondary battery electrolyte solution via the non-aqueous secondary battery electrolyte manufacturing method. Can be implemented.
A lithium ion secondary battery according to a preferred embodiment of the present invention includes a nonaqueous secondary battery electrolyte according to the present invention and a positive electrode (positive electrode current collector, positive electrode active material layer) capable of inserting and releasing lithium ions. And a negative electrode (negative electrode current collector, negative electrode active material layer) capable of inserting and releasing lithium ions or dissolving and depositing lithium ions. In addition to these essential members, in consideration of the purpose for which the battery is used, the shape of the potential, and the like, the separator may be configured to be disposed between the positive electrode and the negative electrode, a current collecting terminal, and an outer case. . If necessary, a protective element may be attached to at least one of the inside of the battery and the outside of the battery. With such a structure, lithium ions are exchanged in the electrolytic solution, charging and discharging can be performed, and operation or power storage can be performed via the operation mechanism via the circuit wiring. Hereinafter, each of these members will be described.
(Electrode mixture)
The electrode mixture is obtained by applying a dispersion of an active material and a conductive agent, a binder, a filler, etc. on a current collector (electrode substrate). In a lithium battery, the active material is a positive electrode active material. It is preferable to use a negative electrode mixture in which the positive electrode mixture and the active material are a negative electrode active material. Next, each component in the dispersion (electrode composition) constituting the electrode mixture will be described.
・正極活物質
正極活物質にはリチウム含有遷移金属酸化物を用いることが好ましく、中でも、遷移元素Ma(Co、Ni、Fe、Mn、Cu、Vから選択される1種以上の元素)を有することが好ましい。また、混合元素Mb(リチウム以外の金属周期律表の第1(Ia)族の元素、第2(IIa)族の元素、Al、Ga、In、Ge、Sn、Pb、Sb、Bi、Si、P、Bなど)を混合してもよい。この、リチウム含有遷移金属酸化物として例えば、下記式(MA)〜(MC)のいずれかで表されるものを含む特定遷移金属酸化物、あるいはその他の遷移金属酸化物としてV2O5、MnO2等が挙げられる。正極活物質には、粒子状の正極活物質を用いてもよい。具体的に、可逆的にリチウムイオンを挿入・放出できる遷移金属酸化物を用いることができるが、上記特定遷移金属酸化物を用いるのが好ましい。
-Positive electrode active material It is preferable to use a lithium-containing transition metal oxide for the positive electrode active material. Among them, a transition element M a (one or more elements selected from Co, Ni, Fe, Mn, Cu, V) is used. It is preferable to have. Further, mixed element M b (elements of the first (Ia) group of the metal periodic table other than lithium, elements of the second (IIa) group, Al, Ga, In, Ge, Sn, Pb, Sb, Bi, Si , P, B, etc.) may be mixed. As the lithium-containing transition metal oxide, for example, specific transition metal oxides including those represented by any of the following formulas (MA) to (MC), or other transition metal oxides such as V 2 O 5 , MnO 2 etc. are mentioned. As the positive electrode active material, a particulate positive electrode active material may be used. Specifically, a transition metal oxide capable of reversibly inserting and releasing lithium ions can be used, but the specific transition metal oxide is preferably used.
リチウム含有遷移金属酸化物としては、上記遷移元素Maを含む酸化物等が好適に挙げられる。このとき混合元素Mb(好ましくはAl)などを混合してもよい。混合量としては、遷移金属の量に対して0〜30mol%が好ましい。Li/Maのモル比が0.3〜2.2になるように混合して合成されたものが、より好ましい。 Examples of the lithium-containing transition metal oxides, oxides containing the above transition element M a is preferably exemplified. At this time, a mixed element M b (preferably Al) or the like may be mixed. The mixing amount is preferably 0 to 30 mol% with respect to the amount of the transition metal. That the molar ratio of li / M a is synthesized by mixing so that 0.3 to 2.2 is more preferable.
〔式(MA)で表される遷移金属酸化物(層状岩塩型構造)〕
リチウム含有遷移金属酸化物としては中でも下式で表されるものが好ましい。
LiaM1Ob ・・・ (MA)
[Transition metal oxide represented by formula (MA) (layered rock salt structure)]
As the lithium-containing transition metal oxide, those represented by the following formula are preferable.
Li a M 1 O b (MA)
式中、M1は上記Maと同義である。aは0〜1.2を表し、0.1〜1.15であることが好ましく、さらに0.6〜1.1であることが好ましい。bは1〜3を表し、2であることが好ましい。M1の一部は上記混合元素Mbで置換されていてもよい。上記式(MA)で表される遷移金属酸化物は典型的には層状岩塩型構造を有する。
上記遷移金属化合物の具体例を示すと、LiCoO2(コバルト酸リチウム[LCO])、LiNi2O2(ニッケル酸リチウム)LiNi0.85Co0.01Al0.05O2(ニッケルコバルトアルミニウム酸リチウム[NCA])、LiNi0.33Co0.33Mn0.33O2(ニッケルマンガンコバルト酸リチウム[NMC])、LiNi0.5Mn0.5O2(マンガンニッケル酸リチウム)である。
Wherein, M 1 is as defined above Ma. a represents 0 to 1.2, preferably 0.1 to 1.15, and more preferably 0.6 to 1.1. b represents 1-3 and is preferably 2. A part of M 1 may be substituted with the mixed element M b . The transition metal oxide represented by the above formula (MA) typically has a layered rock salt structure.
Specific examples of the transition metal compound include LiCoO 2 (lithium cobaltate [LCO]), LiNi 2 O 2 (lithium nickelate) LiNi 0.85 Co 0.01 Al 0.05 O 2 (nickel cobalt aluminum acid Lithium [NCA]), LiNi 0.33 Co 0.33 Mn 0.33 O 2 (lithium nickel manganese cobaltate [NMC]), LiNi 0.5 Mn 0.5 O 2 (lithium manganese nickelate).
〔式(MB)で表される遷移金属酸化物(スピネル型構造)〕
リチウム含有遷移金属酸化物としては中でも下記式(MB)で表されるものも好ましい。
LicM2 2Od ・・・ (MB)
[Transition metal oxide represented by formula (MB) (spinel structure)]
Among the lithium-containing transition metal oxides, those represented by the following formula (MB) are also preferable.
Li c M 2 2 O d (MB)
式中、M2は上記Maと同義である。cは0〜2を表し、0.1〜1.15であることが好ましく、さらに0.6〜1.5であることが好ましい。dは3〜5を表し、4であることが好ましい。
上記遷移金属化合物の具体例を示すと、LiMn2O4、LiMn1.5Ni0.5O4である。
Wherein, M 2 is as defined above Ma. c represents 0 to 2, preferably 0.1 to 1.15, and more preferably 0.6 to 1.5. d represents 3 to 5 and is preferably 4.
Specific examples of the transition metal compound are LiMn 2 O 4 and LiMn 1.5 Ni 0.5 O 4 .
式(MB)で表される遷移金属酸化物はさらに下記で表されるものも好ましい例として挙げられる。
(a) LiCoMnO4
(b) Li2FeMn3O8
(c) Li2CuMn3O8
(d) Li2CrMn3O8
(e) Li2NiMn3O8
高容量、高出力の観点で上記のうちNiを含む電極が更に好ましい。
Preferred examples of the transition metal oxide represented by the formula (MB) include those represented by the following.
(A) LiCoMnO 4
(B) Li 2 FeMn 3 O 8
(C) Li 2 CuMn 3 O 8
(D) Li 2 CrMn 3 O 8
(E) Li 2 NiMn 3 O 8
Of these, an electrode containing Ni is more preferable from the viewpoint of high capacity and high output.
〔式(MC)で表される遷移金属酸化物〕
リチウム含有遷移金属酸化物としてはリチウム含有遷移金属リン酸化物を用いることも好ましく、中でも下記式(MC)で表されるものも好ましい。
LieM3(PO4)f ・・・ (MC)
[Transition metal oxide represented by formula (MC)]
As the lithium-containing transition metal oxide, it is also preferable to use a lithium-containing transition metal phosphor oxide, and among them, one represented by the following formula (MC) is also preferable.
Li e M 3 (PO 4 ) f ... (MC)
式中、eは0〜2を表し、0.1〜1.15であることが好ましく、さらに0.5〜1.5であることが好ましい。fは1〜5を表し、0.5〜2であることが好ましい。 In the formula, e represents 0 to 2, preferably 0.1 to 1.15, and more preferably 0.5 to 1.5. f represents 1 to 5 and is preferably 0.5 to 2.
上記M3はV、Ti、Cr、Mn、Fe、Co、Ni、Cuから選択される一種以上の元素を表す。上記M3は、上記の混合元素Mbのほか、Ti、Cr、Zn、Zr、Nb等の他の金属で置換していてもよい。具体例としては、例えば、LiFePO4、Li3Fe2(PO4)3等のオリビン型リン酸鉄塩、LiFeP2O7等のピロリン酸鉄類、LiCoPO4等のリン酸コバルト類、Li3V2(PO4)3(リン酸バナジウムリチウム)等の単斜晶ナシコン型リン酸バナジウム塩が挙げられる。
なお、Liの組成を表す上記a,c,e値は、充放電により変化する値であり、典型的には、Liを含有したときの安定な状態の値で評価される。上記式(a)〜(e)では特定値としてLiの組成を示しているが、これも同様に電池の動作により変化するものである。
特に好ましい正極活物質の具体例としては下記が挙げられる。
LiNi0.33Co0.33Mn0.33O2
LiNi0.6Co0.2Mn0.2O2
LiNi0.5Co0.3Mn0.2O2
LiNi0.5Mn0.5O2
LiNi0.5Mn1.5O4
これらは高電位で使用できるため電池容量を大きくすることができ、また高電位で使用しても容量維持率が高いため特に好ましい。
The M 3 represents one or more elements selected from V, Ti, Cr, Mn, Fe, Co, Ni, and Cu. The M 3 are, in addition to the mixing element M b above, Ti, Cr, Zn, Zr, may be substituted by other metals such as Nb. Specific examples include, for example, olivine-type iron phosphates such as LiFePO 4 and Li 3 Fe 2 (PO 4 ) 3 , iron pyrophosphates such as LiFeP 2 O 7 , cobalt phosphates such as LiCoPO 4 , and Li 3. Monoclinic Nasicon type vanadium phosphate salts such as V 2 (PO 4 ) 3 (lithium vanadium phosphate) can be mentioned.
The a, c, e values representing the composition of Li are values that change due to charge / discharge, and are typically evaluated as values in a stable state when Li is contained. In the above formulas (a) to (e), the composition of Li is shown as a specific value, but this also varies depending on the operation of the battery.
Specific examples of particularly preferable positive electrode active materials include the following.
LiNi 0.33 Co 0.33 Mn 0.33 O 2
LiNi 0.6 Co 0.2 Mn 0.2 O 2
LiNi 0.5 Co 0.3 Mn 0.2 O 2
LiNi 0.5 Mn 0.5 O 2
LiNi 0.5 Mn 1.5 O 4
Since these can be used at a high potential, the battery capacity can be increased, and even when used at a high potential, the capacity retention rate is high, which is particularly preferable.
本発明の非水二次電池において、用いられる正極活物質の平均粒子サイズは特に限定されないが、0.1μm〜50μmが好ましい。比表面積としては特に限定されないが、BET法で0.01m2/g〜50m2/gであるのが好ましい。また、正極活物質5gを蒸留水100mlに溶かした時の上澄み液のpHとしては、7以上12以下が好ましい。 In the non-aqueous secondary battery of the present invention, the average particle size of the positive electrode active material used is not particularly limited, but is preferably 0.1 μm to 50 μm. No particular limitation is imposed on the specific surface area, preferably from 0.01m 2 / g~50m 2 / g by the BET method. Further, the pH of the supernatant when 5 g of the positive electrode active material is dissolved in 100 ml of distilled water is preferably 7 or more and 12 or less.
正極活物質の配合量は特に限定されないが、活物質層を構成するための分散物(合剤)中、固形成分100質量%において、60〜98質量%であることが好ましく、70〜95質量%であることがより好ましい。
・負極活物質
負極活物質としては、可逆的にリチウムイオンを挿入・放出できるものが好ましく、特に制限はなく、炭素質材料、酸化錫や酸化ケイ素等の金属酸化物、金属複合酸化物、リチウム単体やリチウムアルミニウム合金等のリチウム合金、及び、SnやSi等のリチウムと合金形成可能な金属等が挙げられる。
これらは、1種を単独で用いても、2種以上を任意の組み合わせ及び比率で併用しても良い。なかでも炭素質材料又はリチウム複合酸化物が信頼性の点から好ましく用いられる。
また、金属複合酸化物としては、リチウムを吸蔵、放出可能であるものが好ましく、構成成分としてチタン及び/又はリチウムを含有していることが、高電流密度充放電特性の観点で好ましい。
Although the compounding quantity of a positive electrode active material is not specifically limited, In the dispersion (mixture) for comprising an active material layer, it is preferable that it is 60-98 mass% in 100 mass% of solid components, and is 70-95 mass. % Is more preferable.
・ Negative electrode active material As the negative electrode active material, those capable of reversibly inserting and releasing lithium ions are preferable, and there is no particular limitation. Carbonaceous materials, metal oxides such as tin oxide and silicon oxide, metal composite oxides, lithium Examples thereof include a single alloy and a lithium alloy such as a lithium aluminum alloy, and a metal capable of forming an alloy with lithium such as Sn and Si.
These may be used individually by 1 type, or may use 2 or more types together by arbitrary combinations and a ratio. Of these, carbonaceous materials or lithium composite oxides are preferably used from the viewpoint of reliability.
Moreover, as a metal complex oxide, what can occlude and discharge | release lithium is preferable, and it is preferable from a viewpoint of a high current density charge / discharge characteristic that it contains titanium and / or lithium as a structural component.
負極活物質として用いられる炭素質材料とは、実質的に炭素からなる材料である。例えば、石油ピッチ、天然黒鉛、気相成長黒鉛等の人造黒鉛、及びポリアクリロニトリル系の樹脂やフルフリルアルコール樹脂等の各種の合成樹脂を焼成した炭素質材料を挙げることができる。さらに、ポリアクリロニトリル系炭素繊維、セルロース系炭素繊維、ピッチ系炭素繊維、気相成長炭素繊維、脱水ポリビニルアルコール系炭素繊維、リグニン炭素繊維、ガラス状炭素繊維、活性炭素繊維等の各種炭素繊維類、メソフェーズ微小球体、グラファイトウィスカー、平板状の黒鉛等を挙げることもできる。
金属酸化物及び金属複合酸化物としては、特に非晶質酸化物が好ましく、さらに金属元素と周期律表第16族の元素との反応生成物であるカルコゲナイトも好ましく用いられる。好ましい非晶質酸化物及びカルコゲナイドの具体例としては、例えば、Ga2O3、SiO、GeO、SnO、SnO2、PbO、PbO2、Pb2O3、Pb2O4、Pb3O4、Sb2O3、Sb2O4、Sb2O5、Bi2O3、Bi2O4、SnSiO3、GeS、SnS、SnS2、PbS、PbS2、Sb2S3、Sb2S5、SnSiS3などが好ましく挙げられる。また、これらは、酸化リチウムとの複合酸化物、例えば、Li2SnO2であってもよい。
The carbonaceous material used as the negative electrode active material is a material substantially made of carbon. Examples thereof include carbonaceous materials obtained by firing artificial graphite such as petroleum pitch, natural graphite, and vapor-grown graphite, and various synthetic resins such as polyacrylonitrile resin and furfuryl alcohol resin. Furthermore, various carbon fibers such as polyacrylonitrile-based carbon fiber, cellulose-based carbon fiber, pitch-based carbon fiber, vapor-grown carbon fiber, dehydrated polyvinyl alcohol-based carbon fiber, lignin carbon fiber, glassy carbon fiber, activated carbon fiber, Examples thereof include mesophase microspheres, graphite whiskers, and flat graphite.
As the metal oxide and metal complex oxide, amorphous oxide is particularly preferable, and chalcogenite, which is a reaction product of a metal element and an element of Group 16 of the periodic table, is also preferably used. Specific examples of preferable amorphous oxides and chalcogenides include, for example, Ga 2 O 3 , SiO, GeO, SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 2 O 4 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 , Bi 2 O 3 , Bi 2 O 4 , SnSiO 3 , GeS, SnS, SnS 2 , PbS, PbS 2 , Sb 2 S 3 , Sb 2 S 5 , such as SnSiS 3 may preferably be mentioned. Moreover, these may be a complex oxide with lithium oxide, for example, Li 2 SnO 2 .
上記負極活物質の平均粒子サイズは、0.1μm〜60μmが好ましい。 The average particle size of the negative electrode active material is preferably 0.1 μm to 60 μm.
Sn、Si、Geを中心とする非晶質酸化物負極活物質に併せて用いることができる負極活物質としては、リチウムイオン又はリチウム金属を吸蔵・放出できる炭素材料や、リチウム、リチウム合金、リチウムと合金可能な金属が好適に挙げられる。 Examples of the negative electrode active material that can be used in combination with the amorphous oxide negative electrode active material centering on Sn, Si, and Ge include carbon materials that can occlude and release lithium ions or lithium metal, lithium, lithium alloys, lithium A metal that can be alloyed with is preferable.
電極合材をなす分散物(合剤)中、負極活物質の配合量は特に限定されないが、固形成分100質量%において60〜98質量%であることが好ましく、70〜95質量%であることがより好ましい。 Although the compounding quantity of a negative electrode active material is not specifically limited in the dispersion (mixture) which comprises an electrode compound material, It is preferable that it is 60-98 mass% in 100 mass% of solid components, and it is 70-95 mass%. Is more preferable.
・導電材
導電材は、構成された二次電池において、化学変化を起こさない電子伝導性材料が好ましく、公知の導電材を任意に用いることができる。通常、天然黒鉛(鱗状黒鉛、鱗片状黒鉛、土状黒鉛など)、人工黒鉛、カーボンブラック、アセチレンブラック、ケッチェンブラック、炭素繊維や金属粉(銅、ニッケル、アルミニウム、銀(特開昭63−10148,554号に記載)等)、金属繊維あるいはポリフェニレン誘導体(特開昭59−20,971号に記載)などの導電性材料を1種又はこれらの混合物として含ませることができる。その中でも、黒鉛とアセチレンブラックの併用がとくに好ましい。上記導電材の添加量としては、1〜50質量%が好ましく、2〜30質量%がより好ましい。カーボンや黒鉛の場合は、2〜15質量%が特に好ましい。
-Conductive material The conductive material is preferably an electron conductive material that does not cause a chemical change in the configured secondary battery, and a known conductive material can be arbitrarily used. Usually, natural graphite (scale-like graphite, scale-like graphite, earth-like graphite, etc.), artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber and metal powder (copper, nickel, aluminum, silver (Japanese Patent Laid-Open No. Sho 63- 10148,554)), metal fibers or polyphenylene derivatives (described in JP-A-59-20971) can be contained as a single type or a mixture thereof. Among these, the combined use of graphite and acetylene black is particularly preferable. As addition amount of the said electrically conductive material, 1-50 mass% is preferable and 2-30 mass% is more preferable. In the case of carbon or graphite, 2 to 15% by mass is particularly preferable.
・結着剤
結着剤としては、多糖類、熱可塑性樹脂及びゴム弾性を有するポリマーなどが挙げられ、その中でも、ポリアクリル酸エステル系のラテックス、カルボキシメチルセルロース、ポリテトラフロロエチレン、ポリフッ化ビニリデンが、より好ましい。
-Binders Examples of binders include polysaccharides, thermoplastic resins, and polymers having rubber elasticity. Among them, polyacrylate ester latex, carboxymethylcellulose, polytetrafluoroethylene, and polyvinylidene fluoride are included. More preferable.
結着剤は、一種単独又は二種以上を混合して用いることができる。結着剤の添加量が少ないと、電極合剤の保持力・凝集力が弱くなる。多すぎると電極体積が増加し電極単位体積あるいは単位質量あたりの容量が減少する。このような理由で結着剤の添加量は1〜30質量%が好ましく、2〜10質量%がより好ましい。 A binder can be used individually by 1 type or in mixture of 2 or more types. When the amount of the binder added is small, the holding power and cohesive force of the electrode mixture are weakened. If the amount is too large, the electrode volume increases and the capacity per electrode unit volume or unit mass decreases. For this reason, the addition amount of the binder is preferably 1 to 30% by mass, and more preferably 2 to 10% by mass.
・フィラー
電極合材は、フィラーを含んでいてもよい。フィラーを形成する材料は、本発明の二次電池において、化学変化を起こさない繊維状材料が好ましい。通常、ポリプロピレン、ポリエチレンなどのオレフィン系ポリマー、ガラス、炭素などの材料からなる繊維状のフィラーが用いられる。フィラーの添加量は特に限定されないが、分散物中、0〜30質量%が好ましい。
-Filler The electrode compound material may contain the filler. The material forming the filler is preferably a fibrous material that does not cause a chemical change in the secondary battery of the present invention. Usually, fibrous fillers made of materials such as olefin polymers such as polypropylene and polyethylene, glass, and carbon are used. Although the addition amount of a filler is not specifically limited, 0-30 mass% is preferable in a dispersion.
・集電体
正・負極の集電体としては、本発明の非水電解質二次電池において化学変化を起こさない電子伝導体が用いられる。正極の集電体としては、アルミニウム、ステンレス鋼、ニッケル、チタンなどの他にアルミニウムやステンレス鋼の表面にカーボン、ニッケル、チタンあるいは銀を処理させたものが好ましく、その中でも、アルミニウムやステンレス鋼の表面にカーボン、ニッケル、チタンあるいは銀を処理させたものが好ましい。
-Current collector As the positive / negative electrode current collector, an electron conductor that does not cause a chemical change in the nonaqueous electrolyte secondary battery of the present invention is used. As the current collector for the positive electrode, in addition to aluminum, stainless steel, nickel, titanium and the like, those obtained by treating the surface of aluminum or stainless steel with carbon, nickel, titanium or silver are preferable. Those whose surfaces are treated with carbon, nickel, titanium or silver are preferred.
負極の集電体としては、アルミニウム、銅、銅合金、ステンレス鋼、ニッケル、チタンが好ましく、アルミニウム、銅、銅合金がより好ましい。 As the negative electrode current collector, aluminum, copper, copper alloy, stainless steel, nickel, and titanium are preferable, and aluminum, copper, and copper alloy are more preferable.
上記集電体の形状としては、通常フィルムシート状のものが使用されるが、ネット、パンチされたもの、ラス体、多孔質体、発泡体、繊維群の成形体なども用いることができる。上記集電体の厚みとしては、特に限定されないが、1μm〜500μmが好ましい。また、集電体表面は、表面処理により凹凸を付けることも好ましい。
これらの材料から適宜選択した部材によりリチウム二次電池の電極合材が形成される。
As the shape of the current collector, a film sheet shape is usually used, but a net, a punched material, a lath body, a porous body, a foamed body, a molded body of a fiber group, and the like can also be used. Although it does not specifically limit as thickness of the said electrical power collector, 1 micrometer-500 micrometers are preferable. Moreover, it is also preferable that the current collector surface is roughened by surface treatment.
An electrode mixture of the lithium secondary battery is formed by a member appropriately selected from these materials.
(セパレータ)
本発明の非水二次電池に用いられるセパレータは、正極と負極を電子的に絶縁する機械的強度、イオン透過性、及び正極と負極の接触面で酸化・還元耐性のある材料で構成されていることが好ましい。このような材料として多孔質のポリマー材料や無機材料、有機無機ハイブリッド材料、あるいはガラス繊維などが用いられる。これらセパレータは信頼性確保のためのシャットダウン機能、すなわち、80℃以上で隙間を閉塞して抵抗を上げ、電流を遮断する機能を持つことが好ましく、閉塞温度は90℃以上、180℃以下であることが好ましい。
(Separator)
The separator used in the non-aqueous secondary battery of the present invention is made of a material that mechanically insulates the positive electrode and the negative electrode, has ion permeability, and has oxidation / reduction resistance at the contact surface between the positive electrode and the negative electrode. Preferably it is. As such a material, a porous polymer material, an inorganic material, an organic-inorganic hybrid material, glass fiber, or the like is used. These separators preferably have a shutdown function for ensuring reliability, that is, a function of closing a gap at 80 ° C. or higher to increase resistance and blocking current, and a closing temperature is 90 ° C. or higher and 180 ° C. or lower. It is preferable.
上記セパレータの孔の形状は、通常は円形や楕円形で、大きさは0.05μm〜30μmであり、0.1μm〜20μmが好ましい。さらに延伸法、相分離法で作った場合のように、棒状や不定形の孔であってもよい。これらの隙間の占める比率すなわち気孔率は、20%〜90%であり、35%〜80%が好ましい。 The shape of the holes of the separator is usually a circle or an ellipse, and the size is 0.05 μm to 30 μm, preferably 0.1 μm to 20 μm. Furthermore, it may be a rod-like or irregular-shaped hole as in the case of making by a stretching method or a phase separation method. The ratio of these gaps, that is, the porosity, is 20% to 90%, preferably 35% to 80%.
上記ポリマー材料としては、セルロース不織布、ポリエチレン、ポリプロピレンなどの単一の材料を用いたものでも、2種以上の複合化材料を用いたものであってもよい。孔径、気孔率や孔の閉塞温度などを変えた2種以上の微多孔フィルムを積層したものが、好ましい。 As said polymer material, the thing using a single material, such as a cellulose nonwoven fabric, polyethylene, a polypropylene, or a composite material of 2 or more types may be used. What laminated | stacked the 2 or more types of microporous film which changed the hole diameter, the porosity, the obstruction | occlusion temperature of a hole, etc. is preferable.
上記無機材料としては、アルミナや二酸化珪素等の酸化物類、窒化アルミや窒化珪素等の窒化物類、硫酸バリウムや硫酸カルシウム等の硫酸塩類が用いられ、粒子形状もしくは繊維形状のものが用いられる。形態としては、不織布、織布、微多孔性フィルム等の薄膜形状のものが用いられる。薄膜形状では、孔径が0.01μm〜1μm、厚さが5μm〜50μmのものが好適に用いられる。上記の独立した薄膜形状以外に、上記無機物の粒子を含有する複合多孔層を樹脂製の結着剤を用いて正極及び/又は負極の表層に形成させてなるセパレータを用いることができる。例えば、正極の両面に90%粒径が1μm未満のアルミナ粒子をフッ素樹脂の結着剤を用いて多孔層として形成させることが挙げられる。 Examples of the inorganic material include oxides such as alumina and silicon dioxide, nitrides such as aluminum nitride and silicon nitride, and sulfates such as barium sulfate and calcium sulfate, and those having a particle shape or fiber shape are used. . As the form, a thin film shape such as a non-woven fabric, a woven fabric, or a microporous film is used. In the thin film shape, those having a pore diameter of 0.01 μm to 1 μm and a thickness of 5 μm to 50 μm are preferably used. In addition to the above-described independent thin film shape, a separator formed by forming a composite porous layer containing the inorganic particles on the surface layer of the positive electrode and / or the negative electrode using a resin binder can be used. For example, alumina particles having a 90% particle diameter of less than 1 μm are formed on both surfaces of the positive electrode as a porous layer using a fluororesin binder.
(非水二次電池の作製)
本発明の非水二次電池の形状としては、シート状、角型、シリンダー状などいずれの形にも適用できる。正極活物質や負極活物質の合剤は、集電体の上に、塗布(コート)、乾燥、圧縮されて、主に用いられる。各部材の選択や設計、これらの組み立ては定法によればよく、この種の製品の一般的な技術を適宜適用することができる。
(Production of non-aqueous secondary battery)
The shape of the nonaqueous secondary battery of the present invention can be applied to any shape such as a sheet shape, a square shape, and a cylinder shape. A positive electrode active material or a mixture of negative electrode active materials is mainly used after being applied (coated), dried and compressed on a current collector. The selection and design of each member and the assembly thereof may be performed by a regular method, and general techniques of this type of product can be applied as appropriate.
以下に、本発明を実施例により詳細に説明するが、本発明はこれらにより限定して解釈されるものではない。 EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention should not be construed as being limited thereto.
<実施例1>
窒素フロー下、500mL三口フラスコに、ヘキサフルオロホスファゼン(東京化成社品)40.0g(0.16mol)、アセトニトリル200mLを仕込み、氷/メタノール浴で冷やしながら塩化アルミニウム21.33g(0.16mol)を少量ずつ添加した。次に、−10℃〜0℃にてジメチルアミンガス(Aldrich社製)21.64g(0.48mol)を0.3g/minの速度でバブリングした。
次に、内温45〜50℃に加熱しながら2時間反応を行った。反応の進行状態を、内標にモノフッ化ベンゼンを用いて19F−NMRにて確認したところ、反応転換率99%であり、二置換体は確認されなかった。そのNMRスペクトルを図1に示す。
反応終了後、分液や減圧蒸留精製により、無色透明の化合物(1−1)39.46g、収率90%で得た。化合物(1−1)の1H、19F−NMRスペクトルを図3(図3−1、図3−2)に示す。また、純度をガスクロマトグラフィーで確認したところ、純度99.99%以上であった。
<Example 1>
In a 500 mL three-necked flask under nitrogen flow, 40.0 g (0.16 mol) of hexafluorophosphazene (product of Tokyo Chemical Industry Co., Ltd.) and 200 mL of acetonitrile were charged, and 21.33 g (0.16 mol) of aluminum chloride was cooled while cooling in an ice / methanol bath. Small portions were added. Next, 21.64 g (0.48 mol) of dimethylamine gas (manufactured by Aldrich) was bubbled at a rate of 0.3 g / min at −10 ° C. to 0 ° C.
Next, reaction was performed for 2 hours, heating to 45-50 degreeC of internal temperature. When the progress of the reaction was confirmed by 19F-NMR using monofluorinated benzene as the internal standard, the reaction conversion rate was 99%, and no disubstituted product was confirmed. The NMR spectrum is shown in FIG.
After completion of the reaction, 39.46 g of a colorless and transparent compound (1-1) was obtained with a yield of 90% by liquid separation or vacuum distillation purification. 1H and 19F-NMR spectra of the compound (1-1) are shown in FIG. 3 (FIGS. 3-1 and 3-2). Further, when the purity was confirmed by gas chromatography, the purity was 99.99% or more.
<実施例2>
窒素フロー下、500mL三口フラスコに、ヘキサフルオロホスファゼン(東京化成社品)40.0g(0.16mol)、アセトニトリル200mLを仕込み、氷浴で冷やしながら塩化マグネシウム15.23g(0.16mol)を少量ずつ添加した。次に、0℃〜5℃にてジメチルアミンガス(Aldrich社製)21.64g(0.48mol)を0.3g/minの速度でバブリングした。
次に、内温45〜50℃に加熱しながら2時間反応を行った。反応の進行状態を、内標にモノフッ化ベンゼンを用いて19F−NMRにて確認したところ、反応転換率95%であり、二置換体は確認されなかった。
反応終了後、分液や減圧蒸留精製により、無色透明の化合物(1−1)38.58g、収率88%で得た。また、純度をガスクロマトグラフィーで確認したところ、純度99.99%以上であった。
<Example 2>
Under a nitrogen flow, 40.0 g (0.16 mol) of hexafluorophosphazene (product of Tokyo Chemical Industry Co., Ltd.) and 200 mL of acetonitrile are charged into a 500 mL three-necked flask, and 15.23 g (0.16 mol) of magnesium chloride is added little by little while cooling in an ice bath. Added. Next, 21.64 g (0.48 mol) of dimethylamine gas (manufactured by Aldrich) was bubbled at a rate of 0.3 g / min at 0 ° C. to 5 ° C.
Next, reaction was performed for 2 hours, heating to 45-50 degreeC of internal temperature. When the progress of the reaction was confirmed by 19F-NMR using monofluorinated benzene as an internal standard, the reaction conversion rate was 95%, and no disubstituted product was confirmed.
After completion of the reaction, 38.58 g of a colorless and transparent compound (1-1) was obtained with a yield of 88% by liquid separation or vacuum distillation purification. Further, when the purity was confirmed by gas chromatography, the purity was 99.99% or more.
<実施例3>
窒素フロー下、500mL三口フラスコに、ヘキサフルオロホスファゼン(東京化成社品)40.0g(0.16mol)、アセトニトリル200mLを仕込み、氷/メタノール浴で冷やしながら三塩化鉄(III)29.95g(0.16mol)を少量ずつ添加した。−10℃〜0℃にてジエチルアミン(和光純薬社品)35.11g(0.48mol)を滴下した。
次に、内温45〜50℃に加熱しながら2時間反応を行った。
反応終了後、分液や減圧蒸留精製により、無色透明の化合物(1−3)41.08g、収率85%で得た。化合物(1−3)の1H、19F−NMRスペクトルを図4(図4−1、図4−2)に示す。また、純度をガスクロマトグラフィーで確認したところ、純度99.99%以上であった。
<Example 3>
In a 500 mL three-necked flask under nitrogen flow, 40.0 g (0.16 mol) of hexafluorophosphazene (product of Tokyo Chemical Industry Co., Ltd.) and 200 mL of acetonitrile were charged, and 29.95 g (0) of iron (III) trichloride was cooled in an ice / methanol bath. .16 mol) was added in small portions. At −10 ° C. to 0 ° C., 35.11 g (0.48 mol) of diethylamine (Wako Pure Chemical Industries, Ltd.) was added dropwise.
Next, reaction was performed for 2 hours, heating to 45-50 degreeC of internal temperature.
After completion of the reaction, 41.08 g of colorless and transparent compound (1-3) was obtained with a yield of 85% by liquid separation or vacuum distillation purification. 1H and 19F-NMR spectra of the compound (1-3) are shown in FIG. 4 (FIGS. 4-1 and 4-2). Further, when the purity was confirmed by gas chromatography, the purity was 99.99% or more.
<実施例4>
窒素フロー下、500mL三口フラスコに、ヘキサフルオロホスファゼン(東京化成社品)40.0g(0.16mol)、アセトニトリル200mLを仕込み、氷浴で冷やしながら臭化リチウム13.90g(0.16mol)を少量ずつ添加した。次に、0℃〜5℃にてジメチルアミンガス(Aldrich社製)14.43g(0.32mol)を0.3g/minの速度でバブリングした。
次に、内温45〜50℃に加熱しながら2時間反応を行った。反応の進行状態を、内標にモノフッ化ベンゼンを用いて19F−NMRにて確認したところ、反応転換率96%であり、二置換体は確認されなかった。
反応終了後、分液や減圧蒸留精製により、無色透明の化合物(1−1)38.49g、収率88%で得た。また、純度をガスクロマトグラフィーで確認したところ、純度99.99%以上であった。
<Example 4>
Under a nitrogen flow, 40.0 g (0.16 mol) of hexafluorophosphazene (product of Tokyo Chemical Industry Co., Ltd.) and 200 mL of acetonitrile are charged into a 500 mL three-necked flask, and a small amount of 13.90 g (0.16 mol) of lithium bromide is cooled in an ice bath. Added in increments. Next, 14.43 g (0.32 mol) of dimethylamine gas (manufactured by Aldrich) was bubbled at a rate of 0.3 g / min at 0 to 5 ° C.
Next, reaction was performed for 2 hours, heating to 45-50 degreeC of internal temperature. When the progress of the reaction was confirmed by 19F-NMR using monofluorinated benzene as an internal standard, the reaction conversion rate was 96%, and no disubstituted product was confirmed.
After completion of the reaction, 38.49 g of a colorless and transparent compound (1-1) was obtained with a yield of 88% by liquid separation or vacuum distillation purification. Further, when the purity was confirmed by gas chromatography, the purity was 99.99% or more.
<実施例5>
窒素フロー下、500mL三口フラスコに、ヘキサフルオロホスファゼン(東京化成社品)40.0g(0.16mol)、アセトニトリル200mLを仕込み、氷浴で冷やしながらジクロロジメチルシラン10.4g(0.08mol)を少量ずつ添加した。次に、0℃〜5℃にてジメチルアミンガス(Aldrich社製)14.43g(0.32mol)を0.3g/minの速度でバブリングした。
次に、内温を5℃以下に保ちながら0.5時間反応を行った。反応の進行状態を、内標にモノフッ化ベンゼンを用いて19F−NMRにて確認したところ、反応転換率89%であり、二置換体は確認されなかった。
反応終了後、分液や減圧蒸留精製により、無色透明の化合物(1−1)34.63g、収率79%で得た。また、純度をガスクロマトグラフィーで確認したところ、純度99.89%であった。
<Example 5>
In a 500 mL three-necked flask under nitrogen flow, 40.0 g (0.16 mol) of hexafluorophosphazene (product of Tokyo Chemical Industry Co., Ltd.) and 200 mL of acetonitrile are charged, and 10.4 g (0.08 mol) of dichlorodimethylsilane is cooled in an ice bath. Added in increments. Next, 14.43 g (0.32 mol) of dimethylamine gas (manufactured by Aldrich) was bubbled at a rate of 0.3 g / min at 0 to 5 ° C.
Next, the reaction was carried out for 0.5 hours while maintaining the internal temperature at 5 ° C. or lower. When the progress of the reaction was confirmed by 19F-NMR using monofluorinated benzene as an internal standard, the reaction conversion rate was 89%, and no disubstituted product was confirmed.
After completion of the reaction, 34.63 g of colorless and transparent compound (1-1) was obtained with a yield of 79% by liquid separation or vacuum distillation purification. Further, when the purity was confirmed by gas chromatography, the purity was 99.89%.
<実施例6>
窒素フロー下、500mL三口フラスコに、ヘキサフルオロホスファゼン(東京化成社品)40.0g(0.16mol)、アセトニトリル200mLを仕込み、氷/メタノール浴で冷やしながら塩化銅(II)21.51g(0.16mol)を少量ずつ添加した。次に、−10℃〜0℃にてジメチルアミンガス(Aldrich社製)21.64g(0.48mol)を0.3g/minの速度でバブリングした。
次に、内温45〜50℃に加熱しながら2時間反応を行った。反応の進行状態を、内標にモノフッ化ベンゼンを用いて19F−NMRにて確認したところ、反応転換率94%であり、二置換体は確認されなかった。
反応終了後、分液や減圧蒸留精製により、無色透明の化合物(1−1)39.00g、収率89%で得た。また、純度をガスクロマトグラフィーで確認したところ、純度99.99%以上であった。
<Example 6>
Under a nitrogen flow, 40.0 g (0.16 mol) of hexafluorophosphazene (manufactured by Tokyo Chemical Industry Co., Ltd.) and 200 mL of acetonitrile were charged into a 500 mL three-necked flask and cooled with an ice / methanol bath, 21.51 g of copper chloride (II). 16 mol) was added in small portions. Next, 21.64 g (0.48 mol) of dimethylamine gas (manufactured by Aldrich) was bubbled at a rate of 0.3 g / min at −10 ° C. to 0 ° C.
Next, reaction was performed for 2 hours, heating to 45-50 degreeC of internal temperature. When the progress of the reaction was confirmed by 19F-NMR using monofluorinated benzene as an internal standard, the reaction conversion rate was 94%, and no disubstituted product was confirmed.
After completion of the reaction, 39.00 g of colorless and transparent compound (1-1) was obtained in 89% yield by liquid separation or vacuum distillation purification. Further, when the purity was confirmed by gas chromatography, the purity was 99.99% or more.
<実施例7>
実施例6の塩化銅(II)を三塩化ホウ素に代えて反応を行ったところ、同様に高い反応転換率で化合物(1−1)を得た。
<Example 7>
When the reaction was carried out by replacing the copper (II) chloride of Example 6 with boron trichloride, the compound (1-1) was similarly obtained at a high reaction conversion rate.
<実施例8>
窒素フロー下、500mL三口フラスコに、ヘキサフルオロホスファゼン(東京化成社品)40.0g(0.16mol)、アセトニトリル200mLを仕込み、氷浴で冷やしながらトリメチルクロロシラン17.38g(0.08mol)を少量ずつ添加した。次に、0℃〜5℃にてジメチルアミンガス(Aldrich社製)14.43g(0.32mol)を0.3g/minの速度でバブリングした。
次に、内温を5℃以下に保ちながら0.5時間反応を行った。反応の進行状態を、内標にモノフッ化ベンゼンを用いて19F−NMRにて確認したところ、反応転換率88%であり、二置換体は確認されなかった。
反応終了後、分液や減圧蒸留精製により、無色透明の化合物(1−1)34.81g、収率79%で得た。また、純度をガスクロマトグラフィーで確認したところ、純度99.85%であった。
<Example 8>
In a 500 mL three-necked flask under nitrogen flow, 40.0 g (0.16 mol) of hexafluorophosphazene (product of Tokyo Chemical Industry Co., Ltd.) and 200 mL of acetonitrile are charged, and 17.38 g (0.08 mol) of trimethylchlorosilane is added little by little while cooling in an ice bath. Added. Next, 14.43 g (0.32 mol) of dimethylamine gas (manufactured by Aldrich) was bubbled at a rate of 0.3 g / min at 0 to 5 ° C.
Next, the reaction was carried out for 0.5 hours while maintaining the internal temperature at 5 ° C. or lower. When the progress of the reaction was confirmed by 19F-NMR using monofluorinated benzene as an internal standard, the reaction conversion rate was 88%, and no disubstituted product was confirmed.
After completion of the reaction, 34.81 g of colorless and transparent compound (1-1) was obtained with a yield of 79% by liquid separation or vacuum distillation purification. Further, when the purity was confirmed by gas chromatography, the purity was 99.85%.
<実施例9>
窒素フロー下、500mL三口フラスコに、ヘキサフルオロホスファゼン(東京化成社品)40.0g(0.16mol)、アセトニトリル42mLを仕込み、氷/メタノール浴で冷やしながら塩化アルミニウム7.11g(0.053mol)を少量ずつ添加した。次に、−10℃〜0℃にてジメチルアミンガス(Aldrich社製)14.43g(0.32mol)を0.3g/minの速度でバブリングした。
次に、内温45〜50℃に加熱しながら2時間反応を行った。反応の進行状態を、内標にモノフッ化ベンゼンを用いて19F−NMRにて確認したところ、反応転換率98%であり、二置換体は確認されなかった。
反応終了後、分液や減圧蒸留精製により、無色透明の化合物(1−1)38.23g、収率87%で得た。また、純度をガスクロマトグラフィーで確認したところ、純度99.99%以上であった。
<Example 9>
In a 500 mL three-necked flask under nitrogen flow, 40.0 g (0.16 mol) of hexafluorophosphazene (product of Tokyo Chemical Industry Co., Ltd.) and 42 mL of acetonitrile were charged, and 7.11 g (0.053 mol) of aluminum chloride was cooled while cooling in an ice / methanol bath. Small portions were added. Next, 14.43 g (0.32 mol) of dimethylamine gas (manufactured by Aldrich) was bubbled at a rate of 0.3 g / min at −10 ° C. to 0 ° C.
Next, reaction was performed for 2 hours, heating to 45-50 degreeC of internal temperature. When the progress of the reaction was confirmed by 19F-NMR using monofluorinated benzene as the internal standard, the reaction conversion rate was 98%, and no disubstituted product was confirmed.
After completion of the reaction, 38.23 g of colorless and transparent compound (1-1) was obtained with a yield of 87% by liquid separation or vacuum distillation purification. Further, when the purity was confirmed by gas chromatography, the purity was 99.99% or more.
<実施例10>
窒素フロー下、500mL三口フラスコに、ヘキサフルオロホスファゼン(東京化成社品)40.0g(0.16mol)、アセトニトリル42mLを仕込み、氷浴で冷やしながら塩化マグネシウム7.65g(0.08mol)を少量ずつ添加した。次に、0℃〜5℃にてジメチルアミンガス(Aldrich社製)14.43g(0.32mol)を0.3g/minの速度でバブリングした。
次に、内温0℃に保ったまま1時間反応を行った。反応の進行状態を、内標にモノフッ化ベンゼンを用いて19F−NMRにて確認したところ、反応転換率97%であり、二置換体は確認されなかった。
反応終了後、分液や減圧蒸留精製により、無色透明の化合物(1−1)39.76g、収率91%で得た。また、純度をガスクロマトグラフィーで確認したところ、純度99.99%以上であった。
<Example 10>
In a 500 mL three-necked flask under nitrogen flow, 40.0 g (0.16 mol) of hexafluorophosphazene (product of Tokyo Chemical Industry Co., Ltd.) and 42 mL of acetonitrile were charged, and 7.65 g (0.08 mol) of magnesium chloride was added in small portions while cooling in an ice bath. Added. Next, 14.43 g (0.32 mol) of dimethylamine gas (manufactured by Aldrich) was bubbled at a rate of 0.3 g / min at 0 to 5 ° C.
Next, the reaction was carried out for 1 hour while maintaining the internal temperature at 0 ° C. When the progress of the reaction was confirmed by 19F-NMR using monofluorinated benzene as the internal standard, the reaction conversion rate was 97%, and no disubstituted product was confirmed.
After completion of the reaction, 39.76 g of colorless and transparent compound (1-1) was obtained with a yield of 91% by liquid separation or vacuum distillation purification. Further, when the purity was confirmed by gas chromatography, the purity was 99.99% or more.
<実施例11>
窒素フロー下、500mL三口フラスコに、ヘキサフルオロホスファゼン(東京化成社品)40.0g(0.16mol)、アセトニトリル42mLを仕込み、氷/メタノール浴で冷やしながら臭化リチウム13.90g(0.16mol)を少量ずつ添加した。次に、−10℃〜0℃にてジメチルアミンガス(Aldrich社製)14.43g(0.32mol)を0.3g/minの速度でバブリングした。
次に、内温−10℃に保ったまま1時間反応を行った。反応の進行状態を、内標にモノフッ化ベンゼンを用いて19F−NMRにて確認したところ、反応転換率95%であり、二置換体は確認されなかった。
反応終了後、分液や減圧蒸留精製により、無色透明の化合物(1−1)38.93g、収率89%で得た。また、純度をガスクロマトグラフィーで確認したところ、純度99.99%以上であった。
<Example 11>
Under a nitrogen flow, 40.0 g (0.16 mol) of hexafluorophosphazene (product of Tokyo Chemical Industry Co., Ltd.) and 42 mL of acetonitrile are charged into a 500 mL three-necked flask and cooled in an ice / methanol bath, 13.90 g (0.16 mol) of lithium bromide. Was added in small portions. Next, 14.43 g (0.32 mol) of dimethylamine gas (manufactured by Aldrich) was bubbled at a rate of 0.3 g / min at −10 ° C. to 0 ° C.
Next, the reaction was carried out for 1 hour while maintaining the internal temperature at -10 ° C. When the progress of the reaction was confirmed by 19F-NMR using monofluorinated benzene as an internal standard, the reaction conversion rate was 95%, and no disubstituted product was confirmed.
After completion of the reaction, 38.93 g of colorless and transparent compound (1-1) was obtained with a yield of 89% by liquid separation or vacuum distillation purification. Further, when the purity was confirmed by gas chromatography, the purity was 99.99% or more.
<実施例12>
窒素フロー下、500mL三口フラスコに、ヘキサフルオロホスファゼン(東京化成社品)40.0g(0.16mol)、アセトニトリル42mLを仕込み、氷浴で冷やしながら塩化マグネシウム7.65g(0.08mol)を少量ずつ添加した。次に、0℃〜5℃にてモノメチルアミンガス9.93g(0.32mol)を0.3g/minの速度でバブリングした。
次に、内温0℃に保ったまま1時間反応を行った。反応の進行状態を、内標にモノフッ化ベンゼンを用いて19F−NMRにて確認したところ、反応転換率95%であり、二置換体は確認されなかった。
反応終了後、分液や減圧蒸留精製により、無色透明の化合物(1−9)37.00g、収率89%で得た。また、純度をガスクロマトグラフィーで確認したところ、純度99.99%以上であった。
<Example 12>
In a 500 mL three-necked flask under nitrogen flow, 40.0 g (0.16 mol) of hexafluorophosphazene (product of Tokyo Chemical Industry Co., Ltd.) and 42 mL of acetonitrile were charged, and 7.65 g (0.08 mol) of magnesium chloride was added in small portions while cooling in an ice bath. Added. Next, 9.93 g (0.32 mol) of monomethylamine gas was bubbled at a rate of 0.3 g / min at 0 ° C. to 5 ° C.
Next, the reaction was carried out for 1 hour while maintaining the internal temperature at 0 ° C. When the progress of the reaction was confirmed by 19F-NMR using monofluorinated benzene as an internal standard, the reaction conversion rate was 95%, and no disubstituted product was confirmed.
After completion of the reaction, 37.00 g of colorless and transparent compound (1-9) was obtained with a yield of 89% by liquid separation or vacuum distillation purification. Further, when the purity was confirmed by gas chromatography, the purity was 99.99% or more.
<実施例13>
窒素フロー下、500mL三口フラスコに、ヘキサフルオロホスファゼン(東京化成社品)40.0g(0.16mol)、アセトニトリル200mLを仕込み、氷浴で冷やしながら塩化マグネシウム15.3g(0.16mol)を少量ずつ添加した。次に、0℃〜5℃にてジメチルアミンガス(Aldrich社製)19.86g(0.64mol)を0.3g/minの速度でバブリングした。
次に、内温30℃に保ったまま2時間反応を行った。反応の進行状態を、内標にモノフッ化ベンゼンを用いて19F−NMRにて確認したところ、反応転換率90%であり、一置換体、三置換体は確認されなかった。
反応終了後、分液や減圧蒸留精製により、無色透明の化合物(1−4)38.92g、収率81%で得た。また、純度をガスクロマトグラフィーで確認したところ、純度99.89%以上であった。
<Example 13>
Under a nitrogen flow, 40.0 g (0.16 mol) of hexafluorophosphazene (product of Tokyo Chemical Industry Co., Ltd.) and 200 mL of acetonitrile are charged into a 500 mL three-necked flask, and 15.3 g (0.16 mol) of magnesium chloride is added little by little while cooling in an ice bath. Added. Next, 19.86 g (0.64 mol) of dimethylamine gas (manufactured by Aldrich) was bubbled at a rate of 0.3 g / min at 0 ° C. to 5 ° C.
Next, the reaction was carried out for 2 hours while maintaining the internal temperature at 30 ° C. When the progress of the reaction was confirmed by 19F-NMR using monofluorinated benzene as an internal standard, the reaction conversion rate was 90%, and no mono- or tri-substituted products were confirmed.
After completion of the reaction, 38.92 g of colorless and transparent compound (1-4) was obtained with a yield of 81% by liquid separation or vacuum distillation purification. Further, when the purity was confirmed by gas chromatography, the purity was 99.89% or more.
<比較例1>
窒素フロー下、500mL三口フラスコに、ヘキサフルオロホスファゼン(東京化成社品)40.0g(0.16mol)、炭酸ナトリウム16.96g(0.16mol)、アセトニトリル200mLを仕込み、氷/メタノール浴で−10℃〜0℃に保ちながら、ジメチルアミンガス(Aldrich社製)7.21g(0.16mol)を0.3g/minの速度でバブリングした。
次に、室温(約23℃)で2時間反応を行った。反応の進行状態を、内標にモノフッ化ベンゼンを用いて19F−NMRにて確認したところ、目的生成物への反応転換率は50%であり、二置換体が6%生成していた。また、そのほか未同定の副生成物の生成が確認できた。そのNMRスペクトルを図2に示す。
反応終了後、分液や減圧蒸留精製により、無色透明の化合物(1−1)18.35g、収率42%で得た。また、純度をガスクロマトグラフィーで確認したところ、純度99.11%であった。
<Comparative Example 1>
Under nitrogen flow, 40.0 g (0.16 mol) of hexafluorophosphazene (product of Tokyo Chemical Industry Co., Ltd.), 16.96 g (0.16 mol) of sodium carbonate and 200 mL of acetonitrile are charged into a 500 mL three-necked flask and −10 in an ice / methanol bath. While maintaining the temperature at 0 ° C to 0 ° C, 7.21 g (0.16 mol) of dimethylamine gas (Aldrich) was bubbled at a rate of 0.3 g / min.
Next, the reaction was performed at room temperature (about 23 ° C.) for 2 hours. When the progress of the reaction was confirmed by 19F-NMR using monofluorinated benzene as an internal standard, the reaction conversion rate to the target product was 50%, and 6% of a disubstituted product was produced. In addition, the generation of unidentified by-products could be confirmed. The NMR spectrum is shown in FIG.
After completion of the reaction, 18.35 g of a colorless and transparent compound (1-1) was obtained with a yield of 42% by liquid separation or vacuum distillation purification. Further, when the purity was confirmed by gas chromatography, the purity was 99.11%.
<比較例2>
非特許文献1に記載の方法で反応を行った。窒素フロー下、500mL三口フラスコに、ジメチルアミンガス17g(0.38mol)、ジエチルエーテル50mlを仕込み、氷浴で0〜5℃に保ちながら、ヘキサフルオロホスファゼン(東京化成社品)38.9g(0.16mol)のジエチルエーテル200ml溶液を滴下した。
次に、室温(約23℃)にて2時間反応を行った。反応の進行状態を、内標にモノフッ化ベンゼンを用いて19F−NMRにて確認したところ、一置換体である目的生成物への反応転換率は64%であり、二置換体15%が生成していた。
反応終了後、減圧蒸留精製により、無色透明の化合物(1−1)22.80g、収率52%で得られた。また、純度をガスクロマトグラフィーで確認したところ、純度98.78%であった。
<Comparative example 2>
The reaction was performed by the method described in
Next, the reaction was performed at room temperature (about 23 ° C.) for 2 hours. When the progress of the reaction was confirmed by 19F-NMR using monofluorinated benzene as the internal standard, the reaction conversion rate to the target product, which was a mono-substituted product, was 64%, and a di-substituted product was produced by 15%. Was.
After completion of the reaction, 22.80 g of a colorless and transparent compound (1-1) was obtained by distillation under reduced pressure in a yield of 52%. Further, when the purity was confirmed by gas chromatography, the purity was 98.78%.
<比較例3>
窒素フロー下、500mL三口フラスコに、ヘキサフルオロホスファゼン(東京化成社品)40.0g(0.16mol)、炭酸ナトリウム16.96g(0.16mol)、アセトニトリル200mLを仕込み、氷浴で0℃に保ちながら、エタノール7.37g(0.16mol)を滴下した。
次に、70℃で5時間反応を行った。反応の進行状態を、内標にモノフッ化ベンゼンを用いて19F−NMRにて確認したところ、目的生成物への反応転換率は35%であり、二置換体が9%生成していた。また、そのほか未同定の副生成物の生成が確認できた。
反応終了後、分液や減圧蒸留精製により、無色透明の化合物(c1)11.4g、収率26%で得た(図5−1、図5−2)。また、純度をガスクロマトグラフィーで確認したところ、純度99.35%であった。
<Comparative Example 3>
Under a nitrogen flow, a 500 mL three-necked flask was charged with 40.0 g (0.16 mol) of hexafluorophosphazene (Tokyo Kasei Co., Ltd.), 16.96 g (0.16 mol) of sodium carbonate and 200 mL of acetonitrile, and kept at 0 ° C. in an ice bath. Then, 7.37 g (0.16 mol) of ethanol was added dropwise.
Next, reaction was performed at 70 degreeC for 5 hours. When the progress of the reaction was confirmed by 19F-NMR using monofluorinated benzene as an internal standard, the reaction conversion rate to the target product was 35%, and 9% of a disubstituted product was produced. In addition, the generation of unidentified by-products could be confirmed.
After completion of the reaction, 11.4 g of a colorless and transparent compound (c1) was obtained in a yield of 26% by liquid separation or vacuum distillation purification (FIGS. 5-1 and 5-2). Further, when the purity was confirmed by gas chromatography, the purity was 99.35%.
<比較例4>
窒素フロー下、500mL三口フラスコに、ヘキサフルオロホスファゼン(東京化成社品)40.0g(0.16mol)、トリエチルアミン16.19g(0.16mol)、アセトニトリル200mLを仕込み、氷/メタノール浴で0℃に冷やした。0℃にてエタノール7.37g(0.16mol)を滴下した。
次に、0℃保ちながら1時間反応を行った。反応の進行状態を、内標にモノフッ化ベンゼンを用いて19F−NMRにて確認したところ、目的性生物への反応転換率は60%であり、二置換体が11%生成していた。
反応終了後、分液や減圧蒸留精製により、無色透明の化合物(c1)21.56g、収率49%で得た。
<Comparative Example 4>
Under a nitrogen flow, a 500 mL three-necked flask was charged with 40.0 g (0.16 mol) of hexafluorophosphazene (product of Tokyo Chemical Industry Co., Ltd.), 16.19 g (0.16 mol) of triethylamine, and 200 mL of acetonitrile, and brought to 0 ° C. in an ice / methanol bath. Chilled. At 0 ° C., 7.37 g (0.16 mol) of ethanol was added dropwise.
Next, the reaction was performed for 1 hour while maintaining at 0 ° C. When the progress of the reaction was confirmed by 19F-NMR using monofluorinated benzene as the internal standard, the reaction conversion rate to the target organism was 60%, and 11% of the disubstituted product was produced.
After completion of the reaction, 21.56 g of a colorless and transparent compound (c1) was obtained with a yield of 49% by liquid separation or vacuum distillation purification.
上記の結果を以下の表1にまとめて示す。
ex:実施例
cex:比較例
HFP:ヘキサフルオロホスファゼン
DMA:ジメチルアミン
MMA:モノメチルアミン
DEA:ジエチルアミン
TEA:トリエチルアミン
EtOH:エタノール
Me2SiCl2:ジクロロジメチルシラン[(CH3)2SiCl2]
TMS−Cl:トリメチルクロロシラン[(CH3)3SiCl]
cex.4のTEAの添加は系内の中和目的
ex.3の転換率および選択率は、鉄の影響のためNMR測定ができず、空欄とした。
r.t.:室温(約23℃)
The above results are summarized in Table 1 below.
ex: EXAMPLE cex: Comparative Example HFP: hexafluoropropylene phosphazene DMA: dimethylamine MMA: monomethylamine DEA: diethylamine TEA: triethylamine EtOH: ethanol Me 2 SiCl 2: dichlorodimethylsilane [(CH 3) 2 SiCl 2 ]
TMS-Cl: Trimethylchlorosilane [(CH 3 ) 3 SiCl]
cex.4 TEA is added to neutralize the system
The conversion rate and selectivity of ex.3 were left blank because NMR measurement was not possible due to the influence of iron.
r. t. : Room temperature (about 23 ° C)
表1中の選択率とは、反応系での目的置換体の生成割合を表す。
選択率(%)= [目的置換体転換率/(目的置換体転換率+他置換体転換率)]
The selectivity in Table 1 represents the production rate of the target substitution product in the reaction system.
Selectivity (%) = [target substitution product conversion rate / (target substitution product conversion rate + other substitution product conversion rate)]
上記各実施例で得られたアミノ置換ホスファゼン化合物を用い、これを添加した非水二次電池用の電解液を調製した。上記電解液を用いた非水二次電池は良好な充放電性能を示し、しかも上記置換ホスファゼン化合物を添加したことによる電解液の優れた難燃性を発揮することを確認した。 Using the amino-substituted phosphazene compound obtained in each of the above Examples, an electrolyte solution for a non-aqueous secondary battery to which this was added was prepared. It was confirmed that the non-aqueous secondary battery using the electrolytic solution exhibited good charge / discharge performance, and exhibited excellent flame retardancy of the electrolytic solution by adding the substituted phosphazene compound.
実施例1のジメチルアミンに代え、所定のアミン化合物を用いて、上記の例示化合物1−7、1−8、1−12の合成を行った。良好な収率および選択性で目的化合物が得られることを確認した。 Instead of the dimethylamine of Example 1, the above-mentioned exemplary compounds 1-7, 1-8, and 1-12 were synthesized using a predetermined amine compound. It was confirmed that the target compound was obtained with good yield and selectivity.
実施例1の塩化アルミニウムに代え、ZrCl4、ZrOCl2、LiCl、SiCl4を触媒に用いて同様の合成を行った。良好な収率および選択性で目的化合物が得られることを確認した。 The same synthesis was performed using ZrCl 4 , ZrOCl 2 , LiCl, and SiCl 4 as catalysts instead of the aluminum chloride of Example 1. It was confirmed that the target compound was obtained with good yield and selectivity.
Claims (11)
式中、Mは金属原子、半金属原子であり、Zはハロゲン原子である。 The process according to prior Symbol Lewis acid catalyst, any one of claims 1 to 4 comprising a compound having at least one M-Z bond.
In the formula, M is a metal atom or a metalloid atom, and Z is a halogen atom.
Meはメチル基を表す。TMSはトリメチルシリル基を表す。 Before SL Lewis acid catalyst is selected from AlCl 3, MgCl 2, LiCl, LiBr, CuCl 2, FeCl 3, ZrCl 4, ZrOCl 2, SiCl 4, Me 2 SiCl 2, TMS-Cl, and the group consisting of BCl 3 It is at least 1 type, The manufacturing method of any one of Claims 1-8 .
Me represents a methyl group. TMS represents a trimethylsilyl group.
Through the manufacturing method according to claim 10, positive electrode, a negative electrode and a front KiHisui nonaqueous secondary battery manufacturing method of manufacturing a nonaqueous secondary battery comprising an electrolyte solution for a secondary battery.
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Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |