CA2314739C - Ionic metal complex and process for synthesizing same - Google Patents
Ionic metal complex and process for synthesizing same Download PDFInfo
- Publication number
- CA2314739C CA2314739C CA002314739A CA2314739A CA2314739C CA 2314739 C CA2314739 C CA 2314739C CA 002314739 A CA002314739 A CA 002314739A CA 2314739 A CA2314739 A CA 2314739A CA 2314739 C CA2314739 C CA 2314739C
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- Canada
- Prior art keywords
- group
- alkyl group
- halogenated
- ion
- aryl group
- Prior art date
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- Expired - Fee Related
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- 150000004696 coordination complex Chemical class 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims description 33
- 230000002194 synthesizing effect Effects 0.000 title claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 51
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims abstract description 26
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 26
- -1 triphenylmethyl ion Chemical class 0.000 claims abstract description 23
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims abstract description 21
- 150000002367 halogens Chemical class 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 17
- 150000002500 ions Chemical class 0.000 claims abstract description 16
- 230000000737 periodic effect Effects 0.000 claims abstract description 12
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 9
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 8
- 150000004010 onium ions Chemical class 0.000 claims abstract description 7
- 125000006832 (C1-C10) alkylene group Chemical group 0.000 claims abstract description 6
- 125000005843 halogen group Chemical group 0.000 claims abstract 8
- 150000001875 compounds Chemical class 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 30
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 19
- 229910001416 lithium ion Inorganic materials 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Chemical group 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 4
- 150000007942 carboxylates Chemical class 0.000 claims description 4
- 239000013522 chelant Substances 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 206010011416 Croup infectious Diseases 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- 229910052785 arsenic Inorganic materials 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 201000010549 croup Diseases 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 150000004679 hydroxides Chemical class 0.000 claims description 3
- 229910001507 metal halide Inorganic materials 0.000 claims description 3
- 150000005309 metal halides Chemical class 0.000 claims description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 3
- 150000004692 metal hydroxides Chemical class 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 150000004703 alkoxides Chemical class 0.000 claims description 2
- 239000000543 intermediate Substances 0.000 claims 4
- 125000005210 alkyl ammonium group Chemical group 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 abstract description 11
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 8
- 239000002685 polymerization catalyst Substances 0.000 abstract description 4
- 229920000098 polyolefin Polymers 0.000 abstract description 4
- 239000003115 supporting electrolyte Substances 0.000 abstract description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 24
- 239000000047 product Substances 0.000 description 23
- ZQBFAOFFOQMSGJ-UHFFFAOYSA-N hexafluorobenzene Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1F ZQBFAOFFOQMSGJ-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 238000010494 dissociation reaction Methods 0.000 description 7
- 230000005593 dissociations Effects 0.000 description 7
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000003595 spectral effect Effects 0.000 description 6
- CMQUGOHGJUTDGZ-UHFFFAOYSA-N 3,3,3-trifluoro-2-hydroxy-2-(trifluoromethyl)propanoic acid Chemical compound OC(=O)C(O)(C(F)(F)F)C(F)(F)F CMQUGOHGJUTDGZ-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- WEVYAHXRMPXWCK-FIBGUPNXSA-N acetonitrile-d3 Chemical compound [2H]C([2H])([2H])C#N WEVYAHXRMPXWCK-FIBGUPNXSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000004293 19F NMR spectroscopy Methods 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910013075 LiBF Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- BVKGUTLIPHZYCX-UHFFFAOYSA-N 3,3,3-trifluoro-2-hydroxypropanoic acid Chemical compound OC(=O)C(O)C(F)(F)F BVKGUTLIPHZYCX-UHFFFAOYSA-N 0.000 description 1
- NOHJBOWARMTILE-UHFFFAOYSA-N 4,4,4-trifluoro-3-hydroxy-3-(trifluoromethyl)butanoic acid Chemical compound OC(=O)CC(O)(C(F)(F)F)C(F)(F)F NOHJBOWARMTILE-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 239000008896 Opium Substances 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 210000004013 groin Anatomy 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 229960001027 opium Drugs 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- SZWHXXNVLACKBV-UHFFFAOYSA-N tetraethylphosphanium Chemical compound CC[P+](CC)(CC)CC SZWHXXNVLACKBV-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- BXYHVFRRNNWPMB-UHFFFAOYSA-N tetramethylphosphanium Chemical compound C[P+](C)(C)C BXYHVFRRNNWPMB-UHFFFAOYSA-N 0.000 description 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 1
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- GZBUMTPCIKCWFW-UHFFFAOYSA-N triethylcholine Chemical compound CC[N+](CC)(CC)CCO GZBUMTPCIKCWFW-UHFFFAOYSA-N 0.000 description 1
- ZFEAYIKULRXTAR-UHFFFAOYSA-M triphenylsulfanium;chloride Chemical compound [Cl-].C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 ZFEAYIKULRXTAR-UHFFFAOYSA-M 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
-
- 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
- H01M10/056—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
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/04—Esters of boric acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/069—Aluminium compounds without C-aluminium linkages
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/04—Esters of silicic acids
- C07F7/07—Cyclic esters
-
- 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
- C07F9/6571—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 oxygen atoms as the only ring hetero atoms
-
- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
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Abstract
The invention relates an ionic metal complex represented by the general formula (1):
Description
IONIC METAL COMPLEX AND PROCESS FOR
SYNTHESIZING SAME
BACKGROUND OF THE INVENTION
The present invention relates to an ionic metal complex having a novel chemical structure and a process for synthesizing the ionic metal complex that is used as a supporting electrolyte for lithium batteries, lithium ion batteries, electrical double-layer capacitors and other electrochemical devices, a polymerization catalyst for polyolefins and so forth, or a catalyst for organic synthesis.
Ionic complexes, such as PFs', BF4' and AsFs', formed by bonding of Lewis acids with F ion have been used in applications such as supporting electrolytes for electrochemical devices, polymerization catalysts for polyolefins and so forth or catalysts for organic synthesis due to their solubility and ion dissociation characteristics.
As the application range of these ionic complexes becomes increasingly diverse, efforts are being made to search for the optimum ionic complex for each application, and these ionic complexes are being required to have properties including heat resistance, hydrolysis resistance, low toxicity and recycleability.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a useful, novel, ionic metal complex and a process for synthesizing the same.
As a result of earnest studies, the inventors of the present invention found an ionic metal complex having a novel chemical structure and a process for synthesizing the same, thereby leading to completion of the present invention.
According to the present invention, there is provided an ionic metal complex represented by the general formula (1):
x . . z R. ~~ ~
a+ Q ~ ~ 3 ~1) p ~ )n . ~ (~ .) q ~E?
m wherein M is a transition metal selected from the group consisting of elements of groups 3-11. of the periodic table, or an element selected from the croup consisting of elements of groups 12-15 of the periodic table; Aa+
represents a metal ion, onium ion, triphenylmethyl ion, metallocenium ion, or proton; provided that M is not B when Aa+ is Cs+; a represents a number from 1 to 3; b represents a number from 1 to 3; p is b/a; m represents a number from 1 to 3; n represents a number from 0 to 4; q is 0 or 1; X1 represents O or S; each of R1 and R2 independently represents H, a halogen, a C1-C10 alkyl group or C~-C~~
halogenated alkyl group; R3 represents a C1-C10 alkylene group, C1-C10 halogenated alkylene group, C6-C20 aryl group or C6-C20 halogenated aryl group; R~ represents a halogen, C1-C10 alkyl group, C1-C10 halogenated alkyl group, C6-C20 aryl group, C6-C20 halogenated aryl group or X2R~; X2 represents O, S or NRS; R5 represents H or a C1-C10 alkyl group; and R~ represents a C1-C10 alkyl group, C1-C10 halogenated alkyl group, C6-C20 aryl group or Cg-C20 halogenated aryl group.
According to the present invention, there is provided a first process comprises reacting a compound represented by the general formula (2) with a metal complex represented by the general formula (3). This compound contains at least two active hydrogens.
SYNTHESIZING SAME
BACKGROUND OF THE INVENTION
The present invention relates to an ionic metal complex having a novel chemical structure and a process for synthesizing the ionic metal complex that is used as a supporting electrolyte for lithium batteries, lithium ion batteries, electrical double-layer capacitors and other electrochemical devices, a polymerization catalyst for polyolefins and so forth, or a catalyst for organic synthesis.
Ionic complexes, such as PFs', BF4' and AsFs', formed by bonding of Lewis acids with F ion have been used in applications such as supporting electrolytes for electrochemical devices, polymerization catalysts for polyolefins and so forth or catalysts for organic synthesis due to their solubility and ion dissociation characteristics.
As the application range of these ionic complexes becomes increasingly diverse, efforts are being made to search for the optimum ionic complex for each application, and these ionic complexes are being required to have properties including heat resistance, hydrolysis resistance, low toxicity and recycleability.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a useful, novel, ionic metal complex and a process for synthesizing the same.
As a result of earnest studies, the inventors of the present invention found an ionic metal complex having a novel chemical structure and a process for synthesizing the same, thereby leading to completion of the present invention.
According to the present invention, there is provided an ionic metal complex represented by the general formula (1):
x . . z R. ~~ ~
a+ Q ~ ~ 3 ~1) p ~ )n . ~ (~ .) q ~E?
m wherein M is a transition metal selected from the group consisting of elements of groups 3-11. of the periodic table, or an element selected from the croup consisting of elements of groups 12-15 of the periodic table; Aa+
represents a metal ion, onium ion, triphenylmethyl ion, metallocenium ion, or proton; provided that M is not B when Aa+ is Cs+; a represents a number from 1 to 3; b represents a number from 1 to 3; p is b/a; m represents a number from 1 to 3; n represents a number from 0 to 4; q is 0 or 1; X1 represents O or S; each of R1 and R2 independently represents H, a halogen, a C1-C10 alkyl group or C~-C~~
halogenated alkyl group; R3 represents a C1-C10 alkylene group, C1-C10 halogenated alkylene group, C6-C20 aryl group or C6-C20 halogenated aryl group; R~ represents a halogen, C1-C10 alkyl group, C1-C10 halogenated alkyl group, C6-C20 aryl group, C6-C20 halogenated aryl group or X2R~; X2 represents O, S or NRS; R5 represents H or a C1-C10 alkyl group; and R~ represents a C1-C10 alkyl group, C1-C10 halogenated alkyl group, C6-C20 aryl group or Cg-C20 halogenated aryl group.
According to the present invention, there is provided a first process comprises reacting a compound represented by the general formula (2) with a metal complex represented by the general formula (3). This compound contains at least two active hydrogens.
R~~2 ~~-~i t~3~ (2) q ~~ a--v.
~z+ t~4~_~ ~Rs~ (3) 1a ~s 2m wherein Xz, Rz, R2, R3, R4, M, Aa+, q, a, b, p, m, and n are defined as above, R8 represents a halogen, hydroxyl group, hydrogen, Cz'Czo alkyl group, Cl-Czo halogenated alkyl group, C6 c20 aryl group , ~ -C halogenated aryl group or X3R9~ X3 :represents 0, S
C . 20 or t~t5 where R~ is defined as above and R9 represents a Cz'Czo alkyl group, Cz'Czo halogenated alkyl group , C6-C2~ary1 group or C6 C2phalogenated aryl group.
According to the present invention, there is ;provided a second process for synthesizing the ionic metal complex. The second process comprises (a) reacting a first compound represented by the general formula (2) with a metal complex represented by the general formula (4), thereby obtaining an intermediate and (b) reacting the intermediate with a second compour.~d, thereby obtaining the ionic metal complex. The first compound contains 2~ at least two active hydrogens. The second compound contains a cation represented by Aa* defined as above and ie~ selected from the group consisting of metal halides, metal alkoxidea, metal carboxylates, metal hydroxides; metal oxides, metal carbonates, quaternary alkylonium halides, quaternary alkylonium hydroxides and quaternary alk-ylonium caxboxylates.
_,_ ~~~2 (j~.3~9 (2) ~_I-O
() ~~Zd~ n M ~R8~ (~) 2rra-.1 wherein Xl, Rl, R~, R3, R4, R8, M, q, m, and n are defined as above.
According to the present invention, there is provided a third process for synthesizing the ionic metal complex. The third process comprises (a) reacting a first compound represented by the general formula (2) with a second compound containing an alkali metal or alkali-earth metal, thereby obtaining an intermediate and (b) reacting the intermediate with a metal complex represented by the general formula (5), H X --~ (2>
I~-O---O
C~4~n ~ ~~1Q~ (5) 2m wherein X1, R1, R2, R3, R4, NI, Aa+, q, a, b, p, m, and n are ~~efined as above, R1~ represents a halogen or hydroxyl group.
According to yet another aspect of the invention, there is provided an ionic metal complex represented by the following formula:
r3c ~ cr3 -Li+
0 0' ' o' o The above-mentioned ionic metal complex has a novel chemical structure and can be used as a supporting electrolyte for lithium batteries, lithium ion batteries, electrical double-layer 4a capacitors and other electrochemical devices, a polymerization catalyst for polyolefins and so forth, or a catalyst for organic synthesis. The ionic metal complex can be synthesized by each of the above-mentioned first, second and third processes.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
According to the invention, the alkyl groups, halogenated alkyl groups, aryl groups and halogenated aryl groups, which are contained in the ionic metal complex and the raw materials for synthesizing the same, may be branched and/or may have other functional groups such as hydroxyl groups and ether bonds.
The followings are specific nine examples of the ionic metal complex represented by the general formula (1) of the present invention.
F3 C C F3 " CF3 Li+ F3C O~~ O CF3 Li+ FHB O CF3 _ " F p O O O O O
H' ,CF3 - F3C CF3 _ Li+ F3C ~O~ ~O CF3 r3C O~ ~O CF3 B Li+
F3C' 'O~ O O OBQ
II ~CF3 O O
.+ F3 O\ /O CF3 ~ ,+ FyO. Cc~3 _ Ll B\ Li F ~P~
O fl O ~O F F . O O
Fs . CF3 F3C CF3 _ _ O O F3C ~ CF3 Li+ ~ \ AI I \ L~+ F C ~~B N CF3 O O ~ 3 O O
O O
O O
r r3c z _ r3c v cF3 o,Q.o cr (Li+)z O~,Si.o 3 S O O O
x,,:~c cr3 Here, although lithium ion is indicated as an example of Aa+
of the general formula (1), examples of other cations that can be used other than lithium ion include sodium ion, potassium ion, magnesium ion, calcium ion, barium ion, cesium ion, silver ion, zinc ion, copper ion, cobalt ion, iron ion, nickel ion, manganese ion, titanium ion, lead ion, chromium ion, vanadium ion, ruthenium ion, yttrium ion, lanthanoid ion, actinoid ion, tetrabutylammonium ion, tetraethylammonium ion, tetramethylammonium ion, triethylmethylammonium ion, triethylammonium ion, pyridinium ion, imidazolium ion, proton, tetraethylphosphonium ion, tetramethylphosphonium ion, tetraphenylphosphonium ion, triphenylsulfonium ion, triethylsulfonium ion and triphenylmethyl ion. In the case of considering the application of the ionic metal complex for electrochemical devices and the like, lithium ion, tetraalkylammonium ion and proton are preferable. In addition, in the case of the application of the ionic metal complex for catalyst, lithium ion, proton, triphenylmethyl ion, trialkylammonium ion and metallocenium ion are preferable. As shown in the general formula (1), the valency (valence) of the Aa+
cation is preferably from 1 to 3. If the valency is larger than 3, the problem occurs in which it becomes difficult to dissolve the ionic metal complex in solvent due to the increase in crystal lattice energy. Consequently, in the case of requiring solubility of the ionic metal complex, a valency of 1 is preferable. As shown in the general formula (1), the valency (b-) of the anion is similarly preferably from 1 to 3, and a valency of 1 is particularly preferable.
The constant p expresses the ratio of the valency of the anion to the valency of the cation, namely b/a.
In the general formula (1), M at the center of the ionic metal complex of the present invention is selected from elements of groups 3-15 of the periodic table. It is preferably Al, B, V, Ti, Si, Zr, Ge, Sn, Cu, Y, Zn, Ga, Nb, Ta, Bi, P, As, Sc, Hf or Sb, and more preferably Al, B or P. Although it is possible to use various elements for the M other than these preferable examples, synthesis is relatively easy in the case of using Al, B, V, Ti, Si, Zr, Ge, Sn, Cu, Y, Zn, Ga, Nb, Ta, Bi, P, As, Sc, Hf or Sb. In addition to ease of synthesis, the ionic metal complex has excellent properties in terms of low toxicity, stability and production cost in the case of using Al, B or P.
In the general formula (1), the organic or inorganic portion bonded to M is referred to as the ligand. As mentioned above, X1 in the general formula (1) represents O or S, and is bonded to M through its hetero atom (O, S or N). Although the bonding of an atom other than O, S or N is not impossible, the synthesis becomes extremely bothersome. The ionic metal complex represented by the general formula (1) is characterized by these ligands forming a chelate structure with M since there is bonding with M by a carboxyl group (-COO-) other than X1 within the same ligand. As a result of this chlelation, the heat resistance, chemical stability and hydrolysis resistance of the ionic metal complex are improved. Although constant q in this ligand is either 0 or 1, in the case of 0 in particular, since the chelate ring becomes a five-member ring, chelating effects are demonstrated most prominently, making this preferable due to the resulting increase in stability. In addition, since the negative charge of the central M is dissipated by electron attracting effects of the carbonyl group (s) resulting in an increase in electrical stability of the anion, ion dissociation becomes extremely easy resulting in corresponding increases of the ionic metal comple:~ in solvent solubility, ion conductivity, catalyst activity and so forth. In addition, the other properties of heat resistance, chemical stability and hydrolysis resistance are also improved. .
In the general formula (1), each of RI and RZ is independently selected from IZ, halogen, Ci-Clo alkyl groups and Cz-Cio halogenated alkyl groups. At least one of either ftl and R2 is preferably a fluorinated alkyl group, and more preferably, at least one of R~ and R2 is a trifluoromethyl group. Due to the presence of an electron-attracting halogen and/or a halogen:ated alkyl group for Rl and R2, the negative charge of the central NT is dissipated.
This results in an increase of the axuon of the general. formula (I) in electrical stability. With this, the ion dissociation becomes extremely easy resulting in an increase of the ionic metal complex IS in solvent solubility, ion conductivity, catalyst activity and so forth.
In addition, other properties of heat resistance, chemical stability and hydrolysis resistance are also improved. The case in which the halogen is fluorine in particular has significaxit advantageous effects, while the case of a trifluoromethyl group has the greatest advantageous effect.
in the general formula (1), R3 is selected from Cl'Cio alkylene groups, Cl-Clo halogenated alkylene groups . c6 c.2~xyl groups ana .c -c h~ogenated aryl groups. R3 is preferably one which forms a ~ to 10-membered ring when a chelate rixig is formed with the central M. The case of a ring having more than 10 members is not preferable, since chelating advantageous effects are reduced.
In addition, in the case R3 has a portion of hydroxyl group or carboxyl group, it is possible to form a bond betwE:en the central M
and this portion.
In the general formula (1), R4 is selected from halogens, C1'Clo alkyl groups, C1'Clo halogenated alkyl groups, c6-C2p aryl groups, c6-c20 alogenated aryl groups and X'R~. Of these, fluorine is preferable. X' represents 0, S or NR~~ aid bonds to _g_ M through one of these heteroatoms (O, :3 and N). Although the bonding of an atom other than O, S or N is not impossible, the synthesis becomes extremely bothersome. R5 is selected from H and C1-C1p alkyl groin>s. R5 differs from other groups (e.g., R1 and R2) in that is not required to be an electron attracting group. In the ease of introducing an electron attracting group as R5, the electron density on N of NR5 decreases, thereby preventing coordination on the central M. R? is selected from C~=Clo alkyl groups, Cz-Czo so halogenated alkyl groups; ~6-C2Qaxy1 groups and ~6-X20 halogenated aryl groups. Of these, a Cz-Czo fluorinated alkyl groups is preferable. Due to the presence of an electron-attracting halogenated alkyl group as R7, this negative charge of the central M is dissipated. Since this inc~°eases the electrical stability of the anion of the general formula (I), ion dissociation becomes extremely easy resulting in an increase of the ionic metal complex in solvent solubility, ion conductivity and catalyst activity. In addition, other properties of heat resistance, chemical stability and hydrolysis resistance are also 'improved.
The case in. which the halogenated alkyl group as R7 is a fluorinated alkyl group in particular results in even greater advantageous effects.
In the general formula (1), the values of the constants m and n relating to the number of the above-mentioned ligands depend on the type of the central M. In fact, m is preferably from 1 to 3, while n is preferably from 0 to 4.
Next, the follov~iing provides an explanation of t:he process fax synthesizing the ionic metal complex of the present i:n.vention. As a result of earnest studies, the synthesis process broadly divided into three types (i.e., the above-mentioned fzxst, second and third processes) were found to obtain the target compound, the ionic metal complex.
~z+ t~4~_~ ~Rs~ (3) 1a ~s 2m wherein Xz, Rz, R2, R3, R4, M, Aa+, q, a, b, p, m, and n are defined as above, R8 represents a halogen, hydroxyl group, hydrogen, Cz'Czo alkyl group, Cl-Czo halogenated alkyl group, C6 c20 aryl group , ~ -C halogenated aryl group or X3R9~ X3 :represents 0, S
C . 20 or t~t5 where R~ is defined as above and R9 represents a Cz'Czo alkyl group, Cz'Czo halogenated alkyl group , C6-C2~ary1 group or C6 C2phalogenated aryl group.
According to the present invention, there is ;provided a second process for synthesizing the ionic metal complex. The second process comprises (a) reacting a first compound represented by the general formula (2) with a metal complex represented by the general formula (4), thereby obtaining an intermediate and (b) reacting the intermediate with a second compour.~d, thereby obtaining the ionic metal complex. The first compound contains 2~ at least two active hydrogens. The second compound contains a cation represented by Aa* defined as above and ie~ selected from the group consisting of metal halides, metal alkoxidea, metal carboxylates, metal hydroxides; metal oxides, metal carbonates, quaternary alkylonium halides, quaternary alkylonium hydroxides and quaternary alk-ylonium caxboxylates.
_,_ ~~~2 (j~.3~9 (2) ~_I-O
() ~~Zd~ n M ~R8~ (~) 2rra-.1 wherein Xl, Rl, R~, R3, R4, R8, M, q, m, and n are defined as above.
According to the present invention, there is provided a third process for synthesizing the ionic metal complex. The third process comprises (a) reacting a first compound represented by the general formula (2) with a second compound containing an alkali metal or alkali-earth metal, thereby obtaining an intermediate and (b) reacting the intermediate with a metal complex represented by the general formula (5), H X --~ (2>
I~-O---O
C~4~n ~ ~~1Q~ (5) 2m wherein X1, R1, R2, R3, R4, NI, Aa+, q, a, b, p, m, and n are ~~efined as above, R1~ represents a halogen or hydroxyl group.
According to yet another aspect of the invention, there is provided an ionic metal complex represented by the following formula:
r3c ~ cr3 -Li+
0 0' ' o' o The above-mentioned ionic metal complex has a novel chemical structure and can be used as a supporting electrolyte for lithium batteries, lithium ion batteries, electrical double-layer 4a capacitors and other electrochemical devices, a polymerization catalyst for polyolefins and so forth, or a catalyst for organic synthesis. The ionic metal complex can be synthesized by each of the above-mentioned first, second and third processes.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
According to the invention, the alkyl groups, halogenated alkyl groups, aryl groups and halogenated aryl groups, which are contained in the ionic metal complex and the raw materials for synthesizing the same, may be branched and/or may have other functional groups such as hydroxyl groups and ether bonds.
The followings are specific nine examples of the ionic metal complex represented by the general formula (1) of the present invention.
F3 C C F3 " CF3 Li+ F3C O~~ O CF3 Li+ FHB O CF3 _ " F p O O O O O
H' ,CF3 - F3C CF3 _ Li+ F3C ~O~ ~O CF3 r3C O~ ~O CF3 B Li+
F3C' 'O~ O O OBQ
II ~CF3 O O
.+ F3 O\ /O CF3 ~ ,+ FyO. Cc~3 _ Ll B\ Li F ~P~
O fl O ~O F F . O O
Fs . CF3 F3C CF3 _ _ O O F3C ~ CF3 Li+ ~ \ AI I \ L~+ F C ~~B N CF3 O O ~ 3 O O
O O
O O
r r3c z _ r3c v cF3 o,Q.o cr (Li+)z O~,Si.o 3 S O O O
x,,:~c cr3 Here, although lithium ion is indicated as an example of Aa+
of the general formula (1), examples of other cations that can be used other than lithium ion include sodium ion, potassium ion, magnesium ion, calcium ion, barium ion, cesium ion, silver ion, zinc ion, copper ion, cobalt ion, iron ion, nickel ion, manganese ion, titanium ion, lead ion, chromium ion, vanadium ion, ruthenium ion, yttrium ion, lanthanoid ion, actinoid ion, tetrabutylammonium ion, tetraethylammonium ion, tetramethylammonium ion, triethylmethylammonium ion, triethylammonium ion, pyridinium ion, imidazolium ion, proton, tetraethylphosphonium ion, tetramethylphosphonium ion, tetraphenylphosphonium ion, triphenylsulfonium ion, triethylsulfonium ion and triphenylmethyl ion. In the case of considering the application of the ionic metal complex for electrochemical devices and the like, lithium ion, tetraalkylammonium ion and proton are preferable. In addition, in the case of the application of the ionic metal complex for catalyst, lithium ion, proton, triphenylmethyl ion, trialkylammonium ion and metallocenium ion are preferable. As shown in the general formula (1), the valency (valence) of the Aa+
cation is preferably from 1 to 3. If the valency is larger than 3, the problem occurs in which it becomes difficult to dissolve the ionic metal complex in solvent due to the increase in crystal lattice energy. Consequently, in the case of requiring solubility of the ionic metal complex, a valency of 1 is preferable. As shown in the general formula (1), the valency (b-) of the anion is similarly preferably from 1 to 3, and a valency of 1 is particularly preferable.
The constant p expresses the ratio of the valency of the anion to the valency of the cation, namely b/a.
In the general formula (1), M at the center of the ionic metal complex of the present invention is selected from elements of groups 3-15 of the periodic table. It is preferably Al, B, V, Ti, Si, Zr, Ge, Sn, Cu, Y, Zn, Ga, Nb, Ta, Bi, P, As, Sc, Hf or Sb, and more preferably Al, B or P. Although it is possible to use various elements for the M other than these preferable examples, synthesis is relatively easy in the case of using Al, B, V, Ti, Si, Zr, Ge, Sn, Cu, Y, Zn, Ga, Nb, Ta, Bi, P, As, Sc, Hf or Sb. In addition to ease of synthesis, the ionic metal complex has excellent properties in terms of low toxicity, stability and production cost in the case of using Al, B or P.
In the general formula (1), the organic or inorganic portion bonded to M is referred to as the ligand. As mentioned above, X1 in the general formula (1) represents O or S, and is bonded to M through its hetero atom (O, S or N). Although the bonding of an atom other than O, S or N is not impossible, the synthesis becomes extremely bothersome. The ionic metal complex represented by the general formula (1) is characterized by these ligands forming a chelate structure with M since there is bonding with M by a carboxyl group (-COO-) other than X1 within the same ligand. As a result of this chlelation, the heat resistance, chemical stability and hydrolysis resistance of the ionic metal complex are improved. Although constant q in this ligand is either 0 or 1, in the case of 0 in particular, since the chelate ring becomes a five-member ring, chelating effects are demonstrated most prominently, making this preferable due to the resulting increase in stability. In addition, since the negative charge of the central M is dissipated by electron attracting effects of the carbonyl group (s) resulting in an increase in electrical stability of the anion, ion dissociation becomes extremely easy resulting in corresponding increases of the ionic metal comple:~ in solvent solubility, ion conductivity, catalyst activity and so forth. In addition, the other properties of heat resistance, chemical stability and hydrolysis resistance are also improved. .
In the general formula (1), each of RI and RZ is independently selected from IZ, halogen, Ci-Clo alkyl groups and Cz-Cio halogenated alkyl groups. At least one of either ftl and R2 is preferably a fluorinated alkyl group, and more preferably, at least one of R~ and R2 is a trifluoromethyl group. Due to the presence of an electron-attracting halogen and/or a halogen:ated alkyl group for Rl and R2, the negative charge of the central NT is dissipated.
This results in an increase of the axuon of the general. formula (I) in electrical stability. With this, the ion dissociation becomes extremely easy resulting in an increase of the ionic metal complex IS in solvent solubility, ion conductivity, catalyst activity and so forth.
In addition, other properties of heat resistance, chemical stability and hydrolysis resistance are also improved. The case in which the halogen is fluorine in particular has significaxit advantageous effects, while the case of a trifluoromethyl group has the greatest advantageous effect.
in the general formula (1), R3 is selected from Cl'Cio alkylene groups, Cl-Clo halogenated alkylene groups . c6 c.2~xyl groups ana .c -c h~ogenated aryl groups. R3 is preferably one which forms a ~ to 10-membered ring when a chelate rixig is formed with the central M. The case of a ring having more than 10 members is not preferable, since chelating advantageous effects are reduced.
In addition, in the case R3 has a portion of hydroxyl group or carboxyl group, it is possible to form a bond betwE:en the central M
and this portion.
In the general formula (1), R4 is selected from halogens, C1'Clo alkyl groups, C1'Clo halogenated alkyl groups, c6-C2p aryl groups, c6-c20 alogenated aryl groups and X'R~. Of these, fluorine is preferable. X' represents 0, S or NR~~ aid bonds to _g_ M through one of these heteroatoms (O, :3 and N). Although the bonding of an atom other than O, S or N is not impossible, the synthesis becomes extremely bothersome. R5 is selected from H and C1-C1p alkyl groin>s. R5 differs from other groups (e.g., R1 and R2) in that is not required to be an electron attracting group. In the ease of introducing an electron attracting group as R5, the electron density on N of NR5 decreases, thereby preventing coordination on the central M. R? is selected from C~=Clo alkyl groups, Cz-Czo so halogenated alkyl groups; ~6-C2Qaxy1 groups and ~6-X20 halogenated aryl groups. Of these, a Cz-Czo fluorinated alkyl groups is preferable. Due to the presence of an electron-attracting halogenated alkyl group as R7, this negative charge of the central M is dissipated. Since this inc~°eases the electrical stability of the anion of the general formula (I), ion dissociation becomes extremely easy resulting in an increase of the ionic metal complex in solvent solubility, ion conductivity and catalyst activity. In addition, other properties of heat resistance, chemical stability and hydrolysis resistance are also 'improved.
The case in. which the halogenated alkyl group as R7 is a fluorinated alkyl group in particular results in even greater advantageous effects.
In the general formula (1), the values of the constants m and n relating to the number of the above-mentioned ligands depend on the type of the central M. In fact, m is preferably from 1 to 3, while n is preferably from 0 to 4.
Next, the follov~iing provides an explanation of t:he process fax synthesizing the ionic metal complex of the present i:n.vention. As a result of earnest studies, the synthesis process broadly divided into three types (i.e., the above-mentioned fzxst, second and third processes) were found to obtain the target compound, the ionic metal complex.
3 o As stated above, the first pr ocess fox synthesizing the ionic metal complex comprises reacting a compound represented by the general formula (2) with a metal complex xepreserited by the general formula (3). Symbols other than R$ in the general formulas (2) and (3) are the same as those of the general formula (1). In fact, R8 is selected from halogens, hydroxyl group, hydrogen atom, Ci-Cio alkyl groups, C1-Cio halogenated alkyl groups, C6-C2~arY1 groups,, C6-CZ~ alogenated aryl groups and X3R9. Furthermore, R9 is selected from C1-Cio alkyl groups, CuC~.o halogenated alkyl groups., C6 C2~ aryl group and C6 C20 halogenated aryl groups, and Xs is O, S or NR,5 .
Mixing I mole of the compound represented lby the general formula (2) with 1/m moles, where m is defined as in the general formula (3), of the metal complex represented by t;he general formula (3) results in addition of the active hydrogens (i.e., hydrogens respectively bonded to Xl and O in the general formula (2)) of the compound of the general formula (2) to R8 of the general formula (3), followed by dissociation in the form of RBH. With this, the target ionic metal complex of the general formula (1) is obtaine d.
As stated above, the second process fox synthesizing the ionic metal complex comprises (a) reacting a first compound represented by the general formula (2) with a metal complex represented by the general formula (4), thereby obtaining an intermediate a.nd (b) reacting the intermediate with a second compound, thereby obtaining the ionic metal complex.
The first compound contains at least two active h.ydxogens, as show n in the general formula (2). The second compound contains a cation represented by Aa* that is a metal ion or opium ion. The 3a second compound is selected from the group consisting of metal halides, metal alkoxides, metal carboxylates, metal hydroxides, metal oxides, metal carbonates, quaternary alky:lonium halides, quaternary alkylonium hydroxides and quaternary alkylonium carboxylates. The symbols used in the formulas (2) and (4) are the same as those used in the general formulas (1) and (3).
Mixing 1 mole of the first compound of the general formula (2) with 1/m moles of the second compound of the general formula (4) S results in addition of the active hydrogens of the first compound of the general formula (2) to R8 of the general formula (4), followed by dissociation in the form of R8H. However, the number of Rg, that is, "2m-1" is deficient by one in the general formula (4), as compared with the number of active hydrogens in the general formula (2). Therefore, the surplus active hydrogen turns into a hydrogen ion (proton), and another active hydrogen that has formed a pair with the surplus active hydrogen is bonded to M.
With this, there is obtained an intermediate represented by the general formula (1) wherein Aa+ is the proton. Then, this intermediate is reacted with the second compound containing Aa+
that is a metal ion or onium ion to conduct an ion-exchange between the proton of the intermediate and Aa+ of the second compound, thereby obtaining the ionic metal complex.
As stated above, the third process for synthesizing the ionic metal complex comprises:
(a) reacting a first compound represented by the general formula (2) with a second compound containing an alkali metal or alkali-earth metal, thereby obtaining an intermediate and (b) reacting the intermediate with a metal complex represented by the general formula (5).
Symbols in the formulas (2) and (5) are the same as those of the general formula (1) with the exception of Rlo. In fact, Rlo represents a halogen or hydroxyl group. By the step (a), active hydrogens of the first compound in an amount of 1 mole can be replaced with the alkali metal or alkali-earth metal of the second compound. The resulting intermediate can be mixed with the metal complex in an amount of 1/m moles to conduct the step (b).
With this, the alkaline metal or alkaline earth metal ions of the intermediate are added to Rl~ of the metal complex, followed by dissociation of the alkaline metal salt or alkaline earth metal salt of Rl~ having low solubility in the form of precipitate. Thus, the target ionic metal complex of the general formula (1) is obtained.
Solvent can be used in the above-mentioned first, second and third processes, and it is not particularly limited as long as it can dissolve the raw materials even in minute amounts. The solvent is preferably an inert solvent, which does not react with compounds in the reaction system. Furthermore, the solvent is preferably one having a dielectric constant of at least 2. The use of a solvent having no dissolving power whatsoever is not preferable, since the reaction proceeds extremely slowly. Even if the solvent has only slight solubility, since the solubility of the target ionic metal complex is extremely large, the reaction proceeds rapidly. Examples of the solvent that can be used in the first, second and third processes include carbonates, esters, ethers, lactones, nitriles, amides, sulfones, alcohols and aromatics, and these solvents can either be used alone or in the form of a mixed solvent of two or more types. Specific examples of the solvent include propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, methylethyl carbonate, dimethoxyethane, acetonitrile, propionitrile, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, nitromethane, N,N-dimethylformamide, dimethylsulfoxide, sulfolane, y-butyrolactone, toluene, ethanol, methanol and water.
The first, second third processes can be conducted at a reaction temperature of -80°C to 100°C, preferably 0°C to 80°C.
The reaction may not proceed sufficiently at a temperature lower than -80°C. Decomposition of the raw materials may occur at a temperature above 100°C. A temperature range of 0°C to 80°C is optimum in order to obtain a sufficient reaction rate while also preventing the occurrence of decomposition.
Since many of the raw materials used in the first, second and third processes are hydrolytic, it is preferable to carry out them in an atmosphere of air, nitrogen or argon and so forth having a low moisture content.
The following nonlimitative examples are illustrative of the present invention.
In a glove box having an atmosphere of a dew point of -50°C, 20.2 g of hexafluoro-2-hydroxyisobutyric acid (HOC(CFs)~COOH) were dissolved in 20 ml of dimethyl carbonate. Next, 6.8 g of lithium tetrakis(methoxy)borate (LiB(OCHs)4) were slowly added to this solution. After this addition, the solution was heated to 60°C and allowed to react for 3 hours. Dimethyl carbonate was removed from the resulting reaction solution under a reduced pressure condition of 1'70°C and 1 tort, thereby obtaining 20.0 g of a white solid as a product. This product was identified by NMR
spectrum and elementary analysis as being LiB(OC(CFs)zC00)a having the following formula.
Lip ~3C ~ B ~ CF3 i 0 0 ° o The NMR spectral data of the product is shown below.
19F-NMR (hexafluorobenzene standard, solvent: CD3CN) 88.1 ppm (6F, q, J = 8 Hz) 88.3 ppm (6F, q, J = 8 Hz) mB-NhlR, (B(OCHs)s standard, solvent: CDsCN) -8.5 ppm (s) EXAIyIPLE 2 10.0 g of hexafluoro-2-hydroxyisobutyric acid (HOC(CFs)2COOH) were dissolved in 20 ml of acetonitrile. Next, 3.4 g of triethylborate (B(OC?H~)s) were slowly added to this solution. After this addition, the solution was heated to 80°C and allowed to react for 3 hours while stirring. 3.5 g of hydroxytetraethyl ammonium ((C~H5)4NOH) were added to the resulting reaction solution, and after stirring at 80°C the solvent, acetonitrile, and by-products, water and ethanol, were removed under a reduced pressure condition of 170°C and 1 torr, thereby obtaining 10.3 g of a white solid as a product. This product was identified by NMR spectrum and elementary analysis as being (C2H5)~NB(OC(CFs)~COO)~.
The NMR spectral data of the product is shown below.
IsF.NMR (hexafluorobenzene standard, solvent: CD3CN) 88:1 ppm (6F, q, J = 8 Hz) 88.3 ppm (6F, q, J = 8 Hz) mB-NMR (B(OCHs)s standard, solvent: CD3CN) -8.5 ppm (s) 10.0 g of hexafluoro-2-hydroxyisobutyric acid (HOC(CFs)aCOOH) were dissolved in 20 ml of acetonitrile. Next, 1.5 g of boric acid (B(OHs)) were slowly added to this solution.
After this addition, the solution was heated to 60°C and allowed to react for 3 hours while stirring. 1.0 g of lithium chloride were added to the resulting reaction solution, and after stirring at 80°C
the solvent, acetonitrile, and a by-product, water, were removed under a reduced pressure condition of 1~0°C and 1 torr, thereby obtaining 10.3 g of a white solid as a product. This product was identified by NMR spectrum and elementary analysis as being LiB(OC(CFs)~COO)~
The NMR spectral data of the product is shown below.
isF-NMR (hexafluorobenzene standard, solvent: CDaCN) 88.1 ppm (6F, q, J = 8 Hz) 88.3 ppm (6F, q, J = 8 Hz) 11B-Nl~2R (B(OCHs)s standard, solvent: CDsCN) -8.5 ppm (s) E1~1NIPLE 4 In a glove box having an atmosphere of a dew point of -50°C, 10.0 g of hexafluoro-2-hydroxyisobutyric acid (HOC(CFs)2COOH) were dissolved in 20 ml of dimethyl carbonate. Next, a lithium methoxidelmethanol solution containing 3.6 g of lithium methoxide (LiOCHs) was slowly added to this solution. The dimethyl carbonate and methanol were removed under a reduced pressure condition of 40°C and 1 tort, thereby obtaining LiOC(CF3)2COOLi as a product. After suspending this compound in acetonitrile, 2.2 g of LiBF~ were added to this solution, followed by heating to 60°C and allowing to react for 10 hours. After filtering the LiF precipitate that formed during the reaction, the acetonitrile was removed under a reduced pressure condition of 170°C and 1 tort, thereby obtaining 10.3 g of a white solid as a product. This product was identified by NMR spectrum and elementary analysis as being LiB(OC(CFs)2C00)2.
The NMRspectral data of the product is shown below.
1~F-NNIR (hexafluorobenzene standard, solvent: CDsCN) 88.1 ppm (6F, q, J = 8 Hz) 88.3 ppm (6F, q, J = 8 Hz) iiB-NMR (B(OCHs)s standard, solvent: CDsCN) -8.5 ppm (s) In a glove box having an atmosphere of a dew point of -50°C, 10.0 g of hexafluoro-2-hydroxyisobutyric acid (HOC(CFs)zCOOH) were dissolved in 20 ml of dimethyl carbonate. Next, a lithium methoxide/methanol solution containing 3.6 g of lithium methoxide (Li0CH3) was slowly added to this solution. The dimethyl carbonate and methanol were removed under a reduced pressure condition of 60°C and 1 torn, thereby obtaining LiOC(CF,3)~COOLi as a product. After dissolving this compound in acetonitrile, 4.4 g of LiBF:~ were added to this solution, followed by heating to 60°C and allowing to react for 10 hours. After filtering the LiF precipitate that formed during the reaction, the dimethyl carbonate was removed under a reduced pressure condition of SO°C and 1 torr, thereby obtaining 12.5 g of a white solid as a product. This product was identified by NMR spectrum and elementary analysis as being LiBFz(OC(CF3)?C00) having the following formula.
CF3 _ Lip FHB O ~F3 .
O
The N1~IR spectral data of the products is shown below.
19F-NMR (hexafluorobenzene standard, solvent: CD3CN) 15.3 ppm (2F, s) 88.2 ppm (6F, s) mB-Nl~~IR (B(OCHa)s standard, solvent: CD3CN) 1~ -14.1 ppm (t, J = 4 Hz) In a glove box having an atmosphere of a dew point of -50°C, 10.0 g of triffuorolactic acid (HOCH(CFs)COOH) were dissolved in ml of dimethyl carbonate. Next, 4.9 g of lithium 20 tetrakis(methoxy)borate (LiB(OCHs)4) were slowly added to this solution. After this addition, the solution was heated to 60°C and allowed to react for 3 hours. Dimethyl carbonate was removed from the resulting reaction solution under a reduced pressure condition of 170°C and 1 torr, thereby obtaining 10.4 g of a white solid as a product. This product was identified by NMR spectrum and elementary analysis as being LiB(OCH(CF3)COO)~.
Lip ~$v 0/ ~'O O O
The N1~IR spectral data of the product is shown below.
1~F-Ni~-IR (hexafluorobenzene standard, solvent: CD3Ch,T) 87.12 ppm (3F, d, J = 8 Hz) 87.18 ppm (3F, d, J = 8 Hz) 87.32 ppm (3F, d, J = 8 Hz) Since the raw material, trifluorolactic acid, is a racemic S modification having two types of optical isomers, three types of peaks were observed in 19F-NMR due to three combinations of (R,R), (S,S) and (R,S).
Mixing I mole of the compound represented lby the general formula (2) with 1/m moles, where m is defined as in the general formula (3), of the metal complex represented by t;he general formula (3) results in addition of the active hydrogens (i.e., hydrogens respectively bonded to Xl and O in the general formula (2)) of the compound of the general formula (2) to R8 of the general formula (3), followed by dissociation in the form of RBH. With this, the target ionic metal complex of the general formula (1) is obtaine d.
As stated above, the second process fox synthesizing the ionic metal complex comprises (a) reacting a first compound represented by the general formula (2) with a metal complex represented by the general formula (4), thereby obtaining an intermediate a.nd (b) reacting the intermediate with a second compound, thereby obtaining the ionic metal complex.
The first compound contains at least two active h.ydxogens, as show n in the general formula (2). The second compound contains a cation represented by Aa* that is a metal ion or opium ion. The 3a second compound is selected from the group consisting of metal halides, metal alkoxides, metal carboxylates, metal hydroxides, metal oxides, metal carbonates, quaternary alky:lonium halides, quaternary alkylonium hydroxides and quaternary alkylonium carboxylates. The symbols used in the formulas (2) and (4) are the same as those used in the general formulas (1) and (3).
Mixing 1 mole of the first compound of the general formula (2) with 1/m moles of the second compound of the general formula (4) S results in addition of the active hydrogens of the first compound of the general formula (2) to R8 of the general formula (4), followed by dissociation in the form of R8H. However, the number of Rg, that is, "2m-1" is deficient by one in the general formula (4), as compared with the number of active hydrogens in the general formula (2). Therefore, the surplus active hydrogen turns into a hydrogen ion (proton), and another active hydrogen that has formed a pair with the surplus active hydrogen is bonded to M.
With this, there is obtained an intermediate represented by the general formula (1) wherein Aa+ is the proton. Then, this intermediate is reacted with the second compound containing Aa+
that is a metal ion or onium ion to conduct an ion-exchange between the proton of the intermediate and Aa+ of the second compound, thereby obtaining the ionic metal complex.
As stated above, the third process for synthesizing the ionic metal complex comprises:
(a) reacting a first compound represented by the general formula (2) with a second compound containing an alkali metal or alkali-earth metal, thereby obtaining an intermediate and (b) reacting the intermediate with a metal complex represented by the general formula (5).
Symbols in the formulas (2) and (5) are the same as those of the general formula (1) with the exception of Rlo. In fact, Rlo represents a halogen or hydroxyl group. By the step (a), active hydrogens of the first compound in an amount of 1 mole can be replaced with the alkali metal or alkali-earth metal of the second compound. The resulting intermediate can be mixed with the metal complex in an amount of 1/m moles to conduct the step (b).
With this, the alkaline metal or alkaline earth metal ions of the intermediate are added to Rl~ of the metal complex, followed by dissociation of the alkaline metal salt or alkaline earth metal salt of Rl~ having low solubility in the form of precipitate. Thus, the target ionic metal complex of the general formula (1) is obtained.
Solvent can be used in the above-mentioned first, second and third processes, and it is not particularly limited as long as it can dissolve the raw materials even in minute amounts. The solvent is preferably an inert solvent, which does not react with compounds in the reaction system. Furthermore, the solvent is preferably one having a dielectric constant of at least 2. The use of a solvent having no dissolving power whatsoever is not preferable, since the reaction proceeds extremely slowly. Even if the solvent has only slight solubility, since the solubility of the target ionic metal complex is extremely large, the reaction proceeds rapidly. Examples of the solvent that can be used in the first, second and third processes include carbonates, esters, ethers, lactones, nitriles, amides, sulfones, alcohols and aromatics, and these solvents can either be used alone or in the form of a mixed solvent of two or more types. Specific examples of the solvent include propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, methylethyl carbonate, dimethoxyethane, acetonitrile, propionitrile, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, nitromethane, N,N-dimethylformamide, dimethylsulfoxide, sulfolane, y-butyrolactone, toluene, ethanol, methanol and water.
The first, second third processes can be conducted at a reaction temperature of -80°C to 100°C, preferably 0°C to 80°C.
The reaction may not proceed sufficiently at a temperature lower than -80°C. Decomposition of the raw materials may occur at a temperature above 100°C. A temperature range of 0°C to 80°C is optimum in order to obtain a sufficient reaction rate while also preventing the occurrence of decomposition.
Since many of the raw materials used in the first, second and third processes are hydrolytic, it is preferable to carry out them in an atmosphere of air, nitrogen or argon and so forth having a low moisture content.
The following nonlimitative examples are illustrative of the present invention.
In a glove box having an atmosphere of a dew point of -50°C, 20.2 g of hexafluoro-2-hydroxyisobutyric acid (HOC(CFs)~COOH) were dissolved in 20 ml of dimethyl carbonate. Next, 6.8 g of lithium tetrakis(methoxy)borate (LiB(OCHs)4) were slowly added to this solution. After this addition, the solution was heated to 60°C and allowed to react for 3 hours. Dimethyl carbonate was removed from the resulting reaction solution under a reduced pressure condition of 1'70°C and 1 tort, thereby obtaining 20.0 g of a white solid as a product. This product was identified by NMR
spectrum and elementary analysis as being LiB(OC(CFs)zC00)a having the following formula.
Lip ~3C ~ B ~ CF3 i 0 0 ° o The NMR spectral data of the product is shown below.
19F-NMR (hexafluorobenzene standard, solvent: CD3CN) 88.1 ppm (6F, q, J = 8 Hz) 88.3 ppm (6F, q, J = 8 Hz) mB-NhlR, (B(OCHs)s standard, solvent: CDsCN) -8.5 ppm (s) EXAIyIPLE 2 10.0 g of hexafluoro-2-hydroxyisobutyric acid (HOC(CFs)2COOH) were dissolved in 20 ml of acetonitrile. Next, 3.4 g of triethylborate (B(OC?H~)s) were slowly added to this solution. After this addition, the solution was heated to 80°C and allowed to react for 3 hours while stirring. 3.5 g of hydroxytetraethyl ammonium ((C~H5)4NOH) were added to the resulting reaction solution, and after stirring at 80°C the solvent, acetonitrile, and by-products, water and ethanol, were removed under a reduced pressure condition of 170°C and 1 torr, thereby obtaining 10.3 g of a white solid as a product. This product was identified by NMR spectrum and elementary analysis as being (C2H5)~NB(OC(CFs)~COO)~.
The NMR spectral data of the product is shown below.
IsF.NMR (hexafluorobenzene standard, solvent: CD3CN) 88:1 ppm (6F, q, J = 8 Hz) 88.3 ppm (6F, q, J = 8 Hz) mB-NMR (B(OCHs)s standard, solvent: CD3CN) -8.5 ppm (s) 10.0 g of hexafluoro-2-hydroxyisobutyric acid (HOC(CFs)aCOOH) were dissolved in 20 ml of acetonitrile. Next, 1.5 g of boric acid (B(OHs)) were slowly added to this solution.
After this addition, the solution was heated to 60°C and allowed to react for 3 hours while stirring. 1.0 g of lithium chloride were added to the resulting reaction solution, and after stirring at 80°C
the solvent, acetonitrile, and a by-product, water, were removed under a reduced pressure condition of 1~0°C and 1 torr, thereby obtaining 10.3 g of a white solid as a product. This product was identified by NMR spectrum and elementary analysis as being LiB(OC(CFs)~COO)~
The NMR spectral data of the product is shown below.
isF-NMR (hexafluorobenzene standard, solvent: CDaCN) 88.1 ppm (6F, q, J = 8 Hz) 88.3 ppm (6F, q, J = 8 Hz) 11B-Nl~2R (B(OCHs)s standard, solvent: CDsCN) -8.5 ppm (s) E1~1NIPLE 4 In a glove box having an atmosphere of a dew point of -50°C, 10.0 g of hexafluoro-2-hydroxyisobutyric acid (HOC(CFs)2COOH) were dissolved in 20 ml of dimethyl carbonate. Next, a lithium methoxidelmethanol solution containing 3.6 g of lithium methoxide (LiOCHs) was slowly added to this solution. The dimethyl carbonate and methanol were removed under a reduced pressure condition of 40°C and 1 tort, thereby obtaining LiOC(CF3)2COOLi as a product. After suspending this compound in acetonitrile, 2.2 g of LiBF~ were added to this solution, followed by heating to 60°C and allowing to react for 10 hours. After filtering the LiF precipitate that formed during the reaction, the acetonitrile was removed under a reduced pressure condition of 170°C and 1 tort, thereby obtaining 10.3 g of a white solid as a product. This product was identified by NMR spectrum and elementary analysis as being LiB(OC(CFs)2C00)2.
The NMRspectral data of the product is shown below.
1~F-NNIR (hexafluorobenzene standard, solvent: CDsCN) 88.1 ppm (6F, q, J = 8 Hz) 88.3 ppm (6F, q, J = 8 Hz) iiB-NMR (B(OCHs)s standard, solvent: CDsCN) -8.5 ppm (s) In a glove box having an atmosphere of a dew point of -50°C, 10.0 g of hexafluoro-2-hydroxyisobutyric acid (HOC(CFs)zCOOH) were dissolved in 20 ml of dimethyl carbonate. Next, a lithium methoxide/methanol solution containing 3.6 g of lithium methoxide (Li0CH3) was slowly added to this solution. The dimethyl carbonate and methanol were removed under a reduced pressure condition of 60°C and 1 torn, thereby obtaining LiOC(CF,3)~COOLi as a product. After dissolving this compound in acetonitrile, 4.4 g of LiBF:~ were added to this solution, followed by heating to 60°C and allowing to react for 10 hours. After filtering the LiF precipitate that formed during the reaction, the dimethyl carbonate was removed under a reduced pressure condition of SO°C and 1 torr, thereby obtaining 12.5 g of a white solid as a product. This product was identified by NMR spectrum and elementary analysis as being LiBFz(OC(CF3)?C00) having the following formula.
CF3 _ Lip FHB O ~F3 .
O
The N1~IR spectral data of the products is shown below.
19F-NMR (hexafluorobenzene standard, solvent: CD3CN) 15.3 ppm (2F, s) 88.2 ppm (6F, s) mB-Nl~~IR (B(OCHa)s standard, solvent: CD3CN) 1~ -14.1 ppm (t, J = 4 Hz) In a glove box having an atmosphere of a dew point of -50°C, 10.0 g of triffuorolactic acid (HOCH(CFs)COOH) were dissolved in ml of dimethyl carbonate. Next, 4.9 g of lithium 20 tetrakis(methoxy)borate (LiB(OCHs)4) were slowly added to this solution. After this addition, the solution was heated to 60°C and allowed to react for 3 hours. Dimethyl carbonate was removed from the resulting reaction solution under a reduced pressure condition of 170°C and 1 torr, thereby obtaining 10.4 g of a white solid as a product. This product was identified by NMR spectrum and elementary analysis as being LiB(OCH(CF3)COO)~.
Lip ~$v 0/ ~'O O O
The N1~IR spectral data of the product is shown below.
1~F-Ni~-IR (hexafluorobenzene standard, solvent: CD3Ch,T) 87.12 ppm (3F, d, J = 8 Hz) 87.18 ppm (3F, d, J = 8 Hz) 87.32 ppm (3F, d, J = 8 Hz) Since the raw material, trifluorolactic acid, is a racemic S modification having two types of optical isomers, three types of peaks were observed in 19F-NMR due to three combinations of (R,R), (S,S) and (R,S).
4.57 ppm (1H, q, J = 8 Hz) 11B-NNIR (B(OCHs)s standard, solvent: CDsCN) -8.03 ppm (s) In a glove box having an atmosphere of a dew point of -50°C, 4.2 g of 4,4,4-trifluoro-3-hydroxy-3-(trifluoromethyl)butyric acid 1S (HOC(CFs)2CHzCOOH) were dissolved in 20 ml of dimethyl carbonate. Next, 1.3 g of lithium tetrakis(methoxy)borate (LiB(OCHs)~ were slowly added to this solution. After this addition, the solution was heated to 60°C and allowed to react for 10 hours. Dimethyl carbonate was removed from the resulting reaction solution under a reduced pressure condition of 120°C and 1 tore, thereby obtaining 4.3 g of a white solid as a product. This product was identified by NMR spectrum and elementary analysis as being LiB(OC(CFs)zCH~C00)z.
C CF3 CF~F _ 3 . ~ 3 Lip H B H
H // O v . H
O O
The N1~IR spectral data of the product is shown below.
1~F-NI~IR (hexafluorobenzene standard, solvent: CDsCN) 85.0 ppm (12F, s) 1H-N~,-IR
2.86 ppm (2H, d, J = 16 Hz) 2.75 ppm (2H, d, J = 16 Hz)
C CF3 CF~F _ 3 . ~ 3 Lip H B H
H // O v . H
O O
The N1~IR spectral data of the product is shown below.
1~F-NI~IR (hexafluorobenzene standard, solvent: CDsCN) 85.0 ppm (12F, s) 1H-N~,-IR
2.86 ppm (2H, d, J = 16 Hz) 2.75 ppm (2H, d, J = 16 Hz)
Claims (20)
1. An ionic metal complex represented by the general formula (1):
wherein M is a transition metal selected from the group consisting of elements of groups 3-11 of the periodic table, or an element selected from the croup consisting of elements of groups 12-15 of the periodic table; A a+
represents a metal ion, onium ion, triphenylmethyl ion, metallocenium ion, or proton; provided that M is not B when A a+ is Cs+; a represents a number from 1 to 3; b represents a number from 1 to 3; p is b/a; m represents a number from 1 to 3; n represents a number from 0 to 4; q is 0 or 1; X1 represents O or S; each of R1 and R2 independently represents H, a halogen, a C1-C10 alkyl group or C1-C10 halogenated alkyl group; R3 represents a C1-C10 alkylene group, C1-Cl0 halogenated alkylene group, C6-C20 aryl group or C6-C20 halogenated aryl group; R4 represents a halogen, Cl-C10 alkyl group, C1-C10 halogenated alkyl group, C6-C20 aryl group, C6-C20 halogenated aryl group or X2R7; X2 represents O, S or NR5; R5 represents H or a C1-C10 alkyl group; and R7 represents a C1-C10 alkyl group, C1-C10 halogenated alkyl group, C6-C20 aryl group or C6-C20 halogenated aryl group.
wherein M is a transition metal selected from the group consisting of elements of groups 3-11 of the periodic table, or an element selected from the croup consisting of elements of groups 12-15 of the periodic table; A a+
represents a metal ion, onium ion, triphenylmethyl ion, metallocenium ion, or proton; provided that M is not B when A a+ is Cs+; a represents a number from 1 to 3; b represents a number from 1 to 3; p is b/a; m represents a number from 1 to 3; n represents a number from 0 to 4; q is 0 or 1; X1 represents O or S; each of R1 and R2 independently represents H, a halogen, a C1-C10 alkyl group or C1-C10 halogenated alkyl group; R3 represents a C1-C10 alkylene group, C1-Cl0 halogenated alkylene group, C6-C20 aryl group or C6-C20 halogenated aryl group; R4 represents a halogen, Cl-C10 alkyl group, C1-C10 halogenated alkyl group, C6-C20 aryl group, C6-C20 halogenated aryl group or X2R7; X2 represents O, S or NR5; R5 represents H or a C1-C10 alkyl group; and R7 represents a C1-C10 alkyl group, C1-C10 halogenated alkyl group, C6-C20 aryl group or C6-C20 halogenated aryl group.
2. An ionic metal complex according to claim 1, wherein said M is an element selected from the group consisting of Al, B, V, Ti, Si, Zr, Ge, Sn, Cu, Y, Zn, Ga, Nb, Ta, Bi, P, As, Sc, Hf and Sb.
3. An ionic metal complex according to claim 2, wherein said M is an element selected from the group consisting of Al, B and P.
4. An ionic metal complex according to claim 1, wherein said A a+ is a lithium ion, quaternary alkyl ammonium ion or proton.
5. An ionic metal complex according to claim 1, wherein said A a+ is a lithium ion, proton or trialkylammonium ion.
6. An ionic metal complex according to claim 1, wherein at least one of R1 and said R2 is a fluorinated alkyl group.
7. An ionic metal complex according to claim 6, wherein said fluorinated alkyl group is a trifluoromethyl group.
8. An ionic metal complex according to claim 1, wherein said R3 is such that a chelate ring containing said M in the general formula (1) is a closed loop of bonded atoms of 5-10 in number.
9. An ionic metal complex according to claim 1, wherein said R7 is a C1-C10 fluorinated alkyl group.
10. A process for synthesizing an ionic metal complex represented by the general formula (1):
wherein M is a transition metal selected from the group consisting of elements of groups 3-11 of the periodic table, or an element selected from the group consisting of elements of groups 12-15 of the periodic table; A a+
represents a metal ion, onium ion, triphenylmethyl ion, metallocenium ion, or proton; provided that M is not B when A a+ is Cs+; a represents a number from 1 to 3; b represents a number from 1 to 3; p is b/a; m represents a number from 1 to 3; n represents a number from 0 to 4; q is 0 or 1; X1 represents O or S; each of R1 and R2 independently represents H, a halogen, a C1-C10 alkyl group or C1-C10 halogenated alkyl group; R3 represents a C1-C10 alkylene group, C1-C10 halogenated alkylene group, C6-C20 aryl group or C6-C20 halogenated aryl group; R4 represents a halogen, C1-C10 alkyl group, C1-C10 halogenated alkyl group, C6-C20 aryl group, C6-C20 halogenated aryl group or X2R7; X2 represents O, S or NR5; R5 represents H or a C1-C10 alkyl group; and R7 represent s a C1-C10 alkyl group, C1-C10 halogenated alkyl group, C6-C20 aryl group or C6-C20 halogenated aryl group, said process comprising reacting a compound represented by the general formula (2) with a metal complex represented by the general formula (3), said compound containing at least two active hydrogens, wherein X1, R1, R2, R3, R4, M, A a+, q, a, b, p, m, and n are defined as above, R8 represents a halogen, hydroxyl group, hydrogen, C1-C10 alkyl group, C1-C10 halogenated alkyl group, C6-C20 aryl group, C6-C20 halogenated aryl group or X3R9; X3 represents O, S or NR5 where R5 is defined as above; and R9 represents a C1-C10 alkyl group, C1-C10 halogenated alkyl group, C6-C20 aryl group or C6-C20 halogenated aryl group.
wherein M is a transition metal selected from the group consisting of elements of groups 3-11 of the periodic table, or an element selected from the group consisting of elements of groups 12-15 of the periodic table; A a+
represents a metal ion, onium ion, triphenylmethyl ion, metallocenium ion, or proton; provided that M is not B when A a+ is Cs+; a represents a number from 1 to 3; b represents a number from 1 to 3; p is b/a; m represents a number from 1 to 3; n represents a number from 0 to 4; q is 0 or 1; X1 represents O or S; each of R1 and R2 independently represents H, a halogen, a C1-C10 alkyl group or C1-C10 halogenated alkyl group; R3 represents a C1-C10 alkylene group, C1-C10 halogenated alkylene group, C6-C20 aryl group or C6-C20 halogenated aryl group; R4 represents a halogen, C1-C10 alkyl group, C1-C10 halogenated alkyl group, C6-C20 aryl group, C6-C20 halogenated aryl group or X2R7; X2 represents O, S or NR5; R5 represents H or a C1-C10 alkyl group; and R7 represent s a C1-C10 alkyl group, C1-C10 halogenated alkyl group, C6-C20 aryl group or C6-C20 halogenated aryl group, said process comprising reacting a compound represented by the general formula (2) with a metal complex represented by the general formula (3), said compound containing at least two active hydrogens, wherein X1, R1, R2, R3, R4, M, A a+, q, a, b, p, m, and n are defined as above, R8 represents a halogen, hydroxyl group, hydrogen, C1-C10 alkyl group, C1-C10 halogenated alkyl group, C6-C20 aryl group, C6-C20 halogenated aryl group or X3R9; X3 represents O, S or NR5 where R5 is defined as above; and R9 represents a C1-C10 alkyl group, C1-C10 halogenated alkyl group, C6-C20 aryl group or C6-C20 halogenated aryl group.
11. A process according to claim 10, wherein said reacting is conducted in a solvent having a dielectric constant of at least 2.
12. A process according to claim 10, wherein said reacting is conducted at a temperature from 0 to 80°C.
13. A process for synthesizing an ionic metal complex represented by the general formula (1):
wherein M is a transition metal selected from the group consisting of elements of groups 3-11. of the periodic table, or an element selected from the croup consisting of elements of groups 12-15 of the periodic table; A a+
represents a metal ion, onium ion, triphenylmethyl ion, metallocenium ion, or proton; provided that M is not B when A a+ is Cs+; a represents a number from 1 to 3; b represents a number from 1 to 3; p is b/a; m represents a number from 1 to 3; n represents a number from 0 to 4; q is 0 or 1; X1 represents O or S; each of R1 and R2 independently represents H, a halogen, a C1-C10 alkyl group or C1-C10 halogenated alkyl group; R3 represents a C1-C10 alkylene group, C1-C10 halogenated alkylene group, C6-C20 aryl group or C6-C20 halogenated aryl group; R~ represents a halogen, C1-C10 alkyl group, C1-C10 halogenated alkyl group, C6-C20 aryl group, C6-C20 halogenated aryl group or X2R7; X2 represents 0, S or NR5; R5 represents H or a C1-C10 alkyl group; and R7 represents a C1-C1p alkyl group, C1-C10 halogenated alkyl group, C6-C20 aryl group or C6-C20 halogenated aryl group, said process comprising:
reacting a first compound represented by the general formula (2) with a metal complex represented by the general formula (4), said first compound containing at least two active hydrogens, thereby obtaining an intermediates; and reacting said intermediate with a second compound, said second compound containing a canon represented by A a+ defined as above and being selected from the group consisting of metal halides, metal alkoxides, metal carboxylytes, metal hydroxides, metal oxides, metal carbonates, quaternary alkylonium halides, quaternary alkylonium hydroxides and quaternary alkylonium carboxylates, thereby obtaining said ionic metal complex, wherein X1, R1, R2, R3, R4, M, q, m, and n are defined as above, R8 represents a halogen, hydroxyl group, hydrogen, C1-C10 alkyl group, C1-C10 halogenated alkyl group, C6-C20 aryl group, C6-C20 halogenated aryl group or X3R9; X3 represents O, S or NR5 where R5 is defined as above and R9 represents a C1-C10 alkyl group, C1-C10 halogenated alkyl group, C6-C20 aryl group or C6-C20 halogenated aryl group.
wherein M is a transition metal selected from the group consisting of elements of groups 3-11. of the periodic table, or an element selected from the croup consisting of elements of groups 12-15 of the periodic table; A a+
represents a metal ion, onium ion, triphenylmethyl ion, metallocenium ion, or proton; provided that M is not B when A a+ is Cs+; a represents a number from 1 to 3; b represents a number from 1 to 3; p is b/a; m represents a number from 1 to 3; n represents a number from 0 to 4; q is 0 or 1; X1 represents O or S; each of R1 and R2 independently represents H, a halogen, a C1-C10 alkyl group or C1-C10 halogenated alkyl group; R3 represents a C1-C10 alkylene group, C1-C10 halogenated alkylene group, C6-C20 aryl group or C6-C20 halogenated aryl group; R~ represents a halogen, C1-C10 alkyl group, C1-C10 halogenated alkyl group, C6-C20 aryl group, C6-C20 halogenated aryl group or X2R7; X2 represents 0, S or NR5; R5 represents H or a C1-C10 alkyl group; and R7 represents a C1-C1p alkyl group, C1-C10 halogenated alkyl group, C6-C20 aryl group or C6-C20 halogenated aryl group, said process comprising:
reacting a first compound represented by the general formula (2) with a metal complex represented by the general formula (4), said first compound containing at least two active hydrogens, thereby obtaining an intermediates; and reacting said intermediate with a second compound, said second compound containing a canon represented by A a+ defined as above and being selected from the group consisting of metal halides, metal alkoxides, metal carboxylytes, metal hydroxides, metal oxides, metal carbonates, quaternary alkylonium halides, quaternary alkylonium hydroxides and quaternary alkylonium carboxylates, thereby obtaining said ionic metal complex, wherein X1, R1, R2, R3, R4, M, q, m, and n are defined as above, R8 represents a halogen, hydroxyl group, hydrogen, C1-C10 alkyl group, C1-C10 halogenated alkyl group, C6-C20 aryl group, C6-C20 halogenated aryl group or X3R9; X3 represents O, S or NR5 where R5 is defined as above and R9 represents a C1-C10 alkyl group, C1-C10 halogenated alkyl group, C6-C20 aryl group or C6-C20 halogenated aryl group.
14. A process according to claim 13, wherein said reacting is conducted in a solvent having a dielectric constant of at least 2.
15. A process according to claim 13, wherein, said reacting is conducted at a temperature from 0 to 80°C.
16. A process for synthesizing an ionic metal complex represented by the general formula (1):
wherein M is a transition metal selected from the group consisting of elements of groups 3-11 of the periodic table, or an element selected from the group consisting of elements of groups 12-15 of the periodic table; A a+
represents a metal ion, onium ion, triphenylmethyl ion, metallocenium ion, or proton; provided that M is not B when A a+ is Cs+; a represents a number from 1 to 3; b represents a number from 1 to 3; p is b/a; m represents a number from 1 to 3; n represents a number from 0 to 4; q is 0 or 1; X1 represents O or S; each of R1 and R2 independently represents H, a halogen, a C1-C10 alkyl group or C1-C10 halogenated alkyl group; R3 represents a C1-C10 alkylene group, C1-C10 halogenated alkylene group, C6-C20 aryl group or C6-C20 halogenated aryl group; R4 represents a halogen, C1-C10 alkyl group, C1-C10 halogenated alkyl group, C6-C20 aryl group, C6-C20 halogenated aryl group or X2R7; X2 represents O, S or NR5 ; R5 represents H or a C1-C10 alkyl group; and R7 represents a C1-C10 alkyl group, C1-C10 halogenated alkyl group, C6-C20 aryl group or C6-C20 halogenated aryl group, said process comprising:
reacting a first compound represented by the general formula (2) with a second compound containing an alkali metal or alkali-earth metal, thereby obtaining an intermediate and reacting said intermediate with a metal complex represented by the general formula (5), wherein X1, R1, R2, R3, R4, M, A a+, q, a, b, p, m, and n are defined as above, R10 represents a halogen or hydroxyl group.
wherein M is a transition metal selected from the group consisting of elements of groups 3-11 of the periodic table, or an element selected from the group consisting of elements of groups 12-15 of the periodic table; A a+
represents a metal ion, onium ion, triphenylmethyl ion, metallocenium ion, or proton; provided that M is not B when A a+ is Cs+; a represents a number from 1 to 3; b represents a number from 1 to 3; p is b/a; m represents a number from 1 to 3; n represents a number from 0 to 4; q is 0 or 1; X1 represents O or S; each of R1 and R2 independently represents H, a halogen, a C1-C10 alkyl group or C1-C10 halogenated alkyl group; R3 represents a C1-C10 alkylene group, C1-C10 halogenated alkylene group, C6-C20 aryl group or C6-C20 halogenated aryl group; R4 represents a halogen, C1-C10 alkyl group, C1-C10 halogenated alkyl group, C6-C20 aryl group, C6-C20 halogenated aryl group or X2R7; X2 represents O, S or NR5 ; R5 represents H or a C1-C10 alkyl group; and R7 represents a C1-C10 alkyl group, C1-C10 halogenated alkyl group, C6-C20 aryl group or C6-C20 halogenated aryl group, said process comprising:
reacting a first compound represented by the general formula (2) with a second compound containing an alkali metal or alkali-earth metal, thereby obtaining an intermediate and reacting said intermediate with a metal complex represented by the general formula (5), wherein X1, R1, R2, R3, R4, M, A a+, q, a, b, p, m, and n are defined as above, R10 represents a halogen or hydroxyl group.
17. A process according to claim 16, wherein said reacting is conducted in a solvent having a dielectric constant of at least 2.
18. A process according to claim 16, wherein said reacting is conducted at a temperature from 0 to 80°C.
19. An ionic metal complex according to claim 1, wherein each of R1 and R2 independently represents a halogen or C1-C10 halogenated alkyl group.
20. A process according to claim 13, wherein each of R1 and R2 independently represents a halogen or C1-C10 halogenated alkyl group.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21904599 | 1999-08-02 | ||
| JP11-219045 | 1999-08-02 | ||
| JP2000069201A JP3824465B2 (en) | 1999-08-02 | 2000-03-13 | Synthesis of ionic complexes |
| JP2000-069201 | 2000-03-13 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2314739A1 CA2314739A1 (en) | 2001-02-02 |
| CA2314739C true CA2314739C (en) | 2006-01-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002314739A Expired - Fee Related CA2314739C (en) | 1999-08-02 | 2000-07-31 | Ionic metal complex and process for synthesizing same |
Country Status (7)
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| US (1) | US6407232B1 (en) |
| EP (1) | EP1074555A3 (en) |
| JP (1) | JP3824465B2 (en) |
| KR (1) | KR100367254B1 (en) |
| CN (1) | CN1321967C (en) |
| CA (1) | CA2314739C (en) |
| TW (1) | TWI283244B (en) |
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| JP3498905B2 (en) * | 1999-08-02 | 2004-02-23 | セントラル硝子株式会社 | Electrolyte for electrochemical devices |
| JP3463926B2 (en) * | 1999-11-15 | 2003-11-05 | セントラル硝子株式会社 | Electrolyte for electrochemical devices |
| DE19959722A1 (en) * | 1999-12-10 | 2001-06-13 | Merck Patent Gmbh | Alkyl spiroborate salts for use in electrochemical cells |
| CN1182617C (en) | 2000-05-08 | 2004-12-29 | 森陶硝子株式会社 | Electrolyte used for electrochemical equipment |
| US7504473B2 (en) | 2000-06-16 | 2009-03-17 | Arizona Board Of Regents For And On Behalf Of Arizona State University | Conductive polymeric compositions for lithium batteries |
| US7527899B2 (en) | 2000-06-16 | 2009-05-05 | Arizona Board Of Regents For And On Behalf Of Arizona State University | Electrolytic orthoborate salts for lithium batteries |
| EP1195834B1 (en) | 2000-10-03 | 2010-09-15 | Central Glass Company, Limited | Electrolyte for electrochemical device |
| US6787267B2 (en) | 2000-11-28 | 2004-09-07 | Central Glass Company, Limited | Electrolyte for electrochemical device |
| DE10108592C1 (en) * | 2001-02-22 | 2002-08-14 | Chemetall Gmbh | Borchelate complexes, processes for their preparation and their use |
| DE10139409A1 (en) * | 2001-08-17 | 2003-02-27 | Merck Patent Gmbh | Polymer electrolytes and their use in galvanic cells |
| US6849752B2 (en) * | 2001-11-05 | 2005-02-01 | Central Glass Company, Ltd. | Process for synthesizing ionic metal complex |
| WO2004094487A1 (en) * | 2003-03-21 | 2004-11-04 | Dow Global Technologies, Inc. | Morphology controlled olefin polymerization process |
| US20060216612A1 (en) * | 2005-01-11 | 2006-09-28 | Krishnakumar Jambunathan | Electrolytes, cells and methods of forming passivation layers |
| US20080026297A1 (en) * | 2005-01-11 | 2008-01-31 | Air Products And Chemicals, Inc. | Electrolytes, cells and methods of forming passivaton layers |
| JP5211422B2 (en) | 2005-01-24 | 2013-06-12 | セントラル硝子株式会社 | Synthesis of ionic complexes |
| US7820323B1 (en) | 2006-09-07 | 2010-10-26 | The United States Of America As Represented By The Secretary Of The Army | Metal borate synthesis process |
| JP5767915B2 (en) * | 2011-09-06 | 2015-08-26 | 株式会社日本触媒 | Boron-containing compounds |
| JP6031828B2 (en) * | 2012-05-30 | 2016-11-24 | セントラル硝子株式会社 | Method for producing tetrafluoro (oxalato) phosphate solution |
| EP3058613A1 (en) | 2013-10-17 | 2016-08-24 | Lubrizol Advanced Materials, Inc. | Copolymers with a polyacrylic acid backbone as performance enhancers for lithium-ion cells |
| CN104362306B (en) * | 2014-09-19 | 2017-02-15 | 中国科学院宁波材料技术与工程研究所 | Chain-like bidentatum dicarboxylic acid-metallic composite material and preparation and application thereof |
| JP7304880B2 (en) | 2018-03-30 | 2023-07-07 | ダウ グローバル テクノロジーズ エルエルシー | Dinuclear olefin polymerization activator |
| JP7495880B2 (en) | 2018-03-30 | 2024-06-05 | ダウ グローバル テクノロジーズ エルエルシー | Highly soluble alkyl-substituted carbenium borates as cocatalysts for olefin polymerization |
| EP3774942A1 (en) | 2018-03-30 | 2021-02-17 | Dow Global Technologies LLC | Olefin polymerization activators |
| KR102729476B1 (en) | 2018-03-30 | 2024-11-14 | 다우 글로벌 테크놀로지스 엘엘씨 | Olefin polymerization activator |
| US12037440B2 (en) | 2018-03-30 | 2024-07-16 | Dow Global Technologies Llc | Highly soluble bis-borate as binuclear co-catalysts for olefin polymerization |
| EP4037056B1 (en) * | 2021-01-29 | 2026-03-25 | Innolith Technology AG | So2-based electrolyte for rechargeable battery cell and rechargeable battery cell |
| GB2626595A (en) * | 2023-01-27 | 2024-07-31 | Sumitomo Chemical Co | Compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1020331B (en) * | 1953-01-02 | 1957-12-05 | Advance Produktion G M B H Deu | Process for the production of new organotin compounds |
| US3403304A (en) * | 1966-02-07 | 1968-09-24 | Sprague Electric Co | Electrolytic capacitor with an electrolyte of an ammonium organoboron compound |
| US3403305A (en) * | 1966-11-10 | 1968-09-24 | Sprague Electric Co | Electrolytic capacitor having an electrolyte containing a borate coordination compound |
| GB2143228A (en) * | 1983-07-13 | 1985-02-06 | Standard Telephones Cables Ltd | Electrolytes |
| JPH0448709A (en) * | 1990-06-15 | 1992-02-18 | Japan Carlit Co Ltd:The | Manufacture of solid electrolytic capacitor |
| JPH05150555A (en) * | 1991-11-18 | 1993-06-18 | Japan Carlit Co Ltd:The | Electrophotographic toner |
| GB9218779D0 (en) * | 1992-09-04 | 1992-10-21 | Unilever Plc | Antiperspirant actives and compositions |
| DE4316104A1 (en) * | 1993-05-13 | 1994-11-17 | Manfred Wuehr | Electrolyte for use in a galvanic cell |
| EP0907217B1 (en) * | 1993-06-18 | 2006-02-15 | Hitachi Maxell Ltd. | Organic electrolytic solution cell |
| DE19633027A1 (en) * | 1996-08-16 | 1998-02-19 | Merck Patent Gmbh | Process for the production of new lithium borate complexes |
-
2000
- 2000-03-13 JP JP2000069201A patent/JP3824465B2/en not_active Expired - Fee Related
- 2000-07-17 TW TW089114249A patent/TWI283244B/en not_active IP Right Cessation
- 2000-07-19 EP EP00115578A patent/EP1074555A3/en not_active Ceased
- 2000-07-25 US US09/625,349 patent/US6407232B1/en not_active Expired - Lifetime
- 2000-07-31 CA CA002314739A patent/CA2314739C/en not_active Expired - Fee Related
- 2000-08-01 KR KR10-2000-0044549A patent/KR100367254B1/en not_active Expired - Fee Related
- 2000-08-02 CN CNB001224697A patent/CN1321967C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1321967C (en) | 2007-06-20 |
| JP3824465B2 (en) | 2006-09-20 |
| CN1282726A (en) | 2001-02-07 |
| EP1074555A2 (en) | 2001-02-07 |
| JP2001106694A (en) | 2001-04-17 |
| US6407232B1 (en) | 2002-06-18 |
| TWI283244B (en) | 2007-07-01 |
| KR20010049956A (en) | 2001-06-15 |
| KR100367254B1 (en) | 2003-01-10 |
| CA2314739A1 (en) | 2001-02-02 |
| EP1074555A3 (en) | 2005-09-07 |
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