WO2007091867A1 - Novel crosslinker and solid polymer electrolyte using the same - Google Patents
Novel crosslinker and solid polymer electrolyte using the same Download PDFInfo
- Publication number
- WO2007091867A1 WO2007091867A1 PCT/KR2007/000724 KR2007000724W WO2007091867A1 WO 2007091867 A1 WO2007091867 A1 WO 2007091867A1 KR 2007000724 W KR2007000724 W KR 2007000724W WO 2007091867 A1 WO2007091867 A1 WO 2007091867A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- polymer electrolyte
- reaction scheme
- compounds
- cdcl
- Prior art date
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- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 69
- 239000004971 Cross linker Substances 0.000 title claims abstract description 48
- 239000007787 solid Substances 0.000 title claims abstract description 48
- -1 acryl group Chemical group 0.000 claims abstract description 70
- 150000001875 compounds Chemical class 0.000 claims abstract description 60
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- 150000001412 amines Chemical group 0.000 claims abstract description 20
- 125000006575 electron-withdrawing group Chemical group 0.000 claims abstract description 20
- 229920000233 poly(alkylene oxides) Polymers 0.000 claims abstract description 16
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical group CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 53
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 28
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 28
- 229920001223 polyethylene glycol Polymers 0.000 claims description 24
- 239000003999 initiator Substances 0.000 claims description 20
- 239000002202 Polyethylene glycol Substances 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 17
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 15
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 12
- 238000001723 curing Methods 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- 239000004014 plasticizer Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 230000002687 intercalation Effects 0.000 claims description 8
- 238000009830 intercalation Methods 0.000 claims description 8
- 150000008427 organic disulfides Chemical class 0.000 claims description 8
- 229920000767 polyaniline Polymers 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 229920001451 polypropylene glycol Polymers 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 7
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 7
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 6
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 150000001350 alkyl halides Chemical class 0.000 claims description 6
- 150000001983 dialkylethers Chemical class 0.000 claims description 6
- 238000010494 dissociation reaction Methods 0.000 claims description 5
- 230000005593 dissociations Effects 0.000 claims description 5
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 238000000016 photochemical curing Methods 0.000 claims description 5
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 claims description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- SESFRYSPDFLNCH-UHFFFAOYSA-N benzyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1=CC=CC=C1 SESFRYSPDFLNCH-UHFFFAOYSA-N 0.000 claims description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 238000013007 heat curing Methods 0.000 claims description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 4
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 4
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical compound O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 claims description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- 229910012761 LiTiS2 Inorganic materials 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 2
- YNSNJGRCQCDRDM-UHFFFAOYSA-N 1-chlorothioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl YNSNJGRCQCDRDM-UHFFFAOYSA-N 0.000 claims description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 2
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 claims description 2
- CERJZAHSUZVMCH-UHFFFAOYSA-N 2,2-dichloro-1-phenylethanone Chemical compound ClC(Cl)C(=O)C1=CC=CC=C1 CERJZAHSUZVMCH-UHFFFAOYSA-N 0.000 claims description 2
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 claims description 2
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 claims description 2
- NACPTFCBIGBTSJ-UHFFFAOYSA-N 2-hydroxy-2-phenyl-1-(2-propan-2-ylphenyl)ethanone Chemical compound CC(C)C1=CC=CC=C1C(=O)C(O)C1=CC=CC=C1 NACPTFCBIGBTSJ-UHFFFAOYSA-N 0.000 claims description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- AXYQEGMSGMXGGK-UHFFFAOYSA-N 2-phenoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(=O)C(C=1C=CC=CC=1)OC1=CC=CC=C1 AXYQEGMSGMXGGK-UHFFFAOYSA-N 0.000 claims description 2
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 claims description 2
- UGVRJVHOJNYEHR-UHFFFAOYSA-N 4-chlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 UGVRJVHOJNYEHR-UHFFFAOYSA-N 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 2
- 229910000733 Li alloy Inorganic materials 0.000 claims description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 claims description 2
- 229910013265 LiMOS2 Inorganic materials 0.000 claims description 2
- 229910002993 LiMnO2 Inorganic materials 0.000 claims description 2
- 229910013406 LiN(SO2CF3)2 Inorganic materials 0.000 claims description 2
- 229910003005 LiNiO2 Inorganic materials 0.000 claims description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N Vanadium(V) oxide Inorganic materials O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 2
- YZSKZXUDGLALTQ-UHFFFAOYSA-N [Li][C] Chemical compound [Li][C] YZSKZXUDGLALTQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 2
- 150000004056 anthraquinones Chemical class 0.000 claims description 2
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical compound C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- 229960002903 benzyl benzoate Drugs 0.000 claims description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 2
- 229920001400 block copolymer Polymers 0.000 claims description 2
- 229960004132 diethyl ether Drugs 0.000 claims description 2
- 238000006471 dimerization reaction Methods 0.000 claims description 2
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 150000002596 lactones Chemical class 0.000 claims description 2
- 239000001989 lithium alloy Substances 0.000 claims description 2
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 claims description 2
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 claims description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 2
- 229910021450 lithium metal oxide Inorganic materials 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 2
- 150000005677 organic carbonates Chemical class 0.000 claims description 2
- 230000002441 reversible effect Effects 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims description 2
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims 1
- VWIIJDNADIEEDB-UHFFFAOYSA-N 3-methyl-1,3-oxazolidin-2-one Chemical compound CN1CCOC1=O VWIIJDNADIEEDB-UHFFFAOYSA-N 0.000 claims 1
- 229910014114 LiNi1-xMxO2 Inorganic materials 0.000 claims 1
- 229910014907 LiNi1−xMxO2 Inorganic materials 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 152
- 238000002360 preparation method Methods 0.000 description 145
- 238000006243 chemical reaction Methods 0.000 description 136
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 135
- 238000005160 1H NMR spectroscopy Methods 0.000 description 53
- 238000000034 method Methods 0.000 description 47
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 30
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 24
- 239000012299 nitrogen atmosphere Substances 0.000 description 24
- 239000010408 film Substances 0.000 description 19
- 239000011259 mixed solution Substances 0.000 description 19
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 18
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 description 18
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- 229910018963 Pt(O) Inorganic materials 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000000178 monomer Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 229940086542 triethylamine Drugs 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
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- SJNALLRHIVGIBI-UHFFFAOYSA-N allyl cyanide Chemical compound C=CCC#N SJNALLRHIVGIBI-UHFFFAOYSA-N 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 229910003002 lithium salt Inorganic materials 0.000 description 6
- 159000000002 lithium salts Chemical class 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 239000001294 propane Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
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- 239000002244 precipitate Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
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- 238000004519 manufacturing process Methods 0.000 description 4
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- 238000003756 stirring Methods 0.000 description 4
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 description 4
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 description 3
- 238000004293 19F NMR spectroscopy Methods 0.000 description 3
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 3
- 0 CC(CCCCCCC1)C[S+]C(*)(*)OC(C)(C)[S+](C)(*)OC1*(C)(*)N Chemical compound CC(CCCCCCC1)C[S+]C(*)(*)OC(C)(C)[S+](C)(*)OC1*(C)(*)N 0.000 description 3
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- 229940052303 ethers for general anesthesia Drugs 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 239000005041 Mylar™ Substances 0.000 description 2
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000012320 chlorinating reagent Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- QPJDMGCKMHUXFD-UHFFFAOYSA-N cyanogen chloride Chemical compound ClC#N QPJDMGCKMHUXFD-UHFFFAOYSA-N 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 235000019256 formaldehyde Nutrition 0.000 description 2
- RILRLUYRESTKJF-UHFFFAOYSA-N imidazol-2-ylidenemethanone;methoxymethane Chemical compound COC.O=C=C1N=CC=N1 RILRLUYRESTKJF-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
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- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- CFVVSQSFKWLGAX-UHFFFAOYSA-N phenol;propane Chemical compound CCC.OC1=CC=CC=C1 CFVVSQSFKWLGAX-UHFFFAOYSA-N 0.000 description 2
- ORYMXRYDDDAXDD-UHFFFAOYSA-N phenyl prop-2-enoate propane Chemical compound C(C=C)(=O)OC1=CC=CC=C1.CCC ORYMXRYDDDAXDD-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- JPSIUEJLDNCSHS-UHFFFAOYSA-N propane;prop-2-enoic acid Chemical compound CCC.OC(=O)C=C JPSIUEJLDNCSHS-UHFFFAOYSA-N 0.000 description 2
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 2
- GFADZIUESKAXAK-UHFFFAOYSA-N tetrafluorohydrazine Chemical compound FN(F)N(F)F GFADZIUESKAXAK-UHFFFAOYSA-N 0.000 description 2
- HVHZEKKZMFRULH-UHFFFAOYSA-N 2,6-ditert-butyl-4-methylpyridine Chemical compound CC1=CC(C(C)(C)C)=NC(C(C)(C)C)=C1 HVHZEKKZMFRULH-UHFFFAOYSA-N 0.000 description 1
- DIOZVWSHACHNRT-UHFFFAOYSA-N 2-(2-prop-2-enoxyethoxy)ethanol Chemical compound OCCOCCOCC=C DIOZVWSHACHNRT-UHFFFAOYSA-N 0.000 description 1
- QIRNGVVZBINFMX-UHFFFAOYSA-N 2-allylphenol Chemical compound OC1=CC=CC=C1CC=C QIRNGVVZBINFMX-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical class OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- BSMGLVDZZMBWQB-UHFFFAOYSA-N 2-methyl-1-phenylpropan-1-one Chemical compound CC(C)C(=O)C1=CC=CC=C1 BSMGLVDZZMBWQB-UHFFFAOYSA-N 0.000 description 1
- GCYHRYNSUGLLMA-UHFFFAOYSA-N 2-prop-2-enoxyethanol Chemical compound OCCOCC=C GCYHRYNSUGLLMA-UHFFFAOYSA-N 0.000 description 1
- ZSPTYLOMNJNZNG-UHFFFAOYSA-N 3-Buten-1-ol Chemical compound OCCC=C ZSPTYLOMNJNZNG-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- OEFATZRUDCDCEI-UHFFFAOYSA-P CC(CCCOCC(CO1)OC1=O)O[Si+](C)(CCCOCC(CO1)OC1=O)O[S+](C)(C)(CCCOCC(CO1)OC1=O)O[SH+](C)(CCCOCC(CO1)OC1=O)OS Chemical compound CC(CCCOCC(CO1)OC1=O)O[Si+](C)(CCCOCC(CO1)OC1=O)O[S+](C)(C)(CCCOCC(CO1)OC1=O)O[SH+](C)(CCCOCC(CO1)OC1=O)OS OEFATZRUDCDCEI-UHFFFAOYSA-P 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 229910007857 Li-Al Inorganic materials 0.000 description 1
- 229910007912 Li-Cd Inorganic materials 0.000 description 1
- 229910013232 LiMoO2 Inorganic materials 0.000 description 1
- 229910014912 LiNi1−xMx Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910015103 LixWO2 Inorganic materials 0.000 description 1
- 229910008447 Li—Al Inorganic materials 0.000 description 1
- 229910008299 Li—Cd Inorganic materials 0.000 description 1
- DRBBFCLWYRJSJZ-UHFFFAOYSA-N N-phosphocreatine Chemical compound OC(=O)CN(C)C(=N)NP(O)(O)=O DRBBFCLWYRJSJZ-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000012494 Quartz wool Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- FCCRGBVYSYHQRQ-UHFFFAOYSA-N [ethenyl(dimethyl)silyl]oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)(C)C=C FCCRGBVYSYHQRQ-UHFFFAOYSA-N 0.000 description 1
- HFEHLDPGIKPNKL-UHFFFAOYSA-N allyl iodide Chemical compound ICC=C HFEHLDPGIKPNKL-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- JKJWYKGYGWOAHT-UHFFFAOYSA-N bis(prop-2-enyl) carbonate Chemical compound C=CCOC(=O)OCC=C JKJWYKGYGWOAHT-UHFFFAOYSA-N 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- OPHUWKNKFYBPDR-UHFFFAOYSA-N copper lithium Chemical compound [Li].[Cu] OPHUWKNKFYBPDR-UHFFFAOYSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- ZZTSQZQUWBFTAT-UHFFFAOYSA-N diethylcyanamide Chemical compound CCN(CC)C#N ZZTSQZQUWBFTAT-UHFFFAOYSA-N 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000004404 heteroalkyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- YWVYZMVYXAVAKS-UHFFFAOYSA-N pyridin-1-ium;trifluoromethanesulfonate Chemical compound C1=CC=[NH+]C=C1.[O-]S(=O)(=O)C(F)(F)F YWVYZMVYXAVAKS-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- XPDWGBQVDMORPB-UHFFFAOYSA-N trifluoromethane acid Natural products FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
- H01M6/181—Cells with non-aqueous electrolyte with solid electrolyte with polymeric electrolytes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- 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
-
- 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
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
- H01M6/188—Processes of manufacture
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
Definitions
- the present invention relates to a novel crosslinker compound, and a crosslinkable solid polymer electrolyte containing the same. More specifically, the present invention relates to a novel crosslinker, which has acryl group or phenylacryl group crosslinkable by heat treatment or light irradiation at two terminal groups and/or in linear chain of methyl siloxane polymer having an amine substituted with electron withdrawing groups, or at least one of polyalkylene oxide group, cyano group and propylene carbonate group as a side branch in addition to the amine substituted with electron withdrawing groups, and a gel or solid polymer electrolyte containing the novel crosslinker.
- Solid polymer electrolytes are not only convenient to use because they do not cause liquid leakage and are superior in vibration-shock resistance, but also suitable for use in light, small portable electronics equipments, wireless information & communication equipments and home appliances, and high capacity lithium polymer secondary batteries for electric vehicles because they have very low self-discharge and can be used even at a high temperature. Therefore, many extensive researches have been done on improvement of these performances.
- a PAO (polyalkylene oxide) type solid polymer electrolyte was first discovered by P. V. Wright (British Polymer Journal, 7, 319), and it was named as an "ionic conductive polymer" by M. Armand in 1978.
- a solid polymer electrolyte is composed of lithium salt complexes and a polymer containing electron-donating atoms, such as, oxygen, nitrogen and phosphor.
- a solid polymer electrolytes is polyethylene oxide (PEO) and lithium salt complexes thereof. Because these have ionic conductivity as low as 10 "8 S/cm at room temperature, they cannot be applied to electrochemical devices that usually operate at room temperature. A reason why the PAO type solid polymer electrolytes have very low ionic conductivity at room temperature is because they are easily crystallized and thus, motion of molecular chains therein is restricted.
- ionic conductivity of such electrolytes at room temperature is as low as lO ⁇ -lO "4 S/cm, which may have poor mechanical properties when they were formed into films.
- Abraham et al. introduced polyethylene oxide with low molecular weight into a vinylidenhexaf ⁇ uoride - hexafluoropropene copolymer to enhance ionic couductivity (Chem. Mater., 9 (1997) 1978).
- the CF 3 radical thusly produced takes a hydrogen atom from the PEO polymer chain and forms HCF 3 .
- a C-O-C- group is formed and the main chain of the polymer therein is cut off.
- CH 3 produced by chain scission together with the CF 3 radical attack the chain or break a C-O bond.
- a Li-O-R compound thusly formed is attached to the electrode surface and the electrode surface is passivated. Therefore, there is a need to develop a novel substance which replaces the PAO type plasticizer having the above drawbacks.
- Anion receptors improve anion stability by the interaction between a Lewis acid and a Lewis base.
- These anion receptors are compounds having electron deficient atoms (N and B), which facilitate the movement of lithium cations (Li + ) by coordinating electron-rich anions around to interfere with forming ion pairs between the anions and the lithium cations.
- the first known anion receptors are aza-ether compounds containing cyclic or linear amides, by which N atoms in amides substituted by perfluoroalkylsulfonyl group become electron deficient and interact with electron-rich anions through coulombic attraction (J. Electrochem. Soc, 143 (1996) 3825, 147 (2000) 9).
- aza-ethers have drawbacks that they exhibit limited solubility in polar solvents adopted to the typical nonaqueous electrolytes and electrochemical stability window of electrolytes containing LiCl salt does not meet the commercial need of battery voltage 4.0V required of cathode materials.
- aza- ethers are unstable to LiPF 6 (Electrochem. Solid-State Lett., 5 (2002) A248). That is, chemically and thermally unstable LiPF 6 is in equilibrium with solid LiF and PF 5 gas even at room temperature, and production of PF 5 gas makes the equilibrium moved towards generating PF 5 gas.
- PF 5 has a tendency to initiate a series of reactions such as ring-opening polymerization or breaking an ether bond composed of atoms having a lone- pair electron, e.g., oxygen or nitrogen.
- PF 5 a relatively strong Lewis acid, is known to attack electron pairs (J. Power Sources, 104 (2002) 260). Due to high electron density, aza-ethers are promptly attached by PF 5 . Therefore, in order to solve the above-described problems, there is a need to develop a novel substance capable of resolving the electrochemical instability and the instability towards lithium salts and offering enhanced ionic conductivity by designing a compound which does not have an easily attacked nitrogen or oxygen atom in the middle
- an object of the present invention to provide a novel crosslinker, which has acryl group or phenylacryl group crosslinkable by heat treatment or light irradiation at two terminal groups and/or in linear chain of methyl siloxane polymer having an amine substituted with electron withdrawing groups, or at least one of polyalkylene oxide group, cyano group and propylene carbonate group as a side branch in addition to the amine substituted with electron withdrawing groups.
- a crosslinker represented by the following Formula 1 : [Formula 1] wherein R 1 and R 2 each independently represents a hydrogen atom, or an electron withdrawing functional group selected from the group consisting of -SO 2 CF 3 , -CN, -F, -Cl, -COCF 3 , -BF 3 and -SO 2 CN, but do not both simultaneously represent a hydrogen atom; R 3 represents a hydrogen atom or a cyano group;
- R 4 is a hydrogen atom
- R 5 and R 6 independently represents a hydrogen atom or a methyl group
- R 7 and the other R 7 in the formula 1 independently represents an alkyl, an alkenyl, an alkyl halide, an alkenyl halide, an alkanol, a halogen, a hydrogen atom or a hydroxy group
- Rg and the other R 8 in the formula 1 independently represents an alkyl, an alkenyl,
- R 9 represents a hydrogen atom or a methyl group
- R 1O represents -CH 2 -, R 11 and the other R 11 in the formula 1 independently represents an alkyl, an alkenyl, an alkyl halide, an alkenyl halide;
- Y and Z each independently represent -O-, -S-, -CO-, -OCO-, -OCOO- or -COO-;
- n is an integer from 1 to 100;
- o, p, q, t and u are integers from O to 100, respectively;
- r and s are integers from O to 20, respectively, whose sum is at least 1 ;
- v represents integer from 1 to 6;
- w represents integer from O to 4.
- the compound represented by the Formula 1 has a main structure of methyl siloxane polymer having an amine substituted with electron withdrawing groups, or at least one of polyalkylene oxide group, cyano group and propylene carbonate group as a side branch in addition to the amine substituted with electron withdrawing groups, and the compound has two to four acryl functional groups or two phenylacryl functional groups at its two terminal groups and/or in the middle of the chain.
- the amine substituted with electron withdrawing groups increases the dissociation of alkali metal salts and therefore, enhances electronegativity and cation transference number.
- nitrogen in the amine becomes electron deficient by electron withdrawing groups, such as -SO 2 CF 3 , - CN, -F, -Cl, -COCF 3 , -BF 3 and -SO 2 CN, and forms electrically neutral complexes with anions of alkali metal salts.
- electron withdrawing groups such as -SO 2 CF 3 , - CN, -F, -Cl, -COCF 3 , -BF 3 and -SO 2 CN
- the compound of Formula 1 can be easily approached by bulky and soft anion such as trifluoromethane sulfone imide since the center of the nitrogen atom is exposed, therefore dissociation of lithium salt is promoted, the complex can be formed more effectively. As a result, alkali metal cationic mobility is increased and thus, high ionic conductivity can be achieved.
- polyalkylene oxide group, cyano group and propylene carbonate group and the like also include atoms with high electronegativity such as oxygen and nitrogen, and thus enhance ionic conductivity by increasing alkali metal cationic mobility.
- the crosslinker of the present invention comprises flexible polymethyl siloxane polymer as a main chain, therefore complements mechanical properties such as drawing and bending properties, and also contains amine substituted with electron withdrawing groups, polyalkylene oxide group, cyano group and propylene carbonate group as a side branch to improve compatibility of plasticizer added in order to enhance ionic conductivity.
- the crosslinker of the present invention has a structure containing two to four acryl functional groups or two phenylacryl functional groups at its two terminal groups and/or in the middle of the chain, therefore it makes the solid polymer electrolyte form three dimensional net-shaped structure after crosslinking.
- the crosslinker represented by the Formula 1 can be synthesized by any known method.
- the compound of the Formula 1 can be synthesized by: hydrosilylating a polymethylcyclo polysiloxane (D t+n+o+ p + qH) represented by the following Formula 3 (the starting material) with allyl trifluoro sulfonamide, polyalkylene glycol allyl ether, allyl cyanide, and allyl propylene carbonate to synthesize the compound represented
- the present invention provides gel polymer electrolytes and solid polymer electrolytes containing the crosslinker represented by Formula 1.
- the present invention provides a gel polymer electrolyte, which comprises (i) a crosslinker of the Formula 1 ; (ii) a nonaqueous solvent; (iii) an anion receptor; (iv) a curing initiator; and (v) an alkali metal ion containing substance.
- a solid polymer electrolyte which comprises (i) a crosslinker of the Formula 1; (ii) plasticizer; (iii) a curing initiator; and (iv) an alkali metal ion containing substance.
- the nonaqueous solvent used for the electrolyte includes ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), propylene carbonate, ether, organic carbonate, lactone, formate, ester, sulfonate, nitrite, oxazolidinone, tetrahydrofuran, 2- methyltetrahydrofuran, 4-methyl-l,3-dioxolane, 1,3-dioxolane, 1,2-dimethoxylethane,
- the gel polymer electrolytes of the present invention use the anion receptor, for example, linear or cyclic siloxane compounds having amine substituted with electron withdrawing groups, or at least one of polyalkylene oxide group, cyano group and propylene carbonate group as a side branch in addition to the amine substituted with electron withdrawing groups; linear or cyclic hydrocarbon compounds having amine substituted with electron withdrawing groups at its terminal group; or aromatic hydrocarbon compounds having amine substituted with electron withdrawing groups and the like.
- the anion receptor for example, linear or cyclic siloxane compounds having amine substituted with electron withdrawing groups, or at least one of polyalkylene oxide group, cyano group and propylene carbonate group as a side branch in addition to the amine substituted with electron withdrawing groups; linear or cyclic hydrocarbon compounds having amine substituted with electron withdrawing groups at its terminal group; or aromatic hydrocarbon compounds having amine substituted with electron withdrawing groups and the like.
- the alkali metal ion containing substance includes LiSO 3 CF 3 , LiCOOC 2 Fs, LiN(SO 2 CF 3 ) 2 , LiC(SO 2 CF 3 ) 3 , LiClO 4 , LiAsF 6 , LiBF 4 , LiPF 6 , LiSbF 6 , LiI, LiBr, LiCl or a mixture thereof.
- the gel polymer electrolyte contains a curing initiator.
- a curing initiator a photocuring initiator, a heat-curing initiator, or a mixture thereof can be used.
- Preferred examples of the photocuring initiator is selected from the group consisting of dimethoxyphenyl acetophenone (DMPA), t-butylperoxypivalate, ethyl benzoin ether, isopropyl benzoin ether, ⁇ -methyl bezoin ethyl ether, benzoin phenyl ether,
- DMPA dimethoxyphenyl acetophenone
- t-butylperoxypivalate ethyl benzoin ether
- isopropyl benzoin ether ⁇ -methyl bezoin ethyl ether
- benzoin phenyl ether benzoin phenyl ether
- heat-curing initiator examples include azoisobutyrontrile compounds, peroxide compounds or mixtures thereof.
- the solid polymer electrolyte of the present invention may contain plasticizer in order to enhance conductivity by elevating dissociation of metal salts and conductivity of lithium ion.
- the plasticizer may include one or combination selected from the group consisting of an anion receptor, a polyalkyleneglycol dialkylether and a
- the present invention may use the anion receptor such as linear of cyclic siloxane compound, linear hydrocarbon compounds and aromatic hydrocarbon compound having amine substituted with electron withdrawing groups in order to solve the problems caused by low molecular weight polyethyleneglycol dimethylether (PEGDME) used for enhancing conductivity.
- anion receptor such as linear of cyclic siloxane compound, linear hydrocarbon compounds and aromatic hydrocarbon compound having amine substituted with electron withdrawing groups
- polyalkyleneglycol dialkylether which is used as other plasticizer
- polyethyleneglycol dimethylether PEGDME
- polyethyleneglycol diethylether polyethyleneglycol dipropylether
- polyethyleneglycol dibutylether polyethyleneglycol diglycidylether, polypropyleneglycol dimethylether, polypropyleneglycol diglycidylether
- polypropyleneglycol/polyethyleneglycol copolymer terminated with dibutylether polyethyleneglycol/polypropyleneglycol/polyethyleneglycol block copolymer terminated with dibutylether.
- the gel polymer electrolyte of the present invention preferably contains 1 - 40 parts by weight of the crosslinker, 0.5 - 86.5 parts by weight of the nonaqueous solvent, 0 - 30 parts by weight of the anion receptor, 3 - 60 parts by weight of the alkali metal ion containing substance, and 0.5 - 5 parts by weight of a curing initiator.
- the solid polymer electrolyte of the present invention preferably contains 10 - 95 parts by weight of the crosslinker, 0.5 - 86.5 parts by weight of one or more substance(s) selected from the anion receptor, polyalkyleneglycol dialkylether, nonaqueous solvent and mixtures thereof, 3 — 60 parts by weight of the alkali metal ion containing substance, and
- the present invention provides an electrochemical cell comprising the gel polymer electrolyte or solid polymer electrolyte containing the above crosslinker, a cathode and an anode.
- an electrochemical cell comprising the gel polymer electrolyte or solid polymer electrolyte containing the above crosslinker, a cathode and an anode.
- a cathode is composed of a cathode, an anode, and a separator, while a cell using the solid polymer electrolyte is composed of a cathode and an anode.
- an anode and a cathode used in the electrochemical cell of the present invention are manufactured by any known method of manufacturing anodes and cathodes used in conventional cells. Also, the components of the electrochemical cell of the present invention can be assembled by any known method.
- the anode is made of a material selected from the group that consists of lithium; lithium alloys, such as Li-Al, Li-Si, or Li-Cd; lithium-carbon intercalation compounds; lithium-graphite intercalation compounds; lithium metal oxide intercalation compounds, such as Li x WO 2 or LiMoO 2 ; lithium metal sulfide intercalation compounds, such as LiTiS 2 ; mixtures thereof; and mixtures of these and alkali metals.
- lithium alloys such as Li-Al, Li-Si, or Li-Cd
- lithium-carbon intercalation compounds lithium-graphite intercalation compounds
- lithium metal oxide intercalation compounds such as Li x WO 2 or LiMoO 2
- lithium metal sulfide intercalation compounds such as LiTiS 2 ; mixtures thereof; and mixtures of these and alkali metals.
- the cathode is made of a material selected from the group that consists of transition metal oxides, transition metal chalcogenides, poly(carbondisulfide)polymers, organic
- disulfide redox polymers polyaniline, organic disulfide/polyaniline complexes, and mixtures of these and oxychlorides.
- transition metal oxides are Li 2 5 V 6 O 13 , Li 1 2 V 2 O 5 , LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , LiMnO 2 , LiNi 1-x M x 0 2 (wherein M is Co, Mg, Al or Ti) and the like.
- transition metal chalcogenides are LiNbSe 3 , LiTiS 2 , LiMoS 2 and the like.
- the organic disulfide redox polymers are prepared by reversible electrochemical dimerization/scission or polymerization/depolymerization of the organic disulfide polymers.
- the organic disulfide/polyaniline complexes are preferably mixtures of polyaniline and 2,5-dimercapto-l,3,4-thiadiazole.
- the present invention provides a polymer electrolyte film using the gel polymer electrolyte or the solid polymer electrolyte of the present invention.
- a preparation method of a gel or solid polymer electrolyte film containing the components of the present invention is as follows:
- a nonaqueous solvent, an anion receptor and an alkali metal ion containing substance are mixed in a vessel at an appropriate mixing ratio, and are stirred by a stirrer.
- a crosslinker of the present invention is then added to the solution and mixed together.
- a composite mixture for preparing a gel polymer electrolyte film is made.
- the solution thusly prepared is coated onto a support substrate made of glass or polyethylene, or a commercially available Mylar film to an appropriate thickness.
- the coated substrate is dried, exposed to electron beams, UV rays or ⁇ -rays, or heated to cause the hardening reaction, and a desired film is obtained.
- a plasticizer and an alkali metal ion containing material are mixed in a vessel at an appropriate mixing ratio, and are stirred by a stirrer.
- a crosslinker compound of the present invention is added to the solution and mixed together.
- a curing initiator is added to the solution, and a composite mixture for preparing a solid polymer electrolyte film is made.
- the solution thusly prepared is coated onto a support substrate made of glass or polyethylene, or a commercially available Mylar film to an appropriate thickness.
- the coated substrate is
- Another example of the preparation method for a film is as follows.
- a spacer for regulating the thickness is fixed on both ends of the support substrate. Then, another support substrate is placed thereon and is hardened with the radiator or a heat source to prepare a solid polymer electrolyte film.
- FIG. 1 is a graph showing a property of ionic conductivity of the solid polymer electrolytes of the present invention (Experimental example 3).
- THF dried over Na.
- the reaction mixture was refluxed for 24 hours under nitrogen atmosphere.
- the THF was evaporated under reduced pressure and the residual was dissolved in chloroform or methylene chloride and extracted three times with 5wt% NaOH solution.
- Preparation Examples 276 - 291 Compounds (Preparation Examples 276 - 291) of the Formula 4 in the Reaction Scheme 1 were prepared using the procedures described in Preparation Examples 3, 4 and 7-12 in the weight ratio shown in Table 10 below. [Table 10]
- Preparation Example 425 Preparation of Di-l,3-di(propane acrylate) (DaDi) (Step 1) 2.6g of 3-butene-l-ol instead of 3-allyloxy-l,2-propanediol and 3.Og of 1,1,3,3- tetramethyldisiloxane (D 2 , 0.0223 mol) were reacted under the same method as in (step 1) of Preparation Example 424 to obtain D 2 -l,3-di(propanol) (see the Reaction Scheme 29).
- the crosslinker compound represented by Formula 1 is all of compounds synthesized by the same method described in the following Examples in combination of the monomer (Formula 4) in Reaction Scheme 1 prepared from Preparation Examples 1 to 423 and polymerization terminators substituted with acryl or phenyl acryl group in the Reaction Scheme 1 prepared from Preparation Examples 424 to 426, but are limited to the compounds prepared in the following Examples.
- reaction products were added to 50ml of chloroform and 30ml of saturated aqueous Na 2 SO 4 solution, and neutralized and washed with 5 wt% of Na 2 CO 3 aqueous solution until neutrality was reached.
- MgSO 4 was added to the neutralized reactants and the mixture was stirred.
- the precipitates were filtered, hydroquinone (100 ppm) as a polymerization inhibitor was added thereto, and the resultant was evaporated under the reduced pressure to obtain Ta-0.86TFSI-10TEGMP (see
- crosslinker compounds of Formula 1 (Examples 5 to 6) having a composition (weight ratio) shown in Table 24 were prepared by the same method as in Example 1. [Table 24]
- Solid polymer electrolyte films were prepared having a composition shown in Table 25 by using the crosslinker Ta-xTFSI-y TEGMP of Examples 1 to 3 and the crosslinker of Ta-IOTEGMP of Comparative Example 1. Then, ionic conductivities of the solid polymer electrolyte films were measured as follows. First, a solid polymer electrolyte composition was coated onto a conductive glass substrate or onto a lithium- copper foil, photocured, and dried sufficiently. Under nitrogen atmosphere, AC impedance between band shaped (or sandwich shaped) electrodes was measured, and the measurement was analyzed with a frequency response analyzer to interpret complex impedance.
- Solid polymer electrolyte films were prepared having a composition shown in Table 26 by using the crosslinker Pha-xTFSI-yTEGMP of Examples 4 to 6. Then, ionic
- Solid polymer electrolyte films were prepared having a composition shown in Table 27 by using the crosslinker Ta-2.58TFSI-10TEGMP of Example 3. Then, ionic
- FIG. 1 shows a change of the ionic conductivities according to the temperature when the crosslinker Ta-2.58TFSI-10TEGMP and anion receptor C 4 -TFSI as a plasticizer were used.
- the solid polymer electrolyte composition of the present invention has excellent mechanical properties such as drawing and bending properties owing to the skeletal structure of the added crosslinker, and offers substantially enhanced ionic conductivities at a room temperature to prepare the electrolyte thin film.
- the electrolyte thin film of the present invention has good film-forming properties and electrochemical stabilities, so they are for a broad range of applications which include small lithium polymer secondary cells used in portable information terminals, e.g., cell phones, notebook computers, etc., and all kinds of electronic equipments, e.g., camcorders, and large capacity lithium polymer secondary cells used in power storage systems for power equalization and electric vehicles.
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Abstract
Disclosed is a novel crosslinker compound, and a crosslinkable solid polymer electrolyte containing the same. More specifically, the present invention relates to a novel crosslinker, which has acryl group or phenylacryl group crosslinkable by heat treatment or light irradiation at two terminal groups and/or in linear chain of methyl siloxane polymer having an amine substituted with electron withdrawing groups, or at least one of polyalkylene oxide group, cyano group and propylene carbonate group as a side branch in addition to the amine substituted with electron withdrawing groups; a gel or solid polymer electrolyte containing the novel crosslinker; and a electrochemical cell containing the same.
Description
NOVEL CROSSLINKER AND SOLID POLYMER ELECTROLYTE USING THE
SAME
Field of the Invention The present invention relates to a novel crosslinker compound, and a crosslinkable solid polymer electrolyte containing the same. More specifically, the present invention relates to a novel crosslinker, which has acryl group or phenylacryl group crosslinkable by heat treatment or light irradiation at two terminal groups and/or in linear chain of methyl siloxane polymer having an amine substituted with electron withdrawing groups, or at least one of polyalkylene oxide group, cyano group and propylene carbonate group as a side branch in addition to the amine substituted with electron withdrawing groups, and a gel or solid polymer electrolyte containing the novel crosslinker.
Description of the Related Art Solid polymer electrolytes are not only convenient to use because they do not cause liquid leakage and are superior in vibration-shock resistance, but also suitable for use in light, small portable electronics equipments, wireless information & communication equipments and home appliances, and high capacity lithium polymer secondary batteries for electric vehicles because they have very low self-discharge and can be used even at a high temperature. Therefore, many extensive researches have been done on improvement of these performances. In 1975, a PAO (polyalkylene oxide) type solid polymer electrolyte was first discovered by P. V. Wright (British Polymer Journal, 7, 319), and it was named as an "ionic conductive polymer" by M. Armand in 1978. Typically, a solid polymer electrolyte is composed of lithium salt complexes and a polymer containing electron-donating atoms, such as, oxygen, nitrogen and phosphor. One of the most well-
known solid polymer electrolytes is polyethylene oxide (PEO) and lithium salt complexes thereof. Because these have ionic conductivity as low as 10"8 S/cm at room temperature, they cannot be applied to electrochemical devices that usually operate at room temperature. A reason why the PAO type solid polymer electrolytes have very low ionic conductivity at room temperature is because they are easily crystallized and thus, motion of molecular chains therein is restricted. In order to increase mobility of molecular chains, the crystalline area existing in the polymer structure should be minimized while the amorphous area therein should be expanded. A research to achieve such has been and is under way by using a siloxane having a flexible molecular chain (Marcromol. Rapid Commun., 7 (1986) 115) or a phosphagen (J. Am. Chem. Soc, 106 (1984) 6854) as a main chain, or by introducing PAO having a relatively short molecular length as a side branch (Electrochem. Acta, 34 (1989) 635). According to another research in progress, net-shaped solid polymer electrolytes are prepared by introducing at least one crosslinkable functional group to the PAO as a terminal group. Unfortunately however, ionic conductivity of such electrolytes at room temperature is as low as lO^-lO"4 S/cm, which may have poor mechanical properties when they were formed into films. As a result of continuous researches, Abraham et al. introduced polyethylene oxide with low molecular weight into a vinylidenhexafϊuoride - hexafluoropropene copolymer to enhance ionic couductivity (Chem. Mater., 9 (1997) 1978). In addition, by adding lower molecular weight PEGDME (polyethyleneglycol dimethylether) to a photocuring type crosslinking agent having a siloxane based main chain and a PEO side branch, the ionic conductivity was increased to δxlO"4 S/cm at room temperature under film forming conditions (J. Power Sources 119- 121 (2003) 448). However, cycling efficiency on a Ni electrode was about 53% at most mainly because the newly deposited lithium surface rapidly eroded, thereby passivating the
electrode surface (Solid State Ionics 119 (1999) 205, Solid State Ionics 135 (2000) 283). That is, according to Vincent, lithium metal reacts with a lithium salt as follows (Solid
State Chem. 17 (1987) 145):
LiSO3CF3 + Li (s) → 2Li+ + SO3 2" + CF3- The CF3 radical thusly produced takes a hydrogen atom from the PEO polymer chain and forms HCF3. In result, a =C-O-C- group is formed and the main chain of the polymer therein is cut off. At this time, CH3 produced by chain scission together with the CF3 radical attack the chain or break a C-O bond. A Li-O-R compound thusly formed is attached to the electrode surface and the electrode surface is passivated. Therefore, there is a need to develop a novel substance which replaces the PAO type plasticizer having the above drawbacks.
On the other hand, Anion receptors improve anion stability by the interaction between a Lewis acid and a Lewis base. These anion receptors are compounds having electron deficient atoms (N and B), which facilitate the movement of lithium cations (Li+) by coordinating electron-rich anions around to interfere with forming ion pairs between the anions and the lithium cations. The first known anion receptors are aza-ether compounds containing cyclic or linear amides, by which N atoms in amides substituted by perfluoroalkylsulfonyl group become electron deficient and interact with electron-rich anions through coulombic attraction (J. Electrochem. Soc, 143 (1996) 3825, 147 (2000) 9). However, these aza-ethers have drawbacks that they exhibit limited solubility in polar solvents adopted to the typical nonaqueous electrolytes and electrochemical stability window of electrolytes containing LiCl salt does not meet the commercial need of battery voltage 4.0V required of cathode materials. In addition, it has been discovered that aza- ethers are unstable to LiPF6 (Electrochem. Solid-State Lett., 5 (2002) A248). That is,
chemically and thermally unstable LiPF6 is in equilibrium with solid LiF and PF5 gas even at room temperature, and production of PF5 gas makes the equilibrium moved towards generating PF5 gas.
LiPF6 (s) ^=- LiF (s) + PF5 (g)
In a nonaqueous solvent, PF5 has a tendency to initiate a series of reactions such as ring-opening polymerization or breaking an ether bond composed of atoms having a lone- pair electron, e.g., oxygen or nitrogen. Meanwhile, PF5, a relatively strong Lewis acid, is known to attack electron pairs (J. Power Sources, 104 (2002) 260). Due to high electron density, aza-ethers are promptly attached by PF5. Therefore, in order to solve the above-described problems, there is a need to develop a novel substance capable of resolving the electrochemical instability and the instability towards lithium salts and offering enhanced ionic conductivity by designing a compound which does not have an easily attacked nitrogen or oxygen atom in the middle
of a compound as in aza-ether compounds or PAO. Solid polymer electrolyte reinforced mechanical properties was reported by using crosslinker including three ethylene glycol acrylates in the center of cyclic alkyl or hetero alkyl molecules [Korean patent laid-open No. 2004-4121 and Korean patent application No. 2001-12913]. In particular, it is expected that the polysiloxane polymers containing polyethylene oxide group as a side branch enhance molecule chain movement since the polysiloxane polymers have characteristic flexibility and low glass transition temperature. Therefore the research of applying the polysiloxane polymer to the basic skeletal structure of polyalkylene oxide type crosslinkable and comb-shaped solid polymer electrolyte was proceeding [Macromol. Chem. Rapid Commun., 7 (1986) 115, USP 4,673,718, USP 4,766,185, USP 5,227,043, USP 5,440,011, Japanese Patent laid-open No. 1993-290616 et
al.]. However polysiloxane solid polymer electrolyte is improper for used in lithium cell functioned at room temperature since it is weak in mechanical property and low ionic
conductivity of 10"5 S/cm.
Detailed Description of the Invention
Technical Subject
It is, therefore, an object of the present invention to provide a novel crosslinker, which has acryl group or phenylacryl group crosslinkable by heat treatment or light irradiation at two terminal groups and/or in linear chain of methyl siloxane polymer having an amine substituted with electron withdrawing groups, or at least one of polyalkylene oxide group, cyano group and propylene carbonate group as a side branch in addition to the amine substituted with electron withdrawing groups.
It is another object of the present invention to provide a gel or solid polymer electrolyte containing the novel crosslinkers. It is still another object of the present invention to provide an electrochemical cell which uses an electrolyte containing the novel crosslinkers.
Technical Solution
To achieve the above objects and advantages, there is provided a crosslinker represented by the following Formula 1 : [Formula 1]
wherein R1 and R2 each independently represents a hydrogen atom, or an electron withdrawing functional group selected from the group consisting of -SO2CF3, -CN, -F, -Cl, -COCF3, -BF3 and -SO2CN, but do not both simultaneously represent a hydrogen atom; R3 represents a hydrogen atom or a cyano group;
R4 is a hydrogen atom,
R5 and R6 independently represents a hydrogen atom or a methyl group; R7 and the other R7 in the formula 1 independently represents an alkyl, an alkenyl, an alkyl halide, an alkenyl halide, an alkanol, a halogen, a hydrogen atom or a hydroxy group;
Rg and the other R8 in the formula 1 independently represents an alkyl, an alkenyl,
an alkyl halide, an alkenyl halide or
;
R9 represents a hydrogen atom or a methyl group;
R1O represents -CH2-,
R11 and the other R11 in the formula 1 independently represents an alkyl, an alkenyl,
an alkyl halide, an alkenyl halide;
Y and Z each independently represent -O-, -S-, -CO-, -OCO-, -OCOO- or -COO-; n is an integer from 1 to 100; o, p, q, t and u are integers from O to 100, respectively; r and s are integers from O to 20, respectively, whose sum is at least 1 ; v represents integer from 1 to 6; and
w represents integer from O to 4.
The compound represented by the Formula 1 has a main structure of methyl siloxane polymer having an amine substituted with electron withdrawing groups, or at least one of polyalkylene oxide group, cyano group and propylene carbonate group as a side branch in addition to the amine substituted with electron withdrawing groups, and the compound has two to four acryl functional groups or two phenylacryl functional groups at its two terminal groups and/or in the middle of the chain. Among the functional groups introduced as a side branch, the amine substituted with electron withdrawing groups increases the dissociation of alkali metal salts and therefore, enhances electronegativity and cation transference number. In detail, nitrogen in the amine becomes electron deficient by electron withdrawing groups, such as -SO2CF3, - CN, -F, -Cl, -COCF3, -BF3 and -SO2CN, and forms electrically neutral complexes with anions of alkali metal salts. In this manner, the dissociation of alkali metal salts into ions is promoted. Unlike a family of aza-ether based compounds disclosed in U.S. Pat. Nos. 5,705,689 and 6,120,941 where an easily attackable nitrogen atom existing in the middle of a compound causes electrochemical instability and instability to lithium salts (especially, LiPF6) and steric hindrance, the compound of the present invention resolved these
problems. The compound of Formula 1 can be easily approached by bulky and soft anion such as trifluoromethane sulfone imide since the center of the nitrogen atom is exposed, therefore dissociation of lithium salt is promoted, the complex can be formed more effectively. As a result, alkali metal cationic mobility is increased and thus, high ionic conductivity can be achieved. On the other hand, polyalkylene oxide group, cyano group and propylene carbonate group and the like also include atoms with high electronegativity such as oxygen and nitrogen, and thus enhance ionic conductivity by increasing alkali metal cationic mobility.
In addition, the crosslinker of the present invention comprises flexible polymethyl siloxane polymer as a main chain, therefore complements mechanical properties such as drawing and bending properties, and also contains amine substituted with electron withdrawing groups, polyalkylene oxide group, cyano group and propylene carbonate group as a side branch to improve compatibility of plasticizer added in order to enhance ionic conductivity. The crosslinker of the present invention has a structure containing two to four acryl functional groups or two phenylacryl functional groups at its two terminal groups and/or in the middle of the chain, therefore it makes the solid polymer electrolyte form three dimensional net-shaped structure after crosslinking.
The crosslinker represented by the Formula 1 can be synthesized by any known method.
For example, the compound of the Formula 1 can be synthesized by: hydrosilylating a polymethylcyclo polysiloxane (Dt+n+o+p+qH) represented by the following Formula 3 (the starting material) with allyl trifluoro sulfonamide, polyalkylene glycol allyl ether, allyl cyanide, and allyl propylene carbonate to synthesize the compound represented
g
by the following Formula (4); and reacting the compound of Formula (4) with a polymerization terminator represented by the following Formula (5) using a fuming H2SO4
as a catalyst. [Reaction Scheme 1]
,N R2
(3) _Z (CH2CHO)- (CH2CHO)- CH3
R5 R6
Pt(O) THF
(5)
Fuming H2SO4
(1)
The present invention provides gel polymer electrolytes and solid polymer electrolytes containing the crosslinker represented by Formula 1.
In detail, the present invention provides a gel polymer electrolyte, which comprises (i) a crosslinker of the Formula 1 ; (ii) a nonaqueous solvent; (iii) an anion receptor; (iv) a curing initiator; and (v) an alkali metal ion containing substance.
In addition, the present invention provides a solid polymer electrolyte, which comprises (i) a crosslinker of the Formula 1; (ii) plasticizer; (iii) a curing initiator; and (iv) an alkali metal ion containing substance.
The nonaqueous solvent used for the electrolyte includes ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), propylene carbonate, ether, organic carbonate, lactone, formate, ester, sulfonate, nitrite, oxazolidinone, tetrahydrofuran, 2- methyltetrahydrofuran, 4-methyl-l,3-dioxolane, 1,3-dioxolane, 1,2-dimethoxylethane,
dimethoxymethane, γ-butyrolactone, methyl formate, sulforane, acetonitrile, 3-methyl-2-
oxazolidinone, N-methyl-2-pyrrolidinone or mixtures thereof. In addition, the gel polymer electrolytes of the present invention use the anion receptor, for example, linear or cyclic siloxane compounds having amine substituted with electron withdrawing groups, or at least one of polyalkylene oxide group, cyano group and propylene carbonate group as a side branch in addition to the amine substituted with electron withdrawing groups; linear or cyclic hydrocarbon compounds having amine substituted with electron withdrawing groups at its terminal group; or aromatic hydrocarbon compounds having amine substituted with electron withdrawing groups and the like.
The alkali metal ion containing substance includes LiSO3CF3, LiCOOC2Fs, LiN(SO2CF3)2, LiC(SO2CF3)3, LiClO4, LiAsF6, LiBF4, LiPF6, LiSbF6, LiI, LiBr, LiCl or a mixture thereof.
The gel polymer electrolyte contains a curing initiator. As for the curing initiator, a photocuring initiator, a heat-curing initiator, or a mixture thereof can be used.
Preferred examples of the photocuring initiator is selected from the group consisting of dimethoxyphenyl acetophenone (DMPA), t-butylperoxypivalate, ethyl
benzoin ether, isopropyl benzoin ether, α-methyl bezoin ethyl ether, benzoin phenyl ether,
α-acyloxime ester, α,α-diethoxyacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-
methyl-1-phenylpropane-l-on, 1-hydroxycyclohexyl phenyl ketone, anthraquinone, thioxanthone, isopropyl thioxanthone, chlorothioxanthone, benzophenone, p- chlorobenzophenone, benzyl benzoate, benzoyl benzoate, Michler's ketone and a mixture thereof.
Examples of the heat-curing initiator include azoisobutyrontrile compounds, peroxide compounds or mixtures thereof.
In addition, the solid polymer electrolyte of the present invention may contain plasticizer in order to enhance conductivity by elevating dissociation of metal salts and conductivity of lithium ion. The plasticizer may include one or combination selected from the group consisting of an anion receptor, a polyalkyleneglycol dialkylether and a
nonaqueous solvent.
In particular, the present invention may use the anion receptor such as linear of cyclic siloxane compound, linear hydrocarbon compounds and aromatic hydrocarbon compound having amine substituted with electron withdrawing groups in order to solve the problems caused by low molecular weight polyethyleneglycol dimethylether (PEGDME) used for enhancing conductivity.
Examples of the polyalkyleneglycol dialkylether which is used as other plasticizer include polyethyleneglycol dimethylether (PEGDME), polyethyleneglycol diethylether, polyethyleneglycol dipropylether, polyethyleneglycol dibutylether, polyethyleneglycol diglycidylether, polypropyleneglycol dimethylether, polypropyleneglycol diglycidylether; polypropyleneglycol/polyethyleneglycol copolymer terminated with dibutylether; or polyethyleneglycol/polypropyleneglycol/polyethyleneglycol block copolymer terminated
with dibutylether.
More particularly, the gel polymer electrolyte of the present invention preferably contains 1 - 40 parts by weight of the crosslinker, 0.5 - 86.5 parts by weight of the nonaqueous solvent, 0 - 30 parts by weight of the anion receptor, 3 - 60 parts by weight of the alkali metal ion containing substance, and 0.5 - 5 parts by weight of a curing initiator.
The solid polymer electrolyte of the present invention preferably contains 10 - 95 parts by weight of the crosslinker, 0.5 - 86.5 parts by weight of one or more substance(s) selected from the anion receptor, polyalkyleneglycol dialkylether, nonaqueous solvent and mixtures thereof, 3 — 60 parts by weight of the alkali metal ion containing substance, and
0.5 - 5 parts by weight of a curing initiator.
In addition, the present invention provides an electrochemical cell comprising the gel polymer electrolyte or solid polymer electrolyte containing the above crosslinker, a cathode and an anode. Particularly, a cell using the gel polymer electrolyte of the present
invention is composed of a cathode, an anode, and a separator, while a cell using the solid polymer electrolyte is composed of a cathode and an anode.
Here, an anode and a cathode used in the electrochemical cell of the present invention are manufactured by any known method of manufacturing anodes and cathodes used in conventional cells. Also, the components of the electrochemical cell of the present invention can be assembled by any known method.
The anode is made of a material selected from the group that consists of lithium; lithium alloys, such as Li-Al, Li-Si, or Li-Cd; lithium-carbon intercalation compounds; lithium-graphite intercalation compounds; lithium metal oxide intercalation compounds, such as LixWO2 or LiMoO2; lithium metal sulfide intercalation compounds, such as
LiTiS2; mixtures thereof; and mixtures of these and alkali metals.
The cathode is made of a material selected from the group that consists of transition metal oxides, transition metal chalcogenides, poly(carbondisulfide)polymers, organic
disulfide redox polymers, polyaniline, organic disulfide/polyaniline complexes, and mixtures of these and oxychlorides.
Examples of the transition metal oxides are Li2 5V6O13, Li1 2V2O5, LiCoO2, LiNiO2, LiMn2O4, LiMnO2, LiNi1-xMx02 (wherein M is Co, Mg, Al or Ti) and the like. Examples of the transition metal chalcogenides are LiNbSe3, LiTiS2, LiMoS2 and the like. The organic disulfide redox polymers are prepared by reversible electrochemical dimerization/scission or polymerization/depolymerization of the organic disulfide polymers. The organic disulfide/polyaniline complexes are preferably mixtures of polyaniline and 2,5-dimercapto-l,3,4-thiadiazole.
Moreover, the present invention provides a polymer electrolyte film using the gel polymer electrolyte or the solid polymer electrolyte of the present invention.
A preparation method of a gel or solid polymer electrolyte film containing the components of the present invention is as follows:
First, in case of a gel polymer electrolyte, a nonaqueous solvent, an anion receptor and an alkali metal ion containing substance are mixed in a vessel at an appropriate mixing ratio, and are stirred by a stirrer. A crosslinker of the present invention is then added to the solution and mixed together. In this manner, a composite mixture for preparing a gel polymer electrolyte film is made. The solution thusly prepared is coated onto a support substrate made of glass or polyethylene, or a commercially available Mylar film to an appropriate thickness. The coated substrate is dried, exposed to electron beams, UV rays
or γ-rays, or heated to cause the hardening reaction, and a desired film is obtained.
In case of a solid polymer electrolyte, on the other hand, a plasticizer and an alkali metal ion containing material are mixed in a vessel at an appropriate mixing ratio, and are stirred by a stirrer. A crosslinker compound of the present invention is added to the solution and mixed together. Meanwhile, a curing initiator is added to the solution, and a composite mixture for preparing a solid polymer electrolyte film is made. The solution thusly prepared is coated onto a support substrate made of glass or polyethylene, or a commercially available Mylar film to an appropriate thickness. The coated substrate is
dried, exposed to electron beams, UV rays or γ-rays, or heated to cause the hardening
reaction, and a desired film is obtained.
Another example of the preparation method for a film is as follows.
After the support substrate is coated with the composite mixture, a spacer for regulating the thickness is fixed on both ends of the support substrate. Then, another support substrate is placed thereon and is hardened with the radiator or a heat source to prepare a solid polymer electrolyte film.
Brief Description of the Drawings
FIG. 1 is a graph showing a property of ionic conductivity of the solid polymer electrolytes of the present invention (Experimental example 3).
Preferred Embodiments
A preferred embodiment of the present invention will be described herein below. It is also to be understood that examples herein are for the purpose of describing the present invention only, and are not intended to be limiting.
I. Synthesis of monomer of Formula (4) in the Reaction Scheme 1
Preparation Example 1
(Step 1)
[Reaction Scheme 2]
1.Og of allylamine (17.5mmol) and 2.Og of triethylamine (20mmol) were mixed with 40ml of chloroform at -4O0C, and 5.Og of triflic anhydride (18mmol) was added
dropwise to the mixture under nitrogen atmosphere. The solution was stirred at room temperature for four hours, and volatile substances were removed under reduced pressure. The remaining viscous liquid was dissolved in 30ml of 4M NaOH, and washed with chloroform. Then, an organic extract was dried over anhydrous MgSO4 and filtered. The chloroform was removed under vacuum to yield N-Ally-C,C,C-trifluoro- methanesulfonamide (Allyl-TFSA) (see the Reaction Scheme 2).
1H NMR (300MHz, CDCl3): ppm 3.9 (m, 2H), 4.9 (s-broad, IH), 5.35 (m, 2H), 5.9
(m, 1 H); 19F NMR (CDCl3): ppm -77.9 (s)
(Step 2) [Reaction Scheme 3]
C4-4TFSA
3.Og of 2,4,6,8-tetramethylcyclotetrasiloxane (D4H) (0.0125mol) was dissolved in 50ml of toluene, and a mixed solution of 10.3g of allyl-TFSA (0.055mol) obtained from Preparation Example 1 and 50ml of toluene was added dropwise thereto. The reaction ran with the presence of a catalyst, Pt(O)-l,3-divinyl-l,l,3,3-tetramethyl disiloxane complex (Pt(O)). The mixture was refluxed for 8 hours at HO0C under nitrogen atmosphere and was cooled to room temperature. Active carbon was then added thereto, stirred and filtered. The toluene was evaporated under reduced pressure to yield C4-4TFSA (see the Reaction Scheme 3). 1H NMR (300MHz, CDCl3): ppm 0.00(s, 3H), 0.46-0.5 l(m, 2H), 1.49-1.54(m, 2H),
3.13-3.15(m, 2H), 5.64-5.68(m, IH) Preparation Example 2 [Reaction Scheme 4]
C4-4TFSA C4-4TFSI
99.7g of Q-4TFSA obtained from (step 2) of Preparation Example 1 and 24.3g of triethylamine were dissolved in 100ml of chloroform -250C. Then, 62.1g of triflic anhydride was added dropwise to the reaction mixture under nitrogen atmosphere. The 5 resulting solution was stirred at room temperature for 1 hour, and distilled water was poured therein to separate an organic layer. The organic layer thusly obtained was washed three times with distilled water. Then, an organic extract was dried over anhydrous MgSO4 and filtered. The chloroform was removed under vacuum to yield Q-4TFSI (see the Reaction Scheme 4).
10 1H NMR (300MHz, CDCl3): ppm 0.00(s, 3H), 0.46-0.51(m, 2H), 1.49-1.54(m, 2H),
3.13-3.15(m, 2H) Preparation Example 3 (Step 1) [Reaction Scheme 5]
-CH2CHCH2NH2Cl
J 5 Allylmonocyanamide Allyldicyanamide
86g of cyanogen chloride (1.4mol) was dissolved in 150ml of cold anhydrous ether (-1O0C). A mixed solution of 57.1g of allylamine and 200ml of anhydrous ether was added thereto over 2 hours while keeping the temperature below -50C. The reaction mixture was
set aside until room temperature for 12 hours. A white precipitate thusly produced was
collected and washed once with 100ml of anhydrous ether and twice more with 75ml of anhydrous ether. Then, a mixed solution of 30.7g of cyanogen chloride (0.5mol) and 150ml of cold anhydrous ether (-150C) was added dropwise to the filtrate while stirring. At the same time, another mixed solution of 50.6g of triethylamine (0.5mol) and 150ml of anhydrous ether was added dropwise to the filtrate while keeping the temperature below - 1O0C. Stirring and cooling was continued for an additional 15 minutes and the temperature of the reaction mixture was raised to +1O0C. A precipitate was filtered and washed once with 100ml of anhydrous ether and twice more with 75ml of anhydrous ether. The ether solution was evaporated and the residue was fractionally distilled over a 15cm Vigreux column under nitrogen atmosphere. To obtain dicyanamide free of diethyl cyanamide, the crude product was distilled once more over the Vigreux column to yield allyldicyanamide (Allyl-DCN) (see the Reaction Scheme 5).
1H NMR (300MHz, CDCl3): ppm 4.02 (m, 2H), 5.25 (m, 2H)3 6.63 (m, IH) (Step 2)
[Reaction Scheme 6]
C-4IX'N
3.Og of 2,4,6,8-tetramethylcyclotetrasiloxane (D4H) (0.0125mol) was dissolved in 50ml of toluene, and a mixed solution of 5.9g of allyl-DCN (0.055mol) obtained from (step 1) and 50ml of toluene was added dropwise thereto. The reaction ran with the presence of a catalyst, Pt(O)-l,3-divinyl-l,l,3,3-tetramethyl disiloxane complex (Pt(O)).
The mixture was refluxed for 8 hours at 110°C under nitrogen atmosphere and was cooled
to room temperature. Active carbon was then added thereto, stirred and filtered. The toluene was evaporated under reduced pressure to yield C4-4DCN (see the Reaction Scheme 6).
1H NMR (300MHz, CDCl3): ppm 0.00(s, 3H), 0.48-0.52(m, 2H), 1.51-1.57(m, 2H)5 3.17-3.19(m, 2H)
Preparation Example 4
(Step 1)
[Reaction Scheme 7]
16.8g of allyl iodide (lOOmmol) and 35ml of tetrachloroethane were placed in a
100ml round flask connected to a glass manifold system having an expansion valve, and the entire system went through 3 freezing - defreezing cycles under vacuum to remove air therein. The system was then filled with 6.7Og of tetrafluorohydrazine (64mmol), and the mixture was heated at 6O0C for 2 hours. During the heating process, the pressure was dropped from the lowest 525mmHg to 368mmHg. When excess gas fraction was analyzed by mass spectroscopy, it was discovered that 5.63g of tetrafluorohydrazine (54mmol) was consumed. Obtained dark colored solution was treated with mercury to remove iodine
therein. A substantially transparent solution thusly obtained was then distilled to yield allyldifluoroamine (allyl-DFA) (see the Reaction Scheme 7).
1H NMR (300MHz, CDCl3): ppm 4.26 (m, 2H), 5.37 (m, 2H), 5.97 (m, IH) ; 19F NMR (CDCl3): ppm -53.7 (s) (Step 2) [Reaction Scheme 8]
C-4-4DFΛ
3.Og of 2,4,6,8-tetramethylcyclotetrasiloxane (D4H) (0.0125mol) was dissolved in 50ml of toluene, and a mixed solution of 5.1g of allyl-DFA (0.055mol) obtained from (step 1) and 50ml of toluene was added dropwise thereto. The reaction ran with the presence of a catalyst, Pt(O)-l,3-divinyl-l,l,3,3-tetramethyl disiloxane complex (Pt(O)). The mixture
was refluxed for 8 hours at 110°C under nitrogen atmosphere and was cooled to room
temperature. Active carbon was then added thereto, stirred and filtered. The toluene was evaporated under reduced pressure to yield C4-4DFA (see the Reaction Scheme 8). 1H NMR (300MHz, CDCl3): ppm 0.00(s, 3H), 0.48-0.52(m, 2H), 1.51-1.57(m, 2H),
3.17-3.19(m, 2H) Preparation Example 5 (Step 1)
[Reaction Scheme 9]
N,N-Dichloroallylamine
A mixture of 106g of chromatographic alumina and 4Og of N-chlorosuccinimide, a chlorinating agent (0.3mol) was packed into a reactor tube (60cm x 40cm). Then, the chlorinating agent was horizontally split between two pieces of quartz wool being 50cm apart from each other. 5.7g of allylamine which was precooled to -3O0C was slowly introduced into the system over 1 hour. Later, vapor was condensed in liquid nitrogen trap to yield N, N-dichloroallylamine (Allyl-DCA) (see the Reaction Scheme 9).
1H NMR (300MHz, CDCl3): ppm 5.2 (m, 2H), 5.4 (m, 2H), 5.95 (m, IH) (Step 2)
[Reaction Scheme 10]
C-4DCΛ
3.0g of 2,4,6,8-tetramethylcyclotetrasiloxane (D4H) (0.0125mol) was dissolved in 50ml of toluene, and a mixed solution of 6.9g of allyl-DCA (0.055mol) obtained from (step 1) and 50ml of toluene was added dropwise thereto. The reaction ran with the presence of a catalyst, Pt(O)-l,3-divinyl-l,l,3,3-tetramethyl disiloxane complex (Pt(O)).
The mixture was refluxed for 8 hours at 11O0C under nitrogen atmosphere and was cooled to room temperature. Active carbon was then added thereto, stirred and filtered. The toluene was evaporated under reduced pressure to yield C4-4DCA (see the Reaction Scheme 10).
5 1H NMR (300MHz, CDCl3): ppm 0.00(s, 3H), 0.46-0.5 l(m, 2H), 1.49-1.54(m, 2H),
3.13-3.15(m, 2H)
Preparation Example 6 (Step 1) [Reaction Scheme 11]
I r\ N-allyl-2,2,2-trifluoro-N-trifluoroacetyl-actamide
0.119g of allylamine (2.08mmol) and 0.49g of anhydrous trifluoroacetic acid
(3.2mmol) were reacted with a mixed solution of 3ml of carbon tetrachloride and 0.637g of
2,6-di-tertiary-butyl-4-methyl-pyridine (3.1 lmmol) for four hours. Pyridinium triflate was filtered and removed to yield N-allyl-2,2,2-trifluoro-N-trifluoroacetyl-acetamide (Allyl-
15 TFAC) (see the Reaction Scheme 11).
1H NMR (300MHz, CDCl3): ppm 4.37 (m, 2H), 5.07-5.26 (m, 2H), 5.80 (m, IH) ) ; 19F NMR (CDCl3): ppm -71.3 (s) (Step 2) [Reaction Scheme 12]
3.Og of 2,4,6,8-tetramethylcyclotetrasiloxane (D4H) (0.0125mol) was dissolved in 50ml of toluene, and a mixed solution of 13.7g of allyl-TFAC (0.055mol) obtained from (step 1) and 50ml of toluene was added dropwise thereto. The reaction ran with the presence of a catalyst, Pt(O)- 1,3 -divinyl- 1,1,3 ,3 -tetramethyl disiloxane complex (Pt(O)). The mixture was refluxed for 8 hours at 11O0C under nitrogen atmosphere and was cooled to room temperature. Active carbon was then added thereto, stirred and filtered. The toluene was evaporated under reduced pressure to yield Q-4TFAC (see the Reaction Scheme 12). 1H NMR (300MHz, CDCl3): ppm 0.00(s, 3H), 0.46-0.51(m, 2H), 1.49-1.54(m, 2H),
3.13-3.15(m, 2H) Preparation Example 7 (Step 1) [Reaction Scheme 13]
-Br + HO (CH2CH2O)nCH3 »~ -^- ^-0(CH2CH2O)nCH3
TEGM164Ae (n=3) PEGM3S0Ae (n=7.2)
6.Og of NaOH and 20.525g of tri(ethylene glycol)monomethylether (TEGMe, Mw=I 64.2) were put into 50ml THF dried over Na. A small amount of copper(II) chloride
as a polymerization inhibitor was added thereto under nitrogen atmosphere, and 18.2g of allylbromide was then added dropwise. The reaction mixture was refluxed for 12 hours. When the reaction was completed, extra NaOH and the product NaBr were filtered and the THF was evaporated under reduced pressure. The residual was dissolved in chloroform or methylene chloride and extracted three times with 5wt% NaOH solution. An organic layer
thusly obtained was dried over anhydrous MgSO4 and dried under vacuum to yield tri(ethylene glycol) monomethyl monoallyl ether [TEGMAe (n=3)] (see the Reaction Scheme 13).
1H NMR (300MHz, CDCl3): 3.37 ppm (s, 3H), 3.54-3.67 (m, 12H), 4.02 (d, 2H), 5.25 (m, 2H); 13C NMR (300MHz, CDCl3): ppm 58.99, 69.41, 70.51, 70.61, 71.92, 72.18, 116.99, 134.78
(Step 2) [Reaction Scheme 14]
C4-2TFSA-2TEGMP (n=3) C4-2TFSA-2PEGMP (n=7.2)
3.Og of 2,4,6,8-tetramethylcyclotetrasiloxane (D4H) (0.0125mol) was dissolved in
50ml of toluene, and a mixed solution of 5.1g of allyl-TFSA (0.0275mol) obtained from
Preparation Example 1, 5.6g of TEGMAe (0.0275mol) obtained from (step 1) and 50ml of toluene was added dropwise thereto. The reaction ran with the presence of a catalyst,
Pt(O)-l,3-divinyl-l,l,3,3-tetramethyl disiloxane complex (Pt(O)). The mixture was refluxed for 8 hours at HO0C under nitrogen atmosphere and was cooled to room temperature. Active carbon was then added thereto, stirred and filtered. The toluene was evaporated under reduced pressure to yield C4-2TFSA-2TEGMP (see the Reaction Scheme 14).
1H NMR (300MHz, CDCl3): ppm 0.00(s, 3H), 0.40-0.45(m, 2H), 1.49-1.59(m, 2H), 3.13-3.15(m, 2H), 3.31-3.60(m, 17H), 5.66-5.71 (m, IH)
Preparation Example 8 (Step 1)
Under the same conditions as in (step 1) of Preparation Example 7, 43.8g of poly(ethylene glycol) monomethyl ether (PEGMe, Mw=350) and 18.2g of allylbromide were reacted to yield poly(ethylene glycol) monomethyl monoallyl ether [PEGMAe (n=7.2)] (see the Reaction Scheme 13).
1H NMR (300MHz, CDCl3): ppm 3.52 (s, 3H), 3.66-3.86 (m, 28.8H), 4.14-4.18 (d, 2H), 5.25-5.50 (m, IH), 5.95-6.15(m, 2H); 13C NMR (300MHz, CDCl3): ppm 59.31, 69.73, 70.81, 70.88, 72.23, 72.50, 117.32, 135.09 (Step 2)
Under the same conditions as in (step 2) of Preparation Example 7, 3.0g of D4H, 5.1g of ally-TFSA obtained from Preparation Example 1, and 10.7g of PEGMAe obtained from (step 1) were reacted to yield C4-2TFSA-2PEGMP (see the Reaction Scheme 14).
1H NMR (300MHz, CDCl3): ppm 0.00(s, 3H), 0.39-0.43(m, 2H), 1.50-1.62(m, 2H), 3.13-3.15(m, 2H), 3.31-3.59(m, 33.8H), 5.63-5.68(m, IH) Preparation Example 9 (Step 1) [Reaction Scheme 15]
TEGMCI (n=3) PEGMCI (n=7.2)
16.4g of tri(ethylene glycol)monomethylether (TEGMe) and 19.5g of 1,1- carbodiimidazole were put into 200ml THF dried over Na. The reaction ran at a temperature range of 40 - 5O0C for 5 - 6 hours under nitrogen atmosphere. When the
reaction was completed, extra carbodiimidazole was filtered and extracted three times with chloroform or methylchloride and 5wt% NaOH solution. An organic layer was separated, dried over anhydrous MgSO4 and dried under vacuum to yield tri(ethylene glycol) monomethyl ether carbonylimidazole [TEGMCI, n=3, Mw=258.2] (see the Reaction Scheme 15).
1H NMR (300MHz, CDCl3): ppm 3.52 (s, 3H), 3.66-3.86 (m, 12H), 7.07 (s, IH), 7.44 (s, IH) (Step 2) [Reaction Scheme 16]
TEGMAC (n=3) PEGMAC (n=7.2)
25.8g of TEGMCI obtained from (step 1) and 6.4g of allylalcohol were added into
50ml THF dried over Na. The reaction mixture was refluxed for 24 hours under nitrogen atmosphere. When the reaction was completed, the THF was evaporated under reduced pressure and the residual was dissolved in chloroform or methylene chloride and extracted three times with 5wt% NaOH solution. An organic layer thusly separated was dried over anhydrous MgSO4 and dried under vacuum to yield TEGMAC (n=3, Mw=249.2) into which allyl carbonate was introduced (see the Reaction Scheme 16).
1H NMR (300MHz, CDCl3): ppm 3.52 (s, 3H), 3.66-3.86 (m, 12H), 4.63-4.61 (d, 2H), 5.39-5.24 (m, 2H), 5.99-5.89 (m, IH) (Step 3)
[Reaction Scheme 17]
TEGMAC (n=3)
D4H PEGMAC (n=7.2)
C4-2TFSA-2TEGMPC (n=3) C4-2TFSA-2PEGMPC (n=7.2)
3.Og of 2,4,6,8-tetramethylcyclotetrasiloxane (D4H) (0.0125mol) was dissolved in 50ml of toluene, and a mixed solution of 5.1g of allyl-TFSA (0.0275mol) obtained from Preparation Example 1, 6.9g of TEGMAC (0.0275mol) obtained from (step 2) and 50ml of toluene was added dropwise thereto. The reaction ran with the presence of a catalyst, Pt(O)- 1,3 -divinyl- 1,1,3 ,3 -tetramethyl disiloxane complex (Pt(O)). The mixture was refluxed for 8 hours at HO0C under nitrogen atmosphere and was cooled to room temperature. Active carbon was then added thereto, stirred and filtered. The toluene was evaporated under reduced pressure to yield Q-2TFSA-2TEGMPC (see the Reaction Scheme 17).
1H NMR (300MHz, CDCl3): ppm 0.00(s, 3H), 0.40-0.45(m, 2H), 1.49-1.59(m, 2H), 3.13-3.15(m, 2H), 3.31-3.60(m, 17H), 5.64-5.68(m, IH) Preparation Example 10 (Step 1) Under the same conditions as in (step 1) of Preparation Example 9, 35.0g of
poly(ethylene glycol) monomethyl ether (PEGMe) and 19.5g of 1,1-carbodiimidazole were reacted to yield poly(ethylene glycol) monomethyl ether carbonylimidazole (PEGMCI, n=7.2, Mw=444) (see the Reaction Scheme 15).
1H NMR (300MHz, CDCl3): ppm 3.52 (s, 3H), 3.66-3.86 (m, 28.8H), 7.07 (s, IH), 7.44 (s, IH) (Step 2)
Under the same conditions as in (step 2) of Preparation Example 9, 44.4g of PEGMCI obtained form (step 1) and 5.8g of allylalcohol were reacted to yield PEGMAC (n=7.2, Mw=435) (see the Reaction Scheme 16). 1H NMR (300MHz, CDCl3): ppm 3.52 (s, 3H), 3.66-3.86 (m, 28.8H), 4.63-4.61 (d,
2H), 5.39-5.24 (m, 2H), 5.99-5.89 (m, IH) (Step 3)
Under the same conditions as in (step 3) of Preparation Example 9, 3.0g of D4H, 5.1g of ally-TFSA obtained from Preparation Example 1, and 12.Og of PEGMAC obtained from (step 2) were reacted to yield Q-2TFSA-2PEGMPC (see the Reaction Scheme 17).
1H NMR (300MHz5 CDCl3): ppm 0.00(s, 3H), 0.39-0.43(m, 2H), 1.50-1.62(m, 2H), 3.13-3.15(m, 2H), 3.31-3.59(m, 33.8H), 5.63-5.68(m, IH) Preparation Example 11 [Reaction Scheme 18]
D.H
C4-2TFSA-2CN
3.Og of 2,4,6,8-tetramethylcyclotetrasiloxane (D4H) (0.0125mol) was dissolved in 50ml of toluene, and a mixed solution of 5.1g of allyl-TFSA (0.0275mol) obtained from (step 1) of Preparation Example 1, 1.8g of allyl cyanide (0.0275mol) and 50ml of toluene was added dropwise thereto. The reaction ran with the presence of a catalyst, Pt(O)-1, 3- di vinyl- 1,1,3 ,3 -tetramethyl disiloxane complex (Pt(O)). The mixture was refluxed for 8 hours at HO0C under nitrogen atmosphere and was cooled to room temperature. Active carbon was then added thereto, stirred and filtered. The toluene was evaporated under reduced pressure to yield Q-2TFSA-2CN (see the Reaction Scheme 18).
1H NMR (300MHz, CDCl3): ppm 0.15(s, 3H), 0.74(m, 2H), 1.71(m, 2H), 2.4(m, 2H), 5.63-5.68(m, IH)
Preparation Example 12 (Step 1)
[Reaction Scheme 19]
384ml of diethyl carbonate, 192ml of 3-(allyloxy)-l,2-propanediol, and 32g (dry) of potassium carbonate were added into a 1,000ml round flask which was fitted with a
magnetic stirring bar and a Dean Stark trap with a water cooled condenser in order to collect ethanol, one of the products. The reaction mixture was heated at 12O0C for 24 hours and the resulting ethanol was distilled. When the reaction was completed, the reaction mixture was cooled to room temperature and filtered, and a solid phase carbonate in the solution was removed. Meanwhile, the residue was vacuum distilled at a pressure of lOmmHg to yield (cyclic-allyloxy)methylethylene ester carboxylic acid (CAMEECA, Mw=I 58). Among the fractional distillates, a distillate obtained at a temperature of 150 - 1520C was chosen as a final product (see the Reaction Scheme 19). 1H NMR (300MHz, CDCl3): ppm 3.66 (m, 2H), 4.05 (d, 2H), 4.48 (m, 2H), 4.818
(m, IH), 5.25 (m, 2H), 5.86(m, IH) (Step 2) [Reaction Scheme 20]
C-2TFSA-2CPP
3.Og of 2,4,6,8-tetramethylcyclotetrasiloxane (D4H) (0.0125mol) was dissolved in 50ml of toluene, and a mixed solution of 5.1g of allyl-TFSA (0.0275mol) obtained from Preparation Example 1, 4.3g of CAMEECA (0.0275mol) obtained from (step 1) and 50ml of toluene was added dropwise thereto. The reaction ran with the presence of a catalyst, Pt(O)-l,3-divinyl-l,l,3,3-tetramethyl disiloxane complex (Pt(O)). The mixture was refluxed for 8 hours at HO0C under nitrogen atmosphere and was cooled to room temperature. Active carbon was then added thereto, stirred and filtered. The toluene was evaporated under reduced pressure to yield C4-2TFSA-2CPP (see the Reaction Scheme 20).
1H NMR (300MHz, CDCl3): ppm 0.19(s, 3H), 0.62(m, 2H), 1.70(m, 2H), 3.51(m, 2H), 3.74(m, 2H), 4.37(m, 2H), 4.96(s, IH), 5.64-5.68(m, IH)
Preparation Examples 13 - 47
Compounds (Preparation Examples 13 - 47) of the Formula 4 in the Reaction Scheme 1 were prepared using the procedures described in Preparation Examples 1 and 7- 12 in the weight ratio shown in Table 1 below. [Table 1]
TEGMP-
37 2.8 g 5.4 g 2.2 g
PEGMP-
CPP
C4-TFSA-
TEGMP-
38 2.8 g 6.O g 0.9 g
PEGMPC-
CN
C4-TFSA-
PEGMP-
39 5.4 g 6.O g 0.9 g
PEGMPC-
CN
C4-TFSA- TEGMPC-
40 3.4 g 6.O g 0.9 g PEGMPC-
CN
C4-TFSA-
TEGMP-
41 2.8 g 3.4 g 0.9 g
TEGMPC-
CN
C4-TFSA-
PEGMP-
42 5.4 g 3.4 g 0.9 g
TEGMPC-
CN
C4-TFSA- TEGMP-
43 2.8 g 5.4 g 0.9 g PEGMP-
CN
C4-TFSA-
TEGMP-
44 2.8 g 3.4g 0.6 g
TEGMPC-
PEGMPC
C4-TFSA-
PEGMP-
45 5.4 g 3.4 g 0.6 g
TEGMPC-
PEGMPC
C4-TFSA- TEGMP-
46 2.8 g 5.4 g 0.6 g PEGMP- PEGMPC
C4-TFSA- TEGMP-
47 2.8 g 5.4 g 3.4 g PEGMP- TEGMPC
Preparation Examples 48 - 88
Compounds (Preparation Examples 48 - 88) of the Formula 4 in the Reaction Scheme 1 were prepared using the procedures described in Preparation Examples 3 and 7- 12 in the weight ratio shown in Table 2 below.
[Table 2]
66 2.8 g 3.4 g TEGMP- TEGMPC
C4-2 DCN -
67 5.4 g 3.4 g PEGMP- TEGMPC
C4-2 DCN ■
68 2.8 g 5.4 g TEGMP- TEGMP
C4- DCN -
69 1.5 g 2.8 g 0.9 g 2.2 g TEGMP- CN-CPP
C4- DCN -
70 5.4 g 0.9 g 2.2 g PEGMP- CN-CPP
C4- DCN -
71 3.4 g 0.9 g 2.2 g TEGMPC-
CN-CPP
C4- DCN -
72 6.O g 0.9 g 2.2 g PEGMPC-
CN-CPP
C4- DCN -
TEGMP-
73 2.8 g 6.O g 2.2 g
PEGMPC-
CPP
C4- DCN -
PEGMP-
74 5.4 g 6.O g 2.2 g
PEGMPC-
CPP
C4- DCN -
TEGMPC-
75 3.4 g 6.O g 2-2 g
PEGMPC-
CPP
C4- DCN -
TEGMP-
76 2.8 g 3.4 g 2.2 g
TEGMPC-
CPP
C4- DCN -
PEGMP-
77 5.4 g 3.4 g 2.2 g
TEGMPC-
CPP
C4- DCN -
TEGMP-
78 2.8 g 5.4 g 2.2 g
PEGMP-
CPP
C4- DCN -
TEGMP-
79 2.8 g 6.O g 0.9 g
PEGMPC-
CN
C4- DCN -
PEGMP-
80 5.4 g 6.O g 0.9 g
PEGMPC-
CN
Preparation Examples 89 - 129
Compounds (Preparation Examples 89 - 129) of the Formula 4 in the Reaction Scheme 1 were prepared using the procedures described in Preparation Examples 4 and 7- 12 in the weight ratio shown in Table 3 below. [Table 3]
90 10.7 g -2PEGMP
C4-2 DFA
91 6.9 g
2TEGMP C
C4-2 DFA
92 12.O g
2PEGMP C
C4-2 DFA
93 1.8 g
-2CN
C4-2 DFA
94 4.3 g -2CPP
C4-2 DFA
95 2.8 g 2.2 g -TEGMP-
CPP
C4-2 DFA
96 5.4 g 2.2 g -PEGMP-
CPP
C4-2 DFA
97 3.4 g 2.2 g
TEGMPC -CPP
C4-2 DFA
98 6.O g 2.2 g
PEGMPC -CPP
C4-2 DFA
99 0.9 g 2.2 g -CN-CPP
C4-2 DFA
100 2.8 g 0.9 g -TEGMP-
CN
C4-2 DFA
101 5.4 g 0.9 g -PEGMP-
CN
C4-2 DFA
102 3.4 g 0.9 g
TEGMPC
-CN
C4-2 DFA
103 6.O g 0.9 g
PEGMPC
-CN
C4-2 DFA
104 2.8 g 6.O g -TEGMP- PEGMPC
C4-2 DFA
105 5.4 g 6.O g -PEGMP- PEGMPC
C4-2 DFA
106 3.4 g 6.Og TEGMPC
PEGMPC
C4-2 DFA
107 2.8 g 3.4 g -TEGMP- TEGMPC
C4-2 DFA
108 5.4 g 3.4 g -PEGMP- TEGMPC
C4-2 DFA
109 2.8 g 5.4 g -TEGMP-
TEGMP
C4- DFA -
110 1.3 g 2.8 g 0.9 g 2.2 g TEGMP- CN-CPP
C4- DFA -
111 5.4 g 0.9 g 2.2 g PEGMP- CN-CPP
C4- DFA -
112 3.4 g 0.9 g 2.2 g TEGMPC -CN-CPP
C4- DFA -
113 6.O g 0.9 g 2.2 g PEGMPC -CN-CPP
C4- DFA -
TEGMP-
114 2.8 g 6.O g 2.2 g
PEGMPC
-CPP
C4- DFA -
PEGMP-
115 5.4 g 6.O g 2.2 g
PEGMPC
-CPP
C4- DFA - TEGMPC
116 3.4 g 6.O g 2.2 g
PEGMPC -CPP
C4- DFA -
TEGMP-
117 2.8 g 3.4 g 2.2 g
TEGMPC
-CPP
C4- DFA -
PEGMP-
118 5.4 g 3.4 g 2.2 g
TEGMPC
-CPP
C4- DFA -
TEGMP-
119 2.8 g 5.4 g 2.2 g
PEGMP-
CPP
C4- DFA -
TEGMP-
120 2.8 g 6.O g 0.9 g
PEGMPC
-CN
C4- DFA - PEGMP-
121 5.4 g 6.O g 0.9 g PEGMPC
-CN
Preparation Examples 130 - 170
Compounds (Preparation Examples 130 - 170) of the Formula 4 in the Reaction Scheme 1 were prepared using the procedures described in Preparation Examples 5 and 7- 12 in the weight ratio shown in Table 4 below. [Table 4]
151 1-7 g 2.8 g 0.9 g 2.2 g TEGMP- CN-CPP
C4- DCA -
152 5.4 g 0.9 g 2.2 g PEGMP- CN-CPP
C4- DCA -
153 3.4 g 0.9 g 2.2 g TEGMPC-
CN-CPP
C4- DCA -
154 6.0g 0.9 g 2.2 g PEGMPC-
CN-CPP
C4- DCA -
TEGMP-
155 2.8 g 6.Og 2.2 g
PEGMPC-
CPP
C4- DCA -
PEGMP-
156 5.4 g 6.Og 2.2 g
PEGMPC-
CPP
C4- DCA -
TEGMPC-
157 3.4 g 6.Og 2.2 g
PEGMPC-
CPP
C4- DCA -
TEGMP-
158 2.8 g 3.4 g 2.2 g
TEGMPC-
CPP
C4- DCA -
PEGMP-
159 5.4 g 3.4 g 2.2 g
TEGMPC-
CPP
C4- DCA -
TEGMP-
160 2.8 g 5.4 g 2.2 g
PEGMP-
CPP
C4- DCA -
TEGMP-
161 2.8 g 6.Og 0.9 g PEGMPC-
CN
C4- DCA -
PEGMP-
162 5.4 g 6.Og 0.9 g PEGMPC-
CN
C4- DCA - TEGMPC-
163 3.4 g 6.Og 0.9 g PEGMPC-
CN
C4- DCA -
TEGMP-
164 2.8 g 3.4 g 0.9 g
TEGMPC-
CN
C4- DCA -
PEGMP-
165 5.4 g 3.4 g 0.9 g TEGMPC-
CN
Preparation Examples 171 - 211
Compounds (Preparation Examples 171 - 211) of the Formula 4 in the Reaction Scheme 1 were prepared using the procedures described in Preparation Examples 6 and 7- 12 in the weight ratio shown in Table 5 below. [Table 5]
PEGMP-
197 5.4 g 6.O g 2.2 g
PEGMPC-
CPP
C4- TFAC -
TEGMPC-
198 3.4 g 6.O g 2.2 g
PEGMPC-
CPP
C4- TFAC -
TEGMP-
199 2.8 g 3.4 g 2.2 g
TEGMPC-
CPP
C4- TFAC -
PEGMP-
200 5.4 g 3.4 g 2.2 g
TEGMPC-
CPP
C4- TFAC -
TEGMP-
201 2.8 g 5.4 g 2.2 g
PEGMP-
CPP
C4- TFAC -
TEGMP-
202 2.8 g 6.O g 0.9 g
PEGMPC-
CN
C4- TFAC -
PEGMP-
203 5.4 g 6.O g 0.9 g
PEGMPC-
CN
C4- TFAC - TEGMPC-
204 3.4 g 6.O g 0.9 g PEGMPC-
CN
C4- TFAC -
TEGMP-
205 2.8 g 3.4 g 0.9 g
TEGMPC-
CN
C4- TFAC -
PEGMP-
206 5.4 g 3.4 g 0.9 g
TEGMPC-
CN
C4- TFAC -
207 2.8 g 5.4 g 0.9 g TEGMP-
PEGMP-CN
C4- TFAC- TEGMP-
208 2.8 g 3.4g 0.6 g
TEGMPC- PEGMPC
C4- TFAC- PEGMP-
209 5.4 g 3.4 g 0.6 g
TEGMPC- PEGMPC
C4- TFAC - TEGMP-
210 2.8 g 5.4 g 0.6 g PEGMP- PEGMPC
Preparation Examples 212 - 227
Compounds (Preparation Examples 212 - 227) of the Formula 4 in the Reaction Scheme 1 were prepared using the procedures described in Preparation Examples 1, 3 and 7-12 in the weight ratio shown in Table 6 below. [Table 6]
Preparation Examples 228 - 243
Compounds (Preparation Examples 228 - 243) of the Formula 4 in the Reaction Scheme 1 were prepared using the procedures described in Preparation Examples 1, 4 and 7-12 in the weight ratio shown in Table 7 below. [Table 7]
Preparation Examples 244 - 259
Compounds (Preparation Examples 244 - 259) of the Formula 4 in the Reaction Scheme 1 were prepared using the procedures described in Preparation Examples 1, 5 and 7-12 in the weight ratio shown in Table 8 below. [Table 8]
TFSA- DCA-
254 2.8 g 6.O g TEGM
P- PEGM
PC
C4-
TFSA- DCA-
255 5.4 g 6.O g PEGM
P- PEGM
PC
C4-
TFSA- DCA-
256 3.4 g 6.Og TEGM
PC- PEGM
PC
C4-
TFSA- DCA-
257 2.8 g 3.4 g TEGM
P- TEGM
PC
C4-
TFSA- DCA-
258 5.4 g 3.4 g PEGM
P- TEGM
PC
C4-
TFSA- DCA-
259 2.8 g 5.4 g TEGM
P- TEGM
P
Preparation Examples 260 - 275
Compounds (Preparation Examples 260 - 275) of the Formula 4 in the Reaction Scheme 1 were prepared using the procedures described in Preparation Examples 1, 6 and 7-12 in the weight ratio shown in Table 9 below. [Table 9]
C4-
TFSA-
269 6.O g 0.9 g TFAC- PEGM PC-CN
C4-
TFSA- TFAC-
270 2.8 g 6.O g TEGM
P- PEGM
PC
C4-
TFSA- TFAC-
271 5.4 g 6.O g PEGM
P- PEGM
PC
C4-
TFSA- TFAC-
272 3.4 g 6.Og TEGM
PC- PEGM
PC
C4-
TFSA- TFAC-
273 2.8 g 3.4 g TEGM
P- TEGM
PC
C4-
TFSA- TFAC-
274 5.4 g 3.4 g PEGM
P- TEGM
PC
C4-
TFSA- TFAC-
275 2.8 g 5.4 g TEGM
P- PEGM
P
Preparation Examples 276 - 291
Compounds (Preparation Examples 276 - 291) of the Formula 4 in the Reaction Scheme 1 were prepared using the procedures described in Preparation Examples 3, 4 and 7-12 in the weight ratio shown in Table 10 below. [Table 10]
Preparation Examples 292 - 307
Compounds (Preparation Examples 292 — 307) of the Formula 4 in the Reaction Scheme 1 were prepared using the procedures described in Preparation Examples 3, 5 and 7-12 in the weight ratio shown in Table 11 below. [Table 11]
DCA-
294 5.4 g 2.2 g PEGMP-
CPP C4- DCN-
DCA-
295 3.4 g 2.2 g TEGMPC
-CPP C4- DCN-
DCA-
296 6.Og 2.2 g PEGMPC
-CPP C4- DCN-
297 0.9 g 2.2 g DCA- CN-CPP C4- DCN-
DCA-
298 2.8 g 0.9 g TEGMP-
CN C4- DCN-
DCA-
299 5.4 g 0.9 g PEGMP-
CN C4- DCN-
DCA-
300 3.4 g 0.9 g TEGMPC
-CN C4- DCN-
DCA-
301 6.Og 0.9 g PEGMPC
-CN C4- DCN-
DCA-
302 2.8 g 6.Og TEGMP- PEGMPC C4- DCN-
DCA-
303 5.4 g 6.Og PEGMP- PEGMPC C4- DCN-
DCA-
304 3.4 g 6.Og TEGMPC
PEGMPC C4- DCN-
DCA-
305 2.8 g 3.4 g TEGMP- TEGMPC C4- DCN-
DCA-
306 5.4 g 3.4 g PEGMP- TEGMPC C4- DCN-
DCA-
307 2.8 g 5.4 g TEGMP- TEGMP
Preparation Examples 308 - 323
Compounds (Preparation Examples 308 - 323) of the Formula 4 in the Reaction Scheme 1 were prepared using the procedures described in Preparation Examples 3, 6 and 7-12 in the weight ratio shown in Table 12 below. [Table 12]
Preparation Examples 324 - 339
Compounds (Preparation Examples 324 — 339) of the Formula 4 in the Reaction Scheme 1 were prepared using the procedures described in Preparation Examples 4, 5 and 7-12 in the weight ratio shown in Table 13 below. [Table 13]
324 2.6 g 3.5 g DFA-2
DCA
C4-DFA-
DCA-
325 1.3 g 1-7 g 2.8 g 2.2 g TEGMP-
CPP
C4-DFA-
DCA-
326 5.4 g 2.2 g
PEGMP-
CPP
C4-DFA-
DCA-
327 3.4 g 2.2 g
TEGMPC
-CPP
C4-DFA-
DCA-
328 6.Og 2.2 g
PEGMPC
-CPP
C4-DFA-
329 0.9 g 2.2 g DCA-
CN-CPP
C4-DFA-
DCA-
330 2.8 g 0.9 g
TEGMP-
CN
C4-DFA-
DCA-
331 5.4 g 0.9 g
PEGMP-
CN
C4-DFA-
DCA-
332 3.4 g 0.9 g
TEGMPC
-CN
C4-DFA-
DCA-
333 6.Og 0.9 g
PEGMPC
-CN
C4-DFA-
DCA-
334 2.8 g 6.Og
TEGMP-
PEGMPC
C4-DFA-
DCA-
335 5.4 g 6.Og
PEGMP-
PEGMPC
C4-DFA-
DCA-
336 3.4 g 6.Og TEGMPC
PEGMPC C4-DFA- DCA-
337 2.8 g 3.4 g TEGMP- TEGMPC
Preparation Examples 340 - 355
Compounds (Preparation Examples 340 - 355) of the Formula 4 in the Reaction Scheme 1 were prepared using the procedures described in Preparation were prepared using the procedures described in Examples 4, 6 and 7-12 in the weight ratio shown in
Table 14 below. [Table 14]
346 2.8 g 0.9 g TEGMP-
CN
C4-DFA- TFAC-
347 5.4 g 0.9 g PEGMP-
CN
C4-DFA-
TFAC-
348 3.4 g 0.9 g
TEGMPC
-CN
C4-DFA-
TFAC-
349 6.Og 0.9 g
PEGMPC
-CN
C4-DFA-
TFAC-
350 2.8 g 6.Og
TEGMP-
PEGMPC
C4-DFA-
TFAC-
351 5.4 g 6.Og
PEGMP-
PEGMPC
C4-DFA-
TFAC-
352 3.4 g 6.Og TEGMPC
PEGMPC
C4-DFA-
TFAC-
353 2.8 g 3.4 g
TEGMP-
TEGMPC
C4-DFA-
TFAC-
354 5.4 g 3.4 g
PEGMP-
TEGMPC
C4-DFA- TFAC-
355 2.8 g 5.4 g TEGMP- TEGMP
Preparation Examples 356 - 371
Compounds (Preparation Examples 356-371) of the Formula 4 in the Reaction Scheme 1 were prepared using the procedures described in Preparation Examples 5, 6 and 7-12 in the weight ratio shown in Table 15 below. [Table 15]
Preparation Examples 372 - 377
Compounds (Preparation Examples 372 - 377) of the Formula 4 in the Reaction Scheme 1 were prepared using the procedures described in Preparation Examples 1, 3, 6 and 7-12 in the weight ratio shown in Table 16 below. [Table 16]
Preparation Examples 378 - 383
Compounds (Preparation Examples 378 - 383) of the Formula 4 in the Reaction Scheme 1 were prepared using the procedures described in Preparation Examples 1, 4, 6 and 7-12 in the weight ratio shown in Table 17 below. [Table 17]
Preparation Examples 384 - 389
Compounds (Preparation Examples 384 - 389) of the Formula 4 in the Reaction Scheme 1 were prepared using the procedures described in Preparation Examples 1, 5, 6 and 7-12 in the weight ratio shown in Table 18 below. [Table 18]
Preparation Examples 390 - 395
Compounds (Preparation Examples 390 - 395) of the Formula 4 in the Reaction Scheme 1 were prepared using the procedures described in Preparation Examples 1, 3, 5 and 7-12 in the weight ratio shown in Table 19 below. [Table 19]
Preparation Examples 396 - 401
Compounds (Preparation Examples 396 - 401) of the Formula 4 in the Reaction Scheme 1 were prepared using the procedures described in Preparation Examples 1, 4, 5 and 7-12 in the weight ratio shown in Table 20 below. [Table 20]
PreparaProduct
Reagent tion Code
Preparation Examples 402- 407
Compounds (Preparation Examples 402 - 407) of the Formula 4 in the Reaction Scheme 1 were prepared using the procedures described in Preparation Examples 1, 3, 4 and 7-12 in the weight ratio shown in Table 21 below. [Table 21]
Preparation Examples 408 - 412
Compounds (Preparation Examples 408 - 412) of the Formula 4 in the Reaction Scheme 1 were prepared using the procedures described in Preparation Examples 1, 3, 4, 5 and 6 in the weight ratio shown in Table 22 below.
[Table 22]
Preparation Example 413
[Reaction Scheme 21]
D4H
C-4TEGMP (n=3) C4-4PEGMP (n=7.2)
3.Og of 2,4,6,8-tetramethylcyclotetrasiloxane (D4H) (0.0125mol) was dissolved in 50ml of toluene, and a mixed solution of 11.2g of TEGMAe (0.055mol) obtained from (step 1) of Preparation Example 7 and 50ml of toluene was added dropwise thereto. The reaction ran with the presence of a catalyst, Pt(O)-l,3-divinyl-l,l,3,3-tetramethyl disiloxane complex (Pt(O)). The mixture was refluxed for 8 hours at 11O0C under nitrogen atmosphere and was cooled to room temperature. Active carbon was then added thereto, stirred and filtered. The toluene was evaporated under reduced pressure to yield C4- 4TEGMP (see the Reaction Scheme 21).
1H NMR (300MHz, CDCl3): ppm 0.00(s, 3H), 0.40-0.45(m, 2H), 1.49-1.59(m,
2H), 3.13-3.15(m, 2H), 3.31-3.60(m, 17H)
13C NMR (300MHz, CDCl3): ppm 0.00, 13.76, 23.74, 59.75, 70.71, 71.23, 71.32,
72.64, 74.66
Preparation Example 414
3.Og of D4H and 21.4g of PEGMAe obtained from (step 1) of Preparation Example 8 are reacted under the same condition as in (step 2) of Preparation Example 8 to obtain Q-4PEGMP (see the Reaction Scheme 21).
1H NMR (300MHz, CDCl3): ppm 0.00(s, 3H), 0.39-0.43(m, 2H), 1.50-1.62(m,
2H), 3.31-3.59(m, 33.8H)
13C NMR (300MHz, CDCl3): ppm 0.00, 13.75, 23.73, 59.77, 70.70, 71.28, 72.65, 74.69 Preparation Example 415 [Reaction Scheme 22]
D,H
C4-4TEGMPC (n=3) C4-4PEGMPC (n=7.2)
3.Og of 2,4,6,8-tetramethylcyclotetrasiloxane (D4H) (0.0125mol) was dissolved in 50ml of toluene, and a mixed solution of 13.8g of TEGMAC (0.055mol) obtained from (step 2) of Preparation Example 9 and 50ml of toluene was added dropwise thereto. The reaction ran with the presence of a catalyst, Pt(O)- 1,3 -divinyl- 1,1,3 ,3 -tetramethyl disiloxane complex (Pt(O)). The mixture was refluxed for 8 hours at HO0C under nitrogen atmosphere and was cooled to room temperature. Active carbon was then added thereto,
stirred and filtered. The toluene was evaporated under reduced pressure to yield C4-
4TEGMPC (see the Reaction Scheme 22).
1H NMR (300MHz, CDCl3): ppm 0.00(s, 3H), 0.40-0.45(m, 2H), 1.49-1.59(m, 2H), 3.31-3.60(m, 17H) Preparation Example 416
3.Og ofD4H and 24.Og of PEGMAC obtained from (step 2) of Preparation Example 10 are reacted under the same condition as in (step 3) of Preparation Example 9 to obtain Q-4PEGMPC (see the Reaction Scheme 22).
1H NMR (300MHz, CDCl3): ppm 0.00(s, 3H), 0.39-0.43(m, 2H), 1.50-1.62(m, 2H), 3.13-3.59(m, 33.8H)
Preparation Example 417 [Reaction Scheme 23]
C4-4CN
3.0g of 2,4,6,8-tetramethylcyclotetrasiloxane (D4H) (0.0125mol) was dissolved in 50ml of toluene, and a mixed solution of 3.6 of allyl cyanide (0.055mol) and 50ml of toluene was added dropwise thereto. The reaction ran with the presence of a catalyst, Pt(O)-l,3-divinyl-l,l,3,3-tetramethyl disiloxane complex (Pt(O)). The mixture was refluxed for 8 hours at HO0C under nitrogen atmosphere and was cooled to room
temperature. Active carbon was then added thereto, stirred and filtered. The toluene was evaporated under reduced pressure to yield C4-4CN (see the Reaction Scheme 23).
1H NMR (300MHz, CDCl3): ppm 0.00(s, 3H), 1.3(m, 2H), 1.7(m, 2H), 2.41(m, 2H) Preparation Example 418 [Reaction Scheme 24]
D4H
3.0g of 2,4,6,8-tetramethylcyclotetrasiloxane (D4H) (0.0125mol) was dissolved in 50ml of toluene, and a mixed solution of 8.6g of CAMEECA (0.055mol) obtained from (step 1) of Preparation Example 12 and 50ml of toluene was added dropwise thereto. The reaction ran with the presence of a catalyst, Pt(O)-l,3-divinyl-l,l,3,3-tetramethyl
disiloxane complex (Pt(O)). The mixture was refluxed for 8 hours at 11O0C under nitrogen atmosphere and was cooled to room temperature. Active carbon was then added thereto,
stirred and filtered. The toluene was evaporated under reduced pressure to yield C4-4CPP (see the Reaction Scheme 24).
1H NMR (300MHz, CDCl3): ppm 0.14(s, 3H), 1.3(m, 2H), 1.5(m, 2H), 3.37(m, 2H), 3.61(m, 2H), 4.52(m, IH), 4.16(s, 2H)
Preparation Example 419 (Step 1)
3.Og of 2,4,6,8-tetramethylcyclotetrasiloxane (D4H) (0.0125mol) was dissolved in 50ml of toluene, and a mixed solution of 3.19g of allyl alcohol (0.055mol) and 50ml of toluene was added dropwise thereto. The reaction ran with the presence of a catalyst, Pt(O)- 1,3 -di vinyl- 1,1,3 ,3 -tetramethyl disiloxane complex (Pt(O)). The mixture was refluxed for 8 hours at HO0C under nitrogen atmosphere and was cooled to room temperature. Active carbon was then added thereto, stirred and filtered. The toluene was evaporated under reduced pressure to yield C4-4POH (see the Reaction Scheme 26).
1H NMR (300MHz, CDCl3): ppm 0.00(s, 12H), 1.30-1.35(m, 8H), 1.49-1.52(m, 8H), 3.51-3.60(m, 8H)), 3.89 (m, 4H) (Step 2)
In three neck flask, 23.7g of C4-4POH obtained from (step 1) and 20.74g of triethylamine were dissolved in 100ml of THF, and 18.2g of acryloyl chloride dissolved in
100ml of THF was added dropwise thereto with stirring at 0°C . After reaction for 2 hours,
the precipitates were filtered and distilled under reduced pressure. Yellow viscous liquid product is dissolved in chloroform and extracted several times with water. Chloroform layer was separated, dried over anhydrous MgSO4, and then evaporated under reduced pressure to obtain C4-4PAcr (see the Reaction Scheme 27).
1H NMR(300MHz, CDCl3) : ppm 0.00(s, 3H), 1.36-1.51(m, 2H), 1.59-1.64(m, 2H),
4.13-4.15(m, 2H), 5.78 ~ 5.84(m, IH), 6.09 ~ 6.15(m, IH), 6.33 ~ 6.39(m, IH) ; 13C
NMR(300MHz, CDCl3) : ppm 3.7, 15.8, 17.3, 70.0, 128.6, 130.2, 165.1
Preparation Example 420
(Step 1) [Reaction Scheme 25]
^Br + HO (CH2CH2O)nH *- ^^ ^0(CH2CH2O)nH
EGMAe (n=l) DEGMAe (n=2) TEGMAe (n=3) TrEGMAe (n=4)
To 500ml of THF dried over Na were added 6.Og of NaOH and 7.76g of ethylene glycol. A small amount of copper(II) chloride as a polymerization inhibitor was added thereto under nitrogen atmosphere, and 18.2g of allylbromide was then added dropwise. The reaction mixture was refluxed for 12 hours. When the reaction was completed, extra NaOH and the product NaBr were filtered and the THF was evaporated under reduced pressure. The residual was dissolved in chloroform or methylene chloride and extracted three times with 5wt% NaOH aqueous solution. An organic layer thusly obtained was dried over anhydrous MgSO4 and dried under vacuum to yield ethylene glycol monoallyl ether [EGMAe (n=l)] (see the Reaction Scheme 25).
1H NMR (300MHz, CDCl3): 3.56-3.70 ppm (m, 4H), 4.04 (d, 2H), 5.23 (m, IH),
5.24 (m, IH), 5.89 (m, IH); 13C NMR (300MHz, CDCl3): ppm 58.99, 69.41, 70.51, 70.61,
71.92, 72.18, 116.99, 134.78
(Step 2)
[Reaction Scheme 26]
C4-4POH (n=0) C4-4EGP (n=l) C4-4DEGP (n=2) C4-4TEGP (n=3) C4-4TrEGP (n=4)
3.Og of 2,4,6,8-tetramethylcyclotetrasiloxane (D4H) (0.0125mol) and 5.62g of
EGMAe (0.055mol) obtained from (step 1) are reacted under the same method as in (step
1) of Preparation Example 419 to obtain monomer C4-4EGP (see the Reaction Scheme 26).
1H NMR (300MHz, CDCl3): ppm 0.00(s, 12H), 1.30-1.35(m, 8H), 1.49-1.52(m,
8H), 3.32-3.35(m, 8H), 3.51-3.60(m, 8H), 3.71-3.75(m, 8H), 3.89 (m, 4H)
(Step 3) [Reaction Scheme 27]
C4-O1OH (n=0)
04EGP (Ii=I) C,-4DEGP (n=2) C,-4TBGP (n=3) C( -4TrECS1 (n=4)
33.2g of C4-4EGP (0.05mol) obtained from (step 2), 20.74g of triethyl amine (0.2mol) and 18.2g of acryloyl chloride (0.2mol) are reacted under the same method as in (step 2) of Preparation Example 419 to obtain monomer C4-4EGPAcr (see the Reaction Scheme 27).
1H NMR(300MHz, CDCl3) : ppm 0.00(s, 3H), 0.46-0.5 l(m, 2H), 1.49~1.54(m, 2H), 3.23~3.25(m, 2H), 3.63~3.65(m, 2H), 4.33~4.35(m, 2H), 5.78(m, IH), 6.09(m, IH),
6.39(m, IH) ; 13C NMR(300MHz, CDCl3) : ppm 3.7, 15.8, 18.3, 67.5, 69.8, 73.0, 128.6, 130.3, 165.1
Preparation Example 421 (Step 1) The procedure of (step 1 ) of Preparation Example 420 was repeated using 13.26g of diethylene glycol instead of ethylene glycol to obtain diethylene glycol monoallyl ether [DEGMAe (n=2)] (see the Reaction Scheme 25).
1H NMR (300MHz, CDCl3): 3.54-3.70 ppm (m, 8H), 4.04 (d, 2H), 5.23 (m, IH),
5.24 (m, IH), 5.89 (m, IH); 13C NMR (300MHz, CDCl3): ppm 62.7, 70.2, 72.1, 73.4,
114.9, 134.7
(Step 2)
3.0g of 2,4,6,8-tetramethylcyclotetrasiloxane (D4H) (0.0125mol) and 8.04g of DEGMAe (0.055mol) obtained from (step 1) are reacted under the same method as in (step 1) of Preparation Example 419 to obtain monomer C4-4DEGP (see the Reaction Scheme 26).
1H NMR (300MHz, CDCl3): ppm 0.00(s, 12H), 1.30~1.35(m, 8H), 1.49~1.52(m, 8H), 3.32~3.35(m, 8H), 3.51~3.60(m, 20H), 3.71~3.75(m, 8H), 3.89 (m, 4H) (Step 3)
41.3g of C4-4DEGP (0.05mol) obtained from (step 2), 20.74g of triethyl amine (0.2mol) and 18.2g of acryloyl chloride (0.2mol) are reacted under the same method as in (step 2) of Preparation Example 419 to obtain monomer C4-4DEGPAcr (see the Reaction Scheme 27).
1H NMR(300MHz, CDCl3) : ppm 0.00(s, 3H), 0.46-0.5 l(m, 2H), 1.49~1.54(m,
2H), 3.33~3.35(m, 2H), 3.53~3.55(m, 4H), 3.63~3.65(m, 2H), 4.33~4.35(m, 2H), 5.80(m,
IH), 6.09(m, IH), 6.41(m, IH) ; 13C NMR(300MHz, CDCl3) : ppm 3.7, 15.8, 18.3, 67.5,
69.8, 70.6, 70.9, 73.0, 128.7, 130.3, 165.1 Preparation Example 422 (Step 1) The procedure of (step 1) of Preparation Example 420 was repeated using 18.76g of
Methylene glycol instead of ethylene glycol to obtain Methylene glycol monoallyl ether [TEGMAe (n=3)] (see the Reaction Scheme 25).
1H NMR (300MHz, CDCl3): 3.54 ~3.70ppm (m, 12H), 4.04 (d, 2H), 5.23 (m, IH),
5.24 (m, IH), 5.89 (m, IH); 13C NMR (300MHz, CDCl3): ppm 63.7, 70.9, 71.1, 73.4,
114.9, 134.7
(Step 2)
3.Og of 2,4,6,8-tetramethylcyclotetrasiloxane (D4H) (0.0125mol) and 10.46g of TEGMAe (0.055mol) obtained from (step 1) are reacted under the same method as in (step 1) of Preparation Example 419 to obtain monomer Q-4TEGP (see the Reaction Scheme 26).
1H NMR (300MHz, CDCl3): ppm 0.00(s, 12H), 1.30-1.35(m, 8H), 1.49-1.52(m, 8H), 3.32-3.35(m, 8H), 3.51-3.60(m, 40H), 3.71-3.75(m, 8H), 3.89 (m, 4H) (Step 3)
50.0g of Q-4TEGP (0.05mol) obtained from (step 2), 20.74g of triethyl amine (0.2mol) and 18.2g of acryloyl chloride (0.2mol) are reacted under the same method as in (step 2) of Preparation Example 419 to obtain monomer C4-4TEGPAcr (see the Reaction Scheme 27).
1H NMR(300MHz, CDCl3) : ppm 0.00(s, 3H), 0.46-0.5 l(m, 2H), 1.49-1.54(m, 2H), 3.33-3.35(m, 2H), 3.53-3.55(m, 8H), 3.63-3.65(m, 2H), 4.33-4.35(m, 2H), 5.80(m, IH),
6.09(m5 IH), 6Λl(m, IH) ; 13C NMR(300MHz, CDCl3) : ppm 3.7, 15.8, 18.3, 67.5, 69.8,
70.6, 70.9, 73.0, 128.7, 130.3, 165.1
Preparation Example 423 (Step 1) The procedure of (step 1) of Preparation Example 420 was repeated using 24.26g of tetraethylene glycol instead of ethylene glycol to obtain tetraethylene glycol monoallyl ether [TrEGMAe (n=4)] (see the Reaction Scheme 25).
1H NMR (300MHz, CDCl3): 3.54 ~3.70ppm (m, 16H), 4.04 (d, 2H), 5.23 (m, IH),
5.24 (m, IH), 5.89 (m, IH); 13C NMR (300MHz, CDCl3): ppm 63.7, 70.9, 71.1, 73.1, 73.4,
114.9, 134.7
(Step 2)
3.0g of 2,4,6,8-tetramethylcyclotetrasiloxane (D4H) (0.0125mol) and 12.88g of TrEGMAe (0.055mol) obtained from (step 1) are reacted under the same method as in (step 1) of Preparation Example 419 to obtain monomer C4-4TrEGP (see the Reaction Scheme 26).
1H NMR (300MHz, CDCl3): ppm 0.00(s, 12H), 1.30-1.35(m, 8H), 1.49-1.52(m, 8H), 3.32-3.35(m, 8H), 3.51-3.60(m, 56H), 3.71-3.75(m, 8H), 3.89 (m, 4H) (Step 3)
58.9g of C4-4TrEGP (0.05mol) obtained from (step 2), 20.74g of triethyl amine (0.2mol) and 18.2g of acryloyl chloride (0.2mol) are reacted under the same method as in (step 2) of Preparation Example 419 to obtain monomer C4-4TrEGPAcr (see the Reaction Scheme 27).
1H NMR(SOOMHZ, CDCl3) : ppm 0.00(s, 3H), 0.46-0.51(m, 2H), 1.49-1.54(m, 2H), 3.33-3.35(m, 2H), 3.53-3.55(m, 12H), 3.63-3.65(m, 2H), 4.33-4.35(m, 2H), 5.80(m, IH),
6.09(m, IH), 6.41(m, IH) ; 13C NMR(300MHz, CDCl3) : ppm 3.7, 15.8, 18.3, 67.5, 69.8,
70.6, 70.9, 73.0, 128.7, 130.3, 165.1
II. Synthesis of polymerization terminator substituted with acryl or phenyl acryl group in the Reaction Scheme 1 Preparation Example 424. Preparation of D2-l,3-di(propoxy-6,7-propane diacrylate)
(TaD2)
(Step 1)
In three neck flask, 3.0g of 1,1,3,3-tetramethyldisiloxane (D2) was dissolved in
50ml of toluene, and a mixed solution of 7.1g of 3-allyloxy-l,2-propanediol and 50ml of toluene was added dropwise thereto. The reaction ran with the presence of a Pt(O) catalyst.
The mixture was refluxed for 12 hours at 11O0C under nitrogen atmosphere and was cooled to room temperature. Active carbon was then added thereto, stirred and filtered. The toluene was evaporated under reduced pressure to yield D2-l,3-di(propoxy-6,7- propanediol) (see the Reaction Scheme 28). 1H-NMR(SOOMHz, CDCl3): ppm 0.00~0.05(m, 12H), 0.41 ~0.46(m, 4H),
1.52~ 1.58(m, 4H), 2.1 l(s, 2H), 2.96(s, 2H), 3.35 ~3.81(m, 14H); 13C-NMR(300MHz,
CDCl3) : ppm 0.00, 13.83, 23.03, 63.81, 70.42, 71.93, 73.99.
(Step 2)
In three neck flask, 20.Og of D2-l,3-di(propoxy-6,7-propanediol) obtained from (step 1) and 20.74g of triethylamine were dissolved in 100ml of THF, and 18.2g of acryloyl chloride dissolved in 100ml of THF was added dropwise thereto with stirring at
0 °C . After reaction for 2 hours, the precipitates were filtered and distilled under reduced
pressure. Yellow viscous liquid product is dissolved in chloroform and extracted several times with water. Chloroform layer was separated, dried over anhydrous MgSO4, and then
evaporated under reduced pressure to obtain D2-l,3-di(propoxy-6,7-propane diacrylate) (see the Reaction Scheme 28).
1H NMR(300MHz, CDCl3) : ppm 0.00~0.04(m, 12H), 0.41 ~0.46(m, 4H), 1.49~ 1.54(m, 4H), 3.37~3.58(m, 8H), 4.30~4.39(m, 4H), 5.19~5.23(m, 2H), 5.78~5.84(m, 4H), 6.09~6.15(m, 4H), 6.33 ~6.39(m, 4H) ; 13C NMR(300MHz, CDCl3) : ppm 0.0, 13.9, 23.1, 62.8, 68.5, 70.2, 74.1, 127.7, 127.9, 131.0, 131.2, 165.1,165.5 [Reaction Scheme 28]
triethylamine
Preparation Example 425. Preparation of Di-l,3-di(propane acrylate) (DaDi) (Step 1)
2.6g of 3-butene-l-ol instead of 3-allyloxy-l,2-propanediol and 3.Og of 1,1,3,3- tetramethyldisiloxane (D2, 0.0223 mol) were reacted under the same method as in (step 1) of Preparation Example 424 to obtain D2-l,3-di(propanol) (see the Reaction Scheme 29).
1H-NMR (300MHz, CDCl3): ppm 0.00-0.03(m, 12H), 0.43-0.48(m, 4H), 1.49-
5 1.64(m, 4H), 2.28(m, 2H), 3.45~3.53(s, 4H); 13C-NMR (300MHz, CDCl3): ppm 0.0, 13.73,
26.25, 73.12
(Step 2)
6.2g of D2-l,3-di(propanol) and 4.5g of acryloyl chloride were reacted under the same method as in (step 2) of Preparation Example 424 to obtain D2-l,3-di(propane 10 acrylate) (DaD2) (see the Reaction Scheme 29).
1H-NMR (300MHz, CDCl3): ppm 0.00-0.04(m, 12H), 0.44-0.50(m, 4H), 1.53-
1.63(m, 4H), 4.02-4.06(m, 4H), 5.73-5.77(d, 2H), 6.30-6.37(d, 2H); 13C-NMR (300MHz,
CDCl3): ppm 0.00, 13.8, 22.4, 66.7, 128.4, 130.2, 166.0
[Reaction Scheme 29]
D2-l,3-di(propanol)
J 5 D2- 1 ,3-di(propane acrylate)
Preparation Example 426. Preparation of D2-l,3-di(propane phenyl acrylate) (DPhaD?)
(Step 1)
6.Og of allyl phenol instead of 3-allyloxy-l,2-propanediol and 3.Og of 1,1,3,3- tetramethyldisiloxane (D2, 0.0223mol) were reacted under the same method as in (step 1) of Preparation Example 424 to obtain D2-l,3-di(propane phenol) (see the Reaction Scheme 30).
1H-NMR (300MHz, CDCl3): ppm 0.00-0.03(m, 12H), 0.51-0.57(m, 4H), 1.57- 1.62(m, 4H), 2.54-2.60(m, 4H), 4.81(s, 2H), 6.69-6.84(m, 4H), 7.01-7.12(m, 4H); 13C- NMR (300MHz, CDCl3) : ppm 0.0, 17.9, 23.4, 33.2, 114.9, 120.4, 127.9, 153.1
(Step 2)
10.0g of D2-l,3-di(propane phenol) and 4.5g of acryloyl chloride were reacted under the same method as in (step 2) of Preparation Example 424 to obtain D2- 1,3- diφropane phenyl acrylate) (DPhaD2) (see the Reaction Scheme 30). 1H-NMR (300MHz, CDCl3): ppm 0.00-0.04(m, 12H), 0.49-0.54(m, 4H), 1.53-
1.59(m, 4H), 2.49-2.54(m, 4H), 5.98-6.02(m, 2H), 6.28-6.34(m, 2H), 6.56-6.62(m, 2H), 7.07(m, 4H), 7.18-7.25(m, 4H); 13C-NMR (300MHz, CDCl3): ppm 0.1, 17.5, 23.4, 117.5, 127.9, 128.5, 133.1, 135.6, 150.4, 162.0 [Reaction Scheme 30]
D2-l,3-di(propane phenyl aciylate)
III. Synthesis of the compound of Formula 1
The crosslinker compound represented by Formula 1 is all of compounds synthesized by the same method described in the following Examples in combination of the monomer (Formula 4) in Reaction Scheme 1 prepared from Preparation Examples 1 to 423 and polymerization terminators substituted with acryl or phenyl acryl group in the Reaction Scheme 1 prepared from Preparation Examples 424 to 426, but are limited to the compounds prepared in the following Examples. <ExampIe 1> Preparation of a crosslinker (Ta-xTFSI-yTEGMP) [Reaction Scheme 31]
0.6 Ig of C4-4TFSI (compound A) obtained from Preparation Example 2, 5.0Og of
Q-4TEGMP (compound B) obtained from Preparation Example 3 and 1.16g of D2- 1,3- di(propoxy-6,7-propane diacrylate) (compound C) obtained from Preparation Example 424 were added to three neck flask, 0.03ml of fuming H2SO4 was added dropwise thereto and
then the mixture stirred for 6 hours at 30 to 35 °C . 0.03ml of distilled water was added
thereto and stirred for 1 hour. The reaction products were added to 50ml of chloroform and 30ml of saturated aqueous Na2SO4 solution, and neutralized and washed with 5 wt% of Na2CO3 aqueous solution until neutrality was reached. MgSO4 was added to the neutralized reactants and the mixture was stirred. The precipitates were filtered, hydroquinone (100 ppm) as a polymerization inhibitor was added thereto, and the resultant was evaporated under the reduced pressure to obtain Ta-0.86TFSI-10TEGMP (see
Reaction Scheme 31).
1H-NMR (300MHz, CDCl3) : ppm 0.00(m, 45H), 0.39-0.45(m, 26H), 1.51-1.59(m, 26H), 3.31-3.36(m, 26H), 3.47-3.65(m, 150H), 4.21-4.48(m, 8H), 5.10-5.35(m, 2H), 5.81(m, 4H), 6.06-6.12(m, 4H), 6.34-6.48(m, 4H) <Examples 2~3> The crosslinker compounds of Formula 1 (Examples 2 to 3) having a composition
(weight ratio) shown in Table 23 were prepared by the same method as in Example 1. <Comparative Example 1>
5.0Og of C4-4TEGMP obtained from Preparation Example 3 and 1.16g of D2-l,3- di(propoxy-6,7-propane diacrylate) obtained from Preparation Example 424 were reacted under the same method as in Example 1 to obtain crosslinker Ta-IOTEGMP.
1H-NMR (300MHz, CDCl3) : ppm 0.00(m, 42H), 0.32-0.58(m, 24H), 1.41-1.68(m, 24H), 3.31-3.59(m, 174H), 3.94-4.43(m,8H), 5.24-5.29(m,2H), 5.79-5.82(m, 4H), 6.01- 6.12(m, 4H), 6.37-6.48(m, 4H); 13C-NMR (300MHz, CDCl3) : ppm 0.00, 13.9, 23.1, 59.8, 62.8, 68.5, 70.2. 70.7. 71.2, 71.3, 72.6 74.1, 127.7, 127.9, 131.0, 131.2, 165.1, 165.5 [Table 23]
<Example 4> Preparation of a crosslinker (Pha-nTFSI-nTEGMP)
[Reaction Scheme 32]
Fuming H2SO4
0.72g of C4-4TFSI (compound A) obtained from Preparation Example 2, 5.0Og of C4-4TEGMP (compound B) obtained from Preparation Example 3 and 1.0 Ig of D2- 1,3- di(propane phenyl acrylate) (compound C) obtained from Preparation Example 426 were added to three neck flask and reacted under the same method as in Example 1 to obtain crosslinker Pha-1 TFSI-I OTEGMP (see Reaction Scheme 32).
1H-NMR (300MHz5 CDCl3) : ppm 0.00(m, 45H), 0.39-0.45(m, 26H), 1.51-1.59(m, 26H), 3.31-3.36(m, 26H), 3.47-3.65(m, 150H), 6.06(m, 2H), 6.34(m, 4H), 7.02-7.26(m, 8H) <Examples 5~6>
The crosslinker compounds of Formula 1 (Examples 5 to 6) having a composition (weight ratio) shown in Table 24 were prepared by the same method as in Example 1. [Table 24]
<Example 7> Manufacture of Conductive Thin Film 0.7g of crosslinker Pha-3 TFSI-I OTEGMP obtained from the Example 5 and 0.3g of the plasticizer Q-4TFSI obtained from the Preparation Example 2 were mixed with 0.123g of lithium trifluoromethane sulfonate (LiSO3CF3). To this mixture, 0.021 g of dimethoxyphenyl acetophenone (DMPA) was added. Then, the resulting mixture was coated onto a conductive glass substrate and exposed to 350nm UV rays for 30 minutes under nitrogen atmosphere. With this radiation, a transparent solid polymer electrolyte with good adhesion property was prepared.
[Experimental Example 11 Ionic Conductivity Test of the Crosslinker (Ta-xTFSI- vTEGMP)
Solid polymer electrolyte films were prepared having a composition shown in Table 25 by using the crosslinker Ta-xTFSI-y TEGMP of Examples 1 to 3 and the crosslinker of Ta-IOTEGMP of Comparative Example 1. Then, ionic conductivities of the solid polymer electrolyte films were measured as follows. First, a solid polymer electrolyte composition was coated onto a conductive glass substrate or onto a lithium- copper foil, photocured, and dried sufficiently. Under nitrogen atmosphere, AC impedance between band shaped (or sandwich shaped) electrodes was measured, and the measurement was analyzed with a frequency response analyzer to interpret complex impedance. To manufacture the band shaped electrodes, masking tapes having a width between 0.5mm and 2mm were adhered to the center of a conductive glass (ITO) at intervals of 0.5 — 2mm, etched in an etching solution, washed and dried. Ionic conductivity of the solid polymer electrolyte film thusly obtained was measured at a room temperature. Results are shown in Table 25. [Table 25] Ionic Conductivity of the Crosslinker (Ta-xTFSI-yTEGMP)
Solid polymer electrolyte films were prepared having a composition shown in Table 26 by using the crosslinker Pha-xTFSI-yTEGMP of Examples 4 to 6. Then, ionic
conductivities of the solid polymer electrolyte films were measured by the same method as in Experimental Example 1. [Table 26] Ionic Conductivity of the Crosslinker (Pha-xTFSI-yTEGMP)
[Experimental Example 31 Ionic Conductivity Test of the crosslinker (Ta-2.58TFSI- 1 OTEGMP) containing an anion receptors 0-4TFSI as a plasticizer
Solid polymer electrolyte films were prepared having a composition shown in Table 27 by using the crosslinker Ta-2.58TFSI-10TEGMP of Example 3. Then, ionic
conductivities of the solid polymer electrolyte films were measured by the same method as in Experimental Example 1. [Table 27]
Ionic Conductivity of the Crosslinker (Ta-2.58TFSI-10TEGMP) containing an anion receptors (C4-4TFSI)
FIG. 1 shows a change of the ionic conductivities according to the temperature when the crosslinker Ta-2.58TFSI-10TEGMP and anion receptor C4-TFSI as a plasticizer were used.
Industrial Applicability
As described above, the solid polymer electrolyte composition of the present invention has excellent mechanical properties such as drawing and bending properties owing to the skeletal structure of the added crosslinker, and offers substantially enhanced ionic conductivities at a room temperature to prepare the electrolyte thin film. Ln addition, the electrolyte thin film of the present invention has good film-forming properties and electrochemical stabilities, so they are for a broad range of applications which include small lithium polymer secondary cells used in portable information terminals, e.g., cell phones, notebook computers, etc., and all kinds of electronic equipments, e.g., camcorders, and large capacity lithium polymer secondary cells used in power storage systems for power equalization and electric vehicles.
Claims
[Formula 1]
R3 represents a hydrogen atom or a cyano group;
R4 is a hydrogen atom, 
R5 and R6 independently represents a hydrogen atom or a methyl group;
R7 and the other R7 in the formula 1 independently represents an alkyl, an alkenyl, an alkyl halide, an alkenyl halide, an alkanol, a halogen, a hydrogen atom or a hydroxyl group;
R8 and the other R8 in the formula 1 independently represents an alkyl, an alkenyl,
an alkyl halide, an alkenyl halide or 
R9 represents a hydrogen atom or a methyl group; R10 
R11 and the other R11 in the formula 1 independently represents an alkyl, an alkenyl, an alkyl halide, an alkenyl halide;
Y and Z each independently represent -O-, -S-, -CO-, -OCO-, -OCOO- or -COO-; n is an integer from 1 to 100; o, p, q, t and u are integers from 0 to 100, respectively; r and s are integers from 0 to 20, respectively, whose sum is at least 1 ; v represents integer from 1 to 6; and w represents integer from 0 to 4.
2. A gel or solid polymer electrolyte comprising the compound of claim 1.
3. The polymer electrolyte of claim 2, wherein the gel polymer electrolyte comprises: (i) a crosslinker of the compound of claim 1 ;
(ii) a nonaqueous solvent;
(iii) an anion receptor;
(iv) a curing initiator; and
(v) an alkali metal ion containing substance.
4. The polymer electrolyte of claim 2, wherein the solid polymer electrolyte comprises: (i) a crosslinker of the compound of claim 1; (ii) a plasticizer; (iii) a curing initiator; and (iv) an alkali metal ion containing substance.
5. The polymer electrolyte of claim 4, wherein the solid polymer electrolyte further comprises the substance selected from the group consisting of an anion receptor, polyalkyleneglycol dialkylether, a nonaqueous solvent and a mixture thereof as a plasticizer.
6. The polymer electrolyte of claim 3 to 5, wherein the anion receptor is selected from the group consisting of linear or cyclic siloxane compounds having amine substituted with electron withdrawing groups, or at least one of polyalkylene oxide group, cyano group and propylene carbonate group as a side branch in addition to the amine substituted with electron withdrawing groups; linear hydrocarbon compounds having amine substituted with electron withdrawing groups at its terminal group; and aromatic hydrocarbon compounds having amine substituted with electron withdrawing groups.
7. The polymer electrolyte of claim 5, wherein the polyalkyleneglycol dialkylether is selected from the group consisting of: polyethyleneglycol dimethylether
(PEGDME), polyethyleneglycol diethylether, polyethyleneglycol dipropylether, polyethyleneglycol dibutylether, polyethyleneglycol diglycidylether, polypropyleneglycol dimethylether, polypropyleneglycol diglycidylether, polypropyleneglycol/polyethyleneglycol copolymer terminated with dibutylether, and polyethyleneglycol/polypropyleneglycol/polyethyleneglycol block copolymer terminated with dibutylether.
8. The polymer electrolyte of one of claims 3 to 5, wherein the nonaqueous solvent is selected from the group consisting of: ethylene carbonate, dimethyl carbonate, diethyl carbonate, propylene carbonate, ether, organic carbonate, lactone, formate, ester, sulfonate, nitrite, oxazolidinone, tetrahydrofuran, 2-methyltetrahydrofuran, 4-methyl-l,3-
dioxolane, 1,3-dioxolane, 1,2-dimethoxyethane, dimethoxymethane, γ-butyrolactone,
methyl formate, sulforane, acetonitrile, 3-methyl-2-oxazolidinone, N-methyl-2- pyrrolidinone and mixtures thereof.
9. The polymer electrolyte of claim 3 or 4, wherein the alkali metal ion
containing substance is selected from the group consisting of LiSO3CF3, LiCOOC2F5, LiN(SO2CF3)2, LiC(SO2CF3)3, LiClO4, LiAsF6, LiBF4, LiPF6, LiSbF6, LiI, LiBr, LiCl, and a mixture thereof.
10. The polymer electrolyte of claim 3 or 4, wherein the curing initiator is selected from the group consisting of: a photocuring initiator, a heat-curing initiator, and a mixture thereof.
11. The polymer electrolyte of claim 10, wherein the photocuring initiator is selected from the group consisting of: dimethoxyphenyl acetophenone (DMPA), t-
butylperoxypivalate, ethyl benzoin ether, isopropyl benzoin ether, α-methyl bezoin ethyl
ether, benzoin phenyl ether, α-acyloxime ester, α,α-diethoxyacetophenone, 1,1- dichloroacetophenone, 2-hydroxy-2-methyl- 1 -phenylpropane- 1 -on, 1 -hydroxycyclohexyl
phenyl ketone, anthraquinone, thioxanthone, isopropyl thioxanthone, chlorothioxanthone, benzophenone, p-chlorobenzophenone, benzyl benzoate, benzoyl benzoate, Michler's ketone, and a mixture thereof; and wherein the heat-curing initiator is selected from the group consisting of: azoisobutyrontrile compounds, peroxide compounds and mixtures thereof.
12. The polymer electrolyte of claim 3, comprising 1 - 40 parts by weight of the crosslinker, 0.5 - 86.5 parts by weight of the nonaqueous solvent, 0 - 30 parts by weight of the anion receptor, 3 - 60 parts by weight of the alkali metal ion containing substance, and 0.5 — 5 parts by weight of a curing initiator.
13. The polymer electrolyte of claim 4, comprising 10 - 95 parts by weight of the crosslinker, 0.5 — 86.5 parts by weight of the substance selected from the group consisting of an anion receptor, polyalkyleneglycol dialkylether, a nonaqueous solvent and a mixture thereof, 3 - 60 parts by weight of the alkali metal ion containing substance, and 0.5 - 5 parts by weight of the curing initiator.
14. An electrochemical cell comprising an anode, a cathode and the electrolyte of claim 2.
15. The electrochemical cell of claim 14, wherein the anode is made of a material selected from the group that consists of lithium; lithium alloys; lithium-carbon intercalation compounds; lithium-graphite intercalation compounds; lithium metal oxide intercalation compounds; lithium metal sulfide intercalation compounds; mixtures thereof; and mixtures of these and alkali metals, and wherein, the cathode is made of a material selected from the group that consists of transition metal oxides, transition metal chalcogenides, poly(carbondisulfide)polymers, organic disulfide redox polymers, polyaniline, organic disulfide/polyaniline complexes, and mixtures of these and oxychlorides.
16. The electrochemical cell of claim 15, wherein the transition metal oxides is selected from the group consisting of Li25V6O13, LiL2V2O5, LiCoO2, LiNiO2, LiMn2O4, LiMnO2, and LiNi1-xMxO2 (wherein M is Co, Mg, Al or Ti); wherein the transition metal chalcogenides is selected from the group consisting of: LiNbSe3, LiTiS2, and LiMoS2; wherein the organic disulfide redox polymers are prepared by reversible electrochemical dimerization/division or polymerization/dissociation; and wherein the organic disulfide/polyaniline complexes are mixtures of polyaniline and 2,5-dimercapto-l ,3,4-thiadiazole.
17. A gel polymer electrolyte film manufactured using the gel polymer electrolyte of claim 3.
18. A solid polymer electrolyte film manufactured using the solid polymer electrolyte of claim 4.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011184333A (en) * | 2010-03-05 | 2011-09-22 | Shin-Etsu Chemical Co Ltd | Fluorine-containing organosilicon compound and method for producing the same |
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| CN111370758A (en) * | 2020-03-16 | 2020-07-03 | 中山大学 | A polymer solid electrolyte based on the principle of bulk plasticization and its preparation method |
| CN115428219A (en) * | 2020-06-30 | 2022-12-02 | 詹正雄 | Crosslinking agent for electrolyte, electrolyte composition comprising same, and lithium ion battery |
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| US9065150B2 (en) * | 2009-12-09 | 2015-06-23 | Nippon Shokubai Co., Ltd. | Electrolyte material, and battery material and secondary battery using said electrolyte material |
| US20120244427A1 (en) * | 2009-12-09 | 2012-09-27 | Nippon Shokubai Co., Ltd. | Electrolyte material, and battery material and secondary battery using said electrolyte material |
| JP2011184333A (en) * | 2010-03-05 | 2011-09-22 | Shin-Etsu Chemical Co Ltd | Fluorine-containing organosilicon compound and method for producing the same |
| US20120283378A1 (en) * | 2011-05-02 | 2012-11-08 | Ricoh Company, Ltd., | A silicone compound, photocurable liquid ink using the silicone compound, and method of manufacturing the ink |
| JP2013166908A (en) * | 2011-05-02 | 2013-08-29 | Ricoh Co Ltd | Silicone compound, photocurable liquid ink using the silicone compound, and method of manufacturing the ink |
| US8871861B2 (en) * | 2011-05-02 | 2014-10-28 | Ricoh Company, Ltd. | Silicone compound, photocurable liquid ink using the silicone compound, and method of manufacturing the ink |
| WO2013113593A1 (en) * | 2012-01-31 | 2013-08-08 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Polar functionalized oligomers, polymer compound having blended polar functionalized oligomers, method for production thereof, and use thereof |
| CN110915034A (en) * | 2017-11-20 | 2020-03-24 | 株式会社Lg化学 | Metal oxide coated with conductive polymer, electrode for electrochemical device comprising same, and method for producing metal oxide |
| CN110915034B (en) * | 2017-11-20 | 2022-05-31 | 株式会社Lg化学 | Metal oxide coated with conductive polymer, electrode for electrochemical device comprising the same, and method for preparing metal oxide |
| US11870062B2 (en) | 2017-11-20 | 2024-01-09 | Lg Energy Solution, Ltd. | Metal oxide coated with conductive polymer, electrode for electrochemical device comprising the same, and method of producing the metal oxide |
| CN111370758A (en) * | 2020-03-16 | 2020-07-03 | 中山大学 | A polymer solid electrolyte based on the principle of bulk plasticization and its preparation method |
| CN111370758B (en) * | 2020-03-16 | 2022-04-05 | 中山大学 | A polymer solid electrolyte based on the principle of bulk plasticization and its preparation method |
| CN115428219A (en) * | 2020-06-30 | 2022-12-02 | 詹正雄 | Crosslinking agent for electrolyte, electrolyte composition comprising same, and lithium ion battery |
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