CN110140187B - Electrolyte comprising 3,4-ethylenedioxythiophene, electrolytic capacitor comprising the same, and raw material for electronic material - Google Patents
Electrolyte comprising 3,4-ethylenedioxythiophene, electrolytic capacitor comprising the same, and raw material for electronic material Download PDFInfo
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- CN110140187B CN110140187B CN201780081684.4A CN201780081684A CN110140187B CN 110140187 B CN110140187 B CN 110140187B CN 201780081684 A CN201780081684 A CN 201780081684A CN 110140187 B CN110140187 B CN 110140187B
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- China
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- chemical formula
- ethylenedioxythiophene
- carbon number
- dihydrothieno
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- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000003792 electrolyte Substances 0.000 title claims abstract description 41
- 239000002994 raw material Substances 0.000 title claims abstract description 7
- 239000003990 capacitor Substances 0.000 title claims description 130
- 239000012776 electronic material Substances 0.000 title abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 120
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 34
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 20
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 11
- 125000000732 arylene group Chemical group 0.000 claims abstract description 10
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 42
- 229910052799 carbon Inorganic materials 0.000 claims description 42
- 229920001577 copolymer Polymers 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- 125000006267 biphenyl group Chemical group 0.000 claims 1
- 239000003431 cross linking reagent Substances 0.000 abstract description 31
- 239000000178 monomer Substances 0.000 description 93
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 91
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 87
- 238000006243 chemical reaction Methods 0.000 description 86
- 239000012044 organic layer Substances 0.000 description 72
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 69
- 238000002360 preparation method Methods 0.000 description 69
- 229910052782 aluminium Inorganic materials 0.000 description 62
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 62
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 56
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 51
- 230000000052 comparative effect Effects 0.000 description 50
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 45
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 42
- -1 3, 4-dimethoxythiophene (3, 4-dimethoxythiothiophene) Chemical compound 0.000 description 33
- 239000000243 solution Substances 0.000 description 31
- 238000005160 1H NMR spectroscopy Methods 0.000 description 30
- 230000015556 catabolic process Effects 0.000 description 30
- 229910052938 sodium sulfate Inorganic materials 0.000 description 29
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 28
- 239000000203 mixture Substances 0.000 description 23
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 22
- 235000011152 sodium sulphate Nutrition 0.000 description 22
- 238000004440 column chromatography Methods 0.000 description 21
- 239000010410 layer Substances 0.000 description 21
- 238000000746 purification Methods 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 239000000377 silicon dioxide Substances 0.000 description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000011734 sodium Substances 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 17
- 235000012239 silicon dioxide Nutrition 0.000 description 16
- 125000004429 atom Chemical group 0.000 description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 14
- 239000001301 oxygen Substances 0.000 description 14
- 229910000104 sodium hydride Inorganic materials 0.000 description 14
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 13
- 239000011541 reaction mixture Substances 0.000 description 13
- 239000012312 sodium hydride Substances 0.000 description 13
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 12
- 229940125810 compound 20 Drugs 0.000 description 12
- JAXFJECJQZDFJS-XHEPKHHKSA-N gtpl8555 Chemical compound OC(=O)C[C@H](N)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](C(C)C)C(=O)N[C@@H](C(C)C)C(=O)N1CCC[C@@H]1C(=O)N[C@H](B1O[C@@]2(C)[C@H]3C[C@H](C3(C)C)C[C@H]2O1)CCC1=CC=C(F)C=C1 JAXFJECJQZDFJS-XHEPKHHKSA-N 0.000 description 12
- 238000004804 winding Methods 0.000 description 12
- 229920001940 conductive polymer Polymers 0.000 description 11
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 11
- 239000002480 mineral oil Substances 0.000 description 11
- 235000010446 mineral oil Nutrition 0.000 description 11
- 239000007800 oxidant agent Substances 0.000 description 11
- 239000010453 quartz Substances 0.000 description 11
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 10
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 10
- 239000011888 foil Substances 0.000 description 9
- 230000001590 oxidative effect Effects 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 125000005055 alkyl alkoxy group Chemical group 0.000 description 8
- 238000000605 extraction Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 239000007832 Na2SO4 Substances 0.000 description 7
- BKOYXHHPFBFYFR-UHFFFAOYSA-N 3,4-dimethoxythiophene Chemical compound COC1=CSC=C1OC.COC1=CSC=C1OC BKOYXHHPFBFYFR-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 101100402127 Escherichia coli (strain K12) moaA gene Proteins 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 239000005518 polymer electrolyte Substances 0.000 description 6
- 125000004311 dioxin-2-yl group Chemical group [H]C1=C([H])OC(*)=C([H])O1 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 125000006850 spacer group Chemical group 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- ZNYRFEPBTVGZDN-UHFFFAOYSA-N 5S,6S-epoxy-15R-hydroxy-ETE Chemical compound COCCOCCOCCOCCO ZNYRFEPBTVGZDN-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- WHRAZOIDGKIQEA-UHFFFAOYSA-L iron(2+);4-methylbenzenesulfonate Chemical compound [Fe+2].CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 WHRAZOIDGKIQEA-UHFFFAOYSA-L 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 125000005767 propoxymethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])[#8]C([H])([H])* 0.000 description 3
- OVPQPMTZOLCPHB-UHFFFAOYSA-N 2-(2-heptoxyethoxy)ethanol Chemical compound CCCCCCCOCCOCCO OVPQPMTZOLCPHB-UHFFFAOYSA-N 0.000 description 2
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 description 2
- QGGOWKVZAAUUNJ-UHFFFAOYSA-N 2-hexoxyethyl 4-methylbenzenesulfonate Chemical compound CCCCCCOCCOS(=O)(=O)C1=CC=C(C)C=C1 QGGOWKVZAAUUNJ-UHFFFAOYSA-N 0.000 description 2
- SSZWWUDQMAHNAQ-UHFFFAOYSA-N 3-chloropropane-1,2-diol Chemical compound OCC(O)CCl SSZWWUDQMAHNAQ-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- LNUFLCYMSVYYNW-ZPJMAFJPSA-N [(2r,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[[(3s,5s,8r,9s,10s,13r,14s,17r)-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-3-yl]oxy]-4,5-disulfo Chemical compound O([C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1C[C@@H]2CC[C@H]3[C@@H]4CC[C@@H]([C@]4(CC[C@@H]3[C@@]2(C)CC1)C)[C@H](C)CCCC(C)C)[C@H]1O[C@H](COS(O)(=O)=O)[C@@H](OS(O)(=O)=O)[C@H](OS(O)(=O)=O)[C@H]1OS(O)(=O)=O LNUFLCYMSVYYNW-ZPJMAFJPSA-N 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 2
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- ZITKDVFRMRXIJQ-UHFFFAOYSA-N dodecane-1,2-diol Chemical compound CCCCCCCCCCC(O)CO ZITKDVFRMRXIJQ-UHFFFAOYSA-N 0.000 description 2
- 229940093476 ethylene glycol Drugs 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
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- ZYZCALPXKGUGJI-DDVDASKDSA-M (e,3r,5s)-7-[3-(4-fluorophenyl)-2-phenyl-5-propan-2-ylimidazol-4-yl]-3,5-dihydroxyhept-6-enoate Chemical compound C=1C=C(F)C=CC=1N1C(\C=C\[C@@H](O)C[C@@H](O)CC([O-])=O)=C(C(C)C)N=C1C1=CC=CC=C1 ZYZCALPXKGUGJI-DDVDASKDSA-M 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- YMMGRPLNZPTZBS-UHFFFAOYSA-N 2,3-dihydrothieno[2,3-b][1,4]dioxine Chemical class O1CCOC2=C1C=CS2 YMMGRPLNZPTZBS-UHFFFAOYSA-N 0.000 description 1
- SCOBKWYTBDRAOQ-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethyl 4-methylbenzenesulfonate Chemical compound CCCCOCCOCCOCCOS(=O)(=O)C1=CC=C(C)C=C1 SCOBKWYTBDRAOQ-UHFFFAOYSA-N 0.000 description 1
- VYVPNTJBGPQTFA-UHFFFAOYSA-N 2-[2-(4-methylphenyl)sulfonyloxyethoxy]ethyl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OCCOCCOS(=O)(=O)C1=CC=C(C)C=C1 VYVPNTJBGPQTFA-UHFFFAOYSA-N 0.000 description 1
- CRLOMMYKVYXMLY-UHFFFAOYSA-N 2-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]ethyl 4-methylbenzenesulfonate Chemical compound COCCOCCOCCOCCOS(=O)(=O)C1=CC=C(C)C=C1 CRLOMMYKVYXMLY-UHFFFAOYSA-N 0.000 description 1
- NPRYCHLHHVWLQZ-TURQNECASA-N 2-amino-9-[(2R,3S,4S,5R)-4-fluoro-3-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-7-prop-2-ynylpurin-8-one Chemical compound NC1=NC=C2N(C(N(C2=N1)[C@@H]1O[C@@H]([C@H]([C@H]1O)F)CO)=O)CC#C NPRYCHLHHVWLQZ-TURQNECASA-N 0.000 description 1
- UPGSWASWQBLSKZ-UHFFFAOYSA-N 2-hexoxyethanol Chemical compound CCCCCCOCCO UPGSWASWQBLSKZ-UHFFFAOYSA-N 0.000 description 1
- BKXFVDQXVXORRV-UHFFFAOYSA-N 3-(butoxymethyl)-2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1C(COCCCC)COC2=CSC=C21 BKXFVDQXVXORRV-UHFFFAOYSA-N 0.000 description 1
- ZNZXGOFZNBGIQC-UHFFFAOYSA-N 3-[2-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]ethoxymethyl]-2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound C(OCCOCCOCCOCCOC)C1COC=2C(O1)=CSC=2 ZNZXGOFZNBGIQC-UHFFFAOYSA-N 0.000 description 1
- NOSFOHBDBNIIJQ-UHFFFAOYSA-N 4-methyl-2-[2-(5-methyl-2-sulfophenyl)ethyl]benzenesulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C(CCC=2C(=CC=C(C)C=2)S(O)(=O)=O)=C1 NOSFOHBDBNIIJQ-UHFFFAOYSA-N 0.000 description 1
- BNNMDMGPZUOOOE-UHFFFAOYSA-N 4-methylbenzenesulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1.CC1=CC=C(S(O)(=O)=O)C=C1 BNNMDMGPZUOOOE-UHFFFAOYSA-N 0.000 description 1
- YZYYIAXSSKVOGE-UHFFFAOYSA-N 6-(4-methylphenyl)sulfonyloxyhexyl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OCCCCCCOS(=O)(=O)C1=CC=C(C)C=C1 YZYYIAXSSKVOGE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
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- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
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- FHKPLLOSJHHKNU-INIZCTEOSA-N [(3S)-3-[8-(1-ethyl-5-methylpyrazol-4-yl)-9-methylpurin-6-yl]oxypyrrolidin-1-yl]-(oxan-4-yl)methanone Chemical compound C(C)N1N=CC(=C1C)C=1N(C2=NC=NC(=C2N=1)O[C@@H]1CN(CC1)C(=O)C1CCOCC1)C FHKPLLOSJHHKNU-INIZCTEOSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- UEDLGMJYAZLEHS-UHFFFAOYSA-N [4-[(4-methylphenyl)sulfonyloxymethyl]cyclohexyl]methyl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OCC1CCC(COS(=O)(=O)C=2C=CC(C)=CC=2)CC1 UEDLGMJYAZLEHS-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- WNQKPOBAKJQOKF-UHFFFAOYSA-L benzenesulfonate;iron(2+) Chemical compound [Fe+2].[O-]S(=O)(=O)C1=CC=CC=C1.[O-]S(=O)(=O)C1=CC=CC=C1 WNQKPOBAKJQOKF-UHFFFAOYSA-L 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
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- 238000003763 carbonization Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 125000002668 chloroacetyl group Chemical group ClCC(=O)* 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- YSRSBDQINUMTIF-UHFFFAOYSA-N decane-1,2-diol Chemical compound CCCCCCCCC(O)CO YSRSBDQINUMTIF-UHFFFAOYSA-N 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
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- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- GGHPFIYIFKEQCM-UHFFFAOYSA-L iron(2+);naphthalene-1-sulfonate Chemical compound [Fe+2].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1.C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 GGHPFIYIFKEQCM-UHFFFAOYSA-L 0.000 description 1
- FYMCOOOLDFPFPN-UHFFFAOYSA-K iron(3+);4-methylbenzenesulfonate Chemical compound [Fe+3].CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 FYMCOOOLDFPFPN-UHFFFAOYSA-K 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- LYQJBZLAANNIER-UHFFFAOYSA-N octyl 4-methylbenzenesulfonate Chemical compound CCCCCCCCOS(=O)(=O)C1=CC=C(C)C=C1 LYQJBZLAANNIER-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-M toluene-4-sulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-M 0.000 description 1
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Abstract
The invention discloses an electrolyte containing a 3,4-ethylenedioxythiophene cross-linking agent and having high withstand voltage and low equivalent series resistance, and a raw material for an electronic material containing the same. The electrolyte comprises more than one 3,4-ethylenedioxythiophene derivatives represented by chemical formula 1 in the specification. In the chemical formula 1, l and n are each independently an integer of 0 to 3, a is absent or is an alkyl group or an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, a cyclic or chain alkylene group having 4 to 15 carbon atoms, or the like, which contains 0 to 5 oxygen atoms (O), B is an alkyl group having 1 to 20 carbon atoms, or the like, but l + n is an integer of 3 or less.
Description
Technical Field
The present invention relates to an electrolyte containing 3,4-ethylenedioxythiophene, an electrolytic capacitor containing the same, and a raw material for an electronic material, and more particularly, to an electrolyte containing 3,4-ethylenedioxythiophene having a high withstand voltage and a low equivalent series resistance, an electrolytic capacitor containing the same, and a raw material for an electronic material (conductive).
Background
Recently, as electronic devices have been improved in performance and miniaturized, the frequency of using electronic devices not only in a fixed place but also in the process of moving, as in the case of mobile devices, has been increasing. For example, in a severe environment having many electronic devices such as an electric vehicle, it is important to ensure long-term reliability of the electronic devices in order to achieve smooth driving.
In the electrolytic capacitor used for the electronic device as described above, aluminum, tantalum, or the like is used as the positive electrode-side counter electrode, a dielectric is formed on the positive electrode foil, a spacer is interposed between the positive electrode foil and the negative electrode foil (between the positive electrode foil and the negative electrode foil), and then the capacitor device is formed by winding, and the electrolytic layer is formed on the formed capacitor device, whereby the capacitor device is sealed in a metal case made of aluminum or the like or a case made of synthetic resin.
Generally, as a conductive polymer used as the electrolyte, a conductive polymer prepared by mixing a polymerizable monomer such as 3,4-ethylenedioxythiophene and an oxidizing agent solution and polymerizing the mixture is known.
Conventionally synthesized 3,4-ethylenedioxythiophene monomers are formed in a form in which withstand voltage characteristics are improved by a structure in which the monomer is polymerized only as a single monomer or is singly substituted at a tertiary carbon site (see laid-open patent No. 2012-0113701).
However, although improvement of the withstand voltage characteristics to some extent can be expected by homopolymerization of 3,4-ethylenedioxythiophene substituted with an alkyl group as described above, there is a problem that it is difficult to produce an electrolyte having high withstand voltage characteristics, and an electrolyte having high withstand voltage characteristics can be produced by introducing a long alkyl group, but in this case, there is also a problem that the Equivalent Series Resistance (ESR) becomes excessively high.
Disclosure of Invention
Technical subject
Accordingly, an object of the present invention is to provide an electrolyte containing 3,4-ethylenedioxythiophene, which has improved withstand voltage characteristics, low equivalent series resistance, and long-term reliability, and an electrolytic capacitor and a (conductive) material for electronic materials containing the electrolyte.
In order to achieve the object, an electrolyte comprising one or more 3,4-ethylenedioxythiophene derivatives represented by the following chemical formula 1 is provided.
Chemical formula 1
In the chemical formula 1, l and n are each independently an integer of 0 to 3, a is absent (the left side chain of a is connected to the right side chain of a by a single bond) or is an alkyl or alkylene group having a carbon number of 1 to 20, an arylene group having a carbon number of 6 to 20, a cyclic or chain alkylene group having a carbon number of 4 to 15, which contains 0 to 5 oxygen atoms (O), and B is a carbon number of 1 to 20Alkyl or
However, l + n is an integer of 3 or less.
Further, the present invention provides an electrolytic capacitor comprising: a positive electrode layer having an oxide film; a negative electrode layer; and a separator and an electrolyte between the positive and negative electrode layers, the electrolyte comprising one or more 3,4-ethylenedioxythiophene derivatives represented by the chemical formula 1.
Effects of the invention
The electrolyte of the present invention uses a 3,4-ethylenedioxythiophene derivative, and has excellent withstand voltage characteristics and low equivalent series resistance. The capacitor of the present invention has excellent withstand voltage characteristics, low equivalent series resistance, and excellent long-term reliability. Furthermore, the 3,4-ethylenedioxythiophene derivative of the present invention has very excellent conductivity.
Drawings
Fig. 1 is a perspective view of an electrolytic capacitor as an example of the capacitor of the present invention.
Detailed Description
The present invention will be described in more detail below with reference to the accompanying drawings.
The electrolyte of the present invention comprises one or more 3,4-Ethylenedioxythiophene Derivatives (EDOT).
The 3,4-ethylenedioxythiophene derivative improves voltage Resistance characteristics and has a low Equivalent Series Resistance (ESR) by including an alkyl group and/or an alkoxy group, which is represented by the following chemical formula 1.
Chemical formula 1
In the chemical formula 1, l and n are each independently an integer of 0 to 3, specifically an integer of 0 to 2, and A is absent (the left-side chain group of A is linked to the right-side chain of A by a single bond)Linked with a group) or an alkyl or alkylene group having 1 to 20 carbon atoms (e.g., chain or the like) containing 0 to 5 oxygen atoms (O) or an arylene group having 6 to 20 carbon atoms, and specifically may be a cyclic or chain alkylene group having 4 to 15 carbon atoms or a phenylene, biphenyl or naphthyl group having 6 to 15 carbon atoms, and for example, may be
And, B may be an alkyl group (e.g., chain) having a carbon number of 1 to 20 or
Wherein,
this means a bonding portion, but l + n is an integer of 3 or less.
Specifically, the 3,4-ethylenedioxythiophene derivative may be represented by the following chemical formula 2 or 3.
In the chemical formulas 2 and 3, l and a are the same as defined in chemical formula 1, and p is an integer of 1 to 19, specifically 1 to 10, more specifically 1 to 7.
The 3,4-ethylenedioxythiophene derivatives of the present invention may be used alone or in combination of the compounds represented by the above chemical formulae 2 and 3, or may be used in combination with one or more compounds represented by the following chemical formula 4, for example, a mixture of (a) one or more 3,4-ethylenedioxythiophene derivatives represented by chemical formula 2, (b) one or more 3,4-ethylenedioxythiophene derivatives represented by chemical formula 3, (c) one or more 3,4-ethylenedioxythiophene derivatives represented by chemical formula 2 and one or more 3,4-ethylenedioxythiophene derivatives represented by chemical formula 4, (d) one or more 3,4-ethylenedioxythiophene derivatives represented by chemical formula 3 and one or more 3 represented by chemical formula 4, a mixture of 4-ethylenedioxythiophene derivatives, (e) a mixture of one or more 3,4-ethylenedioxythiophene derivatives represented by chemical formula 2, one or more 3,4-ethylenedioxythiophene derivatives represented by chemical formula 3, and one or more 3,4-ethylenedioxythiophene derivatives represented by chemical formula 4. In this case, the withstand voltage characteristic is more excellent, and the equivalent series resistance can be lower, and therefore, the present invention is effective. In this case, a mixture means a copolymer which is simply mixed or copolymerized, and specifically means a copolymer.
In the chemical formula 4, R is hydrogen or an alkyl group having a carbon number of 1 to 20, specifically, an alkyl group having a carbon number of 3 to 10 (e.g., a chain alkyl group).
In the electrolyte of the present invention, in the case of using the compounds represented by chemical formulas 2 to 4 in admixture, the content of the 3,4-ethylenedioxythiophene derivative represented by chemical formula 3 is 0.1 to 10 parts by weight, specifically 0.5 to 5 parts by weight, more specifically 1 to 3 parts by weight, and the content of the 3,4-ethylenedioxythiophene derivative represented by chemical formula 2 and/or 4 is each 1 to 99 mol%, specifically 20 to 80 mol%, more specifically 50 to 50 mol%, relative to 100 parts by weight of the electrolyte. If the content of a plurality of the 3,4-ethylenedioxythiophene derivatives exceeds the range, the withstand voltage characteristics and the equivalent series resistance may be poor due to low concentration between the 3,4-ethylenedioxythiophene polymers, or the equivalent series resistance may become excessively high due to high concentration of the 3,4-ethylenedioxythiophene polymers.
In the electrolyte of the present invention, when the compound represented by the chemical formula 3 forms a polymer in the electrolyte, as shown in the following structure 1, it may act as a cross-linking agent between polymers different from each other, in which case, the bonding between the 3,4-ethylenedioxythiophene polymers is made stronger, thereby improving the withstand voltage characteristics and having a low Equivalent Series Resistance (ESR).
Structure 1
In the structure 1, R, l, p and a are the same as defined in the chemical formula 1.
In the electrolyte of the present invention, the weight average molecular weight of the 3,4-ethylenedioxythiophene derivative represented by chemical formula 1 is not particularly limited, and is usually 1000 to 500000, specifically 5000 to 20000, as long as it can function as a conductive polymer electrolyte. If the value of the weight average molecular weight is too low, the dielectric oxide film layer may not exhibit sufficient withstand voltage characteristics, and leak current may become high, and if it is too large, the 3,4-ethylenedioxythiophene derivative may not be completely dissolved, and a strong and uniform electrolyte layer may not be formed, and the efficiency of withstand voltage characteristics and low equivalent series resistance may be lowered.
In the method for preparing the 3,4-ethylenedioxythiophene derivative represented by the chemical formula 2, there is no particular limitation as long as it can be prepared, and for example, as shown in the following reaction formulas 1 and 2, first, a compound e is reacted with tosyl chloride in triethylamine to prepare a compound f (a first intermediate of chemical formula 2). Next, compound h (a second intermediate of chemical formula 2) is prepared by reacting 3, 4-dimethoxythiophene with compound g in p-toluenesulfonic acid, and then compound i is prepared by reacting the prepared compound h with chloroacetyl in dimethyl sulfoxide (dimethyl sulfoxide). Then, the prepared compound i is reacted with sodium hydroxide to prepare a compound j (a third intermediate of chemical formula 2), and then, the prepared compound j, a compound f and sodium hydride are reacted in dimethylformamide to prepare the compound j. In the following reaction formulas 1 and 2, l and p are the same as defined in the chemical formula 2.
Reaction scheme 1
As described above, the preparation method of the cross-linking agent represented by the chemical formula 3 is not particularly limited, and for example, as shown in the following reaction formulas 3 and 4, first, the compound a and tosyl chloride (toluensulfonyl chloride) are reacted in Triethylamine (TEA) and dichloromethane (MC) to prepare the compound b (the first intermediate of the chemical formula 3). Then, the compound b, the compound j, and sodium hydride (NaH) can be reacted with Dimethylformamide (DMF).
The preparation method of the 3,4-ethylenedioxythiophene derivative represented by the chemical formula 4 is not particularly limited, and for example, as shown in the following reaction formula 4, 3, 4-dimethoxythiophene (3, 4-dimethoxythiothiophene) may be reacted with a diol (diol) compound represented by compound d.
The electrolyte of the present invention can be formed by polymerizing the crosslinking agent and the 3,4-ethylenedioxythiophene derivative, and the method is not particularly limited, and for example, the electrolyte can be formed by any of chemical oxidative polymerization and electrolytic oxidative polymerization, and specifically, a copolymer can be produced by chemical oxidative polymerization. For example, the crosslinking agent and the 3,4-ethylenedioxythiophene derivative may be mixed with a solution in which an oxidizing agent is dissolved, and then heated to polymerize the compound.
As the oxidizing agent, iron (iii) organic sulfonate can be used, and specifically, iron p-toluenesulfonate, iron benzenesulfonate, iron naphthalenesulfonate, and the like can be used. Also, as the above solvent in which the oxidizing agent is dissolved, n-butanol, ethanol, toluene, or the like can be used, and as the oxidizing agent, a solvent in which 20 to 90% by weight, specifically 30 to 80% by weight, more specifically 40 to 70% by weight of the oxidizing agent is dissolved in an alcohol can be used.
Next, the electrolytic capacitor of the present invention will be explained. Fig. 1 is a perspective view of an electrolytic capacitor as an example of the capacitor of the present invention. As shown in fig. 1, the electrolytic capacitor of the present invention includes: a positive electrode layer 1 having an oxide film; a negative electrode layer 2; and a separator (separator)5 and an electrolyte between the positive electrode layer and the negative electrode layer. The electrolyte is a polymer including one or more monomers of 3,4-ethylenedioxythiophene derivatives represented by the chemical formula 1 (e.g., the monomers of the chemical formulas 2 and 4 and the cross-linking agent of the chemical formula 3). The spacer 5 is cellulose having excellent impregnation property and acrylic having excellent pressure resistance, and when the crosslinking agent and the 3,4-ethylenedioxythiophene derivative of the present invention are used, nylon having no carbonization step is preferably used because of low density, but the spacer is not limited to nylon.
In order to produce the electrolytic capacitor of the present invention, first, a spacer 5 is provided between the positive electrode layer 1 having the oxide film and the negative electrode layer 2. Next, a monomer containing one or more 3,4-ethylenedioxythiophene derivatives represented by the chemical formula 1 and an oxidizing agent are impregnated between the positive electrode layer 1 and the negative electrode layer 2, and the monomer is heated to form an electrolyte, and the impregnation may be performed for 120 seconds. Then, for the formed capacitor device, the capacitor case was prepared using an epoxy resin, and an electrolytic capacitor was prepared by applying a voltage of 4V to the positive electrode and then performing an aging treatment.
The electrolytic capacitor of the present invention has a high withstand voltage and a low equivalent series resistance, and therefore, can be used for various electronic components, for example, circuits using capacitors such as a central processing circuit and a power supply circuit, which can be used for various digital devices such as a computer, a server, a video camera, a game machine, a DVD device, an AV device, and a mobile phone, and electronic devices such as various power supplies, and the 3,4-ethylenedioxythiophene derivative of the present invention has excellent conductivity and can be used as a material for electrodes of a transparent conductive liquid crystal display, an electroluminescent display, an electrochromic display, a solar cell, a touch panel, and the like, and for substrates of an electromagnetic shielding material and the like.
EMBODIMENTS FOR CARRYING OUT THE INVENTION
The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.
Preparation example 1: preparation of monomer of chemical formula 4
As shown in the following reaction scheme 5, 3, 4-dimethoxythiophene (3, 4-dimethoxythiophene) 1(30.00g, 208.06mmol), ethylene glycol (ethyleneglycol)2(25.83g, 416.12mmol), p-toluenesulfonic acid (p-toluenesulfonic acid) (3.96g, 20.81mmol) and 300mL of toluene were mixed, and the mixture was stirred at 100 ℃ for 12 hours to effect a reaction. The reaction mixture was completely dissolved by adding ethyl acetate, and the mixture was extracted with water and then with sodium sulfate (Na)2SO4) The organic layer was dried and the remaining organic layer was concentrated. By means of silicon dioxide (SiO)2) Column chromatography and using hexane: ethyl acetate 10: the concentrated organic layer was developed from the 1 (volume ratio) mixed solution and subjected to column purification, thereby obtaining compound 3(20.70g, 70% yield) as 3,4-Ethylenedioxythiophene (3,4-Ethylenedioxythiophene, EDOT).
1H-NMR(CDCl3，Varian 400MHz)：δ4.18(4H，s)，6.31(2H，s)
Preparation example 2: preparation of monomer of chemical formula 4
As shown in the following reaction scheme 6, 3, 4-dimethoxythiophene 1(30.00g, 208.06mmol), 1,2-pentanediol (1,2-pentanediol)4(43.34g, 416.12mmol), p-toluenesulfonic acid (3.96g, 20.81mmol) and 300mL of toluene were mixed, and the mixture was stirred at 110 ℃ for 9 hours and reacted. The reaction solution was completely dissolved by adding ethyl acetate, and after extraction with water, the organic layer was dried over sodium sulfate, and the remaining organic layer was concentrated. Column chromatography over silica and using hexane: ethyl acetate 10: 1 (volume ratio) of the mixed solution to spread the concentrated organic layer and carry out column purification, thereby obtaining 2-propyl-2,3-dihydrothieno [3,4-b ] as a 2-propyl-2,3-dihydrothieno [3,4-b ]][1,4]II
English (2-Propyl-2,3-dihydrothieno [3, 4-b)][1,4]dioxine, propyl-EDOT) (25.00g, 70% yield).
1H-NMR(CDCl3，Varian 400MHz)：δ0.88(3H，t，J＝12Hz)，1.31-1.70(4H，m)，3.86(1H，dd，J＝8.0，3.2Hz)，4.10-4.16(2H，m)，6.30(2H，s)。
Reaction formula 6
Preparation example 3: preparation of monomer of chemical formula 4
As shown in the following reaction scheme 7, 3, 4-dimethoxythiophene 1(50.00g, 346.76mmol), 1,2-decanediol (1, 2-decanodiol) 6(120.87g, 693.52mmol), p-toluenesulfonic acid (6.60g, 34.68mmol) and 500mL of toluene were mixed, and the mixture was stirred at 110 ℃ for 9 hours to effect a reaction. Ethyl acetate was added to completely dissolve the reaction mixture,extracting with water, and extracting with sodium sulfate (Na)2SO4) The organic layer was dried and the remaining organic layer was concentrated. Column chromatography over silica and using hexane: ethyl acetate 10: the concentrated organic layer was developed from the 1 (volume ratio) mixed solution and subjected to column purification, to thereby obtain 2-octyl-2,3-dihydrothieno [3,4-b ]][1,4]II
English (2-Octyl-2,3-dihydrothieno [3, 4-b)][1,4]dioxine, octyl-EDOT) compound 7(57.33g, 65% yield).
1H-NMR(CDCl3，Varian 400MHz)：δ0.88(3H，t，J＝12Hz)，1.27-1.71(14H，m)，3.86(1H，dd，J＝8.0，3.2Hz)，4.07-4.15(2H，m)，6.29(2H，s)。
Reaction formula 7
Preparation example 4: preparation of monomer of chemical formula 4
As shown in the following reaction scheme 8, 3, 4-dimethoxythiophene 1(30.00g, 208.06mmol), 1,2-dodecanediol (1,2-dodecanediol)8(42.07g, 416.12mmol), p-toluenesulfonic acid (3.96g, 20.81mmol) and 300mL of toluene were mixed, stirred at 110 ℃ for 9 hours and reacted. Ethyl acetate was added to completely dissolve the reaction solution, and after extraction with water, the organic layer was dried over sodium sulfate, and the remaining organic layer was concentrated. Column chromatography over silica and using hexane: ethyl acetate 10: 1 (volume ratio) of the mixed solution was developed into a concentrated organic layer and subjected to column purification, thereby obtaining 2-decyl-2,3-dihydrothieno [3,4 ]][1,4]II
English (2-Decyl-2,3-dihydrothieno [3, 4-b)][1,4]dioxine, decyl-EDOT) compound 9(38.20g, 65% yield).
1H-NMR(CDCl3，Varian 400MHz)：δ0.88(3H，t，J＝12Hz)，1.27-1.71(18H，m)，3.86(1H，dd，J＝8.0，3.2Hz)，4.07-4.15(2H，m)，6.29(2H，s)。
Reaction formula 8
Preparation example 5: first intermediate for preparing monomer of chemical formula 2
As shown in the following reaction scheme 9-1, n-Propanol (n-Propanol)10(100g, 0.524mol) and Triethylamine (TEA) (108.95mL, 0.786mol) were dissolved in Dichloromethane (DCM) (1000mL, 10mL/g), and then Tosyl chloride (Tosyl chloride) (100g, 0.524mol) was added at 0 ℃ and stirred at room temperature for 20 hours. After the reaction was complete, it was extracted with Dichloromethane (DCM) using anhydrous Na2SO4The organic layer was dried and concentrated to obtain compound 10-1(105.5g, 94% yield) as a liquid.
1H NMR：δ0.87-0.90(3H，t，J＝7.6Hz)，1.63-1.68(2H，m)，2.43(3H，s)，3.96-3.99(2H，t，J＝6.8Hz)，7.32-7.34(2H，d，J＝8.4Hz)，7.77-7.79(2H，d，J＝8.0Hz)。
Reaction formula 9-1
Preparation example 6: first intermediate for preparing monomer of chemical formula 2
As shown in the following reaction scheme 9-2, n-Butanol (n-Butanol)11(130mL, 1.416mol) and triethylamine (98.15mL, 0.708mol) were dissolved in Dichloromethane (DCM) (9000mL, 10mL/g), followed by addition of tosyl chloride (90g, 0.472mol) at 0 ℃ and stirring at room temperature for 20 hours. After the reaction was completed, extraction was performed with dichloromethane and anhydrous Na2SO4The organic layer was dried and concentrated to obtain the liquid compound 11-1(89.9g, 89% yield).
1H NMR：δ0.82-0.86(3H，t，J＝7.6Hz)，1.27-1.37(2H，m)，1.57-1.64(2H，m)2.43(3H，s)，3.99-4.2(2H，t，J＝6.8Hz)，7.32-7.34(2H，d，J＝8.4Hz)，7.76-7.78，d，J＝8.0Hz)。
Reaction formula 9-2
Preparation example 7: first intermediate for preparing monomer of chemical formula 2
As shown in the following reaction scheme 9-3, diethylene glycol monoethyl ether (diethylene glycol monoethyl ether) 12(20g, 149.05mmol) and triethylamine (31.18mL, 223.58mmol) were dissolved in methylene chloride (200mL, 10mL/g), and then tosyl chloride (25.57g, 134.15mmol) was added at 0 ℃ and stirred at room temperature for 3 hours. After the reaction was completed, by extraction using dichloromethane with anhydrous Na2SO4The organic layer was dried and concentrated to obtain the compound 12-1(35.0g, 81% yield) as a liquid of 2- (2-ethoxyethoxy) ether 4-methylbenzenesulfonate (2- (2-ethoxyyethoxy) ether 4-methyllbenzenesulfonate).
1H-NMR(CDCl3，Varian 400MHz)：δ1.19(3H，t，J＝7.2Hz)，2.45(3H，s)，3.47-3.53(4H，m)，3.57-3.59(2H，m)，3.70(2H，t，J＝4.8Hz)4.17(2H，t，J＝5.2Hz)，7.34(2H，d，J＝8.0Hz)，7.80(2H，d，J＝8.4Hz)。
Reaction formula 9-3
Preparation example 8: first intermediate for preparing monomer of chemical formula 2
As shown in the following reaction scheme 9-4, after dissolving 1-octanol (1-octanol)13(20g, 153.57mmol) and triethylamine (32.13mL, 230.36mmol) in dichloromethane (200mL, 10mL/g), tosyl chloride (26.35g, 138.21mmol) was added at 0 ℃ and stirred at normal temperature for 3 hours. After the reaction was completed, extraction was performed using dichloromethane using anhydrous Na2SO4Is driedAnd the organic layer was concentrated to obtain compound 13-1(34.0g, 78% yield) as a liquid of Octyl 4-methylbenzenesulfonate (Octyl 4-methylb zenesulfonate).
1H-NMR(CDCl3，Varian 400MHz)：δ0.87(3H，t，J＝7.2Hz)，1.21-1.28(10H，s)，1.60-1.67(2H，m)，2.45(3H，s)，4.02(2H，t，J＝6.4Hz)，7.34(2H，d，J＝8.0Hz)，7.79(2H，d，J＝8.0Hz)。
Reaction formula 9-4
Preparation example 9: first intermediate for preparing monomer of chemical formula 2
As shown in the following reaction scheme 9-5, ethylene glycol monohexyl ether (20g, 136.77mmol) 14 and triethylamine (28.61mL, 205.16mmol) were dissolved in dichloromethane (200mL, 10mL/g), after which tosyl chloride (23.47g, 123.09mmol) was added at 0 ℃ and stirred at normal temperature for 3 hours. After the reaction was complete, it was extracted with Dichloromethane (DCM) using anhydrous Na2SO4The organic layer was dried and concentrated to obtain the liquid compound 14-1(34.0g, 92% yield) as 2- (hexyloxy) ethyl 4-methylbenzenesulfonate (2- (hexyloxy) ethyl 4-methylb enzenesulfonate).
1H-NMR(CDCl3，Varian 400MHz)：δ0.88(3H，t，J＝6.8Hz)，1.24-1.32(7H，m)，1.47-1.50(2H，m)，2.45(2H，s)，3.37(2H，t，J＝7.2Hz)，3.60(2H，t，J＝4.8Hz)，4.16(2H，t，J＝5.2Hz)，7.34(2H，d，J＝8.0Hz)，7.81(2H，d，J＝8.0Hz)。
Reaction formula 9-5
Preparation example 10: first intermediate for preparing monomer of chemical formula 2
As shown in the following reaction scheme 9-6, in methylene chloride (200mL, 10)mL/g) was dissolved with triethyleneglycol monobutylether (triethyleneglycol monobutylether) 15(20g, 96.96mmol) and triethylamine (20.29mL, 145.44mmol), and then, tosyl chloride (16.64g, 87.26mmol) was added at 0 ℃ and stirred at room temperature for 3 hours. After the reaction was completed, extraction was performed with dichloromethane and anhydrous Na2SO4The organic layer was dried and concentrated to obtain liquid compound 15-1(24.90g, 71% yield) as 2- (2- (2-butoxyethoxy) ethoxy) ethyl 4-methylbenzenesulfonate (2- (2- (2-butoxyethoxy) ethoxy) ethyl 4-methylbenzene sulfonate).
1H-NMR(CDCl3，Varian 400MHz)：δ0.90(3H，t，J＝7.2Hz)，1.30-1.39(2H，m)，1.51-1.59(2H，m)，2.44(3H，s)，3.44(2H，t，J＝6.4Hz)，3.54-3.61(8H，m)，3.68(2H，t，J＝4.8Hz)，4.15(2H，t，J＝4.8Hz)，7.33(2H，d，J＝8.0Hz)，7.79(2H，d，J＝8.0Hz)。
Reaction formula 9-6
Preparation example 11: first intermediate for preparing monomer of chemical formula 2
As shown in the following reaction scheme 9-7, 2,5,8,11-tetraoxatridecan-13-ol (2,5,8,11-tetraoxatridecan-13-ol)16(20g, 96.04mmol) and triethylamine (20.08mL, 144.06mmol) were dissolved in dichloromethane (200mL, 10mL/g), followed by addition of tosyl chloride (16.48g, 86.43mmol) at 0 ℃ and stirring at room temperature for 3 hours. After the reaction was completed, extraction was performed using dichloromethane using anhydrous Na2SO4The organic layer was dried and concentrated to obtain 16-1(30.1g, 86% yield) as a liquid compound of 2,5,8, 11-tetraoxatridec-13-yl 4-methylbenzenesulfonate (2,5,8, 11-tetraoxatrin can-13-yl 4-methyllbenzenesulfonate).
1H-NMR(CDCl3，Varian 400MHz)：δ2.44(3H，s)，3.30(3H，s)，3.54-3.65(12H，m)，3.70(2H，t，J＝4.8Hz)，4.17(2H，t，J＝5.2Hz)，7.33(2H，d，J＝8.0Hz)，7.79(2H，d，J＝8.0Hz)。
Reaction formula 9-7
Preparation example 12: second intermediate for preparing monomer of chemical formula 2
As shown in the following reaction scheme 11, 3, 4-dimethoxythiophene 1(200.00g, 1.387mol), 3-Chloro-1,2-propanediol (3-Chloro-1,2-propanediol)17(306.65g, 2.774mol) p-toluenesulfonic acid (26.38g, 0.138mol) and 2000mL of toluene were mixed, stirred at 110 ℃ for 15 hours and reacted. The reaction mixture was completely dissolved by adding ethyl acetate, and the mixture was extracted with water and then with sodium sulfate (Na)2SO4) The organic layer was dried and the remaining organic layer was concentrated. By means of silicon dioxide (SiO)2) Column chromatography and developing the concentrated organic layer with hexane solution and performing column purification to obtain 2-chloro-2,3-dihydrothieno [3,4-b ]][1,4]II
English (2-chloro-2,3-dihydrothieno [3, 4-b)][1,4]dioxine) compound 18(120.0g, 45% yield).
1H-NMR(CDCl3，Varian 400MHz)：δ3.64-3.75(2H，m)，4.11-4.18(1H，m)，4.27-4.30(1H，m)，4.35-4.44(1H，m)，6.36(2H，s)。
Reaction formula 11
Preparation example 13: a third intermediate for preparing the monomer of chemical formula 2
As shown in the following reaction scheme 12, Compound 18(60.00g, 314.71mmol), sodium acetate (38.72g, 472.07mmol) and 900mL of dimethyl sulfoxide were mixed, stirred at 110 ℃ for 2 hours and reacted. Dichloromethane was added to dissolve the reaction solution completely, water extraction was performed, then the organic layer was dried over sodium sulfate, and concentratedThe organic layer remained. Mixing the concentrated Compound 19(2, 3-Dihydrothieno [3,4-b ]][1,4]II
En-2-yl) methyl acetate (2,3-dihydrothieno [3, 4-b)][1,4]dioxin-2-yl) methyl acetate), sodium hydroxide (44.12g, 1.102mol) and 1200mL of water were stirred at 100 ℃ for 4 hours and reacted. After the reaction was completed, the temperature was lowered to normal temperature, hydrochloric acid (hydrochloric acid) was added dropwise until pH3, the organic layer was dried with sodium sulfate after water extraction, and the remaining organic layer was concentrated. Column chromatography over silica and using hexane: ethyl acetate ═ 1: the 3 (volume ratio) mixed solution was developed into a concentrated organic layer and subjected to column purification, thereby obtaining (2,3-dihydrothieno [3,4-b ]][1,4]II
En-2-yl) methanol (2,3-dihydrothieno [3, 4-b)][1,4]dioxin-2-yl) methanol) compound 20(38.20g, 70% yield).
1H-NMR(CDCl3，Varian 400MHz)：δ1.87(1H，s)，3.83-3.88(2H，m)，4.08-4.13(1H，m)，4.22-4.26(1H，m)，6.35(2H，s)。
Reaction formula 12
Preparation example 14: preparation of monomer of chemical formula 2
As shown in the following reaction formula 13, compound 20(7.00g, 40.65mmol) was mixed in 70mL of N, N-dimethylformamide and the temperature was lowered to 0 ℃, after which sodium hydride (60% dispersion in mineral oil) (1.63g, 40.65mmol) was added to raise the temperature to normal temperature and stirred for 30 minutes. After the temperature was again lowered to 0 ℃, compound 10-1(9.58g, 44.72mmol) was added to stir for 12 hours and the reaction was carried out. The reaction mixture was completely dissolved by adding ethyl acetate, and the mixture was extracted with water and then with sodium sulfate (Na)2SO4) The organic layer was dried and the remaining organic layer was concentrated. By means of silicon dioxide (SiO)2) Column chromatography and using hexane: ethyl acetate ═ 1: the 1 (volume ratio) solution was developed into a concentrated organic layer and subjected to column purification, thereby obtaining 2- (propoxymethyl) -2,3-dihydrothieno [3,4-b ] as a 2- (propoxymethyl) -2,3-dihydrothieno [3,4-b ]][1,4]II
English (2- (prolymethyl) -2,3-dihydrothieno [3, 4-b)][1,4]dioxine, 5-EDOT-1) (7.5g, 86% yield).
1H-NMR(CDCl3，Varian 400MHz)：δ0.89(3H，t，J＝7.2Hz)，1.54(2H，t，J＝8.8Hz)，3.45(2H，t，J＝6.8Hz)，3.57-3.70(1H，m)，4.00-4.18(1H，m)，4.23-4.33(1H，m)，6.25(2H，s)。
Reaction formula 13
Preparation example 15: preparation of monomer of chemical formula 2
As shown in the following reaction formula 14, compound 20(7.00g, 40.65mmol) was mixed in 70mL of N, N-dimethylformamide and the temperature was lowered to 0 ℃, after which sodium hydride (60% dispersed in mineral oil) (1.63g, 40.65mmol) was added to raise the temperature to normal temperature and stirred for 30 minutes. After the temperature was again lowered to 0 ℃, compound 11-1(10.21g, 44.72mmol) was added, stirred for 12 hours and reacted. The reaction mixture was completely dissolved by adding ethyl acetate, and the mixture was extracted with water and then with sodium sulfate (Na)2SO4) The organic layer was dried and the remaining organic layer was concentrated. By means of silicon dioxide (SiO)2) Column chromatography and using hexane: ethyl acetate ═ 1: the concentrated organic layer was developed from the 1 (vol/vol) solution and subjected to column purification, to thereby obtain 2 (butoxymethyl) -2,3-dihydrothieno [3,4-b ] as a solution][1,4]II
English (2- (butoxymethyl))-2,3-dihydrothieno[3,4-b][1,4]dioxine, 6-EDOT-1) (6.0g, 65% yield).
1H-NMR(CDCl3，Varian 400MHz)：δ0.90(3H，t，J＝7.2Hz)，1.44-55(4H，m)，3.45(2H，t，J＝6.8Hz)，3.58(2H，t，J＝6.8Hz)，3.57-3.70(1H，m)，4.00-4.18(1H，m)，4.23-4.33(1H，m)，6.27(2H，s)。
Reaction formula 14
Preparation example 16: preparation of monomer of chemical formula 2
As shown in the following reaction formula 15, compound 20(7.00g, 40.65mmol) was mixed in 70mL of N, N-dimethylformamide and the temperature was lowered to 0 ℃, then sodium hydride (60% dispersed in mineral oil) (1.63g, 40.65mmol) was added, and the temperature was raised to normal temperature and stirred for 30 minutes. After the temperature was again lowered to 0 ℃, compound 12-1(12.89g, 44.72mmol) was added, stirred for 12 hours and reacted. The reaction mixture was completely dissolved by adding ethyl acetate, and the mixture was extracted with water and then with sodium sulfate (Na)2SO4) The organic layer was dried and the remaining organic layer was concentrated. By means of silicon dioxide (SiO)2) Column chromatography and using hexane: ethyl acetate ═ 1: the 1 (volume ratio) solution was developed into a concentrated organic layer and subjected to column purification to obtain 2((2- (2-ethoxyethoxy) ethoxy) methyl) -2,3-dihydrothieno [3,4-b ] as a 2][1,4]II
English (2- (2-ethoxyyethoxy) methyl) -2,3-dihydrothieno [3, 4-b)][1,4]dioxine, 10-EDOT-3) (11.50g, 98% yield).
1H-NMR(CDCl3，Varian 400MHz)：δ1.21(3H，t，J＝6.8Hz)，3.53(2H，dd，J＝7.2Hz)，3.58-3.60(2H，m)，3.64-3.79(8H，m)，4.04-4.15(1H，m)，4.24-4.35(2H，m)，6.32(2H，s)。
Reaction formula 15
Preparation example 17: preparation of monomer of chemical formula 2
As shown in the following reaction formula 16, compound 20(5.00g, 29.04mmol) was mixed with 50mL of N, N-dimethylformamide and the temperature was lowered to 0 ℃, and then sodium hydride (1.70g, 29.04mmol, 60% dispersed in mineral oil) was added to raise the temperature to normal temperature and stirred for 30 minutes. After the temperature was again lowered to 0 ℃, compound 13-1(9.08g, 31.94mmol) was added, stirred for 12 hours and reacted. The reaction mixture was completely dissolved by adding ethyl acetate, and the mixture was extracted with water and then with sodium sulfate (Na)2SO4) The organic layer was dried and the remaining organic layer was concentrated. By means of silicon dioxide (SiO)2) Column chromatography and using hexane: ethyl acetate ═ 5: 1 (volume ratio) solution was developed into a concentrated organic layer and subjected to column purification to obtain 2- (octyloxymethyl) 2,3-dihydrothieno [3,4-b ]][1,4]II
English (2- (octyloxymethyl) -2, 3-dihydrotho [3, 4-b)][1,4]dioxine, 10-EDOT-1) (5.30g, 64% yield).
1H-NMR(CDCl3，Varian 400MHz)：δ0.88(3H，t，J＝7.2Hz)，1.22-1.32(12H，m)，1.63(2H，t，J＝8.8Hz)，3.49(2H，t，J＝6.8Hz)，3.57-3.70(1H，m)，4.00-4.15(1H，m)，4.23-4.33(1H，m)，6.32(2H，s)。
Reaction formula 16
Preparation example 18: preparation of monomer of chemical formula 2
As shown in the following reaction scheme 17, compound 20(6.00g, 34.84mmol) was mixed in 60mL of N, N-dimethylformamide and the temperature was lowered to 0 deg.CThereafter, sodium hydride (1.39g, 34.84mmol, 60% dispersion in mineral oil) was added to raise the temperature to normal temperature and stirred for 30 minutes. After the temperature was again lowered to 0 ℃, compound 14-1(9.42g, 31.36mmol) was added, stirred for 12 hours and reacted. The reaction mixture was completely dissolved by adding ethyl acetate, and the mixture was extracted with water and then with sodium sulfate (Na)2SO4) The organic layer was dried and the remaining organic layer was concentrated. By means of silicon dioxide (SiO)2) Column chromatography and using hexane: ethyl acetate ═ 5: the 1 (volume ratio) solution was developed into a concentrated organic layer and subjected to column purification to obtain 2- ((2- (hexyloxy) ethoxy) methyl) -2,3-dihydrothieno [3,4-b ] as a 2- ((2- (hexyloxy) ethoxy) methyl) -2,3-dihydrothieno [3,4-b ] salt][1,4]II
English (2- ((2- (hexyloxy) ethoxy) methyl) -2,3-dihydrothieno [3, 4-b)][1,4]dioxine, 11-EDOT-2) (5.30g, 54% yield).
1H-NMR(CDCl3，Varian 400MHz)：δ0.89(3H，t，J＝6.8Hz)，1.24-1.35(6H，m)，1.54-1.60(2H，m)，3.45(2H，t，J＝7.2Hz)，3.57-3.60(2H，m)，3.66-3.80(4H，m)，4.04-4.13(1H，m)，4.24-4.36(2H，m)，6.32(2H，t，J＝4.4Hz)。
Reaction formula 17
Preparation example 19: preparation of monomer of chemical formula 2
Compound 20(6.85g, 39.76mmol) was mixed in 70mL of N, N-dimethylformamide and the temperature was reduced to 0 ℃, after which sodium hydride (1.59g, 39.76mmol, 60% dispersed in mineral oil) was added to raise the temperature to normal temperature and stirred for 30 minutes as in the following reaction formula 18. After the temperature was again lowered to 0 ℃, compound 15-1(12.90g, 35.79mmol) was added, stirred for 12 hours and reacted. The reaction mixture was completely dissolved by adding ethyl acetate, and the mixture was extracted with water and then with sodium sulfate (Na)2SO4) The organic layer was dried and the remaining organic layer was concentrated. Through twoSilicon oxide (SiO)2) Column chromatography and using hexane: ethyl acetate ═ 2: 1 (volume ratio) solution to develop a concentrated organic layer and to perform column purification, thereby obtaining 2,2,5,8,11-tetraoxapentadecyl-2,3-dihydrothieno [3,4-b ] as a 2,2,5,8,11-tetraoxapentadecyl group][1,4]II
English (2,2,5,8,11-tetraoxapentadecyl-2,3-dihydrothieno [3, 4-b)][1,4]dioxine, 15-EDOT-4) (7.10g, 50% yield).
1H-NMR(CDCl3，Varian 400MHz)：δ0.91(3H，t，J＝7.6Hz)，1.31-1.40(2H，m)，1.52-1.58(2H，m)，3.45(2H，t，J＝6.8Hz)，3.57(2H，d，J＝4.8Hz)，3.63-3.79(12H，m)，4.04-4.13(1H，m)，4.24-4.34(2H，m)，6.32(2H，s)。
Reaction formula 18
Preparation example 20: preparation of monomer of chemical formula 2
As shown in the following reaction formula 19, compound 20(6.00g, 34.84mmol) was mixed with 60mL of N, N-dimethylformamide and the temperature was lowered to 0 ℃, and then sodium hydride (1.39g, 34.84mmol, 60% dispersed in mineral oil) was added to raise the temperature to normal temperature and stirred for 30 minutes. After the temperature was again lowered to 0 ℃, compound 16-1(11.37g, 31.36mmol) was added, stirred for 12 hours and reacted. The reaction mixture was completely dissolved by adding ethyl acetate, and the mixture was extracted with water and then with sodium sulfate (Na)2SO4) The organic layer was dried and the remaining organic layer was concentrated. By means of silicon dioxide (SiO)2) Column chromatography and using hexane: ethyl acetate ═ 5: 1 (volume ratio) solution to develop a concentrated organic layer and to perform column purification, thereby obtaining 2-2,5,8,11,14-pentaoxapentadecyl-2, 3-dihydrothieno [3,4-b ] as a 2-2,5,8,11,14-pentaoxapentadecyl group][1,4]II
English (2-2,5,8,11, 14-pentaoxapentadecanyl-2, 3-dihydrothieno[3,4-b][1,4]dioxine, 15-EDOT-5) (6.50g, 52% yield).
1H-NMR(CDCl3，Varian 400MHz)：δ3.30(3H，t，J＝7.6Hz)，3.54-3.65(18H，m)，4.04-4.13(1H，m)，4.24-4.34(2H，m)，6.32(2H，s)。
Reaction formula 19
Preparation example 21: preparation of the first intermediate of chemical formula 3
As shown in the following reaction scheme 20, triethylene glycol (triethylene glycol)28(30g, 199.77mmol) and triethylamine (84mL, 599.32mol) were dissolved in methylene chloride (300mL, 10mL/g), and then tosyl chloride (114.26g, 599.31mmol) was added at 0 ℃ and stirred at normal temperature for 6 hours. The reaction solution was completely dissolved, extracted with water, and then with sodium sulfate (Na)2SO4) The organic layer was dried and the remaining organic layer was concentrated. By means of silicon dioxide (SiO)2) Column chromatography and using hexane: 1-dichloromethane: the concentrated organic layer was developed from the 1 (vol) — solution and column purification was performed, thereby obtaining compound 28-1(54.20g, 59% yield) as 2,2'- (ethane-1,2-diylbis (oxy)) bis (ethane-2, 1-diylbis (4-methylbenzenesulfonate) (2,2' - (ethane-1,2-diylbis (oxy)) bis (ethane-2,1-diyl) bis (4-methylzenesulfonate)).
1H-NMR(CDCl3，Varian 400MHz)：δ2.45(6H，s)，3.53(4H，s)，3.66(4H，t，J＝4.8Hz)，4.14(4H，t，J＝4.8Hz)，7.34(4H，d，J＝8.0Hz)，7.79(4H，d，J＝8.0Hz)。
Reaction scheme 20
Preparation example 22: preparation of the first intermediate of chemical formula 3
As shown in the following reaction scheme 21, in dichloromethane (300 m)L, 10mL/g) was dissolved in 1,4-cyclohexanedimethanol (1, 4-cyclohexadimethanol) 29(30g, 208.03mmol) and triethylamine (87mL, 624.09mol), and then tosyl chloride (118.98g, 624.09mmol) was added at 0 ℃ and stirred at room temperature for 6 hours. The reaction solution was completely dissolved, extracted with water, and then with sodium sulfate (Na)2SO4) The organic layer was dried and the remaining organic layer was concentrated. By means of silicon dioxide (SiO)2) Column chromatography and using hexane: 1-dichloromethane: the concentrated organic layer was spread out from the 1 (vol%) solution and subjected to column purification, thereby obtaining compound 29-1(38.50g, 41% yield) as Cyclohexane-1,4-diylbis (methylene) bis (4-methylbenzenesulfonate) (Cyclohexane-1,4-diylbis (methyl) bis (4-methylb enzenesulfonate)).
1H-NMR(CDCl3，Varian 400MHz)：δ0.90(4H，t，J＝9.2Hz)，1.58(2H，m)，1.73(4H，d，J＝7.2Hz)，2.44(6H，s)，3.80(4H，d，J＝6.4Hz)，7.34(4H，d，J＝8.0Hz)，7.77(4H，d，J＝8.0Hz)。
Reaction formula 21
Preparation example 23: preparation of the first intermediate of chemical formula 3
As shown in the following reaction scheme 22, 1,6-hexanediol (1,6-hexanediol)30(30g, 253.85mmol) and triethylamine (106mL, 761.55mmol) were dissolved in dichloromethane (300mL, 10mL/g), followed by addition of tosyl chloride (118.98g, 624.09mmol) at 0 ℃ and stirring at ordinary temperature for 6 hours. The reaction solution was completely dissolved, extracted with water, and then with sodium sulfate (Na)2SO4) The organic layer was dried and the remaining organic layer was concentrated. By means of silicon dioxide (SiO)2) Column chromatography and using hexane: 1-dichloromethane: the concentrated organic layer was developed from the 1 (vol%) solution and subjected to column purification, thereby obtaining compound 30-1(50.65g, 57% yield) as hexane-1, 6-diylbis (4-methylbenzenesulfonate).
1H-NMR(CDCl3，Varian 400MHz)：δ1.27(4H，s)，1.58-1.62(4H，m)，2.44(6H，s)，3.98(4H，t，J＝7.6Hz)，7.35(4H，d，J＝8.4Hz)，7.78(4H，d，J＝8.4Hz)。
Reaction formula 22
Preparation example 24: preparation of the first Polymer of chemical formula 3
As shown in the following reaction scheme 23, diethylene glycol 31(10g, 94.23mmol) and triethylamine (39mL, 282.70mol) were dissolved in methylene chloride (100mL, 10mL/g), followed by addition of tosyl chloride (53.89g, 282.70mmol) at 0 ℃ and stirring at room temperature for 6 hours. The reaction solution was completely dissolved, extracted with water, and then with sodium sulfate (Na)2SO4) The organic layer was dried and the remaining organic layer was concentrated. By means of silicon dioxide (SiO)2) Column chromatography and using hexane: 1-dichloromethane: the concentrated organic layer was developed from the 1 (volume ratio) solution and subjected to column purification, thereby obtaining compound 31-1(28.0g, 72% yield) as 2,2'-oxybis (ethane-2,1-diyl) bis (4-methylbenzenesulfonate) (2,2' -oxybis (ethane-2,1-diyl) bis (4-methylzenesulfonate)).
1H-NMR(CDCl3，Varian 400MHz)：δ2.34(6H，s)，3.56(4H，t，J＝4.8Hz)，3.70(4H，t，J＝4.8Hz)，7.34(4H，d，J＝8.0Hz)，7.79(4H，d，J＝8.0Hz)。
Reaction formula 23
Preparation example 25: preparation of the crosslinking agent (A-1) of chemical formula 1
As shown in the following reaction scheme 24, compound 20(4.09g, 23.75mmol) was mixed in 400mL of N, N-dimethylformamide and the temperature was lowered to 0 ℃, then sodium hydride (0.95g, 23.75mmol, 60% dispersed in mineral oil) was added to raise the temperature to normal temperature and stirredStirring for 30 minutes. After the temperature was again lowered to 0 ℃, compound 28-1(5.11g, 11.16mmol) was added, stirred for 12 hours and reacted. The reaction mixture was completely dissolved by adding Dichloromethane (DCM), extracted with water, and then extracted with sodium sulfate (Na)2SO4) The organic layer was dried and the remaining organic layer was concentrated. By means of silicon dioxide (SiO)2) Column chromatography and using hexane: ethyl acetate ═ 1: the 1 (volume ratio) solution was developed into a concentrated organic layer and subjected to column purification to obtain 1,12-bis (2,3-dihydrothieno [3,4-b ]][1,4]II
En-2-yl) -2,5,8,11-tetraoxadodecane (1,12-bis (2,3-dihydrothieno [3, 4-b) ]][1,4]dioxin-2-yl) -2,5,8, 11-tetraoxadocane) compound 32(3.10g, 61% yield).
1H-NMR(CDCl3，Varian 400MHz)：δ3.65-3.78(16H，m)，4.03-4.06(2H，dd，J＝11.6Hz)，4.23-4.33(4H，m)。
Reaction formula 24
Preparation example 26: preparation of the crosslinking agent (A-2) of chemical formula 1
As shown in the following reaction formula 25, compound 20(9.8g, 56.91mmol) was mixed with 100mL of N, N-dimethylformamide and the temperature was lowered to 0 ℃, after which sodium hydride (2.28g, 56.91mmol, 60% dispersed in mineral oil) was added to raise the temperature to normal temperature and stirred for 30 minutes. After the temperature was again lowered to 0 ℃, compound 29-1(12.11g, 26.75mmol) was added, stirred for 12 hours and reacted. The reaction mixture was completely dissolved by adding ethyl acetate, and the mixture was extracted with water and then with sodium sulfate (Na)2SO4) The organic layer was dried and the remaining organic layer was concentrated. By means of silicon dioxide (SiO)2) Column chromatography and using hexane: ethyl acetate ═ 1: the 1 (volume ratio) solution spreads the concentrated organic layer and is subjected to column purification, thereby obtaining 1,4-bis (((2,3-dihydrothieno [3,4-b ]) as a][1,4]II
En-2-yl) methoxy) methylcyclohexane (1,4-bis (((2,3-dihydrothieno [3, 4-b))][1,4]dioxin-2-yl) methoxy) methyl) cyclohexane) (6.50g, 54% yield).
1H-NMR(CDCl3，Varian 400MHz)：δ0.96(4H，t，J＝6.0Hz)，1.80(4H，d，J＝7.6Hz)，3.36(4H，d，J＝7.6Hz)，3.56-3.70(4H，m)，4.03-4.08(2H，m)，4.23-4.32(4H，m)，6.33(4H，s)。
Reaction formula 25
Preparation example 27: preparation of the crosslinking agent (A-3) of chemical formula 1
As shown in the following reaction formula 26, compound 20(15.0g, 87.11mmol) was mixed in 150mL of N, N-dimethylformamide and the temperature was lowered to 0 ℃, after which the temperature was raised to normal temperature by adding sodium hydride (3.48g, 87.11mmol, 60% dispersed in mineral oil) and stirred for 30 minutes. After the temperature was again lowered to 0 ℃, compound 30-1(17.46g, 40.94mmol) was added, stirred for 12 hours and reacted. Dichloromethane was added to completely dissolve the reaction solution, and after extraction with water, sodium sulfate (Na) was used2SO4) The organic layer was dried and the remaining organic layer was concentrated. By means of silicon dioxide (SiO)2) Column chromatography and using hexane: ethyl acetate ═ 3: the 1 (volume ratio) solution was developed into a concentrated organic layer and subjected to column purification to obtain 1,6-bis ((2,3-dihydrothieno [3, 4-b))][1,4]II
En-2-yl) methoxy) hexane (1,6-bis ((2,3-dihydrothieno [3, 4-b)][1,4]dioxin-2-yl) methoxy) hexane) (4.90g, 28% yield).
1H-NMR(CDCl3，Varian 400MHz)：δ1.35-1.38(4H，m)，1.57-1.61(4H，m)，3.48-3.52(4H，m)，3.57-3.70(4H，m)，4.05(2H，dd，J＝11.6Hz)，4.22-4.32(4H，m)，6.33(4H，s)。
Reaction formula 26
Preparation example 28: preparation of the crosslinking agent (A-4) of chemical formula 1
As shown in the following reaction formula 27, compound 20(2.0g, 11.62mmol) was mixed in 20mL of N, N-dimethylformamide and the temperature was lowered to 0 ℃, after which sodium hydride (0.46g, 11.62mmol, 60% dispersed in mineral oil) was added to raise the temperature to normal temperature and stirred for 30 minutes. After the temperature was again lowered to 0 ℃, compound 31-1(2.26g, 5.46mmol) was added, stirred for 12 hours and reacted. The reaction mixture was completely dissolved by adding Dichloromethane (DCM), extracted with water, and then extracted with sodium sulfate (Na)2SO4) The organic layer was dried and the remaining organic layer was concentrated. By means of silicon dioxide (SiO)2) Column chromatography and using hexane: ethyl acetate ═ 1: the 1 (volume ratio) solution was developed into a concentrated organic layer and subjected to column purification to obtain 2,2'- (2,2' -oxybis (ethane-2,1-diyl) bis (oxy)) bis (methylene) bis (2,3-dihydrothieno [3,4-b ]) as a solution][1,4]II
English (2,2'- (2,2' -oxydis (ethane-2,1-diyl) bis (oxy)) bis (methyl) bis (2,3-dihydrothieno [3, 4-b))][1,4]dioxine)) compound 35(2.05g, 88% yield).
1H-NMR(CDCl3，Varian 400MHz)：δ3.65-3.79(12H，m)，4.06(2H，dd，J＝7.2Hz)，4.23-4.34(4H，m)，6.32(4H，s)。
Reaction formula 27
Preparation example 29: first intermediate for preparing monomer of chemical formula 2
As a liquid compound 36-1(28.50g, 81% yield) as 2- (2- (heptyloxy) ethoxy) ethyl 4-methylbenzenesulfonate (2- (2- (heptyloxy) ethoxy) ethyl 4-methylbenzenesulfonate), a compound was obtained in the same manner as in production example 11 except that 2- (2- (heptyloxy) ethoxy) ethanol (2- (2- (2- (heptyloxy) ethoxy) ethanol 36(20.0g, 97.89mmol) was used in place of 2,5,8,11-tetraoxatridecan-13-ol (2,5,8,11-tetraoxatridecan-13-ol)16 in production example 11.
1H-NMR(CDCl3，Varian 400MHz)：δ0.90(3H，t，J＝7.2Hz)，1.30-1.43(8H，m)，1.51-1.59(2H，m)，2.44(3H，s)，3.44(2H，t，J＝6.4Hz)，3.54-3.61(8H，m)，7.33(2H，d，J＝8.0Hz)，7.79(2H，d，J＝8.0Hz)。
Reaction formula 27-1
Preparation example 30: preparation of monomer of chemical formula 2
Synthesized in the same manner as in preparation example 20, except for using compound 36-1 of preparation example 29 in place of compound 16-1 of preparation example 20, obtained as 2- ((2-2- (heptyloxy) ethoxy) methyl) -2-3-dihydrothieno [3, 4-b)][1,4]II
English (2- ((2- (2- (hexyloxy) ethoxy) ethoxy) methyl) -2,3-dihydrothieno [3, 4-b)][1,4]dioxide, 15-EDOT-3) (6.10g, 50% yield).
1H-NMR(CDCl3，Varian 400MHz)：δ0.89(3H，t，J＝6.8Hz)，1.29-1.35(8H，m)，1.54-1.62(2H，m)，3.45(2H，t，J＝7.2Hz)，3.57-3.60(6H，m)，3.66-3.80(4H，m)，4.04-4.13(1H，m)，4.24-4.36(2H，m)，6.32(2H，t，J＝4.4Hz)。
Reaction formula 28
Comparative example 1: production of aluminum wound electrolytic capacitor (Poly-mono-propyl EDOT)
First, an aluminum foil was used as a positive electrode side counter electrode, and the surface of the positive electrode foil was subjected to etching treatment, and then, chemical conversion treatment was performed to attach a lead terminal to the positive electrode having a dielectric layer formed of an oxide film formed on the surface of the aluminum foil. Next, lead terminals were attached to the negative electrode made of aluminum foil, and the positive electrode and the negative electrode to which the lead terminals were attached were wound with a nylon-based spacer to prepare a capacitor device.
Then, (2-propyl 2, 3-dihydrothieno) bis
English) monomer, then, a conductive polymer electrolyte solution was prepared using a 50% iron p-toluenesulfonate/n-butanol solution of an oxidant in a weight ratio of 1: 2.5, the capacitor device was immersed in the conductive polymer electrolyte solution and extracted, and the capacitor device was heated at 45 ℃ for 2 hours, 105 ℃ for 35 minutes, and 125 ℃ for 1 hour to undergo oxidative polymerization, thereby forming an electrolyte layer made of a conductive polymer. Finally, the electrolyte layer was externally coated with an external material, and an aging treatment was performed by applying a voltage of 4V to the positive electrode to prepare an aluminum-wound electrolytic capacitor.
Comparative example 2: production of aluminum wound electrolytic capacitor (Poly-monooctyl-EDOT)
Using (2-octyl 2, 3-dihydrothieno) bis
English) monomer instead of (2-propyl 2, 3-dihydrothieno) bis
Quartz) and other than the monomer, a capacitor device and an aluminum wound electrolytic capacitor were produced in the same manner as in comparative example 1.
Comparative example 3: production of aluminum wound electrolytic capacitor (Poly-monodecyl-EDOT)
Using (2-decyl 2, 3-dihydrothieno) bis
English) monomer instead of (2-propyl 2, 3-dihydrothieno) bis
Quartz) and other than the monomer, a capacitor device and an aluminum wound electrolytic capacitor were produced in the same manner as in comparative example 1.
Comparative example 4: production of aluminum winding type electrolytic capacitor (Poly- (15-EDOT-5))
Using 2-2,5,8,11,14-pentaoxapentadecyl-2, 3-dihydrothieno [3,4-b ]][1,4]II
In place of (2-propyl 2, 3-dihydrothieno) bis
Quartz) and other than the monomer, a capacitor device and an aluminum wound electrolytic capacitor were produced in the same manner as in comparative example 1.
Comparative example 5: production of aluminum winding type electrolytic capacitor (Poly- (5-EDOT-1))
Using 2- (propoxymethyl) -2,3-dihydrothieno [3,4-b][1,4]II
In place of (2-propyl 2, 3-dihydrothieno) bis
Quartz) and other than the monomer, a capacitor device and an aluminum wound electrolytic capacitor were produced in the same manner as in comparative example 1.
Example 1: production of aluminum winding type electrolytic capacitor (Poly- (6-EDOT-1))
Using 2 (butoxymethyl) -2,3-dihydrothieno [3,4-b ]][1,4]II
In place of (2-propyl 2, 3-dihydrothieno) bis
Quartz) and other than the monomer, a capacitor device and an aluminum wound electrolytic capacitor were produced in the same manner as in comparative example 1.
Example 2: production of aluminum winding type electrolytic capacitor (Poly- (10-EDOT-3))
Using (2- ((2- (2-ethoxyethoxy) ethoxy) methyl) -2,3-dihydrothieno [3, 4-b)][1,4]II
English) monomer instead of (2-propyl 2, 3-dihydrothieno) bis
Quartz) and other than the monomer, a capacitor device and an aluminum wound electrolytic capacitor were produced in the same manner as in comparative example 1.
Example 3: production of aluminum winding type electrolytic capacitor (Poly- (10-EDOT-1))
Using (2- (octyloxymethyl) -2,3-dihydrothieno [3, 4-b)][1,4]II
English) monomer instead of (2-propyl 2, 3-dihydrothieno) bis
Quartz) and other than the monomer, a capacitor device and an aluminum wound electrolytic capacitor were produced in the same manner as in comparative example 1.
Example 4: production of aluminum winding type electrolytic capacitor (Poly- (11-EDOT-2))
Using 2- ((2- (hexyloxy) ethoxy) methyl) -2,3-dihydrothieno [3,4-b][1,4]II
In place of (2-propyl 2, 3-dihydrothieno) bis
Quartz) and other than the monomer, a capacitor device and an aluminum wound electrolytic capacitor were produced in the same manner as in comparative example 1.
Example 5: production of aluminum winding type electrolytic capacitor (Poly- (15-EDOT-4))
Using 2,2,5,8,11-tetraoxapentadecyl-2,3-dihydrothieno [3,4-b ]][1,4]II
In place of (2-propyl 2, 3-dihydrothieno) bis
Quartz) and other than the monomer, a capacitor device and an aluminum wound electrolytic capacitor were produced in the same manner as in comparative example 1.
Example 6: production of an aluminum wound-type electrolytic capacitor (Poly EDOT: 10-EDOT-1)
A capacitor device was produced in the same manner as in comparative example 1, and a compound for polymerization was produced by the following method.
First, 3,4-ethylenedioxythiophene monomer and (2- (octyloxymethyl) -2,3-dihydrothieno [3,4-b ] were mixed in a molar ratio of 50% (1: 1), respectively][1,4]II
English) monomers and preparation, and then, a conductive polymer electrolyte solution was prepared using an oxidant 50% iron p-toluenesulfonate/n-butanol solution in a weight ratio of 1: 2.5. Next, the capacitor device was immersed in the conductive polymer electrolyte solution and extracted, and heated at 45 ℃ for 2 hours, 105 ℃ for 35 minutes, and 125 ℃ for 1 hour to perform oxidative polymerization, thereby forming an electrolyte layer made of a conductive polymer. The conductor electrolyte layer was externally coated with an external material, and an aging treatment was performed by applying a voltage of 4V to the positive electrode to prepare an aluminum wound electrolytic capacitor.
Example 7: production of an aluminum wound-type electrolytic capacitor (Poly EDOT: 15-EDOT-4)
First, a capacitor device was prepared in the same manner as in comparative example 1.
Then, 3,4-ethylenedioxythiophene monomer and (2,2,5,8,11-tetraoxapentadecyl-2,3-dihydrothieno [3,4-b ] are used][1,4]II
The English monomer replaces 3,4-ethylenedioxythiophene monomer and (2- (octyloxymethyl) -2,3-dihydrothieno [3,4-b ]][1,4]II
Quartz) monomer, and an aluminum wound type electrolytic capacitor was produced in the same manner as in example 6, except for the above.
Example 8: preparation of an aluminum wound-type electrolytic capacitor (Polypropylene-EDOT: 15-EDOT-4)
First, a capacitor device was prepared in the same manner as in comparative example 1.
Then, 2-propyl-2,3-dihydrothieno [3,4-b ] is used][1,4]II
British monomers and (2,2,5,8,11-tetraoxapentadecyl-2,3-dihydrothieno [3,4-b ]][1,4]II
The English monomer replaces 3,4-ethylenedioxythiophene monomer and (2- (octyloxymethyl) -2,3-dihydrothieno [3,4-b ]][1,4]II
Quartz) monomer, and an aluminum wound type electrolytic capacitor was produced in the same manner as in example 6, except for the above.
Example 9: production of an aluminum wound-type electrolytic capacitor (Poly EDOT: 10-EDOT-3)
First, a capacitor device was prepared in the same manner as in comparative example 1.
Then, 3,4-ethylenedioxythiophene monomer and 2((2- (2-ethoxyethoxy) ethoxy) methyl) -2,3-dihydrothieno [3,4-b ] are used][1,4]II
The English monomer replaces 3,4-ethylenedioxythiophene monomer and (2- (octyloxymethyl) -2,3-dihydrothieno [3,4-b ]][1,4]II
Quartz) monomer, and an aluminum wound type electrolytic capacitor was produced in the same manner as in example 6, except for the above.
Example 10: production of an aluminum wound-type electrolytic capacitor (Poly EDOT: 11-EDOT-2)
First, a capacitor device was prepared in the same manner as in comparative example 1.
Then, 3,4-ethylenedioxythiophene monomer and (2- ((2- (hexyloxy) ethoxy) methyl) -2,3-dihydrothieno [3,4-b ] are used][1,4]II
English) monomer instead of 3,4-ethylenedioxythiophene monomer and (2- (octyloxymethyl) -2,3-dihydrothieno [3,4-b ]][1,4]II
Quartz) monomer, and an aluminum wound type electrolytic capacitor was produced in the same manner as in example 6, except for the above.
Example 11: preparation of an aluminum wound electrolytic capacitor (Polyoctyl-EDOT: A-1)
First, a capacitor device was prepared in the same manner as in comparative example 1.
Subsequently, (2-octyl 2, 3-dihydrothieno) bis(s) were prepared separately
Quartz) monomer, (1,12-bis (2,3-dihydrothieno [3, 4-b) ] monomer as a crosslinking agent is mixed (mixing) in a weight ratio of 100 to 2][1,4]II
In-2-yl) -2,5,8,11-tetraoxadodecane) and prepared, then a conductive polyelectrolyte was prepared using a 1: 2.5 weight ratio oxidant 50% ferric p-toluenesulfonate/n-butanol solutionAnd (3) solution.
Next, the capacitor device was immersed in the conductive polymer electrolyte solution and extracted, and heated at 45 ℃ for 2 hours, 105 ℃ for 35 minutes, and 125 ℃ for 1 hour to perform oxidative polymerization, thereby forming an electrolyte layer made of a conductive polymer. The electrolyte layer was externally coated with an external material, and an aging treatment was performed by applying a voltage of 4V to the positive electrode to prepare an aluminum wound electrolytic capacitor.
Example 12: preparation of an aluminum wound electrolytic capacitor (Polyoctyl-EDOT: A-2)
First, a capacitor device was prepared in the same manner as in comparative example 1.
Next, as a crosslinking agent, (1,4-bis (((2,3-dihydrothieno [3,4-b ]) is used][1,4]II
En-2-yl) methoxy) methyl) cyclohexane) instead of (1,12-bis (2,3-dihydrothieno [3, 4-b)][1,4]II
In-2-yl) -2,5,8,11-tetraoxadodecane), an oxidizer aluminum coiled electrolytic capacitor was prepared in the same manner as in example 11.
Example 13: preparation of an aluminum wound electrolytic capacitor (Polyoctyl-EDOT: A-3)
First, a capacitor device was prepared in the same manner as in comparative example 1.
Next, as a crosslinking agent, (1,6-bis ((2,3-dihydrothieno [3,4-b ]) was used][1,4]II
En-2-yl) methoxy) hexene) instead of (1,12-bis (2,3-dihydrothieno [3, 4-b)][1,4]II
In-2-yl) -2,5,8,11-tetraoxadodecane), an aluminum wound type electrolytic capacitor was produced in the same manner as in example 11 except for the above.
Example 14: preparation of an aluminum wound electrolytic capacitor (Polyoctyl-EDOT: A-4)
First, a capacitor device was prepared in the same manner as in comparative example 1.
Then, (2,2'- (2,2' -oxybis (ethylene-2, 1-diyl) bis (oxy)) bis (methylene) bis (2, 3-dihydrothieno) [3,4-b ] was used as a crosslinking agent][1,4]II
English) instead of (1,12-bis (2,3-dihydrothieno [3, 4-b)][1,4]II
In-2-yl) -2,5,8,11-tetraoxadodecane), an aluminum wound type electrolytic capacitor was produced in the same manner as in example 11 except for the above.
Example 15: preparation of an aluminum wound electrolytic capacitor (Poly 10-EDOT-3: A-1)
First, a capacitor device was prepared in the same manner as in comparative example 1.
Then, (2- ((2- (2-ethoxyethoxy) ethoxy) methyl) -2,3-dihydrothieno [3, 4-b)][1,4]II
English) monomer instead of (2-octyl 2, 3-dihydrothieno) bis
A monomer, and as a crosslinking agent, (1,12-bis (2,3-dihydrothieno [3,4-b ]) is used][1,4]II
ININ-2-YL) -2,5,8, 11-TETRAOXODODECANE) FOR (1,12-BIS (2,3-DIHYDROTHIENO [3, 4-b)][1,4]II
In-2-yl) -2,5,8,11-tetraoxadodecane), an aluminum wound type electrolytic capacitor was produced in the same manner as in example 11 except for the above.
Example 16: preparation of an aluminum wound electrolytic capacitor (Poly 10-EDOT-3: A-4)
First, a capacitor device was prepared in the same manner as in comparative example 1.
Then, (2- ((2- (2-ethoxyethoxy) ethoxy) methyl) -2,3-dihydrothieno [3, 4-b)][1,4]II
English) monomer instead of (2-octyl 2, 3-dihydrothieno) bis
A monomer, and as a crosslinking agent, (2,2'- (2,2' -oxybis (ethylene-2, 1-diyl) bis (oxy)) bis (methylene) bis (2, 3-dihydrothieno) [3,4-b ] is used][1,4]II
English) instead of (1,12-bis (2,3-dihydrothieno [3, 4-b)][1,4]II
In-2-yl) -2,5,8,11-tetraoxadodecane), an aluminum wound type electrolytic capacitor was produced in the same manner as in example 11 except for the above.
Example 17: preparation of an aluminum wound electrolytic capacitor (Poly 11-EDOT-2: A-1)
First, a capacitor device was prepared in the same manner as in comparative example 1.
Then, (2- ((2- (hexyloxy) ethoxy) methyl) -2,3-dihydrothieno [3,4-b ] is used][1,4]II
English) monomer instead of (2-octyl 2, 3-dihydrothieno) bis
A monomer, and as a crosslinking agent, (1,12-bis (2,3-dihydrothieno [3,4-b ]) is used][1,4]II
En-2-yl) -2,5,8,11-tetraoxadodecane) instead of (1,12-bis (2,3-dihydrothieno [3, 4-b)][1,4]II
In-2-yl) -2,5,8,11-tetraoxadodecane), an aluminum wound type electrolytic capacitor was produced in the same manner as in example 11.
Example 18: preparation of an aluminum wound electrolytic capacitor (Poly 11-EDOT-2: A-4)
First, a capacitor device was prepared in the same manner as in comparative example 1.
Then, (2- ((2- (hexyloxy) ethoxy) methyl) -2,3-dihydrothieno [3,4-b ] is used][1,4]II
English) monomer instead of (2-octyl 2, 3-dihydrothieno) bis
A monomer, and as a crosslinking agent, (2,2'- (2,2' -oxybis (ethylene-2, 1-diyl) bis (oxy)) bis (methylene) bis (2, 3-dihydrothieno) [3,4-b ] is used][1,4]II
English) instead of (1,12-bis (2,3-dihydrothieno [3, 4-b)][1,4]II
In-2-yl) -2,5,8,11-tetraoxadodecane), an aluminum wound type electrolytic capacitor was produced in the same manner as in example 11 except for the above.
Example 19: preparation of an aluminum wound electrolytic capacitor (Poly-EDOT: 10-EDOT-1: A-1)
First, a capacitor device was prepared in the same manner as in comparative example 1.
Then, 3,4-ethylenedioxythiophene monomer and (2- (octyloxymethyl) -2,3-dihydrothieno [3,4-b ] were used in a molar ratio of 50% (1: 1), respectively][1,4]II
English) monomer instead of (2-octyl 2, 3-dihydrothieno) bis
A monomer, and as a crosslinking agent, (1,12-bis (2,3-dihydrothieno [3,4-b ]) is used][1,4]II
ININ-2-YL) -2,5,8, 11-TETRAOXODODECANE) FOR (1,12-BIS (2,3-DIHYDROTHIENO [3, 4-b)][1,4]II
In-2-yl) -2,5,8,11-tetraoxadodecane), an aluminum wound type electrolytic capacitor was produced in the same manner as in example 11 except for the above.
Example 20: preparation of an aluminum wound electrolytic capacitor (Poly EDOT: 11-EDOT-2: A-1)
First, a capacitor device was prepared in the same manner as in comparative example 1.
Then, the ratio of 20%: 80% molar ratio of 3,4-ethylenedioxythiophene monomer and (2- ((2- (hexyloxy) ethoxy) methyl) -2,3-dihydrothieno [3,4-b ] respectively][1,4]II
English) monomer instead of (2-octyl 2, 3-dihydrothieno) bis
A monomer, and as a crosslinking agent, (1,12-bis (2,3-dihydrothieno [3,4-b ]) is used][1,4]II
ININ-2-YL) -2,5,8, 11-TETRAOXODODECANE) FOR (1,12-BIS (2,3-DIHYDROTHIENO [3, 4-b)][1,4]II
In-2-yl) -2,5,8,11-tetraoxadodecane), an aluminum wound type electrolytic capacitor was produced in the same manner as in example 11.
Example 21: preparation of an aluminum wound electrolytic capacitor (Poly EDOT: 15-EDOT-4: A-1)
First, a capacitor device was prepared in the same manner as in comparative example 1.
Then, the ratio of 20%: 80% by mole of 3,4-ethylenedioxythiophene monomer and (2,2,5,8,11-tetraoxapentadecyl-2,3-dihydrothieno [3,4-b ]][1,4]II
Replacement of (2-octyl 2, 3-dihydrothieno) bis with English monomer
A monomer, and as a crosslinking agent, (1,12-bis (2,3-dihydrothieno [3,4-b ]) is used][1,4]II
ININ-2-YL) -2,5,8, 11-TETRAOXODODECANE) FOR (1,12-BIS (2,3-DIHYDROTHIENO [3, 4-b)][1,4]II
In-2-yl) -2,5,8,11-tetraoxadodecane), an aluminum wound type electrolytic capacitor was produced in the same manner as in example 11 except for the above.
Example 22: production of aluminum winding type electrolytic capacitor (Poly-15-EDOT-3)
Using 2- ((2-2- (heptyloxy) ethoxy) methyl) -2-3-dihydrothieno [3,4-b][1,4]II
In place of (2-propyl 2, 3-dihydrothieno) bis
Quartz) and other than the monomer, a capacitor device and an aluminum wound electrolytic capacitor were produced in the same manner as in comparative example 1.
The 3,4-ethylenedioxythiophene derivatives used in the comparative examples 1 to 5 and examples 1 to 22, their composition ratios, and crosslinking agents were collated and are shown in the following tables 1 and 2.
TABLE 1
TABLE 2
Experimental example 1: evaluation of aluminum-wound electrolytic capacitor 1
For the aluminum-wound electrolytic capacitors prepared in comparative examples 1 to 5 and examples 1 to 22, the Equivalent Series Resistance (ESR) was measured at 100kHz under a temperature condition of 25 ℃ and the electrostatic capacity was measured at 120Hz using an LCR tester (4284A) from hewlett packard (HEWLETTPACKARD), and the breakdown voltage was measured by increasing the voltage at a rate of 1V/min under a condition of 25 ℃ using PRk650-2.5 manufactured by Matsusada Precision, and the results thereof are shown in tables 1 to 8 below. In tables 3 to 10 below, 10 average values of the equivalent series resistance and the capacitance were obtained, and the second digit of the decimal point was rounded, and the breakdown voltage value was rounded below the decimal point (device size of 6.3X 6, operating voltage: 50V, capacitance: 10. mu.F).
TABLE 3
| Provision for | Number of chains | Electrostatic capacity (μ F) | ESR(mΩ) | Leakage current (μ A) | Breakdown voltage (V) |
| Comparative example 1 | 3 | 11.0 | 24 | 0.05 | 40 |
| Comparative example 2 | 8 | 10.4 | 38 | 0.15 | 50 |
| Comparative example 3 | 10 | 10.0 | 285 | 0.15 | 68 |
As shown in Table 3, in comparative examples 1 to 3, in which the winding type aluminum electrolytic capacitor was prepared by polymerizing only the monomer substituted with a single alkyl group having a structure that is mono-substituted at the tertiary carbon position of the 3,4-ethylenedioxythiophene monomer, the breakdown voltage was explained as follows, that is, in comparative examples 1 to 3, comparative example 3 has a higher breakdown voltage due to the winding type aluminum electrolytic capacitor having a long alkyl chain having 3 to 10 carbon atoms because the breakdown voltage is higher as the alkyl chain is increased. However, if the number of chains exceeds 10, it is not possible to obtain a high breakdown voltage, and it is confirmed that ESR is rapidly increased as shown in comparative example 3.
Table 3 shows that the ESR also increases as the number of chains increases, although the breakdown voltage is high. In order to solve the above problem, an alkylalkoxy group having a solubility superior to that of an alkyl group formed only of carbon (C) is introduced by introducing an oxygen (O) atom into the alkyl group.
TABLE 4
| Provision for | Number of chains | Electrostatic capacity (μ F) | ESR(mΩ) | Leakage current (μ A) | Breakdown voltage (V) |
| Comparative example 5 | 5 | 10.9 | 28 | 0.03 | 40 |
| Example 1 | 6 | 11.0 | 34 | 0.04 | 54 |
| Example 2 | 10 | 10.0 | 60 | 0.03 | 58 |
| Example 3 | 10 | 9.7 | 159 | 0.04 | 72 |
| Example 4 | 11 | 10.5 | 106 | 0.05 | 72 |
| Example 5 | 15 | 9.9 | 152 | 0.05 | 80 |
As shown in said table 4, in examples 1 to 5, the winding type aluminum electrolytic capacitors were prepared using only the monomer substituted with the alkylalkoxy group at the monomer mono-substituted at the tertiary carbon position of 3, 4-ethylenedioxythiophene. The breakdown voltages in examples 1 to 5 are explained below, and it is understood that the high breakdown voltage characteristics are exhibited as the number of chains increases, as in table 2. Also, in examples 2 and 3 having an alkylalkoxy group in which the alkyl chain includes an oxygen (O) group, lower ESR characteristics can be exhibited with the same chain number as compared to comparative example 3 in which the alkyl group is formed of only carbon (C).
As shown in table 4, comparative example 5 has been described in that, when the number of chains is 5, the breakdown voltage is 40V, which is low, and therefore, it is difficult to exhibit effective withstand voltage characteristics, and when the number of chains is 6 or more, the breakdown voltage is 50V or more, which exhibits excellent withstand voltage characteristics. Further, if the number of chains is 16 or more, there is a disadvantage that the ESR value becomes significantly higher than that of the high withstand voltage characteristic.
From the results, in order to compare the cases when there is an oxygen (O) atom and when there is no oxygen (O) atom in the same number of chains, the cases of comparative example 3, example 2 and example 3 having the same number of chains are compared in table 5.
Comparative example 3 in which the alkyl chain is formed only of carbon (C), example 2 in which 3 oxygen (O) atoms are present between carbon (C) atoms of the alkyl chain, and example 3 in which 1 oxygen (O) atom is present between carbon (C) atoms were designed, and characteristics of the cases in which the same alkyl chain has an oxygen (O) atom were compared. As a result, it was confirmed that the breakdown voltage of example 2 was slightly decreased, but the ESR value was significantly decreased, as compared with comparative example 3. In the case of example 3, it was confirmed that the breakdown voltage was rather higher and the ESR value was significantly reduced as compared with comparative example 1.
TABLE 5
When oxygen (O) atoms are introduced into the alkyl chain using the results, the withstand voltage characteristics are not greatly lowered and the ESR characteristics are remarkably improved.
However, according to table 6, in the structure in which an oxygen (O) atom is introduced into an alkyl group, an alkylalkoxy group having 15 chain numbers is compared. In comparative example 4 having 15 chains and having 5 oxygen (O) atoms, in example 5 having 15 chains and having 4 oxygen (O) atoms, and in example 22 having 15 chains and having 3 oxygen (O) atoms, the description about the breakdown voltage is as follows, that is, comparative example 4 having 5 oxygen (O) atoms has a low breakdown voltage compared to example 5 and example 22. It was confirmed that the ESR characteristics also have significantly higher values than those of examples 5 and 22. If the number of oxygen (O) atoms in such a long chain is more than 5, the breakdown voltage characteristics are rather lowered and the ESR characteristics are rather improved.
TABLE 6
When an alkylalkoxy group is introduced, the breakdown voltage and ESR characteristics are significantly improved as compared to 3,4-ethylenedioxythiophene derivatives in which the alkyl chain is formed only from carbon (C), but in order to further improve the ESR characteristics, one or more kinds of monomers each having an alkylalkoxy group substituted at the tertiary carbon position of a 3,4-ethylenedioxythiophene monomer and a monomer derived from chemical formula 4 are mixed to prepare a wound aluminum electrolytic capacitor as in examples 6 to 10 of table 6.
TABLE 7
According to the results of said table 7, the breakdown voltage was about 54V to 68V in examples 6 to 10, which had a low breakdown voltage but a great improvement in ESR characteristics as compared with the electrolytic capacitors homopolymerized with alkylalkoxy groups of example 3 and example 5 of table 4. Although ESR characteristics are greatly improved, breakdown voltage is lost to some extent, and in order to minimize the loss, an experiment for compensating for withstand voltage characteristics was performed by adding a cross-linking agent derived from chemical formula 3. In table 8 below, a plurality of compounds (crosslinking agents) represented by chemical formula 3 were added at a prescribed weight ratio by examples 11 to 18 to improve withstand voltage characteristics.
TABLE 8
As shown in Table 8, in examples 11 to 14, (2-octyl 2, 3-dihydrothieno) bis
English) as a monomer, each of the crosslinking agents of types A-1, A-2, A-3 and A-4 prepared in the above preparation examples 25 to 28 was added, and an experiment for improving withstand voltage characteristics was performed in a state where ESR characteristics were maintained. In the case of examples 11 to 14, it was confirmed that the ESR characteristics were maintained and the breakdown voltage characteristics were significantly improved as compared with comparative example 2.
Therefore, in the previous experiments, the crosslinking agents of A-1 and A-4 were added to examples 2 and 4, respectively, having alkylalkoxy groups, which are superior in ESR characteristics and breakdown voltage characteristics, and the ESR characteristics and breakdown voltage characteristics were observed.
TABLE 9
As shown in table 9, in the cases of examples 15 to 18, it was confirmed that the voltage was higher than that when the crosslinking agent was not added and the polymerization was performed in examples 2 and 4. By adding such a crosslinking agent, the crosslinking agent derived from chemical formula 3 is positioned between the polymers and crosslinks, thereby making the bonding stronger (see the structure 1).
According to the results of Table 9, in the case of examples 19 to 21, in homopolymerization was performed by a mixed composition of non-single monomers, 3,4-ethylenedioxythiophene monomers (compositions of 5: 5, 8: 2 and 8: 2) of different compositions were mixed respectively in 10-EDOT-1, 11-EDOT-2 and 15-EDOT-4 as monomers of examples 2 to 4 excellent in breakdown voltage characteristics, and a crosslinking agent A-1 was added to perform polymerization (Table 9).
Watch 10
At the same composition, the breakdown voltage characteristics of example 19, in which crosslinker a-1 was added, were improved compared to example 6, and similarly, examples 20 to 21 also had lower ESR values at higher breakdown voltages.
In particular, in example 20, the ESR was 58m Ω or less, which was a target value (60m Ω) or less, and the breakdown voltage was 72V, which was a high breakdown voltage.
As shown in tables 3 to 10, it is understood that the 3,4-ethylenedioxythiophene derivatives of the present invention have excellent withstand voltage characteristics, low equivalent series resistance, and very excellent conductivity.
Claims (15)
1. An electrolyte for an electrolytic capacitor comprising one or more 3,4-ethylenedioxythiophene derivatives represented by the following chemical formula 1,
chemical formula 1
In the chemical formula 1, l and n are each independently an integer of 0 to 3, a is absent or is an alkyl or alkylene group having a carbon number of 1 to 20 containing 0 to 3 oxygen atoms (O), an arylene group having a carbon number of 6 to 20, and B is an alkyl group having a carbon number of 1 to 20 or
However, l + n is 3 or lessThe number of the integer (c) of (d),
wherein, when A is absent, l + n is an integer of 1 to 3, and when l + n is 0, A contains 1 to 3 oxygen atoms, 3,4-ethylenedioxythiophene group is removed, and the number of oxygen atoms of chemical formula 1 is less than or equal to 4.
2. The electrolyte for electrolytic capacitors as claimed in claim 1, the 3,4-ethylenedioxythiophene derivative is represented by the following chemical formula 2,
chemical formula 2
In the chemical formula 2, l is an integer of 1 to 3, and p is an integer of 1 to 19.
3. The electrolyte for electrolytic capacitors as claimed in claim 1, the 3,4-ethylenedioxythiophene derivative is represented by the following chemical formula 3,
chemical formula 3
In the chemical formula 3, a is an alkyl or alkylene group having a carbon number of 1 to 20, an arylene group having a carbon number of 6 to 20, containing 1 or 2 oxygen atoms (O).
4. The electrolyte for electrolytic capacitors as claimed in claim 1, the 3,4-ethylenedioxythiophene derivative is a copolymer comprising compounds represented by the following chemical formulae 2 and 3,
chemical formula 2
Chemical formula 3
In the chemical formulas 2 and 3, l is an integer of 1 to 3, p is an integer of 1 to 19, and a is an alkylene group having a carbon number of 1 to 20, an arylene group having a carbon number of 6 to 20, which contains 1 or 2 oxygen atoms (O).
5. The electrolyte for electrolytic capacitors as claimed in any one of claims 1 to 4, further comprising one or more compounds represented by the following chemical formula 4:
chemical formula 4
In the chemical formula 4, R is hydrogen or an alkyl group having a number of carbon atoms of 1 to 20.
6. The electrolyte for electrolytic capacitors as claimed in claim 1, the A is a cyclic or chain alkylene group having a carbon number of 4 to 15 or a phenylene group, biphenyl group or naphthyl group having a carbon number of 6 to 15.
7. The electrolyte for electrolytic capacitors as claimed in claim 3 or 4, the alkylene group having a carbon number of 1 to 20 is a cyclic or chain alkylene group having a carbon number of 4 to 15.
8. An electrolytic capacitor, comprising:
a positive electrode layer having an oxide film;
a negative electrode layer; and
a separator and an electrolyte between the positive electrode layer and the negative electrode layer,
and comprises one or more 3,4-ethylenedioxythiophene derivatives represented by the following chemical formula 1,
chemical formula 1
In the chemical formula 1, l and n are each independently an integer of 0 to 3, a is absent or is an alkyl or alkylene group having a carbon number of 1 to 20 containing 0 to 3 oxygen atoms (O), an arylene group having a carbon number of 6 to 20, and B is an alkyl group having a carbon number of 1 to 20 or
However, l + n is an integer of 3 or less,
wherein, when A is absent, l + n is an integer of 1 to 3, and when l + n is 0, A contains 1 to 3 oxygen atoms, 3,4-ethylenedioxythiophene group is removed, and the number of oxygen atoms of chemical formula 1 is less than or equal to 4.
9. The electrolytic capacitor according to claim 8, wherein the 3,4-ethylenedioxythiophene derivative is represented by the following chemical formula 2,
chemical formula 2
In the chemical formula 2, l is an integer of 1 to 3, and p is an integer of 1 to 19.
10. The electrolytic capacitor according to claim 8, wherein the 3,4-ethylenedioxythiophene derivative is represented by the following chemical formula 3,
chemical formula 3
In the chemical formula 3, a is an alkyl or alkylene group having a carbon number of 1 to 20, an arylene group having a carbon number of 6 to 20, containing 1 or 2 oxygen atoms (O).
11. The electrolytic capacitor according to claim 8, the 3,4-ethylenedioxythiophene derivative is a copolymer comprising compounds represented by the following chemical formulae 2 and 3,
chemical formula 2
Chemical formula 3
In the chemical formulas 2 and 3, l is an integer of 1 to 3, p is an integer of 1 to 19, and a is an alkylene group having a carbon number of 1 to 20, an arylene group having a carbon number of 6 to 20, which includes 1 to 3 oxygen atoms (O).
12. The electrolytic capacitor according to any one of claims 8 to 11, further comprising a compound represented by the following chemical formula 4,
chemical formula 4
In the chemical formula 4, R is hydrogen or an alkyl group having a number of carbon atoms of 1 to 20.
13. The electrolytic capacitor as recited in claim 8, 10 or 11, the alkylene group having a carbon number of 1 to 20 being a cyclic or chain alkylene group having a carbon number of 4 to 15.
14. A raw material for electrolytic capacitors comprising one or more 3,4-ethylenedioxythiophene derivatives represented by the following chemical formula 1,
chemical formula 1
In the chemical formula 1, l and n are each independently an integer of 0 to 3, a is absent or is an alkyl or alkylene group having a carbon number of 1 to 20 containing 0 to 3 oxygen atoms (O), an arylene group having a carbon number of 6 to 20, and B is an alkyl group having a carbon number of 1 to 20 or
However, l + n is an integer of 3 or less,
wherein, when A is absent, l + n is an integer of 1 to 3, and when l + n is 0, A contains 1 to 3 oxygen atoms, 3,4-ethylenedioxythiophene group is removed, and the number of oxygen atoms of chemical formula 1 is less than or equal to 4.
15. The raw material for electrolytic capacitors as claimed in claim 14, wherein the alkylene group having a carbon number of 1 to 20 is a cyclic or chain alkylene group having a carbon number of 4 to 15.
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| KR10-2016-0184115 | 2016-12-30 | ||
| KR1020160184115A KR20180078874A (en) | 2016-12-30 | 2016-12-30 | Solid electrolyte including 3,4-ethylenedioxythiophene, electrolytic capacitor and electronic material including the same |
| PCT/KR2017/014931 WO2018124574A1 (en) | 2016-12-30 | 2017-12-18 | Electrolyte comprising 3,4-ethylenedioxythiophene, and electrolytic capacitor and material for electronic material including same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1526148A (en) * | 2001-05-31 | 2004-09-01 | �ձ��ֹ���ʽ���� | Solid electrolytic capacitor |
| KR20100110622A (en) * | 2009-04-03 | 2010-10-13 | 허문석 | Conducting polymer, a capacitor comprising conducting polymer and method for manufacturing the same |
| CN104081269A (en) * | 2011-09-19 | 2014-10-01 | 魁北克电力公司 | Flexible transparent electrochomic device, and a method for the preparation thereof |
| CN104428341A (en) * | 2012-07-03 | 2015-03-18 | 东曹株式会社 | Polythiophenes, water-soluble conductive polymer using same, and method for producing same |
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| US7105620B2 (en) * | 2001-12-20 | 2006-09-12 | Agfa Gevaert | 3,4-alkylenedioxy-thiophene copolymers |
| CN104577200A (en) * | 2015-02-06 | 2015-04-29 | 宁德新能源科技有限公司 | Electrolyte additive and application thereof |
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2016
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1526148A (en) * | 2001-05-31 | 2004-09-01 | �ձ��ֹ���ʽ���� | Solid electrolytic capacitor |
| KR20100110622A (en) * | 2009-04-03 | 2010-10-13 | 허문석 | Conducting polymer, a capacitor comprising conducting polymer and method for manufacturing the same |
| CN104081269A (en) * | 2011-09-19 | 2014-10-01 | 魁北克电力公司 | Flexible transparent electrochomic device, and a method for the preparation thereof |
| CN104428341A (en) * | 2012-07-03 | 2015-03-18 | 东曹株式会社 | Polythiophenes, water-soluble conductive polymer using same, and method for producing same |
Non-Patent Citations (5)
| Title |
|---|
| Eiichi Nakamura等.Electropolymerized Conjugated Polyelectrolytes with Tunable Work Function and Hydrophobicity as an Anode Buffer in Organic Optoelectronics.《American Chemical Society》.2012, * |
| Electropolymerized Conjugated Polyelectrolytes with Tunable Work Function and Hydrophobicity as an Anode Buffer in Organic Optoelectronics;Eiichi Nakamura等;《American Chemical Society》;20120627;3396-3404 * |
| Hydrophilic Oligo(oxyethylene)-Derivatized Poly(3,4-ethylenedioxythiophenes): Cation-Responsive Optoelectroelectrochemical Properties and Solid-State Chromism;Igor F. Perepichka等;《 American Chemical Society》;20021231;449-457 * |
| One-step electrodeposition of free-standing flexible conducting PEDOT derivative film and its electrochemical capacitive and thermoelectric performance;Xuemin Duan等;《Electrochimica Acta》;20161208;125-132 * |
| Xuemin Duan等.One-step electrodeposition of free-standing flexible conducting PEDOT derivative film and its electrochemical capacitive and thermoelectric performance.《Electrochimica Acta》.2016, * |
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| JP7167031B2 (en) | 2022-11-08 |
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| KR20180078874A (en) | 2018-07-10 |
| CN110140187A (en) | 2019-08-16 |
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