TWI447163B - 非極性有機溶劑中之新穎聚噻吩-聚陰離子錯合物 - Google Patents
非極性有機溶劑中之新穎聚噻吩-聚陰離子錯合物 Download PDFInfo
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- TWI447163B TWI447163B TW098115216A TW98115216A TWI447163B TW I447163 B TWI447163 B TW I447163B TW 098115216 A TW098115216 A TW 098115216A TW 98115216 A TW98115216 A TW 98115216A TW I447163 B TWI447163 B TW I447163B
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- Prior art keywords
- optionally substituted
- group
- iii
- alkyl group
- formula
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- 229920000447 polyanionic polymer Polymers 0.000 title claims description 29
- 239000003960 organic solvent Substances 0.000 title description 6
- -1 chlorocarbon hydrocarbons Chemical class 0.000 claims description 41
- 229920000123 polythiophene Polymers 0.000 claims description 41
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 34
- 239000002904 solvent Substances 0.000 claims description 23
- 229930192474 thiophene Natural products 0.000 claims description 22
- 229920001577 copolymer Polymers 0.000 claims description 19
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 239000007800 oxidant agent Substances 0.000 claims description 11
- 150000003577 thiophenes Chemical class 0.000 claims description 11
- 239000012454 non-polar solvent Substances 0.000 claims description 10
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims description 7
- 125000002853 C1-C4 hydroxyalkyl group Chemical group 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000005915 C6-C14 aryl group Chemical group 0.000 claims description 5
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000006833 (C1-C5) alkylene group Chemical group 0.000 claims description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 229920000642 polymer Polymers 0.000 description 24
- 239000000243 solution Substances 0.000 description 23
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 239000006185 dispersion Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000000758 substrate Substances 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 8
- 229920001940 conductive polymer Polymers 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 239000002798 polar solvent Substances 0.000 description 8
- 230000001590 oxidative effect Effects 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 125000002091 cationic group Chemical group 0.000 description 6
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 6
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 238000006277 sulfonation reaction Methods 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229920001400 block copolymer Polymers 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 3
- HVOAFLJLVONUSZ-UHFFFAOYSA-N 2-ethylperoxythiophene Chemical compound CCOOC1=CC=CS1 HVOAFLJLVONUSZ-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 2
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 2
- WJNKJKGZKFOLOJ-UHFFFAOYSA-N 1-dodecyl-4-ethenylbenzene Chemical compound CCCCCCCCCCCCC1=CC=C(C=C)C=C1 WJNKJKGZKFOLOJ-UHFFFAOYSA-N 0.000 description 2
- KMWWHLYDEIGCHS-UHFFFAOYSA-N 1-phenyl-3-propylundecan-1-one Chemical compound CCCCCCCCC(CCC)CC(=O)C1=CC=CC=C1 KMWWHLYDEIGCHS-UHFFFAOYSA-N 0.000 description 2
- LDVYZGRGZMIMKW-UHFFFAOYSA-N 2-(4-dodecylphenyl)ethanol Chemical compound CCCCCCCCCCCCC1=CC=C(CCO)C=C1 LDVYZGRGZMIMKW-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical class NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical class C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- YAUZJFRMTBUCGL-UHFFFAOYSA-N ethyl 4-ethenylbenzenesulfonate Chemical compound CCOS(=O)(=O)C1=CC=C(C=C)C=C1 YAUZJFRMTBUCGL-UHFFFAOYSA-N 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 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 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 239000003495 polar organic solvent Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical group [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 2
- ZPKUAUXTKVANIS-UHFFFAOYSA-N tetradec-1-enylbenzene Chemical compound CCCCCCCCCCCCC=CC1=CC=CC=C1 ZPKUAUXTKVANIS-UHFFFAOYSA-N 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- YMMGRPLNZPTZBS-UHFFFAOYSA-N 2,3-dihydrothieno[2,3-b][1,4]dioxine Chemical compound O1CCOC2=C1C=CS2 YMMGRPLNZPTZBS-UHFFFAOYSA-N 0.000 description 1
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- VYDVLDNLTSOBLM-UHFFFAOYSA-N 2-ethoxythiophene Chemical compound CCOC1=CC=CS1 VYDVLDNLTSOBLM-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- MCLMZMISZCYBBG-UHFFFAOYSA-N 3-ethylheptanoic acid Chemical compound CCCCC(CC)CC(O)=O MCLMZMISZCYBBG-UHFFFAOYSA-N 0.000 description 1
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- SKSFSYQOVIHZRG-UHFFFAOYSA-N C(CCCCCCCCCCC)S(=O)(=O)O.C Chemical compound C(CCCCCCCCCCC)S(=O)(=O)O.C SKSFSYQOVIHZRG-UHFFFAOYSA-N 0.000 description 1
- FFAVGNNPTJLHKO-UHFFFAOYSA-N CC(CCCCCCCCCBr)(C)C Chemical compound CC(CCCCCCCCCBr)(C)C FFAVGNNPTJLHKO-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical group SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002675 Polyoxyl Polymers 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 240000006394 Sorghum bicolor Species 0.000 description 1
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical group 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- IYYIVELXUANFED-UHFFFAOYSA-N bromo(trimethyl)silane Chemical compound C[Si](C)(C)Br IYYIVELXUANFED-UHFFFAOYSA-N 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 235000014121 butter Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- MIOPJNTWMNEORI-UHFFFAOYSA-N camphorsulfonic acid Chemical compound C1CC2(CS(O)(=O)=O)C(=O)CC1C2(C)C MIOPJNTWMNEORI-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical compound OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 description 1
- 125000005392 carboxamide group Chemical group NC(=O)* 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- ITZXULOAYIAYNU-UHFFFAOYSA-N cerium(4+) Chemical class [Ce+4] ITZXULOAYIAYNU-UHFFFAOYSA-N 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical class CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- LEDCJBCTEYLBJO-UHFFFAOYSA-N ethyl 2-phenylethenesulfonate Chemical compound CCOS(=O)(=O)C=CC1=CC=CC=C1 LEDCJBCTEYLBJO-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 235000000396 iron Nutrition 0.000 description 1
- AWRGYUYRFKKAID-UHFFFAOYSA-L iron(2+);phenylmethanesulfonate Chemical compound [Fe+2].[O-]S(=O)(=O)CC1=CC=CC=C1.[O-]S(=O)(=O)CC1=CC=CC=C1 AWRGYUYRFKKAID-UHFFFAOYSA-L 0.000 description 1
- VPCCKEJZODGJBT-UHFFFAOYSA-K iron(3+) phenylmethanesulfonate Chemical compound [Fe+3].[O-]S(=O)(=O)Cc1ccccc1.[O-]S(=O)(=O)Cc1ccccc1.[O-]S(=O)(=O)Cc1ccccc1 VPCCKEJZODGJBT-UHFFFAOYSA-K 0.000 description 1
- CXLAITXNPDDBEZ-UHFFFAOYSA-N iron(3+) toluene Chemical compound [Fe+3].C1(=CC=CC=C1)C CXLAITXNPDDBEZ-UHFFFAOYSA-N 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([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
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 229920000582 polyisocyanurate Polymers 0.000 description 1
- 239000011495 polyisocyanurate Substances 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- FOWDZVNRQHPXDO-UHFFFAOYSA-N propyl hydrogen carbonate Chemical compound CCCOC(O)=O FOWDZVNRQHPXDO-UHFFFAOYSA-N 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- FHGWPYOZXJCPRJ-UHFFFAOYSA-M silver;4-ethenylbenzenesulfonate Chemical compound [Ag+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 FHGWPYOZXJCPRJ-UHFFFAOYSA-M 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 150000003470 sulfuric acid monoesters Chemical class 0.000 description 1
- 239000010414 supernatant solution Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003568 thioethers Chemical group 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
- H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/16—Homopolymers or copolymers of alkyl-substituted styrenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L41/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur; Compositions of derivatives of such polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Description
本發明係關於新穎的聚噻吩-聚陰離子錯合物,其可溶解或分散於非極性有機溶劑中,及其用途。
導電性聚合物獲得日益增加的經濟重要性,因為聚合物對於可加工性、重量、及藉化學修飾將性能控制調整,均較金屬優越。習知的π-共軛聚合物實例為:聚吡咯、聚噻吩、聚苯胺、聚乙炔、聚伸苯基、及聚(對-伸苯基-伸乙烯基)。導電性聚合物層具有各種工業用途,例如:於電容器中作為聚合的反電極(counterelectrode)、或用作印刷電路板之貫穿接點。導電性聚合物係自單體的前驅物,例如:任選地經取代之噻吩、吡咯、與苯胺、及其個別的衍生物,其可為寡聚物,藉由化學或電化學之氧化法製備。化學地氧化聚合反應是普遍的,因為其技術上可容易地於一種液體介質及於各種基材上達成。
一種特別重要且工業上所使用的聚噻吩為聚(伸乙基-3,4-二氧噻吩)(PEDOT或PEDT),例如:被敘述於EP 339340 A2中,其係藉化學地聚合伸乙基-3,4-二氧噻吩(EDOT或EDT)製得,以及其於氧化形態具有非常高的導電度。許多聚(伸烷基-3,4-二氧噻吩)衍生物,特別是聚(伸乙基-3,4-二氧噻吩)衍生物,及其單體單元、合成反應、與應用被回顧於:L.Groenendaal,F.Jonas,D.Freitag,H.Pielartzik及J.R.Reynolds,Adv.Mater.,第12
期(2000年),第481至494頁中。
PEDOT與聚苯乙烯磺酸(PSS)之分散液得到特別的工業重要性,例如於EP 0440957B1中所揭示。自這些分散液可獲得透明的導電性薄膜,其已發現許多的應用,例如:作為抗靜電塗層或於有機發光二極體中作為電洞注射(hole injection)層。
EDT於PSS水溶液中聚合生成一種PEDT/PSS錯合物。陽離子性聚噻吩,其包含聚合的陰離子作為用於電荷補償之相對離子,通常於技術領域中亦常被稱為聚噻吩/聚陰離子錯合物。由於PEDT作為聚陽離子及PSS作為聚陰離子之高分子電解質性能,此錯合物並非一真溶液,但實為一種分散液。聚合物或部份的聚合物被溶解或分散至何種程度係依下者而定:聚陽離子與聚陰離子之質量比、聚合物之電荷密度、環境之鹽濃度、及周遭介質之性能(V.Kabanov,蘇聯化學回顧,第74期,2005年,第3至20頁)。此轉變可為流體,因此爾後在詞句”分散的”與”溶解的”之間不予區分。同樣地,對”分散液”與”溶液”之間、或”分散劑”與”溶劑”之間亦不予區分。反而,於後將這些詞句以等同的方式使用。
於先前技藝中,至今僅有於極性溶劑中製備聚噻吩-聚陰離子錯合物為可行。EP 0440957-A2敘述一種聚噻吩-聚陰離子錯合物之製法,其僅能於非常極性的溶劑中進行,因為例舉敘述的聚陰離子,聚苯乙烯磺酸及聚(甲基)丙烯酸,僅能溶解於極性溶劑如:水或較低醇類中。僅有於水中進行PEDT之聚合反應被特別地敘述。於此方法中之一缺點為溶劑之選擇被限制於極性溶劑,亦即:非極性溶劑無法被用於此聚噻吩-聚陰離子錯合物之製備方法中。
EP 1373356 B1及WO 2003/048228敘述於無水或低水溶劑中製備聚噻吩-聚陰離子錯合物。於此案例中,水溶劑被另一種水-可溶混的有機溶劑所替換。對於此,係於添加第二種溶劑後將水藉例如:蒸餾予以移除。此程序具有缺點:由於蒸餾,必須使用一種二階段的程序。此外,所添加的溶劑必須為水-可溶混,此同樣地造成侷限於極性溶劑。
Otani等人於JP 2005-068166中敘述一種方法,其中首先將一種導電聚合物,如PEDOT,乾燥,隨後分散於一種有機溶劑中。被提及之有機溶劑特別是那些具有一介電常數為5或更多者。實例指明為異丙醇及γ-丁內酯。此法亦具有缺點:需要使用極性溶劑予以再溶解。此法中之另一缺點為必須先合成導電聚合物,而後接著予以再分散。Otani等人未揭示任何聚噻吩-聚陰離子錯合物。
於2002年,H.Okamura等人(聚合物2002年,第43期,第3155至3162頁)敘述合成一種苯乙烯與苯乙烯磺酸之嵌段共聚物。改變該二種共聚單體之比例,並且發現共聚物可溶解於四氫呋喃、氯仿、丙酮、二甲基甲醯胺、甲醇、及水中。然而,該共聚物未被發現有任何溶解度於脂肪族或芳族碳氫化合物,如:己烷、甲苯、或苯中。未使用任何導電聚合物製備任何錯合物,例如:聚噻吩/聚陰離子錯合物,亦未曾研究薄膜之導電性或電阻。因此Okamura等人所敘述之聚合物不適合用於確認聚合物錯合物於十分非極性溶劑(如:甲苯)中之溶解度。
一系列的研究亦敘述如何達成聚噻吩之溶解度,其係藉由將側基團接附於噻吩單體,隨後進行聚合反應,或藉由製備一種噻吩單元與用以增強溶解度之單元的嵌段共聚物。
例如:Luebben等人於聚合材料:科學&工程2004年,第91期,第979頁中所敘述:製備一種PEDOT和聚乙二醇的嵌段共聚物。於此所使用之相對離子為過氯酸鹽及對-甲苯磺酸。聚合物皆溶解於極性有機溶劑,如:伸丙基碳酸鹽及硝基甲烷中,測得導電度為10-4
S/公分至1 S/公分。然而,此嵌段共聚物具有缺點:其僅可溶解於非常極性的溶劑中。此外,所選擇的相對離子未參與薄膜之生成,故導電薄膜無法使用這些嵌段共聚物生成。
其他的出版品敘述製備有機聚噻吩溶液,其藉由引入側基團至噻吩上,其可增強溶解度。例如:Yamamoto等人於聚合物第43期,2002年,第711至719頁中敘述製備PEDOT之己基衍生物,其為一種未帶電的分子,可溶解於有機溶劑中。摻加或使用碘進行氧化反應亦被敘述。然而,未指示導電薄膜是否可製自經摻加或氧化的噻吩有機溶液。於此方法中之另一缺點為:聚合物分子量是低的,且因此薄膜的生成性能是不佳的。於前引述之出版品中,分子量(Mw
)可達2400公克/莫耳及8500公克/莫耳。由於聚噻吩同時充當一種薄膜-生成聚合物及一種導電聚合物,此二性能無法各自獨立地建構。原則上,此方法具有缺點:引入側基團至噻吩上不僅影響溶解度性能,亦影響分子之電子性能。
因此對導電性聚噻吩於非極性溶劑中之分散液具有需求,用此可製得導電性薄膜。此需求係基於下列事實:此類分散液至今僅有於非常極性的溶劑中者。更特別是對下者具有需求:於非極性溶劑中之分散液,其具有良好的薄膜-生成性能及顯示導電性。因為許多塗覆系統為基於非極性溶劑,故對於可溶解或分散於非極性溶劑中之導電性聚噻吩具有甚大的需求。
因此本發明之目的為製備聚噻吩的分散液,其可溶解於非極性溶劑中,及可自其製造導電薄膜。本發明之另一目的為製備此類分散液,於合成時所使用的溶劑同時為最終分散液之溶劑,因此無需置換溶劑。
如今已令人驚訝地發現任選地經取代的聚噻吩和聚陰離子之錯合物,該聚陰離子包括共聚物,可解決此難題。
本發明因此提供一種包括一任選地經取代的聚噻吩及一聚陰離子之錯合物,其特徵在於該聚陰離子包含一共聚物,其具通式(I)及(II)之重複單元,或通式(I)及(III)之重複單元,或通式(II)及(III)之重複單元,或通式(I),(II)及(III)之重複單元:
通式(II)應被明瞭為取代基R可被結合至芳族環上x次。
於本發明之一較佳實施例中,錯合物的聚陰離子為一具式(II)及(III)之重複單元的共聚物。
於本發明之甚至更佳的實施例中,聚陰離子為一具式(IIa)及(III)之重複單元的共聚物
具通式(I),(II)及(III)之重複單元於整體聚合物中之比例分別為a、b及c,a、b及c為介於0至100%間之質量百分率。a及b較佳地介於0至50%之間,其中a及b必須非二者皆為0%。c之比例以介於20至100%之間為較佳。
於本發明說明書中,C1
-C18
-烷基代表線性或分支之C1
-C18
-烷基基團,例如:甲基、乙基、正-或異丙基、正-,異-,二級-,或三級-丁基、正戊基、1-甲基丁基、2-甲基丁基、3-甲基丁基、1-乙基丙基、1,1-二甲基丙基、1,2-二甲基丙基、2,2-二-甲基丙基、正-己基、正-庚基、正-辛基、2-乙基己基、正-壬基、正-癸基、正-十一基、正-十二基、正-十三基、正-十四基、正-十六基、正-十七基、或正-十八基;C1
-C30
-烷基代表線性或分支之C1
-C30
-烷基基團,其連同前述之C1
-C18
-烷基基團,包括烷基基團如:正-十九基、正-二十烷基、正-二十一烷基、正-二十二烷基、正-二十三烷基、正-二十四烷基、正-二十五烷基、正-二十六烷基、正-二十七烷基、正-二十八烷基、正-二十九烷基、或正-三十烷基。於本發明說明書中之C1
-C18
-烷氧基基團代表對應於前示C1
-C18
-烷基基團之烷氧基基團。於本發明說明書中,C5
-C12
-環烷基代表C5
-C12
-環烷基基團,如:環戊基、環己基、環庚基、環辛基、環壬基或環癸基,C6
-C14
-芳基代表C6
-C14
-芳基基團,如:苯基或萘基,及C7
-C18
-芳烷基代表C7
-C18
芳烷基基團,如:苄基、鄰-、間-、對-甲苯基、2,3-,2,4-,2,5-,2,6-,3,4-,3,5-二甲苯基或2,4,6-三甲苯基。於本發明說明書中,C1
-C4
-羥基烷基被明瞭意指C1
-C4
-烷基基團,其具有一羥基基團作為取代基,而且C1
-C4
-烷基基團可為如:甲基、乙基、正-或異丙基、正-,異-,二級-,或三級-丁基;C1
-C5
-伸烷基基團被明瞭意指伸甲基、伸乙基、正-伸丙基、正-伸丁基或正-伸戊基。於前列舉者係作為實例藉以說明本發明,而不應被視為唯一者。
於本發明說明書中,聚陰離子具有一重量平均分子量(Mw
)介於2000至5000000公克/莫耳之間,以介於10000至1000000公克/莫耳之間為較佳,以介於40000公克/莫耳與600000公克/莫耳之間為最佳。
聚陰離子之分子量可藉凝膠滲透層析法(GPC)予以測定。關於此,將聚合物溶解於一溶劑中(例如:氯仿或四氫呋喃),並且通過一GPC管柱。所使用的參考標準品可為聚苯乙烯於相同的溶劑中。所使用的偵測器可為紫外光偵測器或折射率偵測器。
聚陰離子可製自對應的單體。於聚合物中之重複單元的比率可經由所使用單體之比率予以決定,其中由於不同的反應速率,故前述之比率無需等同。聚合反應可使用自由基、陰離子或陽離子引發劑予以引發。此外,過渡金屬錯合物亦可用於引發。製備聚合物之合成方法被敘述於H.-G.Elias所著的手冊”Makromolekle”[大分子],第1冊中。
除了於前詳細界定的聚陰離子外,此新穎的錯合物包括任選地經取代的聚噻吩,其包含通式(IV)之重複單元
於較佳的實施例中,包含通式(IV)之重覆單元之聚噻吩為那些包含通式(IV-a)及/或通式(IV-b)之重覆單元者
通式(IV-a)應被明瞭為取代基R可被結合至伸烷基基團A上y次。
於另一較佳的實施例中,包含通式(IV)之重覆單元之聚噻吩為那些包含通式(IV-aa)及/或通式(IV-ab)之重覆單元者
於另一較佳的實施例中,包含通式(IV)之重覆單元之聚噻吩為那些包含通式(IV-aaa)及/或通式(IV-aba)之聚噻吩者
於本發明說明書中,字首”聚-”應被明瞭為有多於一個相同或相異的重覆單元存在於聚噻吩中。聚噻吩總計包含n個通式(IV)之重覆單元,其中n可為一自2至2000之整數,以2至100為較佳。於聚噻吩中,通式(IV)之重覆單元可各為相同或相異。較佳者為於每個案例中,聚噻吩包含相同的通式(IV)的重覆單元。
於端基基團上,聚噻吩較佳地各具有H。
於特佳的實施例中,具有通式(I)的重覆單元之聚噻吩為聚(3,4-伸乙基二氧噻吩)、聚(3,4-伸乙基氧硫噻吩)、或聚(噻吩並[3,4-b]噻吩),亦即:一種包括式(IV-aaa)、(IV-aba)或(IV-b)之重覆單元的均聚噻吩。
於另一特佳的實施例中,具有通式(IV)之重覆單元的聚噻吩為一共聚物,其包含通式(IV-aaa)與(IV-aba)、(IV-aaa)與(IV-b)、(IV-aba)與(IV-b)、或(IV-aaa)、(IV-aba)與(IV-b)之重覆單元,較佳者為具有式(IV-aaa)與(IV-aba)、及(IV-aaa)與(IV-b)之重覆單元的共聚物。
於本發明說明書中,C1
-C5
-伸烷基基團A為亞甲基、伸乙基、正-伸丙基、正-伸丁基、或正-伸戊基;以及另外C1
-C8
-伸烷基基團為正-伸己基、正-伸庚基及正-伸辛基。於本發明說明書中,C1
-C8
-亞烷基基團為前示之C1
-C8
伸烷基基團,其包含至少一個雙鍵。於本發明說明書中,C1
-C8
-二氧伸烷基基團、C1
-C8
-氧硫伸烷基基團及C1
-C8
-二硫伸烷基基團為:C1
-C8
-二氧伸烷基基團、C1
-C8
-氧硫伸烷基基團及C1
-C8
-二硫伸烷基基團,其對應於前示之C1
-C8
-伸烷基基團者。C1
-C18
-烷基、C5
-C12
-環烷基、C6
-C14
-芳基、C7
-C18
-芳烷基、C1
-C18
-烷氧基及C1
-C4
-羥基烷基各同前述之定義。前示者係作為實例藉以說明本發明,而不應被視為唯一者。
前述基團之其他可能取代基包括許多有機基團,例如:烷基、環烷基、芳基、鹵素、醚、硫醚、二硫化物、亞碸、碸、磺酸鹽、胺基、醛、酮、羧酸酯、羧酸、碳酸鹽、羧酸鹽、氰基、烷基矽烷及烷氧基矽烷基團、以及碳醯胺(carboxamide)基團。
供製備通式(IV)聚噻吩及其衍生物用之單體前驅物,其製備方法對於本技術領域中具有通常知識者為習知,被敘述於如:L.Groenendaal,F.Jonas,D.Freitag,H.Pielartzik及J.R.Reynolds著,Adv.Mater.第12期(2000年),第481至494頁,及其中所引述之文獻。
於本發明說明書中,前示噻吩之衍生物被明瞭意指例如:這些噻吩之二聚物或三聚物。較高分子量的衍生物,亦即:單體前驅物之四聚物,五聚物等,亦可為衍生物。這些衍生物可由相同或相異的單體單元所生成,並且可以純的形態或以一種與彼此及/或與前述噻吩之混合物使用。於本發明說明書中,這些噻吩及噻吩衍生物之經氧化或還原的形態亦被包括於”噻吩及噻吩衍生物”一詞中,其聚合反應會生成與前示噻吩及噻吩衍生物案例中相同的導電聚合物。
分散液或溶液可另外包括至少一種聚合的黏結劑。適合的黏結劑為聚合的有機黏結劑,例如:聚乙烯基醇類、聚乙烯基吡咯啶酮、聚乙烯基氯化物、聚乙烯基乙酸酯、聚乙烯基丁酸酯、聚丙烯酸酯、聚丙烯醯胺、聚甲基丙烯酸酯、聚甲基丙烯醯胺、聚丙烯腈、苯乙烯/丙烯酸酯、乙酸乙烯酯/丙烯酸酯與乙烯/乙酸乙烯酯共聚物、聚丁二烯、聚異戊二烯、聚苯乙烯、聚醚、聚酯、聚碳酸酯、聚胺基甲酸酯、聚醯胺、聚醯亞胺、聚碸、蜜胺-甲醛樹脂、環氧樹脂、聚矽氧樹脂、或纖維素。
任選地經取代之聚噻吩為陽離子性,”陽離子性”僅指位於聚噻吩主鏈上之電荷。依R基團上之取代基,聚噻吩可於結構單元中帶有正及負電荷,於此案例中,正電荷位於聚噻吩主鏈上及負電荷可位於經磺酸鹽或羧酸鹽基團取代之R基團上。於此案例中,聚噻吩主鏈之正電荷可部份地或完全地被存在於R基團上之任意陰離子基團所飽和。整體而言,於這些案例中之聚噻吩可為陽離子性、未帶電、或甚至為陰離子性。然而,於本發明說明書中,其皆被視為陽離子性聚噻吩,因為於聚噻吩主鏈上之正電荷具關鍵性。於分子式中正電荷未予顯示,因為其準確的數目及位置無法被確切地陳述。但正電荷之數目至少為1及最多為n,其中n為於聚噻吩內所有重覆單元(相同或相異)之總數。
發明的聚噻吩/聚陰離子錯合物可溶解或分散於一種水不溶混的溶劑中。適合的溶劑特別包括下列有機溶劑,其於反應條件下為惰性:芳族碳氫化合物,例如:甲苯及二甲苯;脂肪族碳氫化合物,例如:己烷、庚烷及環己烷;脂肪族羧酸酯類,例如:乙酸乙酯;氯碳氫化合物,例如:二氯甲烷及二氯乙烷;脂肪族及芳脂族醚類,例如:二乙醚或四氫呋喃。特佳者為脂肪族及芳族碳氫化合物。
通式(IV)之任選地經取代的聚噻吩,可藉將通式(V)之任選地經取代的噻吩經氧化聚合反應製得
對於通式(V)之任選地經取代的噻吩,其較佳的領域與通式(IV)之任選地經取代的聚噻吩相同。
對於此氧化聚合反應,可使用適合噻吩之氧化聚合反應的氧化劑,且其對本技術領域中具有通常知識者為習知,這些被敘述於如:美國化學學會期刊,第85期,第454頁(1963年)。於本發明說明書中,所使用的氧化劑可為H2
O2
、K2
C2
O7
、鹼金屬及過氧二硫酸銨,例如:過氧二硫酸鈉或鉀、鹼金屬之過硼酸鹽、高錳酸鉀、銅鹽,例如:四氟硼酸銅、或鈰(IV)鹽或CeO2
。較佳者為價廉及容易處理的氧化劑,如:無機酸之鐵(III)鹽類,例如:FeCl3
、Fe(ClO4
)3
、及有機酸及具有有機基團之無機酸之鐵(III)鹽類。
具有有機基團之無機酸之鐵(III)鹽類,其實例包括:C1
-C20
-烷醇之硫酸單酯之鐵(III)鹽類,例如:月桂基硫酸鹽之鐵(III)鹽。有機酸之鐵(III)鹽類實例包括:下列者之鐵(III)鹽類:C1
-C20
-烷磺酸(alkanesulphonic acid),如:甲烷-及十二烷磺酸、脂肪族C1
-C20
-羧酸,如:2-乙基己基羧酸、脂肪族過氟羧酸,如:三氟乙酸、及過氟辛酸、脂肪族二羧酸,如:草酸,及特別是任選地經C1
-C20
-烷基基團取代之芳族磺酸,如:苯磺酸、對-甲苯磺酸、及十二基苯磺酸、及環烷磺酸,如:樟腦磺酸。
於本發明說明書中,C1
-C20
-烷醇(alkanol)代表一元醇(monohydric alcohol)類,其具有一1至20個碳原子之烷基基團,C1
-C20
-烷磺酸代表一元(monobasic)磺酸,其具有一1至20個碳原子之烷基基團,及C1
-C20
-羧酸代表一元(monobasic)羧酸,其具有一1至20個碳原子之烷基基團。
如今令人驚訝地發現對於通式(V)之任選地經取代噻吩之聚合反應,於反應介質中,亦即:非極性溶劑,僅需要使用一種低溶解度的氧化劑,例如:甲苯磺酸鐵(III)實質上不溶於甲苯。然而,EDT於甲苯中可藉甲苯磺酸鐵(III)予以聚合得到PEDT。
本發明因此進一步提供一種方法,於聚陰離子之存在下製備通式(IV)之任選地經取代的聚噻吩,其特徵在於通式(V)任選地經取代之噻吩的氧化聚合反應係於非極性溶劑中進行,
較佳的氧化劑為脂肪族及芳族磺酸之鐵(III)鹽類,以對-甲苯磺酸鐵(III)為更佳。特佳的莫耳比率為每莫耳噻吩之1至3莫耳對-甲苯磺酸鐵(III)。所使用的溶劑可為前示之水不混溶的溶劑。
於本發明說明書中,可使用前述這些有機酸之鐵(III)鹽類之混合物。前述的鐵(III)鹽類可併同其他氧化劑任選地被用作催化劑。對於式(V)任選地經取代之噻吩的氧化聚合反應,就理論上而言,每莫耳噻吩需要2.25當量的氧化劑(參見如:聚合物科學期刊,部份A,聚合物化學,第26期,第1287頁(1988年))。然而,亦可使用較高或較低當量的氧化劑。
本發明另外提供一種共聚物,其至少包含通式(IIa)及(III)之重覆單元
於此所示之C1
-C18
-烷基基團及所示之C1
-C30
-烷基基團,其定義對應於前述這些烷基基團之定義。
於共聚物中通式(IIa)及(III)之重覆單元可個別為相同或相異。較佳者為於個別案例中之共聚物具有相同的通式(IIa)及(III)之重覆單元。
於本發明說明書中,發明的共聚物具有一分子量,其介於2000至5000000公克/莫耳之間,以介於10000至1000000公克/莫耳之間為較佳,以介於40000與600000公克/莫耳之間為最佳。
通式(IIa)及(III)之重覆單元,其質量比經由元素分析及1
H NMR予以比較。於元素分析中,將計算及發現的百分率進行比較。於1
H NMR光譜中,將特殊重覆單元之特性信號相互比較。
發明的共聚物可溶解或分散於一種水-不溶混的溶劑中。適合的溶劑為前示之溶劑,較佳的溶劑為芳族或脂肪族碳氫化合物。
本發明另外提供使用此發明錯合物於製造導電薄膜或塗覆系統,或者於有機發光二極體中作為電洞注射層之用途。
下列實例僅係藉舉例方式解說本發明,不應被解說為一限制。
於氬氣下將氯化鋁(227.114公克=1.7莫耳)懸浮於二氯甲烷(800毫升)中,並冷卻至0℃。於30分鐘(min.)內將溶解於100毫升二氯甲烷中之醋酸酐(89.872公克=0.88莫耳)緩慢地滴加至其中。持續攪拌此混合物約15分鐘,隨後於冷卻下,在30分鐘內滴加溶解於CH2
Cl2
(於0℃)中之十二基苯(99.267公克=0.4莫耳)。此反應於未加冷卻下進一步徹夜攪拌。將獲得之橘黃色反應液緩慢地倒至1.5公升之碎冰上,並自水相分離,水相則予以棄置。萃取有機相,藉各使用500毫升之下者予以震盪二次:約10%之鹽酸、飽和碳酸鈉溶液及飽和氯化鈉溶液。使用無水硫酸鎂乾燥有機相,並以旋轉式蒸發器移除溶劑。將獲得之棕色固體於甲醇中再結晶。結晶係於4℃下經徹夜後達成。產率:106.669公克=0.37莫耳=理論值之92.4%分析:250 MHz,CDCl3
;δ=0.90(dd,3H,J=5.7,6.9 Hz),1.28(m,18H),1.56-1.60(m,2H),2.61(s,3H),2.65(t,2H,J=7.3 Hz),7.27(d,2H,J=8.2 Hz),7.89(d,2H,J=8.2 Hz)。
將4-十二基苯乙酮(106.669公克=0.37莫耳)起始地加入甲醇(1.1公升)中,並於氬氣下冷卻至0℃。以5分鐘之間隔,將總計10份的NaBH4
(20.39公克=0.54莫耳)加至此溶液。在氣體強烈釋出減輕後,移開冰浴,及於室溫下進一步徹夜攪拌反應液。將此溶液濃縮至乾,並將白色結晶殘餘物加至1公升的己烷中。萃取獲得之懸浮液,藉每次使用500毫升之下者予以震盪二次:約10%之鹽酸,其可完全地溶解剩餘的固體。有機相係藉由各使用500毫升飽和氯化鈉溶液予以震盪二次而萃取、使用硫酸鎂加以乾燥、經過濾,而後以旋轉式蒸發器進行濃縮,及於-20℃下結晶。將結晶過濾並予乾燥。
產率:100.032公克=0.35莫耳=理論值之93.4%分析:250MHz,CDCl3
;δ=0.90(dd,3H,J=5.4,6.9 Hz),1.20-1.35(m,18H),1.51(d,3H,J=6.3 Hz),1.54-1.65(m,2H),1.81(d,1H,J=1.9 Hz),2.60(t,2H,J=7.9 Hz),4.86(m,1H),7.20(d,2H,J=7.9 Hz),7.31(d,2H,J=7.9 Hz)。
於一只裝設水分離器及迴流冷凝器之2公升圓底燒瓶中起始地加入1.2公升甲苯,隨後添加(對-十二基苯基)甲基甲醇(50.082公克=0.173莫耳)及單水對-甲苯磺酸(0.679公克=3.6毫莫耳)。於持續攪拌下將混合物加熱至迴流,及維持沸騰直至不再有水被分離出來。反應混合物一經冷卻至室溫時,有機相係藉由每次使用500毫升水予以震盪二次及使用250毫升飽和氯化鈉溶液震盪一次而萃取。使用硫酸鎂加以乾燥後,以旋轉式蒸發器移除溶劑。獲得一種黃油。其後合併二個批次。粗產物係藉由管柱層析法在400公克矽凝膠60上使用己烷作為洗提液而純化,並選擇100毫升之級分大小。
Rf
(甲醇)=0(己烷)
Rf
(副產物)=0.70(己烷)
Rf
(正-十二基苯乙烯)=0.50(己烷)
產率:97.934公克=0.36莫耳分析:250MHz,CDCl3
;δ=0.90(t,3H,J=6.6 Hz),1.20-1.4(m,18H),1.60(m,2H),2.60(t,2H,J=7.55 Hz),5.22(d,1H,J=7.85 Hz),5.73(d,1H,J=17.6 Hz),6.71(q,1H),7.15(d,2H,J=8.0 Hz),7.35(d,2H,J=7.9 Hz)。
於一500毫升圓底燒瓶中起始地加入400毫升之水,且於室溫(RT)攪拌下,將45.046公克對-苯乙烯磺酸鈉(45.046公克=0.200莫耳)溶解於其中。為確保無光照射,以鋁箔包裹燒瓶外圍。將溶液冷卻至0℃及以數部份與34.225公克之硝酸銀(34.225公克=0.200莫耳)摻混,其隨即產生一種粉紅色沉澱物。所有後續的操作皆以儘可能避光的方式進行。混合物於0℃下再予攪拌30分鐘,以及藉由一D2玻璃熔塊濾除固體。獲得之濾餅分3部份使用150毫升之冰水清洗,及使用少量二乙醚重複地搗成泥漿予以乾燥。米色的固體加入500毫升乙腈,以及經由一D4玻璃熔塊濾除未溶解的固體。濃縮溶液至乾燥,並將獲得之固體於冷凍箱中儲存過夜。產率:47.890公克=0.165莫耳=理論值之82.5%。
於一經鋁箔包裹之250毫升圓底燒瓶,起始地加入於390毫升乙腈中之47.890公克苯乙烯-4-磺酸銀鹽(47.890公克=0.165莫耳),並使用一大攪拌子攪拌時,與35.77公克乙基溴化物(35.77公克=0.33莫耳)摻混。將一只類同的經鋁箔包裹之迴流冷凝器接附至燒瓶,其被供給一只充滿氬氣之氣球。反應混合物於70℃下攪拌5小時(h),並經冷卻至室溫後,將所生成之溴化銀經由一D4玻璃熔塊濾除及使用旋轉式蒸發器將濾液濃縮。剩餘的油加入400毫升二氯甲烷(DCM),並通過一只具有5公分高矽凝膠層之D4玻璃熔塊予以濾除。過濾得到之物料每次使用50毫升DCM重覆地萃取,及移除溶劑。獲得一種黃色非常高黏度的油。
產率:29.457公克=0.139莫耳=理論值之84.2%分析:250MHz,CDCl3
;δ=1.30(t,3H,J=7.3 Hz),4.12(q,2H,J=7.3 Hz),5.46(d,1H,J=11.1 Hz),5.96(d,1H,J=17.7 Hz),6.77(dd,1H,J=11.1,17.4 Hz),7.65(d,2H,J=8.2 Hz),7.86(d,2H,J=8.2 Hz)。
在氬氣環境下,於一500毫升燒瓶中起始地加入二氯乙烷(250公克)作為溶劑。於添加35.0公克對-十二基苯乙烯(35.0公克=128.45毫莫耳;其製備敘述於實例3)及7.28公克對-苯乙烯磺酸乙酯(7.28公克=34.30毫莫耳;其製備敘述於實例5)後,藉一只氣體入口管將混合物以氬氣飽和。對於此,將氬氣持續通過混合物15分鐘。於此期間,加熱混合物至60℃。所使用之自由基引發物為偶氮二異丁腈(AIBN),其經氬氣予以飽和後,溶解於一些二氯乙烷中,通過一隔膜予以添加。聚合反應液再以氬氣清除5分鐘,隨後於60℃下徹夜完成聚合。些微黏稠的聚合溶液經冷卻後,聚合物在攪拌下於甲醇中進行沉澱。將經沉澱後獲得之聚合物再溶解於四氫呋喃(THF)中,及再度於甲醇中沉澱。經分離後的白色聚合物於高度真空下予以乾燥。
產率:18公克=理論值之42.6%分析(GPC):分子量(相對於四氫呋喃中之PS):120000公克/莫耳,多分散性D(Mw
/Mn
):1.5分析(NMR):250MHz,CDCl3
;δ=0.88(3H),1.20-1.30(-CH2-,-CH-),1.40-1.45(3H,CH3酯),1.45-1.55(2H),2.50-2.60(2H),4.0-4.1(2H,CH2-酯),6.0-7.0(4H),7.3-7.6(4H,-CH-酯)
可使用NMR光譜分析測定磺化的程度,對於此,於0.88 ppm之波峰(十二基基團之終端CH3
),及4.0-4.1 ppm(乙酯之CH2
)被認為彼此相關。此導致十二基苯乙烯對於苯乙烯磺酸乙酯之經積分校準的比率為1:5.6,此比率對應於聚合物的磺化程度為21.09%。
由此導致之磺化程度為:
將15.0公克聚(乙基對-苯乙烯磺酸酯-共-對-十二基苯乙烯)(其製備敘述於實例6)溶解於50毫升之二氯甲烷及100毫升之甲苯中,並加熱至100℃。於加熱期間,溶液以氬氣予以除氣。於5分鐘的時間,通過一隔膜加入60公克三甲基矽烷基溴化物(TMSBr)(60公克=16.33毫莫耳)。此黃色溶液於100℃迴流下攪拌60小時,隨後予以濃縮,及將聚合物於甲醇/水中沉澱。沉澱後獲得之聚合物而後再溶解於四氫呋喃(THF)中,再於甲醇中沉澱。經分離後的黃色聚合物於高度真空下予以乾燥。
產率:10公克分析(EA):
分析(NMR):250MHz,CDCl3
;δ=0.88(3H),1.20-1.40(-CH2
-,-CH-),1.45-1.55(2H),2.50-2.60(2H),6.0-7.0(4H),7.3-7.6(-CH-芳族之酯)
可使用NMR光譜測定酯之水解程度,對於此,於0.88 ppm之波峰(十二基基團之終端CH3
),及於4.11 ppm之波峰(乙酯之CH2
),其勉強可識別,被認為彼此相關(1:53.3)。此導致酯之水解程度為約86.7%。
分析(GPC):
將樣品溶解於四氫呋喃中。所使用之校準標準品為聚苯乙烯。使用之偵測器為紫外光偵測器及折射率偵測器(RI)。
於一50毫升圓底燒瓶中起始地加入12.5公克甲苯及1公克得自實例7之聚(對-苯乙烯磺酸-共-對-十二基苯乙烯),並攪拌10分鐘。隨後添加0.3公克(2.1毫莫耳)伸乙基二氧噻吩(Clevios M V2,H.C.Starck GmbH)。而後,加入1.33公克甲苯磺酸鐵(III)(2.3毫莫耳),並將混合物於室溫下攪拌24小時。其後,關閉攪拌器,並於10分鐘後將所產生的分散液輕輕倒出。再經48小時後,將混合物過濾通過一具有孔隙尺寸為0.45微米之過濾器。
測定固體含量,將2公克樣品於100℃下乾燥16小時。使用起始重量及乾燥含量測得固體含量為8.11%。
將得自實例8之聚(3,4-伸乙基二氧噻吩/聚(對-苯乙烯磺酸-共-對-十二基苯乙烯)錯合物之發明調配物用於建構一種有機發光二極體(OLED)。製造OLED之程序如下:
ITO-塗覆之玻璃(Merck Balzers AG,FL,Part.No.253674 XO)切割成50毫米x 50毫米小塊(基材)。隨後將基材於3%水性Mucasol溶液之超音波浴中清洗15分鐘。這些基材而後以蒸餾水沖洗,並於離心機中旋轉乾燥。重複此沖洗及乾燥操作10次。緊接於塗覆前,將經ITO-塗覆之側於一紫外光/臭氧反應器(PR-100,UVP公司,劍橋,英國)中清洗10分鐘。
將約5毫升得自實例8之發明分散液過濾(Millipore HV,0.45微米)。洗淨的ITO-塗覆基材置放於一旋轉塗覆器上,並將已過濾的溶液分佈於基材之ITO-塗覆側上。隨後藉以1500rpm轉動此板片歷時30秒鐘。而後將已塗覆的基材於加熱板上以130℃乾燥15分鐘。層厚為500奈米(Tencor,Alphastep 500)。
所有其他的操作步驟皆於純N2
氛圍下進行(惰性氣體手套箱系統,M.Braun,Garching),已塗覆的基材被移轉至其內。首先,將使用得自實例8分散液塗覆之基材於加熱板上以180℃後-乾燥5分鐘。於個別層上測定得自實例8分散液之導電率,藉施加,通過一陰影掩膜,間隔0.5毫米之長度2.5公分Ag電極(類似操作步驟4)。使用靜電計測定之表面電阻率與層厚相乘,藉以獲得電的比電阻率。這些層之比電阻率為約100 000 000歐姆.公分。
將一白色聚合發射體之5毫升1重量%二甲苯溶液予以過濾(Millipore HV,0.45微米),並分佈於經乾燥的電洞注射層上。隨後藉以2500rpm轉動此板片,關閉蓋子,歷時30秒鐘將發射體的上澄溶液(supernatant solution)旋轉去除。而後將此層於加熱板上以180℃乾燥10分鐘。總層厚為585奈米。
施加一只金屬電極作為發射層之陰極。關於此,將基材以發射層朝下置於一陰影掩膜上,其包含直徑為2.5毫米之電洞。自二只壓力為p=10-3帕之蒸汽沉積船,藉蒸汽沉積接續地施加一5奈米厚的Ba層及一200奈米厚的Ag層。蒸汽沉積速率對於鋇為10/秒及對於銀為20/秒。分隔的金屬電極具有一面積為4.9毫米2
。
有機LED的二只電極經由電導線被(接觸-)連接至一電壓來源。正極連接至ITO電極,負極經由一細的可撓的Au線連接至金屬電極。將OLED電流及電致發光強度(此係使用一光電二極體偵測(EG&G C30809E))對於電壓之依賴予以記錄。而後測定使用壽命,其係藉流動固定的電流I=60微安培通過此裝置,及監控電壓及光強度對於時間之函數。
因此,製得之OLED顯現典型的有機發光二極體之二極體性能(參見第1圖)。於施加12伏特電壓U時,正向電流I為0.57安培/平方公分及亮度L為9.2燭光/平方公尺。界定為發光衰退至起始亮度之一半的使用壽命為60小時,於一固定的二極體電流為60微安培。
因此得以證實以得自實例8之發明分散液為基礎之無水包含PEDOT的溶液之基本適用性。
第1圖為製得之OLED所顯現典型的有機發光二極體之二極體性能
Claims (10)
- 一種錯合物,其包括一任選地經取代的聚噻吩及一聚陰離子,其特徵在於該聚陰離子包含一共聚物,其具有通式(I)及(III)之重複單元,或通式(II)及(III)之重複單元,或通式(I),(II)及(III)之重複單元:
- 根據申請專利範圍第1項之錯合物,其特徵在於該聚陰離子為一具式(II)及(III)之重複單元之共聚物。
- 根據申請專利範圍第2項之錯合物,其特徵在於該聚陰離子包含一具式(IIa)及(III)之重複單元之共聚物
- 根據申請專利範圍第1至3項中任一項之錯合物,其特徵在於該聚陰離子之分子量介於2000至5000000公克/莫耳之間。
- 根據申請專利範圍第1至3項中任一項之錯合物,其特徵在於該任選地經取代的聚噻吩包含通式(IV)之重複單元
- 根據申請專利範圍第1至3項中任一項之錯合物,其特徵在於該任選地經取代的聚噻吩包含通式(IV-aaa)及/或通式(IV-aba)之重複單元
- 根據申請專利範圍第1至3項中任一項之錯合物,其特徵在於該錯合物可溶解或分散於水不溶混的溶劑中,該溶劑係選自由芳族及脂肪族碳氫化合物、脂肪族羧酸酯類、氯碳氫化合物、脂肪族或芳脂族醚類所組成之群組。
- 一種共聚物,其特徵在於其至少包含通式(IIa)及(III)之重複單元
- 一種在聚陰離子之存在下用於製備根據申請專利範圍第1至3項中任一項之錯合物之方法,其特徵在於使用氧化劑進行通式(V)任選地經取代之噻吩的氧化聚合反應
- 一種根據申請專利範圍第1至3項中任一項之錯合物之用途,其係用於製造導電薄膜或塗覆系統,或者於有機發光二極體中作為電洞注射層。
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Families Citing this family (57)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2537874B1 (en) | 2006-07-21 | 2021-05-19 | Nissan Chemical Corporation | Sulfonation of conducting polymers and oled, photovoltaic, and esd devices |
US8094434B2 (en) | 2008-04-01 | 2012-01-10 | Avx Corporation | Hermetically sealed capacitor assembly |
JP5359132B2 (ja) * | 2008-09-05 | 2013-12-04 | コニカミノルタ株式会社 | 透明電極及び該透明電極を有する有機エレクトロルミネッセンス素子 |
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US8576543B2 (en) | 2010-12-14 | 2013-11-05 | Avx Corporation | Solid electrolytic capacitor containing a poly(3,4-ethylenedioxythiophene) quaternary onium salt |
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US8451588B2 (en) | 2011-03-11 | 2013-05-28 | Avx Corporation | Solid electrolytic capacitor containing a conductive coating formed from a colloidal dispersion |
US8300387B1 (en) | 2011-04-07 | 2012-10-30 | Avx Corporation | Hermetically sealed electrolytic capacitor with enhanced mechanical stability |
US8947857B2 (en) | 2011-04-07 | 2015-02-03 | Avx Corporation | Manganese oxide capacitor for use in extreme environments |
US8379372B2 (en) | 2011-04-07 | 2013-02-19 | Avx Corporation | Housing configuration for a solid electrolytic capacitor |
US9767964B2 (en) | 2011-04-07 | 2017-09-19 | Avx Corporation | Multi-anode solid electrolytic capacitor assembly |
JP5763960B2 (ja) * | 2011-04-08 | 2015-08-12 | Necトーキン株式会社 | 導電性高分子懸濁水溶液およびその製造方法、導電性有機材料、ならびに固体電解コンデンサおよびその製造方法 |
DE102013101443A1 (de) | 2012-03-01 | 2013-09-05 | Avx Corporation | Ultrahigh voltage solid electrolytic capacitor |
US8971019B2 (en) | 2012-03-16 | 2015-03-03 | Avx Corporation | Wet capacitor cathode containing an alkyl-substituted poly(3,4-ethylenedioxythiophene) |
JP2013219362A (ja) | 2012-04-11 | 2013-10-24 | Avx Corp | 過酷な条件下で強化された機械的安定性を有する固体電解コンデンサ |
US9548163B2 (en) | 2012-07-19 | 2017-01-17 | Avx Corporation | Solid electrolytic capacitor with improved performance at high voltages |
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DE102013213723A1 (de) | 2012-07-19 | 2014-01-23 | Avx Corporation | Festelektrolytkondensator mit erhöhter Feucht-zu-Trocken-Kapazität |
JP5933397B2 (ja) | 2012-08-30 | 2016-06-08 | エイヴィーエックス コーポレイション | 固体電解コンデンサの製造方法および固体電解コンデンサ |
GB2512480B (en) | 2013-03-13 | 2018-05-30 | Avx Corp | Solid electrolytic capacitor for use in extreme conditions |
US9324503B2 (en) | 2013-03-15 | 2016-04-26 | Avx Corporation | Solid electrolytic capacitor |
US9824826B2 (en) | 2013-05-13 | 2017-11-21 | Avx Corporation | Solid electrolytic capacitor containing conductive polymer particles |
US9892862B2 (en) | 2013-05-13 | 2018-02-13 | Avx Corporation | Solid electrolytic capacitor containing a pre-coat layer |
US9472350B2 (en) | 2013-05-13 | 2016-10-18 | Avx Corporation | Solid electrolytic capacitor containing a multi-layered adhesion coating |
JP6250340B2 (ja) * | 2013-09-18 | 2017-12-20 | テイカ株式会社 | 正孔輸送材料、エレクトロルミネッセンス素子および薄膜太陽電池 |
EP2940079B1 (en) * | 2014-04-30 | 2017-08-23 | Agfa-Gevaert | Non-aqueous dispersions of a conductive polymer |
EP3024042B1 (en) | 2014-11-21 | 2017-07-19 | Heraeus Deutschland GmbH & Co. KG | PEDOT in perovskite solar cells |
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US10014108B2 (en) | 2015-03-13 | 2018-07-03 | Avx Corporation | Low profile multi-anode assembly |
US9928963B2 (en) | 2015-03-13 | 2018-03-27 | Avx Corporation | Thermally conductive encapsulant material for a capacitor assembly |
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US9754730B2 (en) | 2015-03-13 | 2017-09-05 | Avx Corporation | Low profile multi-anode assembly in cylindrical housing |
US20210210691A1 (en) * | 2015-12-24 | 2021-07-08 | Dow Global Technologies Llc | Polymeric layer and organic electronic device comprising same. |
WO2017200936A1 (en) * | 2016-05-19 | 2017-11-23 | Kemet Electronics Corporation | Polyanion copolymers for use with conducting polymers in solid electrolytic capacitors |
US11396594B2 (en) * | 2016-05-19 | 2022-07-26 | Kemet Electronics Corporation | Formulation for use with conducting polymers in solid electrolytic capacitors |
US10431389B2 (en) | 2016-11-14 | 2019-10-01 | Avx Corporation | Solid electrolytic capacitor for high voltage environments |
CN109119180A (zh) * | 2017-06-22 | 2019-01-01 | 宁德时代新能源科技股份有限公司 | 导电材料、电极片及电化学储能装置 |
US10943742B2 (en) * | 2017-10-18 | 2021-03-09 | Kemet Electronics Corporation | Conductive polymer dispersion for improved reliability |
WO2020033817A1 (en) | 2018-08-10 | 2020-02-13 | Avx Corporation | Solid electrolytic capacitor containing polyaniline |
WO2020033819A1 (en) | 2018-08-10 | 2020-02-13 | Avx Corporation | Solid electrolytic capacitor containing an intrinsically conductive polymer |
US11081288B1 (en) | 2018-08-10 | 2021-08-03 | Avx Corporation | Solid electrolytic capacitor having a reduced anomalous charging characteristic |
WO2020033820A1 (en) | 2018-08-10 | 2020-02-13 | Avx Corporation | Solid electrolytic capacitor formed from conductive polymer particles |
US11380492B1 (en) | 2018-12-11 | 2022-07-05 | KYOCERA AVX Components Corporation | Solid electrolytic capacitor |
WO2020123577A1 (en) | 2018-12-11 | 2020-06-18 | Avx Corporation | Solid electrolytic capacitor containing an intrinsically conductive polymer |
CN113853662B (zh) | 2019-05-17 | 2023-08-04 | 京瓷Avx元器件公司 | 固体电解电容器 |
DE112020004416T5 (de) | 2019-09-18 | 2022-06-15 | KYOCERA AVX Components Corporation | Festelektrolytkondensator zur Verwendung bei hohen Spannungen |
CN110818863B (zh) * | 2019-11-01 | 2021-08-17 | 中国科学院长春应用化学研究所 | 一种基于聚噻吩的两亲嵌段聚合物、其制备方法和电活性胶束 |
DE112020006024T5 (de) | 2019-12-10 | 2022-10-06 | KYOCERA AVX Components Corporation | Tantalkondensator mit erhöhter Stabilität |
US11756742B1 (en) | 2019-12-10 | 2023-09-12 | KYOCERA AVX Components Corporation | Tantalum capacitor with improved leakage current stability at high temperatures |
WO2021119065A1 (en) | 2019-12-10 | 2021-06-17 | Avx Corporation | Solid electrolytic capacitor containing a pre-coat and intrinsically conductive polymer |
US11763998B1 (en) | 2020-06-03 | 2023-09-19 | KYOCERA AVX Components Corporation | Solid electrolytic capacitor |
US11631548B2 (en) | 2020-06-08 | 2023-04-18 | KYOCERA AVX Components Corporation | Solid electrolytic capacitor containing a moisture barrier |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI235171B (en) * | 2001-03-29 | 2005-07-01 | Agfa Gevaert | Aqueous composition containing a polymer or copolymer of a 3,4-dialkoxythiophene and a non-Newtonian binder for use in a method for preparing a conductive layer |
CN1654506A (zh) * | 2004-02-10 | 2005-08-17 | H.C.施塔克股份有限公司 | 用于改进有机发光二极管的聚噻吩制剂 |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3843412A1 (de) * | 1988-04-22 | 1990-06-28 | Bayer Ag | Neue polythiophene, verfahren zu ihrer herstellung und ihre verwendung |
EP0440957B1 (de) | 1990-02-08 | 1996-03-27 | Bayer Ag | Neue Polythiophen-Dispersionen, ihre Herstellung und ihre Verwendung |
EP1801143B1 (en) * | 2000-06-26 | 2009-03-11 | Agfa-Gevaert | Redispersible latex comprising a polythiophene |
DE10111790A1 (de) * | 2001-03-12 | 2002-09-26 | Bayer Ag | Neue Polythiophen-Dispersionen |
EP1390422B1 (en) * | 2001-03-29 | 2004-11-03 | Agfa-Gevaert | Thiophenes and polymers derived therefrom |
KR100875219B1 (ko) * | 2001-06-22 | 2008-12-19 | 아그파-게바에르트 | 전기전도성 패턴 형성용 물질 및 전기전도성 패턴 형성 방법 |
KR100936426B1 (ko) | 2001-12-04 | 2010-01-12 | 아그파-게바에르트 | 폴리티오펜 또는 티오펜 공중합체의 수성 또는 비수성의용액 또는 분산액을 제조하는 방법 |
MXPA05010361A (es) * | 2003-04-02 | 2005-11-17 | Starck H C Gmbh | Agentes de oxidacion especificos para producir polimeros conductores. |
DE10324534A1 (de) * | 2003-04-02 | 2004-10-14 | H.C. Starck Gmbh | Retardierende Oxidationsmittel zur Herstellung leitfähiger Polymere |
JP4387131B2 (ja) | 2003-06-30 | 2009-12-16 | 富山薬品工業株式会社 | 導電性高分子物質の有機溶剤分散液及びその製造方法 |
DE102004022110A1 (de) * | 2004-05-05 | 2005-12-01 | H.C. Starck Gmbh | Verfahren zur Herstellung von Elektrolytkondensatoren |
US7985490B2 (en) * | 2005-02-14 | 2011-07-26 | Samsung Mobile Display Co., Ltd. | Composition of conducting polymer and organic opto-electronic device employing the same |
CN101309949B (zh) * | 2005-11-17 | 2012-05-09 | 长濑化成株式会社 | 聚(3,4-二烷氧基噻吩)和聚阴离子的复合体的水分散体的制造方法 |
DE102005060159A1 (de) * | 2005-12-14 | 2007-06-21 | H. C. Starck Gmbh & Co. Kg | Transparente polymere Elektrode für elektro-optische Aufbauten |
DE102006002798A1 (de) * | 2006-01-20 | 2007-08-09 | H. C. Starck Gmbh & Co. Kg | Polythiophenformulierungen zur Verbesserung von organischen Leuchtdioden |
JP5374841B2 (ja) | 2006-07-18 | 2013-12-25 | 荒川化学工業株式会社 | 導電性高分子/ドーパント錯体有機溶媒分散体、その製造方法および当該導電性高分子/ドーパント錯体有機溶媒分散体を含有する組成物 |
JP4975403B2 (ja) * | 2006-09-08 | 2012-07-11 | 信越ポリマー株式会社 | 導電性高分子溶液及び導電性塗膜 |
-
2008
- 2008-05-09 DE DE102008023008A patent/DE102008023008A1/de not_active Ceased
-
2009
- 2009-04-20 US US12/991,050 patent/US8721929B2/en active Active
- 2009-04-20 EP EP09741970.9A patent/EP2286416B1/de active Active
- 2009-04-20 KR KR1020107026362A patent/KR101575918B1/ko active IP Right Grant
- 2009-04-20 WO PCT/EP2009/054650 patent/WO2009135752A1/de active Application Filing
- 2009-04-20 JP JP2011507861A patent/JP5815401B2/ja active Active
- 2009-04-20 CN CN200980126271.9A patent/CN102089831B/zh active Active
- 2009-05-08 TW TW098115216A patent/TWI447163B/zh active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI235171B (en) * | 2001-03-29 | 2005-07-01 | Agfa Gevaert | Aqueous composition containing a polymer or copolymer of a 3,4-dialkoxythiophene and a non-Newtonian binder for use in a method for preparing a conductive layer |
CN1654506A (zh) * | 2004-02-10 | 2005-08-17 | H.C.施塔克股份有限公司 | 用于改进有机发光二极管的聚噻吩制剂 |
Non-Patent Citations (1)
Title |
---|
3、Tae-Woo Lee, O Ok Park, Lee-Mi Do, Taehyoung Zyung, Taek Ahn, and Hong-Ku Skim, Polymer light-emitting devices using ionomers as an electron injecting and hole blocking layer, Journal of Applied Physics, American Institute of Physics, 2001, V90 N5, P2128-2134 * |
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