TWI488868B - 用於製造導電聚合物之方法 - Google Patents
用於製造導電聚合物之方法 Download PDFInfo
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- TWI488868B TWI488868B TW098102153A TW98102153A TWI488868B TW I488868 B TWI488868 B TW I488868B TW 098102153 A TW098102153 A TW 098102153A TW 98102153 A TW98102153 A TW 98102153A TW I488868 B TWI488868 B TW I488868B
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- TW
- Taiwan
- Prior art keywords
- polythiophene
- polyanion
- substituted
- aqueous
- unsubstituted
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229920001940 conductive polymer Polymers 0.000 title description 18
- 229920000123 polythiophene Polymers 0.000 claims description 48
- 239000006185 dispersion Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 37
- 125000002091 cationic group Chemical group 0.000 claims description 18
- 229920000447 polyanionic polymer Polymers 0.000 claims description 18
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- 229940005642 polystyrene sulfonic acid Drugs 0.000 claims description 11
- 239000012429 reaction media Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- -1 polyphenylenes Polymers 0.000 description 39
- 239000000243 solution Substances 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 239000002904 solvent Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 150000001450 anions Chemical class 0.000 description 12
- 229930192474 thiophene Natural products 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 150000003577 thiophenes Chemical class 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
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- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 5
- HVOAFLJLVONUSZ-UHFFFAOYSA-N 2-ethylperoxythiophene Chemical compound CCOOC1=CC=CS1 HVOAFLJLVONUSZ-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 3
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- 150000007513 acids Chemical class 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
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- 238000003756 stirring Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 125000006833 (C1-C5) alkylene group Chemical group 0.000 description 2
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 2
- RHUYHJGZWVXEHW-UHFFFAOYSA-N 1,1-Dimethyhydrazine Chemical compound CN(C)N RHUYHJGZWVXEHW-UHFFFAOYSA-N 0.000 description 2
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 description 2
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 2
- RALRVIPTUXSBPO-UHFFFAOYSA-N 4-[4-chloro-3-(trifluoromethyl)phenyl]piperidin-4-ol Chemical compound C=1C=C(Cl)C(C(F)(F)F)=CC=1C1(O)CCNCC1 RALRVIPTUXSBPO-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
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- 230000002378 acidificating effect Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
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- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
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- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
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- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
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- SXPGQGNWEWPWQZ-UHFFFAOYSA-N 4-(triethoxymethyl)dodecan-1-amine Chemical compound NCCCC(C(OCC)(OCC)OCC)CCCCCCCC SXPGQGNWEWPWQZ-UHFFFAOYSA-N 0.000 description 1
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- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229960002380 dibutyl phthalate Drugs 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- CJMZLCRLBNZJQR-UHFFFAOYSA-N ethyl 2-amino-4-(4-fluorophenyl)thiophene-3-carboxylate Chemical compound CCOC(=O)C1=C(N)SC=C1C1=CC=C(F)C=C1 CJMZLCRLBNZJQR-UHFFFAOYSA-N 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 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
- 238000000265 homogenisation Methods 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 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
- 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 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 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
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-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
- 125000000962 organic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000003544 oxime group Chemical group 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
- GJVFBWCTGUSGDD-UHFFFAOYSA-L pentamethonium bromide Chemical compound [Br-].[Br-].C[N+](C)(C)CCCCC[N+](C)(C)C GJVFBWCTGUSGDD-UHFFFAOYSA-L 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
- JGTNAGYHADQMCM-UHFFFAOYSA-N perfluorobutanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-N 0.000 description 1
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-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
- PJGSXYOJTGTZAV-UHFFFAOYSA-N pinacolone Chemical compound CC(=O)C(C)(C)C PJGSXYOJTGTZAV-UHFFFAOYSA-N 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 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
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate 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
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 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
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical group [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003568 thioethers Chemical group 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- GBXQPDCOMJJCMJ-UHFFFAOYSA-M trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C GBXQPDCOMJJCMJ-UHFFFAOYSA-M 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical class OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
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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
- 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
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- 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
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Description
本發明係關於一種用於在聚陰離子之存在下製備導電聚合物之新穎方法、關於經由此種方法而製備之水性或非水性分散液或溶液及關於彼等之用途。
由於關於加工性、關於重量及關於性質經由化學修飾之受控制之調節,聚合物具有優於金屬之優點,因此導電聚合物獲得逐漸增加之經濟重要性。已為吾人所知之π-共軛聚合物之實例係聚吡咯類、聚噻吩類、聚苯胺類、聚乙炔類、聚伸苯基類及聚(對伸苯基-伸乙烯基類)。導電聚合物之層具有多種工業用途,例如作為於電容器中之聚合之對極電極(counterelectrode)、作為抗靜電之塗膜及用於電子電路板之貫穿接觸(through-contacting)。
導電聚合物係經由自單體先質(例如視需要經取代噻吩類、吡咯類及苯胺類及可係低聚合之彼等之分別之衍生物類)之化學或電化學,氧化之方法而製備。尤其以化學之方式氧化之聚合作用係普及的,此因為於液體介質中及於多種基材上達成聚合作用係技術上容易之緣故。
一種特別重要並且工業上使用之聚噻吩係聚(伸乙基-3,4-二氧基噻吩)(PEDOT或PEDT),其係經由以化學之方式聚合伸乙基-3,4-二氧基噻吩(EDOT或EDT)而製備及其,於其之已經氧化之形式中,具有很高之導電係數及係,例如,於EP 339 340 A2中敍述。多種聚(伸烷基-3,4-二氧基噻吩)衍生物(尤其聚(伸乙基-3,4-二氧基噻吩)衍生物)、及單體單元、其等之合成及應用之縱覽係由L. Groenendaal,F. Jonas,D. Freitag,H. Pielartzik & J. R. Reynolds,Adv. Mater.12,
(2000)p. 481-494提供。
特殊之工業重要性係已經由PEDOT以聚苯乙烯磺酸(PSS)之分散液而獲得,如例如,於EP 0440 957中敍述。WO 2007/031206敍述用於電容器之內部浸漬之低黏度PEDOT/PSS分散液之製備。於該處敍述之製造方法具有長反應時間,及因此,於分散液之製備後,需要另外之方法階段以降低該分散液之黏度(例如經由高壓均質化作用)之缺點。
因此,對於用於製備具有低黏度之導電聚合物之方法,仍然具有需要。
因此提供此種方法係本發明之一種目的。
令人驚訝地,頃已發現,當具有低黏度之導電聚合物之製備係以超聲波輻射實施時,可於短暫之反應時間內製備該等導電聚合物-無另外之方法步驟。
本發明因此提供一種用於製備包含至少一種導電聚合物與至少一種聚陰離子之水性或非水性分散液或溶液之方法,其特徵為該聚合作用係以超聲波輻射進行。
於本發明之情況中,導電聚合物可係視需要經取代之聚吡咯類、視需要經取代之聚苯胺類或視需要經取代之聚噻吩類。其亦可係經由根據本發明之方法而製備之兩種或兩種以上之此等導電聚合物之混合物。
特別較佳之導電聚合物類係包含通式(I)之重複單元之視需要經取代之聚噻吩類
其中R1
及R2
各自獨立地係H、視需要經取代之C1
-C18
-烷基或視需要經取代之C1
-C18
-烷氧基,或R1
及R2
共同地係視需要經取代之C1
-C8
-伸烷基(其中一個或一個以上碳原子可係由一個或一個以上選自O及S之相同或不同之雜原子所取代,較佳地C1
-C8
-二氧基伸烷基、視需要經取代之C1
-C8
-氧基硫基伸烷基或視需要經取代之C1
-C8
-二硫基伸烷基)、或其中至少一個碳原子可係視需要由一個選自O及S之雜原子所取代之視需要經取代之C1
-C8
-亞烷基
於較佳之具體實施例中,包含通式(I)之重複單元之聚噻吩類係包含通式(I-a)之重複單元及/或通式(I-b)之重複單元者
其中A 係視需要經取代之C1
-C5
-伸烷基,較佳地視需要經取代之C2
-C3
-伸烷基,Y 係O或S,R 係線性或分枝,視需要經取代之C1
-C18
-烷基(較佳地線性或分枝,視需要經取代之C1
-C14
-烷基)、視需要經取代之C5
-C12
-環烷基、視需要經取代之C6
-C14
-芳基、視需要經取代之C7
-C18
-芳烷基、視需要經取代之C1
-C4
-羥基烷基或羥基,x 係0至8之整數,較佳地0、1或2,更佳地0或1,及於該案例中複數個之R基係鍵結至A,彼等可係相同或不同的。
應瞭解,通式(I-a)係致使取代基R可係鍵結x次至伸烷基A者。
於另外之較佳具體實施例中,包含通式(I)之重複單元之聚噻吩類係包含通式(I-aa)之重複單元及/或通式(I-ab)之重複單元者
其中R及x各係如以上定義。
於再另外之較佳具體實施例中,包含通式(I)之重複單元之聚噻吩類係包含通式(I-aaa)之重複單元及/或通式(I-aba)之重複單元者。
於本發明之情況中,瞭解字首“聚”係致使超過一個相同或不同之重複單元存在於聚噻吩中者。聚噻吩類包含總量n個重複單元之通式(I),其中n可係2至2,000之整數,較佳地2至100。於聚噻吩之內,通式(I)之重複單元每個可係相同或不同的。較佳者係於各案例中包含通式(I)之相同之重複單元之聚噻吩類。
於端基上,於各案例中聚噻吩類較佳地具有H。
於特別較佳之具體實施例中,具有通式(I)之重複單元之聚噻吩係聚(3,4-伸乙基二氧基噻吩)、聚(3,4-伸乙基氧基硫基噻吩)或聚(噻吩并[3,4-b]噻吩),即由式(I-aaa)、(I-aba)或(I-b)之重複單元組成之同元聚噻吩,其中於式(I-b)中之Y係S。
於另外之特別較佳之具體實施例中,具有通式(I)之重複單元之聚噻吩係自式(I-aaa)與(I-aba)、(I-aaa)與(I-b)、(I-aba)與(I-b)、或(I-aaa)、(I-aba)、與(I-b)之重複單元生成之共聚物,較佳者係自式(I-aaa)與(I-aba)、及亦(I-aaa)與(I-b)之重複單元生成之共聚物類。
於本發明之情況中,C1
-C5
-伸烷基A係亞甲基、伸乙基、正伸丙基、正伸丁基或正伸戊基;C1
-C8
-伸烷基另外係正伸己基、正伸庚基及正伸辛基。於本發明之情況中,C1
-C8
-亞烷基係包含至少一個雙鍵之以上列舉之C1
-C8
-伸烷基。於本發明之情況中,C1
-C8
-二氧基伸烷基、C1
-C8
-氧基硫基伸烷基及C1
-C8
-二硫基伸烷基係對應於以上列舉之C1
-C8
-伸烷基之C1
-C8
-二氧基伸烷基、C1
-C8
-氧基硫基伸烷基及C1
-C8
-二硫基伸烷基。於本發明之情況中,C1
-C18
-烷基代表線性或分枝之C1
-C18
-烷基,例如甲基、乙基、正或異丙基、正-、異-、第二-或第三-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、正十六基或正十八基,C5
-C12
-環烷基代表C5
-C12
-環烷基諸如環戊基、環己基、環庚基、環辛基、環壬基或環癸基,C6
-C14
-芳基代表C6
-C14
-芳基諸如苯基或萘基,及C7
-C18
-芳烷基代表C7
-C18
-芳烷基,例如苄基、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。於本發明之情況中,C1
-C18
-烷氧基係對應於以上列舉之C1
-C18
-烷基之烷氧基。以上之列舉發揮作用以實例之方式舉例說明本發明及不應被認為係排他的。
以上自由基之選用之另外取代基包括多種之有機基,例如烷基、環烷基、芳基、鹵素、醚、硫醚、二硫化物、亞碸、碸、磺酸基、胺基、醛、酮基、羧酸酯、羧酸、碳酸基、羧酸基、氰基、烷基矽烷及烷氧基矽烷基、及亦羧醯胺基。
上述之水性分散液或溶液(較佳地包含聚(伸烷基-3,4-二氧基噻吩)類)可係,例如,相似於EP 440 957中敘述之具有超聲波輻射之方法而製備。對於此種目的,例如,於反應介質中懸掛一種超聲波手指狀裝置(finger)係可能的。然而,泵送該反應介質通過超聲波流動室(flow cell),亦係可能的。此處,能量輸入可係於10與1,000W/升(w/l)之反應介質之間,較佳地於20與500W/升之反應介質之間,更佳地於20與200W/升之反應介質之間。
對於根據本發明之方法,使用於20與200kHz之間之超聲波頻率,較佳地於20與100kHz之間,更佳地於22與50kHz之間。有用之氧化劑及溶液同樣地包括於EP 440 957中列舉者。
於本發明之分散液之製備後,該等分散液較佳地係以鹼性及酸性之離子交換器處理,以移出無機鹽類。
於本發明之情況中,瞭解水性分散液或溶液係意表包含至少50重量百分點(重量%)之水(更佳地至少90重量%之水)、及視需要溶劑之分散液或溶液,該等溶劑係-至少部分地-與水互溶混的,諸如醇類(例如甲醇、乙醇、正丙醇、異丙醇、丁醇或辛醇)、二醇類及二醇醚類(例如乙二醇、二甘醇、1,2-丙二醇、1,3-丙二醇或二丙二醇二甲基醚)、或酮類(例如丙酮或甲基乙基酮)。於該水性分散液或溶液中,視需要經取代之聚噻吩類(尤其包含通式(I)之重複單元之視需要經取代之聚噻吩類)之固體含量可係於0.05與4.0重量%之間,較佳地於0.1與2.0重量%之間。
於本發明之情況中,瞭解低黏度分散液係意表一種分散液,其於1.0-1.5重量%之視需要經取代之聚噻吩類之固體含量,於各案例中具有於1與100mPas之間之以流變計於100/秒之切變速率測量之於20℃之黏度,較佳地於4與80mPas之間,更佳地於6與60mPas之間。
對於通式(I)之聚噻吩類及其衍生物類之製備,用於製備單體之先質之方法係已為熟悉此項技藝者所知的及係,例如,於L. Groenendaal,F. Jonas,D. Freitag,H. Pielartzik & J. R. Reynolds,Adv. Mater. 12(2000)481-494及於其中引用之文獻中敘述。
於本發明之情況中,瞭解以上提及之噻吩之衍生物類係意表,例如,此等噻吩之二聚物類或三聚物類。單體之先質之較高分子量衍生物類,即四聚物類、五聚物類、及其類似物,作為衍生物類亦係可能的。該等衍生物可係自相同或不同之單體單元生成,及係以純粹之形式或者以與另一種及/或與以上提及之噻吩類之混合物使用。於本發明之情況中,此等噻吩類及噻吩衍生物類之氧化及還原之形式亦係由術語“噻吩類及噻吩衍生物類”涵蓋,其限制條件為彼等之聚合作用生成與於以上列舉之噻吩類及噻吩衍生物類之案例中相同之導電聚合物。
該等噻吩可係視需要以溶液之形式使用。適合之溶劑特定言之包括於反應條件下係惰性之下列有機溶劑:脂族醇類諸如甲醇、乙醇、異丙醇及丁醇;脂族酮類諸如丙酮及甲基乙基酮;脂族羧酸酯類諸如乙酸乙酯及乙酸丁酯;芳族烴類諸如甲苯及二甲苯;脂族烴類諸如己烷、庚烷及環己烷;氯烴類諸如二氯甲烷及二氯乙烷;脂族腈類諸如乙腈;脂族亞碸類及碸類諸如二甲亞碸及環丁碸;脂族羧醯胺類諸如甲基乙醯胺、二甲基乙醯胺及二甲基甲醯胺;脂族及芳脂族醚類諸如二乙基醚及苯基甲基醚。此外,使用水或水與前述有機溶劑之混合物作為溶劑,亦係可能的。較佳之溶劑係醇類及水、及亦包含醇類或水之混合物、或醇類與水之混合物。於氧化作用條件下係液體之噻吩類亦可係於溶劑之不存在下聚合。
該水性分散液或溶液可另外包含至少一種聚合之黏合劑。適合之黏合劑係聚合之有機黏合劑,例如聚乙烯醇類、聚乙烯基吡咯啶酮類、聚氯乙烯類、聚乙酸乙烯酯類、聚丁酸乙烯酯類、聚丙烯酸酯類、聚丙烯醯胺類、聚甲基丙烯酸酯類、聚甲基丙烯醯胺類、聚丙烯腈類、苯乙烯/丙烯酸酯、乙酸乙烯酯/丙烯酸酯及乙烯/乙酸乙烯酯共聚物、聚丁二烯類、聚異戊二烯類、聚苯乙烯類、聚醚類、聚酯類、聚碳酸酯類、聚胺甲酸乙酯類、聚醯胺類、聚醯亞胺類、聚環丁碸類、三聚氰胺-甲醛樹脂類、環氧樹脂類、聚矽氧樹脂類或纖維素類。聚合之黏合劑之固體含量係於0與5.0重量%之間,較佳地於0與2.0重量%之間。
該分散液或溶液可另外包含黏附促進劑,例如有機官能之矽烷類或其等之水解產物,例如3-去水甘油基氧基丙基三烷氧基矽烷、3-胺基丙基三乙氧基矽烷、3-氫硫基丙基三甲氧基矽烷、3-甲基丙醯基氧基丙基三甲氧基矽烷、乙烯基三甲氧基矽烷或辛基三乙氧基矽烷。
於本發明之情況中,包含至少一種導電聚合物(較佳地視需要經取代之聚噻吩類)、與至少一種聚陰離子之非水性分散液或溶液可係以相似於EP 1 373 356中揭示之方法製備:於第一方法階段中,經由根據本發明之方法製備水性分散液或溶液;於第二方法階段中,將與水互溶混之溶劑或與水互溶混之溶劑混合物加入此種水性分散液或溶液中,然後自生成之混合物至少部分地移出水及視需要以有機溶劑稀釋該混合物。關於此點,有用之溶劑係醯胺型溶劑類(例如甲醯胺、N-甲基乙醯胺、N,N-二甲基乙醯胺、N-甲基吡咯啶酮、N-甲基己內醯胺或N-甲基甲醯胺)、醇類及醚類(例如乙二醇、丙三醇、乙二醇二甲基醚、乙二醇單甲基醚、乙二醇單丁基醚或二烷)。較佳者係醯胺型溶劑及於標準壓力具有超過100℃之沸點之溶劑、及與水形成共沸液之與水互溶混之溶劑或與水互溶混之溶劑混合物。可移出該水,例如,經由薄膜方法諸如超過濾、或經由蒸餾。倘若具有以有機溶劑之稀釋作用,則較佳之溶劑係以上提及之溶劑類及脂族醇類(例如甲醇、乙醇、正丙醇、異丙醇、正丁醇、異丁醇、第三丁醇、戊醇、異戊醇、新戊醇)、脂族酮類(例如丙酮、甲基乙基酮、甲基異丁基酮、甲基第三丁基酮)、醚類(例如四氫呋喃、甲基第三丁基醚)、脂族及芳族羧酸之酯類(例如乙酸乙酯、乙酸丁酯、乙二醇單甲基醚乙酸酯、酞酸丁酯)、或脂族或芳族烴類(諸如戊烷、己烷、環己烷、辛烷、異辛烷、癸烷、甲苯、鄰二甲苯、間二甲苯或對二甲苯)。
該等導電聚合物類,尤其該等聚噻吩類,可係不帶電荷的或陽離子型的。於較佳具體實施例中,彼等係陽離子型的,“陽離子型的”僅係關於存在於聚噻吩主鏈上之電荷。根據於R基上之取代基,聚噻吩於結構單元中可帶有正及負電荷,於該案例中正電荷係存在於聚噻吩主鏈上及負電荷,倘若存在,則於經由磺酸基或羧酸基而取代之R基上。聚噻吩主鏈之正電荷可係經由陰離子基(其等可係存在於R基上)而部分地或完全地飽和。整體觀之,於此等案例中之聚噻吩類可係陽離子型的、不帶電荷的或甚至陰離子型的。雖然如此,於本發明之情況中,因為於聚噻吩主鏈上之正電荷係有決定性的,因此彼等皆被認為係陽離子型聚噻吩。由於正電荷之精確數目及位置不能明白地陳述,因此於式中不顯示正電荷。然而,正電荷之數目係至少1及最多n,其中n係於聚噻吩之內之所有重複單元(相同或不同的)之總數目。
為了補償該正電荷,倘若此尚未經由視需要以磺酸基或以羧酸基取代及因此帶負電荷之R基而達成,則該陽離子型聚噻吩類需要陰離子作為相對離子。
有用之相對離子包括單體或聚合之陰離子,於後文中後者亦如聚陰離子提及。
使用之單體之陰離子係,例如,屬於C1
-C20
-烷烴磺酸類(諸如甲烷-、乙烷-、丙烷-或丁烷磺酸、或高級磺酸,諸如十二烷磺酸)者、屬於脂族全氟磺酸類(諸如三氟甲烷磺酸、全氟丁烷磺酸或全氟辛烷磺酸)者、屬於脂族C1
-C20
-羧酸類諸如2-乙基己基甲酸者、屬於脂族全氟羧酸類(諸如三氟乙酸或全氟辛酸)者、及屬於視需要以C1
-C20
-烷基取代之芳族磺酸類(諸如苯磺酸、鄰甲苯磺酸、對甲苯磺酸、十二基苯磺酸、二壬基萘磺酸或二壬基萘二磺酸)者、及屬於環烷烴磺酸類諸如樟腦磺酸、或四氟硼酸鹽類、六氟磷酸鹽類、過氯酸鹽類、六氟銻酸鹽類、六氟砷酸鹽類或六氯銻酸鹽類者。
特別較佳者係對甲苯磺酸、甲烷磺酸或樟腦磺酸之陰離子。
所使用之氧化劑之陰離子或於還原作用後自其生成之陰離子充當相對離子,致使另外之相對離子之添加不是絕對必要,亦係可能的。
較佳之聚合之陰離子係,例如,聚合之羧酸類(諸如聚丙烯酸類、聚甲基丙烯酸類或聚順丁烯二酸類)、或聚合之磺酸類(諸如聚苯乙烯磺酸類及聚乙烯磺酸類)之陰離子。此等聚羧酸類及聚磺酸類亦可係乙烯基羧酸類及乙烯基磺酸類與其他可聚合之單體(諸如丙烯酸酯類及苯乙烯)之共聚物類。彼等亦可係,例如,包含SO3 -
M+
或COO-
M+
基團之已經部分地氟化或已經全氟化之聚合物類,其中M+
係,例如,Li+
、Na+
、K+
、Rb+
、Cs+
或NH4 +
,較佳地H+
、Na+
或K+
。
一種特別較佳之聚合之陰離子係作為相對離子之聚苯乙烯磺酸(PSS)之陰離子。
產生聚陰離子之聚酸類之分子量較佳地係1,000至2,000,0000,更佳地2,000至500,0000。該等聚酸類或彼等之鹼金屬鹽類係市售的,例如聚苯乙烯磺酸類及聚丙烯酸類,或者係經由已為吾人所知之方法而可製備的(見,例如,Houben Weyl,Methoden der organischen Chemie[Methods of organic chemistry],Vol. E 20 Makromolekulare Stoffe[Macromolecular substances],part 2,(1987),P. 1141 ff.)。
於技術領域中,作為用於電荷補償之相對離子之包含陰離子之陽離子型聚噻吩類時常亦係如聚噻吩/(聚)陰離子複合物提及。
該聚合作用較佳地係於0-35℃之範圍內之溫度進行,更佳地於5-25℃之範圍內之溫度及最佳地於10-20℃之範圍內之溫度。
聚合作用時間係於0.1與48小時之間,較佳地於0.5與24小時之間,更佳地於1.0與10小時之間。
本發明進一步提供一種用於製備包含至少一種導電聚合物與至少一種聚陰離子之水性或非水性分散液或溶液之方法,其特徵為該方法包含下列階段:
1) 僅於已經以惰性氣體之協助使反應介質變成惰性之後將至少一種氧化劑加入,
2) 以超聲波輻射進行該聚合作用。
於本發明之情況中,當惰性氣體已流動通過反應介質歷時至少5分鐘(較佳地至少20分鐘)後,認為該反應介質係已變成惰性。適合之惰性氣體係,例如,氬、氦或氮。當已降低反應容器之內壓力至少一次及隨後已經由將惰性氣體加入而升高該內壓力時,亦認為反應介質係已變成惰性。
DE 10 2007 041722.7,其於本發明之專利優先權日期(priority date)時係尚未公告,敍述導電聚合物於降低之壓力下之製備。
本發明再進一步提供一種用於製備包含至少一種導電聚合物與至少一種聚陰離子之水性或非水性分散液或溶液之方法,其特徵為該方法包含下列階段:於比大氣壓力較低之壓力及以超聲波輻射進行該聚合作用。
此處該聚合作用較佳地係於低於800hPa之壓力進行,較佳地低於200hPa,最佳地低於50hPa。
對於根據本發明之此等兩種另外方法,如同對於載明之根據本發明之第一種方法,應用相同之較佳範圍,例如對於至少一種導電聚合物、至少一種聚陰離子及超聲波輻射。
於本發明之情況中,為了增進水性或非水性分散液或溶液之傳導係數,添加傳導係數增進劑諸如二甲亞碸,係可能的。然而,亦可使用其他傳導係數增進劑作為於本發明之情況中之傳導係數增進劑,如於EP 0686662中或由Ouyang等人,Polymer,45(2004),p. 8443-8450揭示。可獲得之傳導係數可係至多2,000S/cm,較佳地至多1,000S/cm。
本發明進一步提供經由根據本發明之方法而製備之水性或非水性分散液或溶液,及亦此等水性或非水性分散液或溶液用於製造導電塗膜之用途。如此製造之塗膜之傳導係數係至少150S/cm,較佳地至少200S/cm。
隨後之實例僅發揮作用以實例之方式舉例說明本發明及不應解釋如一種限制。
最初以79.74克之水及0.39克之3,4-伸乙基二氧基噻吩裝載具有冷卻套之200毫升玻璃容器。乳液係於水冷卻下藉由磁性攪拌器攪拌。其後,將15.03克之具有70,000克/莫耳之平均分子量Mw
及5%之固體含量之水性聚苯乙烯磺酸、溶解於3.87克之水中之0.22克之硫酸鐵(Ⅲ)、及0.76克之過氧二硫酸鈉加入。其後於水冷卻下藉由磁性攪拌器攪拌反應混合物歷時另外3小時,於其過程中該分散液變成很黏性。於已關閉磁性攪拌器後,溶液形成乳膠體(gelated)。
最初以79.74克之水及0.39克之3,4-伸乙基二氧基噻吩裝載具有冷卻套之200毫升玻璃容器。以超聲波手指狀裝置(24kHz,功率100W,Hielscher UP 200 S超聲波處理器)乳化該乳液同時以水外部地冷卻歷時15分鐘。其後,將15.03克之具有70,000克/莫耳之平均分子量Mw
及5%之固體含量之水性聚苯乙烯磺酸、溶解於3.87克之水中之0.22克之硫酸鐵(Ⅲ)、及0.76克之過氧二硫酸鈉加入。其後反應混合物係以超聲波手指狀裝置(Hielscher UP 200 S超聲波處理器,24kHz,功率100W)照射同時以水外部地冷卻歷時另外3小時。於此時間內,反應溫度自20℃升高至35℃。於已結束反應之後,分散液係經由添加26克之Lewatit MP 62(鹼性離子交換器,Lanxess AG)及45克之Lewatit S 100(酸性離子交換器,Lanxess AG)連同藉由磁性攪拌器之攪拌歷時2小時而脫鹽,不使用超聲波。然後通過濾布過濾出離子交換器。
如此獲得之本發明之PEDOT/PSS分散液具有1.0重量%之固體含量及於100/秒之切變速率之7.9mPas之黏度(以流變計於20℃測量)。
將19克之此種分散液與1克之二甲亞碸摻和。將一片清潔之玻璃基板置於旋轉塗布器上,及將10毫升之上述之混合物分佈於該基板上。其後,經由旋轉該板而通過離心力作用旋轉拋出(spun off)上層澄清溶液。其後,於130℃之熱板上乾燥如此塗布之基板歷時15分鐘。層厚度係70奈米(Tencor,Alphastep 500)。
傳導係數係經由於10毫米之距離藉由一種遮蔽屏(shadowmask)施加長度2.5厘米之銀電極而測定。以層厚度乘以用靜電計(Keithly 614)測定之表面電阻,俾能獲得電阻率(electrical specific resistivity)。該層之電阻率係0.005747ohm‧cm。此相當於174S/cm之傳導係數。如此製造之層係透明的。
最初經由沈管,以1,389克之去離子水裝載具有冷卻套、攪拌器、氮入口及出口、液體入口及出口之2升之於攪拌中之容器。其後,將74.4克之具有70,000克/莫耳之平均分子量Mw
之25%之聚苯乙烯磺酸水溶液加入。溶液係經由於攪拌下引進氮歷時2小時而除去氧。於氮之下將7.4克之3,4-伸乙基二氧基噻吩之加入之後,溶液係於攪拌下以10升/小時之速率泵送通過一種來自Dr. Hielscher GmbH,Stuttgart之超聲波流動室(Flow Cell D22K,Ultrasonic Processor UP400S)及以400W之功率、24kHz之超聲波照射歷時30分鐘。其後,於氮之下將溶解於80克之水中之0.14克之硫酸鐵(Ⅲ)與10.0克之過氧二硫酸鈉加入。溶液係於攪拌下泵送通過該超聲波流動室及照射歷時另外之3小時。其後,於氮之下將溶解於80克之水中之8.4克之過氧二硫酸鈉加入,及溶液係於攪拌下泵送通過該超聲波流動室及照射歷時另外之8小時。於整個反應時間之期間,溶液係經由外部冷卻而維持於25℃。
於反應之完成後,分散液係排出及經由添加172克之Lewatit MP 62(鹼性離子交換器,Lanxess AG)及148克之Lewatit S 100(酸性離子交換器,Lanxess AG)連同藉由磁性攪拌器之攪拌歷時2小時而脫鹽,不使用超聲波。通過濾布過濾出離子交換器。
如此獲得之本發明之PEDOT/PSS分散液具有1.35重量%之固體含量及於100/秒之切變速率之55mPas之黏度(以流變計於20℃測量)。電傳導係數係如以上敍述於添加二甲亞碸之後測定及係245S/cm。
Claims (10)
- 一種用於製備包含至少一種陽離子型聚噻吩與至少一種聚陰離子之水性或非水性分散液或溶液之方法,其中該陽離子型聚噻吩與該聚陰離子係以聚噻吩/聚陰離子-複合物形式存在,其特徵為該陽離子型聚噻吩係在聚陰離子存在下製得,且該聚合作用係以超聲波輻射進行。
- 一種用於製備包含至少一種陽離子型聚噻吩與至少一種聚陰離子之水性或非水性分散液或溶液之方法,其中該陽離子型聚噻吩與該聚陰離子係以聚噻吩/聚陰離子-複合物形式存在,其特徵為該陽離子型聚噻吩係在聚陰離子存在下製得,且該方法包含下列階段:1)僅於已經以惰性氣體之協助使該反應介質變成惰性之後將至少一種氧化劑加入,2)以超聲波輻射進行該聚合作用。
- 一種用於製備包含至少一種陽離子型聚噻吩與至少一種聚陰離子之水性或非水性分散液或溶液之方法,其中該陽離子型聚噻吩與該聚陰離子係以聚噻吩/聚陰離子-複合物形式存在,其特徵為該陽離子型聚噻吩係在聚陰離子存在下製得,且該方法包含下列階段:於低於大氣壓力之壓力及以超聲波輻射進行該聚合作用。
- 如申請專利範圍第1至3項中任一項之方法,其特徵為該至少一種陽離子型聚噻吩係包含通式(I)之重複單 元之經取代或未經取代之聚噻吩
- 如申請專利範圍第4項之方法,其特徵為該至少一種陽離子型聚噻吩係包含通式(I-aaa)之重複單元、通式(I-aba)之重複單元、或通式(I-aaa)與通式(I-aba)之重複單元之聚噻吩
- 如申請專利範圍第5項之方法,其特徵為該聚陰離子係聚苯乙烯磺酸。
- 如申請專利範圍第1至3項中任一項之方法,其特徵為將傳導係數增進劑加入該水性或非水性分散液中。
- 如申請專利範圍第1至3項中任一項之方法,其中得自該方法之分散液或溶液於20℃下具有於1與100mPas之間之黏度,其係以流變計於100/秒之切變速率、於1.0-1.5重量%之聚噻吩類之固體含量下測量。
- 一種水性或非水性分散液或溶液,其係根據申請專利範圍第1至3項中任一項之方法製備。
- 一種根據申請專利範圍第9項之水性或非水性分散液或溶液之用途,其係用於製造導電塗膜。
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2008
- 2008-01-22 DE DE102008005568A patent/DE102008005568A1/de not_active Ceased
- 2008-12-18 KR KR1020107018612A patent/KR101561595B1/ko active IP Right Grant
- 2008-12-18 US US12/864,007 patent/US8721928B2/en active Active
- 2008-12-18 CN CN2008801281931A patent/CN101977960A/zh active Pending
- 2008-12-18 JP JP2010543406A patent/JP5485174B2/ja active Active
- 2008-12-18 EP EP08871431.6A patent/EP2238194B1/de active Active
- 2008-12-18 WO PCT/EP2008/067884 patent/WO2009092503A1/de active Application Filing
-
2009
- 2009-01-21 TW TW098102153A patent/TWI488868B/zh active
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2014
- 2014-02-19 JP JP2014029854A patent/JP2014159567A/ja active Pending
Patent Citations (2)
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US5300575A (en) * | 1990-02-08 | 1994-04-05 | Bayer Aktiengesellschaft | Polythiophene dispersions, their production and their use |
CN1839448A (zh) * | 2003-06-20 | 2006-09-27 | 爱克发-格法特公司 | 制备导电涂层的方法 |
Non-Patent Citations (2)
Title |
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W. M. de Azevedo, R. A. de Barros and E. F. da Silva Jr, "Conductive polymer preparation under extreme or non-classical conditions", J. Mater Sci, 2008, Vol. 43, pages 1400-1405. * |
Weikuan Li, Juan Chen, Junjun Zhao, Jianrong Zhang and Junjie Zhu,"Application of ultrasonic irradiation in preparing conducting polymer as active materials for supercapacitor", Materials Letters, 2005, Vol. 59, pages 800-803 * |
Also Published As
Publication number | Publication date |
---|---|
EP2238194A1 (de) | 2010-10-13 |
CN101977960A (zh) | 2011-02-16 |
EP2238194B1 (de) | 2018-02-07 |
KR20110014554A (ko) | 2011-02-11 |
JP2014159567A (ja) | 2014-09-04 |
US8721928B2 (en) | 2014-05-13 |
KR101561595B1 (ko) | 2015-10-20 |
JP2011510141A (ja) | 2011-03-31 |
JP5485174B2 (ja) | 2014-05-07 |
WO2009092503A1 (de) | 2009-07-30 |
DE102008005568A1 (de) | 2009-07-23 |
US20110049433A1 (en) | 2011-03-03 |
TW200944543A (en) | 2009-11-01 |
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