JP4283815B2 - Aqueous solution and organic solution containing conductive polymer, and support containing conductive polymer obtained from the solution - Google Patents
Aqueous solution and organic solution containing conductive polymer, and support containing conductive polymer obtained from the solution Download PDFInfo
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- JP4283815B2 JP4283815B2 JP2006060238A JP2006060238A JP4283815B2 JP 4283815 B2 JP4283815 B2 JP 4283815B2 JP 2006060238 A JP2006060238 A JP 2006060238A JP 2006060238 A JP2006060238 A JP 2006060238A JP 4283815 B2 JP4283815 B2 JP 4283815B2
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- Japan
- Prior art keywords
- group
- general formula
- conductive polymer
- sulfonic acid
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 229920001940 conductive polymer Polymers 0.000 title claims description 29
- 239000007864 aqueous solution Substances 0.000 title claims description 15
- 239000000243 solution Substances 0.000 title claims description 11
- 239000002152 aqueous-organic solution Substances 0.000 title 1
- 125000001424 substituent group Chemical group 0.000 claims description 30
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 30
- 229920001577 copolymer Polymers 0.000 claims description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 13
- 125000003545 alkoxy group Chemical group 0.000 claims description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- 229910052736 halogen Inorganic materials 0.000 claims description 12
- 150000002367 halogens Chemical class 0.000 claims description 12
- 229920006395 saturated elastomer Polymers 0.000 claims description 12
- 125000005907 alkyl ester group Chemical group 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 150000001768 cations Chemical class 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 6
- 150000001204 N-oxides Chemical class 0.000 claims description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 5
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 5
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 5
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 claims description 5
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 5
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 5
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical group C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims description 4
- 125000001302 tertiary amino group Chemical group 0.000 claims description 4
- 125000004953 trihalomethyl group Chemical group 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 60
- 150000001875 compounds Chemical class 0.000 description 55
- 239000000126 substance Substances 0.000 description 41
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 32
- 238000004519 manufacturing process Methods 0.000 description 28
- -1 heteropolycyclic compound Chemical class 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000011734 sodium Substances 0.000 description 18
- 229930192474 thiophene Natural products 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 150000002391 heterocyclic compounds Chemical class 0.000 description 10
- 150000001491 aromatic compounds Chemical class 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000006467 substitution reaction Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 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 7
- 238000000862 absorption spectrum Methods 0.000 description 7
- 239000007800 oxidant agent Substances 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- LYTMVABTDYMBQK-UHFFFAOYSA-N 2-benzothiophene Chemical compound C1=CC=CC2=CSC=C21 LYTMVABTDYMBQK-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- QGGSWEDJFFDTIQ-UHFFFAOYSA-N benzo[f][2]benzothiole Chemical compound C1=CC=CC2=CC3=CSC=C3C=C21 QGGSWEDJFFDTIQ-UHFFFAOYSA-N 0.000 description 4
- 238000000502 dialysis Methods 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000003456 ion exchange resin Substances 0.000 description 4
- 229920003303 ion-exchange polymer Polymers 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-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
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 229920001429 chelating resin Polymers 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 229920000767 polyaniline Polymers 0.000 description 3
- 125000004585 polycyclic heterocycle group Chemical group 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 229920000123 polythiophene Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 3
- GJSDSQMOVFARPY-UHFFFAOYSA-N 1,3-dihydrobenzo[f][2]benzothiole Chemical compound C1=CC=C2C=C3CSCC3=CC2=C1 GJSDSQMOVFARPY-UHFFFAOYSA-N 0.000 description 2
- UXGVMFHEKMGWMA-UHFFFAOYSA-N 2-benzofuran Chemical compound C1=CC=CC2=COC=C21 UXGVMFHEKMGWMA-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical group CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- YPEFMQGGABUYFX-UHFFFAOYSA-N benzo[g][2]benzothiole Chemical group C1=CC=C2C3=CSC=C3C=CC2=C1 YPEFMQGGABUYFX-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- IZJIQLPALMMUNB-UHFFFAOYSA-N naphtho[2,3-f][2]benzothiole Chemical compound C1=CC=CC2=CC3=CC4=CSC=C4C=C3C=C21 IZJIQLPALMMUNB-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical group CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 2
- HAABYBOJPNPZFS-UHFFFAOYSA-N 1,1,3,3-tetrachlorobenzo[f][2]benzothiole-5-sulfonic acid Chemical compound C1=C2C(S(=O)(=O)O)=CC=CC2=CC2=C1C(Cl)(Cl)SC2(Cl)Cl HAABYBOJPNPZFS-UHFFFAOYSA-N 0.000 description 1
- OYSTYTODULUPHW-UHFFFAOYSA-N 1,2,3,4-tetrahydrothieno[2,3-c]pyridazine Chemical compound N1NCCC2=C1SC=C2 OYSTYTODULUPHW-UHFFFAOYSA-N 0.000 description 1
- TZPKMQPRMAOCJX-UHFFFAOYSA-N 1,3-dibromo-5,7-dimethoxybenzo[f][2]benzothiole-6-sulfonic acid Chemical compound C1=C2C(OC)=C(S(O)(=O)=O)C(OC)=CC2=CC2=C(Br)SC(Br)=C21 TZPKMQPRMAOCJX-UHFFFAOYSA-N 0.000 description 1
- WREOKJLAVYHGIB-UHFFFAOYSA-N 1,3-dibromobenzo[f][2]benzothiole-5-sulfonic acid Chemical compound C1=C2C(S(=O)(=O)O)=CC=CC2=CC2=C(Br)SC(Br)=C21 WREOKJLAVYHGIB-UHFFFAOYSA-N 0.000 description 1
- KDSGILOODZIIFK-UHFFFAOYSA-N 1,3-dichlorobenzo[f][2]benzothiole-5-sulfonic acid Chemical compound C1=C2C(S(=O)(=O)O)=CC=CC2=CC2=C(Cl)SC(Cl)=C21 KDSGILOODZIIFK-UHFFFAOYSA-N 0.000 description 1
- HGFCFLSFSLDKOL-UHFFFAOYSA-N 1,3-dihydrobenzo[f][2]benzothiole-5-sulfonic acid Chemical compound C1=C2C(S(=O)(=O)O)=CC=CC2=CC2=C1CSC2 HGFCFLSFSLDKOL-UHFFFAOYSA-N 0.000 description 1
- XYKKCSYBZSFSSG-UHFFFAOYSA-N 1,3-dihydrobenzo[f][2]benzothiole-6-sulfonic acid Chemical compound C1=C2CSCC2=CC2=CC(S(=O)(=O)O)=CC=C21 XYKKCSYBZSFSSG-UHFFFAOYSA-N 0.000 description 1
- SLXFEEBANGECTR-UHFFFAOYSA-N 1,3-dihydrobenzo[g][2]benzothiole Chemical compound C1=CC2=CC=CC=C2C2=C1CSC2 SLXFEEBANGECTR-UHFFFAOYSA-N 0.000 description 1
- SZPBGJCUNGGYDV-UHFFFAOYSA-N 1,3-dihydronaphtho[2,3-f][2]benzothiole Chemical compound C1=CC=C2C=C(C=C3CSCC3=C3)C3=CC2=C1 SZPBGJCUNGGYDV-UHFFFAOYSA-N 0.000 description 1
- GDGMWOJNRJRHJX-UHFFFAOYSA-N 1,3-dihydronaphtho[2,3-g][2]benzothiole Chemical compound C1=CC2=CC3=CC=CC=C3C=C2C2=C1CSC2 GDGMWOJNRJRHJX-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 125000006018 1-methyl-ethenyl group Chemical group 0.000 description 1
- SJNUXEAPCYTTDZ-UHFFFAOYSA-N 2,3-dihydrothieno[2,3-c]pyridine Chemical compound C1=NC=C2SCCC2=C1 SJNUXEAPCYTTDZ-UHFFFAOYSA-N 0.000 description 1
- IAQQDIGGISSSQO-UHFFFAOYSA-N 2-(4-fluorophenyl)piperidine Chemical compound C1=CC(F)=CC=C1C1NCCCC1 IAQQDIGGISSSQO-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- VRGCYEIGVVTZCC-UHFFFAOYSA-N 3,4,5,6-tetrachlorocyclohexa-3,5-diene-1,2-dione Chemical compound ClC1=C(Cl)C(=O)C(=O)C(Cl)=C1Cl VRGCYEIGVVTZCC-UHFFFAOYSA-N 0.000 description 1
- JNGDCMHTNXRQQD-UHFFFAOYSA-N 3,6-dioxocyclohexa-1,4-diene-1,2,4,5-tetracarbonitrile Chemical compound O=C1C(C#N)=C(C#N)C(=O)C(C#N)=C1C#N JNGDCMHTNXRQQD-UHFFFAOYSA-N 0.000 description 1
- XLTSMRQOOSSQAL-UHFFFAOYSA-N 4,5,6,9-tetrahydroacenaphthyleno[1,2-c]thiophene Chemical group C1=CC=C2CCCC3=C2C1=C1C3=CSC1 XLTSMRQOOSSQAL-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- LZELNNFVHLFICJ-UHFFFAOYSA-N 6,7-dimethyl-1,3-dihydrobenzo[f][2]benzothiole-5-sulfonic acid Chemical compound C1=C2C(S(O)(=O)=O)=C(C)C(C)=CC2=CC2=C1CSC2 LZELNNFVHLFICJ-UHFFFAOYSA-N 0.000 description 1
- DMUSVQPHYBEXRB-UHFFFAOYSA-N 6-(trifluoromethyl)-1,3-dihydrobenzo[f][2]benzothiole-8-sulfonic acid Chemical compound C1=C2C(S(=O)(=O)O)=CC(C(F)(F)F)=CC2=CC2=C1CSC2 DMUSVQPHYBEXRB-UHFFFAOYSA-N 0.000 description 1
- YCOCETGGDYSKET-UHFFFAOYSA-N 6-bromo-1,3-dihydrobenzo[f][2]benzothiole-8-sulfonic acid Chemical compound C1=C2C(S(=O)(=O)O)=CC(Br)=CC2=CC2=C1CSC2 YCOCETGGDYSKET-UHFFFAOYSA-N 0.000 description 1
- AAWORGHKWMMWII-UHFFFAOYSA-N 6-cyano-1,3-dihydrobenzo[f][2]benzothiole-8-sulfonic acid Chemical compound C1=C2C(S(=O)(=O)O)=CC(C#N)=CC2=CC2=C1CSC2 AAWORGHKWMMWII-UHFFFAOYSA-N 0.000 description 1
- XQGWRGVPTFXDLM-UHFFFAOYSA-N 6-nitro-1,3-dihydrobenzo[f][2]benzothiole-8-sulfonic acid Chemical compound C1=C2C(S(=O)(=O)O)=CC([N+]([O-])=O)=CC2=CC2=C1CSC2 XQGWRGVPTFXDLM-UHFFFAOYSA-N 0.000 description 1
- JBGCKUDROXIEDO-UHFFFAOYSA-N 6-thiapentacyclo[11.8.0.03,11.04,8.015,20]henicosa-1(21),2,4(8),9,11,13,15,17,19-nonaene Chemical compound C1=CC=C2C=C(C=C3C=4CSCC=4C=CC3=C3)C3=CC2=C1 JBGCKUDROXIEDO-UHFFFAOYSA-N 0.000 description 1
- XFZQZFHGOHSLIJ-UHFFFAOYSA-N 7-methyl-1,3-dihydrobenzo[f][2]benzothiole-6-sulfonic acid Chemical compound C1=C2C=C(S(O)(=O)=O)C(C)=CC2=CC2=C1CSC2 XFZQZFHGOHSLIJ-UHFFFAOYSA-N 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
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- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
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- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- KKOWKMBHRUCNHB-UHFFFAOYSA-N thieno[3,4-b]quinoxaline Chemical compound C1=CC=CC2=NC3=CSC=C3N=C21 KKOWKMBHRUCNHB-UHFFFAOYSA-N 0.000 description 1
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- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Non-Insulated Conductors (AREA)
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Description
本発明は、溶媒に対して高い溶解度を有し極めて安定な導電性重合体およびその製造方法に関する。更に詳しくは、本発明は、電気、電子工業の分野において、加工性要求度の高い電極、センサー、エレクトロニクス表示素子、非線形光学素子、光電変換素子、帯電防止剤ほか、各種導電材料あるいは光学材料として用いるのに特に適した導電性重合体の製造方法に関するものである。 The present invention relates to a highly stable conductive polymer having high solubility in a solvent and a method for producing the same. More specifically, the present invention relates to electrodes, sensors, electronic display elements, non-linear optical elements, photoelectric conversion elements, antistatic agents, various conductive materials or optical materials that have a high degree of workability in the electrical and electronic industries. The present invention relates to a method for producing a conductive polymer particularly suitable for use.
π電子共役系の発達した導電性重合体は、導電性のみならず金属／半導体転移における化学的あるいは物理的状態変化などの特異な物性のために工業的に注目され、多くの用途を目指した研究がなされてきた。 縮合ヘテロ多環式化合物のうち、π共役構造がキノイド構造を有するイソチアナフテン、ベンゾ［ｃ］フラン、ナフト［２，３−ｃ］チオフェンなどは極めて反応性が高く、単離するために特別の工夫を要する化合物であることが知られている（Journal of Organic Chemistry誌、３６巻、３９３２頁、１９７１年及びRecl. Trav. Chim. Pays-Bas誌、８７巻、１００６頁、１９６８年）。 Conducting polymers with developed π-electron conjugated systems have attracted industrial attention due to their unique physical properties such as chemical or physical change in the metal / semiconductor transition as well as conductivity, and have aimed for many applications. Research has been done. Among the condensed heteropolycyclic compounds, isothianaphthene, benzo [c] furan, naphtho [2,3-c] thiophene, etc. whose π-conjugated structure has a quinoid structure are extremely reactive and special for isolation. (Journal of Organic Chemistry, 36, 3932, 1971 and Recl. Trav. Chim. Pays-Bas, 87, 1006, 1968).
これらのうち、ヘテロ二環式導電性重合体であるイソチアナフテン構造を有する重合体は、Journal of Organic Chemistry誌、４９巻、３３８２頁、１９８４年等に電気化学的重合法及び化学的酸化重合法と共に特徴が開示されており、エネルギーギャップ（Ｅｇ）が１．１ｅＶと極めて小さく安定な導電状態を示すことが知られている。しかしながら、製造されたポリイソチアナフテンが不溶不融であるために、加工性が制限される欠点があった。そのため、アルキル基あるいはアルコキシ基を繰返し構造単位中に導入することにより、有機溶媒に可溶とする方法が特開平２−２４２８１６号等に開示されている。 Among these, a polymer having an isothianaphthene structure, which is a heterobicyclic conductive polymer, was published in Journal of Organic Chemistry, 49, 3382, 1984, etc. The characteristics are disclosed together with the law, and it is known that the energy gap (Eg) is as small as 1.1 eV and shows a stable conductive state. However, since the produced polyisothianaphthene is insoluble and infusible, there is a drawback that processability is limited. Therefore, JP-A-2-242816 discloses a method for making an organic solvent soluble by introducing an alkyl group or an alkoxy group repeatedly into a structural unit.
スルホン酸基を有しない１，３−ジヒドロイソチアナフテンの酸化的化学重合法については、例えば、特開昭６３−１１８３２３号公報及びＵＳＰ４７８９７４８号公報）にそれぞれ製造方法が示されている。 Regarding the oxidative chemical polymerization method of 1,3-dihydroisothianaphthene having no sulfonic acid group, for example, JP-A-63-1118323 and USP47878948) each show a production method.
また繰返し構造単位のイソチアナフテニレン骨格に電子吸引性基や電子供与性基を導入すると、半導体としての電子状態に影響を与えることをBredasらは計算結果によって報告している（Journal of Chemical Physics 誌、８５巻（８）、４６７３頁、１９８６年）。また、関連する例としては、ハロゲンを置換基とした重合体（特開昭６３−３０７６０４号）や、電子吸引性基を置換基とする重合体を列挙した公報（特開平２−２５２７２７号）もあるが、その製造方法について具体的な開示はされていない。また、ヘテロ三環式導電性重合体であるナフト［２，３−ｃ］チオフェン構造を有する重合体は、Synthetic Metals誌、３５巻、２６３頁、１９９０年に製造方法が報告されている。 In addition, Bredas et al. Have reported that the introduction of electron-withdrawing groups and electron-donating groups into the isothianaphthenylene skeleton of repeating structural units affects the electronic state of semiconductors (Journal of Chemical Physics). Magazine, 85 (8), 4673, 1986). Further, as related examples, there are listed polymers having halogen as a substituent (Japanese Patent Laid-Open No. 63-307604) and polymers having an electron-withdrawing group as a substituent (Japanese Patent Laid-Open No. 2-252727). However, there is no specific disclosure about the manufacturing method. A method for producing a polymer having a naphtho [2,3-c] thiophene structure, which is a heterotricyclic conductive polymer, was reported in Synthetic Metals, 35, 263, 1990.
しかしながら、何れも本発明に関するスルホン酸置換基を有する縮合ヘテロ多環式重合体についての特性に関し何ら記載されておらず、その製造方法についても具体的な開示はない。 However, none of them describes anything about the characteristics of the condensed heteropolycyclic polymer having a sulfonic acid substituent related to the present invention, and there is no specific disclosure about its production method.
一方、スルホン酸のようなブレンステッド酸基をポリマ−主鎖に直接またはスペーサーを介して間接的に共有結合させることにより得られる水溶性の自己ドープ型のπ電子共役系ポリマーは、外来ドーパントの寄与なしに長期間にわたって安定な導電状態を示す点で注目されてきた。 On the other hand, a water-soluble self-doped π-electron conjugated polymer obtained by covalently bonding a Bronsted acid group such as a sulfonic acid directly or indirectly via a spacer to a polymer main chain is a foreign dopant. It has attracted attention in that it exhibits a stable conductive state over a long period of time without contribution.
具体的な例として、例えばアルカンスルホン酸基を有するポリチオフェン誘導体（F.Wudlら Journal of American Chemical Society 誌、１０９巻、１８５８頁、１９８７年や E.E.HavingaらPolymer Bulletin誌、１８巻、２７７頁、１９８７年）、Aldissi のポリチオフェン誘導体やポリピロ−ル誘導体（米国特許４８８０５０８号）、ポリアニリンの芳香環に置換基としてアルカンスルホン酸基やアルキルカルボン酸基を有する重合体（特開昭６３−３９９１６号）、ピロールのＮ位にプロパンスルホン酸基が置換した重合体（Journal of Chemical Society 、Chemical Communication誌、６２１頁、１９８７年）、Ｎ位にプロパンスルホン酸基が置換したポリアニリン誘導体（Journal of Chemical Society 、Chemical Communication誌、１８０頁、１９９０年やSynthetic Metals誌、３１巻、３６９頁、１９８９年）、芳香環に直接スルホン酸基が置換したポリアニリン誘導体（Journal of American Chemical Society誌、１１２巻、２８００頁、１９９０年）、Ｎ位にアルカンスルホン酸基が置換したポリカルバゾール誘導体（ＵＳＰ５，１３０，４１２号公報）などが製造法と共に開示されている。また、特開平２−１８９３３３号公報には、アルカンスルホン酸基を有するチオフェン誘導体モノマーの酸化的化学重合法が開示されている。 Specific examples include polythiophene derivatives having an alkanesulfonic acid group (F. Wudl et al. Journal of American Chemical Society, 109, 1858, 1987, EEHavinga et al., Polymer Bulletin, 18, 277, 1987). Aldissi polythiophene derivatives and polypyrrole derivatives (US Pat. No. 4,880,508), polymers having an alkanesulfonic acid group or alkylcarboxylic acid group as a substituent on the aromatic ring of polyaniline (Japanese Patent Laid-Open No. 63-39916), A polymer having a propanesulfonic acid group substituted at the N-position of pyrrole (Journal of Chemical Society, Chemical Communication, 621, 1987), a polyaniline derivative substituted with a propanesulfonic acid group at the N-position (Journal of Chemical Society, Chemical Communication magazine, 180 pages, 1990, Synthetic Metals magazine, 31 pages, 369 pages, 1 989), a polyaniline derivative in which an aromatic ring is directly substituted with a sulfonic acid group (Journal of American Chemical Society, 112, 2800, 1990), a polycarbazole derivative in which an N-position is substituted with an alkanesulfonic acid group (USP 5, 130, 412) and the like are disclosed together with the manufacturing method. Japanese Laid-Open Patent Publication No. 2-189333 discloses an oxidative chemical polymerization method of a thiophene derivative monomer having an alkanesulfonic acid group.
しかしながら、上記の何れの製造法も、本発明に係わるスルホン酸基を有する縮合ヘテロ多環式化合物の化学的重合反応に関しては具体的に開示していない。 However, none of the above production methods specifically disclose the chemical polymerization reaction of the condensed heteropolycyclic compound having a sulfonic acid group according to the present invention.
本発明は、スルホン酸基を有する縮合ヘテロ多環式化合物を原料として重合させることにより、スルホン酸基を有する縮合ヘテロ多環式化合物構造を含む導電性重合体の製造方法を提供することにある。また、本発明は、スルホン酸基を有する縮合ヘテロ多環式化合物を原料として、単独、もしくは他の芳香族化合物及び／または複素環化合物及び／またはπ電子共役構造を形成し得る化合物と共に重合させることにより、スルホン酸基を有する縮合ヘテロ多環式化合物構造を含む導電性重合体の製造方法を提供することにある。 An object of the present invention is to provide a method for producing a conductive polymer having a condensed heteropolycyclic compound structure having a sulfonic acid group by polymerizing a condensed heteropolycyclic compound having a sulfonic acid group as a raw material. . In the present invention, a condensed heteropolycyclic compound having a sulfonic acid group is used as a raw material to be polymerized alone or together with another aromatic compound and / or heterocyclic compound and / or a compound capable of forming a π-electron conjugated structure. Accordingly, an object of the present invention is to provide a method for producing a conductive polymer including a condensed heteropolycyclic compound structure having a sulfonic acid group.
本発明は 一般式（Ｉ） The present invention relates to the general formula (I)
また、同様に前記一般式（Ｉ）（式中、Ｒ1 、Ｒ2 、Ｒ3 、Ｒ4 、Ｒ5 、Ｘ1 、Ｘ2 、Ｘ3 、Ｘ4 、Ｍ及びｋは前記と同じ。）で表わされる構造の化合物を、単独で、または他の芳香族化合物及び／または複素環式化合物及び／またはπ電子共役構造を形成し得る化合物と共に重合させて、下記一般式（ＩＩＩ） Similarly, the general formula (I) (wherein R 1 , R 2 , R 3 , R 4 , R 5 , X 1 , X 2 , X 3 , X 4 , M and k are the same as above). A compound having a structure represented by the following general formula (III) is polymerized alone or together with another aromatic compound and / or a heterocyclic compound and / or a compound capable of forming a π-electron conjugated structure:
また、同様に前記一般式（Ｉ）（式中、Ｒ1 、Ｒ2 、Ｒ3 、Ｒ4 、Ｒ5 、Ｘ1 、Ｘ2 、Ｘ3 、Ｘ4 及びＭは前記と同じ。ｋは０である。）で表わされる化合物を、単独で、または他の芳香族化合物及び／または複素環式化合物及び／またはπ電子共役構造を形成し得る化合物と共に重合させて、下記一般式（ＶＩ） Similarly, in the general formula (I) (wherein R 1 , R 2 , R 3 , R 4 , R 5 , X 1 , X 2 , X 3 , X 4 and M are the same as above, k is 0) And a compound represented by the following general formula (VI), which is polymerized alone or together with another aromatic compound and / or a heterocyclic compound and / or a compound capable of forming a π-electron conjugated structure.
一般式（Ｉ）で示される構造の縮合ヘテロ多環式化合物は、一般式（Ｉ）においてジヒドロチオフェン環と置換基Ｒ1 乃至Ｒ3 を有するベンゼン環に囲まれた縮合環の数を表わすｋが０乃至３の範囲の整数で表わされる化合物であり、一般式（Ｉ）の縮合環には窒素またはＮ−オキシドを任意に含んでもよい。窒素またはＮ−オキシドを含む化合物の例としては、チエノ［３，４−ｂ］キノキサリン、チエノ［３，４−ｂ］キノキサリン−４，９−ジオキド等が挙げられる。Ｒ1 、Ｒ2 、Ｒ3 、Ｒ4 またはＲ5 の炭化水素鎖は互いに任意の位置で結合して、かかる基により置換を受けている炭素原子と共に、少なくとも１つ以上の３乃至７員環の飽和または不飽和炭化水素の環状構造を形成する二価鎖を少なくとも１つ以上形成してもよい。Ｒ1 、Ｒ2 、Ｒ3 、Ｒ4 及びＲ5 のアルキル基、アルコキシ基、アルキルエステル基またはそれらによって形成される環状炭化水素鎖にはカルボニル、エーテル、エステル、アミド、スルフィド、スルフィニル、スルホニル、イミノ等の結合を任意に含んでもよい。 The condensed heteropolycyclic compound having the structure represented by the general formula (I) represents the number of condensed rings surrounded by the dihydrothiophene ring and the benzene ring having substituents R 1 to R 3 in the general formula (I). Is a compound represented by an integer in the range of 0 to 3, and the condensed ring of the general formula (I) may optionally contain nitrogen or N-oxide. Examples of the compound containing nitrogen or N-oxide include thieno [3,4-b] quinoxaline, thieno [3,4-b] quinoxaline-4,9-dioxide, and the like. The hydrocarbon chains of R 1 , R 2 , R 3 , R 4 or R 5 are bonded to each other at any position, and together with the carbon atom substituted by such a group, at least one 3- to 7-membered ring At least one divalent chain forming a cyclic structure of the saturated or unsaturated hydrocarbon may be formed. The alkyl group, alkoxy group, alkyl ester group of R 1 , R 2 , R 3 , R 4 and R 5 or the cyclic hydrocarbon chain formed by them include carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl, A bond such as imino may optionally be included.
一般式（Ｉ）で示される構造の具体的な縮合ヘテロ多環式化合物の基本骨格の例として、１，３−ジヒドロイソチアナフテン（一般式（Ｉ）の式中のｋが０、Ｘ1 、Ｘ2 、Ｘ3 及びＸ4 がＨである化合物）、１，３−ジクロロイソチアナフテン（一般式（Ｉ）の式中のｋが０、Ｘ1 及びＸ3 がＣｌ、Ｘ2 及びＸ4 がＨである化合物）、１，１，３，３−テトラクロロイソチアナフテン（一般式（Ｉ）の式中のｋが０、Ｘ1 Ｘ2 、Ｘ3 及びＸ4 がＣｌである化合物）、１，３−ジヒドロナフト［１，２−ｃ］チオフェン（一般式（Ｉ）のｋが１、Ｘ1 、Ｘ2 、Ｘ3 及びＸ4 がＨである化合物）、１，３−ジヒドロナフト［２，３−ｃ］チオフェン（一般式（Ｉ）のｋが１、Ｘ1 、Ｘ2 、Ｘ3 及びＸ4 がＨである化合物）、１，３−ジクロロナフト［２，３−ｃ］チオフェン（一般式（Ｉ）のｋが１、Ｘ1 及びＸ3 がＣｌ、Ｘ2 及びＸ4 がＨである化合物）、１，３−ジヒドロアントラ［１，２−ｃ］チオフェン（一般式（Ｉ）のｋが２、Ｘ1 、Ｘ2 、Ｘ3 及びＸ4 がＨである化合物）、１，３−ジヒドロアントラ［２，３−ｃ］チオフェン（一般式（Ｉ）のｋが２、Ｘ1 、Ｘ2 、Ｘ3 及びＸ4 がＨである化合物）、１，３−ジヒドロフェナントラ［１，２−ｃ］チオフェン（一般式（Ｉ）のｋが２、Ｘ1 、Ｘ2 、Ｘ3 及びＸ4 がＨである化合物）、１，３−ジヒドロフェナントラ［２，３−ｃ］チオフェン（一般式（Ｉ）のｋが２、Ｘ1 、Ｘ2 、Ｘ3 及びＸ4 がＨである化合物）、１，３−ジヒドロフェナントラ［３，４−ｃ］チオフェン（一般式（Ｉ）のｋが２、Ｘ1 、Ｘ2 、Ｘ3 及びＸ4 がＨである化合物）、１，３−ジヒドロフェナントラ［９，１０−ｃ］チオフェン（一般式（Ｉ）のｋが２、Ｘ1 、Ｘ2 、Ｘ3 及びＸ4 がＨである化合物）、１，３−ジヒドロナフタセノ［１，２−ｃ］チオフェン（一般式（Ｉ）のｋが３、Ｘ1 、Ｘ2 、Ｘ3 及びＸ4 がＨである化合物）、１，３−ジヒドロナフタセノ［２，３−ｃ］チオフェン（一般式（Ｉ）のｋが３、Ｘ1 、Ｘ2 、Ｘ3 及びＸ4 がＨである化合物）等が挙げられるが、本発明はこれらに限定されるものではない。 As an example of a basic skeleton of a specific condensed heteropolycyclic compound having a structure represented by the general formula (I), 1,3-dihydroisothianaphthene (k in the formula of the general formula (I) is 0, X 1 , X 2 , X 3 and X 4 are H), 1,3-dichloroisothianaphthene (k in the general formula (I) is 0, X 1 and X 3 are Cl, X 2 and X A compound in which 4 is H), 1,1,3,3-tetrachloroisothianaphthene (a compound in which k is 0, X 1 X 2 , X 3 and X 4 are Cl in the formula (I)) ), 1,3-dihydronaphtho [1,2-c] thiophene (a compound in which k in formula (I) is 1, X 1 , X 2 , X 3 and X 4 are H), 1,3-dihydro naphtho [2,3-c] thiophene (k is 1, X 1, X 2, compound X 3 and X 4 are H in the general formula (I)), 1,3 Jikuroronafuto [2, -C] thiophene (compound of general formula k is 1, X 1 and X 3 is Cl, X 2 and X 4 are H in (I)), 1,3-dihydroanthra [1,2-c] thiophene ( A compound in which k in the general formula (I) is 2, X 1 , X 2 , X 3 and X 4 are H), 1,3-dihydroanthra [2,3-c] thiophene (k in the general formula (I) Is a compound in which X 1 , X 2 , X 3 and X 4 are H), 1,3-dihydrophenanthra [1,2-c] thiophene (k in the general formula (I) is 2, X 1 , X 2 , X 3 and X 4 are H), 1,3-dihydrophenanthra [2,3-c] thiophene (k in formula (I) is 2, X 1 , X 2 , X A compound in which 3 and X 4 are H), 1,3-dihydrophenanthra [3,4-c] thiophene (k in the general formula (I) is 2, X 1 , X 2 , X 3 and X 4 are H Compound), 1,3-dihydro-phenanthraquinone [9,10-c] thiophene k is 2, X 1, X 2, compound X 3 and X 4 are H in (formula (I)), 1 , 3-Dihydronaphthaceno [1,2-c] thiophene (a compound in which k in the general formula (I) is 3, X 1 , X 2 , X 3 and X 4 are H), 1,3-dihydronaphthaceno [2,3-c] thiophene (compounds in which k in general formula (I) is 3, X 1 , X 2 , X 3 and X 4 are H) and the like are exemplified, but the present invention is limited to these. It is not a thing.
また、置換基Ｒ1 、Ｒ2 、Ｒ3 、Ｒ4 またはＲ5 の炭化水素鎖が互いに任意の位置で結合して３乃至７員環の飽和または不飽和炭化水素の環状構造を形成した例としては、１，３−ジヒドロペリロ［ｃ］チオフェン、１，３−ジヒドロアセナフト［ｃ］チオフェン構造等が挙げられるが、本発明はこれらに限定されるものではない。
また、前記一般式（Ｉ）で示される構造の、縮合環に窒素等を含んだ縮合ヘテロ環式化合物の例としては、下記の化合物等が挙げられるが、本発明はこれらに限定されるものではない。
Examples where the hydrocarbon chains of the substituents R 1 , R 2 , R 3 , R 4 or R 5 are bonded to each other at an arbitrary position to form a cyclic structure of a 3 to 7-membered saturated or unsaturated hydrocarbon. Examples include 1,3-dihydroperillo [c] thiophene and 1,3-dihydroacenaphtho [c] thiophene structures, but the present invention is not limited thereto.
Examples of the condensed heterocyclic compound having the structure represented by the general formula (I) and containing a condensed ring containing nitrogen and the like include the following compounds, but the present invention is not limited thereto. is not.
本発明において、ひとつの好ましい基本骨格の例として、１，３−ジヒドロイソチアナフテン構造を有する一般式（ＩＶ） In the present invention, as an example of one preferable basic skeleton, the general formula (IV) having a 1,3-dihydroisothianaphthene structure is used.
本発明の一般式（Ｉ）、（ＩＩ）、（ＩＩＩ）または（ＶＩＩ）における置換基Ｒ1 、Ｒ2 、Ｒ3 、Ｒ4 、またはＲ5 として有用な例、あるいは一般式（ＩＶ）または（ＶＩ）における置換基Ｒ1 、Ｒ2 またはＲ3 として有用な例としては、水素、ハロゲン、ＳＯ3 -Ｍ、飽和アルキル基、不飽和アルキル基、飽和アルコキシ基、不飽和アルコキシ基、飽和アルキルエステル基、不飽和アルキルエステル基、ニトロ基、シアノ基等が挙げられる。これらの置換基を更に詳しく例示すれば、ハロゲンとしては塩素、臭素、フッ素、よう素等、飽和、不飽和アルキルまたはアルキルエステル基の炭化水素鎖としては、メチル、エチル、プロピル、イソプロピル、ブチル、ｔ−ブチル、ペンチル、ヘキシル、オクチル、ドデシル、テトラデシル、メトキシエチル、エトキシエチル、（２−メトキシ）エチル、アセトニル、ビニル、１−メチルエテニル、２−メチルエテニル、クロトニル、アリル、フェニル、トシル、キシリル、フェナシル等が挙げられる。アルコキシ基としてはメトキシ、エトキシ、（２−メトキシ）エトキシ、プロポキシ、イソプロポキシ、ヘキシルオキシ、オクチルオキシ、ドデシルオキシ等の基が挙げられる。
さらに、上記以外に置換基の例として、メチルアミノ、エチルアミノ、ジフェニルアミノ、アニリノ等のアミノ基、トリフルオロメチル、クロロフェニル、アセトアミド等の基が挙げられる。
Examples useful as substituents R 1 , R 2 , R 3 , R 4 , or R 5 in general formula (I), (II), (III) or (VII) of the present invention, or general formula (IV) or useful examples as the substituents R 1, R 2 or R 3 in (VI) is hydrogen, halogen, SO 3 - M, saturated alkyl group, unsaturated alkyl groups, saturated alkoxy group, an unsaturated alkoxy group, saturated alkyl Examples include an ester group, an unsaturated alkyl ester group, a nitro group, and a cyano group. Illustrating these substituents in more detail, as halogen, chlorine, bromine, fluorine, iodine, etc., saturated, unsaturated alkyl or alkyl ester groups as hydrocarbon chains, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, octyl, dodecyl, tetradecyl, methoxyethyl, ethoxyethyl, (2-methoxy) ethyl, acetonyl, vinyl, 1-methylethenyl, 2-methylethenyl, crotonyl, allyl, phenyl, tosyl, xylyl, phenacyl Etc. Examples of the alkoxy group include groups such as methoxy, ethoxy, (2-methoxy) ethoxy, propoxy, isopropoxy, hexyloxy, octyloxy, dodecyloxy and the like.
In addition to the above, examples of the substituent include amino groups such as methylamino, ethylamino, diphenylamino, and anilino, and groups such as trifluoromethyl, chlorophenyl, and acetamide.
本発明の一般式（Ｉ）、（ＩＶ）または（ＶＩＩ）において、置換基Ｘ1 、Ｘ2 、Ｘ3 、またはＸ4 として有用な例としては、水素、Ｆ、Ｃｌ、Ｂｒ、Ｉが挙げられる。 Examples of useful substituents X 1 , X 2 , X 3 , or X 4 in the general formula (I), (IV) or (VII) of the present invention include hydrogen, F, Cl, Br, and I. It is done.
一般式（ＩＶ）で表わされる化合物の例を更に詳しく例示すれば、例えば、１，３−ジヒドロイソチアナフテン−５−スルホン酸、１，３−ジクロロイソチアナフテン−５−スルホン酸、１，３−ジブロモイソチアナフテン−５−スルホン酸、１，１，３，３−テトラクロロイソチアナフテン−５−スルホン酸、１，３−ジヒドロ−６−メトキシイソチアナフテン−５−スルホン酸、１，３−ジクロロ−６−メトキシイソチアナフテン−５−スルホン酸、１，３−ジヒドロ−６−ブトキシイソチアナフテン−５−スルホン酸、１，３−ジヒドロ−６−デシルオキシイソチアナフテン−５−スルホン酸、１，３−ジヒドロ−６−メトキシカルボニルイソチアナフテン−５−スルホン酸、１，３−ジヒドロ−４，７−ジメトキシイソチアナフテン−５−スルホン酸、１，３−ジヒドロイソチアナフテン−５，６−ジスルホン酸、１，３−ジブロモ−４，７−ジメトキシイソチアナフテン−５−スルホン酸、１，３−ジヒドロ−５，６−ジオキシメチレンイソチアナフテン−４−スルホン酸、１，３−ジヒドロ−６−ニトロイソチアナフテン−５−スルホン酸、１，３−ジヒドロ−６−ブロモイソチアナフテン−５−スルホン酸、１，３−ジヒドロ−６−シアノイソチアナフテン−５−スルホン酸、１，３−ジヒドロ−６−アミノイソチアナフテン−５−スルホン酸、１，３−ジヒドロ−６−トリフルオロメチルイソチアナフテン−５−スルホン酸等及びかかるスルホン酸誘導体のリチウム塩、ナトリウム塩、カリウム塩、アンモニウム塩、四級アンモニウム塩等が挙げられるが、本発明はこれらに限定されるものではない。 If the example of a compound represented by general formula (IV) is illustrated in more detail, for example, 1,3-dihydroisothianaphthene-5-sulfonic acid, 1,3-dichloroisothianaphthene-5-sulfonic acid, 3-dibromoisothianaphthene-5-sulfonic acid, 1,1,3,3-tetrachloroisothianaphthene-5-sulfonic acid, 1,3-dihydro-6-methoxyisothianaphthene-5-sulfonic acid, 1 , 3-Dichloro-6-methoxyisothianaphthene-5-sulfonic acid, 1,3-dihydro-6-butoxyisothianaphthene-5-sulfonic acid, 1,3-dihydro-6-decyloxyisothianaphthene-5 -Sulfonic acid, 1,3-dihydro-6-methoxycarbonylisothianaphthene-5-sulfonic acid, 1,3-dihydro-4,7-dimethoxyisothianaphthene 5-sulfonic acid, 1,3-dihydroisothianaphthene-5,6-disulfonic acid, 1,3-dibromo-4,7-dimethoxyisothianaphthene-5-sulfonic acid, 1,3-dihydro-5,6 -Dioxymethyleneisothianaphthene-4-sulfonic acid, 1,3-dihydro-6-nitroisothianaphthene-5-sulfonic acid, 1,3-dihydro-6-bromoisothianaphthene-5-sulfonic acid, 1 , 3-Dihydro-6-cyanoisothianaphthene-5-sulfonic acid, 1,3-dihydro-6-aminoisothianaphthene-5-sulfonic acid, 1,3-dihydro-6-trifluoromethylisothianaphthene- Examples include 5-sulfonic acid and the like, and lithium salts, sodium salts, potassium salts, ammonium salts, quaternary ammonium salts and the like of the sulfonic acid derivatives. But it is not limited thereto.
また、一般式（ＶＩＩ）で表わされる化合物の例を更に詳しく例示すれば、例えば、１，３−ジヒドロナフト［２，３−ｃ］チオフェン−５−スルホン酸、１，３−ジクロロナフト［２，３−ｃ］チオフェン−５−スルホン酸、１，３−ジブロモナフト［２，３−ｃ］チオフェン−５−スルホン酸、１，３−ジヒドロナフト［２，３−ｃ］チオフェン−６−スルホン酸、１，１，３，３−テトラクロロナフト［２，３−ｃ］チオフェン−５−スルホン酸、１，３−ジヒドロ−７−メトキシナフト［２，３−ｃ］チオフェン−６−スルホン酸、１，３−ジヒドロ−５，７−ジメトキシナフト［２，３−ｃ］チオフェン−６−スルホン酸、１，３−ジブロモ−５，７−ジメトキシナフト［２，３−ｃ］チオフェン−６−スルホン酸、１，３−ジヒドロ−６，７−ジオキシメチレンナフト［２，３−ｃ］チオフェン−５−スルホン酸、１，３−ジヒドロ−８−メトキシカルボニルナフト［２，３−ｃ］チオフェン−６−スルホン酸、１，３−ジヒドロ−７−ニトロナフト［２，３−ｃ］チオフェン−５−スルホン酸、７−ブロモ−１，３−ジヒドロナフト［２，３−ｃ］チオフェン−５−スルホン酸、７−シアノ−１，３−ジヒドロナフト［２，３−ｃ］チオフェン−５−スルホン酸、１，３−ジヒドロ−７−メチルナフト［２，３−ｃ］チオフェン−６−スルホン酸、１，３−ジヒドロ−６，７−ジメチルナフト［２，３−ｃ］チオフェン−５−スルホン酸、１，３−ジヒドロ−７−トリフルオロメチルナフト［２，３−ｃ］チオフェン−５−スルホン酸等及びかかるスルホン酸誘導体のリチウム塩、ナトリウム塩、カリウム塩、アンモニウム塩、四級アンモニウム塩等が挙げられるが、本発明はこれらに限定されるものではない。 Moreover, if the example of a compound represented by general formula (VII) is illustrated in more detail, for example, 1,3-dihydronaphtho [2,3-c] thiophene-5-sulfonic acid, 1,3-dichloronaphtho [2 , 3-c] thiophene-5-sulfonic acid, 1,3-dibromonaphtho [2,3-c] thiophene-5-sulfonic acid, 1,3-dihydronaphtho [2,3-c] thiophene-6-sulfone Acid, 1,1,3,3-tetrachloronaphtho [2,3-c] thiophene-5-sulfonic acid, 1,3-dihydro-7-methoxynaphtho [2,3-c] thiophene-6-sulfonic acid 1,3-dihydro-5,7-dimethoxynaphtho [2,3-c] thiophene-6-sulfonic acid, 1,3-dibromo-5,7-dimethoxynaphtho [2,3-c] thiophene-6 Sulfonic acid, 1,3-dihy B-6,7-dioxymethylenenaphtho [2,3-c] thiophene-5-sulfonic acid, 1,3-dihydro-8-methoxycarbonylnaphtho [2,3-c] thiophene-6-sulfonic acid, 1 , 3-Dihydro-7-nitronaphtho [2,3-c] thiophene-5-sulfonic acid, 7-bromo-1,3-dihydronaphtho [2,3-c] thiophene-5-sulfonic acid, 7-cyano- 1,3-dihydronaphtho [2,3-c] thiophene-5-sulfonic acid, 1,3-dihydro-7-methylnaphtho [2,3-c] thiophene-6-sulfonic acid, 1,3-dihydro-6 , 7-dimethylnaphtho [2,3-c] thiophene-5-sulfonic acid, 1,3-dihydro-7-trifluoromethylnaphtho [2,3-c] thiophene-5-sulfonic acid and the like, and such sulfonic acid derivatives Lithium salts, sodium salts, potassium salts, ammonium salts, such as quaternary ammonium salts, the present invention is not limited thereto.
一般式（Ｉ）、（ＩＶ）または（ＶＩＩ）で表わされる化合物，一般式（ＩＩ）で表わされる構造単位の少なくとも１つを繰返し単位として含む導電性重合体及び一般式（ＩＩＩ）または（ＶＩ）で表わされる構造を含む導電性共重合体において、スルホン酸イオンの対カチオンとして、Ｈ+ またはＮａ+ 、Ｌｉ+ 、Ｋ+ 等のアルカリ金属イオンまたはＮＨ4 +、ＮＨ（ＣＨ3)3 +、Ｎ（ＣＨ3)4 +、ＮＨ（Ｃ2 Ｈ5)3 +、Ｎ（Ｃ6 Ｈ5)4 +、ＰＨ4 +、Ｐ（ＣＨ3)4 +、Ｐ（Ｃ6 Ｈ5)4 +、ＡｓＨ4 +、Ａｓ（ＣＨ3)4 +、Ａｓ（Ｃ6 Ｈ5)4 +等のごときＶｂ族元素の非置換型または炭素数１乃至３０、望ましくは炭素数１乃至２０、さらに望ましくは炭素数１乃至１２のアルキル置換型または炭素数６乃至３０、望ましくは炭素数６乃至２０、さらに望ましくは炭素数６乃至１６のアリール置換型カチオンが用いられる。また、これらの一般式において、Ｍとして前記カチオンのうち異なる複数のカチオンが共存していてもよい。特定のカチオンに変換するには、通常のイオン交換樹脂や透析膜を通して任意のカチオンにイオン交換することができる。 Compounds represented by general formula (I), (IV) or (VII), conductive polymers containing at least one structural unit represented by general formula (II) as a repeating unit, and general formula (III) or (VI In the conductive copolymer including the structure represented by), H + or an alkali metal ion such as Na + , Li + , K + or NH 4 + , NH (CH 3 ) 3 + , N (CH 3 ) 4 + , NH (C 2 H 5 ) 3 + , N (C 6 H 5 ) 4 + , PH 4 + , P (CH 3 ) 4 + , P (C 6 H 5 ) 4 + , AsH 4 + , As (CH 3 ) 4 + , As (C 6 H 5 ) 4 + or the like, an unsubstituted type of a Vb group element or 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably C1-C12 alkyl-substituted type or C6-C30, preferably C6-C20 More preferably used is an aryl-substituted type cation having 6 to 16 carbon atoms. In these general formulas, a plurality of different cations among the cations may coexist as M. In order to convert to a specific cation, it can be ion-exchanged into an arbitrary cation through a normal ion exchange resin or a dialysis membrane.
一般式（Ｉ）、（ＩＶ）および（ＶＩＩ）において、Ｘ1 、Ｘ2 、Ｘ3 及びＸ4 は、それぞれ独立に水素、またはハロゲンを表わす。ハロゲンとしては、Ｃｌ、Ｂｒ、Ｉが好ましく、Ｃｌ、Ｂｒが特に好ましい。 In the general formulas (I), (IV) and (VII), X 1 , X 2 , X 3 and X 4 each independently represent hydrogen or halogen. As the halogen, Cl, Br, and I are preferable, and Cl and Br are particularly preferable.
一般式（ＩＩ）、（ＩＩＩ）、または（ＶＩ）で表わされる化学構造を含む、主鎖がπ電子共役構造を有する導電性重合体において、Ｍで表わされるカチオンがＨ＋ の場合、水溶液中において外来のドーパントがなくても自己ドーピング状態を示し、特に高濃度ではゲル状態を示すこともある。また、Ｍで表わされるカチオンを変えることにより、種々の溶媒に対する溶解性や溶媒親和性などを変えることができる。 In a conductive polymer containing a chemical structure represented by general formula (II), (III), or (VI) and having a π-electron conjugated structure in the main chain, when the cation represented by M is H +, Even if there is no exogenous dopant, it shows a self-doping state, and may show a gel state particularly at a high concentration. Also, by changing the cation represented by M, solubility in various solvents, solvent affinity, and the like can be changed.
本発明の一般式（ＩＩＩ）で表わされる化学構造を含む導電性共重合体は、前記一般式（ＩＩ）で表わされる構造単位の少なくとも１つを繰返し単位として含みかつ重合体の主鎖構造に他のπ電子共役構造系を繰返し単位として含む共重合体であり、かかるπ電子共役構造系繰返し単位としては、ビニレン、芳香族構造及び複素ヘテロ環構造が挙げられる。更に、かかる芳香族構造及び複素ヘテロ環構造としては、例えばイソチアナフテニレン、イソベンゾフリレン、イソベンゾインドリレン、イソベンゾセレニレン、イソベンゾテルリレン、チエニレン、ピロリレン、フリレン、セレニレン、テルリレン、イミノフェニレン、フェニレン構造等が挙げられる。また、これらの骨格構造が複数含まれていてもよい。また、前記π電子共役構造系の繰返し単位には重合を阻害しない置換基が置換されていてもよい。例えば、好ましい置換基としては、前記置換基Ｒ1 、Ｒ2 、Ｒ3 、Ｒ4 及びＲ5 の具体例で示したものと同じものが挙げられる。 The conductive copolymer containing the chemical structure represented by the general formula (III) of the present invention contains at least one of the structural units represented by the general formula (II) as a repeating unit, and has a main chain structure of the polymer. It is a copolymer containing another π-electron conjugated structure system as a repeating unit, and examples of the π-electron conjugated structure system repeating unit include vinylene, an aromatic structure, and a heterocyclic structure. Further, examples of the aromatic structure and the heterocyclic structure include isothianaphthenylene, isobenzofurylene, isobenzoindylene, isobenzoselenylene, isobenzotellylene, thienylene, pyrrolylene, furylene, selenylene, tellurylene, Examples include iminophenylene and a phenylene structure. A plurality of these skeleton structures may be included. The repeating unit of the π electron conjugated structure system may be substituted with a substituent that does not inhibit polymerization. For example, preferable substituents include the same substituents as those shown in the specific examples of the substituents R 1 , R 2 , R 3 , R 4 and R 5 .
一般式（ＩＩＩ）で表わされる化学構造を含む導電性共重合体において、前述のようにｍ及びｎは共重合体中のそれぞれの繰返し単位のモル分率を示す。従って一般式（ＩＩＩ）においてｍ、ｎはブロック共重合体を示すために用いられているものではない。前記共重合体の組成モル分率（ｍ：ｎ、但しｍ＋ｎ＝１）としては、前記化学式（ＩＩ）で表わされる構造単位からなる繰返し単位のモル分率であるｍが０．０５から０．９５の範囲であることが望ましい。ｍは０．２から０．９の範囲が望ましく、０．４から０．９の範囲が更に望ましい。ｍの割合が大きくなるに従い、水溶性の特性が強く現れる。 In the conductive copolymer including the chemical structure represented by the general formula (III), m and n indicate the mole fraction of each repeating unit in the copolymer as described above. Therefore, in the general formula (III), m and n are not used to indicate a block copolymer. As the composition mole fraction (m: n, where m + n = 1) of the copolymer, m, which is the mole fraction of the repeating unit composed of the structural unit represented by the chemical formula (II), is 0.05 to 0.00. A range of 95 is desirable. m is preferably in the range of 0.2 to 0.9, and more preferably in the range of 0.4 to 0.9. As the proportion of m increases, water-soluble properties become stronger.
一般式（ＩＩ）で表わされる構造単位の少なくとも１つを繰返し単位として含む重合体及び一般式（ＩＩＩ）または（ＶＩ）で表わされる化学構造を含む共重合体の分子量は、１０００〜５０００００、好ましくは１００００〜１０００００の範囲である。 The molecular weight of the polymer containing at least one structural unit represented by general formula (II) as a repeating unit and the copolymer containing a chemical structure represented by general formula (III) or (VI) is 1000 to 500,000, preferably Is in the range of 10,000 to 100,000.
次に、一般式（Ｉ）、（ＩＶ）もしくは（ＶＩＩ）で表わされる化学構造を有する化合物、または該化合物と他の芳香族化合物及び／または複素ヘテロ環式化合物及び／またはπ電子共役構造を形成し得る化合物とを単独重合または共重合させることにより一般式（ＩＩ）で表わされる化学構造を含む導電性重合体または（ＩＩＩ）もしくは（ＶＩ）で表わされる構造を含む導電性共重合体を製造する方法について説明する。 Next, a compound having a chemical structure represented by the general formula (I), (IV) or (VII), or other aromatic compound and / or heterocyclic compound and / or π-electron conjugated structure with the compound A conductive polymer containing a chemical structure represented by the general formula (II) or a conductive copolymer containing a structure represented by (III) or (VI) by homopolymerizing or copolymerizing with a compound that can be formed A manufacturing method will be described.
一般式（Ｉ）、（ＩＶ）もしくは（ＶＩＩ）で表わされる化学構造を有する化合物は、単独または他のπ電子共役構造の芳香族化合物及び／または複素ヘテロ環式化合物及び／またはπ電子共役構造を形成し得る化合物の共存下で、加温下、常温もしくは低温で、酸化剤を作用することによって重合させることができ、一般式（ＩＩ）の化学構造を含む重合体、あるいは一般式（ＩＩＩ）もしくは（ＶＩ）で表わされる化学構造を含む共重合体を極めて効率よく製造することができる。 The compound having the chemical structure represented by the general formula (I), (IV) or (VII) is an aromatic compound and / or a heterocyclic compound having a single or other π electron conjugated structure and / or a π electron conjugated structure. Can be polymerized by the action of an oxidizing agent in the presence of a compound that can form a compound at room temperature or low temperature under heating, and can be a polymer containing a chemical structure of the general formula (II) or a general formula (III ) Or (VI), a copolymer containing the chemical structure can be produced very efficiently.
特に、一般式（Ｉ）、（ＩＶ）もしくは（ＶＩＩ）で表わされる化学構造を有する化合物の重合反応を、スルホン酸基が脱離しやすい高温下で行わせた場合、一般式（ＩＩＩ）もしくは（ＶＩ）で表わされる化学構造を含む共重合体が得られる。 In particular, when the polymerization reaction of the compound having the chemical structure represented by the general formula (I), (IV) or (VII) is performed at a high temperature at which the sulfonic acid group is easily removed, the general formula (III) or ( A copolymer containing the chemical structure represented by VI) is obtained.
重合反応における酸化的脱水素反応を起こさせる酸化剤としては、一般に硫酸、発煙硫酸、三酸化硫黄、クロロ硫酸、フルオロ硫酸、アミド硫酸等のスルホン化剤、オゾン、パーオキサイド、過酸、２，３−ジクロロ−５，６−ジシアノ−１，４−ベンゾキノン、テトラクロロ−１，２−ベンゾキノン、テトラクロロー１，４−ベンゾキノン、テトラシアノ−１，４−ベンゾキノン等のキノン類、よう素、臭素等のハロゲン類、無水塩化アルミニウム／塩化第一銅、無水塩化第二鉄及びバナジウム系、マンガン系、ニッケル系等の金属錯体を用いた酸素酸化剤等、及びこれら複数の酸化剤の組合せが挙げられるが、特に限定されるものではない。 As an oxidizing agent that causes an oxidative dehydrogenation reaction in a polymerization reaction, generally, a sulfonating agent such as sulfuric acid, fuming sulfuric acid, sulfur trioxide, chlorosulfuric acid, fluorosulfuric acid, amidosulfuric acid, ozone, peroxide, peracid, 2, Quinones such as 3-dichloro-5,6-dicyano-1,4-benzoquinone, tetrachloro-1,2-benzoquinone, tetrachloro-1,4-benzoquinone, tetracyano-1,4-benzoquinone, iodine, bromine, etc. Examples include halogens, anhydrous aluminum chloride / cuprous chloride, anhydrous ferric chloride and oxygen oxidizers using vanadium-based, manganese-based, nickel-based and other metal complexes, and combinations of these oxidizers. There is no particular limitation.
酸化剤の使用量は、一般式（Ｉ）、（ＩＶ）もしくは（ＶＩＩ）で表わされる化学構造を有する化合物や酸化剤の種類によって異なるので一概には決められないが、一般には該化合物の１．１倍等量から２０倍等量の範囲で用いるのが望ましく、２倍から５倍等量の範囲が更に望ましい。 The amount of the oxidizing agent to be used varies depending on the type of the compound having the chemical structure represented by the general formula (I), (IV) or (VII) and the type of the oxidizing agent. It is desirable to use in the range of 1 to 20 equivalents, and more preferably in the range of 2 to 5 equivalents.
本製造法に用いられる一般式（Ｉ）、（ＩＶ）もしくは（ＶＩＩ）で表わされる化学構造を有する化合物の濃度は、その化合物の種類や反応スケールまたは溶媒等の化合物の種類や存否によって異なるが、一般には１０-3から１０モル／リットルの範囲が望ましく、１０-2から１モル／リットルの範囲が更に望ましい。 The concentration of the compound having the chemical structure represented by the general formula (I), (IV) or (VII) used in this production method varies depending on the type of the compound, the reaction scale, the type of the compound such as a solvent, and the presence or absence of the compound. In general, the range of 10 −3 to 10 mol / liter is desirable, and the range of 10 −2 to 1 mol / liter is more desirable.
また反応温度は、各々の反応方法によって定められるもので、特に限定できるものではないが一般には−７０℃から２５０℃の温度範囲が望ましく、更に好ましくは０℃から１５０℃の温度範囲で行われることが望ましい。また、化学構造によって限定できるものではないが、一般式（Ｉ）、（ＩＶ）もしくは（ＶＩＩ）で示される化学構造の化合物を単独で用いて、前記一般式（ＩＩＩ）もしくは（ＶＩ）で表わされる化学構造を含む共重合体を製造する場合は、好ましくは７０℃以上の温度が望ましい。 The reaction temperature is determined by each reaction method and is not particularly limited. However, in general, a temperature range of −70 ° C. to 250 ° C. is desirable, and a temperature range of 0 ° C. to 150 ° C. is more preferable. It is desirable. Further, although not limited by the chemical structure, the compound having the chemical structure represented by the general formula (I), (IV) or (VII) is used alone, and is represented by the general formula (III) or (VI). When a copolymer having a chemical structure is produced, a temperature of 70 ° C. or higher is desirable.
反応時間は、反応方法及び反応温度、反応圧力あるいは化合物の化学構造等によって異なるので一概には規定できないが、通常は０．０１時間から２４０時間が望ましく、０．１時間から２４時間の範囲が更に望ましい。反応圧力は、常圧で行われることが好ましいが、１０-5気圧から１００気圧下で行うことができ、１気圧から１０気圧の範囲で行うことが更に望ましい。
重合体繰返し単位のスルホン酸基による置換率（重合体中の全繰返し単位に対するスルホン酸基を有する繰返し単位のモル分率）は、重合反応中に反応温度を上昇させることにより減少させることができ、例えば、重合反応中に反応温度を上昇させて６０℃から１５０℃の範囲の温度に１０分間から２０時間、望ましくは８０℃から１２０℃の範囲の温度に３０分間から１０時間保つことにより、該置換率を減少させることができる。
The reaction time varies depending on the reaction method and reaction temperature, reaction pressure, chemical structure of the compound, etc., and thus cannot be specified unconditionally. However, it is generally desirable that the reaction time ranges from 0.01 hours to 240 hours, and ranges from 0.1 hours to 24 hours. More desirable. The reaction pressure is preferably carried out at normal pressure, but can be carried out at 10 −5 atm to 100 atm, and more preferably at 1 atm to 10 atm.
The rate of substitution of polymer repeating units with sulfonic acid groups (molar fraction of repeating units having sulfonic acid groups relative to all repeating units in the polymer) can be reduced by increasing the reaction temperature during the polymerization reaction. For example, by increasing the reaction temperature during the polymerization reaction and keeping it at a temperature in the range of 60 ° C. to 150 ° C. for 10 minutes to 20 hours, preferably at a temperature in the range of 80 ° C. to 120 ° C. for 30 minutes to 10 hours, The substitution rate can be reduced.
必要に応じて、用いられる反応溶媒は、反応温度や反応時間、または用いられる酸化剤や化合物の化学構造によって異なるので一概には規定できないが、化合物及び酸化剤を溶解し、かつ重合反応を阻害しないならば、如何なる溶媒であっても良い。例えば具体的には水、硫酸、発煙硫酸、蟻酸、酢酸、プロピオン酸、無水酢酸、あるいはテトラヒドロフラン、ジオキサン、ジエチルエーテル等のエーテル類、ジメチルホルムアミド、アセトニトリル、ベンゾニトリル、Ｎ−メチルピロリドン（ＮＭＰ）、ジメチルスルホキシド（ＤＭＳＯ）等の極性溶媒、酢酸エチル、酢酸ブチル等のエステル類、クロロホルム、塩化メチレン等の非芳香族性の塩素系溶媒等が用いられる。さらにはこれらの混合溶媒を用いることもできる。 If necessary, the reaction solvent used varies depending on the reaction temperature, reaction time, or the chemical structure of the oxidizing agent or compound used, but it cannot be specified unconditionally, but it dissolves the compound and the oxidizing agent and inhibits the polymerization reaction. If not, any solvent may be used. For example, water, sulfuric acid, fuming sulfuric acid, formic acid, acetic acid, propionic acid, acetic anhydride, ethers such as tetrahydrofuran, dioxane, diethyl ether, dimethylformamide, acetonitrile, benzonitrile, N-methylpyrrolidone (NMP), Polar solvents such as dimethyl sulfoxide (DMSO), esters such as ethyl acetate and butyl acetate, and non-aromatic chlorine-based solvents such as chloroform and methylene chloride are used. Furthermore, these mixed solvents can also be used.
上述の製造方法により得られた一般式（ＩＩ）で表わされる構造単位の少なくとも１つを繰返し単位として含む重合体や、あるいは一般式（ＩＩＩ）もしくは（ＶＩ）で表わされる化学構造を含む共重合体は、溶媒に対して高い溶解性を示し、特にスルホン酸基の寄与により水溶性も併せ持つ。そして、この特性から限外ろ過、透析及び／またはイオン交換操作によって単離精製する事ができる。さらに一般式（ＩＩ）の化学構造を含む重合体や一般式（ＩＩＩ）もしくは（ＶＩ）で表わされる共重合体が反応溶媒から析出物として得られる場合には、ろ過、再沈澱及び／または溶媒分別法等によって単離精製を行なうことができる。 A polymer containing at least one structural unit represented by the general formula (II) obtained by the above-mentioned production method as a repeating unit, or a co-polymer containing a chemical structure represented by the general formula (III) or (VI) The coalescence shows high solubility in a solvent, and also has water solubility particularly due to the contribution of sulfonic acid groups. And from this characteristic, it can be isolated and purified by ultrafiltration, dialysis and / or ion exchange operation. Furthermore, when the polymer containing the chemical structure of the general formula (II) or the copolymer represented by the general formula (III) or (VI) is obtained as a precipitate from the reaction solvent, filtration, reprecipitation and / or solvent Isolation and purification can be performed by a fractionation method or the like.
一般式（Ｉ）、（ＩＶ）もしくは（ＶＩＩ）で表わされる化合物と、他のπ電子共役構造の芳香族化合物及び／または複素ヘテロ環式化合物、または反応後にπ電子共役構造を形成できる化合物とを共存させ、あるいは順次追添によって重合させることで、一般式（ＩＩＩ）もしくは（ＶＩ）で表わされる化学構造を含む共重合体が製造される。ここで用いられる芳香族化合物や複素ヘテロ環式化合物としては、イソチアナフテン、イソベンゾフラン、イソベンゾインドリン、イソベンゾセレナフェン、イソベンゾテレナフェン、チオフェン、ピロール、フラン、セレノフェン、テルロフェン、アニリン、ベンゼン、ナフト［２，３−ｃ］チオフェン、アントラ［２，３−ｃ］チオフェン、ナフタセノ［２，３−ｃ］チオフェン、ペンタセノ［２，３−ｃ］チオフェン、ペリロ［２，３−ｃ］チオフェン、アセナフト［２，３−ｃ］チオフェン及びそれらの各種置換基を有する誘導体が挙げられる。ここで好ましい置換基としては、前記置換基Ｒ1 、Ｒ2 、Ｒ3 、Ｒ4 及びＲ5 で示したものと同じものが挙げられる。反応後に共役構造を形成できる化合物としては、上記イソチアナフテン、５−アルコキシ−イソチアナフテン、５，６−ジアルコキシ−イソチアナフテン、ナフト［２，３−ｃ］チオフェン、アントラ［２，３−ｃ］チオフェン、ナフタセノ［２，３−ｃ］チオフェン、ペンタセノ［２，３−ｃ］チオフェン、ペリロ［２，３−ｃ］チオフェン、アセナフト［２，３−ｃ］チオフェンの１，３−ジヒドロ体、１，３−ジハロゲノ体、１，１，３，３−テトラハロゲノ体及び２−オキサイド体等が挙げられる。また、縮合環に窒素等を含んだ、１，３−ジヒドロチエノ［ｃ］ピリジン、１，３−ジヒドロチエノ［ｃ］ピラジン、１，３−ジヒドロチエノ［ｃ］ピリダジン、１，３−ジヒドロチエノ［ｃ］キノキサリンが用いられる。なかでも、好適にはチオフェン、イソチアナフテン、ピロ−ル、アニリン及びナフト［ｃ］チオフェン構造を形成できる化合物を用いることができる。 A compound represented by the general formula (I), (IV) or (VII), an aromatic compound and / or a heterocyclic compound having another π electron conjugated structure, or a compound capable of forming a π electron conjugated structure after the reaction; Copolymers containing a chemical structure represented by the general formula (III) or (VI) are produced by polymerizing by coexistence or by sequential addition. The aromatic compounds and heterocyclic compounds used here are isothianaphthene, isobenzofuran, isobenzoindoline, isobenzoselenaphene, isobenzoterenaphene, thiophene, pyrrole, furan, selenophene, tellurophene, aniline, benzene. , Naphtho [2,3-c] thiophene, anthra [2,3-c] thiophene, naphthaceno [2,3-c] thiophene, pentaseno [2,3-c] thiophene, perilo [2,3-c] thiophene , Acenaphtho [2,3-c] thiophene and derivatives having various substituents thereof. Preferred examples of the substituent include the same substituents as those described for the substituents R 1 , R 2 , R 3 , R 4 and R 5 . Compounds that can form a conjugated structure after the reaction include isothianaphthene, 5-alkoxy-isothianaphthene, 5,6-dialkoxy-isothianaphthene, naphtho [2,3-c] thiophene, anthra [2,3 -C] thiophene, naphthaceno [2,3-c] thiophene, pentaseno [2,3-c] thiophene, perilo [2,3-c] thiophene, 1,3-dihydro of acenaphtho [2,3-c] thiophene Body, 1,3-dihalogeno body, 1,1,3,3-tetrahalogeno body, 2-oxide body and the like. In addition, 1,3-dihydrothieno [c] pyridine, 1,3-dihydrothieno [c] pyrazine, 1,3-dihydrothieno [c] pyridazine, 1,3-dihydrothieno [c] quinoxaline containing nitrogen or the like in the condensed ring Is used. Among them, a compound capable of forming a thiophene, isothianaphthene, pyrrole, aniline and naphtho [c] thiophene structure can be preferably used.
本発明にもとづく、共重合体を製造する方法において、一般式（Ｉ）、（ＩＶ）もしくは（ＶＩＩ）で表わされる化合物と、芳香族化合物あるいは複素環化合物や共役構造を形成できる化合物との仕込割合をかえることによって、一般式（ＩＩＩ）もしくは（ＶＩ）で表わされる化学構造を含む重合体中のスルホン酸基の含有率（重合体繰返し単位のスルホン酸基による置換率）をきわめて簡便に制御できる。また、共重合させる芳香族化合物、複素環化合物あるいは共役構造を形成できる化合物の種類や割合を変えることにより、一般式（ＩＩＩ）もしくは（ＶＩ）で表わされる化学構造を含む重合体の物性を容易に制御できる。 In the method for producing a copolymer based on the present invention, the compound represented by the general formula (I), (IV) or (VII) is charged with an aromatic compound, a heterocyclic compound or a compound capable of forming a conjugated structure. By changing the ratio, the content of sulfonic acid groups in the polymer containing the chemical structure represented by general formula (III) or (VI) (substitution rate of polymer repeating units by sulfonic acid groups) can be controlled very easily. it can. In addition, by changing the type and ratio of the aromatic compound, heterocyclic compound or compound capable of forming a conjugated structure to be copolymerized, the physical properties of the polymer containing the chemical structure represented by the general formula (III) or (VI) can be easily obtained. Can be controlled.
本発明の前記一般式（Ｉ）、（ＩＶ）あるいは（ＶＩＩ）で表わされる化学構造の化合物を重合して得られる水あるいは有機溶媒可溶性導電性重合体は、公知の導電性重合体、例えばポリチオフェン誘導体（特開平２−２４２８１６号）と比較すると、半導体としてのエネルギーギャップが小さく、低いドーピングレベルで高い導電性を示すことからその導電状態が極めて安定であるという特徴を持つ。また、置換基のスルホン酸基の影響から自己ドーピング状態が容易に発現する。 The water or organic solvent-soluble conductive polymer obtained by polymerizing the compound having the chemical structure represented by the general formula (I), (IV) or (VII) of the present invention is a known conductive polymer such as polythiophene. Compared with a derivative (Japanese Patent Laid-Open No. Hei 2-242816), the energy gap as a semiconductor is small, and since it exhibits high conductivity at a low doping level, its conductive state is extremely stable. In addition, the self-doping state easily develops due to the influence of the sulfonic acid group of the substituent.
本発明においては、スルホン酸基を有する、一般式（Ｉ）で表わされる縮合ヘテロ多環式化合物に酸化剤を作用させることにより、一般式（ＩＩ）あるいは一般式（ＩＩＩ）で表される化学構造を含む導電性重合体が極めて効率よく製造できることに基づくものである。これまで、イソチアナフテンやナフト［ｃ］チオフェンのようなπ電子共役系の縮合ヘテロ多環式化合物は、非常に反応性が高く、それ故に製造上の取扱が難しかった。しかしながら、本発明の一般式（Ｉ）で表わされるスルホン酸基を有する１，３−ジヒドロヘテロ多環式化合物は、極めて安定であり、該化合物製造における単位操作において容易に取り扱うことができる。すなわち、本発明により、スルホン酸基置換の１，３−ジヒドロ構造の縮合ヘテロ多環式化合物をモノマーとして用いた重合によりスルホン酸基を有する導電性高分子及び共重合体が製造できるものである。 In the present invention, the chemistry represented by the general formula (II) or the general formula (III) is obtained by allowing an oxidizing agent to act on the condensed heteropolycyclic compound represented by the general formula (I) having a sulfonic acid group. This is based on the fact that a conductive polymer including a structure can be produced very efficiently. Up to now, π-electron conjugated fused heteropolycyclic compounds such as isothianaphthene and naphtho [c] thiophene have been very reactive and therefore difficult to handle in production. However, the 1,3-dihydroheteropolycyclic compound having a sulfonic acid group represented by the general formula (I) of the present invention is extremely stable and can be easily handled in unit operations in the production of the compound. That is, according to the present invention, a conductive polymer and a copolymer having a sulfonic acid group can be produced by polymerization using a sulfonic acid group-substituted 1,3-dihydro-structured condensed heteropolycyclic compound as a monomer. .
以下実施例によって、本発明をさらに詳しく説明する。しかし、本発明の技術的範囲をこれらの実施例によって限定されるものでない。
（実施例１）
一般式（Ｉ）におけるｋが０である一般式（ＩＶ）で表わされる化合物の製造方法＜Ｒ1 ＝Ｒ2 ＝Ｒ3 ＝Ｈ、Ｘ1 ＝Ｘ2 ＝Ｘ3 ＝Ｘ4 ＝Ｈ、Ｍ＝Ｎａ+ ＞
２０℃以下に冷却した４ｍｌの発煙硫酸（２０％ＳＯ3 ）に、公知な１，３−ジヒドロイソチアナフテン１ｇを撹拌しながらゆっくりと加え、室温下で４時間撹拌した。反応混合物を氷水１５０ｍｌ中に注ぎ入れ、塩化ナトリウム２０ｇを加えて１，３−ジヒドロイソチアナフテン−５−スルホン酸ナトリウムを塩析させ、遠心分離機により単離した。真空乾燥して灰色粉末の化合物を８５０ｍｇ得た。
The following examples further illustrate the present invention. However, the technical scope of the present invention is not limited by these examples.
Example 1
Production method of compound represented by general formula (IV) in which k in general formula (I) is 0 <R 1 = R 2 = R 3 = H, X 1 = X 2 = X 3 = X 4 = H, M = Na + >
1 g of known 1,3-dihydroisothianaphthene was slowly added to 4 ml of fuming sulfuric acid (20% SO 3 ) cooled to 20 ° C. or lower with stirring, and the mixture was stirred at room temperature for 4 hours. The reaction mixture was poured into 150 ml of ice water, 20 g of sodium chloride was added to salt out sodium 1,3-dihydroisothianaphthene-5-sulfonate and isolated by a centrifuge. Vacuum drying gave 850 mg of a gray powder compound.
（実施例２）
一般式（ＩＩ）におけるｋが０である下記一般式（Ｖ）
(Example 2)
The following general formula (V) wherein k in general formula (II) is 0
５．５ｇの塩化第２鉄を過酸化水素水（３０％）１ｍｌと水１０ｍｌの混合した系に実施例１と同様の方法で製造した１，３−ジヒドロイソチアナフテン−５−スルホン酸ナトリウム１ｇを撹拌しながらゆっくりと加えた。室温下で１日撹拌を続けたところ粘調な黒色反応液が得られた。
反応混合物を真空乾燥した後、１００ｍｌのアセトン中に投入し、沈澱した重合物を遠心分離機により分離した。乾燥後、重合体を０．１Ｎ ＮａＯＨ水溶液７００ｍｌに溶解し、遠心分離により不溶物を除去、さらに１μｍの濾過膜に通して不純物を除去した。さらに、Ｈ形のイオン交換樹脂（アンバーライトＩＲ−１２０Ｂ）を用いてＮａ+ イオンをＨ+ へと変換した。水溶液から水を留去し、真空乾燥して青色ポリマー０．２ｇを得た。重合体繰返し単位のスルホン酸基による置換率をアルカリによる中和滴定で求めたところ、スルホン酸置換体組成がほぼ１００モル％（モル分率で１．０）の重合体であった。分子量は、ＧＰＣ測定から数平均分子量が１８０００であった（ポリスチレンスルホン酸ナトリウム換算）。
Sodium 1,3-dihydroisothianaphthene-5-sulfonate prepared in the same manner as in Example 1 in a mixed system of 5.5 g of ferric chloride with 1 ml of hydrogen peroxide (30%) and 10 ml of water 1 g was added slowly with stirring. When stirring was continued for 1 day at room temperature, a viscous black reaction solution was obtained.
The reaction mixture was vacuum dried and then poured into 100 ml of acetone, and the precipitated polymer was separated by a centrifuge. After drying, the polymer was dissolved in 700 ml of 0.1N NaOH aqueous solution, insoluble matters were removed by centrifugation, and impurities were removed by passing through a 1 μm filter membrane. Further, Na + ions were converted to H + using an H-type ion exchange resin (Amberlite IR-120B). Water was distilled off from the aqueous solution and vacuum dried to obtain 0.2 g of a blue polymer. When the substitution rate of the polymer repeating unit by the sulfonic acid group was determined by neutralization titration with alkali, the polymer had a sulfonic acid substitution product composition of approximately 100 mol% (mol fraction: 1.0). As for the molecular weight, the number average molecular weight was 18000 from GPC measurement (in terms of sodium polystyrene sulfonate).
（実施例３）
一般式（ＩＩＩ）におけるｋが０である一般式（ＶＩ）で表わされる化学構造を含む重合体の製造方法＜Ｒ1 ＝Ｒ2 ＝Ｒ3 ＝Ｈ、Ｍ＝Ｎａ+ 、ｍ＝０．８、ｎ＝０．２、Ａｒ＝１，３−イソチアナフテニレン＞
１０℃以下に保持した硫酸２５ｍｌ中に実施例１と同様の方法で製造した１，３−ジヒドロイソチアナフテン−５−スルホン酸ナトリウム１ｇを撹拌しながらゆっくりと加えた。そして室温下１時間撹拌すると、反応液は赤紫色を呈した。さらに、８０℃で２時間加熱した後、得られた黒色の反応混合物を６０ｍｌの０．１Ｎ ＮａＯＨ／ＭｅＯＨ中に投入した。析出した重合物を遠心分離機により単離し、水１００ｍｌに溶解して透析膜を通して不純物の硫酸ナトリウムを除去した。水溶液から水を留去した後、真空乾燥して青色ポリマー０．３ｇを得た。得られた重合体の可視近赤外吸収スペクトルを図１に示す。
元素分析結果は次の通り。
計算値（Ｃ8 Ｈ3 Ｓ2 Ｏ3 Ｎａ）0.8 （Ｃ8 Ｈ4 Ｓ）0.2 ）；Ｃ：４４．２７，Ｈ：２．９６，Ｓ：２６．５９，Ｎａ：８．４８，測定値；Ｃ：４４．５２，Ｈ：３．２３，Ｓ：２６．４１，Ｎａ：８．９２。
次に、重合体繰返し単位のスルホン酸基による置換率を測定するために、得られた重合物０．２ｇを水に溶かしてＨ形イオン交換樹脂（アンバーライトＩＲ−１２０Ｂ）でＮａ+ 体からＨ+ 体へと変換した。水溶液から水を留去し、真空乾燥して青色ポリマー１２０ｍｇを得た。
このポリマーは、中和滴定により求めた該置換率が、平均モル分率で０．８の共重合体であった。これは、重合反応中に一部のスルホン酸基が脱離して共重合体を与えたものである。
(Example 3)
Production Method of Polymer Containing Chemical Structure Represented by General Formula (VI) where k in General Formula (III) is 0 <R 1 = R 2 = R 3 = H, M = Na + , m = 0.8 , N = 0.2, Ar = 1,3-isothianaphthenylene>
1 g of sodium 1,3-dihydroisothianaphthene-5-sulfonate prepared in the same manner as in Example 1 was slowly added to 25 ml of sulfuric acid kept at 10 ° C. or lower with stirring. And when it stirred at room temperature for 1 hour, the reaction liquid exhibited reddish purple. Furthermore, after heating at 80 ° C. for 2 hours, the resulting black reaction mixture was poured into 60 ml of 0.1N NaOH / MeOH. The precipitated polymer was isolated with a centrifuge, dissolved in 100 ml of water, and impurities sodium sulfate was removed through a dialysis membrane. Water was distilled off from the aqueous solution, followed by vacuum drying to obtain 0.3 g of a blue polymer. The visible near infrared absorption spectrum of the obtained polymer is shown in FIG.
The results of elemental analysis are as follows.
Calculated value (C 8 H 3 S 2 O 3 Na) 0.8 (C 8 H 4 S) 0.2 ); C: 44.27, H: 2.96, S: 26.59, Na: 8.48, measured value C: 44.52, H: 3.23, S: 26.41, Na: 8.92.
Next, in order to measure the substitution rate of the polymer repeating unit with a sulfonic acid group, 0.2 g of the obtained polymer was dissolved in water, and the H + ion exchange resin (Amberlite IR-120B) was used to form the Na + form. Converted to H + form. Water was distilled off from the aqueous solution and vacuum-dried to obtain 120 mg of a blue polymer.
This polymer was a copolymer having a substitution ratio of 0.8 determined by neutralization titration as an average molar fraction. This is one in which a part of the sulfonic acid group is eliminated during the polymerization reaction to give a copolymer.
（実施例４）
一般式（ＩＩＩ）におけるｋが０である一般式（ＶＩ）の化学構造で表わされる重合体の製造方法＜Ｒ1 ＝Ｒ2 ＝Ｒ3 ＝Ｈ、Ｍ＝Ｈ+ 、ｍ＝０．６、ｎ＝０．４、Ａｒ＝１，３−イソチアナフテニレン＞
１０℃以下に保持した５ｍｌの硫酸に、実施例１と同様の方法で製造した１，３−ジヒドロイソチアナフテン−５−スルホン酸ナトリウム ０．７ｇ、および１，３−ジヒドロイソチアナフテン０．２８ｇを撹拌しながらゆっくりと加えた。室温下で１時間撹拌を続けたところ反応液は紫色を呈し、その後９０℃で３時間加熱すると反応液は黒色に変化した。反応混合物を６０ｍｌの０．１ＮのＮａＯＨ／ＭｅＯＨ中に投入し、沈澱した重合物を遠心分離機により分離した。重合体を水１００ｍｌに溶解し透析膜に通して不純物の硫酸ナトリウムを除去した。
さらに、Ｈ形イオン交換樹脂（アンバーライトＩＲ−１２０Ｂ）を用いてＮａ+ イオンをＨ+ へと変換した。水溶液から水を留去し、真空乾燥して青色ポリマー０．５ｇを得た。得られたポリマーの可視近赤外吸収スペクトルを図２に示す。
このポリマーは、中和滴定により求めた重合体繰返し単位のスルホン酸基による置換率が、平均モル分率で０．６の共重合体であった。
(Example 4)
Production method of polymer represented by chemical structure of general formula (VI) wherein k in general formula (III) is 0 <R 1 = R 2 = R 3 = H, M = H + , m = 0.6, n = 0.4, Ar = 1,3-isothianaphthenylene>
To 5 ml of sulfuric acid kept at 10 ° C. or lower, 0.7 g of sodium 1,3-dihydroisothianaphthene-5-sulfonate prepared in the same manner as in Example 1, and 1,3-dihydroisothianaphthene 28 g was added slowly with stirring. When the stirring was continued at room temperature for 1 hour, the reaction solution became purple, and when heated at 90 ° C. for 3 hours, the reaction solution turned black. The reaction mixture was poured into 60 ml of 0.1N NaOH / MeOH and the precipitated polymer was separated by a centrifuge. The polymer was dissolved in 100 ml of water and passed through a dialysis membrane to remove the sodium sulfate as an impurity.
Further, Na + ions were converted to H + using an H-type ion exchange resin (Amberlite IR-120B). Water was distilled off from the aqueous solution, followed by vacuum drying to obtain 0.5 g of a blue polymer. The visible near infrared absorption spectrum of the obtained polymer is shown in FIG.
This polymer was a copolymer having a substitution rate of sulfonic acid groups of polymer repeating units determined by neutralization titration in an average molar fraction of 0.6.
（実施例５）
一般式（Ｉ）におけるｋが１である一般式（ＶＩＩ）で表わされる化合物の製造方法＜Ｒ1 ＝Ｒ2 ＝Ｒ3 ＝Ｒ4 ＝Ｒ5 ＝Ｈ、Ｘ1 ＝Ｘ2 ＝Ｘ3 ＝Ｘ4 ＝Ｈ、Ｍ＝Ｎａ+ ＞
実施例１の１，３−ジヒドロイソチアナフテンの代わりに、公知の１，３−ナフト［２，３−ｃ］チオフェンを１ｇ使用し、同様にスルホン化反応を施して灰色粉末の１，３−ナフト［２，３−ｃ］チオフェンスルホン酸ナトリウム化合物４２０ｍｇを得た。
(Example 5)
Production method of compound represented by general formula (VII) in which k in general formula (I) is 1 <R 1 = R 2 = R 3 = R 4 = R 5 = H, X 1 = X 2 = X 3 = X 4 = H, M = Na + >
Instead of 1,3-dihydroisothianaphthene of Example 1, 1 g of known 1,3-naphtho [2,3-c] thiophene was used, and a sulfonation reaction was similarly performed to obtain 1,3 of gray powder. -420 mg of sodium naphtho [2,3-c] thiophenesulfonate compound was obtained.
（実施例６）
一般式（ＩＩ）におけるｋが１である下記一般式（ＶＩＩＩ）
(Example 6)
The following general formula (VIII) wherein k in the general formula (II) is 1
実施例２の方法に準じ、１，３−ジヒドロイソチアナフテンの代わりにモノマ−として、実施例５の方法に従って製造した１，３−ジヒドロナフト［２，３−ｃ］チオフェン−６−スルホン酸ナトリウム７００ｍｇを用いた。実施例２と同様に重合、及び後処理を経て酸形の重合物２００ｍｇを得た。重合体繰返し単位のスルホン酸基による置換率はほぼ１００％であった。この重合物を水に溶かしてアンモニウム水を過剰に入れ、減圧留去してアンモニウム塩の重合体を得た。重合体を再度水に溶かして、可視近赤外吸収スペクトルを測定した（図３）。
According to the method of Example 2, 1,3-dihydronaphtho [2,3-c] thiophene-6-sulfonic acid prepared according to the method of Example 5 as a monomer instead of 1,3-dihydroisothianaphthene Sodium 700 mg was used. In the same manner as in Example 2, after polymerization and post-treatment, 200 mg of an acid polymer was obtained. The substitution rate of the polymer repeating unit by the sulfonic acid group was almost 100%. This polymer was dissolved in water and excess ammonium water was added and distilled off under reduced pressure to obtain an ammonium salt polymer. The polymer was dissolved again in water and the visible near infrared absorption spectrum was measured (FIG. 3).
（実施例７）
一般式（Ｉ）におけるｋが０である一般式（ＩＶ）で表わされる化合物の製造方法〈Ｒ1 ＝Ｒ2 ＝Ｒ3 ＝Ｈ、Ｘ1 ＝Ｘ2 ＝Ｘ3 ＝Ｘ4 ＝Ｈ、Ｍ＝（ＣＨ3 ）3 （Ｎ+ ｎ−Ｃ8 Ｈ17）〉
精製水１００ｍｌに、１，３−ジヒドロイソチアナフテン−５−スルホン酸ナトリウム３ｇ（１２．７ミリモル）を２０℃に保ちながら溶解させ、この系にｎ−オクチルトリメチルアンモニウムブロミド（東京化成（株）製）３．２０ｇ（１２．７ミリモル）を撹拌しながら加えた。３０分後にクロロホルムで３回抽出（２０ｍｌ×３回）後、無水硫酸ナトリウムでクロロホルム層を乾燥、減圧留去してイオンコンプレックス体のオイル状半固体を取得した（得量４．３５ｇ、収率８９％）。得られたポリマーは、クロロホルム、トルエン、ジメチルスルホキシド、テトラヒドロフラン及びジメチルホルムアミドに可溶であった。
(Example 7)
Production method of compound represented by general formula (IV) in which k in general formula (I) is 0 <R 1 = R 2 = R 3 = H, X 1 = X 2 = X 3 = X 4 = H, M = (CH 3 ) 3 (N + n-C 8 H 17 )>
In 100 ml of purified water, 3 g (12.7 mmol) of sodium 1,3-dihydroisothianaphthene-5-sulfonate was dissolved at 20 ° C., and n-octyltrimethylammonium bromide (Tokyo Chemical Industry Co., Ltd.) was dissolved in this system. 3.20 g (12.7 mmol) was added with stirring. After 30 minutes extraction with chloroform three times (20 ml × 3 times), the chloroform layer was dried over anhydrous sodium sulfate and distilled under reduced pressure to obtain an oily semisolid of an ion complex (yield 4.35 g, yield). 89%). The obtained polymer was soluble in chloroform, toluene, dimethyl sulfoxide, tetrahydrofuran and dimethylformamide.
（実施例８）
一般式（Ｉ）におけるｋが０であり、Ｘ1 及びＸ3 がＣｌであり、Ｘ2 及びＸ4 がＨである化合物を経由して、一般式（ＩＩ）におけるｋが０で表わされる一般式（Ｖ）で表される化学構造を含む重合体の製造方法〈Ｒ1 ＝Ｒ2 ＝Ｒ3 ＝Ｈ、Ｍ＝Ｎａ+ 〉
実施例７において得られたイオンコンプレックス体（４．３５ｇ）に、乾燥したクロロホルム２０ｍｌを加え、Ｎ−クロロサクシンイミド（ＮＣＳ）を３．１７ｇ（２３．７ミリモル）加えた。この時、１，３−ジクロロイソチアナフテン−５−スルホン酸アンモニウム塩は系内に精製するが、単離することなく、２時間加熱還流すると黒青色の溶液が得られた。冷却後、反応液から不溶物を除き、有機層を減圧乾燥し、次いで０．１Ｎ ＮａＯＨを２００ｍｌ加えて水溶性のッポリマー溶液を得た。この溶液を、更に、酸型イオン交換カラムに通すことにより、酸型のポリマー水溶液を得た（ｐＨ１．８）。この溶液の可視近赤外吸収スペクトルは、図２と同じドープした曲線を与えた。
(Example 8)
K in general formula (I) is 0, X 1 and X 3 are Cl, and X 2 and X 4 are H. Production method of polymer containing chemical structure represented by formula (V) <R 1 = R 2 = R 3 = H, M = Na + >
To the ion complex (4.35 g) obtained in Example 7, 20 ml of dried chloroform was added, and 3.17 g (23.7 mmol) of N-chlorosuccinimide (NCS) was added. At this time, although 1,3-dichloroisothianaphthene-5-sulfonic acid ammonium salt was purified in the system, it was heated and refluxed for 2 hours without isolation to obtain a black-blue solution. After cooling, insoluble matters were removed from the reaction solution, the organic layer was dried under reduced pressure, and then 200 ml of 0.1N NaOH was added to obtain a water-soluble polymer solution. The solution was further passed through an acid type ion exchange column to obtain an acid type polymer aqueous solution (pH 1.8). The visible near infrared absorption spectrum of this solution gave the same doped curve as in FIG.
（実施例９）
硝子板を支持体として、その表面に実施例４に記載の方法で製造した導電性重合体の１０重量％水溶液を塗布し乾燥した。更に真空乾燥した後、硝子板より剥離させ厚さ約３０μｍの自立膜を得た。この自立膜の室温における電気伝導度（４端子測定系）はσ＝５×１０-2Ｓ／ｃｍであった。この自立膜の空気中室温下における電気伝導度の値は３ヶ月後も安定に維持されていた。
Example 9
Using a glass plate as a support, a 10% by weight aqueous solution of a conductive polymer produced by the method described in Example 4 was applied to the surface and dried. Furthermore, after vacuum-drying, it peeled from the glass plate and obtained the self-supporting film | membrane with a thickness of about 30 micrometers. The electric conductivity (4-terminal measurement system) of this free-standing film at room temperature was σ = 5 × 10 −2 S / cm. The value of the electric conductivity of the self-supporting film at room temperature in air was stably maintained even after 3 months.
（実施例１０）
一般式（Ｉ）におけるｋが０である一般式（ＩＶ）で表わされる化合物の製造方法〈Ｒ1 ＝Ｃ10Ｈ21Ｏ−、Ｒ2 ＝Ｒ3 ＝Ｈ、Ｘ1 ＝Ｘ2 ＝Ｘ3 ＝Ｘ4 ＝Ｈ、Ｍ＝Ｎａ+ 〉
２ｍｌの発煙硫酸（２０％ＳＯ3 ）を含む硫酸溶液８ｍｌを２０℃以下に冷却し、公知な５−デシルオキシ−１，３−ジヒドロイソチアナフテン５００ｍｇを撹拌しながらゆっくりと加え、室温下で３時間撹拌した。反応混合物を氷水１００ｍｌ中に注ぎ入れ、塩化ナトリウム１４ｇを加えて、５−デシルオキシ−１，３−ジヒドロイソチアナフテン−６−スルホン酸ナトリウムを塩析させ、遠心分離機により分離した。真空乾燥して、１８０ｍｇの灰色粉末状化合物を得た。
(Example 10)
Production method of compound represented by general formula (IV) in which k in general formula (I) is 0 <R 1 = C 10 H 21 O—, R 2 = R 3 = H, X 1 = X 2 = X 3 = X 4 = H, M = Na + >
8 ml of a sulfuric acid solution containing 2 ml of fuming sulfuric acid (20% SO 3 ) is cooled to 20 ° C. or lower, and 500 mg of known 5-decyloxy-1,3-dihydroisothianaphthene is slowly added with stirring. Stir for hours. The reaction mixture was poured into 100 ml of ice water, 14 g of sodium chloride was added to salt out sodium 5-decyloxy-1,3-dihydroisothianaphthene-6-sulfonate and separated by a centrifuge. Vacuum drying gave 180 mg of a gray powdery compound.
（実施例１１）
一般式（ＩＩ）におけるｋが０である前記一般式（Ｖ）で表わされる重合体の製造方法〈Ｒ1 ＝Ｃ10Ｈ21Ｏ−、Ｒ2 ＝Ｒ3 ＝Ｈ、Ｍ＝Ｈ+ 〉
６００ｍｇの塩化第二鉄と１００ｍｇの５−デシルオキシ−１，３−ジヒドロイソチアナフテン−６−スルホン酸の混合物に１ｍｌの水をゆっくり加え、室温下で３０分間撹拌したところ、粘調な黒色反応物が得られた。反応混合物を１０ｍｌのアセトン中に注ぎ込み、析出した重合物を遠心分離機により分離した。
乾燥後重合物を１００ｍｌの０．１Ｎ−ＮａＯＨ水溶液に溶解させ、不溶物を１μｍのフィルター膜で除去した。重合体を含んだアルカリ水溶液を、１Ｎ−ＨＣｌを加えて酸性化し、Ｈ型の重合体に変換した。水溶液をクロロホルムで３回抽出し、クロロホルムを留去して５５ｍｇの重合体を得た。
(Example 11)
Production method of polymer represented by general formula (V) wherein k in general formula (II) is 0 <R 1 = C 10 H 21 O—, R 2 = R 3 = H, M = H + >
1 ml of water was slowly added to a mixture of 600 mg of ferric chloride and 100 mg of 5-decyloxy-1,3-dihydroisothianaphthene-6-sulfonic acid, and the mixture was stirred at room temperature for 30 minutes. Things were obtained. The reaction mixture was poured into 10 ml of acetone, and the precipitated polymer was separated by a centrifuge.
After drying, the polymer was dissolved in 100 ml of 0.1N NaOH aqueous solution, and insoluble matter was removed with a 1 μm filter membrane. The alkaline aqueous solution containing the polymer was acidified by adding 1N-HCl to convert it into an H-type polymer. The aqueous solution was extracted three times with chloroform, and chloroform was distilled off to obtain 55 mg of a polymer.
（実施例１２）
硝子板を支持体として、その表面に実施例２に記載の方法で製造した水溶性導電性高分子を１重量％含む水溶液をスピンコーター（室温下、回転数１０００ｒｐｍ）を用いて塗布し、約０．０５μｍ（デクタク式触針法で測定）の薄膜を形成した。この薄膜と硝子板との密着性は良好であり、表面抵抗は約７．６×１０5Ω／□であった。また５００ｎｍの可視光の透過率は９６％であった。このように、該重合体は、極めて透明性の優れた導電膜を与えた。
同様にスピンコーターの回転数を変えて薄膜を作製し、得られた特性を表１に示す。
Example 12
Using a glass plate as a support, an aqueous solution containing 1% by weight of a water-soluble conductive polymer produced by the method described in Example 2 was applied to the surface using a spin coater (room temperature, rotation speed: 1000 rpm), and about A thin film having a thickness of 0.05 μm (measured by a dictacle stylus method) was formed. The adhesion between the thin film and the glass plate was good, and the surface resistance was about 7.6 × 10 5 Ω / □. The transmittance for visible light at 500 nm was 96%. Thus, the polymer gave a conductive film with extremely excellent transparency.
Similarly, thin films were prepared by changing the rotation speed of the spin coater, and the obtained characteristics are shown in Table 1.
本発明の製造法で製造された導電性重合体は、水溶性及び／または有機溶媒可溶性であり加工性の優れた高い導電性重合体である。そのため精密な加工が要求される電極、センサー、エレクトロニクス表示素子、非線形光学素子、光学変換素子、帯電防止材など各種導電材料あるいは光学材料として有用なものである。
また、本発明の製造法によって、ホモポリマーだけでなく、π共役系主鎖骨格を構成する共重合体組成を制御して容易に共重合体を製造することができる。また、重合体がスルホン酸基を有することから自己ドーピング機能を持った電導度の安定な重合体を与えることができる。さらには、原料として用いられるスルホン酸置換基を有する多環複素ヘテロ系化合物はきわめて安定な化合物であり、穏和な条件で高い導電性を有する重合体を効率よく製造するのに特に有用である。
The conductive polymer produced by the production method of the present invention is a conductive polymer that is water-soluble and / or organic solvent-soluble and excellent in processability. Therefore, it is useful as various conductive materials or optical materials such as electrodes, sensors, electronic display elements, nonlinear optical elements, optical conversion elements, and antistatic materials that require precise processing.
Moreover, according to the production method of the present invention, a copolymer can be easily produced by controlling not only the homopolymer but also the composition of the copolymer constituting the π-conjugated main chain skeleton. In addition, since the polymer has a sulfonic acid group, a polymer having a self-doping function and a stable conductivity can be provided. Furthermore, the polycyclic hetero-hetero compound having a sulfonic acid substituent used as a raw material is a very stable compound, and is particularly useful for efficiently producing a polymer having high conductivity under mild conditions.
Claims (5)
A self-supporting film peeled from the support according to claim 4.
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