JPH02180922A - Conductive polymer - Google Patents
Conductive polymerInfo
- Publication number
- JPH02180922A JPH02180922A JP33560088A JP33560088A JPH02180922A JP H02180922 A JPH02180922 A JP H02180922A JP 33560088 A JP33560088 A JP 33560088A JP 33560088 A JP33560088 A JP 33560088A JP H02180922 A JPH02180922 A JP H02180922A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- polymerization
- group
- pyrrole
- bond
- 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.)
- Pending
Links
- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 14
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 40
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 125000005194 alkoxycarbonyloxy group Chemical group 0.000 claims abstract description 3
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 125000005362 aryl sulfone group Chemical group 0.000 claims abstract description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Chemical group 0.000 claims description 2
- 239000011669 selenium Chemical group 0.000 claims description 2
- 125000001174 sulfone group Chemical group 0.000 claims description 2
- 239000011593 sulfur Chemical group 0.000 claims description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical group [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 34
- -1 poly(pyrrolo[3,4-c]pyrrole) Polymers 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 4
- 239000004020 conductor Substances 0.000 abstract description 3
- 239000002019 doping agent Substances 0.000 abstract description 3
- 239000007772 electrode material Substances 0.000 abstract description 3
- 150000001449 anionic compounds Chemical class 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 150000002891 organic anions Chemical class 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 abstract description 2
- 125000002618 bicyclic heterocycle group Chemical group 0.000 abstract 1
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 20
- 239000000178 monomer Substances 0.000 description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 239000007800 oxidant agent Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000000921 elemental analysis Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229920001197 polyacetylene Polymers 0.000 description 3
- 229920000128 polypyrrole Polymers 0.000 description 3
- 229920000123 polythiophene Polymers 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 229940005561 1,4-benzoquinone Drugs 0.000 description 2
- MWZNHLWZWUMQOV-UHFFFAOYSA-N 3,4-bis(chloromethyl)-1H-pyrrole Chemical compound ClCc1c[nH]cc1CCl MWZNHLWZWUMQOV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 description 1
- NFAFONDHZNZQCA-UHFFFAOYSA-N 3,4-bis(chloromethyl)furan Chemical compound ClCC1=COC=C1CCl NFAFONDHZNZQCA-UHFFFAOYSA-N 0.000 description 1
- HRLQHOSRQDOYMF-UHFFFAOYSA-N 3,4-bis(chloromethyl)thiophene Chemical group ClCC1=CSC=C1CCl HRLQHOSRQDOYMF-UHFFFAOYSA-N 0.000 description 1
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000555825 Clupeidae Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000004422 alkyl sulphonamide group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 125000004421 aryl sulphonamide group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- GCPNLDYWHHIXMX-UHFFFAOYSA-H hexalithium;hexachloride Chemical compound [Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-] GCPNLDYWHHIXMX-UHFFFAOYSA-H 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- HNQIVZYLYMDVSB-UHFFFAOYSA-N methanesulfonimidic acid Chemical compound CS(N)(=O)=O HNQIVZYLYMDVSB-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- ABHHITAVUODQNA-UHFFFAOYSA-M potassium;benzenesulfonate Chemical compound [K+].[O-]S(=O)(=O)C1=CC=CC=C1 ABHHITAVUODQNA-UHFFFAOYSA-M 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 235000019512 sardine Nutrition 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- MABNMNVCOAICNO-UHFFFAOYSA-N selenophene Chemical compound C=1C=C[se]C=1 MABNMNVCOAICNO-UHFFFAOYSA-N 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 1
- WAGFXJQAIZNSEQ-UHFFFAOYSA-M tetraphenylphosphonium chloride Chemical compound [Cl-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WAGFXJQAIZNSEQ-UHFFFAOYSA-M 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、ドーピング状態で高い導電性と優れた安定性
を有する新規な導電性重合体に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to novel electrically conductive polymers having high electrical conductivity and excellent stability in the doped state.
本発明の導電性重合体は、電気・電子工業の分野におい
て導電材料、電極材料、表示材料、電磁波遮蔽材料等に
用いることが出来る。The conductive polymer of the present invention can be used for conductive materials, electrode materials, display materials, electromagnetic wave shielding materials, etc. in the electrical and electronic industries.
（従来の技術）
近年エレクトロニクス産業において、導電性高分子は金
属にはない様々な特性を有する新素材として注目され、
その実用化が待たれている１代表的な導電性重合体とし
てはポリアセチレンや、複素五員環構造をもつポリピロ
ール、ポリチオフェン等が挙げられる。しかしながらポ
リアセチレンは、例えば「ネイチャー」、４０３頁（１
９８７年）に記載されているように、ヨウ素ドーピング
により金属並みの高い導電性を示すものの、安定性が極
めて悪いという欠点を有する。一方ポリピロール、ポリ
チオフェン等は、ポリアセチレンに比較して合成が容易
でかつ安定性に優れているために盛んに研究が進められ
てきたが、その安定性は実用的に十分とは言えず、未だ
実用化には到っていないのが現状である。(Conventional technology) In recent years, conductive polymers have attracted attention in the electronics industry as new materials with various properties not found in metals.
Typical conductive polymers whose practical application is awaited include polyacetylene, polypyrrole having a five-membered heterocyclic ring structure, and polythiophene. However, polyacetylene, for example, "Nature", p. 403 (1)
987), although it exhibits high conductivity comparable to that of metals by doping with iodine, it has the drawback of extremely poor stability. On the other hand, polypyrrole, polythiophene, etc. have been actively researched because they are easier to synthesize and have superior stability compared to polyacetylene, but their stability is still not sufficient for practical use. The current situation is that this has not yet been achieved.
（発明が解決しようとする課題）
本発明は従来の導電性重合体の安定性における問題点を
解決し、実用上十分な安定性をもつ新規な導電性重合体
を提供するものである。(Problems to be Solved by the Invention) The present invention solves problems in the stability of conventional conductive polymers and provides a novel conductive polymer having sufficient stability for practical use.
（課題を解決するための手段）
本発明者は上記諸点に鑑み、導電性重合体の安定性を改
善すべく鋭意検討した結果、特定の構造を有する重合体
が、高い導電性と優れた安定性を有することを見出し、
遂に本発明を完成するに到った。すなわち本発明は下記
−数式（Ｉ）で示される構造を有する°導電性重合体で
ある。(Means for Solving the Problems) In view of the above points, the inventors of the present invention conducted extensive studies to improve the stability of conductive polymers, and found that a polymer having a specific structure has high conductivity and excellent stability. discovered that it has a sexual nature,
We have finally completed the present invention. That is, the present invention is a conductive polymer having a structure represented by the following formula (I).
Ｒ’ｍ
Ｒ” （１）
（但し、式中Ｒ１は炭素数１〜５のアルキル基、炭素数
１〜１０のアルキルスルホン基又はアリールスルホン基
又は炭素数１〜５のアルコキシカルボニルオキシ基であ
り、Ｒ２は水素、炭素数１〜１゜のアルキル基、アリー
ル基又はベンジル基、Ｘは炭素、Ｙは窒素、酸素、硫黄
、セレン又はテルルである。Ｘ−Ｎ間の結合は、−重結
合又は二重結合であり、二重結合のときｍは０又はｌで
あり、−重結合のときｍは１又は２である。ｎは重合度
を表す５〜５００の整数である。）
本発明重合体は、具体的には、ポリ（ピロロ［３，４−
ｃ］ピａ−ル）、ポリ（フラノ［３，４−ｃ］ピロール
）、ポリ（チェノ［３，４−ｃ ］ピロール）、ポリ（
セレノ［３，４−ｃ ］ピロール）、ポリ（テルロ［３
，４−ｃ］ピロール）及びその誘導体であり、当該単量
体を電解重合又は酸化剤による化学重合によって酸化重
合することにより得られる。なお単量体は一般に、以下
に述べる方法に従って合成される。R'm R" (1) (However, in the formula, R1 is an alkyl group having 1 to 5 carbon atoms, an alkyl sulfone group having 1 to 10 carbon atoms, an arylsulfone group having 1 to 5 carbon atoms, or an alkoxycarbonyloxy group having 1 to 5 carbon atoms. , R2 is hydrogen, an alkyl group having 1 to 1 degrees of carbon atoms, an aryl group, or a benzyl group, X is carbon, and Y is nitrogen, oxygen, sulfur, selenium or tellurium. The bond between X and N is a - double bond or a double bond; when it is a double bond, m is 0 or l; when it is a double bond, m is 1 or 2; n is an integer from 5 to 500 representing the degree of polymerization.) This invention Specifically, the polymer is poly(pyrrolo[3,4-
c] pearl), poly(furano[3,4-c]pyrrole), poly(cheno[3,4-c]pyrrole), poly(
seleno[3,4-c]pyrrole), poly(telluro[3
, 4-c]pyrrole) and derivatives thereof, which are obtained by oxidative polymerization of the monomers by electrolytic polymerization or chemical polymerization using an oxidizing agent. Note that the monomer is generally synthesized according to the method described below.
即ち、ピロール、フラン、チオフェン、セレノフェン、
テルルフェン等の複素五員環構造を有する化合物の３及
び４位をハロゲン化メチルで置換したものと、１級又は
２級のアミン類、アルキルスルホンアミド類又はアリー
ルスルホンアミド類とを反応させて五員環構造を形成さ
せる。さらに必要に応じて、これを塩基で処理するが又
は加熱処理すればよい、後半の塩基処理又は加熱処理は
重合反応の前に行って、得られたちの単量体として重合
することも出来るが、塩基処理又は加熱処理を重合後に
行うことも出来、る、この場合には、塩基処理又は加熱
処理を行う前の重合体が、−ｍに用いられている有機溶
剤又は水に可溶性であるために、任意の形状に加工して
後、塩基処理又は加熱処理を行うことが可＃１．１！：
なる。Namely, pyrrole, furan, thiophene, selenophene,
A compound having a five-membered heterocyclic structure such as tellulfene, in which the 3 and 4 positions are substituted with methyl halide, is reacted with primary or secondary amines, alkylsulfonamides, or arylsulfonamides. Forms a membered ring structure. Furthermore, if necessary, this may be treated with a base or heat treated. The latter half of the base treatment or heat treatment can be performed before the polymerization reaction, and the resulting monomer can be polymerized. Base treatment or heat treatment can also be carried out after polymerization. In this case, the polymer before base treatment or heat treatment is soluble in the organic solvent or water used in -m. After processing into any shape, base treatment or heat treatment can be performed #1.1! :
Become.
上記の単量体誘導体の具体例としては、各単量体につい
て一般式（１）におけるＲ１が、メチル基、エチル基、
ｎ−プロピル基、バラ−トルエンスルホン基、メタンス
ルホン基、メトキシカルボニルオキシ基が挙げられる。As specific examples of the above monomer derivatives, for each monomer, R1 in general formula (1) is a methyl group, an ethyl group,
Examples include n-propyl group, para-toluenesulfone group, methanesulfone group, and methoxycarbonyloxy group.
上記の塩基処理で用いられる塩基としては、カリウム
ｔｅｒＬ−ブトキシド、ナトリウム ｔｅｒ ｔ−ブト
キシド、ナトリウムエトキシド、水素化カルシウム、水
素化ナトリウム等が挙げられる。また加熱処理における
条件は、特に限定されないが、一般に５０〜３００℃の
範囲で実施される。The base used in the above base treatment is potassium
Examples include terL-butoxide, sodium tert-butoxide, sodium ethoxide, calcium hydride, and sodium hydride. Further, the conditions for the heat treatment are not particularly limited, but the heat treatment is generally carried out in the range of 50 to 300°C.
上記の単量体を電解重合又は酸化剤による化学酸化重合
する際に用いられる溶媒としては、アルゴン等の不活性
ガスで置換したものを用い、また単量体を扱うすべての
反応操作を不活性ガス雰囲気下で行うのが好ましい。さ
らに−層好ましくは単量体を合成した際に、単量体を単
離することなく、単量体を含有する溶液をそのまま重合
反応溶液とすることが推奨される。すなわち単量体を合
成して得られる、単量体を含有する溶液に必要に応じて
電解質を添加して、これを電解液として電解重合を行う
か、又は単量体を含有する溶液に酸化剤を添加して化学
重合を行うことが好ましい。When carrying out electrolytic polymerization or chemical oxidative polymerization using an oxidizing agent, the above monomers are subjected to electrolytic polymerization or chemical oxidative polymerization using an oxidizing agent. Preferably, this is carried out under a gas atmosphere. Furthermore, it is recommended that when the monomers are synthesized, the monomer-containing solution is used directly as a polymerization reaction solution without isolating the monomers. That is, an electrolyte is added as necessary to a monomer-containing solution obtained by synthesizing the monomer, and electrolytic polymerization is performed using this as an electrolytic solution, or the monomer-containing solution is oxidized. It is preferable to carry out chemical polymerization by adding an agent.
また単量体の酸化電位よりも高い電圧を印加した電極を
予め浸漬した溶液中で単量体を生成せしめるか、又は予
め酸化剤が存在する系内で単量体を生成せしめることに
よって、より効率的に重合反応を行うことも出来る。Furthermore, by generating the monomer in a solution in which an electrode is previously immersed with a voltage higher than the oxidation potential of the monomer, or by generating the monomer in a system where an oxidizing agent is present in advance, it is possible to It is also possible to carry out polymerization reactions efficiently.
本発明の重合体の合成を、当該単量体の電解重合によっ
て実施する際の反応装置は、通常ピロール、チオフェン
等の電解重合で用いられるものと同様の装置が用いられ
る。When the polymer of the present invention is synthesized by electrolytic polymerization of the monomer, a reaction apparatus similar to that normally used for electrolytic polymerization of pyrrole, thiophene, etc. is used.
なお電解重合で用いられる溶媒は特に限定されないが、
その代表例としてはアセトニトリル、ベンゾニトリル、
プロピオニトリル、ジオキサン、テトラヒドロフラン、
スルホラン、プロピレンカーボネート、ニトロベンゼン
、Ｎ、Ｎ−ジメチルホルムアミド等が挙げられる。Note that the solvent used in electrolytic polymerization is not particularly limited, but
Typical examples are acetonitrile, benzonitrile,
Propionitrile, dioxane, tetrahydrofuran,
Examples include sulfolane, propylene carbonate, nitrobenzene, N,N-dimethylformamide, and the like.
また使用される電解質としては、テトラエチルアンモニ
ウムプロミド、テトラエチルアンモニウムクロリド、テ
トラｎ−ブチルアンモニウムプロミド、テトラｎ−ブチ
ルアンモニウムクロリド、テトラフェニルホスホニウム
プロミド、テトラフェニルホスホニウムクロリド、リチ
ウムバークロレート、リチウムへキサフロロボレート、
テトラエチルアンモニウムテトラフロロボレート、テト
ラｎ−ブチルアンモニウムへキサフロロアンチモン、テ
トラｎ−ブチルアンモニウムへキサフロロフォスフェー
ト、ベンゼンスルホン酸カリウム塩、トルエンスルホン
酸ナトリウム塩硫酸、塩酸、トリフロロ酢酸等が挙げら
れる。これからの電解質の陰イオンは電解重合時、ドー
パントとして重合体中に取り込まれる。The electrolytes used include tetraethylammonium bromide, tetraethylammonium chloride, tetra n-butylammonium bromide, tetra n-butylammonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium chloride, lithium verchlorate, and lithium hexachloride. fluoroborate,
Examples include tetraethylammonium tetrafluoroborate, tetra n-butylammonium hexafluoroantimony, tetra n-butylammonium hexafluorophosphate, benzenesulfonic acid potassium salt, toluenesulfonic acid sodium salt sulfuric acid, hydrochloric acid, trifluoroacetic acid, and the like. The anion of the electrolyte is incorporated into the polymer as a dopant during electrolytic polymerization.
上記の単量体及び電解質を含有する溶液中に電極板を浸
漬し、定電位法又は定電流法で電圧を印加することによ
り、陽極板上にフィルム状の所望重合体が得られる。こ
の際、電解質として高分子電解質を用いることによって
、より可とう性に優れたフィルムを得ることも出来る。By immersing the electrode plate in a solution containing the above-mentioned monomer and electrolyte and applying a voltage using a constant potential method or a constant current method, a desired polymer in the form of a film can be obtained on the anode plate. At this time, by using a polymer electrolyte as the electrolyte, a film with even better flexibility can be obtained.
電解重合時の単量体濃度は特に限定されないが、効率的
な重合を行うためには０．０５〜５ｓｏｌ／１の範囲で
あることが好ましい、しかしながら、より高い導電性の
重合体を所望する場合は、０．００１〜０．１ｍｏｌ／
１の範囲にあるのがよい、電解質の濃度は、電解重合
を効率的に行うためには少なくとも０９１１０１７１以
上であることが好ましい、電解重合の際の電流密度は特
に限定されないが、好ましくは１．０〜５．０ｍ＾／ｉ
である。重合温度は特に定めないが、約−８０〜１００
°Ｃの範囲で重合するのが望ましい、しかしながら、よ
り高い導電性をもつ重合体を得るためには、約−２０〜
０℃の範囲が一層望ましい０重合時間は所望する重合体
フィルムの膜厚等によって定められるものであるが、通
常的０．１−１００時間で重合される。The monomer concentration during electrolytic polymerization is not particularly limited, but is preferably in the range of 0.05 to 5 sol/1 in order to perform efficient polymerization. However, a polymer with higher conductivity is desired. In case, 0.001 to 0.1 mol/
The concentration of the electrolyte is preferably at least 09110171 or higher in order to efficiently carry out electrolytic polymerization.The current density during electrolytic polymerization is not particularly limited, but is preferably within the range of 1. 0~5.0m^/i
It is. The polymerization temperature is not particularly determined, but is about -80 to 100
It is desirable to polymerize in the range of -20 °C, however, to obtain polymers with higher conductivities,
The zero polymerization time, which is more preferably in the range of 0°C, is determined depending on the desired thickness of the polymer film, etc., but polymerization is usually carried out in 0.1 to 100 hours.
本発明の重合体の合成を、当該単量体の化学重合によっ
て実施する際に用いられる溶媒としてはジクロルメタン
、クロロホルム、四塩化炭素、ジクロルエタン、テトラ
クロルエタン、ニトロメタン、ニトロエタン、ニトロベ
ンゼン、クロルベンゼン、Ｎ−メチル−２−ピロリドン
、二硫化炭素等が挙げられる。また化学重合で使用され
る酸化剤としては、テトラクロル−１，２−ベンゾキノ
ン、テトラクロル−１，４−ベンゾキノン、２，３−ジ
クロル−５，６−ジチアツー１．４−ベンゾキノン等の
キノン系酸化剤、ヨウ素、臭素、塩素等のハロゲン系酸
化剤、硝酸、塩酸、硫酸等の無機酸又はアルミニウム、
錫、クロム、マンガン、鉄、銅、モリブデン、タングス
テン、ルテニウム、パラジウム、白金などの金属の塩化
物、硫酸塩及び硝酸塩、さらに過硫酸ナトリウム、過硫
酸カリウム、過硫酸アンモニウム等の過硫酸塩が挙げら
れる。Solvents used in the synthesis of the polymer of the present invention by chemical polymerization of the monomers include dichloromethane, chloroform, carbon tetrachloride, dichloroethane, tetrachloroethane, nitromethane, nitroethane, nitrobenzene, chlorobenzene, N -Methyl-2-pyrrolidone, carbon disulfide and the like. Oxidizing agents used in chemical polymerization include quinone oxidizing agents such as tetrachlor-1,2-benzoquinone, tetrachlor-1,4-benzoquinone, and 2,3-dichloro-5,6-dithiazo-1,4-benzoquinone. , halogen-based oxidizing agents such as iodine, bromine, and chlorine, inorganic acids such as nitric acid, hydrochloric acid, and sulfuric acid, or aluminum;
Examples include chlorides, sulfates, and nitrates of metals such as tin, chromium, manganese, iron, copper, molybdenum, tungsten, ruthenium, palladium, and platinum, as well as persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate. .
本発明の重合体の電解重合及び化学重合に際しては、上
記の溶媒電解質、酸化剤のそれぞれの中から、２種類以
上を組合せて用いることも出来る。In the electrolytic polymerization and chemical polymerization of the polymer of the present invention, two or more of the above-mentioned solvent electrolytes and oxidizing agents can be used in combination.
また重合時に、他の重合性単量体を共存させることによ
って共重合体を得ることも出来る。さらに重合反応系中
に、他の絶縁性重合体を共存させることによって、導電
性複合材料を得ることも可能である。A copolymer can also be obtained by coexisting other polymerizable monomers during polymerization. Furthermore, it is also possible to obtain a conductive composite material by coexisting other insulating polymers in the polymerization reaction system.
電解重合又は化学重合によって得られた重合体は、さら
に酸化剤で処理することによって導電性を向上させるこ
とが出来る。The conductivity of a polymer obtained by electrolytic polymerization or chemical polymerization can be improved by further treating it with an oxidizing agent.
以上かかる方法によって得られた本発明の重合体は、ド
ーパントとして無機又は有機の陰イオンを含有すること
によって高い導電性を発現する。The polymer of the present invention obtained by the method described above exhibits high electrical conductivity by containing an inorganic or organic anion as a dopant.
該陰イオンとしてはＣｌ−１Ｂｒ−５■＝、ＣｌＯ４−
１ｔｌＦ、−ＰＦ、−１ＡｓＦ、”、５ｂｉ−１ＡＩＣ
Ｉ４−５ＡＩＢｒ３ＣＩ−１ＦｅＣＩａ−１ＳｎＣＩｚ
−、ＣＬＣ＊ＨｓＳＯ３−１Ｃ１１ｔＳＯｓ−１ＣＰ３
ＳＯ！−及びｌｌ５Ｏ，−から選ばれる陰イオンが挙げ
られる。The anions include Cl-1Br-5■=, ClO4-
1tlF, -PF, -1AsF,", 5bi-1AIC
I4-5AIBr3CI-1FeCIa-1SnCIz
-, CLC*HsSO3-1C11tSOs-1CP3
SO! Examples include anions selected from - and ll5O,-.
なおドーピング状態、脱ドーピングの状態でそれぞれ特
有の色調を育し、これら２つの状態を可逆的にとる過程
で、鮮明な色調変化を示す、特に、重合反応の前又は後
に塩基処理又は加熱処理の過程を経て得られた重合体に
おいては、ドーピング状態で可視領域の吸収が減少し、
着色の少ない透明性を有する導電性重合体となり得る。Note that the doped state and undoped state each develop a unique color tone, and in the process of reversibly changing between these two states, a clear color tone change occurs.Especially, when base treatment or heat treatment is performed before or after the polymerization reaction, In the polymer obtained through this process, absorption in the visible region decreases in the doped state,
It can be a conductive polymer with little coloring and transparency.
（実施例）
以下実施例を示し、本発明をさらに具体的に説明するが
、この実施例をもって本発明の技術的範囲を限定するも
のではない。(Example) The present invention will be explained in more detail by referring to Examples below, but the technical scope of the present invention is not limited by these Examples.
なお本実施例で用いた溶媒はすべて、通常の方法に従っ
て乾燥蒸留した後、乾燥した窒素で３０分以上バブリン
グしたものを用い、またすべての反応操作は窒素雰囲気
下で行った。Note that all the solvents used in this example were dry distilled according to a conventional method and then bubbled with dry nitrogen for 30 minutes or more, and all reaction operations were performed under a nitrogen atmosphere.
実施例１
［ポリ（ピロロ［３，４−ｃ ］ビロール）の合成］３
．４−ジ（クロロメチル）ピロールとパラ−トルエンス
ルホンアミドをＮ、Ｎ−ジメチルホルムアミド中、水素
化ナトリウムの存在下、反応させて得たＮ−バラ−トリ
ルスルホニルジヒドロピロロ［３，４−Ｃ］ ピロール
２．３ｇを、Ｎ、Ｎ−ジメチルホルムアミド４５ｍ１に
溶解させた。この溶液にカリウム ｔａｒ ｔ−ブトキ
シド１．０ｇを添加した後、室温で１０分間撹拌し、次
いでテトラｎ−ブチルアンモニウムプロミド１１．０ｇ
を添加、溶解させた。この溶液を電解液とし、白金板を
陰極、ネサガラスを陽極、Ｌｉ／Ｌｉ”を参照電極とし
て１，８〜５．０ｍＡ／ｃ４の電流密度で電圧を印加し
たところ、陽極板上にフィルム状生成物が得られた。こ
の生成物を電極板より剥離して、アセトニトリル次いで
アセトンで十分洗浄した後、真空乾燥した。この重合体
の室温における導電率を直流四端子法で測定したところ
、２．５Ｘ１０’ Ｓ／ ｃｒｓであった６得られた重
合体の元素分析結果は表１に示すように、重合体の構造
を次式と推定したときの理論計算値によく一致していた
。Example 1 [Synthesis of poly(pyrrolo[3,4-c]virol)] 3
．． N-bara-tolylsulfonyldihydropyrrolo[3,4-C] obtained by reacting 4-di(chloromethyl)pyrrole and para-toluenesulfonamide in N,N-dimethylformamide in the presence of sodium hydride 2.3 g of pyrrole was dissolved in 45 ml of N,N-dimethylformamide. After adding 1.0 g of potassium tar t-butoxide to this solution, it was stirred at room temperature for 10 minutes, and then 11.0 g of tetra n-butylammonium bromide.
was added and dissolved. When this solution was used as an electrolyte and a voltage was applied at a current density of 1.8 to 5.0 mA/c4 using the platinum plate as a cathode, Nesa glass as an anode, and Li/Li'' as a reference electrode, a film-like substance was formed on the anode plate. A product was obtained. This product was peeled off from the electrode plate, thoroughly washed with acetonitrile and then acetone, and then dried in vacuum. The electrical conductivity of this polymer at room temperature was measured by the DC four-terminal method, and it was found to be 2. As shown in Table 1, the elemental analysis results of the obtained polymer, which was 5X10' S/crs, were in good agreement with the theoretically calculated value when the structure of the polymer was estimated as the following formula.
■
実施例２
［ポリ（フラノ［３，４−ｃｌピロール）の合成］実施
例１で用いた３、４−ジ（クロロメチル）ピロールの代
わりに、３．４−ジ（クロロメチル）フランを用いて、
以下実施例１と同様にＮ−パラ−トリルスルホニルジヒ
ドロフラノ［３，４−Ｃ］ビロールを得、さらに塩基処
理の後、引き続いて電解重合したところ、陽極板上にフ
ィルム状生成物が得られた。この生成物を電極板より剥
離して、以下実施例１と同様に洗浄、乾燥してその導電
率を測定したところ、１．５Ｘ１０’ Ｓ／ＣＩであっ
た。得られた重合体の元素分析結果は、表１に示すよう
に、重合体の構造を次式と推定したときの理論計算値に
よく一致していた。■ Example 2 [Synthesis of poly(furano[3,4-clpyrrole)] Instead of 3,4-di(chloromethyl)pyrrole used in Example 1, 3,4-di(chloromethyl)furan was used. make use of,
Next, N-para-tolylsulfonyldihydrofurano[3,4-C]virol was obtained in the same manner as in Example 1, further treated with a base, and then electrolytically polymerized. A film-like product was obtained on the anode plate. Ta. This product was peeled off from the electrode plate, washed and dried in the same manner as in Example 1, and its conductivity was measured and found to be 1.5X10' S/CI. As shown in Table 1, the elemental analysis results of the obtained polymer were in good agreement with the theoretically calculated values when the structure of the polymer was estimated as the following formula.
実施例３
［ポリ（チェノ［３，４−ｃｌピロール）の合成］実施
例１で用いた３、４−ジ（クロロメチル）ピロールの代
わりに、３．４−ジ（クロロメチル）チオフェンを用い
て、以下実施例１と同様にＮ−バラ−トリルスルホニル
ジヒドロチエノ”［３，４−ｃ］ビロールを得、さらに
塩基処理の後、引き続いて電解重合したところ、陽極板
上にフィルム状生成物が得られた。この生成物を電極板
より剥離して、以下実施例１と同様に洗浄、乾燥してそ
の導電率を測定したところ、？、５ｘｌＯ’ ３７ｃｍ
であった。得られた重合体の元素分析結果は、表１に示
すように、重合体の構造を下式と推定したときの理論計
算値によ（一致していた。Example 3 [Synthesis of poly(cheno[3,4-cl-pyrrole)] 3,4-di(chloromethyl)pyrrole used in Example 1 was replaced with 3,4-di(chloromethyl)thiophene. Then, in the same manner as in Example 1, N-bara-tolylsulfonyldihydrothieno"[3,4-c]pyrrole was obtained, further treated with a base, and then subjected to electrolytic polymerization. As a result, a film-like product was formed on the anode plate. This product was peeled off from the electrode plate, washed and dried in the same manner as in Example 1, and its conductivity was measured.
Met. As shown in Table 1, the elemental analysis results of the obtained polymer were in agreement with the theoretically calculated values when the structure of the polymer was estimated as the following formula.
実施例４
［ポリ（セレノ［３，４−ｃｌピロール）の合成］実施
例１で用いた３、４−ジ（クロロメチル）ビロールの代
わりに３．４−ジ（クロロメチル）セレノフェンを用い
て、以下実施例１と同様にＮ−バラ−トリルスルホニル
ジヒドロセレノ ［３，４−ｃｌ ピロールを得、さら
に塩基処理の後、引き続いて電解重合したところ、陽極
板上にフィルム状生成物が得られた。この生成物を電極
板より剥離して、以下実施例１と同様に洗浄、乾燥して
その導電率を測定したところ、３．２Ｘ１０’ Ｓ／ｃ
箇であった。得られた重合体の元素分析結果は、表１に
示すように、重合体の構造を下式と推定したときの理論
計算値によく一致していた。Example 4 [Synthesis of poly(seleno[3,4-clpyrrole)] Using 3,4-di(chloromethyl)selenophene instead of 3,4-di(chloromethyl)virol used in Example 1 , N-bara-tolylsulfonyl dihydroseleno [3,4-cl pyrrole was obtained in the same manner as in Example 1, and after further treatment with a base, electrolytic polymerization was performed, and a film-like product was obtained on the anode plate. Ta. This product was peeled off from the electrode plate, washed and dried in the same manner as in Example 1, and its conductivity was measured; it was found to be 3.2X10' S/c.
It was an item. As shown in Table 1, the elemental analysis results of the obtained polymer were in good agreement with the theoretically calculated values when the structure of the polymer was estimated as the following formula.
実施例５
［ポリ（テルロ［３，４−ｃ］ピロール）の合成］実施
例１で用いた３、４−ジ（クロロメチル）とロールの代
わりに３，４−ジ（クロロメチル）テルルフェ／を用い
て、以下実施例１と同様にＮ−バラートリルスルホニル
ンヒドロテルロ［３，４−ｃｌ ビロールを得、さらに
塩基処理の後、引き続いて電解重合したところ、陽極板
上にフィルム状生成物が得られた。この生成物を電極板
より剥離して、以下実施例１と同様に洗浄、乾燥してそ
の導電率を測定したところ、２．９ Ｘ １０−’ Ｓ
／ ｃｍであった。得られた重合体の元素分析結果は、
表１に示すように、重合体の構造を下式と推定したとき
の理論計算値によく一致していた。Example 5 [Synthesis of poly(telluro[3,4-c]pyrrole)] 3,4-di(chloromethyl)tellurfe/instead of 3,4-di(chloromethyl) and roll used in Example 1 was used to obtain N-valatrilsulfonylonhydrotello[3,4-cl pyrrole] in the same manner as in Example 1, and after further treatment with a base, subsequent electropolymerization was performed, resulting in a film-like product on the anode plate. was gotten. This product was peeled off from the electrode plate, washed and dried in the same manner as in Example 1, and its conductivity was measured.
/cm. The elemental analysis results of the obtained polymer are as follows:
As shown in Table 1, the structure was in good agreement with the theoretically calculated value when the structure of the polymer was estimated as the following formula.
実施例６
［ポリ（ピロロ［３，４−ｃ ］ピロール）の合成１実
施例１で用いたパラ−トルエンスルホンアミドの代わり
にメタンスルホンアミドを用いて、Ｎメチルスルホニル
ジヒドロピロロ［３，４−ｃ］ピロールを得た。得られ
たＮ−メチルスルホニルジヒドロピロロ［３，４−ｃｌ
ピロール１．５ｇとテトラＮ−ブチルアンモニウムプ
ロミド１０．５ｇをアセトニトリル４０ｍ１に溶解させ
た。得られた溶液を電解液として、実施例１と同様の条
件で電解重合したところ陽極板上にフィルム状生成物が
得られた。この生成物を電極板より剥離して、以下実施
例１と同様に洗浄、乾燥してその導電率を測定したとこ
ろ、９゜８ Ｘ １０”’ Ｓ ／ ｃｍであった。得
られた重合体の元素分析結果は、表１に示すように、重
合体の構造を下式と推定したときの理論計算値によく一
致していた。Example 6 Synthesis of [poly(pyrrolo[3,4-c]pyrrole) 1 Using methanesulfonamide instead of para-toluenesulfonamide used in Example 1, N-methylsulfonyldihydropyrrolo[3,4- c] Pyrrole was obtained. The obtained N-methylsulfonyldihydropyrrolo[3,4-cl
1.5 g of pyrrole and 10.5 g of tetra-N-butylammonium bromide were dissolved in 40 ml of acetonitrile. When the obtained solution was used as an electrolytic solution and electrolytically polymerized under the same conditions as in Example 1, a film-like product was obtained on the anode plate. This product was peeled off from the electrode plate, washed and dried in the same manner as in Example 1, and its conductivity was measured to be 9°8 x 10''' S/cm.The obtained polymer As shown in Table 1, the elemental analysis results of were in good agreement with the theoretically calculated values when the structure of the polymer was estimated as the following formula.
Ｌ
ＳＯ□
シト１．０ｇを添加して６０°Ｃで１２時間加熱撹拌し
たところ、黒縁色の沈・澱物が得られた。この沈澱物を
クロロホルム次いでアセトンでソックスレー抽出した後
、真空乾燥してその導電率を測定したところ、４．２
Ｘ ＩＱ’ Ｓ ／ ｃｔｓであった。得られた重合体
の赤外吸収スペクトルは実施例１で得られた重合体のそ
れに一致していた。When 1.0 g of LSO□ was added and the mixture was heated and stirred at 60°C for 12 hours, a black-rimmed precipitate was obtained. This precipitate was subjected to Soxhlet extraction with chloroform and then acetone, dried in vacuum, and its electrical conductivity was measured, and it was found to be 4.2.
X IQ' S/cts. The infrared absorption spectrum of the obtained polymer matched that of the polymer obtained in Example 1.
次に実施例１〜６で得られた導電性重合体を、それぞれ
ヨウ素蒸気にさらしてヨウ素ドーピングした。ヨウ素ド
ーピング後の導電率、及びその後１年間室温空気中に放
置したときの導電率を表２に示す、なお比較例としてそ
れぞれ通常の化学重合、及び電解重合で合成したポリピ
ロール、ポリチオフェンにおける値を併せて記する。Next, the conductive polymers obtained in Examples 1 to 6 were each exposed to iodine vapor to be doped with iodine. Table 2 shows the electrical conductivity after iodine doping and the electrical conductivity when left in air at room temperature for one year.As a comparative example, the values for polypyrrole and polythiophene synthesized by ordinary chemical polymerization and electrolytic polymerization are also included. I will write it down.
■
さらにこの重合体０．５ｇをＮ、Ｎ−ジメチルホルムア
ミド１５ｍ１に溶解させた後、カリウムｔｅｒ ｔ−ブ
トキ表
１６．３１％）、Ｓ力＜１６．３６％σ１峠酊６．３４
鰯分析された。■ Furthermore, after dissolving 0.5 g of this polymer in 15 ml of N,N-dimethylformamide, potassium tert-butoxide table 16.31%), S force <16.36% σ1 6.34
Sardines were analyzed.
（発明の効果）
本発明の導電性重合体は、ドーピング状態で高い導電性
と優れた安定性を有することから、電気・電子工業の分
野において導電材料半導体材料として有用なものである
。また本発明の重合体の酸化還元反応に基づく吸収スペ
クトルの変化、又はエネルギー変化を利用した、表示素
子、電極材料等への応用が可能である。(Effects of the Invention) The conductive polymer of the present invention has high conductivity and excellent stability in a doped state, and is therefore useful as a conductive material and a semiconductor material in the fields of electrical and electronic industries. Further, it is possible to apply the present invention to display elements, electrode materials, etc. by utilizing changes in the absorption spectrum or energy changes based on the redox reaction of the polymer of the present invention.
特許出願人 東洋紡績株式会社Patent applicant: Toyobo Co., Ltd.
Claims (1)
性重合体。 ▲数式、化学式、表等があります▼（ I ） （但し、式中Ｒ＾１は炭素数１〜５のアルキル基、炭素
数１〜１０のアルキルスルホン基又はアリールスルホン
基又は炭素数１〜５のアルコキシカルボニルオキシ基で
あり、Ｒ＾２は水素、炭素数１〜１０のアルキル基、ア
リール基又はベンジル基、Ｘは炭素、Ｙは窒素、酸素、
硫黄、セレン又はテルルである。Ｘ−Ｎ間の結合は、一
重結合又は二重結合であり、二重結合のときｍは０又は
１であり、一重結合のときｍは１又は２である。ｎは重
合度を表す５〜５００の整数である。）(1) A conductive polymer having a structure represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (However, in the formula, R^1 is an alkyl group having 1 to 5 carbon atoms, an alkyl sulfone group having 1 to 10 carbon atoms, or an arylsulfone group having 1 to 5 carbon atoms. is an alkoxycarbonyloxy group, R^2 is hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group or a benzyl group, X is carbon, Y is nitrogen, oxygen,
Sulfur, selenium or tellurium. The bond between X-N is a single bond or a double bond, m is 0 or 1 when it is a double bond, and m is 1 or 2 when it is a single bond. n is an integer from 5 to 500 representing the degree of polymerization. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33560088A JPH02180922A (en) | 1988-12-29 | 1988-12-29 | Conductive polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33560088A JPH02180922A (en) | 1988-12-29 | 1988-12-29 | Conductive polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02180922A true JPH02180922A (en) | 1990-07-13 |
Family
ID=18290395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33560088A Pending JPH02180922A (en) | 1988-12-29 | 1988-12-29 | Conductive polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02180922A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004005297A1 (en) * | 2002-07-05 | 2004-01-15 | Nippon Soda Co.,Ltd. | Pyrrole derivative and process for producing the same |
| JP2008163348A (en) * | 2008-03-13 | 2008-07-17 | Konica Minolta Holdings Inc | Organic semiconductor material and field-effect transistor using the same |
| JP2008202053A (en) * | 2008-03-13 | 2008-09-04 | Konica Minolta Holdings Inc | Organic semiconductor material and field effect transistor using the same |
| WO2009034571A2 (en) * | 2007-09-10 | 2009-03-19 | Yeda Research And Development Co. Ltd. | Selenophenes and selenophene-based polymers, their preparation and uses thereof |
| JP2011032426A (en) * | 2009-08-05 | 2011-02-17 | Sumitomo Chemical Co Ltd | Conjugated polymer compound and organic semiconductor device containing the same |
| WO2013047225A1 (en) * | 2011-09-28 | 2013-04-04 | 富士フイルム株式会社 | Organic thin film solar cell, organic semiconductor polymer used in same, and composition for organic semiconductor materials |
-
1988
- 1988-12-29 JP JP33560088A patent/JPH02180922A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004005297A1 (en) * | 2002-07-05 | 2004-01-15 | Nippon Soda Co.,Ltd. | Pyrrole derivative and process for producing the same |
| WO2009034571A2 (en) * | 2007-09-10 | 2009-03-19 | Yeda Research And Development Co. Ltd. | Selenophenes and selenophene-based polymers, their preparation and uses thereof |
| WO2009034571A3 (en) * | 2007-09-10 | 2010-01-07 | Yeda Research And Development Co. Ltd. | Selenophenes and selenophene-based polymers, their preparation and uses thereof |
| JP2008163348A (en) * | 2008-03-13 | 2008-07-17 | Konica Minolta Holdings Inc | Organic semiconductor material and field-effect transistor using the same |
| JP2008202053A (en) * | 2008-03-13 | 2008-09-04 | Konica Minolta Holdings Inc | Organic semiconductor material and field effect transistor using the same |
| JP2011032426A (en) * | 2009-08-05 | 2011-02-17 | Sumitomo Chemical Co Ltd | Conjugated polymer compound and organic semiconductor device containing the same |
| WO2013047225A1 (en) * | 2011-09-28 | 2013-04-04 | 富士フイルム株式会社 | Organic thin film solar cell, organic semiconductor polymer used in same, and composition for organic semiconductor materials |
| JP2013074137A (en) * | 2011-09-28 | 2013-04-22 | Fujifilm Corp | Organic thin film solar cell, and organic semiconductor polymer and composition for organic semiconductor material used for the same |
| US9214634B2 (en) | 2011-09-28 | 2015-12-15 | Fujifilm Corporation | Organic photovoltaic cell, organic semiconductor polymer and composition for organic semiconductor material used therefor |
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