KR20100084479A - Dopant for conductive polymer and conductive polymer using the same - Google Patents
Dopant for conductive polymer and conductive polymer using the same Download PDFInfo
- Publication number
- KR20100084479A KR20100084479A KR1020100003680A KR20100003680A KR20100084479A KR 20100084479 A KR20100084479 A KR 20100084479A KR 1020100003680 A KR1020100003680 A KR 1020100003680A KR 20100003680 A KR20100003680 A KR 20100003680A KR 20100084479 A KR20100084479 A KR 20100084479A
- Authority
- KR
- South Korea
- Prior art keywords
- conductive polymer
- dopant
- group
- quaternary phosphonium
- phosphonium salt
- Prior art date
Links
- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 88
- 239000002019 doping agent Substances 0.000 title claims abstract description 25
- 150000004714 phosphonium salts Chemical class 0.000 claims abstract description 76
- 238000002844 melting Methods 0.000 claims abstract description 21
- 230000008018 melting Effects 0.000 claims abstract description 21
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 44
- -1 n-octyl group Chemical group 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 19
- 239000008151 electrolyte solution Substances 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 16
- 150000001450 anions Chemical class 0.000 claims description 11
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 229920000128 polypyrrole Polymers 0.000 claims description 5
- 229920000123 polythiophene Polymers 0.000 claims description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 3
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 abstract 1
- 125000005496 phosphonium group Chemical group 0.000 abstract 1
- 239000000047 product Substances 0.000 description 36
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 27
- 239000003792 electrolyte Substances 0.000 description 23
- 238000000034 method Methods 0.000 description 22
- 230000015572 biosynthetic process Effects 0.000 description 21
- 238000003786 synthesis reaction Methods 0.000 description 21
- 239000002608 ionic liquid Substances 0.000 description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 238000005259 measurement Methods 0.000 description 17
- 238000005406 washing Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000005481 NMR spectroscopy Methods 0.000 description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 10
- 238000005979 thermal decomposition reaction Methods 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000003153 chemical reaction reagent Substances 0.000 description 9
- 229910052698 phosphorus Inorganic materials 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 229910052736 halogen Inorganic materials 0.000 description 8
- 150000002367 halogens Chemical class 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 239000003115 supporting electrolyte Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000003993 interaction Effects 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 150000004996 alkyl benzenes Chemical class 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 125000004437 phosphorous atom Chemical group 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 238000012790 confirmation Methods 0.000 description 5
- 150000003949 imides Chemical class 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 238000003918 potentiometric titration Methods 0.000 description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 5
- 229910001961 silver nitrate Inorganic materials 0.000 description 5
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- 238000005349 anion exchange Methods 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 3
- 229940073608 benzyl chloride Drugs 0.000 description 3
- VHTDHSVPBYDDAM-UHFFFAOYSA-N benzyl(triethyl)phosphanium Chemical compound CC[P+](CC)(CC)CC1=CC=CC=C1 VHTDHSVPBYDDAM-UHFFFAOYSA-N 0.000 description 3
- HYNYWFRJHNNLJA-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;trihexyl(tetradecyl)phosphanium Chemical compound FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.CCCCCCCCCCCCCC[P+](CCCCCC)(CCCCCC)CCCCCC HYNYWFRJHNNLJA-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical class C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical class C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-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
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- WCHPXAFAEZGCMB-UHFFFAOYSA-M benzyl(tributyl)phosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CC1=CC=CC=C1 WCHPXAFAEZGCMB-UHFFFAOYSA-M 0.000 description 2
- OZXRLJIEKITDLN-UHFFFAOYSA-M benzyl(triethyl)phosphanium;chloride Chemical compound [Cl-].CC[P+](CC)(CC)CC1=CC=CC=C1 OZXRLJIEKITDLN-UHFFFAOYSA-M 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 2
- 150000004693 imidazolium salts Chemical class 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000012454 non-polar solvent Substances 0.000 description 2
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 229920001197 polyacetylene Polymers 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- GKNWQHIXXANPTN-UHFFFAOYSA-M 1,1,2,2,2-pentafluoroethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)F GKNWQHIXXANPTN-UHFFFAOYSA-M 0.000 description 1
- KZWJWYFPLXRYIL-UHFFFAOYSA-M 1,1,2,2-tetrafluoroethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)F KZWJWYFPLXRYIL-UHFFFAOYSA-M 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229920003026 Acene Polymers 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical group S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical class C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- VJGNLOIQCWLBJR-UHFFFAOYSA-M benzyl(tributyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 VJGNLOIQCWLBJR-UHFFFAOYSA-M 0.000 description 1
- IKNWWJMESJSJDP-UHFFFAOYSA-N benzyl(tributyl)phosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CC1=CC=CC=C1 IKNWWJMESJSJDP-UHFFFAOYSA-N 0.000 description 1
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 1
- VUUQSOCJUCSVBN-UHFFFAOYSA-M benzyl(trioctyl)phosphanium;chloride Chemical compound [Cl-].CCCCCCCC[P+](CCCCCCCC)(CCCCCCCC)CC1=CC=CC=C1 VUUQSOCJUCSVBN-UHFFFAOYSA-M 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- WVQUCYVTZWVNLV-UHFFFAOYSA-N boric acid;oxalic acid Chemical compound OB(O)O.OC(=O)C(O)=O WVQUCYVTZWVNLV-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000005421 electrostatic potential Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000003884 phenylalkyl group Chemical group 0.000 description 1
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- WGHUNMFFLAMBJD-UHFFFAOYSA-M tetraethylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CC[N+](CC)(CC)CC WGHUNMFFLAMBJD-UHFFFAOYSA-M 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- JFZKOODUSFUFIZ-UHFFFAOYSA-N trifluoro phosphate Chemical compound FOP(=O)(OF)OF JFZKOODUSFUFIZ-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/54—Quaternary phosphonium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/50—Phosphorus bound to carbon only
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
- H01G9/035—Liquid electrolytes, e.g. impregnating materials
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Power Engineering (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Secondary Cells (AREA)
Abstract
Description
본 발명은 4급 포스포늄염으로 이루어지는 도전성 고분자용 도펀트 및 그것을 사용하여 얻어지는 도전성 고분자에 관한 것이다.The present invention relates to a dopant for conductive polymers composed of quaternary phosphonium salts and to conductive polymers obtained using the same.
폴리피롤, 폴리티오펜, 폴리아세틸렌 등의 일차원 π 전자 공액 구조를 갖는 고분자 화합물은 도전성 고분자라 불리고 있고, 전해 컨덴서나 전자 기기의 백업용 전지, 휴대 전화나 노트북 컴퓨터에 사용되고 있는 리튬 이차 전지의 전극 등에 사용되고 있다. 또한, 도전성 고분자는 도전성 뿐만 아니라 발광성을 가지며 성막성을 갖기 때문에, 플렉시블 디스플레이의 실현이 가능한 유기 전계 발광(유기 EL), 유기 반도체로 구성되는 유기 트랜지스터, 도전성 고분자를 잉크로서 잉크젯 기술 등을 이용하여 직접 기판에 패턴을 만드는 프린터블 회로 등에도 응용되고 있다.Polymer compounds having one-dimensional π electron conjugated structures such as polypyrrole, polythiophene, and polyacetylene are called conductive polymers, and are used in electrolytic capacitors, backup batteries for electronic devices, and electrodes of lithium secondary batteries used in mobile phones and notebook computers. have. In addition, since the conductive polymer has not only conductivity but also luminescence and film-forming property, it is possible to realize organic electroluminescence (organic EL), organic transistor composed of an organic semiconductor, and conductive polymer using inkjet technology as ink as an ink. It is also applied to a printable circuit which directly forms a pattern on a board.
π 전자 공액계 도전성 고분자의 합성법으로서는, 화학 산화 중합법(예를 들면 특허문헌 1)과 전해 중합법(예를 들면 특허문헌 2)이 널리 알려져 있다. 화학 산화 중합법은 산화제를 사용하여 용액 중에서 단량체를 산화 중합시키는 방법이며, 대량 생산에 적합하지만, 중합 시간이 길고, 얻어지는 도전성 고분자의 전기 전도율이 낮다고 하는 문제점이 있다. 한편, 전해 중합법은 단량체를 함유하는 전해액 중에서 전해를 행함으로써 귀금속 등의 전극 상에 도전성 고분자막을 형성하는 방법이며, 전극 전위나 전류 밀도를 조정함으로써 중합 시간의 제어가 용이하고, 얻어지는 도전성 고분자의 전기 전도성도 높다고 하는 이점을 갖는다.As a synthesis method of (pi) electron conjugated system conductive polymer, the chemical oxidation polymerization method (for example, patent document 1) and the electrolytic polymerization method (for example, patent document 2) are known widely. The chemical oxidation polymerization method is a method of oxidatively polymerizing monomers in a solution using an oxidizing agent, and is suitable for mass production, but has a problem that the polymerization time is long and the electrical conductivity of the obtained conductive polymer is low. On the other hand, the electrolytic polymerization method is a method of forming a conductive polymer film on an electrode such as a noble metal by conducting electrolysis in an electrolyte solution containing monomers, and controlling the polymerization time by adjusting the electrode potential and the current density is easy, It has the advantage that electrical conductivity is also high.
일반적으로 전해 중합법에서는, 아세토니트릴이나 에틸렌카르보네이트 등의 유기 용제에 리튬염, 나트륨염, 4급 암모늄염과 같은 지지 전해질을 용해시켜 전해액으로 하고, 상기 전해액에 단량체를 함유시킨 전해질 조성물을 사용한다. 이들 지지 전해질은 전해액의 전기 전도성을 확보하는 목적 뿐만 아니라, 얻어지는 도전성 고분자 중에 취입(取入)되어 도전성 고분자 자체의 전기 전도율을 높이는 도펀트로서도 거동한다. 따라서, 도전성 고분자의 전기 전도성은 지지 전해질의 종류, 전해액 중의 농도 등의 조건에 크게 의존한다. 또한, 전기 전도성 뿐만 아니라 도전성 고분자의 안정성이나 용해성 등의 특성도 크게 영향을 받는다.Generally, in the electrolytic polymerization method, a supporting electrolyte such as lithium salt, sodium salt or quaternary ammonium salt is dissolved in an organic solvent such as acetonitrile or ethylene carbonate to form an electrolyte, and an electrolyte composition containing monomers in the electrolyte is used. do. These supporting electrolytes act not only for securing the electrical conductivity of the electrolyte solution, but also act as a dopant which is blown into the obtained conductive polymer to increase the electrical conductivity of the conductive polymer itself. Therefore, the electrical conductivity of the conductive polymer largely depends on the conditions such as the type of the supporting electrolyte and the concentration in the electrolyte solution. In addition, not only electrical conductivity but also properties such as stability and solubility of the conductive polymer are greatly affected.
또한, 이온 농도가 높고, 불휘발성이며 인화성이 없는 이온 액체(상온 용융염)를 전해질로서 사용하는 방법이 제안되어 있다(예를 들면 비특허문헌 1). 이온 액체로서 사용되는 것은, 주로 이미다졸륨염, 피리디늄염, 4급 암모늄염, 피롤리디늄염, 피페리디늄염과 같은 질소 함유 양이온을 갖는 화합물이다. 그러나, 이들 이온 액체를 전해질로서 사용한 전해 중합 반응용 전해액의 경우, 이온 액체의 높은 점성에 의해 전기 전도성이 낮아서 전해 중합 반응의 효율을 충분히 높일 수 없다고 하는 문제가 있다.Moreover, the method of using the ionic liquid (room temperature molten salt) which is high in ion concentration, nonvolatile, and inflammable as an electrolyte is proposed (for example, nonpatent literature 1). It is mainly used as an ionic liquid is a compound having a nitrogen-containing cation such as imidazolium salt, pyridinium salt, quaternary ammonium salt, pyrrolidinium salt, piperidinium salt. However, in the case of the electrolyte solution for the electrolytic polymerization reaction using these ionic liquids as an electrolyte, there is a problem that the electrical conductivity is low due to the high viscosity of the ionic liquid and the efficiency of the electrolytic polymerization reaction cannot be sufficiently increased.
한편, 인계의 4급 포스포늄 양이온을 주체로 하는 이온 액체도 알려져 있다. 4급 포스포늄염은 화학적 및 열적으로 안정한 것이 알려져 있고, 또한 인을 함유하는 것에 의한 난연성을 갖는 것도 알려져 있다. 4급 포스포늄염의 전해 중합 반응용 전해액에의 응용에 대해서는, 예를 들면 비특허문헌 2에 트리헥실(테트라데실)포스포늄비스(트리플루오로메틸술포닐)이미드를 전해질로서 사용한 피롤의 전해 산화 중합 반응이 기재되어 있다. 그러나, 동 문헌에 기재된 4급 포스포늄염 이온 액체는 현저히 고점성이며 저전기 전도성이고, 전해질로서 사용하기 위해서는 불리할 뿐만 아니라, 동 문헌에는 4급 포스포늄염이 갖는 특징에 대해서는 전혀 기재되어 있지 않다.On the other hand, ionic liquids mainly composed of phosphorus quaternary phosphonium cations are also known. It is known that quaternary phosphonium salts are chemically and thermally stable, and are also known to have flame retardancy by containing phosphorus. For application of the quaternary phosphonium salt to the electrolytic solution for electrolytic polymerization reaction, for example, electrolysis of pyrrole using trihexyl (tetradecyl) phosphonium bis (trifluoromethylsulfonyl) imide as an electrolyte in Non-Patent Document 2 Oxidative polymerization reactions are described. However, quaternary phosphonium salt ionic liquids described in this document are notably high viscosity, low electrical conductivity, disadvantageous for use as an electrolyte, and the document does not describe at all the features of quaternary phosphonium salts. not.
본 발명의 목적은, 상술한 종래 기술이 갖는 전해 중합 반응에 있어서의 여러 가지 결점을 해소할 수 있는 화합물 및 그것을 사용하여 얻어지는 도전성 고분자를 제공하는 것에 있다.An object of the present invention is to provide a compound capable of eliminating various drawbacks in the electrolytic polymerization reaction of the above-described prior art and a conductive polymer obtained using the same.
이러한 실정에 있어서, 본 발명자들은 예의 검토한 결과, 특정 4급 포스포늄염으로 이루어지는 이온 액체는 전기 전도성이 높고, 상기 이온 액체를 전해 중합 반응에 사용하면 상기 이온 액체가 도핑되어 전기 전도성이 높으며 내열성ㆍ난연성이 우수한 도전성 고분자가 얻어지기 때문에, 상기 이온성 액체는 도전성 고분자용 도펀트로서 바람직한 것을 발견하고, 본 발명을 완성하기에 이르렀다.In this situation, the present inventors have diligently investigated that the ionic liquid consisting of a particular quaternary phosphonium salt has high electrical conductivity, and when the ionic liquid is used in an electrolytic polymerization reaction, the ionic liquid is doped to have high electrical conductivity and heat resistance. Since the conductive polymer excellent in flame retardancy is obtained, the ionic liquid was found to be suitable as a dopant for the conductive polymer, and thus the present invention was completed.
즉, 본 발명은 하기 화학식 1로 표시되는 4급 포스포늄염으로 이루어지는 것을 특징으로 하는 도전성 고분자용 도펀트를 제공하는 것이다.That is, the present invention is to provide a dopant for a conductive polymer, characterized in that consisting of a quaternary phosphonium salt represented by the formula (1).
(식 중, R1, R2 및 R3은 탄소수 1 내지 8의 알킬기를 나타내며, 서로 동일하거나 상이할 수도 있고, R1과 R2가 결합하여 환을 형성할 수도 있고, n은 메틸렌기의 수를 나타내며, n=1 내지 6이고, R4 내지 R8은 수소 원자 또는 치환기를 나타내며, 서로 동일하거나 상이할 수도 있고, X-는 음이온을 나타낸다.)(In formula, R <1> , R <2> and R <3> represent a C1-C8 alkyl group, and may mutually be same or different, R <1> and R <2> may combine and form a ring, n is a methylene group Number, n = 1 to 6, R 4 to R 8 represent a hydrogen atom or a substituent, may be the same or different from each other, and X − represents an anion.)
또한, 본 발명은 상기 도전성 고분자용 도펀트가 도핑되어 있는 것을 특징으로 하는 도전성 고분자를 제공하는 것이다.The present invention also provides a conductive polymer, wherein the dopant for the conductive polymer is doped.
또한, 본 발명은 상기 도전성 고분자의 제조 방법으로서, 상기 도전성 고분자용 도펀트의 존재하에 중합성 단량체를 전해 중합시키는 것을 특징으로 하는 도전성 고분자의 제조 방법을 제공하는 것이다.The present invention also provides a method for producing a conductive polymer, wherein the polymerizable monomer is electrolytically polymerized in the presence of the dopant for the conductive polymer.
또한, 본 발명은 상기 도전성 고분자를 사용한 것을 특징으로 하는 전기 화학 디바이스를 제공하는 것이다.Moreover, this invention provides the electrochemical device characterized by using the said conductive polymer.
또한, 본 발명은 상기 도전성 고분자용 도펀트를 함유하는 것을 특징으로 하는 중합성 단량체의 전해 중합용 전해액 조성물을 제공하는 것이다.Moreover, this invention provides the electrolyte solution composition for electrolytic polymerization of the polymerizable monomer characterized by containing the said dopant for conductive polymers.
본 발명에 따른 4급 포스포늄염은 전기 전도성이 높으며 내열성 및 난연성이 풍부한 것으로, 도전성 고분자용 도펀트로서 높은 기능을 가짐과 동시에 전해 중합 반응용 전해질로서도 바람직하고, 또한 전해 중합 반응용 전해액 조성물로서 사용할 수도 있다. 따라서, 상기 포스포늄염으로 이루어지는 본 발명의 도전성 고분자용 도펀트의 존재하에 중합성 단량체를 전해 중합시킴으로써, 빠르게 전해 중합 반응이 진행되어 효율적으로 도전성 고분자를 얻을 수 있고, 게다가 얻어지는 도전성 고분자의 전기 도전성, 내열성 및 난연성도 높일 수 있다. 또한, 전해 중합 반응에 적용되는 전해액 조성물의 내열성 및 난연성도 높일 수 있다.The quaternary phosphonium salt according to the present invention has high electrical conductivity, is rich in heat resistance and flame retardancy, has a high function as a dopant for conductive polymers, is also suitable as an electrolyte for an electrolytic polymerization reaction, and can be used as an electrolyte composition for an electrolytic polymerization reaction. It may be. Therefore, by electrolytically polymerizing the polymerizable monomer in the presence of the dopant for the conductive polymer of the present invention made of the phosphonium salt, the electrolytic polymerization reaction proceeds rapidly, so that the conductive polymer can be efficiently obtained, and the electrical conductivity of the obtained conductive polymer, Heat resistance and flame retardancy can also be improved. Moreover, the heat resistance and flame retardance of the electrolyte solution composition applied to an electrolytic polymerization reaction can also be improved.
이하, 본 발명을 그의 바람직한 실시 형태에 기초하여 설명한다. 화학식 1로 표시되는 4급 포스포늄염에 있어서의 4개의 기 중 3개는 알킬기이고, 나머지 중 1개는 알킬렌기 -(CH2)n-로 연결된 비치환 또는 치환 페닐기이다. 이러한 구조의 4급 포스포늄염은, 인에 결합하는 기가 전부 비치환 알킬기인 4급 포스포늄염에 비해 전기 전도성이 높아지며 내열성도 각별히 높아진다. 그 이유는 현시점에서는 완전히 해명되지는 않았지만, 페닐기의 π 전자와 인 원자의 d 궤도와의 상호 작용에서 기인한다고 생각된다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated based on the preferable embodiment. Three of the four groups in the quaternary phosphonium salt represented by the general formula (1) are alkyl groups, and one of the remaining groups is an unsubstituted or substituted phenyl group linked by an alkylene group-(CH 2 ) n- . The quaternary phosphonium salt having such a structure has higher electrical conductivity and higher heat resistance than the quaternary phosphonium salt in which all of the groups bonded to phosphorus are unsubstituted alkyl groups. Although the reason is not fully understood at this time, it is thought that it originates from interaction of the pi atom of a phenyl group, and the d orbit of a phosphorus atom.
또한, 화학식 1로 표시되는 4급 포스포늄염은, 하기 (a)에 나타낸 바와 같이 인 원자가 갖는 빈 d 궤도와 도전성 고분자 주쇄와의 상호 작용, 벤질기의 π 전자와 도전성 고분자의 π 공액계와의 π-π 상호 작용을 나타낸다. 이들 상호 작용에 의해, 화학식 1로 표시되는 4급 포스포늄염은 도전성 고분자 중에 도핑되기 쉬워진다고 생각되고, 얻어지는 도전성 고분자의 전기 전도성 및 내열성의 향상에도 크게 기여한다. 한편, 4급 암모늄염이면, 하기 (b)에 나타낸 바와 같이, 벤질기의 π 전자와 도전성 고분자의 π 공액계와의 π-π 상호 작용은 나타내지만, 질소 원자와 도전성 고분자 주쇄와의 상호 작용이나 빈 d 궤도와 도전성 고분자 주쇄와의 상호 작용은 나타내지 않기 때문에, 4급 포스포늄염에 비해 도핑 효율이 뒤떨어진다고 생각된다.In addition, the quaternary phosphonium salt represented by the general formula (1) has an interaction between the empty d orbit of the phosphorus atom and the conductive polymer backbone, the π electron of the benzyl group and the π conjugated system of the conductive polymer, as shown in the following (a). Represents the π-π interaction. By these interactions, the quaternary phosphonium salt represented by the general formula (1) is thought to be easily doped in the conductive polymer, and contributes greatly to the improvement of the electrical conductivity and heat resistance of the obtained conductive polymer. On the other hand, if it is a quaternary ammonium salt, as shown to (b) below, although the (pi)-(pi) interaction of the (pi) electron of a benzyl group and (pi) conjugated system of a conductive polymer is shown, interaction of a nitrogen atom and a conductive polymer main chain, Since the interaction between the empty d orbit and the conductive polymer backbone is not shown, it is considered that the doping efficiency is inferior to that of the quaternary phosphonium salt.
화학식 1 중의 R1, R2, R3으로 표시되는 탄소수 1 내지 8의 알킬기는 직쇄상, 분지상, 환상 중 어느 것일 수도 있고, 그의 구체적인 예로서는, 메틸기, 에틸기, n-프로필기, n-부틸기, n-펜틸기, n-헥실기, n-헵틸기, n-옥틸기, i-프로필기, i-부틸기, i-펜틸기, i-헥실기, i-헵틸기, i-옥틸기, 시클로펜틸기, 시클로헥실기, 시클로헵틸기, 시클로옥틸기 등을 들 수 있다. 이들 기 중, 4급 포스포늄염의 융점을 내리고 전기 전도성을 높여 이온 액체성을 높인다는 관점에서, R1, R2 및 R3의 모두가 동일한 알킬기인 것이 바람직하고, 에틸기, 프로필기, 부틸, 옥틸기인 것이 더욱 바람직하다. 특히, R1, R2 및 R3의 전부가 동일한 직쇄 알킬기인 것이 바람직하고, 특별히 에틸기, n-프로필기, n-부틸, n-옥틸기인 것이 바람직하다. 4급 포스포늄염의 내열성을 높인다는 관점에서는, R1, R2 및 R3의 전부가 에틸기인 것이 가장 바람직하다.The alkyl group having 1 to 8 carbon atoms represented by R 1 , R 2 , and R 3 in the general formula (1) may be linear, branched or cyclic. Specific examples thereof include methyl group, ethyl group, n-propyl group and n-butyl Group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, i-propyl group, i-butyl group, i-pentyl group, i-hexyl group, i-heptyl group, i-jade A methyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, etc. are mentioned. Among these groups, from the viewpoint of lowering the melting point of the quaternary phosphonium salt and increasing the electrical conductivity to increase the ionic liquidity, it is preferable that all of R 1 , R 2 and R 3 are the same alkyl group, and ethyl group, propyl group, butyl, It is more preferable that it is an octyl group. In particular, it is preferable that all of R <1> , R <2> and R <3> are the same linear alkyl groups, and it is especially preferable that they are an ethyl group, n-propyl group, n-butyl, n-octyl group. From the viewpoint of increasing the heat resistance of the quaternary phosphonium salt, it is most preferable that all of R 1 , R 2 and R 3 are ethyl groups.
화학식 1 중의 알킬렌기 -(CH2)n-의 메틸렌기의 수 n은 1 내지 6이다. 4급 포스포늄염의 전기 전도성과 내열성을 높인다는 관점에서는, n=1인 것이 바람직하다.The number n of the methylene groups of the alkylene group-(CH 2 ) n -in the general formula (1) is 1 to 6. It is preferable that n = 1 from a viewpoint of raising the electrical conductivity and heat resistance of a quaternary phosphonium salt.
화학식 1 중의 R4, R5, R6, R7, R8은 수소 원자 또는 치환기이고, 치환기의 구체적인 예로서는, 알킬기, 메톡시기, 에톡시기 및 프로폭시기 등의 알콕시기, 히드록실기, 니트릴기, 니트로기, 카르복실기, 아세틸기, 벤조일기, 술폰기 등을 들 수 있다. 상기 알킬기로서는, 메틸기, 에틸기, n-프로필기, n-부틸기, n-펜틸기, n-헥실기, i-프로필기, i-부틸기, i-펜틸기, i-헥실기, 시클로펜틸기, 시클로헥실기 등의 비치환 알킬기를 들 수 있다. 상기 알킬기로서는, 치환 알킬기를 사용할 수도 있다. 치환기로서는, 알콕시기, 시아노기, 할로겐 원자 등을 들 수 있다. 치환 알킬기의 구체적인 예로서는, 메톡시메틸기, 2-메톡시에틸기, 3-메톡시프로필기, 4-메톡시부틸기, 5-메톡시펜틸기, 6-메톡시헥실기, 에톡시메틸기, 2-에톡시에틸기, 3-에톡시프로필기, 4-에톡시부틸기, 5-에톡시펜틸기, 6-에톡시헥실기, 시아노메틸기, 시아노에틸기, 트리플루오로메틸기, 펜타플루오로에틸기 등을 들 수 있다.R <4> , R <5> , R <6> , R <7> and R <8> in general formula (1) are a hydrogen atom or a substituent, As a specific example of a substituent, Alkoxy groups, such as an alkyl group, a methoxy group, an ethoxy group, and a propoxy group, a hydroxyl group, and a nitrile A group, a nitro group, a carboxyl group, an acetyl group, a benzoyl group, a sulfone group, etc. are mentioned. As said alkyl group, a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, i-propyl group, i-butyl group, i-pentyl group, i-hexyl group, cyclophene Unsubstituted alkyl groups, such as a methyl group and a cyclohexyl group, are mentioned. As said alkyl group, you may use a substituted alkyl group. As a substituent, an alkoxy group, a cyano group, a halogen atom, etc. are mentioned. As a specific example of a substituted alkyl group, a methoxymethyl group, 2-methoxyethyl group, 3-methoxypropyl group, 4-methoxybutyl group, 5-methoxypentyl group, 6-methoxyhexyl group, ethoxymethyl group, 2- Ethoxyethyl group, 3-ethoxypropyl group, 4-ethoxybutyl group, 5-ethoxypentyl group, 6-ethoxyhexyl group, cyanomethyl group, cyanoethyl group, trifluoromethyl group, pentafluoroethyl group, etc. Can be mentioned.
특히, 4급 포스포늄염의 내열성을 높인다는 관점에서는, R4, R5, R6, R7, R8은 이들 전부가 동일한 기인 것이 바람직하고, 특히 모든 기가 수소 원자, 메틸기 또는에틸기인 것이 바람직하다. 4급 포스포늄염의 융점을 내리고 전기 전도성을 높여서 이온 액체성을 높인다는 관점에서는, 모든 기가 수소 원자인 것이 특히 바람직하다.In particular, from the viewpoint of increasing the heat resistance of the quaternary phosphonium salt, R 4 , R 5 , R 6 , R 7 , and R 8 are all preferably the same group, and in particular, all the groups are preferably a hydrogen atom, a methyl group or an ethyl group. Do. From the viewpoint of lowering the melting point of the quaternary phosphonium salt and increasing the electrical conductivity to increase the ionic liquidity, it is particularly preferable that all the groups are hydrogen atoms.
화학식 1 중의 X-의 음이온 성분으로서는, 4급 포스포늄염이 사용되는 온도에서 상기 염이 이온 액체가 되는 것이면 특별히 제한되지 않는다. 예를 들면, 테트라플루오로보레이트(BF4), 헥사플루오로포스페이트(PF6), 비스(트리플루오로메틸술포닐)이미드(N(SO2CF3)2), 비스(플루오로술포닐)이미드(N(SO2F)2), 트리플루오로메탄술포네이트(SO3CF3), 펜타플루오로에탄술포네이트(SO3CF2CF3), 테트라플루오로에탄술포네이트(SO3CHFCF3), 메탄술포네이트(SO3CH3), 트리스(펜타플루오로에틸)트리플루오로포스페이트((C2H5)3PF3), 트리플루오로아세트산(CF3COO), 아미노산, 비스옥살레이트보레이트(B(C2O4)2), p-톨루엔술포네이트(SO3C6H4CH3), 티오시아네이트(SCN), 디시안아미드(N(CN)2), 테트라시아노보레이트(B(CN)4), 디알킬인산((RO)2POO), 디알킬디티오인산((RO)2PSS), 지방족 카르복실산(RCOO) 등을 들 수 있다. 이들 중에서, 4급 포스포늄염의 융점을 내리고 전기 전도성을 높여서 이온 액체성을 높인다는 관점에서, 비스(트리플루오로메틸술포닐)이미드, 비스(플루오로술포닐)이미드, 디시안아미드 및 테트라시아노보레이트를 음이온 성분으로서 사용하는 것이 바람직하다. 특히, 비스(트리플루오로메틸술포닐)이미드는, 4급 포스포늄염이 우수한 내전압성 및 내열성을 부여할 수 있기 때문에 특별히 바람직한 음이온 성분이다.The anion component of X − in the formula (1) is not particularly limited as long as the salt becomes an ionic liquid at the temperature at which the quaternary phosphonium salt is used. For example, tetrafluoroborate (BF 4 ), hexafluorophosphate (PF 6 ), bis (trifluoromethylsulfonyl) imide (N (SO 2 CF 3 ) 2 ), bis (fluorosulfonyl ) Imide (N (SO 2 F) 2 ), trifluoromethanesulfonate (SO 3 CF 3 ), pentafluoroethanesulfonate (SO 3 CF 2 CF 3 ), tetrafluoroethanesulfonate (SO 3 CHFCF 3 ), methanesulfonate (SO 3 CH 3 ), tris (pentafluoroethyl) trifluorophosphate ((C 2 H 5 ) 3 PF 3 ), trifluoroacetic acid (CF 3 COO), amino acids, bis Oxalate borate (B (C 2 O 4 ) 2 ), p-toluenesulfonate (SO 3 C 6 H 4 CH 3 ), thiocyanate (SCN), dicyanamide (N (CN) 2 ), tetracy Anborate (B (CN) 4 ), dialkylphosphoric acid ((RO) 2 POO), dialkyldithiophosphoric acid ((RO) 2 PSS), aliphatic carboxylic acid (RCOO) and the like. Among them, bis (trifluoromethylsulfonyl) imide, bis (fluorosulfonyl) imide, dicyamide and the like from the viewpoint of lowering the melting point of the quaternary phosphonium salt and increasing the electrical conductivity to increase the ionic liquidity. It is preferable to use tetracyanoborate as an anion component. In particular, bis (trifluoromethylsulfonyl) imide is a particularly preferable anion component because the quaternary phosphonium salt can impart excellent voltage resistance and heat resistance.
화학식 1로 표시되는 4급 포스포늄염의 바람직한 구체적인 예로서는, 4급 포스포늄염의 융점을 내리고 전기 전도성을 높인다는 관점에서, 트리에틸벤질포스포늄비스(트리플루오로메틸술포닐)이미드, 트리-n-부틸벤질포스포늄비스(트리플루오로메틸술포닐)이미드, 트리에틸벤질포스포늄비스(플루오로술포닐)이미드, 트리-n-부틸벤질포스포늄비스(플루오로술포닐)이미드, 트리에틸벤질포스포늄디시안아미드, 트리-n-부틸벤질포스포늄디시안아미드, 트리에틸벤질포스포늄테트라시아노보레이트 및 트리-n-부틸벤질포스포늄테트라시아노보레이트를 들 수 있다. 특히, 트리에틸벤질포스포늄비스(트리플루오로메틸술포닐)이미드는 내전압성 및 내열성이 우수하기 때문에 특별히 바람직한 물질이다. Preferred specific examples of the quaternary phosphonium salt represented by the formula (1) include triethylbenzylphosphonium bis (trifluoromethylsulfonyl) imide and tri-n from the viewpoint of lowering the melting point of the quaternary phosphonium salt and increasing the electrical conductivity. -Butylbenzylphosphonium bis (trifluoromethylsulfonyl) imide, triethylbenzylphosphonium bis (fluorosulfonyl) imide, tri-n-butylbenzylphosphonium bis (fluorosulfonyl) imide, Triethyl benzyl phosphonium dicyanamide, tri-n-butyl benzyl phosphonium dicyanamide, triethyl benzyl phosphonium tetracyanoborate, and tri-n-butyl benzyl phosphonium tetracyanoborate. In particular, triethylbenzylphosphonium bis (trifluoromethylsulfonyl) imide is a particularly preferable substance because of its excellent voltage resistance and heat resistance.
화학식 1로 표시되는 4급 포스포늄염은 그의 사용 환경하에서 전기 전도성을 갖는 액상체, 즉 이온 액체이다. 그의 융점은 100 ℃ 이하인 것이 바람직하다. 이 4급 포스포늄염의 융점은 더욱 바람직하게는 50 ℃ 이하, 더욱 바람직하게는 25 ℃ 이하, 가장 바람직하게는 0 ℃ 이하이다. 융점이 50 ℃ 이하인 경우에는, 융해에 요하는 가열량을 적게 할 수 있기 때문에 유리하다. 또한, 융점이 25 ℃ 이하이면 상온에서 액상이기 때문에, 가열 융해시킬 필요가 없기 때문에 유리하다. 4급 포스포늄염의 융점의 하한값에 특별히 제한은 없고, 낮으면 낮을수록 바람직하지만, 0 ℃ 이하이면 액상 온도 영역이 넓고, 저온으로부터 고온까지의 넓은 온도 범위에서 사용가능해진다고 하는 관점에서 바람직하다.The quaternary phosphonium salt represented by the formula (1) is a liquid body, ie an ionic liquid, having electrical conductivity under its use environment. It is preferable that the melting point is 100 degrees C or less. The melting point of this quaternary phosphonium salt is more preferably 50 ° C. or less, more preferably 25 ° C. or less, and most preferably 0 ° C. or less. When melting | fusing point is 50 degrees C or less, since the amount of heating required for melting can be reduced, it is advantageous. Moreover, since melting | fusing point is 25 degrees C or less, since it is a liquid at normal temperature, it does not need to heat-melt, and it is advantageous. There is no restriction | limiting in particular in the lower limit of the melting | fusing point of a quaternary phosphonium salt, It is preferable that it is low, but it is preferable at the point of 0 degrees C or less from a viewpoint that it can use in the wide temperature range from low temperature to high temperature.
화학식 1로 표시되는 4급 포스포늄염은 4급 포스포늄할라이드와 음이온 성분의 금속염을 통상법에 따라서 반응시켜 음이온 교환함으로써 얻을 수 있다. 4급 포스포늄할라이드란, 화학식 1로 표시되는 4급 포스포늄염에 있어서의 음이온 부분이 할로겐인 것의 총칭이다. 4급 포스포늄할라이드는, 예를 들면 이하와 같이 하여 합성할 수 있을 뿐 아니라, 닛본 가가꾸 고교(주) 등으로부터 시판되고 있는 제품을 사용할 수도 있다.The quaternary phosphonium salt represented by the formula (1) can be obtained by reacting a quaternary phosphonium halide with a metal salt of an anion component according to a conventional method and performing anion exchange. The quaternary phosphonium halide is a generic term for the anion moiety in the quaternary phosphonium salt represented by the general formula (1) being halogen. A quaternary phosphonium halide can be synthesize | combined as follows, for example, and can also use the product marketed from Nippon Chemical Industries, Ltd. etc.
4급 포스포늄할라이드가 트리알킬(페닐알킬)포스포늄할라이드인 경우, 이 화합물은, 예를 들면 트리알킬포스핀과 할로겐화알킬벤젠을 반응시켜 얻을 수 있다. 특히, 인 원자에 결합되어 있는 3개의 알킬기가 동일한 트리알킬포스핀[화학식 :(Ra)3P(Ra는 R1 내지 R3에 대응하는 알킬기)]와, 할로겐화알킬벤젠[화학식: X-(CH2)n-φ(X는 할로겐 원자, φは R4 내지 R8을 갖는 벤젠환)]을 반응시키는 방법을 채용하면 불순물이 적은 목적물을 얻을 수 있기 때문에 바람직하다. 또한, 4급 포스포늄할라이드의 할로겐이 브롬이나 요오드이면, 4급 포스포늄할라이드를 재결정에 의해 정제할 수 있기 때문에 바람직하다. 이 관점에서, 할로겐화알킬벤젠으로서 브롬화알킬벤젠이나 요오드화알킬벤젠을 사용하는 것이 바람직하다. 또한, 4급 포스포늄할라이드에 있어서의 할로겐이 브롬 및 요오드 이외의 원소인 경우, 예를 들면 염소이어도 요오드화나트륨 등을 사용함으로써, 염소를 요오드 또는 브롬으로 치환할 수 있다.When the quaternary phosphonium halide is trialkyl (phenylalkyl) phosphonium halide, this compound can be obtained, for example, by reacting trialkylphosphine with a halogenated alkylbenzene. In particular, three alkyl groups bonded to the phosphorus atom are the same trialkylphosphine [Formula: (R a ) 3 P (R a is an alkyl group corresponding to R 1 to R 3 )], and a halogenated alkylbenzene [Formula X: -(CH 2 ) n -φ (X is a halogen atom, a benzene ring having phi R 4 to R 8 )] is adopted in order to obtain a target product having few impurities. If the halogen of the quaternary phosphonium halide is bromine or iodine, the quaternary phosphonium halide can be purified by recrystallization, which is preferable. From this point of view, it is preferable to use brominated alkylbenzenes or iodide alkylbenzenes as halogenated alkylbenzenes. In the case where the halogen in the quaternary phosphonium halide is an element other than bromine and iodine, chlorine can be replaced with iodine or bromine by using sodium iodide or the like even if it is chlorine.
4급 포스포늄할라이드를 합성하여 얻기 위해서는, 우선 트리알킬포스핀에 대하여 할로겐화알킬벤젠을 바람직하게는 0.5 내지 2배 몰, 더욱 바람직하게는 0.9 내지 1.2배 몰 첨가한다. 또한, 염소를 포함하지 않는 불활성 용매 중, 예를 들면 톨루엔 중에서, 바람직하게는 20 내지 150 ℃, 더욱 바람직하게는 30 내지 100 ℃에서, 바람직하게는 3 시간 이상, 더욱 바람직하게는 5 내지 12 시간 반응시킨다. 반응 분위기는 산소가 존재하지 않는 분위기가 바람직하다. 예를 들면 질소 분위기 또는 아르곤 분위기가 바람직하다. 산소가 존재하는 분위기 중에서 트리알킬포스핀과 할로겐화알킬벤젠을 반응시키면, 트리알킬포스핀에 산소가 결합된 트리알킬포스핀옥시드가 생성되어 수율이 저하되는 경향이 있다. 트리알킬포스핀옥시드는 적절하게 유기 용매로 세정함으로써 제거할 수 있지만, 4급 포스포늄할라이드의 탄소수의 총 수가 커지면, 4급 포스포늄할라이드도 유기 용매에 용해되는 경향이 있기 때문에 제거가 곤란해진다. 따라서, 트리알킬포스핀옥시드를 생성시키지 않도록 하기 위해서, 불활성 분위기하에서 반응을 행하는 것이 바람직하다.In order to synthesize | combine a quaternary phosphonium halide, the halogenated alkylbenzene is preferably added 0.5 to 2 times mole, more preferably 0.9 to 1.2 times mole relative to trialkylphosphine. Moreover, in an inert solvent which does not contain chlorine, for example in toluene, Preferably it is 20-150 degreeC, More preferably, it is 30-100 degreeC, Preferably it is 3 hours or more, More preferably, it is 5-12 hours. React. The reaction atmosphere is preferably an atmosphere in which oxygen is not present. For example, nitrogen atmosphere or argon atmosphere is preferable. When trialkyl phosphine and halogenated alkylbenzene are reacted in the atmosphere in which oxygen exists, the trialkyl phosphine oxide which oxygen couple | bonded with trialkyl phosphine produces | generates, and there exists a tendency for a yield to fall. Although trialkylphosphine oxide can be removed by washing with an organic solvent suitably, when the total number of carbon number of a quaternary phosphonium halide becomes large, since quaternary phosphonium halide tends to melt | dissolve in an organic solvent, removal becomes difficult. Therefore, in order not to produce trialkylphosphine oxide, it is preferable to perform reaction in inert atmosphere.
음이온 교환에 의해 4급 포스포늄할라이드에 필요한 음이온 X-를 도입하기 위해서 사용되는 음이온 성분의 금속염으로서는, 예를 들면 상기 음이온 성분의 Li염 등의 알칼리 금속염을 사용할 수 있다. 알칼리 금속염을 사용하면, 상기 염과 4급 포스포늄할라이드와의 반응에 의해 목적물인 4급 포스포늄염이 생성될 때에 생성되는 할로겐화 알칼리(부생물)을, 수세나 흡착제에 의해서 용이하게 제거할 수 있기 때문에 바람직하다.As a metal salt of the anion component used in order to introduce the anion X <-> required for quaternary phosphonium halide by anion exchange, alkali metal salts, such as Li salt of the said anion component, can be used, for example. When the alkali metal salt is used, the halogenated alkali (by-product) generated when the quaternary phosphonium salt is produced by the reaction between the salt and the quaternary phosphonium halide can be easily removed by washing with water or an adsorbent. It is preferable because there is.
수세에 사용되는 물은 초순수나 탈이온수를 사용할 수 있다. 수세는 불순물 함유량이 저하될 때까지 적절하게 반복하여 행하는 것이 바람직하다. 수세에 의해 제거해야 할 불순물로서는, 미반응 원료 및 할로겐화 알칼리 등을 들 수 있다. 또한, 미반응 원료나 부생물 등을 제거하기 위해서, 적절하게 유기 용매에 의한 세정을 행할 수도 있다. 세정에 사용할 수 있는 유기 용매로서는, 염소를 포함하지 않은 비극성 용매, 예를 들면 펜탄, 헥산, 헵탄 등을 사용하는 것이 바람직하다. 이들 비극성 용매를 사용함으로써, 4급 포스포늄염을 용해시키지 않고 불순물 등의 비극성 유기 화합물을 효율적으로 제거할 수 있다.Ultra pure water or deionized water may be used for the water used for washing. It is preferable to perform water washing repeatedly suitably until an impurity content falls. As an impurity which should be removed by water washing | cleaning, an unreacted raw material, a halogenated alkali, etc. are mentioned. Moreover, in order to remove an unreacted raw material, a by-product, etc., you may wash with an organic solvent suitably. As an organic solvent which can be used for washing | cleaning, it is preferable to use the nonpolar solvent which does not contain chlorine, for example, pentane, hexane, heptane, etc. By using these nonpolar solvents, nonpolar organic compounds such as impurities can be efficiently removed without dissolving quaternary phosphonium salts.
물이나 유기 용매로 세정한 4급 포스포늄염은, 수분이나 유기 용매를 제거하기 위해서 정제되는 것이 바람직하다. 정제법으로서는, 분자체 등의 건조제에 의한 탈수 및 진공 건조에 의한 탈용매 등의 방법을 들 수 있다. 불순물의 혼입을 방지하고, 수분과 유기 용매를 한번에 제거할 수 있기 때문에 진공 건조에 의한 정제가 바람직하다. 진공 건조에 의한 정제에서는, 건조 온도가 바람직하게는 70 내지 120 ℃, 더욱 바람직하게는 80 내지 100 ℃이고, 진공도가 바람직하게는 0.1 내지 1.0 kPa, 더욱 바람직하게는 0.1 내지 0.5 kPa이다. 시간은 바람직하게는 2 내지 8 시간 정도, 더욱 바람직하게는 5 내지 12 시간 정도이다.It is preferable that the quaternary phosphonium salt wash | cleaned with water or an organic solvent is refine | purified in order to remove water and an organic solvent. As a purification method, methods, such as dehydration by drying agents, such as a molecular sieve, and desolvent by vacuum drying, are mentioned. Purification by vacuum drying is preferable because the incorporation of impurities can be prevented and moisture and the organic solvent can be removed at once. In the purification by vacuum drying, the drying temperature is preferably 70 to 120 ° C, more preferably 80 to 100 ° C, and the degree of vacuum is preferably 0.1 to 1.0 kPa, more preferably 0.1 to 0.5 kPa. The time is preferably about 2 to 8 hours, more preferably about 5 to 12 hours.
이와 같이 하여 얻어진 화학식 1로 표시되는 4급 포스포늄염은 높은 전기 전도성, 적절한 용해성, 화학적 안정성 및 열 안정성이라는 성질을 갖는다. 이러한 성질을 갖는 4급 포스포늄염을 도전성 고분자에 도핑함으로써, 상기 도전성 고분자에 전기 전도성을 비롯한 각종 유리한 특성을 부여할 수 있다. 또한, 이 4급 포스포늄염을 도전성 고분자의 전해 중합 반응에 사용되는 전해액 조성물에 함유시킴으로써, 전해 중합 반응의 효율이 현저히 향상된다. 이러한 이점 뿐만 아니라, 도전성 고분자 중에 4급 포스포늄염을 도핑하는 효율이 향상되는 경향이 있고, 얻어지는 도전성 고분자의 전기 전도성을 높일 수 있다고 하는 이점도 있다. 이들 이점은, 4급 포스포늄염 이온 액체에 페닐기가 도입되어 있는 것에 의한 높은 전기 전도성에서 기인한다고 생각된다.The quaternary phosphonium salt represented by the general formula (1) thus obtained has properties of high electrical conductivity, proper solubility, chemical stability and thermal stability. By doping a quaternary phosphonium salt having such a property to the conductive polymer, various advantageous properties including electrical conductivity can be imparted to the conductive polymer. Moreover, the efficiency of an electrolytic polymerization reaction improves remarkably by containing this quaternary phosphonium salt in the electrolyte solution composition used for the electrolytic polymerization reaction of a conductive polymer. In addition to these advantages, the efficiency of doping the quaternary phosphonium salt in the conductive polymer tends to be improved, and there is also an advantage that the electrical conductivity of the obtained conductive polymer can be enhanced. These advantages are considered to be due to the high electrical conductivity by introducing a phenyl group into the quaternary phosphonium salt ionic liquid.
또한, 화학식 1로 표시되는 4급 포스포늄염은 그의 구조에서 유래하여 난연성 및 자기 소화성을 발현하는 것이다. 특히, 상기 4급 포스포늄염은 알킬기가 짧고(탄소수 1 내지 8), 분자량이 작기 때문에 인 원자의 비율이 높고, 적절한 난연성 및 자기 소화성을 갖는다. 따라서, 상기 4급 포스포늄염이 도핑된 도전성 고분자에는, 인 원자 유래의 내열성이 부여된다. 또한, 상기 도전성 고분자를 전해 중합으로 합성할 때에 사용되는 전해액 조성물에 상기 4급 포스포늄염을 함유시킴으로써, 상기 전해액 조성물의 안전성을 높일 수도 있다.The quaternary phosphonium salt represented by the formula (1) is derived from its structure and expresses flame retardancy and self-extinguishing. In particular, the quaternary phosphonium salts have a short alkyl group (1 to 8 carbon atoms), a low molecular weight, high proportion of phosphorus atoms, and have an appropriate flame retardancy and self-extinguishing ability. Therefore, heat resistance derived from a phosphorus atom is provided to the conductive polymer doped with the quaternary phosphonium salt. Moreover, the safety of the said electrolyte solution composition can also be improved by containing the said quaternary phosphonium salt in the electrolyte solution composition used when synthesize | combining the said conductive polymer by electrolytic polymerization.
이상의 설명으로부터 분명한 바와 같이, 화학식 1로 표시되는 4급 포스포늄염은 그의 구조 중에 페닐기를 가지고 있기 때문에, 상기 4급 포스포늄염이 도핑된 도전성 고분자는 전기 전도성, 내열성 및 난연성이 높은 것이 된다. 또한, 상기 도전성 고분자를 전해 중합으로 합성할 때에 사용되는 전해액 조성물에 상기 4급 포스포늄염을 함유시킴으로써, 높은 전해 중합 반응 효율이 얻어진다. 따라서, 상기 4급 포스포늄염은 도전성 고분자의 도펀트 및 도전성 고분자의 전해 중합 반응에 사용되는 전해액 조성물에 유리하게 사용할 수 있는 것이다.As is clear from the above description, since the quaternary phosphonium salt represented by the formula (1) has a phenyl group in its structure, the conductive polymer doped with the quaternary phosphonium salt is highly conductive, heat resistant and flame retardant. Moreover, high electrolytic polymerization reaction efficiency is obtained by containing the said quaternary phosphonium salt in the electrolyte solution composition used when synthesize | combining the said conductive polymer by electrolytic polymerization. Therefore, the quaternary phosphonium salt can be advantageously used in the electrolyte solution composition used for the dopant of the conductive polymer and the electrolytic polymerization reaction of the conductive polymer.
화학식 1로 표시되는 4급 포스포늄염으로 이루어지는 도전성 고분자용 도펀트가 도핑된 도전성 고분자는, 주쇄가 π 전자 공액계로 구성되어 있는 유기 고분자이고, 그의 예로서는 폴리피롤류, 폴리티오펜류, 폴리아닐린류, 폴리아세틸렌류, 폴리페닐렌류, 폴리페닐렌비닐렌류, 폴리아센류, 폴리티오펜비닐렌류 및 이들의 공중합체 등을 들 수 있다. 이들 도전성 고분자 중, 폴리피롤류, 폴리티오펜류 등의 5원 복소환을 구성 단위로 하는 것 및 폴리아닐린류가 전해 중합 반응의 반응성의 관점에서 바람직하다. 특히, 높은 내열성을 갖는 도전성 고분자인 폴리피롤류가 바람직하다.The conductive polymer doped with a dopant for a conductive polymer composed of a quaternary phosphonium salt represented by the formula (1) is an organic polymer whose main chain is composed of a π-electron conjugated system, and examples thereof include polypyrroles, polythiophenes, polyanilines, and poly Acetylene, polyphenylene, polyphenylene vinylene, polyacene, polythiophene vinylene, copolymers thereof, and the like. Among these conductive polymers, those having five-membered heterocycles such as polypyrroles and polythiophenes as structural units and polyanilines are preferred from the viewpoint of reactivity of the electrolytic polymerization reaction. In particular, polypyrroles which are conductive polymers having high heat resistance are preferable.
도전성 고분자에 있어서의 화학식 1로 표시되는 4급 포스포늄염의 함유량은, 인 원자로 환산하여 바람직하게는 1 내지 50,000 ppm, 더욱 바람직하게는 100 내지 20,000 ppm이다.The content of the quaternary phosphonium salt represented by the formula (1) in the conductive polymer is preferably 1 to 50,000 ppm, more preferably 100 to 20,000 ppm in terms of phosphorus atoms.
화학식 1로 표시되는 4급 포스포늄염이 도핑된 도전성 고분자를 제조하기 위한 바람직한 방법은 다음과 같다. 즉, 상기 도전성 고분자는 화학식 1로 표시되는 4급 포스포늄염의 존재하에 도전성 고분자의 원료인 중합성 단량체를 전해 중합함으로써 얻을 수 있다. 화학식 1로 표시되는 4급 포스포늄염은 전해 중합 반응에 있어서의 전해액에 함유된다. 이 전해액은 전해질이 매체에 용해되어 이루어지는 것인 바, 4급 포스포늄염은 (a) 매체로서 사용되거나 또는 (b) 전해질로서 사용된다. 4급 포스포늄염을 매체로서 사용하여도 또는 전해질로서 사용하여도, 상기 4급 포스포늄염은 목적으로 하는 도전성 고분자에 도핑되어, 전기 전도성 및 내열성 등이 우수한 도전성 고분자를 높은 반응 효율로 얻을 수 있다.Preferred methods for preparing the conductive polymer doped with the quaternary phosphonium salt represented by the formula (1) are as follows. That is, the conductive polymer can be obtained by electropolymerizing a polymerizable monomer which is a raw material of the conductive polymer in the presence of a quaternary phosphonium salt represented by the formula (1). The quaternary phosphonium salt represented by General formula (1) is contained in the electrolyte solution in electrolytic polymerization reaction. The electrolyte is obtained by dissolving an electrolyte in a medium. The quaternary phosphonium salt is used as (a) a medium or (b) as an electrolyte. Even if a quaternary phosphonium salt is used as a medium or as an electrolyte, the quaternary phosphonium salt can be doped into a target conductive polymer to obtain a conductive polymer having excellent electrical conductivity and heat resistance, etc. with high reaction efficiency. have.
우선, 상기 (a)의 실시 형태, 즉 화학식 1로 표시되는 4급 포스포늄염을 매체로서 사용하는 경우에 대하여 설명한다. 상기 4급 포스포늄염은 그 자체가 전기 전도성을 갖기 때문에, 이것에 지지 전해질을 특별히 첨가하지 않아도, 그 단독으로 전해 중합용 전해액으로서 사용할 수 있다. 특히, 종래 전해 중합에 사용되고 있는 용매나 지지 전해질을 상기 4급 포스포늄염에 첨가하는 것은 무방하다. 그러한 용매로서는, 아세토니트릴, 메탄올, 톨루엔, 크실렌, 프로필렌카르보네이트, 에틸렌카르보네이트, 에틸메틸카르보네이트 등을 들 수 있다. 지지 전해질로서는, 리튬염, 나트륨염, 칼륨염, 이미다졸륨염, 피라졸륨염, 4급 암모늄염, 4급 포스포늄염, 피리디늄염, 피롤리디늄염, 피페리디늄염, 술포늄염 등을 들 수 있다. 이들 용매나 지지 전해질을 사용하는 경우에는, 이들의 합계 함유량은 전해액 조성물 중에서의 중량％ 농도로, 바람직하게는 0.01 내지 50.0 ％, 더욱 바람직하게는 0.05 내지 10.0 ％, 한층 바람직하게는 0.1 내지 5.0 ％이다.First, the case of using the embodiment of said (a), ie, the quaternary phosphonium salt represented by General formula (1) as a medium, is demonstrated. Since the quaternary phosphonium salt itself has electrical conductivity, it can be used alone as an electrolytic polymerization electrolyte even without adding a supporting electrolyte thereto. In particular, a solvent or supporting electrolyte conventionally used for electrolytic polymerization may be added to the quaternary phosphonium salt. Examples of such a solvent include acetonitrile, methanol, toluene, xylene, propylene carbonate, ethylene carbonate, ethyl methyl carbonate, and the like. Examples of the supporting electrolyte include lithium salts, sodium salts, potassium salts, imidazolium salts, pyrazolium salts, quaternary ammonium salts, quaternary phosphonium salts, pyridinium salts, pyrrolidinium salts, piperidinium salts, and sulfonium salts. have. When using these solvents and a supporting electrolyte, these total content is the weight% concentration in electrolyte composition, Preferably it is 0.01-50.0%, More preferably, it is 0.05-10.0%, More preferably, it is 0.1-5.0% to be.
전해 중합에 사용되는 중합성 단량체의 양은, 전해액 조성물에 있어서의 상기 중합성 단량체의 농도가 0.01 내지 1.5 mol/L, 특히 0.05 내지 0.5 mol/L가 되도록 하는 양인 것이 바람직하다. 또한, 중합성 단량체는 목적으로 하는 도전성 고분자의 종류에 맞는 것을 사용하면 좋다.The amount of the polymerizable monomer used for the electrolytic polymerization is preferably such that the concentration of the polymerizable monomer in the electrolytic solution composition is 0.01 to 1.5 mol / L, in particular 0.05 to 0.5 mol / L. In addition, what is necessary is just to use the polymerizable monomer suitable for the kind of conductive polymer made into the objective.
전해 중합 반응은 작용극, 상대극, 참조극으로 구성되는 삼극식 전해셀로 행할 수 있다. 이에 의해서, 화학식 1로 표시되는 4급 포스포늄염이 도핑된 도전성 고분자가 작용극 상에 생성된다. 작용극 및 상대극은 모두 이들 자신이 반응하지 않고 안정적으로 전해 중합 반응을 진행시킬 수 있는 것이면 그 종류에 특별히 한정은 없다. 예를 들면 작용극 및 상대극으로서 백금, 금, 팔라듐과 같은 귀금속, 글래시 카본, 주석 첨가 산화인듐(ITO), 산화주석(SnO2), 불소 첨가 산화주석(FTO), 산화아연(ZnO) 등의 투명 산화물 등이 사용된다. 참조극으로서는, 예를 들면 은-염화은 전극, 포화 칼로멜 전극(SCE), 백금선, 금선, 은선 등을 들 수 있다.The electrolytic polymerization reaction can be performed with a tripolar electrolytic cell composed of a working electrode, a counter electrode and a reference electrode. As a result, a conductive polymer doped with a quaternary phosphonium salt represented by Formula 1 is formed on the working electrode. The working electrode and the counter electrode are not particularly limited as long as they can stably advance the electrolytic polymerization reaction without reacting themselves. For example, precious metals such as platinum, gold and palladium, glass carbon, tin indium oxide (ITO), tin oxide (SnO 2 ), fluorinated tin oxide (FTO) and zinc oxide (ZnO) Transparent oxides, such as these, are used. As a reference electrode, a silver-silver chloride electrode, a saturated calomel electrode (SCE), a platinum wire, a gold wire, a silver wire, etc. are mentioned, for example.
이와 같이 하여 구성된 삼극식 셀을 이용하는 전해 중합 반응은 공지된 정전위 전해법 또는 정전류 전해법으로 행할 수 있다. 정전위 전해법에 있어서는 작용극의 전위를 일정하게 유지하면서 전해 중합 반응을 진행시킨다. 정전위 전해법에서는, 반응의 진행에 따라서 전류 밀도가 감소되고, 반응 시간이 길어지는 경향이 있다. 한편, 정전류 전해법에 있어서는 전류 밀도를 일정하게 유지하여 전해 중합 반응을 진행시킨다. 정전류 전해법은 반응 시간의 제어가 용이하기 때문에 실용적이지만, 작용극의 전위가 반응 진행과 함께 상승하기 때문에, 셀 전압의 상승이나 부반응의 병발 등의 문제가 발생하는 경우가 있다. 화학식 1로 표시되는 4급 포스포늄염은, 높은 전기 전도성을 갖기 때문에 작용극의 전위 상승을 최소한으로 억제할 수 있으므로 정전류 전해법에 바람직하다.The electrolytic polymerization reaction using the tripolar cell configured in this way can be carried out by known electrostatic potential electrolysis or constant current electrolysis. In the electropotential electrolytic method, the electrolytic polymerization reaction is advanced while the potential of the working electrode is kept constant. In the electropotential electrolytic method, the current density decreases as the reaction proceeds, and the reaction time tends to be long. On the other hand, in the constant current electrolytic method, the current density is kept constant to advance the electrolytic polymerization reaction. The constant current electrolytic method is practical because it is easy to control the reaction time. However, since the potential of the working electrode rises with the progress of the reaction, problems such as an increase in the cell voltage and a side reaction may occur. The quaternary phosphonium salt represented by the general formula (1) is preferable for the constant current electrolytic method because it has high electrical conductivity and can suppress the potential rise of the working electrode to a minimum.
정전류 전해법에 있어서의 전류 밀도는 사용되는 중합성 단량체의 종류에도 의존하지만, 일반적으로 0.1 내지 5,000 mA/dm2, 특히 0.5 내지 50 mA/dm2로 하는 것이 바람직하다. 이 전해 중합에 의해서 중합성 단량체가 중합되어 도전성 고분자가 생성됨과 동시에, 4급 포스포늄염이 도전성 고분자 내에 취입된다(도핑된다). 이 취입은 중합 반응의 진행에 따라서 자발적으로 발생하는 것이며, 특별한 조작을 요구하는 것은 아니다.Although the current density in the constant current electrolysis method also depends on the kind of polymerizable monomer used, it is generally preferable to set it as 0.1-5,000 mA / dm <2> , especially 0.5-50 mA / dm <2> . By this electrolytic polymerization, a polymerizable monomer is polymerized to produce a conductive polymer, and a quaternary phosphonium salt is blown into the conductive polymer (doped). This blowing occurs spontaneously with the progress of the polymerization reaction and does not require special operation.
이상이 화학식 1로 표시되는 4급 포스포늄염을 매체로서 사용하는 경우의 설명인 바, 상기 (b)의 실시 형태, 즉 상기 4급 포스포늄염을 전해질로서 사용하는 경우에는, 상기 전해질의 매체로서, (a)의 실시 형태에 대하여 서술한 아세토니트릴 등을 사용할 수 있다. 상기 매체를 주된 구성 성분으로 하는 전해액 조성물에 있어서는, 4급 포스포늄염의 농도는 0.05 내지 2 mol/L, 특히 0.1 내지 1 mol/L로 하는 것이 바람직하다. 4급 포스포늄염을 전해질로서 사용하는 경우에는, 상기 4급 포스포늄염만을 전해질로서 사용할 수도 있고, 또는 상기 4급 포스포늄염에 부가하여 다른 염류를 전해질로서 사용할 수도 있다. 4급 포스포늄염과 병용되는 염류의 농도는, 전해액 조성물 중에서 0.05 내지 2 mol/L, 특히 0.1 내지 1 mol/L로 하는 것이 바람직하다. 염류로서는, 상술한 각종 지지 전해질을 사용할 수 있다. 또한, (b)의 실시 형태에 대하여 특별히 설명하지 않는 점에 대해서는, (a)의 실시 형태에 대하여 상술한 설명이 적절하게 적용된다.The above is the description of the case where the quaternary phosphonium salt represented by the formula (1) is used as a medium. In the case of using the embodiment of the above (b), that is, the quaternary phosphonium salt as the electrolyte, As acetonitrile etc. which were described about embodiment of (a) can be used. In the electrolyte composition containing the medium as the main constituent, the concentration of the quaternary phosphonium salt is preferably 0.05 to 2 mol / L, particularly 0.1 to 1 mol / L. When the quaternary phosphonium salt is used as the electrolyte, only the quaternary phosphonium salt may be used as the electrolyte, or other salts may be used as the electrolyte in addition to the quaternary phosphonium salt. The concentration of the salts used in combination with the quaternary phosphonium salt is preferably 0.05 to 2 mol / L, particularly 0.1 to 1 mol / L, in the electrolyte composition. As the salts, the various supporting electrolytes described above can be used. In addition, about the point which does not describe in particular about embodiment of (b), the above-mentioned description applies suitably to embodiment of (a).
이와 같이 하여, 화학식 1로 표시되는 4급 포스포늄염이 도핑된 도전성 고분자가 얻어진다. 이 도전성 고분자는, 4급 포스포늄염이 적절히 도핑되어 있는 것에서 기인하여, 전기 전도성 및 내열성 등이 우수한 것이다. 따라서, 이 도전성 고분자는, 예를 들면 전해 컨덴서, 전기 이중층 캐패시터 및 리튬 이차 전지와 같은 축전 디바이스나, 유기 EL, 유기 트랜지스터, 발광 다이오드, 유기 박막 태양 전지 및 색소 증감 태양 전지와 같은 광전 변환 디바이스의 등의 전기 화학 디바이스의 전극 재료나 전해질 재료에 바람직하게 사용할 수 있다.In this way, a conductive polymer doped with a quaternary phosphonium salt represented by the formula (1) is obtained. This conductive polymer is excellent in electrical conductivity, heat resistance, etc., because it is doped with quaternary phosphonium salt suitably. Therefore, this conductive polymer is, for example, of a power storage device such as an electrolytic capacitor, an electric double layer capacitor and a lithium secondary battery, or of a photoelectric conversion device such as an organic EL, an organic transistor, a light emitting diode, an organic thin film solar cell and a dye-sensitized solar cell. It can be used suitably for electrode materials and electrolyte materials of electrochemical devices, such as these.
<실시예><Examples>
이하에 실시예를 들어 본 발명을 구체적으로 설명한다. 특별히 언급하지 않는 한 「％」는 「중량％」를 의미한다.An Example is given to the following and this invention is concretely demonstrated to it. "%" Means "weight%" unless there is particular notice.
[합성예 1] 트리에틸벤질포스포늄비스(트리플루오로메틸술포닐)이미드의 합성 및 물성 측정Synthesis Example 1 Synthesis and Measurement of Physical Properties of Triethylbenzylphosphoniumbis (trifluoromethylsulfonyl) imide
(1) 합성(1) synthetic
트리에틸포스핀 25 ％ 톨루엔 용액(닛본 가가꾸 고교 가부시끼가이샤 제품명: 히시코린(등록 상표) P-2) 236 g(0.5 mol)에 염화벤질(도쿄 가세이 고교 가부시끼가이샤 시약) 64 g(0.5 mol)을 적하하고, 50 내지 60 ℃에서 6 시간 반응시켰다. 반응 종료 후에 헥산을 첨가하여 결정화시키고, 트리에틸벤질포스포늄클로라이드의 결정을 116 g 얻었다(수율 95 ％). 이 트리에틸벤질포스포늄클로라이드 73 g(0.3 mol)에 리튬비스(트리플루오로메틸술포닐)이미드(간토 가가꾸 가부시끼가이샤 시약) 86 g(0.3 mol)을 첨가하고, 수계에서 반응시켜 음이온 교환을 하였다. 이어서 실온에서 3 시간 교반하여 숙성시켰다. 교반 종료 후, 하층(생성물)을 분리하였다. 분리된 생성물에 대하여 순수 세정을 5회 행하고, 계속해서 헥산 세정을 5회 행하였다. 세정 종료 후, 100 ℃, 진공도 0.5 kPa에서 5 시간 진공 건조시켰다. 이와 같이 하여 얻어진 생성물이 목적물인 것에 대한 확인을 1H-NMR, 13C-NMR, 19F-NMR로 행하였다. 질산은을 사용한 전위차 적정법에 의해, 얻어진 생성물 중의 잔류 할로겐이 50 ppm 이하인 것을 확인하였다. 생성물(무색 투명 액체)의 수량은 132 g(수율 90 ％)이고, 31P-NMR로부터 순도 98 ％ 이상인 것을 확인하였다. NMR의 동정 데이터는 이하와 같았다.236 g (0.5 mol) of triethylphosphine 25% toluene solution (Nippon Kagaku Kogyo Co., Ltd. product name: Hishkorin (registered trademark) P-2) 64 g (0.5 g) of benzyl chloride (Tokyo Kasei Kogyo Co., Ltd. reagent) mol) was added dropwise and reacted at 50 to 60 ° C for 6 hours. Hexane was added and crystallized after completion | finish of reaction, and 116g of crystals of triethylbenzylphosphonium chloride were obtained (yield 95%). To 73 g (0.3 mol) of this triethylbenzylphosphonium chloride, 86 g (0.3 mol) of lithium bis (trifluoromethylsulfonyl) imide (Kanto Chemical Co., Ltd. reagent) was added and reacted in an aqueous system to react with anion. Exchange was made. Then, the mixture was stirred at room temperature for 3 hours to mature. After stirring was complete, the lower layer (product) was separated. The separated product was washed five times with pure water, followed by hexane washing five times. After washing, vacuum drying was performed at 100 ° C. and vacuum degree of 0.5 kPa for 5 hours. Thus, the confirmation that the obtained product was a target object was performed by 1 H-NMR, 13 C-NMR, and 19 F-NMR. The potentiometric titration method using silver nitrate confirmed that the residual halogen in the obtained product was 50 ppm or less. The yield of the product (colorless transparent liquid) was 132 g (yield 90%), and it confirmed that it was 98% or more of purity from 31 P-NMR. The identification data of NMR were as follows.
(2) 물성 측정(2) property measurement
상기 (1)에서 얻어진 생성물의 융점을 시차 주사 열량 분석(세이코 인스트루멘탈 가부시끼가이샤, DSC6200)에 의해 측정하였다. 또한, 전기 전도도를 교류 2극식 셀을 이용하여 측정하였다 (Ivium Technologies, Compact Stat). 또한, 전기 전도도는 측정 조건에 의해 ±5 ％ 정도의 오차가 생겼다. 또한, 열 분해 온도(10 ％ 중량 감소)를 열 중량 분석 장치(세이코 인스트루멘탈 가부시끼가이샤, TG/DTA6300)를 이용하여 측정하였다. 측정 결과를 이하의 표 1에 나타내었다. 이상의 측정은 전부 건조 질소 분위기하에서 행하였다.Melting | fusing point of the product obtained by said (1) was measured by differential scanning calorimetry (Seiko Instruments Co., Ltd., DSC6200). In addition, electrical conductivity was measured using an alternating dipolar cell (Ivium Technologies, Compact Stat). Moreover, the electrical conductivity produced the error of about +/- 5% by measurement conditions. In addition, the thermal decomposition temperature (10% weight reduction) was measured using the thermogravimetric analyzer (Seiko Instruments Co., Ltd., TG / DTA6300). The measurement results are shown in Table 1 below. All the above measurements were performed in dry nitrogen atmosphere.
[합성예 2] 트리-n-부틸벤질포스포늄비스(트리플루오로메틸술포닐)이미드의 합성 및 물성 측정Synthesis Example 2 Synthesis and Physical Properties of Tri-n-Butylbenzylphosphoniumbis (trifluoromethylsulfonyl) imide
(1) 합성(1) synthetic
트리-n-부틸포스핀(닛본 가가꾸 고교 가부시끼가이샤 제품명: 히시코린(등록상표) P-4) 101 g(0.5 mol)에 염화벤질(도쿄 가세이 고교 가부시끼가이샤 시약) 64 g(0.5 mol)을 적하하고, 50 내지 60 ℃에서 6 시간 반응시켰다. 반응 종료 후에 헥산을 첨가하여 결정화시키고, 트리-n-부틸벤질포스포늄클로라이드의 결정을 156 g 얻었다(수율 95 ％). 이 트리-n-부틸벤질포스포늄클로라이드 99 g(0.3 mol)에 리튬비스(트리플루오로메틸술포닐)이미드(간토 가가꾸 가부시끼가이샤 시약) 86 g(0.3 mol)을 첨가하고, 수계에서 반응시켜 음이온 교환을 하였다. 이어서 디클로로메탄 100 ml를 첨가하고, 실온에서 3 시간 교반하여 숙성시켰다. 교반 종료 후, 하층(생성물)을 분리하였다. 분리된 생성물에 대하여 순수 세정을 5회 행하고, 계속해서 헥산 세정을 5회 행하였다. 세정 종료 후에 디클로로메탄을 감압 증류 제거하고, 잔존 성분을 100 ℃, 진공도 0.5 kPa에서 5 시간 진공 건조시켰다. 이와 같이 하여 얻어진 생성물이 목적물인 것에 대한 확인을, 1H-NMR, 13C-NMR, 19F-NMR로 행하였다. 질산은을 사용한 전위차 적정법에 의해, 얻어진 생성물 중의 잔류 할로겐이 50 ppm 이하인 것을 확인하였다. 생성물(백색 고체)의 수량은 160 g(수율 93 ％)이고, 31P-NMR로부터 순도 98 ％ 이상인 것을 확인하였다. NMR의 동정 데이터는 이하와 같았다.To tri-n-butyl phosphine (Nipbon Chemical Co., Ltd. product name: Hishicholine (trademark) P-4) 101 g (0.5 mol) 64 g (0.5 mol) of benzyl chloride (Tokyo Kasei Kogyo Co., Ltd. reagent) ) Was added dropwise and reacted at 50 to 60 ° C for 6 hours. Hexane was added and crystallized after completion | finish of reaction, and 156g of crystals of tri-n-butylbenzylphosphonium chloride were obtained (yield 95%). To 99 g (0.3 mol) of this tri-n-butylbenzylphosphonium chloride, 86 g (0.3 mol) of lithium bis (trifluoromethylsulfonyl) imide (Kanto Chemical Co., Ltd. reagent) was added, The reaction was carried out for anion exchange. Then 100 ml of dichloromethane were added and aged by stirring at room temperature for 3 hours. After stirring was complete, the lower layer (product) was separated. The separated product was washed five times with pure water, followed by hexane washing five times. Dichloromethane was distilled off under reduced pressure after completion | finish of washing | cleaning, and the remaining component was vacuum-dried at 100 degreeC and vacuum degree of 0.5 kPa for 5 hours. Thus, the confirmation that the obtained product was a target object was performed by 1 H-NMR, 13 C-NMR, and 19 F-NMR. The potentiometric titration method using silver nitrate confirmed that the residual halogen in the obtained product was 50 ppm or less. The yield of the product (white solid) was 160 g (yield 93%), and it confirmed that it was 98% or more of purity from 31 P-NMR. The identification data of NMR were as follows.
(2) 물성 측정(2) property measurement
상기 (1)에서 얻어진 생성물의 융점, 전기 전도도 및 열 분해 온도를 합성예 1과 동일하게 측정하였다. 측정 결과를 이하의 표 1에 나타내었다.Melting point, electrical conductivity and thermal decomposition temperature of the product obtained in the above (1) were measured in the same manner as in Synthesis example 1. The measurement results are shown in Table 1 below.
[합성예 3]Synthesis Example 3
트리-n-옥틸벤질포스포늄비스(트리플루오로메틸술포닐)이미드의 합성 및 물성 측정Synthesis and Properties of Tri-n-Octylbenzylphosphoniumbis (trifluoromethylsulfonyl) imide
(1) 합성(1) synthetic
트리-n-옥틸포스핀(닛본 가가꾸 고교 가부시끼가이샤 제품명: 히시코린(등록상표) P-8) 185 g(0.5 mol)에 염화벤질(도쿄 가세이 고교 가부시끼가이샤 시약) 64 g(0.5 mol)을 적하하고, 50 내지 60 ℃에서 6 시간 반응시켰다. 얻어진 조(粗) 트리-n-옥틸벤질포스포늄클로라이드에 리튬비스(트리플루오로메틸술포닐)이미드(간토 가가꾸 가부시끼가이샤 시약) 151 g(0.5 mol)을 첨가하고, 수계에서 반응시켜 음이온 교환을 하였다. 이어서 헥산 500 ml를 첨가하고, 실온에서 3 시간 교반하여 숙성시켰다. 교반 종료 후, 상층(생성물)을 분리하였다. 분리된 생성물에 대하여 순수 세정을 5회 행하였다. 세정 종료 후에 헥산을 감압 증류 제거하고, 잔존 성분을 100 ℃, 진공도 0.5 kPa에서 5 시간 진공 건조시켰다. 이와 같이 하여 얻어진 생성물이 목적물인 것에 대한 확인을, 1H-NMR, 13C-NMR, 19F-NMR로 행하였다. 질산은을 사용한 전위차 적정법에 의해, 얻어진 생성물 중의 잔류 할로겐이 50 ppm 이하인 것을 확인하였다. 생성물(무색 투명 액체)의 수량은 352 g(수율 95％)이고, 31P-NMR로부터 순도 98 ％ 이상인 것을 확인하였다.To 185 g (0.5 mol) of tri-n-octyl phosphine (Nippon Chemical Co., Ltd. product name: Hishkorin (registered trademark) P-8) benzyl chloride (Tokyo Kasei Kogyo Co., Ltd. reagent) 64 g (0.5 mol) ) Was added dropwise and reacted at 50 to 60 ° C for 6 hours. 151 g (0.5 mol) of lithium bis (trifluoromethylsulfonyl) imide (Kanto Chemical Co., Ltd. reagent) was added to the obtained tri-n-octylbenzylphosphonium chloride, and it was made to react in water system. Anion exchange was performed. 500 ml of hexane was then added and aged by stirring at room temperature for 3 hours. After stirring was complete, the upper layer (product) was separated. The pure product was washed five times with respect to the separated product. Hexane was distilled off under reduced pressure after completion | finish of washing | cleaning, and the remaining component was vacuum-dried at 100 degreeC and vacuum degree of 0.5 kPa for 5 hours. Thus, the confirmation that the obtained product was a target object was performed by 1 H-NMR, 13 C-NMR, and 19 F-NMR. The potentiometric titration method using silver nitrate confirmed that the residual halogen in the obtained product was 50 ppm or less. The yield of the product (colorless transparent liquid) was 352 g (yield 95%), and it confirmed that it was 98% or more of purity from 31 P-NMR.
(2) 물성 측정(2) property measurement
상기 (1)에서 얻어진 생성물의 융점, 전기 전도도 및 열 분해 온도를 합성예 1과 동일하게 측정하였다. 측정 결과를 이하의 표 1에 나타내었다.Melting point, electrical conductivity and thermal decomposition temperature of the product obtained in the above (1) were measured in the same manner as in Synthesis example 1. The measurement results are shown in Table 1 below.
[합성예 4(비교)]Synthesis Example 4 (Comparative)
트리에틸벤질암모늄비스(트리플루오로메틸술포닐)이미드의 합성 및 물성 측정Synthesis and Properties of Triethylbenzylammoniumbis (trifluoromethylsulfonyl) imide
(1) 합성(1) synthetic
트리에틸벤질암모늄클로라이드(도쿄 가세이 고교 가부시끼가이샤 시약) 68 g(0.3 mol)에 리튬비스(트리플루오로메틸술포닐)이미드(간토 가가꾸 가부시끼가이샤 시약) 86 g(0.3 mol)을 첨가하여 수계에서 반응시켰다. 이어서 디클로로메탄 100 ml를 첨가하고, 실온에서 3 시간 교반하여 숙성시켰다. 교반 종료 후, 하층(생성물)을 분리하였다. 분리한 생성물에 대하여 순수 세정을 5회 행하고, 계속해서 헥산 세정을 5회 행하였다. 세정 종료 후에 디클로로메탄을 감압 증류 제거하고, 잔존 성분을 100 ℃, 진공도 0.5 kPa에서 5 시간 진공 건조시켰다. 이와 같이 하여 얻어진 생성물이 목적물인 것에 대한 확인을, 1H-NMR, 13C-NMR, 19F-NMR로 행하였다. 질산은을 사용한 전위차 적정법에 의해, 얻어진 생성물 중의 잔류 할로겐이 50 ppm 이하인 것을 확인하였다. 생성물(백색 고체)의 수량은 135 g(수율 95 ％)이고, 31P-NMR로부터 순도 98 ％ 이상인 것을 확인하였다.To 68 g (0.3 mol) of triethylbenzyl ammonium chloride (Tokyo Kasei Kogyo Co., Ltd. reagent) add 86 g (0.3 mol) of lithium bis (trifluoromethylsulfonyl) imide (Kanto Chemical Co., Ltd.) The reaction was carried out in an aqueous system. Then 100 ml of dichloromethane were added and aged by stirring at room temperature for 3 hours. After stirring was complete, the lower layer (product) was separated. The separated product was washed five times with pure water, followed by hexane washing five times. Dichloromethane was distilled off under reduced pressure after completion | finish of washing | cleaning, and the remaining component was vacuum-dried at 100 degreeC and vacuum degree of 0.5 kPa for 5 hours. Thus, the confirmation that the obtained product was a target object was performed by 1 H-NMR, 13 C-NMR, and 19 F-NMR. The potentiometric titration method using silver nitrate confirmed that the residual halogen in the obtained product was 50 ppm or less. The yield of the product (white solid) was 135 g (yield 95%), and it confirmed that it was 98% or more of purity from 31 P-NMR.
(2) 물성 측정(2) property measurement
상기 (1)에서 얻어진 생성물의 융점, 전기 전도도 및 열 분해 온도를 합성예 1과 동일하게 측정하였다. 측정 결과를 이하의 표 1에 나타내었다.Melting point, electrical conductivity and thermal decomposition temperature of the product obtained in the above (1) were measured in the same manner as in Synthesis example 1. The measurement results are shown in Table 1 below.
[합성예 5(비교)]Synthesis Example 5 (Comparative)
트리-n-부틸벤질암모늄비스(트리플루오로메틸술포닐)이미드의 합성 및 물성 측정Synthesis and Properties of Tri-n-Butylbenzylammoniumbis (trifluoromethylsulfonyl) imide
(1) 합성(1) synthetic
트리-n-부틸벤질암모늄클로라이드(도쿄 가세이 고교 가부시끼가이샤 시약) 94 g(0.3 mol)에 리튬비스(트리플루오로메틸술포닐)이미드(간토 가가꾸 가부시끼가이샤 시약) 86 g(0.3 mol)을 첨가하여 수계에서 반응시켰다. 이어서 디클로로메탄 100 ml를 첨가하고, 실온에서 3 시간 교반하여 숙성시켰다. 교반 종료 후, 하층(생성물)을 분리하였다. 분리된 생성물에 대하여 순수 세정을 5회 행하고, 계속해서 헥산 세정을 5회 행하였다. 세정 종료 후에 디클로로메탄을 감압 증류 제거하고, 잔존 성분을 100 ℃, 진공도 0.5 kPa에서 5 시간 진공 건조시켰다. 이와 같이 하여 얻어진 생성물이 목적물인 것에 대한 확인을, 1H-NMR, 13C-NMR, 19F-NMR로 행하였다. 질산은을 사용한 전위차 적정법에 의해, 얻어진 생성물 중의 잔류 할로겐이 50 ppm 이하인 것을 확인하였다. 생성물(백색 고체)의 수량은 154 g(수율 92 ％)이고, 31P-NMR로부터 순도 98 ％ 이상인 것을 확인하였다.94 g (0.3 mol) of tri-n-butylbenzyl ammonium chloride (Tokyo Kasei Kogyo Co., Ltd. reagent) 86 g (0.3 mol) of lithium bis (trifluoromethylsulfonyl) imide (Kanto Chemical Co., Ltd.) ) Was added and reacted in water. Then 100 ml of dichloromethane were added and aged by stirring at room temperature for 3 hours. After stirring was complete, the lower layer (product) was separated. The separated product was washed five times with pure water, followed by hexane washing five times. Dichloromethane was distilled off under reduced pressure after completion | finish of washing | cleaning, and the remaining component was vacuum-dried at 100 degreeC and vacuum degree of 0.5 kPa for 5 hours. Thus, the confirmation that the obtained product was a target object was performed by 1 H-NMR, 13 C-NMR, and 19 F-NMR. The potentiometric titration method using silver nitrate confirmed that the residual halogen in the obtained product was 50 ppm or less. The yield of the product (white solid) was 154 g (yield 92%), and it confirmed that it was 98% or more of purity from 31 P-NMR.
(2) 물성 측정(2) property measurement
상기 (1)에서 얻어진 생성물의 융점, 전기 전도도 및 열 분해 온도를 합성예 1과 동일하게 측정하였다. 측정 결과를 이하의 표 1에 나타내었다. Melting point, electrical conductivity and thermal decomposition temperature of the product obtained in the above (1) were measured in the same manner as in Synthesis example 1. The measurement results are shown in Table 1 below.
[합성예 6(비교)]Synthesis Example 6 (Comparative)
트리헥실테트라데실포스포늄비스(트리플루오로메틸술포닐)이미드의 물성 측정Measurement of physical properties of trihexyl tetradecyl phosphonium bis (trifluoromethylsulfonyl) imide
트리헥실테트라데실포스포늄비스(트리플루오로메틸술포닐)이미드(간토 가가꾸 가부시끼가이샤 시약, 융점 및 열 분해 온도는 표 1에 기재된 바와 같음) 전기 전도도를 합성예 1과 동일하게 측정하였다. 측정 결과를 이하의 표 1에 나타내었다.Trihexyl tetradecylphosphonium bis (trifluoromethylsulfonyl) imide (Kanto Chemical Co., Ltd. reagent, melting point and thermal decomposition temperature are as shown in Table 1) electrical conductivity was measured in the same manner as in Synthesis Example 1 . The measurement results are shown in Table 1 below.
표 1에 나타내는 결과로부터 분명한 바와 같이, 합성예 1 및 2의 4급 포스포늄염 이온 액체는, 대응하는 4급 암모늄염 이온 액체(각각 합성예 4 및 5)에 비교하여 저융점이며 고전기 전도성을 나타내고, 또한 열 분해 온도도 높으며 내열성이 우수한 것을 알 수 있었다. 합성예 3의 4급 포스포늄염 이온 액체도 저융점이며 고전기 전도성을 나타내고, 또한 열 분해 온도도 높아서 내열성이 우수한 것을 알 수 있었다. 치환기가 전부 알킬기인 4급 포스포늄염 이온 액체(합성예 6)는 저융점이며 실온(25 ℃)에서도 전기 전도성을 나타내지만, 그의 전기 전도성은 낮으며 내열성도 열악한 것을 알 수 있었다.As is apparent from the results shown in Table 1, the quaternary phosphonium salt ionic liquids of Synthesis Examples 1 and 2 exhibit low melting point and high electric conductivity compared to the corresponding quaternary ammonium salt ionic liquids (Synthesis Examples 4 and 5, respectively). In addition, it was also found that the thermal decomposition temperature was high and the heat resistance was excellent. It was found that the quaternary phosphonium salt ionic liquid of Synthesis Example 3 also had a low melting point, exhibited high electric conductivity, and also had high thermal decomposition temperature and excellent heat resistance. The quaternary phosphonium salt ionic liquid (Synthesis Example 6) in which all of the substituents are alkyl groups has a low melting point and exhibits electrical conductivity even at room temperature (25 ° C.), but its electrical conductivity is low and the heat resistance is also poor.
[실시예 1 내지 3및 비교예 1 내지 2][Examples 1-3 and Comparative Examples 1-2]
합성예 1, 3, 4에서 얻어진 이온 액체를 사용하여, 이하의 절차로 전해액 조성물을 제조하였다. 이 전해액 조성물을 사용하여 중합성 단량체의 전해 중합 반응을 행하고, 도전성 고분자를 얻었다. 또한, 얻어진 도전성 고분자의 내열성 평가를 행하였다. 또한, 실시예 1 및 비교예 1에서는, 얻어진 도전성 고분자의 인 농도 측정도 행하였다. 그 결과를 표 2에 나타내었다.Using the ionic liquids obtained in Synthesis Examples 1, 3, and 4, an electrolyte composition was prepared by the following procedure. The electrolytic polymerization reaction of the polymerizable monomer was performed using this electrolyte solution composition, and the conductive polymer was obtained. Moreover, heat resistance evaluation of the obtained conductive polymer was performed. In Example 1 and Comparative Example 1, phosphorus concentration measurement of the obtained conductive polymer was also performed. The results are shown in Table 2.
전해액 조성물은, 표 2에 나타내는 이온 액체 10 ml에 0.3 mol/l의 농도가 되도록 중합성 단량체(피롤 또는 티오펜)를 용해시켜 제조하였다. 전해 중합 반응에는, 인듐주석 산화물 전극을 작용극, 백금판을 상대극, 은-염화은 전극(염교(鹽橋): 과염소산테트라에틸암모늄아세토니트릴 용액)을 참조극으로 하는 삼전극식 셀을 이용하였다. 이들 삼극식 셀 중에 전해액 조성물을 주입하고, 전해 전원으로서 포텐쇼갈바노스탯(호꾸또 덴꼬 가부시끼가이샤, HABF5001)을 이용하여 전해 산화 중합 반응을 행하고, 작용극 상에 도전성 고분자를 생성시켰다. 통전 조건으로서는 전류 밀도를 20 mA/dm2로 하는 정전류 전해법을 채용하고, 전해 반응 중의 작용극의 전위를 관측하였다. 모든 측정은 25 ℃ 상압의 조건에서 행하였다. 작용극 상에 생성된 도전성 고분자를 분취하여 건조시킨 후, 마이크로열 중량 측정 장치(가부시끼가이샤 시마즈 세이사꾸쇼, TGA-50/50H)를 이용하여 도전성 고분자의 열 분해 온도(10 ％ 중량 감소)를 측정하였다. 승온 속도는 5.0 ℃/분, 사용 가스는 질소, 가스 유량은 20 ml/ml, 사용 셀은 백금으로 하였다. 또한, 에너지 분산형 원소 분석 기능 장착 주사형 전자 현미경(니혼 덴시 가부시끼가이샤, JSM-6400)을 이용한 원소 분석에 의해서 도전성 고분자 중의 인의 농도를 측정하였다.The electrolyte composition was prepared by dissolving a polymerizable monomer (pyrrole or thiophene) in 10 ml of the ionic liquid shown in Table 2 so as to have a concentration of 0.3 mol / l. In the electrolytic polymerization reaction, a trielectrode cell was used in which an indium tin oxide electrode was used as a reference electrode, a platinum plate was a counter electrode, and a silver-silver chloride electrode (a salt bridge: tetraethylammonium perchlorate solution) was used as a reference electrode. . The electrolytic solution composition was inject | poured into these tripolar cells, the electrolytic oxidation polymerization reaction was performed using the pot tenshogalbanostat (HAKUF5001) as an electrolytic power supply, and the electroconductive polymer was produced | generated on the working electrode. As the energization condition, a constant current electrolysis method with a current density of 20 mA / dm 2 was employed, and the potential of the working electrode during the electrolytic reaction was observed. All measurements were performed on 25 degreeC atmospheric pressure conditions. After the conductive polymer produced on the working electrode was aliquoted and dried, a thermal decomposition temperature (10% weight reduction) of the conductive polymer was obtained by using a microthermal gravimetric apparatus (TGA-50 / 50H, Shimadzu Corporation). Was measured. The temperature increase rate was 5.0 degree-C / min, the gas used was nitrogen, the gas flow volume was 20 ml / ml, and the cell used was platinum. In addition, the concentration of phosphorus in the conductive polymer was measured by elemental analysis using a scanning electron microscope (Nihon Denshi Co., Ltd., JSM-6400) equipped with an energy dispersive element analysis function.
표 2에 나타내는 결과로부터 분명한 바와 같이, 각 실시예에서 얻어진 도전성 고분자(본 발명품)은, 비교예에서 얻어진 도전성 고분자보다 열 분해 온도가 높고, 내열성이 우수한 것을 알았다. 또한, 전기 전도성도 높은 것을 알았다. 또한, 각 실시예에 있어서 행한 전해 중합 반응에서는, 시간의 경과에 의한 작용극의 전위 상승이 관찰되지 않기 때문에, 전압 부가가 적고, 효율적으로 전해 중합 반응이 진행되고 있음을 알았다. 이에 대하여, 비교예에 있어서는 전해 중합 반응의 작용극 전위가 시간의 경과에 따라 상승하고, 전압 부가가 높아지며, 최종적으로는 반응이 진행되지 않게 되었다.As is clear from the results shown in Table 2, it was found that the conductive polymer (the present invention) obtained in each example had a higher thermal decomposition temperature and superior heat resistance than the conductive polymer obtained in the comparative example. Moreover, it turned out that electrical conductivity is also high. Moreover, in the electrolytic polymerization reaction performed in each Example, since the potential rise of the working electrode was not observed over time, it turned out that the voltage addition is small and the electrolytic polymerization reaction advances efficiently. On the other hand, in the comparative example, the working electrode potential of the electrolytic polymerization reaction increased with time, the voltage addition became high, and finally, the reaction did not proceed.
Claims (12)
<화학식 1>
(식 중, R1, R2 및 R3은 탄소수 1 내지 8의 알킬기를 나타내며, 서로 동일하거나 상이할 수도 있고, R1과 R2가 결합하여 환을 형성할 수도 있고, n은 메틸렌기의 수를 나타내며, n=1 내지 6이고, R4 내지 R8은 수소 원자 또는 치환기를 나타내며, 서로 동일하거나 상이할 수도 있고, X-는 음이온을 나타낸다.)A dopant for a conductive polymer, comprising a quaternary phosphonium salt represented by the following formula (1).
<Formula 1>
(In formula, R <1> , R <2> and R <3> represent a C1-C8 alkyl group, and may mutually be same or different, R <1> and R <2> may combine and form a ring, n is a methylene group Number, n = 1 to 6, R 4 to R 8 represent a hydrogen atom or a substituent, may be the same or different from each other, and X − represents an anion.)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JPJP-P-2009-007763 | 2009-01-16 | ||
| JP2009007763A JP2010163396A (en) | 2009-01-16 | 2009-01-16 | Dopant for electroconductive polymer, and electroconductive polymer using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20100084479A true KR20100084479A (en) | 2010-07-26 |
Family
ID=42579868
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020100003680A KR20100084479A (en) | 2009-01-16 | 2010-01-15 | Dopant for conductive polymer and conductive polymer using the same |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2010163396A (en) |
| KR (1) | KR20100084479A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110039467A1 (en) | 2009-08-11 | 2011-02-17 | H&C Chemical | Ionic liquid flame retardants |
-
2009
- 2009-01-16 JP JP2009007763A patent/JP2010163396A/en active Pending
-
2010
- 2010-01-15 KR KR1020100003680A patent/KR20100084479A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| JP2010163396A (en) | 2010-07-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7432340B2 (en) | Fluorinated alkyl substituted-thieno[3,4-]thiophene monomers and polymers therefrom | |
| US7572879B2 (en) | Fluorinated alkyl substituted-thieno[3,4-b]thiophene monomers and polymers therefrom | |
| US7071289B2 (en) | Polymers comprising thieno [3,4-b]thiophene and methods of making and using the same | |
| KR100736194B1 (en) | Pentafluorosulfanyl-substituted thienothiophene monomers and conducting polymers | |
| KR101828731B1 (en) | New tetracyano-anthraquino-dimethane polymers and use thereof | |
| CN1760196A (en) | Substituted thienothiophene monomers and conducting polymers | |
| US10957907B2 (en) | Use of certain polymers as a charge store | |
| US20120208978A1 (en) | Novel heterocyclic aromatic compound and polymer | |
| US5405937A (en) | Polymers derived from fluorinated thiophenes, and conductive polymers derived therefrom | |
| JP2005317528A (en) | Conductive substrate formed from conductive polyaniline dispersion, photoelectric transfer element using it, and dye-sensitized solar cell | |
| CN107531894A (en) | Purposes of some polymer as charge accumulator | |
| KR20090020527A (en) | Electrolyte composition for photoelectric conversion device, and photoelectric conversion device using the same | |
| KR20130135858A (en) | Ionic gelling agent, gel, process for production of gel, and crosslinking agent | |
| US6617462B1 (en) | Bithienylnaphthalene-and bis(3,4-ethylenedioxythienyl)naphthalene-based monomers and polymers | |
| US6291621B1 (en) | Bithienylnaphthalene-based monomers and polymers | |
| KR20100084479A (en) | Dopant for conductive polymer and conductive polymer using the same | |
| US8168671B2 (en) | Synthesis of thieno[3,4-b]thiophene, thieno[3,4-b]furan, related compounds and their derivatives and use thereof | |
| JP4500523B2 (en) | Onium salt | |
| US6814888B2 (en) | Dopant agent and electroconductive polymer material comprising the same | |
| US7094365B2 (en) | Pentafluorosulfanyl-substituted thienothiophene monomers and conducting polymers | |
| Qian et al. | The influence of pendent anions on electrochemical and electrochromic properties of thiophene-triphenylamine-based polymeric ionic liquids | |
| JPH0574467A (en) | Macromolecular solid electrolyte | |
| JP6303263B2 (en) | Method for producing acidic group-substituted conductive polymer | |
| US5162470A (en) | Polymers with electrical and nonlinear optical properties | |
| KR100655656B1 (en) | Polythiophene Derivatives Having Improved Electrical Properties and Process for Preparing Thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WITN | Withdrawal due to no request for examination |