CN1018874B - Polymer having isothianaphthene structure and electrochromic display - Google Patents
Polymer having isothianaphthene structure and electrochromic displayInfo
- Publication number
- CN1018874B CN1018874B CN90100116A CN90100116A CN1018874B CN 1018874 B CN1018874 B CN 1018874B CN 90100116 A CN90100116 A CN 90100116A CN 90100116 A CN90100116 A CN 90100116A CN 1018874 B CN1018874 B CN 1018874B
- Authority
- CN
- China
- Prior art keywords
- isothianaphthene
- polymer
- poly
- polymerization
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 77
- LYTMVABTDYMBQK-UHFFFAOYSA-N 2-benzothiophene Chemical group C1=CC=CC2=CSC=C21 LYTMVABTDYMBQK-UHFFFAOYSA-N 0.000 title abstract description 67
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 48
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 11
- 239000011593 sulfur Substances 0.000 claims abstract description 10
- 239000011244 liquid electrolyte Substances 0.000 claims abstract description 8
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 4
- 239000011669 selenium Chemical group 0.000 claims abstract description 4
- 229910052714 tellurium Chemical group 0.000 claims abstract description 4
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical group [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 4
- -1 methoxyl group Chemical group 0.000 claims description 26
- 230000003647 oxidation Effects 0.000 claims description 19
- 238000007254 oxidation reaction Methods 0.000 claims description 19
- 150000001450 anions Chemical class 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 14
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 9
- 239000005864 Sulphur Substances 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 230000002441 reversible effect Effects 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- 239000000243 solution Substances 0.000 description 31
- 229920000000 Poly(isothianaphthene) Polymers 0.000 description 30
- 239000000463 material Substances 0.000 description 21
- 238000002360 preparation method Methods 0.000 description 20
- 239000002904 solvent Substances 0.000 description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 20
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 17
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 16
- 239000003792 electrolyte Substances 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 14
- 239000003115 supporting electrolyte Substances 0.000 description 14
- 238000002329 infrared spectrum Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 11
- 238000001228 spectrum Methods 0.000 description 11
- 239000002585 base Substances 0.000 description 10
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 9
- 150000001721 carbon Chemical group 0.000 description 9
- 239000011521 glass Substances 0.000 description 9
- 229910052697 platinum Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000010538 cationic polymerization reaction Methods 0.000 description 8
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 8
- 229920000123 polythiophene Polymers 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 229930192474 thiophene Natural products 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 229920001197 polyacetylene Polymers 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 229940075397 calomel Drugs 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920006254 polymer film Polymers 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229920001940 conductive polymer Polymers 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000000269 nucleophilic effect Effects 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000002322 conducting polymer Substances 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 3
- 229920000379 polypropylene carbonate Polymers 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 3
- 238000007738 vacuum evaporation Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 description 2
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 238000012412 chemical coupling Methods 0.000 description 2
- 239000002772 conduction electron Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- WACQKHWOTAEEFS-UHFFFAOYSA-N cyclohexane;ethyl acetate Chemical compound CCOC(C)=O.C1CCCCC1 WACQKHWOTAEEFS-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 2
- QNFCBQVDIQELAS-UHFFFAOYSA-N quinoline;cyanide Chemical class N#[C-].N1=CC=CC2=CC=CC=C21 QNFCBQVDIQELAS-UHFFFAOYSA-N 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N thianaphthalene Natural products C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical group C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- VQYOBXIWVQFHNU-UHFFFAOYSA-N 3-ethenyl-2-thiophen-2-ylthiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1C=C VQYOBXIWVQFHNU-UHFFFAOYSA-N 0.000 description 1
- PMZBHPUNQNKBOA-UHFFFAOYSA-N 5-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=CC(C(O)=O)=CC(C(O)=O)=C1 PMZBHPUNQNKBOA-UHFFFAOYSA-N 0.000 description 1
- HAIFXFCUOPTEIQ-UHFFFAOYSA-N 8-bromo-5,5-dioxodibenzothiophen-2-ol Chemical class BrC1=CC=C2S(=O)(=O)C3=CC=C(O)C=C3C2=C1 HAIFXFCUOPTEIQ-UHFFFAOYSA-N 0.000 description 1
- 229910016467 AlCl 4 Inorganic materials 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- YTMGLVBZNZLLIF-UHFFFAOYSA-N C(C)P(O)(O)O Chemical compound C(C)P(O)(O)O YTMGLVBZNZLLIF-UHFFFAOYSA-N 0.000 description 1
- HMOFGIBUFYFSJH-UHFFFAOYSA-N C1=CC=C2C=CC=C12.[S] Chemical compound C1=CC=C2C=CC=C12.[S] HMOFGIBUFYFSJH-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- CZGGKXNYNPJFAX-UHFFFAOYSA-N Dimethyldithiophosphate Chemical compound COP(S)(=S)OC CZGGKXNYNPJFAX-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- AVQZBDBKHBIDJA-UHFFFAOYSA-M [F-].[Li+].B(O)(O)O Chemical compound [F-].[Li+].B(O)(O)O AVQZBDBKHBIDJA-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical class C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- GATNOFPXSDHULC-UHFFFAOYSA-N ethylphosphonic acid Chemical compound CCP(O)(O)=O GATNOFPXSDHULC-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000009661 fatigue test Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000002650 habitual effect Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- ARRNBPCNZJXHRJ-UHFFFAOYSA-M hydron;tetrabutylazanium;phosphate Chemical compound OP(O)([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC ARRNBPCNZJXHRJ-UHFFFAOYSA-M 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- GRPQBOKWXNIQMF-UHFFFAOYSA-N indium(3+) oxygen(2-) tin(4+) Chemical compound [Sn+4].[O-2].[In+3] GRPQBOKWXNIQMF-UHFFFAOYSA-N 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- NALMPLUMOWIVJC-UHFFFAOYSA-N n,n,4-trimethylbenzeneamine oxide Chemical compound CC1=CC=C([N+](C)(C)[O-])C=C1 NALMPLUMOWIVJC-UHFFFAOYSA-N 0.000 description 1
- SKECXRFZFFAANN-UHFFFAOYSA-N n,n-dimethylmethanethioamide Chemical compound CN(C)C=S SKECXRFZFFAANN-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- BSCHIACBONPEOB-UHFFFAOYSA-N oxolane;hydrate Chemical compound O.C1CCOC1 BSCHIACBONPEOB-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000003969 polarography Methods 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229940032753 sodium iodate Drugs 0.000 description 1
- 235000015281 sodium iodate Nutrition 0.000 description 1
- 239000011697 sodium iodate Substances 0.000 description 1
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Inorganic materials [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The present invention relates to an electrochromic display which is composed of a conductive film with large molecular weight and a counter electrode, wherein the conductive film is attached on a conductive transparent base, and the counter electrode is arranged below a liquid electrolyte. The conductive film with large molecular weight is a polymer with an isothianaphthene structure, and can be reversely oxidized or reduced. The polyisothianaphthene disclosed in the formula (Ia) and/or the formula (Ib) can be prepared by an electrochemical polymerization method or other polymerization methods. In the formula, R<1> and R<2> are hydrogen or alkyl which can be connected into condensed rings; X is sulfur, selenium or tellurium.
Description
The application is dividing an application of CN85105974.
In recent years, Electrical and Electronic equipment makes remarkable progress aspect light, thin, microminiaturized, and not only used various electric conducting materials need develop to light, thin, microminiaturized direction, and material itself also needs new developing.
People have known can use various sulfur heterocyclic ring polymer, as, the luxuriant polymer of sulphur, and referring to US Patent No 2,552,796 and U.S. Patent No. 2,658,902; The dibenzothiophenes polymer is referring to U.S. Patent No. 3,585,163; Vinyl bithiophene polymer is referring to U.S. Patent No. 3,615,384; Various substituted thiophene polymer are referring to U.S. Patent No. 3,725,362; 2-bromo-8-hydroxyl-5,5-dioxo dibenzothiophenes polymer is referring to United States Patent (USP) NO.3,775,368; Four sulphur pentalene polymer are referring to U.S. Patent No. 4111,857
In the conducting polymer body field that develops rapidly (" conducting polymer body physics and chemical international conference collected works ", J.physique.Colloque, 1983, c-3), heterocycle polymer is subjected to people and notes, this is because they are easy to film forming, and when exposing in atmosphere, it has better stability than polyacetylene or poly-(phenylene).About in the application aspect the stabilization of semiconductor surface, referring to R.Noufi etc., J.Amer.Chem.Soe.1981, volume 183,184 and lists of references wherein, the research work for polythiophene that we carry out in the recent period is exactly the continuity of this respect work.
Carried out the broad research work of novel conductive high polymer.For example, studying the polyacetylene class, they may be used as batteries electrode material because with the pentafluoride of iodine or arsenic mix the back (referring to, synthetic metal (synthetic metals), volume 1, No.2.101(1979/1980)), their excellent electric conductivity is up to 10
2To 10
3S/cm, and have excellent charging one discharge performance.Also make solar cell material with the polyacetylene class in research, this be because their extinction characteristic than near sunlight.But the polyacetylene class also has shortcoming, and itself is easy to oxidation polyacetylene, and (dopped) polyacetylene class of mixing is very responsive to moisture.
Polythiophene class not only can be used as electric conducting material, or as battery electrode material, this is to have the particular electrical minor structure because of them, it is similar to the conjugated structure of cis-polyacetylene, and sulfur atom-containing, in addition, utilize the dopant states change color, people also study with them as electrochromic material.For example, people such as A.M.Druy once reported, made 2,2 '-two thiophene electrochemical polymerizations generate the polymer with invertibity variable color, be that the blue look invertibityization of oxidation state becomes and goes back the ortho states redness, utilize this color change, this polymer can be used as electrochromic material.(referring to Journal de physigue, volume 44, No.6, C3-595(1983))
In view of the above problems, the inventor has carried out broad research, and we find that the polymer with indene structure different sulfur is a compound also highly stable in air, and can be in oxidation-reduction process invertibity ground conversion color, variation pattern is stable, is enough to reuse, in addition, this polymer also belongs to a kind of new polymers, it is oozing assortedly habitual when oozing assorted agent, is easy to demonstrate the conductivity higher than 10s/cm, thereby just finishes the present invention.
We have now synthesized the present invention's poly-(isothianaphthene), a kind of atypia thiophen polymer (M.P.Carn etc., Acc.Chem.Res, 1975, volume 8,139).Be not bound by any theory, we think, the stability (perhaps conductivity) of poly-(isothianaphthene) is higher than poly-(thiophene), this is because resonance component 1c shown in Figure 1 and 1d play a major role aspect shell molecular forms (1c) stable opening, and, be the high main cause of conductance along the delocalization of skeleton (backbone) (I d).
The similar resonant structure (particularly 1d analog) that can not look to gathering (thiophene) electronic structure can become important component, and only under poly-(benzo-thiophene) structure, this is because of 3 of thiophene, 4 keys are incorporated phenyl ring into, produced stability, and this stability improves greatly because of its resonant structure.
Among the preparation method of poly-(thiophene), in two kinds of methods the simplest, the one, the anode electrochemical polymerization of pure thiophene (A.Diaz, chem.Scripta, 1981, volume 17,145; G.Tourillon etc., J.Elechroanal, Chem.1982, volume 135,173, C.Kossmehl etc., Makromol.Chem.Rapid Commun, 1981, volume 2,551; J.Bargon, IBM, J.of Resand Dev., 1983, volume 27,330; K.Kaneto etc., J.Chem.Soc.Chem Com., 1983,382) another kind is 2,5-two fontanels are for chemical coupling (M.Kobayashi etc., Syhthetic Metals, 1984, the volume 9,77 of thiophene; T.yamamoto etc., J.polym SCi., Polym, lett.1980. volume 18,9; J.Lin etc., J.Polym.SCi.Polym, Chem, Edition, volume 18,2869).As with 2,2 '-dithienyl makes parent material, carries out polymerization with first method, improve to some extent (M.A.Druy, J.Physigue, Collogue of the material property of gained then, 1983, volume c-3,595) and electrolysis can the low applied voltage of electricity (～carry out under 3.5V).From practical viewpoint, cathode electrochemical polymerization more caters to the need, and it is easy, and product is more tough and tensile Lan-Hei filminess.The chemical coupling rule has more theoretical value, because product is a crystalline solid, number-average molecular weight is known, but the product of being produced always is Powdered.
We find that the most desirable poly-(isothianaphthene) preparation method makes the isothianaphthene galvanic coupling.(monomer preparation, referring to J.A.Gadvsz etc., Te Trahedron, 1979, volume, 35,2239; M.P.Cara etc., J.Amer.Chem.Soe., 1959, volume 89,4266; M.P.Cara etc., J.Org.Chem., 1971, volume 36,3932.)
In this patent, we will narrate the preparation method (electrochemical and chemical) of poly-(isothianaphthene) from hereinafter seeing, only need can produce needed unsaturated polymer carrying out electrochemical polymerization under the specific condition slightly.
As everyone knows, liquid crystal indicator has obtained development as a kind of need with energy display unit seldom, and be widely used in various aspects, still, liquid-crystal apparatus also exists the problem that relies on the visual angle, in addition, also have some other shortcoming, poor as display resolution, memoryless function, do not reach large tracts of land and show, or the like.In order to overcome these shortcomings, the ECD device has been carried out research completely, and the ECD device also belongs to the low power consuming type, and it utilizes so-called electrochromism (electrochromism), in the electrochromism body, optical absorption characteristics is different and different with voltage that applies or electric current.Used electrochromic material is divided into inorganic material and organic material in the ECD device.Be considered to the oxide that useful inorganic material mainly comprises transition metal, special case is a tungsten oxide, but their available color is limited, and when with proton as quality (colorforming) although reaction speed is very high during ion, can cause that the electrochemistry wash-out (elution) of film or electrode are rotten.On the other hand, organic material comprises the viologen dyestuff, phthalocyaninato complex, or the like.But the shortcoming of viologen dyestuff is the precipitation that can cause insoluble matter in repeated use, and phthalocyaninato complex also has the adhesion problem between a vacuum-evaporated film and the substrate still unresolved,
In addition, in the recent period the electrochromic material of suggestion also comprises polyaniline, referring to A.F.Dia2 etc., and Journal of Elechro-Analytical Chemistry, volume .111,111(1980) or Yoneyama, etc., ibid, volume 161,419(1984); Polypyrrole, referring to A.F.Diaz, etc., ibid, volume 101, (1983) and polythiophene are referring to M.A.Druy, Deng, Journl de physigue, volume 44, page or leaf June, page or leaf C-595(1983) or Kaneto etc., Japan Journal of Applied physics, volume, 23, No, 7, page or leaf L412(1983), come into operation but go back neither one in these materials.Especially, electrochromic material should be swift in response, the contrast height, and it is low to consume energy, and manifests excellent tone, or the like, in addition, electrochromic material also should be able to manifest colourless tone, and this can greatly open device range of application.Yet these complex conjugate type high molecular weight materials are gone back variable color the ortho states process being transformed into from oxidation state entirely.Improve the method for contrast, for example, use the white background plate, setting about studying, but also do not finishing.
Briefly, the present invention is the polymer with indene structure different sulfur, general formula as (I is a) and/or shown in (I b):
In the formula, R
1And R
2Represent hydrogen atom separately or contain the alkyl of 1 to 5 carbon atom, as methyl, methoxyl group and sulphomethyl, condition is R
1And R
2Can link to each other, form condensed ring, i.e. a naphthalene along phenyl ring; X is a sulphur, selenium or tellurium; Y
-Be electrolytic anion; Z is 0.01 to 1, the anion ratio of the every mole of monomer of this numeral; N is 5 to 100, this numeral degree of polymerization.
Show in the body in electrochromism, on the conductive, transparent base, form macromolecule conductive film, this conducting film is used as and shows that counterelectrode is placed under the liquid dielectric, characteristics of the present invention are that this HMW conducting film is the polymer with indene structure different sulfur, and this polymer can be by reversibly oxidation and reduction.
In electric, electronic application field, can use above-mentioned polymer as electrode or electrochromic display device, or be used to produce solar cell, the electricity of electromagnetic wire engages, fixing and conversion equipment, or as the reversible redox system.
Use various polymerizations, can easily synthesize the present invention's polymer.
Poly-(isothianaphthene) can prepare with several distinct methods with some relevant polymer.During with electrochemical method polymerization isothianaphthene, very strong to the electrolyte dependence.At nucleophilic anion (Rr
-, Cl
-) exist down, form poly-(benzo-thiophene).No matter at Bronsted acid (HSO
4NH
2O) still under the chloride doped forms, the conductivity of poly-(benzo-thiophene) can both be than high about 1 order of magnitude of polythiophene for doped forms.
For example, make general formula as (II a) 1,3-dihydro isothianaphthene-2-oxide or derivatives thereof,
In solvent,, then generate the polymer of required needs as reacting in the concentrated sulfuric acid with dehydration and oxidation effectiveness.
In addition, needed polymer also can be from can producing as the isothianaphthene or derivatives thereof of (II b) from general formula,
(II b) isothianaphthene can be produced, and for example, (II compound a) dewaters in the presence of aluminium oxide and distils, and prepares (II b) isothianaphthene to make general formula.Make formula (II b) isothianaphthene carry out following reaction, (ⅰ) in the presence of dielectric, in to aprotic solvent, carry out electrochemical polymerization, (ⅱ), carry out cationic polymerization, make two Hydrogen polymer of gained and oxidant reaction then with dehydrogenation using solvent or not using under the solvent condition; (ⅲ) oxidation polymerization; Or carry out polymerization with other similar approach.
The used solvent of above-mentioned monomer polymerization is not very strict, can select suitable solvent for use according to polymerization.Usually, when the isothianaphthene or derivatives thereof of formula (II b) carries out electrochemical polymerization in the presence of dielectric, can select the sub-atent solvent of confrontation for use, as, acetonitrile, benzonitrile, propionitrile, diox, oxolane, sulforan, propylene carbonate, or the like.When the isothianaphthene or derivatives thereof of formula (II b) carried out cationic polymerization, available solvent comprised: carrene, and chloroform, carbon tetrachloride, dichloroethanes, HFC-134a, nitromethane, nitroethane, nitrobenzene, carbon disulfide, or the like.When formula (II dihydro isothianaphthene-2-oxide or derivatives thereof a) dewaters-during polymerization, useable solvents has, for example, the concentrated sulfuric acid and polyphosphoric acids.In addition, when the isothianaphthene or derivatives thereof of formula (II b) carries out the oxidation addition polymerization, the solvent mixture and the Friedel-Crafts catalyst that can adopt cationic polymerization to use.
Polymerization temperature in the above-mentioned process for polymerizing monomers can determine that not strict especially, usually, polymerization reaction will be carried out according to concrete polymerization under-80 ℃ to 200 ℃.The method that polymerization time also can adopt, polymerization temperature, monomer structure or the like come to determine, and be general, polymerization time with 0.25 hour to 200 hours for well.
Above-mentioned formula (II a) and the monomeric compound of formula (II b) can be synthetic with known method, for example, referring to the described method of following file, M.P.Cara, etc., Journal of American Chemcal Soeiety, volume 81,4266(1959), and M.P.Cara. etc., Journal of Organic Chemrstry, volume 36, No, 25,3932(1971).In addition, in order to provide 1, the yield of 3-dihydro isothianaphthene can adopt the dissolubility lithium sulfide, the dissolubility lithium sulfide can prepare by making lithium triethylborohydride and reaction of Salmon-Saxl, referring to J.A.Gradysz, etc., Tetrahedron letters, volume, 35,2329(1979).
The present invention also comprises the preparation of this new polymers.
The purpose of this invention is to provide a kind of new polymers.
More particularly, the purpose of this invention is to provide a kind of novel conductive polymer.
Another object of the present invention also is to provide the new method of producing novel polyisothianaphthene base polymer.
Another object of the present invention and advantage, by the detailed description of bottom, more clear.
Please see accompanying drawing:
Fig. 1 is the infrared absorpting light spectra of the polymer of example 1 preparation.
Fig. 2 is the infrared absorpting light spectra of the polymer of routine II preparation.
Fig. 3 is the nmr spectrum of the polymer of routine II preparation.
Fig. 4 is an infrared absorpting light spectra of handling the polymer that polymer obtained of routine II preparation with chloranil.
Fig. 5 is the polarographic analysis result diagram of the polymer that obtained of example 5 electrochromic material service tests.
Fig. 6 is the relation curve of light absorption and voltage, and the HMW conducting film of routine X IV is immersed in the tetrahydrofuran solution, and every liter of tetrahydrofuran solution contains 0.53 mole of Liclo
4, make counterelectrode with lithium.
Fig. 7 is the cyclic voltammetry spectrum of the HMW conducting film of routine X IV, with (C
4H
9)
4NCLO
4Measure, it is dissolved in the acetonitrile, is electrolyte, voltage be+1.0V to-0.7V.(and standard calomel electrode comparison)
Fig. 8 is the cross section sketch of the present invention's ECD device.Among the figure, numeral 1 is represented the clear glass base, and 2 is show electrode, and 3 is electrochromic material, and 4 is liquid electrode, and 5 is electrode, and 6 is protective layer, and 7 are lead-in wire.
Fig. 9 represents to gather the invertibity electrochemical doping of (isothianaphthene).Make an electrode (band standard calomel reference electrode) with aluminium, make another electrode with poly-(isothianaphthene), the polypropylene carbonate ester solution of using the fluoro lithium borate can see that as electrolyte the present invention's polymer can be used as battery electrode.
Fig. 9 test also shows the electrochromic property of the present invention's new polymers.
Have novel structure fully according to the prepared polymer of the present invention, can not only demonstrate significant high conductivity by top layer, and can repeat electrochemical oxidation-reduction reaction, meanwhile, present the inherent colour of each state.In addition, the present invention's polyisothianaphthene is a kind of interesting especially polymer, even because its transparency can not weaken in the further state of oxidation yet.Therefore, the present invention's the polymer with indene structure different sulfur is of great use in Electrical and Electronic industry, for example, make electrode, electrochromic display device, solar cell, the electricity of electromagnetic wire engages, fixing and conversion equipment, and is used for the invertibity oxidation-reduction system.
The son of will giving an example illustrates details, but the present invention's scope is not limited by example.In following, make internal standard with TMS, the spectrophotometer EM-360A mensuration NMR spectrum that usefulness Varian/Analytical Div. makes (' H-NMR); The light photometer Model281 that makes with Perkin-Elmer company measures infrared absorption spectroscopy (IR),
Example 1
Handle 1 in the concentrated sulfuric acid, 3-dihydro isothianaphthene-2-oxide prepares polyisothianaphthene
(a) .1,3-dihydro isothianaphthene-2-oxygen synthetic
The lithium triethylborohydride that under room temperature and blanket of nitrogen, 200ml is contained 1mol/l add to fill 3.219(0.1mol) in the SChlenR flask of sulphur powder, reaction takes place at once, the dissolving of sulphur powder forms a yellow suspension.Owing to contact with micro-air.This suspension has become light yellow transparent solution.
Be furnished with dropping funel for one, blender, four neck flasks of 2 liter capacities of thermometer and nitrogen intake add 26.4g(0.1mol respectively under blanket of nitrogen) anhydrous tetrahydro furan of xylylene bromide and 1 liter forms solution.During stirring, the tetrahydrofuran solution of the lithium sulfide for preparing above at room temperature dropwise added with 1.5 hours.After this, oxolane is removed in decompression distillation, and further distillation leftover is so that obtaining boiling point is the colourless 1 of 74～76 ℃/3mmHg, 3-dihydro isothianaphthene 10.9g(productive rate: 80%).The infrared spectrum of product is 3060,3026, and 1582 and 1485cm
-1Shown absorption based on phenyl; 2910,2840 and 1450cm
-1Shown absorption based on benzylidene; At 1195cm
-1Based on 1,2-substituted-phenyl plane inner deformation has shown absorption; Absorption at 760cm 0-substituted-phenyl; At 740cm
-1The absorption of thioether.At CHCL
3In with tetramethylsilane (TMS) as the nulcear magnetic resonance (NMR) of internal standard (' H-NMR), measurement result is as follows:
4.22（S，4H）;7.20（S，4H）
This compound is very unstable, even be kept at still can be black from xanthochromia under light shield and the air-proof condition.
Then, thus obtained 1,3-dihydro isothianaphthene add 450ml above-mentioned be dissolved with 18.6%(0.086mol) sodium iodate 50%.Methanol aqueous solution, mixture at room temperature stirred 12 hours, isolated the precipitation of generation with filtration method.Filter cake 50ml washed with methanol.Washing lotion and filtrate are mixed and decompression concentrates.Yellowish white solid recrystallization from ethyl acetate-cyclohexane of Xing Chenging thus obtains at molten o'clock little yellow crystals of 87～89 ℃.
Resulting crystal further from ethyl acetate-cyclohexane recrystallization so that obtain at molten o'clock at 90～91 ℃ crystal.The crystal infrared spectrum shows, except isothianaphthene absorbs, and the absorption thioether that also splits by force at 1035cm, and at 740cm
-1Thioether absorb to disappear.At CHCl
3Middle as follows as the nuclear magnetic resoance spectrum of internal standard measurement with methyl-monosilane:
4.65（S，4H），7.20（S，4H）
C
8H
8The SO elementary analysis:
Calculated value: (%): C63.16; H5.26; S21.05
Measured value: (%): C63.08; H5.15; S20.87
(b) from 1.3-dihydro isothianaphthene-2-oxide (II a, R
1=R
2=H) synthetic polyisothianaphthene
Add the concentrated sulfuric acid of 1ml in the 1.3-dihydro isothianaphthene of 500 milligrams (3.29mmol), become kermesinus in the reaction system at once.Mixture was put 70 hours under the greenhouse, injected the methyl alcohol of 400ml after solidifying basically etc. system.The brown precipitate that generates is separated water cleaning down and with centrifugal filtration 60 ℃ of one nights of vacuumize.The polymer that obtains is placed in the Soxhlet's extractor, extracted successively 12 hours with carrene and chlorobenzene respectively, obtain the chlorobenzene insoluble matter of 203mg.The infrared spectrum of resulting polymers as shown in Figure 1.The result of elementary analysis is C:67.26%; H:3.12%; S:23.59%, if with according to repetitive with following structure
Calculated value (C:67.19%; H:3.32%; S:23.54%) quite consistent.
The conductivity of polymer (6RT) is to measure with four-terminal-network conductivity measurement device under the room temperature, is 2 * 10
-2S/cm.
The example II
Prepare polyisothianaphthene with the oxidant oxidation from the poly-dihydro isothianaphthene that the cationic polymerization of isothianaphthene obtains
(a). synthetic (II 6, the R '=R=H) of isothianaphthene.
With 300 milligrams (1.97mmol) according to routine 1(a) synthetic 1.3-dihydro isothianaphthene-2-oxide and 450mg(4.41mmol) neutral alumina abundant pulverize in mortar, and fully mix, be placed on then in the sublimation apparatus, decompression is heated in an oil bath down.Cooling segment at sublimation apparatus has thoroughly obtained 250mg(1.87mmol) the isothianaphthene white, needle-shaped crystals, be right after thereafter, resulting monomer is dissolved in the carrene alkane of the 5ml purifying degassing, adds the 10mg trifluoroacetic acid then, then mixture is placed a night.When 50ml methyl alcohol injects reactant mixture, get a white depositions.Resulting polymers dissolves in the N-methylacetamide at chloroform, chlorobenzene, oxolane and N.The infrared spectrum of this polymer and ' the H-nuclear magnetic resoance spectrum respectively as shown in Figures 2 and 3.
In addition, the tetrahydrofuran solution of this polymer is transformed into polystyrene with gel permeation chromatography (Varian5000), confirms that the molecular weight of polymer is 2000.
At room temperature, the polymer conductivity (σ that measures in example 1 same mode
RT) be 10
-8S/cm or low.
(C
8H
6S) elementary analysis:
Calculated value: (%): C71.64; H4.48; S23.88
Measured value: (%): C71.27; H4.54; S23.96
Except make polymerization initiator replacement trifluoroacetic acid with methanesulfonic acid, repeat above-mentioned identical operation and obtain-polymer.The resulting polymers infrared spectrum is consistent with Fig. 2 fully.
These polymer dissolution are handled with the chloranil of twice mole in the 5ml chlorobenzene, form black precipitate.Under the room temperature, the conductivity of resulting polymers (δ RT) is 9 * 10 S/cm, and a kind of polymer conductivity of the iodine that mixes is 9 * 10 S/cm.The infrared spectrum of this polymer is shown in Figure 4.Even the polymer compound room temperature of doping iodine is placed down in a week in the air, conductivity can not cause change yet.
Except using the 5ml chloroform to replace chlorobenzene; 1.1 doubly the N-chlorosuccinimide of mole replaces outside the chloranil, with above-mentioned same method make a black, fully with Fig. 4 in the identical polymer of illustrated infrared spectrum.Record the conductivity (σ that knows this polymer
RT) be 2.6 * 10
-1S/cm.
Example 3
Oxidation step polymerization isothianaphthene prepares polyisothianaphthene
Example 2(a) same method is synthesized isothianaphthene.Under 35～37 ℃ of temperature, make the isothianaphthene of 250mg, the anhydrous methylene chloride of 5ml, the mixture reaction of the anhydrous Aluminum chloride of 134mg and the anhydrous cupric chloride of 134mg 1 hour produces black precipitate.Such reactant mixture is preserved the methanol solution that will precipitate after 12 hours with hcl acidifying and is handled under said temperature, the water cleaning down is also dry.Use hot methanol successively, hot carrene and the extraction of hot chlorobenzene be the polymer of drying, obtains the black polymer of 205mg.The infrared spectrum of this product is fully consistent with Fig. 4, conductivity (σ
RT) be 2.8 * 10 S/cm.
Example 4
The electrochemical polymerization isothianaphthene prepares polyisothianaphthene
The isothianaphthene electrochemical polymerization method is as follows:
Under room temperature and constant voltage, the platinum plate is made sample panel; Aluminium sheet is made counterelectrode; In official hour, make isothianaphthene make electrolyte shown in the table 1 and isothianaphthene be dissolved in and carry out electrochemical polymerization in the electrolytic solution made in the polar solvent to be dissolved in normal concentration.On platinum plate anode, generated the polyisothianaphthene film.Helium bubbling in above-mentioned electrolytic solution was blown over 30 minutes at least, so that deoxidation in advance.Constant voltage is 1.5V in the polymerization.
The film of Sheng Chenging is used acetonitrile and carrene cleaning down and vacuumize successively thus.The result that the electrical property of mensuration film obtains is shown in the appended table 1.
Table 1 note:
P
4ASCl: Lvization Si Ben Arsenic
P
4PCl: chlorinated tetraphenenyl phosphorus
Bu
4NBr: bromination four (normal-butyl) ammonium
LiBr: lithium bromide
Bu
4NPF
6: hexafluoro phosphorus four (normal-butyl) ammonium
Bu
4NClO
4: perchloric acid four (normal-butyl) ammonium
CH
3CN: acetonitrile
PCN: benzonitrile
Implement 5
Polyisothianaphthene is as the electrochemistry display element, the use of battery material etc.
Repeat the same operation of routine 4-2, but, polymer chemistry is deposited on the electro-conductive glass thereon with the platinum plate among electro-conductive glass (the vacuum evaporation indium oxide is made anode) the replacement example 4-2.The polymer-coated electro-conductive glass of gained is made the work electrode, the platinum line is made counterelectrode, standard calomel electrode is made reference electrode, carries out the cyclic voltammetry measurement method by use polarographic analyze (the 174A type that EG and G company make) under the room temperature in the acetonitrile solution of the TBAP that contains 292mmol.The voltage scan rate of using is 20mv/sec, sweep limits from+1.0V to-0.7V(with respect to standard calomel electrode).Fig. 5 has shown resulting result.
As shown in Figure 5 ,+0.58V and-the 0.15V polymer has shown oxidation peak and reduction peak respectively, and coloured variation: from-0.7V～+ avy blue in the 0.6V voltage range become+0.6V～+ super transparent light green color in the 1.0V voltage range.These results show: the avy blue state is a condition in the polymer, and polymer is the green color of highly transparent under oxidation state and doping attitude.
Test as battery
The polyisothianaphthene that obtains among the routine 4-1 is cut into the long test piece of the wide and 3cm of 1cm, and one of test piece is with on the electroconductive binder cementation one platinum line.The mode that can permeate fully inwards with electrolyte, by means of 1 porous polypropylene diffusion barrier that 1cm is thick, test piece is placed on the onesize lithium paper tinsel, then, this system is soaked in the propylene carbonate solution of the lithium perchlorate degree of depth 2cm that contains 0.5mol/l, Zhi Bei battery (wherein polyisothianaphthene is a negative electrode, and the lithium paper tinsel is an anode) is 2.0mA/cm in charging current thus
2And under argon atmospher, charged 30 minutes.After the charging fully at once discharging current be 2.0mA/cm discharge down, when cell voltage drops to 1V, under above-mentioned similarity condition, charge once more simultaneously.When discharging and recharging operation when repeating with said method, note repetition 590 times, be reduced to 50% up to efficiency for charge-discharge efficient.In addition, 5 times are repeated efficiency for charge-discharge is 99%, and in addition, after battery was in 48 hours charged states, self-discharge rate was 3.2%.
Example 6
Electrochemical polymerization method preparation poly-(dihydro isothianaphthene)
The monomer isothianaphthene is with document (people such as J.A.Gladysz, Tetrahedron, 1979 volumes 35,2239; People such as M.P.Ca Va, J.Amer.chem, Soc., 1959, volume 81,4266; People such as M.P.Ca Va, J.Ora.Chem., 1971, volume 36,3932) the method preparation described, make the back and directly use.Poly-(dihydro isothianaphthene) carries out electrochemical oxidation to this monomer and makes in two electrodes, separating diaphragm battery, platinized platinum is made anode, and graphite oxide is made negative electrode.The isothianaphthene and the 0.30M electrolyte Bu that in acetonitrile, add 0.23M
4NPF
6, this anhydrous clear solution is used for polymerization reaction.Directly use acetonitrile (Mallinckrodt) and do not need to be further purified, make power supply with the 1.5V battery of series connection.
All experiments are carried out in dried nitrogen, when these battery two ends connect 4.5V voltage, occur many white powders near the anode immediately, turn off battery after ten minutes.This poly-(dihydro isothianaphthene) white powder separates by suction strainer, with acetonitrile and diethyl ether flushing and vacuumize.For carrying out elementary analysis, resulting solid precipitates with oxolane-water again and obtains purifying.
When the isothianaphthene sample of new system at hydrogen battery utmost point layer (Bu
4Nclo
4Or BU
4NBF
4Make supporting electrolyte, the glass (TOG) of tin oxide coating is made anode) during the electrolysis of lining, a large amount of white precipitate (" WP ") has been full of anode layer.Find that after examining anode at first (instantaneous) has covered extremely thin blue film, after this begins to generate WP immediately.The outward appearance of WP and electrode material, solvent, or temperature is irrelevant.Separate, CHARACTERISTICS IDENTIFICATION (infrared ray, flexibility analysis) and chemical operation (face as follows) prove: WP is exactly poly-(dihydro isothianaphthene).It should be noted that under these conditions (poly-(isothianaphthene) of doping that the chances are, when being transformed into poly-(dihydro isothianaphthene), thiophene has produced the thin polymer film of partial oxidation (" doping ") having precipitated extremely thin blue film when isothianaphthene.For the unique proper explanations of this wonderful observation be: the effect that poly-(isothianaphthene) takes on the isothianaphthene cationic polymerization initiators.In order to verify this section hypothesis, we are exposed to the isothianaphthene solution of new system in some typical catalyst and cause for cation, find to make the isothianaphthene polymerization to some extent under all occasions, but the most interesting result is the dichloromethane solution effect for sulfuric acid, at this moment, isothianaphthene is transformed into poly-(the dihydro isothianaphthene) of the hydration sulfuric acid doping of blue black.Obviously, acid has not only played catalyst, and has played oxidant.To " concentrating " test stone of top hypothesis insurance is that the product of tetrachloro-P-benzoquinones dehydrogenation is poly-(a dihydro isothianaphthene) and demonstrate the sulfuric acid polymerized product that is equal to infrared spectrum.For the unique proper explanations of this observation be, the infrared spectrum of mix poly-(isothianaphthene) is subjected to because the absorption of conduction electron is controlled, and because the absorption of intramolecule vibration is the weakness of spectrum.When the additional control of shortage is tested, be difficult to concrete mechanism of supposition and explain this electrolytical effect.
We infer that sulfuric acid can directly change into poly-(isothianaphthene), (H to dihydro isothianaphthene-S-oxide
2SO
4)
x(H
2O)
ySolid dihydro isothianaphthene-S-oxide is added in 98% the sulfuric acid, has in fact generated poly-(isothianaphthene) (following Fig. 1) that desired part is mixed really.
Fig. 1
In addition, 7,7,8,8 ,-four cyanide quinolines and bismethane can be as the catalyst of cationic polymerization.But product does not demonstrate than the poly-higher conductivity of (isothianaphthene) compound of any other doping, points out that acceptor does not probably relate to the conductivity of solid.For the sort of observation, two kinds of judgements may be advanced, and promptly the acceptor molecule probably is not deposited in the small crystals zone, and/or exists charge transfer completely.
The above results is explained the essence of the process that poly-(dihydro isothianaphthene) forms, and for the chemical synthesis of poly-(isothianaphthene), has found method cleverly, and The above results still can not provide the way of isothianaphthene electrochemical polymerization.This just needs discover method, prevents that catalyst is owing to " nascent state " doping poly-(isothianaphthene) forms poly-(dihydro isothianaphthene).We find that if having in the reaction medium than the more molecule formation of nucleophilic of isothianaphthene, chain growth is cut off step and will be damaged.One related to before electrolysis and iodide to be added to detection in the anode layer the experiment failed of success, because iodine is oxidized under the electrolytic condition.However, with LiBr, Bu
4NBr or the most handy Ph
4ASCl can produce fabulous film during electrolysis on platinum or TOG.The unique proper explanations of this observation is, being subjected to because the control of the absorption of conduction electron of poly-(isothianaphthene) infrared spectrum of doping, and the absorption of intramolecule vibration is the weakness of spectrum.When lacking additional control test, be difficult to infer a this electrolytical effect of concrete mechanism explain.
C
8H
6S analytical calculation value: C11.60; H4.51; S23.89;
Measured value: C71.27; H4.54; S23.96
LiBF and BuNCLO can be used as the electrolyte of this reaction.
According to the present invention, have been found that at least and can aggregate into the metastable state isothianaphthene high conducting polymer with three kinds of distinct methods with excellent characteristic; One relates to when having the anion of nucleophilic, and by the isothianaphthene polymerization, electrochemical preparation is gathered (dihydro isothianaphthene).
Have found that poly-(isothianaphthene) is than the better conductor of polythiophene.
Embodiment 7
With chemical cationic polymerization preparation poly-(dihydro isothianaphthene)
(396mg 2.96mmol) is dissolved in 10ml and gives earlier through P the monomer isothianaphthene
2O
5In the dry carrene, in this liquid, add a methanesulfonic acid, at once from the colourless redness that becomes, after 90 minutes, become purple in the reactant mixture.After carrene was removed in evaporation, residue dissolved with oxolane.After this solution injected methyl alcohol, poly-(dihydro isothianaphthene) settled out from solution.Separate vacuumize with centrifugal filtration.Infrared spectrum is identical with poly-(dihydro isothianaphthene) above-mentioned.
Following Example is the present invention's application success example on the spot, but does not plan to limit invention.
Poly-(isothianaphthene) that the electrochemical polymerization method preparation is mixed
Polymerization is identical with above-mentioned example 6 poly-(dihydro isothianaphthene) basically.The most important is an electrolyte.When lithium bromide is used as electrolyte, connect a 1.5V battery, poly-(isothianaphthene) blue film of doping is gone up at anode (electro-conductive glass) at once and is generated.Bu
4NBr and Ph
4AsCl also can be as the electrolyte of this reaction.
Embodiment 9
Carry out poly-(isothianaphthene) that chemical cationic oxidation polymerization preparation is mixed with sulfuric acid
Sulfuric acid (5ml) be added to the monomer isothianaphthene (396mg, 2.96mmol) in, the color of monomer becomes red-black from leucismus at once.After stirring a night, reactant mixture is injected 400ml methyl alcohol, the doping of brown ceramic powder poly-(isothianaphthene) settles out from this solution.Then, centrifugation with the extraction of soxhlet extractor, is adopted carrene and chlorobenzene, then vacuumize.This reaction also can be carried out with the carrene suspension of sulfuric acid.
Embodiment 10
Use TCNQ(7,7,8,8-four cyanide quinolines and bismethane) carry out poly-(isothianaphthene) that chemical cationic oxidation polymerization preparation is mixed.
Monomer isothianaphthene (238mg, 1.77mmol) solution in the 5ml carrene.Add after a few gram TCNO in solution, its color becomes redness very slowly.After stirring a night, this color becomes blue black.Thereafter, add the TCNQ that doubles monomer isothianaphthene mole to this solution, heating is until 110 ℃ and kept 1 hour.Behind this solution injection methyl alcohol, the blackish green powder is precipitated out from solution.In the Soxhlet extractor, adopt the flushing of methyl alcohol and chlorobenzene, and vacuumize.
From poly-(dihydro isothianaphthene) preparation poly-(isothianaphthene)
Poly-(the dihydro isothianaphthene) of electrochemical polymerization preparation dissolves in hot chlorobenzene, and this is a light brown solution.When tetrachloro-P-benzoquinones was added in this solution, solution colour became dark green at once.By cooling, powder is precipitated out from this solution, and through suction strainer, with washed with methanol and vacuumize, this precipitation obtains separating.Implement the identical infrared spectrum that 7～10 all substances of mentioning show.
Therefore, the invention provides the route of three kinds of alternative preparations poly-(isothianaphthene):
1. when having the nucleophilic anion to exist, make isothianaphthene carry out electrochemical polymerization.
2. having in the presence of the cationic polymerization catalyst, making isothianaphthene or dihydro isothianaphthene-s-oxide carry out chemical polymerization.
3. poly-(dihydro isothianaphthene) carries out dehydrogenation.
The PRELIMINARY RESULTS of conductivity measurement is collected in the table 2, and poly-(isothianaphthene) band edge is estimated as～1ev(1.1 μ) (under low-doped degree, passing through film transfer), this be lower than polythiophene (1～2ev, 620nm)
3Nearly 1ev.
Table 2
Poly-(isothianaphthene) compacting conductivity table mixes
Compound (S/cm)
a
Poly-(isothianaphthene) Cl
x-embodiment 8 4.0 * 10
-1
Poly-(isothianaphthene) (HSO
4)
0.05(H
2O)
0.033
Implement I b 2.0 * 10
-2
Poly-(isothianaphthene) (AlCl
4)
x-embodiment 3 2.8 * 10
-2
Gather (isothianaphthene) (TCNQ)
x-embodiment 10 1.5 * 10
-2
Poly-(isothianaphthene) (tetrachloro-P-benzoquinones)
4x-embodiment 11 1.3 * 10
-2
Fig. 9 surface the reversible electrochemical of poly-(isothianaphthene) mix.Therefore, make an electrode (using the standard calomel reference electrode) with aluminium, poly-(isothianaphthene) makes another electrode, and the polypropylene carbonate ester solution of lithium fluoroborate is an electrolyte, and as can be seen, polymer of the present invention can be used as battery electrode.
The test of Fig. 9 also shows the polymer electrochromic feature that the present invention is new.
In Fig. 6, we prove electrochromic effect; Alloy is clO
- 4, reference electrode is a lithium.Energy source is penetrated in the incident width of cloth, and 0～1st, at infrared region, 1～2nd, visible light is transferred to the spectrum ultraviolet part gradually more than 2.Result displayed has further been pointed out the application of polymer of the present invention in device for converting solar energy among Fig. 6, because semiconductor energy gap and solar spectrum coupling are fine.
The inventor has carried out extensive studies to the electrochromic property of polymer with isothianaphthene mechanism, found that: above-mentioned polymer is novel electric type off-color material, its response has colourless tone rapidly basically under oxidation state, therefore reached purpose of the present invention.This discovery is beyond thought, and is unknown because this colourless basically electrochromic material still belongs to so far.According to the present invention, electrochromic display device (ECD) (ECD) by on it by the conductive, transparent base of the conducting film of a molecular weight and be placed on its down the counterelectrode under liquid electrolyte form, the conducting film that it is characterized in that described macromolecule is the polymer with indene structure different sulfur, reversibly oxidation or reduction." liquid electrolyte " used herein speech is meant the dispersion or the solution of supporting electrolyte in the solvent.
The macromolecule conductive film can be used as electrochromic film according to the present invention, its reversibly oxidation or reduction and be the polymer with indene structure different sulfur (the formula III is represented):
R wherein
1And R
2Represent hydrogen or have the hydro carbons of 1～5 carbon, X is sulphur, selenium or tellurium, Y
-Represent anion.Z is a value between 0～0.40, represents anionic ratio in each indene structure different sulfur unit, and N represents 5～500 the degree of polymerization, be to produce through electrochemical polymerization by the isothianaphthene compound that the following formula IV is represented,
R in the formula
1, R
2Identical with X and above-mentioned definition.
The isothianaphthene compound object lesson of formula (IV ') representative comprises 1,3-isothianaphthene, 5-methyl isophthalic acid, 3-isothianaphthene, 5,6-dimethyl isothianaphthene, 5-ethyl-1,3-isothianaphthene, 5-methyl-6-ethyl-1,3-isothianaphthene or the like.
The electrochemical polymerization of above-mentioned isothianaphthene compound can be carried out [for example, at Solid state communication, rolling up 46, the 5, the 389(1983) method of Miao Shuing] according to the method that generally is used for electrochemical polymerization thiophene, pyrroles or the like.Particularly can use two control potential electrolysis or Control current electrolysis, and wish by using the conductive, transparent base on transparent base, to form thin polymer film as sample electrode.
Can be used as transparent base of the present invention comprises: contain transparent insulator (for example: glass, polyester film etc.), have thereon vacuum evaporation indium oxide-Xi, tin oxide, platinum, or the like, use sputter or similar approach.These materials are easy to buy as industrial goods.The thin polymer film that electrochemical polymerization generates, thickness be from 0.03～30 μ m, 0.05～22 μ m preferably, and the best is 0.1～10 μ m.Film thickness can be subjected to the control of the magnitude of current in the electrochemical polymerization, when film thickness during less than 0.03 μ m, can not get contrast clearly, therefore as then having considerable damage on the display material economic worth.On the contrary, thickness surpasses 30 μ m provides contrast clearly, but is unfavorable with regard to film strength or response speed.
Counterelectrode is inserted in the liquid electrolyte, refills and mix the polymer that is obtained, promptly produce the ECD display instrument.Employed liquid electrolyte is the dispersion of the supporting electrolyte in solvent or solution.Operable supporting electrolyte comprises that anion combines with cationic among the present invention, and (ⅰ) anion (is Y in the formula III
-), resemble the fontanelle compound anionic species of Va elements, for example PF
- 6, SbF
- 6,
ASF
- 6And SbCl
- 6; The fontanel anionic species of III a family column element is as BF
- 4; Halide anion, for example I
-(I
- 3), Br
-And Cl
-; Perchloric acid anionic species, for example ClO
- 4; And (ⅱ)
Resemble the alkali metal ion cationoid, for example Li
+, Na
+And K
+; Quaternary ammonium ion, for example R
4N
+(wherein R represents to have the alkyl of 1～20 carbon atom; Yi is Ji Phosphonium ion, for example (C
6H
5)
4P
+But these combinations are not restrictive.
Is LiPF by above-mentioned anion (x) and cation in conjunction with the object lesson of the supporting electrolyte that constitutes
6, LiSbF
6, LiAsF
6, LiClO
4, NaI, NaSbF
6, NaAsF
6, NaClO
4, KI, KPF
6, KSbF
6, KA
sF
6, KClO
4, [(n-Bu)
4N]
+(ASF
6)
-, [(n-Bu)
4N]
+(PF
6)
-, [(n-Bu)
4N
+] ClO
4, LiALCl
4, Li, BF
4, (C
6H
5) PBF
4, (C
6H
5)
4PAsF
6(C
6H
5)
4PClO
4, but these examples are not restrictive.These supporting electrolytes can use separately, if necessary or two or more combine use.Except that the above-mentioned anion of enumerating, also can use HF
- 2Anion.Spendable cation also further comprises pyrrole except that the above-mentioned cation of enumerating
Or pyridylium (following formula (V) is represented) and carbocation (following formula (VI) or (VII) are represented:
Z represention oxygen atom or nitrogen-atoms in the formula; R ' represents hydrogen atom.An alkyl or a 6-15 carbon atom aryl that has 1～15 carbon atom; R " represents halogen atom, an aryl that has the alkyl of 1～10 carbon atom or have 6～15 carbon atoms; When Z is an oxygen atom, m is zero or when Z was nitrogen-atoms, m was 1; P is zero or integer between 1～5.
R in the formula
3, R
4, R
5Each represents a hydrogen atom, has the alkyl of 1～15 carbon atom, a pi-allyl, aryl that has 6～15 carbon atoms or-OR
7, R in the base
7Represent the alkyl of 1～10 carbon atom or have the aryl of 6～15 carbon atoms, condition is R
3, R
4And R
5Not hydrogen atom simultaneously; R
6Represent hydrogen atom, an aryl that has the alkyl of 1～15 carbon or 6～15 carbon are arranged.
Operable HF
- 2Anion normally by the dissolving following formula (VIII), (IV) or (X) expression compound (hydrofluoride) and obtain,
M·HF
2（Ⅸ）
" each represents a hydrogen atom, an aryl that has the alkyl of 1～15 carbon atom or have 6～15 carbon atoms for R ' and R in the formula; " ' representative has the alkyl of 1～15 carbon atom or has the aryl of 6～15 carbon atoms R; Z represention oxygen atom or nitrogen-atoms; Q representative zero or one 5 or 5 following integers; M represents alkali metal as a kind of supporting electrolyte in appropriate solvent.By following formula (VIII), the compound object lesson of (IV) and (X) representative comprises H
4NHF
2; Bu
4NHF
2, N
aHF
2, KHF
2, LiHF
2With
The pyrrole of formula 3 representatives
Or pyridylium can dissolution type (V) representative cation and anion (X) ClO for example
4, BF
- 4, AlCl
- 4, FCl
- 4, SnCl
- 5, PF
- 6, PCl
- 6, SbF
- 6, AsF
- 6, CF
3SO
- 3, HF
- 2Or the like) between form in appropriate solvent, obtain as the salt of supporting electrolyte.The object lesson of this salt is:
Above-mentioned formula (VI) or VII) object lesson of carbocation of representative comprises (C
6H
5)
3C
+, (CH
3)
3C
+,
These carbocations can or be dispersed in the salt that forms as supporting electrolyte in the appropriate solvent between cation and the anion (X) (being carbon salt) by dissolving and obtain.The available anion (X) of typical case comprises (BF
- 4, AlCl
- 4, AlBr
3Cl
-, FeCl
- 4, PF
- 6, PCl
- 6, SbCl
- 6SbF
- 6, ClO
- 4, CF
3SO
- 3Deng, for example carbon salt is particularly including (C
6H
5)
3CBF
4, (CH
3)
3CBF
4, HCOAlCl
4, HCOBF
4, C
6H
5COSnCl
4Or the like.
Available solvent both can be that aqueous solvent also can be a nonaqueous solvents among the present invention, but supporting electrolyte solution noted earlier is relatively good in non-aqueous organic solvent, and organic solvent used herein is aprotic solvent preferably, and high dielectric constant is arranged.For example, can use ether, ketone, nitrile, amine, acid amides, sulphur compound, phosphotidic compound, inferior phosphotidic compound, boric acid ester compound, chlorinated hydrocabon, ester, carbonic ester, nitro compound and all classes.Certainly, preferably ether, ketone, nitrile, phosphotidic compound, inferior phosphotidic compound, boric acid ester compound, chlorinated hydrocabon and carbonic ester.The object lesson of these solvents comprises oxolane, 2-methyltetrahydrofuran, 1-4-diox, Monoethylene Glycol (MEG) dimethyl ether, acetonitrile, propionitrile, 4-methyl-2 pentanone, butyronitrile, valeronitrile, benzonitrile 1-2-dichloroethanes, r-butyrolactone, valerolactone, dimethoxy-ethane methyl formate, propylene carbonate, ethylene carbonate, dimethyl formamide, dimethyl sulfoxide (DMSO), dimethyl thioformamide, ethyl phosphonic acid ester, methyl phosphorodithioate, the inferior phosphide of ethyl phosphorous acid METH, 3-trimethyl sulforan or the like.In order to improve response speed, in the middle of them, with nitrile and carbonic ester especially for well.
These organic solvents can use separately also can two kinds, two or more being used in combination.
Oxygen and water in these (proton) solvents make ECD display instrument performance depreciation sometimes, and this depends on the model of employed ECD display instrument or the type of electrodes of use.In this case, preferably give elder generation's purification solvent in normal way, in this external ECD display instrument of the present invention except that can using above-mentioned electrolyte, can also use the organic solvent that only spreads to supporting electrolyte, perhaps ionic conduction high, by polyethylene oxide and Na I, the organic solid electrolyte based that Na SCN etc. form.
The supporting electrolyte that uses in the ECD display instrument of the present invention, its concentration depend on use solvent species, apply current/voltage value, working temperature, supporting electrolyte kind and like that, therefore, generally can not fix.Liquid electrolyte can be homogeneous phase also can be heterogeneous, but normally used concentration range is between 0.001～10mol/l.Distance generally be can not determine between macromolecule conducting film and counterelectrode, because the kind of supporting electrolyte, the electric current that applies and magnitude of voltage, ECD display instrument display list area and all classes are depended in their variation, but preferably from 0.05～5mm.As counterelectrode, according to the purpose purposes, can use multiple material in addition, promptly when transmitted light was used to show, aforesaid transparent material was preferably as counterelectrode.On the other hand, with regard to the emission light that uses, also can be used as the counterelectrode use and resemble the opaque electric conducting material of tinsel class, for example nickel or platinum and woven wire.In addition, because the ECD display instrument provides colourless substantially tone, just can select the base plate of different tones for use.Therefore, the ECD display instrument that the present invention obtains can be used for extensive use owing to extensively select the material of use.
Now, explanation the present invention that reference example is more detailed, but should be appreciated that the present invention is not limited to these examples.
Example 12
Containing (the C of 0.08mol/l
6H
5)
4Dissolve 0.0788mol/ll in the acetonitrile solution of PCl, [compound of formula (IV) is R wherein for the 3-isothianaphthene
1=R
2=H] preparation electrolyte.Use above-mentioned electrolyte, a glass plate (tin indium oxide is vacuum evaporation thereon) is made sample electrode, and an aluminium sheet is made counterelectrode, is that electrochemical polymerization was carried out in energising in 20 minutes under the 2mA/cm in room temperature and current density.Scribbling on the indium oxide tin glass plate anode, obtaining the slight avy blue polymer that mixes of electrochemistry.The demonstration base that obtains is also dry with the acetonitrile flushing, and dry polymer film is 10 μ m.
Consequent demonstration base is immersed in and contains 0.53mol/l LiClO
4Tetrahydrofuran solution in, measure applying the dependence of voltage as counterelectrode energising with lithium.The result who obtains is shown in Figure 6.As shown in Figure 6, polymer at 2.50V(to lithium electrode) under have blue look, but be transformed into transparent light green at 3.50V.Confirm that also this variation is reversible.
In acetonitrile, use (C then
4H
9)
4NClO
4As electrolyte, applying voltage-0.7V～1.0V(to standard calomel electrode) under carry out voltammertry.The result who obtains shows in Fig. 7, as can be seen from Figure 7, voltage+0.6～-0.7V between polymer film have avy blue, and voltage becomes the light green of highly transparent between+0.6～1.0V.
According to these results, produced the ECD display instrument shown in Fig. 8.Contain 0.53mol/l LiBF
4The polypropylene carbonate ester solution add liquid electrolyte, sealing then.Under the 1HZ frequency to the ECD display instrument apply+0.8V～-square wave of 0.4V so that finish fatigue test.As a result, even 2 * 10
4After inferior variable color and the decolouring work, do not observe the rotten of electrochromic material yet.
Fully describe the present invention, be intended that the restriction that the present invention only is subjected to the scope of law of claim.
Claims (1)
1, electrochromic display device (ECD) (electrochromic display), wherein, the HMW conducting film that forms on the conductive, transparent base is used as and shows base (display base), counterelectrode places it down through liquid electrolyte, it is characterized in that this HMW conducting film is the polymer that indene structure different sulfur is arranged that can carry out reversible oxidation or reduction, this have indene structure different sulfur polymer structural formula for (I a) and/or (I b):
In the formula, R
1And R
2Respectively do for oneself hydrogen atom or contain the alkyl of 1 to 5 carbon atom, as methyl, methoxyl group and sulphomethyl, condition is R
1And R
2Can link to each other and form condensed ring, i.e. naphthalene along phenyl ring; X is sulphur, selenium or tellurium; Y is an electrolytic anion; Z is 0.01 to 1, the anionic ratio of the every mole of monomer of this numeral; N is 5 to 500, this numeral degree of polymerization.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85105974A CN1007815B (en) | 1985-08-07 | 1985-08-07 | Process for preparing polymer having isothiaindene structure and electro-chromic display properties |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85105974A Division CN1007815B (en) | 1985-08-07 | 1985-08-07 | Process for preparing polymer having isothiaindene structure and electro-chromic display properties |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1045410A CN1045410A (en) | 1990-09-19 |
| CN1018874B true CN1018874B (en) | 1992-10-28 |
Family
ID=4794806
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85105974A Expired CN1007815B (en) | 1985-08-07 | 1985-08-07 | Process for preparing polymer having isothiaindene structure and electro-chromic display properties |
| CN90100116A Expired CN1018874B (en) | 1985-08-07 | 1985-08-07 | Polymer having isothianaphthene structure and electrochromic display |
| CN92100766A Expired - Lifetime CN1023527C (en) | 1985-08-07 | 1992-02-09 | Process for preparation of polymer having isothianaphthene structure and electrochromic display |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85105974A Expired CN1007815B (en) | 1985-08-07 | 1985-08-07 | Process for preparing polymer having isothiaindene structure and electro-chromic display properties |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92100766A Expired - Lifetime CN1023527C (en) | 1985-08-07 | 1992-02-09 | Process for preparation of polymer having isothianaphthene structure and electrochromic display |
Country Status (1)
| Country | Link |
|---|---|
| CN (3) | CN1007815B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1271227A1 (en) * | 2001-06-26 | 2003-01-02 | Nanomat Limited | Electrochromic display for high resolution and method of producing the same |
| CN101343352B (en) * | 2002-06-20 | 2011-08-17 | 华南理工大学 | Polymer containing selenium heterocyclic compound and application in preparing luminescent material |
| CN101885836B (en) * | 2002-06-20 | 2011-08-17 | 华南理工大学 | Polymer of selenium-contained heterocyclic compound and application thereof in preparation of luminescent material |
| DE602004020114D1 (en) * | 2003-01-31 | 2009-04-30 | Ntera Ltd | Electrochromic display device and its production method |
| TW200619301A (en) * | 2004-09-22 | 2006-06-16 | Showa Denko Kk | The water-soluable composition of antistatic agent, the antistatic agent, the method of forming antistatic film, coated products and pattern by using the same the agent |
| CN110139859A (en) * | 2016-12-28 | 2019-08-16 | 昭和电工株式会社 | It condenses miscellaneous polycyclic compound and has used the manufacturing method of the electric conductive polymer of the compound |
| CN114920911B (en) * | 2016-12-28 | 2024-05-03 | 株式会社力森诺科 | Method for producing polyisothiaindene conductive polymer |
-
1985
- 1985-08-07 CN CN85105974A patent/CN1007815B/en not_active Expired
- 1985-08-07 CN CN90100116A patent/CN1018874B/en not_active Expired
-
1992
- 1992-02-09 CN CN92100766A patent/CN1023527C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1007815B (en) | 1990-05-02 |
| CN1045410A (en) | 1990-09-19 |
| CN1063293A (en) | 1992-08-05 |
| CN85105974A (en) | 1987-02-04 |
| CN1023527C (en) | 1994-01-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN87108150A (en) | Conduction be with substituent polyisothianaphthene class | |
| CN86107279A (en) | Method of preparation of self-doped polymers | |
| KR0162864B1 (en) | Process for preparing electrically conductive polypyrrole having excellent solubility | |
| US4640748A (en) | Polyisothianaphtene, a new conducting polymer | |
| JP2014169271A (en) | Amide perfluoride salt and method for using the same as an ion-conductive substance | |
| CN1822410A (en) | Preparing organic light emitting film by electrochemical deposition and use in electroluminescence device | |
| US5405937A (en) | Polymers derived from fluorinated thiophenes, and conductive polymers derived therefrom | |
| CN1023527C (en) | Process for preparation of polymer having isothianaphthene structure and electrochromic display | |
| US4772940A (en) | Polymer having isothianaphthene structure and electrochromic display | |
| JPH075716B2 (en) | Process for producing N, N'-diphenylbenzidine polymer | |
| CN112271314A (en) | Flow battery positive electrode electrolyte based on tetrathiafulvalene dicarboxylic acid ethyl ester and preparation method thereof | |
| EP0164974B1 (en) | Polymer having isothianaphthene structure and electrochromic display | |
| Dai et al. | Dithenylpyrrole structure bridged with phenyl or biphenyl rings: Molecular configuration and electrochromic properties | |
| JPS6411207B2 (en) | ||
| JPH07130356A (en) | Electrode for secondary battery and secondary battery having the electrode | |
| CN1024067C (en) | Conducting substituted polyisothianaphthenes | |
| JP2012074209A (en) | Organic radical compound, battery electrode including the same, and battery | |
| JP2644800B2 (en) | Pyrrole polymer | |
| JPS63280727A (en) | Electrolytic polymerized film | |
| JP2862244B2 (en) | Pyrrole derivatives and polymers thereof | |
| JPS60203608A (en) | Preparation of electrically conductive polymer | |
| CN116082345A (en) | PMDQ, NTDQ, PTDQ and preparation method and application thereof | |
| JPS63196622A (en) | Production of polymer having isothianaphthene structure | |
| JPS62197421A (en) | Production of benzene polymer | |
| JPS63250482A (en) | Electrically conductive polymer composite and its production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C13 | Decision | ||
| GR02 | Examined patent application | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CX01 | Expiry of patent term |