CN101293961B - Electrochromic polymeric compounds, preparing method and application thereof - Google Patents
Electrochromic polymeric compounds, preparing method and application thereof Download PDFInfo
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- CN101293961B CN101293961B CN2008101081049A CN200810108104A CN101293961B CN 101293961 B CN101293961 B CN 101293961B CN 2008101081049 A CN2008101081049 A CN 2008101081049A CN 200810108104 A CN200810108104 A CN 200810108104A CN 101293961 B CN101293961 B CN 101293961B
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- 229920000642 polymer Polymers 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000000126 substance Substances 0.000 claims abstract description 34
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 27
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 26
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- 229930192474 thiophene Natural products 0.000 claims abstract description 19
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical group C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000003647 oxidation Effects 0.000 claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920000547 conjugated polymer Polymers 0.000 claims abstract description 7
- 238000006056 electrooxidation reaction Methods 0.000 claims abstract description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 42
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 32
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- -1 tetrafluoroborate ion Chemical class 0.000 claims description 21
- 229960001701 chloroform Drugs 0.000 claims description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 19
- 239000011521 glass Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- 150000002500 ions Chemical class 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- 239000000376 reactant Substances 0.000 claims description 12
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 claims description 9
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N pentanoic acid group Chemical group C(CCCC)(=O)O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 9
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 239000003115 supporting electrolyte Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- 239000007818 Grignard reagent Substances 0.000 claims description 6
- 238000002484 cyclic voltammetry Methods 0.000 claims description 6
- 150000004795 grignard reagents Chemical class 0.000 claims description 6
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 claims description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-Bis(diphenylphosphino)propane Substances C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 claims description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 5
- 150000001448 anilines Chemical class 0.000 claims description 5
- 150000001716 carbazoles Chemical class 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 5
- 150000002902 organometallic compounds Chemical class 0.000 claims description 5
- 150000003577 thiophenes Chemical class 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Chemical group O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 150000001642 boronic acid derivatives Chemical class 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000008151 electrolyte solution Substances 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000011133 lead Substances 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 101150003085 Pdcl gene Proteins 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229910001414 potassium ion Inorganic materials 0.000 claims description 2
- OGFYIDCVDSATDC-UHFFFAOYSA-N silver silver Chemical group [Ag].[Ag] OGFYIDCVDSATDC-UHFFFAOYSA-N 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 claims description 2
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 claims description 2
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims description 2
- 229940070710 valerate Drugs 0.000 claims description 2
- 230000004044 response Effects 0.000 abstract description 10
- 230000008859 change Effects 0.000 abstract description 2
- 238000002848 electrochemical method Methods 0.000 abstract description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 abstract 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 230000008021 deposition Effects 0.000 abstract 1
- 229910052731 fluorine Inorganic materials 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 239000000741 silica gel Substances 0.000 description 9
- 229910002027 silica gel Inorganic materials 0.000 description 9
- 238000004587 chromatography analysis Methods 0.000 description 8
- 238000000605 extraction Methods 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 description 7
- ZRJUDAZGVGIDLP-UHFFFAOYSA-N 2-bromo-1,10-phenanthroline Chemical class C1=CN=C2C3=NC(Br)=CC=C3C=CC2=C1 ZRJUDAZGVGIDLP-UHFFFAOYSA-N 0.000 description 5
- 238000004528 spin coating Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- YYJBWYBULYUKMR-UHFFFAOYSA-N 2-bromo-3-methylthiophene Chemical compound CC=1C=CSC=1Br YYJBWYBULYUKMR-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003233 pyrroles Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000004832 voltammetry Methods 0.000 description 2
- RXHZHGKMSAKVQN-UHFFFAOYSA-N 2-bromothiophene Chemical compound BrC1=CC=[C]S1 RXHZHGKMSAKVQN-UHFFFAOYSA-N 0.000 description 1
- 240000007582 Corylus avellana Species 0.000 description 1
- 235000007466 Corylus avellana Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 1
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- 150000002240 furans Chemical class 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention discloses an electrochromic polymer and a preparation method and an application thereof. The electrochromic polymer is a conjugated polymer containing phenanthroline groups in a main chain, showed in the general formula (I). In the formula (I), Ar is an electron-rich unit which is selected from units using thiophene, carbazole, diphenylamine, triphenylamine or fluorine as a main body; and n is a number from 3 to 20 and represents polymerization degree. The electrochromic polymer can be polymerized from the activated monomer in the structural formula (II) by an electrochemical oxidation method or a chemical oxidation method, and be applied to electrochromic devices. The electrochromic polymer can be reversibly oxidized or reduced to produce color change, and has the advantages of good stability and short response time. The film is directly and uniformly deposited and formed by the electrochemical method and the film thickness is adjusted by different deposition modes.
Description
(1) technical field
The present invention relates to a kind of electrochromic polymer, this electrochromic polymer can be used in the electrochromic device.
(2) background technology
Electrochromic material is promptly through electrooxidation and variable color or electroreduction and the material of variable color.The most important classes of compounds that shows electrochromic effect has: the coordination compound of transition metal oxide, Prussian blue system, viologen compound, conduction high polymer, transition metal and lanthanon.Wherein the superpolymer electrochromic material is a kind of novel electrochromic material; Because its in light weight, easy processing; Resistance can be regulated in a big way and to the characteristics such as good stability of environment; It is gathered around aspect electrochromic device have broad application prospects, become the focus of research over past ten years, and obtained a lot of achievements in research.
Mostly electrochromic polymer is conjugated structure, has certain specific conductivity and electrochemical activity, and the colour-change of certain limit can be provided during redox.At present research is more be through as the chemistry of the aromatic substance of pyrroles, thiophene, aniline, furans, carbazole, indoles or the polymkeric substance of electrochemical polymerization formation.The film of poly pyrrole of doping attitude is bluish voilet (λ max=670nm), obtains the not doping attitude of yellow-green colour (λ max=420nm) behind the electrochemical reduction.The verivate of polypyrrole also be widely used as electrochromic material (high tinkling of pieces of jades, the week fragrant I, Fan Guangyu. grip the present Research of superpolymer base intelligent glass window altogether. material Leader .1995 (2): 52-57.).Inganas etc. discover and carry out copolymerization to a plurality of electrochromism polymers; Transformation region that can controlling polymers; They have obtained material (Inganas O, Johansson T that the electrochromism response is exceedingly fast with verivate enedioxy thiophene and pyrroles's copolymerization of thiophene; Ghosh S.Phase Engineering for Enhanced Electrochromism in ConjugatedPolymers. [J] Electrochimica Acta.2001,46:2031-2034.).It is reported that CONTROLLED POTENTIAL is between 0.2V-0.6V; The color of polyaniline film can stably change between pale yellow-green more than 106 times reversiblely; Time of response 100ms (TETSUHIKO KOBAYASHI; HIROSHI YONEYAMA, HIDEO TAMURA.Polyaniline Film-CoatedElectrochromic Display Devices. [J] Electroanal Chem.1984,161:419-423).Also published summary about other electrochromic polymer materials in addition.(N.Rowley; R.Mortimer.New Electrochromic Materials. [J] ScienceProgress, 2002,85 (3): 243-262 and K.Ho; C.Greenberg; D.Macarthur.Electrochromic Materials. [J] Proceedings of the Electrochemical Society, 1997,96:23).The problem that exists at present is many electrochromic polymer stable limited at oxidation or reduced state.And because gegenion must be diffused in the polymer layer or from polymer layer and diffuse out, to keep charge balance, this process is restricted the time of response of electrochromic polymer.
(3) summary of the invention
The technical problem that the present invention will solve provides a kind of electrochromic polymer, and this polymkeric substance can reversible ground oxidation/reduction produce metachromatism, good stability, and the time of response is short.
The technical scheme that the present invention adopted is: a kind of electrochromic polymer, said electrochromic polymer are the conjugated polymers that main chain contains the phenanthroline group; Said conjugated polymers is shown in general formula (I):
In the formula (I); Ar is the electron rich unit, and said electron rich unit is selected from the unit that thiophene, carbazole, pentanoic, triphenylamine or fluorenes are main body, and described main body is meant on the ring of thiophene, carbazole, pentanoic, triphenylamine or fluorenes can not have substituting group; Also can have one or more substituting groups; Said substituting group can be alkyl, alkoxyl group etc., and preferred, said substituting group is selected from the alkyl of C1-C12, the alkoxyl group of C1-C12.N is 3～20, and is preferred 3～10, and n represents the polymerization degree.
Electrochromic polymer according to the invention is to be obtained through electrochemical oxidation or chemical oxidising polymerisation by reactive monomer, and the structural formula of said reactive monomer is suc as formula shown in (II):
In the formula (II); Ar is the electron rich unit, and said electron rich unit is selected from the unit that thiophene, carbazole, pentanoic, triphenylamine or fluorenes are main body, and described main body is meant on the ring of thiophene, carbazole, pentanoic, triphenylamine or fluorenes can not have substituting group; Also can have one or more substituting groups; Said substituting group is alkyl, alkoxyl group etc., and preferred, said substituting group is selected from the alkyl of C1-C12, the alkoxyl group of C1-C12.
The above-mentioned reactive monomer that is used to prepare electrochromic polymer can be through following method preparation:
Under the nitrogen protection, reactant A, catalyzer and phenanthroline bromide are added in the anhydrous and oxygen-free organic solvent B, fully reaction under-80～100 ℃ condition, reaction product obtains described reactive monomer through separating to purify.Described reactant A is for being organometallic compound or the boronic acid compounds that raw material makes with thiophene, substituted thiophene, carbazole, substituted carbazole, fluorenes, substituted fluorene, pentanoic, triphenylamine or substituted aniline; Said organometallic compound comprises Grignard reagent and organo-tin compound; The substituting group of said substituted thiophene, substituted carbazole, substituted fluorene or substituted aniline is one or more, and said substituting group is selected from alkyl, alkoxyl group etc., and preferred, said substituting group is selected from the alkyl of C1-C12, the alkoxyl group of C1-C12.
In the reactive monomer preparation, the anhydrous and oxygen-free operation is adopted in the reaction of reactant A and phenanthroline bromide, and generally with THF, DMAC N,N, N, dinethylformamide is as organic solvent B.The amount of substance ratio of said reactant A and phenanthroline bromide is 2～3: 1, is preferably 2.2～2.5: 1.Said catalyzer is the custom catalysts of general linked reaction, can select NiCl
2(dppp), PdCl
2(PPh
3)
2, Pd (PPh
3)
4Deng, catalyst consumption is a conventional amount used, catalyst concn is 10 in the recommendation response system
-3～10
-1Mol/L is preferably 5 * 10
-2～5 * 10
-1Mol/L.Said temperature of reaction is preferably 0～90 ℃, and is concrete, and according to the difference of reactant A, the preferable range of temperature of reaction is also different, preferred 0～70 ℃ of grignard reagent, preferred 80～90 ℃ of organo-tin compound, preferred 65～75 ℃ of boronic acid compounds.The linked reaction time is recommended as 2～30h, is preferably 8～12h.The separation of reaction product is purified can adopt following steps: with organic solvent (like trichloromethane, ether etc.) extraction, after sodium-chlor or the sodium hydroxide solution washing, use chromatographic separation (like silica gel again; Trichloromethane/n-hexane 1: 1); Remove and desolvate, vacuum-drying promptly obtains reactive monomer.Reactant A according to the invention is organometallic compound or the boronic acid compounds that raw material makes with thiophene, substituted thiophene, carbazole, substituted carbazole, fluorenes, substituted fluorene, pentanoic, triphenylamine or substituted aniline promptly, all can prepare according to existing method.
Concrete, the preparation method of the polymkeric substance described in the present invention has following two kinds:
(1) adopt electrochemical polymerization to prepare said electrochromic polymer; This preparation method is: electroanalysis solvent, reactive monomer and supporting electrolyte are added in the three-electrode cell form electrolytic solution; Adopt potentiostatic method, galvanostatic method or cyclic voltammetry galvanic deposit on working electrode to obtain polymeric film, the polymeric film that obtains promptly gets described electrochromic polymer through aftertreatment; The starting point concentration of reactive monomer is 10 in the said electrolytic solution
-3～10mol/L is preferably 10
-2Mol/L, the concentration of supporting electrolyte is 10
-3～10
-1Mol/L is preferably 10
-2Mol/L.
In above-mentioned electrochemical polymerization process; Described supporting electrolyte is supporting electrolyte commonly used; Generally be made up of in 1: 1 ratio negatively charged ion and positively charged ion, said negatively charged ion is perchlorate, tetrafluoroborate ion, hexafluorophosphoricacid acid ions, hexafluoroarsenate radical ion, nitrate ion, sulfonate ion, sulfate ion, formate ion, acetate ion, propionate ion, butyrate ion, valerate ion or phosphate anion; Said positively charged ion is sodium ion, potassium ion, lithium ion, hydrogen ion, ammonium radical ion, tetramethyl ammonium, tetraethyl ammonium ion, TBuA ion, four n-propyl ammonium ions or four n-hexyl ammonium ions.
Described electroanalysis solvent also is a common solvent; Like sulfuric acid, fluosulfonic acid, hydrogen fluoride, acetic acid, water, ammoniacal liquor, N; N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide, acetonitrile, toluene, ethanol, methyl alcohol, trichloromethane, methylene dichloride, THF, hexanaphthene, pyridine, propylene carbonate, benzyl cyanide, ether, acetate, formic acid, hydrochloric acid, phosphoric acid, sherwood oil etc.
In described three-electrode cell, working electrode can be gold, platinum, lead, titanium, graphite, glass carbon or ITO electrode; Supporting electrode can be gold, platinum, lead, titanium, Graphite Electrodes or ITO electrode; Reference electrode generally is silver-silver ion electrode, silver-silver chloride electrode or SCE.
Available cycles voltammetry of the present invention, potentiostatic method or galvanostatic method are carried out electrochemical polymerization, and those of ordinary skills can be through adjusting some electrochemical parameter settings so that film reaches desired thickness.
When adopting cyclic voltammetry to carry out galvanic deposit; The concrete recommendation carried out according to following steps: working electrode is applied triangular signal; The positive potential scope of triangular signal is-2～2V; The negative potential scope of triangular signal is-3～0.1V, and the time cycle is 10s～10min, thereby galvanic deposit obtains the polymeric film that thickness is 10～1000nm on working electrode.
When adopting potentiostatic method to carry out galvanic deposit; The concrete recommendation carried out according to following steps: working electrode is applied the constant potential signal; The constant potential range of signal is 1.2～2V, and the time is 200～1200s, thereby galvanic deposit obtains the film that thickness is 10～1000nm on working electrode.
When adopting galvanostatic method to carry out galvanic deposit, the concrete recommendation carried out according to following steps: working electrode is applied the continuous current signal, and the continuous current range of signal is 0.01～10mA/cm
2, the time is 200～1200s, thus galvanic deposit obtains the film that thickness is 10～1000nm on working electrode.
The film polymer that adopts electrochemical oxidation method to obtain among the present invention need be carried out aftertreatment usually, promptly cleans, drying, and concrete steps are following:
Can clean unreacted monomer residual on the electrodeposited film with solvent earlier; The solvent of selecting for use can be that purity is 5%～100% N; N-N,N-DIMETHYLACETAMIDE, N; Dinethylformamide, acetonitrile, toluene, ethanol, methyl alcohol, trichloromethane, methylene dichloride, THF, hexanaphthene, pyridine, propylene carbonate, benzyl cyanide, ether, acetate, formic acid or sherwood oil, scavenging period be recommended as 30 seconds～and 30 minutes; Electrodeposited film after the cleaning is dried under vacuum condition, and temperature is 10～50 ℃; Also available nitrogen dries up or natural air drying, obtains dry film.Drying mode and temperature can be confirmed according to the boiling point of solvent.
(2) adopt chemical oxidative polymerization method to prepare above-mentioned electrochromic polymer, this preparation process is:
In organic solvent C, be 1: 1～10 ratio mixed with reactive monomer and oxygenant by the amount of substance ratio, fully reaction under-40～60 ℃ of temperature obtains the conjugated polymers powder through separating to purify.Described oxygenant is one of following: FeCl
3, tosic acid iron, Witco 1298 Soft Acid iron; It is one of following that said organic solvent C can be selected from: DMAC N,N, N, dinethylformamide, acetonitrile, toluene, trichloromethane, methylene dichloride, THF, hexanaphthene, pyridine, propylene carbonate, benzyl cyanide, ether, sherwood oil etc.
Above-mentioned chemical oxidation method prepares in the electrochromic polymer process, and the reaction times is 1～20h, is preferably 8～12h.Preferred 15～25 ℃ of described temperature of reaction, said reactive monomer and FeCl
3The amount of substance ratio that feeds intake be preferably 1: 1～1.5.
Described separation is purified can adopt following steps: reaction product is directly poured in the water, and with same organic solvent C extraction, organic phase is washed respectively with saturated NaCl solution and pure water; Steam and remove organic solvent; Crude product removes and desolvates with (silica gel, trichloromethane/n-hexane 1: 1) chromatography; Drying gets final product.
The present invention can be dissolved in organic solvent C with the above-mentioned final product polymer powder that makes according to chemical oxidation method, adopts spin-coating method to make polymeric film.
Electrochromic polymer of the present invention can be applicable in the electrochromic device.
Electrochromic polymer according to the invention, can the oxidation of reversible ground reduction produce metachromatism, good stability, the time of response is short.Wherein electrochemical method can directly deposit film forming uniformly, and can regulate according to the difference of depositional mode the thickness of film.
(4) description of drawings
Fig. 1 be the electrochromic polymer film that makes of embodiment 2 when different voltage the UV-Vis abosrption spectrogram.
Fig. 2 is the variable color stability test figure of the electrochromic polymer film that makes of embodiment 1.
(5) embodiment
With specific embodiment technical scheme of the present invention is further described below, but protection scope of the present invention is not limited thereto.
Embodiment 1
3, the electrochemical synthesis of 8-two (2,2 '-thiophene)-phenanthroline polymkeric substance.
(1) 3,8-two (2,2 '-thiophene)-phenanthroline is monomeric synthetic
(0.72g 30mmol) transfers to round-bottomed flask with exsiccant THF (15ml) with the magnesium powder under nitrogen protection.(1.6g 10mmol), made the mixture room temperature reaction 2 hours to careful dropping 2 bromo-thiophene under constant speed stirs.After the filtration, through the careful Grignard reagent that drips preparation in advance of sleeve pipe to containing 3,8-two bromo-phenanthrolines (1.34g, 4mmol), [NiCl
2(dppp)] (0.070g, 0.127mmol) with three mouthfuls of round-bottomed flasks of exsiccant THF (15ml) mixture in, and in frozen water, be cooled to 0 ℃.Kept mixture 2 hours under the room temperature, 60 ℃ were refluxed 12 hours again.Use saturated NH
4The Cl aqueous solution finally goes out reactant, uses chloroform extraction, after the sodium chloride solution washing, and with (silica gel, trichloromethane/n-hexane 1: 1) chromatography.Remove and desolvate, vacuum-drying obtains yellow powder (1.24g, 90%).
(2) 3,8-two (2,2 '-thiophene)-phenanthroline polymkeric substance synthetic
With 3,8-two (2,2 '-thiophene)-phenanthroline monomer is dissolved in the methylene dichloride, and concentration is 10
-3～10
-1Mol/L, and add tetrabutylammonium perchlorate 10
-2Mol/L is as ionogen.Join in the three-electrode cell, wherein working electrode is an ito glass; Counter electrode is a platinized platinum; Reference electrode is a silver-silver chloride electrode.Adopt potentiostatic method to carry out polymerization, polymerization potential is 1.2V.Polymerization time 1000 seconds.After treating that polymerization is accomplished, will be with 3, the ito glass of 8-two (2,2 '-thiophene)-phenanthroline polymeric film cleaned in absolute ethyl alcohol 30 seconds.Obtain the exsiccant polymeric film behind the natural air drying.Utilize MALDI-TOF-MS to measure the polymerization degree of solid product, recording n is 3～8.
Embodiment 2
3, the electrochemical synthesis of 8-two (2,2 '-3 methyl thiophene)-phenanthroline polymkeric substance
(1) 3,8-two (2,2 '-3 methyl thiophene)-phenanthroline is monomeric synthetic
(0.72g 30mmol) transfers to round-bottomed flask with exsiccant THF (15ml) with activated carbon under nitrogen protection.(1.99g 11.25mmol), made the mixture room temperature reaction 2 hours to careful dropping 3-methyl-2-bromo-thiophene under constant speed stirs.Through filtering; Through the careful Grignard reagent that drips preparation in advance of sleeve pipe to containing 3; 8-two bromo-phenanthroline (1.51g; 4.5mmol), [NiCl2 (dppp)] (0.070g, 0.127mmol) with three mouthfuls of round-bottomed flasks of exsiccant THF (15ml) mixture in, and in frozen water, be cooled to 0 ℃.Kept mixture 2 hours under the room temperature, 60 ℃ were refluxed 12 hours again.Use saturated NH
4The Cl aqueous solution finally goes out reactant, uses chloroform extraction, after the sodium chloride solution washing, and with (silica gel, trichloromethane/n-hexane 1: 1) chromatography.Remove and desolvate, vacuum-drying obtains yellow powder (1.50g, 93%).
(2) 3,8-two (2,2 '-3 methyl thiophene)-phenanthroline polymkeric substance synthetic
3,8-two (2,2 '-3 methyl thiophene)-phenanthroline monomer is dissolved in the methylene dichloride, and concentration is 10
-3～10
-1Mol/L, and add tetrabutylammonium perchlorate 10
-2Mol/L is as ionogen.Join in the three-electrode cell, wherein working electrode is an ito glass; Counter electrode is a platinized platinum; Reference electrode is a silver-silver chloride electrode.Adopt potentiostatic method to carry out polymerization, polymerization potential is 1.2V.Polymerization time 1000 seconds.After treating that polymerization is accomplished, will be with 3, the ito glass of 8-two (2,2 '-3 methyl thiophene)-phenanthroline polymeric film cleaned in absolute ethyl alcohol 30 seconds.Obtain the exsiccant polymeric film behind the natural air drying.
Embodiment 3
3, the chemical oxidation of 8-two (2,2 '-3 methyl thiophene)-phenanthroline polymkeric substance is synthetic
(1) 3,8-two (2,2 '-3 methyl thiophene)-phenanthroline is monomeric to synthesize that (0.72g 30mmol) transfers to round-bottomed flask with exsiccant THF (15ml) with activated carbon under nitrogen protection.(1.99g 11.25mmol), made the mixture room temperature reaction 2 hours to careful dropping 3-methyl-2-bromo-thiophene under constant speed stirs.Through filtering; Through the careful Grignard reagent that drips preparation in advance of sleeve pipe to containing 3; 8-two bromo-phenanthroline (1.51g; 4.5mmol), [NiCl2 (dppp)] (0.070g, 0.127mmol) with three mouthfuls of round-bottomed flasks of exsiccant THF (15ml) mixture in, and in frozen water, be cooled to 0 ℃.Kept mixture 2 hours under the room temperature, 60 ℃ were refluxed 12 hours again.Use saturated NH
4The Cl aqueous solution finally goes out reactant, uses chloroform extraction, after the sodium chloride solution washing, and with (silica gel, trichloromethane/n-hexane 1: 1) chromatography.Remove and desolvate, vacuum-drying obtains yellow powder (1.50g, 93%).
(2) 3,8-two (2,2 '-3 methyl thiophene)-phenanthroline polymkeric substance synthetic
With 3,8-two (2,2 '-3 methyl thiophene)-(0.75g 2mmol) is dissolved in the methylene dichloride phenanthroline monomer; Concentration is 0.2mol/L, adds tosic acid iron 5g, reacts at normal temperatures 8 hours; The product of reaction is directly poured in the water, used dichloromethane extraction, saturated NaCl solution and pure water wash respectively three times; Steam with underspin at 40 ℃ and to remove methylene dichloride, product is with (silica gel, trichloromethane/n-hexane 1: 1) chromatography.Remove and desolvate, vacuum-drying gets brown look pressed powder (0.43g.57%).Utilize MALDI-TOF-MS to measure the polymerization degree of solid product, recording n is 4～8.
Spin coating: get the polymkeric substance 0.2g that makes and be dissolved in the 20ml methylene dichloride, spin-coating on the ito glass of cleaning obtains the polymeric film that thickness is 100nm.
Embodiment 4
3, the chemical oxidation of 8-two (2,2 '-3,4-two-butyl thiophene)-phenanthroline polymkeric substance is synthetic
(1) 3,8-two (2,2 '-3,4-dibutyl thiophene)-phenanthroline is monomeric synthetic
Under nitrogen protection with exsiccant 2-tributyl tin-3,4-dibutyl thiophene (3.57g, 10mmol), 3,8-two bromo-phenanthrolines (1.51g, 4.5mmol) and triphenylphosphine palladium chloride PdCl
2(PPh
3)
2(0.14g 2.5mmol) is dissolved in N, in the dinethylformamide (150ml), stirs down at 90 ℃, and keeps temperature 8 hours.Reaction has been distilled N after finishing, dinethylformamide, and product is with (silica gel, methyl alcohol/trichloromethane of 0.2%) chromatography.Remove and desolvate, vacuum-drying gets yellow solid powder (2.12g.60%).
Synthesizing of (2) 3,8-two (2,2 '-3,4-dibutyl thiophene)-phenanthroline polymkeric substance
With 3, (2,2 '-3,4-dibutyl thiophene)-(1.06g 2mmol) is dissolved in the methylene dichloride phenanthroline monomer 8-two, and concentration is 0.2mol/L, adds anhydrous FeCl
33g reacted 8 hours at normal temperatures, and the product of reaction is directly poured in the water, use dichloromethane extraction, and saturated NaCl solution and pure water wash respectively three times, removed methylene dichloride at 40 ℃ with underspin steaming, product usefulness (silica gel, trichloromethane/n-hexane 1: 1) chromatography.Remove and desolvate, vacuum-drying gets brown look pressed powder (0.68g.64%).Utilize MALDI-TOF-MS to measure the polymerization degree of solid product, recording n is 5～8.
Spin coating: get the polymkeric substance 0.2g that makes and be dissolved in the 20ml methylene dichloride, spin-coating on the ito glass of cleaning obtains the polymeric film that thickness is 100nm.
Embodiment 5
3, the electrochemical synthesis of 8-two (2,2 '-9,9-dibutyl fluorenes)-phenanthroline polymkeric substance
(1) 3,8-two (2,2 '-9,9-dibutyl fluorenes)-phenanthroline is monomeric synthetic
Under nitrogen protection with exsiccant 9,9-dibutyl fluorenes-hypoboric acid (3.25g, 10mmol), 3,8-two bromo-phenanthrolines (1.51g, 4.5mmol) and tetra-triphenylphosphine palladium Pd (PPh
3)
4(0.57g 0.5mmol) is dissolved in toluene (25ml), ethanol (12.5ml) and saturated NaCO
3In the mixing solutions (12.5ml), stir down, and kept temperature 24 hours at 70 ℃.Be cooled to room temperature, directly in entry, product is used chloroform extraction earlier, uses the NaCl solution washing then three times, uses (silica gel, normal hexane/trichloromethane 1: 1) chromatography at last.Remove and desolvate, vacuum-drying obtains white solid powder (2.72g.82.4%).
Synthesizing of (2) 3,8-two (2,2 '-9,9-dibutyl fluorenes)-phenanthroline polymkeric substance
With 3, (1.1g, 1.5mmol) in the methylene dichloride, concentration is 10 to 8-two (2,2 '-9,9-dibutyl fluorenes)-phenanthroline monomer
-3～10
-1Mol/L, and add tetrabutylammonium perchlorate 10
-2Mol/L is as ionogen.Join in the three-electrode cell, wherein working electrode is an ito glass; Counter electrode is a platinized platinum; Reference electrode is a silver-silver chloride electrode.Adopt galvanostatic method to carry out polymerization, the polymerization current density is 2mA/cm
2Polymerization time 600 seconds.After treating that polymerization is accomplished, will be with 3, the ito glass of 8-two (2,2 '-9,9-dibutyl fluorenes)-phenanthroline polymeric film cleaned in absolute ethyl alcohol 30 seconds.Use N
2Obtain the exsiccant polymeric film after drying up.Utilize MALDI-TOF-MS to measure the polymerization degree of solid product, recording n is 3～8.
Embodiment 6
3,8-two (2,2 '-thiophene)-electrochromism of phenanthroline polymkeric substance in acetonitrile
With the 3-thiophene-phenanthroline polymeric film on the ito glass that is attached to of preparation among the embodiment 1, put into three-electrode cell, Chi Zhongwei is dissolved with tetrabutylammonium perchlorate's acetonitrile solution.Wherein working electrode is for 3, the ito glass of 8-two (2,2 '-thiophene)-phenanthroline polymeric film; Counter electrode is a platinized platinum; Reference electrode is a silver-silver chloride electrode.Adopt cyclic voltammetry to scan, potential range is 0～1.5V, and sweep velocity is 3V/S, scans for 500 weeks.Can observe with the naked eye the rising of film, become cyan by brown with voltage, and behind loss of voltage, the color reverses back brown, so repeatedly.Response frequency with sweep speed identical.Relation on the record volt-ampere curve between redox peak and the polymeric film color.See table 1:
Table 1: the relation between redox peak and the polymeric film color
| Voltage range | 0～1.1V | 1.1～1.5V |
| Color | Brown | Cyan |
Embodiment 7
3,8-two (2,2 '-3 methyl thiophene)-electrochromism of phenanthroline polymkeric substance in acetonitrile
With 3 on the ito glass that be attached to of preparation among the embodiment 2,8-two (2,2 '-3 methyl thiophene)-the phenanthroline polymeric film, put into three-electrode cell, Chi Zhongwei is dissolved with tetrabutylammonium perchlorate's acetonitrile solution.Wherein working electrode is for 3, the ito glass of 8-two (2,2 '-3 methyl thiophene)-phenanthroline polymeric film; Counter electrode is a platinized platinum; Reference electrode is a silver-silver chloride electrode.Adopt the ladder voltammetry to scan, potential range is 0～1.5V, and sweep velocity is 20 seconds/rank, and every rank current potential increases 0.2V.Relation between record current potential and the polymeric film color.See table 2
Table 2: the relation between current potential and the polymeric film color
| Voltage | 0V | 0.2V | 0.4V | 0.6V | 0.8V | 1.0V | 1.2V | 1.4V | 1.6V |
| Color | Vandyke brown | Vandyke brown | Brown | Brown | Filbert | Nattierblue | Cyan | Cyan | Darkcyan |
In addition, the UV-Vis absorption spectrum of the polymeric film when measuring 1.0V-1.5V, resulting absorption peak.See Fig. 1.
Embodiment 8
3,8-two (2,2 '-thiophene)-the electrochromism response speed of phenanthroline polymkeric substance in acetonitrile
With 3 on the ito glass that be attached to of preparation among the embodiment 1,8-two (2,2 '-thiophene)-the phenanthroline polymeric film, put into three-electrode cell, Chi Zhongwei is dissolved with tetrabutylammonium perchlorate's acetonitrile solution.Wherein working electrode is for 3, the ito glass of 8-two (2,2 '-thiophene)-phenanthroline polymeric film; Counter electrode is a platinized platinum; Reference electrode is a silver-silver chloride electrode.The scanning of employing chronoamperometry: low potential is 0V; Noble potential is 1.5V; Potential pulse width 0.2～1 second; Scan 320 times.Can observe with the naked eye the film color with voltage pulse conversion between brown and cyan repeatedly.Response frequency is identical with the potential pulse width.
Embodiment 9
3,8-two (2,2 '-thiophene)-stability of phenanthroline polymkeric substance in acetonitrile
With 3 on the ito glass that be attached to of preparation among the embodiment 1,8-two (2,2 '-thiophene)-the phenanthroline polymeric film, put into three-electrode cell, Chi Zhongwei is dissolved with tetrabutylammonium perchlorate's acetonitrile solution.Wherein working electrode is for 3, the ito glass of 8-two (2,2 '-thiophene)-phenanthroline polymeric film; Counter electrode is a platinized platinum; Reference electrode is a silver-silver chloride electrode.Adopt cyclic voltammetry to scan, potential range is 0～1.5V, and sweep velocity is 3V/S, scans for 5000 weeks.Behind the end of scan, film portion dissolving attenuation, but variable color still exists.Fig. 2 is seen at redox peak before and after the scanning.
Claims (14)
1. an electrochromic polymer is characterized in that said electrochromic polymer is the conjugated polymers that main chain contains the phenanthroline group; Said conjugated polymers is shown in general formula (I):
In the formula (I), Ar is the electron rich unit, and said electron rich unit is selected from the unit that thiophene, carbazole, pentanoic, triphenylamine or fluorenes are main body, and n is 3～20, and n represents the polymerization degree.
2. one kind is used to prepare the reactive monomer of electrochromic polymer according to claim 1, and the structural formula of said reactive monomer is suc as formula shown in (II):
In the formula (II), Ar is the electron rich unit, and said electron rich unit is selected from the unit that thiophene, carbazole, pentanoic, triphenylamine or fluorenes are main body.
3. method for preparing electrochromic polymer as claimed in claim 1; It is characterized in that described electrochromic polymer is to be obtained through the electrochemical oxidation method polymerization suc as formula reactive monomer shown in (II) by structural formula; Said electrochemical oxidation method is following: electroanalysis solvent, reactive monomer and supporting electrolyte are added in the three-electrode cell form electrolytic solution; Adopt potentiostatic method, galvanostatic method or cyclic voltammetry galvanic deposit on working electrode to obtain polymeric film, the polymeric film that obtains promptly gets described electrochromic polymer through aftertreatment; The starting point concentration of reactive monomer is 10 in the said electrolytic solution
-3～10mol/L, the concentration of supporting electrolyte is 10
-3～10
-1Mol/L;
4. the preparation method of electrochromic polymer as claimed in claim 3; It is characterized in that described reactive monomer prepares according to following method: under the nitrogen protection; Reactant A, catalyzer and phenanthroline bromide are added in the anhydrous and oxygen-free organic solvent B; Fully reaction under-80～100 ℃ condition, reaction product obtains described reactive monomer through separating to purify; Said reactant A is for being organometallic compound or the boronic acid compounds that raw material makes with thiophene, substituted thiophene, carbazole, substituted carbazole, fluorenes, substituted fluorene, pentanoic, triphenylamine or substituted aniline; Described organometallic compound is Grignard reagent or organo-tin compound; The substituting group of said substituted thiophene, substituted carbazole, substituted fluorene, substituted aniline is one or more, and said substituting group is selected from alkyl, alkoxyl group; The amount of substance ratio of said reactant A and phenanthroline bromide is 2～3: 1, and described catalyzer is NiCl
2(dppp), PdCl
2(PPh
3)
2Or Pd (PPh
3)
4, described organic solvent B is THF, DMAC N,N or N, dinethylformamide.
5. the preparation method of electrochromic polymer as claimed in claim 4 is characterized in that in the catalyst concentration described in the reaction system be 10
-3～10
-1Mol/L.
6. like the preparation method of the described electrochromic polymer of one of claim 3～5; It is characterized in that described supporting electrolyte is made up of in 1: 1 ratio negatively charged ion and positively charged ion, said negatively charged ion is perchlorate, tetrafluoroborate ion, hexafluorophosphoricacid acid ions, hexafluoroarsenate radical ion, nitrate ion, sulfonate ion, sulfate ion, formate ion, acetate ion, propionate ion, butyrate ion, valerate ion or phosphate anion; Said positively charged ion is sodium ion, potassium ion, lithium ion, hydrogen ion, ammonium radical ion, tetramethyl ammonium, tetraethyl ammonium ion, TBuA ion, four n-propyl ammonium ions or four n-hexyl ammonium ions.
7. like the preparation method of the described electrochromic polymer of one of claim 3～5; It is characterized in that described electroanalysis solvent is one of following: sulfuric acid, fluosulfonic acid, hydrogen fluoride, water, ammoniacal liquor, N; N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide, acetonitrile, toluene, ethanol, methyl alcohol, trichloromethane, methylene dichloride, THF, hexanaphthene, pyridine, propylene carbonate, benzyl cyanide, ether, acetate, formic acid, hydrochloric acid, phosphoric acid, sherwood oil.
8. like the preparation method of the described electrochromic polymer of one of claim 3～5, it is characterized in that in the described three-electrode cell that working electrode is gold, platinum, lead, titanium, graphite, glass carbon or ITO electrode; Supporting electrode is gold, platinum, lead, titanium, Graphite Electrodes or ITO electrode; Reference electrode is silver-silver ion electrode, silver-silver chloride electrode or SCE.
9. like the preparation method of the described electrochromic polymer of one of claim 3～5; When it is characterized in that adopting cyclic voltammetry to carry out galvanic deposit; Specifically carry out according to following steps: working electrode is applied triangular signal, and the positive potential scope of triangular signal is-2～2V that the negative potential scope of triangular signal is-3～0.1V; Time cycle is 10s～10min, thereby galvanic deposit obtains the polymeric film that thickness is 10～1000nm on working electrode.
10. like the preparation method of the described electrochromic polymer of one of claim 3～5; When it is characterized in that adopting potentiostatic method to carry out galvanic deposit; Specifically carry out: working electrode is applied the constant potential signal according to following steps; The constant potential range of signal is 1.2～2V, and the time is 200～1200s, thereby galvanic deposit obtains the film that thickness is 10～1000nm on working electrode.
11. preparation method like the described electrochromic polymer of one of claim 3～5; When it is characterized in that adopting galvanostatic method to carry out galvanic deposit; Specifically carry out according to following steps: working electrode is applied the continuous current signal, and the continuous current range of signal is 0.01～10mA/cm
2, the time is 200～1200s, thus galvanic deposit obtains the film that thickness is 10～1000nm on working electrode.
12. preparation method like the described electrochromic polymer of one of claim 3～5; It is characterized in that the polymeric film that obtains carries out aftertreatment according to following steps: with solvent D unreacted monomer residual on the electrodeposited film is cleaned earlier; Described solvent D is the N of purity 5%～100%; N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide, acetonitrile, toluene, ethanol, methyl alcohol, trichloromethane, methylene dichloride, THF, hexanaphthene, pyridine, propylene carbonate, benzyl cyanide, ether, acetate, formic acid or sherwood oil; Electrodeposited film after the cleaning is through being drying to obtain product to the end.
13. the preparation method of an electrochromic polymer as claimed in claim 1; It is characterized in that described electrochromic polymer is to be obtained through the chemical oxidation method polymerization suc as formula reactive monomer shown in (II) by structural formula; Said chemical oxidation method is following: in organic solvent C; Described reactive monomer and oxygenant are pressed amount of substance than 1: 1～10 ratio mixed, and fully reaction under-40～60 ℃ of temperature obtains described electrochromic polymer through separating to purify; Described oxygenant is one of following: FeCl
3, tosic acid iron, Witco 1298 Soft Acid iron; Described organic solvent C is one of following: DMAC N,N, N, dinethylformamide, acetonitrile, toluene, trichloromethane, methylene dichloride, THF, hexanaphthene, pyridine, propylene carbonate, benzyl cyanide, ether, sherwood oil;
14. the application of electrochromic polymer as claimed in claim 1 in electrochromic device.
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| CN104628928B (en) * | 2015-01-29 | 2017-02-22 | 华南理工大学 | Photochromic fluorocarbon resin as well as preparation method and application thereof |
| CN106058067A (en) | 2016-08-19 | 2016-10-26 | 深圳市华星光电技术有限公司 | Organic electroluminescence diode and preparation method of cavity transmission layer thereof |
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| CN107991819B (en) * | 2017-11-23 | 2020-07-03 | 北京工业大学 | Method for improving Prussian blue electrochromic film on LiClO4Method for cyclic stability in PC electrolytes |
| CN109096507B (en) * | 2018-07-09 | 2021-04-06 | 浙江工业大学 | Triphenylamine derivative material based on imidazole type ionic liquid modification and preparation method and application thereof |
| CN110003233A (en) * | 2019-04-04 | 2019-07-12 | 西安交通大学 | Purple sieve essence small molecule, polymer, derivative and its application of a kind of chalcogen bridging |
| CN112430312B (en) * | 2019-08-26 | 2023-05-23 | 上海戎科特种装备有限公司 | Electrochromic polymer containing carbazole structure, preparation method, polymer film and application |
| CN111944108B (en) * | 2020-08-21 | 2022-04-08 | 中国人民解放军96901部队25分队 | Optical chirality adjustable electrochromic polymer, device and preparation method thereof |
| CN114316216B (en) * | 2021-11-17 | 2023-07-07 | 厦门华厦学院 | Symmetrical polymer based on dithieno quinoxaline matrix as center and flexible electrochromic device |
| CN114230580B (en) * | 2021-12-24 | 2023-01-24 | 吉林大学 | Multidentate organic ligand, preparation method and application thereof, metal supramolecular polymer and preparation method thereof |
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