CN105623642A - Novel electrochromic material P(6NIIn-co-EDOT) and preparation method thereof - Google Patents
Novel electrochromic material P(6NIIn-co-EDOT) and preparation method thereof Download PDFInfo
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- CN105623642A CN105623642A CN201610101394.9A CN201610101394A CN105623642A CN 105623642 A CN105623642 A CN 105623642A CN 201610101394 A CN201610101394 A CN 201610101394A CN 105623642 A CN105623642 A CN 105623642A
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- 6niin
- edot
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- nitroindoline
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- 239000000463 material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 60
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000000178 monomer Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 10
- LTNYDSMDSLOMSM-UHFFFAOYSA-N 6-nitro-2,3-dihydro-1h-indole Chemical compound [O-][N+](=O)C1=CC=C2CCNC2=C1 LTNYDSMDSLOMSM-UHFFFAOYSA-N 0.000 claims description 36
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- GOMPLJOPYGQBPL-UHFFFAOYSA-K [F-].[F-].[F-].F.[B+3] Chemical compound [F-].[F-].[F-].F.[B+3] GOMPLJOPYGQBPL-UHFFFAOYSA-K 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000007334 copolymerization reaction Methods 0.000 claims description 9
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 8
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 239000010935 stainless steel Substances 0.000 claims description 8
- 239000012790 adhesive layer Substances 0.000 claims description 7
- 238000005868 electrolysis reaction Methods 0.000 claims description 7
- 239000004576 sand Substances 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- YMMGRPLNZPTZBS-UHFFFAOYSA-N 2,3-dihydrothieno[2,3-b][1,4]dioxine Chemical compound O1CCOC2=C1C=CS2 YMMGRPLNZPTZBS-UHFFFAOYSA-N 0.000 claims 2
- 239000000126 substance Substances 0.000 abstract description 10
- PSWCIARYGITEOY-UHFFFAOYSA-N 6-nitro-1h-indole Chemical compound [O-][N+](=O)C1=CC=C2C=CNC2=C1 PSWCIARYGITEOY-UHFFFAOYSA-N 0.000 abstract 1
- -1 tetrabutylammonium tetrafluoroborate Chemical compound 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 description 17
- 239000012153 distilled water Substances 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 229920001940 conductive polymer Polymers 0.000 description 5
- 238000011010 flushing procedure Methods 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000002322 conducting polymer Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 125000000449 nitro group Chemical class [O-][N+](*)=O 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- WHLUQAYNVOGZST-UHFFFAOYSA-N tifenamil Chemical group C=1C=CC=CC=1C(C(=O)SCCN(CC)CC)C1=CC=CC=C1 WHLUQAYNVOGZST-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229940054051 antipsychotic indole derivative Drugs 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/29—Coupling reactions
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/44—Electrochemical polymerisation, i.e. oxidative or reductive coupling
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/54—Physical properties electrochromatic
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Abstract
The invention relates to a novel electrochromic material P(6NIIn-co-EDOT) and a preparation method thereof.The novel electrochromic material P(6NIIn-co-EDOT) is synthesized from two monomers of 6-nitroindole and 3,4-ethylenedioxythiophene in an acetonitrile solution system containing tetrabutylammonium tetrafluoroborate (TBATFB) through an electrochemical polymerization method.The prepared novel electrochromic material P(6NIIn-co-EDOT) has the stable chemical property, is good in thermal stability, wide in color-changing range and good in electrochromic property and is the electrochromic material which has the higher promotion value and good market prospect.
Description
Technical field
The present invention relates to a kind of novel electrochromic material and preparation method thereof, be specifically related to a kind of conducting polymer prepared by 6-nitroindoline and 3,4-ethylenedioxy thiophene copolymerization and preparation method thereof.
Background technology:
The research emphasis field requirement of " state natural sciences fund " 12 " development plan ", the design of study emphasis photoelectric material and preparation, the preparation of photoelectricity antetype device and performance characterization. Electrochromic material and device development are one of study hotspots of the outer photoelectric functional material of Present Domestic. There is the preparation of the conducting polymer of electrochromic property and performance all the time extensively by the concern of domestic and international research worker, people have done many explorations in electrochemical polymerization, wherein copolymerization can overcome the limitation of monomeric species as a kind of approach that can obtain novel conductive polymer, prepare the copolymer with good electric chemical property, optical property and high conductivity, especially there is better electrochromic property, present the material of particular color.
3,4-ethylenedioxy thiophenes serve not only as the monomer of a kind of high-performance polymer, also receive the concern of people as the excellent monomer of a kind of copolymerization. Poly-(3,4-ethylenedioxy thiophene) (PEDOT) not only have high conductivity, good chemical stability and activity, also having the electrochromic property of excellence, but its color can only change from light blue to navy blue, color change interval is comparatively single. On the other hand, Polyindole derivatives polymer has good redox active, electrochemical stability and heat stability, but electrical conductivity is relatively low. Accordingly, it is considered to the method for electrochemistry copolymerization prepares a kind of novel electrochromic polymeric material having advantage concurrently.
Summary of the invention:
The invention provides a kind of novel electrochromic material P (6NIIn-co-EDOT) and preparation method thereof, this polymer formulae is as shown in Figure 1. P (6NIIn-co-EDOT) is synthesized by electrochemical polymerization method in the acetonitrile solution system containing tetrafluoride boron TBuA (TBATFB) by two kinds of monomer 6-nitroindolines and 3,4-ethylenedioxy thiophenes, and polymerization current potential is low. Accompanying drawing 2 is the electrochemistry copolymerization route map of 6-nitroindoline and 3,4-ethylenedioxy thiophene.
The copolymer p (6NIIn-co-EDOT) of preparation has good electrochemical properties and good electrochromic property. Nitro is as a class electron withdraw group, it is possible to reduce energy barrier, improves the performance of conducting polymer, has very big effect in preparing conjugated conductive polymer. The research of the less electrochromic property to 6-nitroindoline in this area before this, but 6-nitroindoline has higher electro-chemical activity, is a kind of important indole derivatives.
The preparation method of novel electrochromic material P (6NIIn-co-EDOT) in the present invention comprises the following steps:
(1) Ag silk is in hydrochloric acid solution after potentiostatic deposition certain time, and Surface Creation AgCl adhesive layer, as reference electrode. Ito glass electrode is clean by alcohol wipe, as working electrode. The stainless steel electrode sand papering of 1200 orders, rinses successively with water, ethanol, acetone afterwards and dries up, as to electrode.
(2) by good for three combination of electrodes in step (1), put into tetrafluoride boron TBuA (TBATFB) acetonitrile solution containing 6-nitroindoline and 3,4-ethylenedioxy thiophenes, apply voltage, react certain time.
(3) working electrode in step (2) is taken out, with pocket knife, the polymeric film on working electrode is taken off, be placed in distilled water and soak 3 days, afterwards repeatedly with acetone and distilled water flushing, vacuum drying under uniform temperature.
Novel electrochromic material P (6NIIn-co-EDOT) prepared in the present invention has good electrochromic property. P (6NIIn-co-EDOT) being positioned over the light admission port place of ultraviolet spectrophotometer, can observe with the naked eye when applying the voltage of-0.4��1.0V, when P (6NIIn-co-EDOT) film is in reduction-state, the color of film is yellowish-brown; But when current potential is gradually increased, P (6NIIn-co-EDOT) film is oxidized gradually, the absorption that ��-�� * transition causes is gradually lowered, because polymer can form polaron and bipolaron when oxidation state, so that the color significant change of polymer, when P (6NIIn-co-EDOT) film is in oxidation state, the color of film is changed to nattierblue. Additionally in the indexs such as contrast, response time and coloration efficiency, P (6NIIn-co-EDOT) also has good performance.
Generally speaking, novel electrochromic material P (6NIIn-co-EDOT) prepared by the present invention has stable chemical property, good thermal stability, color change interval is relatively wide and electrochromic property is good, is a kind of electrochromic material with higher promotional value and bright market prospects.
Accompanying drawing explanation
The structural formula of Fig. 1 P (6NIIn-co-EDOT)
The electrochemistry copolymerization route map of Figure 26-nitroindoline and 3,4-ethylenedioxy thiophene
The infrared spectrum of copolymer in Figure 36-nitroindoline, 3,4-ethylenedioxy thiophenes and embodiment 1, wherein A is 6-nitroindoline monomer, and B is P (6NIIn-co-EDOT), C is 3,4-ethylenedioxy thiophene monomers
The nucleus magnetic hydrogen spectrum figure of copolymer in Figure 46-nitroindoline, 3,4-ethylenedioxy thiophenes and embodiment 1, wherein A is 6-nitroindoline monomer, and B is constant potential 1.35V P (6NIIn-co-EDOT), the C prepared is 3,4-ethylenedioxy thiophene monomers
The P (6NIIn-co-EDOT) of the preparation cyclic voltammetry curve that scanning 1000 is enclosed continuously in the acetonitrile/tetrafluoride boron TBuA solution of monomer-free, sweep speed: 100mVs in Fig. 5 embodiment 1-1
Prepare under Figure 66-nitroindoline, the polymer of 3,4-ethylenedioxy thiophene and different potentials
The thermal gravimetric analysis curve of P (6NIIn-co-EDOT), wherein A is poly-(6-nitroindoline), in B, C, D respectively embodiment 2,3,4 current potential 1.35,1.45, the P (6NIIn-co-EDOT) for preparing of 1.55V, E is poly-(3,4-ethylenedioxy thiophene)
In Fig. 7 embodiment 5, the P (6NIIn-co-EDOT) of preparation electrochromism-light at 465nm, 910nm place absorbs transformation curve
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be further described, but technical scheme is not limited in the description in embodiment.
Embodiment 1
(1) Ag silk is at 6molL-1In hydrochloric acid solution under constant potential 1.5V electrolysis 100s, Surface Creation AgCl adhesive layer, as reference electrode. Platinum electrode is calcination on alcohol burner, as working electrode. The stainless steel electrode sand papering of 1200 orders, rinses successively with water, ethanol, acetone afterwards and dries up, as to electrode.
(2) by good for above-mentioned three combination of electrodes, put in 0.1mol/L tetrafluoride boron TBuA (TBATFB) acetonitrile solution containing 6-nitroindoline and 3,4-ethylenedioxy thiophenes, apply the voltage of 1.35Vvs.SCE, react 10000s. Wherein: 6-nitroindoline monomer concentration is 0.02molL-1, the concentration of 3,4-ethylenedioxy thiophene monomer is 0.04molL-1. Its process for preparation is as follows: weighs solid tetrafluoride boron TBuA 0.1646g, solid 6-nitroindoline 0.0162g respectively, is dissolved in 5mL acetonitrile solution; Weighing solid tetrafluoride boron TBuA 0.1646g, liquid 3,4-ethylenedioxy thiophene 11.2uL is dissolved in 5mL acetonitrile solution; Weighing solid tetrafluoride boron TBuA 0.1646g, solid 6-nitroindoline 0.0162g respectively, liquid 3,4-ethylenedioxy thiophene 22.4uL is dissolved in 5mL acetonitrile solution.
(3) with pocket knife, the polymeric film on working electrode is taken off a part, is placed in distilled water and soaks 3 days, afterwards repeatedly with acetone and distilled water flushing, vacuum drying 48h at 60 DEG C, after be ground the sample as next step sign with mortar.
(4) working electrode being put into continuous scan cycle volt-ampere 1000 in the acetonitrile/TBATFB solution without monomer enclose, scanning voltage ranges for-0.2V to 1.5V, and sweep speed is 100mVs-1��
The infrared spectrogram of the three kinds of materials of copolymer prepared in 6-nitroindoline, 3,4-ethylenedioxy thiophenes and the present embodiment is shown in accompanying drawing 3, and wherein A is 6-nitroindoline monomer, and B is P (6NIIn-co-EDOT), C is 3,4-ethylenedioxy thiophene monomers. 6-nitroindoline is at 1600cm-1Place and 1300cm-1The absorption that antisymmetry is flexible and symmetry is flexible that two characteristic absorption peaks at place are nitro functions produces, the infrared spectrum of both copolymers have also been obtained close similar absworption peak, but there is skew somewhat, this existence that can illustrate to have 6-nitroindoline unit in copolymer. At 766cm-1And 820cm-1Locating two more weak absworption peaks is the absworption peak that in poly-(6-nitroindoline), C-H out-of-plane bending vibration produces, and this illustrates that phenyl ring occurs 1,2,4-tri-to replace, and illustrates to be polymerized on phenyl ring simultaneously. By C2-H and C3The disappearance of the absworption peak that deformation vibration produces inside and outside-H plane, it is possible to inferring, the polymerization site of 6-nitroindoline is the C shown in accompanying drawing 22And C3Position. Poly-(3,4-ethylenedioxy thiophene) is at 1088cm-1The characteristic absorption peak at place be by 3,4-ethylenedioxy thiophenes=stretching vibration of C-O key absorbs and produces, and also has similar absworption peak in the spectrogram of both copolymers herein. Simultaneously in the infrared spectrogram of P (6NIIn-co-EDOT) film, the rocking vibration of the C-S key of thiphene ring absorbs 975,920 and 836cm-1Place produces the absworption peak that intensity is general, and this shows that 3,4-ethylenedioxy thiophene unit are the same with 6-nitroindoline unit, has been embedded in the main chain of copolymer and has gone. It should be noted that in the infrared spectrogram of copolymer, at 1552cm-1Place yet suffers from the stretching vibration of N-H key and the absworption peak of bending vibration. This can illustrate, copolymer still contains N-H key, and the site at atom N place is not polymerization site during polymerization, and this has further demonstrated that the C at indole occurs in copolymerization site2And C3Position.
Accompanying drawing 4 is the nucleus magnetic hydrogen spectrum of the three kinds of materials of copolymer prepared in 6-nitroindoline, 3,4-ethylenedioxy thiophenes and the present embodiment, and wherein A is 6-nitroindoline monomer, and B is P (6NIIn-co-EDOT), C is 3,4-ethylenedioxy thiophene monomers. The spectrogram of 6-nitroindoline demonstrates five groups of chemical shift of proton, respectively: �� 6.6 (H-3), �� 7.8 (H-5 and H-2), �� 7.9 (H-4), �� 8.3 (H-7) and �� 12.1 (H-1). The spectrogram of 3,4-ethylenedioxy thiophenes demonstrates two groups of chemical shifts, respectively: �� 4.2 (aliphatic c h bond), �� 6.5 (thiphene ring c h bond). Wide than corresponding monomer of the chemical shift of proton of copolymer, this is because copolymer has wider molecular weight distribution. As shown in Figure 4, copolymer is primarily present four groups of chemical shifts, and the three groups of proton peak being wherein positioned at �� 7.9 (H-4 and H-5), �� 8.8 (H-7) and �� 12.3 (H-1) are to be produced by the phenyl ring in 6-nitroindoline unit. The chemical shift of proton being arranged in �� 4.2 is produced by 3,4-ethylenedioxy thiophene unit aliphatic c h bond. This illustrates that 6-nitroindoline is consistent with the conclusion of the Mechanism of Copolymerization of 3,4-ethylenedioxy thiophene Yu infrared spectrum gained.
In order to study the electrochemical stability of P (6NIIn-co-EDOT) film, in the acetonitrile without monomer/TBATFB solution, continuous scan cycle volt-ampere 1000 encloses, as shown in Figure 5. Along with cyclic voltammetric continuous print scans, P (6NIIn-co-EDOT) film is by oxidoreduction repeatedly, as seen from Figure 5, the electric current density at peak is in a slight decrease, and P (6NIIn-co-EDOT) film slightly degrades, after scanning 1000 is enclosed continuously, peak current density declines about 20%, and this shows that co-polymer membrane has good electrochemical stability.
Embodiment 2
(1) Ag silk is at 6molL-1In hydrochloric acid solution under constant potential 1.6V electrolysis 100s, Surface Creation AgCl adhesive layer, as reference electrode. Platinum electrode is calcination on alcohol burner, as working electrode. The stainless steel electrode sand papering of 1200 orders, rinses successively with water, ethanol, acetone afterwards and dries up, as to electrode.
(2) by good for above-mentioned three combination of electrodes, put in 0.1mol/L tetrafluoride boron TBuA (TBATFB) acetonitrile solution containing 6-nitroindoline and 3,4-ethylenedioxy thiophenes, apply the voltage of 1.35V.vs.SCE, react 10000s. Wherein: 6-nitroindoline monomer concentration is 0.02molL-1, the concentration of 3,4-ethylenedioxy thiophene monomer is 0.04molL-1. Its process for preparation is as follows: weighs solid tetrafluoride boron TBuA 0.1646g, solid 6-nitroindoline 0.0162g respectively, is dissolved in 5mL acetonitrile solution; Weighing solid tetrafluoride boron TBuA 0.1646g, liquid 3,4-ethylenedioxy thiophene 11.2uL is dissolved in 5mL acetonitrile solution; Weighing solid tetrafluoride boron TBuA 0.1646g, solid 6-nitroindoline 0.0162g respectively, liquid 3,4-ethylenedioxy thiophene 22.4uL is dissolved in 5mL acetonitrile solution.
(3) working electrode in step (2) is taken out, with pocket knife, the polymeric film on working electrode is taken off, be placed in distilled water and soak 3 days, afterwards repeatedly with acetone and distilled water flushing, vacuum drying 48h at 60 DEG C.
Embodiment 3
(1) Ag silk is at 6molL-1In hydrochloric acid solution under constant potential 1.5V electrolysis 100s, Surface Creation AgCl adhesive layer, as reference electrode. Platinum electrode is calcination on alcohol burner, as working electrode. The stainless steel electrode sand papering of 1200 orders, rinses successively with water, ethanol, acetone afterwards and dries up, as to electrode.
(2) by good for above-mentioned three combination of electrodes, put in 0.1mol/L tetrafluoride boron TBuA (TBATFB) acetonitrile solution containing 6-nitroindoline and 3,4-ethylenedioxy thiophenes, apply the voltage of 1.45V.vs.SCE, react 9000s. Wherein: 6-nitroindoline monomer concentration is 0.02molL-1, the concentration of 3,4-ethylenedioxy thiophene monomer is 0.04molL-1��
(3) working electrode in step (2) is taken out, with pocket knife, the polymeric film on working electrode is taken off, be placed in distilled water and soak 3 days, afterwards repeatedly with acetone and distilled water flushing, vacuum drying 48h at 60 DEG C.
Embodiment 4
(1) Ag silk is at 6molL-1In hydrochloric acid solution under constant potential 1.5V electrolysis 100s, Surface Creation AgCl adhesive layer, as reference electrode. Platinum electrode is calcination on alcohol burner, as working electrode. The stainless steel electrode sand papering of 1200 orders, rinses successively with water, ethanol, acetone afterwards and dries up, as to electrode.
(2) by good for above-mentioned three combination of electrodes, put in 0.2mol/L tetrafluoride boron TBuA (TBATFB) acetonitrile solution containing 6-nitroindoline and 3,4-ethylenedioxy thiophenes, apply the voltage of 1.55V.vs.SCE, react 8000s. Wherein: 6-nitroindoline monomer concentration is 0.02molL-1, the concentration of 3,4-ethylenedioxy thiophene monomer is 0.04molL-1��
(3) working electrode in step (2) is taken out, with pocket knife, the polymeric film on working electrode is taken off, be placed in distilled water and soak 3 days, afterwards repeatedly with acetone and distilled water flushing, vacuum drying 48h at 60 DEG C.
Accompanying drawing 6 is poly-(6-nitroindoline), gathers (3,4-ethylenedioxy thiophene) and embodiment 2,3,4 in the thermal gravimetric analysis curve of P (6NIIn-co-EDOT) film of preparation, polymerization current potential respectively 1.35V, 1.45V and 1.55V. Can intuitively being found out by Fig. 6, poly-(3,4-ethylenedioxy thiophene) heat stability is bad, and weightless ratio is very fast. When 350K owing to moisture evaporation starts weightlessness, reaching most degradation speed between 420K to 650K, mass loss is about 45%, and when temperature reaches 1050K, the mass loss of poly-(3,4-ethylenedioxy thiophene) is about about 74%. The heat stability of P (6NIIn-co-EDOT) film and poly-(6-nitroindoline) has similarity, and before 560K, thermogravimetric curve is basically identical. The thermal property of P (6NIIn-co-EDOT) film prepared under three kinds of current potentials is similar, has maximum degradation rate between 600K to 670K, and thermal loss total before 1050K is about 58%. As can be seen here, the heat stability of P (6NIIn-co-EDOT) film is better than gathering (3,4-ethylenedioxy thiophene).
Embodiment 5
(1) Ag silk is at 6molL-1In hydrochloric acid solution under constant potential 1.5V electrolysis 100s, Surface Creation AgCl adhesive layer, as reference electrode. Platinum electrode is calcination on alcohol burner, as working electrode. The stainless steel electrode sand papering of 1200 orders, rinses successively with water, ethanol, acetone afterwards and dries up, as to electrode.
(2) by good for above-mentioned three combination of electrodes, put in 0.1mol/L tetrafluoride boron TBuA (TBATFB) acetonitrile solution containing 6-nitroindoline and 3,4-ethylenedioxy thiophenes, apply the voltage of 1.35V.vs.SCE, react 15000s. Wherein: 6-nitroindoline monomer concentration is 0.01molL-1, the concentration of 3,4-ethylenedioxy thiophene monomer is 0.02molL-1��
(3) working electrode in step (2) is taken out, it is positioned over the light admission port place of ultraviolet spectrophotometer, adopt the method that square wave current potential and spectral absorption combine, primary voltage is changed at interval of 5s, under the scanning of square-wave voltage-0.4V and 1.0V, record co-polymer membrane is at 465nm and the 910nm optic response located, as shown in Figure 7.
Can drawing from figure at 465nm, optical contrast ratio is that transmitance converts response time required when 95%, it is necessary to 0.5s is painted, and 1.4s is reduced, and coloration efficiency is 192cm2C-1. At 910nm place, optical contrast ratio is that transmitance converts response time required when 95%, it is necessary to 0.6s is painted, and 2.2s is reduced, and coloration efficiency is 285cm2C-1, this is significantly larger than the value (50-70cm of the polypyrrole that document is recorded2C-1)��
Claims (10)
1. novel electrochromic material P (6NIIn-co-EDOT), it is characterised in that the structural formula of described P (6NIIn-co-EDOT) is as follows:
2. novel electrochromic material P (6NIIn-co-EDOT) as claimed in claim 1, it is characterized in that: described novel electrochromic material P (6NIIn-co-EDOT) is prepared from by electrochemical polymerization method copolymerization in acetonitrile/tetrafluoride boron TBuA solution system by monomer 6-nitroindoline and 3,4-ethylenedioxy thiophenes.
3. novel electrochromic material P (6NIIn-co-EDOT) as claimed in claim 1, it is characterised in that: polymerization adopts three-electrode system.
4. the preparation method according to arbitrary described novel electrochromic material P (6NIIn-co-EDOT) of claim 1-3, it is characterized in that: after good for three combination of electrodes, put into the 3 of the 6-nitroindoline containing 0.01-0.04mol/L and 0.02-0.05mol/L, in 0.05-0.25mol/L tetrafluoride boron TBuA (TBATFB) acetonitrile solution of 4-ethylenedioxy thiophene, apply the voltage of 1.2-1.55V.vs.SCE, react 5000-15000s.
5. method according to claim 4, it is characterized in that, after good for three combination of electrodes, put into the 3 of the 6-nitroindoline containing 0.02mol/L and 0.04mol/L, in 0.1mol/L tetrafluoride boron TBuA (TBATFB) acetonitrile solution of 4-ethylenedioxy thiophene, apply the voltage of 1.35V.vs.SCE, react 10000s.
6. the method as described in claim 4 or 5, it is characterised in that: adopting AgCl as reference electrode, ito glass electrode is as working electrode, and stainless steel electrode is as to electrode.
7. method as claimed in claim 6, it is characterised in that: being put into by Ag silk in the hydrochloric acid solution that concentration is 6mol/L, after electrolysis 100-150s under constant potential 1.4-1.6V, the AgCl adhesive layer that Surface Creation is red, as reference electrode.
8. method as claimed in claim 7, it is characterised in that: constant potential is 1.5V, electrolysis time 100s.
9. method as claimed in claim 6, it is characterised in that: the stainless steel electrode sand papering of 1200 orders, rinse successively with water, ethanol, acetone afterwards and dry up, as to electrode.
10. method as claimed in claim 6, it is characterised in that: ito glass electrode is clean by alcohol wipe, as working electrode.
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| WO2011042117A1 (en) * | 2009-10-09 | 2011-04-14 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Electrorheological fluid comprising organic dopants, and use thereof |
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| WO2011042117A1 (en) * | 2009-10-09 | 2011-04-14 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Electrorheological fluid comprising organic dopants, and use thereof |
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