CN104725611A - Carbazole-thiophene copolymer and application thereof - Google Patents
Carbazole-thiophene copolymer and application thereof Download PDFInfo
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- VFFMMTGRCBFHJJ-UHFFFAOYSA-N c1c[s]c(-c(cc2c3c4)ccc2[nH]c3ccc4-c2ccc[s]2)c1 Chemical compound c1c[s]c(-c(cc2c3c4)ccc2[nH]c3ccc4-c2ccc[s]2)c1 VFFMMTGRCBFHJJ-UHFFFAOYSA-N 0.000 description 2
- FIHILUSWISKVSR-UHFFFAOYSA-N Brc(cc1c2c3)ccc1[nH]c2ccc3Br Chemical compound Brc(cc1c2c3)ccc1[nH]c2ccc3Br FIHILUSWISKVSR-UHFFFAOYSA-N 0.000 description 1
- ARYHTUPFQTUBBG-UHFFFAOYSA-N OB(c1ccc[s]1)O Chemical compound OB(c1ccc[s]1)O ARYHTUPFQTUBBG-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a carbazole-thiophene copolymer and an application thereof. The carbazole-thiophene copolymer is obtained by polymerizing active monomers A and B with mole ratio of 1:(1-10) through electrochemical oxidation, wherein the active monomer A is a ferrocene group modified 3,6-dithiophene carbazole molecule, and a structural formula of the active monomer A is shown in a formula (I) in the specification; and the active monomer B is 3,4-ethylenedioxythiophene, and the structural formula of the active monomer B is shown in a formula (II) in the specification. The carbazole-thiophene copolymer can be used as an electrochromic material, is easy to prepare and low in cost, can realize reversible colour change at different voltages, and is rich in developing, good in cycling stability and excellent in response time and optical contrast.
Description
(1) technical field
The present invention relates to a kind of based on carbazole-thiophene-based electrochromic copolymer and the application as electrochromic material thereof.
(2) background technology
Along with socioeconomic high speed development, the energy and environmental problem become increasingly conspicuous, and the exploitation seeking the efficiency utilization of the energy and novel material is extremely urgent.Electrochromic material, as the novel energy-conserving and environment-protective material of a class, has potential application prospect in fields such as automobile rearview mirror, smart window, flexible membrane display screens.
The early stage research of electrochromic material focuses mostly in mineral-type materials, mainly because inorganic electrochromic material has good life-time service stability, but its materials processing is poor, color is dull and plasticity-is not strong, coloration efficiency is general not high, limits its large-scale application in productive life.
And organic electrochromic material can be divided into small molecules class electrochromic material and the large class of conductive polymers class electrochromic material two.Wherein organic molecule class fast response time, advantage that coloration efficiency is high, but the shortcoming having that colour-change is relatively dull, stability is not high, processability is poor equally.
Conductive polymers class electrochromic material is relative to traditional mineral-type and organic molecule class material, and have the advantage that they can not compare, such as raw material is cheaply easy to get, structure easily regulates, response speed very fast, coloration efficiency is more high.Therefore, conductive polymers is acknowledged as the main direction of studying of electrochromic material.For the application of display device aspect, polymer class electrochromic material also poor, the response speed of existence and stability comparatively slow, can not the problem of total colouring, also do not reach the requirement of marketization application.
Therefore prepare and multicolor displaying, fast response, polymer electrochromic material steady in a long-term can have great scientific meaning and practical value for the commercial applications realizing electrochromic device.
(3) summary of the invention
The technical problem to be solved in the present invention is to provide a kind of carbazole-thiophene-based multipolymer and the application as electrochromic material thereof, this polymkeric substance is prepared easy, with low cost, reversible colour-change can be realized under different voltage, colour developing is abundant, good cycling stability, the time of response and optical contrast more excellent.
Below the technical solution used in the present invention is illustrated.
The invention provides a kind of carbazole-thiophene-based multipolymer, described multipolymer is that the reactive monomer A of 1:1 ~ 1:10 and reactive monomer B to be polymerized by electrochemical oxidation method and to obtain by mol ratio, described reactive monomer A is 3 of ferrocene group modification, 6-bis-thiophene carbazole molecules (BTC-H-Fc), its structural formula is such as formula shown in (I); Described reactive monomer B is 3,4-rthylene dioxythiophene (EDOT), and its structural formula, as shown in (II), is purchased from Energy Reagent Company;
Further, described electrochemical oxidation method comprises the steps:
(1) be the reactive monomer A of 1:1 ~ 1:10 and reactive monomer B and supporting electrolyte by mol ratio, electroanalysis solvent adds in three-electrode cell and be mixed with electrolytic solution, in described electrolytic solution, the starting point concentration scope of two kinds of reactive monomers is all at 0.001 ~ 0.01mol/L, the concentration of supporting electrolyte is 0.001 ~ 0.1mol/L, electrolytic solution is polymerized at employing potentiostatic method in three-electrode cell, and galvanic deposit obtains co-polymer membrane on the working electrode (s;
(2) dedoping process is carried out to obtained co-polymer membrane, obtain the carbazole-thiophene-based co-polymer membrane deposited on the working electrode (s.
Further, in described step (1), described supporting electrolyte by negatively charged ion and positively charged ion in molar ratio 1 ︰ 1 ratio form, described negatively charged ion is that following one or more mix arbitrarily: perchlorate, tetrafluoroborate ion or hexafluorophosphoricacid acid ions, and described positively charged ion is that following one or more mix arbitrarily: lithium ion, tetramethyl ammonium, tetraethyl ammonium ion or TBuA ion; Described supporting electrolyte is preferably tetrabutylammonium perchlorate, lithium perchlorate or 4-butyl ammonium fluoroborate.Described supporting electrolyte concentration is in the electrolytic solution preferably 0.01 ~ 0.1mol/L.
Further, in described step (1), described electroanalysis solvent is selected from one of following: acetonitrile, trichloromethane or methylene dichloride, is preferably acetonitrile.
Further, in described step (1), described three-electrode cell is with gold, platinum or indium tin oxide-coated glass (ITO) electrode (being preferably ITO conductive glass electrode) are working electrode, with gold or platinum electrode (preferred platinum electrode) for supporting electrode, (biliquid direct type silver/silver chloride electrode is preferably with silver-silver chloride electrode, be that the first liquid connects with saturated potassium chloride solution, be that the second liquid connects with supporting electrolyte and corresponding electroanalysis solvent) for reference electrode, at constant potential 1.0 ~ 2.0V (preferably 1.0 ~ 1.5V, more preferably 1.22 ~ 1.38V) under condition, adopt potentiostatic method to carry out polyreaction (at room temperature to carry out, usual room temperature is 20 ~ 30 DEG C), polyreaction terminal judges according to consumes power 0.04 ~ 0.08C, the usual reaction times is 50 ~ 400s.
Further, in described step (2), described dedoping process is specially: the co-polymer membrane that step (1) is obtained is placed in same electrolytic solution, controlling potential is between-0.4 to-0.6V, first time dedoping process 100-200s is carried out to depositing co-polymer membrane working electrode, and then by (preferably one of following: acetonitrile for the working electrode electroanalysis solvent after first time dedoping process, trichloromethane or methylene dichloride, be more preferably acetonitrile) be placed in blank solution again after drip washing, the composition of the electrolytic solution that described blank solution uses with first time dedoping is distinguished and is only the former not containing reactive monomer A and reactive monomer B, control dedoping current potential and process 100s-200s between-0.4V to-0.6V, carry out the process of secondary dedoping, obtain the co-polymer membrane through dedoping process.
The co-polymer membrane that the present invention obtains after step (2) dedoping process does not need to peel off with working electrode, can be directly used in follow-up various tests.Also aftertreatment can be carried out according to application requiring to the co-polymer membrane through dedoping process, such as described electrochemical oxidation method can also comprise step (3): carried out by the co-polymer membrane through dedoping process cleaning, dry, cleaning solvent is acetonitrile, trichloromethane or methylene dichloride, is preferably acetonitrile; Dry 12 ~ 24 hours are recommended in 60 ~ 90 DEG C after cleaning.
The present invention is characterized by scanning electron microscope (SEM) pattern to multipolymer, confirms the formation of multipolymer.And carried out the structure of characterize polymers film by infrared spectra, further demonstrate that the formation of multipolymer.
Present invention also offers the application of described carbazole-thiophene-based multipolymer as electrochromic material.
The present invention has carried out electrochemical property test by ultraviolet electrochemistry spectrum to obtained multipolymer, test chart understands that multipolymer has outstanding electrochromic property, namely distinct colors change can be realized under different current potentials, and by the cyclic voltammetry curve of test polymer film under different scanning rates, even if find the polymeric film that generates very high sweep speed under remain non-diffusing control process, illustrates that the polymeric film obtained has the electrochromic property of excellence.
The present invention has also carried out contrast gradient test by ultraviolet electrochemistry spectrum to multipolymer, and has carried out stability analysis by electrochemical workstation to it.
Compared with prior art, the beneficial effect of the preparation method of the multipolymer described in the present invention is mainly reflected in:
(1) preparation method of the present invention is easy, does not need harsh reaction conditions, just can operate under room temperature, and does not need complicated purification process, and product purity is high;
(2) resulting polymers nearly cover is at whole electrode surface, and macroscopic view presents membranaceous, so can directly be used for doing various test, avoids the complex process that chemical oxidising polymerisation obtains wanting when pulverous product does various test wiring solution-forming film.
(3) multipolymer prepared has electrochromic performance, namely can produce distinct colors change under different applying current potentials, thus can be applied to liquid-crystal display, the fields such as smart window.
(4) accompanying drawing explanation
Fig. 1 is the SEM figure of the copolymer film that the embodiment of the present invention 1 obtains.
Fig. 2 is the infrared spectrogram of the copolymer film that the embodiment of the present invention 1,2,3 obtains.
Fig. 3 is the ultraviolet spectrogram of the copolymer film that the embodiment of the present invention 1 obtains.
Fig. 4 is the colour developing figure of copolymer film under different voltage that the embodiment of the present invention 1 obtains, and colour developing is from left to right changed to yellow-green colour, careless look, Mu Zeise, cyanosis look.
Fig. 5 is the stable form curves of copolymer film circulation 300 circle that the embodiment of the present invention 1 obtains.
Fig. 6 is that the obtained copolymer film of the embodiment of the present invention 1 is respectively at the contrast gradient figure of 390nm, 690nm and 1100nm.
Fig. 7 is the SEM figure of the copolymer film that the embodiment of the present invention 2 obtains;
Fig. 8 is the ultraviolet spectrogram of the copolymer film that the embodiment of the present invention 2 obtains.
Fig. 9 is the obtained colour developing figure of copolymer film under different voltage of the embodiment of the present invention 2, and colour developing is from left to right changed to cyanosis look, shallow sapanwood look, mouse look, pine needle look, rattan receive Kobe, dark purple is blue.
Figure 10 is the stable form curves of copolymer film circulation 300 circle that the embodiment of the present invention 2 obtains.
Figure 11 is that the obtained copolymer film of the embodiment of the present invention 2 is respectively at the contrast gradient figure of 408nm, 710nm and 1100nm.
Figure 12 is the SEM figure of the copolymer film that the embodiment of the present invention 3 obtains;
Figure 13 is the ultraviolet spectrogram of the copolymer film that the embodiment of the present invention 3 obtains.
Figure 14 is the obtained colour developing figure of copolymer film under different voltage of the embodiment of the present invention 3, and colour developing is from left to right changed to atropurpureus, Red sea dark brown, mouse look, rotten leaf look, Qiang shallow green onion look, pine needle look, secret look, blueness always.
Figure 15 is the stable form curves of copolymer film circulation 300 circle that the embodiment of the present invention 3 obtains.
Figure 16 is that the obtained copolymer film of the embodiment of the present invention 3 is respectively at the contrast gradient figure of 410nm, 570nm and 1100nm.
(5) embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this:
The present invention adopts constant potential polymerization to prepare co-polymer membrane.The instrument adopted in whole preparation process is electrochemical workstation (CHI660C, Shanghai Chen Hua instrument company) and three-electrode system.
The preparation embodiment of BTC-H-Fc:
Synthetic route is:
(1) synthesis of BTC: by 3; 6-dibromo carbazole (1.43g; 3mmol); 2-thienyl boric acid (0.48g; 7mmol); four (triphenyl phosphorus) palladium (0.2mmol) and sodium carbonate (2.0M, 5mL) are dissolved in the mixing solutions of tetrahydrofuran (THF) (20mL) and toluene (30mL) under nitrogen protection, system back flow reaction 48 hours.With deionized water and dichloromethane extraction after system cooling, after gained organic phase adds anhydrous MgSO4 drying, use column chromatography purification again, stationary phase is 300 order silica gel, moving phase is ethyl acetate/petroleum ether (1:20, V), finally obtain the target product 0.68g of white solid state, productive rate is 68%.
(2) synthesis of Fc-H-Cl: by ferrocenecarboxylic acid (1.15g, 5mmol) join in methylene dichloride, at room temperature stir 20 minutes, then EDCI (1.15g is added, 6mmol) with DMAP (0.31g, 2.5mmol), after dissolving, add 6-bromine hexanol (0.88g, 6.5mmol), at room temperature stir after 24 hours and terminate to react.Reactant deionized water and dichloromethane extraction, after gained organic phase adds anhydrous MgSO4 drying, use column chromatography purification again, stationary phase is 300 order silica gel, moving phase is ethyl acetate/petroleum ether (1:150, V), finally obtain the target product 1.3g of reddish-brown oily, productive rate is 77%.
(3) synthesis of BTC-H-Fc: added by potassium hydroxide in DMF, stirs and adds carbazole after 10 minutes, continues stirring and adds Fc-H-Cl after 1 hour.Reaction system is warming up to 50 DEG C, stirs after 24 hours and terminates reaction.Cross leaching filter residue after adding a large amount of frozen water, after deionized water wash drying, then use column chromatography purification, stationary phase is 300 order silica gel, and moving phase is ethyl acetate/petroleum ether (1:30, V), finally obtain the target product 0.89g of reddish-brown oily, productive rate is 69%.
Embodiment 1
Two kinds of monomer A (BTC-H-Fc, the thiophene carbazole derivative that a kind of ferrocene is modified) and B (EDOT) carry out electrochemistry copolymerization according to mol ratio 1:1 and obtain P (BTC-H-FC/EDOT)-1.
Operating process:
(1) preparation of the co-polymer membrane of monomer A and monomers B: monomer A (initial oxidation current potential: 0.72V), monomers B (initial oxidation current potential: 1.27V) and tetrabutylammonium perchlorate's (TBuA ion is 1:1 with the mol ratio of perchlorate) are mixed with acetonitrile, is mixed with the mixing solutions 100mL that monomer A and monomers B starting point concentration are 0.001mol/L, supporting electrolyte concentration 0.1mol/L.Adopt tetrabutylammonium perchlorate's (mol ratio of TBuA ion and perchlorate is 1:1) as supporting electrolyte, three-electrode system selected by electrolyzer, using ITO conductive glass as working electrode (successively at trichloromethane, acetone, supersound washing 10min in ethanol), using polished platinized platinum (surface-brightening is smooth) as supporting electrode (Pt, 2cm × 2cm), reference electrode adopts biliquid direct type silver/silver chloride electrode (Ag/AgCl, saturated potassium chloride solution connects as the first liquid, the dichloromethane solution of 0.1mol/L tetrabutylammonium perchlorate connects as the second liquid).Under room temperature (25 DEG C) condition, adopt constant potential anodic oxidation polymerization legal system for co-polymer membrane, i.e. polyreaction 100s under polymerization potential is 1.36V vs.Ag/AgCl, consumes power is 0.05C, polymerization terminates, working electrode ITO conductive glass surface deposited the polymeric film of blue layer, dedoping process is carried out to obtained co-polymer membrane, namely in same electrolytic solution, controlling potential is-0.6V vs.Ag/AgCl, a dedoping process 200s is carried out to the working electrode after polyreaction, blank solution (i.e. the acetonitrile solution of 0.1mol/L tetrabutylammonium perchlorate) will be placed in again after the drip washing of working electrode acetonitrile, in blank solution, control dedoping current potential is again-0.6V vs.Ag/AgCl, time is 100s, carry out the process of secondary dedoping, obtain the working electrode of surface deposition copolymer film.
(2) the electrochromic property test of P (BTC-H-FC/EDOT)-1
Can the surperficial microstructure of test polymer film by scanning electron microscope.The scanning electron microscope analysis of P (BTC-H-FC/EDOT)-1, as Fig. 1, can see copolymer film surfacing, exquisiteness, and the PEC device of smooth, fine and smooth surface to processability excellence is very favorable.
The test of ultraviolet uv-absorbing, the test of contrast gradient and the calculating of time of response can be carried out to polymeric film by electrochemical workstation and ultraviolet-visible spectrophotometer coupling.When being applied to 0V voltage on P (BTC-H-Fc/EDOT)-1 film, the maximum absorption band that film is corresponding is positioned at 390nm place, this absorption be by polymer chain on π – π * transition cause.Along with executing alive increase; the intensity of π – π * transition reduces gradually, causes the absorption peak strength at 390nm place to reduce gradually, the doping level of EC polymkeric substance is deepened gradually simultaneously, create polaron, cause the new absorption peak of the appearance near 690nm place and 1100nm.Ultraviolet electrochemistry spectrum test (shown in Fig. 3) shows that multipolymer carries out oxide treatment under different potentials between-0.4 ~ 1.8V, presents the change (Fig. 4) of yellowish green (-0.2V), careless look (0.4V), scouring rush's look (1.2V), cyanosis (1.6V) 4 kinds of distinct colors.
With electrochemical workstation and ultraviolet-spectrophotometer coupling, kinetic test is carried out to electronic color-changing material.Optical contrast and time of response are also the important parameters of electrochromic material two.According to ultraviolet spectrogram before, to P (BTC-H-Fc/EDOT)-1, we have selected 390nm and 690nm two visible region wavelength and 1100nm near infrared wavelength.Fig. 6 record be the optical contrast of P (BTC-H-Fc/EDOT)-1 film at different wave length place and time of response test pattern.Current potential switches between 0V and 1.4V, and step time is 5s.Analysis chart 6 is known, and polymer P (BTC-H-Fc/EDOT)-1 is respectively 11%, 15% and 27% in the contrast gradient at 390nm, 690nm and 1100nm place, and the time of response is respectively 1.7s, 1.9s and 1.9s.
The stability of co-polymer membrane P (BTC-H-FC-EDOT)-1 is tested by cyclic voltammetry.The polymeric film obtained with constant potential polymerization process is placed in blank solution and carries out cyclic voltammetry, electric potential scanning scope is-0.4V-1.45V, and sweep velocity is 300mVs
-1.We delineate the scanning curve (Fig. 5) of P (BTC-H-FC/EDOT)-1 the 1st week and the 300th week.Analyze known, after scanning 300 weeks, P (BTC-H-Fc/EDOT)-1 copolymer film maintains the electroactive of original state 36.9%.
Embodiment 2
Two kinds of monomer A (BTC-H-Fc, the thiophene carbazole derivative that a kind of ferrocene is modified) and the ratio of monomers B (EDOT) become 1:5 from the 1:1 of embodiment 1, and polymerization obtains P (BTC-H-FC/EDOT)-5.
Operating process:
(1) preparation of the co-polymer membrane of monomer A and monomers B: monomer A (initial oxidation current potential: 0.72V), monomers B (initial oxidation current potential: 1.27V) and tetrabutylammonium perchlorate's (TBuA ion is 1:1 with the mol ratio of perchlorate) are mixed with acetonitrile, be mixed with monomer A and starting point concentration be 0.001mol/L, monomers B starting point concentration is the mixing solutions 100mL of 0.005mol/L, supporting electrolyte concentration 0.1mol/L.Adopt tetrabutylammonium perchlorate's (mol ratio of TBuA ion and perchlorate is 1:1) as supporting electrolyte, three-electrode system selected by electrolyzer, using ITO conductive glass as working electrode (successively at trichloromethane, acetone, supersound washing 10min in ethanol), using polished platinized platinum (surface-brightening is smooth) as supporting electrode (Pt, 2cm × 2cm), reference electrode adopts biliquid direct type silver/silver chloride electrode (Ag/AgCl, saturated potassium chloride solution connects as the first liquid, the dichloromethane solution of 0.1mol/L tetrabutylammonium perchlorate connects as the second liquid).Under room temperature (25 DEG C) condition, adopt constant potential anodic oxidation polymerization legal system for co-polymer membrane, i.e. polyreaction 100s under polymerization potential is 1.36V vs.Ag/AgCl, consumes power is 0.05C, polymerization terminates, working electrode ITO conductive glass surface deposited the polymeric film of blue layer, dedoping process is carried out to obtained co-polymer membrane, namely in same electrolytic solution, controlling potential is-0.6V vs.Ag/AgCl, a dedoping process 200s is carried out to the working electrode after polyreaction, by working electrode acetonitrile, blank solution (i.e. the acetonitrile solution of 0.1mol/L tetrabutylammonium perchlorate) is placed in again after trichloromethane or eluent methylene chloride, in blank solution, control dedoping current potential is again-0.6V vs.Ag/AgCl, time is 100s, carry out the process of secondary dedoping, obtain the working electrode of surface deposition copolymer film.
(2) the electrochromic property test of P (BTC-H-FC/EDOT)-5
Can the surperficial microstructure of test polymer film by scanning electron microscope.The scanning electron microscope analysis of P (BTC-H-FC/EDOT)-5, as Fig. 7, can see that copolymer film surface is also very smooth, fine and smooth, and the PEC device of smooth, fine and smooth surface to processability excellence is very favorable.
The test of ultraviolet uv-absorbing, the test of contrast gradient and the calculating of time of response can be carried out to polymeric film by electrochemical workstation and ultraviolet-visible spectrophotometer coupling.When being applied to 0V voltage on P (BTC-H-Fc/EDOT)-5 film, the maximum absorption band that film is corresponding is positioned at 408nm place, this absorption be by polymer chain on π – π * transition cause.Along with executing alive increase; the intensity of π – π * transition reduces gradually, causes the absorption peak strength at 408nm place to reduce gradually, the doping level of EC polymkeric substance is deepened gradually simultaneously, create polaron, cause the new absorption peak of the appearance near 770nm place and 1100nm.Ultraviolet electrochemistry spectrum test (Fig. 8 shown in) shows that multipolymer carries out oxide treatment under different potentials between-0.4 ~ 1.8V, presents cyanosis (-0.6V), change (Fig. 9) that shallow sapanwood (0.2V), mouse look (0.4V), pine needle look (0.6V), rattan receive Kobe (0.8V), dark purple indigo plant (1.2V) 6 kinds of distinct colors.
With electrochemical workstation and ultraviolet-spectrophotometer coupling, kinetic test is carried out to electronic color-changing material.Optical contrast and time of response are also the important parameters of electrochromic material two.According to ultraviolet spectrogram before, to P (BTC-H-Fc/EDOT)-5, we have selected 408nm and 770nm two visible region wavelength and 1100nm near infrared wavelength.Figure 11 record be the optical contrast of P (BTC-H-Fc/EDOT)-5 film at different wave length place and time of response test pattern.Current potential switches between 0V and 1.4V, and step time is 5s.Analysis Figure 11 is known, and polymer P (BTC-H-Fc/EDOT)-5 is respectively 20%, 27% and 30.1% in the contrast gradient at 474nm, 750nm and 1100nm place, and the time of response is respectively 2.5s, 1.2s and 1.7s.
The stability of co-polymer membrane P (BTC-H-FC-EDOT)-5 is tested by cyclic voltammetry.The polymeric film obtained with constant potential polymerization process is placed in blank solution and carries out cyclic voltammetry, electric potential scanning scope is-0.4V-1.45V, and sweep velocity is 300mVs
-1.We delineate the scanning curve (Figure 10) of P (BTC-H-FC/EDOT)-5 the 1st weeks and the 300th week.Analyze known, after scanning 300 weeks, P (BTC-H-Fc/EDOT)-5 copolymer film maintains the electroactive of original state 70%.
Embodiment 3
Two kinds of monomer A (BTC-H-Fc, the thiophene carbazole derivative that a kind of ferrocene is modified) and the ratio of B (EDOT) become 1:10, and polymerization obtains P (BTC-H-FC/EDOT)-10.
Operating process:
(1) preparation of the co-polymer membrane of monomer A and monomers B: monomer A (initial oxidation current potential: 0.72V), monomers B (initial oxidation current potential: 1.27V) and tetrabutylammonium perchlorate's (TBuA ion is 1:1 with the mol ratio of perchlorate) are mixed with acetonitrile, is mixed with that monomer A starting point concentration is 0.001mol/L, monomers B starting point concentration is 0.01mol/L, the mixing solutions 100mL of supporting electrolyte concentration 0.1mol/L.Adopt tetrabutylammonium perchlorate's (mol ratio of TBuA ion and perchlorate is 1:1) as supporting electrolyte, three-electrode system selected by electrolyzer, using ITO conductive glass as working electrode (successively at trichloromethane, acetone, supersound washing 10min in ethanol), using polished platinized platinum (surface-brightening is smooth) as supporting electrode (Pt, 2cm × 2cm), reference electrode adopts biliquid direct type silver/silver chloride electrode (Ag/AgCl, saturated potassium chloride solution connects as the first liquid, the dichloromethane solution of 0.1mol/L tetrabutylammonium perchlorate connects as the second liquid).Under room temperature (25 DEG C) condition, adopt constant potential anodic oxidation polymerization legal system for co-polymer membrane, i.e. polyreaction 100s under polymerization potential is 1.36V vs.Ag/AgCl, consumes power is 0.05C, polymerization terminates, working electrode ITO conductive glass surface deposited the polymeric film of blue layer, dedoping process is carried out to obtained co-polymer membrane, namely in same electrolytic solution, controlling potential is-0.4V vs.Ag/AgCl, a dedoping process 200s is carried out to the working electrode after polyreaction, by working electrode acetonitrile, blank solution is placed in again after trichloromethane or eluent methylene chloride, be preferably acetonitrile.In blank solution (i.e. the acetonitrile solution of 0.1mol/L tetrabutylammonium perchlorate), controlling dedoping current potential is again-0.4Vvs.Ag/AgCl, and the time is 100s, carries out the process of secondary dedoping, obtains the working electrode of surface deposition copolymer film.
(2) the electrochromic property test of P (BTC-H-FC/EDOT)-10
Can the surperficial microstructure of test polymer film by scanning electron microscope.The scanning electron microscope analysis of P (BTC-H-FC/EDOT)-10 is as Figure 12, can see that copolymer film surface is more evenly fine and smooth compared to P (BTC-H-FC/EDOT)-1 and P (BTC-H-FC/EDOT)-5, and more smooth, fine and smooth surface to the PEC device of processability excellence advantageously.
The test of ultraviolet uv-absorbing, the test of contrast gradient and the calculating of time of response can be carried out to polymeric film by electrochemical workstation and ultraviolet-visible spectrophotometer coupling.When being applied to 0V voltage on P (BTC-H-Fc/EDOT)-10 film, the maximum absorption band that film is corresponding is positioned at 410nm place, this absorption be by polymer chain on π – π * transition cause.Along with executing alive increase; the intensity of π – π * transition reduces gradually, causes the absorption peak strength at 410nm place to reduce gradually, the doping level of EC polymkeric substance is deepened gradually simultaneously, create polaron, cause the new absorption peak of the appearance near 570nm place and 1100nm.Ultraviolet electrochemistry spectrum test (shown in Figure 13) shows that multipolymer carries out oxide treatment under different potentials between-0.4 ~ 1.8V, presents the change (Figure 14) of purple black (-0.6V), the old tea in Red sea (0.2V), mouse look (0.3V), rotten leaf look (0.4V), the shallow green onion of Qiang (0.6V), pine needle look (0.8V), secret look (0.9V), blue (1.4V) 8 kinds of distinct colors.
With electrochemical workstation and ultraviolet-spectrophotometer coupling, kinetic test is carried out to electronic color-changing material.Optical contrast and time of response are also the important parameters of electrochromic material two.According to ultraviolet spectrogram before, to P (BTC-H-Fc/EDOT)-10, we have selected 410nm and 570nm two visible region wavelength and 1100nm near infrared wavelength.Figure 16 record be the optical contrast of P (BTC-H-Fc/EDOT)-10 film at different wave length place and time of response test pattern.Current potential switches between 0V and 1.4V, and step time is 5s.Analysis Figure 16 is known, and polymer P (BTC-H-Fc/EDOT)-10 is respectively 17%, 15% and 25% in the contrast gradient at 474nm, 750nm and 1100nm place, and the time of response is respectively 3.1s, 1.7s and 2.5s.
The stability of co-polymer membrane P (BTC-H-FC-EDOT)-10 is tested by cyclic voltammetry.The polymeric film obtained with constant potential polymerization process is placed in blank solution and carries out cyclic voltammetry, electric potential scanning scope is-0.4V-1.45V, and sweep velocity is 300mVs
-1.We delineate the scanning curve (Figure 15) of P (BTC-H-FC/EDOT)-10 the 1st weeks and the 300th week.Analyze known, after scanning 300 weeks, P (BTC-H-Fc/EDOT)-10 copolymer film maintains the electroactive of original state 77.8%.
Claims (10)
1. carbazole-thiophene-based multipolymer, described multipolymer is that the reactive monomer A of 1:1 ~ 1:10 and reactive monomer B to be polymerized by electrochemical oxidation method and to obtain by mol ratio, described reactive monomer A is 3 of ferrocene group modification, 6-bis-thiophene carbazole molecules, its structural formula is such as formula shown in (I); Described reactive monomer B is 3,4-rthylene dioxythiophene, and its structural formula is as (II);
2. carbazole-thiophene-based multipolymer as claimed in claim 1, is characterized in that described electrochemical oxidation method comprises the steps:
(1) be the reactive monomer A of 1:1 ~ 1:10 and reactive monomer B and supporting electrolyte by mol ratio, electroanalysis solvent adds in three-electrode cell and be mixed with electrolytic solution, in described electrolytic solution, the starting point concentration scope of two kinds of reactive monomers is all at 0.001 ~ 0.01mol/L, the concentration of supporting electrolyte is 0.001 ~ 0.1mol/L, then be polymerized at employing potentiostatic method in three-electrode cell, galvanic deposit obtains co-polymer membrane on the working electrode (s;
(2) dedoping process is carried out to obtained co-polymer membrane, obtain the carbazole-thiophene-based co-polymer membrane deposited on the working electrode (s.
3. carbazole-thiophene-based multipolymer as claimed in claim 1 or 2, it is characterized in that: in described step (1), described supporting electrolyte is made up of in total mol ratio 1 ︰ 1 ratio negatively charged ion and positively charged ion, described negatively charged ion is that following one or more mix arbitrarily: perchlorate, tetrafluoroborate ion or hexafluorophosphoricacid acid ions, and described positively charged ion is that following one or more mix arbitrarily: lithium ion, tetramethyl ammonium, tetraethyl ammonium ion or TBuA ion.
4. carbazole-thiophene-based multipolymer as claimed in claim 3, is characterized in that: described supporting electrolyte is tetrabutylammonium perchlorate, lithium perchlorate or 4-butyl ammonium fluoroborate.
5. carbazole-thiophene-based multipolymer as claimed in claim 1 or 2, is characterized in that: in described step (1), and described electroanalysis solvent is selected from one of following: acetonitrile, trichloromethane or methylene dichloride.
6. carbazole-thiophene-based multipolymer as claimed in claim 1 or 2, it is characterized in that: in described step (1), described three-electrode cell with gold, platinum or indium tin oxide-coated glass electrode for working electrode, with gold or platinum electrode for supporting electrode, take silver-silver chloride electrode as reference electrode, under constant potential 1.0 ~ 2.0V condition, adopt potentiostatic method to carry out polyreaction, polyreaction terminal judges according to consumes power 0.04 ~ 0.08C.
7. carbazole-thiophene-based multipolymer as claimed in claim 1 or 2, it is characterized in that: in described step (2), described dedoping process is specially: the co-polymer membrane that step (1) is obtained is placed in same electrolytic solution, controlling potential is between-0.4V to-0.6V, first time dedoping process 100-200s is carried out to depositing co-polymer membrane working electrode, and then be placed in blank solution again by after the working electrode eluent solvent after first time dedoping process, the composition of the electrolytic solution that described blank solution uses with first time dedoping is distinguished and is only the former not containing reactive monomer A and reactive monomer B, control dedoping current potential and process 100s-200s between-0.4V to-0.6V, carry out the process of secondary dedoping, obtain the co-polymer membrane through dedoping process.
8. carbazole-thiophene-based multipolymer as claimed in claim 1 or 2, is characterized in that: described electrochemical oxidation method also comprises step (3): carried out by the co-polymer membrane through dedoping process cleaning, dry; Cleaning solvent is acetonitrile, trichloromethane or methylene dichloride.
9. carbazole-thiophene-based multipolymer as claimed in claim 8, is characterized in that: in described step (3), after the co-polymer membrane cleaning of dedoping process in 60 ~ 90 DEG C dry 12 ~ 24 hours.
10. carbazole-thiophene-based multipolymer as claimed in claim 1 is as the application of electrochromic material.
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| CN103450700A (en) * | 2013-08-23 | 2013-12-18 | 中山大学 | Tree-based organic dyestuff based on carbazole or triphenylamine derivatives and application thereof in preparation of dye-sensitized solar cell |
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| CN102376899A (en) * | 2010-08-06 | 2012-03-14 | 株式会社理光 | Light emitting device and display unit |
| CN103450700A (en) * | 2013-08-23 | 2013-12-18 | 中山大学 | Tree-based organic dyestuff based on carbazole or triphenylamine derivatives and application thereof in preparation of dye-sensitized solar cell |
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