CN101591425A - Novel electrochromic copolymer and its production and application - Google Patents
Novel electrochromic copolymer and its production and application Download PDFInfo
- Publication number
- CN101591425A CN101591425A CNA2009101002268A CN200910100226A CN101591425A CN 101591425 A CN101591425 A CN 101591425A CN A2009101002268 A CNA2009101002268 A CN A2009101002268A CN 200910100226 A CN200910100226 A CN 200910100226A CN 101591425 A CN101591425 A CN 101591425A
- Authority
- CN
- China
- Prior art keywords
- electrochromic
- copolymer
- formula
- ion
- compound shown
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The invention discloses a kind of novel electrochromic copolymer and its production and application, this electrochromic copolymer is suc as formula the compound shown in the II and 3 with structure compound shown by formula I or structure, the 4-ethene dioxythiophene is as comonomer, adopt the electrochemically oxidative polymerization method to make, the polymerization degree is 6～30; Its Chinese style I compound and 3, the molar ratio of 4-ethene dioxythiophene 10: 90～90: 10, formula II compound and 3, the molar ratio of 4-ethene dioxythiophene are 20: 80～80: 20.Described electrochromic copolymer red green and blue three primary colors can be applicable in the electrochromic device.Electrochromic polymer of the present invention, reversibly redox produces metachromatism, electrochemical stability is good, the variable color time of response is short, and the electrochemical filming method is easy and simple to handle, resulting film is smooth smooth, and film thickness can be provided with difference according to depositional mode and parameter and regulate and control.
Description
Technical field
The present invention relates to a kind of electrochromic copolymer and its production and application, these electrochromic polymer can be applied in the electrochromic device.
Background technology
Electrochromic material is meant that under the extra electric field effect optical property of material (comprising transmissivity, specific absorption and emittance etc.) possesses reversible transformation in visible wavelength range, but macro manifestations is that the color of material is with extra electric field effect generation inverse conversion.Electrochromic material is divided into inorganic and the organic electrochromic material by kind, and the latter can be divided into organic molecule and conductive polymers electrochromic material again.That the conductive polymers electrochromism has is of a great variety, colour-change obviously, characteristics such as good processability, therefore gather around and have broad application prospects, such as smart window, mobile electrochromism screen, camouflage clothes etc. in the electrochromic device association area.
The more electrochromic conducting polymer material of research mainly comprises polyaniline, polypyrrole, Polythiophene, polycarbazole and corresponding derivative etc. at present.In the Polythiophene system, what research was comparatively concentrated as electrochromic material is to gather 3,4-ethene dioxythiophene (PEDOT) and its derivative.Under the doping attitude, PEDOT has good electrical conductivity, electrochemical stability and excellent photoelectric properties, and presents light blue.What obtain after the PEDOT electrochemical reduction then is navy blue dedoping attitude.Electrochromic material requires to have as far as possible that abundant colors changes, and except selecting for use and develop different types of conductive polymers monomer, realizes by methods such as complexing, function doping, blend, compound and copolymerization toward contact.Wherein the method for modification by copolymerization can remedy electrochromism homopolymer deficiency separately, obtain the electrochromic material of many novelties, be widely used in central (the Li upstart of preparation electrochromic material, Xia Yu, Huang Meirong. the electrochromism of conducting polymer and the application on smart window thereof. the exploitation of material and application 2004,19 (2): 31-35.).
Deng find with EDOT and pyrroles carry out copolymerization can obtain a class electrochromism respond the type material that is exceedingly fast (
O., JohanssonT., Ghosh S.Phase Engineering for Enhanced Electrochromism inConjugated Polymers.Electrochimica Acta 2001,46 (13): 2031-2034.).People such as Pozo-Gonzalo C. adopt chemical method to synthesize dipolymer in pyrroles and thiophene or thiophene derivant in advance, then adopt electrochemical production to obtain electrochromic conducting polymer (the Pozo-Gonzalo C. of series of displays multicolour conversion as polymerization single polymerization monomer these dipolymers, Salsamendi M., Pomposo J.A., Grande H.J., Schmidt E.Y., Rusakov Y.Y., Trofimov B.A.Influence of the introduction of short alkyl chains inpoly (2-(2-thienyl)-1H-pyrrole) on its electrochromic behavior.Macromolecules 2008,41 (19): 6886-6894.).One of subject matter of current electrochromic polymer research is when how to guarantee the stability of material, gives the material conversion of rich colors more.In addition, because gegenion must be diffused in the polymer layer or from polymer layer and diffuse out, to keep charge balance, this process can make the variable color time of response of electrochromic polymer be restricted.Consider to the present invention proposes two class novel electrochromic polymeric systems based on above-mentioned two problems, especially two analog copolymer systems not only have good electrochemical stability, and have red green blue tricolor electrochromism ability.
In general, the common preparation method of electrochromic polymer has chemical polymerization and electrochemical polymerization.
Electrochemical polymerization is meant the polyreaction that electroactive polymerization single polymerization monomer Applied Electrochemistry method is carried out on working electrode.Prepare electrochromic polymer than chemical polymerization, it is simple that electrochemical method has preparation, and the polymkeric substance thickness is controlled, advantages such as technology environmental protection.
Summary of the invention
The primary technical problem that the present invention will solve is to provide a kind of electrochromic copolymer, these electrochromic copolymer red green and blue three primary colors, and reversibly redox produces metachromatism, and the variable color time of response is short, and electrochemical stability is good.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
A kind of electrochromic copolymer, be with structure compound shown by formula I or structure suc as formula the compound shown in the II and 3, the 4-ethene dioxythiophene makes by the electrochemically oxidative polymerization method as comonomer; Structure compound shown by formula I and 3 wherein, the molar ratio of 4-ethene dioxythiophene 10: 90～90: 10, structure is suc as formula the compound shown in the II and 3, and the molar ratio of 4-ethene dioxythiophene is 20: 80～80: 20;
Further, structure compound shown by formula I and 3, the molar ratio of 4-ethene dioxythiophene is preferably 40: 60～and 60: 40.Structure is suc as formula the compound shown in the II and 3, and the molar ratio of 4-ethene dioxythiophene is preferably 40: 60～and 60: 40.
The electrochromic copolymer that the present invention makes, the polymerization degree are 6～30, preferred 6～20.The polymerization degree of the present invention is the comonomer quantity of the participation copolyreaction that contains in the electrochromic copolymer molecule.
Second technical problem that the present invention will solve is to provide a kind of preparation method of described electrochromic copolymer.
The present invention adopts following technical scheme: the structure compound shown by formula I and 3 that with mol ratio is 10: 90～90: 10, the 4-ethene dioxythiophene is comonomer or is that 20: 80～80: 20 structure is suc as formula the compound shown in the II and 3 with mol ratio, 4-ethene dioxythiophene (EDOT) is a comonomer, adopts the electrochemically oxidative polymerization method to prepare the electrochromic copolymer film;
Electrochemically oxidative polymerization method of the present invention recommends to carry out according to following: comonomer, supporting electrolyte and organic solvent are added in the three-electrode cell form electrolytic solution, galvanic deposit obtains copolymer film on working electrode, and copolymer film is through cleaning, be drying to obtain described electrochromic polymer; The initial total concn of comonomer is 10 in the described electrolytic solution
-3～10molL
-1, preferred 10
-3～10
-2Mol/L, supporting electrolyte concentration is 10
-3～10
-1MolL
-1, preferred 10
-2～10
-1Mol/L.
In above-mentioned electrochemically oxidative polymerization process, described supporting electrolyte is supporting electrolyte commonly used, and composition generally comprises negatively charged ion and positively charged ion.Negatively charged ion can be selected from following one or more: perchlorate, tetrafluoroborate ion, hexafluorophosphoricacid acid ions, sulfonate ion, formate ion, butyrate ion, valerate ion, phosphate anion; Positively charged ion can be selected from following one or more: lithium ion, ammonium radical ion, tetramethyl ammonium, tetraethyl ammonium ion, TBuA ion, four n-propyl ammonium ions, four n-hexyl ammonium ions.
Electrolyte solvent of the present invention is an organic solvent commonly used, as N, and dinethylformamide, methylene dichloride, acetonitrile, ethanol, methyl alcohol or tetrahydrofuran (THF) etc.
In described three-electrode cell, working electrode can be gold and silver, platinum, lead, graphite, glass carbon or ITO electrode; Supporting electrode can be gold and silver, platinum, lead, titanium or Graphite Electrodes; Reference electrode can be silver-silver ion electrode, silver-silver chloride electrode or saturated calomel electrode.
Electrochromic polymer of the present invention can adopt galvanostatic method, potentiostatic method or cyclic voltammetry to carry out the electrochemical oxidation preparation, and those of ordinary skills can regulate and control the thickness of polymeric film by adjusting electrochemical parameter.
When adopting galvanostatic method to prepare described electrochromic polymer, the concrete recommendation carried out according to following steps: working electrode is applied the continuous current signal, and the current density range of signal is 10
-1～10mAcm
-2, the time cycle is 100～1500s, thereby obtains the polymeric film that thickness is 10～1000nm on working electrode.
When adopting potentiostatic method to prepare described electrochromic polymer, the concrete recommendation carried out according to following steps: working electrode is applied the constant potential signal, the CONTROLLED POTENTIAL scope is 0.5～1.8V, time cycle is 10～1500s, thereby obtains the polymeric film that thickness is 10～1000nm on working electrode.
When adopting cyclic voltammetry to prepare described electrochromic polymer, the concrete recommendation carried out according to following steps: working electrode is applied triangular signal, triangular signal positive potential scope is-0.5～2.5V, the negative potential scope of triangular signal is-3.0～0.1V, time cycle is 10～1000s, thereby galvanic deposit obtains the polymeric film that thickness is 10～500nm on working electrode.
The copolymer film that adopts the electrochemically oxidative polymerization method to obtain among the present invention need carry out such as aftertreatments such as cleaning, dryings usually, and concrete steps are as follows:
With purity 80%～100% N, dinethylformamide, acetonitrile, ethanol, methyl alcohol, trichloromethane, methylene dichloride, tetrahydrofuran (THF), hexanaphthene, benzyl cyanide, ether, acetate, sherwood oil or water clean unreacted monomer residual on the electrodeposited film, and the time is 1～30min; Electrodeposited film after the cleaning is dried under vacuum condition, and temperature is 10～60 ℃; Also available rare gas element dries up or dries naturally, obtains dry purified polymer film.Drying mode and temperature can be determined according to the boiling point of solvent.
Electrochromic copolymer red green and blue three primary colors of the present invention can be applicable in the electrochromic device.
Beneficial effect of the present invention is: electrochromic polymer of the present invention, reversibly redox produces metachromatism, electrochemical stability is good, the variable color time of response is short, and the electrochemical filming method is easy and simple to handle, resulting film is smooth smooth, and film thickness can be provided with difference according to depositional mode and parameter and regulate and control.
Description of drawings
Formula I compound and EDOT copolymer film (50/50) observed surface topography map under scanning electron microscope that Fig. 1 adopts potentiostatic method to make for embodiment 1.
Formula I compound and EDOT copolymer film (50/50) observed surface topography map under scanning electron microscope that Fig. 2 adopts galvanostatic method to make for embodiment 2.
Formula I compound that Fig. 3 makes for embodiment 1 and EDOT copolymer film (50/50) produce UV, visible light (UV-Vis) spectrogram of red green blue tricolor under different potentials.
Fig. 4 is the formula I compound described in the embodiment 22 and the variable color stability test figure of EDOT copolymer film (40/60), sweep velocity: 1000mvs
-1, solid line was the 1st week, dotted line was the 2000th week.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is described further, but protection scope of the present invention is not limited to this.
Embodiment 1
The electrochemistry potentiostatic method synthesize (S)-1,1 '-dinaphthol-2,2 '-two-(6-1H-pyrroles's capronate) (structural formula I) and EDOT multipolymer (monomer mole ratio is 50/50)
Is 50/50 to be dissolved in the acetonitrile structural formula I monomer and EDOT monomer with mol ratio, and being mixed with total concn is 10
-2MolL
-1Solution, and adding tetrabutylammonium perchlorate controlling concn is 10
-1MolL
-1, as supporting electrolyte.The above-mentioned electrolytic solution that configures is joined in the three-electrode cell, select for use ito glass as working electrode; The platinized platinum electrode is as supporting electrode; Silver-silver chloride biliquid receiving electrode is as reference electrode.Adopt potentiostatic method to carry out polymerization, polymerization potential is 1.27V, and polymerization time is 1500s.After polymerization is finished, will in clean acetonitrile solution, clean 5min, treat to obtain after nature dries dry pure co-polymer membrane with the ito glass of the copolymer film of structural formula I and EDOT.Utilize MALDI-TOF-MS to measure the solid product polymerization degree n, recording n is 6～15.Co-polymer membrane surface looks adopt scanning electron microscopic observation to see Fig. 1, find that the surfacing of prepared electrochromic copolymer film is smooth.
Embodiment 2
The electrochemistry galvanostatic method synthesize (S)-1,1 '-dinaphthol-2,2 '-two-(6-1H-pyrroles's capronate) (structural formula I) and EDOT multipolymer (monomer mole ratio is 50/50)
Operating process just replaces potentiostatic method to carry out the preparation of multipolymer, controlled polymerization current density 2mAcm with galvanostatic method with embodiment 1
-2, polymerization time is 1500s.Utilize MALDI-TOF-MS to measure the solid product polymerization degree n, recording n is 7～14.The co-polymer membrane surface topography is observed and is seen Fig. 2, finds that the surfacing of prepared electrochromic copolymer film is smooth.
Embodiment 3
The electrochemistry galvanostatic method synthesize (S)-1,1 '-dinaphthol-2,2 '-two-(6-1H-pyrroles's capronate) (structural formula I) and EDOT multipolymer (monomer mole ratio is 40/60)
Operating process is with embodiment 2, controlled polymerization current density 2mAcm
-2, polymerization time is 1500s.Utilize MALDI-TOF-MS to measure the solid product polymerization degree n, recording n is 9～18.
Embodiment 4
The electrochemistry galvanostatic method synthesize (S)-1,1 '-dinaphthol-2,2 '-two-(6-1H-pyrroles's capronate) (structural formula I) and EDOT multipolymer (monomer mole ratio is 60/40)
Operating process is with embodiment 2, controlled polymerization current density 10mAcm
-2, polymerization time is 800s.Utilize MALDI-TOF-MS to measure the solid product polymerization degree n, recording n is 6～14.
Embodiment 5
Electrochemical cyclic voltammetry synthesize (S)-1,1 '-dinaphthol-2,2 '-two-(6-1H-pyrroles's capronate) (structural formula I) and EDOT multipolymer (monomer mole ratio is 10/90)
Is 10/90 to be dissolved in the acetonitrile structural formula I monomer and EDOT monomer with mol ratio, and being mixed with total concn is 10
-2MolL
-1Solution, and adding tetrabutylammonium perchlorate controlling concn is 10
-1MolL
-1, as supporting electrolyte.The above-mentioned electrolytic solution that configures is joined in the three-electrode cell, select for use ito glass as working electrode; The platinized platinum electrode is as supporting electrode; Silver-silver chloride biliquid receiving electrode is as reference electrode.Adopt cyclic voltammetric to carry out polymerization, the polymerization potential scope is-0.50～2.00V, and sweep velocity is 100mV s
-1, scanning 500s.After polymerization is finished, will in clean acetonitrile solution, clean 5min, treat to obtain after nature dries dry pure co-polymer membrane with the ito glass of the copolymer film of structural formula I and EDOT.Utilize MALDI-TOF-MS to measure the solid product polymerization degree n, recording n is 10～18.
Embodiment 6
Electrochemical cyclic voltammetry synthesize (S)-1,1 '-dinaphthol-2,2 '-two-(6-1H-pyrroles's capronate) (structural formula I) and EDOT multipolymer (monomer mole ratio is 90/10)
Operating process just becomes the polymerization potential scope-0.60～1.80V with embodiment 5, and polymerization time is 1500s.Utilize MALDI-TOF-MS to measure the solid product polymerization degree n, recording n is 6～16.
Embodiment 7
The electrochemistry potentiostatic method synthesize (S)-1,1 '-dinaphthol-2,2 '-two-(6-1H-pyrroles's benzoic ether) (structural formula II) and EDOT multipolymer (monomer mole ratio is 60/40)
Operating process is just carried out the preparation of multipolymer with structural formula II substitute structure formula I with embodiment 1, and controlled polymerization current potential 1.25V, polymerization time are 1500s.Utilize MALDI-TOF-MS to measure the solid product polymerization degree n, recording n is 6～10.
Embodiment 8
The electrochemistry potentiostatic method synthesize (S)-1,1 '-dinaphthol-2,2 '-two-(6-1H-pyrroles's benzoic ether) (structural formula II) and EDOT multipolymer (monomer mole ratio is 20/80)
Operating process just becomes 1.30V with polymerization potential by 1.25V with embodiment 7, and adopts tetrabutylammonium perchlorate lithium (10
-2Mol L
-1) replace the tetrabutylammonium perchlorate as supporting electrolyte, as solvent, polymerization time is 1000s with tetrahydrofuran (THF).Utilize MALDI-TOF-MS to measure the solid product polymerization degree n, recording n is 12～20.
Embodiment 9
The electrochemistry potentiostatic method synthesize (S)-1,1 '-dinaphthol-2,2 '-two-(6-1H-pyrroles's benzoic ether) (structural formula II) and EDOT multipolymer (monomer mole ratio is 40/60)
Operating process just becomes 1.30V with polymerization potential by 1.25V with embodiment 7, and adopts tetrabutylammonium perchlorate lithium (10
-1MolL
-1) replace the tetrabutylammonium perchlorate as supporting electrolyte, as solvent, polymerization time is 1000s with tetrahydrofuran (THF).Utilize MALDI-TOF-MS to measure the solid product polymerization degree n, recording n is 13～20.
Embodiment 10
The electrochemistry potentiostatic method synthesize (S)-1,1 '-dinaphthol-2,2 '-two-(6-1H-pyrroles's benzoic ether) (structural formula II) and EDOT multipolymer (monomer mole ratio is 80/20)
Operating process just becomes 1.20V with polymerization potential by 1.25V with embodiment 7, and adopts tetrabutylammonium perchlorate lithium (10
-1MolL
-1) replace the tetrabutylammonium perchlorate as supporting electrolyte, as solvent, polymerization time is 1500s with tetrahydrofuran (THF).Utilize MALDI-TOF-MS to measure the solid product polymerization degree n, recording n is 8～14.
Embodiment 11
(S)-1,1 '-dinaphthol-2,2 '-two-(6-1H-pyrroles's capronate) (structural formula I) and the electrochromism of EDOT multipolymer (monomer mole ratio is 50/50) in acetonitrile solution
Put into three-electrode cell with prepared ito glass electrode among the embodiment 1 as working electrode, contain acetonitrile solution in the pond, and be 10 with volumetric molar concentration with structural formula I and EDOT co-polymer membrane (50/50)
-1MolL
-1The tetrabutylammonium perchlorate is as supporting electrolyte.Supporting electrode is selected the platinized platinum electrode for use; Reference electrode is selected silver-silver chloride biliquid receiving electrode for use.Adopt cyclic voltammetry to carry out the electrochromism of sweep test homopolymer, potential range is set at-0.8～1.4V, and sweep velocity is 3Vs
-1, scanned for 400 weeks.Can become pink by yellow by being observed visually the rising of film color with current potential, after current potential was replied, color became yellow again again, so repeatedly.Response frequency with sweep speed identical.Corresponding relation between redox peak and the co-polymer membrane color on the record volt-ampere curve.See Table 1, reversible transition can take place with the current potential conversion in this copolymer membrane color.
Corresponding relation between table 1 redox peak and its polymers film (structural formula I/EDOT=50/50) color
| Potential range | -0.8～-0.2V | -0.2～0.3V | 0.3～0.4V | 0.4～1.0V | 1.0～1.2V | 1.2～1.4V |
| The film color | Red | Pink | Yellow-green colour | Green | Light blue | Blue |
Embodiment 12
(S)-1,1 '-dinaphthol-2,2 '-two-(6-1H-pyrroles's capronate) (structural formula I) and the electrochromism of EDOT multipolymer (monomer mole ratio is 40/60) in acetonitrile solution
Operating process is with embodiment 11, is that the multipolymer modification ito glass of 40/60 structural formula I and EDOT is as working electrode with mol ratio just.Corresponding relation between redox peak and the co-polymer membrane color on the record volt-ampere curve.See Table 2.Reversible transition can take place with the current potential conversion in this copolymer membrane color.
Corresponding relation between table 2 redox peak and co-polymer membrane (structural formula I/EDOT=40/60) color
| Potential range | -0.8～0.0V | 0.0～0.3V | 0.3～1.0V | 1.0～1.2V | 1.2～1.4V |
| The film color | Red | Yellow-green colour | Green | Light blue | Blue |
Embodiment 13
(S)-1,1 '-dinaphthol-2,2 '-two-(6-1H-pyrroles's capronate) (structural formula I) and the electrochromism of EDOT multipolymer (monomer mole ratio is 60/40) in acetonitrile solution
Operating process is with embodiment 11, is that the multipolymer modification ito glass of 60/40 structural formula I and EDOT is as working electrode with mol ratio just.Corresponding relation between redox peak and the co-polymer membrane color on the record volt-ampere curve.See Table 3.Reversible transition can take place with the current potential conversion in this copolymer membrane color.
Corresponding relation between table 3 redox peak and co-polymer membrane (structural formula I/EDOT=60/40) color
| Potential range | -0.8～-0.2V | -0.2～0.2V | 0.2～0.4V | 0.4～1.2V | 1.2～1.4V |
| The film color | Red | Pink | Grass green | Light blue | Blue |
Embodiment 14
(S)-1,1 '-dinaphthol-2,2 '-two-(6-1H-pyrroles's benzoic ether) (structural formula II) and the electrochromism of EDOT multipolymer (monomer mole ratio is 60/40) in acetonitrile solution
Operating process just covers the ito glass electrode as working electrode with structural formula II and EDOT multipolymer (monomer mole ratio is 60/40) with embodiment 11.Corresponding relation between redox peak and the homopolymer film color on the record volt-ampere curve.See Table 4.Reversible transition can take place with the current potential conversion in this copolymer membrane color.
Table 4 redox peak and the co-polymer membrane (corresponding relation between the color of structural formula II/EDOT=60/40)
| Potential range | -0.8～-0.4V | -0.4～0.1V | 0.1～0.3V | 0.3～0.8V | 0.8～1.3V | 1.3～1.4V |
| The film color | Red | Pink | Yellow-green colour | Grass green | Light blue | Blue |
Embodiment 15
(S)-1,1 '-dinaphthol-2,2 '-two-(6-1H-pyrroles's benzoic ether) (structural formula II) and the electrochromism of EDOT multipolymer (monomer mole ratio is 40/60) in acetonitrile solution
Operating process just covers the ito glass electrode as working electrode with structural formula II and EDOT multipolymer (monomer mole ratio is 40/60) with embodiment 11.Corresponding relation between redox peak and the homopolymer film color on the record volt-ampere curve.See Table 5.Reversible transition can take place with the current potential conversion in this copolymer membrane color.
Table 5 redox peak and the co-polymer membrane (corresponding relation between the color of structural formula II/EDOT=40/60)
| Potential range | -0.8～-0.5V | -0.5～0.2V | 0.2～0.3V | 0.3～0.4V | 0.4～1.2V | 1.2～1.4V |
| The film color | Red | Pink | Yellow-green colour | Grass green | Light blue | Blue |
Embodiment 16
(S)-1,1 '-dinaphthol-2,2 '-two-(6-1H-pyrroles's capronate) (structural formula I) and the electrochromism of EDOT multipolymer (monomer mole ratio is 10/90) in acetonitrile solution
Operating process is with embodiment 11, is that the multipolymer modification ito glass of 10/90 structural formula I and EDOT is as working electrode with mol ratio just.Corresponding relation between redox peak and the co-polymer membrane color on the record volt-ampere curve.See Table 6.Reversible transition can take place with the current potential conversion in this copolymer membrane color.
Corresponding relation between table 6 redox peak and co-polymer membrane (structural formula I/EDOT=10/90) color
| Potential range | -0.8～0.2V | 0.2～0.4V | 0.4～1.4V |
| The film color | Pink | Yellow-green colour | Grey |
Embodiment 17
(S)-1,1 '-dinaphthol-2,2 '-two-(6-1H-pyrroles's capronate) (structural formula I) and the electrochromism of EDOT multipolymer (monomer mole ratio is 90/10) in acetonitrile solution
Operating process is with embodiment 11, is that the multipolymer modification ito glass of 90/10 structural formula I and EDOT is as working electrode with mol ratio just.Corresponding relation between redox peak and the co-polymer membrane color on the record volt-ampere curve.See Table 7.Reversible transition can take place with the current potential conversion in this copolymer membrane color.
Corresponding relation between table 7 redox peak and co-polymer membrane (structural formula I/EDOT=90/10) color
| Potential range | -0.8～0.1V | 0.1～0.3V | 0.3～1.4V |
| The film color | Orange | Yellow-green colour | Grey |
Embodiment 18
(S)-1,1 '-dinaphthol-2,2 '-two-(6-1H-pyrroles's benzoic ether) (structural formula II) and the electrochromism of EDOT multipolymer (monomer mole ratio is 20/80) in acetonitrile solution
Operating process just covers the ito glass electrode as working electrode with structural formula II and EDOT multipolymer (monomer mole ratio is 20/80) with embodiment 11.Corresponding relation between redox peak and the homopolymer film color on the record volt-ampere curve.See Table 8.Reversible transition can take place with the current potential conversion in this copolymer membrane color.
Table 8 redox peak and the co-polymer membrane (corresponding relation between the color of structural formula II/EDOT=20/80)
| Potential range | -0.8～0.2V | 0.2～0.3V | 0.3～1.4V |
| The film color | Pink | Faint yellow | Grey |
Embodiment 19
(S)-1,1 '-dinaphthol-2,2 '-two-(6-1H-pyrroles's benzoic ether) (structural formula II) and the electrochromism of EDOT multipolymer (monomer mole ratio is 80/20) in acetonitrile solution
Operating process just covers the ito glass electrode as working electrode with structural formula II and EDOT multipolymer (monomer mole ratio is 80/20) with embodiment 11.Corresponding relation between redox peak and the homopolymer film color on the record volt-ampere curve.See Table 9.Reversible transition can take place with the current potential conversion in this copolymer membrane color.
Table 9 redox peak and the co-polymer membrane (corresponding relation between the color of structural formula II/EDOT=80/20)
| Potential range | -0.8～0.1V | 0.1～0.4V | 0.4～1.4V |
| The film color | Orange | Faint yellow | Grey |
Embodiment 20
(S)-1,1 '-dinaphthol-2,2 '-two-(6-1H-pyrroles's capronate) (structural formula I) and the uv-vis spectra scanning of EDOT multipolymer (monomer mole ratio is 50/50) in acetonitrile solution under the different potentials
With preparation among the embodiment 1 be coated with structural formula I/EDOT be the ITO electrode of 50/50 co-polymer membrane as working electrode, the platinized platinum electrode is as supporting electrode, silver-silver chloride biliquid receiving electrode is as reference electrode, and to contain 10
-1MolL
-1Tetrabutylammonium perchlorate's acetonitrile solution utilizes cuvette to form electrolyzer, and working electrode and counter electrode is connected to the electrochemical workstation corresponding interface as electrolytic solution.Successively electropotential is adjusted to-0.8V, 0.4V, 1.0V, carry out the uv-vis spectra sweep test of co-polymer membrane after the wait system is stable, the co-polymer membrane transmittance is seen Fig. 3 with the wavelength change curve under the record different potentials.Can find that blue shift takes place film UV, visible light transmittance peak value gradually along with current potential is elevated to 1.0V by-0.8V, film transmittance peak value wave band under each current potential is corresponding with red, green and blue wave band respectively.
Embodiment 21
(S)-1,1 '-dinaphthol-2,2 '-two-(6-1H-pyrroles's capronate) (structural formula I) and the electrochromism response speed of EDOT multipolymer (monomer mole ratio is 50/50) in acetonitrile solution
Cover the ito glass electrode and place three-electrode cell with structural formula I prepared among the embodiment 1 and EDOT multipolymer (monomer mole ratio is 50/50) as working electrode.Contain 10 in the pond
-1MolL
-1Tetrabutylammonium perchlorate's acetonitrile solution.Supporting electrode is the platinized platinum electrode, and reference electrode is selected silver-silver chloride biliquid receiving electrode for use.The scanning of employing chronoamperometry specifically is provided with as follows:
Redness and green conversion: low potential is-0.8V, and noble potential is 0.4V, and the potential pulse width is 0.1～1s, scans 200 times.By visual inspection co-polymer membrane color with voltage pulse conversion between redness and green repeatedly.Response frequency is identical with the potential pulse width.
Green and blue conversion: low potential is 0.4V, and noble potential is 1.4V, and the potential pulse width is 0.1～1s, scans 200 times.By visual inspection co-polymer membrane color with voltage pulse conversion between green and blueness repeatedly.Response frequency is identical with the potential pulse width.
Red and blue conversion: low potential is-0.8V, and noble potential is 1.4V, and the potential pulse width is 0.3～1.5s, scans 200 times.By visual inspection co-polymer membrane color with voltage pulse conversion between green and blueness repeatedly.Response frequency is identical with the potential pulse width.
Embodiment 22
(S)-1,1 '-dinaphthol-2,2 '-two-(6-1H-pyrroles's capronate) (structural formula I) and EDOT multipolymer (monomer mole ratio is 40/60) electrochemical stability in acetonitrile solution
Adopting method described in the embodiment 3 to prepare structural formula I and EDOT mol ratio is 40/60 co-polymer membrane covering ito glass electrode, puts into three-electrode cell, and Chi Zhongwei contains 10
-1MolL
-1Tetrabutylammonium perchlorate's acetonitrile solution.Wherein working electrode is that covered structure formula I and EDOT mol ratio are the ito glass electrode of 40/60 multipolymer, and supporting electrode is the platinized platinum electrode, and reference electrode is selected silver-silver chloride biliquid receiving electrode for use.Adopt cyclic voltammetry to scan, potential range is set at-0.2～1.4V, and sweep velocity is set at 1000mV s
-1, scanning all numbers was 2000 weeks.Behind the end of scan, the above-mentioned copolymer film of visual inspection is partly dissolved attenuate, but metachrosis still exists.Fig. 4 is seen at the redox peak before and after the scanning.
Claims (10)
1, a kind of electrochromic copolymer, be with structure compound shown by formula I or structure suc as formula the compound shown in the II and 3, the 4-ethene dioxythiophene adopts the electrochemically oxidative polymerization method to make as comonomer; Structure compound shown by formula I and 3 wherein, the molar ratio of 4-ethene dioxythiophene 10: 90～90: 10, structure is suc as formula the compound shown in the II and 3, and the molar ratio of 4-ethene dioxythiophene is 20: 80～80: 20; The polymerization degree of described electrochromic copolymer is 6～30;
2, electrochromic copolymer as claimed in claim 1 is characterized in that structure compound shown by formula I and 3, and the molar ratio of 4-ethene dioxythiophene is 40: 60～60: 40.
3, electrochromic copolymer as claimed in claim 1 is characterized in that structure suc as formula the compound shown in the II and 3, and the molar ratio of 4-ethene dioxythiophene is 40: 60～60: 40.
4, electrochromic copolymer as claimed in claim 1, the polymerization degree that it is characterized in that described electrochromic copolymer is 6～20.
5, a kind of preparation method of electrochromic copolymer as claimed in claim 1, it is characterized in that described preparation method is as follows: the structure compound shown by formula I and 3 that with mol ratio is 10: 90～90: 10, the 4-ethene dioxythiophene is comonomer or is that 20: 80～80: 20 structure is suc as formula the compound shown in the II and 3 with mol ratio, the 4-ethene dioxythiophene is a comonomer, adopts the electrochemically oxidative polymerization method to prepare the electrochromic copolymer film; Described electrochemical oxidation method is specific as follows: comonomer, supporting electrolyte and organic solvent are added in the three-electrode cell form electrolytic solution, galvanic deposit obtains copolymer film on working electrode, and copolymer film is through cleaning, be drying to obtain described electrochromic copolymer; The initial total concn of comonomer is 10 in the described electrolytic solution
-3～10molL
-1, supporting electrolyte concentration is 10
-3～10
-1MolL
-1
6, the preparation method of electrochromic copolymer as claimed in claim 5, it is characterized in that described supporting electrolyte comprises negatively charged ion and positively charged ion, described negatively charged ion be selected from following one or more: perchlorate, tetrafluoroborate ion, hexafluorophosphoricacid acid ions, sulfonate ion, formate ion, butyrate ion, valerate ion, phosphate anion; Described positively charged ion be following one or more: lithium ion, ammonium radical ion, tetramethyl ammonium, tetraethyl ammonium ion, TBuA ion, four n-propyl ammonium ions, four n-hexyl ammonium ions.
7, the preparation method of electrochromic copolymer as claimed in claim 5, it is one of following to it is characterized in that described organic solvent is selected from: N, dinethylformamide, methylene dichloride, acetonitrile, ethanol, methyl alcohol, tetrahydrofuran (THF).
8, the preparation method of electrochromic copolymer as claimed in claim 5 is characterized in that described working electrode is gold and silver, platinum, lead, graphite, glass carbon or ITO electrode.
9,, it is characterized in that adopting the galvanic deposit on working electrode of galvanostatic method, potentiostatic method or cyclic voltammetry to obtain copolymer film as the preparation method of the described electrochromic copolymer of one of claim 5～8.
10, the application of electrochromic copolymer as claimed in claim 1 in electrochromic device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009101002268A CN101591425A (en) | 2009-06-25 | 2009-06-25 | Novel electrochromic copolymer and its production and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009101002268A CN101591425A (en) | 2009-06-25 | 2009-06-25 | Novel electrochromic copolymer and its production and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101591425A true CN101591425A (en) | 2009-12-02 |
Family
ID=41406316
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2009101002268A Pending CN101591425A (en) | 2009-06-25 | 2009-06-25 | Novel electrochromic copolymer and its production and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101591425A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103772664A (en) * | 2013-12-06 | 2014-05-07 | 京东方科技集团股份有限公司 | Green polythiophenes electrochromic material and preparation method thereof as well as component |
| CN104375349A (en) * | 2014-11-18 | 2015-02-25 | 辽宁大学 | Polyacid-based pure inorganic multi-color electrochromic film |
| CN107674181A (en) * | 2017-10-13 | 2018-02-09 | 安徽建筑大学 | Poly- dicarboxylate basic ring butane trimethylene dioxy thiophene blue-tinted transparent electrochromic material and preparation method, component and application |
| WO2018214416A1 (en) * | 2017-05-24 | 2018-11-29 | 华南理工大学 | Manufacturing method for high-resolution array organic film, and use thereof |
| CN109438678A (en) * | 2018-05-21 | 2019-03-08 | 浙江工业大学 | A kind of D-A-D` unsymmetric structure polymer film PSWE and the preparation method and application thereof |
| CN112186173A (en) * | 2020-09-21 | 2021-01-05 | 湖南艾华集团股份有限公司 | Negative electrode with high rate performance, preparation method and lithium ion battery |
-
2009
- 2009-06-25 CN CNA2009101002268A patent/CN101591425A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103772664A (en) * | 2013-12-06 | 2014-05-07 | 京东方科技集团股份有限公司 | Green polythiophenes electrochromic material and preparation method thereof as well as component |
| US9926406B2 (en) | 2013-12-06 | 2018-03-27 | Boe Technology Group Co., Ltd. | Green polythiophene electrochromic materials, method for preparation thereof, and assembly comprising the same |
| CN104375349A (en) * | 2014-11-18 | 2015-02-25 | 辽宁大学 | Polyacid-based pure inorganic multi-color electrochromic film |
| CN104375349B (en) * | 2014-11-18 | 2017-02-22 | 辽宁大学 | Polyacid-based pure inorganic multi-color electrochromic film |
| WO2018214416A1 (en) * | 2017-05-24 | 2018-11-29 | 华南理工大学 | Manufacturing method for high-resolution array organic film, and use thereof |
| CN107674181A (en) * | 2017-10-13 | 2018-02-09 | 安徽建筑大学 | Poly- dicarboxylate basic ring butane trimethylene dioxy thiophene blue-tinted transparent electrochromic material and preparation method, component and application |
| CN109438678A (en) * | 2018-05-21 | 2019-03-08 | 浙江工业大学 | A kind of D-A-D` unsymmetric structure polymer film PSWE and the preparation method and application thereof |
| CN109438678B (en) * | 2018-05-21 | 2020-10-27 | 浙江工业大学 | D-A-D' asymmetric structure polymer film PSWE and preparation method and application thereof |
| CN112186173A (en) * | 2020-09-21 | 2021-01-05 | 湖南艾华集团股份有限公司 | Negative electrode with high rate performance, preparation method and lithium ion battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105887126B (en) | It is poly-（3,4 ethylenedioxy thiophenes）Nano wire film and its synthetic method and application | |
| Cihaner et al. | A Novel Neutral State Green Polymeric Electrochromic with Superior n‐and p‐Doping Processes: Closer to Red‐Blue‐Green (RGB) Display Realization | |
| CN103582844B (en) | Stable electrochromic module | |
| Lo et al. | Fine-tuning the color hue of π-conjugated black-to-clear electrochromic random copolymers | |
| CN101591425A (en) | Novel electrochromic copolymer and its production and application | |
| CN106543415B (en) | Thin polymer film and the preparation method and application thereof based on intersection construction conjugated molecule | |
| CN110262152A (en) | A kind of electrochromic device and its assemble method of high color contrast | |
| Xu et al. | Triphenylamine-based multielectrochromic material and its neutral green electrochromic devices | |
| CN107153311A (en) | Based on tungstic acid and Prussian blue double-function device | |
| Wang et al. | Electrosynthesis and characterization of an electrochromic material from poly (1, 4-bis (3-methylthiophen-2-yl) benzene) and its application in electrochromic device | |
| CN105372896A (en) | Solid electrolyte electrochromism flexible device preparation based on conductive polymer | |
| CN110592609B (en) | Method for improving cycling stability of polymer electrochromic film | |
| Tang et al. | Black-to-transmissive polymer films via electrochemical copolymerization with high-performance electrochromic and supercapacitor bifunction | |
| Wu et al. | Incorporating electrospun nanofibers of TEMPO-grafted PVDF-HFP polymer matrix in viologen-based electrochromic devices | |
| Zeng et al. | Transparent-to-black electrochromic smart windows based on N, N, N′, N′-Tetraphenylbenzidine derivatives and tungsten trioxide with high adjustment ability for visible and near-infrared light | |
| CN105368443A (en) | Application of oxygen-nitrogen free radical group containing triphenylamine derivate polymer containing as electrochromic material | |
| Xue et al. | Effects on optoelectronic performances of EDOT end-capped oligomers and electrochromic polymers by varying thienothiophene cores | |
| Wang et al. | Synthesis and electropolymerization of 9H-carbazol-9-ylpyrene and its electrochromic properties and electrochromic device application | |
| Zhang et al. | Pulsed electrodeposition of nanostructured polythiothene film for high-performance electrochromic devices | |
| Xu et al. | Novel multicolored electrochromic polymers containing phenanthrene-9, 10-quinone and thiophene derivatives moieties | |
| Xu et al. | Effect of counter anion on the uniformity, morphology and electrochromic properties of electrodeposited poly (3, 4-ethylenedioxythiophene) film | |
| CN109293889A (en) | A kind of poly- 3,4- ethene dioxythiophene mesh nanometer film PEDOT-TD and the preparation method and application thereof | |
| OUYANG et al. | Enhanced film-forming and electrochromic properties by incorporating bithiophene into triphenylamine | |
| Collomb-Dunand-Sauthier et al. | Spectroelectrochemical behaviour of poly (3-octylthiophene): application to electrochromic windows with polyaniline and iridium oxide | |
| CN103387343A (en) | Preparation method of nickel oxide/poly(3,4- ethylenedioxythiophene) compound electrochromic film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Open date: 20091202 |