CN105368443A - Application of oxygen-nitrogen free radical group containing triphenylamine derivate polymer containing as electrochromic material - Google Patents
Application of oxygen-nitrogen free radical group containing triphenylamine derivate polymer containing as electrochromic material Download PDFInfo
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Abstract
The invention discloses an application ofoxygen-nitrogen free radical group containing triphenylamine derivate polymer as an electrochromic material. The structure of the triphenylamine derivate polymer is shown as the formula (1), and in the formula (1), n represents the average degree of polymerization, and n ranges from 10 to 2,000. Compared with other existing electrochromic materials, the prepared electrochromic material has short response time, the large color contrast ratio and good stability, when the electrochromic material is tested at the position of the visible wavelength of 1,100 nm, the contrast ratio is 47.3%, the response time is 0.43 s, and 96.8% of initial electrochemical activity is still kept after cyclic voltammetry continuous scanning is carried out for 300 circles. The formula I is shown in the specification.
Description
Technical field
The invention belongs to electrochromic material technical field, particularly relate to a kind of application of triphenylamine derivative polymkeric substance as electrochromic material containing aerobic nitrogen free radical group, this electrochromic polymer can be used in electrochromic device.
Background technology
Electrochromism refers under DC Electric Field, by injection and the extraction of current carrier, makes the optical property of material possess reversible transformation in visible wavelength region, and macro manifestations is that the color of material and transparency are with DC Electric Field generation reversible transformation.From Deb.S.K Late Cambrian WO in 1969
3the electrochromism phenomenon of film also, since proposing " Lacking oxygen colour center " mechanism, has obtained research about electrochromic material in a large number.Research in early days for electrochromic material mainly concentrates on inorganic electrochromic material, as WO
3, IrO
2, the transition metal oxide such as NiO, the title complex class electrochromic material of Prussian blue system, purple sieve Compounds, conductive polymers, transition metal and lanthanon is found gradually and studies subsequently.Wherein, conductive polymers class electrochromic material has that kind is many, color plasticity-is strong, contrast gradient is high, good processability, the advantages such as controlled and fast response time can be with to receive much concern, and is expected to one of developing direction becoming electrochromic material of future generation.
The metachromatic principle of conductive polymers is mainly doping and dedoping process, adulterates and the essence of dedoping is, under the effect of electric field or voltage, and ion (H
+, Li
+, ClO
4 -deng) behavior of moving into and moving out in conductive polymer subchain, simultaneously with the gain and loss of electronics, can find out that the doping process of conductive polymers is exactly a reversible redox process.In recent years, conducting electricity poly-triphenylamine and derivative thereof studies widely because low, the easy protonic acid doping of its oxidizing potential, the advantage such as color contrast is high, environmental stability is good receive in electrochromic material field.The preparation method of current conduction poly-triphenylamine material has chemical polymerization and electrochemical polymerization method, and due to the existence of dimerization reaction, simple poly-triphenylamine cannot be obtained by electrochemical polymerization method.The a series of poly-triphenylamine derivative of people's design and synthesis such as Guey-ShengLiou, mainly containing the triphenylamine derivative of dicarboxyl, a series of not only there is electroluminescent but also there is electrochromic polymkeric substance with the diamines containing distinct fragrance group by obtaining after chemical polymerization thing; Seminar of ox naval has synthesized a series of triphenylamine derivative with amino, and the dialdehyde-based containing distinct fragrance group with centre obtains a series of polymkeric substance by chemical polymerization, is tested by electrochromic property, the large multipotency multicolor displaying of this series material.Above-mentioned is all the triphenylamine derivative polymeric film prepared by chemical polymerization, but chemical method preparation technology is comparatively complicated, adds preparation cost, and becomes film uniformity also relatively poor.
Summary of the invention
The object of this invention is to provide the described application of triphenylamine derivative polymkeric substance as electrochromic material containing aerobic nitrogen free radical group, the oxidation/reduction that this polymkeric substance can be reversible produces metachromatism, and good stability, the time of response is short.
Below technical scheme of the present invention is illustrated.
The invention provides a kind of application of triphenylamine derivative polymkeric substance as electrochromic material containing aerobic nitrogen free radical group, its structure is such as formula shown in (I):
In formula (I), n represents mean polymerisation degree, and n is 10 ~ 2000.
Obtained by the triphenylamine derivative monomer polymerization containing aerobic nitrogen free radical group such as shown in formula II such as formula the triphenylamine derivative polymkeric substance containing aerobic nitrogen free radical group shown in (I), the chemistry 4-diphenylamino phenylformic acid-4-(1-oxygen nitrogen free radical) 2 by name entirely of the monomer as shown in formula II, 2,6,6-tetramethyl piperidine ester:
The triphenylamine derivative monomer containing aerobic nitrogen free radical group shown in described formula II can adopt following synthetic route to prepare:
Concrete, the preparation method of the triphenylamine derivative monomer containing aerobic nitrogen free radical group shown in described formula II comprises the steps:
(1) synthesis of 4-diphenylamino cyanobenzene: at N, dinethylformamide solvent adds sodium hydride, after dissolving completely, add the p-Fluorophenyl cyanide shown in the pentanoic shown in formula (III) and formula (IV), react under the protection of nitrogen, fully after reaction, gained reaction solution a obtains the 4-diphenylamino cyanobenzene shown in formula (V) through separation and purification;
(2) the benzoic synthesis of 4-diphenylamino: add the 4-diphenylamino cyanobenzene shown in potassium hydroxide and formula (V) in the mixed solvent of second alcohol and water, fully after reaction, gained reaction solution b obtains the 4-diphenylamino phenylformic acid shown in formula VI through separation and purification;
(3) 4-diphenylamino phenylformic acid-4-(1-oxygen nitrogen free radical) 2, 2, 6, the synthesis of 6-tetramethyl piperidine ester (TPAT): in organic solvent, described organic solvent is methylene dichloride, ethyl acetate or tetrahydrofuran (THF), 1-oxygen nitrogen free radical-2 shown in 4-diphenylamino phenylformic acid shown in formula VI and formula (VII), 2, 6, 6-tetramethylpiperidinol reacts under the effect of condensing agent 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDCI) and catalyzer DMAP (DMAP), after abundant reaction, gained reaction solution c obtains the 4-diphenylamino phenylformic acid-4-(1-oxygen nitrogen free radical) 2 shown in formula II through separation and purification, 2, 6, 6-tetramethyl piperidine ester.
Further, in described step (1), the ratio of the amount of substance that feeds intake of the pentanoic shown in formula (III), the p-Fluorophenyl cyanide shown in formula (IV), sodium hydride is 1:1 ~ 1.3:1 ~ 3.
In described step (1), the temperature of reaction is 100 ~ 110 DEG C, and the reaction times is 12 ~ 24h.
In step (1), the purification procedures of described reaction solution a is: after reaction terminates, reaction solution a methylene dichloride and water washing, extraction, steam after getting the drying of oil phase extraction liquid and desolventize, resultant product silica gel column chromatography separating-purifying, with the mixed solvent of normal hexane, ethyl acetate volume ratio 50:1 for eluent, collects the elutriant containing product, steaming desolventizes, obtained 4-diphenylamino cyanobenzene shown in formula (V).
In described step (1), the volumetric usage of DMF solvent generally counts 5 ~ 20mL/g with the quality of the pentanoic shown in formula (III).
Further, in described step (2), in the mixed solvent of second alcohol and water, the volume ratio of second alcohol and water is 2:1.
In step (2), the 4-diphenylamino cyanobenzene shown in formula (V) is 1:8 ~ 12 with the ratio of the amount of substance that feeds intake of potassium hydroxide, preferred 1:10.
In described step (2), temperature of reaction is the heating reflux reaction reaction times is 24 ~ 72h, preferred 48h.
In described step (2), the volumetric usage of the mixed solvent of second alcohol and water generally counts 50 ~ 150mL/g with the quality of the 4-diphenylamino cyanobenzene shown in formula (V).
In described step (2), the purification procedures of described reaction solution b is: after reaction terminates, reaction solution b under agitation adds dilute hydrochloric acid, and (concentration of dilute hydrochloric acid is generally 0.5 ~ 2mol/L, preferred 1mol/L), adjust ph, to 1 ~ 2, separates out white precipitate, subsequent filtration, filter cake is dry with massive laundering final vacuum, obtained 4-diphenylamino phenylformic acid shown in formula VI.
Further, in described step (3), the 1-oxygen nitrogen free radical-2,2 shown in the 4-diphenylamino phenylformic acid shown in formula VI and formula (VII), the ratio of the amount of substance that feeds intake of 6,6-tetramethylpiperidinol, EDCI, DMAP is 1:1 ~ 1.3:1 ~ 1.2:0.5.
Further, in step (3), temperature of reaction is 0 ~ 70 DEG C, preferably 20 ~ 30 DEG C; Reaction times is 12 ~ 48h, preferably 24 hours.
In described step (3), the preferred methylene dichloride of described organic solvent.
In described step (3), the volumetric usage of described organic solvent generally counts 20 ~ 50mL/g with the benzoic quality of 4-diphenylamino shown in formula VI.
In step (3), the purification procedures of described reaction solution c is: after reaction terminates, reaction solution c dichloromethane extraction, gets organic phase steaming and desolventizes, resultant product silica gel column chromatography carries out separating-purifying, with the mixed solvent of normal hexane, ethyl acetate volume ratio 80:1 for eluent, collect the elutriant containing product, steaming desolventizes, obtained 4-diphenylamino phenylformic acid-4-(1-oxygen nitrogen free radical) 2 shown in formula II, 2,6,6-tetramethyl piperidine ester.
Further, the present invention also provides the electrochemical preparation method of the triphenylamine derivative polymkeric substance containing aerobic nitrogen free radical group shown in formula (I), described method is: by electroanalysis solvent, the triphenylamine derivative monomer (TPAT) containing aerobic nitrogen free radical group shown in formula II and supporting electrolyte composition electrolytic solution, add in three-electrode cell, adopt potentiostatic method, galvanostatic method or cyclic voltammetry on the working electrode (s galvanic deposit obtain polymeric film, polymeric film is through cleaning, be drying to obtain the triphenylamine derivative polymkeric substance (PTPAT) containing aerobic nitrogen free radical group shown in described formula (I).
Further, described supporting electrolyte is conventional supporting electrolyte, generally be made up of in mole number 1:1 ratio negatively charged ion and positively charged ion, described negatively charged ion is perchlorate, tetrafluoroborate ion, hexafluorophosphoricacid acid ions, hexafluoroarsenate radical ion, nitrate ion, sulfonate ion, sulfate ion, formate ion, acetate ion, propionate ion, butyrate ion, valerate ion or phosphate anion; Described positively charged ion is sodium ion, potassium ion, lithium ion, hydrogen ion, ammonium radical ion, tetramethyl ammonium, tetraethyl ammonium ion, TBuA ion, four n-propyl ammonium ions or four n-hexyl ammonium ions.
Preferred supporting electrolyte is LiClO
4.
Further, described electroanalysis solvent is common solvent, as sulfuric acid, fluosulfonic acid, hydrogen fluoride, acetic acid, water, ammoniacal liquor, N, dinethylformamide, N,N-dimethylacetamide, acetonitrile, toluene, ethanol, methyl alcohol, trichloromethane, methylene dichloride, tetrahydrofuran (THF), hexanaphthene, pyridine, propylene carbonate, benzyl cyanide, ether, acetic acid, formic acid, hydrochloric acid, phosphoric acid or sherwood oil etc.
Preferred electroanalysis solvent is acetonitrile.
Further, in described electrolytic solution, the concentration of the triphenylamine derivative monomer (TPAT) containing aerobic nitrogen free radical group shown in formula II is 10
-3~ 10mol/L, preferably 10
-3~ 10
-1mol/L, is more preferably 10
-2mol/L, the concentration of supporting electrolyte is 10
-3~ 10
-1mol/L, is preferably 10
-2mol/L.
Further, in described three-electrode cell, working electrode can be gold, platinum, lead, titanium, Graphite Electrodes or ITO electrode; Reference electrode is generally silver-silver ion electrode, silver-silver chloride electrode or saturated calomel electrode, adopts platinum filament as to electrode.
Further, preferably adopt cyclic voltammetry to be polymerized, sweep voltage scope is 0.4V ~ 1.2V, and sweep velocity is 100mV/s.
The triphenylamine derivative polymkeric substance (PTPAT) containing aerobic nitrogen free radical group shown in formula provided by the invention (I) can be applied as electrochromic material.
Electrochromic polymer material provided by the invention, oxidation/reduction that can be reversible produces metachromatism, and good stability, the time of response is short.
PTPAT provided by the invention, along with the rising of voltage, become blackish green from yellow, and when after loss of voltage, color becomes yellow again again.
Compared with prior art, advantage of the present invention is:
(1) the present invention is by introducing the oxygen nitrogen free radical group with excellent electrochemical performance in poly-triphenylamine contraposition, and solve as capping group the problem that simple poly-triphenylamine cannot be prepared by electrochemical polymerization, adopt the method for electrochemical polymerization to have the advantages such as technique is simple, cost is low, good film-forming property compared to chemical polymerization.
(2) electrochromic material prepared of the present invention is compared with other electrochromic materials existing, there is time of response, larger color contrast and good stability faster, wherein test at visible wavelength 1100nm place, its contrast gradient is 47.3%, time of response is 0.43s, and cyclic voltammetric continuous sweep still maintains the initial electrochemical activity of 96.8% after 300 weeks.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of PTPAT polymeric film.
Fig. 2 is the stereoscan photograph of PTPAT polymeric film.
Fig. 3 is the cyclic voltammetric polymerization graphic representation of PTPAT polymeric film.
Fig. 4 is the cyclic voltammetry curve of PTPAT polymeric film in blank solution under different scanning speed and peak current and sweep velocity linear fit graphic representation.Wherein the upper figure of Fig. 4 is the cyclic voltammetry curve figure under different scanning speed, and figure below is peak current and sweep velocity linear fit graphic representation.
Fig. 5 is the spectroelectrochemistry graphic representation of PTPAT polymeric film.
Fig. 6 is the time of response of PTPAT polymeric film under 409nm and 1100nm wavelength and contrast curves figure.
Fig. 7 is the cyclical stability graphic representation of PTPAT polymeric film.
Embodiment
By the following examples technical scheme of the present invention is described further, but protection scope of the present invention is not limited thereto.
The electrochemical synthesis of embodiment 1:PTPAT
(1) synthesis of 4-diphenylamino cyanobenzene
In the 250mL there-necked flask of drying treatment, adding the anhydrous DMF of 50mL (DMF) in advance, adding sodium hydride (1.5g) subsequently, fully stirring to remove in dissolution process a large amount of bubbles produced.Treat that bubble-free produces, add pentanoic (III) (5.1g) and be warming up to 110 DEG C, reaction solution presents smears tea green, and add subsequently p-Fluorophenyl cyanide (IV) (4.5g), reaction solution is transformed into scarlet, reacts at N
2the lower reaction 12h of protection reaches reaction end.Reacting coarse product methylene dichloride and water washing, extraction, Rotary Evaporators is adopted to remove solvent after getting the drying of oil phase extraction liquid, and carry out separating-purifying by column chromatography by revolving the resultant product after steaming, stationary phase selects 300 order silica gel, moving phase selects the mixed solvent of normal hexane, ethyl acetate volume ratio 50:1, collects the elutriant containing product, and elutriant steams to desolventize and obtains 4-diphenylamino cyanobenzene (V) 4.98g, productive rate 61.1%, product is faint yellow solid powder.
1HNMR(CDCl
3,500MHz)d/ppm:6.94(d,2H),7.20(d,4H),7.25(d,2H),7.39(t,4H),8.05(d,2H).MS:m/z(EI):270.12.
(2) the benzoic synthesis of 4-diphenylamino
The mixed solvent of ethanol (60mL)/water (30mL) is being added in advance in the 250mL there-necked flask of drying treatment.Add potassium hydroxide (2.0761g) and 4-diphenylamino cyanobenzene (V) (1.0g) subsequently, stirring and dissolving is also warming up to 85 DEG C of back flow reaction 48h.After reaction terminates, be cooled to room temperature, drip hydrochloric acid soln (1mol/L) to reaction solution while stirring and regulate the pH value of reaction solution to about 1, now separate out a large amount of white depositions in reaction solution, subsequent filtration also uses massive laundering.By the filter cake vacuum-drying 24h at 60 DEG C obtained.Obtain product 4-diphenylamino phenylformic acid (VI) 0.82g, productive rate 82%, product is white solid powder.
1HNMR(CDCl
3,500MHz)d/ppm:7.00(t,2H),7.17(m,6H),7.34(t,4H),7.92(d,2H),10.43(s,1H,sharpCOOH).MS:m/z(EI):288.
(3) synthesis of 4-diphenylamino phenylformic acid-4-(1-oxygen nitrogen free radical) 2,2,6,6-tetramethyl piperidine ester (TPAT)
Be dissolved in CH adding 4-diphenylamino phenylformic acid (VI) (2.0473g) in advance in the 250mL there-necked flask of drying treatment
2cl
2(50mL), solution is placed in ice-water bath and is cooled to 0 DEG C, be stirred to and dissolve completely.Add EDCI (1.6287g) and DMAP (0.4325g) subsequently, after stirring 1h at 0 DEG C, add 1-oxygen nitrogen free radical-2,2,6,6-tetramethylpiperidinol (1.5846g), stirring at room temperature reaction 24h.Dichloromethane extraction is used after reaction terminates.Oil phase extraction liquid Rotary Evaporators removes desolventizing, resultant product adopts column chromatography to carry out separating-purifying, stationary phase selects 300 order silica gel, moving phase selects the mixed solvent of normal hexane, ethyl acetate volume ratio 80:1, collect the elutriant containing product, elutriant steams to desolventize and finally obtains TPAT1.9416g, productive rate 61.8%, and product is pink solid.MS:m/z(EI):443。
(4) synthesis of 4-diphenylamino phenylformic acid-1-oxygen nitrogen free radical-2,2,6,6-tetramethyl piperidine ester polymer (PTPAT)
In advance through the 100mL beaker of drying treatment as three-electrode cell, add 50mL and contain 10
-2mol/LTPAT monomer and 10
-2mol/LLiClO
4/ acetonitrile solution is as electrolytic solution, and ito glass is as working electrode, and platinum filament is as to electrode, and silver-silver chloride electrode is as reference electrode.Adopt cyclic voltammetry to be polymerized, sweep voltage scope is 0.4V ~ 1.2V, and sweep velocity is 100mV/s, scans 10 weeks.To be polymerized complete after, in dehydrated alcohol, clean 30s by with the ITO electrode of PTPAT polymeric film, use N
2dry polymeric film is obtained after drying up.
We have carried out Infrared spectroscopy to the polymkeric substance of preparation.Result as shown in Figure 1, is as can be seen from the figure positioned at 1593.2,1497.5 and 1322.3cm
-1the peak at place belongs to the charateristic avsorption band of trianilino group, correspond to the stretching vibration peak of C=C key, C-C key and c h bond respectively.Be positioned at 1292.1 and 828.9cm
-1the peak at place belongs to the out-of-plane vibration peak of c h bond on the C-N key stretching vibration peak of tertiary amine structure and contraposition disubstituted benzene ring respectively.Be positioned at 1692.5cm
-1the peak at place belongs to the stretching vibration peak of C=O key, and is positioned at 1112.2,1164.9 and 1221.1cm
-1the spy that the peak at place then belongs to ester bond place C-O-C shakes peak.In addition, 1434.7 and 1463.0cm is positioned at
-1the peak at place belongs to-CH on oxygen nitrogen free radical group
3with-CH
2-the stretching vibration peak of c h bond.These results all show that prepared polymkeric substance has successfully connected oxygen nitrogen free radical group, and in the course of the polymerization process, oxygen nitrogen free radical is not all destroyed.In addition, we use the scanning electron microscopic observation microscopic appearance of polymkeric substance, and as shown in Figure 2, in Fig. 2,4 little figure are different amplification.Fig. 2 shows, and polymeric film shows comparatively smooth pattern, and single polymer particle diameters is less, and between 50 ~ 300nm, the maximum ga(u)ge can observing polymeric film from sectional view is about 437nm.
Fig. 3 is the cyclic voltammogram of polymerization process, the increase along with scanning times can be observed, the peak current of cyclic voltammogram increases gradually, area under the curve also increases gradually, this shows that polymkeric substance successfully gathers in ito glass substrate, and along with the increase of scanning times, the amount of polymerization also increases thereupon.Subsequently, we using the film be polymerized as working electrode, platinum filament as to electrode, silver-silver chloride electrode as reference electrode, 10
-2mol/LLiClO
4/ acetonitrile solution is as electrolytic solution, the cyclic voltammetry under different scanning speed is carried out in three electrodes, result as shown in Figure 4, the upper figure of Fig. 4 is the cyclic voltammetry curve under different scanning speed, the increase along with sweep velocity can be found, the peak current at redox peak also increases thereupon, figure below of Fig. 4 is peak current and sweep velocity linear fit graphic representation, by making graph discovery, oxidation peak and reduction peak current and sweep velocity linear, this polymeric film showing that we prepare is attached to the charge transfer of ito glass on the surface and in polymeric film uniformly by the restriction of diffusion, show satisfactory stability.
The electrochromism of embodiment 2:PTPAT in acetonitrile
The PTPAT polymeric film be attached on ito glass of preparation in embodiment 1 is put into three-electrode cell, to be dissolved with 10 in pond
-2mol/LLiClO
4/ acetonitrile solution is as electrolytic solution, and wherein working electrode is the ito glass with PTPAT polymeric film, and be platinum filament to electrode, reference electrode is silver-silver chloride electrode.Adopt cyclic voltammetry to scan, sweep voltage scope is 0.4V ~ 1.2V, and sweep velocity is 100mV/s, scans 300 weeks.Can observe with the naked eye the rising of film along with voltage, be become from yellow blackish green, and when after loss of voltage, color becomes yellow again again, so repeatedly.Relation on record cyclic voltammetry curve between redox peak and polymeric film color.In table 1:
Relation between table 1 redox peak and polymeric film color
Voltage range | 0~0.9V | 0.9V~1.2V |
Color | Yellow | Blackish green |
The PTPAT polymeric film be attached on ito glass of preparation in embodiment 1 is put into three-electrode cell, to be dissolved with 10 in pond by the electrochromism response speed of embodiment 3:PTPAT in acetonitrile and contrast gradient
-2mol/LLiClO
4/ acetonitrile solution is as electrolytic solution, and wherein working electrode is the ito glass with PTPAT polymeric film, and be platinum filament to electrode, reference electrode is silver-silver chloride electrode.Adopt electrochemical workstation and ultraviolet spectrometer coupling technique, electrochemical workstation is set to many potential steps method, and UV spectrum is set to uv-absorbing, and sweep limit is 1100 ~ 300nm.As shown in Figure 5, Fig. 5 can find out the data finally obtained, and under the condition of middle condition 0V, PTPAT has an absorption peak at 409nm place, belongs to the π-π of main polymer chain
*the characteristic peak of transfer transport, along with the increase of operating voltage, intensity diminishes gradually at this peak, this shows the generation gradually of the trianilino group oxidizing reaction of main chain, in addition along with operating voltage raises, produce new peak gradually in 700 and 1100nm place, this is because the generation of current carrier polaron and bipolaron causes.By this figure, we can observe in 409nm and 1100nm place uv-absorbing Strength Changes maximum, and when this shows that voltage changes under these two wavelength, the colour-change of PTPAT polymkeric substance is the most obvious.
In order to detect response speed and the contrast gradient of PTPAT polymkeric substance, we adopt electrochemical workstation and ultraviolet spectrometer coupling technique, and electrochemical workstation is set to timing scanning method: low potential is 0.4V, and noble potential is 1.5V, potential pulse width is 5s, and sweep time is 200s; UV spectrum is set to spectrum kinetics, and wavelength is set to 409nm and 1100nm respectively.As shown in Figure 6, Fig. 6 can find out the data finally obtained, and at 409nm place, the contrast gradient of PTPAT polymeric film is 29.9%, and the time of response is 0.74s; At 1100nm place, the contrast gradient of PTPAT polymeric film is 47.3%, and the time of response is 0.43s.
The electrochromism stability of embodiment 4:PTPAT in acetonitrile
The PTPAT polymeric film be attached on ito glass of preparation in embodiment 1 is put into three-electrode cell, and Chi Zhongwei is dissolved with 10
-2mol/LLiClO
4/ acetonitrile solution is as electrolytic solution, and wherein working electrode is the ito glass with PTPAT polymeric film, and be platinum filament to electrode, reference electrode is silver-silver chloride electrode.Adopt cyclic voltammetry to scan, sweep voltage scope is 0.4V ~ 1.2V, and sweep velocity is 200mV/s, scans 300 weeks.As shown in Figure 7, Fig. 7 can find out the cyclical stability graphic representation of PTPAT polymeric film, and first time circulation is compared with the 300th scan round, still maintains the initial electrochemical activity of 96.8% after 300 ends of scan.
Claims (8)
1. one kind such as formula the triphenylamine derivative polymkeric substance containing aerobic nitrogen free radical group shown in (I) as the application of electrochromic material:
In formula (I), n represents mean polymerisation degree, and n is 10 ~ 2000.
2. apply as claimed in claim 1, prepare by the following method such as formula the triphenylamine derivative polymkeric substance containing aerobic nitrogen free radical group shown in (I) described in it is characterized in that:
By the triphenylamine derivative monomer containing aerobic nitrogen free radical group shown in electroanalysis solvent, formula II and supporting electrolyte composition electrolytic solution, add in three-electrode cell, employing potentiostatic method, galvanostatic method or cyclic voltammetry on the working electrode (s galvanic deposit obtain polymeric film, and polymeric film is through cleaning, being drying to obtain the triphenylamine derivative polymkeric substance containing aerobic nitrogen free radical group shown in described formula (I);
3. apply as claimed in claim 2, it is characterized in that described supporting electrolyte is made up of in mole number 1:1 ratio negatively charged ion and positively charged ion, described negatively charged ion is perchlorate, tetrafluoroborate ion, hexafluorophosphoricacid acid ions, hexafluoroarsenate radical ion, nitrate ion, sulfonate ion, sulfate ion, formate ion, acetate ion, propionate ion, butyrate ion, valerate ion or phosphate anion; Described positively charged ion is sodium ion, potassium ion, lithium ion, hydrogen ion, ammonium radical ion, tetramethyl ammonium, tetraethyl ammonium ion, TBuA ion, four n-propyl ammonium ions or four n-hexyl ammonium ions.
4. apply as claimed in claim 2, it is characterized in that described electroanalysis solvent is sulfuric acid, fluosulfonic acid, hydrogen fluoride, acetic acid, water, ammoniacal liquor, N, dinethylformamide, N,N-dimethylacetamide, acetonitrile, toluene, ethanol, methyl alcohol, trichloromethane, methylene dichloride, tetrahydrofuran (THF), hexanaphthene, pyridine, propylene carbonate, benzyl cyanide, ether, acetic acid, formic acid, hydrochloric acid, phosphoric acid or sherwood oil.
5. apply as claimed in claim 3, it is characterized in that described supporting electrolyte is LiClO
4.
6. apply as claimed in claim 4, it is characterized in that described electroanalysis solvent is acetonitrile.
7. apply as claimed in claim 2, it is characterized in that in described electrolytic solution, the concentration of the triphenylamine derivative monomer containing aerobic nitrogen free radical group shown in formula II is 10
-3~ 10mol/L, the concentration of supporting electrolyte is 10
-3~ 10
-1mol/L.
8. apply as claimed in claim 2, it is characterized in that in described three-electrode cell, working electrode is gold, platinum, lead, titanium, Graphite Electrodes or ITO electrode; Reference electrode, for being silver-silver ion electrode, silver-silver chloride electrode or saturated calomel electrode, adopts platinum filament as to electrode.
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