CN105885019B - Based on triphenylamine conjugated polymer electrochromic material and its preparation method and application - Google Patents

Based on triphenylamine conjugated polymer electrochromic material and its preparation method and application Download PDF

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CN105885019B
CN105885019B CN201610237191.2A CN201610237191A CN105885019B CN 105885019 B CN105885019 B CN 105885019B CN 201610237191 A CN201610237191 A CN 201610237191A CN 105885019 B CN105885019 B CN 105885019B
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thiophene
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CN105885019A (en
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林保平
戴斌
孙莹
杨洪
张雪勤
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Southeast University
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Abstract

One kind is based on triphenylamine conjugated polymer electrochromic material and its preparation method and application.Compound is：Under the conditions of preparation method is anhydrous and oxygen-free, by monomer M and Ar in Pd (PPh3)4Or Pd2(dba)3、P(o‑tol)3Under co-catalysis effect, polymer PC HO is obtained by Suzuki or Stille coupling reactions, again by PCHO and acceptor material A, target product two dimension conjugated organic polymer electrochromic material is obtained by knoevenagel condensation reactions under the alkaline environment that triethylamine provides.

Description

Based on triphenylamine conjugated polymer electrochromic material and its preparation method and application
Technical field
It is organic poly- more particularly, to a kind of two-dimentional conjugated type based on triphenylamine the present invention relates to electrochromic material field Compound electrochromic material and its preparation method and application.
Background technology
Electrochromism (Electrochromism, EC) refers to material under applied voltage effect, the optical property ratio of material Such as transmissivity, absorptivity and emissivity, there occurs reversible change, and are to pass through, absorb in visible ray IR absorbing area The continuously adjustable change procedure of proportionate relationship between reflection.Its macro manifestations occurs bright for the color and transparency of material Change aobviously.Under DC Electric Field, the N atoms in polymer contained by triphenylamine become amine ion after losing lone pair electrons The structure of free radical, causes the dihedral angle of polymer to diminish, and flatness improves, and the band gap of polymer reduces therewith, so polymerization The absorption spectrum of thing changes, so as to show that the color of polymer can changed conclusion.
Nowadays, conjugated polymer electrochromic material is because it easily adjusts with structure, color change is enriched, optical contrast The high extensive concern that people are caused with properties such as response time fast, easy processing processing of degree.Structures shape property, polymer are intrinsic Optical and electrical properties are determined that the polymer for designing and synthesizing low forbidden band is the hot spot of research by the forbidden band of its own.Electrostrictive polymer mutagens Color property can change with the change of band gap.The structure of polymeric material is easier to adjust.Donor-receptor type conjugation is poly- Compound is copolymerized to obtain by electron unit and electrophilic unit, passes through the combination of different donors and receptor unit, it is possible to obtain The different electrochromic material of structure, band gap, color.We can both be adjusted on electron unit, can also inhale Make an issue of on electronic unit, can be adjusted with backbone structure, be copolymerized the methods of adjusting, side chain modification, functional group adjusting to adjust The structure of polymeric material is saved, achievees the purpose that polymer band gap changes.So far, existing a variety of donor-receptor type conjugated polymers Thing is applied in electrochromic material.
By the development of decades, electrochromic material has been served in Intelligent life, industry and military affairs, with science and technology Progress, some electrochromic devices have begun to industrial production, such as information display in terms of size from the experimental stage Part, electrochromic intelligent window, color-changing solar glasses, without string mesh automobile rearview mirror, electronic storage device, color-changing solar mirror, military affairs Stealth material etc..
The content of the invention
The present invention provides one kind based on triphenylamine conjugated polymer electrochromic material and its preparation method and application, described Electrochromic polymeric compounds main chain contains trianilino group.Electrochromic polymeric compounds of the present invention can by Stille or Suzuki coupling reactions obtain, which can reversibly aoxidize, reduce generation metachromatism, and stability is good, the response time It is short.
To reach above-mentioned purpose, the present invention adopts the following technical scheme that：
One kind is based on triphenylamine conjugated polymer electrochromic material, it is characterised in that its molecular structure leads to for having structure Any one of formula：
N=10-30, represents the degree of polymerization.The X is S, O or Se, R C6~C12Alkyl chain or oxyalkyl chain, A is CNCH2COOC8H17、CNCH2CN orY is one kind in S, O, Se.
Present invention also offers a kind of preparation method, i.e.,：
Electrochromic polymeric compounds are first passed through by activated monomer M carried out again after Stille or Suzuki coupling reactions obtain after Post-polymerization functionalization obtains, and idiographic flow is：
X in wherein monomer M is one kind in S, O, Se.- Ar- represent Ar organo-tin compound or boronic acid compounds and Boric acid ester compound, Y can be S, O, Se, R C6~C12Alkyl chain or oxyalkyl chain.
The concrete technical scheme of preparation method of the present invention is as follows：
A kind of preparation method based on triphenylamine conjugated polymer electrochromic material, comprises the following steps that：(1) anhydrous nothing Under the conditions of oxygen, by monomer M and-Ar- in Pd (PPh3)4Or Pd2(dba)3、P(o-tol)3Under co-catalysis effect, pass through Suzuki Or Stille coupling reactions obtain polymer PC HO, wherein, monomer M is- Ar- represents the organotin of Ar Compound or boronic acid compounds and boric acid ester compound, Ar are aromatic ring structure, selected from diazosulfide and its derivative, benzo Dithiophene and its derivative, bicyclopentadiene 1,4-Dithiapentalene and its derivative；(2) by PCHO and acceptor material A, carried in triethylamine Target product two dimension conjugated organic polymer electrochromism is obtained by knoevenagel condensation reactions under the alkaline environment of confession Material, wherein, A CNCH2COOC8H17、CNCH2CN or
Preparation method can also further take following Optimized Measures：
Monomer M is 1: 1~1: 1.1, preferably 1: 1 with-Ar- amount ratios；Catalyst is Pd2(dba)3, catalyst amount for change The 5%~10% of compound 4, preferably 5%；Ligand is P (o-tol)3, ligand dosage is 3-5 times, preferably 3 times of catalyst amount； Reaction dissolvent is toluene, and reaction temperature is 90~110 DEG C, preferably 110 DEG C；Reaction time is 40~60h, preferably 48h.
Compound PCHO is 1: 5~1: 7, preferably 1: 6 with acceptor material A amount ratios；Triethylamine dosage is compound PCHO 1%~2%, preferably 1%；Reaction dissolvent is dry chloroform, and reaction temperature is 20~30 DEG C, preferably 25 DEG C；Reaction time For 24~36h, preferably 30h.
In above-mentioned preparation method, the specific synthesis step of the monomer M is as follows：
Step 1：Under the conditions of anhydrous and oxygen-free, 1 part of 4,7- bis- bromo- 2,1,3- diazosulfide and 2- (tributylstamlyl) Thiophene is in Pd2(PPh3)2Cl2Catalytic action under, the bromo- 7- thiophene -2,1 of 4-, 3- benzos are obtained by Stille single substitution reactions Thiadiazoles, is compound 1；
Step 2：By compound 1 and phosphorus oxychloride, dimethylformamide react to obtain the bromo- 7- of 4- (2- formylthiophenes base)- 2,1,3- diazosulfides, are compound 2；
Step 3：Under oxygen free condition, alkaline environment that compound 2 and 4- (diphenyl amino) phenyl boric acids are provided in potassium carbonate Under lower and four triphenylphosphine palladiums catalytic action, react to obtain 5- [7- (4- diphenyl aminos-phenyl)-benzene by Suzuki And [1,2,5] thiadiazoles -4- bases]-thiophene -2-formaldehyde, it is compound 3；
Step 4：By compound 3 and N- bromo-succinimides under the conditions of 0 DEG C of lucifuge, obtained by electrophilic substitution reaction 5- [7- (4- (4,4 '-dibromo)-diphenyl amino-phenyl)-benzo [1,2,5] thiadiazoles -4- bases]-thiophene -2-formaldehyde, for list Body M.
Prepared by monomer M can also further take following Optimized Measures：
The amount ratio of 4,7- bis- bromo- 2 in step 1,1,3- diazosulfide and 2- (tributylstamlyl) thiophene is 1: 1 ~1: 1.2, preferably 1: 1.05；Catalyst is Pd2(PPh3)2Cl2, catalyst amount 4,7- bis- bromo- 2,1,3- diazosulfide 5%~10%, preferably 5%；Reaction dissolvent is tetrahydrofuran, and reaction temperature is 60~70 DEG C, preferably 70 DEG C；Reaction time is 6~10h, preferably 8h.
Compound 1 and phosphorus oxychloride amount ratio are 1: 1.2~1: 1.5, preferably 1: 1.3 in step 2；Compound 1 and diformazan Base formamide amount ratio is 1: 1.5~1: 1.8, preferably 1: 1.6；Reaction dissolvent is 1,2- dichloroethanes, reaction temperature for 90~ 100 DEG C, preferably 95 DEG C；Reaction time is 12~15h, preferably 12h.
Compound 2 and 4- (diphenyl amino) phenyl boric acids amount ratio are 1: 1~1: 1.3, preferably 1: 1.1 in step 3；Chemical combination The amount ratio of thing 2 and potassium carbonate is 1: 2.5~1: 3.5, preferably 1: 3；Catalyst is Pd (PPh3)4, catalyst amount be compound The 5%~10% of 2, preferably 5%；Reaction dissolvent is toluene, and reaction temperature is 90~110 DEG C, preferably 110 DEG C；Reaction time is 20~24h, preferably 24h.
Compound 3 and N- bromo-succinimides amount ratio are 1: 2~1: 2.1, preferably 1: 2.05 in step 4；React molten Agent is chloroform, and reaction temperature is 0 DEG C, and the reaction time is 20~24h, preferably 24h.
Compared with prior art, the present invention has the advantages that：
Triphenylamine units are non-planar configurations, and backbone structure distorts, and in the case where applying voltage conditions, polymer plane increases Add so that larger change occurs for conjugated degree, causes band gap that significant changes occur, so as to show the larger change of color. Two-dimentional conjugated polymer structure is constructed using triphenylamine in the present invention, electrophilic conjugation group is introduced in polymer lateral chain, can increase Strong Intramolecular electron transfer, to widen polymeric material absorption spectrum and electrochromic range.Because two-dimentional conjugated type polymer Band gap it is relatively low, and polymer electrochromic property can change with the change of band gap, design and synthesize low forbidden band Organic polymer electrochromic material be research hot spot.The structure of two-dimensional polymer material is easier to adjust, and can pass through Backbone structure adjusts, is copolymerized the methods of adjusting, side chain modification, functional group adjusting to adjust the structure of polymeric material, reaches The purpose that polymer band gap changes.
The two-dimentional conjugated organic polymer that the main chain prepared using the above method contains triphenylamine electron donating group is electroluminescent Off-color material has excellent solubility property (dissolubility among chloroform can reach 30mg/mL) and filming performance, Ke Yizhi Connect spraying, be spin-coated on the surface filming of the electro-conductive glass such as ITO and FTO, can reversibly aoxidize, reduce generation metachromatism, surely Qualitative good, the response time is short, and color is pure, military available for no string mesh automobile rearview mirror, electrochromic intelligent window, Electronic Paper Stealth material etc..
Brief description of the drawings
Fig. 1 is UV-vis abosrption spectrogram of the thin polymer film made from embodiment 1 under different voltages.
Fig. 2 is thin polymer film transmissivity-time graph made from embodiment 1.
Embodiment
The synthesis of 1 polymer P 1 of embodiment
1) the bromo- 7- thiophene -2,1 of 4-, the synthesis of 3- diazosulfides
4,7- bis- bromo- 2,1,3- diazosulfide (20mmol), (the butyl first stannanes of 2- tri- are added in the eggplant-shape bottle of 50mL Base) thiophene (21mmol), dry THF (20mL), after solution leads to nitrogen bubbling deoxygenation 30min, be rapidly added Pd2(PPh3)2Cl2(1mmol), the back flow reaction 8h at 70 DEG C；After reaction, reaction mixture is poured into 150mL deionized waters and washed, Dichloromethane extracts three times, merges organic phase, anhydrous sodium sulfate drying, after removing solvent, crude product utilizes two in silicagel column Chloromethanes: n-hexane (1: 4, V: V) obtains the bromo- 7- thiophene -2,1 of dark yellow solid product 4-, 3- benzene for eluant, eluent separating-purifying And thiadiazoles, yield 68%.1H-NMR (500MHz, CDCl3, ppm) and δ=8.10 (d, 1H), 7.85 (m, 1H), 7.73 (d, 2H), 7.48 (d, 1H).
2) the bromo- 7- of 4- (2- formylthiophenes base) -2, the synthesis of 1,3- diazosulfide
In 100mL there-necked flasks, the addition bromo- 7- thiophene -2,1 of 4-, 3- diazosulfides (10mmol), DMF (16mmol), 0 DEG C of 1,2- dichloroethanes 40mL, be added dropwise POCl3(13mmol), be refluxed reaction 12h at 95 DEG C；After reaction The bromo- 7- of yellow solid compound 4- (2- formylthiophenes base) -2 are obtained through separating-purifying, vacuum drying, 1,3- diazosulfide, Yield is 83%.1H-NMR (500MHz, CDCl3, ppm) and δ=9.99 (s, 1H), 8.19 (d, 1H), 7.91-7.94 (d, 1H), 7.84-7.86 (t, 2H).
3) synthesis of 5- [7- (4- diphenyl aminos-phenyl)-benzo [1,2,5] thiadiazoles -4- bases]-thiophene -2-formaldehyde
The bromo- 7- of 4- (2- formylthiophenes base) -2,1,3- diazosulfide, (6mmol), 4- are added in the eggplant-shape bottle of 50mL (diphenyl amino) phenyl boric acid (6.6mmol), dry toluene 8mL, 2M wet chemical (9mL), solution lead to nitrogen bubbling After deoxygenation 30min, Pd (PPh are rapidly added3)4(0.3mmol), 110 DEG C of back flow reaction 24h；After reaction, reaction is mixed Thing is poured into deionized water and washed, and dichloromethane extracts three times, merges organic phase, anhydrous magnesium sulfate drying, will after removing solvent Crude product utilizes dichloromethane in silicagel column: n-hexane (1: 1, V: V) obtains dark red solid production for eluant, eluent separating-purifying Thing 5- [7- (4- diphenyl aminos-phenyl)-benzo [1,2,5] thiadiazoles -4- bases]-thiophene -2-formaldehyde, yield 80%.1H- NMR (300MHz, DMSO, ppm) δ=10.00 (s, 1H), 8.35-8.38 (d, 1H), 8.28-8.30 (d, 1H), 8.12-8.14 (d, 1H), 7.93-8.02 (m, 3H), 7.34-7.40 (t, 4H), 7.08-7.14 (m, 8H).
4) 5- [7- (4- (4,4 '-dibromo)-diphenyl amino-phenyl)-benzo [1,2,5] thiadiazoles -4- bases]-thiophene - The synthesis of 2- formaldehyde
In the there-necked flask of 50mL, 5- [7- (4- diphenyl aminos-phenyl)-benzo [1,2,5] thiadiazoles -4- are added Base]-thiophene -2-formaldehyde (4mmol), N- bromo-succinimides (8.2mmol), chloroform 20mL, reacted under the conditions of 0 DEG C of lucifuge 24h；After reaction, reaction mixture is poured into deionized water and washed, dichloromethane extracts three times, merges organic phase, nothing Water magnesium sulfate is dried, and after removing solvent, crude product is utilized dichloromethane in silicagel column: n-hexane (1: 2, V: V) is elution Agent separating-purifying obtain shiny red solid chemical compound 5- [7- (4- (4,4 '-dibromo)-diphenyl amino-phenyl)-benzo [1,2, 5] thiadiazoles -4- bases]-thiophene -2-formaldehyde, yield 91%.1H-NMR (300MHz, DMSO, ppm) δ=10.01 (s, 1H), 8.38-8.41 (d, 1H), 8.30-8.32 (d, 1H), 8.14-8.15 (d, 1H), 8.03-8.06 (d, 2H), 7.96-7.99 (d, 1H), 7.51-7.54 (d, 4H), 7.17-7.20 (d, 2H), 7.05-7.08 (d, 4H).
5) synthesis of polymer PC HO-1
5- [7- (4- (4,4 '-dibromo)-diphenyl amino-phenyl)-benzos [1,2,5] are added in the eggplant-shape bottle of 25mL Thiadiazoles -4- bases]-thiophene -2-formaldehyde (2mmol), 4,4,9,9- tetra- (4- hexyls phenyl) -2,7- bis- (tin trimethyl)-draw and reach 1,4-Dithiapentalene (2mmol), dry toluene 8mL are saved, solution is rapidly added Pd after leading to nitrogen bubbling deoxygenation 30min2(dba)3 (0.1mmol)、P(o-tol)3(0.3mmol) back flow reaction 48h；Treat that system is cooled to room temperature after reaction, reaction is mixed Liquid is added dropwise in 200mL methanol, and vacuum filter collects the precipitating thing of generation, and precipitating thing is purified using Soxhlet extraction device, Period is washed with acetone and n-hexane successively, after with chloroform purify out product.Through evaporating, concentrating, being dried to obtain kermesinus Polymer PC HO-1, yield 85%.
6) synthesis of organic polymer electrochromic material P1
In the eggplant-shape bottle of 25mL, add polymer PC HO-1 (1mmol), dry chloroform 10mL, 0.01mmol triethylamine, Cyanoacetic acid n-octyl (6mmol) or malononitrile or 1,3- diethyl -2- thiobarbituricacidα-s, in this narration cyanoacetic acid just Specific experiment step of the monooctyl ester as acceptor material, the experimental method of other acceptor materials is similar, and under nitrogen protection 25 DEG C reaction 30h；After reaction, reaction mixture is added dropwise in 200mL methanol, vacuum filter collects the precipitating of generation Thing, is then dissolved in chloroform and is added dropwise in 200mL methanol, and vacuum filter collects the precipitating thing of generation, repeats above-mentioned Operating procedure one time, vacuum drying gained precipitating thing can obtain organic polymer electrochromic material P1, yield 78%.Through Gel permeation chromatography is characterized, number-average molecular weight 32923, molecular weight distribution 1.39；Copolymer material has excellent molten Solve performance and filming performance.
The synthesis of 2 polymer P 2 of embodiment
1) synthesis of polymer PC HO-2
5- [7- (4- (4,4 '-dibromo)-diphenyl amino-phenyl)-benzos [1,2,5] are added in the eggplant-shape bottle of 25mL Thiadiazoles -4- bases]-thiophene -2-formaldehyde (2mmol), double [4- hexyls -5- (the trimethylstannyl) -2- thienyls] -2,1 of 4,7-, 3- diazosulfides (2mmol), dry toluene 8mL, solution are rapidly added Pd after leading to the deoxygenation of nitrogen bubbling 30 minutes2(dba)3 (0.1mmol)、P(o-tol)3(0.3mmol) back flow reaction 48h；Treat that system is cooled to room temperature after reaction, reaction is mixed Liquid is added dropwise in 200mL methanol, and vacuum filter collects the precipitating thing of generation, and precipitating thing is purified using Soxhlet extraction device, Period is washed with acetone and n-hexane successively, after with chloroform purify out product.Through evaporating, concentrating, being dried to obtain dark brown Polymer PC HO-2, yield 85%.
2) synthesis of organic polymer electrochromic material P2
In the eggplant-shape bottle of 25mL, polymer PC HO-2 (1mmol), dry tri- second of chloroform 10mL, 0.01mmol are added Amine, cyanoacetic acid n-octyl (6mmol), specific experiment step of the cyanoacetic acid n-octyl as acceptor material is described at this, The experimental method of other acceptor materials is similar, under nitrogen protection 25 DEG C of reaction 30h；After reaction, reaction is mixed Liquid is added dropwise in 200mL methanol, and vacuum filter collects the precipitating thing of generation, is then dissolved in chloroform and is added dropwise to In 200mL methanol, vacuum filter collects the precipitating thing of generation, repeats aforesaid operations step one time, vacuum drying gained precipitating thing It can obtain organic polymer electrochromic material P2, yield 72%.Characterized through gel permeation chromatography, number-average molecular weight For 26136, molecular weight distribution 1.25；Copolymer material has excellent solubility property and filming performance.
The synthesis of 3 polymer P 3 of embodiment
1) synthesis of polymer PC HO-3
5- [7- (4- (4,4 '-dibromo)-diphenyl amino-phenyl)-benzos [1,2,5] are added in the eggplant-shape bottle of 25mL Thiadiazoles -4- bases]-thiophene -2-formaldehyde (2mmol), the double (trimethyls of double [5- (2- ethylhexyls) thiophene -2- bases] -2, the 6- of 4,8- Stannyl) benzo [1,2-b：4,5-b] Dithiophene (2mmol), dry toluene 8mL, solution lead to nitrogen bubbling deoxygenation 30min After be rapidly added Pd2(dba)3(0.1mmol)、P(o-tol)3(0.3mmol) back flow reaction 48h；Treat that system is cold after reaction But to room temperature, reaction mixture is added dropwise in 200mL methanol, vacuum filter collects the precipitating thing of generation, utilizes Soxhlet Extraction element purifies precipitating thing, is during which washed successively with acetone and n-hexane, after with chloroform purify out product.Through evaporating, Concentrate, be dried to obtain kermesinus polymer PC HO-3, yield 85%.
2) synthesis of organic polymer electrochromic material P3
In the eggplant-shape bottle of 25mL, add polymer PC HO-3 (1mmol), dry chloroform 10mL, 0.01mmol triethylamine, Cyanoacetic acid n-octyl (6mmol), specific experiment step of the cyanoacetic acid n-octyl as acceptor material is described at this, other The experimental method of acceptor material is similar, under nitrogen protection 25 DEG C of reaction 30h；After reaction, by reaction mixture by It is added dropwise in 200mL methanol, vacuum filter collects the precipitating thing of generation, is then dissolved in chloroform and is added dropwise to In 200mL methanol, vacuum filter collects the precipitating thing of generation, repeats aforesaid operations step one time, vacuum drying gained precipitating thing It can obtain organic polymer electrochromic material P3, yield 83%.Characterized through gel permeation chromatography, number-average molecular weight For 31096, molecular weight distribution 1.32；Copolymer material has excellent solubility property and filming performance.
Embodiment 4
Electrochromism of the polymer P 1 in propene carbonate
1 10mg of polymer P prepared in Example 1 is dissolved in 1mL chloroforms, is rotated and is applied on clean FTO glass Film, obtained film is put into three-electrode cell, carbonic allyl ester solutions of the Chi Zhongwei dissolved with lithium perchlorate.Wherein work Electrode is the FTO glass with 1 film of polymer P；It is platinum electrode to electrode；Reference electrode is silver-silver chloride electrode.Using Cyclic voltammetry is scanned, potential range 0-1.4V, sweep speed 100mV/s.Film can be observed with the naked eye with electricity The rise of pressure, is changed into green from brown, and after voltage reduces, color reverses back brown, so repeatedly.Record on volt-ampere curve Relation between redox peaks and thin polymer film color.It is shown in Table 1：
Table 1：Relation between redox peaks and thin polymer film color
Voltage 0.0~0.6V 0.7~0.9V 1.0~1.1V 1.2V 1.3~1.4V
Color Dark brown It is light brown Light green color Green It is blackish green
In addition, measurement 0.6V-1.4V when polymer film UV-vis absorption spectrums, obtained absworption peak, see Fig. 1- 1, as can be seen from Figure as absorption intensity of the increase polymer of voltage at 453nm weakens, but new absworption peak exists 672nm occurs.
Embodiment 5
Electrochromism response speed of the polymer P 1 in propene carbonate
Obtained 1 film of polymer P is put into three-electrode cell, propene carbonates of the Chi Zhongwei dissolved with lithium perchlorate Solution.Wherein working electrode is the FTO glass with 1 film of polymer P；It is platinum electrode to electrode；Reference electrode is silver-chlorine Change silver electrode.Scanned using chronoamperometry：Low potential is 0V, high potential 1.4V, can observe with the naked eye film color with Voltage pulse converts between brown and green repeatedly.Transmissivity-time graph is shown in Fig. 1-2, response time 1.39s.

Claims (4)

1. one kind is based on triphenylamine conjugated polymer electrochromic material, it is characterised in that its molecular structure is having structure general formula Any one of：
The A is：
Middle one kind, n=10~30,
X is one kind in S, O or Se, one kind in Y S, O or Se, R C6~C12Alkyl chain or oxyalkyl chain.
A kind of 2. preparation method based on triphenylamine conjugated polymer electrochromic material described in claim 1, it is characterised in that Comprise the following steps that：(1) under the conditions of anhydrous and oxygen-free, by monomer M and-Ar- in Pd (PPh3)4Or Pd2(dba)3、P(o-tol)3Altogether With under catalytic action, polymer PC HO is obtained by Suzuki or Stille coupling reactions, wherein, monomer M is- Ar- represents the organo-tin compound of Ar, one kind in boronic acid compounds or boric acid ester compound, and Ar is virtue Fragrant ring structure, selected from diazosulfide and its derivative, benzene thiophene and its derivative, indacene 1,4-Dithiapentalene and its derivative Thing；(2) by PCHO and acceptor material, mesh is obtained by knoevenagel condensation reactions under the alkaline environment that triethylamine provides Product is marked, wherein, acceptor material CNCH2COOC8H17、CNCH2CN orOne kind therein.
3. preparation method according to claim 2, it is characterised in that the specific synthesis step of monomer M is as follows：
Step 1：Under the conditions of anhydrous and oxygen-free, 1 part of 4,7- bis- bromo- 2,1,3- diazosulfide and 2- (tributylstamlyl) thiophene In Pd2(PPh3)2Cl2Catalytic action under, the bromo- 7- thiophene -2,1 of 4-, 3- benzos thiophene two are obtained by Stille single substitution reactions Azoles, is compound 1；
Step 2：Compound 1 and phosphorus oxychloride, dimethylformamide are reacted to obtain the bromo- 7- of 4- (2- formylthiophenes base) -2,1, 3- diazosulfides, are compound 2；
Step 3：Under oxygen free condition, compound 2 and 4- (diphenyl amino) phenyl boric acids under the alkaline environment that potassium carbonate provides and Under the catalytic action of four triphenylphosphine palladiums, by Suzuki react to obtain 5- [7- (4- diphenyl aminos-phenyl)-benzo [1, 2,5] thiadiazoles -4- bases]-thiophene -2-formaldehyde is compound 3；
Step 4：By compound 3 and N- bromo-succinimides under the conditions of 0 DEG C of lucifuge, 5- is obtained by electrophilic substitution reaction [7- (4- (4,4 '-dibromo)-diphenyl amino-phenyl)-benzo [1,2,5] thiadiazoles -4- bases]-thiophene -2-formaldehyde, is monomer M。
4. according to the application based on triphenylamine conjugated polymer electrochromic material described in claim 1 mainly including no string Mesh automobile rearview mirror, electrochromic intelligent window, Electronic Paper.
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