CN109161169B - D-A-D' asymmetric structure polymeric membrane PSWT as well as preparation method and application thereof - Google Patents

D-A-D' asymmetric structure polymeric membrane PSWT as well as preparation method and application thereof Download PDF

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CN109161169B
CN109161169B CN201810491726.8A CN201810491726A CN109161169B CN 109161169 B CN109161169 B CN 109161169B CN 201810491726 A CN201810491726 A CN 201810491726A CN 109161169 B CN109161169 B CN 109161169B
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张�诚
李林
刘军磊
欧阳密
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Zhejiang University of Technology ZJUT
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Abstract

The invention provides a DAD' asymmetric structure polymeric membrane PSWT as well as a preparation method and application thereof, wherein the method comprises the following steps: the preparation method comprises the following steps of carrying out coupling reaction on 2, 7-dibromo-9 fluorenone shown in a formula 1 under the action of an electron donating group to form an asymmetric DAD ' structural monomer, polymerizing the asymmetric DAD ' structural monomer in a three-electrode electrolytic cell system, and carrying out polymerization reaction at room temperature by adopting a cyclic voltammetry polymerization method to obtain a D-A-D ' asymmetric structural polymer film PSWT deposited on a working electrode. The invention has simple operation method, higher monomer yield and higher purity of the polymeric membrane, and the prepared product has more prominent multicolor display and excellent electrochromic property, and the material can be applied to electrochromic devices.

Description

D-A-D' asymmetric structure polymeric membrane PSWT as well as preparation method and application thereof
Technical Field
The invention relates to a polymeric film PSWT with a multicolor display D-A-D '(donor-acceptor-donor') asymmetric structure and a preparation method thereof, and the material can be applied to the preparation of electrochromic devices.
Technical Field
Since the discovery of Polymer Electrochromic (PEC) materials, it is considered to be one of the development directions of the next-generation EC materials because of its advantages of easy structure modification, high coloring efficiency, high optical contrast, and fast response speed, compared to inorganic electrochromic materials. At present, the method for realizing multicolor display of electrochromic polymers through molecular design or modification mainly comprises the design of a donor-acceptor (D-A) molecular structure and copolymerization among different molecules, wherein a copolymerization product is not beneficial to the mechanism research on the color change performance of electrochromic materials and the quality control in actual production due to the uncertainty of the molecular structure.
The D-A structure can effectively regulate and control the molecular energy band and the electrochromic property of the polymer. At present, various D-A structure conjugated polymers are reported, such as D-A structure copolymers taking benzothiadiazole, benzoquinoxaline, thiophene pyrazine, fluorenone and derivatives thereof as receptors. However, the understanding of the mechanism and the application of the material are still limited, and in order to deeply understand the relationship between the molecular structure of the conjugated polymer electrochromic material and the photoelectric property thereof, the problems that the oxidation potential is single, the color change shows single optical contrast and the like in the electrochromic property of the existing D-A-D symmetrical conjugated polymer PSWS (the molecular polymer with the same thiophene groups introduced at the two ends of fluorenone) are solved. We design a fluorenone-based D-A-D' asymmetric conjugated polymer PSWT (a molecular polymer with different groups of thiophene and triphenylamine introduced at two ends of fluorenone), study the influence of a molecular structure on the performances of color display, aggregation state morphology, optical contrast and the like, and find that the polymer has more excellent electrochromic performance compared with the PSWS.
Disclosure of Invention
In order to solve the problems of single oxidation potential, single color change display single optical contrast and the like of the existing D-A-D symmetrical conjugated polymer PSWS, the invention aims to provide a D-A-D' asymmetrical structure polymer PSWT as well as a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a polymer film PSWT with a D-A-D' asymmetric structure is prepared according to the following method:
(1) mixing 2, 7-dibromo-9 fluorenone shown in formula 1 with 2-thiopheneboronic acid and tetra (tri) phenylphosphoric palladium, dissolving in an organic solvent A under the action of an alkaline substance A under the condition of nitrogen protection, reacting at a reflux temperature for 8-12 hours to obtain a reaction mixed solution B, and carrying out post-treatment to obtain a product 2-thiophene-7-bromo-9-fluorenone shown in formula 2; the amount ratio of the 2, 7-dibromo-9 fluorenone to the 2-thiopheneboronic acid and the tetra (tri) phenylphosphide palladium shown in the formula 1 is 1: 0.5-1: 0.001-0.005; the alkaline substance A is added in the form of aqueous solution, and the addition amount of the water is based on just dissolving the alkaline substance A; the adding amount of the alkaline substance A is 2-4 mol/L based on the volume of the organic solvent A; the addition amount of the organic solvent A is 10-100 mL/mmol based on the amount of the 2, 7-dibromo-9 fluorenone substance shown in the formula 1;
(2) dissolving 2-thiophene-7-bromo-9-fluorenone shown in formula 2, 4- (diphenylamino) phenylboronic acid and tetra (tri) phenylphosphide palladium in an organic solvent B under the action of an alkaline substance B under the condition of nitrogen protection, reacting at a reflux temperature for 12-24 hours to obtain a reaction mixed solution C, and performing post-treatment to obtain a D-A-D' asymmetric structure monomer SWT shown in formula 3; the amount ratio of the 2-thiophene-7-bromo-9-fluorenone to the 4- (diphenylamino) phenylboronic acid to the tetra (tri) phenylphosphide palladium is 1: 1 to 2: 0.001 to 0.005; the alkaline substance B is added in the form of aqueous solution, and the addition amount of the water is based on just dissolving the alkaline substance B; the adding amount of the alkaline substance B is 2-4 mol/L based on the volume of the organic solvent B; the addition amount of the organic solvent B is 10-100 mL/mmol based on the amount of the 2-thiophene-7-bromo-9-fluorenone substance shown in the formula 2;
(3) dissolving the D-A-D 'asymmetric structure monomer SWT and supporting electrolyte shown in the formula 3 obtained in the step (2) in an electrolytic solvent to obtain an electrolyte, adding the electrolyte into a three-electrode electrolytic cell system, connecting the three-electrode electrolytic cell system into an electrochemical workstation, performing a deposition reaction by adopting a cyclic voltammetry anodic oxidation polymerization method under the conditions that the polymerization voltage range is 0-1.6V vs. Ag/AgCl and the number of polymerization cycles is 2-26, obtaining a polymer film deposited on a working electrode after the reaction is completed, and cleaning and drying by using an organic solvent to obtain a D-A-D' asymmetric structure polymer film PSWT shown in a formula 4; the supporting electrolyte is ammonium salt, lithium salt or 1-butyl-3-methylimidazolium tetrafluoroborate; the electrolytic cell solvent is a mixed solvent of acetonitrile (chromatographic grade) and dichloromethane (chromatographic grade) with the volume ratio of 1: 0.1-10; the addition amount of the SWT or the supporting electrolyte is calculated by the volume of the electrolytic solvent, the initial final concentration of the SWT is 0.1-10 mmol/L of the electrolytic solvent, and the initial final concentration of the supporting electrolyte is 0.01-1 mol/L of the electrolytic solvent;
the three-electrode system consists of an electrolytic cell, a working electrode, an auxiliary electrode and a reference electrode, wherein the working electrode is an Indium Tin Oxide (ITO) conductive glass, FTO or PET conductive film electrode, the auxiliary electrode is a platinum electrode or a platinum carbon electrode, the reference electrode is Ag/AgCl and takes 3mol/L potassium chloride aqueous solution as a first liquid connection, and the electrolyte is taken as a second liquid connection;
Figure BDA0001667190460000021
further, the 2, 7-dibromo-9 fluorenone represented by formula 1 may be prepared according to the following method:
taking fluorenone as a raw material, iodine as a catalyst and water as a solvent, dropwise adding liquid bromine under the stirring state, carrying out bromination reaction for 4-6 hours at 100 ℃ to obtain a reaction mixed solution A, carrying out suction filtration after the system is cooled, washing the obtained filter cake with a saturated sodium bisulfite solution and deionized water in sequence, and drying to obtain 2, 7-dibromo-9 fluorenone shown in formula 1; the amount ratio of iodine to fluorenone to liquid bromine is 1: 150: 300-450; the addition amount of the water is 1.5-2 ml/mmol based on the amount of the fluorenone substance.
In step (1), the alkaline substance a is sodium carbonate, sodium bicarbonate, potassium carbonate or the like, preferably potassium carbonate.
Furthermore, in the step (1), the organic solvent a is a mixed solvent of tetrahydrofuran and toluene mixed at any ratio, and preferably a mixed solution of tetrahydrofuran and toluene at a volume ratio of 1: 0.5-2.
Furthermore, in the step (1), the post-treatment process of the obtained reaction mixed liquid B is as follows: after the reaction is finished, adding a mixed reagent of deionized water and dichloromethane into the obtained reaction mixed solution B for extraction, combining organic phases, drying by using anhydrous magnesium sulfate, carrying out rotary evaporation and sample mixing, taking a mixed solvent of Petroleum Ether (PE) and Dioxymethane (DCM) with the volume ratio of 1: 0.5-2.5 as a mobile phase component, and carrying out column chromatography separation to obtain a product 2-thiophene-7-bromo-9-fluorenone shown in a formula 2;
in step (2), the basic substance B is sodium carbonate, sodium bicarbonate, potassium carbonate or the like, preferably potassium carbonate.
Furthermore, in the step (2), the organic solvent B is a mixed solvent of tetrahydrofuran and toluene in any proportion, and the volume ratio of tetrahydrofuran to toluene is preferably 1: 0.5-2.
Furthermore, in the step (2), the post-treatment process of the obtained reaction mixed liquid C is as follows: after the reaction is finished, adding a mixed reagent of deionized water and dichloromethane into the obtained reaction mixed solution C for extraction, combining organic phases, drying by using anhydrous magnesium sulfate, carrying out rotary evaporation on a mixed sample, taking a mixed solvent of Petroleum Ether (PE) and Dichloromethane (DCM) with the volume ratio of 1: 0.5-2.5 as a mobile phase component, and carrying out chromatographic separation to obtain a D-A-D' asymmetric structure monomer SWT shown in a formula 3;
further, in the step (3), the ammonium salt is tetrabutyl ammonium perchlorate (TBAP) or tetrabutyl ammonium hexafluorophosphate (TBAPF)6)。
Further, in the step (3), the physical salt is hexafluorophosphoric acid, tetrafluoroboric acid or trifluoromethanesulfonic acid.
And (3) mixing acetonitrile and dichloromethane in a volume ratio of 1: 0.1-10 to obtain the organic solvent for cleaning.
In the step (3), the working electrode is sequentially subjected to ultrasonic washing in 0.1% sodium hydroxide solution, absolute ethyl alcohol, acetone, toluene, absolute ethyl alcohol, toluene and acetone, preferably, the ultrasonic time is 15min each.
Further, in the step (3), the auxiliary electrode needs to be polished.
The thickness of the polymer film is 30-630 nm.
The structure of the monomer of the invention is characterized by nuclear magnetic resonance hydrogen (NMR) and mass spectra; the polymers were characterized by scanning electron microscopy (sEM), ultraviolet-visible spectroscopy (UV), electrochemical workstation. From the NMR and mass spectra of the monomers, the formation of the monomers was confirmed; the ultraviolet-visible spectrum (UV) and the electrochemical workstation are used together to obtain the ultraviolet-visible spectrum absorption under different voltages and the contrast and response time under different spectra, thereby directly proving that the D-A-D' asymmetric structure improves the color display, optical contrast or response time of the electrochromic material under certain conditions; the appearance of the obtained polymer film is characterized by a Scanning Electron Microscope (SEM), and the D-A-D' asymmetric structure brings great influence on the aggregation appearance of the electrochromic material relative to the D-A-D symmetric structure.
The D-A-D' asymmetric structure polymer film PSWT is applied to the preparation of an electrochromic device, and the electrochromic device can be color-changing glass or a flexible color-changing film.
Compared with the prior art, the invention has the beneficial effects that:
(1) by the method of the present invention, the synthesis of the D-A-D' asymmetric structural monomer adopts a stepwise synthesis method, and the method has fewer byproducts than a one-step method.
(2) The polymerization preparation method of the D-A-D' asymmetric structure material is simple and convenient, does not need harsh reaction conditions, can be operated at room temperature, does not need a complex purification process, has high product purity and low preparation energy consumption, and is favorable for production and utilization.
(3) The film-shaped material is electrochemically prepared, the film is uniform in appearance, and the forming process of the material is eliminated, so that the method is simple and convenient to operate, low in cost and easy to control the structure (size, thickness, properties and the like), and the D-A-D' asymmetric structure polymeric film has a fluffier aggregation appearance compared with a D-A-D symmetric structure.
(4) In the invention, the electrochemical cyclic voltammetry curve of the polymeric membrane shows that the conjugated polymer with the D-A-D' asymmetric structure has more redox sites, namely has more metastable states.
(5) The D-A-D' asymmetric structure conjugated polymer PSWT has more oxidation reduction peaks and more abundant color display. With the increase of voltage, when the absorbance change of the material in a visible light spectrum region is consistent with the luminosity change of the intrinsic film, the PSWT has more colors, namely the material is wheat in a PSWT neutral state, when the voltage is 1.05V, the material shows reddish brown, and with the continuous increase of the voltage, the material shows dark navy green; while PSWS is amber in neutral state and bluish in oxidized state.
(6) The film thickness of the material under different polymerization turns is measured by a Dektak-XT surface profiler, and the fact that the film thickness of the D-A-D' asymmetric structure material PSWT is increased faster along with the cyclic voltammetry polymerization turns compared with the D-A-D symmetric structure material PSWS is found, and the phenomenon can be related to the solubility of a material monomer (in a polymerization solvent, an SWS monomer is difficult to dissolve) and a film structure (in a SWT monomer structure, electrochemical sites are more, and a film with a higher cross-linking structure is easier to form).
(7) At the same film thickness, at 1100nm, the contrast is increased from 17.7% of PSWS to 75.9% of PSWT; at 650nm, the contrast ratio is increased from 29.7% of the PSWS to 36.1%, and the introduction of triphenylamine groups greatly changes the optical contrast ratio of the PSWS relative to the polymeric film with a D-A-D symmetrical structure.
(8) The coloring efficiency of PSWS at 1100nm is 14.08cm under the same film thickness2C-1Coloring efficiency at 650nm of 37.06cm2C-1Coloring efficiency at 394nm of 6.71cm2C-1(ii) a The coloring efficiency of PSWT at 1100nm, 650nm and 400nm was 157.78cm2C-1、85.48cm2C-1And 82.75cm2C-1Therefore, the coloring efficiency of PSWT at 1100nm, 650nm and 400nm is obviously improved, wherein the coloring efficiency at 1100nm and 400nm is improved by more than 10 times.
Drawings
FIG. 1 is an SEM photograph of a polymer film produced in a comparative example (left is before cycle and right is after cycle);
FIG. 2 is a cyclic voltammogram of a polymerization of a monomer in a comparative example;
FIG. 3 is a cyclic voltammogram of the polymeric membrane of the comparative example;
FIG. 4 is an SEM photograph of the polymer film obtained in example 1 (left before and right after cycles);
FIG. 5 is a cyclic voltammogram of the polymerization of monomers in example 1;
FIG. 6 is a cyclic voltammogram of the polymer film of example 1;
FIG. 7 is a graph showing the measurement of the film thickness of polymer films in comparative examples and examples (using a Dektak-XT surface profiler);
FIG. 8 is a graph showing the optical contrast of the polymer films PSWS and PSWT at the same film thickness.
Detailed Description
The invention is further described below by means of specific examples, without restricting its scope to these. The invention adopts cyclic voltammetry polymerization to prepare the polymer film, and the instruments adopted in the whole preparation process are an electrochemical workstation (CHI660E, Shanghai Chenghua instruments Co.) and a three-electrode system.
In the embodiment, the voltage range of the PSWT polymeric film during the photoelectric property test is 0-1.6V vs.
Firstly, preparing 2, 7-dibromo-9 fluorenone, adding 4g of fluorenone, 35mL of aqueous solvent and 0.015g of iodine catalyst into a 100mL clean flask, dropwise adding 3mL of bromine under stirring, heating at 100 ℃ for 6 hours, performing suction filtration after a system is cooled, washing an obtained filter cake with saturated sodium bisulfite solution and deionized water in sequence, and drying to obtain a yellow solid target product.
Comparative example
(1) Preparation of monomeric SWS
Dissolving 2, 7-dibromo-9-fluorenone (3mmol, 1.014g), 2-boronic acid thiophene (7mmol, 0.8957g), potassium carbonate (3mmol, 1.3821g) and tetrakis (tri) phenylphosphoric palladium (0.025mmol, 0.0311g) in a mixed solution of tetrahydrofuran (20ML) and toluene (30ML), adding 2ML of deionized water, refluxing for 24 hours in a nitrogen atmosphere, cooling the system, extracting with a mixed reagent of deionized water and dichloromethane, adding anhydrous magnesium sulfate to the obtained organic phase, drying, carrying out rotary evaporation and sample mixing, selecting a corresponding mobile phase (PE: DCM ═ 1: 1-2), and carrying out chromatography on the column to obtain a monomer (SWS). (1H NMR (500MHz, CDCl 3): 7.95(d, J ═ 1.4Hz, 1H), 7.76(dd, J ═ 7.8, 1.7Hz, 1H), 7.55(d, J ═ 7.8Hz, 1H), 7.41(d, J ═ 3.5Hz, 1H), 7.35(d, J ═ 5.0Hz, 1H), 7.13(dd, J ═ 4.9, 3.7Hz, 1H).) MALDI-TOF-ms (m/z): 345.2[ M + H ] +.
(2) Preparation of Polymer (PSWS) Material
SWS monomer (0.001mmol, 0.0035g) and tetrabutylammonium perchlorate (1mmol, 0.342g) are dissolved in a mixed solution of 7ml of dichloromethane and 3ml of acetonitrile to prepare a mixed solution with the monomer concentration of 0.005mol/L and the supporting electrolyte concentration of 0.1mol/L as an electrolyte. Selecting a three-electrode electrolytic cell system, taking indium tin conductive glass (ITO) as a working electrode (ultrasonic washing is carried out in 0.1% sodium hydroxide solution, absolute ethyl alcohol, acetone, toluene, absolute ethyl alcohol, toluene and acetone for 15min in sequence), taking a polished platinum wire as an auxiliary electrode (the length of the platinum wire is 4cm), taking a double-liquid-connection type silver/silver chloride electrode as a reference electrode (Ag/AgCl, 3mol/L potassium chloride aqueous solution is taken as a first liquid connection, and taking the prepared electrolyte as a second liquid connection); at room temperature (25 ℃), a polymer film is prepared by an electrochemical workstation through a cyclic voltammetry anodic oxidation polymerization method, wherein cyclic voltammetry refers to that a linear scanning voltage is applied to an electrode, scanning is carried out at a constant change speed, and when a certain set termination voltage is reached, the linear scanning voltage reversely returns to the originally set initial voltage. Therefore, firstly, setting the initial voltage 0v, the termination voltage 1.6v and the scanning rate 0.1v/s of the monomer polymerization, setting the number of polymerization cycles to be 26 (the thickness of the obtained polymerization film is 630nm), and starting the electrochemical workstation; referring to FIG. 2, which is a graph showing the cyclic voltammetry polymerization of a monomer, it can be seen that the oxidation potential of the monomer is 1.48v, and the polymerization ability of the monomer molecule is poor. After polymerization, a layer of polymer film is deposited on the surface of the ITO conductive glass of the working electrode, the ITO conductive glass is cleaned by dichloromethane and dried to obtain the working electrode with the polymer film deposited on the surface, as shown in figure 1, the aggregation state of the surface of the polymer film is uniform and fluffy as seen by an electron scanning microscope, and after 500 cyclic voltammetry stability tests, the polymer film forms large holes, which indicates that the polymer film is damaged and has poor film forming property.
(3) Polymer (PSWS) electrochemical Performance test
Dissolving tetrabutylammonium perchlorate (1mmol, 0.342g) in a mixed solution of 6ml dichloromethane and 4ml acetonitrile to prepare an electrolyte solution with the concentration of 0.1mol/L, selecting a three-electrode electrolytic cell system, taking a polymeric membrane PSWS as a working electrode, taking a polished platinum wire as an auxiliary electrode (the length of the platinum wire is 4cm), taking a double-liquid-connection type silver/silver chloride electrode as a reference electrode (an Ag/AgCl, 3mol/L potassium chloride aqueous solution is taken as a first liquid connection, and preparing the electrolyte solution with the concentration of 0.1mol/LThe resulting electrolyte was prepared as a second electrolyte). At room temperature, the cyclic voltammetry curve of the polymeric film is tested, namely, under the polymerization voltage range of 0-1.6V vs. Ag/AgC1, the working electrode containing the polymeric film is subjected to cyclic voltammetry scanning for one week at the rate of 0.1V/s, as can be seen from figure 3, the polymeric film only has one pair of redox peaks and has poor reversibility, besides, the polymeric film has single color change, and shows amber color in a neutral state, and the oxidation state changes into medium bluish color along with the increase of voltage, and as can be seen from the optical contrast, the PSWS film has 29.68% at 650nm of a visible light spectrum and 17.66% at 1100nm of a near infrared spectrum. Calculated from its response time, the coloration response time at 1100nm was 3.14s, the discoloration response time was 0.28 s; the coloration response time at 650nm was 2.99s and the fading response time was 0.55 s. The coloring efficiency at 1100nm is 14.08cm2C-1(ii) a Coloring efficiency at 650nm was 37.06cm2C-1(ii) a The coloring efficiency at 394nm was 6.71cm2C-1；
Example 1
(1) Preparation of monomeric SWT
Dissolving 2, 7-dibromo-9-fluorenone (3mmol, 1.044g), 2-thiopheneboronic acid (1.5mmol, 0.4335g), potassium carbonate (2mmol, 0.2764g) and tetra (tri) phenylphosphoric palladium (0.0025mmol, 0.0311g) in a mixed solution of tetrahydrofuran (20ML) and toluene (30ML) under the condition of nitrogen protection, adding 2ML of deionized water, refluxing for 8 hours, extracting with a mixed reagent of the deionized water and dichloromethane after a system is cooled, adding magnesium sulfate into an obtained organic phase, drying, carrying out rotary evaporation on the obtained organic phase, selecting a corresponding mobile phase to carry out chromatography on a column, and finally obtaining a 2-thiophene-7-bromo-9-fluorenone monomer; then, the obtained 2-thiophene-7-bromo-9-fluorenone monomer (3mmol, 1.022g), 4- (diphenylamino) phenylboronic acid (3mmol, 0.876g), potassium carbonate (2mmol, 0.2815g) and tetrakis (tri) phenylphosphoric palladium (0.025mmol, 0.031g) were dissolved in a mixed solution of tetrahydrofuran (20mL) and toluene (30mL), 2mL of deionized water was added, reflux was carried out in a nitrogen atmosphere for 24 hours, after the system was cooled, a mixed reagent of deionized water and dichloromethane was used for extraction, the obtained organic phase was dried over magnesium sulfate, and then the sample was stirred by rotary evaporation, and the corresponding mobile phase (PE: DCM 1: 2) was selected for chromatography on a column, thus obtaining the monomer (SWT). (1H NMR (500MHz, DMSO)7.95-7.91(m, 1H), 7.88(dd, J ═ 10.1, 5.0Hz, 2H), 7.75-7.70(m, 1H), 7.63(dd, J ═ 5.1, 1.1Hz, 1H), 7.36(dd, J ═ 8.4, 7.5Hz, 2H), 7.19(dd, J ═ 5.1, 3.6Hz, 1H), 7.14-7.07(m, 3H), 7.05(d, J ═ 8.7Hz, 1H)), MALDI-TOF-ms (m/z): 506.2[ M + H ] +.
(2) Preparation of Polymer (PSWT) Material
SWT monomer (0.001mmol, 0.0051g) and tetrabutylammonium perchlorate (1mmol, 0.342g) are dissolved in a mixed solution of 7ml of dichloromethane and 3ml of acetonitrile to prepare a mixed solution with the monomer concentration of 0.005mol/L and the supporting electrolyte TBAP concentration of 0.1mol/L as an electrolyte. A three-electrode electrolytic cell system is selected, indium tin conductive glass (ITO) is used as a working electrode (sequentially washed in 0.1% sodium hydroxide solution, absolute ethyl alcohol, acetone, toluene, absolute ethyl alcohol, toluene and acetone for 15min in an ultrasonic mode), a polished platinum wire is used as an auxiliary electrode (the length of the platinum wire is 4cm), a double-liquid-connection type silver/silver chloride electrode is used as a reference electrode (Ag/AgCl, 3mol/L potassium chloride aqueous solution is used as a first liquid connection, and the prepared electrolyte is used as a second liquid connection). At room temperature (25 ℃), preparing a polymer film by adopting a cyclic voltammetry anodic oxidation polymerization method, firstly setting the initial voltage 0v, the final voltage 1.6v and the scanning rate 0.1v/s of the monomer polymerization, setting the polymerization cycle solid number to be 19 (the thickness of the obtained polymerization film is 630nm), and starting the working procedure of an electrochemical workstation. As shown in fig. 5, which is a graph showing cyclic voltammetry polymerization curves of monomers, it is understood that the oxidation potentials of the monomers are 1.09v and 1.43v, and the monomer molecules have excellent polymerization film forming ability, and thus, compared to SWS, the structural monomer SWT has advantages of an increased number of oxidation potentials, a decreased oxidation potential, a strong polymerization film forming ability of the monomer molecules, and the like. After polymerization, a layer of polymer film is deposited on the surface of the ITO conductive glass of the working electrode, the ITO conductive glass is cleaned by dichloromethane and dried to obtain the working electrode with the polymer film deposited on the surface, as can be seen from figure 4, as shown in a scanning electron microscope image, the surface of the polymer film is fluffy and agglomerated into a sphere, after 500 cycles (stability test), the polymer film has no holes, and compared with a polymer PSWS with a D-A-D symmetrical structure, the film forming property is good.
(3) Polymer (PSWT) electrochemical Performance test
Tetrabutylammonium perchlorate (1mmol, 0.342g) is dissolved in a mixed solution of 6ml dichloromethane and 4ml acetonitrile to prepare an electrolyte solution with the concentration of 0.1mol/L, a three-electrode electrolytic cell system is selected, a polymeric membrane PSWT is used as a working electrode, a polished platinum wire is used as an auxiliary electrode (the length of the platinum wire is 4cm), a double liquid connection type silver/silver chloride electrode is used as a reference electrode (an Ag/AgCl, 3mol/L potassium chloride aqueous solution is used as a first liquid connection, and the prepared electrolyte is used as a second liquid connection). At room temperature, testing a cyclic voltammetry curve of the polymeric film, namely, under a polymerization voltage range of 0-1.6V vs. Ag/AgCl, carrying out cyclic voltammetry scanning on a working electrode containing the polymeric film at a rate of 0.1V/s for one week, as can be seen from fig. 6, the polymeric film has more oxidation-reduction potential than a symmetrical polymeric film PSWS, namely, two pairs of oxidation-reduction peaks exist, and in a neutral state, the film shows wheat color, slowly shows dark blue along with the increase of voltage, then the voltage is reduced, when the voltage reaches 1.2V, the polymeric film suddenly changes into red brown until 1.4V, the material shows dark sea green, and therefore, the D-A-D' asymmetric structure polymer electrochromic material PSWT has more abundant color change. As shown in FIG. 8 and Table 1, the optical contrast of the polymerized film was 36.1% and 75.9% at 650nm in the visible region and 1100nm in the near infrared region, respectively. The response time of the film at 1100nm was calculated as 2.2s for coloration and 1.45s for discoloration; (ii) a The coloration response time at 650nm is 2.99s, the fading response time is 1.23 s; the coloring efficiency at 1100nm, 650nm and 400nm is 157.78cm2C-1、85.48cm2C-1And 82.75cm2C-1. Therefore, under the same film thickness, the contrast of the material relative to the PSWS with the D-A-D symmetrical structure is greatly improved, the response time is not changed greatly, but the coloring efficiency of the polymeric film PSWT under different spectra is greatly improved. Therefore, the asymmetric structure of D-A-D' not only enriches the color change of the polymer PSWT under different voltages, but also greatly improves the optical contrast of the polymer PSWT under visible-near infrared spectrum, andthe coloring efficiency is improved, and the specific spectral dynamic performance is shown in Table 1.
Table 1 shows the spectral dynamic properties of the polymer films PSWS and PSWT in comparative example and example 1
Figure BDA0001667190460000071
Example 2
(1) Preparation of monomeric SWT
Dissolving 2, 7-dibromo-9-fluorenone (3mmol, 1.044g), 2-thiopheneboronic acid (1.5mmol, 0.4335g), potassium carbonate (2mmol, 0.2764g) and tetra (tri) phenylphosphoric palladium (0.0025mmol, 0.0311g) in a mixed solution of tetrahydrofuran (20ML) and toluene (30ML) under the condition of nitrogen protection, adding 2ML of deionized water, refluxing for 8 hours, extracting with a mixed reagent of the deionized water and dichloromethane after a system is cooled, adding magnesium sulfate into an obtained organic phase, drying, carrying out rotary evaporation on the obtained organic phase, selecting a corresponding mobile phase to carry out chromatography on a column, and finally obtaining a 2-thiophene-7-bromo-9-fluorenone monomer; then, the obtained 2-thiophene-7-bromo-9-fluorenone monomer (3mmol, 1.022g), 4- (diphenylamino) phenylboronic acid (3mmol, 0.876g), potassium carbonate (2mmol, 0.2815g) and tetrakis (tri) phenylphosphoric palladium (0.025mmol, 0.031g) were dissolved in a mixed solution of tetrahydrofuran (20mL) and toluene (30mL), 2mL of deionized water was added, reflux was carried out in a nitrogen atmosphere for 24 hours, after the system was cooled, a mixed reagent of deionized water and dichloromethane was used for extraction, the obtained organic phase was dried over magnesium sulfate, and then the sample was stirred by rotary evaporation, and the corresponding mobile phase (PE: DCM 1: 2) was selected for chromatography on a column, thus obtaining the monomer (SWT). (1HNMR (500MHz, DMSO)7.95-7.91(m, 1H), 7.88(dd, J ═ 10.1, 5.0Hz, 2H), 7.75-7.70(m, 1H), 7.63(dd, J ═ 5.1, 1.1Hz, 1H), 7.36(dd, J ═ 8.4, 7.5Hz, 2H), 7.19(dd, J ═ 5.1, 3.6Hz, 1H), 7.14-7.07(m, 3H), 7.05(d, J ═ 8.7Hz, 1H)), MALDI-TOF-ms (m/z): 506.2[ M + H ] +.
(2) Preparation of Polymer (PSWT) Material
SWT monomer (0.001mmol, 0.0051g) and hexafluorophosphoric acid (1mmol, 0.152g) were dissolved in a mixed solution of 7ml of methylene chloride and 3ml of acetonitrile to prepare a mixed solution of a monomer concentration of 0.005mol/L and a supporting electrolyte lithium hexafluorophosphate concentration of 0.1mol/L as an electrolytic solution. A two-electrode electrolytic cell system is selected, indium tin conductive glass (ITO) is used as a working electrode (the indium tin conductive glass is subjected to ultrasonic washing in 0.1% sodium hydroxide solution, absolute ethyl alcohol, acetone, toluene, absolute ethyl alcohol, toluene and acetone for 15min in sequence), a polished platinum wire is used as an auxiliary electrode (the length of the platinum wire is 4cm), a double-liquid-connection type silver/silver chloride electrode is used as a reference electrode (Ag/AgCl, 3mol/L potassium chloride aqueous solution is used as a first liquid connection, and the prepared electrolyte is used as a second liquid connection). Preparing a polymer film by adopting a cyclic voltammetry anodic oxidation polymerization method at room temperature (25 ℃), firstly setting the initial voltage 0v, the final voltage 1.6v and the scanning rate 0.1v/s of the monomer polymerization, setting the number of polymerization cycles to be 19 (the thickness of the obtained polymerized film is 630nm), and starting the working procedure of an electrochemical workstation. From the cyclic voltammetry polymerization curves of the monomers, the oxidation potentials of the monomers are 1.09v and 1.43v, and the monomer molecules have excellent polymerization film forming ability, so that the structural monomer SWT has the advantages of an increased number of oxidation potentials, a decreased oxidation potential, strong polymerization film forming ability of the monomer molecules, and the like compared with the SWS. After polymerization, a layer of polymer film is deposited on the surface of the ITO conductive glass of the working electrode, the ITO conductive glass is cleaned by dichloromethane and dried to obtain the working electrode with the polymer film deposited on the surface, the surface of the polymer film is fluffy and agglomerated into a sphere through electron scanning microscopy, after 500 cycles (stability test), the polymer film has no holes, and compared with a D-A-D symmetrical polymer PSWS, the film forming property is good.
(3) Polymer (PSWT) electrochemical Performance test
Dissolving lithium hexafluorophosphate (1mmol, 0.152g) in a mixed solution of 6ml dichloromethane and 4ml acetonitrile to prepare an electrolyte solution with the concentration of 0.1mol/L, selecting a three-electrode electrolytic cell system, taking a polymeric membrane PSWT as a working electrode, taking a polished platinum wire as an auxiliary electrode (the length of the platinum wire is 4cm), taking a double liquid connection type silver/silver chloride electrode as a reference electrode (an Ag/AgCl, 3mol/L potassium chloride aqueous solution is taken as a first liquid connection, and the prepared electrolyte is taken as a second liquid connection). Testing a cyclic voltammetry curve of the polymeric film at room temperature, namely, under the condition that the polymerization voltage range is 0-1.6V vs. Ag/AgCl, carrying out cyclic voltammetry scanning on a working electrode containing the polymeric film at the rate of 0.1V/s for one cycle to obtain that the oxidation-reduction potential of the polymeric film is more than that of a symmetrical polymeric film PSWS, namely two pairs of oxidation-reduction peaks exist; from cyclic voltammetry tests of the polymeric film, it was found that the film exhibited a wheat color when in a neutral state, slowly exhibited a deep blue color with an increase in voltage, and then the voltage was decreased, and when the voltage reached 1.2V, the polymeric film suddenly turned reddish brown until 1.4V, and the material exhibited a dark green color, and thus it was found that the D-a-D' asymmetric structure polymer electrochromic material PSWT had a more abundant color change. The optical contrast of the polymeric film was 36.1% and 75.9% at 650nm in the visible and 1100nm in the near infrared spectral region, respectively. The film had a coloration response time of 2.2s at 1100nm and a fade response time of 1.45 s; (ii) a The coloration response time at 650nm is 2.99s, the fading response time is 1.23 s; the coloring efficiency at 1100nm, 650nm and 400nm is 157.78cm2C-1、85.48cm2C-1And 82.75cm2C-1。
Example 3
(1) Preparation of monomeric SWT
Dissolving 2, 7-dibromo-9-fluorenone (3mmol, 1.044g), 2-thiopheneboronic acid (1.5mmol, 0.4335g), potassium carbonate (2mmol, 0.2764g) and tetra (tri) phenylphosphoric palladium (0.0025mmol, 0.0311g) in a mixed solution of tetrahydrofuran (20ML) and toluene (30ML) under the condition of nitrogen protection, adding 2ML of deionized water, refluxing for 8 hours, extracting with a mixed reagent of the deionized water and dichloromethane after a system is cooled, adding magnesium sulfate into an obtained organic phase, drying, carrying out rotary evaporation on the obtained organic phase, selecting a corresponding mobile phase to carry out chromatography on a column, and finally obtaining a 2-thiophene-7-bromo-9-fluorenone monomer; then, the obtained 2-thiophene-7-bromo-9-fluorenone monomer (3mmol, 1.022g), 4- (diphenylamino) phenylboronic acid (3mmol, 0.876g), potassium carbonate (2mmol, 0.2815g) and tetrakis (tri) phenylphosphoric palladium (0.025mmol, 0.031g) were dissolved in a mixed solution of tetrahydrofuran (20mL) and toluene (30mL), 2mL of deionized water was added, reflux was performed in a nitrogen atmosphere for 24 hours, after the system was cooled, a mixed reagent of deionized water and dichloromethane was used for extraction, the obtained organic phase was dried over magnesium sulfate, and then a stirring rod was evaporated in a rotary manner, and the corresponding mobile phase (PE: DCM 1: 2) was selected for chromatography on a column, thereby obtaining a monomer (SWT). (1H NMR (500MHz, DMSO)7.95-7.91(m, 1H), 7.88(dd, J ═ 10.1, 5.0Hz, 2H), 7.75-7.70(m, 1H), 7.63(dd, J ═ 5.1, 1.1Hz, 1H), 7.36(dd, J ═ 8.4, 7.5Hz, 2H), 7.19(dd, J ═ 5.1, 3.6Hz, 1H), 7.14-7.07(m, 3H), 7.05(d, J ═ 8.7Hz, 1H)), MALDI-TOF-ms (m/z): 506.2[ M + H ] +.
(2) Preparation of Polymer (PSWT) Material
SWT monomer (0.001mmol, 0.0051g) and tetrabutylammonium perchlorate (1mmol, 0.342g) are dissolved in a mixed solution of 7ml of dichloromethane and 3ml of acetonitrile to prepare a mixed solution with the monomer concentration of 0.005mol/L and the supporting electrolyte TBAP concentration of 0.1mol/L as an electrolyte. A three-electrode electrolytic cell system is selected, indium tin conductive glass (ITO) is used as a working electrode (sequentially washed in 0.1% sodium hydroxide solution, absolute ethyl alcohol, acetone, toluene, absolute ethyl alcohol, toluene and acetone for 15min in an ultrasonic mode), a polished platinum wire is used as an auxiliary electrode (the length of the platinum wire is 4cm), a double-liquid-connection type silver/silver chloride electrode is used as a reference electrode (Ag/AgCl, 3mol/L potassium chloride aqueous solution is used as a first liquid connection, and the prepared electrolyte is used as a second liquid connection). Preparing a polymer film by adopting a cyclic voltammetry anodic oxidation polymerization method at room temperature (25 ℃), firstly setting the initial voltage 0v, the final voltage 1.6v and the scanning rate 0.05v/s of the monomer polymerization, setting the number of polymerization cycles to be 19 (the thickness of the obtained polymerized film is 630nm), and starting the working procedure of an electrochemical workstation. From the cyclic voltammetry polymerization curves of the monomers, the oxidation potentials of the monomers are 1.09v and 1.43v, and the monomer molecules have excellent polymerization film forming ability, so that the structural monomer SWT has the advantages of an increased number of oxidation potentials, a decreased oxidation potential, strong polymerization film forming ability of the monomer molecules, and the like compared with the SWS. After polymerization, a layer of polymer film is deposited on the surface of the ITO conductive glass of the working electrode, the ITO conductive glass is cleaned by dichloromethane and dried to obtain the working electrode with the polymer film deposited on the surface, the surface of the polymer film is fluffy and agglomerated into a sphere through an electron scanning microscope, after 500 cycles (stability test), the polymer film has no holes, and compared with a D-A-D symmetrical polymer PSWS, the film forming property is good.
(3) Polymer (PSWT) electrochemical Performance test
Tetrabutylammonium perchlorate (1mmol, 0.342g) is dissolved in a mixed solution of 6ml dichloromethane and 4ml acetonitrile to prepare an electrolyte solution with the concentration of 0.1mol/L, a three-electrode electrolytic cell system is selected, a polymeric membrane PSWT is used as a working electrode, a polished platinum wire is used as an auxiliary electrode (the length of the platinum wire is 4cm), a double liquid connection type silver/silver chloride electrode is used as a reference electrode (an Ag/AgCl, 3mol/L potassium chloride aqueous solution is used as a first liquid connection, and the prepared electrolyte is used as a second liquid connection). Testing a cyclic voltammetry curve of the polymeric film at room temperature, namely, under the condition that the polymerization voltage range is 0-1.6V vs. Ag/AgCl, carrying out cyclic voltammetry scanning on a working electrode containing the polymeric film at the rate of 0.05V/s for one cycle, and comparing the oxidation-reduction potential of the polymeric film with that of a symmetrical polymeric film PSWS, namely, two pairs of oxidation-reduction peaks exist; from cyclic voltammetry tests of the polymeric film, it was found that the film exhibited a wheat color when in a neutral state, slowly exhibited a deep blue color with an increase in voltage, and then the voltage was decreased, and when the voltage reached 1.2V, the polymeric film suddenly turned reddish brown until 1.4V, and the material exhibited a dark green color, and thus it was found that the D-a-D' asymmetric structure polymer electrochromic material PSWT had a more abundant color change. The optical contrast of the polymeric film was 36.1% and 75.9% at 650nm in the visible and 1100nm in the near infrared spectral region, respectively. The film had a coloration response time of 2.2s at 1100nm and a fade response time of 1.45 s; (ii) a The coloration response time at 650nm is 2.99s, the fading response time is 1.23 s; the coloring efficiency at 1100nm, 650nm and 400nm is 157.78cm2C-1、85.48cm2C-1And 82.75cm2C-1。
Example 4
(1) Preparation of monomeric SWT
Dissolving 2, 7-dibromo-9-fluorenone (3mmol, 1.044g), 2-thiopheneboronic acid (1.5mmol, 0.4335g), potassium carbonate (2mmol, 0.2764g) and tetra (tri) phenylphosphoric palladium (0.0025mmol, 0.0311g) in a mixed solution of tetrahydrofuran (20ML) and toluene (30ML) under the condition of nitrogen protection, adding 2ML of deionized water, refluxing for 8 hours, extracting with a mixed reagent of the deionized water and dichloromethane after a system is cooled, adding magnesium sulfate into an obtained organic phase, drying, carrying out rotary evaporation on the obtained organic phase, selecting a corresponding mobile phase to carry out chromatography on a column, and finally obtaining a 2-thiophene-7-bromo-9-fluorenone monomer; then, the obtained 2-thiophene-7-bromo-9-fluorenone monomer (3mmol, 1.022g), 4- (diphenylamino) phenylboronic acid (3mmol, 0.876g), potassium carbonate (2mmol, 0.2815g) and tetrakis (tri) phenylphosphoric palladium (0.025mmol, 0.031g) were dissolved in a mixed solution of tetrahydrofuran (20mL) and toluene (30mL), 2mL of deionized water was added, reflux was carried out in a nitrogen atmosphere for 12 hours, after the system was cooled, a mixed reagent of deionized water and dichloromethane was used for extraction, the obtained organic phase was dried over magnesium sulfate, and then the sample was stirred by rotary evaporation, and the corresponding mobile phase (PE: DCM 1: 2) was selected for chromatography on a column, thus obtaining the monomer (SWT). (1H NMR (500MHz, DMSO)7.95-7.91(m, 1H), 7.88(dd, J ═ 10.1, 5.0Hz, 2H), 7.75-7.70(m, 1H), 7.63(dd, J ═ 5.1, 1.1Hz, 1H), 7.36(dd, J ═ 8.4, 7.5Hz, 2H), 7.19(dd, J ═ 5.1, 3.6Hz, 1H), 7.14-7.07(m, 3H), 7.05(d, J ═ 8.7Hz, 1H)), MALDI-TOF-ms (m/z): 506.2[ M + H ] +.
(2) Preparation of Polymer (PSWT) Material
SWT monomer (0.001mmol, 0.0051g) and tetrabutylammonium perchlorate (1mmol, 0.342g) are dissolved in a mixed solution of 7ml of dichloromethane and 3ml of acetonitrile to prepare a mixed solution with the monomer concentration of 0.005mol/L and the supporting electrolyte TBAP concentration of 0.1mol/L as an electrolyte. A three-electrode electrolytic cell system is selected, indium tin conductive glass (ITO) is used as a working electrode (sequentially washed in 0.1% sodium hydroxide solution, absolute ethyl alcohol, acetone, toluene, absolute ethyl alcohol, toluene and acetone for 15min in an ultrasonic mode), a polished platinum wire is used as an auxiliary electrode (the length of the platinum wire is 4cm), a double-liquid-connection type silver/silver chloride electrode is used as a reference electrode (Ag/AgCl, 3mol/L potassium chloride aqueous solution is used as a first liquid connection, and the prepared electrolyte is used as a second liquid connection). Preparing a polymer film by adopting a cyclic voltammetry anodic oxidation polymerization method at room temperature (25 ℃), firstly setting the initial voltage 0v, the final voltage 1.6v and the scanning rate 0.1v/s of the monomer polymerization, setting the number of polymerization cycles to be 19 (the thickness of the obtained polymerized film is 630nm), and starting the working procedure of an electrochemical workstation. From the cyclic voltammetry polymerization curves of the monomers, the oxidation potentials of the monomers are 1.09v and 1.43v, and the monomer molecules have excellent polymerization film forming ability, so that the structural monomer SWT has the advantages of an increased number of oxidation potentials, a decreased oxidation potential, strong polymerization film forming ability of the monomer molecules, and the like compared with the SWS. After polymerization, a layer of polymer film is deposited on the surface of the ITO conductive glass of the working electrode, the ITO conductive glass is cleaned by dichloromethane and dried to obtain the working electrode with the polymer film deposited on the surface, the surface of the polymer film is fluffy and agglomerated into a sphere through an electron scanning microscope, after 500 cycles (stability test), the polymer film has no holes, and compared with a D-A-D symmetrical polymer PSWS, the film forming property is good.
(3) Polymer (PSWT) electrochemical Performance test
Tetrabutylammonium perchlorate (1mmol, 0.342g) is dissolved in a mixed solution of 6ml dichloromethane and 4ml acetonitrile to prepare an electrolyte solution with the concentration of 0.1mol/L, a three-electrode electrolytic cell system is selected, a polymeric membrane PSWT is used as a working electrode, a polished platinum wire is used as an auxiliary electrode (the length of the platinum wire is 4cm), a double liquid connection type silver/silver chloride electrode is used as a reference electrode (an Ag/AgCl, 3mol/L potassium chloride aqueous solution is used as a first liquid connection, and the prepared electrolyte is used as a second liquid connection). Testing a cyclic voltammetry curve of the polymeric film at room temperature, namely, under the condition that the polymerization voltage range is 0-1.6V vs. Ag/AgCl, carrying out cyclic voltammetry scanning on a working electrode containing the polymeric film at the rate of 0.1V/s for one cycle, and comparing the oxidation-reduction potential of the polymeric film with that of a symmetrical polymeric film PSWS, namely, two pairs of oxidation-reduction peaks exist; from the cyclic voltammetry test of the polymeric film, it was found that the film exhibited a wheat color when it was in a neutral state, slowly exhibited a deep blue color with an increase in voltage, and then the voltage was decreased, and when the voltage reached 1.2V, the polymeric film suddenly turned reddish brown until 1.4V, and the material exhibited a dark green color, whereby it was found that the D-A-D' asymmetric structure polymer electrochromic material PSWT had a more excellent colorRich color change. The optical contrast of the polymeric film was 36.1% and 75.9% at 650nm in the visible and 1100nm in the near infrared spectral region, respectively. The film had a coloration response time of 2.2s at 1100nm and a fade response time of 1.45 s; (ii) a The coloration response time at 650nm is 2.99s, the fading response time is 1.23 s; the coloring efficiency at 1100nm, 650nm and 400nm is 157.78cm2C-1、85.48cm2C-1And 82.75cm2C-1。
Example 5
(1) Preparation of monomeric SWT
Dissolving 2, 7-dibromo-9-fluorenone (3mmol, 1.044g), 2-thiopheneboronic acid (1.5mmol, 0.4335g), potassium carbonate (2mmol, 0.2764g) and tetra (tri) phenylphosphoric palladium (0.0025mmol, 0.0311g) in a mixed solution of tetrahydrofuran (20ML) and toluene (30ML) under the condition of nitrogen protection, adding 2ML of deionized water, refluxing for 8 hours, extracting with a mixed reagent of the deionized water and dichloromethane after a system is cooled, adding magnesium sulfate into an obtained organic phase, drying, carrying out rotary evaporation on the obtained organic phase, selecting a corresponding mobile phase to carry out chromatography on a column, and finally obtaining a 2-thiophene-7-bromo-9-fluorenone monomer; then, the obtained 2-thiophene-7-bromo-9-fluorenone monomer (3mmol, 1.022g), 4- (diphenylamino) phenylboronic acid (3mmol, 0.876g), potassium carbonate (2mmol, 0.2815g) and tetrakis (tri) phenylphosphoric palladium (0.025mmol, 0.031g) were dissolved in a mixed solution of tetrahydrofuran (20mL) and toluene (30mL), 2mL of deionized water was added, reflux was performed in a nitrogen atmosphere for 24 hours, after the system was cooled, a mixed reagent of deionized water and dichloromethane was used for extraction, the obtained organic phase was dried over anhydrous magnesium sulfate, and then a sample was evaporated in a rotary manner, and a corresponding mobile phase (PE: DCM 1: 2) was selected for chromatography on a column, thereby obtaining a monomer (SWT). (1H NMR (500MHz, DMSO)7.95-7.91(m, 1H), 7.88(dd, J ═ 10.1, 5.0Hz, 2H), 7.75-7.70(m, 1H), 7.63(dd, J ═ 5.1, 1.1Hz, 1H), 7.36(dd, J ═ 8.4, 7.5Hz, 2H), 7.19(dd, J ═ 5.1, 3.6Hz, 1H), 7.14-7.07(m, 3H), 7.05(d, J ═ 8.7Hz, 1H)), MALDI-TOF-ms (m/z): 506.2[ M + H ] +.
(2) Preparation of Polymer (PSWT) Material
SWT monomer (0.001mmol, 0.0051g) and tetrabutylammonium perchlorate (1mmol, 0.342g) are dissolved in a mixed solution of 7ml of dichloromethane and 3ml of acetonitrile to prepare a mixed solution with the monomer concentration of 0.005mol/L and the supporting electrolyte TBAP concentration of 0.1mol/L as an electrolyte. A three-electrode electrolytic cell system is selected, indium tin conductive glass (ITO) is used as a working electrode (sequentially washed in 0.1% sodium hydroxide solution, absolute ethyl alcohol, acetone, toluene, absolute ethyl alcohol, toluene and acetone for 15min in an ultrasonic mode), a polished platinum wire is used as an auxiliary electrode (the length of the platinum wire is 4cm), a double-liquid-connection type silver/silver chloride electrode is used as a reference electrode (Ag/AgCl, 3mol/L potassium chloride aqueous solution is used as a first liquid connection, and the prepared electrolyte is used as a second liquid connection). Preparing a polymer film by adopting a cyclic voltammetry anodic oxidation polymerization method at room temperature (25 ℃), firstly setting the initial voltage 0v, the final voltage 1.6v and the scanning rate 0.1v/s of the monomer polymerization, setting the number of polymerization cycles to be 19 (the thickness of the obtained polymerized film is 630nm), and starting the working procedure of an electrochemical workstation. From the cyclic voltammetry polymerization curves of the monomers, the oxidation potentials of the monomers are 1.09v and 1.43v, and the monomer molecules have excellent polymerization film forming ability, so that the structural monomer SWT has the advantages of an increased number of oxidation potentials, a decreased oxidation potential, strong polymerization film forming ability of the monomer molecules, and the like compared with the SWS. After polymerization, a layer of polymer film is deposited on the surface of the ITO conductive glass of the working electrode, the ITO conductive glass is cleaned by dichloromethane and dried to obtain the working electrode with the polymer film deposited on the surface, the surface of the polymer film is fluffy and agglomerated into a sphere through an electron scanning microscope, after 500 cycles (stability test), the polymer film has no holes, and compared with a D-A-D symmetrical polymer PSWS, the film forming property is good.
(3) Polymer (PSWT) electrochemical Performance test
Tetrabutylammonium perchlorate (1mmol, 0.342g) is dissolved in a mixed solution of 5ml dichloromethane and 5ml acetonitrile to prepare an electrolyte solution with the concentration of 0.1mol/L, a three-electrode electrolytic cell system is selected, a polymeric membrane PSWT is taken as a working electrode, a polished platinum wire is taken as an auxiliary electrode (the length of the platinum wire is 4cm), and a double-liquid-connection type silver/silver chloride electrode is taken as a reference electrode (Ag/AgCl, 3mol/L potassium chloride water-soluble solution)The solution was used as the first solution and the electrolyte prepared as described above was used as the second solution). Testing a cyclic voltammetry curve of the polymeric film at room temperature, namely, under the condition that the polymerization voltage range is 0-1.6V vs. Ag/AgCl, carrying out cyclic voltammetry scanning on a working electrode containing the polymeric film at the rate of 0.1V/s for one cycle, and comparing the oxidation-reduction potential of the polymeric film with that of a symmetrical polymeric film PSWS, namely, two pairs of oxidation-reduction peaks exist; from the cyclic voltammetry test of the polymeric film, it was found that the film exhibited a wheat color in a neutral state, slowly exhibited a deep blue color with an increase in voltage, and then the voltage was decreased, and when the voltage reached 1.2V, the polymeric film suddenly changed into a reddish brown packet until 1.4V, and the material exhibited a dark sea green color, and thus it was found that the D-a-D' asymmetric structure polymer electrochromic material PSWT had more abundant color changes. The optical contrast of the polymeric film was 36.1% and 75.9% at 650nm in the visible and 1100nm in the near infrared spectral region, respectively. The film had a coloration response time of 2.2s at 1100nm and a fade response time of 1.45 s; (ii) a The coloration response time at 650nm is 2.99s, the fading response time is 1.23 s; the coloring efficiency at 1100nm, 650nm and 400nm is 157.78cm2C-1、85.48cm2C-1And 82.75cm2C-1。

Claims (10)

1. A polymeric film PSWT of D-A-D' asymmetric structure, comprising: the D-A-D' asymmetric structure polymeric membrane PSWT is prepared by the following method:
(1) mixing 2, 7-dibromo-9-fluorenone shown in formula 1 with 2-thiopheneboronic acid and tetra (tri) phenylphosphine palladium, dissolving in an organic solvent A under the protection of nitrogen under the action of an alkaline substance A, reacting at a reflux temperature for 8-12 hours to obtain a reaction mixed solution B, and carrying out post-treatment to obtain a product 2-thiophene-7-bromo-9-fluorenone shown in formula 2; the amount ratio of the 2, 7-dibromo-9 fluorenone to the 2-thiopheneboronic acid and the tetrakis (tri) phenylphosphine palladium shown in the formula 1 is 1: 0.5-1: 0.001-0.005; the adding amount of the alkaline substance A is 2-4 mol/L based on the volume of the organic solvent A; the alkaline substance A is added in the form of aqueous solution, and the addition amount of the water is based on just dissolving the alkaline substance A; the addition amount of the organic solvent A is 10-100 mL/mmol based on the amount of the 2, 7-dibromo-9 fluorenone substance shown in the formula 1;
(2) dissolving 2-thiophene-7-bromo-9-fluorenone shown in formula 2, 4- (diphenylamino) phenylboronic acid and tetra (tri) phenylphosphine palladium in an organic solvent B under the protection of nitrogen under the action of an alkaline substance B, reacting at a reflux temperature for 12-24 hours to obtain a reaction mixed solution C, and performing post-treatment to obtain a D-A-D' asymmetric structure monomer SWT shown in formula 3; the amount ratio of the 2-thiophene-7-bromo-9-fluorenone to the 4- (diphenylamino) phenylboronic acid to the tetra (tri) phenylphosphine palladium is 1: 1-2: 0.001-0.005; the alkaline substance B is added in the form of aqueous solution, and the addition amount of the water is based on just dissolving the alkaline substance B; the adding amount of the alkaline substance B is 2-4 mol/L based on the volume of the organic solvent B; the addition amount of the organic solvent B is 10-100 mL/mmol based on the amount of the 2-thiophene-7-bromo-9-fluorenone substance shown in the formula 2;
(3) dissolving the D-A-D 'asymmetric structure monomer SWT and supporting electrolyte shown in the formula 3 obtained in the step (2) in an electrolytic solvent to obtain an electrolyte, adding the electrolyte into a three-electrode electrolytic cell system, connecting the three-electrode electrolytic cell system into an electrochemical workstation, performing a deposition reaction by adopting a cyclic voltammetry anodic oxidation polymerization method under the conditions that the polymerization voltage range is 0-1.6V vs. Ag/AgCl and the number of polymerization cycles is 2-26, obtaining a polymer film deposited on a working electrode after the reaction is completed, and cleaning and drying by using an organic solvent to obtain a D-A-D' asymmetric structure polymer film PSWT shown in a formula 4; the supporting electrolyte is ammonium salt, lithium salt or 1-butyl-3-methylimidazolium tetrafluoroborate; the electrolytic solvent is a mixed solvent of acetonitrile and dichloromethane with the volume ratio of 1: 0.1-10; the addition amount of the D-A-D 'asymmetric structure monomer SWT or the supporting electrolyte shown in the formula 3 is calculated by the volume of the electrolytic solvent, the initial final concentration of the D-A-D' asymmetric structure monomer SWT shown in the formula 3 is 0.1-10 mmol/L of the electrolytic solvent, and the initial final concentration of the supporting electrolyte is 0.01-1 mol/L of the electrolytic solvent;
the three-electrode system consists of an electrolytic cell, a working electrode, an auxiliary electrode and a reference electrode, wherein the working electrode is Indium Tin Oxide (ITO) conductive glass, FTO or PET conductive film electrode, the auxiliary electrode is a platinum electrode or a platinum carbon electrode, the reference electrode is Ag/AgCl and takes 3mol/L potassium chloride aqueous solution as a first liquid connection, and the electrolyte is taken as a second liquid connection;
Figure FDA0002717115150000021
Figure FDA0002717115150000031
2. the D-a-D' asymmetric structured polymeric film PSWT according to claim 1, wherein: in the step (1), the alkaline substance A is sodium carbonate, sodium bicarbonate or potassium carbonate.
3. The D-a-D' asymmetric structured polymeric film PSWT according to claim 1, wherein: in the step (1), the organic solvent A is a mixed solvent of tetrahydrofuran and toluene in any proportion.
4. The D-a-D' asymmetric structured polymeric film PSWT according to claim 1, wherein: in the step (2), the alkaline substance B is sodium carbonate, sodium bicarbonate or potassium carbonate.
5. The polymeric film PSWT of claim 1, wherein the polymeric film comprises: in the step (2), the organic solvent B is a mixed solvent of tetrahydrofuran and toluene in any proportion.
6. The D-a-D' asymmetric structured polymeric film PSWT according to claim 1, wherein: in the step (2), the post-treatment process of the obtained reaction mixed liquid C is as follows: and after the reaction is finished, adding a mixed reagent of deionized water and dichloromethane into the obtained reaction mixed solution C for extraction, combining organic phases, drying by using anhydrous magnesium sulfate, carrying out rotary evaporation and sample mixing, taking a mixed solvent of petroleum ether and dichloromethane with the volume ratio of 1: 0.5-2.5 as a mobile phase component, and carrying out chromatographic separation to obtain the D-A-D' asymmetric structure monomer SWT shown in the formula 3.
7. The D-a-D' asymmetric structured polymeric film PSWT according to claim 1, wherein: in the step (3), the ammonium salt is tetrabutylammonium perchlorate or tetrabutylammonium hexafluorophosphate.
8. The D-a-D' asymmetric structured polymeric film PSWT according to claim 1, wherein: in the step (3), the lithium salt is lithium hexafluorophosphate, lithium tetrafluoroborate or lithium trifluoromethanesulfonate.
9. The D-a-D' asymmetric structured polymeric film PSWT according to claim 1, wherein: in the step (3), the organic solvent for cleaning is a mixed solvent of acetonitrile and dichloromethane with the volume ratio of 1: 0.1-10.
10. Use of the D-a-D' asymmetric-structured polymeric film PSWT of claim 1 for the preparation of electrochromic devices.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104387566A (en) * 2014-11-25 2015-03-04 江西科技师范大学 D-A-D electrochromic polymer utilizing pyridino-heterocycle as receptor
CN105887126A (en) * 2016-04-21 2016-08-24 浙江工业大学 Poly (3,4-ethylenedioxythiophene) nanowire thin film and synthetic method and application thereof
WO2016182025A1 (en) * 2015-05-14 2016-11-17 株式会社昭和 Dye-sensitized solar cell having counter electrode that is provided with collector electrode
CN106543415A (en) * 2016-09-29 2017-03-29 浙江工业大学 Thin polymer film based on chi structure conjugated molecule and preparation method and application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104387566A (en) * 2014-11-25 2015-03-04 江西科技师范大学 D-A-D electrochromic polymer utilizing pyridino-heterocycle as receptor
WO2016182025A1 (en) * 2015-05-14 2016-11-17 株式会社昭和 Dye-sensitized solar cell having counter electrode that is provided with collector electrode
CN105887126A (en) * 2016-04-21 2016-08-24 浙江工业大学 Poly (3,4-ethylenedioxythiophene) nanowire thin film and synthetic method and application thereof
CN106543415A (en) * 2016-09-29 2017-03-29 浙江工业大学 Thin polymer film based on chi structure conjugated molecule and preparation method and application

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