A star-shaped carbazole derivative, a preparation method thereof and a carbazole conductive polymer

Abstract

The application belongs to the technical field of organic synthesis, and provides a star structure carbazole derivative, a preparation method thereof and a carbazole conductive polymer. The application obtains an intermediate by mixing 10-phenyl-10H-phenothiazine, N-bromosuccinimide and a first organic solvent for reaction; obtains the star structure carbazole derivative by mixing the intermediate, 9H-carbazole-2-boronic acid pinacol ester, tetrakis(triphenylphosphine)palladium, an accelerator and a second organic solvent for reaction; and obtains the carbazole conductive polymer by mixing the star structure carbazole derivative and an electrolyte solution for cyclic voltammetry electrochemical polymerization. The method is simple, has few by-products, and the star structure carbazole derivative obtained by the method is a non-coplanar star structure, which is beneficial to the embedding and discharging of electrolyte ions, so that the carbazole conductive polymer has excellent electrochemical performance and energy storage properties, and the conductive polymer also has excellent electrochromic performance.

Description

Technical Field

[0001] The present invention relates to the technical field of organic synthesis, in particular to a star-shaped carbazole derivative and a preparation method thereof, and a carbazole conductive polymer. Background Art

[0002] Conductive polymers, with their high electrical conductivity, low equivalent circuit impedance, and reversible optical tunability, are highly suitable for electrochromic applications, particularly in smart windows and intelligent electronic displays. However, current shortcomings of conductive polymers, such as poor cycling stability, difficult processing, and monotonous color, limit their practical application.

[0003] Phenothiazine and its derivatives have attracted significant attention in the field of organic optoelectronic functional materials due to their excellent optoelectronic properties, including photochromic and electrochromic characteristics, as well as highly reversible redox properties. Furthermore, phenothiazine is widely studied as a strong electron donor due to its structure containing electron-rich nitrogen and sulfur atoms, its facile synthesis, and its ease of modification.

[0004] Polycarbazole-based conductive polymers with phenothiazine as their core are characterized by readily available raw materials, low cost, and simple synthesis. Furthermore, they exhibit advantages such as high specific capacity, high conductivity, and numerous active sites during redox reactions. Consequently, polycarbazole-based conductive polymers have emerged as a key electrode material for electrochromic supercapacitors. However, existing polycarbazole-based conductive polymers still suffer from shortcomings such as poor cycling stability, difficult processing, and a single color. Summary of the Invention

[0005] In view of this, the present invention provides a star-shaped carbazole derivative and a preparation method thereof, and a carbazole conductive polymer to solve the problems of poor cycle stability, great processing difficulty and single color of existing conductive polymer materials.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions:

[0007] The present invention provides a star-shaped carbazole derivative, the structural formula of which is shown in Formula I:

[0008]

[0009] The present invention also provides a method for preparing a star-shaped carbazole derivative, comprising the following steps:

[0010] 1) mixing 10-phenyl-10H-phenothiazine, N-bromosuccinimide and a first organic solvent to carry out a bromination reaction to obtain an intermediate;

[0011] 2) coupling reaction of the intermediate obtained in step 1) with 9H-carbazole-2-boronic acid pinacol ester, tetrakis(triphenylphosphine)palladium, a promoter and a second organic solvent to obtain the star-shaped carbazole derivative shown in formula I;

[0012] The intermediate has a structural formula shown in formula II:

[0013] Preferably, the molar ratio of the 10-phenyl-10H-phenothiazine to N-bromosuccinimide in step 1) is 1:8-10; the volume / mass ratio of the first organic solvent to 10-phenyl-10H-phenothiazine is 30-50 mL:1 g; the temperature of the bromination reaction in step 1) is -5-10℃, and the time is 3-6 h.

[0014] Preferably, the first organic solvent includes one or more of anhydrous tetrahydrofuran, anhydrous N,N-dimethylformamide, anhydrous toluene, and anhydrous dimethyl sulfoxide.

[0015] Preferably, the molar ratio of the intermediate to 9H-carbazole-2-boronic acid pinacol ester and the promoter in step 2) is 1:3-3.5:2-5; the mass ratio of the tetrakis(triphenylphosphine)palladium to the intermediate is 0.001-0.01:1; the volume / mass ratio of the second organic solvent to the intermediate is 30-50 mL:1 g; the temperature of the coupling reaction in step 2) is 80-90℃, and the time is 36-48 h.

[0016] Preferably, the second organic solvent includes toluene and / or tetrahydrofuran; and the promoter is a mixture of tetrabutylammonium bromide and potassium carbonate.

[0017] The application further provides a carbazole conductive polymer prepared from the star-shaped carbazole derivative shown in formula I prepared by the preparation method.

[0018]

[0019] The n of the carbazole conductive polymer is 10-2000.

[0020] The preparation method of the carbazole conductive polymer includes the following steps:

[0021] The star-shaped carbazole derivative shown in formula I is mixed with an electrolyte solution to perform cyclic voltammetry electrochemical polymerization to obtain the carbazole conductive polymer.

[0022] Preferably, the electrolyte in the electrolyte solution comprises one or more of tetrabutylammonium hexafluorophosphate, tetrabutylammonium perchlorate, lithium tetrafluoroborate and lithium perchlorate; the solvent in the electrolyte solution comprises one or more of dichloromethane, acetonitrile and propylene carbonate; and the average polymerization degree of the carbazole-based conductive polymer is 10-2000.

[0023] Preferably, the working electrode for the cyclic voltammetry electrochemical polymerization is ITO glass, the counter electrode is platinum, the reference electrode is Ag and / or AgCl, the voltage is 0-1.5 V, and the number of polymerization circles is 8-12.

[0024] The application further provides a use of the above-mentioned carbazole-based conductive polymer in the preparation of electrochromic materials and supercapacitor materials.

[0025] Compared with the prior art, the application has the following beneficial effects:

[0026] The star-shaped carbazole derivative has a phenothiazine as a central core and a carbazole as a peripheral structure, and has abundant active sites and reaction selectivity. Meanwhile, the star-shaped carbazole derivative has a non-coplanar star-shaped structure, and can form a reticular microporous structure during electrochemical polymerization, so that the prepared carbazole-based conductive polymer film has a more loose structure.

[0027] The carbazole-based conductive polymer film can display multiple color changes under different voltages, is colorless and transparent at 0 V, is bright yellow at 1.0 V, and is olive green at 1.5 V, and has excellent electrochromic performance. In addition, the carbazole-based conductive polymer film has a more loose surface morphology, so that electrolyte ions are more easily embedded and extracted in the conductive polymer material, which not only can improve the electrochromic property of the carbazole-based conductive polymer, but also can improve the energy storage property of the carbazole-based conductive polymer. Therefore, the carbazole-based conductive polymer provided by the application has great application prospects in the fields of electrochromic and supercapacitor.

[0028] The preparation method is simple, has few by-products, is easy to separate and purify, and has a high yield, and thus has a very wide application prospect. BRIEF DESCRIPTION OF DRAWINGS

[0029] In order to more clearly illustrate the technical solutions in the embodiments of the application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiments or the prior art description. Obviously, the drawings in the following description only constitute the embodiments of the application, and for those skilled in the art, other drawings can also be obtained without creative labor on the basis of the provided drawings.

[0030] Figure 1Cyclic voltammogram of the carbazole derivative prepared in Example 1, in which the abscissa is voltage and the ordinate is current;

[0031] Figure 2 Electrochemical impedance plot of the carbazole conductive polymer thin film prepared in Example 1, in which the abscissa is real part impedance and the ordinate is imaginary part impedance;

[0032] Figure 3 Cyclic voltammogram of the carbazole conductive polymer thin film prepared in Example 1 at different scan rates, in which the abscissa is voltage and the ordinate is current;

[0033] Figure 4 UV-visible absorption spectrum of the carbazole conductive polymer thin film prepared in Example 1 at different voltages, in which the abscissa is wavelength and the ordinate is absorbance;

[0034] Figure 5 Electrochromic response time plot of the carbazole conductive polymer thin film prepared in Example 1 at 430 nm wavelength, in which the abscissa is time and the ordinate is transmittance;

[0035] Figure 6 Electrochromic response time plot of the carbazole conductive polymer thin film prepared in Example 1 at 780 nm wavelength, in which the abscissa is time and the ordinate is transmittance;

[0036] Figure 7 Electrochromic response time plot of the carbazole conductive polymer thin film prepared in Example 1 at 1100 nm wavelength, in which the abscissa is time and the ordinate is transmittance;

[0037] Figure 8 Optical contrast plot of the carbazole conductive polymer thin film prepared in Example 1 at 430 nm wavelength, in which the abscissa is time and the ordinate is transmittance;

[0038] Figure 9 Optical contrast plot of the carbazole conductive polymer thin film prepared in Example 1 at 780 nm wavelength, in which the abscissa is time and the ordinate is transmittance;

[0039] Figure 10 Optical contrast plot of the carbazole conductive polymer thin film prepared in Example 1 at 1100 nm wavelength, in which the abscissa is time and the ordinate is transmittance;

[0040] Figure 11 Cyclic stability plot of the carbazole conductive polymer thin film prepared in Example 1 at 430 nm wavelength, in which the abscissa is time and the ordinate is transmittance;

[0041] Figure 12 A cycle stability graph of the carbazole-based conductive polymer thin film prepared in Example 1 at a wavelength of 780 nm, wherein the abscissa is time and the ordinate is transmittance;

[0042] Figure 13 A cycle stability graph of the carbazole-based conductive polymer thin film prepared in Example 1 at a wavelength of 1100 nm, wherein the abscissa is time and the ordinate is transmittance;

[0043] Figure 14 A color change graph of the carbazole-based conductive polymer thin film prepared in Example 1 at different voltages;

[0044] Figure 15 A charge-discharge curve graph of the carbazole-based conductive polymer thin film prepared in Example 1 at different current densities, wherein the abscissa is time and the ordinate is voltage. DETAILED DESCRIPTION

[0045] The present application provides a star structure carbazole derivative, the structural formula of the star structure carbazole derivative is shown as formula I:

[0046]

[0047] In the present application, the preparation method of the star structure carbazole derivative comprises the following steps:

[0048] 1) mixing 10-phenyl-10H-phenothiazine, N-bromosuccinimide and a first organic solvent to carry out bromination reaction, to obtain an intermediate;

[0049] 2) mixing the intermediate obtained in step 1) with 9H-carbazole-2-boronic acid pinacol ester, tetrakis(triphenylphosphine)palladium, a promoter and a second organic solvent to carry out coupling reaction, to obtain the star structure carbazole derivative shown as formula I;

[0050] The intermediate has a structural formula shown as formula II:

[0051] In the present application, the chemical reaction equation of the bromination reaction in step 1) is as follows:

[0052]

[0053] In the present application, the molar ratio of 10-phenyl-10H-phenothiazine to N-bromosuccinimide in step 1) is 1:8-10, preferably 1:8.5-9.5, more preferably 1:9; the volume / mass ratio of the first organic solvent to 10-phenyl-10H-phenothiazine is 30-50 mL:1 g, preferably 35-45 mL:1 g, more preferably 40 mL:1 g.

[0054] In the present application, the temperature of the bromination reaction in step 1) is -5-10℃, preferably -3-8℃, further preferably 0-6℃, more preferably 2-5℃; the time of the bromination reaction is 3-6 h, preferably 3.5-5.5 h, more preferably 5 h.

[0055] In the present application, the first organic solvent comprises one or more of anhydrous tetrahydrofuran, anhydrous N,N-dimethylformamide, anhydrous toluene, anhydrous dimethyl sulfoxide.

[0056] In the present application, the coupling reaction in step 2) is a Suzuki coupling reaction, and the chemical reaction equation of the coupling reaction is as follows:

[0057]

[0058] In the present application, the molar ratio of the intermediate to 9H-carbazole-2-boronic acid pinacol ester and the promoter in step 2) is 1:3-3.5:2-5, preferably 1:3.1-3.3:2.5-4.5, more preferably 1:3.2:3; the mass ratio of the tetrakis(triphenylphosphine)palladium to the intermediate is 0.001-0.01:1, preferably 0.005-0.009:1; the volume / mass ratio of the second organic solvent to the intermediate is 30-50 mL:1 g, preferably 35-45 mL:1 g, more preferably 40 mL:1 g.

[0059] In the present application, the temperature of the coupling reaction in step 2) is 80-90℃, preferably 82-88℃, more preferably 85℃; the time of the coupling reaction is 36-48 h, preferably 38-45 h, more preferably 43 h.

[0060] In the present application, the second organic solvent comprises toluene and / or tetrahydrofuran, and when the second organic solvent is a mixed solvent of toluene and tetrahydrofuran, the volume ratio of toluene to tetrahydrofuran is preferably 1:1-2:1, more preferably 1.5:1; the promoter is a mixture of tetrabutylammonium bromide and potassium carbonate.

[0061] The present application also provides a carbazole conductive polymer prepared from the star-shaped structure carbazole derivative represented by formula I prepared by the preparation method of the star-shaped structure carbazole derivative, and the structural formula of the carbazole conductive polymer is shown in formula III.

[0062]

[0063] n of the carbazole conductive polymer is 10-2000, preferably 100-1500, further preferably 200-1000, and more preferably 500-800;

[0064] The preparation method of the carbazole conductive polymer comprises the following steps:

[0065] The star-shaped carbazole derivative shown in Formula I is mixed with an electrolyte solution to perform cyclic voltammetry electrochemical polymerization, so as to obtain the carbazole conductive polymer.

[0066] In the present application, the preparation method of the carbazole conductive polymer is preferably as follows: the star-shaped carbazole derivative shown in Formula I is dissolved in a solvent together with an electrolyte, then cyclic voltammetry electrochemical polymerization is performed with ITO glass as a working electrode, platinum wire as a counter electrode, and Ag / AgCl as a reference electrode, and then de-doping, cleaning and drying are performed, so as to obtain the carbazole conductive polymer shown in Formula III.

[0067] In the present application, the electrolyte of the electrolyte solution comprises one or more of tetrabutylammonium hexafluorophosphate, tetrabutylammonium perchlorate, lithium tetrafluoroborate and lithium perchlorate, and is preferably tetrabutylammonium perchlorate; and the solvent of the electrolyte solution comprises one or more of dichloromethane, acetonitrile and propylene carbonate, and is preferably chromatographic grade dichloromethane.

[0068] In the present application, the working electrode of the cyclic voltammetry electrochemical polymerization is ITO glass, the counter electrode is platinum, the reference electrode is Ag and / or AgCl, and the voltage is 0-1.5V, and the polymerization number of cycles is 8-12.

[0069] In the present application, the voltage of the cyclic voltammetry electrochemical polymerization is preferably 0.5-1.2V, further preferably 0.8-1.0V, and more preferably 0.9V; and the polymerization number of cycles is preferably 9-11, and more preferably 10.

[0070] In the present application, the chemical reaction formula of the cyclic voltammetry electrochemical polymerization is as shown below:

[0071]

[0072] In the present application, the voltage of the de-doping is preferably -0.3--0.1V, and more preferably -0.2V; and the time of the de-doping is preferably 30-60s, further preferably 40-50s, and more preferably 45s.

[0073] In the present application, the cleaning solvent is preferably a mixed solution of chromatographic grade with a volume ratio (dichloromethane: acetonitrile) = 2:3; the drying temperature is preferably 40-60°C, further preferably 45-55°C, and more preferably 50°C; and the drying time is preferably 1-3h, further preferably 1.5-2.5h, and more preferably 2h.

[0074] The present application also provides a use of the above-mentioned carbazole conductive polymer in the preparation of electrochromic materials and supercapacitor materials.

[0075] The technical solutions provided by the present application will be described in detail below in conjunction with the embodiments, but they should not be understood as limiting the scope of protection of the present application.

[0076] Example 1

[0077] 1. Preparation of intermediate (3Br-FSQ)

[0078] 10-phenyl-10H-phenothiazine (500 mg, 2.5 mmol) and N-bromosuccinimide NBS (4.02 g, 22.6 mmol) were sequentially added to a single-mouth round-bottom flask, and anhydrous N,N-dimethylformamide (20 mL) was added as a reaction solvent, then the bromination reaction was carried out by stirring in an ice-water mixture bath at 0°C for 8 hours. After the reaction was completed, the reaction solution was poured into 200 mL of deionized water, and extracted with 400 mL of dichloromethane 6 times to extract the N,N-dimethylformamide completely. The extracted solution was concentrated and dried with anhydrous sodium sulfate to remove water, then the sample was mixed with crude silica gel, and column chromatography was performed with fine silica gel as the stationary phase and dichloromethane and petroleum ether as the mobile phase (dichloromethane: petroleum ether = 1:3) to purify the eluent containing the intermediate. Finally, the eluent was rotary evaporated to remove the solvent and dried to obtain the pure product intermediate 3Br-FSQ, with a yield of 85%, and the chemical reaction formula is as follows:

[0079]

[0080] 2. Preparation of star-shaped carbazole derivative (3CB-FSQ)

[0081] The intermediate 3Br-FSQ prepared in step 1 (500 mg, 1.15 mmol), 9H-carbazole-2-boronic acid pinacol ester (1.16 g, 4.03 mmol), tetrakis(triphenylphosphine)palladium 5 mg, tetrabutylammonium bromide (5 mg, 0.02 mmol) and K2CO3 (476.10 mg, 3.45 mmol) were sequentially added into a 100 mL two-mouth round-bottom flask, then toluene (15 mL) and tetrahydrofuran (10 mL) were added as reaction solvents under N2 protection, 3 mL of deionized water was added, and the Suzuki coupling reaction was carried out at 90°C under reflux for 48 hours. After the reaction was completed, the product was extracted with dichloromethane for 3 times, and then the extracted solution was concentrated and dried with anhydrous sodium sulfate to remove water. Then, the sample was mixed with silica gel, and column chromatography was performed with fine silica gel as the stationary phase and dichloromethane and petroleum ether as the mobile phase (dichloromethane: petroleum ether = 1:5) to purify the star-structured carbazole derivative. The eluent containing the star-structured carbazole derivative was collected, and the solvent was removed by rotary evaporation and dried to obtain the star-structured carbazole derivative 3CB-FSQ with a yield of 82%, and the chemical reaction formula is as shown below:

[0082]

[0083] 3. Preparation of a carbazole conductive polymer (p3CB-FSQ)

[0084] The star-structured carbazole derivative 3CB-FSQ monomer 7.80 mg (molar concentration of 1 mmol / L) prepared in step 2 was added to a 10 mL volumetric flask, then 0.342 g (molar concentration of 0.1 mol / L) of tetrabutylammonium perchlorate was added as an electrolyte, and then the volume was adjusted with chromatographic grade dichloromethane. After ultrasonic treatment for 3 min at a power of 600 W, cyclic voltammetry was carried out under the following conditions: the working electrode was ITO glass (0.9 x 4 cm), the counter electrode was platinum wire, the reference electrode was Ag / AgCl, and the voltage was 1.5 V. The polymerization number was 10 cycles. Then, the sample was de-doped in a blank electrolyte solution (a mixture of 0.1 mol / L tetrabutylammonium perchlorate and dichloromethane) for 60 s (voltage of -0.2 V), and then washed with a mixture of dichloromethane and acetonitrile (2:3) to obtain a carbazole conductive polymer film p3CB-FSQ with a thickness of 220 nm and an average polymerization degree of 1800. The chemical reaction formula is as shown below:

[0085]

[0086] The cyclic voltammetry polymerization curve of the carbazole conductive polymer film in the preparation process of the present embodiment is shown in Figure 1 Figure 1 ​As can be seen from the figure, with the increase of the polymerization circle number, the peak current intensity of the carbazole conductive polymer gradually increases, indicating that the carbazole conductive polymer is successfully deposited on the ITO conductive glass.

[0087] Example 2

[0088] The difference between this example 2 and example 1 is only that the bromination reaction temperature in step 1 is-5℃; the yield of the finally obtained intermediate 3CB-FSQ is 83%.

[0089] Example 3

[0090] The difference between this example 3 and example 1 is only that the bromination reaction temperature in step 1 is 10℃; the yield of the finally obtained intermediate 3CB-FSQ is 81%.

[0091] Example 4

[0092] The difference between this example 4 and example 1 is only that the molar ratio of the intermediate 3Br-FSQ and 9H-carbazole-2-boronic acid pinacol ester in step 2 is 1:3.3, specifically, the added molar amount of the intermediate 3Br-FSQ is 1.15mmol, and the added molar amount of the 9H-carbazole-2-boronic acid pinacol ester is 3.79mmol; the yield of the finally obtained star-shaped carbazole derivative is 73%.

[0093] Example 5

[0094] The difference between this example 5 and example 1 is only that the molar ratio of the intermediate 3Br-FSQ and 9H-carbazole-2-boronic acid pinacol ester in step 2 is 1:3, specifically, the added molar amount of the intermediate 3Br-FSQ is 1.15mmol, and the added molar amount of the 9H-carbazole-2-boronic acid pinacol ester is 3.45mmol; the yield of the finally obtained star-shaped carbazole derivative is 65%.

[0095] Example 6

[0096] The difference between this example 6 and example 1 is only that the coupling reaction temperature in step 2 is 80℃; the yield of the finally obtained star-shaped carbazole derivative is 67%.

[0097] Example 7

[0098] The difference between this example 7 and example 1 is only that the coupling reaction temperature in step 2 is 85℃; the yield of the finally obtained star-shaped carbazole derivative is 73%.

[0099] Example 8

[0100] The embodiment 8 is different from the embodiment 1 only in that the number of cycles of cyclic voltammetric electrochemical polymerization in step 3 is 8 cycles; finally, a carbazole conductive polymer film with a thickness of 160 nm and an average polymerization degree of 1500 is obtained.

[0101] Embodiment 9

[0102] The embodiment 9 is different from the embodiment 1 only in that the number of cycles of cyclic voltammetric electrochemical polymerization in step 3 is 12 cycles; finally, a carbazole conductive polymer film with a thickness of 280 nm and an average polymerization degree of 2000 is obtained.

[0103] Experimental Example 1

[0104] The carbazole conductive polymer film prepared in the embodiment 1 is subjected to electrochemical impedance performance test.

[0105] The specific test method is as follows: 0.342 g of tetrabutylammonium perchlorate (molar concentration of 0.1 mol / L) is added into a 10 mL volumetric flask, which is then diluted with chromatographic grade dichloromethane to serve as a blank supporting electrolyte solution; then, the carbazole conductive polymer film prepared in the embodiment 1 is used as a working electrode, Ag / AgCl is used as a reference electrode, and a platinum wire is used as a counter electrode to test the electrochemical impedance performance of the carbazole conductive polymer film under different states. The test results are shown in Figure 2 , and it can be seen from Figure 2 that the carbazole conductive polymer film only shows a diffusion-controlled kinetic process at 0 V, and the carbazole conductive polymer film almost only shows a charge transfer-controlled kinetic process at 1.5 V, which indicates that ions can realize effective doping and dedoping on the carbazole conductive polymer film, thereby bringing changes in the electrochemical properties of the carbazole conductive polymer film.

[0106] Experimental Example 2

[0107] The carbazole conductive polymer film prepared in the embodiment 1 is subjected to cyclic voltammetry performance test.

[0108] The specific test method is as follows: 0.342 g of tetrabutylammonium perchlorate (molar concentration of 0.1 mol / L) is added into a 10 mL volumetric flask, which is then diluted with chromatographic grade dichloromethane to serve as a blank supporting electrolyte solution; then, the carbazole conductive polymer film prepared in the embodiment 1 is used as a working electrode, Ag / AgCl is used as a reference electrode, and a platinum wire is used as a counter electrode to test the cyclic voltammetry performance of the carbazole conductive polymer film under different scan rates, and the voltage window is 0-1.5 V. The test results are shown in Figure 3 , and it can be seen from Figure 3It can be seen that the carbazole conductive polymer shows obvious redox peaks, which indicates that the polymer has good redox activity. With the continuous increase of the scanning rate, the area of the CV curve of the polymer continuously increases, which indicates that the carbazole conductive polymer can be well attached to the surface of the ITO conductive substrate, and the redox behavior is reversible and is controlled by non-diffusion.

[0109] Experimental Example 3

[0110] The carbazole conductive polymer film prepared in Example 1 was subjected to ultraviolet-visible absorption spectrum test.

[0111] The specific test method is as follows: 0.342 g of tetrabutylammonium perchlorate (molar concentration of 0.1 mol / L) was added to a 10 mL volumetric flask, which was diluted with chromatographic grade dichloromethane to serve as a blank supporting electrolyte solution; then the carbazole conductive polymer film prepared in Example 1 was used as a working electrode, Ag / AgCl was used as a reference electrode, and a platinum wire was used as a counter electrode, and the ultraviolet-visible absorption spectrum of the carbazole conductive polymer film at different voltages was tested, and the test results are shown in Figure 4 The ultraviolet-visible absorption spectrum of Figure 4 It can be seen from the ultraviolet-visible absorption spectrum that the carbazole conductive polymer film has obvious absorption changes at wavelengths of 430 nm, 780 nm and 1100 nm, respectively, showing obvious electrochromic performance and excellent light modulation ability.

[0112] Experimental Example 4

[0113] The electrochromic performance of the carbazole conductive polymer film prepared in Example 1 was tested.

[0114] The specific test method is as follows: 0.342 g of tetrabutylammonium perchlorate (molar concentration of 0.1 mol / L) was added to a 10 mL volumetric flask, which was diluted with chromatographic grade dichloromethane to serve as a blank supporting electrolyte solution; then the carbazole conductive polymer film prepared in Example 1 was used as a working electrode, Ag / AgCl was used as a reference electrode, and a platinum wire was used as a counter electrode, and the electrochromic performance of the carbazole conductive polymer film was tested. The test results are shown in Figures 5 to 14 The electrochromic response time graph of Figures 5-7 It can be seen from the electrochromic response time graph that the coloring time of the film at wavelengths of 430 nm, 780 nm and 1100 nm is 1.71 s, 1.28 s and 1.35 s, respectively, and the bleaching time is 0.99 s, 1.25 s and 1.21 s, respectively, which indicates that the carbazole conductive polymer has a fast response time and meets the requirements for application in the field of smart windows and camouflage; and Figures 8-10The optical contrast graph shows that the optical contrast of the film can reach 31.3%, 12.5% ​​and 29.5% at wavelengths of 430nm, 780nm and 1100nm, respectively, indicating that the carbazole conductive polymer film has obvious electrochromic properties and can achieve a wide range of light modulation effects, and has good application prospects in the fields of smart windows and camouflage. Figures 11-13 The cyclic stability diagram shows that after 1500s of dynamic testing, the film can maintain a contrast ratio of more than 60% at wavelengths of 430nm, 780nm and 1100nm, showing relatively good electrochromic performance. Figure 14 From the color change diagram of the carbazole conductive polymer film at different voltages, it can be seen that the film is colorless and transparent at 0V, bright yellow at 1.0V, and military green at 1.5V, which further demonstrates that the film has excellent electrochromic properties.

[0115] Experimental Example 5

[0116] The charge and discharge performance of the carbazole conductive polymer film prepared in Example 1 was tested.

[0117] The specific test method is as follows: 0.342 g of tetrabutylammonium perchlorate (molar concentration of 0.1 mol / L) is added to a 10 mL volumetric flask, and the volume is fixed with chromatographic grade dichloromethane to use as a blank electrolyte solution; then the blank electrolyte solution is used as the test solution, the carbazole conductive polymer film prepared in Example 1 is used as the working electrode, the platinum wire is used as the counter electrode, and Ag / AgCl is used as the reference electrode to form a three-electrode system, the test voltage window is 0-1.5 V, and the current density is 1 A / cm 3 , 3A / cm 3 , 5A / cm 3 , 10A / cm 3 and 20A / cm 3 The charge and discharge performance of the carbazole conductive polymer film was tested under constant current conditions. Figure 15 As shown by Figure 15 It can be seen that the constant current charge-discharge curve of the carbazole conductive polymer shows obvious supercapacitive properties; it can be calculated that at 1A / cm 3 , 3A / cm 3 , 5A / cm 3 , 10A / cm 3 and 20A / cm 3 At a current density of 48.6 F / cm 3 , 45.8F / cm 3 , 43.3F / cm 3 、41.8F / cm 3and 39.4 F / cm 3 It can be seen that the carbazole conductive polymer has high volume specific capacity and good charge-discharge rate performance. The volume specific capacity of the carbazole conductive polymer is calculated by formula (1):

[0118] Cs=IΔt / ΔV (1)

[0119] In the formula, Cs is the volume specific capacity of the carbazole conductive polymer (F·cm -3 ), I is the discharge current density (A·cm -3 ), Δt is the discharge time (s), and ΔV is the voltage window (V).

[0120] The raw materials and equipment used in the present application are conventional raw materials and equipment in the field unless otherwise specified; the methods used in the present application are conventional methods in the field unless otherwise specified.

[0121] The above only describes the preferred embodiments of the present application, and it should be pointed out that for ordinary skilled persons in the art, several improvements and refinements can be made without departing from the principles of the present application, and these improvements and refinements should also be considered as the protection scope of the present application.

Claims

1. A star-shaped carbazole derivative, characterized in that: The structural formula of the star-shaped structure carbazole derivative is shown as Formula I:

2. A method for preparing a star-shaped carbazole derivative according to claim 1, characterized in that: The method comprises the following steps: 1) mixing 10-phenyl-10H-phenothiazine, N-bromosuccinimide and a first organic solvent to perform a bromination reaction to obtain an intermediate; 2) mixing the intermediate obtained in step 1) with 9H-carbazole-2-boronic acid pinacol ester, tetrakis(triphenylphosphine)palladium, a promoter and a second organic solvent to perform a coupling reaction to obtain the star-shaped structure carbazole derivative shown as Formula I; The intermediate has a structural formula as shown in Formula II:

3. The method for preparing a star-shaped carbazole derivative according to claim 2, wherein: The molar ratio of 10-phenyl-10H-phenothiazine to N-bromosuccinimide in step 1) is 1:8-10; The volume-mass ratio of the first organic solvent to 10-phenyl-10H-phenothiazine is 30-50 mL:1 g; The temperature of the bromination reaction in step 1) is -5-10 ℃, and the time is 3-6 h.

4. The method for preparing a star-shaped carbazole derivative according to claim 3, wherein: The first organic solvent comprises one or more of anhydrous tetrahydrofuran, anhydrous N,N-dimethylformamide, anhydrous toluene and anhydrous dimethyl sulfoxide.

5. The method for preparing a star-shaped carbazole derivative according to any one of claims 2 to 4, characterized in that: The molar ratio of the intermediate to 9H-carbazole-2-boronic acid pinacol ester and the promoter in step 2) is 1:3-3.5:2-5; The mass ratio of tetrakis(triphenylphosphine)palladium to the intermediate is 0.001-0.01:1; The volume-mass ratio of the second organic solvent to the intermediate is 30-50 mL:1 g; The temperature of the coupling reaction in step 2) is 80-90 ℃, and the time is 36-48 h.

6. The method for preparing a star-shaped carbazole derivative according to claim 5, characterized in that: The second organic solvent comprises toluene and / or tetrahydrofuran; The promoter is a mixture of tetrabutylammonium bromide and potassium carbonate.

7. A conductive polymer of the carbazole series prepared using the star-shaped carbazole derivative according to claim 1, characterized by, The structural formula of the carbazole conductive polymer is shown as Formula III: n of the carbazole conductive polymer is 10-2000; The preparation method of the carbazole conductive polymer comprises the following steps: Mixing the star-shaped structure carbazole derivative shown as Formula I with an electrolyte solution to perform cyclic voltammetry electrochemical polymerization to obtain the carbazole conductive polymer.

8. The carbazole-based electrically conductive polymer according to claim 7, characterized by The electrolyte in the electrolyte solution comprises one or more of tetrabutylammonium hexafluorophosphate, tetrabutylammonium perchlorate, lithium tetrafluoroborate and lithium perchlorate; The solvent in the electrolyte solution comprises one or more of dichloromethane, acetonitrile and propylene carbonate.

9. The carbazole-based electrically conductive polymer according to claim 8, characterized by The working electrode of the cyclic voltammetry electrochemical polymerization is ITO glass, the counter electrode is platinum, the reference electrode is Ag and / or AgCl, the voltage is 0-1.5 V, and the polymerization circle number is 8-12 circles.

10. The carbazole conductive polymer according to any one of claims 7-9 is used in the preparation of electrochromic materials and supercapacitor materials.

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