Carbazole derivative with star-shaped structure, preparation method of carbazole derivative and carbazole conductive polymer

Abstract

The invention 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 preparation method comprises the following steps: mixing 10-phenyl-10H-phenothiazine, N-bromosuccinimide and a first organic solvent for reaction to obtain an intermediate; and mixing the intermediate with 9H-carbazole-2-boronic acid pinacol ester, tetra (triphenylphosphine) palladium, an accelerant and a second organic solvent for reaction to obtain the star structure carbazole derivative. And mixing the star-structure carbazole derivative with an electrolyte solution, and carrying out cyclic voltammetry electrochemical polymerization to obtain the carbazole conductive polymer. The method is simple and few in by-products, and the star-structure carbazole derivative obtained by the method is of a non-coplanar star structure and is beneficial to intercalation and deintercalation of electrolyte ions, so that the carbazole conductive polymer has excellent electrochemical performance and energy storage property, and meanwhile, the conductive polymer also has excellent electrochromism performance.

Description

Technical Field

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

[0002] Conductive polymer materials have the characteristics of high conductivity, low equivalent circuit impedance and reversible optical adjustability, which are very suitable as electrochromic materials, especially in the fields of smart windows, smart electronic displays, etc. At present, conductive polymer materials still have disadvantages such as poor cycle stability, difficult processing and monotonous color, which limit their practical application.

[0003] Phenothiazine and its derivatives have attracted great attention in the field of organic optoelectronic functional materials due to their excellent optoelectronic properties, photochromic and electrochromic properties, and highly reversible redox properties. At the same time, because phenothiazine contains electron-rich nitrogen and sulfur atoms in its structure, and its synthesis is simple and easy to modify, it is usually widely studied as a strong electron donor group.

[0004] Polycarbazole conductive polymers with phenothiazine as the core have the characteristics of easy availability of raw materials, low cost, simple synthesis, etc. In addition, they have advantages such as high specific capacity, high conductivity and more active sites during redox. Therefore, polycarbazole conductive polymers stand out among many electrode materials and are one of the main electrode materials for electrochromic supercapacitors. However, existing polycarbazole conductive polymers still have disadvantages such as poor cycle stability, difficult processing and 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 existing in existing conductive polymer materials.

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

[0007] The present invention provides a star-shaped carbazole derivative, the structural formula of the star-shaped carbazole derivative 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) 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 for a coupling reaction to obtain a star-shaped carbazole derivative as shown in formula I;

[0012] The structural formula of the intermediate is shown in Formula II:

[0013] Preferably, 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°C, and the time is 3-6 hours.

[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-boric 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 30-50mL:1g; the temperature of the coupling reaction in step 2) is 80-90°C, and the time is 36-48h.

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

[0017] The present invention also provides a carbazole conductive polymer prepared from a star-shaped carbazole derivative shown in Formula I prepared by the above-mentioned preparation method of a star-shaped carbazole derivative, wherein the structural formula of the carbazole conductive polymer is shown in Formula III:

[0018]

[0019] The n of the carbazole conductive polymer is 10 to 2000;

[0020] The method for preparing the carbazole conductive polymer comprises the following steps:

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

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

[0023] Preferably, 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 to 1.5 V, and the number of polymerization cycles is 8 to 12 cycles.

[0024] The present invention also provides an application of the above-mentioned carbazole conductive polymer in preparing electrochromic materials and supercapacitor materials.

[0025] It can be seen from the above technical solution that compared with the prior art, the present invention has the following beneficial effects:

[0026] The star-shaped carbazole derivative of the present invention has phenothiazine as the central core and carbazole as the peripheral structure, and has abundant active sites and reaction selectivity. At the same time, the star-shaped carbazole derivative of the present invention is a non-coplanar star-shaped structure, which forms a mesh microporous structure during electrochemical polymerization, thereby making the structure of the prepared carbazole conductive polymer film more loose.

[0027] The carbazole conductive polymer film of the present invention can show a variety of color changes under different voltages, which is colorless and transparent at 0V, bright yellow at 1.0V, and military green at 1.5V, and has excellent electrochromic performance. In addition, since the carbazole conductive polymer film of the present invention has a looser surface morphology, it is easier for electrolyte ions to embed and escape in the conductive polymer material, which can not only improve the electrochromic properties of the carbazole conductive polymer, but also improve the energy storage properties of the carbazole conductive polymer. Therefore, the carbazole conductive polymer provided by the present invention has a huge application prospect in the fields of electrochromism and supercapacitors.

[0028] The preparation method of the present invention is simple, has few by-products, is easy to separate and purify, has a significant yield, and has broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the provided drawings without paying creative work.

[0030] Figure 1The cyclic voltammetric polymerization curve of the carbazole derivative prepared in Example 1 is shown in FIG. 1 , wherein the abscissa represents voltage and the ordinate represents current;

[0031] Figure 2 This is an electrochemical impedance curve of the carbazole conductive polymer film prepared in Example 1, wherein the abscissa is the real impedance and the ordinate is the imaginary impedance;

[0032] Figure 3 The cyclic voltammetry curves of the carbazole conductive polymer film prepared in Example 1 at different scan rates, wherein the abscissa is voltage and the ordinate is current;

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

[0034] Figure 5 This is a graph showing the electrochromic response time of the carbazole conductive polymer film prepared in Example 1 at a wavelength of 430 nm, wherein the abscissa represents time and the ordinate represents transmittance;

[0035] Figure 6 This is a graph showing the electrochromic response time of the carbazole conductive polymer film prepared in Example 1 at a wavelength of 780 nm, wherein the abscissa represents time and the ordinate represents transmittance;

[0036] Figure 7 This is a graph of the electrochromic response time of the carbazole conductive polymer film prepared in Example 1 at a wavelength of 1100 nm, wherein the abscissa is time and the ordinate is transmittance;

[0037] Figure 8 This is an optical contrast diagram of the carbazole conductive polymer film prepared in Example 1 at a wavelength of 430 nm, wherein the abscissa is time and the ordinate is transmittance;

[0038] Fig. 9 This is an optical contrast diagram of the carbazole conductive polymer film prepared in Example 1 at a wavelength of 780 nm, wherein the abscissa is time and the ordinate is transmittance;

[0039] Fig.10 This is an optical contrast diagram of the carbazole conductive polymer film prepared in Example 1 at a wavelength of 1100 nm, wherein the abscissa is time and the ordinate is transmittance;

[0040] Fig.11 This is a cyclic stability diagram of the carbazole conductive polymer film prepared in Example 1 at a wavelength of 430 nm, wherein the abscissa is time and the ordinate is transmittance;

[0041] Fig.12 This is a cyclic stability diagram of the carbazole conductive polymer film prepared in Example 1 at a wavelength of 780 nm, wherein the abscissa is time and the ordinate is transmittance;

[0042] Fig.13 This is a cyclic stability diagram of the carbazole conductive polymer film prepared in Example 1 at a wavelength of 1100 nm, wherein the abscissa is time and the ordinate is transmittance;

[0043] Fig.14 This is a diagram showing the color change of the carbazole conductive polymer film prepared in Example 1 at different voltages;

[0044] Fig.15 This is a charge and discharge curve diagram of the carbazole conductive polymer film prepared in Example 1 at different current densities, wherein the abscissa is time and the ordinate is voltage. DETAILED DESCRIPTION

[0045] The present invention provides a star-shaped carbazole derivative, the structural formula of the star-shaped carbazole derivative is shown in Formula I:

[0046]

[0047] In the present invention, the preparation method of the star-shaped carbazole derivative comprises the following steps:

[0048] 1) mixing 10-phenyl-10H-phenothiazine, N-bromosuccinimide and a first organic solvent to carry out a 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 for a coupling reaction to obtain a star-shaped carbazole derivative as shown in formula I;

[0050] The structural formula of the intermediate is shown in Formula II:

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

[0052]

[0053] In the present invention, the molar ratio of 10-phenyl-10H-phenothiazine to N-bromosuccinimide in step 1) is 1:8-10, preferably 1:8.5-9.5, and 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, and more preferably 40 mL:1 g.

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

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

[0056] In the present invention, 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 invention, the molar ratio of the intermediate to 9H-carbazole-2-boric 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, and 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, and more preferably 40 mL:1 g.

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

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

[0061] The present invention also provides a carbazole conductive polymer prepared from a star-shaped carbazole derivative shown in Formula I prepared by the above-mentioned preparation method of a star-shaped carbazole derivative, wherein the structural formula of the carbazole conductive polymer is shown in Formula III:

[0062]

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

[0064] The method for preparing 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 carry out cyclic voltammetry electrochemical polymerization to obtain a carbazole conductive polymer.

[0066] In the present invention, the preparation method of the carbazole conductive polymer is preferably: dissolving the star-shaped carbazole derivative shown in formula I and an electrolyte in a solvent, then performing cyclic voltammetry electrochemical polymerization using ITO glass as a working electrode, platinum wire as a counter electrode, and Ag / AgCl as a reference electrode, and then dedoping, washing and drying to obtain a carbazole conductive polymer shown in formula III.

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

[0068] In the present invention, 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 0-1.5V, and the number of polymerization cycles is 8-12 cycles.

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

[0070] In the present invention, the chemical reaction formula of the cyclic voltammetry electrochemical polymerization is as follows:

[0071]

[0072] In the present invention, the dedoping voltage is preferably -0.3 to -0.1 V, more preferably -0.2 V; the dedoping time is preferably 30 to 60 s, more preferably 40 to 50 s, more preferably 45 s.

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

[0074] The present invention also provides an application of the above-mentioned carbazole conductive polymer in preparing electrochromic materials and supercapacitor materials.

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

[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 added to a single-mouth round-bottom flask in sequence, and anhydrous N,N-dimethylformamide (20 mL) was added as a reaction solvent. The mixture was stirred in an ice-water mixed bath at 0°C for 8 hours for bromination reaction. After the reaction was completed, the reaction solution was poured into 200 mL of deionized water and extracted 6 times with 400 mL of dichloromethane to extract N,N-dimethylformamide. The extracted extract was concentrated and dried with anhydrous sodium sulfate to remove water. The sample was then mixed with coarse 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 product. The eluent containing the intermediate was collected. Finally, the eluent was evaporated to remove the solvent and dried to obtain the pure product intermediate 3Br-FSQ with a yield of 85%. The chemical reaction formula is shown below:

[0079]

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

[0081] The intermediate 3Br-FSQ (500 mg, 1.15 mmol) prepared in step 1, 9H-carbazole-2-boronic acid pinacol ester (1.16 g, 4.03 mmol), 5 mg of tetrakis(triphenylphosphine)palladium, tetrabutylammonium bromide (5 mg, 0.02 mmol) and K2CO3 (476.10 mg, 3.45 mmol) were added to a 100 mL two-necked round-bottom flask, and then toluene (15 mL) and tetrahydrofuran (10 mL) were added as reaction solvents under N2 protection, and 3 ml of deionized water was added. , heated to reflux at 90°C for 48 hours for Suzuki coupling reaction, after the reaction, extracted with dichloromethane for 3 times, and then the extract obtained by extraction was concentrated and dried with anhydrous sodium sulfate to remove water, and then mixed with coarse silica gel, and purified by column chromatography with fine silica gel as the stationary phase and dichloromethane and petroleum ether as the mobile phase (dichloromethane: petroleum ether = 1:5), and the eluent containing the star-shaped carbazole derivative was collected, and finally the eluent was evaporated to remove the solvent and dried to obtain the star-shaped carbazole derivative 3CB-FSQ, with a yield of 82%. The chemical reaction formula is as follows:

[0082]

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

[0084] 7.80 mg (molar concentration of 1 mmol / L) of the star-shaped carbazole derivative 3CB-FSQ monomer prepared in step 2 was added to a 10 mL volumetric flask, and then 0.342 g (molar concentration of 0.1 mol / L) of tetrabutylammonium perchlorate was added as an electrolyte, and then the volume was fixed with chromatographic grade dichloromethane. After ultrasonication at a power of 600 W for 3 min, the working electrode was ITO glass (0.9×4 cm), the counter electrode was platinum wire, the reference electrode was Ag / AgCl, and the voltage was 1 Cyclic voltammetry electrochemical polymerization was carried out under the condition of 0.5V, and the number of polymerization cycles was 10; then, it was dedoped in a blank electrolyte solution (a mixture of 0.1 mol / L tetrabutylammonium perchlorate and dichloromethane) for 60s (voltage was -0.2V), and then washed with a chromatographic grade mixed solution of dichloromethane: acetonitrile = 2:3, and dried at a temperature of 50°C for 2 hours to obtain a carbazole conductive polymer film p3CB-FSQ with a thickness of 220nm and an average degree of polymerization of 1800. The chemical reaction formula is as follows:

[0085]

[0086] The cyclic voltammetry polymerization curve of the carbazole conductive polymer film in the preparation process of this embodiment is as follows: Figure 1 As shown, from Figure 1It can be seen that with the increase of the number of polymerization cycles, 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 Example 2 and Example 1 is that the bromination reaction temperature in step 1 is -5°C; the yield of the intermediate 3CB-FSQ obtained finally is 83%.

[0089] Example 3

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

[0091] Example 4

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

[0093] Example 5

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

[0095] Example 6

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

[0097] Example 7

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

[0099] Example 8

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

[0101] Example 9

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

[0103] Experimental Example 1

[0104] The electrochemical impedance performance of the carbazole conductive polymer film prepared in Example 1 was tested.

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

[0106] Experimental Example 2

[0107] The cyclic voltammetry performance of the carbazole conductive polymer film prepared in Example 1 was tested.

[0108] The specific test method is: add 0.342g of tetrabutylammonium perchlorate (molar concentration is 0.1mol / L) into a 10mL volumetric flask, dilute with chromatographic grade dichloromethane, and use it as a blank supporting electrolyte solution; then use the carbazole conductive polymer film prepared in Example 1 as the working electrode, Ag / AgCl as the reference electrode, and platinum wire as the counter electrode to test the cyclic voltammetry performance of the carbazole conductive polymer film at different scan rates, with a voltage window of 0 to 1.5V. The test results are as follows: Figure 3 As shown, from Figure 3It can be seen that the carbazole conductive polymer exhibits obvious redox peaks, which indicates that the polymer has good redox activity. As the scanning rate continues to increase, the area of ​​the CV curve of the polymer continues to increase, 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 non-diffusion controlled.

[0109] Experimental Example 3

[0110] The carbazole conductive polymer film prepared in Example 1 was tested by UV-visible absorption spectrum.

[0111] The specific test method is: 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, which is used as a blank supporting electrolyte solution; then the carbazole conductive polymer film prepared in Example 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, and the ultraviolet-visible absorption spectrum of the carbazole conductive polymer film under different voltages is tested. The test results are as follows: Figure 4 As shown by Figure 4 It can be seen from the UV-visible absorption spectrum that the carbazole conductive polymer film has obvious absorption changes at wavelengths of 430nm, 780nm and 1100nm, respectively, showing obvious electrochromic properties 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: add 0.342g of tetrabutylammonium perchlorate (molar concentration is 0.1mol / L) into a 10mL volumetric flask, dilute with chromatographic grade dichloromethane, and use it as a blank supporting electrolyte solution; then use the carbazole conductive polymer film prepared in Example 1 as the working electrode, Ag / AgCl as the reference electrode, and platinum wire as the counter electrode, and test the electrochromic performance of the carbazole conductive polymer film. The test results are as follows: Figures 5 to 14 As shown, among which, Figures 5 to 7 From the electrochromic response time diagram, it can be seen that the coloring time of the film at wavelengths of 430nm, 780nm and 1100nm is 1.71s, 1.28s and 1.35s respectively, and the fading time is 0.99s, 1.25s and 1.21s respectively, which shows that the carbazole conductive polymer has a fast response time and meets the requirements for application in the fields of smart windows and camouflage. Figures 8 to 10From the optical contrast diagram, it can be seen that the optical contrast of the film can reach 31.3%, 12.5% ​​and 29.5% at wavelengths of 430nm, 780nm and 1100nm, respectively, which shows that the carbazole conductive polymer film has obvious electrochromic properties, can achieve a wide range of light modulation, and has good application prospects in the fields of smart windows and camouflage; Figures 11 to 13 From the cyclic stability diagram, it can be seen that after 1500s of kinetic testing, the film can maintain a contrast ratio of more than 60% at wavelengths of 430nm, 780nm and 1100nm, showing relatively good electrochromic performance. Fig.14 From the color change diagram of the carbazole conductive polymer film under 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 illustrates 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: 0.342g of tetrabutylammonium perchlorate (molar concentration of 0.1mol / L) is added to a 10mL volumetric flask, and the volume is fixed with chromatographic grade dichloromethane to use it 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 0-1.5V, and the current density is 1A / 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. Fig.15 As shown by Fig.15 It can be seen that the constant current charge-discharge curve of carbazole conductive polymers 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 39.4F / cm 3 It can be seen that the carbazole conductive polymer has a higher volumetric capacity and better charge-discharge rate performance. The volumetric capacity of the carbazole conductive polymer is calculated by formula (1):

[0118] Cs=IΔt / ΔV (1)

[0119] Where Cs is the volumetric 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 invention, unless otherwise specified, are all commonly used raw materials and equipment in the art; the methods used in the present invention, unless otherwise specified, are all conventional methods in the art.

[0121] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

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

2. A method for preparing a star-shaped carbazole derivative according to claim 1, characterized in that: The steps include: 1) mixing 10-phenyl-10H-phenothiazine, N-bromosuccinimide and a first organic solvent to carry out 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 for a coupling reaction to obtain a star-shaped carbazole derivative as shown in formula I; The structural formula of the intermediate is shown in Formula II:

3. The method for preparing a star-shaped carbazole derivative according to claim 2, characterized in that: 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 to 10°C and the time is 3 to 6 hours.

4. The method for preparing a star-shaped carbazole derivative according to claim 3, characterized in that: The first organic solvent includes 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 to 0.01:1; The volume mass ratio of the second organic solvent to the intermediate is 30-50 mL: 1 g; The coupling reaction temperature in step 2) is 80-90°C and the time is 36-48h.

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 accelerator is a mixture of tetrabutylammonium bromide and potassium carbonate.

7. A carbazole conductive polymer prepared by using the star-shaped carbazole derivative according to claim 1, characterized in that: The structural formula of the carbazole conductive polymer is shown in Formula III: The n of the carbazole conductive polymer is 10 to 2000; The method for preparing the carbazole conductive polymer comprises the following steps: The star-shaped carbazole derivative shown in formula I is mixed with an electrolyte solution and subjected to cyclic voltammetry electrochemical polymerization to obtain a carbazole conductive polymer.

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

9. The carbazole conductive polymer according to claim 8, characterized in that: 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 0-1.5V, and the number of polymerization cycles is 8-12 cycles.

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

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