An electrochromic monomer compound, a polymer and a preparation method thereof

Abstract

The application belongs to the technical field of photoelectric materials, and particularly relates to an electrochromic monomer compound, a polymer and a preparation method thereof. The application takes oxidized calix[3]dihydroacridine as a central core, and 3,4-ethylenedioxythiophene (EDOT) as a monomer of an electroactive polymer unit. The prepared material can form a uniform and smooth polymer film through electrochemical polymerization. The polymer film can realize multi-color reversible switching from yellow to purple to blue when different voltages are applied. The optical contrast is 30%, and the response time is 1.6 s and 2.0 s. The electrochromic polymer film prepared by the application has short response time, rich color change and the ability to quickly adjust light, is an electrochromic material with good application prospect, and can be applied to the fields of intelligent display screens, windows, super capacitors and the like.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of photoelectric materials, and particularly relates to an electrochromic monomer compound, a polymer, a material and a preparation method thereof. BACKGROUND

[0002] Electrochromic materials refer to materials capable of causing stable and reversible changes in optical properties such as reflectivity, transmittance and absorptivity due to oxidation-reduction reactions and ion intercalation and deintercalation processes occurring in the materials when an external electric field is applied. As a new type of functional material, electrochromic materials have the advantages of self-color change and energy saving, and have been vigorously developed in the global environment of energy saving and emission reduction. Electrochromic materials are widely used in intelligent glass, automobile anti-dazzling rearview mirror, electronic tags, mobile phone accessories, displays, thermal control and other fields.

[0003] Electrochromic materials are divided into inorganic and organic types, and inorganic types are mainly various metal oxides, such as nickel oxide, tungsten oxide and titanium oxide. These materials have been widely used in commercial electrochromic devices, and have certain technical maturity and market acceptance. However, they have the disadvantages of single color change, high material cost and slow switching speed, which greatly limits their application in multi-color display. In contrast, electrochromic devices based on conductive polymer (CP) materials in organic electrochromic materials have the advantages of color change diversity, high controllability and high optical contrast.

[0004] However, in order to meet the actual industrial production and obtain better electrochemical redox reversibility, higher electrochromic rate, suitable potential window, excellent cycle capacity and chemical stability, it is still necessary to continue to explore and design new material structures and continuously optimize the electrochromic performance. SUMMARY

[0005] In order to overcome the above-mentioned shortcomings and deficiencies, the purpose of the present application is to provide an electrochromic conductive polymer monomer capable of realizing multi-color reversible change, which is specifically realized by the following technical scheme:

[0006] An electrochromic monomer compound, the structural formula of which is shown as formula (I):

[0007]

[0008] The preparation method of the electrochromic monomer compound comprises the following steps:

[0009] (1) 9,10-dihydro-9,9-dimethylacridine undergoes Ullmann coupling reaction with p-bromoiodobenzene to obtain acridine derivative DMAC-Ph-Br (III), and the structural formula of DMAC-Ph-Br is as follows:

[0010]

[0011] (2) DMAC-Ph-Br (III) and paraformaldehyde undergo Friedel-Crafts alkylation reaction to obtain acridine derivative-based cyclic compound 3DMAC-Ph-Br (IV), the structure of which is as follows:

[0012]

[0013] (3) 3DMAC-Ph-Br (IV) and phenylseleninic anhydride undergo oxidation reaction to obtain carbonylated acridine derivative-based cyclic compound 3DMACO-Ph-Br (V), the structure of which is as follows:

[0014]

[0015] (4) EDOT and tributyltin chloride undergo substitution reaction to obtain tinized EDOT derivative EDOT-Sn (VI), the structure of which is as follows:

[0016]

[0017] (5) 3DMACO-Ph-Br (V) and EDOT-Sn (VI) undergo Stille coupling reaction under catalysis of palladium catalyst to obtain target product 3DMACO-EDOT (I).

[0018] As a preference, the Ullmann coupling reaction in step (1) is specifically as follows: 9,10-dihydro-9,9-dimethylacridine, p-bromoiodobenzene, cuprous iodide, sodium tert-butoxide, 1,2-diaminocyclohexane, 1,4-dioxane are sequentially added into a two-necked flask, and refluxed for 3-12 h under nitrogen atmosphere, and DMAC-Ph-Br (III) is obtained after post-treatment; the molar ratio of 9,10-dihydro-9,9-dimethylacridine, p-bromoiodobenzene, cuprous iodide, sodium tert-butoxide, 1,2-diaminocyclohexane is 1:(1-1.2):(0.01-0.03):(1.8-2.2):(0.08-0.12); the volume of anhydrous 1,4-dioxane added is 7-13 mL / g based on the mass of 9,10-dihydro-9,9-dimethylacridine. The method of post-treatment is specifically as follows: after the reaction is completed, the obtained reaction solution is poured into deionized water for mixing, and the precipitate is collected by filtration, then the precipitate is extracted with saturated sodium chloride and dichloromethane, the organic phase is collected and dried with anhydrous sodium sulfate, and finally, petroleum ether and dichloromethane are used as mobile phases for purification by silica gel column chromatography; in the mobile phase, the volume ratio of petroleum ether and dichloromethane is (3-8):1.

[0019] As preferred, the Friedel-Crafts alkylation reaction in step (2) is specifically as follows: DMAC-Ph-Br (III), paraformaldehyde and dichloromethane are sequentially added into a single-neck flask, stirred for 10 minutes, then iron trichloride hexahydrate is added, and then reacted at room temperature for 3-24 hours, and then the post-treatment is performed to obtain 3DMAC-Ph-Br (IV); the molar ratio of the DMAC-Ph-Br (III), paraformaldehyde and iron trichloride hexahydrate is 1:(3-3.2):(0.1-0.12); the volume of the dichloromethane added is 200-300 mL / g based on the mass of the monomer III. The method of the post-treatment is specifically as follows: after the reaction is completed, the obtained reaction solution is poured into deionized water for mixing, the precipitate is collected by filtration, then the precipitate is extracted with saturated sodium chloride and dichloromethane, the organic phase is collected and dried with anhydrous sodium sulfate, and finally, petroleum ether and dichloromethane are used as the mobile phase for purification by silica gel column chromatography; in the mobile phase, the volume ratio of the petroleum ether and dichloromethane is (2-5):1.

[0020] As preferred, the oxidation reaction in step (3) is specifically as follows: 3DMAC-Ph-Br (IV), phenyl seleninic anhydride and chlorobenzene are sequentially added into a two-neck flask, refluxed under nitrogen atmosphere for 30-36 hours, and then the post-treatment is performed to obtain 3DMACO-Ph-Br (V); the molar ratio of the 3DMAC-Ph-Br (IV) and phenyl seleninic anhydride is 1:(3.2-3.8); the volume of the chlorobenzene added is 50-80 mL / g based on the mass of the 3DMAC-Ph-Br (IV). The method of the post-treatment is specifically as follows: after the reaction is completed, the obtained reaction solution is poured into deionized water for mixing, the precipitate is collected by filtration, then the precipitate is extracted with saturated sodium chloride and dichloromethane, the organic phase is collected and dried with anhydrous sodium sulfate, and finally, petroleum ether and ethyl acetate are used as the mobile phase for purification by silica gel column chromatography; in the mobile phase, the volume ratio of the petroleum ether and ethyl acetate is (3-8):1.

[0021] As preferred, the substitution reaction in step (4) is specifically as follows: 3,4-ethylenedioxythiophene (EDOT) is dissolved in tetrahydrofuran under nitrogen protection, then n-butyllithium is added at-78°C, after stirring for 1 hour, tributyltin chloride is added, the temperature is restored to room temperature, and then stirred for 24 hours, and then the post-treatment is performed to obtain compound EDOT-Sn (VI); the molar ratio of the EDOT, n-butyllithium and tributyltin chloride is 1:(1-1.2):(1-1.6); wherein, the n-butyllithium is a 1-3 mol / L n-butyllithium solution, and the tributyltin chloride is a 1-5 g / mL tributyltin chloride solution; the volume of the tetrahydrofuran added is 15-25 mL / g based on the mass of the EDOT. The method of the post-treatment is specifically as follows: after the reaction is completed, the obtained reaction solution is separated and purified by an alumina chromatographic column.

[0022] As preferred, the step (5) Stille coupling reaction is specifically: under nitrogen protection, monomer 3DMACO-Ph-Br (V), EDOT-Sn (VI), and palladium catalyst are sequentially added into a two-neck flask, then DMF is added, and the mixture is stirred and refluxed for 48 h, and the target product 3DMACO-EDOT (I) is obtained after post-treatment; the molar ratio of the 3DMACO-Ph-Br (V), EDOT-Sn (VI), and palladium catalyst is 1: (3-6): (0.001-0.01); wherein the palladium catalyst is any one of palladium acetate, tetrakis (triphenylphosphine) palladium, or dichlorobis (triphenylphosphine) palladium; the volume of the added DMF is 15-25 mL / g based on the mass of the monomer V. The specific method of the post-treatment is as follows: after the reaction is completed, the obtained reaction solution is poured into deionized water, the precipitate is collected by filtration, then the precipitate is extracted with saturated sodium chloride and dichloromethane, the organic phase is collected and dried with anhydrous sodium sulfate, and finally, the purified product is obtained by silica gel column chromatography with petroleum ether and dichloromethane as the mobile phase; the volume ratio of petroleum ether to dichloromethane in the mobile phase is (0.5-2): 1.

[0023] An electrochromic polymer, the structural formula of which is shown in formula (II):

[0024]

[0025] In formula (II), n represents the average polymerization degree, and n is 100-2000.

[0026] An electrochromic material is prepared from the electrochromic monomer compound of any one of the above, or the electrochromic monomer compound prepared by the preparation method of any one of the above, or the electrochromic polymer of the above.

[0027] A preparation method of an electrochromic material, comprising the following steps: dissolving 3DMACO-EDOT (I) in a mixed chromatographic grade solution of dichloromethane and acetonitrile, adding tetrabutylammonium perchlorate as an electrolyte, and electrochemically polymerizing into a film by cyclic voltammetry to prepare a multifunctional electrochromic material; the volume ratio of dichloromethane to acetonitrile is (3-5): 1; the concentration of 3DMACO-EDOT is 0.5-1 mmol / L; and the concentration of tetrabutylammonium perchlorate is 0.05-0.1 mol / L. The electrochemical polymerization by cyclic voltammetry refers to that in a three-electrode system, ITO conductive glass is used as a working electrode, a platinum wire is used as a counter electrode, and Ag / AgCl is used as a reference electrode, electrochemical polymerization is carried out, a thin film attached to the ITO glass is obtained, and the multifunctional electrochromic material capable of realizing multicolor reversible conversion is obtained; the scanning speed of the cyclic voltammetry is 100 mV / s, the voltage is 0-1.1 V, and the cycle number is 5-10 cycles.

[0028] Compared with the prior art, the application has the following beneficial effects:

[0029] 1、 The application provides a three-branch type material easy to form a network structure, which is a monomer compound with an acridine derivative as a central core and 3,4-ethylenedioxythiophene (EDOT) as an electroactive polymerization unit, and can form a uniform and smooth polymer film (p3DMACO-EDOT) through electrochemical polymerization, and the porous network structure in the material can store multiple electrons, which shows development potential in energy storage applications such as supercapacitors.

[0030] 2、 The polymer film prepared by electrochemical polymerization of the electrochromic monomer compound has the advantages of simple preparation method, fast color changing speed, good cycle stability, wide optical modulation range and the like, and can exhibit yellow, purple, blue and other colorful colors in the process of applying voltage.

[0031] 3、 The multifunctional electrochromic polymer of the application is simple to prepare and easy to popularize, and provides a reference for the development of electrochromic glasses and colorful displays, and plays a promoting role in the marketization process of electrochromic glasses and displays. BRIEF DESCRIPTION OF DRAWINGS

[0032] Figure 1 is a synthesis route diagram of the monomer compound (3DMACO-EDOT) described in the application;

[0033] Figure 2 is an electrochemical polymerization curve diagram of the monomer compound (3DMACO-EDOT) described in the application;

[0034] Figure 3 is an ultraviolet-visible absorption spectrum diagram of the electrochromic polymer described in the application under different voltages;

[0035] Figure 4 is an optical contrast and response time diagram of the electrochromic polymer film described in the application under a 1100 nm wave band;

[0036] Figure 5 is a charge and discharge curve diagram of the electrochromic polymer film described in the application under a current density of 0.2 mA / cm 2 ; and

[0037] Figure 6 is a structure schematic diagram of the electrochromic monomer compound described in the application. DETAILED DESCRIPTION

[0038] The application will be described further in conjunction with specific examples. A person of ordinary skill in the art will be able to implement the application based on these descriptions. In addition, the embodiments of the application involved in the following descriptions are generally only a part of the embodiments of the application, rather than all the embodiments. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments in the application without creative labor should fall within the scope of protection of the application.

[0039] Example 1: Synthesis of DMAC-Ph-Br

[0040] 9,10-dihydro-9,9-dimethylacridine 1.14 g (5.45 mmol), p-bromoiodobenzene 1.7 g (6 mmol), cuprous iodide 0.021 g (0.11 mmol), sodium tert-butoxide 1.05 g (10.9 mmol), 1,2-diaminocyclohexane 0.063 g (0.55 mmol), 12 mL of anhydrous 1,4-dioxane were sequentially added into a 100 mL two-necked flask, and refluxed under a nitrogen atmosphere for 6 h. After the reaction was completed, the obtained reaction solution was poured into 100 mL of deionized water, and the precipitate was collected by filtration. Then, the precipitate was extracted with saturated sodium chloride solution and dichloromethane, and the organic phase was collected and dried with anhydrous sodium sulfate. Finally, DMAC-Ph-Br was obtained by purification through a silica gel column chromatography with petroleum ether:dichloromethane (volume ratio 5:1) as the mobile phase. The structural formula of the DMAC-Ph-Br is as shown in Formula III.

[0041]

[0042] In some embodiments, the refluxing is performed under a nitrogen atmosphere for 3-12 h; the molar ratio of 9,10-dihydro-9,9-dimethylacridine, p-bromoiodobenzene, cuprous iodide, sodium tert-butoxide, 1,2-diaminocyclohexane is 1:(1-1.2):(0.01-0.03):(1.8-2.2):(0.08-0.12); the volume of anhydrous 1,4-dioxane added is 7-13 mL / g based on the mass of 9,10-dihydro-9,9-dimethylacridine; and the volume ratio of petroleum ether and dichloromethane is (3-8):1.

[0043] Example 2: Synthesis of 3DMAC-Ph-Br

[0044] DMAC-Ph-Br 1 g (2.75 mmol), paraformaldehyde 0.247 g (8.25 mmol), 250 mL dry dichloromethane were added into a 500 mL single neck flask in sequence, after stirring for 10 min, iron trichloride hexahydrate 0.074 g (0.275 mmol) was added, then the reaction was carried out at room temperature for 6 h, after the reaction was completed, the obtained reaction solution was poured into 100 mL deionized water, the precipitate was collected by filtration, then the precipitate was extracted with saturated sodium chloride solution and dichloromethane, the organic phase was collected and dried with anhydrous sodium sulfate, finally, the product monomer 3DMAC-Ph-Br was purified by silica gel column chromatography with petroleum ether:dichloromethane (volume ratio 3:1) as the mobile phase, and the structural formula of the monomer 3DMAC-Ph-Br is as shown in formula IV.

[0045]

[0046] In some embodiments, the reaction was carried out at room temperature for 3-24 h; the molar ratio of DMAC-Ph-Br (III), paraformaldehyde, iron trichloride hexahydrate was 1:(3-3.2):(0.1-0.12); the volume of dichloromethane added was 200-300 mL / g based on the mass of monomer III; the volume ratio of petroleum ether and dichloromethane was (2-5):1.

[0047] Example 3: Synthesis of 3DMACO-Ph-Br

[0048] 3DMAC-Ph-Br 0.2 g (0.17 mmol), phenyl seleninic anhydride 0.23 g (0.63 mmol), 15 mL chlorobenzene were added into a two-neck flask in sequence, and refluxed under nitrogen atmosphere for 30-36 h, after the reaction was completed, the obtained reaction solution was poured into deionized water, the precipitate was collected by filtration, then the precipitate was extracted with saturated sodium chloride solution and dichloromethane, the organic phase was collected and dried with anhydrous sodium sulfate, finally, the product monomer 3DMACO-Ph-Br (V) was purified by silica gel column chromatography with petroleum ether:ethyl acetate (volume ratio 3:1) as the mobile phase, and the structural formula of the monomer 3DMACO-Ph-Br is as shown in formula V.

[0049]

[0050] In some embodiments, the molar ratio of 3DMAC-Ph-Br (IV), phenyl seleninic anhydride was 1:(3.2-3.8); the volume of chlorobenzene added was 50-80 mL / g based on the mass of 3DMAC-Ph-Br (IV); the volume ratio of petroleum ether and ethyl acetate was (3-8):1.

[0051] Example 4: Synthesis of EDOT-Sn

[0052] EDOT 1 g (7.03 mmol) was dissolved in 20 mL of anhydrous tetrahydrofuran under nitrogen protection, then 3.37 mL (8.4 mmol, 2.5 mol / L stored in hexane solution) of n-butyllithium solution was added dropwise at -78°C, after stirring at this temperature for 1 h, 2.97 g (9.14 mmol) of tributyltin chloride was added, after the addition of tributyltin chloride was completed, it was restored to room temperature and stirred for 24 h, after the reaction was completed, the obtained reaction liquid was separated and purified by alumina column chromatography to obtain the crude product of compound EDOT-Sn, the yield was 80%, and the structural formula of the compound EDOT-Sn was as formula VI.

[0053]

[0054] In some embodiments, the molar ratio of EDOT, n-butyllithium, and tributyltin chloride is 1:(1-1.2):(1-1.6); wherein the n-butyllithium is 1-3 mol / L of n-butyllithium solution, the tributyltin chloride is 1-5 g / mL of tributyltin chloride solution; and the volume of tetrahydrofuran added is 15-25 mL / g based on the mass of EDOT.

[0055] Example 5: Synthesis of 3DMACO-EDOT

[0056] Under nitrogen protection, 3DMACO-Ph-Br 0.35 g (0.44 mmol), EDOT-Sn 0.95 g (2.2 mmol), and tetrakis(triphenylphosphine)palladium 40 mg (0.35 mmol) were sequentially added to a two-necked round-bottom flask, then 10 mL of anhydrous DMF was added, the reaction was refluxed under stirring for 48 h, after the reaction was completed, the obtained reaction liquid was poured into 100 mL of deionized water, the precipitate was collected by filtration, then the precipitate was extracted with saturated sodium chloride solution and dichloromethane, the organic phase was collected and dried with anhydrous sodium sulfate, finally, petroleum ether:dichloromethane (volume ratio 1:1) was used as the mobile phase to purify the target product 3DMACO-EDOT by silica gel column chromatography, and the structural formula of the monomer 3DMACO-EDOT was as formula I.

[0057]

[0058] In some embodiments, the molar ratio of 3DMACO-Ph-Br (V), EDOT-Sn (VI), and palladium catalyst is 1:(3-6):(0.001-0.01); wherein the palladium catalyst is any one of palladium acetate, tetrakis(triphenylphosphine)palladium, or dichlorobis(triphenylphosphine)palladium; the volume of DMF added is 15-25 mL / g based on the mass of monomer V; and the volume ratio of petroleum ether and dichloromethane is (0.5-2):1.

[0059] Example 6: Preparation of electrochromic material

[0060] The monomer 3DMACO-EDOT was dissolved in a mixed chromatographic grade solution of dichloromethane and acetonitrile, the volume ratio of dichloromethane to acetonitrile was 8:2, the concentration of 3DMACO-EDOT was 1 mmol / L, then tetrabutylammonium perchlorate was added as an electrolyte, the concentration was 0.1 mol / L, and cyclic voltammetry was carried out in a three-electrode system (ITO conductive glass as the working electrode, platinum wire as the counter electrode, and Ag / AgCl as the reference electrode) to obtain an electrochromic polymer film (p3DMACO-EDOT) attached to the ITO glass, which is a multifunctional electrochromic polymer material; the scan rate of the cyclic voltammetry was 100 mV / s, the voltage was 0-1.4 V, and the number of cycles was 11.

[0061] In some embodiments, the volume ratio of dichloromethane to acetonitrile was (3-5):1; the concentration of 3DMACO-EDOT was 0.5-1 mmol / L; and the concentration of tetrabutylammonium perchlorate was 0.05-0.1 mol / L. The scan rate of the cyclic voltammetry was 100 mV / s, the voltage was 0-1.1 V, and the number of cycles was 5-10.

[0062] Performance test

[0063] The CV curve of the prepared film, the ultraviolet-visible light absorption at different voltages, the bleaching time and coloring time of the film at a specific wavelength, the relationship between the transmittance and time at a specific wavelength, and the film stability test at a step voltage were tested using an electrochemical workstation combined with an ultraviolet-visible spectrophotometer in a 0.1 M tetrabutylammonium perchlorate / acetonitrile solution, and the data processing results are shown in the figures.

[0064] Figure 2 For the electrochemical polymerization curve of the monomer 3DMACO-EDOT, it can be seen that the current response signal increases with the increase of the number of cycles, indicating that the monomer is successfully polymerized on the surface of the ITO glass. From the CV curve of the polymer film, it can be seen that the current response signal increases with the increase of the number of cycles, indicating that the monomer is successfully polymerized on the surface of the ITO glass. Figure 3 It can be seen that the polymer film is yellow at 0 V in the neutral state, and as the applied voltage increases, an absorption peak appears at about 510 nm when a voltage of 1.1 V is applied, at which time the film exhibits a purple color; when the voltage continues to increase to 1.4 V, the absorption peak intensity at 510 nm becomes weaker, and an absorption peak begins to appear at about 700 nm, and the near-infrared region also begins to peak, at which time the film color changes from purple to blue; as the applied voltage continues to increase, a strong absorption peak appears at 800 nm, at which time the polymer film is blue. Figure 4The electrochemical workstation-ultraviolet-visible spectrophotometer combination test is used to test the spectral dynamic change, optical contrast and response time diagram of the polymer thin film at 0V and 1.7V under 1100nm wave band. It can be seen that the optical contrast of the thin film under 1100nm is 30%, and the color response time is 1.6s and 2.0s respectively. Figure 5 The electrochemical workstation is used to test the charge-discharge performance of the polymer thin film at different current densities under the voltage range of 0.7-1.4V. The diagram can show that the thin film exhibits a surface capacitance of 4.57mF / cm 2 under the current density of 0.2mA / cm 2 .

[0065] In summary, the polymer thin film material prepared by electrochemical polymerization of the electrochromic monomer compound has the advantages of simple preparation method, fast color changing speed, good cycle stability, wide optical modulation range and the like. In the process of applying voltage, the polymer thin film material can exhibit yellow, purple, blue and other colorful colors.

Claims

1. An electrochromic monomer compound characterized in that, The structural formula is shown as formula (I):

2. Process for the preparation of the electrochromic monomeric compound according to claim 1, characterized in that, The method comprises the following steps: (1) Ullmann coupling reaction of 9,10-dihydro-9,9-dimethylacridine and p-bromoiodobenzene to obtain acridine derivative DMAC-Ph-Br (III), and the structural formula of DMAC-Ph-Br is as follows: (2) Friedel-Crafts alkylation reaction of DMAC-Ph-Br (III) and paraformaldehyde to obtain acridine derivative-based cyclic compound 3DMAC-Ph-Br (IV), and the structural formula of 3DMAC-Ph-Br is as follows: (3) Oxidation reaction of 3DMAC-Ph-Br (IV) and phenylseleninic anhydride to obtain carbonylated acridine derivative-based cyclic compound 3DMACO-Ph-Br (V), and the structural formula of 3DMACO-Ph-Br is as follows: (4) Substitution reaction of EDOT and tributyltin chloride to obtain tinized EDOT derivative EDOT-Sn (VI), and the structural formula of EDOT-Sn is as follows: (5) Stille coupling reaction of 3DMACO-Ph-Br (V) and EDOT-Sn (VI) under the catalysis of a palladium catalyst to obtain the target product.

3. The method for preparing the electrochromic monomer compound according to claim 2, characterized in that, In step (1), the Ullmann coupling reaction is specifically as follows: 9,10-dihydro-9,9-dimethylacridine, p-bromoiodobenzene, cuprous iodide, sodium tert-butoxide, 1,2-diaminocyclohexane and 1,4-dioxane are sequentially added into a two-necked flask, and refluxed for 3-12 hours under a nitrogen atmosphere, and then DMAC-Ph-Br (III) is obtained after post-treatment; the molar ratio of 9,10-dihydro-9,9-dimethylacridine, p-bromoiodobenzene, cuprous iodide, sodium tert-butoxide and 1,2-diaminocyclohexane is 1:(1-1.2):(0.01-0.03):(1.8-2.2):(0.08-0.12); and the volume of 1,4-dioxane added is 7-13 mL / g based on the mass of 9,10-dihydro-9,9-dimethylacridine.

4. The method for preparing the electrochromic monomer compound according to claim 2, characterized in that, In step (2), the Friedel-Crafts alkylation reaction is specifically as follows: DMAC-Ph-Br (III), paraformaldehyde and dichloromethane are sequentially added into a single-necked flask, stirred, and then hexahydrated ferric chloride is added for reaction, and 3DMAC-Ph-Br (IV) is obtained after post-treatment; the molar ratio of DMAC-Ph-Br (III), paraformaldehyde and hexahydrated ferric chloride is 1:(3-3.2):(0.1-0.12); and the volume of dichloromethane added is 200-300 mL / g based on the mass of monomer DMAC-Ph-Br (III).

5. The method for preparing the electrochromic monomer compound according to claim 2, characterized in that, In step (3), the oxidation reaction is specifically as follows: 3DMAC-Ph-Br (IV), phenylseleninic anhydride and chlorobenzene are sequentially added into a two-necked flask, refluxed for 30-36 hours under a nitrogen atmosphere, and then 3DMACO-Ph-Br (V) is obtained after post-treatment; the molar ratio of 3DMAC-Ph-Br and phenylseleninic anhydride is 1:(3.2-3.8); and the volume of chlorobenzene added is 50-80 mL / g based on the mass of 3DMAC-Ph-Br (IV).

6. The method for preparing the electrochromic monomer compound according to claim 2, characterized in that, The step (4) is a substitution reaction, specifically: under nitrogen protection, 3,4-ethylenedioxythiophene (EDOT) is dissolved in tetrahydrofuran, then n-butyllithium is added at-78℃, after stirring, tributyltin chloride is added, stirring is resumed to room temperature, and after treatment, compound EDOT-Sn(Ⅵ) is obtained; the molar ratio of the EDOT, n-butyllithium and tributyltin chloride is 1:(1-1.2):(1-1.6); wherein the n-butyllithium is a 1-3 mol / L n-butyllithium solution, the tributyltin chloride is a 1-5 g / mL tributyltin chloride solution; the volume of the tetrahydrofuran added is 15-25 mL / g based on the mass of the EDOT.

7. The method for preparing the electrochromic monomer compound according to claim 2, characterized in that, The step (5) is a Stille coupling reaction, specifically: under nitrogen protection, monomer 3DMACO-Ph-Br (Ⅴ), EDOT-Sn(Ⅵ) and a palladium catalyst are sequentially added to a two-necked flask, then DMF is added, stirring is performed under reflux, and after treatment, the target product is obtained; the molar ratio of the 3DMACO-Ph-Br (Ⅴ), EDOT-Sn(Ⅵ) and the palladium catalyst is 1:(3-6):(0.001-0.01); wherein the palladium catalyst is any one of palladium acetate, tetrakis(triphenylphosphine)palladium or dichlorobis(triphenylphosphine)palladium; the volume of the DMF added is 15-25 mL / g based on the mass of the monomer Ⅴ.

8. An electrochromic polymer characterized in that, The structural formula is shown in formula (Ⅱ): In formula (Ⅱ), n represents an average polymerization degree, and n is 100-2000.

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