Fluorescent polymers based on benzothiazole derivatives, their preparation methods and applications

Abstract

This invention discloses a fluorescent polymer based on benzothiazole derivatives, its preparation method, and its applications. By adjusting the length of the alkane side chains, the modified benzothiazole derivative monomer is copolymerized with a 3,4-ethylenedioxythiophene derivative monomer via direct arylation coupling polymerization. By adjusting the degree of π-conjugation and the band structure of the polymer, the color of the polymer changes from yellow to blue-green. The introduction of side chains enables the polymer to be soluble. The polymer provided by this invention has solution-processable characteristics and has potential applications in the field of electrochromism. Furthermore, the polymer provided by this invention exhibits selectivity and sensitivity to iron and ruthenium ions, and can be used as a metal ion probe.

Description

Technical Field

[0001] This invention relates to a fluorescent polymer based on benzothiazole derivatives, its preparation method, and its multifunctional applications as an electrochromic material and ion probe. Background Technology

[0002] Because the presence and concentration of metal ions seriously affect human health, efficient and selective probes for metal ions in water and in vivo samples have attracted great attention. 3+ As a trace element, ruthenium participates in many fundamental physiological processes in living tissues and cells. Excessive iron ions in the body can lead to coma, metabolic acidosis, shock, and even death. Furthermore, insufficient iron intake can cause iron-deficiency anemia. In recent years, heavy metals have played a wide role in drug development. All drugs have advantages and disadvantages, depending on the dosage and the nature of the receptor. Excessive use of heavy metals in drugs, even at appropriate dosages, can lead to harm to human health. Excessive exposure to ruthenium is corrosive and destructive to the respiratory tract, eyes, skin, and digestive tract. Therefore, developing a simple qualitative and quantitative method for the determination of iron and ruthenium ions is particularly important and urgent.

[0003] On the other hand, energy conservation is a crucial issue that should be addressed. The broad prospects of electrochromic materials in various fields make them an important component of energy-saving materials. The successful application of dimmable windows on the Boeing 787 Dreamliner has greatly inspired scientists' enthusiasm for electrochromic materials. Early electrochromic research was mainly dominated by transition metal oxides and small organic molecules, but due to the ease of modification of the molecular structure of electrochromic polymers (ECPs), their high coloring efficiency, high contrast, and fast response speed, they have become the most powerful competitors for next-generation electrochromic materials. Currently, most ECP materials are insoluble polymers obtained through electrochemical or chemical polymerization, but this is not conducive to the large-scale preparation of large-size ECP materials and devices. Solution processing methods such as spin coating, spraying, inkjet printing, and roll-to-roll can prepare large-size ECP materials and devices at low cost and on a large scale. Therefore, researchers have begun to focus on designing and synthesizing novel solution-processable ECPs. Among them, benzothiazole (BTA) is a bicyclic heterocyclic compound with strong electron-withdrawing ability, found in various natural products and drugs, and is commonly used as an electron acceptor in the field of electroluminescence. The corresponding benzothiazolium compounds exhibit good chemical and thermal stability, but they have not been applied in the field of electrochromism.

[0004] Therefore, it is of great significance to seek an organic electrochromic material that can be solution-processed and also used as a metal ion probe. Summary of the Invention

[0005] The purpose of this invention is to provide a method for preparing a solution-processable electrochromic polymer with a DA structure, using 3,3-dimethyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxane as a donor and 4,7-dibromo-2-(hept-3-yl)benzo[d]thiazole as an acceptor, as well as the preparation of its thin film and its application as Fe 3 +,Ru 3 +Application of metal ion probes.

[0006] To achieve the above objectives, the technical solution of the present invention is as follows:

[0007] This invention provides a polymer of formula (Ⅰ):

[0008]

[0009] Where n is 2-2000, and R is C1-C 10 Alkyl group, R is preferred

[0010] The present invention also provides a method for preparing the polymer shown in formula (I), wherein the preparation method is as follows:

[0011] Under a protective atmosphere (such as nitrogen or argon, preferably nitrogen), compound (II), compound (V), neopentanoic acid, palladium acetate, and potassium carbonate are added to N,N-dimethylacetamide and reacted at 130°C to 140°C for 36 to 48 hours (preferably 140°C for 48 hours). The resulting reaction solution E is then post-treated to obtain the polymer shown in formula (I). The molar ratio of compound (II), compound (V), neopentanoic acid, potassium carbonate, and palladium acetate is 1:1:0.3 to 0.4:2 to 2.5:0.04 to 0.08 (preferably 1:1:0.3:2:0.04).

[0012]

[0013] In equations (I), (II), and (V), n is 2-2000, and R is C1-C2. 10 One of the alkyl groups.

[0014] Preferably, the N,N-dimethylacetamide is 30-40 mL / g based on the mass of the compound of formula (V), more preferably 31 mL / g.

[0015] Further, the post-treatment E is as follows: after the reaction solution E is cooled to room temperature, it is poured into methanol to precipitate solids, filtered, and the resulting filter cake is successively subjected to Soxhlet extraction with methanol, n-hexane, acetone and chloroform. The chloroform washing liquid is collected, the solvent is removed by rotary evaporation and dried to obtain the polymer shown in formula (I).

[0016] In one embodiment of the present invention, the volume ratio of methanol to N,N-dimethylacetamide is 6:1.

[0017] Furthermore, the present invention provides a method for preparing a compound of formula (II), wherein the compound of formula (II) is prepared by the following method:

[0018] 3,4-Dimethoxythiophene, neopentyl glycol, and p-toluenesulfonic acid are added to toluene and reacted at 110°C to 120°C for 16 to 24 hours (preferably 110°C for 16 hours). The resulting reaction solution A is post-treated to obtain compound (3,4-ethylenedioxythiophene derivative EDOT-CH3) of formula (II). The molar ratio of 3,4-dimethoxythiophene to neopentyl glycol is 1:2 to 3 (preferably 1:2); the molar ratio of 3,4-dimethoxythiophene to p-toluenesulfonic acid is 3 to 10:1 (preferably 10:1).

[0019] Furthermore, the volume of toluene, based on the mass of the 3,4-dimethoxythiophene, is 15-20 mL / g (preferably 20.8 mL / g).

[0020] Furthermore, the post-treatment A is as follows: after adding saturated saline solution to the reaction solution A, extract with dichloromethane (three times), combine the organic phases, concentrate, remove water with anhydrous sodium sulfate, and perform column chromatography purification using a mixed solution of dichloromethane and petroleum ether with a volume ratio of 1:3-4 as the mobile phase. Collect the eluent containing the target compound, remove the solvent by rotary evaporation and dry to obtain the compound of formula (II).

[0021] Furthermore, the present invention also provides a method for preparing a compound of formula (V), wherein the compound of formula (V) is prepared according to the following method:

[0022] (1) 1,4-Dibromo-2-nitrobenzene and iron powder are mixed in glacial acetic acid and reacted at 70℃~80℃ for 5~8h (preferably 70℃ for 5h). The resulting reaction mixture is cooled to room temperature and extracted with dichloromethane. The resulting organic phase is washed with water, the organic layer is collected, dried on anhydrous MgSO4, and the solvent is removed under reduced pressure to obtain crude 2,5-dibromoaniline. The crude 2,5-dibromoaniline is dissolved in pyridine and reacted under a protective atmosphere B (such as nitrogen or argon, preferably nitrogen). The acyl chloride of formula (VI) is slowly added to the mixture, and the reaction is carried out at 110°C to 120°C for 2 to 4 hours (preferably 110°C for 2 hours). The resulting reaction solution B is then post-treated to obtain compound (III). The molar ratio of 1,4-dibromo-2-nitrobenzene to iron powder is 1:2 to 1:3 (preferably 1:2). The molar ratio of the acyl chloride of formula (VI) to 2,5-dibromoaniline (based on 100% purity) is 1:1 to 1.5 (preferably 1:1).

[0023]

[0024] (2) The compound of formula (III) and phosphorus pentasulfide described in step (1) are added to anhydrous toluene and reacted at 110°C to 120°C for 3 to 4 hours (preferably at 110°C for 3 hours) in a protective atmosphere C (such as nitrogen or argon, preferably nitrogen). The resulting reaction solution C is then post-treated to obtain compound (IV). The molar ratio of compound of formula (III) to phosphorus pentasulfide is 2 to 1:1 (preferably 2:1).

[0025]

[0026] (3) The compound of formula (IV) described in step (2), sodium hydroxide, and potassium ferricyanide are added to a mixed solvent of water and ethanol with a volume ratio of 15-20:1. The mixture is reacted at 90°C to 100°C for 2-4 hours (preferably at 95°C for 3 hours) under a protective atmosphere D (such as nitrogen or argon, preferably nitrogen). The resulting reaction solution D is then post-treated to obtain compound (V). The molar ratio of compound of formula (IV), potassium ferricyanide, and sodium hydroxide is 1:4 to 5:8 to 10 (preferably 1:4:8).

[0027]

[0028] In equations (Ⅲ), (Ⅳ), and (Ⅴ), n is 2-2000, and R is C1-C 10 One of the alkyl groups.

[0029] Preferably, the volume of glacial acetic acid in step (1) is 15-20 mL / g based on the mass of 1,4-dibromo-2-nitrobenzene; and the volume of pyridine is 15-20 mL / g based on the mass of 2,5-dibromoaniline.

[0030] Further, the post-treatment B in step (1) is as follows: the reaction solution B is poured into ice water, extracted with ethyl acetate, the organic layers are combined, dried with anhydrous magnesium sulfate, filtered, the filtrate is concentrated by vacuum evaporation, and silica gel column chromatography is performed using a mixed solution of dichloromethane and petroleum ether with a volume ratio of 1:1-4 (preferably 1:4) as the mobile phase. The eluent containing the target compound is collected, the solvent is removed by rotary evaporation and dried to obtain the compound of formula (Ⅲ).

[0031] Preferably, the volume of anhydrous toluene in step (2) is 15-20 mL / g based on the mass of the compound of formula (III).

[0032] Further, the post-treatment C in step (2) is as follows: the reaction solution C is cooled to 0°C and filtered, the resulting filter cake is dissolved in ethyl acetate and washed with water (three times), the resulting organic phase is concentrated, water is removed by anhydrous sodium sulfate, silica gel column chromatography is performed using a mixed solution of dichloromethane and petroleum ether with a volume ratio of 1:1-4 (preferably 1:4) as the mobile phase, the eluent containing the target compound is collected, the solvent is removed by rotary evaporation and dried to obtain the compound of formula (Ⅳ).

[0033] Preferably, the volume of the mixed solvent of water and ethanol in step (3) is 18 to 20 mL / g based on the mass of the compound of formula (IV).

[0034] Further, the post-treatment D in step (3) is as follows: the obtained reaction solution D is cooled in an ice bath, the obtained precipitate is filtered, the obtained filter cake is washed with water, dissolved in ethyl acetate, dehydrated with anhydrous sodium sulfate, concentrated by vacuum evaporation, and subjected to silica gel column chromatography with a mixed solution of dichloromethane and petroleum ether in a volume ratio of 1:1-5 (preferably 1:5) as the mobile phase. The eluent containing the target compound is collected, the solvent is removed by rotary evaporation and dried to obtain the compound of formula (V).

[0035] The present invention also provides an application of the polymer shown in formula (I) above as an electrochromic material.

[0036] In addition, the present invention provides an application of the polymer shown in formula (I) above as an ion probe, particularly in the detection of iron ions and ruthenium ions.

[0037] Specifically, the present invention provides a method for using it as an ion probe: the polymer shown in formula (I) is dissolved in an organic solvent (tetrahydrofuran, with a concentration of 0.01 mg / mL in one embodiment of the present invention) to obtain a polymer precursor solution, which is then added to the test solution and mixed evenly. The presence of metal ions can then be detected by ultraviolet-visible spectroscopy or fluorescence spectroscopy.

[0038] Furthermore, the volume ratio of the test solution to the polymer precursor solution is 1:40.

[0039] Compared with the prior art, the beneficial effects of the present invention are as follows: The present invention provides a benzothiazolyl derivative

[0040]

[0041] The electrochromic polymer of the substance has the general molecular formula: where n is 2-2000, and R is C1-C2. 10 One of the alkyl groups.

[0042] Compared with existing technologies, the beneficial effects of this invention are as follows: This invention adjusts the different lengths of the alkyl side chains, and then copolymerizes the modified benzothiazolyl derivative monomer with the 3,4-ethylenedioxythiophene derivative monomer through a direct arylation coupling condensation reaction. By adjusting the degree of n-conjugation and the band structure of the polymer, the color change of the polymer can be controlled, achieving a transition from yellow to a high blue-green hue. The polymer provided by this invention has potential for electrochromic applications and is soluble. The material has high ionic conductivity, and after applying voltage, a large number of electrolyte ions rapidly diffuse into the polymer material to balance the charge, accelerating the color change speed, improving its response rate, and enhancing contrast. In addition, the provided polymer is selective for metal ions and can be used as a metal ion probe. Attached Figure Description

[0043] Figure 1 This invention describes a synthetic route for a soluble electrochromic polymer that ranges from a neutral yellow state to an oxidized blue-green state.

[0044] Figure 2 This is a UV-Vis absorption spectrum of a soluble electrochromic polymer film, ranging from neutral yellow to oxidized blue-green, under different voltages according to the present invention. Inset: Color of the soluble electrochromic polymer film in the neutral and oxidized states.

[0045] Figure 3 This invention relates to the electrochromic properties of a soluble electrochromic polymer film that ranges from a neutral yellow state to an oxidized blue-green state.

[0046] Figure 4 This invention relates to the influence of different metal ions on the ultraviolet absorption of soluble electrochromic polymers.

[0047] Figure 5 Fluorescence spectral changes of different metal ions added to a tetrahydrofuran solution of a soluble electrochromic polymer (excitation wavelength: 350 nm, inset: polymer solution with Fe added) 3+ and Ru 3+ (Fluorescent color change).

[0048] Figure 6 Fluorescence spectra of soluble electrochromic polymers in tetrahydrofuran solution with Fe 3+ The graph shows the change in concentration of Fe (excitation wavelength: 350 nm; inset shows fluorescence intensity versus Fe). 3+ Concentration relationship graph).

[0049] Figure 7 The fluorescence spectrum of soluble electrochromic polymers in tetrahydrofuran solution varies with Ru 3+ The concentration variation graph (excitation wavelength: 350 nm; inset shows fluorescence intensity versus Ru) 3+Concentration relationship graph). Detailed Implementation

[0050] The technical solution of the present invention will be further described below with specific embodiments, but the protection scope of the present invention is not limited to the embodiments described below;

[0051] Example 1:

[0052] A molecular structure is The color can change from neutral purple to oxidized blue-green.

[0053]

[0054] The reactive synthesis formula of the soluble electrochromic polymer is shown below:

[0055] The preparation steps are as follows:

[0056] (1) 3,4-Dimethoxythiophene (1.44 g, 10 mmol), neopentyl glycol (2.08 g, 20 mmol), p-toluenesulfonic acid (0.18 g, 1 mmol), and 30 mL of anhydrous toluene were sequentially added to a two-necked round-bottom flask. The mixture was heated to reflux at 110 °C for 16 hours and then cooled to room temperature. After the reaction was complete, saturated brine was added, and the mixture was extracted three times with dichloromethane. The extract was concentrated and dehydrated with anhydrous sodium sulfate, and then purified by column chromatography using silica gel as the stationary phase and dichloromethane and petroleum ether as the mobile phase (volume ratio of dichloromethane to petroleum ether: 1:3). The eluent containing the target compound was collected, the solvent was removed by rotary evaporation, and the eluent was dried to obtain 1.66 g of the 3,4-ethylenedioxythiophene derivative EDOT-CH3, with a yield of 90%. Its 1H NMR spectrum is characterized as follows: 1H NMR (400 MHz, CDCl3) δ 6.47 (s, 2H), 3.72 (s, 4H), 1.02 (s, 6H).

[0057] (2) Mix 1,4-dibromo-2-nitrobenzene (5 g, 17.8 mmol) and iron powder (10.0 g, 35.6 mmol) in AcOH (75 mL) and stir at 70 °C for 5 h. The resulting reaction mixture was cooled to room temperature and extracted with dichloromethane. The resulting organic phase was washed with water, and the organic layer was collected and dried over anhydrous MgSO4. The solvent was removed under reduced pressure to obtain crude 2,5-dibromoaniline (4.8 g, 96% yield). The crude 2,5-dibromoaniline was dissolved in pyridine. Under a nitrogen atmosphere, 2-ethylhexanoyl chloride (1.94 g, 12.1 mmol) was slowly added to the above solution of 2,5-dibromoaniline (3.0 g, 12.1 mmol) in pyridine (45 mL). The mixture was heated to reflux at 110 °C for 2 h. The cooled solution was poured into ice water (200 mL), and then ethyl acetate (100 mL) was added. The aqueous layer was extracted with ethyl acetate (200 mL). The synthesized organic layer was dried over anhydrous MgSO4, filtered, and concentrated by vacuum evaporation. Using silica gel as the stationary phase and a mixed solution of dichloromethane and petroleum ether in a volume ratio of 1:4 as the mobile phase, the eluent containing the target compound was collected by TLC thin-layer chromatography. The solvent was removed by rotary evaporation and dried to finally obtain compound III (4.0 g, 80%) as a white solid. Its 1H NMR spectrum is characterized as follows: 1H NMR (600MHz, CDCl3) δ 8.66 (d, J = 2.2Hz, 1H), 7.62 (s, 1H), 7.40 (d, J = 8.5Hz, 1H), 7.12 (dd, J = 8.5, 2.4Hz, 1H), 2.22–2.18 (m, 1H), 1.77–1.71 (m, 2H), 1.65–1.56 (m, 2H), 1.39–1.33 (m, 4H), 1.00 (t, J = 7.4Hz, 3H), 0.92 (t, J = 7.0Hz, 3H).

[0058] (3) Compound III (2 g, 5.08 mmol) was added to a mixture of phosphorus pentasulfide (0.56 g, 2.54 mmol) and anhydrous toluene (30 mL). The bright yellow suspension was heated under nitrogen and gently refluxed at 110 °C for 3 h. The solution was then cooled to 0 °C and filtered. The insoluble portion was dissolved in ethyl acetate (50 mL) and extracted three times with water. The extracted organic phase was concentrated and dehydrated with anhydrous sodium sulfate. Column chromatography was performed for purification. Silica gel was used as the stationary phase, and a mixture of dichloromethane and petroleum ether (volume ratio 1:4) was used as the mobile phase. The eluent containing the target compound was collected by TLC thin-layer chromatography. The solvent was removed by rotary evaporation and dried to obtain compound (IV). (1.8.0 g, 75%) was an orange solid. Its 1H NMR spectrum is characterized as follows: 1H NMR (600MHz, CDCl3) δ 8.83 (d, J = 2.2Hz, 1H), 8.68 (s, 1H), 7.48 (d, J = 8.5Hz, 1H), 7.29–7.26 (m, 1H), 2.57 (tt, J = 9.4, 4.9Hz, 1H), 1.88–1.82 (m, 2H), 1.69 (ddd, J = 13.6, 9.9, 6.3Hz, 1H), 1.39–1.29 (m, 5H), 0.97 (t, J = 7.4Hz, 3H), 0.90 (t, J = 6.8Hz, 3H).

[0059] (4) Compound IV (4.2 g, 10.68 mmol), potassium ferricyanide (14.06 g, 42.72 mmol), and sodium hydroxide (3.41 g, 85.44 mmol) were added to a water-ethanol solution (75.6 mL – 4.2 mL), and stirred at 95 °C for 3 hours under nitrogen. The mixture was cooled in an ice bath to obtain a precipitate. The precipitate was then filtered, washed with water, and dissolved in ethyl acetate. After dehydration with anhydrous sodium sulfate, the precipitate was concentrated by vacuum evaporation. Using silica gel as the stationary phase and a 1:5 volume ratio of dichloromethane and petroleum ether as the mobile phase, the eluent containing the target compound was collected by TLC thin-layer chromatography. The solvent was removed by rotary evaporation and dried to obtain compound (V) (2.1 g, 50%) as a yellow oil. Its 1H NMR spectrum is characterized as follows: 1H NMR (600MHz, CDCl3) δ 7.53–7.51 (m, 1H), 7.35–7.33 (m, 1H), 3.15 (ddd, J = 14.3, 7.1, 4.3 Hz, 1H), 1.87–1.74 (m, 4H), 1.35–1.24 (m, 4H), 0.94 (t, J = 7.4 Hz, 3H), 0.87 (t, J = 7.1 Hz, 3H).

[0060] (5) 3,4-ethylenedioxythiophene derivative EDOT-CH3 (0.37 g, 2.01 mmol), potassium carbonate (0.55 g, 4.02 mmol), palladium acetate (20.5 mg, 0.089 mmol), and neopentanoic acid (63.35 mg, 0.607 mmol) were sequentially added to a two-necked round-bottom flask. Under nitrogen protection, compound V (0.8 g, 2.01 mmol) and 25 mL of anhydrous N,N-dimethylacetamide were added. The mixture was reacted at 140 °C for 48 hours and then cooled to room temperature. After the reaction was complete, the reaction solution was poured into 300 mL of methanol to precipitate a solid. The solid was filtered to obtain the crude product. The crude product was then subjected to Soxhlet extraction with methanol, petroleum ether, acetone, and chloroform sequentially. The washings from the chloroform fraction were collected and evaporated to dryness to obtain a yellow solid product (0.83 g, yield 86%). GPC data are as follows: M n =15.2kDa, M w =34.3kDa, PDI=2.2.

[0061] Example 2: Performance testing and ion probe performance testing of electrochromic materials based on electrochromic polymer I (effect experiments and data).

[0062] The electrochromic polymer I based on benzothiazolyl derivatives prepared in Example 1 was dissolved in chloroform solvent and spin-coated onto an ITO glass substrate. After drying, a polymer film was obtained. Using 0.1 M tetrabutylammonium hexafluorophosphate as the electrolyte and acetonitrile as the solvent, a three-electrode system was used to spin-coat the polymer film onto the ITO substrate (rotation speed 1000 r / s, time 1 min). The polymer film served as the working electrode, a platinum wire as the counter electrode, and a silver wire as the reference electrode. Spectroelectrochemical measurements were performed, and the spectroelectrochemical spectra (e.g., ...) were obtained. Figure 2 (As shown). The color-changing properties of the polymer film indicate that the polymer film of this embodiment can change from a neutral yellow state to an oxidized blue-green state. (As shown) Figure 3 As shown, the electrochromic properties of this polymer film are as follows: the coloring time at 445 nm is 0.7 s, the fading time is 2.3 s, and the contrast ratio is 39%.

[0063] Example 3: Application of the fluorescent probe of the present invention.

[0064] 1 mg of the electrochromic polymer I of a benzothiazolyl derivative was dissolved in 1 mL of tetrahydrofuran to prepare a stock solution (1 mg / mL). Metal ions were dissolved in Milli-Q water to obtain various metal ion stock solutions (1 × 10⁻⁶). -2(mol / L). The entire metal ion titration experiment was conducted as follows: 30 μL of polymer stock solution (1 mg / mL) was added to 2970 μL of tetrahydrofuran and mixed thoroughly to obtain a polymer precursor solution. Then, 50 μL of different metal ion stock solutions were added to 2 mL of the polymer precursor solution and mixed thoroughly. The changes in absorption spectra before and after the addition of metal ions were recorded using a UV-Vis spectrometer, and the changes in fluorescence spectra before and after the addition of metal ions were recorded using a fluorescence spectrometer. Electrochromic polymer I based on benzothiazolyl derivatives exhibited high sensitivity and high selectivity for recognizing iron and ruthenium ions, such as... Figure 4 , 5 As shown in Figures 6 and 7, its application in the identification and detection of metal ions in biological tissues and the environment has promising prospects.

Claims

1. A polymer of formula (Ⅰ): （I） in, n is 2-2000, R is C1-C 10 alkyl.

2. The polymer of formula (I) as described in claim 1, characterized in that: R is .

3. The method for preparing the polymer of formula (I) as described in claim 1, characterized in that... The preparation method is as follows: Under a protective atmosphere, compound (II), compound (V), neopentanoic acid, palladium acetate, and potassium carbonate were added to N,N-dimethylacetamide and reacted at 130℃~140℃ for 36h~48h. The resulting reaction solution E was post-treated to obtain the polymer shown in formula (I). The molar ratio of compound (II), compound (V), neopentanoic acid, potassium carbonate, and palladium acetate was 1:1:0.3~0.4:2~2.5:0.04~0.

08. (Ⅱ) (Ⅴ) （I） In equations (I), (II), and (V), n is 2-2000, and R is C1-C2. 10 One of the alkyl groups.

4. The method for preparing the polymer of formula (I) as described in claim 3, characterized in that: The protective atmosphere is nitrogen or argon.

5. The method for preparing the polymer of formula (I) as described in claim 3, characterized in that: The N,N-dimethylacetamide is 30-40 mL / g based on the mass of the compound shown in formula (V).

6. The method for preparing the polymer of formula (I) as described in claim 3, characterized in that: The post-treatment E is as follows: after the reaction solution E is cooled to room temperature, it is poured into methanol to precipitate solids, filtered, and the resulting filter cake is successively subjected to Soxhlet extraction with methanol, n-hexane, acetone and chloroform. The chloroform washing liquid is collected, the solvent is removed by rotary evaporation and dried to obtain the polymer shown in formula (I).

7. The method for preparing the polymer of formula (I) as described in claim 6, characterized in that: The volume ratio of methanol to N,N-dimethylacetamide is 6:

1.

8. The use of the polymer of formula (I) as described in claim 1 in the preparation of electrochromic materials.

9. The application of the polymer of formula (I) as described in claim 1 in the preparation of ion probes, characterized in that... The application is as follows: the polymer shown in formula (Ⅰ) is used as an ion probe to detect iron ions and ruthenium ions.

Images