A conductive polymer material, a preparation method and applications

Abstract

This invention relates to the field of organic electrochromic materials, specifically to a conductive polymer material, its preparation method, and its applications. The main chain of this conductive polymer material is composed of aryl groups, with dihydrophenazine located on the side chain. This structure combines the advantages of small-molecule dihydrophenazine as an anodic electrochromic material with the good conductivity of aromatic amine polymers. By changing the types of substituents, a polymer material with good anodic electrochromic properties can be obtained and applied to electrochromic devices.

Description

Technical Field

[0001] This invention relates to the field of organic light-emitting materials, specifically to a conductive polymer material, its preparation method, and its application. Background Technology

[0002] Electrochromism is a phenomenon in which colors can change reversibly under voltage regulation. Due to its low energy consumption, memory properties, simple structure, and low cost, electrochromic devices have long been considered promising for commercial passive display applications, such as electronic tags and electronic paper. Since the 1970s, research on electrochromic devices has primarily focused on inorganic materials such as tungsten oxide. However, the development of inorganic electrochromic devices has also revealed some drawbacks that have hindered large-scale commercialization. The most significant problems are slow switching response and limited color options, which are mainly determined by the inherent characteristics of inorganic materials.

[0003] In liquid devices, 5,10-dimethyl-5,10-dihydrophenazine anodic electrochromic material, when matched with viologen, can be used to prepare electrochromic devices with good performance (ZL200580041480.5). However, as a small molecule material, its presence in a solution state in electrochromic devices poses a risk of leakage. Summary of the Invention

[0004] In view of the many shortcomings of existing electrochromic materials, this invention provides a conductive polymer material, a preparation method, and an application.

[0005] The technical solution of the present invention is achieved in the following way: a conductive polymer material is provided, the molecular formula of which is as follows:

[0006]

[0007] Where n is a positive integer; n = 1 ~ 100.

[0008] R is selected from alkyl (C) m H 2m+1 (m is a natural number from 1 to 20), benzyl, substituted benzyl, phenyl, substituted phenyl;

[0009] Ar is aryl or substituted aryl.

[0010] Preferably, the Ar is selected from the following:

[0011]

[0012] Wherein, R′ is selected from H, alkyl (C m H 2m+1 (m is a natural number from 1 to 20), alkoxy groups, oligoether groups ( ).

[0013] Preferably, the conductive polymer material is selected from:

[0014]

[0015]

[0016]

[0017] .

[0018] In a second aspect of the present invention, a method for preparing the conductive polymer material is provided, the preparation process of which is as follows:

[0019]

[0020] Specifically, the steps include the following:

[0021] S1, 5,10-dihydro-phenazine (I) was dissolved in a solvent, and a catalyst and a haloalkanes (II) were added. The mixture was stirred until the reaction was complete, and the mixture was separated and purified to obtain 5-substituted-5,10-dihydro-phenazine (III).

[0022] S2, 1,4-dihydroxy-2,5-bis(bromomethyl)benzene (IV) and 2 equivalents of 5-substituted-5,10-dihydro-phenazine (III) reacted completely in a solvent to isolate the intermediate compound (V).

[0023] S3, intermediate compound (V) undergoes esterification with p-toluenesulfonyl chloride (molar ratio 1:2) to give compound (VI);

[0024] S4, compound (VI) and aryl diboronic acid ester derivative (B) (reaction in a 1:1 molar ratio) undergo a Suzuki coupling reaction with tetrakis(triphenylphosphine)palladium as catalyst and toluene as solvent to obtain the target polymer (P).

[0025] Preferably, in step S1, the solvent is dimethoxyethane and the catalyst is n-butyllithium hexane;

[0026] After the reaction was complete, a saturated aqueous solution of sodium dithionate was added, and the mixture was extracted three times with dichloromethane. After drying with anhydrous sodium sulfate, the mixture was concentrated and 5-substituted-5,10-dihydro-phenazine (III) was obtained by dichloromethane / petroleum ether column chromatography.

[0027] Preferably, in step S2, the reaction is carried out in potassium carbonate and dichloromethane overnight at room temperature, washed three times with water, the organic phase is dried with anhydrous sodium sulfate, concentrated, and separated by column chromatography to obtain intermediate compound (V).

[0028] In a third aspect of the invention, the application of the aforementioned conductive polymer material in electrochromic devices is also provided.

[0029] The beneficial effects are as follows:

[0030] Small-molecule dihydrophenazine compounds have exhibited excellent device performance as anodic electrochromic materials. However, as integrated liquid devices, they pose risks of leakage and sinking. This invention combines the excellent color-changing properties of the dihydrophenazine structure with the conductivity of the main chain having a conjugated system to obtain a conductive polymer material containing dihydrophenazine functional groups with good conductivity. Large-area thin film devices can be prepared by solution spin coating / printing / coating and other processes and applied to electrochromic devices. Detailed Implementation

[0031] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below in conjunction with specific embodiments. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0032] Based on the material synthesis, electrochromic thin film devices were prepared, and their device performance was investigated.

[0033] Fabrication of electrochromic devices:

[0034] Transparent ITO conductive glass cut into different sizes was first soaked in a mixed solvent of ammonia / hydrogen peroxide, then ultrasonically treated sequentially with deionized water, acetone, and isopropanol to obtain cleaned ITO glass. After removal, it was dried with dry nitrogen gas. A polymer sample was dissolved in toluene to prepare a 40 mg / mL solution, which was then spin-coated onto an ITO plate. This was then bonded to another ITO plate with adhesive, and an electrolyte solution was further injected using a liquid-filling method. The color change was observed by applying a voltage. Its electrochromic response time and driving voltage were tested.

[0035] Example 1: Synthesis of a representative conductive polymer material P-1 containing 5,10-dihydro-5-methylphenazine.

[0036] The synthesis route is shown below:

[0037]

[0038] 5,10-Dihydrophenazine (I, 56 g, 300 mmol) was dissolved in 250 mL of dimethoxyethane. At room temperature, 320 mL of 2 mol / L n-butyllithium hexane solution was added dropwise. After the addition was complete, 20 mL (320 mmol) of iodomethane (II) was added. The mixture was stirred for another 30 minutes at room temperature, then saturated sodium dithionate aqueous solution was added. The mixture was extracted three times with dichloromethane, dried over anhydrous sodium sulfate, concentrated, and purified by dichloromethane / petroleum ether column chromatography to obtain 42 g of 5-methyl-5,10-dihydrophenazine (III). 1HNMR (500 MHz, Chloroform) δ 7.73 (s, 1H), 7.14 (dd, J = 11.1, 7.0 Hz, 4H), 6.95 (dd, J = 11.1, 7.0 Hz, 4H), 3.20 (s, 3H).

[0039] 29.5 g (100 mmol) of 1,4-dihydroxy-2,5-bis(bromomethyl)benzene (A1) was reacted with 39.2 g (200 mmol) of 5-methyl-5,10-dihydrophenazine (III) and 41.4 g (300 mmol) of potassium carbonate in 1000 mL of dichloromethane at room temperature overnight. The mixture was washed three times with water, dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography to give intermediate compound A3. 1 HNMR (500 MHz, Chloroform) δ 7.13 (dt, J = 14.9, 7.5 Hz, 4H), 7.06 – 6.80 (m,4H), 6.68 (s, 1H), 5.43 (s, 2H), 4.31 (s, 1H), 3.20 (s, 3H).

[0040] 25.7 g (50 mmol) of hydroxyl-containing intermediate A3 and 22.7 g (120 mmol) of p-toluenesulfonyl chloride were dissolved and stirred in 1000 mL of dichloromethane at room temperature. The reaction was monitored by thin-layer chromatography until complete. The mixture was washed three times with saturated sodium bicarbonate aqueous solution, then three times with water, dried over anhydrous sodium sulfate, and concentrated to obtain the crude product. The crude product was subjected to column chromatography in dichloromethane and petroleum ether to obtain 38.5 g of sulfonated intermediate A4. 1 H NMR (500 MHz, Chloroform ) δ 7.81 – 7.58 (m,2H), 7.53 – 7.35 (m, 2H), 7.09 (dt, J= 14.9, 7.4 Hz, 4H), 6.99 – 6.77 (m, 4H), 6.64 (s, 1H), 5.67 (s, 2H), 3.18 (s, 3H), 2.41 (s, 3H).

[0041] 8.35 g (10 mmol) of sulfonated intermediate compound A5 and 5.58 g (10 mmol) of diboronate compound (B1) were dissolved in 250 mL of toluene. 10 mL of 2 mol / L potassium carbonate aqueous solution was added, and the mixture was purged with nitrogen for 30 min. 20 mmol × 1% (0.23 g) of Pd(PPh3)4 was added, and the mixture was heated under reflux and stirred overnight under nitrogen. After cooling to room temperature, the mixture was poured into 500 mL of methanol and filtered to obtain the crude product. The filter cake was successively extracted with methanol, acetone, n-hexane, and chloroform using a Soxhlet extractor to obtain the target polymer P-1.Mw:9863. 1 H NMR (500 MHz, Chloroform) δ 7.94 (d, J = 8.8 Hz, 1H),7.29 (s, 1H), 7.20 – 7.05 (m, 4H), 7.02 – 6.81 (m, 4H), 5.43 (d, J = 5.3 Hz, 2H), 4.11 (t, J = 14.8 Hz, 2H), 3.20 (s, 3H), 1.81 (dq, J = 29.6, 14.7 Hz, 2H), 1.59 – 1.33 (m, 2H), 1.33 – 1.14 (m, 6H), 1.02 – 0.76 (m, 3H).

[0042] Example 2: Synthesis of P-2, a representative conductive polymer material containing 5,10-dihydro-5-methylphenazine.

[0043]

[0044] 8.35 g (10 mmol) of sulfonated intermediate compound A5 and 5.56 g (10 mmol) of diboronate compound (B2) were dissolved in 250 mL of toluene. 10 mL of 2 mol / L potassium carbonate aqueous solution was added, and the mixture was purged with nitrogen for 30 min. 20 mmol × 1% (0.23 g) of Pd(PPh3)4 was added, and the mixture was heated under reflux and stirred overnight under nitrogen. After cooling to room temperature, the mixture was poured into 500 mL of methanol and filtered to obtain the crude product. The filter cake was successively extracted with methanol, acetone, n-hexane, and chloroform using a Soxhlet extractor to obtain the target polymer P-2.Mw:2541. 1 H NMR (500 MHz, Chloroform) δ 7.85 (d, J = 72.0 Hz, 2H),7.29 (s, 1H), 7.14 (dt, J = 19.1, 7.7 Hz, 9H), 7.04 – 6.84 (m, 8H), 5.26 (d, J =6.4 Hz, 4H), 4.31 (t, J = 14.1 Hz, 4H), 3.77 (t, J = 14.1 Hz, 4H), 3.61 – 3.47(m, 8H), 3.40 (s, 6H), 3.20 (s, 6H).

[0045] Example 3: Synthesis of P-3, a representative conductive polymer material containing 5,10-dihydro-5-methylphenazine.

[0046]

[0047] 8.35 g (10 mmol) of sulfonated intermediate compound A5 and 3.80 g (10 mmol) of diboronate compound (B3) were dissolved in 250 mL of toluene. 10 mL of 2 mol / L potassium carbonate aqueous solution was added, and the mixture was purged with nitrogen for 30 min. 20 mmol × 1% (0.23 g) of Pd(PPh3)4 was added, and the mixture was heated under reflux and stirred overnight under nitrogen. After cooling to room temperature, the mixture was poured into 500 mL of methanol and filtered to obtain the crude product. The filter cake was successively extracted with methanol, acetone, n-hexane, and chloroform using a Soxhlet extractor to obtain the target polymer P-3.Mw:18740. 1 H NMR (500 MHz, Chloroform ) δ 8.07 – 7.71 (m, 5H), 7.64– 7.50 (m, 2H), 7.38 (dd, J= 15.0, 3.1 Hz, 1H), 7.22 – 7.07 (m, 8H), 7.02 –6.82 (m, 8H), 5.44 (d, J = 29.9 Hz, 4H), 3.20 (s, 6H).

[0048] Example 4: Synthesis of P-4, a representative conductive polymer material containing 5,10-dihydro-5-methylphenazine.

[0049]

[0050] 8.35 g (10 mmol) of sulfonated intermediate compound A5 and 6.14 g (10 mmol) of diboronate compound (B4) were dissolved in 250 mL of toluene. 10 mL of 2 mol / L potassium carbonate aqueous solution was added, and the mixture was purged with nitrogen for 30 min. 20 mmol × 1% (0.23 g) of Pd(PPh3)4 was added, and the mixture was heated under reflux and stirred overnight under nitrogen. After cooling to room temperature, the mixture was poured into 500 mL of methanol and filtered to obtain the crude product. The filter cake was successively extracted with methanol, acetone, n-hexane, and chloroform using a Soxhlet extractor to obtain the target polymer P-4.Mw:15574. 1 H NMR (500 MHz, Chloroform) δ 8.17 – 7.39 (m, 8H), 7.23 – 7.05 (m, 8H), 7.01 – 6.84 (m, 8H), 5.32 (d, J = 53.3 Hz, 4H), 3.20 (s,6H), 2.07 – 1.84 (m, 4H), 1.55 – 1.13 (m, 21H), 1.00 – 0.75 (m, 6H).

[0051] Example 5: Synthesis of P-5, a representative conductive polymer material containing 5,10-dihydro-5-methylphenazine.

[0052]

[0053] 8.35 g (10 mmol) of sulfonated intermediate compound A5 and 6.22 g (10 mmol) of diboronate compound (B5) were dissolved in 250 mL of toluene. 10 mL of 2 mol / L potassium carbonate aqueous solution was added, and the mixture was purged with nitrogen for 30 min. 20 mmol × 1% (0.23 g) of Pd(PPh3)4 was added, and the mixture was heated under reflux and stirred overnight under nitrogen. After cooling to room temperature, the mixture was poured into 500 mL of methanol and filtered to obtain the crude product. The filter cake was successively extracted with methanol, acetone, n-hexane, and chloroform using a Soxhlet extractor to obtain the target polymer P-5.Mw:12732. 1 H NMR (500 MHz, Chloroform ) δ 8.23 ​​– 8.03 (m, 2H), 8.00 – 7.67 (m, 4H), 7.58 – 7.38 (m, 2H), 7.24 – 7.07 (m, 8H), 7.03 – 6.86(m, 8H), 5.36 (d, J = 35.2 Hz, 4H), 3.63 – 3.44 (m, 8H), 3.43 – 3.28 (m, 10H), 3.20 (s, 6H), 2.23 – 2.01 (m, 4H).

[0054] Example 6: Synthesis of P-6, a representative conductive polymer material containing 5,10-dihydro-5-methylphenazine.

[0055]

[0056] 8.35 g (10 mmol) of sulfonated intermediate compound A5 and 5.17 g (10 mmol) of diboronate compound (B6) were dissolved in 250 mL of toluene. 10 mL of 2 mol / L potassium carbonate aqueous solution was added, and the mixture was purged with nitrogen for 30 min. 20 mmol × 1% (0.23 g) of Pd(PPh3)4 was added, and the mixture was heated under reflux and stirred overnight under nitrogen. After cooling to room temperature, the mixture was poured into 500 mL of methanol and filtered to obtain the crude product. The filter cake was successively extracted with methanol, acetone, n-hexane, and chloroform using a Soxhlet extractor to obtain the target polymer P-6. Mw:19872. 1 H NMR (500 MHz, Chloroform) δ 7.99 – 7.26 (m, 8H), 7.21 – 7.01 (m, 8H), 7.00 – 6.80 (m, 8H), 5.28 (d, J = 41.9 Hz, 4H), 4.14 (t, J=21.5 Hz, 2H), 3.19 (s, 6H), 1.95 – 1.56 (m, 2H), 1.49 – 1.10 (m, 8H), 1.01 –0.74 (m, 3H).

[0057] Example 7: Synthesis of P-7, a representative conductive polymer material containing 5,10-dihydro-5-methylphenazine.

[0058]

[0059] 8.35 g (10 mmol) of sulfonated intermediate compound A5 and 5.21 g (10 mmol) of diboronate compound (B7) were dissolved in 250 mL of toluene. 10 mL of 2 mol / L potassium carbonate aqueous solution was added, and the mixture was purged with nitrogen for 30 min. 20 mmol × 1% (0.23 g) of Pd(PPh3)4 was added, and the mixture was heated under reflux and stirred overnight under nitrogen. After cooling to room temperature, the mixture was poured into 500 mL of methanol and filtered to obtain the crude product. The filter cake was successively extracted with methanol, acetone, n-hexane, and chloroform using a Soxhlet extractor to obtain the target polymer P-7.Mw:27580. 1 H NMR (500 MHz, Chloroform ) δ 7.98 – 7.56 (m, 6H), 7.50 – 7.35 (m, 2H), 7.21 – 7.07 (m, 8H), 7.01 – 6.86 (m, 8H), 5.39 (d, J = 44.3 Hz, 4H), 4.45 (td, J = 18.9, 0.6 Hz, 2H), 3.83 – 3.62 (m, 2H), 3.53 (td, J = 6.7, 1.3Hz, 4H), 3.40 (s, 3H), 3.20 (s, 6H).

[0060] Example 8: Synthesis of P-8, a representative conductive polymer material containing 5,10-dihydro-5-methylphenazine.

[0061]

[0062] 8.35 g (10 mmol) of sulfonated intermediate compound A5 and 6.70 g (10 mmol) of diboronate compound (B8) were dissolved in 250 mL of toluene. 10 mL of 2 mol / L potassium carbonate aqueous solution was added, and the mixture was purged with nitrogen for 30 min. 20 mmol × 1% (0.23 g) of Pd(PPh3)4 was added, and the mixture was heated under reflux and stirred overnight under nitrogen. After cooling to room temperature, the mixture was poured into 500 mL of methanol and filtered to obtain the crude product. The filter cake was successively extracted with methanol, acetone, n-hexane, and chloroform using a Soxhlet extractor to obtain the target polymer P-8.Mw:19578. 1 H NMR (500 MHz, Chloroform) δ 7.87 (dd, J = 83.5, 48.5Hz, 4H), 7.20 – 7.01 (m, 8H), 6.96 – 6.76 (m, 8H), 5.38 (d, J = 51.8 Hz, 4H), 4.08 (t, J = 20.2 Hz, 4H), 3.18 (s, 6H), 1.79 (dqd, J = 24.7, 19.9, 2.3 Hz, 4H), 1.58 – 1.09 (m, 17H), 0.99 – 0.69 (m, 6H).

[0063] Example 9: Synthesis of P-9, a representative conductive polymer material containing 5,10-dihydro-5-methylphenazine.

[0064]

[0065] 8.35 g (10 mmol) of sulfonated intermediate compound A5 and 6.78 g (10 mmol) of diboronate compound (B9) were dissolved in 250 mL of toluene. 10 mL of 2 mol / L potassium carbonate aqueous solution was added, and the mixture was purged with nitrogen for 30 min. 20 mmol × 1% (0.23 g) of Pd(PPh3)4 was added, and the mixture was heated under reflux and stirred overnight under nitrogen. After cooling to room temperature, the mixture was poured into 500 mL of methanol and filtered to obtain the crude product. The filter cake was successively extracted with methanol, acetone, n-hexane, and chloroform using a Soxhlet extractor to obtain the target polymer P-9.Mw:21431. 1 H NMR (500 MHz, Chloroform) δ 8.06 (s, 1H), 7.87 (d, J= 49.5 Hz, 3H), 7.24 – 7.06 (m, 8H), 7.02 – 6.80 (m, 8H), 5.39 (d, J = 49.1Hz, 4H), 4.31 (td, J = 17.7, 1.0 Hz, 4H), 3.77 (td, J = 17.8, 0.9 Hz, 4H), 3.60 –3.47 (m, 8H), 3.40 (s, 6H), 3.20 (s, 6H).

[0066] Example 10: Synthesis of P-10, a representative conductive polymer material containing 5,10-dihydro-5-methylphenazine.

[0067]

[0068] 8.35 g (10 mmol) of sulfonated intermediate compound A5 and 6.05 g (10 mmol) of diboronate compound (B10) were dissolved in 250 mL of toluene. 10 mL of 2 mol / L potassium carbonate aqueous solution was added, and the mixture was purged with nitrogen for 30 min. 20 mmol × 1% (0.23 g) of Pd(PPh3)4 was added, and the mixture was heated under reflux and stirred overnight under nitrogen. After cooling to room temperature, the mixture was poured into 500 mL of methanol and filtered to obtain the crude product. The filter cake was successively extracted with methanol, acetone, n-hexane, and chloroform using a Soxhlet extractor to obtain the target polymer P-10.Mw:12237. 1 H NMR (500 MHz, Chloroform) δ 7.99 (d, J = 58.4 Hz,2H), 7.26 – 7.06 (m, 8H), 7.04 – 6.79 (m, 8H), 5.62 (d, J = 166.9 Hz, 4H), 4.11(t, J = 20.3 Hz, 4H), 3.20 (s, 6H), 1.99 – 1.61 (m, 4H), 1.57 – 1.07 (m, 17H), 1.01 – 0.76 (m, 6H).

[0069] Example 11: Synthesis of P-11, a representative conductive polymer material containing 5,10-dihydro-5-methylphenazine.

[0070]

[0071] 8.35 g (10 mmol) of sulfonated intermediate compound A5 and 6.28 g (10 mmol) of diboronate compound (B11) were dissolved in 250 mL of toluene. 10 mL of 2 mol / L potassium carbonate aqueous solution was added, and the mixture was purged with nitrogen for 30 min. 20 mmol × 1% (0.23 g) of Pd(PPh3)4 was added, and the mixture was heated under reflux and stirred overnight under nitrogen. After cooling to room temperature, the mixture was poured into 500 mL of methanol and filtered to obtain the crude product. The filter cake was successively extracted with methanol, acetone, n-hexane, and chloroform using a Soxhlet extractor to obtain the target polymer P-11.Mw:21472. 1 H NMR (500 MHz, Chloroform) δ 8.01 (d, J = 81.0 Hz,2H), 7.21 – 7.04 (m, 8H), 7.02 – 6.83 (m, 8H), 5.49 (d, J = 160.1 Hz, 4H), 4.31(td, J = 17.7, 1.0 Hz, 4H), 3.77 (td, J = 17.8, 0.9 Hz, 4H), 3.61 – 3.45 (m, 8H), 3.40 (s, 6H), 3.20 (s, 6H).

[0072] Example 12: Synthesis of P-12, a representative conductive polymer material containing 5,10-dihydro-5-methylphenazine.

[0073]

[0074] 8.35 g (10 mmol) of sulfonated intermediate compound A5 and 4.48 g (10 mmol) of diboronate compound (B12) were dissolved in 250 mL of toluene. 10 mL of 2 mol / L potassium carbonate aqueous solution was added, and the mixture was purged with nitrogen for 30 min. 20 mmol × 1% (0.23 g) of Pd(PPh3)4 was added, and the mixture was heated under reflux and stirred overnight under nitrogen. After cooling to room temperature, the mixture was poured into 500 mL of methanol and filtered to obtain the crude product. The filter cake was successively extracted with methanol, acetone, n-hexane, and chloroform using a Soxhlet extractor to obtain the target polymer P-12. Mw: 21352. 1 H NMR (500 MHz, Chloroform) δ 7.95 (d, J= 24.2 Hz, 2H), 7.46 (s, 1H), 7.33 – 7.03 (m, 8H), 7.02 – 6.78 (m, 8H), 5.51 (d, J = 78.0Hz, 4H), 3.20 (s, 6H), 2.68 (t, J = 22.9 Hz, 2H), 1.65 – 1.36 (m, 2H), 1.35 –1.11 (m, 10H), 1.01 – 0.65 (m, 3H).

[0075] Example 13: Synthesis of P-13, a representative conductive polymer material containing phenathiazide.

[0076] The synthesis route is shown below:

[0077]

[0078] 5,10-Dihydro-5-methylphenazine (i, 56 g, 300 mmol) was dissolved in 250 mL of dimethoxyethane. At room temperature, 320 mL of 2 mol / L n-butyllithium hexane solution was added dropwise in steps. After the addition was complete, 54 g (320 mmol) of iodomethane was added (ii). The mixture was stirred for another 30 minutes at room temperature, then saturated sodium dithionate aqueous solution was added. The mixture was extracted three times with dichloromethane, dried over anhydrous sodium sulfate, concentrated, and purified by dichloromethane / petroleum ether column chromatography to obtain 45 g of 5-benzyl-5,10-dihydro-5-methylphenazine (iii). 1 H NMR (500 MHz, Chloroform) δ 7.80 (s, 1H), 7.37 – 7.22 (m, 5H), 7.18 – 7.09 (m, 4H), 7.02 – 6.89 (m, 4H), 5.31 (s, 2H).

[0079] 29.5 g (100 mmol) of 1,4-dihydroxy-2,5-bis(bromomethyl)benzene (B1) was reacted with 54.4 g (200 mmol) of 5-benzyl-5,10-dihydro-5-methylphenazine (iii) and 41.4 g (300 mmol) of potassium carbonate in 1000 mL of dichloromethane at room temperature overnight. The mixture was washed three times with water, dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography to give intermediate compound B3. 1H NMR (500 MHz, Chloroform ) δ 7.41 – 7.22 (m, 10H), 7.21 – 7.03 (m,8H), 7.02 – 6.82 (m, 8H), 6.68 (s, 2H), 5.51 (s, 4H), 5.39 (s, 4H), 4.33 (s,2H).

[0080] 33.9 g (50 mmol) of hydroxyl-containing intermediate B3 and 22.7 g (120 mmol) of p-toluenesulfonyl chloride were dissolved and stirred in 1000 mL of dichloromethane at room temperature. The reaction was monitored by thin-layer chromatography until complete. The mixture was washed three times with saturated sodium bicarbonate aqueous solution, then three times with water, dried over anhydrous sodium sulfate, and concentrated to obtain the crude product. The crude product was subjected to column chromatography in dichloromethane and petroleum ether to obtain 42.3 g of sulfonated intermediate B4. 13 C NMR (125 MHz, Common NMR Solvents ) δ 141.97(s), 141.51 (s), 137.64 (s), 136.99 (d, J = 12.4 Hz), 131.41 (s), 129.60 (s), 128.99 (s), 128.47 (d, J = 14.3 Hz), 128.03 (s), 124.32 (s), 119.27 (s), 118.33(s), 53.26 (s), 51.28 (s), 21.15 (s).

[0081] 9.86 g (10 mmol) of sulfonated intermediate compound B5 and 5.58 g (10 mmol) of diboronate compound (B1) were dissolved in 250 mL of toluene. 10 mL of 2 mol / L potassium carbonate aqueous solution was added, and the mixture was purged with nitrogen for 30 min. 20 mmol × 1% (0.23 g) of Pd(PPh3)4 was added, and the mixture was heated under reflux and stirred overnight under nitrogen. After cooling to room temperature, the mixture was poured into 500 mL of methanol and filtered to obtain the crude product. The filter cake was successively extracted with methanol, acetone, n-hexane, and chloroform using a Soxhlet extractor to obtain the target polymer P-13.Mw:21612. 1H NMR (500 MHz, Chloroform ) δ 8.22 (s, 1H), 7.93(s, 1H), 7.38 – 7.25 (m, 11H), 7.21 – 7.05 (m, 9H), 7.03 – 6.84 (m, 8H), 5.41(s, 2H), 5.38 (s, 6H), 4.11 (t, J = 14.8 Hz, 4H), 2.01 – 1.67 (m, 4H), 1.52 –1.34 (m, 4H), 1.32 – 1.13 (m, 12H), 1.03 – 0.76 (m, 6H).

[0082] Example 14: Synthesis of P-14, a representative conductive polymer material containing 5,10-dihydro-5-methylphenazine.

[0083]

[0084] 9.86 g (10 mmol) of sulfonated intermediate compound B5 and 5.56 g (10 mmol) of diboronate compound (B2) were dissolved in 250 mL of toluene. 10 mL of 2 mol / L potassium carbonate aqueous solution was added, and the mixture was purged with nitrogen for 30 min. 20 mmol × 1% (0.23 g) of Pd(PPh3)4 was added, and the mixture was heated under reflux and stirred overnight under nitrogen. After cooling to room temperature, the mixture was poured into 500 mL of methanol and filtered to obtain the crude product. The filter cake was successively extracted with methanol, acetone, n-hexane, and chloroform using a Soxhlet extractor to obtain the target polymer P-14.Mw:31632. 1 H NMR (500 MHz, Chloroform ) δ 8.15 (s, 1H), 7.90 (s,1H), 7.37 (s, 1H), 7.32 – 7.20 (m, 11H), 7.17 – 7.05 (m, 8H), 6.99 – 6.84 (m,8H), 5.40 (s, 4H), 5.33 (s, 4H), 4.29 (t, J = 14.1 Hz, 4H), 3.75 (dd, J = 21.3,7.3 Hz, 4H), 3.62 – 3.46 (m, 8H), 3.39 (s, 6H).

[0085] Example 15: Synthesis of P-15, a representative conductive polymer material containing 5,10-dihydro-5-methylphenazine.

[0086]

[0087] 9.86 g (10 mmol) of sulfonated intermediate compound B5 and 3.80 g (10 mmol) of diboronate compound (B3) were dissolved in 250 mL of toluene. 10 mL of 2 mol / L potassium carbonate aqueous solution was added, and the mixture was purged with nitrogen for 30 min. 20 mmol × 1% (0.23 g) of Pd(PPh3)4 was added, and the mixture was heated under reflux and stirred overnight under nitrogen. After cooling to room temperature, the mixture was poured into 500 mL of methanol and filtered to obtain the crude product. The filter cake was successively extracted with methanol, acetone, n-hexane, and chloroform using a Soxhlet extractor to obtain the target polymer P-15.Mw:31734. 1 H NMR (500 MHz, Chloroform) δ 7.99 (dd, J = 15.0, 3.1 Hz,1H), 7.93 (s, 1H), 7.83 (t, J = 3.0 Hz, 1H), 7.77 (dd, J = 15.0, 2.9 Hz, 1H),7.59 – 7.47 (m, 2H), 7.38 (dd, J = 15.0, 3.1 Hz, 1H), 7.35 – 7.21 (m, 10H), 7.20 – 7.04 (m, 8H), 7.03 – 6.86 (m, 8H), 6.08 (s, 1H), 5.67 (s, 4H), 5.08(s, 2H), 4.89 (s, 2H).

[0088] Example 16: Synthesis of P-16, a representative conductive polymer material containing 5,10-dihydro-5-methylphenazine.

[0089]

[0090] 9.86 g (10 mmol) of sulfonated intermediate compound B5 and 6.14 g (10 mmol) of diboronate compound (B4) were dissolved in 250 mL of toluene. 10 mL of 2 mol / L potassium carbonate aqueous solution was added, and the mixture was purged with nitrogen for 30 min. 20 mmol × 1% (0.23 g) of Pd(PPh3)4 was added, and the mixture was heated under reflux and stirred overnight under nitrogen. After cooling to room temperature, the mixture was poured into 500 mL of methanol and filtered to obtain the crude product. The filter cake was successively extracted with methanol, acetone, n-hexane, and chloroform using a Soxhlet extractor to obtain the target polymer P-16.Mw:41752. 1H NMR (500 MHz, Chloroform) δ 8.26 (s, 1H), 8.07(dd, J = 13.2, 9.0 Hz, 2H), 7.91 (d, J = 15.0 Hz, 2H), 7.77 (dd, J = 14.9, 3.0 Hz,1H), 7.43 (s, 4H), 7.36 – 7.23 (m, 10H), 7.13 (dt, J = 14.8, 7.4 Hz, 8H), 7.03– 6.84 (m, 8H), 5.74 (s, 1H), 5.51 (s, 2H), 5.40 (s, 2H), 1.93 (t, J = 15.2 Hz, 4H), 1.53 – 1.14 (m, 20H), 1.01 – 0.74 (m, 6H).

[0091] Example 17: Synthesis of P-17, a representative conductive polymer material containing 5,10-dihydro-5-methylphenazine.

[0092]

[0093] 9.86 g (10 mmol) of sulfonated intermediate compound B5 and 6.22 g (10 mmol) of diboronate compound (B5) were dissolved in 250 mL of toluene. 10 mL of 2 mol / L potassium carbonate aqueous solution was added, and the mixture was purged with nitrogen for 30 min. 20 mmol × 1% (0.23 g) of Pd(PPh3)4 was added, and the mixture was heated under reflux and stirred overnight under nitrogen. After cooling to room temperature, the mixture was poured into 500 mL of methanol and filtered to obtain the crude product. The filter cake was successively extracted with methanol, acetone, n-hexane, and chloroform using a Soxhlet extractor to obtain the target polymer P-17.Mw:31931. 1 H NMR (500 MHz, Chloroform) δ 8.38 (s, 1H), 8.06(d, J = 14.8 Hz, 1H), 7.88 (d, J= 14.8 Hz, 2H), 7.83 – 7.67 (m, 2H), 7.38 – 7.21(m, 10H), 7.20 – 7.06 (m, 8H), 6.99 – 6.84 (m, 8H), 5.78 (s, 1H), 5.75 (s,4H), 5.46 (s, 2H), 5.07 (s, 2H), 3.64 – 3.30 (m, 18H), 2.11 (t, J = 14.6 Hz, 4H).

[0094] Example 18: Synthesis of P-18, a representative conductive polymer material containing 5,10-dihydro-5-methylphenazine.

[0095]

[0096] 9.86 g (10 mmol) of sulfonated intermediate compound B5 and 5.17 g (10 mmol) of diboronate compound (B6) were dissolved in 250 mL of toluene. 10 mL of 2 mol / L potassium carbonate aqueous solution was added, and the mixture was purged with nitrogen for 30 min. 20 mmol × 1% (0.23 g) of Pd(PPh3)4 was added, and the mixture was heated under reflux and stirred overnight under nitrogen. After cooling to room temperature, the mixture was poured into 500 mL of methanol and filtered to obtain the crude product. The filter cake was successively extracted with methanol, acetone, n-hexane, and chloroform using a Soxhlet extractor to obtain the target polymer P-18.Mw:21741. 1 H NMR (500 MHz, Chloroform ) δ 8.05 (s, 1H), 7.92 (s, 1H), 7.82 (d, J = 15.0 Hz, 1H), 7.64 (dd, J = 24.9, 9.0 Hz, 2H), 7.41 (dd, J =15.0, 2.9 Hz, 1H), 7.36 – 7.26 (m, 10H), 7.20 – 7.07 (m, 8H), 7.01 – 6.83 (m,8H), 5.90 (d, J = 2.9 Hz, 1H), 5.63 – 5.21 (m, 9H), 4.16 (t, J = 21.5 Hz, 2H), 1.99 – 1.54 (m, 2H), 1.49 – 1.13 (m, 9H), 1.04 – 0.75 (m, 3H).

[0097] Example 19: Synthesis of P-19, a representative conductive polymer material containing 5,10-dihydro-5-methylphenazine.

[0098]

[0099] 9.86 g (10 mmol) of sulfonated intermediate compound B5 and 5.21 g (10 mmol) of diboronate compound (B7) were dissolved in 250 mL of toluene. 10 mL of 2 mol / L potassium carbonate aqueous solution was added, and the mixture was purged with nitrogen for 30 min. 20 mmol × 1% (0.23 g) of Pd(PPh3)4 was added, and the mixture was heated under reflux and stirred overnight under nitrogen. After cooling to room temperature, the mixture was poured into 500 mL of methanol and filtered to obtain the crude product. The filter cake was successively extracted with methanol, acetone, n-hexane, and chloroform using a Soxhlet extractor to obtain the target polymer P-19.Mw:21874. 1 H NMR (500 MHz, Chloroform ) δ 8.25 (s, 1H), 7.93 (s,1H), 7.82 (d, J = 15.0 Hz, 1H), 7.72 (d, J = 2.9 Hz, 1H), 7.62 (d, J = 15.0 Hz, 1H), 7.42 (dd, J = 15.0, 2.9 Hz, 1H), 7.36 – 7.25 (m, 10H), 7.21 – 7.06 (m,8H), 7.04 – 6.84 (m, 12H), 6.01 (d, J = 2.9 Hz, 1H), 5.51 (s, 2H), 5.39 (dd, J =15.0, 3.1 Hz, 1H), 5.29 (s, 2H), 4.16 (t, J = 21.5 Hz, 2H), 1.91 – 1.61 (m,2H), 1.53 – 1.11 (m, 9H), 1.06 – 0.79 (m, 3H).

[0100] Example 20: Synthesis of P-20, a representative conductive polymer material containing 5,10-dihydro-5-methylphenazine.

[0101]

[0102] 9.86 g (10 mmol) of sulfonated intermediate compound B5 and 6.70 g (10 mmol) of diboronate compound (B8) were dissolved in 250 mL of toluene. 10 mL of 2 mol / L potassium carbonate aqueous solution was added, and the mixture was purged with nitrogen for 30 min. 20 mmol × 1% (0.23 g) of Pd(PPh3)4 was added, and the mixture was heated under reflux and stirred overnight under nitrogen. After cooling to room temperature, the mixture was poured into 500 mL of methanol and filtered to obtain the crude product. The filter cake was successively extracted with methanol, acetone, n-hexane, and chloroform using a Soxhlet extractor to obtain the target polymer P-20.Mw:31522. 1 H NMR (500 MHz, Chloroform ) δ 8.07 (s, 1H), 7.97 –7.71 (m, 3H), 7.39 – 7.23 (m, 10H), 7.21 – 7.06 (m, 8H), 7.03 – 6.84 (m, 8H), 5.55 (s, 2H), 5.40 (s, 4H), 5.35 (s, 2H), 4.11 (t, J = 20.2 Hz, 4H), 1.94 –1.66 (m, 4H), 1.60 – 1.14 (m, 16H), 1.02 – 0.70 (m, 6H).

[0103] Example 21: Synthesis of P-21, a representative conductive polymer material containing 5,10-dihydro-5-methylphenazine.

[0104]

[0105] 9.86 g (10 mmol) of sulfonated intermediate compound B5 and 6.78 g (10 mmol) of diboronate compound (B9) were dissolved in 250 mL of toluene. 10 mL of 2 mol / L potassium carbonate aqueous solution was added, and the mixture was purged with nitrogen for 30 min. 20 mmol × 1% (0.23 g) of Pd(PPh3)4 was added, and the mixture was heated under reflux and stirred overnight under nitrogen. After cooling to room temperature, the mixture was poured into 500 mL of methanol and filtered to obtain the crude product. The filter cake was successively extracted with methanol, acetone, n-hexane, and chloroform using a Soxhlet extractor to obtain the target polymer P-21.Mw:41642. 1 H NMR (500 MHz, Chloroform) δ 8.10 (d, J= 13.2 Hz,1H), 7.93 (s, 1H), 7.79 (s, 1H), 7.38 – 7.19 (m, 5H), 7.19 – 7.06 (m, 4H), 6.98 – 6.85 (m, 4H), 5.50 (s, 1H), 5.43 (s, 2H), 5.37 (s, 1H), 4.31 (td, J =17.7, 1.0 Hz, 2H), 3.77 (td, J = 17.8, 1.0 Hz, 2H), 3.61 – 3.47 (m, 4H), 3.40(s, 3H).

[0106] Example 22: Synthesis of P-22, a representative conductive polymer material containing 5,10-dihydro-5-methylphenazine.

[0107]

[0108] 9.86 g (10 mmol) of sulfonated intermediate compound B5 and 6.05 g (10 mmol) of diboronate compound (B10) were dissolved in 250 mL of toluene. 10 mL of 2 mol / L potassium carbonate aqueous solution was added, and the mixture was purged with nitrogen for 30 min. 20 mmol × 1% (0.23 g) of Pd(PPh3)4 was added, and the mixture was heated under reflux and stirred overnight under nitrogen. After cooling to room temperature, the mixture was poured into 500 mL of methanol and filtered to obtain the crude product. The filter cake was successively extracted with methanol, acetone, n-hexane, and chloroform using a Soxhlet extractor to obtain the target polymer P-22.Mw:32117. 1 H NMR (500 MHz, Chloroform ) δ 8.02 (s, 1H), 7.91(s, 1H), 7.40 – 7.22 (m, 10H), 7.19 – 7.05 (m, 8H), 7.01 – 6.83 (m, 8H), 5.81(s, 2H), 5.55 (s, 2H), 5.34 (s, 4H), 4.10 (t, J = 20.2 Hz, 4H), 1.95 – 1.66 (m,4H), 1.53 – 1.11 (m, 17H), 1.03 – 0.68 (m, 6H).

[0109] Example 23: Synthesis of P-23, a representative conductive polymer material containing 5,10-dihydro-5-methylphenazine.

[0110]

[0111] 9.86 g (10 mmol) of sulfonated intermediate compound B5 and 6.28 g (10 mmol) of diboronate compound (B11) were dissolved in 250 mL of toluene. 10 mL of 2 mol / L potassium carbonate aqueous solution was added, and the mixture was purged with nitrogen for 30 min. 20 mmol × 1% (0.23 g) of Pd(PPh3)4 was added, and the mixture was heated under reflux and stirred overnight under nitrogen. After cooling to room temperature, the mixture was poured into 500 mL of methanol and filtered to obtain the crude product. The filter cake was successively extracted with methanol, acetone, n-hexane, and chloroform using a Soxhlet extractor to obtain the target polymer P-23.Mw:21879. 1 H NMR (500 MHz, Chloroform ) δ 8.04 (s, 1H), 7.93(s, 1H), 7.44 – 7.24 (m, 10H), 7.22 – 7.06 (m, 8H), 7.04 – 6.84 (m, 8H), 5.81(s, 2H), 5.55 (s, 2H), 5.35 (s, 4H), 4.31 (td, J = 17.8, 1.0 Hz, 4H), 3.77 (td, J = 17.8, 0.9 Hz, 4H), 3.65 – 3.44 (m, 8H), 3.40 (s, 6H).

[0112] Example 24: Synthesis of P-24, a representative conductive polymer material containing 5,10-dihydro-5-methylphenazine.

[0113]

[0114] 9.86 g (10 mmol) of sulfonated intermediate compound B5 and 4.48 g (10 mmol) of diboronate compound (B12) were dissolved in 250 mL of toluene. 10 mL of 2 mol / L potassium carbonate aqueous solution was added, and the mixture was purged with nitrogen for 30 min. 20 mmol × 1% (0.23 g) of Pd(PPh3)4 was added, and the mixture was heated under reflux and stirred overnight under nitrogen. After cooling to room temperature, the mixture was poured into 500 mL of methanol and filtered to obtain the crude product. The filter cake was successively extracted with methanol, acetone, n-hexane, and chloroform using a Soxhlet extractor to obtain the target polymer P-24.Mw:31152. 1H NMR (500 MHz, Chloroform ) δ 8.31 (s, 1H), 7.93 (s, 1H), 7.46 – 7.24 (m, 11H), 7.22 – 7.07 (m, 8H), 7.02 – 6.85 (m, 8H), 5.61– 5.32 (m, 8H), 2.68 (t, J = 11.6 Hz, 2H), 1.64 – 1.39 (m, 2H), 1.36 – 1.13 (m,10H), 1.01 – 0.65 (m, 3H).

[0115] Example 25: Fabrication of Electrochromic Devices

[0116] The materials synthesized in Examples 1-24 above were prepared into a chloroform solution of 50 mg / mL for later use.

[0117] Transparent ITO conductive glass, cut to 3cm x 5cm, was first soaked in a mixed solvent of ammonia / hydrogen peroxide, then ultrasonically treated with deionized water, acetone, and isopropanol to obtain cleaned ITO glass. After removal, it was dried with dry nitrogen gas. The prepared solution was then spin-coated onto an ITO piece. This was then bonded to another ITO piece with adhesive, and further injected using a solution containing 0.1 mol / L tetrabutylammonium hexafluorophosphate and 0.01 mol / L ethyl amethyst hexafluorophosphate in propylene carbonate electrolyte solution. The connection was then sealed with UV adhesive. A voltage was applied between the electrodes, and the color change of the electrochromic device was observed. The specific results are shown in Table 1 below.

[0118] Table 1

[0119]

[0120] The polymer structures listed above are only a partial representation; other conductive polymer materials containing the same concept are all within the scope of this patent protection.

[0121] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention.

Claims

1. A conductive polymer material, characterized in that, Its molecular formula is as follows: Where n is a positive integer; R is selected from alkyl, benzyl, substituted benzyl, phenyl, substituted phenyl; Ar is selected from any one of the following C1 to C7: R′ is selected from H, alkyl, alkoxy, and oligoether groups.

2. The conductive polymer material according to claim 1, characterized in that, Choose from any one of the following pages: P1 to P24 。 3. A method for preparing the conductive polymer material according to any one of claims 1-2, characterized in that, The preparation process is as follows: Specifically, the steps include the following: S1, 5,10-dihydrophenazine (I) was dissolved in a solvent, and a catalyst and a haloalkane RX (II) were added. The mixture was stirred until the reaction was complete, and the reaction was separated and purified to obtain 5-substituted-5,10-dihydrophenazine (III); R was selected from alkyl, benzyl, substituted benzyl, phenyl, and substituted phenyl; X was selected from Cl, Br, and I; S2, 1,4-dihydroxy-2,5-bis(bromomethyl)benzene (IV) and 2 equivalents of 5-substituted-5,10-dihydrophenazine (III) reacted completely in a solvent, and the intermediate compound (V) was isolated. S3, intermediate compound (V) undergoes esterification with p-toluenesulfonyl chloride to give compound (VI); S4, compound (VI) and compound (B) undergo a Suzuki coupling reaction in the presence of tetrakis(triphenylphosphine)palladium as a catalyst and toluene as a solvent to obtain the target polymer (P).

4. The preparation method according to claim 3, characterized in that, In step S1, the solvent is dimethoxyethane and the catalyst is n-butyllithium hexane. After the reaction was complete, a saturated aqueous solution of sodium dithionate was added, and the mixture was extracted three times with dichloromethane. After drying with anhydrous sodium sulfate, the mixture was concentrated and 5-substituted-5,10-dihydrophenazine (III) was obtained by dichloromethane / petroleum ether column chromatography.

5. The preparation method according to claim 3, characterized in that, In step S2, the reaction is carried out in potassium carbonate and dichloromethane overnight at room temperature. The mixture is washed three times with water, dried with anhydrous sodium sulfate, concentrated, and separated by column chromatography to obtain intermediate compound (V).

6. The application of the conductive polymer material according to any one of claims 1-2 in electrochromic devices.

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