A conductive polymer material, a preparation method and applications

Abstract

The application relates to the field of organic electrochromic materials, in particular to a conductive polymer material, a preparation method and application. The main chain of the conductive polymer is a polyaromatic hydrocarbon structure, has good conductivity, and introduces a triphenylamine structure unit on the side chain; the neutral state triphenylamine compound is colorless and transparent; after power is added, the color changes from the colorless / light yellow neutral state to the colored oxidized state, and the triphenylamine-containing polyimide and polyamide polymer material can solve the problems of poor conductivity, high driving voltage and poor cycle stability in the electrochromic performance, and can be applied to the field of electrochromic devices.

Description

Technical Field

[0001] The present invention relates to the field of organic electrochromic materials, and in particular to a conductive polymer material, a preparation method and an application thereof. Background Art

[0002] Electrochromism is a phenomenon that produces reversible color changes under voltage control. Due to their low energy consumption, memory properties, simple structure, and low cost, electrochromic devices have long been considered promising for commercial passive display devices such as electronic tags and e-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 exposed several shortcomings, hindering their large-scale commercialization. The most prominent issues are slow switching response and a single color, primarily due to the inherent characteristics of the inorganic materials.

[0003] Triphenylamine, a classic electrochromic functional group, has been shown to exhibit excellent thermal stability, good processability, and reasonable hole mobility. The nitrogen atom in the triphenylamine group possesses a lone pair of electrons, creating an electron-rich center. Triphenylamine compounds can undergo a single-electron oxidation process to form a stable triphenylamine cation. In the absence of electron acceptors for charge transfer, the neutral state of triphenylamine compounds is colorless and transparent. As the oxidation process progresses, a color change from a colorless / light yellow neutral state to a vibrant oxidized state can be observed. Over the past few decades, research on triphenylamine-based polymers has primarily focused on polyimides and polyamides, which offer good solubility and exceptional thermal stability. However, polyimides and polyamides are inherently non-conductive and are insulators. The electrochromic functional group triphenylamine is located on the polymer backbone or side chains, resulting in incomplete conjugation. This prevents electron transfer within the polymer backbone, leading to poor conductivity. This is reflected in the high driving voltage and poor cycling stability of the electrochromic materials. Summary of the Invention

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

[0005] The technical solution of the present invention is achieved by providing a conductive polymer material having the following molecular formula:

[0006]

[0007] Wherein, n is a positive integer; n=1 to 100.

[0008] R1, R2, R3, R4, R5, R6, R7, R8, R9, R10 are each independently selected from H, alkyl (C m H 2m+1 , m is a natural number of 1-20), alkoxy, oligoether group; at least two of R1, R2, R3, R4, and R5 are H;

[0009] Ar is an aryl group or a substituted aryl group.

[0010] Preferably, R1=R10, R2=R9, R3=R8, R4=R7, and R5=R6.

[0011] Further preferably, R1=R10=H;

[0012] R2=R9=H, alkoxy, oligoether group;

[0013] R3=R8=alkoxy, oligoether group;

[0014] R4=R7=H, alkoxy, oligoether group;

[0015] R5=R6=H.

[0016] Preferably, Ar is selected from the following:

[0017]

[0018] Wherein, R is selected from H, alkyl (C m H 2m+1 , m is a natural number of 1-20), alkoxy, oligoether

[0019] Preferably, the conductive polymer material is selected from:

[0020]

[0021]

[0022]

[0023]

[0024]

[0025]

[0026]

[0027] In a second aspect of the present invention, a method for preparing the conductive polymer material is provided, and the preparation process is as follows:

[0028]

[0029] The specific steps include:

[0030] S1. Boric acid or boric acid ester of substituted triphenylamine (A) and 2,5-dibromo-1,4-benzenediol (B) are reacted at a molar ratio of 2:1 in the presence of tetrakistriphenylphosphine palladium as a catalyst and toluene as a solvent to undergo Suzuki coupling reaction to obtain intermediate compound C;

[0031] S2. The intermediate compound C reacts with p-toluenesulfonyl chloride in a ratio of 1:2 to produce an esterification reaction to obtain compound D;

[0032] S3 and an aryl diboronate derivative of compound D were mixed in a 1:1 ratio of substance and subjected to Suzuki coupling reaction in the presence of tetrakistriphenylphosphine palladium as a catalyst and toluene as a solvent to obtain the target polymer T.

[0033] In the third aspect of the present invention, the application of the conductive polymer material in an electrochromic device is also provided.

[0034] The beneficial effects are as follows:

[0035] The present invention application intends to combine the excellent color-changing properties of the triphenylamine structure with a polymer having a conjugated system in the main chain. The main chain of the conductive polymer is a polyaromatic hydrocarbon structure with good conductivity. The triphenylamine structural unit is introduced into the side chain. The neutral triphenylamine compound is colorless and transparent. After power is applied, the color changes from a colorless / light yellow neutral state to a colored oxidized state. It is expected to solve the problems of poor conductivity of existing polyimide and polyamide polymer materials containing triphenylamine, and the problems of high driving voltage and poor cycle stability in electrochromic performance, thereby being applied to the field of electrochromic devices. DETAILED DESCRIPTION

[0036] To make the objectives, technical solutions, and advantages of the present invention more clear, the technical solutions of the present invention will be clearly and completely described below in conjunction with specific embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0037] The present invention prepares an electrochromic thin film device on the basis of material synthesis and examines the device performance.

[0038] Preparation of electrochromic devices:

[0039] Transparent ITO conductive glass cut into different sizes was first soaked in a mixture of ammonia and hydrogen peroxide, then ultrasonically treated in deionized water, acetone, and isopropyl alcohol to obtain clean ITO glass. After removal, the glass was blown dry with dry nitrogen and set aside. A polymer sample was dissolved in chlorobenzene to a 20 mg / mL solution and spin-coated onto an ITO sheet. This was then bonded to another ITO sheet using adhesive and further filled with an electrolyte solution using a liquid filling method. A voltage was applied to observe the color change. The electrochromic response time and driving voltage were then tested.

[0040] Example 1 Synthesis of Representative Triphenylamine Conductive Polymer Material T-1

[0041] The synthetic route is as follows:

[0042]

[0043] 26.5 g (100 mmol) of 2,5-dibromo-hydroquinone (T1-1) and 150 g (250 mmol) of 4-(heptyloxy)-N-(4-heptyloxy)-(4-pinacol borate)phenylaniline (T1-2) were dissolved in 500 mL of toluene, 100 mL of 2 mol / L potassium carbonate aqueous solution was added, and nitrogen was blown for 30 min. 250 mmol×1% (2.89 g) of Pd(PPh3)4 was added, and the mixture was heated under reflux with stirring overnight under a nitrogen environment. The mixture was cooled to room temperature and poured into 1000 mL of methanol. The crude product was filtered and further purified by column chromatography using dichloromethane and petroleum ether as eluents to obtain 75.4 g of the intermediate compound (T1-3). 1 H NMR (500MHz, CDCl3) δ7.63–7.45(m,4H),7.43–7.26(m,4H),7.25–7.09(m,10H),6.87–6.72(m,8H),4.51(s,2H), 4.11(t,J=14.9Hz,8H),1.74(qd,J=16.0,1.3Hz,8H),1.55–1.32(m,8H),1.33–1.16(m,24H),1.01–0.76(m,12H).

[0044] 52.6 g (50 mmol) of the hydroxyl-containing intermediate compound T1-3 and 22.7 g (120 mmol) of p-toluenesulfonyl chloride were dissolved in 1000 mL of dichloromethane and stirred at room temperature. The reaction was complete after thin-layer chromatography. The product was washed three times with a saturated aqueous sodium bicarbonate solution and three times with water, dried over anhydrous sodium sulfate, and concentrated to obtain a crude product. The crude product was purified by column chromatography using dichloromethane and petroleum ether to obtain 46.5 g of the sulfonylated intermediate compound T1-5. 1H NMR (500MHz, CDCl3) δ7.88–7.65(m,4H),7.59–7.52(m,4H),7.51–7.43(m,4H),7.41–7.32(m,4H),7.18(dt,J=5.3,3.2Hz,10H),6.9 2–6.68(m,8H),4.11(t,J=14.9Hz,8H),2.43(s,6H),1.89–1.58(m,8H),1.50–1.30(m,9H),1.31–1.11(m,24H),0.99–0.77(m,12H).

[0045] 13.6 g (10 mmol) of the sulfonylated intermediate compound T1-5 and 5.58 g (10 mmol) of the diboronate compound (T1-6) were dissolved in 200 mL of toluene, 10 mL of a 2 mol / L aqueous potassium carbonate solution was added, and nitrogen was blown for 30 min. 20 mmol × 1% (0.23 g) of Pd(PPh3)4 was added, and the mixture was heated under reflux with stirring overnight under a nitrogen atmosphere. The mixture was cooled to room temperature and poured into 500 mL of methanol. The crude product was filtered and the filter cake was extracted with methanol, acetone, n-hexane, and chloroform in sequence to obtain the target polymer T-1. Mw: 24512, 1 H NMR(500MHz, CDCl3)δ7.69(s,2H),7.54–7.39(m,4H),7.39–7.27(m,4H),7.20–6.97(m,10H),6.85–6.57 (m,8H),4.09(t,J=14.9Hz,12H),1.74(tt,J=16.0,8.1Hz,12H),1.49–1.14(m,50H),0.96–0.74(m,18H).

[0046] Example 2 Synthesis of Representative Triphenylamine Conductive Polymer Material T-2

[0047] The synthetic route is as follows:

[0048]

[0049] 13.6 g (10 mmol) of the sulfonylated intermediate compound T1-5 and 5.66 g (10 mmol) of the diboronate compound (T2-1) were dissolved in 200 mL of toluene, 10 mL of a 2 mol / L aqueous potassium carbonate solution was added, and nitrogen was blown for 30 min. 20 mmol × 1% (0.23 g) of Pd(PPh3)4 was added, and the mixture was heated under reflux with stirring overnight under a nitrogen atmosphere. The mixture was cooled to room temperature and poured into 500 mL of methanol. The crude product was filtered and the filter cake was extracted with methanol, acetone, n-hexane, and chloroform in sequence to obtain the target polymer T-2. Mw: 34150,1 H NMR(500MHz,Chloroform)δ7.72(s,2H),7.63(s,2H),7.56–7.46(m,4H),7.39–7. 26(m,4H),7.19–7.03(m,10H),6.84–6.66(m,8H),4.30(td,J=17.8,1.0Hz,4H),4 .10(t,J=20.2Hz,8H),3.76(td,J=17.8,1.0Hz,4H),3.57–3.44(m,8H),3.39(s,6 H),1.73(dqd,J=24.6,19.9,2.8Hz,8H),1.56–1.09(m,33H),0.98–0.72(m,12H).

[0050] Example 3 Synthesis of Representative Triphenylamine Conductive Polymer Material T-3

[0051] The synthetic route is as follows:

[0052]

[0053] 13.6 g (10 mmol) of the sulfonylated intermediate compound T1-5 and 3.8 g (10 mmol) of the diboronate compound (T3-1) were dissolved in 200 mL of toluene, 10 mL of a 2 mol / L aqueous potassium carbonate solution was added, and nitrogen was blown in for 30 min. 20 mmol × 1% (0.23 g) of Pd(PPh3)4 was added, and the mixture was heated under reflux with stirring overnight under a nitrogen atmosphere. The mixture was cooled to room temperature and poured into 500 mL of methanol. The crude product was filtered and the filter cake was extracted with methanol, acetone, n-hexane, and chloroform in sequence to obtain the target polymer T-3. Mw: 25791, 1 H NMR(500MHz,Chloroform)δ8.17(s,1H),7.98(ddd,J=10.3,7.2,3.0Hz,2H),7.71(ddd,J=58.4,15.0,2.9Hz,2H),7.60–7.44(m,5H),7.44–7.28(m ,5H),7.29–7.05(m,8H),6.95–6.60(m,8H),4.11(t,J=20.2Hz,8H),1.74 (dqd,J=24.8,20.1,2.8Hz,8H),1.58–1.06(m,33H),0.96–0.65(m,11H).

[0054] Example 4 Synthesis of Representative Triphenylamine Conductive Polymer Material T-4

[0055] The synthetic route is as follows:

[0056]

[0057] 13.6 g (10 mmol) of the sulfonylated intermediate compound T1-5 and 6.42 g (10 mmol) of the diboronate compound (T4-1) were dissolved in 200 mL of toluene. 10 mL of a 2 mol / L aqueous potassium carbonate 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 with stirring overnight under a nitrogen atmosphere. The mixture was cooled to room temperature and poured into 500 mL of methanol. The crude product was filtered and the filter cake was extracted with methanol, acetone, n-hexane, and chloroform in sequence to obtain the target polymer T-4. Mw: 31528. 13 C NMR(125MHz,Chloroform)δ160.21,150.17,148.32,143.63,143.58,143.31,143.12,14 0.89,140.71,137.29,137.07,134.72,133.95,130.44,129.89,129.31,127.98,127.52, 127.34,125.80,124.94,123.77,123.42,123.22,123.09,122.11,120.20,120.05,116.04,69.66,53.42,40.17,31.73,29.54,29.15,29.04,28.80,26.58,25.54,23.16,14.00.

[0058] Example 5 Synthesis of Representative Triphenylamine Conductive Polymer Material T-5

[0059] The synthetic route is as follows:

[0060]

[0061] 13.6 g (10 mmol) of the sulfonylated intermediate compound T1-5 and 6.50 g (10 mmol) of the diboronate compound (T5-1) were dissolved in 200 mL of toluene. 10 mL of a 2 mol / L aqueous potassium carbonate 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 with stirring overnight under a nitrogen atmosphere. The mixture was cooled to room temperature and poured into 500 mL of methanol. The crude product was filtered and the filter cake was extracted with methanol, acetone, n-hexane, and chloroform in sequence to obtain the target polymer T-5. Mw: 22795. 13C NMR(125MHz,Chloroform)δ160.21,150.17,148.32,143.63,143.58,143.31,143.12,140. 89,140.71,137.29,137.07,134.72,133.95,130.44,129.89,129.31,127.98,127.52,127 .34,125.80,124.94,123.77,123.42,123.22,123.09,122.11,120.20,120.05,116.04,70.00,69.97,69.66,66.81,53.39,42.47,31.73,29.15,28.80,26.58,23.16,14.84,14.00.

[0062] Example 6 Synthesis of Representative Triphenylamine Conductive Polymer Material T-6

[0063] The synthetic route is as follows:

[0064]

[0065] 13.6 g (10 mmol) of the sulfonylated intermediate compound T1-5 and 5.31 g (10 mmol) of the diboronate compound (T6-1) were dissolved in 200 mL of toluene, 10 mL of a 2 mol / L aqueous potassium carbonate solution was added, and nitrogen was blown in for 30 min. 20 mmol × 1% (0.23 g) of Pd(PPh3)4 was added, and the mixture was heated under reflux with stirring overnight under a nitrogen atmosphere. The mixture was cooled to room temperature and poured into 500 mL of methanol. The crude product was filtered and the filter cake was extracted with methanol, acetone, n-hexane, and chloroform in sequence to obtain the target polymer T-6. Mw: 37654. 1 H NMR(500MHz,Chloroform)δ8.18(s,1H),8.03–7.68(m,5H),7.68–7.41(m,6H),7.41–7.25(m,4H),7.30–7.09(m,8H),6.93– 6.65(m,8H),4.14(dt,J=23.7,20.8Hz,10H),1.74(dqd,J=24.7,19.9,2.8Hz,10H),1.52–1.11(m,44H),1.00–0.71(m,15H).

[0066] Example 7 Synthesis of Representative Triphenylamine Conductive Polymer Material T-7

[0067] The synthetic route is as follows:

[0068]

[0069] 13.6 g (10 mmol) of the sulfonylated intermediate compound T1-5 and 5.35 g (10 mmol) of the diboronate compound (T7-1) were dissolved in 200 mL of toluene, 10 mL of a 2 mol / L aqueous potassium carbonate solution was added, and nitrogen was blown in for 30 min. 20 mmol × 1% (0.23 g) of Pd(PPh3)4 was added, and the mixture was heated under reflux with stirring overnight under a nitrogen atmosphere. The mixture was cooled to room temperature and poured into 500 mL of methanol. The crude product was filtered and the filter cake was extracted with methanol, acetone, n-hexane, and chloroform in sequence to obtain the target polymer T-7. Mw: 27458. 1 H NMR(500MHz,Chloroform)δ8.17(s,1H),8.00–7.73(m,5H),7.66–7.40(m,6H), 7.41–7.28(m,4H),7.24–6.99(m,8H),6.86–6.61(m,8H),4.45(td,J=18.9,0.6 Hz,2H),4.11(t,J=20.2Hz,8H),3.71(td,J=19.0,0.8Hz,2H),3.56–3.11(m,6H ),1.74(dqd,J=24.8,19.9,2.8Hz,8H),1.56–1.01(m,38H),1.01–0.75(m,12H).

[0070] Example 8 Synthesis of Representative Triphenylamine Conductive Polymer Material T-8

[0071] The synthetic route is as follows:

[0072]

[0073] 13.6 g (10 mmol) of the sulfonylated intermediate compound T1-5 and 6.55 g (10 mmol) of the diboronate compound (T8-1) were dissolved in 200 mL of toluene, 10 mL of a 2 mol / L aqueous potassium carbonate solution was added, and nitrogen was blown in for 30 min. 20 mmol × 1% (0.23 g) of Pd(PPh3)4 was added, and the mixture was heated under reflux with stirring overnight under a nitrogen atmosphere. The mixture was cooled to room temperature and poured into 500 mL of methanol. The crude product was filtered and the filter cake was extracted with methanol, acetone, n-hexane, and chloroform in sequence to obtain the target polymer T-8. Mw: 24751. 13C NMR(125MHz,Chloroform)δ160.21,150.30,149.59,143.58,143.12,140.10,1 39.93,138.42,137.07,133.95,131.07,130.44,129.89,129.31,129.09,128.3 6,127.60,127.53,127.40,127.34,127.12,126.82,126.13,124.46,124.23,123.09,122.11,116.04,72.69,69.66,31.73,29.15,28.80,26.58,23.16,14.00.

[0074] Example 9 Synthesis of Representative Triphenylamine Conductive Polymer Material T-9

[0075] The synthetic route is as follows:

[0076]

[0077] 13.6 g (10 mmol) of the sulfonylated intermediate compound T1-5 and 6.78 g (10 mmol) of the diboronate compound (T-9-1) were dissolved in 200 mL of toluene, 10 mL of a 2 mol / L aqueous potassium carbonate 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 with stirring overnight under a nitrogen atmosphere. The mixture was cooled to room temperature and poured into 500 mL of methanol. The crude product was filtered and the filter cake was extracted with methanol, acetone, n-hexane, and chloroform to obtain the target polymer T-9. Mw: 25472. 13 C NMR(125MHz,Chloroform)δ160.21,150.30,149.59,143.58,143.12,140.10,139.93, 138.42,137.07,133.95,131.07,130.44,129.89,129.31,129.09,128.36,127.60,127 .53,127.40,127.34,127.12,126.82,126.13,124.46,124.23,123.09,122.11,116.04,73.68,70.26,70.17,69.66,69.54,57.86,31.73,29.15,28.80,26.58,23.16,14.00.

[0078] Example 10 Synthesis of Representative Triphenylamine Conductive Polymer Material T-10

[0079] The synthetic route is as follows:

[0080]

[0081] 13.6 g (10 mmol) of the sulfonylated intermediate compound T1-5 and 6.28 g (10 mmol) of the diboronate compound (T10-1) were dissolved in 200 mL of toluene, 10 mL of a 2 mol / L aqueous potassium carbonate solution was added, and nitrogen was blown for 30 min. 20 mmol × 1% (0.23 g) of Pd(PPh3)4 was added, and the mixture was heated under reflux with stirring overnight under a nitrogen atmosphere. The mixture was cooled to room temperature and poured into 500 mL of methanol. The crude product was filtered and the filter cake was extracted with methanol, acetone, n-hexane, and chloroform to obtain the target polymer T-10. Mw: 32147. 13 C NMR(125MHz,Chloroform)δ160.21,153.68,147.44,143.58,143.12,140.97, 138.49,137.07,134.37,133.95,130.44,129.89,129.36,129.31,127.57,12 7.34,126.13,123.09,122.11,116.04,109.48,93.72,73.68,70.38,69.66,69.54,67.01,57.86,57.53,56.68,31.73,29.15,28.80,26.58,23.16,14.00.

[0082] Example 11 Synthesis of Representative Triphenylamine Conductive Polymer Material T-11

[0083] The synthetic route is as follows:

[0084]

[0085] 13.6 g (10 mmol) of the sulfonylated intermediate compound T1-5 and 6.20 g (10 mmol) of the diboronate compound (T11-1) were dissolved in 200 mL of toluene, 10 mL of a 2 mol / L aqueous potassium carbonate solution was added, and nitrogen was blown for 30 min. 20 mmol × 1% (0.23 g) of Pd(PPh3)4 was added, and the mixture was heated under reflux with stirring overnight under a nitrogen atmosphere. The mixture was cooled to room temperature and poured into 500 mL of methanol. The crude product was filtered and the filter cake was extracted with methanol, acetone, n-hexane, and chloroform in sequence to obtain the target polymer T-11. Mw: 31475. 13C NMR(125MHz,Chloroform)δ160.21,153.68,147.44,143.58,143.12,140.97,138.49,137.07,134.37,133.95,130.44,129.89,129.36,129.31,127 .57,127.34,126.13,123.09,122.11,116.04,109.48,93.72,72.14,69.6 6,69.42,57.53,56.68,31.73,29.32,29.15,28.80,26.58,23.16,14.00.

[0086] Example 12 Synthesis of Representative Triphenylamine Conductive Polymer Material T-12

[0087] The synthetic route is as follows:

[0088]

[0089] 13.6 g (10 mmol) of the sulfonylated intermediate compound T1-5 and 4.48 g (10 mmol) of the diboronate compound (T12-1) were dissolved in 200 mL of toluene. 10 mL of a 2 mol / L aqueous potassium carbonate 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 with stirring overnight under a nitrogen atmosphere. The mixture was cooled to room temperature and poured into 500 mL of methanol. The crude product was filtered and the filter cake was extracted with methanol, acetone, n-hexane, and chloroform in sequence to obtain the target polymer T-12. Mw: 28941. 1 H NMR(500MHz,Chloroform)δ7.93(s,1H),7.81(s,1H),7.55(d,J=7.5Hz,4H),7.37(d,J=7.5Hz,4H),7.16(t,J=14.6Hz,9H),6.7 9(d,J=7.5Hz,8H),4.11(t,J=10.2Hz,8H),2.68(t,J=11.6Hz,2H),1.85–1.64(m,8H),1.57–1.13(m,44H),1.02–0.70(m,15H).

[0090] Example 13 Synthesis of Representative Triphenylamine Conductive Polymer Material T-13

[0091] The synthetic route is as follows:

[0092]

[0093] 26.5 g (100 mmol) of 2,5-dibromo-hydroquinone (T1-1) and 151.75 g (250 mmol) of substituted triphenylamine pinacol borate (T13-1) were dissolved in 500 mL of toluene, and 100 mL of 2 mol / L potassium carbonate aqueous solution was added. The mixture was purged with nitrogen for 30 min, and 250 mmol × 1% (2.89 g) of Pd(PPh3)4 was added. The mixture was heated under reflux with stirring overnight under a nitrogen atmosphere, cooled to room temperature, poured into 1000 mL of methanol, and filtered to obtain a crude product. 81.2 g of the intermediate compound (T13-2) was obtained by column chromatography using dichloromethane and petroleum ether as eluents. 1 H NMR(500MHz,Chloroform)δ7.55(d,J=7.5Hz,4H),7.37(d,J=7.5Hz,4H),7.22–7.04(m,10H),6.79(d,J=7.5H z,8H),4.52(s,2H),4.31(t,J=7.2Hz,8H),3.77(t,J=7.3Hz,8H),3.53(pd,J=6.5,1.2Hz,16H),3.40(s,12H).

[0094] 53.4 g (50 mmol) of the hydroxyl-containing intermediate compound T13-2 and 22.7 g (120 mmol) of p-toluenesulfonyl chloride were dissolved in 1000 mL of dichloromethane and stirred at room temperature. The reaction was complete after thin-layer chromatography. The product was washed three times with a saturated aqueous sodium bicarbonate solution and three times with water, dried over anhydrous sodium sulfate, and concentrated to obtain a crude product. The crude product was purified by column chromatography using dichloromethane and petroleum ether to obtain 47.9 g of the sulfonylated intermediate compound T13-3. 1 H NMR(500MHz,Chloroform)δ7.75(d,J=7.5Hz,4H),7.55(d,J=7.5Hz,4H),7.48(d,J=7.5Hz,4H),7.37(d,J=7.5Hz,4H),7.25–7. 09(m,10H),6.79(d,J=7.5Hz,8H),4.31(t,J=7.2Hz,8H),3.77(t,J=7.3Hz,8H),3.63–3.45(m,16H),3.40(s,12H),2.43(s,6H).

[0095] 12.2 g (10 mmol) of the sulfonylated intermediate compound T13-3 and 5.58 g (10 mmol) of the diboronate compound (T1-6) were dissolved in 200 mL of toluene. 10 mL of a 2 mol / L aqueous potassium carbonate 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 with stirring overnight under a nitrogen atmosphere. The mixture was cooled to room temperature and poured into 500 mL of methanol. The crude product was filtered and the filter cake was extracted with methanol, acetone, n-hexane, and chloroform in sequence to obtain the target polymer T-13. Mw: 24178. 13 C NMR(125MHz,Chloroform)δ160.21,153.08,152.19,143.58,143.12,142.90,14 2.77,137.07,137.04,134.32,133.95,130.44,129.89,129.31,129.12,127.83 ,127.34,125.09,123.09,122.11,117.05,116.04,115.27,113.65,73.68,70.37,70.17,69.66,69.54,67.73,57.86,31.73,29.15,28.80,26.58,23.16,14.00.

[0096] Example 14 Synthesis of Representative Triphenylamine Conductive Polymer Material T-14

[0097] The synthetic route is as follows:

[0098]

[0099] 12.2 g (10 mmol) of the sulfonylated intermediate compound T13-3 and 5.66 g (10 mmol) of the diboronate compound (T2-1) were dissolved in 200 mL of toluene. 10 mL of a 2 mol / L aqueous potassium carbonate 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 with stirring overnight under a nitrogen atmosphere. The mixture was cooled to room temperature and poured into 500 mL of methanol. The crude product was filtered to obtain the crude product. The filter cake was sequentially extracted with methanol, acetone, n-hexane, and chloroform to obtain the target polymer T-14. Mw: 41275. 13C NMR(125MHz,Chloroform)δ160.21,153.08,152.19,143.58,143.12,142.90,142.77,137.07,137.04,134.32,133.95,130.44,129.89 ,129.31,129.12,127.83,127.34,125.09,123.09,122.11,117.05,116.04,115.27,113.65,73.68,70.17,69.54,68.31,67.73,57.86.

[0100] Example 15 Synthesis of Representative Triphenylamine Conductive Polymer Material T-15

[0101] The synthetic route is as follows:

[0102]

[0103] 12.2 g (10 mmol) of the sulfonylated intermediate compound T13-3 and 3.8 g (10 mmol) of the diboronate compound (T3-1) were dissolved in 200 mL of toluene. 10 mL of a 2 mol / L aqueous potassium carbonate 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 with stirring overnight under a nitrogen atmosphere. The mixture was cooled to room temperature and poured into 500 mL of methanol. The crude product was filtered to obtain the crude product. The filter cake was sequentially extracted with methanol, acetone, n-hexane, and chloroform to obtain the target polymer T-15. Mw: 24514. 1 H NMR(500MHz,Chloroform)δ8.16(s,1H),8.03–7.91(m,2H),7.86(s,1H),7.77(dd,J=7.5,1.6Hz,1H),7.66(dd,J=7.5,1.5Hz,1H),7.61–7.47(m,5H ),7.46–7.30(m,5H),7.18(d,J=7.5Hz,8H),6.79(d,J=7.5Hz,8H),4.31( t,J=8.9Hz,8H),3.77(t,J=8.9Hz,8H),3.61–3.44(m,16H),3.40(s,12H).

[0104] Example 16 Synthesis of Representative Triphenylamine Conductive Polymer Material T-16

[0105] The synthetic route is as follows:

[0106]

[0107] 12.2 g (10 mmol) of the sulfonylated intermediate compound T13-3 and 6.42 g (10 mmol) of the diboronate compound (T4-1) were dissolved in 200 mL of toluene. 10 mL of a 2 mol / L aqueous potassium carbonate 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. The mixture was heated under reflux with stirring overnight under a nitrogen atmosphere. The mixture was cooled to room temperature and poured into 500 mL of methanol. The crude product was filtered to obtain the crude product. The filter cake was sequentially extracted with methanol, acetone, n-hexane, and chloroform to obtain the target polymer T-16. Mw: 35414. 13 C NMR(125MHz,Chloroform)δ160.21,150.17,148.32,143.63,143.58,143.31,143.12,140.8 9,140.71,137.29,137.07,134.72,133.95,130.44,129.89,129.31,127.98,127.52,127.34 ,125.80,124.94,123.77,123.42,123.22,123.09,122.11,120.20,120.05,116.04,73.68,70.17,69.54,67.73,57.86,53.42,40.17,31.73,29.54,29.15,29.04,25.54,23.16,14.00.

[0108] Example 17 Synthesis of Representative Triphenylamine Conductive Polymer Material T-17

[0109] The synthetic route is as follows:

[0110]

[0111] 12.2 g (10 mmol) of the sulfonylated intermediate compound T13-3 and 6.5 g (10 mmol) of the diboronate compound (T5-1) were dissolved in 200 mL of toluene. 10 mL of a 2 mol / L aqueous potassium carbonate 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 with stirring overnight under a nitrogen atmosphere. The mixture was cooled to room temperature and poured into 500 mL of methanol. The crude product was filtered and the filter cake was extracted with methanol, acetone, n-hexane, and chloroform to obtain the target polymer T-17. Mw: 24514. 13C NMR(125MHz,Chloroform)δ160.21,150.17,148.32,143.63,143.58,143.31,143.12,1 40.89,140.71,137.29,137.07,134.72,133.95,130.44,129.89,129.31,127.98,127. 52,127.34,125.80,124.94,123.77,123.42,123.22,123.09,122.11,120.20,120.05,116.04,73.68,70.17,70.00,69.97,69.54,67.73,66.81,57.86,53.39,42.47,14.84.

[0112] Example 18 Synthesis of Representative Triphenylamine Conductive Polymer Material T-13

[0113] The synthetic route is as follows:

[0114]

[0115] 12.2 g (10 mmol) of the sulfonylated intermediate compound T13-3 and 5.31 g (10 mmol) of the diboronate compound (T6-1) were dissolved in 200 mL of toluene. 10 mL of a 2 mol / L aqueous potassium carbonate 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 with stirring overnight under a nitrogen atmosphere. The mixture was cooled to room temperature and poured into 500 mL of methanol. The crude product was filtered and the filter cake was extracted with methanol, acetone, n-hexane, and chloroform in sequence to obtain the target polymer T-18. Mw: 35410. 1 H NMR(500MHz,Chloroform)δ8.18(s,1H),8.01–7.72(m,5H),7.67–7.45(m,6H),7 .37(d,J=7.5Hz,4H),7.18(d,J=7.5Hz,8H),6.79(d,J=7.5Hz,8H),4.31(t,J=8. 9Hz,8H),4.16(t,J=10.8Hz,2H),3.77(t,J=8.9Hz,8H),3.59–3.47(m,16H),3.4 0(s,12H),1.73(dd,J=22.3,11.1Hz,2H),1.41–1.06(m,10H),0.99–0.71(m,3H).

[0116] Example 19 Synthesis of Representative Triphenylamine Conductive Polymer Material T-31

[0117] The synthetic route is as follows:

[0118]

[0119] 26.5 g (100 mmol) of 2,5-dibromo-hydroquinone (T1-1) and 264 g (250 mmol) of substituted triphenylamine pinacol borate (T31-1) were dissolved in 500 mL of toluene, and 100 mL of 2 mol / L potassium carbonate aqueous solution was added. The mixture was purged with nitrogen for 30 min, and 250 mmol × 1% (2.89 g) of Pd(PPh3)4 was added. The mixture was heated under reflux with stirring overnight under a nitrogen atmosphere, cooled to room temperature, poured into 1000 mL of methanol, and filtered to obtain a crude product. The crude product was further purified by column chromatography using dichloromethane and petroleum ether as eluents to obtain 184.6 g of the intermediate compound (T31-2).

[0120] 98.3 g (50 mmol) of the hydroxyl-containing intermediate compound T31-2 and 22.7 g (120 mmol) of p-toluenesulfonyl chloride were dissolved in 1000 mL of dichloromethane and stirred at room temperature. The reaction was complete after thin-layer chromatography. The product was washed three times with a saturated aqueous sodium bicarbonate solution and three times with water, dried over anhydrous sodium sulfate, and concentrated to obtain a crude product. The crude product was purified by column chromatography using dichloromethane and petroleum ether to obtain 116.5 g of the sulfonylated intermediate compound T31-3.

[0121] 22.7 g (10 mmol) of the sulfonylated intermediate compound T31-3 and 5.58 g (10 mmol) of the diboronate compound (T1-6) were dissolved in 500 mL of toluene. 10 mL of a 2 mol / L aqueous potassium carbonate 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 with stirring overnight under a nitrogen atmosphere. The mixture was cooled to room temperature and poured into 500 mL of methanol. The crude product was filtered to obtain the crude product. The filter cake was sequentially extracted with methanol, acetone, n-hexane, and chloroform to obtain the target polymer T-31. Mw: 24514. 1H NMR(500MHz,Chloroform-d)δ8.72(s,1H),8.11(d,J=7.4Hz,1H),7.98(dd,J=7.5,1.5Hz,1H),7.9 1–7.76(m,2H),7.62–7.43(m,6H),7.26(d,J=1.4Hz,1H),7.14–6.98(m,4H),6.56(s,8H),4.17(t,J =7.1Hz,2H),4.04(dt,J=8.2,7.1Hz,24H),3.76(t,J=7.0Hz,2H),3.66–3.58(m,4H),3.53(q,J=8.0 Hz,2H),1.79(pd,J=7.1,1.2Hz,24H),1.56–1.39(m,24H),1.39–1.16(m,73H),0.99–0.71(m,36H).

[0122] Example 20 Synthesis of Representative Triphenylamine Conductive Polymer Material T-32

[0123] The synthetic route is as follows:

[0124]

[0125] 22.7 g (10 mmol) of the sulfonylated intermediate compound T31-3 and 6.7 g (10 mmol) of the diboronate compound (T32-1) were dissolved in 500 mL of toluene. 10 mL of a 2 mol / L aqueous potassium carbonate 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 with stirring overnight under a nitrogen atmosphere. The mixture was cooled to room temperature and poured into 500 mL of methanol. The crude product was filtered to obtain the crude product. The filter cake was sequentially extracted with methanol, acetone, n-hexane, and chloroform to obtain the target polymer T-32. Mw: 1 H NMR(500MHz,Chloroform-d)δ8.55(s,1H),7.87(s,1H),7.68–7.33(m,6H),7.06(dd,J=24.0,7 .5Hz,4H),6.56(s,8H),1.79(pd,J=7.1,1.1Hz,28H),1.58–1.14(m,110H),0.97–0.68(m,42H).

[0126] Example 21 Synthesis of Representative Triphenylamine Conductive Polymer Material T-33

[0127] The synthetic route is as follows:

[0128]

[0129] 22.7 g (10 mmol) of the sulfonylated intermediate compound T31-3 and 6.78 g (10 mmol) of the diboronate compound (T33-1) were dissolved in 500 mL of toluene. 10 mL of a 2 mol / L aqueous potassium carbonate 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 with stirring overnight under a nitrogen atmosphere. The mixture was cooled to room temperature and poured into 500 mL of methanol. The crude product was filtered and the filter cake was extracted with methanol, acetone, n-hexane, and chloroform in sequence to obtain the target polymer T-33. Mw: 34641. 1 H NMR(500MHz,Chloroform-d)δ8.55(s,1H),7.87(s,1H),7.66–7.33(m,6H),7.06(dd,J=24.1,7.6Hz,4H),6.56(s,8H),4.16(t,J=7.1Hz,4H),4.04(dt ,J=8.3,7.1Hz,24H),3.84–3.49(m,12H),3.37(s,6H),1.79(pd,J=7.1,1. 3Hz, 24H), 1.45 (p, J = 7.0Hz, 24H), 1.37–1.17 (m, 69H), 0.99–0.74 (m, 36H).

[0130] Example 22 Synthesis of Representative Triphenylamine Conductive Polymer Material T-34

[0131] The synthetic route is as follows:

[0132]

[0133] 22.7 g (10 mmol) of the sulfonylated intermediate compound T31-3 and 6.28 g (10 mmol) of the diboronate compound (T10-1) were dissolved in 500 mL of toluene. 10 mL of a 2 mol / L aqueous potassium carbonate 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 with stirring overnight under a nitrogen atmosphere. The mixture was cooled to room temperature and poured into 500 mL of methanol. The crude product was filtered and the filter cake was extracted with methanol, acetone, n-hexane, and chloroform in sequence to obtain the target polymer T-34. Mw: 54124. 1H NMR(500MHz,Chloroform-d)δ7.92(s,2H),7.68(s,2H),7.53(dd,J=9.2,7.4Hz,8H),7.25–6.76(m,24H),6.56(s,8H),4.38–4.18(m,8H) ,4.11–3.91(m,34H),3.86–3.51(m,26H),3.37(s,12H),1.92–1.65(m,32H),1.53–1.37(m,32H),1.37–1.13(m,91H),1.08–0.75(m,48H).

[0134] Example 23 Synthesis of Representative Triphenylamine Conductive Polymer Material T-35

[0135] The synthetic route is as follows:

[0136]

[0137] 22.7 g (10 mmol) of the sulfonylated intermediate compound T31-3 and 6.20 g (10 mmol) of the diboronate compound (T11-1) were dissolved in 500 mL of toluene. 10 mL of a 2 mol / L aqueous potassium carbonate 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 with stirring overnight under a nitrogen atmosphere. The mixture was cooled to room temperature and poured into 500 mL of methanol. The crude product was filtered and the filter cake was extracted with methanol, acetone, n-hexane, and chloroform in sequence to obtain the target polymer T-35. Mw: 24514. 1 H NMR(500MHz,Chloroform-d)δ7.92(s,1H),7.68(s,1H),7.60–7.43(m,4H),7.26–6.82(m,4H),6.56(s,8H),4.0 4(dt,J=8.1,7.0Hz,29H),3.81(d,J=7.1Hz,1H),1.96–1.56(m,28H),1.54–1.11(m,109H),1.08–0.57(m,42H).

[0138] Example 24 Synthesis of Representative Triphenylamine Conductive Polymer Material T-36

[0139] The synthetic route is as follows:

[0140]

[0141] 22.7 g (10 mmol) of the sulfonylated intermediate compound T31-3 and 4.48 g (10 mmol) of the diboronate compound (T12-1) were dissolved in 500 mL of toluene. 10 mL of a 2 mol / L aqueous potassium carbonate 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 with stirring overnight under a nitrogen atmosphere. The mixture was cooled to room temperature and poured into 500 mL of methanol. The crude product was filtered and the filter cake was extracted with methanol, acetone, n-hexane, and chloroform in sequence to obtain the target polymer T-36. Mw: 25641. 1 H NMR(500MHz,Chloroform-d)δ8.61(s,1H),7.91(s,1H),7.32–6.85(m,5H),6.56(s,8H),4.04(dt,J=8 .2,7.1Hz,24H),2.71(t,J=7.1Hz,2H),1.97–1.53(m,26H),1.54–1.16(m,103H),1.03–0.60(m,39H).

[0142] Example 25 Synthesis of Representative Triphenylamine Conductive Polymer Material T-37

[0143] The synthetic route is as follows:

[0144]

[0145] 26.5 g (100 mmol) of 2,5-dibromo-hydroquinone (T1-1) and 270 g (250 mmol) of substituted triphenylamine pinacol borate (T37-1) were dissolved in 500 mL of toluene, and 100 mL of 2 mol / L potassium carbonate aqueous solution was added. The mixture was purged with nitrogen for 30 min, and 250 mmol × 1% (2.89 g) of Pd(PPh3)4 was added. The mixture was heated under reflux with stirring overnight under a nitrogen atmosphere, cooled to room temperature, poured into 1000 mL of methanol, and filtered to obtain a crude product. The crude product was further purified by column chromatography using dichloromethane and petroleum ether as eluents to obtain 175.4 g of the intermediate compound (T37-2).

[0146] 100.7 g (50 mmol) of the hydroxyl-containing intermediate compound T37-2 and 22.7 g (120 mmol) of p-toluenesulfonyl chloride were dissolved in 1000 mL of dichloromethane and stirred at room temperature. The reaction was detected by thin layer chromatography until completion. The mixture was washed 3 times with a saturated aqueous sodium bicarbonate solution and 3 times with water. The mixture was dried over anhydrous sodium sulfate and concentrated to obtain a crude product. The crude product was purified by column chromatography with dichloromethane and petroleum ether to obtain 121.5 g of the sulfonylated intermediate compound T37-3. 23.2 g (10 mmol) of the sulfonylated intermediate compound T37-3 and 5.58 g (10 mmol) of the diboronate compound (T1-6) were dissolved in 500 mL of toluene and 10 mL of the mixture was added. 2 mol / L potassium carbonate aqueous solution was purged with nitrogen for 30 min, 20 mmol×1% (0.23 g) Pd(PPh3)4 was added, and the mixture was heated under reflux with stirring overnight under nitrogen. The mixture was cooled to room temperature and poured into 500 mL of methanol. The crude product was filtered and the filter cake was extracted with methanol, acetone, n-hexane and chloroform in sequence to obtain the target polymer T-37. Mw: 35418. 1 H NMR(500MHz,Chloroform-d)δ8.61(s,1H),7.91(s,1H),7.32–6.85(m,5H),6.56(s,8H),4.04(dt,J=8 .2,7.1Hz,24H),2.71(t,J=7.1Hz,2H),1.97–1.53(m,26H),1.54–1.16(m,103H),1.03–0.60(m,39H).

[0147] Example 26 Synthesis of Representative Triphenylamine Conductive Polymer Material T-38

[0148] The synthetic route is as follows:

[0149]

[0150] 23.2 g (10 mmol) of the sulfonylated intermediate compound T37-3 and 5.66 g (10 mmol) of the diboronate compound (T2-1) were dissolved in 500 mL of toluene. 10 mL of a 2 mol / L aqueous potassium carbonate 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 with stirring overnight under a nitrogen atmosphere. The mixture was cooled to room temperature and poured into 500 mL of methanol. The crude product was filtered and the filter cake was extracted with methanol, acetone, n-hexane, and chloroform in sequence to obtain the target polymer T-38. Mw: 25478. 1H NMR(500MHz,Chloroform-d)δ8.69(s,1H),7.91(s,1H),7.75–7.40(m,4H),7.28 –6.90(m,6H),6.57(s,8H),4.16(dt,J=21.9,7.1Hz,28H),3.93–3.22(m,126H).

[0151] Example 27 Synthesis of Representative Triphenylamine Conductive Polymer Material T-39

[0152] The synthetic route is as follows:

[0153]

[0154] 23.2 g (10 mmol) of the sulfonylated intermediate compound T37-3 and 3.80 g (10 mmol) of the diboronate compound (T3-1) were dissolved in 500 mL of toluene. 10 mL of a 2 mol / L aqueous potassium carbonate 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 with stirring overnight under a nitrogen atmosphere. The mixture was cooled to room temperature and poured into 500 mL of methanol. The crude product was filtered and the filter cake was extracted with methanol, acetone, n-hexane, and chloroform in sequence to obtain the target polymer T-39. Mw: 65412. 1 H NMR (500MHz, Chloroform-d) δ8.72(s,1H),8.09–7.45(m,11H),7.26–6.82(m,4H),6.56(s,8H),4.16(dt,J=21.8,7.1Hz,24H),3.90–3.16(m,108H).

[0155] Example 28 Synthesis of Representative Triphenylamine Conductive Polymer Material T-40

[0156] The synthetic route is as follows:

[0157]

[0158] 23.2 g (10 mmol) of the sulfonylated intermediate compound T37-3 and 6.42 g (10 mmol) of the diboronate compound (T4-1) were dissolved in 500 mL of toluene. 10 mL of a 2 mol / L aqueous potassium carbonate 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 with stirring overnight under a nitrogen atmosphere. The mixture was cooled to room temperature and poured into 500 mL of methanol. The crude product was filtered to obtain the crude product. The filter cake was sequentially extracted with methanol, acetone, n-hexane, and chloroform to obtain the target polymer T-40. Mw: 54175.1 H NMR(500MHz,Chloroform-d)δ8.72(s,1H),8.07–7.33(m,11H),7.26–6.97(m,4H),6.56(s,8H),4.16(d t,J=21.8,7.1Hz,24H),3.91–3.25(m,108H),2.17–1.69(m,4H),1.51–1.05(m,23H),1.02–0.71(m,6H).

[0159] Example 29 Synthesis of Representative Triphenylamine Conductive Polymer Material T-41

[0160] The synthetic route is as follows:

[0161]

[0162] 23.2 g (10 mmol) of the sulfonylated intermediate compound T37-3 and 6.50 g (10 mmol) of the diboronate compound (T5-1) were dissolved in 500 mL of toluene. 10 mL of a 2 mol / L aqueous potassium carbonate 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 with stirring overnight under a nitrogen atmosphere. The mixture was cooled to room temperature and poured into 500 mL of methanol. The crude product was filtered and the filter cake was extracted with methanol, acetone, n-hexane, and chloroform to obtain the target polymer T-41. Mw: 25794. 1 H NMR(500MHz,Chloroform-d)δ8.72(s,1H),7.97–7.31(m,11H),7.26–6.90(m,4H),6.57(s,8H),4.4 0–4.04(m,24H),3.90–3.18(m,120H),2.39(ddt,J=124.7,12.3,7.1Hz,4H),1.20(t,J=8.0Hz,6H).

[0163] Example 30 Synthesis of Representative Triphenylamine Conductive Polymer Material T-42

[0164] The synthetic route is as follows:

[0165]

[0166] 23.2 g (10 mmol) of the sulfonylated intermediate compound T37-3 and 5.31 g (10 mmol) of the diboronate compound (T6-1) were dissolved in 500 mL of toluene. 10 mL of a 2 mol / L aqueous potassium carbonate 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 with stirring overnight under a nitrogen atmosphere. The mixture was cooled to room temperature and poured into 500 mL of methanol. The crude product was filtered and the filter cake was extracted with methanol, acetone, n-hexane, and chloroform in sequence to obtain the target polymer T-42. Mw: 54791. 1 H NMR(500MHz,Chloroform-d)δ8.72(s,1H),8.23–6.94(m,15H),6.57(s,8H),4.38–3.97(m ,26H),3.85–3.14(m,108H),1.85(p,J=7.2Hz,2H),1.44–1.19(m,10H),1.05–0.68(m,3H).

[0167] Example 31 Preparation of electrochromic device

[0168] The above-synthesized materials T-1, T-2, T-3, T-4, T-5, T-6, T-7, T-8, T-9, T-10, T-11, T-12, T-13, T-14, T-15, T-16, T-17, T-18, T-31, T-32, T-33, T-34, T-35, T-36, T-37, T-38, T-39, T-40, T-41, and T-42 were prepared into a 20 mg / mL chlorobenzene solution for use.

[0169] Cut a piece of transparent ITO conductive glass into 3cm*5cm pieces and soak it in a mixture of ammonia and hydrogen peroxide. Then, ultrasonicate it in deionized water, acetone, and isopropyl alcohol to clean the ITO glass. Remove it and blow it dry with dry nitrogen until ready for use. Spin-coat the prepared solutions of T-1, T-2, T-3, T-4, T-5, T-6, T-7, T-8, T-9, T-10, T-11, T-12, T-13, T-14, T-15, T-16, T-17, T-18, T-31, T-32, T-33, T-34, T-35, T-36, T-37, T-38, T-39, T-40, T-41, and T-42 onto an ITO sheet. Then, it was bonded to another ITO sheet using adhesive. A 0.1 mol / L tetrabutylammonium hexafluorophosphate propylene carbonate electrolyte solution was then poured into the device using the liquid filling method. The device was then sealed with UV adhesive. Voltage was applied to the two electrodes, and the color change of the electrochromic device was observed. The specific results are shown in Table 1:

[0170] Table 1

[0171]

[0172]

[0173] The polymer structures listed above are only partial representatives, and other conductive polymer materials containing the same concept are within the scope of protection of this patent.

[0174] Although the embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and are not to be construed as limitations on the present invention. A person skilled in the art may change, modify, replace and modify the above embodiments within the scope of the present invention.

Claims

1. A conductive polymer material, characterized in that The molecular formula is as follows: Wherein, n is a positive integer; R1, R2, R3, R4, R5, R6, R7, R8, R9, and R10 are each independently selected from H, an alkyl group, an alkoxy group, and an oligoether group; at least two of R1, R2, R3, R4, and R5 are H; Ar is selected from any one of the following A1 to A7: Wherein, R is selected from H, alkyl, alkoxy, and oligoether groups.

2. The conductive polymer material according to claim 1, characterized in that Select any one of the following T1 to T48:

3. The method for preparing a conductive polymer material according to any one of claims 1 to 2, characterized in that: The preparation process is as follows: The specific steps include: S1. Boric acid A substituted with triphenylamine and 2,5-dibromo-1,4-diphenol B in a molar ratio of 2:1, using tetrakistriphenylphosphine palladium as a catalyst and toluene as a solvent, undergoes a Suzuki coupling reaction to obtain an intermediate compound C; S2. The intermediate compound C reacts with p-toluenesulfonyl chloride in a ratio of 1:2 to produce an esterification reaction to obtain compound D; S3, compound D and compound E were mixed in a 1:1 ratio, using tetrakistriphenylphosphine palladium as a catalyst and toluene as a solvent, to undergo Suzuki coupling reaction to obtain the target polymer T.

4. Use of the conductive polymer material according to any one of claims 1 to 2 in an electrochromic device.

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