Conductive polymer material, preparation method and application

Abstract

The invention relates to the field of organic electrochromic materials, in particular to a conductive polymer material, a preparation method and application. As one of classical conductive polymer electrochromic materials, polyaniline (PANI) has the advantages of rich color change, lower oxidation-reduction potential, low cost, simple preparation method and the like, but the solubility, response time, cycling stability and optical modulation range of polyaniline (PANI) are still not ideal enough, and the development of polyaniline (PANI) in actual life is limited. Based on some defects of single polyaniline, a conductive polymer material is designed based on polyaniline, and different side chains are mainly introduced to nitrogen atoms of aniline, so that regulation and control of the material are realized, and relatively excellent device performance is realized. The electrochromic performance in multiple aspects such as response time, coloring efficiency, color change types, cycle test stability and optical modulation range can be effectively improved.

Description

Technical Field

[0001] The 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 in which the absorbance, transmittance or reflectance of a material undergoes a stable and reversible change through a redox process under the control of an external voltage or current. Essentially, it stems from changes in the number of occupied electron states within the material. Among the many methods of regulating color, similar to the color changes of "thermochromism" and "photochromism" caused by "heat" and "light", electrochromism has attracted much attention as a new generation of display imaging devices because of its controllability, low driving voltage, low energy consumption, simple device structure, low cost, fast response time and excellent memory performance. Electrochromic devices have been widely used in military camouflage, smart display, energy-saving glass, energy storage and other fields. Since the 1970s, the research on electrochromic devices has been mainly focused on inorganic materials. However, in the development process of inorganic electrochromic devices, the slow response of switches and the single color determined by the characteristics of inorganic materials themselves gradually emerged, hindering the goal of large-scale commercialization. In contrast, organic materials are of various types, have structural designability, solution processability and color adjustability, and are increasingly widely used in the field of electrochromism.

[0003] In liquid devices, N-phenyl-1,4-phenylenediamine electrochromic materials can be matched with viologen materials to prepare electrochromic devices with good performance. However, as a small molecule material, there is a risk of leakage when it is presented in the electrochromic device in solution. Summary of the invention

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

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

[0006]

[0007] Wherein, n is a natural number, n=1 to 100;

[0008] Ar is an aromatic group.

[0009] In a specific embodiment of the present invention, the Ar substituent of the conductive polymer material is selected from the following groups:

[0010]

[0011] Wherein, R and R' are each independently selected from H, alkyl (Cm H 2m+1 , m is a natural number of 1-20), alkoxy, oligoether

[0012] In a specific embodiment of the present invention, the conductive polymer material is selected from the following:

[0013]

[0014]

[0015] On the other hand, the present invention also provides a method for preparing a conductive polymer material, the preparation process is as follows:

[0016]

[0017] The specific steps include:

[0018] Aniline reacts with an aryl bromide derivative (B) and is purified to obtain an intermediate compound (II);

[0019] The intermediate compound (II) reacts with 1-bromo-4-nitrobenzene (III) and is purified to obtain the intermediate compound (IV);

[0020] The intermediate compound (Ⅳ) is subjected to a reduction reaction with hydrogen and Pd / C in tetrahydrofuran to obtain compound (V);

[0021] The compound (V) undergoes polymerization reaction under the action of a catalyst to produce the target polymer (P).

[0022] In a specific embodiment of the present invention, aniline (I) is dissolved in toluene, and 0.8 equivalent of aryl bromide derivative (B) is added at room temperature. After the addition is completed, Breetphos Pd G3, Ruphos and tBuONa are added; stirring is continued at 110° C. under a nitrogen atmosphere until the reaction is complete, filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed by dichloromethane / petroleum ether column to obtain intermediate compound (II);

[0023] The intermediate compound (II) was reacted with 1.2 equivalents of 1-bromo-4-nitrobenzene (III) in Pd(amphos)Cl2, tBuONa and toluene at 110°C overnight, filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain the intermediate compound (IV);

[0024] The intermediate compound (Ⅳ) is subjected to a reduction reaction with hydrogen and Pd / C in tetrahydrofuran to obtain compound (V);

[0025] Compound (V) is polymerized in potassium dichromate dissolved in hydrochloric acid under stirring at room temperature. After the reaction is completed, it is repeatedly washed with hydrochloric acid and filtered to obtain the target polymer (P).

[0026] In a third aspect, the present invention also provides application of the above conductive polymer material in an electrochromic device.

[0027] The beneficial effects are as follows: Based on the fact that the solubility, response time, cycle stability and optical modulation range of single polyaniline are still not ideal, which limits its development in real life, the present invention designs a conductive polymer material based on polyaniline, mainly by introducing different side chains on the nitrogen atoms of aniline, thereby realizing the regulation of the material and achieving relatively excellent device performance. It can effectively improve the electrochromic performance in many aspects such as response time, coloring efficiency, color change types, cycle test stability and optical modulation range. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 The figure is a schematic diagram of the structure of a top emission device made by using the bismuth-containing compound of the present invention. DETAILED DESCRIPTION

[0029] In order to make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be clearly and completely described below in conjunction with the specific embodiments of the present invention and the corresponding drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0030] The present invention is further described in detail below with reference to the accompanying drawings and embodiments.

[0031] The present invention combines the excellent color-changing performance of the N-phenyl-1,4-phenylenediamine structure with an aromatic group or a substituted aromatic group with excellent performance to form a polymer, thereby obtaining a polymer material containing N-phenyl-1,4-phenylenediamine with good conductivity, thereby obtaining an electrochromic device with excellent performance.

[0032] Based on the material synthesis, electrochromic thin film devices were prepared and their device performance was investigated. The specific structure is as follows Figure 1 shown.

[0033] Preparation of electrochromic devices:

[0034] The transparent ITO conductive glass cut into different sizes was first soaked in a mixed solvent of ammonia / hydrogen peroxide for a period of time, and then ultrasonicated three times in deionized water, acetone, and isopropanol to obtain the cleaned ITO glass. After taking it out, it was blown dry with dry nitrogen for standby use. The polymer sample was dissolved in toluene to make a 40mg / mL solution, and then spin-coated on an ITO. Then it was glued with another ITO, and the electrolyte solution was further poured into it by the liquid filling method. By applying voltage, its color change was observed. Its electrochromic response time and driving voltage and other properties were tested.

[0035] Example 1 Synthesis of Representative Conductive Polymer Material P-1 Containing N-phenyl-1,4-phenylenediamine

[0036] The synthetic route is shown in the figure below:

[0037]

[0038] Aniline (I, 23.26 g, 250 mmol) was dissolved in 300 ml toluene. 1-bromo-4-octylbenzene (C1, 53.62 g, 200 mmol) was added at room temperature. After the addition was completed, 11.31 g (12.5 mmol) of Bretphos Pd G3, 11.67 g (25 mmol) of Ruphos and 60.06 g (625 mmol) of tBuONa were added. Stirring was continued at 110° C. for 2 h under nitrogen atmosphere until the reaction was complete. The mixture was filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and 40.49 g of 4-octyl-N-phenylaniline (II-1) was obtained by column chromatography with dichloromethane / petroleum ether. 1 H NMR(500MHz,Chloroform-d)δ7.24–7.17(m,2H),7.09(dt,J=7.8,1.0Hz,2H),7.07–7.01(m,2H),6.88(tt,J=6.8,1.1Hz,1 H),6.86–6.81(m,2H),6.25(s,1H),2.59(tt,J=8.0,1.0Hz,2H),1.66–1.56(m,1H),1.36–1.23(m,10H),0.94–0.85(m,3H).

[0039] 4-Octyl-N-phenylaniline (II-1, 28.12 g, 100 mmol) and 1-bromo-4-nitrobenzene (III, 24.11 g, 120 mmol) were reacted in 0.35 g (0.5 mmol) Pd(amphos)Cl2, 19.22 g (200 mmol) tBuONa and 250 ml toluene at 110°C for 4 h, filtered, washed three times with water, extracted three times with dichloromethane, dried over anhydrous sodium sulfate, concentrated, and chromatographed on a dichloromethane / petroleum ether column to obtain 26.55 g 4-nitro-N-(4-octylphenyl)-N-aniline (IV-1). 1 H NMR(500MHz,Chloroform-d)δ8.15–8.10(m,1H),7.39–7.34(m,1H),7.32–7.25(m,1H),7.16(dt,J=8.2,1.0Hz,1H),7.13– 7.08(m,1H),7.07–7.02(m,1H),2.59(tt,J=8.0,1.0Hz,1H),1.60(q,J=7.7Hz,1H),1.36–1.23(m,5H),0.92–0.86(m,1H).

[0040] 4-Nitro-N-(4-octylphenyl)-N-aniline (IV-1, 20.11 g, 50 mmol) was reduced with hydrogen and 2 g Pd / C in tetrahydrofuran for 3 h. Filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 15.63 g N 1 -(4-octylphenyl)-N 1 -phenylbenzene-1,4-diamine (V-1). 1 H NMR(500MHz,Chloroform-d)δ7.32–7.25(m,2H),7.16(dt,J=8.2,1.0Hz,2H),7.16–7.08(m,2H),7.09–7.00(m,5H),6.71–6.65(m,2H), 3.99(d,J=5.6Hz,1H), 3.94(d,J=5.7Hz,1H), 2.59(tt,J=8.0,1.0Hz,2H), 1.60(q,J=7.7Hz,2H), 1.36–1.23(m,10H), 0.94–0.85(m,3H).

[0041] N 1 -(4-octylphenyl)-N 1-phenylbenzene-1,4-diamine (V-1, 11.18 g, 30 mmol) was dissolved in 2.0 mol / L hydrochloric acid aqueous solution, 2.21 g (7.5 mmol) potassium dichromate was dissolved in 2.0 mol / L hydrochloric acid aqueous solution, the potassium dichromate solution was added dropwise to the hydrochloric acid aniline solution using a dropping funnel, and the mixture was reacted at room temperature for 2 h. After the reaction was completed, the mixture was cooled to room temperature, poured into 500 mL of methanol, filtered to obtain a crude product, and then washed with hydrochloric acid aqueous solution until the filtrate was colorless, poured into 500 mL of methanol, filtered, and the filter cake was extracted with methanol, acetone, n-hexane and chloroform in turn, and vacuum dried to obtain the target polymer (P-1) 1 H NMR (500 MHz, Chloroform-d) δ7.16 (dt, J=8.2, 1.0 Hz, 2H), 7.10–6.99 (m, 8H), 6.69–6.64 (m, 2H), 5.73 (q, J=4.8 Hz, 1H), 2.91 (d, J=4.8 Hz, 3H), 2.59 (tt, J=8.1, 1.0 Hz, 2H), 2.35 (s, 2H), 1.66–1.56 (m, 2H), 1.36–1.23 (m, 10H), 0.94–0.85 (m, 3H). The molecular weight of the polymer measured by GPC was 32987.

[0042] Example 2 Synthesis of Representative Conductive Polymer Material P-2 Containing N-phenyl-1,4-phenylenediamine

[0043]

[0044] Aniline (I, 23.26 g, 250 mmol) was dissolved in 300 ml toluene. 1-bromo-4-(heptyloxy)benzene (C2, 54.01 g, 200 mmol) was added at room temperature. After the addition was completed, 11.31 g (12.5 mmol) of Breetphos Pd G3, 11.67 g (25 mmol) of Ruphos and 60.06 g (625 mmol) of tBuONa were added. Stirring was continued at 110° C. for 2 h under nitrogen atmosphere until the reaction was complete. The mixture was filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and 42.48 g of 4-(heptyloxy)-N-aniline (II-2) was obtained by column chromatography with dichloromethane / petroleum ether. 1H NMR(500MHz,Chloroform-d)δ7.24–7.17(m,3H),7.09–7.00(m,7H),6.91–6.83(m,4H),4.00(t,J=6.3Hz,3H),1.8 0–1.71(m,2H),1.46(dq,J=7.8,7.0Hz,3H),1.37–1.30(m,1H),1.33(s,1H),1.33–1.23(m,7H),0.94–0.85(m,4H).

[0045] 4-(Heptyloxy)-N-aniline (II-2, 28.32 g, 100 mmol) and 1-bromo-4-nitrobenzene (III, 24.11 g, 120 mmol) were reacted in 0.35 g (0.5 mmol) Pd(amphos)Cl2, 19.22 g (200 mmol) tBuONa and 250 ml toluene at 110°C for 4 h, filtered, washed three times with water, extracted three times with dichloromethane, dried over anhydrous sodium sulfate, concentrated, and chromatographed on a dichloromethane / petroleum ether column to obtain 27.49 g 4-(heptyloxy)-N-(4-nitrophenyl)-N-aniline (IV-2). 1 H NMR(500MHz,Chloroform-d)δ8.16–8.10(m,2H),7.39–7.34(m,2H),7.28(tt,J=7.7,1.5Hz,2H),7.14–7.08(m,4H),7.04(tt,J=7.7,1.4Hz,1H),6 .91–6.85(m,2H),4.00(t,J=6.3Hz,2H),1.80–1.71(m,1H),1.46(dq,J=7 .8,7.0Hz,2H),1.37–1.28(m,4H),1.31–1.23(m,2H),0.94–0.85(m,3H).

[0046] 4-(Heptyloxy)-N-(4-nitrophenyl)-N-aniline (IV-2, 20.21 g, 50 mmol) was reduced with hydrogen and 2 g Pd / C in tetrahydrofuran for 3 h. Filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 16.65 g N 1 -(4-(heptyloxy)phenyl)-N 1 -phenylbenzene-1,4-diamine (V-2). 1H NMR(500MHz,Chloroform-d)δ7.32–7.25(m,2H),7.14–7.09(m,4H),7.07(d,J=1.4Hz,1H),7.07–7.00(m,2H),6.91–6.85(m,2H),6.71–6. 65(m,2H),4.03–3.97(m,3H),3.94(d,J=5.7Hz,1H),1.80–1.71(m,1H),1.46(dq,J=7.8,7.0Hz,2H),1.37–1.23(m,6H),0.94–0.85(m,3H).

[0047] N 1 -(4-(heptyloxy)phenyl)-N 1 -phenylbenzene-1,4-diamine (V-2, 11.23g, 30mmol) was dissolved in 2.0mol / L hydrochloric acid aqueous solution, 2.21g (7.5mmol) potassium dichromate was dissolved in 2.0mol / L hydrochloric acid aqueous solution, and the potassium dichromate solution was added dropwise to the hydrochloric acid aniline solution using a dropping funnel, and the mixture was reacted at room temperature for 2h. After the reaction was completed, the mixture was cooled to room temperature, poured into 500mL methanol, filtered to obtain a crude product, and then washed with hydrochloric acid aqueous solution until the filtrate was colorless, and then poured into 500mL methanol, filtered, and the filter cake was extracted with methanol, acetone, n-hexane and chloroform in turn, and vacuum dried to obtain the target polymer (P-2) 1 H NMR (500 MHz, Chloroform-d) δ7.14–7.07 (m, 2H), 7.10–7.03 (m, 4H), 7.05–6.99 (m, 2H), 6.91–6.85 (m, 2H), 6.69–6.64 (m, 2H), 5.73 (q, J = 4.8 Hz, 1H), 4.00 (t, J = 6.3 Hz, 2H), 2.91 (d, J = 4.8 Hz, 3H), 2.35 (s, 2H), 1.75 (tt, J = 7.4, 6.3 Hz, 2H), 1.46 (dq, J = 7.9, 7.0 Hz, 2H), 1.37–1.23 (m, 6H), 0.94–0.85 (m, 3H). The molecular weight of the polymer measured by GPC was 34561.

[0048] Example 3 Synthesis of Representative Conductive Polymer Material P-3 Containing N-phenyl-1,4-phenylenediamine

[0049]

[0050] Aniline (I, 23.26 g, 250 mmol) was dissolved in 300 ml of toluene. At room temperature, 1-bromo-4-(2-(2-methoxyethoxy)ethoxy)benzene (C3, 54.80 g, 200 mmol) was added. After the addition was completed, 11.31 g (12.5 mmol) of BreetphosPd G3, 11.67 g (25 mmol) of Ruphos and 60.06 g (625 mmol) of tBuONa were added. Stirring was continued at 110° C. for 2 h under a nitrogen atmosphere until the reaction was complete. The mixture was filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and 40.78 g of 4-(2-(2-methoxyethoxy)ethoxy)-N-phenylaniline (II-3) was obtained by column chromatography with dichloromethane / petroleum ether. 1 H NMR(500MHz,Chloroform-d)δ7.24–7.17(m,1H),7.09–7.00(m,3H),6.91–6.85(m, 1H), 4.13 (t, J=5.0Hz, 1H), 3.75 (t, J=5.0Hz, 1H), 3.64–3.55 (m, 2H), 3.37 (s, 1H).

[0051] 4-(2-(2-methoxyethoxy)ethoxy)-N-phenylaniline (II-3, 28.72 g, 100 mmol) and 1-bromo-4-nitrobenzene (III, 24.11 g, 120 mmol) were reacted in 0.35 g (0.5 mmol) of Pd(amphos)Cl2, 19.22 g (200 mmol) of tBuONa and 250 ml of toluene at 110°C for 4 h, filtered, washed three times with water, extracted three times with dichloromethane, dried over anhydrous sodium sulfate, concentrated, and chromatographed on a dichloromethane / petroleum ether column to obtain 29.80 g of 4-(2-(2-methoxyethoxy)ethoxy)-N-(4-nitrophenyl)-N-aniline (IV-3). 1 H NMR(500MHz,Chloroform-d)δ8.16–8.10(m,1H),7.39–7.34(m,1H),7.32–7.25(m,1H),7.11(dt,J=7.1,1.2Hz,2H),7.04 (tt,J=7.7,1.4Hz,0H),6.93–6.87(m,1H),4.13(t,J=5.0Hz,1H),3.75(t,J=5.0Hz,1H),3.64–3.55(m,2H),3.37(s,1H).

[0052] 4-(2-(2-methoxyethoxy)ethoxy)-N-(4-nitrophenyl)-N-aniline (Ⅳ-3, 20.41 g, 50 mmol) was reduced with hydrogen and 2 g Pd / C in tetrahydrofuran for 3 h. Filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 16.76 g N 1 -(4-(2-(2-)methoxyethoxy)phenyl)-N 1 -phenylbenzene-1,4-diamine (V-3). 1 H NMR(500MHz,Chloroform-d)δ7.32–7.25(m,2H),7.11(dt,J=7.1,1.2Hz,4H),7.09–7.03(m,2H),7.07–7.01(m,1H),6.93–6.87(m,2H),6.7 1–6.65(m,2H),4.13(t,J=5.0Hz,2H),3.99(d,J=5.7Hz,1H),3.94(d,J=5.7Hz,1H),3.75(t,J=5.0Hz,2H),3.64–3.55(m,4H),3.37(s,2H).

[0053] N 1 -(4-(2-(2-)methoxyethoxy)phenyl)-N 1 -phenylbenzene-1,4-diamine (V-3, 11.34 g, 30 mmol) was dissolved in 2.0 mol / L hydrochloric acid aqueous solution, 2.21 g (7.5 mmol) potassium dichromate was dissolved in 2.0 mol / L hydrochloric acid aqueous solution, the potassium dichromate solution was added dropwise to the hydrochloric acid aniline solution using a dropping funnel, and the mixture was reacted at room temperature for 2 h. After the reaction was completed, the mixture was cooled to room temperature, poured into 500 mL of methanol, filtered to obtain a crude product, and then washed with hydrochloric acid aqueous solution until the filtrate was colorless, poured into 500 mL of methanol, filtered, and the filter cake was extracted with methanol, acetone, n-hexane and chloroform in turn, and vacuum dried to obtain the target polymer (P-3) 1 H NMR (500 MHz, Chloroform-d) δ7.14–6.99 (m, 3H), 6.93–6.87 (m, 1H), 6.69–6.64 (m, 1H), 4.13 (t, J=5.0 Hz, 1H), 3.75 (t, J=5.0 Hz, 1H), 3.64–3.55 (m, 2H), 3.37 (s, 1H), 2.91 (d, J=4.8 Hz, 1H), 2.35 (s, 1H). The molecular weight of the polymer measured by GPC was 37650.

[0054] Example 4 Synthesis of Representative Conductive Polymer Material P-4 Containing N-phenyl-1,4-phenylenediamine

[0055]

[0056] Aniline (I, 23.26 g, 250 mmol) was dissolved in 300 ml toluene, and 2-bromo-6-octylnaphthalene (C4, 63.62 g, 200 mmol) was added at room temperature. After addition, 11.31 g (12.5 mmol) of Breetphos Pd G3, 11.67 g (25 mmol) of Ruphos and 60.06 g (625 mmol) of tBuONa were added. Stirring was continued at 110° C. for 2 h under nitrogen atmosphere until the reaction was complete, filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and 49.68 g of 6-octyl-N-phenylnaphthalene-2-amine (II-4) was obtained by column chromatography with dichloromethane / petroleum ether. 1 H NMR(500MHz,Chloroform-d)δ7.74(dd,J=8.2,1.9Hz,1H),7.68(dd,J=8.2,2.3Hz,1H),7.45(d,J=4.0Hz,0H),7.26–7.14(m,6H), 7.07–7.01(m,2H),6.88(tt,J=6.8,1.1Hz,1H),2.62(t,J=8.0Hz,2H),1.62–1.52(m,1H),1.36–1.23(m,10H),0.94–0.85(m,3H).

[0057] 6-Octyl-N-phenylnaphthalene-2-amine (II-4, 33.12 g, 100 mmol) and 1-bromo-4-nitrobenzene (III, 24.11 g, 120 mmol) were reacted in 0.35 g (0.5 mmol) Pd(amphos)Cl2, 19.22 g (200 mmol) tBuONa and 250 ml toluene at 110°C for 4 h, filtered, washed three times with water, extracted three times with dichloromethane, dried over anhydrous sodium sulfate, concentrated, and chromatographed on a dichloromethane / petroleum ether column to obtain 28.49 g N-(4-nitrophenyl)-6-octyl-N-phenylnaphthalene-2-amine (IV-4). 1H NMR(500MHz,Chloroform-d)δ8.16–8.10(m,2H),7.69(ddd,J=8.0,5.7,2.1Hz,2H),7.42(t,J=2.1Hz,1H),7.40–7.34(m,3H),7.32–7.25(m,2H),7.21(ddd ,J=15.7,7.8,2.2Hz,2H),7.14–7.08(m,2H),7.04(tt,J=7.7,1.4Hz,1H),2.6 2(t,J=8.0Hz,2H),1.62–1.52(m,1H),1.36–1.23(m,10H),0.94–0.85(m,3H).

[0058] N-(4-nitrophenyl)-6-octyl-N-phenylnaphthalen-2-amine (Ⅳ-4, 22.61 g, 50 mmol) was reduced with hydrogen and 2 g Pd / C in tetrahydrofuran for 3 h. Filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 18.58 g N 1 -(6-octylnaphthalen-2-yl)-N 1 -phenylbenzene-1,4-diamine (V-4). 1 H NMR(500MHz,Chloroform-d)δ7.69(ddd,J=8.0,5.7,2.1Hz,2H),7.42(t,J=2.1Hz ,1H),7.38(s,1H),7.32–7.17(m,4H),7.14–7.08(m,2H),7.07(d,J=1.5Hz,1H),7 .07–7.00(m,2H),6.71–6.65(m,2H),3.99(d,J=5.6Hz,1H),3.94(d,J=5.7Hz,1H) ,2.62(t,J=8.0Hz,2H),1.62–1.52(m,1H),1.36–1.23(m,10H),0.94–0.85(m,3H).

[0059] N 1 -(6-octylnaphthalen-2-yl)-N 1-phenylbenzene-1,4-diamine ((Ⅴ-4, 12.67g, 30mmol) was dissolved in 2.0mol / L hydrochloric acid aqueous solution, 2.21g (7.5mmol) potassium dichromate was dissolved in 2.0mol / L hydrochloric acid aqueous solution, and the potassium dichromate solution was added dropwise to the hydrochloric acid aniline solution using a dropping funnel, and the mixture was reacted at room temperature for 2h. After the reaction was completed, the mixture was cooled to room temperature, poured into 500mL methanol, filtered to obtain a crude product, and then washed with hydrochloric acid aqueous solution until the filtrate was colorless, poured into 500mL methanol, filtered, and the filter cake was extracted with methanol, acetone, n-hexane and chloroform Soxhlet in turn, and vacuum dried to obtain the target polymer (P-4) 1 H NMR(500MHz,Chloroform-d)δ7.69(ddd,J=8.0,5.7,2.1Hz,2H),7.42(d,J=2.1Hz,1H), 7.41–7.36(m,1H),7.26–7.17(m,2H),7.10–7.01(m,4H),7.02(d,J=8.2Hz,2H),6.69–6. 64 (m, 2H), 5.73 (q, J = 4.8 Hz, 1H), 2.91 (d, J = 4.8 Hz, 3H), 2.62 (t, J = 8.0 Hz, 2H), 2.35 (s, 2H), 1.62–1.52 (m, 2H), 1.36–1.23 (m, 10H), 0.94–0.85 (m, 3H). The molecular weight of the polymer obtained by GPC test was 34126.

[0060] Example 5 Synthesis of Representative Conductive Polymer Material P-5 Containing N-phenyl-1,4-phenylenediamine

[0061]

[0062] Aniline (I, 23.26 g, 250 mmol) was dissolved in 300 ml of toluene. At room temperature, 2-bromo-6-(heptyloxy)naphthalene (C5, 64.02 g, 200 mmol) was added. After addition, 11.31 g (12.5 mmol) of Breetphos Pd G3, 11.67 g (25 mmol) of Ruphos and 60.06 g (625 mmol) of tBuONa were added. Stirring was continued at 110° C. for 2 h under nitrogen atmosphere until the reaction was complete. The mixture was filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and 51.31 g of 6-(heptyloxy)-N-phenylnaphthalene-2-amine (II-5) was obtained by column chromatography with dichloromethane / petroleum ether. 1H NMR(500MHz,Chloroform-d)δ7.72(ddd,J=7.8,7.0,2.0Hz,2H),7.24–7.16(m,4H),7.14–7.09(m,1H),7.07–7.01(m,2H),6.98–6.84(m,3H),4 .02(t,J=6.3Hz,2H),1.76(ddd,J=13.6,7.4,6.3Hz,2H),1.46(dq,J=7. 8,7.0Hz,2H),1.37–1.28(m,4H),1.31–1.23(m,2H),0.94–0.85(m,3H).

[0063] 6-(Heptyloxy)-N-phenylnaphthalene-2-amine (II-5, 33.31 g, 100 mmol) and 1-bromo-4-nitrobenzene (III, 24.11 g, 120 mmol) were reacted in 0.35 g (0.5 mmol) Pd(amphos)Cl2, 19.22 g (200 mmol) tBuONa and 250 ml toluene at 110°C for 4 h, filtered, washed three times with water, extracted three times with dichloromethane, dried over anhydrous sodium sulfate, concentrated, and chromatographed on a dichloromethane / petroleum ether column to obtain 29.98 g 6-(heptyloxy)-N-(4-nitrophenyl)-N-phenylnaphthalene-2-amine (IV-5). 1 HNMR(500MHz,Chloroform-d)δ8.16–8.10(m,2H),7.73(dd,J=8.4,2.4Hz,1H),7.66(dd,J=7.4,1.9 Hz,1H),7.39–7.34(m,3H),7.32–7.26(m,2H),7.24(dd,J=7.5,2.2Hz,1H),7.14–7.08(m,2H),7.04( tt,J=7.7,1.4Hz,1H),6.95(dd,J=8.4,2.4Hz,1H),6.91(t,J=2.2Hz,1H),4.02(t,J=6.3Hz,2H),1. 76(ddd,J=13.6,7.4,6.3Hz,2H),1.46(dq,J=7.8,7.0Hz,2H),1.37–1.23(m,6H),0.94–0.85(m,3H).

[0064] 6-(Heptyloxy)-N-(4-nitrophenyl)-N-phenylnaphthalen-2-amine (IV-5, 22.71 g, 50 mmol) was reduced with hydrogen and 2 g Pd / C in tetrahydrofuran for 3 h. Filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 19.30 g N 1-(6-(heptyloxy)naphthalen-2-yl)-N 1 -phenylbenzene-1,4-diamine (V-5). 1 H NMR(500MHz,Chloroform-d)δ7.73(dd,J=8.3,2.4Hz,1H),7.66(dd,J=7.4,1.9Hz,1H),7.36(t,J=2.4Hz,1H ),7.32–7.26(m,2H),7.24(dd,J=7.5,2.2Hz,1H),7.14–7.08(m,2H),7.07(d,J=1.4Hz,1H),7.07–7.00(m,2H ),6.95(dd,J=8.4,2.4Hz,1H),6.91(t,J=2.2Hz,1H),6.71–6.65(m,2H),4.05–3.97(m,3H),3.94(d,J=5.7Hz ,1H),1.76(ddd,J=13.6,7.4,6.3Hz,2H),1.46(dq,J=7.8,7.0Hz,2H),1.37–1.23(m,6H),0.94–0.85(m,3H).

[0065] N 1 -(6-(heptyloxy)naphthalen-2-yl)-N 1 -phenylbenzene-1,4-diamine ((Ⅴ-5, 12.73g, 30mmol) was dissolved in 2.0mol / L hydrochloric acid aqueous solution, 2.21g (7.5mmol) potassium dichromate was dissolved in 2.0mol / L hydrochloric acid aqueous solution, and the potassium dichromate solution was added dropwise to the hydrochloric acid aniline solution using a dropping funnel, and the mixture was reacted at room temperature for 2h. After the reaction was completed, the mixture was cooled to room temperature, poured into 500mL methanol, filtered to obtain a crude product, and then washed with hydrochloric acid aqueous solution until the filtrate was colorless, and then poured into 500mL methanol, filtered, and the filter cake was extracted with methanol, acetone, n-hexane and chloroform Soxhlet in turn, and vacuum dried to obtain the target polymer (P-5) 1H NMR(500MHz,Chloroform-d)δ7.73(dd,J=8.4,2.4Hz,1H),7.66(dd,J=7.4,1.9Hz,1H),7.36(t,J=2.3Hz,1H ),7.24(dd,J=7.5,2.2Hz,1H),7.10–6.99(m,6H),6.95(dd,J=8.4,2.4Hz,1H),6.91(t,J=2.2Hz,1H),6.69– 6.64 (m, 2H), 5.73 (q, J = 4.8 Hz, 1H), 4.02 (t, J = 6.3 Hz, 2H), 2.91 (d, J = 4.8 Hz, 3H), 2.35 (s, 3H), 1.76 (tt, J = 7.4, 6.3 Hz, 2H), 1.46 (dq, J = 7.8, 7.0 Hz, 2H), 1.37–1.23 (m, 6H), 0.94–0.85 (m, 3H). The molecular weight of the polymer obtained by GPC test was 29871.

[0066] Example 6 Synthesis of Representative Conductive Polymer Material P-6 Containing N-phenyl-1,4-phenylenediamine

[0067]

[0068] Aniline (I, 23.26 g, 250 mmol) was dissolved in 300 ml of toluene. At room temperature, 2-bromo-6-(2-(2-methoxyethoxy)ethoxy)naphthalene (C6, 64.81 g, 200 mmol) was added. After addition, 11.31 g (12.5 mmol) of BreetphosPd G3, 11.67 g (25 mmol) of Ruphos and 60.06 g (625 mmol) of tBuONa were added. Stirring was continued at 110° C. for 2 h under nitrogen atmosphere until the reaction was complete. The mixture was filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and 53.95 g of 6-(2-(2-methoxyethoxy)ethoxy)-N-phenylnaphthalene-2-amine (II-6) was obtained by column chromatography with dichloromethane / petroleum ether. 1H NMR(500MHz,Chloroform-d)δ7.72(ddd,J=7.8,7.0,2.0Hz,2H),7.24–7.16(m,4H),7.14–7.09(m,1H),7.07–7.01(m,2H),6.96(dd,J=8.3 ,2.4Hz,1H),6.95–6.90(m,1H),6.88(tt,J=6.9,1.1Hz,1H),4.17(t,J=5.0Hz,2H),3.76(t,J=5.0Hz,2H),3.64–3.55(m,4H),3.37(s,3H).

[0069] 6-(2-(2-methoxyethoxy)ethoxy)-N-phenylnaphthalene-2-amine (II-6, 33.72 g, 100 mmol) and 1-bromo-4-nitrobenzene (III, 24.11 g, 120 mmol) were reacted in 0.35 g (0.5 mmol) of Pd(amphos)Cl2, 19.22 g (200 mmol) of tBuONa and 250 ml of toluene at 110°C for 4 h, filtered, washed three times with water, extracted three times with dichloromethane, dried over anhydrous sodium sulfate, concentrated, and chromatographed on a dichloromethane / petroleum ether column to obtain 31.61 g of 6-(2-(2-methoxyethoxy)ethoxy)-N-(4-nitrophenyl)-N-phenylnaphthalene-2-amine (IV-6). 1 H NMR(500MHz,Chloroform-d)δ8.16–8.10(m,2H),7.73(dd,J=8.4,2.3Hz,1H),7.66(dd,J =7.4,1.9Hz,1H),7.39–7.34(m,3H),7.32–7.26(m,2H),7.24(dd,J=7.5,2.2Hz,1H),7.14 –7.08(m,2H),7.04(tt,J=7.7,1.4Hz,1H),6.96(dd,J=8.3,2.4Hz,1H),6.92(dd,J=2.4, 1.6Hz,1H),4.17(t,J=5.0Hz,2H),3.76(t,J=5.0Hz,2H),3.64–3.55(m,4H),3.37(s,3H).

[0070] 6-(2-(2-methoxyethoxy)ethoxy)-N-(4-nitrophenyl)-N-phenylnaphthalen-2-amine (IV-6, 22.91 g, 50 mmol) was reduced with hydrogen and 2 g Pd / C in tetrahydrofuran for 3 h. Filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 20.55 g N 1-(6-(2-(2-)methoxyethoxy)ethoxy)naphthalen-2-yl)-N 1 -phenylbenzene-1,4-diamine (V-6). 1 H NMR(500MHz,Chloroform-d)δ7.73(dd,J=8.3,2.3Hz,1H),7.66(dd,J=7.4,1.9Hz,1H),7.36(t,J=2.4H z,1H),7.32–7.26(m,2H),7.24(dd,J=7.5,2.2Hz,1H),7.14–7.08(m,2H),7.08–7.04(m,2H),7.04–7.00 (m,1H),6.96(dd,J=8.2,2.4Hz,1H),6.92(dd,J=2.4,1.6Hz,1H),6.71–6.65(m,2H),4.17(t,J=5.0Hz,2 H),3.99(d,J=5.7Hz,1H),3.94(d,J=5.7Hz,1H),3.76(t,J=5.0Hz,2H),3.64–3.55(m,4H),3.37(s,3H).

[0071] N 1 -(6-(2-(2-)methoxyethoxy)ethoxy)naphthalen-2-yl)-N 1 -phenylbenzene-1,4-diamine (V-6, 12.85g, 30mmol) was dissolved in 2.0mol / L hydrochloric acid aqueous solution, 2.21g (7.5mmol) potassium dichromate was dissolved in 2.0mol / L hydrochloric acid aqueous solution, and the potassium dichromate solution was added dropwise to the hydrochloric acid aniline solution using a dropping funnel, and the mixture was reacted at room temperature for 2h. After the reaction was completed, the mixture was cooled to room temperature, poured into 500mL methanol, filtered to obtain a crude product, and then washed with hydrochloric acid aqueous solution until the filtrate was colorless, and then poured into 500mL methanol, filtered, and the filter cake was extracted with methanol, acetone, n-hexane and chloroform in turn, and vacuum dried to obtain the target polymer (P-6) 1H NMR(500MHz,Chloroform-d)δ7.73(dd,J=8.4,2.4Hz,1H),7.66(dd,J=7.4,1.9Hz,1H),7.36(t,J=2 .4Hz,1H),7.24(dd,J=7.5,2.2Hz,1H),7.10–6.99(m,6H),6.96(dd,J=8.3,2.4Hz,1H),6.92(dd,J= 2.5,1.6Hz,1H),6.69–6.64(m,2H),5.73(q,J=4.8Hz,1H),4.17(t,J=5.0Hz,2H),3.76(t,J=5.0Hz,2H),3.64–3.55(m,4H),3.37(s,3H),2.91(d,J=4.8Hz,3H),2.35(s,3H). The molecular weight of the polymer obtained by GPC test is 35618.

[0072] Example 7 Synthesis of Representative Conductive Polymer Material P-7 Containing N-phenyl-1,4-phenylenediamine

[0073]

[0074] Aniline (I, 23.26 g, 250 mmol) was dissolved in 500 ml of toluene. At room temperature, 2-bromo-7,9,9-trioctyl-9H-fluorene (C7, 116.07 g, 200 mmol) was added. After the addition was completed, 11.31 g (12.5 mmol) of Breetphos Pd G3, 11.67 g (25 mmol) of Ruphos and 60.06 g (625 mmol) of tBuONa were added. Stirring was continued at 110 ° C for 2 h under nitrogen atmosphere until the reaction was complete. The mixture was filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and 51.04 g of 7,9,9-trioctyl-N-phenyl-9H-fluorene-2-amine (II-7) was obtained by column chromatography with dichloromethane / petroleum ether. 1 H NMR(500MHz,Chloroform-d)δ7.24–7.15(m,4H),7.15(d,J=1.8Hz,0H),7.07–7.01(m,2H),6.92–6.84(m,2H),6.82–6.76(m,2H),2.59(t,J =8.0Hz,2H),1.98–1.90(m,2H),1.84(dt,J=13.8,7.2Hz,2H),1.62–1.52(m,1H),1.43–1.32(m,5H),1.36–1.23(m,31H),0.94–0.85(m,9H).

[0075] 7,9,9-Trioctyl-N-phenyl-9H-fluorene-2-amine (II-7, 59.35 g, 100 mmol) and 1-bromo-4-nitrobenzene (III, 24.11 g, 120 mmol) were reacted in 0.35 g (0.5 mmol) Pd(amphos)Cl2, 19.22 g (200 mmol) tBuONa and 250 ml toluene at 110 ° C for 4 hours, filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 31.44 g N-(4-nitrophenyl)-7,9,9-trioctyl-N-phenyl-9H-fluorene-2-amine (IV-7). 1 H NMR(500MHz,Chloroform-d)δ8.16–8.10(m,2H),7.74(d,J=7.1Hz,1H),7.67(d,J=7.8Hz,1H),7.39–7.3 4(m,2H),7.32–7.25(m,2H),7.19–7.14(m,2H),7.14–7.08(m,2H),7.04(tt,J=7.7,1.4Hz,1H),6.87(d,J =2.3Hz,1H),6.80(d,J=2.0Hz,1H),2.59(d,J=16.0Hz,2H),1.98–1.92(m,2H),1.84(dt,J=13.8,7.2Hz,2 H),1.57(p,J=7.8Hz,2H),1.43–1.35(m,5H),1.35–1.30(m,12H),1.30–1.26(m,18H),0.94–0.85(m,9H).

[0076] N-(4-nitrophenyl)-7,9,9-trioctyl-N-phenyl-9H-fluorene-2-amine (Ⅳ-7, 35.72 g, 50 mmol) was reduced with hydrogen and 2 g Pd / C in tetrahydrofuran for 3 h. Filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 29.29 g N 1 -phenyl-N 1 -(7,9,9-Trioctyl-9H-fluoren-2-yl)benzene-1,4-diamine (V-7). 1H NMR(500MHz,Chloroform-d)δ7.32–7.25(m,1H),7.19–7.00(m,3H),6.71–6.65(m,1H),2.59(d,J=16.0Hz,1H),1.93(dt,J=13 .9,7.3Hz,1H),1.84(dt,J=13.8,7.2Hz,1H),1.57(p,J=7.8Hz,1H),1.43–1.33(m,3H),1.33–1.23(m,13H),0.94–0.85(m,4H).

[0077] N 1 -phenyl-N 1 -(7,9,9-trioctyl-9H-fluorene-2-yl)benzene-1,4-diamine (V-7, 20.54 g, 30 mmol) was dissolved in 2.0 mol / L hydrochloric acid aqueous solution, 2.21 g (7.5 mmol) potassium dichromate was dissolved in 2.0 mol / L hydrochloric acid aqueous solution, the potassium dichromate solution was added dropwise to the hydrochloric acid aniline solution using a dropping funnel, and the mixture was reacted at room temperature for 2 hours. After the reaction was completed, the mixture was cooled to room temperature, poured into 500 mL of methanol, filtered to obtain a crude product, and then washed with hydrochloric acid aqueous solution until the filtrate was colorless, poured into 500 mL of methanol, filtered, and the filter cake was extracted with methanol, acetone, n-hexane and chloroform in turn, and vacuum dried to obtain the target polymer (P-7) 1 H NMR(500MHz,Chloroform-d)δ7.74(d,J=7.1Hz,1H),7.67(d,J=7.8Hz,1H),7.19–7.12(m,2H),7.10–6.99(m,6H ),6.87(d,J=2.3Hz,1H),6.80(d,J=2.0Hz,1H),6.69–6.64(m,2H),5.73(q,J=4.8Hz,1H),2.91(d,J=4.8Hz,3H) ,2.59(t,J=8.0Hz,2H),2.35(d,J=1.0Hz,3H),1.94–1.89(m,1H),1.83(dd,J=13.9,7.2Hz,2H),1.57(p,J=7.8Hz,2H),1.43–1.35(m,4H),1.35–1.30(m,11H),1.30–1.23(m,19H),0.94–0.85(m,9H). The molecular weight of the polymer obtained by GPC test was 69563.

[0078] Example 8 Synthesis of Representative Conductive Polymer Material P-8 Containing N-phenyl-1,4-phenylenediamine

[0079]

[0080] Aniline (I, 23.26 g, 250 mmol) was dissolved in 500 ml of toluene. At room temperature, 2-bromo-7-(heptyloxy)-9,9-dioctyl-9H-fluorene (C8, 116.47 g, 200 mmol) was added. After the addition was completed, 11.31 g (12.5 mmol) of BreetphosPd G3, 11.67 g (25 mmol) of Ruphos and 60.06 g (625 mmol) of tBuONa were added. Stirring was continued at 110° C. for 2 h under nitrogen atmosphere until the reaction was complete. The mixture was filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and 48.83 g of 7-(heptyloxy)-9,9-dioctyl-N-phenyl-9H-fluorene-2-amine (II-8) was obtained by column chromatography with dichloromethane / petroleum ether. 1 H NMR(500MHz,Chloroform-d)δ7.81(d,J=7.8Hz,1H),7.68(d,J=8.0Hz,1H),7.24–7.16(m,3H),7. 07(d,J=2.3Hz,1H),7.07–7.01(m,2H),6.93(dd,J=8.0,1.9Hz,1H),6.90–6.86(m,1H),6.84(d,J =2.0Hz,1H),6.78(s,1H),4.00(t,J=6.3Hz,2H),1.99–1.93(m,2H),1.89–1.80(m,2H),1.75(tt, J=7.5,6.3Hz,2H),1.51–1.41(m,2H),1.41–1.33(m,7H),1.33–1.23(m,25H),0.94–0.85(m,9H).

[0081] 7-(Heptyloxy)-9,9-dioctyl-N-phenyl-9H-fluorene-2-amine (II-8, 59.55 g, 100 mmol) and 1-bromo-4-nitrobenzene (III, 24.11 g, 120 mmol) were reacted in 0.35 g (0.5 mmol) Pd(amphos)Cl2, 19.22 g (200 mmol) tBuONa and 250 ml toluene at 110°C for 4 h, filtered, washed three times with water, extracted three times with dichloromethane, dried over anhydrous sodium sulfate, concentrated, and chromatographed on a dichloromethane / petroleum ether column to obtain 45.14 g 7-(heptyloxy)-N-(4-nitrophenyl)-9,9-dioctyl-N-phenyl-9H-fluorene-2-amine (IV-8). 1H NMR(500MHz,Chloroform-d)δ8.15–8.10(m,2H),7.73(d,J=7.3Hz,1H),7.68(d,J=8.0Hz,1H),7.39–7.34(m,2H),7.32–7.25(m,2 H),7.14(dd,J=7.1,2.2Hz,1H),7.14–7.08(m,2H),7.04(tt,J=7.7,1.4Hz,1H),6.93(dd,J=8.0,1.9Hz,1H),6.84(dd,J=6.5,2.2H z,2H),4.00(t,J=6.3Hz,2H),1.99–1.93(m,1H),1.92(d,J=7.2Hz,1H),1.84(dt,J=13.9,7.3Hz,2H),1.80–1.71(m,2H),1.46(dq ,J=7.9,7.0Hz,2H),1.43–1.33(m,5H),1.36–1.30(m,4H),1.33–1.27(m,13H),1.30–1.23(m,9H),1.26(s,0H),0.94–0.85(m,9H).

[0082] N-(4-nitrophenyl)-7,9,9-trioctyl-N-phenyl-9H-fluorene-2-amine (Ⅳ-8, 35.82 g, 50 mmol) was reduced with hydrogen and 2 g Pd / C in tetrahydrofuran for 3 h. Filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 30.21 g N 1 -(7-(Heptyloxy)-9,9-dioctyl-9H-fluoren-2-yl)-N 1 -phenylbenzene-1,4-diamine (V-8). 1H NMR(500MHz,Chloroform-d)δ7.73(d,J=7.3Hz,1H),7.68(d,J=8.0Hz,1H),7.32–7.25(m,2H),7.17–7.14(m,1H),7. 14–7.08(m,2H),7.08–7.04(m,2H),7.04–7.00(m,1H),6.93(dd,J=8.0,1.9Hz,1H),6.84(dd,J=6.5,2.2Hz,2H),6.7 1–6.65(m,2H),4.03–3.97(m,3H),3.94(d,J=5.6Hz,1H),1.99–1.93(m,2H),1.89–1.80(m,2H),1.75(tt,J=7.5,6.3 Hz,2H),1.46(dq,J=7.9,7.0Hz,2H),1.42–1.33(m,7H),1.33–1.29(m,11H),1.29–1.23(m,13H),0.94–0.85(m,9H).

[0083] N 1 -(7-(Heptyloxy)-9,9-dioctyl-9H-fluoren-2-yl)-N 1 -phenylbenzene-1,4-diamine (V-8, 20.60g, 30mmol) was dissolved in 2.0mol / L hydrochloric acid aqueous solution, 2.21g (7.5mmol) potassium dichromate was dissolved in 2.0mol / L hydrochloric acid aqueous solution, and the potassium dichromate solution was added dropwise to the hydrochloric acid aniline solution using a dropping funnel, and the mixture was reacted at room temperature for 2h. After the reaction was completed, the mixture was cooled to room temperature, poured into 500mL methanol, filtered to obtain a crude product, and then washed with hydrochloric acid aqueous solution until the filtrate was colorless, and then poured into 500mL methanol, filtered, and the filter cake was extracted with methanol, acetone, n-hexane and chloroform in turn, and vacuum dried to obtain the target polymer (P-8) 1H NMR(500MHz,Chloroform-d)δ7.73(d,J=7.3Hz,1H),7.68(d,J=8.0Hz,1H),7.14(dd,J=7.2,2.3Hz,1H),7.10–6.99(m,6H),6. 93(dd,J=8.0,1.9Hz,1H),6.84(dd,J=6.7,2.2Hz,2H),6.69–6.64(m,2H),5.73(q,J=4.8Hz,1H),4.00(t,J=6.3Hz,2H),2.91(d ,J=4.8Hz,3H),2.35(d,J=1.0Hz,3H),1.97(d,J=7.3Hz,1H),1.95–1.90(m,2H),1.89–1.80(m,2H),1.75(tt,J=7.5,6.3Hz,2H),1.51–1.44(m,2H),1.44–1.33(m,6H),1.33–1.30(m,10H),1.30–1.26(m,16H),0.94–0.85(m,9H). The molecular weight of the polymer obtained by GPC test was 65901.

[0084] Example 9 Synthesis of Representative Conductive Polymer Material P-9 Containing N-phenyl-1,4-phenylenediamine

[0085]

[0086] Aniline (I, 23.26 g, 250 mmol) was dissolved in 500 ml of toluene. At room temperature, 2-bromo-7-(2-(2-methoxyethoxy)ethoxy)-9,9-dioctyl-9H-fluorene (C9, 117.26 g, 200 mmol) was added. After the addition was completed, 11.31 g (12.5 mmol) of Breetphos Pd G3, 11.67 g (25 mmol) of Ruphos and 60.06 g (625 mmol) of tBuONa were added. Stirring was continued at 110° C. for 2 h under nitrogen atmosphere until the reaction was complete. The mixture was filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and 63.54 g of 7-(2-(2-methoxyethoxy)ethoxy)-9,9-dioctyl-N-phenyl-9H-fluorene-2-amine (II-9) was obtained by column chromatography with dichloromethane / petroleum ether. 1H NMR(500MHz,Chloroform-d)δ7.81(d,J=7.8Hz,1H),7.66(d,J=8.0Hz,1H),7.24–7 .16(m,3H),7.09–7.01(m,3H),6.94(dd,J=8.1,1.8Hz,1H),6.91–6.84(m,2H),6.7 8(s,1H),4.16(t,J=5.1Hz,2H),3.76(t,J=5.0Hz,2H),3.64–3.55(m,4H),3.37(s, 3H),1.99–1.93(m,2H),1.89–1.80(m,2H),1.43–1.23(m,25H),0.94–0.85(m,6H).

[0087] 7-(2-(2-methoxyethoxy)ethoxy)-9,9-dioctyl-N-phenyl-9H-fluorene-2-amine (II-9, 59.94 g, 100 mmol) and 1-bromo-4-nitrobenzene (III, 24.11 g, 120 mmol) were reacted in 0.35 g (0.5 mmol) of Pd(amphos)Cl2, 19.22 g (200 mmol) of tBuONa and 250 ml of toluene at 110°C for 4 h, filtered, washed three times with water, extracted three times with dichloromethane, dried over anhydrous sodium sulfate, concentrated, and chromatographed on a dichloromethane / petroleum ether column to obtain 45.39 g of 7-(2-(2-methoxyethoxy)ethoxy)-N-(4-nitrophenyl)-9,9-dioctyl-N-phenyl-9H-fluorene-2-amine (IV-9). 1 H NMR(500MHz,Chloroform-d)δ8.15–8.10(m,2H),7.73(d,J=7.3Hz,1H),7.66(d,J=8.1Hz,1H),7.3 9–7.34(m,2H),7.32–7.25(m,2H),7.14–7.08(m,3H),7.04(tt,J=7.7,1.4Hz,1H),6.94(dd,J=8.1, 1.8Hz,1H),6.85(dd,J=17.0,2.2Hz,2H),4.16(t,J=5.1Hz,2H),3.76(t,J=5.0Hz,2H),3.64–3.55 (m,4H),3.37(s,3H),1.99–1.93(m,2H),1.89–1.80(m,2H),1.43–1.23(m,25H),0.94–0.85(m,6H).

[0088] 7-(2-(2-methoxyethoxy)ethoxy)-N-(4-nitrophenyl)-9,9-dioctyl-N-phenyl-9H-fluorene-2-amine (IV-9, 36.02 g, 50 mmol) was reduced with hydrogen and 2 g Pd / C in tetrahydrofuran for 3 h. Filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 31.42 g N 1 -(7-(2-(2-)methoxyethoxy)ethoxy)-9,9-dioctyl-9H-fluoren-2-yl)-N 1 -phenylbenzene-1,4-diamine (V-9). 1 H NMR(500MHz,Chloroform-d)δ7.73(d,J=7.3Hz,1H),7.66(d,J=8.1Hz,1H),7.32–7.25(m,2H),7.17–7.14(m,1H),7.14–7. 08(m,2H),7.08–7.00(m,3H),6.94(dd,J=8.1,1.8Hz,1H),6.85(dd,J=16.9,2.1Hz,2H),6.71–6.65(m,2H),4.16(t,J=5.1 Hz,2H),3.99(d,J=5.6Hz,1H),3.94(d,J=5.7Hz,1H),3.76(t,J=5.0Hz,2H),3.64–3.55(m,4H),3.37(s,3H),1.99–1.93(m ,2H),1.89–1.80(m,2H),1.43–1.38(m,2H),1.38–1.34(m,2H),1.34–1.30(m,8H),1.30–1.26(m,12H),0.94–0.85(m,6H).

[0089] N 1 -(7-(2-(2-)methoxyethoxy)ethoxy)-9,9-dioctyl-9H-fluoren-2-yl)-N 1 -phenylbenzene-1,4-diamine (V-9, 20.71g, 30mmol) was dissolved in 2.0mol / L hydrochloric acid aqueous solution, 2.21g (7.5mmol) potassium dichromate was dissolved in 2.0mol / L hydrochloric acid aqueous solution, and the potassium dichromate solution was added dropwise to the hydrochloric acid aniline solution using a dropping funnel, and the mixture was reacted at room temperature for 2h. After the reaction was completed, the mixture was cooled to room temperature, poured into 500mL methanol, filtered to obtain a crude product, and then washed with hydrochloric acid aqueous solution until the filtrate was colorless, and then poured into 500mL methanol, filtered, and the filter cake was extracted with methanol, acetone, n-hexane and chloroform in turn, and vacuum dried to obtain the target polymer (P-9) 1H NMR(500MHz,Chloroform-d)δ7.73(d,J=7.3Hz,1H),7.66(d,J=8.1Hz,1H),7.14(dd,J=7.2,2.3Hz,1H),7.10–6.99(m,6H),6.94 (dd,J=8.1,1.8Hz,1H),6.85(dd,J=17.2,2.1Hz,2H),6.69–6.64(m,2H),5.73(q,J=4.8Hz,1H),4.16(t,J=5.1Hz,2H),3.76(t,J =5.0Hz, 2H), 3.64–3.55(m, 4H), 3.37(s, 3H), 2.91(d, J=4.8Hz, 3H), 2.35(d, J=1.1Hz, 3H), 1.97(d, J=7.3Hz, 1H), 1.95–1.90(m, 2H), 1.89–1.80(m, 2H), 1.43–1.32(m, 6H), 1.32–1.29(m, 10H), 1.29–1.23(m, 10H), 0.94–0.85(m, 6H). The molecular weight of the polymer obtained by GPC test was 50981.

[0090] Example 10 Synthesis of Representative Conductive Polymer Material P-10 Containing N-phenyl-1,4-phenylenediamine

[0091]

[0092] Aniline (I, 223.26 g, 250 mmol) was dissolved in 500 ml toluene. 2-bromo-7,9-dioctyl-9H-carbazole (C10, 93.85 g, 200 mmol) was added at room temperature. After the addition was completed, 11.31 g (12.5 mmol) of Breetphos Pd G3, 11.67 g (25 mmol) of Ruphos and 60.06 g (625 mmol) of tBuONa were added. Stirring was continued at 110 ° C for 2 h under nitrogen atmosphere until the reaction was complete. The mixture was filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and 58.36 g of 7,9-dioctyl-N-phenyl-9H-carbazole-2-amine (II-10) was obtained by column chromatography with dichloromethane / petroleum ether. 1H NMR(500MHz,Chloroform-d)δ7.95(dd,J=25.6,7.6Hz,2H),7.25–7.15(m,4H),7.12(d,J=2.2Hz,1H),7.09–7.01(m,4H),6.88(tt,J=6.9, 1.1Hz,1H),4.26(t,J=5.8Hz,2H),2.76(t,J=8.0Hz,2H),1.84(p,J=5.9Hz,2H),1.62–1.52(m,2H),1.37–1.23(m,20H),0.94–0.85(m,6H).

[0093] 7,9-dioctyl-N-phenyl-9H-carbazole-2-amine (II-10, 48.24 g, 100 mmol) and 1-bromo-4-nitrobenzene (III, 24.11 g, 120 mmol) were reacted in 0.35 g (0.5 mmol) Pd(amphos)Cl2, 19.22 g (200 mmol) tBuONa and 250 ml toluene at 110 ° C for 4 h, filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and 43.44 g N-(4-nitrophenyl)-7,9-dioctyl-N-phenyl-9H-carbazole-2-amine (IV-10) was obtained by dichloromethane / petroleum ether column chromatography. 1 H NMR(500MHz,Chloroform-d)δ8.15–8.10(m,2H),7.97(d,J=7.0Hz,1H),7.92(d, J=7.9Hz,1H),7.39–7.34(m,2H),7.32–7.25(m,2H),7.22(d,J=2.0Hz,1H),7.15 –7.08(m,3H),7.08–7.00(m,3H),4.26(t,J=5.8Hz,2H),2.76(t,J=8.0Hz,2H),1 .84(p,J=5.9Hz,2H),1.62–1.52(m,2H),1.37–1.23(m,20H),0.94–0.85(m,6H).

[0094] N-(4-nitrophenyl)-7,9-dioctyl-N-phenyl-9H-carbazole-2-amine (Ⅳ-10, 30.17 g, 50 mmol) was reduced with hydrogen and 2 g Pd / C in tetrahydrofuran for 3 h. Filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 25.31 g N 1 -(7,9-dioctyl-9H-carbazol-2-yl)-N 1 -phenylbenzene-1,4-diamine (V-10).1 H NMR(500MHz,Chloroform-d)δ7.95(dd,J=22.9,7.4Hz,1H),7.32–7.25(m,1H),7.15–7.09(m,2H),7.09–7.00(m,3H),6.71–6.65(m,1H),4.2 6(t,J=5.8Hz,1H),2.76(t,J=8.0Hz,1H),1.84(p,J=5.9Hz,1H),1.62–1.52(m,1H),1.36–1.29(m,5H),1.29–1.23(m,6H),0.94–0.85(m,3H).

[0095] N 1 -(7,9-dioctyl-9H-carbazol-2-yl)-N 1 -phenylbenzene-1,4-diamine (V-10, 17.20 g, 30 mmol) was dissolved in 2.0 mol / L hydrochloric acid aqueous solution, 2.21 g (7.5 mmol) potassium dichromate was dissolved in 2.0 mol / L hydrochloric acid aqueous solution, and the potassium dichromate solution was added dropwise to the hydrochloric acid aniline solution using a dropping funnel, and the mixture was reacted at room temperature for 2 h. After the reaction was completed, the mixture was cooled to room temperature, poured into 500 mL of methanol, filtered to obtain a crude product, and then washed with hydrochloric acid aqueous solution until the filtrate was colorless, and then poured into 500 mL of methanol, filtered, and the filter cake was extracted with methanol, acetone, n-hexane and chloroform in turn, and vacuum dried to obtain the target polymer (P-10) 1 H NMR(500MHz,Chloroform-d)δ7.97(d,J=7.0Hz,1H),7.92(d,J=7.9Hz,1H),7.22(s,1H),7.13(d, J=2.4Hz,1H),7.10–6.99(m,8H),6.69–6.64(m,2H),5.73(q,J=4.8Hz,1H),4.26(t,J=5.8Hz,2H), 2.91 (d, J = 4.8 Hz, 3H), 2.76 (t, J = 8.0 Hz, 2H), 2.35 (d, J = 1.1 Hz, 3H), 1.84 (p, J = 5.9 Hz, 2H), 1.62–1.52 (m, 2H), 1.36–1.28 (m, 17H), 1.28–1.23 (m, 3H), 0.94–0.85 (m, 6H). The molecular weight of the polymer obtained by GPC test was 56918.

[0096] Example 11 Synthesis of Representative Conductive Polymer Material P-11 Containing N-phenyl-1,4-phenylenediamine

[0097]

[0098] Aniline (I, 23.26 g, 250 mmol) was dissolved in 500 ml toluene. At room temperature, 2-bromo-7-(heptyloxy)-9-octyl-9H-carbazole (C11, 94.24 g, 200 mmol) was added. After the addition was completed, 11.31 g (12.5 mmol) of Breetphos PdG3, 11.67 g (25 mmol) of Ruphos and 60.06 g (625 mmol) of tBuONa were added. Stirring was continued at 110° C. for 2 h under nitrogen atmosphere until the reaction was complete. The mixture was filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and 61.03 g of 7-(heptyloxy)-9-octyl-N-phenyl-9H-carbazole-2-amine (II-11) was obtained by column chromatography with dichloromethane / petroleum ether. 1 H NMR(500MHz,Chloroform-d)δ7.96(d,J=7.8Hz,1H),7.87(d,J=7.8Hz,1H),7.24–7 .15(m,3H),7.10–7.07(m,2H),7.07–7.01(m,2H),6.96(d,J=2.0Hz,1H),6.92–6.8 4(m,2H),4.25(t,J=5.7Hz,2H),4.01(t,J=6.3Hz,2H),1.84(p,J=5.9Hz,2H),1.80 –1.71(m,2H),1.46(dq,J=7.9,7.0Hz,2H),1.37–1.23(m,16H),0.94–0.85(m,6H).

[0099] 7-(Heptyloxy)-9-octyl-N-phenyl-9H-carbazole-2-amine (II-11, 48.24 g, 100 mmol) and 1-bromo-4-nitrobenzene (III, 24.11 g, 120 mmol) were reacted in 0.35 g (0.5 mmol) Pd(amphos)Cl2, 19.22 g (200 mmol) tBuONa and 250 ml toluene at 110°C for 4 h, filtered, washed three times with water, extracted three times with dichloromethane, dried over anhydrous sodium sulfate, concentrated, and chromatographed on a dichloromethane / petroleum ether column to obtain 43.58 g 7-(heptyloxy)-N-(4-nitrophenyl)-9-octyl-N-phenyl-9H-carbazole-2-amine (IV-11). 1H NMR(500MHz,Chloroform-d)δ8.16–8.10(m,2H),7.95(d,J=7.0Hz,1H),7.87(d,J=7.8Hz, 1H),7.39–7.34(m,2H),7.32–7.25(m,2H),7.14–7.00(m,5H),6.96(d,J=1.8Hz,1H),6.90 (dd,J=8.0,1.9Hz,1H),4.25(t,J=5.7Hz,2H),4.01(t,J=6.3Hz,2H),1.84(p,J=5.9Hz,2H ),1.80–1.71(m,2H),1.46(dq,J=7.9,7.0Hz,2H),1.37–1.23(m,16H),0.94–0.85(m,6H).

[0100] 7-(Heptyloxy)-N-(4-nitrophenyl)-9-octyl-N-phenyl-9H-carbazole-2-amine (IV-11, 30.27 g, 50 mmol) was reduced with hydrogen and 2 g Pd / C in tetrahydrofuran for 3 h. Filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 27.62 g N 1 -(7-(Heptyloxy)-9-octyl-9H-carbazol-2-yl)-N 1 -phenylbenzene-1,4-diamine (V-11). 1 H NMR(500MHz,Chloroform-d)δ7.95(d,J=7.0Hz,1H),7.87(d,J=7.8Hz,1H),7.32–7.25(m,2H), 7.14–7.07(m,4H),7.07–7.00(m,3H),6.96(d,J=1.8Hz,1H),6.90(dd,J=8.0,1.9Hz,1H),6.71 –6.65(m,2H),4.25(t,J=5.7Hz,2H),4.04–3.97(m,3H),3.94(d,J=5.6Hz,1H),1.84(p,J=5.9H z,2H),1.80–1.71(m,2H),1.46(dq,J=7.9,7.0Hz,2H),1.37–1.23(m,16H),0.94–0.85(m,6H).

[0101] N 1 -(7-(Heptyloxy)-9-octyl-9H-carbazol-2-yl)-N 1-phenylbenzene-1,4-diamine (V-11, 17.26g, 30mmol) was dissolved in 2.0mol / L hydrochloric acid aqueous solution, 2.21g (7.5mmol) potassium dichromate was dissolved in 2.0mol / L hydrochloric acid aqueous solution, and the potassium dichromate solution was added dropwise to the hydrochloric acid aniline solution using a dropping funnel, and the mixture was reacted at room temperature for 2h. After the reaction was completed, the mixture was cooled to room temperature, poured into 500mL methanol, filtered to obtain a crude product, and then washed with hydrochloric acid aqueous solution until the filtrate was colorless, and then poured into 500mL methanol, filtered, and the filter cake was extracted with methanol, acetone, n-hexane and chloroform in turn, and vacuum dried to obtain the target polymer (P-11) 1 H NMR(500MHz,Chloroform-d)δ7.95(d,J=7.0Hz,1H),7.87(d,J=7.8Hz,1H),7.11–7.06(m,4H),7.06–7.02(m,4H),7.01 (d,J=1.4Hz,1H),6.96(d,J=1.8Hz,1H),6.90(dd,J=8.0,1.9Hz,1H),6.69–6.64(m,2H),5.73(q,J=4.8Hz,1H),4.25(t, J=5.7Hz, 2H), 4.01(t, J=6.3Hz, 2H), 2.91(d, J=4.8Hz, 3H), 2.35(d, J=1.1Hz, 3H), 1.84(p, J=5.9Hz, 2H), 1.80–1.71(m, 2H), 1.46(dq, J=7.9,7.0Hz, 2H), 1.37–1.30(m, 6H), 1.30–1.23(m, 11H), 0.94–0.85(m, 6H). The molecular weight of the polymer obtained by GPC test was 46781.

[0102] Example 12 Synthesis of Representative Conductive Polymer Material P-12 Containing N-phenyl-1,4-phenylenediamine

[0103]

[0104] Aniline (I, 23.26 g, 250 mmol) was dissolved in 500 ml toluene. At room temperature, 2-bromo-7-(2-(2-methoxyethoxy)ethoxy)-9-octyl-9H-carbazole (C12, 95.03 g, 200 mmol) was added. After the addition was completed, 11.31 g (12.5 mmol) of Breetphos Pd G3, 11.67 g (25 mmol) of Ruphos and 60.06 g (625 mmol) of tBuONa were added. Stirring was continued at 110° C. for 2 h under nitrogen atmosphere until the reaction was complete. The mixture was filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and 65.24 g of 7-(2-(2-methoxyethoxy)ethoxy)-9-octyl-N-phenyl-9H-carbazole-2-amine (II-12) was obtained by column chromatography with dichloromethane / petroleum ether. 1 H NMR(500MHz,Chloroform-d)δ7.96(d,J=7.8Hz,1H),7.87(d,J=7.9Hz,1H),7.24–7. 15(m,3H),7.10–7.01(m,4H),6.95(d,J=1.9Hz,1H),6.93–6.84(m,2H),4.25(t,J=5 .7Hz,2H),4.16(t,J=5.0Hz,2H),3.76(t,J=5.0Hz,2H),3.64–3.55(m,4H),3.37(s, 3H),1.84(q,J=5.9Hz,2H),1.36–1.29(m,5H),1.29–1.23(m,5H),0.94–0.85(m,3H).

[0105] 7-(2-(2-methoxyethoxy)ethoxy)-9-octyl-N-phenyl-9H-carbazole-2-amine (II-12, 48.83 g, 100 mmol) and 1-bromo-4-nitrobenzene (III, 24.11 g, 120 mmol) were reacted in 0.35 g (0.5 mmol) of Pd(amphos)Cl2, 19.22 g (200 mmol) of tBuONa and 250 ml of toluene at 110°C for 4 h, filtered, washed three times with water, extracted three times with dichloromethane, dried over anhydrous sodium sulfate, concentrated, and chromatographed on a dichloromethane / petroleum ether column to obtain 41.23 g of 7-(2-(2-methoxyethoxy)ethoxy)-N-(4-nitrophenyl)-9-octyl-N-phenyl-9H-carbazole-2-amine (IV-12). 1H NMR(500MHz,Chloroform-d)δ8.16–8.10(m,2H),7.95(d,J=7.1Hz,1H),7.87(d,J=7.9Hz,1 H),7.39–7.34(m,2H),7.32–7.25(m,2H),7.14–7.00(m,5H),6.95(d,J=1.6Hz,1H),6.91(dd ,J=8.0,1.9Hz,1H),4.25(t,J=5.7Hz,2H),4.16(t,J=5.0Hz,2H),3.76(t,J=5.0Hz,2H),3. 64–3.55(m,4H),3.37(s,3H),1.84(q,J=5.9Hz,2H),1.36–1.23(m,10H),0.92–0.86(m,3H).

[0106] 7-(2-(2-methoxyethoxy)ethoxy)-N-(4-nitrophenyl)-9-octyl-N-phenyl-9H-carbazole-2-amine (Ⅳ-12, 30.47 g, 50 mmol) was reduced with hydrogen and 2 g Pd / C in tetrahydrofuran for 3 h. Filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 25.49 g N 1 -(7-(2-(2-)methoxyethoxy)-9-octyl-9H-carbazol-2-yl)-N 1 -phenylbenzene-1,4-diamine (V-12). 1 H NMR(500MHz,Chloroform-d)δ7.95(d,J=7.0Hz,1H),7.87(d,J=7.9Hz,1H),7.32–7.25(m,2H),7.14–7.07( m,3H),7.09–7.00(m,4H),6.95(d,J=1.6Hz,1H),6.91(dd,J=8.0,1.9Hz,1H),6.71–6.65(m,2H),4.25(t,J= 5.7Hz,2H),4.16(t,J=5.0Hz,2H),3.99(d,J=5.7Hz,1H),3.94(d,J=5.7Hz,1H),3.76(t,J=5.0Hz,2H),3.64 –3.55(m,4H),3.37(s,2H),1.84(q,J=5.9Hz,2H),1.36–1.29(m,2H),1.32–1.23(m,8H),0.94–0.85(m,3H).

[0107] N 1-(7-(2-(2-)methoxyethoxy)-9-octyl-9H-carbazol-2-yl)-N 1 -phenylbenzene-1,4-diamine ((Ⅴ-12, 17.38g, 30mmol) was dissolved in 2.0mol / L hydrochloric acid aqueous solution, 2.21g (7.5mmol) potassium dichromate was dissolved in 2.0mol / L hydrochloric acid aqueous solution, and the potassium dichromate solution was added dropwise to the hydrochloric acid aniline solution using a dropping funnel, and the mixture was reacted at room temperature for 2h. After the reaction was completed, the mixture was cooled to room temperature, poured into 500mL methanol, filtered to obtain a crude product, and then washed with hydrochloric acid aqueous solution until the filtrate was colorless, poured into 500mL methanol, filtered, and the filter cake was extracted with methanol, acetone, n-hexane and chloroform Soxhlet in turn, and vacuum dried to obtain the target polymer (P-12) 1 H NMR(500MHz,Chloroform-d)δ7.95(d,J=7.0Hz,1H),7.87(d,J=7.9Hz,1H),7.11–6.99(m,9H),6.95(d,J=1. 6Hz,1H),6.91(dd,J=8.0,1.9Hz,1H),6.69–6.64(m,2H),5.73(q,J=4.8Hz,1H),4.25(t,J=5.7Hz,2H),4.16 (t, J = 5.0 Hz, 2H), 3.76 (t, J = 5.0 Hz, 2H), 3.64–3.55 (m, 4H), 3.37 (s, 2H), 2.91 (d, J = 4.8 Hz, 3H), 2.35 (s, 3H), 1.84 (p, J = 5.9 Hz, 2H), 1.36–1.29 (m, 3H), 1.32–1.24 (m, 8H), 0.94–0.85 (m, 3H). The molecular weight of the polymer obtained by GPC test was 30985.

[0108] Example 13 Synthesis of Representative Conductive Polymer Material P-13 Containing N-phenyl-1,4-phenylenediamine

[0109]

[0110] Aniline (I, 23.26 g, 250 mmol) was dissolved in 300 ml toluene. 2-bromo-4-octanthiophene (C13, 54.81 g, 200 mmol) was added at room temperature. After the addition was completed, 11.31 g (12.5 mmol) of Breetphos Pd G3, 11.67 g (25 mmol) of Ruphos and 60.06 g (625 mmol) of tBuONa were added. Stirring was continued at 110 ° C for 2 h under nitrogen atmosphere until the reaction was complete. The mixture was filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and 39.63 g of 4-octyl-N-phenylthiophene-2-amine (II-13) was obtained by column chromatography with dichloromethane / petroleum ether. 1 H NMR(500MHz,Chloroform-d)δ8.68(s,1H),7.32–7.22(m,4H),6.93(tt,J=6.7,1.5Hz,1H),6.11(d,J=1.6Hz,1 H),5.78(d,J=1.7Hz,1H),2.56(t,J=7.7Hz,2H),1.56(q,J=7.6Hz,2H),1.37–1.23(m,10H),0.94–0.85(m,3H).

[0111] 4-Octyl-N-phenylthiophene-2-amine (II-13, 28.72 g, 100 mmol) and 1-bromo-4-nitrobenzene (III, 24.11 g, 120 mmol) were reacted in 0.35 g (0.5 mmol) Pd(amphos)Cl2, 19.22 g (200 mmol) tBuONa and 250 ml toluene at 110°C for 4 h, filtered, washed three times with water, extracted three times with dichloromethane, dried over anhydrous sodium sulfate, concentrated, and chromatographed on a dichloromethane / petroleum ether column to obtain 32.64 g N-(4-nitrophenyl)-4-octyl-N-phenylthiophene-2-amine (IV-13). 1 H NMR(500MHz,Chloroform-d)δ8.16–8.10(m,2H),7.44–7.39(m,2H),7.32–7.25(m,2H),7.13(dd,J=7.1,1.5Hz,3H),7.04(tt,J=7.8,1. 4Hz, 1H), 6.02 (d, J = 1.7Hz, 1H), 2.55 (t, J = 7.7Hz, 2H), 1.56 (q, J = 7.6Hz, 2H), 1.37–1.30 (m, 1H), 1.34–1.23 (m, 9H), 0.94–0.85 (m, 3H).

[0112] N-(4-nitrophenyl)-4-octyl-N-thiophene-2-amine (Ⅳ-13, 20.41 g, 50 mmol) was reduced with hydrogen and 2 g Pd / C in tetrahydrofuran for 3 h. Filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 17.61 g N 1 -(4-octylthiophene-2-yl)-N 1 -phenylbenzene-1,4-diamine (V-13). 1 H NMR(500MHz,Chloroform-d)δ7.32–7.25(m,2H),7.16–7.10(m,5H),7.04(tt,J=7.8,1.4Hz,1H),6.71–6.65(m,2H),6.02(d,J=1.7Hz, 1H), 3.99 (d, J = 5.6Hz, 1H), 3.94 (d, J = 5.7Hz, 1H), 2.55 (t, J = 7.7Hz, 2H), 1.56 (q, J = 7.6Hz, 2H), 1.37–1.23 (m, 10H), 0.94–0.85 (m, 3H).

[0113] N 1 -(4-octylthiophene-2-yl)-N 1 -phenylbenzene-1,4-diamine ((Ⅴ-13, 11.35g, 30mmol) was dissolved in 2.0mol / L hydrochloric acid aqueous solution, 2.21g (7.5mmol) potassium dichromate was dissolved in 2.0mol / L hydrochloric acid aqueous solution, and the potassium dichromate solution was added dropwise to the hydrochloric acid aniline solution using a dropping funnel, and the mixture was reacted at room temperature for 2h. After the reaction was completed, the mixture was cooled to room temperature, poured into 500mL methanol, filtered to obtain a crude product, and then washed with hydrochloric acid aqueous solution until the filtrate was colorless, poured into 500mL methanol, filtered, and the filter cake was extracted with methanol, acetone, n-hexane and chloroform Soxhlet in turn, and vacuum dried to obtain the target polymer (P-13) 1 H NMR (500 MHz, Chloroform-d) δ7.18–7.11 (m, 3H), 6.69–6.63 (m, 2H), 6.02 (d, J=1.6 Hz, 1H), 5.73 (q, J=4.8 Hz, 1H), 2.91 (d, J=4.8 Hz, 3H), 2.55 (t, J=7.7 Hz, 2H), 1.57 (p, J=7.5 Hz, 2H), 1.37–1.23 (m, 11H), 0.94–0.85 (m, 3H). The molecular weight of the polymer measured by GPC was 39810.

[0114] Example 14 Synthesis of Representative Conductive Polymer Material P-14 Containing N-phenyl-1,4-phenylenediamine

[0115]

[0116] Aniline (I, 23.26 g, 250 mmol) was dissolved in 300 ml of toluene. At room temperature, 2-bromo-4-(heptyloxy)thiophene (C14, 55.20 g, 200 mmol) was added. After the addition was completed, 11.31 g (12.5 mmol) of Breetphos Pd G3, 11.67 g (25 mmol) of Ruphos and 60.06 g (625 mmol) of tBuONa were added. Stirring was continued at 110° C. under nitrogen atmosphere for 2 h until the reaction was complete. The mixture was filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and 45.36 g of 4-(heptyloxy)-N-phenylthiophene-2-amine (II-14) was obtained by column chromatography with dichloromethane / petroleum ether. 1 H NMR(500MHz,Chloroform-d)δ8.18(s,1H),7.29(dd,J=7.9,6.5Hz,2H),7.29–7.22(m,2H),6.93(tt,J=6.7,1.5Hz,1H),5.99(d,J=1.6Hz ,1H),5.77(d,J=1.6Hz,1H),4.01(t,J=6.3Hz,2H),1.80–1.71(m,1H),1.46(dq,J=7.8,7.0Hz,2H),1.37–1.23(m,6H),0.94–0.85(m,3H).

[0117] 4-(Heptyloxy)-N-phenylthiophene-2-amine (II-14, 28.92 g, 100 mmol) and 1-bromo-4-nitrobenzene (III, 24.11 g, 120 mmol) were reacted in 0.35 g (0.5 mmol) Pd(amphos)Cl2, 19.22 g (200 mmol) tBuONa and 250 ml toluene at 110°C for 4 h, filtered, washed three times with water, extracted three times with dichloromethane, dried over anhydrous sodium sulfate, concentrated, and chromatographed on a dichloromethane / petroleum ether column to obtain 29.57 g 4-(heptyloxy)-N-(4-nitrophenyl)-N-phenylthiophene-2-amine (IV-14). 1HNMR(500MHz,Chloroform-d)δ8.16–8.10(m,2H),7.44–7.38(m,2H),7.32–7.26(m,2H),7.15–7.09(m,2H),7.04(tt,J=7.6,1.4Hz,1H),6.70(d, J=1.6Hz,1H),5.87(d,J=1.6Hz,1H),4.01(t,J=6.3Hz,2H),1.80–1.71(m ,2H),1.46(dq,J=7.8,7.0Hz,2H),1.37–1.23(m,6H),0.94–0.85(m,3H).

[0118] 4-(Heptyloxy)-N-(4-nitrophenyl)-N-thiophene-2-amine (IV-14, 20.51 g, 50 mmol) was reduced with hydrogen and 2 g Pd / C in tetrahydrofuran for 3 h. Filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 18.21 g N 1 -(4-(heptyloxy)thiophen-2-yl)-N 1 -phenylbenzene-1,4-diamine (V-14). 1 H NMR(500MHz,Chloroform-d)δ7.32–7.26(m,2H),7.12(dt,J=7.0,1.5Hz,4H),7.04(tt,J=7.6,1.4Hz,1H),6.72–6.65(m,3H),5.87(d,J=1 .6Hz,1H),4.04–3.97(m,3H),3.94(d,J=5.7Hz,1H),1.80–1.71(m,1H),1.46(dq,J=7.8,7.0Hz,2H),1.37–1.23(m,6H),0.94–0.85(m,3H).

[0119] N 1 -(4-(heptyloxy)thiophen-2-yl)-N 1 -phenylbenzene-1,4-diamine ((Ⅴ-14, 11.40g, 30mmol) was dissolved in 2.0mol / L hydrochloric acid aqueous solution, 2.21g (7.5mmol) potassium dichromate was dissolved in 2.0mol / L hydrochloric acid aqueous solution, and the potassium dichromate solution was added dropwise to the hydrochloric acid aniline solution using a dropping funnel, and the mixture was reacted at room temperature for 2h. After the reaction was completed, the mixture was cooled to room temperature, poured into 500mL methanol, filtered to obtain a crude product, and then washed with hydrochloric acid aqueous solution until the filtrate was colorless, poured into 500mL methanol, filtered, and the filter cake was extracted with methanol, acetone, n-hexane and chloroform Soxhlet in turn, and vacuum dried to obtain the target polymer (P-14) 1H NMR (500 MHz, Chloroform-d) δ7.18–7.13 (m, 2H), 7.05 (s, 4H), 6.70 (d, J = 1.6 Hz, 1H), 6.69–6.63 (m, 2H), 5.87 (d, J = 1.6 Hz, 1H), 5.73 (q, J = 4.8 Hz, 1H), 4.01 (t, J = 6.3 Hz, 2H), 2.91 (d, J = 4.8 Hz, 3H), 1.75 (tt, J = 7.5, 6.3 Hz, 2H), 1.46 (dq, J = 7.9, 7.0 Hz, 2H), 1.37–1.23 (m, 6H), 0.94–0.85 (m, 3H). The molecular weight of the polymer measured by GPC was 29018.

[0120] Example 15 Synthesis of Representative Conductive Polymer Material P-15 Containing N-phenyl-1,4-phenylenediamine

[0121]

[0122] Aniline (I, 23.26 g, 250 mmol) was dissolved in 300 ml of toluene. At room temperature, 2-bromo-4-(2-(2-methoxyethoxy)ethoxy)thiophene (C15, 56.00 g, 200 mmol) was added. After the addition was completed, 11.31 g (12.5 mmol) of Breetphos Pd G3, 11.67 g (25 mmol) of Ruphos and 60.06 g (625 mmol) of tBuONa were added. Stirring was continued at 110° C. for 2 h under a nitrogen atmosphere until the reaction was complete. The mixture was filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and 43.24 g of 4-(2-(2-methoxyethoxy)ethoxy)-N-phenylthiophene-2-amine (II-15) was obtained by column chromatography with dichloromethane / petroleum ether. 1 H NMR(500MHz,Chloroform-d)δ8.18(s,1H),7.29(dd,J=7.9,6.6Hz,2H),7.29–7.22(m,2H),6.93(tt,J=6.7,1.5Hz,1H),5 .99(d,J=1.6Hz,1H),5.77(d,J=1.6Hz,1H),4.20(t,J=5.0Hz,2H),3.76(t,J=5.0Hz,2H),3.64–3.55(m,4H),3.37(s,2H).

[0123] 4-(2-(2-methoxyethoxy)ethoxy)-N-phenylthiophene-2-amine (II-15, 29.31 g, 100 mmol) and 1-bromo-4-nitrobenzene (III, 24.11 g, 120 mmol) were reacted in 0.35 g (0.5 mmol) of Pd(amphos)Cl2, 19.22 g (200 mmol) of tBuONa and 250 ml of toluene at 110°C for 4 h, filtered, washed three times with water, extracted three times with dichloromethane, dried over anhydrous sodium sulfate, concentrated, and chromatographed on a dichloromethane / petroleum ether column to obtain 32.59 g of 4-(2-(2-methoxyethoxy)ethoxy)-N-(4-nitrophenyl)-N-phenylthiophene-2-amine (IV-15). 1 H NMR(500MHz,Chloroform-d)δ8.16–8.10(m,2H),7.44–7.38(m,2H),7.32–7.26(m,2H),7.15–7.09(m,2H),7.04(tt,J=7.7,1.4Hz ,1H),6.70(d,J=1.6Hz,1H),5.87(d,J=1.6Hz,1H),4.20(t,J=5.0Hz,2H),3.76(t,J=5.0Hz,2H),3.64–3.55(m,4H),3.37(s,2H).

[0124] 4-(2-(2-methoxyethoxy)ethoxy)-N-(4-nitrophenyl)-N-phenylthiophene-2-amine (IV-15, 20.71 g, 50 mmol) was reduced with hydrogen and 2 g Pd / C in tetrahydrofuran for 3 h. Filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 17.93 g N 1 -(4-(2-(2-)methoxyethoxy)thiophen-2-yl)-N 1 -phenylbenzene-1,4-diamine (V-15). 1 H NMR(500MHz,Chloroform-d)δ7.32–7.26(m,2H),7.12(dt,J=7.0,1.5Hz,4H),7.04(tt,J=7.7,1.4Hz,1H),6.72–6.65(m,3H),5.87(d,J =1.6Hz,1H),4.20(t,J=5.0Hz,2H),3.99(d,J=5.7Hz,1H),3.94(d,J=5.7Hz,1H),3.76(t,J=5.0Hz,2H),3.64–3.55(m,4H),3.37(s,2H).

[0125] N 1-(4-(2-(2-)methoxyethoxy)thiophen-2-yl)-N 1 -phenylbenzene-1,4-diamine ((Ⅴ-15, 11.52g, 30mmol) was dissolved in 2.0mol / L hydrochloric acid aqueous solution, 2.21g (7.5mmol) potassium dichromate was dissolved in 2.0mol / L hydrochloric acid aqueous solution, and the potassium dichromate solution was added dropwise to the hydrochloric acid aniline solution using a dropping funnel, and the mixture was reacted at room temperature for 2h. After the reaction was completed, the mixture was cooled to room temperature, poured into 500mL methanol, filtered to obtain a crude product, and then washed with hydrochloric acid aqueous solution until the filtrate was colorless, poured into 500mL methanol, filtered, and the filter cake was extracted with methanol, acetone, n-hexane and chloroform in turn, and vacuum dried to obtain the target polymer (P-15) 1 H NMR (500 MHz, Chloroform-d) δ7.18–7.13 (m, 2H), 6.70 (d, J=1.6 Hz, 1H), 6.69–6.63 (m, 2H), 5.87 (d, J=1.6 Hz, 1H), 5.73 (q, J=4.8 Hz, 1H), 4.20 (t, J=5.0 Hz, 2H), 3.76 (t, J=5.0 Hz, 2H), 3.64–3.55 (m, 4H), 3.37 (s, 2H), 2.91 (d, J=4.8 Hz, 3H). The molecular weight of the polymer measured by GPC was 19078.

[0126] Example 16 Synthesis of Representative Conductive Polymer Material P-16 Containing N-phenyl-1,4-phenylenediamine

[0127]

[0128] Aniline (I, 23.26 g, 250 mmol) was dissolved in 300 ml of toluene. At room temperature, 3-bromo-6-octylthiophene [3,2-b] thiophene (C16, 66.00 g, 200 mmol) was added. After the addition was completed, 11.31 g (12.5 mmol) of Breetphos Pd G3, 11.67 g (25 mmol) of Ruphos and 60.06 g (625 mmol) of tBuONa were added. Stirring was continued at 110 ° C for 2 h under nitrogen atmosphere until the reaction was complete. The mixture was filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and 51.47 g of 6-octyl-N-phenylthiophene [3,2-b] thiophene-3-amine (II-16) was obtained by column chromatography with dichloromethane / petroleum ether. 1H NMR(500MHz,Chloroform-d)δ7.38(s,1H),7.24–7.16(m,3H),6.99(s,1H),6.88(tt,J=6.9,1.2Hz,1H), 6.82–6.76(m,2H),2.69(t,J=7.5Hz,2H),1.57(q,J=7.4Hz,2H),1.38–1.23(m,10H),0.94–0.85(m,3H).

[0129] 6-Octyl-N-phenylthiophene[3,2-b]thiophene-3-amine (II-16, 34.31 g, 100 mmol) and 1-bromo-4-nitrobenzene (III, 24.11 g, 120 mmol) were reacted in 0.35 g (0.5 mmol) Pd(amphos)Cl2, 19.22 g (200 mmol) tBuONa and 250 ml toluene at 110 ° C for 4 h, filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed on a dichloromethane / petroleum ether column to obtain 35.74 g N-(4-nitrophenyl)-6-octyl-N-phenylthiophene[3,2-b]thiophene-3-amine (IV-16). 1 H NMR(500MHz,Chloroform-d)δ8.16–8.10(m,2H),7.47–7.41(m,2H),7.39(s,1H),7.32–7.25(m,2H),7.21(s,1H),7.14–7.08(m,2H) ,7.04(tt,J=7.7,1.4Hz,1H),2.69(t,J=7.5Hz,2H),1.57(q,J=7.4Hz,2H),1.38–1.27(m,6H),1.30–1.23(m,4H),0.94–0.85(m,3H).

[0130] N-(4-nitrophenyl)-6-octyl-N-phenylthiophen[3,2-b]thiophene-3-amine (Ⅳ-16, 23.21 g, 50 mmol) was reduced with hydrogen and 2 g Pd / C in tetrahydrofuran for 3 h. Filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 20.28 g N 1 -(6-octylthiophen[3,2-b]thiophen-3-yl)-N 1 -phenylbenzene-1,4-diamine (V-16). 1H NMR(500MHz,Chloroform-d)δ7.39(s,1H),7.32–7.25(m,2H),7.21(s,1H),7 .16–7.08(m,4H),7.04(tt,J=7.7,1.4Hz,1H),6.71–6.65(m,2H),3.99(d,J=5 .7Hz,1H),3.94(d,J=5.7Hz,1H),2.69(t,J=7.5Hz,2H),1.57(q,J=7.4Hz,2H) ,1.38–1.29(m,5H),1.31–1.26(m,4H),1.29–1.23(m,1H),0.94–0.85(m,3H).

[0131] N 1 -(6-octylthiophen[3,2-b]thiophen-3-yl)-N 1 -phenylbenzene-1,4-diamine ((Ⅴ-16, 13.02g, 30mmol) was dissolved in 2.0mol / L hydrochloric acid aqueous solution, 2.21g (7.5mmol) potassium dichromate was dissolved in 2.0mol / L hydrochloric acid aqueous solution, and the potassium dichromate solution was added dropwise to the hydrochloric acid aniline solution using a dropping funnel, and the mixture was reacted at room temperature for 2h. After the reaction was completed, the mixture was cooled to room temperature, poured into 500mL methanol, filtered to obtain a crude product, and then washed with hydrochloric acid aqueous solution until the filtrate was colorless, poured into 500mL methanol, filtered, and the filter cake was extracted with methanol, acetone, n-hexane and chloroform Soxhlet in turn, and vacuum dried to obtain the target polymer (P-16) 1 H NMR (500 MHz, Chloroform-d) δ7.39 (s, 1H), 7.21 (s, 1H), 7.17–7.11 (m, 2H), 7.05 (d, J=2.7 Hz, 4H), 6.69–6.64 (m, 2H), 5.73 (q, J=4.8 Hz, 1H), 2.91 (d, J=4.8 Hz, 3H), 2.69 (t, J=7.5 Hz, 2H), 1.58 (p, J=7.4 Hz, 2H), 1.37–1.23 (m, 10H), 0.92–0.85 (m, 3H). The molecular weight of the polymer measured by GPC was 30912.

[0132] Example 17 Synthesis of Representative Conductive Polymer Material P-17 Containing N-phenyl-1,4-phenylenediamine

[0133]

[0134] Aniline (I, 23.26 g, 250 mmol) was dissolved in 300 ml of toluene. At room temperature, 3-bromo-6-(heptyloxy)thieno[3,2-b]thiophene (C17, 66.40 g, 200 mmol) was added. After the addition was completed, 11.31 g (12.5 mmol) of BreetphosPd G3, 11.67 g (25 mmol) of Ruphos and 60.06 g (625 mmol) of tBuONa were added. Stirring was continued at 110°C for 2 h under nitrogen atmosphere until the reaction was complete. The mixture was filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and 48.92 g of 6-(heptyloxy)-N-phenylthiopheno[3,2-b]thiophene-3-amine (II-17) was obtained by column chromatography with dichloromethane / petroleum ether. 1 H NMR(500MHz,Chloroform-d)δ7.36(s,1H),7.24–7.17(m,2H),7.04(s,1H),6.88(tt,J=6.9,1.2Hz,1H),6.82–6.76(m ,2H),6.49(s,1H),4.00(t,J=6.1Hz,2H),1.82–1.73(m,2H),1.51–1.41(m,2H),1.37–1.23(m,6H),0.94–0.85(m,3H).

[0135] 6-(Heptyloxy)-N-phenylthiophene[3,2-b]thiophene-3-amine (II-17, 34.51 g, 100 mmol) and 1-bromo-4-nitrobenzene (III, 24.11 g, 120 mmol) were reacted in 0.35 g (0.5 mmol) Pd(amphos)Cl2, 19.22 g (200 mmol) tBuONa and 250 ml toluene at 110 ° C for 4 hours, filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed by dichloromethane / petroleum ether column to obtain 33.26 g 6-(heptyloxy)-N-(4-nitrophenyl)-N-phenylthiophene[3,2-b]thiophene-3-amine (IV-17). 1 H NMR(500MHz,Chloroform-d)δ8.16–8.10(m,2H),7.47–7.41(m,3H),7.32–7.25(m,2H),7.14–7.08(m,2H),7.04(tt,J=7.7, 1.4Hz,1H),6.56(s,1H),4.00(t,J=6.0Hz,2H),1.82–1.73(m,2H),1.51–1.41(m,2H),1.37–1.23(m,6H),0.94–0.85(m,3H).

[0136] 6-(Heptyloxy)-N-(4-nitrophenyl)-N-benzothieno[3,2-b]thiophene-3-amine (IV-17, 23.31 g, 50 mmol) was reduced with hydrogen and 2 g Pd / C in tetrahydrofuran for 3 h. Filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 21.29 g N 1 -(6-(heptyloxy)thieno[3,2-b]thiophen-3-yl)-N 1 -phenylbenzene-1,4-diamine (V-17). 1 H NMR(500MHz,Chloroform-d)δ7.42(s,1H),7.32–7.25(m,2H),7.16–7.08(m,4H),7.04(tt,J=7.7,1.4Hz,1H),6.71–6.65(m,2H),6 .56(s,1H),4.03–3.97(m,3H),3.94(d,J=5.7Hz,1H),1.82–1.73(m,2H),1.51–1.41(m,2H),1.37–1.23(m,7H),0.94–0.85(m,3H).

[0137] N1-(6-(Heptyloxy)thieno[3,2-b]thiophene-3-yl)-N1-phenylbenzene-1,4-diamine ((Ⅴ-17, 13.08 g, 30 mmol) was dissolved in 2.0 mol / L aqueous hydrochloric acid solution, 2.21 g (7.5 mmol) potassium dichromate was dissolved in 2.0 mol / L aqueous hydrochloric acid solution, the potassium dichromate solution was added dropwise to the hydrochloric acid aniline solution using a dropping funnel, and the mixture was reacted at room temperature for 2 h. After the reaction was completed, the mixture was cooled to room temperature, poured into 500 mL of methanol, filtered to obtain a crude product, and then washed with aqueous hydrochloric acid solution until the filtrate was colorless, poured into 500 mL of methanol, filtered, and the filter cake was extracted with methanol, acetone, n-hexane and chloroform in turn, and vacuum dried to obtain the target polymer (P-17) 1 H NMR (500 MHz, Chloroform-d) δ7.42 (s, 1H), 7.17–7.11 (m, 2H), 7.05 (d, J=2.7 Hz, 4H), 6.69–6.64 (m, 2H), 6.56 (s, 1H), 5.73 (q, J=4.8 Hz, 1H), 4.00 (t, J=6.0 Hz, 2H), 2.91 (d, J=4.8 Hz, 3H), 1.77 (tt, J=7.4, 6.1 Hz, 2H), 1.51–1.41 (m, 2H), 1.37–1.28 (m, 3H), 1.32–1.23 (m, 3H), 0.94–0.85 (m, 3H). The molecular weight of the polymer measured by GPC was 29871.

[0138] Example 18 Synthesis of Representative Conductive Polymer Material P-18 Containing N-phenyl-1,4-phenylenediamine

[0139]

[0140] Aniline (I, 23.26 g, 250 mmol) was dissolved in 300 ml of toluene. At room temperature, 3-bromo-6-(2-(2-methoxyethoxy)ethoxy)thieno[3,2-b]thiophene (C18, 67.19 g, 200 mmol) was added. After the addition was completed, 11.31 g (12.5 mmol) of Breetphos Pd G3, 11.67 g (25 mmol) of Ruphos and 60.06 g (625 mmol) of tBuONa were added. Stirring was continued at 110°C for 2 h under nitrogen atmosphere until the reaction was complete. The mixture was filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and 50.96 g of 6-(2-(2-methoxyethoxy)ethoxy)-N-phenylthieno[3,2-b]thiophene-3-amine (II-18) was obtained by column chromatography with dichloromethane / petroleum ether. 1 H NMR(500MHz,Chloroform-d)δ7.36(s,1H),7.24–7.17(m,2H),7.04(s,1H),6.88(tt,J=6.8,1.2Hz,1H),6. 82–6.76(m,2H),6.48(s,1H),4.23(t,J=4.9Hz,2H),3.77(t,J=4.9Hz,2H),3.64–3.55(m,4H),3.37(s,2H).

[0141] 6-(2-(2-methoxyethoxy)ethoxy)-N-phenylthieno[3,2-b]thiophene-3-amine (II-18, 34.91 g, 100 mmol) and 1-bromo-4-nitrobenzene (III, 24.11 g, 120 mmol) were reacted in 0.35 g (0.5 mmol) Pd(amphos)Cl2, 19.22 g (200 mmol) tBuONa and 250 ml toluene at 110 ° C for 4 hours, filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed on a dichloromethane / petroleum ether column to obtain 35.66 g 6-(2-(2-methoxyethoxy)ethoxy)-N-(4-nitrophenyl)-N-phenylthieno[3,2-b]thiophene-3-amine (IV-18). 1H NMR(500MHz,Chloroform-d)δ8.16–8.10(m,1H),7.47–7.41(m,1H),7.32–7.25(m,1H),7.14–7.08(m,1H), 7.04(tt,J=7.7,1.4Hz,0H),4.23(t,J=4.9Hz,1H),3.77(t,J=4.9Hz,1H),3.64–3.55(m,2H),3.37(s,1H).

[0142] 6-(2-(2-methoxyethoxy)ethoxy)-N-(4-nitrophenyl)-N-phenylthiophen[3,2-b]thiophene-3-amine (Ⅳ-18, 23.50 g, 50 mmol) was reduced with hydrogen and 2 g Pd / C in tetrahydrofuran for 3 h. Filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 21.12 g N 1 -(6-(2-(2-)methoxyethoxy)thieno[3,2-b]thiophen-3-yl)-N 1 -phenylbenzene-1,4-diamine (V-18). 1 HNMR(500MHz,Chloroform-d)δ7.42(s,1H),7.32–7.25(m,2H),7.16–7.08(m,4H),7.04(tt,J=7.7,1.4Hz,1H),6.71–6.65(m,2H),6. 56(s,1H),4.23(t,J=4.9Hz,2H),3.99(d,J=5.7Hz,1H),3.94(d,J=5.7Hz,1H),3.77(t,J=4.9Hz,2H),3.64–3.55(m,4H),3.37(s,2H).

[0143] N 1 -(6-(2-(2-)methoxyethoxy)thieno[3,2-b]thiophen-3-yl)-N 1 -phenylbenzene-1,4-diamine (V-18, 13.20 g, 30 mmol) was dissolved in 2.0 mol / L hydrochloric acid aqueous solution, 2.21 g (7.5 mmol) potassium dichromate was dissolved in 2.0 mol / L hydrochloric acid aqueous solution, and the potassium dichromate solution was added dropwise to the hydrochloric acid aniline solution using a dropping funnel, and the mixture was reacted at room temperature for 2 h. After the reaction was completed, the mixture was cooled to room temperature, poured into 500 mL of methanol, filtered to obtain a crude product, and then washed with hydrochloric acid aqueous solution until the filtrate was colorless, and then poured into 500 mL of methanol, filtered, and the filter cake was extracted with methanol, acetone, n-hexane and chloroform in turn, and vacuum dried to obtain the target polymer (P-18) 1H NMR (500 MHz, Chloroform-d) δ7.42 (s, 1H), 7.17–7.11 (m, 2H), 7.05 (d, J=2.7 Hz, 4H), 6.69–6.64 (m, 2H), 6.56 (s, 1H), 5.73 (q, J=4.8 Hz, 1H), 4.23 (t, J=4.9 Hz, 2H), 3.77 (t, J=4.9 Hz, 2H), 3.64–3.55 (m, 4H), 3.37 (s, 2H), 2.91 (d, J=4.8 Hz, 3H). The molecular weight of the polymer measured by GPC was 31987.

[0144] Example 19 Synthesis of Representative Conductive Polymer Material P-19 Containing N-phenyl-1,4-phenylenediamine

[0145]

[0146] Aniline (I, 23.26 g, 250 mmol) was dissolved in 500 ml toluene. At room temperature, 4-bromo-8-octylbenzo[1,2-b:4,5-b']dithiophene (C19, 76.01 g, 200 mmol) was added. After the addition was completed, 11.31 g (12.5 mmol) BretphosPd G3, 11.67 g (25 mmol) Ruphos and 60.06 g (625 mmol) tBuONa were added. Stirring was continued at 110 ° C for 2 h under nitrogen atmosphere until the reaction was complete. The mixture was filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and 42.36 g 8-octyl-N-phenylbenzo[1,2-b:4,5-b']dithiophene-4-amine (II-19) was obtained by column chromatography with dichloromethane / petroleum ether. 1 H NMR(500MHz,Chloroform-d)δ7.63(d,J=5.3Hz,1H),7.48–7.39(m,3H),7.24–7.17(m,2H),6.91–6.82(m,3H),3.08(t,J=7.8Hz,2H),1.60(q, J=7.6Hz,2H),1.40–1.33(m,2H),1.33(dd,J=3.9,3.0Hz,1H),1.33–1.27(m,5H),1.28(d,J=1.1Hz,2H),1.30–1.23(m,1H),0.94–0.85(m,3H).

[0147] 8-Octyl-N-phenylbenzo[1,2-b:4,5-b']dithiophene-4-amine (II-19, 39.32 g, 100 mmol) and 1-bromo-4-nitrobenzene (III, 24.11 g, 120 mmol) were reacted in 0.35 g (0.5 mmol) Pd(amphos)Cl2, 19.22 g (200 mmol) tBuONa and 250 ml toluene at 110 ° C for 4 hours, filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 32.39 g N-(4-nitrophenyl)-8-octyl-N-phenylbenzo[1,2-b:4,5-b']dithiophene-4-amine (IV-19). 1 H NMR(500MHz,Chloroform-d)δ8.15–8.10(m,2H),7.62(d,J=5.7Hz,1H),7.52(d,J=5.5Hz,1H),7.50–7.45(m,2H),7.42(d,J=5.6Hz,2H),7.32–7 .25(m,2H),7.17–7.11(m,2H),7.04(tt,J=7.7,1.4Hz,1H),3.08(t,J=7 .8Hz,2H),1.60(q,J=7.6Hz,2H),1.40–1.23(m,10H),0.94–0.85(m,3H).

[0148] N-(4-nitrophenyl)-8-octyl-N-phenylbenzo[1,2-b:4,5-b']dithiophene-4-amine (Ⅳ-19, 25.71 g, 50 mmol) was reduced with hydrogen and 2 g Pd / C in tetrahydrofuran for 3 h. Filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 22.52 g N 1 -(8-octylbenzo[1,2-b:4,5-b']dithiophen-4-yl)-N 1 -phenylbenzene-1,4-diamine (V-19). 1H NMR(500MHz,Chloroform-d)δ7.62(d,J=5.7Hz,1H),7.52(d,J=5.5Hz,1H),7.42(d,J=5.6Hz, 2H),7.32–7.25(m,2H),7.13(td,J=7.1,1.4Hz,4H),7.04(tt,J=7.7,1.4Hz,1H),6.71–6.65(m ,2H),3.99(d,J=5.7Hz,1H),3.94(d,J=5.7Hz,1H),3.08(t,J=7.8Hz,2H),1.65–1.56(m,1H),1 .40–1.34(m,1H),1.37–1.31(m,1H),1.34–1.28(m,3H),1.31–1.23(m,5H),0.94–0.85(m,3H).

[0149] N 1 -(8-octylbenzo[1,2-b:4,5-b']dithiophen-4-yl)-N 1 -phenylbenzene-1,4-diamine (V-19, 14.53g, 30mmol) was dissolved in 2.0mol / L hydrochloric acid aqueous solution, 2.21g (7.5mmol) potassium dichromate was dissolved in 2.0mol / L hydrochloric acid aqueous solution, and the potassium dichromate solution was added dropwise to the hydrochloric acid aniline solution using a dropping funnel, and the mixture was reacted at room temperature for 2h. After the reaction was completed, the mixture was cooled to room temperature, poured into 500mL methanol, filtered to obtain a crude product, and then washed with hydrochloric acid aqueous solution until the filtrate was colorless, and then poured into 500mL methanol, filtered, and the filter cake was extracted with methanol, acetone, n-hexane and chloroform in turn, and vacuum dried to obtain the target polymer (P-19) 1 H NMR(500MHz,Chloroform-d)δ7.62(d,J=5.7Hz,1H),7.52(d,J=5.5Hz,1H),7.42(s,1H) ,7.18–7.12(m,2H),7.06(s,4H),6.69–6.64(m,2H),5.73(q,J=4.8Hz,1H),3.08(t,J=7. 8Hz, 2H), 2.91(d, J=4.8Hz, 3H), 1.61(p, J=7.5Hz, 2H), 1.40–1.34(m, 1H), 1.37–1.32(m, 1H), 1.34–1.29(m, 2H), 1.32–1.23(m, 6H), 0.94–0.85(m, 3H). The molecular weight of the polymer obtained by GPC test was 30965.

[0150] Example 20 Synthesis of Representative Conductive Polymer Material P-20 Containing N-phenyl-1,4-phenylenediamine

[0151]

[0152] Aniline (I, 23.26 g, 250 mmol) was dissolved in 500 ml toluene. At room temperature, 4-bromo-8-(heptyloxy)benzo[1,2-b:4,5-b']dithiophene (C20, 76.40 g, 200 mmol) was added. After the addition was completed, 11.31 g (12.5 mmol) Breetphos Pd G3, 11.67 g (25 mmol) Ruphos and 60.06 g (625 mmol) tBuONa were added. Stirring was continued at 110 ° C for 2 h under nitrogen atmosphere until the reaction was complete. The mixture was filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and 52.68 g 8-(heptyloxy)-N-phenylbenzo[1,2-b:4,5-b']dithiophene-4-amine (II-20) was obtained by column chromatography with dichloromethane / petroleum ether. 1 H NMR(500MHz,Chloroform-d)δ7.55(dd,J=5.4,3.2Hz,2H),7.44–7.37(m,3H),7.24–7.17(m,2H),6.88(tt,J=7.0,1.2Hz,1H),6.88– 6.82(m,2H),4.03(t,J=6.0Hz,2H),1.86–1.77(m,1H),1.51–1.41(m,2H),1.37–1.28(m,4H),1.31–1.23(m,2H),0.94–0.85(m,3H).

[0153] 8-(Heptyloxy)-N-phenylbenzo[1,2-b:4,5-b']dithiophene-4-amine (II-20, 39.51 g, 100 mmol) and 1-bromo-4-nitrobenzene (III, 24.11 g, 120 mmol) were reacted in 0.35 g (0.5 mmol) Pd(amphos)Cl2, 19.22 g (200 mmol) tBuONa and 250 ml toluene at 110 ° C for 4 h, filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 36.23 g 8-(heptyloxy)-N-(4-nitrophenyl)-N-phenylbenzo[1,2-b:4,5-b']dithiophene-4-amine (IV-20). 1H NMR(500MHz,Chloroform-d)δ8.16–8.10(m,2H),7.62(d,J=5.5Hz,1H),7.56(d,J=5.7Hz,1H),7.51–7.45(m,2H),7.43(dd,J=5.6,1.0Hz,2H),7.32–7.25( m,2H),7.17–7.11(m,2H),7.04(tt,J=7.7,1.4Hz,1H),4.03(t,J=6.0Hz,2H) ,1.86–1.77(m,1H),1.51–1.41(m,2H),1.37–1.23(m,6H),0.94–0.85(m,3H).

[0154] 8-(Heptyloxy)-N-(4-nitrophenyl)-N-phenylbenzo[1,2-b:4,5-b']dithiophene-4-amine (IV-20, 25.81 g, 50 mmol) was reduced with hydrogen and 2 g Pd / C in tetrahydrofuran for 3 h. Filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 23.09 g N 1 -(8-(heptyloxy)benzo[1,2-b:4,5-b']dithiophen-4-yl)-N 1 -phenylbenzene-1,4-diamine (V-20). 1 H NMR(500MHz,Chloroform-d)δ7.62(d,J=5.5Hz,1H),7.56(d,J=5.7Hz,1H),7.43(dd,J =5.6,1.0Hz,2H),7.32–7.25(m,2H),7.13(td,J=7.1,1.4Hz,4H),7.04(tt,J=7.7,1.4 Hz,1H),6.71–6.65(m,2H),4.03(t,J=6.0Hz,2H),3.99(d,J=5.7Hz,1H),3.94(d,J=5. 7Hz,1H),1.86–1.77(m,1H),1.51–1.41(m,2H),1.37–1.23(m,6H),0.94–0.85(m,3H).

[0155] N 1 -(8-(heptyloxy)benzo[1,2-b:4,5-b']dithiophen-4-yl)-N 1-phenylbenzene-1,4-diamine (V-20, 14.58g, 30mmol) was dissolved in 2.0mol / L hydrochloric acid aqueous solution, 2.21g (7.5mmol) potassium dichromate was dissolved in 2.0mol / L hydrochloric acid aqueous solution, and the potassium dichromate solution was added dropwise to the hydrochloric acid aniline solution using a dropping funnel, and the mixture was reacted at room temperature for 2h. After the reaction was completed, the mixture was cooled to room temperature, poured into 500mL methanol, filtered to obtain a crude product, and then washed with hydrochloric acid aqueous solution until the filtrate was colorless, and then poured into 500mL methanol, filtered, and the filter cake was extracted with methanol, acetone, n-hexane and chloroform in turn, and vacuum dried to obtain the target polymer (P-20) 1 H NMR (500 MHz, Chloroform-d) δ7.62 (d, J=5.5 Hz, 1H), 7.56 (d, J=5.7 Hz, 1H), 7.43 (dd, J=5.6, 1.0 Hz, 2H), 7.18–7.12 (m, 2H), 6.69–6.64 (m, 2H), 5.73 (q, J=4.8 Hz, 1H), 4.03 (t, J=6.0 Hz, 2H), 2.91 (d, J=4.8 Hz, 3H), 1.82 (tt, J=7.4, 6.1 Hz, 2H), 1.51–1.41 (m, 2H), 1.37–1.23 (m, 6H), 0.94–0.85 (m, 3H). The molecular weight of the polymer measured by GPC was 48761.

[0156] Example 21 Synthesis of Representative Conductive Polymer Material P-21 Containing N-phenyl-1,4-phenylenediamine

[0157]

[0158] Aniline (I, 23.26 g, 250 mmol) was dissolved in 500 ml of toluene. At room temperature, 4-bromo-8-(2-(2-methoxyethoxy)ethoxy)benzo[1,2-b:4,5-b']dithiophene (C21, 77.19 g, 200 mmol) was added. After the addition was complete, 11.31 g (12.5 mmol) of Breetphos Pd G3, 11.67 g (25 mmol) of Ruphos and 60.06 g (625 mmol) of tBuONa were added. Stirring was continued at 110 °C under nitrogen atmosphere for 2 h until the reaction was complete, filtered, washed three times with water, extracted three times with dichloromethane, dried over anhydrous sodium sulfate, concentrated, and chromatographed by dichloromethane / petroleum ether column to obtain 53.48 g of 8-(2-(2-methoxyethoxy)ethoxy)-N-phenylbenzo[1,2-b:4,5-b']dithiophene-4-amine (II-21). 1H NMR(500MHz,Chloroform-d)δ7.55(dd,J=5.4,3.2Hz,1H),7.44–7.37(m,1H),7.24–7.17(m,1H), 6.91–6.82(m,2H),4.28(t,J=4.9Hz,1H),3.80(t,J=4.9Hz,1H),3.64–3.55(m,2H),3.37(s,1H).

[0159] 8-(2-(2-methoxyethoxy)ethoxy)-N-phenylbenzo[1,2-b:4,5-b']dithiophene-4-amine (II-21, 39.91 g, 100 mmol) and 1-bromo-4-nitrobenzene (III, 24.11 g, 120 mmol) were reacted in 0.35 g (0.5 mmol) Pd(amphos)Cl2, 19.22 g (200 mmol) tBuONa and 250 ml toluene at 110 ° C for 4 hours, filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed on a dichloromethane / petroleum ether column to obtain 35.89 g 8-(2-(2-methoxyethoxy)ethoxy)-N-(4-nitrophenyl)-N-phenylbenzo[1,2-b:4,5-b']dithiophene-4-amine (IV-21). 1 H NMR(500MHz,Chloroform-d)δ8.16–8.10(m,2H),7.62(d,J=5.5Hz,1H),7.56(d,J=5.7Hz,1H),7.51–7.45(m,2H),7.43(dd,J=5.6,1.0Hz,2H),7 .32–7.25(m,2H),7.17–7.11(m,2H),7.04(tt,J=7.7,1.4Hz,1H),4.28( t,J=4.9Hz,2H),3.80(t,J=4.9Hz,2H),3.64–3.55(m,4H),3.37(s,2H).

[0160] 8-(2-(2-methoxyethoxy)ethoxy)-N-(4-nitrophenyl)-N-phenylbenzo[1,2-b:4,5-b']dithiophene-4-amine (Ⅳ-21, 26.00 g, 50 mmol) was reduced with hydrogen and 2 g Pd / C in tetrahydrofuran for 3 h. Filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 23.89 g N 1 -(8-(2-(2-)methoxyethoxy)ethoxy)benzo[1,2-b:4,5-b']dithiophen-4-yl)-N 1 -phenylbenzene-1,4-diamine (V-21).1 H NMR(500MHz,Chloroform-d)δ7.62(d,J=5.5Hz,1H),7.56(d,J=5.7Hz,1H),7.43 (dd,J=5.6,1.0Hz,2H),7.32–7.25(m,2H),7.13(td,J=7.1,1.4Hz,4H),7.04(tt, J=7.7,1.4Hz,1H),6.71–6.65(m,2H),4.28(t,J=4.9Hz,2H),3.99(d,J=5.7Hz,1 H),3.94(d,J=5.7Hz,1H),3.80(t,J=4.9Hz,2H),3.64–3.55(m,4H),3.37(s,2H).

[0161] N 1 -(8-(2-(2-)methoxyethoxy)ethoxy)benzo[1,2-b:4,5-b']dithiophen-4-yl)-N 1 -phenylbenzene-1,4-diamine (V-21, 14.70g, 30mmol) was dissolved in 2.0mol / L hydrochloric acid aqueous solution, 2.21g (7.5mmol) potassium dichromate was dissolved in 2.0mol / L hydrochloric acid aqueous solution, and the potassium dichromate solution was added dropwise to the hydrochloric acid aniline solution using a dropping funnel, and the mixture was reacted at room temperature for 2h. After the reaction was completed, the mixture was cooled to room temperature, poured into 500mL methanol, filtered to obtain a crude product, and then washed with hydrochloric acid aqueous solution until the filtrate was colorless, and then poured into 500mL methanol, filtered, and the filter cake was extracted with methanol, acetone, n-hexane and chloroform in turn, and vacuum dried to obtain the target polymer (P-21) 1 H NMR (500 MHz, Chloroform-d) δ7.62 (d, J=5.5 Hz, 1H), 7.56 (d, J=5.7 Hz, 1H), 7.43 (dd, J=5.6, 1.0 Hz, 2H), 7.18–7.12 (m, 2H), 6.69–6.64 (m, 2H), 5.73 (q, J=4.8 Hz, 1H), 4.28 (t, J=4.9 Hz, 2H), 3.80 (t, J=4.9 Hz, 2H), 3.64–3.55 (m, 4H), 3.37 (s, 2H), 2.91 (d, J=4.8 Hz, 3H). The molecular weight of the polymer measured by GPC was 39870.

[0162] Example 22 Synthesis of Representative N-phenyl-1,4-phenylenediamine-containing Conductive Polymer Material P-22

[0163]

[0164] Aniline (I, 23.26 g, 250 mmol) was dissolved in 500 ml of toluene. 4-bromo-2,6,8-trioctyl-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindole (C22, 114.88 g, 200 mmol) was added at room temperature. After the addition was complete, 11.31 g (12.5 mmol) of Breetphos Pd G3, 11.67 g (25 mmol) of Ruphos and 60.06 g (625 mmol) of tBuONa were added. Stirring was continued at 110 °C under nitrogen atmosphere for 2 h until the reaction was complete, filtered, washed three times with water, extracted three times with dichloromethane, dried over anhydrous sodium sulfate, concentrated, and chromatographed by dichloromethane / petroleum ether column to obtain 65.88 g of 2,6,8-trioctyl-N-phenyl-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindol-4-amine (II-22). 1 H NMR(500MHz,Chloroform-d)δ7.24–7.17(m,1H),6.91–6.81(m,1H),4.28(s,2H),3.80(s,2H),2.62(t,J=8.3Hz,1H),2. 51(t,J=5.9Hz,2H),1.62–1.50(m,3H),1.40–1.31(m,2H),1.29(dddd,J=12.3,5.0,3.0,2.0Hz,13H),0.94–0.85(m,4H).

[0165] 2,6,8-Trioctyl-N-phenyl-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindole-4-amine (II-22, 58.75 g, 100 mmol) and 1-bromo-4-nitrobenzene (III, 24.11 g, 120 mmol) were reacted in 0.35 g (0.5 mmol) Pd(amphos)Cl2, 19.22 g (200 mmol) tBuONa and 250 ml toluene at 110 ° C for 4 h, filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed on a dichloromethane / petroleum ether column to obtain 43.93 g N-(4-nitrophenyl)-2,6,8-trioctyl-N-phenyl-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindole-4-amine (IV-22). 1H NMR(500MHz,Chloroform-d)δ8.16–8.10(m,1H),7.45–7.39(m,1H),7.32–7.25(m,1H),7.16–7.10(m,1H),7.04(tt,J=7.7,1.4Hz,0H),4.29(s ,2H),3.79(s,2H),2.62(t,J=8.3Hz,1H),2.51(t,J=5.9Hz,2H),1.62– 1.54(m,1H),1.58–1.50(m,2H),1.40–1.23(m,15H),0.94–0.85(m,4H).

[0166] N-(4-nitrophenyl)-2,6,8-trioctyl-N-phenyl-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindol-4-amine (Ⅳ-22, 35.43 g, 50 mmol) was reduced with hydrogen and 2 g Pd / C in tetrahydrofuran for 3 h. Filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 31.55 g N 1 -phenyl-N 1 -(2,6,8-trioctyl-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindol-4-yl)benzene-1,4-diamine (V-22). 1 H NMR(500MHz,Chloroform-d)δ7.32–7.25(m,1H),7.16–7.08(m,2H),7.04(tt,J=7.7,1.4Hz,0H),6.71–6.65(m,1H),4.29(s,1H),3.7 9(s,2H),2.62(t,J=8.3Hz,1H),2.51(d,J=11.8Hz,1H),1.62–1.54(m,1H),1.58–1.50(m,2H),1.40–1.23(m,14H),0.94–0.85(m,4H).

[0167] N 1 -phenyl-N 1-(2,6,8-trioctyl-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindol-4-yl)benzene-1,4-diamine (V-22, 20.36 g, 30 mmol) was dissolved in 2.0 mol / L hydrochloric acid aqueous solution, 2.21 g (7.5 mmol) potassium dichromate was dissolved in 2.0 mol / L hydrochloric acid aqueous solution, the potassium dichromate solution was added dropwise to the hydrochloric acid aniline solution using a dropping funnel, and the mixture was reacted at room temperature for 2 hours. After the reaction was completed, the mixture was cooled to room temperature, poured into 500 mL of methanol, filtered to obtain a crude product, and then washed with hydrochloric acid aqueous solution until the filtrate was colorless, poured into 500 mL of methanol, filtered, and the filter cake was extracted with methanol, acetone, n-hexane and chloroform in turn, and vacuum dried to obtain the target polymer (P-22) 1 H NMR (500 MHz, Chloroform-d) δ7.17–7.11 (m, 2H), 7.05 (s, 3H), 6.69–6.64 (m, 2H), 5.73 (q, J=4.8 Hz, 1H), 4.29 (s, 3H), 3.79 (s, 3H), 2.91 (d, J=4.8 Hz, 3H), 2.62 (t, J=8.3 Hz, 2H), 2.51 (t, J=5.9 Hz, 4H), 2.35 (s, 3H), 1.62–1.54 (m, 3H), 1.57–1.50 (m, 3H), 1.40–1.32 (m, 2H), 1.35–1.23 (m, 28H), 0.94–0.85 (m, 9H). The molecular weight of the polymer measured by GPC was 46781.

[0168] Example 23 Synthesis of Representative Conductive Polymer Material P-23 Containing N-phenyl-1,4-phenylenediamine

[0169]

[0170] Aniline (I, 23.26 g, 250 mmol) was dissolved in 500 ml of toluene. At room temperature, 4-bromo-8-(heptyloxy)-2,6-dioctyl-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindole (C23, 115.27 g, 200 mmol) was added. After the addition was complete, 11.31 g (12.5 mmol) of Breetphos Pd G3, 11.67 g (25 mmol) of Ruphos and 60.06 g (625 mmol) of tBuONa were added. Stirring was continued at 110 °C under nitrogen atmosphere for 2 h until the reaction was complete, filtered, washed three times with water, extracted three times with dichloromethane, dried over anhydrous sodium sulfate, concentrated, and chromatographed by dichloromethane / petroleum ether column to obtain 75.39 g of 2-(heptyloxy)-6,8-dioctyl-N-phenyl-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindol-4-amine (II-23).1 H NMR(500MHz,Chloroform-d)δ7.24–7.17(m,1H),6.91–6.81(m,2H),4.28(s,1H) ,4.07(s,1H),4.00(s,1H),3.80(s,1H),3.65(t,J=5.8Hz,1H),2.64(t,J=8.2Hz, 1H),2.51(t,J=5.9Hz,1H),1.68–1.50(m,3H),1.42–1.35(m,1H),1.38–1.33(m, 1H),1.35–1.30(m,2H),1.33–1.27(m,6H),1.30–1.23(m,5H),0.92–0.85(m,5H).

[0171] 2-(Heptyloxy)-6,8-dioctyl-N-phenyl-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindol-4-amine (II-23, 58.95 g, 100 mmol) and 1-bromo-4-nitrobenzene (III, 24.11 g, 120 mmol) were reacted in 0.35 g (0.5 mmol) Pd(amphos)Cl2, 19.22 g (200 mmol) tBuONa and 250 ml toluene at 110 ° C for 4 h, filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 44.76 g 8-(Heptyloxy)-N-(4-nitrophenyl)-2,6-dioctyl-N-phenyl-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindol-4-amine (IV-23). 1 H NMR(500MHz,Chloroform-d)δ8.16–8.10(m,1H),7.45–7.39(m,1H),7.32–7.25(m,1H), 7.16–7.10(m,1H),7.04(tt,J=7.7,1.4Hz,1H),4.12(t,J=4.7Hz,1H),4.07–4.02(m,1H) ,3.98(t,J=6.0Hz,1H),3.86(s,2H),2.51(t,J=5.9Hz,2H),1.81(tt,J=7.5,6.1Hz,1H) ,1.59–1.51(m,2H),1.46(dq,J=7.9,6.9Hz,1H),1.37–1.24(m,13H),0.94–0.85(m,5H).

[0172] 8-(Heptyloxy)-N-(4-nitrophenyl)-2,6-dioctyl-N-phenyl-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindol-4-amine (Ⅳ-23, 35.52 g, 50 mmol) was reduced with hydrogen and 2 g Pd / C in tetrahydrofuran for 3 h. Filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 31.64 g N 1 -(8-(Heptyloxy)-2,6-dioctyl-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindol-4-yl)-N 1 -phenylbenzene-1,4-diamine (V-23). 1 H NMR(500MHz,Chloroform-d)δ7.32–7.25(m,1H),7.16–7.08(m,2H),7.04(tt,J=7 .7,1.4Hz,1H),6.71–6.65(m,1H),4.12(t,J=4.7Hz,1H),4.07–4.02(m,1H),4.02– 3.91(m,2H),3.86(s,2H),2.51(t,J=5.9Hz,2H),1.81(tt,J=7.5,6.1Hz,1H),1.59 –1.51(m,2H),1.46(dq,J=7.9,6.9Hz,1H),1.37–1.24(m,14H),0.94–0.85(m,5H).

[0173] N1-(8-(Heptyloxy)-2,6-dioctyl-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindol-4-yl)-N1-phenylbenzene-1,4-diamine (V-23, 20.42 g, 30 mmol) was dissolved in 2.0 mol / L hydrochloric acid aqueous solution, 2.21 g (7.5 mmol) potassium dichromate was dissolved in 2.0 mol / L hydrochloric acid aqueous solution, the potassium dichromate solution was added dropwise to the hydrochloric acid aniline solution using a dropping funnel, and the mixture was reacted at room temperature for 2 h. After the reaction was completed, the mixture was cooled to room temperature, poured into 500 mL of methanol, filtered to obtain a crude product, and then washed with hydrochloric acid aqueous solution until the filtrate was colorless, poured into 500 mL of methanol, filtered, and the filter cake was extracted with methanol, acetone, n-hexane and chloroform in turn, and vacuum dried to obtain the target polymer (P-23) 1H NMR(500MHz,Chloroform-d)δ7.17–7.11(m,1H),7.05(s,2H),6.69–6.64(m,1H),5.73(q,J=4.8Hz, 0H),4.12(t,J=4.7Hz,1H),4.07–4.02(m,1H),3.98(t,J=6.0Hz,1H),3.86(s,2H),2.91(d,J=4.8Hz ,1H),2.51(t,J=5.9Hz,2H),2.35(s,1H),1.81(tt,J=7.5,6.1Hz,1H),1.55(td,J=6.4,5.9,5.4Hz,1H),1.46(dq,J=7.9,6.9Hz,1H),1.37–1.24(m,12H),0.94–0.85(m,4H). The molecular weight of the polymer obtained by GPC test was 30987.

[0174] Example 24 Synthesis of Representative N-phenyl-1,4-phenylenediamine-containing Conductive Polymer Material P-24

[0175]

[0176] Aniline (I, 23.26 g, 250 mmol) was dissolved in 500 ml of toluene. At room temperature, 4-bromo-8-(2-(2-methoxyethoxy)ethoxy)-2,6-dioctyl-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindole (C24, 116.06 g, 200 mmol) was added. After the addition was complete, 11.31 g (12.5 mmol) of Breetphos Pd G3, 11.67 g (25 mmol) of Ruphos and 60.06 g (625 mmol) of tBuONa were added. Stirring was continued at 110 °C under nitrogen atmosphere for 2 h until the reaction was complete, filtered, washed three times with water, extracted three times with dichloromethane, dried over anhydrous sodium sulfate, concentrated, and chromatographed by dichloromethane / petroleum ether column to obtain 80.71 g of 8-(2-(2-methoxyethoxy)ethoxy)-2,6-dioctyl-N-phenyl-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindol-4-amine (II-24). 1H NMR(500MHz,Chloroform-d)δ7.24–7.17(m,1H),6.91–6.81(m,2H),4.30(s,2H),4.18(t,J=4.9Hz,1H),3.89(s,2H),3.78(t,J =4.9Hz,1H),3.64–3.55(m,2H),3.37(s,1H),2.51(t,J=5.9Hz,2H),1.59–1.50(m,2H),1.36–1.23(m,10H),0.94–0.85(m,3H).

[0177] 8-(2-(2-methoxyethoxy)ethoxy)-2,6-dioctyl-N-phenyl-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindol-4-amine (II-24, 59.35 g, 100 mmol) and 1-bromo-4-nitrobenzene (III, 24.11 g, 120 mmol) were reacted in 0.35 g (0.5 mmol) Pd(amphos)Cl2, 19.22 g (200 mmol) tBuONa and 250 ml toluene at 110 ° C for 4 h, filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 42.15 g 8-(2-(2-methoxyethoxy)ethoxy)-N-(4-nitrophenyl)-2,6-dioctyl-N-phenyl-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindol-4-amine (IV-24). 1 H NMR(500MHz,Chloroform-d)δ8.16–8.10(m,1H),7.45–7.39(m,1H),7.32–7.25( m,1H),7.16–7.10(m,1H),7.04(tt,J=7.7,1.4Hz,1H),4.31(s,2H),4.18(t,J=4 .9Hz,1H),3.87(s,2H),3.78(t,J=4.9Hz,1H),3.64–3.55(m,2H),3.37(s,1H),2 .51(t,J=5.9Hz,2H),1.59–1.50(m,1H),1.36–1.23(m,10H),0.94–0.85(m,3H).

[0178] 8-(2-(2-methoxyethoxy)ethoxy)-N-(4-nitrophenyl)-2,6-dioctyl-N-phenyl-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindol-4-amine (Ⅳ-24, 35.72 g, 50 mmol) was reduced with hydrogen and 2 g Pd / C in tetrahydrofuran for 3 h. Filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 30.46 g N 1 -(8-(2-(2-)methoxyethoxy)ethoxy)-2,6-dioctyl-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindol-4-yl)-N 1 -phenylbenzene-1,4-diamine (V-24). 1 H NMR(500MHz,Chloroform-d)δ7.32–7.25(m,2H),7.12(ddd,J=12.8,7.0,1.3Hz,4H),7.04(tt,J =7.7,1.4Hz,1H),6.71–6.65(m,2H),4.31(s,3H),4.18(t,J=4.9Hz,2H),3.99(d,J=5.6Hz,1H), 3.94(d,J=5.7Hz,1H),3.87(s,4H),3.78(t,J=4.9Hz,2H),3.64–3.55(m,4H),3.37(s,2H),2.51 (t,J=5.9Hz,4H),1.59–1.50(m,2H),1.36–1.29(m,3H),1.32–1.23(m,17H),0.94–0.85(m,6H).

[0179] N 1 -(8-(2-(2-)methoxyethoxy)ethoxy)-2,6-dioctyl-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindol-4-yl)-N 1 -phenylbenzene-1,4-diamine (V-24, 20.54 g, 30 mmol) was dissolved in 2.0 mol / L hydrochloric acid aqueous solution, 2.21 g (7.5 mmol) potassium dichromate was dissolved in 2.0 mol / L hydrochloric acid aqueous solution, and the potassium dichromate solution was added dropwise to the hydrochloric acid aniline solution using a dropping funnel, and the mixture was reacted at room temperature for 2 h. After the reaction was completed, the mixture was cooled to room temperature, poured into 500 mL of methanol, filtered to obtain a crude product, and then washed with hydrochloric acid aqueous solution until the filtrate was colorless, and then poured into 500 mL of methanol, filtered, and the filter cake was extracted with methanol, acetone, n-hexane and chloroform in turn, and vacuum dried to obtain the target polymer (P-24) 1H NMR(500MHz,Chloroform-d)δ7.17–7.11(m,1H),7.05(s,2H),6.69–6.64(m,1H),5.73(q,J= 4.8Hz,0H),4.31(s,2H),4.18(t,J=4.9Hz,1H),3.87(s,2H),3.78(t,J=4.9Hz,1H),3.64–3. 55(m, 2H), 3.37(s, 1H), 2.91(d, J=4.8Hz, 1H), 2.51(t, J=5.9Hz, 2H), 2.35(s, 1H), 1.55(ddd, J=12.8, 6.9, 5.9Hz, 2H), 1.36–1.24(m, 10H), 0.94–0.85(m, 3H). The molecular weight of the polymer obtained by GPC test was 65971.

[0180] Example 25 Synthesis of Representative N-phenyl-1,4-phenylenediamine-containing Conductive Polymer Material P-25

[0181]

[0182] Aniline (I, 23.26 g, 250 mmol) was dissolved in 500 ml toluene. Bromobenzene (C25, 31.40 g, 200 mmol) was added at room temperature. After the addition was completed, 11.31 g (12.5 mmol) of Bretphos Pd G3, 11.67 g (25 mmol) of Ruphos and 60.06 g (625 mmol) of tBuONa were added. Stirring was continued at 110 ° C for 2 h under nitrogen atmosphere until the reaction was complete. The mixture was filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed by dichloromethane / petroleum ether column to obtain 23.35 g of diphenylamine (II-25). 1 H NMR (500MHz, Chloroform-d) δ7.24–7.17(m,4H),7.07–7.01(m,4H),6.88(tt,J=6.8,1.1Hz,2H),6.20(s,1H).

[0183] Diphenylamine (II-25, 16.92 g, 100 mmol) and 1-bromo-4-nitrobenzene (III, 24.11 g, 120 mmol) were reacted in 0.35 g (0.5 mmol) Pd(amphos)Cl2, 19.22 g (200 mmol) tBuONa and 250 ml toluene at 110°C for 4 h, filtered, washed three times with water, extracted three times with dichloromethane, dried over anhydrous sodium sulfate, concentrated, and chromatographed by dichloromethane / petroleum ether column to obtain 22.05 g 4-nitro-N,N-diphenylamine (IV-25). 1H NMR (500MHz, Chloroform-d) δ8.16–8.10(m,1H),7.39–7.34(m,1H),7.32–7.25(m,2H),7.14–7.08(m,2H),7.04(tt,J=7.7,1.4Hz,1H).

[0184] 4-Nitro-N,N-diphenylamine (IV-25, 14.50 g, 50 mmol) was reduced in tetrahydrofuran with hydrogen and 1 g Pd / C for 3 h. Filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 11.84 g N 1 , N 1 -diphenylbenzene-1,4-diamine (V-25). 1 H NMR (500MHz, Chloroform-d) δ7.32–7.25(m,3H),7.14–7.08(m,4H),7.08–7.00(m,4H),6.71–6.65(m,2H),3.99(d,J=5.7Hz,1H),3.94(d,J=5.7Hz,1H).

[0185] N1, N1-diphenylbenzene-1,4-diamine (V-25, 7.81 g, 30 mmol) was dissolved in 2.0 mol / L hydrochloric acid aqueous solution, 2.21 g (7.5 mmol) potassium dichromate was dissolved in 2.0 mol / L hydrochloric acid aqueous solution, the potassium dichromate solution was added dropwise to the hydrochloric acid aniline solution using a dropping funnel, and the mixture was reacted at room temperature for 2 hours. After the reaction was completed, the mixture was cooled to room temperature, poured into 500 mL of methanol, filtered to obtain a crude product, and then washed with hydrochloric acid aqueous solution until the filtrate was colorless, poured into 500 mL of methanol, filtered, and the filter cake was extracted with methanol, acetone, n-hexane and chloroform in turn, and vacuum dried to obtain the target polymer (P-25) 1 H NMR (500 MHz, Chloroform-d) δ7.32–7.25 (m, 2H), 7.14–6.99 (m, 9H), 6.69–6.64 (m, 2H), 5.73 (q, J=4.8 Hz, 1H), 2.91 (d, J=4.8 Hz, 3H). The molecular weight of the polymer measured by GPC was 25416.

[0186] Example 26 Synthesis of Representative Conductive Polymer Material P-26 Containing N-phenyl-1,4-phenylenediamine

[0187]

[0188] Aniline (I, 23.26 g, 250 mmol) was dissolved in 500 ml toluene. At room temperature, 4-bromobenzo[1,2-b:4,5-b']dithiophene (C26, 53.83 g, 200 mmol) was added. After the addition was completed, 11.31 g (12.5 mmol) Breetphos Pd G3, 11.67 g (25 mmol) Ruphos and 60.06 g (625 mmol) tBuONa were added. Stirring was continued at 110 ° C for 2 h under nitrogen atmosphere until the reaction was complete. The mixture was filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and 37.71 g N-phenylbenzo[1,2-b:4,5-b']dithiophene-4-amine (II-26) was obtained by column chromatography with dichloromethane / petroleum ether. 1 H NMR(500MHz,Chloroform-d)δ7.65(d,J=5.3Hz,1H),7.52(dd,J=10.4,5.3Hz,2H),7.43(d,J=2.1Hz, 1H),7.32(dd,J=5.3,2.2Hz,1H),7.24–7.17(m,2H),6.88(tt,J=7.0,1.2Hz,1H),6.88–6.82(m,2H).

[0189] N-phenylbenzo[1,2-b:4,5-b']dithiophene-4-amine (II-26, 28.14 g, 100 mmol) and 1-bromo-4-nitrobenzene (III, 24.11 g, 120 mmol) were reacted in 0.35 g (0.5 mmol) Pd(amphos)Cl2, 19.22 g (200 mmol) tBuONa and 250 ml toluene at 110 ° C for 4 hours, filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 28.58 g N-(4-nitrophenyl)-N-phenylbenzo[1,2-b:4,5-b']dithiophene-4-amine (IV-26). 1 H NMR(500MHz,Chloroform-d)δ8.16–8.10(m,2H),7.66(d,J=5.7Hz,1H),7.53(dd,J=10.4,5.5Hz,2H),7.50– 7.45(m,3H),7.34(dd,J=5.3,2.2Hz,1H),7.32–7.25(m,2H),7.17–7.11(m,2H),7.04(tt,J=7.7,1.4Hz,1H).

[0190] N-(4-nitrophenyl)-N-phenylbenzo[1,2-b:4,5-b']dithiophene-4-amine (Ⅳ-26, 20.12 g, 50 mmol) was reduced with hydrogen and 1 g Pd / C in tetrahydrofuran for 3 h. Filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 16.93 g N 1 -(Benzo[1,2-b:4,5-b']dithiophen-4-yl)-N 1 -phenylbenzene-1,4-diamine (V-26). 1 H NMR(500MHz,Chloroform-d)δ7.66(d,J=5.7Hz,1H),7.53(dd,J=10.3,5.5Hz,2H),7.48(d,J=2.1Hz,1H),7.34(dd,J=5.3,2.2Hz,1H),7.3 2–7.25(m,2H),7.13(td,J=7.1,1.4Hz,4H),7.04(tt,J=7.7,1.4Hz,1H),6.71–6.65(m,2H),3.99(d,J=5.7Hz,1H),3.94(d,J=5.7Hz,1H).

[0191] N 1 -(Benzo[1,2-b:4,5-b']dithiophen-4-yl)-N 1 -phenylbenzene-1,4-diamine (V-26, 11.18 g, 30 mmol) was dissolved in 2.0 mol / L hydrochloric acid aqueous solution, 2.21 g (7.5 mmol) potassium dichromate was dissolved in 2.0 mol / L hydrochloric acid aqueous solution, the potassium dichromate solution was added dropwise to the hydrochloric acid aniline solution using a dropping funnel, and the mixture was reacted at room temperature for 2 h. After the reaction was completed, the mixture was cooled to room temperature, poured into 500 mL of methanol, filtered to obtain a crude product, and then washed with hydrochloric acid aqueous solution until the filtrate was colorless, poured into 500 mL of methanol, filtered, and the filter cake was extracted with methanol, acetone, n-hexane and chloroform in turn, and vacuum dried to obtain the target polymer (P-26) 1 H NMR (500 MHz, Chloroform-d) δ7.66 (d, J=5.7 Hz, 1H), 7.53 (dd, J=10.3, 5.5 Hz, 2H), 7.48 (d, J=2.1 Hz, 1H), 7.34 (dd, J=5.3, 2.2 Hz, 1H), 7.18–7.12 (m, 2H), 7.06 (s, 4H), 6.69–6.64 (m, 2H), 5.73 (q, J=4.8 Hz, 1H), 2.91 (d, J=4.8 Hz, 3H). The molecular weight of the polymer measured by GPC was 31287.

[0192] Example 27 Synthesis of Representative N-phenyl-1,4-phenylenediamine-containing Conductive Polymer Material P-27

[0193]

[0194] Aniline (I, 23.26 g, 250 mmol) was dissolved in 500 ml of toluene. At room temperature, 4-bromo-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindole (C27, 47.82 g, 200 mmol) was added. After the addition was completed, 11.31 g (12.5 mmol) of Breetphos Pd G3, 11.67 g (25 mmol) of Ruphos and 60.06 g (625 mmol) of tBuONa were added. Stirring was continued at 110 ° C for 2 h under nitrogen atmosphere until the reaction was complete. The mixture was filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed by dichloromethane / petroleum ether column to obtain 32.67 g of N-phenyl-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindole-4-amine (II-27). 1 H NMR(500MHz,Chloroform-d)δ7.24–7.17(m,1H),7.04–6.98(m,1H),6.91–6.81(m,2H),4. 15–4.09(m,1H),4.06(qt,J=4.4,0.8Hz,1H),3.88(d,J=4.4Hz,2H),2.78(p,J=4.2Hz,1H).

[0195] N-phenyl-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindole-4-amine (II-27, 25.13 g, 100 mmol) and 1-bromo-4-nitrobenzene (III, 24.11 g, 120 mmol) were reacted in 0.35 g (0.5 mmol) Pd(amphos)Cl2, 19.22 g (200 mmol) tBuONa and 250 ml toluene at 110 ° C for 4 hours, filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 26.44 g N-(4-nitrophenyl)-N-phenyl-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindole-4-amine (IV-27). 1H NMR(500MHz,Chloroform-d)δ8.16–8.10(m,1H),7.44–7.39(m,1H),7.32–7.25(m,1H),7.13(dd,J=7.1,1.4H z,1H),7.09–7.00(m,1H),4.11–4.05(m,1H),4.05–3.99(m,1H),3.85(d,J=4.6Hz,2H),2.94(p,J=4.3Hz,1H).

[0196] N-(4-nitrophenyl)-N-phenyl-1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindol-4-amine (Ⅳ-27, 18.62 g, 50 mmol) was reduced with hydrogen and 1 g Pd / C in tetrahydrofuran for 3 h. Filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 15.58 g N 1 -(1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindol-4-yl)-N 1 -phenylbenzene-1,4-diamine (V-27). 1 H NMR(500MHz,Chloroform-d)δ7.32–7.25(m,1H),7.16–7.08(m,2H),7.08–7.00(m,1H),6.71–6.6 5(m,1H),4.11–3.97(m,3H),3.94(d,J=5.7Hz,1H),3.85(d,J=4.6Hz,2H),2.94(p,J=4.3Hz,1H).

[0197] N 1 -(1,2,3,5,6,7-hexahydropyrrolo[3,4-f]isoindol-4-yl)-N 1 -phenylbenzene-1,4-diamine (V-27, 10.27 g, 30 mmol) was dissolved in 2.0 mol / L hydrochloric acid aqueous solution, 2.21 g (7.5 mmol) potassium dichromate was dissolved in 2.0 mol / L hydrochloric acid aqueous solution, the potassium dichromate solution was added dropwise to the hydrochloric acid aniline solution using a dropping funnel, and the mixture was reacted at room temperature for 2 h. After the reaction was completed, the mixture was cooled to room temperature, poured into 500 mL of methanol, filtered to obtain a crude product, and then washed with hydrochloric acid aqueous solution until the filtrate was colorless, poured into 500 mL of methanol, filtered, and the filter cake was extracted with methanol, acetone, n-hexane and chloroform in turn, and vacuum dried to obtain the target polymer (P-27) 1H NMR (500 MHz, Chloroform-d) δ7.17–7.11 (m, 2H), 7.06 (p, J = 0.9 Hz, 1H), 7.05 (s, 4H), 6.69–6.64 (m, 2H), 5.73 (q, J = 4.8 Hz, 1H), 4.11–4.05 (m, 2H), 4.05–3.99 (m, 2H), 3.85 (d, J = 4.6 Hz, 4H), 2.94 (p, J = 4.3 Hz, 2H), 2.91 (d, J = 4.8 Hz, 3H). The molecular weight of the polymer measured by GPC was 18765.

[0198] Example 28 Synthesis of Representative Conductive Polymer Material P-28 Containing N-phenyl-1,4-phenylenediamine

[0199]

[0200] Aniline (I, 23.26 g, 250 mmol) was dissolved in 500 ml toluene, and 2-bromo-6-pentylnaphthalene (C28, 55.44 g, 200 mmol) was added at room temperature. After the addition was completed, 11.31 g (12.5 mmol) of Bretphos Pd G3, 11.67 g (25 mmol) of Ruphos and 60.06 g (625 mmol) of tBuONa were added. Stirring was continued at 110 ° C for 2 h under nitrogen atmosphere until the reaction was complete, filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and 36.47 g of 6-pentyl-N-phenylnaphthalene-2-amine (II-28) was obtained by dichloromethane / petroleum ether column chromatography. 1 H NMR(500MHz,Chloroform-d)δ7.74(dd,J=8.3,2.0Hz,1H),7.68(dd,J=8.2,2.3Hz,1H),7.45(t,J=2.2Hz,1H),7.26–7.14(m,6H),7. 07–7.01(m,2H),6.88(tt,J=6.8,1.1Hz,1H),2.59(t,J=7.7Hz,2H),1.58(p,J=7.5Hz,2H),1.43–1.27(m,5H),0.89(t,J=6.7Hz,3H).

[0201] 6-Pentyl-N-phenylnaphthalene-2-amine (II-28, 28.94 g, 100 mmol) and 1-bromo-4-nitrobenzene (III, 24.11 g, 120 mmol) were reacted in 0.35 g (0.5 mmol) Pd(amphos)Cl2, 19.22 g (200 mmol) tBuONa and 250 ml toluene at 110°C for 4 h, filtered, washed three times with water, extracted three times with dichloromethane, dried over anhydrous sodium sulfate, concentrated, and chromatographed on a dichloromethane / petroleum ether column to obtain 29.53 g N-(4-nitrophenyl)-6-pentyl-N-phenylnaphthalene-2-amine (IV-28). 1 H NMR(500MHz,Chloroform-d)δ8.16–8.10(m,2H),7.69(ddd,J=8.0,5.7,2.1Hz,2 H),7.42(t,J=2.1Hz,1H),7.38(t,J=2.3Hz,1H),7.39–7.34(m,2H),7.32–7.25( m,2H),7.25–7.17(m,2H),7.14–7.08(m,2H),7.04(tt,J=7.7,1.4Hz,1H),2.59( t,J=7.7Hz,2H),1.58(p,J=7.5Hz,2H),1.43–1.27(m,4H),0.89(t,J=6.7Hz,3H).

[0202] N-(4-nitrophenyl)-6-pentyl-N-phenylnaphthalen-2-amine (IV-28, 20.51 g, 50 mmol) was reduced with hydrogen and 1 g Pd / C in tetrahydrofuran for 3 h. Filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 17.68 g N 1 -(6-pentylnaphth-2-yl)-N 1- Phenylbenzene-1,4-diamine (V-28). 1H NMR(500MHz,Chloroform-d)δ7.69(ddd,J=8.0,5.7,2.1Hz,2H),7.42(t,J=2.1Hz,1 H),7.38(t,J=2.3Hz,1H),7.32–7.25(m,2H),7.25–7.17(m,2H),7.14–7.08(m,2H),7 .08–7.00(m,3H),6.71–6.65(m,2H),3.99(d,J=5.7Hz,1H),3.94(d,J=5.7Hz,1H),2. 59(t,J=7.7Hz,2H),1.58(p,J=7.5Hz,2H),1.43–1.27(m,5H),0.89(t,J=6.7Hz,3H).

[0203] N 1 -(6-pentylnaphth-2-yl)-N 1- Phenylbenzene-1,4-diamine (V-28, 11.41 g, 30 mmol) was dissolved in 2.0 mol / L hydrochloric acid aqueous solution, 2.21 g (7.5 mmol) potassium dichromate was dissolved in 2.0 mol / L hydrochloric acid aqueous solution, the potassium dichromate solution was added dropwise to the hydrochloric acid aniline solution using a dropping funnel, and the mixture was reacted at room temperature for 2 hours. After the reaction was completed, the mixture was cooled to room temperature, poured into 500 mL of methanol, filtered to obtain a crude product, and then washed with hydrochloric acid aqueous solution until the filtrate was colorless, poured into 500 mL of methanol, filtered, and the filter cake was extracted with methanol, acetone, n-hexane and chloroform in turn, and vacuum dried to obtain the target polymer (P-28) 1 H NMR(500MHz,Chloroform-d)δ7.69(ddd,J=8.0,5.7,2.1Hz,2H),7.42(d,J=2.1Hz,1H),7. 38(t,J=2.5Hz,1H),7.26–7.17(m,2H),7.10–7.03(m,4H),7.07–6.99(m,2H),6.69–6.64( m, 2H), 5.73 (q, J = 4.8 Hz, 1H), 2.91 (d, J = 4.8 Hz, 3H), 2.59 (t, J = 7.7 Hz, 2H), 2.35 (s, 3H), 1.58 (p, J = 7.5 Hz, 2H), 1.43–1.27 (m, 5H), 0.89 (t, J = 6.7 Hz, 3H). The molecular weight of the polymer obtained by GPC test was 29870.

[0204] Example 29 Synthesis of Representative Conductive Polymer Material P-29 Containing N-phenyl-1,4-phenylenediamine

[0205]

[0206] Aniline (I, 23.26 g, 250 mmol) was dissolved in 500 ml toluene, and 2-bromo-6-butoxynaphthalene (C29, 55.84 g, 200 mmol) was added at room temperature. After the addition was completed, 11.31 g (12.5 mmol) of Bretphos Pd G3, 11.67 g (25 mmol) of Ruphos and 60.06 g (625 mmol) of tBuONa were added. Stirring was continued at 110 ° C for 2 h under nitrogen atmosphere until the reaction was complete, filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and 40.21 g of 6-butoxy-N-phenylnaphthalene-2-amine (II-29) was obtained by column chromatography with dichloromethane / petroleum ether. 1 H NMR(500MHz,Chloroform-d)δ7.72(ddd,J=7.7,7.0,2.0Hz,2H),7.24–7.16(m,4H),7.11(dt,J=2.4,1.2Hz,1H),7.07–7.01(m,2H),6.98–6.93(m,1H) ,6.92(t,J=2.2Hz,1H),6.88(tt,J=6.9,1.1Hz,1H),4.02(t,J=6.4Hz,2H), 1.78(p,J=6.7Hz,2H), 1.48(dt,J=13.9,6.9Hz,2H), 0.98(t,J=7.0Hz,3H).

[0207] 6-Butoxy-N-phenylnaphthalene-2-amine (II-29, 29.14 g, 100 mmol) and 1-bromo-4-nitrobenzene (III, 24.11 g, 120 mmol) were reacted in 0.35 g (0.5 mmol) Pd(amphos)Cl2, 19.22 g (200 mmol) tBuONa and 250 ml toluene at 110°C for 4 h, filtered, washed three times with water, extracted three times with dichloromethane, dried over anhydrous sodium sulfate, concentrated, and chromatographed on a dichloromethane / petroleum ether column to obtain 30.09 g 6-butoxy-N-(4-nitrophenyl)-N-phenylnaphthalene-2-amine (IV-29). 1H NMR(500MHz,Chloroform-d)δ8.16–8.10(m,2H),7.73(dd,J=8.4,2.4Hz,1H),7.66(dd,J=7. 4,2.0Hz,1H),7.39–7.34(m,3H),7.32–7.26(m,2H),7.24(dd,J=7.5,2.2Hz,1H),7.14–7.08( m,2H),7.04(tt,J=7.7,1.4Hz,1H),6.95(dd,J=8.4,2.4Hz,1H),6.91(t,J=2.2Hz,1H),4.02 (t,J=6.4Hz,2H),1.78(p,J=6.7Hz,2H),1.48(dt,J=13.9,6.9Hz,2H),0.98(t,J=7.0Hz,3H).

[0208] 6-Butoxy-N-(4-nitrophenyl)-N-phenylnaphthalen-2-amine (IV-29, 20.61 g, 50 mmol) was reduced with hydrogen and 1 g Pd / C in tetrahydrofuran for 3 h. Filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 18.36 g N 1 -(6-Butyloxynaphthalen-2-yl)-N 1 -phenylbenzene-1,4-diamine (V-29). 1 H NMR(500MHz,Chloroform-d)δ7.73(dd,J=8.4,2.4Hz,1H),7.66(dd,J=7.4,2.0Hz,1H),7.36(t,J=2.4 Hz,1H),7.32–7.26(m,2H),7.24(dd,J=7.5,2.2Hz,1H),7.14–7.08(m,2H),7.08–7.00(m,3H),6.95(dd ,J=8.4,2.4Hz,1H),6.91(t,J=2.2Hz,1H),6.71–6.65(m,2H),4.02(t,J=6.4Hz,2H),3.99(d,J=5.7Hz, 1H), 3.94 (d, J = 5.7Hz, 1H), 1.78 (p, J = 6.7Hz, 2H), 1.48 (dt, J = 13.9, 6.9Hz, 2H), 0.98 (t, J = 7.0Hz, 3H).

[0209] N 1 -(6-Butyloxynaphthalen-2-yl)-N 1-phenylbenzene-1,4-diamine (V-29, 11.48 g, 30 mmol) was dissolved in 2.0 mol / L hydrochloric acid aqueous solution, 2.21 g (7.5 mmol) potassium dichromate was dissolved in 2.0 mol / L hydrochloric acid aqueous solution, the potassium dichromate solution was added dropwise to the hydrochloric acid aniline solution using a dropping funnel, and the mixture was reacted at room temperature for 2 h. After the reaction was completed, the mixture was cooled to room temperature, poured into 500 mL of methanol, filtered to obtain a crude product, and then washed with hydrochloric acid aqueous solution until the filtrate was colorless, poured into 500 mL of methanol, filtered, and the filter cake was extracted with methanol, acetone, n-hexane and chloroform in turn, and vacuum dried to obtain the target polymer (P-29) 1 H NMR(500MHz,Chloroform-d)δ7.73(dd,J=8.4,2.3Hz,1H),7.66(dd,J=7.4,2.0Hz,1H),7.36(t,J=2.4Hz, 1H),7.24(dd,J=7.5,2.2Hz,1H),7.10–6.99(m,6H),6.95(dd,J=8.4,2.4Hz,1H),6.91(t,J=2.1Hz,1H),6 .69–6.64 (m, 2H), 5.73 (q, J = 4.8 Hz, 1H), 4.02 (t, J = 6.4 Hz, 2H), 2.91 (d, J = 4.8 Hz, 3H), 2.35 (d, J = 0.8 Hz, 3H), 1.78 (p, J = 6.7 Hz, 2H), 1.48 (dt, J = 13.9, 6.9 Hz, 2H), 0.98 (t, J = 7.0 Hz, 3H). The molecular weight of the polymer obtained by GPC test was 46981.

[0210] Example 30 Synthesis of Representative Conductive Polymer Material P-30 Containing N-Phenyl-1,4-Phenylenediamine

[0211]

[0212] Aniline (I, 23.26 g, 250 mmol) was dissolved in 500 ml toluene. At room temperature, 2-bromo-6-(2-methoxyethoxy)naphthalene (C30, 56.23 g, 200 mmol) was added. After addition, 11.31 g (12.5 mmol) of Breetphos Pd G3, 11.67 g (25 mmol) of Ruphos and 60.06 g (625 mmol) of tBuONa were added. Stirring was continued at 110° C. for 2 h under nitrogen atmosphere until the reaction was complete. The mixture was filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and 40.24 g of 6-(2-methoxyethoxy)-N-phenylnaphthalene-2-amine (II-30) was obtained by column chromatography with dichloromethane / petroleum ether. 1H NMR(500MHz,Chloroform-d)δ7.72(ddd,J=7.8,7.0,2.0Hz,2H),7.24–7.16(m,3H),7.14–7.09(m,1H),7.07–7.01(m,2H),6.96(dd,J =8.3, 2.4Hz, 1H), 6.92 (dd, J = 2.5, 1.8Hz, 1H), 6.88 (tt, J = 6.9, 1.1Hz, 1H), 4.19 (t, J = 4.9Hz, 2H), 3.54 (t, J = 4.9Hz, 2H), 3.37 (s, 2H).

[0213] 6-(2-Methoxyethoxy)-N-phenylnaphthalene-2-amine (II-30, 29.34 g, 100 mmol) and 1-bromo-4-nitrobenzene (III, 24.11 g, 120 mmol) were reacted in 0.35 g (0.5 mmol) Pd(amphos)Cl2, 19.22 g (200 mmol) tBuONa and 250 ml toluene at 110°C for 4 h, filtered, washed three times with water, extracted three times with dichloromethane, dried over anhydrous sodium sulfate, concentrated, and chromatographed on a dichloromethane / petroleum ether column to obtain 28.60 g 6-(2-methoxyethoxy)-N-(4-nitrophenyl)-N-phenylnaphthalene-2-amine (IV-30). 1 H NMR(500MHz,Chloroform-d)δ8.16–8.10(m,2H),7.73(dd,J=8.3,2.3Hz,1H),7.66( dd,J=7.4,1.9Hz,1H),7.39–7.34(m,3H),7.32–7.26(m,2H),7.24(dd,J=7.5,2.2Hz, 1H),7.14–7.08(m,2H),7.04(tt,J=7.7,1.4Hz,1H),6.96(dd,J=8.2,2.4Hz,1H),6. 92(dd,J=2.4,1.6Hz,1H),4.19(t,J=4.9Hz,2H),3.54(t,J=4.9Hz,2H),3.37(s,2H).

[0214] 6-(2-methoxyethoxy)-N-(4-nitrophenyl)-N-phenylnaphthalen-2-amine (IV-30, 20.72 g, 50 mmol) was reduced with hydrogen and 1 g Pd / C in tetrahydrofuran for 3 h. Filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 17.88 g N 1 -(6-(2-methoxyethoxy)naphthalen-2-yl)-N 1 -phenylbenzene-1,4-diamine (V-30).1 H NMR(500MHz,Chloroform-d)δ7.73(dd,J=8.4,2.4Hz,1H),7.66(dd,J=7.4,2.0Hz,1H),7.36(t,J =2.4Hz,1H),7.32–7.26(m,2H),7.24(dd,J=7.5,2.2Hz,1H),7.14–7.08(m,2H),7.07(s,1H),7.07 –7.00(m,2H),6.96(dd,J=8.2,2.4Hz,1H),6.92(dd,J=2.4,1.6Hz,1H),6.71–6.65(m,2H),4.19( t,J=4.9Hz,2H),3.99(d,J=5.7Hz,1H),3.94(d,J=5.7Hz,1H),3.54(t,J=4.9Hz,2H),3.37(s,2H).

[0215] N 1 -(6-(2-methoxyethoxy)naphthalen-2-yl)-N 1 -phenylbenzene-1,4-diamine (V-30, 11.53 g, 30 mmol) was dissolved in 2.0 mol / L hydrochloric acid aqueous solution, 2.21 g (7.5 mmol) potassium dichromate was dissolved in 2.0 mol / L hydrochloric acid aqueous solution, the potassium dichromate solution was added dropwise to the hydrochloric acid aniline solution using a dropping funnel, and the mixture was reacted at room temperature for 2 h. After the reaction was completed, the mixture was cooled to room temperature, poured into 500 mL of methanol, filtered to obtain a crude product, and then washed with hydrochloric acid aqueous solution until the filtrate was colorless, poured into 500 mL of methanol, filtered, and the filter cake was extracted with methanol, acetone, n-hexane and chloroform in turn, and vacuum dried to obtain the target polymer (P-30) 1 H NMR(500MHz,Chloroform-d)δ7.73(dd,J=8.3,2.3Hz,1H),7.66(dd,J=7.4,2.0Hz,1H),7.36(t ,J=2.4Hz,1H),7.24(dd,J=7.5,2.2Hz,1H),7.10–6.99(m,6H),6.96(dd,J=8.3,2.4Hz,1H),6. 92 (dd, J = 2.5, 1.6 Hz, 1H), 6.69–6.64 (m, 2H), 5.73 (q, J = 4.8 Hz, 1H), 4.19 (t, J = 4.9 Hz, 2H), 3.54 (t, J = 4.9 Hz, 2H), 3.37 (s, 2H), 2.91 (d, J = 4.8 Hz, 3H), 2.35 (s, 3H). The molecular weight of the polymer obtained by GPC test was 37801.

[0216] Example 31 Synthesis of Representative Conductive Polymer Material P-31 Containing N-phenyl-1,4-phenylenediamine

[0217]

[0218] Aniline (I, 23.26 g, 250 mmol) was dissolved in 500 ml of toluene. At room temperature, 3-bromo-6-undecylthiophene [3, 2-b] thiophene (C31, 74.68 g, 200 mmol) was added. After the addition was completed, 11.31 g (12.5 mmol) of Breetphos Pd G3, 11.67 g (25 mmol) of Ruphos and 60.06 g (625 mmol) of tBuONa were added. Stirring was continued at 110 ° C for 2 h under nitrogen atmosphere until the reaction was complete. The mixture was filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and 58.26 g of N-phenyl-6-undecylthiophene [3, 2-b] thiophene-3-amine (II-31) was obtained by column chromatography with dichloromethane / petroleum ether. 1 H NMR(500MHz,Chloroform-d)δ7.38(s,1H),7.24–7.16(m,3H),6.99(s,1H),6.88(tt,J=6.9,1.2Hz,1H),6.79(dd,J=7.7,1.2Hz,2 H),2.69(t,J=7.5Hz,2H),1.57(q,J=7.4Hz,2H),1.38–1.29(m,3H),1.33–1.25(m,8H),1.27(t,J=1.0Hz,6H),0.94–0.85(m,3H).

[0219] N-phenyl-6-undecylthiophene[3,2-b]thiophene-3-amine (II-31, 38.56 g, 100 mmol) and 1-bromo-4-nitrobenzene (III, 24.11 g, 120 mmol) were reacted in 0.35 g (0.5 mmol) Pd(amphos)Cl2, 19.22 g (200 mmol) tBuONa and 250 ml toluene at 110 ° C for 4 hours, filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 35.98 g N-(4-nitrophenyl)-N-phenyl-6-undecylthiophene[3,2-b]thiophene-3-amine (IV-31). 1H NMR(500MHz,Chloroform-d)δ8.16–8.10(m,2H),7.47–7.41(m,2H),7.39(s,1H),7.32–7.25(m,2H),7.21(s,1H),7.14–7.08(m,2H), 7.04(tt,J=7.7,1.4Hz,1H),2.69(t,J=7.5Hz,2H),1.57(q,J=7.4Hz,2H),1.38–1.29(m,4H),1.32–1.24(m,12H),0.94–0.85(m,3H).

[0220] N-(4-nitrophenyl)-N-phenyl-6-undecylthieno[3,2-b]thiophene-3-amine (Ⅳ-31, 25.34 g, 50 mmol) was reduced with hydrogen and 1 g Pd / C in tetrahydrofuran for 3 h. Filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 22.65 g N 1 -phenyl-N 1 -(6-Undecylthieno[3,2-b]thiophen-3-yl)benzene-1,4-diamine (V-31). 1 H NMR(500MHz,Chloroform-d)δ7.39(s,1H),7.32–7.25(m,2H),7.21(s,1H),7.16–7.08(m,4H),7.04(tt,J=7.7,1.4Hz,1H),6.71–6.65(m,2H),3.9 9(d,J=5.6Hz,1H),3.94(d,J=5.7Hz,1H),2.69(t,J=7.5Hz,2H),1.57(q, J=7.4Hz,2H),1.38–1.29(m,4H),1.32–1.24(m,12H),0.94–0.85(m,3H).

[0221] N 1 -phenyl-N 1-(6-Undecylthieno[3,2-b]thiophene-3-yl)benzene-1,4-diamine (V-31, 14.30 g, 30 mmol) was dissolved in 2.0 mol / L hydrochloric acid aqueous solution, 2.21 g (7.5 mmol) potassium dichromate was dissolved in 2.0 mol / L hydrochloric acid aqueous solution, the potassium dichromate solution was added dropwise to the hydrochloric acid aniline solution using a dropping funnel, and the mixture was reacted at room temperature for 2 hours. After the reaction was completed, the mixture was cooled to room temperature, poured into 500 mL of methanol, filtered to obtain a crude product, and then washed with hydrochloric acid aqueous solution until the filtrate was colorless, poured into 500 mL of methanol, filtered, and the filter cake was extracted with methanol, acetone, n-hexane and chloroform in turn, and vacuum dried to obtain the target polymer (P-31) 1 H NMR (500 MHz, Chloroform-d) δ7.39 (s, 1H), 7.21 (s, 1H), 7.17–7.11 (m, 2H), 7.09–7.01 (m, 4H), 6.69–6.64 (m, 2H), 5.73 (q, J=4.8 Hz, 1H), 2.91 (d, J=4.8 Hz, 3H), 2.69 (t, J=7.5 Hz, 2H), 1.58 (p, J=7.4 Hz, 2H), 1.38–1.24 (m, 16H), 0.94–0.85 (m, 3H). The molecular weight of the polymer measured by GPC was 38704.

[0222] Example 32 Synthesis of Representative N-phenyl-1,4-phenylenediamine-containing Conductive Polymer Material P-32

[0223]

[0224] Aniline (I, 23.26 g, 250 mmol) was dissolved in 500 ml of toluene. At room temperature, 3-bromo-6-(decyloxy)thieno[3,2-b]thiophene (C32, 75.08 g, 200 mmol) was added. After the addition was completed, 11.31 g (12.5 mmol) of BreetphosPd G3, 11.67 g (25 mmol) of Ruphos and 60.06 g (625 mmol) of tBuONa were added. Stirring was continued at 110 ° C for 2 h under nitrogen atmosphere until the reaction was complete. The mixture was filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and 53.12 g of 6-(decyloxy)-N-phenylthiophene[3,2-b]thiophene-3-amine (II-32) was obtained by column chromatography with dichloromethane / petroleum ether. 1H NMR(500MHz,Chloroform-d)δ7.36(s,1H),7.24–7.17(m,2H),7.04(s,1H),6.88(tt,J=6.8,1.2Hz,1H),6.82–6.76(m, 2H),6.49(s,1H),4.00(t,J=6.1Hz,2H),1.82–1.73(m,2H),1.48–1.39(m,2H),1.35–1.23(m,13H),0.94–0.85(m,3H).

[0225] 6-(Decyloxy)-N-phenylthiophene[3,2-b]thiophene-3-amine (II-32, 38.76 g, 100 mmol) and 1-bromo-4-nitrobenzene (III, 24.11 g, 120 mmol) were reacted in 0.35 g (0.5 mmol) Pd(amphos)Cl2, 19.22 g (200 mmol) tBuONa and 250 ml toluene at 110 ° C for 4 hours, filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed on a dichloromethane / petroleum ether column to obtain 38.66 g 6-(decyloxy)-N-(4-nitrophenyl)-N-phenylthiophene[3,2-b]thiophene-3-amine (IV-32). 1 H NMR(500MHz,Chloroform-d)δ8.16–8.10(m,2H),7.47–7.41(m,3H),7.32–7.25(m,2H),7.14–7.08(m,2H),7.04(tt,J=7.7,1 .4Hz,1H),6.56(s,1H),4.00(t,J=6.0Hz,2H),1.82–1.73(m,1H),1.48–1.39(m,2H),1.35–1.23(m,13H),0.94–0.85(m,3H).

[0226] 6-(Decyloxy)-N-(4-nitrophenyl)-N-benzothieno[3,2-b]thiophene-3-amine (Ⅳ-32, 25.44 g, 50 mmol) was reduced with hydrogen and 1 g Pd / C in tetrahydrofuran for 3 h. Filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 22.24 g N 1 -(6-(Decyloxy)thieno[3,2-b]thiophen-3-yl)-N 1 -phenylbenzene-1,4-diamine (V-32). 1H NMR(500MHz,Chloroform-d)δ7.42(s,1H),7.32–7.25(m,2H),7.16–7.08(m,4H),7.04(tt,J=7.7,1.4Hz,1H),6.71–6.65(m,2H),6.56( s,1H),4.03–3.97(m,3H),3.94(d,J=5.7Hz,1H),1.77(tt,J=7.4,6.0Hz,2H),1.47–1.39(m,2H),1.35–1.23(m,12H),0.92–0.86(m,3H).

[0227] N 1 -(6-(Decyloxy)thieno[3,2-b]thiophen-3-yl)-N 1 -phenylbenzene-1,4-diamine (V-32, 14.35g, 30mmol) was dissolved in 2.0mol / L hydrochloric acid aqueous solution, 2.21g (7.5mmol) potassium dichromate was dissolved in 2.0mol / L hydrochloric acid aqueous solution, and the potassium dichromate solution was added dropwise to the hydrochloric acid aniline solution using a dropping funnel, and the mixture was reacted at room temperature for 2h. After the reaction was completed, the mixture was cooled to room temperature, poured into 500mL methanol, filtered to obtain a crude product, and then washed with hydrochloric acid aqueous solution until the filtrate was colorless, and then poured into 500mL methanol, filtered, and the filter cake was extracted with methanol, acetone, n-hexane and chloroform in turn, and vacuum dried to obtain the target polymer (P-32) 1 H NMR (500 MHz, Chloroform-d) δ7.42 (s, 1H), 7.17–7.11 (m, 2H), 7.09–7.01 (m, 4H), 6.69–6.64 (m, 2H), 6.56 (s, 1H), 5.73 (q, J = 4.8 Hz, 1H), 4.00 (t, J = 6.0 Hz, 2H), 2.91 (d, J = 4.8 Hz, 3H), 1.77 (tt, J = 7.4, 6.0 Hz, 2H), 1.48–1.39 (m, 2H), 1.35–1.23 (m, 12H), 0.94–0.85 (m, 3H). The molecular weight of the polymer measured by GPC was 38019.

[0228] Example 33 Synthesis of Representative N-phenyl-1,4-phenylenediamine-containing Conductive Polymer Material P-33

[0229]

[0230] Aniline (I, 23.26 g, 250 mmol) was dissolved in 500 ml of toluene. At room temperature, 3-bromo-6-(2-(2-(2-)methoxyethoxy)ethoxy)thieno[3,2-b]thiophene (C33, 76.26 g, 200 mmol) was added. After the addition was complete, 11.31 g (12.5 mmol) of Breetphos Pd G3, 11.67 g (25 mmol) of Ruphos and 60.06 g (625 mmol) of tBuONa were added. The mixture was stirred at 110 °C for 2 h under a nitrogen atmosphere until the reaction was complete, filtered, washed three times with water, extracted three times with dichloromethane, dried over anhydrous sodium sulfate, concentrated, and chromatographed by dichloromethane / petroleum ether column to obtain 51.69 g of 6-(2-(2-(2-methoxyethoxy)ethoxy)-N-phenylthieno[3,2-b]thiophene-3-amine (II-33). 1 H NMR(500MHz,Chloroform-d)δ7.36(s,1H),7.24–7.17(m,2H),7.04(s,1H),6.88(tt,J=6.8,1.2Hz,1H),6.82–6.76(m,2H),6.48 (s,1H),4.23(t,J=4.9Hz,2H),3.77(t,J=4.9Hz,2H),3.68–3.61(m,3H),3.62(d,J=1.2Hz,1H),3.64–3.55(m,4H),3.37(s,2H).

[0231] 6-(2-(2-(2-)2-methoxyethoxy)ethoxy)-N-phenylthieno[3,2-b]thiophene-3-amine (II-33, 39.35 g, 100 mmol) and 1-bromo-4-nitrobenzene (III, 24.11 g, 120 mmol) were reacted in 0.35 g (0.5 mmol) Pd(amphos)Cl2, 19.22 g (200 mmol) tBuONa and 250 ml toluene at 110 ° C for 4 h, filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed on a dichloromethane / petroleum ether column to obtain 37.05 g 6-(2-(2-(2-)methoxyethoxy)ethoxy)-N-(4-nitrophenyl)-N-phenylthieno[3,2-b]thiophene-3-amine (IV-33). 1HNMR(500MHz,Chloroform-d)δ8.16–8.10(m,1H),7.47–7.41(m,1H),7.32–7.25(m,1H),7.14–7.08(m,1H),7.04(tt ,J=7.7,1.4Hz,0H),4.23(t,J=4.9Hz,1H),3.77(t,J=4.9Hz,1H),3.68–3.59(m,3H),3.60–3.55(m,1H),3.37(s,1H).

[0232] 6-(2-(2-(2-)methoxyethoxy)ethoxy)-N-(4-nitrophenyl)-N-thiophen[3,2-b]thiophene-3-amine (Ⅳ-33, 25.73 g, 50 mmol) was reduced with hydrogen and 1 g Pd / C in tetrahydrofuran for 3 h. Filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 22.54 g N 1 -(6-(2-(2-(2-)2-methoxyethoxy)ethoxy)ethoxy)thiothio[3,2-b]thiophen-3-yl)-N 1 -phenylbenzene-1,4-diamine (V-33). 1 H NMR(500MHz,Chloroform-d)δ7.32–7.25(m,1H),7.16–7.08(m,2H),7.04(tt,J=7.7,1.4Hz,1H),6.71–6.65(m,1H),4.2 3(t,J=4.9Hz,1H),3.99(d,J=5.7Hz,0H),3.94(d,J=5.7Hz,0H),3.77(t,J=4.9Hz,1H),3.68–3.55(m,4H),3.37(s,1H).

[0233] N 1 -(6-(2-(2-(2-)2-methoxyethoxy)ethoxy)ethoxy)thiothio[3,2-b]thiophen-3-yl)-N 1 -phenylbenzene-1,4-diamine (V-33, 14.54 g, 30 mmol) was dissolved in 2.0 mol / L hydrochloric acid aqueous solution, 2.21 g (7.5 mmol) potassium dichromate was dissolved in 2.0 mol / L hydrochloric acid aqueous solution, the potassium dichromate solution was added dropwise to the hydrochloric acid aniline solution using a dropping funnel, and the mixture was reacted at room temperature for 2 h. After the reaction was completed, the mixture was cooled to room temperature, poured into 500 mL of methanol, filtered to obtain a crude product, and then washed with hydrochloric acid aqueous solution until the filtrate was colorless, poured into 500 mL of methanol, filtered, and the filter cake was extracted with methanol, acetone, n-hexane and chloroform in turn, and vacuum dried to obtain the target polymer (P-33)1 H NMR (500 MHz, Chloroform-d) δ7.42 (s, 1H), 7.17–7.11 (m, 2H), 7.09–7.01 (m, 4H), 6.69–6.64 (m, 2H), 6.56 (s, 1H), 5.73 (q, J = 4.8 Hz, 1H), 4.23 (t, J = 4.9 Hz, 2H), 3.77 (t, J = 4.9 Hz, 2H), 3.68–3.62 (m, 2H), 3.65–3.55 (m, 6H), 3.37 (s, 2H), 2.91 (d, J = 4.8 Hz, 3H). The molecular weight of the polymer measured by GPC was 40761.

[0234] Example 34 Synthesis of Representative N-phenyl-1,4-phenylenediamine-containing Conductive Polymer Material P-34

[0235]

[0236] Aniline (I, 23.26 g, 250 mmol) was dissolved in 500 ml of toluene. At room temperature, 2-bromo-7-octyl-9H-carbazole (C34, 71.66 g, 200 mmol) was added. After the addition was completed, 11.31 g (12.5 mmol) of Breetphos Pd G3, 11.67 g (25 mmol) of Ruphos and 60.06 g (625 mmol) of tBuONa were added. Stirring was continued at 110° C. for 2 h under nitrogen atmosphere until the reaction was complete. The mixture was filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and 51.13 g of 7-octyl-N-phenyl-9H-carbazole-2-amine (II-34) was obtained by column chromatography with dichloromethane / petroleum ether. 1 H NMR (500MHz, Chloroform-d) δ9.44 (s, 1H), 8.15 (d, J = 8.0 Hz, 1H), 7.85 (d, J = 8. 2Hz,1H),7.28(d,J=2.2Hz,1H),7.24(dd,J=8.2,2.3Hz,1H),7.24–7.17(m,2H) ,7.20–7.15(m,2H),7.04(dt,J=8.0,1.3Hz,3H),6.88(tt,J=6.8,1.1Hz,1H),2 .98–2.82(m,2H),1.56(q,J=7.8Hz,2H),1.36–1.23(m,10H),0.94–0.85(m,3H).

[0237] 7-Octyl-N-phenyl-9H-carbazole-2-amine (II-34, 37.05 g, 100 mmol) and 1-bromo-4-nitrobenzene (III, 24.11 g, 120 mmol) were reacted in 0.35 g (0.5 mmol) Pd(amphos)Cl2, 19.22 g (200 mmol) tBuONa and 250 ml toluene at 110 ° C for 4 hours, filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed on a dichloromethane / petroleum ether column to obtain 33.56 g N-(4-nitrophenyl)-7-octyl-N-phenyl-9H-carbazole-2-amine (IV-34). 1 HNMR(500MHz,Chloroform-d)δ8.16(d,J=7.5Hz,0H),8.14–8.10(m,1H),7.85(d,J=8.1Hz,0H),7.43(d,J=2.3Hz,0H),7.39–7.34(m,1H),7.32–7.2 5(m,1H),7.20–7.13(m,1H),7.13–7.08(m,1H),7.08–7.00(m,1H),2.98– 2.82(m,1H),1.56(q,J=7.8Hz,1H),1.36–1.23(m,5H),0.94–0.85(m,2H).

[0238] N-(4-nitrophenyl)-7-octyl-N-phenyl-9H-carbazole-2-amine (Ⅳ-34, 24.58 g, 50 mmol) was reduced with hydrogen and 1 g Pd / C in tetrahydrofuran for 3 h. Filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 20.29 g N 1 -(7-octyl-9H-carbazol-2-yl)-N 1 -phenylbenzene-1,4-diamine (V-34). 1 H NMR(500MHz,Chloroform-d)δ9.39(s,1H),8.16(d,J=7.5Hz,1H),7.85(d,J=8.1Hz ,1H),7.43(d,J=2.3Hz,1H),7.32–7.25(m,2H),7.20–7.13(m,2H),7.13–7.08(m,2H ),7.08–7.00(m,4H),6.71–6.65(m,2H),3.99(d,J=5.6Hz,1H),3.94(d,J=5.7Hz,1H ),2.98–2.82(m,2H),1.56(q,J=7.7Hz,2H),1.36–1.23(m,10H),0.94–0.85(m,3H).

[0239] N 1 -(7-octyl-9H-carbazol-2-yl)-N 1 -phenylbenzene-1,4-diamine (V-34, 13.85g, 30mmol) was dissolved in 2.0mol / L hydrochloric acid aqueous solution, 2.21g (7.5mmol) potassium dichromate was dissolved in 2.0mol / L hydrochloric acid aqueous solution, and the potassium dichromate solution was added dropwise to the hydrochloric acid aniline solution using a dropping funnel, and the mixture was reacted at room temperature for 2h. After the reaction was completed, the mixture was cooled to room temperature, poured into 500mL methanol, filtered to obtain a crude product, and then washed with hydrochloric acid aqueous solution until the filtrate was colorless, and then poured into 500mL methanol, filtered, and the filter cake was extracted with methanol, acetone, n-hexane and chloroform Soxhlet in turn, and vacuum dried to obtain the target polymer (P-34) 1 H NMR(500MHz,Chloroform-d)δ9.39(s,1H),8.16(d,J=7.5Hz,1H),7.85(d,J=8.0Hz, 1H),7.43(d,J=2.3Hz,1H),7.20–7.13(m,2H),7.10–6.99(m,7H),6.69–6.64(m,2H), 5.73 (q, J = 4.8 Hz, 1H), 2.98–2.88 (m, 4H), 2.87 (dt, J = 12.5, 8.1 Hz, 1H), 2.35 (s, 2H), 1.62–1.52 (m, 2H), 1.36–1.23 (m, 10H), 0.94–0.85 (m, 3H). The molecular weight of the polymer obtained by GPC test was 34098.

[0240] Example 35 Synthesis of Representative N-phenyl-1,4-phenylenediamine-containing Conductive Polymer Material P-35

[0241]

[0242] Aniline (I, 23.26 g, 250 mmol) was dissolved in 500 ml toluene. At room temperature, 2-bromo-9-octyl-9H-carbazole (C35, 71.66 g, 200 mmol) was added. After the addition was completed, 11.31 g (12.5 mmol) of Breetphos Pd G3, 11.67 g (25 mmol) of Ruphos and 60.06 g (625 mmol) of tBuONa were added. Stirring was continued at 110 ° C for 2 h under nitrogen atmosphere until the reaction was complete, filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and 52.36 g of 9-octyl-N-phenyl-9H-carbazole-2-amine (II-35) was obtained by dichloromethane / petroleum ether column chromatography. 1H NMR(500MHz,Chloroform-d)δ7.97(d,J=7.9Hz,1H),7.96–7.91(m,1H),7.42–7.36(m,1H),7.35–7.27(m,2H),7.24–7.14(m,3H),7.11(d,J=2. 0Hz,1H),7.09–7.01(m,3H),6.88(tt,J=6.8,1.1Hz,1H),4.26(t,J=5.7Hz,2H),1.84(q,J=5.9Hz,2H),1.36–1.23(m,11H),0.94–0.85(m,3H).

[0243] 9-Octyl-N-phenyl-9H-carbazole-2-amine (II-35, 37.05 g, 100 mmol) and 1-bromo-4-nitrobenzene (III, 24.11 g, 120 mmol) were reacted in 0.35 g (0.5 mmol) Pd(amphos)Cl2, 19.22 g (200 mmol) tBuONa and 250 ml toluene at 110 ° C for 4 hours, filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed on a dichloromethane / petroleum ether column to obtain 31.75 g N-(4-nitrophenyl)-9-octyl-N-phenyl-9H-carbazole-2-amine (IV-35). 1 HNMR(500MHz,Chloroform-d)δ8.16–8.10(m,2H),7.99–7.90(m,2H),7.43–7.36(m,1H),7.40–7.34(m,2H),7.34–7.25(m,4 H),7.14–7.08(m,3H),7.08–7.00(m,2H),4.26(t,J=5.8Hz,2H),1.89–1.80(m,1H),1.36–1.23(m,10H),0.94–0.85(m,3H).

[0244] N-(4-nitrophenyl)-9-octyl-N-phenyl-9H-carbazole-2-amine (Ⅳ-35, 24.58 g, 50 mmol) was reduced with hydrogen and 1 g Pd / C in tetrahydrofuran for 3 h. Filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 20.12 g N 1 -(9-octyl-9H-carbazol-2-yl)-N 1 -phenylbenzene-1,4-diamine (V-35). 1H NMR(500MHz,Chloroform-d)δ7.99–7.90(m,2H),7.43–7.36(m,1H),7.35–7.25(m,4H),7.14–7.08(m,3H),7.11–7.00(m,4H),6.71–6.65( m,2H),4.26(t,J=5.8Hz,2H),3.99(d,J=5.6Hz,1H),3.94(d,J=5.7Hz,1H),1.84(q,J=5.9Hz,2H),1.36–1.23(m,10H),0.92–0.86(m,3H).

[0245] N 1 -(9-octyl-9H-carbazol-2-yl)-N 1 -phenylbenzene-1,4-diamine (V-35, 13.85g, 30mmol) was dissolved in 2.0mol / L hydrochloric acid aqueous solution, 2.21g (7.5mmol) potassium dichromate was dissolved in 2.0mol / L hydrochloric acid aqueous solution, and the potassium dichromate solution was added dropwise to the hydrochloric acid aniline solution using a dropping funnel, and the reaction was allowed to proceed for 2h at room temperature. After the reaction was completed, the mixture was cooled to room temperature, poured into 500mL methanol, filtered to obtain a crude product, and then washed with hydrochloric acid aqueous solution until the filtrate was colorless, and then poured into 500mL methanol, filtered, and the filter cake was extracted with methanol, acetone, n-hexane and chloroform in turn, and vacuum dried to obtain the target polymer (P-35) 1 H NMR (500 MHz, Chloroform-d) δ7.99–7.90 (m, 2H), 7.42–7.36 (m, 1H), 7.35–7.27 (m, 2H), 7.13–7.03 (m, 5H), 7.06–6.99 (m, 2H), 6.69–6.64 (m, 2H), 5.73 (q, J = 4.8 Hz, 1H), 4.26 (t, J = 5.8 Hz, 2H), 2.91 (d, J = 4.8 Hz, 3H), 2.35 (s, 2H), 1.84 (p, J = 5.9 Hz, 2H), 1.36–1.23 (m, 10H), 0.94–0.85 (m, 3H). The molecular weight of the polymer measured by GPC was 37691.

[0246] Example 36 Synthesis of Representative N-phenyl-1,4-phenylenediamine-containing Conductive Polymer Material P-36

[0247]

[0248] Aniline (I, 23.26 g, 250 mmol) was dissolved in 500 ml of toluene. At room temperature, 2-bromo-9-(heptyloxy)-7-(2-(2-methoxyethoxy)ethoxy)-9H-carbazole (C36, 95.69 g, 200 mmol) was added. After the addition was completed, 11.31 g (12.5 mmol) of Breetphos Pd G3, 11.67 g (25 mmol) of Ruphos and 60.06 g (625 mmol) of tBuONa were added. Stirring was continued at 110° C. for 2 h under nitrogen atmosphere until the reaction was complete. The mixture was filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and 69.32 g of 9-(heptyloxy)-7-(2-(2-methoxyethoxy)ethoxy)-N-phenyl-9H-carbazole-2-amine (II-36) was obtained by column chromatography with dichloromethane / petroleum ether. 1 H NMR(500MHz,Chloroform-d)δ8.11(d,J=7.7Hz,1H),7.94–7.88(m,1H),7.43(d,J=2.2Hz,1H), 7.24–7.17(m,2H),7.13(dd,J=7.8,2.3Hz,1H),7.07–7.01(m,2H),6.93–6.88(m,2H),6.88(tt ,J=6.9,1.1Hz,1H),4.16(t,J=5.0Hz,2H),3.75(td,J=4.9,3.8Hz,4H),3.64–3.55(m,4H),3.3 7(s,2H),1.70(tt,J=6.7,4.8Hz,2H),1.43–1.32(m,3H),1.35–1.23(m,6H),0.94–0.85(m,3H).

[0249] 9-(Heptyloxy)-7-(2-(2-methoxyethoxy)ethoxy)-N-phenyl-9H-carbazole-2-amine (II-36, 49.06 g, 100 mmol) and 1-bromo-4-nitrobenzene (III, 24.11 g, 120 mmol) were reacted in 0.35 g (0.5 mmol) Pd(amphos)Cl2, 19.22 g (200 mmol) tBuONa and 250 ml toluene at 110°C for 4 h, filtered, washed three times with water, extracted three times with dichloromethane, dried over anhydrous sodium sulfate, concentrated, and chromatographed on a dichloromethane / petroleum ether column to obtain 42.21 g 9-(heptyloxy)-7-(2-(2-methoxyethoxy)ethoxy)-N-(4-nitrophenyl)-N-phenyl-9H-carbazole-2-amine (IV-36). 1H NMR(500MHz,Chloroform-d)δ8.15–8.10(m,3H),7.93–7.88(m,1H),7.46(d,J=2.3H z,1H),7.39–7.34(m,2H),7.32–7.25(m,2H),7.14–7.08(m,2H),7.08–7.00(m,2H),6 .93–6.88(m,2H),4.16(t,J=5.0Hz,2H),3.75(td,J=4.8,3.8Hz,4H),3.64–3.55(m, 4H),3.37(s,2H),1.70(tt,J=6.7,4.8Hz,2H),1.43–1.23(m,9H),0.94–0.85(m,3H).

[0250] 9-(Heptyloxy)-7-(2-(2-methoxyethoxy)ethoxy)-N-(4-nitrophenyl)-N-phenyl-9H-carbazole-2-amine (IV-36, 30.59 g, 50 mmol) was reduced with hydrogen and 1 g Pd / C in tetrahydrofuran for 3 h. Filtered, washed with water three times, extracted with dichloromethane three times, dried over anhydrous sodium sulfate, concentrated, and chromatographed with dichloromethane / petroleum ether to obtain 27.89 g N 1 -(9-(heptyloxy)-7-(2-(2-methoxyethoxy)ethoxy)-9H-carbazol-2-yl)-N 1 -phenylbenzene-1,4-diamine (V-36). 1 H NMR(500MHz,Chloroform-d)δ8.13(d,J=7.1Hz,1H),7.93–7.88(m,1H),7.46(d,J=2.4Hz,1H),7.32– 7.25(m,2H),7.14–7.08(m,2H),7.08–7.00(m,4H),6.93–6.88(m,2H),6.71–6.65(m,2H),4.16(t,J=5 .0Hz,2H),3.99(d,J=5.7Hz,1H),3.94(d,J=5.7Hz,1H),3.75(td,J=4.8,3.8Hz,4H),3.64–3.55(m,4H ),3.37(s,2H),1.70(tt,J=6.7,4.8Hz,2H),1.43–1.30(m,4H),1.34–1.23(m,5H),0.94–0.85(m,3H).

[0251] N 1 -(9-(heptyloxy)-7-(2-(2-methoxyethoxy)ethoxy)-9H-carbazol-2-yl)-N 1-phenylbenzene-1,4-diamine (V-36, 17.45g, 30mmol) was dissolved in 2.0mol / L hydrochloric acid aqueous solution, 2.21g (7.5mmol) potassium dichromate was dissolved in 2.0mol / L hydrochloric acid aqueous solution, and the potassium dichromate solution was added dropwise to the hydrochloric acid aniline solution using a dropping funnel, and the mixture was reacted at room temperature for 2h. After the reaction was completed, the mixture was cooled to room temperature, poured into 500mL methanol, filtered to obtain a crude product, and then washed with hydrochloric acid aqueous solution until the filtrate was colorless, and then poured into 500mL methanol, filtered, and the filter cake was extracted with methanol, acetone, n-hexane and chloroform in turn, and vacuum dried to obtain the target polymer (P-36) 1 H NMR(500MHz,Chloroform-d)δ8.13(d,J=7.1Hz,1H),7.93–7.88(m,1H),7.46(d,J=2.4Hz,1H),7.10–6.99( m,7H),6.93–6.88(m,2H),6.69–6.64(m,2H),5.73(q,J=4.8Hz,1H),4.16(t,J=5.0Hz,2H),3.75(td,J=4.8 ,3.8Hz,4H),3.64–3.55(m,4H),3.37(s,2H),2.91(d,J=4.8Hz,3H),2.35(s,2H),1.70(tt,J=6.7,4.7Hz,2H),1.43–1.35(m,2H),1.38–1.32(m,1H),1.35–1.24(m,5H),0.94–0.85(m,3H). The molecular weight of the polymer obtained by GPC test was 59871.

[0252] Example 37 Preparation of electrochromic device

[0253] The above-synthesized materials P-1 to P-36 were prepared into 50 mg / mL chloroform solution for later use.

[0254] Cut the transparent ITO conductive glass into 3cm×5cm size and soak it in a mixed solvent of ammonia / hydrogen peroxide, then ultrasonicate it in deionized water, acetone, and isopropanol in turn to obtain the cleaned ITO glass. Take it out and blow it dry with dry nitrogen for standby use. Spin coat the above-prepared P-1~P-36 solutions on an ITO by spin coating. Then glue it with another ITO, and further use the liquid filling method to fill it with propylene carbonate electrolyte solution containing 0.1mol / L tetrabutylammonium hexafluorophosphate and 0.01mol / L ethyl amethyst hexafluorophosphate, and seal it with UV glue. Apply voltage to the two poles and observe the color change of the electrochromic device. The specific results are as follows:

[0255]

[0256]

[0257] The polymer structures listed above are only partial representatives, and other electrochromic materials containing the same concept are within the scope of protection of this patent.

[0258] Although the embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations of the present invention. A person skilled in the art may change, modify, replace and vary the above embodiments within the scope of the present invention.

Claims

1. A conductive polymer material, characterized in that: The structural formula is as follows: Wherein, n is a natural number, n=1 to 100; Ar is an aromatic group.

2. The conductive polymer material according to claim 1, characterized in that The Ar substituent is selected from the following groups: Wherein, R and R' are independently selected from H, alkyl, alkoxy, and oligoether groups.

3. The conductive polymer material according to claim 1, characterized in that Selected from:

4. The method for preparing a conductive polymer material according to any one of claims 1 to 3, characterized in that: The preparation process is as follows: The specific steps include: Aniline reacts with an aryl bromide derivative (B) and is purified to obtain an intermediate compound (II); The intermediate compound (II) reacts with 1-bromo-4-nitrobenzene (III) and is purified to obtain the intermediate compound (IV); The intermediate compound (Ⅳ) is subjected to a reduction reaction with hydrogen and Pd / C in tetrahydrofuran to obtain compound (V); The compound (V) undergoes polymerization reaction under the action of a catalyst to produce the target polymer (P).

5. Use of the conductive polymer material according to any one of claims 1 to 3 in an electrochromic device.

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