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. The TPA molecule has a propeller type three-dimensional structure, and has good thermal stability and optical and electrical properties. In a TPA molecule, an N atom has a lone pair of electrons, so that the TPA easily loses one electron under electrochemical oxygen to form a single cation free radical, and the color change is accompanied; therefore, triphenylamine and derivatives thereof are commonly used as electrochromic materials. Based on the excellent performance of a triphenylamine material, the invention designs a conductive polymer for an electrochromic material, which is mainly characterized in that different side chains are connected to three para-positions of a triphenylamine nitrogen atom to form a star-shaped polymer. And thus, the material is regulated and controlled, 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 refers to the phenomenon that the optical properties (absorbance / transmittance / reflectivity) of a material undergo reversible changes through an electrochemical redox process under the action of an external voltage or current. Generally, electrochromic materials can switch between monochrome and colorless, or between two or even multiple colors; essentially, it stems from the change in the number of occupied electron states inside the material. As the core of electrochromic technology, after decades of development, the electrochromic material system has been fully expanded and improved. For example, according to the type of coloring, it can be classified as an anodic coloring material (coloring when oxidized) or a cathodic coloring material (coloring when reduced). Electrochromic materials can be divided into visible photochromic materials (wavelength 380-780nm) suitable for smart windows and indicators, and near-infrared electrochromic materials (wavelength 780-2500nm) suitable for thermal modulation technology and national defense military applications. According to the type of material, there are mainly inorganic, organic and organic-inorganic hybrid electrochromic materials. Inorganic electrochromic materials are mainly transition metal oxides, organic electrochromic materials include small molecule electrochromic materials, conjugated polymers and aromatic polymers, and organic-inorganic hybrid materials refer to metal-supramolecular polymers and metal organic frameworks (MOFs). Among them, inorganic materials have excellent long-term stability compared with organic materials; however, considering the structural diversity, flexibility and low-cost solution processability, organic electrochromic materials have more advantages. At the same time, the slow response of the switch and the single color determined by the characteristics of the inorganic materials themselves gradually appear, 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, replacing ProDot triphenylamine electrochromic materials and matching them with viologen materials can produce 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 shortcomings of electrochromic materials, the present invention provides a bismuth-containing compound, a preparation method and application.

[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] R is selected from alkyl, alkoxy, alkyl alkoxy chain, oxygen-substituted alkyl chain, oligoether group, benzyl, substituted benzyl, phenyl, substituted phenyl.

[0010] In a specific embodiment of the present invention, the Ar substituent of the conductive polymer material is as follows:

[0011]

[0012] Wherein, R' is selected from H, alkyl (C m H 2m+1 , m is a natural number of 1-20), alkoxy, oligoether

[0013] In a specific embodiment of the present invention, the conductive polymer material is selected from the following:

[0014]

[0015]

[0016]

[0017]

[0018] On the other hand, the present invention also provides a method for preparing a conductive polymer material, the preparation process is as follows:

[0019]

[0020] 3,3-disubstituted ProDot (I) reacts with tri-n-butyltin chloride and purifies to obtain an intermediate compound (II);

[0021] Tri(4-bromophenyl)amine (III) reacts with the intermediate compound (II) and purifies to obtain the intermediate compound (IV);

[0022] The intermediate compound (IV) and the aromatic dibromide derivative undergo polymerization reaction under the action of a catalyst to produce the target polymer (P).

[0023] In a specific embodiment of the present invention, 3,3-disubstituted ProDot (I) is dissolved in tetrahydrofuran (THF), and 2.0 equivalents of n-butyl lithium are added dropwise at -78°C, and stirred at room temperature for 5 minutes after the addition, and then 2.0 equivalents of tri-n-butyltin chloride are added dropwise at -78°C, and stirred at room temperature after the addition until the reaction is complete, water is added, and the product is extracted with ethyl acetate. The organic layer is washed with brine, dried over anhydrous sodium sulfate, concentrated, and column chromatography is used to obtain the intermediate compound (II);

[0024] Tri(4-bromophenyl)amine (III) and 5.0 equivalents of intermediate compound (II) were dissolved in an appropriate amount of tetrahydrofuran, 0.3 equivalents of Pd(PPh3)2Cl2 were added, and the mixture was reacted at 100°C overnight under an argon atmosphere, cooled to room temperature, the solvent was removed, and the intermediate compound (IV) was obtained by column chromatography;

[0025] The intermediate compound (IV) and 1.2 equivalents of an aromatic dibromide derivative are dissolved in an appropriate amount of dimethylacetamide, and 3.0 equivalents of potassium carbonate, 0.3 equivalents of pivalic acid and 0.02 equivalents of Pd(OAC)2 are added. The reaction is completed under a nitrogen atmosphere. After dilution, the mixture is precipitated with methanol, filtered, and the solid is vacuum dried 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 superior performance of triphenylamine materials, the present invention designs a conductive polymer for electrochromic materials, mainly by inserting different side chains at the three positions of the nitrogen atom of triphenylamine to form a star polymer. This enables the regulation of the material and achieves relatively excellent device performance. It can effectively improve the electrochromic performance in many aspects, such as response time, coloring efficiency, color change type, 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 substituted ProDot triphenylamine structure with an aromatic group or a substituted aromatic group having excellent performance to form a polymer, thereby obtaining a polymer material containing substituted ProDot triphenylamine 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: After the transparent ITO conductive glass cut into different sizes is soaked in a mixed solvent of ammonia / hydrogen peroxide for a period of time, it is ultrasonicated three times in deionized water, acetone, and isopropanol in turn to obtain the cleaned ITO glass. After taking it out, it is blown dry with dry nitrogen for standby use. The polymer sample is dissolved in toluene to make a 40mg / mL solution, and is spin-coated on an ITO. Then it is glued with another ITO, and the electrolyte solution is further poured into it by the liquid filling method. By applying voltage, its color change is observed. Its electrochromic response time and driving voltage and other performances are tested.

[0034] Example 1 Synthesis of Representative Conductive Polymer Material P-1 Containing Substituted ProDot Triphenylamine

[0035]

[0036] 3,3-Didecyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepene (IA, 43.63 g, 100 mmol) was dissolved in 200 ml of tetrahydrofuran (THF), and 12.81 g (200 mmol) of n-butyl lithium was added dropwise at -78°C, and the mixture was stirred at room temperature for 5 min after the addition was completed. Then, 65.10 g (200 mmol) of tri-n-butyltin chloride was added dropwise at -78°C, and the mixture was stirred at room temperature for 30 min after the addition was completed. Water was added, and the product was extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous sodium sulfate, and concentrated. 62.47 g of tributyl(3,3-didecyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepene-6-yl)stannane (II-A) was obtained by column chromatography. 1 H NMR(500MHz,Chloroform-d)δ1.53–1.39(m,2H),1.38–1.30(m,2H),1.33–1. 27(m,1H),1.30–1.26(m,2H),1.29–1.21(m,4H),0.89(td,J=6.8,3.4Hz,3H).

[0037] Tri(4-bromophenyl)amine (III, 2.394 g, 5 mmol) and 18.16 g (25 mmol) of tributyl(3,3-didecyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-6-yl)tinane (II-A) were dissolved in 150 ml of tetrahydrofuran, and 1.05 g (0.0015 mmol) of Pd(PPh3)2Cl2 were added. The mixture was reacted at 100°C overnight under an argon atmosphere, cooled to room temperature, and the solvent was removed. 5.64 g of tri(4-(3,3-didecyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-6-yl)phenyl)amine (IV-A) was obtained by column chromatography. 1 H NMR(500MHz,Chloroform-d)δ7.23–7.18(m,1H),7.04–6.98(m,1H),3.99(d,J=1.8H z,2H),1.46–1.39(m,2H),1.38–1.28(m,3H),1.32–1.24(m,13H),0.94–0.85(m,3H).

[0038] After multiple cumulative amounts, tri(4-(3,3-didecyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepane-6-yl)phenyl)amine (IV-A, 15.48 g, 10 mmol) and 1,4-dibromo-2,5-dioctylbenzene (C-1, 18.33 g, 40 mmol) were dissolved in 50 ml of dimethylacetamide, and 4.15 g (30 mmol) of potassium carbonate, 0.31 g (3 mmol) of pivalic acid and 0.05 g (0.2 mmol) of Pd(OAC)2 were added. The reaction was completed under a nitrogen atmosphere. After dilution, the mixture was precipitated with methanol, filtered, and the solid was vacuum dried to obtain the target polymer (P-1). 1 H NMR (500 MHz, Chloroform-d) δ7.40–7.35 (m, 1H), 7.22–7.17 (m, 1H), 4.01 (s, 1H), 2.65 (dtd, J=15.9, 8.1, 1.1 Hz, 2H), 1.65–1.52 (m, 2H), 1.43 (td, J=7.4, 1.3 Hz, 2H), 1.38–1.31 (m, 2H), 1.34–1.24 (m, 23H), 0.94–0.85 (m, 6H). The molecular weight of the polymer obtained by GPC test was 98076.

[0039] Example 2 Synthesis of Representative Conductive Polymer Material P-2 Containing Substituted ProDot Triphenylamine

[0040]

[0041] Tri(4-(3,3-didecyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-6-yl)phenyl)amine (IV-A, 15.48 g, 10 mmol) and 1,4-dibromo-2,5-bis(2-(2-methoxyethoxy)ethoxy)benzene (C-2, 18.80 g, 40 mmol) were dissolved in 50 ml of dimethylacetamide, and 4.15 g (30 mmol) of potassium carbonate, 0.31 g (3 mmol) of pivalic acid and 0.05 g (0.2 mmol) of Pd(OAC)2 were added. The reaction was completed under a nitrogen atmosphere. After dilution, the mixture was precipitated with methanol, filtered, and the solid was vacuum dried to obtain the target polymer (P-2). 1 H NMR (500 MHz, Chloroform-d) δ7.40–7.35 (m, 1H), 7.22–7.17 (m, 1H), 6.69 (s, 0H), 4.24 (t, J = 4.9 Hz, 1H), 4.16 (t, J = 4.9 Hz, 1H), 4.01 (s, 1H), 3.75 (t, J = 4.9 Hz, 1H), 3.66 (t, J = 4.9 Hz, 1H), 3.64–3.55 (m, 4H), 3.37 (s, 2H), 1.43 (td, J = 7.2, 1.2 Hz, 2H), 1.38–1.30 (m, 2H), 1.34–1.23 (m, 14H), 0.94–0.85 (m, 3H). The molecular weight of the polymer measured by GPC was 80971.

[0042] Example 3 Synthesis of Representative Conductive Polymer Material P-3 Containing Substituted ProDot Triphenylamine

[0043]

[0044] Tri(4-(3,3-didecyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-6-yl)phenyl)amine (IV-A, 15.48 g, 10 mmol) and 2,6-dibromonaphthalene (C-3, 11.37 g, 40 mmol) were dissolved in 50 ml of dimethylacetamide, and 4.15 g (30 mmol) of potassium carbonate, 0.31 g (3 mmol) of pivalic acid and 0.05 g (0.2 mmol) of Pd(OAC)2 were added. The reaction was completed under a nitrogen atmosphere. After dilution, the mixture was precipitated with methanol, filtered, and the solid was vacuum dried to obtain the target polymer (P-3). 1HNMR (500 MHz, Chloroform-d) δ7.40–7.35 (m, 1H), 7.22–7.17 (m, 1H), 4.01 (s, 1H), 1.43 (td, J=7.3, 1.2 Hz, 1H), 1.38–1.23 (m, 10H), 0.94–0.85 (m, 2H). The molecular weight of the polymer obtained by GPC test was 109872.

[0045] Example 4 Synthesis of Representative Conductive Polymer Material P-4 Containing Substituted ProDot Triphenylamine

[0046]

[0047] Tri(4-(3,3-didecyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-6-yl)phenyl)amine (IV-A, 15.48 g, 10 mmol) and 2,7-dibromo-9,9-dimethyl-9H-fluorene (C-4, 14.00 g, 40 mmol) were dissolved in 50 ml of dimethylacetamide, and 4.15 g (30 mmol) of potassium carbonate, 0.31 g (3 mmol) of pivalic acid and 0.05 g (0.2 mmol) of Pd(OAC)2 were added. The reaction was completed under a nitrogen atmosphere. After dilution, the mixture was precipitated with methanol, filtered, and the solid was vacuum dried to obtain the target polymer (P-4). 1 H NMR (500 MHz, Chloroform-d) δ7.65–7.56 (m, 1H), 7.40–7.34 (m, 1H), 7.26–7.17 (m, 2H), 4.01 (s, 1H), 2.31 (s, 1H), 1.43 (td, J=7.2, 1.2 Hz, 2H), 1.38–1.31 (m, 1H), 1.34–1.23 (m, 13H), 0.94–0.85 (m, 3H). The molecular weight of the polymer measured by GPC was 120875.

[0048] Example 5 Synthesis of Representative Conductive Polymer Material P-5 Containing Substituted ProDot Triphenylamine

[0049]

[0050] Tri(4-(3,3-didecyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-6-yl)phenyl)amine (IV-A, 15.48 g, 10 mmol) and 2,7-dibromo-9-(2-(2-methoxyethoxy)ethoxy)-9H-carbazole (C-5, 17.63 g, 40 mmol) were dissolved in 50 ml of dimethylacetamide, and 4.15 g (30 mmol) of potassium carbonate, 0.31 g (3 mmol) of pivalic acid and 0.05 g (0.2 mmol) of Pd(OAC)2 were added. The reaction was completed under a nitrogen atmosphere. After dilution, the mixture was precipitated with methanol, filtered, and the solid was vacuum dried to obtain the target polymer (P-5). 1 H NMR (500MHz, Chloroform-d) δ7.40-7.33 (m, 1H), 7.22-7.17 (m, 1H), 4.12 (t, J = 4.6 Hz, 1H), 4.01 (s, 1H), 3.67 (t, J = 4.6 Hz, 1H), 3.64-3.55 (m, 1H), 3.37 (s, 1H), 1.43 (td, J = 7.3, 1.3 Hz, 1H), 1.38-1.23 (m, 11H), 0.94-0.85 (m, 2H). The molecular weight of the polymer obtained by GPC test is 80765.

[0051] Example 6 Synthesis of Representative Conductive Polymer Material P-6 Containing Substituted ProDot Triphenylamine

[0052]

[0053] Tri(4-(3,3-didecyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-6-yl)phenyl)amine (IV-A, 15.48 g, 10 mmol) and 2,7-dibromo-9-(heptyloxy)-9H-carbazole (C-6, 17.47 g, 40 mmol) were dissolved in 50 ml of dimethylacetamide, and 4.15 g (30 mmol) of potassium carbonate, 0.31 g (3 mmol) of pivalic acid and 0.05 g (0.2 mmol) of Pd(OAC)2 were added. The reaction was completed under a nitrogen atmosphere. After dilution, the mixture was precipitated with methanol, filtered, and the solid was vacuum dried to obtain the target polymer (P-6). 1H NMR (500 MHz, Chloroform-d) δ7.40–7.32 (m, 1H), 7.22–7.17 (m, 1H), 4.01 (s, 1H), 3.75 (t, J = 4.8 Hz, 1H), 1.70 (tt, J = 6.7, 4.8 Hz, 1H), 1.43 (dd, J = 7.3, 1.3 Hz, 1H), 1.43–1.35 (m, 1H), 1.39–1.32 (m, 1H), 1.35–1.28 (m, 2H), 1.32–1.24 (m, 10H), 0.94–0.85 (m, 3H). The molecular weight of the polymer measured by GPC was 157098.

[0054] Example 7 Synthesis of Representative Conductive Polymer Material P-7 Containing Substituted ProDot Triphenylamine

[0055]

[0056] Tri(4-(3,3-didecyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepane-6-yl)phenyl)amine (IV-A, 15.48 g, 10 mmol) and 2,5-dibromo-3-(heptyloxy)thiophene (C-7, 14.17 g, 40 mmol) were dissolved in 50 ml of dimethylacetamide, and 4.15 g (30 mmol) of potassium carbonate, 0.31 g (3 mmol) of pivalic acid and 0.05 g (0.2 mmol) of Pd(OAC)2 were added. The reaction was completed under a nitrogen atmosphere. After dilution, the mixture was precipitated with methanol, filtered, and the solid was vacuum dried to obtain the target polymer (P-7). 1 H NMR (500 MHz, Chloroform-d) δ4.03–3.94 (m, 1H), 1.51–1.39 (m, 1H), 1.38–1.30 (m, 1H), 1.34–1.25 (m, 4H), 1.27 (d, J=1.0 Hz, 1H), 0.92–0.86 (m, 1H). The molecular weight of the polymer obtained by GPC test was 78051.

[0057] Example 8 Synthesis of Representative Conductive Polymer Material P-8 Containing Substituted ProDot Triphenylamine

[0058]

[0059] Tri(4-(3,3-didecyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepane-6-yl)phenyl)amine (IV-A, 15.48 g, 10 mmol) and 2,5-dibromo-3-octylthiophene (C-8, 14.07 g, 40 mmol) were dissolved in 50 ml of dimethylacetamide, and 4.15 g (30 mmol) of potassium carbonate, 0.31 g (3 mmol) of pivalic acid and 0.05 g (0.2 mmol) of Pd(OAC)2 were added. The reaction was completed under a nitrogen atmosphere. After dilution, the mixture was precipitated with methanol, filtered, and the solid was vacuum dried to obtain the target polymer (P-8). 1 H NMR (500 MHz, Chloroform-d) δ7.42–7.36 (m, 1H), 7.22–7.17 (m, 1H), 4.01 (d, J=0.7 Hz, 2H), 2.66 (t, J=7.9 Hz, 1H), 1.57 (p, J=7.6 Hz, 1H), 1.43 (td, J=7.3, 1.3 Hz, 2H), 1.38–1.24 (m, 21H), 0.94–0.85 (m, 4H). The molecular weight of the polymer measured by GPC was 119081.

[0060] Example 9 Synthesis of Representative Conductive Polymer Material P-9 Containing Substituted ProDot Triphenylamine

[0061]

[0062] Tri(4-(3,3-didecyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepane-6-yl)phenyl)amine (IV-A, 15.48 g, 10 mmol) and 2,5-dibromo-3,6-bis(heptyloxy)thieno[3,2-b]thiophene (C-9, 20.97 g, 40 mmol) were dissolved in 50 ml of dimethylacetamide, and 4.15 g (30 mmol) of potassium carbonate, 0.31 g (3 mmol) of pivalic acid and 0.05 g (0.2 mmol) of Pd(OAC)2 were added. The reaction was completed under a nitrogen atmosphere. After dilution, the mixture was precipitated with methanol, filtered, and the solid was vacuum dried to obtain the target polymer (P-9). 1H NMR (500 MHz, Chloroform-d) δ7.42–7.36 (m, 1H), 7.22–7.17 (m, 1H), 4.07–3.99 (m, 4H), 1.82 (tt, J=7.5, 6.0 Hz, 2H), 1.51–1.39 (m, 4H), 1.38–1.32 (m, 2H), 1.35–1.29 (m, 3H), 1.32–1.23 (m, 17H), 0.94–0.85 (m, 6H). The molecular weight of the polymer obtained by GPC test was 90876.

[0063] Example 10 Synthesis of Representative Conductive Polymer Material P-10 Containing Substituted ProDot Triphenylamine

[0064]

[0065] Tri(4-(3,3-didecyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepane-6-yl)phenyl)amine (IV-A, 15.48 g, 10 mmol) and 2,6-dibromo-4,8-dioctylbenzo[1,2-b:4,5-b']dithiophene (C-10, 22.80 g, 40 mmol) were dissolved in 50 ml of dimethylacetamide, and 4.15 g (30 mmol) of potassium carbonate, 0.31 g (3 mmol) of pivalic acid and 0.05 g (0.2 mmol) of Pd(OAC)2 were added. The reaction was completed under a nitrogen atmosphere. After dilution, the mixture was precipitated with methanol, filtered, and the solid was vacuum dried to obtain the target polymer (P-10). 1 H NMR (500 MHz, Chloroform-d) δ7.43–7.36 (m, 1H), 7.22–7.17 (m, 1H), 4.01 (s, 0H), 2.71 (t, J = 7.8 Hz, 1H), 1.61 (p, J = 7.5 Hz, 1H), 1.43 (td, J = 7.3, 1.3 Hz, 1H), 1.39–1.30 (m, 3H), 1.32–1.27 (m, 3H), 1.27 (td, J = 3.2, 1.1 Hz, 7H), 0.94–0.85 (m, 3H). The molecular weight of the polymer measured by GPC was 162038.

[0066] Example 11 Synthesis of Representative Conductive Polymer Material P-11 Containing Substituted ProDot Triphenylamine

[0067]

[0068] Tri(4-(3,3-didecyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-6-yl)phenyl)amine (IV-A, 15.48 g, 10 mmol) and 2,6-dibromo-4,8-bis(heptyloxy)benzo[1,2-b:4,5-b']dithiophene (C-11, 22.97 g, 40 mmol) were dissolved in 50 ml of dimethylacetamide, and 4.15 g (30 mmol) of potassium carbonate, 0.31 g (3 mmol) of pivalic acid and 0.05 g (0.2 mmol) of Pd(OAC)2 were added. The reaction was completed under a nitrogen atmosphere. After dilution, the mixture was precipitated with methanol, filtered, and the solid was vacuum dried to obtain the target polymer (P-11). 1 H NMR (500 MHz, Chloroform-d) δ7.43–7.36 (m, 1H), 7.22–7.17 (m, 0H), 4.06–3.99 (m, 2H), 1.82 (tt, J = 7.4, 6.1 Hz, 1H), 1.47 (dt, J = 8.0, 7.1 Hz, 1H), 1.46–1.39 (m, 1H), 1.38–1.33 (m, 1H), 1.32 (dt, J = 3.3, 2.0 Hz, 1H), 1.30 (ddd, J = 7.0, 2.5, 1.4 Hz, 2H), 1.30–1.23 (m, 7H), 0.94–0.85 (m, 3H). The molecular weight of the polymer measured by GPC was 176509.

[0069] Example 12 Synthesis of Representative Conductive Polymer Material P-12 Containing Substituted ProDot Triphenylamine

[0070]

[0071] Tri(4-(3,3-didecyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-6-yl)phenyl)amine (IV-A, 15.48 g, 10 mmol) and 4,7-dibromobenzo[c][1,2,5]thiadiazole (C-12, 11.67 g, 40 mmol) were dissolved in 50 ml of dimethylacetamide, and 4.15 g (30 mmol) of potassium carbonate, 0.31 g (3 mmol) of pivalic acid and 0.05 g (0.2 mmol) of Pd(OAC)2 were added. The reaction was completed under a nitrogen atmosphere. After dilution, the mixture was precipitated with methanol, filtered, and the solid was vacuum dried to obtain the target polymer (P-12). 1H NMR(500MHz,Chloroform-d)δ7.62(d,J=9.0Hz,0H),7.40–7.35(m,1H),7.21(ddt,J=8.7,7. 5,1.4Hz,2H),4.16(d,J=4.0Hz,3H),3.63(d,J=11.5Hz,1H),3.51(d,J=11.7Hz,1H),3.41(t, J=5.3Hz, 3H), 2.63(d, J=1.1Hz, 2H), 1.60–1.51(m, 2H), 1.40–1.30(m, 5H), 1.30(d, J=2.5Hz, 1H), 1.29(d, J=1.8Hz, 2H), 1.30–1.23(m, 6H), 0.94–0.85(m, 4H). The molecular weight of the polymer obtained by GPC test was 157641.

[0072] Example 13 Synthesis of Representative Conductive Polymer Material P-13 Containing Substituted ProDot Triphenylamine

[0073]

[0074] 3,3-bis((octyloxy)methyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepene (ID, 44.03 g, 100 mmol) was dissolved in 200 ml of tetrahydrofuran (THF). 12.81 g (200 mmol) of n-butyl lithium was added dropwise at -78°C. After the addition, the mixture was stirred at room temperature for 5 min. Then, 65.10 g (200 mmol) of tri-n-butyltin chloride was added dropwise at -78°C. After the addition, the mixture was stirred at room temperature for 30 min. Water was added and the product was extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous sodium sulfate, concentrated, and 58.36 g of (3,3-bis((octyloxy)methyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepene-6-yl)tributyltinane (II-D) was obtained by column chromatography. 1 H NMR(500MHz,Chloroform-d)δ4.11(s,1H),4.02(s,1H),3.63(d,J=11.5Hz,1H),3.51(d,J=11.7H z,1H),3.41(t,J=5.3Hz,2H),1.60–1.43(m,5H),1.40–1.21(m,17H),0.89(td,J=6.8,3.4Hz,7H).

[0075] Tri(4-bromophenyl)amine (III, 2.394 g, 5 mmol) and 18.26 g (25 mmol) of (3,3-bis((octyloxy)methyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-6-yl)tributyltinane (II-D) were dissolved in 150 ml of tetrahydrofuran, and 1.05 g (0.0015 mmol) of Pd(PPh3)2Cl2 were added. The mixture was reacted at 100°C overnight under an argon atmosphere, cooled to room temperature, and the solvent was removed. 5.45 g of tri(4-(3,3-bis((octyloxy)methyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-6-yl)phenyl)amine (IV-D) was obtained by column chromatography. 1 H NMR(500MHz,Chloroform-d)δ7.23–7.18(m,1H),7.04–6.98(m,1H),4.13(d,J =10.8Hz,2H),3.63(d,J=11.5Hz,1H),3.51(d,J=11.7Hz,1H),3.41(t,J=5.3Hz ,2H),1.60–1.51(m,2H),1.40–1.34(m,1H),1.36–1.31(m,1H),1.34–1.28(m, 3H),1.29(d,J=2.8Hz,3H),1.28(s,1H),1.30–1.23(m,2H),0.94–0.85(m,3H).

[0076] After multiple cumulative amounts, tri(4-(3,3-bis((octyloxy)methyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-6-yl)phenyl)amine (IV-D, 15.60 g, 10 mmol) and 1,4-dibromo-2,5-dioctylbenzene (C-13, 18.47 g, 40 mmol) were dissolved in 50 ml of dimethylacetamide, and 4.15 g (30 mmol) of potassium carbonate, 0.31 g (3 mmol) of pivalic acid and 0.05 g (0.2 mmol) of Pd(OAC)2 were added. The reaction was completed under a nitrogen atmosphere, and after dilution, the mixture was precipitated with methanol. After filtration, the solid was vacuum dried and collected to obtain the target polymer (P-13). 1H NMR (500 MHz, Chloroform-d) δ7.40–7.35 (m, 0H), 4.16 (d, J = 4.0 Hz, 1H), 3.98 (dt, J = 12.0, 6.1 Hz, 1H), 3.41 (t, J = 5.3 Hz, 1H), 1.82–1.73 (m, 1H), 1.55 (tt, J = 7.5, 5.3 Hz, 1H), 1.46 (dq, J = 7.8, 7.0 Hz, 1H), 1.40–1.32 (m, 1H), 1.35–1.29 (m, 2H), 1.29 (ddq, J = 5.5, 3.1, 1.4 Hz, 5H), 0.94–0.85 (m, 3H). The molecular weight of the polymer measured by GPC was 90879.

[0077] Example 14 Synthesis of Representative Conductive Polymer Material P-14 Containing Substituted ProDot Triphenylamine

[0078]

[0079] Tris(4-(3,3-bis((octyloxy)methyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-6-yl)phenyl)amine (IV-D, 15.60 g, 10 mmol) and 2,6-dibromonaphthalene (C-14, 11.37 g, 40 mmol) were dissolved in 50 ml of dimethylacetamide, and 4.15 g (30 mmol) of potassium carbonate, 0.31 g (3 mmol) of pivalic acid and 0.05 g (0.2 mmol) of Pd(OAC)2 were added. The reaction was completed under a nitrogen atmosphere. After dilution, the mixture was precipitated with methanol, filtered, and the solid was vacuum dried to obtain the target polymer (P-14). 1 H NMR (500 MHz, Chloroform-d) δ7.40–7.35 (m, 1H), 7.22–7.17 (m, 1H), 4.15 (s, 1H), 3.63 (d, J=11.5 Hz, 0H), 3.51 (d, J=11.7 Hz, 0H), 3.44–3.38 (m, 1H), 1.60–1.51 (m, 1H), 1.40–1.23 (m, 6H), 0.94–0.85 (m, 2H). The molecular weight of the polymer was 80998 as determined by GPC.

[0080] Example 15 Synthesis of Representative Conductive Polymer Material P-15 Containing Substituted ProDot Triphenylamine

[0081]

[0082] Tris(4-(3,3-bis((octyloxy)methyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-6-yl)phenyl)amine (IV-D, 15.60 g, 10 mmol) and 2,7-dibromo-9,9-dimethyl-9H-fluorene (C-15, 14.00 g, 40 mmol) were dissolved in 50 ml of dimethylacetamide, and 4.15 g (30 mmol) of potassium carbonate, 0.31 g (3 mmol) of pivalic acid and 0.05 g (0.2 mmol) of Pd(OAC)2 were added. The reaction was completed under a nitrogen atmosphere. After dilution, the mixture was precipitated with methanol, filtered, and the solid was vacuum dried to obtain the target polymer (P-15). 1 H NMR(500MHz,Chloroform-d)δ7.65–7.56(m,1H),7.40–7.34(m,1H),7.26–7.17(m,2H),7 .14(d,J=2.0Hz,0H),4.15(s,2H),3.63(d,J=11.5Hz,1H),3.51(d,J=11.7Hz,1H),3.41( t, J = 5.3 Hz, 2H), 2.31 (d, J = 0.8 Hz, 1H), 1.60–1.51 (m, 2H), 1.40–1.33 (m, 1H), 1.36–1.28 (m, 3H), 1.29 (tdd, J = 4.2, 2.8, 1.2 Hz, 6H), 0.94–0.85 (m, 3H). The molecular weight of the polymer obtained by GPC test was 167098.

[0083] Example 16 Synthesis of Representative Conductive Polymer Material P-16 Containing Substituted ProDot Triphenylamine

[0084]

[0085] Tris(4-(3,3-bis((octyloxy)methyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-6-yl)phenyl)amine (IV-D, 15.60 g, 10 mmol) and 2,7-dibromo-9-octyl-9H-carbazole (C-16, 17.40 g, 40 mmol) were dissolved in 50 ml of dimethylacetamide, 4.15 g (30 mmol) of potassium carbonate, 0.31 g (3 mmol) of pivalic acid and 0.05 g (0.2 mmol) of Pd(OAC)2 were added, and the reaction was completed under a nitrogen atmosphere. After dilution, the reaction was precipitated with methanol, and the solid was vacuum dried and collected after filtration to obtain the target polymer (P-16). 1H NMR (500 MHz, Chloroform-d) δ8.03 (dd, J=6.8, 1.3 Hz, 0H), 7.41–7.33 (m, 2H), 7.22–7.17 (m, 1H), 4.26 (t, J=5.7 Hz, 1H), 4.15 (s, 1H), 3.63 (d, J=11.5 Hz, 1H), 3.51 (d, J=11.7 Hz, 1H), 3.41 (t, J=5.3 Hz, 2H), 1.85 (p, J=5.9 Hz, 1H), 1.55 (tt, J=7.5, 5.3 Hz, 2H), 1.40–1.23 (m, 13H), 0.94–0.85 (m, 4H). The molecular weight of the polymer measured by GPC was 145623.

[0086] Example 17 Synthesis of Representative Conductive Polymer Material P-17 Containing Substituted ProDot Triphenylamine

[0087]

[0088] Tris(4-(3,3-bis((octyloxy)methyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-6-yl)phenyl)amine (IV-D, 15.60 g, 10 mmol) and 2,7-dibromo-9-(heptyloxy)-9H-carbazole (C-17, 16.12 g, 40 mmol) were dissolved in 50 ml of dimethylacetamide, and 4.15 g (30 mmol) of potassium carbonate, 0.31 g (3 mmol) of pivalic acid and 0.05 g (0.2 mmol) of Pd(OAC)2 were added. The reaction was completed under a nitrogen atmosphere. After dilution, the mixture was precipitated with methanol, filtered, and the solid was vacuum dried to obtain the target polymer (P-17). 1H NMR(500MHz,Chloroform-d)δ7.41–7.35(m,1H),7.38–7.32(m,1H),7.22–7.17(m,1H),7.09(ddt,J=9.7,8.0, 1.2Hz,1H),4.15(s,2H),3.75(t,J=4.8Hz,1H),3.63(d,J=11.6Hz,1H),3.51(d,J=11.7Hz,1H),3.41(t,J=5.3 Hz, 2H), 2.42(s, 1H), 1.70(tt, J=6.6,4.7Hz,1H), 1.55(tt, J=7.5,5.3Hz,2H), 1.43–1.35(m, 1H), 1.38–1.31(m, 3H), 1.31(dd, J=4.5,2.6Hz,3H), 1.28(dq, J=4.3,1.8Hz,9H), 0.94–0.85(m, 5H). The molecular weight of the polymer obtained by GPC test was 130982.

[0089] Example 18 Synthesis of Representative Conductive Polymer Material P-18 Containing Substituted ProDot Triphenylamine

[0090]

[0091] Tris(4-(3,3-bis((octyloxy)methyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-6-yl)phenyl)amine (IV-D, 15.60 g, 10 mmol) and 2,5-dibromo-3-(heptyloxy)thiophene (C-18, 14.17 g, 40 mmol) were dissolved in 50 ml of dimethylacetamide, and 4.15 g (30 mmol) of potassium carbonate, 0.31 g (3 mmol) of pivalic acid and 0.05 g (0.2 mmol) of Pd(OAC)2 were added. The reaction was completed under a nitrogen atmosphere. After dilution, the mixture was precipitated with methanol, filtered, and the solid was vacuum dried to obtain the target polymer (P-18). 1 H NMR(500MHz,Chloroform-d)δ7.42–7.36(m,1H),7.22–7.17(m,1H),4.16(d,J=4.0Hz,2H),3.97(t,J=6.1Hz,1H),3.63(d,J=11.6Hz,1H),3.51(d ,J=11.7Hz,1H),3.41(t,J=5.3Hz,2H),1.77(tt,J=7.3,6.0Hz,1H),1.60 –1.53(m,1H),1.56–1.41(m,1H),1.40–1.23(m,10H),0.94–0.85(m,3H).

[0092] The molecular weight of the polymer was 193101 as determined by GPC.

[0093] Example 19 Synthesis of Representative Conductive Polymer Material P-19 Containing Substituted ProDot Triphenylamine

[0094]

[0095] Tris(4-(3,3-bis((octyloxy)methyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-6-yl)phenyl)amine (IV-D, 15.60 g, 10 mmol) and 2,5-dibromo-3-(2-(2-methoxyethoxy)ethoxy)thiophene (C-19, 14.30 g, 40 mmol) were dissolved in 50 ml of dimethylacetamide, and 4.15 g (30 mmol) of potassium carbonate, 0.31 g (3 mmol) of pivalic acid and 0.05 g (0.2 mmol) of Pd(OAC)2 were added. The reaction was completed under a nitrogen atmosphere. After dilution, the mixture was precipitated with methanol, filtered, and the solid was vacuum dried to obtain the target polymer (P-19). 1 H NMR(500MHz,Chloroform-d)δ7.42–7.36(m,1H),7.22–7.17(m,1H),6.83(d,J=5.4Hz,0H),4. 22(t,J=5.0Hz,1H),4.16(d,J=4.0Hz,2H),3.76(t,J=4.9Hz,1H),3.66–3.55(m,2H),3.51(d, J=11.7Hz,1H),3.41(t, J=5.3Hz,2H),3.37(s,1H),2.46(d, J=0.7Hz,0H),1.55(tt, J=7.5,5.3Hz,2H),1.40–1.26(m,9H),1.29–1.23(m,1H),0.94–0.85(m,3H). The molecular weight of the polymer obtained by GPC test was 70589.

[0096] Example 20 Synthesis of Representative Conductive Polymer Material P-20 Containing Substituted ProDot Triphenylamine

[0097]

[0098] Tris(4-(3,3-bis((octyloxy)methyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-6-yl)phenyl)amine (IV-D, 15.60 g, 10 mmol) and 2,5-dibromo-3,6-dioctylthieno[3,2-b]thiophene (C-20, 20.80 g, 40 mmol) were dissolved in 50 ml of dimethylacetamide, 4.15 g (30 mmol) of potassium carbonate, 0.31 g (3 mmol) of pivalic acid and 0.05 g (0.2 mmol) of Pd(OAC)2 were added, and the reaction was completed under a nitrogen atmosphere. After dilution, the reaction was precipitated with methanol, and the solid was filtered and vacuum dried to obtain the target polymer (P-20). 1 H NMR(500MHz,Chloroform-d)δ7.42–7.36(m,1H),7.22–7.17(m,1H),4.16(d,J=4.0Hz,2H),3.63(d,J=11 .5Hz,1H),3.51(d,J=11.7Hz,1H),3.41(t,J=5.3Hz,2H),2.99(t,J=7.5Hz,1H),2.81–2.65(m,1H),1.64 –1.55(m,2H),1.54(dt,J=7.5,5.2Hz,2H),1.40–1.33(m,2H),1.36–1.33(m,1H),1.33(dd,J=5.2,2.6Hz,2H),1.33–1.27(m,6H),1.29(s,3H),1.30–1.23(m,5H),0.94–0.85(m,5H). The molecular weight of the polymer obtained by GPC test was 148792.

[0099] Example 21 Synthesis of Representative Conductive Polymer Material P-21 Containing Substituted ProDot Triphenylamine

[0100]

[0101] Tris(4-(3,3-bis((octyloxy)methyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-6-yl)phenyl)amine (IV-D, 15.60 g, 10 mmol) and 2,5-dibromo-3,6-bis(2-(2-methoxyethoxy)ethoxy)thieno[3,2-b]thiophene (C-21, 21.27 g, 40 mmol) were dissolved in 50 ml of dimethylacetamide, 4.15 g (30 mmol) of potassium carbonate, 0.31 g (3 mmol) of pivalic acid and 0.05 g (0.2 mmol) of Pd(OAC)2 were added, and the reaction was completed under a nitrogen atmosphere. After dilution, the reaction was precipitated with methanol, and the solid was filtered and vacuum dried to obtain the target polymer (P-21).1 H NMR(500MHz,Chloroform-d)δ7.42–7.36(m,1H),7.22–7.17(m,1H),4.28(dt,J=7.4,4.9Hz,2H ),4.16(d,J=4.0Hz,2H),3.79(td,J=4.9,3.4Hz,2H),3.66–3.58(m,3H),3.60–3.55(m,2H),3. 51 (d, J = 11.7 Hz, 1H), 3.41 (t, J = 5.3 Hz, 2H), 3.37 (s, 2H), 1.55 (tt, J = 7.5, 5.3 Hz, 2H), 1.40–1.31 (m, 2H), 1.34–1.27 (m, 4H), 1.31–1.23 (m, 5H), 0.94–0.85 (m, 3H). The molecular weight of the polymer obtained by GPC test was 127351.

[0102] Example 22 Synthesis of Representative Conductive Polymer Material P-22 Containing Substituted ProDot Triphenylamine

[0103]

[0104] Tris(4-(3,3-bis((octyloxy)methyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-6-yl)phenyl)amine (IV-D, 15.60 g, 10 mmol) and 2,6-dibromo-4,8-bis(heptyloxy)benzo[1,2-b:4,5-b']dithiophene (C-22, 22.97 g, 40 mmol) were dissolved in 50 ml of dimethylacetamide, 4.15 g (30 mmol) of potassium carbonate, 0.31 g (3 mmol) of pivalic acid and 0.05 g (0.2 mmol) of Pd(OAC)2 were added, and the reaction was completed under a nitrogen atmosphere. After dilution, the reaction was precipitated with methanol, and the solid was filtered and vacuum dried to obtain the target polymer (P-22). 1 H NMR (500 MHz, Chloroform-d) δ7.43–7.36 (m, 1H), 7.22–7.17 (m, 0H), 4.16 (d, J = 4.0 Hz, 1H), 4.03 (t, J = 6.0 Hz, 1H), 3.41 (t, J = 5.3 Hz, 1H), 1.82 (tt, J = 7.4, 6.1 Hz, 1H), 1.55 (tt, J = 7.5, 5.3 Hz, 1H), 1.51–1.41 (m, 1H), 1.40–1.32 (m, 1H), 1.35–1.30 (m, 1H), 1.31 (s, 1H), 1.32–1.23 (m, 5H), 0.94–0.85 (m, 3H). The molecular weight of the polymer measured by GPC was 90870.

[0105] Example 23 Synthesis of Representative Conductive Polymer Material P-23 Containing Substituted ProDot Triphenylamine

[0106]

[0107] Tris(4-(3,3-bis((octyloxy)methyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-6-yl)phenyl)amine (IV-D, 15.60 g, 10 mmol) and 2,6-dibromo-4,8-bis(2-(2-methoxyethoxy)ethoxy)benzo[1,2-b:4,5-b']dithiophene (C-23, 22.97 g, 40 mmol) were dissolved in 50 ml of dimethylacetamide, and 4.15 g (30 mmol) of potassium carbonate, 0.31 g (3 mmol) of pivalic acid and 0.05 g (0.2 mmol) of Pd(OAC)2 were added. The reaction was completed under a nitrogen atmosphere. After dilution, the mixture was precipitated with methanol, filtered, and the solid was vacuum dried to obtain the target polymer (P-23). 1 H NMR (500 MHz, Chloroform-d) δ7.43–7.36 (m, 1H), 4.28 (t, J = 4.9 Hz, 1H), 4.16 (d, J = 4.0 Hz, 1H), 3.80 (t, J = 4.9 Hz, 1H), 3.66–3.55 (m, 2H), 3.41 (t, J = 5.3 Hz, 1H), 3.37 (s, 1H), 1.55 (tt, J = 7.5, 5.3 Hz, 1H), 1.40–1.30 (m, 1H), 1.33–1.23 (m, 3H), 0.92–0.86 (m, 1H). The molecular weight of the polymer measured by GPC was 165491.

[0108] Example 24 Synthesis of Representative Conductive Polymer Material P-24 Containing Substituted ProDot Triphenylamine

[0109]

[0110] Tris(4-(3,3-bis((octyloxy)methyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepin-6-yl)phenyl)amine (IV-D, 15.60 g, 10 mmol) and 4,7-dibromobenzo[c][1,2,5]thiadiazole (C-24, 11.70 g, 40 mmol) were dissolved in 50 ml of dimethylacetamide, and 4.15 g (30 mmol) of potassium carbonate, 0.31 g (3 mmol) of pivalic acid and 0.05 g (0.2 mmol) of Pd(OAC)2 were added. The reaction was completed under a nitrogen atmosphere. After dilution, the mixture was precipitated with methanol, filtered, and the solid was vacuum dried to obtain the target polymer (P-24). 1 H NMR(500MHz,Chloroform-d)δ7.62(d,J=9.0Hz,0H),7.40–7.35(m,1H),7.21(ddt,J=8.7,7. 5,1.4Hz,2H),4.16(d,J=4.0Hz,3H),3.63(d,J=11.5Hz,1H),3.51(d,J=11.7Hz,1H),3.41(t, J=5.3Hz, 3H), 2.63(d, J=1.1Hz, 2H), 1.60–1.51(m, 2H), 1.40–1.30(m, 5H), 1.30(d, J=2.5Hz, 1H), 1.29(d, J=1.8Hz, 2H), 1.30–1.23(m, 6H), 0.94–0.85(m, 4H). The molecular weight of the polymer obtained by GPC test was 109827.

[0111] Example 25 Synthesis of Representative Conductive Polymer Material P-25 Containing Substituted ProDot Triphenylamine

[0112]

[0113] 3,3-Dipentyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxazepine (IE, 29.65 g, 100 mmol) was dissolved in 200 ml tetrahydrofuran (THF), and 12.81 g (200 mmol) of n-butyl lithium was added dropwise at -78 °C. After the addition, the mixture was stirred at room temperature for 5 min, and then 65.10 g (200 mmol) of tri-n-butyltin chloride was added dropwise at -78 °C. After the addition, the mixture was stirred at room temperature for 30 min. Water was added and the product was extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous sodium sulfate, concentrated, and 53.26 g of tributyl(3,3-dipentyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxaglycone-6-yl)stannane (II-E) was obtained by column chromatography. 1H NMR (500MHz, Chloroform-d) δ1.53–1.21 (m, 1H), 0.89 (td, J = 6.8, 3.5Hz, 0H).

[0114] Tri(4-bromophenyl)amine (III, 2.394 g, 5 mmol) and 14.64 g (25 mmol) of tributyl(3,3-dipentyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxol-6-yl)stannane (II-E) were dissolved in 150 ml of tetrahydrofuran, and 1.05 g (0.0015 mmol) of Pd(PPh3)2Cl2 was added. The mixture was reacted at 100°C overnight under an argon atmosphere, cooled to room temperature, the solvent was removed, and column chromatography was used to obtain 5.15 g of tri(4-(3,3-dipentyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxol-6-yl)phenyl)amine (IV-E). 1 H NMR(500MHz,Chloroform-d)δ7.23–7.18(m,1H),7.04–6.98(m,1H),3.99(d,J=1.8H z,2H),1.47–1.37(m,2H),1.40–1.29(m,2H),1.33–1.20(m,4H),0.94–0.86(m,3H).

[0115] After multiple cumulative amounts, tri(4-(3,3-dipentyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxo-6-yl)phenyl)amine (IV-E, 11.29 g, 10 mmol) and 1,4-dibromobenzene (C-25, 9.43 g, 40 mmol) were dissolved in 50 ml of dimethylacetamide, and 4.15 g (30 mmol) of potassium carbonate, 0.31 g (3 mmol) of pivalic acid and 0.05 g (0.2 mmol) of Pd(OAC)2 were added. The reaction was completed under a nitrogen atmosphere. After dilution, the mixture was precipitated with methanol, filtered, and the solid was vacuum dried to obtain the target polymer (P-25). 1 H NMR (500 MHz, Chloroform-d) δ7.51–7.45 (m, 1H), 7.40–7.34 (m, 1H), 7.25–7.17 (m, 2H), 4.01 (s, 2H), 1.48–1.38 (m, 2H), 1.41–1.30 (m, 2H), 1.33–1.25 (m, 1H), 1.29–1.20 (m, 3H), 0.94–0.85 (m, 3H). The molecular weight of the polymer obtained by GPC test was 189721.

[0116] Example 26 Synthesis of Representative Conductive Polymer Material P-26 Containing Substituted ProDot Triphenylamine

[0117]

[0118] Tri(4-(3,3-dipentyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxo-6-yl)phenyl)amine (IV-E, 11.29 g, 10 mmol) and 1,4-dibromo-2,5-bis(2-methoxyethoxy)benzene (C-26, 15.36 g, 40 mmol) were dissolved in 50 ml of dimethylacetamide, and 4.15 g (30 mmol) of potassium carbonate, 0.31 g (3 mmol) of pivalic acid and 0.05 g (0.2 mmol) of Pd(OAC)2 were added. The reaction was completed under a nitrogen atmosphere. After dilution, the mixture was precipitated with methanol, filtered, and the solid was vacuum dried to obtain the target polymer (P-26). 1 H NMR (500 MHz, Chloroform-d) δ7.40–7.35 (m, 1H), 4.21 (dt, J=21.7, 4.9 Hz, 1H), 4.01 (s, 1H), 3.56 (t, J=4.9 Hz, 1H), 3.37 (s, 1H), 1.42 (ddd, J=8.5, 6.4, 2.8 Hz, 1H), 1.41–1.20 (m, 3H), 0.94–0.85 (m, 2H). The molecular weight of the polymer obtained by GPC test was 80981.

[0119] Example 27 Synthesis of Representative Conductive Polymer Material P-27 Containing Substituted ProDot Triphenylamine

[0120]

[0121] Tri(4-(3,3-dipentyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxo-6-yl)phenyl)amine (IV-E, 11.29 g, 10 mmol) and 2,6-dibromonaphthalene (C-3, 11.44 g, 40 mmol) were dissolved in 50 ml of dimethylacetamide, and 4.15 g (30 mmol) of potassium carbonate, 0.31 g (3 mmol) of pivalic acid and 0.05 g (0.2 mmol) of Pd(OAC)2 were added. The reaction was completed under a nitrogen atmosphere. After dilution, the mixture was precipitated with methanol, filtered, and the solid was vacuum dried to obtain the target polymer (P-27). 1HNMR(500MHz,Chloroform-d)δ8.00(t,J=2.1Hz,1H),7.89(dd,J=8.1,2.1Hz,1H),7.84(dd,J=7. 8,2.0Hz,1H),7.78–7.73(m,1H),7.44(dd,J=7.8,2.0Hz,1H),7.40–7.35(m,3H),7.22–7.17(m,2H ),4.01(s,4H),2.50–2.46(m,2H),1.48–1.38(m,4H),1.40–1.32(m,3H),1.35–1.30(m,1H),1.32–1.26(m,2H),1.29–1.23(m,5H),1.26–1.20(m,1H),0.94–0.85(m,6H). The molecular weight of the polymer obtained by GPC test was 125698.

[0122] Example 28 Synthesis of Representative Conductive Polymer Material P-28 Containing Substituted ProDot Triphenylamine

[0123]

[0124] Tri(4-(3,3-dipentyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxo-6-yl)phenyl)amine (IV-E, 11.29 g, 10 mmol) and 2,7-dibromo-9,9-dibutyl-9H-fluorene (C-28, 17.45 g, 40 mmol) were dissolved in 50 ml of dimethylacetamide, and 4.15 g (30 mmol) of potassium carbonate, 0.31 g (3 mmol) of pivalic acid and 0.05 g (0.2 mmol) of Pd(OAC)2 were added. The reaction was completed under a nitrogen atmosphere. After dilution, the mixture was precipitated with methanol, filtered, and the solid was vacuum dried to obtain the target polymer (P-28). 1 H NMR (500 MHz, Chloroform-d) δ7.83 (d, J=7.6 Hz, 0H), 7.62–7.54 (m, 1H), 7.40–7.35 (m, 1H), 7.24–7.17 (m, 2H), 4.01 (s, 1H), 1.96–1.87 (m, 2H), 1.48–1.31 (m, 7H), 1.34–1.26 (m, 1H), 1.29–1.24 (m, 2H), 1.26–1.22 (m, 1H), 0.95–0.85 (m, 6H). The molecular weight of the polymer measured by GPC was 159632.

[0125] Example 29 Synthesis of Representative Conductive Polymer Material P-29 Containing Substituted ProDot Triphenylamine

[0126]

[0127] Tri(4-(3,3-dipentyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxo-6-yl)phenyl)amine (IV-E, 11.29 g, 10 mmol) and 2,7-dibromo-9-(2-(2-(2-)methoxyethoxy)ethoxy)-9H-carbazole (C-29, 19.49 g, 40 mmol) were dissolved in 50 ml of dimethylacetamide, and 4.15 g (30 mmol) of potassium carbonate, 0.31 g (3 mmol) of pivalic acid and 0.05 g (0.2 mmol) of Pd(OAC)2 were added. The reaction was completed under a nitrogen atmosphere. After dilution, the mixture was precipitated with methanol, filtered, and the solid was vacuum dried to obtain the target polymer (P-29). 1 H NMR(500MHz,Chloroform-d)δ8.20(t,J=7.0Hz,1H),7.89(d,J=7.9Hz,1H),7.74–7.69(m,1H),7.63(ddd,J=18.7,7.5,2.2Hz, 1H),7.40–7.33(m,2H),7.24–7.17(m,2H),7.10(ddd,J=7.7,1.4,0.7Hz,1H),4.12(t,J=4.6Hz,2H),4.01(s,3H),3.90(s,1H) ,3.67(t,J=4.6Hz,2H),3.66–3.59(m,6H),3.60–3.55(m,2H),3.37(s,2H),2.85–2.75(m,1H),2.42(d,J=0.9Hz,2H),1.49–1.42(m,1H),1.45–1.38(m,3H),1.41–1.27(m,4H),1.29(s,1H),1.30–1.20(m,8H),0.94–0.86(m,6H). The molecular weight of the polymer obtained by GPC test was 96325.

[0128] Example 30 Synthesis of Representative Conductive Polymer Material P-30 Containing Substituted ProDot Triphenylamine

[0129]

[0130] Tri(4-(3,3-dipentyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxo-6-yl)phenyl)amine (IV-E, 11.29 g, 10 mmol) and 2,7-dibromo-9-butoxy-9H-carbazole (C-30, 15.88 g, 40 mmol) were dissolved in 50 ml of dimethylacetamide, and 4.15 g (30 mmol) of potassium carbonate, 0.31 g (3 mmol) of pivalic acid and 0.05 g (0.2 mmol) of Pd(OAC)2 were added. The reaction was completed under a nitrogen atmosphere. After dilution, the mixture was precipitated with methanol, filtered, and the solid was vacuum dried to obtain the target polymer (P-30). 1 H NMR(500MHz,Chloroform-d)δ8.21(d,J=7.5Hz,1H),7.89(d,J=8.0Hz,1H),7.71(d,J=2.2H z,1H),7.61(dd,J=7.5,2.2Hz,1H),7.40–7.32(m,3H),7.22–7.17(m,2H),7.10(ddd,J=7.8, 1.6, 0.9 Hz, 1H), 4.01 (s, 4H), 3.79 (t, J = 5.1 Hz, 2H), 2.42 (s, 2H), 1.69 (tt, J = 6.5, 5.1 Hz, 2H), 1.48–1.20 (m, 19H), 0.95 (t, J = 7.0 Hz, 3H), 0.92–0.85 (m, 6H). The molecular weight of the polymer obtained by GPC test was 96145.

[0131] Example 31 Synthesis of Representative Conductive Polymer Material P-31 Containing Substituted ProDot Triphenylamine

[0132]

[0133] 3,3-bis(butoxymethyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxazepine (IF, 32.85 g, 100 mmol) was dissolved in 200 ml tetrahydrofuran (THF), and 12.81 g (200 mmol) of n-butyl lithium was added dropwise at -78°C. After the addition, the mixture was stirred at room temperature for 5 min, and then 65.10 g (200 mmol) of tri-n-butyltin chloride was added dropwise at -78°C. After the addition, the mixture was stirred at room temperature for 30 min. Water was added and the product was extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous sodium sulfate, concentrated, and column chromatography was used to obtain 52.55 g of (3,3-bis(butoxymethyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxaglycone-6-yl)tributyltinane (II-F). 1H NMR(500MHz,Chloroform-d)δ4.11(s,1H),4.02(s,1H),3.63(d,J=11.5Hz,1H),3.51(d,J=11.7Hz,1H),3.43(td,J=5.6,2.9Hz,2 H),1.60–1.52(m,2H),1.52–1.43(m,3H),1.42–1.36(m,1H),1.38–1.29(m,4H),1.32–1.21(m,3H),0.91(dt,J=14.8,6.8Hz,8H).

[0134] Tri(4-bromophenyl)amine (III, 2.394 g, 5 mmol) and 15.46 g (25 mmol) of (3,3-bis(butoxymethyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxopyran-6-yl)tributyltinane (II-F) were dissolved in 150 ml of tetrahydrofuran, and 1.05 g (0.0015 mmol) of Pd(PPh3)2Cl2 was added. The mixture was reacted at 100°C overnight under an argon atmosphere, cooled to room temperature, and the solvent was removed. 5.23 g of tri(4-(3,3-bis(butoxymethyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxopyran-6-yl)phenyl)amine (IV-F) was obtained by column chromatography. 1 H NMR(500MHz,Chloroform-d)δ7.23–7.18(m,1H),7.04–6.98(m,1H),4.13(d,J=10.8Hz,2H),3.63(d,J=11.5Hz,1H),3.51(d, J=11.7Hz,1H),3.43(td,J=5.6,2.9Hz,2H),1.60–1.52(m,2H),1.42–1.36(m,1H),1.38–1.32(m,1H),0.93(t,J=7.0Hz,3H).

[0135] After multiple cumulative doses, tris(4-(3,3-bis(butoxymethyl)-3,4-dihydro-2H-thieno)

[0136] [3,4-b][1,4]dioxaglycone-6-yl)phenyl)amine (IV-F, 12.54 g, 10 mmol) and 2,5-dibromothiophene (C-31, 9.43 g, 40 mmol) were dissolved in 50 ml of dimethylacetamide, and 4.15 g (30 mmol) of potassium carbonate, 0.31 g (3 mmol) of pivalic acid and 0.05 g (0.2 mmol) of Pd(OAC)2 were added. The reaction was completed under a nitrogen atmosphere. After dilution, the mixture was precipitated with methanol, filtered, and the solid was vacuum dried to obtain the target polymer (P-31).1 H NMR (500 MHz, Chloroform-d) δ7.42–7.36 (m, 1H), 7.22–7.17 (m, 1H), 6.83 (d, J = 5.9 Hz, 1H), 6.74–6.69 (m, 0H), 4.16 (d, J = 4.0 Hz, 2H), 3.63 (d, J = 11.5 Hz, 1H), 3.51 (d, J = 11.7 Hz, 1H), 3.43 (td, J = 5.6, 2.9 Hz, 2H), 2.46 (d, J = 0.7 Hz, 2H), 1.60–1.52 (m, 2H), 1.42–1.32 (m, 2H), 0.93 (t, J = 7.0 Hz, 3H). The molecular weight of the polymer measured by GPC was 120365.

[0137] Example 32 Synthesis of Representative Conductive Polymer Material P-32 Containing Substituted ProDot Triphenylamine

[0138]

[0139] Tris(4-(3,3-bis(butoxymethyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxo-6-yl)phenyl)amine (IV-F, 12.54 g, 10 mmol) and 2,5-dibromo-3,6-dipentylthienyl[3,2-b]thiophene (C-32, 17.53 g, 40 mmol) were dissolved in 50 ml of dimethylacetamide, and 4.15 g (30 mmol) of potassium carbonate, 0.31 g (3 mmol) of pivalic acid and 0.05 g (0.2 mmol) of Pd(OAC)2 were added. The reaction was completed under a nitrogen atmosphere. After dilution, the mixture was precipitated with methanol, filtered, and the solid was vacuum dried to obtain the target polymer (P-32). 1 H NMR (500 MHz, Chloroform-d) δ7.42–7.36 (m, 1H), 7.22–7.17 (m, 1H), 4.16 (d, J = 4.0 Hz, 2H), 3.63 (d, J = 11.5 Hz, 1H), 3.51 (d, J = 11.7 Hz, 1H), 3.43 (td, J = 5.6, 2.9 Hz, 2H), 2.94 (t, J = 7.1 Hz, 1H), 2.73 (t, J = 7.3 Hz, 1H), 2.28 (s, 1H), 1.67–1.52 (m, 4H), 1.43–1.29 (m, 7H), 0.91 (dt, J = 17.8, 6.8 Hz, 6H). The molecular weight of the polymer measured by GPC was 102365.

[0140] Example 33 Synthesis of Representative Conductive Polymer Material P-33 Containing Substituted ProDot Triphenylamine

[0141]

[0142] Tris(4-(3,3-bis(butoxymethyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxo-6-yl)phenyl)amine (IV-F, 12.54 g, 10 mmol) and 2,5-dibromo-3,6-bis(2-(2-(2-)methoxyethoxy)ethoxy)thieno[3,2-b]thiophene (C-33, 24.90 g, 40 mmol) were dissolved in 50 ml of dimethylacetamide, and 4.15 g (30 mmol) of potassium carbonate, 0.31 g (3 mmol) of pivalic acid and 0.05 g (0.2 mmol) of Pd(OAC)2 were added. The reaction was completed under a nitrogen atmosphere. After dilution, the mixture was precipitated with methanol, filtered, and the solid was vacuum dried to obtain the target polymer (P-33). 1 H NMR(500MHz,Chloroform-d)δ7.42–7.36(m,1H),7.22–7.17(m,1H),4.28(dt,J=7.4,4.9Hz,2H),4.16( d,J=4.0Hz,2H),3.79(td,J=5.0,3.3Hz,2H),3.73–3.62(m,3H),3.63(d,J=0.7Hz,1H),3.64–3.57(m,5H ),3.60–3.55(m,1H),3.51(d,J=11.7Hz,1H),3.43(td,J=5.6,2.9Hz,2H),3.37(s,2H),1.56(tt,J=6.9,5.5Hz,2H),1.42–1.32(m,2H),1.18(t,J=7.5Hz,0H),0.93(t,J=7.0Hz,3H). The molecular weight of the polymer obtained by GPC test was 142036.

[0143] Example 34 Synthesis of Representative Conductive Polymer Material P-34 Containing Substituted ProDot Triphenylamine

[0144]

[0145] Tris(4-(3,3-bis(butoxymethyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxo-6-yl)phenyl)amine (IV-F, 12.54 g, 10 mmol) and 2,6-dibromo-4,8-dibutoxybenzo[1,2-b:4,5-b']dithiophene (C-34, 19.69 g, 40 mmol) were dissolved in 50 ml of dimethylacetamide, and 4.15 g (30 mmol) of potassium carbonate, 0.31 g (3 mmol) of pivalic acid and 0.05 g (0.2 mmol) of Pd(OAC)2 were added. The reaction was completed under a nitrogen atmosphere. After dilution, the mixture was precipitated with methanol, filtered, and the solid was vacuum dried to obtain the target polymer (P-34). 1 H NMR (500 MHz, Chloroform-d) δ7.43–7.36 (m, 1H), 7.22–7.17 (m, 0H), 4.16 (d, J = 4.0 Hz, 1H), 4.05 (t, J = 6.4 Hz, 1H), 3.43 (td, J = 5.6, 2.9 Hz, 1H), 2.47 (s, 1H), 1.69 (p, J = 6.6 Hz, 1H), 1.60–1.44 (m, 2H), 1.42–1.32 (m, 1H), 0.95 (dt, J = 26.3, 7.0 Hz, 3H). The molecular weight of the polymer measured by GPC was 130236.

[0146] Example 35 Synthesis of Representative Conductive Polymer Material P-35 Containing Substituted ProDot Triphenylamine

[0147]

[0148] Tris(4-(3,3-bis(butoxymethyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxo-6-yl)phenyl)amine (IV-F, 12.54 g, 10 mmol) and 2,6-dibromo-4,8-bis(2-methoxyethoxy)benzo[1,2-b:4,5-b']dithiophene (C-35, 19.85 g, 40 mmol) were dissolved in 50 ml of dimethylacetamide, and 4.15 g (30 mmol) of potassium carbonate, 0.31 g (3 mmol) of pivalic acid and 0.05 g (0.2 mmol) of Pd(OAC)2 were added. The reaction was completed under a nitrogen atmosphere. After dilution, the mixture was precipitated with methanol, filtered, and the solid was vacuum dried to obtain the target polymer (P-35). 1H NMR(500MHz,Chloroform-d)δ7.43–7.36(m,2H),7.22–7.17(m,1H),4.28(t,J=4.9Hz, 2H),4.16(d,J=4.0Hz,2H),3.63(d,J=11.5Hz,1H),3.59(t,J=4.9Hz,2H),3.51(d,J=1 1.7Hz,1H),3.43(td,J=5.6,2.9Hz,2H),3.37(s,2H),2.47(s,1H),1.60–1.52(m,2H),1.42–1.36(m,1H),1.38–1.32(m,1H),0.93(t,J=7.0Hz,3H). The molecular weight of the polymer obtained by GPC test was 96320.

[0149] Example 36 Synthesis of Representative Conductive Polymer Material P-36 Containing Substituted ProDot Triphenylamine

[0150]

[0151] Tris(4-(3,3-bis(butoxymethyl)-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxo-6-yl)phenyl)amine (IV-F, 12.54 g, 10 mmol) and 4,7-dibromobenzo[c][1,2,5]thiadiazole (C-36, 11.76 g, 40 mmol) were dissolved in 50 ml of dimethylacetamide, and 4.15 g (30 mmol) of potassium carbonate, 0.31 g (3 mmol) of pivalic acid and 0.05 g (0.2 mmol) of Pd(OAC)2 were added. The reaction was completed under nitrogen atmosphere. After dilution, the mixture was precipitated with methanol, filtered, and the solid was vacuum dried to obtain the target polymer (P-35). 1 H NMR (500 MHz, Chloroform-d) δ7.62 (d, J = 9.0 Hz, 1H), 7.40–7.35 (m, 2H), 7.21 (ddt, J = 8.7, 7.5, 1.4 Hz, 2H), 4.16 (d, J = 4.0 Hz, 3H), 3.63 (d, J = 11.5 Hz, 1H), 3.51 (d, J = 11.7 Hz, 1H), 3.43 (td, J = 5.6, 2.9 Hz, 3H), 2.63 (d, J = 0.9 Hz, 2H), 1.60–1.52 (m, 2H), 1.42–1.32 (m, 3H), 0.93 (t, J = 7.0 Hz, 5H). The molecular weight of the polymer measured by GPC was 87632.

[0152] Example 37 Preparation of electrochromic device

[0153] The above-synthesized materials P-1 to P-36 were prepared into 50 mg / mL chloroform solutions for later use.

[0154] 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 solution of the above-prepared synthesized materials P-1 to P-36 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:

[0155] Material Color Change Driving voltage Response time Material Color Change Driving voltage Response time P-1 Transparent-Black 1.46V 1.6s / 2.6s P-19 Transparent-reddish brown 1.64V 1.5s / 2.6s P-2 Transparent-Black 1.65V 1.3s / 1.2s P-20 Transparent-reddish brown 1.76V 1.6s / 1.5s P-3 Transparent-Black 1.61V 1.5s / 2.5s P-21 Transparent-reddish brown 1.61V 1.6s / 1.5s P-4 Transparent-Black 1.31V 1.5s / 2.5s P-22 Transparent-reddish brown 1.67V 1.5s / 2.3s P-5 Transparent-Black 1.62V 0.7s / 1.1s P-23 Transparent-reddish brown 1.17V 1.2s / 1.4s P-6 Transparent-Black 1.35V 1.4s / 1.2s P-24 Transparent-reddish brown 1.57V 2.1s / 1.6s P-7 Transparent-Black 1.69V 1.4s / 2.7s P-25 Transparent-reddish brown 1.68V 1.1s / 2.3s P-8 Transparent-Black 1.18V 1.6s / 2.7s P-26 Transparent-reddish brown 1.76V 1.4s / 1.1s P-9 Transparent-Black 1.26V 1.3s / 3.7s P-27 Transparent-reddish brown 1.67V 1.4s / 1.2s P-10 Transparent-Black 1.11V 1.6s / 2.6s P-28 Transparent-reddish brown 1.47V 1.5s / 2.2s P-11 Transparent-Black 1.24V 1.5s / 2.1s P-29 Transparent-reddish brown 1.14V 1.6s / 1.1s P-12 Transparent-Black 1.52V 1.1s / 2.2s P-30 Transparent-reddish brown 1.57V 2.4s / 1.6s P-13 Transparent-Black 1.66V 1.2s / 1.1s P-31 Transparent-reddish brown 1.60V 1.5s / 2.2 P-14 Transparent-Black 1.16V 1.7s / 2.6s P-32 Transparent-reddish brown 1.72V 1.1s / 1.2s P-15 Transparent-Black 1.31V 1.3s / 2.7s P-33 Transparent-reddish brown 1.01V 1.6s / 1.1s P-16 Transparent-Black 1.64V 0.3s / 1.5s P-34 Transparent-reddish brown 1.67V 1.5s / 2.3s P-17 Transparent-Black 1.64V 0.5s / 1.2s P-35 Transparent-reddish brown 1.17V 1.2s / 1.2s P-18 Transparent-Black 1.06V 1.6s / 2.5s P-36 Transparent-reddish brown 1.55V 2.3s / 1.6s

[0156] 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.

[0157] 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; R is selected from alkyl, alkoxy, alkyl alkoxy chain, oxygen-substituted alkyl chain, oligoether group, benzyl, substituted benzyl, phenyl, substituted phenyl.

2. The conductive polymer material according to claim 1, characterized in that The Ar substituent is selected from the following groups Wherein, R' is 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: 3,3-disubstituted ProDot (I) reacts with tri-n-butyltin chloride and purifies to obtain an intermediate compound (II); Tri(4-bromophenyl)amine (III) reacts with the intermediate compound (II) and purifies to obtain the intermediate compound (IV); The intermediate compound (IV) and the aromatic dibromide derivative undergo 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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