Black conductive polymer material and applications

Abstract

The present application relates to the field of electrochromic materials, and particularly relates to a black conductive polymer material. The black conductive polymer has a full absorption effect in the visible light region, has an ultra-low driving voltage, an ultra-long cycle stability and a high coloring efficiency. The black conductive polymer can realize an ultra-long color change effect from black to transparent. The black conductive polymer can be effectively used as a material of a color change layer of an organic electrochromic element. In addition, an organic electrochromic device in which an organic layer contains the compound of the present application greatly improves the performance of the device in terms of color change performance, driving voltage, service life, response time and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of electrochromic materials, in particular to a black conductive polymer material and applications thereof. BACKGROUND

[0002] Traditional electrochromic materials have some limitations in color control, optical performance, and stability. Conjugated polymers have wide application potential in the field of electrochromic materials due to their unique electrical properties and structural characteristics. Therefore, it is necessary to provide a conjugated polymer-based electrochromic material to meet the more extensive application requirements. Smart window technology, as an important part of modern building and automotive industries, has always been a hot research field. This technology allows dynamic adjustment of window light transmittance, thereby providing optimization of energy efficiency, comfort, and privacy. Traditional smart window technology relies on liquid crystals or metal oxide films, which are effective but have limitations in cost, durability, and color selection. In particular, existing technologies are difficult to achieve deep color tones such as black, which limits the choices of designers and architects in terms of aesthetics and functionality. In recent years, electrochromic (EC) technology has attracted attention as a new solution for smart windows. Electrochromic materials change their color by applying a voltage, thereby adjusting the transmittance of light. Although this technology has great potential in terms of energy efficiency and user control, most existing electrochromic materials are mainly based on inorganic compounds, which are usually transparent or light-colored and have high manufacturing costs, limiting their widespread application in the market. Therefore, the development of a new type of black organic electrochromic material is not only a technological innovation, but also meets the market demand for more diverse and affordable smart window solutions.

[0003] Compared with traditional inorganic materials, organic electrochromic materials are more flexible in synthesis and can achieve a wide range of color adjustments, including deeper color tones such as black, through molecular design. In addition, the manufacturing process of these materials is more economical, which is expected to reduce the overall cost of smart windows and make them more popular. In addition, black organic electrochromic materials provide unique advantages in terms of visual effects and energy efficiency. Black not only provides more choices in terms of aesthetics, but also performs well in energy saving due to its excellent light-to-heat conversion efficiency. The development of this material can significantly improve the energy efficiency of smart windows while providing architects and designers with more innovative design space. SUMMARY

[0004] In view of the above many deficiencies of existing black organic electrochromic materials, the application provides a bismuth-containing compound, a preparation method and applications. The purpose of the application is to develop a new type of black organic electrochromic material, which not only can provide improved optical performance and higher energy efficiency, but also can be realized at a lower cost, so that the intelligent window technology becomes feasible and economical in a wider application field. Through the innovation of this material, the application is expected to promote the development of intelligent window technology and bring revolutionary changes to the building and automotive industries

[0005] The technical solution of the application is realized by providing a black conductive polymer material with the following molecular formula:

[0006]

[0007] wherein y=1, x+z+w=1; x>0, z>0, w>0; at most one of x, z and w is 0;

[0008] n is a natural number less than 100; R5 is a branched or straight alkyl chain of 1-20 carbons.

[0009] R1=R2, R3=R4; R1 and R3 are each independently selected from hydroxyl, carbonyl, carboxyl, sulfide group, ester group, ether group, nitro group, halogen, C1-C20 hydroxyl, C2-C20 carbonyl, C2-C40 carboxyl, C3-C20 sulfide group, C1-C20 ester group, C2-C20 ether group, C2-C60 nitro group, halogen-containing C1-C20 alkyl chain, silyl group, C1-C20 aryl silyl group.

[0010] In one embodiment of the application, R1 is selected from the following groups:

[0011]

[0012] R3 is selected from the following groups:

[0013]

[0014] In one embodiment of the application, the polymer material is selected from the following:

[0015]

[0016]

[0017] The application also provides the black conductive polymer material and its application in electrochromic devices.

[0018] The beneficial effects are as follows:

[0019] The black conductive polymer of the present application has a full absorption effect in the visible light region, and the conductive polymer has an ultra-low driving voltage, an ultra-long cycle stability and a high coloring efficiency. An ultra-long color change effect from black to transparent can be achieved. It can be effectively used as a color change layer material of an organic electrochromic element. In addition, the organic electrochromic device in which the organic layer contains the compound of the present application greatly improves the performance of the device in terms of color change performance, driving voltage, life, response time, etc.

[0020] The material is mainly used in the fields of smart windows, high-end display technology and energy-saving buildings. The core of the present application is to use a specific conjugated organic polymer combined with advanced preparation process to achieve reversible change from black to transparent under voltage excitation. The material uses a unique conjugated polymer structure, which optimizes the light absorption properties of the material by precisely controlling the molecular arrangement and electron conjugation length, so that it has a short response time under a specific voltage. The design of the conjugated polymer also considers its electrochemical stability and color retention ability under long-term use. The preparation method includes a series of organic synthesis steps for building a conjugated polymer with a specific molecular structure, and subsequent material processing technology to ensure the uniformity and functionality of the material. The black conjugated electrochromic material of the present application has high adaptability and excellent performance, providing new possibilities for the use of electrochromic technology in various high-demand applications, especially in situations requiring long-life and fast-response color control. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 Structure diagram of an electrochromic device using the polymer material of the present application.

[0022] Figure 2 CV curve diagram of an electrochromic device using the polymer material of the present application.

[0023] Figure 3 Comparison diagram of an electrochromic device using the polymer material of the present application in neutral state and colored state. DETAILED DESCRIPTION

[0024] In order to make the purpose, technical scheme and advantages of the present application clearer, the technical scheme of the present application will be described in detail below in combination with specific embodiments of the present application and corresponding drawings. Obviously, the described embodiments are only part of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0025] The present application will be further described in detail below in combination with the drawings and embodiments.

[0026] The electrochromic device according to the present application is mainly composed of an electrochromic layer, a conductive layer, an ion conductor (electrolyte), a counter electrode, a substrate, and a power source. The electrochromic layer can be composed of a single compound or a mixture of multiple compounds, and can be formed by a solution coating method, including but not limited to spin coating, dip coating, blade coating, inkjet printing, or thermal transfer printing. In addition, the substrate type in the present application is not particularly limited, and can include a silicon wafer, quartz, a glass plate, a metal plate, a plastic film, etc.

[0027] DETAILED EMBODIMENT

[0028] Example 1: Synthesis of black conjugated polymer P1

[0029] P1 is a polar conductive polymer containing spirofluorene as the main body, and its synthesis route is shown in the general formula below.

[0030]

[0031] A-1 (4.53 g, 4.66 mmol), A-2 (10 g, 18.63 mmol), A-3 (3.28 g, 11.18 mmol), A-4 (0.95 g, 2.79 mmol), Pd(OAC)2 (0.083 g, 0.37 mmol), PiVOH (0.57 g, 5.5 mmol), and K2CO3 (5.14 g, 37.27 mmol) were dissolved in N,N-dimethylacetamide (DMAc) (6 mL) and heated at 130°C under a nitrogen atmosphere for 48 hours. The polymer was precipitated in methanol and filtered to obtain P1 polymer.

[0032] A-1: 1 H NMR (500 MHz, Chloroform-d) δ 7.58 (d, J = 8.2 Hz, 2H), 7.54 - 7.49 (m, 2H), 7.48 (d, J = 3.6 Hz, 2H), 7.43 (d, J = 1.8 Hz, 2H), 7.18 (dd, J = 8.8, 2.6 Hz, 2H), 6.88 (d, J = 8.8 Hz, 2H), 4.27 (q, J = 7.1 Hz, 4H), 4.16 (t, J = 5.1 Hz, 4H), 3.87 (t, J = 5.1 Hz, 4H), 3.74 (dd, J = 5.9, 3.7 Hz, 4H), 3.67 - 3.62 (m, 9H), 3.57 (dd, J = 6.0, 3.6 Hz, 4H), 3.50 (q, J = 7.0 Hz, 5H), 1.31 (t, J = 7.1 Hz, 7H), 1.19 (t, J = 7.0 Hz, 6H).

[0033] A-2: 1H NMR (400 MHz, Chloroform-d) δ 4.08 (s, 4H), 3.73 - 3.60 (m, 14H), 3.60 - 3.51 (m, 15H), 3.51 (d, J = 7.0 Hz, 3H), 1.19 (t, J = 7.0 Hz, 7H).

[0034] A-3: 1 H NMR (400 MHz, Chloroform-d) δ 7.66 (s, 2H).

[0035] A-4: 1 H NMR (500 MHz, Chloroform-d) δ 3.99 (q, J = 5.1 Hz, 2H), 1.29 (t, J = 5.0 Hz, 3H). P1: 13 C NMR (400 MHz, Chloroform-d) δ 169.35, 164.67, 161.49, 153.27, 149.82, 144.41, 140.11, 137.98, 134.01, 133.79, 132.47, 131.59, 130.69, 129.42, 124.15, 119.05, 116.19, 113.50, 113.01, 99.68, 63.01, 45.12, 35.06, 14.28, 14.10.

[0036] Example 2: Synthesis of black conjugated polymer P2

[0037]

[0038] B-1 (4.53 g, 4.66 mmol), B-2 (10 g, 18.63 mmol), B-3 (2.73 g, 9.32 mmol), B-4 (1.51 g, 4.66 mmol), Pd(OAC)2 (0.083 g, 0.37 mmol), PiVOH (0.57 g, 5.5 mmol) and K2CO3 (5.14 g, 37.27 mmol) were dissolved in N,N-dimethylacetamide (DMAc) (6 mL) and heated at 130 °C under nitrogen atmosphere for 48 h. The polymer was precipitated in methanol and filtered to obtain P2 polymer.

[0039] B-1: 1H NMR (400 MHz, Chloroform-d) δ 7.58 (d, J = 8.2 Hz, 2H), 7.54 - 7.49 (m, 2H), 7.48 (d, J = 3.6 Hz, 2H), 7.43 (d, J = 1.8 Hz, 2H), 7.18 (dd, J = 8.8, 2.6 Hz, 2H), 6.88 (d, J = 8.8 Hz, 2H), 4.27 (q, J = 7.1 Hz, 4H), 4.16 (t, J = 5.1 Hz, 4H), 3.87 (t, J = 5.1 Hz, 4H), 3.74 (dd, J = 5.9, 3.7 Hz, 4H), 3.67 - 3.62 (m, 9H), 3.57 (dd, J = 6.0, 3.6 Hz, 4H), 3.50 (q, J = 7.0 Hz, 5H), 1.31 (t, J = 7.1 Hz, 7H), 1.19 (t, J = 7.0 Hz, 6H).

[0040] B-2: 1 H NMR (400 MHz, Chloroform-d) δ 4.08 (s, 4H), 3.73 - 3.60 (m, 14H), 3.60 - 3.51 (m, 15H), 3.51 (d, J = 7.0 Hz, 3H), 1.19 (t, J = 7.0 Hz, 7H).

[0041] B-3: 1 H NMR (400 MHz, Chloroform-d) δ 7.66 (s, 2H).

[0042] B-4: 1 H NMR (500 MHz, Chloroform-d) δ 3.99 (q, J = 5.1 Hz, 2H), 1.29 (t, J = 5.0 Hz, 3H).P2: 13 C NMR (400 MHz, Chloroform-d) δ 169.35, 164.67, 161.49, 153.27, 149.82, 144.41, 140.11, 137.98, 134.01, 133.79, 132.47, 131.59, 130.69, 129.42, 124.15, 119.05, 116.19, 113.50, 113.01, 99.68, 63.01, 45.12, 35.06, 14.28, 14.10.

[0043] Example 3: Synthesis of black conjugated polymer P3

[0044]

[0045] C-1 (4.53 g, 4.66 mmol), C-2 (10 g, 18.63 mmol), C-3 (2.19 g, 7.45 mmol), C-4 (3.62 g, 11.18 mmol), Pd(OAC)2 (0.083 g, 0.37 mmol), PiVOH (0.57 g, 5.5 mmol) and K2CO3 (5.14 g, 37.27 mmol) were dissolved in N,N-dimethylacetamide (DMAc) (6 mL) and heated at 130 °C under nitrogen atmosphere for 48 h. The polymer was precipitated in methanol and filtered to obtain P3 polymer.

[0046] C-1: 1 H NMR (400 MHz, Chloroform-d) δ 7.58 (d, J = 8.2 Hz, 2H), 7.54 - 7.49 (m, 2H), 7.48 (d, J = 3.6 Hz, 2H), 7.43 (d, J = 1.8 Hz, 2H), 7.18 (dd, J = 8.8, 2.6 Hz, 2H), 6.88 (d, J = 8.8 Hz, 2H), 4.27 (q, J = 7.1 Hz, 4H), 4.16 (t, J = 5.1 Hz, 4H), 3.87 (t, J = 5.1 Hz, 4H), 3.74 (dd, J = 5.9, 3.7 Hz, 4H), 3.67 - 3.62 (m, 9H), 3.57 (dd, J = 6.0, 3.6 Hz, 4H), 3.50 (q, J = 7.0 Hz, 5H), 1.31 (t, J = 7.1 Hz, 7H), 1.19 (t, J = 7.0 Hz, 6H).

[0047] C-2: 1 H NMR (400 MHz, Chloroform-d) δ 4.08 (s, 4H), 3.73 - 3.60 (m, 14H), 3.60 - 3.51 (m, 15H), 3.51 (d, J = 7.0 Hz, 3H), 1.19 (t, J = 7.0 Hz, 7H).

[0048] C-3: 1 H NMR (400 MHz, Chloroform-d) δ 7.66 (s, 2H).

[0049] C-4: 1 H NMR (500 MHz, Chloroform-d) δ 3.99 (q, J = 5.1 Hz, 2H), 1.29 (t, J = 5.0 Hz, 3H). P3: 13C NMR (400 MHz, Chloroform-d) δ 167.36, 164.67, 156.80, 153.27, 149.80, 144.41, 139.66, 137.98, 137.84, 137.38, 134.01, 132.47, 130.69, 130.42, 128.93, 124.15, 119.05, 118.76, 114.79, 113.01, 99.68, 93.03, 92.63, 91.93, 63.65, 63.01, 62.08, 60.86, 45.12, 35.06, 15.23, 14.28, 14.10.

[0050] Example 4: Synthesis of black conjugated polymer P4

[0051]

[0052] D-1 (5.43 g, 5.59 mmol), D-2 (10 g, 18.63 mmol), D-3 (2.19 g, 2.74 mmol), D-4 (1.21 g, 3.72 mmol), Pd(OAC)2 (0.083 g, 0.37 mmol), PiVOH (0.57 g, 5.5 mmol) and K2CO3 (5.14 g, 37.27 mmol) were dissolved in N,N-dimethylacetamide (DMAc) (6 mL) and heated at 130 °C under nitrogen atmosphere for 48 h. The polymer was precipitated in methanol and filtered to obtain P4 polymer. The polymer was further purified by dialysis against water for 3 days.

[0053] D-1: 1 H NMR (500 MHz, Chloroform-d) δ 7.58 (d, J = 8.2 Hz, 2H), 7.54 - 7.49 (m, 2H), 7.48 (d, J = 3.6 Hz, 2H), 7.43 (d, J = 1.8 Hz, 2H), 7.18 (dd, J = 8.8, 2.6 Hz, 2H), 6.88 (d, J = 8.8 Hz, 2H), 4.27 (q, J = 7.1 Hz, 4H), 4.16 (t, J = 5.1 Hz, 4H), 3.87 (t, J = 5.1 Hz, 4H), 3.74 (dd, J = 5.9, 3.7 Hz, 4H), 3.67 - 3.62 (m, 9H), 3.57 (dd, J = 6.0, 3.6 Hz, 4H), 3.50 (q, J = 7.0 Hz, 5H), 1.31 (t, J = 7.1 Hz, 7H), 1.19 (t, J = 7.0 Hz, 6H).

[0054] D-2: 1H NMR (400 MHz, Chloroform-d) δ 4.08 (s, 4H), 3.73 - 3.60 (m, 14H), 3.60 - 3.51 (m, 15H), 3.51 (d, J = 7.0 Hz, 3H), 1.19 (t, J = 7.0 Hz, 7H).

[0055] D-3: 1 H NMR (400 MHz, Chloroform-d) δ 7.66 (s, 2H).

[0056] D-4: 1 H NMR (500 MHz, Chloroform-d) δ 3.99 (q, J = 5.1 Hz, 2H), 1.29 (t, J = 5.0 Hz, 3H).P4: 13 C NMR (400 MHz, Chloroform-d) δ 167.36, 164.67, 156.80, 153.27, 149.80, 144.41, 139.66, 137.98, 137.84, 137.38, 134.01, 132.47, 130.69, 130.42, 128.93, 124.15, 119.05, 118.76, 114.79, 113.01, 99.68, 93.03, 92.63, 91.93, 63.65, 63.01, 62.08, 60.86, 45.12, 35.06, 15.23, 14.28, 14.10.

[0057] Example 5: Synthesis of black conjugated polymer P5

[0058]

[0059] E-1 (9.06 g, 9.32 mmol), E-2 (10 g, 18.63 mmol), D-3 (2.74 g, 9.32 mmol), Pd(OAC)2 (0.083 g, 0.37 mmol), PiVOH (0.57 g, 5.5 mmol) and K2CO3 (5.14 g, 37.27 mmol) were dissolved in N,N-dimethylacetamide (DMAc) (6 mL) and heated at 130 °C under nitrogen atmosphere for 48 h. The polymer was precipitated in methanol and filtered to obtain P5 polymer.

[0060] E-1: 1H NMR (400 MHz, Chloroform-d) δ 7.58 (d, J = 8.2 Hz, 2H), 7.54 - 7.49 (m, 2H), 7.48 (d, J = 3.6 Hz, 2H), 7.43 (d, J = 1.8 Hz, 2H), 7.18 (dd, J = 8.8, 2.6 Hz, 2H), 6.88 (d, J = 8.8 Hz, 2H), 4.27 (q, J = 7.1 Hz, 4H), 4.16 (t, J = 5.1 Hz, 4H), 3.87 (t, J = 5.1 Hz, 4H), 3.74 (dd, J = 5.9, 3.7 Hz, 4H), 3.67 - 3.62 (m, 9H), 3.57 (dd, J = 6.0, 3.6 Hz, 4H), 3.50 (q, J = 7.0 Hz, 5H), 1.31 (t, J = 7.1 Hz, 7H), 1.19 (t, J = 7.0 Hz, 6H).

[0061] E-2: 1 H NMR (400 MHz, Chloroform-d) δ 4.08 (s, 4H), 3.73 - 3.60 (m, 14H), 3.60 - 3.51 (m, 15H), 3.51 (d, J = 7.0 Hz, 3H), 1.19 (t, J = 7.0 Hz, 7H).

[0062] E-3: 1 H NMR (400 MHz, Chloroform-d) δ 7.66 (s, 2H).

[0063] P5: 13 C NMR (400 MHz, Chloroform-d) δ 167.36, 164.67, 156.80, 153.27, 149.80, 144.41, 139.66, 137.98, 137.84, 137.38, 134.01, 132.47, 130.69, 130.42, 128.93, 124.15, 119.05, 118.76, 114.79, 113.01, 99.68, 93.03, 92.63, 91.93, 63.65, 63.01, 62.08, 60.86, 45.12, 35.06, 15.23, 14.28, 14.10.

[0064] Example 6: Synthesis of black conjugated polymer P6

[0065]

[0066] F-1 (4.43 g, 5.59 mmol), F-2 (10 g, 18.63 mmol), F-3 (3.83 g, 13.04 mmol), Pd(OAC)2 (0.083 g, 0.37 mmol), PiVOH (0.57 g, 5.5 mmol) and K2CO3 (5.14 g, 37.27 mmol) were dissolved in N,N-dimethylacetamide (DMAc) (6 mL) and heated at 130 °C under nitrogen atmosphere for 48 h. The polymer was precipitated in methanol and filtered to obtain P6 polymer.

[0067] F-1: 1 H NMR (400 MHz, Chloroform-d) δ 7.58 (d, J = 8.2 Hz, 2H), 7.54 - 7.49 (m, 2H), 7.48 (d, J = 3.6 Hz, 2H), 7.43 (d, J = 1.8 Hz, 2H), 7.18 (dd, J = 8.8, 2.6 Hz, 2H), 6.88 (d, J = 8.8 Hz, 2H), 4.27 (q, J = 7.1 Hz, 4H), 4.16 (t, J = 5.1 Hz, 4H), 3.87 (t, J = 5.1 Hz, 4H), 3.74 (dd, J = 5.9, 3.7 Hz, 4H), 3.67 - 3.62 (m, 9H), 3.57 (dd, J = 6.0, 3.6 Hz, 4H), 3.50 (q, J = 7.0 Hz, 5H), 1.31 (t, J = 7.1 Hz, 7H), 1.19 (t, J = 7.0 Hz, 6H).

[0068] F-2: 1 H NMR (400 MHz, Chloroform-d) δ 7.58 (d, J = 8.2 Hz, 2H), 7.54 - 7.49 (m, 2H), 7.48 (d, J = 3.6 Hz, 2H), 7.43 (d, J = 1.8 Hz, 2H), 7.18 (dd, J = 8.8, 2.6 Hz, 2H), 6.88 (d, J = 8.8 Hz, 2H), 4.27 (q, J = 7.1 Hz, 4H), 4.16 (t, J = 5.1 Hz, 4H), 3.87 (t, J = 5.1 Hz, 4H), 3.74 (dd, J = 5.9, 3.7 Hz, 4H), 3.67 - 3.62 (m, 9H), 3.57 (dd, J = 6.0, 3.6 Hz, 4H), 3.50 (q, J = 7.0 Hz, 5H), 1.31 (t, J = 7.1 Hz, 7H), 1.19 (t, J = 7.0 Hz, 6H).

[0069] F-3: 1 H NMR (400 MHz, Chloroform-d) δ 7.66 (s, 2H).

[0070] P6: 13C NMR (400 MHz, Chloroform-d) δ 167.36, 164.67, 156.80, 153.27, 149.80, 144.41, 139.66, 137.98, 137.84, 137.38, 134.01, 132.47, 130.69, 130.42, 128.93, 124.15, 119.05, 118.76, 114.79, 113.01, 99.68, 93.03, 92.63, 91.93, 63.65, 63.01, 62.08, 60.86, 45.12, 35.06, 15.23, 14.28, 14.10.

[0071] Example 7: Synthesis of black conjugated polymer P7

[0072]

[0073] G-1 (12.68 g, 13.04 mmol), G-2 (10 g, 18.63 mmol), G-3 (1.81 g, 5.59 mmol), Pd(OAC)2 (0.083 g, 0.37 mmol), PiVOH (0.57 g, 5.5 mmol) and K2CO3 (5.14 g, 37.27 mmol) were dissolved in N,N-dimethylacetamide (DMAc) (6 mL) and heated at 130 °C under nitrogen atmosphere for 48 h. The polymer was precipitated in methanol and filtered to obtain P7 polymer.

[0074] G-1: 1 H NMR (500 MHz, Chloroform-d) δ 7.58 (d, J = 8.2 Hz, 2H), 7.54 - 7.49 (m, 2H), 7.48 (d, J = 3.6 Hz, 2H), 7.43 (d, J = 1.8 Hz, 2H), 7.18 (dd, J = 8.8, 2.6 Hz, 2H), 6.88 (d, J = 8.8 Hz, 2H), 4.27 (q, J = 7.1 Hz, 4H), 4.16 (t, J = 5.1 Hz, 4H), 3.87 (t, J = 5.1 Hz, 4H), 3.74 (dd, J = 5.9, 3.7 Hz, 4H), 3.67 - 3.62 (m, 9H), 3.57 (dd, J = 6.0, 3.6 Hz, 4H), 3.50 (q, J = 7.0 Hz, 5H), 1.31 (t, J = 7.1 Hz, 7H), 1.19 (t, J = 7.0 Hz, 6H).

[0075] G-2: 1H NMR (400 MHz, Chloroform-d) δ 4.08 (s, 4H), 3.73 - 3.60 (m, 14H), 3.60 - 3.51 (m, 15H), 3.51 (d, J = 7.0 Hz, 3H), 1.19 (t, J = 7.0 Hz, 7H).

[0076] G-3: 1 H NMR (400 MHz, Chloroform-d) δ 7.66 (s, 2H).

[0077] P7: 13 C NMR (400 MHz, Chloroform-d) δ 167.36, 164.67, 156.80, 153.27, 149.80, 144.41, 139.66, 137.98, 137.84, 137.38, 134.01, 132.47, 130.69, 130.42, 128.93, 124.15, 119.05, 118.76, 114.79, 113.01, 99.68, 93.03, 92.63, 91.93, 63.65, 63.01, 62.08, 60.86, 45.12, 35.06, 15.23, 14.28, 14.10.

[0078] Example 8: Synthesis of black conjugated polymer P8

[0079]

[0080] H-1 (16.31 g, 16.77 mmol), H-2 (10 g, 18.63 mmol), H-3 (0.60 g, 1.86 mmol), Pd(OAC)2 (0.083 g, 0.37 mmol), PiVOH (0.57 g, 5.5 mmol) and K2CO3 (5.14 g, 37.27 mmol) were dissolved in N,N-dimethylacetamide (DMAc) (6 mL) and heated at 130 °C under nitrogen atmosphere for 48 h. The polymer was precipitated in methanol and filtered to obtain P8 polymer.

[0081] H-1: 1H NMR (400 MHz, Chloroform-d) δ 7.58 (d, J = 8.2 Hz, 2H), 7.54 - 7.49 (m, 2H), 7.48 (d, J = 3.6 Hz, 2H), 7.43 (d, J = 1.8 Hz, 2H), 7.18 (dd, J = 8.8, 2.6 Hz, 2H), 6.88 (d, J = 8.8 Hz, 2H), 4.27 (q, J = 7.1 Hz, 4H), 4.16 (t, J = 5.1 Hz, 4H), 3.87 (t, J = 5.1 Hz, 4H), 3.74 (dd, J = 5.9, 3.7 Hz, 4H), 3.67 - 3.62 (m, 9H), 3.57 (dd, J = 6.0, 3.6 Hz, 4H), 3.50 (q, J = 7.0 Hz, 5H), 1.31 (t, J = 7.1 Hz, 7H), 1.19 (t, J = 7.0 Hz, 6H).

[0082] H-2: 1 H NMR (400 MHz, Chloroform-d) δ 4.08 (s, 4H), 3.73 - 3.60 (m, 14H), 3.60 - 3.51 (m, 15H), 3.51 (d, J = 7.0 Hz, 3H), 1.19 (t, J = 7.0 Hz, 7H).

[0083] H-3: 1 H NMR (400 MHz, Chloroform-d) δ 3.99 (q, J = 5.1 Hz, 2H), 1.29 (t, J = 5.0 Hz, 3H). P8: 13 C NMR (400 MHz, Chloroform-d) δ 167.36, 164.67, 156.80, 153.27, 149.80, 144.41, 139.66, 137.98, 137.84, 137.38, 134.01, 132.47, 130.69, 130.42, 128.93, 124.15, 119.05, 118.76, 114.79, 113.01, 99.68, 93.03, 92.63, 91.93, 63.65, 63.01, 62.08, 60.86, 45.12, 35.06, 15.23, 14.28, 14.10.

[0084] Example 9: Synthesis of black conjugated polymer P9

[0085]

[0086] I-1 (10.97 g, 13.68 mmol), I-2 (10 g, 27.36 mmol), I-3 (4.43 g, 13.68 mmol), Pd(OAC)2 (0.083 g, 0.37 mmol), PiVOH (0.57 g, 5.5 mmol) and K2CO3 (5.14 g, 37.27 mmol) were dissolved in N,N-dimethylacetamide (DMAc) (6 mL) and heated at 130 °C under nitrogen atmosphere for 48 h. The polymer was precipitated in methanol and filtered to obtain P9 polymer.

[0087] I-1: 1 H NMR (500 MHz, Chloroform-d) δ 7.58 (d, J = 8.2 Hz, 2H), 7.54 - 7.49 (m, 2H), 7.48 (d, J = 3.6 Hz, 2H), 7.43 (d, J = 1.8 Hz, 2H), 7.18 (dd, J = 8.8, 2.6 Hz, 2H), 6.88 (d, J = 8.8 Hz, 2H), 4.27 (q, J = 7.1 Hz, 4H), 4.16 (t, J = 5.1 Hz, 4H), 3.87 (t, J = 5.1 Hz, 4H), 3.74 (dd, J = 5.9, 3.7 Hz, 4H), 3.67 - 3.62 (m, 9H), 3.57 (dd, J = 6.0, 3.6 Hz, 4H), 3.50 (q, J = 7.0 Hz, 5H), 1.31 (t, J = 7.1 Hz, 7H), 1.19 (t, J = 7.0 Hz, 6H).

[0088] I-2: 1 H NMR (400 MHz, Chloroform-d) δ 4.08 (s, 4H), 3.73 - 3.60 (m, 14H), 3.60 - 3.51 (m, 15H), 3.51 (d, J = 7.0 Hz, 3H), 1.19 (t, J = 7.0 Hz, 7H).

[0089] I-3: 1 H NMR (500 MHz, Chloroform-d) δ 3.99 (q, J = 5.1 Hz, 2H), 1.29 (t, J = 5.0 Hz, 3H). P9: 13C NMR (400 MHz, Chloroform-d) δ 167.36, 164.67, 156.80, 153.27, 149.80, 144.41, 139.66, 137.98, 137.84, 137.38, 134.01, 132.47, 130.69, 130.42, 128.93, 124.15, 119.05, 118.76, 114.79, 113.01, 99.68, 93.03, 92.63, 91.93, 63.65, 63.01, 62.08, 60.86, 45.12, 35.06, 15.23, 14.28, 14.10.

[0090] Example 10: Synthesis of black conjugated polymer P10

[0091]

[0092] J-1 (2.19 g, 2.74 mmol), J-2 (10 g, 27.36 mmol), J-3 (7.97 g, 24.62 mmol), Pd(OAC)2 (0.083 g, 0.37 mmol), PiVOH (0.57 g, 5.5 mmol) and K2CO3 (5.14 g, 37.27 mmol) were dissolved in N,N-dimethylacetamide (DMAc) (6 mL) and heated at 130 °C under nitrogen atmosphere for 48 h. The polymer was precipitated in methanol and filtered to obtain P10 polymer.

[0093] J-1: 1 H NMR (500 MHz, Chloroform-d) δ 7.58 (d, J = 8.2 Hz, 2H), 7.54 - 7.49 (m, 2H), 7.48 (d, J = 3.6 Hz, 2H), 7.43 (d, J = 1.8 Hz, 2H), 7.18 (dd, J = 8.8, 2.6 Hz, 2H), 6.88 (d, J = 8.8 Hz, 2H), 4.27 (q, J = 7.1 Hz, 4H), 4.16 (t, J = 5.1 Hz, 4H), 3.87 (t, J = 5.1 Hz, 4H), 3.74 (dd, J = 5.9, 3.7 Hz, 4H), 3.67 - 3.62 (m, 9H), 3.57 (dd, J = 6.0, 3.6 Hz, 4H), 3.50 (q, J = 7.0 Hz, 5H), 1.31 (t, J = 7.1 Hz, 7H), 1.19 (t, J = 7.0 Hz, 6H).

[0094] J-2: 1H NMR (400 MHz, Chloroform-d) δ 4.08 (s, 4H), 3.73 - 3.60 (m, 14H), 3.60 - 3.51 (m, 15H), 3.51 (d, J = 7.0 Hz, 3H), 1.19 (t, J = 7.0 Hz, 7H).

[0095] J-3: 1 H NMR (500 MHz, Chloroform-d) δ 3.99 (q, J = 5.1 Hz, 2H), 1.29 (t, J = 5.0 Hz, 3H).P10: 13 C NMR (400 MHz, Chloroform-d) δ 167.36, 164.67, 156.80, 153.27, 149.80, 144.41, 139.66, 137.98, 137.84, 137.38, 134.01, 132.47, 130.69, 130.42, 128.93, 124.15, 119.05, 118.76, 114.79, 113.01, 99.68, 93.03, 92.63, 91.93, 63.65, 63.01, 62.08, 60.86, 45.12, 35.06, 15.23, 14.28, 14.10.

[0096] Example 11: Synthesis of black conjugated polymer P11

[0097]

[0098] K-2 (10 g, 13.68 mmol), K-3 (4.02 g, 13.68 mmol), K-4 (4.43 g, 13.68 mmol), Pd(OAC)2 (0.083 g, 0.37 mmol), PiVOH (0.57 g, 5.5 mmol) and K2CO3 (5.14 g, 37.27 mmol) were dissolved in N,N-dimethylacetamide (DMAc) (6 mL) and heated at 130 °C under nitrogen atmosphere for 48 hours. The polymer was precipitated in methanol and filtered to obtain P11 polymer.

[0099] K-1: 1 H NMR (400 MHz, Chloroform-d) δ 4.08 (s, 4H), 3.73 - 3.60 (m, 14H), 3.60 - 3.51 (m, 15H), 3.51 (d, J = 7.0 Hz, 3H), 1.19 (t, J = 7.0 Hz, 7H).

[0100] K-2: 1H NMR (400 MHz, Chloroform-d) δ 7.66 (s, 2H).

[0101] K-3: 1 H NMR (500 MHz, Chloroform-d) δ 3.99 (q, J = 5.1 Hz, 2H), 1.29 (t, J = 5.0 Hz, 3H).

[0102] P11:13C NMR (400 MHz, Chloroform-d) δ 164.67, 153.27, 144.41, 137.98, 134.01, 130.69, 113.01, 99.68, 63.01, 45.12, 35.06, 14.10.

[0103] A novel black conductive polymer is introduced in this invention. The device of this polymer has ultra-low driving voltage, ultra-long cycle stability and high coloration efficiency. Specifically, a black high-performance conductive polymer is obtained by copolymerization of four monomers. In addition, this polymer has a highest occupied molecular orbital (HOMO) energy level of -4.21 to -4.47 eV and a lowest unoccupied molecular orbital (LUMO) energy level of -2.52 to -2.78 eV. The molecular weight of each polymer material in the foregoing examples is shown in Table 1 below.

[0104] Table 1. Polymer molecular weight

[0105]

[0106] The use of this compound as a color-changing layer material in an organic electrochromic device can improve the service life and coloration efficiency of the device. The structure of the electrochromic device is shown in Figure 1 The CV curve of the device made of black conjugated polymer P5 in Example 5 is shown in Figure 2 The comparison of the photos of the neutral state black and the colored state transparent color of the device made of black conjugated polymer P5 is shown in Figure 3

[0107] The above-mentioned polymer structures are only part of the representatives, and other black conductive polymer molecules containing the same idea are within the scope of this patent.

[0108] Although the embodiments of the present application have been shown and described above, it should be understood by those skilled in the art that the above-mentioned embodiments are exemplary and cannot be understood as limiting the present application, and those skilled in the art can make changes, modifications, replacements and variations to the above-mentioned embodiments within the scope of the present application.​

Claims

1. A black conductive polymer material, characterized in that, The molecular formula is as follows: Where y = 1, x + z + w = ​​1; x ≥ 0, z ≥ 0, w > 0; at most one of x and z is 0; n is a natural number less than 100; R5 is a branched or straight-chain alkyl chain with 1 to 20 carbon atoms; R1 = R2, R3 = R4; R1 and R3 are each independently selected from the following:

2. The black conductive polymer material according to claim 1, characterized in that, Selected from the following:

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

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