A deuterium-containing polymer, and a preparation method and application thereof

Abstract

The application provides a deuterium-containing polymer and a preparation method and application thereof. The polymer is based on a polymer containing a deuterium element acceptor unit, that is, isotopes of hydrogen elements, namely deuterium atoms, are introduced into an electron acceptor unit benzene ring or anthracene ring, and a thiophene derivative is used as a terminal donor unit. The deuterium-containing polymer has good electrochromic performance, such as fast response time, good optical transmittance and good stability, and has a wide application in the preparation of electrochromic devices. The application further provides a preparation method and application of the deuterium-containing polymer.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of polymer materials, and particularly relates to a deuterium-containing polymer and a preparation method and application thereof. BACKGROUND

[0002] In recent years, with the development of portable electronic devices, energy storage devices that can display working status have become increasingly important. Electrochromism is based on electrochemical reactions or the influence of electric fields on the electronic structure of materials. Under the action of an electric field, the redox state of the material changes, causing changes in its optical properties. This change is usually manifested as a change in color, including changes in transmittance.

[0003] Electrochromic materials can be divided into two categories: inorganic materials (such as tungstate and vanadate) and organic materials (such as electrochromic polymers). Inorganic electrochromic materials generally have high stability and fast response speed, while organic electrochromic materials have advantages in flexibility and processability, making electrochromic technology widely used in many fields, such as smart windows, automotive rearview mirrors, display technology, aerospace, etc.

[0004] Despite the wide application potential of electrochromic technology, there are still some challenges, such as material cost, service life, response speed, and environmental stability. Future research will focus on improving material performance, reducing costs, and expanding application areas to further develop and popularize electrochromic technology.

[0005] Therefore, exploring and developing new types of electrochromic polymers with novel structures is a problem that needs to be solved today. SUMMARY

[0006] The present application aims to at least solve one of the above technical problems existing in the prior art. To this end, the present application provides a deuterium-containing polymer. The deuterium-containing polymer introduces the isotope deuterium of hydrogen atom and a specific donor-acceptor-donor (D-A-D) structure design, which can improve the electrochromic performance of the polymer, such as coloring efficiency, response time, etc.

[0007] The present application also provides a method for preparing a deuterium-containing polymer.

[0008] The present application also provides an electrochromic material.

[0009] The present application also provides the use of a deuterium-containing polymer in the preparation of an electrochromic device.

[0010] To achieve the above-mentioned purposes, the technical solutions adopted by the present application are as follows:

[0011] The first aspect of the present application provides a deuterium-containing polymer having a structure as shown in any one of formula (I) to formula (IV):

[0012] (I), (II),

[0013] (III), (IV),

[0014] In formula (I)-(IV), X1-X4 are each independently O, S, Se; Y1-Y8 are each independently O or S; R1-R4 are each independently C2-C20 alkyl; n1-n4 are each independently 3-200. 12

[0015] The technical solution of the present application has at least the following beneficial effects: the introduction of deuterium helps to improve the ion migration rate of electrochromic polymers, and the deuterium-containing polymer of the present application can improve the response speed (T ox =0.1 s) of electrochromic materials when used in electrochromic materials, so that color change can be achieved faster in application.

[0016] According to some preferred embodiments of the present application, X1-X4 are each independently S.

[0017] According to some preferred embodiments of the present application, Y1-Y8 are each independently O.

[0018] According to some preferred embodiments of the present application, R1-R4 are each independently C5-C20 alkyl. 10

[0019] According to some more preferred embodiments of the present application, R1-R4 are each independently C 10 H 21 .

[0020] According to some specific embodiments of the present application, the deuterium-containing polymer has a structure as shown in any one of formula (1)-(4):

[0021] (1),

[0022] (2),

[0023] (3),

[0024] (4),

[0025] In formula (1)-(4), n1-n4 are each independently 3-200.

[0026] ​​The second aspect of the present application provides a method for preparing the deuterium-containing polymer of the first aspect of the present application, comprising the following steps: subjecting an active precursor of the deuterium-containing polymer to an electrochemical polymerization reaction to obtain the deuterium-containing polymer, the active precursor of the deuterium-containing polymer having a structure represented by any one of formula (I') to formula (IV'):

[0027] (I'),

[0028] (II'),

[0029] (III'),

[0030] (IV'),

[0031] In formula (I') to formula (IV'), X1 to X4, Y1 to Y8 and R1 to R4 are defined as above.

[0032] The preparation method of the present application does not require expensive equipment and complex process control, the reaction conditions are not harsh, the raw materials are easy to obtain, the production cost is low, and the industrialized production is easy.

[0033] According to some embodiments of the present application, the method for preparing the active precursor comprises: subjecting an acceptor compound and a donor compound to a cross-coupling reaction in a solvent in the presence of a catalyst to obtain the active precursor.

[0034] The acceptor compound is: (I'') or (II'');

[0035] The donor compound is: (I''') or (II''');

[0036] The catalyst comprises Pd(PPh3)4 and / or Pd(PPh3)2Cl2.

[0037] The solvent comprises at least one of benzene, toluene or DMF.

[0038] According to some embodiments of the present application, in the method for preparing the active precursor, the solvent comprises toluene and DMF.

[0039] According to some preferred embodiments of the present application, in the method for preparing the active precursor, the volume ratio of toluene to DMF in the solvent is (3-5):1, for example, about 4:1.

[0040] According to some embodiments of the present application, in the preparation method of the active precursor, the molar ratio of the acceptor compound to the donor compound is 1: (2-3), for example, about 1:2.5.

[0041] According to some embodiments of the present application, in the preparation method of the active precursor, the molar ratio of the acceptor compound to the catalyst is 1: (0.01-0.1), further preferably 1: (0.03-0.05).

[0042] According to some embodiments of the present application, in the preparation method of the active precursor, the molar amount of the acceptor compound to the volume of the solvent is 1 mmol: (50-200) mL, for example, about 1 mmol: 100 mL or about 1 mmol: 150 mL.

[0043] According to some embodiments of the present application, in the preparation method of the active precursor, the temperature of the cross-coupling reaction is 100-140℃; further preferably 110-130℃, for example, about 120℃.

[0044] According to some embodiments of the present application, in the preparation method of the active precursor, the time of the cross-coupling reaction is 24-72h; further preferably 36-60h, for example, about 48h.

[0045] According to some embodiments of the present application, in the preparation method of the active precursor, the cross-coupling reaction further comprises a purification step; further preferably, the purification is chromatographic separation purification.

[0046] According to some embodiments of the present application, the chromatographic column used for chromatographic separation purification is selected from a silica gel column.

[0047] According to some embodiments of the present application, the eluent used for chromatographic separation purification comprises dichloromethane (DCM) and petroleum ether (PE); further preferably, the volume ratio of dichloromethane to petroleum ether is 1: (1-3), for example, about 1:2.

[0048] In the preparation method of the active precursor of the present application, the cross-coupling reaction is Stille or Suzuki palladium-catalyzed cross-coupling reaction, and through the cross-coupling reaction, the active precursor based on the deuterium element intermediate, i.e., the active precursor represented by formula (I')-(IV'), can be prepared.

[0049] According to some embodiments of the present application, in the preparation method of the active precursor, the cross-coupling reaction is carried out in an inert gas atmosphere. In a specific embodiment of the present application, the inert gas is selected from nitrogen.

[0050] According to some embodiments of the present application, the electrochemical polymerization reaction comprises electrodepositing in a three-electrode system consisting of a reference electrode, a counter electrode and a working electrode, using a solution containing the active precursor as an electrolyte solution, to obtain the polymer on the working electrode.

[0051] According to some embodiments of the present application, the solvent of the electrolyte solution comprises at least one of dichloromethane (CH2Cl2), trichloromethane (CHCl3) or acetonitrile (MeCN).

[0052] According to some embodiments of the present application, the electrolyte solution further contains a supporting electrolyte.

[0053] According to some embodiments of the present application, the supporting electrolyte comprises at least one of tetrabutylammonium hexafluorophosphate (PF6), tetrabutylammonium tetrafluoroborate (BF4) or lithium perchlorate.

[0054] According to some embodiments of the present application, the concentration of the active precursor in the electrolyte solution is 0.0005-0.01 mol·L -1 , for example about 0.001 mol·L -1 , about 0.005 mol·L -1 , or about 0.01 mol·L -1 .

[0055] According to some embodiments of the present application, the concentration of the supporting electrolyte in the electrolyte solution is 0.01-0.2 mol·L -1 , 0.1 mol·L -1 , or about 0.15 mol·L -1 .

[0056] According to some embodiments of the present application, the reference electrode is selected from Ag / AgCl electrode.

[0057] According to some embodiments of the present application, the counter electrode is selected from platinum electrode.

[0058] According to some embodiments of the present application, the working electrode is selected from Pt, glassy carbon or ITO conductive glass electrode.

[0059] According to some embodiments of the present application, the electrodepositing in the electrochemical polymerization reaction is performed by constant potential method, constant current method or cyclic voltammetry.

[0060] According to some embodiments of the present application, the electrochemical polymerization reaction is performed under a protective gas atmosphere.

[0061] In some embodiments of the present application, the protective gas is selected from argon.

[0062] In some embodiments of the application, the D-A-D polymer thin film material of the application is electrodeposited on the working electrode using a constant potential method. Preferably, the constant potential used is 1.15V-1.5V, for example about 1.2V, about 1.3V or about 1.4V; the deposition time is 20s-50s; for example about 30s or 40s.

[0063] A third aspect of the application provides an electrochromic material comprising the deuterium-containing polymer of the first aspect of the application or the deuterium-containing polymer produced by the method of the second aspect of the application.

[0064] A fourth aspect of the application provides the use of the deuterium-containing polymer of the first aspect of the application or the deuterium-containing polymer produced by the method of the second aspect of the application in the preparation of an electrochromic device.

[0065] According to some embodiments of the application, the electrochromic device comprises one or both of a display device or a light-transmitting device; further preferably, the electrochromic device comprises at least one of a display, electrochromic glass, a smart window or a rearview mirror.

[0066] The application has at least the following beneficial effects:

[0067] The polymer of the application is based on a polymer containing a deuterium element acceptor unit, i.e. an isotope of the hydrogen element, deuterium, is introduced into the benzene ring or anthracene ring of the electron acceptor unit (a deuterated benzene ring or anthracene ring as the acceptor unit), with a thiophene derivative as the terminal donor unit. Since deuterium atoms have strong chemical stability, replacing hydrogen atoms with deuterium atoms can reduce the participation of benzene rings or anthracene rings in electrochemical reactions, thereby improving the stability of the polymer. Moreover, the deuterium-containing polymer of the application has good electrochromic performance under different voltages, such as fast response time, good optical transmittance, high coloration efficiency and good stability, and has wide application in the preparation of electrochromic devices.

[0068] In summary, the application provides a polymer based on a deuterium element-containing acceptor unit. The presence of deuterium can reduce the reactivity of the polymer material in chemical reactions or high-temperature environments, thereby enhancing the chemical stability of the polymer; at the same time, the conjugated polymer of the application, in which the deuterium-containing acceptor is combined with a donor unit with strong electron-donating ability, exhibits faster response time (T ox =0.1 s) and higher coloration efficiency (613.8 cm 2 C -1 ). BRIEF DESCRIPTION OF DRAWINGS

[0069] Figure 1 The 4D-EDOT active precursor of Example 1 was electrodeposited in DCM-Bu4NPF6(0.1 mol·L-1 Electrochemical polymerization diagram in the system.

[0070] Figure 2 The polymer P(4D-EDOT) of Example 1 was used in MeCN-Bu4NPF6 (0.1 mol·L⁻¹). -1 ) spectroelectrochemical diagrams of the system.

[0071] Figure 3 The transmittance-time curve of polymer P(4D-EDOT) in Example 1 is shown.

[0072] Figure 4 For Comparative Example 1, polymer P (EDOT-Ph-EDOT) was used in MeCN-Bu4NPF6 (0.1 mol·L⁻¹). -1 ) spectroelectrochemical diagrams of the system.

[0073] Figure 5 The transmittance-time curve of polymer P(EDOT-Ph-EDOT) in Comparative Example 1 is shown.

[0074] Figure 6 The polymer P(4AhD-EDOT) of Example 2 was used in MeCN-Bu4NPF6 (0.1 mol·L⁻¹). -1 ) spectroelectrochemical diagrams of the system.

[0075] Figure 7 The transmittance-time curve of polymer P(4AhD-EDOT) in Example 2 is shown. Detailed Implementation

[0076] The following specific embodiments further illustrate the content of the present invention in detail. It should also be understood that the following embodiments are only for further explanation of the present invention and should not be construed as limiting the scope of protection of the present invention. Non-essential improvements and adjustments made by those skilled in the art based on the principles described herein are all within the scope of protection of the present invention. The specific process parameters, etc., in the following examples are merely examples within a suitable range; that is, those skilled in the art can make selections within a suitable range based on the description herein, and are not intended to be limited to the specific data in the examples below. Unless otherwise specified, the raw materials, reagents, or apparatus used in the following embodiments and comparative examples can be obtained from conventional commercial sources or by existing known methods.

[0077] Unless otherwise indicated herein, the description herein of ranges of values is intended to serve as a shorthand method of referring individually to each separate value falling within the range, and each individual value is incorporated into the specification as if it were individually recited herein. Unless otherwise indicated herein, all precise values provided herein represent respective approximations (e.g., all precise exemplary values provided in relation to a particular factor or measurement can be considered to provide respective approximate measurements, as modified by "about" where appropriate).

[0078] As used herein, the term "about," when used in connection with a numerical value, means including a range or set of values. For example, "about" means a range of values that includes ±5%, ±2%, ±1%, ±0.5%, ±0.2%, or ±0.1% of the value. In one embodiment, the term "about" refers to a range of values that is 5% more or less than a particular value. In another embodiment, the term "about" refers to a range of values that is 2% more or less than a particular value. In another embodiment, the term "about" refers to a range of values that is 1% more or less than a particular value.

[0079] The experimental methods used in the examples are conventional methods unless otherwise specified; the materials, reagents, etc. used are commercially available reagents and materials unless otherwise specified. The same parameter values are used in the same parameter in each example unless otherwise specified. The examples described below are illustrative and are intended to explain the present application, and are not to be construed as limiting the present application.

[0080] It should be noted that in the examples of the present application, the coloring efficiency refers to the ratio of the change in absorbance of the electrochromic material at a given wavelength to the total electronic injection or extraction.

[0081] For an electrochromic material, the coloring efficiency CE (cm 2 ·C -1 ) is an important parameter for evaluating the performance of the material. The study of the coloring efficiency of conductive polymers needs to combine the electrochemical and spectral change processes of the electrochromic film, in which Q d (C·cm -2 ) refers to the amount of charge injected / extracted per unit area, and the calculation formula is as follows:

[0082] CE = ΔOD / Q d ;

[0083] In which, the change in optical contrast (ΔOD) refers to the logarithmic value of the ratio of the transmittance (T max (%) of the polymer film in the doped state and the transmittance T ox (%) in the neutral state when the polymer film is electrochemically oxidized and reduced at a specific wavelength λ red , and is calculated by the following formula:

[0084] ΔOD = log (T ox / T red ).

[0085] Example 1

[0086] Electrochemical synthesis of polymer P(4D-EDOT):

[0087] (1) Synthesis of 4D-EDOT active precursor:

[0088]

[0089] In a nitrogen atmosphere, 1,4-dibromobenzene-2,3,5,6-d4 (2.08 mmol, 0.5 g), tributyl(2,3-dihydro[3,4-b][1,4]dioxin-5-yl)stannane (5.20 mmol, 2.25 g), and catalyst Pd(PPh3)4 (0.08 mmol, 0.096 g) were placed in a 250 mL single-necked flask, stirred uniformly with the addition of DMF (20 mL) and dry toluene (80 mL), heated to 120°C, and condensed to reflux for 48 hours. After the system was cooled, the product was poured into saturated brine, extracted with dichloromethane 4-5 times, and then the organic layer was washed with a small amount of water, followed by removal of the solvent by reduced pressure distillation, rotary evaporation, separation by silica gel column chromatography, and elution with DCM:PE = 1:2 to obtain the product 4D-EDOT as a light yellow powder with a yield of 67%.

[0090] (2) Electrochemical polymerization of polymer P(4D-EDOT):

[0091]

[0092] The electrochemical polymerization was carried out in a three-electrode system under an argon atmosphere, with a silver / silver chloride electrode as the reference electrode, a platinum wire as the counter electrode, and a glassy carbon as the working electrode; 10 mL of dichloromethane was used as the solvent, 4D-EDOT (0.00362 g, 0.01 mmol) as the polymerization monomer, and a mixture of 10 mL of acetonitrile and tetrabutylammonium hexafluorophosphate (0.3874 g, 1 mmol) as the supporting electrolyte solution; the polymerization was carried out in the monomer solution containing the electrolyte by constant potential method, with a polymerization potential of 1.15 V, a scan rate of 100 mV / s, and a deposition time of 50 s; the polymer film obtained by electrodeposition was soaked and rinsed with acetonitrile to remove the electrolyte solution and precursor in the polymer, thereby obtaining the polymer P(4D-EDOT).

[0093] wherein, Figure 1 shows the 4D-EDOT active precursor (0.0005 mol·L -1) in DCM-Bu4NPF6(0.1 mol·L -1 ) solution. It can be seen that 4D-EDOT has good electrochemical polymerization behavior.

[0094] Electrochromic performance research:

[0095] (1) The spectroelectrochemical diagram of polymer P(4D-EDOT) in MeCN-Bu4NPF6(0.1 mol·L -1 ) system was tested, as shown in Figure 2 , and the color change of the polymer material was observed by naked eye. It can be seen that as the potential increases, the color of the polymer material changes from dark yellow to gray blue (dark yellow in the completely dedoped state), because the neutral state of the polymer material has an absorption peak in the purple light region and the red light region, and the color of the neutral state of the polymer material is dark yellow; after the polymer material is oxidized, the absorption peak in the purple light region gradually weakens, the absorption peak in the red light region gradually weakens, and finally completely disappears; therefore, the completely dedoped state of the polymer material is dark yellow, and the doped state of the polymer material is gray blue.

[0096] (2) The transmittance-time curves of polymer P(4D-EDOT) at 460 nm, 675 nm and 1100 nm wavelengths were tested. The response time and coloring efficiency calculated from the time-transmittance curve are shown in Table 1, wherein T red is the transmittance of the polymer film in the neutral state, T ox is the transmittance of the polymer film in the doped state, T=T red -T ox . From Table 1, it can be seen that the response time of the polymer P(4D-EDOT) is fast, and the coloring efficiency is high.

[0097] Table 1 Electrochromic parameters of polymer P(4D-EDOT)

[0098]

[0099] The optical transmittance of P(4D-EDOT) was studied by chronosorption method at 460 nm, 675 nm and 1100 nm wavelengths, respectively. During the experiment, the time interval of the potential step change was 5 s, as shown in Figure 3 . At the three specific wavelengths, the polymer material showed certain optical contrast and good optical stability; in addition, the optical transmittance had a great influence on the color change of the polymer material, and the polymer material could change from dark yellow in the completely dedoped state to gray blue in the doped state.

[0100] Example 2

[0101] Electrochemical synthesis of polymer P(4AhD-EDOT):

[0102] (1) Synthesis of 4AhD-EDOT active precursor:

[0103]

[0104] 9,10-dibromoanthracene-1,2,3,4,5,6,7,8-d8 (1.45 mmol, 0.5 g), tributyl(2,3-dihydro[3,4-b][1,4]dioxin-5-yl)stannane (3.22 mmol, 1.201 g), and catalyst Pd(PPh3)4 (0.06 mmol, 0.04 g) were placed in a 250 mL single-necked flask under nitrogen atmosphere, stirred uniformly after adding DMF (20 mL) and dry toluene (80 mL), heated to 120 °C, and condensed to reflux for 48 hours. After the system was cooled, the product was poured into saturated brine, extracted with dichloromethane 4-5 times, and then the organic layer was washed with a small amount of water, followed by removal of the solvent by reduced pressure distillation, rotary evaporation, separation by silica gel column chromatography, and elution with DCM:PE = 1:2 to obtain orange-red solid 4AhD-EDOT with a yield of 58.7%.

[0105] (2) Synthesis of polymer P(4AhD-EDOT):

[0106]

[0107] Electrochemical polymerization was carried out in a three-electrode system under argon atmosphere, with a silver / silver chloride electrode as the reference electrode, a platinum wire as the counter electrode, and a glassy carbon as the working electrode; 10 mL of dichloromethane was used as the electrolyte, 4AhD-EDOT (0.00466 g, 0.01 mmol) as the polymerization monomer, and a mixture of 10 mL of acetonitrile and tetrabutylammonium hexafluorophosphate (0.3874 g, 1 mmol) as the supporting electrolyte; constant potential method was used for polymerization, the polymerization potential was 1.08 V, the scan rate was 100 mV / s, and the deposition time was 50 s; the polymer film obtained by electrodeposition was soaked and washed with acetonitrile to remove the electrolyte solution and precursor in the polymer, and polymer P(4AhD-EDOT) was obtained.

[0108] Electrochromic performance research:

[0109] The spectroelectrochemical diagram of polymer P(4AhD-EDOT) in MeCN-Bu4NPF6 (0.1 mol·L -1 ) system is shown in Figure 6As shown in the figure, and in combination with the color change of the polymer material observed by naked eye, it can be seen that as the potential increases, the color of the polymer material changes from yellow to blue (yellow in the completely dedoped state), which is due to the fact that the neutral state polymer material has an absorption peak in the violet and red light regions, and the color of the neutral state polymer material is yellow; after the polymer material is oxidized, the absorption peak in the violet region gradually weakens, the absorption peak in the red region gradually weakens, and finally completely disappears.

[0110] The transmittance-time curve of the polymer P(4AhD-EDOT) at 522 nm and 682 nm was tested. The response time and coloring efficiency calculated from the time-transmittance curve are shown in Table 2. As can be seen from Table 2, the response time of the polymer P(4AhD-EDOT) is fast, and the coloring efficiency is high.

[0111] Table 2 Electrochromic parameters of the polymer P(4AhD-EDOT)

[0112]

[0113] The optical transmittance of P(4AhD-EDOT) at 522 nm and 682 nm was studied by chronosorption method, and the time interval of the potential step change was 5 s during the experiment, as shown in Figure 7 At the three wavelengths, the polymer material showed a certain optical contrast and good optical stability; in addition, the optical transmittance had a great influence on the color change of the polymer material, and the polymer material could change from yellow in the completely dedoped state to blue in the doped state.

[0114] Example 3

[0115] Electrochemical synthesis of the polymer P(4D-ProEDOT):

[0116] (1) Synthesis of 4D-ProEDOT active precursor:

[0117]

[0118] Under a nitrogen atmosphere, 1,4-dibromophenyl-2,3,5,6-deuterium (2.08 mmol, 0.5 g), tributyltin (3,3-decyl-3,4-dihydro-2H-thiophene[3,4-b][1,4]dioxane-6-yl) (4.30 mmol, 1.52 g), and catalyst Pd(PPh3)4 (0.08 mmol, 0.096 g) were placed in a 250 mL single-necked flask, DMF (20 mL) and dry toluene (80 mL) were added, and the mixture was stirred until homogeneous. The mixture was heated to 120 °C and refluxed for 48 hours. After the system was cooled, the product was poured into saturated brine and extracted 4-5 times with dichloromethane. The organic layer was then washed with a small amount of water. The solvent was removed by vacuum distillation and rotary evaporation. The product was then separated by silica gel chromatography with DCM:PE = 1:2 as the eluent. The purified product was a pale yellow powder, 4D-ProEDOT, with a yield of 48.3%.

[0119] (2) Synthesis of polymer P(4D-ProEDOT):

[0120]

[0121] Electrochemical polymerization was carried out in a three-electrode system under an argon atmosphere, with a silver / silver chloride electrode as the reference electrode, a platinum wire as the counter electrode, and glassy carbon as the working electrode. 10 mL of dichloromethane was used as the electrolyte, 4D-ProEDOT (0.00951 g, 0.01 mmol) as the monomer, and a mixed solution of 10 mL acetonitrile and tetrabutylammonium hexafluoride (0.3874 g, 1 mmol) as the supporting electrolyte. Polymerization was performed using a potentiostatic method at a polymerization potential of 1.2 V, a scan rate of 100 mV / s, and a deposition time of 50 s. The electrodeposited polymer film was immersed and rinsed with acetonitrile to remove the electrolyte solution and precursor from the polymer, yielding polymer P(4D-ProEDOT).

[0122] Example 4

[0123] Electrochemical synthesis of polymer P(4AhD-ProEDOT):

[0124] (1) Synthesis of the active precursor of 4AhD-ProEDOT:

[0125]

[0126] Under nitrogen atmosphere, 9,10-dibromoanthracene-1,2,3,4,5,6,7,8-d8 (1.45 mmol, 0.5 g), tributyl(3,3-didecyl-3,4-dihydro-2H-thiopheno[3,4-b][1,4]dioxepen-6-yl)tin (4.30 mmol, 1.52 g), and catalyst Pd(PPh3)4 (0.029 mmol, 0.025 g) were placed in a 250 mL single-necked flask, stirred uniformly after adding DMF (20 mL) and dry toluene (80 mL), heated to 120 °C, and condensed to reflux for 48 hours. After the system was cooled, the product was poured into saturated brine, extracted with dichloromethane 4-5 times, and then the organic layer was washed with a small amount of water, and then the solvent was removed by reduced pressure distillation, rotary evaporation, and separation by silica gel column chromatography with eluent (DCM:PE = 1:2) to obtain red solid 4AhD-ProEDOT with a yield of 45.0%.

[0127] (2) Synthesis of polymer P(4AhD-ProEDOT):

[0128]

[0129] Under argon atmosphere, electrochemical polymerization was carried out in a three-electrode system, with a silver / silver chloride electrode as the reference electrode, a platinum wire as the counter electrode, and a glassy carbon as the working electrode; 10 mL of dichloromethane was used as the electrolyte, 4AhD-ProEDOT (0.01055 g, 0.01 mmol) was used as the polymerization monomer, and a mixture of 10 mL of acetonitrile and tetrabutylammonium hexafluorophosphate (0.3874 g, 1 mmol) was used as the supporting electrolyte; constant potential method was used for polymerization, the polymerization potential was 1.05 V, the scan rate was 100 mV / s, and the deposition time was 50 s; the polymer film obtained by electrodeposition was soaked and washed with acetonitrile to remove the electrolyte solution and precursor in the polymer, and the polymer P(4AhD-ProEDOT) was obtained.

[0130] Comparative Example 1

[0131] Electrochemical synthesis of polymer P(EDOT-Ph-EDOT):

[0132] (1) Synthesis of EDOT-Ph-EDOT active precursor:

[0133]

[0134] Under nitrogen atmosphere, 1, 4-dibromobenzene (2.08 mmol, 0.5 g), tributyl(2, 3-dihydro[3, 4-b][1, 4]dioxin-5-yl)stannane (5.8 mmol, 2.25 g), and catalyst Pd(PPh3)4(0.08 mmol, 0.096 g) were placed in a 250 mL single-necked flask, stirred uniformly after adding DMF (20 mL) and dry toluene (80 mL), heated to 120°C, and condensed to reflux for 48 hours. After the system was cooled, the product was poured into saturated brine, extracted with dichloromethane 4-5 times, washed with a small amount of water, and then the solvent was removed by vacuum distillation and rotary evaporation, and the product was separated by silica gel column chromatography with eluent (DCM: PE = 1:2) to obtain a light yellow powder of EDOT-Ph-EDOT with a yield of 74%.

[0135] (2) Synthesis of polymer P(EDOT-Ph-EDOT):

[0136]

[0137] The electrochemical polymerization was carried out in a three-electrode system under argon atmosphere protection, with a silver / silver chloride electrode as the reference electrode, a platinum wire as the counter electrode, and a glassy carbon as the working electrode; 10 mL of dichloromethane was used as the electrolyte, EDOT-Ph-EDOT (0.00362 g, 0.01 mmol) as the polymerization monomer, and a mixture of 10 mL of acetonitrile and tetrabutylammonium hexafluorophosphate (0.3874 g, 1 mmol) as the supporting electrolyte; the polymerization was carried out by cyclic voltammetry with a polymerization potential of 1.15 V, a scan rate of 100 mV / s, and a deposition time of 50 s; the polymer film obtained by electrodeposition was soaked and washed with acetonitrile to remove the electrolyte solution and precursor in the polymer, thereby obtaining the polymer P(EDOT-Ph-EDOT).

[0138] Electrochromic performance research:

[0139] (1) The spectroelectrochemical diagram of the polymer P(EDOT-Ph-EDOT) in the MeCN-Bu4NPF6(0.1 mol·L -1 ) system was tested, as shown in Figure 4 , and the color change of the polymer material was observed by the naked eye. It can be seen that as the potential increases, the color of the polymer material changes from dark red to blue (dark red in the completely dedoped state), which is because the neutral state of the polymer material has an absorption peak in the violet and red light regions, and the color of the neutral state of the polymer material appears dark red; after the polymer material is oxidized, the absorption peak in the violet light region gradually weakens, the absorption peak in the red light region gradually weakens, and finally completely disappears; therefore, the polymer material in the completely dedoped state appears dark red, and the doped state of the polymer material appears blue.

[0140] (2) The transmittance-time curves of polymer P(EDOT-Ph-EDOT) at wavelengths of 460 nm, 675 nm and 1100 nm were tested. The response time and coloring efficiency calculated from the time-transmittance curves are shown in Table 3.

[0141] Table 3 Electrochromic parameters of P(EDOT-Ph-EDOT)

[0142]

[0143] The optical transmittance of P(EDOT-Ph-EDOT) was studied using time-lapse absorption chromatography at wavelengths of 460 nm, 700 nm, and 1100 nm. During the experiment, the time interval between potential step changes was 5 s. Figure 5 As shown, the polymer material exhibits certain optical contrast and good optical stability at three specific wavelengths. Furthermore, the optical transmittance has a significant impact on the color change of the polymer material, which can transform from a dark red state in a completely dedoped state to a blue state in a doped state.

[0144] Comparing Example 1 and Comparative Example 1, it was found that replacing H atoms with deuterium atoms significantly improved the colorimetric efficiency (123.5 cm⁻¹) of (P₄D-EDOT) in the near-infrared region (1100 nm) (123.5 cm⁻¹). 2 ·C -1 and high optical contrast. (T=34.0%). The introduction of deuterium isotopes is expected to extend the polymer into the field of near-infrared OLEDs, thereby enhancing the performance potential of near-infrared OLEDs. This will provide an effective strategy for development in the field of electrochromic technology in the near-infrared region. Furthermore, as shown in Example 2, the deuterium-containing polymer prepared in this invention can achieve colorimetric efficiencies of 360.7 cm⁻¹ at wavelengths of 522 nm and 682 nm, respectively. 2 C -1 613.8cm 2 C -1 The redox switching time at 682 nm is even less than 1.0 s, indicating that the deuterium-containing polymer of the present invention has excellent electrochromic properties, especially with a significant improvement in coloring efficiency and response time.

[0145] From the above, the polymer of the present application is a polymer based on deuterium-containing acceptor units, that is, the hydrogen element isotope-deuterium atom is introduced on the benzene ring or anthracene ring of the electron acceptor unit, and a thiophene derivative is used as a terminal donor unit. Because the deuterium atom has strong chemical stability, replacing the hydrogen atom with the deuterium atom can reduce the participation of the benzene ring or the anthracene ring in the electrochemical reaction, thereby improving the chemical stability of the polymer. Moreover, the deuterium-containing polymer of the present application has good electrochromic performance, such as fast response time, good optical transmittance, high coloring efficiency and the like, and has a wide application in the preparation of electrochromic devices.

[0146] In summary, the present application provides a polymer based on deuterium-containing acceptor units. The presence of deuterium can reduce the reactivity of the polymer material in chemical reactions or high-temperature environments, thereby enhancing the chemical stability of the polymer; at the same time, the conjugated polymer of the present application containing deuterium atoms combined with strong electron-donating donor units exhibits faster response time (T ox =0.1 s) and higher coloring efficiency (613.8 cm 2 ·C -1 ) in electrochromism.

[0147] The above describes the present application in detail in combination with the embodiments, but the present application is not limited to the above embodiments, and various changes can be made within the knowledge range possessed by those skilled in the art without departing from the purpose of the present application.

Claims

1. A deuterium-containing polymer, characterized by, having a structure as shown in formula (I) or formula (III): (I)， (III), In formula (I) and (III), X1 and X3 are each independently O, S, Se; Y1~Y2 and Y5-Y6 are each independently O or S; n1 and n3 are each independently 3~200.

2. The deuterium-containing polymer of claim 1, wherein In formula (I) and formula (III), X1 and X3 are each independently S; and / or, Y1~Y2 and Y5-Y6 are each independently O.

3. The deuterium-containing polymer of claim 2, wherein The deuterium-containing polymer has a structure as shown in formula (1) or formula (3): （1）， （3）， In formula (1) and formula (3), n1 and n3 are each independently 3~200.

4. A method of producing the deuterium-containing polymer as claimed in any one of claims 1 to 3, characterized by, comprising the following steps: carrying out electrochemical polymerization reaction on the active precursor of the deuterium-containing polymer to obtain the deuterium-containing polymer, the active precursor of the deuterium-containing polymer having a structure as shown in formula (I') or formula (III'): （I’）， (III'), In formula (I') and formula (III'), X1 and X3, Y1~Y2 and Y5-Y6 are as defined in any one of claims 1~3.

5. The method of claim 4, wherein, The preparation method of the active precursor comprises: carrying out cross-coupling reaction on an acceptor compound and a donor compound in a solvent in the presence of a catalyst to obtain the active precursor; The acceptor compound is: (I") or (II"); The donor compound is: (I''); The catalyst comprises tetrakis-triphenylphosphine palladium and / or bis-triphenylphosphine palladium dichloride; The solvent comprises at least one of benzene, toluene or N,N-dimethylformamide.

6. The method of claim 4, wherein, The electrochemical polymerization reaction comprises: taking a solution containing the active precursor as an electrolyte solution, carrying out electrodeposition in a three-electrode system composed of a reference electrode, a counter electrode and a working electrode to obtain the polymer on the working electrode; the reference electrode is selected from Ag / AgCl electrode; the counter electrode is selected from platinum electrode; and the working electrode is selected from Pt, glassy carbon or ITO conductive glass electrode.

7. The method of claim 6, wherein, The solvent of the electrolyte solution comprises at least one of dichloromethane, trichloromethane or acetonitrile; and / or, the electrolyte solution further contains a supporting electrolyte; the supporting electrolyte comprises at least one of tetrabutylammonium hexafluorophosphate, tetrabutylammonium tetrafluoroborate or lithium perchlorate.

8. The method of claim 7, wherein, The concentration of the active precursor in the electrolyte solution is 0.0005-0.01 mol·L -1 ; and / or, the concentration of the supporting electrolyte is 0.01-0.2 mol·L -1 .

9. An electrochromic material characterized in that, It comprises the deuterium-containing polymer of any one of claims 1 to 3 or the deuterium-containing polymer prepared by the method of any one of claims 4 to 8.

10. Use of the deuterium-containing polymer of any one of claims 1 to 3 or the deuterium-containing polymer prepared by the method of any one of claims 4 to 8 in the preparation of an electrochromic device.

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