CN112898543A - Thiophene polymer film and preparation method and application thereof - Google Patents
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Abstract
The invention provides a thiophene polymer film and application thereof in preparing an electrochromic material, wherein the thiophene polymer film is composed of a polymer (P (E2SBFE2)) shown in a formula 1. P (EDOT) in comparison with PEDOT film2‑SBF‑EDOT2) The film has richer color change in a voltage range of 0-0.5V: at 0V, P (EDOT)2‑SBF‑EDOT2) The film appeared cyan, at 0.5V, P (EDOT)2‑SBF‑EDOT2) The film appeared red.
Description
Technical Field
The invention relates to a novel thiophene polymer film polymer, a preparation method thereof and application thereof in the field of electrochromism.
Background
The thiophene polymer poly 3, 4-ethylenedioxythiophene (PEDOT) is a conductive polymer material with good conductivity and high stability, and is widely applied to the field of photoelectricity. PEDOT can change color from deep blue (-0.5V) to light blue (0.8V) under different voltages, so that PEDOT can be applied to products such as electrochromic intelligent windows and electrochromic automobile anti-glare rearview mirrors. However, the unicity of PEDOT color change becomes a key factor restricting the application of PEDOT color change in the electrochromic field. Therefore, the design of a novel thiophene polymer with electrochromic properties different from that of PEDOT has wide research and application prospects.
Disclosure of Invention
In order to solve the problems, the invention provides a novel thiophene polymer film with excellent electrochromic performance, a preparation method thereof and application in the field of electrochromism.
In order to achieve the purpose, the invention adopts the following technical scheme:
the present invention provides a thiophene polymer film which is composed of a polymer (P (E2SBFE2)) represented by formula 1.
Further, the thiophene polymer film is prepared according to the following method:
adopting a three-electrode system, taking Indium Tin Oxide (ITO) glass as a working electrode, a platinum sheet as a counter electrode, silver/silver chloride as a reference electrode, dissolving monomers 2, 7-bis (2,2 ', 3, 3' -tetrahydro-5, 5 '-dithieno [3,4-b ] [1,4] dioxin) -9,9' -spirobifluorene (E2SBFE2 for short) and tetrabutyl ammonium hexafluorophosphate in dichloromethane as electrolyte, carrying out electrochemical polymerization, replacing the electrolyte with dichloromethane solution of tetrabutyl ammonium hexafluorophosphate after the electrochemical polymerization is finished, and carrying out 60s dedoping by-0.2V by adopting a potentiostatic method to obtain the thiophene polymer film; in the electrolyte, the concentration of the monomer 2, 7-bis (2,2 ', 3, 3' -tetrahydro-5, 5 '-dithieno [3,4-b ] [1,4] dioxin) -9,9' -spirobifluorene is 0.1mmol/L to 100mmol/L (preferably 1mmol/L), and the concentration of tetrabutylammonium hexafluorophosphate is 0.01mol/L to 0.5mol/L (preferably 0.1 mol/L); the concentration of the tetrabutyl ammonium hexafluorophosphate in the dichloromethane solution of the tetrabutyl ammonium hexafluorophosphate is 0.01 mol/L-0.5 mol/L (preferably 0.1 mol/L).
Further, the electrochemical polymerization is carried out at room temperature by a constant potential polymerization method at a voltage of 1.2 to 1.5V (preferably 1.4V) and an electric quantity of 0.02C to 0.2C (preferably 0.05C).
The electrochemical polymerization condition can also adopt a cyclic voltammetry polymerization method to carry out polymerization by scanning for 3-30 cycles (preferably 5 cycles) at a scanning speed of 100mv/s and 0-1.4V.
The invention also provides an application of the thiophene polymer film in preparing electrochromic materials.
The invention characterizes the photophysical properties and the electrochromic performance of the electrochemical workstation by the absorption spectrum of ultraviolet-visible light.
Compared with the prior art, the invention has the following beneficial effects:
p (EDOT) in comparison with PEDOT film2-SBF-EDOT2) The film has richer color change in a voltage range of 0-0.5V: at 0V, P (EDOT)2-SBF-EDOT2) The film appeared cyan, at 0.5V, P (EDOT)2-SBF-EDOT2) The film appeared red.
Drawings
FIG. 1 is a scanning electron micrograph (magnification: 10 ten thousand times) of a P (E2SBFE2) thin film obtained in example 1;
FIG. 2 is a graph showing the UV absorption of the P (E2SBFE2) film obtained in example 1;
FIG. 3 is a graph showing the contrast of the P (E2SBFE2) film obtained in example 1;
FIG. 4 is a graph of the response time of the P (E2SBFE2) film prepared in example 1;
FIG. 5 is a memory effect diagram of the P (E2SBFE2) film obtained in example 1;
FIG. 6 is a nuclear magnetic hydrogen spectrum of monomer E2SBFE 2;
FIG. 7 is a mass spectrum of monomer E2SBFE 2;
FIG. 8 is a graph showing the response time of the P (E2SBFE2) film obtained in example 2.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto.
Preparation of E2SBFE2 monomer:
(1) adding 20g of 3, 4-ethylenedioxythiophene into 500 ml of ultra-dry dichloromethane under the nitrogen atmosphere, placing the mixture in an environment at 0 ℃, dropwise adding 70 ml of 2.4mol/L n-butyllithium n-hexane solution into the obtained solution, continuously stirring the solution for 1 hour, then dropwise adding 50 g of tributyltin chloride into the solution, further stirring the solution for 1 hour, taking the solution out of the environment at 0 ℃, placing the solution at normal temperature, and continuously stirring the solution for 12 hours. Adding 600mL of dichloromethane and 600mL of sodium chloride saturated solution into 600mL of solution obtained after the reaction is finished, extracting for 3 times, combining the obtained organic phases, adding 20g of anhydrous sodium sulfate into the solution, stirring for 30 minutes, drying, performing suction filtration after the completion of the reaction to remove the sodium sulfate, adding 40g of silica gel powder into the dried organic phase, removing the organic solution by using a rotary evaporator, separating and purifying the obtained crude product by chromatographic column chromatography, wherein the adsorption phase is 100-200-mesh aluminum oxide, the eluent is dichloromethane, performing TLC identification, collecting the eluent containing the target product, and removing the solvent by rotary evaporation to obtain 45g of tributyl (2, 3-dihydrothieno [3,4-b ] [1,4] dioxanone) stannane.
(2) Adding 10g of 2, 7-dibromo-9, 9' -spirobifluorene, 442 mg of bistriphenylphosphine palladium dichloride and 20g of tributyl (2, 3-dihydrothieno [3,4-b ] [1,4] dioxane) stannane prepared in (1) into 900mL of toluene under a nitrogen atmosphere, heating and refluxing for 24 hours, cooling to room temperature, adding 900mL of dichloromethane and 900mL of a sodium chloride saturated solution into 900mL of the solution obtained after the reaction is finished, extracting for 3 times, combining the obtained organic phases, adding 20g of anhydrous sodium sulfate thereto, stirring for 30 minutes, drying, performing suction filtration after completion, removing the sodium sulfate therefrom, adding 10g of silica gel powder into the dried organic phase and removing the organic solution by using a rotary evaporator, and separating and purifying the obtained crude product by chromatography, wherein the adsorption phase is 300-mesh 400-mesh silica gel, the eluent is dichloromethane and petroleum ether is 1:3(v/v), TLC identification is carried out, eluent containing the target product is collected, and the solvent is removed through rotary evaporation to obtain 12g of the product 2, 7-bis (2, 3-dihydrothieno [3,4-b ] [1,4] dioxin) -9,9' -spirobifluorene.
(3) Adding 10g of 2, 7-bis (2, 3-dihydrothieno [3,4-b ] [1,4] dioxanone) -9,9' -spirobifluorene and 6.7 g of N-bromosuccinimide into 300mL of tetrahydrofuran in a dark environment, standing the mixture at room temperature, stirring the mixture for 24 hours, adding 300mL of dichloromethane and 300mL of saturated sodium chloride solution into the 300mL of solution after the reaction is finished, extracting the mixture for 3 times, combining the obtained organic phases, adding 20g of anhydrous sodium sulfate into the combined organic phases, stirring the combined organic phases for 30 minutes, drying the mixture, performing suction filtration after the reaction is finished, removing the sodium sulfate from the combined organic phases, adding 10g of silica gel powder into the dried organic phases, removing the organic solution by using a rotary evaporator, separating and purifying the obtained crude product by a chromatographic column chromatography, wherein the adsorption phase is 300-400-mesh silica gel, the dichloromethane is petroleum ether which is 1:4(v/v), TLC identification, collecting the eluent containing the target product, and removing the solvent by rotary evaporation to obtain 11g of the product 2, 7-bis (7-bromo-2, 3-dithieno [3,4-b ] [1,4] dioxin) -9,9' -spirobifluorene.
(4) 10g of 2, 7-bis (7-bromo-2, 3-dithieno [3,4-b ] [1,4] dioxin) -9,9' -spirobifluorene obtained in (3) and 12g of tributyl (2, 3-dihydrothieno [3,4-b ] [1,4] dioxane) stannane prepared in (1) were added to 900mL of toluene under nitrogen atmosphere and heated under reflux for 24 hours, after cooling to room temperature, 900mL of methylene chloride and 900mL of a saturated solution of sodium chloride were added to 900mL of the reaction liquid obtained after the completion of the reaction, the obtained organic phases were combined, 20g of anhydrous sodium sulfate was added thereto and stirred for 30 minutes to dry, suction filtration was performed after completion, the sodium sulfate therein was removed, 8g of a silica gel powder was added to the dried organic phase and the organic solution was removed by means of a rotary evaporator, the obtained crude product is separated and purified by chromatographic column chromatography, wherein the adsorption phase is 300-400 mesh silica gel, the eluent is dichloromethane and petroleum ether which are 1:2(v/v), TLC identification is carried out, the eluent containing the target product is collected, and the solvent is removed by rotary evaporation, so that 7.2g of the product E2SBFE2 is obtained, and the nuclear magnetic spectrum and the mass spectrum of the product are shown in figures 6 and 7.
Example 1
0.2g E2SBFE2 and 0.4g tetrabutylammonium hexafluorophosphate as supporting electrolyte were dissolved in 100ml of dichloromethane to give the electrolyte required for the electrochemical polymerization. The electrochemical polymerization adopts a three-electrode system, indium tin oxide glass (ITO) is used as a working electrode, a platinum sheet is used as a counter electrode, and silver/silver chloride is used as a reference electrode. The polymerization was carried out at room temperature using a potentiostatic method at a voltage of 1.4V and a coulometric quantity of 0.05C. After the polymerization is finished, the electrolyte is replaced by a dichloromethane solution of 4.0g/L tetrabutyl ammonium hexafluorophosphate, and the solution is dedoped for 60s at minus 0.2V by adopting a constant potential method to obtain a P (E2SBFE2) film.
Scanning electron microscope analysis is carried out on the P (E2SBFE2) film loaded on the ITO glass prepared in example 1, and as shown in figure 1, the surface morphology of the polymer film is formed by close packing of nano spherical small particles.
The P (E2SBFE2) film supported on ITO glass prepared in example 1 was subjected to uv absorption test in a three-electrode system, as shown in fig. 2, and significant changes in absorption values occurred at about 520nm and 725nm respectively under different voltages, indicating that the polymer film had electrochromic phenomenon.
The ITO glass-supported P (E2SBFE2) film prepared in example 1 was subjected to a contrast test in a three-electrode system, as shown in FIG. 3, with a maximum contrast of about 56% at 520nm and a maximum contrast of about 59% at 725nm, indicating that the polymer film had a relatively high color-change contrast.
The ITO glass-supported P (E2SBFE2) film prepared in example 1 was tested for response time in a three-electrode system, and as shown in FIG. 4, the polymer film showed faster discoloration-associated speed with coloring time at 520nm of 6.4s, fading time of 3.6s, coloring time at 725nm of 3.5s and fading time of 4.4 s.
When the memory effect test is performed on the ITO glass-supported P (E2SBFE2) film prepared in example 1, as shown in FIG. 5, the absorption spectrum of the film after oxidation is in an oxidized state and is left for 150h to be almost unchanged, which indicates that the polymer film has a relatively stable oxidized state, i.e. the polymer film has an excellent memory effect.
The working electrode of the three-electrode system is ITO glass loaded with a P (E2SBFE2) film, the counter electrode is a platinum electrode, the reference electrode is an Ag/AgCl electrode, and the electrolyte is 0.1mol/L dichloromethane solution of tetrabutylammonium hexafluorophosphate. The test voltage range of the cyclic voltammetry is 0-1.4V, and the sweep rate is 0.1V/s. The contrast test uses 0V and 0.5V step voltages and 10s step time.
The ultraviolet absorption test, the contrast test and the contrast stability test are realized by an ultraviolet absorption instrument and an electrochemical workstation, the test wavelength range is 300nm-1100nm, the model of the ultraviolet absorption instrument is UV-1800, and the model of the electrochemical workstation is CHI 660E.
Example 2
0.2g E2SBFE2 and 0.4g tetrabutylammonium hexafluorophosphate serving as a supporting electrolyte are dissolved in 100ml methylene chloride serving as an electrolytic solvent chromatographic grade to obtain an electrolyte required by electrochemical polymerization. The electrochemical polymerization adopts a three-electrode system, indium tin oxide glass (ITO) is used as a working electrode, a platinum sheet is used as a counter electrode, and silver/silver chloride is used as a reference electrode. The polymerization was carried out at room temperature using cyclic voltammetry, scanning from 0V forward to 1.4V at a rate of 100mV/s for 5 cycles. And after scanning, replacing the electrolyte with a chromatographic grade dichloromethane solution of 4.0g/L tetrabutylammonium hexafluorophosphate, and performing doping removal at-0.2V for 60s by adopting a constant potential method to obtain a P (E2SBFE2) film.
The ITO glass-supported P (E2SBFE2) film prepared in example 2 was tested for response time in a three-electrode system, and as shown in FIG. 8, the coloration time at 520nm was 3.2s, the discoloration time was 6.0s, the coloration time at 725nm was 3.8s, and the discoloration time was 4.4 s.
Claims (10)
1. A thiophene-based polymer film, characterized in that: the thiophene polymer film is composed of a polymer P (E2SBFE2) shown in a formula 1;
2. the thiophene-based polymer film of claim 1, wherein: the thiophene polymer film is prepared according to the following method:
adopting a three-electrode system, taking indium tin oxide glass as a working electrode, a platinum sheet as a counter electrode, silver/silver chloride as a reference electrode, dissolving 2, 7-bis (2,2 ', 3, 3' -tetrahydro-5, 5 '-dithieno [3,4-b ] [1,4] dioxin) -9,9' -spirobifluorene and tetrabutyl ammonium hexafluorophosphate in dichloromethane to be used as electrolyte, carrying out electrochemical polymerization, replacing the electrolyte with dichloromethane solution of tetrabutyl ammonium hexafluorophosphate after the electrochemical polymerization is finished, and carrying out 60s dedoping by adopting a constant potential method at-0.2V to obtain the thiophene polymer film; in the electrolyte, the concentration of a monomer 2, 7-bis (2,2 ', 3, 3' -tetrahydro-5, 5 '-dithieno [3,4-b ] [1,4] dioxin) -9,9' -spirobifluorene is 0.1 mmol/L-100 mmol/L, and the concentration of tetrabutylammonium hexafluorophosphate is 0.01 mol/L-0.5 mol/L; the concentration of the tetrabutyl ammonium hexafluorophosphate in the dichloromethane solution of the tetrabutyl ammonium hexafluorophosphate is 0.01 mol/L-0.5 mol/L.
3. The thiophene-based polymer film of claim 1, wherein: in the electrolyte, the concentration of the monomer 2, 7-bis (2,2 ', 3, 3' -tetrahydro-5, 5 '-dithieno [3,4-b ] [1,4] dioxin) -9,9' -spirobifluorene is 1 mmol/L.
4. The thiophene-based polymer film of claim 2, wherein: in the electrolyte, the concentration of tetrabutylammonium hexafluorophosphate is 0.1 mol/L.
5. The thiophene-based polymer film of claim 2, wherein: the concentration of the tetrabutylammonium hexafluorophosphate in the dichloromethane solution of the tetrabutylammonium hexafluorophosphate is 0.1 mol/L.
6. The thiophene-based polymer film of claim 2, wherein: the electrochemical polymerization adopts a constant potential polymerization method to carry out polymerization at room temperature at the voltage of 1.2-1.5V and the electric quantity of 0.02-0.2C.
7. The thiophene-based polymer film of claim 6, wherein: the conditions of the electrochemical polymerization were that the polymerization was carried out at a voltage of 1.4V and a charge of 0.05C.
8. The thiophene-based polymer film of claim 2, wherein: the electrochemical polymerization adopts a cyclic voltammetry polymerization method to carry out polymerization by scanning for 3-30 cycles at a scanning speed of 0-1.4V and 100 mv/s.
9. The thiophene-based polymer film of claim 8, wherein: the electrochemical polymerization is carried out by scanning for 5 cycles.
10. Use of the thiophene-based polymer film of claim 1 in the preparation of an electrochromic material.
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| CN114605620A (en) * | 2022-04-18 | 2022-06-10 | 上海戎科特种装备有限公司 | Electrochromic polymer, preparation method thereof and electrochromic film |
| CN114853987A (en) * | 2022-04-12 | 2022-08-05 | 上海戎科特种装备有限公司 | Electrochromic copolymer containing dioxythiophene and 9,9' -spirobifluorene structure, preparation method thereof and polymer film |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114853987A (en) * | 2022-04-12 | 2022-08-05 | 上海戎科特种装备有限公司 | Electrochromic copolymer containing dioxythiophene and 9,9' -spirobifluorene structure, preparation method thereof and polymer film |
| CN114853987B (en) * | 2022-04-12 | 2023-09-15 | 上海戎科特种装备有限公司 | Electrochromic copolymer containing dioxythiophene and 9,9' -spirobifluorene structure, preparation method thereof and polymer film |
| CN114605620A (en) * | 2022-04-18 | 2022-06-10 | 上海戎科特种装备有限公司 | Electrochromic polymer, preparation method thereof and electrochromic film |
| CN114605620B (en) * | 2022-04-18 | 2023-09-15 | 上海戎科特种装备有限公司 | Electrochromic polymer, preparation method thereof and electrochromic film |
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