CN111635143A - Method for preparing porphyrin-based polymer electrochromic film through electrodeposition - Google Patents
Method for preparing porphyrin-based polymer electrochromic film through electrodeposition Download PDFInfo
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- CN111635143A CN111635143A CN202010489734.6A CN202010489734A CN111635143A CN 111635143 A CN111635143 A CN 111635143A CN 202010489734 A CN202010489734 A CN 202010489734A CN 111635143 A CN111635143 A CN 111635143A
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- porphyrin
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1516—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising organic material
- G02F1/15165—Polymers
Abstract
The invention relates to a method for preparing a porphyrin-based polymer electrochromic film by electrodeposition, which comprises the following steps: the electric polymerization method deposits the polyporphyrin film on the ITO conductive glass. The preparation method realizes the preparation of the multicolor electrochromic electrode by a simple method, and has definite application prospect in the fields of display devices, intelligent wearing, optical camouflage and the like.
Description
Technical Field
The invention belongs to the field of preparation of electrochromic films, and particularly relates to a method for preparing a porphyrin-based polymer electrochromic film through electrodeposition.
Background
Electrochromism refers to the phenomenon that the optical characteristics of a material generate stable reversible change under the action of an applied electric field, and the material is represented as reversible change of color and transparency in appearance. The electrochromic material has bistable performance, and the electrochromic display device does not need background light, does not consume power when maintaining color, and has excellent energy-saving effect. In the closed environment such as buildings, airplanes, automobiles and the like, the transmittance of light rays with different wavelengths is adjusted through the electrochromic film attached to the surface of the glass, so that the internal temperature can be reduced and adjusted under the condition of reducing or not using air conditioning equipment. Compared with the traditional polythiophene polymer such as CN 109942797A, the polyporphyrin cross-linked polymer is used as a novel electrochromic material, and the internal pore channels are favorable for ion transmission in the electrochromic process, so that the electrochromism material has higher discoloration speed and higher discoloration efficiency.
The polyporphyrin as a novel electrochromic material has the characteristics of low synthesis cost and the like, and has good conductivity and transparency. At present, most porphyrin polymerization methods such as acid-base oxidation and the like are complex and are not suitable for large-scale production.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for preparing a porphyrin-based polymer electrochromic film by electrodeposition, which overcomes the defects of complex process and unsuitability for large-scale production in the prior art. The invention adopts a simple electropolymerization method to realize the preparation of the polyporphyrin electrochromic film.
The structural formula of the electrochromic polymer material is shown as follows:
poly (5, 10,15, 20-tetra (4-N, N-diphenylaminophenyl) porphyrin, with the polymerization degree N ranging from 1 to 9000.
The invention discloses a preparation method of an electrochromic film, which comprises the following steps:
(1) preparing electrolyte containing porphyrin monomers;
(2) a glass substrate is taken as a working electrode and is immersed into electrolyte for electropolymerization, and post-treatment is carried out to obtain a load of the electrolyte
Electrochromic films of electrochromic polymeric materials.
The preferred mode of the above preparation method is as follows:
the electrolyte in the step (1) is composed of tetrabutyl ammonium hexafluorophosphate electrolyte and porphyrin monomer dissolved in dichloromethane, wherein the concentration of tetrabutyl ammonium hexafluorophosphate is 0.01-1 mol/L, and the concentration of porphyrin monomer is 0.001-1 mol/L.
The porphyrin monomer in the step (1) is prepared by the following method: under the protection of inert gas, dispersing 4- (N, N-diphenylamino) benzaldehyde and pyrrole in dichloromethane, adding trifluoroacetic acid, reacting in inert gas, and purifying to obtain the final product.
Further, synthesis of 5,10,15, 20-tetrakis (4-N, N-diphenylaminophenyl) porphyrin polymerized monomer: under the protection of inert gas, dispersing reactants 4- (N, N-diphenylamino) benzaldehyde and pyrrole in a 500ml dichloromethane in proportion, adding trifluoroacetic acid, continuing to react in the inert gas for a period of time, sequentially filtering, drying and recrystallizing in trichloromethane to obtain a light yellow solid; the molar ratio of the reactant 4- (N, N-diphenylamino) benzaldehyde to pyrrole is 1: 1-8: 1; the concentration of the trifluoroacetic acid is 0.001-0.1 mol/L, the reaction temperature is 30-100 ℃, and the reaction time is 4-24 h.
And (3) carrying out ultrasonic washing on the glass substrate in the step (2) by sequentially using a surfactant deionized water mixed solution, deionized water, ethanol and acetone.
And (3) in the step (2), the glass is used as a working electrode and is immersed in the electrolyte, meanwhile, a platinum sheet is used as a counter electrode, and the distance between the ITO glass and the platinum sheet is 0.5-2 cm.
In the step (2), the electropolymerization voltage is 0.8-1.8V, the polymerization temperature is 20-60 ℃, and the polymerization time is 1-10 min.
And (3) in the step (2), the post-treatment is to soak the materials in dichloromethane for 10-48 h at room temperature.
The invention relates to an electrochromic film prepared by the method.
The electrochromic film has a definite application prospect in the fields of display devices, intelligent wearing, optical camouflage and the like.
Advantageous effects
(1) The invention utilizes the electric polymerization method to deposit the polyporphyrin film on the surface of the glass, has simple preparation method and no special equipment requirement, and is suitable for industrial production;
(2) according to the invention, by adjusting the process parameters such as polymerization voltage and time, the thickness and the surface appearance of the polyporphyrin film can be effectively regulated, and by increasing the contact area between the surface of the film and the electrolyte, the ion transmission distance in the electrochromic process is shortened, so that the electrochromic performance is improved;
(3) the invention realizes the multi-color conversion (0V yellow, 0.9V red, 1.1V green and 1.5V blue) of the material at lower voltage (-1-2V), and provides possibility for low-energy display and other applications.
Drawings
FIG. 1 is a nuclear magnetic spectrum of a polymerized monomer of 5,10,15, 20-tetrakis (4-N, N-diphenylaminophenyl) porphyrin prepared in example 1 of the present invention;
FIG. 2 is a picture of a polyporphyrin thin film in example 1;
FIG. 3 is a graph of the UV absorption spectrum of an electrode prepared in example 2 of the present invention as a function of voltage;
FIG. 4 is a graph showing the transmittance spectra of the color-changing electrode at wavelengths of 720nm and 1350nm as a function of voltage in example 3 of the present invention.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Description of the raw materials of the invention: tetrabutylammonium hexafluorophosphate (99%), 4- (N, N-diphenylamino) benzaldehyde (99%), propylene carbonate (99%), pyrrole (98%), dichloromethane (99%) were purchased from Bailingwei chemical technology, Inc. ITO glass is purchased from Wuhan lattice Inc., and other reagents are commercially available.
Example 1
(1) And (3) ultrasonically washing the glass substrate for 15min by sequentially using a surfactant aqueous solution, deionized water, ethanol and acetone, and drying for later use.
(2) The reactants 0.1mol of 4- (N, N-diphenylamino) benzaldehyde and 0.1mol of pyrrole are dispersed in 500ml of dichloromethane under inert gas. Adding 0.002ml of trifluoroacetic acid, continuously reacting in inert gas at 35 ℃ for 4h, sequentially filtering, drying and recrystallizing in chloroform to obtain the porphyrin polymerization monomer.
(3) 0.02mol of tetrabutylammonium hexafluorophosphate and 0.003mol of porphyrin monomer were dissolved in 500ml of methylene chloride to prepare an electrolyte, and ITO glass was immersed in the electrolyte and kept at a distance of 0.5cm from a platinum sheet counter electrode.
(4) And applying 1V voltage to the ITO glass, polymerizing for 4min at the temperature of 25 ℃, taking out the ITO glass, and soaking in dichloromethane for 40h at room temperature to obtain the electrochromic electrode.
The nuclear magnetic resonance spectrum of the porphyrin polymerization monomer obtained in the example is shown in FIG. 1, and no redundant hetero-peak appears in the graph, which indicates that the purity of the prepared porphyrin monomer is high.
The electrochromism of the polyporphyrin obtained in the example is shown in FIG. 2, and it can be seen that the thin film obtained by the electropolymerization method is relatively flat and uniform.
Example 2
(1) And (3) ultrasonically washing the glass substrate for 10min by sequentially using a surfactant aqueous solution, deionized water, ethanol and acetone, and drying for later use.
(2) The reactants 0.4mol of 4- (N, N-diphenylamino) benzaldehyde and 0.1mol of pyrrole are dispersed in 500ml of dichloromethane under inert gas. After 0.01ml of trifluoroacetic acid is added and reaction is continued in inert gas at 60 ℃ for 10h, the obtained product is sequentially filtered, dried and recrystallized in trichloromethane to obtain the porphyrin polymerization monomer.
(3) 0.04mol of tetrabutylammonium hexafluorophosphate and 0.006mol of porphyrin monomer were dissolved in 500ml of dichloromethane to prepare an electrolyte, and ITO glass was immersed in and held at a distance of 2cm from a platinum sheet counter electrode.
(4) And applying 0.8V voltage to the ITO glass, polymerizing for 10min at the temperature of 40 ℃, taking out the ITO glass, and soaking in dichloromethane for 30h at room temperature to obtain the electrochromic electrode.
The ultraviolet absorption spectrum of the electrode obtained in step (3) of this example is shown in fig. 3 with the voltage change, and the absorption of light with wavelength from 300nm to 800nm of the electrode changes with the voltage from 0V to 1.5V, and is represented as 0V yellow, 0.9V red, 1.1V green, and 1.5V blue.
Example 3
(1) And (3) ultrasonically washing the glass substrate for 20min by sequentially using a surfactant aqueous solution, deionized water, ethanol and acetone, and drying for later use.
(2) The reactants 0.8mol of 4- (N, N-diphenylamino) benzaldehyde and 0.1mol of pyrrole are dispersed in 500ml of dichloromethane under inert gas. After 0.009ml of trifluoroacetic acid is added and the reaction is continued in inert gas at 100 ℃ for 6 hours, the obtained product is sequentially filtered, dried and recrystallized in trichloromethane to obtain the porphyrin polymerization monomer.
(3) 0.04mol of tetrabutylammonium hexafluorophosphate and 0.006mol of porphyrin monomer were dissolved in 500ml of dichloromethane to prepare an electrolyte, and ITO glass was immersed in and held at a distance of 1cm from a platinum sheet counter electrode.
(4) And applying a voltage of 0.9V to the ITO glass, polymerizing for 10min at the temperature of 45 ℃, taking out the ITO glass, and soaking in dichloromethane for 20h at room temperature to obtain the electrochromic electrode.
The transmission spectrum of the electrochromic electrode obtained in the step (3) of the embodiment along with the voltage change is shown in fig. 3, and due to the cross-linked porous characteristic of the polyporphyrin film, the coloring time and the fading time of the electrode at 720nm are respectively 0.3 and 0.5 seconds, and the coloring time and the fading time at 1350nm are respectively 0.4 and 0.9 seconds, which are higher than those of the known polythiophene electrochromic materials.
Claims (10)
1. An electrochromic polymer material, characterized by the structural formula:
poly (5, 10,15, 20-tetra (4-N, N-diphenylaminophenyl) porphyrin, with the polymerization degree N ranging from 1 to 9000.
2. A preparation method of an electrochromic film comprises the following steps:
(1) preparing electrolyte containing porphyrin monomers;
(2) and (3) taking a glass substrate as a working electrode, immersing the glass substrate into electrolyte for carrying out electropolymerization reaction, and carrying out aftertreatment to obtain the electrochromic film loaded with the polymer material of claim 1.
3. The preparation method according to claim 1, wherein the electrolyte in the step (1) is composed of tetrabutylammonium hexafluorophosphate electrolyte and porphyrin monomer dissolved in dichloromethane, wherein the concentration of tetrabutylammonium hexafluorophosphate is 0.01-1 mol/L, and the concentration of porphyrin monomer is 0.001-1 mol/L.
4. The method according to claim 1, wherein the porphyrin monomer in step (1) is prepared by the following method: under the protection of inert gas, dispersing 4- (N, N-diphenylamino) benzaldehyde and pyrrole in dichloromethane, adding trifluoroacetic acid, reacting in inert gas, and purifying to obtain the final product.
5. The preparation method according to claim 1, wherein the glass substrate in the step (2) is Indium Tin Oxide (ITO) conductive glass; the glass substrate is subjected to ultrasonic washing by sequentially using a surfactant deionized water mixed solution, deionized water, ethanol and acetone.
6. The preparation method according to claim 1, wherein in the step (2), the glass is used as a working electrode and is immersed in the electrolyte, a platinum sheet is used as a counter electrode, and the distance between the glass and the platinum sheet is 0.5-2 cm.
7. The preparation method according to claim 1, wherein the electropolymerization voltage in the step (2) is 0.8-1.8V, the polymerization temperature is 20-60 ℃, and the polymerization time is 1-10 min.
8. The preparation method according to claim 1, wherein the post-treatment in the step (2) is soaking in dichloromethane for 10-48 h at room temperature.
9. An electrochromic film prepared by the method of claim 1.
10. Use of an electrochromic film as claimed in claim 9.
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| CN202010489734.6A CN111635143A (en) | 2020-06-02 | 2020-06-02 | Method for preparing porphyrin-based polymer electrochromic film through electrodeposition |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114005684A (en) * | 2021-11-05 | 2022-02-01 | 吉林大学 | Electrochemical polymerization film of unsaturated chlorophyll and application thereof in super capacitor |
| CN115079480A (en) * | 2022-03-31 | 2022-09-20 | 中国人民解放军国防科技大学 | Porphyrin MOF-based electrochromic film material and preparation method thereof |
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| CN102702461A (en) * | 2012-05-24 | 2012-10-03 | 黑龙江大学 | Polyurethane with electrochromism performance and preparation method thereof |
| CN103342471B (en) * | 2013-07-05 | 2015-10-21 | 西北师范大学 | A kind of Photoelectric nanometer composite membrane material and its preparation method and application |
| CN109651602A (en) * | 2018-12-12 | 2019-04-19 | 浙江工业大学 | A kind of preparation method of quick response electrochromism PTBTPA film |
| CN110592609A (en) * | 2019-08-30 | 2019-12-20 | 浙江工业大学 | Method for improving cycling stability of polymer electrochromic film |
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2020
- 2020-06-02 CN CN202010489734.6A patent/CN111635143A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102702461A (en) * | 2012-05-24 | 2012-10-03 | 黑龙江大学 | Polyurethane with electrochromism performance and preparation method thereof |
| CN103342471B (en) * | 2013-07-05 | 2015-10-21 | 西北师范大学 | A kind of Photoelectric nanometer composite membrane material and its preparation method and application |
| CN109651602A (en) * | 2018-12-12 | 2019-04-19 | 浙江工业大学 | A kind of preparation method of quick response electrochromism PTBTPA film |
| CN110592609A (en) * | 2019-08-30 | 2019-12-20 | 浙江工业大学 | Method for improving cycling stability of polymer electrochromic film |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114005684A (en) * | 2021-11-05 | 2022-02-01 | 吉林大学 | Electrochemical polymerization film of unsaturated chlorophyll and application thereof in super capacitor |
| CN114005684B (en) * | 2021-11-05 | 2023-05-05 | 吉林大学 | Electrochemical polymerized film of unsaturated chlorophyll and application thereof in super capacitor |
| CN115079480A (en) * | 2022-03-31 | 2022-09-20 | 中国人民解放军国防科技大学 | Porphyrin MOF-based electrochromic film material and preparation method thereof |
| CN115079480B (en) * | 2022-03-31 | 2023-12-29 | 中国人民解放军国防科技大学 | Electrochromic film material based on porphyrin MOF and preparation method thereof |
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Application publication date: 20200908 |