CN117164826A - Electrochromic polymer and preparation method and application thereof - Google Patents
Electrochromic polymer and preparation method and application thereof Download PDFInfo
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Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention relates to the technical field of organic photoelectric functional materials, in particular to an electrochromic polymer, a preparation method and application thereof, wherein the electrochromic polymer is shown as a formula (I):in the formula (I), R is C 5 ~C 30 Is a chain of an alkane; the electrochromic polymer has a number average molecular weight mn=5000 to 200000. The invention prepares a novel electrochromic polymer with simpler structure by a simple chemical polymerization mode, and the electrochromic polymer is yellow in a neutral state and green in an oxidation state after film formation; furthermore, the electrochromic polymer preparedThe compound has good solubility in common organic solvents, can realize large-area preparation of film materials by a solution processing method, can realize stable and reversible conversion from neutral yellow to oxidation green at low voltage (about 1.2V), and has potential application value in the fields of military camouflage, displays and the like.
Description
Technical Field
The invention relates to the technical field of organic photoelectric functional materials, in particular to an electrochromic polymer and a preparation method and application thereof.
Background
Electrochromic (EC) refers to a device in which oxidation-reduction can be performed by external current, and simultaneously doping and dedoping of electrolyte ions are performed, so that optical properties (such as contrast and color) of the device are changed stably and reversibly, and the device macroscopically shows reversible changes of color. The electrochromic material is discovered to be a novel functional material, has the advantages of autonomous color change and energy conservation, is greatly developed in a global environment advocating energy conservation and emission reduction, and has certain application in partial fields, such as the fields of intelligent glass, automobile anti-glare rearview mirrors, electronic tags, mobile phone accessories, displays, thermal control and the like. Recent research has further combined electrochromic technology with military equipment (e.g., weaponry, smart wearable apparel) to achieve the effect of a plausible false in order to achieve the winning of war.
Pseudo-fitting is a mature technique in nature. Camouflage is a skill developed by animals in biological terms to increase survival. In war, camouflage technology is applied to better protect ground-based fixed and mobile military targets. The self-adaptive camouflage technology is a novel camouflage technology which can automatically and continuously respond under the change of the battlefield conditions such as environment or enemy threat and the like and keeps good camouflage effect, and is the development direction of the current intelligent camouflage field. The electrochromic can just meet the self-adaptive effect, the phenomenon that the optical property (color) of the material is reversibly changed when the electrochromic is subjected to an external electric field can be controlled by an external circuit, the effect consistent with the environmental background is achieved, and the purpose of camouflage is achieved. The electrochromic material has the advantages of simple control, quick response and the like due to low-voltage control, has a wide spectrum adjusting range and rich material types, and becomes a hot spot for the study of intelligent camouflage equipment. Among the existing electrochromic materials, red and blue colors are mostly, green colors are less, and high requirements are placed on the structural design of the polymer materials and the synthesis of the polymer materials, so that the development of a new yellow-to-green electrochromic material is important for the camouflage field.
The Chinese patent application No. 201910834430.6 discloses a preparation method and application of a yellow-to-green quick response electrochromic film. The invention utilizes the color-changing effect of the tungsten oxide film or the molybdenum oxide film to compound the yellow back, and realizes the conversion of yellow and green by the compound color development principle. The technology obtains a yellow back through depositing a gold film, so that the cost of the electrochromic device is increased; and the electrochromic device related to the technology needs to use propylene carbonate electrolyte, and the electrolyte can leak in a bending state, so that the technology cannot be applied to flexible devices, and the application of the material in the camouflage field is limited.
The original green electrochromic material is prepared by electrochemical polymerization, and has the defect of being incapable of being prepared in large quantities. Although more and more yellow to green reversible electrochromic materials are gradually designed and prepared, the materials are basically copolymerized by more than two monomers, have complex structures and still have the defect of being incapable of being prepared in large quantities. Therefore, the design and synthesis of the electrochromic material with simple structure and large-scale preparation possibility has important significance for the research and application of the electrochromic material of the yellow-green color system.
Disclosure of Invention
The invention aims to overcome the problems and the defects in the prior art, provides an electrochromic polymer and a preparation method thereof, and is applied to the fields of military camouflage and displays, so as to solve the problems that yellow-to-green electrochromic materials are fewer, the structure is complex and the electrochromic polymer cannot be prepared in a large scale in the prior art.
In order to achieve the above purpose, the present invention is realized by the following technical scheme:
in a first aspect, the present invention provides an electrochromic polymer, as shown in formula (I):
(Ⅰ)in the formula (I), R is C 5 ~C 30 Is a chain of an alkane;
the electrochromic polymer has a number average molecular weight mn=5000 to 200000.
3, 4-Ethylenedioxythiophene (EDOT) is a monomer material of poly 3, 4-ethylenedioxythiophene (PEDOT), and a poly 3, 4-ethylenedioxythiophene (PEDOT) film may be prepared by an electrochemical polymerization method. The poly 3, 4-ethylenedioxythiophene (PEDOT) has the advantages of low energy gap, low electrochemical doping potential, short response time, high contrast of color change, good stability and the like, and is a research hot spot of the international organic electrochromic material. Poly (3, 4-ethylenedioxythiophene) (PEDOT) can undergo reversible color change between sky blue and transparent under the action of an applied electric field. Perylene and nitrogen are an aza aromatic ring. The monomer composed of 3, 4-ethylenedioxythiophene and perylene nitrogen units forms a red polymer film after electrochemical polymerization, and is oxidized to light green at a voltage of 1.1V. Since the polymer film formed by the monomer composed of 3, 4-ethylenedioxythiophene and perylene nitrogen unit after electrochemical polymerization is red in neutral state, the absorption spectrum of the polymer film is changed from red to yellow, and the blue shift is necessary. The inventor finds that when EDOT is changed into propylene dioxythiophene (proDot) on one hand and perylene nitrogen in the relative receptor is changed into perylene sulfur on the other hand, namely N atoms in the relative receptor are changed into S atoms of the same main group, the electrochromic polymer prepared by chemical polymerization is yellow in a neutral state and green in an oxidation state after being formed into a film, the structure of the polymer is simpler, and the formed film can realize stable and reversible conversion from the neutral state yellow to the oxidation state green under low voltage (about 1.2V).
Preferably, R in formula (I) is C 5 ~C 20 The number average molecular weight mn=10000 to 50000 of the electrochromic polymer.
In a second aspect, the present invention provides a process for preparing an electrochromic polymer as described above, comprising the steps of:
(1) Adding a compound shown in a formula (II) and a compound shown in a formula (III) into an organic solvent containing a palladium catalyst, and treating after the reaction is finished to obtain a compound shown in a formula (IV);
(2) Adding a compound shown as a formula (IV) into an organic solvent containing ferric trichloride, and treating after the reaction is finished to obtain the electrochromic polymer;
(Ⅱ)(Ⅲ)/>(Ⅳ)r in the formulae (II) and (IV) is C 5 ~C 30 Is a chain of an alkane.
The invention firstly prepares the compound shown in the formula (IV) through the compound shown in the formula (II) and the compound shown in the formula (III), and then the electrochromic polymer is obtained through polymerizing the compound shown in the formula (IV) as a monomer. The use of a single monomer for polymerization can avoid the non-uniformity between different monomers and the introduction of impurities, thereby achieving higher purity and consistency of the polymer. The efficiency and yield of the polymerization reaction are generally higher since only one monomer is involved, which makes it possible to mass-produce the electrochromic polymer of the invention for industrial applications.
Preferably, in the step (1), the molar ratio of the compound shown in the formula (II) to the compound shown in the formula (III) is (2-4): 1, and the molar ratio of the compound shown in the formula (II) to the palladium catalyst is (0.03-0.1).
Preferably, the palladium catalyst in the step (1) is one or two of tetra (triphenylphosphine) palladium and dichloro di (triphenylphosphine) palladium, and the organic solvent is one or more of N-methylpyrrolidone, dimethylformamide and dimethylacetamide.
Preferably, in the polymerization reaction in the step (2), the feeding molar ratio of the compound shown as the formula (IV) to the ferric trichloride is 1 (6-10).
Preferably, the organic solvent in the step (2) is one or more of dichloromethane, chloroform and tetrahydrofuran.
Preferably, the reaction temperature in the step (1) is 100-160 ℃ and the reaction time is 12-36 h; the reaction temperature in the step (2) is 20-30 ℃ and the reaction time is 12-36 h.
The invention controls the input amount of the reaction materials and the reaction conditions in the step (1) and the step (2) in the preparation method, and when the input molar ratio is lower or higher than the input molar ratio, a plurality of monosubstituted monomers in the step (1) or a plurality of side reactions in the step (2) can be caused; when the reaction temperature and time are lower or higher than the above ranges, a large number of side reactions are liable to occur, and the electrochromic polymer of the present invention represented by the formula (I) cannot be produced. In the step (1), polar organic solvents such as N-methyl pyrrolidone, dimethylformamide, dimethylacetamide and the like and palladium catalysts are adopted to help improve the yield of the coupling reaction; in the step (2), dichloromethane, chloroform and tetrahydrofuran are adopted to be more favorable for dissolving electrochromic polymers serving as reaction products and for carrying out the reaction.
In a third aspect, the present invention provides an electrochromic polymer film processed from an electrochromic polymer as described above or an electrochromic polymer prepared by the method described above.
The polymer has good solubility in common organic solvents, and can realize large-area preparation of film materials by a solution processing method. The solution processing film comprises the following concrete steps: and (3) dissolving the electrochromic polymer in a solvent to obtain a solution, coating the solution on a conductive substrate, and drying to obtain the electrochromic polymer film.
More preferably, the solvent is dichloromethane, chloroform, tetrahydrofuran, toluene, dimethylformamide.
The coating mode can be spray coating, spin coating, screen printing and the like. The conductive substrate can be ITO glass, FTO glass, ITO-PET substrate, FTO-PET substrate and the like.
In a fourth aspect, the present invention provides the use of said electrochromic polymer film in military camouflage, display applications.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention prepares a novel electrochromic polymer with simpler structure by a simple chemical polymerization mode, and the electrochromic polymer is yellow in a neutral state and green in an oxidation state after film formation;
(2) The electrochromic polymer prepared by the method has good solubility in common organic solvents, can realize large-area preparation of film materials by a solution processing method, can realize stable and reversible conversion from neutral yellow to oxidation green at low voltage (about 1.2V), and has potential application value in the fields of military camouflage, displays and the like; (3) The preparation method of the electrochromic polymer is simple, and provides possibility for industrial application of preparing the electrochromic polymer in large scale.
Drawings
FIG. 1 is a CV curve of a film made of the polymer prepared in example 1 of the present invention.
FIG. 2 is an optical absorption diagram of films made from the polymer produced in example 1 of the present invention at various voltages.
FIG. 3 is a graph showing the coloring time and the fading time of a film made of the polymer produced in example 1 of the present invention.
FIG. 4 is a graph showing the transmittance over time of a film formed from the polymer prepared in example 1 of the present invention at a specific wavelength in a multi-potential step of 0 to 1.2V.
Detailed Description
The invention is further described below with reference to the drawings and specific examples. Those of ordinary skill in the art will be able to implement the invention based on these descriptions. In addition, the embodiments of the present invention referred to in the following description are typically only some, but not all, embodiments of the present invention. Therefore, all other embodiments, which can be made by one of ordinary skill in the art without undue burden, are intended to be within the scope of the present invention, based on the embodiments of the present invention.
See, for synthesis of compounds of formula (ii): kerszulis JustinA., amb ChadM., dyerAubrey L., et al Follow the yellow brick road: structural optimization of vibrant yellow-to-transmissive electrochromic conjugatedpolymers [ J ], macromolecules,2014,47 (16): 5462-5469; see for synthesis of compounds of formula (iii): chen Huajie, guo Yunlong, sun Xiangin, et al Synthesis and characterization of phenanthrocarbazole-diketopyrrolopyrrole copolymer for high-performance field-effect transistors [ J ], journal of Polymer Science Part A: polymer Chemistry,2013,51 (10): 2208-2215 and Atakan Gizem, gunbas Gorkem, anovel red to transmissive electrochromic polymer based on phenanthrocarbazole [ J ], RSCAddees, 2016,6 (30): 25620-25623.
Example 1 preparation of electrochromic Polymer
(1) The compound (3.65 g,1 eq.) as shown in formula (II) was added to 30ml of an N, N-dimethylformamide solution containing the compound (2.2 g,0.5 eq.) as shown in formula (III), tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) (105 mg,0.03 eq.) at 120 ℃ under reflux for 12 hours, extracting with water and dichloromethane after the reaction, drying, and separating by column chromatography to obtain the compound shown as the formula (IV).
(2) Adding a compound (1.42 g,1 eq.) shown in a formula (IV) into 20ml of chloroform containing ferric trichloride (1.28 g,8 eq.) for reaction for 24 hours at 30 ℃, pouring the solution into methanol after the reaction is finished, filtering, drying, sequentially extracting with methanol, acetone, hexane and chloroform, collecting a polymer dissolved in the chloroform, and spinning to obtain the electrochromic polymer.
The electrochromic polymer is synthesized as follows:
example 2 preparation of electrochromic Polymer
(1) The compound (3.65 g,1 eq.) as shown in formula (II) was added to 30ml of an N, N-dimethylformamide solution containing the compound (1.1 g,0.25 eq.) as shown in formula (III), tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) (350 mg,0.1 eq.) at 120 ℃ under reflux for 12 hours, extracting with water and dichloromethane after the reaction, drying, and separating by column chromatography to obtain the compound shown as the formula (IV).
(2) The compound (1.42 g,1 eq.) shown in formula (IV) is added into 20ml of chloroform containing ferric trichloride (0.96 g,6 eq.) to react for 24 hours at 30 ℃, after the reaction is finished, the solution is poured into methanol, filtered, dried, sequentially extracted with methanol, acetone, hexane and chloroform, the polymer dissolved in the chloroform is collected, and the electrochromic polymer is obtained after spin drying.
Example 3 preparation of electrochromic Polymer
(1) The compound (3.65 g,1 eq.) as shown in formula (II) was added to 30ml of an N, N-dimethylformamide solution containing the compound (1.45 g,0.33 eq.) as shown in formula (III), tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) (210 mg,0.06 eq.) at 120 ℃ under reflux for 12 hours, extracting with water and dichloromethane after the reaction, drying, and separating by column chromatography to obtain the compound shown in the formula (IV).
(2) The compound (1.42 g,1 eq.) shown in formula (IV) is added into 20ml of chloroform containing ferric trichloride (1.6 g,10 eq.) to react for 24 hours at 30 ℃, after the reaction is finished, the solution is poured into methanol, filtered, dried, sequentially extracted with methanol, acetone, hexane and chloroform, the polymer dissolved in the chloroform is collected, and the electrochromic polymer is obtained after spin drying.
Example 4 preparation of electrochromic Polymer
(1) The compound (3.65 g,1 eq.) as shown in formula (II) was added to 30ml of an N, N-dimethylformamide solution containing the compound (2.2 g,0.5 eq.) as shown in formula (III), tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) (105 mg,0.03 eq.) at 100 ℃ under reflux for 36 hours, extracting with water and dichloromethane after the reaction, drying, and separating by column chromatography to obtain the compound shown in the formula (IV).
(2) Adding a compound (1.42 g,1 eq.) shown in a formula (IV) into 20ml of chloroform containing ferric trichloride (1.28 g,8 eq.) for reaction for 36 hours at 20 ℃, pouring the solution into methanol after the reaction is finished, filtering, drying, sequentially extracting with methanol, acetone, hexane and chloroform, collecting a polymer dissolved in the chloroform, and spinning to obtain the electrochromic polymer.
Example 5 preparation of electrochromic Polymer
(1) The compound (3.65 g,1 eq.) as shown in formula (II) was added to 30ml of an N, N-dimethylformamide solution containing the compound (2.2 g,0.5 eq.) as shown in formula (III), tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 ) (105 mg,0.03 eq.) at 160 ℃ under reflux for 20 hours, extracting with water and dichloromethane after the reaction, drying, and separating by column chromatography to obtain the compound shown as the formula (IV).
(2) The compound (1.42 g,1 eq.) shown in formula (IV) is added into 20ml of chloroform containing ferric trichloride (1.28 g,8 eq.) to react for 12 hours at 25 ℃, after the reaction is finished, the solution is poured into methanol, filtered, dried, sequentially extracted with methanol, acetone, hexane and chloroform, the polymer dissolved in the chloroform is collected, and the electrochromic polymer is obtained after spin drying.
Example 6 preparation of electrochromic Polymer
(1) The compound (3.65 g,1 eq.) represented by the formula (II) was added to a 30ml N-methylpyrrolidone solution containing the compound (2.2 g,0.5 eq.) represented by the formula (III), and bis (triphenylphosphine) palladium (105 mg,0.03 eq.) was added thereto, and the mixture was reacted at 120℃under reflux for 12 hours, and after completion of the reaction, extracted with water and methylene chloride, dried, and separated by column chromatography to obtain the compound represented by the formula (IV).
(2) The compound (1.42 g,1 eq.) shown in formula (IV) is added into 20ml tetrahydrofuran containing ferric trichloride (1.28 g,8 eq.) to react for 24 hours at 30 ℃, after the reaction is finished, the solution is poured into methanol, filtered, dried, sequentially extracted with methanol, acetone, hexane and chloroform, the polymer dissolved in the chloroform is collected, and the electrochromic polymer is obtained after spin drying.
[ Performance test ]
The electrochromic polymer prepared in example 1 was dissolved in chloroform to obtain a polymer solution, the polymer solution obtained by dissolution was spin-coated on an ITO substrate to form a film, and dried to obtain an electrochromic polymer film. Wherein the concentration of the polymer solution is 12mg/ml, the spin coating rotating speed is 1000r/min, and the time is 1min.
Using an electrochemical workstation and an ultraviolet-visible spectrophotometer combined device, in 0.1M tetrabutylammonium hexafluorophosphate/acetonitrile solution, performing electrochromic performance test on the prepared electrochromic polymer film, and respectively testing the prepared film: (1) CV curve; (2) uv-vis absorption at different voltages; (3) The fade time and the color time of the film at a particular wavelength; (4) The transmittance at a specific wavelength and time, and the film stability at a step voltage were tested, and the data processing results are shown in fig. 1 to 4, respectively.
As can be seen from FIG. 1, the electrochromic polymer film has a pair of redox peaks at 1.1V/0.85V. The color of the electrochromic polymer film in the neutral state and the oxidized state can be seen from the absorption spectrum in fig. 2, and the film in the oxidized state has an absorption peak at about 400nm and 700nm and a valley at 500nm, which is green. The absorption peak of the neutral state is at 484nm, and the pi-pi conjugated absorption is yellow. That is, the polymer film is yellow in a neutral state of 0V and green after oxidation at a voltage of 1.2V. From FIG. 3, it can be seen that the electrochromic polymer film has a multi-potential step transmittance of 0 to 1.2V at 684nm as a function of time, wherein the time to complete oxidation to green is 1.4s, the time to complete reduction to yellow is 1.6s, and the contrast ratio of the film at 684nm is 36.5%. From fig. 4 it can be seen that the stability test (5 s step time) of the electrochromic polymer film, after 250 cycles, the contrast remains 55%.
Claims (10)
1. An electrochromic polymer characterized by the formula (i):
(Ⅰ)
in the formula (I), R is C 5 ~C 30 Is a chain of an alkane;
the electrochromic polymer has a number average molecular weight mn=5000 to 200000.
2. An electrochromic polymer according to claim 1, wherein R in formula (I) is C 5 ~C 20 The number average molecular weight mn=10000 to 50000 of the electrochromic polymer.
3. A process for preparing an electrochromic polymer according to claim 1 or 2, characterized in that it comprises the following steps:
(1) Adding a compound shown in a formula (II) and a compound shown in a formula (III) into an organic solvent containing a palladium catalyst, and treating after the reaction is finished to obtain a compound shown in a formula (IV);
(2) Adding a compound shown as a formula (IV) into an organic solvent containing ferric trichloride, and treating after the reaction is finished to obtain the electrochromic polymer;
(Ⅱ)(Ⅲ)/>(Ⅳ)/>r in the formulae (II) and (IV) is C 5 ~C 30 Is a chain of an alkane.
4. The process according to claim 3, wherein the molar ratio of the compound of formula (II) to the compound of formula (III) in step (1) is 1 to 2, and the molar ratio of the compound of formula (II) to the palladium catalyst is 1 to 0.03 to 0.1.
5. The preparation method according to claim 3 or 4, wherein the palladium catalyst in the step (1) is one or two of tetra (triphenylphosphine) palladium and dichloro di (triphenylphosphine) palladium, and the organic solvent is one or more of N-methylpyrrolidone, dimethylformamide and dimethylacetamide.
6. The method according to claim 3, wherein the molar ratio of the compound represented by the formula (IV) to the iron trichloride in the polymerization reaction in the step (2) is 1 (6-10).
7. The process according to claim 3 or 6, wherein the organic solvent in the step (2) is one or more of dichloromethane, chloroform and tetrahydrofuran.
8. The method according to claim 3, wherein the reaction temperature in the step (1) is 100 to 160 ℃ and the reaction time is 12 to 36 hours; the reaction temperature in the step (2) is 20-30 ℃ and the reaction time is 12-36 h.
9. An electrochromic polymer film, characterized in that the electrochromic polymer according to claim 1 or 2 or the electrochromic polymer according to any one of claims 3 to 8 is processed.
10. Use of the electrochromic polymer film of claim 9 in military camouflage, display applications.
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