CN116110639A - Thermally reversible self-repairing silver nanowire flexible transparent conductive film and preparation method thereof - Google Patents
Thermally reversible self-repairing silver nanowire flexible transparent conductive film and preparation method thereof Download PDFInfo
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000002042 Silver nanowire Substances 0.000 title claims abstract description 64
- 230000002441 reversible effect Effects 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920002635 polyurethane Polymers 0.000 claims abstract description 16
- 239000004814 polyurethane Substances 0.000 claims abstract description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 75
- 238000006243 chemical reaction Methods 0.000 claims description 44
- 238000000576 coating method Methods 0.000 claims description 43
- 239000011248 coating agent Substances 0.000 claims description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 29
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 25
- 229920006264 polyurethane film Polymers 0.000 claims description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 23
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- DDRPCXLAQZKBJP-UHFFFAOYSA-N furfurylamine Chemical compound NCC1=CC=CO1 DDRPCXLAQZKBJP-UHFFFAOYSA-N 0.000 claims description 13
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 12
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims description 11
- 238000010907 mechanical stirring Methods 0.000 claims description 11
- 238000005266 casting Methods 0.000 claims description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 239000005457 ice water Substances 0.000 claims description 8
- 239000012948 isocyanate Substances 0.000 claims description 8
- 150000002513 isocyanates Chemical class 0.000 claims description 8
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 238000004448 titration Methods 0.000 claims description 4
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- 229920003192 poly(bis maleimide) Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
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- 229920000867 polyelectrolyte Polymers 0.000 description 2
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- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
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Abstract
The invention discloses a thermally reversible self-repairing flexible transparent conductive film and a preparation method thereof. The thermally reversible self-repairing flexible transparent conductive film is composed of a transparent conductive layer and a thermally reversible DA-reactive polyurethane basal layer; the transparent conductive layer is formed by a silver nanowire conductive network. The thermally reversible self-repairing flexible transparent conductive film has high transparency, good thermal repairing performance, good conductivity and light transmittance after repeated thermal repairing and high repairing efficiency.
Description
Technical Field
The invention belongs to the field of electronic functional materials, and particularly relates to a thermally reversible self-repairing silver nanowire flexible transparent conductive film and a preparation method thereof.
Background
In recent years, with the development of portable electronic devices and flexible wearable electronic devices, flexible optoelectronic devices have received high attention from academia and industry because of their advantages of thinness, portability, flexibility, good conformality, strong durability, and the like. The flexible transparent conductive film or electrode as the basic conductor of the flexible photoelectric device has great influence on the device performance, and is the core and key of the flexible photoelectric industry.
The proper operation of an electronic device depends on the electronic circuitry being conductive. However, the flexible transparent conductive film or electrode is easy to generate local microcracks or micro-damages due to repeated abrasion, bending, impact or scraping in use, and the macroscopic cracks are caused to generate cracks, so that the device cannot work normally, and even becomes electronic garbage. Early repair of cracks, particularly self-repair, is a real and important problem.
The self-repairing material is a novel intelligent material capable of imitating the autonomous healing of organisms when damaged, namely, the damaged part of the material is automatically healed through a substance or energy supply mechanism. Depending on the material and the manner of energy supply, it is generally classified into an implantable self-repairing and an intrinsic self-repairing. The intrinsic self-repairing material does not need to be added with a repairing agent in advance. When the material is damaged, the molecular chain segments are dissociated, recombined and wound under the stimulation of external light, electricity, magnetism, solvent and the like, so that the repaired material is realized. The material is mainly a polymer or a supermolecular polymer combined by reversible covalent bonds such as hydrogen bonding, metal coordination, pi-pi action and the like or non-covalent bonds such as acylhydrazone bond systems, disulfide bonds and Diels-Alder (DA) reactions.
Although research on self-repairing materials has been greatly advanced, only a few self-repairing material systems can be applied to the electronic field due to special requirements of electronic components on electricity, heat, force, environment and the like. The self-repairing conductive film is formed by dispersing conductive nano materials (such as metal nanowires, carbon nanotubes, graphene, conductive polymers, graded nano composite materials and the like) into a self-repairing polymer or a thermoplastic elastomer, and then forming a film through processes such as casting. Although the method has the characteristics of simple and quick operation, low cost and the like, the self-repairing conductive film prepared by the method is generally opaque, and greatly restricts the popularization and application of the material on flexible photoelectric devices.
In order to develop a flexible transparent electrode with self-healing function, researchers have tried several schemes such as drop-coating silver nanowires or surface-modified carbon nanotube suspensions on the surface of a Layer-by-Layer assembled polyelectrolyte multilayer film, polyelectrolyte hydrogel or ionic liquid-containing polymer gel, hot-pressing a silver nanowire film on the surface of a self-healing polyurethane film, and the like. Although the conductive film and the hydrogel conductive film assembled by the Layer-by-Layer have certain light transmittance, the circuit is short-circuited and even the self-repairing performance is lost due to water shortage in the water self-repairing process, and the conductive film obtained from the surface of the self-repairing polyurethane film through hot pressing has the problems that the transparency is relatively poor, the repairing efficiency is rapidly reduced along with the increase of the repairing times, and the like.
Disclosure of Invention
Aiming at the defects of low photoelectric performance, poor repeated repair performance and the like of the conventional self-repair flexible transparent conductive film, the invention provides a thermally reversible self-repair silver nanowire flexible transparent conductive film and a preparation method thereof. According to the method, a polyurethane film with a heat reversible Diels-Alder (DA) bond is used as a substrate, silver nanowires are coated on the surface of the heat reversible DA-reactive polyurethane film, and then the silver nanowires are adhered on the surface of the heat reversible DA-reactive polyurethane film through heat treatment to prepare the heat reversible self-repairing flexible transparent conductive film. The thermally reversible self-repairing flexible conductive film prepared by the method has the characteristics of excellent conductivity, light transmittance, high first repairing rate of more than 95%, good transparency and conductivity after five times of repairing, high repairing efficiency and the like.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of the thermally reversible self-repairing flexible transparent conductive film, which comprises the following steps:
pouring polytetrahydrofuran glycol into a reaction vessel, introducing nitrogen into the reaction vessel, heating to 50-70 ℃ under mechanical stirring, adding 4,4' -diphenylmethane diisocyanate into the reaction vessel after the temperature is constant, adding dimethylformamide solvent, and carrying out polymerization reaction under mechanical stirring in nitrogen atmosphere until the isocyanate content in the reactant reaches a theoretical end point (toluene-di-n-butylamine titration method) to obtain an-NCO terminated prepolymer;
cooling the reaction vessel temperature of the-NCO end-capped prepolymer to 0 ℃ by using ice water bath, then adding furfuryl amine and additional dimethylformamide solvent into the-NCO end-capped prepolymer, and continuing to perform polymerization reaction to obtain furan ring end-capped prepolymer;
and adding diphenylmethane bismaleimide and a dimethylformamide solvent into the furan ring blocked isocyanate, and continuing to perform chain extension reaction under the condition of nitrogen to obtain the thermoreversible DA-reactive polyurethane prepolymer.
And (3) casting the thermal reversible DA-reactive polyurethane prepolymer into a film, and then performing heat treatment in a drying oven at 60-80 ℃ for 24-2 hours to obtain the thermal reversible DA-reactive polyurethane film.
Preferably, in the polymerization reaction of the-NCO end-capped prepolymer, the mass content of polytetrahydrofuran glycol is 39.65-39.75 percent, and the mass content of 4,4' -diphenylmethane diisocyanate is 19.8-19.9 percent; the temperature of the polymerization reaction is 50-70 ℃ and the time is 2.5-3.5 hours.
Preferably, in the furan ring end-capped prepolymer polymerization reaction, the mass content of furfuryl amine is 6.0-6.1%, and the amount of the added dimethylformamide solvent is 7.4-7.5% of the mass of the reaction mixture.
Preferably, in the synthesis reaction of the thermal reversible DA-reactive polyurethane prepolymer, the mass content of the diphenylmethane bismaleimide is 9.8-9.9%, and the amount of the added dimethylformamide solvent is 11.1-11.4% of the mass of the reaction mixture; the temperature of the chain extension reaction is 50-70 ℃ and the time is 20-25 hours, and the thermoreversible DA reaction polyurethane prepolymer is obtained.
Preferably, the thermal reversible DA-reactive polyurethane prepolymer is cast into a film, and then the film is obtained in a drying oven at 60-80 ℃ for 24-32 hours.
The process for coating the silver nanowires on the surface of the thermally reversible self-repairing polyurethane basal layer comprises the following steps: firstly, coating a layer of absolute ethyl alcohol on the surface of a thermally reversible self-repairing polyurethane substrate layer, and waiting for 5-15 seconds; then coating silver nanowire solution on the surface of a substrate, and performing heat treatment in a drying oven at 60-80 ℃ until the weight is constant, so as to obtain a thermally reversible self-repairing flexible transparent conductive film; the concentration of silver nanowires in the silver nanowire solution is 4-8 mg/mL, and the solvent is absolute ethyl alcohol.
The invention provides a flexible transparent conductive film of a thermally reversible self-repairing silver nanowire, which comprises a transparent conductive layer and a thermally reversible DA-reactive polyurethane basal layer; the transparent conductive layer is a silver nanowire network layer. The method comprises the steps of taking a polyurethane film with a heat reversible Diels-Alder (DA) bond as a substrate, coating silver nanowires on the surface of the heat reversible DA-reactive polyurethane film, and then adhering the silver nanowires on the surface of the heat reversible DA-reactive polyurethane film through heat treatment to prepare the heat reversible self-repairing flexible transparent conductive film.
In order to realize uniform deposition of the silver nanowires on the surface of the thermoreversible DA-reactive polyurethane, before the silver nanowires are coated, a layer of absolute ethyl alcohol is coated on the surface of the substrate, so that the surface layer of the substrate is properly dissolved. The thermal reversible self-repairing flexible conductive film prepared by the method has 15.8-118.2 ohms/square resistance at room temperature, has high transparency and conductivity at 550nm light transmittance of 82.3-63.7%, is subjected to heat treatment at 140 ℃ for 10-20 minutes, and then is put into a baking oven at 70 ℃ for heat treatment for 24 hours, so that surface microcracks are self-repaired, the first repair rate is higher than 95%, and after three repairs, the thermal reversible self-repairing flexible conductive film still has good transparency and conductivity, and the repair efficiency is high.
Description of the embodiments
The invention provides a thermally reversible self-repairing flexible transparent conductive film, which comprises a transparent conductive layer and a thermally reversible DA (DA) reactive polyurethane basal layer; the transparent conductive layer is a silver nanowire conductive network; the thermoreversible DA-reactive polyurethane basal layer is synthesized by DA reaction of furan-terminated polyurethane prepolymer and bismaleimide.
The heat reversible self-repairing flexible transparent conductive film comprises a heat reversible DA (DA) reactive polyurethane basal layer, wherein the thickness of the heat reversible DA reactive polyurethane basal layer is preferably 100-200 mu m, and the light transmittance is 94-89% at 550 nm; in embodiments of the invention, it is specifically 100 μm or 200 μm. The thermal reversible DA-reactive polyurethane has good light transmittance, and is used as a substrate, and in the heat treatment and thermal repair process, the thermal reversible DA-reactive polyurethane is melted, flows and the thermal reversible DA-reactive polyurethane is subjected to self-repair of the substrate, and simultaneously drives the silver nanowire conductive mesh to be reconstructed, so that the electrical property of the film is repaired.
The thermally reversible self-repairing flexible transparent conductive film provided by the invention comprises a transparent conductive layer, wherein the transparent conductive layer is a silver nanowire conductive net. The transparent conductive layer is preferably composed of 2-6 layers of silver nanowire conductive networks; the corresponding transparent conductive layer has a total thickness of about 70 to 280 a nm a. The silver nanowire conductive net is used as the transparent conductive layer, so that the film has conductive performance.
The invention provides a preparation method of a thermally reversible self-repairing flexible transparent conductive film, which comprises the following steps: and coating a layer of absolute ethyl alcohol on the surface of the thermoreversible DA-reactive polyurethane substrate by adopting a coating process to enable the surface of the substrate to be properly dissolved, coating silver nanowires on the surface of the substrate by adopting the coating process, forming a transparent conductive layer on the surface of the substrate, and drying to obtain the thermoreversible self-repairing flexible transparent conductive film.
In the present invention, the raw materials used are commercially available products well known in the art, unless specifically described otherwise.
The invention adopts a coating process to coat silver nanowire transparent conduction on the surface of a substrate, and forms a transparent conductive layer on the surface of the substrate.
In the present invention, the process of coating the transparent conductive layer of silver nanowires on the surface of the substrate by using the coating method preferably includes: mixing silver nanowires with ethylene glycol to obtain silver nanowire conductive ink; and coating the silver-penetrating nanowire conductive ink on the surface of a substrate to form a silver nanowire transparent conductive network pattern.
According to the invention, silver nanowires and ethylene glycol are mixed to obtain transparent conductive ink. In the present invention, the length of the silver nanowire is preferably 40 to 60 μm, and the diameter is preferably 30 to 40 nm; in the invention, the concentration of the silver nanowires in the transparent conductive ink is preferably 2-8 mg/mL, more preferably 3-5 mg/mL; the invention has no special requirement on the mixing process, and can be used in any mode of uniformly mixing the two.
The present invention preferably uses a coater to perform the coating. The invention has no special requirements on the specific model of the coater, and the coater well known in the art can be adopted. In the invention, the speed of the coating machine in the process of coating the absolute ethyl alcohol is preferably 80-120 m/min, more preferably 80-100 m/min, and the speed of the coating machine in the process of coating the silver nanowire is preferably 10-40 m/min, more preferably 20-30 m/min; the invention has no special requirement on the specific shape of the silver nanowire transparent conductive layer, and the silver nanowire transparent conductive layer can be designed by a person skilled in the art according to the needs under the condition of ensuring good conductivity of the silver nanowire conductive layer. The present invention preferably coats multiple silver nanowire conductive layers to achieve a target thickness.
After the coating is completed, the present invention preferably further includes heat treating the sample. In the present invention, the temperature of the heat treatment is preferably 70 ℃; and adhering the silver nanowires on the surface of the thermally reversible DA-reactive polyurethane substrate after heat treatment in the curing process to obtain the thermally reversible self-repairing flexible transparent conductive film.
The preparation of the thermoreversible DA-reactive polyurethane film is described first.
In the present invention, the method for preparing the thermoreversible DA-reactive polyurethane film preferably comprises the steps of:
pouring polytetrahydrofuran glycol into a reaction vessel, introducing nitrogen into the reaction vessel, heating to 50-70 ℃ under mechanical stirring, adding 4,4' -diphenylmethane diisocyanate into the reaction vessel after the temperature is constant, adding dimethylformamide solvent, and carrying out polymerization reaction under mechanical stirring in nitrogen atmosphere until the isocyanate content in the reactant reaches a theoretical end point (toluene-di-n-butylamine titration method) to obtain an-NCO terminated prepolymer;
cooling the reaction vessel temperature of the-NCO end-capped prepolymer to 0 ℃ by using ice water bath, then adding furfuryl amine and additional dimethylformamide solvent into the-NCO end-capped prepolymer, and continuing to perform polymerization reaction to obtain furan ring end-capped prepolymer;
and adding diphenylmethane bismaleimide and a dimethylformamide solvent into the furan ring blocked isocyanate, and continuing to perform chain extension reaction under the condition of nitrogen to obtain the thermoreversible DA-reactive polyurethane prepolymer.
And (3) casting the thermal reversible DA-reactive polyurethane prepolymer into a film, and then performing heat treatment in a drying oven at 60-80 ℃ for 24-2 hours to obtain the thermal reversible DA-reactive polyurethane film.
Preferably, in the polymerization reaction of the-NCO end-capped prepolymer, the mass content of polytetrahydrofuran glycol is 39.65-39.75 percent, and the mass content of 4,4' -diphenylmethane diisocyanate is 19.8-19.9 percent; the polymerization reaction is carried out at a temperature of 50 to 70℃for a period of 2.5 to 3.5 hours, preferably 60℃for a period of 3 hours. In the present invention, the polymerization of the-NCO-terminated prepolymer is preferably carried out under stirring conditions, and the stirring conditions are not particularly limited in the present invention, and stirring equipment well known in the art may be used;
preferably, in the furan ring end-capped prepolymer polymerization reaction, the mass content of furfuryl amine is 6.0-6.1%, and the amount of the added dimethylformamide solvent is 7.4-7.5% of the mass of the reaction mixture.
In the present invention, the process of adding furfuryl amine and replenishing the solvent to the-NCO-terminated prepolymer preferably comprises:
cooling the prepolymer reaction vessel with-NCO end to 0 ℃ by using ice water bath, dropwise adding furfuryl amine and adding solvent, and returning the temperature to room temperature after the dropwise adding is finished. As the prepolymer with the end capped by the-NCO and the furfuryl amine are extremely easy to react, the temperature of the prepolymer with the end capped by the-NCO is reduced to 0 ℃, and meanwhile, the furfuryl amine is added in a dropwise manner, so that the too fast occurrence of the polymerization reaction can be prevented. The invention has no special requirement on the dropping speed, and can prevent the reaction from happening too fast.
In the present invention, the polymerization temperature of the furan ring-terminated prepolymer is preferably room temperature. The present invention has no special requirement on the polymerization time of the furan ring-terminated prepolymer, and the reaction end point is preferably determined by detecting the disappearance of the-NCO characteristic absorption peak at about 2270 cm-1 by infrared spectroscopy.
After the furan ring end-capped prepolymer is obtained, diphenylmethane bismaleimide and additional dimethylformamide are directly added into the furan ring end-capped prepolymer, and then chain extension reaction is carried out under the condition of nitrogen, so that the thermoreversible DA-reactive polyurethane prepolymer is obtained.
In the invention, in the thermal reversible DA reaction polyurethane prepolymer reaction, the mass content of the diphenylmethane bismaleimide is preferably 9.8-9.9%, and the amount of the added solvent is preferably 11.1-11.4% of the mass of the mixture.
In the present invention, the temperature of the chain extension reaction is preferably 50 to 70 ℃, more preferably 60 ℃; the time is preferably 20 to 25 hours, more preferably 24 hours. The chain extension reaction is preferably carried out under stirring conditions, and the stirring speed is not particularly required in the present invention, and stirring speeds well known in the art are adopted.
After the chain extension reaction is completed, the reaction product is preferably cooled to room temperature to obtain the thermo-reversible DA-reactive polyurethane prepolymer.
And (3) casting the thermal reversible DA-reactive polyurethane prepolymer into a film, and drying the film in a drying oven at 60-80 ℃ until the weight is constant, thus obtaining the thermal reversible DA-reactive polyurethane film.
In the present invention, the cast film is not particularly required, and the thickness of the film is ensured to be 100 to 200 μm, preferably 120 μm, and the temperature is preferably 70 ℃ by using a casting device well known in the art, and the present invention has no particular requirement for the drying time and can be dried to constant weight. The drying process is a process of forming the thermoreversible DA-reactive polyurethane film by solidifying the thermoreversible DA-reactive polyurethane prepolymer.
The thermally-modified flexible transparent conductive film and the method of producing the same according to the present invention will be described in detail with reference to examples, but they should not be construed as limiting the scope of the present invention. Example 1
Preparation of thermoreversible DA-reactive polyurethane film: : 30.0126 g of polytetrahydrofuran diol is added into a three-neck flask, and then nitrogen is introduced; 30.0126 g of N, N-dimethylformamide is added into a beaker, 15.0063 g of 4 '-diphenylmethane diisocyanate is added into the beaker, stirred until the 4' -diphenylmethane diisocyanate is completely dissolved, then the mixture is added into a three-neck flask filled with polytetrahydrofuran glycol, and the mixture is reacted for 3 hours at 60 ℃ under the mechanical stirring speed of 250 rpm to generate a prepolymer terminated by-NCO; reducing the temperature of the three-neck flask to 0 ℃ by using an ice water bath, dropwise adding 5.3205 g of furfuryl amine at the rate of 6 drops per second, supplementing 6.5107 g of N, N-dimethylformamide, and after the dropwise adding is finished, recovering the reaction temperature to room temperature, and continuing to react under the protection of nitrogen to obtain furan ring end-capped prepolymer; 10.9702 g of bismaleimide is added into the furan ring end-capped prepolymer system, 13.4108 g of solvent N, N-dimethylformamide is added, and chain extension reaction is carried out for 24 hours at 60 ℃; cooling to room temperature after the reaction is completed to obtain a thermo-reversible DA-reactive polyurethane prepolymer; and (3) casting the thermoreversible DA-reactive polyurethane prepolymer into a film, and then drying the film to constant weight in a drying oven at 70 ℃ to obtain the thermoreversible DA-reactive polyurethane film.
Preparation of a thermally reversible self-repairing silver nanowire flexible transparent conductive film: adding 10 mg silver nanowires (with the length of 40-60 mu m and the diameter of 30-40 nm) into 10 mL absolute ethyl alcohol to obtain silver nanowire conductive ink; coating absolute ethyl alcohol on the surface of the thermoreversible DA-reactive polyurethane film by using a coating machine at the coating rate of 100 m/min, and waiting for 10 seconds; and then coating silver nanowire conductive ink, wherein the coating speed is 20 m/min, repeatedly coating 4 layers to obtain a silver nanowire conductive layer, and then carrying out heat treatment on the coated sample in a drying oven at the temperature of 70 ℃ until the weight is constant, thus obtaining the thermally reversible DA self-repairing flexible transparent conductive film.
The transmittance of the prepared thermal reversible DA self-repairing flexible transparent conductive film at 550nm is 78.9%, and the sheet resistance is 28.1 ohm/square.
Marking out scratches with a length of 1 cm on the surface of the conductive film by using a craft knife, then placing the conductive film in a 140 ℃ oven for heat treatment for 10 minutes, and then placing the conductive film in a 70 ℃ oven for heat treatment for 24 hours, so that surface microcracks disappear; the transmittance of the repaired conductive film at 550nm is 78.6%, and the sheet resistance is 22.3 ohm/square; repeating the above process for the second time at the repaired wound, and measuring the light transmittance of the repaired conductive film at 550nm to be 78.2% and the square resistance to be 26.5 ohm/square; and repeating the process for the third time at the repaired wound, wherein the transmittance of the repaired conductive film at 550nm is 71.5%, and the sheet resistance is 69.6 ohms/square. Example 2
Preparation of thermoreversible DA-reactive polyurethane film: 30.0126 g of polytetrahydrofuran diol is added into a three-neck flask, and then nitrogen is introduced; 30.0126 g of N, N-dimethylformamide is added into a beaker, 15.0063 g of 4 '-diphenylmethane diisocyanate is added into the beaker, stirred until the 4' -diphenylmethane diisocyanate is completely dissolved, then the mixture is added into a three-neck flask filled with polytetrahydrofuran glycol, and the mixture is reacted for 3 hours at 60 ℃ under the mechanical stirring speed of 250 rpm to generate a prepolymer terminated by-NCO; reducing the temperature of the three-neck flask to 0 ℃ by using an ice water bath, dropwise adding 5.3205 g of furfuryl amine at the rate of 6 drops per second, supplementing 6.5107 g of N, N-dimethylformamide, and after the dropwise adding is finished, recovering the reaction temperature to room temperature, and continuing to react under the protection of nitrogen to obtain furan ring end-capped prepolymer; 10.9702 g of bismaleimide is added into the furan ring end-capped prepolymer system, 13.4108 g of solvent N, N-dimethylformamide is added, and chain extension reaction is carried out for 24 hours at 60 ℃; cooling to room temperature after the reaction is completed to obtain a thermo-reversible DA-reactive polyurethane prepolymer; and (3) casting the thermoreversible DA-reactive polyurethane prepolymer into a film, and then drying the film to constant weight in a drying oven at 70 ℃ to obtain the thermoreversible DA-reactive polyurethane film.
Preparation of a thermally reversible self-repairing silver nanowire flexible transparent conductive film: adding 10 mg silver nanowires (with the length of 40-60 mu m and the diameter of 30-40 nm) into 10 mL absolute ethyl alcohol to obtain silver nanowire conductive ink; coating absolute ethyl alcohol on the surface of the thermoreversible DA-reactive polyurethane film by using a coating machine at the coating rate of 100 m/min, and waiting for 10 seconds; then coating silver nanowire conductive ink, wherein the coating speed is 20 m/min, repeatedly coating 5 layers to obtain a silver nanowire conductive layer, and then carrying out heat treatment on the coated sample in a drying oven at the temperature of 70 ℃ until the weight is constant, thus obtaining the thermally reversible DA self-repairing flexible transparent conductive film.
The transmittance of the prepared thermal reversible DA self-repairing flexible transparent conductive film at 550nm is 71.2%, and the sheet resistance is 14.5 ohms/square.
Marking out scratches with a length of 1 cm on the surface of the conductive film by using a craft knife, then placing the conductive film in a 140 ℃ oven for heat treatment for 10 minutes, and then placing the conductive film in a 70 ℃ oven for heat treatment for 24 hours, so that surface microcracks disappear; the transmittance of the repaired conductive film at 550nm is 70.1%, and the sheet resistance is 15.6 ohm/square; repeating the above process for the second time at the repaired wound, and measuring the transmittance of the repaired conductive film at 550nm to be 67.2% and the square resistance to be 20.5 ohm/square; and repeating the process for the third time at the repaired wound, wherein the transmittance of the repaired conductive film at 550nm is measured to be 62.7%, and the sheet resistance is measured to be 59.2 ohms/square. Example 3
Preparation of thermoreversible DA-reactive polyurethane film: 30.0126 g of polytetrahydrofuran diol is added into a three-neck flask, and then nitrogen is introduced; 30.0126 g of N, N-dimethylformamide is added into a beaker, 15.0063 g of 4 '-diphenylmethane diisocyanate is added into the beaker, stirred until the 4' -diphenylmethane diisocyanate is completely dissolved, then the mixture is added into a three-neck flask filled with polytetrahydrofuran glycol, and the mixture is reacted for 3 hours at 60 ℃ under the mechanical stirring speed of 250 rpm to generate a prepolymer terminated by-NCO; reducing the temperature of the three-neck flask to 0 ℃ by using an ice water bath, dropwise adding 5.3205 g of furfuryl amine at the rate of 6 drops per second, supplementing 6.5107 g of N, N-dimethylformamide, and after the dropwise adding is finished, recovering the reaction temperature to room temperature, and continuing to react under the protection of nitrogen to obtain furan ring end-capped prepolymer; 10.9702 g of bismaleimide is added into the furan ring end-capped prepolymer system, 13.4108 g of solvent N, N-dimethylformamide is added, and chain extension reaction is carried out for 24 hours at 60 ℃; cooling to room temperature after the reaction is completed to obtain a thermo-reversible DA-reactive polyurethane prepolymer; and (3) casting the thermoreversible DA-reactive polyurethane prepolymer into a film, and then drying the film to constant weight in a drying oven at 70 ℃ to obtain the thermoreversible DA-reactive polyurethane film.
Preparation of a thermally reversible self-repairing silver nanowire flexible transparent conductive film: adding 10 mg silver nanowires (with the length of 40-60 mu m and the diameter of 30-40 nm) into 10 mL absolute ethyl alcohol to obtain silver nanowire conductive ink; coating absolute ethyl alcohol on the surface of the thermoreversible DA-reactive polyurethane film by using a coating machine at the coating rate of 100 m/min, and waiting for 10 seconds; and then coating silver nanowire conductive ink, wherein the coating speed is 20 m/min, repeatedly coating 2 layers to obtain a silver nanowire conductive layer, and then carrying out heat treatment on the coated sample in a drying oven at the temperature of 70 ℃ until the weight is constant, thus obtaining the thermally reversible DA self-repairing flexible transparent conductive film.
The transmittance of the prepared thermal reversible DA self-repairing flexible transparent conductive film at 550nm is 81.9%, and the sheet resistance is 108.2 ohm/square.
Marking out scratches with a length of 1 cm on the surface of the conductive film by using a craft knife, then placing the conductive film in a 140 ℃ oven for heat treatment for 10 minutes, and then placing the conductive film in a 70 ℃ oven for heat treatment for 24 hours, so that surface microcracks disappear; the transmittance of the repaired conductive film at 550nm is 80.6%, and the sheet resistance is 118.2 ohm/square; repeating the above process for the second time at the repaired wound, and measuring the light transmittance of the repaired conductive film at 550nm to be 79.2% and the square resistance of 136.7 ohm/square; and repeating the process for the third time at the repaired wound, wherein the transmittance of the repaired conductive film at 550nm is 74.5%, and the sheet resistance is 168.2 ohms/square.
The applicant states that the detailed method of the present invention is illustrated by the above examples, but the present invention is not limited to the detailed method described above, i.e. it does not mean that the present invention must be practiced in dependence upon the detailed method described above. It should be apparent to those skilled in the art that any modification of the present invention, effective replacement of raw materials and addition of auxiliary components of the product of the present invention, selection of specific modes, etc. fall within the scope of the present invention and the scope of disclosure.
Claims (3)
1. The thermally reversible self-repairing flexible transparent conductive film is characterized by comprising a transparent conductive layer and a thermally reversible DA-reactive polyurethane basal layer; the transparent conductive layer is a silver nanowire conductive network; the thermal reversible D-reactive polyurethane substrate layer thermal reversible DA-reactive polyurethane prepolymer is prepared by the following steps: the preparation method of the thermoreversible DA-reactive polyurethane prepolymer comprises the following steps: pouring polytetrahydrofuran glycol into a reaction vessel, introducing nitrogen into the reaction vessel, heating to 50-70 ℃ under mechanical stirring, adding 4,4' -diphenylmethane diisocyanate into the reaction vessel after the temperature is constant, adding dimethylformamide solvent, and carrying out polymerization reaction under mechanical stirring in nitrogen atmosphere until the isocyanate content in the reactant reaches a theoretical end point (toluene-di-n-butylamine titration method) to obtain an-NCO terminated prepolymer; cooling the reaction vessel temperature of the-NCO end-capped prepolymer to 0 ℃ by using ice water bath, then adding furfuryl amine and additional dimethylformamide solvent into the-NCO end-capped prepolymer, and continuing to perform polymerization reaction to obtain furan ring end-capped prepolymer; and adding diphenylmethane bismaleimide and a dimethylformamide solvent into the furan ring blocked isocyanate, and continuing to perform chain extension reaction under the condition of nitrogen to obtain the thermoreversible DA-reactive polyurethane prepolymer.
2. The method for preparing a thermally reversible self-healing flexible transparent conductive film according to claim 1, comprising the steps of: and (3) casting the thermoreversible DA-reactive polyurethane prepolymer into a film, and then carrying out heat treatment for 24-32 hours at 60-80 ℃ in a drying oven to obtain the thermoreversible DA-reactive polyurethane film. Coating a layer of absolute ethyl alcohol on the surface of the thermal reversible DA reaction polyurethane film, waiting for 5-15 seconds, then coating silver nanowire solution, and placing a sample in a drying oven for heat treatment at 60-80 ℃ until the weight is constant, thus obtaining the thermal reversible DA reaction self-repairing flexible transparent conductive film; the preparation method of the thermoreversible DA-reactive polyurethane prepolymer comprises the following steps: pouring polytetrahydrofuran glycol into a reaction vessel, introducing nitrogen into the reaction vessel, heating to 50-70 ℃ under mechanical stirring, adding 4,4' -diphenylmethane diisocyanate into the reaction vessel after the temperature is constant, adding dimethylformamide solvent, and carrying out polymerization reaction under mechanical stirring in nitrogen atmosphere until the isocyanate content in the reactant reaches a theoretical end point (toluene-di-n-butylamine titration method) to obtain an-NCO terminated prepolymer; cooling the reaction vessel temperature of the-NCO end-capped prepolymer to 0 ℃ by using ice water bath, then adding furfuryl amine and additional dimethylformamide solvent into the-NCO end-capped prepolymer, and continuing to perform polymerization reaction to obtain furan ring end-capped prepolymer; and adding diphenylmethane bismaleimide and a dimethylformamide solvent into the furan ring blocked isocyanate, and continuing to perform chain extension reaction under the condition of nitrogen to obtain the thermoreversible DA-reactive polyurethane prepolymer.
3. The method of claim 2, wherein the coating process of the silver nanowire conductive network on the surface of the substrate comprises: mixing the silver nanowires with absolute ethyl alcohol to obtain silver nanowire conductive ink; firstly, coating a layer of absolute ethyl alcohol on the surface of a substrate at the coating rate of 80-120 m/min, properly dissolving the surface of a base, and coating the silver nanowire conductive ink on the surface of the substrate to form a silver nanowire transparent conductive layer at the coating rate of 10-40 m/min; the concentration of the silver nanowire conductive ink is 2-8 mg/mL, and the silver nanowire transparent conductive layer consists of 2-6 layers of silver nanowire conductive networks.
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