CN111471125B - Method for preparing transparent conductive material from Pickering emulsion - Google Patents
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Abstract
The invention relates to a method for preparing a transparent conductive material by Pickering emulsion, which comprises the following steps: the method comprises the following steps: preparing a Pickering emulsifier; step two: preparing a Pickering pre-emulsion; step three: preparing core-shell structure conductive dispersion emulsion; step four: and preparing the transparent conductive material. According to the invention, the one-dimensional nano conductive metal material is modified to prepare the Pickering emulsion agent, and then the dispersion emulsion of the core-shell structure conductive material is obtained through polymerization, and the dispersion emulsion can be used for conveniently realizing the preparation of the transparent conductive material in a coating or printing mode. The conductive ink prepared by the invention has good stability and is easy to store for a long time; the conductive ink prepared by the invention has good interface wettability, is easy to print and coat to prepare a material with uniform conductivity, and has good adhesive force.
Description
Technical Field
The invention relates to a method for preparing a transparent conductive material, in particular to a method for preparing a transparent conductive material from Pickering emulsion, belonging to the field of preparation of high polymers and conductive materials.
Background
A transparent conductive material is a material having a good transmittance in the visible light range and also having good conductivity. Many electronic products require good visible light transmittance and good electrical conductivity, and for example, optoelectronic products such as flat panel displays, touch panels, solar cells, electronic paper, and OLED lighting require transparent conductive materials. In addition, the rapid development of electronic devices and the rapid advance of computer network technologies greatly promote the development of human society, bring great convenience to daily life of people, and bring potential safety hazards such as electromagnetic interference, electromagnetic radiation, information leakage and the like. The visible part of the electronic device needs to be effectively protected from electromagnetic radiation by a thin film material with high light transmittance and high electromagnetic shielding performance, and the electromagnetic protection of the visible part is mainly realized by a transparent conductive material. The transparent conductive material mainly includes a metal film system, an oxide film system, other compound film system, a polymer film system, a composite film system, and the like.
The Transparent Conductive Oxide (TCO) semiconductor film mainly comprises oxides of In, Sn, Zn and Cd and a composite multi-element oxide film, specifically comprises ITO, FTO, AZO and the like, wherein the ITO (indium tin oxide) film is a transparent conductive material which is researched and applied most at present. The metal grid material is also a material which is applied to a transparent conductive material in a large number, and common preparation processes of the metal grid material comprise a photoetching method, a nano-imprinting method, a self-assembly method and the like. The metal nanowires are transparent conductive materials which are mostly researched and applied except for an ITO shielding film at present, and comprise gold nanowires (AuNWs), copper nanowires (CuNWs), silver nanowires (AgNWs) and the like. The metal nano wire transparent conductive material is prepared by preparing metal into a nano-scale long linear material and forming a conductive grid through random overlapping. Compared with a metal grid material, the diameter of the metal nanowire is smaller, the grid wires are more dense, and the conductivity and the light transmittance of the material are greatly improved. When the transparent conductive material is prepared, the conductivity of the composite material prepared from the carbon-based material is far from the requirement, so that the application of the composite material as the transparent conductive material is limited.
Disclosure of Invention
The invention aims to provide a simple method for preparing a transparent conductive material from Pickering emulsion with excellent performance.
The purpose of the invention is realized as follows:
a method for preparing a transparent conductive material by Pickering emulsion comprises the following steps:
the method comprises the following steps: preparation of Pickering emulsifier: mixing the one-dimensional nano metal material with a modifier A and a modifier B in a solvent, performing ultrasonic treatment, centrifuging, and freeze-drying to obtain a modified nano metal material, namely a Pickering emulsifier;
step two: preparation of Pickering pre-emulsion: adding the Pickering emulsifier obtained in the step one into deionized water, and adding an initiator and a polymer monomer A under the stirring or ultrasonic condition to obtain a Pickering pre-emulsion;
step three: preparing the core-shell structure conductive dispersion emulsion: adding a polymer monomer B into the Pickering pre-emulsion in the second step in a dropwise manner, stirring in the dropwise process, and reacting for a period of time after dropwise addition to obtain the core-shell structure conductive dispersion emulsion;
step four: preparing a transparent conductive material: and (3) coating and printing the conductive dispersion liquid obtained in the third step on a transparent substrate to obtain the transparent conductive material.
The one-dimensional nano material in the first step is one or more of a nano copper wire, a nano silver wire, a nano gold wire and a nano nickel wire;
the modifier A in the first step is a water-based modifier, and is one or more of sulfhydryl polyethylene glycol carboxyl, sulfhydryl polyethylene glycol, 16-sulfhydryl hexadecyl acid and amino acid; the modifier B is an oily modifier and is one or more of n-hexanoic acid, n-hexylmercaptan, n-propylmercaptan, octadecanol and octadecylamine; the molar ratio of the modifier A to the modifier B is (1-20) to (1-20);
the glass transition temperature of the polymer monomer A in the second step is less than 60 ℃, and the polymer monomer A is one or more of butyl acrylate, methyl acrylate, ethyl acrylate and isobutyl acrylate;
in the third step, the glass transition temperature of the polymer monomer B is more than 80 ℃, and the polymer monomer B is one or more of isobornyl methacrylate, methyl methacrylate, styrene and acrylonitrile;
the molar ratio of the polymer A to the polymer B is (1-10): (1-10).
Compared with the prior art, the invention has the beneficial effects that:
the invention modifies the surface of a one-dimensional nano metal material by a simple method to obtain an interface hydrophilic oleophilic nano metal material, and then obtains conductive ink by Pickering emulsion polymerization, and the invention has the following advantages: the conductive ink prepared by the invention has good stability and is easy to store for a long time; the conductive ink prepared by the invention has good interface wettability, is easy to print and coat to prepare a material with uniform conductivity, and has good adhesive force.
The preparation method of the conductive dispersion emulsion is simple, and the obtained transparent conductive material has good conductivity, high transparency and good adhesive force and is easy for industrial application.
Detailed Description
The invention is described in more detail below by way of example, describing embodiments and specific procedures:
the invention discloses a conductive ink and a preparation method of a transparent conductive film thereof, aiming at meeting the requirement of industrialization on application of transparent conductive materials. According to the invention, the one-dimensional nano conductive metal material is modified to prepare the Pickering emulsion agent, and then the dispersed emulsion of the core-shell structure conductive material is obtained through polymerization, and the dispersed emulsion can be used for conveniently realizing the preparation of the transparent conductive material in a coating or printing mode.
The invention adopts a Pickering emulsion method to obtain a conductive material dispersion emulsion with a core-shell structure, and then the transparent conductive material can be easily prepared, and the preparation steps are as follows:
(1) a Pickering emulsifier was prepared. Mixing the one-dimensional nano metal material with the modifier A and the modifier B in a solvent, performing ultrasonic treatment, centrifuging, and freeze-drying to obtain the modified nano metal material, namely the Pickering emulsifier.
(2) A Pickering pre-emulsion was prepared. Adding the Pickering emulsifier obtained in the step (1) into deionized water, and adding an initiator and a polymer monomer A under the stirring or ultrasonic condition to obtain the Pickering pre-emulsion.
(3) Preparing the core-shell structure conductive dispersion emulsion. And (3) adding the polymer monomer B into the Pickering pre-emulsion in the step (2) in a dropwise manner, stirring in the dropwise process, and reacting for a period of time after dropwise addition to obtain the core-shell structure conductive dispersion emulsion.
(4) And preparing the transparent conductive material. And (3) coating and printing the conductive dispersion liquid obtained in the step (3) on a transparent substrate to obtain the transparent conductive material.
The one-dimensional nano material adopted by the Pickering emulsifier in the step 1) can be one or more of nano copper wires, nano silver wires, nano gold wires, nano nickel wires and the like;
the modifier A adopted in the preparation of the Pickering emulsifier in the step 1) is a water-based modifier which can be one or more of sulfhydryl polyethylene glycol carboxyl, sulfhydryl polyethylene glycol, 16-sulfhydryl hexadecyl acid, amino acid and the like; the modifier B is an oily modifier which can be one or more of n-hexanoic acid, n-hexylmercaptan, n-propylmercaptan, octadecanethiol, octadecylamine and the like; the molar ratio of the modifier A to the modifier B can be (1-20) to (1-20);
the preparation method of the Pickering emulsifier comprises the following steps of 1) preparing the Pickering emulsifier by using an ultrasonic power of 50-200W and an ultrasonic time of 1-5 min;
the initiator used for preparing the Pickering pre-emulsion in the step 2) can be one or more of benzoyl peroxide, cumene hydroperoxide, potassium persulfate, azobisisobutyronitrile and the like;
the glass transition temperature of a polymer monomer A adopted for preparing the Pickering pre-emulsion in the step 2) is less than 60 ℃, and the polymer monomer A can be one or more of butyl acrylate, methyl acrylate, ethyl acrylate, isobutyl acrylate and the like;
the glass transition temperature of the polymer monomer B adopted for preparing the core-shell structure conductive dispersion emulsion in the step 3) is more than 80 ℃, and the polymer monomer B can be one or more of isobornyl methacrylate, methyl methacrylate, styrene, acrylonitrile and the like;
the molar ratio of the polymer A to the polymer B adopted for preparing the Pickering pre-emulsion in the step 2) and the core-shell structure conductive dispersion emulsion in the step 3) can be (1-10): (1-10);
the coating and printing mode adopted by the preparation of the transparent conductive material in the step 4) can be one of slit coating, micro-concave coating, scraper coating, ink-jet printing and the like;
the transparent base material adopted for preparing the transparent conductive material in the step 4) can be one of polymethacrylic resin, inorganic glass, polyimide, polypropylene, polyethylene glycol terephthalate and the like;
example 1
Step 1, preparing a Pickering emulsifier.
Mixing 100 parts of nano copper wire with 10 parts of modifying agent sulfhydryl polyethylene glycol and 20 parts of modifying agent n-hexylmercaptan in tetrahydrofuran solvent, carrying out ultrasonic treatment with 50W power for 2 minutes, centrifuging, and freeze-drying to obtain a modified nano copper wire material, namely a Pickering emulsifier.
Step 2, preparing Pickering pre-emulsion.
Adding 1 part of Pickering emulsifier obtained in the step 1 into deionized water, and adding 1 part of cumene hydroperoxide as an initiator and 50 parts of polymer monomer butyl acrylate under the condition of stirring at 600 revolutions per minute to obtain the Pickering pre-emulsion.
And 3, preparing the core-shell structure conductive dispersion emulsion.
And (3) adding 100 parts of polymer monomer methyl methacrylate into the Pickering pre-emulsion in the step (2) in a dropwise manner, stirring in the dropwise process, and reacting for 6 hours after dropwise addition to obtain the core-shell structure conductive dispersion emulsion.
And 4, preparing the transparent conductive material.
And (3) coating the conductive dispersion liquid obtained in the step (3) on the transparent substrate polyethylene terephthalate by means of slit coating to obtain the transparent conductive material.
Example 2
Step 1, preparing a Pickering emulsifier.
100 parts of nano silver wire is mixed with 5 parts of 16-mercapto hexadecyl acid as a modifier and 30 parts of octadecanethiol as a modifier in N-methylpyrrolidone as a solvent, ultrasonic treatment is carried out for 1 minute at the power of 80W, and the modified nano silver wire material, namely the Pickering emulsifier, is obtained by freeze drying after centrifugation.
Step 2, preparing Pickering pre-emulsion.
Adding 0.5 part of Pickering emulsifier obtained in the step 1 into deionized water, and adding 1 part of azoisobutyronitrile as an initiator and 30 parts of polymer monomer isobutyl acrylate under the condition of stirring at 700 revolutions per minute to obtain Pickering pre-emulsion.
And 3, preparing the core-shell structure conductive dispersion emulsion.
And (3) adding 150 parts of polymer monomer styrene into the Pickering pre-emulsion in the step (2) in a dropwise manner, stirring in the dropwise process, and reacting for 8 hours after dropwise addition to obtain the core-shell structure conductive dispersion emulsion.
And 4, preparing the transparent conductive material.
And (3) printing the conductive dispersion liquid obtained in the step (3) on the transparent base polyimide by an ink-jet printing mode to obtain the transparent conductive material.
Example 3
Step 1, preparing a Pickering emulsifier.
Mixing 100 parts of nano nickel wire with 10 parts of modifier amino acid and 20 parts of modifier n-hexanoic acid in tetrahydrofuran solvent, carrying out ultrasonic treatment with 100W power for 1 minute, centrifuging, and freeze-drying to obtain a modified nano copper wire material, namely a Pickering emulsifier.
Step 2, preparing Pickering pre-emulsion.
Adding 1 part of Pickering emulsifier obtained in the step 1 into deionized water, and adding 1 part of initiator benzoyl peroxide and 50 parts of polymer monomer methyl acrylate under the condition of stirring at 600 revolutions per minute to obtain Pickering pre-emulsion.
And 3, preparing the core-shell structure conductive dispersion emulsion.
And (3) adding 100 parts of polymer monomer acrylonitrile into the Pickering pre-emulsion in the step (2) in a dropwise manner, stirring in the dropwise process, and reacting for 6 hours after dropwise addition to obtain the core-shell structure conductive dispersion emulsion.
And 4, preparing the transparent conductive material.
And (3) coating the conductive dispersion liquid obtained in the step (3) on a transparent base polypropylene film in a blade coating mode to obtain the transparent conductive material.
Example 4
Step 1, preparing a Pickering emulsifier.
50 parts of nano copper wire and 50 parts of nano silver wire are mixed with 10 parts of modifying agent sulfhydryl polyethylene glycol carboxyl and 10 parts of modifying agent n-octadecanethiol in toluene solvent, ultrasonic treatment with the power of 80W is carried out for 1 minute, and the mixture material of the modified nano copper wire and the nano silver wire, namely the Pickering emulsifier, is obtained by freeze drying after centrifugation.
Step 2, preparing Pickering pre-emulsion.
Adding 2 parts of Pickering emulsifier obtained in the step 1 into deionized water, and adding 2 parts of cumene hydroperoxide as an initiator and 150 parts of polymer monomer butyl acrylate under the condition of stirring at 700 revolutions per minute to obtain the Pickering pre-emulsion.
And 3, preparing the core-shell structure conductive dispersion emulsion.
And (3) adding 100 parts of polymer monomer isobornyl methacrylate into the Pickering pre-emulsion in the step (2) in a dropwise adding manner, stirring in the dropwise adding process, and reacting for 6 hours to obtain the core-shell structure conductive dispersion emulsion.
And 4, preparing the transparent conductive material.
And (3) coating the conductive dispersion liquid obtained in the step (3) on the transparent base polyimide by means of slit coating to obtain the transparent conductive material.
Example 5
Step 1, preparing a Pickering emulsifier.
70 parts of nano copper wire and 30 parts of nano gold wire are mixed with 10 parts of modifying agent sulfhydryl polyethylene glycol and 20 parts of modifying agent n-hexylmercaptan in tetrahydrofuran solvent, ultrasonic treatment is carried out for 5 minutes under the power of 50W, and the modified nano copper wire and the nano gold wire material, namely the Pickering emulsifier, are obtained after centrifugation and freeze drying.
Step 2, preparing Pickering pre-emulsion.
Adding 1 part of Pickering emulsifier obtained in the step 1 into deionized water, and adding 1 part of cumene hydroperoxide as an initiator, 50 parts of polymer monomer butyl acrylate and 50 parts of methyl acrylate under the condition of stirring at 800 r/min to obtain the Pickering pre-emulsion.
And 3, preparing the core-shell structure conductive dispersion emulsion.
And (3) adding 150 parts of polymer monomer isobornyl methacrylate into the Pickering pre-emulsion in the step (2) in a dropwise adding manner, stirring in the dropwise adding process, and reacting for 6 hours to obtain the core-shell structure conductive dispersion emulsion.
And 4, preparing the transparent conductive material.
And (3) printing the conductive dispersion liquid obtained in the step (3) on inorganic glass by means of printing and coating to obtain the transparent conductive material.
Example 6
Step 1, preparing a Pickering emulsifier.
80 parts of nano silver wire and 20 parts of nano gold wire are mixed with 5 parts of modifier amino acid and 15 parts of modifier n-octadecylamine in an ethanol solvent, ultrasonic treatment is carried out for 1 minute at the power of 200W, and the mixture is centrifuged and freeze-dried to obtain modified nano copper wire and nano gold wire materials, namely a Pickering emulsifier.
Step 2, preparing Pickering pre-emulsion.
Adding 1 part of Pickering emulsifier obtained in the step 1 into deionized water, and adding 1 part of cumene hydroperoxide as an initiator and 50 parts of polymer monomer ethyl acrylate under the condition of stirring at 500 revolutions per minute to obtain the Pickering pre-emulsion.
And 3, preparing the core-shell structure conductive dispersion emulsion.
And (3) adding 100 parts of polymer monomer methyl methacrylate into the Pickering pre-emulsion in the step (2) in a dropwise manner, stirring in the dropwise process, and reacting for 6 hours after dropwise addition to obtain the core-shell structure conductive dispersion emulsion.
And 4, preparing the transparent conductive material.
And (3) coating the conductive dispersion liquid obtained in the step (3) on a transparent matrix polymethacrylic resin by means of slit coating to obtain the transparent conductive material.
The embodiments described above are intended to facilitate one of ordinary skill in the art in understanding and using the present invention. Therefore, the invention is not limited to the embodiments and other embodiments, and the technical solutions formed by equivalent replacement or equivalent transformation are all within the protection scope of the invention.
In summary, the following steps: the invention discloses a preparation method of conductive ink prepared from Pickering emulsion and a transparent conductive material thereof. The invention firstly modifies a one-dimensional nano metal material, secondly takes the modified nano metal material as a Pickering emulsion agent, polymerizes to obtain a conductive material dispersion emulsion taking polyacrylic resin and the like as a core and taking a conductive nano metal material as a shell, and finally prints on a transparent base material in a coating or printing mode and dries to obtain the transparent conductive material. The preparation method of the conductive dispersion emulsion obtained by the method is simple, and the obtained transparent conductive material has good conductivity, high transparency and good adhesive force and is easy for industrial application.
Claims (3)
1. A method for preparing a transparent conductive material by Pickering emulsion is characterized by comprising the following steps:
the method comprises the following steps: preparation of Pickering emulsifier: mixing the one-dimensional nano metal material with a modifier A and a modifier B in a solvent, performing ultrasonic treatment, centrifuging, and freeze-drying to obtain a modified nano metal material, namely a Pickering emulsifier;
step two: preparation of Pickering pre-emulsion: adding the Pickering emulsifier obtained in the step one into deionized water, and adding an initiator and a monomer A under the stirring or ultrasonic condition to obtain a Pickering pre-emulsion;
step three: preparing the core-shell structure conductive dispersion emulsion: adding the monomer B into the Pickering pre-emulsion in the second step in a dropwise manner, stirring in the dropwise process, and reacting for a period of time after dropwise addition to obtain the core-shell structure conductive dispersion emulsion;
step four: preparing a transparent conductive material: coating and printing the conductive dispersion liquid obtained in the third step on a transparent substrate to obtain a transparent conductive material;
the glass transition temperature of the monomer A in the second step is less than 60 ℃, and the monomer A is one or more of butyl acrylate, methyl acrylate and isobutyl acrylate;
in the third step, the glass transition temperature of the monomer B is more than 80 ℃, and the monomer B is one or more of isobornyl methacrylate, methyl methacrylate, styrene and acrylonitrile;
the modifier A in the first step is a water-based modifier, and is one or more of sulfhydryl polyethylene glycol carboxyl, sulfhydryl polyethylene glycol, 16-sulfhydryl hexadecyl acid and amino acid; the modifier B is an oily modifier and is one or more of n-hexanoic acid, n-hexylmercaptan, n-propylmercaptan, octadecanol and octadecylamine; the molar ratio of the modifier A to the modifier B is (1-20) to (1-20).
2. The method for preparing a transparent conductive material from Pickering emulsion as claimed in claim 1, wherein the one-dimensional nanomaterial in the first step is one or more of nano copper wire, nano silver wire, nano gold wire and nano nickel wire.
3. The method for preparing the transparent conductive material from the Pickering emulsion as claimed in claim 1 or 2, wherein the molar ratio of the monomer A to the monomer B is (1-10): (1-10).
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