KR20170019721A - Graphene oxide-polyimide composite material and method for manufacturing the same - Google Patents
Graphene oxide-polyimide composite material and method for manufacturing the same Download PDFInfo
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Abstract
A graphene oxide-polyimide composite material and its manufacturing method are disclosed. One embodiment of the present invention is a method for preparing a graphene oxide dispersion, comprising the steps of: preparing a graphene oxide dispersion; Preparing a polyamic acid mixed solution containing the graphene oxide dispersion; And a step of obtaining a graphene oxide-polyimide composite material by using the mixed solution. The present invention also provides a method for producing a graphene oxide-polyimide composite material.
Description
The present invention relates to a graphene oxide-polyimide composite material and a method of manufacturing the same.
Graphene is a semimetallic nanomaterial with a thickness of one atom, which is a honeycomb arrangement of carbon atoms on a two-dimensional sp 2 bond. It is very stable both structurally and chemically, has excellent electrical and thermal conductivity, Are known as materials that can be applied to transparent conductive coatings, electronic devices, sensors, supercapacitors, batteries, solar cells, heat dissipation materials, smart window materials and transistors as well as carbon nanotubes. For this application, it is necessary to mass-produce graphene.
Generally, graphene is produced by a method in which graphene is directly grown from a copper plate or a catalyst substrate by a chemical vapor deposition method, a graphene oxide is separated by oxidizing the graphite, and the graphene is reduced by a reducing agent or heat treatment, There is a method of manufacturing graphene.
The chemical vapor deposition method is difficult to apply to a large area, and in particular, it is difficult to transfer to a large area on a glass surface. Therefore, a reduction graphene method for producing and reducing oxidized graphite from graphite is being actively studied.
According to the present redox process, various processes such as oxidation and reduction steps are required, and thus it takes much time to manufacture graphene.
On the other hand, when a composite film of graphene and polymer is produced, graphene is mainly dispersed in a polymer solution. Since it does not have excellent dispersibility, a more efficient method of forming a graphene-polymer composite film is required.
An embodiment of the present invention is to provide a graphene oxide-polyimide composite material which is simple, quick, and has excellent dispersion properties and a method for producing the same.
One embodiment of the present invention is a method for preparing a graphene oxide dispersion, comprising the steps of: preparing a graphene oxide dispersion; Preparing a polyamic acid mixed solution containing the graphene oxide dispersion; And a step of obtaining a graphene oxide-polyimide composite material by using the mixed solution. The present invention also provides a method for producing a graphene oxide-polyimide composite material.
Preparing the graphene oxide dispersion; Preparing graphite; And acid treating the graphite with super acid, followed by washing to obtain an aqueous solution of graphene oxide.
The graphite may be nano-sized graphite having a particle diameter of 50 to 1,000 nm.
The super acid may include sulfuric acid, methanesulfonic acid, or a combination thereof.
Acid treating the graphite with super acid and washing to obtain an aqueous graphene oxide solution; Thereafter, the graphene oxide aqueous solution is dried to obtain a graphene oxide powder; And dispersing the graphene oxide powder in a solvent to prepare a graphene oxide dispersion.
Acid treating the graphite with super acid and washing to obtain an aqueous graphene oxide solution; And then replacing the solvent of the graphene oxide aqueous solution to prepare a graphene oxide dispersion.
Acid treating the graphite with super acid and washing to obtain an aqueous graphene oxide solution; Thereafter, the method may further include reducing the graphene oxide aqueous solution to an aqueous graphene solution, and then replacing the solvent to prepare a graphene dispersion.
The reduction is sodium hydroxide (NaOH), potassium hydroxide (KOH), ammonium hydroxide (NH 4 OH), sodium borohydride (NaBH 4), hydrazine (N 2 H 4), Hi give iodine (HI), or a combination thereof Can be used as a reducing agent.
The solvent is selected from the group consisting of N-methyl-2-pyrrolidone, distilled water, acetone, methyl ethyl ketone, methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, ethylene glycol, polyethylene glycol, tetrahydrofuran, And examples of the organic solvent include amides, dimethylacetamide, hexane, cyclohexanone, toluene, chloroform, dichlorobenzene, dimethylbenzene, trimethylbenzene, pyridine, methylnaphthalene, nitromethane, acrylonitrile, octadecylamine, aniline, Lt; / RTI >
The graphene oxide dispersion and the graphene dispersion may be formed using a homogenizer, an ultrasonic machine, a high pressure homogenizer, or a combination thereof.
The step of preparing a polyamic acid mixture solution containing the graphene oxide dispersion comprises: dispersing the graphene oxide dispersion in an organic solvent for polyamic acid polymerization; And dissolving a dianhydride compound and a diamine compound in an organic solvent for polyamic acid polymerization in which the graphene oxide dispersion is dispersed, followed by condensation polymerization in situ .
The dianhydride compound may be selected from the group consisting of benzophenonetetracarboxylic dianhydride (BTDA), pyromellitic dianhydride (PMDA), biphenyltetracarboxylic dianhydride (4,4 ' -Biphenyltetracarboxylic Dianhydride (BPDA), 4,4-Hexafluoroisopylidene Diphthalic Anhydride (FDPA), or a combination thereof.
The diamine compound may be oxydianiline (ODA), 4,4'-Diaminodiphenyl Methane (MDA), 4,4'-Biphenyltetracarboxylic Dianhydride (BPDA) ), Or a combination thereof.
The step of obtaining a graphene oxide-polyimide composite material using the mixed solution may include heating the mixture to remove the solvent in the mixture.
The step of obtaining a graphene oxide-polyimide composite material using the mixed solution may be performed by solvent casting, spray coating, bar coating, spin coating, or a combination thereof.
In the step of obtaining a graphene oxide-polyimide composite material by using the mixed solution, the graphene content of the polyimide in the composite material may be more than 0 and 3 wt% or less.
Another embodiment of the present invention provides a graphene oxide-polyimide composite material produced by the above-described method for producing a graphene oxide-polyimide composite material.
The graphene oxide-polyimide composite material may be in the form of a film or a fiber.
The graphene content of the polyimide may be greater than 0 and less than or equal to 3 wt%.
According to one embodiment of the present invention, there can be provided a graphene oxide-polyimide composite material which is simple, quick, and has good dispersion characteristics and a method for producing the same.
FIG. 1 is an optical microscope photograph showing dispersion characteristics of a film prepared using nano graphite according to the weight of graphene oxide in Experimental Example 3. FIG.
FIG. 2 is an optical microscope photograph showing dispersion characteristics of graphene oxide in a film produced using micron-graphite in Experimental Example 3 according to the weight of graphene oxide.
Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.
Throughout the specification, when an element is referred to as " comprising ", it means that it can include other elements as well, without excluding other elements unless specifically stated otherwise.
One embodiment of the present invention is directed to a method for preparing a graphene oxide dispersion, comprising: (S1) preparing a graphene oxide dispersion; (S2) a polyamic acid mixture solution containing the graphene oxide dispersion; And a step (S3) of obtaining a graphene oxide-polyimide composite material by using the mixed solution. The present invention also provides a method for producing a graphene oxide-polyimide composite material.
First, in one embodiment of the present invention, step (S1) of preparing a graphene oxide dispersion comprises: preparing graphite (S11); And acid treating the graphite with super acid, followed by washing to obtain an aqueous graphene oxide solution (S12).
Here, the graphite may be flake graphite, expanded graphite, nano graphite, or a combination thereof, but is preferably nano graphite. More specifically, it is preferable that the particle size of the nano graphite is 50 to 1,000 nm. When the particle diameter of the nano-graphite is within the above range, the oxidizing action between the graphite layers during the oxidation process is easy, and more functional groups are attached to the nano-graphite particles, which results in an increase in the yield of graphene oxide.
The particle size in this specification means the average diameter of the spherical material present in the unit of measurement. If the material is an acetal, it means the diameter of the sphere calculated by approximating the spherical material to the spherical shape.
In this case, the step (S12) of obtaining an aqueous solution of graphene oxide by acid-treating the graphite with super acid and then washing the graphite oxide may be carried out by using super acid After the acid treatment, the purified graphite oxide may be stripped to form graphene oxide. Here, the superacid can include, for example, sulfuric acid, methanesulfonic acid, or a combination thereof.
The acid treatment may be carried out in a suitable solvent such as a stoichiometric method (L. Staudenmaier, Ber. Dtsch. Chem. Ges., 31, 1481-1499, 1898), Hummus method (W. Hummers et al., J. Am. Chem. Modified methods for more effective oxidation and exfoliation of graphite are known, and the present invention also relates to a method for the production of graphite, .
For example, in one embodiment of the present invention, step (S1) of preparing a graphene oxide dispersion comprises: acid-treating the graphite with super acid and washing to obtain an aqueous solution of graphene oxide; (S12); Thereafter, the step (S13a) of drying the graphene oxide aqueous solution to obtain a graphene oxide powder; And dispersing the graphene oxide powder in a solvent to prepare a graphene oxide dispersion (S14a).
As another example, in one embodiment of the present invention, the step (S1) of preparing a graphene oxide dispersion comprises: acid-treating the graphite with super acid, washing and washing the graphene oxide aqueous solution Obtaining (S12); Subsequently, a step (S13b) of preparing a graphene oxide dispersion by replacing the solvent of the graphene oxide aqueous solution may be further included.
More specifically, this is accomplished by replacing water as a solvent of the graphene oxide aqueous solution with an organic solvent which is a polyamic acid polymerization solvent without converting the graphene oxide aqueous solution into a dried graphene oxide as described above, Centrifugal separation is repeated several times to prepare a graphene oxide dispersion in which the organic solvent is dispersed.
When the graphene oxide aqueous solution is dried, the graphene oxide layers having strong pi-pi (π-π) bond attraction are again multilayer-bonded in the step of drying the graphene oxide, It is difficult to disperse the graphene oxide in an exfoliated graphene oxide even if it is dispersed by a method such as dispersion. On the other hand, when water serving as a solvent of the graphene oxide aqueous solution is replaced with an organic solvent which is a polyamic acid polymerization solvent, There is an advantage that a graphene oxide dispersion which is well dispersed in a final polyamic acid polymerization solvent can be obtained by performing solvent substitution without a state in which graphene oxide dispersed in an exfoliated state is dried in the presence of a solvent, The solvent may be N-methyl-2-pyrrolidone, distilled water, acetone, methyl ethyl ketone, methyl alcohol, ethyl But are not limited to, alcohols such as methanol, ethanol, isopropyl alcohol, butyl alcohol, ethylene glycol, polyethylene glycol, tetrahydrofuran, dimethylformamide, dimethylacetamide, hexane, cyclohexanone, toluene, chloroform, dichlorobenzene, Pyridine, methylnaphthalene, nitromethane, acrylonitrile, octadecylamine, aniline, dimethylsulfoxide, or combinations thereof.
In addition, the graphene oxide dispersion may be formed using a homogenizer, an ultrasonic machine, a high-pressure homogenizer, or a combination thereof.
As another example, in one embodiment of the present invention, the step (S2) of preparing a graphene dispersion comprises: acid-treating the graphite with super acid, washing, and washing the graphene oxide aqueous solution Obtaining (S12); Thereafter, the method may further include a step (S13c) of reducing the graphene oxide aqueous solution to a graphene aqueous solution and then replacing the solvent to prepare a graphene oxide dispersion.
Here, the reduction is sodium hydroxide (NaOH), potassium hydroxide (KOH), ammonium hydroxide (NH 4 OH), sodium borohydride (NaBH 4), hydrazine (N 2 H 4), Hi give iodine (HI), or And a combination thereof may be used as a reducing agent.
The solvent is selected from the group consisting of N-methyl-2-pyrrolidone, distilled water, acetone, methyl ethyl ketone, methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, ethylene glycol, polyethylene glycol, tetrahydrofuran, And examples of the organic solvent include amides, dimethylacetamide, hexane, cyclohexanone, toluene, chloroform, dichlorobenzene, dimethylbenzene, trimethylbenzene, pyridine, methylnaphthalene, nitromethane, acrylonitrile, octadecylamine, aniline, Lt; / RTI >
In addition, the graphene dispersion may be formed using a homogenizer, an ultrasonic machine, a high-pressure homogenizer, or a combination thereof.
In one embodiment of the present invention, the step (S2) of preparing a polyamic acid mixture solution containing the graphene oxide dispersion comprises: (S21) dispersing the graphene oxide dispersion in an organic solvent for polyamic acid polymerization; And a step (S22) of dissolving a dianhydride compound and a diamine compound in an organic solvent for polyamic acid polymerization in which the graphene oxide dispersion is dispersed, followed by condensation polymerization in situ Lt; / RTI >
In one embodiment of the present invention, the step (S3) of obtaining a graphene oxide-polyimide composite material using the mixed solution comprises: (S31) heating the mixture to remove the solvent in the mixture; .
Here, the step of obtaining a graphene oxide-polyimide composite material using the mixed solution may be performed by solvent casting, spray coating, bar coating, spin coating, or a combination thereof.
At this time, in the step of obtaining the graphene oxide-polyimide composite material using the mixed solution, the content of the graphene to the polyimide in the mixed solution may be more than 0 and 3 wt% or less, more specifically, 0.1 to 0.7 wt%. When the content of the graphene to the polyimide is in the above range, not only the mechanical and optical properties of the film and the fibrous composite material in the resulting graphene oxide-polyimide composite material are excellent, There is one advantage.
Another embodiment of the present invention provides a graphene oxide-polyimide composite material produced by the above-described method for producing a graphene oxide-polyimide composite material.
At this time, the graphene oxide-polyimide composite material may be in the form of a film or a fiber, but is not limited thereto.
In the graphene oxide-polyimide composite material, the content of the graphene to the polyimide may be more than 0 and 3 wt% or less, more preferably 0.1 to 0.7 wt%. When the content of the graphene relative to the polyimide is in the above range, not only the mechanical and optical properties of the film, ribbon, and fiber-shaped composite material are excellent, but their physical properties are stable and uniform. This is because it is important that the thickness of the thin film or the composite material in the form of fibers increases the probability of graphene oxide and / or grafting reinforcing filler particles protruding to the surface, so that the content thereof is minimized and uniformly dispersed Because.
Hereinafter, preferred embodiments and comparative examples of the present invention will be described. However, the following examples are only a preferred embodiment of the present invention, and the present invention is not limited to the following examples.
Manufacturing example
Manufacturing example One: Grapina Oxide ( graphene oxide, GO) dispersion
1 g of various kinds of graphite described in the following [Table 1] was put into a 250 ml beaker together with 0.5 g of sodium nitrate and 23 ml of sulfuric acid, and the mixture was stirred at 0 ° C for 15 minutes on a mechanical stirrer stirrer.
After that, 3 g of potassium permanganate was added and the mixture was cooled for 15 minutes and then stirred for another 1 hour.
Thereafter, the temperature is maintained at 35 DEG C for 30 minutes, then 46 mL of water is added for 10 minutes, and the mixture is diluted with 140 mL of warm water.
Then, add 5 ml of H 2 O 2 (30 wt%) to remove remaining manganese ions, and slowly add 7.5 ml of hydrochloric acid for 3 minutes for washing.
Then, the solution was filtered and washed several times with deionized water until the pH reached 7, thereby producing a graphene oxide dispersion.
At this time, the graphene oxide dispersion was dried in a vacuum oven at 60 DEG C for 24 hours to obtain graphene oxide powder, and the yield of graphene oxide produced by each graphite was compared.
(g)
(g)
(ml)
(g)
(ml)
(ml)
(ml)
(ml)
Referring to Table 1, when graphene oxide was prepared by the method of W. Hummers, the weight (yield) of graphite oxide relative to the initial graphite raw material was increased, because oxidizing functional groups such as OH and COOH were added to graphite This is accompanied by an increase in weight.
Further, the yield of graphene oxide using nano graphite of 1 to 1,000 nm was higher than that of the case of using micron graphite (manufactured by Samjung C & G) in the range of 1 to 1,000 μm size. This is because the size of the nano-graphite is small, and the oxidizing action between the graphite layers and the edges is easy during the oxidation process, and more functional groups are attached to the nano-graphite particles, resulting in a high yield. Therefore, it can be deduced that the dispersibility is high when the graphene oxide dispersion is prepared.
The prepared graphene oxide aqueous solution was centrifuged to recover graphene oxide, which was then dried to form a powder, which was put into a solvent of N-methyl-2-pyrrolidone (NMP) And subjected to ultrasonic treatment to prepare a graphene oxide / NMP dispersion.
Manufacturing example 2: Continuous method Grapina Oxide ( graphene oxide, GO) dispersion
Two types of graphite shown in Table 2 below were filtered and washed with deionized water several times until the pH reached 7 by the same method as in Production Example 1. [ Thereafter, unlike Production Example 1, a graphene oxide dispersion in which water was used as a solvent was prepared, and then the dispersion was centrifuged continuously without drying to partially remove water in the supernatant. Then, NMP (N-methyl-2-pyrrolidone) solvent was added to the amount of the removed water, and the same was repeated to prepare a graphene oxide / NMP dispersion in which the solvent was substituted with 99.9% or more NMP. The concentration of graphene oxide was determined by taking a portion of the dispersion, drying it, and weighing it.
Oxide
Agriculture
(mg / ml)
(g)
(g)
(ml)
(g)
(ml)
(ml)
(ml)
(ml)
Referring to Table 2, the graphite oxide concentration (yield) of the graphite oxide was higher than that of Table 1 in the case of Production Example 1, in which the graphite suspension with water as a solvent was dried, It was deduced that the oxidative functional groups were decomposed in the part.
In addition, in the case of graphene oxide obtained by using a nano graphite raw material ranging from 1 to 1,000 nm in size, the yield was higher than that in the case of using a micron graphite raw material ranging from 1 to 1,000 μm in size. It can be inferred together.
Therefore, when a polyamic acid / NMP mixture is prepared by using the graphene oxide / NMP dispersion obtained through the continuous process of preparing a graphene oxide dispersion and a graphene oxide-polyimide composite material is produced from the mixture, It is possible to predict improvement of mechanical and optical properties through improvement of acidity.
Manufacturing example 3: Supercharging method Grapina Oxide ( graphene oxide, GO) dispersion
1.0 g of nano-graphite was added to 60 ml of methanesulfonic acid, which was a strong acid, and then subjected to a reaction for exfoliation for 2 hours using a low-power-bath type ultrasonic wave.
The reaction was centrifuged at 3,000 rpm to remove the supernatant. After the supernatant was removed from the reaction mixture, the remaining precipitate was washed several times with deionized water to a pH of 7 by the same method as in Preparation Example 2.
Thereafter, water was replaced with NMP solvent using a centrifugal separation process, and a graft oxide / NMP dispersion in which the solvent was substituted with NMP was prepared. Also, the concentration of nano-graphene oxide was measured by taking a part of the above dispersion and drying it, and it was found to be 2.05 mg / ml.
Manufacturing example 4: Grapina Oxide - Polyamic acid Preparation of mixed liquid
38 ml of the nano-graphene oxide / NMP dispersion obtained by the methods of Production Examples 1 to 3 were added to a 300-ml resin kettle, and an anhydrous benzophenone tetracarboxylic dianhydride ( 9.67 g (30 mmol) of benzophenonetetracarboxylic dianhydride (BTDA) and 88.82 g of NMP (N-methyl-2-pyrrolidone) solvent were stirred for 1 hour in a stream of nitrogen.
When BTDA was dissolved, 6.01 g (30 mmol) of a second monomer, oxydianiline (ODA), was added to the resin cake and in-situ polycondensation was performed at room temperature for 24 hours.
As a result, a viscous graphene oxide-polyamic acid mixture was prepared, and the concentration of the polyamic acid polymer was about 11 wt%.
Manufacturing example 5: Grapina Oxide - Preparation of polyimide composite material
The graphene oxide-polyimide composite material can be prepared by using the nano-graphene oxide-polyamic acid mixture solution obtained through Production Example 4. Thus, a method for producing a graphene oxide-polyimide composite material film is as follows.
First, the glass substrate for film casting and the graphene oxide-polyamic acid mixture were preheated in an oven at 60 ° C for 20 minutes, and then a graphene oxide-polyamic acid mixture was poured onto a glass substrate and coated with a bar.
Thereafter, the coated glass substrate was placed in an electric furnace and then heat-treated in accordance with the temperature rising profile shown in Table 3 below.
As a result, the graphene oxide-polyimide composite film was produced by removing the NMP solvent and imidizing the polyamic acid with polyimide.
Example And Comparative Example
Example One
In Example 1, a graphene oxide-polyamic acid mixture solution was prepared by using the graphene oxide / NMP dispersion obtained in Production Example 1, using the in-situ condensation polymerization method according to Production Example 4. [
The prepared graphene oxide-polyamic acid mixture was bar-coated on a glass substrate through the method described in Production Example 5 and then heat-treated in an oven to obtain a graphene oxide-polyimide composite film.
Example 2
In Example 2, a graphene oxide-polyamic acid mixture was prepared by using the graphene oxide / NMP dispersion obtained in Production Example 2, using the in-situ condensation polymerization method according to Production Example 4. [
The prepared graphene oxide-polyamic acid mixture was bar-coated on a glass substrate through the method described in Production Example 5 and then heat-treated in an oven to obtain a graphene oxide-polyimide composite film.
Example 3
In Example 3, a graphene oxide-polyamic acid mixture was prepared by using the graphene oxide / NMP dispersion obtained in Production Example 3, using the in-situ condensation polymerization method according to Production Example 4. [
The prepared graphene oxide-polyamic acid mixture was bar-coated on a glass substrate through the method described in Production Example 5 and then heat-treated in an oven to obtain a graphene oxide-polyimide composite film.
Comparative Example One
Comparative Example 1 produced a polyimide film containing no graphene oxide.
Comparative Example 2
In Comparative Example 2, the graphene oxide / NMP dispersion obtained in Preparation Example 1, which was prepared by preparing an aqueous solution of graphene oxide by the Hummus method and then redispersing the aqueous solution of graphene oxide in an NMP solvent after centrifugation, Was used.
The graphene oxide / polyamic acid dispersion obtained in Preparation Example 1 was mechanically stirred in a polyamic acid containing no graphene to prepare a graphene oxide-polyamic acid mixture.
In addition, although the graphene oxide-polyimide composite material film was produced through the film casting method, the composite material film exhibits properties similar to those of the polyimide self-film without graphene.
Experimental Example
Experimental Example One: Example And Comparative example Mechanical properties evaluation
Using the thus obtained examples and comparative examples, the mechanical properties of the film were evaluated. The mechanical properties of the film were evaluated using an UTM instrument of Instron (USA). The results are shown in Table 4 below.
[Mu m]
[
Mpa
]
[
Mpa
]
[%]
As shown in Table 4, the films of Examples 1 to 3 are superior to the films of Comparative Examples 1 and 2 in mechanical properties such as tensile strength and elongation.
More specifically, it can be seen that the mechanical properties are better in the second embodiment than in the first embodiment. More specifically, it can be seen that the mechanical properties of Example 3 are better than those of Example 2.
This is the same as Example 3 in which a film was prepared using the graphene oxide / NMP dispersion obtained by the superacoustic method of Production Example 3, compared with Examples 1 and 2, in which the film was produced using the graphene oxide / NMP dispersion obtained by the Hummus method The mechanical properties of the resin are better.
Experimental Example 2: Evaluation of mechanical properties according to the average particle size of graphite raw material
Experimental Example 2 evaluates the mechanical properties of the film according to the grain size of graphite, which is a raw material for obtaining graphene oxide.
More specifically, the graphene oxide / NMP dispersion obtained by the method of Production Example 3 is used. In the preparation of the dispersion, nanocrystals of 1 to 1,000 nm in size or micron graphite of 1 to 1,000 μm in size are used to prepare a dispersion .
Thereafter, a graphene oxide-polyamic acid mixture solution was prepared by the in-situ condensation polymerization method of Production Example 4, and then a graphene oxide-polyimide composite material film was obtained by the method of Production Example 5. [
The mechanical properties of the films prepared using dispersions having different sizes of graphite were evaluated using UTM equipment of Instron (USA), and the results are shown in Table 5 below.
Composite film
[
wt%
]
[Mu m]
[
Mpa
]
[
Mpa
]
[%]
0.1
0.3
0.5
0.7
0.1
0.3
0.5
0.7
As shown in Table 5, it can be seen that the nano-graphene oxide-polyimide composite material film obtained using nano-sized graphite as a raw material has better physical properties than the micron graphene oxide-polyimide composite material film.
More specifically, when the average particle diameter of the nano-graphite was 50 to 1,000 nm, it was confirmed that the physical properties were better. This is because the oxidizing action between the graphite layers during the oxidation process is easy and the yield is high.
Experimental Example 3: Grapina Oxide Evaluation of dispersion characteristics
Experimental Example 3 evaluates the dispersion characteristics of graphene oxide.
More specifically, using the film described in Experimental Example 2, the dispersion characteristics were evaluated according to the weight of graphene oxide in the nano unit or the weight of graphene oxide in the micron unit.
The dispersion characteristics of the films prepared using dispersions having different sizes and weights were evaluated using an STM6-F10-2 optical microscope from Olympus (Japan), and the results are as shown in Fig.
FIG. 1 is an optical microscope photograph showing the dispersion characteristics of graphene oxide in a film produced using nano graphite in Experimental Example 3. FIG.
FIG. 2 is an optical microscope photograph showing dispersion characteristics of graphene oxide in a film produced using micron-graphite in Experimental Example 3. FIG.
Referring to FIG. 1, in the case of the graphene oxide-polyimide composite film produced using nano-graphite, the graphene oxide portion on the polyimide matrix increases as the fraction of graphene oxide in the film increases have. Further, it can be seen that the graphene oxide is uniformly dispersed.
On the other hand, in the case of the graphene oxide-polyimide composite film produced using the micron graphite of FIG. 2, it can be seen that the graphene oxide aggregated portion increases. In addition, it can be seen that the size of the agglomerated graphene oxide increases. Since the agglomerated graphene oxide acts as a weak point in the measurement of mechanical properties, the mechanical properties may be lower than that in the case of producing a film using nano-sized graphite.
It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.
Claims (15)
Preparing a polyamic acid mixed solution containing the graphene oxide dispersion; And
Obtaining a graphene oxide-polyimide composite material using the mixed solution;
Wherein the graphene oxide-polyimide composite material is a graphene oxide-polyimide composite material.
Preparing the graphene oxide dispersion,
Preparing graphite; And
Acid treating the graphite with super acid and washing to obtain an aqueous graphene oxide solution;
Wherein the graphene oxide-polyimide composite material is a graphene oxide-polyimide composite material.
Wherein the graphite is a nano-sized graphite having a particle size of 50 to 1,000 nm.
Wherein the graphene oxide is contained in an amount of 0.1 to 3% by weight based on 100% by weight of the total aqueous solution.
Wherein the super acid comprises sulfuric acid, methanesulfonic acid, or a combination thereof. ≪ RTI ID = 0.0 > 11. < / RTI >
Acid treating the graphite with super acid and washing to obtain an aqueous graphene oxide solution; Since the,
Drying the graphene oxide aqueous solution to obtain graphene oxide powder; And
Dispersing the graphene oxide powder in a solvent to prepare a graphene oxide dispersion;
Wherein the graphene oxide-polyimide composite material further comprises a polyimide precursor.
Acid treating the graphite with super acid and washing to obtain an aqueous graphene oxide solution; Since the,
Replacing the solvent of the graphene oxide aqueous solution to prepare a graphene oxide dispersion;
Wherein the graphene oxide-polyimide composite material further comprises a polyimide precursor.
Acid treating the graphite with super acid and washing to obtain an aqueous graphene oxide solution; Since the,
Reducing the graphene oxide aqueous solution to a graphene aqueous solution and replacing the solvent to prepare a graphene dispersion;
Wherein the graphene oxide-polyimide composite material further comprises a polyimide precursor.
The reduction is sodium hydroxide (NaOH), potassium hydroxide (KOH), ammonium hydroxide (NH 4 OH), sodium borohydride (NaBH 4), hydrazine (N 2 H 4), Hi give iodine (HI), or a combination thereof Wherein the graphene oxide-polyimide composite material is used as a reducing agent.
The solvent is selected from the group consisting of N-methyl-2-pyrrolidone, distilled water, acetone, methyl ethyl ketone, methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, ethylene glycol, polyethylene glycol, tetrahydrofuran, And examples of the organic solvent include amides, dimethylacetamide, hexane, cyclohexanone, toluene, chloroform, dichlorobenzene, dimethylbenzene, trimethylbenzene, pyridine, methylnaphthalene, nitromethane, acrylonitrile, octadecylamine, aniline, Wherein the graphene oxide-polyimide composite material is a composite.
Preparing a polyamic acid mixture solution containing the graphene oxide dispersion,
Dispersing the graphene oxide dispersion in an organic solvent for polyamic acid polymerization; And
Dissolving a dianhydride compound and a diamine compound in an organic solvent for polyamic acid polymerization in which the graphene oxide dispersion is dispersed, followed by condensation polymerization in situ;
Wherein the graphene oxide-polyimide composite material is a polyimide composite material.
The step of obtaining a graphene oxide-polyimide composite material using the mixed solution may include heating the mixed solution to remove the solvent in the mixed solution; / RTI >
Wherein the content of said graphene to said polyimide in said composite material is greater than 0 and 3 wt% or less.
In the step of obtaining a graphene oxide-polyimide composite material using the mixed solution,
Wherein the graphene content of the polyimide in the composite material is greater than 0 and less than or equal to 3 wt%.
Wherein the graphene content with respect to the polyimide is greater than 0 and less than or equal to 3 wt%.
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| KR20200126287A (en) * | 2019-04-29 | 2020-11-06 | 한국전기연구원 | Carbon nanotube oxide composites for stretchable energy storage element, and method for producing carbon nanotube oxide composites, and stretchable energy storage element including the same |
| KR102203211B1 (en) * | 2019-09-17 | 2021-01-14 | 피아이첨단소재 주식회사 | Manufacturing method of polyimide powder and polyimide powder manufactured by the same |
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| KR20200126287A (en) * | 2019-04-29 | 2020-11-06 | 한국전기연구원 | Carbon nanotube oxide composites for stretchable energy storage element, and method for producing carbon nanotube oxide composites, and stretchable energy storage element including the same |
| KR102203211B1 (en) * | 2019-09-17 | 2021-01-14 | 피아이첨단소재 주식회사 | Manufacturing method of polyimide powder and polyimide powder manufactured by the same |
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| CN113185906A (en) * | 2021-05-18 | 2021-07-30 | 扬州工业职业技术学院 | Water-based anticorrosive paint |
| CN113277504A (en) * | 2021-05-18 | 2021-08-20 | 扬州工业职业技术学院 | Multifunctional auxiliary agent containing graphene nano material and preparation method thereof |
| CN113185906B (en) * | 2021-05-18 | 2021-11-30 | 扬州工业职业技术学院 | Water-based anticorrosive paint |
| CN113277504B (en) * | 2021-05-18 | 2022-03-04 | 扬州工业职业技术学院 | Multifunctional auxiliary agent containing graphene nano material and preparation method thereof |
| KR102375039B1 (en) * | 2021-06-18 | 2022-03-17 | 한국화학연구원 | Method for Preparing Dispersion of Carbon Material and Dispersion of Carbon Material |
| WO2023101433A1 (en) * | 2021-11-30 | 2023-06-08 | 피아이첨단소재 주식회사 | Polyimide powder with improved conductivity using graphene and manufacturing method therefor |
| CN116375472A (en) * | 2023-02-28 | 2023-07-04 | 安徽国风新材料股份有限公司 | Super-thick polyimide-based graphite film and preparation method thereof |
| CN117185826A (en) * | 2023-09-19 | 2023-12-08 | 佛山市陶莹新型材料有限公司 | High-temperature-resistant ceramic material and preparation method and application thereof |
| CN117924701A (en) * | 2024-01-30 | 2024-04-26 | 延边大学 | Superhard composite material containing diamond and graphene and preparation method |
| CN117924701B (en) * | 2024-01-30 | 2024-06-11 | 延边大学 | Superhard composite material containing diamond and graphene and preparation method |
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