WO2016171490A1 - Membrane formant barrière aux gaz utilisant de l'oxyde de graphène préparé par procédé de mélange en solution, et procédé de préparation correspondant - Google Patents

Membrane formant barrière aux gaz utilisant de l'oxyde de graphène préparé par procédé de mélange en solution, et procédé de préparation correspondant Download PDF

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WO2016171490A1
WO2016171490A1 PCT/KR2016/004159 KR2016004159W WO2016171490A1 WO 2016171490 A1 WO2016171490 A1 WO 2016171490A1 KR 2016004159 W KR2016004159 W KR 2016004159W WO 2016171490 A1 WO2016171490 A1 WO 2016171490A1
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gas barrier
graphene oxide
solution
barrier membrane
present
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PCT/KR2016/004159
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English (en)
Korean (ko)
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이중희
김남훈
라마 칸타 라익
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전북대학교산학협력단
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids

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  • the present invention relates to a gas barrier membrane prepared by a solution mixing method and a method of manufacturing the same, and more particularly, a gas barrier membrane having improved gas barrier properties by including graphene oxide having an interlocking laminated structure manufactured by a solution mixing method and its It relates to a manufacturing method.
  • graphene oxide Graphene oxide
  • reduced graphene oxide rGO, reduced graphene oxide
  • the reduced graphene oxide sheet has a property of forming agglomerates in a liquid phase and most organic solvents, it is difficult to form a reduced graphene oxide based coating.
  • the inventors of the present invention found that the formation of graphene oxide having a laminated structure interlocked with each other improves the gas barrier property, thereby completing the gas barrier layer according to the present invention.
  • the present invention has been devised to solve the above problems, and an object of the present invention is to provide a gas barrier film having improved gas barrier properties and a method of manufacturing the same by including graphene oxide having a laminated structure engaged with each other.
  • the present invention provides a gas barrier membrane comprising a graphene oxide and a polyvinyl alcohol binder resin in a weight ratio of 50 to 99: 1 to 50.
  • hydrogen gas permeability when the thickness of the gas barrier membrane is 0.5 ⁇ m ⁇ 500 ⁇ m, hydrogen gas permeability may be 0.01 ⁇ 100 cc / m 2 atm day.
  • Another aspect of the present invention is a step of preparing a graphene oxide solution by dissolving the graphene oxide in water; Step 2 to increase the concentration by vacuum filtration of the graphene oxide solution; Preparing a mixed solution by mixing the polyvinyl alcohol solution with the graphene oxide having increased concentration; And applying a mixed solution prepared in step 3 to produce a gas barrier membrane. 4.
  • the concentration of the graphene oxide solution of the first step is 0.1 to 5 mg / ml, the concentration can be increased 1.5 to 20 times by vacuum filtration of graphene oxide in the second step. .
  • the graphene oxide and the polyvinyl alcohol solution in the third step may be mixed in a weight ratio of 50 ⁇ 99: 1 ⁇ 50.
  • the mixed solution in the step 4 may be applied using one method selected from the group consisting of spin coating method, spray coating method and dip coating method.
  • the gas barrier membrane according to the present invention can improve gas barrier properties by reducing gas permeability and transmission coefficient by up to 95 times or more.
  • FIG. 1 is a schematic view showing a method of manufacturing a gas barrier film according to an embodiment of the present invention.
  • Example 2 is a spectrum showing the FTIR results of Example 1 and Comparative Examples 2 to 3 of the present invention.
  • Example 3 is a graph showing the WAXS pattern of Example 1 and Comparative Examples 1 and 2 according to the present invention.
  • Figure 4 (a) and (b) is a field scanning electron microscope image of the cross-sectional view of Example 1 and Example 2 according to the present invention, (c) and (d) is Example 1 and according to the present invention Field emission scanning electron microscope image of the surface of Example 2.
  • FIG. 5 is a field emission scanning electron microscope image of a cross section of Comparative Example 2.
  • FIG. 6 is a field emission scanning electron microscope image of a cross section of Comparative Example 3.
  • Example 7 is a graph showing the coating film thickness of Example 1 and Comparative Examples 2 to 3.
  • Graphene oxide (GO, Graphene oxide) and reduced graphene oxide (rGO, reduced graphene oxide) (rGO) can be prepared in large quantities for the production of nanocomposites with improved gas barrier properties, the reduced graphene oxide sheet is a liquid and Since there is a property of forming agglomerates in most organic solvents, there is a problem that it is difficult to form a reduced graphene oxide based coating.
  • graphene oxide has a problem of less gas barrier properties than reduced graphene oxide because of many defects, but is easy to coat on a polymer substrate.
  • the present invention provides a gas barrier membrane comprising a graphene oxide and a polyvinyl alcohol binder resin in a weight ratio of 50 to 99: 1 to 50.
  • the gas barrier membrane may block hydrogen gas and oxygen gas, and the gas barrier membrane may be improved as the thickness of the gas barrier membrane increases, and thus the gas barrier membrane may be applied to a substrate, a hydrogen storage tank, and used for various purposes and uses.
  • the present invention will be described in more detail by component.
  • the gas barrier membrane according to the present invention includes graphene oxide and polyvinyl alcohol binder resin in a weight ratio of 50 to 99: 1 to 50.
  • the graphene oxide may be formed in a layered structure interlocked with each other to improve gas barrier properties, and polyvinyl alcohol is added to serve as a binder resin.
  • the graphene oxide and the polyvinyl alcohol solution may be mixed in a weight ratio of 50 to 99: 1 to 50, and more preferably in a weight ratio of 80 to 99: 1 to 20.
  • the graphene oxide and the polyvinyl alcohol solution are mixed at a weight ratio of less than 50:50, gas barrier properties are difficult to be sufficiently improved, and when mixed at a weight ratio of 99: 1, it is difficult to form a coating layer. have.
  • hydrogen gas permeability when the thickness of the gas barrier membrane according to the present invention is 0.5 ⁇ m ⁇ 500 ⁇ m, hydrogen gas permeability may be 0.01 ⁇ 100 cc / m 2 atm day.
  • the hydrogen gas permeability when the thickness of the coating film is 0.5 ⁇ m to 3 ⁇ m, the hydrogen gas permeability may be 1 to 25 cc / m 2 atm day, and when the thickness of the gas barrier film is 0.5 ⁇ m to 2 ⁇ m, the hydrogen gas permeability is 1 to It may be 15 cc / m 2 atm day, more preferably, when the thickness of the coating film is 0.5 ⁇ m ⁇ 1 ⁇ m, hydrogen gas permeability may be 1 ⁇ 10 cc / m 2 atm day.
  • the transmission coefficient of hydrogen gas may be 0.1 ⁇ 2.5 cc mm / m 2 atm day.
  • the transmission coefficient may be 0.1 ⁇ 2 cc mm / m 2 atm day, more preferably, when the thickness of the gas barrier membrane is 0.5 ⁇ m ⁇ 1 ⁇ m,
  • the modulus may be between 0.1 and 1 cc mm / m 2 atm day.
  • the gas barrier membrane according to the present invention has an oxygen gas permeability of 0.1 to 1 cc / m 2 atm day and a transmission coefficient when the thickness of the substrate is 100 ⁇ m to 120 ⁇ m, and the thickness of the gas barrier membrane is 0.5 ⁇ m to 1 ⁇ m. May be 0.01 to 0.1 cc mm / m 2 atm day.
  • Gas barrier membrane according to the invention can be prepared by the following manufacturing method.
  • the present invention is a step of preparing a graphene oxide solution by dissolving the graphene oxide in water; Step 2 to increase the concentration by vacuum filtration of the graphene oxide solution; Preparing a mixed solution by mixing the polyvinyl alcohol solution with the graphene oxide having increased concentration; And forming a gas barrier layer by coating the mixed solution prepared in step 3 on the substrate to form a gas barrier layer, thereby forming graphene oxide having a laminated structure interlocked with each other. It provides a gas barrier membrane and a method for manufacturing the same improved gas barrier properties.
  • the present invention will be described in more detail step by step.
  • the first step is to prepare a graphene oxide solution by dissolving the graphene oxide in water, wherein the graphene oxide solution is at this time, the graphene oxide solution of The concentration may be 0.1-5 mg / ml.
  • the graphene oxide may be prepared using a Hummer's method or a modified Hummer's method as a known method, but is not particularly limited thereto.
  • a Hummer's method or a modified Hummer's method as a known method, but is not particularly limited thereto.
  • the second step is to increase the concentration by vacuum filtration of the graphene oxide solution.
  • Graphene oxide has fewer gas barrier properties than reduced graphene oxide because of many defects, but has an advantage of easy coating on a polymer substrate. Therefore, the graphene oxide with the increased concentration as described above is formed in a layered structure interlocked with each other in the solution to improve the gas barrier properties can be produced a gas barrier film excellent in gas barrier properties.
  • the concentration of 1.5 to 20 times by vacuum filtration of graphene oxide in the second step preferably 5 to 10 times, and more preferably 8 to 10 times.
  • concentration is increased to less than 1.5 times, there is a problem that it is difficult to form a layered structure, when the concentration is increased by more than 20 times, graphene oxide may aggregate to form agglomeration, and become a gel state rather than a solution. There is this.
  • the third step is to prepare a mixed solution by mixing the polyvinyl alcohol solution to the graphene oxide having increased concentration, the polyvinyl alcohol solution is a graphene oxide It can serve as a binder for fixing.
  • the graphene oxide and the polyvinyl alcohol solution in the third step may be mixed in a weight ratio of 50 to 99: 1 to 50, more preferably 80 to 99: 1 to 20 by weight ratio.
  • the graphene oxide and the polyvinyl alcohol solution are mixed at a weight ratio of less than 50:50, gas barrier properties are difficult to be sufficiently improved, and when mixed at a weight ratio of 99: 1, it is difficult to form a coating layer. have.
  • the fourth step is to prepare a gas barrier membrane by applying the mixed solution prepared in step 3, wherein the mixed solution prepared in step 3 is a substrate or a tank for storing hydrogen It is possible to improve the gas barrier properties by applying to the surface, such as to form a coating film.
  • the substrate may be any commercially available polymer substrate, and is not particularly limited.
  • the substrate is a polyethylene substrate, polypropylene, polyethylene terephthalate, polyethylene terephthalate glycol, polycarbonate, polystyrene, polyamide, poly It may include at least one substrate selected from the group consisting of butylene terephthalate, polymethyl pentene, polyvinyl chloride, nylon and copolymers thereof, more preferably polyethylene substrate, polypropylene, polyethylene terephthalate, nylon And one or more substrates selected from the group consisting of copolymers thereof.
  • the coating film may control the thickness of the coating film by adjusting the volume of the mixed solution to be applied, it is preferable to apply 0.5 ⁇ 3 ml per unit area (cm 2 ), more preferably per unit area (cm 2 ) It is recommended to apply 1.5 to 3 ml.
  • a coating film of 0.5 ⁇ m ⁇ 3 ⁇ m thick When applied as described above may be prepared a coating film of 0.5 ⁇ m ⁇ 3 ⁇ m thick.
  • the mixed solution in the step 4 may be used any method as long as it is a commercial method for applying to the substrate, preferably one method selected from the group consisting of spin coating method, spray coating method and dip coating method It can apply
  • Graphene oxide was prepared using a modified human method. 100 mL of graphene oxide at a concentration of 1 mg / mL was concentrated to 8 mg / ml using a vacuum filter. A polyvinyl alcohol (PVA, sigma aldrich) solution was mixed with the concentrated graphene oxide solution at a weight ratio of 8: 2 to prepare a GO / PVA mixed solution.
  • PVA polyvinyl alcohol
  • a gas barrier film was prepared in the same manner as in Example 1, except that 6 ml of the GO / PVA mixed solution was coated on a substrate to form a coating film having a thickness of 1.56 ⁇ m.
  • a gas barrier film was prepared in the same manner as in Example 1 except that 9 ml of the GO / PVA mixed solution was coated on a substrate to form a coating film having a thickness of 2.56 ⁇ m.
  • PET polyethylene terephthalate
  • the gas barrier membrane was manufactured by the method.
  • a gas barrier film was prepared in the same manner as in Example 1 except that the PVA was applied by a spin coating method.
  • Example 1 and Comparative Examples 2 to 3 prepared according to the present invention was measured by Fourier transform infrared spectroscopy (FTIR) to measure the interaction between the graphene side and polyvinyl alcohol, the results are shown in FIG.
  • FTIR Fourier transform infrared spectroscopy
  • the PVA has a broad peak at 3445 cm ⁇ 1 , which is manifested by the intermolecular interaction of the —OH group bound to the H-group, while the peak at 3410 cm ⁇ 1 for graphene oxide for the same bond Appears.
  • the GO / PVA nanocomposite has a peak at 3432 cm ⁇ 1 , unlike the peaks of GO and PVA, respectively, and the width of the peak is also relatively narrow.
  • PVA has a peak for unhydrated ester groups at 1730 cm -1
  • GO has a peak at 1718 cm -1 for COOH groups.
  • GO / PVA nanocomposites can be seen that has a peak at 1724 cm -1 .
  • the intermolecular H-bonds between the GO sheet or PVA chain disappears and new bonds are formed in the GO and PVA molecules.
  • GO had a peak at 1622 cm ⁇ 1 for unoxidized graphite or inserted water molecules, which shifted to 1634 cm ⁇ 1 in the GO / PVA complex.
  • GO sheets are known to exhibit a highly ordered structure with a space between two layers that are highly adjacent.
  • the GO / PVA composite can be seen that the diffraction peak shifts to a lower angle than when measured by the GO sheet alone, and it can be inferred that the space between the GO sheets is expanded by introducing PVA into the space between the GO sheets. have.
  • Comparative Examples 2 to 3 it was confirmed that the coating film is formed in a thin thickness compared to Example 1. This is because the density of the PVA is smaller than the GO, so that the PVA penetrates into the GO, and therefore, in Comparative Example 3 in which only the PVA is coated, the coating film is formed in a relatively thin thickness compared to Comparative Example 2 in which only the GO is coated.
  • Example 1 0.82 110.82 21 2.32
  • Example 2 1.56 111.56 14 1.56
  • Example 3 2.56 112.56 5 0.56 Comparative Example 1 - 110 122 13.42 Comparative Example 2 0.52 110.52 69 7.62 Comparative Example 3 0.280 110.28 110 12.40
  • Example 1 0.82 110.82 0.78 0.086 Comparative Example 1 - 110 21.2 2.23
  • the gas barrier film is 0.5 ⁇ m to 3 ⁇ m
  • the hydrogen gas permeability is 1 to 25 cc / m 2 atm day
  • the transmission coefficient is It can be seen that 0.1 ⁇ 2.5 cc mm / m 2 atm day.
  • the thickness of the gas barrier membrane may be 0.5 to 3 ⁇ m, preferably 1 to 3 ⁇ m, more preferably 2 to 3 ⁇ m. It can be seen that the hydrogen permeability and the coefficient of permeability decrease according to the thickness of the coating film. When the thickness of the coating film is 2.56 ⁇ m, it was confirmed that the hydrogen transmittance is reduced by 96% compared to Comparative Example 1 without the coating film, it was confirmed that the transmission coefficient is also reduced to 95%.
  • the thickness of the substrate is 100 ⁇ m ⁇ 120 ⁇ m
  • the thickness of the coating film is 0.5 ⁇ m ⁇ 1 ⁇ m
  • the oxygen gas permeability is 0.1 ⁇ 1 cc / m 2 atm day
  • the transmission coefficient is 0.01 ⁇ 0.1 cc mm / m 2 atm day
  • the gas barrier membrane according to the present invention was confirmed that the hydrogen gas and oxygen gas blocking ability is remarkably excellent.

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Abstract

La présente invention concerne une membrane formant barrière aux gaz préparée par un procédé de mélange en solution, et un procédé pour la produire et, plus particulièrement, une membrane formant barrière aux gaz présentant une propriété améliorée de barrière aux gaz en ce qu'elle comprend un oxyde de graphène qui est préparé par un procédé de mélange en solution et qui présente une structure stratifiée interdigitée ; et un procédé pour la préparer. Plus spécifiquement, la présente invention concerne un procédé de préparation d'une membrane formant barrière aux gaz comprenant : une première étape de préparation d'oxyde de graphène selon un procédé en solution ; une deuxième étape de filtration sous vide de l'oxyde de graphène préparé selon le procédé en solution pour accroître de là sa concentration ; une troisième étape de mélange d'une solution de poly(alcool de vinyle) avec l'oxyde de graphène à une concentration accrue pour ainsi préparer une solution mixte ; et une quatrième étape d'application de la solution mixte préparée dans la troisième étape sur un substrat pour ainsi préparer une membrane formant barrière aux gaz.
PCT/KR2016/004159 2015-04-23 2016-04-21 Membrane formant barrière aux gaz utilisant de l'oxyde de graphène préparé par procédé de mélange en solution, et procédé de préparation correspondant WO2016171490A1 (fr)

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CN114455576B (zh) * 2022-01-24 2023-11-10 南方电网科学研究院有限责任公司 一种高灵敏检测压力变化的石墨烯复合材料的制备方法

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