WO2014200232A1 - Dispersion stabilizer for graphene exfoliation, graphene-alkali metal salt composite comprising same, and method for preparing graphene using same - Google Patents

Dispersion stabilizer for graphene exfoliation, graphene-alkali metal salt composite comprising same, and method for preparing graphene using same Download PDF

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WO2014200232A1
WO2014200232A1 PCT/KR2014/005057 KR2014005057W WO2014200232A1 WO 2014200232 A1 WO2014200232 A1 WO 2014200232A1 KR 2014005057 W KR2014005057 W KR 2014005057W WO 2014200232 A1 WO2014200232 A1 WO 2014200232A1
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graphene
compound
group
dispersion stabilizer
alkali metal
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Korean (ko)
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강병남
이동현
이종찬
안자은
최지은
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주식회사 동진쎄미켐
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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
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/19—Preparation by exfoliation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/16—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C317/22—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/205—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring the aromatic ring being a non-condensed ring
    • C07C43/2055—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring the aromatic ring being a non-condensed ring containing more than one ether bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
    • C07F9/3804—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se) not used, see subgroups
    • C07F9/3834—Aromatic acids (P-C aromatic linkage)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6558—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system
    • C07F9/65586—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system at least one of the hetero rings does not contain nitrogen as ring hetero atom

Definitions

  • the present invention relates to a dispersion stabilizer for graphene peeling, a graphene-alkali metal salt composite including the same, and a method for preparing graphene using the same, and more particularly, graphene capable of efficiently peeling graphene from graphite.
  • the present invention relates to a dispersion stabilizer for peeling, a graphene-alkali metal salt composite including the same, and a method of preparing graphene using the same.
  • Graphene is a carbon crystal in which carbon atoms are connected in a hexagonal honeycomb shape to have a two-dimensional sheet shape, and a plurality of graphene sheets are stacked to form graphite. Therefore, when the graphite is exfoliated, a sheet-like graphene composed of one or more layers can be obtained.
  • Graphene is a material having both metal and nonmetal properties, and has good electrical and thermal conductivity as metals, and has high thermal stability and chemical inertness as nonmetals. Graphene can be applied to various applications such as electric devices, batteries, fuel cells, refractory materials, and the like.
  • the mechanical peeling method is a method of mechanically grinding or using an adhesive tape, in which graphite is simply mechanically crushed, or an adhesive tape is attached to the graphite and then peeled off to obtain graphene that is attached to the adhesive tape and peeled off.
  • graphite is prepared by oxidizing graphite with an oxidizing agent, and then a solvent such as water is inserted between the surfaces of the graphite oxide to increase the spacing between the layers, stirring or ultrasonic grinding, After peeling off the graphene oxide, it is reduced again to prepare a graphene.
  • a solvent such as water
  • the vinol sodium salt improves the dispersity of graphene oxide in water, and the two naphthalene groups improve the separation properties of graphene, as well as due to weak ⁇ - ⁇ interaction, And by washing with an organic solvent, it can be easily removed from the graphene without affecting the properties of the reduced graphene.
  • the method of manufacturing the graphene excellent in solubility by adding a dispersing agent to the graphite peeled by the mechanical peeling method is also studied.
  • a method of separating graphite using ⁇ - ⁇ interaction by mixing graphite and a metal salt aqueous solution, intercalation of metal salts between graphite, or intercalation of aromatic cyclic compounds between graphite has been studied (patent publication). 10-2012-0095907 et al.).
  • the metal salt or aromatic compound dissolved in the aqueous solution is intercalated between the layers of graphite, thereby increasing the interlayer distance of graphite.
  • An object of the present invention is not only excellent dispersibility in aqueous and organic solvents, but also graphene peeling dispersion stabilizer and graphene containing the same, which can improve the intercalation and dispersion characteristics of alkali metal salts in graphite. It provides an alkali metal salt complex.
  • Another object of the present invention is to provide a method for producing graphene, which is easy to mass-produce graphene, and can stably and easily prepare graphene.
  • the present invention provides a dispersion stabilizer for graphene peeling having a structure of the formula (1).
  • Ar is an aromatic group having 4 to 100 carbon atoms
  • M is an alkali metal
  • X is an oxide group (-O-), carboxylate group (-COO-) capable of ion bonding with the alkali metal M
  • Y is -CH 2 -or -CF 2-
  • n is 0 to 10
  • m is an integer from 1 to 3
  • Z is absent, or -CH 2- , -NH-, -O-, -S-, -SO 2- , -CO- or -CF 2-
  • E is -H, -CH 3 , -SH, -OH, -NH 2 or -CH 2 NH 2
  • p is an integer from 1 to 100
  • l is 1 or 2.
  • the present invention provides a graphene-alkali metal salt complex having a graphene peeling dispersion stabilizer represented by Chemical Formula 1 interposed between the layer and the layer of graphene.
  • the present invention by mixing the graphite stabilizer dispersion stabilizer and graphite in the presence of a solvent, so that the graphene release dispersion stabilizer is inserted between the graphite layer and the layer, the interlayer of graphite Increasing the interval; Dispersing the graphite having the graphene peeling dispersion stabilizer inserted therein to prepare a graphene-alkali metal salt composite having a graphene peeling dispersion stabilizer inserted between the graphene layer and the layer; And by washing the graphene-alkali metal salt complex with a solvent, to provide a graphene manufacturing method comprising the step of removing the dispersion stabilizer for graphene peeling from the graphene-alkali metal salt complex.
  • the dispersion stabilizer for graphene peeling according to the present invention may not only have excellent dispersion in aqueous and organic solvents, but also improve insertion and dispersion characteristics of alkali metal salts in graphite. Hydrophobic graphite is agglomerated due to the strong attraction between each other, the dispersion stabilizer having a hydrophilic group according to the present invention can prevent the agglomeration of the graphite, it can be easily dispersed in various solvents by modifying the dispersion stabilizer . In addition, according to the method for producing graphene according to the present invention, it is possible to stably produce a large amount of graphene.
  • FIG. 1 is a schematic diagram showing a process of peeling off the graphene using the dispersion stabilizer for graphene peeling according to the present invention.
  • Figure 2 is a photograph showing the long-term stability of the graphene-graphene peeling dispersion stabilizer composite prepared using NaOH and the dispersion stabilizer for graphene peeling of the present invention.
  • Figure 3 is an electron scanning micrograph of the graphene prepared using NaOH and the dispersion stabilizer for graphene peeling of the present invention.
  • Dispersion stabilizer for graphene peeling according to the present invention is inserted between the layer and the layer of graphite, by increasing the interlayer distance of the graphite, as a material to promote the peeling of the graphene from graphite, having a structure of formula (1).
  • Ar is an aromatic group having 4 to 100 carbon atoms, preferably 5 to 50 carbon atoms, for example, 6 to 20 carbon atoms
  • M is an alkali metal such as Li, Na, K
  • X is an alkali metal M
  • Oxide groups (Oxide, -O-), carboxylate groups (Carboxylate, -COO-), sulfonate groups (Sulfonate, -SO 3- ), sulfonyl groups (Sulfonyl, -SO 2- ) Or a phosphite group (Phosphite, -PO 3- )
  • Y is -CH 2 -or -CF 2-
  • n is 0 to 10, preferably 0 to 5, for example an integer of 1, 2 or 3
  • m is the number of functional groups containing alkali metal M connected to aromatic group Ar, which is an integer of 1 to 3.
  • Z is absent or is -CH 2- , -NH-, -O-, -S-, -SO 2- , -CO- or -CF 2-
  • E is -H, -CH 3 ,- SH, -OH, -NH 2 or -CH 2 NH 2
  • p is an integer from 1 to 100, preferably from 1 to 25, for example from 2 to 10
  • l is an ethylene glycol chain linked to the aromatic group Ar As the number of, 1 or 2.
  • the aromatic group Ar may include one or more hydrocarbon aromatic groups or heterocyclic aromatic groups, preferably an aromatic group having a planarity, for example, Aromatic groups, such as these, may be sufficient.
  • A is each independently O, S, Se or NH
  • n is an integer from 0 to 10, preferably 0 to 5, for example 1, 2 or 3
  • v and w is an integer of 0 to 1
  • each R is independently a hydrogen atom, an alkyl group having 1 to 50 carbon atoms, for example, an alkyl group having 1 to 20 carbon atoms or an alkoxy group, having 2 to 50 carbon atoms,
  • an alkene or alkyne having 3 to 20 carbon atoms
  • an aryl or heteroaryl group having 4 to 50 carbon atoms for example, 5 to 20 carbon atoms.
  • the alkyl group, alkene group or alkyne group may have a branched (branched chain) or cyclic structure, such as linear, iso alkyl (iso alkyl).
  • the said R may be substituted by substituents, such as an amine.
  • binding salts of the alkali metals M, X, and Y may be exemplified.
  • M, Y and n are as described in the formula (1).
  • graphene peeling dispersion stabilizer represented by Formula 1 may include a compound represented by the following formula (1a) to 1j.
  • FIG. 1 is a schematic diagram showing a process of peeling off the graphene using the dispersion stabilizer for graphene peeling according to the present invention.
  • the dispersion stabilizer for graphene peeling according to the present invention is inserted between the layer of graphite (A of Figure 1) and the layer (B of Figure 1), by increasing the interlayer distance of graphite, graphite The graphene is peeled off (FIG. 1C).
  • the dispersion stabilizer for graphene peeling according to the present invention is an aromatic compound having an alkali metal salt and a hydrophilic alkyl chain in the form of ethylene glycol, and has excellent dispersity and solubility in aqueous and organic solvents, and graphite It can be effectively penetrated (inserted) between layers of and.
  • an alkali metal salt is intercalated between the layer and the layer of graphite to increase the interlayer distance of the graphite, and also has excellent planarity of the dispersion stabilizer.
  • an oxide group (-O-), a carboxylate group (-COO-), a sulfonate group (-SO 3- ), a sulfonyl group (-SO 2- ), and a phosphate at one end of the graphene peeling dispersion stabilizer By introducing a fighter group (-PO 3- ) and the like and stably coordinating the metal salt using the same, the stability of the metal salt can be improved.
  • the dispersion stabilizer for peeling graphene since the oxygen atoms constituting the alkyl chain in the form of ethylene glycol have unshared electron pairs, the oxygen atoms surround some alkali metal salts (Li + , Na + , K +, etc.). As a result, metal salts can be stably coordinated in a form similar to crown ethers. In this case, since the metal salt is located at both ends of the graphene peeling dispersion stabilizer, when the graphene peeling dispersion stabilizer penetrates between the graphite layer and the layer, the dispersibility of the graphite can be further improved.
  • the dispersion stabilizer for graphene peeling according to the present invention can be prepared by reacting an aromatic compound having a hydroxy group with ethylene glycol and a metal salt, as shown in the following examples.
  • a graphene peeling dispersion stabilizer represented by the formula (1) and graphite are mixed, The interlayer spacing of graphite is increased by inserting a dispersion stabilizer for peeling graphene between layers.
  • the amount of the graphene peeling dispersion stabilizer represented by the formula (1) is 10 to 90% by weight, preferably 50 to 90% by weight, more preferably based on the total content of the graphene peeling dispersion stabilizer and graphite. 80 to 90% by weight.
  • the amount of the dispersion stabilizer for peeling graphene may be 2 to 10 times by weight.
  • the amount of the graphene peeling dispersion stabilizer is too small, there is a concern that the peeling of graphite may be insufficient.
  • the amount of the graphene peeling dispersion stabilizer is too large, the electrical conductivity of the resulting graphene is lowered. There is a risk of becoming unfavorable and economically undesirable without any particular benefit.
  • a conventional aqueous or organic solvent may be used without particular limitation, and for example, water, ethanol, isopropyl alcohol, dimethyl sulfoxide, dichloromethane, carbon disulfide , Acetone, chloroform, carbon tetrachloride, 1,4-dioxane, methyl acetate, pyridine, m-cresol, phenol, dimethylformamide, dimethylacetamide, sulfuric acid, N-methyl-2-pyrrolidone and pyridine
  • One or more solvents selected may be used.
  • the amount of the solvent is not particularly limited and may be set as needed.
  • 500 to 9900 parts by weight preferably 2000 to 9900, based on 100 parts by weight of the dispersion stabilizer for graphene and the total graphite. Parts by weight. If the amount of the solvent is too small, the dispersion stabilizer for graphene peeling and graphite may not be sufficiently dissolved. If the amount of the solvent is too high, the production efficiency of graphene may be lowered.
  • the mixing temperature of the solvent, the dispersion stabilizer for graphene peeling, and graphite may also be appropriately set as necessary, for example, 0 to 200 ° C, preferably 25 to 50 ° C.
  • a graphene-alkali metal salt composite having a graphene peeling dispersion stabilizer is inserted between the graphene layer and the layer.
  • the dispersing step may be performed by peeling and pulverizing graphite into which the dispersion stabilizer for graphene peeling is inserted, by stirring or ultrasonically pulverizing the graphite solution into which the dispersion stabilizer for graphene peeling is inserted.
  • the content of the dispersion stabilizer for graphene peeling is 10 to 90% by weight, preferably 50 to 90% by weight, and more, based on the total content of the graphene-alkali metal salt composite. Preferably it is 80 to 90 weight%.
  • the composite in which the dispersion stabilizer for graphene peeling is inserted between the layer and the layer of graphene thus prepared is referred to as "graphene-alkali metal salt complex" or "graphene-graphene dispersion stabilizer composite".
  • the solution containing the graphene-alkali metal salt composite is referred to as "graphene-alkali metal salt composite ink.”
  • the graphene-alkali metal salt composite is washed with a solvent to remove the graphene peeling dispersion stabilizer from the graphene-alkali metal salt composite, thereby obtaining pure graphene.
  • a solvent used in the washing step, one or more of the solvent used for mixing the graphene peeling dispersion stabilizer and graphite may be appropriately selected and used as necessary, and water may be preferably used.
  • the method for producing graphene according to the present invention as an organic-inorganic complex compound having a safe and inexpensive alkali metal salt and a hydrophilic alkyl chain, using a graphene peeling dispersion stabilizer represented by the formula (1), By peeling the pins, it is possible to produce graphene easily, stably, and inexpensively as compared to a method of simply peeling graphite using an alkali metal.
  • the method for producing graphene according to the present invention it is possible to mass-produce graphene without undergoing an environmentally undesirable chemical reduction process.
  • the graphene prepared according to the present invention may be used as various electrical and electronic materials such as electrostatic discharge (ESD) devices such as antistatic films, electromagnetic interference (EMI) devices such as electromagnetic shielding films, electrodes, and heat radiating materials.
  • ESD electrostatic discharge
  • EMI electromagnetic interference
  • reaction solution was raised to 60 ° C., stirred for 2 hours, and then cooled to room temperature to obtain a white solid material.
  • 2.50 g (4.62 mmol) of the obtained compound (35) were dissolved in 16 ml of acetonitrile (MeCN), cooled to 0 ° C., and 0.53 ml (3.99 mmol) of bromotrimethylsilane was added thereto. , And reacted at room temperature for 17 hours to synthesize compound (36). While slowly adding 2M aqueous NaOH solution (aq) to the synthesized compound (36), the pH was adjusted to 8, and then precipitated with ethanol to obtain a phosphate type compound (37).
  • the graphene-graphene peeling dispersion stabilizer composite ink obtained in Example 8 was filtered under reduced pressure, and then washed several times with water to remove the graphene peeling dispersion stabilizer from the graphene-graphene peeling dispersion stabilizer composite. Pins were prepared.
  • the remaining powder (graphene without dispersion stabilizer) was added to water, ethanol, isopropyl alcohol, dimethyl sulfoxide, dichloromethane, carbon disulfide, acetone, chloroform, carbon tetrachloride, 1,4-dioxane , Methyl acetate, pyridine, m-cresol, phenol, dimethylformamide, dimethylacetamide, sulfuric acid, N-methyl-2-pyrrolidone and pyridine was prepared.
  • SEM scanning electron microscope, Hitachi S-4800

Abstract

Disclosed are a dispersion stabilizer for graphene exfoliation capable of effectively exfoliating graphene from graphite, a graphene-alkali metal salt composite comprising the same, and a method for preparing graphene using the same. The dispersion stabilizer for graphene exfoliation has a structure of chemical formula 1. In chemical formula 1: Ar is a C4-100 aromatic group; M is an alkali metal; X is an oxide group (-O-), a carboxylate group (-COO-), a sulfonate group (-SO3-), a sulfonyl group (-SO2-) or a phosphite group (-PO3-) capable of binding to the alkali metal M by ionic bond; Y is -CH2- or -CF2-; n is an integer of 0-10; m is an integer of 1-3; Z does not exist or is -CH2-, -NH-, -O-, -S-, -SO2-, -CO- or -CF2-; E is -H, -CH3, -SH, -OH, -NH2 or -CH2NH2; p is an integer of 1-100; and l is 1 or 2.

Description

그래핀 박리용 분산 안정제, 이를 포함하는 그래핀-알칼리 금속염 복합체, 및 이를 이용한 그래핀의 제조방법Dispersion stabilizer for graphene peeling, graphene-alkali metal salt composite comprising the same, and method for producing graphene using the same
본 발명은 그래핀 박리용 분산 안정제, 이를 포함하는 그래핀-알칼리 금속염 복합체, 및 이를 이용한 그래핀의 제조방법에 관한 것으로서, 더욱 상세하게는, 그래파이트로부터 그래핀을 효율적으로 박리할 수 있는 그래핀 박리용 분산 안정제, 이를 포함하는 그래핀-알칼리 금속염 복합체, 및 이를 이용한 그래핀의 제조방법에 관한 것이다.The present invention relates to a dispersion stabilizer for graphene peeling, a graphene-alkali metal salt composite including the same, and a method for preparing graphene using the same, and more particularly, graphene capable of efficiently peeling graphene from graphite. The present invention relates to a dispersion stabilizer for peeling, a graphene-alkali metal salt composite including the same, and a method of preparing graphene using the same.
그래핀(graphene)은 탄소 원자가 6각형 벌집 모양으로 연결되어 2차원 시이트(sheet) 형상을 가지는 탄소 결정으로서, 다수의 그래핀 시이트가 적층되어 그래파이트(graphite)를 형성한다. 따라서, 그래파이트를 박리(exfoliation)시키면, 한층 또는 다수층으로 이루어진 시이트 형태의 그래핀을 얻을 수 있다. 그래핀은 금속의 성질 및 비금속의 성질을 모두 가지는 물질로서, 금속의 성질로서 양호한 전기 전도성 및 열 전도성을 가지며, 비금속의 성질로서 높은 열안정성 및 화학적 불활성을 가진다. 그래핀은 전기 소자, 배터리, 연료 전지, 내화성 재료 등의 다양한 용도에 적용될 수 있다.Graphene is a carbon crystal in which carbon atoms are connected in a hexagonal honeycomb shape to have a two-dimensional sheet shape, and a plurality of graphene sheets are stacked to form graphite. Therefore, when the graphite is exfoliated, a sheet-like graphene composed of one or more layers can be obtained. Graphene is a material having both metal and nonmetal properties, and has good electrical and thermal conductivity as metals, and has high thermal stability and chemical inertness as nonmetals. Graphene can be applied to various applications such as electric devices, batteries, fuel cells, refractory materials, and the like.
전기적, 광학적 및 기계적 특성이 우수한 그래핀을 얻기 위해서는, 그래파이트로부터 그래핀을 효율적으로 박리하여야 한다. 그래파이트로부터 그래핀을 박리하는 방법으로는, 기계적 박리법과 화학적 박리법이 알려져 있다. 기계적 박리법은 기계적 분쇄 또는 접착 테이프를 이용하는 방법으로서, 그래파이트를 단순히 기계적으로 분쇄하거나, 그래파이트에 접착 테이프를 붙인 다음 떼어 내어, 접착 테이프에 부착되어 박리되는 그래핀을 얻는 방법이다. 화학적 박리법은, 그래파이트를 산화제로 산화시켜 산화 그래파이트를 제조한 다음, 산화 그래파이트의 면과 면 사이에 물 등의 용매를 삽입하여, 층과 층 사이의 간격을 증가시키고, 교반 또는 초음파 분쇄하여, 산화 그래핀을 박리시킨 다음, 이를 다시 환원시켜 그래핀을 제조하는 방법이다. 예를 들면, Chem. Commun., 2012, 48, 7732-7734 "Binol salt as a completely removable graphene surfactant"에는, 그래파이트를 산화시켜 그래핀 옥사이드(graphene oxide: GO)를 제조하고, 제조된 그래핀 옥사이드와 비놀(Binol) 및 수산화나트륨(NaOH)을 혼합하여, 비놀 나트륨염(Binol sodium salt)이 그래핀 옥사이드의 층과 층 사이에 삽입되도록 한 다음, 그래핀 옥사이드를 환원 및 박리시켜, 비놀 나트륨염이 삽입된 그래핀(그래핀 옥사이드의 환원 생성물)을 제조한 다음, 생성물을 물로 세척하여, 비놀 나트륨염을 제거함으로써, 순수한 그래핀을 얻는 방법이 개시되어 있다. 상기 비놀 나트륨염은 물에 대한 그래핀 옥사이드의 분산성(dispersity)을 향상시키고, 두 개의 나프탈렌 그룹이 그래핀의 분리 특성을 향상시킬 뿐만 아니라, 약한 π-π 상호 작용(interaction)으로 인하여, 수계 및 유기계 용매를 이용한 세척에 의하여, 환원된 그래핀의 특성에 영향을 미치지 않고, 그래핀으로부터 용이하게 제거될 수 있다.In order to obtain graphene having excellent electrical, optical and mechanical properties, it is necessary to efficiently peel graphene from graphite. As a method of peeling graphene from graphite, mechanical peeling and chemical peeling are known. The mechanical peeling method is a method of mechanically grinding or using an adhesive tape, in which graphite is simply mechanically crushed, or an adhesive tape is attached to the graphite and then peeled off to obtain graphene that is attached to the adhesive tape and peeled off. In the chemical exfoliation method, graphite is prepared by oxidizing graphite with an oxidizing agent, and then a solvent such as water is inserted between the surfaces of the graphite oxide to increase the spacing between the layers, stirring or ultrasonic grinding, After peeling off the graphene oxide, it is reduced again to prepare a graphene. For example, Chem. Commun., 2012, 48, 7732-7734 "Binol salt as a completely removable graphene surfactant", by oxidizing graphite to produce graphene oxide (GO), and the prepared graphene oxide and binol (Binol) and Sodium hydroxide (NaOH) is mixed so that the binol sodium salt is inserted between the layers of graphene oxide, and then the graphene oxide is reduced and exfoliated to form the graphene containing the nonol sodium salt ( A method of obtaining pure graphene is disclosed by preparing a reduced product of graphene oxide) and then washing the product with water to remove the vinol sodium salt. The vinol sodium salt improves the dispersity of graphene oxide in water, and the two naphthalene groups improve the separation properties of graphene, as well as due to weak π-π interaction, And by washing with an organic solvent, it can be easily removed from the graphene without affecting the properties of the reduced graphene.
최근에는, 기계적 박리법으로 박리된 그래파이트에 분산제를 첨가하여, 용해도가 우수한 그래핀을 제조하는 방법도 연구되고 있다. 예를 들면, 그래파이트와 금속염 수용액을 혼합하여, 그래파이트 사이에 금속염을 삽입하거나(intercalation), 그래파이트 사이에 방향족 고리화합물을 삽입시켜 π-π 상호작용을 이용한 그래파이트의 분리 방법이 연구되고 있다(특허 공개 10-2012-0095907 등 참조). 상기 방법에서는, 수용액에 용해된 금속염 또는 방향족 화합물이 그래파이트의 층과 층 사이에 삽입(intercalation)되어, 그래파이트의 층간 거리를 증가시킨다.In recent years, the method of manufacturing the graphene excellent in solubility by adding a dispersing agent to the graphite peeled by the mechanical peeling method is also studied. For example, a method of separating graphite using π-π interaction by mixing graphite and a metal salt aqueous solution, intercalation of metal salts between graphite, or intercalation of aromatic cyclic compounds between graphite has been studied (patent publication). 10-2012-0095907 et al.). In this method, the metal salt or aromatic compound dissolved in the aqueous solution is intercalated between the layers of graphite, thereby increasing the interlayer distance of graphite.
본 발명의 목적은, 수계 및 유기계 용매에 대한 분산도가 우수할 뿐만 아니라, 그래파이트 내부에서 알칼리 금속염의 삽입(intercalation) 및 분산 특성을 향상시킬 수 있는 그래핀 박리용 분산 안정제 및 이를 포함하는 그래핀-알칼리 금속염 복합체를 제공하는 것이다.An object of the present invention is not only excellent dispersibility in aqueous and organic solvents, but also graphene peeling dispersion stabilizer and graphene containing the same, which can improve the intercalation and dispersion characteristics of alkali metal salts in graphite. It provides an alkali metal salt complex.
본 발명의 다른 목적은, 그래핀의 대량 생산이 용이하며, 그래핀을 안정하고간편하게 제조할 수 있는 그래핀의 제조방법을 제공하는 것이다.Another object of the present invention is to provide a method for producing graphene, which is easy to mass-produce graphene, and can stably and easily prepare graphene.
상기 목적을 달성하기 위하여, 본 발명은 하기 화학식 1의 구조를 가지는 그래핀 박리용 분산 안정제를 제공한다.In order to achieve the above object, the present invention provides a dispersion stabilizer for graphene peeling having a structure of the formula (1).
[화학식 1][Formula 1]
Figure PCTKR2014005057-appb-I000001
Figure PCTKR2014005057-appb-I000001
상기 화학식 1에서, Ar은 탄소수 4 내지 100의 방향족기이고, M은 알칼리 금속이고, X는 알칼리 금속 M과 이온 결합할 수 있는 옥사이드기(-O-), 카르복실레이트기(-COO-), 설포네이트기(-SO3-), 설포닐기(-SO2-) 또는 포스파이트기(-PO3-)이고, Y는 -CH2- 또는 -CF2- 이고, n은 0 내지 10의 정수이고, m은 1 내지 3의 정수이고, Z는 존재하지 않거나, -CH2-, -NH-, -O-, -S-, -SO2-, -CO- 또는 -CF2-이고, E는 -H, -CH3, -SH, -OH, -NH2 또는 -CH2NH2이고, p는 1 내지 100의 정수이며, l은 1 또는 2이다. In Formula 1, Ar is an aromatic group having 4 to 100 carbon atoms, M is an alkali metal, X is an oxide group (-O-), carboxylate group (-COO-) capable of ion bonding with the alkali metal M , A sulfonate group (-SO 3- ), a sulfonyl group (-SO 2- ) or a phosphite group (-PO 3- ), Y is -CH 2 -or -CF 2- , n is 0 to 10 Integer, m is an integer from 1 to 3, Z is absent, or -CH 2- , -NH-, -O-, -S-, -SO 2- , -CO- or -CF 2- , E is -H, -CH 3 , -SH, -OH, -NH 2 or -CH 2 NH 2 , p is an integer from 1 to 100, l is 1 or 2.
또한, 본 발명은 그래핀의 층과 층 사이에 상기 화학식 1로 표시되는 그래핀 박리용 분산 안정제가 삽입되어 있는 그래핀-알칼리 금속염 복합체를 제공한다. 또한, 본 발명은, 용매의 존재 하에서, 상기 화학식 1로 표시되는 그래핀 박리용 분산 안정제와 그래파이트를 혼합하여, 그래파이트의 층과 층 사이에 그래핀 박리용 분산 안정제가 삽입되도록 함으로써, 그래파이트의 층간 간격을 증가시키는 단계; 상기 그래핀 박리용 분산 안정제가 삽입된 그래파이트를 분산시켜, 그래핀의 층과층 사이에 그래핀 박리용 분산 안정제가 삽입된 그래핀-알칼리 금속염 복합체를 제조하는 단계; 및 용매로 상기 그래핀-알칼리 금속염 복합체를 세척하여, 그래핀-알칼리 금속염 복합체로부터 그래핀 박리용 분산 안정제를 제거하는 단계를 포함하는 그래핀의 제조방법을 제공한다.In addition, the present invention provides a graphene-alkali metal salt complex having a graphene peeling dispersion stabilizer represented by Chemical Formula 1 interposed between the layer and the layer of graphene. In addition, the present invention, by mixing the graphite stabilizer dispersion stabilizer and graphite in the presence of a solvent, so that the graphene release dispersion stabilizer is inserted between the graphite layer and the layer, the interlayer of graphite Increasing the interval; Dispersing the graphite having the graphene peeling dispersion stabilizer inserted therein to prepare a graphene-alkali metal salt composite having a graphene peeling dispersion stabilizer inserted between the graphene layer and the layer; And by washing the graphene-alkali metal salt complex with a solvent, to provide a graphene manufacturing method comprising the step of removing the dispersion stabilizer for graphene peeling from the graphene-alkali metal salt complex.
본 발명에 따른 그래핀 박리용 분산 안정제는, 수계 및 유기계 용매에 대한 분산도가 우수할 뿐만 아니라, 그래파이트 내부에서 알칼리 금속염의 삽입 및 분산 특성을 향상시킬 수 있다. 소수성의 그래파이트들은 서로간의 강력한 인력으로 인해 응집되는 현상이 발생하는데, 본 발명에 따른 친수성기를 가지는 분산 안정제는 그래파이트들의 응집 현상을 방지하며, 분산 안정제를 변형하여 다양한 용매에 용이하게 분산되도록 할 수 있다. 또한, 본 발명에 따른 그래핀의 제조방법에 의하면, 그래핀을 안정하게 대량 생산할 수 있다.The dispersion stabilizer for graphene peeling according to the present invention may not only have excellent dispersion in aqueous and organic solvents, but also improve insertion and dispersion characteristics of alkali metal salts in graphite. Hydrophobic graphite is agglomerated due to the strong attraction between each other, the dispersion stabilizer having a hydrophilic group according to the present invention can prevent the agglomeration of the graphite, it can be easily dispersed in various solvents by modifying the dispersion stabilizer . In addition, according to the method for producing graphene according to the present invention, it is possible to stably produce a large amount of graphene.
도 1은 본 발명에 따른 그래핀 박리용 분산 안정제를 이용하여 그래핀을 박리시키는 과정을 보여주는 모식도.1 is a schematic diagram showing a process of peeling off the graphene using the dispersion stabilizer for graphene peeling according to the present invention.
도 2는 NaOH 및 본 발명의 그래핀 박리용 분산 안정제를 사용하여 제조한 그래핀-그래핀 박리용 분산 안정제 복합체의 장기 안정성을 보여주는 사진.Figure 2 is a photograph showing the long-term stability of the graphene-graphene peeling dispersion stabilizer composite prepared using NaOH and the dispersion stabilizer for graphene peeling of the present invention.
도 3은 NaOH 및 본 발명의 그래핀 박리용 분산 안정제룰 사용하여 제조한 그래핀의 전자주사현미경 사진.Figure 3 is an electron scanning micrograph of the graphene prepared using NaOH and the dispersion stabilizer for graphene peeling of the present invention.
이하, 첨부된 도면을 참조하여 본 발명을 상세히 설명한다. 본 발명에 따른 그래핀 박리용 분산 안정제는 그래파이트의 층과 층 사이에서 삽입되어, 그래파이트의 층간 거리를 증가시킴으로써, 그래파이트로부터 그래핀의 박리를 촉진시키는 물질로서, 하기 화학식 1의 구조를 가진다. Hereinafter, with reference to the accompanying drawings will be described in detail the present invention. Dispersion stabilizer for graphene peeling according to the present invention is inserted between the layer and the layer of graphite, by increasing the interlayer distance of the graphite, as a material to promote the peeling of the graphene from graphite, having a structure of formula (1).
화학식 1
Figure PCTKR2014005057-appb-C000001
 Formula 1
Figure PCTKR2014005057-appb-C000001
상기 화학식 1에서, Ar은 탄소수 4 내지 100, 바람직하게는 탄소수 5 내지 50, 예를 들면 탄소수 6 내지 20의 방향족기이고, M은 Li, Na, K 등의 알칼리 금속이고, X는 알칼리 금속 M과 이온 결합할 수 있는 옥사이드기(Oxide, -O-), 카르복실레이트기(Carboxylate, -COO-), 설포네이트기(Sulfonate, -SO3-), 설포닐기(Sulfonyl, -SO2-) 또는 포스파이트기(Phosphite, -PO3-)이고, Y는 -CH2- 또는 -CF2- 이고, n은 0 내지 10, 바람직하게는 0 내지 5, 예를 들면 1, 2 또는 3의 정수이고, m은 방향족기 Ar에 연결되는 알칼리 금속 M을 포함하는 작용기의 개수로서, 1 내지 3의 정수이다. 또한, Z는 존재하지 않거나, -CH2-, -NH-, -O-, -S-, -SO2-, -CO- 또는 -CF2-이고, E는 -H, -CH3, -SH, -OH, -NH2 또는 -CH2NH2이고, p는 1 내지 100, 바람직하게는 1 내지 25, 예를 들면 2 내지 10의 정수이며, l은 방향족기 Ar에 연결되는 에틸렌글리콜 사슬의 개수로서, 1 또는 2이다.In Formula 1, Ar is an aromatic group having 4 to 100 carbon atoms, preferably 5 to 50 carbon atoms, for example, 6 to 20 carbon atoms, M is an alkali metal such as Li, Na, K, and X is an alkali metal M Oxide groups (Oxide, -O-), carboxylate groups (Carboxylate, -COO-), sulfonate groups (Sulfonate, -SO 3- ), sulfonyl groups (Sulfonyl, -SO 2- ) Or a phosphite group (Phosphite, -PO 3- ), Y is -CH 2 -or -CF 2- , n is 0 to 10, preferably 0 to 5, for example an integer of 1, 2 or 3 And m is the number of functional groups containing alkali metal M connected to aromatic group Ar, which is an integer of 1 to 3. In addition, Z is absent or is -CH 2- , -NH-, -O-, -S-, -SO 2- , -CO- or -CF 2- , E is -H, -CH 3 ,- SH, -OH, -NH 2 or -CH 2 NH 2 , p is an integer from 1 to 100, preferably from 1 to 25, for example from 2 to 10, l is an ethylene glycol chain linked to the aromatic group Ar As the number of, 1 or 2.
상기 화학식 1에서, 방향족기 Ar은 탄화수소 방향족기 또는 헤테로고리 방향족기를 하나 이상 포함할 수 있고, 바람직하게는 평면성을 가지는 방향족기이고, 예를 들면,
Figure PCTKR2014005057-appb-I000002
Figure PCTKR2014005057-appb-I000003
Figure PCTKR2014005057-appb-I000004
Figure PCTKR2014005057-appb-I000005
Figure PCTKR2014005057-appb-I000006
Figure PCTKR2014005057-appb-I000007
Figure PCTKR2014005057-appb-I000008
등의 방향족기일 수 있다. 여기서, 굴곡선은 결합부를 나타내며, A는 각각 독립적으로 O, S, Se 또는 NH 이고, n은 0 내지 10, 바람직하게는 0 내지 5, 예를 들면 1, 2 또는 3의 정수이고, v 및 w는 각각 0 내지 1 의 정수이고, R은 각각 독립적으로, 수소원자(hydrogen atom), 탄소수 1 내지 50, 예를 들면, 탄소수 1 내지 20의 알킬기 또는 알콕시기(alkoxy), 탄소수 2 내지 50, 예를 들면, 탄소수 3 내지 20의 알켄기(alkene) 또는 알킨기(alkyne), 탄소수 4 내지 50, 예를 들면 탄소수 5 내지 20의 아릴기(aryl) 또는 헤테로아릴기(heteroaryl)이다. 여기서, 상기 알킬기, 알켄기 또는 알킨기는 선형, 이소 알킬(iso alkyl) 등의 가지형(branched chain) 또는 고리형 구조를 가질 수 있다. 또한, 필요에 따라, 상기 R은 아민(amine) 등의 치환기로 치환되어 있을 수도 있다. In Formula 1, the aromatic group Ar may include one or more hydrocarbon aromatic groups or heterocyclic aromatic groups, preferably an aromatic group having a planarity, for example,
Figure PCTKR2014005057-appb-I000002
Figure PCTKR2014005057-appb-I000003
Figure PCTKR2014005057-appb-I000004
Figure PCTKR2014005057-appb-I000005
Figure PCTKR2014005057-appb-I000006
Figure PCTKR2014005057-appb-I000007
Figure PCTKR2014005057-appb-I000008
Aromatic groups, such as these, may be sufficient. Wherein the curve represents the bond, A is each independently O, S, Se or NH, n is an integer from 0 to 10, preferably 0 to 5, for example 1, 2 or 3, v and w is an integer of 0 to 1, and each R is independently a hydrogen atom, an alkyl group having 1 to 50 carbon atoms, for example, an alkyl group having 1 to 20 carbon atoms or an alkoxy group, having 2 to 50 carbon atoms, For example, an alkene or alkyne having 3 to 20 carbon atoms, an aryl or heteroaryl group having 4 to 50 carbon atoms, for example, 5 to 20 carbon atoms. Here, the alkyl group, alkene group or alkyne group may have a branched (branched chain) or cyclic structure, such as linear, iso alkyl (iso alkyl). In addition, as needed, the said R may be substituted by substituents, such as an amine.
또한, 상기 알칼리 금속 M, X 및 Y의 결합 형태로는, 하기 결합 염(salt)들을 예시할 수 있다. 여기서, M, Y 및 n은 화학식 1에서 설명한 바와 같다.In addition, the binding salts of the alkali metals M, X, and Y may be exemplified. Here, M, Y and n are as described in the formula (1).
Figure PCTKR2014005057-appb-I000009
Figure PCTKR2014005057-appb-I000009
상기 화학식 1로 표시되는 그래핀 박리용 분산 안정제의 구체적인 예로는 하기 화학식 1a 내지 1j로 표시되는 화합물을 예시할 수 있다. Specific examples of the graphene peeling dispersion stabilizer represented by Formula 1 may include a compound represented by the following formula (1a) to 1j.
[화합물 1a][Compound 1a]
Figure PCTKR2014005057-appb-I000010
Figure PCTKR2014005057-appb-I000010
[화합물 1b][Compound 1b]
Figure PCTKR2014005057-appb-I000011
Figure PCTKR2014005057-appb-I000011
[화합물 1c][Compound 1c]
Figure PCTKR2014005057-appb-I000012
Figure PCTKR2014005057-appb-I000012
[화합물 1d][Compound 1d]
Figure PCTKR2014005057-appb-I000013
Figure PCTKR2014005057-appb-I000013
[화합물 1e][Compound 1e]
Figure PCTKR2014005057-appb-I000014
Figure PCTKR2014005057-appb-I000014
[화합물 1f][Compound 1f]
Figure PCTKR2014005057-appb-I000015
Figure PCTKR2014005057-appb-I000015
[화합물 1g][Compound 1g]
Figure PCTKR2014005057-appb-I000016
Figure PCTKR2014005057-appb-I000016
[화합물 1h][Compound 1h]
Figure PCTKR2014005057-appb-I000017
Figure PCTKR2014005057-appb-I000017
[화합물 1i][Compound 1i]
Figure PCTKR2014005057-appb-I000018
Figure PCTKR2014005057-appb-I000018
[화합물 1j][Compound 1j]
Figure PCTKR2014005057-appb-I000019
Figure PCTKR2014005057-appb-I000019
[화합물 1k][Compound 1k]
Figure PCTKR2014005057-appb-I000020
Figure PCTKR2014005057-appb-I000020
[화합물 1l][Compound 1l]
Figure PCTKR2014005057-appb-I000021
Figure PCTKR2014005057-appb-I000021
[화합물 1m][Compound 1m]
Figure PCTKR2014005057-appb-I000022
Figure PCTKR2014005057-appb-I000022
[화합물 1n][Compound 1n]
Figure PCTKR2014005057-appb-I000023
Figure PCTKR2014005057-appb-I000023
[화합물 1o][Compound 1o]
Figure PCTKR2014005057-appb-I000024
Figure PCTKR2014005057-appb-I000024
[화합물 1p][Compound 1p]
Figure PCTKR2014005057-appb-I000025
Figure PCTKR2014005057-appb-I000025
[화합물 1q][Compound 1q]
Figure PCTKR2014005057-appb-I000026
Figure PCTKR2014005057-appb-I000026
도 1은 본 발명에 따른 그래핀 박리용 분산 안정제를 이용하여 그래핀을 박리시키는 과정을 보여주는 모식도이다. 도 1에 도시된 바와 같이, 본 발명에 따른 그래핀 박리용 분산 안정제는 그래파이트(도 1의 A)의 층과 층 사이에서 삽입되어(도 1의 B), 그래파이트의 층간 거리를 증가시킴으로써, 그래파이트로부터 그래핀을 박리시킨다(도 1의 C). 본 발명에 따른 그래핀 박리용 분산 안정제는, 알칼리 금속염 및 에틸렌글리콜(ethylene glycol) 형태의 친수성 알킬 체인을 가지는 방향족 화합물로서, 수계 및 유기계 용매에 대한 분산성(dispersity) 및 용해도가 우수하고, 그래파이트의 층과 층 사이로 효과적으로 침투(삽입)될 수 있다. 본 발명에 따른 그래핀 박리용 분산 안정제가 그래파이트의 층과 층 사이로 삽입되면, 알칼리 금속염이 그래파이트의 층과 층 사이로 침투(intercalation)하여 그래파이트의 층간 거리를 증가시키고, 또한, 분산 안정제의 평면성이 우수한 방향족 부분과 그래파이트 사이의 π-π 상호 작용에 의해, 그래파이트의 층간 분리가 더욱 촉진된다. 또한, 그래핀 박리용 분산 안정제의 한쪽 말단에 옥사이드기(-O-), 카르복실레이트기(-COO-), 설포네이트기(-SO3-), 설포닐기(-SO2-), 포스파이트기(-PO3-) 등을 도입하고, 이를 이용하여 금속염을 안정하게 배위시킴으로써, 금속염의 안정성을 향상시킬 수 있다. 본 발명에 따른 그래핀 박리용 분산 안정제에 있어서, 에틸렌글리콜 형태의 알킬 체인을 구성하는 산소 원자들은 비공유 전자쌍을 가지므로, 상기 산소 원자가 일부 알칼리 금속염(Li+, Na+, K+ 등)을 둘러 싸서, 크라운 에테르(crown ether)와 유사한 형태로 금속염을 안정하게 배위할 수 있다. 이 경우, 그래핀 박리용 분산 안정제의 양쪽 말단에 금속염이 위치하는 형태가 되므로, 그래핀 박리용 분산 안정제가 그래파이트의 층과 층 사이에 침투되는 경우, 그래파이트의 분산성을 더욱 향상시킬 수 있다. 본 발명에 따른 그래핀 박리용 분산 안정제는, 하기 실시예에 나타낸 바와 같이, 히드록시기를 가지는 방향족 화합물과 에틸렌글리콜 및 금속염을 반응시켜 제조할 수 있다.1 is a schematic diagram showing a process of peeling off the graphene using the dispersion stabilizer for graphene peeling according to the present invention. As shown in Figure 1, the dispersion stabilizer for graphene peeling according to the present invention is inserted between the layer of graphite (A of Figure 1) and the layer (B of Figure 1), by increasing the interlayer distance of graphite, graphite The graphene is peeled off (FIG. 1C). The dispersion stabilizer for graphene peeling according to the present invention is an aromatic compound having an alkali metal salt and a hydrophilic alkyl chain in the form of ethylene glycol, and has excellent dispersity and solubility in aqueous and organic solvents, and graphite It can be effectively penetrated (inserted) between layers of and. When the dispersion stabilizer for graphene peeling according to the present invention is inserted between the layer and the layer of graphite, an alkali metal salt is intercalated between the layer and the layer of graphite to increase the interlayer distance of the graphite, and also has excellent planarity of the dispersion stabilizer. By the π-π interaction between the aromatic moiety and the graphite, the interlayer separation of graphite is further promoted. Further, an oxide group (-O-), a carboxylate group (-COO-), a sulfonate group (-SO 3- ), a sulfonyl group (-SO 2- ), and a phosphate at one end of the graphene peeling dispersion stabilizer By introducing a fighter group (-PO 3- ) and the like and stably coordinating the metal salt using the same, the stability of the metal salt can be improved. In the dispersion stabilizer for peeling graphene according to the present invention, since the oxygen atoms constituting the alkyl chain in the form of ethylene glycol have unshared electron pairs, the oxygen atoms surround some alkali metal salts (Li + , Na + , K +, etc.). As a result, metal salts can be stably coordinated in a form similar to crown ethers. In this case, since the metal salt is located at both ends of the graphene peeling dispersion stabilizer, when the graphene peeling dispersion stabilizer penetrates between the graphite layer and the layer, the dispersibility of the graphite can be further improved. The dispersion stabilizer for graphene peeling according to the present invention can be prepared by reacting an aromatic compound having a hydroxy group with ethylene glycol and a metal salt, as shown in the following examples.
본 발명에 따른 그래핀 박리용 분산 안정제를 이용하여 그래핀을 제조(박리)하기 위해서는, 먼저, 용매의 존재 하에서, 상기 화학식 1로 표시되는 그래핀 박리용 분산 안정제와 그래파이트를 혼합하여, 그래파이트의 층과 층 사이에 그래핀 박리용 분산 안정제가 삽입되도록 함으로써, 그래파이트의 층간 간격을 증가시킨다. 상기 화학식 1로 표시되는 그래핀 박리용 분산 안정제의 사용량은, 상기 그래핀 박리용 분산 안정제 및 그래파이트의 전체 함량에 대하여, 10 내지 90 중량%, 바람직하게는 50 내지 90 중량%, 더욱 바람직하게는 80 내지 90 중량%이다. 예를 들면, 상기 그래파이트에 대하여, 상기 그래핀 박리용 분산 안정제의 사용량은 중량비로 2 내지 10 배일 수 있다. 여기서, 상기 그래핀 박리용 분산 안정제의 사용량의 너무 작으면, 그래파이트의 박리가 불충분하게 수행될 우려가 있고, 상기 그래핀 박리용 분산 안정제의 사용량의 너무 많으면, 생성된 그래핀의 전기전도도가 저하될 우려가 있고, 특별한 이익이 없이, 경제적으로 바람직하지 못하다. 상기 그래핀 박리용 분산 안정제 및 그래파이트가 혼합되는 용매로는 통상의 수계 또는 유기계 용매를 특별한 제한 없이 사용할 수 있고, 예를 들면, 물, 에탄올, 이소프로필알콜, 디메틸설폭사이드, 디클로로메탄, 이황화탄소, 아세톤, 클로로포름, 사염화탄소, 1,4-디옥산, 메틸아세테이트, 피리딘, m-크레졸, 페놀, 디메틸포름아미드, 디메틸아세트아미드, 황산, N-메틸-2-피롤리돈 및 피리딘으로 이루어진 군에서 선택된 하나 이상의 용매를 사용할 수 있다. 상기 용매의 사용량은 특별히 제한되지 않고, 필요에 따라 설정될 수 있으나, 예를 들면, 상기 그래핀 박리용 분산 안정제 및 그래파이트 전체 100 중량부에 대하여, 500 내지 9900 중량부, 바람직하게는 2000 내지 9900 중량부이다. 여기서, 상기 용매의 사용량이 너무 적으면, 그래핀 박리용 분산 안정제 및 그래파이트가 충분히 용해되지 않을 우려가 있으며, 너무 많으면, 그래핀의 제조 효율이 저하될 우려가 있다. 상기 용매와 그래핀 박리용 분산 안정제 및 그래파이트의 혼합 온도도 필요에 따라 적절히 설정될 수 있으며, 예를 들면, 0 내지 200 ℃, 바람직하게는 25 내지 50 ℃이다. In order to prepare (peel) the graphene using the graphene peeling dispersion stabilizer according to the present invention, first, in the presence of a solvent, a graphene peeling dispersion stabilizer represented by the formula (1) and graphite are mixed, The interlayer spacing of graphite is increased by inserting a dispersion stabilizer for peeling graphene between layers. The amount of the graphene peeling dispersion stabilizer represented by the formula (1) is 10 to 90% by weight, preferably 50 to 90% by weight, more preferably based on the total content of the graphene peeling dispersion stabilizer and graphite. 80 to 90% by weight. For example, with respect to the graphite, the amount of the dispersion stabilizer for peeling graphene may be 2 to 10 times by weight. Here, if the amount of the graphene peeling dispersion stabilizer is too small, there is a concern that the peeling of graphite may be insufficient. If the amount of the graphene peeling dispersion stabilizer is too large, the electrical conductivity of the resulting graphene is lowered. There is a risk of becoming unfavorable and economically undesirable without any particular benefit. As the solvent in which the dispersion stabilizer for graphene peeling and graphite are mixed, a conventional aqueous or organic solvent may be used without particular limitation, and for example, water, ethanol, isopropyl alcohol, dimethyl sulfoxide, dichloromethane, carbon disulfide , Acetone, chloroform, carbon tetrachloride, 1,4-dioxane, methyl acetate, pyridine, m-cresol, phenol, dimethylformamide, dimethylacetamide, sulfuric acid, N-methyl-2-pyrrolidone and pyridine One or more solvents selected may be used. The amount of the solvent is not particularly limited and may be set as needed. For example, 500 to 9900 parts by weight, preferably 2000 to 9900, based on 100 parts by weight of the dispersion stabilizer for graphene and the total graphite. Parts by weight. If the amount of the solvent is too small, the dispersion stabilizer for graphene peeling and graphite may not be sufficiently dissolved. If the amount of the solvent is too high, the production efficiency of graphene may be lowered. The mixing temperature of the solvent, the dispersion stabilizer for graphene peeling, and graphite may also be appropriately set as necessary, for example, 0 to 200 ° C, preferably 25 to 50 ° C.
다음으로, 상기 그래핀 박리용 분산 안정제가 삽입된 그래파이트를 분산시켜, 그래핀의 층과 층 사이에 그래핀 박리용 분산 안정제가 삽입된 그래핀-알칼리 금속염 복합체를 제조한다. 상기 분산 단계는, 그래핀 박리용 분산 안정제가 삽입된 그래파이트 용액을 교반하거나 초음파 분쇄하는 등의 방법으로, 그래핀 박리용 분산 안정제가 삽입된 그래파이트를 박리 및 분쇄시켜 수행될 수 있다. 상기 그래핀-알칼리 금속염 복합체에 있어서, 상기 그래핀 박리용 분산 안정제의 함량은, 상기 그래핀-알칼리 금속염 복합체의 전체 함량에 대하여, 10 내지 90 중량%, 바람직하게는 50 내지 90 중량%, 더욱 바람직하게는 80 내지 90 중량%이다. 본 명세서에 있어서, 이와 같이 제조된 그래핀의 층과 층 사이에 그래핀 박리용 분산 안정제가 삽입된 복합체를 "그래핀-알칼리 금속염 복합체" 또는 "그래핀-그래핀 박리용 분산 안정제 복합체"라 하고, 상기 그래핀-알칼리 금속염 복합체를 포함하는 용액을 "그래핀-알칼리 금속염 복합체 잉크(ink)"라 한다. 이와 같이 잉크 상태의 복합체를 제조한 다음, 용매로 상기 그래핀-알칼리 금속염 복합체를 세척하여, 그래핀-알칼리 금속염 복합체로부터 그래핀 박리용 분산 안정제를 제거하면, 순순한 그래핀을 얻을 수 있다. 상기 세척 단계에 사용되는 용매로는 상기 그래핀 박리용 분산 안정제 및 그래파이트의 혼합에 사용되는 용매의 하나 이상을 필요에 따라 적절히 선택하여 사용할 수 있고, 바람직하게는 물을 사용할 수 있다.Next, by dispersing graphite in which the dispersion stabilizer for graphene peeling is inserted, a graphene-alkali metal salt composite having a graphene peeling dispersion stabilizer is inserted between the graphene layer and the layer. The dispersing step may be performed by peeling and pulverizing graphite into which the dispersion stabilizer for graphene peeling is inserted, by stirring or ultrasonically pulverizing the graphite solution into which the dispersion stabilizer for graphene peeling is inserted. In the graphene-alkali metal salt composite, the content of the dispersion stabilizer for graphene peeling is 10 to 90% by weight, preferably 50 to 90% by weight, and more, based on the total content of the graphene-alkali metal salt composite. Preferably it is 80 to 90 weight%. In the present specification, the composite in which the dispersion stabilizer for graphene peeling is inserted between the layer and the layer of graphene thus prepared is referred to as "graphene-alkali metal salt complex" or "graphene-graphene dispersion stabilizer composite". In addition, the solution containing the graphene-alkali metal salt composite is referred to as "graphene-alkali metal salt composite ink." After preparing the composite in the ink state as described above, the graphene-alkali metal salt composite is washed with a solvent to remove the graphene peeling dispersion stabilizer from the graphene-alkali metal salt composite, thereby obtaining pure graphene. As the solvent used in the washing step, one or more of the solvent used for mixing the graphene peeling dispersion stabilizer and graphite may be appropriately selected and used as necessary, and water may be preferably used.
본 발명에 따른 그래핀의 제조 방법에 의하면, 안전하고 저렴한 알칼리 금속염 및 친수성 알킬 체인을 가지는 유ㆍ무기 복합 화합물로서, 상기 화학식 1로 표시되는 그래핀 박리용 분산 안정제를 이용하여, 간단한 공정으로 그래핀을 박리함으로써, 단순히 알칼리 금속을 사용하여 그래파이트를 박리시키는 방법과 비교하여, 용이하고, 안정하며, 저렴하게 그래핀을 제조할 수 있다. 또한, 본 발명에 따른 그래핀의 제조 방법에 의하면, 환경적으로 바람직하지 못한 화학적 환원과정을 거치지 않고, 그래핀을 대량 생산할 수 있다. 본 발명에 따라 제조된 그래핀은, 대전방지막 등의 ESD (Electrostatic Discharge) 소자, 전자파 차폐 필름 등의 EMI(electromagnetic interference) 소자, 전극, 방열소재 등의 다양한 전기 및 전자 재료로 사용될 수 있다.According to the method for producing graphene according to the present invention, as an organic-inorganic complex compound having a safe and inexpensive alkali metal salt and a hydrophilic alkyl chain, using a graphene peeling dispersion stabilizer represented by the formula (1), By peeling the pins, it is possible to produce graphene easily, stably, and inexpensively as compared to a method of simply peeling graphite using an alkali metal. In addition, according to the method for producing graphene according to the present invention, it is possible to mass-produce graphene without undergoing an environmentally undesirable chemical reduction process. The graphene prepared according to the present invention may be used as various electrical and electronic materials such as electrostatic discharge (ESD) devices such as antistatic films, electromagnetic interference (EMI) devices such as electromagnetic shielding films, electrodes, and heat radiating materials.
이하, 구체적인 실시예를 통하여 본 발명을 더욱 상세히 설명한다. 하기 실시예는 본 발명을 예시하기 위한 것으로서, 본 발명이 하기 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to specific examples. The following examples are intended to illustrate the invention, and the invention is not limited by the following examples.
[실시예 1] 그래핀 박리용 분산 안정제의 합성 Example 1 Synthesis of Dispersion Stabilizer for Graphene Peeling
하기 반응식 1에 나타낸 바와 같이, 질소 분위기에서, 하이드로퀴논(Hydroquinone, 화합물 1) 10.00 g (90.82 mmol), p-벤조퀴논(benzoquinone) 980 mg (9.99 mmol), H2SO4 1.10 mL 및 트리에틸렌글리콜모노메틸에테르 (triethylene glycol monomethyl ether, p= 2) 14.5 mL (90.82 mmol)을 혼합하고, 80 ℃에서 24 시간 동안 교반하면서 반응시켰다. 디클로로메텐을 첨가하여, 반응액을 완전히 용해시키고, 물로 추출한 다음, 유기층을 MgSO4로 건조하고, 남은 유기층을 230 ℃, 1 mmHg의 조건에서 분별증류하여, 화합물 (2) 13.96 g을 얻었다(수율: 60%, 1H-NMR (CDCl3, Varian 400 MHz): δ 6.94 (1H, s), 6.74 (4H, s), 4.00-4.03 (2H, m), 3.79- 3.81 (2H, m), 3.64-3.71 (6H, m), 3.54-3.56 (2H, m), 3.36 (3H, s)).As shown in Scheme 1 below, in a nitrogen atmosphere, 10.00 g (90.82 mmol) of hydroquinone (Compound 1), 980 mg (9.99 mmol) of p-benzoquinone, 1.10 mL of H 2 SO 4 and triethylene 14.5 mL (90.82 mmol) of triethylene glycol monomethyl ether (p = 2) was mixed and reacted with stirring at 80 ° C. for 24 hours. Dichloromethene was added, the reaction solution was completely dissolved, extracted with water, and the organic layer was dried over MgSO 4 , and the remaining organic layer was fractionally distilled under the conditions of 230 ° C. and 1 mmHg to give 13.96 g of compound (2) (yield) : 60%, 1 H-NMR (CDCl 3 , Varian 400 MHz): δ 6.94 (1H, s), 6.74 (4H, s), 4.00-4.03 (2H, m), 3.79-3.81 (2H, m), 3.64-3.71 (6H, m), 3.54-3.56 (2H, m), 3.36 (3H, s)).
질소 분위기에서, 합성된 화합물 (2) 3.00 g을 이소프로필알콜(IPA) 42.0 mL에 용해시킨 후, 메탄올(MeOH) 20.0 mL에 NaOH 560 mg이 용해된 알칼리 금속 용액을 혼합하고, 80 ℃에서 24 시간 동안 교반하면서 반응시키고, IPA를 감압하여 제거하여, 펜옥사이드(Phenoxide type) 타입의 화합물 (3, M = Na) 3.0 g합성하였다(수율: 92 %, 1H-NMR (D2O, Varian 400 MHz): δ 6.65-6.67 (2H, d), 6.39-6.41 (2H, d), 3.94-3.95 (2H, m), 3.65- 3.67 (2H, m), 3.58-3.43 (8H, m), 3.20 (3H, s))In a nitrogen atmosphere, 3.00 g of the synthesized compound (2) was dissolved in 42.0 mL of isopropyl alcohol (IPA), followed by mixing an alkali metal solution in which 560 mg of NaOH was dissolved in 20.0 mL of methanol (MeOH), and 24 at 80 ° C. The reaction was stirred for a while, and the IPA was removed under reduced pressure to synthesize 3.0 g of a compound of the Phenoxide type (3, M = Na) (yield: 92%, 1 H-NMR (D 2 O, Varian). 400 MHz): δ 6.65-6.67 (2H, d), 6.39-6.41 (2H, d), 3.94-3.95 (2H, m), 3.65- 3.67 (2H, m), 3.58-3.43 (8H, m), 3.20 (3H, s))
[반응식 1]Scheme 1
Figure PCTKR2014005057-appb-I000027
Figure PCTKR2014005057-appb-I000027
[실시예 2] 그래핀 박리용 분산 안정제의 합성 Example 2 Synthesis of Dispersion Stabilizer for Graphene Peeling
하기 반응식 2에 나타낸 바와 같이, 질소 분위기에서, 실시예 1에서 합성된 화합물 (2) 1.00 g (3.9 mmol)을, 톨루엔(Toluene, PhMe) 10.0 mL에 용해시킨 후, NaH (60 % dispersion in mineral oil) 0.35 g (1.5 eq)을 넣고, 0 ℃에서 30분 동안 교반하면서 반응시킨 후, 1,3-프로판설톤(propanesultone, 화합물 (5)) 0.57 g (4.68 mmol)을 넣고, 110 ℃에서 4시간 동안 교반하면서 반응시켜, 알킬설포네이트(Alkylsurfonate) 타입의 화합물 (6, M = Na)을 합성하였다.As shown in Scheme 2, 1.00 g (3.9 mmol) of the compound (2) synthesized in Example 1 was dissolved in 10.0 mL of toluene (Toluene, PhMe) in a nitrogen atmosphere, followed by NaH (60% dispersion in mineral). 0.35 g (1.5 eq) of oil) was added and reacted with stirring at 0 ° C. for 30 minutes. Then, 0.57 g (4.68 mmol) of 1,3-propanesultone (Compound (5)) was added thereto, followed by 4 at 110 ° C. The reaction was carried out with stirring for a time to synthesize an alkylsulfonate (Alkylsurfonate) type compound (6, M = Na).
[반응식 2]Scheme 2
Figure PCTKR2014005057-appb-I000028
Figure PCTKR2014005057-appb-I000028
[실시예 3] 그래핀 박리용 분산 안정제의 합성 Example 3 Synthesis of Dispersion Stabilizer for Graphene Peeling
하기 반응식 3에 나타낸 바와 같이, 질소 분위기에서, 소디움 4-하이드록시벤젠설포네이트 디하이드레이트(Sodium 4-hydroxybenzenesulfonate dehydrate, 화합물 7 ) 1.0 g (4.31 mmol), p-벤조퀴논 51.0 mg (0.474 mmol), H2SO4 0.1 mL 및 트리에틸렌글리콜 모노메틸에테르(p= 2) 0.690 mL (4.31 mmol)을 혼합하고, 80 ℃에서 24 시간 동안 교반하면서 반응시켰다. 반응 종결 후, 반응액을 냉각하고, 용매를 농축하고, 에탄올을 첨가한 다음, 반응액을 여과하였다. 여과물(Filtrate)을 메탄올에 용해시킨 후, 클로로포름(Chloroform)을 첨가하여, 결정을 생성시키고, 여과하여, 화합물 (8)를 합성하였다. 합성된 화합물 (8)에 2M NaOH 수용액(aq)을 천천히 첨가하면서, pH를 8로 맞춘 후, 에탄올로 침전시켜, 설포네이트(surfonate) 타입의 화합물 (9, M = Na)을 합성하였다.As shown in Scheme 3 below, in a nitrogen atmosphere, 1.0 g (4.31 mmol) of sodium 4-hydroxybenzenesulfonate dehydrate (Compound 7), 51.0 mg (0.474 mmol) of p-benzoquinone, 0.1 mL of H 2 SO 4 and 0.690 mL (4.31 mmol) of triethylene glycol monomethyl ether (p = 2) were mixed and reacted with stirring at 80 ° C. for 24 hours. After completion of the reaction, the reaction solution was cooled, the solvent was concentrated, ethanol was added, and the reaction solution was filtered. After the filtrate was dissolved in methanol, chloroform was added to form crystals and filtered to synthesize Compound (8). While slowly adding 2M aqueous NaOH solution (aq) to the synthesized compound (8), the pH was adjusted to 8, and then precipitated with ethanol to synthesize a sulfonate type compound (9, M = Na).
[반응식 3] Scheme 3
Figure PCTKR2014005057-appb-I000029
Figure PCTKR2014005057-appb-I000029
[실시예 4] 그래핀 박리용 분산 안정제의 합성 Example 4 Synthesis of Dispersion Stabilizer for Graphene Peeling
하기 반응식 4에 나타낸 바와 같이, 4-브로모페놀(4-bromophenol, 화합물 10) 4.00 g (23.1 mmol), 2-[2-(2-메톡시에톡시)에톡시]-1-(4-메틸벤젠설포네이트)에탄 (2-[2-(2-methoxyethoxy)ethoxy]-1-(4-methylbenzenesulfonate)ethane, 화합물 11) 8.09 g (25.41 mmol) 및 K2CO3 7.70 g (55.4 mmol)을 반응기에 넣고 질소로 치환시킨 뒤, 무수 디메틸포름아미드(DMF) 60 ml를 넣어, 반응액을 용해시켰다. 반응액을 80 ℃에서 24시간 동안 교반하면서 반응시킨 후, 에틸아세테이트를 넣어 완전히 용해시키고, 물로 추출한 다음, 유기층을 MgSO4로 건조시키고, 남은 유기층을 농축하였다. 농축된 유기층을 헥산 : 에틸아세테이트 = 1:1 (부피비) 혼합 용액으로 전개하면서, 컬럼 정제하여 화합물 (12) 6.83 g을 얻었다(수율: 95%, 1H-NMR (DMSO, Varian 400 MHz): δ 7.36 (2H, d, J = 8.8 Hz), 6.80 (2H, d, J = 9.2 Hz), 4.1-4.07 (2H, m), 3.85- 3.83 (2H, m), 3.73-3.68 (6H, m), 3.55-3.53 (2H, m), 3.37 (3H, s)).As shown in Scheme 4, 4.00 g (23.1 mmol) of 4-bromophenol (Compound 10), 2- [2- (2-methoxyethoxy) ethoxy] -1- (4- Methylbenzenesulfonate) ethane (2- [2- (2-methoxyethoxy) ethoxy] -1- (4-methylbenzenesulfonate) ethane, compound 8.11 g (25.41 mmol) and 7.70 g (55.4 mmol) K 2 CO 3 The mixture was placed in a reactor, replaced with nitrogen, and 60 ml of anhydrous dimethylformamide (DMF) was added thereto to dissolve the reaction solution. After the reaction solution was stirred at 80 ° C. for 24 hours with stirring, ethyl acetate was added to dissolve completely, extracted with water, the organic layer was dried over MgSO 4 , and the remaining organic layer was concentrated. The concentrated organic layer was developed with hexane: ethyl acetate = 1: 1 (volume ratio) mixed solution, and column purified to give 6.83 g of compound (12) (yield: 95%, 1 H-NMR (DMSO, Varian 400 MHz): δ 7.36 (2H, d, J = 8.8 Hz), 6.80 (2H, d, J = 9.2 Hz), 4.1-4.07 (2H, m), 3.85-3.83 (2H, m), 3.73-3.68 (6H, m ), 3.55-3.53 (2H, m), 3.37 (3H, s)).
얻어진 화합물 (12) 3.35 g (10.5 mmol)을 반응기에 넣고, 질소 치환한 다음, 무수 테트라히드로퓨란(THF) 30 ml를 첨가하여, 용해시켰다. 반응액을 -78 ℃로 냉각하고, n-부틸리튬(n-BuLi) 7.87 ml를 천천히 첨가한 후, 1.5시간 동안 교반하고, 디에틸클로로포스페이트(Diethyl chlorophosphate) 2.27 ml (15.75 mmol)를 첨가한 다음, 동일한 온도에서 3시간 동안 더 교반하면서 반응시켰다. 암모늄클로라이드를 첨가하여, 반응을 종료한 뒤, 에틸아세테이트를 첨가하여, 반응물을 완전히 용해시키고, 물로 추출한 다음, 유기층을 MgSO4로 건조하고, 남은 유기층을 농축하였다. 농축된 유기층을 에틸아세테이트 : 메탄올 = 10:1 (부피비)의 혼합 용액으로 전개하면서, 컬럼 정제하여 화합물 (13) 1.86 g을 얻었다(수율: 45%, 1H-NMR (CDCl3, Varian 400 MHz): δ 7.65 (2H, dd), 7.09 (2H, dd), 4.17-4.15 (2H, m), 3.99- 3.93 (4H, m), 3.76-3.74 (2H, m), 3.59-3.57 (2H, m), 3.53-3.50 (4H, m) 3.49-3.40 (2H, m) 3.32 (2H, s), 3.22 (3H, s), 1.21 (6H, m)).3.35 g (10.5 mmol) of the obtained compound (12) were placed in a reactor, replaced with nitrogen, and 30 ml of anhydrous tetrahydrofuran (THF) was added to dissolve it. The reaction solution was cooled to -78 ° C, 7.87 ml of n-butyllithium (n-BuLi) was slowly added, stirred for 1.5 hours, and 2.27 ml (15.75 mmol) of diethyl chlorophosphate were added. Next, the reaction was further stirred at the same temperature for 3 hours. Ammonium chloride was added, the reaction was completed, ethyl acetate was added, the reaction was completely dissolved, extracted with water, the organic layer was dried over MgSO 4 , and the remaining organic layer was concentrated. The concentrated organic layer was developed with a mixed solution of ethyl acetate: methanol = 10: 1 (volume ratio), and the column was purified to obtain 1.86 g of compound (13) (yield: 45%, 1 H-NMR (CDCl 3 , Varian 400 MHz) ): δ 7.65 (2H, dd), 7.09 (2H, dd), 4.17-4.15 (2H, m), 3.99-3.93 (4H, m), 3.76-3.74 (2H, m), 3.59-3.57 (2H, m), 3.53-3.50 (4H, m) 3.49-3.40 (2H, m) 3.32 (2H, s), 3.22 (3H, s), 1.21 (6H, m)).
상기 화합물 (13) 1.74 g (4.62 mmol)을 아세토나이트릴(acetonitrile, MeCN) 16 ml에 용해시킨 후, 0 ℃로 냉각하고, 브로모트리메틸실란(Bromotrimethylsilane) 0.53 ml (3.99 mmol)을 첨가한 다음, 상온에서 17 시간 동안 반응시켜, 화합물 (14)을 합성하였다. 합성된 화합물 (14)에 2M NaOH 수용액(aq)을 천천히 첨가하면서, pH를 8로 맞춘 후, 에탄올로 침전시켜, 포스페이트(phosphate) 타입의 화합물 (15) 1.37 g을 얻었다(수율: 80%, 1H-NMR (D2O, Varian 400 MHz): δ 7.68 (2H, dd), 7.03 (2H, dd), 4.16-4.14 (2H, m), 3.81- 3.79 (2H, m), 3.66-3.65 (2H, m), 3.60-3.55 (4H, m), 3.49-3.47 (2H, m)).1.74 g (4.62 mmol) of the compound (13) was dissolved in 16 ml of acetonitrile (MeCN), cooled to 0 ° C., and 0.53 ml (3.99 mmol) of bromotrimethylsilane was added thereto. , And reacted at room temperature for 17 hours to synthesize compound (14). While slowly adding 2M aqueous NaOH solution (aq) to the synthesized compound (14), the pH was adjusted to 8, and then precipitated with ethanol to obtain 1.37 g of a compound of the phosphate type (15) (yield: 80%, 1 H-NMR (D 2 O, Varian 400 MHz): δ 7.68 (2H, dd), 7.03 (2H, dd), 4.16-4.14 (2H, m), 3.81-3.79 (2H, m), 3.66-3.65 (2H, m), 3.60-3.55 (4H, m), 3.49-3.47 (2H, m)).
[반응식 4] Scheme 4
Figure PCTKR2014005057-appb-I000030
Figure PCTKR2014005057-appb-I000030
[실시예 5] 그래핀 박리용 분산 안정제의 합성 Example 5 Synthesis of Dispersion Stabilizer for Graphene Peeling
하기 반응식 5에 나타낸 바와 같이, 9,9'-스피로바이플루오렌(9,9'- spirobifluorene, 화합물 16) 6.52 g (20.6 mmol)과 무수 FeCl3 10 mg을 클로로포롬(CHCl3) 60 ml에 용해시킨 후, 10 mL의 클로로포롬에 브로민(bromine) 2.24 mL (43.6 mmol)을 희석시킨 용액을, 0 ℃에서 1시간에 걸쳐 천천히 떨어뜨려 첨가하였다. 24시간 후, 반응물을 포화 소디움 싸이오설페이트(Na2S2O3) 용액과 물로 세척하여, 잔류 브로민을 제거하였다. 유기층을 소디움 설페이트로(Na2SO4)로 건조하고, 유기용매를 제거하고, CHCl3/에탄올(EtOH)로 재결정하여 화합물 (17) 8.8 g을 얻었다(수율: 88%, 1H-NMR (CDCl3, Varian 300 MHz): δ 7.83-7.80 (2H, d), 7.72-7.69 (2H, d), 7.52-7.49 (2H, dd), 7.41-7.37 (2H, t), 7.18-7.13 (2H, t), 6.84-6.83 (2H, d), 6.73-6.70 (2H, d)). As shown in Scheme 5, 6.52 g (20.6 mmol) of 9,9'-spirobifluorene (Compound 16) and 10 mg of anhydrous FeCl 3 were added to 60 ml of chloroform (CHCl 3 ). After dissolving, a solution of 2.24 mL (43.6 mmol) of bromine diluted in 10 mL of chloroform was added slowly dropwise at 0 ° C. over 1 hour. After 24 hours, the reaction was washed with saturated sodium thiosulfate (Na 2 S 2 O 3 ) solution and water to remove residual bromine. The organic layer was dried over sodium sulfate (Na 2 SO 4 ), the organic solvent was removed, and recrystallized with CHCl 3 / ethanol (EtOH) to give 8.8 g of the compound (17) (yield: 88%, 1 H-NMR ( CDCl 3 , Varian 300 MHz): δ 7.83-7.80 (2H, d), 7.72-7.69 (2H, d), 7.52-7.49 (2H, dd), 7.41-7.37 (2H, t), 7.18-7.13 (2H , t), 6.84-6.83 (2H, d), 6.73-6.70 (2H, d)).
화합물 (17) 2 g (4.21 mmol)을 50 mL 테트라하이드로퓨란(THF)에 용해시키고, -78 ℃로 냉각하고, n-부틸리튬(n-BuLi) 2.87 ml을 천천히 넣어준 후, 20분 후에 트리메틸보레이트(B(OMe)3) 0.65 g(6.31 mmol) 을 넣고, 약 20분 교반 후, 상온으로 온도를 상승시켰다. 다음으로, 과산화수소(H2O2) 10 mL와 소디움 옥사이드(NaOH) 0.5 g을 넣고, 12 시간 동안 교반하고, 메틸렌클로라이드(CH2Cl2)와 물로 추출한 다음, MgSO4로 유기층을 건조하고, 컬럼으로 분리하여 화합물 (18)을 얻었다. 메탄올 16 mL에 포타슘 하이드록사이드(KOH) 1.23 g(21.9 mmol)을 용해시킨 후, 화합물 (18) 3 g(7.30 mmol)을 0 ℃에서 첨가하였다. 반응액을 같은 온도에서 1시간 교반한 후, N,N-디메틸싸이오카바모일 클로라이드 (N,N-dimethylthiocarbamoyl chloride) 2.71 g (21.9 mmol)을 첨가하였다. 반응액의 온도를 60 ℃까지 올리고, 2시간 동안 교반한 후, 상온으로 냉각하여, 흰색의 고체 물질을 얻었다. 얻어진 물질을 MeOH/H2O (1:1 v/v) 혼합 용액으로 세척하고, 메틸렌클로라이드 및 핵산의 혼합 용액(CH2Cl2 : hexane = 2:1)으로 컬럼 정제하여 화합물 (19)를 얻었다. 2 g (4.21 mmol) of Compound (17) was dissolved in 50 mL tetrahydrofuran (THF), cooled to -78 ° C, and slowly added 2.87 ml of n-butyllithium (n-BuLi), and after 20 minutes 0.65 g (6.31 mmol) of trimethylborate (B (OMe) 3 ) was added thereto, followed by stirring for about 20 minutes, and the temperature was increased to room temperature. Next, 10 mL of hydrogen peroxide (H 2 O 2 ) and 0.5 g of sodium oxide (NaOH) were added thereto, stirred for 12 hours, extracted with methylene chloride (CH 2 Cl 2 ) and water, and the organic layer was dried over MgSO 4 , Compound (18) was obtained by column separation. After dissolving 1.23 g (21.9 mmol) of potassium hydroxide (KOH) in 16 mL of methanol, 3 g (7.30 mmol) of compound (18) were added at 0 ° C. After the reaction solution was stirred at the same temperature for 1 hour, 2.71 g (21.9 mmol) of N, N-dimethylthiocarbamoyl chloride was added. The temperature of the reaction solution was raised to 60 ° C., stirred for 2 hours, and then cooled to room temperature to obtain a white solid material. The obtained material was washed with a mixed solution of MeOH / H 2 O (1: 1 v / v), and column purified with a mixed solution of methylene chloride and nucleic acid (CH 2 Cl 2 : hexane = 2: 1) to obtain compound (19). Got it.
화합물 (19) 2 g(4.01 mmol)을 디페닐에테르(diphenylether) 3 mL에 용해시킨 후, 280 ℃에서 3.5 시간 동안 교반하였다. 반응액을 상온으로 냉각하고, 메탄올 40 mL 을 첨가하여, 노란 고체 물질 침전을 얻고, 감압 여과하였다. 여과된 고체 물질을 차가운 MeOH/H2O(1:1 v/v) 혼합 용액으로 세척하고, 에틸아세테이트(Ethylacetate) 10 mL 로 15분 동안 초음파 처리하여, 재결정시켜, 화합물 (20)을 얻었다. 질소 분위기에서, 얻어진 화합물 (20) 0.2 g(0.40 mmol) 및 포타슘하이드록사이드(KOH) 0.17 g (3.00 mmol)을 에탄올(EtOH) 5 mL에 용해시킨 후, 70 ℃에서 22 시간 동안 교반하였다. 반응액을 상온으로 냉각하고, H2O 20 mL 및 3M HCl(aq) 15 mL를 첨가하여, 침전된 화합물 (21)을 얻었다.2 g (4.01 mmol) of Compound (19) were dissolved in 3 mL of diphenylether, and then stirred at 280 ° C. for 3.5 hours. The reaction solution was cooled to room temperature, and 40 mL of methanol was added to give a yellow solid substance precipitate, which was filtered under reduced pressure. The filtered solid material was washed with cold MeOH / H 2 O (1: 1 v / v) mixed solution, sonicated with 10 mL of ethylacetate for 15 minutes, and recrystallized to obtain compound (20). In a nitrogen atmosphere, 0.2 g (0.40 mmol) of the obtained compound (20) and 0.17 g (3.00 mmol) of potassium hydroxide (KOH) were dissolved in 5 mL of ethanol (EtOH), followed by stirring at 70 ° C. for 22 hours. The reaction solution was cooled to room temperature, and 20 mL of H 2 O and 15 mL of 3M HCl (aq) were added to obtain precipitated compound (21).
화합물 (21) 2 g(2.34 mmol)을 디메틸포름아마이드(DMF) 20 mL 에 용해시킨 후, 2-(2-(2-메톡시에톡시에톡시)에틸-4-메틸설포네이트(2-(2-(2-methoxyethoxy ethoxy) ethyl-4-methylsulfonate) 2.24 g (7.02 mmol) 및 포타슘하이드록사이드(KOH) 0.39 g (7.02 mmol)을 첨가하였다. 반응액의 온도를 100 ℃로 온도를 올리고 4 시간 동안 교반한 후, 상온으로 온도를 내리고, 감압여과 후, DMF를 감압 증류하여 제거한 다음, 디클로로메탄(CH2Cl2)과 물로 반응물을 추출하고, 유기층을 MgSO4로 건조하고, 페트롤륨 에테르/디에틸에테르(petroleum ether/diethylether) 1:1 혼합 용액을 이용하여, 컬럼 정제하여 화합물 (22)를 얻었다. 화합물 (22) 3.35 g (5.84 mmol)을 반응기에 넣고, 질소 치환한 다음, 무수 테트라히드로퓨란(THF) 30 ml를 첨가하여, 용해시켰다. 반응액을 -78 ℃로 냉각하고, n-부틸리튬(n-BuLi) 4.37 ml를 천천히 첨가한 후, 1.5시간 동안 교반하고, 디에틸클로로포스페이트(Diethyl chlorophosphate) 1.26 ml (8.76 mmol)를 첨가한 다음, 동일한 온도에서 3시간 동안 더 교반하면서 반응시켰다. 암모늄클로라이드를 첨가하여, 반응을 종료한 뒤, 에틸아세테이트를 첨가하여, 반응물을 완전히 용해시키고, 물로 추출한 다음, 유기층을 MgSO4로 건조하고, 남은 유기층을 농축하였다. 농축된 유기층을 에틸아세테이트 : 메탄올 = 10:1 (부피비)의 혼합 용액으로 전개하면서, 컬럼 정제하여 화합물 (23)을 얻었다.2 g (2.34 mmol) of Compound (21) were dissolved in 20 mL of dimethylformamide (DMF), followed by 2- (2- (2-methoxyethoxyethoxy) ethyl-4-methylsulfonate (2- ( 2.24 g (7.02 mmol) of 2- (2-methoxyethoxy ethoxy) ethyl-4-methylsulfonate and 0.39 g (7.02 mmol) of potassium hydroxide (KOH) were added to raise the temperature of the reaction solution to 100 ° C. After stirring for an hour, the temperature was reduced to room temperature, and the filtrate under reduced pressure, the DMF was distilled off under reduced pressure, the reaction was extracted with dichloromethane (CH 2 Cl 2 ) and water, the organic layer was dried over MgSO 4 , petroleum ether Compound purification (22) was obtained by column purification using a mixed solution of diethylether (petroleum ether / diethylether) 1. 3.35 g (5.84 mmol) of compound (22) were placed in a reactor, nitrogen-substituted, and then anhydrous. 30 ml of tetrahydrofuran (THF) was added to dissolve The reaction was cooled to -78 ° C and 4.37 ml of n-butyllithium (n-BuLi) was slowly After the addition, the mixture was stirred for 1.5 hours, 1.26 ml (8.76 mmol) of diethyl chlorophosphate was added, followed by further stirring at the same temperature for 3 hours. Then, ethyl acetate was added, the reaction was completely dissolved, extracted with water, the organic layer was dried over MgSO 4 , and the remaining organic layer was concentrated: The concentrated organic layer was mixed with ethyl acetate: methanol = 10: 1 (volume ratio). Compound (23) was obtained by column purification while developing into a solution.
화합물 (23) 2.91 g(4.62 mmol)을 아세토나이트릴(acetonitrile, MeCN) 16 ml에 용해시킨 후, 0 ℃로 냉각하고, 브로모트리메틸실란(Bromotrimethylsilane) 0.53 ml (3.99 mmol)을 첨가한 다음, 상온에서 17 시간 동안 반응시켜, 화합물 (24)을 합성하였다. 합성된 화합물 (24)에 2M NaOH 수용액(aq)을 천천히 첨가하면서, pH를 8로 맞춘 후, 에탄올로 침전시켜, 포스페이트(phosphate) 타입의 화합물 (25)를 얻었다.2.91 g (4.62 mmol) of Compound (23) was dissolved in 16 ml of acetonitrile (MeCN), cooled to 0 ° C., and 0.53 ml (3.99 mmol) of bromotrimethylsilane was added thereto. By reacting at room temperature for 17 hours, compound (24) was synthesized. The pH was adjusted to 8 while slowly adding 2M aqueous NaOH solution (aq) to the synthesized compound (24), followed by precipitation with ethanol to obtain a phosphate type compound (25).
[반응식 5]Scheme 5
Figure PCTKR2014005057-appb-I000031
Figure PCTKR2014005057-appb-I000031
[실시예 6] 그래핀 박리용 분산 안정제의 합성 Example 6 Synthesis of Dispersion Stabilizer for Graphene Peeling
하기 반응식 6에 나타낸 바와 같이, 질소 분위기에서, 1,5-디히드록시나프탈렌(1,5-Dihydroxynaphthalene, 화합물 (26)) 14.55 g(90.82 mmol), p-벤조퀴논(benzoquinone) 980 mg(9.99 mmol), H2SO4 1.10 mL 및 트리에틸렌글리콜모노메틸에테르(triethyleneglycol monomethyl ether, p= 2) 14.5 mL (90.82 mmol)을 혼합하고, 80 ℃에서 24 시간 동안 교반하면서 반응시켰다. 디클로로메텐을 첨가하여, 반응액을 완전히 용해시키고, 물로 추출한 다음, 유기층을 MgSO4로 건조하고, 남은 유기층을 230 ℃, 1 mmHg의 조건에서 분별증류하여, 화합물 (27)을 얻었다. 질소 분위기에서, 합성된 화합물 (27) 3.00 g(9.79 mmol)을 이소프로필알콜(IPA) 42.0 mL에 용해시킨 후, 메탄올(MeOH) 20.0 mL에 NaOH 0.47 g이 용해된 알칼리 금속 용액을 혼합하고, 80 ℃에서 24 시간 동안 교반하면서 반응시키고, IPA를 감압 제거하여, 펜옥사이드(Phenoxide type) 타입의 화합물 (28)을 얻었다.As shown in Scheme 6 below, in a nitrogen atmosphere, 14.55 g (90.82 mmol) of 1,5-dihydroxynaphthalene (Compound (26)) and 980 mg (9.99 of p-benzoquinone) were used. mmol), 1.10 mL of H 2 SO 4 and 14.5 mL (90.82 mmol) of triethyleneglycol monomethyl ether (p = 2) were mixed and reacted with stirring at 80 ° C. for 24 hours. Dichloromethene was added, the reaction solution was completely dissolved, extracted with water, the organic layer was dried over MgSO 4 , the remaining organic layer was fractionated and distilled under conditions of 230 ° C. and 1 mmHg to obtain a compound (27). In a nitrogen atmosphere, 3.00 g (9.79 mmol) of the synthesized compound (27) was dissolved in 42.0 mL of isopropyl alcohol (IPA), followed by mixing an alkali metal solution in which 0.47 g of NaOH was dissolved in 20.0 mL of methanol (MeOH), The reaction was stirred at 80 ° C. for 24 hours, and IPA was removed under reduced pressure to obtain a phenoxide type compound (28).
[반응식 6]Scheme 6
Figure PCTKR2014005057-appb-I000032
Figure PCTKR2014005057-appb-I000032
[실시예 7] 그래핀 박리용 분산 안정제의 합성 Example 7 Synthesis of Dispersion Stabilizer for Graphene Peeling
하기 반응식 7에 나타낸 바와 같이, 2-요오드티오펜(화합물 (29), 2-iodo thiophene) 3 g (14.28 mmol)과 티오펜-2-보론산(화합물 (30), thiophene- 2-boronic acid) 1.66 g(13.00 mmol), 포타슘카보네이트(K2CO3) 4.93 g (35.7 mmol)을 H2O 1.65 mL 에 용해시킨 후, Pd-PSPEG-adppp complex(P-P chelate palladium complex of N-anchored 2-aza-1,3-bis(diphenylphosphino)propane ligand) 33 mg을 넣고, 50 ℃에서 12 시간 동안 교반한 다음, 잔류 반응물을 감압 여과하고, 헥산으로 컬럼 정제하여, 화합물 (31)을 얻었다. 화합물 (31) 3g (18.04 mmol)을 클로로포름(CHCl3) 200 mL에 용해시킨 후, N-브로모석신이미드(N-bromosuccineimide, NBS) 3.53 g(19.84 mmol)을 천천히 첨가하였다. 반응액을 24 시간 동안 교반하고, 메틸렌클로라이드(CH2Cl2)와 물로 추출한 후, 유기층을 MgSO4로 건조하고, 컬럼으로 분리하여 화합물 (32)를 얻었다. 화합물 (32) 3 g(9.26 mmol), 4-트리에틸렌글리콜 모노에틸에테르 페닐보로닉 엑씨드(4-triethyleneglycol monomethyleter phenylboronic acid, 화합물 (33)) 3.65 g (9.26 mmol), 포타슘카보네이트(K2CO3) 3.20 g(23.15 mmol) 및 Pd(PPh3)4 1.07 g(0.93 mmol)을 넣고, THF 50 mL에 용해시킨 후, 80 ℃에서 12시간 동안 교반하고, 반응액을 상온으로 냉각하고, 메틸렌클로라이드(CH2Cl2)와 물로 추출한 후, 유기층을 MgSO4로 건조하고, 컬럼으로 분리하여 화합물 (34)를 얻었다.As shown in Scheme 7 below, 3 g (14.28 mmol) of 2-iodinethiophene (Compound (29), 2-iodo thiophene) and thiophene-2-boronic acid (Compound (30), thiophene-2-boronic acid ) 1.66 g (13.00 mmol) and potassium carbonate (K 2 CO 3 ) 4.93 g (35.7 mmol) are dissolved in 1.65 mL of H 2 O, followed by Pd-PSPEG-adppp complex (PP chelate palladium complex of N-anchored 2- 33 mg of aza-1,3-bis (diphenylphosphino) propane ligand) was added thereto, stirred at 50 ° C. for 12 hours, and the residue was filtered under reduced pressure and purified by column with hexane to obtain compound (31). 3 g (18.04 mmol) of Compound (31) was dissolved in 200 mL of chloroform (CHCl 3 ), and then 3.53 g (19.84 mmol) of N-bromosuccineimide (NBS) was slowly added. The reaction solution was stirred for 24 hours, extracted with methylene chloride (CH 2 Cl 2 ) and water, and then the organic layer was dried over MgSO 4 and separated by column to obtain compound (32). 3 g (9.26 mmol) of compound (32), 3.65 g (9.26 mmol) of 4-triethyleneglycol monomethyleter phenylboronic acid (Compound (33)), potassium carbonate (K 2 CO 3) 3.20 g (23.15 mmol ) and placed Pd (PPh 3) 4 1.07 g (0.93 mmol), and was dissolved in THF 50 mL, was stirred at 80 ℃ for 12 hours, the reaction solution was cooled to room temperature, After extraction with methylene chloride (CH 2 Cl 2 ) and water, the organic layer was dried over MgSO 4 and separated by column to obtain compound (34).
화합물 (34) 5.07 g(10.5 mmol)을 반응기에 넣고, 질소 치환한 다음, 무수 테트라히드로퓨란(THF) 100 ml를 첨가하여 용해시켰다. 반응액을 -78 ℃로 냉각하고, n-부틸리튬(n-BuLi) 7.87 ml를 천천히 첨가한 후, 1.5시간 동안 교반하고, 디에틸클로로포스페이트(Diethyl chlorophosphate) 2.27 ml (15.75 mmol)를 첨가한 다음, 동일 온도에서 3시간 동안 더 교반하면서 반응시켰다. 암모늄클로라이드를 첨가하여, 반응을 종료한 뒤, 에틸아세테이트를 첨가하여, 반응물을 완전히 용해시키고, 물로 추출한 다음, 유기층을 MgSO4로 건조하고, 남은 유기층을 농축하였다. 농축된 유기층을 에틸아세테이트 : 메탄올 = 10:1 (부피비)의 혼합 용액으로 전개하면서, 컬럼 정제하여 화합물 (35)를 얻었다. 얻어진 화합물 (35) 2.50 g(4.62 mmol)을 아세토나이트릴(acetonitrile, MeCN) 16 ml에 용해시킨 후, 0 ℃로 냉각하고, 브로모트리메틸실란(Bromotrimethylsilane) 0.53 ml(3.99 mmol)을 첨가한 다음, 상온에서 17 시간 동안 반응시켜, 화합물 (36)을 합성하였다. 합성된 화합물 (36)에 2M NaOH 수용액(aq)을 천천히 첨가하면서, pH를 8로 맞춘 후, 에탄올로 침전시켜, 포스페이트(phosphate) 타입의 화합물 (37)을 얻었다.5.07 g (10.5 mmol) of Compound (34) were placed in a reactor, replaced with nitrogen, and dissolved by adding 100 ml of anhydrous tetrahydrofuran (THF). The reaction solution was cooled to -78 ° C, 7.87 ml of n-butyllithium (n-BuLi) was slowly added, stirred for 1.5 hours, and 2.27 ml (15.75 mmol) of diethyl chlorophosphate were added. Next, the reaction was further stirred at the same temperature for 3 hours. Ammonium chloride was added, the reaction was completed, ethyl acetate was added, the reaction was completely dissolved, extracted with water, the organic layer was dried over MgSO 4 , and the remaining organic layer was concentrated. The concentrated organic layer was developed with a mixed solution of ethyl acetate: methanol = 10: 1 (volume ratio), and column purified to obtain compound (35). 2.50 g (4.62 mmol) of the obtained compound (35) were dissolved in 16 ml of acetonitrile (MeCN), cooled to 0 ° C., and 0.53 ml (3.99 mmol) of bromotrimethylsilane was added thereto. , And reacted at room temperature for 17 hours to synthesize compound (36). While slowly adding 2M aqueous NaOH solution (aq) to the synthesized compound (36), the pH was adjusted to 8, and then precipitated with ethanol to obtain a phosphate type compound (37).
[반응식 7]Scheme 7
Figure PCTKR2014005057-appb-I000033
Figure PCTKR2014005057-appb-I000033
[실시예 8] 그래핀-그래핀 박리용 분산 안정제 복합체의 제조 Example 8 Preparation of Graphene-Graphene Peeling Dispersion Stabilizer Composite
물 90 mL에 그래파이트 1 g을 넣은 후, 실시예 1에서 합성된 그래핀 박리용 분산 안정제(화합물 (3)) 5 g을 상온에서 물 10 mL에 완전히 용해시킨 용액을 첨가하였다. 그래파이트 및 그래핀 박리용 분산 안정제의 혼합 용액을 초음파 분쇄기로 6 시간 이상 분쇄하여, 그래핀-그래핀 박리용 분산 안정제 복합체를 제조하였다. 제조된 그래핀-그래핀 박리용 분산 안정제 복합체의 시간에 따른 분산 특성 및 화합물 (3) 대신 NaOH를 첨가한 경우의 분산 특성을 하기 표 1에 나타내었다. 하기 표 1에서, ○: 분산이 잘 됨, △: 약간 분산, X: 침전을 나타낸다. After adding 1 g of graphite to 90 mL of water, a solution in which 5 g of the graphene release dispersion stabilizer (Compound (3)) synthesized in Example 1 was completely dissolved in 10 mL of water at room temperature was added thereto. A mixed solution of graphite and graphene peeling dispersion stabilizer was ground for 6 hours or more using an ultrasonic mill to prepare a graphene-graphene peeling dispersion stabilizer composite. Dispersion characteristics over time of the prepared graphene-graphene peeling dispersion stabilizer composite and the dispersion characteristics when NaOH was added instead of compound (3) are shown in Table 1 below. In Table 1 below,?: Shows good dispersion,?: Slightly dispersed, and X: shows precipitation.
표 1
화합물 3 NaOH
반응 직후 ○ △
1 시간 이후 ○ X
5 시간 이후 ○ X
1 일 이후 ○ X
10 일 이후 ○ X
30 일 이후 ○ X
Table 1
Compound 3 NaOH
Immediately after the reaction ○ △
After 1 hour ○ X
After 5 hours ○ X
After 1 day ○ X
After 10 days ○ X
After 30 days ○ X
또한, 상기 그래핀-그래핀 박리용 분산 안정제(화합물 (3)) 복합체 및 대조군으로 NaOH를 그래핀 박리용 분산 안정제로 사용하여 제조한 그래핀-그래핀 박리용 분산 안정제(NaOH) 복합체의 장기 안정성을 보여주는 사진을 도 2에 나타내었다. 도 2에 도시된 바와 같이, 화합물 3 및 NaOH 염을 이용하여 그래핀-그래핀 박리용 분산 안정제 복합체를 제조하면, 초기에는 모두 양호한 분산성을 보이지만(도 3의 A), 시간의 경과에 따라, 화합물 3을 이용한 그래핀-그래핀 분산 안정제 복합체는 우수한 분산 특성을 유지하는 반면, 그래핀-그래핀 박리용 분산 안정제(NaOH) 복합체는 분산 상태를 유지하지 못하고, 침천되었다(도 3의 B 및 C).In addition, the long term of the graphene-graphene peeling dispersion stabilizer (Compound (3)) complex and the graphene-graphene peeling dispersion stabilizer (NaOH) complex prepared using NaOH as a dispersion stabilizer for graphene peeling as a control A photo showing the stability is shown in FIG. 2. As shown in FIG. 2, when the dispersion stabilizer composite for graphene-graphene peeling was prepared using the compound 3 and the NaOH salt, all of them initially showed good dispersibility (A in FIG. 3), but over time. , Graphene-graphene dispersion stabilizer composite using compound 3 maintains excellent dispersion properties, whereas graphene-graphene dispersion stabilizer (NaOH) complex for separation did not maintain a dispersed state, and was precipitated (FIG. 3B). And C).
[실시예 9] 분산 안정제가 제거된 그래핀의 제조 Example 9 Preparation of Graphene with Dispersion Stabilizers Removed
실시예 8에서 얻은 그래핀-그래핀 박리용 분산 안정제 복합체 잉크를 감압하여 필터링한 후, 물로 수회 세척하여, 그래핀-그래핀 박리용 분산 안정제 복합체로부터 그래핀 박리용 분산 안정제를 제거함으로써, 그래핀을 제조하였다. 0 내지 200 ℃의 온도에서, 남은 파우더(분산 안정제가 제거된 그래핀)를 물, 에탄올, 아이소프로필알콜, 디메틸설폭사이드, 디클로로메탄, 이황화탄소, 아세톤, 클로로포름, 사염화탄소, 1,4-디옥산, 메틸아세테이트, 피리딘, m-크레졸, 페놀, 디메틸포름아미드, 디메틸아세트아미드, 황산, N-메틸-2-피롤리돈 및 피리딘으로 이루어진 군에서 선택된 적어도 1종의 용매에 용해시켜, 그래핀 용액을 제조하였다.The graphene-graphene peeling dispersion stabilizer composite ink obtained in Example 8 was filtered under reduced pressure, and then washed several times with water to remove the graphene peeling dispersion stabilizer from the graphene-graphene peeling dispersion stabilizer composite. Pins were prepared. At a temperature of 0 to 200 ° C., the remaining powder (graphene without dispersion stabilizer) was added to water, ethanol, isopropyl alcohol, dimethyl sulfoxide, dichloromethane, carbon disulfide, acetone, chloroform, carbon tetrachloride, 1,4-dioxane , Methyl acetate, pyridine, m-cresol, phenol, dimethylformamide, dimethylacetamide, sulfuric acid, N-methyl-2-pyrrolidone and pyridine Was prepared.
그래파이트, 그래핀 박리용 분산 안정제로서 NaOH를 사용하여 실시예 8 및 9와 동일한 방법으로 제조한 그래핀, 그래핀 박리용 분산 안정제로서 화합물 (3)의 화합물을 사용하여 실시예 8 및 9에 따라 제조한 그래핀의 전자주사현미경 사진(SEM: scanning electron microscope, Hitachi사 S-4800)을 각각 도 3의 A, B 및 C에 나타내었다. 도 3에 도시된 바와 같이, 분산 안정제로서 NaOH를 사용하면(도 3의 B), 그래파이트의 층간 간격을 약간 벌리지만, 분산 효과는 크지 않은 반면, 분산 안정제로서 화합물 3을 사용하면(도 3의 C), 그래파이트의 층과 층사이로 분산 안정제가 효과적으로 침투하여, 초음파 분쇄에 의해 그래파이트의 층간 사이를 효과적으로 벌리면서 그래핀이 제조된다.Graphene prepared in the same manner as in Examples 8 and 9 using NaOH as the dispersion stabilizer for graphite and graphene peeling, according to Examples 8 and 9 using the compound of Compound (3) as the dispersion stabilizer for graphene peeling. Electron scanning micrographs (SEM: scanning electron microscope, Hitachi S-4800) of the prepared graphene are shown in Figures A, B and C of Figure 3, respectively. As shown in FIG. 3, the use of NaOH as the dispersion stabilizer (FIG. 3B) widens the interlayer spacing of the graphite slightly, while the dispersion effect is not great, while using compound 3 as the dispersion stabilizer (FIG. 3). C), the dispersion stabilizer effectively penetrates between the layers and layers of graphite, and graphene is produced while effectively spreading the interlayers of graphite by ultrasonic grinding.

Claims (10)

  1. 하기 화학식 1의 구조를 가지는 그래핀 박리용 분산 안정제.Dispersion stabilizer for graphene peeling having a structure of formula (1).
    [화학식 1][Formula 1]
    Figure PCTKR2014005057-appb-I000034
    Figure PCTKR2014005057-appb-I000034
    상기 화학식 1에서, Ar은 탄소수 4 내지 100의 방향족기이고, M은 알칼리 금속이고, X는 알칼리 금속 M과 이온 결합할 수 있는 옥사이드기(-O-), 카르복실레이트기(-COO-), 설포네이트기(-SO3-), 설포닐기(-SO2-) 또는 포스파이트기(-PO3-)이고, Y는 -CH2- 또는 -CF2- 이고, n은 0 내지 10의 정수이고, m은 1 내지 3의 정수이고, Z는 존재하지 않거나, -CH2-, -NH-, -O-, -S-, -SO2-, -CO- 또는 -CF2-이고, E는 -H, -CH3, -SH, -OH, -NH2 또는 -CH2NH2이고, p는 1 내지 100의 정수이며, l은 1 또는 2이다. In Formula 1, Ar is an aromatic group having 4 to 100 carbon atoms, M is an alkali metal, X is an oxide group (-O-), carboxylate group (-COO-) capable of ion bonding with the alkali metal M , A sulfonate group (-SO 3- ), a sulfonyl group (-SO 2- ) or a phosphite group (-PO 3- ), Y is -CH 2 -or -CF 2- , n is 0 to 10 Integer, m is an integer from 1 to 3, Z is absent, or -CH 2- , -NH-, -O-, -S-, -SO 2- , -CO- or -CF 2- , E is -H, -CH 3 , -SH, -OH, -NH 2 or -CH 2 NH 2 , p is an integer from 1 to 100, l is 1 or 2.
  2. 청구항 1에 있어서, 상기 방향족기 Ar은 탄소수 6 내지 20의 방향족기로서,탄화수소 방향족기 또는 헤테로고리 방향족기를 하나 이상 포함하는 것인, 그래핀 박리용 분산 안정제.The dispersion stabilizer according to claim 1, wherein the aromatic group Ar is an aromatic group having 6 to 20 carbon atoms, and includes at least one hydrocarbon aromatic group or heterocyclic aromatic group.
  3. 청구항 1에 있어서, 상기 방향족기 Ar은The method according to claim 1, wherein the aromatic group Ar is
    Figure PCTKR2014005057-appb-I000035
    Figure PCTKR2014005057-appb-I000036
    Figure PCTKR2014005057-appb-I000037
    Figure PCTKR2014005057-appb-I000038
    Figure PCTKR2014005057-appb-I000039
    Figure PCTKR2014005057-appb-I000040
    Figure PCTKR2014005057-appb-I000041
    Figure PCTKR2014005057-appb-I000035
    Figure PCTKR2014005057-appb-I000036
    Figure PCTKR2014005057-appb-I000037
    Figure PCTKR2014005057-appb-I000038
    Figure PCTKR2014005057-appb-I000039
    Figure PCTKR2014005057-appb-I000040
    Figure PCTKR2014005057-appb-I000041
    (여기서, 굴곡선은 결합부를 나타내며, A는 각각 독립적으로 O, S, Se 또는 NH 이고, n은 0 내지 10의 정수이고, v와 w는 0 내지 1 의 정수이고, R은 각각 독립적으로, 수소원자, 탄소수 1 내지 50의 알킬기 또는 알콕시기, 탄소수 2 내지 50의 알켄기 또는 알킨기, 탄소수 4 내지 50의 아릴기 또는 헤테로아릴기이다.)로 이루어진 군으로부터 선택되는 것인, 그래핀 박리용 분산 안정제.(Wherein, the bend line represents a bond, A is each independently O, S, Se or NH, n is an integer of 0 to 10, v and w are an integer of 0 to 1, and R is each independently, Graphene peeling, selected from the group consisting of a hydrogen atom, an alkyl or alkoxy group having 1 to 50 carbon atoms, an alkene or alkyne group having 2 to 50 carbon atoms, an aryl group or a heteroaryl group having 4 to 50 carbon atoms. Dispersion stabilizer.
  4. 청구항 1에 있어서, 상기 그래핀 박리용 분산 안정제는 하기 화학식 1a 내지 1q로 표시되는 화합물로 이루어진 군으로부터 선택되는 것인, 그래핀 박리용 분산 안정제.The dispersion stabilizer according to claim 1, wherein the dispersion stabilizer for graphene peeling is selected from the group consisting of compounds represented by the following Chemical Formulas 1a to 1q.
    [화합물 1a] [Compound 1a]
    Figure PCTKR2014005057-appb-I000042
    Figure PCTKR2014005057-appb-I000042
    [화합물 1b][Compound 1b]
    Figure PCTKR2014005057-appb-I000043
    Figure PCTKR2014005057-appb-I000043
    [화합물 1c][Compound 1c]
    Figure PCTKR2014005057-appb-I000044
    Figure PCTKR2014005057-appb-I000044
    [화합물 1d][Compound 1d]
    Figure PCTKR2014005057-appb-I000045
    Figure PCTKR2014005057-appb-I000045
    [화합물 1e][Compound 1e]
    Figure PCTKR2014005057-appb-I000046
    Figure PCTKR2014005057-appb-I000046
    [화합물 1f][Compound 1f]
    Figure PCTKR2014005057-appb-I000047
    Figure PCTKR2014005057-appb-I000047
    [화합물 1g][Compound 1g]
    Figure PCTKR2014005057-appb-I000048
    Figure PCTKR2014005057-appb-I000048
    [화합물 1h][Compound 1h]
    Figure PCTKR2014005057-appb-I000049
    Figure PCTKR2014005057-appb-I000049
    [화합물 1i][Compound 1i]
    Figure PCTKR2014005057-appb-I000050
    Figure PCTKR2014005057-appb-I000050
    [화합물 1j][Compound 1j]
    Figure PCTKR2014005057-appb-I000051
    Figure PCTKR2014005057-appb-I000051
    [화합물 1k][Compound 1k]
    Figure PCTKR2014005057-appb-I000052
    Figure PCTKR2014005057-appb-I000052
    [화합물 1l][Compound 1l]
    Figure PCTKR2014005057-appb-I000053
    Figure PCTKR2014005057-appb-I000053
    [화합물 1m][Compound 1m]
    Figure PCTKR2014005057-appb-I000054
    Figure PCTKR2014005057-appb-I000054
    [화합물 1n][Compound 1n]
    Figure PCTKR2014005057-appb-I000055
    Figure PCTKR2014005057-appb-I000055
    [화합물 1o][Compound 1o]
    Figure PCTKR2014005057-appb-I000056
    Figure PCTKR2014005057-appb-I000056
    [화합물 1p][Compound 1p]
    Figure PCTKR2014005057-appb-I000057
    Figure PCTKR2014005057-appb-I000057
    [화합물 1q][Compound 1q]
    Figure PCTKR2014005057-appb-I000058
    Figure PCTKR2014005057-appb-I000058
  5. 그래핀의 층과 층 사이에 하기 화학식 1로 표시되는 그래핀 박리용 분산 안정제가 삽입되어 있는 그래핀-알칼리 금속염 복합체.Graphene-alkali metal salt composite having a graphene peeling dispersion stabilizer represented by the following Chemical Formula 1 interposed between the layer and the layer of graphene.
    [화학식 1][Formula 1]
    Figure PCTKR2014005057-appb-I000059
    Figure PCTKR2014005057-appb-I000059
    상기 화학식 1에서, Ar은 탄소수 4 내지 100의 방향족기이고, M은 알칼리 금속이고, X는 알칼리 금속 M과 이온 결합할 수 있는 옥사이드기(-O-), 카르복실레이트기(-COO-), 설포네이트기(-SO3-), 설포닐기(-SO2-) 또는 포스파이트기(-PO3-)이고, Y는 -CH2- 또는 -CF2- 이고, n은 0 내지 10의 정수이고, m은 1 내지 3의 정수이고, Z는 존재하지 않거나, -CH2-, -NH-, -O-, -S-, -SO2-, -CO- 또는 -CF2-이고, E는 -H, -CH3, -SH, -OH, -NH2 또는 -CH2NH2이고, p는 1 내지 100의 정수이며, l은 1 또는 2이다. In Formula 1, Ar is an aromatic group having 4 to 100 carbon atoms, M is an alkali metal, X is an oxide group (-O-), carboxylate group (-COO-) capable of ion bonding with the alkali metal M , A sulfonate group (-SO 3- ), a sulfonyl group (-SO 2- ) or a phosphite group (-PO 3- ), Y is -CH 2 -or -CF 2- , n is 0 to 10 Integer, m is an integer from 1 to 3, Z is absent, or -CH 2- , -NH-, -O-, -S-, -SO 2- , -CO- or -CF 2- , E is -H, -CH 3 , -SH, -OH, -NH 2 or -CH 2 NH 2 , p is an integer from 1 to 100, l is 1 or 2.
  6. 청구항 5에 있어서, 상기 그래핀 박리용 분산 안정제의 함량은, 상기 그래핀-알칼리 금속염 복합체의 전체 함량에 대하여 10 내지 90 중량%인 것인, 그래핀-알칼리 금속염 복합체.The graphene-alkali metal salt composite according to claim 5, wherein the content of the dispersion stabilizer for graphene peeling is 10 to 90 wt% with respect to the total content of the graphene-alkali metal salt composite.
  7. 용매의 존재 하에서, 하기 화학식 1로 표시되는 그래핀 박리용 분산 안정제와 그래파이트를 혼합하여, 그래파이트의 층과 층 사이에 그래핀 박리용 분산 안정제가 삽입되도록 함으로써, 그래파이트의 층간 간격을 증가시키는 단계;In the presence of a solvent, by mixing the graphene peeling dispersion stabilizer represented by the following formula (1) and graphite, the graphene peeling dispersion stabilizer is inserted between the layer and the layer of graphite, thereby increasing the interlayer spacing of the graphite;
    상기 그래핀 박리용 분산 안정제가 삽입된 그래파이트를 분산시켜, 그래핀의 층과층 사이에 그래핀 박리용 분산 안정제가 삽입된 그래핀-알칼리 금속염 복합체를 제조하는 단계; 및 Dispersing the graphite having the graphene peeling dispersion stabilizer inserted therein to prepare a graphene-alkali metal salt composite having a graphene peeling dispersion stabilizer inserted between the graphene layer and the layer; And
    용매로 상기 그래핀-알칼리 금속염 복합체를 세척하여, 그래핀-알칼리 금속염 복합체로부터 그래핀 박리용 분산 안정제를 제거하는 단계를 포함하는 그래핀의 제조방법.Washing the graphene-alkali metal salt complexes with a solvent to remove the graphene-alkali metal salt complex from the graphene peeling dispersion stabilizer comprising the step of removing the stabilizer.
    [화학식 1][Formula 1]
    Figure PCTKR2014005057-appb-I000060
    Figure PCTKR2014005057-appb-I000060
    상기 화학식 1에서, Ar은 탄소수 4 내지 100의 방향족기이고, M은 알칼리 금속이고, X는 알칼리 금속 M과 이온 결합할 수 있는 옥사이드기(-O-), 카르복실레이트기(-COO-), 설포네이트기(-SO3-), 설포닐기(-SO2-) 또는 포스파이트기(-PO3-)이고, Y는 -CH2- 또는 -CF2- 이고, n은 0 내지 10의 정수이고, m은 1 내지 3의 정수이고, Z는 존재하지 않거나, -CH2-, -NH-, -O-, -S-, -SO2-, -CO- 또는 -CF2-이고, E는 -H, -CH3, -SH, -OH, -NH2 또는 -CH2NH2이고, p는 1 내지 100의 정수이며, l은 1 또는 2이다.In Formula 1, Ar is an aromatic group having 4 to 100 carbon atoms, M is an alkali metal, X is an oxide group (-O-), carboxylate group (-COO-) capable of ion bonding with the alkali metal M , A sulfonate group (-SO 3- ), a sulfonyl group (-SO 2- ) or a phosphite group (-PO 3- ), Y is -CH 2 -or -CF 2- , n is 0 to 10 Integer, m is an integer from 1 to 3, Z is absent, or -CH 2- , -NH-, -O-, -S-, -SO 2- , -CO- or -CF 2- , E is -H, -CH 3 , -SH, -OH, -NH 2 or -CH 2 NH 2 , p is an integer from 1 to 100, l is 1 or 2.
  8. 청구항 7에 있어서, 상기 그래핀 박리용 분산 안정제의 사용량은, 상기 그래핀 박리용 분산 안정제 및 그래파이트의 전체 함량에 대하여 10 내지 90 중량%인 것인, 그래핀의 제조방법.The method according to claim 7, wherein the amount of the graphene peeling dispersion stabilizer is 10 to 90% by weight based on the total content of the graphene peeling dispersion stabilizer and graphite.
  9. 청구항 7에 있어서, 상기 용매는 물, 에탄올, 이소프로필알콜, 디메틸설폭사이드, 디클로로메탄, 이황화탄소, 아세톤, 클로로포름, 사염화탄소, 1,4-디옥산, 메틸아세테이트, 피리딘, m-크레졸, 페놀, 디메틸포름아미드, 디메틸아세트아미드, 황산, N-메틸-2-피롤리돈 및 피리딘으로 이루어진 군에서 선택된 하나 이상의 용매인 것인, 그래핀의 제조방법.The method of claim 7, wherein the solvent is water, ethanol, isopropyl alcohol, dimethyl sulfoxide, dichloromethane, carbon disulfide, acetone, chloroform, carbon tetrachloride, 1,4-dioxane, methyl acetate, pyridine, m-cresol, phenol, It is at least one solvent selected from the group consisting of dimethylformamide, dimethylacetamide, sulfuric acid, N-methyl-2-pyrrolidone and pyridine, a method for producing graphene.
  10. 청구항 7에 있어서, 상기 분산 단계는, 그래핀 박리용 분산 안정제가 삽입된 그래파이트 용액을 교반하거나 초음파 분쇄하여 수행되는 것인, 그래핀의 제조방법.The method of claim 7, wherein the dispersing is performed by stirring or ultrasonically grinding the graphite solution in which the dispersion stabilizer for graphene peeling is inserted.
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