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WO2011071295A2 - Composite nanotubes de carbone/liquide ionique polymère, et composite nanotubes de carbone/polymère conducteur préparé à l'aide de ce dernier - Google Patents

Composite nanotubes de carbone/liquide ionique polymère, et composite nanotubes de carbone/polymère conducteur préparé à l'aide de ce dernier Download PDF

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WO2011071295A2
WO2011071295A2 PCT/KR2010/008709 KR2010008709W WO2011071295A2 WO 2011071295 A2 WO2011071295 A2 WO 2011071295A2 KR 2010008709 W KR2010008709 W KR 2010008709W WO 2011071295 A2 WO2011071295 A2 WO 2011071295A2
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carbon nanotube
ionic liquid
polymer
conductive polymer
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WO2011071295A3 (fr
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서광석
김종은
김태영
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
    • H—ELECTRICITY
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    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/142—Side-chains containing oxygen
    • C08G2261/1424—Side-chains containing oxygen containing ether groups, including alkoxy
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/43—Chemical oxidative coupling reactions, e.g. with FeCl3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/51—Charge transport
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/70—Post-treatment
    • C08G2261/79—Post-treatment doping
    • C08G2261/794—Post-treatment doping with polymeric dopants
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/12—Polymers characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2439/00—Characterised by the use 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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes

Definitions

  • the present invention relates to a carbon nanotube-polymer ionic liquid composite and a carbon nanotube-conductive polymer composite prepared using the same, and more particularly, to a carbon nanotube-polymer by introducing a polymer ionic liquid onto a surface of the carbon nanotube.
  • the present invention relates to a carbon nanotube-conductive polymer composite for preparing an ionic liquid composite, and using the same as a template polymerization derivative of a conductive polymer to produce a conductive polymer, and a method of manufacturing the same.
  • Carbon nanotubes which are known to have excellent electrical conductivity, have both metallic and semiconducting properties, depending on the angle and structure of the graphite sheet winding.
  • single-walled carbon nanotubes SWNT
  • multi-walled carbon nanotubes MWN
  • the carbon nanotubes have very high electrical conductivity, and many attempts have been made to apply them to the display industry such as transparent electrode materials.
  • a method of mixing conductive polymers together may be used when preparing a coating solution including carbon nanotubes.
  • the most commonly used conductive polymer is poly (3,4-ethylenedioxythiophene) (PEDOT) / poly (styrenesulfonate) (PSS) complex, which is a conductive polymer of H. C. Starck, Germany.
  • PES poly (styrenesulfonate)
  • the carbon nanotubes when preparing a conductive coating solution containing carbon nanotubes, the carbon nanotubes must be uniformly dispersed in a suitable solvent such as water or alcohol, which causes many problems.
  • the conductive coating solution using carbon nanotubes is mainly manufactured in the form of a composite of carbon nanotubes and a general insulating binder or a conductive polymer, wherein the binder is mixed by the strong van der Waals force of the carbon nanotubes.
  • it is easy to agglomerate in the coating solution it becomes difficult to have a high electrical conductivity when agglomeration occurs, and the light transmittance is reduced because the size of the carbon nanotubes also increases to a micrometer size.
  • the present invention is to improve the dispersibility of the carbon nanotubes in the production of a conductive coating liquid in the form of a mixture of carbon nanotubes and a conductive polymer while minimizing the decrease in electrical conductivity or manufactured through the same It is an object to provide a carbon nanotube-conductive polymer composite.
  • the present invention in order to provide a carbon nanotube-conductive polymer composite having good solvent dispersion, a method of attaching a polymer ionic liquid to the surface of the carbon nanotube and a composite polymer obtained by synthesizing a conductive polymer using the template polymer derivative as a simple ion Finally, the present invention provides a carbon nanotube-conductive polymer composite and a solution having good dispersibility in an organic solvent.
  • the carbon nanotube-polymer ionic liquid complex in which the polymer ionic liquid is introduced to the surface of the carbon nanotubes acts as a dopant, so that the conductive polymer is polymerized on the surface of the carbon nanotubes.
  • the present invention provides a carbon nanotube-polymer ionic liquid complex made by combining the polymer ionic liquid to introduce a functional group on the surface of the carbon nanotube and to surround the carbon nanotube through the chemical bond with the functional group,
  • the carbon nanotube-polymer ionic liquid composite can be used for the production of carbon nanotube-conductive polymer composite.
  • a functional group such as -COOH group is introduced through the acid treatment on the surface of the carbon nanotube, and then the polymer ionic liquid is introduced to the carbon nanotube wall by binding the ionic liquid monomer to the -COOH group on the wall of the carbon nanotube.
  • the carbon nanotube-polymer ionic liquid composite thus prepared is used as a template polymerization derivative, and the carbon nanotube-conductive polymer composite is synthesized by mixing together a monomer for synthesizing a conductive polymer and an oxidizing agent.
  • the ionic liquid monomer has a functional group capable of polymerizing in a polymer form such as vinyl group, allyl group, acrylate group, methacrylate group, and alkylimidazolium or alkylpyridinium, alkylpyrrolidinium, alkylpyridazinium, Alkylpyrimidinium, Alkylpyrazinium, Alkylpyrazolium, Alkylpiperidinium, Alkylpiperidinium, Alkylthiazolium, Alkyloxazolium, Alkyltriazolium, Alkylmorpholinium, Alkylphosphonium, Alkyl ammonium and their available, regardless of its kind as a monomer a derivative of the shape, and Br as a counter anion of the cation of the ionic liquid -, Cl -, I -, BF 4 -, PF 6 -, ClO 4 -, nO 3 -, AlCl 4 -, Al 2 Cl 7 -,
  • the carbon nanotubes used may be used regardless of the type.
  • all kinds of carbon nanotubes may be used, such as single-walled carbon nanotubes, multi-walled carbon nanotubes, purified carbon nanotubes, unrefined carbon nanotubes, and carbon nanotubes produced by different methods. .
  • Monomers for synthesizing conductive polymers include pyrrole, aniline, thiophene, 3,4-ethylenedioxythiophene, 3,4-alkylenedioxythiophene, 3,4-dialkylthiophene, 3,4-dialkoxyti
  • a material containing offen and 3,4-cycloalkylthiophene and the like can be used, considering the light transmittance of the coating solution, it is most effective to use 3,4-ethylenedioxythiophene (EDOT).
  • the conductive polymer is synthesized on the surface of the carbon nanotube by overcoming the phase separation problem of the conductive polymer and the carbon nanotube component, which is the biggest disadvantage of the simple mixture of the two components in the preparation of the conductive polymer and the carbon nanotube mixture.
  • Complexes in the form can be prepared.
  • this composite can obtain the effect of improving the dispersibility to the organic solvent through a simple ion exchange.
  • conductive material carbon black, surfactants, conductive polymers can be produced a conductive coating material stable electrical properties. It can be applied to flat panel display products, flexible displays and solar cells using carbon nanotubes and conductive polymers, which are relatively inexpensive and easy to supply and replace expensive indium-tin oxide, and can be used for hole transport layers or hole injection of organic light emitting devices. The great advantage is that it can be used as a layer.
  • FIG. 1 is a view showing a method for synthesizing a carbon nanotube-polymer ionic liquid composite according to the present invention.
  • FIG. 2 is a view showing an example of ion exchange through the lithium salt of the carbon nanotube-polymer ionic liquid composite according to the present invention.
  • FIG. 3 is a diagram illustrating a method of synthesizing a carbon nanotube-conductive polymer composite as an example of the carbon nanotube-conductive polymer composite of the present invention.
  • Figure 4 is a view showing a transmission electron micrograph of the carbon nanotube-polymer ionic liquid composite made of the present invention.
  • FIG. 5 is a diagram showing a transmission electron micrograph of a carbon nanotube-PEDOT composite using a carbon nanotube-polymer ionic liquid composite according to the present invention.
  • the present invention can be described by dividing into a step of making a carbon nanotube-polymer ionic liquid composite and a step of synthesizing a carbon nanotube-conductive polymer composite prepared using the same.
  • the carbon nanotube-polymer ionic liquid composite preparation is divided into a surface treatment of carbon nanotubes and a step of introducing a polymer ionic liquid onto the surface of the carbon nanotubes.
  • the polymer ionic liquid may be prepared by synthesizing a conductive polymer on the surface of the carbon nanotubes using a material (carbon nanotube-polymer ionic liquid complex) introduced into the surface of the carbon nanotubes as a template polymer and a dispersant. have.
  • the present invention as described above can be described in largely divided into three steps, first step for the purification and surface treatment of carbon nanotubes, and then a second step for introducing a polymer ionic liquid to the surface of the carbon nanotubes And a third step of synthesizing a conductive polymer (eg, poly (3,4-ethylenedioxythiophene): PEDOT) on the surface of the carbon nanotubes using the material produced in the second step as a template polymer and a dispersant. .
  • a conductive polymer eg, poly (3,4-ethylenedioxythiophene): PEDOT
  • FIG. 1 is a view showing a method for producing a carbon nanotube-polymer ionic liquid composite
  • FIG. 2 is a method for synthesizing a carbon nanotube-conductive polymer composite using a carbon nanotube-polymer ionic liquid composite according to the present invention
  • FIG. 3 is a diagram illustrating a process of performing ion exchange to disperse the prepared carbon nanotube-conductive polymer composite in an organic solvent.
  • FIG. 1 shows the second step below and FIG. 2 shows the reaction of the third step.
  • the carbon nanotube purification method used in the present invention and the step of introducing a functional group such as -COOH group on the surface will be described.
  • the purification process of the first step may be omitted.
  • Carbon nanotubes manufactured by the electric discharge method or other methods have a purity of about 60%, and have high electrical conductivity because impurities such as amorphous carbon, fullerene, and metal catalysts coexist in addition to the carbon nanotubes.
  • impurities such as amorphous carbon, fullerene, and metal catalysts coexist in addition to the carbon nanotubes.
  • the method for removing such impurities is not particularly limited, and the purity of the purified carbon nanotubes is preferably 90% or more.
  • the purity of the carbon nanotubes is less than 90%, the electrical conductivity is lowered due to various impurities, so in the present invention, it is preferable to use those having a purity of 90% or more.
  • the method for purifying carbon nanotubes in the present invention is not significantly different from those described in various documents such as Korean Patent Publication No. 10-2005-0097711, US Patent No. 6878361, and the like.
  • the carbon nanotubes are oxidized at a high temperature of 300-800 o C for 10-60 minutes to remove amorphous carbon, which is then refluxed in a solution of nitric acid, sulfuric acid, or hydrochloric acid or sonicated for 10-120 minutes to react with the metal catalyst.
  • Carbon nanotubes with more than 90% purity can be obtained by further removing amorphous carbon, filtering and drying.
  • the compound used at this time is a carboxyl group, an amine group, a nitrate group, a cyan group, It is preferable to use a substance capable of bonding an acryl group, an amide group, an ethylenoxide group, or the like. More preferably, carbon nanotubes having functional groups such as carboxyl groups (hereinafter referred to as carbon nanotubes-COOH) are added to a solution of nitric acid, sulfuric acid, hydrochloric acid alone or mixed acid thereof, refluxed at room temperature to 200 ° C. or sonicated for 1 to 48 hours. To be prepared).
  • the carbon nanotube-COOH prepared in the first step is dispersed in a solvent with a polymerizable monomer as a polymer ionic liquid, and then a polymerization initiator is added to the surface of the carbon nanotube by adding a reaction initiator. do.
  • the ionic liquid monomers that can be used in this step are not particularly limited but are preferably 1-vinyl-3-ethylimidazolium bromide and their modified ionic liquids structurally vinyl, allyl, acrylate, methacrylate, etc.
  • their molecular weight is also not very limited, but if the molecular weight is 500,000 grams / mole or more, the carbon nanotubes weaken the electrical conductivity, and if the molecular weight is less than 5,000 grams / mole, the molecular weight is 5,000-500,000 grams.
  • Polymeric ionic liquids / mole are suitable.
  • the amount of the carbon nanotube-COOH introduced with the functional group prepared in the first step is not limited, but preferably 0.01-20 parts by weight based on 100 parts by weight of the total solution to be used.
  • the solvent may be prepared by dispersing the prepared carbon nanotube-COOH in water or an alcohol solvent such as methanol, ethanol, or chloroform alone or in a mixed solvent thereof, and then 1 to 1000 times by weight of the carbon nanotube. After stirring by adding 1-vinyl-3-ethylimidazolium bromide, 2 parts by weight of azobis (isobutylnitrile), a polymerization initiator, is added to 100 parts by weight of the polymer ionic liquid monomer, Stir for 12-72 hours in a nitrogen atmosphere.
  • azobis isobutylnitrile
  • the thickness of the polymer ionic liquid covering the surface of the carbon nanotubes varies depending on the degree of washing.
  • the polymer ionic liquid composite thus obtained, the polymer ionic liquid (PIL (Br): anion: bromine ions) is bonded to the single-walled carbon nanotube (SWNT) as shown in FIG. 4.
  • This step will be described the step of synthesizing the conductive polymer in the carbon nanotube-polymer ionic liquid composite dispersion prepared in the second step.
  • the reaction of this step may be conventionally used a method of making an organic solvent dispersible conductive polymer.
  • the carbon nanotube-polymer ionic liquid composite prepared by the above-described method is dispersed in 0.001-20 parts by weight based on 100 parts by weight of the total solution.
  • the method of dispersing is not limited, but preferably ultrasonic waves may be used. In this case, if the content is less than 0.001 parts by weight, the solid content is too low. If the content is more than 20 parts by weight, the solid content is too high, making dispersion difficult.
  • dispersing solvents are not limited but depend on the counter anion of the polymer ionic liquid, for example, water or methanol, ethanol, n-propyl alcohol, isopropyl alcohol, normal butanol, isobutanol, hexanol, Ethylene glycol, glycerol, benzene, chlorobenzene, nitromethane, toluene, ethyl acetate, hexane, cyclohexane, 2-methoxyethanol, 2-butoxyethanol, 2-ethoxyethanol, xylene, chloroform, tetrahydrofuran, Dimethylformamide, methylethylketone, N-methyl-2-pyrrolidone, 2-pyrrolidone, N-vinyl-2-pyrrolidone, N-methylformamide, dimethylsulfoxide, acetone, n-butyro Solvents such as lactone may be used alone or in combination
  • Monomers for the synthesis of conductive polymers include 3,4-ethylenedioxythiophene or other thiophene-based monomers, such as 3,4-dialkylthiophene, 3,4-dialkoxythiophene and 3,4-cycloalkylthiophene.
  • the monomer or modified monomer derived from these may be used.
  • other types of conductive polymer synthesis monomers such as pyrrole and aniline may be used. If the light transmittance is good, 3,4-ethylenedioxythiophene or other light transmittance monomer may be used.
  • a monomer, an oxidizing agent and a carbon nanotube-polymer ionic liquid are mixed at a predetermined ratio. Induce synthesis after.
  • the monomer used is 3,4-ethylenedioxythiophene
  • the oxidizing agent is water as the solvent
  • ammonium peroxydisulfate (APS), potassium persulfate (KPS), etc. can be used, and other organic solvents are used.
  • Fe (ClO 4 ) 3 or the like which can be dissolved in an organic solvent can be used.
  • the conductive polymer monomer used can be adjusted from 0.1 to 1,000 parts by weight relative to 100 parts by weight of the carbon nanotube-polymer ionic liquid composite.
  • the conductive polymer is carbon nanotube-polymer ionic liquid.
  • the conductive polymer monomer introduced as shown in FIG. 5 surrounds the surface of the carbon nanotube-polymer ionic liquid.
  • the solution obtained by this method is hereinafter referred to as carbon nanotube-polymer ionic liquid-conductive polymer solution or carbon nanotube-conductive polymer dispersion.
  • the carbon nanotube-conductive polymer solution may be subjected to a separate washing process or may be used as it is.
  • An example of the carbon nanotube-PEDOT composite thus obtained is shown in the transmission electron micrograph of FIG. 5, wherein poly (3,4-ethylendioxythiophene) (PEDOT) is bonded to a single-wall carbon nanotube (SWNT) as shown in the photograph. Will be.
  • the carbon nanotube-conductive polymer solution prepared by the above method is a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diethyl ether, dipropyl ether, dibutyl ether, butyl ethyl ether, tetra Ether solvents such as hydrofuran, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, alcohol ether solvents such as N-methyl-2-pyridyridone and 2-pyrily Amide solvents such as dinon, N-methylformamide, N, N-dimethylformamide, sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, sulfone solvents such as diethyl sulfone and tetramethylene sulfone, acet
  • Carboxylic ester solvents such as ester solvents, ethyl acetate, butyl acetate, aromatic hydrocarbon solvents such as benzene, ethylbenzene, chlorobenzene, toluene, xylene, aliphatic hydrocarbon solvents such as hexane, heptane, cyclohexane, chloroform, tetrachloro Halogenated hydrocarbon solvents such as ethylene, carbon tetrachloride, dichloromethane, dichloroethane, propylene carbonate, ethylene carbonate, dimethyl carbonate, dibutyl carbonate, ethyl methyl carbonate, dibutyl carbonate, nitromethane, nitrobenzene, etc. Dispersion is possible by mixing the above.
  • the content of the carbon nanotube-conductive polymer is less than 0.001 part by weight.
  • the content of the conductive polymer component is too low and the conductivity is too low to be disadvantageous. If the content is 20 parts by weight or more, the solid content is too high, rather the dispersibility is poor and the coating film formation by the coating is disadvantageous.
  • the conductive coating liquid containing the carbon nanotube-conductive polymer prepared by the above method may be used as it is, and binders and other additives may be further added to improve electrical conductivity and improve coating properties.
  • the carbon nanotube-polymer ionic liquid composite aqueous dispersion solution prepared by the above method was diluted with water to 0.1 weight percent, and lithium (trifluoromethanesulfonyl) imide (LiTFSI) was dissolved in water to perform ion exchange.
  • LiTFSI lithium (trifluoromethanesulfonyl) imide
  • the anion of the polymer ionic liquid is substituted from Br ⁇ to TFSI ⁇ .
  • the substituted carbon nanotube-polymer ionic liquid composite is precipitated and the precipitated carbon nanotube-polymer ionic liquid composite is obtained, and then the polymer ionic liquid of the carbon nanotube-polymer ionic liquid composite: ethylene
  • dioxythiophene 0.2 g: 10 g
  • FeClO 4 was diluted with propylene carbonate in 10% by weight with 1.2 molar ratio of ethylenedioxythiophene and proceeded for 48 hours at room temperature while slowly dropping.
  • the unreacted compound was filtered with a polycarbonate filter of 0.2 ⁇ m, washed 10 times with water, ethanol and methanol and dried in a vacuum oven for 24 hours to obtain a carbon nanotube-PEDOT composite.
  • 0.1 g of the prepared carbon nanotube-PEDOT composite was mixed with 9.9 g of acetonitrile, dispersed for 20 minutes by ultrasound, and coated on a polyester film. The surface resistance was measured at 5 ⁇ 10 5 ohms / area. The prepared solution lasted more than a month without precipitation.
  • the carbon nanotube-COOH prepared in Example 1 was mixed with dimethylformamide at 0.1 wt% and sonicated for 20 minutes to prepare a carbon nanotube-COOH dispersion.
  • the surface resistance was measured by 3 ⁇ 10 4 ohms / area. The solution produced precipitated after 3 hours.
  • Example 2 After mixing the carbon nanotube-COOH prepared in Example 1 to 0.1% by weight in water, and sonicated for 20 minutes to prepare a carbon nanotube-COOH dispersion.
  • the 10 g of the dispersed solution was mixed with 1 g of a solution in which the polyethylene dioxythiophene / polystyrene sulfonate complex was dispersed at 1.3 weight percent and 1 g of isopropyl alcohol to prepare a carbon nanotube-conductive polymer mixture.
  • the surface resistance was measured to 1 ⁇ 10 5 ohms / area.
  • the prepared solution was phase separated after one week and precipitation occurred.
  • the mixture is placed in water so that the content of the polymer ionic liquid complex is 0.5% by weight, and then the mixture is added with a polymer ionic liquid: ethylenedioxythiophene: ammoniumperoxydisulfate (1: 1: 1.2 molar ratio) for 24 hours at room temperature. Proceed. After the completion of the reaction, the unreacted compound was washed 10 times with water, ethanol and methanol, filtered through a 0.2 ⁇ m polycarbonate filter and dried for 24 hours in a vacuum oven to obtain a polymer ionic liquid-PEDOT composite.
  • ethylenedioxythiophene ammoniumperoxydisulfate (1: 1: 1.2 molar ratio
  • TFSI trifluoro methane sulfonyl imide
  • Polymeric ionic liquid of the carbon nanotube-polymer ionic liquid composite Ethylenedioxythiophene (0.2 g: 20 g) was added thereto, followed by stirring for 10 minutes, and FeClO 4 was propylene carbonate at 10% by weight in a 1.2 molar ratio of ethylenedioxythiophene. It is the same as in Example 1 except that the synthesis is carried out for 48 hours at room temperature while slowly diluting to. When applied to the polyester film, the surface resistance was measured to 7 ⁇ 10 5 ohms / area. The prepared solution lasted more than a month without precipitation.
  • Polymeric ionic liquid of carbon nanotube-polymeric ionic liquid composite Ethylenedioxythiophene (0.2 g: 5 g) was added thereto, followed by stirring for 10 minutes, and FeClO 4 was propylene carbonate at 10% by weight in 1.2 molar ratio of ethylenedioxythiophene. It was the same as in Example 1 except that the mixture was diluted to and slowly dropped to proceed for 48 hours at room temperature. When applied to the polyester film, the surface resistance was measured to 3 ⁇ 10 5 ohms / area. The prepared solution lasted more than a month without precipitation.
  • the surface resistance of the carbon nanotube-conductive polymer composite was changed according to the synthesis ratio, and the surface of the carbon nanotube-COOH was wrapped with a polymer ionic liquid, followed by carbon nanotube- It can be seen that the conductive polymer composite is advantageous in terms of electrical conductivity than the conductive polymer and the polymer ionic liquid composite. In addition, it was confirmed that the dispersion stability of the solution is poor when the carbon nanotube-COOH simply mixed with the conductive polymer composite.
  • the conductive coating solution prepared by introducing a polymer ionic liquid on the surface of the modified carbon nanotube which is the technique of the present invention, by chemical bonding and synthesizing the conductive polymer on the carbon nanotube wall using the template as a conductive polymer and carbon nano It is possible to overcome the phase separation problem between the conductive polymer and the carbon nanotube component, which is the biggest disadvantage of the simple mixture of the two components in the preparation of the tube mixture, and has an effect of improving the dispersibility of a solvent such as a polar organic solvent of the composite. It can be seen.
  • the carbon nanotube-conductive polymer composite of the present invention can be used in the display industry such as transparent electrode materials. In addition, it can be applied to a flexible display, a solar cell, etc., can be used as a hole transport layer or a hole injection layer of the organic light emitting device.

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Abstract

La présente invention concerne une technologie de préparation d'un composite nanotubes de carbone/liquide ionique par l'application d'un liquide ionique polymère sur les surfaces de nanotubes de carbone, et un procédé de préparation d'un composite nanotubes de carbone/polymère conducteur présentant de bonnes caractéristiques de dispersion par utilisation du composite nanotubes de carbone/liquide ionique comme dérivé de polymérisation formant matrice et d'un dopant dans un procédé de synthèse de polymère conducteur. Selon le concept technique de la présente invention, dans un procédé de préparation d'un mélange d'un polymère conducteur et de nanotubes de carbone, le problème de séparation de phases entre le polymère conducteur et les nanotubes de carbone, qui peut être le principal inconvénient d'un mélange simple à deux composants, peut être surmonté. De plus, la dispersion dans un solvant organique peut être largement améliorée par une méthode simple d'échange d'ions.
PCT/KR2010/008709 2009-12-07 2010-12-07 Composite nanotubes de carbone/liquide ionique polymère, et composite nanotubes de carbone/polymère conducteur préparé à l'aide de ce dernier Ceased WO2011071295A2 (fr)

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US10134995B2 (en) 2016-01-29 2018-11-20 University Of Kentucky Research Foundation Water processable N-type organic semiconductor
US10295367B2 (en) 2012-10-02 2019-05-21 Japan Science And Technology Agency Signal detection device and signal detection method
WO2024002397A1 (fr) * 2022-06-29 2024-01-04 Centrum organické chemie, s.r.o. Composite hybride pour la préparation de couches conductrices minces, procédé de préparation associé et couche conductrice mince préparée à partir du composite hybride
CN117467226A (zh) * 2023-12-28 2024-01-30 上海拜安传感技术有限公司 组合物、传感薄膜、传感器、制备方法及应用

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US20070101824A1 (en) * 2005-06-10 2007-05-10 Board Of Trustees Of Michigan State University Method for producing compositions of nanoparticles on solid surfaces
KR100801595B1 (ko) 2006-11-09 2008-02-05 제일모직주식회사 탄소나노튜브 복합체 조성물 및 이를 이용한 투명 전도성필름
KR100945568B1 (ko) 2007-09-18 2010-03-09 이화여자대학교 산학협력단 금속 나노입자가 고정화된 이온성 액체-탄소나노튜브 지지체의 복합체 및 이의 제조방법

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CN104583118B (zh) * 2012-08-23 2018-02-16 独立行政法人科学技术振兴机构 碳纳米材料、组合物、导电性材料及其制造方法
US10295367B2 (en) 2012-10-02 2019-05-21 Japan Science And Technology Agency Signal detection device and signal detection method
US10134995B2 (en) 2016-01-29 2018-11-20 University Of Kentucky Research Foundation Water processable N-type organic semiconductor
WO2024002397A1 (fr) * 2022-06-29 2024-01-04 Centrum organické chemie, s.r.o. Composite hybride pour la préparation de couches conductrices minces, procédé de préparation associé et couche conductrice mince préparée à partir du composite hybride
CN117467226A (zh) * 2023-12-28 2024-01-30 上海拜安传感技术有限公司 组合物、传感薄膜、传感器、制备方法及应用
CN117467226B (zh) * 2023-12-28 2024-03-19 上海拜安传感技术有限公司 组合物、传感薄膜、传感器、制备方法及应用

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