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WO2010128660A1 - Agent de dispersion/solubilisation de nanotubes de carbone - Google Patents

Agent de dispersion/solubilisation de nanotubes de carbone Download PDF

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Publication number
WO2010128660A1
WO2010128660A1 PCT/JP2010/057760 JP2010057760W WO2010128660A1 WO 2010128660 A1 WO2010128660 A1 WO 2010128660A1 JP 2010057760 W JP2010057760 W JP 2010057760W WO 2010128660 A1 WO2010128660 A1 WO 2010128660A1
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carbon nanotube
carbon
solubilizing agent
branched structure
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Japanese (ja)
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直也 西村
将大 飛田
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Nissan Chemical Corp
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Nissan Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40—Nitrogen atoms
    • C07D251/54—Three nitrogen atoms
    • C07D251/70—Other substituted melamines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • C01B32/158—Carbon nanotubes
    • C01B32/168—After-treatment
    • C01B32/174—Derivatisation; Solubilisation; Dispersion in solvents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40—Nitrogen atoms
    • C07D251/42—One nitrogen atom
    • C07D251/44—One nitrogen atom with halogen atoms attached to the two other ring carbon atoms
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0273—Polyamines containing heterocyclic moieties in the main chain
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • C08G73/0644—Poly(1,3,5)triazines
    • 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
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/002—Dendritic macromolecules
    • C08G83/005—Hyperbranched macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic

Definitions

  • the present invention relates to a carbon nanotube dispersing / solubilizing agent, and more specifically to a carbon nanotube dispersing / solubilizing agent comprising a highly branched polymer containing a triazine ring as a repeating unit.
  • Carbon nanotubes (hereinafter sometimes abbreviated as CNTs) are being studied as a useful material for nanotechnology, and their potential for application in a wide range of fields. There are many applications such as a method using a single CNT itself, such as a transistor or a probe for a microscope, an electron emission electrode, a fuel cell electrode, or a conductive composite in which CNTs are dispersed. The CNTs are roughly divided into methods that are used as a bulk.
  • a method for modifying the surface of CNT for example, there is a method of adding CNT to an aqueous solution containing a surfactant such as sodium dodecyl sulfonate (see Patent Document 1: Japanese Patent Laid-Open No. 6-228824).
  • a surfactant such as sodium dodecyl sulfonate
  • CNT is added to a solvent containing poly-m-phenylene vinylene-co-dioctoxy-p-phenylene vinylene
  • Patent Document 2 Japanese Patent Laid-Open No. 2000-44216
  • this polymer has an incomplete conjugated system, and in this case also, the conductivity of CNT Will not be damaged.
  • Non-patent Document 1 Science, vol. 282, 1998.
  • the ⁇ -conjugated system constituting the CNT is easily destroyed by chemical modification, and in this case, the original characteristics of the CNT are impaired.
  • the dispersibility of the CNT is improved to some extent, but another problem arises that the original characteristics of the CNT such as high conductivity are impaired.
  • Patent Document 2 shows that a polymer is attached around one CNT.
  • the technique of this document is to disperse to a certain extent and then aggregate and precipitate to capture CNT. It is not intended to store CNTs in an isolated and dissolved state over a long period of time.
  • Patent Document 1 by using a conjugated polymer as a solubilizer (dispersant), the surface of the CNT is covered with the conjugated polymer. As a result, the CNT is uniformly dispersed in the resin. It has been reported that the electrical conductivity of is exhibited.
  • a conjugated polymer used as a dispersant has a characteristic that it has an advantage in the case of utilizing electrical conductivity and semiconductor characteristics because a conjugated structure is developed.
  • Patent Document 1 only a linear polymer is disclosed as a conjugated polymer, and knowledge about a highly branched polymer is not clarified.
  • Non-patent Document 2 Carbon, vol. 41, pp. 797-809, 2003
  • its application range is limited because it is water-soluble.
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2008-245678
  • Patent Document 4 Japanese Patent Laid-Open No. 2005-75661
  • Patent Document 5 JP-A-2005-162877
  • Patent Document 6 JP-A-2008-24522
  • the polymer used as the dispersant is a linear polymer, and the knowledge about the hyperbranched polymer has not been clarified.
  • Non-patent Document 3 Proceedings of the 56th Annual Meeting of the Society of Polymer Science, vol. 56, No. 1, p. 1463, 2007.
  • the hyperbranched polymer is a polymer having a branch in the skeleton, such as a star polymer, a dendrimer classified as a dendritic (dendritic) polymer, or a hyperbranched polymer.
  • These hyperbranched polymers have a string-like shape, while conventional polymers generally have a branched shape. Therefore, by using this as a dispersant, a linear polymer can be obtained.
  • Non-Patent Document 3 in order to maintain the isolated dispersion state of CNTs over a long period of time, heat treatment is necessary in addition to mechanical treatment. The solubilizing ability was not so high.
  • the present invention has been made in view of such circumstances, and an object of the present invention is to provide a carbon nanotube solubilizing agent / dispersing agent that can dissolve carbon nanotubes in an organic solvent or the like in a single size up to a single size.
  • the present inventors have found that a highly branched polymer containing a triazine ring as a repeating unit is excellent in the ability to disperse and dissolve carbon nanotubes, and that this highly branched polymer is made of carbon.
  • the present inventors When used as a nanotube dispersing / solubilizing agent, the present inventors have found that carbon nanotubes (at least a part thereof) can be isolated and dissolved up to their single size, thereby completing the present invention.
  • the present invention Dispersion / solubilization of carbon nanotubes comprising a highly branched polymer containing a triazine ring as a repeating unit and having a weight average molecular weight of 1,000 to 4,000,000 as measured by polystyrene by gel permeation chromatography Agent, 2. 1 is a carbon nanotube dispersion / solubilizing agent represented by the following formula (1): (In the formula, R and R ′ represent a hydrogen atom or an alkyl group which may have a branched structure having 1 to 10 carbon atoms, and Ar represents an aryl group which may have a substituent. ) 3.
  • R 1 to R 80 are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfone group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or a carbon number of 1 Represents an alkoxy group which may have a branched structure of ⁇ 10, W 1 and W 2 are each independently a single bond, CR 81 R 82 (R 81 and R 82 are each independently hydrogen; An atom or an alkyl group which may have a branched structure having 1 to 10 carbon atoms (however, they may be combined to form a ring), C ⁇ O, O, S , SO, SO 2 , or NR 83 (R 83 represents a hydrogen atom or an alkyl group which may have a branched structure having 1 to 10 carbon atoms), and
  • FIG. 1 is a diagram showing a 1 H-NMR chart of a polymer compound [1] obtained in Example 1.
  • FIG. 3 is a diagram showing a 1 H-NMR chart of a polymer compound [2] obtained in Example 2.
  • FIG. 3 is a diagram showing a 1 H-NMR chart of the polymer compound [3] obtained in Example 3.
  • 4 is a diagram showing a 1 H-NMR chart of a polymer compound [4] obtained in Example 4.
  • FIG. FIG. 6 is a diagram showing a 1 H-NMR chart of the polymer compound [4] obtained in Example 5.
  • FIG. 6 is a diagram showing a 1 H-NMR chart of the polymer compound [4] obtained in Example 6.
  • FIG. 4 is a graph showing an ultraviolet-visible-near infrared absorption spectrum of the polymer compound [4] / SWCNT dispersion obtained in Example 11.
  • FIG. 4 is a graph showing an ultraviolet-visible-near infrared absorption spectrum of the polymer compound [4] / SWCNT dispersion obtained in Example 12.
  • 2 is a diagram showing an ultraviolet-visible-near infrared absorption spectrum of a PVP / SWCNT dispersion obtained in Comparative Example 1.
  • the carbon nanotube dispersing / solubilizing agent according to the present invention contains a triazine ring as a repeating unit, and has a weight average molecular weight of 1,000 to 4,000,000 measured in terms of polystyrene by gel permeation chromatography (hereinafter referred to as GPC).
  • GPC gel permeation chromatography
  • 000 is a highly branched polymer.
  • the hyperbranched polymer containing the triazine ring as a repeating unit is excellent in stability and exhibits excellent hole transport properties, and therefore is expected to be applied to organic EL.
  • an appropriate dopant for example, an anion such as perchlorate ion, iodine ion, bromine ion, sulfate ion, it can be expected to be used as a conductive polymer.
  • the solubilizing ability of the carbon nanotubes may be remarkably lowered or the solubilizing ability may not be exhibited, and exceeds 4,000,000.
  • the solubilizing ability of the carbon nanotubes may be remarkably lowered or the solubilizing ability may not be exhibited, and exceeds 4,000,000.
  • Highly branched polymers having a weight average molecular weight of 1,000 to 2,000,000 are more preferred.
  • the repeating unit containing a triazine ring is not particularly limited, but those represented by the following formula (1) are preferred in the present invention.
  • the alkyl group which may have a branched structure having 1 to 10 carbon atoms is not particularly limited, and examples thereof include a methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n- Butyl, isobutyl, s-butyl, t-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl, 2 -Methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-
  • the aryl group which may have a substituent is not particularly limited.
  • the following formula It is preferable to use at least one of the compounds represented by (2) to (12), and since it provides a highly branched polymer having more excellent ability to dissolve (disperse) carbon nanotubes, in particular, the formulas (4), (6) and (12 An aryl group represented by
  • R 1 to R 80 are each independently a hydrogen atom, a halogen atom, a carboxyl group, a sulfone group, or an alkyl group optionally having a branched structure having 1 to 10 carbon atoms. Or an alkoxy group which may have a branched structure having 1 to 10 carbon atoms.
  • W 1 and W 2 are each independently a single bond, CR 81 R 82 (R 81 and R 82 are each independently a hydrogen atom or a branched structure having 1 to 10 carbon atoms.
  • An alkyl group which may be combined to form a ring), C ⁇ O, O, S, SO, SO 2 , or NR 83 (R 83 is hydrogen) Represents an atom or an alkyl group which may have a branched structure having 1 to 10 carbon atoms.
  • Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Examples of the alkyl group which may have a branched structure having 1 to 10 carbon atoms include the same ones as described above.
  • Examples of the ring formed by R 81 and R 82 together include a cyclopentane ring and a cyclohexane ring.
  • Examples of the alkoxy group which may have a branched structure having 1 to 10 carbon atoms include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, s-butoxy group and t-butoxy group. And n-pentoxy group.
  • X 1 and X 2 each independently represent a single bond, an alkylene group which may have a branched structure having 1 to 10 carbon atoms, or a group represented by the formula (13).
  • R 84 to R 87 are independently of each other a hydrogen atom, a halogen atom, a carboxyl group, a sulfone group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, or a branched group having 1 to 10 carbon atoms.
  • An alkoxy group which may have a structure is represented, and Y 1 and Y 2 each independently represent an alkylene group which may have a single bond or a branched structure having 1 to 10 carbon atoms. Examples of the halogen atom, the alkyl group and the alkoxy group which may have a branched structure having 1 to 10 carbon atoms are the same as those described above.
  • alkylene group that may have a branched structure having 1 to 10 carbon atoms include a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, and a pentamethylene group.
  • aryl group represented by the above formulas (2) to (12) include those represented by the following formula, but are not limited thereto.
  • repeating unit containing a triazine ring in the hyperbranched polymer suitably used in the present invention include those represented by the following formulas (14) to (16), but are not limited thereto. .
  • a hyperbranched polymer having a repeating structure (15 ′) is obtained by reacting a cyanuric halide (17) and a bisaminophenylfluorene compound (18) having an amino group in a suitable organic solvent. It can obtain by making it react.
  • the hyperbranched polymer having a repeating structure (15 ′) is obtained by using cyanuric halide (17) and a bisaminophenylfluorene compound (18) having an amino group in a suitable organic solvent.
  • the amount of each raw material charged is arbitrary as long as the target polymer can be obtained, but the diamino compound (18) 0.01 relative to 1 equivalent of the halogenated cyanuric compound (17). ⁇ 10 equivalents are preferred.
  • organic solvent various solvents usually used in this kind of reaction can be used, for example, tetrahydrofuran, dioxane, N, N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, tetramethylurea, Hexamethylphosphoramide, N, N-dimethylacetamide, N-methyl-2-piperidone, N, N-dimethylethyleneurea, N, N, N ′, N′-tetramethylmalonic acid amide, N-methylcaprolactam, N-acetylpyrrolidine, N, N-diethylacetamide, N-ethyl-2-pyrrolidone, N, N-dimethylpropionic acid amide, N, N-dimethylisobutyramide, N-methylformamide, N, N'-dimethylpropylene urea Amide solvents such as, and mixed solvents thereof Among these, N, N-dimethylformamide, dimethyl s thereof,
  • the reaction temperature may be appropriately set in the range from the melting point of the solvent to be used to the boiling point of the solvent, but is preferably about 0 to 150 ° C., preferably 60 to 100 ° C. is more preferable.
  • the reaction temperature may be appropriately set in the range from the melting point of the solvent to be used to the boiling point of the solvent, but is preferably about ⁇ 10 to 50 ° C., and preferably ⁇ 10 to 10 ° C. More preferred.
  • various commonly used bases can be used.
  • this base include potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, sodium bicarbonate, sodium ethoxide, sodium acetate, triethylamine, lithium carbonate, lithium hydroxide, lithium oxide, potassium acetate, magnesium oxide.
  • the amount of the base added is preferably 1 to 100 equivalents, more preferably 1 to 10 equivalents, relative to 1 equivalent of the halogenated cyanuric compound (17).
  • These bases may be used as an aqueous solution.
  • the raw material components do not remain, but some raw materials remain unless the effects of the present invention are impaired. It may be.
  • the product can be easily purified by a reprecipitation method or the like.
  • At least one of the halogen atoms of the terminal triazine ring is substituted with an alkyl group, an aralkyl group, an aryl group, an alkylamino group, an alkoxysilyl group-containing alkylamino group, an aralkylamino group, an arylamino group, You may cap by an alkoxy group, an aralkyloxy group, an aryloxy group, an ester group, etc.
  • the alkyl group and alkoxy group are the same as those described above.
  • Specific examples of the ester group include a methoxycarbonyl group and an ethoxycarbonyl group.
  • aryl group examples include phenyl group, o-chlorophenyl group, m-chlorophenyl group, p-chlorophenyl group, o-fluorophenyl group, p-fluorophenyl group, o-methoxyphenyl group, p-methoxy group.
  • aralkyl group examples include benzyl group, p-methylphenylmethyl group, m-methylphenylmethyl group, o-ethylphenylmethyl group, m-ethylphenylmethyl group, p-ethylphenylmethyl group, 2-propylphenyl group.
  • examples include a methyl group, 4-isopropylphenylmethyl group, 4-isobutylphenylmethyl group, ⁇ -naphthylmethyl group, and the like.
  • alkylamino group examples include methylamino group, ethylamino group, n-propylamino group, isopropylamino group, n-butylamino group, isobutylamino group, s-butylamino group, t-butylamino group, n -Pentylamino group, 1-methyl-n-butylamino group, 2-methyl-n-butylamino group, 3-methyl-n-butylamino group, 1,1-dimethyl-n-propylamino group, 1,2 -Dimethyl-n-propylamino group, 2,2-dimethyl-n-propylamino group, 1-ethyl-n-propylamino group, n-hexylamino group, 1-methyl-n-pentylamino group, 2-methyl -N-pentylamino group, 3-methyl-n-pentylamino group, 4-methyl-n-pentyl
  • arylamino group examples include phenylamino group, methoxycarbonylphenylamino group, ethoxycarbonylphenylamino group, naphthylamino group, methoxycarbonylnaphthylamino group, ethoxycarbonylnaphthylamino group, anthranylamino group, pyrenylamino group, biphenylamino. Group, terphenylamino group, fluorenylamino group and the like.
  • the alkoxysilyl group-containing alkylamino group may be any of a monoalkoxysilyl group-containing alkylamino group, a dialkoxysilyl group-containing alkylamino group, or a trialkoxysilyl group-containing alkylamino group.
  • aryloxy group examples include a phenoxy group, a naphthoxy group, an anthranyloxy group, a pyrenyloxy group, a biphenyloxy group, a terphenyloxy group, and a fluorenyloxy group.
  • aralkyloxy group examples include benzyloxy group, p-methylphenylmethyloxy group, m-methylphenylmethyloxy group, o-ethylphenylmethyloxy group, m-ethylphenylmethyloxy group, p-ethylphenylmethyl group. Examples include an oxy group, 2-propylphenylmethyloxy group, 4-isopropylphenylmethyloxy group, 4-isobutylphenylmethyloxy group, ⁇ -naphthylmethyloxy group, and the like.
  • the carbon nanotube-containing composition according to the present invention contains the carbon nanotube dispersing / solubilizing agent described above and carbon nanotubes.
  • Carbon nanotubes (CNT) are produced by an arc discharge method, a chemical vapor deposition method (CVD method), a laser ablation method, or the like.
  • the CNT used in the present invention was obtained by any method. May be.
  • single-walled CNT hereinafter referred to as SWCNT in which one carbon film (graphene sheet) is wound in a cylindrical shape and two-layered CNT in which two graphene sheets are wound in a concentric shape.
  • DWCNT multi-layer CNT
  • MWCNT multi-layer CNT
  • SWCNT, DWCNT, and MWCNT are each a single unit, Or a combination of several can be used.
  • the electrical characteristics of CNTs vary from metallic to semiconducting depending on how the graphene sheet is wound (helicality, chirality).
  • the triazine hyperbranched polymer of the present invention as a solubilizer (dispersant) for CNTs, there is a possibility that a composition in which CNTs having a specific chirality are selectively dissolved can be obtained. .
  • the composition of the present invention may further contain an organic solvent having the ability to dissolve the dispersing / solubilizing agent (highly branched polymer).
  • organic solvents include ether compounds such as THF and diethyl ether; halogenated hydrocarbons such as methylene chloride and chloroform; amide compounds such as dimethylformamide and N-methylpyrrolidone (NMP); acetone, methyl ethyl ketone, methyl Ketone compounds such as isobutyl ketone and cyclohexanone; alcohols such as methanol, ethanol, isopropanol and propanol; aliphatic hydrocarbons such as normal heptane, normal hexane and cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene Among them, THF, chloroform, NMP, and cyclohexane are preferable.
  • the said organic solvent can be used individually by 1 type or in mixture of 2 or more types.
  • THF and NMP are preferable from the viewpoint that the ratio of isolated dissolution of CNTs can be improved, and an NMP single solvent or a solvent containing the NMP that can also improve the film forming property of the composition is preferable.
  • the preparation method of the composition of the present invention is arbitrary, and when the dispersion / solubilizer (polymer) is in a liquid state, the dispersion / solubilizer and CNT are mixed as appropriate, and the dispersion / solubilizer is solid. In some cases, it can be prepared by melting it and then mixing it with CNTs. When an organic solvent is used, a composition may be prepared by mixing the dispersing / solubilizing agent, CNT, and organic solvent in an arbitrary order. At this time, it is preferable to solubilize a mixture comprising a dispersing / solubilizing agent, CNT, and an organic solvent, and this treatment can further improve the ratio of isolated dissolution of CNT.
  • solubilization treatment examples include wet treatment using a ball mill, bead mill, jet mill, etc., and ultrasonic treatment using a bath type or probe type sonicator. However, in consideration of treatment efficiency, ultrasonic treatment is preferable. .
  • the time for the solubilization treatment is arbitrary, but is preferably about 5 minutes to 10 hours, more preferably about 30 minutes to 5 hours. In addition, you may heat-process suitably before the said solubilization process.
  • the mixing ratio of the solubilizer and CNT in the composition of the present invention can be about 1000: 1 to 1: 100 by mass ratio.
  • the concentration of the solubilizer in the composition using the organic solvent is not particularly limited as long as it is a concentration capable of solubilizing the CNT in the organic solvent. About 0.001 to 20% by mass is preferable, and about 0.005 to 10% by mass is more preferable.
  • the concentration of CNTs in this composition is arbitrary as long as at least a part of the CNTs is isolated and dissolved (solubilized). In the present invention, the concentration of CNTs is about 0.0001 to 10% by mass in the composition. The amount is preferably about 0.001 to 5% by mass. In the composition of the present invention prepared as described above, it is presumed that the solubilizer is attached to the surface of CNT to form a complex.
  • composition of the present invention can be mixed and mixed with a general-purpose synthetic resin soluble in the various organic solvents described above.
  • a general-purpose synthetic resin include polyolefin resins such as polyethylene (PE), polypropylene (PP), ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), and polystyrene (PS).
  • Styrene resins such as high impact polystyrene (HIPS), acrylonitrile-styrene copolymer (AS), acrylonitrile-butadiene-styrene copolymer (ABS), vinyl chloride resin, polyurethane resin, phenol resin, epoxy resin, amino Examples thereof include resins and unsaturated polyester resins.
  • HIPS high impact polystyrene
  • AS acrylonitrile-styrene copolymer
  • ABS acrylonitrile-butadiene-styrene copolymer
  • vinyl chloride resin polyurethane resin
  • phenol resin phenol resin
  • epoxy resin epoxy resin
  • amino examples thereof include resins and unsaturated polyester resins.
  • general-purpose synthetic engineering plastics include polyamide resins, polycarbonate resins, polyphenylene ether resins, modified polyphenylene ether resins, polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), polyacetal resins, polysulfone resins, and polyphenylene sulfide resins. And polyimide resin.
  • the CNT-containing composition of the present invention is formed by coating on a suitable substrate such as PET, glass, ITO or the like by an appropriate method such as a casting method, a spin coating method, a bar coating method, a roll coating method, or a dip coating method. Is possible.
  • the obtained thin film can be suitably used for an antistatic film utilizing the metallic properties of carbon nanotubes, a conductive material such as a transparent electrode, a photoelectric conversion device utilizing the semiconductor properties, an electroluminescent device, and the like.
  • Naphthalene-1,5-diamine (6.33 g, 0.02 mol) was dissolved in 220 mL of tetrahydrofuran (THF) in a 500 mL four-necked flask equipped with a reflux tower and cooled to 3 ° C. with an ice bath. After cooling, 2,4,6-trichloro-1,3,5-triazine (3.68 g, 0.02 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 30 mL of THF was slowly added dropwise, followed by stirring for 10 minutes. did. The flask was transferred from the ice bath to an oil bath, the temperature was raised to 70 ° C., and a 10% aqueous potassium carbonate solution was added dropwise.
  • THF tetrahydrofuran
  • the obtained polymer compound [1] is a compound having a structural unit represented by the formula (1), and the weight average molecular weight Mw measured in terms of polystyrene by GPC is 1,500, and the polydispersity Mw (weight) The average molecular weight / Mn (number average molecular weight) was 1.13.
  • Example 2 Synthesis was performed in the same manner as in Example 1 except that naphthalene-1,5-diamine used in Example 1 was replaced with 9,9-bis (4-aminophenyl) fluorene (manufactured by Aldrich). Molecular compound [2] (1.74 g) was obtained. The measurement result of the 1 H-NMR spectrum of the polymer compound [2] is shown in FIG. The obtained polymer compound [2] is a compound having a structural unit represented by the formula (1).
  • the weight average molecular weight Mw measured in terms of polystyrene by GPC is 2,700, and the polydispersity Mw (weight average) Molecular weight) / Mn (number average molecular weight) was 1.40.
  • the target polymer compound [3] (1.68 g) was synthesized in the same manner as in Example 1 except that naphthalene-1,5-diamine used in Example 1 was replaced with 3,4-diaminobenzophenone. Got.
  • the measurement result of the 1 H-NMR spectrum of the polymer compound [3] is shown in FIG.
  • the obtained polymer compound [3] is a compound having a structural unit represented by the formula (1), and has a weight average molecular weight Mw measured in terms of polystyrene by GPC of 2,100, polydispersity Mw (weight).
  • the average molecular weight / Mn number average molecular weight
  • the obtained HB-TFA90 is a compound having a structural unit represented by the formula (1), the weight average molecular weight Mw measured by polystyrene conversion by GPC is 9,200, and the polydispersity Mw / Mn is 2. 33.
  • Example 5 Synthesis of polymer compound [4] with terminal aniline caps having different molecular weights 9,9-bis (4-aminophenyl) fluorene (6.93 g, 0.020 mol), 1,3,5-trichloro- Polymer synthesized using 2,4,6-triazine (3.69 g, 0.020 mol) and aniline (3.36 g, 0.036 mol) in the same manner as in Example 4 and having a molecular weight different from that of Example 4. 10.2 g of compound [4] (hereinafter abbreviated as HB-TFA42) was obtained. The measurement result of 1 H-NMR spectrum of HB-TFA42 is shown in FIG.
  • the obtained HB-TFA56 is a compound having a structural unit represented by the formula (1), the weight average molecular weight Mw measured by polystyrene conversion by GPC is 4,200, and the polydispersity Mw / Mn is 1. 96.
  • HB-TFA20 is a compound having the structural unit represented by the formula (1), and the weight average molecular weight Mw measured by polystyrene conversion by GPC is 2,900, and the polydispersity Mw / Mn is 1.68. It was.
  • Example 7 Preparation of SWCNT dispersion 1 mg of the polymer compound [1] obtained in Example 1 was dissolved in 5 mL of NMP to prepare an NMP solution, and SWCNT (Unydim, Inc. product name Unydim (registered) Trademark Carbon Nanotubes) 0.5 mg was added.
  • SWCNT Unydim, Inc. product name Unydim (registered) Trademark Carbon Nanotubes
  • Ultrasonic treatment was performed at room temperature for 1 hour using a bath-type ultrasonic irradiation device (Fine FU-6H type, manufactured by Tokyo Glass Instrument Co., Ltd.), and further centrifuged at 10,000 G for 1 hour (room temperature) (compact high-speed cooling centrifuge) Machine, SRX-201 manufactured by Tommy Seiko Co., Ltd.) to obtain a black transparent SWCNT-containing solution as a supernatant.
  • a bath-type ultrasonic irradiation device Fluor FU-6H type, manufactured by Tokyo Glass Instrument Co., Ltd.
  • SRX-201 compact high-speed cooling centrifuge
  • Example 8 Preparation of SWCNT dispersion A black transparent SWCNT-containing solution was obtained in the same manner as in Example 7 except that the polymer compound [2] obtained in Example 2 was used.
  • Example 9 Preparation of SWCNT dispersion A black transparent SWCNT-containing solution was obtained in the same manner as in Example 7 except that the polymer compound [3] obtained in Example 3 was used.
  • Example 11 Preparation of SWCNT dispersion A black transparent SWCNT-containing solution was obtained in the same manner as in Example 7 except that the polymer compound [4] (HB-TFA42) obtained in Example 5 was used. .

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Abstract

La présente invention concerne un agent de dispersion/solubilisation de nanotubes de carbone qui est composé d'un polymère hyper-ramifié qui contient un cycle triazine représenté, par exemple, par la formule (14), (15) ou (16) comme unité récurrente et qui a un poids moléculaire moyen en poids de 1 000 à 4 000 000 par rapport au polystyrène tel que déterminé par chromatographie d'exclusion diffusion. Comme le polymère hyper-ramifié a un excellent pouvoir de dissolution des nanotubes de carbone, une composition dans laquelle des nanotubes de carbone sont dissous de manière isolée peut être obtenue en utilisant le polymère hyper-ramifié comme agent de solubilisation.
PCT/JP2010/057760 2009-05-07 2010-05-06 Agent de dispersion/solubilisation de nanotubes de carbone Ceased WO2010128660A1 (fr)

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JP2012031372A (ja) * 2010-07-09 2012-02-16 Tosoh Corp 新規アリールアミンデンドリマー状化合物、その製造方法およびその用途
WO2012060286A1 (fr) * 2010-11-02 2012-05-10 日産化学工業株式会社 Composition filmogène
JP2013036021A (ja) * 2011-07-08 2013-02-21 Ube Industries Ltd ポリアミック酸からなるカーボンナノチューブ分散剤
CN103059272A (zh) * 2013-01-17 2013-04-24 山东轻工业学院 一种超支化共轭聚合物及其制备方法与应用
JP2013129584A (ja) * 2011-12-22 2013-07-04 Osaka Gas Co Ltd 亜鉛化合物被覆炭素材及びその製造方法、並びに該亜鉛化合物被覆炭素材を用いた複合材
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JP2015096625A (ja) * 2015-02-13 2015-05-21 日産化学工業株式会社 高分岐ポリマー
JP2015227253A (ja) * 2014-05-30 2015-12-17 国立大学法人 熊本大学 グラフェン分散液及びグラフェンの製造方法
WO2016117531A1 (fr) * 2015-01-23 2016-07-28 日産化学工業株式会社 Procédé de purification d'un polymère contenant un cycle de triazine
WO2017138547A1 (fr) * 2016-02-09 2017-08-17 日産化学工業株式会社 Polymère contenant un cycle triazine et composition le contenant

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JP7002517B2 (ja) * 2019-11-15 2022-01-20 花王株式会社 半導体型単層カーボンナノチューブ分散液の製造方法
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JP2012031372A (ja) * 2010-07-09 2012-02-16 Tosoh Corp 新規アリールアミンデンドリマー状化合物、その製造方法およびその用途
US9243110B2 (en) * 2010-11-01 2016-01-26 Nissan Chemical Industries, Ltd. Triazine ring-containing polymer and film-forming composition containing same
US20130289203A1 (en) * 2010-11-01 2013-10-31 Nissan Chemical Industries, Ltd. Triazine ring-containing polymer and film-forming composition containing same
US9469729B2 (en) 2010-11-01 2016-10-18 Nissan Chemical Industries, Ltd. Triazine ring-containing polymer and film-forming composition containing same
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US20130281620A1 (en) * 2010-11-02 2013-10-24 Nissan Chemical Industries, Ltd. Film-forming composition
JPWO2012060286A1 (ja) * 2010-11-02 2014-05-12 日産化学工業株式会社 膜形成用組成物
JP2013036021A (ja) * 2011-07-08 2013-02-21 Ube Industries Ltd ポリアミック酸からなるカーボンナノチューブ分散剤
JP2013129584A (ja) * 2011-12-22 2013-07-04 Osaka Gas Co Ltd 亜鉛化合物被覆炭素材及びその製造方法、並びに該亜鉛化合物被覆炭素材を用いた複合材
CN103059272A (zh) * 2013-01-17 2013-04-24 山东轻工业学院 一种超支化共轭聚合物及其制备方法与应用
JPWO2015016316A1 (ja) * 2013-07-31 2017-03-02 日産化学工業株式会社 炭素材料分散膜形成用組成物
WO2015016316A1 (fr) 2013-07-31 2015-02-05 日産化学工業株式会社 Composition de formation de film dans lequel une matière carbonée est dispersée
JP2015227253A (ja) * 2014-05-30 2015-12-17 国立大学法人 熊本大学 グラフェン分散液及びグラフェンの製造方法
WO2016117531A1 (fr) * 2015-01-23 2016-07-28 日産化学工業株式会社 Procédé de purification d'un polymère contenant un cycle de triazine
JPWO2016117531A1 (ja) * 2015-01-23 2017-11-02 日産化学工業株式会社 トリアジン環含有ポリマーの精製方法
JP2015096625A (ja) * 2015-02-13 2015-05-21 日産化学工業株式会社 高分岐ポリマー
WO2017138547A1 (fr) * 2016-02-09 2017-08-17 日産化学工業株式会社 Polymère contenant un cycle triazine et composition le contenant
KR20180104323A (ko) * 2016-02-09 2018-09-20 닛산 가가쿠 가부시키가이샤 트라이아진환 함유 중합체 및 그것을 포함하는 조성물
JPWO2017138547A1 (ja) * 2016-02-09 2018-11-29 日産化学株式会社 トリアジン環含有重合体およびそれを含む組成物
CN109071807A (zh) * 2016-02-09 2018-12-21 日产化学株式会社 含有三嗪环的聚合物和包含该聚合物的组合物
US10928729B2 (en) 2016-02-09 2021-02-23 Nissan Chemical Corporation Triazine-ring-containing polymer and composition including same
CN109071807B (zh) * 2016-02-09 2021-07-06 日产化学株式会社 含有三嗪环的聚合物和包含该聚合物的组合物
KR102641678B1 (ko) 2016-02-09 2024-02-28 닛산 가가쿠 가부시키가이샤 트라이아진환 함유 중합체 및 그것을 포함하는 조성물

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