WO2018168867A1 - Dispersants à base d'oxazoline pour matériaux carbonés et matériaux composites carbonés dans lesquels ceux-ci sont utilisés - Google Patents

Dispersants à base d'oxazoline pour matériaux carbonés et matériaux composites carbonés dans lesquels ceux-ci sont utilisés Download PDF

Info

Publication number
WO2018168867A1
WO2018168867A1 PCT/JP2018/009780 JP2018009780W WO2018168867A1 WO 2018168867 A1 WO2018168867 A1 WO 2018168867A1 JP 2018009780 W JP2018009780 W JP 2018009780W WO 2018168867 A1 WO2018168867 A1 WO 2018168867A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbon
carbon material
copolymer
dispersion
materials
Prior art date
Application number
PCT/JP2018/009780
Other languages
English (en)
Japanese (ja)
Inventor
明理 平田
学士 丸山
後藤晃哉
高橋辰宏
雅彦 瀧
Original Assignee
Ｋｊケミカルズ株式会社
国立大学法人山形大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=63522291&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2018168867(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Ｋｊケミカルズ株式会社, 国立大学法人山形大学 filed Critical Ｋｊケミカルズ株式会社
Priority to JP2019502033A priority Critical patent/JP6617229B2/ja
Publication of WO2018168867A1 publication Critical patent/WO2018168867A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
    • 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
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—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
    • C08F226/06—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 by a heterocyclic ring containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/27—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of alkylpolyalkylene glycol esters of unsaturated carboxylic acids

Definitions

  • the present invention relates to a dispersion accelerator for carbon materials, an adhesion improver, a sizing agent for fibrous carbon materials, a surface-modified carbon material and a carbon composite material modified to these.
  • carbon materials are generally composed of carbon atoms, and show various forms and functions depending on the bonding mode and aggregation mode of carbon atoms. Among them, graphite, fullerene, carbon nanotube, carbon nanohorn, carbon nanobrush, fullerene , Graphene, carbon fiber (carbon fiber), activated carbon, diamond-like carbon, carbon black, etc.
  • reinforcing materials aircraft, automobiles, sports equipment, tires
  • catalyst carriers electrode materials (dry cells, fuel cells), Widely used as molecular sieve membranes, adsorbents for water purification, deodorants, cosmetics, shampoos, face masks, surface coats, electromagnetic shielding materials, heat dissipation materials, pharmaceuticals (adsorbents).
  • Non-patent Document 1 Since carbon materials have a 6-membered ring structure of carbon atoms and are not polar, they have poor wettability and dispersibility for general-purpose materials and have insufficient adhesion to matrix resins.
  • Surface hydrophilization treatment has been carried out by conventional methods. For example, by introducing an amino group on the surface of carbon fiber, the adhesiveness with the epoxy resin is improved (Non-patent Document 1), and the epoxy resin and 1,3-phenylenebis-2- It was reported that fuzzing could be prevented by attaching oxazoline (Patent Document 1), and further, a fiber sizing agent containing an acrylic resin and an aqueous medium was reported from a polyoxyalkylene group and an amide group or cyano group. (Patent Document 2).
  • Non-patent Document 2 oxygen-containing functional groups such as hydroxyl groups are introduced to the surface by using strong acid treatment at high temperatures or ultraviolet irradiation in the presence of hydrogen peroxide using diamond powder and fine particles, and in general solvents such as water and alcohol.
  • Patent Documents 3 and 4 A method for producing a diamond that can be stably dispersed has been disclosed.
  • Carbon nanotubes have a fibrous structure having a diameter of several to several tens of nanometers and a length of several to several hundreds of micrometers, and have been actively studied as a typical nano-sized carbon material in recent years.
  • CNT has a very large aspect, so it exhibits excellent electrical, thermal and mechanical properties, but it is very easy to get entangled, and not only for general-purpose resin and metal, but also for similar carbon matrix
  • wettability, interfacial adhesion and adhesion are poor, and a high-performance composite material utilizing the characteristics of CNTs has not yet been obtained.
  • Non-Patent Document 3 describes a method in which silicon is sublimated in a vacuum high temperature (1400 ° C.) state, vapor-deposited on the CNT surface, a SiC layer is formed on the CNT surface by a high-temperature reaction, and an alloy serving as a base material is adhered by improving wettability. Proposed.
  • heat treatment 2000 ° C.
  • surface treatment is performed using hydrogen peroxide and ultraviolet rays, and then a resin composite material using polycarbonate as a base material is produced.
  • a method to improve the mechanical strength of the steel was proposed.
  • these CNT surface modification methods are carried out under vacuum or ultra-high temperature conditions, special equipment is required, and it cannot be said that they are industrial production methods from the viewpoint of equipment and cost. .
  • Patent Document 5 in the first step, a polymer having an oxazoline group in the side chain, a thermoplastic resin and a modified thermoplastic resin are melt-kneaded at 180 ° C. for 10 minutes by a twin-screw extruder, and a resin composition for filler dispersion is obtained. I got a thing.
  • the filler-dispersed resin composition obtained in the first step and the CNT filler are melt-kneaded again at 180 ° C. for 10 minutes using a twin-screw extruder to obtain a thermoplastic resin exhibiting conductivity.
  • thermoplastic resin but is not compatible with a high melting point or heat decomposable thermoplastic resin, a polymer having an oxazoline group in the side chain or a modified thermoplastic resin, or a thermosetting resin.
  • metal-based materials, carbon materials, and the like cannot be melt-kneaded, a filler-dispersing resin composition cannot be obtained, and the composite with CNT is not as expected.
  • the present invention does not require special dispersion and surface treatment techniques and equipment, and does not impair the original characteristics of the carbon material, and can facilitate imparting hydrophilicity and adhesion to the surface of various carbon materials by a simple method. It is an object of the present invention to provide a sizing agent, an adhesion improver, and a sizing agent for a fibrous carbon material, and to provide a carbon material (surface modified carbon material) whose surface is modified using the adhesion improver.
  • the adhesion improver and the surface-modified carbon material can be produced in high yield by industrial means, and by using these, a suitable carbon composite material having specific performance can be obtained by reacting with various solid materials. The subject is to provide.
  • the present inventors have found that a co-polymer containing a 2-oxazoline monomer (a) and a low Tg (glass transition temperature) vinyl monomer (b) as structural units. It has been found that the polymer exhibits unique properties for promoting the dispersion of carbon materials into other types of materials, improving the surface adhesion of carbon materials, and imparting the convergence of fibrous carbon materials. Moreover, the surface modification carbon material to which adhesiveness was provided was able to be acquired by making it react with various carbon materials using the adhesive improvement agent which consists of the said copolymer.
  • the present invention (1) 2-oxazoline monomer (a) 5 to 98 mol% and homopolymer glass transition temperature (Tg) -100 to 80 ° C. vinyl monomer (b) 2 to 95 mol% as structural units Containing copolymer (A), (2) The vinyl monomer (b) having a glass transition temperature (Tg) of the homopolymer of ⁇ 100 to 80 ° C.
  • the copolymer (A) of the present invention comprises a vinyl monomer (b) 2 to 5 having a 2-oxazoline monomer (a) of 5 to 98 mol% and a homopolymer having a glass transition temperature (Tg) of ⁇ 100 to 80 ° C. 95 mol% is contained as a structural unit. If the contents of (a) and (b) are within this range, the resulting copolymer (A) is a homopolymer of 2-oxazoline monomer, a vinyl monomer having a Tg of ⁇ 100 to 80 ° C.
  • the copolymer (A) of the present invention has a flexibility derived from a low Tg (-100 ° C. to 80 ° C.) vinyl monomer and an oxazoline group highly reactive with a carboxylic acid or a phenolic hydroxyl group on the surface of a carbon material. Even a carbon material having a large aspect such as CNT can be easily dispersed in water, an organic solvent, or a plastic resin, and re-aggregation is suppressed, so that a stable dispersed state can be maintained. In addition, excellent convergence can be provided for the fibrous carbon material.
  • the adhesion improver By using the copolymer (A) of the present invention as an adhesion improver and reacting with various carbon materials under mild conditions, the adhesion improver is uniformly covered on the surface of the carbon material, and the carbon material is removed. A surface-modified carbon material that is not separated can be easily produced by an industrial technique.
  • various solid materials for example, the same or different carbon materials, carboxyl groups that can react with oxazoline groups, phenolic hydroxyl groups, acid anhydrides
  • a solid thermoplastic resin having one or more functional groups selected from the group consisting of functional groups, epoxy groups, thiol groups, amine groups and amides It is possible to easily obtain a carbon composite material having.
  • the copolymer (A) of the present invention is characterized in that it contains a 2-oxazoline monomer (a) and a vinyl monomer (b) having a Tg of ⁇ 100 to 70 ° C. as structural units. Since the vinyl monomer (b) has a low Tg and high flexibility, it exhibits the effect of promoting the dispersion of the carbon material in organic or inorganic liquids or solids in other types of materials, and has an oxazoline group. Has a high reactivity with the carboxylic acid or phenolic hydroxyl group on the surface of the carbon material, and can prevent re-aggregation of the carbon material once dispersed, thereby providing a stable dispersion effect.
  • the copolymer (A) contains (a) and (b) in a specific blending ratio, that is, (a) contains 5 to 98 mol% and (b) contains 2 to 95 mol%. Is preferred. If the content of (a) is less than 5 mol%, there is a risk that reaggregation after dispersion may not be sufficiently suppressed in a carbon material having a very large aspect such as CNT, and when used as an adhesion improver. Since it is difficult to cover the entire surface of the carbon material uniformly and uniformly, there is a possibility that a sufficient effect of improving adhesiveness cannot be obtained.
  • the copolymer of the present invention, and the dispersion accelerator, adhesion improver and sizing agent of the fibrous carbon material obtained therefrom are the reaggregation suppressing effect and the adhesion improving effect due to the reactivity of the oxazoline group of (a), (b) Therefore, it is considered that excellent dispersibility, dispersion stability, adhesion improvement, and focusing effect can be maximized.
  • the copolymer (A) is not only uniformly arranged on the surface of the carbon material, but also strongly bonded to the carbon material through a chemical bond formed by a chemical reaction, and reacts with the hydrophilicity on the surface of the carbon material. Therefore, the most specific effect that can be provided as the adhesion improver of the present invention is that it easily adheres to the surface of the carbon material and does not leave semipermanently.
  • 2-Oxazoline monomers (a) are 2-vinyl-2-oxazoline, 4-methyl-2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, 4-ethyl-2-vinyl- 2-oxazoline, 5-ethyl-2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-2-oxazoline, 4,4-diethyl-2-vinyl-2-oxazoline, 4,5-dimethyl- 2-vinyl-2-oxazoline, 4,5-diethyl-2-vinyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 4-methyl-2-isopropenyl-2-oxazoline, 5-methyl-2- Isopropenyl-2-oxazoline, 4-ethyl-2-isopropenyl-2-oxazoline, 5-ethyl-2-isopropenyl-2-oxazoline, , 4-Dimethyl-2
  • 2-vinyl-2-oxazoline 2-isopropenyl, which has high reactivity with functional groups such as a carboxyl group, a phenolic hydroxyl group, an acid anhydride group, and a thiol group.
  • 2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, and 4,4-dimethyl-2-vinyl-2-oxazoline are preferable, and 2-vinyl-2-oxazoline and 2-isopropenyl-2-oxazoline are more preferable. Most preferred.
  • the low Tg vinyl monomer (b) is a vinyl monomer having a homopolymer glass transition temperature (Tg) of ⁇ 100 to 70 ° C., specifically, methyl acrylate (Tg: 8 ° C.), acrylic acid Ethyl (Tg: ⁇ 22 ° C.), butyl acrylate (Tg: ⁇ 54 ° C.), 2-ethylhexyl acrylate (Tg: ⁇ 70 ° C.), octyl acrylate (Tg: ⁇ 65 ° C.), nonyl acrylate (Tg: -58 ° C), dodecyl acrylate (Tg: -3 ° C), cyclohexyl acrylate (Tg: 15 ° C), 2-hydroxy-3-phenoxypropyl acrylate (Tg: 17 ° C), ethyl methacrylate (Tg: 65 ° C) ), N-butyl methacrylate (Tg: 20 ° C.), is
  • aqueous dispersion is an aqueous solution in which the copolymer (A) is dissolved in water and / or a dispersion in which the copolymer (A) is dispersed in water.
  • the copolymerization method of the 2-oxazoline monomer (a) and the low Tg vinyl monomer (b) is not particularly limited, and can be carried out by a known radical polymerization method. Examples thereof include solution polymerization, suspension polymerization, emulsion polymerization, and bulk polymerization in an organic solvent such as alcohol and ethyl acetate.
  • a polymerization solvent such as alcohol and ethyl acetate.
  • polymerization initiator used for copolymerization examples include generally known polymerization initiators such as azo, organic peroxide, inorganic peroxide, and redox.
  • the amount of the polymerization initiator used is usually about 0.001 to 10 mol% with respect to the total amount of the polymerizable monomer components.
  • a normal radical polymerization technique such as adjustment of molecular weight by a chain transfer agent is applied.
  • the 2-oxazoline monomer (a) and the low Tg vinyl monomer (b) can be copolymerized as a structural unit with other copolymerizable vinyl monomers.
  • Other copolymerizable vinyl monomers include (meth) acrylates having 1 to 12 carbon chain alkyl groups, N-alkyl (meth) acrylamides having 1 to 12 carbon chain alkyl groups, the same or different N, N-dialkyl (meth) acrylamide having two alkyl groups of 1 to 12 carbon chains, (meth) acrylate or (meth) acrylamide having an aromatic substituent, hydroxyalkyl (C1-12) (meth) acrylate or (Meth) acrylamide, (meth) acrylonitrile, (meth) acrylic acid and the like can be mentioned.
  • These copolymerizable vinyl monomers may be used alone or in combination of two or more.
  • the total molar fraction of various other copolymerizable vinyl monomers to be blended is 30 It is prefer
  • the molecular weight of the copolymer (A) of the present invention is 1,000 to 500,000 on a weight average. Further, it is preferably 1,500 to 100,000, more preferably 2,000 to 80,000. When the weight average molecular weight is less than 1,000, initial dispersion failure of a hardly dispersible carbon material such as CNT may occur, and uneven adhesion to the carbon material surface is likely to occur as an adhesion improver, As a sizing agent for a fibrous carbon material, a sufficiently satisfactory effect may not be achieved, which is not preferable.
  • the glass transition temperature (Tg) of the copolymer (A) of the present invention is ⁇ 80 to 75 ° C. Further, it is preferably ⁇ 70 to 70 ° C., more preferably ⁇ 50 to 65 ° C. If the Tg is less than -80 ° C, the strength of the copolymer (A) may be significantly reduced and may not be suitable for use as an adhesion improver. On the other hand, if the Tg exceeds 75 ° C, the copolymer The flexibility of (A) is insufficient and it is easy to peel off from the surface of the carbon material due to friction or the like, and the carbon fiber bundled as a sizing agent may become hard and workability may be lowered. When the carbon composite material is formed, the affinity with the resin is insufficient, and the mechanical strength of the resulting composite material cannot be satisfied, which is not preferable.
  • the glass transition temperature (Tg) of the copolymer (A) is a value calculated based on the well-known Fox formula below.
  • Tg the glass transition temperature (unit: K) of the copolymer (A)
  • Tgi (i 1, 2,...
  • glass transition temperature when homopolymer is formed means “glass transition temperature of homopolymer of the monomer”.
  • the carbon material used in the present invention is a material mainly composed of carbon (carbon material), and can be broadly divided into carbon fibers and nanocarbon materials.
  • carbon fibers include polyacrylonitrile (PAN), pitch, rayon, and plant-derived materials.
  • Nanocarbon materials include fullerenes, carbon nanotubes (CNT), vapor-grown carbon fibers (nano Fiber), graphene, graphite, carbon nanoparticles, diamond, artificial diamond, nanodiamond particles, graphite, and other nanocarbons.
  • PAN-based carbon fiber is more preferable as a fiber system because it is excellent in strength per unit weight and elastic modulus and has a large production amount, and CNT can control the structure at the nanometer level, and is inexpensive and industrially useful as a new functional material. Since it can be manufactured at a level, it is preferable as a nano-based carbon material. Moreover, even if these carbon materials are used as they are on the market, they may be used after a treatment for producing a large number of carboxyl groups and phenolic hydroxyl groups on the surface by a treatment method such as oxidation.
  • the carbon materials used in the present invention may be used alone or in combination of two or more according to their respective purposes.
  • these carbon materials can be used as they are on the market, but physical dispersion treatments such as washing with water and solvent, bead mill dispersion treatment and ultrasonic dispersion treatment for entanglement of CNTs are implemented. The use after that is more preferable.
  • organic solvents and water that are liquid at room temperature are preferable.
  • Solvents include alcohols such as methanol, ethanol, isopropyl alcohol (IPA) and butanol, ketones such as acetone, methyl ethyl ketone (MEK) and methyl isobutyl ketone, esters such as ethyl acetate, propyl acetate and butyl acetate, ethylene glycol Ethers such as monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether, ethylene glycol monomethyl ether, tetrahydrofuran (THF), toluene, xylene, chloroform, N-methylpyrrolidone (NMP), N-methylformamide (NMF), N, N-dimethylformamide (DMF), N-methylacetamide, dimethylacetamide,
  • a hydrophilic solvent having a nitrogen atom or a sulfur atom in the above has a strong interaction with the copolymer (A) of the present invention, thereby having an effect of preventing reaggregation of a carbon material such as CNT, and is stable. Since a dispersion liquid is easy to be formed, it is preferable. Further, when water is used as a dispersant, there is an environmentally friendly merit because it does not have an organic solvent to be discarded.
  • the copolymer (A) of the present invention as a dispersion accelerator, the dispersibility of the carbon material that is difficult to disperse in water is improved, and an environmentally friendly dispersion of the carbon material is easily obtained. be able to.
  • the copolymer (A) of the present invention has a blending amount as a carbon material dispersion accelerator, an adhesion improver, and a sizing agent for a fibrous carbon material. Although it varies greatly depending on the presence and absence and the method, it is preferably 0.01 to 20% by mass with respect to the dispersant and 0.1 to 100 mg / m 2 with respect to the carbon material. In particular, in carbon fibers (CF) and carbon nanotubes (CNT) having a highly difficult dispersion aspect, 0.01 to 10% by mass with respect to the dispersant and 0.1 to 80 mg / m with respect to the carbon material. 2 is more preferable.
  • CF carbon fibers
  • CNT carbon nanotubes
  • the blending amount of the copolymer (A) is less than 0.01% by mass with respect to the dispersant, there may be a problem in that it cannot be sufficiently dispersed depending on the type and concentration of the carbon material. Even when the liquid is obtained, when the carbon material is subsequently adhered to the solid material using the dispersion, the effect as an adhesion improver cannot be sufficiently provided, and a uniform and high strength carbon material adhesion layer can be obtained. There is a possibility that there is no possibility, or when used as a sizing agent for a fibrous carbon material, fiber fluffing or yarn breakage may occur, and there is a possibility that a satisfactory sizing effect cannot be obtained.
  • the blending amount of the copolymer (A) exceeds 20% by mass with respect to the dispersant, the effect of promoting the dispersion of the carbon material is high and there is no problem in forming a uniform dispersion, but the adhesion improver When it is used as a fibrous carbon fiber, it is not preferable because the concentration is high and the physical properties are likely to vary.
  • the carbon material can be adhered to the solid material by using the obtained carbon material dispersion, and the fibrous carbon material can be focused. Further, when the blending amount of the copolymer (A) as an adhesion improver or a sizing agent is 0.1 to 100 mg / m 2 with respect to the carbon material, the carbon material is uniformly and strongly bonded to a solid substance. Or can uniformly cover the carbon fiber, which is preferable.
  • the carbon material dispersion accelerator, carbon material adhesion improver and fibrous carbon material sizing agent of the present invention are all characterized by containing a copolymer (A).
  • the copolymers (A) contained therein may have the same composition and structure, or may have different compositions and structures, and can be used alone or in combination. Further, from the viewpoint of low cost and easy process control, it is preferably a dispersion accelerator and at the same time, an adhesion improver and a sizing agent for fibrous carbon materials.
  • the method for producing a surface-modified carbon material according to the present invention includes a dispersion accelerator, an adhesion improver, a type of sizing agent for fibrous carbon material (hereinafter abbreviated as a dispersion accelerator, etc.), a carbon material, an adhesion improver, and a sizing agent. It can be roughly divided into two types according to the reaction method. One is a method in which an adhesion improver or sizing agent comprising a copolymer (A) is heated in contact with the surface of a carbon material in a liquid medium, and the other is an adhesion improver or sizing agent. It is the method of heating after making it contact the surface of the carbon material in a liquid medium.
  • a liquid dispersant such as a solvent or water, a dispersion accelerator composed of the copolymer (A), and a carbon material such as CNT are mixed, and the carbon material is dispersed while heating, and at the same time, carbon
  • a method of producing a surface-modified carbon material by adhering the copolymer (A) to the surface of the material (2)
  • the copolymer (A) is attached to the carbon material from the carbon material dispersion obtained in (1) above.
  • a method of taking out the composite and producing a surface-modified carbon material by heating can be mentioned.
  • a solvent having a high boiling point and high thermal stability and having no reactivity with an oxazoline group can be used as a dispersant or the like.
  • the temperature of the dispersion step varies depending on the type of carbon material and the composition and structure of the copolymer (A), but is preferably 40 to 200 ° C., preferably 60 to It is more preferable that it is 180 degreeC. When the temperature is lower than 40 ° C., the dispersion time may be prolonged or the reaction for adhesion or modification may not proceed sufficiently.
  • the temperature is higher than 200 ° C.
  • a lump of carbon material is generated or settled. It was difficult to obtain a stable dispersion.
  • a stirrer having a mixing effect, an ultrasonic cleaner, a bead mill disperser, or the like is used. Is more preferable.
  • the required treatment time varies depending on the dispersion method, apparatus and temperature, but it is preferably 10 minutes to 10 hours.
  • the obtained surface-modified carbon material may be used in the next step while being dispersed in the dispersion, and can be used after being taken out from the dispersion and weighted or dried.
  • the present invention is applied to a low-boiling solvent, water, a thermally unstable or solvent that reacts with an oxazoline group as a dispersant.
  • the temperature is preferably ⁇ 20 to 40 ° C. and the treatment time is preferably 10 minutes to 10 hours.
  • the carbon material with the copolymer (A) attached to the surface is taken out of the dispersion and dried by heating, and the carboxylic acid group or phenolic hydroxyl group on the surface of the carbon material is converted into the oxazoline group of the copolymer (A).
  • the surface-modified carbon material can be obtained by taking out the carbon material to which the copolymer (A) is attached from the mixed solution, drying and heating (baking).
  • the carbon material to which the copolymer (A) is attached can be separated from the dispersant by one or a combination of two or more methods such as filtration, membrane separation, dialysis, and centrifugation.
  • the temperature of the firing step is 40 to 240 ° C, preferably 60 to 220 ° C, more preferably 80 to 200 ° C. If the calcination temperature is less than 40 ° C., there is a possibility that those having low reactivity cannot react sufficiently due to the structure of the oxazoline group, and if the calcination temperature exceeds 240 ° C., thermal decomposition of the copolymer (A) And oxidation are likely to occur, which is not preferable.
  • the surface-modified carbon material produced by this method is a solid and can be used as it is or after being redispersed in a dispersant.
  • the carbon composite material of the present invention is obtained by a reaction between a surface-modified carbon material and a solid material.
  • the solid material referred to here is a functional group that is solid at room temperature and has reactivity with the oxazoline group, such as a carboxyl group, a phenolic hydroxyl group, an acid anhydride functional group, an epoxy group, a thiol group, and an amine group. It is characterized by having at least one functional group selected from the group consisting of amide groups. These functional groups react with the oxazoline group on the surface of the surface-modified carbon material, and the generated chemical bond exists between the surface-modified carbon material and the solid material, thereby providing the effect of a crosslinking agent or a linking agent.
  • Examples of the solid material used in the present invention include thermoplastic resins, moldable low molecular weight thermosetting resins, and carbon materials. These solid materials may be used alone or in combination.
  • the compounding ratio with the surface-modified carbon material varies depending on the type, structure, physical properties and application of the solid material.For example, applications such as reinforcement of thermoplastic resin and low molecular weight thermosetting resin, addition of antistatic property, improvement of heat resistance, etc. If so, 0.01 to 80% by mass, preferably 0.05 to 70% by mass of the surface-modified carbon material can be blended with respect to the thermoplastic resin. Moreover, since a more uniform carbon composite material is easy to be obtained by diluting and using a high concentration product of a surface-modified carbon material as a master batch, it is preferable. On the other hand, for applications such as surface coating, surface modification, and surface modification of carbon materials, 0.001 to 20% by mass, preferably 0.005 to 10% by mass of surface-modified carbon material is added to the carbon material. be able to.
  • Polyolefins such as polyethylene (PE) and polypropylene (PP) as thermoplastic resins, polyamides such as nylon 6 (PA6, nylon 66 (PA66), polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), Examples include polyurethanes, acrylic resins, ABS (acrylonitrile butadiene styrene) resins, polystyrene (PS), thermoplastic polyimide, polycarbonates, and thermoplastic resins such as carboxylic acid and maleic anhydride modified resins of these general-purpose resins.
  • PE polyethylene
  • PP polypropylene
  • thermoplastic resins polyamides such as nylon 6 (PA6, nylon 66 (PA66)
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • examples include polyurethanes, acrylic resins, ABS (acrylonitrile butadiene styrene) resins, polystyrene (PS),
  • thermosetting resin examples include phenol resin, epoxy resin, polyimide resin, melamine resin, urea resin, unsaturated polyester resin, diallyl phthalate resin, polyurethane resin, and silicon resin. These resins are not limited to one type may be used in combination of plural kinds.
  • Examples of the carbon material include carbon fiber (CF), carbon nanotube (CNT), carbon nanofiber (CNF), graphene, graphite, natural or synthetic diamond.
  • CF, CNT, CNF, diamond particles and powders are widely used in various fields, and it is preferable because commercially available products are easily available.
  • These carbon materials are not limited to one type, and a plurality of types can be used in combination. Moreover, even if these carbon materials are used as they are on the market, they may be used after a treatment for producing a large number of carboxyl groups and phenolic hydroxyl groups on the surface by a treatment method such as oxidation.
  • thermoplastic resin-based carbon composite material having a thermoplastic resin as a main component and a carbon material or a carbon-based carbon composite material having a carbon material as a main component, or a carbon material as a main component.
  • a new carbon composite material with improved strength and toughness can be produced.
  • the blending ratio of the carbon material or the carbon-based carbon composite material is 80% by mass or less with respect to the thermoplastic resin or the thermoplastic resin-based carbon composite material. Preferably there is.
  • the manufacturing method of the carbon composite material is roughly divided into a solution immersion method and a melt-kneading method depending on the structure of the main component.
  • various organic solvents and water used as a dispersant for the carbon material can be used as well.
  • the carbon material and the surface-modified carbon material can be reacted, and the method for producing the carbon composite can be roughly divided into two as described above.
  • One is to disperse the surface-modified carbon material in a liquid medium, immerse the carbon material in the obtained dispersion liquid for a certain residence time, and directly contact the surface of the carbon material and the surface of the surface-modified carbon material,
  • the other is a method of heating while rubbing, and the other is a method in which the surface of the carbon material and the surface of the surface-modified carbon material are brought into contact with each other and then taken out from the dispersion and heated.
  • the reaction between the carbon material and the surface-modified carbon material is to react the oxazoline group possessed on the surface of the surface-modified carbon material with the carboxyl group or phenolic hydroxyl group possessed on the surface of the carbon material.
  • the reaction can be carried out under similar conditions (reaction temperature, reaction time, etc.).
  • thermoplastic resin a thermoplastic resin-based carbon composite material mainly composed of a thermoplastic resin
  • carbon-based carbon composite mainly composed of a surface-modified carbon material and a carbon material
  • a reaction may be performed by melt kneading while heating using a melt extruder or the like.
  • the kneading extrusion temperature varies greatly depending on the type of resin, but if it is within the range of 150 to 280 ° C, both the melting of the resin and the reaction with the carbon material proceed sufficiently, and the carbon composite material produced is thermally decomposed. Can be prevented, which is preferable.
  • the residence time in the extrusion group is preferably 0.1 to 30 minutes from the viewpoint of balancing the reactivity and the suppression of decomposition.
  • thermoplastic resins used for thermal treatment such as melt kneading and processing
  • polyolefins such as polyethylene (PE) and polypropylene (PP)
  • polyamides such as nylon 6 (PA6, nylon 66 (PA66)
  • Polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), polyurethanes, acrylic resins, ABS (acrylonitrile butadiene styrene) resins, polystyrene (PS), polycarbonates and carboxylic acids and maleic anhydrides of these general-purpose resins
  • thermoplastic resins such as acid-modified resins, etc.
  • Oxazoline on the surface of the surface-modified carbon material of the present invention so that the properties of the carbon material such as high strength, high flexibility, heat resistance, and conductivity can be fully utilized.
  • a master batch of a surface-modified carbon material may be first prepared and pelletized and then kneaded with a thermoplastic resin-based carbon composite material mainly containing various resins and thermoplastic resins.
  • melt-kneader used in the melt-kneading step examples include known melt-kneaders such as a Banbury mixer, a plast mill, a Brabender plastograph, a single screw extruder, a twin screw extruder, and the like. From the viewpoint of satisfactorily dispersing the filler and improving the heat resistance and rigidity of the polyolefin resin composition, it is preferably melt-kneaded by a single screw extruder or a twin screw extruder, and particularly preferably a twin screw extruder.
  • Applications of the carbon composite material of the present invention include injection molding materials, extrusion molding materials, press molding materials, blow molding materials, film molding materials, etc., manufactured by the melt extrusion method.
  • it is preferably an application that requires rigidity and impact resistance, and examples thereof include materials for automobiles and materials for household appliances.
  • various molding methods used for ordinary CFRP are also applied.
  • a molding method (hand lay-up method) in which a reinforcing material such as carbon fiber is charged in advance in a mold and the resin is impregnated with a brush or roller and laminated to a predetermined thickness while defoaming (hand layup method), roving
  • a molding method (filament winding method) in which resin is impregnated, tension is applied to a rotating core (mandrel), and is continuously wound at a predetermined angle (mold winding method).
  • Molding method autoclave method
  • sheet winding method suitable mainly for cylindrical shape molding method in which an intermediate base material impregnated with resin in chopped strands and coated on both sides with gin sheet is charged to the mold and heated and pressurized ( SMC method)
  • SMC method heating and pressurized
  • BMC method molding method in which an intermediate base material kneaded with chopped strands and a matrix is made into a lump (ball shape)
  • a molding method hot press method in which heat and pressure is applied with a cavity core mold, a stamped sheet
  • the RFI (Resin Film Infusion) method, the CPM (Compression Press Molding) method, etc. are mentioned.
  • the beads were milled by stirring at 1000 rpm for 1.5 hours, and then all the beads were put in a 1 L beaker, ion-exchanged water was added and shaken lightly, and the supernatant was removed to float in the supernatant. This process was repeated many times to completely separate the carbon nanotubes and zirconia beads, and then the supernatant was filtered and vacuum dried at 80 ° C. for 4 hours to obtain a black powder.
  • VGCF Carbon nanofiber
  • VGCF-H Carbon nanofiber
  • CF1 Carbon fiber (manufactured by Toray Industries, Inc., PAN-based CF, trade name “TORAYCA Yarn T700 12K”, diameter 7 ⁇ m) Washed with acetone and dried.
  • CF2 CF1 was cut into 5 mm chops, washed with acetone and dried.
  • PP Polypropylene resin (Nippon Polypro Co., Ltd., MA3)
  • PMP maleic anhydride modified polypropylene (manufactured by Sanyo Chemical Industries, Ltd., Umex 1010)
  • PA Polymethylpentene resin (manufactured by Mitsui Chemicals, TPX MX002)
  • PMA acid-modified polymethylpentene resin (manufactured by Mitsui Chemicals, TPX MM-101B)
  • AIBN Azobisbutyronitrile (Wako Pure Chemicals, Reagents)
  • NMP N-methylpyrrolidone EtOH: ethyl alcohol
  • DMF N, N-dimethylformamide “KJCMPA”: 3-methoxy-N, N-dimethylpropanamide (manufactured by KJ Chemicals, Inc., registered trademark “KJCMPA”)
  • ⁇ Dispersibility The dispersion state of the produced carbon material dispersion was observed with an optical microscope (manufactured by HiROX, digital optical microscope power high scope KH-2700), the black ratio was calculated, and the dispersibility was evaluated in four stages.
  • preparation of the sample for observation and the calculation method of a black rate are as follows. Sample preparation: Take 5 ⁇ L of the dispersion, drop 1 drop on the hole slide glass, and when the flow of the solution stops, perform microscopic observation and take a photograph. Black rate calculation: An optical microscope image at 10 arbitrary points was converted into a black and white image (FIG.
  • Black rate (%) number of black pixels / (number of black pixels + number of white pixels) ⁇ 100% A: Black ratio is less than 5% B: Black ratio is 5% or more and less than 10% ⁇ : Black ratio is 10% or more and less than 15% X: Black ratio is 15% or more ⁇ Dispersion stability (storage stability) ) >>: Using the produced carbon material dispersion, it was allowed to stand at 25 ° C. for 90 days, the subsequent state was observed with an optical microscope, the black rate was calculated, and the dispersibility was evaluated in four steps as described above.
  • copolymer (A-1) Absorption (1635 to 1640 cm ⁇ 1 ) of vinyl groups derived from these monomers was not detected, confirming the formation of copolymer (A-1).
  • the Tg of the copolymer (A-1) was ⁇ It calculated as 26 degreeC.
  • Mw weight average molecular weight of the copolymer was analyzed by GPC method (standard polystyrene) and confirmed to be 20,670.
  • a 1 H-NMR (CDCl 3 ) chart of the copolymer (A-1) is shown in FIG.
  • Synthesis Examples 2 to 10 and Synthesis Comparative Examples 1 to 4 As in Synthesis Example 1, 2-oxazoline monomer (a), low Tg vinyl monomer (b), other copolymerizable vinyl monomer (c), and AIBN in predetermined amounts shown in Table 1 Polymerization in Synthesis Examples 2 to 10 and Synthesis Comparative Examples 1 to 4 was carried out using the above, and the resulting polymer was purified in the same manner as in Synthesis Example 1, and the respective polymers (A-2 to A-10 and P -1 to P-4) were obtained as a solid product from a pale yellow viscous liquid. As in Synthesis Example 1, the identification (IR), Tg analysis, molecular weight measurement (GPC), and composition ratio calculation ( 1 H-NMR) of polymers A-2 to A-10 and polymers P-1 to P-4 were performed. The results are shown in Table 1.
  • the composition ratio of the obtained copolymer is slightly different from the molar ratio of the monomers charged in the polymerization reaction. That is, it can be confirmed that the 2-oxazoline monomer (a) is contained in the copolymer more than charged. This is presumably because the monomer (a) is more reactive to radicals during polymerization than the low Tg vinyl monomer (b), and the resulting copolymer (A) contains monomer ( It is suggested that the random arrangement of a) and (b) has a partial block structure, and since it has such a unique structure, it is possible to provide a dispersion promoting effect and an adhesion improving effect that are superior to carbon materials. The present inventors presume.
  • FIG. 3 shows optical micrographs immediately after preparation of the dispersions of Dispersion Examples 2 and 5 (Dispersion Liquids 2 and 5) and Dispersion Comparison Examples 1 to 3 (Dispersion Comparison Solutions 1 to 3).
  • a homopolymer of 2-oxazoline monomer (a) (dispersion comparative example 2), a copolymer having a content of 2-oxazoline monomer (a) of less than 5 mol% (dispersion comparative example 4), 2-oxazoline,
  • the content of the monomer (a) exceeds 98 mol% (dispersion comparative example 7), and homopolymers and mixtures of these copolymers (dispersion comparative examples 6 and 8)
  • the carbon material be dispersed uniformly? Re-aggregation was likely to occur, and a stable dispersion could not be obtained.
  • the copolymer of the specific composition consisting of the monomer (a) and the monomer (b) proposed in the present invention is used as a dispersion accelerator, the dispersibility and the dispersion stability can be satisfied, and it is uniform and stable. A dispersion could be obtained.
  • the copolymer (A) of the present invention can be used as a carbon material dispersion accelerator and simultaneously as an adhesion improver for carbon materials and as a sizing agent for fibrous carbon materials. At this time, the dispersion accelerator / adhesion improver made of the copolymer (A) in the liquid medium promotes the dispersion of the carbon material, and then is heated while being in contact with the surface of the carbon material.
  • the oxazoline group of (A) reacts with a carboxyl group or phenolic hydroxyl group on the surface of the carbon material, and the copolymer (A) is fixed to the surface of the carbon material through a chemical bond, thereby producing a surface-modified carbon material. be able to.
  • Example 1 of surface-modified carbon material production (Modification Example 1) The dispersion obtained in Dispersion Example 1 was transferred to a flask and heated at 100 ° C. for 1 hour with stirring. Thereafter, the dispersant was removed by reduced pressure evaporation, and washing was performed twice with ethanol using a lab shaker (200 rpm, 15 minutes / once) to remove the unreacted copolymer (A). The solid after washing was dried under vacuum to obtain solid powdered surface modified CNT (AC-1). About 5 mg of the obtained AC-1 was used and weighed with a thermogravimetric analyzer (Q-600, TA INSTRUMENT), and the temperature was raised from room temperature to 600 ° C. at 10 ° C./minute in a nitrogen atmosphere.
  • Q-600 thermogravimetric analyzer
  • the adhesion amount of the copolymer (A) adhered to the surface of -1 was calculated to be 5.24%. Furthermore, based on the physical property values (density 2 g / cm 3 , diameter 11 nm) of CNTs, it was confirmed that the copolymer adhesion amount per surface area was 0.300 mg / m 2 .
  • Examples 2 to 8 and Comparative Examples 1 to 6 for producing surface modified carbon materials (Modified Examples 2 to 8 and Modified Comparative Examples 1 to 6)
  • a surface-modified carbon material was prepared, and solid powdery surface-modified CNTs (AC-2 to 8) were obtained.
  • PC-1 to PC-6 were obtained as powder solids by the same operation as in Modification Example 1 using the mixed solution prepared in each dispersion comparative example.
  • polymers attached to the surface of the carbon material were quantified by thermogravimetric analysis, and the calculation results are shown in Table 3.
  • Examples 9 to 12 and Comparative Examples 7 to 9 for producing surface-modified carbon materials (Modified Examples 9 to 12 and Modified Comparative Examples 7 to 9)
  • the copolymer (A) and the dispersant (solvent) were mixed in the ratio shown in Table 4, and treated with a bath-type ultrasonic device (ELMA, S30) at 25 ° C. for 30 minutes.
  • ELMA, S30 bath-type ultrasonic device
  • a solution was obtained.
  • a predetermined amount of carbon material (CF, appropriately cut to 1 mm to 2 cm) shown in Table 4 was added to the solution, and heating was performed under the predetermined conditions (temperature and time) shown in Table 4.
  • the obtained solid is filtered, washed with ethanol twice using a lab shaker (200 rpm, 15 minutes / once), and the washed solid is dried under vacuum to obtain a solid powdery surface.
  • Modified carbon materials AC-9 to 12
  • the adhesion amount of the copolymer (A) adhered to the surface was similarly calculated by thermogravimetric analysis. Further, based on the physical properties of CF (density 2 g / cm 3, diameter 7 ⁇ m), the amount of copolymer adhering per surface area was calculated and shown in Table 4.
  • Modification Comparative Examples 7 to 9 were produced according to the conditions shown in Table 4, and PC-7 to 9 were obtained as a powdered solid. Similarly, the amount of polymer attached per surface area of PC-7 to 9 was calculated by thermogravimetric analysis and is shown in Table 4.
  • the copolymer (A) of the present invention dissolves the copolymer (A) in a liquid medium (organic solvent or water) when used as an adhesion improver for carbon materials and a sizing agent for fibrous carbon materials. After the carbon material is added, the copolymer (A) is attached to the surface of the carbon material, and then the carbon material attached to the copolymer (A) is taken out of the solution and heated to produce the copolymer (A ) Reacts with a carboxyl group or a phenolic hydroxyl group on the surface of the carbon material, and the copolymer (A) is fixed to the surface of the carbon material through a chemical bond to produce a surface-modified carbon material.
  • a solvent having a low boiling point or reactivity with an oxazoline group is used, or when it is difficult to prepare a dispersion of a large size carbon material, the surface-modified carbon material can be easily produced by this method.
  • Examples 13 to 15 and Comparative Example 10 for producing surface-modified carbon materials (Modified Examples 13 to 15 and Modified Comparative Example 10)
  • a predetermined amount of a carbon material (CF, appropriately cut to 1 mm to 2 cm) was added to the copolymer solution shown in Table 4, and treated at 25 ° C. for 30 minutes with a bath-type ultrasonic device. Thereafter, the solid material is filtered and subjected to heat treatment (firing) under the predetermined conditions shown in Table 4. Similarly, ethanol washing is performed twice, the washed solid material is dried, and solid powdery surface-modified carbon is obtained. Material (AC-13) was obtained.
  • a carbon material (CF 3 m) cut to a length of 3 m was passed through the copolymer solution shown in Table 4 through a copolymer solution tank having a width of 300 mm at a speed of 1 mm / second, and heated under predetermined conditions shown in Table 4 After the treatment (firing), the product is passed through an ethanol bath of the same width twice (2 mm / second), the washed fibrous solid is dried, and the solid fibrous surface-modified carbon material (AC-14, 15 ). Further, as in Modification Example 13, Modification Comparative Example 10 was prepared according to the conditions in Table 4 to obtain PC-10 as a powdery solid. Similarly, the amount of polymer attached per surface area of PC-10 was calculated by thermogravimetric analysis and is shown in Table 4.
  • Example 1 of evaluation of sizing agent for fibrous carbon material Carbon material CF1 cut to a length of 6 cm is dipped in an aqueous solution of copolymer (A-1) (concentration 1 wt%), impregnated for 5 minutes at room temperature, and then removed from the aqueous solution at a rate of 0.03 mm / second.
  • the sizing CF bundle (SAC-1) was obtained by pulling up and placing in a vacuum dryer set at 100 ° C. and performing heat treatment for 1 hour under vacuum.
  • the weight of the copolymer adhered to the fiber bundle by thermogravimetric analysis was calculated to be 0.72, and the physical property value of CF1 (the amount per surface area by weight% was calculated). Based on the physical property values of CF1 (density 2 g / cm 3 , diameter 7 ⁇ m), it was confirmed that the copolymer adhesion amount per surface area was 25.94 mg / m 2 .
  • CF1 was treated with water, a 1% by weight aqueous solution of homopolymer (P-1), and a 1% by weight aqueous solution of homopolymer (P-2).
  • Carbon composite material composed of carbon material and surface-modified carbon material
  • This type of composite material is similar to the production of the surface-modified carbon material, such as a simultaneous heating method in which the carbon material and the surface-modified carbon material are contacted with each other by heating in a liquid medium, or the carbon material and the surface in a liquid medium.
  • Carbon composite material (resin / copolymer / carbon) composed of thermoplastic resin and surface-modified carbon material
  • This type of composite material can be manufactured by a melt-kneading method in which a surface-modified carbon material and a general-purpose resin are dry-blended and the resin reacts in contact with the surface-modified carbon material in a molten state by a melt extruder or the like. This method is preferred because the resulting carbon composite can be formed directly.
  • Carbon composite material (resin / carbon / copolymer / carbon) composed of thermoplastic resin, carbon material and surface-modified carbon material
  • This type of carbon composite material can be manufactured by dry blending a surface-modified carbon material, a carbon material, and a general-purpose resin, and then reacting them by melt-kneading.
  • the “carbon / co-polymer” obtained in (1) above can be used. It can also be produced by melt-kneading a polymer / carbon type carbon composite material with a general-purpose resin.
  • Carbon composite material production example 1 (composite example 1) Disperse 20 g of dispersion 1 obtained in dispersion example 1 and 1 g of chopped carbon fiber CF2 cut into 5 mm into a 100 mL screw tube, close the lid, and use a lab shaker at room temperature for 60 minutes at a speed of 200 rpm. Vibrated. Then, the CF2 after the treatment is taken out with a 50 ⁇ m mesh filtration device, heated at 80 ° C. for 2 hours, and further dried at 40 ° C. under vacuum for 2 hours to obtain a solid carbon composite material (CAC-1) did.
  • CAC-1 solid carbon composite material
  • the obtained CAC-1 was washed twice with ethanol using a laboratory shaker (200 rpm, 15 minutes / once), and the washed solid was dried under vacuum to obtain the ethanol of the carbon composite material CAC-1. Acquired cleaning products.
  • the surface state of the untreated cut product CF2 and the surface state of the carbon composite material CAC-1 and its ethanol-cleaned product were observed with a scanning electron microscope (FE-SEM, JEOL JIS-6700F), and respective photographs are shown in FIG. .
  • Examples 2 and 3 (Composite Examples 2 and 3) for producing carbon composite materials
  • the surface-modified carbon materials AC-1, CF2 and NMP obtained in Example 1 for producing the surface-modified carbon material were weighed at a weight ratio of 1:10:89, and treated for 30 minutes at 25 ° C. with a bath-type ultrasonic device. . Thereafter, the mixture is heated at 150 ° C. for 0.5 hours, and the resulting black solid is separated by filtration, and washed twice with ethanol using a lab shaker (200 rpm, 15 minutes / once). The subsequent solid matter was dried under vacuum to obtain a solid carbon composite material (CAC-2). Washing with ethanol was performed in the same manner as in Composite Example 1 to obtain a washed product of CAC-2.
  • Examples 4 and 5 (Composite Examples 4 and 5) for producing carbon composite materials
  • the surface-modified carbon material AC-1 and NMP were weighed at a weight ratio of 2:98, and treated for 30 minutes at 25 ° C. with a bath-type ultrasonic device. Thereafter, the mixed liquid is heated to 150 ° C., and a carbon material (CF1 3 m) cut to a length of 3 m is passed through a tank filled with the mixed liquid having a width of 300 mm at a speed of 0.5 mm / second, and the ethanol tank having the same width is passed. Was passed twice (2 mm / second), and the washed fibrous solid was dried to obtain a solid fibrous carbon composite material (CAC-4).
  • CAC-4 solid fibrous carbon composite material
  • a carbon material (CF1 3 m) cut to a length of 3 m was passed through a tank filled with the mixed solution having a width of 300 mm at a speed of 1 mm / second, and 200 ° C. Baked by heating for 0.1 hour, passed through an ethanol bath of the same width twice (2 mm / second), dried the washed fibrous solid, and obtained a solid fibrous carbon composite material (CAC-5). ).
  • Examples 6 to 9 for producing carbon composite materials (Composite Examples 6 to 9) Using the surface-modified carbon material AC-2 obtained in Example 2 for producing the surface-modified carbon material and the surface-modified carbon material AC-3 obtained in Example 3 for producing the surface-modified carbon material, the predetermined conditions shown in Table 5 were used. Based on the conditions, Examples 6 to 9 were performed to obtain a solid carbon composite material (CAC-6 to 9).
  • Comparative examples 1 to 4 for producing carbon composite materials were performed under the conditions shown in Table 5 to obtain a fibrous carbon composite material (CPC-1). Further, according to the procedures of Examples 2 and 3 for producing the carbon composite material, Comparative Examples 2 to 4 were carried out under the conditions shown in Table 5 to obtain solid carbon composite materials (CPC-2 to 4). CPC-4 is obtained by directly attaching CNT and CF without using any dispersion accelerator such as a copolymer or improving adhesiveness. Further, ethanol washing was performed in the same manner as in Composite Example 1, and washed products of CPC-1 to 4 were obtained. The surface states of CPC-1, CPC-2 and their washed products were observed with a scanning electron microscope, and the photograph is shown in FIG.
  • the carbon composite material formed via the copolymer (A) of the present invention has the CNT firmly coated on the CF surface.
  • the carbon composite material of the present invention can be produced by various methods such as simultaneous heating and post-heating, and the oxazoline group in the copolymer (A) has high reactivity, and the formed chemical bond is Strongly attached to a carbon material such as CNT or CF at room temperature, and sufficiently adhered to the surface. Further, a strong chemical bond is formed by heating. It was confirmed that the CNTs were uniformly fixed to each other.
  • resin composite materials composed of resin / surface modified carbon material / carbon composite material
  • a 200 ⁇ m-thick film was prepared from the obtained resin composite material using a hot press machine (miniTEST PRESS-10 manufactured by Toyo Seiki Co., Ltd.) (molding temperature 235 ° C., pressure 5 MPa after pressurizing for 2 minutes) A press film was prepared by rapid cooling in 1 minute.) A dumbbell test piece having a length of 35 mm and a width of 2.5 mm was punched out from the obtained press film, and a tensile tester (universal test manufactured by Toyo Seiki Co., Ltd.) with 15 mm between chucks. The tensile test was performed at a speed of 10 mm / min. In each Example and Comparative Example, the average value of the tensile strength of five test pieces is taken and shown in Table 6.
  • the resin composite material formed through the copolymer (A) of the present invention was modified with a copolymer on the surface of CF or CNT (resin / surface modified carbon material, resin / carbon composite). Material), the adhesion to polyolefin general-purpose resins and their acid-modified resins was improved, and the mechanical strength of the resulting resin composite was improved. In addition, when the resin / surface-modified carbon material / carbon composite material was added to the general-purpose resin, it was confirmed that the mechanical strength of the resin composite material was further improved by the reinforcing effect of both CNT and CF.
  • the resin cannot disperse and adhere to the carbon material. No improvement in strength was confirmed. Further, in the homopolymer of 2-oxazoline monomer (a) and the polymer outside the range of the copolymer composition ratio specified in the present invention, the effect of improving the dispersibility and adhesiveness due to their blending is low, so The improvement in strength was extremely low. In particular, when nothing was present between CF and CNT, adhesion imparting and reinforcing effects were not shown at all.
  • Resin composite material production example 9 (resin composite example 9) and comparative example 7 (resin composite comparative example 7) 0.1 g of copolymer A-1 obtained in the synthesis example was dissolved in 99.9 g of water to prepare an aqueous solution of polymer A-1 having a concentration of 0.1% by weight.
  • an aqueous solution of the homopolymer P-1 of 2-oxazoline monomer (a) obtained in Synthesis Comparative Example 1 was prepared. Two bundles of CF1 cut to 10 cm were prepared, and the bundles of CF1 were put in the polymer solutions of A-1 and P-1, respectively, and impregnated for 5 minutes to perform sizing treatment. Thereafter, vacuum drying was performed at 100 ° C.
  • FIG. 8 shows photographs and enlarged photographs of resin-impregnated composite materials COPA-1-PP and COPP-1-PP.
  • the copolymer A-1 of the present invention has a low Tg, it has a high affinity and adhesiveness with PP resin, the resin uniformly penetrates into the fiber bundle, the resin adheres closely to the fiber surface, and the fiber is moderately dissolved. That is, a fiber bundle excellent in resin impregnation property was obtained.
  • the homopolymer P-1 had a high Tg (108 ° C.) and the treated fiber was hard, so the affinity and adhesion to the PP resin were low, and the impregnation property was poor.
  • Photo for dispersibility evaluation (a) Optical microscope image, (b) Black and white image 1 H-NMR chart of copolymer A-1 Photos immediately after preparation of dispersions of dispersion examples and comparative dispersion examples (a) Dispersion Example 2, (b) Dispersion Example 5, (c) Dispersion Comparison Example 1, (d) Dispersion Comparison Example 2, (e) Dispersion Comparative Example 3 Photograph after processing of focusing example and focusing comparison example (a) Focusing example 1 (SC-1), (b) Focusing comparison example 1 (PC-0), Focusing comparison example 2 (PC-1) SEM photograph of carbon composite material Example 1 (a) Surface photograph of untreated cut product CF2, (b) Surface photograph of carbon composite material CAC-1, (c) Surface photograph of carbon composite material CAC-1 washed product SEM photographs of carbon composite materials Examples 2 and 3.
  • the copolymer of the present invention exhibits unique properties such as promoting dispersion of carbon materials into other types of materials, improving the surface adhesion of carbon materials, and improving the convergence of fibrous carbon materials.
  • Dispersion accelerators, adhesion improvers, bundling agents, sizing agents, etc. do not require special dispersion and surface treatment techniques and equipment, and do not impair the original properties of carbon materials, and various carbon materials can be used in a simple manner. Hydrophilicity and adhesiveness can be imparted to the surface of the film.
  • Carbon materials whose surfaces have been modified using the adhesion improver surface-modified carbon materials
  • a suitable carbon composite material having performance can be provided.
  • thermoplastic resins such as polyolefins and thermosetting resins such as epoxy and polyimide
  • general-purpose thermoplastic resins such as polyolefins and thermosetting resins such as epoxy and polyimide
  • general-purpose thermoplastic resins such as polyolefins and thermosetting resins such as epoxy and polyimide
  • Related products such as interior / exterior parts, household appliances, furniture, miscellaneous goods, molded products of medical materials, food containers, food packaging, packaging materials such as general packaging, coating materials such as electric wires and cables, architecture / civil engineering, stationery / It is suitable for industrial materials such as office supplies, compatibilizers or adhesives for various polymer alloys.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

Le problème décrit par la présente invention est de fournir un promoteur de dispersion, un agent améliorant l'adhérence et un agent d'encollage avec lesquels il est possible de conférer une hydrophilicité et une adhésivité à la surface de divers matériaux carbonés et de conférer des propriétés d'encollage à des matériaux carbonés fibreux par un procédé simple qui ne nécessite pas de techniques ou d'équipements spécifiques pour la dispersion et le traitement de surface et qui ne nuit pas aux propriétés inhérentes des matériaux carbonés, et de fournir également des matériaux carbonés à surface modifiée et des matériaux composites carbonés dont la surface est modifiée à l'aide de l'agent améliorant l'adhérence/agent d'encollage. La solution selon l'invention porte sur la découverte qu'un copolymère (A) contenant des monomères à base de 2-oxazoline (a) et des monomères à base de vinyle à faible Tg (b) en tant que motifs structuraux favorise la dispersion de matériaux carbonés dans d'autres types de matériaux, améliore l'adhésivité de surface des matériaux carbonés, et présente des performances uniques conférant des propriétés d'encollage à des matériaux carbonés fibreux. De plus, il était possible d'obtenir des matériaux carbonés à surface modifiée auxquels une adhésivité a été conférée et divers types de matériaux composites carbonés par réaction avec divers matériaux carbonés à l'aide d'un agent améliorant l'adhérence qui comprend le copolymère.
PCT/JP2018/009780 2017-03-15 2018-03-13 Dispersants à base d'oxazoline pour matériaux carbonés et matériaux composites carbonés dans lesquels ceux-ci sont utilisés WO2018168867A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2019502033A JP6617229B2 (ja) 2017-03-15 2018-03-13 炭素材料用オキサゾリン系分散剤等及びそれらを用いた炭素複合材料

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017049785 2017-03-15
JP2017-049785 2017-03-15

Publications (1)

Publication Number Publication Date
WO2018168867A1 true WO2018168867A1 (fr) 2018-09-20

Family

ID=63522291

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/009780 WO2018168867A1 (fr) 2017-03-15 2018-03-13 Dispersants à base d'oxazoline pour matériaux carbonés et matériaux composites carbonés dans lesquels ceux-ci sont utilisés

Country Status (3)

Country Link
JP (1) JP6617229B2 (fr)
TW (1) TWI753133B (fr)
WO (1) WO2018168867A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6806964B1 (ja) * 2019-12-25 2021-01-06 ダイセルミライズ株式会社 炭素繊維強化樹脂組成物
WO2022163358A1 (fr) * 2021-01-29 2022-08-04 ナガセケムテックス株式会社 Composition de résine pour photoformage tridimensionnel
JP7428985B2 (ja) 2018-12-26 2024-02-07 Ｋｊケミカルズ株式会社 炭素材料を含有する積層体と複合体

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008088404A (ja) * 2006-09-04 2008-04-17 Nippon Shokubai Co Ltd 水性樹脂組成物
WO2015029949A1 (fr) * 2013-08-27 2015-03-05 日産化学工業株式会社 Agent pour disperser un matériau carboné électroconducteur, et dispersion de matériau carboné électroconducteur
JP2017203236A (ja) * 2016-05-13 2017-11-16 株式会社日本触媒 強化繊維用サイジング剤
JP2018024788A (ja) * 2016-08-10 2018-02-15 Ｋｊケミカルズ株式会社 炭素材料用接着性向上剤及びそれを用いた複合材料

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3222512B2 (ja) * 1991-11-11 2001-10-29 三菱レイヨン株式会社 炭素繊維用サイジング剤

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008088404A (ja) * 2006-09-04 2008-04-17 Nippon Shokubai Co Ltd 水性樹脂組成物
WO2015029949A1 (fr) * 2013-08-27 2015-03-05 日産化学工業株式会社 Agent pour disperser un matériau carboné électroconducteur, et dispersion de matériau carboné électroconducteur
JP2017203236A (ja) * 2016-05-13 2017-11-16 株式会社日本触媒 強化繊維用サイジング剤
JP2018024788A (ja) * 2016-08-10 2018-02-15 Ｋｊケミカルズ株式会社 炭素材料用接着性向上剤及びそれを用いた複合材料

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7428985B2 (ja) 2018-12-26 2024-02-07 Ｋｊケミカルズ株式会社 炭素材料を含有する積層体と複合体
JP6806964B1 (ja) * 2019-12-25 2021-01-06 ダイセルミライズ株式会社 炭素繊維強化樹脂組成物
JP2021102735A (ja) * 2019-12-25 2021-07-15 ダイセルミライズ株式会社 炭素繊維強化樹脂組成物
WO2022163358A1 (fr) * 2021-01-29 2022-08-04 ナガセケムテックス株式会社 Composition de résine pour photoformage tridimensionnel

Also Published As

Publication number Publication date
JPWO2018168867A1 (ja) 2019-06-27
TWI753133B (zh) 2022-01-21
JP6617229B2 (ja) 2019-12-11
TW201841959A (zh) 2018-12-01

Similar Documents

Publication Publication Date Title
Liu et al. An effective surface modification of carbon fiber for improving the interfacial adhesion of polypropylene composites
Yang et al. Enhancement of stiffness, strength, ductility and toughness of poly (ethylene oxide) using phenoxy-grafted multiwalled carbon nanotubes
Blond et al. Enhancement of modulus, strength, and toughness in poly (methyl methacrylate)‐based composites by the incorporation of poly (methyl methacrylate)‐functionalized nanotubes
Xia et al. Polymer-encapsulated carbon nanotubes prepared through ultrasonically initiated in situ emulsion polymerization
Martínez-Hernández et al. Carbon nanotubes composites: processing, grafting and mechanical and thermal properties
Al-Saleh et al. Review of the mechanical properties of carbon nanofiber/polymer composites
JP6617229B2 (ja) 炭素材料用オキサゾリン系分散剤等及びそれらを用いた炭素複合材料
McClory et al. Polymer/carbon nanotube composites
Che et al. Epoxy composite fibers reinforced with aligned single-walled carbon nanotubes functionalized with generation 0− 2 dendritic poly (amidoamine)
US9115220B2 (en) Method for functionalization of nanoscale fibers and nanoscale fiber films
JP2009197359A (ja) 強化繊維、および繊維強化複合材料
JP6076484B2 (ja) 炭素ナノ物質が結合された熱可塑性高分子及びその製造方法
Gupta et al. Rheologic and mechanical properties of multiwalled carbon nanotubes-reinforced poly (trimethylene terephthalate) composites
Mozaffarinasab et al. Surface modification of carbon nanotubes by a bifunctional amine silane; effects on physical/mechanical/thermal properties of epoxy nanocomposite
Choi et al. Fabrication of MA-EPDM grafted MWCNTs by reactive extrusion for enhanced interfacial adhesion and mechanical properties of PP/MA-EPDM composite
Mourad et al. Wet lay-up technique for manufacturing of advanced laminated composites
JP6805415B2 (ja) 炭素材料用接着性向上剤及びそれを用いた複合材料
JP5989914B2 (ja) 炭素ナノ物質含有樹脂組成物及びプラスチック成形品
Nayak et al. Dispersion of SiC coated MWCNTs in PEI/silicone rubber blend and its effect on the thermal and mechanical properties
JP7428985B2 (ja) 炭素材料を含有する積層体と複合体
JP2018145245A (ja) 炭素繊維複合材料
KR20130036114A (ko) 탄소나노튜브 강화된 폴리프로필렌 제조방법
Park et al. Surface modification of carbon nanotubes for high-performance polymer composites
Kim et al. Influence of surface treatment of multi-walled carbon nanotubes on interfacial interaction of nanocomposites
Gantayat et al. Structural and mechanical properties of functionalized carbon nanofiber/epoxy nanocomposites

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18766872

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019502033

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18766872

Country of ref document: EP

Kind code of ref document: A1