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WO2011102400A1 - Procédé de fabrication de fibre de précurseur destinée à obtenir une fibre de carbone de résistance mécanique et de module d'élasticité élevés - Google Patents

Procédé de fabrication de fibre de précurseur destinée à obtenir une fibre de carbone de résistance mécanique et de module d'élasticité élevés Download PDF

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Publication number
WO2011102400A1
WO2011102400A1 PCT/JP2011/053317 JP2011053317W WO2011102400A1 WO 2011102400 A1 WO2011102400 A1 WO 2011102400A1 JP 2011053317 W JP2011053317 W JP 2011053317W WO 2011102400 A1 WO2011102400 A1 WO 2011102400A1
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Prior art keywords
carbon
carbon nanotubes
spinning
spinning dope
fiber
Prior art date
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PCT/JP2011/053317
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English (en)
Japanese (ja)
Inventor
浩和 西村
公一 平尾
信輔 山口
卓也 赤石
義弘 渡辺
文志 古月
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hokkaido University NUC
Japan Exlan Co Ltd
Toyobo Co Ltd
Original Assignee
Hokkaido University NUC
Japan Exlan Co Ltd
Toyobo Co Ltd
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Application filed by Hokkaido University NUC, Japan Exlan Co Ltd, Toyobo Co Ltd filed Critical Hokkaido University NUC
Priority to JP2012500633A priority Critical patent/JPWO2011102400A1/ja
Publication of WO2011102400A1 publication Critical patent/WO2011102400A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
    • 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
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/71—Ceramic products containing macroscopic reinforcing agents
    • C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
    • C04B35/80—Fibres, filaments, whiskers, platelets, or the like
    • C04B35/83—Carbon fibres in a carbon matrix
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52—Constituents or additives characterised by their shapes
    • C04B2235/5284—Hollow fibers, e.g. nanotubes
    • C04B2235/5288—Carbon nanotubes

Definitions

  • the present invention relates to a method for producing a precursor fiber for obtaining a carbon fiber having high strength and high elastic modulus.
  • the present invention also relates to a precursor fiber obtained by such a production method and a high-strength and high-modulus carbon fiber obtained from such a precursor fiber. Furthermore, the present invention relates to a spinning dope used for the production of such precursor fibers.
  • carbon fiber Since carbon fiber has extremely excellent physical properties such as light weight, high strength, and high elastic modulus, it forms exercise equipment such as fishing rods, golf clubs and skis, CNG tanks, flywheels, wind turbines for wind power generation, turbine blades, etc. It is used as a reinforcing material for structures such as materials, roads and piers, as well as aircraft and space materials, and its uses are expanding.
  • Carbon fibers are roughly classified into PAN-based carbon fibers made from polyacrylonitrile and pitch-based carbon fibers made from coal-derived coal tar, petroleum-derived decant oil, ethylene bottom, and the like. Any carbon fiber is manufactured by first producing a precursor fiber from these raw materials and heating the precursor fiber at a high temperature to make it flame resistant, pre-carbonized, and carbonized.
  • PAN-based carbon fibers can achieve a very high tensile strength of about 6 GPa at the maximum, but it is difficult to develop a tensile elastic modulus and remains at a maximum of about 300 GPa.
  • pitch-based carbon fibers that are currently available on the market can achieve a very high tensile elastic modulus of about 800 GPa at the maximum, but the tensile strength is difficult to develop and remains at about 3 GPa at the maximum.
  • a carbon fiber having a high tensile strength and a high tensile modulus is desirable, but there is no carbon fiber currently proposed that satisfies this requirement.
  • precursor fibers carbon nanotube-containing PAN precursor fibers obtained by adding carbon nanotubes to a polyacrylonitrile-based polymer and spinning them are higher than conventional PAN-based precursor fibers. It is disclosed to exhibit a tensile modulus.
  • the precursor fiber obtained by the method of Patent Document 1 is excellent in terms of tensile elastic modulus, since the cross-sectional shape is not circular but is distorted greatly, the carbon fiber obtained from this precursor fiber is a conventional PAN-based carbon. Does not show high tensile strength like fibers. Therefore, after all, a carbon fiber having both the high tensile strength and the high tensile elastic modulus has not been obtained yet.
  • the present invention has been created in view of the current state of the prior art, and its purpose is to provide precursor fibers capable of producing carbon fibers having high tensile strength and high tensile modulus, and industrially advantageous production thereof. It is to provide a method.
  • the present inventor has intensively studied the improvement of the method of Patent Document 1, and as a result, in the case of a carbon nanotube-containing PAN precursor fiber obtained by the method of Patent Document 1, Since dimethylformamide (DMF) is used, carbon nanotubes easily aggregate and precipitate instantly when the carbon nanotube dispersion is added to the spinning dope. Also, the carbon nanotubes are added to the DMF using ultrasonic waves in advance. Even if it is dispersed, the stability of the dispersed state is low, and agglomeration / precipitation occurs during the preparation of the spinning stock solution.
  • DMF dimethylformamide
  • the present inventors further provide a method for suppressing the precipitation of carbon nanotubes in the spinning stock solution while using dimethylformamide (DMF), dimethyl sulfoxide (DMSO), or dimethylacetamide (DMAc) as a solvent for the spinning stock solution.
  • DMF dimethylformamide
  • DMSO dimethyl sulfoxide
  • DMAc dimethylacetamide
  • amphoteric molecules contained in the spinning dope are extracted into the coagulation bath during spinning and hardly remain in the yarn, so that it is found that the effect of improving the physical properties of the yarn by adding carbon nanotubes is high, thereby completing the present invention. It came.
  • a method for producing a carbon fiber precursor fiber which comprises the following steps: (1) a step of preparing a solution of amphoteric molecules of dimethylformamide, dimethylsulfoxide, or dimethylacetamide; (2) adding carbon nanotubes to this amphoteric molecule solution, dispersing the carbon nanotubes, and preparing a carbon nanotube dispersion; (3) A step of mixing the carbon nanotube dispersion and the polyacrylonitrile polymer to prepare a spinning dope; (4) A step of obtaining a coagulated yarn from the spinning dope by a wet or dry wet spinning method; and (5) a step of drawing the coagulated yarn to obtain a carbon fiber precursor fiber.
  • the spinning dope prepared in step (3) contains 5 to 35% by weight of polyacrylonitrile-based polymer, and further 0.01 to 5% by weight with respect to the polyacrylonitrile-based polymer. Carbon nanotubes and 0.01-5.0 wt% amphoteric molecules.
  • the wetting treatment is performed before the carbon nanotubes are dispersed in the step (2), and the carbon nanotube dispersion is further stabilized.
  • a carbon fiber precursor fiber produced by the above method wherein the carbon fiber precursor fiber has a substantially circular cross section and includes carbon nanotubes.
  • a carbon fiber produced by flame-proofing, pre-carbonizing and carbonizing the precursor fiber characterized by having a high tensile strength and a high tensile elastic modulus. Fiber is provided.
  • a spinning dope comprising a solution of dimethylformamide, dimethyl sulfoxide, or dimethylacetamide containing a polyacrylonitrile-based polymer, carbon nanotubes, and amphoteric molecules, and the carbon nanotubes are dispersed by the action of the amphoteric molecules.
  • a spinning dope is provided that is dispersed in a solution.
  • amphoteric molecules suppress aggregation and precipitation of carbon nanotubes from the spinning dope as a dispersant, and the amphoteric molecules are extracted into a coagulation bath during spinning.
  • the obtained yarn does not contain a lump of aggregates and precipitates, and can be sufficiently stretched to orient the polymer chains and the carbon nanotubes. Therefore, carbon fibers obtained from such precursor fibers have a high tensile elastic modulus in addition to the high tensile strength that is characteristic of PAN-based carbon fibers due to the inclusion of appropriately oriented carbon nanotubes and the orientation of polymer chains. Indicates.
  • the spinning dope used in the production method of the present invention is different from the spinning dope using a dispersing agent usually used for dispersion of carbon nanotubes, and it is necessary to perform ultrasonic irradiation and centrifugation during dispersion of the carbon nanotubes. Therefore, the production method of the present invention is very suitable for industrial production.
  • step (1) a solution of amphoteric molecule DMF, DMSO, or DMAc is prepared (step (1)).
  • the amphoteric molecule used in the present invention is a molecule having a positive charge group and a negative charge group in one molecule, and each group forms a salt with a counter ion.
  • amphoteric molecules can be used alone or in admixture of two or more, and can also be used in combination with a cationic surfactant, an anionic surfactant or a neutral surfactant. .
  • Preparation of amphoteric molecule DMF, DMSO, or DMAc solution can be easily performed by adding amphoteric molecule to DMF, DMSO, or DMAc and stirring at room temperature.
  • DMF, DMSO, or DMAc may be used singly or as a mixture thereof.
  • the concentration of the amphoteric molecule is preferably 0.01 to 5.0% by weight, more preferably 0.1 to 2.0% by weight. If the amount is less than the above lower limit, the effect of the carbon nanotube as a dispersant may not be sufficiently exhibited. On the other hand, if the above upper limit is exceeded, there is a possibility that the effect of the carbon nanotube as a dispersant will not be sufficiently exhibited.
  • carbon nanotubes are added to the DMF, DMSO, or DMAc solution of the amphoteric molecule to disperse the carbon nanotubes, thereby preparing a carbon nanotube dispersion (step (2)).
  • the carbon nanotube used in the present invention may be a single-walled carbon nanotube, a double-walled carbon nanotube, a multi-walled carbon nanotube, or a mixture thereof.
  • the ends of various carbon nanotubes may be closed or perforated.
  • the diameter of the carbon nanotube is preferably 0.4 nm or more and 100 nm or less, and more preferably 0.8 nm or more and 80 nm or less.
  • the length of the carbon nanotube is not limited, and an arbitrary length can be used, but it is preferably 0.6 ⁇ m or more and 200 ⁇ m or less.
  • the purity of the carbon nanotubes used in the present invention is preferably 80% or more as carbon purity, more preferably 90% or more, and still more preferably 95% or more. Carbon purity is determined by differential thermal analysis.
  • Examples of carbon nanotube impurities include amorphous carbon components and catalytic metals.
  • the amorphous carbon component can be removed by heating in air at 200 ° C. or higher or by washing with hydrogen peroxide.
  • the catalyst metal during the production of carbon nanotubes such as iron can be removed by washing with water.
  • the amount of carbon nanotube added is preferably 0.01 to 5% by weight, more preferably 0.1 to 3% by weight, based on the amount of polyacrylonitrile-based polymer to be mixed in the next step (3). preferable. If it is less than the said minimum, there exists a possibility that the amount of carbon nanotubes in the precursor fiber obtained may decrease and a sufficiently high tensile elastic modulus cannot be achieved. On the other hand, if the above upper limit is exceeded, the spinning dope loses spinnability, and spinning may be difficult.
  • Dispersion of carbon nanotubes is necessary in order to loosen the bundled carbon nanotubes.
  • amphoteric molecules When amphoteric molecules are used, they are dispersed if gently stirred, but they are also industrially efficient and evenly dispersed. It is better to disperse by applying physical force.
  • the dispersion method include a ball mill, a bead mill, and dispersion using a plurality of three or more rolls. If the dispersion becomes black and transparent visually, the carbon nanotubes are sufficiently dispersed.
  • the wetting treatment refers to a treatment for creating a trigger for the dispersion of the carbon nanotubes by allowing the amphoteric molecules as a dispersant to penetrate between the bundled carbon nanotubes.
  • the amphoteric molecules are used, carbon nanotubes are gradually dispersed by electrostatic force only by applying gentle stirring.
  • the amphoteric molecules are infiltrated between the carbon nanotubes by a physical method, and the dispersion is completed in a short time without unevenness.
  • a temperature is applied to a system in which carbon nanotubes exist in an autoclave to swell the bundle of carbon nanotubes, and then a pressure is applied.
  • the temperature range at this time is 50 to 150 ° C., more preferably 80 to 150 ° C., and the pressure range is 1.1 to 2.0 atm.
  • the stabilization treatment is a treatment for preventing the dispersed carbon nanotubes from reaggregating, and has an effect of preventing a change with time when the carbon nanotube dispersion liquid is not used immediately.
  • Stabilizers include polyhydric alcohols such as polyhydric alcohols such as glycerol and ethylene glycol, polyvinyl alcohol, polyoxyethylenes such as polyoxyethylenated fatty acids and ester derivatives thereof, polysaccharides, For example, water-soluble cellulose, water-soluble starch, water-soluble glycogen, derivatives thereof such as cellulose acetate, amylopectin, and amines such as alkylamine are exemplified. These stabilizers may be used alone or in combination of two or more. The amount of the stabilizer added is preferably 0.006 to 3% by weight, more preferably 0.06 to 1.2% by weight, based on the amount of the carbon nanotube dispersion.
  • step (3) the carbon nanotube dispersion and the polyacrylonitrile polymer are mixed to prepare a spinning dope.
  • a polyacrylonitrile-based polymer may be added to the carbon nanotube dispersion, or a polymer solution obtained by dissolving a polyacrylonitrile-based polymer in DMF, DMSO, or DMAc and a carbon nanotube dispersion are mixed. Also good. Further, a polymer solution in which a small amount of polyacrylonitrile-based polymer is dissolved in the carbon nanotube dispersion liquid and a polymer solution in which only the polyacrylonitrile-based polymer is dissolved in DMF, DMSO, or DMAc may be mixed. Mixing does not have to be performed at once, and may be performed separately.
  • polyacrylonitrile-based polymer used in the present invention polyacrylonitrile and a copolymer composed of a vinyl monomer copolymerizable with acrylonitrile can be used.
  • the copolymer include acrylonitrile-methacrylic acid copolymer, acrylonitrile-methyl methacrylate copolymer, acrylonitrile-acrylic acid copolymer, acrylonitrile-itaconic acid copolymer, acrylonitrile Examples include methacrylic acid-itaconic acid copolymer, acrylonitrile-methyl methacrylate-itaconic acid copolymer, and acrylonitrile-acrylic acid-itaconic acid copolymer.
  • the acrylonitrile component should be 85 mol% or more. Is preferred.
  • These polymers may form a salt with alkali metal or ammonia. These polymers can be used alone or as a mixture of two or more.
  • the amount of polyacrylonitrile-based polymer added is preferably such that it is 5 to 35% by weight, more preferably 10 to 25% by weight in the spinning dope. If it is less than the above lower limit, the spinning tension cannot be applied, and the orientation of the carbon itself and the carbon nanotubes in the yarn is insufficient, which may cause insufficient strength. On the other hand, if the above lower limit is exceeded, there is a risk of increasing the back pressure during spinning.
  • the spinning dope obtained by the above step (3) consists of a solution of DMF, DMSO, or DMAc containing polyacrylonitrile-based polymer, carbon nanotubes, and amphoteric molecules.
  • the carbon nanotubes are stably dispersed in DMF, DMSO, or DMAc due to the dispersing action of amphoteric molecules, and are difficult to precipitate even if any impact is applied.
  • the viscosity of the spinning dope of the present invention is usually 30 ° C., preferably 2 to 20 Pa ⁇ sec for wet spinning, and preferably 100 to 500 Pa ⁇ sec for dry and wet spinning.
  • the range is below the above range, there is a possibility that the spinning solution may adhere to the nozzle surface at the time of spinning, or there is a problem of cutting of the discharged yarn or quality unevenness. This may cause problems in spinning operability, such as inability to perform stable spinning.
  • a coagulated yarn is obtained from this spinning dope by a wet or dry wet spinning method (step (4)).
  • the hole diameter of the spinneret is usually preferably from 0.03 to 0.1 mm for wet spinning, and preferably from 0.1 to 0.3 mm for dry and wet spinning.
  • the draft ratio may decrease during spinning and the productivity may be significantly impaired, and there is a problem of cutting of the discharged yarn and quality unevenness.
  • the discharge linear velocity of the spinning dope becomes low. Therefore, there is a possibility that problems may occur in the operability of spinning, such as an increase in yarn tension in the coagulation bath.
  • the coagulation bath it is preferable to use a mixture of DMF, DMSO, or DMAc and a so-called coagulation promoting component.
  • a component that does not dissolve the polyacrylonitrile-based polymer and is compatible with the solvent (DMF, DMSO, or DMAc) used in the polymer solution is preferable. Specifically, water may be used. preferable.
  • the coagulation bath used in dry-wet spinning has a high concentration of DMF, DMSO, or DMAc within a range in which the cross-section of the single fiber constituting the coagulated yarn is a perfect circle and the side surface of the fiber is smooth. It is preferable to set the temperature low.
  • the temperature of the coagulation bath is preferably 5 ° C. to 20 ° C., for example. If it is less than 5 ° C., the rate of solidification is slow and the take-off rate is lowered. If it exceeds 20 ° C., the yarns are liable to be fused, which is not preferable.
  • the coagulation water washing step may be performed in a single step, but is preferably performed in a multi-step process while gradually reducing the concentration.
  • a precursor fiber having a substantially circular cross section can be obtained, and the tensile strength can be further increased.
  • the second and subsequent water washing steps may be performed during or after the stretching step described later.
  • the first stage coagulation bath is preferably washed with water in a concentration range of 70% by weight or more and less than 90% by weight of DMF, DMSO, or DMAc. If the concentration of DMF, DMSO, or DMAc is less than 70% by weight, only the surface layer of the fiber may solidify first, and the fiber cross section may become distorted. Further, if the concentration of DMF, DMSO, or DMAc is 90% by weight or more, a careful water washing step may be required.
  • the second stage coagulation bath is preferably washed with water in a concentration range of 5% by weight or more and less than 30% by weight of DMF, DMSO, or DMAc.
  • the concentration of DMF, DMSO, or DMAc is less than 5% by weight, DMF, DMSO, or DMAc in the fiber cannot be removed in a short time, and a more careful washing step may be required later. Further, when the concentration of DMF, DMSO, or DMAc is 30% by weight or more, there is no change in the concentration of DMF, DMSO, or DMAc in the fiber after water washing, and there is a possibility that water washing is not substantially performed. In the case where the water washing step is performed in three or more stages, it is preferable to further solidify by lowering the concentration of DMF, DMSO, or DMAc.
  • the take-up speed during spinning is preferably in the range of 3 to 20 m / min. If it is less than 3 m / min, the productivity may be extremely low. On the other hand, if it exceeds 20 m / min, yarn breakage frequently occurs in the vicinity of the spinneret and the operability may be significantly impaired.
  • the coagulated yarn obtained in the step (4) is drawn to obtain a carbon fiber precursor fiber (step (5)).
  • a carbon fiber excellent in mechanical properties can be obtained by increasing the orientation of molecular chains in the fiber.
  • the stretching is preferably performed so that the total stretching ratio is 4 to 12 times, and more preferably, the total stretching ratio is 5 to 7 times. If the total draw ratio is less than the above lower limit, the orientation of the carbon nanotubes in the yarn is insufficient, and there is a possibility that a carbon fiber precursor in which the polyacrylonitrile-based polymer is densely oriented cannot be obtained. Further, when the total draw ratio exceeds the above upper limit, yarn breakage frequently occurs during drawing and there is a possibility that the drawing stability may be lacking.
  • the stretching operation may be any of cold stretching, stretching in hot water, and stretching in steam. Moreover, even if it extends
  • the precursor fibers obtained by the above steps (1) to (5) have a substantially circular cross section necessary for exhibiting high tensile strength, and carbon nanotubes that provide high tensile elastic modulus in an appropriate orientation. Including. Therefore, if this precursor fiber is flame-resistant, pre-carbonized, and carbonized, a carbon fiber having extremely high tensile strength and tensile elastic modulus can be obtained.
  • the flame resistance, pre-carbonization, and carbonization of the precursor fiber may be performed according to conventional methods.
  • the precursor fiber is first stretched in air at a stretch ratio of 0.8 to 2.5. Flame resistance at 200 to 300 ° C., and then pre-carbonized by heating to 300 to 800 ° C. while stretching in an inert gas at a stretch ratio of 0.9 to 1.5, and further stretching in an inert gas
  • Carbon fibers can be obtained by heating to 1000 to 2000 ° C. at a ratio of 0.9 to 1.1 for carbonization.
  • Examples of the inert gas used during the preliminary carbonization treatment and the carbonization treatment include nitrogen, argon, xenon, and carbon dioxide. Nitrogen is preferably used from an economical viewpoint.
  • the maximum temperature achieved during the carbonization treatment is set between 1200 ° C. and 3000 ° C. depending on the desired mechanical properties of the carbon fiber. Generally, the higher the maximum temperature reached in the carbonization treatment, the higher the tensile modulus of the carbon fiber obtained. On the other hand, the tensile strength reaches a maximum at 1500 ° C.
  • the carbonization treatment is performed at 1000 to 2000 ° C., more preferably at 1200 to 1700 ° C., and even more preferably at 1300 to 1600 ° C., so that the two mechanical properties of tensile modulus and tensile strength can be maximized. It is possible.
  • the tensile strength and tensile modulus of the carbon fiber obtained in this example were measured using a tensile tester “TG200NB” manufactured by NMB in accordance with JIS R7606 (2000) “Testing Method for Tensile Properties of Carbon Fiber-Single Fiber”. It was measured.
  • Example 1A Preparation of stock solution for spinning: 5 g of amphoteric molecule 3- (N, N-dimethylmyristylammonio) propanesulfonate was added to 1000 g of DMF and stirred at room temperature for 5 minutes. To this was added 5 g of double-walled carbon nanotubes (Unimid's XO grade), and then wet treatment was performed at 130 ° C. and 1.5 atm for about 2 hours using an autoclave (manufactured by Hirayama, HICLAB HG-50).
  • the carbon nanotubes were dispersed in the amphoteric molecule solution for about 90 minutes while stirring at 40 Hz using a bead mill (Dyno-mill, manufactured by Switzerland, zirconium beads, diameter 0.65 mm). Further, 3 g of polyoxyethylene alkyl lauryl ether sulfonate was added and the mixture was gently stirred for about 5 minutes to perform a stabilization treatment, thereby obtaining a carbon nanotube dispersion. 46 g of the carbon nanotube dispersion, 23 g of AN94-MAA6 copolymer, and 31 g of DMF were mixed and stirred for 1 hour at room temperature to obtain a spinning dope. The composition of the obtained spinning dope is shown in Table 1.
  • Spinning The above spinning solution is extruded from a spinneret having a pore diameter of 0.15 mm and a number of holes of 10 at 80 ° C., and a coagulation bath (1%) of 77 wt% DMF controlled to a temperature of 15 ° C. through an air gap length of 5 mm. Spinning was performed by a dry and wet spinning method introduced into the stage) to obtain a coagulated yarn. Thereafter, it was washed with a 10% by weight DMF aqueous solution (second stage), then stretched twice in air at room temperature, and further washed with water (third stage). Thereafter, the yarn was further stretched 3 times in boiling water, an amino-modified silicone oil agent was applied, and the yarn was dried at 150 ° C. for 5 minutes to obtain a precursor fiber having a single yarn fineness of 1.3 dTex. When the cross-sectional shape of the obtained precursor fiber was confirmed with an electron microscope, it was a substantially circular cross-section.
  • Flameproofing treatment The above precursor fibers were heated in air at a constant length for 1 hour at the first stage 220 ° C, the second stage 230 ° C, the third stage 240 ° C, and the fourth stage 250 ° C, respectively. A 1.38 flameproof yarn was obtained.
  • Precarbonization treatment The flameproofing yarn was heated at 700 ° C. for 2 minutes in a nitrogen stream at a constant length to obtain a precarbonized yarn.
  • Carbonization treatment The precarbonized yarn was heated at 1300 ° C. for 2 minutes in a nitrogen stream at a constant length to obtain carbon fibers. Table 2 shows the tensile strength and tensile modulus of the obtained carbon fiber.
  • Example 2A A spinning dope was obtained in the same manner as in Example 1A using single-walled carbon nanotubes (Hipco manufactured by CNI) instead of double-walled carbon nanotubes.
  • the composition of the obtained spinning dope is shown in Table 1. This was further stirred for 3 hours with a rotation / revolution mixer to obtain the final spinning dope. Spinning, preliminary carbonization treatment, and carbonization treatment were carried out in the same manner as in Example 1A to obtain carbon fibers.
  • Table 2 shows the tensile strength and tensile modulus of the obtained carbon fiber.
  • the cross-sectional shape of the precursor fiber was confirmed with an electron microscope, it was a substantially circular cross-section as in Example 1A.
  • Example 3A A spinning dope was obtained in the same manner as in Example 1A, except that multi-walled carbon nanotubes (Baytubes manufactured by Bayer) were used instead of double-walled carbon nanotubes in Example 1A.
  • the composition of the obtained spinning dope is shown in Table 1.
  • carbon fibers were obtained in the same manner as in Example 1A.
  • Table 2 shows the tensile strength and tensile modulus of the obtained carbon fiber.
  • the cross-sectional shape of the precursor fiber was confirmed with an electron microscope, it was a substantially circular cross-section as in Example 1A.
  • Example 4A A spinning dope was obtained in the same manner as in Example 1A, except that AN95-MA5 copolymer was used instead of AN94-MAA6 copolymer in Example 1A.
  • the composition of the obtained spinning dope is shown in Table 1.
  • carbon fibers were obtained in the same manner as in Example 1A.
  • Table 2 shows the tensile strength and tensile modulus of the obtained carbon fiber.
  • the cross-sectional shape of the precursor fiber was confirmed with an electron microscope, it was a substantially circular cross-section as in Example 1A.
  • Example 5A A spinning dope was obtained in the same manner as in Example 3A, except that AN95-MAA4-IA1 copolymer was used instead of AN94-MAA6 copolymer in Example 3A.
  • the composition of the obtained spinning dope is shown in Table 1.
  • carbon fibers were obtained in the same manner as in Example 3A.
  • Table 2 shows the tensile strength and tensile modulus of the obtained carbon fiber.
  • the cross-sectional shape of the precursor fiber was confirmed with an electron microscope, it was a substantially circular cross-section as in Example 1A.
  • Example 6A A spinning dope was obtained in the same manner as in Example 1A, except that PAN was used instead of the AN94-MAA6 copolymer in Example 1A.
  • the composition of the obtained spinning dope is shown in Table 1.
  • carbon fibers were obtained in the same manner as in Example 1A.
  • Table 2 shows the tensile strength and tensile modulus of the obtained carbon fiber.
  • the cross-sectional shape of the precursor fiber was confirmed with an electron microscope, it was a substantially circular cross-section as in Example 1A.
  • Example 7A In Example 6A, single-walled carbon nanotubes were used instead of double-walled carbon nanotubes, and a spinning dope was produced by stirring for 3 hours with a rotation / revolution mixer in the same manner as in Example 2A. A spinning dope was obtained. The composition of the obtained spinning dope is shown in Table 1. Using this spinning dope, carbon fibers were obtained in the same manner as in Example 6A. Table 2 shows the tensile strength and tensile modulus of the obtained carbon fiber. In addition, when the cross-sectional shape of the precursor fiber was confirmed with an electron microscope, it was a substantially circular cross-section as in Example 1A.
  • Example 8A A spinning dope was obtained in the same manner as in Example 4A, except that multi-walled carbon nanotubes were used instead of double-walled carbon nanotubes in Example 4A.
  • the composition of the obtained spinning dope is shown in Table 1.
  • carbon fibers were obtained in the same manner as in Example 4A.
  • Table 2 shows the tensile strength and tensile modulus of the obtained carbon fiber.
  • the cross-sectional shape of the precursor fiber was confirmed with an electron microscope, it was a substantially circular cross-section as in Example 1A.
  • Example 9A A spinning dope was obtained in the same manner as in Example 1A, except that 1.0 g of double-walled carbon nanotubes was used in Example 1A.
  • the composition of the obtained spinning dope is shown in Table 1.
  • carbon fibers were obtained in the same manner as in Example 1A.
  • Table 2 shows the tensile strength and tensile modulus of the obtained carbon fiber.
  • the cross-sectional shape of the precursor fiber was confirmed with an electron microscope, it was a substantially circular cross-section as in Example 1A.
  • Example 10A A stock solution for spinning was obtained in the same manner as in Example 3A, except that 5 g of 3- (N, N-dimethylstearylammonio) propanesulfonate was used as the amphoteric molecule in Example 3A.
  • the composition of the obtained spinning dope is shown in Table 1.
  • carbon fibers were obtained in the same manner as in Example 3A.
  • Table 2 shows the tensile strength and tensile modulus of the obtained carbon fiber.
  • the cross-sectional shape of the precursor fiber was confirmed with an electron microscope, it was a substantially circular cross-section as in Example 1A.
  • Example 11A A stock spinning solution was obtained in the same manner as in Example 1A, except that 5 g of 3-[(3-cholamidopropyl) dimethylammonio] -1-propanesulfonate was used as the amphoteric molecule in Example 1A.
  • the composition of the obtained spinning dope is shown in Table 1.
  • carbon fibers were obtained in the same manner as in Example 1A.
  • Table 2 shows the tensile strength and tensile modulus of the obtained carbon fiber.
  • the cross-sectional shape of the precursor fiber was confirmed with an electron microscope, it was a substantially circular cross-section as in Example 1A.
  • Comparative Example 1A DMF77g and AN94-MAA6 copolymer 23g were stirred at room temperature for 1 hour to obtain a spinning dope. Using this spinning dope, carbon fibers were obtained in the same manner as in Example 1A. Table 2 shows the tensile strength and tensile modulus of the obtained carbon fiber. In addition, when the cross-sectional shape of the precursor fiber was confirmed with an electron microscope, it was a substantially circular cross-section as in Example 1A.
  • the above spinning solution is extruded from a spinneret having a hole diameter of 0.15 mm and a hole number of 1 at 80 ° C., introduced into a coagulation bath consisting of 15 l of methanol cooled to ⁇ 60 ° C. through an air gap length of 40 mm, and the yarn is wound I took it. After dipping the yarn for one day in methanol at -60 ° C, it is stretched 9 times, applied with an amino-modified silicone oil, and dried at 150 ° C for 5 minutes to give a precursor fiber having a single yarn fineness of 1.8 dTex. Got. When the cross-sectional shape of the obtained precursor fiber was confirmed with an electron microscope, it was not a substantially circular cross-section but a distorted shape.
  • Example 1A shows the tensile strength and tensile modulus of the obtained carbon fiber.
  • the cross-sectional shape of the precursor fiber was confirmed with an electron microscope, it was a substantially circular cross-section as in Example 1A. In Reference Example 1A, it took about three times longer to disperse the carbon nanotubes than in Examples 1A to 11A.
  • carbon nanotubes are dispersed in an amphoteric molecule solution for about 90 minutes with stirring at 40 Hz. Got. No stabilization treatment was performed on any of them.
  • these dispersions were allowed to stand for 2 weeks, the carbon nanotubes aggregated with each other, and a black solid appeared at the bottom of the container.
  • the carbon nanotube dispersion prepared by performing the stabilization treatment as in Examples 1A to 11A, 1B to 11B, or 1C to 11C does not show aggregation of the carbon nanotubes even after standing for 2 weeks. It was.
  • Examples 1B to 11B, Comparative Examples 1B to 2B, Reference Example 1B A spinning dope was prepared in the same manner as in Examples 1A to 11A, Comparative Examples 1A to 2A, and Reference Example 1A, except that DMSO was used instead of DMF, to obtain carbon fibers.
  • Table 3 shows the cross-sectional shape of the precursor fiber and the physical properties of the carbon fiber.
  • Examples 1C to 11C, Comparative Examples 1C to 2C, Reference Example 1C A spinning dope was prepared in the same manner as in Examples 1A to 11A, Comparative Examples 1A to 2A, and Reference Example 1A, except that DMAc was used instead of DMF, to obtain carbon fibers.
  • Table 4 shows the cross-sectional shape of the precursor fiber and the physical properties of the carbon fiber.
  • Examples 1A to 11A, 1B to 11B, 1C to 11C and Reference Examples 1A to 1C in which carbon nanotubes were added and amphoteric molecules were used as a dispersant, all had high tensile strength and While carbon fibers having a tensile modulus were obtained, Comparative Examples 1A to 1C (conventional general PAN carbon fibers) that did not use carbon nanotubes and did not use amphoteric molecules had a tensile strength of Although it was high, the tensile elastic modulus was inferior. Further, Comparative Examples 2A to 2C, which used carbon nanotubes but did not use amphoteric molecules, had higher tensile elastic modulus than Comparative Examples 1A to 1C, but were inferior in tensile strength.
  • carbon fiber having both high tensile strength and high tensile elastic modulus can be obtained.
  • Such carbon fibers are extremely useful as aircraft materials and spacecraft materials.

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Abstract

L'invention concerne un procédé de fabrication de fibre de précurseur qui permet de fabriquer une fibre de carbone dotée d'une résistance mécanique et d'un module d'élasticité élevés. Ce procédé de fabrication comporte : une étape de préparation d'une solution de diméthylformamide, de diméthylsulfoxyde, ou de diméthylacétamide de molécules amphotères; une étape de préparation d'une dispersion de nanotubes de carbone par ajout de nanotubes de carbone dans cette solution de diméthylacétamide de molécules amphotères, et par dispersion des nanotubes de carbone; une étape de préparation d'une solution de matière première de filage par mélange d'un polymère de polyacrylonitrile avec cette dispersion de nanotubes de carbone; une étape d'obtention d'un fil solidifié au moyen d'un procédé de filage par voie humide ou par voie sèche-humide à partir de cette solution de matière première de filage; et une étape d'obtention d'une fibre de précurseur pour fibre de carbone par étirage de ce fil solidifié.
PCT/JP2011/053317 2010-02-22 2011-02-17 Procédé de fabrication de fibre de précurseur destinée à obtenir une fibre de carbone de résistance mécanique et de module d'élasticité élevés Ceased WO2011102400A1 (fr)

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CN102517671A (zh) * 2011-12-09 2012-06-27 东华大学 水相悬浮和溶液聚合两步法制备碳纤维原丝的方法
JP2013100206A (ja) * 2011-11-09 2013-05-23 Hitachi Chemical Co Ltd カーボンナノチューブの分散液、及びカーボンナノチューブの分散液の製造方法
JP2014084255A (ja) * 2012-10-24 2014-05-12 Hokkaido Univ カーボンナノチューブ薄膜、透明電極及びフォトリソグラフィ用電極
JP2016540131A (ja) * 2013-06-21 2016-12-22 コーロン インダストリーズ インク 炭素繊維用ポリアクリロニトリル系前駆体繊維及びその製造方法
JP2018020933A (ja) * 2016-08-03 2018-02-08 ナノサミット株式会社 カーボンナノチューブを含有する三次元多孔質体及びその製造方法
JP2024025248A (ja) * 2022-08-11 2024-02-26 株式会社豊田中央研究所 繊維束の加熱方法およびその加熱装置
WO2025023970A1 (fr) * 2023-07-25 2025-01-30 Zeon Corporation Solution de nanotubes, tissu de nanotubes de carbone et procédé de production d'une solution de nanotubes

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JP2013100206A (ja) * 2011-11-09 2013-05-23 Hitachi Chemical Co Ltd カーボンナノチューブの分散液、及びカーボンナノチューブの分散液の製造方法
CN102517671A (zh) * 2011-12-09 2012-06-27 东华大学 水相悬浮和溶液聚合两步法制备碳纤维原丝的方法
JP2014084255A (ja) * 2012-10-24 2014-05-12 Hokkaido Univ カーボンナノチューブ薄膜、透明電極及びフォトリソグラフィ用電極
JP2016540131A (ja) * 2013-06-21 2016-12-22 コーロン インダストリーズ インク 炭素繊維用ポリアクリロニトリル系前駆体繊維及びその製造方法
JP2018020933A (ja) * 2016-08-03 2018-02-08 ナノサミット株式会社 カーボンナノチューブを含有する三次元多孔質体及びその製造方法
JP2024025248A (ja) * 2022-08-11 2024-02-26 株式会社豊田中央研究所 繊維束の加熱方法およびその加熱装置
JP7644060B2 (ja) 2022-08-11 2025-03-11 株式会社豊田中央研究所 繊維束の加熱方法およびその加熱装置
WO2025023970A1 (fr) * 2023-07-25 2025-01-30 Zeon Corporation Solution de nanotubes, tissu de nanotubes de carbone et procédé de production d'une solution de nanotubes

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