WO2004050764A1 - 全芳香族ポリアミドとカーボンナノチューブとからなるコンポジットファイバー - Google Patents
全芳香族ポリアミドとカーボンナノチューブとからなるコンポジットファイバー Download PDFInfo
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- WO2004050764A1 WO2004050764A1 PCT/JP2003/015487 JP0315487W WO2004050764A1 WO 2004050764 A1 WO2004050764 A1 WO 2004050764A1 JP 0315487 W JP0315487 W JP 0315487W WO 2004050764 A1 WO2004050764 A1 WO 2004050764A1
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- carbon nanotube
- composite fiber
- carbon nanotubes
- treatment
- aromatic polyamide
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Classifications
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino-carboxylic acids or of polyamines and polycarboxylic acids
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- 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
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- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
- D01F6/605—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides from aromatic polyamides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2929—Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
Definitions
- Composite fiber consisting of wholly aromatic polyamide and carbon nanotube
- the present invention relates to a composite fiber comprising a wholly aromatic polyamide and a carbon nanotube, which is characterized in that a carbon nanotube is oriented in the direction of an i-axis and has excellent mechanical properties.
- the wholly aromatic polyamide has a structure in which rigid aromatic rings are connected, and as a material with excellent heat resistance, mechanical properties, chemical resistance, etc. »Electric insulation material in the form of a film or various reinforcements, various reinforcements Although it is widely used and widely used in industrial applications, such as chemicals and bulletproof fibers, it is becoming increasingly important for resins to have more advanced properties depending on the intended use. Was.
- WO 03/085049 also describes a method for producing a composition comprising single-walled carbon nanotubes and an aromatic polyamide, and a method for preparing a composition comprising an aromatic polyamide in an anhydrous sulfuric acid solution.
- the method of adding carbon nanotubes to carbon fiber is preferred.There is no description of the dispersion and orientation of carbon nanotubes in the composite fiber and its effect on physical properties, and the effect of improving the mechanical properties of the fiber is unknown. It is.
- An object of the present invention is to provide a composite fiber comprising a wholly aromatic polyamide and a carbon nanotube having improved mechanical properties, particularly elastic modulus and strength. That is, the following formulas (A) and (B)
- Ar 1 and Ar 2 each independently represent a divalent aromatic group having 620 carbon atoms.
- a composite fiber characterized in that carbon nanotubes are oriented in the fiber axis direction.
- ⁇ is the azimuth in X-ray diffraction measurement
- I is the diffraction intensity of the 002 crystal plane of the multi-walled carbon nanotube.
- the orientation coefficient F of the carbon nanotube determined by the above is 0.1 or more.
- the G-band intensity when the laser polarization plane is arranged parallel to the fiber axis is I ⁇
- the G-band intensity when the laser polarization plane is arranged perpendicular to the fiber axis is I ⁇ .
- the degree of orientation P represented by satisfies 0 to 0.7.
- the present invention is a method for producing the above composite fiber.
- FIG. 1 is an electron microscope (TEM) photograph observed from a cross section of a fiber cut in a direction substantially parallel to a fiber axis of a composite fiber manufactured in Example 2.
- the arrow in the figure is in the direction of the fiber axis, and the white line is the trace of the carbon nanotube dragged by the cutter when cutting ⁇ t.
- FIG. 2 is an electron microscope (TEM) photograph observed from a fiber cross section of the composite fiber manufactured in Example 3 cut in a direction substantially parallel to the fiber axis.
- the arrow in the figure is in the direction of the fiber axis, and the white line is the trace of the carbon nanotube dragged by the cutter when cutting the fiber.
- FIG. 3 is an electron microscope (TEM) photograph observed from a cross section of the fiber of the composite fiber manufactured in Example 5, which was cut in a direction substantially parallel to the fiber axis.
- the arrow in the figure is in the direction of the fiber axis, and the white line is the trace of the carbon nanotube dragged by the cutter when ⁇ was cut.
- the carbon nanotube in the composite fiber of the present invention has an average diameter of 300 nm or less, preferably 0.3 to 250 nm, more preferably 0.3 to 200 nm, and still more preferably 0.4. ⁇ : 100 nm. Those having a diameter of less than 0.3 nm are substantially difficult to produce, and those having a diameter of more than 300 nm are not preferred because they are difficult to disperse in a solvent.
- the average diameter and the aspect ratio of the carbon nanotube can be determined by observation with an electron microscope. For example, a TEM (transmission electron microscope) measurement can be performed, and the diameter and the length in the longitudinal direction of the carbon nanotube can be directly measured from the image.
- the morphology of carbon nanotubes in the composite fiber can be determined by, for example, TEM (transmission electron microscope) measurement of a cross section of the fiber cut parallel to the H! Axis.
- the graph ensheet is wound in a cylindrical shape, so that the cylinder may have a single-layer structure or a multi-layer structure.
- Darafuen sheets may be stacked in a cup shape.
- preferred examples of the carbon nanotube in the present invention include a single-walled carbon nanotube, a multi-walled carbon nanotube, and a cup-stacked carbon nanotube.
- These carbon nanotubes are produced by a conventionally known method, and include, but are not limited to, a gas-phase flow method, a catalyst-supported gas-phase flow method, a laser ablation method, a high-pressure carbon monoxide method, an arc discharge method, and the like. Not something.
- the wholly aromatic polyamide in the composite fiber of the present invention substantially has the following formulas (A) and (B)
- Ar 1 and Ar 2 each independently represent a divalent aromatic group having 6 to 20 carbon atoms.
- Ar 1 and Ar 2 are each independently a divalent aromatic group having 6 to 20 carbon atoms. Specific examples thereof include a metaphenylene group, a paraphenylene group, an orthophenylene group, and 2,6.
- One or more of the hydrogen atoms of these aromatic groups are each independently a halogen group such as fluorine, chlorine, and bromine; an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a hexyl group.
- a cycloalkyl group having 5 to 10 carbon atoms such as a cyclopentyl group and a cyclohexyl group; and a cycloalkyl group having 6 to 10 carbon atoms such as a phenyl group.
- the structural units of the above formulas (A), Z and (B) may be copolymers composed of two or more aromatic groups.
- Ar 1 is preferably a metaphenylene group, a paraphenylene group, or a 3,4'-dipheneneethenole group, and a paraphenylene group or a paraphenylene group or a 3,4'-diphenylene group. It is more preferable to use an ether group in combination, and when a paraphenylene group and a 3,4′-diphenylene ether group are used in combination, the molar ratio is 1: 0.8 to: I: 1. More preferably, it is in the range of 2.
- a r 2 is Metafue - Len group, Parafue two alkylene groups are preferred, more preferably Parafue two alkylene groups.
- the copolymer preferably used in the present invention is a copolymer in which Ar 1 is a paraphenylene group and a 3,4′-diphenylene ether group, and Ar 2 is a paraphenylene group. And its copolymerization ratio (monole ratio of the paraphenylene group of Ar 1 to the 3,4'-diphenylene ether group) S1: 0.8 to: 1: a wholly aromatic polyamide in the range of 1.2 , And a wholly aromatic polyamide in which Ar 1 and Ar 2 are both paraphenylene groups.
- These wholly aromatic polyamides can be produced by a conventionally known method such as a solution polymerization method, an interfacial polymerization method, and a melt polymerization method.
- the degree of polymerization can be controlled by the ratio of the aromatic diamine component to the aromatic dicarboxylic acid component.
- the obtained polymer has a molecular weight of a solution prepared by dissolving 0.5 gZl in 98% by weight concentrated sulfuric acid at a concentration of 00 mL.
- the inherent viscosity ⁇ inh measured at 30 ° C. is preferably 0.05 to 2 dLZg, more preferably 1.0 to 10 dL / g.
- composition As for the composition of the composite fiber of the present invention, 0.01 to 100 parts by weight, preferably 0.1 to 60 parts by weight, and more preferably 0.1 to 60 parts by weight of carbon nanotubes with respect to 100 parts by weight of a wholly aromatic polyamide. Preferably it is 1 to 10 parts by weight. If the amount of carbon nanotubes is less than 0.01 part by weight, the effect of improving mechanical characteristics is hardly observed, and if the amount is more than 100 parts by weight, spinning becomes difficult.
- the present invention is characterized in that the carbon nanotubes in the composite fiber are oriented in the fiber axis direction.
- the present invention evaluates the orientation of the strong carbon nanotube by X-ray diffraction measurement or deflected Raman spectroscopy.
- the carbon nanotube is a multi-walled carbon nanotube, the following formula (1)
- An orientation coefficient F represented by 2 can be used. (Masao Kadomoto, et al. “Polymer X-ray diffraction” 1996 S, Maruzen)
- ⁇ is the azimuth angle in the X-ray diffraction measurement
- I represents the diffraction intensity of the 02 crystal plane of the multi-walled carbon nanotube.
- the value of the orientation coefficient F of the multi-walled carbon nanotube is preferably 0.1 or more. It is more preferably at least 0.2, more preferably at least 0.3. The higher the value of F, the better, but the theoretical upper limit when the multi-walled carbon nanotubes are fully oriented is 1.0.
- Polarized Raman spectroscopy refers to the Raman spectrum derived from carbon nanotubes when the incident laser is irradiated on the side of the fiber from the direction perpendicular to the fiber axis.
- the G-band intensity when the laser polarization plane is arranged parallel to the fiber axis is I ⁇
- the G-band intensity when the laser polarization plane is arranged perpendicular to the fiber axis is I ⁇ .
- Such deflected Raman spectroscopy is particularly effective for single-walled carbon nanotubes, but can also be applied to multi-walled carbon nanotubes.
- the content of the multi-walled carbon nanotube is small and the X-ray diffraction peak of the carbon nanotube is hidden in the diffraction pattern of the polymer, it is preferable to measure the degree of orientation by polarized Raman spectroscopy.
- the upper limit of the value of ⁇ is more preferably 0.5, further preferably 0.3, and the closer to 0, the more preferable.
- the value of ⁇ tends to be higher than in the case of single-walled carbon nanotubes, as described in the literature (AM Rao et al., Phys. Rev. 84 (8), 1820).
- the wholly aromatic polyamide in the composite fiber is also preferably oriented in the fiber axis direction, and the orientation coefficient F is preferably 0.5 or more. It is more preferably at least 0.6, and even more preferably at least 0.7.
- the orientation coefficient F is obtained by paying attention to the diffraction intensity I of the 200 crystal plane of the wholly aromatic polyamide in equation (1).
- the degree of increase of the orientation coefficient F is preferably 0.01 or more, more preferably 0.05 or more, and more preferably 0.1 or more.
- the degree of decrease in the orientation P is preferably at least 0.01, more preferably at least 0.05, and even more preferably at least 0.1.
- Solvents used for the application include amide solvents such as dimethylacetamide and N-methyl-1-pyrrolidone, or 100% sulfuric acid, phosphoric acid, polyphosphoric acid, methanesulfonic acid, etc. Acid solvent.
- any known method can be applied. For example, (1) add solid carbon nanotubes to a solution of a wholly aromatic polyamide.
- carbon nanotubes themselves have low solubility and are highly entangled, they generally have poor dispersibility in solvents.Therefore, in the present invention, a carbon nanotube dispersion in a good dispersion state is used. It is desirable to obtain.
- the particle size distribution of carbon nanotubes can be measured by dynamic light scattering, laser diffraction, or the like.
- the dispersibility of carbon nanotubes in a solvent and in a mixed solution In order to enhance the dispersibility of the carbon nanotubes, it is preferable to perform some treatment on the carbon nanotubes in advance.
- the treatment method is not particularly limited as long as the tube structure of the carbon nanotube is maintained, but specific examples include ultrasonic treatment, physical refinement treatment, strong acid treatment, and surface treatment such as zeological surface treatment. Can be mentioned.
- Examples of the physical fine treatment include a dry mill treatment using a ball mill, a wet mill treatment using a bead mill, and a shear treatment using a homogenizer or the like. These treatments can make the carbon nanotubes finer and increase their dispersibility.However, too much treatment can cause a significant decrease in the aspect ratio and damage to the nanotube structure itself. It is necessary to keep this in mind.
- As the strong acid treatment for the carbon nanotube specifically, treatment with a strong acid having pH of 0.01 to 2 can be mentioned. By the strong acid treatment, carbon nanotubes having a carboxylic acid or a hydroxyl group as a substituent can be obtained, and the dispersibility can be improved by increasing the affinity for the solvent / all aromatic polyamide.
- Examples of the strong acid of pHO.1-2 which can be used include nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, dichromic acid, and a mixed acid thereof, among which nitric acid, sulfuric acid and nitric acid, It is preferable to use a mixed acid of the above, or a mixed acid of dichromic acid and sulfuric acid, particularly preferably a high concentration.
- Anhydrous acids such as sulfuric anhydride are not preferred for the purpose of introducing carboxylic acid as a substituent.
- the strong acid treatment is preferably performed in the presence of ultrasonic waves. After strong acid treatment, the carbon nanotubes can be isolated by dispersing the treatment liquid in water, followed by filtration and washing.
- the nanotube structure may be damaged.
- a carbon nanotube having an appropriate proportion of oxygen atoms By performing a strong strong acid treatment, a carbon nanotube having an appropriate proportion of oxygen atoms can be obtained.However, the proportion of oxygen atoms on the surface of carbon nanotubes is 2 to 25 per 100 carbon atoms. Is preferably within the range. Force The presence of oxygen atoms on the carbon nanotube surface is confirmed by surface analysis methods such as ESCA. You can bite.
- examples of the esterification method include a method in which a carboxylic acid in carbon nanotubes after strong acid treatment is reacted with diaryl carbonate to obtain an arylester compound.
- the reaction is preferably carried out in the presence of a catalyst.
- the catalyst include 4-aminopyridine, 4-dimethylaminopyridine, 4-ethylpyraminopyridine, 4-pyrrolidinopyridine, 4-piperidinopyridine, Examples thereof include pyridine-based compounds such as 4-pyrrolinopyridine and 2-methinole-4-dimethinoleaminopyridine. Of these, 4-dimethylaminopyridine and 4-pyrrolidinopyridine are particularly preferred.
- an aryl compound of a carbon nanotube obtained by subjecting to a strong acid treatment followed by esterification is added to an amine compound such as aniline, naphthylamine, parafulenylenediamine, and metaphenylenediamine. Is reacted.
- the orientation of the wholly aromatic polyamide and the carbon nanotubes can be enhanced by performing flow orientation, liquid crystal orientation, shear orientation, or stretch orientation to improve mechanical properties.
- the wholly aromatic polyamide is, for example, Ar 1 is a paraphenylene group and a 3,4′-diphenylene ether group, and A r 2 Is a paraphenylene group, and its copolymerization ratio (molar ratio of the paraphenylene group of Ar 1 to 3,4 ′ diphenylene ether group) is in the range of 1: 0.8 to 1: 1.2.
- a composite fiber can be obtained by stretching and orienting.
- the stretching ratio is preferably 2 to 40 times, more preferably 5 to 30 times. Stretching as close as possible to the maximum stretching ratio (MDR) is desirable from the viewpoint of mechanical properties.
- a preferred temperature during stretching orientation is 100 ° C to 800 ° C, more preferably 200 ° C. C to 600 ° C.
- the wholly aromatic polyamide is, for example, poly (paraphenylene terephthalenoamide) in which both Ar 1 and Ar 2 are paraphenylene groups
- a composite fiber can be obtained by liquid crystal spinning using an acid solvent such as an acid as a mixed solvent.
- the orientation can usually be achieved by spinning the solution from the cap at a high draft ratio.
- the composite fiber comprising a wholly aromatic polyamide and carbon nanotubes obtained by the present invention has excellent mechanical properties, especially elastic modulus and tensile strength, because the carbon nanotubes in the composition are oriented in the fiber axis direction. .
- Average diameter and average aspect ratio of carbon nanotubes Measured using a TEM (transmission electron microscope, model H-800) manufactured by Hitachi, Ltd. After dispersing the carbon nanotubes at a concentration of 0.1 mg / mL in N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) under ultrasonic treatment, the dispersion is dropped on a TEM measurement grid, The sample obtained by drying under reduced pressure was observed. The diameter and length were measured directly from the image, and the average was determined.
- NMP N-methyl-2-pyrrolidone
- X-ray diffraction measurement An X-ray generator (RU-B, manufactured by Rigaku Denki) was measured under the conditions of a target CuKa ray, a voltage of 45 kV, and a current of 7 OmA. The incident X-rays were condensed and monochromated by an Osmic multilayer mirror, and the cross section of the sample was measured by the vertical transmission method. X-ray diffraction was measured using an imaging plate (manufactured by Fuji Photo Film) with a size of 20 Omm x 250 mm and a camera length of 25 Omm.
- an imaging plate manufactured by Fuji Photo Film
- a micro-laser Raman spectrometer (LabRamHR manufactured by Horiba Joban Yvon) was used as the Raman spectrometer.
- a semiconductor laser with a wavelength of 785 nm was used as the excitation laser light source, and the laser beam diameter was focused to about 1 / zm.
- polarized Raman spectroscopy was performed as follows. When measuring the Raman spectrum of carbon nanotubes by irradiating the side surface of the fiber composition with the incident laser from the direction perpendicular to the nl axis, the Raman shift wave number when the laser polarization plane is arranged parallel to the fiber axis is 1580 cm.
- the G-band intensity (I xx ) derived from the graphite structure near —1 and the G-band intensity ( ⁇ ⁇ ) when the laser polarization plane was arranged perpendicular to the fiber axis were measured.
- Elemental analysis of carbon nanotube surface Evaluated by ESCA (X-ray photoelectron spectroscopy). The measurement was performed using VG E SCALAB-200 at an MgKa line (300 w) and a photoelectron extraction angle of 45 degrees.
- Reference Example 1 Preparation of aramide resin solution
- the FeZCo catalyst was supported on zeolite using Y-type zeolite powder (Tosoh; HSZ-32 ONAA) as the porous carrier and ferric acetate and cobalt acetate as the catalytic metal compounds.
- the supported amount of each catalyst was adjusted to 2.5% by weight.
- the catalyst powder was placed on a stone boat, placed in the quartz tube of the CVD system, evacuated, and heated from room temperature to 800 ° C while introducing Ar gas at a flow rate of 1 OmLZ. After reaching the predetermined temperature of 800 ° C, ethanol vapor was introduced at a flow rate of 300 OmL / min, and kept in an ArZ ethanol atmosphere for 30 minutes.
- the resulting black product was analyzed by laser-Raman spectroscopy and transmission electron microscopy, and it was confirmed that single-walled carbon nanotubes had been formed.
- the resulting product (single-walled carbon nanotube zeolite metal catalyst) is immersed in 10% hydrofluoric acid for 3 hours, and washed with ion-exchanged water until neutral to remove zeolite and metal catalyst. Then, the carbon nanotube was purified. Observation of the obtained carbon nanotubes with a TEM revealed that the average diameter was 1.2 nm and the average aspect ratio was 100 or more. However, many had a bundle structure of about 10 nm in width.
- Reference Example 3 Synthesis of multi-walled carbon nanotube
- the single fiber diameter of the fiber was 1.58 dtex, and the X-ray diffraction measurement of the drawn fiber determined that the orientation coefficient F of carbon nanotubes was 0.25 and the orientation coefficient F of aramid resin was 0.750. Was called.
- the elastic modulus was 75.4 GPa and the strength was 26.2 cN / dtex.
- Example 2 5 g of the multi-walled carbon nanotubes synthesized in Reference Example 3 was added to 904 g of NMP, and the NMP dispersion was circulated using 0.3 mm zirconia beads using a wet disperser DYNO-MILL (TYPE KDL).
- the average diameter of the carbon nanotubes after the strong acid treatment was 26 nm, and the average aspect ratio was 56 ′.
- the average particle size determined by dynamic light scattering measurement was 552 nm. Elemental analysis of the surface with ESCA showed that the carbon content was 92.6% and oxygen was 7.4%.
- Spinning was performed in the same manner as in Example 1 to obtain a composite fiber. Table 1 shows various physical properties of the fiber.
- Example 6 Similar to the case of Example 3, a TEM (transmission electron microscope) measurement of the fiber cross section cut almost parallel to the fiber axis of the composite fiber was performed (Fig. 3), and the carbon nanotubes were oriented along the fiber axis direction. I confirmed that Example 6
- the final temperature in the system was set to 320 ° (: The degree of vacuum was set to about 0.5 mmHg (66.7 Pa).
- dichloromethane was added to the residue, and the mixture was suction-filtered through a 0.2 m pore-size membrane filter made of Teflon (Millipore). The remaining phenol and diphenyl carbonate were removed to separate and purify 0.8 g of carbon nanotubes.
- the average diameter of the carbon nanotubes after the reaction was 28 nm and the average aspect ratio was 50 based on TEM measurement.
- a composite fiber was obtained according to Example 2 except that a multi-walled carbon nanotube (trade name: VGCF) manufactured by Showa Denko KK was used. After the bead mill treatment, the carbon nanotubes had an average diameter of 107 nm and an average aspect ratio of 31. The average particle size determined by dynamic light scattering measurement was 1010 nm. Table 1 shows the physical properties of this fiber.
- VGCF multi-walled carbon nanotube
- a composite fiber was obtained in accordance with Example 4 except that a multilayer carbon nanotube (trade name: VGCF) manufactured by Showa Denko KK was used.
- the average diameter of the carbon nanotubes after the strong acid treatment was 94 nm, and the average aspect ratio was 28.
- the average particle size determined by dynamic light scattering measurement was 682 nm. Table 1 shows the physical properties of this fiber.
- Example 10
- the average diameter of the carbon nanotubes after the strong acid treatment was 1. 1 nm, and the average aspect ratio was 100 or more. However, many of them had a bundle structure with a width of about 10 nm, as before.
- the average particle size determined by dynamic light scattering measurement was 189 nm, which was smaller than 250 nm before the treatment.
- the elemental analysis of the surface by ESCA revealed that it was 93.4% carbon and 6.6% oxygen. Performed using 0.15 g of this carbon nanotube.
- ⁇ Alamide resin ⁇ Carbon nanotube A mixed dose of 99/1 (weight ratio) was obtained. Observation of the mixed dope with an optical microscope confirmed that the dispersibility of the carbon nanotubes was high. Spinning was performed in the same manner as in Example 1 to obtain a composite fiber. Table 1 shows the physical properties of this fiber. Comparative Example 1
- Example 1 In the spinning step in Example 1, the composite fiber after being dried by a drying roller at 120 ° C. before stretching was taken out, and various physical properties were evaluated. Table 1 shows the results.
- Example 6 MWNT 5 21.5 1.55 0.430-0.750 74.5 27.7
- Example 7 MWNT 5 Strong acid treatment ⁇ amidation 20.0 1.52 0.487-0.754 75.1 28.0
- Example 8 MWNT 2 Bead mill treatment 19.5 1.43 0.54 0.734 79.3 27.6
- Example 9 MWNT 2 Strong acid treatment 19.2 1.58-0.60 0.742 74.2 27.0
- Example 1 0 SWNT 1 Untreated 19.7 1.53-0.18 0J51 76.8 26.5
- Example 1 1
- SWNT 1 Strong acid treatment 21.2 1.48-0.23 0J46 74.1 27.2 Comparative example 1-0-21.7 1.52--0J50 74.0 25.6
- Comparative example 2 MWNT 5 Super positive wave treatment only 1 37.0 0.093 -0.104 6.7 1.1
Abstract
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Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
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AT03777210T ATE510881T1 (de) | 2002-12-04 | 2003-12-03 | Verbundfaser mit vollaromatischem polyamid und kohlenstoffnanoröhrchen |
AU2003289145A AU2003289145A1 (en) | 2002-12-04 | 2003-12-03 | Composite fiber comprising wholly aromatic polyamide and carbon nanotube |
JP2004556902A JP4209845B2 (ja) | 2002-12-04 | 2003-12-03 | 全芳香族ポリアミドとカーボンナノチューブとからなるコンポジットファイバー |
EP03777210A EP1574551B1 (en) | 2002-12-04 | 2003-12-03 | Composite fiber comprising wholly aromatic polyamide and carbon nanotube |
US10/537,781 US20060188718A1 (en) | 2002-12-04 | 2003-12-03 | Composite fiber including wholly aromatic polyamide and carbon nanotube |
CA2508577A CA2508577C (en) | 2002-12-04 | 2003-12-03 | Composite fiber comprising wholly aromatic polyamide and carbon nanotubes |
HK06105777.2A HK1085754A1 (en) | 2002-12-04 | 2006-05-18 | Composite fiber comprising wholly aromatic polyamide and carbon nanotube |
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JP2002-352178 | 2002-12-04 | ||
JP2002352178 | 2002-12-04 |
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WO2004050764A1 true WO2004050764A1 (ja) | 2004-06-17 |
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US (1) | US20060188718A1 (ja) |
EP (1) | EP1574551B1 (ja) |
JP (1) | JP4209845B2 (ja) |
KR (1) | KR101016591B1 (ja) |
CN (1) | CN100549094C (ja) |
AT (1) | ATE510881T1 (ja) |
AU (1) | AU2003289145A1 (ja) |
CA (1) | CA2508577C (ja) |
HK (1) | HK1085754A1 (ja) |
TW (1) | TWI276649B (ja) |
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Cited By (5)
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- 2003-12-03 EP EP03777210A patent/EP1574551B1/en not_active Expired - Lifetime
- 2003-12-03 US US10/537,781 patent/US20060188718A1/en not_active Abandoned
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- 2003-12-03 CN CN200380105262.4A patent/CN100549094C/zh not_active Expired - Fee Related
- 2003-12-03 AT AT03777210T patent/ATE510881T1/de not_active IP Right Cessation
- 2003-12-03 WO PCT/JP2003/015487 patent/WO2004050764A1/ja active Application Filing
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2008508433A (ja) * | 2004-07-27 | 2008-03-21 | ディーエスエム アイピー アセッツ ビー.ブイ. | カーボンナノチューブ/超高分子量ポリエチレン複合繊維を製造するための方法 |
JP4669876B2 (ja) * | 2004-07-27 | 2011-04-13 | ディーエスエム アイピー アセッツ ビー.ブイ. | カーボンナノチューブ/超高分子量ポリエチレン複合繊維を製造するための方法 |
JP2006207965A (ja) * | 2005-01-31 | 2006-08-10 | Teijin Techno Products Ltd | 防弾衣料用布帛 |
JP2006307367A (ja) * | 2005-04-27 | 2006-11-09 | Teijin Ltd | 全芳香族ポリアミドと薄層カーボンナノチューブとからなるコンポジットファイバー |
JP4647384B2 (ja) * | 2005-04-27 | 2011-03-09 | 帝人株式会社 | 全芳香族ポリアミドと薄層カーボンナノチューブとからなるコンポジットファイバー |
JP2008285789A (ja) * | 2007-05-18 | 2008-11-27 | Teijin Ltd | 全芳香族ポリアミドと多層カーボンナノチューブとからなるコンポジットファイバー |
JP2015105441A (ja) * | 2013-11-28 | 2015-06-08 | 日本ゼオン株式会社 | カーボンナノチューブ含有繊維の製造方法およびカーボンナノチューブ含有繊維 |
Also Published As
Publication number | Publication date |
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JPWO2004050764A1 (ja) | 2006-03-30 |
HK1085754A1 (en) | 2006-09-01 |
CA2508577C (en) | 2011-11-29 |
CN100549094C (zh) | 2009-10-14 |
AU2003289145A1 (en) | 2004-06-23 |
JP4209845B2 (ja) | 2009-01-14 |
US20060188718A1 (en) | 2006-08-24 |
KR101016591B1 (ko) | 2011-02-22 |
CA2508577A1 (en) | 2004-06-17 |
EP1574551B1 (en) | 2011-05-25 |
TWI276649B (en) | 2007-03-21 |
EP1574551A4 (en) | 2008-02-27 |
KR20050085337A (ko) | 2005-08-29 |
EP1574551A1 (en) | 2005-09-14 |
ATE510881T1 (de) | 2011-06-15 |
CN1720295A (zh) | 2006-01-11 |
TW200422350A (en) | 2004-11-01 |
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