EP0304010B1 - Verfahren zum Herstellen von Kohlenstoffmaterialien - Google Patents

Verfahren zum Herstellen von Kohlenstoffmaterialien Download PDF

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Publication number
EP0304010B1
EP0304010B1 EP88113265A EP88113265A EP0304010B1 EP 0304010 B1 EP0304010 B1 EP 0304010B1 EP 88113265 A EP88113265 A EP 88113265A EP 88113265 A EP88113265 A EP 88113265A EP 0304010 B1 EP0304010 B1 EP 0304010B1
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EP
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Prior art keywords
raw material
carbon materials
spinning
fiber
material composition
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Expired - Lifetime
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EP88113265A
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English (en)
French (fr)
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EP0304010A3 (en
EP0304010A2 (de
Inventor
Koji Sakata
Kouji Sakawaki
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Mitsui Mining Co Ltd
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Mitsui Mining Co Ltd
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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
    • D01F9/24—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • This invention relates to a process for producing carbon materials which can be used either in the form of fibers or various molded articles as fillers for various composite materials, heat insulating materials and ablation materials, or in the form of activated carbon materials including molecular sieve carbon materials, activated carbon fibers and the like as adsorbent or separating materials.
  • carbon fibers are produced by spinning rayon, lignin, polyacrylonitrile (hereinafter referred to as PAN), pitch or the like, rendering the spun fiber infusible, carbonizing it at a temperature of 1,000 to 1,600°C, or further graphitizing the resulting carbon fiber at a temperature of 2,000 to 3,000°C.
  • PAN polyacrylonitrile
  • molecular sieve carbon fibers and activated carbon fibers are produced either by spinning a raw material as described above, rendering the spun fiber infusible, and then activating it, or by rendering the spun fiber infusible, carbonizing it, and then activating the resulting carbon fiber.
  • a process for producing carbon materials which comprises the steps of preparing a raw material composition comprising an organic compound which can be carbonized by a carbonization treatment and a solvent, spinning or molding the raw material composition, and carbonizing the spun fiber or molding article, characterized in that the organic compound is a methylene type linkage-containing condensation product of an aromatic sulfonic acid or a salt thereof, the condensation product having been formed by means of a linkage of the formula -(CH2) n -T x -(CHR) m - where T is a benzene or naphthalene ring, R is a hydrogen atom, an alkyl group of 1 to 4 carbon atoms, or a benzene ring, and each of n, m and x is 0 or 1, but n and m should not be zero at the same time.
  • aromatic sulfonic acids can be obtained by sulfonating the corresponding aromatic compounds according to any of various well-known methods.
  • ammonium salts are preferred because of the ease with which the spun fiber can be handled in the carbonization step.
  • preferred salts may vary according to the desired type of carbon material. That is, ammonium salts are preferred for the production of carbon materials requiring strength. In order to produce porous adsorbent materials or separating materials, ammonium salts can be used satisfactorily, but sodium and calcium salts are more preferred.
  • Condensation products of the above-described aromatic sulfonic acids or salts thereof can be prepared according to any of various well-known methods. However, it is common practice to condensate an aromatic sulfonic acid or a salt thereof with the aid of formalin, paraformaldehyde, hexamethylenetetramine or other aldehyde. It is also possible to use a methylene type linkage-containing polymer (such as polystyrenesulfonic acid) obtained by polymerizing an aromatic sulfonic acid having a vinyl group.
  • a methylene type linkage-containing polymer such as polystyrenesulfonic acid
  • linkage connecting molecules of the aromatic sulfonic acid may be any of the linkages within the scope of formula (1)
  • the -CH2- linkage is especially preferred because methylene-linked condensation products are easy to prepare or obtain.
  • the linkage in a methylene type linkage-containing condensation product of an aromatic sulfonic acid or a salt thereof as said in the present invention includes not only those which connect directly with an aromatic ring but also those which connect by means of side chains as in the case of a polystyrenesulfonic acid.
  • condensation products can be obtained, depending on the type of aromatic compound used, the conditions of sulfonation and condensation reactions, and the like. Of course, these condensation products may be used alone or in admixture of two or more, and may also be used in the form of polycondensation products.
  • condensation product obtained by condensing ammonium naphthalene- ⁇ -sulfonate with the aid of formaldehyde.
  • This condensation product is a mixture of monomer and various polymers having polymerization degrees of up to about 200, and has a number-average molecular weight of about 2,000 to 50,000.
  • This condensation product is a solid at ordinary temperatures, sparingly soluble in organic solvents such as benzene, toluene and acetone, and readily soluble in aqueous solvents.
  • a 60% (w/w) aqueous solution thereof has a viscosity of about 1 to 2000 Pa ⁇ s (10 to 20,000 poises)at 60°C and exhibits adequate spinnability and moldability.
  • this condensation product is carbonized at a temperature of 800 to 1,000°C, the yield of the resulting carbon material is about 50% by weight.
  • condensation product is only one example of the condensation products useful in the process of the present invention, and it is to be understood that the range of the polymerization degree, or number-average molecular weight, of a condensation product useful in the process of the present invention depends on the type of the aromatic sulfonic acid, or salt thereof, constituting the condensation product.
  • a useful condensation product of sulfonated creosote oil is a mixture of monomer and various polymers having polymerization degrees of up to about 40, and has a number-average molecular weight of about 2,000 to about 5,000.
  • a useful condensation product of phenanthrenesulfonic acid is a mixture of monomer and various polymers having polymerization degrees of up to about 30, and has a number-average molecular weight of about 2,500 to about 5,000.
  • the above-defined condensation product or polymer of aromatic sulfonic acid or salt thereof is dissolved or dispersed in a solvent to prepare a raw material composition. If necessary, the viscosity of this raw material composition is adjusted by suitable means such as dilution and concentration. Then, the raw material composition is spun into fibrous form or molded into any desired shape such as block, column, plate, film or honeycomb. Finally, the spun fiber or molded article is carbonized to obtain a carbon material.
  • the solvent used in the process of the present invention is preferably selected from polar solvents including water, alcohols (such as methanol), acetonitrile and the like. Among others, it is most preferable to use water or an aqueous solvent comprising a mixture of water and a suitable water-soluble solvent.
  • the aromatic sulfonic acid used as the raw material contains a high proportion of unsulfonated aromatic compounds, because they make the resulting carbon fibers inhomogeneous and cause a reduction in strength.
  • the methylene type linkage-containing condensation products of unsulfonated aromatic compounds can be removed by using water as the solvent. That is, since the methylene-linked condensation products of unsulfonated aromatic compounds are hardly soluble in water and, therefore, can be separated from the spinning solution according to suitable techniques such as filtration, centrifugation and dialysis.
  • suitable techniques such as filtration, centrifugation and dialysis.
  • the use of an aqueous solvent is preferred from operational points of view, because the spinning atmosphere can be controlled easily and there is no risk of ignition or explosion.
  • the spinnability and moldability of the raw material composition can further be improved by adding a water-soluble polymeric compound, as a spinning or molding aid, to the raw material composition in an amount of 0.02 to 20 parts by weight per 100 parts by weight of the solid constituent of the raw material composition.
  • a water-soluble polymeric compound used in the present invention can be any of various polymeric compounds that are soluble or colloidally dispersible in water and aqueous solvents.
  • polyalkylene oxide compounds such as condensation products of ethylene oxide, propylene oxide, etc., and condensation products obtained by the reaction of these compounds with various alcohols, fatty acids, alkylamines and alkylphenols; polyvinyl compounds such as polyvinyl alcohol and polyvinyl pyrrolidone; polyacrylic compounds such as polyacrylic acid, polyacrylamide and acrylic acid-acrylamide copolymer; and the like.
  • polyalkylene oxide compounds such as condensation products of ethylene oxide, propylene oxide, etc., and condensation products obtained by the reaction of these compounds with various alcohols, fatty acids, alkylamines and alkylphenols
  • polyvinyl compounds such as polyvinyl alcohol and polyvinyl pyrrolidone
  • polyacrylic compounds such as polyacrylic acid, polyacrylamide and acrylic acid-acrylamide copolymer
  • those having high solubility in water such as polystyrenesulfonic acid
  • water-soluble polymeric compound such as polystyrenesulfonic
  • water-soluble polymeric compound is effective in accelerating the spinning speed, making it easy to handle the spun fiber or molded article prior to carbonization, and increasing the strength of the resulting carbon fiber or molded product. If the amount of water-soluble polymeric compound added is less than 0.02 part by weight, a satisfactory effect for further improving cannot be obtained. If it is greater than 20 parts by weight, the fiber or the like is liable to fusion during the heating operation for carbonization. This is undesirable because a separate step of rendering it infusible is required.
  • the methylene type linkage-containing condensation product of aromatic sulfonic acid or salt thereof which is used in the process of the present invention, can be spun or molded and then carbonized to produce carbon materials in fibrous form and in various other forms.
  • the process of the present invention is particularly suitable for the production of carbon materials in fibrous form.
  • the content of the condensation product in the raw material composition for spinning may vary according to the types of the condensation product, water-soluble polymeric compound and solvent. However, it is generally in the range of 20 to 80% by weight and preferably in the range of 40 to 70% by weight.
  • the spinning material liquid there are sometimes produced impurities from the raw materials or derivative substances, whether in solid or gel, resulted from reaction by-products among the raw materials.
  • the removal of such impurities or substances is effective in gaining a high-spinnability or an improved quality of carbon materials in fibrous form. Though it can be made outside a spinning machine, the removal can be far effectively carried out by placing a sintered metal filter, a sintered metal fibrous filter, a sintered metal wire netting filter or a pack filter of various metal fillers upon a spinneret.
  • the spinning temperature may vary according to the composition of the spinning material, the desired shape of fiber, and the like. However, where water is used as the solvent, the spinning temperature is preferably in the range of 20 to 100°C.
  • the fiber emerging from the spinneret is drawn out by means of a wind-up roll, godet rolls, an air sucker or the like, is wound up or is accumulated in a receiver after having been dried within a barrel dryer equipped under the spinneret, preferably in a heated-air stream flowing in parallel to the progress of the fiber.
  • a draft ratio i.e., the spinneret's diameter/the spun fiber's diameter
  • the fiber is drawn out can be 100 to 2; however, a preferable range of it is 10 to 5.
  • a fiber with a big surface can be also produced by applying a spinneret of irregular form in order to ease the drying of the fiber and enhance the fibrous strength.
  • the diameter of the spun fiber may be determined aribitrarily, it is preferably in the range of 2 to 100 ⁇ m and more preferably in the range of 8 to 20 ⁇ m.
  • the spun fiber might absorb humidity and melt into another one because of its hygroscopicity if it is left for a long time in the open air. Accordingly, it is favorable soon to send the spun fiber to the carbonization process or to stock it in the dry air when necessary.
  • the spun fiber can be carbonized without being rendered infusible.
  • the spun fiber is fired by heating at a thermal ascending speed of 1 to 2,000°C/min., preferably 10 to 500°C/min., up to a temperature of 500 to 2,000°C, but under a non-oxidation atmosphere such as in a stream of N2 or other non-activated gases.
  • the raw material being an ammonium salt of a methylene type condensation product of an aromatic sulfonic acid
  • a sulfurous acid and an ammonium root are eliminated in the principal range of 250 to 350°C during the carbonization, when the raw material of about 50% by weight is lost.
  • thermal ascending is made at a gentle speed in the range of 250 to 350°C or that a thermal retention time in the same thermal range is included in a thermal program for the carbonization.
  • the fiber may further be fired at a temperature of 2,000 to 3,000°C to obtain a carbon fiber comprising graphite.
  • its properties e.g., tensile strength
  • the content of the condensation product in the raw material composition for molding may vary according to the types of the condensation product, water-soluble polymeric compound and solvent. However, it is generally in the range of 20 to 90% by weight and preferably in the range of 40 to 80% by weight.
  • the molded article can be carbonized under substantially the same conditions as employed for the spun fiber.
  • a continuous process which comprises sulfonating the aromatic compound used as the raw material, condensing it with the aid of formalin or the like while controlling the water content and pH of the reaction system, neutralizing the condensation product, removing any insoluble matter according to the need, adjusting the viscosity of the condensation product (e.g., by controlling its water content) to prepare a spinning or molding material, spinning or molding it, and then carbonizing the spun fiber or molded article to obtain a carbon material.
  • better results can be obtained by adding the above-described water-soluble polymeric compound at the time of preparation of the spinning or molding material.
  • the properties of carbon fibers produced by the process of the present invention will vary according to the type of the aromatic compound, or salt thereof, used in the spinning material, the diameter of the fiber, and the like. More specifically, the strength of the resulting fiber increases with a rise in carbonization temperature. For example, the fiber fired at 600°C has a strength of 196 to 490 MPa (20 to 50 kg/mm2) and the fiber fired at 1,200°C has a strength of 392 MPa to 1960 MPa (40 to 200 kg/mm2).
  • the carbon materials produced by the process of the present invention have a relatively large specific surface area because the elimination of sulfonic groups occurs in the carbonization step. Moreover, since the raw material is sulfonated while it is in the low-molecular-weight state, the sulfonic groups are distributed evenly. Therefore, the carbon materials produced by the present invention are more homogeneous and have more excellent properties than those produced by conventional methods such as the treatment of polymers with sulfuric acid. These carbon materials, especially in fibrous form, can be used as fillers for various composite materials and as heat insulating materials. Moreover, by further subjecting them to an activation treatment, they can also be used as adsorbent or separating materials, including molecular sieve carbon materials, activated carbon fibers and the like.
  • the activation treatment can be carried out in the same manner as for the preparation of ordinary activated carbon and the like.
  • the carbon materials of the present invention may be activated by suitable gases such as steam, air and CO2 or by suitable chemicals such as zinc chloride or sulfuric acid.
  • the activation treatment may be carried out after the spun fiber or molded article has been carbonized, or while the spun fiber or molded article is being carbonized.
  • the spun fiber or molded article (not carbonized) is heated at a temperature of 350°C or above, preferably 450°C or above, in an atmosphere of an inert gas and then treated with steam at a temperature of 700 to 900°C for 10 to 120 minutes.
  • the spun fiber or molded article may be directly treated with steam at a temperature of 700 to 1,000°C for 10 to 180 minutes without heating at a lower temperature.
  • carbon materials having excellent properties and useful in wide applications can be produced by much simpler operation, as compared with prior art processes. Moreover, because of the regular elimination of sulfonic groups, the carbon materials produced thereby have good homogeneity and high activity and, therefore, are of great industrial value.
  • 1,280 g of naphthalene having a purity of 95% was mixed with 1,050 g of 98% sulfuric acid and sulfonated at 160°C for 2 hours. Unreacted naphthalene and the water formed by the reaction were removed from the system by distillation under reduced pressure. Then, 857 g of 35% formalin was added and the resulting mixture was reacted at 105°C for 5 hours to obtain a methylene-linked condensation product of naphthalene- ⁇ -sulfonic acid. Furthermore, this condensation product was neutralized with aqueous ammonia and then filtered through No. 5 filter paper (manufactured by Toyoroshi Kaisha, Ltd.).
  • the filtrate was concentrated to obtain a spinning material in the form of a solution containing 34% by weight of water and having a viscosity of 0.1 Pa ⁇ s (100 centipoises) at 85°C.
  • the resulting salt of the condensation product had a number-average molecular weight of 4,300.
  • This spinning material was dry-spun using a stainless steel spinneret having an orifice diameter of 0.1 mm.
  • the spun fiber was directly subjected to a carbonization step. Specifically, the fiber was fired in a stream of N2 by raising the temperature from room temperature to 800°C at a rate of 10°C/min.
  • the resulting carbon fiber had a diameter of 12 ⁇ m, a tensile strength of 637 MPa (65 kg/mm2), a specific surface area of 250 m2/g as measured by the CO2 BET method, and a specific surface area of 30 m2/g as measured by the N2 BET method.
  • its equilibrium CO2 adsorption was 188 ml/g and its equilibrium N2 adsorption was 25 ml/g.
  • the above fiber was activated by treatment with steam at 850°C for 60 minutes.
  • the resulting fiber had a specific surface area of 1,470 m2/g as measured by the CO2 BET method, and a specific surface area of 1,560 m2/g as measured by the N2 BET method.
  • spinning material A was obtained in the form of a solution having a viscosity of 0.1 Pa ⁇ s (100 centipoises) at 85°C.
  • spinning material B was prepared by taking a part of spinning solution A, neutralizing it with sodium hydroxide, purifying it again by filtration, and then adjusting the filtrate to a water content of 40% by weight.
  • Spinning material A was spun using a platinum spinneret. The spun fiber was directly subjected to a carbonization step where it was fired in a stream of N2 by raising the temperature from room temperature to 1,200°C at a rate of 10°C/min.
  • the resulting carbon fiber had a diameter of 15 ⁇ m and a tensile strength of 504 MPa (52 kg/mm2).
  • Spinning material B was spun using a stainless steel spinneret. The spun fiber was directly subjected to a carbonization step where it was fired in a stream of N2 by raising the temperature from room temperature to 800°C at a rate of 10°C/min and then to an activation step by steam at a temperature of 900°C for 15 minutes.
  • the resulting carbon fiber had a diameter of 12 ⁇ m, a tensile strength of 294 MPa (30 kg/mm2), a specific surface area of 720 m2/g as measured by the CO2 BET method, and a specific surface area of 870 m2/g as measured by the N2 BET method.
  • 1,280 g of naphthalene having a purity of 95% was mixed with 1,050 g of 98% sulfuric acid and sulfonated at 158°C for 1 hour. Unreacted naphthalene and the water formed by the reaction were removed from the system by distillation under reduced pressure. However, 0.6% (based on the charged amount) of unreacted naphthalene remained in the system. Then, 875 g of 35% formalin was added and the resulting mixture was reacted at 105°C for 5 hours to obtain a methylene-linked condensation product of naphthalene- ⁇ -sulfonic acid. This condensation product had a number-average molecular weight of 3,200.
  • condensation product was neutralized with ammonia and then filtered through No. 5C filter paper (manufactured by Toyoroshi Kaisha, Ltd.).
  • To the filtrate was added a specified amount of an aqueous solution of Poval PVA-217 (manufactured by Kuraray Co., Ltd.; polymerization degree 1,700-2,400).
  • the filtrate containing the water-soluble polymeric compound was concentrated to obtain a spinning material having a viscosity of 2 Pa ⁇ s (20 poises) as measured at 85°C with a Brookfield type viscometer. This spinning material was dry-spun at about 60°C using a stainless steel spinneret having an orifice diameter of 0.2 mm.
  • the spun fiber was directly subjected to a carbonization step. Specifically, the fiber was placed in a stream of N2 and heated from room temperature to 1,000°C at a rate of 200°C/min. on the average. During this carbonization process, the fiber was held at 250°C for 5 minutes and at 1,000°C for 5 minutes.
  • the spinnability of spinning materials containing various amounts of PVA and some properties of the carbon fibers formed from these spinning materials are shown in Table 1.
  • the carbon fiber having a PVA content of 0.8% was activated by treatment with steam at 850°C for 60 minutes.
  • the resulting fiber had a specific surface area of 1,400 m2/g as measured by the CO2 BET method, and a specific surface area of 1,520 m2/g as measured by the N2 BET method.
  • creosote oil 2,000 g was mixed with 1,050 g of 98% sulfuric acid and sulfonated at 158°C for 1 hour. Unreacted oil and the water formed by the reaction were removed from the system by distillation. Then, 357 g of a 35% aqueous solution of formalin was added and the resulting mixture was reacted at 105°C for 5 hours to obtain a methylene-linked condensation product of aromatic sulfonic acids, which had a number average molecular weight of 5600. This condensation product was mixed with 37 g of calcium hydroxide to convert the excess sulfuric acid to gypsum, and then centrifuged to remove any insoluble solid matter.
  • the filtrate was neutralized with ammonia and divided into five equal parts. To four of these parts were added specified amounts of aqueous solutions of polystyrene-sulfonic acid sodium salt (PS-100, manufactured by Tosoh Co., Ltd.; average molecular weight 800,000-1,200,000), polyacrylic acid sodium salt (Aqualic MP-30, manufactured by Japan Catalytic Chemical Industry Co., Ltd.; average molecular weight 40,000), polyacrylamide (Hopelon A-10, manufactured by Mitsui-Toatsu Chemicals Inc.; average molecular weight 600,000-700,000) and polyethylene glycol (PEO-3, manufactured by Seitetsu Kagaku Co., Ltd.; average molecular weight 600,000-1,100,000), respectively.
  • PS-100 polystyrene-sulfonic acid sodium salt
  • Aqualic MP-30 manufactured by Japan Catalytic Chemical Industry Co., Ltd.; average molecular weight 40,000
  • polyacrylamide Hopelon A-10, manufactured by Mitsui-

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Inorganic Fibers (AREA)
  • Artificial Filaments (AREA)
  • Separation Of Gases By Adsorption (AREA)
  • Carbon And Carbon Compounds (AREA)

Claims (6)

  1. Ein Verfahren zum Herstellen von Kohlenstoffmaterialien, das die Schritte umfaßt, daß eine Ausgangsmaterialzusammensetzung, die eine durch eine Carbonisierungsbehandlung carbonisierbare organische Verbindung und ein Lösungsmittel umfaßt, hergestellt wird, die Ausgangsmaterialzusammensetzung versponnen oder ausgeformt wird und die gesponnene Faser oder der ausgeformte Gegenstand carbonisiert wird, dadurch gekennzeichnet, daß die organische Verbindung ein Kondensationsprodukt mit methylenartiger Bindung einer aromatischen Sulfonsäure oder eines Salzes derselben ist, worbei das Kondensationsprodukt mittels einer Verbindung der Formel



            -(CH₂)n-Tx-(CHR)m-



    gebildet worden ist, worin T ein Benzol- oder Nahphtalinring ist, R ein Wasserstoffatom, eine Alkylgruppe mit 1 bis 4 Kohlenstoffatomen oder ein Benzolring ist und jedes von n, m und x 0 oder 1 ist, wobei n und m nicht gleichzeitig null sein sollten.
  2. Ein Verfahren zum Herstellen von Kohlenstoffmaterialien nach Anspruch 1, bei dem die Verbindung der Formel (1) -CH₂- ist.
  3. Ein Verfahren zum Herstellen von Kohlenstoffmaterialien nach Anspruch 1 oder 2, bei dem vor dem Spinn- oder Ausformschritt eine wasserlösliche polymere Verbindung zu der Ausgangsmaterialzusammensetzung in einer Menge von 0,02 bis 20 Gewichtsteilen pro 100 Gewichtsteilen des festen Bestandteils der Ausgangsmaterialzusammensetzung hinzugegeben wird.
  4. Ein Verfahren zum Herstellen von Kohlenstoffmaterialien nach einem der Ansprüche 1 bis 3, bei dem das Produkt, das von dem Carbonisierungsschritt herrührt, weiterhin einer Aktivierungsbehandlung unterworfen wird.
  5. Ein Verfahren zum Herstellen von Kohlenstoffmaterialien nach einem der Ansprüche 1 bis 4, bei dem die Ausgangsmaterialzusammensetzung gesponnen wird, um ein Kohlenstoffmaterial in faseriger Form zu erhalten.
  6. Ein Verfahren zum Herstellen von Kohlenstoffmaterialien nach einem der Ansprüche 1 bis 4, bei dem die Ausgangsmaterialzusammensetzung ausgeformt wird, um ein Kohlenstoffmaterial in Form eines ausgeformten Gegenstandes zu erhalten.
EP88113265A 1987-08-21 1988-08-16 Verfahren zum Herstellen von Kohlenstoffmaterialien Expired - Lifetime EP0304010B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP206476/87 1987-08-21
JP20647687 1987-08-21
JP53802/88 1988-03-09
JP63053802A JPH01132832A (ja) 1987-08-21 1988-03-09 炭素材料の製造方法

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EP0304010A2 EP0304010A2 (de) 1989-02-22
EP0304010A3 EP0304010A3 (en) 1990-02-28
EP0304010B1 true EP0304010B1 (de) 1994-03-09

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DE (1) DE3888260T2 (de)

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JP2857169B2 (ja) * 1989-05-22 1999-02-10 三井鉱山株式会社 スルホン基含有耐熱性高分子材料およびその製造方法
WO2012050171A1 (ja) 2010-10-13 2012-04-19 三菱レイヨン株式会社 炭素繊維前駆体繊維束、炭素繊維束、及びそれらの利用
TWI532755B (zh) 2011-07-22 2016-05-11 三菱麗陽股份有限公司 聚丙烯腈系共聚物、碳纖維用聚丙烯腈系前驅體纖維、碳纖維束、阻焰纖維束的製造方法及碳纖維束的製造方法
ES2610219T3 (es) * 2012-07-12 2017-04-26 Dow Global Technologies Llc Procesos para la preparación de fibras de carbono mediante el uso de trióxido de azufre en un disolvente halogenado
JP6604118B2 (ja) * 2015-09-29 2019-11-13 日本製紙株式会社 炭素繊維シートの製造方法
JP6657712B2 (ja) * 2015-09-29 2020-03-04 日本製紙株式会社 炭素繊維及び炭素繊維シートの製造方法

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Publication number Priority date Publication date Assignee Title
BE757620A (fr) * 1969-10-17 1971-04-16 Bayer Ag Procede de preparation de fibres de carbone
JPS5263209A (en) * 1975-11-20 1977-05-25 Hitachi Chemical Co Ltd Manufacture of carbon bodies

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI, no. 72-82 897 DERWENT PUBLICATIONS LTD., London, GB & JP-B-72-049992 *
DATABASE WPI, no. 77-47 802 DERWENT PUBLICATIONS LTD., London, GB & JP-A-52-063209 *

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Publication number Publication date
JPH0440452B2 (de) 1992-07-03
DE3888260D1 (de) 1994-04-14
DE3888260T2 (de) 1994-09-29
EP0304010A3 (en) 1990-02-28
EP0304010A2 (de) 1989-02-22
CA1324469C (en) 1993-11-23
JPH01132832A (ja) 1989-05-25

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