EP0175200B1 - Procédé pour fabriquer une fibre de carbone à partir d'un brai - Google Patents

Procédé pour fabriquer une fibre de carbone à partir d'un brai Download PDF

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Publication number
EP0175200B1
EP0175200B1 EP85111031A EP85111031A EP0175200B1 EP 0175200 B1 EP0175200 B1 EP 0175200B1 EP 85111031 A EP85111031 A EP 85111031A EP 85111031 A EP85111031 A EP 85111031A EP 0175200 B1 EP0175200 B1 EP 0175200B1
Authority
EP
European Patent Office
Prior art keywords
pitch
fibers
carbon fiber
precursory
silicone oil
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP85111031A
Other languages
German (de)
English (en)
Other versions
EP0175200A3 (en
EP0175200A2 (fr
Inventor
Masami Kagizaki
Tsuyoshi Takakura
Hiroshi Tahara
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.)
Mitsubishi Chemical Corp
Original Assignee
Mitsubishi Kasei Corp
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Publication date
Application filed by Mitsubishi Kasei Corp filed Critical Mitsubishi Kasei Corp
Publication of EP0175200A2 publication Critical patent/EP0175200A2/fr
Publication of EP0175200A3 publication Critical patent/EP0175200A3/en
Application granted granted Critical
Publication of EP0175200B1 publication Critical patent/EP0175200B1/fr
Anticipated expiration legal-status Critical
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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
    • D01F9/145—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues
    • D01F9/155—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues from petroleum pitch
    • 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
    • D01F9/145—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues
    • D01F9/15—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues from coal pitch

Definitions

  • the present invention relates to a process for producing a carbon fiber from pitch material such as a coal-originated pitch, a petroleum pitch or a baked polymer pitch. More particularly, it relates to a process for producing such a pitch-type carbon fiber of high quality which is composed of carbon fiber monofilaments bound together without direct adhesion or fusion to one another, and which is easy to handle.
  • pitch material such as a coal-originated pitch, a petroleum pitch or a baked polymer pitch. More particularly, it relates to a process for producing such a pitch-type carbon fiber of high quality which is composed of carbon fiber monofilaments bound together without direct adhesion or fusion to one another, and which is easy to handle.
  • Pitch-type carbon fibers are produced usually by melt-spinning the pitch material to form precursory pitch fibers and subjecting the precursory pitch fibers to infusible treatment and carbonization treatment.
  • Such pitch-type carbon fibers have an advantage that they can be produced in good yield and at low costs as compared with carbon fibers made of e.g. polyacrylonitriles.
  • they have a disadvantage that the precursory pitch fibers are extremely brittle and difficult to handle for the infusible treatment or carbonization treatment.
  • the precursory pitch fibers are likely to undergo fluffing, twine round guide rollers or break during such treatments. Further, there are additional difficulties such that adhesion or fusion is likely to take place among the precursory pitch fibers during the infusible treatment and the carbonization treatment, and the resulting carbon fiber surface is susceptible to damages.
  • the tow withdrawn from the spinning bath is subjected to flame resistant treatment in an oxidizing atmosphere at a temperature of from 200 to 300°C and then to carbonization treatment in an inert atmosphere at a temperature of from 300 to 1400°C.
  • a lubricant such as polyethylene glycol or polypropylene glycol
  • a lubricant such as polyethylene glycol or polypropylene glycol
  • the bundling can smoothly be conducted.
  • the silicone oil may be applied excessively. While not adversely affecting the bundling operation, such excessive application of silicone oil is likely to lead to difficulties such that the tow of precursory pitch fibers tends to be stiff after the infusible treatment or the carbonization treatment, and in an extreme case, the pitch fibers tend to fuse one another to form a tow which is hardly unbound or separated into individual fibers.
  • the present inventors have conducted further researches to overcome these difficulties. As a result, they have found it effective to use an aqueous emulsion of a silicone oil as the oiling agent.
  • the present invention has been accomplished based on this discovery.
  • the present invention provides a process for producing a carbon fiber from pitch material, which comprises melt spinning pitch material in a gaseous atmosphere to form precursory pitch fibers and bundling the precursory pitch fibers, followed by infusible treatment and carbonization and optionally by graphitization, characterized in that an aqueous emulsion of a silicone oil is applied as an oiling agent to the precursory pitch fibers prior to or during the bundling operation.
  • the pitch material to be used in the present invention there may be mentioned a coal-originated pitch such as coal tar pitch or liquefied coal; a petroleum pitch such as a distillation residue obtained by the distillation of crude oil under atmospheric or reduced pressure or a heat-treated product thereof, or a heat-treated product of by-product tar obtained by the pyrolysis of naphtha; and a baked polymer pitch obtained by the carbonization of a synthetic or natural resin.
  • a coal-originated pitch such as coal tar pitch or liquefied coal
  • a petroleum pitch such as a distillation residue obtained by the distillation of crude oil under atmospheric or reduced pressure or a heat-treated product thereof, or a heat-treated product of by-product tar obtained by the pyrolysis of naphtha
  • a baked polymer pitch obtained by the carbonization of a synthetic or natural resin.
  • the melt spinning of the pitch material is conducted by extruding it into a gaseous atmosphere through spinning nozzles in the same manner as in the case of the dry melt spinning of ordinary synthetic fibers. It is preferred to employ a method wherein the pitch material is melted by an extruder or the like and extruded into a gaseous atmosphere from spinning nozzles directed downwardly, whereupon the extruded fibers are cooled and solidified. It is usual to employ spinning nozzles with discharge outlets havinag a diameter of from 0.1 to 0.5 mm.
  • the temperature of the spinning nozzles is determined depending upon the type of the pitch material to provide a melt viscosity most suitable for spinning, and it is usually selected within a range of from 250 to 350°C. It is effective for the stabilization of spinning to provide temperature- keeping cylinders below the spinning nozzles.
  • an aqueous emulsion of a silicone oil is applied as an oiling agent to the precursory pitch fibers obtained by the spinning, prior to or during the bundling operation.
  • a silicone oil dimethylpolysiloxane is usually employed.
  • modified dimethylpolysiloxane derivatives obtained by introducing various groups to dimethylpolysiloxane there may be mentioned, for example, methylphenylpolysiloxane or hydrodiene- polysiloxane.
  • silicone oils may be used alone or in combination as a mixture of at least two different kinds.
  • the aqueous emulsion of a silicone oil may be prepared by mixing the silicone oil with water by means of a common mixing device such as a high speed mixer, a colloid mill or a homogenizer so that the silicone oil constitutes from 0.1 to 35% by weight in the mixture.
  • a common mixing device such as a high speed mixer, a colloid mill or a homogenizer
  • an emulsifier may be added.
  • an emulsifier there may be employed conventional emulsifiers.
  • a nonionic emulsifier such as a sorbitan fatty acid ester e.g.
  • sorbitan palmitic acid ester sorbitan stearic acid ester, polyoxyethylene sorbitan fatty acid ester or polyoxyethylene sorbitan caproic acid ester, polyoxyethylene lauric acid ester, acetylated monoglyceride, acetylated glyceryl monostearate or a polyoxyethylene lanolin derivative; an anionic emulsifier such as an alkyl sulfate, sodium laurylsulfate, sodium cetylsulfate, a dialkyl sulfosuccinate or sodium di-2-ethylhexyl sulfosuccinate; or a cationic emulsifier such as alkyl pyridinium chloride. Further, a small amount of fine solid particles may be added to the aqueous emulsion of a silicone oil.
  • fine solid,partides there may be employed, for instance, fine carbonaceous particles, fine inorganic oxide particles, fine inorganic salt particles or a mixture thereof.
  • fine particles of graphite, carbon black, silica, calcium carbonate, titanium oxide, talc, clay, barium sulfate, potassium titanate or molybdenum disulfide there may be mentioned fine particles of graphite, carbon black, silica, calcium carbonate, titanium oxide, talc, clay, barium sulfate, potassium titanate or molybdenum disulfide.
  • the oiling agent may be applied to the precursory pitch fibers by various methods such as a spraying method, a roller coating method or a dipping method.
  • the amount of the deposition of the oiling agent onto the fibers is usually from 1 to 15% by weight, preferably from 2 to 10% by weight. If the amount of the deposition is less than 1 % by weight, it is difficult to maintain the bundled state of the spun fibers adequately, whereby it becomes difficult to handle the bundled fibers, and the fibers are likely to be damaged.
  • the amount exceeds 15% by weight, depending upon the concentration of the oiling agent, the evaporation at the time of the infusible treatment will be inadequate, and the agent will remain on the filaments and thus hinders the infusible reaction, and a low molecular weight gas genertated from the fibers during the infusible treatment will not sufficiently be dissipated, whereby the strength of the carbon fiber will be reduced.
  • the precursory pitch fibers having the aqueous solution of a silicone oil applied thereon and bundled, are subjected to infusible treatment and carbonization treatment in accordance with known methods.
  • the infusible treatment may be conducted by heating the tow of fibers at a temperature of from 150 to 360°C for from 5 minutes to 10 hours in an oxidizing atmosphere such as oxygen, ozone, air, a nitrogen oxide, halogen or sulfur dioxide.
  • the carbonization treatment may be conducted by heating the tow of fibers at a temperature of from 1000 to 2500°C for from 0.5 minute to 10 hours in an inert gas atmosphere such as nitrogen or argon.
  • the graphitization may be conducted by heating the tow of fibers at a temperature of from 2500 to 3500°C for from 1 second to 1 hour.
  • a load or tension may be applied to the tow of fibers to some extent during the infusible treatment, the carbonization treatment or the graphitization treatment for the purpose of preventing shrinkage or deformation.
  • the infusible treatment it is desirable to preliminarily adjust the deposition of water on the precursory pitch fibers to a level of at most 0.1 % by weight either by providing a drier immediately before the infusible treatment furnace, or by drying, at the initial stage of the infusible treatment, the precursory pitch fibers at from 50 to 100°C for 5 minutes to 2 hours.
  • the handling of brittle fibers can be made easy and it is possible to prevent the adhesion or fusion of the fibers to one another or to prevent the damages to the fiber surface, by a simple operation of applying an aqueous emulsion of a silicone oil to the precusory pitch fibers.
  • a pitch-type carbon fiber having good quality is obtainable in the form of a continuous fiber in an industrially advantageous manner and condition.
  • the heat-treatments can thereby be conducted under uniform and sufficient tension, whereby a pitch-type carbon fiber having superior properties is obtainable at low costs.
  • Coal tar-originated pitch material (meso-phase pitch having an optical anisotropy of 100%) was melt- spun into a gaseous atmosphere at a spinneret temperature of 330°C. Then, an oiling agent as identified in Table 1 was applied by spraying to the precursory pitch fibers having a diameter of 10 pm thereby obtained, and the fibers were bundled together.
  • the bundled fiber i.e. tow
  • the fiber was subjected to carbonization treatment by heating it in argon from room temperature to 1,400°C over a period of 2 hours 20 minutes, and then maintaining it at that temperature for one hour, whereby a carbon fiber was obtained.
  • Example 1 The operation was conducted in the same manner as in Example 1 except that no oiling agent was used or the amount or the type of the oiling agent was varied. The results are shown in Table 1.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Fibers (AREA)

Claims (3)

1. Procédé de fabrication de fibres de carbone à partir d'une matière du type brai, qui comprend le filetage à l'etat fondu de la matière du type brai, dans une atmosphère gazeuse, pour former des fibres de brai précurseurs, et la mise sous forme de faisceaux des fibres de brai précurseurs, en faisant suivre par un traitement destiné à rendre ces dernières infusibles et une carbonisation et, facultativement, une graphitisation, caractérisé par le fait qu'on applique une émulsion aqueuse d'une huile de silicone, en tant qu'agent de lubrification, sur les fibres de brai précurseurs, avant ou pendant l'opération de mise sous forme de faisceaux.
2. Procédé selon la revendication 1, dans lequel la concentration de l'huile de silicone dans l'agent de lubrification va de 0,1 à 35% en poids.
3. Procédé selon la revendication 1, suivant lequel on applique l'agent de lubrification en une quantité allant de 1 à 15% en poids par rapport aux fibres.
EP85111031A 1984-09-11 1985-09-02 Procédé pour fabriquer une fibre de carbone à partir d'un brai Expired - Lifetime EP0175200B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP59190404A JPH06102852B2 (ja) 1984-09-11 1984-09-11 ピッチ系炭素繊維の製造法
JP190404/84 1984-09-11

Publications (3)

Publication Number Publication Date
EP0175200A2 EP0175200A2 (fr) 1986-03-26
EP0175200A3 EP0175200A3 (en) 1987-08-05
EP0175200B1 true EP0175200B1 (fr) 1990-06-27

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Application Number Title Priority Date Filing Date
EP85111031A Expired - Lifetime EP0175200B1 (fr) 1984-09-11 1985-09-02 Procédé pour fabriquer une fibre de carbone à partir d'un brai

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EP (1) EP0175200B1 (fr)
JP (1) JPH06102852B2 (fr)
DE (1) DE3578440D1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62156316A (ja) * 1985-12-26 1987-07-11 Toa Nenryo Kogyo Kk 炭素繊維及び黒鉛繊維の製造方法
DE3775834D1 (de) * 1986-06-12 1992-02-20 Mitsubishi Chem Ind Verfahren zum herstellen von pech-kohlenstoffasern.
US5256343A (en) * 1987-01-28 1993-10-26 Petoca Ltd. Method for producing pitch-based carbon fibers
JPH0737689B2 (ja) * 1987-04-23 1995-04-26 東燃株式会社 炭素繊維及び黒鉛繊維の製造方法
JP2760397B2 (ja) * 1987-07-16 1998-05-28 三菱化学株式会社 ピッチ系炭素繊維用処理剤

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4009248A (en) * 1975-04-04 1977-02-22 Japan Exlan Company Limited Process for producing carbon fibers

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1275138A (en) * 1969-12-19 1972-05-24 Rolls Royce Method of treating polymeric fibres
US4582662A (en) * 1983-05-27 1986-04-15 Mitsubishi Chemical Industries Ltd. Process for producing a carbon fiber from pitch material
JPS60134027A (ja) * 1983-12-20 1985-07-17 Nippon Oil Co Ltd ピツチ系炭素繊維の製造方法
JPS60173121A (ja) * 1984-02-16 1985-09-06 Toa Nenryo Kogyo Kk 炭素繊維及び黒鉛繊維の製造方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4009248A (en) * 1975-04-04 1977-02-22 Japan Exlan Company Limited Process for producing carbon fibers

Also Published As

Publication number Publication date
JPS6170017A (ja) 1986-04-10
EP0175200A3 (en) 1987-08-05
EP0175200A2 (fr) 1986-03-26
JPH06102852B2 (ja) 1994-12-14
DE3578440D1 (de) 1990-08-02

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