KR101795909B1 - Process for the preparation of high strength carbon fiber - Google Patents

Process for the preparation of high strength carbon fiber Download PDF

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KR101795909B1
KR101795909B1 KR1020160018072A KR20160018072A KR101795909B1 KR 101795909 B1 KR101795909 B1 KR 101795909B1 KR 1020160018072 A KR1020160018072 A KR 1020160018072A KR 20160018072 A KR20160018072 A KR 20160018072A KR 101795909 B1 KR101795909 B1 KR 101795909B1
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South Korea
Prior art keywords
carbon fiber
mesh
emulsion
high strength
bath
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KR1020160018072A
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Korean (ko)
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KR20170096671A (en
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최미영
방윤혁
김성룡
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주식회사 효성
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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
    • 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
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/02—Preparation of spinning solutions
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/06—Washing or drying
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/04—Dry spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods
    • 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
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2101/00—Inorganic fibres
    • D10B2101/10—Inorganic fibres based on non-oxides other than metals
    • D10B2101/12—Carbon; Pitch
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/06—Load-responsive characteristics
    • D10B2401/061—Load-responsive characteristics elastic
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/06—Load-responsive characteristics
    • D10B2401/063—Load-responsive characteristics high strength

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Fibers (AREA)

Abstract

The present invention relates to a method for producing high strength carbon fibers, which comprises injecting acrylonitrile as a main component, itaconic acid as a main component, dimethylsulfoxide as a solvent into a reaction vessel, adding azobisisobutyronitrile as a reaction initiator and thioglycol In an amount of 2 hours to prepare an acrylic polymer dope; The dope solution is solidified in a dimethylsulfoxide coagulating bath using a nozzle to produce coagulation; Characterized in that the coagulum is rinsed in a rinsing bath equipped with a mesh and then an emulsion is added in an oil bath in which a mesh is provided. To produce high strength carbon fibers by producing precursor fibers with little or no foreign matter incorporation and using them to produce chlorinated yarns and extending and shrinking them.

Description

Technical Field [0001] The present invention relates to a high strength carbon fiber,

The present invention relates to a method for producing a high strength carbon fiber, and more particularly, to a method for producing carbon fiber precursor fibers excellent in quality without foreign matters or surface defects and using the same to produce high strength and high elasticity carbon fibers will be.

In order to produce a high-strength and high-elastic carbon fiber, it is necessary to first reduce foreign matter contained in or attached to the carbon fiber precursor fiber. There has been proposed a method of strengthening the filtration of a monomer or polymer stock solution in order to reduce foreign matter and voids present in each fiber constituting the carbon fiber precursor.

Also, in order to suppress the generation of surface defects, a method of controlling the shape of the fiber guide used in the manufacturing process of the precursor fiber or the tension of the fiber in contact with the guide has been proposed, and a technique of suppressing the formation of voids or defects has been proposed . By optimizing the coagulation bath condition, the non-drawn filament is compacted or the coagulation bath is drawn at a high temperature to compact the drawn filament. However, such a densification improving technique tends to lower the oxygen permeability to the fibers in the chlorination process, and tends to lower the resin-impregnated strand tensile strength of the finally obtained carbon fiber.

Japanese Patent Application Laid-Open No. 10-2011-0078280 (published on July 7, 2011) discloses a dope preparation step of preparing a dope using a polyacrylonitrile polymer; A precursor fiber preparation step in which the dope is wet-laid or dry-wet-spinned to produce a PAN-based precursor fiber; A dechlorination step of dechlorinating the precursor fiber; And a carbonization step of carbonizing the dechlorinated fiber, wherein the polyacrylonitrile polymer comprises 95 wt% or more of acrylonitrile and 5 wt% or less of comonomer, Wherein the comonomer comprises at least two monomers selected from the group consisting of methyl acrylate, acrylic acid, methacrylic acid, and itaconic acid, and wherein the precursor The method of manufacturing a carbon fiber according to the present invention includes the steps of washing a fiber and washing the fiber. The method includes the steps of passing the fiber through a washing tank equipped with an ultrasonic generator to remove foreign matter present in the precursor fiber Based carbon fiber manufacturing method, In the process for producing polyacrylonitrile (PAN) precursor fibers, 1) a PAN-based polymer is mixed with acrylonitrile as a main monomer component, AN) and a copolymer component using aqueous suspension polymerization, 2) producing a fibrous form of coagulation by wet or dry wet spinning of the PAN-based polymer, and 3) A step of removing metal impurities while passing through a water washing bath of an aqueous ammonia solution, and the like, which is characterized in that in the water washing step, a water bath of an aqueous ammonia solution And then removing the metal impurities contained in the fibers. In Japanese Unexamined Patent Publication (Kokai) No. 10-1999-0035887 (published May 25, 1999), in the carbon fiber composed of a plurality of short fibers, the average short fiber diameter of the short fibers is d (unit: And a tensile strength of a resin impregnated strand of the carbon fiber is sigma (unit: GPa), the following relationship is satisfied: < EMI ID = 2.0 > And a technique of removing only impurities or voids in the process, as well as a technique of suppressing adhesion of only short fibers.

Accordingly, the present invention relates to a method for suppressing or preventing foreign matter on the surface of a carbon fiber precursor fiber, and more particularly, to a method for manufacturing a filter, such as a mesh (mesh) filter for each step of a water- To provide a method of manufacturing a high strength carbon fiber having excellent quality without surface defects by preventing foreign matter or single yarn from adhering to the fiber surface by water flow or fiber progression by providing a filter (porous membrane) It has its purpose.

In order to solve the above-mentioned problems, the present invention provides a method for producing high strength carbon fibers, which comprises reacting acrylonitrile as a main component, itaconic acid as an auxiliary component, dimethylsulfoxide as a solvent and azobisisobutyronitrile A thioglycol as a polymerization degree regulator is injected and reacted within 2 hours to prepare an acrylic polymer dope; The dope solution is solidified in a dimethylsulfoxide coagulating bath using a nozzle to produce coagulation; Characterized in that the coagulum is rinsed in a water bath equipped with a mesh and then added with an emulsion in an oil bath provided with a mesh

The method of manufacturing high strength carbon fibers as described above can reduce the surface defects of the carbon fiber precursor fibers to enable production of high strength and high-elasticity carbon fibers, and excellent quality of the precursor fibers for carbon fibers. It has the advantage of being able to give.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view showing the position of a mesh and the fiber advancing direction of the present invention. FIG.

Hereinafter, the present invention will be described in detail. However, the following description is intended to illustrate the present invention, and the present invention is not limited thereto.

The method for producing the high strength carbon fiber of the present invention comprises:

After the injection of acrylonitrile as a main component, itaconic acid as an auxiliary component and dimethyl sulfoxide as a solvent, azobisisobutyronitrile as a reaction initiator and thioglycol as a polymerization degree regulator were injected and reacted within 2 hours to obtain an acrylic polymer dope solution ;

The dope solution is solidified in a dimethylsulfoxide coagulating bath using a nozzle to produce coagulation; The coagulum is washed with water in a water bath equipped with a mesh and then added with an emulsion in an oil bath provided with a mesh to produce precursor fibers having little or no foreign matter incorporation and using the salt, And a high strength carbon fiber is produced by lengthening and lengthening the luster.

The mesh installed in the water washing bath and the oil bath is preferably 50 to 100 mesh, and when the water mesh is set to 50 mesh or less, the removal efficiency of foreign matter and disposal is decreased. When 100 mesh or more is installed, And since the flow of the emulsion is not smooth, desolvation is reduced in the water washing bath and the emulsion is unevenly adhered in the emulsion bath so that the quality of the carbon fiber may deteriorate.

In the present invention, an emulsion containing a silicone type emulsion, a modified epoxy emulsion, and an ammonium compound may be used.

It is preferable that the mesh according to the present invention is provided in at least two of the washing bath and the oil bath.

The type of the mesh is preferably at least one of steel or a synthetic resin such as polyethylene, polypropylene, polystyrene, polycarbonate, polyphenylene sulfide, etc. Steel is most preferable in terms of corrosion resistance and durability Do.

Hereinafter, the present invention will be described in more detail by way of examples. It is to be understood that the following embodiments are for the purpose of illustration only and are not intended to limit the scope of the present invention.

[ Example  ]

Example  One

Acrylonitrile as a main component, itaconic acid as an auxiliary component, and dimethylsulfoxide as a solvent are injected into the polymerization reactor preferentially. At this time, the polymerization composition was 98 wt% of acrylonitrile, 2 wt% of itaconic acid, dimethylsulfoxide was added so that the concentration of the monomer (main component and auxiliary component) was 22 wt% with respect to the total amount of injection, and azobisisobutyl Ronitril (AIBN) is injected at 0.1 wt% relative to the total monomer, and Thioglycol, a polymerization regulator, is injected at 0.2 wt% of the total monomer.

After injection of all monomers, solvents, additives (initiator and polymerization degree regulator) is completed within 2 hours, stirring is carried out to make a homogeneous solution. Polymerization was carried out at 65 占 폚 for 14 hours to prepare an acrylonitrile polymer dopant stock solution containing 20 wt% of a copolymer having an intrinsic viscosity of 2.0.

The dope stock solution was prepared by dry wet spinning with a gap of 5 m in a coagulation bath controlled at 3 ° C and a dimethyl sulfoxide concentration of 35 wt% using three 0.14 mm diameter 4000 Hole nozzles. And solidified. The resulting coagulum was rinsed in a water bath equipped with a 60 mesh mesh, and then extended to hot water of 60 ° C or higher to give an emulsion containing a silicone type emulsion, a modified epoxy emulsion and an ammonium compound. This was dried and densified using a heating roller at 150 DEG C, and subjected to a pressure steam process of 0.5 MPa to prepare precursor fibers for carbon fibers.

The carbon fiber precursor was used to shrink 10% at a temperature of 240 캜 while making a salt-resistant phosphor having a fiber specific gravity of 1.35, extended 3% under a nitrogen atmosphere at 450 캜 and then shrunk 5% under a nitrogen atmosphere at 1350 캜, .

Example  2

The emulsion containing a silicone type emulsion, a modified epoxy emulsion, and an ammonium compound was applied to the emulsion bath having a mesh, and the remaining steps were carried out in the same manner as in Example 1 to prepare carbon fibers.

Example  3

The water washing was carried out in a water bath equipped with a mesh, and an emulsion containing a silicone type emulsion, a modified epoxy emulsion and an ammonium compound was provided in an emulsion bath equipped with a mesh, and the remaining steps were carried out in the same manner as in Example 1 Carbon fiber.

[ Comparative Example ]

Comparative Example

The mesh was removed in the washing bath used in Example 1, and the remaining process was carried out in the same manner as in Example 1.

 [ Experimental Example ]

Table 1 shows the surface foreign matter of the carbon fiber precursor fibers produced in Examples 1 to 3 and Comparative Examples, and the strength and the strength CV (%) of the carbon fiber strand produced using the same.

division Example 1 Example 2 Example 3 Comparative Example Mesh installation location Water bath Emulsion bath Water bath
Emulsion bath X Precursor fiber Surface foreign matter ○ △ ◎ X Carbon fiber
Strand Tensile Strength (GPa) 5.5 5.2 5.9 4.3 Tensile strength CV
(%) 5.4 6.0 4.8 9.4

* Surface foreign matter evaluation standard

Good (◎): 3 gae / ㎛ 2 or less, good (○): 4 ~ 8 gae / ㎛ 2, ordinary (△): 9 ~ 12 gae / ㎛ 2, Bad (×): 13 gae / ㎛ 2 or more

Claims (9)

After the injection of acrylonitrile as a main component, itaconic acid as an auxiliary component and dimethyl sulfoxide as a solvent, azobisisobutyronitrile as a reaction initiator and thioglycol as a polymerization degree regulator were injected and reacted within 2 hours to obtain an acrylic polymer dope solution ;
A method for producing a carbon fiber for producing coagulation by solidifying a fiber in a dimethyl sulfoxide coagulating bath using a dope liquid as a nozzle,
After preparing the test piece; Characterized in that the coagulum is rinsed in a rinsing bath equipped with a mesh and then an emulsion is added in an oil bath in which a mesh is provided.
The carbon fiber strand has a tensile strength of 5.9 GPa or more and a tensile strength CV (%) of the carbon fiber strand is higher than that of the carbon fiber strand. 4.8 or less. The method of claim 1, wherein the mesh is 50 to 100 mesh. The method of producing a high strength carbon fiber according to claim 1, wherein two or more meshes are provided in the water bath and the oil bath. The method according to claim 1, wherein the mesh is made of steel or a synthetic resin such as polyethylene, polypropylene, polystyrene, polycarbonate or polyphenylene sulfide. delete The method for producing a high strength carbon fiber according to claim 1, wherein the emulsion is an emulsion containing a silicone oil emulsion, a modified epoxy emulsion, and an ammonium compound. The method for producing a high strength carbon fiber according to claim 1, wherein the emulsion is densified by using a heating roller at 150 캜 and subjected to a hot pressurization process at a high temperature to produce a carbon fiber precursor. The method according to claim 1, wherein the carbon fiber precursor fibers are shrunk 10% at a temperature of 240 ° C to produce a high strength carbon fiber having a fiber weight ratio of 1.35 The method according to claim 1, wherein the chlorinated chloride is 3% extended in a nitrogen atmosphere at 450 ° C and shrunk 5% in a nitrogen atmosphere at 1350 ° C.
KR1020160018072A 2016-02-16 2016-02-16 Process for the preparation of high strength carbon fiber KR101795909B1 (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003201620A (en) * 2001-12-26 2003-07-18 Kanegafuchi Chem Ind Co Ltd Method for removing solvent in acrylic fiber and apparatus therefor

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003201620A (en) * 2001-12-26 2003-07-18 Kanegafuchi Chem Ind Co Ltd Method for removing solvent in acrylic fiber and apparatus therefor

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