[go: up one dir, main page]

WO2015076534A1 - Brai isotrope à des fins de fabrication de fibre de carbone et son procédé de préparation - Google Patents

Brai isotrope à des fins de fabrication de fibre de carbone et son procédé de préparation Download PDF

Info

Publication number
WO2015076534A1
WO2015076534A1 PCT/KR2014/010968 KR2014010968W WO2015076534A1 WO 2015076534 A1 WO2015076534 A1 WO 2015076534A1 KR 2014010968 W KR2014010968 W KR 2014010968W WO 2015076534 A1 WO2015076534 A1 WO 2015076534A1
Authority
WO
WIPO (PCT)
Prior art keywords
pitch
isotropic pitch
carbon fiber
producing
isotropic
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.)
Ceased
Application number
PCT/KR2014/010968
Other languages
English (en)
Korean (ko)
Inventor
김진홍
박성범
유도애
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.)
SK Innovation Co Ltd
SK Geo Centric Co Ltd
Original Assignee
SK Innovation Co Ltd
SK Global Chemical Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by SK Innovation Co Ltd, SK Global Chemical Co Ltd filed Critical SK Innovation Co Ltd
Publication of WO2015076534A1 publication Critical patent/WO2015076534A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • 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
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C1/00—Working-up tar
    • C10C1/19—Working-up tar by thermal treatment not involving distillation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C3/00—Working-up pitch, asphalt, bitumen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C3/00—Working-up pitch, asphalt, bitumen
    • C10C3/002—Working-up pitch, asphalt, bitumen by thermal means
    • 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

Definitions

  • the present invention relates to an isotropic pitch for producing carbon fibers and a method for manufacturing the same. Specifically, the present invention relates to an isotropic pitch having a specific range of physical properties and structure, and is used to prepare carbon fibers having high strength and high elasticity compared to conventional isotropic carbon fibers. It relates to an isotropic pitch and a method for producing the same.
  • Body weight reduction can also be achieved by the use of high strength steels, aluminum alloys, etc., but carbon fiber reinforced plastics are highly effective, and engine hoods, propeller shafts and hydrogen tanks in automobiles. The trend is already in use.
  • CFRP CFRP is used as the main material of the body structure, weight reduction of about 50% is possible, and the impact energy absorption performance is also improved. Best of all, the lightest car bodies available today can be manufactured, and research is being conducted around the world.
  • CFRP also has a weak point. Tensile strength is weak compared to compression, and interlayer separation is likely to occur due to lamination. After impact, the compressive strength is drastically reduced. In addition, there is a disadvantage that the manufacturing cost is expensive, many applications are difficult. .
  • the carbon fibers included in CFRP may be classified into rayon, PAN, and pitch based on precursors.
  • liquid crystal pitch based carbon fibers and isotropic pitch based on pitch types of precursors It can be divided into carbon fiber.
  • isotropic pitch-based carbon fiber is called general-purpose carbon fiber because it has lower price than high performance grade, and it is produced in staple type carbon island channel by melt blown method, so it can be used as high temperature insulation material or filter. It is used as activated carbon fiber.
  • Japanese Patent Application Laid-Open No. 1996-144131 claims a round pitch for producing carbon fibers having a specific molecular weight, but has a low softening point of 180 to 200 ° C. and a tensile strength of the carbon fiber prepared from the pitch. Its strength is 89.3 kg / mitf (approximately 0.893 GPa) and shows low physical properties to be used for CFRP purposes for automotive steel plates.
  • Patent Document 1 Republic of Korea Patent Publication No. 2013-0059174 (June 05, 2013)"
  • Patent Document 2 Japanese Patent Laid-Open Publication 1996-144131 (June 04, 1996) ''
  • the present inventors conducted a study to solve the above problems, and as a result, invented a method for producing an isotropic pitch having a specific range of physical properties, molecular structure and laminated structure, the isotropic pitch prepared from the conventional isotropic carbon fiber It can be used to make carbon fibers with superior mechanical properties.
  • the present invention is the average diameter of the laminated structure formed by the condensed aromatic ring compound layer
  • An isotropic pitch includes a structure represented by an average number (M) of condensed aromatic ring compound layers included in the laminated structure, which can be represented by distance (d Y ) and (L c / d m ) + l.
  • the present invention is a pre-treatment of any one or a mixture of petroleum heavy oil, high-boiling residue, aromatic hydrocarbon mono- and naphtha cracking process residue to produce a raw material, in the raw material prepared It provides a filtration step of removing the solid material, polymerizing the filtered raw material to produce a basic pitch, and heating the basic pitch to produce the isotropic pitch.
  • the round pitch of the present invention has a softening point and a molecular weight in a specific range, and the generation of insoluble solids and mesophase is suppressed to the maximum in the pitch, so that the spinning property is excellent, the elongation is high, and the tensile strength is remarkably high. Increased to provide isotropic pitch-based carbon fibers that can be used for carbon composite applications.
  • FIG. 1 is a flowchart of a carbon fiber manufacturing process according to a preferred embodiment of the present invention.
  • FIG. 2 is an X-ray diffraction analysis of isotropic pitch in a manufacturing method including a halogenation step.
  • L 4 is an isotropic pitch structure analysis through X-ray diffraction analysis, where d 'is the average distance between condensed aromatic ring compounds in the laminated structure, and ⁇ is the average distance between aliphatic chains connected to the condensed aromatic ring compound.
  • L c is the average diameter of the laminated structure formed by the condensed aromatic ring compound layer
  • L a is the average diameter of the condensed aromatic ring compound layer
  • M is the average number of the condensed aromatic ring compound layers included in the laminated structure. to be.
  • the present invention relates to an isotropic pitch for producing carbon fibers, in which a layer of condensed aromatic cyclic compounds forms a laminated structure.
  • an isotropic pitch for producing carbon fibers and a method for producing the same, wherein the condensed aromatic ring compound is linked with an aliphatic chain.
  • the isotropic pitch of the present invention is excellent in spinning property, so that melt spinning is possible. No single yarn is generated or extremely rare during spinning, and the carbon fiber prepared therefrom has maximized physical properties of high strength and high elasticity.
  • the gamma band ( ⁇ -band) of the al iphat ic chain is found at 17 ⁇ 2 ⁇ ⁇ 18 in X-ray diffraction (XRD). It is an isotropic pitch that includes a structure in which a (002) plane band appears at 23 ⁇ 2 ⁇ ⁇ 25 and a (10) band appears at 43 ⁇ 2 ⁇ ⁇ 45, where the condensed aromatic ring compound is connected by an aliphatic chain.
  • the above structure has an average diameter of the laminated structure formed by the condensed aromatic ring compound layer.
  • the condensed aromatic ring compound may be different depending on the condensed structure but includes at least 2 to 7 aromatic rings, and the condensed aromatic ring compound layer is preferably aromatic.
  • It may be a layer consisting of a compound in which the rings are condensed or a compound layer containing a condensed aromatic ring compound, which may be connected by an aliphatic chain.
  • the laminated structure formed by the condensed aromatic Chora compound layer may be expressed as a nano cluster, and each measurement result of the crystal structure may be represented by XRD measurement results, Bragg equations, and scherrer equations. Can be represented by
  • (L c ) is 10 to 25, preferably 15 to 20, and the level of the condensed aromatic ring compound layer Average diameter (LJ is 5 to 15, preferably 8 to 12, and average distance between condensed aromatic ring compound layers in a laminated structure (dj is 3.50 to 4.50, preferably 3.55 to 4.00, and an aliphatic linked to the condensed aromatic ring compound
  • the average distance between chains ( ⁇ ) is from 4.50
  • the isotropic pitch prepared in the present invention has excellent radioactivity only when the structure satisfies the above range, and there is a very small amount such that non-fused solids and mesofaces are not produced or measured, and the mechanical properties of the carbon fiber produced therefrom This can be maximized.
  • the isotropic pitch of the present invention can be expressed as follows according to the analysis result.
  • the round pitch of the present invention has a (002) plane band at 23 ⁇ 2 ⁇ ⁇ 25, and the following formulas (1) to (4) in which the condensed aromatic ring compound is connected with an aliphatic chain It is an isotropic pitch for producing carbon fiber with a satisfactory structure.
  • the molecular weight of the isotropic pitch is too small, and thus the objective of the isotropic pitch of the present invention It does not satisfy the tensile strength of the carbon fiber, the elongation is too high, the elastic modulus falls.
  • the molecular weight of the isotropic pitch is not only low, but also Tensile strength is significantly reduced.
  • the isotropic pitch may be represented in more detail by further expressing an average distance dy between aliphatic chains connected to the condensed aromatic ring compound in the structure included in the isotropic pitch.
  • an isotropic pitch having better physical properties and radioactivity The mechanical properties of the high strength and high elasticity of the isotropic pitch-based carbon fiber can be produced and can be further maximized.
  • the isotropic pitch softening point of the present invention is 255 to 275 ° C., preferably 260 to
  • the isotropic pitch average molecular weight (Mw) of the present invention is 1500 to 3000, preferably
  • Isotropic pitches having an average molecular weight in the above preferred range can significantly increase the tensile strength in the production of carbon fibers and further increase the elongation rate.
  • the isotropic pitch viscosity is 200 to 500, but may be appropriately adjusted according to the method of producing carbon fibers.
  • the filtration step of b) in the above manufacturing method may be performed even after preparing the basic pitch of C), and the basic pitch of C) is an intermediate material for producing an isotropic pitch. Physical properties may vary.
  • the raw material may include pyrolysis fuel oil (PF0), which is a kind of naphtha decomposition residue oil.
  • PF0 is produced at the bottom (bottom) of the naphtha cracking center (NCC) and has a high degree of aromaticity and abundant resin, which can be used as a raw material of the present invention.
  • Aromatic hydrocarbons are ethyl benzene (ethylbenzene), 1-butenyl eu eu 3-methylbenzene (l- e thenyl-3- methyl benzene ), indene (Indene), 1-ethyl-3-methylbenzene (l -ethyl-3-methyl benzene), 1-methylethyl benzene, 2-ethyl-1,3-dimethylbenzene, 2-dime (hyl benzene), propylenebenzene ( propyl benzene), 1-methyl-4- (2-propenyl) -benzene (l-methyl-4- (2-propenyl) benzene), 1,1a, 6, 6a-tetrahydro-cyclopropanedene (1 , La , 6 , 6a-tetrahydro-
  • Raw material according to an embodiment of the present invention may further include a high boiling point oil.
  • the high boiling fraction according to an embodiment of the present invention refers to a component having a high boiling point and a high carbon number among components that can be obtained by fractional distillation of crude oil, and mainly a hard or heavy aromatic naphtha having 5 or more carbon atoms, preferably 7 or more carbon atoms. May include
  • the high boiling point oil may include an oil having 9 carbon atoms.
  • it may be made of styrene, vinyltoluene, indene, alphamethylstyrene and benzene / luluene / xylene (BTX).
  • the oil having 9 carbon atoms may preferably include indene.
  • Indene is combined with the side chain of the aromatic component in the raw material to prevent the tendency to dehydrate and etherify as the side chain of the aromatic component is oxidized in the stabilization step after melt spinning, resulting in lowering carbonization temperature and time. Can contribute.
  • the high boiling fraction is preferably contained in an amount of 5 to 15% by weight based on 100% by weight of the total raw material. If the content is less than 5% by weight, the effect may be insignificant. The effect may not be obvious
  • the degree of aroma (fa) of the raw material may be 0.7 to 0.9. If the degree of aroma is less than 0.7, the carbonization yield may be lowered. There is no particular limitation on the case where the aromaticity is higher than 0.9, but when the aromaticity is 0.9 or more, the effect by the series of pitch synthesis methods disclosed in the present invention may not be significant.
  • the molecular weight of the raw material may have a distribution of 75 to 350, and preferably may have a distribution of 100 to 250.
  • step a removes low molecular weight substances that are less likely to form oligomers by a polymerization reaction among the compounds included in the raw material, and simultaneously reacts reactions between the compounds contained in the raw material. This is a step of converting a highly reactive and unstable compound contained in the raw material into a more stable and effective compound for producing isotropic pitch.
  • the pretreatment may be carried out by atmospheric distillation at a temperature of 130 to 240 ° C., preferably 150 to 230 ° C., more preferably 190 to 220 ° C. until no volatiles are generated. have.
  • the heating temperature can affect the physical properties of the basic pitch and isotropic pitch, such as the composition ratio of the raw materials and the degree of aroma, and also the mechanical properties of the carbon fibers.
  • the pretreatment step may proceed at atmospheric pressure, but may proceed under reduced pressure. At this time, the pretreatment process may be performed at a lower temperature through decompression, and the pressure and temperature may be freely adjusted within a range capable of obtaining the same effect as the normal pressure.
  • step b) is a filtration step of the pretreated fuel to remove the solid material, and the solid material is a residue of a solid phase containing impurities such as metal, sulfur, and nitrogen from the isotropic pitch. It can act as a cracker in the structure of the carbon fiber to be produced may cause a decrease in strength.
  • Filtration may be carried out in a manner conventionally performed in the art, for example, by filtration, centrifugation, sedimentation, adsorption, extraction, etc.
  • ⁇ 62> filtration step may also be performed after the polymerization of the basic pitch diameter: Yiwu thus is the pre-treatment step may be carried out all of the following basic pitch and polymerization steps. That is, the manufacturing method may be performed after step (c), and in some cases, may be performed after steps (a) and (c), respectively.
  • step C) is a basic pitch manufacturing step, in which a raw pitch having a high softening point is produced without generating mesophases by heating the raw material that has undergone the filtration step at the same time. It can proceed by law or thermal polymerization.
  • the halogenation method may proceed by heating after further adding a halogen compound and a radical initiator, and preferably by adding and mixing a halogen compound after the addition of the radical initiator.
  • Halogenated compounds are chlorine (Cl 2 ), thionyl chloride (S0C 1 2 ), sulfuryl chloride
  • radical initiator is benzoyl peroxide (B enZ0 yi peroxide), di-butyl hydroperoxide oxazol id (di-t-butyl hydroperoxide) , acetyl peroxide (Acetyl peroxide) such yugigwa oxide (Organi c Peroxide) and, Azo Azo compounds such as bisisobutyronitrile (AIBN; ⁇ , ⁇ '-Azobisisobutyroni tr ile), azobismethylisobutylate ( ⁇ , a' -Azobi smethyl i sobutyrate), or a group consisting of a combination of two or more of these The one selected from can be used.
  • the radical initiator may be included in an amount of 1 to 30 parts by weight, more preferably 5 to 20 parts by weight, based on 100 parts by weight of the halogen compound.
  • Halogenation is carried out by halogenation reaction at 100 to 12 (0.5 to 2 hours at C to replace hydrogen in the aromatic alkyl group with halogen, followed by polymerization by dehalogenation reaction at 300 to 330 ° C. for 2 to 4 hours.
  • the dehalogenation reaction can further enhance the purity of the basic pitch produced by decomposing halogen compounds and radical initiators that may remain in the basic pitch after the reaction, particularly in the dehalogenation reaction.
  • banung temperature is good is not more than 330 ° C, 330 ° C in excess of, the process advances upset anisotropic screen or coking of the basic pitch of the excess polymerization only occurs actively decomposition of the halogenated compound and a radical initiator as a result of the carbon fiber machine Physical properties are greatly reduced.
  • the basic pitch prepared by the halogenation method may have a softening point of 70 to 130 C, preferably 115 to 125 ° C.
  • Thermal polymerization can be carried out at 350 to 380 ° C. for 0.1 to 2 hours.
  • the thermal polymerization method may proceed in an inert gas atmosphere, and may proceed by fractionating gaseous by-products generated during the process of nitrogen and polycondensat ion.
  • the reaction temperature should not exceed 380 ° C. However, when the reaction temperature exceeds 380 ° C, the reaction temperature exceeds the range of uniform anisotropy pitch for the present invention, as in the halogenation method. Excess mesophase may be produced or coking may result in uneven carbon fibers.
  • the basic pitch prepared by the thermal polymerization method may have a softening point of 85 to 140 ° C., preferably 115 to 125 ° C.
  • the physical properties of the basic pitch can be adjusted according to the configuration convenience.
  • the condensation aromatics of the basic pitch manufactured from the step (c) To the absolute amount of the ligomer linked to the ring compound It may further include a compound having a low boiling point in a range that does not significantly affect.
  • step (c) is carried out under pressurization, where the ' softening point of the basic pitch is applied to the physical properties, molecular structure and laminated structure of the isotropic pitch that is finally manufactured according to the convenience of the process configuration. You can freely adjust the range without affecting it.
  • step d) may be a process of manufacturing isotropic pitch capable of suppressing mesophase generation by promoting evaporation by heating the basic pitch as an isotropic manufacturing step.
  • the isotropic pitch manufacturing step may proceed with a conventional thin film distillation method, and thus, there is an advantage that an additional process of suppressing the formation of mesophase and removing insoluble solids is not necessary.
  • the isotropic pitch manufacturing step according to an embodiment of the present invention may correspond to the composition and state change of the isotropic pitch manufactured with a multi-stage thin film distillation apparatus.
  • the isotropic pitch manufacturing step may be performed by heating in a vacuum atmosphere for 0.1 to 1 hour at 300 to 350 ° C.
  • the heating temperature exceeds 350 ° C.
  • meso phases are partially formed, and insoluble carbon solids may be generated by the continuous heating, and it is preferable to observe the heating temperature and the heating time.
  • Isotropic pitch may have a softening point of 255 to 275 ° C, preferably 260 to 270 ° C.
  • the isotropic pitch average molecular weight (Mw) of the present invention may be 1500 to 3000, preferably 1700 to 2850. Since the average molecular weight and softening point of the isotropic pitch can greatly affect the physical properties of the carbon fibers to be produced, it is preferable to comply with the manufacturing process conditions.
  • the isotropic pitch produced in the present invention is capable of melt spinning, and does not have single yarn or extremely rare spinning when spinning.
  • Melt spinning is a method of melting polymer materials or pitches into continuous fibers, eliminating the need for expensive solvents for spinning, and simplifying the construction of spinning processes and significantly reducing costs. Way.
  • pitch spinning should be excellent, but the isotropic pitch prepared according to the present invention has very good spinning property, and melt spinning for carbon fiber manufacturing is possible, but the single yarn is extremely rare. Does not happen.
  • the isotropic pitch capable of melt-spinning of the present invention has a very high radioactivity compared to the isotropic pitch which was used to produce short fibers through melt-blowing, and thus it has high strength and high elastic carbon long fibers. It can also be manufactured. According to one embodiment of the present invention, as a result of measuring the isotropic pitch for 20 minutes in a row with the frequency of melt spinning off as a single shot frequency, it can be seen that the single yarn frequency corresponds to 0, which is very excellent in radioactivity.
  • the isotropic pitch of the present invention can be carbonized at a low temperature of 700 to 1200 ° C or less to minimize the energy consumption during the carbonization process.
  • the isotropic pitch prepared according to the present invention may produce carbon fibers through a stabilization step and a carbonization step after melt spinning.
  • the carbon fiber is manufactured from the isotropic pitch prepared according to the embodiment of the present invention, it is possible to produce an isotropic pitch-based carbon fiber having a high tensile strength of at least 1.5 GPa or more and an elongation rate of at least 1.5 GPa.
  • the isotropic pitch-based carbon fiber as described above is maximized in physical properties, unlike conventional isotropic pitch-based carbon fiber is used as a general-purpose carbon material can be used in various ways to the carbon composite material required high strength, high elastic carbon fiber.
  • the isotropic pitch of the present invention is preferably used for producing carbon fibers, but is not limited thereto, and may be used for manufacturing various carbon materials.
  • Yield Yield was calculated by the weight of the final pitch obtained relative to the weight of the naphtha cracking residue oil charged.
  • the stress-strain curve was measured with a UTM Jniversal Test Machine equipped with a 2N load cell on a sample of carbon fiber. Calculated from the diameter of the fiber analyzed by and electron microscopy.
  • the molecular composition of the pitch was analyzed by GOAED and the distribution of molecular weight was measured by GPC and the average molecular weight was obtained from the results.
  • X-ray diffractometer for molecular structure analysis of isotropic pitch uses Cu cathode.
  • the K-c wavelength was 1.540598, the voltage of the X-ray generator was 40KV, and the tube current was 3 (1 ⁇ 2A).
  • JE0L's T0F-MS was used to analyze the molecular structure.
  • the laser source was analyzed using Nd: YAG, laser intensity 5OT, mass range 10-3,000 and spiral measurement mode.
  • Oi KNCBO Oi KNCBO
  • Examples 1 to 4 prepared NCB0 at 190, 200, 210 and 220 ° C., respectively.
  • Comparative Example 3 was each subjected to a pretreatment step at 250 ° C. atmospheric distillation, after which the solid material was removed by filtration. In Comparative Example 1, the solid material was removed by filtration without performing the pretreatment step.
  • the structure of the prepared isotropic pitch was analyzed by X-ray diffractometer, and the gamma band ( ⁇ -band) of aliphatic chain was found in XRD of 17 ⁇ 2 ⁇ ⁇ 18, In the laminate structure of the condensed aromatic ring compound at 23 ⁇ 2 ⁇ ⁇ 25, the (10) plane band was shown at 43 ⁇ 2 ⁇ ⁇ 45 (FIG. 2). Table 6 below shows the results of the structural analysis.
  • Examples 5 to 8 performed the pre-treatment steps of the prepared NCB0 at 190, 200, 210, and 220 ° C, respectively, in Comparative Example 4 at 120 ° C, and Comparative Example 5 by atmospheric distillation at 250 ° C. The solids were removed by filtration. Comparative Example 3 removed the solid material through filtration without performing the pretreatment step.
  • an isotropic pitch was prepared by heating the basic pitches in a vacuum atmosphere at 340 ° C. for 30 minutes. After the process was completed, the softening point, viscosity and average molecular weight of the isotropic pitch were measured and described in Table 8 below.
  • the isotropic pitch produced by the halogenation method and the thermal polymerization method in the manufacturing step of the basic pitch was 17 ⁇ 2 ⁇ ⁇ 18 and the gamma band ( ⁇ ) of aliphatic chain ( ⁇ ) — Band), the (002) plane and the (10) plane band appeared at 43 ⁇ 2 ⁇ ⁇ 45 in the laminate structure of the condensed aromatic ring compound at 23 ⁇ 2 ⁇ ⁇ 25.
  • Table 10 shows the measurement results of the physical properties and structures of the isotropic pitch prepared according to all the above Examples and Comparative Examples.
  • the condensed aromatic ring compound in the structure of the isotropic pitch contained at least 2 to 7 aromatic rings, and in Table 10, the average interplanar distance (d m ) of the condensed aromatic ring compound layer was 3.594-3.965 A. Average diameter ( ⁇ ) of aliphatic chains connected to the condensed aromatic ring compound was 4.829--5.172A, and the average diameter of the isotropic pitch cluster ( L c ) belongs to 16-20 A.
  • the average number of condensed aromatic ring compound layers stacked in an isotropic pitch cluster (M) can be expressed as (L c / d + l and in 5.3 to 6.5 genus did.
  • the average number (M) of condensed aromatic ring compound layers stacked in an isotropic pitch cluster can be expressed as (L c / d + l and belongs to 5.3 to 6.5.
  • Carbon fibers were prepared using an isotropic pitch.
  • an isotropic pitch was injected into a cylindrical container, and then melt spun by applying a pressure of 0.8 kgf / cm 2 in a nitrogen atmosphere. At this time, the diameter of the winding machine was 150 ⁇ , the winding speed was 700rpm.
  • the spun fibers were each charged in a tubular electric furnace and then fed with air at a flow rate of 150 i / min.
  • the temperature was raised at a rate of 1 ° C / min, stabilized by maintaining for 1 hour after reaching 290 ° C.
  • nitrogen was injected at a rate of 150ml / min and at the same time heated up at a rate of 5 ° C / niin to reach 800 ° C and maintained for 0.5 hours to prepare a carbon fiber.
  • the radioactivity of the isotropic pitch and the physical properties of the prepared carbon fiber are shown in Table 1 below.
  • Comparative Examples and Examples were melt-spun, and in Table 11, high-strength carbon fibers having a tensile strength of at least 1.5 GPa and at most 2.0 GPa without single yarns were produced in each Example. 2. It belongs to 1 ⁇ 2.7%, and the diameter of carbon fiber belongs to 4.30-11.40 ⁇ . On the other hand, Comparative Example 1 has a low elastic modulus due to excessively high elongation ratio of 3.2 GPa to 3.2%, and Comparative Example 2 l.
  • the elastic modulus was low because the elongation ratio was too high compared to the tensile strength of lGPa, and Comparative Examples 3 and 4 had a high single yarn frequency, and Comparative Examples 4, 5, and 6 each carried out a tensile strength of 0.7, 0.9, and 0.9, respectively. Compared to yes Significantly lowered tensile strength.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Materials Engineering (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Working-Up Tar And Pitch (AREA)
  • Inorganic Fibers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne un brai isotrope à des fins de fabrication de fibre de carbone et son procédé de préparation, un brai isotrope ayant des plages particulières se rapportant à un point de ramollissement, une viscosité, un poids moléculaire, et une structure cristalline pouvant être préparé, et une telle caractéristique pouvant maximaliser les propriétés mécaniques de la fibre de carbone en supprimant au maximum la génération de solides insolubles et la mésophase du brai, et pouvant aussi réduire la consommation d'énergie étant donné qu'un procédé de carbonisation est effectué à basse température.
PCT/KR2014/010968 2013-11-19 2014-11-14 Brai isotrope à des fins de fabrication de fibre de carbone et son procédé de préparation Ceased WO2015076534A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2013-0140340 2013-11-19
KR20130140340 2013-11-19

Publications (1)

Publication Number Publication Date
WO2015076534A1 true WO2015076534A1 (fr) 2015-05-28

Family

ID=53179750

Family Applications (3)

Application Number Title Priority Date Filing Date
PCT/KR2014/010968 Ceased WO2015076534A1 (fr) 2013-11-19 2014-11-14 Brai isotrope à des fins de fabrication de fibre de carbone et son procédé de préparation
PCT/KR2014/010969 Ceased WO2015076535A1 (fr) 2013-11-19 2014-11-14 Procédé de préparation d'une longue fibre de carbone en utilisant du brai à l'huile isotrope et longue fibre de carbone préparée par celui-ci
PCT/KR2014/010967 Ceased WO2015076533A1 (fr) 2013-11-19 2014-11-14 Procédé de préparation de brai isotrope pour la production de fibre de carbone

Family Applications After (2)

Application Number Title Priority Date Filing Date
PCT/KR2014/010969 Ceased WO2015076535A1 (fr) 2013-11-19 2014-11-14 Procédé de préparation d'une longue fibre de carbone en utilisant du brai à l'huile isotrope et longue fibre de carbone préparée par celui-ci
PCT/KR2014/010967 Ceased WO2015076533A1 (fr) 2013-11-19 2014-11-14 Procédé de préparation de brai isotrope pour la production de fibre de carbone

Country Status (2)

Country Link
KR (4) KR102236622B1 (fr)
WO (3) WO2015076534A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102079363B1 (ko) * 2017-05-26 2020-02-19 엘지전자 주식회사 탄소 히터의 제조 방법
KR102477035B1 (ko) * 2019-07-23 2022-12-13 오씨아이 주식회사 석유계 고연화점 피치의 제조방법
KR102498310B1 (ko) * 2021-01-18 2023-02-10 오씨아이 주식회사 함침 피치의 제조 방법
KR102565168B1 (ko) 2021-07-01 2023-08-08 한국화학연구원 고수율 메조페이스 피치 제조방법 및 이로부터 제조된 메조페이스 피치
KR102764056B1 (ko) * 2022-01-19 2025-02-07 주식회사 킬링턴머티리얼즈 Mcmb 제조방법
EP4570882A4 (fr) * 2022-08-11 2025-11-12 Oci Co Ltd Procédé destiné à la production de brai à haut point de ramollissement à base de pétrole
KR102803018B1 (ko) * 2022-08-11 2025-05-09 오씨아이 주식회사 석유계 고연화점 피치의 제조방법

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR920010266B1 (ko) * 1990-04-06 1992-11-21 한일시멘트공업 주식회사 등방성 핏치계 탄소섬유의 제조방법
KR19990012608A (ko) * 1997-07-30 1999-02-25 손건래 고연화점 광학적 등방성 핏치의 제조방법
US6303096B1 (en) * 1998-11-10 2001-10-16 Mitsubishi Chemical Corporation Pitch based carbon fibers
KR20130059174A (ko) * 2011-11-28 2013-06-05 지에스칼텍스 주식회사 탄소섬유용 핏치의 제조방법
KR20130100588A (ko) * 2012-03-02 2013-09-11 오씨아이 주식회사 고강도 고탄성 피치계 등방성 탄소섬유 및 그 제조 방법

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5876523A (ja) * 1981-10-29 1983-05-09 Nippon Oil Co Ltd ピツチ系炭素繊維の製造方法
JPS6187790A (ja) * 1984-10-05 1986-05-06 Kawasaki Steel Corp 炭素繊維用プリカ−サ−ピツチの製造方法
CA1302934C (fr) * 1987-06-18 1992-06-09 Masatoshi Tsuchitani Mode de preparation de brais mesophases
US5182011A (en) * 1987-06-18 1993-01-26 Maruzen Petrochemical Co., Ltd. Process for preparing pitches
JPH0258596A (ja) * 1988-08-25 1990-02-27 Maruzen Petrochem Co Ltd 高性能炭素繊維製造用ピッチと汎用炭素繊維製造用ピッチの併産方法
JP2704499B2 (ja) * 1994-08-01 1998-01-26 大阪瓦斯株式会社 等方性ピッチの製造法
JPH08120282A (ja) * 1994-10-25 1996-05-14 Showa Shell Sekiyu Kk 炭素繊維用等方性ピッチの製造法
JPH08144131A (ja) 1994-11-16 1996-06-04 Showa Shell Sekiyu Kk 炭素繊維製造用等方性石油ピッチ
JP3695007B2 (ja) 1996-09-06 2005-09-14 三菱瓦斯化学株式会社 光学的等方性ピッチの製造法
JP3695077B2 (ja) 1997-08-19 2005-09-14 ブラザー工業株式会社 インク噴射装置
JP4349627B2 (ja) 2003-09-25 2009-10-21 株式会社クレハ 球状活性炭の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR920010266B1 (ko) * 1990-04-06 1992-11-21 한일시멘트공업 주식회사 등방성 핏치계 탄소섬유의 제조방법
KR19990012608A (ko) * 1997-07-30 1999-02-25 손건래 고연화점 광학적 등방성 핏치의 제조방법
US6303096B1 (en) * 1998-11-10 2001-10-16 Mitsubishi Chemical Corporation Pitch based carbon fibers
KR20130059174A (ko) * 2011-11-28 2013-06-05 지에스칼텍스 주식회사 탄소섬유용 핏치의 제조방법
KR20130100588A (ko) * 2012-03-02 2013-09-11 오씨아이 주식회사 고강도 고탄성 피치계 등방성 탄소섬유 및 그 제조 방법

Also Published As

Publication number Publication date
KR102220800B1 (ko) 2021-03-02
KR102236622B1 (ko) 2021-04-07
KR102249296B1 (ko) 2021-05-07
KR20150058007A (ko) 2015-05-28
KR102220717B1 (ko) 2021-03-02
WO2015076535A1 (fr) 2015-05-28
WO2015076533A1 (fr) 2015-05-28
KR20150058010A (ko) 2015-05-28
KR20150058009A (ko) 2015-05-28
KR20150058011A (ko) 2015-05-28

Similar Documents

Publication Publication Date Title
WO2015076534A1 (fr) Brai isotrope à des fins de fabrication de fibre de carbone et son procédé de préparation
Kim et al. Enhancing the tensile strength of isotropic pitch-based carbon fibers by improving the stabilization and carbonization properties of precursor pitch
Kim et al. Preparation of carbon fibers with excellent mechanical properties from isotropic pitches
Kumar et al. Mesophase formation behavior in petroleum residues
CN111575037B (zh) 一种高模量碳纤维与其前驱体中间相沥青的制备方法
Guo et al. Preparation of mesophase pitch with domain textures by molecular regulation of ethylene tar pitch for boosting the performance of its carbon materials
Jiang et al. Controlling spinning pitch property by tetrahydrofuran-soluble fraction of coal tar pitch co-carbonization with petrolatum
CA3124537C (fr) Production de fibre de carbone a partir d'asphaltenes
US20230357026A1 (en) Production of carbon fiber from asphaltenes
CN111575053B (zh) 一种体积排阻分离-热缩聚制备中间相沥青的方法及其应用
CN107201248A (zh) 一种fcc油浆组分切割‑沉降分离制备中间相沥青的方法
KR102247155B1 (ko) 하이브리드 전구체 섬유로부터 제조된 탄소섬유 및 이의 제조방법
Delport et al. Production of a self-adhering mesophase powder from anthracene oil for low pressure forming of graphite artefacts
Vekariya et al. Microstructural investigation and performance of carbon matrix composites developed through facile pitch modification route
Xi et al. Synthesizing mesophase carbon fibers from co-polymerization of coal liquefaction pitch and anthracene oil with the synergistic effect of molecular structure
Chen et al. Study on spinning stability and microstructure of mesophase pitch
Zishuo et al. Preparation and coking properties of binder pitch prepared by a two-step method of oxidation and mild-polymerization
CN120465134A (zh) 一种自由基引发诱导缩聚制备可纺中间相沥青和沥青基碳纤维的方法
Tabassum Melt Spinning of Carbon Fibers from Asphaltene-Additive Blend
Savage Thermoplastic matrix precursors
CN121377805A (en) SiC reinforced high heat-resistant regenerated CFCM composite material and preparation method thereof
MOCHIDA et al. 10 Preparation and Properties of Mesophase Pitches
島ノ江明生 A study on the low cost production methods of mesophase pitch based carbon fiber: Enhancement of the yield of mesophase pitch and shortening of the oxidation/stabilization time
JPH11302086A (ja) 炭素繊維強化炭素複合材料及びその製造方法
Franck et al. Production and uses of carbon products from mixtures of condensed aromatics

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14864152

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14864152

Country of ref document: EP

Kind code of ref document: A1