WO2022107978A1 - 그래핀 복합 섬유 및 이의 제조방법 - Google Patents
그래핀 복합 섬유 및 이의 제조방법 Download PDFInfo
- Publication number
- WO2022107978A1 WO2022107978A1 PCT/KR2020/017333 KR2020017333W WO2022107978A1 WO 2022107978 A1 WO2022107978 A1 WO 2022107978A1 KR 2020017333 W KR2020017333 W KR 2020017333W WO 2022107978 A1 WO2022107978 A1 WO 2022107978A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- graphene
- composite fiber
- graphene composite
- fiber
- solution
- Prior art date
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 120
- 239000000835 fiber Substances 0.000 title claims abstract description 76
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 238000009987 spinning Methods 0.000 claims abstract description 21
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000006185 dispersion Substances 0.000 claims abstract description 8
- 238000005520 cutting process Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 239000005871 repellent Substances 0.000 claims description 21
- 230000002940 repellent Effects 0.000 claims description 20
- 238000006116 polymerization reaction Methods 0.000 claims description 19
- 229920001778 nylon Polymers 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 238000009792 diffusion process Methods 0.000 claims description 7
- -1 polypropylene Polymers 0.000 claims description 7
- 239000004743 Polypropylene Substances 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 6
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 6
- 229920002292 Nylon 6 Polymers 0.000 claims description 5
- 239000004480 active ingredient Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 229920006231 aramid fiber Polymers 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 239000003995 emulsifying agent Substances 0.000 claims description 3
- 239000004677 Nylon Substances 0.000 claims description 2
- 239000004760 aramid Substances 0.000 claims description 2
- 239000003814 drug Substances 0.000 claims 1
- 229940079593 drug Drugs 0.000 claims 1
- 239000000243 solution Substances 0.000 description 20
- 230000008569 process Effects 0.000 description 8
- 238000005229 chemical vapour deposition Methods 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 238000009830 intercalation Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000010923 batch production Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 238000002074 melt spinning Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000005355 Hall effect Effects 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003102 growth factor Substances 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
- C08J3/2053—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the additives only being premixed with a liquid phase
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- 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
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt 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
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
-
- 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
- D01D5/38—Formation of filaments, threads, or the like during polymerisation
-
- 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
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Definitions
- the present invention relates to a fiber and a method for manufacturing the same, and more particularly, to a graphene composite fiber capable of producing a composite fiber using graphene and a heterogeneous raw material, and a method for manufacturing the same
- Graphene is a material in which carbon is connected to each other in a hexagonal shape to form a honeycomb-shaped two-dimensional planar structure, and is known to have excellent physical strength, excellent thermal conductivity, and electrical properties. Recently, due to such excellent properties of graphene, many attempts have been made to apply graphene to transparent electrodes, flexible displays, composite reinforcement materials, filters, biosensors, and integrated circuit packaging materials.
- Graphene can be divided into four major methods for its synthesis.
- the first method may refer to chemical vapor deposition (CVD) and epitaxial growth.
- the second method is a scotch tape or peel-off method, and the third method is an epitaxial growth method by electrically insulating the surface.
- This method refers to the removal of graphite crystals with weak bonding of van der Waals bonds by mechanical force.
- Graphene can be manufactured in this way because the surface of graphene has a smooth structure when the electrons of the pi orbital are widely spread and distributed on the surface.
- the chemical exfoliation method means dispersing the graphene pieces exfoliated from the graphite crystals in a solution phase through chemical treatment. If graphite is oxidized and then pulverized through ultrasonic waves, etc., graphene oxide uniformly dispersed in an aqueous solution can be produced. have. However, in the case of the final graphene obtained in this way, even if a reducing agent is used, the reduction process is not performed perfectly. On the other hand, in the case of graphene separated using a surfactant, etc., the electrical properties are improved compared to the graphene obtained by the aforementioned reduction process, but due to the interlayer resistance between the graphene pieces, it does not show a practical level of sheet resistance characteristics. has a
- This method means that carbon adsorbed or contained in the crystal at high temperature grows into graphene along the surface texture.
- the peel-off method belongs to a top-down method, and the other methods belong to a bottom-up method.
- Graphene obtained by the top-down method has excellent crystallinity (high conductivity and few defects), but its production efficiency is low, which is not sufficient for practical application.
- the bottom-up method can control the number of graphene layers and growth factors using various types of substrates.
- CVD synthesis method large-area, high-quality, high-purity graphene can be produced, enabling mass production.
- the CVD synthesis method is the most used for mass production of high-quality graphene films.
- the CVD synthesis method is a bottom-up method that directly grows graphene on a substrate using a carbon source such as methane.
- a carbon source such as methane.
- Large-area single-layer graphene grown on a catalytic metal foil such as copper can be transferred to a desired target substrate.
- the technical problem to be achieved by the present invention is to provide a graphene composite fiber capable of expressing the characteristics of graphene to the extent of adding a small amount of graphene to a polymer and capable of mass production, and a method for manufacturing the same.
- a first solution preparation step of dispersing graphene with a dispersion solvent to prepare a first solution; a second solution preparation step of preparing a second solution by adding a polymer to the first solution; a graphene master chip preparation step of preparing a plurality of graphene master chips by solidifying the second solution and then cutting; and a graphene composite fiber preparation step of preparing the graphene composite fiber by spinning the plurality of graphene master chips and the polymer with a fiber spinning device may be provided.
- the plurality of graphene master chips may include 0.03 to 0.4 parts by weight.
- the dispersion solvent may include ethylene glycol.
- the emulsion may contain 70 to 80% by weight of a leveling agent.
- the water repellent agent may have a weight average molecular weight of the active ingredient of 2,868, and the PDI may have 1.2.
- water and an emulsifier may be added to increase the diffusion efficiency of the agent.
- the polymer is polyester (POLYRSTER), nylon 6 (NYLON6), nylon 66 (NYLON66), polypropylene (POLYPROPYLENE), polyethylene (POLYETHYLEN), composite yarn (N/C, P/C), carbon fiber (CARBON FIBER) , may include one selected from aramid fibers (ARAMID FIBER) and mono fibers (MONO FIBER).
- the graphene composite fiber prepared by the one method described above may be provided.
- the graphene composite fiber may include nylon 2.9 denier or polyethylene terephthalate (RV 0.80) 1.7 denier.
- a plurality of graphene master chips are prepared using 0.3 to 1.5 nano-graphene and poly polymer or nylon polymer, and the plurality of graphene master chips are used together with poly polymer or nylon polymer as a fiber spinning device.
- graphene properties can be expressed to the extent of adding a small amount of graphene to the polymer, and graphene composite fibers can be produced in large quantities.
- FIG. 1 is a view schematically showing a method of manufacturing a graphene composite fiber according to an embodiment of the present invention.
- FIG. 2 is a schematic diagram schematically illustrating the manufacturing method shown in FIG. 1 .
- FIG 3 is a view showing a graphene composite fiber prepared according to the present embodiment.
- FIG. 4 is a table showing a comparison between the graphene composite fiber and the normal fiber prepared according to this embodiment.
- FIG. 5 is a table showing a comparison between the graphene composite fiber and general PP prepared according to this example.
- FIG. 1 is a view schematically showing a method of manufacturing a graphene composite fiber according to an embodiment of the present invention
- FIG. 2 is a schematic view schematically showing the manufacturing method shown in FIG. 1
- FIG. 3 is in this embodiment It is a view showing the graphene composite fiber prepared by It is a diagram showing the comparison of the fin composite fiber and general PP in a table.
- a graphene master chip preparation step (S30) to prepare, and a graphene composite fiber preparation step (S40) of preparing a graphene composite fiber by spinning a plurality of graphene master chips 20 and a polypolymer or nylon polymer with a fiber spinning device ) is provided.
- the first solution preparation step ( S10 ) is a step of preparing a first solution by dispersing 0.3 to 1.5 nano graphene 10 in a dispersion solvent.
- the dispersion solvent may include an organic solvent.
- the organic solvent is ethylene glycol (dimethyl sulfoxide, DMSO), N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF) ) may be any one of.
- a stirring process may be performed with respect to the solvent to which the graphene 10 is added in order to improve the dispersibility of the graphene 10 in the solvent.
- the graphene 10 may have an average diameter of 20 to 200 nm or 50 to 500 nm.
- the second solution preparation step S0 is a step of preparing a second solution by adding a poly polymer or a nylon polymer to the first solution.
- polyurethane may be added to the second solution in addition to the poly polymer or nylon polymer.
- the graphene master chip preparation step (S30) is a step of preparing a plurality of graphene master chips 20 by solidifying the second solution and then cutting it.
- a plurality of graphene master chips 20 may be manufactured using 0.3 to 1.5 nano-graphene 10 and a polypolymer or nylon polymer.
- the plurality of graphene master chips 20 thus manufactured may be supplied to a fiber spinning device and manufactured into graphene composite fibers by melt extrusion in the fiber spinning device.
- the graphene composite fiber preparation step (S40) is a step of preparing a graphene composite fiber by spinning a plurality of graphene master chips 20 and a poly polymer or a nylon polymer with a fiber spinning device.
- the plurality of graphene master chips 20 may be provided in an amount of 0.03 to 0.4 parts by weight.
- the fiber spinning apparatus may manufacture graphene composite fibers by melt extrusion.
- the graphene composite fiber produced by this embodiment may be polyethylene terephthalate (RV 0.80) 1.7 denier, which is the graphene composite PET fiber shown in FIG. It may be nylon 6 2.9 denier, which is a graphene composite nylon fiber.
- Figure 3 (a) shows a 0.2% graphene composite PET fiber
- Figure 3 (b) shows 0.2% and 0.05% graphene composite nylon fiber.
- the graphene composite PET fiber and the graphene composite nylon fiber prepared according to this embodiment are superior in far-infrared rays, anti-static, UV protection and antibacterial effects compared to general fibers. .
- the graphene composite polypolymer fiber prepared according to the present embodiment is superior to the general polypolymer fiber in the effect of craw value, thermal insulation rate, flame retardancy, heat transfer coefficient, air permeability, etc. have.
- polyester industrial yarn is a yarn with high strength properties and is manufactured by melt spinning a high molecular weight polymer to increase the degree of orientation and crystallinity of the yarn. Since there is a limit to raising the molecular weight with only general melt polymerization, solid state polymerization can be used to obtain molecular weight and intrinsic viscosity capable of expressing high strength properties.
- the polymerization reaction proceeds by raising the temperature to a solid-state polymerization possible. Because melt polymerization proceeds in a molten state, diffusion is fast and there is little difference in molecular weight and intrinsic viscosity.
- the reaction rate is determined by the diffusion of end groups and the movement rate of reaction by-products.
- the rate is slow and the difference in molecular weight and intrinsic viscosity may increase due to various conditions of solid-state polymerization. has This difference causes a difference in the degree of orientation between the filaments of the fiber during melt spinning, which causes breakage in the filament with a high degree of orientation where the drawing stress is concentrated. Due to this, the Max Draw Ratio, which is a measure of drawability, may be lowered.
- the effect of crystallization conditions was improved except for other conditions of solid-state polymerization.
- the spherulite shape was confirmed in the solid-state polymerization crystallization step on the inside as well as on the surface of the resin (chip) through observation with a polarized optical microscope.
- Solid-state polymerization is divided into batch and continuous processes. In the case of the batch process, the spheroid shape is uniform, whereas in the continuous process, various types of spheroids were found.
- the structure formed in the crystallization stage was maintained until the end of the solid-state polymerization, but due to the difference in the spherical structure between the resins, the diffusion rate of the terminal groups and the reaction by-products and the reaction rate of the solid-state polymerization may vary, which causes a difference in molecular weight and viscosity (intrinsic viscosity and melt viscosity) confirmed that
- the continuous process is a process adopted by most manufacturers because of its high productivity and competitive manufacturing cost. Due to the nature of the process, it has a relatively high crystallization temperature condition. Here, the temperature of the 1st and 2nd crystallization tanks is lowered by 15 degrees to ensure a uniform spherical shape, such as in the batch process, so that the melting temperature, molecular weight, intrinsic viscosity and melt viscosity of the resin are determined. It was possible to reduce the deviation, thereby raising the maximum stretch ratio, which is a measure of stretchability, from 6.28 to 6.71.
- Polyester Water Repellent Yarn (Low Wick Yarn) is an industrial yarn widely used for PVC coated fabrics such as outdoor billboards and playground roofs. Because the intended use requires shape stability, the yarn must have high strength and low shrinkage physical properties, and since it is exposed to the outside air for a long period of time, it must have excellent water repellency to prevent deterioration of quality such as stains caused by moisture penetration. . Manufacturing cost competitiveness is the most important factor for commercialization of water repellent yarn.
- the 1-step high-speed spinning process should be applied and the pickup of the expensive water repellent (Low Wick Chemical), which accounts for the largest portion of the manufacturing cost increase, should be minimized.
- This process is a process of supplying a water repellent agent at high speed (3,000 m/min level) before winding after supplying an oil agent (Spin Finish) before drawing, expressing the physical properties of the fiber through drawing and heat treatment.
- the water repellent yarn has a thin layer of an oil agent and a water repellent agent on the surface of the fiber, but since it is a high-speed process and the fiber has a large surface area (192 filaments), it is very difficult to evenly disperse the water repellent agent on the emulsion layer.
- the design for each is important.
- the surface energy is different when supplied in the spinning process and when the active ingredient, Fluoropolymer, remains on the fiber surface after water is evaporated.
- the oil agent has increased the hydrophobicity by raising the content of the lubricant from 45% to 75% within the range applicable to the spraying, and in the case of the water repellent agent, the weight average molecular weight of the active ingredient is increased. 2,868, by lowering the Polydisperisty Index (PDI, molecular weight distribution) to 1.2, the surface tension of the polymer was lowered to improve the interfacial compatibility between the emulsion and the active water repellent agent.
- PDI Polydisperisty Index
- a plurality of graphene master chips are prepared using 0.3 to 1.5 nano-nano graphene and polypolymer or nylon polymer, and the plurality of graphene master chips are fiber together with polypolymer or nylon polymer.
- graphene properties can be expressed to the extent that a small amount of graphene is added to the polymer, and graphene composite fibers can be produced in large quantities.
- graphene properties can be expressed to the extent that a small amount of graphene is added to the polymer, and graphene composite fibers can be produced in large quantities.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Artificial Filaments (AREA)
- Inorganic Fibers (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Description
Claims (9)
- 그래핀을 분산 용매로 분산시켜 제1 용액을 마련하는 제1 용액 마련 단계;상기 제1 용액에 폴리머를 첨가하여 제2 용액을 마련하는 제2 용액 마련 단계;상기 제2 용액을 응고시킨 후 절단하여 복수의 그래핀 마스터칩을 마련하는 그래핀 마스터칩 마련 단계; 및상기 복수의 그래핀 마스터칩과 상기 폴리머를 섬유 방사 장치로 방사시켜 그래핀 복합 섬유를 마련하는 그래핀 복합 섬유 마련 단계를 포함하는 그래핀 복합 섬유의 제조방법.
- 청구항 1에 있어서,상기 그래핀 복합 섬유 마련 단계에서 상기 복수의 그래핀 마스터칩은 0.03 내지 0.4 중량부를 포함하는 그래핀 복합 섬유의 제조방법.
- 청구항 1에 있어서,상기 분산 용매는 에틸렌 글리콜을 포함하는 그래핀 복합 섬유의 제조방법.
- 청구항 1에 있어서,상기 방사 시 고상중합 공정을 거치고,상기 고상중합 공정에서 유제는 평활제 함량을 70 내지 80 중량% 포함하는 그래핀 복합 섬유의 제조방법.
- 청구항 4에 있어서,상기 고상중합 공정에서 발수 약제는 유효성분의 중량평균분자량을 2,868, PDI는 1.2를 갖는 그래핀 복합 섬유의 제조방법.
- 청구항 4에 있어서,상기 발수 약제의 공급 시에 약제의 확산 효율은 높이기 위해 물과 유화제를 첨가하는 그래핀 복합 섬유의 제조방법.
- 청구항 1에 있어서,상기 폴리머는 폴리에스테르(POLYRSTER), 나일론6(NYLON6), 나일론66(NYLON66), 폴리프로필렌(POLYPROPYLENE), 폴리에틸렌(POLYETHYLEN), 복합사(N/C, P/C), 카본 섬유(CARBON FIBER), 아라미드 섬유(ARAMID FIBER) 및 모노 섬유(MONO FIBER) 중 선택된 하나를 포함하는 그래핀 복합 섬유의 제조방법.
- 그래핀 복합 섬유에 있어서,상기 그래핀 복합 섬유는 상기 청구항 1 내지 청구항 7 중 하나의 방법으로 제조되는 그래핀 복합 섬유.
- 청구항 8에 있어서,그래핀 복합 섬유는 나일론 2.9 데니아 또는 폴리에틸렌 테레프탈레이트(RV 0.80) 1.7 데니아를 포함하는 그래핀 복합 섬유.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202080107404.4A CN116507766A (zh) | 2020-11-23 | 2020-11-30 | 石墨烯复合纤维及其制造方法 |
US18/037,070 US20240003062A1 (en) | 2020-11-23 | 2020-11-30 | Graphene composite fiber and manufacturing method therefor |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020200158116A KR20220070983A (ko) | 2020-11-23 | 2020-11-23 | 그래핀 복합 섬유 및 이의 제조방법 |
KR10-2020-0158116 | 2020-11-23 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2022107978A1 true WO2022107978A1 (ko) | 2022-05-27 |
Family
ID=81709157
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR2020/017333 WO2022107978A1 (ko) | 2020-11-23 | 2020-11-30 | 그래핀 복합 섬유 및 이의 제조방법 |
Country Status (4)
Country | Link |
---|---|
US (1) | US20240003062A1 (ko) |
KR (1) | KR20220070983A (ko) |
CN (1) | CN116507766A (ko) |
WO (1) | WO2022107978A1 (ko) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115928279A (zh) * | 2022-12-31 | 2023-04-07 | 武汉纺织大学 | 石墨烯/硅橡胶同轴纤维基弹性包芯纱及其制备与应用 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20010037164A (ko) * | 1999-10-14 | 2001-05-07 | 조정래 | 산업용 폴리에스터 섬유 및 그의 제조방법 |
US20140231718A1 (en) * | 2013-02-21 | 2014-08-21 | Yi-Jun Lin | Process for Producing Highly conducting and Transparent Films From Graphene Oxide-Metal Nanowire Hybrid Materials |
KR20170078620A (ko) * | 2015-10-27 | 2017-07-07 | 지난 셩취엔 그룹 쉐어 홀딩 코., 엘티디. | 복합 폴리에스테르 재료, 복합 폴리에스테르 섬유 및 그 제조방법과 용도 |
KR20180085768A (ko) * | 2015-11-20 | 2018-07-27 | 지난 셩취엔 그룹 쉐어 홀딩 코., 엘티디. | 개질 섬유 및 그 제조방법 |
KR20190071614A (ko) * | 2017-12-14 | 2019-06-24 | 한양대학교 산학협력단 | 그래핀 복합 섬유 및 그 제조장치, 및 그 제조방법 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101782725B1 (ko) | 2016-04-11 | 2017-09-29 | 한양대학교 산학협력단 | 그래핀 섬유 및 그 제조 방법 |
-
2020
- 2020-11-23 KR KR1020200158116A patent/KR20220070983A/ko active Search and Examination
- 2020-11-30 CN CN202080107404.4A patent/CN116507766A/zh active Pending
- 2020-11-30 US US18/037,070 patent/US20240003062A1/en active Pending
- 2020-11-30 WO PCT/KR2020/017333 patent/WO2022107978A1/ko active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20010037164A (ko) * | 1999-10-14 | 2001-05-07 | 조정래 | 산업용 폴리에스터 섬유 및 그의 제조방법 |
US20140231718A1 (en) * | 2013-02-21 | 2014-08-21 | Yi-Jun Lin | Process for Producing Highly conducting and Transparent Films From Graphene Oxide-Metal Nanowire Hybrid Materials |
KR20170078620A (ko) * | 2015-10-27 | 2017-07-07 | 지난 셩취엔 그룹 쉐어 홀딩 코., 엘티디. | 복합 폴리에스테르 재료, 복합 폴리에스테르 섬유 및 그 제조방법과 용도 |
KR20180085768A (ko) * | 2015-11-20 | 2018-07-27 | 지난 셩취엔 그룹 쉐어 홀딩 코., 엘티디. | 개질 섬유 및 그 제조방법 |
KR20190071614A (ko) * | 2017-12-14 | 2019-06-24 | 한양대학교 산학협력단 | 그래핀 복합 섬유 및 그 제조장치, 및 그 제조방법 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115928279A (zh) * | 2022-12-31 | 2023-04-07 | 武汉纺织大学 | 石墨烯/硅橡胶同轴纤维基弹性包芯纱及其制备与应用 |
Also Published As
Publication number | Publication date |
---|---|
KR20220070983A (ko) | 2022-05-31 |
CN116507766A (zh) | 2023-07-28 |
US20240003062A1 (en) | 2024-01-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN110982114B (zh) | 芳纶/碳纳米管杂化气凝胶薄膜、其制备方法及应用 | |
JP6634064B2 (ja) | ナノファイバーのリボンおよびシートならびにナノファイバーの撚り糸および無撚り糸の製造および適用 | |
US11149129B2 (en) | Graphene composite material and preparation method thereof | |
Okuzaki et al. | Highly conductive PEDOT/PSS microfibers fabricated by wet-spinning and dip-treatment in ethylene glycol | |
WO2012124937A2 (ko) | 그라핀 복합 섬유 및 이의 제조 방법 | |
WO2017066937A1 (zh) | 一种石墨烯-涤纶纳米复合纤维的制备方法 | |
WO2018105767A1 (ko) | 종이 집전체, 이의 제조방법 및 이를 포함하는 전기화학소자 | |
KR102556948B1 (ko) | 탄소나노튜브 나노복합 전도성 다섬유 및 그 제조방법 | |
WO2022107978A1 (ko) | 그래핀 복합 섬유 및 이의 제조방법 | |
CN107275498B (zh) | 一种柔性电致发光器件及其制备方法 | |
WO2017068603A1 (en) | Composite fibers having aligned inorganic nano structures of high aspect ratio and preparation method | |
KR101572194B1 (ko) | 은 나노와이어 네트워크가 내장된 투명 폴리이미드층을 이용한 투명 전극 및 그 제조방법 | |
KR20230034275A (ko) | 그래핀 복합 섬유 및 이의 제조방법 | |
WO2012008632A1 (ko) | 인장방법에 의한 정렬된 금속나노선 필름 제조방법 | |
Gao et al. | Polyacrylonitrile/electroconductive TiO 2 nanoparticles composite fibers via wet-spinning | |
KR102183500B1 (ko) | 그래핀 복합 섬유의 제조방법 | |
KR20210028597A (ko) | 그래핀 복합 섬유 및 이의 제조방법 | |
CN107326474B (zh) | 一种帘子线用石墨烯涤纶复合纤维及其制备方法 | |
KR20180024670A (ko) | 시스코어 복합방사로 제조된 원착 폴리페닐렌 설파이드 복합 섬유 | |
CN114249921B (zh) | 电容膜用纳米纤维填料、包含其的电容膜、以及电容膜的制备方法 | |
Yao et al. | Carbon Nanotube Fibers for Wearable Devices | |
Bkkar et al. | Properties optimization of electrospun polymer: organic-free perovskite nanofibers by controlling solution concentration | |
Rana et al. | Polymer Nanocomposite Fibers Based on Carbon Nanomaterial for Enhanced Electrical Properties | |
KR20200122003A (ko) | Pan-그래핀 복합 섬유 및 그 제조 방법 | |
EP0867042A1 (en) | Method for producing and/or treating refractory filaments, especially superconductive filaments |
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: 20962584 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 18037070 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 202080107404.4 Country of ref document: CN |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 20962584 Country of ref document: EP Kind code of ref document: A1 |