JP2020196984A - 炭素繊維の製造方法 - Google Patents
炭素繊維の製造方法 Download PDFInfo
- Publication number
- JP2020196984A JP2020196984A JP2020074014A JP2020074014A JP2020196984A JP 2020196984 A JP2020196984 A JP 2020196984A JP 2020074014 A JP2020074014 A JP 2020074014A JP 2020074014 A JP2020074014 A JP 2020074014A JP 2020196984 A JP2020196984 A JP 2020196984A
- Authority
- JP
- Japan
- Prior art keywords
- acrylonitrile
- glycol
- based polymer
- carbon fibers
- fiber
- 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.)
- Granted
Links
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 97
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 97
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims description 35
- 238000000034 method Methods 0.000 title abstract description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 138
- 229920000642 polymer Polymers 0.000 claims abstract description 112
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 109
- 239000000835 fiber Substances 0.000 claims abstract description 102
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 150000001875 compounds Chemical class 0.000 claims abstract description 39
- 230000006641 stabilisation Effects 0.000 claims abstract description 27
- 238000011105 stabilization Methods 0.000 claims abstract description 27
- 238000002074 melt spinning Methods 0.000 claims abstract description 25
- 238000003763 carbonization Methods 0.000 claims abstract description 17
- 238000009835 boiling Methods 0.000 claims abstract description 11
- 238000004804 winding Methods 0.000 claims description 47
- 238000004519 manufacturing process Methods 0.000 claims description 36
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 33
- 239000000178 monomer Substances 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 11
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 claims description 11
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 11
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- -1 glycol compound Chemical class 0.000 claims description 10
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 5
- 229940051250 hexylene glycol Drugs 0.000 claims description 5
- 230000000087 stabilizing effect Effects 0.000 claims description 5
- 238000010000 carbonizing Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000009987 spinning Methods 0.000 abstract description 31
- 239000000243 solution Substances 0.000 description 23
- 239000002904 solvent Substances 0.000 description 22
- 238000002844 melting Methods 0.000 description 16
- 230000008018 melting Effects 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 230000001965 increasing effect Effects 0.000 description 11
- 238000002166 wet spinning Methods 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 238000000578 dry spinning Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 239000004014 plasticizer Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 230000008863 intramolecular interaction Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—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
- D01F9/225—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 from stabilised polyacrylonitriles
-
- 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
-
- 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
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Fibers (AREA)
- Artificial Filaments (AREA)
Abstract
Description
a)アクリロニトリル系重合体溶液を、沸点が180〜210℃のグリコール系化合物を含むグリコール系化合物溶液に投入し、アクリロニトリル系重合体を沈殿させるステップと、
b)前記アクリロニトリル系重合体を溶融紡糸して紡糸繊維を得るステップと、
c)前記紡糸繊維を安定化および炭化して炭素繊維を得るステップと、を含む。
1.引張強度、引張弾性率、および伸び
ASTM D 3379−75(Standard Test Method for Tensile Strength and Young’s Modulus for High−Modulus Single−Filament Materials)に準じて測定用試験片を作製し、FAVIMATを用いて引張強度、引張弾性率、および伸びを測定した。
実施例および比較例の炭素繊維を、光学顕微鏡(Nikon E200 LED Trino+)を用いて平均直径を観察した。
アクリロニトリル単量体およびメチルアクリレート単量体を90:10モル比で混合した単量体混合物100モルに対して、2,2´−アゾビスイソブチロニトリル(AIBN)0.015モル比、1−ドデカンチオール(CTA)0.001モル比で混合して混合物を製造した。単量体混合物100モルに対して、2倍含量のジメチルスルホキシド(DMSO)溶媒に前記混合物を混合し、60℃の温度で16時間重合することで、アクリロニトリル系重合体溶液を製造した。
前記実施例1において、アクリロニトリル系重合体の沈殿時に、エチレングリコールではなくプロピレングリコールが40体積%で溶解された水溶液を投入して沈殿させ、アクリロニトリル系重合体を得た。その後、前記アクリロニトリル系重合体を常温で24時間乾燥した後、60℃で12時間真空乾燥した。この際、アクリロニトリル系重合体中におけるプロピレングリコールの総含量は10.2重量%であり、重量平均分子量は121,000g/molであった。
前記実施例1において、アクリロニトリル系重合体の沈殿時に、エチレングリコールではなくブチレングリコールが40体積%で溶解された水溶液を投入して沈殿させ、アクリロニトリル系重合体を得た。その後、前記アクリロニトリル系重合体を常温で24時間乾燥した後、60℃で12時間真空乾燥した。この際、アクリロニトリル系重合体中におけるブチレングリコールの総含量は11重量%であり、重量平均分子量は125,000g/molであった。
前記実施例1において、アクリロニトリル系重合体の沈殿時に、エチレングリコールではなくペンチレングリコールが40体積%で溶解された水溶液を投入して沈殿させ、アクリロニトリル系重合体を得た。その後、前記アクリロニトリル系重合体を常温で24時間乾燥した後、60℃で12時間真空乾燥した。この際、アクリロニトリル系重合体中におけるペンチレングリコールの総含量は9.5重量%であり、重量平均分子量は122,500g/molであった。
前記実施例1において、アクリロニトリル系重合体の沈殿時に、エチレングリコールではなくヘキシレングリコールが40体積%で溶解された水溶液を投入して沈殿させ、アクリロニトリル系重合体を得た。その後、前記アクリロニトリル系重合体を常温で24時間乾燥した後、60℃で12時間真空乾燥した。この際、アクリロニトリル系重合体中におけるヘキシレングリコールの総含量は10重量%であり、重量平均分子量は126,000g/molであった。
前記実施例1において、エチレングリコールが60体積%で溶解された水溶液に投入して沈殿させ、真空乾燥されたアクリロニトリル系重合体中におけるエチレングリコールの総含量が17重量%であることを除き、同様にアクリロニトリル系重合体を得た。
前記実施例1で製造されたアクリロニトリル系重合体溶液を蒸留水に沈殿させてアクリロニトリル系重合体を得た。
前記実施例1で製造されたアクリロニトリル系重合体溶液を蒸留水に沈殿させてアクリロニトリル系重合体を得た。その後、前記アクリロニトリル系重合体を常温で24時間乾燥した後、60℃で16時間真空乾燥した。
Claims (13)
- a)アクリロニトリル系重合体溶液を、沸点が180〜210℃のグリコール系化合物を含むグリコール系化合物溶液に投入し、アクリロニトリル系重合体を沈殿させるステップと、
b)前記アクリロニトリル系重合体を溶融紡糸して紡糸繊維を得るステップと、
c)前記紡糸繊維を安定化および炭化して炭素繊維を得るステップと、
を含む炭素繊維の製造方法。 - 前記グリコール系化合物がC2−C10アルキレングリコールである、請求項1に記載の炭素繊維の製造方法。
- 前記グリコール系化合物が、エチレングリコール、プロピレングリコール、ブチレングリコール、ペンチレングリコール、およびヘキシレングリコールからなる群から選択される何れか1つまたは2つ以上の混合物である、請求項2に記載の炭素繊維の製造方法。
- 前記アクリロニトリル系重合体が、アクリロニトリル単量体およびアクリル系単量体から誘導された繰り返し単位を含む、請求項1に記載の炭素繊維の製造方法。
- 前記b)ステップの後に、紡糸繊維を100〜3,000m/minの巻取速度で巻き取るステップをさらに含む、請求項1に記載の炭素繊維の製造方法。
- 前記紡糸繊維は、巻き取り後の平均直径が1〜50μmである、請求項5に記載の炭素繊維の製造方法。
- 前記アクリロニトリル系重合体は、アクリロニトリル単量体50〜97モル%およびアクリル系単量体3〜50モル%の繰り返し単位を含む、請求項4に記載の炭素繊維の製造方法。
- 前記a)ステップの後に、前記アクリロニトリル系重合体を乾燥するステップをさらに含む、請求項1に記載の炭素繊維の製造方法。
- 前記乾燥後、アクリロニトリル系重合体は、総重量に対して、グリコール系化合物を5〜15重量%で含む、請求項8に記載の炭素繊維の製造方法。
- 前記b)ステップの後に、紡糸繊維を延伸するステップをさらに含む、請求項1に記載の炭素繊維の製造方法。
- 前記延伸は100〜250℃で行う、請求項10に記載の炭素繊維の製造方法。
- 前記c)ステップにおいて、安定化は120〜300℃で行う、請求項1に記載の炭素繊維の製造方法。
- 前記c)ステップにおいて、炭化は、不活性気体雰囲気下、800〜3,000℃で行う、請求項1に記載の炭素繊維の製造方法。
Applications Claiming Priority (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2019-0064909 | 2019-05-31 | ||
KR20190064909 | 2019-05-31 | ||
KR20190093174 | 2019-07-31 | ||
KR10-2019-0093174 | 2019-07-31 | ||
KR10-2020-0012719 | 2020-02-03 | ||
KR10-2020-0012745 | 2020-02-03 | ||
KR1020200012745A KR102115961B1 (ko) | 2019-05-31 | 2020-02-03 | 탄소섬유의 제조방법 |
KR1020200012719A KR102115967B1 (ko) | 2019-07-31 | 2020-02-03 | 탄소섬유의 제조방법 |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2020196984A true JP2020196984A (ja) | 2020-12-10 |
JP6899469B2 JP6899469B2 (ja) | 2021-07-07 |
Family
ID=70227832
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2020074014A Active JP6899469B2 (ja) | 2019-05-31 | 2020-04-17 | 炭素繊維の製造方法 |
Country Status (4)
Country | Link |
---|---|
US (1) | US11268215B2 (ja) |
EP (1) | EP3744879A1 (ja) |
JP (1) | JP6899469B2 (ja) |
CN (1) | CN112011855B (ja) |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62231078A (ja) * | 1985-12-27 | 1987-10-09 | 東レ株式会社 | 炭素繊維製造用アクリル系前駆体の製造法 |
JPH07278397A (ja) * | 1994-04-15 | 1995-10-24 | Toray Ind Inc | アクリル系重合体組成物の製造方法 |
JPH07331528A (ja) * | 1994-06-06 | 1995-12-19 | Toray Ind Inc | アクリル系繊維の製造法 |
JP2012522142A (ja) * | 2009-03-31 | 2012-09-20 | ドンファ ユニバーシティー | 炭素繊維及びその原糸、プレ酸化繊維の製造方法 |
US20160258082A1 (en) * | 2015-03-06 | 2016-09-08 | Ut-Battelle, Llc | Low temperature stabilization process for production of carbon fiber having structural order |
WO2017167335A1 (en) * | 2016-03-31 | 2017-10-05 | Vestas Wind Systems A/S | Improvements relating to the interconnection of multiple renewable energy power plants |
JP2017530231A (ja) * | 2014-09-29 | 2017-10-12 | フラウンホーファー・ゲゼルシャフト・ツール・フェルデルング・デア・アンゲヴァンテン・フォルシュング・エー・ファウ | ポリアクリロニトリルからの溶融紡糸可能なコポリマー、溶融紡糸を用いて繊維又は繊維前駆体を製造するための方法、及び当該方法により製造された繊維 |
CN109402792A (zh) * | 2018-10-31 | 2019-03-01 | 北京化工大学 | 一种低直径高强度的聚丙烯腈基碳纤维及其制备方法 |
JP2019513167A (ja) * | 2016-03-22 | 2019-05-23 | フラウンホーファー・ゲゼルシャフト・ツール・フェルデルング・デア・アンゲヴァンテン・フォルシュング・エー・ファウ | 溶融紡糸可能なポリアクリロニトリル系コポリマー、溶融紡糸によって繊維又は繊維前駆体を製造する方法、及びその方法で製造された繊維 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SE403141B (sv) | 1973-02-05 | 1978-07-31 | American Cyanamid Co | Smeltspinningsforfarande for framstellning av en akrylnitrilpolymerfiber |
US4921656A (en) * | 1988-08-25 | 1990-05-01 | Basf Aktiengesellschaft | Formation of melt-spun acrylic fibers which are particularly suited for thermal conversion to high strength carbon fibers |
US4981752A (en) * | 1989-07-06 | 1991-01-01 | Basf Aktiengesellschaft | Formation of melt-spun acrylic fibers which are well suited for thermal conversion to high strength carbon fibers |
KR101342176B1 (ko) * | 2006-10-18 | 2013-12-16 | 도레이 카부시키가이샤 | 폴리아크릴로니트릴계 중합체와 그의 제조 방법, 탄소 섬유 전구체 섬유의 제조 방법, 및 탄소 섬유와 그의 제조 방법 |
WO2015175050A2 (en) * | 2014-02-14 | 2015-11-19 | The Board Of Regents Of The Univeristy Of Texas System | Carbon fiber compositions and methods of making |
US20170217125A1 (en) * | 2014-09-11 | 2017-08-03 | Agency For Science, Technology And Research | Electrospun conductive carbon fibers |
DE102015222585A1 (de) | 2015-11-16 | 2017-05-18 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Verfahren zur Herstellung von thermisch stabilen schmelzspinnbaren PAN-Copolymeren, PAN-Copolymere, hieraus gebildete Formkörper sowie Verfahren zur Herstellung dieser Formkörper |
DE112016006681A5 (de) * | 2016-03-29 | 2019-01-03 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Schmelzspinnbare Copolymere vom Polyacrylnitril, Verfahren zur Herstellung von Fasern oder Faserprecursoren mittels Schmelzspinnen und entsprechend hergestellte Fasern |
-
2020
- 2020-04-02 CN CN202010254131.8A patent/CN112011855B/zh active Active
- 2020-04-07 EP EP20168440.4A patent/EP3744879A1/en active Pending
- 2020-04-10 US US16/845,570 patent/US11268215B2/en active Active
- 2020-04-17 JP JP2020074014A patent/JP6899469B2/ja active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62231078A (ja) * | 1985-12-27 | 1987-10-09 | 東レ株式会社 | 炭素繊維製造用アクリル系前駆体の製造法 |
JPH07278397A (ja) * | 1994-04-15 | 1995-10-24 | Toray Ind Inc | アクリル系重合体組成物の製造方法 |
JPH07331528A (ja) * | 1994-06-06 | 1995-12-19 | Toray Ind Inc | アクリル系繊維の製造法 |
JP2012522142A (ja) * | 2009-03-31 | 2012-09-20 | ドンファ ユニバーシティー | 炭素繊維及びその原糸、プレ酸化繊維の製造方法 |
JP2017530231A (ja) * | 2014-09-29 | 2017-10-12 | フラウンホーファー・ゲゼルシャフト・ツール・フェルデルング・デア・アンゲヴァンテン・フォルシュング・エー・ファウ | ポリアクリロニトリルからの溶融紡糸可能なコポリマー、溶融紡糸を用いて繊維又は繊維前駆体を製造するための方法、及び当該方法により製造された繊維 |
US20160258082A1 (en) * | 2015-03-06 | 2016-09-08 | Ut-Battelle, Llc | Low temperature stabilization process for production of carbon fiber having structural order |
JP2019513167A (ja) * | 2016-03-22 | 2019-05-23 | フラウンホーファー・ゲゼルシャフト・ツール・フェルデルング・デア・アンゲヴァンテン・フォルシュング・エー・ファウ | 溶融紡糸可能なポリアクリロニトリル系コポリマー、溶融紡糸によって繊維又は繊維前駆体を製造する方法、及びその方法で製造された繊維 |
WO2017167335A1 (en) * | 2016-03-31 | 2017-10-05 | Vestas Wind Systems A/S | Improvements relating to the interconnection of multiple renewable energy power plants |
CN109402792A (zh) * | 2018-10-31 | 2019-03-01 | 北京化工大学 | 一种低直径高强度的聚丙烯腈基碳纤维及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
JP6899469B2 (ja) | 2021-07-07 |
EP3744879A1 (en) | 2020-12-02 |
CN112011855A (zh) | 2020-12-01 |
US11268215B2 (en) | 2022-03-08 |
US20200378034A1 (en) | 2020-12-03 |
CN112011855B (zh) | 2023-04-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US9334586B2 (en) | Process of melt-spinning polyacrylonitrile fiber | |
Frank et al. | High-performance PAN-based carbon fibers and their performance requirements | |
US8906278B2 (en) | Process of melt-spinning polyacrylonitrile fiber | |
CN102733009A (zh) | 一种具有规整表面沟槽的高强度聚丙烯腈基碳纤维及其制备方法 | |
JP2010242248A (ja) | 超微細炭素繊維の製造方法 | |
US20150118142A1 (en) | Formation of carbon nanotube-enhanced fibers and carbon nanotube-enahnced hybrid structures | |
CN107904698A (zh) | 一种沥青基碳纤维的制备方法 | |
KR20130060464A (ko) | 중공 탄소섬유의 제조방법 | |
KR20120126426A (ko) | 마이크로웨이브를 이용한 탄소섬유 제조용 폴리아크릴로니트릴계 중합체의 제조 방법 및 이를 이용한 탄소섬유의 제조 방법 | |
KR102115961B1 (ko) | 탄소섬유의 제조방법 | |
JP6899469B2 (ja) | 炭素繊維の製造方法 | |
JP2021175843A (ja) | 炭素材料の製造方法 | |
JP2016532021A (ja) | 小直径ポリオレフィン繊維 | |
JP2021500488A (ja) | 塩素化ポリ塩化ビニルから形成された炭素繊維及びその製造方法 | |
KR102115967B1 (ko) | 탄소섬유의 제조방법 | |
KR20120007183A (ko) | 보풀발생이 억제되는 탄소섬유의 제조방법 | |
KR20110130186A (ko) | 보풀발생이 억제되는 탄소섬유의 제조방법 | |
JPH03260109A (ja) | 気相成長炭素繊維混入有機繊維 | |
JP7159563B2 (ja) | ガス分離用炭素膜の製造方法 | |
KR20110079369A (ko) | 탄소섬유용 폴리아크릴로니트릴계 전구체의 도프원액 제조 방법 | |
JPH11124742A (ja) | 炭素繊維の製造法 | |
JP2015071833A (ja) | 溶融ブレンド繊維及びそれを用いた炭素繊維の製造方法 | |
KR101429381B1 (ko) | 탄소섬유 전구체의 제조방법 | |
JPH02145814A (ja) | 改良された黒鉛繊維の製造方法 | |
KR20110134136A (ko) | 섬도편차가 감소되는 탄소섬유의 제조방법 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20200417 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20210422 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20210518 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20210614 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6899469 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313113 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313113 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |