NZ617199B2 - Method for the production of lignin-containing precursor fibres and also carbon fibres - Google Patents
Method for the production of lignin-containing precursor fibres and also carbon fibres Download PDFInfo
- Publication number
- NZ617199B2 NZ617199B2 NZ617199A NZ61719912A NZ617199B2 NZ 617199 B2 NZ617199 B2 NZ 617199B2 NZ 617199 A NZ617199 A NZ 617199A NZ 61719912 A NZ61719912 A NZ 61719912A NZ 617199 B2 NZ617199 B2 NZ 617199B2
- Authority
- NZ
- New Zealand
- Prior art keywords
- fibre
- lignin
- solution
- sort
- production
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 61
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229920005610 lignin Polymers 0.000 title claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000002243 precursor Substances 0.000 title claims abstract description 15
- 239000000835 fiber Substances 0.000 claims abstract description 24
- 238000009987 spinning Methods 0.000 claims abstract description 14
- 229920000642 polymer Polymers 0.000 claims abstract description 10
- 229920002678 cellulose Polymers 0.000 claims abstract description 8
- 239000001913 cellulose Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 230000015271 coagulation Effects 0.000 claims abstract 9
- 238000005345 coagulation Methods 0.000 claims abstract 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract 9
- 239000004753 textile Substances 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 6
- 239000007788 liquid Substances 0.000 claims 6
- 150000003512 tertiary amines Chemical class 0.000 claims 5
- 238000001035 drying Methods 0.000 claims 4
- 239000002608 ionic liquid Substances 0.000 claims 4
- 239000000203 mixture Substances 0.000 claims 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical group CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims 3
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 claims 3
- 238000013019 agitation Methods 0.000 claims 3
- -1 imidazolium compound Chemical class 0.000 claims 3
- 238000004898 kneading Methods 0.000 claims 3
- 238000007493 shaping process Methods 0.000 claims 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims 2
- 150000008431 aliphatic amides Chemical class 0.000 claims 2
- 238000003763 carbonization Methods 0.000 claims 2
- 239000002798 polar solvent Substances 0.000 claims 2
- 238000004804 winding Methods 0.000 claims 2
- LCRZZBQGAWGKFB-UHFFFAOYSA-N 1-butyl-2-methyl-1h-imidazol-1-ium;chloride Chemical compound [Cl-].CCCCN1C=C[NH+]=C1C LCRZZBQGAWGKFB-UHFFFAOYSA-N 0.000 claims 1
- XXQGYGJZNMSSFD-UHFFFAOYSA-N 2-[2-(dimethylcarbamoyl)phenoxy]acetic acid Chemical compound CN(C)C(=O)C1=CC=CC=C1OCC(O)=O XXQGYGJZNMSSFD-UHFFFAOYSA-N 0.000 claims 1
- HMHBUOQAUCQVFH-UHFFFAOYSA-N 3-ethyl-2-methyl-1h-imidazol-3-ium;acetate Chemical compound CC([O-])=O.CC[NH+]1C=CN=C1C HMHBUOQAUCQVFH-UHFFFAOYSA-N 0.000 claims 1
- DWYIRCDOZWPXKS-UHFFFAOYSA-N 3-pentyl-1h-imidazol-3-ium;acetate Chemical compound CC([O-])=O.CCCCC[N+]=1C=CNC=1 DWYIRCDOZWPXKS-UHFFFAOYSA-N 0.000 claims 1
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims 1
- 102100022443 CXADR-like membrane protein Human genes 0.000 claims 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims 1
- 102000004190 Enzymes Human genes 0.000 claims 1
- 108090000790 Enzymes Proteins 0.000 claims 1
- 229920002488 Hemicellulose Polymers 0.000 claims 1
- 229920001732 Lignosulfonate Polymers 0.000 claims 1
- 239000004117 Lignosulphonate Substances 0.000 claims 1
- 239000003513 alkali Substances 0.000 claims 1
- 230000029087 digestion Effects 0.000 claims 1
- 229920005611 kraft lignin Polymers 0.000 claims 1
- 235000019357 lignosulphonate Nutrition 0.000 claims 1
- 150000004682 monohydrates Chemical class 0.000 claims 1
- 239000002244 precipitate Substances 0.000 claims 1
- 238000004537 pulping Methods 0.000 claims 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 claims 1
- 239000002023 wood Substances 0.000 claims 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 abstract description 5
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 abstract description 3
- 239000007858 starting material Substances 0.000 abstract 2
- 238000010276 construction Methods 0.000 description 3
- 229920002239 polyacrylonitrile Polymers 0.000 description 3
- 239000002131 composite material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/05—Filamentary, e.g. strands
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D99/00—Subject matter not provided for in other groups of this subclass
- B29D99/0078—Producing filamentary materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
- B29K2033/18—Polymers of nitriles
- B29K2033/20—PAN, i.e. polyacrylonitrile
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/731—Filamentary material, i.e. comprised of a single element, e.g. filaments, strands, threads, fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
-
- 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
-
- 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
- D01F9/16—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate
- D01F9/17—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate from lignin
Abstract
Disclosed is a method for the production of a precursor fibre for the production of carbon- and activated carbon fibres according to the wet- or air-gap spinning method, in which a solution of lignin and a fibre-forming polymer selected from cellulose derivatives, in a suitable solvent is extruded through the holes of a spinning nozzle into a coagulation bath, the formed thread is stretched and subsequently treated, dried at an elevated temperature and then wound up. The lignin-containing thread is an economical starting material for the production of carbon and activated carbon fibres. Also disclosed is a method for the production of a carbon fibre from the precursor fibre by carbonising above 800 °C and subjecting the fibre to water vapour. hrough the holes of a spinning nozzle into a coagulation bath, the formed thread is stretched and subsequently treated, dried at an elevated temperature and then wound up. The lignin-containing thread is an economical starting material for the production of carbon and activated carbon fibres. Also disclosed is a method for the production of a carbon fibre from the precursor fibre by carbonising above 800 °C and subjecting the fibre to water vapour.
Description
Method for the production of lignin—containing precursor fibres and also
carbon fibres
The invention s to a method for the production of a precursor for
the production of carbon- and activated carbon fibres according to the
wet- or air—gap ng method, in which a solution of lignin and a
fibrewforming polymer in a suitable solvent is extruded through the
holes of a spinning nozzle into a ation bath, the formed thread is
stretched and subsequently treated, dried at an elevated temperature
and then wound up. The lignin—containing thread is an economical
starting al for the production of carbon- and activated carbon
fibres.
Carbon fibres are high—performance reinforcing fibres which are used
essentially for composite materials in aircraft construction, high-
performance vehicle construction (Formula I, high-performance sailing
ships etc), for sports equipment and increasingly for wind energy
plants. Currently, extensive efforts are being made worldwide to
introduce carbon fibres of average quality (at a reduced price level) into
mass applications in automobile construction, the development of
-reduced electric vehicles which is sought ly in the
meantime enting an essential driving force.
Carbon fibres are produced by heat treatment above 1,000°C of organic
precursor fibres. The first carbon fibres were developed on the basis of
cellulose precursors and used as filaments in lamps. Nowadays,
polyacrylonitrile or copolymers of rylonitrile are the dominating
polymers for the production of precursors for carbon fibres. The palette
of carbon fibres based on PAN is supplemented by high-modulus carbon
fibre made from pitch. For PAN-based carbon fibres, the estimated
annual capacity in 2010 was at approx. 77,000 t and, for based
carbon fibres, at 1,830 t (technical textiles
Claims (47)
1. A method for the production of a lignin-containing precursor fibre for the production of carbon fibres and/or activated carbon fibres, comprising a) forming a solution, comprising at least one sort of lignin and also at least one fibreforming polymer selected from the group consisting of cellulose or cellulose derivatives, in at least one solvent selected from the group consisting of tertiary amine oxides, and b) transferring the solution into a coagulation bath by extruding the solution through a spinning nozzle by an air-gap spinning method, wherein the lignin-containing precursor fibre precipitates when the solution is extruded, and c) stretching the lignin-containing precursor fibre to at least 1.1 times its length, at a temperature of at least 60C in the coagulation bath, in air, or in water vapour.
2. The method according to claim 1, characterised in that the solution used in step a) is produced by agitation or kneading of the at least one sort of lignin and also of the at least one fibre-forming polymer in the at least one solvent.
3. The method according to claim 1 or claim 2, wherein the solution used in step a) is produced by agitation or kneading of the at least one sort of lignin and also of the at least one fibre-forming polymer in the at least one solvent at a temperature of 60°C or more.
4. The method according to any one of claims 1 to 3, wherein the solution used in step a) is produced by agitation or kneading of the at least one sort of lignin and also of the at least one fibre-forming polymer in the at least one solvent at a temperature of 80°C or more.
5. The method according to any one of the preceding claims, wherein the solution is filtered before introduction into the coagulation bath.
6. The method according to any one of the preceding claims, wherein the spinning hole diameter of the spinning nozzle is from 50 to 600 µm. 15 (11065938_1):JJP
7. The method according to any one of the preceding claims, wherein the spinning hole diameter of the spinning nozzle is from 100 to 500 µm.
8. The method according to claim 6 or claim 7, wherein the shaping is performed by the air-gap spinning method.
9. The method according to claim 8, wherein the shaping is performed by the air-gap spinning method wherein the air gap is at least 10 mm.
10. The method according to claim 8 or claim 9, wherein the shaping is performed by the air-gap spinning method wherein the air gap is at least 20 mm and at most 500 mm.
11. The method according to any one of the preceding claims, wherein the lignincontaining precursor fibre d) is washed e) is treated subsequently with textile aids for improving the thread strength and for avoiding electrostatic charges, f) is dried and/or g) is wound up.
12. The method according to claim 11, wherein in step c), the lignin-containing fibre according to b) is stretched to 1.1 to 12 times its length.
13. The method according to claim 11 or claim 12, wherein in step c), the lignin-containing fibre according to b) is stretched to 1.5 times its length.
14. The method according to claim 11 or claim 12, wherein in step c), the lignin-containing fibre according to b) is stretched to 2 times its length. 16 (11065938_1):JJP
15. The method according to any one of claims 11 to 14, wherein in step c), the stretching is performed at a temperature of at least 80°C.
16. The method according to any one of claims 11 to 14, wherein in step c), the stretching is performed at a temperature of at least 90°C.
17. The method according to any one of claims 11 to 14, wherein in step c), the stretching is performed at a temperature of at least 100°C.
18. The method according to any one of claims 11 to 17, wherein in step c), the stretching is implemented in the coagulation bath, in air or in water vapour.
19. The method according to any one of claims 11 to 18, wherein in step d), the lignincontaining fibre according to b) is washed with demineralised water.
20. The method according to any one of claims 11 to 19, wherein in step f), the lignincontaining fibre according to b) is dried by winding up or winding round of the fibre onto or around heated rollers and/or by through flow drying at a temperature of at least 80°C.
21. The method according to claim 20, wherein the temperature is at least 100°C.
22. The method according to any one of claims 11 to 21, wherein the fibre is treated with a spinning oil before drying, after drying or before and after drying.
23. The method according to any one of the preceding claims, wherein, respectively relative to the entire solution, the concentration a) of the at least one sort of lignin is from 1 to 99% by weight, and/or b) of the at least one fibre-forming polymer is from 1 to 99% by weight.
24. The method according to claim 2523 wherein, respectively relative to the entire solution, the concentration a) of the at least one sort of lignin is from 2 to 30% by weight. 17 (11065938_1):JJP
25. The method according to claim 23, wherein, respectively relative to the entire solution, the concentration a) of the at least one sort of lignin is from 3 to 20% by weight.
26. The method according to any one of claims 23 to 25, wherein, respectively relative to the entire solution, the concentration b) of the at least one fibre-forming polymer is from 5 to 40% by weight.
27. The method according to any one of claims 23 to 25, wherein, respectively relative to the entire solution, the concentration b) of the at least one fibre-forming polymer is from 7 to 30% by weight.
28. The method according to any one of the preceding claims, wherein the coagulation bath comprises water or a mixture of water and an organic liquid.
29. The method according to claim 28, wherein the organic liquid is an aprotic polar solvent.
30. The method according to claim 29, wherein the aprotic polar solvent is DMSO.
31. The method according to claim 28, wherein the organic liquid is an aliphatic amide which is liquid at room temperature.
32. The method according to claim 31, wherein the aliphatic amide is dimethylformamide (DMF) or dimethylacetamide (DMAc).
33. The method according to claim 28, wherein the organic liquid is a tertiary amine oxide.
34. The method according to claim 33, wherein the tertiary amine oxide is Nmethylmorpholine-N- oxide. 18 (11065938_1):JJP
35. The method according to claim 28, wherein the organic liquid is an ionic liquid.
36. The method according to claim 35, wherein the ionic liquid is selected from the group consisting of an imidazolium compound, a pyridinium compound or a tetraalkylammonium compound.
37. The method according to claim 35 or claim 36, wherein the ionic liquid is 1-butyl methylimidazolium chloride, 1- butylmethylimidazolium acetate, or 1 -ethyl methylimidazolium acetate.
38. The method according to any one of claims 28 to 37, wherein the pH value of the coagulation bath is between 1 and 7.
39. The method according to any one of claims 28 to 38, wherein the pH value of the coagulation bath is between 2 and 5.
40. The method according to any one of the preceding claims, wherein the tertiary amine oxide is aqueous N-methylmorpholine-N-oxide (NMMO).
41. The method according to claim 40, wherein the tertiary amine oxide is aqueous Nmethylmorpholine-N-oxide (NMMO) monohydrate.
42. The method according to any one of the preceding claims, wherein the cellulose and/or cellulose derivatives, are selected from the group consisting of cellulose carbamate, cellulose allophanate, and hemicellulose; and/or mixtures or blends thereof.
43. The method according to any one of the preceding claims, wherein the at least one sort of lignin results from wood and annual plant pulping methods and is selected from the group consisting of alkali lignin, kraft lignin, lignosulphonate, thiolignin, organosolvlignin, ASAM lignin, lignins from digestion processes by means of ionic liquids or enzymes and/or combinations or mixtures thereof. 19 (11065938_1):JJP
44. A precursor fibre, produced according to the method of any one of claims 1 to 43.
45. A method for the production of a carbon fibre in which a precursor fibre according to claim 44 is stabilised at temperatures between 100 and 600°C and is carbonised above 800°C under inert conditions.
46. The method according to claim 45, wherein the carbon fibre is subjected to water vapour, after the carbonisation, at temperatures > 200°C.
47. The method according to claim 46, wherein the carbon fibre is subjected to water vapour, after the carbonisation, at temperatures > 300°C.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP11004131A EP2524980A1 (en) | 2011-05-18 | 2011-05-18 | Method for producing precursor fibres and carbon fibres containing lignine |
| EP11004131.6 | 2011-05-18 | ||
| PCT/EP2012/059112 WO2012156441A1 (en) | 2011-05-18 | 2012-05-16 | Method for the production of lignin-containing precursor fibres and also carbon fibres |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| NZ617199A NZ617199A (en) | 2017-03-31 |
| NZ617199B2 true NZ617199B2 (en) | 2017-07-04 |
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