US20170298539A1 - Method for the thermal stabilisation of fibres and said type of stabilised fibres - Google Patents
Method for the thermal stabilisation of fibres and said type of stabilised fibres Download PDFInfo
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- US20170298539A1 US20170298539A1 US15/513,454 US201515513454A US2017298539A1 US 20170298539 A1 US20170298539 A1 US 20170298539A1 US 201515513454 A US201515513454 A US 201515513454A US 2017298539 A1 US2017298539 A1 US 2017298539A1
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- Prior art keywords
- fibre
- mol
- fibres
- solvent
- stabilisation
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- 238000000034 method Methods 0.000 title claims abstract description 29
- 230000006641 stabilisation Effects 0.000 title claims description 17
- 239000000835 fiber Substances 0.000 claims abstract description 37
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 238000002074 melt spinning Methods 0.000 claims abstract description 11
- 239000012670 alkaline solution Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 229920002972 Acrylic fiber Polymers 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 4
- 230000007423 decrease Effects 0.000 claims description 4
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 230000003019 stabilising effect Effects 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 229920001567 vinyl ester resin Polymers 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims 2
- 150000001447 alkali salts Chemical class 0.000 claims 1
- -1 alkoxyalkyl acrylate Chemical compound 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 0 *OCOC(=O)C=C.C.C Chemical compound *OCOC(=O)C=C.C.C 0.000 description 4
- 125000002560 nitrile group Chemical group 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000009987 spinning Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N C=CC(C)=O Chemical compound C=CC(C)=O FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 229920000965 Duroplast Polymers 0.000 description 1
- 239000004638 Duroplast Substances 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000000578 dry spinning Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 230000008863 intramolecular interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/40—Modacrylic fibres, i.e. containing 35 to 85% acrylonitrile
-
- 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
- D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
- D01F9/1277—Other organic compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
-
- 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
- D01D10/02—Heat treatment
-
- 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
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
- D01F11/06—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent
-
- 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
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- D—TEXTILES; PAPER
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
- D06M13/232—Organic carbonates
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
- D06M13/268—Sulfones
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- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/35—Heterocyclic compounds
- D06M13/352—Heterocyclic compounds having five-membered heterocyclic rings
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- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/402—Amides imides, sulfamic acids
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
- D06M2101/28—Acrylonitrile; Methacrylonitrile
Definitions
- the invention relates to a method for the production of thermally stabilised melt spun fibres, in which polyacrylonitrile (PAN) fibres or PAN fibre precursors produced by melt spinning are treated in an aqueous alkaline solution which comprises in addition a solvent for PAN.
- PAN polyacrylonitrile
- the invention relates to fibres which are producible according to this method.
- Carbon fibres which are gaining ever greater importance in the field of technical fibres are produced, according to the state of the art, by thermal conversion of separately produced precursor fibres.
- Materials for the precursor fibres are above all PAN (co)polymers (acrylic precursors) and also pitch.
- Acrylic precursor fibres have been produced commercially to date exclusively via wet- or dry-spinning methods. For this purpose, a solution of polymers with concentrations ⁇ 20% are spun either in a coagulation bath or a hot steam atmosphere, the solvent diffusing out of the fibre. In this way, qualitatively high-value precursors are produced, however, the costs of the methods are comparatively high. This results, on the one hand, from the required solvents and handling thereof, on the other hand, from the relatively low throughput in solution spinning methods.
- the melting point of PAN at 320° C. is above the decomposition temperature of the polymer. This means that melt spinning of pure PAN is not possible, the polymer does not behave as a thermoplast but rather as a duroplast. At the same time, the possibility for the production of precursor fibres by means of melt spinning would however imply a significant cost saving in the precursor production since the throughput during melt spinning is substantially higher and in addition no solvents incur which cause costs for purchasing and recycling/disposal.
- melt spun PAN fibres against the actual oxidative stabilisation/carbonisation is one of the crucial problems which needs to be solved in the context of melt spinnable PAN precursors.
- the stabilisation is normally implemented in the temperature range between 200° C. and 300° C. under air atmosphere. It is obvious that the above-described melt spun PAN precursor fibres soften/melt under these conditions and hence would make a stabilisation with simultaneous maintenance of the fibre properties impossible. This means that the fibre has to be put firstly into an unmeltable state after spinning.
- a method for the production of thermally stabilised, melt spun acrylic fibres in which a fibre produced by melt spinning or a fibre precursor is pre-stabilised with a mixture comprising a solvent for PAN, in particular selected from the group consisting of dimethylsulphoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylene carbonate, propylene carbonate, aqueous sodium rhodanide solutions and mixtures hereof and an aqueous alkaline solution.
- a solvent for PAN in particular selected from the group consisting of dimethylsulphoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylene carbonate, propylene carbonate, aqueous sodium rhodanide solutions and mixtures hereof and an aqueous alkaline solution.
- the mixture comprises from 0.1 to 60% by volume of the PAN solvent and from 40 to 99.9% by volume of the aqueous alkaline solution.
- the pre-stabilisation is preferably implemented in a modification bath comprising the mixture at a temperature of 20 to 80° C., preferably of 40 to 65° C., within a dwell time of 5 s to 2 min, preferably of 10 s to 60 s.
- the aqueous alkaline solution comprises from 3 to 15 mol/l of at least one alkali- or alkaline earth hydroxide, preferably an alkali hydroxide, particularly preferably potassium hydroxide or sodium hydroxide.
- the ratios of PAN solvent and aqueous alkaline solution in the mixture are preferably adjusted as a function of the titre of the corresponding fibre.
- the fibres are preferably carbon fibres, the fibre precursors consisting of a copolymer of polyacrylonitrile or essentially comprising this.
- the copolymer preferably has a melt viscosity which remains constant or decreases with increasing temperature up to 240° C., in particular up to 260° C.
- the copolymerisation can thereby be effected preferably by precipitation polymerisation, emulsion polymerisation and/or polymerisation in a solvent.
- the solvent is preferably selected from the group consisting of dimethylsulphoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylene carbonate, propylene carbonate, aqueous sodium rhodanide solution and mixtures hereof.
- fibres which are producible according to the previously described method are likewise provided. This hereby concerns in particular carbon fibres.
- FIG. 1 shows, with reference to a schematic diagram, the temperature dependency of the storage modulus of standard non-meltable acrylic fibres and meltable acrylic precursors before the treatment according to the invention.
- FIG. 2 shows, with reference to a diagram, the temperature dependency of the storage modulus of an untreated fibre
- FIG. 3 shows an IR spectrum of an untreated fibre
- FIG. 4 shows, with reference to a diagram, the temperature dependency of the storage modulus of a fibre treated according to the invention
- FIG. 6 shows a photo of an untreated (at the top) and a multifilament (at the bottom), treated according to the invention, made of 42 fibres which were both subjected to an oxidative stabilisation at 230° C. Melting of the untreated filament can be clearly recognised, the treated filament melts and does not bond.
- Approx. 500 mg fibre short section is placed between aluminium foil and incubated in the drying cabinet with loading by a weight of approx. 100 g at various temperatures respectively for 10 min. It is recorded from what temperature the result is bonding of the aluminium foil by the fibres. This temperature corresponds to a softening- or melting temperature.
- the thermal behaviour of the fibres is observed under the melting table microscope. It is recorded whether melting of the fibres can be detected.
- the storage modulus of a fibre of 10 cm length is determined as a function of the temperature.
- FIGS. 2 and 4 describe the basic course of the curves.
- Non-modified PAN (not meltable) shows a loss of the storage modulus with the temperature up to approx. 140° C., thereafter a constant residual storage modulus is maintained which ensures the mechanical stability of the fibre.
- Meltable PAN which was not treated, shows a loss of the storage modulus up to approx. 80° C., at this temperature the modulus has decreased to 0. Above 80° C., the fibre is so soft that it is no longer mechanically loadable and tears (see FIG. 1 ).
- a melt spun fibre treated according to the invention made of a copolymer with 10% methoxyethylacrylate and a molar mass of 15,000 g/mol, individual fibre titre 0.82 tex, was examined.
- the fibre described in the comparative example was, for this purpose, placed in a modification bath of the composition 50% DMSO and 50% 4.5 M aqueous KOH for 60 s at 70° C. The fibre discolours to reddish brown. Subsequently, it is washed neutrally and dried in a vacuum at 50° C.
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Abstract
Description
- The invention relates to a method for the production of thermally stabilised melt spun fibres, in which polyacrylonitrile (PAN) fibres or PAN fibre precursors produced by melt spinning are treated in an aqueous alkaline solution which comprises in addition a solvent for PAN. Likewise, the invention relates to fibres which are producible according to this method.
- Carbon fibres which are gaining ever greater importance in the field of technical fibres are produced, according to the state of the art, by thermal conversion of separately produced precursor fibres. Materials for the precursor fibres are above all PAN (co)polymers (acrylic precursors) and also pitch. Acrylic precursor fibres have been produced commercially to date exclusively via wet- or dry-spinning methods. For this purpose, a solution of polymers with concentrations ≦20% are spun either in a coagulation bath or a hot steam atmosphere, the solvent diffusing out of the fibre. In this way, qualitatively high-value precursors are produced, however, the costs of the methods are comparatively high. This results, on the one hand, from the required solvents and handling thereof, on the other hand, from the relatively low throughput in solution spinning methods.
- Because of the strong inter- and intramolecular interactions of the nitrile groups, the melting point of PAN at 320° C. is above the decomposition temperature of the polymer. This means that melt spinning of pure PAN is not possible, the polymer does not behave as a thermoplast but rather as a duroplast. At the same time, the possibility for the production of precursor fibres by means of melt spinning would however imply a significant cost saving in the precursor production since the throughput during melt spinning is substantially higher and in addition no solvents incur which cause costs for purchasing and recycling/disposal.
- Efforts have been made for several decades to make PAN amenable to processing by means of melt spinning. In principle, approaches by way of an external softening (mixing of the polymer with additives) and internal softening (copolymerisation) must thereby be differentiated. In both cases, the interaction of the nitrile groups is thereby disturbed so that the melting is effected below the decomposition temperature of the polymer.
- An essential prerequisite for the further processing to form carbon fibres is the possibility of stabilising the fibres subsequently oxidatively. This process is implemented at temperatures above 200° C. and results in the formation of cyclic structures which firstly enable the subsequent carbonisation. Of course, this can only succeed when the fibres do not melt at the stabilisation temperatures—which represents an additional problem to be solved since the stabilisation temperatures are in general higher than the processing temperatures during melt spinning.
- As already mentioned, the pre-stabilisation of melt spun PAN fibres against the actual oxidative stabilisation/carbonisation is one of the crucial problems which needs to be solved in the context of melt spinnable PAN precursors. The stabilisation is normally implemented in the temperature range between 200° C. and 300° C. under air atmosphere. It is obvious that the above-described melt spun PAN precursor fibres soften/melt under these conditions and hence would make a stabilisation with simultaneous maintenance of the fibre properties impossible. This means that the fibre has to be put firstly into an unmeltable state after spinning.
- The only path shown to be as practicable to date for this purpose in the literature is the crosslinking of the finished fibre by UV- or electron radiation (Mukundan et al.; Polymer 2006 47: 4163-4171), the former demanding the incorporation of an additional photosensitive comonomer, the second sensitisation of the polymer to the electron beams for example by an introduced crosslinker (triallylisocyanurate or comparable). The disadvantages of the methods are obvious; apart from the commercial availability of UV-active monomers which in practice does not exist, further imperfections are introduced into the fibre which have a negative effect on the properties of the resulting carbon fibre.
- Starting herefrom, it was the object of the present invention to optimise the thermal stability of melt spun acrylic fibres such that the fibres, after spinning, are present in an unmeltable state for further processing.
- This object is achieved by the method having the features of
claim 1 and also by the melt spun fibres having the features of claim 14. The further dependent claims reveal advantageous developments. - According to the invention, a method for the production of thermally stabilised, melt spun acrylic fibres is provided, in which a fibre produced by melt spinning or a fibre precursor is pre-stabilised with a mixture comprising a solvent for PAN, in particular selected from the group consisting of dimethylsulphoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylene carbonate, propylene carbonate, aqueous sodium rhodanide solutions and mixtures hereof and an aqueous alkaline solution.
- Surprisingly, it was established that a fibre produced by melt spinning can be converted into an unmeltable state by treatment with such a solution.
- It is thereby preferred that the mixture comprises from 0.1 to 60% by volume of the PAN solvent and from 40 to 99.9% by volume of the aqueous alkaline solution.
- The pre-stabilisation is preferably implemented in a modification bath comprising the mixture at a temperature of 20 to 80° C., preferably of 40 to 65° C., within a dwell time of 5 s to 2 min, preferably of 10 s to 60 s.
- Preferably, the aqueous alkaline solution comprises from 3 to 15 mol/l of at least one alkali- or alkaline earth hydroxide, preferably an alkali hydroxide, particularly preferably potassium hydroxide or sodium hydroxide.
- The ratios of PAN solvent and aqueous alkaline solution in the mixture are preferably adjusted as a function of the titre of the corresponding fibre.
- Preferably an oxidative stabilisation follows the pre-stabilisation. The oxidative stabilisation is thereby implemented preferably at temperatures of 200 to 350° C. in an oxygen- or air-containing atmosphere.
- According to the invention, the fibres are preferably carbon fibres, the fibre precursors consisting of a copolymer of polyacrylonitrile or essentially comprising this.
- It is thereby preferred that the fibre precursor is producible by a method in which
-
- i. a copolymerisation of 95 to 80% by mol of acrylonitrile with at least one comonomer selected from
- a) 5 to 20% by mol of at least one alkoxyalkylacrylate of general formula I
- i. a copolymerisation of 95 to 80% by mol of acrylonitrile with at least one comonomer selected from
-
-
- with
- R=CnH2n+1 and n=1-8 and m=1-8, in particular n=1-4 and m=1-4
- b) 0 to 10% by mol of at least one alkylacrylate of general formula II
-
-
-
- with
- R=CnH2n+1 and n=1-18,
- c) 0 to 10% by mol of at least one vinyl ester of general formula III
-
-
-
- with
- R=CnH2n1 and n=1-18,
- is implemented in the presence of at least one initiator and
- ii. the copolymer is spun with an extruder with at least one nozzle, suitable for spinning, at the extruder outlet to form mono- or multifilaments.
-
- The copolymer preferably has a melt viscosity which remains constant or decreases with increasing temperature up to 240° C., in particular up to 260° C.
- It is further preferred that 8 to 12% by mol of the comonomer in a) and/or 1 to 5% by mol of the comonomer in b) and/or 1 to 5% by mol of the comonomer in c) are present.
- The copolymerisation can thereby be effected preferably by precipitation polymerisation, emulsion polymerisation and/or polymerisation in a solvent.
- The solvent is preferably selected from the group consisting of dimethylsulphoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylene carbonate, propylene carbonate, aqueous sodium rhodanide solution and mixtures hereof.
- According to the invention, fibres which are producible according to the previously described method are likewise provided. This hereby concerns in particular carbon fibres.
- The subject according to the invention is intended to be explained in more detail with reference to the subsequent examples and Figures, without wishing to restrict said subject to the specific embodiments shown here.
-
FIG. 1 shows, with reference to a schematic diagram, the temperature dependency of the storage modulus of standard non-meltable acrylic fibres and meltable acrylic precursors before the treatment according to the invention. -
FIG. 2 shows, with reference to a diagram, the temperature dependency of the storage modulus of an untreated fibre -
FIG. 3 shows an IR spectrum of an untreated fibre -
FIG. 4 shows, with reference to a diagram, the temperature dependency of the storage modulus of a fibre treated according to the invention -
FIG. 5 shows an IR spectrum of a fibre treated according to the invention -
FIG. 6 shows a photo of an untreated (at the top) and a multifilament (at the bottom), treated according to the invention, made of 42 fibres which were both subjected to an oxidative stabilisation at 230° C. Melting of the untreated filament can be clearly recognised, the treated filament melts and does not bond. - The effect of the treatment is described with the following tests:
- Approx. 500 mg fibre short section is placed between aluminium foil and incubated in the drying cabinet with loading by a weight of approx. 100 g at various temperatures respectively for 10 min. It is recorded from what temperature the result is bonding of the aluminium foil by the fibres. This temperature corresponds to a softening- or melting temperature.
- The thermal behaviour of the fibres is observed under the melting table microscope. It is recorded whether melting of the fibres can be detected.
- Approx. 500 mg fibre short section is stored in 10 ml MDSO and it is noted after what time the fibres dissolve. Crosslinkings are detected with this test method.
- The storage modulus of a fibre of 10 cm length is determined as a function of the temperature.
FIGS. 2 and 4 describe the basic course of the curves. Non-modified PAN (not meltable) shows a loss of the storage modulus with the temperature up to approx. 140° C., thereafter a constant residual storage modulus is maintained which ensures the mechanical stability of the fibre. Meltable PAN, which was not treated, shows a loss of the storage modulus up to approx. 80° C., at this temperature the modulus has decreased to 0. Above 80° C., the fibre is so soft that it is no longer mechanically loadable and tears (seeFIG. 1 ). - An untreated melt spun fibre made of a PAN copolymer with 10% methoxyethylacrylate and a molar mass of 15,000 g/mol, individual fibre titre 0.82 tex, was examined.
- It was thereby shown during the bonding test that the fibres bond from 80° C. On the melting table microscope, complete melting at 185° C. could be observed. During the solubility test, the fibres were completely dissolved within 2 min. During the DMA, the modulus decreases, up to 100° C., to 0 (see
FIG. 2 ). - From the IR spectrum (
FIG. 3 ), an ester grouping at 1,730 cm−1 can be clearly detected, just as a nitrile group at 2,240 cm−1. Further characteristic bands are not present. - A melt spun fibre treated according to the invention, made of a copolymer with 10% methoxyethylacrylate and a molar mass of 15,000 g/mol, individual fibre titre 0.82 tex, was examined. The fibre described in the comparative example was, for this purpose, placed in a modification bath of the composition 50% DMSO and 50% 4.5 M aqueous KOH for 60 s at 70° C. The fibre discolours to reddish brown. Subsequently, it is washed neutrally and dried in a vacuum at 50° C.
- During the bonding test, it was shown that the fibres do not bond up to a temperature of 230° C. On the melting table microscope, no melting of the fibres could be observed up to 250° C., merely the colour of the fibres changed from reddish via reddish brown to black. The result of the solubility test is that the fibres are maintained entirely after 24 h. During the DMA, the modulus decreases to 250° C., but still has a value greater than 0 even at this temperature (see
FIG. 4 ). - From the IR spectrum (
FIG. 5 ), it results, in comparison to the IR spectrum inFIG. 3 , that the intensity of the band of the ester grouping at 1,730 cm−1 has decreased significantly, whilst the intensity of the band of the nitrile group is constant at 2,240 cm−1. Furthermore, a band which can be ascribed to the formation of the PAN conductor structure occurs at 1,570 cm−1.
Claims (16)
Applications Claiming Priority (3)
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DE102014219708.2A DE102014219708A1 (en) | 2014-09-29 | 2014-09-29 | Process for the thermal stabilization of fibers and fibers stabilized in this way |
DE102014219708.2 | 2014-09-29 | ||
PCT/EP2015/070771 WO2016050479A1 (en) | 2014-09-29 | 2015-09-10 | Method for the thermal stabilisation of fibres and said type of stabilised fibres |
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US20170298539A1 true US20170298539A1 (en) | 2017-10-19 |
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ID=54106355
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US15/513,454 Abandoned US20170298539A1 (en) | 2014-09-29 | 2015-09-10 | Method for the thermal stabilisation of fibres and said type of stabilised fibres |
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---|---|
US (1) | US20170298539A1 (en) |
EP (1) | EP3201375B1 (en) |
JP (1) | JP2017529464A (en) |
KR (1) | KR20170065524A (en) |
CN (1) | CN107002297A (en) |
DE (1) | DE102014219708A1 (en) |
WO (1) | WO2016050479A1 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3872103A1 (en) | 2020-02-25 | 2021-09-01 | DWI - Leibniz-Institut für Interaktive Materialien e.V. | Melt-processable acrylonitrile-based copolymers and their acidic prestabilization for conversion into carbon fibers and workpieces |
US11180869B2 (en) | 2016-03-22 | 2021-11-23 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Melt spinnable copolymers from polyacrylonitrile, method for producing fibers or fiber precursors by means of melt spinning, and fibers produced accordingly |
US11203656B2 (en) | 2015-11-16 | 2021-12-21 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Method for producing thermally stable melt-spinnable pan copolymers, pan copolymers, molded bodies made thereof, and a method for producing said molded bodies |
US11242623B2 (en) | 2017-01-10 | 2022-02-08 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Continuous method for producing a thermally stabilized multifilament thread, multifilament thread, and fiber |
US11649567B2 (en) | 2016-05-11 | 2023-05-16 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Method for producing a multifilament yarn |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106592020B (en) * | 2015-10-19 | 2019-02-19 | 中国石油化工股份有限公司 | The preparation method of polyacrylonitrile-radical thermostabilization fiber |
DE102016011991B4 (en) * | 2016-10-10 | 2020-02-20 | Universität Augsburg | Method and device for producing a carbon fiber and intermediate product for producing a carbon fiber and device for producing an intermediate fiber |
JP7311649B2 (en) * | 2017-01-10 | 2023-07-19 | フラウンホーファー-ゲゼルシャフト ツゥア フェアデルング デア アンゲヴァンドテン フォァシュング エー.ファウ. | Continuous method for producing heat stabilized multifilament yarn, multifilament yarn and fiber |
DE102017127629B4 (en) | 2017-11-22 | 2020-07-09 | Deutsche Institute Für Textil- Und Faserforschung Denkendorf | Precursor molded articles, a process for their production and their use for the production of carbon molded articles |
KR102257840B1 (en) * | 2018-10-10 | 2021-05-28 | 대한민국 | Frame Structure of Flame Retardant Tent |
CN113311112B (en) * | 2021-05-22 | 2024-03-29 | 威海市计量所 | Carbon fiber precursor coagulation bath production site simulation device, platform and method device |
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JPS5266800A (en) * | 1975-11-28 | 1977-06-02 | Monsanto Co | Production of flame proofing acrylic fiber |
JPS5658063A (en) * | 1979-10-09 | 1981-05-20 | Japan Exlan Co Ltd | Production of water swellable fiber |
JPS59163413A (en) * | 1983-03-04 | 1984-09-14 | Asahi Chem Ind Co Ltd | Melt spinning of acrylic polymer composition |
JPS62149918A (en) * | 1985-12-25 | 1987-07-03 | Mitsubishi Rayon Co Ltd | Production of heat-resistant acrylonitrile yarn |
JPS62268813A (en) * | 1986-05-15 | 1987-11-21 | Mitsubishi Rayon Co Ltd | Production of acrylonitrile fiber |
US5168004A (en) * | 1988-08-25 | 1992-12-01 | Basf Aktiengesellschaft | Melt-spun acrylic fibers possessing a highly uniform internal structure which are particularly suited for thermal conversion to quality carbon fibers |
US4935180A (en) * | 1988-08-25 | 1990-06-19 | Basf Aktiengesellschaft | Formation of melt-spun acrylic fibers possessing a highly uniform internal structure which are particularly suited for thermal conversion to quality carbon fibers |
US4933128A (en) * | 1989-07-06 | 1990-06-12 | Basf Aktiengesellschaft | Formation of melt-spun acrylic fibers which are well suited for thermal conversion to high strength carbon fibers |
JP2001164431A (en) * | 1999-12-10 | 2001-06-19 | Toray Ind Inc | Flame resistant fiber and method for producing carbon fiber |
EP2415913B1 (en) * | 2009-03-31 | 2017-09-06 | Donghua University | Processes for producing carbon fiber precursor |
US8906278B2 (en) * | 2009-03-31 | 2014-12-09 | Donghua University | Process of melt-spinning polyacrylonitrile fiber |
DE102009047514A1 (en) * | 2009-12-04 | 2011-07-07 | Sgl Carbon Se, 65203 | Fibers for the production of composite materials |
-
2014
- 2014-09-29 DE DE102014219708.2A patent/DE102014219708A1/en not_active Ceased
-
2015
- 2015-09-10 EP EP15763299.3A patent/EP3201375B1/en not_active Not-in-force
- 2015-09-10 CN CN201580052684.2A patent/CN107002297A/en active Pending
- 2015-09-10 WO PCT/EP2015/070771 patent/WO2016050479A1/en active Application Filing
- 2015-09-10 KR KR1020177009018A patent/KR20170065524A/en unknown
- 2015-09-10 US US15/513,454 patent/US20170298539A1/en not_active Abandoned
- 2015-09-10 JP JP2017516867A patent/JP2017529464A/en not_active Ceased
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DE2603029A1 (en) * | 1976-01-28 | 1977-08-04 | Hoechst Ag | Cyclising of polyacrylonitrile fibres by alkaline treatment - carried out continuously after spinning, etc. |
US20070196648A1 (en) * | 2004-03-11 | 2007-08-23 | Makoto Endo | Carbon fiber, process for production thereof, prepregs, and golf club shafts |
US20130133819A1 (en) * | 2011-11-30 | 2013-05-30 | Hyundai Motor Company | Preparation method for hollow carbon fiber using supercritical fluid |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11203656B2 (en) | 2015-11-16 | 2021-12-21 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Method for producing thermally stable melt-spinnable pan copolymers, pan copolymers, molded bodies made thereof, and a method for producing said molded bodies |
US11180869B2 (en) | 2016-03-22 | 2021-11-23 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Melt spinnable copolymers from polyacrylonitrile, method for producing fibers or fiber precursors by means of melt spinning, and fibers produced accordingly |
US11649567B2 (en) | 2016-05-11 | 2023-05-16 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Method for producing a multifilament yarn |
US11242623B2 (en) | 2017-01-10 | 2022-02-08 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Continuous method for producing a thermally stabilized multifilament thread, multifilament thread, and fiber |
EP3872103A1 (en) | 2020-02-25 | 2021-09-01 | DWI - Leibniz-Institut für Interaktive Materialien e.V. | Melt-processable acrylonitrile-based copolymers and their acidic prestabilization for conversion into carbon fibers and workpieces |
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EP3201375A1 (en) | 2017-08-09 |
DE102014219708A1 (en) | 2016-03-31 |
WO2016050479A1 (en) | 2016-04-07 |
KR20170065524A (en) | 2017-06-13 |
CN107002297A (en) | 2017-08-01 |
EP3201375B1 (en) | 2018-11-07 |
JP2017529464A (en) | 2017-10-05 |
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