EP3433292A1 - Melt spinnable copolymers from polyacrylonitrile, method for producing fibers or fiber precursors by means of melt spinning, and fibers produced accordingly - Google Patents
Melt spinnable copolymers from polyacrylonitrile, method for producing fibers or fiber precursors by means of melt spinning, and fibers produced accordinglyInfo
- Publication number
- EP3433292A1 EP3433292A1 EP16714305.6A EP16714305A EP3433292A1 EP 3433292 A1 EP3433292 A1 EP 3433292A1 EP 16714305 A EP16714305 A EP 16714305A EP 3433292 A1 EP3433292 A1 EP 3433292A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- mol
- copolymer
- melt
- fibers
- copolymer according
- 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.)
- Withdrawn
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 41
- 229920002239 polyacrylonitrile Polymers 0.000 title claims abstract description 27
- 238000002074 melt spinning Methods 0.000 title claims abstract description 22
- 239000002243 precursor Substances 0.000 title claims abstract description 16
- 229920001577 copolymer Polymers 0.000 title claims description 41
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 239000004014 plasticizer Substances 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 11
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 9
- -1 alkoxyalkyl acrylate Chemical compound 0.000 claims description 9
- 239000004917 carbon fiber Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000007334 copolymerization reaction Methods 0.000 claims description 8
- 238000009987 spinning Methods 0.000 claims description 8
- 230000006641 stabilisation Effects 0.000 claims description 7
- 238000011105 stabilization Methods 0.000 claims description 7
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 6
- 229920001567 vinyl ester resin Polymers 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 5
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 claims description 5
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 4
- 150000002334 glycols Chemical class 0.000 claims description 4
- 239000002608 ionic liquid Substances 0.000 claims description 4
- 125000004971 nitroalkyl group Chemical group 0.000 claims description 4
- 150000002978 peroxides Chemical class 0.000 claims description 4
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 2
- 230000003247 decreasing effect Effects 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 150000002432 hydroperoxides Chemical class 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 125000005342 perphosphate group Chemical group 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 238000012673 precipitation polymerization Methods 0.000 claims description 2
- 239000012966 redox initiator Substances 0.000 claims description 2
- 239000012736 aqueous medium Substances 0.000 claims 2
- 230000000630 rising effect Effects 0.000 claims 1
- 239000012670 alkaline solution Substances 0.000 abstract description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 13
- 239000000243 solution Substances 0.000 description 7
- 229920001169 thermoplastic Polymers 0.000 description 7
- 239000004416 thermosoftening plastic Substances 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 125000002560 nitrile group Chemical group 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 150000003926 acrylamides Chemical class 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000007380 fibre production Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000002166 wet spinning Methods 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003118 aryl group Chemical group 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
- 239000003054 catalyst Substances 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
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 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
- 239000004815 dispersion polymer Substances 0.000 description 1
- 238000000578 dry spinning Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 229920003247 engineering thermoplastic Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical class NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 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
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical class C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 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
- 201000006292 polyarteritis nodosa Diseases 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
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- 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
- 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
-
- 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
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/16—Monomers containing no hetero atoms other than the ether oxygen
- C08F216/18—Acyclic compounds
-
- 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
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
-
- 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
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
-
- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- 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
-
- 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
Definitions
- the invention relates to a process for producing thermally stabilized melt-spun fibers in which melt-spun polyacrylonitrile (PAN) fibers or PAN fiber precursors are treated in an aqueous alkaline solution which additionally contains a solvent for PAN.
- PAN polyacrylonitrile
- the invention relates to fibers that can be produced according to this method.
- Carbon fibers are produced according to the prior art by thermal conversion of separately prepared precursor fibers.
- Materials for the precursor fibers are mainly PAN (co) polymers (acrylic precursor) and pitch.
- Acrylic Precursorfasern be commercially produced so far only by wet or dry spinning.
- a solution of the polymers with concentrations ⁇ 20% either in a coagulation bath or spun a hot vapor atmosphere with the solvent diffusing out of the fiber.
- high-quality precursors are produced, but the costs of the methods are comparatively high. This results on the one hand from the required solvents and their handling, on the other hand from the relatively low throughput of solution spinning processes.
- the melting point of PAN at 320 ° C is above the decomposition temperature of the polymer. This means that a melt spinning of pure PAN is not possible, the polymer behaves not like a thermoplastic but as a thermoset. At the same time, however, the possibility of producing precursor fibers by means of melt spinning would mean a significant cost savings in the production of precursors, since the throughput in melt spinning is considerably higher and, in addition, no solvents are incurred, which cause costs for procurement and recycling / disposal.
- the polymers - including homopolymers of the PAN - could be processed to monofilaments at temperatures of 250 ° C to 295 ° C. GB 1,294,044
- EP 0 030 666 describes thermoplastic acrylonitrile copolymers with up to 96% acrylonitrile content for hoses and films prepared by grafting acrylonitrile onto a
- thermoplastic acrylonitrile copolymers consisting of 50-95% of acrylonitrile and 5-50% of a comonomer, wherein first of all all conceivable comonomer classes (acrylates, methacrylates, acrylamides, methacrylamides, acrylamide derivatives, methacrylamide derivatives, nyl esters, vinyl ethers, vinylamides, vinyl ketones, styrene, halogen-containing monomers, ionic monomers, acid group-containing monomers,
- the examples give methylstyrene, styrene, vinyl acetate, methyl acrylate and methyl methacrylate with at least 15wt% share (corresponds to about 10 mol% for methyl acrylate) on the copolymer.
- the copolymers could be extruded at 200 ° C.
- US Pat. No. 6,114,034 describes the preparation of fibers from precisely these copolymers, with only methyl acrylate and vinyl acetate being used as comonomers in the exemplary embodiments, in a proportion of 15-25% by weight.
- Methyl acrylate and a molecular weight of 68,000 g / mol still an increase in the complex viscosity by 10%. This is also confirmed by the scientific literature (Bhanu et al., Polymer 43 (2002) 4841-4850).
- the polymer still contains the outer plasticizers, so that a lower quality precursor fiber and a reduction in carbon yield in the carbonization are inevitable.
- the oxidative stabilization of the fibers is for low-boiling plasticizers such as water and / or the o.
- said organic solvents thermoplastic fibers made no challenge; after evaporation of the outer plasticizer, the fiber is again infusible and can be stabilized analogous to solution-spun PAN fibers.
- the thermal stability of the melt-spinnable copolymers is the decisive criterion for a technically feasible melt spinning process. Any thermal instability prevents a long-term stable spinning process. It leads to cracks in hotspots in the spinning extruder, the spinning pump and the spinneret and defects in the spun fiber. This problem arises with all the solutions of the inner and outer plasticizing described in the prior art. Based on this, it was an object of the present invention to provide precursors based on polyacrylonitrile, which show an improved suitability for melt spinning processes.
- the copolymer preferably with the addition of at least one outer plasticizer, in the temperature range of 160 to 220 ° Cverspinnbar.
- the copolymer according to the invention preferably has, with the addition of at least one outer plasticizer, a constant or decreasing melt viscosity with increasing temperature up to 240 ° C., in particular up to 260 ° C. This proves that the copolymer of the invention has a particularly high stability of the melt viscosity.
- the copolymerization is carried out by a precipitation polymerization, an emulsion polymerization and / or a polymerization in a solvent.
- the solvent is preferably selected from the group consisting of dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylene carbonate, propylene carbonate, aqueous sodium thiocyanate solution and mixtures thereof.
- the proportion of the at least one alkoxyalkyl acrylate is preferably 3.0 to 4.9 mol%, particularly preferably 3.5 to 4.8 mol%.
- Alkyl acrylate is present.
- the proportion of the at least one alkyl acrylate may preferably be in the range from 1 to 5 mol%.
- a further preferred embodiment provides that a mixture of at least one alkoxyalkyl acrylate and at least one vinyl ester is present.
- the proportion of the at least one vinyl ester is preferably in the range from 1 to 5 mol%. It is further preferred that the copolymer has a weight average molar mass (Mw) in the range of 15,000 to 80,000 g / mol.
- the comonomers used are alkoxyalkyl acrylates in combination with alkyl acrylates and vinyl esters.
- a method for producing fibers or fiber precursors by melt spinning, in which i. a copolymerization of 99.9 to 80 mol% of acrylonitrile with at least one comonomer selected from a) from 0.1 to less than 5 mol%, in particular from 0.1 to 4.9 mol%, of at least one alkoxyalkyl acrylate of the general formula I,
- the copolymer in the presence of at least one initiator, ii. the copolymer is spun into mono- or multi-filaments with a melt spinning unit containing an extruder, a melt pump and at least one nozzle suitable for spinning.
- At least one plasticizer is added, which is in particular selected from the group consisting of water, acetonitrile, nitroalkanes, alkyl alcohols, ionic liquids, glycols, dimethyl sulfoxide, dimethylformamide, dimethylacetamide , N-methylpyrrolidone, ethylene carbonate, propylene carbonate, aqueous sodium thiocyanate solution and mixtures thereof. If a plasticizer is added, the spinneret can be followed by a pressure chamber to prevent explosive evaporation of plasticizers boiling below processing temperatures.
- the following two subsequent steps are preferably carried out: i. a stabilization of the filaments by a temperature treatment at temperatures of 200 to 350 ° C and ii. a carbonization of the filaments at temperatures of 800 to 1200 ° C.
- the stabilization of the filaments is preferably carried out at temperatures of 220 to 320 ° C, more preferably in the range of 250 to 300 ° C.
- the radical polymerization initiator is selected from the group consisting of azo compounds, peroxides, hydroperoxides, alkyl peroxides,
- fibers are also provided, in particular carbon fibers, which can be produced by the method described above.
- a PAN copolymer having the following characteristics was prepared in an emulsion polymerization with a final solids content of 20%:
- composition 4.4 mol% methoxyethyl acrylate, 3.1 mol% methyl acrylate, 0.5 mol% itaconic acid
- the polymer dispersion was precipitated in 0.1% aluminum sulfate solution, the precipitated polymer washed extensively with water and ethanol and dried in vacuo at 50 ° C.
- the relative viscosity of a 1% DMSO solution at 30 ° C is 1.8.
- the polymer powder was mixed in a mixer with acetonitrile and water such that the total mixture contained 14wt% acetonitrile and 14wt% water. Subsequently, the polymer could be melt-spun using a 40-hole die at a die temperature of 190 ° C., the melt spinning unit used being equipped with a pressure chamber downstream of the spinneret in accordance with US 5,168,004.
- the fibers had a single filament denier of 5 dtex, a round cross-section, and a compact, void-free internal structure.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Artificial Filaments (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Inorganic Fibers (AREA)
Abstract
Description
Claims
Applications Claiming Priority (1)
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PCT/EP2016/056194 WO2017162268A1 (en) | 2016-03-22 | 2016-03-22 | Melt spinnable copolymers from polyacrylonitrile, method for producing fibers or fiber precursors by means of melt spinning, and fibers produced accordingly |
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EP3433292A1 true EP3433292A1 (en) | 2019-01-30 |
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EP16714305.6A Withdrawn EP3433292A1 (en) | 2016-03-22 | 2016-03-22 | Melt spinnable copolymers from polyacrylonitrile, method for producing fibers or fiber precursors by means of melt spinning, and fibers produced accordingly |
Country Status (5)
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US (1) | US11180869B2 (en) |
EP (1) | EP3433292A1 (en) |
JP (1) | JP2019513167A (en) |
KR (1) | KR20180125482A (en) |
WO (1) | WO2017162268A1 (en) |
Families Citing this family (8)
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DE102015222585A1 (en) | 2015-11-16 | 2017-05-18 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Process for the preparation of thermally stable melt-spinnable PAN copolymers, PAN copolymers, moldings formed therefrom and process for the preparation of these moldings |
CN109721678B (en) * | 2017-10-27 | 2021-09-07 | 中国石油化工股份有限公司 | Method for preparing polyacrylonitrile resin for carbon fibers by adopting water-phase precipitation continuous polymerization process |
CN109721677A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of preparation method of polyacrylonitrile spinning solution for carbon fiber |
CN108752521A (en) * | 2018-06-22 | 2018-11-06 | 王进军 | The method for preparing polyacrylonitrile-based carbon fibre polymer using mixed solvent |
CN112011855B (en) | 2019-05-31 | 2023-04-07 | 卡邦材料公司 | Method for producing carbon fiber |
KR102115967B1 (en) * | 2019-07-31 | 2020-05-27 | (주)에이치피케이 | The manufacturing method of carbon fiber |
KR102115961B1 (en) * | 2019-05-31 | 2020-05-27 | (주)에이치피케이 | The manufacturing method of carbon fiber |
CN113402658B (en) * | 2021-07-08 | 2022-04-15 | 长春工业大学 | Polyacrylonitrile and preparation method and application thereof |
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DE102014219707A1 (en) | 2014-09-29 | 2016-03-31 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Melt spinnable copolymers of polyacrylonitrile, process for producing fibers or fiber precursors by means of melt spinning and correspondingly produced fibers |
-
2016
- 2016-03-22 EP EP16714305.6A patent/EP3433292A1/en not_active Withdrawn
- 2016-03-22 KR KR1020187027213A patent/KR20180125482A/en not_active Application Discontinuation
- 2016-03-22 WO PCT/EP2016/056194 patent/WO2017162268A1/en active Application Filing
- 2016-03-22 JP JP2018546460A patent/JP2019513167A/en not_active Ceased
- 2016-03-22 US US16/087,015 patent/US11180869B2/en active Active
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JP2019513167A (en) | 2019-05-23 |
US20190100856A1 (en) | 2019-04-04 |
WO2017162268A1 (en) | 2017-09-28 |
KR20180125482A (en) | 2018-11-23 |
US11180869B2 (en) | 2021-11-23 |
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