EP3414374B1 - Procédé de production de fibres de carbone à partir de fibres de cellulose traitées avec des sels d'acide sulfonique - Google Patents

Procédé de production de fibres de carbone à partir de fibres de cellulose traitées avec des sels d'acide sulfonique Download PDF

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EP3414374B1
EP3414374B1 EP17705035.8A EP17705035A EP3414374B1 EP 3414374 B1 EP3414374 B1 EP 3414374B1 EP 17705035 A EP17705035 A EP 17705035A EP 3414374 B1 EP3414374 B1 EP 3414374B1
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Prior art keywords
cellulose
weight
fibers
fiber
cellulose fibers
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EP3414374C0 (fr
EP3414374B8 (fr
EP3414374A1 (fr
Inventor
Falko ABELS
Martin Merger
Tomasz CWIK
Klemens Massonne
Johanna SPÖRL
Frank Hermanutz
Michael R. Buchmeiser
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Technikum Laubholz GmbH TLH
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Technikum Laubholz GmbH TLH
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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/16—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
    • 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
    • D01F11/02—Chemical after-treatment of artificial filaments or the like during manufacture of cellulose, cellulose derivatives, or proteins
    • 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
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/02—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from solutions of cellulose in acids, bases or salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • D06M13/256—Sulfonated compounds esters thereof, e.g. sultones
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic

Definitions

  • the invention relates to a method for producing carbon fibers from cellulose fibers.
  • the cellulose fibers containing a sulfonic acid salt of contain, where R 1 is a hydrocarbon group and K + is a cation, are converted into carbon fibers.
  • Carbon fibers can be produced by pyrolysis of polyacrylonitrile fibers or cellulose fibers.
  • cellulose fibres e.g. cotton
  • synthetically produced cellulose fibres which are obtained by digesting wood. Because of the large and inexpensive raw material base, synthetically produced cellulose fibers are particularly interesting starting materials for the production of carbon fibers.
  • EP-A 1669480 describes the production of carbon fibers from cellulose fibers.
  • the cellulose fibers used are impregnated with a polysiloxane.
  • Viscose fibers are used as cellulose fibers.
  • An additive is added to the cellulose fibers to increase their strength.
  • WO 2015/173243 A1 describes a process for producing carbon fibers from cellulose fibers, in which the cellulose fibers obtained from a spinning bath are not dried before they are subsequently finished with additives.
  • the viscose fibers contain ammonium compounds as an additive to increase strength.
  • Ammonium imidosulfonate thiourea is also used as the ammonium compound.
  • suitable additives are salts or acids, for example inorganic salts, inorganic acids, organic salts or organic acids.
  • Suitable organic acids are, in particular, carboxylic acids, sulfonic acids or phosphonic acids.
  • Suitable organic salts are, in particular, salts of the above organic acids, which can be metal salts, especially alkali metal salts, or salts with organic cations.
  • the carbon yield should be as high as possible, which means that the carbon in the starting fiber should be converted as completely as possible into the carbon fiber. In previously known processes for producing carbon fibers from cellulose fibers, the carbon yield is not yet satisfactory.
  • the object of the present invention was therefore an improved process for producing carbon fibers from cellulose fibers.
  • the method defined at the outset was further developed such that the cellulose fiber contains the salt of sulfonic acid in such an amount that the sulfur content is 0.1 to 3% by weight, based on the total weight of the dried cellulose fiber.
  • the cellulosic fibers which are converted to carbon fibers contain a sulfonic acid salt of formula I above.
  • sulfonic acid salt also includes mixtures of sulfonic acid salts.
  • R 1 preferably represents a hydrocarbon group having 1 to 20 carbon atoms, particularly preferably a hydrocarbon group having 2 to 15 carbon atoms and very particularly preferably a hydrocarbon group having 5 to 15 carbon atoms.
  • R 1 is an aromatic group or contains an aromatic group.
  • R 1 may be an optionally substituted aryl group, eg an optionally substituted phenyl, diphenyl or naphthyl group, or R 1 may be an alkaryl group, e.g. B. an optionally substituted phenyl, diphenyl or naphthyl group bonded to the sulfur atom via an alkylene group.
  • R 1 is a group of formula III or IV wherein R a to R e independently represent an H atom or a C 1 - to C 4 -alkyl group and R x represents a C 1 - to C 4 -alkylene group.
  • At least 3 of the radicals R a to R e are an A atom.
  • R 1 represents a phenyl, tolyl or xylyl group, in particular a tolyl group.
  • the cation in formula I can be any inorganic or organic cation, e.g. a metal cation or a cationic, organic ring system of carbon atoms and optionally heteroatoms such as N, O or S.
  • R 2 to R 5 independently represent an H atom or an organic group having 1 to 20 carbon atoms.
  • R 2 to R 5 independently represent an H atom or an alkyl group having 1 to 4 carbon atoms.
  • at least two of the radicals R 2 to R 5 are an H atom.
  • the cation is very particularly preferably ammonium, ie (NH 4 ) + .
  • the sulfonic acid salt of the formula I preferably has a solubility in water of at least 10 parts by weight, particularly preferably at least 20 parts by weight of sulfonic acid salt, per 100 parts by weight of water under standard conditions (20° C., 1 bar).
  • the sulfonic acid salt is ammonium tosylate.
  • the cellulose fiber contains the sulfonic acid salt in such an amount that the content of sulfur caused by the sulfonic acid salt is 0.1 to 3% by weight, based on the total weight of the dried cellulosic fiber;
  • the sulfur content caused by the sulfonic acid salt is particularly preferably at least 0.2% by weight, in particular at least 0.5% by weight, based on the total weight of the dried cellulose fiber.
  • the sulfur content caused by the sulfonic acid salt is particularly preferably in the range from 0.5 to 2% by weight, based on the total weight of the dried cellulose fiber.
  • Cellulosic fibers are understood here to mean fibers which consist of more than 60% by weight, in particular more than 80% by weight, particularly preferably more than 90% by weight, of cellulose or modified cellulose. In a particular embodiment, the cellulose fibers consist of more than 98% by weight, very particularly preferably 100% by weight, of cellulose or modified cellulose.
  • Modified cellulose is understood as meaning cellulose in which the hydroxyl groups are etherified or esterified.
  • it may be cellulose acetate, cellulose formate, cellulose propionate, cellulose carbamate or cellulose allophanate.
  • the cellulose fibers are preferably fibers which contain more than 60% by weight, in particular more than 80% by weight, particularly preferably more than 90% by weight and in the particularly preferred embodiments more than 98% by weight. , or 100% by weight of cellulose.
  • the cellulose fibers have a water content of more than 20 parts by weight of water, in particular more than 30 parts by weight of water, particularly preferably more than 50 parts by weight of water, very particularly preferably more than 70 parts by weight of water, based on 100 parts by weight of cellulose fibers, have.
  • the water content is not more than 500, in particular not more than 300, parts by weight of water based on 100 parts by weight of cellulose fiber.
  • the cellulose fiber having the above water content can be easily obtained, for example, by immersing a dried cellulose fiber in water. Both natural cellulose fibers and synthetic cellulose fibers are suitable for this purpose.
  • synthetic cellulosic fibers are used.
  • synthetic cellulose fibers are used which have been produced immediately beforehand by a spinning process.
  • the contact with water is preferably carried out in such a way that the cellulose fiber absorbs water in the desired amount specified above.
  • the cellulose fiber can be immersed in water for a sufficient time or passed through a sufficiently long water bath in a continuous process.
  • cellulose fibers In the production of the cellulose fibers, preferably no process measures are taken for drying.
  • the cellulose fiber obtained in the spinning process is washed with water without prior drying and then brought into contact with the solution of the additive, naturally again without prior drying. It is therefore a so-called "never dried” cellulose fiber which has the above water content.
  • the cellulosic fibers preferably the aqueous cellulosic fibers (never dried), are contacted with a solution of the sulfonic acid salt of formula I above.
  • hydrophilic solvent in particular in water or in a hydrophilic organic solvent, for example alcohols or ethers, or mixtures thereof.
  • hydrophilic solvents are water or mixtures of water with other hydrophilic organic solvents which are fully miscible with water, the proportion of water in the solvent mixture in a preferred embodiment being at least 50% by weight in the latter case.
  • the concentration of the sulfonic acid salts in the solution and the contact times of the fiber with the solution are chosen so that the above content of sulfonic acid salt in the dried fiber is obtained.
  • the cellulose fiber can be immersed in the solution for a sufficient time or be guided through a sufficiently long solution bath in the continuous process.
  • the cellulose fiber is continuously passed through the solution of the sulfonic acid salts.
  • the content of sulfonic acid salts in the solution is, for example, 0.05 to 5 moles per liter of solution, preferably 0.1 mole to 2 moles per liter of solution.
  • the contact time of the cellulose fiber with the solution of the sulfonic acid salts is preferably at least 0.5 seconds, more preferably at least 2 and most preferably at least 10 seconds. In general, it is no longer than 100 seconds, preferably no longer than 30 seconds.
  • the cellulose fiber can also be equipped with other additives.
  • the solution of the sulfonic acid salt can contain such further additives; however, the cellulose fiber can also be brought into contact with solutions of other additives in further process steps.
  • Particularly suitable as further additives are compounds which have a solubility in water of at least 10 parts by weight, preferably at least 20 parts by weight, in particular at least 30 parts by weight, per 100 parts by weight of water under normal conditions (20° C., 1 bar).
  • the additives are preferably low molecular weight compounds which have a molar weight of at most 1000 g/mol, particularly preferably at most 500 g/mol, in particular at most 300 g/mol.
  • Salts or acids for example inorganic salts, inorganic acids, organic salts or organic acids, such as carboxylic acids or phosphonic acids, are suitable as further additives.
  • salts which may be mentioned are phosphates, hydrogen phosphates, phosphites, hydrogen phosphites, sulfates or sulfites, or chlorides.
  • the cations of the above can be, for example, metal cations, preferably alkali metal cations such as Na + or K + , or ammonium (NH 4 + ).
  • the cellulose fiber contains predominantly or exclusively sulfonic acid salts of the formula I as an additive.
  • more than 50% by weight, particularly preferably more than 80% by weight, very particularly preferably more than 90% by weight, of the total amount of additives with which the cellulose fibers are finished are sulfonic acid salts of the formula I.
  • the additives with which the carbon fiber is finished are exclusively sulfonic acid salts of the formula I.
  • the production of the cellulose fiber in the spinning process and subsequent further processing by washing the cellulose fiber and bringing the cellulose fiber into contact with the solution of the additives are preferably components of a continuous overall process. After production, the cellulose fibers are generally fed to the individual further processing steps via moving rollers.
  • excess solvent can be removed from the solution of the additives by squeezing and the cellulose fiber with additives can be rolled up.
  • the additized cellulose fiber can be dried, e.g. at temperatures of 50 to 300° C. Such drying is recommended if the additized cellulose fiber is to be stored or transported before it is converted into a carbon fiber.
  • the additized cellulose fiber is converted into a carbon fiber by pyrolysis.
  • the pyrolysis is generally carried out at temperatures from 500 to 1600°C. It can be carried out, for example, under air or under an inert gas, e.g. nitrogen or helium. It is preferably carried out under an inert gas.
  • an inert gas e.g. nitrogen or helium. It is preferably carried out under an inert gas.
  • the cellulose fiber Before pyrolysis, the cellulose fiber can be dried. In the case of cellulosic fibers that have already been dried and stored, drying can be repeated if necessary.
  • a multi-stage process in which the cellulose fibers are dried at temperatures in the range from 50 to 300.degree. C. and then pyrolysis is carried out at temperatures in the range from 500 to 1600.degree. C., preferably 700 to 1500.degree. C., can be considered.
  • the temperature can be increased in stages or continuously.
  • drying in two or more stages can be considered, for example at 50 to 100° C. in a first stage and at 100 to 200° C. in a second stage.
  • the contact time can be, for example, 5 to 300 seconds in each stage and 10 to 500 seconds in total during drying.
  • a possible option is pyrolysis, for example, in which the temperature is continuously increased, e.g. starting at 200° C. and finally reaching 1600 or 1400 or 1200° C.
  • the temperature can be increased at 1 to 20 Kelvin/minute, for example.
  • the cellulose fiber should preferably be exposed to a temperature in the range from 900 to 1600° C. for a period of 10 to 60 minutes.
  • the carbon yield in the pyrolysis is generally 20 to 95% by weight; that is, the carbon fiber contains 20 to 95% by weight of the carbon contained in the cellulose fiber.
  • the carbon yield is in particular 70 to 95, particularly preferably 70 to 90, very particularly preferably 70 to 85% by weight.
  • the carbon fiber obtained has very good mechanical properties, in particular good strength and elasticity.
  • a synthetic, tear-resistant cellulose fiber which is used for the production of car tires, is used as the cellulose fiber in the example and in the comparative examples.
  • Such cellulosic fibers are known as tire cord fibers.
  • the cellulose fiber used was made from cellulose dissolved in an ionic liquid.
  • the cellulose fiber was obtained from the spinning bath by coagulation of the cellulose and has not been dried since its manufacture. It had a water content of more than 70 parts by weight of water to 100 parts by weight of cellulose, hence the name "never-dried tire cord fiber".
  • the cellulose fibers are finished and dried in a continuous process on godets. Godets are rollers that enable the fiber to run continuously along the system. 4 of these godets are used.
  • the fibers are loaded with the additives via an immersion bath between the first and the second godet. Between the third and fourth godet there is a hot air channel in which drying takes place. At the end, a tension-controlled winder winds up the finished and dried fiber material.
  • Example 1 the resulting, dried cellulose fiber was also carbonized in a continuous process; in Comparative Examples 2 and 3, it was carried out batchwise.
  • the never-dried tire cord fiber was wound 2 turns around godet 1 (room temperature, 6.5 m/min) and pulled through a 0.3 molar aqueous solution of ammonium tosylate and 6 turns around godet 2 (room temperature, 6.5 m/min). min) and then wrapped in 7 turns around godet 3 (80° C, 6.5 m/min).
  • the fiber was wound through a heating duct (120°C, length: 1.5 m) onto godet 4 (room temperature, 6.5 m/min) and then onto a bobbin.
  • the sulfur content of the dried fiber was 1% by weight.
  • the cellulose fiber produced in this way was continuously derivatized and stabilized under protective gas.
  • the residence times were 13.8 minutes at 200° C., 27.7 minutes at 210° C. and 13.8 minutes at 240° C.
  • the total residence time during stabilization was correspondingly 55.2 minutes.
  • the yarn tension was 0.34 cN /tex.
  • the stabilized fiber obtained was then continuously carbonized under protective gas. To do this, the fiber was subjected to tensile stress.
  • the yarn tension was 2.6 cN/tex.
  • the residence times were 1.58 minutes at 310 and 510° C., 4.74 minutes at 750° C., 1.58 minutes at 971° C. and 4.74 minutes at 1400° C., corresponding to a total of 12.65 minutes.
  • Comparative Example 1 was carried out exactly as Example 1 except as follows.
  • the never-dried tire cord fiber was not drawn through a 0.3 molar solution of ammonium tosylate, but through a 1 molar solution of ammonium hydrogen phosphate.
  • the phosphorus content of the dried fiber was 1% by weight.
  • the total dwell time during stabilization was accordingly 55.2 minutes.
  • the yarn tension was 0.38 cN/tex.
  • the yarn tension during carbonization was 1.1 cN/tex.
  • the thread tension was increased, the fiber tore.
  • Comparative Example 2 was carried out exactly as Example 1 except as noted below.
  • the never-dried tire cord fiber was not drawn through a 0.3 molar solution of ammonium tosylate but through a 0.3 molar solution of p-toluenesulfonic acid.
  • the sulfur content of the dried fiber was 1% by weight.
  • Comparative Example 3 was carried out like Comparative Example 2, but with the exception that the never-dried tire cord fiber was not treated with any additive, neither with ammonium tosylate nor with toluenesulfonic acid, before it was dried.
  • the never-dried tire cord fiber was dried in 7 wraps around godet 1 (80°C, 6.5 m/min) and through a heating duct (120°C) on godet 2 (room temperature, 6.5 m/min) and then wound on a spool.
  • the textile-mechanical properties of the fiber were determined by a tensile test using the "Favimat” device from theTextechno company.
  • the carbonization yield indicates how much carbon of the cellulose in the cellulose fiber has been converted into carbon of the carbon fiber.
  • the carbon content indicates how much percent by weight the carbon fiber consists of carbon.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)
  • Inorganic Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Claims (12)

  1. Procédé de fabrication de fibres de carbone à partir de fibres de cellulose, caractérisé en ce que des fibres de cellulose qui contiennent un sel d'acide sulfonique de formule I
    Figure imgb0009
     dans laquelle R1 représente un groupe hydrocarboné et K+ un cation, sont transformées en fibres de carbone, la fibre de cellulose contenant le sel de l'acide sulfonique en une telle quantité que la teneur en soufre est de 0,1 à 3 % en poids, par rapport au poids total des fibres de cellulose séchées.
  2. Procédé selon la revendication 1, caractérisé en ce que R1 représente un groupe hydrocarboné ayant de 1 à 20 atomes de C.
  3. Procédé selon l'une des revendications 1 ou 2, caractérisé en ce que R1 est un groupe aromatique ou contient un groupe aromatique.
  4. Procédé selon l'une des revendications 1 à 3, caractérisé en ce que le cation est un cation de formule II
    Figure imgb0010
     dans laquelle R2 à R5 représentent indépendamment les uns des autres un atome de H ou un groupe organique ayant de 1 à 20 atomes de C.
  5. Procédé selon l'une des revendications 1 à 4, caractérisé en ce que le cation est de l'ammonium, c'est-à-dire du (NH4)+.
  6. Procédé selon l'une des revendications 1 à 5, caractérisé en ce que le sel d'acide sulfonique présente une solubilité dans l'eau d'au moins 10 parties en poids pour 100 parties en poids d'eau dans des conditions normales (20°C, 1 bar).
  7. Procédé selon l'une des revendications 1 à 6, caractérisé en ce que le sel d'acide sulfonique est le tosylate d'ammonium.
  8. Procédé selon l'une des revendications 1 à 7, caractérisé en ce que ledit procédé est un procédé selon lequel
    a) des fibres de cellulose sont fabriquées,
    b) les fibres de cellulose sont mises en contact avec le sel d'acide sulfonique de formule I, les fibres de cellulose contenant le sel de l'acide sulfonique en une telle quantité que la teneur en soufre est de 0,1 à 3 % en poids, par rapport au poids total des fibres de cellulose séchées, et ensuite
    c) les fibres de cellulose qui contiennent le sel d'acide sulfonique de formule I sont transformées en fibres de carbone.
  9. Procédé selon la revendication 8, caractérisé en ce que les fibres de cellulose sont obtenues à l'étape de procédé a) par filage des fibres de cellulose à partir d'une solution de filage et lavage consécutif des fibres de cellulose avec de l'eau.
  10. Procédé selon la revendication 8 ou 9, caractérisé en ce que, à l'étape de procédé b), des fibres de cellulose qui ont une teneur en eau supérieure à 20 parties en poids d'eau pour 100 parties en poids de fibres de cellulose sont mises en contact avec une solution du sel de l'acide sulfonique.
  11. Procédé selon la revendication 10, caractérisé en ce que les fibres de cellulose contiennent plus de 50 parties en poids d'eau pour 100 parties en poids de cellulose.
  12. Procédé selon l'une des revendications 8 à 11, caractérisé en ce qu'aucune mesure de procédé pour le séchage des fibres de cellulose ne s'effectue jusqu'à la réalisation de l'étape de procédé b).
EP17705035.8A 2016-02-11 2017-02-01 Procédé de production de fibres de carbone à partir de fibres de cellulose traitées avec des sels d'acide sulfonique Active EP3414374B8 (fr)

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FR3083547B1 (fr) * 2018-07-09 2021-07-30 Inst De Rech Tech Jules Verne Fibre de carbone et procede de fabrication d’une telle fibre de carbone a partir de cellulose
TW202022182A (zh) * 2018-10-10 2020-06-16 德商商先創國際股份有限公司 穩定先質纖維或薄膜以生產碳纖維或薄膜的方法
DE102020113807A1 (de) 2020-05-22 2021-11-25 centrotherm international AG Endlosfasern auf Basis von Cellulose und/oder Cellulosederivaten, Verfahren zu deren Herstellung sowie deren Verwendung
CN115368474B (zh) * 2022-09-06 2023-11-28 绍兴文理学院 一种酒糟基莱赛尔纤维浆粕的制备方法

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US3179605A (en) 1962-10-12 1965-04-20 Haveg Industries Inc Manufacture of carbon cloth
JPS5330810B2 (fr) 1974-05-16 1978-08-29
JPS61113826A (ja) 1984-11-07 1986-05-31 Nitto Boseki Co Ltd 不燃性繊維材料の製造方法
AT413824B (de) * 2001-11-02 2006-06-15 Chemiefaser Lenzing Ag Verfahren zur behandlung von lösungsmittelgesponnenen cellulosischen fasern
EP2984214A1 (fr) 2013-04-12 2016-02-17 The Procter & Gamble Company Structures à fibres de polymères hydroxylés comprenant des sels de sulfonate d'alkyle d'ammonium et procédés de fabrication correspondants
WO2015173243A1 (fr) 2014-05-16 2015-11-19 Basf Se Procédé de production de fibres de carbone à partir de fibres de cellulose

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CA3014258C (fr) 2023-12-19
PL3414374T3 (pl) 2023-09-25
CA3014258A1 (fr) 2017-08-17
ES2954633T3 (es) 2023-11-23
EP3414374C0 (fr) 2023-06-07
EP3414374B8 (fr) 2023-07-19
US10995429B2 (en) 2021-05-04
EP3414374A1 (fr) 2018-12-19
WO2017137285A1 (fr) 2017-08-17
US20190062954A1 (en) 2019-02-28

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