EP3143187B1 - Method for producing carbon fibers from cellulose fibers - Google Patents

Method for producing carbon fibers from cellulose fibers Download PDF

Info

Publication number
EP3143187B1
EP3143187B1 EP15721717.5A EP15721717A EP3143187B1 EP 3143187 B1 EP3143187 B1 EP 3143187B1 EP 15721717 A EP15721717 A EP 15721717A EP 3143187 B1 EP3143187 B1 EP 3143187B1
Authority
EP
European Patent Office
Prior art keywords
cellulose
weight
additives
parts
fibers
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.)
Active
Application number
EP15721717.5A
Other languages
German (de)
French (fr)
Other versions
EP3143187A1 (en
Inventor
Sunghee Son
Klemens Massonne
Frank Hermanutz
Johanna SPOERL
Michael R. Buchmeiser
Ronald BEYER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Deutsche Institute fuer Textil und Faserforschung Stuttgart
Original Assignee
Deutsche Institute fuer Textil und Faserforschung Stuttgart
Deutsche Institute fuer Textil und Faserforschung Denkendorf DITF
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Deutsche Institute fuer Textil und Faserforschung Stuttgart, Deutsche Institute fuer Textil und Faserforschung Denkendorf DITF filed Critical Deutsche Institute fuer Textil und Faserforschung Stuttgart
Publication of EP3143187A1 publication Critical patent/EP3143187A1/en
Application granted granted Critical
Publication of EP3143187B1 publication Critical patent/EP3143187B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/06—Washing or drying
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods

Definitions

  • the invention relates to a method for producing carbon fibers from cellulose fibers, characterized in that cellulose fibers which have a water content of more than 30 parts by weight of water per 100 parts by weight of cellulose fiber and during their production no process measures for drying are brought into contact with a solution of additives and then the additized cellulose fibers, which contain at least 1 part by weight of additives per 100 parts by weight of cellulose, are converted into carbon fibers, the additives being inorganic salts in the form of phosphate, hydrogen phosphate, phosphite, hydrogen phosphite, sulphate or sulphite and their solution being a single additive or may contain a mixture of different additives.
  • Carbon fibers can be produced by pyrolysis of polyacrylonitrile fibers or cellulose fibers. As a renewable raw material, cellulose fibers are becoming increasingly important for the growing carbon fiber market.
  • Fanlong Zeng, Ding Pan and Ning Pan use viscose fibers to produce carbon fibers (Journal of Inorganic and Organometallic Polymers and Materials, Vol.15, No.2 June 2005 ).
  • dried cellulose fibers are treated with solutions of additives and then converted into carbon fibers.
  • Hui Li, Yonggang Yang, Yuefang Wen and Lang Liu impregnate the viscose fibers with an organic silicon compound before drying.
  • the cellulose fiber is usually treated with additives, here with an aqueous solution of ammonium sulfate and ammonium chloride, and finally carbonization.
  • Cellulose which has been dissolved in ionic liquid, is also according to CN 101871140 used to manufacture carbon fibers.
  • EP 1669480 A1 discloses a process for the production of yarns or fiber sheets made of carbon starting from a cellulose material which are impregnated with an aqueous emulsion of an organosilicon additive.
  • the carbon yield should be as high as possible, that is, the carbon of the starting fiber should be converted as completely as possible into the carbon fiber.
  • the carbon yield is not yet satisfactory. Part of the carbon in the cellulose is lost through breakdown into carbon monoxide and carbon dioxide.
  • the mechanical properties of the carbon fibers obtained from cellulose fibers should also be improved.
  • the object of the present invention was therefore an improved process for the production of carbon fibers from cellulose fibers.
  • Cellulose fibers are the starting material for the process.
  • Cellulose 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.
  • 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 to mean cellulose in which hydroxyl groups are etherified or esterified, e.g. B. it can be cellulose acetate, cellulose formate, cellulose propionate, cellulose carbamate or cellulose allophanate.
  • cellulose fibers which consist of cellulose in the minimum amounts specified above.
  • the cellulose fibers which are brought into contact with the solution of an additive have a water content of more than 30 parts by weight of water, in particular more than 50 parts by weight of water, particularly preferably more than 70 parts by weight of water per 100 parts by weight of cellulose fiber.
  • the water content is not higher than 500, in particular not higher than 300 parts by weight of water per 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.
  • Natural cellulose fibers are in particular cellulose fibers obtained from cotton.
  • synthetic cellulose fibers are used
  • synthetic cellulose fibers are used which were produced immediately beforehand by a spinning process.
  • the cellulose fibers obtained are washed with water in order to remove adhering solvent or adhering additives from the spinning bath.
  • the contact with water is 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 it can be passed through a sufficiently long water bath in a continuous process.
  • cellulose fibers In the production of the cellulose fibers, there are preferably no process measures for drying.
  • the cellulose fiber obtained in the spinning process is washed with water without prior drying and then, of course, again without prior drying, brought into contact with the solution of the additive. It is therefore a so-called "never dried" cellulose fiber.
  • the aqueous cellulose fibers are brought into contact with a solution of additives.
  • hydrophilic solvent in particular in water, hydrophilic organic solvents, for example alcohols or ethers, or mixtures thereof.
  • hydrophilic organic solvents for example alcohols or ethers, or mixtures thereof.
  • Particularly preferred hydrophilic solvents are water or mixtures of water with other hydrophilic organic solvents which are infinitely miscible with water, in the latter case the water content in the solvent mixture in a preferred embodiment being at least 50% by weight.
  • the solution contains a single additive or a mixture of different additives.
  • Particularly suitable 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 molecular weight of at most 1000 g / mol, particularly preferably at most 500 g / mol, in particular at most 300 g / mol.
  • the additives are inorganic salts in the form of phosphate, hydrogen phosphate, phosphite, hydrogen phosphite, sulfate or sulfite, it being possible for them to be metal salts, in particular alkali metal salts, or salts with organic cations.
  • the cations of the above inorganic salts can in particular be metal cations, preferably alkali metal cations such as Na + or K + , or ammonium (NH 4 + ). Examples are (NH 4 ) 2 HPO 4 , NH 4 SO 4 or NH 4 Cl.
  • additives are often additives which are also used as flame retardants. It can be assumed that these additives interact with the primary hydroxyl group of the glucose ring (ie the CH 2 OH group) and counteract the breakdown of cellulose into volatile carbon compounds during pyrolysis.
  • the total amount of all additives in the solution is e.g. B. 0.05 to 5 mol / per liter of solution, preferably 0.1 mol to 2 mol / per liter of solution.
  • the contact with the solution of the additives is carried out in such a way that the cellulose fiber absorbs additives in the desired amount.
  • the cellulose fiber can be immersed in the solution for a sufficient time or it can be passed through a sufficiently long solution bath in a continuous process.
  • the cellulose fiber is passed continuously through the solution of the additive.
  • the contact time of the cellulose fiber with the solution of the additives is preferably at least 0.5 seconds, particularly preferably at least 2 and very particularly preferably at least 10 seconds. Generally it is no longer than 100 seconds, preferably no longer than 30 seconds.
  • the additized cellulose fiber obtained contains at least 5 parts by weight of additives per 100 parts by weight of cellulose.
  • the additized cellulose fiber particularly preferably contains at least 1 part by weight, very particularly preferably at least 3 parts by weight of additives per 100 parts by weight of cellulose fiber.
  • the cellulose fiber contains not more than 30 parts by weight of additives, in particular not more than 10 or not more than 5 parts by weight of additives per 100 parts by weight of cellulose fiber.
  • 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 its production, the cellulose fiber is generally fed to the individual further processing steps via movable rollers.
  • excess solvent can be removed from the solution of the additives by squeezing off and the cellulose fiber with the additive can be rolled up.
  • the additized cellulose fiber can be dried, e.g. B. at temperatures of 50 to 300 ° C. Such drying is recommended if the cellulose fiber with the additive 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 of 500 to 1600 ° C. You can, for example, under air or under protective gas, z. B. nitrogen or helium can be carried out. It is preferably carried out under a protective gas.
  • the cellulose fiber can be dried before pyrolysis. In the case of cellulose fibers that have already been dried and stored, drying can be repeated if necessary.
  • the temperature can be increased gradually or continuously.
  • drying in two or more stages is possible, for example at 50 to 100 ° C. in a first stage and at 100 to 200 ° C. in a second stage.
  • the contact time in the individual stages can be, for example, 5 to 300 seconds each and a total of 10 to 500 seconds during the drying.
  • a pyrolysis in which the temperature is continuously increased, e.g. B. starting at 200 ° C and finally reaching 1600 or 1400 or 1200 ° C.
  • the temperature increase can take place, for example, at 1 to 20 Kelvin / minute.
  • 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 pyrolysis is generally 20 to 95% by weight; that is, the carbon fiber contains 20 to 95 percent 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 process according to the invention enables an increased carbon yield.
  • 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.
  • Such cellulose fibers are known as tire cord fibers.
  • the cellulose fiber in the example has not been dried since its manufacture, hence the name "never-dried tire cord fiber".
  • the cellulose fiber in the comparative example was dried; Cellulose fibers usually contain bound residual water, so the water content of dried cellulose fibers can e.g. B. up to 20 wt.%.
  • a never-dried tire cord fiber with a water content of 150% and a single filament titer of 2.2 dtex with 1000 filaments is presented.
  • the finishing and drying of the fibers takes place in a continuous process on godets.
  • Godets are rollers that enable the fibers to run continuously along the system. 4 of these godets are used.
  • the fibers are loaded with the additives via an immersion bath.
  • a tension-controlled winder spools up the finished and dried fiber material.
  • the first godet serves as an unwinding unit for the never dried tire cord fibers stored in water.
  • the fiber is wound around the godet twice, which corresponds to a contact time of 10 seconds.
  • the fiber is then passed through an immersion bath with an ammonium dihydrogen phosphate solution (concentration of ammonium hydrogen phosphate of 0.54 mol / l).
  • the dwell time here is about one second.
  • the material is now wound around the second godet six times. This step is used to drain excess equipment and to bring about a homogeneous distribution of the ammonium hydrogen phosphate in the fiber.
  • the contact time here is 72 seconds. This is followed by drying on the third godet heated to 80 ° C.
  • 10 windings correspond to a contact time of 100 seconds.
  • the fiber is now guided through a hot air duct at 150 ° C.
  • the dwell time is 12 seconds.
  • the dry thread is now wound 4 times around the last godet (contact time 24 seconds) before a tension-controlled winder winds the material with a pretension of 0.1 cN / tex.
  • the cellulose fiber equipped with the additive is then carbonized in two stages under protective gas. In the first stage, it is heated at 2 ° K / min to 260 ° C and, after a dwell time of 10 min, heated at 10k / min to 1400 ° C and then cooled.
  • the carbon yield is 80% by weight, the strength of the fiber 1.4 Gpa and the elongation at break 3.1%.
  • a dried tire cord fiber with a water content of less than 20% by weight and a single filament denier of 2.2 dtex with 1000 filaments is presented.
  • the test procedure corresponds to example 1.
  • the carbon yield is 65% by weight, the strength of the fiber is 1.1 Gpa and the elongation at break is 2.2%.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Fibers (AREA)
  • Artificial Filaments (AREA)

Description

Die Erfindung betrifft ein Verfahren zur Herstellung von Carbonfasern aus Cellulosefasern, dadurch gekennzeichnet, dass Cellulosefasern, welche einen Wassergehalt von mehr als 30 Gewichtsteilen Wasser auf 100 Gewichtsteile Cellulosefaser haben und bei deren Herstellung keine Verfahrensmaßnahmen zur Trocknung erfolgen, mit einer Lösung von Additiven in Kontakt gebracht werden und danach die additivierten Cellulosefasern, welche mindestens 1 Gewichtsteil Additive auf 100 Gewichtsteile Cellulose enthalten, in Carbonfasern überführt werden, wobei die Additive anorganische Salze in Form von Phosphat, Hydrogenphosphat, Phosphit, Hydrogenphosphit, Sulfat oder Sulfit darstellen und deren Lösung ein einziges Additiv oder ein Gemisch verschiedener Additive enthalten kann.The invention relates to a method for producing carbon fibers from cellulose fibers, characterized in that cellulose fibers which have a water content of more than 30 parts by weight of water per 100 parts by weight of cellulose fiber and during their production no process measures for drying are brought into contact with a solution of additives and then the additized cellulose fibers, which contain at least 1 part by weight of additives per 100 parts by weight of cellulose, are converted into carbon fibers, the additives being inorganic salts in the form of phosphate, hydrogen phosphate, phosphite, hydrogen phosphite, sulphate or sulphite and their solution being a single additive or may contain a mixture of different additives.

Carbonfasern können durch Pyrolyse von Polyacrylnitrilfasern oder Cellulosefasern hergestellt werden. Als nachwachsende Rohstoffe gewinnen die Cellulosefasern für den wachsenden Markt der Carbonfasern zunehmend an Bedeutung.Carbon fibers can be produced by pyrolysis of polyacrylonitrile fibers or cellulose fibers. As a renewable raw material, cellulose fibers are becoming increasingly important for the growing carbon fiber market.

Mingqiu Zhang, S. Zhu, H. Zeng, Y. Lu beschreiben in Die Angewandte Makromolekulare Chemie 222 (1994), 147 -163 (Nr.3908) die Herstellung von Carbonfasern aus Sisalfasern . Die Sisalfasern werden mit Wasser gewaschen und getrocknet. Danach werden sie mit einer Lösung von (NH4)2HPO4 in Wasser behandelt, erneut getrocknet und durch Pyrolyse in Carbonfasern überführt. Mingqiu Zhang, S. Zhu, H. Zeng, Y. Lu describe in Die Angewandte Makromolekulare Chemie 222 (1994), 147-163 (No. 3908) the production of carbon fibers from sisal fibers . The sisal fibers are washed with water and dried. Then they are treated with a solution of (NH 4 ) 2 HPO 4 in water, dried again and converted into carbon fibers by pyrolysis.

Fanlong Zeng, Ding Pan und Ning Pan verwenden Viskosefasern zur Herstellung von Carbonfasern (Journal of Inorganic and Organometallic Polymers and Materials, Vol.15, No.2 June 2005 ). Auch hier werden getrocknete Cellulosefasern mit Lösungen von Additiven behandelt und danach in Carbonfasern überführt. Fanlong Zeng, Ding Pan and Ning Pan use viscose fibers to produce carbon fibers (Journal of Inorganic and Organometallic Polymers and Materials, Vol.15, No.2 June 2005 ). Here, too, dried cellulose fibers are treated with solutions of additives and then converted into carbon fibers.

Hui Li, Yonggang Yang, Yuefang Wen und Lang Liu (Composites Science and Technology 67 (2007) 2675-2682 ) imprägnieren die Viskosefasern vor der Trocknung mit einer organischen Siliciumverbindung. Nach Trocknung der so vorbehandelten Faser erfolgt eine übliche Behandlung der Cellulosefaser mit Additiven, hier mit einer wässrigen Lösung von Ammoniumsulfat und Ammoniumchlorid, und abschließend die Carbonisierung. Hui Li, Yonggang Yang, Yuefang Wen and Lang Liu (Composites Science and Technology 67 (2007) 2675-2682 ) impregnate the viscose fibers with an organic silicon compound before drying. After the fiber pretreated in this way has been dried, the cellulose fiber is usually treated with additives, here with an aqueous solution of ammonium sulfate and ammonium chloride, and finally carbonization.

Auch Cellulose, welche in ionischer Flüsssigkeit gelöst wurde, wird gemäß CN 101871140 zur Herstellung von Carbonfasern verwendet.Cellulose, which has been dissolved in ionic liquid, is also according to CN 101871140 used to manufacture carbon fibers.

EP 1669480 A1 offenbart ein Verfahren zur Herstellung von Garnen oder Faserblättern aus Kohlenstoff ausgehend von einem Cellulosematerial welche mit einer wässerigen Emulsion eines Organosilikon-Additives imprägniert werden. EP 1669480 A1 discloses a process for the production of yarns or fiber sheets made of carbon starting from a cellulose material which are impregnated with an aqueous emulsion of an organosilicon additive.

Bei Verfahren zur Herstellung von Carbonfasern soll die Kohlenstoffausbeute möglichst hoch sein, das heißt, dass der Kohlenstoff der Ausgangsfaser möglichst vollständig in die Carbonfaser überführt wird. Bei der Verwendung von Cellulosefasern ist die Kohlenstoffausbeute noch nicht befriedigend. Ein Teil des Kohlenstoff der Cellulose geht durch Abbau in letztendlich Kohlenmonoxid und Kohlendioxid verloren. Auch sollten die mechanischen Eigenschaften der aus Cellulosefasern erhaltenen Carbonfasern noch verbessert werden.In processes for the production of carbon fibers, the carbon yield should be as high as possible, that is, the carbon of the starting fiber should be converted as completely as possible into the carbon fiber. When using cellulose fibers, the carbon yield is not yet satisfactory. Part of the carbon in the cellulose is lost through breakdown into carbon monoxide and carbon dioxide. The mechanical properties of the carbon fibers obtained from cellulose fibers should also be improved.

Aufgabe der vorliegenden Erfindung war daher ein verbessertes Verfahren zur Herstellung von Carbonfasern aus Cellulosefasern.The object of the present invention was therefore an improved process for the production of carbon fibers from cellulose fibers.

Demgemäß wurde das eingangs definierte Verfahren gefunden.We have found that this object is achieved by the process defined at the beginning.

Zu den CellulosefasernTo the cellulose fibers

Cellulosefasern sind der Ausgangstoff des Verfahrens. Unter Cellulosefasern werden hier Fasern verstanden, welche zu mehr als 60 Gew. %, insbesondere mehr als 80 Gew. %, besonders bevorzugt mehr als 90 Gew. % aus Cellulose oder modifizierter Cellulose bestehen.Cellulose fibers are the starting material for the process. Cellulose 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 einer besonderen Ausführungsform bestehen die Cellulosefasern zu mehr als 98 Gew. %, ganz besonders bevorzugt zu 100 Gew. % aus Cellulose oder modifizierter 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.

Unter modifizierter Cellulose wird Cellulose verstanden, bei denen Hydroxylgrupen verethert oder verestert sind, z. B. kann es sich im Celluloseacetat, Celluloseformiat, Cellulosepropionat, Cellulosecarbamat oder Celluloseallophanat handeln.Modified cellulose is understood to mean cellulose in which hydroxyl groups are etherified or esterified, e.g. B. it can be cellulose acetate, cellulose formate, cellulose propionate, cellulose carbamate or cellulose allophanate.

Vorzugsweise handelt es Cellulosefasern, die aus Cellulose in den vorstehend angegebenen Mindestmengen bestehen.It is preferably cellulose fibers which consist of cellulose in the minimum amounts specified above.

Die Cellulosefasern, welche mit der Lösung eines Additivs in Kontakt gebracht werden, haben einen Wassergehalt von mehr als 30 Gewichtsteilen Wasser, insbesondere mehr als 50 Gewichtsteile Wasser, besonders bevorzugt mehr als 70 Gewichtsteile Wasser auf 100 Gewichtsteile Cellulosefaser.The cellulose fibers which are brought into contact with the solution of an additive have a water content of more than 30 parts by weight of water, in particular more than 50 parts by weight of water, particularly preferably more than 70 parts by weight of water per 100 parts by weight of cellulose fiber.

Im Allgemeinen ist der Wassergehalt aber nicht höher als 500, insbesondere nicht höher als 300 Gewichtsteile Wasser auf 100 Gewichtsteile Cellulosefaser.In general, however, the water content is not higher than 500, in particular not higher than 300 parts by weight of water per 100 parts by weight of cellulose fiber.

Die Cellulosefaser mit dem vorstehenden Wassergehalt kann in einfacher Weise zum Beispiel durch Eintauchen einer getrocketen Cellulosefaser in Wasser erhalten werden. Dazu eignen sich sowohl natürliche Cellulosefasern als auch synthetische Cellulosefasern.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.

Natürliche Cellulosefasern sind insbesondere aus Baumwolle gewonnene Cellulosefasern.Natural cellulose fibers are in particular cellulose fibers obtained from cotton.

In einer bevorzugten Ausführungsform werden synthetische Cellulosefasern verwendetIn a preferred embodiment, synthetic cellulose fibers are used

In einer bevorzugten Ausführungsform werden synthetische Cellulosefasern verwendet, welche unmittelbar vorher durch einen Spinnprozess hergestellt wurden.In a preferred embodiment, synthetic cellulose fibers are used which were produced immediately beforehand by a spinning process.

Die Cellulosefasern werden dann vorzugsweise durch

  • Spinnen der Cellulosefasern aus einer Spinnlösung
  • und anschließendes Waschen der Cellulosefasern mit Wasser
erhalten. Bei dem vorstehenden Spinnprozess wird ein Spinnbad durch Auflösen von Cellulose in einem Lösemittel hergestellt. Aus diesem Spinnbad wird die Cellulosefaser durch Koagulation der Cellulose in Form einer Faser gewonnen.The cellulose fibers are then preferably through
  • Spinning the cellulose fibers from a spinning solution
  • and then washing the cellulose fibers with water
receive. In the above spinning process, a spinning bath is produced by dissolving cellulose in a solvent. The cellulose fiber is obtained from this spinning bath by coagulating the cellulose in the form of a fiber.

Je nach im Spinnbad verwendeten Lösemittel und Zusatzstoffen unterscheidet man verschiedene Arten von Cellulosefasern:

  • Viskosefasern, hergestellt nach dem Viskoseverfahren,
  • LyoceII®-fasern, hergestellt aus einer Spinnlösung, welche NMMO (N-Methylmorpholin-N-oxid) als Lösemittel enthält und
  • Cellulosefasern, welche aus Spinnlösungen mit ionischer Flüssigkeit als Lösemittel gewonnen werden, wie es z. B. in WO 2007/076979 beschrieben ist.
Depending on the solvents and additives used in the spinning bath, a distinction is made between different types of cellulose fibers:
  • Viscose fibers, manufactured according to the viscose process,
  • LyoceII® fibers, made from a spinning solution that contains NMMO (N-methylmorpholine-N-oxide) as a solvent and
  • Cellulose fibers, which are obtained from spinning solutions with ionic liquid as a solvent, as it is, for. B. in WO 2007/076979 is described.

In allen vorstehenden Fällen werden die erhaltenen Cellulosefasern mit Wasser gewaschen, um anhaftendes Lösemittel oder anhaftende Additive aus dem Spinnbad zu entfernen.In all of the above cases, the cellulose fibers obtained are washed with water in order to remove adhering solvent or adhering additives from the spinning bath.

Der Kontakt mit Wasser wird so durchgeführt, dass die Cellulosefaser Wasser in der gewünschten, oben angegebenen Menge aufnimmt. Dazu kann die Cellulosefaser für eine ausreichende Zeit in Wasser eingetaucht oder im kontinuierlichen Prozess durch ein ausreichend langes Wasserbad geführt werden.The contact with water is carried out in such a way that the cellulose fiber absorbs water in the desired amount specified above. For this purpose, the cellulose fiber can be immersed in water for a sufficient time or it can be passed through a sufficiently long water bath in a continuous process.

Bei der Herstellung der Cellulosefasern erfolgen vorzugsweise keine Verfahrensmaßnahmen zur Trocknung. Die im Spinnprozess erhaltene Cellulosefaser wird ohne vorherige Trocknung mit Wasser gewaschen und danach, natürlich wiederum ohne vorherige Trocknung, mit der Lösung des Additivs in Kontakt gebracht. Es handelt sich daher um eine sogenannte "never dried" Cellulosefaser.In the production of the cellulose fibers, there are preferably no process measures for drying. The cellulose fiber obtained in the spinning process is washed with water without prior drying and then, of course, again without prior drying, brought into contact with the solution of the additive. It is therefore a so-called "never dried" cellulose fiber.

Zur Additivierung der CellulosfasernFor adding additives to the cellulose fibers

Die wässrigen Cellulosefasern werden mit einer Lösung von Additiven in Kontakt gebracht.The aqueous cellulose fibers are brought into contact with a solution of additives.

Vorzugsweise handelt es sich um eine Lösung von Additiven in einem hydrophilen Lösemittel, insbesondere in Wasser, hydrophile organische Lösemittel, z.B. Alkohole oder Ether, oder deren Gemische. Als hydrophile Lösemittel besonders bevorzugt sind Wasser oder Gemische von Wasser mit anderen, mit Wasser unbegrenzt mischbaren hydrophilen organischen Lösemitteln, wobei im letzten Fall der Wasseranteil im Lösemittelgemisch in einer bevorzugten Ausführungsform mindestens 50 Gew. % beträgt.It is preferably a solution of additives in a hydrophilic solvent, in particular in water, hydrophilic organic solvents, for example alcohols or ethers, or mixtures thereof. Particularly preferred hydrophilic solvents are water or mixtures of water with other hydrophilic organic solvents which are infinitely miscible with water, in the latter case the water content in the solvent mixture in a preferred embodiment being at least 50% by weight.

Insbesondere handelt es sich um eine Lösung von Additiven in Wasser.In particular, it is a solution of additives in water.

Die Lösung enthält ein einziges Additiv oder ein Gemisch von verschiedenen Additiven.The solution contains a single additive or a mixture of different additives.

Als Additive geeignet sind insbesondere Verbindungen, welche eine Löslichkeit in Wasser von mindestens 10 Gewichtsteilen, bevorzugt von mindestens 20 Gewichtsteilen, insbesondere von mindestens 30 Gewichtsteilen auf 100 Gewichtsteile Wasser bei Normalbedingungen (20°C, 1 bar) besitzen.Particularly suitable 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).

Vorzugsweise handelt es sich bei den Additiven um niedermolekulare Verbindungen, welche ein Molgewicht von maximal 1000 g/mol, besonders bevorzugt maximal 500 g/mol, insbesondere von maximal 300 g/mol haben.The additives are preferably low molecular weight compounds which have a molecular weight of at most 1000 g / mol, particularly preferably at most 500 g / mol, in particular at most 300 g / mol.

Die Additive sind anorganische Salze in Form von Phosphat, Hydrogenphosphat, Phosphit, Hydrogenphosphit, Sulfat oder Sulfit wobei es sich um Metallsalze, insbesondere Alkalimetallsalze, oder um Salze mit organischen Kationen handeln kann.The additives are inorganic salts in the form of phosphate, hydrogen phosphate, phosphite, hydrogen phosphite, sulfate or sulfite, it being possible for them to be metal salts, in particular alkali metal salts, or salts with organic cations.

Bei den Kationen der vorstehenden anorganischen Salze kann es sich insbesondere um Metallkationen, vorzugsweise Alkalimetallkationen wie Na+ oder K+, oder Ammonium (NH4 +) handeln. Genannt seien exemplarisch (NH4)2HPO4, NH4SO4 oder NH4Cl.The cations of the above inorganic salts can in particular be metal cations, preferably alkali metal cations such as Na + or K + , or ammonium (NH 4 + ). Examples are (NH 4 ) 2 HPO 4 , NH 4 SO 4 or NH 4 Cl.

Die vorstehenden Additive sind häufig Additive, welche auch als Flammschutzmittel Verwendung finden. Es kann angenommen werden dass diese Additive mit der primären Hydroxylgruppe des Glucoserings (d.h. der CH2OH Gruppe) wechselwirken und während der Pyrolyse einem Abbau der Cellulose zu flüchtigen Kohlenstoffverbindungen entgegenwirken.The above additives are often additives which are also used as flame retardants. It can be assumed that these additives interact with the primary hydroxyl group of the glucose ring (ie the CH 2 OH group) and counteract the breakdown of cellulose into volatile carbon compounds during pyrolysis.

Die Gesamtmenge aller Additive in der Lösung beträgt z. B. 0,05 bis 5 mol/pro Liter Lösung, vorzugsweise 0,1 mol bis 2 mol/pro Liter Lösung.The total amount of all additives in the solution is e.g. B. 0.05 to 5 mol / per liter of solution, preferably 0.1 mol to 2 mol / per liter of solution.

Der Kontakt mit der Lösung der Additive wird so durchgeführt, dass die Cellulosefaser Additive in der gewünschten Menge aufnimmt. Dazu kann die Cellulosefaser für eine ausreichende Zeit in die Lösung eingetaucht oder im kontinuierlichen Prozess durch ein ausreichend langes Lösungsbad geführt werden.The contact with the solution of the additives is carried out in such a way that the cellulose fiber absorbs additives in the desired amount. For this purpose, the cellulose fiber can be immersed in the solution for a sufficient time or it can be passed through a sufficiently long solution bath in a continuous process.

In einer bevorzugten Ausführungsform wird die Cellulosefaser kontinuierlich durch die Lösung des Additivs geführt.In a preferred embodiment, the cellulose fiber is passed continuously through the solution of the additive.

Die Kontaktzeit der Cellulosefaser mit der Lösung der Additive beträgt vorzugsweise mindestens 0,5 Sekunden, besonders bevorzugt mindestens 2 und ganz besonders bevorzugt mindestens 10 Sekunden. Im Allgemeinen ist sie nicht länger als 100 Sekunden, vorzugsweise nicht länger als 30 Sekunden.The contact time of the cellulose fiber with the solution of the additives is preferably at least 0.5 seconds, particularly preferably at least 2 and very particularly preferably at least 10 seconds. Generally it is no longer than 100 seconds, preferably no longer than 30 seconds.

Die erhaltene, additivierte Cellulosefaser enthält in einer bevorzugten Ausführungsform mindestens 5 Gewichtsteil Additive auf 100 Gewichtsteile Cellulose. Besonders bevorzugt enthält die additivierte Cellulosefaser mindestens 1 Gewichtsteil, ganz besonders bevorzugt mindestens 3 Gewichtsteile Additive auf 100 Gewichtsteile Cellulosefaser. Im Allgemeinen enthält die Cellulosefaser nicht mehr als 30 Gewichtsteile Additive, insbesondere nicht mehr als 10 bzw. nicht mehr als 5 Gewichtsteile Additive auf 100 Gewichtsteile Cellulosefaser.In a preferred embodiment, the additized cellulose fiber obtained contains at least 5 parts by weight of additives per 100 parts by weight of cellulose. The additized cellulose fiber particularly preferably contains at least 1 part by weight, very particularly preferably at least 3 parts by weight of additives per 100 parts by weight of cellulose fiber. In general, the cellulose fiber contains not more than 30 parts by weight of additives, in particular not more than 10 or not more than 5 parts by weight of additives per 100 parts by weight of cellulose fiber.

Die Herstellung der Cellulosefaser im Spinnprozess und im Anschluss daran die Weiterverarbeitung durch Waschen der Cellulosefaser und Inkontaktbringen der Cellulosefaser mit der Lösung der Additive sind vorzugsweise Bestandteile eines kontinuierlichen Gesamtprozesses. Dabei wird die Cellulosefaser nach ihrer Herstellung im Allgemeinen über bewegliche Rollen den einzelnen Schritten der Weiterverarbeitung zugeführt.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 its production, the cellulose fiber is generally fed to the individual further processing steps via movable rollers.

Abschließend kann überschüssiges Lösemittel aus der Lösung der Additive durch Abquetschung entfernt werden und die additivierte Cellulosefaser aufgerollt werden.Finally, excess solvent can be removed from the solution of the additives by squeezing off and the cellulose fiber with the additive can be rolled up.

Abschließend kann die additivierte Cellulosefaser getrocknet werden, z. B. bei Temperaturen von 50 bis 300°C. Eine derartige Trocknung empfiehlt sich dann, wenn die additivierte Cellulosefase vor Überführung in eine Carbonfaser zunächst noch gelagert oder transportiert werden soll.Finally, the additized cellulose fiber can be dried, e.g. B. at temperatures of 50 to 300 ° C. Such drying is recommended if the cellulose fiber with the additive is to be stored or transported before it is converted into a carbon fiber.

Schließlich wird die additivierte Cellulosefaser durch Pyrolyse in eine Carbonfaser überführt.Finally, the additized cellulose fiber is converted into a carbon fiber by pyrolysis.

Die Pyrolyse wird im Allgemeinen bei Temperauren von 500 bis 1600°C durchgeführt. Sie kann z.B. unter Luft oder unter Schutzgas, z. B. Stickstoff oder Helium durchgeführt werden. Vorzugsweise wird sie unter einem Schutzgas vorgenommen.The pyrolysis is generally carried out at temperatures of 500 to 1600 ° C. You can, for example, under air or under protective gas, z. B. nitrogen or helium can be carried out. It is preferably carried out under a protective gas.

Vor der Pyrolyse kann die Cellulosefaser getrocknet werden. Bei bereits getrockneten und gelagerten Cellulosefasern kann die Trocknung gegebenenfalls wiederholt werden.The cellulose fiber can be dried before pyrolysis. In the case of cellulose fibers that have already been dried and stored, drying can be repeated if necessary.

In Betracht kommt ein mehrstufiges Verfahren, bei dem die Cellulosefaser bei Temperaturen im Bereich von 50 bis 300°C getrocknet und danach die Pyrolyse bei Temperaturen im Bereich von 500 bis 1600°C, vorzugsweise 700 bis 1500°C, durchgeführt wird.A multistage process in which the cellulose fiber is dried at temperatures in the range from 50 to 300 ° C. and then the pyrolysis is carried out at temperatures in the range from 500 to 1600 ° C., preferably 700 to 1500 ° C., is suitable.

Sowohl bei der Trocknung als auch bei der Pyrolyse kann die Temperatur stufenweise oder kontinuierlich erhöht werden.Both during drying and during pyrolysis, the temperature can be increased gradually or continuously.

In Betracht kommt zum Beispiel eine Trocknung in zwei oder mehr Stufen, zum Beispiel bei 50 bis 100°C in einer ersten Stufe und bei 100 bis 200°C in einer zweiten Stufe. Die Kontaktzeit kann in den einzelnen Stufen zum Beispiel jeweils 5 bis 300 Sekunden und insgesamt während der Trocknung 10 bis 500 Sekunden betragen.For example, drying in two or more stages is possible, for example at 50 to 100 ° C. in a first stage and at 100 to 200 ° C. in a second stage. The contact time in the individual stages can be, for example, 5 to 300 seconds each and a total of 10 to 500 seconds during the drying.

In Betracht kommt zum Beispiel eine Pyrolyse, bei der die Temperatur kontinuierlich erhöht wird, z. B. beginnend ab 200°C bis schließlich zum Erreichen von 1600 oder 1400 oder 1200°C. Die Temperaturerhöhung kann zum Beispiel mit 1 bis 20 Kelvin/Minute erfolgen.For example, a pyrolysis in which the temperature is continuously increased, e.g. B. starting at 200 ° C and finally reaching 1600 or 1400 or 1200 ° C. The temperature increase can take place, for example, at 1 to 20 Kelvin / minute.

Die Cellulosefaser sollte dabei vorzugsweise während einer Zeit von 10 bis 60 Minuten einer Temperatur im Bereich von 900 bis 1600°C ausgesetzt sein.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.

Die Carbonausbeute bei der Pyrolyse beträgt im Allgemeinen 20 bis 95 Gew %; das heißt, dass die Carbonfaser 20 bis 95 Gewichtsprozent des in der Cellulosefaser enthaltenen Kohlenstoffs enthält. Die Carbonausbeute beträgt insbesondere 70 bis 95, besonders bevorzugt 70 bis 90, ganz besonders bevorzugt 70 bis 85 Gew. %.The carbon yield in pyrolysis is generally 20 to 95% by weight; that is, the carbon fiber contains 20 to 95 percent 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.

Durch das erfindungsgemäße Verfahren wird eine erhöhte Carbonausbeute ermöglicht. Die erhaltene Carbonfaser hat sehr gute mechanische Eigenschaften, insbesondere eine gute Festigkeit und Elastizität.The process according to the invention enables an increased carbon yield. The carbon fiber obtained has very good mechanical properties, in particular good strength and elasticity.

BeispieleExamples CellulosefaserCellulose fiber

Als Cellulosefaser wird in dem Beispiel und Vergleichsbeispiel eine synthetische, reißfeste Cellulosefaser, welche zur Herstellung von Autoreifen verwendet werden, eingesetzt. Derartige Cellulosefasern sind als Reifencord-fasern bekannt. Die Cellulosefaser in dem Beispiel wurde seit ihrer Herstellung nicht getrocknet, daher auch die Bezeichnung "never-dried Reifencordfaser". Die Cellulosefaser im Vergleichsbeispiel wurde getrocknet; Cellulosefasern enthalten jedoch üblicherweise gebundenes Restwasser, daher kann der Wassergehalt von getrockneten Cellulosefasern z. B. bis zu 20 Gew. % betragen.In the example and comparative example, a synthetic, tear-resistant cellulose fiber, which is used for the production of car tires, is used as the cellulose fiber. Such cellulose fibers are known as tire cord fibers. The cellulose fiber in the example has not been dried since its manufacture, hence the name "never-dried tire cord fiber". The cellulose fiber in the comparative example was dried; Cellulose fibers usually contain bound residual water, so the water content of dried cellulose fibers can e.g. B. up to 20 wt.%.

Beispiel 1:Example 1:

Zur Ausrüstung mit Additiven wird eine never-dried Reifencordfaser mit einem Wassergehalt von 150 % und einen Einzelfilamenttiter von 2,2 dtex mit 1000 Filamenten vorgelegt.
Die Ausrüstung und Trocknung der Faser erfolgt in einem kontinuierlichen Prozess auf Galetten. Galetten sind Walzen, welche den kontinuierlichen Verlauf der Faser entlang der Anlage ermöglichen. Es kommen 4 dieser Galetten zum Einsatz. Zwischen der ersten und der zweiten Galette erfolgt die Beladung der Faser mir den Additiven über ein Tauchbad. Zwischen der dritten und vierten Galette befindet sich ein Heissluftkanal, in dem eine Trocknung erfolgt. Am Ende spult ein tensionsgesteuerter Wickler das ausgerüstete und getrocknete Fasermaterial auf.For finishing with additives, a never-dried tire cord fiber with a water content of 150% and a single filament titer of 2.2 dtex with 1000 filaments is presented.
The finishing and drying of the fibers takes place in a continuous process on godets. Godets are rollers that enable the fibers to run continuously along the system. 4 of these godets are used. Between the first and the second godet, the fibers are loaded with the additives via an immersion bath. Between the third and fourth godets there is a hot air duct in which drying takes place. At the end, a tension-controlled winder spools up the finished and dried fiber material.

Alle Galetten haben eine Geschwindigkeit von 6 m/min. Die erste Galette dient als Abspuleinheit der in Wasser gelagerten never dried Reifencordfasern. Die Faser wird 2 Mal um die Galette gewickelt, was einer Kontaktzeit von 10 sec entspricht. Anschließend wird die Faser durch ein Tauchbad mit einer Ammoniumdihydrogenphosphatlösung (Konzentration des Ammoniumhydrogenophosphats von 0,54 mol/l) geleitet. Die Verweilzeit liegt hier bei ca. einer Sekunde. Das Material wird nun sechs Mal um die zweite Galette gewunden. Dieser Schritt dient dazu, überflüssige Ausrüstung abtropfen zu lassen und eine homogene Verteilung des Ammoniumhydrogenphosphats in der Faser zu bewirken. Die Kontaktzeit hier beträgt 72 Sekunden. Danach erfolgt die Trocknung auf der mit 80°C beheizten dritten Galette. 10 Wicklungen entsprechen hier einer Kontaktzeit von 100 sec. Die Faser wird nun durch einen 150°C heißen Heißluftkanal geführt. Die Verweilzeit darin beträgt 12 sec. Der trockene Faden wird nun 4 mal um die letzte Galette gewickelt (Kontaktzeit 24 sec) bevor ein tensionsgesteuerter Wickler das Material mit einer Vorspannung von 0,1 cN/tex aufspult.All godets have a speed of 6 m / min. The first godet serves as an unwinding unit for the never dried tire cord fibers stored in water. The fiber is wound around the godet twice, which corresponds to a contact time of 10 seconds. The fiber is then passed through an immersion bath with an ammonium dihydrogen phosphate solution (concentration of ammonium hydrogen phosphate of 0.54 mol / l). The dwell time here is about one second. The material is now wound around the second godet six times. This step is used to drain excess equipment and to bring about a homogeneous distribution of the ammonium hydrogen phosphate in the fiber. The contact time here is 72 seconds. This is followed by drying on the third godet heated to 80 ° C. 10 windings correspond to a contact time of 100 seconds. The fiber is now guided through a hot air duct at 150 ° C. The dwell time is 12 seconds. The dry thread is now wound 4 times around the last godet (contact time 24 seconds) before a tension-controlled winder winds the material with a pretension of 0.1 cN / tex.

Die mit dem Additiv ausgerüstete Cellulosefaser wird anschließend unter Schutzgas in zwei Stufen carbonisert. In der ersten Stufe wird mir 2°K/min auf 260°C aufgeheizt und nach eine Verweilzeit von 10 min mit 10k/min auf 1400°C aufgeheizt und danach abgekühlt.The cellulose fiber equipped with the additive is then carbonized in two stages under protective gas. In the first stage, it is heated at 2 ° K / min to 260 ° C and, after a dwell time of 10 min, heated at 10k / min to 1400 ° C and then cooled.

Die Carbonausbeute beträgt 80 Gew.%, die Festigkeit der Faser 1,4 Gpa und die Bruchdehnung 3,1%.The carbon yield is 80% by weight, the strength of the fiber 1.4 Gpa and the elongation at break 3.1%.

Vergleichsbeispiel mit Trocknung vor der AdditivierungComparative example with drying before additives

Zur Ausrüstung mit Additiven wird eine getrocknete Reifencordfaser mit einem Wassergehalt kleiner 20 Gew.% und einen Einzelfilamenttiter von 2,2 dtex mit 1000 Filamenten vorgelegt. Die Versuchsdurchführung entspricht Beispiel 1.For finishing with additives, a dried tire cord fiber with a water content of less than 20% by weight and a single filament denier of 2.2 dtex with 1000 filaments is presented. The test procedure corresponds to example 1.

Die Carbonausbeute beträgt 65 Gew.%, die Festigkeit der Faser 1,1 Gpa und die Bruchdehnung 2,2 %.The carbon yield is 65% by weight, the strength of the fiber is 1.1 Gpa and the elongation at break is 2.2%.

Claims (12)

  1. Method for producing carbon fibres from cellulose fibres, characterised in that cellulose fibres which have a water content of more than 30 parts by weight of water per 100 parts by weight of cellulose fibres and which do not undergo any drying procedures during their production are contacted with a solution of additives, and then the additised cellulose fibres, which contain at least 1 part by weight of additives per 100 parts by weight of cellulose, are converted into carbon fibres, the additives being inorganic salts in the form of phosphate, hydrogen phosphate, phosphite, hydrogen phosphite, sulphate or sulphite and it being possible for the additive solution to contain a single additive or a mixture of different additives.
  2. Method according to claim 1, characterised in that the cellulose fibres contain more than 50 parts by weight of water, especially more than 70 parts by weight of water, per 100 parts by weight of cellulose.
  3. Method according to claim 1 or claim 2, characterised in that the cations of the inorganic salts are alkali metal cations or ammonium (NH4 +) ions.
  4. Method according to at least one of the preceding claims, characterised in that the inorganic salts are (NH4)2HPO4 or (NH4)2SO4.
  5. Method according to at least one of the preceding claims, characterised in that the solution is a solution of the additives in water, a hydrophilic organic solvent, or mixtures thereof.
  6. Method according to one of claims 1 to 5, characterised in that the cellulose fibre is led through the solution of the additive continuously and the contact time is at least 2 seconds.
  7. Method according to one of claims 1 to 6, characterised in that the obtained additised cellulose fibre contains at least 5 parts by weight of additives per 100 parts by weight of cellulose.
  8. The method according to at least one of the preceding claims, characterised in that the cellulose fibres consist to an extent of more than 60 % by weight, especially to an extent of more than 80 % by weight, especially preferably to an extent of more than 90 % by weight, of cellulose or modified cellulose.
  9. Method according to claim 8, characterised in that the cellulose fibres consist to an extent of more than 98 % by weight, very especially preferably to an extent of 100 % by weight, of cellulose or modified cellulose.
  10. Method according to claim 9, characterised in that the hydroxyl groups of the modified cellulose are etherified or esterified.
  11. Method according to claim 10, characterised in that the modified cellulose is cellulose acetate, cellulose formate, cellulose propionate, cellulose carbamate, or cellulose allophanate.
  12. Method according to one of claims 1 to 11, characterised in that the obtained, additised cellulose fibre is converted into a carbon fibre by pyrolysis.
EP15721717.5A 2014-05-16 2015-05-12 Method for producing carbon fibers from cellulose fibers Active EP3143187B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP14168572 2014-05-16
PCT/EP2015/060479 WO2015173243A1 (en) 2014-05-16 2015-05-12 Method for producing carbon fibers from cellulose fibers

Publications (2)

Publication Number Publication Date
EP3143187A1 EP3143187A1 (en) 2017-03-22
EP3143187B1 true EP3143187B1 (en) 2020-11-11

Family

ID=50771083

Family Applications (1)

Application Number Title Priority Date Filing Date
EP15721717.5A Active EP3143187B1 (en) 2014-05-16 2015-05-12 Method for producing carbon fibers from cellulose fibers

Country Status (4)

Country Link
US (1) US20170081787A1 (en)
EP (1) EP3143187B1 (en)
EA (1) EA201692291A1 (en)
WO (1) WO2015173243A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016078960A1 (en) 2014-11-20 2016-05-26 Basf Se Method for producing carbon fibres from cellulose fibres containing phosphorus
WO2017133995A1 (en) 2016-02-01 2017-08-10 Basf Se Method for producing c4-c15 lactams
ES2954633T3 (en) 2016-02-11 2023-11-23 Technikum Laubholz Gmbh Procedure for producing carbon fibers from cellulose fibers treated with sulfonic acid salts
DE102020113807A1 (en) * 2020-05-22 2021-11-25 centrotherm international AG Continuous fibers based on cellulose and / or cellulose derivatives, processes for their production and their use

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1455531A (en) * 1975-01-02 1976-11-10 Toyo Boseki Process for preparing active carbon fibres machine for attaching components to a printed circuit board
EP1669480A1 (en) * 2004-12-07 2006-06-14 Snecma Propulsion Solide Method of obtaining yarns or fiber sheets of carbon from a cellulose precursor
RU2429316C1 (en) * 2010-03-26 2011-09-20 Юрий Васильевич Карасев Procedure for continuous production of hydrated cellulose of carbon fibre in form of unidirectional braid

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1455531A (en) * 1975-01-02 1976-11-10 Toyo Boseki Process for preparing active carbon fibres machine for attaching components to a printed circuit board
EP1669480A1 (en) * 2004-12-07 2006-06-14 Snecma Propulsion Solide Method of obtaining yarns or fiber sheets of carbon from a cellulose precursor
RU2429316C1 (en) * 2010-03-26 2011-09-20 Юрий Васильевич Карасев Procedure for continuous production of hydrated cellulose of carbon fibre in form of unidirectional braid

Also Published As

Publication number Publication date
EA201692291A1 (en) 2017-04-28
US20170081787A1 (en) 2017-03-23
WO2015173243A1 (en) 2015-11-19
EP3143187A1 (en) 2017-03-22

Similar Documents

Publication Publication Date Title
EP3143187B1 (en) Method for producing carbon fibers from cellulose fibers
EP3414374B1 (en) Method for producing carbon fibres from cellulose fibres treated with sulphonic acid salts
DE1494692A1 (en) Process for the production of shaped articles from solutions of completely aromatic polyamides
EP0119185B1 (en) Method for the preparation of highly fire-retarding, heat-resisting polyimide fibres
DE202013011959U1 (en) Direct-spun cellulose fibers, their preparation and use
DE102013002833B4 (en) A process for the production of regenerated cellulose fibers and the use of regenerated cellulose fibers produced by the process
AT507758A1 (en) YARN AND THREADS FROM BLENDS OF FIBERS AND ARTICLES THEREFROM
AT401063B (en) METHOD FOR PRODUCING CELLULOSIC SHAPED BODIES
DE3336584A1 (en) METHOD FOR PRODUCING CARBON FIBERS OR GRAFIT FIBERS
DE1258544B (en) Process for the production of regenerated cellulose fibers and threads
DE102007014272A1 (en) Process for the flameproofing of cotton
DE212015000267U1 (en) Carbon fibers from phosphorus-containing cellulose fibers
WO1997004148A1 (en) Cellulose fibre
DE102020113807A1 (en) Continuous fibers based on cellulose and / or cellulose derivatives, processes for their production and their use
AT405532B (en) CELLULOSIC MICROFIBER
DE2031308C3 (en) Process for the production of crimped, regenerated cellulose fibers
DE202012013359U1 (en) Carbon fibers and carbon fiber precursors
EP0888467B1 (en) Process for producing cellulosic fibres with reduced tendency to fibrillate
WO1997046745A1 (en) Method of producing a cellulosic yarn
DE2031316B2 (en) Process for the production of highly curled cellulose fibers
AT243428B (en) Process for the production of structures consisting of regenerated cellulose
DE1469064C (en) Process for the production of threads, fibers or foils consisting of regenerated cellulose
DE965150C (en) Process for the production of strong synthetic fibers and threads from viscose
DE876886C (en) Process for the production of cellulose hydrate threads by spinning viscose
DE102012016714A1 (en) Regenerated cellulose fibers which are present as non-fibrillating cellulose filaments present in form of micro- or super-micro-filaments having less titre, useful e.g. as carbon fiber precursors for producing carbon fibers

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20161216

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: DEUTSCHE INSTITUTE FUER TEXTIL- UND FASERFORSCHUNG

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20190328

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20200519

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1333558

Country of ref document: AT

Kind code of ref document: T

Effective date: 20201115

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502015013791

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20201111

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201111

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201111

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210311

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210211

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210212

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210211

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201111

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201111

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201111

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210311

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201111

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201111

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201111

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201111

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201111

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201111

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502015013791

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201111

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20210812

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201111

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201111

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201111

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201111

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201111

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 502015013791

Country of ref document: DE

Owner name: TECHNIKUM LAUBHOLZ GMBH (TLH), DE

Free format text: FORMER OWNER: DEUTSCHE INSTITUTE FUER TEXTIL- UND FASERFORSCHUNG DENKENDORF, 73770 DENKENDORF, DE

Ref country code: DE

Ref legal event code: R081

Ref document number: 502015013791

Country of ref document: DE

Owner name: TECHNIKUM LAUBHOLZ GMBH, DE

Free format text: FORMER OWNER: DEUTSCHE INSTITUTE FUER TEXTIL- UND FASERFORSCHUNG DENKENDORF, 73770 DENKENDORF, DE

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20210512

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210531

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210531

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201111

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210512

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20210531

REG Reference to a national code

Ref country code: AT

Ref legal event code: PC

Ref document number: 1333558

Country of ref document: AT

Kind code of ref document: T

Owner name: TECHNIKUM LAUBHOLZ GMBH, DE

Effective date: 20220314

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210531

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210512

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210512

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210531

PGRI Patent reinstated in contracting state [announced from national office to epo]

Ref country code: LI

Effective date: 20220202

Ref country code: CH

Effective date: 20220202

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210311

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20150512

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201111

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20230523

Year of fee payment: 9

Ref country code: DE

Payment date: 20230530

Year of fee payment: 9

Ref country code: CZ

Payment date: 20230510

Year of fee payment: 9

Ref country code: CH

Payment date: 20230602

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20230519

Year of fee payment: 9

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 502015013791

Country of ref document: DE

Owner name: TECHNIKUM LAUBHOLZ GMBH, DE

Free format text: FORMER OWNER: TECHNIKUM LAUBHOLZ GMBH (TLH), 89143 BLAUBEUREN, DE

Ref country code: DE

Ref legal event code: R081

Ref document number: 502015013791

Country of ref document: DE

Owner name: TECHNIKUM LAUBHOLZ GMBH (TLH), DE

Free format text: FORMER OWNER: TECHNIKUM LAUBHOLZ GMBH (TLH), 89143 BLAUBEUREN, DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201111