WO2016078960A1 - Procédé de production de fibres de carbone à partir de fibres de cellulose contenant du phosphore - Google Patents

Procédé de production de fibres de carbone à partir de fibres de cellulose contenant du phosphore Download PDF

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Publication number
WO2016078960A1
WO2016078960A1 PCT/EP2015/076132 EP2015076132W WO2016078960A1 WO 2016078960 A1 WO2016078960 A1 WO 2016078960A1 EP 2015076132 W EP2015076132 W EP 2015076132W WO 2016078960 A1 WO2016078960 A1 WO 2016078960A1
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WO
WIPO (PCT)
Prior art keywords
cellulose
fiber
phosphorus
ionic liquid
fibers
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PCT/EP2015/076132
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German (de)
English (en)
Inventor
Sunghee Son
Klemens Massonne
Martin Merger
Frank Hermanutz
Johanna SPOERL
Michael R. Buchmeiser
Original Assignee
Basf Se
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Publication date
Application filed by Basf Se filed Critical Basf Se
Priority to DE212015000267.5U priority Critical patent/DE212015000267U1/de
Publication of WO2016078960A1 publication Critical patent/WO2016078960A1/fr

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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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • 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
    • D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
    • 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

Definitions

  • the invention relates to a process for the production of carbon fibers from cellulose fibers, characterized in that a) cellulose with a phosphorus compound in the presence of an ionic liquid to a phosphorus-containing cellulose (P-cellulose) is reacted, b) the P-cellulose in a Cellulose fiber is transferred and c) the cellulose fiber is converted into a carbon fiber.
  • Carbon fibers can be made by pyrolysis of polyacrylonitrile fibers or cellulose fibers. As renewable raw materials, cellulose fibers are becoming increasingly important for the growing market for carbon fibers.
  • WO2012 / 156441 describes the preparation of carbon fibers from lignin fibers as starting material.
  • cellulose or cellulose derivatives can be used.
  • lignin fibers and ionic liquid can be used as a solvent.
  • process step a cellulose is reacted with a phosphorus compound in the presence of an ionic liquid to give a phosphorus-containing cellulose (P-cellulose for short).
  • cellulose is understood here as meaning cellulose and also modified cellulose.
  • Modified cellulose is cellulose whose hydroxyl groups are partially etherified or esterified. It may be z.
  • Each glucose ring of the cellulose carries 3 hydroxyl groups, which are at least partially substituted in the case of a modified cellulose.
  • the degree of substitution can have values from 0 to 3; indicates how many of the hydroxyl groups per glucose ring are substituted on average (e.g., by an ether group or ester group).
  • a degree of substitution of 1 means that, on average, each glucose ring of the cellulose has a substituent and, on average, each glucose ring still has two hydroxy groups.
  • the degree of substitution of the cellulose can be up to 3. With a degree of substitution of three, although all hydroxyl groups are already protected by z. Example, an ester group or ether group substituted, but a reaction with the phosphorus compound is still possible, for. B. by transesterification.
  • the degree of substitution of the cellulose is preferably not more than 2, in particular not more than 1, more preferably not more than 0.5.
  • the cellulose used in process step a) contains no or at most only little phosphorus;
  • the OH groups of the cellulose were therefore not previously or hardly reacted with phosphorus compounds.
  • the phosphorus content of the cellulose used in a) is less than 1% by weight, more preferably less than 0.1% by weight, most preferably less than 0.01% by weight, based on the total weight of the cellulose.
  • the cellulose used in a) still contains no phosphorus.
  • the phosphorus compound is less than 1% by weight, more preferably less than 0.1% by weight, most preferably less than 0.01% by weight, based on the total weight of the cellulose.
  • the cellulose used in a) still contains no phosphorus.
  • Suitable phosphorus compounds which are used in a) are any compounds which contain at least one phosphorus atom and can react with a hydroxyl group of the glucose ring.
  • suitable phosphorus compounds contain 1 to 10, in particular 1 to 3, particularly preferably 1 or 2, phosphorus atoms. In a particular embodiment, they contain only one phosphorus atom.
  • suitable phosphorus compounds have a molecular weight of less than 10000, in particular less than 1000, and more preferably less than 500 g / mol.
  • the phosphorus compounds are low molecular weight compounds having a molecular weight of less than 300 g / mol.
  • Suitable phosphorus compounds are, in particular, acids, salts or esters, in particular those which satisfy the above conditions and preferred conditions.
  • the anion preferably contains the phosphorus atom (s).
  • the cation may be a metal cation or an organic cation.
  • a metal cation it is in particular an alkali metal or alkaline earth metal, preferably an alkali metal, in particular a sodium or potassium cation.
  • an organic cation it is preferably a cation which, together with the phosphorus-containing anion, is an ionic liquid.
  • the phosphorus compound is a phosphorus-containing ester, an acid that may contain ester groups, or a salt with an anion of the acid.
  • R 1 is an H atom, a hydroxy group or a group OR 4 ;
  • R 2 and R 3 independently of one another represent an H atom or a hydrocarbon group having 1 to 10 C atoms and R 4 represents a hydrocarbon group having 1 to 10 C atoms.
  • R 2 and R 3 independently of one another preferably represent an H atom or a hydrocarbon group having 1 to 4 C atoms.
  • R 4 preferably represents a hydrocarbon group having 1 to 4 carbon atoms.
  • phosphorus compounds which may be mentioned are 1-ethyl-3-methylimidazolium diethyl phosphate, dimethylimidazolium monomethyl-H-phosphonate, diethylimidazolium monoethyl H-phosphonate, phosphonic acid, diethyl phosphite
  • the phosphorus compounds are a salt of the anion of the formula II.
  • the phosphorus compounds are a salt of the anion of the formula II, where this salt is an ionic liquid.
  • ionic liquid is understood as meaning salts (compounds of cations and anions) which have a melting point of less than 200 ° C., preferably less than 150 ° C., more preferably less than 100 ° C., under atmospheric pressure (1 bar).
  • ionic liquid will be understood below to mean both individual and mixtures of different ionic liquids.
  • Preferred ionic liquids contain an organic compound as a cation (organic cation). Depending on the valence of the anion, the ionic liquid may contain other cations, including metal cations, in addition to the organic cation.
  • the cations of particularly preferred ionic liquids are exclusively an organic cation or, in the case of polyvalent anions, a mixture of different organic cations.
  • Suitable organic cations are in particular organic compounds with heteroatoms, such as nitrogen, sulfur, oxygen or phosphorus; in particular, the organic cations to compounds with an ammonium group (ammonium cations), an oxonium group (oxonium cations), a sulfonium group (sulfonium cations) or a phosphonium group (phosphonium cations).
  • the organic cations of the ionic liquids are ammonium cations, including non-aromatic compounds with a localized positive charge on the nitrogen atom, for example compounds in which the nitrogen has four bonds (quaternary ammonium compounds, positive charge on the nitrogen atom) N atom) or a double bond and two single bonds
  • aromatic compounds with delocalized positive charge and at least one, preferably one to three nitrogen atoms in the aromatic ring system (delocalized positive charge) are understood.
  • Preferred organic cations are quaternary ammonium cations, preferably those having three or four aliphatic substituents, more preferably C1 to C12 alkyl groups on the nitrogen atom, which may be optionally substituted by hydroxyl groups, and cyclic ammonium cations selected from pyridinium cations, pyridazinium Cations, pyrimidinium cations, pyrazinium cations, imidazolium cations, pyrazolium cations, pyrazolinium cations, imidazolinium cations, thiazolium cations, triazolium cations, pyrrolidinium cations and imidazolidinium cations. These cations are e.g. in WO 2005/1 13702.
  • ammonium cations are quaternary ammonium cations, imidazolium cations, pyrimidinium cations and pyrazolium cations.
  • R 1 is an organic radical having 1 to 20 C atoms
  • R2, R3, R4 and R5 stand for an H atom or an organic radical having 1 to 20 C atoms
  • X stands for an anion
  • R 1 and R 3 are preferably independently an organic radical having 1 to 10 C atoms.
  • R 1 and R 3 are an aliphatic radical, in particular an aliphatic radical without further heteroatoms, eg. B. for an alkyl group.
  • R1 and R3 independently of one another are a C1 to C10 or a C1 to C4 alkyl group.
  • R 2, R 4 and R 5 are preferably independently an H atom or an organic radical having 1 to 10 C atoms; In particular, R 2, R 4 and R 5 represent an H atom or an aliphatic radical. Particularly preferably, R 2, R 4 and R 5 independently of one another are an H atom or an alkyl group, in particular R 2, R 4 and R 5 independently of one another represent an H Atom or a C1 to C4 alkyl group. Most preferably, R2, R4 and R5 are each an H atom. n is preferably 1.
  • Preferred anions are selected from the group of the alkyl or aryl sulfates, in particular of the formula R a OSO 3 -,
  • R a is a C 1 to C 12 alkyl group or a C 5 to C 12 aryl group, preferably a C 1 to C 6 alkyl group or a C 6 aryl group (tosylate), the alkylsulfonates, in particular the formula R a SO 3 -;
  • R a is a C 1 to C 12 alkyl group, preferably a C 1 -C 6 alkyl group, halides, in particular chloride, bromide or iodide and the pseudohalides, such as thiocyanate, dicyanamide, the carboxylates R a COO-;
  • R a is a C1 to C20 alkyl group, preferably a C1-C8 alkyl group, in particular acetate, and the phosphates and phosphonates, especially those of the above formula II.
  • Preferred anions are methanesulfonate, tosylate, trifluoromethanesulfonate, dimethyl phosphate, diethyl phosphate, monoalkylphosphonates, methylsulfate, ethylsulfate, thiocyanate or dicyanamide and the above carboxylates.
  • the ionic liquid very particularly preferably has a phosphorus-containing anion, preferably a phosphate or phosphonate, in particular those of the above formula II.
  • Very particularly preferred ionic liquids are those from an imidazolium cation of the formula II and an anion of the formula II, in short imidazolium phosphates and imidazolium phosphonates.
  • other solvents i. at 20 ° C, 1 bar liquid compounds.
  • alcohols or ketones such as acetone, methanol, ethanol or dioxane, or dimethyl sulfoxide, dimethylacetamide, formamide, N-methylmorpholine-N-oxide or dichloromethane.
  • Cellulose is reacted under a) with a phosphorus-containing compound in the presence of an ionic liquid.
  • the cellulose is dissolved or suspended in a solvent containing the ionic liquid.
  • the solvent may contain, in addition to the ionic liquid, other solvents, e.g. those listed above.
  • the solvent is preferably at least 25% by weight, more preferably at least 60% by weight and most preferably at least 80 or 95% by weight of ionic liquid. In a particular embodiment, it is exclusively ionic liquid.
  • the cellulose, the solvent and the phosphorus-containing compound are preferably brought into contact with each other at an elevated temperature, so that a solution or suspension of the cellulose and the phosphorus-containing compound is formed in the solvent and the reaction takes place in this solution or suspension.
  • the temperature is preferably 20 to 150 ° C, especially 40 to 130 ° C, and more preferably 70 to 120 ° C.
  • An increase in pressure or a pressure reduction is not required, therefore, the preparation of the solution or suspension and the reaction is generally carried out at atmospheric pressure.
  • no further phosphorus-containing compounds need to be included.
  • ionic liquid and phosphorus-containing compound are identical and cellulose is reacted in step a) with the anion of the ionic liquid.
  • the reaction of the cellulose with the phosphorus-containing anion of the ionic liquid proceeds very simply and quickly. Aside from the ionic liquid containing the phosphorus-containing anion, it is, of course, also possible to use further phosphorous-containing compounds, but this is not necessary.
  • the amount of solvent is preferably 200 to 5000 parts by weight, more preferably 500 to 1200 parts by weight per 100 parts by weight of cellulose.
  • the amount of phosphorus-containing compound is generally chosen so that the desired degree of substitution with the phosphorus compound is achieved.
  • the solution or suspension and reaction under process step a) can be carried out in suitable apparatus. Due to the possibly high viscosity, kneaders or other mixing apparatus are also suitable here. Also suitable are thin film evaporators in which a mixture of cellulose, the solvent and optionally a non-solvent, such as. Water is distributed by a rotor in a thin layer on the inner surface of a tube and the non-solvent is distilled off under vacuum if necessary, with heating.
  • the cellulose obtained in process step a) (P-cellulose for short) preferably has a degree of substitution of 0.001 to 3, in particular from 0.005 to 1, very particularly preferably from 0.01 to 0.05, wherein this degree of substitution is substituted only for those substituted with the phosphorus compound Hydroxyl groups of cellulose refers. It is therefore in particular cellulose cellulose or cellulose phosphonate with the above degree of substitution of phosphate or phosphonate.
  • the P-cellulose obtained in process step a) preferably has a phosphorus content of at least 0.1 to 5% by weight, in particular from 0.4 to 2% by weight, calculated in grams of phosphorus per 100 grams of total weight of P-cellulose.
  • the obtained in a) P-cellulose is converted into a cellulose fiber.
  • P-cellulose or else P-cellulose can be converted into a fiber in a mixture with other celluloses or other fiber-forming compounds.
  • Preferred cellulose fibers are fibers which contain more than 40% by weight, in particular more than 60% by weight, particularly preferably more than 90% by weight, of P-cellulose, based on all fibers constituents (such as other cellulose or lignin).
  • the cellulose fibers consist of more than 98% by weight, very particularly preferably 100% by weight of P-cellulose, based on all fiber-forming constituents.
  • Cellulose fibers are generally through
  • the P-cellulose can be separated and then converted by the above method, optionally in admixture with other celluloses, into a cellulose fiber.
  • Viscose fibers produced by the viscose process are Viscose fibers produced by the viscose process
  • Lyocell® fibers made from a spinning solution containing NMMO (N-methylmorpholine-N-oxide) as a solvent, or
  • Cellulose fibers which are obtained from spinning solutions with ionic liquid as a solvent, as z. As described in WO 2007/076979, available.
  • the solution or dispersion obtained under a) is optionally further solvent, in particular further ionic liquid added until the P-cellulose is completely dissolved (spinning bath). If desired, it is additionally possible to add other cellulose as well.
  • the spin bath customary spin additives, z. As matting agents, graphite, carbon black, Carbonanotubes be added.
  • Preferred spinning baths have z.
  • the following composition :
  • Particularly preferred spinning baths have the following composition: 3 to 15% by weight of P-cellulose
  • the production of cellulose fibers from these spinning baths can be carried out by conventional methods.
  • the cellulose fiber is recovered from the spinning bath by coagulation of the cellulose in the form of a fiber.
  • the cellulose fiber obtained in b) can be dried and stored and then converted into a carbon fiber.
  • the cellulose fiber obtained in b) can also be equipped with further additives. In a preferred embodiment, this is done without drying the cellulose fiber obtained in b).
  • the cellulose fiber obtained in b) can be brought into contact with the additives directly after washing with water, before the water content of the cellulose fiber has fallen below 20% by weight, in particular from 50% by weight of water to 100 parts by weight of cellulose.
  • Such a process is described in European Patent Application Serial No. 14168572.7 (PF 76706). Thereafter, drying and storage of the cellulose fiber equipped with additives can again take place.
  • a drying of the cellulose fiber can, for. B. at temperatures of 50 to 300 ° C are performed.
  • Cellulose fiber can be converted to a carbon fiber by known methods of pyrolysis.
  • the pyrolysis is generally carried out at temperatures of 500 to 1600 ° C. It can, for example, under air or under inert gas, for. As nitrogen or helium are performed. Preferably, it is carried out under a protective gas.
  • the cellulose fiber can be dried. For already dried and stored cellulose fibers, the drying may optionally be repeated.
  • 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.
  • the temperature can be increased gradually or continuously.
  • drying may take place in two or more stages, 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 and 10 to 500 seconds in total during the drying.
  • pyrolysis may be considered, in which the temperature is continuously increased, e.g. Starting from 200 ° C until 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 of 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 percent by weight of the carbon contained in the cellulose fiber.
  • the resulting carbon fiber has very good mechanical properties, in particular good strength and elasticity.
  • Example 1 Preparation of cellulose fiber from unmodified cellulose
  • the solution is spun in a dry-wet spinning plant. It is tempered to 65 ° C and with the help of a piston through the spinneret (nozzle hole number: 48, hole diameter: 90 ⁇ ) in a 1 to 5 cm long air gap and an underlying coagulation bath pressed.
  • the delivery rate is 1.65 cm 3 / min.
  • the coagulation bath consists of 50% water and 50% methanol or 100% water.
  • the forming fiber is removed after the coagulation of a godet at 3 m / min and washed in a washing bath at 100 ° C. Then it is dried at 120 ° C on a Bankgalette, wherein the withdrawal speed is 5 m / min. The dried fiber is wound up on spools.
  • Cellulose fiber The P content is 1 .4%, the N content is 1.2%. The fiber fineness is 2.5 dtex. The elongation is 10%, the fineness-related force 20 cN / tex and the E-modulus 1002 cN / tex.
  • Example 2 Production of Cellulose Fiber from Unmodified Cellulose
  • a 12% solution is prepared using a thin film evaporator.
  • the spinning mass is filtered before further processing through a metal filter fabric with a mesh size of 42 ⁇ .
  • the solution is spun analogously to Example 1 in a dry-wet spinning plant (spinning temperature: 80 ° C, nozzle hole number 168, hole diameter: 90 ⁇ ).
  • Cellulose fiber The P content is 1%.
  • the fiber fineness is 3 dtex.
  • the elongation is 6%, the fineness-related force 25 cN / tex and the modulus of elasticity 906 cN / tex
  • Example 3 Preparation of a cellulose fiber from modified cellulose
  • the solution prepared in this way is spun in a dry-wet spinning machine in a manner analogous to Example 1 (spinning temperature: 90 ° C., nozzle hole number: 168, hole diameter: 90 ⁇ m).
  • Cellulose fiber 0.3% P, 0.2% S, The fiber fineness is 2.2 dtex. The elongation is 7%, the fineness-related force 18 cN / tex and the modulus of elasticity 929 cN / tex
  • Example 4 Carbonization of the fibers from Example 1
  • the precursor fiber produced according to Example 1 is carbonized under protective gas in a chamber furnace.
  • the following carbonization program is used: RT - 160 ° C, 1 K / min; Isotherm at 160 ° C for 30 min; 160-400 ° C, 10 K / min; 400 ° C - 1 100 ° C, 3.3 K / min. Carbonization yield 32-35%.
  • Carbon fiber The fibers have a fineness of 1.5 dtex, 2% elongation, a strength of 0.7 GPa and an E-modulus of 42 GPa.
  • Example 5 Carbonization of the fibers from Example 2
  • the precursor fiber prepared according to Example 2 is carbonized as described in Example 4, at a final temperature of 1400 ° C. Carbonization yield 31%.
  • Carbon fiber The fibers have a fineness of 1.6 dtex, 1.4% elongation, a strength of 0.64 GPa and an E modulus of 44 GPa.
  • Example 6 Carbonization of the fibers from Example 3
  • the precursor fiber prepared according to Example 3 is carbonized as described under Example 4 at a final temperature of 1100 ° C. Carbonization yield 32%.
  • Carbon fiber The fibers have a fineness of 1.2 dtex, 1.6% elongation, a strength of 0.8 GPa and an E-modulus of 45 GPa.
  • Example 7 Carbonization of an unmodified, conventional cellulose fiber
  • the unmodified, conventional cellulose fiber is carbonized analogously to Example 4 to a final temperature of 1400 ° C.
  • Carbon fiber The fibers are brittle and brittle, their textile mechanical properties can not be determined.
  • Example 8 Carbonation of a finished viscose fiber
  • a standard textile viscose fiber is subsequently equipped with ammonium hydrogen phosphate via an aqueous bath. After drying, the phosphorus content is adjusted to 1% by weight.
  • the screed viscose fiber is carbonized as in Example 4.
  • Carbon fiber The fibers are brittle and brittle, their textile mechanical properties can not be determined.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)

Abstract

Procédé de production de fibres de carbone à partir de fibres de cellulose, caractérisé en ce que: a) de la cellulose est mise à réagir avec un composé de phosphore en présence d'un liquide ionique pour obtenir une cellulose contenant du phosphore (p-cellulose); b) la p-cellulose est transformée en fibre de cellulose; et c) la fibre de cellulose est transformée en fibre de carbone.
PCT/EP2015/076132 2014-11-20 2015-11-10 Procédé de production de fibres de carbone à partir de fibres de cellulose contenant du phosphore WO2016078960A1 (fr)

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Application Number Priority Date Filing Date Title
DE212015000267.5U DE212015000267U1 (de) 2014-11-20 2015-11-10 Carbonfasern aus Phosphor enthaltenden Cellulosefasern

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EP14194119 2014-11-20
EP14194119.5 2014-11-20

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WO2016078960A1 true WO2016078960A1 (fr) 2016-05-26

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US10618873B2 (en) 2016-02-01 2020-04-14 Basf Se Method for producing C4-C15 lactams
CN113151936A (zh) * 2021-03-24 2021-07-23 湖北文理学院 一种表面呈均匀球凸的碳纤维及其制备方法

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WO2007076979A1 (fr) 2005-12-23 2007-07-12 Basf Se Solution a base de liquides ioniques fondus, sa fabrication et son utilisation pour la fabrication d'hydrates de carbone regeneres
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CN101871140A (zh) 2009-04-24 2010-10-27 李桂云 离子基碳纤维
WO2012156441A1 (fr) 2011-05-18 2012-11-22 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Procédé de production de préfibres contenant de la lignine ainsi que de fibres de carbone
WO2014029748A1 (fr) * 2012-08-22 2014-02-27 Deutsche Institute Für Textil- Und Faserforschung Denkendorf Fibres de cellulose filées directement, leur fabrication et leur utilisation

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10618873B2 (en) 2016-02-01 2020-04-14 Basf Se Method for producing C4-C15 lactams
CN113151936A (zh) * 2021-03-24 2021-07-23 湖北文理学院 一种表面呈均匀球凸的碳纤维及其制备方法

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