WO2013020919A1 - Fibres de précurseur à base de matières premières renouvelables - Google Patents

Fibres de précurseur à base de matières premières renouvelables Download PDF

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Publication number
WO2013020919A1
WO2013020919A1 PCT/EP2012/065255 EP2012065255W WO2013020919A1 WO 2013020919 A1 WO2013020919 A1 WO 2013020919A1 EP 2012065255 W EP2012065255 W EP 2012065255W WO 2013020919 A1 WO2013020919 A1 WO 2013020919A1
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WO
WIPO (PCT)
Prior art keywords
lignin
glucan
derivative
pan
point
Prior art date
Application number
PCT/EP2012/065255
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German (de)
English (en)
Inventor
Hubert JÄGER
Michael Heine
Franz Effenberger
Original Assignee
Sgl Carbon Se
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 Sgl Carbon Se filed Critical Sgl Carbon Se
Publication of WO2013020919A1 publication Critical patent/WO2013020919A1/fr

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Classifications

    • 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
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
    • 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
    • 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
    • D01F9/17—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 from lignin
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles

Definitions

  • the present invention relates to precursor fibers, a process for
  • Carbon fibers are characterized by a very high tensile strength at a very low weight and are also very resistant to chemicals and high temperatures. For this reason, carbon fibers are used in a variety of technical fields, such as in the aerospace, medical and automotive industries.
  • Carbon fibers are usually prepared by first spun from a carbonaceous starting material, such as polyacrylonitrile, pitch or viscose, Precursormaschinen or green fibers, which are subsequently subjected to stabilization and then converted by carbonization and / or graphitization in carbon fibers.
  • the stabilization of the precursor fibers is carried out, for example, in air at a temperature between 200 and 300 ° C.
  • carbon fibers produced from viscose have a comparatively poor carbon structure and therefore a comparatively low thermal and electrical conductivity, which is why these are used primarily as heavy-duty insulating materials
  • the carbon fibers produced from pitch and polyacrylonitrile have high tensile strengths and moduli of elasticity based carbon fibers have a slightly higher modulus of elasticity, but a slightly lower tensile strength than the polyacrylonitrile-based carbon fibers.
  • such carbon fibers for example, the carbon fibers prepared from lignin precursor fibers as described above, have tensile strengths of about 1,000 to 2,000 MPa and flexural moduli of about 100 to 150 GPa, which are about two to three times lower than the tensile strengths and flexural modulus of polyacrylonitrile Precursor fibers made of carbon fibers.
  • cellulosic and lignin precursor fibers are also distinguished by the disadvantage that with carbonylation only a very large proportion of them are present low carbon yield is achieved.
  • chanical properties in particular with a high tensile strength and with a high modulus of elasticity, can be processed.
  • this object is achieved by a precursor fiber which contains polyacrylonitrile and at least one polymer selected from the group consisting of lignin, lignin derivatives, glucans, cellulose and any desired mixtures of two or more of the abovementioned compounds.
  • precursor fibers consist of a binary, ternary or quaternary mixture of poly acrylonitrile and one, two or three sustainable polymers selected from the group consisting of lignin, lignin derivatives and glucans, cellulose despite the content of sustainable starting materials - in contrast to the well-known, on the use of sustainable raw materials based carbon fiber production process - carbon fibers with an excellent carbon structure which is free or at least nearly free of defects, and therefore can be made into carbon fibers having excellent tensile strength and modulus of elasticity.
  • the precursor fibers according to the invention thus combine the advantages of pure polyacrylonitrile precursor fibers, namely the processability to carbon fibers having a high tensile strength and a high modulus of elasticity, with the advantages of known lignin and cellulose precursor fibers, namely high sustainability, while avoiding the disadvantages of polyacrylonitrile Precursor fibers and the known cellulose and lignin precursor fibers. For this reason, the precursor fibers according to the invention are environmentally friendly and resource-saving.
  • carbon fibers with a tensile strength of up to 3,500 MPa and with a flexural modulus of up to 450 GPa can be produced from the precursor fibers according to the invention, ie with mechanical properties which correspond to or at least almost correspond to those of carbon fibers based on pure polyacrylonitrile precursor fibers.
  • the precursor fiber is at least 80 wt .-%, preferably at least 90 wt .-%, more preferably at least 95 wt .-%, particularly preferably at least 98 wt .-%, most preferably at least 99% by weight and most preferably entirely of a mixture of polyacrylonitrile and at least one polymer selected from the group consisting of lignin, lignin derivatives, glucans, cellulose and any of mixtures of two or more of the aforementioned compounds.
  • the Precursormaschine contains apart from any impurities and the aforementioned polymers no further ingredients and in particular - apart from polyacrylonitrile - no petroleum-based polymer, so in particular no pitch.
  • the precursor fiber of the invention should be at most 50% by weight, preferably at most 40% by weight, more preferably at most 30% by weight and most preferably at most 20% by weight .-% polyacrylonitrile contains.
  • This embodiment is particularly advantageous in combination with the aforementioned embodiment, according to which the precursor fiber is completely composed of a mixture of polyacrylonitrile and at least one polymer selected from the group consisting of lignin, lignin derivatives, glucans, cellulose and any mixtures of two or more of the aforementioned compounds because the precursor fibers are then selected from a maximum of 50% by weight, preferably not more than 40% by weight, particularly preferably not more than 30% by weight and very preferably not more than 20% by weight of polyacrylonitrile and otherwise only one or more sustainable polymers the group consisting of lignin, lignin derivatives and glucans.
  • the precursor fiber according to the invention contains - except the polyacrylonitrile - no petroleum-based polymer, so in particular no pitch.
  • the known from the prior art precursor fibers of lignin or cellulose for industrial applications have insufficient mechanical properties and in particular unsatisfactory tensile strengths, it was particularly surprising that only a maximum of 50 wt .-%, preferably not more than 40 wt.
  • Precursorfaser can be processed by a conventional stabilization and carbonization or graphitization treatment to a carbon fiber with excellent tensile strength and with an excellent flexural modulus can be.
  • polyacrylonitrile is understood to mean any acrylonitrile homopolymer and any copolymer containing acrylonitrile groups.
  • copolymer generally refers to polymers which are composed of two or more monomers, that is to say in addition to binary copolymers, in particular also terpolymers, quaternary polymers and the like.
  • the precursor fiber according to the invention may contain as polyacrylonitrile any acrylonitrile homopolymer and any acrylonitrile copolymer, in particular a binary acrylonitrile copolymer or an acrylonitrile terpolymer, in particular those used for conventional polyacrylonitrile fibers.
  • Good results are obtained, for example, when the precursor fiber contains as polyacrylonitrile one or more acrylonitrile homopolymers having a weight-average molecular weight of 50,000 to 400,000 g / mol, and preferably from 120,000 to 250,000 g / mol.
  • the polyacrylonitrile contained in the precursor fiber according to the invention is a binary acrylonitrile copolymer or an acrylonitrile terpolymer, this preferably has an acrylonitrile content of at least 70% by weight, preferably of at least 80% by weight, particularly preferably of at least 85% by weight .-%, more preferably of at least 90 wt .-% and most preferably from 94 to 99 wt .-% to.
  • binary acrylonitrile copolymers and acrylonitrile terpolymers in particular, when the binary acrylonitrile copolymer or the acrylonitrile terpolymer contains, in addition to the acrylic monomer, one or two comonomers which are selected from the group prepared from acrolein, acrylamide, acrylates, acrylic acid, acrylic sulfonic acid and its salts, butyl 2- (1-hydroxy-methyl) -acrylate, ⁇ -chloroacrylonitrile, citraconic acid, crotonic acid, ethacrylic acid, hydroxyalkylacrylic compounds, 2- (1-hydroxybutyl) acrylonitrile, 2- (hydroxybutyl) acrylonitrile, 2- (1-hydroxyethyl) acrylonitrile, 2- (1-hydroxyethylhexyl) acrylonitrile, 2- (1-hydroxymethyl) acrylonitrile, isobutyl methacrylate (IBMA), itac
  • binary acrylonitrile copolymers which are composed of acrylonitrile and up to 6% by weight and preferably up to 2% by weight of a comonomer selected from itaconic acid, methacrylic acid, methyl acrylate and vinyl acetate.
  • acrylonitrile-acrylamide-methacrylic acid terpolymers having an acrylonitrile content of at least 96% by weight, acrylonitrile-methacrylic acid copolymers having an acrylonitrile content of at least 98% by weight, acrylonitrile-itaconic acid copolymers having an acrylonitrile content of at least 99% by weight, acrylonitrile-methyl acrylate copolymers having an acrylonitrile content of at least 95% by weight, acrylonitrile-acrylamide-methacrylate terpolymers having a Acrylitrile content of at least 95% by weight, acrylonitrile-methacrylate
  • the binary acrylonitrile copolymers or acrylonitrile terpolymers preferably also have a weight-average molecular weight of from 50,000 to 400,000 g / mol and more preferably from 120,000 to 250,000 g / mol.
  • the precursor fiber according to the invention may in principle contain any glucan, that is to say each polysaccharide composed only of D-glucose molecules linked together by glycosidic bonds.
  • the at least one glucan contained in the precursor fiber comprise at least 80% by weight, more preferably at least 90% by weight and most preferably at least 95% by weight of a 4-glucosidically linked glucose residues is glucan.
  • the glucan is selected from the group consisting of starch, amylose, amylopectin and mixtures of two or three of the above compounds.
  • Starch and amylopectin are more preferred than amylose because the latter is water-soluble.
  • potato starch has proven to be particularly suitable, which is composed of about 20% by weight of amylose and about 80% by weight of amylopectin.
  • the present invention is not particularly limited. All types of lignin and lignin derivatives can therefore be used, regardless of their source. Thus, for example, hardwood ligines, softwood lignins and grass lignins are equally suitable for the present invention. Also, with respect to the lignin recovery method or lignin digestion method with which the natural source-derived lignin is digested, the present invention is not limited.
  • lignin or lignin derivative it is possible, for example, to use those obtained by a sulphate or kraft process (hereinafter called kraft lignin or alkali lignin) obtained by a sulphite process (hereinafter referred to as lignin sulphonate), which obtained by an organosolv method (hereinafter referred to as organosolv lignin) obtained by a soda-AQ method obtained by the GRANIT method, which was obtained by the Alcell TM method and which was carried out with the organocell TM Procedures were won. Good results are obtained in particular with Kraft lignins, lignin sulphonates and organosolv lignins. While Kraft lignin preferably has a weight average molecular weight of 2,000 to
  • the precursor fiber is composed of a polymer mixture which consists of more than 0 to 50 wt .-%, preferably more than 2 to 40 wt .-%, particularly preferably 5 to 30 wt .-% and most preferably 5 to 20 wt .-% polyacrylonitrile and the remainder of glucan or cellulose.
  • This embodiment is thus a precursor fiber consisting of a binary polymer mixture of polyacrylonitrile and glucan, the glucan content of the polymer mixture being at least 50% by weight, preferably at least 60% by weight, particularly preferably at least 70% by weight. and most preferably at least 80 wt .-% is.
  • the precursor fiber is composed of a polymer mixture which consists of more than 0 to 50 wt .-%, preferably 2 to 40 wt .-%, particularly preferably 5 to 30 wt .-% and 5 to 20% by weight of polyacrylonitrile and the remainder lignin and / or lignin derivative are very particularly preferred.
  • This embodiment is thus a precursor fiber consisting of a binary polymer mixture of polyacrylonitrile and lignin (derivative), the lignin (derivative) content of the polymer mixture being at least 50% by weight, preferably at least 60% by weight, particularly preferably at least 70 wt .-% and most preferably at least 80 wt .-% is.
  • the precursor fiber is composed of a polymer mixture which consists of more than 0 to 50 wt .-%, preferably 2 to 40 wt .-%, particularly preferably 5 to 30 wt .-% and most particularly preferably 5 to 20% by weight of polyacrylonitrile, more than 0 to 99% by weight, preferably 30 to 99 wt .-% and particularly preferably 50 to 99 wt .-% lignin and / or lignin derivative and the remainder glucan.
  • This embodiment is thus a precursor fiber consisting of a ternary polymer mixture of polyacrylonitrile, glucan and lignin (derivative), the lignin (derivative) content of the polymer mixture preferably being at least 30% by weight and particularly preferably at least 50% by weight.
  • Wt .-% is.
  • the precursor fiber is composed of a ternary polymer mixture of i) polyacrylonitrile, ii) glucan and iii) lignin or lignin derivative, the mole fractions of components i), ii) and iii) being within a range of is defined in a ternary diagram by a polygon bounded by the points A, B, C and D, where
  • the precursor fibers according to the present invention can be prepared by all processes known to the person skilled in the art, for example by dry spinning, melt spinning, solution wet spinning, electrospinning, or wet spinning.
  • the precursor fiber is obtainable by wet spinning a spinning solution which is polyacrylonitrile, at least one polymer selected from the group consisting of lignin, lignin derivatives, glucans, cellulose and any mixtures of two or more of the aforementioned
  • Such precursor fibers can be made by conventional stabilization and carbonization and / or graphitization comprehensive process to carbon fibers with particularly good mechanical properties, which have an excellent carbon structure without or at least almost no defects. show, be processed.
  • the solvent diffuses out of the forming precursor fiber in a controlled manner, so that a clean fiber with a morphology that is round in cross-section is obtained.
  • a skin forms on contact with the warm gas phase, resulting in an initially swollen filament which, after the solvent has diffused out converts to a kidney-shaped in cross-section fiber.
  • the density of the precursor fiber is 1 to 1.5 g / cm 3 , preferably about 1.2 g / cm 3 , the crystallinity of the precursor fiber 15 to 25% and preferably about 20% and the average diameter the precursor fiber is less than 10 ⁇ .
  • a further subject of the present invention is a method for producing a precursor fiber, which comprises the following steps:
  • spinning in process step b) preferably takes place by wet spinning.
  • any solvent which has sufficient solubility to give a clear and homogeneous solution with the desired polymer constituents in the desired amounts can be used in the process according to the invention for producing the spinning solution.
  • a solvent which is selected from the group consisting of dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dimethylacetamide (DMAc), N-methyl-2 pyrrolidone (NMP), N-methylmorpholine N-oxide (NMMO), ionic liquids, especially 1-ethyl-3-methylimidazolium chloride (EMICI), N-methylimidazole, alkylphosphonium salts, alkylphenylsulfonate salts and any mixtures of two or more of the foregoing consists.
  • a solvent which is selected from the group consisting of DMSO, DMF, DMAc, NMP, NMMO, EMICI and any desired mixtures of two or more of the abovementioned compounds, DMSO, DMF, DMAc and any mixtures of two or more of the aforementioned compounds are most preferred and DMSO, a mixture of DMSO and DMF and a mixture of DMSO and DMAc are most preferred.
  • the spinning solution prepared in step a) may also be added with one or more additives, such as a wetting agent and / or compatibilizer.
  • a spinning solution in process step b) which has a total polymer content of from 5 to 40% by weight, preferably from 10 to 25% by weight and more preferably from 15 to 20% by weight ,
  • the spinning solution it is preferable not to combine the individual polymer constituents in solid form and then to dissolve this polymer mixture in a solvent, but to mix the individual polymer constituents together in each case in the form of a solution.
  • the solids and solvents can be stirred together for example for several hours at elevated temperature, for example 50 to 90 ° C.
  • step b it is preferable to filter the spinning solution prepared in step a) before spinning according to step b), with good results with a mesh filter of this type of a maximum of 5 ⁇ be obtained. Filtration is preferably carried out at a pressure of several bar.
  • the precursor fiber thus produced may be subjected to a post-treatment comprising, for example, one or more of the washing, drying and stretching steps.
  • the present invention relates to a carbon fiber which is obtainable from a previously described inventive precursor fiber.
  • the carbon fiber has a measured according to DIN EN 1007 Part 4 tensile strength of at least 2,000 MPa, preferably of at least 2,500 MPa and more preferably of at least 3,000 MPa, for example from 3,000 MPa to 3,500 MPa.
  • the carbon fiber has a flexural modulus measured according to DIN EN 1007 part 4 of at least 150 GPa, preferably of at least 250 GPa and more preferably of at least 350 GPa, for example of 350 to 450 GPa.
  • the carbon fiber according to the invention may have a density of 1, 75 to 1, 85 g / cm 3 and a fiber diameter of 6 to 10 ⁇ .
  • the present invention also includes carbon fibers having a smaller fiber diameter than 6 ⁇ m, in which connection reference is made to DE 10 201 1079 506, the description of which is hereby incorporated by reference and is part of the present disclosure.
  • the present invention relates to a method for producing a previously described carbon fiber, which comprises the following steps:
  • the stabilization of the precursor fiber according to method step c) is preferably carried out in air at a temperature of 200 to 300 ° C.
  • the carbonation in the process step d) takes place under non-oxidizing conditions at a temperature of 800 to
  • the precursor fiber in the process step d) is graphitized under non-oxidizing conditions at a temperature of 1,500 to 3,000 ° C. and preferably of 2,000 to 2,500 ° C.
  • Fig. 1 is a ternary diagram for the components polyacrylonitrile
  • PAN starch and lignin, in which a range of quantities preferred for a ternary precursor is marked constituent parts according to an embodiment of the present invention
  • Fig. 2 is a ternary diagram for the components PAN, starch and
  • Lignin in which a preferred for a ternary Precursormaschine mixture amount range of these ingredients according to another embodiment of the present invention is marked.
  • 1 and 2 ternary diagrams for mixtures of PAN, starch and lignin are reproduced, in each of which a preferred according to the present invention for a ternary Precursermaschine of i) polyacrylonitrile, ii) glucan and iii) lignin or lignin derivative range for relative mole fractions of these three constituents is marked.
  • the preferred ranges are limited by a polygon, which is defined by the lines connecting the points A, B, C and D.
  • the lignin may also be replaced by a cellulose.

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

Abstract

L'invention concerne une fibre de précurseur qui contient un mélange polymère de i) polyacrylonitrile, ii) a-1,4-glucane et iii) lignine et/ou dérivé de lignine. Cette fibre de précurseur peut être traitée par carbonisation et/ou graphitage pour donner une fibre de carbone ayant une résistance à la traction très élevée et un excellent module de flexion.
PCT/EP2012/065255 2011-08-05 2012-08-03 Fibres de précurseur à base de matières premières renouvelables WO2013020919A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE201110080548 DE102011080548A1 (de) 2011-08-05 2011-08-05 Precursorfasern auf Basis von nachwachsenden Rohstoffen
DE102011080548.6 2011-08-05

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WO2013020919A1 true WO2013020919A1 (fr) 2013-02-14

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CN103774276A (zh) * 2014-01-13 2014-05-07 东华大学 采用物理共混制备木质素/聚丙烯腈共混熔纺纤维的方法
WO2014161019A1 (fr) * 2013-04-05 2014-10-09 Lenzing Ag Fibres en polysaccharides et leur procédé de fabrication
RU2604620C1 (ru) * 2015-07-15 2016-12-10 Федеральное государственное бюджетное учреждение науки Институт высокомолекулярных соединений Российской академии наук Способ получения композиционного волокнистого адсорбента
US9701800B2 (en) 2013-04-10 2017-07-11 Lenzing Aktiengesellschaft Polysaccharide film and method for the production thereof
US10030323B2 (en) 2013-04-05 2018-07-24 Lenzing Aktiengesellschaft Method for the production of polysaccharide fibers with an increased fibrillation tendency
US10196758B2 (en) 2013-06-18 2019-02-05 Lenzing Aktiengesellschaft Polysaccharide fibers and method for producing same
US10220111B2 (en) 2013-06-17 2019-03-05 Lenzing Aktiengesellschaft Highly absorbent polysaccharide fiber and use thereof
WO2023225010A1 (fr) * 2022-05-16 2023-11-23 North Carolina State University Filage à l'état fondu de fibres de lignine/acrylique

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CN103993382B (zh) * 2014-05-30 2016-06-08 东华大学 一种通过物理共混提高聚丙烯腈纤维预氧化速度的方法

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JPH05195324A (ja) * 1992-01-21 1993-08-03 Toray Ind Inc 炭素繊維製造用プリカーサーおよびその製造法
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WO2014161019A1 (fr) * 2013-04-05 2014-10-09 Lenzing Ag Fibres en polysaccharides et leur procédé de fabrication
CN105074063A (zh) * 2013-04-05 2015-11-18 连津格股份公司 多糖纤维及其制备方法
US10030323B2 (en) 2013-04-05 2018-07-24 Lenzing Aktiengesellschaft Method for the production of polysaccharide fibers with an increased fibrillation tendency
US10221502B2 (en) 2013-04-05 2019-03-05 Lenzing Aktiengesellschaft Polysaccharide fibers and method for the production thereof
US9701800B2 (en) 2013-04-10 2017-07-11 Lenzing Aktiengesellschaft Polysaccharide film and method for the production thereof
US10220111B2 (en) 2013-06-17 2019-03-05 Lenzing Aktiengesellschaft Highly absorbent polysaccharide fiber and use thereof
US10196758B2 (en) 2013-06-18 2019-02-05 Lenzing Aktiengesellschaft Polysaccharide fibers and method for producing same
CN103774276A (zh) * 2014-01-13 2014-05-07 东华大学 采用物理共混制备木质素/聚丙烯腈共混熔纺纤维的方法
RU2604620C1 (ru) * 2015-07-15 2016-12-10 Федеральное государственное бюджетное учреждение науки Институт высокомолекулярных соединений Российской академии наук Способ получения композиционного волокнистого адсорбента
WO2023225010A1 (fr) * 2022-05-16 2023-11-23 North Carolina State University Filage à l'état fondu de fibres de lignine/acrylique

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