EP2636774B1 - Fibres de régénération cellulosiques et leur procédé de fabrication - Google Patents

Fibres de régénération cellulosiques et leur procédé de fabrication Download PDF

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Publication number
EP2636774B1
EP2636774B1 EP13000476.5A EP13000476A EP2636774B1 EP 2636774 B1 EP2636774 B1 EP 2636774B1 EP 13000476 A EP13000476 A EP 13000476A EP 2636774 B1 EP2636774 B1 EP 2636774B1
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European Patent Office
Prior art keywords
process according
weight
carbon nanoparticles
fibres
cellulose
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EP13000476.5A
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German (de)
English (en)
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EP2636774A1 (fr
Inventor
Bernhard Müller
Axel Russler
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Glanzstoff Bohemia sro
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Glanzstoff Bohemia sro
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    • 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
    • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • 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
    • 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
    • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • D01F2/08—Composition of the spinning solution or the bath
    • D01F2/10—Addition to the spinning solution or spinning bath of substances which exert their effect equally well in either

Definitions

  • the invention relates to a process for the production of cellulosic regenerated fibers by spinning from a cellulosic spinning solution admixed with anisotropic carbon nanoparticles, the dimension of which is greater in a particle main axis than in the orthogonal particle secondary axes, and on a cellulosic regenerated fiber produced in particular by this process.
  • a critical factor in the use of cellulosic fibers in the area of mechanically stressed workpieces and products is the tensile fiber elongation or the fiber-specific modulus of elasticity.
  • the viscose process in which cellulose in the form of high-quality pulps is converted to cellulose xanthate by means of alkalization and derivatization with CS 2 and this, in solution in sodium hydroxide in an acidic bath, in turn is regenerated to cellulose, is one of the oldest processes for regenerated cellulose production. It also makes it possible to produce fibers from non-spinnable forms of cellulose and, moreover, to impart to it special properties, in particular special mechanical and morphological properties, which in the case of natural spinnable forms of cellulose, eg. B. the seed hair of cotton, are not found.
  • the filament process as a special form of the viscose process is used to obtain endless, especially mechanically strong cellulose fibers. These fibers are used in particular as reinforcement and reinforcing material. Their main application can be found in the so-called tire cord, where they guarantee the strength and flexibility of the tire material, especially for particularly high-quality tires.
  • hybrid yarns In practical application, for this reason, so-called hybrid yarns must be produced if required by fibers with increased modulus, which in addition to the cellulosic fiber still contain a fiber with a particularly high modulus, in particular aramid is used.
  • the production of such hybrid fibers is expensive and expensive.
  • CFRPs carbon nanotubes
  • CMOS complementary metal-oxide-semiconductor
  • WO 2008/034 939 A1 relates to the production of electrically conductive fibers in the viscose process by the admixture of CNT or other nanoscale carbon species and uses for this purpose the effect that the conductivity of the materials with increasingly higher carbon contents increases, as it has long been known in the addition of conductive carbon black. In this case, relatively high admixtures are required. An influence on the mechanical properties is not considered.
  • the invention has for its object to provide a method of the type mentioned, can be obtained by the cellulosic regenerated without the need for subsequent production of hybrid yarns, but which achieve their mechanical properties.
  • this object is achieved in that the particle main axes are aligned by stretching the freshly spun, still plastic Regeneratmaschinen by at least 20% in accordance with an anisotropy direction parallel to the fiber direction.
  • the improvement of the mechanical properties takes place by means of additives.
  • the aggregates used are special carbon modifications that can be obtained through novel processes and whose industrial use is still limited but in strong growth.
  • These novel carbon species are carbon nanoparticles, which means that at least one of the particle dimensions is in the nanoscale range. Usually, this range is undershot defined by dimensions greater than 100 nm.
  • These nanoscale carbon bodies can roughly be divided into three groups, the carbon tubes (CNT, carbon nanotubes, single walled (SWCNT), double walled (DWCNT) and multi walled (MWCNT) and some other special forms with e.g. B. spiral appearance) with a fibrous form and a slightly different aspect ratio, spherical shaped bodies such as fullerenes and planar carbon species (graphenes), which can occur in one and several layers.
  • CNT carbon tubes
  • SWCNT single walled
  • DWCNT double walled
  • MWCNT multi walled
  • the surfaces of untreated carbon particles are usually hydrophobic due to their aromatic structure. This is not a problem if the particles of a likewise hydrophobic or aromatic embossed matrix, such as those found in many plastics, are to be incorporated. However, if the matrix chosen is of a hydrophilic character, as is the case with cellulose due to the OH groups contained in it thereby impairing the incorporation of the particles into the matrix and thus also the respective power transmission. As a result, the reinforcing potential of the admixture can not be fully exploited.
  • the carbon particles are surface-modified insofar as they carry groups by chemical reaction on their surface, which shift the character of the particles or their behavior from hydrophobic to hydrophilic.
  • Such modifications are possible in particular by the introduction of OH groups or COOH groups by targeted oxidation reactions.
  • the mentioned groups are able to interact with the OH groups of the cellulose and form hydrogen bonds.
  • a much better integration into the cellulose matrix is achieved, and the strength-increasing potential of the admixture can be utilized more favorably.
  • An additional positive side effect of a hydrophilic surface modification of the nanoscale carbon particles is their simplified dispersion in aqueous systems, as a result of which better results in the singulation of the particles are achieved or the mechanical and energy expenditure for sufficient dispersion decreases.
  • Another essential aspect of the invention described here is based on the strong stretching of the spun fiber in combination with a retarded coagulation and regeneration of cellulose xanthate dissolved in sodium hydroxide solution.
  • This retardation of the coagulation and in particular the regeneration process which is brought about for example by the addition of zinc salts, is a customary in the production of high-strength viscose fibers measure.
  • By stretching the freshly regenerated, but still plastic cellulose threads results in an alignment of the individual cellulose chains in the direction of orientation of the fiber produced. This happens a closer approximation of the individual cellulose chains by their molecular orientation and an increase in crystallinity.
  • Exemplary for the production of fibers by the process of the invention is the preparation of viscose from high purity sulphate pulp with an alpha-cellulose content of 97.9% by alkalization in caustic soda, pressing and pre-ripening, sulfidation with CS 2 and dissolving in sodium hydroxide, followed by filtration and degassing and ripeness of the viscose to obtain a spinnable solution.
  • This viscose is mixed with 0.1% MWCNT, based on the mass of cellulose in the viscose solution.
  • MWCNT based on the mass of cellulose in the viscose solution.
  • the appropriate amount of MWCNT is dispersed in an ultrasonic bath and, after successful homogeneous dispersion, mechanically stirred into the spinning mass until again a homogeneous dispersion is present.
  • the resulting MWCNT-containing dope is passed through spinnerets in a sulfuric acid-containing spinning bath and coagulated and regenerated there.
  • the resulting filaments are then directly stretched, washed, dried and wound.
  • the single drawing figure shows force-strain diagrams for three different fiber examples.
  • the short-dashed line labeled "0% CNT best” refers to a fiber without the addition of carbon nanoparticles.
  • the long-dashed or solid line denoted "0.1% CNT variant 1" and "0.1% CNT variant 2" relates to a fiber of the same composition with an addition of 0.1% by weight of CNT, with only the single-dispersion in the dope has been made in various ways.

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

Claims (20)

  1. Procédé de production de fibres cellulosiques régénérées par filage à partir d'une solution de filage cellulosique à laquelle sont ajoutées des nanoparticules de carbone anisotropes dont la dimension dans un axe principal de particule est plus importante que dans les axes secondaires de particule orthogonaux à ce dernier, caractérisé en ce que les axes principaux de particule sont orientés par étirage des fibres régénérées fraîchement filées encore plastiques selon une direction anisotrope parallèle à la direction des fibres, l'étirage des fibres étant d'au moins 20%.
  2. Procédé selon la revendication 1, caractérisé en ce que la teneur en nanoparticules de carbone de la solution de filage est d'au maximum 10 % en poids, notamment d'au maximum 5 % en poids, de préférence d'au maximum 2 % en poids, plus préférablement d'au maximum 1 % en poids et, de la manière la plus appropriée, d'au maximum 0,5 % en poids.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que la teneur en nanoparticules de carbone de la solution de filage est d'au moins 0,01 % en poids, notamment d'au moins 0,05 % en poids, de préférence d'au moins 0,1 % en poids et plus préférablement d'au moins 0,2 % en poids.
  4. Procédé selon l'une des revendications 1 à 3, caractérisé en ce que le procédé est mis en oeuvre en tant que procédé de production de viscose, notamment de fibres sans fin.
  5. Procédé selon l'une des revendications 1 à 4, caractérisé en ce que le procédé est mis en oeuvre dans deux bains de filage successifs sous la forme d'un procédé de filage à deux bains.
  6. Procédé selon l'une des revendications 1 à 5, caractérisé en ce que l'étirage des fibres s'effectue dans une plage allant jusqu'à 120 %, de préférence dans la plage de 40% à 100%.
  7. Procédé selon l'une des revendications 1 à 6, caractérisé en ce que les nanoparticules de carbone sont des nanotubes de carbone à une paroi, double paroi ou multi-paroi, ou bien des fullerènes ou du graphène.
  8. Procédé selon l'une des revendications 1 à 7, caractérisé en ce que les nanoparticules de carbone ne sont pas modifiées en surface.
  9. Procédé selon l'une des revendications 1 à 7, caractérisé en ce que les nanoparticules de carbone sont modifiées en surface.
  10. Procédé selon la revendication 9, caractérisé en ce que la modification de surface est due à l'introduction de groupes hydroxyle (OH-) ou de groupes carboxyle (COOH-).
  11. Procédé selon la revendication 9, caractérisé par une modification de surface d'un genre permettant un bon ancrage dans la matrice cellulosique grâce à la formation de forces intermoléculaires.
  12. Procédé selon la revendication 9, caractérisé par une modification de surface d'un genre permettant une liaison covalente à la cellulose.
  13. Procédé selon l'une des revendications 1 à 12, caractérisé en ce que la longueur des nanoparticules de carbone dans l'axe principal de particule se situe entre 5 nm et 250 nm.
  14. Procédé selon l'une des revendications 1 à 13, caractérisé en ce que la solution de filage est produite au moyen de pâtes à teneur élevée en α-cellulose, notamment supérieure à 94 %, de préférence supérieure à 97 %.
  15. Procédé selon l'une des revendications 1 à 14, caractérisé en ce que les nanoparticules de carbone ajoutées à la solution de filage sont réparties sans agrégats ni conglomérats.
  16. Fibre cellulosique régénérée présentant des nanoparticules de carbone anisotropes intégrées par filage dont la dimension dans un axe principal de particule est plus importante que dans les axes secondaires de particule orthogonaux à ce dernier, caractérisée en ce que les axes principaux de particule sont orientés selon une direction anisotrope parallèle à la direction des fibres.
  17. Fibre cellulosique régénérée selon la revendication 16, caractérisée en ce qu'elle est produite suivant un procédé selon l'une des revendications 1 à 14.
  18. Utilisation d'une fibre sans fin produite suivant un procédé selon l'une des revendications 1 à 15, mis en oeuvre sous la forme d'un procédé de production de filaments, et/ou d'une fibre cellulosique régénérée constituée sous la forme d'une fibre sans fin selon la revendication 16 en tant que matériau d'armure et de renfort et/ou dans une nappe tramée pour pneumatiques.
  19. Nappe tramée pour pneumatiques, caractérisée par une fibre cellulosique régénérée constituée sous la forme d'une fibre sans fin selon la revendication 16 et/ou suivant un procédé mis en oeuvre sous la forme d'un procédé de production de filaments selon l'une des revendications 1 à 15.
  20. Pneumatique, caractérisé en ce que le matériau du pneumatique présente une nappe tramée pour pneumatiques selon la revendication 19.
EP13000476.5A 2012-03-09 2013-01-31 Fibres de régénération cellulosiques et leur procédé de fabrication Active EP2636774B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE201210004807 DE102012004807A1 (de) 2012-03-09 2012-03-09 Cellulosische Regeneratfasern und Verfahren zu deren Herstellung

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EP2636774A1 EP2636774A1 (fr) 2013-09-11
EP2636774B1 true EP2636774B1 (fr) 2015-11-18

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106757790A (zh) * 2017-01-17 2017-05-31 国家纳米科学中心 一种抗氧化静电纺丝膜及其制备方法和应用

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2889400A1 (fr) * 2013-12-24 2015-07-01 SAPPI Netherlands Services B.V. Fibres ou filaments cellulosiques renforcés par des particules inorganiques et leur procédé de production
CN103866421B (zh) * 2014-02-25 2016-03-16 西安工程大学 一种防蚊再生纤维素纤维的制备方法
CN109505020B (zh) * 2018-12-12 2021-06-22 广东双虹新材料科技有限公司 一种含有线圈状碳纤维的粘胶纤维纺丝液、其制备方法及其粘胶纤维

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FR2805179B1 (fr) * 2000-02-23 2002-09-27 Centre Nat Rech Scient Procede d'obtention de fibres et de rubans macroscopiques a partir de particules colloidales, et notamment de nanotubes de carbone
DE10336473A1 (de) * 2003-08-08 2005-03-03 Degussa Ag Elektrisch leitfähige Kunststoffe
KR100595751B1 (ko) * 2004-11-11 2006-07-03 주식회사 효성 셀룰로오스 멀티 필라멘트의 제조방법
DE102006033591B4 (de) * 2006-07-18 2008-10-16 Thüringisches Institut für Textil- und Kunststoff-Forschung e.V. Verfahren zur Stabilisierung der Spinnlösung bei der Herstellung von cellulosischen Verbundformkörpern
US20100234503A1 (en) * 2006-08-10 2010-09-16 Khabashesku Valery N Polymer composites mechanically reinforced with alkyl and urea functionalized nanotubes
WO2008034939A1 (fr) 2006-09-04 2008-03-27 Natucell Ay Nanocomposites et matériaux hybrides comprenant des nanotubes de cellulose- carbone fonctionnalisés
FR2921075B1 (fr) * 2007-09-18 2010-03-12 Arkema France Procede continu d'obtention de fibres composites a base de particules colloidales et dispositif pour sa mise en oeuvre

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106757790A (zh) * 2017-01-17 2017-05-31 国家纳米科学中心 一种抗氧化静电纺丝膜及其制备方法和应用

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DE102012004807A1 (de) 2013-09-12
EP2636774A1 (fr) 2013-09-11

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