EP2268857B1 - Corps moulés cellulosiques - Google Patents

Corps moulés cellulosiques Download PDF

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Publication number
EP2268857B1
EP2268857B1 EP09725538A EP09725538A EP2268857B1 EP 2268857 B1 EP2268857 B1 EP 2268857B1 EP 09725538 A EP09725538 A EP 09725538A EP 09725538 A EP09725538 A EP 09725538A EP 2268857 B1 EP2268857 B1 EP 2268857B1
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EP
European Patent Office
Prior art keywords
cellulosic
cellulose
shaped bodies
solvent
filaments
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.)
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EP09725538A
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German (de)
English (en)
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EP2268857A1 (fr
Inventor
Britta Nicola Zimmerer
Kurt Uihlein
Frank Meister
Birgit Kosan
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Cordenka GmbH and Co KG
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Cordenka GmbH and Co KG
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.)
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Publication date
Application filed by Cordenka GmbH and Co KG filed Critical Cordenka GmbH and Co KG
Priority to PL09725538T priority Critical patent/PL2268857T3/pl
Priority to EP09725538A priority patent/EP2268857B1/fr
Publication of EP2268857A1 publication Critical patent/EP2268857A1/fr
Application granted granted Critical
Publication of EP2268857B1 publication Critical patent/EP2268857B1/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
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • 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
    • 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
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • 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 present invention relates to cellulosic moldings having a maximum tensile force of at least 30 cN / tex, prepared by dry-wet-forming polymer solutions containing predominantly cellulose in a solvent.
  • the present invention relates to so-called technical cellulose multifilament game, which are high-strength molded body made of cellulose with a proportion of less than 50% of other polymers and / or additives.
  • the dry-wet deformation is preferably carried out by precipitation.
  • the DE-A-4 444 140 in the claims solvent-spun cellulosic filaments of a solution of cellulose in a tertiary amine N-oxide and optionally water having a strength of 50 to 80 cN / tex and an elongation at break of 6 to 25%. From the corresponding examples, it can be seen, however, that with a maximum tensile strength or tear strength of 65.3 cN / tex, an elongation of 6.3% is associated and results in a tensile strength of 53.2 cN / tex, an elongation of 13%. Due to lack of feasibility, the claimed areas in the granted patent EP-B-0797694 then limited to a range of 52.7 to 66 cN / tex for the strength and 6 to 13% for the elongation.
  • the WO 2006/000197 discloses a process for the preparation of shaped articles of cellulose with ionic liquids as solvent, in which the cellulose is dissolved, the solution is shaped into fibers or membranes, the cellulose is regenerated by precipitation in aqueous solutions, the solvent is removed by washing and the shaped articles dries. According to WO 2006/000197 In this way fibers with very high tensile strengths and moduli in the conditioned and wet state are obtained. According to the table on page 17 of this prior publication, tensile strengths of up to 67.7 cN / tex in the conditioned state are achieved with simultaneous breaking elongations of 9.0%.
  • tear strength tensile strength, breaking strength and maximum tensile force are used interchangeably in this application and refer to the fineness-related force that has to be used for tearing or breaking the cellulosic molding.
  • the elongation of the molded article measured during tearing or breakage of the molded article is based on its original length and referred to as elongation at break, maximum tensile elongation at break or else elongation at break in the form of the percentage increase in length.
  • the shaped bodies according to the invention thus also show at the same time a very high tear strength and a high elongation at break, a combination which is not disclosed in the prior art.
  • Example 3 in the WO 2007/128268 For example, fibers of a (60:40) mixture of a cotton linter pulp with polyacrylonitrile are disclosed which have a working capacity of about 87 J / g.
  • the in the WO 2007/128268 fibers described at the same time have a very low strength of only 25.4 cN / tex and are therefore not suitable for use as technical multifilament yarns.
  • the WO 97/33020 shows a working capacity of 41 J / g at a distance between nozzle and godet of 12 m, 38 J / g at 25 m and 45.5 J / g at 48 m. An extrapolation to a distance of 0 would consequently result in a working capacity of approx. 50 to 60 J / g, as shown in Table 1 of the WO 97/33030 is shown.
  • WO 02/18682 From the published a few years later WO 02/18682 The skilled person can see that between the working capacity of the fibers (product of tensile strength and elongation at break in J / g) and the strain rate, although a dependency, this is low.
  • the WO 02/18682 contains - despite a corresponding reference to it - no drawings. If one looks in the corresponding priority application, one recognizes that even at an (extrapolated) strain rate of less than 5 sec -1 at the specified constant strength of about 41 cN / tex a working capacity of over 80 J / g would not be achieved.
  • the WO 02/18682 recommends spinning at a strain rate in the range of 15-40 sec- 1 , thus teaching WO 02/18682 a working capacity of about 58 to 65 J / g.
  • the maximum tensile force of the claimed molded articles is in a range of 40 to 90 cN / tex, preferably 45 to 85 cN / tex, more preferably 50 to 80 cN / tex, most preferably 55 to 75 cN / tex.
  • Suitable solvents are the known direct solvents for cellulose, such as N-methylmorpholine-N-oxide (NMMO), into consideration. It is likewise preferred if the solvent from which the cellulosic molded bodies are produced is an ionic liquid or mixtures of ionic liquids.
  • NMMO N-methylmorpholine-N-oxide
  • Preferred ionic liquids are those which have imidazolium-based cations and halide or acetate anions, in particular 1,3-dialkylimidazolium halides and acetates and more preferably the 1-butyl-3-methylimidazolium chloride and the 1-ethyl-3-one methylimidazolium acetate and / or mixtures thereof.
  • the cellulosic shaped bodies preferably consist of a pulp which has an ⁇ -cellulose content of greater than 90%, preferably greater than 96%, and particularly preferably greater than 98%.
  • the cellulose is a pulp which has an average degree of polymerisation (DP), determined by means of the cuoxam method, of> 600, preferably> 650.
  • DP average degree of polymerisation
  • the preparation of the cellulosic molded bodies according to the invention is preferably carried out by enzymatic and / or hydrolytic pretreatment of the pulps used. These pretreatments are used to widen the molecular weight distribution targeted, the molecular weights are reduced.
  • the discontinuity of the spinning solutions can also be adjusted by the targeted mixing of pulps and by the addition of secondary polymers.
  • the cellulosic shaped bodies are filaments or fibers.
  • These fibers or filaments preferably have a cuoxamide DP greater than 550, more preferably greater than 600.
  • the production of the moldings according to the invention succeeds excellently when the angular velocity (or the shear rate proportional thereto) at the "cross-over" is in a range from 0.5 to about 2 rad / sec. If the solvent used is NMMO, this angular velocity is preferably between about 1 and 2 rad / sec, for ionic liquids preferably between about 0.5 and 1.
  • the angular velocity at the "cross-over” corresponds to the width molecular weight distribution and the average molecular weight of the polymers involved in the interlocking network.
  • the "cross over” itself is the crossing point between the memory and loss modulus of the master curve (see: Schrempf, C .; Shield, G .; Rüf, H., "Pulp-NMMO solutions and their flow properties", Das Textil 12 (1995) 748-757 ).
  • the cellulosic shaped bodies are filaments, they preferably have a DP determined by means of Cuoxam of> 550.
  • the invention is therefore also directed to the use of such cellulosic filaments for the production of technical yarns and for the production of tire cords and of cords and textile reinforcement fabrics.
  • the cellulosic filaments of the present invention are particularly useful for reinforcing elastomers, plastics (e.g., thermoplastics, biopolymers, and biodegradable polymers) and thermosetting molding materials (resins).
  • the determination of the textile properties (strength, elongation, fineness) of the fibers and filaments was carried out in the test climate according to DIN 50014-20 / 65 at 20 ° C and 65% relative humidity.
  • the clamping length was 20 mm and the pulling speed was 20 mm / min with a preload weight of 0.6 ⁇ 0.06 cN / tex.
  • the measurements were carried out on 50 fibers each.
  • the rheological characterization of the cellulosic spinning solutions was carried out using a HAAKE MARS rheometer with a cone / plate measuring device (sensor C35 / 4 ° or C20 / 4 °).
  • Zero shear viscosities were measured by creep using a constant shear stress of 90 Pa at a measurement temperature of 85 ° C.
  • the determination of the average degree of polymerization (DP) of the cellulose was carried out by the Cuoxam method.
  • the ⁇ -cellulose content is the part of the pulp which is resistant to 17.5% sodium hydroxide solution in certain types of treatment.
  • the determination of the ⁇ -cellulose content was carried out by treating the pulp with 17.5% aqueous NaOH solution at 20 ° C for 1 h and then washing, drying and reweighing of the pulp.
  • the solids content was determined by precipitation, washing and drying of the cellulose.
  • a lyocell pulp (eucalyptus sulfite pulp, cuoxam DP: 556, ⁇ -cellulose content: 93.8%) was added 1:20 in water to a liquor ratio and pressed to a moisture content of 60% by mass.
  • the solution contains 11.2% by mass of cellulose and 88.8% by mass of BMIMCI, was analytically characterized and formed by dry-wet spinning into 1.73 dtex fibers.
  • the data of the analytical solution characterization, spinning conditions and fiber values are shown in the table.
  • a eucalyptus pulp (8% by mass of moisture, Cuoxam-DP: 556) are dispersed in a liquor ratio of 1:20 to the single fiber and then pressed to a water content of 60% by mass.
  • the cellulose which is moist by press, is introduced into 380 g of an N-methylmorpholine-N-oxide (NMMO) solution with a water content of 50%, which contains as stabilizers propyl gallate (0.03%, based on the polymer solution to be prepared) and sodium hydroxide solution according to the base consumption Contains substances, introduced and dispersed.
  • NMMO N-methylmorpholine-N-oxide
  • the prepared suspension is placed in a vertical kneader, under shear, increasing temperature of 70 to 95 ° C and decreasing pressure of 750 to 50 mbar the water removed to the level of monohydrate and a microscopically homogeneous cellulose solution having the composition 12.3 mass% Cellulose, 76.0% by mass of NMMO and 11.7% by mass of water.
  • the refractive index of the solution at 50 ° C was 1.4876.
  • the prepared solution was analytically characterized and formed by dry-wet spinning to 1.66 dtex fibers. The data of the analytical solution characterization, spinning conditions and fiber values are shown in the table.
  • the pulp used in Comparative Example 3 (Cuoxam DP: 798, 98.4% ⁇ -cellulose) was dispersed in water at a ratio of 1:20 in water and adjusted by the addition of dilute formic acid to a pH of 5.0.
  • an enzymatic pretreatment of the pulp was carried out within 60 minutes with 0.5% of a cellulase with high exoactivity (filter paper activity 90 U / ml), based on cellulose.
  • Enzymatic pretreatment provides only a small reduction in the cuoxam DP of the pulp to a DP of 745, as well as a targeted change in non-uniformity, i. the molecular weight distribution of cellulose.
  • the pulp suspension from the enzyme treatment is pressed after increasing the pH to 11 to a water content of 60% and in each case 78.1 g of this press-moist cellulose used to prepare 12.5% strength cellulose solutions in BMIMCI.
  • the polymer solutions were deformable with very good spinning reliability by means of dry-wet spinning technology into fibers of a fineness of 1.78 or 1.70 dtex.
  • the data of the analytical solution characterization, spinning conditions and fiber values are shown in the table.
  • blends of pulps having a narrow molecular weight distribution and high ⁇ -cellulose contents were prepared.
  • 23.9 g of a pulp (cuoxam-DP: 798, 98.4% ⁇ -cellulose, moisture content: 7%) and 10.1 g of a cotton linter pulp (cuoxam-DP: 443, 98% ⁇ -cellulose) were used.
  • the moist celluloses were suspended in BMIMCI solutions (water content: 30%, stabilizer addition 0.2% NaOH, 0.02% propyl gallate, based on the polymer solution to be prepared) and transferred by means of vertical kneader under dehydration by shear, temperature and vacuum into microscopically homogeneous spinning masses ,
  • the polymer solutions obtained were deformable with very good spinning reliability by means of dry-wet spinning technology into fibers of a fineness of 1.81 or 1.77 dtex.
  • the data of the analytical solution characterization, spinning conditions and fiber values are shown in the table.
  • Example 8 72.4 g of this pretreated, moist cellulose (water content: 60%) was thoroughly mixed with 1.52 g of polyethylene glycol 20000 (OH number: 4-7) and mixed with BMIMCl in a 12.2% by mass, transferred homogeneous dope.
  • the secondary polymers contained polyethylene glycol or polysiloxane each cause a very homogeneous turbidity of the spinning mass and are present in such a finely divided form that microscopically no individual particles could be identified and no adverse effects on the spinning processes took place.
  • the prepared polymer spun masses were characterized analytically and formed by dry-wet spinning process into fibers with finenesses of 1.97 and 1.73 dtex. The data of the analytical solution characterization, spinning conditions and fiber values are shown in the table.
  • the polymer solvent used was a mixture of 2 ionic liquids, BMIMCl and 1-hexyl-3-methylimidazolium chloride (HMIMCI) in a mass ratio of 90:10.
  • the polymer solvent used was a mixture of 2 ionic liquids, BMIMCI and 1-ethyl-3-methylimidazolium acetate (EMIMAc) in a mass ratio of 90:10.
  • a polymer solution was prepared analogously to Example 13 from a cellulose mixture of the pulps used in Example 13 in a mass ratio of 60:40, using as cellulose solvent a mixture of the ionic liquids BMIMCI and 1-butyl-3-methylimidazolium acetate (BMIMAc) in a mass ratio of 90:10.
  • BMIMCI 1-butyl-3-methylimidazolium acetate
  • a microscopically homogeneous polymer solution was obtained, which was 12.6 % By mass cellulose. This was characterized analytically and formed by dry-wet spinning process into fibers of a fineness of 1.72 dtex. The data of the analytical solution characterization, spinning conditions and fiber values are shown in the table.

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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)
  • Dispersion Chemistry (AREA)
  • Artificial Filaments (AREA)

Claims (12)

  1. Corps en cellulose obtenus par filage au solvant, dotés d'une résistance maximale en traction d'au moins 30 cN/tex, préparés par filage par voie hybride (sèche-humide) à partir d'une solution de polymère contenant principalement de la cellulose dans un solvant, caractérisés en ce que ces corps en cellulose présentent une capacité de travail, exprimée par le produit mathématique de la résistance maximale en traction par l'allongement au point de résistance maximale en traction, valant d'au moins 80 J/g à au plus 120 J/g.
  2. Corps en cellulose préparés conformément à la revendication 1, caractérisés en ce que leur résistance maximale en traction se situe dans l'intervalle allant de 30 à 90 cN/tex.
  3. Corps en cellulose préparés conformément à l'une ou plusieurs des revendications précédentes, caractérisés en ce que le solvant est un solvant direct, comme du N-oxyde de N-méthyl-morpholine (NMMO).
  4. Corps en cellulose préparés conformément à l'une ou plusieurs des revendications précédentes, caractérisés en ce que le solvant est un liquide ionique ou un mélange de deux liquides ioniques ou plus.
  5. Corps en cellulose préparés conformément à la revendication 4, caractérisés en ce que le liquide ionique est du chlorure de 1-butyl-3-méthyl-imidazolium ou de l'acétate de 1-éthyl-3-méthyl-imidazolium, ou un mélange de ceux-ci.
  6. Corps en cellulose conformes à l'une ou plusieurs des revendications précédentes, caractérisés en ce que la cellulose est une cellulose dont la teneur en cellulose alpha est supérieure à 90 %, de préférence supérieure à 96 % et mieux encore supérieure à 98 %.
  7. Corps en cellulose conformes à l'une ou plusieurs des revendications précédentes, caractérisés en ce que la cellulose est une cellulose dont le degré moyen de polymérisation est supérieur à 600, et de préférence supérieur à 650.
  8. Corps en cellulose conformes à l'une ou plusieurs des revendications précédentes, caractérisés en ce que ces corps en cellulose sont des filaments ou des fibres.
  9. Procédé de fabrication de filaments ou de fibres en cellulose, conformes à la revendication 8, caractérisé en ce que les filaments ou les fibres en cellulose sont obtenus par filage à partir d'une solution de cellulose dont la vitesse angulaire au "cross-over" se trouve dans l'intervalle allant de 0,5 à environ 2 radians par seconde.
  10. Utilisation de filaments en cellulose conformes à la revendication 9 pour la fabrication de filés techniques, de câbles ou de tissus textiles de renfort.
  11. Utilisation de filaments en cellulose conformes à la revendication 9 pour la fabrication de câbles pour pneumatiques.
  12. Utilisation de filaments en cellulose conformes à la revendication 9 pour le renforcement d'élastomères, de matières synthétiques, en particulier thermoplastiques, de biopolymères et de polymères biodégradables, ainsi que de masses à mouler en plastiques thermodurcissables, en particulier de résines.
EP09725538A 2008-03-27 2009-03-18 Corps moulés cellulosiques Active EP2268857B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PL09725538T PL2268857T3 (pl) 2008-03-27 2009-03-18 Celulozowe wyroby kształtowe
EP09725538A EP2268857B1 (fr) 2008-03-27 2009-03-18 Corps moulés cellulosiques

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP08102964 2008-03-27
EP09725538A EP2268857B1 (fr) 2008-03-27 2009-03-18 Corps moulés cellulosiques
PCT/EP2009/053198 WO2009118262A1 (fr) 2008-03-27 2009-03-18 Corps moulés cellulosiques

Publications (2)

Publication Number Publication Date
EP2268857A1 EP2268857A1 (fr) 2011-01-05
EP2268857B1 true EP2268857B1 (fr) 2012-09-26

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EP09725538A Active EP2268857B1 (fr) 2008-03-27 2009-03-18 Corps moulés cellulosiques

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EP (1) EP2268857B1 (fr)
KR (1) KR101580115B1 (fr)
ES (1) ES2402442T3 (fr)
PL (1) PL2268857T3 (fr)
WO (1) WO2009118262A1 (fr)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012002729A2 (fr) * 2010-06-30 2012-01-05 코오롱인더스트리 주식회사 Dope pour le filage de fibre cellulosique à haute ténacité, procédé pour la préparation de fibre de filament cellulosique à haute ténacité utilisant un tel dope, et procédé pour la préparation de fibre courte de fibre cellulosique à haute ténacité
JP5851418B2 (ja) * 2010-11-30 2016-02-03 株式会社ブリヂストン 精製セルロース繊維の製造方法、繊維−ゴム複合体の製造方法、及びタイヤの製造方法
JP5948141B2 (ja) * 2012-05-21 2016-07-06 株式会社ブリヂストン 精製多糖類繊維、コード、ゴム−コード複合体、タイヤ及びランフラットタイヤの製造方法
JP5948145B2 (ja) * 2012-05-21 2016-07-06 株式会社ブリヂストン 精製多糖類繊維の製造方法、ゴム−繊維複合体の製造方法、ゴム−コード複合体の製造方法、及びタイヤの製造方法
JP5948144B2 (ja) * 2012-05-21 2016-07-06 株式会社ブリヂストン 精製多糖類繊維の製造方法、ゴム−繊維複合体の製造方法、補強用コードの製造方法、ゴム−コード複合体の製造方法、及びタイヤの製造方法
JP5948143B2 (ja) * 2012-05-21 2016-07-06 株式会社ブリヂストン ハイブリッドコードの製造方法、ゴム−コード複合体の製造方法、及びタイヤの製造方法
JP5948142B2 (ja) * 2012-05-21 2016-07-06 株式会社ブリヂストン コードの製造方法、ゴム−コード複合体の製造方法及びタイヤの製造方法
CN104508194A (zh) * 2012-05-21 2015-04-08 株式会社普利司通 帘线、橡胶-帘线复合体和轮胎
PL2981641T3 (pl) 2013-04-04 2024-07-22 Aalto University Foundation Sr Sposób wytwarzania wyrobów kształtowanych z celulozy
EP3414371A1 (fr) 2016-02-11 2018-12-19 Deutsche Institute für Textil- und Faserforschung Denkendorf Procédé pour produire des fibres polymères à partir de polymères dissouts dans des liquides ioniques au moyen d'un procédé de filage avec espace d'air
KR20190013817A (ko) * 2016-05-25 2019-02-11 데이진 아라미드 게엠베하 내관통성 물체
CA3051143A1 (fr) 2017-01-30 2018-08-02 Aalto University Foundation Sr Procede de fabrication d'une fibre ou d'un film de cellulose
JP7252128B2 (ja) 2017-09-29 2023-04-04 古河電気工業株式会社 成形品
JP7203743B2 (ja) 2017-09-29 2023-01-13 古河電気工業株式会社 成形品
CN111148798A (zh) 2017-09-29 2020-05-12 古河电气工业株式会社 成型品
CN111295419B (zh) 2017-10-31 2023-03-10 古河电气工业株式会社 成型品

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DE4444140A1 (de) 1994-12-12 1996-06-13 Akzo Nobel Nv Lösungsmittelgesponnene cellulosische Filamente
AT404032B (de) * 1996-03-04 1998-07-27 Chemiefaser Lenzing Ag Verfahren zur herstellung cellulosischer fasern
DE10043297B4 (de) * 2000-09-02 2005-12-08 Thüringisches Institut für Textil- und Kunststoff-Forschung e.V. Verfahren zur Herstellung von Cellulosefasern und Cellulosefilamentgarnen
DE102006022009B3 (de) * 2006-05-10 2007-12-06 Thüringisches Institut für Textil- und Kunststoff-Forschung e.V. Verfahren zur Herstellung cellulosischer Mehrkomponentenfasern

Also Published As

Publication number Publication date
EP2268857A1 (fr) 2011-01-05
KR101580115B1 (ko) 2016-01-04
PL2268857T3 (pl) 2013-01-31
WO2009118262A1 (fr) 2009-10-01
KR20100129293A (ko) 2010-12-08
ES2402442T3 (es) 2013-05-03

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