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EP1716273A1 - Procede pour produire des fibres et d'autres corps profiles a partir de carbamate de cellulose et/ou de cellulose regenere - Google Patents

Procede pour produire des fibres et d'autres corps profiles a partir de carbamate de cellulose et/ou de cellulose regenere

Info

Publication number
EP1716273A1
EP1716273A1 EP05707477A EP05707477A EP1716273A1 EP 1716273 A1 EP1716273 A1 EP 1716273A1 EP 05707477 A EP05707477 A EP 05707477A EP 05707477 A EP05707477 A EP 05707477A EP 1716273 A1 EP1716273 A1 EP 1716273A1
Authority
EP
European Patent Office
Prior art keywords
cellulose
solution
fibers
nmmno
cellulose carbamate
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.)
Granted
Application number
EP05707477A
Other languages
German (de)
English (en)
Other versions
EP1716273B1 (fr
Inventor
Hans-Peter Fink
Peter Weigel
Rainer Rihm
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
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 Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV filed Critical Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
Publication of EP1716273A1 publication Critical patent/EP1716273A1/fr
Application granted granted Critical
Publication of EP1716273B1 publication Critical patent/EP1716273B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • 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

Definitions

  • the invention relates to high strength fibers and others
  • Moldings made of cellulose carbamate or cellulose which is obtained by regeneration of cellulose carbamate, and their production by extrusion of a solution of cellulose carbamate in N-methylmorpholine-N-oxide (NMMNO).
  • NMMNO N-methylmorpholine-N-oxide
  • a well-known way of producing molded Bodies made from regenerated cellulose consist in the precipitation of a solution of cellulose carbamate (EP-A 57 105, EP-A 178 292), which is formed by reacting cellulose with urea with thermal splitting of the urea into isocyanic acid.
  • Cellulose carbamate is soluble in cold, dilute sodium hydroxide solution and can be regenerated back to cellulose in heated sodium hydroxide solution.
  • “Lyocell” fiber is produced, consists in the precipitation of a solution of cellulose in a system of N-methylmorpholine-N-oxide (NMMNO) and water (US 3,767,756, DE 28 30 685), the solution via an air gap in an aqueous Precipitation bath is extruded.
  • NMMNO N-methylmorpholine-N-oxide
  • US 3,767,756, DE 28 30 685 US 3,767,756, DE 28 30 685
  • the process has the disadvantage of a relatively low variability in the product properties. While the strength of the fibers of 15 to 60 cN / tex can be achieved with the viscose process, the strengths in the NMMNO process are in a relatively narrow range between 30 to 45 cN / tex. The field of use of such fibers is thus severely restricted because fibers with lower strength, which also have a lower tendency to fibrillate, are preferred for the textile sector, and higher strengths are often desired for technical applications (e.g. for tire cord).
  • a method for producing fibers and other shaped bodies in which a lyotropic solution of cellulose carbamate in N-methylmorpholine-N-oxide (NMMNO) is deformed into a precipitation bath by means of extrusion from at least one nozzle via an air gap.
  • NMMNO N-methylmorpholine-N-oxide
  • Variations in the degree of orientation can be achieved by changing the L / D ratio (ratio length / diameter of the nozzle channel) and the draw ratio (ratio take-off speed / nozzle exit speed).
  • L / D ratios of 1 to 20 and drawdown ratios of preferably 5 to 200 are preferably used.
  • the width of the air gap between the nozzle and the precipitation bath is preferably 5 to 250 mm, particularly preferably 10 to 150 mm.
  • the lyotropic solution is preferably prepared by swelling the cellulose carbamate in a 50% strength solution of NMMNO in water and then removing the water to a ratio of NMMNO to water between 80:20 and 90:10, particularly preferably 87:13.
  • the spinning is preferably carried out at a temperature of 80 to 110 ° C, particularly preferably in the range of 85 to 95 ° C.
  • the precipitation bath preferably consists of a solution of NMMNO in water with an NMMNO content of 0.5 to 25 % By weight, particularly preferably 5 to 15% by weight, in each case based on the precipitation bath solution.
  • the cellulose carbamate is regenerated to cellulose in a regeneration bath.
  • the cellulose carbamate is particularly preferably regenerated to cellulose in a regeneration bath from 0.3 to 1% by weight of sodium hydroxide in water at a temperature of 60 to 95.degree.
  • fibers and other molded articles made of cellulose carbamate and / or regenerated cellulose are also provided, which have a strength of at least 60 cN / tex.
  • the fibers and other shaped bodies can preferably be produced by the previously described method.
  • Fig. 1 shows a schematic representation of the process flow according to the invention.
  • Example 1 (comparative example according to the prior art)
  • a spinning solution of 9.5% cellulose in NMMO monohydrate with 0.5 mass% propyl gallate as stabilizing agent was spun on a laboratory spinning system with a 40-hole nozzle at a temperature of 90 ° C., a 10% - as spinning bath (precipitation bath) solution of NMMO in water was used.
  • the filament yarns had a strength of 35 cN / tex and an elongation of 9% with a titer of 8.0 tex.
  • cellulose carbamate (3% nitrogen content, Cuoxam-DP 300) were mixed in a kneader with 1305 g of a 50% aqueous NMMO solution, this solution by removing the excess water under a vacuum of 80 mbar until the NNMO monohydrate - Concentrated and the cellulose carbamate dissolved.
  • the spinning solution had a cellulose content of 25% by mass.
  • This spinning solution was spun on a laboratory spinning system with a 40-hole nozzle at a temperature of 100 ° C., a 10% solution of NMMO in water being used as the spinning bath (precipitation bath).
  • the filament yarns had a tenacity of 65 cN / tex and an elongation of 6% with a titer of 8.1 tex.
  • Precipitation bath a 10% solution of NMMO in water was used.
  • the initially moist threads were subjected to an aftertreatment in 0.5% NaOH solution.
  • the filament yarns had a strength of 69 cN / tex and an elongation of 4.5% with a titer of 7.6 tex.

Landscapes

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

Abstract

La présente invention concerne des fibres de rigidité élevée et d'autres corps profilés en carbamate de cellulose ou en cellulose obtenu par régénération de carbamate de cellulose, ainsi que leur production par extrusion d'une solution de carbamate de cellulose dans du N-oxyde de N-méthylmorpholine (NMMNO).
EP05707477A 2004-02-17 2005-02-17 Procede pour produire des fibres et d'autres corps profiles a partir de carbamate de cellulose et/ou de cellulose regenere Expired - Lifetime EP1716273B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004007616A DE102004007616B4 (de) 2004-02-17 2004-02-17 Verfahren zur Herstellung von Fasern und anderen Formkörpern aus Cellulosecarbamat und/oder regenerierter Cellulose
PCT/EP2005/001642 WO2005080649A1 (fr) 2004-02-17 2005-02-17 Procede pour produire des fibres et d'autres corps profiles a partir de carbamate de cellulose et/ou de cellulose regenere

Publications (2)

Publication Number Publication Date
EP1716273A1 true EP1716273A1 (fr) 2006-11-02
EP1716273B1 EP1716273B1 (fr) 2007-10-31

Family

ID=34813446

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05707477A Expired - Lifetime EP1716273B1 (fr) 2004-02-17 2005-02-17 Procede pour produire des fibres et d'autres corps profiles a partir de carbamate de cellulose et/ou de cellulose regenere

Country Status (5)

Country Link
US (1) US20080023874A1 (fr)
EP (1) EP1716273B1 (fr)
JP (1) JP2007522361A (fr)
DE (2) DE102004007616B4 (fr)
WO (1) WO2005080649A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004007617B4 (de) * 2004-02-17 2007-02-08 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Herstellung eines Vliesstoffes, Vliesstoff und dessen Verwendung
DE102008018746A1 (de) 2008-04-14 2009-10-15 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Cellulosecarbamat-Spinnlösung, Verfahren zur Herstellung eines Cellulosecarbamat-Vliesstoffes, Cellulosecarbamat-Vliesstoff sowie Verwendungszwecke
DE102008018743A1 (de) 2008-04-14 2009-10-22 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Cellulosecarbamat-Spinnlösung, Cellulosecarbamatfaser sowie Verfahren zu deren Herstellung und Verwendungszwecke
DE102008018745A1 (de) * 2008-04-14 2009-10-15 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Cellulosecarbamat-Spinnlösung, Cellulosecarbamat-Blasfolie sowie Verfahren zu deren Herstellung und Verwendungsmöglichkeiten
AT511002A1 (de) * 2011-02-08 2012-08-15 Univ Innsbruck Verfahren zur verformung von cellulosecarbamat und produkte, die nach diesem verfahren hergestellt werden
EP3505659A1 (fr) * 2018-08-30 2019-07-03 Aurotec GmbH Procédé et dispositif de filage des filaments à déviation

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AT16937B (de) * 1903-05-05 1904-07-11 Peter Macmaster Vorrichtung zur Registrierung der Arbeitszeit von Arbeitern.
AT17876B (fr) * 1903-12-24 1904-10-10 Richard Mueller
AT20352B (de) * 1904-05-10 1905-06-10 Hans Ernst Vorrichtung zum Anzeigen der Darmfüllung auf ein bestimmtes Gewicht an Wursfüllmaschinen.
US3767756A (en) * 1972-06-30 1973-10-23 Du Pont Dry jet wet spinning process
IT1077319B (it) * 1977-07-12 1985-05-04 Snam Progetti Processo per la sterilizzazione del latte e prodotti alimentari
US4144080A (en) * 1977-07-26 1979-03-13 Akzona Incorporated Process for making amine oxide solution of cellulose
EP0179822B1 (fr) * 1984-04-27 1988-03-09 Michelin Recherche Et Technique S.A. Compositions anisotropes en esters cellulosiques; procedes pour obtenir ces compositions; fibres en esters cellulosiques ou en cellulose
JPS61501995A (ja) * 1984-04-27 1986-09-11 ミシユラン　ルシエルシユ　エ　テクニク セルロ−ズ　エステルの異方性組成物、このような組成物を得る方法、およびセルロ−ズ　エステル　またはセルロ−ズのフアイバ
FI69852C (fi) * 1984-09-27 1986-05-26 Neste Oy Cykliskt foerfarande foer framstaellning av en alkaliloesning av cellulosakarbamat foer utfaellning av karbamatet och foeraotervinning av kemikalierna
FI69853C (fi) * 1984-09-27 1986-05-26 Neste Oy Cykliskt foerfarande foer framstaellning av en alkaliloesning av cellulosakarbamat foer utfaellning av karbamatet och foeraotervinning av kemikalierna
FI69851C (fi) * 1984-09-27 1986-05-26 Neste Oy Foerfarande foer utfaellning av cellulosakarbamat
AT384813B (de) * 1984-10-09 1988-01-11 Chemiefaser Lenzing Ag Verfahren zur herstellung von cellulosecarbamaten
US5378827A (en) * 1992-12-16 1995-01-03 Zimmer Aktiengesellschaft Process for the production of cellulose carbamate
JPH07102079A (ja) * 1993-10-01 1995-04-18 Mitsubishi Rayon Co Ltd セルロース成形品の製造方法
FR2724662B1 (fr) * 1994-09-19 1997-01-24 Michelin Rech De Tech Sa Solutions cristal-liquide a base de cellulose et d'au moins un acide phosphorique
AT402739B (de) * 1995-09-19 1997-08-25 Chemiefaser Lenzing Ag Verfahren zur herstellung eines cellulosischen formkörpers
BR9711933A (pt) * 1996-10-18 1999-08-24 Michelin Rech Tech Agente coagulante aquoso para solu-Æo de cristal l¡quido - base de materiais celulÄsicos processo de fia-Æo artigo fiado fibra celulÄsica e artigo de borrach(s) ou de material(ais) pl stico(s)
JP3831999B2 (ja) * 1996-11-21 2006-10-11 東洋紡績株式会社 再生セルロース繊維およびその製法
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FR2770232B1 (fr) * 1997-10-27 2000-01-14 Rhodia Ag Rhone Poulenc Procede de preparation d'une fibre ou d'un fil de cellulose regeneree
DE10102172A1 (de) * 2001-01-18 2002-08-01 Zimmer Ag Verfahren und Vorrichtung zur kontinuierlichen Synthese von Cellulosecarbamat
DE10203093A1 (de) * 2002-01-28 2003-07-31 Rudolf Kaempf Verfahren zur Herstellung nicht fibrillierender Cellulosefasern
DE10223174A1 (de) * 2002-05-24 2003-12-11 Fraunhofer Ges Forschung Verfahren zur Herstellung von Cellulosecarbamatformkörpern
DE10223172B4 (de) * 2002-05-24 2004-05-06 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Herstellung von Cellulosecarbamat mittels reaktiver Extrusion und die Verwendung der Verfahrensprodukte zur Herstellung von Formkörpern

Non-Patent Citations (1)

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Title
See references of WO2005080649A1 *

Also Published As

Publication number Publication date
JP2007522361A (ja) 2007-08-09
EP1716273B1 (fr) 2007-10-31
DE502005001826D1 (de) 2007-12-13
US20080023874A1 (en) 2008-01-31
DE102004007616B4 (de) 2005-12-22
WO2005080649A1 (fr) 2005-09-01
DE102004007616A1 (de) 2005-09-01

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