EP1716273A1 - Method for producing fibres and other moulded bodies from cellulose carbamate and/or regenerated cellulose - Google Patents
Method for producing fibres and other moulded bodies from cellulose carbamate and/or regenerated celluloseInfo
- 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
Links
- 229920002678 cellulose Polymers 0.000 title claims abstract description 43
- 239000001913 cellulose Substances 0.000 title claims abstract description 43
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 239000004627 regenerated cellulose Substances 0.000 title claims description 5
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000008929 regeneration Effects 0.000 claims abstract description 7
- 238000011069 regeneration method Methods 0.000 claims abstract description 7
- 238000001125 extrusion Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 25
- 239000000835 fiber Substances 0.000 claims description 19
- 238000001556 precipitation Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 230000002535 lyotropic effect Effects 0.000 claims description 6
- 230000008961 swelling Effects 0.000 claims description 2
- 238000009987 spinning Methods 0.000 description 16
- 229920000297 Rayon Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- ZTHYODDOHIVTJV-UHFFFAOYSA-N Propyl gallate Chemical compound CCCOC(=O)C1=CC(O)=C(O)C(O)=C1 ZTHYODDOHIVTJV-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000004682 monohydrates Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 1
- 229920000433 Lyocell Polymers 0.000 description 1
- -1 NMMO monohydrate Chemical class 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229940075579 propyl gallate Drugs 0.000 description 1
- 235000010388 propyl gallate Nutrition 0.000 description 1
- 239000000473 propyl gallate Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
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
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102004007616A DE102004007616B4 (en) | 2004-02-17 | 2004-02-17 | Process for producing fibers and other shaped articles from cellulose carbamate and / or regenerated cellulose |
PCT/EP2005/001642 WO2005080649A1 (en) | 2004-02-17 | 2005-02-17 | Method for producing fibres and other moulded bodies from cellulose carbamate and/or regenerated cellulose |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1716273A1 true EP1716273A1 (en) | 2006-11-02 |
EP1716273B1 EP1716273B1 (en) | 2007-10-31 |
Family
ID=34813446
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP05707477A Active EP1716273B1 (en) | 2004-02-17 | 2005-02-17 | Method for producing fibres and other moulded bodies from cellulose carbamate and/or regenerated cellulose |
Country Status (5)
Country | Link |
---|---|
US (1) | US20080023874A1 (en) |
EP (1) | EP1716273B1 (en) |
JP (1) | JP2007522361A (en) |
DE (2) | DE102004007616B4 (en) |
WO (1) | WO2005080649A1 (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102004007617B4 (en) * | 2004-02-17 | 2007-02-08 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Process for producing a nonwoven fabric, nonwoven fabric and its use |
DE102008018745A1 (en) | 2008-04-14 | 2009-10-15 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Cellulose carbamate spinning solution, cellulose carbamate blown film and process for their preparation and uses |
DE102008018743A1 (en) | 2008-04-14 | 2009-10-22 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Cellulose carbamate spinning solution, cellulose carbamate fiber and process for their preparation and uses |
DE102008018746A1 (en) | 2008-04-14 | 2009-10-15 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Cellulose-carbamate spinning solution, process for producing a cellulose-carbamate-nonwoven, cellulose-carbamate-nonwoven and uses |
AT511002A1 (en) * | 2011-02-08 | 2012-08-15 | Univ Innsbruck | METHOD FOR THE FORMING OF CELLULOSECARBAMATE AND PRODUCTS MANUFACTURED BY THIS METHOD |
EP3505659A1 (en) * | 2018-08-30 | 2019-07-03 | Aurotec GmbH | Method and device for filament spinning with inflection |
Family Cites Families (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AT16937B (en) * | 1903-05-05 | 1904-07-11 | Peter Macmaster | Device for recording the working hours of workers. |
AT17876B (en) * | 1903-12-24 | 1904-10-10 | Richard Mueller | |
AT20352B (en) * | 1904-05-10 | 1905-06-10 | Hans Ernst | Device for displaying the intestinal filling to a certain weight on sausage filling machines. |
US3767756A (en) * | 1972-06-30 | 1973-10-23 | Du Pont | Dry jet wet spinning process |
IT1077319B (en) * | 1977-07-12 | 1985-05-04 | Snam Progetti | PROCESS FOR THE STERILIZATION OF MILK AND FOOD PRODUCTS |
US4144080A (en) * | 1977-07-26 | 1979-03-13 | Akzona Incorporated | Process for making amine oxide solution of cellulose |
JPS61501995A (en) * | 1984-04-27 | 1986-09-11 | ミシユラン ルシエルシユ エ テクニク | Anisotropic compositions of cellulose esters, methods for obtaining such compositions, and preparations of cellulose esters or cellulose fibers |
DE3561821D1 (en) * | 1984-04-27 | 1988-04-14 | Michelin Rech Tech | Anisotropic compositions of cellulose esters; processes for obtaining said compositions; fibers of cellulosic esters or cellulose |
FI69851C (en) * | 1984-09-27 | 1986-05-26 | Neste Oy | FOERFARANDE FOER UTFAELLNING AV CELLULOSAKARBAMAT |
FI69852C (en) * | 1984-09-27 | 1986-05-26 | Neste Oy | CYCLIC FAR OIL FRAMING PROCESSING AND ENCOALIZATION OF CELLULOSE CARBAMATE FOR UTFAELLING AV CARBAMATE OCH FOERAOTERVINNING AV KEMIKALIERNA |
FI69853C (en) * | 1984-09-27 | 1986-05-26 | Neste Oy | CYCLIC FAR OIL FRAMING PROCESSING AND ENCOALIZATION OF CELLULOSE CARBAMATE FOR UTFAELLING AV CARBAMATE OCH FOERAOTERVINNING AV KEMIKALIERNA |
AT384813B (en) * | 1984-10-09 | 1988-01-11 | Chemiefaser Lenzing Ag | METHOD FOR PRODUCING CELLULOSE CARBAMATES |
US5378827A (en) * | 1992-12-16 | 1995-01-03 | Zimmer Aktiengesellschaft | Process for the production of cellulose carbamate |
JPH07102079A (en) * | 1993-10-01 | 1995-04-18 | Mitsubishi Rayon Co Ltd | Production of cellulose molding |
FR2724662B1 (en) * | 1994-09-19 | 1997-01-24 | Michelin Rech De Tech Sa | CRYSTAL-LIQUID SOLUTIONS BASED ON CELLULOSE AND AT LEAST ONE PHOSPHORIC ACID |
AT402739B (en) * | 1995-09-19 | 1997-08-25 | Chemiefaser Lenzing Ag | METHOD FOR PRODUCING A CELLULOSIC MOLDED BODY |
JP2001505623A (en) * | 1996-10-18 | 2001-04-24 | ミシュラン ルシェルシュ エ テクニーク ソシエテ アノニム | Aqueous coagulant for liquid crystal solution based on cellulose material |
JP3831999B2 (en) * | 1996-11-21 | 2006-10-11 | 東洋紡績株式会社 | Regenerated cellulose fiber and process for producing the same |
DE19721609A1 (en) * | 1997-05-23 | 1998-11-26 | Zimmer Ag | Method and device for spinning cellulose carbamate solutions |
JPH1181033A (en) * | 1997-06-18 | 1999-03-26 | Asahi Chem Ind Co Ltd | Disperse dye-dyeable cellulose fiber and its production and fiber product |
FR2770232B1 (en) * | 1997-10-27 | 2000-01-14 | Rhodia Ag Rhone Poulenc | PROCESS FOR THE PREPARATION OF A REGENERATED CELLULOSE FIBER OR YARN |
DE10102172A1 (en) * | 2001-01-18 | 2002-08-01 | Zimmer Ag | Method and device for the continuous synthesis of cellulose carbamate |
DE10203093A1 (en) * | 2002-01-28 | 2003-07-31 | Rudolf Kaempf | Production of non-fibrillating cellulose fibers involves spinning cellulose N-methylmorpholine-N-oxide water solution so as to form a core-shell structure in a two-phase spinning nozzle |
DE10223174A1 (en) * | 2002-05-24 | 2003-12-11 | Fraunhofer Ges Forschung | Process for the production of cellulose carbamate moldings |
DE10223172B4 (en) * | 2002-05-24 | 2004-05-06 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Process for the production of cellulose carbamate by means of reactive extrusion and the use of the process products for the production of moldings |
-
2004
- 2004-02-17 DE DE102004007616A patent/DE102004007616B4/en not_active Expired - Fee Related
-
2005
- 2005-02-17 EP EP05707477A patent/EP1716273B1/en active Active
- 2005-02-17 US US10/589,573 patent/US20080023874A1/en not_active Abandoned
- 2005-02-17 DE DE502005001826T patent/DE502005001826D1/en active Active
- 2005-02-17 JP JP2006553536A patent/JP2007522361A/en active Pending
- 2005-02-17 WO PCT/EP2005/001642 patent/WO2005080649A1/en active IP Right Grant
Non-Patent Citations (1)
Title |
---|
See references of WO2005080649A1 * |
Also Published As
Publication number | Publication date |
---|---|
DE102004007616A1 (en) | 2005-09-01 |
DE502005001826D1 (en) | 2007-12-13 |
EP1716273B1 (en) | 2007-10-31 |
WO2005080649A1 (en) | 2005-09-01 |
JP2007522361A (en) | 2007-08-09 |
US20080023874A1 (en) | 2008-01-31 |
DE102004007616B4 (en) | 2005-12-22 |
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