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EP1224343A1 - Method for producing cellulose shaped-bodies - Google Patents

Method for producing cellulose shaped-bodies

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Publication number
EP1224343A1
EP1224343A1 EP00978960A EP00978960A EP1224343A1 EP 1224343 A1 EP1224343 A1 EP 1224343A1 EP 00978960 A EP00978960 A EP 00978960A EP 00978960 A EP00978960 A EP 00978960A EP 1224343 A1 EP1224343 A1 EP 1224343A1
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EP
European Patent Office
Prior art keywords
cellulose
bleached
carboxyl group
group content
range
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
EP00978960A
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German (de)
French (fr)
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EP1224343B1 (en
Inventor
Ralf-Uwe Bauer
Uwe Kind
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LL Plant Engineering AG
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Alceru Schwarza GmbH
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Publication of EP1224343A1 publication Critical patent/EP1224343A1/en
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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

Definitions

  • the invention relates to a process for the production of cellulose moldings, such as fibers, filaments or foils, from TCF or ECF bleached cellulose, in which the bleached cellulose is dissolved in an aqueous tertiary amine oxide to form a formable cellulose solution, the cellulose solution is deformed and by Coagulation of the deformed solution forms the shaped body.
  • the invention further relates to the use of a TCF or ECF bleached cellulose for the production of cellulose moldings.
  • the object of the present invention is to create a process for the production of cellulose moldings with reduced cellulose degradation starting from TCF or ECF bleached cellulose.
  • the reduction in cellulose breakdown should be achieved essentially without special measures in the Lyocell process. Further advantages of the invention result from the following description.
  • Pulp and fiber whiteness levels of different pulp provenances were determined, which were either ECF or TCF bleached.
  • the whiteness of the pulp was determined in accordance with DIN 53145, part 2.
  • the whiteness of the fiber was determined by the method described in WO 97/23666, page 6.
  • the average degree of polymerization of the pulps by the Cuoxam method was about 550.
  • the degrees of whiteness measured on the pulp and fiber are summarized in Table 1. Table 1
  • the above-mentioned object is therefore achieved according to the invention in the method mentioned at the outset by reducing of cellulose degradation in the process, a TCF-bleached pulp with a carboxyl group content in the range of 1 to 35 ⁇ mol / g or an ECF-bleached pulp with a carboxyl group content in the range of 1 to 50 ⁇ mol / g is used. It has been shown that the lower the carboxyl group content of the pulp used, the more the cellulose degradation is kept behind in the course of the production and processing of the extrusion solution.
  • TCF and ECF bleached pulps are used in the spinning solution production, the carboxyl group content of which lies in the ranges mentioned. Pulp with the carboxyl group contents mentioned can be produced by various pulp manufacturers.
  • the reduced degradation of the spinning solution components also results in fewer coloring constituents, so that the whiteness of the shaped bodies formed is also improved secondarily.
  • a TCF-bleached cellulose with a carboxyl group content in the range from 15 to 30 ⁇ mol / g or an ECF-bleached cellulose with an arboxyl group content in the range from 25 to 35 ⁇ mol / g is preferably used in the dissolving stage.
  • the carboxyl group content of the cellulose to be used can be determined according to Döring, see K. Goetze, man-made fibers according to the viscose method, 2nd vol. 3rd edition, 1997, p. 1079.
  • NMMO-MH N-methyl 'lmorpholin-N-oxide monohydrate
  • a cellulose solution containing alkali or organic compounds can be formed, the latter containing at least four carbon atoms, at least two conjugated double bonds and at least two substituents -XH, where X is 0 or NR and R can be hydrogen or an alkyl group of 1 to 4 carbon atoms.
  • the low degradation achieved according to the invention can be reduced even further by these solution additives.
  • the amount of the organic compound may be in the range of 0.01 to 0.5% by mass based on the amount of the solvent. Suitable organic compounds are known from EP-A-0047 929. A commonly used compound is isopropyl gallate.
  • the process according to the invention limits cellulose degradation to a proportion in the range from 3 to 20% by mass, based on the pulp used.
  • the cellulose fraction degraded is preferably in the range from 8 to 15% by mass.
  • the invention further relates to the use of a TCF-bleached cellulose or an ECF-bleached cellulose with a carboxyl group content in the range of 1 to 35 ⁇ mol / g or 1 to 50 ⁇ mol / g for the formation of a cellulose solution in a solvent containing tertiary amine oxide for the Production of moldings using the Lyocell process.
  • the use of these pulps not only reduces the degradation in the course of the lyocell process, but also increases the whiteness of the shaped bodies formed.
  • Long fiber sulfite pulp was bleached in a known manner by alkaline, peroxide-enhanced oxygen extraction, then with ozone and with peroxide.
  • the bleaching methods are described, for example, in RP Singh, The Bleaching of Pulp, TAPPI Press, Atlanta, USA. Three different carboxyl group contents were set (Examples 1 to 3). Three more samples of the pulp were bleached with hypochlorite. The degree of polymerization and the initial degree of whiteness of the pulps were determined according to the above-mentioned methods, and the carboxyl and carbonyl group content of the pulp. Spinning solutions with 13% cellulose, 10.5% water and 76.5% NMMO were produced in a known manner from the bleached cellulose.
  • the solutions were spun using the dry-wet process at 95 ° C. with a nozzle with a hole diameter of 65 ⁇ m.
  • the degree of polymerization and the degree of whiteness were determined on the fibers obtained.
  • the degree of polymerization was determined by the Cuoxam method, the degree of fiber whiteness by the method given above. The numerical values determined are given in Table 2.
  • the degree of polymerization, the carboxal group content and the carbonyl group content and the starting whiteness were determined on four bleached dissolving pulps.
  • Four spinning solutions with 13% cellulose, 10.5% water and 76.5% NMMO were produced from the cellulose.
  • the zero shear viscosity was measured at 85 ° C on the spinning masses (Haake RS 75, year of construction 1998).
  • the spinning solutions were spun at 95 ° C. with a nozzle with a hole diameter of 65 ⁇ m by the usual dry-wet method.
  • the degree of polymerization of the cellulose was determined on the spinning solution and the degree of whiteness on the fibers. The results are summarized in Table 3.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Paper (AREA)

Abstract

Process for manufacture of cellulose mouldings, such as fibres, filaments, or films, from TCF-bleached or ECF-bleached cellulose, in which the bleached cellulose is dissolved in an aqueous tertiary aminoxide to form a mouldable cellulose, the cellulose solution deforms, and the moulding comes into being by coagulation of the deformed solution, characterized in that, to reduce the cellulose decomposition in the process, TCF-bleached cellulose is used comprising carboxyl group content in the range from 1 to 35 mumol/g or an ECF-bleached cellulose with carboxyl group content in the range from 1 to 50 mumol/g. Cellulose mouldings having a reduced cellulose decomposition may be formed by said process.

Description

Verfahren zur Herstellung von Cellulose-Formkörpern Process for the production of cellulose moldings
Die Erfindung betrifft ein Verfahren zur Herstellung von Cellulose-Formkörpern, wie Fasern, Filamenten oder Folien, aus TCF- oder ECF-gebleichtem Zellstoff, bei dem man den gebleichten Zellstoff in einem wässrigen tertiären Aminoxid zu einer formbaren Celluloselosung auflöst, die Celluloselosung verformt und durch Koagulation der verformten Lösung den Formkörper bildet. Die Erfindung betrifft ferner die Verwendung eines TCF- oder ECF-ge- bleichten Zellstoffs zur Herstellung von Cellulose-Formkörpern.The invention relates to a process for the production of cellulose moldings, such as fibers, filaments or foils, from TCF or ECF bleached cellulose, in which the bleached cellulose is dissolved in an aqueous tertiary amine oxide to form a formable cellulose solution, the cellulose solution is deformed and by Coagulation of the deformed solution forms the shaped body. The invention further relates to the use of a TCF or ECF bleached cellulose for the production of cellulose moldings.
Die Probleme des Viskoseverfahrens führten zur Entwicklung neuer Verfahren zur Herstellung regenerierter Cellulose-Formkörper, bei denen die Cellulose ohne chemische Modifizierung in Lösung gebracht wird. Die aus diesen Lösungen erhaltenen Fasern und Fila- mente werden unter der Bezeichnung "Lyocell" zusammengefaßt . Besonders geeignete organische Lösungsmittel sind tertiäre Aminoxide, insbesondere N-Methylmorpholin-N-oxid (NMMO) . Ein Verfahren zur Bildung einer Celluloselosung in wässrigem NMMO ist aus DE-A 44 41 468 bekannt. Die Herstellung cellulosischer Formkörper aus diesen Lösungen ist in EP-A 0 574 870 beschrieben.The problems of the viscose process led to the development of new processes for the production of regenerated cellulose moldings in which the cellulose is brought into solution without chemical modification. The fibers and filaments obtained from these solutions are summarized under the name "Lyocell". Particularly suitable organic solvents are tertiary amine oxides, especially N-methylmorpholine-N-oxide (NMMO). A method for forming a cellulose solution in aqueous NMMO is known from DE-A 44 41 468. The production of cellulosic molded articles from these solutions is described in EP-A 0 574 870.
In dieser Lösung erfährt die gelöste Cellulose und das Lösungsmittel unter den thermischen Bedingungen einen chemischen Abbau, was zu Verfärbungen der Spinnlösung führt. Trotz intensiven Aus- waschens der gebildeten cellulosischen Formkörper verbleiben färben- de Stoffe in dem Formkörper, wodurch dessen Weißgrad beeinträchtigt wird. Zur Verringerung des genannten Abbaus wird daher der Spinnlösung ein Stabilisator zugesetzt. Geeignete Stabilisatoren sind aus EP-A 0047 929 und DD 218 104 bekannt.In this solution, the dissolved cellulose and the solvent undergo chemical degradation under the thermal conditions, which leads to discoloration of the spinning solution. Despite intensive washing out of the cellulosic moldings formed, de substances in the molded body, which affects its whiteness. To reduce the degradation mentioned, a stabilizer is therefore added to the spinning solution. Suitable stabilizers are known from EP-A 0047 929 and DD 218 104.
Aus WO 97/23666 ist bekannt, daß der Einsatz von TCF-gebleich- tem Zellstoff beim Lyocell-Verfahren zu Formkörpern mit einem höheren Weißgrad führt als der Einsatz eines ECF-gebleichten Zellstoffs. Beide Zellstoffe werden mit ähnlich hohen Ausgangsweißgraden um 90% und hohen Reinheiten, insbesondere bezüglich des Lignin- gehalts bereitgestellt. Es erschien daher fraglich, ob der TCF-Zellstoff generell bessere Weißgrade der aus diesem Zellstoff hergestellten Cellulose-Formkörper ergibt als ein ECF-Zellstoff.From WO 97/23666 it is known that the use of TCF-bleached cellulose in the Lyocell process leads to moldings with a higher degree of whiteness than the use of an ECF-bleached cellulose. Both pulps are provided with similarly high starting whiteness levels of around 90% and high purities, particularly with regard to the lignin content. It therefore appeared questionable whether the TCF pulp generally gives better degrees of whiteness of the cellulose moldings produced from this pulp than an ECF pulp.
Aufgabe der vorliegenden Erfindung ist die Schaffung eines Verfahrens zur Herstellung von Cellulose-Formkörpern mit verringertem Celluloseabbau ausgehend von TCF- oder ECF-gebleichtem Zellstoff. Die Verringerung des Celluloseabbaus soll im wesentlichen ohne besondere Maßnahmen im Lyocellverfahren erreicht werden. Weitere Vorteile der Erfindung ergeben sich aus der folgenden Beschreibung.The object of the present invention is to create a process for the production of cellulose moldings with reduced cellulose degradation starting from TCF or ECF bleached cellulose. The reduction in cellulose breakdown should be achieved essentially without special measures in the Lyocell process. Further advantages of the invention result from the following description.
Es wurden Zellstoff- und Faserweißgrade verschiedener Zellstoffprovenienzen bestimmt, die entweder ECF- oder TCF-gebleicht waren. Die Bestimmung des Weißgrades an dem Zellstoff wurde nach DIN 53145, Teil 2 durchgeführt. Die Bestimmung des Weißgrades der Faser erfolgte nach der in WO 97/23666, Seite 6, beschriebenen Methode. Der durchschnittliche Polymerisationsgrad der Zellstoffe nach der Cuoxam- methode betru g etwa 550. Die am Zellstoff und an der Faser gemessenen Weißgrade sind in der Tabelle 1 zusammengestellt. Tabelle 1Pulp and fiber whiteness levels of different pulp provenances were determined, which were either ECF or TCF bleached. The whiteness of the pulp was determined in accordance with DIN 53145, part 2. The whiteness of the fiber was determined by the method described in WO 97/23666, page 6. The average degree of polymerization of the pulps by the Cuoxam method was about 550. The degrees of whiteness measured on the pulp and fiber are summarized in Table 1. Table 1
Aus der Tabelle 1 ist ersichtlich, daß bei den. ECF- oder TCF-gebleichten Zellstoffen verschiedener Provenienzen der Weißgrad in einem engen Bereich zwischen 87,5 und 93,7 liegt. Die Weißgrade der er- sponnenen Fasern liegen ebenfalls eng zwischen 55,0 und 58,6 beieinander. Ein höherer Weißgrad der aus TCF-gebleichtem Zellstoff ersponnenen Faser war nicht erkennbar.From Table 1 it can be seen that the. ECF- or TCF-bleached pulps of different origins the whiteness is in a narrow range between 87.5 and 93.7. The whiteness of the spun fibers are also close to one another between 55.0 and 58.6. A higher whiteness of the fiber spun from TCF-bleached pulp was not discernible.
Unsere Untersuchungen haben nun ergeben, daß der Celluloseabbau im Verlauf des Lyocellverfahrens, d.h. im wesentlichen von der Bildung bis zur Koagulation der Spinnlösung, von dem Carboxylgruppengehalt des zur Bildung der Spinnlösung eingesetzten, gebleichten Zellstoffs abhängt. Dabei hat sich gezeigt, daß der Celluloseabbau der ersponnenen Faser umso geringer ist, je geringer der Carboxylgruppengehalt des zur Lösungsbildung eingesetzten Zellstoffs ist. Es lassen sich daher nach dem Lyocellverfahren Cellulosefasern mit verringertem Celluloseabbau dadurch herstellen, daß ein TCF- oder ECF-gebleichter Zellstoff mit niedrig gehaltenem Carboxylgruppengehalt zur Bildung der Spinnlösung eingesetzt wird.Our investigations have now shown that cellulose degradation in the course of the lyocell process, i.e. essentially depends on the formation to the coagulation of the spinning solution, on the carboxyl group content of the bleached pulp used to form the spinning solution. It has been shown that the lower the carboxyl group content of the pulp used to form the solution, the lower the cellulose breakdown of the spun fiber. It can therefore be produced by the Lyocell process cellulose fibers with reduced cellulose degradation in that a TCF or ECF-bleached pulp with a low carboxyl group content is used to form the spinning solution.
Die oben genannte Aufgabe wird daher bei dem eingangs genannten Verfahren erfindungsgemäß dadurch gelöst, daß man zur Verringerung des Celluloseabbaus im Verfahren einen TCF-gebleichten Zellstoff mit einem Carboxylgruppengehalt in dem Bereich von 1 bis 35 μmol/g oder einen ECF-gebleichten Zellstoff mit einem Carboxylgruppengehalt in dem Bereich von 1 bis 50 μmol/g einsetzt. Es hat sich gezeigt, daß der Celluloseabbau im Zuge der Herstellung und Verarbeitung der Extrusionslösung umso mehr hintan gehalten wird, je geringer der Carboxylgruppengehalt des eingesetzten Zellstoffs ist. Um einen geringen Abbau der Cellulose und des Aminoxids beim Lyocellverfahren zu erreichen, werden bei der Spinnlösungsherstel- lung TCF- und ECF-gebleichte Zellstoffe eingesetzt, deren Carboxylgruppengehalt in den genannten Bereichen liegt. Zellstoffe mit den genannten Carboxylgruppengehalten können von verschiedenen Zellstoffherstellern hergestellt werden. Durch den verringerten Abbau der Spinnlösungskomponenten entstehen auch weniger färbende Bestandteile, so daß sekundär auch der Weißgrad der gebildeten Formkörper verbessert wird.The above-mentioned object is therefore achieved according to the invention in the method mentioned at the outset by reducing of cellulose degradation in the process, a TCF-bleached pulp with a carboxyl group content in the range of 1 to 35 μmol / g or an ECF-bleached pulp with a carboxyl group content in the range of 1 to 50 μmol / g is used. It has been shown that the lower the carboxyl group content of the pulp used, the more the cellulose degradation is kept behind in the course of the production and processing of the extrusion solution. In order to achieve a low degradation of the cellulose and the amine oxide in the lyocell process, TCF and ECF bleached pulps are used in the spinning solution production, the carboxyl group content of which lies in the ranges mentioned. Pulp with the carboxyl group contents mentioned can be produced by various pulp manufacturers. The reduced degradation of the spinning solution components also results in fewer coloring constituents, so that the whiteness of the shaped bodies formed is also improved secondarily.
Vorzugsweise setzt man in der Lösestufe einen TCF-gebleichten Zellstoff mit einem Carboxylgruppengehalt in dem Bereich von 15 bis 30 umol/g oder einen ECF-gebleichten Zellstoff mit einem ar- boxylgruppengehalt in dem Bereich von 25 bis 35 μmol/g ein. Die Bestimmung des Carboxylgruppengehalts der einzusetzenden Cellulose kann nach Döring erfolgen, vergl. K. Goetze, Chemiefasern nach dem Viskoseverfahren, 2. Bd. 3. Aufl., 1997, S. 1079.A TCF-bleached cellulose with a carboxyl group content in the range from 15 to 30 µmol / g or an ECF-bleached cellulose with an arboxyl group content in the range from 25 to 35 µmol / g is preferably used in the dissolving stage. The carboxyl group content of the cellulose to be used can be determined according to Döring, see K. Goetze, man-made fibers according to the viscose method, 2nd vol. 3rd edition, 1997, p. 1079.
Das bei dem bevorzugten Verfahren der Erfindung als Lösungsmittel eingesetzte tertiäre Aminoxid ist N-Methy'lmorpholin-N-oxid- Monohydrat (NMMO-MH).The tertiary amine oxide employed as a solvent in the preferred method of the invention is N-methyl 'lmorpholin-N-oxide monohydrate (NMMO-MH).
In weiterer Ausgestaltung der Erfindung kann man eine Celluloselosung mit einem Gehalt an Alkalien oder organischen Verbindungen bilden, wobei die letzteren wenigstens vier Kohlenstoffatome, wenigstens zwei konjugierte Doppelbindungen und wenigstens zwei Substituenten -X-H enthalten, wobei X die Bedeutung von 0 oder NR hat und R Wasserstoff oder eine Alkylgruppe mit 1 bis 4 Kohlenstoffatomen sein kann. Durch diese Lösungszusätze kann der erfindungsgemäß erreichte geringe Abbau noch weiter reduziert werden. Die Menge der organischen Verbindung kann in dem Bereich 0,01 bis 0,5 Masse-%, bezogen auf die Lösungsmittelmenge liegen. Geeignete organische Verbindungen sind aus EP-A-0047 929 bekannt. Eine häufig eingesetzte Verbindung ist Isopropylgallat.In a further embodiment of the invention, a cellulose solution containing alkali or organic compounds can be formed, the latter containing at least four carbon atoms, at least two conjugated double bonds and at least two substituents -XH, where X is 0 or NR and R can be hydrogen or an alkyl group of 1 to 4 carbon atoms. The low degradation achieved according to the invention can be reduced even further by these solution additives. The amount of the organic compound may be in the range of 0.01 to 0.5% by mass based on the amount of the solvent. Suitable organic compounds are known from EP-A-0047 929. A commonly used compound is isopropyl gallate.
Durch das erfindungsgemäße Verfahren wird der Celluloseabbau auf einen Anteil in dem Bereich von 3 bis 20 Masse-%, bezogen auf den eingesetzten Zellstoff, beschränkt. Vorzugsweise liegt der abgebaute Celluloseanteil in dem Bereich von 8 bis 15 Masse-%.The process according to the invention limits cellulose degradation to a proportion in the range from 3 to 20% by mass, based on the pulp used. The cellulose fraction degraded is preferably in the range from 8 to 15% by mass.
Die Erfindung betrifft ferner die Verwendung eines TCF-gebleichten Zellstoffs oder eines ECF-gebleichten Zellstoffs mit einem Carboxylgruppengehalt in dem Bereich von 1 bis 35 umol/g bzw. 1 bis 50 μmol/g zur Bildung einer Celluloselosung in einem tertiäres Aminoxid enthaltenden Lösungsmittel für die Herstellung von Formkörpern nach dem Lyocellverfahren. Durch den Einsatz dieser Zellstoffe wird nicht nur der Abbau im Zuge des Lyocell- verfahrens verringert, sondern auch der Weißgrad der gebildeten Formkörper erhöht.The invention further relates to the use of a TCF-bleached cellulose or an ECF-bleached cellulose with a carboxyl group content in the range of 1 to 35 µmol / g or 1 to 50 µmol / g for the formation of a cellulose solution in a solvent containing tertiary amine oxide for the Production of moldings using the Lyocell process. The use of these pulps not only reduces the degradation in the course of the lyocell process, but also increases the whiteness of the shaped bodies formed.
Die Erfindung wird nun durch die folgenden Beispiele näher erläutert.The invention is illustrated by the following examples.
Beispiele 1 bis 6Examples 1 to 6
Langfaser-Sulfitzellstoff wurde durch alkalische, peroxidverstärkte Sauerstoffextraktion, dann mit Ozon und mit Peroxid in bekannter Weise gebleicht. Die Bleichmethoden sind beispielsweise in R.P. Singh, The Bleaching of Pulp, TAPPI Press, Atlanta, USA beschrieben. Dabei wurden drei verschiedene Carboxylgruppengehalte eingestellt (Beispiele 1 bis 3). Drei weitere Proben des Zellstoffs wurden mit Hypochlorit gebleicht. An den Zellstoffen wurde der Polymerisationsgrad und der Ausgangsweißgrad nach den oben angegebenen Mothoden bestimmt, desgl. der Carboxyl- und Carbonylgruppengehalt des Zellstoffs. Aus den gebleichten Zellstoffen wurden Spinnlösungen mit 13% Cellulose, 10,5% Wasser und 76,5% NMMO in bekannter Weise hergestellt. Die Lösungen wurden nach dem Trocken-Naßverfahren bei 95°C mit einer Düse von 65 μm Lochdurchmesser versponnen. An den erhaltenen Fasern wurde der Polymerisationsgrad und der Weißgrad bestimmt. Die Bestimmung des Polymerisationsgrades erfolgte nach der Cuoxam-Methode, die des Faser-Weißgrades nach der oben angegebenen Methode. Die ermittelten Zahlenwerte sind in der Tabelle 2 angegeben.Long fiber sulfite pulp was bleached in a known manner by alkaline, peroxide-enhanced oxygen extraction, then with ozone and with peroxide. The bleaching methods are described, for example, in RP Singh, The Bleaching of Pulp, TAPPI Press, Atlanta, USA. Three different carboxyl group contents were set (Examples 1 to 3). Three more samples of the pulp were bleached with hypochlorite. The degree of polymerization and the initial degree of whiteness of the pulps were determined according to the above-mentioned methods, and the carboxyl and carbonyl group content of the pulp. Spinning solutions with 13% cellulose, 10.5% water and 76.5% NMMO were produced in a known manner from the bleached cellulose. The solutions were spun using the dry-wet process at 95 ° C. with a nozzle with a hole diameter of 65 μm. The degree of polymerization and the degree of whiteness were determined on the fibers obtained. The degree of polymerization was determined by the Cuoxam method, the degree of fiber whiteness by the method given above. The numerical values determined are given in Table 2.
Tabelle 2Table 2
OBestimmung siehe K. Götze, aaO.For the determination see K. Götze, loc. Cit.
Aus der Tabelle 2 ist ersichtlich, daß mit zunehmendem Carboxylgruppengehalt des TCF-gebleichten Zellstoffs und des ECF-gebleichten Zellstoffs ein erheblicher Abfall des Polymerisationsgrades und des Weißgrades der Fasercellulose zu beobachten ist. Für einen gegebenen gebleichten Zellstoff eröffnet die Einstellung seines Carboxylgruppengehalts damit die Möglichkeit, über den Polymerisa- tionsgrad die textilphysikalischen Eigenschaften der ersponnenen Faser zu verbessern. Durch die reduzierte Farbkörperbildung im Zuge des Verfahrens tritt eine langsamere Verfärbung des Spinnbades ein, wodurch sich Kostenvorteile bei der Lösungsmittelregenerierung ergeben.From Table 2 it can be seen that as the carboxyl group content of the TCF-bleached pulp and the ECF-bleached pulp increases, a considerable drop in the degree of polymerization and the degree of whiteness of the fiber cellulose can be observed. For a given bleached pulp, adjusting its carboxyl group content thus opens up the possibility of using the polymer degree of improvement to improve the textile-physical properties of the spun fiber. The reduced color formation in the course of the process leads to a slower discoloration of the spinning bath, which results in cost advantages in solvent regeneration.
Beispiele 7 bis 10Examples 7 to 10
An vier gebleichten Dissolving-Zellstoffen wurde der Polymerisationsgrad, der Carboxalgruppengehalt sowie der Carbonylgruppengehalt und der Ausgangsweißgrad bestimmt. Aus den Zellstoffen wurden vier Spinnlösungen mit 13% Cellulose, 10,5% Wasser und 76,5% NMMO hergestellt. An den Spinnmassen wurde die Nullscherviskosität bei 85°C gemessen (Haake RS 75, Baujahr 1998). Die Spinnlösungen wurden bei 95°C mit einer Düse von 65 μm Lochdurchmesser nach dem üblichen Trocken-Naßverfahren versponnen. An der Spinnlösung wurde der Polymerisationsgrad der Cellulose bestimmt, ferner an den Fasern der Weißgrad. Die Ergebnisse sind in der Tabelle 3 zusammengefaßt.The degree of polymerization, the carboxal group content and the carbonyl group content and the starting whiteness were determined on four bleached dissolving pulps. Four spinning solutions with 13% cellulose, 10.5% water and 76.5% NMMO were produced from the cellulose. The zero shear viscosity was measured at 85 ° C on the spinning masses (Haake RS 75, year of construction 1998). The spinning solutions were spun at 95 ° C. with a nozzle with a hole diameter of 65 μm by the usual dry-wet method. The degree of polymerization of the cellulose was determined on the spinning solution and the degree of whiteness on the fibers. The results are summarized in Table 3.
Tabelle 3Table 3
Tabelle 3 Table 3
Auch aus den Zahlenwerten der Tabelle 3 ist ersichtlich, daß mit zunehmendem Carboxylgruppengehalt des eingestellten Zellstoffs der Celluloseabbau zunimmt und der Faserweißgrad sich gegenüber dem Ausgangsweißgrad verschlechtert. It can also be seen from the numerical values in Table 3 that as the carboxyl group content of the adjusted pulp increases, the cellulose degradation increases and the degree of fiber whiteness deteriorates compared to the initial degree of whiteness.

Claims

Patentansprüche claims
1. Verfahren zur Herstellung von Cellulose-Formkörpern, wie Fasern, Filamenten oder Folien, aus TCF- oder ECF-gebleichtem Zellstoff, bei dem man den Zellstoff in einem wässrigen tertiären Aminoxid zu einer formbaren Celluloselosung auflöst, die Celluloselosung verformt und durch Koagulation der verformten Lösung den Formkörper bildet, dadurch gekennzeichnet, daß man zur Verringerung des Celluloseabbaus im Verfahren einen TCF-gebleichten Zellstoff mit einem Carboxylgruppengehalt in dem Bereich von 1 bis 35 μmol/g oder einen ECF-gebleichten Zellstoff mit einem Carboxylgruppengehalt in dem Bereich von 1 bis 50 μmol/g einsetzt.1. A process for the production of cellulose moldings, such as fibers, filaments or foils, from TCF or ECF-bleached cellulose, in which the cellulose is dissolved in an aqueous tertiary amine oxide to form a formable cellulose solution, the cellulose solution is deformed and the shaped part is coagulated Solution forms the shaped body, characterized in that in order to reduce the cellulose degradation in the process, a TCF-bleached cellulose with a carboxyl group content in the range from 1 to 35 μmol / g or an ECF-bleached cellulose with a carboxyl group content in the range from 1 to 50 μmol / g.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man in der Lösestufe einen TCF-gebleichten Zellstoff mit einem Carboxylgruppengehalt in dem Bereich von 15 bis 30 μmol/g einsetzt.2. The method according to claim 1, characterized in that in the dissolving step a TCF-bleached cellulose with a carboxyl group content in the range of 15 to 30 μmol / g is used.
3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man in der Lösestufe einen ECF-gebleichten Zellstoff mit einem Carboxylgruppengehalt in dem Bereich von 25 bis 35 μmol/g einsetzt.3. The method according to claim 1, characterized in that in the dissolving step an ECF-bleached cellulose with a carboxyl group content in the range of 25 to 35 μmol / g is used.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß man als tertiäres Aminoxid N-Methylmorpholin-N-oxid einsetzt.4. The method according to any one of claims 1 to 3, characterized in that N-methylmorpholine-N-oxide is used as the tertiary amine oxide.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß man eine Celluloselosung mit einem Gehalt an Alkalien oder organischen Verbindungen bildet, wobei die letzteren wenigstens 4 Kohlenstoffatome, wenigstens zwei konjugierte Doppelbindungen und wenigstens zwei Substituenten -X-H enthalten, wobei X die Bedeutung von 0 oder NR hat und R Wasserstoff oder eine Alkylgruppe mit 1 bis 4 Kohlenstoffatomen ist. 5. The method according to any one of claims 1 to 4, characterized in that a cellulose solution containing alkali or organic compounds is formed, the latter containing at least 4 carbon atoms, at least two conjugated double bonds and at least two substituents -XH, where X is the Has the meaning of 0 or NR and R is hydrogen or an alkyl group having 1 to 4 carbon atoms.
6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß man den Celluloseabbau auf einen Anteil in dem Bereich von 3 bis 20%, bezogen auf eingesetzten Zellstoff, beschränkt.6. The method according to any one of claims 1 to 5, characterized in that the cellulose degradation is limited to a proportion in the range of 3 to 20%, based on the pulp used.
7. Verwendung eines TCF-gebleichten Zellstoffs mit einem Carboxylgruppengehalt in dem Bereich von 1 bis 35 μmol/g zur Bildung einer Celluloselosung in einem tertiäres Aminoxid enthaltenden Lösungsmittel für die Herstellung von Formkörpern nach dem Lyocellverfahren.7. Use of a TCF-bleached pulp with a carboxyl group content in the range from 1 to 35 μmol / g to form a cellulose solution in a solvent containing tertiary amine oxide for the production of moldings by the Lyocell process.
8. Verwendung eines ECF-gebleichten Zellstoffs mit einem Carboxylgruppengehalt in dem Bereich von 1 bis 50 μmol/g zur Bildung einer Celluloselosung in einem tertiäres Aminoxid enthaltenden Lösungsmittel für die Herstellung von Formkörpern nach dem Lyocellverfahren. 8. Use of an ECF-bleached pulp with a carboxyl group content in the range from 1 to 50 μmol / g to form a cellulose solution in a solvent containing tertiary amine oxide for the production of moldings by the Lyocell process.
EP00978960A 1999-10-07 2000-09-29 Method for producing cellulose shaped-bodies Expired - Lifetime EP1224343B1 (en)

Applications Claiming Priority (3)

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DE19948401 1999-10-07
DE19948401A DE19948401C1 (en) 1999-10-07 1999-10-07 Process for the production of cellulose moldings
PCT/DE2000/003408 WO2001025515A1 (en) 1999-10-07 2000-09-29 Method for producing cellulose shaped-bodies

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KR (1) KR100661454B1 (en)
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CN101649061B (en) * 2009-07-13 2012-06-27 潍坊恒联玻璃纸有限公司 Preparing method of cellulose membrane specially used by aviation instrument panel
CN106103820A (en) * 2014-03-11 2016-11-09 智能聚合物有限公司 Flame-retardant cellulose moulded bodies produced according to the direct dissolution method

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DE19948401C1 (en) 2001-05-03
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KR100661454B1 (en) 2006-12-27
ZA200203556B (en) 2003-02-26
NO20021588L (en) 2002-04-04
ATE317027T1 (en) 2006-02-15
NO20021588D0 (en) 2002-04-04
KR20020037378A (en) 2002-05-18
BR0014529A (en) 2002-08-27
CN1180141C (en) 2004-12-15
AU1645601A (en) 2001-05-10
MY129236A (en) 2007-03-30
CA2385227A1 (en) 2001-04-12
CN1377428A (en) 2002-10-30
US7175792B1 (en) 2007-02-13
EA200200382A1 (en) 2002-10-31
WO2001025515A1 (en) 2001-04-12
DE50012169D1 (en) 2006-04-13
EP1224343B1 (en) 2006-02-01

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