EP1040214B1 - Adjuvants pour la production de fibres cellulosiques - Google Patents

Adjuvants pour la production de fibres cellulosiques Download PDF

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Publication number
EP1040214B1
EP1040214B1 EP98963528A EP98963528A EP1040214B1 EP 1040214 B1 EP1040214 B1 EP 1040214B1 EP 98963528 A EP98963528 A EP 98963528A EP 98963528 A EP98963528 A EP 98963528A EP 1040214 B1 EP1040214 B1 EP 1040214B1
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EP
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Prior art keywords
cellulose
formula
xanthate
compounds
solution
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EP98963528A
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German (de)
English (en)
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EP1040214A1 (fr
Inventor
Martin Lagarden
Raymond Mathis
Ursula Kolken
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BASF Personal Care and Nutrition GmbH
Original Assignee
Cognis Deutschland GmbH and Co KG
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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
    • 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
    • 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 present application relates to the use of end group capped alkoxylated amines as auxiliaries in the production of cellulose fibers after Viscose process and a process for the production of cellulose fibers according to the Process viscose.
  • the large-scale production of cellulose fibers mainly takes place after Viscose.
  • the pulp is first in cellulose exanthate, which so-called viscose, transferred and pressed into an acidic precipitation bath.
  • the acidic solution By the Contact with the acidic solution, the xanthate is precipitated and saponified the cellulose is released in the form of a filament.
  • modifiers e.g. B. quaternary ammonium bases, N-substituted dithiocarboxylic acids, polyethylene glycols and aliphatic monoamines and especially oxyethylated amines and amides or their derivatives.
  • DE 28 37 766 describes, for example, alkoxylation products of a polyhydric alcohol and / or a dibasic amine as modifiers.
  • DE 29 21 314 describes a process for producing crimped cellulose fibers, the modifiers used being, inter alia, ethoxylated fatty acid amines having 8 to 20 carbon atoms.
  • alkylamine glycol ethers are widely used as modifiers in the production of viscose.
  • alkoxylated amines preferably alkyl chlorides
  • alkyl halides preferably alkyl chlorides
  • the present application relates to the use of reaction products of the nucleophilic ring opening of epoxides of the formula (I) in which R 1 represents a linear or branched aliphatic alkyl radical having 1 to 22 carbon atoms with compounds of the formula (II) in which R 2 and R 3 independently of one another represent a radical (C n H 2n -O) m -H or a linear or branched, saturated or unsaturated alkyl radical having 1 to 22 C atoms or hydrogen, n is 2 or 3 has and m is a number between 1 and 20, as an aid in the production of cellulose fibers by the viscose process.
  • R 1 represents a linear or branched aliphatic alkyl radical having 1 to 22 carbon atoms
  • R 2 and R 3 independently of one another represent a radical (C n H 2n -O) m -H or a linear or branched, saturated or unsaturated alkyl radical having 1 to 22 C atoms or hydrogen
  • the ring opening products are known compounds, which according to the usual Methods of organic chemistry can be synthesized.
  • the synthesis of such Connections are usually carried out by reacting the epoxides of the formula (I) with Compounds of formula (II) in the presence of suitable, preferably alkaline Catalysts, e.g. Potassium or lithium hydroxide. Potassium hydroxide is preferred used.
  • suitable, preferably alkaline Catalysts e.g. Potassium or lithium hydroxide.
  • Potassium hydroxide is preferred used.
  • By a nucleophilic attack of the oxygen atom of the compounds of the Formula (II) on one of the epoxy carbon atoms opens the ring and it forms ⁇ -hydroxy ether. Details of this reaction can be found, for example, in the article by W. Stein in fats, soaps, paints, No. 2, 84th year 1992, page 51 and the literature cited there.
  • the ring opening reaction takes place preferably under anhydrous conditions Normal pressure instead.
  • reaction temperatures between 100 and 180 ° C. It is preferred that the reaction in the Temperature range from 140 to 160 ° C to perform.
  • the epoxides of the formula (I) are known compounds which are prepared by epoxidizing alpha-olefins which are obtained, for example, by the shop process. Typical examples are the epoxides of Octen-1, Decen-1, Dodecen-1, Tetradecen-1, Octadecen-1 or Octadecen-9. Epoxides of the formula (I) are preferred. in which R 1 is a linear aliphatic alkyl radical having 8 to 14 carbon atoms.
  • the compounds of the formula (II) are also known. It is ethanol or propanolamines and their alkoxylation products. These can, for example by alkoxylation of mono-, di- or trialkanolamines by customary methods be preserved. As alkoxides, ethylene oxide (EO) or propylene oxide (PO) or Mixtures of these alkoxides can be used. Such compounds are preferred of the formula (II) in which m is a number between 10 and 20 and preferably 12 to 18 means. Those compounds are particularly preferred which only Contain ethylene oxide groups. Such ring opening products are preferred used in the preparation of which, if appropriate, ethoxylated trialkanolamines, preferably triethanolamine can be used.
  • connection can be alkoxylated by other alkanolamines, e.g. 2- (dibutylamino) ethanol, 2- (diethylamino) ethanol, 2- (methylamino) ethanol, 2-ethylaminoethanol, 2-dimethylaminoethanol, Ethanolamine or diethanolamine.
  • alkanolamines e.g. 2- (dibutylamino) ethanol, 2- (diethylamino) ethanol, 2- (methylamino) ethanol, 2-ethylaminoethanol, 2-dimethylaminoethanol, Ethanolamine or diethanolamine.
  • the molar ratio between the epoxy (I) and the compound of formula (II) at the ring opening reaction is preferably between 1: 2 and 1: 1 Ring opening products typically have hydroxide numbers of at least 160, preferably from at least 180.
  • the ring opening products are manufactured without the addition of chlorine chemicals. Also there is no salt load when opening the ring, e.g. at Williamson's Ether synthesis occurs.
  • the products obtained by ring opening can be used as modifiers of both Viscose solution are added, as well as the acidic precipitation bath into which the viscose is pressed.
  • the ring opening products are preferably in quantities between 1 and 5% by weight, based on those contained in the viscose or in the precipitation bath Cellulose added.
  • ring opening products as modifiers in the Viscose solution makes spinning easier, one continues to observe one reduced clogging of the spinnerets.
  • the ring opening products as Modifiers used in the acidic precipitation bath are observed to be more uniform Decomposition of xanthate cellulose and slowing of thread formation. This leads to threads with higher mechanical resilience. At the same time, the failures prevents inorganic salts.
  • the modifiers of the invention are suitable for use in all of them Processes known to those skilled in the art for producing cellulose fibers according to the Viscose.
  • viscose process is used industrially Process of cellulose fiber production understood, as described for example in Z.A. Rogowin, chemical fibers, Georg Thieme Verlag, Stuttgart, 1982, pages 67 to 152 is described.
  • step a) Cellulose, for example in the form of pressed sheets, rolled goods, flakes or squeezed, undried pulp, reacted with an alkali, whereby in known form first the alkali cellulose.
  • alkali any can be used as lyes basic systems are used, especially aqueous alkali, such as potassium or Sodium hydroxide solution.
  • concentration usually amounts to 15 to 30% by weight Base, based on the total weight of the lye.
  • Process step b) follows, which comprises the individual steps of pre-ripening, xanthation with carbon disulphide, dissolving the xanthate in alkali metal solution, ripening and deaerating and leading to the spinnable viscose solution. Details of this process are described, for example, in the above-mentioned publication by ZA Rogowin, pages 97 to 119.
  • the modifiers described above are added to the xanthate solution during the dissolution of the cellulose xanthate in alkali metal hydroxide solution and / or during the maturation.
  • the amount of the modifiers is preferably between 1 and 5% by weight, based on the cellulose contained in the solution.
  • the ripened xanthate solution, process step c), is then spun by pressing the solution, which was previously filtered and tempered, through a Spinneret with essentially round nozzle holes in the precipitation bath. Examples of this are spinnerets with 250 to 30,000 holes and a single diameter one Hole from 35 to 100 ⁇ m.
  • the xanthate coagulates into threads and becomes using a protonic acid to regenerate cellulose, salt and carbon disulphide hydrolyzed.
  • the carbon disulfide is returned to the process.
  • Protonic acid can be organic acids such as acetic acid or mineral acids such as salt, nitrate or sulfuric acid can be used. It is preferred to concentrate Sulfuric acid used.
  • the precipitation bath contains certain acids in addition to the acid Metal salts that can slow down xanthate coagulation.
  • examples for such salts are magnesium, aluminum, iron and in particular zinc salts.
  • the Salts are usually used as chlorides, nitrates or sulfates.
  • the concentration of the salts is usually between 2 to 10 g / l.
  • the precipitation bath is described as above Modifiers added, preferably in amounts of 1 to 5% by weight, based on the contained cellulose.
  • the precipitation bath can be used in addition to those described above Modifiers, the acid and the metal salts are still further known to the person skilled in the art Contain aids, e.g. Formaldehyde or other modifiers.
  • Contain aids e.g. Formaldehyde or other modifiers.
  • the so won Cellulose filaments are then spun, cleaned and in a manner known per se further treated.
  • the inventive method is characterized in that at least one of the two process steps b) or c) modifiers of the type described above be used.
  • the method is carried out so that the Modifiers only of the viscose solution before spinning, i.e. in step b), be added.

Landscapes

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

Claims (7)

  1. Utilisation de produits de réaction de l'ouverture de cycle nucléophile d'époxydes de formule (I)
    Figure 00130001
    dans laquelle R1 représente un radical alkyle aliphatique linéaire ou ramifié comportant de 1 à 22 atomes de carbone, avec des composés de formule (II)
    Figure 00130002
    dans laquelle R2 et R3 représentent indépendamment l'un de l'autre un radical (CnH2n-O)m-H ou un radical alkyle saturé ou insaturé linéaire ou ramifié comportant de 1 à 22 atomes de carbone ou un hydrogène, n a la valeur 2 ou 3 et m représente un nombre compris entre 1 et 20,
    comme adjuvants dans la fabrication de fibres de cellulose selon le procédé de la viscose.
  2. Utilisation selon la revendication 1,
    caractérisé en ce que
    dans les composés de formule (II) R2 et R3 représentent des radicaux de formule (CnH2n-O)m-H.
  3. Utilisation selon la revendication 1 ou 2,
    caractérisée en ce que
    dans les composés de formule (II) n a la valeur 2.
  4. Utilisation selon l'une des revendications 1 à 3,
    caractérisée en ce que
    dans les composés de formule (II) m représente un nombre compris entre 12 et 18.
  5. Utilisation selon l'une des revendications 1 à 4,
    caractérisée en ce que
    dans la formule (I) le radical R1 représente un radical alkyle linéaire comportant de 8 à 14 atomes de carbone.
  6. Utilisation selon l'une des revendications 1 à 5,
    caractérisée en ce que
    les produits de réaction présentent des indices d'hydroxyle (OZH) d'au moins 160.
  7. Procédé de fabrication de fibres de cellulose selon le procédé de la viscose, comprenant les étapes de
    a) formation de cellulose alcaline par réaction de cellulose avec une lessive alcaline,
    b) réaction de la cellulose alcaline avec du sulfure de carbone et une lessive avec formation d'une solution de xanthogénate et
    c) filage de la solution de xanthogénate par des buses de filage dans un bain de précipitation aqueux contenant un acide protonique ainsi que des sels métalliques, opération dans laquelle il se forme, avec décomposition du xanthogénate, une fibre de cellulose,
    caractérisé en ce qu'
    on ajoute les produits de réaction selon la revendication 1 à la solution de xanthogénate et/ou au bain de précipitation à des quantités efficaces comme modificateurs.
EP98963528A 1997-12-08 1998-11-28 Adjuvants pour la production de fibres cellulosiques Expired - Lifetime EP1040214B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19754314A DE19754314A1 (de) 1997-12-08 1997-12-08 Hilfsmittel für die Herstellung von Cellulosefasern
DE19754314 1997-12-08
PCT/EP1998/007700 WO1999029937A1 (fr) 1997-12-08 1998-11-28 Adjuvants pour la production de fibres cellulosiques

Publications (2)

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EP1040214A1 EP1040214A1 (fr) 2000-10-04
EP1040214B1 true EP1040214B1 (fr) 2003-03-05

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EP98963528A Expired - Lifetime EP1040214B1 (fr) 1997-12-08 1998-11-28 Adjuvants pour la production de fibres cellulosiques

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US (1) US6475419B1 (fr)
EP (1) EP1040214B1 (fr)
AT (1) ATE233837T1 (fr)
DE (1) DE19754314A1 (fr)
WO (1) WO1999029937A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7247606B2 (en) * 2001-11-05 2007-07-24 Cognis Corporation Branched reaction products
EP2217639B1 (fr) * 2007-11-09 2018-10-24 Basf Se Compositions de nettoyage avec des polyalcanolamines alcoxylées
WO2009060060A1 (fr) * 2007-11-09 2009-05-14 Basf Se Polyalcanolamines alcoxylés
WO2013147062A1 (fr) * 2012-03-28 2013-10-03 Dic株式会社 Procédé de fabrication de nanofibres de cellulose, nanofibres de cellulose, mélange maître et composition de résine

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE547320A (fr) * 1955-06-13
NL228195A (fr) * 1957-06-21
NL234167A (fr) * 1958-01-04 1900-01-01
DE1163489B (de) * 1960-02-17 1964-02-20 Glanzstoff Courtaulds Gmbh Verfahren zur Herstellung von Faeden, Fasern oder Folien aus regenerierter Cellulosedurch Verspinnen von Viskose
NL259963A (fr) * 1960-02-17
CH411221A (de) * 1960-12-23 1966-04-15 Geigy Ag J R Verfahren zur Herstellung spinngefärbter, regenerierter Cellulosefasern
NL293298A (fr) * 1962-05-28
NL130198C (fr) * 1962-10-30
JPS5144143B2 (fr) 1972-06-27 1976-11-26
CH611346A5 (fr) * 1977-09-02 1979-05-31 Ciba Geigy Ag
IT7823984A0 (it) * 1978-05-30 1978-05-30 Snia Viscosa Procedimento per la produzione difibre di cellulosa rigenerata arricciate ed a alto modulo a umido.
DE3614834A1 (de) * 1986-05-02 1987-11-05 Henkel Kgaa Verwendung von aminogruppen enthaltenden polyglykolethern als schaumdrueckende zusaetze in schaumarmen reinigungsmitteln

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WO1999029937A1 (fr) 1999-06-17
DE19754314A1 (de) 1999-06-10
ATE233837T1 (de) 2003-03-15
US6475419B1 (en) 2002-11-05
EP1040214A1 (fr) 2000-10-04

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