EP0126838B1 - Procédé pour la fabrication de fibres insolubles dans l'eau de mono-esters d'acide maléique, succinique et phtalique de cellulose, ayant une capacité d'absorption d'eau et de liquides physiologiques extrêmement grande - Google Patents

Procédé pour la fabrication de fibres insolubles dans l'eau de mono-esters d'acide maléique, succinique et phtalique de cellulose, ayant une capacité d'absorption d'eau et de liquides physiologiques extrêmement grande Download PDF

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Publication number
EP0126838B1
EP0126838B1 EP84100623A EP84100623A EP0126838B1 EP 0126838 B1 EP0126838 B1 EP 0126838B1 EP 84100623 A EP84100623 A EP 84100623A EP 84100623 A EP84100623 A EP 84100623A EP 0126838 B1 EP0126838 B1 EP 0126838B1
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EP
European Patent Office
Prior art keywords
cellulose
acid
water
fibers
esterification
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.)
Expired
Application number
EP84100623A
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German (de)
English (en)
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EP0126838A2 (fr
EP0126838A3 (en
Inventor
Michael Dr. Dipl.-Chem. Diamantoglou
Gerhard Dr. Dipl.-Chem. Meyer
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AKZO PATENTE GmbH
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Akzo Patente GmbH
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Priority to AT84100623T priority Critical patent/ATE42352T1/de
Publication of EP0126838A2 publication Critical patent/EP0126838A2/fr
Publication of EP0126838A3 publication Critical patent/EP0126838A3/de
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Publication of EP0126838B1 publication Critical patent/EP0126838B1/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
    • D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
    • D01F2/28—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate

Definitions

  • the invention relates both to a process for the production of water-insoluble fibers from cellulose monoesters of maleic acid, succinic acid and phthalic acid with an extremely high absorption capacity for water and physiological liquids, and to the fibers themselves.
  • Hydrophilically modified viscose fibers are known under the trade name Viscosorb (cf. Lenzinger reports, issue 51, (1981), pages 34 ff). Their water retention capacity of 140 to 150% or 200 to 210% is not insignificantly increased compared to that of normal viscose (80 - 90%), but appears to be in need of improvement.
  • Fairly water-insoluble crosslinked fibrous salts of carboxymethyl cellulose are known from DT-A-1 912 740. They can have a water retention value of over 3,000. Even so that these fibrous salts are only 5 - 16% soluble, the fibrous water-soluble NaCMC salts initially made from cellulose must be crosslinked with epichlorohydrin or formaldehyde. The fibrous state of the end product only results from the specified short-fiber form of the chemical pulp to be converted, which generally has an average fiber length of 1 to 2.4 mm. The production of normal continuous fibers with targeted mechanical properties is naturally not possible in this way.
  • cellulose acetophthalates which are obtained from hydrolyzed cellulose acetate and an excess of phthalic anhydride in acetone or dioxane (Ullmann, 4th edition, volume 9, page 237). This creates esters of phthalic acid with a free carboxyl group. These products are suitable as water- or alkali-soluble textile sizes and are also used as antistatic agents in film coating.
  • the present invention provides new water-insoluble fibers which represent an interesting enrichment of the corresponding products of the prior art, in particular because of their high and extremely variable absorption capacity for water and physiological liquids.
  • LiCI-containing solutions of activated cellulose in dimethylacetamide or 1-methyl-2-pyrrolidone is known from DT-A-3 027 033. This reference describes several process variants for activating the cellulose and for producing the solutions mentioned.
  • the preservation of water-insoluble fibers of the type mentioned above with an extremely high absorption capacity for water and physiological liquids depends on several variables which are decisively influenced by the constitution of the respective macromolecular substance. To obtain fibers with satisfactory mechanical properties, it is essential to ensure a sufficiently high degree of polymerization. It is therefore important that the activated cellulose initially produced has an average degree of polymerization of 300 to 800, preferably 350-650, which must be largely maintained during the reaction with dicarboxylic acid anhydrides. To avoid degradation of the cellulose, the reaction temperature and reaction time must be coordinated. Extruders or continuous kneaders are suitable for processing more concentrated cellulose solutions (15 - 30% by weight) at temperatures up to 120 ° C and short residence times (e.g. 5 minutes). Reaction temperatures of 40 to 100 ° C. have proven to be particularly advantageous when converting the activated cellulose into cellulose monoesters.
  • esterification catalysts known per se, acids, such as methanesulfonic acid, perchloric acid, formic acid and sulfuric acid, or acid chlorides, such as acetyl chloride and propionyl chloride, are suitable for the esterification reaction. These acidic esterification catalysts can be used in amounts of about 2 to 10 percent by weight, based on the amount of acid anhydride.
  • basic esterification catalysts are also well suited for the esterification reactions in question, especially since they counteract cellulose degradation. Examples include the following tertiary amines: 4-N, N-dimethylaminipyridine, collidine, pyridine and triethylamine. Such basic Esterification catalysts, based on the acid anhydride, are added in equimolar amounts in order to bind the acids liberated in the reaction. The fibrous quaternary ammonium salts obtained after spinning can easily be converted into alkali metal salts or into secondary or tertiary ammonium salts using the methods described below.
  • Basic salts of monocarboxylic acids such as sodium acetate, potassium acetate, sodium propionate, potassium propionate, sodium butyrate and potassium butyrate are particularly suitable as esterification catalysts.
  • these salts are used in amounts of 2 to 10% by weight, preferably 5 to 10% by weight.
  • alkali metal acetates in amounts of 2 to 10% by weight, based on the dicarboxylic acid anhydride used, has proven to be particularly advantageous.
  • the absorption capacity for water and physiological liquids is shown below by the parameters water retention capacity (WRV) and retention capacity of synthetic urine (SURV).
  • the water retention capacity according to DIN 53 814 is a measure of the water retained in the individual fibers after extensive immersion in water and subsequent defined centrifugation. The same applies to the retention capacity of synthetic urine, which was measured according to the same regulation.
  • the cellulose monoester fibers of maleic acid in which the hydroxyl hydrogen of the carboxyl group is not replaced by an alkali metal, have a high water retention capacity (WRV) if their degree of esterification is between about 0.4 and 1.3.
  • the WRV value with a degree of esterification (DS) of 0.4 is 200%. It runs through a maximum at a DS of approximately 0.7 with a WRV value of 1100%, in order to then fall back to a WRV value of 250% up to a degree of esterification of 1.2, with the WRW values at even higher degrees of esterification. Values continue to fall.
  • unneutralized cellulose monoester fibers of maleic acid with a degree of esterification of 0.4 to 1.3 is one of the preferred embodiments of the invention.
  • the PH value of such fibers lies outside of the alkaline range, which is essential in any case for the areas of hygiene and medicine.
  • the cellulose monoester fibers of succinic acid in which the hydroxyl hydrogen of the carboxyl group is not partially or completely replaced by an alkali metal, already have a good water retention capacity of 220% at a degree of esterification of about 0.3. From then on, the WRV value rises in such a surprising manner that the water retention capacity is already almost 5300% at a DS of 0.67. This astonishingly high WRV value drops again with higher degrees of esterification. It reaches 1900% with a DS of 1.7.
  • the production of unneutralized, ie not in salt form, cellulose monoester fibers of succinic acid with a degree of esterification of 0.3 to 1.7 is accordingly a further preferred embodiment of the invention.
  • the cellulose monoester fibers of phthalic acid in which the hydroxyl hydrogen of the carboxyl group is not partially or completely replaced by an alkali metal, have a relatively low WRV value at low degrees of esterification, e.g. B. with a DS of 0.20 a WRV value of 125%, which continues to decrease with increasing DS values.
  • a considerable increase in water retention capacity is achieved according to the invention in the case of such fibers by converting them into the corresponding fibrous salts in an essentially organic solvent by reaction with alkali metal hydroxides and / or alkali metal alcoholates or ammonia or primary or secondary amines.
  • Alcoholic alkali metal hydroxide solutions which are prepared by dissolving NaOH, KOH, LiOH or NH 3 in the corresponding alcohols, such as methanol, ethanol, propanol and butanol, optionally with the use of small amounts of water, are particularly suitable for the implementation of the cellulose monoester fibers.
  • the neutralization should take place at a temperature of 10 to 25 ° C.
  • the corresponding bicarbonates or carbonates in conjunction with low water additions to the alcohols used can also be used for this purpose.
  • primary or secondary amines are also suitable for the reaction, such as. B. diethylamine, propylamine and ethanolamine. Are other organic solvents used, such as. B.
  • acetone or dioxane these should also be added as solubilizers, small amounts of water, usually about 10 to 30 wt .-%. Otherwise, the most suitable amount of water added can easily be determined by an average person skilled in the art by simple experiments, since the upper limit is only on the water swelling capacity of the fibers in question, which in turn is dependent on the degree of esterification.
  • Substantially completely neutralized water-insoluble cellulose monoester fibers of phthalic acid with an extremely high absorption capacity for water and physiological liquids can only be produced in the manner described in the narrowly limited degree of esterification range from 0.1 to 0.4.
  • the cellulose monoester of phthalic acid increases the WRV value from 100 to about 4,000%. With higher degrees of esterification, the fibers become water-soluble.
  • the manufacturability of such fibers is tied to the narrowly limited degree of esterification range from 0.1 to 0.4. Above a degree of esterification of about 0.4, the fibers lose the desired property of being water-insoluble.
  • Another preferred embodiment of the invention is the production of essentially neutralized cellulose monoester fibers of maleic acid, succinic acid and phthalic acid, which have a degree of esterification of 0.1 to 0.4.
  • Such fibers can be used advantageously for the production of absorbent fabrics, such as diapers, wipes and vapor filters.
  • the size of the water retention capacity can be varied in the desired direction, since the WRV values of such partially neutralized fibers lie between those of the unneutralized and completely neutralized cellulose monoester fibers.
  • the fibers according to the invention have fiber strengths of 4-20 cN / tex, preferably 6-15 cN / tex, elongations of 4-20%, preferably 6-16%, and a water retention capacity of> 200%, preferably> 300% , which can generally be increased in the manner described to a WRV value of a few thousand percent.
  • the water-insoluble fibers according to the invention also have an increased water absorbency (WSV).
  • WSV water absorbency
  • the fibers according to the invention are spun from cellulose monoesters of maleic acid, succinic acid and phthalic acid by conventional wet spinning processes and with conventional devices of this type.
  • wet spinning the cellulose monoester solution prepared in this way is pressed out through nozzles with fine bores into a suitable coagulation bath, for example an alcohol bath kept at room temperature.
  • Suitable coagulants are, for example, the alcohols methanol, ethanol, propanol and butanol, ketones such as dimethyl ketone, methyl ethyl ketone, diethyl ketone, dipropyl ketone and dibutyl ketone, and ethers such as dipropyl ether, dibutyl ether, diisoamyl ether and dioxane.
  • ketones such as dimethyl ketone, methyl ethyl ketone, diethyl ketone, dipropyl ketone and dibutyl ketone
  • ethers such as dipropyl ether, dibutyl ether, diisoamyl ether and dioxane.
  • the development of maximum fiber properties can be supported by running the threads combined to form a spun cable through a series of washing baths which contain the abovementioned solvents and, if appropriate, inorganic salts, in order to remove residues of the solvents used and LiCl. At the same time, stretching can be combined with the aftertreatment, which allows the desired fiber properties to be set.
  • the draw ratio can be varied from 1: 1 to 3: 1.
  • the cellulose monophthalate fibers obtained in this way have the following properties:
  • the fibrous sodium salt of cellulose monophthalate has the following swelling values:
  • the cellulose monophthalic acid esters listed in Table 1 are produced in principle by the same method as that given in Example 1. The same applies to their further processing to the claimed saliform fibers.
  • the cellulose maleinate fibers obtained have the following properties:
  • the cellulose maleate fibers are converted to the ammonium salt.
  • the fibrous cellulose maleinate salts obtained in this way have the following swelling values:
  • cellulose monoesters of maleic acid were made and spun into fibers based on the procedure of Example 9 and the reaction conditions of Table 2. Water was used as the coagulant for weakly swelling cellulose derivatives (WRV: ⁇ 200%) and for strongly swelling (WRV:> 200%) ethanol.
  • the resulting cellulose succinate fibers have the following properties:
  • the cellulose succinate fibers produced in this way have the following properties:
  • the fibrous sodium salt of the cellulose succinic acid ester has the following properties:
  • 16.2 g (0.1 mol) of cellulose are dissolved in 278.4 g (3.2 mol) of technical dimethylacetamide and 29 g (0.68 mol) of LiCl.
  • 6.1 g (0.05 mol) of 4-N, N-dimethylaminopyridine and 5 g (0.05 mol) of succinic anhydride are added to the cellulose solution in succession. The mixture is first heated at 40 ° C. for 5 hours, then stirred at room temperature for 15 hours and then precipitated with ethanol, washed and dried.
  • the short-fiber cellulose monoester of succinic acid produced in this way has the following properties:
  • the cellulose ester obtained has a degree of esterification of 0.28.

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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)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Claims (7)

1. Procédé de préparation de fibres insolubles dans l'eau en mono-esters cellulosiques de l'acide maléique, de l'acide succinique et de l'acide phtalique, ayant une capacité d'absorption de l'eau et des liquides physiologiques extrêmement élevée, caractérisé en ce que
a) on prépare, à une température de 20 à 80°C, une solution de cellulose activée dans le diméthylacétamide ou la 1-méthyl-2-pyrrolidone, qui contient 5 à 30 % en poids de cellulose activée ayant un degré de polymérisation moyen de 300 à 800 et 3 à 20 % en poids de LiCI,
b) on fait réagir, à une température de 20 à 120°C, en présence de catalyseurs d'estérification connus en soi, la cellulose ainsi dissoute avec les anhydrides d'acide dicarboxylique correspondants dans un rapport molaire de 1 : 0,20 à 1 : 4, jusqu'à un degré d'estérification de 0,1 à 1,7,
c) on file, par filage par voie humide, les solutions de mono-ester cellulosique obtenues dans un milieu de coagulation et
d) on transforme, dans un solvant essentiellement organique, les fibres en mono-esters cellulosiques d'acide phtalique et éventuellement celles en mono-esters cellulosiques d'acide maléique et d'acide succinique, par reaction avec des hydroxydes de métal alcalin et/ou des alcoolates de métal alcalin ou l'ammoniac ou des amines primaires ou secondaires, partiellement ou totalement en les sels correspondants sous forme de fibres.
2. Procédé selon la revendication 1, caractérisé en ce que la transformation de la cellulose activée en mono- esters cellulosiques a lieu à une température réactionnelle de 40 à 100° C.
3. Procédé selon les revendications 1 et 2, caractérisé en ce que l'on emploie, lors de la réaction de la cellulose activée avec les anhydrides d'acide dicarboxylique, des acétates de métaux alcalins en tant que catalyseurs, à une teneur de 2 à 10 % en poids par rapport à l'anhydride d'acide dicarboxylique mis en réaction.
4. Procédé selon les evendications 1 à 3, caractérisé en ce que l'on file des solutions de monoester cellulosique de l'acide maléique ayant un degré d'estérification de 0,4 à 1,3 et de mono-ester cellulosique de l'acide succinique ayant un degré d'estérification de 0,3 à 1,7 et n'effectue pas une neutralisation subséquente des fibres obtenues.
5. Procédé selon les revendications 1 à 3, caractérisé en ce qu'on neutralise pratiquement totalement les fibres obtenues avec des solutions alcooliques d'hydroxyde de métal alcalin à une température de 10 à 25" C.
6. Procédé selon la revendication 5, caractérisé en ce qu'on transforme en sels, sous forme de fibres, les fibres de mono-ester cellulosique d'acide maléique, d'acide succinique et d'acide phtalique qui présentent un degré d'estérification de 0,1 à 0,4.
7. Fibres insolubles dans l'eau en mono-esters cellulosiques de l'acide maléique, de l'acide succinique et de l'acide phtalique, ayant une capacité d'absorption de l'eau et des liquides physiologiques très élevée, caractérisées en ce qu'elles présentent :
a) un degré d'estérification de 0,1 à 1,7,
b) un degré de polymérisation moyen de 300 à 800,
c) une tenacité de fibres de 4 à 20 cN/tex, à l'état conditionné,
d) un allongement de 4 à 20 % à l'état conditionné et
e) une capacité de rétention de l'eau de 200 à 5300 %.
EP84100623A 1983-04-02 1984-01-20 Procédé pour la fabrication de fibres insolubles dans l'eau de mono-esters d'acide maléique, succinique et phtalique de cellulose, ayant une capacité d'absorption d'eau et de liquides physiologiques extrêmement grande Expired EP0126838B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84100623T ATE42352T1 (de) 1983-04-02 1984-01-20 Verfahren zur herstellung von wasserunloeslichen fasern aus cellulosemonoestern der maleinsaeure, bernsteinsaeure und phthalsaeure mit einem extrem hohen absorptionsvermoegen fuer wasser und physiologische fluessigkeiten.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3312022A DE3312022A1 (de) 1983-04-02 1983-04-02 Verfahren zur herstellung von wasserunloeslichen fasern aus cellulosemonoestern der maleinsaeure, bernsteinsaeure und phthalsaeure mit einem extrem hohen absorptionsvermoegen fuer wasser und physiologische fluessigkeiten
DE3312022 1983-04-02

Publications (3)

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EP0126838A2 EP0126838A2 (fr) 1984-12-05
EP0126838A3 EP0126838A3 (en) 1987-05-27
EP0126838B1 true EP0126838B1 (fr) 1989-04-19

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US (1) US4734239A (fr)
EP (1) EP0126838B1 (fr)
JP (1) JPS59187612A (fr)
AT (1) ATE42352T1 (fr)
CA (1) CA1229208A (fr)
DE (2) DE3312022A1 (fr)

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GB2220881B (en) * 1988-04-28 1992-07-08 Toyo Boseki Improvements in or relating to superabsorbent materials
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DE19856394C1 (de) * 1998-12-07 2000-09-14 Inst Textil & Faserforschung Herstellung von Celluloseestern durch Umsetzung von Cellulose mit Dicarbonsäureanhydriden unter heterogener Reaktionsführung und deren Verwendung
JP2003023893A (ja) * 2001-07-10 2003-01-28 Ajinomoto Co Inc 動物飼育用資材
US6627750B2 (en) 2001-08-03 2003-09-30 Rayonier Inc. Highly carboxylated cellulose fibers and process of making the same
WO2005092828A1 (fr) * 2004-03-25 2005-10-06 Sumitomo Chemical Company, Limited Processus de production de 3-méthyl-2-butényl acétate
JP2006045190A (ja) * 2004-07-02 2006-02-16 Sumitomo Chemical Co Ltd 酢酸３−メチル−２−ブテニルの製造方法
US20070142804A1 (en) * 2005-12-16 2007-06-21 Bernard Bobby L Hollow-core fibers
US11173106B2 (en) * 2009-10-07 2021-11-16 Johnson & Johnson Consumer Inc. Compositions comprising a superhydrophilic amphiphilic copolymer and a micellar thickener
US8399590B2 (en) 2009-10-07 2013-03-19 Akzo Nobel Chemicals International B.V. Superhydrophilic amphiphilic copolymers and processes for making the same
US8258250B2 (en) 2009-10-07 2012-09-04 Johnson & Johnson Consumer Companies, Inc. Compositions comprising superhydrophilic amphiphilic copolymers and methods of use thereof
EP4327790A1 (fr) 2022-08-25 2024-02-28 Corman SpA Produit absorbant biodégradable

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Also Published As

Publication number Publication date
US4734239A (en) 1988-03-29
DE3312022A1 (de) 1984-10-11
CA1229208A (fr) 1987-11-17
JPS59187612A (ja) 1984-10-24
EP0126838A2 (fr) 1984-12-05
DE3477815D1 (en) 1989-05-24
ATE42352T1 (de) 1989-05-15
DE3312022C2 (fr) 1987-02-26
EP0126838A3 (en) 1987-05-27

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