EP0047962B1 - Procédé pour la fabrication de fibres de filaments, objets formés gonflables de polyméres d'acrylonitrile et produits ainsi obtenus - Google Patents

Procédé pour la fabrication de fibres de filaments, objets formés gonflables de polyméres d'acrylonitrile et produits ainsi obtenus Download PDF

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Publication number
EP0047962B1
EP0047962B1 EP81107049A EP81107049A EP0047962B1 EP 0047962 B1 EP0047962 B1 EP 0047962B1 EP 81107049 A EP81107049 A EP 81107049A EP 81107049 A EP81107049 A EP 81107049A EP 0047962 B1 EP0047962 B1 EP 0047962B1
Authority
EP
European Patent Office
Prior art keywords
fibers
filaments
carboxyl groups
acrylonitrile
units
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
EP81107049A
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German (de)
English (en)
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EP0047962A3 (en
EP0047962A2 (fr
Inventor
Bernd Dr. Huber
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoechst AG
Original Assignee
Hoechst AG
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Filing date
Publication date
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Application filed by Hoechst AG filed Critical Hoechst AG
Publication of EP0047962A2 publication Critical patent/EP0047962A2/fr
Publication of EP0047962A3 publication Critical patent/EP0047962A3/de
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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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
    • 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
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
    • D01F11/06—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber

Definitions

  • the invention relates to a process for the production of threads, fibers and structures formed therefrom from acrylic polymers, the thread-forming substance of which consists of acrylonitrile and monomer units copolymerizable with acrylonitrile and has carboxyl groups which have at least partially been converted into the salt form, and the threads and fibers obtained thereby.
  • Acrylic polymer fibers containing salts of carboxyl groups are known.
  • DE-A-2 434 232 describes a process for the production of acrylic fibers with improved hygroscopicity, in which raw materials containing carboxyl groups are spun into fibers, the fibers are then crosslinked and the carboxyl groups are converted to the salt form in an aqueous alkaline medium.
  • polymers with up to 12% acrylic acid (corresponding to 7.5% by weight COOH groups) or 15% methacrylic acid (corresponding to 7.8% by weight COOH groups) are used.
  • the fibers obtained have good textile-technological properties, but due to the crosslinking they have been carried out, they are not swellable or only to a very limited extent.
  • DE-A-2 358 853 describes a process for producing fibers with high water swellability, in which spun fibers are crosslinked with hydroxylamine and then saponified in an aqueous-alkaline medium.
  • the fibers produced in this way occur in a strongly swollen form. If you dry these heavily swollen fibers or threads, you get a very brittle and in some cases also strongly bonded fiber material that cannot be further processed into textile structures such as yarns, knits or fabrics by the conventional method.
  • Alkaline hydrolysis can also be carried out in organic solvents containing alkaline water, such as, for example, glycol or glycerol.
  • alkaline water such as, for example, glycol or glycerol.
  • the products obtained in this way are also brittle in the dry state and cause problems in textile further processing (DE-A-2 903 267).
  • DE-A-2 942 064 describes swellable acrylic fibers with a core-sheath structure in which the sheath is composed of a hydrophilic, carboxyl-containing crosslinked polymer and the core is composed of a normal acrylonitrile polymer and / or another polymer.
  • the process described here in which the cladding layer is produced by alkaline hydrolysis in an aqueous medium, is, however, very complex since the fibers are obtained in a strongly swollen state and have to be dried with high energy input. In addition, there is always the great risk that, despite the crosslinking that has been carried out, the fibers stick strongly to one another during drying.
  • the thread-forming substance consists of an acrylic polymer which, in addition to acrylonitrile units and other units copolymerizable with acrylonitrile, contains 10 to 30% by weight of carboxyl groups.
  • Such threads and fibers can be obtained by spinning a polymer raw material according to the spinning processes customary for acrylic threads and fibers, the polymer raw material used being an acrylonitrile polymer or copolymer which has been partially saponified in the heterogeneous phase by dilute aqueous acids. A dilute aqueous sulfuric acid with a content of 40 to 50% by weight is particularly suitable for the saponification.
  • Such threads and fibers made of carboxyl-containing acrylic polymers, their connection and process for their preparation are the subject of a parallel application on the same day (EP-A-0 048 846).
  • the method according to the invention can also be applied to previously formed structures such as wadding, nonwovens, yarns or other textile fabrics which contain fibers containing carboxyl groups.
  • the swelling capacity can be precisely adjusted by the amount of the bases applied.
  • the reaction of the fibers and threads with free carboxyl groups with gaseous bases is a convenient method for converting the free carboxyl groups into the salt form.
  • Particularly suitable bases are ammonia, hydrazine and basic reacting organic nitrogen compounds, which are evaporable.
  • compounds which can be vaporized at temperatures below 200 ° C., optionally also under reduced pressure, can preferably be used.
  • monomethylamine, dimethylamine, trimethylamine, the corresponding ethyl, propyl, butyl, pentyl and hexylamines and also the corresponding mixed compounds such as methylethylamine or methylbutylamine can be used.
  • Amines which also carry other functional groups for example 2-hydroxyethylamine or compounds in which the other functional group can in turn be an amine, for example 1,2-diaminoethane, are also suitable.
  • Cyclic, saturated or unsaturated nitrogen compounds such as pyrrolidine, pyrroline, pyrol, pyridine and their derivatives are also suitable.
  • other basic organic compounds such as hydrazines can also be used.
  • the fibers and filaments containing carboxyl groups can also be reacted in the anhydrous liquid phase with liquid bases or their solutions in anhydrous organic solvents.
  • liquid bases or their solutions in anhydrous organic solvents In water-free organic solvents it is also possible to use basic compounds which are not very volatile, such as, for example, sodium hydroxide or potassium hydroxide in alcoholic solutions or alcoholates dissolved in alcohols.
  • the threads and fibers according to the invention are particularly suitable for use in the hygiene sector, for example for the production of baby diapers or tampons, as an admixture fiber in fiber or thread fleeces, for example for use as shoe lining, for air-permeable but waterproof fabrics, as filter material, as an artificial nutrient medium for plant crops, as a water-retaining agent for garden soils, as drainage or spacer threads in cables for transmitting messages in order to localize a possible water ingress and the use of e.g. B. in a mixture with other synthetic fibers or threads in the production of synthetic leather.
  • the threads produced according to the invention in which the carboxyl groups are at least partially in the salt form, still have proper textile technology values. They can therefore be processed into shaped structures such as yarns, nonwovens, fiber slats, wadding, textile fabrics, etc., as long as care is taken to ensure that they do not come into contact with large amounts of water.
  • the swellable threads and fibers according to the invention are distinguished by tensile strength of more than 10 cN / tex and knot strengths of more than 6 cN / tex. They can be processed further with the help of conventional textile-technical processes to wadding, yarns and fabrics, since their textile-technological values correspond at least to those of wool.
  • the swellability or the water retention capacity can vary within wide limits depending on the degree of salt formation.
  • the water retention capacity can be set to values of, for example, 50 to 200%.
  • values of the water retention capacity can be set from a few hundred to a few thousand percent.
  • the swellable threads and fibers according to the invention have in their thread-forming substance about 10 to 30% by weight of carboxyl groups which have at least partially been converted into the salt form.
  • Powdery acrylic polymers of 93.7% acrylonitrile, 5.8% methyl acrylate and 0.5% sodium methallyl sulfonate were saponified heterogeneously with 46.2 to 48.2% sulfuric acids. The saponification was carried out under reflux for 2.5 hours. After the reaction solution had cooled, the polymer was filtered off, washed sulfate-free with water and then dried. The partially saponified acrylic polymers obtained were dissolved in dimethylformamide (DMF) to form spinning solutions and spun into threads using the spinning processes known from polyacrylonitrile. The threads were washed, drawn, finished, dried, post-drawn, crimped and then cut into staple fibers with a cutting length of 40 mm in the usual way.
  • DMF dimethylformamide
  • the fibers obtained show the following properties:
  • DMSO dimethyl sulfoxide
  • the factor of the sodium hydroxide solution was determined with oxalic acid, dissolved in 60 ml of water and mixed with 25 ml of DMSO.
  • the actual centrifugation was carried out using a laboratory centrifuge from HERAEUS CHRIST GmbH, type UJO.
  • the containers and samples were centrifuged at 4000 rpm for 30 minutes each.
  • the distance between the cup nets and the axis of the centrifuge was 8.5 cm.
  • the centrifuged fiber samples were then weighed out and then dried in a drying cabinet at 120 ° C. to constant weight. The weight difference between the wet and dried sample, divided by the dry weight, was given in percent as water retention.
  • the staple fiber samples thus produced were further processed into card slivers and stored in this form overnight in glass containers filled with gaseous ammonia.
  • the fibers obtained according to the 4 examples were not glued together, the card slivers could be processed into yarns without difficulty.

Claims (7)

1. Procédé pour la préparation de fils, fibres et matières formées, gonflables, à partir de polymères acryliques, qui contiennent dans le polymère des groupes carboxyle présents sous forme sel, caractérisé en ce que les fils, fibres ou matières formées à partir d'eux, dont la substance fibrogène est constituée d'acrylonitrile et de motifs monomères copolymérisables avec l'acrylonitrile et contient 10 à 30% en poids de groupes carboxyle, est mise à réagir, en l'absence d'eau, avec une quantité de substances basiques telle que les groupes carboxyle soient au moins partiellement convertis en leur forme sel.
2. Procédé selon la revendication 1, caractérisé en ce que le pouvoir gonflant des fils, fibres ou matières formées préparés ajusté par la quantité des substances basiques ajoutées.
3. Procédé selon l'une des revendications 1 ou 2, caractérisé en ce qu'on utilise en tant que substance basique un composé possédant au moins un atome d'azote à réaction basique.
4. Procédé selon la revendication 3, caractérisé en ce que le composé contenant de l'azote est l'ammoniac, l'hydrazine ou un composé azoté organique vaporisable.
5. Procédé selon les revendications 3 ou 4, caractérisé en ce que le composé azoté est mis à réagir à l'état gazeux avec les fils, fibres ou matières formées à utiliser.
6. Fils et fibres gonflables, dont la substance formant les fils est constituée d'un polymère acrylique nonréticulé, qui contient outre des motifs acrylonitrile et d'autres motifs copolymérisables avec l'acrylonitrile jusqu'à environ 30% en poids de groupes carboxyle qui ont été au moins partiellement. convertis en leur forme sel, et dans lesquels les filaments individuels présentent à l'état sec une résistance à la traction supérieure à 10 cN/tex et une stabilité des noeuds supérieure à 6 cN/tex, et qui peuvent être bien transformés, à l'aide des procédés classiques de la technologie des textiles, en ouates, filés et étoffes.
7. Fils et fibres selon la revendication 6, caractérisés en ce qu'ils présentent une stabilité des noeuds de 8 cN/tex, ou plus.
EP81107049A 1980-09-13 1981-09-08 Procédé pour la fabrication de fibres de filaments, objets formés gonflables de polyméres d'acrylonitrile et produits ainsi obtenus Expired EP0047962B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3034660A DE3034660C2 (de) 1980-09-13 1980-09-13 Verfahren zur Herstellung von quellfähigen Fäden, Fasern und geformten Gebilden aus Acrylpolymeren sowie die dabei erhaltenen Produkte
DE3034660 1980-09-13

Publications (3)

Publication Number Publication Date
EP0047962A2 EP0047962A2 (fr) 1982-03-24
EP0047962A3 EP0047962A3 (en) 1983-06-22
EP0047962B1 true EP0047962B1 (fr) 1985-12-04

Family

ID=6111913

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81107049A Expired EP0047962B1 (fr) 1980-09-13 1981-09-08 Procédé pour la fabrication de fibres de filaments, objets formés gonflables de polyméres d'acrylonitrile et produits ainsi obtenus

Country Status (4)

Country Link
US (1) US4600407A (fr)
EP (1) EP0047962B1 (fr)
JP (1) JPS5777312A (fr)
DE (2) DE3034660C2 (fr)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NZ217571A (en) * 1985-09-16 1989-07-27 Dow Chemical Co Treatment of liquids with ethylene copolymer to remove metal ions; copolymers of ethylene with 1-chloro-2-hydroxypropyl-trimethyl ammonium acrylate
US4766036A (en) * 1985-09-16 1988-08-23 The Dow Chemical Company Process for producing porous fibers from orientable olefin polymers having cation-containing, pendent reactive side-groups and the resultant product
JP2605666B2 (ja) * 1986-05-06 1997-04-30 日本エクスラン工業株式会社 水膨潤性繊維
JPS63190077A (ja) * 1986-09-26 1988-08-05 旭化成株式会社 アクリル系吸水繊維の製造方法
JPS63145485A (ja) * 1986-12-05 1988-06-17 旭化成株式会社 吸水性繊維及び該吸水性繊維を含有する水膨潤性組成物
JPH01183515A (ja) * 1987-12-30 1989-07-21 Japan Exlan Co Ltd 吸水性高強度繊維
US5418284A (en) * 1989-05-08 1995-05-23 Cytec Technology Corp. Surface-modified polyacrylonitrile beads
US5494746A (en) * 1991-01-03 1996-02-27 Mitsubishi Kasei Corporation Acrylic fiber and process for producing the same
JP3369380B2 (ja) * 1995-11-29 2003-01-20 東洋紡績株式会社 改善された高吸放湿性繊維及びその製造方法
US6482344B1 (en) 2000-08-23 2002-11-19 Stockhausen Gmbh & Co. Kg Superabsorbent polymer fibers having improved absorption characteristics
US7599589B2 (en) * 2005-07-20 2009-10-06 Draka Comteq B.V. Gel-free buffer tube with adhesively coupled optical element
US7567739B2 (en) * 2007-01-31 2009-07-28 Draka Comteq B.V. Fiber optic cable having a water-swellable element
US8682123B2 (en) 2010-07-15 2014-03-25 Draka Comteq, B.V. Adhesively coupled optical fibers and enclosing tape
DE102013003755A1 (de) * 2013-03-06 2014-09-11 Carl Freudenberg Kg Belüftungseinsatz

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5242916B2 (fr) * 1972-05-31 1977-10-27
JPS5145695B2 (fr) * 1973-08-24 1976-12-04
JPS573700B2 (fr) * 1973-11-06 1982-01-22
DE2607071C2 (de) * 1976-02-21 1985-09-19 Bayer Ag, 5090 Leverkusen Synthesefasern und -fäden mit hoher Feuchtigkeitsaufnahme und großem Wasserrückhaltevermögen
JPS53123453A (en) * 1977-04-05 1978-10-27 Toray Ind Inc Acrylic polymer solution having good fiber-forming proterty
JPS5598915A (en) * 1979-01-16 1980-07-28 Japan Exlan Co Ltd Production of fiber swelling with water
DE2903267A1 (de) * 1979-01-29 1980-08-07 Hoechst Ag Verfahren zur herstellung von acrylpolymeren mit hoher wasserquellfaehigkeit und deren verwendung

Also Published As

Publication number Publication date
DE3034660A1 (de) 1982-04-15
EP0047962A3 (en) 1983-06-22
DE3034660C2 (de) 1982-09-16
JPH0253526B2 (fr) 1990-11-19
US4600407A (en) 1986-07-15
EP0047962A2 (fr) 1982-03-24
DE3173137D1 (en) 1986-01-16
JPS5777312A (en) 1982-05-14

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