EP0089593B1 - Verfahren zur Herstellung von Fäden und Fasern aus Acrylnitrilpolymerisaten - Google Patents

Verfahren zur Herstellung von Fäden und Fasern aus Acrylnitrilpolymerisaten Download PDF

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Publication number
EP0089593B1
EP0089593B1 EP83102492A EP83102492A EP0089593B1 EP 0089593 B1 EP0089593 B1 EP 0089593B1 EP 83102492 A EP83102492 A EP 83102492A EP 83102492 A EP83102492 A EP 83102492A EP 0089593 B1 EP0089593 B1 EP 0089593B1
Authority
EP
European Patent Office
Prior art keywords
copper
ions
solution containing
solution
treatment
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
EP83102492A
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German (de)
English (en)
French (fr)
Other versions
EP0089593A2 (de
EP0089593A3 (en
Inventor
Walter Dr. Fester
Bernd Dr. Huber
Lieselotte Dr. Wappes
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
Priority date (The priority date 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 date listed.)
Filing date
Publication date
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=6158547&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0089593(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Hoechst AG filed Critical Hoechst AG
Priority to AT83102492T priority Critical patent/ATE16120T1/de
Publication of EP0089593A2 publication Critical patent/EP0089593A2/de
Publication of EP0089593A3 publication Critical patent/EP0089593A3/de
Application granted granted Critical
Publication of EP0089593B1 publication Critical patent/EP0089593B1/de
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
    • D06M11/55—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
    • D06M11/56—Sulfates or thiosulfates other than of elements of Groups 3 or 13 of the Periodic Table
    • 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
    • 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
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
    • D06M11/13—Ammonium halides or halides of elements of Groups 1 or 11 of the Periodic Table

Definitions

  • the invention relates to processes for the production of acrylonitrile-containing fibers and threads after a dry or wet spinning process, in which the fibers or threads that have not yet been healed by drying or a thermal treatment above 100 ° C. are continuously treated with an aqueous solution of copper (I) ions .
  • spun cables or strands of single threads which contain acrylonitrile building blocks in their thread-forming substance, absorb large amounts of copper (I) ions from treatment baths even at room temperature, provided that these strands or cables have not yet undergone temperature treatment above 100 ° C or had been subjected to a drying process.
  • the copper (I) ions are absorbed within seconds and can therefore be integrated into the production process of threads and fibers containing acrylonitrile without difficulty. It does not matter whether the threads were produced using a dry or wet spinning process.
  • Copper (I) ions are particularly easily absorbed in wet-spun threads, but it is also possible to load dry-spun threads containing solvent within the washing process or aftertreatment process with copper (I) ions. Depending on the desired amount of copper (1) in the fiber, the treatment can take place before, during or after washing the strands or cables.
  • the copper (I) content in the threads can of course also be influenced by the length of the exposure time and the concentration in the bath liquid.
  • the uptake of the copper (I) ions from a bath or from a spray zone at room temperature is largely reversible; that is, the copper content can be removed by subsequent washes. For this reason, it is necessary to fix the copper content in the fiber.
  • This fixation can be carried out by a temperature treatment above about 60 ° C, preferably above 85 ° C, or by a drying process in which correspondingly high temperatures are also exceeded.
  • the temperature is important for the fixing process, but also the dwell time. While the fixation in z. B. 65 ° C requires longer dwell times, only temperatures of one minute or significantly less are required at temperatures above 100 ° C for the same effect. If the copper (I) ions are taken up from a bath at a temperature of more than about 60 ° C., the copper (I) ions are also fixed in the polymer molecule.
  • the copper (1) content can no longer be washed out; it can be assumed that under these conditions the copper (I) ions have been incorporated into the polyacrylonitrile in a complex manner.
  • a common procedure is to pull the cable or the strands through a copper (I) ion-containing bath and after squeezing off the excess bath liquid z. B. over hot godets of z. B. 100 ° C surface temperature. A further wash can then be provided in order to remove copper salts etc. adhering to the surface from the threads and to apply a customary preparation in a subsequent bath before the threads are finally dried.
  • the cables have a copper (I) ion solution directly before the first drying and to fix them with drying.
  • the threads have copper compounds that are not superficially bound on the surface and can be detached on first contact with water.
  • heat treatment it is also possible to heat treatment to fix the copper content in a steam atmosphere, e.g. B. at temperatures above 95 ° C or using infrared emitters or by guiding over a contact heat path.
  • a copper (I) ion solution can be produced directly by electrolytic reduction of copper (II) solutions or by heating copper (II) salt solutions in the presence of metallic copper, the copper being added in the form of a powder or by electrolysis can be generated.
  • the solution can be prepared by mixing a copper (II) salt solution with a reducing agent.
  • the copper salt CuS0 4 x 5 H 2 0 has proven to be particularly favorable as the usual copper (II) salt.
  • the concentration of copper (I) ions can vary within wide limits depending on the desired fiber properties. If the copper (I) solution is prepared by reducing copper (II) compounds, the reducing agent must be used at least in the stoichiometric amount. A slight excess is preferably used in order to avoid the presence of copper (II) salts. In contrast to the copper (I) compounds, the copper (II) ions cannot be bound in a complex manner by the polymer molecules, so they are washed out in subsequent washes or dyeing processes and pollute the wastewater. A large excess of reducing agents generally has no further advantages. Rather, there is a risk that the copper (I) compound is further reduced to metallic copper, which can then no longer be embedded in the threads or fibers. An exception here seems to be the aldehyde sulfoxylates, in which a larger excess at room temperature does not increase the copper deposition.
  • the copper (I) ion solution can be applied by various known methods, for example B. by passing the cables or strands through a bath. However, it is also possible to apply the solution by spraying or the like. It is advantageous to squeeze the fiber cables or strands as far as possible before and after the treatment with the aqueous copper (I) ion solution. In this way it can be ensured that the carry-over of the copper ions into other baths and an unnecessary dilution of the copper (I) ion treatment bath remains within tolerable limits. Of course, it is advantageous if measures are taken to ensure good and uniform penetration of a thread cable or strand in the treatment liquor. For example, cables should be routed so wide in the treatment bath that depletion of the copper ion concentrations or delayed penetration with the treatment bath inside the cable should be neglected as far as possible.
  • the acrylonitrile-containing polymers used are understood to mean those polymers which are composed of more than 50%, preferably more than 85%, of acrylonitrile units.
  • Other components that can be considered include, for. As acrylic acid, methacrylic acid and their esters and amides, vinyl acetate, vinyl chloride, vinylidene chloride, vinylidene cyanide or other unsaturated compounds copolymerizable with acrylonitrile.
  • the threads and fibers produced according to the invention offer a wide range of possible uses.
  • gently dried fibers that still have a good degree of whiteness can be dyed with acid dyes, they have bactericidal properties and can also be subjected to accelerated pre-oxidation for carbon fiber production.
  • the good dyeability with anionic dyes can be used to carry out the dyeing already during the manufacturing process.
  • Today acrylic fibers are usually dyed with cationic dyes. This concerns both the discontinuous dyeing of the finished fiber and the gel dyeing, in which the fiber is dyed in the gel state during the fiber production process before drying.
  • cationic dyes already have high light fastness on acrylic fibers, the fastness of the dyeing with anionic dyes, such as e.g. can be achieved according to the old cupro-ion process, cannot be achieved. For this reason, when there are high demands on light fastness, such as. B. for fibers for the awning sector, expensive color pigments used in spin dyeing.
  • the dye liquor used can be used together with the copper (I) ion solution or in a separate bath after treatment with the copper (I) salt solution.
  • the freshly spun threads were withdrawn from the precipitation bath at a speed of 4 m / min, subjected to wet drawing at 85 ° C. of 1: 4.05 in a bath which consisted of 60% dimethylformamide and 40% water, and then with Wash water free of solvents at 30 ° C.
  • the sliver was squeezed to remove most of the water and passed through a trough containing an aqueous solution of 100 g / l CuS0 4 x 5 H 2 0 and 20 g / l of the sodium salt of hydroxymethanesulfinic acid (formula: CH 2 SO 2 Na x 2H 2 0), (trade name: Rongalit "C) (residence time 1.5 sec.).
  • the solution simultaneously contained the required fiber preparation.
  • the solution was obtained by continuously metering an aqueous solution of 200 g / l CuS0 4 x 5H 2 0 and an aqueous solution of 40 g / l of the reducing agent. the two solutions occurred shortly before entering the treatment tub.
  • the treatment bath had a temperature of 20 ° C.
  • the copper sulfate solution needed for the strengthening contained the necessary fiber preparation at the same time.
  • the threads obtained were dyed deep blue.
  • the dyed dye could no longer be removed, for example, by washing at 60 ° C.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Artificial Filaments (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Chemical Treatment Of Fibers During Manufacturing Processes (AREA)
EP83102492A 1982-03-18 1983-03-14 Verfahren zur Herstellung von Fäden und Fasern aus Acrylnitrilpolymerisaten Expired EP0089593B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83102492T ATE16120T1 (de) 1982-03-18 1983-03-14 Verfahren zur herstellung von faeden und fasern aus acrylnitrilpolymerisaten.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19823209796 DE3209796A1 (de) 1982-03-18 1982-03-18 Verfahren zur herstellung von faeden und fasern aus acrylnitrilpolymerisaten
DE3209796 1982-03-18

Publications (3)

Publication Number Publication Date
EP0089593A2 EP0089593A2 (de) 1983-09-28
EP0089593A3 EP0089593A3 (en) 1984-01-04
EP0089593B1 true EP0089593B1 (de) 1985-10-16

Family

ID=6158547

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83102492A Expired EP0089593B1 (de) 1982-03-18 1983-03-14 Verfahren zur Herstellung von Fäden und Fasern aus Acrylnitrilpolymerisaten

Country Status (6)

Country Link
US (1) US4507257A (enrdf_load_stackoverflow)
EP (1) EP0089593B1 (enrdf_load_stackoverflow)
JP (1) JPS58169519A (enrdf_load_stackoverflow)
AT (1) ATE16120T1 (enrdf_load_stackoverflow)
DE (2) DE3209796A1 (enrdf_load_stackoverflow)
DK (1) DK153573C (enrdf_load_stackoverflow)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3406910A1 (de) * 1984-02-25 1985-09-05 Hoechst Ag, 6230 Frankfurt Monofile und borsten aus homo- oder copolymerisaten des acrylnitrils und verfahren zu ihrer herstellung
CA2028131A1 (en) * 1989-03-08 1990-09-09 Nippon Kayaku Kabushiki Kaisha Antimicrobial fiber, resin, and method for production thereof
AU6695094A (en) * 1993-11-09 1995-05-29 Kling, Mauricio Aldehyde sulfoxylates systemic fungicides
US6383273B1 (en) 1999-08-12 2002-05-07 Apyron Technologies, Incorporated Compositions containing a biocidal compound or an adsorbent and/or catalyst compound and methods of making and using therefor
WO2007095454A2 (en) * 2006-02-10 2007-08-23 Board Of Supervisors Of Louisiana State University And Agricultural And Mechanical College Carbon-encased metal nanoparticles and sponges, methods of synthesis, and methods of use

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1188128A (fr) * 1957-12-05 1959-09-18 Crylor Nouvelles compositions de noir de carbone et de polyacrylonitrile et procédé pour leur préparation
US3273956A (en) * 1961-08-19 1966-09-20 American Cyanamid Co Method of treating acrylonitrile synthetic fibers
US3281261A (en) * 1963-08-30 1966-10-25 Deering Milliken Res Corp Method of preparing refractory metal oxide coated carbonized acrylic textile fibers
US3242000A (en) * 1963-08-30 1966-03-22 Deering Milliken Res Corp Impregnated carbonized acrylic textile product and method for producing same
US3406145A (en) * 1965-06-21 1968-10-15 Dow Chemical Co Heat stability of acrylonitrile polymer products
GB1288563A (enrdf_load_stackoverflow) * 1969-01-20 1972-09-13
US3917776A (en) * 1970-12-12 1975-11-04 Mitsubishi Rayon Co Process for producing carbon fiber
US3733386A (en) * 1971-04-13 1973-05-15 American Cyanamid Co Process for producing acrylic synthetic fibers improved in the hydrophilicity
BE789557A (fr) * 1971-10-01 1973-03-29 Sandoz Sa Procede pour diminuer le pouvoir d'absorption des colorants basiques par les textiles
JPS4935629A (enrdf_load_stackoverflow) * 1972-08-07 1974-04-02
US4378226A (en) * 1978-10-09 1983-03-29 Nihon Sanmo Dyeing Co., Ltd. Electrically conducting fiber and method of making same
US4267233A (en) * 1979-02-14 1981-05-12 Teijin Limited Electrically conductive fiber and method for producing the same
JPS56148965A (en) * 1980-04-17 1981-11-18 Mitsubishi Rayon Co Durable sterilizable fiber
SU914666A1 (ru) * 1980-08-07 1982-03-23 Aleksandr A Nikitin Способ получения металлизированного волокна 1

Also Published As

Publication number Publication date
DK153573C (da) 1988-12-05
US4507257A (en) 1985-03-26
ATE16120T1 (de) 1985-11-15
DE3209796C2 (enrdf_load_stackoverflow) 1990-03-15
EP0089593A2 (de) 1983-09-28
DE3361014D1 (en) 1985-11-21
JPS58169519A (ja) 1983-10-06
DK123983A (da) 1983-09-19
DK123983D0 (da) 1983-03-17
DK153573B (da) 1988-07-25
EP0089593A3 (en) 1984-01-04
DE3209796A1 (de) 1983-10-13

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