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 by a dry or wet spinning process, in which the fibers or threads which have not yet been healed by drying or a temperature treatment above 100 ° C. are continuously treated with an aqueous solution of copper (I) ions .
• the spinning solution begins to gel and can no longer be spun without interference, while an extrusion of copper (I) salts containing spinning masses into injection molded articles may not yet be hindered.
• spinning cables. or strands of individual 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 been subjected to a temperature treatment above 100 ° C. or 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 doesn't matter. whether the threads were produced by a dry or a wet spinning process.
• the copper (I) ions are particularly easily absorbed in wet-spun threads
• the treatment can take place before, during or after the washing of 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, i.e. the copper content can be removed by subsequent washing. 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 dwell time is important for the fixing process. While the fixation in e.g. 65 ° C longer dwell times, at temperatures above 100 ° C only times of one minute or significantly less are required 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 (I) content can no longer be washed out, it is closed assume 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 the excess bath liquid has been largely squeezed off, e.g. via hot godets from e.g. 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 immediately before the first drying and to fix them with drying.
• the threads have superficially non-complexly bonded copper compounds that can be detached on first contact with water.
• 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 CuS04 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 reduced by reducing copper (II) - Connections produced, the reducing agent is to 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 during subsequent washing 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 even 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 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. It can thus 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 from This is an advantage if measures are taken to ensure good and even 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 treated acrylic fibers are more sensitive to heat than untreated threads.
• the temperatures must be selected so that a good degree of whiteness is maintained.
• 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 possible components are, for example, acrylic acid, metacrylic 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 offer a wide range of applications.
• gently dried fibers that still have good 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 applies both to the discontinuous dyeing of the finished fiber and to 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 by the old cupro-ion process, can not be achieved. For this reason, when there are high demands on light fastness such as for fibers for the awning sector, expensive color pigments used in spin dyeing.
• an intermediate temperature treatment at temperatures below 100 ° C leads to sufficient binding of the copper in the complex state, while the gel structure is still sufficiently preserved to ensure staining with anionic dyes within such a short time that continuous production of the dyed threads or fibers is possible.
• 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 CuSO 4 x 5 H 2 0 and 20 g / l of the sodium salt of hydroxymethanesulfinic acid (trade name: (R ) Rongalit C) contained (residence time 1.5 sec.).
• the solution also contained the required fiber preparation.
• the solution was supplemented by continuous metering of an aqueous solution of 200 g / 1 CuS0 4 x 5 H 2 0 and an aqueous solution of 40 g / l of the reducing agent.
• the two solutions were mixed shortly before entering the treatment tub.
• the treatment bath had a temperature of 20 ° C.
• the sliver was squeezed again and then dried on two heating godets at 140 ° C and then subjected to a stretching of 1: 1.12 to two heating godets at 160 ° C and then a further stretching of 1: 1.54 to two subjected to further heating godets with a surface temperature of 160 ° C and then brought to the reel by means of a cold take-off device.
• the filaments obtained had good whiteness and good drawability for acid dyes.
• the copper content of the fibers was 4.5% Cu.
• the following textile values were determined:
• a spinning mass was spun according to Example 1 through a 300 hole nozzle.
• the nozzle bore diameter was in each case. 60 ⁇ m.
• a mixture of 61% dimethylformamide and 39% water at 50 ° C served as the spinning bath.
• the freshly spun threads were drawn off from the precipitation bath at a speed of 7 m / min, subjected to wet drawing at 99 ° C. of 1: 2.85 in a bath which consisted of 62% dimethylformamide and 38% water, and then with Wash water free of solvents at 80 ° C.
• the fiber sliver was squeezed to remove a large part of the water and passed through a trough which contained an aqueous solution of 29 g / l CuSO 4 x 5 H 2 O and 5.7 g / l of the sodium salt of hydroxymethanesulfinic acid * (residence time 1.5 sec.).
• This bath also contained the necessary preparation components.
• the solution was dosed in accordance with Example 1. After passing through the tub, the sliver was squeezed again and subsequently dried on 2 heating godets at 140 ° C., then subjected to drawing from 1: 1.14 to 2 heating godets at 160 ° C.
• the fibers obtained had a copper content of 1.6% and showed good dyeability with acid dyes.
• the measured textile values were * Formula: CH2 SO 2 Na x 2 H 2 0
• a spinning according to example 3 was carried out.
• the treatment solution consisted of an aqueous solution of 50 g / l CuS0 4 x 5 H 2 0 and 4 g / l metallic copper powder.
• the treatment temperature in this case was 85 ° C.
• care was taken to ensure that the content of metallic copper in the treatment bath was also kept constant.
• the fiber obtained had a copper content of 2.1% and good dyeability with acid dyes.
• the textile data of this fiber was
• the threads obtained were dyed deep blue.
• the dyed dye could no longer be removed, for example, by washing at 60 ° C.

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• 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)

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Publications (3)

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Family Applications (1)

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• 1982
  • 1982-03-18 DE DE19823209796 patent/DE3209796A1/de active Granted
• 1983
  • 1983-03-07 US US06/472,859 patent/US4507257A/en not_active Expired - Fee Related
  • 1983-03-14 EP EP83102492A patent/EP0089593B1/fr not_active Expired
  • 1983-03-14 DE DE8383102492T patent/DE3361014D1/de not_active Expired
  • 1983-03-14 AT AT83102492T patent/ATE16120T1/de not_active IP Right Cessation
  • 1983-03-17 JP JP58043280A patent/JPS58169519A/ja active Pending
  • 1983-03-17 DK DK123983A patent/DK153573C/da not_active IP Right Cessation

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