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
  • D06M11/07—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
• • 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
  • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
  • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
  • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
  • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
  • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
  • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles

Definitions

• the invention relates to continuous processes for producing synthetic threads and fibers insoluble in N, N-dimethylformamide from acrylonitrile polymers, which have a weight loss of at most 20%, preferably 15%, when heated to 400 ° C.
• the spinning solution begins to gel and can no longer be spun without interference, while the extrusion of spinning masses containing copper (I) salts into injection molded articles may not yet be hindered.
• 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.
• the copper (I) ions are naturally particularly easily absorbed with wet-spun threads; However, it is also possible to load dry-spun threads which still contain solvent within the washing process or post-treatment process with copper (I) ions.
• the treatment can be carried out 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, which means that the copper content can be reduced by the following washes can be removed. 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 usually exceeded.
• the dwell time of the threads or cables is important for the fixing process. While the fixation, for example, requires longer dwell times at 65 ° C., at temperatures above 100 ° C., only times of one minute or possibly a few seconds are required for the same effect.
• the copper (I) content can no longer be washed out; it can be assumed that the copper (I) ions have been complexly incorporated into the polyacrylonitrile under these conditions.
• a common procedure consists in pulling the cable or the strands through a copper (I) ion-containing bath and, after the excess bath liquid has been largely squeezed out, for example via hot godets of, for example, 100 ° C. surface temperature. Then, if desired, a further wash can be provided to remove copper salts adhering to the surface etc. from the threads, in order to then apply a customary preparation to the threads or cables in a subsequent bath before they are finally dried.
• a copper (I) ion-containing bath for example via hot godets of, for example, 100 ° C. surface temperature.
• a further wash can be provided to remove copper salts adhering to the surface etc. from the threads, in order to then apply a customary preparation to the threads or cables in a subsequent bath before they 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 CuSO 4 x 5 H 2 0 has proven to be particularly favorable as the usual copper (II) salt.
• Aldehyde sulfoxylates and in particular the sodium salt of hydroxymethanesulfinic acid, are particularly advantageous since high copper (I) ion concentrations with good stability can be obtained with this system.
• the stability can additionally be increased by suitable complexing agents.
• the low temperatures required for the aqueous solutions make a significant contribution to the stability of the copper (I) solutions.
• a temperature close to room temperature is sufficient in almost all cases.
• temperatures slightly above room temperature i.e. from 25 to 30 ° C, for example, can be used, since here the constant temperature of the bath can be ensured by the simplest technical means. If desired, however, it is also possible to work at higher temperatures, for example 60 to 95 ° C.
• a copper (II) salt solution in water and an aqueous solution containing the reducing agent are metered separately into the bath near the entry point of the cable and mixed in the bath. This ensures that fresh copper (I) solution is applied to the cable. Cable and bath liquid move in direct current, excess bath liquid, which is expediently largely used up, is drawn out of the tub near the cable outlet and returned, for example, after refreshing.
• the concentration of copper (I) ions can vary within wide limits depending on the desired fiber properties.
• the reducing agent is use at least in the stoichiometric amount. A slight excess is preferably used in order to avoid the presence of copper (II) salts.
• the copper (II) ions cannot be bound in a complex manner by the polymer molecules, so they are washed out during subsequent washes and pollute the waste water.
• 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, that it can then no longer be incorporated into the threads or fibers.
• the copper (I) ion solution can be applied to the cables or thread strands 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 and other baths does not lead to an unnecessary dilution of the copper (I) ions. treatment bath remains within tolerable limits. Of course, it is advantageous if measures are taken which ensure good and uniform penetration of a thread cable or strand in the treatment liquor. For example, cables should be so wide in the loading treatment bath that a depletion of the copper ion concentration or a delayed penetration with the treatment bath inside the cable should be neglected if possible.
• the acrylonitrile-containing polymers used are understood to be those polymers which are composed of more than 50%, preferably more than 85%, of acrylonitrile units. Particularly good results have been obtained with polyacrylonitriles which are composed of at least 98% acrylonitrile units.
• Other copolymer components that can be considered are, for example, 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 desired good thermal stability ensure the yarns or fibers produced, after drying, if appropriate, also be carried out together with the drying, a further T empera- tur accompaniment that Stell.soll at 200 to 350 ° C, preferably between 250 and 330 ° C. It is necessary to keep the threads under tension, preferably even to subject them to a slight additional stretching.
• the threads can be heated to these temperatures by known, conventional methods, such as For example, multiple routing over heated godets, use of infrared radiators or guiding over a contact heat path.
• Thermoanalyzer 2 from Mettler Instrumente AG, GNeillsee, Zurich, was used as the measuring device. The samples were heated to 400 ° C. with a heating program of 10 ° C./min and an air flow of 5 l / h and the weight loss was then determined.
• the threads thus continuously produced show a weight loss of only a maximum of 20%, preferably less than 15%, in the case of such heating to 400.degree. They can be converted into pre-oxidized fibers or thread strands within a few minutes, which can then be subjected to a carbonization process above 700 ° C.
• such threads and fibers are particularly suitable for technical purposes, such as filter material for hot gas filtration, for the production of protective clothing and the like, and as reinforcing fibers or threads for inorganic and organic materials such as e.g. as asbestos substitute e.g. in friction linings or the like.
• filter material for hot gas filtration
• reinforcing fibers or threads for inorganic and organic materials such as e.g. as asbestos substitute e.g. in friction linings or the like.
• This temperature treatment generally causes the threads treated in this way to crimp.
• the residence time of the thread material at these temperatures naturally also plays a role. Generally, residence times from a few seconds to a few minutes are required to achieve the desired one To achieve effect. In any case, the temperature treatment is so short that it can be integrated into a continuous thread or fiber manufacturing process. If it is not necessary to remove the copper compounds adhering to the surface of the threads or cables, it is possible to combine the copper fixing process with drying and the subsequent heat treatment.
• a 17% solution of polyacrylonitrile in dimethylformamide was spun in a known manner using the wet spinning process.
• the polyacrylonitrile used consisted of 99.5% acrylonitrile building blocks and 0.5% methyl acrylate building blocks and had a relative viscosity of 2.9.
• the relative viscosity was determined in solutions containing 0.5 g of polymer in 100 ml of N, N-dimethylformamide, measuring temperature 25 ° C.
• the temperature of the spinning solution was 90 ° C.
• a 300 perforated nozzle with a bore diameter of 80 ⁇ m was used.
• This spinning solution was spun in a spinning bath of 50% N, N-dimethylformamide (DMF) and 50% water at 50 ° C. and drawn off from the precipitation bath at a speed of 7 m / min, followed by a wet drawing at 60 ° C. in the ratio 1: 2.31 in a bath consisting of 60% DMF and 40% water, and then washed with water at 30 ° C solvent-free. After the wash, the sliver was squeezed to remove most of the water and passed through a trough containing an aqueous solution of 100 g CuSO 4 x 5 H 2 0 per liter and 20 g per liter of the sodium salt of hydroxymethanesulfinic acid. This treatment bath also contained the necessary fiber preparation. Residence time in this bath about 1.5 seconds.
• the treatment solution was supplemented by continuous metering of an aqueous solution of 200 g / 1 CuSO 4 ⁇ 5 H 2 O and an aqueous solution of 40 g / 1 of the sodium salt of hydroxymethanesulfinic acid *. The two solutions were mixed shortly before entering the treatment tub.
• the sliver was squeezed off again and then dried on two heating godets at 130 ° C (contact time 7 seconds) and then on two heating godets at 170 ° C (contact time 14 seconds) subjected to a stretching of 1: 1.85 and on one another godet of 250 ° C (contact time 9 seconds) one Subsequent stretching of 1: 1.61 and then brought to the reel via a cold take-off device.
• the brown-black discolored threads had a strength of 25 cN / dtex, an elongation of 7.8% and an initial modulus of 1000 cN / tex of the single thread titer was 3.0 dtex.
• the sliver was squeezed to remove a large part of the water and passed through a trough which contained an aqueous solution of 75 g / 1 CuSO 4 x 5 H 2 0 and 50 g / l of the sodium salt of hydroxymethanesulfinic acid * and a conventional fiber preparation .
• the solution was supplemented by continuous metering of an aqueous solution of 150 g / 1 CuSO 4 x 5 H 2 0 with an aqueous solution of 100.g / 1 of the sodium salt of hydroxymethanesulfinic acid.
• the two solutions were mixed shortly before entering the treatment tub.
• the copper sulfate solution used to (formula CH 2 SO 2 Na x 2 H 2 O)
• Reinforcement was used also contained the fiber preparation.
• the sliver was squeezed off again and then dried on 2 heating godets at 190 ° C. (contact time 7 seconds) and then subjected to a drawing of 1: 1.54 on 2 heating godets at 310 ° C.
• the cable was then heated on 2 further godets with a surface temperature of 310 and 330 ° C. and then brought to the reel by means of a cold take-off device, again stretching by 1: 1.06.
• the pure contact times of the treated cable at 310 ° C were 50 seconds and at 330 ° C 15.7 seconds.
• the dark-colored individual filaments of the treated cable showed a weight loss of up to 400 ° C of 7%.
• the other technical textile data was
• a spinning was carried out in accordance with Example 2, but the fiber cable treated with the copper solution was subjected to a further wash at 80 ° C. and a preparation after drying at 190 ° (contact time 11 seconds) and then a second drying at 190 ° C. (Contact time 11 seconds).
• the cable was then passed over 4 godets which were heated to a surface temperature of 310, 310, 310 and 330 °.
• the contact time of the cable at 310 ° C was 61 seconds at 330 ° C 18 seconds.
• the fibers were subjected to a drawing of 1: 1.25.
• the thread material obtained was subjected to thermogravimetric analysis and showed a weight loss on heating of up to 400 ° C. of less than 10%.
• the textile data found was
• Initial module 811 cN / tex The fibers or thread strands obtained were subjected to carbonization at temperatures above 700 ° C. after a greatly shortened preoxidation, as is used for the production of carbon fibers.
• the pre-oxidation time for these cable harnesses was less than 7 minutes and thus only a small fraction of the time otherwise required.
• Thread cables corresponding to 3 were produced and these samples were then subjected to heating in a drying cabinet at 250 ° C. for 120 minutes without tension. Fibers with good crimp that were non-flammable were obtained. After this treatment, the fibers had the following textile values

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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Artificial Filaments (AREA)
• Inorganic Fibers (AREA)
• Chemical Treatment Of Fibers During Manufacturing Processes (AREA)
• Chemical Or Physical Treatment Of Fibers (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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Publications (3)

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• 1982
  • 1982-03-18 DE DE19823209795 patent/DE3209795A1/de active Granted
• 1983
  • 1983-03-07 US US06/473,050 patent/US4524041A/en not_active Expired - Fee Related
  • 1983-03-14 AT AT83102493T patent/ATE16119T1/de not_active IP Right Cessation
  • 1983-03-14 EP EP83102493A patent/EP0091567B1/fr not_active Expired
  • 1983-03-14 DE DE8383102493T patent/DE3361015D1/de not_active Expired
  • 1983-03-17 DK DK123883A patent/DK153893C/da not_active IP Right Cessation
  • 1983-03-17 JP JP58043281A patent/JPS58169520A/ja active Granted

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