EP0051203B1 - Trockenspinnverfahren zur Herstellung von Polyacrylnitrilhohlfasern und -fäden - Google Patents

Trockenspinnverfahren zur Herstellung von Polyacrylnitrilhohlfasern und -fäden Download PDF

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Publication number
EP0051203B1
EP0051203B1 EP81108530A EP81108530A EP0051203B1 EP 0051203 B1 EP0051203 B1 EP 0051203B1 EP 81108530 A EP81108530 A EP 81108530A EP 81108530 A EP81108530 A EP 81108530A EP 0051203 B1 EP0051203 B1 EP 0051203B1
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EP
European Patent Office
Prior art keywords
spinning
nozzle
fibers
loop
solvent
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
EP81108530A
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German (de)
English (en)
French (fr)
Other versions
EP0051203A1 (de
Inventor
Ulrich Dr. Reinehr
Kurt Bernklau
Hans Karl Burghartz
Toni Herbertz
Hermann-Josef Jungverdorben
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Bayer AG
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Bayer AG
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    • 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
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
    • 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
    • Y10T428/2929—Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
    • 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
    • Y10T428/2973—Particular cross section
    • Y10T428/2975—Tubular or cellular

Definitions

  • a molten polymer for example a polyester
  • a molten polymer for example a polyester
  • a hollow needle is used, which must be placed in the center of the nozzle hole opening, and gaseous substances or fillers are pumped through the hollow needle.
  • the polymer flows around the needle and the gas fills the cavity in the center and stabilizes the shape until the polymer has cooled.
  • hollow viscose threads are produced in particular, castor oil, for example, being used as the lumen-filling medium.
  • a fixed pin extends into the nozzle hole opening. This is generally a difficult spinning process because the polymer wants to go into a closed form.
  • the method is particularly suitable for cross-sectional modifications, but air must be supplied at the pin end or a vacuum must be applied in order to produce hollow fibers.
  • Hollow threads and fibers have now found many areas of application. So they are z. B. for seawater desalination, for cleaning liquids and gases, as an ion exchanger, for reverse osmosis, dialysis and ultrafiltration (artificial kidneys) and because of their low weight and high bulk used for comfort clothing. Especially the cleaning of fabrics, e.g. B. of industrial gases has recently come to the fore. Summary articles on the production and meaning of synthetic hollow fibers can be found in Encyclopedia of Polymer Science and Technology 15, (1971), pages 258-272, in Acta Polymerica 30, (1979), pages 343-347 and in Chemical Engineering, Feb. 1980 , Page 54-55.
  • the internal channel of the acrylic fibers according to DE-A-2 804 376 is periodically interrupted by webs made of polymeric material.
  • Hollow fibers are understood here to mean fibers which have a continuous, continuously continuous channel arranged in the longitudinal direction inside the fibers.
  • the thread formation is carried out by coagulation of the spinning solution in an aqueous precipitation bath which contains a solvent for polyacrylonitrile, the precipitation bath concentration, temperature and additional coagulating agents, such as, for example, aqueous salt solutions, being able to vary within wide limits.
  • an acrylonitrile copolymer with the chemical composition 93.6% acrylonitrile, 5.7% methyl acrylate and 0.7% sodium methallylsulfonate with a K value of 81 can only be used in a spinning solvent up to a maximum solids concentration of 32% by weight like dimethylformamide dissolve and spin into threads. If an attempt is made to increase the solids content further, such spinning solutions gel on cooling even at temperatures around 50 to 80 ° C., so that trouble-free spinning becomes impossible.
  • the object of the present invention was to provide such a dry spinning process for the production of acrylonitrile hollow fibers because of the versatile application possibilities of such hollow fibers and threads.
  • hollow acrylonitrile threads can also be spun using a dry spinning process, if spinning solutions with a viscosity exceeding a certain value are used, nozzles with loop-shaped nozzle holes are used, which are of certain dimensions and the spinning air in a certain way on the threads can act.
  • the invention therefore relates to a process for the production of hollow polyacrylonitrile threads and fibers which have a continuous, continuous channel arranged in the longitudinal direction in the interior of the fiber or the thread, the thread-forming synthetic polymers being obtained from a solution through a nozzle by a dry spinning process spun with loop-shaped nozzle holes, characterized in that the solution has a viscosity of at least 120 ball falling seconds, measured at 80 ° C or at least 75 ball falling seconds, measured at 100 ° C, the nozzle hole area being less than 0.2 mm 2 , the leg width the loop-shaped nozzle is a maximum of 0.1 mm and the overlap of the two leg ends of the loop-shaped nozzle, measured from the center of the nozzle, forms an angle of 10 to 30 ° and the spinning air acts on the threads from the center of the spinning shaft so that each thread transversely to the leg opening at an angle of Flow is 80 to 100 °.
  • Spinning is followed by the usual further process steps of the polyacrylonitrile dry spinning process.
  • the viscosity in falling ball seconds was determined by the method of K. Jost, Reologica Acta, Volume 1 (1958), page 303.
  • the nozzle hole area is preferably less than 0.1 mm 2 and the leg width is between 0.02 to 0.06 mm. In the case of nozzle hole areas larger than 0.2 mm 2 , the cross-sectional shape is found to flow. You get fuzzy bulbous to formless deformed, playful structures.
  • Spinning solutions of the stated viscosity which also contain a higher concentration of the thread-forming polymer than is customary, are obtained according to DE-A-2 706 032 by preparing appropriately concentrated suspensions of the thread-forming polymer, which are easy to convey, in the desired solvent and this suspension converted to viscosity-stable spinning solutions by briefly heating to temperatures just below the boiling point of the spinning solvent used.
  • the suspensions for the preparation of such spinning solutions are obtained by, if necessary, adding a non-solvent for the polymer to be spun to the spinning solvent and then adding the polymer with stirring.
  • the boiling points of the non-solvents can be both below and above the boiling point of the spinning solvent used.
  • Such substances which can be in solid or liquid state, are, for example, alcohols, esters or ketones and mono- and polysubstituted alkyl ethers and esters of polyhydric alcohols, inorganic or organic acids, salts and the like.
  • Water and, on the other hand, glycerol, mono- and tetraethylene glycol and sugar are used as preferred non-solvents because of their easy handling and removal in the spin shaft without residue formation and recovery.
  • an acrylonitrile copolymer with a K value of 81 and a solids concentration of the spinning solution of 36% by weight made it possible to obtain hollow fibers from the nozzles mentioned by the dry spinning process.
  • the water content of such suspensions Polyacrylonitrile and dimethylformamide are in the range between 2 to 10%, based on the total suspension. Below 2% by weight of water, there is no longer a flowable, transportable suspension, but a thick, sluggish slurry. On the other hand, if the water content is more than 10% by weight, the threads burst during the spinning process below the nozzle because of the high water vapor partial pressure when it emerges from the nozzle holes. The percentage of water in the spinning solution does not affect the profile at the nozzle. The only decisive factor is the polymer solids concentration. With solids contents up to 40% Water proportions of 2 to 3% have been proven to be optimal in order to obtain still flowable, portable suspensions at room temperature.
  • acrylonitrile copolymers with K values less than 81 of course, even more concentrated spinning solutions can be produced.
  • a suspension of 45% copolymer solids content, 4% water and 51% dimethylformamide can be produced from an acrylonitrile copolymer made from 92% acrylonitrile, 6% acrylic acid methyl ester and 2% sodium methallylsulfonate with a K value of 60, which has a viscosity of 142 ball falling seconds, measured at 80 ° C, which is still flowable at room temperature and can be converted into hollow fibers by loosening and spinning from a special profile nozzle.
  • the percentage of non-solvent in the spinning solution does not affect the profile at the nozzle. Rather, the decisive factor is that the spinning solution has a minimum viscosity.
  • non-solvent fractions of 5 to 10% by weight have proven to be optimal in order to obtain hollow acrylic fibers with a water retention capacity of greater than 10%.
  • the solid mass surrounding the continuous continuous channel arranged in the longitudinal direction inside the fiber has a core / shell structure.
  • the thickness of the fiber cladding can be varied within wide limits by the ratio of polymer solid to non-solvent content.
  • the minimum viscosity can be determined at two different temperatures, namely at 80 ° C and 100 ° C.
  • This measure takes into account the fact that, on the one hand, the determination of the viscosity in spinning solutions which contain water as non-solvent is difficult because of the evaporation of the water at 100 ° C., while on the other hand in the determination of the viscosity in other spinning solutions which contain a substance as non-solvent whose boiling point is above that of the spinning solvent can become problematic at 80 ° C due to the tendency to gel.
  • the viscosity of water-containing spinning solutions can also be determined at 100 ° C when working in a closed system.
  • the higher boiling solvents such as dimethylacetamide, dimethyl sulfoxide, ethylene carbonate and N-methylpyrrolidone and the like are also suitable as spinning solvents.
  • a spiral or loop nozzle according to FIG. 1 is particularly advantageous, the overlap angle of the two leg ends of the spiral nozzle holes being 10 to 30 °, preferably 20 °. If the leg end of the spiral nozzle holes is extended, the overlap angle of the two leg ends is 55 °, for example (see Fig.
  • the spinning air does not hit the leg openings of the profile nozzle centrally, but is accessed in the transverse direction at an angle of 80 to 100 °, preferably 90 ° (cf. FIG. 2). If the spinning air arrives directly in the thigh openings (cf. FIG. 3), the threads inflate strongly, in order to then close under the influence of the delay; collapse. Discontinuous cross-sectional shapes and changing cavity parts are obtained.
  • the size of the nozzle hole diameter and the nozzle hole area also play an important role. It has been shown that in the case of special geometrical configurations, sharp contours of the thread cross sections can only be spun up to a certain leg width, depending on the entire nozzle hole area.
  • the leg width of a profile nozzle is understood here to mean the distance between the outer boundary of the predetermined profile shape in mm, but not the distance to the center of the nozzle hole.
  • the fibers according to the invention are particularly notable for their high water retention capacity.
  • textile fabrics made from such fibers have good wearing comfort.
  • the water retention capacity is at least 10% in all cases where there is a closed, self-contained hollow fiber with a constant void fraction.
  • 2 values for the water retention capacity, which fluctuate depending on the proportion of voids, are determined.
  • the water retention capacity is determined on the basis of DIN regulation 53814 (cf. Melliand Textile Reports 4, 1973, page 350).
  • the fiber samples are immersed in water containing 0.1% wetting agent for 2 hours.
  • the fibers are then 10 minutes at an acceleration of 10 000 m / sec 2 centrifuged and the water 2 sermenge gravimetrically determined, which is retained in and between the fibers.
  • To determine the dry weight the fibers are dried to constant moisture at 105 ° C.
  • the water retention capacity (WR) in% by weight is:
  • DMF dimethylformamide
  • 38 kg of an acrylonitrile copolymer composed of 93.6% acrylonitrile, 5.7% methyl acrylate and 0.7% sodium methallysulfonate with a K value of 81 are then metered in with stirring at room temperature.
  • the suspension is pumped via a gear pump into a spinning kettle equipped with an agitator.
  • the suspension which has a solids content of 38% by weight and a water content of 3% by weight, based on the total solution, is heated in a double-walled tube with steam of 4.0 bar.
  • the dwell time in the tube is 7 minutes.
  • the temperature of the solution at the pipe outlet is 138 ° C.
  • the spinning solution which has a viscosity of 176 ball falling seconds at 90 ° C, is filtered after leaving the heating device without intermediate cooling and fed directly to the spinning shaft.
  • the spinning solution is spun dry from a 36-hole nozzle with spiral nozzle holes (see FIG. 1).
  • the nozzle holes are arranged on an annular nozzle in such a way that the openings of the profile nozzle are aligned transversely to the air blowing (see FIG. 2).
  • the nozzle hole area is 0.08 mm 2 and / the leg width is 0.06 mm.
  • the shaft temperature is 160 ° C and the air temperature is 150 ° C.
  • the amount of air that flows through in the immediate vicinity of the spinneret onto the thread bundle emerging from it in the transverse direction to the thread take-off on all sides from the center of the spinning shaft is 30 m 3 / h.
  • the take-off speed is 125 m / min.
  • the spinning material with a titer of 790 dtex is collected on spools and made into a band with a total titer of 1 158,000 dtex fold.
  • the fiber cable is then washed in water at 80 ° C., stretched 1: 4 in boiling water, provided with antistatic preparation, crimped, cut into staple fibers of 60 mm length and then dried on a belt dryer at 120 ° C.
  • the water retention capacity is 37.6%.
  • the fiber capillaries were embedded in methyl methacrylate and cross-cut.
  • the light microscopic images produced in the differential interference contrast method show that the sample cross sections have a perfectly uniform, round cavity structure.
  • the void fraction is around 50% of the total cross-sectional area.
  • the following table shows the limits of the process according to the invention for the production of hollow acrylic fibers according to the dry spinning process using further examples.
  • an acrylonitrile copolymer with the chemical composition of Example 1 is used again and transferred to a spinning solution as described there.
  • the solids concentration and the type and percentage of the non-solvent for polyacrylonitrile were varied.
  • the spinning and post-treatment conditions correspond to the information from Example 1.
  • the viscosities were measured in falling ball seconds at 80 ° C.
  • a part of the folded hollow fiber cable from Example 1 with a total titer of 158,000 dtex was washed in water at 80 ° C., stretched 1: 4 times in boiling water, provided with antistatic preparation and dried under tension at 160 ° C. in a drum dryer. It was then crimped and cut into staple fibers 60 mm long.
  • the hollow fibers, which have a final titer of 6.7 dtex, have a water retention capacity of 14.1%.
  • the sample cross-sections of the fibers show, in addition to approx. 30% in the form of uniform round hollow fibers, approx. 70% in the form of collapsed fibers with fluctuating void portions, partly crescent-shaped to sickle-shaped structures, as well as hollow fibers with several break points in cross-section.
  • Example 2 An acrylonitrile copolymer with the chemical composition of Example 1 was dissolved as described there, filtered and dry spun from a 36-hole nozzle with spiral nozzle holes (see FIG. 3).
  • the overlapping of the leg ends of the nozzle holes is again 20 °, the nozzle hole area 0.08 mm 2 and the leg width 0.06 mm.
  • the remaining spinning and aftertreatment data correspond to the information in Example 1.
  • Example 1 An acrylonitrile copolymer with the chemical composition of Example 1 was dissolved as described there, filtered and dry spun from a 36-hole nozzle with loop-shaped nozzle holes (see dep. 4).
  • One leg end of the loop-shaped nozzle holes is elongated in comparison to the profile nozzle from Example 1 in such a way that the angle of overlap of the leg ends is 55 °, as a result of which the air flow no longer takes place transversely to the leg openings of the profile nozzle, but at an angle of 125 ° (cf. Fig. 5).
  • the nozzle hole area is 0.095 mm 2 and the leg width is 0.06 mm.
  • the other spinning and aftertreatment conditions correspond to the information in Example 1.
  • the fibers, which have a final titer of 6.7 dtex, have a water retention capacity of 10.7%.
  • the sample cross-sections of the fibers show no closed cavity shape, there are crescent-shaped to curved structures.
  • Example 2 An acrylonitrile copolymer with the chemical composition of Example 1 was dissolved as described there, filtered and dry spun from a 36-hole nozzle with loop-shaped nozzle holes (see FIG. 3).
  • One leg end of the loop-shaped nozzle holes is extended as described in Example 5 so that the angle of overlap of the leg ends is 55 °.
  • the nozzle holes are arranged such that the openings of the leg ends of the profile nozzle form an angle of 35 ° to the direction of the spinning air from the center of the spinning shaft, so that the spinning air can only flow obliquely from the inside into the nozzle openings (cf. Fig. 6).
  • the nozzle hole area is 0.095 mm 2 and the leg width is 0.06 mm.
  • the other spinning and aftertreatment conditions correspond to the information in Example 1.
  • the hollow fibers which have a final titer of 6.7 dtex, have a water retention capacity of 20.5%. Samples cross-sections of the fibers show mostly closed, but irregularly shaped tubular to loop-like structures.
  • the viscosity of the spinning solution is 142 ball falling seconds at 80 ° C.
  • the other spinning and aftertreatment conditions correspond to the explanations of Example 1.
  • the water retention capacity is 39%.
  • DMF dimethylformamide
  • 37 kg of an acrylonitrile polymer composed of 93.6% acrylonitrile, 5.7% methyl acrylate and 0.7% sodium methallylsulfonate with a K value of 81 are then metered in with stirring at room temperature.
  • the suspension is pumped via a gear pump into a spinning kettle equipped with an agitator.
  • the suspension which has a solids content of 37% by weight, is heated in a double-walled tube with steam of 4.0 bar.
  • the dwell time in the tube is 7 minutes.
  • the temperature of the solution at the pipe outlet is 138 ° C.
  • the spinning solution which has a viscosity of 186 ball falling seconds at 100 ° C, is filtered after leaving the heating device without intermediate cooling and fed directly to the spinning shaft.
  • the spinning solution is spun dry from a 36-hole nozzle with spiral nozzle holes (see FIG. 1).
  • the nozzle holes are arranged on an annular nozzle so that the openings of the profile nozzle are aligned transversely to the air blowing (see Fig. 2).
  • the nozzle hole area is 0.08 mm 2 and the leg width is 0.06 mm.
  • the shaft temperature was 160 ° C and the air temperature was 150 ° C.
  • the amount of air that flows through in the immediate vicinity of the spinneret onto the thread bundle emerging from it in the transverse direction to the thread take-off on all sides from the center of the spinning shaft is 30 m 3 / h.
  • the take-off speed was 125 m / min.
  • the spinning material with a titer of 790 dtex is collected on spools and into a band with a total titer 158,000 dtex fold.
  • the fiber cable is then washed in water at 80 ° C, stretched 1: 4 in boiling water, provided with antistatic preparation, crimped, cut into staple fibers of 60 mm in length and then dried on a belt dryer at 120 ° C.
  • the water retention capacity is 50.3%.
  • the sample cross-sections have a perfectly uniform, round cavity structure.
  • the void fraction is around 50% of the total cross-sectional area.
  • the solid mass surrounding the cavity consists of a porous core / shell structure.
  • the following table II shows the limits of the process according to the invention for the production of hollow acrylic fibers according to the dry spinning process using further examples.
  • an acrylonitrile copolymer with the chemical composition of Example 9 is used again and transferred to a spinning solution as described there.
  • the solids concentration and the type and percentage of the non-solvent for polyacrylonitrile were varied.
  • the spinning and aftertreatment conditions correspond to the information from Example 9.
  • the viscosities were measured in the falling ball seconds at 100 ° C. as described at the beginning.
  • a portion of the folded hollow fiber cable from Example 9 with a total titre of 158,000 dtex was washed in water at 80 ° C., stretched 1: 4 in boiling water, provided with antistatic preparation and dried under tension at 160 ° C. in a drum dryer. It was then crimped and cut into staple fibers 60 mm long.
  • the hollow fibers which have a final titer of 6.7 dtex, have a water retention capacity of 17.1%.
  • the sample cross-sections of the fibers show, in addition to approx. 30% in the form of uniform round hollow fibers, approx. 70% in the form of collapsed fibers with fluctuating voids, partially crescent-shaped to crescent-shaped structures and hollow fibers with several break points in cross section.
  • Example 9 An acrylonitrile copolymer with the chemical composition of Example 9 was dissolved as described there, filtered and dry spun from a 36-hole nozzle with spiral nozzle holes (see FIG. 1).
  • the overlapping of the leg ends of the nozzle holes is again 20 °, the nozzle hole area 0.08 mm 2 and the leg width 0.06 mm.
  • the remaining spinning and aftertreatment data correspond to the information in Example 9.
  • the hollow fibers which have a final titer of 6.7 dtex, have a water retention capacity of 22.4%.
  • the sample cross-sections of the fibers show irregularly deformed tubular to loop-like collapsed hollow fibers with changing void proportions and partially completely compact cross-sectional structures.
  • Example 9 An acrylonitrile polymer with the chemical composition of Example 9 was dissolved as described there, filtered and dry spun from a 36-hole nozzle with loop-shaped nozzle holes (see FIG. 4).
  • One leg end of the loop-shaped nozzle holes is elongated in comparison to the profile nozzle from Example 1 in such a way that the angle of overlap of the leg ends is 55 °, as a result of which the air flow no longer takes place transversely to the leg openings of the profile nozzle, but at an angle of 125 ° C (cf. Fig. 5).
  • the nozzle hole area is 0.095 mm 2 and the leg width is 0.06 mm.
  • the other spinning and aftertreatment conditions correspond to the information in Example 9.
  • the fibers, which have a final titer of 6.7 dtex, have a water retention capacity of 13.7%.
  • the sample cross-sections of the fibers show no closed cavity shape, there are crescent-shaped to curved structures.
  • Example 9 An acrylonitrile copolymer with the chemical composition of Example 9 was dissolved as described there, filtered and dry spun from a 36-hole nozzle with loop-shaped nozzle holes (cf. FIG. 4).
  • One leg end of the loop-shaped nozzle holes is extended as described in Example 13 so that the angle of overlap of the leg ends is 55 °.
  • the nozzle holes are arranged such that the openings of the leg ends of the profile nozzle form an angle of 35 ° to the direction of the spinning air from the center of the spinning shaft (see FIG. 6), so that the spinning air is only inclined from the inside the nozzle openings can flow.
  • the nozzle hole area is 0.095 mm 2 and the leg width is 0.06 mm.
  • the other spinning and post-treatment conditions correspond to the information in Example 9.
  • the hollow fibers which have a final titer of 6.7 dtex, have a water retention capacity of 24.5%.
  • the sample cross sections of the fibers show mostly closed, but irregularly deformed tubular to loop-like structures with core / shell structures.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
EP81108530A 1980-10-30 1981-10-20 Trockenspinnverfahren zur Herstellung von Polyacrylnitrilhohlfasern und -fäden Expired EP0051203B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3040971 1980-10-30
DE19803040971 DE3040971A1 (de) 1980-10-30 1980-10-30 Trockengesponnene polyacrylnitrilhohlfasern und -faeden und ein verfahren zu ihrer herstellung

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EP0051203A1 EP0051203A1 (de) 1982-05-12
EP0051203B1 true EP0051203B1 (de) 1984-06-27

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US (2) US4457885A (enrdf_load_stackoverflow)
EP (1) EP0051203B1 (enrdf_load_stackoverflow)
JP (1) JPS57106714A (enrdf_load_stackoverflow)
DE (2) DE3040971A1 (enrdf_load_stackoverflow)

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US5972499A (en) * 1997-06-04 1999-10-26 Sterling Chemicals International, Inc. Antistatic fibers and methods for making the same
DE19756760A1 (de) * 1997-12-19 1999-06-24 Pedex & Co Gmbh Verfahren zur Herstellung von Puppenhaar
BRPI0610688A2 (pt) * 2005-04-08 2012-10-30 Huntsman Int Llc aparelho e processo para misturar pelo menos um primeiro e um segundo fluidos e processo para fabricar isocianatos
CA2636098C (en) * 2008-06-25 2012-08-07 Ottawa Fibre L.P. Spinner for manufacturing dual-component irregularly-shaped hollow insulation fiber

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US4176150A (en) * 1977-03-18 1979-11-27 Monsanto Company Process for textured yarn
JPS542419A (en) * 1977-06-01 1979-01-10 Mitsubishi Rayon Co Ltd Special synthetic fiber and its production
JPS546919A (en) * 1977-06-17 1979-01-19 Mitsubishi Rayon Co Ltd Production of acrylic noncircular cross-section filament yarns
DE2804376A1 (de) * 1978-02-02 1979-08-09 Bayer Ag Hydrophile hohlfasern
US4296175A (en) * 1979-02-21 1981-10-20 American Cyanamid Company Hollow acrylonitrile polymer fiber
EP0014803A1 (en) * 1979-02-21 1980-09-03 American Cyanamid Company Process for preparing acrylonitrile polymer fiber of hollow or open structure

Also Published As

Publication number Publication date
JPS57106714A (en) 1982-07-02
EP0051203A1 (de) 1982-05-12
DE3164456D1 (en) 1984-08-02
DE3040971A1 (de) 1982-06-24
JPH0128124B2 (enrdf_load_stackoverflow) 1989-06-01
US4457885A (en) 1984-07-03
US4483903A (en) 1984-11-20

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