EP0030666A2 - Thermoplastic acrylonitrile copolymer fibres, their manufacture and use - Google Patents

Thermoplastic acrylonitrile copolymer fibres, their manufacture and use Download PDF

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Publication number
EP0030666A2
EP0030666A2 EP80107458A EP80107458A EP0030666A2 EP 0030666 A2 EP0030666 A2 EP 0030666A2 EP 80107458 A EP80107458 A EP 80107458A EP 80107458 A EP80107458 A EP 80107458A EP 0030666 A2 EP0030666 A2 EP 0030666A2
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EP
European Patent Office
Prior art keywords
fibers
vinyl
esters
acrylonitrile
manufacture
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.)
Withdrawn
Application number
EP80107458A
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German (de)
French (fr)
Other versions
EP0030666A3 (en
Inventor
Hans Dr. Abrecht
Max Dr. Schuler
Guido Dr. Stampa
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.)
Lonza AG
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Lonza AG
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Filing date
Publication date
Application filed by Lonza AG filed Critical Lonza AG
Publication of EP0030666A2 publication Critical patent/EP0030666A2/en
Publication of EP0030666A3 publication Critical patent/EP0030666A3/en
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • D01D5/42—Formation of filaments, threads, or the like by cutting films into narrow ribbons or filaments or by fibrillation of films or filaments
    • 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
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent

Definitions

  • thermoplastic polymers or mixtures of thermoplastic polymers.
  • fibers are produced by melt spinning or by spinning from solvents.
  • such fibers have too strong textile properties for further processing, in particular into nonwovens, knitted fabrics or fabrics, which in turn are to be used as composite and filling material. This means that such fibers have too great an elongation at break or break.
  • a fiber which has a high tensile strength with the least elongation at break or breaking.
  • the aim of the invention is to produce such fiber material and to use it as described above.
  • copolymers according to the above description are to be understood as meaning polymers made from acrylonitrile and one or more of the compounds mentioned.
  • the copolymer can optionally also contain fillers and pigments, such as carbon black, Ti0 2 , chalk, blast furnace slag, etc.
  • copolymers which have been obtained by grafting a copolymer as defined above onto a submitted elastomer phase.
  • the elastomer phase can, for example, mainly contain proportions of butadiene with acrylonitrile, styrene and / or isoprene.
  • Copolymers which are based on a grafting reaction have improved impact strength; this also increases the draw ratio and results in fibers with higher strength.
  • the finely branched, branched structure of the individual fibers predestines the product produced according to the invention for areas of application which are known under the name of nonwovens.
  • the polar groups of the copolymer give extremely good adhesion, for example to cellulose-containing products or in laminating resins.
  • These adhesive properties predestine the spliced fiber mentioned as a reinforcing and filling material in molded articles of all kinds.
  • the stiffness of the individual fibers in turn emphasizes such possible applications.
  • an extruder which is equipped with a slot die or a blow head, or with a calender is extruded or calendered into tubes or foils and tapes.
  • the processing temperature depends on the copolymer used and can be determined individually by a person skilled in the art according to practical requirements.
  • the hoses, foils or tapes are cooled to temperatures,. which are 10 to 70 ° C above the glass transition temperature and then stretched 2 to 20 times on a fume cupboard.
  • the stretching ratio optimally corresponding to the copolymer used can easily be determined by experiment. In principle, the rule applies that the tendency to splice increases with decreasing stretching temperature, increasing degree of stretching and with increasing stretching speed.
  • the hoses, foils or tapes can be cooled to the appropriate temperatures after the extrusion or calendering process and then stretched. However, it is also possible to cool the products after extrusion or calendering, to store them and to subsequently heat them up to the necessary temperatures and then stretch them.
  • the stretched tubes, foils or tapes are spliced in a manner known per se.
  • the copolymers according to the invention processed in this way have an exceptionally good splicing ability.
  • splicing can be done by needling with needle rollers, carding, twisting, scribing, squeezing, rubbing, brushing or treatment with water jet, ultrasound or compressed air.
  • extruded and stretched foils, tubes or tapes can be spliced, cut in a stack of 2 to 40 mm in length, or the foils, tubes or tapes can be spliced into continuous fibers and, if necessary, these can be cut in a stack of 2 to 40 mm in length.
  • Opening machines are known from the textile industry and belong to the group of tearing machines, which, for example, open up textile waste and unclean cotton or cotton waste for new purposes, ie return it to a fine-fiber form.
  • a 5 sawtooth opening machine is preferably used.
  • a special feature of the latter device is that the so-called opening drum is provided with a sawtooth-like surface.
  • the protection of the invention also extends to the fibers, produced by the method according to the invention.
  • the fibers are used in the form of nonwovens, nets, knits or fabrics.
  • the use of the fiber as such, in short or long fiber form, is in no way excluded.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)
  • Nonwoven Fabrics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Manufacture of fibres from thermoplastic copolymers of acrylonitrile and at least one further monomer component, e.g. acrylic esters, styrenes, vinyl compounds and/or polymerisable hydrocarbons. The copolymer is melt processed into films, ribbons or tubes, which are oriented and split. The splitting is preferably effected with an opener machine.

Description

Es ist bekannt, Fasern aus thermoplastischen Polymerisaten oder Mischungen von thermoplastischen Polymerisaten herzustellen. In der Regel werden Fasern durch Schmelzspinnen oder durch Spinnen aus Lösungsmitteln hergestellt. Für die Weiterverarbeitung, insbesondere zu Vliesen, Gewirken oder Geweben, die ihrerseits als Verbund- und Füllmaterial Verwendung finde sollen, weisen derartige Fasern aber zu starke textile Eigenschaften auf. Das heisst, derartige Fasern weisen eine zu grosse Reiss- oder Bruchdehnung auf.It is known to produce fibers from thermoplastic polymers or mixtures of thermoplastic polymers. As a rule, fibers are produced by melt spinning or by spinning from solvents. However, such fibers have too strong textile properties for further processing, in particular into nonwovens, knitted fabrics or fabrics, which in turn are to be used as composite and filling material. This means that such fibers have too great an elongation at break or break.

Es wird, um eine hohe Verstärkungswirkung zu erzielen, eine Faser benötigt, die eine hohe Reissfestigkeit bei geringster Reiss- oder Bruchdehnung aufweist.In order to achieve a high reinforcing effect, a fiber is required which has a high tensile strength with the least elongation at break or breaking.

Ziel der Erfindung ist es, solches Fasermaterial herzustellen und entsprechend der obigen Beschreibung zum Einsatz zu bringen.The aim of the invention is to produce such fiber material and to use it as described above.

Erfindungsgemäss erfolgt das mit einem Verfahren nach Patentanspruch 1. Es hat sich gezeigt, dass sich bevorzugt extrudierte Folien, Schläuche oder Bänder aus einem Mischpolymerisat des Acrylnitrils mit Estern der Acrylsäure, beispielsweise Acrylsäuremethylester oder Acrylsäureäthylester, Estern der Methacrylsäure, beispielsweise Methacrylsäuremethylester oder Methyacrylsäureäthylester,(wobei die Ester der Acryl- oder Methacrylsäure mit 2 bis 6 Kohlenstoffatomen in der Alkoholgruppe bevorzugt werden) Styrol, Methylstyrol, Vinylchlorid, Vinylidenchlorid, Vinylpyridin, Vinylester, Vinyläther,(wobei die Vinylester oder Vinyläther mit 1 bis 4 Kohlenstoffatomen neben der Vinylgruppe bevorzugt werden) wie beispielsweise Vinylacetat, Methylvinyläther oder Aethylvinyläther, und/oder polymerisierbare Kohlenwasserstoffe, beispielsweise Äthylen, Propylen, Buten-1, Isobuten, Penten-1, Hexen-1, 2-Methylbuten-1, 2-Methylpenten-1, 4-Methylpenten-1 oder Inden, nach dem erfindungsgemässen Verfahren zu Fasern verarbeiten lassen.According to the invention, this is done with a method according to claim 1. It has been found that preferably extruded films, tubes or tapes made from a copolymer of acrylonitrile with esters of acrylic acid, for example methyl acrylate or ethyl acrylate, esters of methacrylic acid, for example methyl methacrylate or Methyl methacrylate (where the esters of acrylic or methacrylic acid with 2 to 6 carbon atoms in the alcohol group are preferred) styrene, methyl styrene, vinyl chloride, vinylidene chloride, vinyl pyridine, vinyl ester, vinyl ether, (where the vinyl ester or vinyl ether with 1 to 4 carbon atoms next to the vinyl group are preferred) such as, for example, vinyl acetate, methyl vinyl ether or ethyl vinyl ether, and / or polymerizable hydrocarbons, for example ethylene, propylene, butene-1, isobutene, pentene-1, hexene-1, 2-methylbutene-1, 2-methylpentene-1, 4- Methyl pentene-1 or inden can be processed into fibers by the process according to the invention.

15Als Mischpolymerisate gemäss obiger Beschreibung sind demzufolge Polymerisate aus Acrylnitril und einer oder mehrerer genannter Verbindungen zu verstehen. 15 Accordingly, copolymers according to the above description are to be understood as meaning polymers made from acrylonitrile and one or more of the compounds mentioned.

20Das Mischpolymerisat kann gegebenenfalls auch Füllstoffe und Pigmente, wie Russ, Ti02, Kreide, Hochofenschlacke etc., enthalten. 20 The copolymer can optionally also contain fillers and pigments, such as carbon black, Ti0 2 , chalk, blast furnace slag, etc.

Von besonderer Bedeutung sind Mischpolymerisate, die durch eine Pfropfungsreaktion eines wie vorstehend definierten Mischpolymerisates auf eine vorgelegte Elastomerphase erhalte wurden. Die Elastomerphase kann beispielsweise hauptsächlich Anteile von Butadien mit Acrylnitril, Styrol und/oder Isopren enthalten.Of particular importance are copolymers which have been obtained by grafting a copolymer as defined above onto a submitted elastomer phase. The elastomer phase can, for example, mainly contain proportions of butadiene with acrylonitrile, styrene and / or isoprene.

Mischpolymerisate, die auf einer Pfropfungsreaktion beruhen, weisen eine verbesserte Schlagzähigkeit auf; damit kann auch das Reckverhältnis erhöht werden und es resultieren Fasern mit höherer Festigkeit.Copolymers which are based on a grafting reaction have improved impact strength; this also increases the draw ratio and results in fibers with higher strength.

Die feinverzeigte, verästelte Struktur der einzelnen Faser prädestiniert das erfindungsgemäss hergestellte Produkt für Einsatzgebiete, die unter der Bezeichnung Nonwovens bekannt sind. Durch die polaren Gruppen des Mischpolymerisates wird eine äusserst gute Haftung, beispielsweise an cellulosehaltigen Produkten oder in Laminierharzen, erreicht. Diese Hafteigenschaften prädestinieren die genannten gespleissten Faser als Verstärkungs- und Füllmaterial in Formkörpern aller Art. Die Steifheit der einzelnen Faser wiederum betont derartige Anwendungsmöglichkeiten.The finely branched, branched structure of the individual fibers predestines the product produced according to the invention for areas of application which are known under the name of nonwovens. The polar groups of the copolymer give extremely good adhesion, for example to cellulose-containing products or in laminating resins. These adhesive properties predestine the spliced fiber mentioned as a reinforcing and filling material in molded articles of all kinds. The stiffness of the individual fibers in turn emphasizes such possible applications.

Zur Ausführung des Verfahrens wird beispielsweise mit einem Extruder, welcher mit einer Breitschlitzdüse oder einem Blaskopf ausgerüstet ist, oder mit einem Kalander zu Schläuchen oder Folien und Bändern extrudiert oder kalandriert. Die Verarbeitungstemperatur richtet sich nach dem zum Einsatz gelangenden Mischpolymerisat und kann vom Fachmann individuell nach den Erfordernissen der Praxis ermittelt werden. Die Schläuche, Folien oder Bänder kühlt man auf Temperaturen ab, . die 10 bis 70°C über der Glasumwandlungstemperatur liegen und reckt dann auf einem Abzugswerk um das 2- bis 20-fache. Das dem eingesetzten Mischpolymerisat optimal entsprechende Reckverhältnis kann leicht durch Versuche ermittelt werden. Grund sätzlich gilt die Regel, dass die Neigung zum Spleissen sich mit abnehmender Reckungstemperatur, zunehmendem Reckungsgrad und mit Erhöhung der Reckgeschwindigkeit vergrössert.To carry out the method, for example, an extruder, which is equipped with a slot die or a blow head, or with a calender is extruded or calendered into tubes or foils and tapes. The processing temperature depends on the copolymer used and can be determined individually by a person skilled in the art according to practical requirements. The hoses, foils or tapes are cooled to temperatures,. which are 10 to 70 ° C above the glass transition temperature and then stretched 2 to 20 times on a fume cupboard. The stretching ratio optimally corresponding to the copolymer used can easily be determined by experiment. In principle, the rule applies that the tendency to splice increases with decreasing stretching temperature, increasing degree of stretching and with increasing stretching speed.

Die Schläuche, Folien oder Bänder können nach dem Extrudier-oder Kalandrierprozess auf die entsprechenden Temperaturen gekühlt und dann gereckt werden. Es ist aber auch möglich, die Produkte nach dem Extrudieren oder Kalandrieren zu kühlen, zu lagern und nachträglich wieder auf die notwendigen Temperaturen zu erwärmen und dann zu recken.The hoses, foils or tapes can be cooled to the appropriate temperatures after the extrusion or calendering process and then stretched. However, it is also possible to cool the products after extrusion or calendering, to store them and to subsequently heat them up to the necessary temperatures and then stretch them.

Die gereckten Schläuche, Folien oder Bänder werden auf an sich bekannte Weise gespleisst. Die derart verarbeiteten erfin-5 dungsgemässen Mischpolymerisate weisen eine aussergewöhnlich gute Spleissfähigkeit auf. So kann das Spleissen beispielsweise durch Nadeln mit Nadelwalzen, Kardieren, Verdrillen, ritzen, Quetschen, Reiben, Bürsten oder Behandlung mit Wasserstrahl, Ultraschall oder Druckluft erfolgen.The stretched tubes, foils or tapes are spliced in a manner known per se. The copolymers according to the invention processed in this way have an exceptionally good splicing ability. For example, splicing can be done by needling with needle rollers, carding, twisting, scribing, squeezing, rubbing, brushing or treatment with water jet, ultrasound or compressed air.

Diese extrudierten und gereckten Folien, Schläuche oder Bänder können, geschnitten im Stapel von 2 bis 40 mm Länge, gespleisst werden, oder die Folien, Schläuche oder Bänder können zu Endlosfasern gespleisst und diese gegebenenfalls im Stapel von 2 bis 40 mm Länge geschnitten werden.These extruded and stretched foils, tubes or tapes can be spliced, cut in a stack of 2 to 40 mm in length, or the foils, tubes or tapes can be spliced into continuous fibers and, if necessary, these can be cut in a stack of 2 to 40 mm in length.

In einer zweckmässigen Ausführungsform spleisst man mit einer Oeffnungsmaschine. Oeffnungsmaschinen sind aus der Textilindustrie bekannt und gehören zur Gruppe der Reissmaschinen, eie beispielsweise textile Abfälle und unsaubere Baumwolle oder Baumwollabfälle für neue Verwendungszwecke aufschliessen, d.h. wieder in eine feinfasrige Form zurückführen.In an expedient embodiment, splicing is carried out using an opening machine. Opening machines are known from the textile industry and belong to the group of tearing machines, which, for example, open up textile waste and unclean cotton or cotton waste for new purposes, ie return it to a fine-fiber form.

Unter der Gruppe der Oeffnungsmaschinen wird bevorzugt eine 5Sägezahn-Oeffnungsmaschine angewendet. Besonderes Merkmal letzteren Gerätes ist, dass der sogenannte Oeffnungs-Tambour mit einer sägezahnartigen Oberfläche versehen ist. Durch die Anwendung von Oeffnungsmaschinen werden die Fasern in Form von Stapelfaserflocken erhalten. Die Fasern liegen dann in feinster Form und anisotrop vor.Among the group of opening machines, a 5 sawtooth opening machine is preferably used. A special feature of the latter device is that the so-called opening drum is provided with a sawtooth-like surface. By using opening machines, the fibers are obtained in the form of staple fiber flakes. The fibers are then in the finest form and anisotropic.

Der Schutz der Erfindung erstreckt sich auch über die Fasern, hergestellt nach dem erfindungsgemässen Verfahren.The protection of the invention also extends to the fibers, produced by the method according to the invention.

Die Fasern werden in Form von Vliesen, Netzen, Gewirken oder Geweben verwendet. Dabei ist die Verwendung der Faser als solche, in kurz- oder langfasriger Form, in keiner Weise ausgeschlossen.The fibers are used in the form of nonwovens, nets, knits or fabrics. The use of the fiber as such, in short or long fiber form, is in no way excluded.

Claims (7)

1. Verfahren zur Herstellung von Fasern aus thermoplastischen Mischpolymerisaten des Acrylnitrils, dadurch gekennzeichnet, dass man Mischpolymerisate mit 45 bis 96 Gew.% Acrylnitril, die hergestellt wurden durch eine Pfropfungsreaktion auf ein vorgelegte Elastomerphase, in einem Schmelzverfahren zu Folien, Bändern oder Schläuchen verarbeitet, diese anschliessend bei Temperaturen, die 10 bis 70° C über der jeweiligen Glasumwandlungstemperatur liegen, durch Recken uniaxial orientiert und aufspleisst.1. A process for the production of fibers from thermoplastic copolymers of acrylonitrile, characterized in that copolymers with 45 to 96 wt. these are then uniaxially oriented and expanded at temperatures that are 10 to 70 ° C above the respective glass transition temperature. 12. Verfahren gemäss Patentanspruch 1, dadurch gekennzeichnet, dass man Mischpolymerisate, enthaltend 45 bis 96 Gew.% Acryl nitril und 4 bis 55 Gew.% Ester der Acrylsäure, Ester der Methacrylsäure, Styrole, Vinylchlorid, Vinylidenchlorid, Vinylpyridin, Vinylester, Vinyläther und/oder polymerisierbare Kohlenwasserstoffe, anwendet.1 2 . Process according to claim 1, characterized in that copolymers containing 45 to 96% by weight of acrylonitrile and 4 to 55% by weight of esters of acrylic acid, esters of methacrylic acid, styrenes, vinyl chloride, vinylidene chloride, vinyl pyridine, vinyl esters, vinyl ethers and / or polymerizable hydrocarbons. 3. Verfahren gemäss Patentansprüchen 1 und 2, dadurch gekennzeichnet, dass man die Folien, Bänder und Schläuche um das 2- bis 20-fache uniaxial reckt.3. The method according to claims 1 and 2, characterized in that the films, tapes and tubes are stretched 2 to 20 times uniaxially. 4. Verfahren gemäss Patentansprüchen 1 bis 3, dadurch gekennzeichnet, dass man das Aufspleissen mit einer Oeffnungsmaschine vornimmt.4. The method according to claims 1 to 3, characterized in that one carries out the splicing with an opening machine. 5. Verfahren gemäss Patentansprüchen 1 bis 3, dadurch gekennzeichnet, dass man das Aufspleissen mit einer Sägezahn- öffnungsmaschine vornimmt.5. The method according to claims 1 to 3, characterized in that one carries out the splicing with a sawtooth opening machine. 6. Fasern, hergestellt nach einem der Verfahren gemäss Patentansprüchen 1 bis 5.6. Fibers produced by one of the processes according to claims 1 to 5. 7. Verwendung von Fasern gemäss Patentanspruch 6 in Form von Vliesen, Netzen, Geweben oder Gewirken.7. Use of fibers according to claim 6 in the form of nonwovens, nets, woven or knitted fabrics.
EP80107458A 1979-12-12 1980-11-28 Thermoplastic acrylonitrile copolymer fibres, their manufacture and use Withdrawn EP0030666A3 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH10992/79 1979-12-12
CH1099279A CH643304A5 (en) 1979-12-12 1979-12-12 METHOD FOR PRODUCING FIBRES FROM THERMOPLASTIC copolymers of acrylonitrile.

Publications (2)

Publication Number Publication Date
EP0030666A2 true EP0030666A2 (en) 1981-06-24
EP0030666A3 EP0030666A3 (en) 1981-08-05

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JP (1) JPS5696912A (en)
CH (1) CH643304A5 (en)
DK (1) DK529680A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0780498A1 (en) * 1995-12-18 1997-06-25 The Standard Oil Company Melt spun acrylonitrile olefinically unsaturated fibers and a process to make fibers
DE102014219707A1 (en) 2014-09-29 2016-03-31 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Melt spinnable copolymers of polyacrylonitrile, process for producing fibers or fiber precursors by means of melt spinning and correspondingly produced fibers
DE102015222585A1 (en) 2015-11-16 2017-05-18 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Process for the preparation of thermally stable melt-spinnable PAN copolymers, PAN copolymers, moldings formed therefrom and process for the preparation of these moldings
WO2017162268A1 (en) 2016-03-22 2017-09-28 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Melt spinnable copolymers from polyacrylonitrile, method for producing fibers or fiber precursors by means of melt spinning, and fibers produced accordingly
WO2017167355A1 (en) 2016-03-29 2017-10-05 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Melt spinnable copolymers from polyacrylonitrile, method for producing fibers or fiber precursors by means of melt spinning, and fibers produced accordingly
EP3872103A1 (en) 2020-02-25 2021-09-01 DWI - Leibniz-Institut für Interaktive Materialien e.V. Melt-processable acrylonitrile-based copolymers and their acidic prestabilization for conversion into carbon fibers and workpieces

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1428992A (en) * 1965-03-29 1966-02-18 Polymer Proc Res Inst Method and device for the continuous manufacture of fibrils

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1428992A (en) * 1965-03-29 1966-02-18 Polymer Proc Res Inst Method and device for the continuous manufacture of fibrils

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
FASERFORSCHUNG UND TEXTILTECHNIK, Band 26, Nr. 3, 1975 Berlin (DE) H. KRASSIG: "Folienbandchen und Splitter- bzw. Spaltfasern", Seiten 135-142. * Seite 137, linke Spalte, Absatz 3 * *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0780498A1 (en) * 1995-12-18 1997-06-25 The Standard Oil Company Melt spun acrylonitrile olefinically unsaturated fibers and a process to make fibers
DE102014219707A1 (en) 2014-09-29 2016-03-31 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Melt spinnable copolymers of polyacrylonitrile, process for producing fibers or fiber precursors by means of melt spinning and correspondingly produced fibers
WO2016050478A1 (en) 2014-09-29 2016-04-07 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Melt spinnable copolymers from polyacrylonitrile, method for producing fibers or fiber precursors by means of melt spinning, and fibers produced accordingly
DE102015222585A1 (en) 2015-11-16 2017-05-18 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Process for the preparation of thermally stable melt-spinnable PAN copolymers, PAN copolymers, moldings formed therefrom and process for the preparation of these moldings
WO2017084853A1 (en) 2015-11-16 2017-05-26 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e. V. Method for producing thermally stable melt-spinnable pan copolymers, pan copolymers, molded bodies made thereof, and a method for producing said molded bodies
US11203656B2 (en) 2015-11-16 2021-12-21 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Method for producing thermally stable melt-spinnable pan copolymers, pan copolymers, molded bodies made thereof, and a method for producing said molded bodies
WO2017162268A1 (en) 2016-03-22 2017-09-28 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Melt spinnable copolymers from polyacrylonitrile, method for producing fibers or fiber precursors by means of melt spinning, and fibers produced accordingly
US11180869B2 (en) 2016-03-22 2021-11-23 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Melt spinnable copolymers from polyacrylonitrile, method for producing fibers or fiber precursors by means of melt spinning, and fibers produced accordingly
WO2017167355A1 (en) 2016-03-29 2017-10-05 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Melt spinnable copolymers from polyacrylonitrile, method for producing fibers or fiber precursors by means of melt spinning, and fibers produced accordingly
EP3872103A1 (en) 2020-02-25 2021-09-01 DWI - Leibniz-Institut für Interaktive Materialien e.V. Melt-processable acrylonitrile-based copolymers and their acidic prestabilization for conversion into carbon fibers and workpieces

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EP0030666A3 (en) 1981-08-05
DK529680A (en) 1981-06-13
CH643304A5 (en) 1984-05-30
JPS5696912A (en) 1981-08-05

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