EP0013541A1 - Process for manufacturing fibres from thermoplastic acrylonitrile polymers - Google Patents

Process for manufacturing fibres from thermoplastic acrylonitrile polymers Download PDF

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Publication number
EP0013541A1
EP0013541A1 EP79810189A EP79810189A EP0013541A1 EP 0013541 A1 EP0013541 A1 EP 0013541A1 EP 79810189 A EP79810189 A EP 79810189A EP 79810189 A EP79810189 A EP 79810189A EP 0013541 A1 EP0013541 A1 EP 0013541A1
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EP
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Prior art keywords
acrylonitrile
polymer
acrylic
polymerisate
fibers
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EP79810189A
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German (de)
French (fr)
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EP0013541B1 (en
Inventor
Guido Dr.-Chem. Stampa
Gero Dr. Dipl.-Ing. Büttiker
Peter Dr.-Chem Meier
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Amrotex AG
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Amrotex AG
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Priority to AT79810189T priority Critical patent/ATE1956T1/en
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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

  • the invention relates to a process for producing fibers from a polymer of acrylonitrile with esters of acrylic and / or methacrylic acid, which has a molar concentration of the acrylonitrile units in the range from 50 to 96%.
  • asbestos fibers are used as reinforcing material and / or filler for the production of components, such as pipes, plates, plant boxes, etc. It is also known that asbestos will not be available in unlimited quantities and must be counted among those natural products whose stocks may soon run out. For this reason, the relevant industry repeatedly tries to replace the asbestos fibers with other fiber material, including fibers made of plastics, such as polypropylene, polyester, polyamide, etc. Polypropylene fibers have the disadvantage that the adhesion with the hydraulic binders or . whose hardening products are bad; therefore, attempts are known to process polypropylene fibers connected in a network.
  • Polyester and polyamide products that can be spliced into fibers also unsuitable because they are not alkali-resistant.
  • Other plastics such as PVC, which, from a chemical point of view, can be suitable for processing together with hydraulic binders, prove to be difficult to split.
  • extruded, stretched and spliced hoses or tapes can be used as continuous fibers or as a reinforcing material cut in a stack from 1 to 10 mm inge.
  • the polymer can also be a graft polymer of acrylonitrile / alkyl ester of acrylic acid and / or methacrylic acid on a copolymer of acrylonitrile / butadiene and / or isoprene or of alkyl acrylates.
  • the polymer can contain fillers and pigments such as carbon black, TiO 2 , circles, blast furnace slag etc.
  • the mixing ratio between fibers and cement is depending on the fiber length, respectively. depending on the requirements placed on the finished product, between 1: 3 and 1: 15.
  • the cut pieces of tubing can only be spliced into the individual fibers when they are mixed with the hydraulic binders.

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  • 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)
  • Reinforced Plastic Materials (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

1. A method for producing fibers from a thermoplastic polymerisate of acrylonitrile with esters of acrylic or methacrylic acid, which polymer has a molar concentration of acrylonitrile units in the range of 50 to 96 %, characterized in that a graft polymerisate of acrylonitril/acrylic or methacrylic acid ester grafted on a copolymerisate of acrylonitril/butadiene and/or -isoprene or of acryloacrylates is used as polymerisate, said polymerisate is extruded to strips or tubes, said strips or tubes are uniaxially stretchend at temperatures between 100 and 150 degrees C and are split after cooling.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung von Fasern aus einem Polymerisat des Acrylnitrils mit Estern der Acryl-und/oder Methacrylsäure, das eine molare Konzentration der Acrylnitrileinheiten im Bereich von 50 bis 96% aufweist.The invention relates to a process for producing fibers from a polymer of acrylonitrile with esters of acrylic and / or methacrylic acid, which has a molar concentration of the acrylonitrile units in the range from 50 to 96%.

Es ist bekannt, dass z.B. für die Fertigung von Bauelementen, wie Rohre, Platten, Pflanzenkasten etc., Asbestfasern als Armierungsmaterial und/oder Füllkörper verwendet werden. Weiter ist bekannt, dass Asbest nicht in unbegrenzten Mengen zur Ver- fügung stehen wird und zu'denjenigen Naturstoffen gezählt werden muss, deren Vorräte sich bald erschöpfen können. Aus diesem Grunde wird von Seiten der einschlägigen Industrie immer wieder versucht, die Asbestfasern durch anderes Fasermaterial zu ersetzen, unter anderem auch durch Fasern aus Kunststoffen, wie Polypropylen, Polyester, Polyamid etc. Polypropylenfasern haben den Nachteil, dass die Adhäsion mit den hydraulischen Bindemitteln resp. deren Erhärtungsprodukten schlecht ist; deshalb sind Versuche bekannt, netzartig verbundene Polypropylenfasern zu verarbeiten. Polyester- und Polyamidprodukte, welche sich zu Fasern aufspleissen lassen,

Figure imgb0001
sich ebenfalls als ungeeignet, weil sie nicht alkali- fest sind. Andere Kunststoffe, wie z.B. PVC, die von ihren chemischen Eigenschaften her gesehen für die Verarbeitung zusammen mit hydraulischen Bindemitteln geeignet sein können, erweisen sich als wenig aufspleissbar.It is known that, for example, asbestos fibers are used as reinforcing material and / or filler for the production of components, such as pipes, plates, plant boxes, etc. It is also known that asbestos will not be available in unlimited quantities and must be counted among those natural products whose stocks may soon run out. For this reason, the relevant industry repeatedly tries to replace the asbestos fibers with other fiber material, including fibers made of plastics, such as polypropylene, polyester, polyamide, etc. Polypropylene fibers have the disadvantage that the adhesion with the hydraulic binders or . whose hardening products are bad; therefore, attempts are known to process polypropylene fibers connected in a network. Polyester and polyamide products that can be spliced into fibers,
Figure imgb0001
also unsuitable because they are not alkali-resistant. Other plastics, such as PVC, which, from a chemical point of view, can be suitable for processing together with hydraulic binders, prove to be difficult to split.

Nun hat sich, für die Fachwelt überraschend, gezeigt, dass sich extrudierte Schläuche oder Bänder aus einem Polymerisat des Acrylnitrils mit Estern der Acryl- und/oder Methacrylsäure, das eine molare Konzentration der Acrylnitrileinheiten im Bereich von 50 bis 96 % aufweist, relativ leicht in feinste Fa- sern aufspleissen lassen, welche ihrerseits, dank der polaren Gruppen dieses Polymerisates, eine äusserst gute Haftung an Erhärtungsprodukten von Bindemitteln, aber auch an cellulosehaltigen Produkten, aufweisen. Diese Hafteigenschaften prädestinieren die genannten gespleissten Fasern, als leichtes Armierungs- und Füllmaterial eingesetzt zu werden.Now, surprisingly for the experts, it has been found that extruded tubes or tapes made of a polymer of acrylonitrile with esters of acrylic and / or methacrylic acid, which has a molar concentration of the acrylonitrile units in the range from 50 to 96%, are relatively easy have the finest fibers spliced on, which in turn, thanks to the polar groups of this polymer, have extremely good adhesion to hardening products of binders, but also to cellulose-containing products. These adhesive properties predestine the spliced fibers mentioned to be used as a light reinforcing and filling material.

Ziel der Erfindung ist es, solches Fasermaterial herzustellen. Erfindungsgemäss wird dies wie folgt erreicht:

  • Mit einem Extruder, welcher mit einer Schlauchdüse ausgerüstet ist, wurde bei einer Temperatur von 170 bis 185° C ein Polymerisat des Acrylnitrils mit Estern der Acryl- und/oder Methacrylsäure, das eine molare Konzentration der Acrylnitrileinheiten im Bereich von 50 bis 96 % aufweist, ein Schlauch von 16/14 mm Durchmesser extrudiert. Dieser Schlauch wurde kurz nach dem Extruder, also noch im thermoplastischen Bereich, um das 2-fache und nach dem Abzugswerk im thermoelastischen Bereich bei einer Temperatur von 100 bis 150° C mittels eines Walzwerkes auf das 3- bis 11-fache gereckt. Es zeigt sich nun, dass die Neigung zum Spleissen sich parallel mit der Erhöhung und Geschwindigkeit der Reckung vergrössert. Vorzugsweise wird 4- bis 8-fach gereckt. Die Feinheit der einzelnen Spleissfasern nimmt in zunehmendem Mass mit dem Anwachsen der Reckstrecke zu.
The aim of the invention is to produce such fiber material. According to the invention, this is achieved as follows:
  • With an extruder equipped with a hose nozzle, a polymer of acrylonitrile with esters of acrylic and / or methacrylic acid was obtained at a temperature of 170 to 185 ° C, which has a molar concentration of acrylonitrile units in the range of 50 to 96%, extruded a 16/14 mm diameter tube. Shortly after the extruder, i.e. still in the thermoplastic range, this tube was stretched 2 to 3 times and after the draw-off unit in the thermoelastic range at a temperature of 100 to 150 ° C. by means of a rolling mill to 3 to 11 times. It can now be seen that the tendency to splice increases in parallel with the increase and speed of stretching. It is preferable to stretch 4 to 8 times. The delicacy of the individual splice fibers increase to an increasing extent with the stretching of the stretching section.

Diese extrudierten, gereckten und gespleissten Schläuche oder Bänder können als Endlosfasern oder im Stapel von 1 bis 10 mm inge geschnitten als Armierungsmaterial eingesetzt werden.These extruded, stretched and spliced hoses or tapes can be used as continuous fibers or as a reinforcing material cut in a stack from 1 to 10 mm inge.

Das Polymerisat kann auch ein Propfpolymerisat von Acrylnitril/ Alkylester der Acrylsäure und/oder Methacrylsäure auf einem Copolymerisat aus Acrylnitril/Butadien und/oder Isopren oder aus Alkylacrylaten sein.The polymer can also be a graft polymer of acrylonitrile / alkyl ester of acrylic acid and / or methacrylic acid on a copolymer of acrylonitrile / butadiene and / or isoprene or of alkyl acrylates.

Vorzugsweise wird ein Copolymerisat aus Acrylnitril und Alkylacrylat, aufgepropft auf ein Copolymerisat aus Acrylnitril/ Butadien, im Handel unter dem Namen BAREX® bekannt, verwendet.A copolymer of acrylonitrile and alkyl acrylate, grafted onto a copolymer of acrylonitrile / butadiene, known commercially under the name BAREX®, is preferably used.

Das Polymerisat kann Füllstoffe und Pigmente, wie Russ, TiO2, Kreise, Hochofenschlacke etc., enthalten.The polymer can contain fillers and pigments such as carbon black, TiO 2 , circles, blast furnace slag etc.

Die Herstellung der hydraulisch gebundenen Bauelemente selbst geschieht nach bekannten Verfahren, die den Fabrikationsprozessen für Papier und Asbestzementplatten und -formstücke nicht unähnlich sind:

  • Aufschlämmen mit Klebstoff resp. Zement und viel Wasser, Bildung eines Faservlieses auf Sieben und Trocknen und Pressen desselben.
The hydraulically bound components themselves are manufactured using known processes, which are not unlike the manufacturing processes for paper and asbestos cement panels and shaped pieces:
  • Slurrying with adhesive resp. Cement and lots of water, formation of a nonwoven fabric on sieving and drying and pressing the same.

Das Mischungsverhältnis zwischen Fasern und Zement liegt je nach Faserlänge resp. je nach den Anforderungen, die an das fertige Produkt gestellt werden, zwischen l : 3 bis 1 : 15. Das Aufspleissen der geschnittenen Schlauchstücke in die einzelnen Fasern kann auch erst beim Mischen mit den hydraulischen Bindemitteln geschehen.

Figure imgb0002
Figure imgb0003
 The mixing ratio between fibers and cement is depending on the fiber length, respectively. depending on the requirements placed on the finished product, between 1: 3 and 1: 15. The cut pieces of tubing can only be spliced into the individual fibers when they are mixed with the hydraulic binders.
Figure imgb0002
Figure imgb0003

Claims (2)

1. Verfahren zur Herstellung von Fasern aus einem thermoplastischen Polymerisat des Acrylnitrils mit Estern der Acryl- und/oder Methacrylsäure, das eine molare Konzentration der Acryl- ! nitrileinheiten im Bereich von 50 bis 96 % aufweist, dadurch gekennzeichnet, dass man das Polymerisat zu Bändern oder Schläuchen extrudiert, diese bei Temperaturen zwischen 100 und 150° C uniaxial reckt und nach Abkühlen aufspleisst.1. Process for the production of fibers from a thermoplastic polymer of acrylonitrile with esters of acrylic and / or methacrylic acid, which has a molar concentration of acrylic! Nitrile units in the range of 50 to 96%, characterized in that the polymer is extruded into strips or tubes, stretched uniaxially at temperatures between 100 and 150 ° C and spliced after cooling. 2. Verfahren nach Patentanspruch 1, dadurch gekennzeichnet, dass man als Polymerisat ein Pfropfpolymerisat von Acrylnitril/Acrylsäureester, aufgepfropft auf ein Copolymerisat aus Acrylnitril-Butadien und/oder Isopren, verwendet.2. The method according to claim 1, characterized in that a graft polymer of acrylonitrile / acrylic acid ester, grafted onto a copolymer of acrylonitrile-butadiene and / or isoprene, is used as the polymer.
EP79810189A 1979-01-04 1979-12-28 Process for manufacturing fibres from thermoplastic acrylonitrile polymers Expired EP0013541B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT79810189T ATE1956T1 (en) 1979-01-04 1979-12-28 PROCESS FOR THE MANUFACTURE OF FIBERS FROM THERMOPLASTIC POLYMERS OF ACRYLIC NITRILE.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH4179 1979-01-04
CH41/79 1979-01-04

Publications (2)

Publication Number Publication Date
EP0013541A1 true EP0013541A1 (en) 1980-07-23
EP0013541B1 EP0013541B1 (en) 1982-12-08

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EP79810189A Expired EP0013541B1 (en) 1979-01-04 1979-12-28 Process for manufacturing fibres from thermoplastic acrylonitrile polymers

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AT (1) ATE1956T1 (en)
DE (1) DE2964235D1 (en)
DK (1) DK4080A (en)

Cited By (1)

* 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

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1208402A (en) * 1957-06-11 1960-02-23 Du Pont Filamentous structures and process for manufacturing them
FR1428992A (en) * 1965-03-29 1966-02-18 Polymer Proc Res Inst Method and device for the continuous manufacture of fibrils
US3364102A (en) * 1964-07-27 1968-01-16 Dow Chemical Co Method for making paper-like and related non-woven products from acrylonitrile polymer fibers
CH450894A (en) * 1964-06-03 1968-05-15 Chemstrand Ltd Process for the manufacture of paper from fibers of acrylonitrile polymers and papers obtained by this process
DE1469160A1 (en) * 1961-08-29 1968-12-05 Schweizerische Viscose Process for producing artificial and synthetic fibers
FR1559289A (en) * 1967-09-20 1969-03-07

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1208402A (en) * 1957-06-11 1960-02-23 Du Pont Filamentous structures and process for manufacturing them
DE1469160A1 (en) * 1961-08-29 1968-12-05 Schweizerische Viscose Process for producing artificial and synthetic fibers
CH450894A (en) * 1964-06-03 1968-05-15 Chemstrand Ltd Process for the manufacture of paper from fibers of acrylonitrile polymers and papers obtained by this process
US3364102A (en) * 1964-07-27 1968-01-16 Dow Chemical Co Method for making paper-like and related non-woven products from acrylonitrile polymer fibers
FR1428992A (en) * 1965-03-29 1966-02-18 Polymer Proc Res Inst Method and device for the continuous manufacture of fibrils
FR1559289A (en) * 1967-09-20 1969-03-07

Cited By (1)

* 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

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Publication number Publication date
ATE1956T1 (en) 1982-12-15
EP0013541B1 (en) 1982-12-08
DE2964235D1 (en) 1983-01-13
DK4080A (en) 1980-07-05

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