EP0098484A2 - Manufacture of polyacrylonitrile filaments containing very few solvents - Google Patents

Manufacture of polyacrylonitrile filaments containing very few solvents Download PDF

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Publication number
EP0098484A2
EP0098484A2 EP83106187A EP83106187A EP0098484A2 EP 0098484 A2 EP0098484 A2 EP 0098484A2 EP 83106187 A EP83106187 A EP 83106187A EP 83106187 A EP83106187 A EP 83106187A EP 0098484 A2 EP0098484 A2 EP 0098484A2
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Prior art keywords
spinning
threads
weight
spun
content
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German (de)
French (fr)
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EP0098484A3 (en
EP0098484B1 (en
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Ulrich Dr. Reinehr
Toni Herbertz
Hermann-Josef Jungverdorben
Hans Dr. Uhlemann
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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
    • D01D5/04—Dry spinning methods

Definitions

  • the invention relates to a process for producing low-solvent polyacrylonitrile spun threads with at least 45% by weight of acrylonitrile units by a dry spinning process in which the threads do not come into contact with an extracting agent for the spinning solvent.
  • Spinning material produced in this way with low residual solvent can be stretched, crimped, relaxed and cut, for example, in one work step without any interruption, and thus converted into finished fibers in a continuous manner.
  • Spun material made from dry-spun acrylic fibers usually has a solvent content of approx. 15-50% by weight. This residual solvent component, for example of dimethylformamide, is removed almost quantitatively by a washing process before, during or after the stretching.
  • US Pat. No. 2,811,409 describes a process for the continuous production of acrylic threads with low residual solvent contents from spinnerets having a low number of holes of max. 200 holes and very long spinning chimneys up to 9 m with several hot air inlets using acrylonitrile copolymers with high viscosities.
  • spinning nozzles with extremely fine bores of e.g. 0.08 mm diameter which leads to extremely low spinning distortions. These low spinning distortions are obviously necessary in order to avoid tears and runs on the bobbins given the high viscosities of the spinning solutions and the high energy loads in the spinning shaft.
  • This process can only be used to produce acrylic silk with low overall titers.
  • the object of the present invention was to provide a process for the production of low-solvent polyacrylonitrile spun filaments after a dry spinning process with high total titers of 100,000 dtex and more, which without an extraction medium for the spinning solvent and avoids static charges.
  • the residual solvent content in the spun material can be controlled by various parameters during dry spinning. Suitable parameters are the temperatures of the shaft and the spinning air to be used, the air volume and the dwell time in the spinning shaft. This in turn can be influenced by the spinning shaft geometry and spinning speed.
  • Suitable parameters are the temperatures of the shaft and the spinning air to be used, the air volume and the dwell time in the spinning shaft. This in turn can be influenced by the spinning shaft geometry and spinning speed.
  • temperatures of the heating medium are between 150 and 300 ° C. with treatment times of 5 seconds to 3 minutes; in the case of saturated steam the temperature is Heating medium preferably 103 to 120 ° C, the exposure time 5 seconds to 5 minutes; and in the case of superheated steam, the temperatures are preferably between 120 and 180 ° C and the treatment times between 5 seconds and 5 minutes.
  • Heating rails, heating brackets and heated godets are also suitable for heat treatment.
  • the spinning delay of the method is preferably greater than 2.
  • the spinning solution has a viscosity of 15 to 50 ball drops at 100 ° C.
  • Spinning delay V is defined as the ratio of take-off speed A to ejection speed S:
  • Acrylonitrile polymers are all acrylics which can be spun into so-called acrylic fibers or modacrylic fibers tril homo- and copolymers suitable, preferably acrylonitrile copolymers with at least 85 wt .-% acrylonitrile units.
  • the polymers are known.
  • the preparation can also contain water as components. Preparation mixtures with a moisture content of more than 50% are not preferred, however, because the group of threads is cooled too much before the subsequent post-treatment steps, such as drawing, crimping, etc., and uniform heating of the spun material before drawing is no longer guaranteed.
  • Suitable lubricants are glycols, their derivatives, silicone oils, ethoxylated fatty acids, alcohols, esters, amides, alkyl ether sulfates, and mixtures thereof.
  • Suitable antistatic agents are the usual cation-active, anion-active or non-ionic compounds, such as long-chain, ethoxylated, sulfated and neutralized alcohols.
  • the preparation is expediently brought into contact with the individual thread ribbons at elevated temperatures of 50-90 ° C. in order to prevent the hot thread sheet from cooling.
  • the one with a spinning machine For example, 20 manhole tapes spun from the total titre 100,000 dtex and more are prepared in this way, bundled after leaving the fusing unit and fed directly to a further aftertreatment, for example with the process steps stretching - crimping - shrinking - cutting.
  • a great advantage of the process according to the invention is that low-solvent spinning threads produced in this way can be aftertreated directly in a continuous process to produce acrylic fibers without any interruption.
  • Another great advantage of the method according to the invention for the production of low-solvent spun threads is furthermore that, due to the elimination of a washing process, a drying unit is no longer necessary. In addition to the lower investment and maintenance costs, energy costs can naturally also be significantly reduced.
  • spinning take-off speeds of up to 100 m / min are completely sufficient to keep the residual solvent content in the spun material clearly below 5% by weight.
  • the low-solvent spinning process according to the invention can also be transferred to so-called nozzle-dyed spinning material. If spinning solutions made of acrylonitrile polymers are added to dyes or pigments, dyed spun material is obtained which can be processed into spun-dyed acrylic fibers.
  • dimethylformamide (DMF) are mixed in a kettle at room temperature with stirring, with 300 kg of an acrylonitrile copolymer made from 93.6% acrylonitrile, 5.7% methyl acrylate and 0.7% sodium methallylsulfonate with a K value of 81.
  • the suspension is pumped via a gear pump into a spinning kettle equipped with an agitator. Then the suspension is heated in a double-walled tube with steam of 4.0 bar. The dwell time in the tube is 5 minutes.
  • the spinning solution which has a temperature of 138 ° C at the tube outlet and a viscosity of 19 ball falling seconds, measured at 100 ° C, is cooled to 90 ° C after leaving the heating device, filtered and fed directly to a spinning system with 20 spinning shafts.
  • the spinning solution is dry spun from 1264-hole nozzles with nozzle hole diameters of 0.25 mm at a take-off speed of 50 m / min.
  • the amount of spinning solution delivered per spinning shaft is 370.8 ccm / min.
  • the shaft temperature is 200 ° C and the air temperature is 360 ° C.
  • the throughput of air is 40 m 3 / h for each shaft.
  • the spinning threads which have been spun with a spinning delay of 2.1, are immediately before leaving the spinning shafts before entering a tube connected behind them with a warming agent containing 80-90 ° C.
  • the preparation is dosed via gear pumps.
  • the tube which is connected horizontally after the spinning machine and through which the filament yarn sheet is guided, is fed with hot air at 300 ° C in countercurrent to the direction of the yarn travel to remove the DMF.
  • the dwell time of the spinning threads in the spinning shafts and the tube fed with hot air is approximately 18 seconds.
  • the amount of hot air sent through the pipe in counterflow is 600 m 3 / h.
  • the warm acrylic cable which has a total titer of 344,000 dtex, still has a residual solvent content of 1.6% by weight of DMF.
  • the cable can then be stretched, crimped, shrunk and cut into staple fibers without interruption.
  • a spinning solution is spun into threads in accordance with Example 1 and, before entering the tube connected behind it, is again wetted with a low-water preparation containing 80-90 ° C. and containing a lubricant and an antistatic.
  • the tube In countercurrent to the direction of the thread, the tube is charged with superheated steam at 110 ° C for DMF removal.
  • the amount of steam is 150 kg / h.
  • the dwell time of the spinning material in the spinning shafts and the tube charged with superheated steam is again approx. 18 seconds.
  • the warm acrylic cable which again has a total titre of 344,000 dtex, be is still a residual solvent content of 1.3 wt .-% of DMF.
  • the cable can then be processed into finished staple fiber without interruption.
  • a spinning solution according to Example 1 is spun into threads, but the take-off speed is 100 m / min and the amount of spinning solution conveyed per spinning shaft is 512 ccm / min.
  • the spinning threads which have been spun with a spinning delay of 3.0, are prepared immediately before leaving the spinning shafts and before entering the tube behind them, and are then fed in the tube in countercurrent to the direction of the thread with hot air at 300 ° C. to remove the DMF .
  • the dwell time of the spinning material in the spinning shafts and the tube fed with hot air is approximately 9 seconds.
  • the amount of hot air sent through the pipe in counterflow is 800 m 3 / h.
  • the warm acrylic cable which has a total titer of 265,500 dtex, still has a residual solvent content of 2.2% by weight of DMF. The cable can then be processed directly into staple fibers without interruption.
  • a spinning solution was prepared, spun and prepared under the conditions given in Example 1.
  • the bundle of threads is then sent over a roller calender with 13 rollers of 40 cm diameter that is electrically heated to 195 ° C.
  • the thread sheet assumes a temperature of 159 ° C, measured without contact with the radiation thermometer KT 15 (manufacturer Heimann GmbH, Wiesbaden, FRG).
  • the dwell time of the threads on the calender rolls is approximately 10 seconds.
  • the roller calender is equipped with a suction device to remove residual amounts of spinning solvent.
  • the warm acrylic cable with a total titre of 344,000 dtex still has a residual solvent content of 0.8% by weight of DMF.
  • the cable can then be stretched, crimped, shrunk and cut into staple fibers without interruption.

Abstract

Polyacrilnitril-Spinnfäden mit einem Restlösungsmittelgehalt unter 5 Gew.-% und einem Gesamttiter über 100 000 dtex lassen sich ohne Kontaktierung mit einem Extraktionsmittel für das Spinnlösungsmittel dadurch herstellen, daß a) eine Spinnlösung versponnen wird, deren Viskosität bei 100 °C 10 bis 60 Kugelfallsekunden beträgt, b) die Fäden unmittelbar am Ende des Spinnschachtes innerhalb oder unmittelbar außerhalb des Schachtendes in noch heißem Zustand mit einer Präparation versehen werden, die ein Gleitmittel und ein Antistatikum enthält und den Fäden einen Feuchtegehalt von maximal 10 Gew.-%, bezogen auf Faserfeststoffgehalt, verleiht und c) die Fäden direkt ohne Abkühlung einer Wärmebehandlung ausgesetzt werden.Polyacrylonitrile spun threads with a residual solvent content of less than 5% by weight and a total titer of more than 100,000 dtex can be produced without contacting an extracting agent for the spinning solvent by a) spinning a spinning solution whose viscosity at 100 ° C. is 10 to 60 ball falling seconds b) the threads immediately at the end of the spinning shaft inside or immediately outside the shaft end, while still hot, are provided with a preparation which contains a lubricant and an antistatic and the threads have a moisture content of at most 10% by weight, based on the fiber solids content , gives and c) the threads are directly exposed to heat treatment without cooling.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung von lösungsmittelarmen Polyacrylnitril-Spinnfäden mit mindestens 45 Gew.-% Acrylnitrileinheiten durch ein Trockenspinnverfahren bei dem die Fäden nicht mit einem Extraktionsmittel für das Spinnlösungsmittel in Berührung kommen. Derartig hergestelltes restlösungsmittelarmes Spinngut läßt sich beispielsweise in einem Arbeitsgang ohne jedwede Unterbrechung direkt Verstrecken, Kräuseln, Relaxieren und Schneiden und somit auf kontinuierliche Weise in fertige Fasern überführen.The invention relates to a process for producing low-solvent polyacrylonitrile spun threads with at least 45% by weight of acrylonitrile units by a dry spinning process in which the threads do not come into contact with an extracting agent for the spinning solvent. Spinning material produced in this way with low residual solvent can be stretched, crimped, relaxed and cut, for example, in one work step without any interruption, and thus converted into finished fibers in a continuous manner.

Spinngut aus trockengesponnenen Acrylfasern weist üblicherweise einen Lösungsmittelgehalt von ca. 15 - 50 Gew.-% auf. Dieser Restlösungsmittelanteil, beispielsweise an Dimethylformamid, wird durch einen Waschprozeß vor, während oder auch nach der Verstreckung nahezu quantitativ entfernt.Spun material made from dry-spun acrylic fibers usually has a solvent content of approx. 15-50% by weight. This residual solvent component, for example of dimethylformamide, is removed almost quantitatively by a washing process before, during or after the stretching.

Die lösungsmittelhaltigen Waschwässer werden aus ökonomischen und ökologischen Gründen destillativ aufgearbeitet. In der US-P 2 811 409 wird ein Verfahren zur kontinuierlichen Herstellung von Acrylfäden mit niedrigen Restlösungsmittelgehalten aus Spinndüsen niedriger Lochzahl von max. 200 Loch und sehr langen Spinnschächten bis zu 9 m mit mehreren Heißlufteinlässen unter Verwendung von Acrylnitrilcopolymerisaten mit hohen Viskositäten beschrieben.The solvent-containing wash water is processed by distillation for economic and ecological reasons. US Pat. No. 2,811,409 describes a process for the continuous production of acrylic threads with low residual solvent contents from spinnerets having a low number of holes of max. 200 holes and very long spinning chimneys up to 9 m with several hot air inlets using acrylonitrile copolymers with high viscosities.

Wie aus den Beispielen ferner hervorgeht, werden für den Spinnprozeß Spinndüsen mit extrem feinen Bohrungen von z.B. 0,08 mm Durchmesser eingesetzt, was zu äußerst niedrigen Spinnverzügen führt. Diese niedrigen Spinnverzüge sind offenbar notwendig, um bei den hohen Viskositäten der Spinnlösungen und den hohen Energiebelastungen im Spinnschacht Abrisse und Aufläufer auf den Spulen zu vermeiden.As can also be seen from the examples, spinning nozzles with extremely fine bores of e.g. 0.08 mm diameter used, which leads to extremely low spinning distortions. These low spinning distortions are obviously necessary in order to avoid tears and runs on the bobbins given the high viscosities of the spinning solutions and the high energy loads in the spinning shaft.

Nach diesem Verfahren lassen sich lediglich Acrylseiden mit niedrigen Gesamttitern herstellen.This process can only be used to produce acrylic silk with low overall titers.

Außerdem treten nach dem.Verfahren der US-PS bei Restlösungsmittelgehalten unter ca. 5 Gew.-% an DMF starke statische Aufladungen der Fäden ein.In addition, strong static charges of the threads occur with residual solvent contents below about 5% by weight of DMF according to the process of the US Pat.

Aufgabe der vorliegenden Erfindung war es, ein Verfahren zur Herstellung von lösungsmittelarmen Polyacrylnitril-Spinnfäden nach einem Trockenspinnprozeß mit hohen Gesamttitern von 100 000 dtex und mehr zur Verfügung zu stellen, welches ohne ein Extraktionsmittel für das Spinnlösungsmittel auskommt und statische Aufladungen vermeidet.The object of the present invention was to provide a process for the production of low-solvent polyacrylonitrile spun filaments after a dry spinning process with high total titers of 100,000 dtex and more, which without an extraction medium for the spinning solvent and avoids static charges.

Wie dem Fachmann bekannt ist, läßt sich beim Trockenspinnen der Restlösungsmittelgehalt im Spinngut über verschiedene Parameter steuern. Geeignete Einflußgrößen sind die Temperaturen des Schachtes und der zu verwendenden Spinnluft, die Luftmenge und die Verweilzeit im Spinnschacht. Diese wiederum läßt sich durch die Spinnschachtgeometrie und Spinngeschwindigkeit beeinflussen. Die vorstehend definierte Aufgabe läßt sich mit dem bekannten Wissen allein jedoch nicht lösen.As is known to the person skilled in the art, the residual solvent content in the spun material can be controlled by various parameters during dry spinning. Suitable parameters are the temperatures of the shaft and the spinning air to be used, the air volume and the dwell time in the spinning shaft. This in turn can be influenced by the spinning shaft geometry and spinning speed. However, the task defined above cannot be solved with the known knowledge alone.

Es wurde nun überraschenderweise gefunden, daß man die vorstehend definierte Aufgabe lösen kann, wenn man eine Spinnlösung bestimmter Viskosität verwendet, das Spinngut unmittelbar am Ende des Spinnschachtes innerhalb oder unmittelbar außerhalb des Schachtendes in noch heißem Zustand mit einer Präparation, die ein Gleitmittel und ein Antistatikum enthält und den Fäden einen Feuchtegehalt (Wasser) von maximal 10 %, bezogen auf Faserfeststoff, verleiht, benetzt und direkt ohne Abkühlung einer Wärmebehandlung aussetzt, z.B. indem man das Spinngut durch ein Rohr leitet, durch welches im Gegenstrom zur Fadenlaufrichtung Heißluft, Sattdampf oder überhitzter Dampf geführt wird oder indem man die Fadenschar über einen beheizten, geschlossenen Walzenkalander mit Absaugvorrichtung für die Lösungsmittelreste führt.It has now surprisingly been found that the object defined above can be achieved if a spinning solution of a certain viscosity is used, the spinning material immediately at the end of the spinning shaft inside or immediately outside the shaft end in a still hot state with a preparation which contains a lubricant and an antistatic contains and gives the threads a moisture content (water) of maximum 10%, based on fiber solids, wetted and directly exposed to heat treatment without cooling, e.g. by passing the spinning material through a tube through which hot air, saturated steam or superheated steam is passed in countercurrent to the direction of the thread, or by passing the thread sheet over a heated, closed roller calender with a suction device for the solvent residues.

Im Falle von Kontakthitze oder Heißluft liegen besonders geeignete Temperaturen des Heizmediums zwischen 150 und 300°C bei Behandlungszeiten von 5 Sekunden bis 3 Minuten; im Falle von Sattdampf beträgt die Temperatur des Heizmediums vorzugsweise 103 bis 120°C, die Einwirkungszeit 5 Sekunden bis 5 Minuten; und im Falle von überhitztem Dampf liegen die Temperaturen bevorzugt zwischen 120 und 180°C und die Behandlungszeiten zwischen 5 Sekunden und 5 Minuten.In the case of contact heat or hot air, particularly suitable temperatures of the heating medium are between 150 and 300 ° C. with treatment times of 5 seconds to 3 minutes; in the case of saturated steam the temperature is Heating medium preferably 103 to 120 ° C, the exposure time 5 seconds to 5 minutes; and in the case of superheated steam, the temperatures are preferably between 120 and 180 ° C and the treatment times between 5 seconds and 5 minutes.

Weiterhin sind zur Wärmebehandlung Heizschiene, Heizbügel und beheizte Galetten geeignet.Heating rails, heating brackets and heated godets are also suitable for heat treatment.

Gegenstand der Erfindung ist daher ein Trockenspinn-Verfahren zur Herstellung von Polyacrylnitrilspinnfäden mit mindestens 45 Gew.-% Acrylnitrileinheiten, einem Restlösungsmittelgehalt unter 5 Gew.-% und einem Gesamttiter über 100 000 dtex ohne Kontaktierung mit einem Extraktionsmittel für das Spinnlösungsmittel durch Verspinnen einer Spinnlösung des Polymerisates, dadurch gekennzeichnet, daß

  • a) eine Spinnlösung versponnen wird, deren Viskosität bei 100°C 10 bis 60 Kugelfallsekunden beträgt,
  • b) die Fäden unmittelbar am Ende des Spinnschachtes innerhalb oder unmittelbar außerhalb des Schachtendes in noch heißem Zustand mit einer Präparation versehen werden, die ein Gleitmittel und ein Antistatikum enthält und den Fäden einen Feuchtegehalt von maximal 10 Gew.-%, bezogen auf Faserfeststoffgehalt, verleiht und
  • c) die Fäden direkt ohne Abkühlung einer Wärmebehandlung ausgesetzt werden.
The invention therefore relates to a dry spinning process for the production of polyacrylonitrile spun threads with at least 45% by weight of acrylonitrile units, a residual solvent content of less than 5% by weight and a total titer of over 100,000 dtex without contacting an extracting agent for the spinning solvent by spinning a spinning solution Polymers, characterized in that
  • a) a spinning solution is spun, the viscosity of which is 10 to 60 falling ball seconds at 100 ° C.,
  • b) the threads immediately at the end of the spinning shaft inside or immediately outside the end of the shaft, while still hot, are provided with a preparation which contains a lubricant and an antistatic and which gives the threads a moisture content of at most 10% by weight, based on the fiber solids content and
  • c) the threads are subjected directly to heat treatment without cooling.

Vorzugsweise ist der Spinnverzug des Verfahrens größer als 2. In einer besonders bevorzugten Ausführungsform weist die Spinnlösung bei 100°C eine Viskosität von 15 bis 50 Kugelfallsenkungen auf.The spinning delay of the method is preferably greater than 2. In a particularly preferred embodiment the spinning solution has a viscosity of 15 to 50 ball drops at 100 ° C.

Der Spinnverzug V ist definiert als Verhältnis von Abzugsgeschwindigkeit A zur Ausspritzgeschwindigkeit S:

Figure imgb0001
Spinning delay V is defined as the ratio of take-off speed A to ejection speed S:
Figure imgb0001

Die Auspritzgeschwindigkeit S ergibt sich zu:

Figure imgb0002
mit

  • F = Fördermenge (cm3/min)
  • Z = Anzahl der Düsenlöcher pro Düse
  • d = Düsenlochdurchmesser (cm)
The ejection speed S results in:
Figure imgb0002
 With
  • F = delivery rate (cm3 / min)
  • Z = number of nozzle holes per nozzle
  • d = nozzle hole diameter (cm)

Vergleiche Faserforschung 16 (1965), Heft 9, Seite 465. Die Fördermenge (Pumpenvolumen mal Umdrehungen pro Minute) läßt sich nach folgender Gleichung errechnen:

Figure imgb0003

  • GST = Gesamtspinntiter (dtex = g/10000m)
  • P = Pumpenvolumen (cm3)
  • U = Umdrehungen pro Minute (min -1)
  • K = Konzentrationen der Spinnlösung (g/cm3)
  • A = Abzugsgeschwindigkeit (m/min)
Compare fiber research 16 (1965), volume 9, page 465. The delivery rate (pump volume times revolutions per minute) can be calculated using the following equation:
Figure imgb0003
  • G ST = total spin titer (dtex = g / 10000m)
  • P = pump volume (cm 3 )
  • U = revolutions per minute (min -1 )
  • K = concentrations of the spinning solution (g / cm 3 )
  • A = take-off speed (m / min)

Als Acrylnitrilpolymerisate sind alle zu sogenannten Acrylfasern bzw. Modacrylfasern verspinnbaren Acrylnitrilhomo- und -copolymerisate geeignet, vorzugsweise Acrylnitrilcopolymerisate mit mindestens 85 Gew.-% Acrylnitrileinheiten. Ganz besonders bevorzugt sind Homopolymere und Terpolymere aus 89 bis 95 Gew.-% Acrylnitril, 4 bis 10 Gew.-% nicht ionogenen Comonomeren, beispielsweise Acrylsäuremethylester, Methacrylsäuremethylester oder Vinylacetat und 0,5 bis 3 Gew.-% ionogenen Comonomeren, beispielsweise Methallylsulfonat oder Styrolsulfonat. Die Polymerisate sind bekannt.Acrylonitrile polymers are all acrylics which can be spun into so-called acrylic fibers or modacrylic fibers tril homo- and copolymers suitable, preferably acrylonitrile copolymers with at least 85 wt .-% acrylonitrile units. Homopolymers and terpolymers made from 89 to 95% by weight of acrylonitrile, 4 to 10% by weight of non-ionic comonomers, for example methyl acrylate, methyl methacrylate or vinyl acetate and 0.5 to 3% by weight of ionogenic comonomers, for example methallylsulfonate or, are very particularly preferred Styrene sulfonate. The polymers are known.

Die Präparation kann auch Wasser als Bestandteile enthalten. Präparationsgemische mit über 50 % Feuchtegehalt werden jedoch nicht bevorzugt, weil die Fadenschar vor den anschließenden Nachbehandlungsschritten, wie Strecken, Kräusel usw., sonst zu stark gekühlt wird und eine gleichmäßige Durchwärmung des Spinngutes vor dem Strecken nicht mehr gewährleistet ist.The preparation can also contain water as components. Preparation mixtures with a moisture content of more than 50% are not preferred, however, because the group of threads is cooled too much before the subsequent post-treatment steps, such as drawing, crimping, etc., and uniform heating of the spun material before drawing is no longer guaranteed.

Als geeignete Gleitmittel kommen Glykole, deren Derivate, Siliconöle, ethoxylierte Fettsäuren, -alkohle, -ester, -amide, -alkylethersulfate, sowie deren Mischungen in Frage.Suitable lubricants are glycols, their derivatives, silicone oils, ethoxylated fatty acids, alcohols, esters, amides, alkyl ether sulfates, and mixtures thereof.

Geeignete Antistatika sind die üblichen kationaktiven, anionaktiven oder nichtionogenen Verbindungen, wie langkettige, ethoxilierte, sulfierte und neutralisierte Alkohole.Suitable antistatic agents are the usual cation-active, anion-active or non-ionic compounds, such as long-chain, ethoxylated, sulfated and neutralized alcohols.

Zweckmäßigerweise bringt man die Präparation bei erhöhten Temperaturen von 50 - 90°C mit den einzelnen Fadenbändchen in Berührung, um eine Abkühlung der heißen Fadenschar zu vermeiden. Die von einer Spinnmaschine mit beispielsweise 20 Spinnschächten ersponnenen Schachtbändchen vom Gesamttiter 100 000 dtex und mehr werden auf diese Weise präpariert, nach Verlassen des Fixieraggregates gebündelt und direkt einer weiteren Nachbehandlung, z.B. mit den Prozeßschritten Strecken - Kräuseln - Schrumpfen - Schneiden, zugeführt.The preparation is expediently brought into contact with the individual thread ribbons at elevated temperatures of 50-90 ° C. in order to prevent the hot thread sheet from cooling. The one with a spinning machine For example, 20 manhole tapes spun from the total titre 100,000 dtex and more are prepared in this way, bundled after leaving the fusing unit and fed directly to a further aftertreatment, for example with the process steps stretching - crimping - shrinking - cutting.

Ein großer Vorteil des erfindungsgemäßen Verfahrens besteht darin, daß sich derartig hergestellte, restlösungsmittelarme Spinnfäden direkt in einem kontinuierlichen Prozeß zu fertigen Acrylfasern ohne jedwede Unterbrechung nachbehandeln lassen.A great advantage of the process according to the invention is that low-solvent spinning threads produced in this way can be aftertreated directly in a continuous process to produce acrylic fibers without any interruption.

Ein weiterer großer Vorteil des erfindungsgemäßen Verfahrens zur Herstellung von restlösungsmittelarmen Spinnfäden besteht ferner darin, daß infolge des Fortfalls eines Waschprozesses auch kein Trockenaggregat mehr notwendig ist. Neben den geringeren Investitions- und Instandhaltungskosten lassen sich naturgemäß auch die Energiekosten deutlich vermindern.Another great advantage of the method according to the invention for the production of low-solvent spun threads is furthermore that, due to the elimination of a washing process, a drying unit is no longer necessary. In addition to the lower investment and maintenance costs, energy costs can naturally also be significantly reduced.

Im allgemeinen reichen Spinnabzugsgeschwindigkeiten bis zu 100 m/min vollkommen aus, um den Restlösungsmittelgehalt im Spinngut deutlich unter 5 Gew.-% zu halten.In general, spinning take-off speeds of up to 100 m / min are completely sufficient to keep the residual solvent content in the spun material clearly below 5% by weight.

Das erfindungsgemäße restlösungsmittelarme Spinnverfahren läßt sich auch auf sogenanntes düsengefärbtes Spinngut übertragen. Setzt man Spinnlösungen aus Acrylnitrilpolymerisaten Farbstoffe oder Pigmente zu, so erhält man gefärbtes Spinngut, das sich zu spinngefärbten Acrylfasern verarbeiten läßt.The low-solvent spinning process according to the invention can also be transferred to so-called nozzle-dyed spinning material. If spinning solutions made of acrylonitrile polymers are added to dyes or pigments, dyed spun material is obtained which can be processed into spun-dyed acrylic fibers.

Die Viskosität in Kugelfallsekunden, gemessen bei 100°C, wurde nach der Methode von K. Jost, Reologica Acta, Band 1 (1958), Seite 303, bestimmt. Es gilt dabei die Umrechnungsformel: 1 Kugelfallsekunde entspricht 4,37 poise.The viscosity in falling ball seconds, measured at 100 ° C., was determined by the method of K. Jost, Reologica Acta, volume 1 (1958), page 303. The conversion formula applies: 1 falling ball corresponds to 4.37 poise.

Beispiel 1example 1

700 kg Dimethylformamid (DMF) werden in einem Kessel bei Raumtemperatur unter Rühren mit 300 kg eines Acrylnitrilcopolymerisates aus 93,6 % Acrylnitril, 5,7 % Acrylsäuremethylester und 0,7 % Natriummethallylsulfonat vom K-Wert 81 vermischt. Die Suspension wird über eine Zahnradpumpe in einen mit einem Rührwerk versehenen Spinnkessel gepumpt. Dann wird die Suspension in einem doppelwandigen Rohr mit Dampf von 4,0 bar erhitzt. Die Verweilzeit im Rohr beträgt 5 Minuten. Die Spinnlösung, welche am Rohrausgang eine Temperatur von 138°C aufweist und eine Viskosität von 19 Kugelfallsekunden, gemessen bei 100°C besitzt, wird nach Verlassen der Aufheizvorrichtung auf 90°C abgekühlt, filtriert und direkt einer Spinnanlage mit 20 Spinnschächten zugeführt.700 kg of dimethylformamide (DMF) are mixed in a kettle at room temperature with stirring, with 300 kg of an acrylonitrile copolymer made from 93.6% acrylonitrile, 5.7% methyl acrylate and 0.7% sodium methallylsulfonate with a K value of 81. The suspension is pumped via a gear pump into a spinning kettle equipped with an agitator. Then the suspension is heated in a double-walled tube with steam of 4.0 bar. The dwell time in the tube is 5 minutes. The spinning solution, which has a temperature of 138 ° C at the tube outlet and a viscosity of 19 ball falling seconds, measured at 100 ° C, is cooled to 90 ° C after leaving the heating device, filtered and fed directly to a spinning system with 20 spinning shafts.

Die Spinnlösung wird aus 1264-Lochdüsen mit Düsenlochdurchmessern von 0,25 mm mit 50 m/min Abzugsgeschwindigkeit trocken versponnen. Die geförderte Spinnlösungsmenge pro Spinnschacht liegt bei 370,8 ccm/min. Die Schachttemperatur liegt bei 200°C und die Lufttemperatur beträgt 360°C. Die durchgesetzte Luftmenge beträgt 40 m3/h für jeden Schacht. Die Spinnfäden, welche mit einem Spinnverzug von 2,1 gesponnen worden sind, werden unmittelbar vor Verlassen der Spinnschächte vor Eintritt in ein dahinter geschaltetes Rohr mit einer 80 - 90°C warmen ein Gleitmittel und ein Antistatikum enthaltenden wasserarmen Präparation derartig benetzt, daß der ölgehalt der Fäden ca. 0,16 Gew.-% und der Gehalt an Antistatikum 0,04 Gew.-%, bezogen auf den Feststoffgehalt, ausmacht. Die Dosierung der Präparation geschieht über Zahnradpumpen. Das waagrecht nach der Spinnmaschine geschaltete Rohr, durch welches die Spinnfadenschar geleitet wird, ist im Gegenstrom zur Fadenlaufrichtung mit heißer Luft von 300°C zur DMF-Entfernung beschickt. Die Verweilzeit der Spinnfäden in den Spinnschächten und dem mit Heißluft beschickten Rohr beträgt ca. 18 Sekunden. Die durch das Rohr im Gegenstrom geschickte Heißluftmenge liegt bei 600 m3/h.The spinning solution is dry spun from 1264-hole nozzles with nozzle hole diameters of 0.25 mm at a take-off speed of 50 m / min. The amount of spinning solution delivered per spinning shaft is 370.8 ccm / min. The shaft temperature is 200 ° C and the air temperature is 360 ° C. The throughput of air is 40 m 3 / h for each shaft. The spinning threads, which have been spun with a spinning delay of 2.1, are immediately before leaving the spinning shafts before entering a tube connected behind them with a warming agent containing 80-90 ° C. containing a lubricant and an antistatic Low-water preparation so wetted that the oil content of the threads is approximately 0.16% by weight and the antistatic content is 0.04% by weight, based on the solids content. The preparation is dosed via gear pumps. The tube, which is connected horizontally after the spinning machine and through which the filament yarn sheet is guided, is fed with hot air at 300 ° C in countercurrent to the direction of the yarn travel to remove the DMF. The dwell time of the spinning threads in the spinning shafts and the tube fed with hot air is approximately 18 seconds. The amount of hot air sent through the pipe in counterflow is 600 m 3 / h.

Das warme Acrylkabel, welches einen Gesamttiter von 344 000 dtex aufweist, besitzt noch einen Restlösungsmittelgehalt von 1,6 Gew.-% an DMF. Das Kabel läßt sich anschließend ohne Unterbrechung verstrecken, kräuseln, schrumpfen und zu Stapfelfasern schneiden.The warm acrylic cable, which has a total titer of 344,000 dtex, still has a residual solvent content of 1.6% by weight of DMF. The cable can then be stretched, crimped, shrunk and cut into staple fibers without interruption.

Beispiel 2Example 2

Eine Spinnlösung wird gemäß Beispiel 1 zu Fäden versponnen und vor Eintritt in das dahinter geschaltete Rohr wieder mit einer 80 - 90°C warmen, ein Gleitmittel und ein Antistatikum enthaltenden wasserarmen Präparation benetzt. Im Gegenstrom zur Fadenlaufrichtung wird das Rohr mit überhitztem Dampf von 110°C zur DMF-Entfernung beschickt. Die Dampfmenge beträgt 150 kg/h. Die Verweilzeit des Spinngutes in den Spinnschächten und dem mit überhitztem Dampf beschickten Rohr beträgt wiederum ca. 18 Sekunden. Das warme Acrylkabel, welches wieder einen Gesamttiter von 344 000 dtex aufweist, besitzt noch einen Restlösungsmittelgehalt von 1,3 Gew.-% an DMF. Das Kabel läßt sich anschließend ohne Unterbrechung zu fertiger Stapelfaser verarbeiten.A spinning solution is spun into threads in accordance with Example 1 and, before entering the tube connected behind it, is again wetted with a low-water preparation containing 80-90 ° C. and containing a lubricant and an antistatic. In countercurrent to the direction of the thread, the tube is charged with superheated steam at 110 ° C for DMF removal. The amount of steam is 150 kg / h. The dwell time of the spinning material in the spinning shafts and the tube charged with superheated steam is again approx. 18 seconds. The warm acrylic cable, which again has a total titre of 344,000 dtex, be is still a residual solvent content of 1.3 wt .-% of DMF. The cable can then be processed into finished staple fiber without interruption.

Beispiel 3Example 3

Eine Spinnlösung gemäß Beispiel 1 wird zu Fäden versponnen, die Abzugsgeschwindigkeit beträgt jedoch 100 m/min und die geförderte Spinnlösungsmenge pro Spinnschacht liegt bei 512 ccm/min. Die Spinnfäden, welche mit einem Spinnverzug von 3,0 gesponnen worden sind, werden unmittelbar vor Verlassen der Spinnschächte und vor Eintritt in das dahinter geschaltete Rohr präpariert und anschließend im Rohr im Gegenstrom zur Fadenlaufrichtung mit heißer Luft von 300°C zur DMF-Entfernung beschickt. Die Verweilzeit des Spinngutes in den Spinnschächten und dem mit Heißluft beschickten Rohr beträgt ca. 9 Sekunden. Die durch das Rohr im Gegenstrom geschickte Heißluftmenge liegt bei 800 m3/h. Das warme Acrylkabel, welches einen Gesamttiter von 265 500 dtex aufweist, besitzt noch einen Restlösungsmittelgehalt von 2,2 Gew.-% an DMF. Das Kabel läßt sich anschließend ohne Unterbrechung direkt weiter zu Stapelfasern verarbeiten.A spinning solution according to Example 1 is spun into threads, but the take-off speed is 100 m / min and the amount of spinning solution conveyed per spinning shaft is 512 ccm / min. The spinning threads, which have been spun with a spinning delay of 3.0, are prepared immediately before leaving the spinning shafts and before entering the tube behind them, and are then fed in the tube in countercurrent to the direction of the thread with hot air at 300 ° C. to remove the DMF . The dwell time of the spinning material in the spinning shafts and the tube fed with hot air is approximately 9 seconds. The amount of hot air sent through the pipe in counterflow is 800 m 3 / h. The warm acrylic cable, which has a total titer of 265,500 dtex, still has a residual solvent content of 2.2% by weight of DMF. The cable can then be processed directly into staple fibers without interruption.

Beispiel 4Example 4

Eine Spinnlösung wurde unter den in Beispiel 1 angegebenen Bedingungen hergestellt, versponnen und präpariert.A spinning solution was prepared, spun and prepared under the conditions given in Example 1.

Die gebündelte Fadenschar wird anschließend über einen auf 195°C elektrisch geheizten Walzenkalander mit 13 Walzen von 40 cm Durchmesser geschickt. Die Fadenschar nimmt dabei eine Temperatur von 159°C an, berührungslos gemessen mit dem Strahlungsthermometer KT 15 (Hersteller Fa. Heimann GmbH, Wiesbaden, BRD). Die Verweilzeit der Fäden auf den Kalanderwalzen beträgt ca. 10 Sekunden. Der Walzenkalander ist mit einer Absaugvorrichtung zur Entfernung restlicher Spinnlösungsmittelmengen ausgerüstet.The bundle of threads is then sent over a roller calender with 13 rollers of 40 cm diameter that is electrically heated to 195 ° C. The thread sheet assumes a temperature of 159 ° C, measured without contact with the radiation thermometer KT 15 (manufacturer Heimann GmbH, Wiesbaden, FRG). The dwell time of the threads on the calender rolls is approximately 10 seconds. The roller calender is equipped with a suction device to remove residual amounts of spinning solvent.

Das warme Acrylkabel vom Gesamttiter 344 000 dtex besitzt noch einen Restlösungsmittelgehalt von 0,8 Gew.-% an DMF. Das Kabel läßt sich anschließend ohne Unterbrechung verstrecken, kräuseln, schrumpfen und zu Stapelfasern schneiden.The warm acrylic cable with a total titre of 344,000 dtex still has a residual solvent content of 0.8% by weight of DMF. The cable can then be stretched, crimped, shrunk and cut into staple fibers without interruption.

Claims (3)

1) Trockenspinnverfahren zur Herstellung von Polyacrylnitril-Spinnfäden mit mindestens 45 Gew.-% Acrylnitrileinheiten, einem Restlösungsmittelgehalt unter 5 Gew.-% und einem Gesamttiter über 100 000 dtex ohne Kontaktierung mit einem Extraktionsmittels für das Spinnlösungsmittel, dadurch gekennzeichnet, daß a) eine Spinnlösung versponnen wird, deren Viskosität bei 100°C 10 bis 60 Kugelfallsekunden beträgt, b) die Fäden unmittelbar am Ende des Spinnschachtes innerhalb oder unmittelbar außerhalb des Schachtendes in noch heißem Zustand mit einer Präparation versehen werden, die ein Gleitmittel und ein Antistatikum enthält und den Fäden einen Feuchtegehalt von maximal 10 Gew.-%, bezogen auf Faserfeststoffgehalt, verleiht und c) die Fäden direkt ohne Abkühlung einer Wärmebehandlung ausgesetzt werden. 1) Dry spinning process for the production of polyacrylonitrile spinning threads with at least 45% by weight of acrylonitrile units, a residual solvent content of less than 5% by weight and a total titer of more than 100,000 dtex without contact with an extracting agent for the spinning solvent, characterized in that a) a spinning solution is spun, the viscosity of which is 10 to 60 falling ball seconds at 100 ° C., b) the threads immediately at the end of the spinning shaft inside or immediately outside the end of the shaft, while still hot, are provided with a preparation which contains a lubricant and an antistatic and which gives the threads a moisture content of at most 10% by weight, based on the fiber solids content and c) the threads are subjected directly to heat treatment without cooling. 2) Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß der Spinnverzug größer als 2 ist und die Spinnlösung eine Viskosität bei 100°C von 15 bis 50 Kugelfallsekunden aufweist.2) Method according to claim 1, characterized in that the spinning delay is greater than 2 and the spinning solution has a viscosity at 100 ° C of 15 to 50 falling ball seconds. 3) Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Polyacrylnitril-Spinnfäden aus Acrylnitrilcopolymerisaten mit mindestens 85 Gew.-% Acrylnitrileinheiten bestehen.3) Method according to claim 1, characterized in that the polyacrylonitrile spinning threads consist of acrylonitrile copolymers with at least 85 wt .-% acrylonitrile units.
EP83106187A 1982-07-06 1983-06-24 Manufacture of polyacrylonitrile filaments containing very few solvents Expired EP0098484B1 (en)

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DE19823225267 DE3225267A1 (en) 1982-07-06 1982-07-06 MANUFACTURE OF LOW-SOLVENT POLYACRYLNITRILE SPIDER THREADS
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JPS6366318A (en) * 1986-09-05 1988-03-25 バイエル・アクチエンゲゼルシヤフト Continuous spinning of acrylonitril filament fiber
DE3634753A1 (en) * 1986-09-05 1988-03-17 Bayer Ag Continuous spinning processes for acrylonitrile filaments and fibres involving steaming of the spun material

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DE3225267A1 (en) 1984-01-12
DE3369350D1 (en) 1987-02-26
EP0098484A3 (en) 1985-09-11
JPS5921712A (en) 1984-02-03
EP0098484B1 (en) 1987-01-21
US4505870A (en) 1985-03-19

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