EP0340572B1 - Melt-spun fibres from at least one aromatic polymer, and process for their preparation - Google Patents
Melt-spun fibres from at least one aromatic polymer, and process for their preparation Download PDFInfo
- Publication number
- EP0340572B1 EP0340572B1 EP89107285A EP89107285A EP0340572B1 EP 0340572 B1 EP0340572 B1 EP 0340572B1 EP 89107285 A EP89107285 A EP 89107285A EP 89107285 A EP89107285 A EP 89107285A EP 0340572 B1 EP0340572 B1 EP 0340572B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- melt
- threads
- diameter
- aromatic
- filament
- 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 - Lifetime
Links
Classifications
-
- 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
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
-
- 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
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/76—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from other polycondensation products
Definitions
- Aromatic polymer threads such as polyether sulfone, are spun from solutions of the polymer. This requires complex solvents which are removed from the spun threads and have to be recovered. Overall, this process is very complex. Attempts have also been made to spin such polymers out of the melt. However, it has been found that such polymers are difficult to spin from the melt, since the threads produced have irregularities and these also result in many thread breaks during the subsequent stretching, which leads to an unusable end product.
- the invention further relates to a process for the production of threads from at least one aromatic polymer, built up from recurring units of the general formula I and / or II, in which a melt of the aromatic polymer with a content of less than 1% by weight is added not homogeneously in the aromatic polymer soluble fractions at a temperature T which is at least 10 ° C below the decomposition temperature of the aromatic polymer and at the temperature T the melt viscosity at a shear rate of 10 to 1000 sec ⁇ 1 less than 1000 Pas, spun into threads .
- the new threads have the advantage that they are characterized by high uniformity and in particular that they are easy to stretch.
- the new threads can be obtained without the use of expensive solvents by spinning from the melt using conventional spinning devices.
- the threads according to the invention generally have a diameter of 20 »to 2 mm, in particular 25» to 1 mm.
- the threads are formed from the melt and essentially consist of at least one aromatic polymer, built up from recurring units of the general formula in which A and B can be the same or different and each denote a 1,4-phenylene radical or 1,7-naphthylene radical and B can also denote a 4,4'-biphenylene radical, which can each contain chlorine atoms as substituents and R1 and R2 are the same or can be different and each represent an alkyl radical having 1 to 6 carbon atoms and / or recurring units of the general formula ⁇ O ⁇ X ⁇ SO2 ⁇ X ⁇ II, in which X denotes a 1,4-phenylene radical, 4,4'-biphenylene radical or a 1,7-naphthylene radical, each of which may have chlorine atoms as substituents.
- a and B each denote a 1,4-phenylene radical which may have 1 to 2 chlorine atoms as substituents, in particular an unsubstituted 1,4-phenylene radical.
- X denotes a 1,4-phenylene radical which has 1 or 2 chlorine atoms as May have substituents, especially an unsubstituted 1,4-phenylene radical.
- aromatic polymers can contain conventional additives, such as stabilizers, in effective amounts.
- the threads according to the invention thus consist essentially of polymers with repeating units of the formula I from polymers with repeating units of the formula II from copolymers with repeating units of the formula I and II, and also from mixtures of such polymers.
- Examples of recurring units of the formula I and II are
- the aromatic polymers advantageously have a relative solution viscosity of 1.40 to 2.0. The preparation of the aromatic polymers is described for example in DE-AS 14 45 806.
- the aforementioned aromatic polymers have a content of less than 1% by weight, e.g. 0.01 to 1% by weight, in particular 0.05 to 0.8% by weight, of non-homogeneously soluble fractions of the aromatic polymers.
- non-homogeneously soluble fractions are, for example, salts from the production of the polymers or gel parts.
- they are non-homogeneously soluble parts with a particle diameter of> 5 »m up to 100» m.
- the content of non-homogeneously soluble fractions is expediently determined using the flow vision device from Schwing Maschinenstechnik on a measuring extruder, with an extruder throughput of 1 kg / h the number of registered insoluble particles which have a diameter of more than 5 »m , should be less than 20 per minute.
- the aromatic polymer advantageously has a relative viscosity of 1.40 to 1.65, while for threads with a diameter of 0.1 to 1 mm, the aromatic polymer advantageously has a relative viscosity Has a viscosity of 1.65 to 2.
- the threads according to the invention are easy to draw.
- Advantageous threads are e.g. stretched 1.2 to 10 times.
- the threads according to the invention are advantageously obtained from a melt of at least one of the aforementioned aromatic polymers with a content of less than 1% by weight of non-homogeneously soluble components in aromatic polymer at a temperature T which is below 10 ° C.
- the decomposition temperature of the aromatic polymer in question and the melt at temperature T has a viscosity of less than 1000 Pas at a shear rate of 10 to 1000 sec ⁇ 1, spins.
- multifilaments with individual thread diameters from 20 to 100 »m but also monofilaments with diameters from 100 to 1500» m can be spun.
- the spinning is usually carried out on conventional spinning devices, such as are known for the production of, for example, polyamide 6 threads.
- the decomposition temperature is understood to be the temperature at which the melt viscosity has increased by more than 10% after heating the aromatic polymer for 10 minutes, or in the TGA curve (TGA: thermogravimetry.
- the sample to be undertaken is at a defined temperature, eg at the above-mentioned decomposition temperature, heated in air for a certain time (for example 10 minutes) and the weight loss measured before and after the treatment) a weight loss of more than 2% by weight of the predried sample occurs, depending on which temperature is lower.
- the spun threads are advantageously drawn 1.2 to 10 times, in particular 1.5 to 8 times, at elevated temperature. Temperatures of 50 to 300 ° C., in particular 75 to 250 ° C., have proven successful.
- the stretching is carried out on conventional stretching devices, e.g. with heated godets.
- the threads according to the invention can also be cut and processed as staple fibers. They are suitable alone or in a mixture with other threads or fibers for the production of articles in which a high heat resistance, a high resistance to chemicals and moist heat or difficult flammability are required.
- the threads had a single thread diameter of 25 »m and a tensile strength of 2.1 cN / dtex and an elongation at break of 14%.
- the threads showed numerous inhomogeneities in the form of bubbles and thickenings and could not be drawn.
- Example 3 The same copolymer as in Example 3 was spun at a temperature of 360 ° C to a monofilament of 0.5 mm2. The monofilaments showed large fluctuations in diameter and were difficult to stretch.
- a copolymer of 75 mol% recurring unit according to Example 1 and 25 mol% recurring unit according to Example 2 with a relative solution viscosity of 1.77 and a melt viscosity of 1052 Pas was at 360 ° C to a multifilament with single thread diameters of ⁇ 0, 1 mm spun. The individual threads showed large fluctuations in diameter and were difficult to stretch.
- a copolymer according to Comparative Example 3 was spun at 360 ° C. to monofilaments of 0.5 and 0.65 mm in diameter and then stretched twice at 220 ° C.
- the monofilaments had a tensile strength of 145 N / mm2 and an elongation at break of 45%.
Description
Fäden aus aromatischen Polymeren, wie Polyethersulfon, werden aus Lösungen des Polymeren ersponnen. Hierbei sind aufwendige Lösungsmittel erforderlich, die aus den ersponnenen Fäden entfernt werden und wiedergewonnen müssen. Insgesamt ist dieses Verfahren sehr aufwendig. Es wurde auch schon versucht, solche Polymere aus der Schmelze zu verspinnen. Es hat sich jedoch herausgestellt, daß solche Polymeren aus der Schmelze schwer verspinnbar sind, da die erzeugten Fäden Unregelmäßigkeiten aufweisen und diese zudem bei der nachfolgenden Verstreckung viele Fadenbrüche ergeben, was zu einem unbrauchbaren Endprodukt führt.Aromatic polymer threads, such as polyether sulfone, are spun from solutions of the polymer. This requires complex solvents which are removed from the spun threads and have to be recovered. Overall, this process is very complex. Attempts have also been made to spin such polymers out of the melt. However, it has been found that such polymers are difficult to spin from the melt, since the threads produced have irregularities and these also result in many thread breaks during the subsequent stretching, which leads to an unusable end product.
Es war deshalb die technische Aufgabe gestellt, aus der Schmelze geformte Fäden aus mindestens einem aromatischen Polymeren zur Verfügung zu stellen, die mit gleichmäßiger Qualität verspinnbar sind und beim Verstrecken eine hohe Ausbeute ergeben. Ferner war die Aufgabe gestellt, ein Verfahren zur Herstellung solcher Fäden zur Verfügung zu stellen.It was therefore the technical task to provide threads formed from the melt from at least one aromatic polymer which can be spun with uniform quality and which give a high yield when drawn. Furthermore, the task was to provide a method for producing such threads.
Diese Aufgabe wird gelöst durch aus der Schmelze geformte Fäden aus mindestens einem Polymeren aufgebaut aus wiederkehrenden Einheiten der allgemeinen Formel
in der A und B gleich oder verschieden sein können und jeweils einen 1, 4-Phenylenrest oder 1, 7-Naphthylenrest bezeichnen und B auch einen 4,4'-Biphenylenrest bezeichnen kann, die jeweils Chloratome als Substituenten enthalten können und R₁ und R₂ gleich oder verschieden sein können und jeweils einen Alkylrest mit 1 bis 4 Kohlenstoffatomen bedeuten und/oder wiederkehrenden Einheiten der allgemeinen Formel
―O―X―SO₂―X― II,
in der X einen 1,4-Phenylenrest, 4,4'-Biphenylenrest oder einen 1,7-Naphthylenrest, die jeweils Chloratome als Substituenten haben können, bedeutet, gekennzeichnet durch einen Gehalt von weniger als 1 Gew.% an nicht homogen in den aromatischen Polymeren löslichen Anteilen.This object is achieved by threads formed from the melt from at least one polymer composed of repeating units of the general formula
in which A and B can be the same or different and each denote a 1,4-phenylene radical or 1,7-naphthylene radical and B can also denote a 4,4'-biphenylene radical, which can each contain chlorine atoms as substituents and R₁ and R₂ are the same or can be different and each represent an alkyl radical having 1 to 4 carbon atoms and / or recurring units of the general formula
―O ― X ― SO₂ ― X― II,
in which X denotes a 1,4-phenylene radical, 4,4'-biphenylene radical or a 1,7-naphthylene radical, each of which may have chlorine atoms as substituents, characterized by a content of less than 1% by weight of non-homogeneous in the aromatic polymers soluble proportions.
Ferner ist ein Gegenstand der Erfindung ein Verfahren zur Herstellung von Fäden aus mindestens einem aromatischen Polymeren, aufgebaut aus wiederkehrender Einheiten der allgemeinen Formel I und/oder II, bei dem man eine Schmelze des aromatischen Polymeren mit einem Gehalt von weniger als 1 Gew.% an nicht homogen in den aromatischen Polymeren löslichen Anteilen bei einer Temperatur T die mindestens 10°C unter der Zersetzungstemperatur des aromatischen Polymeren liegt und bei der Temperatur T die Schmelzviskosität bei einer Schergeschwindigkeit von 10 bis 1000 sec⁻¹ weniger als 1000 Pas beträgt, zu Fäden verspinnt.The invention further relates to a process for the production of threads from at least one aromatic polymer, built up from recurring units of the general formula I and / or II, in which a melt of the aromatic polymer with a content of less than 1% by weight is added not homogeneously in the aromatic polymer soluble fractions at a temperature T which is at least 10 ° C below the decomposition temperature of the aromatic polymer and at the temperature T the melt viscosity at a shear rate of 10 to 1000 sec⁻¹ less than 1000 Pas, spun into threads .
Die neuen Faden haben den Vorteil, daß sie sich durch hohe Gleichmäßigkeit auszeichnen und insbesondere daß sie gut verstreckbar sind. Die neuen Fäden sind ohne Mitverwendung von aufwendigen Lösungsmitteln durch Verspinnen aus der Schmelze unter Verwendung von üblichen Spinnvorrichtungen erhältlich.The new threads have the advantage that they are characterized by high uniformity and in particular that they are easy to stretch. The new threads can be obtained without the use of expensive solvents by spinning from the melt using conventional spinning devices.
Die erfindungsgemäßen Fäden haben in der Regel einen Durchmesser von 20 » bis 2 mm, insbesondere 25 » bis 1 mm.The threads according to the invention generally have a diameter of 20 »to 2 mm, in particular 25» to 1 mm.
Die Fäden sind aus der Schmelze geformt und bestehen im wesentlichen aus mindestens einem aromatischen Polymeren, aufgebaut aus wiederkehrenden Einheiten der allgemeinen Formel
in der A und B gleich oder verschieden sein können und jeweils einen 1,4-Phenylenrest oder 1,7-Naphthylenrest bezeichnen und B auch einen 4,4'-Biphenylenrest bezeichnen kann, die jeweils Chloratome als Substituenten enthalten können und R₁ und R₂ gleich oder verschieden sein können und jeweils einen Alkylrest mit 1 bis 6 Kohlenstoffatomen bedeuten und/oder wiederkehrenden Einheiten der allgemeinen Formel
―O―X―SO₂―X― II,
in der X einen 1,4-Phenylenrest, 4,4'-Biphenylenrest oder einen 1,7-Naphthylenrest, die jeweils Chloratome als Substituenten haben können, bezeichnet.The threads are formed from the melt and essentially consist of at least one aromatic polymer, built up from recurring units of the general formula
in which A and B can be the same or different and each denote a 1,4-phenylene radical or 1,7-naphthylene radical and B can also denote a 4,4'-biphenylene radical, which can each contain chlorine atoms as substituents and R₁ and R₂ are the same or can be different and each represent an alkyl radical having 1 to 6 carbon atoms and / or recurring units of the general formula
―O ― X ― SO₂ ― X― II,
in which X denotes a 1,4-phenylene radical, 4,4'-biphenylene radical or a 1,7-naphthylene radical, each of which may have chlorine atoms as substituents.
In bevorzugten wiederkehrenden Einheiten der allgemeinen Formel I bezeichnen A und B jeweils einen 1,4-Phenylenrest, der 1 bis 2 Chloratome als Substituenten haben kann, insbesondere einen nicht substituierten 1,4-Phenylenrest. In bevorzugten wiederkehrenden Einheiten der Formel II bezeichnet X einen 1,4-Phenylenrest, der 1 oder 2 Chloratome als Substituenten haben kann, insbesondere einen nicht substituierten 1,4-Phenylenrest.In preferred recurring units of the general formula I, A and B each denote a 1,4-phenylene radical which may have 1 to 2 chlorine atoms as substituents, in particular an unsubstituted 1,4-phenylene radical. In preferred recurring units of the formula II, X denotes a 1,4-phenylene radical which has 1 or 2 chlorine atoms as May have substituents, especially an unsubstituted 1,4-phenylene radical.
Daneben können die aromatischen Polymeren übliche Zusätze, wie Stabilisatoren in wirksamen Mengen enthalten.In addition, the aromatic polymers can contain conventional additives, such as stabilizers, in effective amounts.
Die erfindungsgemäßen Fäden bestehen somit im wesentlichen aus Polymeren mit wiederkehrenden Einheiten der Formel I aus Polymeren mit wiederkehrenden Einheiten der Formel II aus Copolymeren mit wiederkehrenden Einheiten der Formel I und II, ferner aus Gemischen solcher Polymeren. Beispiele für wiederkehrende Einheiten der Formel I und II sind
Die aromatischen Polymeren haben vorteilhaft eine relative Lösungsviskosität von 1,40 bis 2,0. Die Herstellung der aromatischen Polymeren wird beispielsweise beschrieben in der DE-AS 14 45 806.The threads according to the invention thus consist essentially of polymers with repeating units of the formula I from polymers with repeating units of the formula II from copolymers with repeating units of the formula I and II, and also from mixtures of such polymers. Examples of recurring units of the formula I and II are
The aromatic polymers advantageously have a relative solution viscosity of 1.40 to 2.0. The preparation of the aromatic polymers is described for example in DE-AS 14 45 806.
Die vorgenannten aromatischen Polymeren haben einen Gehalt von weniger als 1 Gew.%, z.B. 0,01 bis 1 Gew.% insbesondere 0,05 bis 0,8 Gew.% an nicht-homogen an den aromatischen Polymeren löslichen Anteilen. Solche nicht-homogen lösliche Anteile sind beispielsweise Salze aus der Herstellung der Polymeren oder Gelteile. Insbesondere handelt es sich um nicht-homogen lösliche Teile mit einem Teilchendurchmesser von > 5 »m bis zu 100 »m. Der Gehalt an nicht-homogen löslichen Anteilen wird zweckmäßig bestimmt mit dem Flow-Vision-Gerät der Firma Schwing Verfahrenstechnik an einem Meßextruder, wobei bei einem Extruderdurchsatz von 1 kg/h die Zahl der registrierten unlöslichen Teilchen, die einen Durchmesser über 5 »m haben, weniger als 20 pro Minute betragen soll .The aforementioned aromatic polymers have a content of less than 1% by weight, e.g. 0.01 to 1% by weight, in particular 0.05 to 0.8% by weight, of non-homogeneously soluble fractions of the aromatic polymers. Such non-homogeneously soluble fractions are, for example, salts from the production of the polymers or gel parts. In particular, they are non-homogeneously soluble parts with a particle diameter of> 5 »m up to 100» m. The content of non-homogeneously soluble fractions is expediently determined using the flow vision device from Schwing Verfahrenstechnik on a measuring extruder, with an extruder throughput of 1 kg / h the number of registered insoluble particles which have a diameter of more than 5 »m , should be less than 20 per minute.
Für Fäden mit einem Durchmesser von 20 »m bis 0,1 mm hat das aromatische Polymere vorteilhaft eine relative Viskosität von 1,40 bis 1,65, während für Fäden mit einem Durchmesser von 0,1 bis 1 mm das aromatische Polymere vorteilhaft eine relative Viskosität von 1,65 bis 2 hat.For threads with a diameter of 20 .mu.m to 0.1 mm, the aromatic polymer advantageously has a relative viscosity of 1.40 to 1.65, while for threads with a diameter of 0.1 to 1 mm, the aromatic polymer advantageously has a relative viscosity Has a viscosity of 1.65 to 2.
Die erfindungsgemäßen Fäden sind gut verstreckbar. Vorteilhafte Fäden sind z.B. um das 1,2- bis 10-fache verstreckt.The threads according to the invention are easy to draw. Advantageous threads are e.g. stretched 1.2 to 10 times.
Die erfindungsgemäßen Fäden erhält man vorteilhaft, indem man aus einer Schmelze aus mindestens einem der vorher genannten aromatischen Polymeren mit einem Gehalt von weniger als 1 Gew.% an nicht-homogen in aromatischen polymeren löslichen Anteilen bei einer Temperatur T, die mindestens 10°C unter der Zersetzungstemperatur des jeweiligen aromatischen Polymeren liegt und die Schmelze bei der Temperatur T eine Viskosität von weniger als 1000 Pas bei einer Schergeschwindigkeit von 10 bis 1000 sec⁻¹ hat, verspinnt. Hierbei lassen sich Multifile mit Einzelfadendurchmesser von 20 bis 100 »m aber auch Monofile mit Durchmessern von 100 bis 1500 »m erspinnen. Das Verspinnen erfolgt in der Regel auf üblichen Spinnvorrichtungen, wie sie für die Herstellung von beispielsweise Polyamid-6-Fäden bekannt sind.The threads according to the invention are advantageously obtained from a melt of at least one of the aforementioned aromatic polymers with a content of less than 1% by weight of non-homogeneously soluble components in aromatic polymer at a temperature T which is below 10 ° C. the decomposition temperature of the aromatic polymer in question and the melt at temperature T has a viscosity of less than 1000 Pas at a shear rate of 10 to 1000 sec⁻¹, spins. Here multifilaments with individual thread diameters from 20 to 100 »m but also monofilaments with diameters from 100 to 1500» m can be spun. The spinning is usually carried out on conventional spinning devices, such as are known for the production of, for example, polyamide 6 threads.
Als Zersetzungstemperatur sei die Temperatur verstanden, bei der nach 10-minütigem Erhitzen des aromatischen Polymeren die Schmelzviskosität um mehr als 10 % zugenommen hat, bzw. in der TGA-Kurve (TGA: Thermogravimetrie. Dabei wird die zu unternehmende Probe bei einer definierten Temperatur, z.B. bei der oben genannten Zersetzungstemperatur, eine bestimmte zeitlang (z.B. 10 Minuten) in Luft erhitzt und der Gewichtsverlust vor und nach der Behandlung gemessen) ein Gewichtsverlust von mehr als 2 Gew.% der vorgetrockneten Probe auftritt, je nachdem welche Temperatur niedriger liegt.The decomposition temperature is understood to be the temperature at which the melt viscosity has increased by more than 10% after heating the aromatic polymer for 10 minutes, or in the TGA curve (TGA: thermogravimetry. The sample to be undertaken is at a defined temperature, eg at the above-mentioned decomposition temperature, heated in air for a certain time (for example 10 minutes) and the weight loss measured before and after the treatment) a weight loss of more than 2% by weight of the predried sample occurs, depending on which temperature is lower.
Die ersponnenen Fäden werden vorteilhaft bei erhöhter Temperatur um das 1,2- bis 10-fache, insbesondere 1,5- bis 8-fache verstreckt. Hierbei haben sich Temperaturen von 50 bis 300°C, insbesondere von 75 bis 250°C bewährt. Die Verstreckung erfolgt auf üblichen Streckvorrichtungen, z.B. mit beheizten Galetten.The spun threads are advantageously drawn 1.2 to 10 times, in particular 1.5 to 8 times, at elevated temperature. Temperatures of 50 to 300 ° C., in particular 75 to 250 ° C., have proven successful. The stretching is carried out on conventional stretching devices, e.g. with heated godets.
Die erfindungsgemäßen Fäden können auch geschnitten und als Stapelfasern verarbeitet werden. Sie eignen sich allein oder im Gemisch mit anderen Fäden oder Fasern zur Herstellung von Gegenständen, bei denen eine hohe Wärmeformbeständigkeit, eine hohe Resistenz gegenüber Chemikalien und feuchter Hitze oder schwere Brennbarkeit gefordert werden.The threads according to the invention can also be cut and processed as staple fibers. They are suitable alone or in a mixture with other threads or fibers for the production of articles in which a high heat resistance, a high resistance to chemicals and moist heat or difficult flammability are required.
Der Gegenstand der Erfindung sei an folgenden Beispielen veranschaulicht:The subject matter of the invention is illustrated by the following examples:
Ein Polysulfon, aufgebaut aus wiederkehrenden Einheiten der Formel
mit einer relativen Lösungsviskosität von 1,54, gemessen in N-Methylpyrrolidon an einer 1-gew-%igen Lösung bei 20°C, einem Gehalt von 0,75 Gew.% an nicht homogen im Polymeren löslichen Anteilen und einer Schmelzviskosität von 240 Pas, gemessen bei 350°C und einer Belastung von 10 kg sowie einer Zersetzungstemperatur von 385°C, wurde auf einer konventionellen Schmelzspinnvorrichtung bei 370°C zu Fäden mit einem Durchmesser von 35 »m versponnen. Die so erhaltenen Fäden wurden dann bei 90°C um das 1,4-fache verstreckt. Die erhaltenen Fäden hatten eine Reißfestigkeit von 1,13 cN/dtex, eine Bruchdehnung von 55 % und einen Durchmesser von 30 »m.A polysulfone made up of recurring units of the formula
with a relative solution viscosity of 1.54, measured in N-methylpyrrolidone in a 1% strength by weight solution at 20 ° C., a content of 0.75% by weight of non-homogeneously soluble parts in the polymer and a melt viscosity of 240 Pas , measured at 350 ° C and a load of 10 kg and a decomposition temperature of 385 ° C, was spun on a conventional melt spinning device at 370 ° C into threads with a diameter of 35 »m. The threads thus obtained were then drawn 1.4 times at 90 ° C. The threads obtained had a tensile strength of 1.13 cN / dtex, an elongation at break of 55% and a diameter of 30 »m.
Ein Polyethersulfon, aufgebaut aus Einheiten der Formel
mit einem Gehalt von 0,5 Gew.% an nicht homogen im Polymer löslichen Anteilen und einer relativen Lösungsviskosität von 1,49, gemessen als 1 gew.-%ige Lösung in N-Methylpyrrolidon bei 20°C sowie einer Schmelzviskosität von 613 Pas, gemessen bei 350°C unter einer Belastung von 10 kg und einer Zersetzungstemperatur von 375°C wurde bei 365°C zu Fäden mit einem Durchmesser von 30 »m versponnen. Die so ersponnenen Fäden wurden bei 130°C (Hotrole) bzw. 170°C (Hotplate) auf das 2-fache verstreckt. Die Fäden hatten einen Einzelfadendurchmesser von 25 »m und eine Reißfestigkeit von 2,1 cN/dtex und eine Bruchdehnung von 14 %.A polyether sulfone made up of units of the formula
with a content of 0.5% by weight of non-homogeneously soluble parts in the polymer and a relative solution viscosity of 1.49, measured as a 1% by weight solution in N-methylpyrrolidone at 20 ° C. and a melt viscosity of 613 Pas, measured at 350 ° C under a load of 10 kg and a decomposition temperature of 375 ° C was spun at 365 ° C into threads with a diameter of 30 »m. The threads spun in this way were stretched twice at 130 ° C (hot roll) or 170 ° C (hot plate). The threads had a single thread diameter of 25 »m and a tensile strength of 2.1 cN / dtex and an elongation at break of 14%.
Ein Polyethersulfon, gemäß Beispiel 2, jedoch mit einer relativen Lösungsviskosität von 1,73 und einer Schmelzviskosität von > 1000 Pas sowie 1,5 Gew.% salzartigen nicht löslichen Verunreinigungen wurden bei 380°C zu Fäden mit einem Durchmesser von 50 »m versponnen. Die Fäden zeigten zahlreiche Inhomogenitäten in Form von Blasen und Verdickungen und ließen sich nicht verstrecken.A polyether sulfone, according to Example 2, but with a relative solution viscosity of 1.73 and a melt viscosity of> 1000 Pas and 1.5% by weight of salt-like, insoluble impurities, was spun at 380 ° C. into threads with a diameter of 50 μm. The threads showed numerous inhomogeneities in the form of bubbles and thickenings and could not be drawn.
Ein Copolymer, aufgebaut aus 95 Mol.% Polyethersulfon-Einheiten der Formel gemäß Beispiel 2 und 5 Mol.% Polysulfoneinheiten gemäß Beispiel 1 mit einer relativen Lösungsviskosität von 1,65 und einer Schmelzviskosität von 765 Pas bei einer Temperatur von 350°C und einer Belastung von 5 kg mit einem Gehalt an unlöslichen Verunreinigungen von 0,3 Gew.% und einer Zersetzungstemperatur von 380°C wurde bei 360°C zu Fäden mit einem Durchmesser von 50 »m versponnen. Die so erhaltenen Fäden wurden bei 120°C (Heizgalette) und 190°C (Heizplatte) um das 1,5-fache verstreckt. Die Einzelfäden hatten einen Durchmesser von 40 »m, eine Reißfestigkeit von 1,15 cN/dtex und eine Bruchdehnung von 45 %.A copolymer composed of 95 mol% polyethersulfone units of the formula according to Example 2 and 5 mol% polysulfone units according to Example 1 with a relative solution viscosity of 1.65 and a melt viscosity of 765 Pas at a temperature of 350 ° C. and a load of 5 kg with an insoluble impurity content of 0.3% by weight and a decomposition temperature of 380 ° C. was spun at 360 ° C. into threads with a diameter of 50 μm. The threads thus obtained were stretched 1.5 times at 120 ° C (heating godet) and 190 ° C (heating plate). The individual threads had a diameter of 40 »m, a tensile strength of 1.15 cN / dtex and an elongation at break of 45%.
Das gleiche Copolymer wie in Beispiel 3 wurde bei einer Temperatur von 360°C zu einem Monofil von 0,5 mm ² versponnen. Die Monofile zeigten große Durchmesserschwankungen und waren schwer verstreckbar.The same copolymer as in Example 3 was spun at a temperature of 360 ° C to a monofilament of 0.5 mm². The monofilaments showed large fluctuations in diameter and were difficult to stretch.
Ein Copolymer aus 75 Mol.% wiederkehrenden Einheit gemäß Beispiel 1 und 25 Mol.% wiederkehrenden Einheiten gemäß Beispiel 2 mit einer relativen Lösungsviskosität von 1,77 und einer Schmelzviskosität von 1052 Pas wurde bei 360°C zu einem Multifil mit Einzelfadendurchmessern von < 0,1 mm versponnen. Die Einzelfäden zeigten große Durchmesserschwankungen und waren schwer verstreckbar.A copolymer of 75 mol% recurring unit according to Example 1 and 25 mol% recurring unit according to Example 2 with a relative solution viscosity of 1.77 and a melt viscosity of 1052 Pas was at 360 ° C to a multifilament with single thread diameters of <0, 1 mm spun. The individual threads showed large fluctuations in diameter and were difficult to stretch.
Ein Copolymer gemäß Vergleichsbeispiel 3 wurde bei 360°C zu Monofilen von 0,5 und 0,65 mm Durchmesser versponnen und anschließend bei 220°C um das 2-fache verstreckt. Die Monofile hatten eine Reißfestigkeit von 145 N/mm² und eine Bruchdehnung von 45 %.A copolymer according to Comparative Example 3 was spun at 360 ° C. to monofilaments of 0.5 and 0.65 mm in diameter and then stretched twice at 220 ° C. The monofilaments had a tensile strength of 145 N / mm² and an elongation at break of 45%.
Claims (8)
- A melt spun filament from one or more aromatic polymers composed of repeat units of the general formula
-O-X-SO₂-X- II
where X is 1,4-phenylene, 4,4'-biphenylene or 1,7-naphthylene, which each may have chlorine atoms as substituents, containing less than 1% by weight of matter not homogeneously soluble in the aromatic polymers. - A melt spun filament as claimed in claim 1, where the aromatic polymer has a relative solution viscosity of from 1.40 to 2.0.
- A melt spun filament as claimed in claim 1 or 2, which is from 20 »m to 0.1 mm in diameter and where the aromatic polymer has a relative solution viscosity of from 1.40 to 1.65.
- A melt spun filament as claimed in claim 1 or 2, which is from 0.1 to 1.5 mm in diameter and where the aromatic polymer has a relative solution viscosity of from 1.65 to 2.0.
- A melt spun filament as claimed in any of claims 1 to 4, which has been drawn to a draw ratio of from 1.2:1 to 10:1.
- A process for producing from the melt a filament from one or more aromatic polymers composed of repeat units of the general formula
-O-X-SO₂-X- II
where X is 1,4-phenylene, 4,4'-biphenylene or 1,7-naphthylene, which each may have chlorine atoms as substituents, comprises spinning aromatic polymers containing less than 1% by weight of matter not homogeneously soluble in the aromatic polymers, into filaments at a temperature T which is not less than 10°C below the decomposition temperature of the aromatic polymer and at which the viscosity of the melt is less than 1000 Pa.s at a shear rate of from 10 to 1000 s⁻¹. - A process as claimed in claim 6, wherein aromatic polymers having a relative viscosity of from 1.40 to 1.65 are used for a filament from 20 » to 0.1 mm in diameter and aromatic polymers having a relative viscosity of from 1.65 to 2 are used for a filament from 0.1 to 1 mm in diameter.
- A process as claimed in claim 6 or 7, wherein the filament is drawn to a draw ratio of from 1.2:1 to 10:1 at from 50 to 300°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3814715A DE3814715A1 (en) | 1988-04-30 | 1988-04-30 | THREAD MOLDED THREADS FROM AT LEAST ONE AROMATIC POLYMER |
| DE3814715 | 1988-04-30 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0340572A2 EP0340572A2 (en) | 1989-11-08 |
| EP0340572A3 EP0340572A3 (en) | 1990-10-10 |
| EP0340572B1 true EP0340572B1 (en) | 1995-06-28 |
Family
ID=6353304
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP89107285A Expired - Lifetime EP0340572B1 (en) | 1988-04-30 | 1989-04-22 | Melt-spun fibres from at least one aromatic polymer, and process for their preparation |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0340572B1 (en) |
| JP (1) | JPH01314725A (en) |
| DE (2) | DE3814715A1 (en) |
| ES (1) | ES2073415T3 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BRPI0919681A2 (en) | 2008-10-17 | 2017-10-31 | Solvay Advanced Polymers Llc | process for making a fiber or sheet, and fiber or sheet |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1246295A (en) * | 1982-12-23 | 1988-12-06 | Robert A. Clendinning | Aromatic amorphous thermoplastic terpolymers |
| JPH0634910B2 (en) * | 1985-07-19 | 1994-05-11 | 旭化成工業株式会社 | Method for producing polysulfone-based membrane |
| JPS6262835A (en) * | 1985-09-13 | 1987-03-19 | Mitsui Toatsu Chem Inc | Production of formed porous article |
| JPS6353414A (en) * | 1986-08-25 | 1988-03-07 | Hitachi Cable Ltd | Detection for angle of inclination of transmission line steel tower |
| EP0283520B1 (en) * | 1986-09-26 | 1993-12-29 | Toray Industries, Inc. | Polyphenylene sulfone fibers and a method for their production |
| JPS6391102A (en) * | 1986-10-03 | 1988-04-21 | Kanegafuchi Chem Ind Co Ltd | Membrane for separating blood plasma component |
| CA1334469C (en) * | 1988-03-03 | 1995-02-14 | Marvin Edward Sauers | Poly(aryl ether sulfones) with improved environmental stress-crack resistance and medical devices made therefrom |
-
1988
- 1988-04-30 DE DE3814715A patent/DE3814715A1/en not_active Withdrawn
-
1989
- 1989-04-21 JP JP1100369A patent/JPH01314725A/en active Pending
- 1989-04-22 DE DE58909314T patent/DE58909314D1/en not_active Expired - Lifetime
- 1989-04-22 EP EP89107285A patent/EP0340572B1/en not_active Expired - Lifetime
- 1989-04-22 ES ES89107285T patent/ES2073415T3/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| EP0340572A2 (en) | 1989-11-08 |
| DE58909314D1 (en) | 1995-08-03 |
| JPH01314725A (en) | 1989-12-19 |
| DE3814715A1 (en) | 1989-11-09 |
| ES2073415T3 (en) | 1995-08-16 |
| EP0340572A3 (en) | 1990-10-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0503421B1 (en) | Polyester fibres modified with carbodiimides and process for their preparation | |
| DE60125870T2 (en) | METHOD FOR PRODUCING A META FULL-LARMATIC POLYAMIDE FIBER | |
| EP0407901A2 (en) | Process for the fabrication of polyethylene fibres by the high speed spinning of ultra-high molecular weight polyethylene | |
| EP1208255A1 (en) | High-strength polyester threads and method for producing the same | |
| DE2931439C2 (en) | ||
| DE19537726A1 (en) | Spinning cellulose multifilament yarns with high additive content | |
| DE2338477A1 (en) | ANTISTATIC POLYAMIDE FIBERS WITH A REDUCED PROBLEM TO BUBBLE | |
| EP0019870B1 (en) | Filaments and fibres of acrylonitrile copolymer blends, and process for manufacturing them | |
| EP0918894B1 (en) | Method for producing cellulose fibres | |
| DE1256838B (en) | Process for producing threads by wet spinning a polyvinylidene fluoride solution | |
| DE1669453B2 (en) | POLYAMIDE YARN AND THE METHOD FOR MANUFACTURING IT | |
| EP0340572B1 (en) | Melt-spun fibres from at least one aromatic polymer, and process for their preparation | |
| EP0918798B1 (en) | Method for the production of cellulosic shaped bodies | |
| DE3726211C2 (en) | ||
| EP0779382A1 (en) | Hydrolysis resistant polyester fibres and filaments, masterbatches and production process of polyester fibres and filaments | |
| DE1270216B (en) | PROCESS FOR MANUFACTURING FEMES FROM LINEAR POLYESTERS | |
| DE19937727A1 (en) | Polyester staple fibers and process for their manufacture | |
| DE1286684B (en) | Process for the production of threads, fibers or films by wet or dry spinning of an acrylonitrile polymer mixture | |
| EP1208253B1 (en) | Hmls-fibers made of polyester and a spin-stretch process for its production | |
| DE2752683C2 (en) | ||
| DE69924300T2 (en) | POLY (ARYLENE SULFIDE) COMPOSITIONS AND THEIR USE | |
| DE2541482C3 (en) | Process for the production of drawn threads from poly-phenylene-13,4-oxadiazole | |
| EP0013889B1 (en) | Continuous process for the manufacture of filaments or fibres from synthetic polymers of low solubility | |
| DE850213C (en) | Process for the production of shaped structures from polyvinyl or polyacrylic compounds | |
| DE1469093C3 (en) | Process for the production of polycarbonate threads or fibers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): BE CH DE ES FR GB IT LI NL |
|
| PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
| AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): BE CH DE ES FR GB IT LI NL |
|
| 17P | Request for examination filed |
Effective date: 19900906 |
|
| 17Q | First examination report despatched |
Effective date: 19931102 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE CH DE ES FR GB IT LI NL |
|
| REF | Corresponds to: |
Ref document number: 58909314 Country of ref document: DE Date of ref document: 19950803 |
|
| GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 19950710 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2073415 Country of ref document: ES Kind code of ref document: T3 |
|
| ITF | It: translation for a ep patent filed |
Owner name: ING. C. GREGORJ S.P.A. |
|
| ET | Fr: translation filed | ||
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| 26N | No opposition filed | ||
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20030324 Year of fee payment: 15 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20030325 Year of fee payment: 15 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20030331 Year of fee payment: 15 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20030401 Year of fee payment: 15 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20030408 Year of fee payment: 15 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20030425 Year of fee payment: 15 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20030522 Year of fee payment: 15 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040422 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040423 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040430 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040430 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040430 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF THE APPLICANT RENOUNCES Effective date: 20040602 |
|
| BERE | Be: lapsed |
Owner name: *BASF A.G. Effective date: 20040430 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20041101 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20040422 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20041231 |
|
| NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20041101 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20050422 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20040423 |