EP0344590A2 - Fibres from linear thermoplastic polyamides and modified polyphenylene ethers - Google Patents
Fibres from linear thermoplastic polyamides and modified polyphenylene ethers Download PDFInfo
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- EP0344590A2 EP0344590A2 EP89109325A EP89109325A EP0344590A2 EP 0344590 A2 EP0344590 A2 EP 0344590A2 EP 89109325 A EP89109325 A EP 89109325A EP 89109325 A EP89109325 A EP 89109325A EP 0344590 A2 EP0344590 A2 EP 0344590A2
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- European Patent Office
- Prior art keywords
- weight
- melt
- polyamide
- mixing
- polyphenylene ether
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Classifications
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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
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
-
- 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
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
Definitions
- Threads made of polyamides such as polyamide-6 or polyamind-6,6 are industrially manufactured on a large scale and are characterized by high tear strength, bending strength, abrasion resistance, high elasticity and sufficient chemical resistance.
- the disadvantage is their high water absorption and the associated influence on the mechanical properties such.
- B. the modulus of elasticity and associated reduced rigidity due to absorbed water.
- the light and heat stability of these threads is low, which can only be improved over a limited time by adding stabilizers.
- the spinning of polyamide-6,6 in particular requires special measures because of the low thermal stability of the melt, e.g. Steam spinning.
- the previously known measures e.g. The addition of stabilizers to remedy these disadvantages has so far been unsatisfactory.
- the new threads are characterized by improved heat and light stability and low water absorption, while maintaining the mechanical properties.
- the new threads can be spun from the melt without fear of thermal degradation of the melt.
- the threads according to the invention contain 99 to 1% by weight, in particular 50 to 20% by weight, of a linear polyamide e.g. with a relative viscosity of 2.2 to 4.5 measured as a 1% by weight solution in 96% by weight sulfuric acid at 23 ° C.
- a linear polyamide e.g. with a relative viscosity of 2.2 to 4.5 measured as a 1% by weight solution in 96% by weight sulfuric acid at 23 ° C.
- Polyamides derived from lactams with 7 to 13 ring members such as polycaprolactam, polycaprylactam or polylaurine lactam, and polyamides obtained by reacting dicarboxylic acids with diamines, are preferred.
- Suitable dicarboxylic acids which can also be used in any combination, are, for example, alkanedicarboxylic acids having 6 to 12 carbon atoms, in particular 6 to 10 carbon atoms, terephthalic acid, isophthalic acid.
- Suitable diamines which can also be used in any combination, are, for example, alkanediamines having 4 to 12 carbon atoms, in particular 4 to 8 carbon atoms, and also m-xylylenediamine, bis- (4-aminophenyl) methane. It is also possible to use mixtures of the polyamides mentioned. Polyamide-6, polyamide-6,6 and polyamides, which are composed of hexamethylenediamine and isophthalic acid and terephthalic acid, have acquired particular technical importance.
- the threads according to the invention contain 1 to 99% by weight, in particular 80 to 50% by weight, of a reaction product which can be obtained by mixing in the melt, e.g. at a temperature of 250 to 300 ° C, from 99.9 to 35 wt.%, In particular 50 to 80 wt.% of a linear thermoplastic polyamide (component b1) and 0.1 to 65 wt.%, in particular 50 to 20 wt % of a modified polyphenylene ether (component b2).
- a reaction product which can be obtained by mixing in the melt, e.g. at a temperature of 250 to 300 ° C, from 99.9 to 35 wt.%
- a linear thermoplastic polyamide component b1
- 0.1 to 65 wt.% in particular 50 to 20 wt % of a modified polyphenylene ether (component b2).
- modified polyphenylene esters used as component b2 according to the invention are produced from the following components by mixing in the melt at a temperature of 250 to 350 ° C:
- component b 2.1 99.0 to 70% by weight, in particular 90 to 99% by weight, of a polyphenylene ether, it being possible for up to 50% by weight of the polyphenylene ether to be replaced by vinylaromatic polymers.
- the polyphenylene ethers are compounds based on the 2 and / or 6-position to the oxygen-substituted, in particular disubstituted, polyphenylene oxides, the ether oxygen of one unit being bonded to the benzene nucleus of the adjacent unit. At least 50 units are advantageously linked to one another.
- Suitable polyphenylene ethers preferably have alkyl radicals with 1-4 carbon atoms, in particular methyl radicals, in the 2.6 position to the oxygen.
- Examples include poly (2,6-dimethyl-1,4-phenylene) oxide, poly (2,6-diethyl-1,4-phenylene) oxide, poly (2-methyl-6-ethyl-1,4-polyphenylene ) oxide, poly (2-methyl-6-propyl-1,4-phenylene) oxide, poly (2,6-dipropyl-1,4-phenylene) oxide or poly (2-ethyl-6-propyl-1,4 -phenylene) oxide.
- the polyphenylene ethers used advantageously have an intrinsic viscosity of 0.4-0.7 dl / g (measured in chloroform at 30 ° C.). Polyphenylene ethers which are miscible with styrene are particularly preferred.
- Suitable vinyl aromatic polymers are, for example, polystyrene, polyalphamethylstyrene or polyvinyltoluene, in particular polystyrene.
- Component b 2.2 uses 0.1 to 30% by weight, in particular 1 to 10% by weight, of at least one ⁇ , ⁇ -unsaturated aliphatic dicarboxylic acid, its alkyl ester, its half-ester, half-amide or imide and / or a (meth) acrylamide .
- Particularly suitable are fumaric acid C1 to C4 alkyl esters or the corresponding half-ester, fumaric acid half-imide, maleimide or (meth) acrylamide.
- Fumaric acid, C1 to C4 alkyl esters or the corresponding half ester are particularly preferred.
- Beta.-unsaturated aliphatic carboxylic acid or its esters or vinylaromatic monomers can also be used as further component b 2.3 .
- Particularly preferred are acrylic acid, the C1 to C4 alkyl esters of styrene, alphamethylstryrene or vinyl toluene.
- the threads according to the invention optionally contain conventional additives in effective amounts.
- Fillers, matting agents, dye pigments, stabilizers against degradation by the action of heat, atmospheric oxygen and light may be mentioned as additives.
- the threads according to the invention are advantageously produced as follows.
- Component b2 is produced by mixing and reacting components b 2.1 , b 2.2 and optionally b 2.3 in the melt at a temperature of 250 to 350 ° C., poured into strands and granulated.
- the granules obtained in this way are then reacted in the melt, for example at a temperature of 250 to 350 ° C., with the polyamide component b 1, poured into strands and granulated.
- the granules (B) thus obtained are then mixed with component A in the melt, for example at a temperature of 250-350 ° C., and threads are spun from the melt, for example with a diameter of 100 to 10 ⁇ m.
- the threads are advantageously used at elevated temperatures e.g. Stretched 50 to 150 ° C e.g. 1.5 to 10 times, especially 2 to 5 times.
- the threads according to the invention are suitable for the production of technical or textile fabrics such as woven fabrics, knitted fabrics of all kinds, non-woven nonwovens.
- the average residence time in the extruder was 2.5 minutes.
- the melt was poured into strands, cooled, granulated and dried. 40 parts by weight of the granules obtained in this way were reacted with 66 parts by weight of polyamide-6 with a molecular weight M g of 36,000 in a twin-screw extruder at 280 ° C., the residence time in the extruder being 2 minutes.
- the melt was poured into strands, cooled, granulated and the granules dried.
- component B 50 parts of the reaction product thus obtained (component B) were mixed with 50 parts by weight of polyamide-6 with a relative solution viscosity of 2.63, (measured in a solution of 1 g of polymer in 100 ml of 96% by weight sulfuric acid at 25 ° C. ) mixed at a temperature of 275 ° C in the melt, granulated and dried. The dried granules were then spun in a manner known per se on an extruder melt spinning device at a temperature of 290 ° C. and a take-off speed of 800 m / min. The threads obtained were coldly hidden 2.6 times in a manner known per se.
- the hidden threads had the following properties: Titer: 111/20 dtex Tear resistance: 3.6 cN / dtex Elongation at break: 56.5% E-module: 36000 cN / mm2 Water absorption: 1.0% in the standard climate Heat stability: 34% of the initial strength after heating in air at 190 ° C for three hours Light stability: 40% tear strength, based on the initial strength in the Xenotest 450 after 28 days
- Example 1 was repeated with the difference that only polyamide-6 (component A) was spun into threads.
- the threads spun at 290 ° C and coldly stretched 3.5 times had the following properties: Titer: 75/20 dtex Tear resistance: 3.5 cN / dtex Elongation at break: 26% E-module: 29000 cN / mm2 Water absorption: 1.7% in the standard climate Heat stability: 23% measured as in Example 1
- Light stability 20% tear resistance, based on the initial strength of the Xenotest 450 after 28 days
- Example 2 The polyamide-6,6 used in Example 2 was spun into threads and drawn at a temperature of 290 ° C. as in Example 2 without further additives.
- the threads had the following properties: Titer: 94/1 dtex Tear resistance: 3.0 cN / dtex Elongation at break: 30% E-module: 23 cN / dtex
Abstract
Description
Fäden aus Polyamiden wie Polyamid-6 oder Polyamind-6,6 werden im großen Maßstab technisch hergestellt und zeichnen sich durch hohe Reißfestigkeit, Biegefestigkeit, Abriebfestigkeit, hohe Elastizität und ausreichende chemische Beständigkeit aus. Nachteilig ist jedoch ihre hohe Wasseraufnahme und die damit verbundene Beeinflussung der mechanischen Eigenschaften z. B. des E-Moduls und damit verbundene verringerte Steifigkeit durch aufgenommenes Wasser. Ferner ist die Licht- und Hitzestabilität dieser Fäden gering, die durch Zusatz von Stabilisatoren nur über eine begrenzte Zeit verbessert werden kann. Darüber hinaus bedarf die Verspinnung insbesondere von Polyamid-6,6 wegen der geringen thermischen Stabilität der Schmelze spezieller Maßnahmen z.B. Dampfspinnen. Die bisher bekannten Maßnahmen z.B. der Zusatz von Stabilisatoren zur Behebung diesr Nachteile waren bislang unbefriedigend.Threads made of polyamides such as polyamide-6 or polyamind-6,6 are industrially manufactured on a large scale and are characterized by high tear strength, bending strength, abrasion resistance, high elasticity and sufficient chemical resistance. The disadvantage is their high water absorption and the associated influence on the mechanical properties such. B. the modulus of elasticity and associated reduced rigidity due to absorbed water. Furthermore, the light and heat stability of these threads is low, which can only be improved over a limited time by adding stabilizers. In addition, the spinning of polyamide-6,6 in particular requires special measures because of the low thermal stability of the melt, e.g. Steam spinning. The previously known measures e.g. The addition of stabilizers to remedy these disadvantages has so far been unsatisfactory.
Es war deshalb die technische Aufgabe gestellt, diese Nachteile hinsichtlich Verarbeitung und Eigenschaften zu beheben.The technical task was therefore to remedy these disadvantages with regard to processing and properties.
Diese Aufgabe wird gelöst durch Fäden enthaltend als wesentliche Komponenten
- A) 99 bis 1 Gew.% eines linearen thermoplastischen Polyamids
- B) 1 bis 99 Gew.% eines Umsetzungsprodukts erhalten durch Mischen in der Schmelze von b₁) 99,9 bis 35 Gew.% eines linearen Polyamids und
b₂) 0,1 bis 65 Gew.% eines modifizierten Polyphenylenethers hergestellt aus
b2.1 99,0 bis 70 Gew.% eines Polyphenylenethers der bis zu 50 Gew.% durch vinylaromatische Polymeren ersetzt sein kann
b2.2 0,1 bis 30 Gew.% mindestens einer α,β-ungesättigten aliphatischen Dicarbonsäure, deren Alkylester, Halbester, Halbamide oder Imide und/oder eines (Meth)acrylamids
b2.3 0 bis 29,9 Gew.% einer α,β-ungesättigten aliphatischen Carbonsäure oder deren Ester oder vinylaromatische Monomere
durch Mischen der Komponenten b2.1, b2.2 und b2.3 in der Schmelze bei einer Temperatur von 250 bis 350°C, mit der Maßgabe, daß sich die Prozentangaben der Komponenten b2.1, b2.2 und b2.3 jeweils auf 100 Gew.% ergänzen, - C) gegebenenfalls übliche Zusatzstoffe in wirksamen Mengen.
- A) 99 to 1% by weight of a linear thermoplastic polyamide
- B) 1 to 99% by weight of a reaction product obtained by mixing in the melt from b₁) 99.9 to 35% by weight of a linear polyamide and
b₂) 0.1 to 65% by weight of a modified polyphenylene ether made from
b 2.1 99.0 to 70% by weight of a polyphenylene ether which can be replaced by up to 50% by weight with vinyl aromatic polymers
b 2.2 0.1 to 30% by weight of at least one α, β-unsaturated aliphatic dicarboxylic acid, its alkyl esters, half-esters, half-amides or imides and / or a (meth) acrylamide
b 2.3 0 to 29.9% by weight of an α, β-unsaturated aliphatic carboxylic acid or its esters or vinyl aromatic monomers
by mixing components b 2.1 , b 2.2 and b 2.3 in the melt at a temperature of 250 to 350 ° C., with the proviso that the percentages of components b 2.1 , b 2.2 and b 2.3 each add up to 100% by weight , - C) If appropriate, conventional additives in effective amounts.
Die neuen Fäden zeichen sich durch verbesserte Hitze- und Lichtstabilität sowie geringe Wasseraufnahme aus, wobei die mechanischen Eigenschaften erhalten bleiben. Zudem lassen sich die neuen Fäden aus der Schmelze verspinnen, ohne daß ein thermischer Abbau der Schmelze zu befürchten ist.The new threads are characterized by improved heat and light stability and low water absorption, while maintaining the mechanical properties. In addition, the new threads can be spun from the melt without fear of thermal degradation of the melt.
Als Komponente A enthalten die erfindungsgemäßen Fäden 99 bis 1 Gew.%, insbesondere 50 bis 20 Gew.% eines linearen Polyamids z.B. mit einer relativen Viskosität von 2,2 bis 4,5 gemessen als 1 gew.%ige Lösung in 96 gew.%iger Schwefelsäure bei 23°C. Bevorzugt seien genannt Polyamide, die sich von Lactamen mit 7 bis 13 Ringgliedern ableiten, wie Polycaprolactam, Polycaprylactam oder Polylaurinlactam sowie Polyamide die durch Umsetzung von Dicarbonsäuren mit Diaminen erhalten werden. Geeignete Dicarbonsäuren, die auch in beliebigen Kombinationen einsetzbar sind, sind beispielsweise Alkandicarbonsäuren mit 6 bis 12 Kohlenstoffatomen, insbesondere 6 bis 10 Kohlenstoffatomen, Terephthalsäure, Isophthalsäure. Geeignete Diamine, die auch in beliebigen Kombinationen einsetzbar sind, sind beispielsweise Alkandiamine mit 4 bis 12 Kohlenstoffatomen, insbesondere 4 bis 8 Kohlenstoffatomen ferner m-Xylilendiamin, bis- (4-Aminophenyl)methan. Es ist auch möglich, Mischungen der genannten Polyamide zu verwenden. Besondere technische Bedeutung haben Polyamid-6, Polyamid-6,6 sowie Polyamide, die aus Hexamethylendiamin und Isophthalsäure sowie Terephthalsäure aufgebaut sind, erlangt.As component A, the threads according to the invention contain 99 to 1% by weight, in particular 50 to 20% by weight, of a linear polyamide e.g. with a relative viscosity of 2.2 to 4.5 measured as a 1% by weight solution in 96% by weight sulfuric acid at 23 ° C. Polyamides derived from lactams with 7 to 13 ring members, such as polycaprolactam, polycaprylactam or polylaurine lactam, and polyamides obtained by reacting dicarboxylic acids with diamines, are preferred. Suitable dicarboxylic acids, which can also be used in any combination, are, for example, alkanedicarboxylic acids having 6 to 12 carbon atoms, in particular 6 to 10 carbon atoms, terephthalic acid, isophthalic acid. Suitable diamines, which can also be used in any combination, are, for example, alkanediamines having 4 to 12 carbon atoms, in particular 4 to 8 carbon atoms, and also m-xylylenediamine, bis- (4-aminophenyl) methane. It is also possible to use mixtures of the polyamides mentioned. Polyamide-6, polyamide-6,6 and polyamides, which are composed of hexamethylenediamine and isophthalic acid and terephthalic acid, have acquired particular technical importance.
Als Komponente B enthalten die erfindungsgemäßen Fäden 1 bis 99 Gew.%, insbesondere 80 bis 50 Gew.% eines Umsetzungsprodukts, das man durch Mischen in der Schmelze, z.B. bei einer Temperatur von 250 bis 300°C, von 99,9 bis 35 Gew.%, insbesondere 50 bis 80 Gew.% eines linearen thermoplastischen Polyamids (Komponente b₁) und 0,1 bis 65 Gew.%, insbesondere 50 bis 20 Gew.% eines modifizierten Polyphenylenethers (Komponente b₂) erhält.As component B, the threads according to the invention contain 1 to 99% by weight, in particular 80 to 50% by weight, of a reaction product which can be obtained by mixing in the melt, e.g. at a temperature of 250 to 300 ° C, from 99.9 to 35 wt.%, In particular 50 to 80 wt.% of a linear thermoplastic polyamide (component b₁) and 0.1 to 65 wt.%, in particular 50 to 20 wt % of a modified polyphenylene ether (component b₂).
Die als erfindungsgemäße Komponente b₂ verwendeten modifizierten Polyphenylenester werden hergestellt aus folgenden Komponenten durch Mischen in der Schmelze bei einer Temperatur von 250 bis 350°C:The modified polyphenylene esters used as component b₂ according to the invention are produced from the following components by mixing in the melt at a temperature of 250 to 350 ° C:
Als Komponente b2.1 99,0 bis 70 Gew.%, insbesondere 90 bis 99 Gew.%, eines Polyphenylenethers, wobei bis zu 50 Gew.% des Polyphenylenethers durch vinylaromatische Polymere ersetzt sein können.As component b 2.1, 99.0 to 70% by weight, in particular 90 to 99% by weight, of a polyphenylene ether, it being possible for up to 50% by weight of the polyphenylene ether to be replaced by vinylaromatic polymers.
Bei den Polyphenylenethern handelt es sich um Verbindungen auf Basis von 2 und/oder 6 Stellung zum Sauerstoff substituierten, insbesondere disubstituierten Polyphenylenoxiden, wobei der Ethersauerstoff der einen Einheit an den Benzolkern der benachbarten Einheit gebunden ist. Vorteilhaft sind mindestens 50 Einheiten miteinander verknüpft. Geeignete Polyphenylenether haben als Substituenten vorzugsweise in 2,6 Stellung zum Sauerstoff Alkylreste mit 1 - 4 Kohlenstoffatomen, insbesondere Methylreste. Beispielshaft seien genannt Poly(2,6-dimethyl-1,4-phenylen)oxid, Poly(2,6-diethyl-1,4-phenylen)oxid, Poly(2-methyl-6-ethyl-1,4-polyphenylen)oxid, Poly(2-methyl-6-propyl-1,4-phenylen)oxid, Poly(2,6-dipropyl-1,4-phenylen)oxid oder Poly(2-ethyl-6-propyl-1,4-phenylen)-oxid.The polyphenylene ethers are compounds based on the 2 and / or 6-position to the oxygen-substituted, in particular disubstituted, polyphenylene oxides, the ether oxygen of one unit being bonded to the benzene nucleus of the adjacent unit. At least 50 units are advantageously linked to one another. Suitable polyphenylene ethers preferably have alkyl radicals with 1-4 carbon atoms, in particular methyl radicals, in the 2.6 position to the oxygen. Examples include poly (2,6-dimethyl-1,4-phenylene) oxide, poly (2,6-diethyl-1,4-phenylene) oxide, poly (2-methyl-6-ethyl-1,4-polyphenylene ) oxide, poly (2-methyl-6-propyl-1,4-phenylene) oxide, poly (2,6-dipropyl-1,4-phenylene) oxide or poly (2-ethyl-6-propyl-1,4 -phenylene) oxide.
Vorteilhaft haben die verwendeten Polyphenylenether eine Grenzviskosität von 0,4 - 0,7 dl/g (gemessen in Chloroform bei 30°C). Besonders bevorzugt sind Polyphenylenether, die mit Styrol mischbar sind.The polyphenylene ethers used advantageously have an intrinsic viscosity of 0.4-0.7 dl / g (measured in chloroform at 30 ° C.). Polyphenylene ethers which are miscible with styrene are particularly preferred.
Die Polyphenylenether können bis zu 50 Gew.%, insbesondere bis zu 20 Gew.%, durch vinylaromatische Polymere ersetzt sein. Geeignete vinylaromatische Polymere sind beispielsweise Polystyrol, Polyalphamethylstyrol oder Polyvinyltoluol, insbesondere Polystyrol.Up to 50% by weight, in particular up to 20% by weight, of the polyphenylene ethers can be replaced by vinyl aromatic polymers. Suitable vinyl aromatic polymers are, for example, polystyrene, polyalphamethylstyrene or polyvinyltoluene, in particular polystyrene.
Als Komponente b2.2 werden 0,1 bis 30 Gew.%, insbesondere 1 bis 10 Gew.%, mindestens einer α,β-ungesättigten aliphatischen Dicarbonsäure, deren Alkylester, deren Halbester, Halbamide oder Imide und/oder eines (Meth)acrylamids verwendet. Insbesondere sind geeignet Fumarsäure-C₁- bis C₄-Alkylester oder der entsprechende Halbester, Fumarsäurehalbimid, Maleinimid oder (Meth)acrylamid. Besonders bevorzugt sind Fumarsäure, C₁- bis C₄-Alkylester oder der entsprechende Halbester.Component b 2.2 uses 0.1 to 30% by weight, in particular 1 to 10% by weight, of at least one α, β-unsaturated aliphatic dicarboxylic acid, its alkyl ester, its half-ester, half-amide or imide and / or a (meth) acrylamide . Particularly suitable are fumaric acid C₁ to C₄ alkyl esters or the corresponding half-ester, fumaric acid half-imide, maleimide or (meth) acrylamide. Fumaric acid, C₁ to C₄ alkyl esters or the corresponding half ester are particularly preferred.
Als weitere Komponente b2.3 können 0 bis 29,9 Gew.% einer α,β-ungesättigten aliphatischen Carbonsäure oder deren Ester oder vinylaromatische Monomere mitverwendet werden. Besonders bevorzugt sind Acrylsäure, deren C₁- bis C₄-Alkylester ferner Styrol, Alphamethylstryrol oder Vinyltoluol.0 to 29.9% by weight of an .alpha.,. Beta.-unsaturated aliphatic carboxylic acid or its esters or vinylaromatic monomers can also be used as further component b 2.3 . Particularly preferred are acrylic acid, the C₁ to C₄ alkyl esters of styrene, alphamethylstryrene or vinyl toluene.
Es versteht sich, daß sich die Prozentzahlen der Komponenten b2.1, b2.2 und b2.3 jeweils auf 100 % ergänzen.It is understood that the percentages of components b 2.1 , b 2.2 and b 2.3 each add up to 100%.
Als Komponente C enthalten die erfindungsgemäßen Fäden gegebenenfalls übliche Zusätze in wirksamen Mengen. Als Zusatzstoffe seien genannt Füllstoffe, Mattierungsmittel, Farbstoffpigmente, Stabilisatoren gegen Abbau durch Einwirkung von Hitze, Luftsauerstoff und Licht.As component C, the threads according to the invention optionally contain conventional additives in effective amounts. Fillers, matting agents, dye pigments, stabilizers against degradation by the action of heat, atmospheric oxygen and light may be mentioned as additives.
Bevorzugte Fäden bestehen demnach im wesentlichen aus
- A) 50 bis 20 Gew.% eines linearen thermoplastischen Polyamids, insbesondere Polyamid-6 oder Polyamid-6,6
- B) 80 bis 50 Gew.% eines Umsetzungsprodukts erhalten durch Mischen Schmelze von
- b₁) 50 bis 80 Gew.% eines linearen Polyamids, insbesondere Polyamid-6 oder Polyamid-6,6 und
- b₂) 20 bis 50 Gew.% eines modifizierten Polyphenylenethers hergestellt aus
- b2.1 90 bis 99 Gew.% Polyphenylenether, der zu 20 Gew.% durch Polystyrol ersetzt sein kann und
- b2.2 1 bis 10 Gew.% einer Verbindung ausgewählt aus der Gruppe Fumarsäure, dessen Alkylester, dessen Halbester Fumarsäurehalbamid, Maleinimid oder (Meth)acrylamid durch Mischen in der Schmelze bei einer Temperatur von 250 - 350°C sowie
- C gegebenenfalls üblichen Zusätzen in wirksamen Mengen.
- A) 50 to 20% by weight of a linear thermoplastic polyamide, in particular polyamide-6 or polyamide-6,6
- B) 80 to 50% by weight of a reaction product obtained by mixing the melt of
- b₁) 50 to 80 wt.% Of a linear polyamide, in particular polyamide-6 or polyamide-6,6 and
- b₂) 20 to 50 wt.% Of a modified polyphenylene ether made from
- b 2.1 90 to 99% by weight of polyphenylene ether, 20% by weight of which can be replaced by polystyrene and
- b 2.2 1 to 10 wt.% of a compound selected from the group fumaric acid, its alkyl ester, its half-ester fumaric acid halamide, maleimide or (meth) acrylamide by mixing in the melt at a temperature of 250 - 350 ° C and
- C optional additives in effective amounts.
Die erfindungsgemäßen Fäden werden vorteilhaft wie folgt hergestellt. Die Komponente b₂ wird durch Mischen und Umsetzen der Komponenten b2.1, b2.2 und gegebenenfalls b2.3 in der Schmelze bei einer Temperatur von 250 bis 350°C hergestellt, zu Strängen vergossen und granuliert. Das so erhaltene Granulat wird dann in der Schmelze z.B. bei einer Temperatur von 250 bis 350°C, mit der Polyamidkomponente b₁ umgesetzt, in Stränge gegossen und granuliert. Das so erhaltene Granulat (B) wird dann mit der Komponente A in der Schmelze z.B. bei einer Temperatur von 250 - 350°C vermischt und aus der Schmelze Fäden z.B. mit einem Druchmesser von 100 bis 10 µ versponnen.The threads according to the invention are advantageously produced as follows. Component b₂ is produced by mixing and reacting components b 2.1 , b 2.2 and optionally b 2.3 in the melt at a temperature of 250 to 350 ° C., poured into strands and granulated. The granules obtained in this way are then reacted in the melt, for example at a temperature of 250 to 350 ° C., with the polyamide component b 1, poured into strands and granulated. The granules (B) thus obtained are then mixed with component A in the melt, for example at a temperature of 250-350 ° C., and threads are spun from the melt, for example with a diameter of 100 to 10 μm.
Die Fäden werden vorteilhaft bei erhöhter Temperatur z.B. 50 bis 150°C verstreckt z.B. auf das 1,5- bis 10-fache, insbesondere das 2- bis 5-fache.The threads are advantageously used at elevated temperatures e.g. Stretched 50 to 150 ° C e.g. 1.5 to 10 times, especially 2 to 5 times.
Die erfindungsgemäßen Fäden eignen sich für die Herstellung technischer oder textiler Flächengebilde wie Gewebe, Gewirke aller Art, nichtgewebte Vliese.The threads according to the invention are suitable for the production of technical or textile fabrics such as woven fabrics, knitted fabrics of all kinds, non-woven nonwovens.
Der Gegenstand der Erfindung sei an folgenden Beispielen veranschaulicht.The subject matter of the invention is illustrated by the following examples.
90 Gew.% Poly(2,6-dimethyl-1,4-phenylen)oxid mit einer relativen Viskosität von 0,59 (gemessen in 1 gew.%er Lösung in Chloroform bei 25°C), 9 Gew.% Polystyrol (Schmelzflußindex MFI bei 200°C/50 kg Belastung von 524 g/10 Min) und 1 Gew.% Fumarsäuremonomethylester wurden in einem Zweischneckenextruder in einem ersten Teil unter Verwendung von Knetelementen bei 265°C aufgeschmolzen und in einem zweiten Teil unter Kneten und Verwendung von Knetelementen bei 265°C umgesetzt und anschließend in einer Entgasungszone bei 255°C durch Anlegen von Vakuum entgast. Die mittlere Verweilzeit im Extruder betrug 2,5 Minuten. Die Schmelze wurde in Stränge gegossen, gekühlt, granuliert und getrocknet. 40 Gew.Teile des so erhaltenen Granulats wurden mit 66 Gew.Teilen Polyamid-6 mit einem Molekulargewicht Mg von 36 000 in einem Zweischneckenextruder bei 280°C umgesetzt, wobei die Verweilzeit im Extruder 2 Minuten betrug. Die Schmelze wurde in Stränge gegossen, gekühlt, granuliert und das Granulat getrocknet.90% by weight poly (2,6-dimethyl-1,4-phenylene) oxide with a relative viscosity of 0.59 (measured in 1% by weight solution in chloroform at 25 ° C), 9% by weight polystyrene ( Melt flow index MFI at 200 ° C./50 kg load of 524 g / 10 min) and 1% by weight of fumaric acid monomethyl ester were melted in a twin-screw extruder in a first part using kneading elements at 265 ° C. and in a second part using kneading and using Kneading elements implemented at 265 ° C and then degassed in a degassing zone at 255 ° C by applying a vacuum. The average residence time in the extruder was 2.5 minutes. The melt was poured into strands, cooled, granulated and dried. 40 parts by weight of the granules obtained in this way were reacted with 66 parts by weight of polyamide-6 with a molecular weight M g of 36,000 in a twin-screw extruder at 280 ° C., the residence time in the extruder being 2 minutes. The melt was poured into strands, cooled, granulated and the granules dried.
50 Teile des so erhaltenen Umsetzungsprodukts (Komponente B) wurden mit 50 Gew.Teilen Polyamid-6 mit einer relativen Lösungsviskosität von 2,63, (gemessen in einer Lösung von 1 g Polymer in 100 ml 96 gew.%iger Schwefelsäure bei 25°C) bei einer Temperatur von 275°C in der Schmelze gemischt, granuliert und getrocknet. Das getrocknete Granulat wurde dann in an sich bekannter Weise auf einer Extruderschmelzspinnvorrichtung bei einer Temperatur von 290°C und einer Abzugsgeschwindigkeit von 800 m/Min versponnen. Die erhaltenen Fäden wurden in an sich bekannter Weise kalt auf das 2,6-fache versteckt. Die versteckten Fäden hatten folgende Eigenschaften:
Titer: 111/20 dtex
Reißfestigkeit: 3,6 cN/dtex
Bruchdehnung: 56,5 %
E-Modul: 36000 cN/mm²
Wasseraufnahme: 1,0 % im Normklima
Hitzestabilität: 34 % der Ausgangsfestigkeit nach dreistündigem Erhitzen in Luft bei 190°C
Lichtstabilität: 40 % Reißfestigkeit, bezogen auf die Ausgangsfestigkeit im Xenotest 450 nach 28 Tagen50 parts of the reaction product thus obtained (component B) were mixed with 50 parts by weight of polyamide-6 with a relative solution viscosity of 2.63, (measured in a solution of 1 g of polymer in 100 ml of 96% by weight sulfuric acid at 25 ° C. ) mixed at a temperature of 275 ° C in the melt, granulated and dried. The dried granules were then spun in a manner known per se on an extruder melt spinning device at a temperature of 290 ° C. and a take-off speed of 800 m / min. The threads obtained were coldly hidden 2.6 times in a manner known per se. The hidden threads had the following properties:
Titer: 111/20 dtex
Tear resistance: 3.6 cN / dtex
Elongation at break: 56.5%
E-module: 36000 cN / mm²
Water absorption: 1.0% in the standard climate
Heat stability: 34% of the initial strength after heating in air at 190 ° C for three hours
Light stability: 40% tear strength, based on the initial strength in the Xenotest 450 after 28 days
Beispiel 1 wurde wiederholt mit dem Unterschied, daß nur Polyamid-6 (Komponente A) zu Fäden versponnen wurde. Die bei 290°C versponnen und kalt auf das 3,5-fache verstreckten Fäden hatten folgende Eigenschaften:
Titer: 75/20 dtex
Reißfestigkeit: 3,5 cN/dtex
Bruchdehnung: 26 %
E-Modul: 29000 cN/mm²
Wasseraufnahme: 1,7 % im Normklima
Hitzestabilität: 23 % gemessen wie in Beispiel 1
Lichtstabilität: 20 % Reißfestigkeit, bezogen auf die Ausgangsfestigkeit beim Xenotest 450 anch 28 TagenExample 1 was repeated with the difference that only polyamide-6 (component A) was spun into threads. The threads spun at 290 ° C and coldly stretched 3.5 times had the following properties:
Titer: 75/20 dtex
Tear resistance: 3.5 cN / dtex
Elongation at break: 26%
E-module: 29000 cN / mm²
Water absorption: 1.7% in the standard climate
Heat stability: 23% measured as in Example 1
Light stability: 20% tear resistance, based on the initial strength of the Xenotest 450 after 28 days
95 Gew.Teile Poly(2,6-dimethyl-1,4-phenylen)oxid, 3,5 Gew.Teile Polystyrol und 1,5 Gew.Teile Fumarsäuredimethylester wurden analog wie in Beispiel 1 bei 265°C in der Schmelze umgesetzt, entgast und granuliert. 40 Teile des so erhaltenen Granulats wurden bei 300°C in der Schmelze mit 60 Teilen Polyamid-6,6 umgesetzt und wiederum granuliert.95 parts by weight of poly (2,6-dimethyl-1,4-phenylene) oxide, 3.5 parts by weight of polystyrene and 1.5 parts by weight of fumaric acid dimethyl ester were reacted in the melt analogously to Example 1 at 265 ° C. degassed and granulated. 40 parts of the granules thus obtained were reacted in the melt with 60 parts of polyamide-6,6 at 300 ° C. and again granulated.
40 Gew.Teile des so erhaltenen Granulats (B) wurden mit 60 Gew.Teilen Polyamid-6,6 mit einer relativen Viskosität von 2,50 bei einer Temperatur von 287°C in der Schmelze gemischt, granuliert und getrocknet. Das getrocknete Granulat wurde in an sich bekannter Weise bei einer Temperatur von 290°C und einer Abzugsgeschwindigkeit von 750 m/Min versponnen. Die versponnenen Fäden wurden auf das dreifache bei einer Temperatur von 90°C (Streckwalze) und 120°C (Streckplatte) verstreckt. Die verstrecketen Fäden hatten folgende Eigenschaften:
Titer: 74/1 dtex
Bruchdehnung: 12 %
E-Modul: 33 cN/dtex
Reißfestigkeit: 3,4 cN/dtex40 parts by weight of the granules (B) thus obtained were mixed with 60 parts by weight of polyamide-6.6 with a relative viscosity of 2.50 at a temperature of 287 ° C. in the melt, granulated and dried. The dried granules were spun in a manner known per se at a temperature of 290 ° C. and a take-off speed of 750 m / min. The spun threads were drawn three times at a temperature of 90 ° C (drawing roller) and 120 ° C (drawing plate). The drawn threads had the following properties:
Titer: 74/1 dtex
Elongation at break: 12%
E-module: 33 cN / dtex
Tear resistance: 3.4 cN / dtex
Das in Beispiel 2 verwendete Polyamid-6,6 wurde ohne weitere Zusätze bei einer Temperatur von 290°C wie in Beispiel 2 zu Fäden versponnen und verstreckt. Die Fäden hatten folgende Eigenschaften:
Titer: 94/1 dtex
Reißfestigkeit: 3,0 cN/dtex
Bruchdehnung: 30 %
E-Modul: 23 cN/dtexThe polyamide-6,6 used in Example 2 was spun into threads and drawn at a temperature of 290 ° C. as in Example 2 without further additives. The threads had the following properties:
Titer: 94/1 dtex
Tear resistance: 3.0 cN / dtex
Elongation at break: 30%
E-module: 23 cN / dtex
Claims (5)
b₁) 99,9 bis 35 Gew.% eines linearen Polyamids und
b₂) 0,1 bis 65 Gew.% eines Polyphenylenethers hergestellt aus
b2.1 99,0 bis 70 Gew.% eines Polyphenylenethers der bis zu 50 Gew.% durch vinylaromatische Polymere ersetzt sein kann
b2.2 0,1 bis 30 Gew.% mindestens einer α,β-ungesättigten aliphatischen Dicarbonsäure, deren Alkylester, Halbester, Halbamide oder Imide und/oder eines (Meth)acrylamids
b2.3 0 bis 29,9 Gew.% mindestens einer α,β-ungesättigten aliphatischen Carbonsäure deren Ester oder vinylaromatische Monomere
durch Mischen der Komponenten b2.1, b2.2 und b2.3 in der Schmelze bei einer Temperatur von 250 bis 350°C, mit der Maßgabe, daß sich die Summe der Gewichtsprozente von b2.1, b2.2 und b2.3 jeweils auf 100 Gew.% ergänzt, und
b₁) 99.9 to 35% by weight of a linear polyamide and
b₂) 0.1 to 65% by weight of a polyphenylene ether made from
b 2.1 99.0 to 70% by weight of a polyphenylene ether which can be replaced up to 50% by weight with vinyl aromatic polymers
b 2.2 0.1 to 30% by weight of at least one α, β-unsaturated aliphatic dicarboxylic acid, its alkyl esters, half-esters, half-amides or imides and / or a (meth) acrylamide
b 2.3 0 to 29.9% by weight of at least one α, β-unsaturated aliphatic carboxylic acid, its esters or vinyl aromatic monomers
by mixing components b 2.1 , b 2.2 and b 2.3 in the melt at a temperature of 250 to 350 ° C., with the proviso that the sum of the percentages by weight of b 2.1 , b 2.2 and b 2.3 is in each case 100% by weight added, and
b₁) 50 bis 80 Gew.% eines linearen thermoplastischen Polyamids und
b₂) 20 bis 50 Gew.% eines modifizierten Polyphenylenethers hergestellt aus
b2.1 90 bis 99 Gew.% Polyphenylenether der bis zu 20 Gew.% durch Polystyrol ersetzt sein kann und
b2.2 1 bis 10 Gew.% mindestens einer Verbindung ausgewählt aus der Gruppe Fumarsäure deren Alkylester, Halbester, Halbamid, Maleinimid und/oder (Meth)acrylamid
durch Mischen der Komponenten b2.1 und b2.2 in der Schmelze bei einer Temperatur von 250 bis 350°C
b₁) 50 to 80 wt.% Of a linear thermoplastic polyamide and
b₂) 20 to 50 wt.% Of a modified polyphenylene ether made from
b 2.1 90 to 99% by weight of polyphenylene ether which can be replaced by up to 20% by weight of polystyrene and
b 2.2 1 to 10% by weight of at least one compound selected from the group consisting of fumaric acid, its alkyl ester, half-ester, half-amide, maleimide and / or (meth) acrylamide
by mixing components b 2.1 and b 2.2 in the melt at a temperature of 250 to 350 ° C
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3818424 | 1988-05-31 | ||
| DE19883818424 DE3818424A1 (en) | 1988-05-31 | 1988-05-31 | THREADS FROM LINEAR THERMOPLASTIC POLYAMIDES AND MODIFIED POLYPHENYLENE ETHERS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0344590A2 true EP0344590A2 (en) | 1989-12-06 |
| EP0344590A3 EP0344590A3 (en) | 1991-01-23 |
Family
ID=6355473
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19890109325 Withdrawn EP0344590A3 (en) | 1988-05-31 | 1989-05-24 | Fibres from linear thermoplastic polyamides and modified polyphenylene ethers |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0344590A3 (en) |
| JP (1) | JPH02104724A (en) |
| DE (1) | DE3818424A1 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993013251A1 (en) * | 1991-12-24 | 1993-07-08 | Allied-Signal Inc. | Polymeric monofilament and felt made therefrom |
| EP0609792A1 (en) * | 1993-02-03 | 1994-08-10 | Basf Corporation | Modified nylon fibers |
| US5554693A (en) * | 1994-10-11 | 1996-09-10 | General Electric Company | Compositions of polyphenylene ether and polyamide resins containing terpene phenol resins |
| US5869572A (en) * | 1986-01-27 | 1999-02-09 | General Electric Company | Polymer mixture which comprises a polyamide, a polyphenylene ether and an agent to improve the impact resistance |
| WO2012001537A1 (en) * | 2010-06-29 | 2012-01-05 | Sabic Innovative Plastics Ip B.V. | Polyamide-poly(arylene ether) fiber and method for its preparation |
| US9090999B2 (en) | 2011-09-28 | 2015-07-28 | Sabic Global Technologies B.V. | Polyamide/polyphenylene ether fibers and fiber-forming method |
| US20170009385A1 (en) * | 2015-07-07 | 2017-01-12 | Voith Patent Gmbh | Monofilament, fabric and production method |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3950410B2 (en) * | 2002-12-10 | 2007-08-01 | 名古屋油化株式会社 | Fiber, fiber assembly, fiber assembly molding |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0046040A1 (en) * | 1980-08-13 | 1982-02-17 | Asahi Kasei Kogyo Kabushiki Kaisha | A highly heat-resistant thermoplastic resin composition having high oil-resistance and articles molded therefrom |
| EP0253123A1 (en) * | 1986-06-07 | 1988-01-20 | BASF Aktiengesellschaft | Thermoplastic moulding compositions |
| US4745157A (en) * | 1986-12-18 | 1988-05-17 | General Electric Company | Impact modification of polyphenylene ether-polyamide compositions |
| EP0302485A2 (en) * | 1987-08-07 | 1989-02-08 | BASF Aktiengesellschaft | Thermoplastic molding compositions |
| EP0314000A2 (en) * | 1987-10-30 | 1989-05-03 | BASF Aktiengesellschaft | Thermoplastic moulding composition |
-
1988
- 1988-05-31 DE DE19883818424 patent/DE3818424A1/en not_active Withdrawn
-
1989
- 1989-05-24 EP EP19890109325 patent/EP0344590A3/en not_active Withdrawn
- 1989-05-24 JP JP12903389A patent/JPH02104724A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0046040A1 (en) * | 1980-08-13 | 1982-02-17 | Asahi Kasei Kogyo Kabushiki Kaisha | A highly heat-resistant thermoplastic resin composition having high oil-resistance and articles molded therefrom |
| EP0253123A1 (en) * | 1986-06-07 | 1988-01-20 | BASF Aktiengesellschaft | Thermoplastic moulding compositions |
| US4745157A (en) * | 1986-12-18 | 1988-05-17 | General Electric Company | Impact modification of polyphenylene ether-polyamide compositions |
| EP0302485A2 (en) * | 1987-08-07 | 1989-02-08 | BASF Aktiengesellschaft | Thermoplastic molding compositions |
| EP0314000A2 (en) * | 1987-10-30 | 1989-05-03 | BASF Aktiengesellschaft | Thermoplastic moulding composition |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5869572A (en) * | 1986-01-27 | 1999-02-09 | General Electric Company | Polymer mixture which comprises a polyamide, a polyphenylene ether and an agent to improve the impact resistance |
| WO1993013251A1 (en) * | 1991-12-24 | 1993-07-08 | Allied-Signal Inc. | Polymeric monofilament and felt made therefrom |
| EP0609792A1 (en) * | 1993-02-03 | 1994-08-10 | Basf Corporation | Modified nylon fibers |
| US5559194A (en) * | 1993-02-03 | 1996-09-24 | Basf Corportion | Modified nylon fibers |
| US5618885A (en) * | 1993-02-03 | 1997-04-08 | Basf Corporation | Fiber-forming modified polyamide blends |
| US5623024A (en) * | 1993-02-03 | 1997-04-22 | Basf Corporation | Process for melt-spinning fibers from modified polyamide blends |
| US5554693A (en) * | 1994-10-11 | 1996-09-10 | General Electric Company | Compositions of polyphenylene ether and polyamide resins containing terpene phenol resins |
| WO2012001537A1 (en) * | 2010-06-29 | 2012-01-05 | Sabic Innovative Plastics Ip B.V. | Polyamide-poly(arylene ether) fiber and method for its preparation |
| US9090999B2 (en) | 2011-09-28 | 2015-07-28 | Sabic Global Technologies B.V. | Polyamide/polyphenylene ether fibers and fiber-forming method |
| US20170009385A1 (en) * | 2015-07-07 | 2017-01-12 | Voith Patent Gmbh | Monofilament, fabric and production method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02104724A (en) | 1990-04-17 |
| EP0344590A3 (en) | 1991-01-23 |
| DE3818424A1 (en) | 1989-12-07 |
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