EP0474027A2 - Process for the preparation of polyamide fibres with very high molecular weight - Google Patents
Process for the preparation of polyamide fibres with very high molecular weight Download PDFInfo
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- EP0474027A2 EP0474027A2 EP91113961A EP91113961A EP0474027A2 EP 0474027 A2 EP0474027 A2 EP 0474027A2 EP 91113961 A EP91113961 A EP 91113961A EP 91113961 A EP91113961 A EP 91113961A EP 0474027 A2 EP0474027 A2 EP 0474027A2
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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
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
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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
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
- D01F11/08—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Definitions
- the invention relates to a process for the production of particularly high molecular weight polyamide fibers and polyamide fibers produced by this process.
- the so-called technical polyamide fibers are used, among other things. used for netting and cordage, conveyor belt fabrics, industrial machine felts, filters, fishing wires, technical fabrics and guy wires as well as bristles. Since aliphatic polyamides generally have good chemical resistance, they are ideal for paper machine clothing. In addition to general good mechanical properties, such as high tensile strength, high requirements especially for properties that are subject to a bending process, e.g. Flexural strength and abrasion resistance. The latter are heavily dependent on the molecular weight of the polymer. The higher the degree of polymerization of the polymer, the more resistant the fibers are to bending stress.
- the polyamide granules are subjected to a solid-phase condensation, e.g. in US-PS 3 420 804 or in EP-PS 0 098 616.
- the disadvantage of this procedure is that the high molecular weight granulate has a very high melt viscosity and is therefore difficult to spin due to the high pressure build-up in front of the spinneret plate.
- uncontrolled molecular weight degradation occurs in the melt of high molecular weight granules during the spinning process.
- CH-PS 0 359 286 describes a process for the production of high molecular weight polyamide granules according to the post-condensation principle in two steps.
- the post-condensation catalysts are incorporated into the melt of the polyamide starting material and the post-condensation of the plastic parts obtained by injection molding or extrusion molding is then post-condensed. This procedure is unsuitable for the production of high molecular weight polyamide fibers because the incorporated catalysts trigger the post-condensation in an uncontrolled manner even in the hot polyamide spinning melt.
- Japanese Laid-Open Specification 27 719/76 describes the post-condensation of molded polyamide molded parts immersed in catalyst solution in order to increase the service life of molded parts subject to high stress by converting the two-dimensional molecular structure into a three-dimensional, i.e. by crosslinking the polyamide on the surface.
- Superficially cross-linked fibers are, however, severely disadvantaged in terms of staining and permanent bending stress.
- Japanese design specification 27 719/76 does not name fibers, but molded parts such as ring travelers and sliding rollers.
- the invention is therefore based on the object of producing particularly high molecular weight and uncrosslinked polyamide fibers with high flexural strength and good abrasion resistance.
- the invention provides a process for the post-condensation of melt-spun polyamide fibers in the solid phase in the presence of post-condensation catalysts, as well as the fibers produced by this process.
- polyamide fibers can be post-condensed in the solid phase without crosslinking and thus without showing the disadvantageous properties to be expected from their use.
- Normally viscous polyamide fibers are those with relative solution viscosities in H2SO4 of at most 4.2, preferably up to 4.0, particularly preferably those in the viscosity ranges around 3.4 and 3.8, particularly preferably around 3.8. They are made from ⁇ -aminocarboxylic acids or lactams with 4 to 12 carbon atoms or mixtures thereof, but preferably PA-4, PA-6, PA-11 and PA-12, or from aliphatic diamines with 4 to 12 carbon atoms and aliphatic dicarboxylic acids with 5 up to 12 carbon atoms or from their mixtures, but preferably PA-4.6, PA-6.6, PA-6.10 and PA-12.12.
- inorganic phosphorus compounds preferably salts or esters of phosphorous acid or orthophosphoric acid or these acids themselves are used, but particularly preferably H3PO4, H3PO3, Na2HPO4.12H2O, Na2HPO3.5H2O and NaH2PO4.
- the normally viscous polyamide fibers are made in a known manner, e.g. impregnated in a liquor, the catalyst content, based on the fibers to be condensed, being at most 0.5% by weight, preferably 0.1 to 0.3% by weight, particularly preferably 0.2% by weight.
- the post-condensation is carried out at temperatures of 160 to 200 ° C., preferably 170 to 190 ° C., in an inert gas atmosphere or in vacuo for 5 to 48 hours, preferably 6 to 24 hours, particularly preferably 8 to 12 hours.
- All polyamide types contain commercially available heat stabilizers from Ciba-Geigy / Switzerland of the Irganox type, with the exception of Grilon TM 26 highly viscous.
- the relative solution viscosities are measured as a 1% solution in 98% sulfuric acid according to DIN 53727 at 20 ° C.
- 17 dtex-PA-6 fibers of the Grilon TM 26 R type with 11 sheets per cm and relative solution viscosities of 3.36 are thermally post-condensed at 180 ° C. in vacuo during the times indicated in Table 1 without a catalyst.
- the amount of acid used is 0.2% by weight, based on the fibers to be condensed. After filtration and air drying, the mixture is post-condensed in a vacuum at 170 ° C. for 8 hours.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
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- Textile Engineering (AREA)
- Artificial Filaments (AREA)
- Polyamides (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von besonders hochmolekularen Polyamidfasern und nach diesem Verfahren hergestellte Polyamidfasern.The invention relates to a process for the production of particularly high molecular weight polyamide fibers and polyamide fibers produced by this process.
Die sogenannten technischen Polyamidfasern werden u.a. für Netz- und Tauwerk, Transportbandgewebe, Industriemaschinenfilze, Filter, Angeldrähte, technische Gewebe und Abspanndrähte sowie Borsten verwendet. Da aliphatische Polyamide im allgemeinen eine gute Chemikalienbeständigkeit aufweisen, eignen sie sich hervorragend für Papiermaschinenbespannungen. Hierbei werden neben allgemeinen guten mechanischen Eigenschaften, wie z.B. hoher Reissfestigkeit, hohe Anforderungen speziell an Eigenschaften, die einem Biegeprozess unterliegen, wie z.B. Biegesteifigkeit und Scheuerbeständigkeit, gestellt. Letztere sind stark von der Molmasse des Polymeren abhängig. Je höher der Polymerisationsgrad des Polymeren, desto beständiger sind die Fasern gegenüber Biegebeanspruchung.The so-called technical polyamide fibers are used, among other things. used for netting and cordage, conveyor belt fabrics, industrial machine felts, filters, fishing wires, technical fabrics and guy wires as well as bristles. Since aliphatic polyamides generally have good chemical resistance, they are ideal for paper machine clothing. In addition to general good mechanical properties, such as high tensile strength, high requirements especially for properties that are subject to a bending process, e.g. Flexural strength and abrasion resistance. The latter are heavily dependent on the molecular weight of the polymer. The higher the degree of polymerization of the polymer, the more resistant the fibers are to bending stress.
Nach dem Stand der Technik wird, um Polyamidfasern mit hohen Molmassen herstellen zu können, das Polyamidgranulat vor dem Verspinnen zu Fasern einer Festphasenkondensation unterworfen, wie z.B. in der US-PS 3 420 804 oder in der EP-PS 0 098 616 beschrieben. Nachteil dieser Vorgehensweise ist, dass das hochmolekulare Spinngranulat eine sehr hohe Schmelzviskosität besitzt und sich deshalb infolge eines hohen Durckaufbaus vor der Spinndüsenplatte nur noch schlecht verspinnen lässt. Ausserdem tritt in der Schmelze von hochmolekularem Granulat während des Spinnprozesses ein unkontrollierter Molmassenabbau ein. Die CH-PS 0 359 286 beschreibt ein Verfahren zur Herstellung von hochmolekularem Polyamidgranulat nach dem Nachkondensationsprinzip in zwei Schritten.According to the prior art, in order to be able to produce polyamide fibers with high molecular weights, the polyamide granules are subjected to a solid-phase condensation, e.g. in US-PS 3 420 804 or in EP-PS 0 098 616. The disadvantage of this procedure is that the high molecular weight granulate has a very high melt viscosity and is therefore difficult to spin due to the high pressure build-up in front of the spinneret plate. In addition, uncontrolled molecular weight degradation occurs in the melt of high molecular weight granules during the spinning process. CH-PS 0 359 286 describes a process for the production of high molecular weight polyamide granules according to the post-condensation principle in two steps.
Dabei werden die Nachkondensationskatalysatoren in die Schmelze des Polyamidausgangsmaterials eingearbeitet und anschliessend die Nachkondensation der durch Spritzguss oder Strangpressverformung erhaltenen Kunststoffteile nachkondensiert. Diese Verfahrensweise ist für die Herstellung von hochmolekularen Polyamidfasern ungeeignet, da die eingearbeiteten Katalysatoren die Nachkondensation bereits in der heissen Polyamidspinnschmelze in unkontrollierter Weise auslösen.The post-condensation catalysts are incorporated into the melt of the polyamide starting material and the post-condensation of the plastic parts obtained by injection molding or extrusion molding is then post-condensed. This procedure is unsuitable for the production of high molecular weight polyamide fibers because the incorporated catalysts trigger the post-condensation in an uncontrolled manner even in the hot polyamide spinning melt.
Die japanische Auslegeschrift 27 719/76 beschreibt die Nachkondensation von in Katalysatorlösung getauchten Polyamidformteilen in fester Phase zur Erhöhung der Lebensdauer von stark beanspruchten Formteilen durch die Überführung des zweidimensionalen Molekülverbandes in einen dreidimensionalen, d.h. durch Vernetzung des Polyamids an der Oberfläche. Oberflächlich vernetzte Fasern sind jedoch in der Anfärbung und bei Dauerbiegebelastung stark benachteiligt. (Abweichend zum WPI-Abstract nennt die japanische Auslegeschrift 27 719/76 keine Fasern, sondern Formteile wie Ringläufer und Schieberolle.)Japanese Laid-Open Specification 27 719/76 describes the post-condensation of molded polyamide molded parts immersed in catalyst solution in order to increase the service life of molded parts subject to high stress by converting the two-dimensional molecular structure into a three-dimensional, i.e. by crosslinking the polyamide on the surface. Superficially cross-linked fibers are, however, severely disadvantaged in terms of staining and permanent bending stress. (In contrast to the WPI abstract, Japanese design specification 27 719/76 does not name fibers, but molded parts such as ring travelers and sliding rollers.)
Der Erfindung liegt daher die Aufgabe zugrunde, besonders hochmolekulare und unvernetzte Polyamidfasern mit hoher Dauerbiegebelastbarkeit und guter Scheuerbeständigkeit herzustellen.The invention is therefore based on the object of producing particularly high molecular weight and uncrosslinked polyamide fibers with high flexural strength and good abrasion resistance.
Diese Aufgabe wird durch das Verfahren zur Herstellung von Polyamidfasern mit den Merkmalen des Anspruchs 1 bzw. durch Polyamidfasern nach Anspruch 12 gelöst.This object is achieved by the process for the production of polyamide fibers with the features of claim 1 or by polyamide fibers according to claim 12.
Die Erfindung stellt insbesondere ein Verfahren zur Nachkondensation schmelzgesponnener Polyamidfasern in fester Phase in Gegenwart von Nachkondensationskatalysatoren sowie die nach diesem Verfahren hergestellte Fasern zur Verfügung.In particular, the invention provides a process for the post-condensation of melt-spun polyamide fibers in the solid phase in the presence of post-condensation catalysts, as well as the fibers produced by this process.
Überraschenderweise wurde gefunden, dass sich Polyamidfasern in fester Phase nachkondensieren lassen, ohne zu vernetzen und damit ohne die nach dem Stand der Technik zu erwartenden nachteiligen Eigenschaften für ihre Verwendung zu zeigen.Surprisingly, it was found that polyamide fibers can be post-condensed in the solid phase without crosslinking and thus without showing the disadvantageous properties to be expected from their use.
Normalviskose Polyamidfasern sind solche mit relativen Lösungsviskositäten in H₂SO₄ von maximal 4,2, bevorzugt bis 4,0, besonders bevorzugt solche der Viskositätsbereiche um 3,4 und 3,8, besonders bevorzugt um 3,8. Sie sind hergestellt aus ω-Aminocarbonsäuren oder Lactamen mit 4 bis 12 Kohlenstoffatomen oder deren Gemischen, bevorzugt aber PA-4, PA-6, PA-11 und PA-12, oder aus aliphatischen Diaminen mit 4 bis 12 Kohlenstoffatomen und aliphatischen Dicarbonsäuren mit 5 bis 12 Kohlenstoffatomen oder aus deren Gemischen, bevorzugt aber PA-4.6, PA-6.6, PA-6.10 und PA-12.12.Normally viscous polyamide fibers are those with relative solution viscosities in H₂SO₄ of at most 4.2, preferably up to 4.0, particularly preferably those in the viscosity ranges around 3.4 and 3.8, particularly preferably around 3.8. They are made from ω-aminocarboxylic acids or lactams with 4 to 12 carbon atoms or mixtures thereof, but preferably PA-4, PA-6, PA-11 and PA-12, or from aliphatic diamines with 4 to 12 carbon atoms and aliphatic dicarboxylic acids with 5 up to 12 carbon atoms or from their mixtures, but preferably PA-4.6, PA-6.6, PA-6.10 and PA-12.12.
Als Nachkondensationskatalysatoren werden anorganische Phosphorverbindungen, bevorzugt Salze oder Ester der phosphorigen Säure oder der Orthophosphorsäure oder diese Säuren selbst eingesetzt, besonders bevorzugt aber H₃PO₄, H₃PO₃, Na₂HPO₄.12H₂O, Na₂HPO₃.5H₂O sowie NaH₂PO₄.As post-condensation catalysts, inorganic phosphorus compounds, preferably salts or esters of phosphorous acid or orthophosphoric acid or these acids themselves are used, but particularly preferably H₃PO₄, H₃PO₃, Na₂HPO₄.12H₂O, Na₂HPO₃.5H₂O and NaH₂PO₄.
Die normalviskosen Polyamidfasern werden in bekannter Weise, z.B. in einer Flotte, imprägniert, wobei der Katalysatorgehalt, bezogen auf die nachzukondensierenden Fasern, maximal 0,5 Gew.-% beträgt, bevorzugt 0,1 bis 0,3 Gew.-%, besonders bevorzugt 0,2 Gew.-%.The normally viscous polyamide fibers are made in a known manner, e.g. impregnated in a liquor, the catalyst content, based on the fibers to be condensed, being at most 0.5% by weight, preferably 0.1 to 0.3% by weight, particularly preferably 0.2% by weight.
Die Nachkondensation wird bei Temperaturen von 160 bis 200°C, bevorzugt 170 bis 190°C, in Inertgasatmosphäre oder im Vakuum während 5 bis 48 Stunden, bevorzugt 6 bis 24 Stunden, besonders bevorzugt 8 bis 12 Stunden ausgeführt.The post-condensation is carried out at temperatures of 160 to 200 ° C., preferably 170 to 190 ° C., in an inert gas atmosphere or in vacuo for 5 to 48 hours, preferably 6 to 24 hours, particularly preferably 8 to 12 hours.
Das erfindungsgemässe Verfahren hat folgende Vorteile:
- Es kann chargenweise, z.B. in einem Taumeltrockner oder mittels geeigneter Förderelemente kontinuierlich, z.B. in einem geneigten Drehrohrtrockner, ausgeführt werden.
- Ausgehend von normalviskosen, bevorzugt handelsüblichen Polyamidfasern lassen sich besonders hohe Molmassen mit Lösungsviskositäten in H₂SO₄ von mindestens 7,0, bevorzugt mindestens 9,0 erreichen. Fasern mit so extrem hohen Viskositäten können nicht mehr mit konventionellen Verfahren gesponnen werden.
- Mit dem erfindungsgemässen Verfahren lassen sich Polyamidfasern mit hervorragender Scheuerbeständigkeit mit einem vielfach erhöhten Wert der Drahtscheuertouren herstellen. Es lassen sich Fasern aus nicht vernetztem Polyamid herstellen, die gut löslich sind und keine Versprödung zeigen, d.h. Fasern, die keine verschlechterten Eigenschaften aufweisen, wie z.B. eine Erniedrigung der Reissdehnung. Damit darf angenommen werden, dass die erzielte Erhöhung der Molmasse durch weitere Amidbindungen im Polyamid und nicht durch Vernetzung erreicht wird.
- It can be carried out in batches, for example in a tumble dryer, or continuously, for example in an inclined rotary tube dryer, by means of suitable conveying elements.
- Starting from normal viscous, preferably commercially available polyamide fibers, particularly high molar masses with solution viscosities in H₂SO₄ of at least 7.0, preferably reach at least 9.0. Fibers with such extremely high viscosities can no longer be spun using conventional processes.
- With the method according to the invention, polyamide fibers with excellent abrasion resistance can be produced with a much higher value of the wire scrubbing tours. Fibers can be produced from non-crosslinked polyamide which are readily soluble and do not show embrittlement, ie fibers which have no deteriorated properties, such as a reduction in the elongation at break. It can therefore be assumed that the increase in molecular weight achieved is achieved through further amide bonds in the polyamide and not through crosslinking.
Die nachfolgenden Beispiele zeigen Ausführungsformen der Erfindung, ohne sie darauf zu beschränken. Die Ergebnisse der Prüfuntersuchungen sind tabellarisch zusammengefasst.The following examples show embodiments of the invention, without being restricted thereto. The results of the test examinations are summarized in a table.
Die in den Tabellen 1 bis 3 zusammengestellten Ergebnisse belegen, dass durch das erfindungsgemässe Nachkondensationsverfahren ein Anstieg der Lösungsviskosität, welche ein Mass für die Molmasse ist, und ein Anstieg der Drahtscheuertouren, die ein Mass für die Scheuerbeständigkeit sind, erreicht wird, ohne dass andere erwünschte Fasereigenschaften, wie z.B. Titer, Reissfestigkeit und Reissdehnung, negativ beeinflusst werden.The results summarized in Tables 1 to 3 show that the post-condensation process according to the invention achieves an increase in the solution viscosity, which is a measure of the molar mass, and an increase in the wire scrubbing tours, which are a measure of the scrub resistance, without other desired Fiber properties, such as Titer, tensile strength and elongation at break, are adversely affected.
Die in den Beispielen und Tabellen angegebenen Polyamidfasertypen sind:
- Grilon TM 26 R (EMS-CHEMIE AG/Schweiz): eine gekräuselte PA-6-Faser mit einer relativen Lösungsviskosität von ca. 3,30 bis 3,45
- Grilon TM 26/2 R (EMS-CHEMIE AG/Schweiz): eine gekräuselte PA-6-Faser mit einer relativen Lösungsvsikosität von ca. 3,70 bis 3,90
- Grilon TM 26 hochviskos (EMS-CHEMIE AG/Schweiz): eine gekräuselte PA-6-Faser mit einer relativen Lösungsviskosität von ca. 4,45 bis 4,60
- Nylon/T 310 (DuPont/USA): eine gekräuselte PA-6.6-Faser mit einer relativen Lösungsviskosität von ca. 3,00 bis 3,10
- Grilon TM 26 R (EMS-CHEMIE AG / Switzerland): a crimped PA-6 fiber with a relative solution viscosity of approx. 3.30 to 3.45
- Grilon TM 26/2 R (EMS-CHEMIE AG / Switzerland): a crimped PA-6 fiber with a relative solution viscosity of approx. 3.70 to 3.90
- Grilon TM 26 highly viscous (EMS-CHEMIE AG / Switzerland): a crimped PA-6 fiber with a relative solution viscosity of approx. 4.45 to 4.60
- Nylon / T 310 (DuPont / USA): a crimped PA-6.6 fiber with a relative solution viscosity of approx. 3.00 to 3.10
Alle Polyamidtypen enthalten handelsübliche Hitzestabilisatoren der Firma Ciba-Geigy/Schweiz vom Typ Irganox, ausgenommen Grilon TM 26 hochviskos.All polyamide types contain commercially available heat stabilizers from Ciba-Geigy / Switzerland of the Irganox type, with the exception of Grilon TM 26 highly viscous.
Die relativen Lösungsviskositäten werden als 1 %ige Lösung in 98 %iger Schwefelsäure gemäss DIN 53727 bei 20°C gemessen.The relative solution viscosities are measured as a 1% solution in 98% sulfuric acid according to DIN 53727 at 20 ° C.
17 dtex-PA-6-Fasern vom Typ Grilon TM 26 R mit 11 Bögen pro cm und relativen Lösungsviskositäten von 3,36 werden bei 180°C im Vakuum während der in Tabelle 1 angegebenen Zeiten ohne Katalysator thermisch nachkondensiert.17 dtex-PA-6 fibers of the Grilon ™ 26 R type with 11 sheets per cm and relative solution viscosities of 3.36 are thermally post-condensed at 180 ° C. in vacuo during the times indicated in Table 1 without a catalyst.
17 dtex-PA-6-Fasern vom Typ Grilon TM 26 R mit 11 Bögen pro cm und relativen Lösungsviskositäten von 3,36 werden mit einer wässrigen Lösung von Orthophosphorsäure (Verhältnis Faser : Wasser = 1 : 20) ohne Netzmittel 30 Minuten lang bei 95°C behandelt. Die eingesetzte Säuremenge beträgt 0,2 Gew.-% bezogen auf die nachzukondensierenden Fasern. Nach Filtration und Lufttrocknung erfolgt die Nachkondensation der so imprägnierten niederviskosen PA-6-Fasern bei 180°C im Vakuum während der in Tabelle 1 angegebenen Zeiten.17 Grilon TM 26 R dtex-PA-6 fibers with 11 sheets per cm and relative solution viscosities of 3.36 are mixed with an aqueous solution of orthophosphoric acid (ratio fiber: water = 1:20) without wetting agent at 95 for 30 minutes ° C treated. The amount of acid used is 0.2% by weight, based on the fibers to be condensed. After filtration and air drying, the post-condensation of the low-viscosity PA-6 fibers impregnated in this way is carried out at 180 ° C. in vacuo for the times given in Table 1.
Verfahren gemäss Beispiel 2 unter Verwendung von phosphoriger Säure.Process according to Example 2 using phosphorous acid.
Verfahren gemäss Beispiel 2 unter Verwendung von NaH₂PO₄.The method according to Example 2 using NaH₂PO₄.
Verfahren gemäss Beispiel 1 unter Verwendung von Fasern des Typs TM 26/2R-1 mit relativen Lösungsvikositäten von 3,72.Process according to Example 1 using fibers of the type TM 26 / 2R-1 with relative solution viscosities of 3.72.
Verfahren gemäss Beispiel 2 unter Verwendung von Fasern des Typs TM 26/2R-1 mit relativen Lösungsviskositäten von 3,72 und phosphoriger Säure.Process according to Example 2 using fibers of the type TM 26 / 2R-1 with relative solution viscosities of 3.72 and phosphorous acid.
Verfahren gemäss Beispiel 6 unter Verwendung von Orthophosphorsäure.Method according to Example 6 using orthophosphoric acid.
Verfahren gemäss Beispiel 1 unter Verwendung von Fasern des Typs TM 26/2R-2 mit relativen Lösungsviskositäten von 3,86.Process according to Example 1 using fibers of the type TM 26 / 2R-2 with relative solution viscosities of 3.86.
Verfahren gemäss Beispiel 2 unter Verwendung von Fasern des Typs TM 26/2R-2 mit relativen Lösungsviskositäten von 3,86 und phosphoriger Säure.Process according to Example 2 using fibers of the type TM 26 / 2R-2 with relative solution viscosities of 3.86 and phosphorous acid.
Verfahren gemäss Beispiel 9 unter Verwendung von Orthophosphorsäure.Method according to Example 9 using orthophosphoric acid.
Verfahren gemäss Beispiel 1 unter Verwendung von Fasern des Typs TM 26/2R-3 mit relativen Lösungsviskositäten von 3,88.Process according to Example 1 using fibers of the type TM 26 / 2R-3 with relative solution viscosities of 3.88.
Verfahren gemäss Beispiel 2 unter Verwendung von Fasern des Typs TM 26/2R-3 mit relativen Lösungsviskositäten von 3,88 und phosphoriger Säure.Process according to Example 2 using fibers of the type TM 26 / 2R-3 with relative solution viscosities of 3.88 and phosphorous acid.
Verfahren gemäss Beispiel 12 unter Verwendung von Orthophosphorsäure.Process according to Example 12 using orthophosphoric acid.
Verfahren gemäss Beispiel 1 unter Verwendung von Fasern des Typs TM 26/2R-4 mit relativen Lösungsviskositäten von 3,85.Process according to Example 1 using fibers of the type TM 26 / 2R-4 with relative solution viscosities of 3.85.
Verfahren gemäss Beispiel 2 unter Verwendung von Fasern des Typs TM 26/2R-4 mit relativen Lösungsviskositäten von 3,85 und phosphoriger Säure.Process according to Example 2 using fibers of the type TM 26 / 2R-4 with relative solution viscosities of 3.85 and phosphorous acid.
Verfahren gemäss Beispiel 15 unter Verwendung von Orthophosphorsäure.Method according to Example 15 using orthophosphoric acid.
Prüfresultate von gekräuselten PA-6-Fasern des Typs TM 26 hochviskos mit 11 Bögen pro cm und mit relativer Lösungsviskosität von 4,70 ohne Nachkondensation, die aus einer hochmolekularen, industriell nicht mehr verspinnbaren Polyamid-Extrusionsgranulat-Type (Grilon F50) mit relativen Lösungsviskositäten von 5,02 zu Fasern mit dem Titer von etwa 17 dtex versponnen wurden.Test results of crimped PA-6 fibers of the type TM 26 highly viscous with 11 sheets per cm and with a relative solution viscosity of 4.70 without post-condensation, which are made from a high molecular weight, industrially no longer spinnable polyamide extrusion granulate type (Grilon F50) with relative solution viscosities of 5.02 were spun into fibers with a titer of about 17 dtex.
Prüfresultate von 17 dtex PA-6.6-Fasern vom Typ Nylon/T 310 mit 11 Bögen pro cm und relativen Lösungsviskositäten von 3,07.Test results of 17 dtex PA-6.6 fibers of the type Nylon / T 310 with 11 sheets per cm and relative solution viscosities of 3.07.
17 dtex-PA-6.6-Fasern vom Typ Nylon/T 310 mit 11 Bögen pro cm und relativen Lösungsviskositäten von 3,07 werden mit einer wässrigen Lösung von Orthophosphorsäure (Verhältnis Faser : Wasser = 1 : 20) ohne Netzmittel 30 Minuten lang bei 95°C behandelt. Die eingesetzte Säuremenge beträgt 0,2 Gew.-%, bezogen auf die nachzukondensierenden Fasern. Nach Filtration und Lufttrocknung wird 8 Stunden bei 170°C im Vakuum nachkondensiert.17 dtex-PA-6.6 fibers of the type Nylon / T 310 with 11 sheets per cm and relative solution viscosities of 3.07 are mixed with an aqueous solution of orthophosphoric acid (ratio fiber: water = 1:20) without wetting agent at 95 for 30 minutes ° C treated. The amount of acid used is 0.2% by weight, based on the fibers to be condensed. After filtration and air drying, the mixture is post-condensed in a vacuum at 170 ° C. for 8 hours.
Verfahren gemäss Beispiel 19 unter Verwendung von phosphoriger Säure.
Claims (12)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4027063 | 1990-08-27 | ||
| DE4027063A DE4027063C2 (en) | 1990-08-27 | 1990-08-27 | Process for the production of particularly high molecular weight polyamide fibers and polyamide fibers which can be produced by this process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0474027A2 true EP0474027A2 (en) | 1992-03-11 |
| EP0474027A3 EP0474027A3 (en) | 1993-01-13 |
Family
ID=6413011
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19910113961 Withdrawn EP0474027A3 (en) | 1990-08-27 | 1991-08-21 | Process for the preparation of polyamide fibres with very high molecular weight |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5234644A (en) |
| EP (1) | EP0474027A3 (en) |
| JP (1) | JPH05156568A (en) |
| KR (1) | KR920004621A (en) |
| CA (1) | CA2048373C (en) |
| DE (1) | DE4027063C2 (en) |
| ES (1) | ES2033226T1 (en) |
| FI (1) | FI914011A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995016810A1 (en) * | 1993-12-16 | 1995-06-22 | Ems-Inventa Ag | Paper-machine felt |
| EP2188421A1 (en) | 2007-10-17 | 2010-05-26 | Invista Technologies S.A R.L. | Preparation of very high molecular weight polyamide filaments |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4839154A (en) * | 1986-12-29 | 1989-06-13 | Conoco Inc. | Process for converting sulfide ion to innocuous, solubile sulfur species |
| DE4434898C2 (en) * | 1993-12-16 | 1996-05-02 | Inventa Ag | Post-condensed paper machine felt made of polyamide base fabric and process for its production |
| US5677947A (en) * | 1995-08-25 | 1997-10-14 | International Teldata Corporation | Apparatus and method for operating a telephone line telemetry device in a multiple host environment |
| US5682422A (en) * | 1995-08-25 | 1997-10-28 | International Teldata Corporation | Apparatus and method for on-demand activation of telephone line telemetry devices |
| GB2309712A (en) * | 1996-02-05 | 1997-08-06 | Shell Int Research | Papermachine clothing woven from aliphatic polyketone fibres |
| US6083585A (en) * | 1996-09-23 | 2000-07-04 | Bp Amoco Corporation | Oxygen scavenging condensation copolymers for bottles and packaging articles |
| US5955569A (en) * | 1996-11-27 | 1999-09-21 | E.I. Du Pont De Nemours And Company | Method for solid phase polymerization |
| US6235390B1 (en) * | 1998-11-03 | 2001-05-22 | E. I. Du Pont De Nemours And Company | High RV filaments, and apparatus and processes for making high RV flake and the filaments |
| US6316518B1 (en) | 1999-02-05 | 2001-11-13 | Advanced Polymer Technology, Inc. | Methods of treating polymeric materials, methods of forming nylon, and apparatuses |
| US6169162B1 (en) | 1999-05-24 | 2001-01-02 | Solutia Inc. | Continuous polyamidation process |
| FR2796086B1 (en) | 1999-07-06 | 2002-03-15 | Rhodianyl | ABRASION RESISTANT WIRE ARTICLES |
| FR2984332B1 (en) * | 2011-12-15 | 2015-12-11 | Rhodia Operations | PROCESS FOR PREPARING POLYAMIDE PELLETS AND USES |
| ES2849428T3 (en) | 2013-05-02 | 2021-08-18 | Basf Se | Process to produce high viscosity polyamides |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3548584A (en) * | 1967-12-15 | 1970-12-22 | Monsanto Co | High molecular weight oriented polyamide textile yarn |
| US3562206A (en) * | 1967-12-15 | 1971-02-09 | Monsanto Co | Process for producing ultrahigh molecular weight polyamides |
| JPS5127719B1 (en) * | 1973-10-04 | 1976-08-14 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL110071C (en) * | 1955-10-08 | |||
| GB1044128A (en) * | 1964-06-03 | 1966-09-28 | British Nylon Spinners Ltd | Polyamides and a process and apparatus for their production |
| JPS5127719A (en) * | 1974-09-02 | 1976-03-08 | Japan Broadcasting Corp | |
| US4419400A (en) * | 1981-10-26 | 1983-12-06 | Occidental Chemical Corporation | Pultruded reinforced phenolic resin products |
| CA1198255A (en) * | 1982-07-08 | 1985-12-24 | Kazuyuki Kitamura | High tenacity polyhexamethylene adipamide fiber |
-
1990
- 1990-08-27 DE DE4027063A patent/DE4027063C2/en not_active Expired - Fee Related
-
1991
- 1991-08-02 CA CA002048373A patent/CA2048373C/en not_active Expired - Fee Related
- 1991-08-20 JP JP3207780A patent/JPH05156568A/en active Pending
- 1991-08-21 EP EP19910113961 patent/EP0474027A3/en not_active Withdrawn
- 1991-08-21 ES ES199191113961T patent/ES2033226T1/en active Pending
- 1991-08-26 FI FI914011A patent/FI914011A/en unknown
- 1991-08-27 KR KR1019910014834A patent/KR920004621A/en not_active Application Discontinuation
- 1991-08-27 US US07/750,831 patent/US5234644A/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3548584A (en) * | 1967-12-15 | 1970-12-22 | Monsanto Co | High molecular weight oriented polyamide textile yarn |
| US3562206A (en) * | 1967-12-15 | 1971-02-09 | Monsanto Co | Process for producing ultrahigh molecular weight polyamides |
| JPS5127719B1 (en) * | 1973-10-04 | 1976-08-14 |
Non-Patent Citations (2)
| Title |
|---|
| DATABASE WPI Section Ch, Week 7011, Derwent Publications Ltd., London, GB; Class A, AN 70-18519R & JP-B-45 007 025 (TORAY INDUSTRIES) * |
| DATABASE WPI Section Ch, Week 7637, Derwent Publications Ltd., London, GB; Class A, AN 76-69812X & JP-B-51 027 719 (TORAY INDUSTRIES) 15. August 1976 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995016810A1 (en) * | 1993-12-16 | 1995-06-22 | Ems-Inventa Ag | Paper-machine felt |
| US5783501A (en) * | 1993-12-16 | 1998-07-21 | Ems-Inventa Ag | Paper machine felts |
| EP2188421A1 (en) | 2007-10-17 | 2010-05-26 | Invista Technologies S.A R.L. | Preparation of very high molecular weight polyamide filaments |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05156568A (en) | 1993-06-22 |
| DE4027063C2 (en) | 1994-02-03 |
| US5234644A (en) | 1993-08-10 |
| KR920004621A (en) | 1992-03-27 |
| CA2048373A1 (en) | 1992-02-28 |
| CA2048373C (en) | 1998-11-17 |
| DE4027063A1 (en) | 1992-03-05 |
| FI914011A (en) | 1992-02-28 |
| ES2033226T1 (en) | 1993-03-16 |
| EP0474027A3 (en) | 1993-01-13 |
| FI914011A0 (en) | 1991-08-26 |
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