DE3051066C2 - - Google Patents
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- Publication number
- DE3051066C2 DE3051066C2 DE3051066A DE3051066A DE3051066C2 DE 3051066 C2 DE3051066 C2 DE 3051066C2 DE 3051066 A DE3051066 A DE 3051066A DE 3051066 A DE3051066 A DE 3051066A DE 3051066 C2 DE3051066 C2 DE 3051066C2
- Authority
- DE
- Germany
- Prior art keywords
- solvent
- filament
- polyethylene
- filaments
- temperature
- 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.)
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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
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/12—Stretch-spinning methods
- D01D5/16—Stretch-spinning methods using rollers, or like mechanical devices, e.g. snubbing pins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/05—Filamentary, e.g. strands
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0058—Liquid or visquous
- B29K2105/0073—Solution
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Artificial Filaments (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Woven Fabrics (AREA)
Description
Die Erfindung bezieht sich auf Polyäthylenfilamente mit einer Zugfestigkeit von mindestens 1,2 GPa und mit großem Modul; s. US-PS 41 37 394.The invention relates to polyethylene filaments tensile strength of at least 1.2 GPa and high Module; s. U.S. Patent 41 37 394.
Filamente werden normalerweise durch Verspinnen linearer Polymerisate hergestellt. Das Polymerisat wird dabei in eine Flüssigform (Schmelze, Lösung) gebracht und versponnen. Die im gebildeten Filament willkürlich orientierten Molekülketten müssen danach durch Dehnen in die Längsrichtung des Filaments gerichtet werden. Wiewohl auch andere Stoffe verspinnbar sein können, sind kettenförmige Makromoleküle eine wichtige Voraussetzung für die Vorspinnbarkeit zu Filamenten. Verzweigungen beeinflussen die Filamentbildung und die mechanischen Eigenschaften im negativen Sinn. Aus diesem Grund geht man für das Herstellen von Filamenten soviel wie möglich von linearen Polymerisaten aus, wenn auch ein geringes Maß der Verzweigung sich meistens nicht vermeiden läßt und übrigens auch zulässig ist.Filaments are usually made more linear by spinning Polymers made. The polymer is in one Liquid form (melt, solution) brought and spun. The arbitrarily oriented molecular chains in the formed filament must then be stretched in the longitudinal direction of the filament be judged. Although other fabrics can also be spun chain-shaped macromolecules are an important prerequisite for the prefinnability to filaments. Ramifications affect filament formation and mechanical properties in a negative sense. This is why you go for that Make filaments as much as possible from linear Polymers, albeit a small degree of branching can usually not be avoided and, by the way, also permissible is.
Durch das Dehnen von Filamenten werden die kettenförmigen Makromoleküle in die Längsrichtung orientiert, wobei die Festigkeit der Filamente zunimmt. Die Festigkeit bleibt jedoch in vielen Fällen weit unter den Werten, die man theoretisch erwarten dürfte. Es sind bereits viele Versuche unternommen worden, Filamente herzustellen, deren Zugfestigkeit und Modul den theoretischen Möglichkeiten besser entsprechen. Diese Versuche, über die in Veröffentlichungen von Juyn in Plastica, 31 (1978), 262-270, und von Bigg in Polymer Eng. Sci., 16 (1976), 725-734, eine Übersicht gegeben ist, haben keine befriedigenden Ergebnisse gezeigt. In einigen Fällen konnte wohl der Modul, allerdings nicht die Zugfestigkeit, in ausreichendem Maße verbessert werden; außerdem verläuft die Filamentbildung meistens so langsam, daß eine wirtschaftlich vertretbare Produktion nicht möglich ist. Letzteres gilt auch für die Filamente nach der US-PS 41 37 394, deren Herstellungsgeschwindigkeit durch die Kristallisationsgeschwindigkeit in Filament-Längsrichtung limitiert ist.By stretching the filaments, the chain-like Macromolecules oriented in the longitudinal direction, the Strength of the filaments increases. However, the strength remains in many cases far below the values you theoretically expected. Many attempts have already been made been producing filaments, their tensile strength and modulus correspond better to the theoretical possibilities. These attempts on the in publications by Juyn in Plastica, 31 (1978), 262-270, and by Bigg in Polymer Eng. Sci., 16 (1976), 725-734, given an overview, have no satisfactory results shown. In some cases the module could, however not the tensile strength, improved to a sufficient extent will; moreover, filament formation is usually so slow that economically viable production is not is possible. The latter also applies to the filaments after the US-PS 41 37 394, the manufacturing speed of which Crystallization speed in the longitudinal direction of the filament is limited.
Der Erfindung liegt die Aufgabe zugrunde, Polyäthylenfilamente mit hoher Festigkeit und mit unter Zugbelastung praktisch gleichbleibendem, hohem Modul bereitzustellen, die wirtschaftlich herstellbar sind. Diese Aufgabe wird bei Polyäthylenfilamenten eingangs genannter Art durch die mittels der kennzeichnenden Maßnahmen erzielten Eigenschaften gelöst.The invention has for its object polyethylene filaments with high strength and practical with tensile load provide consistent, high module that is economical are producible. This task is done with polyethylene filaments initially mentioned type by means of the characterizing Measures achieved properties solved.
Beim sog. Trockenspinnen, einem in technischem Maßstab angewandten, allgemein bekannten Verfahren, wird eine Lösung eines verspinnbaren Polymerisats in einem Schacht versponnen, durch den - meistens erwärmte - Luft geblasen wird, um das Lösungsmittel ganz oder großenteils aus dem Filament zu verdampfen. Die Temperatur im Schacht ist dabei unter dem Schmelzpunkt des Polymerisats, so daß dies beim Verdampfen des Lösungsmittels niederschlägt, wodurch die mechanische Stärke des Filaments, die beim Austreten aus der Spinnöffnung noch sehr gering ist, zunimmt. Die Stärke wird danach während des Dehnens bei einer Temperatur unter dem Schmelzpunkt des Polymerisats erhöht.In so-called dry spinning, an applied on a technical scale, generally known method, will be a solution to one spinnable polymer spun in a shaft, by which - mostly warmed - air is blown around the solvent evaporate completely or largely from the filament. The temperature in the shaft is below the melting point of the Polymer, so that this when the solvent evaporates precipitates, which increases the mechanical strength of the filament, which is still very small when exiting the spinning opening, increases. The strength will then increase while stretching at one Temperature raised below the melting point of the polymer.
Erfindungsgemäß wird nunmehr das Verdampfen des Lösungsmittels aus dem soeben gesponnenen Filament während dessen Kühlphase nicht gefördert. Das Filament kann in jeder geeigneten Weise bis unter den Lösungspunkt und insbesondere bis unter den Quellpunkt des Polymerisats im Lösungsmittel abgekühlt werden, z. B. indem das Filament in ein Wasserbad oder durch einen Schacht geleitet wird, wobei durch den Schacht keine oder nahezu keine Luft geblasen wird. Eine geringe Verdampfung des Lösungsmittels aus dem Filament wird oft von selbst stattfinden und nicht vermieden werden können. Es schadet nicht im geringsten, solange man die Verdampfung nicht aktiv fördert und die Menge des Lösungsmittels im Filament nicht bis auf einen niedrigen Wert, d. h. nicht unter 25 Gew.-%, vorzugsweise nicht bis unter gleiche Gewichtsmengen an Lösungsmittel in bezug auf das Polymerisat verringert. Unter Umständen kann man eine Verdampfung des Lösungsmittels verringern oder sie verhüten, indem man es in einer Lösungsmitteldampf enthaltenden Atmosphäre verspinnt. The evaporation of the solvent is now according to the invention from the filament just spun during its cooling phase not funded. The filament can be in any suitable way to below the solution point and in particular up to the source point of the polymer are cooled in the solvent, for. B. by placing the filament in a water bath or through a manhole is passed, with no or almost none through the shaft Air is blown. Little evaporation of the solvent often from the filament will take place by itself and not can be avoided. It doesn't hurt in the slightest as long you don't actively promote evaporation and the amount of the solvent in the filament not to a low level Value, d. H. not less than 25% by weight, preferably not to less than equal amounts by weight of solvent with respect to the polymer decreased. Under certain circumstances you can see evaporation reduce or prevent the solvent by using it spun in an atmosphere containing solvent vapor.
Beim Abkühlen bis unter den Lösungspunkt und insbesondere bis unter den Quellpunkt des Polymerisats im Lösungsmittel schlägt sich das Polymerisat aus der Lösung nieder, und es entsteht ein Gel. Ein aus diesem polymeren Gel bestehendes Filament weist eine ausreichende mechanische Stärke auf, um weiterverarbeitet werden zu können, z. B. über in der Spinntechnik übliche Führungselemente, Rollen usw. Ein solches Filament wird bis auf eine Temperatur zwischen dem Quellpunkt des Polymerisats im Lösungsmittel und dem Schmelzpunkt des Polymerisats erwärmt und bei dieser Temperatur gedehnt. Dies kann dadurch geschehen, daß das Filament in eine Zone mit einem gasförmigen oder einen flüssigen Medium eingeleitet wird, die auf der gewünschten Temperatur gehalten wird. Ein Rohrofen mit Luft als gasförmigem Medium ist sehr geeignet, aber man kann auch ein Flüssigkeitsbad oder jede andere dazu geeignete Vorrichtung verwenden. Ein gasförmiges Medium ist leichter zu handhaben und hat den Vorzug.When cooling down to below the solution point and in particular to below the swelling point of the polymer in the solvent the polymer precipitates out of the solution and it forms a gel. A filament made from this polymeric gel has sufficient mechanical strength to be processed to be able to B. over in spinning technology usual guide elements, rollers, etc. Such a filament is brought up to a temperature between the source point of the Polymer in the solvent and the melting point of the polymer warmed and stretched at this temperature. This can done by placing the filament in a zone with a gaseous or a liquid medium is introduced, which is kept at the desired temperature. A tube furnace with air as the gaseous medium is very suitable, however one can also use a liquid bath or any other suitable one Use the device. It is a gaseous medium easier to use and preferred.
Beim Dehnen des Filaments wird Lösungsmittel verdampfen oder - wenn eine Flüssigkeit als Medium eingesetzt wird - sich in der Flüssigkeit auflösen. Vorzugsweise fördert man die Verdampfung durch dazu geeignete Maßnahmen, wie Abfuhr des Lösungsmitteldampfs, z. B. dadurch, daß ein Gas- oder ein Luftstrom in der Dehnzone am Filament entlang geleitet wird. Das Lösungsmittel soll mindestens teilweise verdampfen, aber vorzugsweise läßt man es mindestens großenteils verdampfen, so daß das Filament am Ende der Dehnzone höchstens noch eine geringe Menge, z. B. nicht mehr als einige Prozent, berechnet auf den Feststoff, des Lösungsmittels enthält. Das schließlich erhaltene Filament soll lösungsmittelfrei sein, und zweckmäßig wählt man die Bedingungen derart, daß dieser Zustand bereits in der Dehnzone erreicht wird, jedenfalls nahezu erreicht wird.When the filament is stretched, solvent will evaporate or - if a liquid is used as a medium - in the Dissolve liquid. Evaporation is preferably promoted through suitable measures, such as removal of the solvent vapor, e.g. B. in that a gas or air flow in the Stretch zone along the filament. The solvent should evaporate at least partially, but preferably leaves you evaporate it at least largely so that the filament At the end of the expansion zone, at most a small amount, e.g. B. not more than a few percent, calculated on the solid, contains the solvent. The filament finally received should be solvent-free, and appropriately you choose the conditions such that this condition is already in the expansion zone is achieved, in any case almost reached.
Überraschenderweise sind die erfindungsgemäßen Filamente bedeutend stärker als solche aus dem gleichen Material, die nach einem üblichen Trockenspinnverfahren hergestellt worden sind, d. h., Zugfestigkeit und Modul der in Frage stehenden Filamente sind bedeutend besser. Nach den in den vorstehend genannten Veröffentlichungen von Juyn und Bigg beschriebenen Verfahren ist es zwar gelungen, Filamente mit größerem Modul herzustellen, jedoch läßt die Zugfestigkeit immer noch sehr zu wünschen übrig. Außerdem ist die Produktivität solcher Verfahren niedrig.Surprisingly, the filaments of the invention are important stronger than those made from the same material after a usual dry spinning process have been produced, d. i.e., tensile strength and modulus of the filaments in question are significantly better. After the in the aforementioned publications by Juyn and Bigg described process has succeeded in filaments with larger To produce a module, but the tensile strength is still very high wish left. In addition, the productivity of such processes low.
Eine Bedingung für das Trockenspinnen ist die Löslichkeit des linearen Polymerisats in einem geeigneten Lösungsmittel. Für jedes lösbare Polymerisat ist eine Anzahl Lösungsmittel bekannt. Der Experte kann aus ihnen mühelos ein geeignetes Lösungsmittel herausfinden, dessen Siedepunkt nicht so hoch liegt, daß es sich schwer aus dem Filament verdampfen läßt, und nicht so niedrig, daß es zu flüchtig ist und durch zu schnelle Verdampfung die Filamentbildung stören würde oder sonst unter Druck verarbeitet werden muß.Solubility is a condition for dry spinning of the linear polymer in a suitable solvent. For a number of solvents are known for each soluble polymer. The expert can easily use them to find a suitable solvent find out whose boiling point is not so high that it is difficult to evaporate from the filament, and not so low that it is too volatile and filament formation due to rapid evaporation would interfere or otherwise must be processed under pressure.
Das Auflösen eines Polymerisats in einem geeigneten Lösungsmittel verläuft über Quellung. Unter Aufnahme von Lösungsmittel und Zunahme des Volumens entsteht ein stark gequollenes Gel, das jedoch aufgrund seiner Steifigkeit und seiner Formbeständigkeit noch als eine Art Feststoff zu betrachten ist. Allgemein wird angenommen, daß das Polymerisat aus geordneten (kristallinen) und weniger geordneten (amorphen) Bereichen aufgebaut ist. Die geordneten Bereiche würden jetzt als Verankerungspunkte fungieren und so die Formbeständigkeit des Gels bewerkstelligen. Die Gelbildung und das Auflösen sind temperaturabhängig. Ein bestimmtes Polymerisat kann nur über einer gewissen Temperatur in einem gewissen Lösungsmittel aufgelöst werden. Unter dieser Lösungstemperatur findet nur Quellung statt, und je nachdem die Temperatur niedriger ist, wird die Quellung geringer und ist auf einmal zu vernachlässigen. Als Quellpunkt oder Quelltemperatur wird die Temperatur betrachtet, bei der eine klar wahrnehmbare Volumenvergrößerung und eine deutlich wahrnehmbare Lösungsmittelaufnahme von 5 bis 10% des Polymerisatgewichts eintritt. Einfachheitshalber wählt man als Quelltemperatur, über der gedehnt werden muß, die Temperatur, bei der unzweideutig 10% Lösungsmittel unter Quellung in das Polymerisat aufgenommen werden.Dissolving a polymer in a suitable solvent runs through swelling. Including solvent and Increasing the volume creates a heavily swollen gel, however due to its stiffness and dimensional stability a kind of solid is to be considered. It is generally believed that the polymer from ordered (crystalline) and less ordered (amorphous) areas. The ordered areas would now act as anchoring points and thus the dimensional stability of the gel. The gelation and dissolution are temperature dependent. A certain polymer can only have one certain temperature dissolved in a certain solvent will. Only swelling takes place below this solution temperature, and as the temperature is lower, the swelling becomes less and is suddenly negligible. As source point or Source temperature is considered the temperature at which a clear perceptible volume increase and a clearly perceptible Solvent absorption of 5 to 10% of the polymer weight occurs. For the sake of simplicity, choose the source temperature above which must be stretched, the temperature at which unambiguously 10% Solvents are swelled into the polymer.
Bei üblichen Trockenspinnverfahren verarbeitet man aus spinntechnischen und wirtschaftlichen Gründen meistens 5- bis 30gew.-%ige Lösungen. Diese sind auch für das in Frage stehende Verfahren zur Herstellung der erfindungsgemäßen Filamente geeignet, wenn man dabei auch im allgemeinen weniger konzentrierte Lösungen gebrauchen wird. Zweckmäßig verwendet man 1- bis 5gew.-%ige Lösungen. Auch noch niedrigere Konzentrationen sind möglich, wenn sie auch keine Vorteile ergeben und in wirtschaftlicher Hinsicht unvorteilhaft sind.In conventional dry spinning processes one processes out spinning and economic reasons mostly 5- to 30% by weight solutions. These are also for that in question Processes for producing the filaments according to the invention are suitable, although in general less will use concentrated solutions. One uses expediently 1 to 5% by weight solutions. Even lower concentrations are possible if they do not give any advantages either are economically disadvantageous.
Geeignete Dehnungsverhältnisse lassen sich leicht experimentell feststellen. Die Zugfestigkeit und der Modul der Filamente sind innerhalb gewisser Grenzen etwa proportional zum Dehnungsverhältnis. Je nachdem stärkere Filamente erwünscht sind, wird das Dehnungsverhältnis größer gewählt werden müssen.Suitable expansion ratios can be easily experimented determine. The tensile strength and the modulus of the filaments are within certain limits approximately proportional to the expansion ratio. Depending on which thicker filaments are desired, this will be Elongation ratio must be chosen larger.
Man dehnt mindestens um das Zehnfache, insbesondere mindestens das Zwanzigfache. Große Dehnungsverhältnisse von 30 bis 40 und sogar mehr sind durchaus möglich, und man erhält dabei Filamente, deren Zugfestigkeit und Modul erheblich größer sind als die der nach dem üblichen Verfahren hergestellten Filamente.You stretch at least ten times, especially at least twenty times. Large expansion ratios from 30 to 40 and even more are quite possible and you get filaments, their tensile strength and modulus are considerably larger than that of the usual method manufactured filaments.
Bei üblichen Trockenspinnverfahren sind die Durchmesser der Spinnöffnungen in den Spinndüsen meistens klein. Im allgemeinen sind sie 0,02 bis 1,0 mm. Besonders wenn kleine Spinnöffnungen (<0,2 mm) verwendet werden, ist das Spinnverfahren für Verunreinigungen in der Spinnlösung sehr empfindlich und muß man sie sorgfältigst von festen Verunreinigungen freimachen und -halten. An den Spinndüsen werden meistens Filter angeordnet. Trotzdem müssen sie nach kurzer Zeit gereinigt werden und ergeben sich noch wiederholt Verstopfungen. In conventional dry spinning processes, the diameters are Spinning orifices in the spinnerets are usually small. Generally are they 0.02 to 1.0 mm. Especially when small spinning openings (<0.2 mm) used is the spinning process for impurities in the Spinning solution very sensitive and you have to be careful of it Clear and hold solid contaminants. On the spinnerets filters are usually arranged. Nevertheless, after a short time Time to be cleaned and there are still repeated constipations.
Bei dem in Frage stehenden Verfahren kann man größere Spinnöffnungen von mehr als 0,2 mm, z. B. 0,5 bis 2,0 mm oder mehr, verwenden, und zwar dadurch, daß bedeutend größere Dehnungsverhältnisse und außerdem meistens niedrigere Polymerisatkonzentrationen in der Spinnlösung verwendet werden.In the process in question, one can use larger spinning orifices of more than 0.2 mm, e.g. B. 0.5 to 2.0 mm or more, and indeed by the fact that significantly larger expansion ratios and also usually lower polymer concentrations in the spinning solution be used.
Polyäthylen kann man gut in Kohlenwasserstoffen, wie gesättigten aliphatischen und zyklischen sowie aromatischen Kohlenwasserstoffen oder Gemischen aus diesen, wie Erdölfraktionen, auflösen. Sehr geeignet sind aliphatische oder zyklische Kohlenwasserstoffe, wie Nonan, Decan, Undecan, Dodecan, Tetralin, Decalin usw. oder Erdölfraktionen mit entsprechenden Siedebereichen. Polyäthylen löst man vorzugsweise in Decalin oder Dodecan auf.Polyethylene you can do well in hydrocarbons, like saturated aliphatic and cyclic as well aromatic hydrocarbons or mixtures of these, such as Petroleum fractions, dissolve. Aliphatic or are very suitable cyclic hydrocarbons, such as nonane, decane, undecane, dodecane, Tetralin, decalin etc. or petroleum fractions with corresponding ones Boiling ranges. Polyethylene is preferably dissolved in decalin or dodecane.
Die erfindungsgemäßen Filamente sind für viele Anwendungen geeignet. Man kann sie als Verstärkung in vielen Materialien verwenden, deren Verstärkung mit Fasern oder Filamenten bekannt ist, für Bandgarne und für allerhand mögliche Anwendungen, bei denen ein geringes Gewicht zusammen mit einer großen Stärke gewünscht ist. Selbstverständlich sind die Anwendungsmöglichkeiten nicht auf die genannten beschränkt.The filaments of the invention are for many applications suitable. You can use it as reinforcement in many materials, whose reinforcement with fibers or filaments is known, for ribbon yarns and for all kinds of applications where a light weight together with a great strength is desired is. Of course, the possible uses are not limited to the above.
Die Erfindung wird durch das nachstehende Beispiel erläutert, ohne dadurch beschränkt zu werden.The invention is illustrated by the example below. without being limited by it.
Ein hochmolekulares Polyäthylen mit einem w ≃1,5×10⁶ wird bei 145°C zu einer 2gew.-%igen Lösung A in Decalin aufgelöst, die bei 130°C durch eine Spinndüse mit einer Spinnöffnung Durchmesser 0,5 mm versponnen wird. Das Filament wird in ein auf Zimmertemperatur gehaltenes Wasserbad B eingeleitet und darin abgekühlt. Das abgekühlte, 0,7 mm dicke Filament C, das ein gelartiges Äußeres hat und noch etwa 98% des Lösungsmittels enthält, wird über eine Führungsrolle D dann durch einen auf 120°C geheizten Rohrofen E und über eine Streckrolle F geleitet und mit mehreren Dehnungsverhältnissen gedehnt.A high molecular weight polyethylene with one w ≃1.5 × 10⁶ becomes a 2% by weight solution at 145 ° CA dissolved in decalin, that at 130 ° C through a spinneret with a spinning orifice Diameter 0.5 mm is spun. The filament is in an on Water bath kept at room temperatureB initiated and cooled in it. The cooled, 0.7 mm thick filamentC.which is a gel-like Has exterior and still contains about 98% of the solvent, is about a leadership roleD then through a tube furnace heated to 120 ° CE and over a stretch rollF directed and with stretched several times.
In den Fig. 2 und 3 sind die Zugfestigkeit bzw. der Modul gegen das Dehnungsverhältnis aufgetragen. Es können ein Modul von mehr als 60 GPa und eine Zugfestigkeit von fast 3 erreicht werden, während der Modul und die Zugfestigkeit von auf herkömmliche Weise hergestellten gesponnenen Polyäthylenfilamenten 2 bis 3 GPa bzw. etwa 0,1 GPa betragen. Die in die Fig. 2 und 3 eingetragenen Werte für den Modul und die Zugfestigkeit von Filamenten mit verschiedenen Dehnungsverhältnissen sind in der Tabelle 1 erwähnt.In FIGS. 2 and 3, the tensile strength or the modulus versus the elongation ratio are plotted. A modulus of more than 60 GPa and a tensile strength of almost 3 can be achieved, while the modulus and tensile strength of conventionally produced spun polyethylene filaments are 2 to 3 GPa and approximately 0.1 GPa, respectively. The values for the module and the tensile strength of filaments with different elongation ratios entered in FIGS. 2 and 3 are mentioned in Table 1.
Polyäthylenfilamente mit einer Zugfestigkeit über 1,2 GPa lassen sich leicht nach dem in Frage stehenden Verfahren herstellen. Polyethylene filaments with a tensile strength above 1.2 GPa can be easily manufactured using the process in question.
Claims (1)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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NLAANVRAGE7900990,A NL177840C (en) | 1979-02-08 | 1979-02-08 | METHOD FOR MANUFACTURING A POLYTHENE THREAD |
Publications (1)
Publication Number | Publication Date |
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DE3051066C2 true DE3051066C2 (en) | 1987-12-10 |
Family
ID=19832598
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
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DE19803004699 Granted DE3004699A1 (en) | 1979-02-08 | 1980-02-08 | FILAMENTS WITH GREAT TENSILE STRENGTH AND LARGE MODULE |
DE3051066A Expired DE3051066C2 (en) | 1979-02-08 | 1980-02-08 |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
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DE19803004699 Granted DE3004699A1 (en) | 1979-02-08 | 1980-02-08 | FILAMENTS WITH GREAT TENSILE STRENGTH AND LARGE MODULE |
Country Status (19)
Country | Link |
---|---|
JP (4) | JPS6047922B2 (en) |
AT (1) | AT380033B (en) |
AU (1) | AU532451B2 (en) |
BE (1) | BE881587A (en) |
BR (1) | BR8000775A (en) |
CA (1) | CA1152272A (en) |
CH (1) | CH650535C2 (en) |
CS (1) | CS235001B2 (en) |
DE (2) | DE3004699A1 (en) |
ES (1) | ES488304A1 (en) |
FR (1) | FR2448587B1 (en) |
GB (1) | GB2042414B (en) |
IN (1) | IN152729B (en) |
IT (1) | IT1144056B (en) |
MX (1) | MX6124E (en) |
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- 1980-02-06 AT AT0065280A patent/AT380033B/en not_active IP Right Cessation
- 1980-02-06 FR FR8002571A patent/FR2448587B1/en not_active Expired
- 1980-02-06 CS CS80810A patent/CS235001B2/en unknown
- 1980-02-06 ES ES488304A patent/ES488304A1/en not_active Expired
- 1980-02-07 SU SU802878003A patent/SU1138041A3/en active
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- 1980-02-07 IT IT47840/80A patent/IT1144056B/en active
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- 1980-02-07 GB GB8004157A patent/GB2042414B/en not_active Expired
- 1980-02-07 JP JP55014245A patent/JPS6047922B2/en not_active Expired
- 1980-02-07 SE SE8000997A patent/SE446105B/en not_active IP Right Cessation
- 1980-02-08 IN IN149/CAL/80A patent/IN152729B/en unknown
- 1980-02-08 DE DE19803004699 patent/DE3004699A1/en active Granted
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Also Published As
Publication number | Publication date |
---|---|
BE881587A (en) | 1980-08-07 |
ES488304A1 (en) | 1980-08-01 |
JPS648732B2 (en) | 1989-02-15 |
DE3004699C2 (en) | 1987-10-29 |
NL177840C (en) | 1989-10-16 |
FR2448587A1 (en) | 1980-09-05 |
IT8047840A0 (en) | 1980-02-07 |
NL177840B (en) | 1985-07-01 |
AU532451B2 (en) | 1983-09-29 |
JPS6245714A (en) | 1987-02-27 |
IT1144056B (en) | 1986-10-29 |
SU1138041A3 (en) | 1985-01-30 |
IN152729B (en) | 1984-03-24 |
NL7900990A (en) | 1980-08-12 |
MX6124E (en) | 1984-11-21 |
BR8000775A (en) | 1980-10-21 |
AT380033B (en) | 1986-03-25 |
DE3004699A1 (en) | 1980-08-21 |
GB2042414B (en) | 1982-12-22 |
JPS6075607A (en) | 1985-04-30 |
CH650535A5 (en) | 1985-07-31 |
AU5514880A (en) | 1980-08-14 |
JPS55107506A (en) | 1980-08-18 |
CS235001B2 (en) | 1985-04-16 |
ZA80528B (en) | 1981-01-28 |
CH650535C2 (en) | 1998-02-27 |
CA1152272A (en) | 1983-08-23 |
SE446105B (en) | 1986-08-11 |
SE8000997L (en) | 1980-08-09 |
JPS6075606A (en) | 1985-04-30 |
JPS6047922B2 (en) | 1985-10-24 |
FR2448587B1 (en) | 1985-08-23 |
ATA65280A (en) | 1985-08-15 |
GB2042414A (en) | 1980-09-24 |
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