EP0000583B1 - High impact resistance polyamide compound and its use in mouldings - Google Patents
High impact resistance polyamide compound and its use in mouldings Download PDFInfo
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- EP0000583B1 EP0000583B1 EP78100511A EP78100511A EP0000583B1 EP 0000583 B1 EP0000583 B1 EP 0000583B1 EP 78100511 A EP78100511 A EP 78100511A EP 78100511 A EP78100511 A EP 78100511A EP 0000583 B1 EP0000583 B1 EP 0000583B1
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- polyamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
Definitions
- the invention relates to high-impact polymer alloys based on polyamides, which have a rel. Have a viscosity of at least 3.5 or a k-value of at least 83 (according to Fikentscher).
- the impact strength of moldings made of polyamide plastics depends considerably on the water content of the moldings.
- anhydrous e.g. After the molded articles have been produced by injection molding, those made from easy-flowing polyamide injection molding compositions with a medium molecular weight, and here again the molded articles made from highly crystalline polyamides, are relatively sensitive to impact stress.
- polyamides which have high tensile strength, high heat resistance, good resistance to solvents and easy processing, combined with high impact strength and flexibility.
- the impact resistance of polyamides is improved by admixing polymeric substances.
- Polyethylenes and copolymers of vinyl acetate and ethylene have been used with moderate success.
- GB-A-1 072 635 also teaches to modify polyolefins with 5-50% by weight polyamide to improve the solvent permeability of polyolefins, especially polyethylene.
- the flexibility of polyamides is increased by mixing in polyethylenes containing acid groups, e.g. Copolymers of ethylene and unsaturated acids or polyethylene grafted with unsaturated acids, increased.
- polyethylenes containing acid groups e.g. Copolymers of ethylene and unsaturated acids or polyethylene grafted with unsaturated acids
- Such mixtures are more finely dispersed and show a much lower whiteness when stressed than the mixtures described above, they have, apart from the somewhat improved toughness and flexibility, considerably poorer mechanical properties, such as e.g. Modulus of elasticity, tensile strength, hardness, rigidity as unmixed polyamide molding compounds (FR-A-13 86 563).
- polyamide alloys with a particularly high notched impact strength when freshly injected are obtained if polyamides, in particular polyamide-6 with a rel.
- Polyamide-6 with a relative viscosity of at least 3.5 is preferably used as the polyamide.
- the notched impact strength can be doubled under normal conditions using high-molecular polyamide-6 compared to the normally viscous polyamide-6.
- Polymers of aliphatic monoolefins with C 2 ⁇ C 4 in particular polyethylene or polyethylene / polypropylene copolymers, preferably with melt indices in the range from 5-20 cm / 10 min. (190 ° C.) are preferably used as polymer component 2a.
- Copolymers of ethylene and (meth) acrylic acid or of ethylene and (meth) acrylic ester with C 2 -C 10 , preferably C 2 -C 7 in the alcoholic radical, particularly preferably n- or tert-butyl ester, are preferably used as polymer component 2b whose melting indices are in the range of 2-10 cm / 10 min. at 190 ° C. All or part of the (meth) acrylic acid can be present as a salt, preferably as a sodium or zinc salt.
- the copolymers 2c used are preferably copolymers of styrene, (meth) acrylic acid and (meth) acrylic acid esters with C 4 -C 10 , preferably C 4 -C 7 in the alcoholic component, particularly preferably n- or tert-butyl ester.
- High-molecular polybutadienes and polyisoprenes, and copolymers of butadiene and / or isoprene with acrylonitrile are preferably suitable as polymers according to 2d, the proportion of acyl nitrile preferably being 10-30 mol%.
- the alloys can be produced by mixing the starting components at temperatures above the melting point of the polyamide used, advantageously at temperatures of 200-320 ° C., in particular at 260-290 ° C.
- Devices in which the molding compositions according to the invention can be produced are conventional screw machines.
- Moldings made from the polymer alloys according to the invention have a relative to alloys based on polyamides-6. Viscosity ⁇ 3.5 the same homogeneity and show no tendency to segregate. They show good surface properties and, compared to moldings made from pure polyamides, have a reduced water absorption.
- the molding compounds are particularly suitable for extruder and injection molding processing for the production of various high-impact molded articles, among others. also pipes.
- the relative viscosity of the polyamides is measured on a 1% solution of the polymer in m-cresol at 25 ° C.
- Example 1 In contrast to Example 1, a polyamide-6 with a rel. Viscosity of 3.0, measured as used in Example 1. The - as described in Example 1 - mixed components are extruded at 260 ° C. The product has a rel. Viscosity 17 rel of approx. 3.2, determined according to Example 1. Freshly injected test specimens show excellent homogeneity in alternate bending tests and have a notched impact strength of 12 kJ / m 2 (DIN 53453).
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Description
Gegenstand der Erfindung sind hochschlagzähe Polymerlegierungen auf Basis von Polyamiden, die eine rel. Viskosität von mindestens 3,5 bzw. einen k-Wert von mindestens 83 (nach Fikentscher) haben.The invention relates to high-impact polymer alloys based on polyamides, which have a rel. Have a viscosity of at least 3.5 or a k-value of at least 83 (according to Fikentscher).
Die Schlagzähigkeit von Formkörpern aus Polyamidkunststoffen hängt erheblich vom Wassergehalt der Formkörper ab. In wasserfreiem Zustand, z.B. nach der Herstellung der Formkörper durch Spritzgießen sind besonders die aus leichtfließenden Polyamidspritzgußmassen mit mittlerem Molekulargewicht und hier wiederum die aus hochkristallinen Polyamiden hergestellten Formkörper relativ empfindlich gegen Schlagbeanspruchung. Es besteht daher ein Bedarf nach rasch verarbeitbaren, leichtfließenden Polyamidkunststoffen, aus denen sich Formkörper herstellen lassen, die in trockenem Zustand eine erhöhte Schlagzähigkeit besitzen. Insbesondere sind solche Polyamide von Interesse, die hohe Zugfestigkeit, hohe Wärmestandfestigkeit, gute Beständigkeit gegen Lösungsmittel und leichte Verarbeitbarkeit kombiniert mit einer hohen Schlagzähigkeit und Flexibilität aufweisen.The impact strength of moldings made of polyamide plastics depends considerably on the water content of the moldings. When anhydrous, e.g. After the molded articles have been produced by injection molding, those made from easy-flowing polyamide injection molding compositions with a medium molecular weight, and here again the molded articles made from highly crystalline polyamides, are relatively sensitive to impact stress. There is therefore a need for rapidly processable, easy-flowing polyamide plastics from which molded articles can be produced which have increased impact strength when dry. Of particular interest are those polyamides which have high tensile strength, high heat resistance, good resistance to solvents and easy processing, combined with high impact strength and flexibility.
Es sind bereits verschiedene Verfahren zur Erhöhung der Zähigkeit und Flexibilität von Polyamiden bekannt. So z.B. das Einmischen von niedermolekularen Weichmachern in Polyamide, das aber aus mehreren Gründen keine zufriedenstellende Lösung des Problems bringt. Der größte Teil der für Kunststoffe geeigneten Weichmacher ist mit Polyamiden nicht genügend verträglich und entmischt sich beim Verarbeiten bzw. neigt zum Ausschwitzen. Verträgliche Weichmacher, die mit Polyamiden echte Lösungen bilden, verschlechtern aber meist die guten mechanischen Eigenschaften der Polyamide. Stark polare Stoffe mit niedrigem Molekulargewicht wie Wasser oder Dimethylformamid zeigen zwar eine starke Weichmacherwirking. Sie können jedoch erst nach der Herstellung von Polyamidformkörpern in diese eingearbeitet werden, weil bei der Verarbeitung von entsprechend vorbehandeltem Polyamidgranulat wegen der relativ niedrigen Siedepunkte dieser Weichmacher blasenhaltige Formkörper entstehen würden.Various methods for increasing the toughness and flexibility of polyamides are already known. So e.g. the mixing of low molecular weight plasticizers in polyamides, but for several reasons it does not provide a satisfactory solution to the problem. The majority of plasticizers suitable for plastics are not sufficiently compatible with polyamides and separate during processing or tend to exude. Compatible plasticizers, which form real solutions with polyamides, usually impair the good mechanical properties of the polyamides. Strongly polar substances with a low molecular weight such as water or dimethylformamide show a strong plasticizer effect. However, they can only be incorporated into them after the production of polyamide moldings, because the processing of appropriately pretreated polyamide granules would result in moldings containing bubbles due to the relatively low boiling points of these plasticizers.
Dieses Verfahren ist zudem im allgemeinen zeit- und kosten-aufwendig. Außerdem ist es für die Herstellung dickwandiger Formteile wegen der unregelmäßigen Verteilung des Weichmachers im Formteil unbrauchbar.This method is also generally time-consuming and costly. In addition, it is unusable for the production of thick-walled molded parts because of the irregular distribution of the plasticizer in the molded part.
Obendrein entweichen diese Weichmacher wegen ihres relativ hohen Dampfdruckes teilweise wieder aus dem Polyamid.On top of that, these plasticizers partly escape from the polyamide due to their relatively high vapor pressure.
Nach anderen Verfahren wird die Schlagzähigkeit von Polyamiden durch Zumischen von polymeren Stoffen verbessert. So wurden Poly- äthylene und Copolymerisate aus Vinylacetat und Äthylen mit mäßigem Erfolg eingesetzt.According to other processes, the impact resistance of polyamides is improved by admixing polymeric substances. Polyethylenes and copolymers of vinyl acetate and ethylene have been used with moderate success.
Die Herstellung derartiger Mischungen erfordert ein sehr intensives Kneten. Dennoch treten Entmischungen beim Weiterverarbeiten z.B. im Spritzguß teilweise wieder auf. Daraus hergestellte Formkörper zeigen bei Beanspruchung starken Weißbruch.The preparation of such mixtures requires very intensive kneading. Nevertheless, segregation occurs during further processing e.g. partly in the injection molding again. Shaped articles made from it show strong whitening when stressed.
In dem GB-A-1 072 635 wird außerdem gelehrt, Polyolefine mit 5-50 Gew.-% Polyamid zu modifizieren, um die Lösungsmitteldurchlässigkeit von Polyolefinen, insbesondere von Polyethylen, zu verbessern.GB-A-1 072 635 also teaches to modify polyolefins with 5-50% by weight polyamide to improve the solvent permeability of polyolefins, especially polyethylene.
Nach einem weiteren Verfahren wird die Flexibilität von Polyamiden durch Einmischen von saure Gruppen enthaltenden Polyethylenen, wie z.B. Copolymerisaten aus Ethylen und ungesättigten Säuren oder mit ungesättigten Säuren gepfropftem Polyethylen, erhöht. Derartige Mischungen sind zwar feindisperser und zeigen bei Beanspruchung einen weit geringeren Weißbruch als die oben Beschriebenen Mischungen, Sie besitzen jedoch, abgesehen von der etwas verbesserten Zähigkeit und Flexibilität, erheblich schlechtere mechanische Eigenschaften, wie z.B. E-Modul, Zugfestigkeit, Härte, Steifigkeit als unvermischte Polyamidformmassen (FR-A-13 86 563).According to a further method, the flexibility of polyamides is increased by mixing in polyethylenes containing acid groups, e.g. Copolymers of ethylene and unsaturated acids or polyethylene grafted with unsaturated acids, increased. Although such mixtures are more finely dispersed and show a much lower whiteness when stressed than the mixtures described above, they have, apart from the somewhat improved toughness and flexibility, considerably poorer mechanical properties, such as e.g. Modulus of elasticity, tensile strength, hardness, rigidity as unmixed polyamide molding compounds (FR-A-13 86 563).
Gemäß der Lehre des FR-A-2 037 979 werden Polyamide mit Ethylencopolymeren modifiziert, die ihrerseits hydroxy- oder epoxysubstituierte Ester von a,ß-ungesättigten Säuren als Comonomere enthalten. Trotz des Einsatzes von Polyamid mit unterschiedlichen Viskosität kann dabei keine nennenswerte Beeinflußung der Kerbschlagzähigkeit beobachtet werden.According to the teaching of FR-A-2 037 979, polyamides are modified with ethylene copolymers, which in turn contain hydroxy- or epoxy-substituted esters of α, β-unsaturated acids as comonomers. Despite the use of polyamide with different viscosities, no noteworthy influence on the impact strength can be observed.
Weiterhin wurde auch ein Verfahren beschrieben, bei dem zur Erhöhung der Flexibilität von Polyamiden Copolymerisate aus Ethylen und Estern von (Meth)-Acrylsäure mit tert. Alkoholen eingesetzt werden.Furthermore, a method was also described in which, to increase the flexibility of polyamides, copolymers of ethylene and esters of (meth) acrylic acid with tert. Alcohols are used.
Diese Legierungen weisen eine gute Homogenität auf und lassen sich ohne Neigung zur Entmischung gut verarbeiten. Die an spritzfrischen Probekörpern gemessenen Kerbschlagzähigkeiten dieser Produkte betragen jedoch auch nur 10-12 kJ/m2.These alloys have good homogeneity and can be processed well without any tendency to separate. However, the notched impact strengths of these products measured on freshly molded test specimens are only 10-12 kJ / m 2 .
Überraschend wurde nun gefunden, daß man Polyamidlegierungen mit im spritzfrischen Zustand besonders hoher Kerbschlagzähigkeit erhält, wenn man Polyamide, insbesondere Polyamide-6 mit einer rel. Viskosität von mind. 3,5, bevorzugt mind. 3,8, gemessen an einer 1%igen Lösung des Polyamids in m-Kresol bei 25°C, zur Herstellung von Polyamidlegierungen verwendet.Surprisingly, it has now been found that polyamide alloys with a particularly high notched impact strength when freshly injected are obtained if polyamides, in particular polyamide-6 with a rel. Viscosity of at least 3.5, preferably at least 3.8, measured on a 1% solution of the polyamide in m-cresol at 25 ° C, used for the production of polyamide alloys.
Diese Verbesserung der Kerbschlagzähigkeit durch den Einsatz hochmolekularer Polyamide war völlig überraschend, da die üblicherweise verwendeten techn. Polyamide mit steigendem Molekulargewicht im spritzfrischen Zustand kaum einen Unterschied in der Kerbschlagzähigkeit aufweisen. Obendrein sind die höherviskosen Polyamide schwieriger zu verarbeiten.This improvement in notched impact strength through the use of high molecular weight polyamides was completely surprising, since the techn. Polyamides with increasing molecular weight in the freshly injected state have hardly any difference in notched impact strength. In addition, the higher-viscosity polyamides are more difficult to process.
Gegenstand der Erfindung sind daher im Spritzfrischen, d. h. wasserfreien Zustand, hochschlagzähe Polyamidlegierungen bestehend aus:
- 1) 60-95 Gew.-%, vorzugsweise 70-90 Gew.-%, eines Polyamids
- 2) 5-40 Gew.-%, vorzugsweise 10-30 Gew.-%, mindestens eines weiteren hochmolekularen Polymeren aus der Gruppe der
- a) aliphatischen Polyolefine
- b) olefinischen Copolymerisate, die sich aus
- a) 65-98 Gew.-%, vorzugsweise 75-95 Gew.-%, eines aliphatischen Monoolefins mit C2―C4 und
- ß) 35-2 Gew.-%, vorzugsweise 25-5 Gew.-%, (Methyl)-acrylsäure oder (Meth)-acrylsäureester zusammensetzen,
- c) Copolymerisate aus
- y) 50-70 Gew.-% Styrol,
- E) 5-15 Gew.-% (Meth)acrylsäure und
- p) 20-30 Gew.-% (Meth)acrylsäureester mit C4―C10 in der alkoholischen Komponente
- d) Polymerer aus
- a') 70-100 Gew.-% aliphatischen Dienen mit C4―C5 und
- β') 0-30 Gew.-% Acrylnitril und
- e) hochmolekularer Siliciumorganischer Verbindungen,
mit der Bedingung, daß die Summe aus 1 + 2, a bis e, a + β, α, + ß', bzw. p, ε + p jeweils immer 100 Gew.-% beträgt und die Komponente 2a immer in Mischung entweder mit der Komponente 2b oder mit der Komponente 2c und zwar in Mengen von 99,9-97, vorzugsweise 99-98 Gew.-%, der Komponente 2a, und 0,1-3, vorzugsweise 1-2 Gew.-% der Komponente 2c, verwendet wird, dadurch gekennzeichnet, daß das Polyamid eine relat. Viskosität von mindestens 3,5, gemessen an einer 1 %igen Losung des Polyamids in m-Kresol bei 25°C aufweist. Bevorzugte Legierungen enthalten neben dem Polyamid mit der geforderten Mindestviskosität 99,9-97, vorzugsweise 99-98 Gew.-% der Komponente 2 a und 0,1-3 Gew.-%, vorzugsweise 1-2 Gew.-%, der Komponente 2 c oder nur die Komponente 2 b.
- 1) 60-95% by weight, preferably 70-90% by weight, of a polyamide
- 2) 5-40 wt .-%, preferably 10-30 wt .-%, of at least one other high molecular weight polymer from the group of
- a) aliphatic polyolefins
- b) olefinic copolymers resulting from
- a) 65-98 wt .-%, preferably 75-95 wt .-%, of an aliphatic monoolefin with C 2 ―C 4 and
- ß) 35-2% by weight, preferably 25-5% by weight, of (methyl) acrylic acid or (meth) acrylic acid ester,
- c) copolymers from
- y) 50-70% by weight styrene,
- E ) 5-15 wt .-% (meth) acrylic acid and
- p) 20-30 wt .-% (meth) acrylic acid ester with C 4 ―C 10 in the alcoholic component
- d) polymer
- a ') 70-100 wt .-% aliphatic dienes with C 4 ―C 5 and
- β ') 0-30 wt .-% acrylonitrile and
- e) high molecular weight organosilicon compounds,
with the condition that the sum of 1 + 2, a to e, a + β, α , + ß ', or p, ε + p is always 100% by weight and component 2a is always mixed with either component 2b or with component 2c in amounts of 99.9-97, preferably 99-98% by weight of component 2a, and 0.1-3, preferably 1-2% by weight of component 2c , is used, characterized in that the polyamide has a relat. Viscosity of at least 3.5, measured on a 1% solution of the polyamide in m-cresol at 25 ° C. In addition to the polyamide with the required minimum viscosity, preferred alloys contain 99.9-97, preferably 99-98% by weight of component 2a and 0.1-3% by weight, preferably 1-2% by weight, of the component 2 c or only component 2 b.
Als Polyamid wird vorzugsweise Polyamid-6 mit einer relativen Viskosität von mindestens 3,5 eingesetzt. Überraschenderweise zeigen unter Verwendung der genannten hydrophoben und unpolaren Legierungspartner 2 Polyamide-6 mit einer rel. Viskosität von mindestens 3,5, vorzugsweise von mindestens 3,8, eine gegenüber analogen Legierungen aus Basis von Polyamiden-6 mit der in der Praxis für den Spritzgußsektor üblichen Viskosität ηrel ca. 3,0) eine drastische Verbesserung der Kerbschlagzähigkeit, wie es in diesem Verhältnis bisher nur durch Wasser, das bekanntlich z.T. in die Wasserstoffbrückenbindungen des Polyamids eingebaut ist, möglich war.Polyamide-6 with a relative viscosity of at least 3.5 is preferably used as the polyamide. Surprisingly, using the hydrophobic and non-polar alloy partners mentioned, 2 polyamides-6 with a rel. Viscosity of at least 3.5, preferably of at least 3.8, compared to analog alloys based on polyamides-6 with the viscosity η rel approx. 3.0 which is customary in practice for the injection molding sector, a drastic improvement in the impact strength, as is the case there This ratio has so far only been possible with water, which is known to be partly incorporated into the hydrogen bonds of the polyamide.
Allgemein kann die Kerbschlagzähigkeit bei sonst gleichen Bedingungen unter Verwendung von hochmolekularem Polyamid-6 gegenüber dem normal viskosen Polyamid-6 verdoppelt werden.In general, the notched impact strength can be doubled under normal conditions using high-molecular polyamide-6 compared to the normally viscous polyamide-6.
Um ausgehend von normalviskosem Polyamid-6 einen entsprechenden Anstieg der Kerbschlagzähigkeit zu erreichen, muß mindestens die doppelte Menge an Legierungspartnern verwendet werden. Dabei wird jedoch in der Regel sowohl die Homogenität verschlechtert als auch die Biegefestigkeit erheblich verringert.In order to achieve a corresponding increase in notched impact strength starting from normal-viscosity polyamide-6, at least twice the amount of alloy partners must be used. As a rule, however, both the homogeneity is deteriorated and the bending strength is considerably reduced.
Als Polymerkomponente 2a werden vorzugsweise Polymere von aliphatischen Monoolefinen mit C2―C4, insbesondere Poly- äthylene oder Polyäthylen/Polypropylen-Copolymerisate, vorzugsweise mit Schmelzindices im Bereich von 5-20 cm/10 Min. (190°C) eingesetzt.Polymers of aliphatic monoolefins with C 2 ―C 4 , in particular polyethylene or polyethylene / polypropylene copolymers, preferably with melt indices in the range from 5-20 cm / 10 min. (190 ° C.) are preferably used as polymer component 2a.
Als Polymerkomponente 2b werden vorzugsweise Copolymerisate aus Äthylen und (Meth)-acrylsäure oder aus Äthylen und (Meth)acrylester it C2―C10, vorzugsweise C2―C7 im alkoholischen Rest, besonders bevorzugt -n-oder tert.-butylester verwendet, deren Schmelzindices im Bereich von 2-10 cm/10 Min. bei 190°C liegen. Die (Meth)acrylsäure kann ganz oder teilweise als Salz vorliegen, vorzugsweise als Natrium- oder Zinksalz.Copolymers of ethylene and (meth) acrylic acid or of ethylene and (meth) acrylic ester with C 2 -C 10 , preferably C 2 -C 7 in the alcoholic radical, particularly preferably n- or tert-butyl ester, are preferably used as polymer component 2b whose melting indices are in the range of 2-10 cm / 10 min. at 190 ° C. All or part of the (meth) acrylic acid can be present as a salt, preferably as a sodium or zinc salt.
Als Copolymerisate 2c werden vorzugsweise Copolymere aus Styrol, (Meth)acrylsäure und (Meth)acrylsäureester mit C4―C10, vorzugsweise C4―C7 in der alkoholischen Komponente, besonders bevorzugt n- oder tert.- butylester eingesetzt.The copolymers 2c used are preferably copolymers of styrene, (meth) acrylic acid and (meth) acrylic acid esters with C 4 -C 10 , preferably C 4 -C 7 in the alcoholic component, particularly preferably n- or tert-butyl ester.
Als Polymerisate gemäß 2d eignen sich vorzugsweise hochmolekulare Polybutadiene und Polyisoprene, sowie Copolymere aus Butadien und/oder Isopren mit Acrylnitril, wobei der Anteil des Acylnitrils vorzugsweise 10-30 Mol-% beträgt.High-molecular polybutadienes and polyisoprenes, and copolymers of butadiene and / or isoprene with acrylonitrile are preferably suitable as polymers according to 2d, the proportion of acyl nitrile preferably being 10-30 mol%.
Als hochmolekulare siliciumorganische Verbindungen sind vorzugsweise Polydimethylsiloxane mit Molgewichten von mindestens 10,000 vorzugsweise mindestens 20.000, gut geeignet.Polydimethylsiloxanes with molecular weights of at least 10,000, preferably at least 20,000, are particularly suitable as high molecular weight organosilicon compounds.
Die Legierungen können durch Vermischen der Ausgangskomponenten bei Temperaturen über dem Schmelzpunkt des verwendeten Polyamids, vorteilhaft bei Temperaturen von 200-320°C, insbesondere bei 260-290°C, hergestellt werden.The alloys can be produced by mixing the starting components at temperatures above the melting point of the polyamide used, advantageously at temperatures of 200-320 ° C., in particular at 260-290 ° C.
Vorrichtungen, in denen die erfindungsgemäßen Formmassen hergestellt werden können, sind übliche Schneckenmaschinen.Devices in which the molding compositions according to the invention can be produced are conventional screw machines.
Es sind sowohl Maschinen mit einfachen als auch solche mit Doppelschnecken geeignet. Doppelschneckenextruder werden bevorzugt verwendet.Both single and double screw machines are suitable. Twin screw extruders are preferred.
Es können jedoch auch andere Mischvorrichtungen verwendet werden, die zum Plastifizieren von Kunststoffen geeignet sind.However, other mixing devices that are suitable for plasticizing plastics can also be used.
In die thermoplastischen Formmassen können außer den Polyolefinanteilen und den Copolymerisaten auch Stabilisatoren, Entformungsmittel, Gleitmittel, Kristallisationsbeschleuniger, Weichmacher, Pigmente, Farbstoffe oder Füllstoffe, wie Glasfasern oder Asbest, eingearbeitet werden.In the thermoplastic molding compositions in addition to the polyolefin and the Copolymers, stabilizers, mold release agents, lubricants, crystallization accelerators, plasticizers, pigments, dyes or fillers, such as glass fibers or asbestos, can also be incorporated.
Formkörper aus den erfindungsgemäßen Polymerlegierungen haben gegenüber Legierungen auf Basis von Polyamiden-6 mit einer relat. Viskosität <3,5 die gleiche Homogenität und zeigen keine Neigung zur Entmischung. Sie zeigen gute Oberflächenbeschaffenheiten und im Vergleich zu Formkörpern aus reinen Polyamiden eine verminderte Wasseraufnahme.Moldings made from the polymer alloys according to the invention have a relative to alloys based on polyamides-6. Viscosity <3.5 the same homogeneity and show no tendency to segregate. They show good surface properties and, compared to moldings made from pure polyamides, have a reduced water absorption.
Die Formmassen eignen sich besonders für die Extruder- und Spritzgußverarbeitung zur Herstellung von verschiedenen hochschlagzähen Formkörpern u.a. auch Rohren.The molding compounds are particularly suitable for extruder and injection molding processing for the production of various high-impact molded articles, among others. also pipes.
Die relative Viskosität der Polyamide wird an einer 1%igen Lösung des Polymeren in m-Kresol bei 25°C gemessen.The relative viscosity of the polyamides is measured on a 1% solution of the polymer in m-cresol at 25 ° C.
88 Gew.-Tle eines Polyamids-6 mit einer rel. Viskosität von 4,0 und einer nach DIN 53 453 bestimmten Kerbschlagzähigkeit von 3-4 KJ/m2, 10 Gew.-Tle. eines Polyäthylens mit einem Schmelzindex von 15 g/10 Min. und 2 Gew.-Tle eines Copolymerisats aus 59 Gew.-% Styrol, 29 Gew.-% n-Butylacrylat, 12 Gew.-% Acrylsäure (Grenzvisk. in Tetrahydrofuran: ca. 1,0; Säurezahl: 94) werden in einem Mischgerät 5 Min. gemischt . Die so vorbereitete Komponentenmischung wird in einem Zweiwellenextruder vom Typ ZSK 53 bei 90 U/Min. und 260°C verknetet und extrudiert, die Schmelze in ein Wasserbad abgesponnen, granuliert und dann bei 80°C im Vakuum bis zu einem Wassergehalt von < 0,05 Gew.-% getrocknet. Das Produkt hat (bezogen auf den Polyamidanteil) eine rel. Viskosität, gemessen an einer 1%igen Lösung in m-Kresol bei 25°C in einem Ubbelohde-Viskosimeter, von 4,2. An frisch gespritzten Probekörpern wird durch Wechselbiegeversuche eine gute Homogenität festgestellt und nach DIN 53 453 eine Kerbschlagzähigkeit von 22 kJ/m2 gemessen.88 parts by weight of a polyamide-6 with a rel. Viscosity of 4.0 and a notched impact strength of 3-4 KJ / m 2 , 10 parts by weight, determined according to DIN 53 453. a polyethylene with a melt index of 15 g / 10 min. and 2 parts by weight of a copolymer of 59% by weight styrene, 29% by weight n-butyl acrylate, 12% by weight acrylic acid (intrinsic viscosity in tetrahydrofuran: approx 1.0; acid number: 94) are mixed in a mixer for 5 minutes. The component mixture prepared in this way is run in a ZSK 53 twin-screw extruder at 90 rpm. and kneaded and extruded at 260 ° C., the melt was spun into a water bath, granulated and then dried at 80 ° C. in vacuo to a water content of < 0.05% by weight. The product has (based on the polyamide content) a rel. Viscosity, measured on a 1% solution in m-cresol at 25 ° C in an Ubbelohde viscometer, of 4.2. A good homogeneity is determined on freshly injected test specimens by alternate bending tests and a notched impact strength of 22 kJ / m 2 is measured in accordance with DIN 53 453.
Im Unterschied zu Beispiel 1 wird ein Polyamid-6 mit einer rel. Viskosität von 3,0, gemessen wie in Beispiel 1 eingesetzt. Die - wie in Beispiel 1 beschrieben - gemischten Komponenten werden bei 260°C extrudiert. Das Produkt hat eine rel. Viskosität 17rel von ca. 3,2, bestimmt gemäß Beispiel 1. Frisch gespritzte Prüfkörper zeigen bei Wechselbiegeversuchen hervorragende Homogenität und haben eine Kerbschlagzähigkeit von 12 kJ/m2 (DIN 53453).In contrast to Example 1, a polyamide-6 with a rel. Viscosity of 3.0, measured as used in Example 1. The - as described in Example 1 - mixed components are extruded at 260 ° C. The product has a rel. Viscosity 17 rel of approx. 3.2, determined according to Example 1. Freshly injected test specimens show excellent homogeneity in alternate bending tests and have a notched impact strength of 12 kJ / m 2 (DIN 53453).
Die Beispiele 2-4, die wie in Beispiel 1 beschrieben, durchgeführt wurden, sind in Tab. 1 zusammengefaßt. Vergleichsversuche B-E, ausgehend von 6-Polyamid, wie in Vergleichsversuch A beschrieben, sind ebenfalls in Tab. 1 aufgeführt.
90 Gew.-Tle eines Polyamids-6 mit einer rel. Visk. von 4,2 werden mit 10 Gew.-% eines Butadien/Acrylnitril-Copolymerens (75/25) wie in Beispiel 1 beschrieben, compoundiert. Das Produkt ist eine homogene Legierung mit einer Kerbschlagzähigkeit von 19 kJ/m2.90 parts by weight of a polyamide-6 with a rel. Visc. of 4.2 are compounded with 10% by weight of a butadiene / acrylonitrile copolymer (75/25) as described in Example 1. The product is a homogeneous alloy with a notched impact strength of 19 kJ / m 2 .
Ausgehend von einem Polyamid-6 der rel. Visk. 3,0 erhält man bei 10 Gew.-Tln des gleichen Copolymeren eine Kerbschlagzähigkeit von 9,5 kJ/m2, bei 25 Gew.-Tln des Copolymeren 14 kJ/m2.Starting from a polyamide 6 of rel. Visc. 3.0, a notched impact strength of 9.5 kJ / m 2 is obtained with 10 parts by weight of the same copolymer and 14 kJ / m 2 with 25 parts by weight of the copolymer.
94 Gew.-Tle eines Polyamids-6 mit einer rel. Visk. von 4,2 werden wie in Beispiel 1 beschrieben mit 6 Gew.-Tln eines Polydimethylsiloxans mit einem Molgewicht von ca. 50.000 compoundiert. Man erhält eine homogene Legierung mit einer Kerbschlagzähigkeit von 20 kJ/m2.94 parts by weight of a polyamide-6 with a rel. Visc. of 4.2 are compounded as described in Example 1 with 6 parts by weight of a polydimethylsiloxane with a molecular weight of approximately 50,000. A homogeneous alloy with a notched impact strength of 20 kJ / m 2 is obtained .
Ausgehend von einem Polyamid-6 der rel. Visk. 3,0 erhält man eine homogene Legierung mit einer Kerbschlagzähigkeit von 12 kJ/m2.Starting from a polyamide 6 of rel. Visc. 3.0, a homogeneous alloy with a notched impact strength of 12 kJ / m 2 is obtained .
88 Gew.-Tle eines Polyamids-6 mit einer rel. Visk. von 4,2 werden mit einem Silicongranulat (12 Gew.-Tie), das ein 50:50-Gemisch aus dem in Beispiel 6 beschriebenen Polydimethylsiloxan und Aerosil ist, wie in Beispiel 1 beschrieben, compoundiert. Man erhält ein homogenes Produkt mit einer Kerbschlagzähigkeit von 15 kJ/m2.88 parts by weight of a polyamide-6 with a rel. Visc. of 4.2 are compounded with a silicone granulate (12 parts by weight), which is a 50:50 mixture of the polydimethylsiloxane and Aerosil described in Example 6, as described in Example 1. A homogeneous product with a notched impact strength of 15 kJ / m 2 is obtained .
Ausgehend von einem 6-Polyamid der rel. Visk. 3,0 erhält man eine homogene Legierung mit einer Kerbschlagzähigkeit von 8,5 kJ/m2.Starting from a 6-polyamide of rel. Visc. 3.0, a homogeneous alloy with an impact strength of 8.5 kJ / m 2 is obtained .
Claims (8)
on the condition that the sum of 1 + 2, of a to e, a + β, a' + β, and y, ε and ϕ is in each case always 100% by weight and that component 2a) is invariably used in admixture either with component 2b) or with component 2c) and in amounts of 99.9-97% by weight of component 2a) and 0.1 -3% by weight of component 2c), characterised in that the polyamide has a relative viscosity of at least 3.5, measured using a 1% solution of the polyamide in m-cresol at 25°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2734693 | 1977-08-02 | ||
| DE19772734693 DE2734693A1 (en) | 1977-08-02 | 1977-08-02 | HIGH-IMPACT POLYAMIDE ALLOYS |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| EP0000583A2 EP0000583A2 (en) | 1979-02-07 |
| EP0000583A3 EP0000583A3 (en) | 1979-03-07 |
| EP0000583B1 true EP0000583B1 (en) | 1981-04-08 |
| EP0000583B2 EP0000583B2 (en) | 1990-08-16 |
Family
ID=6015399
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP78100511A Expired - Lifetime EP0000583B2 (en) | 1977-08-02 | 1978-07-26 | High impact resistance polyamide compound and its use in mouldings |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4321336A (en) |
| EP (1) | EP0000583B2 (en) |
| JP (1) | JPS5428360A (en) |
| DE (2) | DE2734693A1 (en) |
| IT (1) | IT1106620B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0094215A2 (en) * | 1982-05-07 | 1983-11-16 | E.I. Du Pont De Nemours And Company | Compositions of imidized acrylic polymers and polyamides |
| FR2532653A1 (en) * | 1982-09-06 | 1984-03-09 | Rhone Poulenc Spec Chim | COMPOSITIONS FOR MOLDING BASED ON SEMI-RIGID COPOLYAMIDES DERIVED FROM FATTY ACID DIMERS, ELASTOMERS AND POSSIBLY CONVENTIONAL POLYAMIDES |
| US4525531A (en) * | 1983-04-26 | 1985-06-25 | Raychem Corporation | Polymeric compositions suitable for use in the medical field and containing a polyolefin, a polysiloxane and an elastomer |
| FR2592388A1 (en) * | 1985-12-30 | 1987-07-03 | Atochem | POLYAMIDE, POLYETHERAMIDE AND THERMOPLASTIC ELASTOMER ALLOYS |
| EP0229298A1 (en) * | 1985-12-18 | 1987-07-22 | BASF Aktiengesellschaft | Thermoplastic moulding compositions comprising polyamides and styrene-containing polymers |
| EP0232878A2 (en) * | 1986-02-12 | 1987-08-19 | BASF Aktiengesellschaft | Thermoplastic moulding compounds on the basis of polyamides and of styrene polymers |
| EP0232879A2 (en) * | 1986-02-12 | 1987-08-19 | BASF Aktiengesellschaft | Thermoplastic moulding compounds on the basis of polyamides |
| EP0234390A1 (en) * | 1986-02-12 | 1987-09-02 | BASF Aktiengesellschaft | Thermoplastic moulding compositions based on polyamides and copolymers of styrene |
| DE3738876A1 (en) * | 1986-11-18 | 1988-05-26 | Mitsubishi Monsanto Chem | MOLDED AMID RESIN PRODUCT AND METHOD FOR THE PRODUCTION THEREOF |
| EP0269832A2 (en) * | 1986-11-05 | 1988-06-08 | Bayer Ag | Impact-resistant dimensionnaly stable polyamide moulding compound |
| EP0269833A2 (en) * | 1986-11-05 | 1988-06-08 | Bayer Ag | Silicon-containing polyamide compositions |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5965666A (en) * | 1919-10-19 | 1999-10-12 | Cheil Industries, Inc. | Thermoplastic resin composition with high impact strength at low temperatures |
| US4346194A (en) * | 1980-01-22 | 1982-08-24 | E. I. Du Pont De Nemours And Company | Toughened polyamide blends |
| US4356286A (en) * | 1981-03-23 | 1982-10-26 | The Firestone Tire & Rubber Company | Thermoplastic elastomer blends of a nitrile rubber and a crystalline polyamide mixture |
| US4383084A (en) * | 1981-05-14 | 1983-05-10 | Standard Oil Company (Indiana) | Polyamide-polyolefin compositions |
| US4415706A (en) * | 1982-11-10 | 1983-11-15 | Rohm And Haas Company | Compatible blends of polyglutarimides and polyamides |
| GB8317223D0 (en) * | 1983-06-24 | 1983-07-27 | Ici Plc | Polyamide articles |
| US4536541A (en) * | 1984-02-27 | 1985-08-20 | E. I. Du Pont De Nemours And Company | High impact resistant polyamide |
| US4562228A (en) * | 1984-02-29 | 1985-12-31 | The Upjohn Company | Polymer blends |
| EP0154037A3 (en) * | 1984-02-29 | 1987-02-04 | The Dow Chemical Company | Blends of aromatic-aliphatic polyamides and impact modifiers |
| US5340876A (en) * | 1987-03-24 | 1994-08-23 | Bayer Aktiengesellschaft | Thermoplastic moulding compounds of polyamides and resin copolymers |
| US4966941A (en) * | 1987-07-14 | 1990-10-30 | E. I. Du Pont De Nemours And Company | Nylon compositions for blowmolding |
| US4885340A (en) * | 1988-03-28 | 1989-12-05 | Asahi Kasei Kogyo Kabushiki Kaisha | High impact polyamide composition |
| IT1245603B (en) * | 1991-03-29 | 1994-09-29 | Montedipe Srl | THERMOPLASTIC COMPOSITIONS WITH IMPROVED MECHANICAL CHARACTERISTICS |
| US6380289B1 (en) | 1993-06-28 | 2002-04-30 | 3M Innovative Properties Company | Thermoplastic composition comprising fluoroaliphatic radical-containing surface-modifying additive |
| US5376712A (en) * | 1993-09-09 | 1994-12-27 | The University Of Akron | High impact strength polyamides |
| US6685871B2 (en) * | 2001-05-15 | 2004-02-03 | Honeywell International Inc. | Toughened biaxially oriented film |
| EP2660372A1 (en) * | 2012-05-04 | 2013-11-06 | LANXESS Deutschland GmbH | Thermoplastic fibres with reduced surface tension |
| US9388312B2 (en) * | 2012-07-26 | 2016-07-12 | Invista North America S.A.R.L. | Thermoplastic composition for use in high impact applications |
| US9056982B2 (en) * | 2012-07-26 | 2015-06-16 | Invista North America S.A.R.L. | Thermoplastic composition for use in high impact applications |
| WO2016012558A1 (en) * | 2014-07-25 | 2016-01-28 | Dsm Ip Assets B.V. | Blow molded container |
| WO2016012563A1 (en) * | 2014-07-25 | 2016-01-28 | Dsm Ip Assets B.V. | Heat stabilized polyamide composition |
| TW201728680A (en) * | 2015-10-30 | 2017-08-16 | 宇部興產股份有限公司 | Polyamide resin composition and film |
| JP7181381B2 (en) | 2019-03-26 | 2022-11-30 | 三井・ダウポリケミカル株式会社 | Resin composition and molding |
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|---|---|---|---|---|
| CA740501A (en) * | 1966-08-09 | E.I. Du Pont De Nemours And Company | Thermoplastic blends of polyamides and acid-containing olefin polymers | |
| US3134746A (en) * | 1961-06-09 | 1964-05-26 | Borg Warner | Blends of epsilon caprolactam polymer and graft copolymer alkenyl cyanide and alkenyl substituted aromatic hydrocarbon on polybutadiene |
| US3218371A (en) * | 1961-07-31 | 1965-11-16 | Borg Warner | Blends of (1) epsilon caprolactam, (2) rubbery butadiene-acrylonitrile copolymers, and (3) resinous styrene-acrylonitrile copolymers |
| FR1386563A (en) * | 1962-12-31 | 1965-01-22 | Du Pont | Thermoplastic mixtures of polyamides and olefin polymers containing acids |
| CH441742A (en) * | 1964-01-31 | 1967-08-15 | Igo Plast Faigle & Co | Plastic material, preferably for bearings and similar machine elements, as well as processes for their manufacture |
| SE315733B (en) * | 1964-06-22 | 1969-10-06 | Continental Can Co | |
| NL6715002A (en) * | 1966-11-04 | 1968-05-06 | ||
| FR1570562A (en) * | 1968-03-22 | 1969-06-13 | ||
| DE1908468B2 (en) | 1969-02-20 | 1976-10-28 | Bayer Ag, 5090 Leverkusen | HOMOGENOUS MIXTURES OF POLYAMIDES AND POLYOLEFINS |
| NL7003304A (en) * | 1969-03-11 | 1970-09-15 | ||
| GB1241361A (en) * | 1969-03-11 | 1971-08-04 | Ici Ltd | Thermoplastic polymer blends |
| US3668274A (en) * | 1970-09-10 | 1972-06-06 | Rohm & Haas | Acrylic modifiers for polycarbonamides |
| US3796771A (en) * | 1970-09-10 | 1974-03-12 | Rohm & Haas | Acrylic modifiers for polycarbonamides |
| JPS5710144B2 (en) * | 1974-03-11 | 1982-02-25 | ||
| JPS51125451A (en) * | 1975-04-03 | 1976-11-01 | Asahi Chem Ind Co Ltd | Polyamide composition |
| NL168540B (en) * | 1975-05-23 | 1981-11-16 | Du Pont | PROCESS FOR PREPARING A TOUGH, THERMOPLASTIC MULTI-PHASE PREPARATION. |
| JPS5280352A (en) * | 1975-12-27 | 1977-07-06 | Asahi Chem Ind Co Ltd | Polyamide compositions |
| DE2612011A1 (en) * | 1976-03-20 | 1977-09-22 | Bayer Ag | PROCESS FOR THE PRODUCTION OF IMPACT TOUGH THERMOPLASTIC MOLDING COMPOUNDS |
| DE2616092A1 (en) * | 1976-04-13 | 1977-11-03 | Bayer Ag | PROCESS FOR PRODUCING POLYMERIDE DISPERGATORS FOR POLYMER ALLOYS |
| CH626108A5 (en) * | 1976-07-22 | 1981-10-30 | Bayer Ag | Polyamide composition |
| JPS5321252A (en) * | 1976-08-10 | 1978-02-27 | Toray Ind Inc | High impact polyamide composition |
| GB1597478A (en) * | 1976-11-30 | 1981-09-09 | Bayer Ag | Polyamide blends |
| DE2654346C2 (en) * | 1976-12-01 | 1984-03-15 | Bayer Ag, 5090 Leverkusen | Polyamide molding compounds |
| US4086295A (en) * | 1976-12-16 | 1978-04-25 | Asahi Kasei Kogyo Kabushiki Kaisha | Polyamide composition |
| JPH04310366A (en) * | 1991-04-09 | 1992-11-02 | Seiko Epson Corp | Polishing method |
-
1977
- 1977-08-02 DE DE19772734693 patent/DE2734693A1/en not_active Withdrawn
-
1978
- 1978-07-26 EP EP78100511A patent/EP0000583B2/en not_active Expired - Lifetime
- 1978-07-26 DE DE7878100511T patent/DE2860599D1/en not_active Expired
- 1978-07-28 IT IT50521/78A patent/IT1106620B/en active
- 1978-07-31 JP JP9269378A patent/JPS5428360A/en active Granted
-
1980
- 1980-02-19 US US06/122,524 patent/US4321336A/en not_active Expired - Lifetime
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0094215A2 (en) * | 1982-05-07 | 1983-11-16 | E.I. Du Pont De Nemours And Company | Compositions of imidized acrylic polymers and polyamides |
| EP0094215A3 (en) * | 1982-05-07 | 1984-11-14 | E.I. Du Pont De Nemours And Company | Compositions of imidized acrylic polymers and polyamides |
| FR2532653A1 (en) * | 1982-09-06 | 1984-03-09 | Rhone Poulenc Spec Chim | COMPOSITIONS FOR MOLDING BASED ON SEMI-RIGID COPOLYAMIDES DERIVED FROM FATTY ACID DIMERS, ELASTOMERS AND POSSIBLY CONVENTIONAL POLYAMIDES |
| EP0109342A1 (en) * | 1982-09-06 | 1984-05-23 | Rhone-Poulenc Chimie | Moulding compositions of semi-rigid copolyamides derived from dimeric fatty acids, elastomers and optionally conventional polyamides |
| US4525531A (en) * | 1983-04-26 | 1985-06-25 | Raychem Corporation | Polymeric compositions suitable for use in the medical field and containing a polyolefin, a polysiloxane and an elastomer |
| EP0229298A1 (en) * | 1985-12-18 | 1987-07-22 | BASF Aktiengesellschaft | Thermoplastic moulding compositions comprising polyamides and styrene-containing polymers |
| FR2592388A1 (en) * | 1985-12-30 | 1987-07-03 | Atochem | POLYAMIDE, POLYETHERAMIDE AND THERMOPLASTIC ELASTOMER ALLOYS |
| EP0233428A1 (en) * | 1985-12-30 | 1987-08-26 | Elf Atochem S.A. | Alloys based on polyamide, polyether amide and thermoplastic elastomer |
| EP0232879A2 (en) * | 1986-02-12 | 1987-08-19 | BASF Aktiengesellschaft | Thermoplastic moulding compounds on the basis of polyamides |
| EP0232878A2 (en) * | 1986-02-12 | 1987-08-19 | BASF Aktiengesellschaft | Thermoplastic moulding compounds on the basis of polyamides and of styrene polymers |
| EP0234390A1 (en) * | 1986-02-12 | 1987-09-02 | BASF Aktiengesellschaft | Thermoplastic moulding compositions based on polyamides and copolymers of styrene |
| EP0232879A3 (en) * | 1986-02-12 | 1989-10-11 | BASF Aktiengesellschaft | Thermoplastic moulding compounds on the basis of polyamides |
| EP0232878A3 (en) * | 1986-02-12 | 1989-10-25 | Basf Aktiengesellschaft | Thermoplastic moulding compounds on the basis of polyamides and of styrene polymers |
| EP0269832A2 (en) * | 1986-11-05 | 1988-06-08 | Bayer Ag | Impact-resistant dimensionnaly stable polyamide moulding compound |
| EP0269833A2 (en) * | 1986-11-05 | 1988-06-08 | Bayer Ag | Silicon-containing polyamide compositions |
| EP0269832A3 (en) * | 1986-11-05 | 1990-07-18 | Bayer Ag | Impact-resistant dimensionnaly stable polyamide moulding compound |
| EP0269833A3 (en) * | 1986-11-05 | 1990-08-01 | Bayer Ag | Silicon-containing polyamide compositions |
| DE3738876A1 (en) * | 1986-11-18 | 1988-05-26 | Mitsubishi Monsanto Chem | MOLDED AMID RESIN PRODUCT AND METHOD FOR THE PRODUCTION THEREOF |
Also Published As
| Publication number | Publication date |
|---|---|
| IT1106620B (en) | 1985-11-11 |
| DE2860599D1 (en) | 1981-04-30 |
| EP0000583B2 (en) | 1990-08-16 |
| DE2734693A1 (en) | 1979-02-15 |
| US4321336A (en) | 1982-03-23 |
| IT7850521A0 (en) | 1978-07-28 |
| JPS6232220B2 (en) | 1987-07-13 |
| EP0000583A3 (en) | 1979-03-07 |
| JPS5428360A (en) | 1979-03-02 |
| EP0000583A2 (en) | 1979-02-07 |
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