EP0000583B2 - High impact resistance polyamide compound and its use in mouldings - Google Patents

High impact resistance polyamide compound and its use in mouldings Download PDF

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EP0000583B2
EP0000583B2 EP78100511A EP78100511A EP0000583B2 EP 0000583 B2 EP0000583 B2 EP 0000583B2 EP 78100511 A EP78100511 A EP 78100511A EP 78100511 A EP78100511 A EP 78100511A EP 0000583 B2 EP0000583 B2 EP 0000583B2
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polyamide
meth
acrylic acid
component
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EP0000583A3 (en
EP0000583B1 (en
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Rolf-Volker Dr. Meyer
Rolf Dr. Dhein
Friedrich Fahnler
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Bayer AG
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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 viscosity of at least 3.5 measured on a 1% solution of the polyamide in m-cresol at 25 ° C.
  • 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 strength of polyamides is improved by adding 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 to 50% by weight polyamide in order to improve the solvent permeability of polyolefins, in particular polyethylene.
  • the flexibility of polyamides is admixed with polyethylenes containing acidic groups, e.g. Copolymerization of ethylene and unsaturated acids or polyethylene grafted with unsaturated acids, increased.
  • Polyethylenes containing acidic groups e.g. Copolymerization of ethylene and unsaturated acids or polyethylene grafted with unsaturated acids
  • Mixtures of this type are more finely dispersed and, when subjected to stress, have a much lower white break than the mixtures described above.
  • they apart from the somewhat improved toughness and flexibility, they have considerably poorer mechanical properties, e.g. Modulus of elasticity, tensile strength, hardness, rigidity as unmixed polyamide molding compounds (FR-A 13 86 563).
  • polyamides are modified with ethylene copolymers, which in turn contain hydroxy- or epoxy-substituted esters of ⁇ , ⁇ -unsaturated acids as comonomers. Due to the use of polyamide with different viscosity, no noteworthy influence on the impact strength can be observed.
  • US Pat. No. 3,676,400 discloses polyamides whose end groups consist of at least 60% amino groups, to be mixed with olefinic copolymers of C 2 -C 1 , a-monoolefins and a, ⁇ -unsaturated monocarboxylic acids such as (meth) acrylic acid containing acid groups, whereby an improvement in the strength properties is achieved and an increase in the melt viscosity which is to be avoided according to the invention.
  • polyamide alloys with a particularly high notched impact strength in the freshly molded state can be obtained if technical polyamides, in particular technical polyamide-6, with a relative viscosity of at least 3.5, preferably at least 3.8, measured on a 1% strength solution of the polyamide in m-cresol at 25 ° C, used for the production of polyamide alloys.
  • Technical polyamide-6 with a relative viscosity of at least 3.5 is preferably used as the technical polyamide.
  • 2 technical polyamides-6 with a relative viscosity of at least 3.5, preferably of at least 3.8 show one in comparison with analog alloys based on polyamides-6 with those in practice for the injection molding sector usual viscosity ( ⁇ rel approx. 3.0) a drastic improvement in the notched impact strength, as was previously only possible in this ratio through water, which is known to be partly built into the hydrogen bonds of 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 polyethylenes or polyethylene / polypropylene copolymers, preferably with melt indices in the range of 5-20 g / 10 minutes (190 ° C.) are preferably used, and copolymers are preferably used as copolymers from ethylene and (meth) acrylic acid or from ethylene and (meth) acrylic acid ester with C 2 ⁇ C 10 , preferably C 2 -C, in the alcoholic radical, particularly preferably -n- or tert-butyl ester, the melt indices of which range from 2 -10 g / 10 minutes 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 2b used are preferably copolymers of styrene, (meth) acrylic acid and (meth) acrylic acid esters with C 4 ⁇ C 10 , preferably C4-C7 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 2 c, the proportion of acrylonitrile 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 from 200 to 320 ° C., in particular at 260 to 290 ° C.
  • Devices in which the molding compositions according to the invention can be produced are conventional screw machines.
  • thermoplastic polyamide molding compositions In addition to the polymers and copolymers mentioned under 2, stabilizers, mold release agents, lubricants, crystallization accelerators, plasticizers, pigments, dyes or fillers such as glass fibers or asbestos can also be incorporated into the thermoplastic polyamide molding compositions.
  • Shaped articles made from the polyamide alloys according to the invention have the same homogeneity as alloys based on polyamide-6 with a relative viscosity ⁇ 3.5 and show no tendency to separate. 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 technical polyamides is measured on a 1% solution of the polymer in m-cresol at 25 ° C.
  • Example 1 94 parts by weight of an industrial polyamide-6 with a relative viscosity 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 / m2 is obtained.
  • 88 parts by weight of a technical polyamide-6 with a relative viscosity of 4.2 are mixed with a silicone granulate (12 parts by weight), which is a 50:50 mixture of the polydimethylsiloxane and Aerosil® described in example 2, such as described in Example 1, compounded.
  • a homogeneous product with a notched impact strength of 15 kJ / m 2 is obtained .

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Description

Gegenstand der Erfindung sind hochschlagzähe Polymerlegierungen auf Basis von Polyamiden, die eine rel. Viskosität von mindestens 3,5 gemessen an einer 1%igen Lösung des Polyamids in m-Kresol bei 25°C haben.The invention relates to high-impact polymer alloys based on polyamides, which have a rel. Have viscosity of at least 3.5 measured on a 1% solution of the polyamide in m-cresol at 25 ° C.

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 sotche 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, when dry, have increased impact strength. Of particular interest are such 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 Weichmacherwirkung. Sie können jedoch erste nach der Herstellung von Polyamidformkörpern in diese eingearbeitet werden, weil bei der Verarbeitung von entsprechend vorbehandeltem Polyamidgranulat wegen der relativ niederen 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 bring 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, have a strong plasticizing effect. However, they can be incorporated into them first after the production of polyamide moldings, because when processing correspondingly pretreated polyamide granules, bubble-containing moldings would result because of the relatively low boiling points of these plasticizers.

Dieses Verfahren ist zudem im allgemeinen zeit- und kostenaufwendig. Außerdem ist es für die Herstellung dickwandiger Formteile wegen der unregelmäßigen Verteilung des Weichmachers im Formteil unbrauchbar.This process is also generally time consuming and costly. It is also 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 because of their relatively high vapor pressure.

Nach anderen Verfahren wird die Schlagzähigkeit von Polyamiden durch Zumischen von polymeren Stoffen verbessert. So wurden Polyethylene und Copolymerisate aus Vinylacetat und Ethylen mit mäßigem Erfolg eingesetzt.According to other processes, the impact strength of polyamides is improved by adding 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 bis 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 to 50% by weight polyamide in order to improve the solvent permeability of polyolefins, in particular polyethylene.

Nach einem weiteren Verfahren wird die Flexibilität von Polyamiden durch Einmischung von saure Gruppen enthaltenden Polyethylenen, wie z.B. Copolymerisation 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 Eingeschaften, wie z.B. E-Modul, Zugfestigkeit, Härte, Steifigkeit als unvermischte Polyamidformassen (FR-A 13 86 563).According to a further method, the flexibility of polyamides is admixed with polyethylenes containing acidic groups, e.g. Copolymerization of ethylene and unsaturated acids or polyethylene grafted with unsaturated acids, increased. Mixtures of this type are more finely dispersed and, when subjected to stress, have a much lower white break than the mixtures described above. However, apart from the somewhat improved toughness and flexibility, they have considerably poorer mechanical properties, e.g. Modulus of elasticity, tensile strength, hardness, rigidity as unmixed polyamide molding compounds (FR-A 13 86 563).

Gemäß der Lehre der FR-A 2 037 979 werden Polyamide mit Ethylencopolymeren modifiziert, die ihrerseits hydroxy- oder epoxy-substituierte Ester von a,ß-ungesättigten Säuren als Comonomere enthalten. Frotz des Einsatzes von Polyamid mit unterschiedlicher 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. Due to the use of polyamide with different viscosity, no noteworthy influence on the impact strength can be observed.

Aus dem US-PS 3 676 400 geht hervor Polyamide, deren Endgruppen zumindest zu 60% aus Aminogruppen bestehen, mit säuregruppenhaltigen olefinischen Copolymerisaten aus C2-C1, a-Monoolefinen und a,ß-ungesättigten Monocarbonsäuren wie (Meth)acrylsäure abzumischen, wobei eine Verbesserung der Festigkeitseigenschaften erzielt werden und ein Anstieg der Schmelzviskosität, der erfindungsgemäß vermieden werden soll.US Pat. No. 3,676,400 discloses polyamides whose end groups consist of at least 60% amino groups, to be mixed with olefinic copolymers of C 2 -C 1 , a-monoolefins and a, β-unsaturated monocarboxylic acids such as (meth) acrylic acid containing acid groups, whereby an improvement in the strength properties is achieved and an increase in the melt viscosity which is to be avoided according to the invention.

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 in 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 strength of these products measured in freshly molded test specimens is only 10-12 kJ / m2 .

Überraschend wurde nun gefunden, daß man Polyamidlegierungen mit im spriztfrischen Zustand besonders hoher Kerbschlagzähigkeit erhält, wenn man technische Polyamide, insbesondere technisches Polyamid-6 mit einer relativen Viskosität von mindestens 3,5, bevorzugt mindestens 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 in the freshly molded state can be obtained if technical polyamides, in particular technical polyamide-6, with a relative viscosity of at least 3.5, preferably at least 3.8, measured on a 1% strength 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 technischen 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 technical polyamides commonly used with increasing molecular weight in the freshly sprayed state show little difference in 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 technischen Polyamids.
  • 2. 5-40 Gew.-%, vorzugsweise 10-30 Gew.-%, mindestens einer weiteren hochmolekularen Polymerkomponente aus der Gruppe von
    • a) Mischungen aus aliphatischen Polyolefinen und olefinischen Copolymerisaten, 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.-%, (Meth)acrylsäure oder (Meth)acrylsäure ester, mit C2―C10 zusammensetzen.
    • b) Copolymerisaten aus
      • y) höchstens 70 Gew.-% Styrol,
      • s) 5-15 Gew.-% (Meth)acrylsäure und
      • 5) 20-30 Gew.-% (Meth)acrylsäureester mit C4-Clo in der alkoholischen Komponente
    • c) Polymeren aus
      • a') 70-100 Gew.-% aliphatischen Dienen mit C4-CS und
      • ß') 0-30 Gew.-% Acrylnitril und
      • d) hochmolekularen siliciumorganischen Verbindungen.
mit den Bendingungen, daß die (Meth)acrylsäure ganz oder teilweise als Salz vorliegen kann und daß die Summe aus 1 + 2, a) bis d), a + β, a' + ß' bzw. y + s + 5 jeweils immer 100 Gew.-% beträgt, dadurch gekennzeichnet, daß das technische Polyamid eine relative Viskosität von mindestens 3,5, gemessen an einer 1 %igen Lösung des Polyamids in m-Kresol bei 25°C aufweist.The invention therefore relates to high-impact polyamide alloys consisting of:
  • 1. 60-95% by weight, preferably 70-90% by weight, of an industrial polyamide.
  • 2. 5-40% by weight, preferably 10-30% by weight, of at least one further high molecular weight polymer component from the group of
    • a) Mixtures of aliphatic polyolefins and olefinic copolymers, which result from
      • a) 65-98 wt .-%, preferably 75-95 wt .-% of an aliphatic monoolefin with C2-C4 and
      • ß) 35-2 wt .-%, preferably 25-5 wt .-%, (meth) acrylic acid or (meth) acrylic acid ester, with C 2― C 10 together.
    • b) copolymers
      • y) at most 70% by weight of styrene,
      • s) 5-15 wt .-% (meth) acrylic acid and
      • 5) 20-30 wt .-% (meth) acrylic acid ester with C 4 -C lo in the alcoholic component
    • c) polymers
      • a ') 70-100 wt .-% aliphatic dienes with C 4 -C S and
      • ß ') 0-30 wt .-% acrylonitrile and
      • d) high molecular weight organosilicon compounds.
with the conditions that the (meth) acrylic acid can be present in whole or in part as a salt and that the sum of 1 + 2, a) to d), a + β, a '+ ß' or y + s + 5 is always in each case 100% by weight, characterized in that the technical polyamide has a relative viscosity of at least 3.5, measured on a 1% solution of the polyamide in m-cresol at 25 ° C.

Als technisches Polyamid wird vorzugsweise technisches Polyamid-6 mit einer relativen Viskosität von mindestens 3,5, eingesetzt. Überraschenderweise zeigen unter Verwendung der genannten hydrophoben und unpolaren Legierungspartner 2 technische Polyamide-6 mit einer relativen Viskosität von mindestens 3,5, vorzugsweise von mindestens 3,8, eine gegenüber analogen Legierungen auf Basis von Polyamiden-6 mit der in der Praxis für den Spritzgußsektor üblichen Viskosität (πrel 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.Technical polyamide-6 with a relative viscosity of at least 3.5 is preferably used as the technical polyamide. Surprisingly, using the hydrophobic and non-polar alloy partners mentioned, 2 technical polyamides-6 with a relative viscosity of at least 3.5, preferably of at least 3.8, show one in comparison with analog alloys based on polyamides-6 with those in practice for the injection molding sector usual viscosity (π rel approx. 3.0) a drastic improvement in the notched impact strength, as was previously only possible in this ratio through water, which is known to be partly built into the hydrogen bonds of the polyamide.

Allgemein kann die Kerbschlagzähigkeit bei sonst gleichen Bedingungen unter Verwendung von hochmolekularem Polyamid-6 gegenüber dem normalviskosen 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.

In der Polymerkomponente 2a werden vorzugsweise Polymere von aliphatischen Monoolefinen mit C2-C4, insbesondere Polyethylene oder Polyethylen/Polypropylen-Copolymerisate, vorzugsweise mit Schmelzindices im Bereich von 5-20 g/ 10 Minuten (190°C) eingesetzt und als Copolymerisate vorzugsweise Copolymerisate aus Ethylen und (Meth)acrylsäure oder aus Ethylen und (Meth)acrylsäureester mit C2―C10, vorzugsweise C2-C, im alkoholischen Rest, besonders bevorzugt -n- oder tert.-Butylester verwendet, deren Schmelzindices im Bereich von 2-10 g/10 Minuten bei 190°C ligen. Die (Meth)acrylsäure kann ganz oder teilweise als Salz vorliegen, vorzugsweise als Natrium oder Zinksalz.In polymer component 2a, polymers of aliphatic monoolefins with C 2 -C 4 , in particular polyethylenes or polyethylene / polypropylene copolymers, preferably with melt indices in the range of 5-20 g / 10 minutes (190 ° C.) are preferably used, and copolymers are preferably used as copolymers from ethylene and (meth) acrylic acid or from ethylene and (meth) acrylic acid ester with C 2 ―C 10 , preferably C 2 -C, in the alcoholic radical, particularly preferably -n- or tert-butyl ester, the melt indices of which range from 2 -10 g / 10 minutes 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 2b 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 2b used are preferably copolymers of styrene, (meth) acrylic acid and (meth) acrylic acid esters with C 4 ―C 10 , preferably C4-C7 in the alcoholic component, particularly preferably n- or tert-butyl ester.

Als Polymerisate gemäß 2 c eignen sich vorzugsweise hochmolekulare Polybutadiene und Polyisoprene, sowie Copolymere aus Butadien und/oder Isopren mit Acrylnitril, wobei der Anteil des Acrylnitrils 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 2 c, the proportion of acrylonitrile preferably being 10-30 mol%.

Als hochmolekulare siliciumorganische Verbindungen sind vorzugsweise Polydimethylsiloxane mit Molegwichten 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 bis 320°C, insbesondere bei 260 bis 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 from 200 to 320 ° C., in particular at 260 to 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 Ptastifizieren von Kunststoffen geeignet sind.However, other mixing devices can also be used, which are suitable for paste-coating plastics.

In die thermoplastischen Polyamid-Formmassen können außer den unter 2. genannten Polymerisaten und den Copolymerisaten auch Stabilisatoren, Entformungsmittel, Gleitmittel, Kristallisationsbeschleuniger, Weichmacher, Pigmente, Farbstoffe oder Füllstoffe, wie Glasfasern oder Asbest, eingearbeitet werden.In addition to the polymers and copolymers mentioned under 2, stabilizers, mold release agents, lubricants, crystallization accelerators, plasticizers, pigments, dyes or fillers such as glass fibers or asbestos can also be incorporated into the thermoplastic polyamide molding compositions.

Formkörper aus den erfindungsgemäßen Polyamidlegierungen haben gegenüber Legierungen auf Basis von Polyamid-6 mit einer relativen 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.Shaped articles made from the polyamide alloys according to the invention have the same homogeneity as alloys based on polyamide-6 with a relative viscosity <3.5 and show no tendency to separate. 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 technischen Polyamide wird an einer 1%igen Lösung des Polymeren in m-Kresol bei 25°C gemessen.The relative viscosity of the technical polyamides is measured on a 1% solution of the polymer in m-cresol at 25 ° C.

Beispiel 1example 1

90 Gew.-Teile einas technischen Polyamid-6 mit einer relativen Lösungsvikositätvon 4,2 und einer nach DIN 53 453 bestimmten Kerbschlagzähigkeit von 3―4 KJ/m2 und 10 Gew.-Teile eines Copolymerisats aus 75 Gew.-% Butadien und 25 Gew.-% Acrylnitril 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. An frisch gespritzten Probekörpern wird durch Wechselbiegeversuche eine gute Homogenität festgestellt und nach DIN 53 453 eine Kerbschlagzähigkeit von 19 kJ/m2 gemessen.90 parts by weight of a technical polyamide-6 with a relative solution viscosity of 4.2 and a notched impact strength of 3―4 KJ / m 2 determined according to DIN 53 453 and 10 parts by weight of a copolymer of 75% by weight of butadiene and 25% % By weight of acrylonitrile is 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. A good homogeneity is determined on freshly injected test specimens by alternate bending tests and a notched impact strength of 19 kJ / m 2 is measured in accordance with DIN 53 453.

Vergleichsversuch:Comparison test:

Ausgehend von einem technischen Polyamid-6 der relativen Viskosität 3,0 erhält man bei 10 Gew.-Teilen des gleichen Copolymeren eine Kerbschlagzähigkeit von 9,5 kJ/m2, bei 25 Gew.-Teilen des Copolymeren 14 kJ/m2.Starting from a technical polyamide-6 with a relative viscosity of 3.0, a notched impact strength of 9.5 kJ / m 2 is obtained for 10 parts by weight of the same copolymer and 14 kJ / m 2 for 25 parts by weight of the copolymer.

Beispiel 2Example 2

94 Gew.-Teile eines technischen Polyamids-6 mit einer relativen Viskosität von 4,2 werden wie in Beispiel 1 beschrieben mit 6 Gew.-Teilen eines Polydimethylsiloxans mit einem Molegwicht von ca. 50.000 compoundiert. Man erhält eine homogene Legierung mit einer Kerbschlagzähigkeit von 20 kJ/m2. 94 parts by weight of an industrial polyamide-6 with a relative viscosity 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 / m2 is obtained.

Vergleichsversuch:Comparison test:

Ausgehend von einem Polyamid-6 der relativen Viskosität 3,0 erhält man eine homogene Legierung mit einer Kerbschlagzähigkeit von 12 kJ/m2.Starting from a polyamide 6 with a relative viscosity of 3.0, a homogeneous alloy with a notched impact strength of 12 kJ / m 2 is obtained .

Beispiel 3Example 3

88 Gew.-Teile eines technischen Polyamids-6 mit einer relativen Viskosität von 4,2 werden mit einem Silikongranulat (12 Gew.-Teile), das ein 50:50-Gemisch aus dem in Beispeil 2 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 technical polyamide-6 with a relative viscosity of 4.2 are mixed with a silicone granulate (12 parts by weight), which is a 50:50 mixture of the polydimethylsiloxane and Aerosil® described in example 2, such as described in Example 1, compounded. A homogeneous product with a notched impact strength of 15 kJ / m 2 is obtained .

Verleichsversuch:Comparison attempt:

Ausgehend von einem technischen Polyamid-6 der relativen Viskosität 3,0 erhält man eine homogene Legierung mit einer Kerbschlagzähigkeit von 8,5 kJ/m2. Starting from a technical polyamide-6 with a relative viscosity of 3.0, a homogeneous alloy with an impact strength of 8.5 kJ / m2 is obtained.

Claims (9)

1. Polyamide alloys with high impact strength, consisting of
1) from 60 to 95% by weight of a commercial polyamide and
2) from 5 to 40% by weight of at least one other high molecular weight polymer component selected from
a) mixtures of aliphatic polyolefines and olefinic copolymers composed of
a) from 65 to 98% by weight of an aliphatic monoolefin having 2 to 4 carbon atoms and
β) from 35 to 2% by weight of (meth)acrylic acid or (meth)acrylic acid esters having 2 to 10 carbon atoms,
b) copolymers of
y) at the most 70% by weight of styrene,
s) from 5 to 15% by weight of (meth)acrylic acid and
5) from 20 to 30% by weight of a (meth)acrylic acid ester having 4 to 10 carbon atoms,
c) polymers of
a') from 70 to 100% by weight of dienes containing 4 to 5 carbon atoms and
β') from 0 to 30% by weight of acrylonitrile and
d) high molecular weight organic silicon compounds

under the conditions that the (meth)acrylic acid may be partly or completely present as salt in the olefinic copolymers in 2a and that the sum of 1 + 2 a) to d), a) + β), a') + β') or y), E) and 5) always amounts to 100% by weight, characterised in that the commercial polyamide has a relative vicosity of at least 3·5, determined on a 1% solution of the polyamide in m-cresol at 25°C.
2. Polyamide alloys according to Claim 1, characterised in that they consist of 70 to 90% by weight of component 1) and 30 to 10% by weight of component 2).
3. Polyamide alloys according to Claim 1, characterised in that they contain commercial polyamide-6 as component 1).
4. Polyamide alloys according to Claim 1, characterised in that they contain, as component 2a), a mixture of polyethylene or a polyethylene/ polyproplyene copolymer and a copolymer of ethylene, (meth)acrylic acid or methacrylic acid esters having 2 to 7 carbon atoms in the alcoholic component.
5. Polyamide alloys according to Claim 1, characterised in that they contain, as component 2b), a copolymer of styrene, (meth)acrylic acid and (meth)acrylic acid esters having 4 to 7 carbon atoms in the alcoholic component.
6. Polyamide alloys according to Claim 1, characterised in that they contain, as component 2c), polybutadiene, polyisoprene or a copolymer of butadiene and/or isoprene with acrylonitrile.
7. Polyamide alloys according to Claim 1, characterised in that they contain, as component 2d), a polydimethyl siloxane having a molecular weight of at least 10,000.
8. Polyamide alloys according to Claims 4 and 5, characterised in that they contain, as (meth)-acrylic acid ester in component 2a) and 2b), (meth)acrylic acid n- or -tert.-butyl ester.
9. Moulded articles of polyamide alloys according to Claims 1 to 8.
EP78100511A 1977-08-02 1978-07-26 High impact resistance polyamide compound and its use in mouldings Expired - Lifetime EP0000583B2 (en)

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DE2734693 1977-08-02
DE19772734693 DE2734693A1 (en) 1977-08-02 1977-08-02 HIGH-IMPACT POLYAMIDE ALLOYS

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DE2734693A1 (en) 1979-02-15
JPS5428360A (en) 1979-03-02
EP0000583A3 (en) 1979-03-07
EP0000583B1 (en) 1981-04-08
DE2860599D1 (en) 1981-04-30
IT1106620B (en) 1985-11-11
IT7850521A0 (en) 1978-07-28
EP0000583A2 (en) 1979-02-07
US4321336A (en) 1982-03-23
JPS6232220B2 (en) 1987-07-13

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