EP0000583B2 - Masse à mouler, de haute résistance aux chocs, à base de polyamide et son utilisation sous forme d'objets moulés - Google Patents

Masse à mouler, de haute résistance aux chocs, à base de polyamide et son utilisation sous forme d'objets moulés Download PDF

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Publication number
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
Authority
EP
European Patent Office
Prior art keywords
weight
polyamide
meth
acrylic acid
component
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.)
Expired - Lifetime
Application number
EP78100511A
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German (de)
English (en)
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EP0000583B1 (fr
EP0000583A3 (en
EP0000583A2 (fr
Inventor
Rolf-Volker Dr. Meyer
Rolf Dr. Dhein
Friedrich Fahnler
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Bayer AG
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Bayer AG
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Publication of EP0000583A2 publication Critical patent/EP0000583A2/fr
Publication of EP0000583A3 publication Critical patent/EP0000583A3/xx
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Classifications

    • 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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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Claims (9)

1. Alliages de polyamides à haute résilience consistant en
1) 60 à 95% en poids d'un polyamide industriel et
2) 5 à 40% en poids d'au moins un autre composant polymère à haut poids moléculaire choisi dans le groupe constitué par
a; les mélanges de polyoléfines aliphatiques et de copolymères oléfiniques qui sont composés de
a) 65 à 98% en poids d'une monooléfine aliphatique en C2―C4 et
β) 35 à 2% en poids d'acide acrylique ou méthacrylique ou d'esters acryliques ou méthacryliques en C2―C10,
b) les copolymères de
y) au plus 70% en poids de styrène,
s) 5 à 15% en poids d'acide acrylique ou méthacrylique et
5) 20 à 30% en poids d'un ester acrylique ou méthacrylique en C4―C10,
c) les polymères de
α') 70 à 100% en poids de diènes en C4―C5 et
β') 0 à 30% en poids d'acrylonitrile et
d) les composés organosiliciés de haut poids moléculaire, avec les conditions que l'acide acrylique ou méthacrylique dans les copolymères oléfiniques dans 2a peut être totalement ou partiellement sous forme de sel et que la somme de 1) + 2), a) à d, a) + β), a') + β') et y, e et 6, respectivement, représentent toujours chaque fois 100% en poids, caractérisés en ce que le polyamide industriel présente un viscosité relative d'au moins, 3,5, mesurée sur un solution à 1% du polyamide dans le m-crésol à 25°C.
2. Alliages de polyamides selon la revendication 1, caractérisé en ce qu'ils consistent en 70 à 90% en poids du composant 1) et 30 à 10% en poids du composé 2).
3. Alliages de polyamides selon la revendication 1, caractérisé en ce qu'ils contiennent un polyamide-6 industriel comme composant 1).
4. Alliages de polyamides selon la revendication 1, caractérisés en ce qu'ils contiennent comme composant 2 a) un mélange de polyéthylène ou d'un copolymère polyéthylène/poly- propylène et d'un copolymère d'éthylène, d'acide acrylique ou méthacrylique ou d'esters méthacryliques contenant 2 à 7 atomes de carbone dans le composant alcoolique.
5. Alliages de polyamides selon la revendication 1, caractérisé en ce qu'ils contiennent comme composant 2 b) un copolymère de styrène, d'acide acrylique ou méthacrylique et d'ester acrylique ou méthacrylique contenant 4 à 7 atomes de carbone dans le composant alcoolique.
6. Alliages de polyamides selon la revendication 1, caractérisé en ce qu'ils contiennent comme composant 2 c) du polybutadiène, du polyiso- prène ou un copolymère du butadiène et/ou d'isoprène avec l'acrylonitrile.
7. Alliages de polyamides selon la revendication 1, caractérisé en ce qu'ils contiennent comme composant 2 d) un polydimethylsiloxanne d'un poids moléculaire d'au moins 10 000.
8. Alliages de polyamides selon la revendications 4 et 5, caractérisé en ce qu'ils contiennent comme ester acrylique ou méthacrylique dans les composants 2 a) et 2 b) l'acrylate ou méthacrylate de n- ou tert-butyle.
9. Corps moulés en alliages de polyamides selon les revendications 1 à 8.
EP78100511A 1977-08-02 1978-07-26 Masse à mouler, de haute résistance aux chocs, à base de polyamide et son utilisation sous forme d'objets moulés Expired - Lifetime EP0000583B2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2734693 1977-08-02
DE19772734693 DE2734693A1 (de) 1977-08-02 1977-08-02 Hochschlagzaehe polyamidlegierungen

Publications (4)

Publication Number Publication Date
EP0000583A2 EP0000583A2 (fr) 1979-02-07
EP0000583A3 EP0000583A3 (en) 1979-03-07
EP0000583B1 EP0000583B1 (fr) 1981-04-08
EP0000583B2 true EP0000583B2 (fr) 1990-08-16

Family

ID=6015399

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100511A Expired - Lifetime EP0000583B2 (fr) 1977-08-02 1978-07-26 Masse à mouler, de haute résistance aux chocs, à base de polyamide et son utilisation sous forme d'objets moulés

Country Status (5)

Country Link
US (1) US4321336A (fr)
EP (1) EP0000583B2 (fr)
JP (1) JPS5428360A (fr)
DE (2) DE2734693A1 (fr)
IT (1) IT1106620B (fr)

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US4874817A (en) * 1982-05-07 1989-10-17 E. I. Du Pont De Nemours And Company Compositions of imidized acrylic polymers and polyamides
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US4415706A (en) * 1982-11-10 1983-11-15 Rohm And Haas Company Compatible blends of polyglutarimides and 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
GB8317223D0 (en) * 1983-06-24 1983-07-27 Ici Plc Polyamide articles
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DE3544761A1 (de) * 1985-12-18 1987-06-19 Basf Ag Thermoplastische formmassen auf der basis von polyamiden und styrolhaltigen polymeren
FR2592388B1 (fr) * 1985-12-30 1988-02-26 Atochem Alliages a base de polyamide, polyetheramide et elastomere thermoplastique
DE3604376A1 (de) * 1986-02-12 1987-08-13 Basf Ag Thermoplastische formmassen
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EP2660372A1 (fr) * 2012-05-04 2013-11-06 LANXESS Deutschland GmbH Fibres thermoplastiques avec une tension de surface réduite
US9388312B2 (en) * 2012-07-26 2016-07-12 Invista North America S.A.R.L. Thermoplastic composition for use in high impact applications
DE112013003661T5 (de) * 2012-07-26 2015-06-25 Invista Technologies S.A.R.L. Thermoplastische Zusammensetzung zur Verwendung in Hochschlagzähanwendungen
WO2016012558A1 (fr) * 2014-07-25 2016-01-28 Dsm Ip Assets B.V. Récipient moulé par soufflage
CN106536632B (zh) * 2014-07-25 2019-06-11 帝斯曼知识产权资产管理有限公司 热稳定的聚酰胺组合物
TW201728680A (zh) * 2015-10-30 2017-08-16 宇部興產股份有限公司 聚醯胺樹脂組成物及薄膜
KR102627867B1 (ko) 2019-03-26 2024-01-23 미츠이·다우 폴리케미칼 가부시키가이샤 수지 조성물 및 성형체

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Also Published As

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

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