EP0000583B1 - 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
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
Authority
EP
European Patent Office
Prior art keywords
weight
component
polyamide
meth
acrylic acid
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
Application number
EP78100511A
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German (de)
English (en)
Other versions
EP0000583B2 (fr
EP0000583A2 (fr
EP0000583A3 (en
Inventor
Rolf-Volker Dr. Meyer
Rolf Dr. Dhein
Friedrich Fahnler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
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Application filed by Bayer AG filed Critical Bayer AG
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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 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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  • 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 (8)

1. Alliages de polyamides à haute résilience, consistant en
1) 60 à 95% en poids d'un polyamide et
2) 5 a 40% en poids d'au moins un autre polymère à haut poids moléculaire pris dans le groupe des
a) polyoléfines aliphatiques,
b) copolymères olifiniques composés de
a) 65 à 98% en poids d'une moncoléfine aliphatique en C2―C4 et
ß) 35 à 2% en poids d'acide acrylique ou méthacrylique ou d'esters acryliques ou méthacryliques en C2―C10,
c) copolymères de
y) 50 à 70% en poids de styrène,
E) 5 à 15% en poids d'acide acrylique ou méthacrylique et
ϕ20 à 30% en poids d'un ester acrylique ou méthacrylique,
d) polymères de
a') 70 à 100% en poids de diènes en C4―C5 et
β, 0 à 30% en poids d'acrylonitrile et
e) des composés organo-siliciés à haut poids moléculaire,

avec les conditions que la somme de 1 + 2, a à e d'a + β, a' + β, et y, ε et ϕ représente toujours 100% en poids et que le composant 2a) est toujours utilisé dans le mélange, soit avec le composant 2b), soit avec le composant 2c), en quantités de 99,9 à 97% en poids du composant 2a) et 0,1 à 3% en poids du composant 2c), caractérisés en ce que le polyamide présente une viscosité relative d'au moins 2,5, mesurée sur une solution à 1% du polyamide dans le m-crésol à 25°C.
2. Alliages de polyamides selon la revendication 1, caractérisés en ce qu'ils consistent en 70 à 90% en poids du composant 1 ) et 30 à 10% en poids du composant 2).
3. Alliages de polyamides selon la revendication 1, caractérisés en ce que le composant 1) est un polyamide-6.
4. Alliages de polyamides selon la revendication 1, caractérisés en ce que le composant 2a) est un polyéthylène ou copolymère poly- éthylène/polypropylène, le composant 2b) est un copolymère de l'éthylène, de l'acide acrylique ou méthacrylique ou d'esters acryliques ou méthacryliques contenant 2 à 7 atomes de carbone dans le composant alcoolique, le composant 2c) est un copolymère du styrène, de l'acide acrylique ou méthacrylique et d'un ester acrylique ou méthacrylique contenant 4 à 7 atomes de carbone dans le composant alcoolique, le composant 2d) est un polybutadiène, un polyisoprène ou un copolymère du butadiène et/ou de l'isoprène avec l'acrylonitrile et le composant 2e) est un polydiméthylsiloxanne présentant un poids moléculaire d'au moins 10000.
5. Alliages de polyamides selon la revendication 4, caractérisés en ce que l'ester acrylique ou méthacrylique des composants 2b) et 2c) est l'acrylate ou le méthacrylate de n- ou de ter- butyle.
6. Alliages de polyamides selon la revendication 1, caractérisés en ce que le mélange consiste en 99 à 98% en poids du composant 2a) et 1 à 2% en poids du composant 2c).
7. Alliages de polyamides selon la revendication 1, caractérisés en ce que le composant 2) consiste uniquement en le composant 2b).
8. Corps moulés en alliages de polyamides selon les revendications 1 à 7.
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 true EP0000583B1 (fr) 1981-04-08
EP0000583B2 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)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0094215A2 (fr) * 1982-05-07 1983-11-16 E.I. Du Pont De Nemours And Company Compositions de polyacrylates imidés et de polyamides
FR2532653A1 (fr) * 1982-09-06 1984-03-09 Rhone Poulenc Spec Chim Compositions pour moulage a base de copolyamides semi-rigides derives de dimeres d'acides gras, d'elastomeres et eventuellement de polyamides conventionnels
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 (fr) * 1985-12-30 1987-07-03 Atochem Alliages a base de polyamide, polyetheramide et elastomere thermoplastique
EP0229298A1 (fr) * 1985-12-18 1987-07-22 BASF Aktiengesellschaft Compositions de moulage thermoplastiques à base de polyamides et de polymères contenant du styrène
EP0232878A2 (fr) * 1986-02-12 1987-08-19 BASF Aktiengesellschaft Masses à mouler thermoplastiques à base de polyamides et de polymères styréniques
EP0232879A2 (fr) * 1986-02-12 1987-08-19 BASF Aktiengesellschaft Masses à mouler thermoplastiques à base de polyamides
EP0234390A1 (fr) * 1986-02-12 1987-09-02 BASF Aktiengesellschaft Compositions à mouler sur base de polyamides et de copolymères de styrène
DE3738876A1 (de) * 1986-11-18 1988-05-26 Mitsubishi Monsanto Chem Geformtes amidharz-produkt und verfahren zu dessen herstellung
EP0269833A2 (fr) * 1986-11-05 1988-06-08 Bayer Ag Compositions à base de polyamides contenant des segments de chaîne polysiloxane
EP0269832A2 (fr) * 1986-11-05 1988-06-08 Bayer Ag Matière à mouler résistante au choc et ayant des dimensions stables à base de polyamide

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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
EP0154037A3 (fr) * 1984-02-29 1987-02-04 The Dow Chemical Company Mélanges de polyamides aromatiques-aliphatiques et de modificateur d'impact
US4562228A (en) * 1984-02-29 1985-12-31 The Upjohn Company Polymer blends
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 (it) * 1991-03-29 1994-09-29 Montedipe Srl Composizioni termoplastiche a migliorate caratteristiche meccaniche
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 (fr) * 2012-05-04 2013-11-06 LANXESS Deutschland GmbH Fibres thermoplastiques avec une tension de surface réduite
DE112013003661T5 (de) * 2012-07-26 2015-06-25 Invista Technologies S.A.R.L. Thermoplastische Zusammensetzung zur Verwendung in Hochschlagzähanwendungen
US9388312B2 (en) * 2012-07-26 2016-07-12 Invista North America S.A.R.L. Thermoplastic composition for use in high impact applications
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
WO2016012558A1 (fr) * 2014-07-25 2016-01-28 Dsm Ip Assets B.V. Récipient moulé par soufflage
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
US20220169848A1 (en) 2019-03-26 2022-06-02 Dow-Mitsui Polychemicals Co., Ltd. Resin composition and molded body

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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 (fr) * 1962-12-31 1965-01-22 Du Pont Mélanges thermoplastiques de polyamides et de polymères d'oléfines contenant des acides
CH441742A (de) * 1964-01-31 1967-08-15 Igo Plast Faigle & Co Kunststoffmaterial, vorzugsweise für Lager und ähnliche Maschinenelemente, sowie Verfahren zu dessen Herstellung
SE315733B (fr) * 1964-06-22 1969-10-06 Continental Can Co
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FR1570562A (fr) * 1968-03-22 1969-06-13
DE1908468B2 (de) 1969-02-20 1976-10-28 Bayer Ag, 5090 Leverkusen Homogene spritzfaehige mischungen von polyamiden und polyolefinen
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GB1241361A (en) * 1969-03-11 1971-08-04 Ici Ltd Thermoplastic polymer blends
US3796771A (en) * 1970-09-10 1974-03-12 Rohm & Haas Acrylic modifiers for polycarbonamides
US3668274A (en) * 1970-09-10 1972-06-06 Rohm & Haas Acrylic modifiers for polycarbonamides
JPS5710144B2 (fr) * 1974-03-11 1982-02-25
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NL168540B (nl) * 1975-05-23 1981-11-16 Du Pont Werkwijze voor het bereiden van een taai, thermoplas- tisch veelfasenpreparaat.
JPS5280352A (en) * 1975-12-27 1977-07-06 Asahi Chem Ind Co Ltd Polyamide compositions
DE2612011A1 (de) * 1976-03-20 1977-09-22 Bayer Ag Verfahren zur herstellung von schlagzaehen thermoplastischen formmassen
DE2616092A1 (de) * 1976-04-13 1977-11-03 Bayer Ag Verfahren zur herstellung von polymeridispergatoren fuer polymerlegierungen
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
JPS5369253A (en) * 1976-11-30 1978-06-20 Bayer Ag Thermoplastic molding composition
DE2654346C2 (de) * 1976-12-01 1984-03-15 Bayer Ag, 5090 Leverkusen Polyamid-Formmassen
US4086295A (en) * 1976-12-16 1978-04-25 Asahi Kasei Kogyo Kabushiki Kaisha Polyamide composition
JPH04310366A (ja) * 1991-04-09 1992-11-02 Seiko Epson Corp 研磨方法

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0094215A2 (fr) * 1982-05-07 1983-11-16 E.I. Du Pont De Nemours And Company Compositions de polyacrylates imidés et de 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 (fr) * 1982-09-06 1984-03-09 Rhone Poulenc Spec Chim Compositions pour moulage a base de copolyamides semi-rigides derives de dimeres d'acides gras, d'elastomeres et eventuellement de polyamides conventionnels
EP0109342A1 (fr) * 1982-09-06 1984-05-23 Rhone-Poulenc Chimie Compositions de moulage à base de copolyamides semi-rigides dérivés de dimères d'acides gras, d'élastomères et éventuellement de polyamides conventionnels
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 (fr) * 1985-12-18 1987-07-22 BASF Aktiengesellschaft Compositions de moulage thermoplastiques à base de polyamides et de polymères contenant du styrène
FR2592388A1 (fr) * 1985-12-30 1987-07-03 Atochem Alliages a base de polyamide, polyetheramide et elastomere thermoplastique
EP0233428A1 (fr) * 1985-12-30 1987-08-26 Elf Atochem S.A. Alliages à base de polyamide, polyétheramide et élastomère thermoplastique
EP0232879A2 (fr) * 1986-02-12 1987-08-19 BASF Aktiengesellschaft Masses à mouler thermoplastiques à base de polyamides
EP0232878A2 (fr) * 1986-02-12 1987-08-19 BASF Aktiengesellschaft Masses à mouler thermoplastiques à base de polyamides et de polymères styréniques
EP0234390A1 (fr) * 1986-02-12 1987-09-02 BASF Aktiengesellschaft Compositions à mouler sur base de polyamides et de copolymères de styrène
EP0232879A3 (fr) * 1986-02-12 1989-10-11 BASF Aktiengesellschaft Masses à mouler thermoplastiques à base de polyamides
EP0232878A3 (en) * 1986-02-12 1989-10-25 Basf Aktiengesellschaft Thermoplastic moulding compounds on the basis of polyamides and of styrene polymers
EP0269833A2 (fr) * 1986-11-05 1988-06-08 Bayer Ag Compositions à base de polyamides contenant des segments de chaîne polysiloxane
EP0269832A2 (fr) * 1986-11-05 1988-06-08 Bayer Ag Matière à mouler résistante au choc et ayant des dimensions stables à base de polyamide
EP0269832A3 (fr) * 1986-11-05 1990-07-18 Bayer Ag Matière à mouler résistante au choc et ayant des dimensions stables à base de polyamide
EP0269833A3 (fr) * 1986-11-05 1990-08-01 Bayer Ag Compositions à base de polyamides contenant des segments de chaíne polysiloxane
DE3738876A1 (de) * 1986-11-18 1988-05-26 Mitsubishi Monsanto Chem Geformtes amidharz-produkt und verfahren zu dessen herstellung

Also Published As

Publication number Publication date
US4321336A (en) 1982-03-23
EP0000583B2 (fr) 1990-08-16
DE2734693A1 (de) 1979-02-15
DE2860599D1 (en) 1981-04-30
JPS6232220B2 (fr) 1987-07-13
IT1106620B (it) 1985-11-11
IT7850521A0 (it) 1978-07-28
JPS5428360A (en) 1979-03-02
EP0000583A2 (fr) 1979-02-07
EP0000583A3 (en) 1979-03-07

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