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WO1998024847A1 - Composition de resine polyamide resistant aux impacts - Google Patents

Composition de resine polyamide resistant aux impacts Download PDF

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Publication number
WO1998024847A1
WO1998024847A1 PCT/US1997/021967 US9721967W WO9824847A1 WO 1998024847 A1 WO1998024847 A1 WO 1998024847A1 US 9721967 W US9721967 W US 9721967W WO 9824847 A1 WO9824847 A1 WO 9824847A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyamide
aliphatic
composition
mixture
diamine
Prior art date
Application number
PCT/US1997/021967
Other languages
English (en)
Inventor
Reiko Koshida
Ryuichi Hayashi
Original Assignee
E.I. Du Pont De Nemours And Company
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
Application filed by E.I. Du Pont De Nemours And Company filed Critical E.I. Du Pont De Nemours And Company
Publication of WO1998024847A1 publication Critical patent/WO1998024847A1/fr

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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
    • 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
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • 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
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids

Definitions

  • the present invention relates to polyamide resin compositions, and particularly such compositions having high impact resistance, high temperature capability, high moisture resistance, and high dimensional stability. They have a wide range of applications, including automotive and electrical/electronic parts.
  • polyamide resins such as nylon 66, nylon 6. nylon 612. etc.
  • nylon 66, nylon 6. nylon 612. etc. are aliphatic polyamide resins with a certain level of heat resistance and excellent mechanical characteristics. Consequently, these resin compositions are used in a wide range of applications, such as resin moldings as substitutes for metal parts and resin moldings as substitutes for parts made of heat-settings resins.
  • resin moldings as substitutes for metal parts
  • resin moldings as substitutes for parts made of heat-settings resins.
  • aliphatic polyamides exhibit characteristic property losses, especially reduced rigidity.
  • Semi-aromatic polyamides whose monomer contains aromatic dicarboxylic acid and/or aromatic diamine, are known to have superior heat and moisture resistance in comparison to the above-mentioned conventional aliphatic polyamides.
  • An example of such polyamide resins can be found in U.S. Patent 5,378,800.
  • the high glass transition temperature of aromatic polyamides is important to provide excellent mechanical properties at high temperature and with moisture.
  • the crystallization in the molded article of aromatic polyamide is incomplete under molding conditions. When cooling occurs with incomplete crystallization, the molded articles undergo dimensional deformation when they are later exposed to temperatures above its glass transition temperature. Such dimensional changes are significant for thin parts such as electric insulators, connecting devices, fasteners, etc.
  • the present invention provides a high-impact polyamide resin composition which comprises: (a) a semi-aromatic polyamide formed from an aromatic dicarboxylic acid and an aliphatic diamine; said aromatic dicarboxylic acid being terephthalic acid or a mixture of terephthalic acid and isophthalic acid; said aliphatic diamine being hexamethylene diamine or a mixture of hexamethylene diamine and 2-methyl pentamethylene diamine;
  • the polyamide resin composition of this invention has good dimensional stability after molding and the molded articles retain properties well at high temperature and with moisture.
  • nylons referred to herein are polycaprolactam, or H-[HN(CH 2 ) 5 CO] justify-OH;
  • Nylon 66 is poly(hexamethylene adipamide), or H-[HN(CH 2 ) 6 NHCO(CH 2 ) 4 CO -OH;
  • Nylon 612 is poly(hexamethylene dodecanoamide), or H-[HN(CH 2 ) 6 NHCO(CH 2 ), 0 CO] n -OH;
  • Nylon 46 is poly(tetramethylene adipamide), or H-[HN(CH 2 ) 4 NHCO(CH 2 ) 4 CO] n -OH;
  • Nylon 11 is poly(l 1-aminoundecanoamide), or H-[HN(CH 2 ) 10 CO] justify-OH;
  • Nylon 12 is polylaurolactam, or H-[HN(CH 2 ) U CO] n -OH.
  • the semi-aromatic polyamide (a) has an intrinsic viscosity in sulfuric acid at 25°C in the range of 0.2 - 3.0. Also, the melting point is in the range of 280 - 330°C.
  • the mixture preferably contains less than 40 mole percent, based on the mixture of isophthalic acid.
  • the mixture of hexamethylene diamine and 2-methylpentamethylene diamine preferably contains at least 40%, preferably 40 - 90 mole percent based on the mixture, of hexamethylene diamine.
  • This semi-aromatic polyamide can be manufactured by means of polycondensation which is, for example, described in U. S. Patent 5,378,800.
  • the aliphatic polyamide (b) is used for adjusting the glass transition temperature of the polyamide resin composition of this invention according to the intended application of use.
  • the polyamide (b) include nylon 66, nylon 6, nylon 610, nylon 612, nylon 46, nylon 11, nylon 12, etc., and mixtures thereof.
  • nylon 66. nylon 6, nylon 612, and nylon 46 are preferably used.
  • nylon 66 and nylon 6 are most preferably used.
  • the semi-aromatic polyamide (a) and the aliphatic polyamide (b) can be mixed in any ratios as desired, but the ratio of (a) to (b) greater than about 1/1 and less than or equal to about 20/1 is preferably used.
  • the resin composition does not have enough high moisture and heat resistance.
  • the ratio (a) to (b) is greater than about 20/1, the glass transition temperature of the resin composition is high, and it causes dimensional deformation of the molded article after molding.
  • the elastomeric polymer (c) is added for impact toughness.
  • elastomeric polymers include ethylene/alpha-olefm polymers, ethylene/propylene/diene polymers, ethylene/aromatic vinyl monomer/diene polymers, ethylene/acrylate/methacrylate/unsaturated epoxy polymers, etc., and a mixture thereof.
  • Polyethylene, polypropylene, other polyolefins, olefin copolymers, and polyolefin copolymer ionomers are also appropriately used as elastomeric polymers in the present invention.
  • Ethylene-propylene polymer, ethylene-propylene-diene monomer polymer, or ethylene-styrene-diene monomer polymer, or a mixture thereof is preferably used.
  • diene monomers include butadiene, 1 ,4-hexadiene, norbornadiene.
  • Elastomeric polymer used in the present invention may be partially modified with grafted unsaturated carboxylic acid. Maleic anhydride is preferably used for such modifications.
  • the polyamide composition preferably contains from 5 weight percent to 30 weight percent of elastomeric polymer in the total of weight of (a), (b) and (c).
  • the resin composition becomes too brittle.
  • the resin composition loses its rigidity.
  • the resin compostion can optionally contain inorganic fillers.
  • inorganic fillers include glass fiber, carbon fiber, potassium titanate, whiskers, talc, mica, etc., and a mixture thereof.
  • the weight percent of an inorganic filler (d) in the total weight of (a), (b), (c), and (d) is less than 65%.
  • the method of manufacturing the polyamide composition of the present invention may be carried out by means of any conventional well-known method.
  • a semi-aromatic polyamide, an aliphatic polyamide, an elastomeric polymer, and optionally an inorganic filler may be dry mixed, melted, kneaded and extruded using a biaxial extruder or other melt-kneader to form pellets.
  • a polyamide resin composition containing an elastomeric polymer and a polyamide resin composition containing inorganic filler may be melted, kneaded, as well as molded, on an injection molding machine to form the polyamide resin compostion of the present invention.
  • additives commonly employed with synthetic resins such as thermal stabilizers, plasticizers, antioxidants, nucleating agents, dyes, pigments, organic fillers, and mold-release agents may be blended with the polyamide resin composition of the present invention, provided that the characteristics are not lost.
  • 2-methylpentamethylene diamine was 50 to 50; produced by E. I. du Pont de Nemours and Company.
  • a mixture of 11.2 kg of material (a); 5.6 kg of material (bl), 3 kg of material (cl); 145 g heat stabilizer and antioxidants; and 70 g talc were dry-blended and fed into a ZSK-40 twin-screw extruder (manufactured by Werner & Pfeiderer Corp.) set at 320°C.
  • the extruded resin was pelletized, molded, and tested.
  • Mechanical properties were measured according to the ASTM, using 1/8-inch thick test pieces molded with mold temperature at 70°C.
  • Conditioned flexural modulus was measured using 1/8-inch thick test pieces which were conditioned in boiling aqueous solution of 50% potassium acetate for 72 hours.
  • Test pieces were prepared and tested as in Example 1 , except that material (bl) was replaced by the same amount of material (b2).
  • Example 3 Test pieces from a mixture of 10.7 kg of material (a); 5.3 kg of material
  • Example 4 A mixture of 7.8 kg of material (a); 3.8 kg of material (bl); 1.36 kg of material (c2); and 0.68 kg of material (c3) were dry-blended and fed into a ZSK-30 extruder set at 310°C. The extruded resin was pelletized and molded and tested for mechanical properties as molded and as conditioned as in the Example 1.
  • Example 5 A mixture of 7.8 kg of material (a); 3.8 kg of material (bl); 1.36 kg of material (c2); and 0.68 kg of material (c3) were dry-blended and fed into 310°C. The extruded resin was pelletized and molded and tested for mechanical properties as molded and as conditioned as in the Example 1.
  • Example 5 A mixture of 7.8 kg of material (a); 3.8 kg of material (bl); 1.36 kg of material (c2); and 0.68 kg of material (c3) were dry-blended and fed into 310°C. The extruded resin was pelletized and molded and tested for mechanical properties as molded
  • Test piecies from a mixture of 13.9 kg of material (a); 2.9 kg of material (bl); 3-kg of material (cl); 145 g heat stabilizer and antioxidants; and 70 g talc were prepared and tested as in the Example 1.
  • Test pieces from a mixture of 3.8 kg of material (a); 7.8 kg of material (bl); 1.36 kg of material (c2); and 0.68 kg of material (c3) were processed and tested as in the Example 4.
  • Test pieces from a mixture of 16.7 kg of material (a); 3 kg of material (cl), 200 g heat stabilizer and antioxidants; and 70 g talc were prepared and tested as in the Example 1.
  • Test pieces from a mixture of 13.2 kg of material (a); 6.6 kg of material (bl); 80 g heat stabilizer; and 70 g talc were prepared and tested for mechanical properties and dimension as in the Example 1.
  • Test pieces from a mixture of 11.6 kg of material (bl); 0.95 kg of material (c2); and 1.09 kg of material (c4) were dry-blended and fed into a ZSK-30 extruder set at 270°C and tested as in the Example 1
  • the polyamide compositions of the present invention retained properties at high temperature and with moisture while its molded articles exhibiting dimensional stability after molding and annealing.
  • compositions of this invention may contain additives commonly employed with synthetic resins, such as colorants, mold release agents, antioxidants, tougheners, nucleating agents, ultraviolet light and heat stabilizers and the like.
  • additives commonly employed with synthetic resins such as colorants, mold release agents, antioxidants, tougheners, nucleating agents, ultraviolet light and heat stabilizers and the like.
  • An example of a common filler is magnesium hydroxide.

Landscapes

  • 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)

Abstract

L'invention concerne une composition de résine polyamide résistant aux impacts, présentant des propriétés de résistance élevée à la chaleur et à l'humidité et une stabilité dimensionnelle élevée.
PCT/US1997/021967 1996-12-04 1997-12-03 Composition de resine polyamide resistant aux impacts WO1998024847A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US3238796P 1996-12-04 1996-12-04
US60/032,387 1996-12-04

Publications (1)

Publication Number Publication Date
WO1998024847A1 true WO1998024847A1 (fr) 1998-06-11

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1997/021967 WO1998024847A1 (fr) 1996-12-04 1997-12-03 Composition de resine polyamide resistant aux impacts

Country Status (1)

Country Link
WO (1) WO1998024847A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1662081A2 (fr) * 2004-11-24 2006-05-31 Aisin Seiki Kabushiki Kaisha Pièces coulissantes d'une composition de résine de polyamide et dispositif d'arrêt de porte de véhicule automobile utilisant ces parts
US20120247602A1 (en) * 2011-03-28 2012-10-04 E.I. Du Pont De Nemours And Company Thermoplastic multilayer tubes and process for manufacturing
JP2019530762A (ja) * 2016-09-28 2019-10-24 ディーエスエム アイピー アセッツ ビー．ブイ．Ｄｓｍ Ｉｐ Ａｓｓｅｔｓ Ｂ．Ｖ． ポリマー組成物、成形部品およびそれを製造するための方法
JP2021516270A (ja) * 2018-03-23 2021-07-01 ディーエスエム アイピー アセッツ ビー．ブイ．Ｄｓｍ Ｉｐ Ａｓｓｅｔｓ Ｂ．Ｖ． ポリアミド及びそれらから製造される成形部品
US11787939B2 (en) 2019-10-24 2023-10-17 Inv Nylon Polymers Americas, Llc Polyamide compositions and articles made therefrom
US12297352B2 (en) 2018-03-23 2025-05-13 Envalior B.V. Polymer composition and molded part made thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0355315A1 (fr) * 1988-07-14 1990-02-28 BASF Aktiengesellschaft Masses à mouler thermoplastiques à partir de mélanges de polyamides
EP0400428A1 (fr) * 1989-05-31 1990-12-05 BASF Aktiengesellschaft Masses à mouler thermoplastiques à partir de copolyamides partiellement aromatiques et amorphes
EP0728812A1 (fr) * 1995-02-08 1996-08-28 Basf Aktiengesellschaft Masses à mouler thermoplastiques à base de copolyamides semi-aromatiques et amorphes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0355315A1 (fr) * 1988-07-14 1990-02-28 BASF Aktiengesellschaft Masses à mouler thermoplastiques à partir de mélanges de polyamides
EP0400428A1 (fr) * 1989-05-31 1990-12-05 BASF Aktiengesellschaft Masses à mouler thermoplastiques à partir de copolyamides partiellement aromatiques et amorphes
EP0728812A1 (fr) * 1995-02-08 1996-08-28 Basf Aktiengesellschaft Masses à mouler thermoplastiques à base de copolyamides semi-aromatiques et amorphes

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1662081A2 (fr) * 2004-11-24 2006-05-31 Aisin Seiki Kabushiki Kaisha Pièces coulissantes d'une composition de résine de polyamide et dispositif d'arrêt de porte de véhicule automobile utilisant ces parts
EP1662081A3 (fr) * 2004-11-24 2010-05-05 Aisin Seiki Kabushiki Kaisha Pièces coulissantes d'une composition de résine de polyamide et dispositif d'arrêt de porte de véhicule automobile utilisant ces parts
US20120247602A1 (en) * 2011-03-28 2012-10-04 E.I. Du Pont De Nemours And Company Thermoplastic multilayer tubes and process for manufacturing
US9200731B2 (en) * 2011-03-28 2015-12-01 E I Du Pont De Nemours And Company Thermoplastic multilayer tubes and process for manufacturing
JP2019530762A (ja) * 2016-09-28 2019-10-24 ディーエスエム アイピー アセッツ ビー．ブイ．Ｄｓｍ Ｉｐ Ａｓｓｅｔｓ Ｂ．Ｖ． ポリマー組成物、成形部品およびそれを製造するための方法
JP2021516270A (ja) * 2018-03-23 2021-07-01 ディーエスエム アイピー アセッツ ビー．ブイ．Ｄｓｍ Ｉｐ Ａｓｓｅｔｓ Ｂ．Ｖ． ポリアミド及びそれらから製造される成形部品
US12297352B2 (en) 2018-03-23 2025-05-13 Envalior B.V. Polymer composition and molded part made thereof
US11787939B2 (en) 2019-10-24 2023-10-17 Inv Nylon Polymers Americas, Llc Polyamide compositions and articles made therefrom

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