WO1998024847A1 - High-impact polyamide resin composition - Google Patents
High-impact polyamide resin composition Download PDFInfo
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- 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
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- WO
- WIPO (PCT)
- Prior art keywords
- polyamide
- aliphatic
- composition
- mixture
- diamine
- Prior art date
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 17
- 229920006122 polyamide resin Polymers 0.000 title claims abstract description 16
- 239000000203 mixture Substances 0.000 claims description 39
- 229920000642 polymer Polymers 0.000 claims description 26
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 18
- -1 aliphatic diamine Chemical class 0.000 claims description 17
- 239000004953 Aliphatic polyamide Substances 0.000 claims description 16
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 16
- 229920003231 aliphatic polyamide Polymers 0.000 claims description 16
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 14
- 229920006012 semi-aromatic polyamide Polymers 0.000 claims description 11
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 8
- 229920002292 Nylon 6 Polymers 0.000 claims description 7
- 150000001993 dienes Chemical class 0.000 claims description 7
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims description 7
- 239000011256 inorganic filler Substances 0.000 claims description 7
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 229920000572 Nylon 6/12 Polymers 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 claims description 5
- 229920003189 Nylon 4,6 Polymers 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical compound C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 description 27
- 238000000465 moulding Methods 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 239000003963 antioxidant agent Substances 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- 239000012760 heat stabilizer Substances 0.000 description 6
- 239000000454 talc Substances 0.000 description 6
- 229910052623 talc Inorganic materials 0.000 description 6
- 238000000137 annealing Methods 0.000 description 5
- 239000004952 Polyamide Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 229920000299 Nylon 12 Polymers 0.000 description 3
- 125000006367 bivalent amino carbonyl group Chemical group [H]N([*:1])C([*:2])=O 0.000 description 3
- 230000001143 conditioned effect Effects 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 2
- 229920000571 Nylon 11 Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical group [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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.
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
A high-impact polyamide resin composition with properties of high temperature capability, high moisture resistance, and high dimensional stability.
Description
TITLE HIGH-IMPACT POLYAMIDE RESIN COMPOSITION
FIELD OF THE INVENTION 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.
PRIOR ART
Conventional polyamide resins, such as 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. However, in applications when moisture is absorbed, 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. However, due to high glass transition temperature, 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. In order to obtain molded articles of such compositions without this problem, it is necessary to carry out molding with a high-temperature mold, or to subject the molded article to heat annealing, but these processes lengthen the molding cycle and decrease productivity.
SUMMARY OF INVENTION
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;
(b) an aliphatic polyamide formed from aliphatic dicarboyxlic acids and aliphatic diamines, or an aliphatic polyamide formed from aliphatic aminocarboxylic acids;
(c) an elastomeric polymer; and (d) optionally an inorganic filler.
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.
DETAILED DESCRIPTION OF THE INVENTION The following are the nylons referred to herein: Nylon 6 is polycaprolactam, or H-[HN(CH2)5 CO]„-OH; Nylon 66 is poly(hexamethylene adipamide), or H-[HN(CH2)6 NHCO(CH2)4 CO -OH; Nylon 612 is poly(hexamethylene dodecanoamide), or H-[HN(CH2)6 NHCO(CH2),0 CO]n-OH;
Nylon 46 is poly(tetramethylene adipamide), or H-[HN(CH2)4 NHCO(CH2)4 CO]n-OH; Nylon 11 is poly(l 1-aminoundecanoamide), or H-[HN(CH2)10 CO]„-OH; Nylon 12 is polylaurolactam, or H-[HN(CH2)U CO]n-OH.
In the present invention, 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. When a mixture of terephthalic acid and isophthalic acid is used as decarboxylic acid defined in (a), 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. Examples of the polyamide (b) include nylon 66,
nylon 6, nylon 610, nylon 612, nylon 46, nylon 11, nylon 12, etc., and mixtures thereof. When these aliphatic polyamides are blended with the semi-aromatic polyamide (a) to form the polyamide resin component of the invention, it is possible to adjust the glass transition temperature of the claimed polyamide resin composition. Among the aliphatic polyamide resins, nylon 66. nylon 6, nylon 612, and nylon 46 are preferably used. Nylon 66 and nylon 6 are most preferably used.
In the present invention 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.
When the ratio (a) to (b) is smaller than 1/1, the resin composition does not have enough high moisture and heat resistance. When 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. Examples of 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. Examples of 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). When less than 5 weight percent of an elastomeric polymer (c) is used, the resin composition becomes too brittle. When more than 30 weight percent of an elastomeric polymer is used, the resin composition loses its rigidity. Most preferably from 10 to 20 weight percent of elastomeric polymer in the total of (a), (b), and (c) is used.
In the present invention, the resin compostion can optionally contain inorganic fillers. Examples of inorganic fillers include glass fiber, carbon fiber, potassium titanate, whiskers, talc, mica, etc., and a mixture thereof. Preferably, 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. For example, 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. Or 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.
EXAMPLES
The present invention is explained in detail below. Materials used in the examples were:
(a) Semi-aromatic polyamide; copolyamide formed from terephthalic acid, hexamethylene diamine, and 2-methylpentamethylene diamine, in which the molar ratio of hexamethylene diamine to
2-methylpentamethylene diamine was 50 to 50; produced by E. I. du Pont de Nemours and Company.
(b) aliphatic polyamide:
(bl) polyamide 66; produced by E. I. du Pont de Nemours and Company.
(b2) polyamide 612; produced by E. I. du Pont de Nemours and
Company. (b3) polyamide 46; produced by DSM.
(c) elastomeric polymer: (cl) maleic anhydride graft modified ethylene/propylene polymer; produced by Mitsui Petrochemical Industries. (c2) maleic anhydride graft modified ethylene/propylene/diene polymer; produced by E. I. du Pont de Nemours and Company. (c3) ethylene/propylene/diene polymer; produced by E. I. du Pont de Nemours and Company.
Following ASTM test methods were used: Tensile strength and elongation: ASTM D638-94b Flexural modulus and strength: ASTM D790-92
Notched Izod impact strength: ASTM D256-93a
Example 1
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. Dimensions were measured before and after annealing at 160°C for 24 hours for 1-mm thick test pieces molded with mold temperature at 40°C , and the change was calculated as (length difference between before and after annealing)/(length before annealing) X 100.
Example 2
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
(b3); 3.6 kg of material (cl); 290 g heat stabilizer and antioxidants; and 80 g talc were prepared and tested as in the Example 1.
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
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.
Example 6
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.
COMPARATIVE EXAMPLES Example 7
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.
Example 8
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.
Example 9
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 test results are shown in Table 1.
Table 1
As has been described above, 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. Although particular embodiments of the present invention have been described in the foregoing description, it will be understood by those skilled in the art that the invention is capable of numerous modifications, substitutions and rearrangements without departing from the spirit or essential attributes of the invention. Reference should be made to the appended claims, rather than to the foregoing specification, as indicating the scope of the invention.
In addition to the components discussed above, the 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. An example of a common filler is magnesium hydroxide.
Claims
1. A high-impact polyamide resin composition comprising:
(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;
(b) an aliphatic polyamide formed from aliphatic dicarboxylic acids and aliphatic diamines, or an aliphatic polyamide formed from aliphatic aminocarboxylic acids; and
(c) an elastomeric polymer.
2. A composition of claim 1 in which said aromatic dicarboxylic acid in (a) is a mixture of terephthalic acid and isophthalic acid, and isophthalic acid is less than 40% molar basis of the total terephthalic acid and isophthalic acid.
3. A composition of claim 1 in which hexamethylene diamine in (a) is at least 40% of said aliphatic diamine on a molar basis.
4. A composition of claim 1 in which said semi-aromatic polyamide (a) has a melting point in the range of 280°C to 330°C .
5. A composition of claim 1 in which said aliphatic polyamide (b) is polyamide 66, polyamide 6, or polyamide 612.
6. A composition of claim 1 in which said aliphatic polyamide (b) is polyamide 46.
7. A composition of claim 1 in which said elastomeric polymer (c) is ethylene/propylene polymer, ethylene/propylene/diene polymer, or ethylene/styrene/diene polymer, or a mixture thereof.
8. A composition of claim 1 in which said elastomeric polymer (c) is partially grafted with maleic anhydride.
9. A composition of claim 1 in which the weight ratio of said semi-aromatic polyamide (a) to said aliphatic polyamide (b) is greater than about 1/1 and less than or equal to about 20/1.
10. A composition of claim 1 in which said elastomeric polymer (c) is greater than 5 weight percent or more, and less than or equal to 30 weight percent, based on the total weight of (a), (b) and (c).
11. A composition of claim 1 further comprising (d) an inorganic filler.
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 (en) | 1998-06-11 |
Family
ID=21864703
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1997/021967 WO1998024847A1 (en) | 1996-12-04 | 1997-12-03 | High-impact polyamide resin composition |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO1998024847A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1662081A2 (en) * | 2004-11-24 | 2006-05-31 | Aisin Seiki Kabushiki Kaisha | Sliding parts of a polyamide resin composition and a vehicle door check using such 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 (en) * | 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． | POLYMER COMPOSITION, MOLDED PART AND METHOD FOR PRODUCING SAME |
| JP2021516270A (en) * | 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． | Polyamides and molded parts made from them |
| US11787939B2 (en) | 2019-10-24 | 2023-10-17 | Inv Nylon Polymers Americas, Llc | Polyamide compositions and articles made therefrom |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0355315A1 (en) * | 1988-07-14 | 1990-02-28 | BASF Aktiengesellschaft | Thermoplastic moulding compositions based on polyamide mixtures |
| EP0400428A1 (en) * | 1989-05-31 | 1990-12-05 | BASF Aktiengesellschaft | Thermoplastic mouldings of partially aromatic and amorphous copolyamides |
| EP0728812A1 (en) * | 1995-02-08 | 1996-08-28 | Basf Aktiengesellschaft | Thermoplastic mouldings from semi-aromatic and amorphous copolyamides |
-
1997
- 1997-12-03 WO PCT/US1997/021967 patent/WO1998024847A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0355315A1 (en) * | 1988-07-14 | 1990-02-28 | BASF Aktiengesellschaft | Thermoplastic moulding compositions based on polyamide mixtures |
| EP0400428A1 (en) * | 1989-05-31 | 1990-12-05 | BASF Aktiengesellschaft | Thermoplastic mouldings of partially aromatic and amorphous copolyamides |
| EP0728812A1 (en) * | 1995-02-08 | 1996-08-28 | Basf Aktiengesellschaft | Thermoplastic mouldings from semi-aromatic and amorphous copolyamides |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1662081A2 (en) * | 2004-11-24 | 2006-05-31 | Aisin Seiki Kabushiki Kaisha | Sliding parts of a polyamide resin composition and a vehicle door check using such parts |
| EP1662081A3 (en) * | 2004-11-24 | 2010-05-05 | Aisin Seiki Kabushiki Kaisha | Sliding parts of a polyamide resin composition and a vehicle door check using such 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 (en) * | 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． | POLYMER COMPOSITION, MOLDED PART AND METHOD FOR PRODUCING SAME |
| JP2021516270A (en) * | 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． | Polyamides and molded parts made from them |
| US11787939B2 (en) | 2019-10-24 | 2023-10-17 | Inv Nylon Polymers Americas, Llc | Polyamide compositions and articles made therefrom |
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