WO2012106319A2 - Thermoplastic melt-mixed composition with heat stabilizer cross reference to related application - Google Patents

Thermoplastic melt-mixed composition with heat stabilizer cross reference to related application Download PDF

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Publication number
WO2012106319A2
WO2012106319A2 PCT/US2012/023295 US2012023295W WO2012106319A2 WO 2012106319 A2 WO2012106319 A2 WO 2012106319A2 US 2012023295 W US2012023295 W US 2012023295W WO 2012106319 A2 WO2012106319 A2 WO 2012106319A2
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Prior art keywords
group
acid
poiy
poly
hexanediamide
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PCT/US2012/023295
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French (fr)
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WO2012106319A3 (en
Inventor
Toshikazu Kobayashi
Jennifer Leigh Thompson
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E. I. Du Pont De Nemours And Company
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Publication of WO2012106319A2 publication Critical patent/WO2012106319A2/en
Publication of WO2012106319A3 publication Critical patent/WO2012106319A3/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0091—Complexes with metal-heteroatom-bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/175—Amines; Quaternary ammonium compounds containing COOH-groups; Esters or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • C08K7/20—Glass

Definitions

  • the present invention relates to the field of poiyamide compositions having improved long-term high temperature aging characteristics.
  • JP 47013882 discloses a molded article or fiber comprising a poiyamide that is surface treated with a chelating chemical solution including nitrogen containing carboxyiic acids including EDTA to improve stability.
  • weight percents of components a), b), c) and d) are based on the totai weight of the thermoplastic melt-mixed composition.
  • Figure 1 illustrates the TGA weight loss curve of an amino acid thermal stabilizer useful in the melt-blended compositions.
  • composition comprising:
  • Diamines can be chosen among diamines having four or more carbon atoms, including, but not limited to tetramethylene diamine, hexamethy!ene diamine, octamethyiene diamine, decamethylene diamine, dodecamethylene diamine, 2 ⁇ methylpentamethyiene diamine, 2-ethy!tetramethylene diamine, 2 ⁇
  • the "6” refers to HMD.
  • the diamine is designated first.
  • the first “6” refers to the diamine HMD
  • the second “6” refers to adipic acid.
  • repeat units derived from other amino acids or lactams are designated as single numbers designating the number of carbon atoms.
  • PA6/612 poly(hexamethyiene tridecanediamide) (PA613), polyihexamethylene pentadecanediamide) (PA615), poly(c ⁇ caprolactam/tetramethy!ene ierephihaiamide) (PA6/4T), poly(c- caprolactam/hexamethy!ene ierephihaiamide) (PA8/6T), polyie- caprolactam/decamethy!ene ierephihaiamide) (PA6/10T), poly(e ⁇ caprolactam/dodecamethyiene ierephihaiamide) (PA6/12T),
  • dodecanediamide PA6/66/612
  • dodecanediamide (PA6/66/610/812), poly(2-methyipentamethylene hexanediamide/hexameihylene hexanediamide/hexameihylene
  • Group (I I) Polyamides are Group (HA) Polyamides having a melting point of at least 210 °C and less than 230 °C and Group (I!B) Potyamides having a melting point of 230 °C or greater; Group (HI) Polyamides having a melting point of greater than 230 °C, and comprising
  • MB Polyamides have a melting point of greater than 230 C C and comprise an aliphatic poiyamide selected from the group consisting of:
  • PA 88/8 polyihexamethyiene hexanediamide
  • PA 86 poly(hexamethylene hexanediamide/hexamethylene decanediamide)
  • PA88/810 polyitetramethylene hexanediamide/2-methylpentamethylene hexanediamide)
  • PA46/D6 polyitetramethylene hexanediamide/2-methylpentamethylene hexanediamide
  • the poiyamide resin comprises one or more polyamides selected from the group consisting of Group (III) Polyamides, Group (IV)
  • the composition comprises about 1.0 to about 5.0 weight percent of an amino acid thermal stabilizer based on the total weight of the melt-mixed composition, in preferred embodiments the melt-mixed composition comprises about 1.2 to 5.0 weight percent, about 1.2 to 4.0 weight percent or about 1.4 to 4.0 weight percent of an amino acid thermal stabilizer based on the total weight of the melt-mixed composition.
  • the amino acid thermal stabilizer comprises at least one or more amino groups, and preferably two or more amino groups; and at least two or more groups selected from carboxylic acid and carboxyiic acid salt; said carboxylic acid and carboxylic acid salt represented by the general formula -CO 2 Y; and the amino acid thermal stabilizer having a number average molecular weight of less than or equal to about 2000, preferably less than 1000, as determined by calculation of molecular weight of the amino acid thermal stabilizer wherein Y is considered to have a molecular weight equal to 1 ; or if the amino acid thermal stabilizer is an oligomeric material, as determined with gel permeation chromatography.
  • the term "at least two or more groups selected from carboxylic acid and carboxyiic acid salt” means the amino acid thermal stabilizer can have two or more carboxyiic acids, two or more carboxyiic acid salts, or a mixture of carboxyiic acids and carboxyiic acid salts.
  • the carboxylic acid salt comprises a carboxylate anion and a positively charged counter-ion.
  • the carboxyiic acid salt can have a single counter-ion or be a mixture of counter-ions.
  • the carboxyiic acid salt groups are available from a parent carboxylic acid by neutralization of the parent carboxylic acid with appropriate metal hydroxides or oxides, ammonium hydroxide, or by ion exchange.
  • Useful carboxyi acid salts include monovalent ion salts, such as Li, Na, K, ammonium and phosphonium ions; divalent ion salts such as g, Ca, Ba, Cu, Fe(il) salts; trivalent ion salts such as Fe(ill) salts; and tetravalent salts such as Ti(IV) and Zr(iV) salts.
  • ammonium ion and phosphonium ion refers to the general classes of R 4 N + and R 4 P * ions wherein R is, independently, selected from the group consisting of H, Ci - C-ie linear or branched alkyl, and phenyl; wherein the linear or branched alkyl groups may have one or two sites of unsaturation, and wherein the linear or branched alkyl groups may be interrupted by one to three heteroatoms selected from oxygen and sulfur.
  • Phosphonium ions may be wherein R is, independently, selected from the group consisting of Ci - Cis linear or branched alkyl.
  • Ammonium ions may be wherein R is, independently, selected from the group consisting of H, Ci - Cis linear or branched alkyl.
  • Ammonium ions may be wherein R is, independently, selected from the group consisting of H, C-i - Cio linear or branched alkyl, and preferably wherein R is, independently, selected from the group consisting of H, d ⁇ ⁇ C 4 linear or branched alkyl.
  • a preferred ammonium ion is NH 4 + .
  • linking groups comprising one or more carbon atoms.
  • the linking groups comprise one or two carbon atoms, and preferably linking groups linking an amino group to a carboxylic acid group comprises one carbon atom.
  • Linking groups between two amino groups may comprise one, two, or more carbon atoms.
  • Linking groups may include one or more heteroatoms such as oxygen or sulfur.
  • the amino acid thermal stabilizer may have one or more hydroxyl groups.
  • the amino acid thermal stabilizers useful in the melt-mixed compositions include those of formula (X) to (XXVII):
  • a counter-ion Y can be H, or 1/x M wherein x is an integer of 1 to 7, and M is a metal ion, ammonium ion or phosphonium ion.
  • the acronym and common names for amino acid thermal stabilizers and various CAS No. for specific amino acid thermal stabilizers represented by the formulas (X) to (XXVII) are listed in Table 1.
  • Specific M +x counterions useful in the carboxyiate salts are listed in Table 2.
  • the amino acid thermal stabilizer useful in the composition may be selected from the group consisting of ethylene diamine-N,N,N',N'-tetra-acetic acid (EDTA), ethylene g!yco!-bis(2-aminoethylether)-N I N,N',N , -tetraacetic acid (EGTA), 1.2-Diaminacyc!ohexanetetraacetic - Acid (CyDTA),
  • EDTA ethylene diamine-N,N,N',N'-tetra-acetic acid
  • EGTA ethylene g!yco!-bis(2-aminoethylether)-N I N,N',N , -tetraacetic acid
  • CyDTA 1.2-Diaminacyc!ohexanetetraacetic - Acid
  • the amino acid thermal stabilizer useful in the composition is selected from the group consisting of ethylene diamine- ⁇ , ⁇ , ⁇ ', ⁇ '- tetra-acetic acid, ethylene glycol-bis(2-aminoethyIether)-N,N,N',N'-tetraacetic acid (EGTA), and 1 ,2-diaminocyc!ohexanetetraacetic acid; and mixtures thereof.
  • the term "and mixtures thereof means that any combination the sodium, potassium, copper (I), copper (M s, iron (II), and Iron (ill) salts of ethylene diamine-N,N,N ⁇ N' etra-acetic acid, ethylene giycol-bis(2- aminoethyiether)-N,N,N',N'-tetraacetic acid (EGTA), and 1 ,2- diaminocyclohexanetetraacetic acid may be used.
  • a mixture of sodium and copper (I) salts of ethylene diamine-N,N,N',N'-teira-acetic acid may be used; and a mixture of sodium and copper (I) salts of ethylene diamine- ⁇ , ⁇ , ⁇ ', ⁇ '-tetra-acetic acid and sodium and copper (I) salts of 1 ,2- diaminocyclohexanetetraacetic acid may be used.
  • a mixture of sodium and copper (II) salts can be used and a mixture of sodium copper (II) and iron (111) salts can be used.
  • the mixtures of salts can be made "in situ" by appropriate addition of reagents to the melt mixed blend.
  • Preferred amino acid thermal stabilizers for the thermoplastic melt-mixed compositions are those having less than 80 % total weight loss up to 250 °C, as measured by thermal gravimetric analysis, at a heating rate of 10 C/min up to 500 °C in air.
  • Glass fibers with noncircular cross-section refer to glass fiber having a cross section having a major axis lying perpendicular to a longitudinal direction of the glass fiber and corresponding to the longest linear distance in the cross section.
  • the non-circular cross section has a minor axis corresponding to the longest linear distance in the cross section in a direction perpendicular to the major axis.
  • the non-circular cross section of the fiber may have a variety of shapes including a cocoon-type (figure-eight) shape, a rectangular shape; an elliptical shape; a roughly triangular shape; a polygonal shape; and an oblong shape.
  • the cross section may have other shapes.
  • the polymeric toughener can be a functionaiized toughener, a
  • nonfunctionalized toughener or blend of the two
  • a functionaiized toughener has attached to it reactive functional groups which can react with the polyamide.
  • Such functional groups are usually amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids, amino acids
  • Ethylene copolymers are an example of a polymeric toughening agent wherein the functional groups are copolymerized into the polymer, for instance, a copolymer of ethylene and a (meth)acrylate monomer containing the appropriate functional group.
  • (meth)acrylate means the compound may be either an acrylate, a methacrylate, or a mixture of the two.
  • Useful (meth)acrylate functional compounds include (meth)acry!ic acid, 2-hydroxyethyl(meth)acryiate, glycidyl(meth)acrylate, and 2-isocyanatoethyl (meth)acrylate.
  • ethylene and a functionaiized (meth)acrylate monomer may be copolymerized into such a polymer, such as vinyl acetate, unfunctionalized (meth)acry!ate esters such as ethyl (meth)acrylate, n-butyl (meth)acryiate, i-butyl (meth)acryiate and cyclohexyl (meth)acryiate.
  • Polymeric tougheners include those listed in U.S. Patent 4,174,358, which is hereby incorporated by reference.
  • Another functionalized toughener is a polymer having carboxylic acid metal salts.
  • Such polymers may be made by grafting or by copolymerizing a carboxyl or carboxylic anhydride containing compound to attach it to the polymer.
  • Useful materials of this sort include Surlyn® ionomers available from E. I. DuPont de Nemours & Co. Inc., Wilmington, DE 19898 USA, and the metal neutralized maleic anhydride grafted ethylene/a-oiefin polymer described above.
  • Preferred metal cations for these carboxylate salts include Zn. Li, Mg and Mn.
  • ethylene copolymers include ethylene terpoiymers and ethylene multi-polymers, i.e. having greater than three different repeat units.
  • Ethylene copolymers useful as polymeric tougheners in the invention include those selected from the group consisting of ethylene copolymers of the formula E/X/Y wherein:
  • E is the radical formed from ethylene
  • X is selected from the group consisting of radicals formed from
  • R is H, CH 3 or C 2 H 5 , and R 2 is an alkyl group having 1 -8 carbon atoms; vinyl acetate; and mixtures thereof; wherein X comprises 0 to 50 weight % of E/X/Y copolymer;
  • Y is one or more radicals formed from monomers selected from the group consisting of carbon monoxide, sulfur dioxide, acrylonitrile, maleic anhydride, maleic acid diesters, (meth)acryiic acid, maleic acid, maleic acid monoesters, itaconic acid, fumaric acid, fumaric acid monoesters and potassium, sodium and zinc salts of said preceding acids, glycidyl (meth)acrylate, 2-hydroxyethyi
  • the functiona!ized toughener contain a minimum of about 0.5, more preferably 1.0, very preferably about 2.5 weight percent of repeat units and/or grafted molecules containing functional groups or carboxylate salts (including the metal), and a maximum of about 15, more preferably about 13, and very preferably about 10 weight percent of monomers containing functional groups or carboxylate salts (including the metal), it is to be understood than any preferred minimum amount may be combined with any preferred maximum amount to form a preferred range.
  • the polymeric toughener comprises about 2.5 to about 10 weight percent of repeat units and/or grafted molecules containing functional groups or carboxylate salts (including the metal).
  • Nonfunctionaiized tougheners may also be present in addition to a functionaiized toughener.
  • Nonfunctionaiized tougheners include polymers such as ethyiene/a-olefin/diene (EPDM) rubber, poiyolefins including polyethylene (PE) and polypropylene, and ethylene/a-o!efin (EP) rubbers such as ethylene/1 - octene copolymer, and the like such as those commercial copolymers under the ENGAGE® brand from Dow Chemical, Midland Michigan.
  • EPDM ethyiene/a-olefin/diene
  • EP ethylene/a-o!efin
  • acryionitriie-butadiene-styrene is a terpolymer made by polymerizing styrene and acry!onitri!e in the presence of polybutadiene.
  • the proportions can vary from 15 to 35% acryionitrile, 5 to 30% butadiene and 40 to 60% styrene.
  • the result is a long chain of polybutadiene criss-crossed with shorter chains of poly(styrene acryionitrile).
  • polymeric tougheners useful in the invention are having a (vinyl aromatic comonomer) core comprising an ethylene copolymer as disclosed above, the core optionally cross-linked and optionally containing a vinyl aromatic comonomer, for instance styrene; and a shell comprising another polymer that may include polymethyl methacry!ate and optionally contain functional groups including epoxy, or amine.
  • the core-shell polymer may be made up of multiple layers, prepared by a multi-stage, sequential polymerization technique of the type described in US4180529. Each successive stage is polymerized in the presence of the previously polymerized stages. Thus, each layer is polymerized as a layer on top of the immediately preceding stage.
  • the minimum amount of polymeric toughener is 0.1 , and preferably 0.5 weight percent. In other embodiments a minimum amount of polymeric
  • toughener is 2, 4, or 8 weight percent, based on the total weight of the melt- mixed composition.
  • the maximum amount of polymeric toughener is about 20, preferably about 15 and more preferably about 12 weight percent. In other embodiments a maximum amount of polymeric toughener is of 8, 5 or 3.5 weight percent, based on the total weight of the melt-mixed composition. It is to be understood than any minimum amount may be combined with any maximum amount to form a preferred weight range.
  • Preferred polymeric tougheners are selected from the group consisting of :
  • thermoplastic melt-mixed composition and thermoplastic articles derived therefrom comprise 0.1 to 3.5 wt % polymeric toughener.
  • Co-stabilizers include copper stabilizers, secondary aryl amines, hindered amine light stabilizers (HALS), hindered phenols, and mixtures thereof.
  • HALS hindered amine light stabilizers
  • melt-mixed compositions may further comprise 0.01 to about 0.10 weight percent of copper (I) iodide stabilizer.
  • polymeric ingredients and non-polymeric ingredients may be fed into a melt mixer, such as single screw extruder or twin screw extruder, agitator, single screw or twin screw kneader, or Banbury mixer, and the addition step may be addition of all ingredients at once or gradual addition in batches.
  • a melt mixer such as single screw extruder or twin screw extruder, agitator, single screw or twin screw kneader, or Banbury mixer
  • the addition step may be addition of all ingredients at once or gradual addition in batches.
  • a part of the polymeric ingredients and/or non-polymeric ingredients is first added, and then is melt-mixed with the remaining polymeric ingredients and non-polymeric ingredients that are subsequently added, until an adequately mixed composition is obtained.
  • drawing extrusion molding may be used to prepare a reinforced composition.
  • the oven test temperatures for the compositions disclosed herein may be 170 °C and 500, 1000, or 2000 hours test periods; 210 °C and 500 hours test periods; and 230 °C and 500 hours test periods.
  • the test samples, after air oven ageing, are tested for tensile strength and elongation to break, according to ISO 527-2/1 BA test method; and compared with unexposed controls having identical composition and shape, that are dry as molded (DAM).
  • the comparison with the DAM controls provides the retention of tensile strength and/or retention of elongation to break, and thus the various compositions can be assessed as to long-term heat stability performance.
  • One embodiment is a molded or extruded thermoplastic article comprising the thermoplastic melt-mixed composition as disclosed in the above embodiments, wherein the polyamide resin comprises one or more Group (I) Polyamides, wherein 2 mm thick test bars, prepared from said melt-mixed composition and tested according to ISO 527-2/1 BA, and exposed at a test temperature of 170 °C for a test period of 500 hours, in an atmosphere of air, have on average, a retention of tensile strength of at least 50 percent, and preferably at least 80, 70, 80, and 90 %, as compared with that of an unexposed control of identical composition and shape.
  • the polyamide resin comprises one or more Group (I) Polyamides, wherein 2 mm thick test bars, prepared from said melt-mixed composition and tested according to ISO 527-2/1 BA, and exposed at a test temperature of 170 °C for a test period of 500 hours, in an atmosphere of air, have on average, a retention of tensile strength of at least 50 percent
  • thermoplastic article comprising the thermoplastic melt-mixed composition, as disclosed in the above
  • the polyamide resin comprises a one or more polyamides selected from the group consisting of Group (MB) Polyamides, Group (III) Polyamides, Group (IV) Polyamides, Group (V) Polyamides, and Group (VI) Polyamides, wherein 2 mm thick test bars, prepared from said melt-mixed composition and tested according to ISO 527-2/1 BA, and exposed at a test temperature of 230 °C for a test period of 500 hours, in an atmosphere of air, have on average, a retention of tensile strength of at least 50 percent, and preferably at least 60, 70, 80, and 90 %, as compared with that of an unexposed control of identical composition and shape
  • the present invention relates to a method for manufacturing an article by shaping the melt-mixed compositions.
  • articles are films or laminates, automotive parts or engine parts or
  • shaping it is meant any shaping technique, such as for example extrusion, injection molding, thermoform molding, compression molding or blow molding.
  • the article is shaped by injection molding or blow molding.
  • the molded or extruded thermoplastic articles disclosed herein may have application in many vehicular components that meet one or more of the following requirements: high impact requirements; significant weight reduction (over conventional metals, for instance); resistance to high temperature; resistance to oil environment; resistance to chemical agents such as coolants; and noise reduction allowing more compact and integrated design.
  • Specific molded or extruded thermoplastic articles are selected from the group consisting of charge air coolers (CAC); cylinder head covers (CHC); oil pans; engine cooling systems, including thermostat and heater housings and coolant pumps; exhaust systems including mufflers and housings for catalytic converters; air intake manifolds (AIM); and timing chain belt front covers.
  • CAC charge air coolers
  • CHC cylinder head covers
  • oil pans oil pans
  • engine cooling systems including thermostat and heater housings and coolant pumps
  • exhaust systems including mufflers and housings for catalytic converters
  • AIM air intake manifolds
  • a charge air cooler is a part of the radiator of a vehicle that improves engine combustion efficiency.
  • Charge air coolers reduce the charge air temperature and increase the density of the air after compression in the turbocharger thus allowing more air to enter into the cylinders to improve engine efficiency. Since the temperature of the incoming air can be more than 200 ° C when it enters the charge air cooler, it is required that this part be made out of a composition maintaining good mechanical properties under high temperatures for an extended period of time.
  • AH Examples and Comparative Examples were prepared by melt blending the ingredients listed in the Tables in a 30 mm twin screw extruder (ZSK 30 by Coperion) operating at about 280 °C for Poiyamide A and PA88 compositions and 310°C barrel setting for Polyamide B compositions, using a screw speed of about 300 rpm, a throughput of 13.8 kg/hour and a melt temperature measured by hand of about 320 - 355°C for the all compositions.
  • the glass fibers were added to the melt through a screw side feeder.
  • Ingredient quantities shown in the Tables are given in weight percent on the basis of the total weight of the thermoplastic composition.
  • the compounded mixture was extruded in the form of laces or strands, cooled in a water bath, chopped into granules and placed into sealed aluminum lined bags in order to prevent moisture pick up.
  • test specimens were heat aged in a re-circulating air ovens (Heraeus type UT8060) according to the procedure detailed in ISO 2578. At various heat aging times, the test specimens were removed from the oven, allowed to cool to room temperature and sealed into aluminum lined bags until ready for testing. The tensile mechanical properties were then measured according to ISO 527 using a Zwick tensile instrument. The average values obtained from 5 specimens are given in the Tables. Retention of tensile strength (TS) and elongation at break (EL) corresponds to the percentage of the tensile strength and elongation at break after heat aging for 500 hours in comparison with the value of specimens non- heat-aged control specimens considered as being 100%.
  • TS tensile strength
  • EL elongation at break
  • Poiyamide A refers to PA66/6T (75/25 molar ratio repeat units) with amine ends approximately 80 meq/kg, having a typical relative viscosity (RV) of 41 , according to ASTM D-789 method, and a typical melt point of 288 °C, that was provided according to the following procedure: Poiyamide 68 salt solution (3928 lbs. of a 51 .7 percent by weight with a pH of 8.1 ) and 2928 lbs of a 25.2% by weight of poiyamide 6T salt solution with a pH of 7.8 were charged into an autoclave with 100 g of a conventional antifoam agent, 20g of sodium
  • Poiyamide B refers Zytei® HTN502HNC010copoiyamide, made from terephthalic acid, adipic acid, and hexamethy!enediamine; wherein the two acids are used in a 55:45 molar ratio (PA 6T/66); having a melting point of about 310 °C and an inherent viscosity (IV), according to ASTM D2857 method, typically about 1 .07, available from E. I. DuPont de Nemours and Company, Wilmington, Delaware, USA.
  • PA86 refers to an aliphatic poiyamide made of 1 ,6-hexanedioic acid and 1 ,6-hexamethylenediamine having a typical relative viscosity of 49 and a melting point of about 283 °C, commercially available from E. I. DuPont de Nemours and Company, Wilmington, Delaware, USA under the trademark Zytel ® 101 NC010 polyamide.
  • TRX@301 copolymer is maieic anhydride modified EPDM from available from E.I. DuPont de Nemours and Company, Wilmington, Delaware, USA.
  • Glass Fiber B refers to CPIC 301 HP chopped glass fiber available from Chongqing Polycomp International Corp. (CPIC), Peoples Republic of China.
  • Licowax OP is a lubricant manufactured by Clariant Corp., Charlotte, NC.
  • Aluminum stearate is a wax supplied by PMC Global, Inc. Sun Valley, CA,
  • Kenamide El 80 refers to a fatty acid amide lubricant available from
  • Black Pigment B refers to 25 wt % carbon black in PA8 carrier.
  • Cu heat stabilizer refers to a mixture of 7 parts of potassium iodide and 1 part of copper iodide in 0.5 part of a stearate wax binder.
  • 2,6-NDA refers to 2,6-napthalene diearboxyiic acid, supplied from BP Amoco, Napier, !L.
  • PEP 191 refers to oxidized polyethylene wax available from Clariant Corp., Charlotte, NC. Shelfplus® 02 2400 refers to 20 weight percent finely divided iron powder dispersed in polyethylene, available from BASF, Germany
  • HEDTA in sodium sail was available from Aldrich Chemical Co.
  • Examples 1 -5 show significant improvement in tensile strength retention after AOA for 500 h at 230 °C, as compared to comparative examples C1 and C2 using traditional copper stabilizer.
  • Examples 1 1 and 12 having a polymer toughener, show significant improvement in tensile strength retention after AOA for 500 h at 230 °C. as compared with comparative example C4 with copper stabilizer.
  • Example 13 shows a surprising effect of added EDTA disodium salt In compositions comprising copper and iron as compared to comparative examples C5 and C8 without the amino acid thermal stabilizer. Although the AOA gives similar high tensile strength retention for C8 and Example 13, Example 13 shows significantly higher absolute tensile strength than 05 or C8.
  • Examples 14-21 show the effect of a variety of amino acid thermal stabilizers on the AOA tensile strength retention in glass filled compositions.

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Abstract

Disclosed is a thermoplastic melt-mixed composition including a) a polyamide resin; b) about 1.0 to about 5.0 weight percent of an amino acid thermal stabilizer; c) 10 to 60 weight percent reinforcing agent; and, optionally, 0 to 30 weight percent polymeric toughener; and molded or extruded thermoplastic articles made therefrom.

Description

Thermoplastic Melt-mixed Composition with Heat Stabiiizer
Cross Reference to Related Application
Field of Invention
The present invention relates to the field of poiyamide compositions having improved long-term high temperature aging characteristics.
BACKGROUND OF INVENTION
High temperature resins based on po!yamides possess desirable chemical resistance, processabiiity and heat resistance. This makes them particularly well suited for demanding high performance automotive and electrical/electronics applications. There is a current and general desire in the automotive field to have high temperature resistant structures since temperatures higher than 15CTC, even higher than 200'C, are often reached in underhood areas of automobiles. When plastic parts are exposed to such high temperatures for a prolonged period, such as in automotive under-the-hood applications or in electrical/electronics applications, the mechanical properties generally tend to decrease due to the thermo-oxidation of the polymer. This phenomenon is called heat aging.
In an attempt to improve heat aging characteristics, it has been the conventional practice to add heat stabilizers (also referred as antioxidants) to thermoplastic compositions comprising poiyamide resins. Examples of such heat stabilizers include hindered phenol antioxidants, amine antioxidants and phosphorus-based antioxidants. For poiyamide compositions, three types of heat stabilizers are conventionally used to retain the mechanicai properties of the composition upon exposure to high temperatures. One is the use of phenolic antioxidants optionally combined with a phosphorus based synergist as previously mentioned, the use of aromatic amines optionally combined with a phosphorus based synergist and the third one is the use of copper salts and derivatives. Phenolic antioxidants are known to improve the mechanical/physical properties of the thermoplastic composition up to an aging temperature of 120°C. US patent 5,985,852 discloses a thermally stable polyamide molding composition containing colloidal copper formed in situ. However, the disclosed compositions exhibit retention of impact strength only for a heat aging at 140°C.
GB patent 839,067 discloses a polyamide composition comprising a copper salt and a haiide of a strong organic base. However, the disclosed compositions exhibit improved bending heat stability performance only for a heat aging at 170°C.
US 2006/0155034 and US 2008/0146718 patent publications disclose polyamide compositions comprising a metal powder as thermal stabilizer with a fibrous reinforcing agent. Disclosed compositions exhibit improved mechanical properties such as tensile strength and elongation at break upon long-term heat aging at 215°C. However, such metal powders are not only expensive but they are also highly unstable because they are prone to spontaneous combustion.
EP 1041 109 discloses a polyamide composition comprising a polyamide resin, a polyhydric alcohol having a melting point of 150 to 280 °C, that has good fluidity and mechanical strength and is useful in injection welding techniques.
JP 1993043798(A) discloses a composition comprising a metallic chelating agent including EDTA, and a mixture of a polyamide, a modified polyoiefin resin, and a polypropylene resin, with high metal haiide resistance.
US 5130198 discloses polymeric containing compositions having improved oxidative stability having a polymer and at least two stabilizing agents including an ethylene diamine tetra-acetic acid compound. The ethylene diamine tetra-acetic acid compound is incorporated into a glass "sizing" coating, the coated glass be useful in preparing glass reinforced molding resins having improved oxidative stability.
US4602058 discloses a blend comprising (a) polyamide, (b) ethylene copolymer containing carboxylic acid groups; and a minor amount of organic carboxylic acid that has improved compatibility and thermal stability in hot melt adhesive applications.
JP 4934749 discloses a fiber composition comprising polyamide (PA8 exemplified) and multi-carboxylic acids containing nitrogen and their salts, that has improved oxidative stability when treated with an aqueous hydrogen peroxide/hydroxyl amine mixture.
JP 47013882 discloses a molded article or fiber comprising a poiyamide that is surface treated with a chelating chemical solution including nitrogen containing carboxyiic acids including EDTA to improve stability.
US 2010-0029819 A1 discloses molded or extruded thermoplastic article having high heat stability over at least 500 hours at least 170 C° including a thermoplastic resin; one or more poiyhydric alcohols having more than two hydroxy! groups and a having a number average molecular weight of less than 2000; one or more reinforcement agents; and optionally, a polymeric toughener.
Unfortunately, with the existing technologies, molded articles based on poiyamide compositions either suffer from an unacceptable deterioration of their mechanical properties upon long-term high temperature exposure or they are very expensive due to the use of high- cost heat stabilizers.
There remains a need for low-cost poiyamide compositions that are suitable for manufacturing articles and that exhibit good mechanical properties after long-term high temperature exposure.
SUMMARY
One embodiment is a thermoplastic melt-mixed composition comprising: a) a poiyamide resin;
b) about 1.0 to about 5.0 weight percent of an amino acid thermal stabilizer, the amino acid thermal stabilizer comprising at least one or more amino groups; and at least two or more groups selected from carboxyiic acid and carboxyiic acid salt, both represented by the genera! formula -CO2Y; the amino acid thermal stabilizer having a number average molecular weight of less than or equal to about 2000, preferably less than 1000, as determined by calculation of molecular weight of the amino acid thermal stabilizer wherein Y is considered to have a molecular weight equal to 1 ; or, if the amino acid thermal stabilizer is an oligomeric material, as determined with gel permeation chromatography;
c) 10 to 80 weight percent reinforcing agent; and d) 0 to 30 weight percent polymeric toughener;
wherein the weight percents of components a), b), c) and d) are based on the totai weight of the thermoplastic melt-mixed composition.
Another embodiment is a molded or extruded thermoplastic article comprising the thermoplastic melt-mixed composition.
BRIEF DESCRIPTION OF THE FIGURES
Figure 1 illustrates the TGA weight loss curve of an amino acid thermal stabilizer useful in the melt-blended compositions.
DETAILED DESCRIPTION
For the purposes of the description, unless otherwise specified, "high- temperature" means a temperature at or higher than 170 °C, preferably at or higher than 210 °C. and most preferably at or higher than 230 °C.
In the present invention, unless otherwise specified, long-term" refers to an aging period equal or longer than 500 hrs.
As used herein, the term "high heat stability", as applied to the poiyamide composition disclosed herein or to an article made from the composition, refers to the retention of physical properties (for instance, tensile strength) of 2 mm thick molded test bars consisting of the poiyamide composition that are exposed to air oven aging (AOA) conditions at a test temperature at 170 °C for a test period of at least 500 h, in an atmosphere of air, and then tested according to
ISO 527-2/1 BA method. The physical properties of the test bars are compared to that of unexposed controls that have identical composition and shape, and are expressed in terms of "% retention". In another preferred embodiment the test temperature is at 210 °C, the test period is at 500 hours and the exposed test bars have a % retention of tensile strength of at least 50 %. Herein "high heat stability" means that said molded test bars, on average, meet or exceed a retention for tensile strength of 50 % when exposed at a test temperature at 170 °C for a test period of at least 500 h. Compositions exhibiting a higher retention of physical properties for a given exposure temperature and time period have better heat stability. The terms "at 170 °C," "at 210 °C" and "at 230 °C" refer to the nominal temperature of the environment to which the test bars are exposed; with the understanding that the actual temperature may vary by +/- 2 °C from the nominal test temperature.
Oligomeric material, as used herein in reference to an oligomeric amino acid thermal stabilizer refers to a composition having a number average molecular weight of less than or equal to about 2000, said composition derived from polymerization of one or more amino acids and/or amino acid thermal stabilizers, as disclosed herein.
The term "(meth)acrylate" is meant to include acrylate esters and methacrylate esters.
One embodiment of the invention is a thermoplastic melt-mixed
composition comprising:
a) a polyamide resin;
b) about 0.25 to about 5.0 weight percent of an amino acid thermal
stabilizer, the amino acid thermal stabilizer comprising at least one or more amino groups; and at least two or more groups selected from carboxyiic acid and carboxylic acid salt, both represented by the general formula -CO2Y; the amino acid thermal stabilizer having a number average molecular weight of less than or equal to about 2000, preferably less than 1000, as determined by calculation of molecular weight of the amino acid thermal stabilizer wherein Y is considered to have a molecular weight equal to 1 ; or, if the amino acid thermal stabilizer is an oligomeric material, as determined with gel permeation chromatography;
c) 10 to 60 weight percent reinforcing agent; and
d) 0 to 30 weight percent polymeric toughener;
wherein the weight percents of components a), b), c) and d) are based on the total weight of the thermoplastic melt-mixed composition.
In another embodiment the thermoplastic melt-mixed composition may consist essentially of components a), b), c), and d), as disclosed above. In another embodiment the thermoplastic melt-mixed composition comprises 40 to about 89 weight percent of a polyamide resin; about 1.0 to about 5.0 weight percent of an amino acid thermal stabilizer as disclosed above, 10 to about 55 weight percent reinforcing agent and, optionally, up to 30 weight percent polymeric toughener.
The polyamide resin useful in the present invention has a melting point and/or glass transition. Herein melting points and glass transitions are as determined with differential scanning calorimetry (DSC) at a scan rate of 10 °C/min in the first heating scan, wherein the melting point is taken at the maximum of the endothermic peak and the glass transition, if evident, is considered the mid-point of the change in enthalpy.
Polyamides are condensation products of one or more dicarboxylic acids and one or more diamines, and/or one or more aminocarboxylic acids, and/or ring-opening polymerization products of one or more cyclic lactams. Suitable cyclic lactams are caprolactam and laurolactam. Polyamides may be fully aliphatic or semi-aromatic.
Fully aliphatic polyamides used in the resin composition of the present invention are formed from aliphatic and alicyclic monomers such as diamines, dicarboxylic acids, lactams, aminocarboxylic acids, and their reactive equivalents. A suitable aminocarboxylic acid is 1 1 -aminododecanoic acid. Suitable lactams are caprolactam and laurolactam. In the context of this invention, the term "fully aliphatic polyamide" also refers to copolymers derived from two or more such monomers and blends of two or more fully aliphatic polyamides. Linear, branched, and cyclic monomers may be used.
Carboxylic acid monomers comprised in the fully aliphatic polyamides include, but are not limited to aliphatic carboxylic acids, such as for example adipic acid (C8), pime!ic acid (C7). suberic acid (C8), azelaic acid (C9).
decanedioic acid (C10), dodecanedioic acid (C12), tridecanedioic acid (C13), tetradecanedioic acid (C14), and pentadecanedioic acid (C15). Diamines can be chosen among diamines having four or more carbon atoms, including, but not limited to tetramethylene diamine, hexamethy!ene diamine, octamethyiene diamine, decamethylene diamine, dodecamethylene diamine, 2~ methylpentamethyiene diamine, 2-ethy!tetramethylene diamine, 2~
methyioctamethylenediamine; trimethylhexamethy!enediamine, meta-xyiylene diamine, and/or mixtures thereof.
The semi-aromatic polyamide is a homopoiymer, a copolymer, a terpo!ymer or more advanced polymers formed from monomers containing aromatic groups. One or more aromatic carboxylic acids may be terephtha!ate or a mixture of terephthaiate with one or more other carboxylic acids, such as isophthaiic acid, phthaiic acid, 2-methyi terephtha!ic acid and naphthalic acid. In addition, the one or more aromatic carboxylic acids may be mixed with one or more aliphatic dicarboxylic acids, as disclosed above. Alternatively, an aromatic diamine such as meta-xyiylene diamine (MXD) can be used to provide a semi-aromatic polyamide, an example of which is MXD6, a homopoiymer comprising MXD and adipic acid.
Preferred poiyamides disclosed herein are homopolymers or copolymers wherein the term copolymer refers to poiyamides that have two or more amide and/or diamide molecular repeat units. The homopolymers and copolymers are identified by their respective repeat units. For copolymers disclosed herein, the repeat units are listed in decreasing order of mole % repeat units present in the copolymer. The following list exemplifies the abbreviations used to identify monomers and repeat units in the homopoiymer and copolymer poiyamides (PA):
HMD hexamethy!ene diamine (or 6 when used in combination with a
diacid)
T Terephthaiic acid
AA Adipic acid
DMD Decamethylenediamine
6 €-Caprolactam
DDA Decanedioic acid
DDDA Dodecanedioic acid
1 Isophthalic acid
MXD meta-xyiylene diamine TMD 1 ,4-tetramethyiene diamine
4T polymer repeat unit formed from TMD and T
8T polymer repeat unit formed from HMD and T
DT polymer repeat unit formed from 2-MPMD and T
MXD6 polymer repeat unit formed from MXD and AA
66 polymer repeat unit formed from HMD and AA
10T polymer repeat unit formed from DMD and T
410 polymer repeat unit formed from TMD and DDA
510 polymer repeat unit formed from 1 ,5-pentanediamine and DDA 610 polymer repeat unit formed from HMD and DDA
612 polymer repeat unit formed from HMD and DDDA
6 polymer repeat unit formed from€-capro!actam
1 1 polymer repeat unit formed from 1 1 -aminoundecanoic acid
12 polymer repeat unit formed from 12-aminododecanoic acid
Note that in the art the term "6" when used alone designates a polymer repeat unit formed from€-caprolactam. Alternatively "6" when used in
combination with a diacid such as T, for instance 6T, the "6" refers to HMD. In repeat units comprising a diamine and diacid, the diamine is designated first. Furthermore, when "6" is used in combination with a diamine, for instance 86, the first "6" refers to the diamine HMD, and the second "6" refers to adipic acid.
Likewise, repeat units derived from other amino acids or lactams are designated as single numbers designating the number of carbon atoms.
in one embodiment the poiyamide resin comprises a one or more polyamides selected from the group consisting of:
Group (I) Polyamides having said melting point of less than 210 °C, and comprising an aliphatic or semi-aromatic poiyamide selected from the group poly(penfamethyiene decanediamide) (PA510), poly(pentamethylene dodecanediamide) (PA512), poly(s~caprolactam/hexamethylene
hexanediamide) (PA6/66), poly(G-capro!actam/hexamethyiene
decanediamide) (PA6/610), poly(G~capro!actam/hexamethylene
dodecanediamide) (PA6/612). poly(hexamethyiene tridecanediamide) (PA613), polyihexamethylene pentadecanediamide) (PA615), poly(c~ caprolactam/tetramethy!ene ierephihaiamide) (PA6/4T), poly(c- caprolactam/hexamethy!ene ierephihaiamide) (PA8/6T), polyie- caprolactam/decamethy!ene ierephihaiamide) (PA6/10T), poly(e~ caprolactam/dodecamethyiene ierephihaiamide) (PA6/12T),
poly(hexameihyiene decanediamide/hexamethylene ierephihaiamide) (PA610/8T), poly(hexameihylene dodecanediamide/hexamethylene ierephihaiamide) (PA612/6T), poly(hexameihylene
tetradecanediamide/hexamethyiene ierephihaiamide) (PA614/6T), polyie- caproiaciam/ hexameihyiene isophihaiamide/hexameihylene
ierephihaiamide) (PA6/6I/6T), po!y(e-caprolactam/hexamethylene hexanediamide/hexameihylene decanediamide) (PA6/66/610), poly(s~ caprolactam/hexamethylene hexanediamide/hexameihylene
dodecanediamide) (PA6/66/612), poly(e-capro!actam/hexamethy!ene hexanediamide/hexameihylene decanediamide/hexamethylene
dodecanediamide) (PA6/66/610/812), poly(2-methyipentamethylene hexanediamide/hexameihylene hexanediamide/hexameihylene
terephthamide) (PA D6/66/6T), poly(2-methylpentamethylene
hexanediamide/hexameihylene hexanediamide/) (PA D6/66),
poiy(decamethyiene decanediamide) (PA1010), poiy(decamethylene dodecanediamide) (PA1012), poly(decamethylene
decanediamide/decamethy!ene terephthaiamide) (PA1010/10T)
poiy(decamethylene decanediamide/dodecamethyiene decanediamide/ decamethylene terephtha!amide/dodecamethylene terephthaiamide
(PA1010/1210/10T/12T), poiy(1 1 -aminoundecanamide) (PA1 1 ), poly(1 1 - aminoundecanamide/tetramethy!ene terephthaiamide) (PA1 1/4T), po!y(1 1 - aminoundecanamide/hexamethyiene terephthaiamide) (PA1 1/ 8T), poiy(1 1 - aminoundecanamide/decamethy!ene terephthaiamide) (PA1 1/10T), poly(1 1 aminoundecanamide/dodecamethylene ierephihaiamide) (PA1 1/12T), poiy(12-aminododecanamide) (PA12), poly(12- aminododecanamide/tetramethyiene ierephihaiamide) (PA12/4T), poly(12- aminododecanamide/hexamethyiene terephthalamide) (PA12/6T), poly(12~ aminododecanamide/decamethy!ene terephthalamide) (PA12/10T) poiy(dodecamethylene dodecanediamide) (PA1212), and
po!y(dodecamethylene dodecanediamide/dodecamethylene
dodecanediamide/dodecamethylene terephthalamide)) (PA1212/12T);
Group (El) Polyamides having said melting point of at least 210 CC, and comprising an aliphatic poiyamide selected from the group consisting of poiy(tetramethyiene hexanediamide) (PA46), po!y( -capro!actam) (PA 8), poiy(hexamethyiene hexanediamide/(e-capro!actam/) (PA 66/6)
poiy(hexamethyiene hexanediamide) (PA 66), poIy(hexamethylene hexanediamide/hexamethy!ene decanediamide) (PA66/610),
poiy(hexamethyiene hexanediamide/hexamethylene dodecanediamide) (PA66/612), poIy(hexamethy!ene hexanediamide/decamethy!ene
decanediamide) (PA66/1010), poly(hexamethy!ene decanediamide) (PA610), poiy(hexamethylene dodecanediamide) (PA612), poly(hexamethy!ene tetradecanediamide) (PA614), po!y(hexamethylene hexadecanediamide) (PA616), and po!y(tetramethylene hexanediamide/2-methylpentamethylene hexanediamide) (PA46/D6); wherein within Group (I I) Polyamides are Group (HA) Polyamides having a melting point of at least 210 °C and less than 230 °C and Group (I!B) Potyamides having a melting point of 230 °C or greater; Group (HI) Polyamides having a melting point of greater than 230 °C, and comprising
(aa) about 20 to about 35 mole percent semi-aromatic repeat units derived from monomers selected from one or more of the group consisting of:
(i) aromatic dicarboxy!ic acids having 8 to 20 carbon atoms and aliphatic diamines having 4 to 20 carbon atoms; and
(bb) about 65 to about 80 mole percent aliphatic repeat units derived from monomers selected from one or more of the group consisting of:
(ii) an aliphatic dicarboxyiic acid having 6 to 20 carbon atoms and said aliphatic diamine having 4 to 20 carbon atoms; and (iii) a lactam and/or aminocarboxylic acid having 4 to 20 carbon atoms;
Group {N) Polyamldes having a melting point of greater than 230 °C, comprising
(cc) about 50 to about 95 mole percent semi-aromatic repeat units derived from monomers selected from one or more of the group consisting of:
(i) aromatic dicarboxy!ic acids having 8 to 20 carbon atoms and aliphatic diamines having 4 to 20 carbon atoms; and
(dd) about 5 to about 50 mole percent aliphatic repeat units derived from monomers selected from one or more of the group consisting of:
(ii) an aliphatic dicarboxyiic acid having 6 to 20 carbon atoms and said aliphatic diamine having 4 to 20 carbon atoms; and
(iii) a lactam and/or aminocarboxylic acid having 4 to 20 carbon atoms;
Group (V) Polyamldes having a melting point of at least 260 °C, and comprising
(ee) greater than 95 mole percent semi-aromatic repeat units derived from monomers selected from one or more of the group consisting of: (i) aromatic dicarboxyiic acids having 8 to 20 carbon atoms and
aliphatic diamines having 4 to 20 carbon atoms; and
(ff) less than 5 mole percent aliphatic repeat units derived from monomers selected from one or more of the group consisting of:
(ii) an aliphatic dicarboxyiic acid having 8 to 20 carbon atoms and said aliphatic diamine having 4 to 20 carbon atoms;
(iii) a lactam and/or aminocarboxylic acid having 4 to 20 carbon atoms; and
Group (VI) PoHyamic!es having no melting point and selected from the group consisting of poiy(hexamethylene isophtha!amide/ hexamethy!ene
terephthalamide) (8I/8T) and poiyihexamethylene isophthalamide/hexamethy!ene terephthalamide/hexamethylene
hexanediamide) (6I/6T/68).
Group (MA) Polyamides have a melting point of at least 210 °C and less than 230 °C and include aliphatic polyamides selected from the group consisting of po!y(e-caprolactam) (PA 8), poly(hexamethylene hexanediamide/(e-caprolactam/) (PA 88/8) poly(hexamethylene hexanediamide/hexamethyiene decanediamide) (PA66/610), poly(hexamethyiene hexanediamide/hexamethylene
dodecanediamide) (PA88/812), poiy(hexamethyiene
hexanediamide/decamethy!ene decanediamide) (PA68/1 Q1 G),
po!y(hexamethylene decanediamide) (PA810), poly(hexamethyiene
dodecanediamide) (PA812), poiy(hexamethy!ene tetradecanediamide) (PA814), po!y(hexamethylene hexadecanediamide) (PA816), and poly(tetramethylene hexanediamide/2-methy!pentamethylene hexanediamide) (PA46/D6). The artisan recognizes that several of the Group (MA) Polyamides melting points including PA 88/6, PA88/810, and PA46/D6, depend upon the ratio of repeat units, and thus Group (MA) Polyamides have a ratio of repeat units that meets the requirement of having a melting point of greater than 230 °C.
Group (MB) Polyamides have a melting point of greater than 230 CC and comprise an aliphatic poiyamide selected from the group consisting of:
poly(tetramethylene hexanediamide) (PA46), poiy(hexamethylene
hexanediamide/(c-caprolactam/) (PA 88/8), polyihexamethyiene hexanediamide) (PA 86), poly(hexamethylene hexanediamide/hexamethylene decanediamide) (PA88/810), and polyitetramethylene hexanediamide/2-methylpentamethylene hexanediamide) (PA46/D6). The artisan recognizes that several of the Group (I IB) Polyamides melting points including PA 68/8, PA86/610, and PA48/D6, depend upon the ratio of repeat units, and thus Group (MB) Polyamides have a ratio of repeat units that meets the requirement of having a melting point of at least 210 °C and less than 230 °C.
in one embodiment the poiyamide resin comprises one or more polyamides selected from the group consisting of Group (III) Polyamides, Group (IV)
Polyamides, Group (V) Polyamides and Group (VI) Polyamides. In another embodiment the poiyamide resin comprises one or more poiyamides selected from the group consisting of Group (IN) Poiyamides, Group (IV) Poiyamides, and Group (V) Poiyamides.
The composition comprises about 1.0 to about 5.0 weight percent of an amino acid thermal stabilizer based on the total weight of the melt-mixed composition, in preferred embodiments the melt-mixed composition comprises about 1.2 to 5.0 weight percent, about 1.2 to 4.0 weight percent or about 1.4 to 4.0 weight percent of an amino acid thermal stabilizer based on the total weight of the melt-mixed composition. The amino acid thermal stabilizer comprises at least one or more amino groups, and preferably two or more amino groups; and at least two or more groups selected from carboxylic acid and carboxyiic acid salt; said carboxylic acid and carboxylic acid salt represented by the general formula -CO2Y; and the amino acid thermal stabilizer having a number average molecular weight of less than or equal to about 2000, preferably less than 1000, as determined by calculation of molecular weight of the amino acid thermal stabilizer wherein Y is considered to have a molecular weight equal to 1 ; or if the amino acid thermal stabilizer is an oligomeric material, as determined with gel permeation chromatography. The term "at least two or more groups selected from carboxylic acid and carboxyiic acid salt" means the amino acid thermal stabilizer can have two or more carboxyiic acids, two or more carboxyiic acid salts, or a mixture of carboxyiic acids and carboxyiic acid salts. Within the term "- CO2Y", the carboxylic acid salt comprises a carboxylate anion and a positively charged counter-ion. The carboxyiic acid salt can have a single counter-ion or be a mixture of counter-ions.
The amino acid thermal stabilizer may have two amino groups, three amino groups, four amino groups, five amino groups, or more than five amino groups. The amino acid thermal stabilizer can have two, three, four, five, or more than five carboxylic acids, carboxyiic acid salt groups, or mixtures thereof.
The carboxyiic acid salt groups are available from a parent carboxylic acid by neutralization of the parent carboxylic acid with appropriate metal hydroxides or oxides, ammonium hydroxide, or by ion exchange. Useful carboxyi acid salts include monovalent ion salts, such as Li, Na, K, ammonium and phosphonium ions; divalent ion salts such as g, Ca, Ba, Cu, Fe(il) salts; trivalent ion salts such as Fe(ill) salts; and tetravalent salts such as Ti(IV) and Zr(iV) salts.
Additionally, the carboxyi acid salts can comprise a mixture of ions such as Na and K ions, Ca and Mg, Na and Cu (I), Na and Cu (Π), Na and Fe(H), and Na and Fe(lii), to mention a few of the mixtures of salts available by appropriate neutralization of the parent amino acids.
Herein the term ammonium ion and phosphonium ion refers to the general classes of R4N+ and R4P* ions wherein R is, independently, selected from the group consisting of H, Ci - C-ie linear or branched alkyl, and phenyl; wherein the linear or branched alkyl groups may have one or two sites of unsaturation, and wherein the linear or branched alkyl groups may be interrupted by one to three heteroatoms selected from oxygen and sulfur. Phosphonium ions may be wherein R is, independently, selected from the group consisting of Ci - Cis linear or branched alkyl. Ammonium ions may be wherein R is, independently, selected from the group consisting of H, Ci - Cis linear or branched alkyl.
Ammonium ions may be wherein R is, independently, selected from the group consisting of H, C-i - Cio linear or branched alkyl, and preferably wherein R is, independently, selected from the group consisting of H, d■■■· C4 linear or branched alkyl. A preferred ammonium ion is NH4 +.
The amino groups and carboxylic acid groups are linked to one another by linking groups comprising one or more carbon atoms. Preferably the linking groups comprise one or two carbon atoms, and preferably linking groups linking an amino group to a carboxylic acid group comprises one carbon atom. Linking groups between two amino groups may comprise one, two, or more carbon atoms. Linking groups may include one or more heteroatoms such as oxygen or sulfur.
The amino acid thermal stabilizer may have one or more hydroxyl groups. The amino acid thermal stabilizers useful in the melt-mixed compositions include those of formula (X) to (XXVII):
Figure imgf000016_0001
Figure imgf000017_0001

Figure imgf000018_0001
Figure imgf000019_0001

Figure imgf000020_0001
(XXVI)
Figure imgf000021_0001
(XXVII);
wherein a counter-ion Y can be H, or 1/x M wherein x is an integer of 1 to 7, and M is a metal ion, ammonium ion or phosphonium ion. The acronym and common names for amino acid thermal stabilizers and various CAS No. for specific amino acid thermal stabilizers represented by the formulas (X) to (XXVII) are listed in Table 1. Specific M+x counterions useful in the carboxyiate salts are listed in Table 2.
Table 1 Specific amino acid thermal stabilizers represented by the formulas (X) to (XXVIi).
Figure imgf000022_0001
(XX!) Y= ί/χΜ" ΤΕΤΗΑ salts Triethylenetetramine- N,N,N',N",N'",N"'-hexaacetic add
salts
(XXi!) Υ - Η PDTA 1 ,3-Propanediamine Tetraacetic 1939-36-2
acid
(ΧΧΗ) Υ = 1/χ Μ+χ PDTA saifs 1 ,3-Propanediamine Tetraacetic
acid salts
(XXSli) Υ = Η GLDA Dicarboxymethyl glutamic acid 51981-21-6
(XXill) Υ= 1/χ +χ GLDA salts Dicarboxymethyl glutamic acid 51981-21-6 (Na4 salt) salts
(XXIV) Υ = Η EDDS (S,S)--Ethylene Diamine 20846-91-7
Disuccinic Acid
(XXIV) Υ= 1/χΜ÷χ EDDS salts (S,S)-Ethyiene Diamine 178949-82-1 (Na2 salt)
Disuccinic Acid salts
(XXV) Υ = Η BCMA N,N~Bls(carboxymethyl)-DL- alanine
(XXV) Υ= 1/χΜ+χ BCMA salts N,N-Bis(carboxymethyl)-DL- 164462-16-2
alanine salts
(XXVi) Υ = Η BC L Na, Na~ B is(carboxy m ethyl )■■ L- !ys i n e 113231-05-3
hydrate
(XXV!) Υ= 1/χΜ+χ BC L salts /Va,/VQ-Bis(carboxymethy!)-L-!ysine
hydrate salts
(XXVII) Υ = Η BCMG N,N-Bis{carboxymethyl)giucamine
(XXVII) Υ = 1/χ Μ"χ BC G salts N,N-Bls(carboxymethyi)glucamlne 49755-02-4 (Na2 salt) salts
Table 2 Counter-ions useful in amino acid carboxylaie salts
Figure imgf000023_0001
The amino acid thermal stabilizer useful in the composition may be selected from the group consisting of ethylene diamine-N,N,N',N'-tetra-acetic acid (EDTA), ethylene g!yco!-bis(2-aminoethylether)-NIN,N',N,-tetraacetic acid (EGTA), 1.2-Diaminacyc!ohexanetetraacetic - Acid (CyDTA),
Diethylenetriaminepentaacetic acid (DTPA), 1 ,3-Diamino-2-hydroxypropane- N.N.N'.N'-tetraacetic acid (1 ,3D2HPTA),Triethylenetetramine-NININ,,N",N,,,,N",- hexaacetic acid (TETHA), N(2-hydroxyethyl)ethyienediamine triacetic acid (HEDTA) ; and their sodium, potassium, copper (I), copper (!l), iron (li), and Iron (Hi) salts; and mixtures thereof. Within this context the term "and mixtures thereof means that any combination the acid and the sodium, potassium, copper (I), copper (Π), iron (N), and Iron (Ml) salt may be used,
In a preferred embodiment the amino acid thermal stabilizer useful in the composition is selected from the group consisting of ethylene diamine-Ν,Ν,Ν',Ν'- tetra-acetic acid, ethylene glycol-bis(2-aminoethyIether)-N,N,N',N'-tetraacetic acid (EGTA), and 1 ,2-diaminocyc!ohexanetetraacetic acid; and mixtures thereof. in another preferred embodiment the amino acid thermal stabilizer useful in the composition is selected from the group consisting of sodium, potassium, copper (1), copper (11), iron (11), Iron (III) salts of ethylene diamine~N,N,N',N'-tetra- acetic acid, ethylene glycol-bis(2-aminoethyiether)-N,N,N',Nl-tetraacetic acid (EGTA), and 1 ,2-diaminocyclohexanetetraacetic acid; and mixtures thereof. Within this context the term "and mixtures thereof means that any combination the sodium, potassium, copper (I), copper (M s, iron (II), and Iron (ill) salts of ethylene diamine-N,N,N\N' etra-acetic acid, ethylene giycol-bis(2- aminoethyiether)-N,N,N',N'-tetraacetic acid (EGTA), and 1 ,2- diaminocyclohexanetetraacetic acid may be used. For instance a mixture of sodium and copper (I) salts of ethylene diamine-N,N,N',N'-teira-acetic acid may be used; and a mixture of sodium and copper (I) salts of ethylene diamine- Ν,Ν,Ν',Ν'-tetra-acetic acid and sodium and copper (I) salts of 1 ,2- diaminocyclohexanetetraacetic acid may be used. A mixture of sodium and copper (II) salts can be used and a mixture of sodium copper (II) and iron (111) salts can be used. The mixtures of salts can be made "in situ" by appropriate addition of reagents to the melt mixed blend.
Preferred amino acid thermal stabilizers for the thermoplastic melt-mixed compositions are those having less than 80 % total weight loss up to 250 °C, as measured by thermal gravimetric analysis, at a heating rate of 10 C/min up to 500 °C in air. Figure 1 illustrates the TGA weight loss curve of EDTA fefrasodium salt (Y = Na4); and shows about 9.5 % weight loss up to 250 °C. in general materials having low weight loss are useful in poiyamide compositions having higher melting points and processing temperatures.
The thermoplastic melt-mixed composition and thermoplastic articles derived therefrom comprise 10 to about 80 weight percent, and preferably about 12.5 to 55 weight percent, and 15 to 50 weight percent, of one or more reinforcement agents. The reinforcement agent may be any filler, but is preferably selected from the group consisting of calcium carbonate, glass fibers with circular cross-section, glass fibers with noncircular cross-section, glass flakes, glass beads, carbon fibers, talc, mica, woilastonite, calcined clay, kaolin, diatomite, magnesium sulfate, magnesium silicate, barium sulfate, titanium dioxide, sodium aluminum carbonate, barium ferrite, potassium titanate and mixtures thereof.
Glass fibers with noncircular cross-section refer to glass fiber having a cross section having a major axis lying perpendicular to a longitudinal direction of the glass fiber and corresponding to the longest linear distance in the cross section. The non-circular cross section has a minor axis corresponding to the longest linear distance in the cross section in a direction perpendicular to the major axis. The non-circular cross section of the fiber may have a variety of shapes including a cocoon-type (figure-eight) shape, a rectangular shape; an elliptical shape; a roughly triangular shape; a polygonal shape; and an oblong shape. As will be understood by those skilled in the art, the cross section may have other shapes. The ratio of the length of the major axis to that of the minor access is preferably between about 1.5:1 and about 6:1. The ratio is more preferably between about 2:1 and 5:1 and yet more preferably between about 3:1 to about 4:1. Suitable glass fiber are disclosed in EP 0 190 001 and EP 0 196 194.
Preferably the reinforcing agent is selected from glass fibers with circular cross-section or glass fibers with noncircular cross-section.
The polymeric toughener is a polymer, typically an elastomer having a melting point and/or glass transition points below 25 °C, or is rubber-like, i.e., has a heat of melting (measured by AST Method D3418-82) of less than about 10 j/g, more preferabl less than about 5 J/g, and/or has a melting point of less than 80 °C, more preferably less than about 60 °C. Preferably the polymeric toughener has a weight average molecular weight of about 5,000 or more, more preferably about 10,000 or more, when measured by gel permeation
chromatography using polyethylene standards.
The polymeric toughener can be a functionaiized toughener, a
nonfunctionalized toughener, or blend of the two,
A functionaiized toughener has attached to it reactive functional groups which can react with the polyamide. Such functional groups are usually
"attached" to the polymeric toughener by grafting small molecules onto an already existing polymer or by copo!ymerizing a monomer containing the desired functional group when the polymeric tougher molecules are made by
copolymerization. As an example of grafting, maleic anhydride may be grafted onto a hydrocarbon rubber (such as an ethylene/a-olefin copolymer, an a-oiefin being a straight chain olefin with a terminal double bond such a propylene or 1 - octene) using free radical grafting techniques. The resulting grafted polymer has carboxylic anhydride and/or carboxyl groups attached to it.
Ethylene copolymers are an example of a polymeric toughening agent wherein the functional groups are copolymerized into the polymer, for instance, a copolymer of ethylene and a (meth)acrylate monomer containing the appropriate functional group. Herein the term (meth)acrylate means the compound may be either an acrylate, a methacrylate, or a mixture of the two. Useful (meth)acrylate functional compounds include (meth)acry!ic acid, 2-hydroxyethyl(meth)acryiate, glycidyl(meth)acrylate, and 2-isocyanatoethyl (meth)acrylate. In addition to ethylene and a functionaiized (meth)acrylate monomer, other monomers may be copolymerized into such a polymer, such as vinyl acetate, unfunctionalized (meth)acry!ate esters such as ethyl (meth)acrylate, n-butyl (meth)acryiate, i-butyl (meth)acryiate and cyclohexyl (meth)acryiate. Polymeric tougheners include those listed in U.S. Patent 4,174,358, which is hereby incorporated by reference. Another functionalized toughener is a polymer having carboxylic acid metal salts. Such polymers may be made by grafting or by copolymerizing a carboxyl or carboxylic anhydride containing compound to attach it to the polymer. Useful materials of this sort include Surlyn® ionomers available from E. I. DuPont de Nemours & Co. Inc., Wilmington, DE 19898 USA, and the metal neutralized maleic anhydride grafted ethylene/a-oiefin polymer described above. Preferred metal cations for these carboxylate salts include Zn. Li, Mg and Mn.
Polymeric tougheners useful in the invention include those selected from the group consisting of ethylene copolymers; ethy!ene/a-olefin or ethy!ene/a- olefin/diene copolymer grafted with an unsaturated carboxylic anhydride; core- shell polymers, and nonfunctiona!ized tougheners, as defined herein.
Herein the term ethylene copolymers include ethylene terpoiymers and ethylene multi-polymers, i.e. having greater than three different repeat units. Ethylene copolymers useful as polymeric tougheners in the invention include those selected from the group consisting of ethylene copolymers of the formula E/X/Y wherein:
E is the radical formed from ethylene;
X is selected from the group consisting of radicals formed from
CH2-CH(R1)-C(0)-GR2
wherein R is H, CH3 or C2H5, and R2 is an alkyl group having 1 -8 carbon atoms; vinyl acetate; and mixtures thereof; wherein X comprises 0 to 50 weight % of E/X/Y copolymer;
Y is one or more radicals formed from monomers selected from the group consisting of carbon monoxide, sulfur dioxide, acrylonitrile, maleic anhydride, maleic acid diesters, (meth)acryiic acid, maleic acid, maleic acid monoesters, itaconic acid, fumaric acid, fumaric acid monoesters and potassium, sodium and zinc salts of said preceding acids, glycidyl (meth)acrylate, 2-hydroxyethyi
(meth)acryiate, 2-isocyanatoethyi (meth)acrylate and glycidyl vinyl ether; wherein Y is from 0.5 to 35 weight % of the E/X/Y copolymer, and preferably 0.5-20 weight percent of the E/X/Y copolymer, and E is the remainder weight percent and preferably comprises 40-90 weight percent of the E/X/Y copolymer. Ιί is preferred that the functiona!ized toughener contain a minimum of about 0.5, more preferably 1.0, very preferably about 2.5 weight percent of repeat units and/or grafted molecules containing functional groups or carboxylate salts (including the metal), and a maximum of about 15, more preferably about 13, and very preferably about 10 weight percent of monomers containing functional groups or carboxylate salts (including the metal), it is to be understood than any preferred minimum amount may be combined with any preferred maximum amount to form a preferred range. There may be more than one type of functional monomer present in the polymeric toughener, and/or more than one polymeric toughener. In one embodiment the polymeric toughener comprises about 2.5 to about 10 weight percent of repeat units and/or grafted molecules containing functional groups or carboxylate salts (including the metal).
It has been found that often the toughness of the composition is increased by increasing the amount of functionaiized toughener and/or the amount of functional groups and/or metal carboxylate groups. However, these amounts should preferably not be increased to the point that the composition may crosslink (thermoset), especially before the final part shape is attained, and/or the first to melt tougheners may crosslink each other. Increasing these amounts may also increase the melt viscosity, and the melt viscosity should also preferably not be increased so much that molding is made difficult.
Nonfunctionaiized tougheners may also be present in addition to a functionaiized toughener. Nonfunctionaiized tougheners include polymers such as ethyiene/a-olefin/diene (EPDM) rubber, poiyolefins including polyethylene (PE) and polypropylene, and ethylene/a-o!efin (EP) rubbers such as ethylene/1 - octene copolymer, and the like such as those commercial copolymers under the ENGAGE® brand from Dow Chemical, Midland Michigan. Other nonfunctional tougheners include the styrene -containing polymers including acryionitri!e- styrene copolymer, acryionitriie-butadiene-styrene copolymer, styrene-isoprene- styrene copolymer, styrene-hydrogenated isoprene-styrene copolymer, styrene- butadiene-styrene copolymer, styrene-hydrogenated butadiene-styrene copolymer, styrenic block copolymer, (are not the above listed polymers block or random polymers?) polystyrene. For example, acryionitriie-butadiene-styrene, or ABS, is a terpolymer made by polymerizing styrene and acry!onitri!e in the presence of polybutadiene. The proportions can vary from 15 to 35% acryionitrile, 5 to 30% butadiene and 40 to 60% styrene. The result is a long chain of polybutadiene criss-crossed with shorter chains of poly(styrene acryionitrile).
Other polymeric tougheners useful in the invention are having a (vinyl aromatic comonomer) core comprising an ethylene copolymer as disclosed above, the core optionally cross-linked and optionally containing a vinyl aromatic comonomer, for instance styrene; and a shell comprising another polymer that may include polymethyl methacry!ate and optionally contain functional groups including epoxy, or amine. The core-shell polymer may be made up of multiple layers, prepared by a multi-stage, sequential polymerization technique of the type described in US4180529. Each successive stage is polymerized in the presence of the previously polymerized stages. Thus, each layer is polymerized as a layer on top of the immediately preceding stage.
The minimum amount of polymeric toughener is 0.1 , and preferably 0.5 weight percent. In other embodiments a minimum amount of polymeric
toughener is 2, 4, or 8 weight percent, based on the total weight of the melt- mixed composition. The maximum amount of polymeric toughener is about 20, preferably about 15 and more preferably about 12 weight percent. In other embodiments a maximum amount of polymeric toughener is of 8, 5 or 3.5 weight percent, based on the total weight of the melt-mixed composition. It is to be understood than any minimum amount may be combined with any maximum amount to form a preferred weight range.
Polymeric tougheners are selected from the group consisting of ethylene copolymers; ethylene/a-oiefin or ethylene/a-oiefin/diene copolymer grafted with an unsaturated carboxylic anhydride; core-shell polymers, and nonfunctionaiized tougheners, as defined herein.
Preferred polymeric tougheners are selected from the group consisting of :
(a) A copolymer of ethylene, g!ycidyl (meth)acrylate, and optionally one or more (meth)acryiate esters. (b) An ethylene/a-o!efin or ethylene/a-oiefin/diene (EPDM) copolymer grafted with an unsaturated carboxylic anhydride such as maleic anhydride.
(c) A copolymer of ethylene, 2-isocyanatoethyl (meth)acryiate. and optionally one or more (meth)acry!ate esters.
(d) a copolymer of ethylene and acrylic acid reacted with a Zn, Li, g or Mn compound to form the corresponding ionomer.
In one embodiment the thermoplastic melt-mixed composition and thermoplastic articles derived therefrom comprise 0.1 to 30 wt % of polymeric toughener.
In one embodiment the thermoplastic melt-mixed composition and thermoplastic articles derived therefrom comprise 0.1 to 30 vvt % of polymeric toughener with the proviso that the polymeric toughener comprises less than 5 weight percent of an ethylene copolymer, based on the total weight of the melt- mixed composition.
In one embodiment the thermoplastic melt-mixed composition and thermoplastic articles derived therefrom comprise 0.1 to 3.5 wt % polymeric toughener.
In the present invention, the polymer composition of the present invention may also comprise other additives commonly used in the art, such other heat stabilizers or antioxidants referred to as "co-stabilizers", antistatic agents, blowing agents, lubricants, plasticizers, and colorant and pigments.
Co-stabilizers include copper stabilizers, secondary aryl amines, hindered amine light stabilizers (HALS), hindered phenols, and mixtures thereof.
The melt-mixed compositions, as disclosed above may further comprise 0.01 to about 0.10 weight percent of copper (I) iodide stabilizer.
The melt-mixed compositions, as disclosed above may further comprise 0.1 to about 5.00 weight percent, and preferably about 0.5 to 4.0 weight percent of iron powder stabilizer. An appropriate source of iron powder is Shelfplus® 02 2400, a branded product, that refers to 20 weight percent finely divided iron powder dispersed in polyethylene, available from BASF, Germany. Herein the thermoplastic composition is a mixture by melt-blending, in which all polymeric ingredients are adequately mixed, and all non-polymeric ingredients are adequately dispersed in a polymer matrix. Any melt-blending method may be used for mixing polymeric ingredients and non-polymeric ingredients of the present invention. For example, polymeric ingredients and non-polymeric ingredients may be fed into a melt mixer, such as single screw extruder or twin screw extruder, agitator, single screw or twin screw kneader, or Banbury mixer, and the addition step may be addition of all ingredients at once or gradual addition in batches. When the polymeric ingredient and non-polymeric ingredient are gradually added in batches, a part of the polymeric ingredients and/or non-polymeric ingredients is first added, and then is melt-mixed with the remaining polymeric ingredients and non-polymeric ingredients that are subsequently added, until an adequately mixed composition is obtained. If a reinforcing filler presents a long physical shape (for example, a long glass fiber), drawing extrusion molding may be used to prepare a reinforced composition.
The melt-mixed compositions, as disclosed above, are useful in increasing long-term thermal stability at high temperatures of molded or extruded articles made therefrom. The long-term heat stability of the articles can be assessed by exposure (air oven ageing) of 2 mm thick test samples at various test
temperatures in an oven for various test periods of time. The oven test temperatures for the compositions disclosed herein may be 170 °C and 500, 1000, or 2000 hours test periods; 210 °C and 500 hours test periods; and 230 °C and 500 hours test periods. The test samples, after air oven ageing, are tested for tensile strength and elongation to break, according to ISO 527-2/1 BA test method; and compared with unexposed controls having identical composition and shape, that are dry as molded (DAM). The comparison with the DAM controls provides the retention of tensile strength and/or retention of elongation to break, and thus the various compositions can be assessed as to long-term heat stability performance.
One embodiment is a molded or extruded thermoplastic article comprising the thermoplastic melt-mixed composition as disclosed in the above embodiments, wherein the polyamide resin comprises one or more Group (I) Polyamides, wherein 2 mm thick test bars, prepared from said melt-mixed composition and tested according to ISO 527-2/1 BA, and exposed at a test temperature of 170 °C for a test period of 500 hours, in an atmosphere of air, have on average, a retention of tensile strength of at least 50 percent, and preferably at least 80, 70, 80, and 90 %, as compared with that of an unexposed control of identical composition and shape.
One embodiment is a molded or extruded thermoplastic article comprising the thermoplastic melt-mixed composition, as disclosed in the above
embodiments, wherein the polyamide resin comprises one or more Group (II) Polyamides, wherein 2 mm thick test bars, prepared from said melt-mixed composition and tested according to ISO 527-2/1 BA, and exposed at a test temperature of 210 °C for a test period of 500 hours, in an atmosphere of air, have on average, a retention of tensile strength of at least 50 percent, and preferably at least 60, 70, 80, and 90 %, as compared with that of an unexposed control of identical composition and shape.
One embodiment is a molded or extruded thermoplastic article comprising the thermoplastic melt-mixed composition, as disclosed in the above
embodiments, wherein the polyamide resin comprises a one or more polyamides selected from the group consisting of Group (MB) Polyamides, Group (III) Polyamides, Group (IV) Polyamides, Group (V) Polyamides, and Group (VI) Polyamides, wherein 2 mm thick test bars, prepared from said melt-mixed composition and tested according to ISO 527-2/1 BA, and exposed at a test temperature of 230 °C for a test period of 500 hours, in an atmosphere of air, have on average, a retention of tensile strength of at least 50 percent, and preferably at least 60, 70, 80, and 90 %, as compared with that of an unexposed control of identical composition and shape
In another aspect, the present invention relates to a method for manufacturing an article by shaping the melt-mixed compositions. Examples of articles are films or laminates, automotive parts or engine parts or
electrical/electronics parts. By "shaping", it is meant any shaping technique, such as for example extrusion, injection molding, thermoform molding, compression molding or blow molding. Preferably, the article is shaped by injection molding or blow molding.
The molded or extruded thermoplastic articles disclosed herein may have application in many vehicular components that meet one or more of the following requirements: high impact requirements; significant weight reduction (over conventional metals, for instance); resistance to high temperature; resistance to oil environment; resistance to chemical agents such as coolants; and noise reduction allowing more compact and integrated design. Specific molded or extruded thermoplastic articles are selected from the group consisting of charge air coolers (CAC); cylinder head covers (CHC); oil pans; engine cooling systems, including thermostat and heater housings and coolant pumps; exhaust systems including mufflers and housings for catalytic converters; air intake manifolds (AIM); and timing chain belt front covers. As an illustrative example of desired mechanical resistance against long-term high temperature exposure, a charge air cooler can be mentioned. A charge air cooler is a part of the radiator of a vehicle that improves engine combustion efficiency. Charge air coolers reduce the charge air temperature and increase the density of the air after compression in the turbocharger thus allowing more air to enter into the cylinders to improve engine efficiency. Since the temperature of the incoming air can be more than 200°C when it enters the charge air cooler, it is required that this part be made out of a composition maintaining good mechanical properties under high temperatures for an extended period of time.
The present invention is further illustrated by the following examples, it should be understood that the following examples are for illustration purposes only, and are not used to limit the present invention thereto.
Methods
Compounding Method
AH Examples and Comparative Examples were prepared by melt blending the ingredients listed in the Tables in a 30 mm twin screw extruder (ZSK 30 by Coperion) operating at about 280 °C for Poiyamide A and PA88 compositions and 310°C barrel setting for Polyamide B compositions, using a screw speed of about 300 rpm, a throughput of 13.8 kg/hour and a melt temperature measured by hand of about 320 - 355°C for the all compositions. The glass fibers were added to the melt through a screw side feeder. Ingredient quantities shown in the Tables are given in weight percent on the basis of the total weight of the thermoplastic composition.
The compounded mixture was extruded in the form of laces or strands, cooled in a water bath, chopped into granules and placed into sealed aluminum lined bags in order to prevent moisture pick up.
Thermal Gravimetric Analysis Method (TGA)
The weight loss of the amino acid thermal stabilizers was determined heating about 15-20 mg sample of compound in a thermal analyzer (TA
Instruments) in air at a rate of 10 °C/min from room temperature to 500 °C. The weight lost was measured as a function of temperature. Mechanical Tensile Properties
Mechanical tensile properties, i.e. E-modulus, stress at break (Tensile strength) and strain at break (elongation at break) were measured according to ISO 527-2/1 BA. Measurements were made on 2 mm thick injection molded ISO tensile bars at a testing speed of 5 mm/min. Moid temperature for PA 6T/DT test specimens was 145-150 °C; moid temperature for PA 6T/88 test specimens was 90 - 100 °C; and melt temperature was 325 - 330 °C for both resins.
Air Oven Ageing (AOA)
The test specimens were heat aged in a re-circulating air ovens (Heraeus type UT8060) according to the procedure detailed in ISO 2578. At various heat aging times, the test specimens were removed from the oven, allowed to cool to room temperature and sealed into aluminum lined bags until ready for testing. The tensile mechanical properties were then measured according to ISO 527 using a Zwick tensile instrument. The average values obtained from 5 specimens are given in the Tables. Retention of tensile strength (TS) and elongation at break (EL) corresponds to the percentage of the tensile strength and elongation at break after heat aging for 500 hours in comparison with the value of specimens non- heat-aged control specimens considered as being 100%.
Materials
Poiyamide A refers to PA66/6T (75/25 molar ratio repeat units) with amine ends approximately 80 meq/kg, having a typical relative viscosity (RV) of 41 , according to ASTM D-789 method, and a typical melt point of 288 °C, that was provided according to the following procedure: Poiyamide 68 salt solution (3928 lbs. of a 51 .7 percent by weight with a pH of 8.1 ) and 2928 lbs of a 25.2% by weight of poiyamide 6T salt solution with a pH of 7.8 were charged into an autoclave with 100 g of a conventional antifoam agent, 20g of sodium
hypophosphite, 220g of sodium bicarbonate, 2478 g of 80% HMD solution in water, and 1584 g of glacial acetic. The solution was then heated while the pressure was allowed to rise to 285 psia at which point, steam was vented to maintain the pressure at 265 psia and heating was continued until the
temperature of the batch reached 250°C. The pressure was then reduced slowly to 8 psia, while the batch temperature was allowed to further rise to 280-290 °C. The pressure was then held at 6 psia and the temperature was held at 280-290 °C for 20 minutes. Finally, the polymer melt was extruded into strands, cooled, and cut into pellets. The resulting poiyamide 88/6T is referred to herein as Poiyamide A
Poiyamide B refers Zytei® HTN502HNC010copoiyamide, made from terephthalic acid, adipic acid, and hexamethy!enediamine; wherein the two acids are used in a 55:45 molar ratio (PA 6T/66); having a melting point of about 310 °C and an inherent viscosity (IV), according to ASTM D2857 method, typically about 1 .07, available from E. I. DuPont de Nemours and Company, Wilmington, Delaware, USA.
PA86 refers to an aliphatic poiyamide made of 1 ,6-hexanedioic acid and 1 ,6-hexamethylenediamine having a typical relative viscosity of 49 and a melting point of about 283 °C, commercially available from E. I. DuPont de Nemours and Company, Wilmington, Delaware, USA under the trademark Zytel® 101 NC010 polyamide.
PA8 refers to U!tramid® B27 polyamide 8 resin (polycaprolactam) available from BASF Corporation, F!orham Park, NJ, 07932.
PA6T/DT refers HTN501 NCQ10, a copoiyamide of terephthaiic acid, hexamethyienediamine, and 2-methyi-pentamethylenediamine having a typical inherent viscosity (IV) of 0.88, according to ASTM D2857 method, and a melting point of about 300 °C, and available from E.I. DuPont de Nemours and Company, Wilmington, Delaware, USA.
TRX@301 copolymer is maieic anhydride modified EPDM from available from E.I. DuPont de Nemours and Company, Wilmington, Delaware, USA.
Engage® 8180 copolymer is an ethyiene/octene copolymer from Dow Chemical, Houston, TX, USA.
Glass Fiber B refers to CPIC 301 HP chopped glass fiber available from Chongqing Polycomp International Corp. (CPIC), Peoples Republic of China.
Licowax OP is a lubricant manufactured by Clariant Corp., Charlotte, NC.
Aluminum stearate is a wax supplied by PMC Global, Inc. Sun Valley, CA,
USA.
Kenamide El 80 refers to a fatty acid amide lubricant available from
Chemtura Corporation.
Black Pigment A refers to 40 vvt % nigrosine black pigment concentrate in a PA66 carrier.
Black Pigment B refers to 25 wt % carbon black in PA8 carrier.
Cu heat stabilizer refers to a mixture of 7 parts of potassium iodide and 1 part of copper iodide in 0.5 part of a stearate wax binder.
Irqanox® 1010 stabilizer is available from Ciba Speciality Chemicals Inc, Switzerland.
2,6-NDA refers to 2,6-napthalene diearboxyiic acid, supplied from BP Amoco, Napier, !L.
PEP 191 refers to oxidized polyethylene wax available from Clariant Corp., Charlotte, NC. Shelfplus® 02 2400 refers to 20 weight percent finely divided iron powder dispersed in polyethylene, available from BASF, Germany
EDTA refers to formula (XV) wherein Y = H, available from Aldrich Chemical Co., Milwaukee, WL
EDTA, di sodium salt refers to formula (XV), wherein Y = H2/Na2, available from Aldrich Chemical Co., Milwaukee, Wi.
EDTA, tetrasodium salt refers to formula (XV), wherein Y = Na4, available from Aldrich Chemical Co., Milwaukee, Wi.
EDTA, Iron (Hi) sodium salt refers to formula (XV), wherein Y = Fe/Na, available from Aldrich Chemical Co., Milwaukee, WL
EDTA, Copper (II) disodium salt refers to formula (XV), wherein Y = Cu/Na2, available from Aldrich Chemical Co., Milwaukee, WL
CvDTA refers to formula (XIX) wherein Y = H, available from Aldrich Chemical Co., Milwaukee, WL
EGTA refers to formula (XVII) wherein Y = H available from Aldrich
Chemical Co., Milwaukee, WL
DTPA refers to formula (XVIII) wherein Y = H available from Aldrich Chemical Co., Milwaukee, WL
HEDTA refers to formula (XVI) wherein Y = H available from Aldrich Chemical Co., Milwaukee, WL
HEDTA in sodium sail was available from Aldrich Chemical Co.,
Milwaukee, WL
IDA refers to formula (X) wherein Y = H available from Aldrich Chemical Co., Milwaukee, WL
IDA disodium salt was available from_A!drich Chemical Co., Milwaukee,
WL
TETHA refers to formula (XXI) wherein Y = H available from Aidrich Chemical Co., Milwaukee, WI.
1.3D2HPTA refers to formula (XX) wherein Y = H available from Aldrich Chemical Co., Milwaukee, WI.
Examples Examples and Comparative Examples (C) listed in Tables 3-12 were melt- blended and tested as disclosed in the methods section.
Examples 1 -5 (Tables 3 and 4) show significant improvement in tensile strength retention after AOA for 500 h at 230 °C, as compared to comparative examples C1 and C2 using traditional copper stabilizer.
Table 3 - EDTA salts in PA68/6T
Figure imgf000038_0001
Examples 6-9, 1 1 and 12, having a poiymer toughener, show significant improvement in tensile strength retention after AOA for 500 h at 230 °C. as compared with comparative example 03, of similar composition without amino acid thermal stabilizer; or 04 with copper stabilizer.
Table 5 - EDTA & EDTA disodium salt in HTN502
Figure imgf000039_0001
Examples 1 1 and 12, having a polymer toughener, show significant improvement in tensile strength retention after AOA for 500 h at 230 °C. as compared with comparative example C4 with copper stabilizer.
Table 8 - EDTA disodium salt with co ei
Figure imgf000040_0001
Example 13 shows a surprising effect of added EDTA disodium salt In compositions comprising copper and iron as compared to comparative examples C5 and C8 without the amino acid thermal stabilizer. Although the AOA gives similar high tensile strength retention for C8 and Example 13, Example 13 shows significantly higher absolute tensile strength than 05 or C8.
Table 7 - EDTA disodium salt with copper & iron
Figure imgf000041_0001
Examples 14-21 show the effect of a variety of amino acid thermal stabilizers on the AOA tensile strength retention in glass filled compositions.
Table 8 - Other Amino Acid Stabilizers
Figure imgf000041_0002
Elongation at Break [%] 1.28 4.52 3.39 3.20
Table 9 - Hydroxy Acid Stabilizers
Figure imgf000042_0001
Comparative Examples C7 and C8 show that 2,8-NDA does not show an improvement in AOA thermal stability
Table 1 1
Figure imgf000043_0001
Examples C10 - C12 show that compositions comprising polymer toughener, no reinforcement agent and amino acid thermal stabilizer have significantly lower thermal stability than comparative example 09 without amino acid thermal stabilizer.
Table 12 - No Reinforcing Agent
Figure imgf000043_0002
Table 13 shows C-14 iliustrating that 0.5 wt % of EDTA disodium salt composition exhibits significantly less tensile strength retention than 1.5 or 3.0 wt % under AOA (230 °C/500 hr) conditions.
Table 13 - EDTA Disodium Salt in PA66/6T
Figure imgf000044_0001
metal salts under AOA (230 °C/500 hr and 1000 hr) conditions,.
Table 14 - Sails of EDTA in PA68/8T
Figure imgf000045_0001
Table 15 - EDTA Disodium Sail and Copper(l)
Figure imgf000046_0001
Table 16 - Amino Acid Sails with Copper in PA88/8T
Figure imgf000047_0001
Table 17 - Various Amino Acids in PA88/8T
Figure imgf000048_0001
Table 18 - Salts of EDTA in PA6T/66
Figure imgf000049_0001
Table 19 - Amino Acid Salts and Copper(i) in PA6T/66
Figure imgf000050_0001
Table 20 - Amino Acid Salts and Copper(l) in PA88
Figure imgf000051_0001
Example 54 blistered in the oven, which may cause low tensile strength.

Claims

We Claim:
1. A thermoplastic melt-mixed composition comprising:
a) a poiyamide resin;
b) about 1.0 to about 5.0 weight percent of an amino acid thermal stabilizer, the amino acid thermal stabilizer comprising at least one or more amino groups; and at least two or more groups selected from carboxyiic acid and carboxylic acid salt, both represented by the general formula -CO2Y; the amino acid thermal stabilizer having a number average molecular weight of less than or equal to about 2000, preferably less than
1000, as determined by calculation of molecular weight of the amino acid thermal stabilizer wherein Y is considered to have a molecular weight equal to 1 ; or, if the amino acid thermal stabilizer is an oiigomeric material, as determined with gel permeation chromatography;
c) 10 to 60 weight percent reinforcing agent; and
d) 0 to 30 weight percent polymeric toughener;
wherein the weight percents of components a), b), c) and d) are based on the total weight of the thermoplastic melt-mixed composition.
2. The thermoplastic melt-mixed composition of Claim 1 wherein the poiyamide resin comprises a one or more polyamides selected from the group consisting of:
Group {I) Polyamides having a melting point of less than 210 °C, and comprising an aliphatic or semi-aromatic poiyamide selected from the group poiy(pentamethyiene decanediamide) (PA510), poly(pentamethylene dodecanediamide) (PA512), poiy(e-caproiactam/hexamethylene
hexanediamide) (PA6/66), poIy(K-caprolactam/hexamethyiene
decanediamide) (PA8/610), poiy(f caprolactam/hexamethyiene
dodecanediamide) (PA6/812), poly(hexamethyiene tridecanediamide) (PA613), poiy(hexamethylene pentadecanediamide) (PA815), poiy(e- caprolactam/tetramethyiene terephthalamide) (PA6/4T), po!y(e- caprolactam/hexamethylene terephthalamide) (PA6/6T), poly(c- caprolactam/decamethy!ene ierephihaiamide) (PA6/10T), poiy(s- caprolactam/dodecamethyiene ierephihaiamide) (PA6/12T),
poiy(hexamethylene decanediamide/hexamethylene ierephihaiamide) (PA810/6T). poiy(hexamethylene dodecanediamide/hexameihyiene ierephihaiamide) (PA612/6T), polyihexamethylene
tetradecanediamide/hexamethyiene ierephihaiamide) (PA614/6T), po!y(e~ caproiaciam/ hexamethylene isophtha!amide/hexamethy!ene
ierephihaiamide) (PA6/6I/6T), poly(e-caprolaciam/hexameihyiene
hexanediamide/hexamethy!ene decanediamide) (PA6/66/610), poly(e- caprolactam/hexamethylene hexanediamide/hexameihy!ene
dodecanediamide) (PA6/66/612), poly(e-capro!actam/hexamethy!ene hexanediamide/hexamethy!ene decanediamide/hexamethylene
dodecanediamide) (PA6/66/610/612), poly(2~methy!pentamethyIene hexanediamide/hexamethy!ene hexanediamide/hexamethylene
ierephihamide) (PA D6/66/6T), poly(2~methylpeniamethylene
hexanediamide/hexamethylene hexanediamide/) (PA D6/66),
po!y(decamethyIene decanediamide) (PA1010), po!y(decamethyIene dodecanediamide) (PA1012), poIy(decamethy!ene
decanediamide/decamethy!ene terephthalamide) (PA1010/10T)
poiy(decamethylene decanediamide/dodecamethylene decanediamide/ decamethylene terephtha!amide/dodecamethylene terephthalamide
(PA1010/1210/10T/12T), poly(1 1 -aminoundecanamide) (PA1 1 ), poly(1 1 - aminoundecanamide/tetramethyiene terephthalamide) (PA1 1/4T), po!y(1 1 - aminoundecanamide/hexamethy!ene terephthalamide) (PA1 1/ 8T), po!y(1 1 - aminoundecanamide/decamethyiene terephthalamide) (PA1 1/10T), poly(1 1 - aminoundecanamide/dodecamethylene ierephihaiamide) (PA1 1/12T), poiy(12-aminododecanamide) (PA12), poly(12- aminododecanamide/tetramethyiene ierephihaiamide) (PA12/4T), poly(12- aminododecanamide/hexamethyiene terephthalamide) (PA12/6T), poly(12- aminododecanamide/decamethyiene ierephihaiamide) (PA12/10T) poiy(dodecameihylene dodecanediamide) (PA1212), and poiy(dadecamethylene dodecanediamide/dodecamethylene
dodecanediamide/dodecamethylene terephtha!amide)) (PA1212/12T);
Group {ll} Pol amicles having a melting point of at least 210 °C, and comprising an aliphatic poiyamide selected from the group consisting of poiy(tetramethylene hexanediamide) (PA48), po!y(G-capro!actam) (PA 8), poly(hexamethyiene hexanediamide/(e-caproiactam/) (PA 66/6)
poiy(hexamethylene hexanediamide) (PA 66), poiyihexamethyiene hexanediamide/hexamethy!ene decanediamide) (PA66/610),
poiy(hexamethyiene hexanediamide/hexamethylene dodecanediamide) (PA66/612), poiy(hexamethylene hexanediamide/decamethyiene
decanediamide) (PA66/1010), poly(hexamethyiene decanediamide) (PA610), poiy(hexamethyiene dodecanediamide) (PA812), poly(hexamethy!ene tetradecanediamide) (PA614), poiyihexamethyiene hexadecanediamide) (PA618), and po!y(tetramethyIene hexanediamide/2-methyIpentamethyIene hexanediamide) (PA46/D6) wherein within Group (II) Po!yamides are Group (HA) Poiyamsdes having a melting point of at least 210 °C and less than 230 °C and Group (MB) Polyamides having a melting point of 230 °C or greater; Group {III} Poiyamsdes having a melting point of greater than 230 °C, and comprising
(aa) about 20 to about 35 mole percent semi-aromatic repeat units derived from monomers selected from one or more of the group consisting of:
i) aromatic dicarboxyiic acids having 8 to 20 carbon atoms and aliphatic diamines having 4 to 20 carbon atoms; and
bb) about 65 to about 80 mole percent aliphatic repeat units derived from monomers selected from one or more of the group consisting of: ii) an aliphatic dicarboxyiic acid having 6 to 20 carbon atoms and said aliphatic diamine having 4 to 20 carbon atoms; and
iii) a lactam and/or aminocarboxylic acid having 4 to 20 carbon atoms; Group {N) Polyamldes having a melting point of greater than 230 °C, comprising
(cc) about 50 to about 95 mole percent semi-aromatic repeat units derived from monomers selected from one or more of the group consisting of:
(j) aromatic dicarboxyiic acids having 8 to 20 carbon atoms and aliphatic diamines having 4 to 20 carbon atoms; and dd) about 5 to about 50 mole percent aliphatic repeat units derived from monomers selected from one or more of the group consisting of:
ii) an aliphatic dicarboxyiic acid having 6 to 20 carbon atoms and said aliphatic diamine having 4 to 20 carbon atoms; and
iii) a lactam and/or aminocarboxylic acid having 4 to 20 carbon atoms;
Group (V) Pofyamides having a melting point of at least 280 °C, and comprising
ee) greater than 95 mole percent semi-aromatic repeat units derived from monomers selected from one or more of the group consisting of:
(j) aromatic dicarboxyiic acids having 8 to 20 carbon atoms and
aliphatic diamines having 4 to 20 carbon atoms; and
ff) less than 5 mole percent aliphatic repeat units derived from monomers selected from one or more of the group consisting of:
ii) an aliphatic dicarboxyiic acid having 6 to 20 carbon atoms and said aliphatic diamine having 4 to 20 carbon atoms;
iii) a lactam and/or aminocarboxylic acid having 4 to 20 carbon atoms; and
Group (VI) Polyamldes having no melting point and selected from the group consisting of poiy(hexamethylene isophthalamide/ hexarnethylene terephthalamide) (6I/6T) and poly(hexamethylene
isophthalamide/hexamethyiene terephtha!amide/hexamethylene hexanediamide) (61/81766).
3. The thermoplastic melt-mixed composition of Claim 1 comprising 0 wt % of polymeric toughener.
4. The thermoplastic melt-mixed composition of Claim 1 comprising 0.1 to 3.5 wt % polymeric toughener.
5. The thermoplastic melt-mixed composition of Claim 1 wherein the reinforcing agent comprises one or more reinforcement agents selected from the group consisting of calcium carbonate, glass fibers with circular cross-section, glass fibers with noncircular cross-section, glass flakes, glass beads, carbon fibers, talc, mica, woilastonite, calcined clay, kaolin, diatomite, magnesium sulfate, magnesium silicate, barium sulfate, titanium dioxide, sodium aluminum carbonate, barium ferrite, potassium titanate and mixtures thereof.
8. The thermoplastic melt-mixed composition of Claim 1 wherein the amino acid thermal stabilizer useful in the composition may be selected from the group consisting of ethylene diamine-N,N,N\N'-tetra-acetic acid (EDTA), ethylene g!yco!-bis(2-aminoethylether)-NIN,N',N'-tetraacetic acid (EGTA), 1 ,2- Diaminocyclohexanetetraacetic acid (CyDTA), Diethy!enetriaminepentaacetic acid (DTPA), 1 ^-Diamino^-hydroxypropane-N.N.N'.N'-tetraacetic acid
(1 ,3D2HPTA),Triethylenetetramine-N,N,N,,N"!N'",N"1-hexaacetic acid (TETHA), N(2-hydroxyethyi)ethylenediamine triacetic acid (HEDTA) ; and their sodium, potassium, copper (i), copper (II), iron (II), and Iron (IN) salts; and mixtures thereof.
7. The thermoplastic melt-mixed composition of Claim 1 wherein the amino acid thermal stabilizer is selected from the group consisting of sodium, potassium, copper (I), copper (II), iron (Π), Iron (ill) salts of ethylene diamine- Ν,Ν,Ν',Ν'-tetra-acetic acid, and mixtures thereof.
8. The thermoplastic melt-mixed composition of Claim 2 wherein the polyamide resin comprises one or more polyamides selected from the group consisting of Group (III) Polyamides, Group (IV) Polyamides, Group (V)
Polyamides and Group (VI) Polyamides.
9. A molded or extruded thermoplastic article comprising the thermoplastic melt-mixed composition of Claims 2 wherein the polyamide resin comprises one or more Group (I) Polyamides, wherein 2 mm thick test bars, prepared from said melt-mixed composition and tested according to ISO 527- 2/1 BA, and exposed at a test temperature of 170 °C for a test period of 500 hours, in an atmosphere of air, have on average, a retention of tensile strength of at least 50 percent, as compared with that of an unexposed contro! of identical composition and shape,
10. A molded or extruded thermoplastic article comprising the
thermoplastic melt-mixed composition of Claim 2 wherein the po!yamide resin comprises one or more Group (II) Polyamides, wherein 2 mm thick test bars, prepared from said melt-mixed composition and tested according to ISO 527- 2/1 BA, and exposed at a test temperature of 210 °C for a test period of 500 hours, in an atmosphere of air, have on average, a retention of tensile strength of at least 50 percent, as compared with that of an unexposed control of identical composition and shape.
1 1. A molded or extruded thermoplastic article comprising the
thermoplastic melt-mixed composition of Claim 2 wherein the polyamide resin comprises a one or more polyamides selected from the group consisting of
Group (MB) Polyamides, Group (III) Polyamides, Group (IV) Polyamides, Group (V) Polyamides, and Group (VI) Polyamides, wherein 2 mm thick test bars, prepared from said melt-mixed composition and tested according to ISO 527- 2/1 BA, and exposed at a test temperature of 230 °C for a test period of 500 hours, in an atmosphere of air, have on average, a retention of tensile strength of at least 50 percent, as compared with that of an unexposed control of identical composition and shape.
12. The molded or extruded thermoplastic article of Claim 9 - 1 1 that is a charge air cooler (CAC); cylinder head cover (CHC); oil pan; engine cooling system, including thermostat and heater housing and coolant pump; exhaust system including muffler and housing for catalytic converter; air intake manifold (AI ); and timing chain belt front cover.
PCT/US2012/023295 2011-01-31 2012-01-31 Thermoplastic melt-mixed composition with heat stabilizer cross reference to related application WO2012106319A2 (en)

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