Heat resistant thermoplastic articles including polyhydroxy polymers

Abstract

Disclosed is a molded or extruded thermoplastic article, including a thermoplastic polyamide composition including (a) a polyamide resin; (b) one or more polyhydroxy polymer(s); (c) one or more co-stabilizer(s); (d) one or more reinforcement agents; (e) and, optionally, a polymeric toughener.

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         16 . A molded or extruded thermoplastic article, comprising a thermoplastic polyamide composition comprising
 (a) a polyamide resin having a melting point and/or glass transition temperature;   (b) 1 to 10 weight percent of one or more polyhydroxy polymer(s) having a number average molecular weight of at least 2000 and selected from the group consisting of ethylene/vinyl alcohol copolymers;   (c) 0.1 to 3 weight percent of one or more co-stabilizer(s) having a 10% weight loss temperature, as determined by thermogravimetric analysis, of greater than 30° C. below said melting point of said polyamide resin if said melting point is present, or at least 250° C. if said melting point is not present, selected from the group consisting of secondary aryl amines, hindered amine light stabilizers, hindered phenols, and mixtures thereof;   (d) 10 to about 60 weight percent of one or more reinforcement agents; and   (e) 0 to 20 weight percent of a polymeric toughener comprising a reactive functional group and/or a metal salt of a carboxylic acid; wherein all weight percentages are based on the total weight of the polyamide composition; wherein molded 4 mm test bars prepared from said polyamide composition, and exposed at a test temperature at 170° C. for a test period of 500 hours, in an atmosphere of air, and tested according to ISO 527-2/1A, 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; and wherein said polyamide resin is selected from Group (II) Polyamides having said melting point of at least 210° C., and comprising an aliphatic polyamide selected from the group consisting of poly(tetramethylene hexanediamide) (PA46), poly(s-caprolactam) (PA 6), poly(hexamethylene hexanediannide/-(ε-caprolactam/) (PA 6616) poly(hexamethylene hexanediamide) (PA 66), poly(hexamethylene hexanediamide/hexamethylene decanediamide) (PA66/610), poly(hexamethylene hexanediamide/hexamethylene dodecanediamide) (PA66/612), poly(hexamethylene hexanediamide/decamethylene decanediamide) (PA66/1010), poly(hexamethylene decanediamide) (PA610), poly(hexamethylene dodecanediamide) (PA612), poly(hexamethylene tetradecanediamide) (PA614), poly(hexamethylene hexadecanediamide) (PA616), and poly(tetramethylene hexanediarnide/2-methylpentamethylene hexanediamide) (PA46/D6).   
     
     
         17 . The molded or extruded thermoplastic article of  claim 16  wherein said polyamide resin additionally comprises a polyamide selected from the group consisting of Group (III) Polyamides, Group (IV) Polyamides, Group (V) Polyamides, and Group (VI) Polyamides, wherein Group (III) Polyamides have a melting point of at least 210° C., and comprise
 (aa) about 20 to about 35 mole percent semiaromatic repeat units derived from monomers selected from one or more of the group consisting of:
 i. aromatic dicarboxylic 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 dicarboxylic 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; and 
 
 Group (IV) Polyamides comprising 
 (cc) about 50 to about 95 mole percent semiaromatic repeat units derived from monomers selected from one or more of the group consisting of:
 i) aromatic dicarboxylic 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 dicarboxylic 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) Polyamides have a melting point of at least 260° C., and comprising 
 (ee) greater than 95 mole percent semiaromatic repeat units derived from monomers selected from one or more of the group consisting of:
 ii) aromatic dicarboxylic 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 dicarboxylic 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; and 
 
 Group (VI) polyamides have melting point, and selected from the group consisting of poly(hexamethylene isophthalamide/hexamethylene terephthalamide) (6I/6T) and poly(hexamethylene isophthalamide/hexamethylene terephthalamide/hexamethylene hexanediamide) (61/61/66). 
 
     
     
         18 . The molded or extruded thermoplastic article of  claim 16  wherein said one or more co-stabilizer(s) is present at 0.1 to about 3 weight percent. 
     
     
         19 . The molded or extruded thermoplastic article of  claim 17  wherein said polyamide resin comprises said Group (II) and Group (V) Polyamides. 
     
     
         20 . The molded or extruded thermoplastic article of  claim 17  wherein said polyamide resin comprises said Group (II) and Group (III) Polyamides. 
     
     
         21 . The molded or extruded thermoplastic article of  claim 16  wherein the one or more polyhydroxy polymer(s) comprises an ethylene/vinyl alcohol copolymer and has a vinyl alcohol content of 40 to 75 mol %, wherein the remainder mol % is ethylene. 
     
     
         22 . The molded or extruded thermoplastic article of  claim 16  wherein the at least one co-stabilizer is one or more secondary aryl amines. 
     
     
         23 . The molded or extruded thermoplastic article of  claim 16  wherein the at least one co-stabilizer is one or more hindered amine light stabilizers. 
     
     
         24 . The molded or extruded thermoplastic article of  claim 16  wherein the at least one co-stabilizer is one or more hindered phenols. 
     
     
         25 . The molded or extruded thermoplastic article of  claim 16  wherein said thermoplastic polyamide composition comprises less than 25 ppm copper as determined with atomic absorption spectroscopy 
     
     
         26 . The molded or extruded thermoplastic article of  claim 16  selected from the group consisting of charge air coolers; cylinder head covers; oil pans;
 engine cooling systems, thermostat and heater housings, coolant pumps, mufflers, housings for catalytic converters; air intake manifolds; and timing chain belt front covers. 
 
     
     
         27 . A molded or extruded thermoplastic article, comprising a thermoplastic polyamide composition comprising
 a) a polyamide resin having a melting point and/or glass transition temperature;   b) 1 to 10 weight percent of one or more polyhydroxy polymer(s) having a number average molecular weight of at least 2000 and selected from the group consisting of ethylene/vinyl alcohol copolymers;   c) 0.1 to 3 weight percent of one or more co-stabilizer(s) having a 10% weight loss temperature, as determined by thermogravirnetric analysis, of greater than 30° C. below said melting point of said polyamide resin if said melting point is present, or at least 250° C. if said melting point is not present, selected from the group consisting of secondary aryl amines, hindered amine light stabilizers, hindered phenols, and mixtures thereof;   d) 10 to about 60 weight percent of one or more reinforcement agents; and   e) 0 to 20 weight percent of a polymeric toughener comprising a reactive functional group and/or a metal salt of a carboxylic acid;   
       wherein all weight percentages are based on the total weight of the polyamide composition; and wherein molded 4 mm test bars prepared from said polyamide composition, and exposed at a test temperature at 210° C. for a test period of 500 hours, in an atmosphere of air, and tested according to ISO 527-2/1A, have, on average, a retention of tensile strength of at least 70 percent, as compared with that of an unexposed control of identical composition and shape; and wherein said polyamide resin is selected from Group (II) Polyamides having said melting point of at least 210° C., and comprising an aliphatic polyamide selected from the group consisting of poly(tetramethylene hexanediamide) (PA46), poly(ε-caprolactam) (PA 6), poly(hexamethylene hexanediamide/(ε-caprolactam/) (PA 66/6) poly(hexamethylene hexanediamide) (PA 66), poly(hexamethylene hexanediamide/hexamethylene decanediamide) (PA66/610), poly(hexamethylene hexanediamide/hexamethylene dodecanediamide) (PA661612), poly(hexamethylene hexanediamide/decamethylene decanediamide) (PA66/1010), poly(hexamethylene decanediamide) (PA610), poly(hexamethylene dodecanediamide) (PA612), poly(hexamethylene tetradecanediamide) (PA614), poly(hexamethylene hexadecanediamide) (PA616), and poly(tetramethylene hexanediamide/2-methylpentamethylene hexanediamide) (PA46/D6).