Thermoplastic articles including polyhydroxy polymers
View Patent ↗Disclosed is a molded or extruded thermoplastic article having high heat stability, including a thermoplastic polyamide composition including (a) a polvamide resin; (b) 0.25 to 20 weight percent of one or more polyhydroxy polymer(s) having a number average molecular weight of at least 2000; (c) 0.1 to 3 weight percent of one or more co-stabilizer(s) selected from the group consisting of secondary aryl amines, hindered amine light stabilizers, hindered phenols, and mixtures thereof; (d) 0 to less than 10 weight percent of one or more reinforcement agents; and (f) 0 to 20 weight percent of a polymeric toughener; wherein the composition has an air oven aging retention of elongation at break of at least 50 percent, as compared to that of an unexposed control of identical composition and shape.
1. 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) 2 to 7 weight percent of one or more polyhydroxy polymer(s) selected from the group consisting of ethylene/vinyl alcohol copolymer having a number average molecular weight of at least 2000;
(c) 0.1 to 1 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 polyamide if said melting point is present, or at least 250° C. if said melting point is not present, said co-stabilizer is one or more secondary aryl amines;
(d) 0 to less than 10 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 molded 4 mm test bars prepared from said polyamide composition, and exposed at an test temperature of 150° 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 elongation at break of at least 50 percent, as compared to that of an unexposed control of the same composition and shape; and wherein said polyamide resin comprises a one or more polyamides independently selected from the groups consisting of Group (III) Polyamides having said melting point of at least 210° C., and comprising
(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 having said 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 having no melting point, and selected from the group consisting of poly(hexamethylene isophthalamide/hexamethylene terephthalamide) (6I/6T) and poly(hexamethylene isophthalamide/hexamethylene terephthalamide/hexannethylene hexanediamide) (6I/6T/66).
2. The molded or extruded thermoplastic article of claim 1 wherein said polyamide resin is selected from Group (III ) Polyamides.
3. The molded or extruded thermoplastic article of claim 1 wherein said polyamide resin is selected from Group (IV) Polyamides.
4. The molded or extruded thermoplastic article of claim 1 wherein said polyamide resin is selected from Group (V) Polyamides.
5. The molded or extruded thermoplastic article of claim 1 wherein said polyamide resin comprises a blend of two or more polyamides selected from the group consisting of Group (I) and Group (III) Polyamide, Group (I) and Group (VI) Polyamides, Group (II) and Group (III) Polyamides, Group (II) and Group (IV) Polyamides, Group (II) and Group (V) Polyamides, Group (II) and Group (VI) Polyamides, Group (III) and Group (VI) Polyamides, and Group (IV) and Group (V) Polyamides; wherein said Group (I) Polyamides have said melting point of less than 210° C., and comprise an aliphatic or semiaromatic polyamide selected from the group consisting of poly(pentamethylene decanediamide) (PA510), poly(pentamethylene dodecanediamide) (PA512), poly(ε-caprolactam/hexamethylene hexanediarnide) (PA6/66), poly(ε-caprolactam/hexamethylene decanediamide) (PA6/610), poly(ε-caprolactam/hexamethylene dodecanediamide) (PA6/612), poly(hexamethylene tridecanediamide) (PA613), poly(hexamethylene pentadecanediamide) (PA615), poly(ε-caprolactam/tetramethylene terephthalamide) (PA6/4T), poly(ε-caprolactam/hexamethylene terephthalamide) (PA6/6T), poly(ε-caprolactam/decamethylene terephthalamide) (PA6/10T), poly(ε-caprolactam/dodecamethylene terephthalamide) (PA6/12T), poly(hexamethylene decanediamide/hexamethylene terephthalamide) (PA610/6T), poly(hexamethylene dodecanediamide/hexamethylene terephthalamide) (PA612/6T), poly(hexamethylene tetradecanediamide/hexamethylene terephthalamide) (PA614/6T), poly(ε-caprolactam/hexamethylene isophthalamide/hexamethylene terephthalamide) (PA6/6I/6T), poly(ε-caprolactam/hexamethylene hexanediamide/hexamethylene decanediamide) (PA6/66/610), poly(ε-caprolactam/hexamethylene hexanediamide/hexamethylene dodecanediamide) (PA6/66/612), poly(ε-caprolactam/hexamethylene hexanediamide/hexamethylene decanediamide/hexamethylene dodecanediamide) (PA6/66/610/612), poly(2-methylpentanriethylene hexanediamide/hexamethylene hexanediamide/hexamethylene terephthamide) (PA D6/66/6T), poly(2-methylpentarnethylene hexanediamide/hexamethylene hexanediamide/) (PA D6/66), poly(decamethylene decanediamide) (PA1010), poly(decamethylene dodecanediamide) (PA1012), poly(decamethylene decanediamide/decamethylene terephthalamide) (PA1010/10T) poly(decamethylene decanediamide/dodecamethylene decanediamide/decamethylene terephthalamide/dodecamethylene terephthalamide (PA1010/1210/10T/12T), poly(11-aminoundecanamide) (PA11), poly(11-aminoundecanamide/tetrannethylene terephthalamide) (PA11/4T), poly(11-aminoundecanamide/hexamethylene terephthalamide) (PA11/6T), poly(11-aminoundecanamide/decamethylene terephthalamide) (PA11/10T), poly(11-aminoundecanannide/dodecamethylene terephthalamide) (PA11/21), poly(12-aminododecanamide) (PA12), poly(12-aminododecanamidenetramethylene terephthalamide) (PA12/4T), poly(12-aminododecanamide/hexamethylene terephthalamide) (PA12/6T), poly(12-aminododecanamide/decamethylene terephthalamide) (PA12/10T) poly(dodecamethylene dodecanediamide) (PA1212), and poly(dodecamethylene dodecanediamide/dodecarnethylene dodecanediarnide/dodecamethylene terephthalamide) (PA1212/12T); and Group (II) Polyamides have said melting point of at least 210° C., and comprise 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) (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-methylpentannethylene hexanediamide) (PA46/D6).
6. The molded or extruded thermoplastic article of claim 5 wherein said polyamide resin comprises a blend of Group (II) and Group (V) Polyamides.
7. The molded or extruded thermoplastic article of claim 6 wherein said polyamide resin comprises a blend comprising poly(hexamethylene hexanediamide) (PA 66) and poly(hexamethylene terephthalamide/2-methylpentamethylene terephthalamide) (PA 6T/DT).
8. The molded or extruded thermoplastic article of claim 1 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.
9. The molded or extruded thermoplastic article of claim 1 wherein said polyamide composition comprises less than 25 ppm copper as determined with atomic absorption spectroscopy.
10. The molded or extruded thermoplastic article of claim 1 wherein the article is selected from the group consisting of pipes for transporting liquids and gases, inner linings for pipes, fuel lines, air break tubes, coolant pipes, air ducts, pneumatic tubes, hydraulic houses, cable covers, cable ties, connectors including electrical/electronic connectors, canisters, and push-pull cables.