Crystalline polyamide composition from dicarboxylic acid mixture and diamine

Abstract

Novel crystalline polyamides having high heat deflection temperatures when filled are prepared from aliphatic diamines and either mixtures of terephthalic acid and adipic acid or mixtures of terephthalic acid, isophthalic acid and adipic acid. The mole ratio of aliphatic diamine to terephthalic acid, isophthalic acid, and adipic acid is in the range of about 100:65-95:25-0:35-5. The polyamides can be filled with about 10 to about 60 parts by weight of a filler. The mechanical properties of these polyamides are largely unaffected by absorbed water.

We claim: .[.1. A resinous polyamide comprising the following recurring units: ##STR2## wherein the mole ratio of the dicarboxylic acid moieties in the A:B:C units is about 65-90:25-0:35-5 with the proviso that the mole ratio of the dicarboxylic acid moieties in the B:C units is less than 3:1 and wherein R, R 1 , and R 2  are, independently, divalent aliphatic hydrocarbyl 
     
        radicals of 2 to 14 carbon atoms..]. .[.2.  The polyamide of claim 1 wherein the mole ratio of the acid moieties in said A:B:C units is about 65-80:25-5:15-10..]. .[.3. The polyamide of claim 1 wherein the mole ratio of said acid moieties in said A:B:C units is about 65:25:10 to about 75:15:10..]. .[.4. The polyamide of claim 1 wherein R, R 1 , and R 2  are hexamethylene with the formula (CH 2 ) 6 ..]. .[.5. A molded object comprising the polyamide of claim 1..]. .[.6. A fiber comprising the polyamide of claim 1..]. .[.7. A laminate comprising the polyamide of claim 1..]. .[.8. A filled composition comprising 90 to 40 parts by weight of the polyamide of claim 1 and 10 to 60 parts by weight 
     
     
        of mineral fiber..]. 9. A filled injection moldable polyamide composition wherein said polyamide comprises the following recurring units: ##STR3## wherein the mole ratio of the dicarboxylic acid moieties in the A:B:C units is about 65-90:25-0:35-5 with the proviso that the mole ratio of the dicarboxylic acid moieties in the B:C units is less than 3:1, wherein R, R 1  and R 2  are, independently, divalent aliphatic hydrocarbyl radicals of 2 to 14 carbon atoms, wherein about 10 to about 60 percent by weight of the filled composition comprises a filler selected from the group consisting of glass fibers.[., glass beads, or.]. .Iadd.and .Iaddend.graphite fibers .[.or mixtures of the same.]. and wherein the filled polyamide composition has a heat deflection temperature .Iadd.determined by ASTM Method D648 .Iaddend.in excess of about 245° C. .Iadd.after being injection molded using a mold temperature 
     
     
        of 250° F.Iaddend.. 10. The composition of claim 9 wherein the filler comprises about 30 to about 60 percent by weight of the filled 
     
     
        composition. 11. The filled injection moldable polyamide composition of claim 9 wherein the mole ratio of the dicarboxylic acid moieties in the 
     
     
        A:B:C units is about 65-80:25-5:15-10. 12. The composition of claim 11 wherein said filler comprises about 30 to about 60 percent by weight of 
     
     
        said composition. 13. The composition of claim 9 wherein said mole ratio of the dicarboxylic acid moieties in the A:B:C units is about 65:25:10 to about 75:15:10 and said filler comprises about 30 to about 60 percent by 
     
     
        weight of said composition. 14. The composition of claim 9 wherein said R, 
     
     
        R 1 , and R 2  are hexamethylene. 15. The composition of claim 13 wherein said R, R 1 , and R 2  are hexamethylene of the formula 
     
     
        (CH 2 ) 6 . 16. The composition of claim 9 in the form of a molded article or a laminate. .[.17. A crystalline polyamide copolymer consisting essentially of the following recurring units: ##STR4## wherein the mole ratio of dicarboxylic acid moieties in I:II is about 65:35 to 95:5, wherein R and R 2  are aliphatic hydrocarbyl radicals of 
     
     
        2 to 14 carbon atoms..]. .[.18.  A molded article comprising the polyamide copolymer of claim 17..]. .[.19. A fiber comprising the polyamide copolymer of claim 17..]. .[.20. A laminate comprising the polyamide copolymer of claim 17..]. .[.21. The polyamide copolymer of claim 17 wherein R and R 2  are hexamethylene of the formula (CH 2 ) 6 ..]. .[.22. A filled composition comprising about 90 to 40 parts by weight of the polyamide copolymer of claim 17 and about 10 to 
     
     
        about 60 parts by weight of a mineral fiber..]. 23. A filled injection moldable polyamide copolymer composition, said copolymer comprising the following recurring units: ##STR5## wherein the mole ratio of the dicarboxylic moieties in I:II is about 65:35 to 95:5, wherein R and R 2  are aliphatic hydrocarbyl radicals of 2 to 14 carbon atoms, and wherein about 10 to about 60 percent by weight of the filled composition comprises a filler selected from the group consisting of glass fibers.[., glass beads, or.]. .Iadd.and .Iaddend.graphite fibers, .[.or mixtures of the same.]. and wherein the filled copolymer has a heat deflection temperature .Iadd.determined by ASTM Method D648 .Iaddend.in excess of about 245° C. .Iadd.after being injection molded using a 
     
     
        mold temperature of 250° F.Iaddend.. 24. The composition of claim 23 wherein said filler comprises about 30 to about 60 percent by weight of said composition. .[.25. The composition of claim 21 wherein R and R 2   
     
     
        are hexamethylene of the formula (CH 2 ) 6 ..]. 26. A blend comprising the composition of claim .[.1.]. .Iadd.9 .Iaddend.and nylon 6,6 wherein said nylon 6,6 comprises from about 1 to about 99 weight percent 
     
     
        of the blend. .[.27.  A blend comprising the copolymer of claim 17 and nylon 6,6 wherein said nylon 6,6 comprises from about 1 to about 99 weight 
     
     
        percent of the blend..]. 28. A process for preparing a polyamide composition having a heat deflection temperature of at least about 245° C., said process comprising compounding about 90 to about 40 parts by weight of a polyamide with about 10 to about 60 parts by weight of a filler, said polyamide comprising the following recurring units: ##STR6## wherein the mole ratio of the dicarboxylic acid moieties in the A:B:C units is about 65-90:25-0:35-5 with the proviso that the mole ratio of the dicarboxylic acid moieties in the B:C units is less than 3:1, and wherein R, R 1 , and R 2  are, independently, divalent aliphatic hydrocarbyl radicals of 2 to 14 carbon atoms, and wherein said filler is selected from the group consisting of glass fibers, .[.glass beads, or graphite 
     
     
        fibers.]. or mixtures of the same. 29. The process of claim 28 wherein R, R 1 , and R 2  are hexamethylene of the formula (CH 2 ) 6 . .[.30. A crystalline injection moldable polyamide copolymer having a heat deflection temperature of at least about 245° C. when molded and filled with glass fibers, glass beads or graphite fibers comprising the following recurring units: ##STR7## wherein the mole ratio of A:B:C units is about 65-90:25-5:30-5..]. 
     
     
        .Iadd.  .  A composition comprising a polyamide copolymer and up to about 60 wt % of at least one filler selected from the group consisting of glass fiber and graphite fibers, said copolymer comprising the following recurring units: ##STR8##.Iaddend. wherein R and R 2  are aliphatic hydrocarbyl radicals of 2 to 14 carbon atoms, and wherein the said copolymer, after being filled with glass fibers and injection molded using a mold temperature of 250° F. has a heat deflection temperature determined by ASTM Method D648 above 
     
     
        about 245° C.  .Iadd.32.  The filled polyamide copolymer composition of claim 31 wherein the said heat deflection temperature determined by ASTM Method D648 is in the range about 245° C. to 
     
     
        305° C. .Iaddend. .Iadd.33.  The filled polyamide copolymer composition of claim 31 wherein said copolymer comprises the following recurring units: ##STR9##.Iaddend. wherein R, R 1  and R 2  are aliphatic hydrocarbyl radicals 
     
     
        of 2 to 14 carbon atoms.  .Iadd.34.  The filled polyamide copolymer composition of claim 31 wherein R and R 2  are --(CH 2 ) 6  --. 
     
     
        .Iaddend. .Iadd.35.  The filled polyamide copolymer composition of claim 31 wherein said copolymer comprises the following recurring units: ##STR10## 
     
     
       .Iaddend.  .Iadd.36.  The filled polyamide copolymer composition of claim 31 comprising up to 60 wt % of at least one filler selected from the group consisting of glass fiber and graphite fiber, said fiber being i the form of cloth. .Iaddend. .Iadd.37. A composition comprising a polyamide copolymer and up to about 60 wt % of at least one filler selected from the group consisting of glass fiber, and graphite fibers, said copolymer comprising the following recurring units: ##STR11##.Iaddend. wherein the mole ratio of the dicarboxylic acid moieties terephthalic acid: adipic acid in the copolymer is at least 0.65, and wherein R and R 2  are aliphatic hydrocarbyl radicals of 2 to 14 carbon atoms, said copolymer filled with glass fibers having a heat deflection temperature determined by ASTM Method D648 above about 245° C. after being injection molded using a mold temperature of 250° F. 
     
     
        .Iadd.38.  The filled polyamide copolymer composition of claim 37, wherein R and R 2  are --(CH 2 ) 6  --. .Iaddend. .Iadd.39. The filled polyamide copolymer composition of claim 37 wherein said copolymer comprises the following recurring units: ##STR12##.Iaddend. wherein R, R 1  and R 2  are aliphatic hydrocarbyl radicals 
     
     
        of 2 to 14 carbon atoms.  .Iadd.40.  The filled polyamide copolymer composition of claim 37 wherein said copolymer comprises the following recurring units: ##STR13## 
     
     
       .Iaddend.  .Iadd.41.  A molded polyamide copolymer article, said copolymer comprising the following recurring units: ##STR14##.Iaddend. wherein R, R 1  and R 2  are aliphatic hydrocarbyl radicals of 2 to 14 carbon atoms, the proportion of the dicarboxylic acid moiety terephthalic acid is at least 55 mole % based on total dicarboxylic acid moieties in the copolymer, and said copolymer filled with glass fibers has a heat deflection temperature determined by ASTM Method D648 above about 245° C. after being injection molded using a mold temperature of 
     
     
        250° F.  .Iadd.42.  A filled composition comprising up to about 60 wt % of at least one filler selected from the group consisting of glass fiber and graphite fiber and a polyamide copolymer comprising the following recurring units: ##STR15##.Iaddend. said filled composition having a heat deflection temperature determined by ASTM Method D648 above about 245° C. when injection 
     
     
        molded using a mold temperature of 250° F.  .Iadd.43.  The filled composition of claim 42 wherein the mole ratio of the dicarboxylic acid moieties terephthalic acid: adipic acid in the copolymer is at least 0.65. .Iaddend. .Iadd.44. The filled composition of claim 42 wherein said copolymer comprises the following recurring units: ##STR16##.Iaddend.