POLYAMIDES AND CORRESPONDING POLYMER COMPOSITIONS AND ARTICLES

Abstract

The present invention relates to a polyamide (PA) comprising recurring units X, Y, and Z and is represented by the following formula (1): wherein—n.sub.x, n.sub.y and n.sub.z are respectively the mole percent (mol. %) of each recurring units X, Y and Z; —10 mol %≤n.sub.x≤90 mol %; —0 mol %≤n.sub.y≤90 mol %; —0 mol %≤n.sub.z≤90 mol %; —n.sub.x+n.sub.y+n.sub.z≤100 mol. %; and —at least one of n.sub.y and n.sub.z is greater than 0 mol. %, and wherein—R.sub.1 is selected from the group consisting of a hydrogen, an alkyl, or an aryl—R′i, at each location, is independently selected from the group consisting of an alkyl, an aryl, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, and a quaternary ammonium; —i is an integer from 0 to 10; —R.sub.2 is selected from the group consisting of a bond, a C.sub.1-C.sub.15 alkyl and a C.sub.6-C.sub.30 aryl, optionally comprising one or more heteroatoms (e.g. O, N or S) and optionally substituted with one or more substituents selected from the group consisting of halogen, hydroxy (—OH), sulfo (—SO.sub.3M), C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 alkylthio, C.sub.1-C.sub.6 acyl, formyl, cyano, C.sub.6-C.sub.15 aryloxy and C.sub.6-C.sub.15 aryl; —R.sub.3 is selected from the group consisting of a C.sub.1-C.sub.20 alkyl, a phenyl, an indanyl, and a napthyl, optionally comprising one or more heteroatoms (e.g. O, N or S) and optionally substituted with one or more substituents selected from the group consisting of halogen, hydroxy (—OH), sulfo (—SO.sub.3M), C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 alkylthio, C.sub.1-C.sub.6 acyl, formyl, cyano, C.sub.6-C.sub.15 aryloxy and C.sub.6-C.sub.15 aryl; and —R.sub.4 is selected from the group consisting of a linear or branched C.sub.6-C.sub.14 alkyl, optionally comprising one or more heteroatoms (e.g. O, N or S) and optionally substituted with one or more substituents selected from the group consisting of a halogen, hydroxy (—OH), sulfo (—SO.sub.3M), C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 alkylthio, C.sub.1-C.sub.6 acyl, formyl, cyano, and C.sub.6-C.sub.15 aryloxy and C.sub.6-C.sub.15 aryl; and —M in each of R.sub.2 to R.sub.4 is independently selected from the group consisting of H, Na, K, Li, Ag, Zn, Mg and Ca; with the provisios that —if recurring unit Y is formed from the condensation of p-xylylene diamine and a C12 dicarboxylic acid then: —30 mol %≤n.sub.x≤90 mol %; —0 mol %≤n.sub.y≤70 mol %; and —0 mol %≤n.sub.z≤70 mol %; —n.sub.x+n.sub.y+n.sub.z≤100 mol. %; and —If recurring unit Y is formed from the condensation of terephthalic acid with a diamine, R.sub.2 is selected from the group consisting of a bond, a C.sub.1-C.sub.9 alkyl, a C.sub.11-C.sub.15 alkyl, and a C.sub.6-C.sub.30 aryl, optionally comprising one or more heteroatoms (e.g. O, N or S) and optionally substituted with one or more substituents selected from the group consisting of halogen, hydroxy (—OH), sulfo (—SO.sub.3M), C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 alkylthio, C.sub.1-C.sub.6 acyl, formyl, cyano, C.sub.6-C.sub.15 aryloxy and C.sub.6-C.sub.15 aryl.

Claims

1-15. (canceled)

16. A polyamide comprising recurring units X, Y, and Z and represented by the following formula (1): ##STR00004## wherein n.sub.x, n.sub.y and n.sub.z are respectively the mole percent (mol %) of each recurring unit X, Y and Z; 10 mol %≤n.sub.x≤90 mol %; 0 mol %≤n.sub.y≤90 mol %; 0 mol %≤n.sub.z≤90 mol %; n.sub.x+n.sub.y+n.sub.z≤100 mol. %; and at least one of n.sub.y and n.sub.z is greater than 0 mol %; and wherein R.sub.1 is selected from the group consisting of a hydrogen, an alkyl, or an aryl R′.sub.i, at each location, is independently selected from the group consisting of an alkyl, an aryl, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, and a quaternary ammonium; i is an integer from 0 to 10; R.sub.2 is selected from the group consisting of a bond, a C.sub.1-C.sub.15 alkyl and a C.sub.6-C.sub.30 aryl, optionally comprising one or more heteroatoms selected from O, N and S, and optionally substituted with one or more substituents selected from the group consisting of halogen, hydroxy (—OH), sulfo (—SO.sub.3M), C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 alkylthio, C.sub.1-C.sub.6 acyl, formyl, cyano, C.sub.6-C.sub.15 aryloxy and C.sub.6-C.sub.15 aryl; R.sub.3 is selected from the group consisting of a C.sub.1-C.sub.20 alkyl, a phenyl, an indanyl, and a napthyl, optionally comprising one or more heteroatoms, selected from O, N and S, and optionally substituted with one or more substituents selected from the group consisting of halogen, hydroxy (—OH), sulfo (—SO.sub.3M), C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 alkylthio, C.sub.1-C.sub.6 acyl, formyl, cyano, C.sub.6-C.sub.15 aryloxy and C.sub.6-C.sub.15 aryl; and R.sub.4 is selected from the group consisting of a linear or branched C.sub.6-C.sub.14 alkyl, optionally comprising one or more heteroatoms, selected from O, N or S, and optionally substituted with one or more substituents selected from the group consisting of a halogen, hydroxy (—OH), sulfo (—SO.sub.3M), C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 alkylthio, C.sub.1-C.sub.6 acyl, formyl, cyano, and C.sub.6-C.sub.15 aryloxy and C.sub.6-C.sub.15 aryl; and M in each of R.sub.2 to R.sub.4 is independently selected from the group consisting of H, Na, K, Li, Ag, Zn, Mg and Ca; with the provisos that if recurring unit Y is formed from the condensation of p-xylylene diamine and a C.sub.12 dicarboxylic acid then: 30 mol %≤n.sub.x≤90 mol %; 0 mol %≤n.sub.y≤70 mol %; and 0 mol %≤n.sub.z≤70 mol %; n.sub.x+n.sub.y+n.sub.z≤100 mol. %; and If recurring unit Y is formed from the condensation of terephthalic acid with a diamine, R.sub.2 is selected from the group consisting of a bond, a C.sub.1-C.sub.9 alkyl, a C.sub.11-C.sub.15 alkyl, and a C.sub.6-C.sub.30 aryl, optionally comprising one or more heteroatoms, selected from O, N or S, and optionally substituted with one or more substituents selected from the group consisting of halogen, hydroxy (—OH), sulfo (—SO.sub.3M), C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 alkylthio, C.sub.1-C.sub.6 acyl, formyl, cyano, C.sub.6-C.sub.15 aryloxy and C.sub.6-C.sub.15 aryl.

17. The polyamide of claim 16, wherein recurring unit X is formed from the condensation of 1,4-aminomethylcyclohexanecarboxylic.

18. The polyamide of claim 17, wherein the polyamide is free of recurring units formed from the condensation of p-xylylene diamine and a C.sub.12 dicarboxylic acid.

19. The polyamide of claim 16, wherein recurring unit Y is formed from the condensation of a dicarboxylic acid component and a diamine component and wherein: the dicarboxylic acid component is selected from the group consisting of adipic acid, azelaic acid, sebacic acid, isophthalic acid, terephthalic acid, 2,6-naphthalene dicarboxylic acid, 4,4′-bibenzoic acid, 5-hydroxyisophthalic acid, 5-sulfophthalic acid, 1,4-cyclohexanedicarboxylic acid and mixture thereof; and the diamine component is selected from the group consisting of 1,4-diaminobutane, 1,5-diamonopentane, 2-methyl-1,5-diaminopentane, hexamethylenediamine, 1,9-diaminononane, 2-methyl-1,8-diaminooctoane, 1,10-diaminodecane, 1,12-diaminododecane H.sub.2N—(CH.sub.2).sub.3—O—(CH.sub.2).sub.2—O(CH.sub.2).sub.3—NH.sub.2, bis(4-amino-3-methylcyclohexyl)methane, m-xylylene diamine, p-xylylene diamine, bis(4-aminocyclohexyl)methane, and mixture thereof.

20. The polyamide of claim 16, wherein recurring unit Y is formed from the condensation of a dicarboxylic acid component and a diamine component, and wherein: the dicarboxylic acid component is selected from the group consisting of adipic acid, sebacic acid, isophthalic acid and terephthalic acid 1,4-cyclohexanedicarboxylic and mixtures thereof; and the diamine component is selected from the group consisting of hexamethylenediamine, 1,12-diaminododecane and mixtures thereof.

21. The polyamide of claim 16, wherein recurring unit Z is formed from the condensation of laurolocatam or 11-aminoundecanoic acid.

22. The polyamide of claim 16, wherein the polyamide is an amorphous polyamide comprising a Tg from 50° C. to 190° C.

23. The polyamide of claim 16, wherein the polyamide is semi-crystalline polyamide comprising a Tg from 60° C. to 170° C.

24. The polyamide of claim 16, wherein the polyamide has a melting temperature of from 170° C. to 400° C.

25. A polymer composition, comprising: the polyamide of claim 16, at least one component selected from the group consisting of reinforcing agents, tougheners, plasticizers, colorants, pigments, antistatic agents, dyes, lubricants, thermal stabilizers, light stabilizers, flame retardants, nucleating agents and antioxidants.

26. The polymer composition of claim 25, comprising a reinforcing fiber having an average length of from 3 mm to 50 mm.

27. The polymer composition of claim 25, comprising from 10 wt. % to 60 wt. % of glass fibers, based on the total weight of the composition.

28. The polymer composition of any claim 25, comprising from 40 wt. % to 70 wt. % of the polyamide.

29. An article comprising the polymer composition of claim 25, wherein the article is a mobile electronic device or component thereof, a composite material or a 3D printed article.

30. The article of claim 29, wherein the article is a mobile electronic device or component thereof, and the mobile electronic device is selected from the group consisting of a mobile phone, a personal digital assistant, a laptop computer, a tablet computer, a wearable computing device, a camera, a portable audio player, a portable radio, a global position system receiver, and a portable game console.

Description

EXAMPLES

[0162] These examples demonstrate the thermal, dielectric and mechanical performances of several inventive or comparative polyamides.

[0163] Raw Materials

[0164] Trans-1,4-AMCC: obtained from Sigma-Aldrich

[0165] Hexamethylenediamine (70 wt. %): obtained from Ascend Performance Materials

[0166] 1,12-diaminododecane: obtained from Invista

[0167] Adipic Acid: obtained from Ascend Performance Materials

[0168] Sebacic Acid: obtained from Sigma-Aldrich

[0169] Isopthalic Acid: obtained from Flint Hilss Resources

[0170] 1,4-Cyclohexane Dicarboxylic Acid: obtained from Eastman Chemical

[0171] Terephthalic Acid: Flint Hills Resources

[0172] Isophthalic Acid: Flint Hills Resources

[0173] Polyamides Preparation

[0174] Synthesis of E1-E3: The molar equivalent amounts of 1,4-AMCC, hexamethylenediamine and isophthalic acid were charged into the agitated reactor and added with DI water (35 wt %). Phosphorus acid (120 ppm equivalent P) was used as an additive in the polymerization. The mixture was heated to 335° C. The steam generated was released and the reacting mixture was further heated at this temperature for another 60 minutes at ambient pressure. Vacuum was applied for 10 minutes before the heating was turned off. The formed polymer was discharged and analyzed for their thermal properties.

[0175] Synthesis of E4: Similar process as for PA E1-E3 was followed to make PA E4 but, instead of isophthalic acid, equivalent molar amount of adipic acid was used.

[0176] Synthesis of E5: Similar process as for PA E1-E3 was followed to make PA E5 but, instead of hexamethylenediamine and isophthalic acid, equivalent molar amounts of dodecamethylenediamine and adipic acid were used.

[0177] Synthesis of E6: Similar process as for PA E1-E3 was followed to make PA E6 but, instead of hexamethylenediamine, equivalent molar amount of dodecamethylenediamine was used.

[0178] Synthesis of E7: Similar process as for PA E1-E3 was followed to make PA E7 but, instead of hexamethylenediamine and isophthalic acid, equivalent molar amounts of dodecamethylenediamine and 1,4-cyclohexane dicarboxylic acid were used.

[0179] Synthesis of E8: Similar process as for PA E1-E3 was followed to make PA E8 but, instead of isophthalic acid, equivalent molar amount of terephthalic acid was used.

[0180] Testing

[0181] Thermal Transitions (Tg, Tm)

[0182] The glass transition and melting temperatures of the various polyamides were measured using differential scanning calorimetry according to ASTM D3418 employing a heating and cooling rate of 20° C./min. Three scans were used for each DSC test: a first heat up to 340° C., followed by a first cool down to 30° C., followed by a second heat up to 350° C. The Tg and the Tm were determined from the second heat up. The glass transition and melting temperatures are tabulated in Table 1 below. In Table 1, Tg and Tm for counterexample CE1 was obtained from U.S. Pat. No. 3,509,105 to Pedersen, issued Apr. 28, 1970; and for counter examples C2 and C3 were obtained from Ellis, Bryan Smith, Ray. (2009). Polymers—A Property Database (2nd Edition), Taylor & Francis, all of which are herein incorporated by reference. Additionally, in Table 1, CHDA refers to 1,4-cyclohexanedicarboxylic acid.

TABLE-US-00001 Intrinsic Example Polyamide Tg Tm ΔH.sub.f Viscosity Number (Molar Ratio) (° C.) (° C.) (J/g) (dL/g) E1 PA 1,4-AMCC/6,I 135 — — 1.30 (20/80) E2 PA 1,4-AMCC/6,I 157 — — 1.16 (42/58) E3 PA 1,4-AMCC/6,I 158 — — 0.77 (60/40) E4 PA 1,4-AMCC/6,6 79 204 28 0.85 (40/60) E5 PA 1,4-AMCC/12,6 61 179 7 0.56 (40/60) E6 PA 1,4-AMCC/12,I 110 — — 0.96 (40/60) E7 PA 1,4-AMCC/12,CHDA 163 271 35 0.72 (40/60) E8 PA 1,4-AMCC/6,T 160 296 28 1.37 (40/60) CE1 PA 1,4-AMCC — >370 — — (100) CE2 PA 6,6 60 265 — — (100) CE3 PA6,I 130 — — —

[0183] Comparison of examples E2-E4 with counter examples CE1-CE3 demonstrates the tunablitity of the Tg of the polyamides (PA). CE1 (homopolymer formed from condensation of 1,4-AMCC) has a Tm in excess of 370° C., which can make melt processing difficult. CE2 (homopolymer formed from the condensation of hexamethylamine diamine and adipic acid), while having a Tm of 265° C., has a Tg of only 60° C. On the other hand, E4 has a significantly increased Tg relative to CE2 and significantly reduced Tm relative to CE1. Additionally, comparison of E2 and E3 with CE3 demonstrates that E2 and E3 has significantly increased Tg, relative to CE3.

[0184] Amorphous copolyamides of example E1, E2, E3 exhibit a significantly higher Tg than polyamide PA 6I, even when as low as 20 mol % of AMCC is used. It is important for applications that require high level of mechanical strength in hot environment.