POLYAMIDES OBTAINABLE FROM 3-(AMINOALKYL)BENZOIC ACID

Abstract

The invention relates to polyamides comprising at least 1 mol. % of 3-(aminoalkyl)benzoic acid (3-AABa), for example 3-(aminoethyl)benzoic acid (3-AEBa). The present invention also relates to polymer compositions comprising such polyamides, as well as articles comprising the same and methods of using said articles in automotive applications, LED packaging, electric and electronics devices, mobile electronics, gas barrier packaging, plumbing and oil and gas applications.

Claims

1. A polyamide, having the following formula (I): ##STR00005## wherein: n.sub.p, n.sub.q, n.sub.r and n.sub.s are respectively the mole % of each recurring units p, q, r and s; recurring units p, q, r and s are arranged in blocks, in alternation or randomly; n.sub.p+n.sub.q+n.sub.r+n.sub.s=100; 1≤n.sub.p≤100; 1≤m≤20; R.sub.1 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 and optionally substituted with one or more substituents selected from the group consisting of halogen, hydroxy, 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.2 is selected from the group consisting of a C.sub.1-C.sub.20 alkyl and a C.sub.6-C.sub.30 aryl, optionally comprising one or more heteroatoms and optionally substituted with one or more substituents selected from the group consisting of halogen, hydroxyl, 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.3 is selected from the group consisting of a C.sub.2-C.sub.20 alkyl and a C.sub.6-C.sub.30 aryl, optionally comprising one or more heteroatoms and optionally substituted with one or more substituent selected from the group consisting of halogen, hydroxy, 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.

2. The polyamide of claim 1, wherein: R.sub.1 is selected from the group consisting of a C.sub.4-C.sub.10 alkyl and a C.sub.6-C.sub.12 aryl, optionally substituted with one or more substituents selected from the group consisting of halogen, hydroxy, 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.2 is selected from the group consisting of a C.sub.4-C.sub.12 alkyl and a C.sub.6-C.sub.12 aryl, optionally comprising one or more heteroatoms; and/or R.sub.3 is selected from the group consisting of a linear or branched C.sub.2-C.sub.20 alkyl, optionally comprising one or more heteroatoms and optionally substituted with one or more substituent selected from the group consisting of halogen, hydroxy, 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.

3. The polyamide of claim 1 or 2, wherein the copolyamide is the condensation product of a mixture comprising: at least 1 mol. % of 3-(aminoalkyl)benzoic acid (3-AABa) of formula (II) or derivative thereof: ##STR00006## wherein 1<m≤20, and at least one of the component selected from the group consisting of: at least one dicarboxylic acid component or derivative thereof, and at least one diamine component, at least one aminocarboxylic acid, and/or at least one lactam.

4. The polyamide of claim 1, wherein the polyamide is the condensation product of a mixture comprising: at least 1 mol. % of 3-(aminoalkyl)benzoic acid (3-AABa) of formula (II) or derivative thereof, a dicarboxylic acid component 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, and mixture thereof, and a diamine component selected from the group consisting of 1,4-diaminobutane, 1,5-diamonopentane, 2-methyl-1,5diaminopentane, hexamethylenediamine, 1,9-diaminononane, 2-methyl-1,8-diaminooctoane, 1,10-diaminedecane, H.sub.2N—(CH.sub.2).sub.3—O—(CH.sub.2).sub.2—O(CH.sub.2).sub.3—NH.sub.2, m-xylylene diamine, p-xylylene and mixture thereof.

5. The polyamide of claim 1, wherein the polyamide is the condensation product of a mixture comprising: at least 1 mol. % of 3-(aminoalkyl)benzoic acid (3-AABa) of formula (II) or derivative thereof, a dicarboxylic acid component selected from the group consisting of adipic acid, terephthalic acid, isopthalic acid and mixture thereof, and a diamine component selected from the group consisting of hexamethylenediamine, m-xylylene diamine, 1,10-decamethylene diamine and mixture thereof.

6. The polyamide of claim 1, wherein the polyamide is the condensation product of a mixture comprising: at least 1 mol. % of 3-(aminoalkyl)benzoic acid (3-AABa) of formula (II) or derivative thereof, and at least one lactam selected from the group consisting of caprolactam, dodecanolactam and mixture thereof.

7. The polyamide of claim 1, wherein the polyamide is such that: 50≤n.sub.p≤100.

8. The polyamide of claim 1, wherein the polyamide has a glass transition temperature of at least 100° C., as determined according to ASTM D3418.

9. A polyamide composition (C), comprising: at least one polyamide according to claim 1, at one least one of components 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.

10. An article comprising the polyamide claim 1.

11. The article of claim 10, being used in air induction systems, cooling and heating systems, drivetrain systems and fuel systems.

12. The article of claim 10, being used in mobile electronics.

13. A method for manufacturing a three-dimensional (3D) object with an additive manufacturing system, comprising: providing a part material comprising the polyamide of claim 1, and printing layers of the three-dimensional object from the part material.

14. An article comprising the composition (C) of claim 9.

15. The article of claim 14, being used in air induction systems, cooling and heating systems, drivetrain systems and fuel systems.

16. The article of claim 14, being used in mobile electronics.

17. A method for manufacturing a three-dimensional (3D) object with an additive manufacturing system, comprising: providing a part material comprising the composition (C) of claim 9, and printing layers of the three-dimensional object from the part material.

Description

EXAMPLES

Raw Materials

[0110] 11-Aminoundecanoic acid (Fisher Scientific)

[0111] 3-AEBa: 3-(2-aminoethyl)benzoic acid prepared according to the following process. A solution of 2.0 g of 3-(Trifluoromethyl)phenylacetonitrile (Sigma Aldrich) in 5 mL of ether was added dropwise to a solution of 0.5 g of lithium aluminum hydride in 20 mL of ether, while cooling at 0° C. The mixture was then stirred at room temperature for 4 hours and then quenched by sequential addition of 0.5 ml of water, 0.5 ml of 15% sodium hydroxide solution and 1.5 mL of water. The mixture was filtered and the filtrate dried over magnesium sulfate. The filtered solution was acidified with a 1N hydrogen chloride solution in ether and the solid which precipitated was collected to give 2-(3-trifluoromethylphenyl) ethyl amine hydrochloride. 1.38 g of 2-(3-trifluoromethylphenyl) ethyl amine hydrochloride was heated to 100° C. in 3.5 g concentrated sulfuric acid for 3 hours. The cooled solution was diluted with 100 mL of ether and the resulting precipitate collected to give 3-(2-aminoethyl)-benzoic acid as the sulfate salt. The so-obtained salt product was then dissolved in 10 mL water and 1N sodium hydroxide solution was added to bring the pH up to 7.

11-Aminoundecanoic acid (Fisher Scientific)

Polyamides Preparation

[0112] The polyamides of the present invention were prepared according to a similar process in an electrically-heated autoclave reactor equipped with a distillate line fitted with a pressure regulation valve. In the preparation of example 2, the reactor was charged with 0.552 g (3.34 mmol) of 3-AEBa, 0.119 g (0.59 mmol) of 11-aminoundecanoic acid and 1 g of deionized water. The reactor was sealed, the pressure release valve was set to 17 bar and the reaction mixture was heated to 285° C. The pressure was reduced to atmospheric and the temperature was increased to 300° C. The reaction mixture was kept at 300° C. for 15 min and then cooled down to 200° C. within 1 hour and then to room temperature. The obtained products were further polymerized for 4 hours at 210° C.

Testing

[0113] Thermal transitions (Tg, Tm)

[0114] The glass transition and melting temperatures of the various copolyamides 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.

TABLE-US-00001 TABLE 1 mol. % Ex 1 Ex 2 3-AEBa 100 85 11-Aminoundecanoic acid — 15 Glass Transition and Melting temperatures Tg (° C.) 139 111 Tm (° C.) 234 236

[0115] Polyamides derived from 3-AEBa present a Tm which is much lower than polyamides derived from 3-(aminomethyl)benzoic acid (Tm=346° C. as described in U.S. Pat. No. 3,438,948). This result is surprising: based on the Tm of 223° C. of PA 6, which differs from PA 5 by only one methylene —CH.sub.2— and has a Tm of 260° C., one would expect a much lower reduction of melting temperature. The polyamide of example 1 has a Tm similar to the melting temperature of the commercially available semi-aromatic MXD6 (Tm=243° C., homopolyamide obtained by reaction of adipic acid with meta-xylylene diamine), but exhibits a Tg significantly higher than MXD6. This makes the polyamides of the present invention well-suited for applications that require a high modulus at the temperature of use like in automotive applications where the temperature is usually above 100° C. under-the-hood.

[0116] Surprisingly, the copolymerization of 15 mol. % 11-undecanoic acid with 85 mol. % 3-AEBa does not impact its melting point, but its Tg is much lower, which is quite unusual for copolyamides.