Semi-aromatic polyamide with low melting temperature

Abstract

The present invention relates to a polyamide (PA) exhibiting a melting temperature Tm strictly below 290 DEG C and comprising repeating units formed by the polycondensation of a diamine component (A) and a dicarboxylic acid component (B) wherein: a) the diamine component (A) comprises:-between 38.0 and 54.0 mol% of 1, 6-diaminohexane; -between 15.0 and 40.0 mol% of a diamine selected from the group consisting of 1, 9-diaminononane, 1, 10-diaminodecane, and a combination of said two diamines; -between 15.0 and 40.0 mol% of a diamine selected from the group consisting of 1, 3-bis (aminomethyl) cyclohexane, 1, 4-bis (aminomethyl) cyclohexane and a combination of said two diamines; the proportions in mol% are based on the total amount of diamines in the diamine component (A); b) the dicarboxylic acid component (B) comprises:-between 95.0 and 100.0 mol% of terephthalic acid; between 0 and 5.0 mol% of another diacid selected from the group consisting of isophthalic acid, adipic acid and a combination of the two said diacids; the proportions in mol% are based on the total amount of diacids in the dicarboxylic acid component (B).

Description

[0001] This application claims priority to U.S. Patent Application No. 63 / 385,648, filed December 1, 2022, and European Patent Application No. 23154138.4, filed January 31, 2023, the contents of which are incorporated herein by reference in their entirety for all purposes. In the event of any inconsistency between the present application and those two (U.S. and European) applications that would affect the clarity of terminology or expression, reference shall be made solely to the present application. [Technical field]

[0002] The present invention relates to a semicrystalline, semiaromatic copolyamide having a combination of a high glass transition temperature and a low melting temperature and other properties that make it suitable for use in the preparation of thermoplastic composites. [Background Technology]

[0003] Aliphatic polyamides (such as the well-known PA6 and PA66) are a very popular class of thermoplastic resins because they are easy to process and generally have high melting points. They also exhibit high heat resistance values, especially when reinforced with fibers or fillers. However, when stored in water, they typically have high water absorption values ​​of up to 10%.

[0004] Aliphatic polyamides cannot be used in many applications with stringent requirements for dimensional stability (including wet or humid conditions). Water absorption alters not only the dimensions but also the mechanical properties. Water absorption reduces stiffness and strength to a fraction of their original values. However, there are many applications that involve mechanical loads in contact with water or ambient moisture.

[0005] Semiaromatic polyamides have been developed to address these issues. Trogamid T5000 is a commercial amorphous polyamide composed of terephthalic acid and a mixture of 2,2,4-TMD and 2,4,4-TMD. This polyamide is inherently amorphous and characterized by high mechanical strength and toughness. However, when exposed to temperatures above its Tg = 150°C (dry state) and in the presence of water, it loses all mechanical integrity due to a high moisture absorption rate of approximately 7.5 wt.%.

[0006] WO 2018 / 234439 discloses a polyamide BACT / 10T / 6T without disclosing any specific composition.

[0007] WO 2018 / 172717 discloses semi-aromatic copolyamides with a BAC content of 1.3. The disclosed polyamides with a BAC content of 1.3 exhibit a Tm above 290°C or are based on different compositions with a higher BAC content.

[0008] WO 2018 / 172718 discloses semi-aromatic copolyamides with a BAC of 1.3. The disclosed polyamides with a BAC of 1.3 exhibit a Tm above 290°C or are based on different compositions.

[0009] US 2008 / 274355 (D1) discloses a polyamide molding composition based on copolyamide 10T / 6T having 40 to 95 mol % of 10T units and 5 to 60 mol % of 6T units.

[0010] US2019 / 338074 and WO 2018 / 011495 / US2018 / 251601 (D2) disclose semiaromatic copolyamides based on 1.3BAC with a melting temperature below 300°C. The copolyamides of D2 preferably exhibit a Tm-Tc (Tm = melting temperature; Tc = crystallization temperature) of <40°C. The two compositions based on 10T, 6T, and BACT disclosed in the experimental sections of US2019 / 338074 and WO 2018 / 011495 are not compositions according to claim 1. D2 more specifically discloses a copolyamide 10T / BACT / 6T exhibiting a low (Tm–Tc) value below 37°C and a heat of fusion Hm above 40.0 J / g.

[0011]

[0012] US2016 / 0152770 discloses a semiaromatic copolyamide comprising the following in copolymerized form: a) 36 to 50 mol% of terephthalic acid, b) 0 to 14 mol% of isophthalic acid, c) 35 to 42.5 mol% of hexamethylenediamine, and d) 7.5 to 15 mol% of at least one cyclic diamine, wherein the cyclic diamine d) comprises isophoronediamine. The proportion of hexamethylenediamine is higher than that in claim 1. Furthermore, bis(aminomethyl)cyclohexane is not mentioned.

[0013] US 2017 / 0107326 discloses polyamides having a higher proportion of 1,6-hexamethylenediamine and a higher melting temperature than in claim 1 .

[0014] WO 2021 / 037850 discloses a polyamide formed from a diamine component (A) and a dicarboxylic acid component (B), wherein the diamine component (A) comprises 55 mol% to 75 mol% of a C4-C8 aliphatic diamine, 25 mol% to 45 mol% of a C9-C 12aliphatic diamine, and 0 mol% to 10 mol% of alicyclic diamine containing a cyclohexyl group, the dicarboxylic acid component (B) comprises: 90 mol% to 100 mol% of terephthalic acid, 0 mol% to 10 mol% of C6-C 18 Aliphatic dicarboxylic acid or C8-C 18 Aromatic dicarboxylic acid, and 0 to 10 mol% of alicyclic dicarboxylic acid containing a cyclohexyl group. The proportion of C4-C8 aliphatic diamine is higher than that of the hexamethylenediamine of claim 1.

[0015] WO 2021 / 224431 discloses a polyamide derived from the polycondensation of monomers in a reaction mixture comprising 20 mol% to 95 mol% of C4 to C 12 A diamine component (A) comprises an aliphatic diamine and 5 to 80 mol% of bis(aminoalkyl)cyclohexane, and a dicarboxylic acid component (B) comprises 30 to 100 mol% of terephthalic acid and 0 to 70 mol% of cyclohexanedicarboxylic acid. WO 2021 / 224431 more specifically discloses a polyamide 6,T / 1,3-BAC,T / 6,CHDA / 1,3-BAC,CHDA having a Tm of 330°C.

[0016] WO 2022 / 180195 discloses a polyamide prepared from a diamine component comprising: 55 to 75 mol% of a C4-C8 diamine; 25 to 45 mol% of a C9 to C 12 and 0 to 10 mol% of an alicyclic diamine containing a cyclohexyl group. Tm is higher than that of claim 1.

[0017] [Technical Issues]

[0018] In the field of polyamide-based thermoplastic composites, a major challenge is to find easily prepared semi-crystalline resins that exhibit a high glass transition temperature (Tg) to allow the polyamide to be used in a wide range of operating temperatures, and a low melting temperature (Tm) to facilitate the processing of the polyamide.

[0019] Furthermore, for the preparation of thermoplastic composites by melt infusion, the polyamide used to prepare the thermoplastic preferably exhibits a "low" crystallization temperature (Tc) (e.g., Tc < 230°C, preferably ≤ 225°C) to produce thermoplastic composites that exhibit less stress and less warpage.

[0020] In addition to the above-mentioned thermal properties, the resin forming the matrix of the composite material should also exhibit high elongation at break and impact resistance. Furthermore, sustainable resins are increasingly sought.

[0021] The polyamide of the present invention is intended to solve this technical problem.

[0022] [General definition]

[0023] These definitions apply to this disclosure.

[0024] Wt.% is the percentage by weight. Mol.% is the percentage by mole.

[0025] Unless stated otherwise, the proportions of the recurring units in the polyamide are given in mol % and are relative to the total proportions of the recurring units in the polyamide.

[0026] When numerical ranges are given herein, the endpoints of those ranges (even open-ended ranges such as those including "at least," "at most," "less than," etc.) are included unless otherwise indicated.

[0027] In this application, unless otherwise indicated, any specific embodiment or technical feature related to one of the subject matters of the present invention is applicable to and interchangeable with another embodiment or technical feature also related to the subject matter and disclosed elsewhere in this application.

[0028] The proportion of diamines in the diamine component (A) is based on the total amount of diamines in the diamine component (A). The proportion of carboxylic diacids in the dicarboxylic acid component (B) is based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B).

[0029] The proportions of the repeating units in the polyamide (PA) are expressed in mol % and are based on the total amount of repeating units in the polyamide (PA).

[0030] [Brief Summary of the Invention]

[0031] The invention is set forth in the appended claims.

[0032] The present invention relates to a polyamide as disclosed in any one of claims 1 to 25.

[0033] The invention also relates to a thermoplastic composite material as defined in claim 26 .

[0034] The invention also relates to the use as defined in claim 27 .

[0035] More precise information and details on these topics are now provided below. [Specific implementation method]

[0036] The present invention relates to a semi-aromatic copolyamide (PA) exhibiting a melting temperature Tm strictly lower than 300° C. (<300° C.), preferably lower than or equal to 296.0° C. (≤296.0° C.), preferably lower than or equal to 295.0° C. (≤295.0° C.), preferably strictly lower than 290° C. (<290° C.), and comprising repeating units formed by the polycondensation of a diamine component (A) and a dicarboxylic acid component (B), wherein:

[0037] a) The diamine component (A) comprises:

[0038] - between 38.0 and 54.0 mol % of 1,6-diaminohexane;

[0039] - between 15.0 and 40.0 mol % of a diamine (D1) chosen from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines;

[0040] - between 15.0 and 40.0 mol % of a diamine (D2) selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane and a combination of said two diamines;

[0041] These proportions in mol % are based on the total amount of diamines in the diamine component (A);

[0042] b) the dicarboxylic acid component (B) comprises:

[0043] - between 95.0 and 100.0 mol % of terephthalic acid;

[0044] - between 0 and 5.0 mol% of another diacid (DI) chosen from the group consisting of isophthalic acid, adipic acid and a combination of said two diacids;

[0045] These proportions in mol % are based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B).

[0046] The polyamide (PA) disclosed in the present invention therefore comprises the diamines of the diamine component (A) and the dicarboxylic acids of the dicarboxylic acid component (B) in reacted form in the proportions indicated therein.

[0047] The polyamide (PA) of the present invention is formed by the polycondensation of a diamine component (A) and a dicarboxylic acid component (B). Therefore, the proportion of -NH2 from the diamine component (A) and the proportion of -COOH from the dicarboxylic acid component (B) are substantially equimolar. The molar ratio of -NH2 from the diamine component (A) / COOH from the dicarboxylic acid component (B) is preferably comprised between 0.9 and 1.1, preferably between 0.95 and 1.05, and even more preferably between 0.98 and 1.02.

[0048] More details regarding the diamine component (A) and the dicarboxylic acid component (B) are now provided below.

[0049] About diamine component (A)

[0050] The diamine component (A) is based on the following diamines: 1,6-diaminohexane (having the formula NH2-(CH2)6-NH2); selected from the group consisting of 1,9-diaminononane (having the formula NH2-(CH2)9-NH2), 1,10-diaminodecane (having the formula NH2-(CH2) 10 -NH2) and a combination of the two diamines (D1); and bis(aminomethyl)cyclohexane (D2).

[0051] The proportion of 1,6-diaminohexane is between 38.0 and 54.0 mol %. More particularly, it can be between 38.0 and 52.0 mol %. More particularly, it can be between 38.0 and 47.0 mol %. It can also be between 42.0 and 47.0 mol %, between 48.0 and 52.0 mol %, or between 38.0 and 42.0 mol %.

[0052] The diamine component (A) further comprises another diamine (D1) selected from the group consisting of 1,9-diaminononane, 1,10-diaminodecane, and a combination of the two diamines. The diamine (D1) may more particularly be 1,9-diaminononane. The diamine (D1) may also more particularly be 1,10-diaminodecane. The proportion of the one or more other diamines (D1) is between 15.0 and 40.0 mol%. The proportion may more particularly be between 18.0 and 40.0 mol%. The proportion may more particularly be between 33.0 and 37.0 mol%, or between 18.0 and 22.0 mol%, or between 23.0 and 27.0 mol%, or between 28.0 and 32.0 mol%.

[0053] The diamine component (A) further comprises bis(aminomethyl)cyclohexane (D2) selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, and a combination of the two diamines. 1,3-bis(aminomethyl)cyclohexane is a diamine having the formula: 1,4-Bis(aminomethyl)cyclohexane is a diamine having the formula: The diamine (D2) may more particularly be 1,3-bis(aminomethyl)cyclohexane. The diamine (D2) may more particularly be 1,4-bis(aminomethyl)cyclohexane. The proportion of the one or more other diamines (D2) may be between 15.0 and 40.0 mol %. The proportion may more particularly be between 18.0 and 40.0 mol %. The proportion may more particularly be between 18.0 and 22.0 mol %, between 28.0 and 32.0 mol %, or between 33.0 and 37.0 mol %.

[0054] According to embodiment (E1), the ratios in the diamine component (A) are the following:

[0055] - between 42.0 and 47.0 mol % of 1,6-diaminohexane;

[0056] - between 33.0 and 37.0 mol % of a diamine (D1) chosen from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines;

[0057] - between 18.0 and 22.0 mol % of a diamine (D2) selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane and a combination of said two diamines;

[0058] These proportions in mol % are based on the total amount of diamines in the diamine component (A).

[0059] According to another embodiment (E2), the ratio of the diamine component (A) is the following ratio:

[0060] - between 48.0 and 52.0 mol % of 1,6-diaminohexane;

[0061] - between 18.0 and 22.0 mol % of a diamine (D1) chosen from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines;

[0062] - between 28.0 and 32.0 mol % of a diamine (D2) selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane and a combination of said two diamines;

[0063] These proportions in mol % are based on the total amount of diamines in the diamine component (A).

[0064] According to another embodiment (E3), the ratio of the diamine component (A) is the following ratio:

[0065] - between 38.0 and 42.0 mol % of 1,6-diaminohexane;

[0066] - between 23.0 and 27.0 mol % of a diamine (D1) chosen from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines;

[0067] - between 33.0 and 37.0 mol % of a diamine (D2) selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane and a combination of said two diamines;

[0068] These proportions in mol % are based on the total amount of diamines in the diamine component (A).

[0069] According to another embodiment (E4), the ratio of the diamine component (A) is the following ratio:

[0070] - between 48.0 and 52.0 mol % of 1,6-diaminohexane;

[0071] - between 28.0 and 32.0 mol % of a diamine (D1) chosen from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines;

[0072] - between 18.0 and 22.0 mol % of a diamine (D2) selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane and a combination of said two diamines;

[0073] These proportions in mol % are based on the total amount of diamines in the diamine component (A).

[0074] According to another embodiment (E5), the ratio of the diamine component (A) is the following ratio:

[0075] - between 48.0 and 52.0 mol % of 1,6-diaminohexane;

[0076] - between 18.0 and 22.0 mol % of a diamine (D1) chosen from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines;

[0077] - between 28.0 and 32.0 mol % of a diamine (D2) selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane and a combination of said two diamines;

[0078] These proportions in mol % are based on the total amount of diamines in the diamine component (A).

[0079] According to another embodiment (E6), the ratio of the diamine component (A) is the following ratio:

[0080] - between 43.0 and 47.0 mol % of 1,6-diaminohexane;

[0081] - between 33.0 and 37.0 mol % of a diamine (D1) chosen from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines;

[0082] - between 18.0 and 22.0 mol % of a diamine (D2) selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane and a combination of said two diamines;

[0083] These proportions in mol % are based on the total amount of diamines in the diamine component (A).

[0084] All details and examples disclosed in this disclosure apply to any of embodiments (E1)-(E6).

[0085] According to an embodiment, the diamine component (A) consists essentially of or consists of the following in the proportions indicated herein: 1,6-diaminohexane; a diamine (D1) selected from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of the two diamines; and a diamine (D2) selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane and a combination of the two diamines. The expression "consists essentially of" means that in the context of the present invention with respect to the diamine component (A), the diamine component (A) comprises the indicated diamine and may further comprise up to 2.0 mol %, preferably up to 1.0 mol %, even more preferably up to 0.5 mol % of at least one further diamine other than the indicated diamine, the proportion in mol % being based on the total amount of diamines in the diamine component (A). Thus, the diamine component (A) consists of: 1,6-diaminohexane; a diamine (D1) selected from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of the two diamines; a diamine (D2) selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane and a combination of the two diamines; and up to 2.0 mol %, preferably up to 1.0 mol %, even more preferably up to 0.5 mol % of at least one further diamine other than 1,6-diaminohexane, D1 and D2, the proportions in mol % being based on the total amount of diamines in the diamine component (A).

[0086] The diamine component (A) may be based on the following diamine combination: 1,6-diaminohexane+(1,9-diaminononane or 1,10-diaminodecane)+1,3-bis(aminomethyl)cyclohexane in the proportions indicated herein. According to an embodiment, the diamine component (A) consists essentially of or consists of [1,6-diaminohexane+1,9-diaminononane or 1,10-diaminodecane+1,3-bis(aminomethyl)cyclohexane], wherein the expression "consisting essentially of" means that the diamine component (A) consists of: 1,6-diaminohexane; 1,9-diaminononane or 1,10-diaminodecane; 1,3-bis(aminomethyl)cyclohexane; and up to 2.0 mol %, preferably up to 1.0 mol %, even more preferably up to 0.5 mol % of at least one further diamine other than 1,6-diaminohexane, 1,9-diaminononane, 1,10-diaminodecane and 1,3-bis(aminomethyl)cyclohexane, the proportion in mol % being based on the total amount of diamines in the diamine component (A).

[0087] The diamine component (A) may be based on the following diamine combination: 1,6-diaminohexane+(1,9-diaminononane or 1,10-diaminodecane)+1,4-bis(aminomethyl)cyclohexane in the proportions indicated herein. According to an embodiment, the diamine component (A) consists essentially of or consists of [1,6-diaminohexane+1,9-diaminononane or 1,10-diaminodecane+1,4-bis(aminomethyl)cyclohexane], wherein the expression "consisting essentially of" means that the diamine component (A) consists of: 1,6-diaminohexane; 1,9-diaminononane or 1,10-diaminodecane; 1,4-bis(aminomethyl)cyclohexane; and up to 2.0 mol %, preferably up to 1.0 mol %, even more preferably up to 0.5 mol % of at least one further diamine other than 1,6-diaminohexane, 1,9-diaminononane, 1,10-diaminodecane and 1,4-bis(aminomethyl)cyclohexane, the proportions in mol % being based on the total amount of diamines in the diamine component (A).

[0088] About dicarboxylic acid component (B)

[0089] The dicarboxylic acid component (B) is based on terephthalic acid as the main component of the dicarboxylic acid component (B).The dicarboxylic acid component (B) may further comprise another diacid (DI) selected from the group consisting of isophthalic acid, adipic acid and a combination of the two diacids.

[0090] The dicarboxylic acid component (B) comprises:

[0091] - between 95.0 and 100.0 mol % of terephthalic acid;

[0092] - between 0 and 5.0 mol% of another diacid (DI) chosen from the group consisting of isophthalic acid, adipic acid and a combination of said two diacids;

[0093] These proportions in mol % are based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B).

[0094] These proportions may more particularly be proportions of between 95.0 and 99.9 mol % of terephthalic acid and between 0.1 and 5.0 mol % of the other diacid(s) (DI).

[0095] These proportions may more particularly be proportions of between 98.0 and 99.9 mol% of terephthalic acid and between 0.1 and 5.0 mol% of the other diacid(s) (DI).

[0096] The diacid (DI) other than terephthalic acid may more particularly be isophthalic acid.

[0097] The diacid (DI) other than terephthalic acid may more particularly be adipic acid.

[0098] The proportions in the dicarboxylic acid component (B) may more particularly be the following proportions:

[0099] - between 98.0 and 100.0 mol % of terephthalic acid;

[0100] - between 0 and 2.0 mol% of another diacid (DI) chosen from the group consisting of isophthalic acid, adipic acid and a combination of said two diacids;

[0101] These proportions in mol % are based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B).

[0102] These proportions may more particularly be proportions of between 98.0 and 99.9 mol% of terephthalic acid and between 0.1 and 2.0 mol% of the other diacid(s) (DI).

[0103] According to an embodiment, the dicarboxylic acid component (B) consists essentially of or consists of terephthalic acid and the diacid (DI). The expression "consists essentially of" means that in the context of the present invention with respect to the dicarboxylic acid component (B), the dicarboxylic acid component (B) consists of terephthalic acid, the diacid (DI) and up to 2.0 mol %, preferably up to 1.0 mol %, even more preferably up to 0.5 mol % of at least one further diacid other than terephthalic acid and the diacid DI, the proportions in mol % being based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B).

[0104] The diamine component (A) and the dicarboxylic acid component (B) preferably do not contain lactams. The diamine component (A) and the dicarboxylic acid component (B) preferably do not contain amino acids. The diamine component (A) and the dicarboxylic acid component (B) preferably do not contain isophoronediamine.

[0105] Example (E): According to a preferred embodiment (E), the dicarboxylic acid component (B) consists essentially of or consists of terephthalic acid.

[0106] The expression "essentially consists of" means that in the context of the present invention in relation to the dicarboxylic acid component (B), the dicarboxylic acid component (B) comprises terephthalic acid and may also comprise up to 2.0 mol %, preferably up to 1.0 mol %, even more preferably up to 0.5 mol %, of at least one further diacid other than terephthalic acid, the proportion in mol %, based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B). Thus, the dicarboxylic acid component (B) consists of terephthalic acid and up to 2.0 mol %, preferably up to 1.0 mol %, even more preferably up to 0.5 mol %, of at least one further diacid other than terephthalic acid, the proportion in mol %, based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B).

[0107] All details and examples disclosed in this disclosure apply to Example (E).

[0108] Under embodiment (E), the skilled person understands that polyamide (PA) can be described as comprising the following repeating units (R PA1 )、(R PA2 ) and (R PA3 ):

[0109]

[0110]

[0111] or the following repeating units (R PA1 )、(R PA2 ) and (R PA3 ):

[0112]

[0113] wherein R1 is hexamethylene -(CH2)6-, and R2 is a divalent radical of a diamine selected from the group consisting of 1,9-diaminononane, 1,10-diaminodecane, and a combination of the two diamines. For clarity, the divalent radical of 1,9-diaminononane is -(CH2)9-, and the divalent radical of 1,10-diaminodecane is -(CH2) 10 .

[0114] RPA1 corresponds to the repeating unit obtained by the reaction of terephthalic acid with 1,6-diaminohexane, and R PA2 corresponds to the repeating units obtained from the reaction of terephthalic acid with the one or more other diamines in C9 and / or C10. Similarly, R PA3 corresponds to the repeating units obtained from the reaction of terephthalic acid with bis(aminomethyl)cyclohexane (eg, 1,3-bis(aminomethyl)cyclohexane and / or 1,4-bis(aminomethyl)cyclohexane).

[0115] All ratios and examples provided herein for the ratios of diamine 1,6-diaminohexane, D1 and D2 in the diamine component (A) can be converted to (R PA1 )、(R PA2 ) and (R PA3 ) of the corresponding proportion.

[0116] The ratio of the repeating units in polyamide (PA) is the following ratio:

[0117] -R PA1 : between 38.0 and 54.0 mol%;

[0118] -R PA2 : between 15.0 and 40.0 mol %;

[0119] -R PA3 : between 15.0 and 40.0 mol %;

[0120] These proportions in mol % are relative to the total amount of repeating units in the polyamide (PA).

[0121] According to an embodiment, the repeating unit (R PA1 )、(R PA2 ) and (R PA3 ) is at least 95.0 mol %, more particularly at least 99.0 mol %.

[0122] According to another embodiment, the repeating units of the polyamide (PA) consist essentially of these repeating units (R PA1 )、(R PA2 ) and (R PA3 ). The expression "essentially consists of" in relation to the repeating units of polyamide (PA) means that the repeating units of the polyamide consist of (R PA1 ), (R PA2 ) and (R PA3 ) and up to 2.0 mol%, preferably up to 1.5 mol%, preferably up to 1.0 mol%, preferably up to 0.5 mol% of other than the repeating unit (R PA1)、(R PA2 ) and (R PA3 ) other than the repeating units.

[0123] R PA1 The proportion of α-Hydroxy-1-oxo ...

[0124] R PA2 The proportion may be between 15.0 and 40.0 mol %. The proportion may more particularly be between 18.0 and 40.0 mol %. The proportion may more particularly be between 18.0 and 40.0 mol %. The proportion may more particularly be between 33.0 and 37.0 mol %, or between 18.0 and 22.0 mol %, or between 23.0 and 27.0 mol %, or between 28.0 and 32.0 mol %.

[0125] R PA3 The proportion may be between 15.0 and 40.0 mol %. The proportion may more particularly be between 18.0 and 40.0 mol %. The proportion may more particularly be between 18.0 and 22.0 mol % or between 28.0 and 32.0 mol % or between 33.0 and 37.0 mol %.

[0126] The polyamide (PA) of the present invention preferably comprises no repeating units derived from lactams or from amino acids.The polyamide (PA) of the present invention preferably comprises no repeating units derived from isophoronediamine.

[0127] The polyamide (PA) of the present invention typically has a number average molecular weight ("Mn") in the range of 1,000 g / mol to 40,000 g / mol, for example 2,000 g / mol to 35,000 g / mol, 4,000 to 30,000 g / mol, or 5,000 g / mol to 20,000 g / mol. Mn may also be between 8,000 and 20,000 g / mol. Mn is preferably strictly above 8,000 g / mol. Mn can be determined by size exclusion chromatography (SEC) with polystyrene standards or by using the following equation (1): Mn=2,000,000 / [EG] (1), where [EG] is the proportion of end groups in the polyamide (PA) (expressed in mmol / kg). The end groups in the polyamide (PA) are typically amine and / or acid moieties. However, when the polycondensation involves the addition of an end-capping agent, the amine end groups are partially or completely converted into one or more modified end groups. For example, when the end cap is an acid such as benzoic acid or acetic acid, the remaining amine groups can be converted in whole or in part to benzamide or acetamide end groups.

[0128] The end groups in the polyamide (PA) are selected from the group consisting of -NH2, -COOH and amide end groups. In fact, the end groups in the polyamide (PA) can be -NH2 or -COOH. However, when the polycondensation involves the addition of an end-capping agent, these end groups can be partially or completely converted into amide end groups.

[0129] The amide end groups are of the formula -NH-C(=O)-R, wherein R is an alkyl, aryl or cycloalkyl group, and / or of the formula -C(=O)-NH-R', wherein R' is an alkyl or cycloalkyl group. R is more particularly a linear or branched C1-C 17 Alkyl or C5-C 10 Cycloalkyl. R' is more particularly a linear or branched C2-C 18 alkyl.

[0130] Amide end groups of the formula -NH-C(=O)-R are produced by the reaction of the end group -NH2 with a monocarboxylic acid of the formula R-COOH (capping agent).

[0131] The monocarboxylic acid (capping agent) may advantageously be selected from the group consisting of: benzoic acid; cyclohexanoic acid; R-COOH, wherein R is a linear or branched C1-C 17 and combinations of two or more of these acids. R is a group derived from an acid having the formula R-COOH.

[0132] The monocarboxylic acid (capping agent) may more particularly be chosen from the group consisting of acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, lauric acid, stearic acid, 2-ethylhexanoic acid, cyclohexanoic acid, benzoic acid and combinations of two or more of these acids.

[0133] The monocarboxylic acid (capping agent) is more particularly a monocarboxylic acid having the formula CH3-(CH2) n -COOH, wherein n is an integer between 0 and 16. The amide end group has the formula -NH-C(=O)-(CH2) n -CH3.

[0134] An amide end group of formula -C(=O)-NH-R' results from the reaction of a terminal group -COOH with a primary amine of formula R'-NH2 (capping agent).

[0135] The primary amine (capping agent) may advantageously be selected from the group consisting of: amines having the formula R'-NH2, wherein R' is a linear or branched C2-C 18 Alkyl. R' is a group derived from an amine having the formula R'-NH2.

[0136] The primary amine (capping agent) is more particularly a amine having the formula CH3-(CH2) n' -NH2, wherein n' is an integer between 2 and 18. The amide end group is of the formula -C(=O)-NH-(CH2) n' -CH3.

[0137] The primary amine (blocking agent) may more particularly be chosen from the group consisting of propylamine, butylamine, pentylamine, hexylamine, 2-ethylhexylamine, n-octylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, stearylamine, cyclohexylamine and combinations of two or more of these amines.

[0138] The proportion of end groups in polyamide (PA) can be determined by 1 Quantification was by H NMR or potentiometry techniques.

[0139] The polyamide (PA) preferably exhibits an inherent viscosity ("IV") of between 0.5 and 1.5 dL / g, more particularly between 0.7 and 1.3 dL / g, more particularly between 0.75 and 1.20 dL / g, as measured according to ASTM D5336. The IV may be between 0.80 and 1.00 dL / g or between 0.90 and 1.20 dL / g. The IV is preferably between 0.95 and 1.20 dL / g. The IV can be conveniently measured in a 60 wt% / 40 wt% phenol / tetrachloroethane mixture.

[0140] Polyamide (PA) can be prepared from the following combinations of monomers as disclosed in Table I or Table III.

[0141] Moisture absorption rate

[0142] The polyamide (PA) advantageously exhibits a water absorption at 23°C of less than 5.0 wt%.

[0143] The water absorption at 23° C. is determined by (i) providing a test specimen formed according to ISO 527 in its dry state (moisture content less than 0.2 wt.%), (ii) immersing the test specimen in deionized water at 23° C. until constant weight is reached, and (iii) calculating the water absorption using the following formula:

[0144]

[0145] Where W 之前 is the weight of the molded specimen in its initial dry state and W 之后 is the weight of the molded specimen after water absorption.

[0146] Biomass content

[0147] Sustainable resins are increasingly sought. That is why polyamides (PA) preferably exhibit a biocontent of at least 10.0%, preferably at least 15.0%, expressed as a % of organic carbon of renewable origin determined according to ASTM D6866-22. The biocontent of polyamides (PA) may be at least 20.0%.

[0148] The biocontent may be between 10.0% and 21.0%.

[0149] Biocontent is defined as the % of organic carbon of renewable origin. It corresponds to the 14 The amount of C is calculated from the C percentage and corrected for the isotope fraction.

[0150] Both the C9 and C10 diamines used to make polyamide (PA) can be bio-based or produced from petroleum or natural gas:

[0151]

[0152]

[0153] Therefore, the polyamide (PA) disclosed herein is preferably prepared from bio-based 1,9-nonanediamine (C9) and / or 1,10-decanediamine (C10). This allows for the production of polyamide (PA) with a high biocontent. The high biocontent of PA comes primarily from C9 and / or C10 diamines.

[0154] According to an embodiment, the polyamide (PA) disclosed herein is prepared from bio-based 1,9-nonanediamine (C9) and / or 1,10-decanediamine (C10), which exhibits a biocontent of at least 99.0%, preferably at least 99.5%, preferably at least 99.9%, expressed as a % of organic carbon of renewable origin measured according to ASTM D6866-22.

[0155] However, the biocontent can also be increased by using bio-based terephthalic acid. Bio-based terephthalic acid can be prepared, for example, from bio-based furfural, as described in Tachibana, Y., Kimura, S. & Kasuya, K.-i. "Synthesis and Verification of Biobased Terephthalic Acid from Furfural," Sci. Rep. 5, 8249; DOI: 10.1038 / srep08249 (2015). The biocontent of the polyamide (PA) as defined above can then be at least 65.0%.

[0156] Thermal properties of polyamide (PA)

[0157] As indicated above, it has surprisingly been found that the polyamides (PA) of the present invention exhibit a combination of thermal properties.Any of the features of thermal properties disclosed below may be used to characterize the polyamides of the present invention.

[0158] 1) Melting point (Tm)

[0159] The polyamide (PA) exhibits a Tm strictly lower than 300°C (<300°C), preferably lower than or equal to 296.0°C (≤296.0°C), preferably lower than or equal to 295.0°C (≤296.0°C), preferably strictly lower than 290°C (<290°C).

[0160] Tm is preferably lower than or equal to 280°C (≤ 280°C).

[0161] The Tm may also be lower than or equal to 270°C (≤ 270°C).

[0162] Tm is generally at least 250°C, preferably at least 260°C.

[0163] The Tm may be between 250°C and 280°C or between 260.0°C and 280.0°C.

[0164] Tm can be measured by differential scanning calorimetry ("DSC") according to ASTM D3418, particularly using heating and cooling rates of 20°C / min.

[0165] Tm can be measured more particularly as described in the experimental section. In fact, Tm can be measured by differential scanning calorimetry ("DSC") according to ASTM D3418 using a heating and cooling rate of 20°C / min. Three scans are used for each DSC test: a first heating to 350°C, followed by a first cooling to 0°C, followed by a second heating to 360°C. Tm is determined from the second heating.

[0166] 2) Glass transition temperature (Tg)

[0167] The polyamide (PA) exhibits a Tg of at least 140°C, preferably at least 145°C.

[0168] Polyamide (PA) typically exhibits a Tg of at most 200°C, or at most 180°C, or at most 160°C.

[0169] The Tg may more particularly be between 145 and 180°C or between 145 and 160°C.

[0170] Tg can be measured by differential scanning calorimetry ("DSC") according to ASTM D3418, particularly using heating and cooling rates of 20°C / min.

[0171] Tg can be measured more specifically as described in the experimental section. In fact, Tg can be measured by differential scanning calorimetry ("DSC") according to ASTM D3418 using a heating and cooling rate of 20°C / min. Three scans are used for each DSC test: a first heating to 350°C, followed by a first cooling to 0°C, followed by a second heating to 360°C. Tg is determined from the second heating.

[0172] According to a preferred embodiment, the polyamide (PA) exhibits a difference (Tm - Tg) below 130°C, preferably below 125°C.

[0173] 3) Crystallization temperature (Tc)

[0174] The polyamide (PA) exhibits a Tc lower than or equal to 225°C, preferably lower than or equal to 220°C.

[0175] Tc is typically at least 170°C or at least 190°C.

[0176] Tc may be between 170°C and 225°C.

[0177] Tc is measured by differential scanning calorimetry ("DSC") according to ASTM D3418, specifically using heating and cooling rates of 20°C / min.

[0178] Tc can be measured by differential scanning calorimetry ("DSC") according to ASTM D3418 using a heating and cooling rate of 20°C / min. Three scans are used for each DSC test: a first heating to 350°C, followed by a first cooling to 0°C, followed by a second heating to 360°C. Tc is determined from the first cooling.

[0179] The lower the Tc, the better for the preparation of thermoplastic composites, because the lower Tc helps minimize warpage and stress in the resin. The polyamide (PA) of the present invention preferably exhibits a difference (Tm-Tc) of at least 50.0°C, preferably at least 55.0°C, preferably at least 60.0°C. (Tm-Tc) can be between 50.0°C and 85.0°C.

[0180] 4) Heat of fusion (Hm)

[0181] Polyamide (PA) is semi-crystalline.

[0182] The polyamide (PA) exhibits a Hm of at least 15.0 J / g, preferably at least 20.0 J / g, preferably at least 25.0 J / g, preferably at least 27.0 J / g.

[0183] Hm may be at most 40.0 J / g or at most 39.0 J / g.

[0184] Hm is preferably between 15.0 and 40.0 J / g, preferably between 15.0 and 40.0 J / g (this latter value being excluded).

[0185] Hm can be measured by differential scanning calorimetry ("DSC") according to ASTM D3418, particularly using heating and cooling rates of 20°C / min.

[0186] Hm can be measured more particularly as described in the experimental section. In fact, Hm can be measured by differential scanning calorimetry ("DSC") according to ASTM D3418 using a heating and cooling rate of 20°C / min. Three scans are used for each DSC test: a first heating to 350°C, followed by a first cooling to 0°C, followed by a second heating to 360°C.

[0187] Hm can be measured as described in the experimental section.

[0188] Method for preparing polyamide (PA)

[0189] The polyamides (PA) described herein can be prepared by any conventional method suitable for the synthesis of polyamides and polyphthalamides.

[0190] Polyamide (PA) is produced by polycondensation.

[0191] Polyamide (PA) can be prepared by heating a reaction mixture (RM) comprising all monomers constituting the polyamide (PA) [e.g., hexamethylenediamine, D1 and D2, terephthalic acid, and optionally DI], preferably in the presence of less than 60 wt.%, preferably less than 30 wt.%, less than 20 wt.%, less than 10 wt.% of water, preferably without adding water. The proportions are based on the total weight of the reaction mixture (RM).

[0192] The temperature to which the reaction mixture (RM) is heated must be high enough to initiate the reaction between the amine and carboxyl groups and to reduce the viscosity of the reaction mixture. This temperature is typically at least 200°C. The reaction mixture (RM) is preferably heated at a temperature ≥ Tm + 25°C. Polycondensation results in the formation of amide bonds and the release of water as a by-product.

[0193] The reaction mixture (RM) comprises the diamines of the diamine component (A) and the one or more diacids of the dicarboxylic acid component (B). As detailed above, the ratio of the two components is such that the reaction mixture contains an amount of monomers such that the ratio of -COOH groups from the dicarboxylic acid and the ratio of -NH2 groups from the diamine are substantially equimolar. The molar ratio of -NH2 from the diamines of the diamine component (A) / -COOH from the dicarboxylic acid of the dicarboxylic acid component (B) is preferably between 0.9 and 1.1, preferably between 0.95 and 1.05, and even more preferably between 0.98 and 1.02.

[0194] Reaction mixture (RM) preferably further comprises catalyzer.Catalyzer can be selected from the group consisting of: phosphoric acid, phosphorous acid, hypophosphorous acid, phenylphosphonic acid, phenylphosphinic acid, the acid and the salt of monovalent to trivalent cation and the ester of the acid.Cation can for example be Na, K, Mg, Ca, Zn or Al.The example of ester is triphenyl phosphate, triphenyl phosphite and tris (nonylphenyl) phosphite.The catalyzer conveniently used is phosphorous acid.

[0195] The proportion of catalyst in the reaction mixture (RM) is preferably between 0.005 and 2.5 wt%, based on the weight of the monomers in the reaction mixture.

[0196] According to embodiments of the present disclosure, the reaction mixture (RM) comprises or consists of:

[0197] - monomers constituting polyamide (PA), as disclosed herein;

[0198] - optionally a catalyst, in particular chosen from the group consisting of phosphorous acid, orthophosphoric acid, metaphosphoric acid, alkali metal hypophosphites such as sodium hypophosphite, and phenylphosphinic acid, and combinations thereof;

[0199] - optionally at least one capping agent selected from the group consisting of monocarboxylic acids, primary amines, and combinations thereof;

[0200] - Water, in a proportion of less than 60 wt.%, preferably less than 30 wt.%, preferably less than 20 wt.%, preferably less than 10 wt.% of water, the proportion being based on the total weight of the reaction mixture (RM). According to an embodiment, no water is added at the start of the polycondensation.

[0201] In order to control the molar mass, at least one chain transfer agent can be used, which is preferably selected from C1-C 18 Monocarboxylic acids and C3-C 18 The chain transfer agent may more particularly be chosen from the group consisting of acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, lauric acid, stearic acid, 2-ethylhexanoic acid, cyclohexanoic acid, benzoic acid, butylamine, pentylamine, hexylamine, 2-ethylhexylamine, n-octylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, stearylamine, cyclohexylamine, and mixtures thereof.

[0202] The polycondensation is advantageously carried out in a well-stirred vessel equipped with a device for removing the volatile products of the reaction. As the viscosity of the reaction mixture increases over time, the stirrer is suitable for providing sufficient stirring for the reaction mixture (RM) at the beginning of the polymerization and when the polycondensation conversion is nearing completion.

[0203] The conditions disclosed in the experimental section can be conveniently used to prepare polyamide (PA).

[0204] Thermoplastic Composites (TC)

[0205] The polyamide (PA) of the present invention is suitable for preparing a thermoplastic composite (TC), which comprises:

[0206] a polymer matrix comprising or consisting of at least one polyamide (PA) and optionally at least one plastic additive; and

[0207] -fiber.

[0208] The proportion of fibers in the thermoplastic composite (TC) is generally at least 40.0 wt%.

[0209] Thermoplastic composites (TC) comprise or consist of a polymer matrix and fibers. The fibers are adhesively or polymerically bonded to the matrix, which typically completely surrounds the fibers.

[0210] The polymer matrix comprises the polyamide (PA) of the present invention and optionally at least one plastic additive blended with the polyamide. The plastic additive may be selected from the group consisting of colorants (e.g., dyes and / or pigments), UV stabilizers, heat stabilizers, antioxidants, acid scavengers, processing aids, internal and / or external lubricants, flame retardants, smoke suppressants, antistatic agents, anti-caking agents, and any combination thereof. The proportion of the one or more plastic additives in the polymer matrix is ​​typically less than 20.0 wt%, based on the total weight of the polymer matrix.

[0211] Fibers generally exhibit high specific stiffness and strength values.

[0212] The fibers may be of inorganic type (eg glass fibers) or of organic type (eg aramid fibers or carbon fibers). Combinations of various fibers may also be used.

[0213] The fibers may be selected from the group consisting of glass fibers, carbon fibers, aramid fibers, stainless steel fibers, potassium titanate whiskers, and combinations of two or more thereof.

[0214] Thermoplastic composites (TC) can be manufactured by methods well known in the art. Generally, regardless of the type of method, composite material manufacturing includes impregnating fibers with a polymer matrix in molten form and then cooling to room temperature. Melt impregnation may further include mechanical compression of the melt on the fibers.

[0215] Thermoplastic composites (TC) can be used to prepare articles for the automotive industry.

[0216] [Experimental part]

[0217] The examples of the present invention illustrate the synthesis, thermal properties and mechanical properties of polyamides. The raw materials used to form the samples are provided below:

[0218] Raw materials used

[0219] The following raw materials were used to prepare the polymer samples:

[0220] Table I

[0221]

[0222] Thermal performance

[0223] Tg, Tm, and Hm are measured by differential scanning calorimetry ("DSC") according to ASTM D3418 using a heating and cooling rate of 20°C / min. Three scans are used for each DSC test: a first heating to 350°C, followed by a first cooling to 0°C, followed by a second heating to 360°C. Tg, Tm, and Hm are determined from the second heating. Tc is determined from the cooling.

[0224] Inherent viscosity (IV)

[0225] Inherent viscosity (IV) was measured according to ASTM D5336 in a 60 wt% phenol - 40 wt% tetrachloroethane mixture.

[0226] Tensile elongation at break

[0227] Measured according to ISO 527 using ISO 1A strips.

[0228] Chordal modulus and notched izod

[0229] Chordal Modulus: Measured according to ISO 527 using ISO 1A strips.

[0230] Shock: Measured according to ISO 180.

[0231] Biomass content

[0232] Determined according to ASTM D6866-22.

[0233] Preparation of copolyamide

[0234] All copolyamides disclosed in Table III were prepared in an autoclave reactor equipped with a distillate line equipped with a pressure control valve.

[0235] All copolyamides were prepared by charging the monomers, water and phosphorous acid in the targeted ratios into a reactor and following the procedure given in Example 1 below.

[0236] Example 1 (E1):Polyamide E1 was prepared by charging a reactor with 1.77 g of 1,6-diaminohexane, 2.05 g of 1,10-diaminodecane, 0.96 g of 1,3-cyclohexane-bis(methylamine), 5.32 g of terephthalic acid, 4.98 g of deionized water, and 0.0033 g of phosphorous acid. The reactor was sealed and purged three times with N2 gas. The reactor was heated to 177°C and held for 30 min, then heated to 232°C and held for 30 min, then heated to 288°C and held for 30 min, then heated to 343°C and held for 35 min. The steam generated was slowly released to keep the internal pressure below 200 psig. Once the temperature was at 343°C for 35 min, the reactor pressure was slowly reduced to atmospheric pressure over 25 min. After the decompression was complete, the reactor was continuously purged with N2 gas over 25 min. Afterwards, the reactor was cooled to room temperature and the polymer was removed from the reactor.

[0237] As can be seen from the results in Table III, a specific ratio of monomers allows for a balance of properties, particularly a high Tg and a low Tm.

[0238] Furthermore, the polyamide of the invention exhibits significantly high elongation at break and notched impact. It also exhibits improved notched impact.

[0239] Table II: Mechanical properties

[0240]

[0241]

Claims

1. A polyamide (PA) exhibiting a melting temperature Tm strictly lower than 300° C. (<300° C.), preferably lower than or equal to 296.0° C. (≤296.0° C.), preferably lower than or equal to 295.0° C. (≤295.0° C.), preferably strictly lower than 290° C. (<290° C.), and comprising repeating units formed by the polycondensation of a diamine component (A) and a dicarboxylic acid component (B), wherein: a) The diamine component (A) comprises: - between 38.0 and 54.0 mol % of 1,6-diaminohexane; - between 15.0 and 40.0 mol % of a diamine (D1) chosen from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines; - between 15.0 and 40.0 mol % of a diamine (D2) selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane and a combination of said two diamines; These proportions in mol % are based on the total amount of diamines in the diamine component (A); b) the dicarboxylic acid component (B) comprises: - between 95.0 and 100.0 mol % of terephthalic acid; - between 0 and 5.0 mol% of another diacid selected from the group consisting of isophthalic acid, adipic acid and a combination of these two said diacids; These proportions in mol % are based on the total amount of diacids in the dicarboxylic acid component (B).

2. The polyamide (PA) according to claim 1, wherein The diamine component (A) consists essentially of or consists of 1,6-diaminohexane; a diamine (D1) selected from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of the two diamines; and a diamine (D2) selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane and a combination of the two diamines, the expression "essentially consisting of" meaning that the diamine component (A) consists of 1,6-diaminohexane, D1 and D2 and up to 2.0 mol %, preferably up to 1.0 mol %, even more preferably up to 0.5 mol %, of at least one further diamine other than 1,6-diaminohexane, D1 and D2, the proportions in mol % being based on the total amount of diamines in the diamine component (A).

3. The polyamide (PA) according to claim 1 or claim 2, wherein The dicarboxylic acid component (B) consists essentially of or consists of terephthalic acid and the one or more other diacids (DI), expressed as "Essentially consisting of" means that the dicarboxylic acid component (B) consists of terephthalic acid, diacid (DI) and up to 2.0 mol %, preferably up to 1.0 mol %, even more preferably up to 0.5 mol % of at least one further diacid other than terephthalic acid and one or more diacids (DI), the proportions in mol % being based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B).

4. The polyamide according to claim 1 or claim 2, wherein The dicarboxylic acid component (B) consists essentially of or consists of terephthalic acid, "Essentially consisting of" means that the dicarboxylic acid component (B) consists of terephthalic acid and up to 2.0 mol %, preferably up to 1.0 mol %, even more preferably up to 0.5 mol % of at least one further diacid other than terephthalic acid, the proportions in mol % being based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B).

5. The polyamide (PA) according to any one of claims 1 to 3, wherein The ratios in the dicarboxylic acid component (B) are the following ratios: - between 95.0 and 99.9 mol % of terephthalic acid and between 0.1 and 5.0 mol % of the one or more other diacids; or - between 98.0 and 99.9 mol % of terephthalic acid and between 0.1 and 2.0 mol % of the other diacid(s).

6. A polyamide (PA), in particular a polyamide (PA) according to any one of the preceding claims, comprising repeating units (R PA1 )、(R PA2 ) and (R PA3 ): and / or or the following repeating units: wherein R1 is -(CH2)6-, and R2 is a divalent radical of a diamine selected from the group consisting of 1,9-diaminononane, 1,10-diaminodecane, and a combination of the two diamines; The ratios in the repeating units are the following: -R PA1 : between 38.0 and 54.0 mol%; -R PA2 : between 15.0 and 40.0 mol %; -R PA3 : between 15.0 and 40.0 mol %; These proportions in mol % are relative to the total amount of repeating units in the polyamide (PA).

7. The polyamide (PA) according to claim 6, wherein Repeating unit (R PA1 )、(R PA2 ) and (R PA3 ) is at least 95.0 mol %, more particularly at least 99.0 mol %.

8. The polyamide (PA) according to claim 6, wherein The repeating units of the polyamide (PA) consist essentially of repeating units (R PA1 )、(R PA2 ) and (R PA3 ) is composed of or consists of, expresses "Essentially consisting of" means that the repeating units of the polyamide (PA) consist of (R PA1 ), (R PA2 ) and (R PA3 ) and up to 2.0 mol%, preferably up to 1.5 mol%, preferably up to 1.0 mol%, preferably up to 0.5 mol% of other than the repeating unit (R PA1 )、(R PA2 ) and (R PA3 ) other than the repeating units.

9. Polyamide (PA) according to any one of the preceding claims, wherein The proportion of 1,6-hexanediamine in the diamine component (A) or R PA1 The ratio is: - between 38.0 and 52.0 mol %; or - between 38.0 and 47.0 mol %; or - between 42.0 and 47.0 mol %; or - between 48.0 and 52.0 mol %; or - between 38.0 and 42.0 mol%.

10. Polyamide (PA) according to any one of the preceding claims, wherein The proportion of the other diamine (D1) selected from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of the two diamines in the diamine component (A) or the R PA2 The ratio is: - between 18.0 and 33.0 mol %; or - between 18.0 and 40.0 mol %; or - between 33.0 and 37.0 mol %; or - between 18.0 and 22.0 mol %; or - between 23.0 and 27.0 mol %; or - between 28.0 and 32.0 mol%.

11. Polyamide (PA) according to any one of the preceding claims, wherein The proportion of the other diamine (D2) selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane and a combination of the two diamines in the diamine component (A) or the R PA3 The ratio is: - between 18.0 and 40.0 mol %; or - between 18.0 and 22.0 mol %; or - between 28.0 and 32.0 mol %; or - between 33.0 and 37.0 mol%.

12. Polyamide (PA) according to any one of the preceding claims, wherein The ratios in the diamine component (A) are as follows: - between 42.0 and 47.0 mol % of 1,6-diaminohexane; - between 33.0 and 37.0 mol % of a diamine (D1) chosen from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines; - between 18.0 and 22.0 mol % of a diamine (D2) selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane and a combination of said two diamines; or the following ratio: - between 48.0 and 52.0 mol % of 1,6-diaminohexane; - between 18.0 and 22.0 mol % of a diamine (D1) chosen from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines; - between 28.0 and 32.0 mol % of a diamine (D2) selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane and a combination of said two diamines; or the following ratio: - between 38.0 and 42.0 mol % of 1,6-diaminohexane; - between 23.0 and 27.0 mol % of a diamine (D1) chosen from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines; - between 33.0 and 37.0 mol % of a diamine (D2) selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane and a combination of said two diamines; or the following ratio: - between 48.0 and 52.0 mol % of 1,6-diaminohexane; - between 28.0 and 32.0 mol % of a diamine (D1) chosen from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines; - between 18.0 and 22.0 mol % of a diamine (D2) selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane and a combination of said two diamines; or the following ratio: - between 48.0 and 52.0 mol % of 1,6-diaminohexane; - between 18.0 and 22.0 mol % of a diamine (D1) chosen from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines; - between 28.0 and 32.0 mol % of a diamine (D2) selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane and a combination of said two diamines; or the following ratio: - between 43.0 and 47.0 mol % of 1,6-diaminohexane; - between 33.0 and 37.0 mol % of a diamine (D1) chosen from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines; - between 18.0 and 22.0 mol % of a diamine (D2) selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane and a combination of said two diamines.

13. The polyamide (PA) according to any one of claims 6 to 12, wherein These ratios are the following: - between 42.0 and 47.0 mol% of R PA1 ; - between 33.0 and 37.0 mol% of R PA2 ; - between 18.0 and 22.0 mol% of R PA3 ; or the following ratio: - between 48.0 and 52.0 mol% of R PA1 ; - between 18.0 and 22.0 mol% of R PA2 ; - between 28.0 and 32.0 mol% of R PA3 ; or the following ratio: - between 38.0 and 42.0 mol% of R PA1 ; - between 23.0 and 27.0 mol% of R PA2 ; - between 33.0 and 37.0 mol% of R PA3 ; or the following ratio: - between 48.0 and 52.0 mol% of R PA1 ; - between 28.0 and 32.0 mol% of R PA2 ; - between 18.0 and 22.0 mol% of R PA3 ; or the following ratio: - between 48.0 and 52.0 mol% of R PA1 ; - between 18.0 and 22.0 mol% of R PA2 ; - between 28.0 and 32.0 mol% of R PA3 ; or the following ratio: - between 43.0 and 47.0 mol% of R PA1 ; - between 33.0 and 37.0 mol% of R PA2 ; - between 18.0 and 22.0 mol% of R PA3 ; These proportions are given relative to the total proportions of the repeating units in the polyamide (PA).

14. Polyamide (PA) according to any one of the preceding claims, wherein The end groups in the polyamide are selected from the group consisting of -NH2, -COOH and amide end groups.

15. The polyamide (PA) according to claim 14, wherein These amide end groups are of the formula -NH-C(=O)-R, wherein R is alkyl, aryl or cycloalkyl, and / or of the formula -C(=O)-NH-R', wherein R' is alkyl or cycloalkyl.

16. Polyamide (PA) according to any one of the preceding claims, wherein The melting temperature Tm of the polyamide (PA) is: - lower than or equal to 280°C (≤280°C) or lower than or equal to 270°C (≤280°C); and / or - at least 250°C, preferably at least 260°C; Tm is measured by DSC according to ASTM D3418, specifically using a heating and cooling rate of 20°C / min.

17. Polyamide (PA) according to any one of the preceding claims, wherein The glass transition temperature Tg of the polyamide (PA) is: - at least 140°C, preferably at least 145°C; and / or - up to 200°C or up to 180°C or up to 160°C; Tg is measured by DSC according to ASTM D3418, specifically using a heating and cooling rate of 20°C / min.

18. Polyamide (PA) according to any of the preceding claims, which exhibits a difference (Tm - Tg) of less than 130°C, preferably less than 125°C, the melting temperature Tm and the glass transition temperature Tg measured by DSC according to ASTM D3418, in particular using a heating and cooling rate of 20°C / min.

19. The polyamide (PA) according to any of the preceding claims, which exhibits a difference (Tm - Tc) of at least 50.0°C, preferably at least 55.0°C, preferably at least 60°C, or between 50.0°C and 85.0°C, the melting temperature Tm and the crystallization temperature Tc being measured by DSC according to ASTM D3418, in particular using a heating and cooling rate of 20°C / min.

20. The polyamide (PA) according to any one of the preceding claims, which exhibits the following heat of fusion Hm: - at least 15.0 J / g, preferably at least 20.0 J / g, preferably at least 25.0 J / g, preferably at least 27.0 J / g; and / or - between 15.0 and 40.0 J / g, preferably between 15.0 and 40.0 J / g (this latter value being excluded); Hm is measured by differential scanning calorimetry ("DSC") according to ASTM D3418, particularly using a heating and cooling rate of 20°C / min; and / or 21. Polyamide (PA) according to any one of the preceding claims, exhibiting an inherent viscosity ("IV") measured according to ASTM D5336 of: - between 0.5 and 1.5 dL / g; or - between 0.7 and 1.3 dL / g; or - between 0.75 and 1.20 dL / g; or - between 0.80 and 1.00 dL / g; or - between 0.90 and 1.20 dL / g; or - Between 0.95 and 1.20 dL / g.

22. The polyamide (PA) according to any one of the preceding claims, exhibiting a number average molecular weight ("Mn") between 8,000 and 20,000 g / mol.

23. The polyamide (PA) according to any one of the preceding claims, prepared from 1,9-diaminononane (C9) and / or 1,10-diaminodecane (C10), exhibiting a biocontent expressed as a % of organic carbon of renewable origin determined according to ASTM D6866-22 of at least 99.0%, preferably at least 99.5%, preferably at least 99.9%.

24. The polyamide (PA) according to any one of the preceding claims, which exhibits a water absorption at 23°C of less than 5.0 wt.%, the water absorption at 23°C being determined by: (i) providing a test specimen formed according to ISO 527 in its dry state (moisture content less than 0.2 wt.%), (ii) immersing the test specimen in deionized water at 23°C until constant weight is reached, (iii) calculating the water absorption using the following formula: Where W 之前 is the weight of the molded specimen in its initial dry state and W 之后 is the weight of the molded specimen after water absorption.

25. The polyamide (PA) according to claim 1 , which is prepared by polycondensation by heating a reaction mixture (RM) comprising all these monomers, the reaction mixture (RM) comprising or consisting in particular of: - the monomers constituting the polyamide (PA); - optionally a catalyst, in particular chosen from the group consisting of phosphorous acid, orthophosphoric acid, metaphosphoric acid, alkali metal hypophosphites such as sodium hypophosphite, and phenylphosphinic acid, and combinations thereof; - optionally at least one capping agent selected from the group consisting of monocarboxylic acids, primary amines, and combinations thereof; - Water, in a proportion of less than 60 wt.%, preferably less than 30 wt.%, preferably less than 20 wt.%, preferably less than 10 wt.% of water, the proportion being based on the total weight of the reaction mixture (RM).

26. A thermoplastic composite (TC) comprising: a polymer matrix comprising or consisting of a polyamide (PA) according to any one of claims 1 to 25 and optionally at least one plastic additive, in particular chosen from the group consisting of: colorants, UV stabilizers, heat stabilizers, antioxidants, acid scavengers, processing aids, internal and / or external lubricants, flame retardants, smoke suppressants, antistatic agents, anti-blocking agents and any combination thereof; and -fiber.

27. Use of the polyamide (PA) according to any one of claims 1 to 25 for producing thermoplastic composite materials.

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