Semi-aromatic polyamides with low melting temperatures

Abstract

The present invention provides a polyamide (PA) that exhibits a melting temperature Tm strictly less than 290°C and comprises repeating units formed by polycondensation of a diamine component (A) and a dicarboxylic acid component (B), wherein a) the diamine component (A) comprises: 38.0 to 54.0 mol % of 1,6-diaminohexane; 15.0 to 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; and 15.0 to 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, these proportions in mol % being based on the total amount of diamines in the diamine component (A); and b) the dicarboxylic acid component (B) comprises: 95.0 to 100.0 mol % of terephthalic acid; 0 to 5.0 mol % of another diacid selected from the group consisting of isophthalic acid, adipic acid and a combination of said two diacids, these proportions in mol % being based on the total amount of diacids in the dicarboxylic acid component (B) in relation to the polyamide (PA).

Description

[Technical Field]

[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 discrepancy between this application and the two U.S. and European applications that would affect the clarity of terminology or wording, only this application shall be referenced.

[0002] The present invention relates to semi-crystalline, semi-aromatic copolyamides having high glass transition temperatures and low melting temperatures, along with a combination of other properties that make them suitable for the preparation of thermoplastic composites. [Background technology]

[0003] Aliphatic polyamides, such as the well-known PA6 and PA66, are a highly valued group of thermoplastics due to their ease of processing and generally 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, up to 10%.

[0004] Aliphatic polyamides cannot be used in many applications where they are applied in wet or moist conditions and have strict requirements for dimensional stability. Water absorption changes not only the dimensions but also the mechanical properties. Water absorption reduces the stiffness and strength to a fraction of their original values. However, many applications involve mechanical loads when in contact with water or ambient moisture.

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

[0006] WO 2018 / 234439 discloses polyamide BACT / 10T / 6T which does not contain a specific composition.

[0007] WO 2018 / 172717 discloses semi-aromatic copolyamides with 1.3BAC, which exhibit a Tm higher than 290°C or are based on different compositions with a higher proportion of BACT.

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

[0009] US Patent Application Publication No. 2008 / 274355 (D1) discloses polyamide molding compositions based on the copolyamide 10T / 6T having 40 to 95 mol % of 10T units and 5 to 60 mol % of 6T units.

[0010] US Patent Application Publication No. 2019 / 338074 and WO 2018 / 011495 / US Patent Application Publication No. 2018 / 251601 (D2) disclose semi-aromatic copolyamides based on 1.3BAC having a melting temperature of less than 300°C. The copolyamides of D2 preferably exhibit a Tm-Tc (Tm = melting temperature, Tc = crystallization temperature) of less than 40°C. Two compositions based on 10T, 6T, and BACT disclosed in the experimental sections of US Patent Application Publication No. 2019 / 338074 and WO 2018 / 011495 do not conform to the composition of claim 1. D2 more specifically discloses the copolyamide 10T / BACT / 6T, which exhibits a low (Tm-Tc) value of less than 37°C and a heat of fusion Hm of greater than 40.0 J / g.

[0011] [Table 1]

[0012] US Patent Application Publication No. 2016 / 0152770 discloses a semi-aromatic copolyamide comprising, 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, where the cyclic diamine d) comprises isophoronediamine. The proportion of hexamethylenediamine is higher than in claim 1. Furthermore, bis(aminomethyl)cyclohexane is not mentioned.

[0013] US Patent Application Publication No. 2017 / 0107326 discloses a polyamide having a certain proportion of 1,6-hexamethylenediamine and a higher melting temperature than claim 1.

[0014] WO 2021 / 037850 describes a copolymer of 55 mol% to 75 mol% of a C4 to C8 aliphatic diamine and 25 mol% to 45 mol% of a C9 to C 12A diamine component (A) containing an aliphatic diamine and 0 mol % to 10 mol % of an alicyclic diamine containing a cyclohexyl group, and a diamine component (B) containing 90 mol % to 100 mol % of terephthalic acid and 0 mol % to 10 mol % of a C6-C 18 C8-C different from aliphatic dicarboxylic acid or terephthalic acid 18 The present invention discloses a polyamide formed from an aromatic dicarboxylic acid and a dicarboxylic acid component (B) containing 0 to 10 mol % of an alicyclic dicarboxylic acid containing a cyclohexyl group. The proportion of C4 to C8 aliphatic diamine is higher than the proportion of hexamethylenediamine described in claim 1.

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

[0016] WO 2022 / 180195 describes a copolymer of 55 to 75 mol% C4 to C8 diamines and 25 to 45 mol% C9 to C 12 The present invention discloses a polyamide prepared from a diamine component containing an aliphatic diamine and 0 to 10 mol % of an alicyclic diamine containing a cyclohexyl group. The Tm is higher than that of claim 1. Summary of the Invention [Problem to be solved by the invention]

[0017] 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), which allows the polyamide to be used over a wide range of operating temperatures, and a low melting temperature (Tm), which makes the polyamide easy to process.

[0018] Furthermore, for the preparation of thermoplastic composites by melt infiltration, the polyamide used in the preparation of the thermoplastic preferably exhibits a "low" crystallization temperature (Tc) (e.g., a Tc below 230°C, preferably 225°C or less) to prepare thermoplastic composites that exhibit less stress and less warpage.

[0019] In addition to the aforementioned thermal properties, the resin forming the matrix of the composite should exhibit high elongation at break and impact resistance. Furthermore, sustainable resins are increasingly being sought.

[0020] The polyamide of the present invention aims to solve this technical problem.

[0021] general definition These definitions apply to this disclosure.

[0022] Wt% is percent by weight. Mole% is percent by mole.

[0023] Unless otherwise specified, the percentage of repeat units in a polyamide is given in mole % relative to the total percentage of repeat units in the polyamide.

[0024] Where numerical ranges are given herein, the endpoints of the range are included (even open-ended ranges, such as those including "at least," "up to," or "less than") unless otherwise expressly stated.

[0025] In this application, unless otherwise indicated, any particular embodiment or technical feature relating to one of the subject matters of the present invention is applicable to and interchangeable with other embodiments or technical features also relating to said subject matter and disclosed elsewhere in this application.

[0026] 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 acids in the dicarboxylic acid component (B) is based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B).

[0027] The proportion of repeating units in the polyamide (PA) is expressed in mole percent and is a relative value based on the total amount of repeating units in the polyamide (PA). [Means for solving the problem]

[0028] The invention is set out in the accompanying set of claims.

[0029] The present invention relates to a polyamide as disclosed in any one of claims 1 to 25.

[0030] The invention also relates to a thermoplastic composite material as defined in claim 26.

[0031] The invention also relates to the use defined in claim 27.

[0032] Further precision and detail on these topics is now provided below. DETAILED DESCRIPTION OF THE INVENTION

[0033] The present invention relates to a semi-aromatic copolyamide (PA) which exhibits a melting temperature Tm strictly below 300°C (<300°C), preferably 296.0°C or less (≦296.0°C), preferably 295.0°C or less (≦295.0°C), preferably strictly below 290°C (<290°C), and which comprises repeating units formed from the polycondensation of a diamine component (A) and a dicarboxylic acid component (B), a) The diamine component (A) is 38.0 to 54.0 mol % of 1,6-diaminohexane, - 15.0 to 40.0 mol % of a diamine (D1) selected from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines, - 15.0 to 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 percentages in mole percent are based on the total amount of diamine in diamine component (A), b) The dicarboxylic acid component (B) is - 95.0 to 100.0 mol % of terephthalic acid, - 0 to 5.0 mole % of another diacid (DI) selected from the group consisting of isophthalic acid, adipic acid and a combination of said two diacids These proportions in mole % relate to the semi-aromatic copolyamide (PA), based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B).

[0034] Thus, the polyamide (PA) disclosed in the present invention comprises, in reacted form, the diamines of the diamine component (A) and the dicarboxylic acids of the dicarboxylic acid component (B) in the proportions indicated herein.

[0035] The polyamide (PA) of the present invention is formed by polycondensation of a diamine component (A) and a dicarboxylic acid component (B). Therefore, the ratio of -NH2 derived from the diamine component (A) and the ratio of -COOH derived from the dicarboxylic acid component (B) are substantially equimolar. The molar ratio of -NH2 derived from the diamine component (A) to COOH derived from the dicarboxylic acid component (B) is preferably between 0.9 and 1.1, preferentially between 0.95 and 1.05, and even more preferentially between 0.98 and 1.02.

[0036] Further details regarding the diamine component (A) and the dicarboxylic acid component (B) are provided below.

[0037] Diamine component (A) The diamine component (A) may be any of the following diamines: 1,6-diaminohexane (of formula NH2-(CH2)6-NH2), 1,9-diaminononane (of formula NH2-(CH2)9-NH2), 1,9-diaminononane (of formula NH2-(CH2) 10 The diamine (D1) is selected from the group consisting of 1,10-diaminodecane (of —NH2) and a combination of the two diamines, and is based on bis(aminomethyl)cyclohexane (D2).

[0038] The proportion of 1,6-diaminohexane is 38.0 to 54.0 mol%. More specifically, this proportion may be 38.0 to 52.0 mol%. More specifically, this proportion may be 38.0 to 47.0 mol%. This proportion may also be 42.0 to 47.0 mol%, or 48.0 to 52.0 mol%, or 38.0 to 42.0 mol%.

[0039] The diamine component (A) also contains another diamine (D1) selected from the group consisting of 1,9-diaminononane, 1,10-diaminodecane, and a combination of the two diamines. More specifically, this diamine (D1) may be 1,9-diaminononane. More specifically, this diamine (D1) may also be 1,10-diaminodecane. The proportion of the other diamine (D1) is 15.0 to 40.0 mol %. More specifically, this proportion may be 18.0 to 40.0 mol %. More specifically, this proportion may be 33.0 to 37.0 mol %, or 18.0 to 22.0 mol %, or 23.0 to 27.0 mol %, or 28.0 to 32.0 mol %.

[0040] The diamine component (A) also contains a 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 has the formula: [ka] and 1,4-bis(aminomethyl)cyclohexane is a diamine of the formula: [ka] The diamine (D2) may be, more specifically, 1,3-bis(aminomethyl)cyclohexane. The diamine (D2) may be, more specifically, 1,4-bis(aminomethyl)cyclohexane. The proportion of the other diamine (D2) is 15.0 to 40.0 mol %. This proportion may be, more specifically, 18.0 to 40.0 mol %. This proportion may be, more specifically, 18.0 to 22.0 mol %, or 28.0 to 32.0 mol %, or 33.0 to 37.0 mol %.

[0041] According to embodiment (E1), the proportions in the diamine component (A) are: 42.0 to 47.0 mol % of 1,6-diaminohexane, - 33.0 to 37.0 mol % of a diamine (D1) selected from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines, - 18.0 to 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 and these percentages in mole percent are based on the total amount of diamine in diamine component (A).

[0042] According to another embodiment (E2), the proportions in the diamine component (A) are: 48.0 to 52.0 mol % of 1,6-diaminohexane, - 18.0 to 22.0 mol % of a diamine (D1) selected from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines, - 28.0 to 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 and these percentages in mole percent are based on the total amount of diamine in diamine component (A).

[0043] According to another embodiment (E3), the proportions in the diamine component (A) are: 38.0 to 42.0 mol % of 1,6-diaminohexane, - 23.0 to 27.0 mol % of a diamine (D1) selected from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines, - 33.0 to 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 and these percentages in mole percent are based on the total amount of diamine in diamine component (A).

[0044] According to another embodiment (E4), the proportions in the diamine component (A) are: 48.0 to 52.0 mol % of 1,6-diaminohexane, - 28.0 to 32.0 mol % of a diamine (D1) selected from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines, - 18.0 to 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 and these percentages in mole percent are based on the total amount of diamine in diamine component (A).

[0045] According to another embodiment (E5), the proportions in the diamine component (A) are: 48.0 to 52.0 mol % of 1,6-diaminohexane, - 18.0 to 22.0 mol % of a diamine (D1) selected from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines, - 28.0 to 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 and these percentages in mole percent are based on the total amount of diamine in diamine component (A).

[0046] According to another embodiment (E6), the proportions in the diamine component (A) are: 43.0 to 47.0 mol % of 1,6-diaminohexane, - 33.0 to 37.0 mol % of a diamine (D1) selected from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines, - 18.0 to 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 and these percentages in mole percent are based on the total amount of diamine in diamine component (A).

[0047] All details and embodiments disclosed in this disclosure are applicable to any one of embodiments (E1) to (E6).

[0048] According to one embodiment, 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, in the proportions indicated herein. In the context of the present invention, the expression "consisting essentially of" with respect to diamine component (A) means that diamine component (A) comprises the indicated diamine and may also contain up to 2.0 mol %, preferably up to 1.0 mol %, and more preferably up to 0.5 mol % of at least one additional diamine different from the indicated one. This proportion in mol % is based on the total amount of diamine in diamine component (A). Thus, diamine component (A) consists of a diamine (D1) selected from the group consisting of 1,6-diaminohexane, 1,9-diaminononane, 1,10-diaminodecane, and combinations of said two diamines, a diamine (D2) selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, and combinations of said two diamines, and up to 2.0 mol %, preferably up to 1.0 mol %, and even more preferably up to 0.5 mol % of at least one additional diamine other than 1,6-diaminohexane, D1, and D2, this proportion in mol % being based on the total amount of diamines in diamine component (A).

[0049] 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 one embodiment, diamine component (A) consists essentially of or consists of [1,6-diaminohexane+1,9-diaminononane or 1,10-diaminodecane+1,3-bis(aminomethyl)cyclohexane], the expression "consisting essentially of" meaning that 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 additional diamine other than 1,6-diaminohexane, 1,9-diaminononane, 1,10-diaminodecane and 1,3-bis(aminomethyl)cyclohexane, this proportion in mol % being based on the total amount of diamines in diamine component (A).

[0050] 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 one embodiment, diamine component (A) consists essentially of or consists of [1,6-diaminohexane+1,9-diaminononane or 1,10-diaminodecane+1,4-bis(aminomethyl)cyclohexane], the expression "consisting essentially of" meaning that 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 additional diamine other than 1,6-diaminohexane, 1,9-diaminononane, 1,10-diaminodecane and 1,4-bis(aminomethyl)cyclohexane, this proportion in mol % being based on the total amount of diamines in diamine component (A).

[0051] Dicarboxylic acid component (B) 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 also contain another diacid (DI) selected from the group consisting of isophthalic acid, adipic acid, and a combination of the two diacids.

[0052] The dicarboxylic acid component (B) is - 95.0 to 100.0 mol % of terephthalic acid, - 0 to 5.0 mole % of another diacid (DI) selected from the group consisting of isophthalic acid, adipic acid and a combination of said two diacids These proportions in mole percent are based on the total amount of dicarboxylic acids in dicarboxylic acid component (B).

[0053] These proportions may be more specifically 95.0 to 99.9 mol % of terephthalic acid and 0.1 to 5.0 mol % of other diacids (DI).

[0054] These proportions may more specifically be 98.0 to 99.9 mol % of terephthalic acid and 0.1 to 5.0 mol % of other diacids (DI).

[0055] The diacid (DI) other than terephthalic acid may more specifically be isophthalic acid.

[0056] The diacid (DI) other than terephthalic acid may more specifically be adipic acid.

[0057] More specifically, the ratio in the dicarboxylic acid component (B) is - 98.0 to 100.0 mol % of terephthalic acid, - 0 to 2.0 mole % of another diacid (DI) selected from the group consisting of isophthalic acid, adipic acid and a combination of said two diacids These proportions in mole percent are based on the total amount of dicarboxylic acid in dicarboxylic acid component (B).

[0058] These proportions may be more specifically 98.0 to 99.9 mol % of terephthalic acid and 0.1 to 2.0 mol % of other diacids (DI).

[0059] According to one embodiment, dicarboxylic acid component (B) consists essentially of or consists of terephthalic acid and diacid (DI). In the context of the present invention, the expression "consisting essentially of" with respect to dicarboxylic acid component (B) means that dicarboxylic acid component (B) consists of terephthalic acid, diacid (DI) and up to 2.0 mol %, preferably up to 1.0 mol %, more preferably up to 0.5 mol % of at least one diacid other than terephthalic acid and DI, this proportion in mol % being based on the total amount of dicarboxylic acids in dicarboxylic acid component (B).

[0060] The diamine component (A) and the dicarboxylic acid component (B) preferably do not contain lactam. The diamine component (A) and the dicarboxylic acid component (B) preferably do not contain amino acid. The diamine component (A) and the dicarboxylic acid component (B) preferably do not contain isophoronediamine.

[0061] Embodiment (E): According to a preferred embodiment (E), the dicarboxylic acid component (B) consists essentially of or consists of terephthalic acid.

[0062] In the context of the present invention, the expression "consisting essentially of" with respect to dicarboxylic acid component (B) means that dicarboxylic acid component (B) comprises terephthalic acid and may also contain up to 2.0 mol %, preferably up to 1.0 mol %, and more preferably up to 0.5 mol % of at least one additional diacid other than terephthalic acid, this proportion in mol % being based on the total amount of dicarboxylic acids in dicarboxylic acid component (B). Thus, dicarboxylic acid component (B) consists of terephthalic acid and up to 2.0 mol %, preferably up to 1.0 mol %, and more preferably up to 0.5 mol % of at least one additional diacid other than terephthalic acid, this proportion in mol % being based on the total amount of dicarboxylic acids in dicarboxylic acid component (B).

[0063] All details and embodiments disclosed in this disclosure are applicable to embodiment (E).

[0064] In embodiment (E), the skilled artisan will recognize that the polyamide (PA) comprises the following repeating units (R PA1 ), (R PA2 ) and (R PA3 ): [ka] or the following repeating unit (R PA1 ), (R PA2 ) and (R PA3 ): [ka] 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 —(CH)—, and the divalent radical of 1,10-diaminodecane is —(CH) 10 is.

[0065] R PA1 corresponds to the repeating unit obtained from the reaction of terephthalic acid with 1,6-diaminohexane, and R PA2 corresponds to the repeat unit obtained from the reaction of terephthalic acid with other diamines in C9 and / or C10. PA3 corresponds to the repeat unit obtained from the reaction of terephthalic acid with bis(aminomethyl)cyclohexane (e.g., 1,3-bis(aminomethyl)cyclohexane and / or 1,4-bis(aminomethyl)cyclohexane).

[0066] All proportions and embodiments provided herein for the proportions of diamine 1,6-diaminohexane, D1 and D2 in diamine component (A) are in the range of (R PA1 ), (R PA2) and (R PA3 ) can be converted into a percentage.

[0067] The proportion of the repeating units in the polyamide (PA) is: -R PA1 : 38.0 to 54.0 mol%, -R PA2 : 15.0 to 40.0 mol%, -R PA3 : 15.0 to 40.0 mol% and these proportions in mole % are relative to the total amount of repeat units in the polyamide (PA).

[0068] According to one embodiment, the repeating units (R PA1 ), (R PA2 ) and (R PA3 ) is at least 95.0 mol %, more specifically at least 99.0 mol %.

[0069] According to one embodiment, the repeating units of the polyamide (PA) are the repeating units (R PA1 ), (R PA2 ) and (R PA3 The expression "consisting essentially of" with respect to the repeating units of polyamide (PA) means that the repeating units of the polyamide are 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 repeating units (R PA1 ), (R PA2 ) and (R PA3 ) and a repeating unit other than the repeating unit.

[0070] R PA1is 38.0 to 54.0 mol%. More specifically, this ratio may be 38.0 to 52.0 mol%. More specifically, this ratio may be 38.0 to 47.0 mol%. This ratio may also be 42.0 to 47.0 mol%, or 48.0 to 52.0 mol%, or 38.0 to 42.0 mol%.

[0071] R PA2 is 15.0 to 40.0 mol%. This ratio may be, more specifically, 18.0 to 40.0 mol%. This ratio may be, more specifically, 18.0 to 40.0 mol%. This ratio may be, more specifically, 33.0 to 37.0 mol%, or 18.0 to 22.0 mol%, or 23.0 to 27.0 mol%, or 28.0 to 32.0 mol%.

[0072] R PA3 is 15.0 to 40.0 mol%. This ratio may be, more specifically, 18.0 to 40.0 mol%. This ratio may be, more specifically, 18.0 to 22.0 mol%, or 28.0 to 32.0 mol%, or 33.0 to 37.0 mol%.

[0073] The polyamide (PA) of the present invention preferably does not contain repeating units derived from lactams or amino acids.The polyamide (PA) of the present invention preferably does not contain repeating units derived from isophoronediamine.

[0074] The polyamides (PA) of the present invention generally have a number average molecular weight ("Mn") ranging from 1,000 g / mol to 40,000 g / mol, e.g., 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 can also be 8,000 to 20,000 g / mol. Mn is preferably strictly greater than 8,000 g / mol. Mn can be determined by size exclusion chromatography (SEC) using polystyrene standards or by using the following formula (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 generally amine and / or acid moieties. However, if the polycondensation involves the addition of an end-capping agent, the amine end groups are partially or completely converted to modified end groups. For example, if the end-capping is an acid such as benzoic acid or acetic acid, the remaining amine groups can be completely or partially converted to benzamide or acetamide end groups.

[0075] The end groups of the polyamide (PA) are selected from the group consisting of -NH2, -COOH and amide end groups. In fact, the end groups of the polyamide (PA) can be -NH2 or -COOH. However, when the polycondensation is accompanied by the addition of an end-capping agent, these end groups can be partially or totally converted into amide end groups.

[0076] The amide end groups are of the formula -NH-C(=O)-R, where R is an alkyl, aryl or cycloalkyl group, and / or -C(=O)-NH-R', where R' is an alkyl or cycloalkyl group. R is more particularly a linear or branched C1-C 17 Alkyl group or C5-C 10 R' is a linear or branched C2-C cycloalkyl group. 18 It is an alkyl group.

[0077] Amide end groups of the formula -NH-C(=O)-R result from the reaction of the end group -NH2 with a monocarboxylic acid (endcapping agent) of the formula R-COOH.

[0078] The monocarboxylic acid (endcapping agent) is advantageously benzoic acid, cyclohexanoic acid, R-COOH (wherein R is a linear or branched C1-C 17 R is a group derived from an acid of formula R-COOH) and combinations of two or more of these acids.

[0079] The monocarboxylic acid (endcapping agent) may more particularly be selected from the group consisting of acetic acid, propanoic 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.

[0080] The monocarboxylic acid (endcapping agent) is more specifically represented by the formula CH3-(CH2) n -COOH, where n is an integer from 0 to 16. In that case, the amide end group has the formula -NH-C(=O)-(CH2) n -CH3.

[0081] Amide end groups of formula -C(=O)-NH-R' result from the reaction of the end group -COOH with a primary amine of formula R'-NH2 (endcapping agent).

[0082] The primary amine (endcapping agent) is advantageously of the formula R'-NH2, where R' is a linear or branched C2-C 18 R' is a group derived from an amine of formula R'-NH2.

[0083] The primary amine (endcapping agent) is more specifically a compound of the formula CH3-(CH2) n’ -NH2, where n' is an integer from 2 to 18. In that case, the amide end group has the formula -C(=O)-NH-(CH2)n’ -CH3.

[0084] The primary amine (endcapping agent) may more particularly be selected 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.

[0085] The proportion of terminal groups in polyamide (PA) is 1 It can be quantified by 1 H NMR or potentiometry.

[0086] The polyamide (PA) preferably exhibits an intrinsic viscosity ("IV"), measured according to ASTM D5336, of 0.5 to 1.5 dL / g, more specifically 0.7 to 1.3 dL / g, and more specifically 0.75 to 1.20 dL / g. The IV may be 0.80 to 1.00 dL / g or 0.90 to 1.20 dL / g. The IV is preferably 0.95 to 1.20 dL / g. The IV may conveniently be measured in a 60% by weight / 40% by weight phenol / tetrachloroethane mixture.

[0087] Polyamide (PA) can be prepared from the following monomer combinations disclosed in Table I or Table III:

[0088] Hygroscopic The polyamide (PA) advantageously exhibits a water absorption rate of less than 5.0% by weight at 23°C.

[0089] The water absorption rate at 23°C was measured by (i) preparing a test specimen molded in accordance with ISO 527 in its dry state (water content less than 0.2% by weight), (ii) immersing the test specimen in deionized water at 23°C until it reaches a certain weight, and (iii) calculating the formula:

number

[0090] Bio content Sustainable resins are increasingly in demand. This is why polyamide (PA) preferably exhibits a bio-content of at least 10.0% by weight, preferably at least 15.0% by weight. Bio-content is expressed as the percentage of organic carbon of renewable origin, as measured according to ASTM D6866-22. The bio-content of polyamide (PA) can be at least 20.0%.

[0091] The bio content can be 10.0-21.0%.

[0092] Biocontent is defined as the % of organic carbon that is of renewable origin. 14 It corresponds to the amount of C calculated from the C percent and corrected for isotopic fraction.

[0093] Both the C9 and C10 diamines used in the preparation of polyamides (PA) can be bio-based or sourced from petroleum or natural gas.

[0094] [Table 2]

[0095] 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 polyamides (PA) with a high bio-content, which is primarily derived from the C9 and / or C10 diamines.

[0096] According to one embodiment, the polyamide (PA) disclosed herein is prepared from bio-based 1,9-nonanediamine (C9) and / or 1,10-decanediamine (C10) exhibiting a bio-content of at least 99.0%, preferably at least 99.5%, preferably at least 99.9%, where the bio-content is expressed as the % of organic carbon of renewable origin, measured according to ASTM D6866-22.

[0097] However, it is also possible to increase the biocontent by using biobased terephthalic acid. Biobased terephthalic acid can be prepared from biobased furfural, as disclosed, for example, 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). In this case, the biocontent of the polyamide (PA) defined above can be at least 65.0%.

[0098] Thermal properties of polyamide (PA) As mentioned above, the polyamides (PA) of the present invention have surprisingly been found to exhibit a combination of thermal properties, any of which features disclosed below can be used to characterize the polyamides of the present invention.

[0099] 1) Melting point (Tm) The polyamide (PA) exhibits a Tm strictly below 300°C (<300°C), preferably not higher than 296.0°C (≦296.0°C), preferably not higher than 295.0°C (≦296.0°C), preferably strictly below 290°C (<290°C).

[0100] Tm is preferably 280°C or less (≦280°C).

[0101] The Tm can also be less than or equal to 270°C (≦270°C).

[0102] The Tm is generally at least 250°C or preferably at least 260°C.

[0103] Tm can be 250°C to 280°C or 260.0°C to 280.0°C.

[0104] Tm can be measured by differential scanning calorimetry ("DSC") according to ASTM D3418, particularly using a heating and cooling rate of 20°C / min.

[0105] Tm can be measured more specifically as described in the experimental section. In practice, 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 were 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 was determined from the second heating.

[0106] 2) Glass transition temperature (Tg) The polyamide (PA) exhibits a Tg of at least 140°C, preferably at least 145°C.

[0107] Polyamides (PA) generally exhibit a Tg of at most 200°C, or at most 180°C, or at most 160°C.

[0108] More specifically, Tg can be 145°C to 180°C or 145°C to 160°C.

[0109] Tg can be measured by differential scanning calorimetry ("DSC") according to ASTM D3418, specifically using a heating and cooling rate of 20°C / min.

[0110] Tg can be measured more specifically as described in the experimental section. In practice, 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 were 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 was determined from the second heating.

[0111] According to a preferred embodiment, the polyamide (PA) exhibits a difference (Tm-Tg) of less than 130°C, preferably less than 125°C.

[0112] 3) Crystallization temperature (Tc) Polyamide (PA) exhibits a Tc of 225°C or less, preferably 220°C or less.

[0113] The Tm is generally at least 170°C or at least 190°C.

[0114] Tc can be between 170°C and 225°C.

[0115] Tc is measured by differential scanning calorimetry ("DSC") according to ASTM D3418, specifically using a heating and cooling rate of 20°C / min.

[0116] 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 heat to 350°C, followed by a first cool to 0°C, followed by a second heat to 360°C. Tc is determined from the first cool.

[0117] The lower the Tc, the better the preparation of thermoplastic composites, since a low 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, and preferably at least 60.0°C. (Tm-Tc) can be from 50.0 to 85.0°C.

[0118] 4) Heat of fusion (Hm) Polyamide (PA) is semi-crystalline.

[0119] The polyamide (PA) exhibits an 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.

[0120] Hm can be up to 40.0 J / g or up to 39.0 J / g.

[0121] Hm is preferably 15.0 to 40.0 J / g, preferably 15.0 to 40.0 J / g (this latter value is excluded).

[0122] Hm can be measured by differential scanning calorimetry ("DSC") according to ASTM D3418, specifically using a heating and cooling rate of 20°C / min.

[0123] More specifically, Hm can be measured as described in the experimental section. In practice, 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 were 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.

[0124] Hm can be measured as described in the experimental section.

[0125] Preparation method of polyamide (PA) The polyamides (PA) described herein can be prepared by any conventional method compatible with the synthesis of polyamides and polyphthalamides.

[0126] Polyamides (PA) are prepared by polycondensation.

[0127] The polyamide (PA) can be prepared by heating a reaction mixture (RM) containing all the monomers that make up the polyamide (PA) (e.g., 1,6-hexanediamine, D1 and D2, terephthalic acid, and optionally DI) in the presence of preferably less than 60% by weight, preferentially less than 30%, 20%, 10% by weight, or less than 10% by weight of water, and preferentially without the addition of water, the proportions being based on the total weight of the reaction mixture (RM).

[0128] The temperature to which the reaction mixture (RM) is heated must be high enough to induce a reaction between the amine and carboxyl groups and reduce the viscosity of the reaction mixture. This temperature is generally at least 200°C. The reaction mixture (RM) is preferably heated to a temperature above Tm + 25°C. Polycondensation forms amide bonds and releases water as a by-product.

[0129] The reaction mixture (RM) comprises a diamine as diamine component (A) and a diacid as dicarboxylic acid component (B). As mentioned above, the ratio of the two components is such that the reaction mixture contains the monomers in amounts such that the proportion of -COOH groups from the dicarboxylic acid and the proportion of -NH2 groups from the diamine are substantially equimolar. The molar ratio of -NH2 from the diamine as diamine component (A) / -COOH from the dicarboxylic acid as dicarboxylic acid component (B) is preferably 0.9 to 1.1, preferentially 0.95 to 1.05, and even more preferentially 0.98 to 1.02.

[0130] The reaction mixture (RM) preferably further comprises a catalyst. The catalyst may be selected from the group consisting of phosphoric acid, phosphorous acid, hypophosphorous acid, phenylphosphonic acid, phenylphosphinic acid, salts of said acids with monovalent to trivalent cations, and esters of said acids. The cation may be, for example, Na, K, Mg, Ca, Zn, or Al. Examples of esters are triphenylphosphate, triphenylphosphite, and tris(nonylphenyl)phosphite. A convenient catalyst used is phosphorous acid.

[0131] The proportion of catalyst (RM) in the reaction mixture is preferably 0.005 to 2.5% by weight based on the weight of monomers in the reaction mixture.

[0132] According to one embodiment of the present disclosure, the reaction mixture (RM) comprises: - the monomers constituting the polyamide (PA) disclosed herein, - optionally a catalyst selected in particular from the group consisting of phosphorous acid, ortho-phosphoric acid, meta-phosphoric acid, alkali metal hypophosphites, such as sodium hypophosphite and phenylphosphinic acid, and combinations thereof, optionally at least one endcapping agent selected from the group of monocarboxylic acids, primary amines, and combinations thereof; - water, the proportion of which is less than 60% by weight, preferably less than 30% by weight, preferably less than 20% by weight, preferably less than 10% by weight, this proportion being given based on the total weight of the reaction mixture (RM); According to one embodiment, no water is added at the start of the polycondensation.

[0133] In order to control the molar mass, preferably C1 to C 18 Monocarboxylic acids and C3-C 18 It is possible to use at least one chain transfer agent selected from monoamines, which may more particularly be selected from the group consisting of acetic acid, propanoic 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.

[0134] The polycondensation is advantageously carried out in a well-stirred vessel equipped with means for removing volatile products of the reaction. Because the viscosity of the reaction mixture increases over time, the agitator is adapted to provide sufficient agitation to the reaction mixture (RM) at the start of the polymerization and when the polycondensation conversion is nearly complete.

[0135] The conditions disclosed in the experimental section can be advantageously used for the preparation of polyamides (PA).

[0136] Thermoplastic composite materials (TC) The polyamide (PA) of the present invention is - a polymer matrix comprising or consisting of at least one polyamide (PA) and optionally at least one plastic additive, - Fiber and The present invention is adapted for use in preparing a thermoplastic composite (TC) comprising:

[0137] The proportion of fibers in a thermoplastic composite (TC) is generally at least 40.0% by weight.

[0138] Thermoplastic composites (TCs) comprise or consist of a polymer matrix and fibers, which are generally adhesively or cohesively bonded to the matrix that completely surrounds the fibers.

[0139] 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), ultraviolet light stabilizers, heat stabilizers, antioxidants, acid scavengers, processing aids, internal and / or external lubricants, flame retardants, smoke suppressants, antistatic agents, antiblocking agents, and any combination thereof. The proportion of the plastic additive in the polymer matrix is ​​generally less than 20.0 wt. %, this proportion being based on the total weight of the polymer matrix.

[0140] Fibers generally exhibit high specific stiffness and strength values.

[0141] The fibers can be of inorganic type (for example glass fibers) or organic type (for example aramid fibers or carbon fibers). It is also possible to use a combination of different fibers.

[0142] 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 of the foregoing fibers.

[0143] Thermoplastic composites (TCs) can be manufactured by methods known in the art. Generally, regardless of the method, composite manufacturing involves impregnating fibers with a polymer matrix in molten form, followed by cooling to room temperature. Melt impregnation can further include mechanically compressing the melt against the fibers.

[0144] Thermoplastic composites (TC) can be used for the preparation of articles for the automotive industry. [Example]

[0145] This example demonstrates the synthesis, thermal and mechanical performance of polyamide. The raw materials used to form the samples are listed below.

[0146] Raw materials used The following raw materials were used to prepare the polymer samples:

[0147] [Table 3]

[0148] thermal performance Tg, Tm, and Hm were measured by differential scanning calorimetry ("DSC") according to ASTM D3418 using a heating and cooling rate of 20°C / min. Three scans were used for each DSC test: a first heat to 350°C, followed by a first cool to 0°C, followed by a second heat to 360°C. Tg, Tm, and Hm were determined from the second heat. Tc was determined from the cool.

[0149] Intrinsic viscosity (IV) Intrinsic viscosity (IV) is measured according to ASTM D5336 in a 60% by weight phenol-40% by weight tetrachloroethane mixture.

[0150] Tensile elongation at break Measured according to ISO 527 using an ISO 1A bar.

[0151] Cord modulus and notched Izod Cord modulus: Measured according to ISO 527 using an ISO 1A bar. Impact: Measured according to ISO 180.

[0152] Bio content Determined in accordance with ASTM D6866-22.

[0153] Preparation of copolyamides All copolyamides disclosed in Table III were prepared in an autoclave reactor equipped with a distillation line fitted with a pressure control valve.

[0154] All copolyamides were prepared by charging the target proportions of monomers, water, and phosphorous acid to a reactor and following the procedure set forth in Example 1 below.

[0155] Example 1 (E1): Polyamide E1 was prepared by adding 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 to a reactor. The reactor was sealed and purged with N2 gas three times. The reactor was heated to 177°C and held for 30 minutes, then to 232°C and held for 30 minutes, then to 288°C and held for 30 minutes, and then to 343°C and held for 35 minutes. The evolved steam was slowly vented to maintain the internal pressure below 200 psig. After holding the temperature at 343°C for 35 minutes, the reactor pressure was slowly reduced to atmospheric pressure over 25 minutes. After the vacuum was removed, the reactor was continuously purged with N2 gas for 25 minutes, after which the reactor was cooled to room temperature and the polymer was recovered from the reactor.

[0156] As can be seen from the results in Table III, a particular ratio of monomers allows for a balance of properties, particularly a high Tg and a low Tm.

[0157] Furthermore, the polyamide of the present invention exhibits significantly higher elongation at break and notch impact. It also exhibits improved notch impact.

[0158] [Table 4]

[0159] [Table 5]

Claims

1. A polyamide (PA) exhibiting a melting temperature Tm strictly below 300°C (<300°C), preferably 296.0°C or less (≦296.0°C), preferably 295.0°C or less (≦295.0°C), preferably strictly below 290°C (<290°C), and comprising repeating units formed by polycondensation of a diamine component (A) and a dicarboxylic acid component (B), a) The diamine component (A) is 38.0 to 54.0 mol % of 1,6-diaminohexane, - 15.0 to 40.0 mol % of a diamine (D1) selected from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines, - 15.0 to 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 wherein the percentage in mole percent is based on the total amount of diamine in the diamine component (A), b) The dicarboxylic acid component (B) is 95.0 to 100.0 mol % of terephthalic acid, - 0 to 5.0 mole % of another diacid selected from the group consisting of isophthalic acid, adipic acid and a combination of said two diacids. wherein the proportion in mole percent is based on the total amount of diacids in the dicarboxylic acid component (B).

2. 2. Polyamide (PA) according to claim 1, wherein the diamine component (A) consists essentially of or consists of a diamine (D1) selected from the group consisting of 1,6-diaminohexane, 1,9-diaminononane, 1,10-diaminodecane and a combination of said 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 said two diamines, the expression "consisting essentially 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 additional diamine other than 1,6-diaminohexane, D1 and D2, said proportions in mol % being based on the total amount of diamines in the diamine component (A).

3. 3. Polyamide (PA) according to claim 1 or 2, wherein the dicarboxylic acid component (B) consists essentially of or consists of terephthalic acid and the other diacid (DI), the expression "consisting essentially of" meaning that 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 additional diacid other than terephthalic acid and the diacid (DI), said proportions in mol % being based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B).

4. 3. The polyamide according to claim 1 or 2, wherein the dicarboxylic acid component (B) consists essentially of or consists of terephthalic acid, the expression "consisting essentially of" meaning 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 additional diacid other than terephthalic acid, said proportions in mol % being based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B).

5. The proportions in the dicarboxylic acid component (B) are as follows: - 95.0 to 99.9 mol % of terephthalic acid and 0.1 to 5.0 mol % of said other diacid, or 98.0 to 99.9 mol % of terephthalic acid and 0.1 to 2.0 mol % of said other diacids The polyamide (PA) according to any one of claims 1 to 3,

6. Repeating unit (R ＰＡ１ ), (R ＰＡ２ ) and (R ＰＡ３ ): 【Chemistry 1】 Or the following: 【Chemistry 2】 (In the formula, R １ is -(CH ２ ) ６ - and R ２ 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 ratio of the repeating units is -R ＰＡ１ : 38.0 to 54.0 mol%, -R ＰＡ２ : 15.0 to 40.0 mol%, -R ＰＡ３ : 15.0 to 40.0 mol% and said proportion in mol % is relative to the total amount of repeat units in the polyamide (PA), in particular according to any one of claims 1 to 5.

7. Repeating unit (R ＰＡ１ ), (R ＰＡ２ ) and (R ＰＡ３ 7. Polyamide (PA) according to claim 6, in which the total proportion of (a) and (b) is at least 95.0 mol%, more particularly at least 99.0 mol%.

8. The repeating unit of the polyamide (PA) is the repeating unit (R ＰＡ１ ), (R ＰＡ２ ) and (R ＰＡ３ The expression "consisting essentially of" means that the repeating units of the polyamide (PA) are 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 repeating units (R ＰＡ１ ), (R ＰＡ２ ) and (R ＰＡ３ 7. The polyamide (PA) according to claim 6, which means that it is composed of repeating units other than .

9. The ratio of 1,6-hexanediamine in the diamine component (A) or R ＰＡ１ The percentage of 38.0 to 52.0 mol %, or 38.0 to 47.0 mol %, or 42.0 to 47.0 mol %, or 48.0 to 52.0 mol %, or 38.0 to 42.0 mol% The polyamide (PA) according to any one of claims 1 to 8,

10. The ratio 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 ratio of R ＰＡ２ The percentage of 18.0 to 33.0 mol %, or 18.0 to 40.0 mol %, or 33.0 to 37.0 mol %, or 18.0 to 22.0 mol %, or 23.0 to 27.0 mol %, or 28.0 to 32.0 mol% The polyamide (PA) according to any one of claims 1 to 9,

11. The ratio 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 ratio of R ＰＡ３ The percentage of 18.0 to 40.0 mol %, or 18.0 to 22.0 mol %, or 28.0 to 32.0 mol %, or 33.0 to 37.0 mol% The polyamide (PA) according to any one of claims 1 to 10,

12. The proportions in the diamine component (A) are as follows: 42.0 to 47.0 mol % of 1,6-diaminohexane, - 33.0 to 37.0 mol % of a diamine (D1) selected from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines, - 18.0 to 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: 48.0 to 52.0 mol % of 1,6-diaminohexane, - 18.0 to 22.0 mol % of a diamine (D1) selected from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines, - 28.0 to 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: 38.0 to 42.0 mol % of 1,6-diaminohexane, - 23.0 to 27.0 mol % of a diamine (D1) selected from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines, 33.0 to 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: 48.0 to 52.0 mol % of 1,6-diaminohexane, - 28.0 to 32.0 mol % of a diamine (D1) selected from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines, - 18.0 to 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: 48.0 to 52.0 mol % of 1,6-diaminohexane, - 18.0 to 22.0 mol % of a diamine (D1) selected from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines, - 28.0 to 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: 43.0 to 47.0 mol % of 1,6-diaminohexane, - 33.0 to 37.0 mol % of a diamine (D1) selected from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines, - 18.0 to 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 The polyamide (PA) according to any one of claims 1 to 11,

13. The proportions are as follows: 42.0 to 47.0 mol% of R ＰＡ１ , 33.0 to 37.0 mol% of R ＰＡ２ , 18.0 to 22.0 mol% of R ＰＡ３ , or The following: 48.0 to 52.0 mol% of R ＰＡ１ , 18.0 to 22.0 mol% of R ＰＡ２ , 28.0 to 32.0 mol% of R ＰＡ３ , or The following: 38.0 to 42.0 mol% of R ＰＡ１ , 23.0 to 27.0 mol% of R ＰＡ２ , 33.0 to 37.0 mol% of R ＰＡ３ , or The following: 48.0 to 52.0 mol% of R ＰＡ１ , 28.0 to 32.0 mol% of R ＰＡ２ , 18.0 to 22.0 mol% of R ＰＡ３ , or The following: 48.0 to 52.0 mol% of R ＰＡ１ , 18.0 to 22.0 mol% of R ＰＡ２ , 28.0 to 32.0 mol% of R ＰＡ３ , or The following: 43.0 to 47.0 mol% of R ＰＡ１ , 33.0 to 37.0 mol% of R ＰＡ２ , 18.0 to 22.0 mol% of R ＰＡ３ The polyamide (PA) according to any one of claims 6 to 12, wherein said proportion is given relative to the total proportion of repeat units in the polyamide (PA).

14. The terminal group in the polyamide is —NH ２ 14. Polyamide (PA) according to any one of claims 1 to 13, wherein the end groups are selected in the group of -COOH and -amide.

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

16. The melting temperature Tm of the polyamide (PA) is - 280°C or less (≦280°C) or 270°C or less (≦280°C), and / or at least 250°C, preferably at least 260°C and Tm is measured by DSC according to ASTM D3418, in particular using a heating and cooling rate of 20°C / min.

17. The glass transition temperature Tg of the polyamide (PA) is at least 140°C, preferably at least 145°C, and / or - Maximum 200°C, or maximum 180°C, or maximum 160°C and Tg is measured by DSC according to ASTM D3418, in particular using a heating and cooling rate of 20°C / min.

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

19. Polyamide (PA) according to any one of claims 1 to 18, exhibiting a difference (Tm-Tc) of at least 50.0°C, preferably at least 55.0°C, preferably at least 60°C or from 50.0 to 85.0°C, said melting temperature Tm and crystallization temperature Tc being measured by DSC according to ASTM D3418, in particular using heating and cooling rates of 20°C / min.

20. 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 - 15.0 to 40.0 J / g, preferably 15.0 to 40.0 J / g (this latter value is excluded) 20. Polyamide (PA) according to any one of claims 1 to 19, exhibiting a heat of fusion Hm of 0.05 to 0.15, Hm being measured by differential scanning calorimetry ("DSC") according to ASTM D3418, in particular using a heating and cooling rate of 20°C / min.

21. 0.5 to 1.5 dL / g, or 0.7 to 1.3 dL / g, or 0.75 to 1.20 dL / g, or 0.80 to 1.00 dL / g, or 0.90 to 1.20 dL / g, or -0.95~1.20dL / g 21. Polyamide (PA) according to any one of claims 1 to 20, exhibiting an intrinsic viscosity ("IV"), measured according to ASTM D5336, of:

22. Polyamide (PA) according to any one of claims 1 to 21, exhibiting a number average molecular weight ("Mn") between 8,000 and 20,000 g / mol.

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

24. The water absorption at 23°C is less than 5.0 wt% and the water absorption at 23°C is determined by (i) providing a test specimen molded in accordance with ISO 527 in its dry state (water content less than 0.2 wt%), (ii) immersing the test specimen in deionized water at 23°C until a constant weight is reached, and (iii) satisfying the formula: [Equation 1] (In the formula, W ｂｅｆｏｒｅ is the weight of the molded specimen in its original dry state, and W ａｆｔｅｒ is the weight of the molded test piece after water absorption) The polyamide (PA) according to any one of claims 1 to 23, wherein the water absorption is determined by calculating the water absorption using:

25. It is prepared by polycondensation by heating a reaction mixture (RM) comprising all said monomers, said reaction mixture (RM) comprising in particular: the monomers constituting the polyamide (PA), optionally a catalyst selected in particular from the group consisting of phosphorous acid, ortho-phosphoric acid, meta-phosphoric acid, alkali metal hypophosphites, such as sodium hypophosphite and phenylphosphinic acid, and combinations thereof, optionally at least one endcapping agent selected from the group of monocarboxylic acids, primary amines and combinations thereof; water, the proportion of which is less than 60% by weight, preferably less than 30% by weight, preferably less than 20% by weight, preferably less than 10% by weight, said proportions being given based on the total weight of the reaction mixture (RM); Polyamide (PA) according to any one of claims 1 to 24, comprising or consisting of:

26. 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 selected in particular from the group consisting of colorants, UV light stabilizers, heat stabilizers, antioxidants, acid scavengers, processing aids, internal and / or external lubricants, flame retardants, smoke suppressants, antistatic agents, antiblocking agents and any combination thereof, - Fiber and A thermoplastic composite (TC) comprising:

27. Use of a polyamide (PA) according to any one of claims 1 to 25 for the preparation of a thermoplastic composite material.

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