Semi-aromatic polyamides with low melting temperatures

Abstract

The present invention relates to a polyamide (PA) which 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 c) the diamine component (A) comprises: - 15.0 to 25.0 mol % of 1,6-hexanediamine; - 18.0 to 30.0 mol % of a diamine selected from the group consisting of 1,9-diaminononane, 1,10-diaminodecane, and a combination of said two diamines; - 50.0 to 64.0 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 d) 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 dicarboxylic acids 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 / 385,647, filed December 1, 2022, and European Patent Application No. 23154136.8, filed January 31, 2023, the contents of which are incorporated herein by reference in their entireties 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 1.3 BAC. The disclosed polyamides with 1.3 BAC are based on different compositions that exhibit a Tm higher than 290°C or have a higher proportion of BACT. For example, WO 2018 / 172717 discloses in Table III a copolyamide 6T (25 mol%) / BACT (75 mol%) with a Tm of 306°C.

[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. 2019 / 338074 (D1) and WO 2018 / 011495 disclose semi-aromatic copolyamides based on 1.3BAC and having a melting temperature below 300°C. The two compositions disclosed in the experimental sections of US Patent Application Publication No. 2019 / 338074 and WO 2018 / 011495 are based on 10T, 6T and BACT repeat units. The composition of claim 1 is not disclosed.

[0010] US Patent Application Publication No. 2016 / 0152770 discloses a semi-aromatic copolyamide comprising, in copolymerized form, a) 30-50 mol% of terephthalic acid, b) 0-14 mol% of isophthalic acid, c) 35-42.5 mol% of hexamethylenediamine, and d) 7.5-15 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.

[0011] 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.

[0012] WO 2021 / 037850 and US 2022 / 289909 describe a 55 mol% to 75 mol% C4 to C8 aliphatic diamine, 25 mol% to 45 mol% C9 to C 12 A 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, 0 mol % to 10 mol % of a C6 to C6 18 C8-C different from aliphatic dicarboxylic acid or terephthalic acid 18 The present invention discloses a polyamide formed from a dicarboxylic acid component (B) containing an aromatic dicarboxylic acid and an alicyclic dicarboxylic acid containing 0 to 10 mol % of a cyclohexyl group. The proportion of 1,6-hexanediamine is higher than that of claim 1.

[0013] WO 2021 / 224431 brochure describes 20 mol% to 95 mol% C4 to C 12WO 2021 / 224431 discloses polyamides formed 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 50 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.

[0014] 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 an alicyclic diamine containing 0 to 10 mol % of a cyclohexyl group. The Tm is higher than that of claim 1.

[0015] US Patent Application Publication No. 2008 / 274355 (D4) is formed from a component (Al) having 40 to 95 mol % of 10T units and a component (A2) having 5 to 60 mol % of 6T units, with the proviso that, independently of each other, in (Al) and / or (A2), up to 30 mol % of terephthalic acid, based on the total dicarboxylic acids, is present in addition to other C6-C 36 up to 30 mol % of 1,10-decanediamine and respectively 1,6-hexanediamine, based on the total diamines, can be substituted for aromatic, aliphatic or cycloaliphatic dicarboxylic acids and in components (A), independently of one another, in (A1) and / or (A2), other C4-C 36 D4 discloses a copolyamide 10T / 6T that can be substituted with diamines. All examples are 10T / 6T copolyamides. D4 does not disclose the claimed copolyamide (PA). Summary of the Invention [Problem to be solved by the invention]

[0016] In the field of polyamide-based thermoplastic composites, a major challenge is to find easy-to-prepare 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 resin easy to process.

[0017] For the preparation of thermoplastic composites by melt impregnation, there is a need for resins with lower melt flow rates (meaning easier processing of the resin in the melt) while maintaining a good balance of mechanical properties (chord modulus).

[0018] There is also a need for resins that are sustainable and have low crystallization temperatures (to reduce warpage and stress in the resin in composites).

[0019] The polyamide of the present invention aims to solve this technical problem. [Means for solving the problem]

[0020] The invention is set out in the accompanying set of claims.

[0021] The present invention relates to a polyamide as disclosed in any one of claims 1 to 29.

[0022] The invention also relates to a thermoplastic composite material as defined in claim 30.

[0023] The invention also relates to the use defined in claim 31.

[0024] Further precision and detail on these subjects is now provided below.

[0025] definition These definitions apply to this disclosure.

[0026] wt% means weight %. Mol% means mole %.

[0027] 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.

[0028] 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.

[0029] 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, in particular in the claims.

[0030] The proportion of diamine in diamine component (A) is expressed in mole % and is based on the total amount of diamine in diamine component (A). The proportion of dicarboxylic acid in dicarboxylic acid component (B) is expressed in mole % and is based on the total amount of dicarboxylic acid in dicarboxylic acid component (B).

[0031] The proportion of repeat units in the polyamide (PA) is expressed in mole % and is based on the total amount of repeat units in the polyamide (PA).

[0032] Dicarboxylic acids are organic compounds containing two carboxyl groups (-COOH). DETAILED DESCRIPTION OF THE INVENTION

[0033] The present invention relates to a semi-aromatic copolyamide (PA) which exhibits a melting temperature Tm strictly below 290°C (<290°C) and comprises repeating units formed from the polycondensation of a diamine component (A) and a dicarboxylic acid component (B), a) The diamine component (A) is 15.0 to 25.0 mol % of 1,6-diaminohexane, - 18.0 to 30.0 mol % of a diamine (D1) selected from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines, - 50.0 to 64.0 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 diacids in the dicarboxylic acid component (B).

[0034] The present invention relates to a semi-aromatic copolyamide (PA) which exhibits a melting temperature Tm strictly below 290°C (<290°C) and comprises repeating units formed from the polycondensation of a diamine component (A) and a dicarboxylic acid component (B), a) The diamine component (A) is 15.0 to 25.0 mol % of 1,6-diaminohexane, - 18.0 to 30.0 mol % of a diamine (D1) selected from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines, - 50.0 to 62.0 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 % are based on the total amount of diacids in the dicarboxylic acid component (B), and also relate to semi-aromatic copolyamides (PA).

[0035] The polyamide (PA) of the present invention is formed by polycondensation of a diamine in the diamine component (A) and a diacid in the dicarboxylic acid component (B). Therefore, the ratio of -NH2 derived from the diamine in the diamine component (A) and the ratio of -COOH derived from the dicarboxylic acid in the dicarboxylic acid component (B) are substantially equimolar. Therefore, the molar ratio of -NH2 derived from the diamine in the diamine component (A) to -COOH derived from the dicarboxylic acid in the 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.

[0036] 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.

[0037] Further details regarding the diamine component (A) and the dicarboxylic acid component (B) are provided below.

[0038] Diamine component (A) The diamine component (A) is selected from the following diamines: 1,6-diaminohexane (of formula NH2-(CH2)6-NH2) and 1,9-diaminononane (of formula NH2-(CH2)9-NH2), 10 The compound is based on and comprises a diamine (D1) selected from the group consisting of 1,10-diaminodecane (of —NH2) and a combination of said two diamines, and bis(aminomethyl)cyclohexane (D2).

[0039] The proportion of 1,6-diaminohexane is 15.0 to 25.0 mol %, more specifically, 15.0 to 20.0 mol %, or 15.0 to 22.0 mol %, or 18.0 to 22.0 mol %.

[0040] 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. This diamine (D1) may be, more specifically, 1,9-diaminononane. This diamine (D1) may also be, more specifically, 1,10-diaminodecane. The proportion of the other diamine (D1) is 18.0 to 30.0 mol % or 18.0 to 27.0 mol %. This proportion of D1 may, more specifically, be 23.0 to 27.0 mol % or 18.0 to 22.0 mol %.

[0041] The diamine component (A) also contains a bis(aminomethyl)cyclohexane (D2) selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane (1,3-BAC), 1,4-bis(aminomethyl)cyclohexane (1,4-BAC), 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] This diamine (D2) may more particularly and preferably be 1,3-bis(aminomethyl)cyclohexane.

[0042] More specifically, the diamine (D2) may be 1,4-bis(aminomethyl)cyclohexane. The proportion of the other diamine (D2) is 50.0 to 64.0 mol % or 50.0 to 62.0 mol %. More specifically, the proportion of D2 may be 53.0 to 62.0 mol %, or 53.0 to 57.0 mol %, or 58.0 to 27.0 mol %, or 58.0 to 62.0 wt %, or 61.0 to 64.0 mol %.

[0043] According to embodiment (E1), the proportion in the diamine component (A) is 18.0 to 22.0 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, - 53.0 to 57.0 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 (E2), the proportion in the diamine component (A) is 18.0 to 22.0 mol % of 1,6-hexanediamine, - 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, - 58.0 to 62.0 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 (E3), the proportion in the diamine component (A) is 15.0 to 20.0 mol % of 1,6-hexanediamine, - 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, - 61.0 to 64.0 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] All details and embodiments disclosed in this disclosure are applicable to any one of embodiments (E1) to (E3).

[0047] According to one embodiment, 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 combinations 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 combinations of said two diamines, in the proportions indicated herein.

[0048] In the context of the present invention, the expression "consisting essentially of" in reference 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 one indicated, this proportion in mol % being based on the total amount of diamines 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] The diamine component (A) may preferably be based on the following diamine combination: 1,6-diaminohexane+(1,9-diaminononane and / or 1,10-diaminodecane)+1,3-bis(aminomethyl)cyclohexane. According to one embodiment, diamine component (A) consists essentially of or consists of [1,6-diaminohexane + 1,9-diaminononane and / 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, 1,10-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 and / 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 and / 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, 1,10-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 in embodiment (E), 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 proportion of diamine in diamine component (a) apply here.

[0067] Therefore, the ratio of the repeating units is: -R PA1 : 15.0 to 25.0 mol%, -R PA2 : 18.0 to 30.0 mol%, -R PA3 : 50.0 to 64.0 mol%, or The following: -R PA1 : 15.0 to 25.0 mol%, -R PA2 : 18.0 to 30.0 mol%, -R PA3 : 50.0 to 62.0 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 unit (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 PA1 The proportion of is 15.0 to 25.0 mol %. More specifically, this proportion may be 15.0 to 20.0 mol %, or 15.0 to 22.0 mol %, or 18.0 to 22.0 mol %.

[0071] R PA2 The proportion of is 18.0 to 30.0 mol % or 18.0 to 27.0 mol %. More specifically, this proportion may be 23.0 to 27.0 mol % or 18.0 to 22.0 mol %.

[0072] R PA3 The proportion of is 50.0 to 64.0 mol % or 50.0 to 62.0 mol %. More specifically, this proportion may be 53.0 to 62.0 mol %, or 53.0 to 57.0 mol %, or 58.0 to 62.0 mol %, or 61.0 to 64.0 mol %.

[0073] According to one embodiment, the ratio is: 15.0 to 25.0 mol% R PA1 , 23.0 to 27.0 mol% R PA2 , 53.0 to 57.0 mol% R PA3 is.

[0074] According to another embodiment, the ratio is: 15.0 to 25.0 mol% R PA1 , 18.0 to 22.0 mol% R PA2 , 58.0 to 62.0 mol% R PA3 is.

[0075] 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.

[0076] 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 a more accurate known method for measuring amine and acid end group concentrations 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 endcapping agent, the amine end groups are partially or completely converted to modified end groups. For example, if the endcapping 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.

[0077] The end groups of the polyamide (PA) are selected from the group consisting of -NH2, -COOH and amide end groups. In practice, 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 entirely converted to amide end groups.

[0078] 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.

[0079] 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.

[0080] 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.

[0081] The monocarboxylic acid (endcapping agent) may more specifically 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.

[0082] 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.

[0083] 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 (an endcapping agent).

[0084] 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.

[0085] Primary amines (endcapping agents) are more specifically those 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.

[0086] The primary amine (endcapping agent) may more specifically 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.

[0087] The proportion of terminal groups in polyamide (PA) is 1 It can be quantified by 1 H NMR or potentiometry.

[0088] The polyamide (PA) preferably exhibits an intrinsic viscosity ("IV") of 0.5 to 1.5 dL / g, more specifically 0.7 to 1.3 dL / g, and even more specifically 0.75 to 1.20 dL / g, measured according to ASTM D5336. The IV may be 0.80 to 1.00 dL / g or 0.90 to 1.20 dL / g. The IV may be conveniently measured in a 60% by weight / 40% by weight phenol / tetrachloroethane mixture. The polyamide (PA) advantageously exhibits a melt flow rate (MFR) of 6.0 g / 10 min or less, preferably 5.0 g / 10 min or less, preferably 4.0 g / 10 min or less, and preferably 3.0 g / 10 min or less. The MFR is measured at Tm+20°C according to ASTM D1238 using a test load of 2.16 kg. The measurement conditions given in the experimental section may be followed.

[0089] Polyamides (PA) can be prepared from combinations of monomers disclosed in Table I or Table II.

[0090] Hygroscopic The polyamide (PA) advantageously exhibits a water absorption rate of less than 5.0% by weight at 23°C.

[0091] The water absorption rate at 23°C was measured by (i) providing 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 a constant weight was reached, and (iii) calculating the formula:

number

[0092] Bio content The polyamide (PA) may exhibit a bio-content of at least 10.0%. Bio-content is expressed as the % of renewable organic carbon determined according to ASTM D6866-22. The bio-content is preferably at least 12.0%. The bio-content may be 10.0-20.0%. Bio-content is defined as the % of renewable organic carbon measured in the sample. 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 1]

[0095] Therefore, the polyamide (PA) disclosed herein is preferably prepared from bio-based 1,9-diaminononane (C9) and / or 1,10-diaminodecane (C10). This allows for the production of polyamide (PA) with a high bio-content, which is primarily derived from C9 and / or C10 diamines.

[0096] According to one embodiment, the polyamide (PA) disclosed herein is prepared from 1,9-diaminononane (C9) and / or 1,10-diaminodecane (C10) exhibiting a biocomponent content of at least 99.0%, preferably at least 99.5%, preferably at least 99.9%, where the biocomponent content is expressed as % of renewable-derived organic carbon as 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, as defined above, can be at least 60.0%.

[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 exhibits a Tm strictly less than 290°C (less than 290°C). The Tm may be less than 285°C, or less than 280°C, or less than 270°C.

[0100] The Tm is generally at least 250°C or preferably at least 260°C.

[0101] Tm can be from 250°C to 290°C or from 250.0°C to 280°C.

[0102] Tm can be measured by differential scanning calorimetry ("DSC") according to ASTM D3418, particularly using a heating and cooling rate of 20°C / min.

[0103] More specifically, Tm can be measured as described in the experimental section.

[0104] Tm may 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 heat to 350°C, followed by a first cool to 0°C, followed by a second heat to 360°C. Tg was determined from the second heat.

[0105] 2) Glass transition temperature (Tg) The polyamide exhibits a Tg of at least 155° C. The Tg of the polyamide (PA) may preferably be at least 165° C., preferably at least 166° C., preferably at least 167° C., preferably at least 168° C., preferably at least 169° C., preferably at least 170° C.

[0106] Polyamides (PA) generally exhibit a Tg of at most 200°C or at most 180°C.

[0107] More specifically, Tg can be 155 to 180°C or 165 to 180°C.

[0108] Tg can be measured by differential scanning calorimetry ("DSC") according to ASTM D3418, specifically using a heating and cooling rate of 20°C / min.

[0109] More specifically, Tg can be measured as described in the experimental section.

[0110] Tg may 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 heat to 350°C, followed by a first cool to 0°C, followed by a second heat to 360°C. Tg was determined from the second heat.

[0111] According to a preferred embodiment, the polyamide (PA) exhibits a difference (Tm-Tg) of less than 130°C, preferably less than 120°C, preferably less than 110°C, preferably less than 100°C.

[0112] 3) Heat of fusion (Hm) Polyamide (PA) is semi-crystalline.

[0113] 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. Hm may be less than or equal to 40.0 J / g (≦40.0 J / g). More specifically, Hm may be at most 39.0 J / g.

[0114] Hm is more particularly 15.0 to 40.0 J / g, more particularly 15.0 to 40.0 J / g (this latter value is excluded).

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

[0116] 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.

[0117] η can be measured as described in the experimental section.

[0118] 4) Crystallization temperature (Tc) Polyamides (PA) exhibit a Tg of up to 210° C. The Tc is generally at least 180° C.

[0119] Tc can be between 180°C and 210°C.

[0120] Tc is measured by differential scanning calorimetry ("DSC") according to ASTM D3418, specifically using a heating and cooling rate of 20°C / min.

[0121] 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 350°C. Tc is determined from the first cool.

[0122] A lower Tc helps minimize warpage and stress in the resin, and therefore the lower the Tc, the better the preparation of thermoplastic composites. The polyamide (PA) of the present invention preferably exhibits a (Tm-Tc) of at least 50.0°C, preferably at least 60.0°C. (Tm-Tc) can be 50.0-75.0°C or 50.0-70.0°C.

[0123] 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.

[0124] Polyamides (PA) are prepared by polycondensation.

[0125] 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).

[0126] 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.

[0127] 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.

[0128] 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.

[0129] 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.

[0130] 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, based on the total weight of the reaction mixture (RM); According to one embodiment, no water is added at the start of the polycondensation.

[0131] 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, more particularly 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.

[0132] 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.

[0133] The conditions disclosed in the experimental section can be advantageously used for the preparation of polyamides (PA).

[0134] 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 to be used for the preparation of a thermoplastic composite (TC) comprising:

[0135] The proportion of fibers in a thermoplastic composite (TC) is generally at least 40.0% by weight.

[0136] Thermoplastic composites (TCs) comprise or consist of a polymer matrix and fibers that are adhesively or cohesively bonded to the matrix, which generally completely surrounds the fibers.

[0137] 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. %, the proportion being based on the total weight of the polymer matrix.

[0138] Fibers generally exhibit high specific stiffness and strength values.

[0139] 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.

[0140] 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.

[0141] 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.

[0142] Thermoplastic composites (TC) can be used in the manufacture of articles for the automotive industry. [Example]

[0143] This example demonstrates the synthesis, thermal and mechanical performance of polyamide. The raw materials used to form the samples are listed below.

[0144] Raw materials used The polyamide was prepared using the following raw materials:

[0145] [Table 2]

[0146] 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 first cool.

[0147] Intrinsic viscosity (IV) Intrinsic viscosity (IV) is measured according to ASTM D5336 in a 60% by weight phenol-40% by weight tetrachloroethane mixture.

[0148] Melt Flow Rate (MFR) Measured according to ASTM D1238 using a 2.16 kg test load. Samples were dried at 225°F for 24 hours before testing.

[0149] Code Modulus Measured according to ISO 527 using an ISO 1A bar.

[0150] Bio content Determined in accordance with ASTM D6866-22.

[0151] Preparation of polyamide All copolyamides disclosed in Table II were prepared in an autoclave reactor equipped with a distillation line fitted with a pressure control valve.

[0152] 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.

[0153] Example 1 (E1): Polyamide E1 was prepared by adding 0.79 g of hexamethylenediamine, 1.46 g of 1,10-diaminodecane, 2.65 g of 1,3-cyclohexane-bis(methylamine), 5.32 g of terephthalic acid, 5.04 g of deionized water, and 0.0034 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 heated to 232°C and held for 30 minutes, then heated to 288°C and held for 30 minutes, and then heated 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.

[0154] As can be seen from the results in Table II, the specific ratio of monomers allows for a balance of properties, particularly a high Tg and a low Tm. Furthermore, the polyamides of the present invention exhibit a balance of MFR at Tm+20°C versus IV.

[0155] [Table 3]

[0156] [Table 4]

Claims

1. A polyamide (PA) exhibiting a melting temperature Tm strictly below 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 15.0 to 25.0 mol % of 1,6-hexanediamine, - 18.0 to 30.0 mol % of a diamine (D1) selected from the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines, 50.0 to 64.0 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), and 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. wherein the proportion in mole percent is based on the total amount of dicarboxylic acids 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 (DI), or 98.0 to 99.9 mol % of terephthalic acid and 0.1 to 2.0 mol % of said other diacid (DI) 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 : 15.0 to 25.0 mol%, -R ＰＡ２ : 18.0 to 30.0 mol%, -R ＰＡ３ : 50.0 to 64.0 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 ) and the expression "consisting essentially of" with respect to said repeating units of polyamide (PA) means that said repeating units of said 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 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 18.0 to 22.0 mol %, or 15.0 to 22.0 mol %, or 18.0 to 22.0 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 27.0 mol %, or 23.0 to 27.0 mol %, 18.0 to 22.0 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 50.0 to 62.0 mol %, or 53.0 to 62.0 mol %, or 53.0 to 57.0 mol %, or 58.0 to 62.0% by weight, or 61.0 to 64.0 mol% The polyamide (PA) according to any one of claims 1 to 10,

12. The proportions in the diamine component (A) are as follows: 18.0 to 22.0 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, - 53.0 to 57.0 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: 18.0 to 22.0 mol % of 1,6-hexanediamine, - 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, - 58.0 to 62.0 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: 15.0 to 20.0 mol % of 1,6-hexanediamine, - 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, 61.0 to 64.0 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: 18.0 to 22.0 mol% of R ＰＡ１ , 23.0 to 27.0 mol% of R ＰＡ２ , 53.0 to 57.0 mol% of R ＰＡ３ , or The following: 18.0 to 22.0 mol% of R ＰＡ１ , 18.0 to 22.0 mol% of R ＰＡ２ , 58.0 to 62.0 mol% of R ＰＡ３ , or The following: 15.0 to 20.0 mol% of R ＰＡ１ , 18.0 to 22.0 mol% of R ＰＡ２ , 61.0 to 64.0 mol% of R ＰＡ３ The polyamide (PA) according to any one of claims 6 to 12,

14. Polyamide (PA) according to any one of claims 1 to 13, which does not contain repeating units derived from lactams or amino acids.

15. The terminal group in the polyamide is —NH ２ , —COOH and amide end groups, the amide end groups being in particular of the formula —NH—C(═O)—R, where R is an alkyl, aryl or cycloalkyl group, and / or of the formula —C(═O)—NH—R′, where R′ is an alkyl or cycloalkyl group.

16. The melting temperature Tm of the polyamide (PA) is - below 285°C, or below 280°C, or below 270°C, and / or at least 250°C, preferably at least 260°C and Tm is measured by differential scanning calorimetry ("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 155°C, preferably at least 165°C, preferably at least 166°C, preferably at least 167°C, preferably at least 168°C, preferably at least 169°C, preferably at least 170°C, and / or - Maximum 200°C or maximum 180°C and Tg is measured by differential scanning calorimetry ("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 120°C, preferably less than 110°C, preferably less than 100°C.

19. Polyamide (PA) according to any one of claims 1 to 18, exhibiting a crystallization temperature (Tc) of at most 210°C.

20. 20. Polyamide (PA) according to any one of the preceding claims, which exhibits a difference (Tm-Tc) of at least 50.0°C, preferably at least 60.0°C, preferably 50.0 to 75.0°C or 50.0 to 70.0°C, said melting temperature Tm and said crystallization temperature Tc being measured by differential scanning calorimetry ("DSC") according to ASTM D3418, in particular using heating and cooling rates of 20°C / min.

21. 21. Polyamide (PA) according to any one of claims 1 to 20, exhibiting a heat of fusion Hm of at least 15.0 J / g, preferably at least 20.0 J / g, preferably at least 25.0 J / g, Hm measured by differential scanning calorimetry ("DSC") according to ASTM D3418, in particular using a heating and cooling rate of 20°C / min.

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

23. 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 23. Polyamide (PA) according to any one of claims 1 to 22, exhibiting an intrinsic viscosity ("IV"), measured according to ASTM D5336, of:

24. Polyamide (PA) according to any one of claims 1 to 23, exhibiting a number average molecular weight ("Mn") between 8,000 and 20,000 g / mol.

25. Polyamide (PA) according to any one of claims 1 to 24, exhibiting a bio-content of at least 10.0%, preferably at least 12.0%, preferably at least 60.0%, said bio-content expressed as % of organic carbon of renewable origin, determined according to ASTM D6866-22.

26. 26. Polyamide (PA) according to any one of the preceding claims, exhibiting a melt flow rate (MFR) of at most 6.0 g / 10 min, preferably at most 5.0 g / 10 min, preferably at most 4.0 g / 10 min, preferably at most 3.0 g / 10 min, said MFR being measured at Tm+20°C according to ASTM D1238 using a test load of 2.16 kg.

27. Polyamide (PA) according to any one of claims 1 to 26, 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.

28. 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 27, wherein the water absorption is determined by calculating the water absorption using:

29. 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 28, comprising or consisting of:

30. a polymer matrix comprising or consisting of a polyamide (PA) according to any one of claims 1 to 28 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:

31. Use of a polyamide (PA) according to any one of claims 1 to 28 for the preparation of a thermoplastic composite (TC).

Images