Bio-based polyamides and corresponding polymer compositions

Abstract

Described herein are bio-based semi-crystalline copolyamides suitable for producing unfilled, fiber-reinforced thermoplastic compounds and composites having a combination of thermal properties prepared from a first diamine (DA1) selected from the group consisting of 2,2,4-trimethyl-1,6-hexanediamine (2,2,4-TMD), 2,4,4-trimethyl-1,6-hexanediamine (2,4,4-TMD), and mixtures thereof, and a second diamine (DA2) selected from the group consisting of 1,9-nonanediamine (C9), 1,10-decanediamine (C10), and mixtures thereof.

Description

[Technical Field]

[0001] This PCT application claims priority to U.S. Patent Application No. 63 / 407853, filed September 19, 2022, and European Patent Application No. 22201546.3, filed October 14, 2022, the contents of which are incorporated herein by reference in their entireties for all purposes. In the event of any discrepancy between this PCT application and the two applications that would affect the clarity of terminology or wording, only this PCT application shall be referenced.

[0002] The present invention relates to bio-based semi-crystalline copolyamides that have a combination of thermal properties and are suitable for preparing unfilled, fiber-reinforced thermoplastic compounds and 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 have high absorption values, typically up to 9%.

[0004] Aliphatic polyamides cannot be used in many applications where stringent dimensional stability requirements apply even in wet or moist conditions. Water absorption not only changes the dimensions but also the mechanical properties. Water absorption reduces stiffness and strength to a fraction of their original values. However, there are many applications involving mechanical loads in contact with water or ambient humidity, where dimensional stability and maintenance of mechanical properties are required.

[0005] To address these challenges, semi-aromatic polyamides have been developed. Trogamid T5000 is a commercially available amorphous polyamide composed of a mixture of 2,2,4-trimethyl-1,6-hexanediamine (2,2,4-TMD) and 2,4,4-trimethyl-1,6-hexanediamine (2,4,4-TMD) and terephthalic acid. This amorphous polyamide exhibits 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 approximately 7.5 wt %.

[0006] U.S. Patent No. 8,871,862 discloses a copolyamide comprising, in reacted form: a) 50 to 95 mole % of a first mixture consisting of terephthalic acid and one diamine selected from the group consisting of 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, and 1,12-dodecanediamine; and b) 5 to 50 mole % of a second mixture consisting of terephthalic acid and at least one diamine selected from the group consisting of 2,2,4-trimethylhexamethylenediamine and 2,4,4-trimethylhexamethylenediamine (the mole % values ​​are based on the total of components a) and b)); and up to 5 mole % of units derived from one or more other monomers selected from the group consisting of acids other than terephthalic acid, lactams, and aminocarboxylic acids. U.S. Patent No. 8,871,862 does not disclose the polyamides of the present invention.

[0007] U.S. Patent No. 4,495,328 describes semi-crystalline polyamides made from a mixture of hexamethylenediamine and TMD and terephthalic acid. The document cites PA6T / TMDT (60 / 40 at 1% mo) with a melting point of 310°C as an example. The high melting point of this polyamide limits its processing window, especially in extrusion, where the polyamide must remain in the molten phase for extended periods.

[0008] U.S. Patent No. 4,476,280 describes copolyamides made from terephthalic acid, isophthalic acid, and adipic acid in combination with fossil-based hexamethylenediamine and TMD. These copolyamides exhibit high moisture absorption.

[0009] U.S. Patent Publication No. 2012 / 095161 (D1) discloses a copolyamide comprising, in reacted form: a) 50 to 95 mol % of a first mixture comprising terephthalic acid and one diamine selected from the group consisting of 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, and 1,12-dodecanediamine; and b) 5 to 50 mol % of a second mixture comprising terephthalic acid and at least one diamine selected from the group consisting of 2,2,4-trimethylhexamethylenediamine and 2,4,4-trimethylhexamethylenediamine. D1 only discloses the use of terephthalic acid in the examples of the invention. According to one embodiment, the copolyamide can contain up to 30 mol %, up to 25 mol %, up to 20 mol %, up to 15 mol %, up to 10 mol %, or up to 5 mol % of units derived from other monomers. D1 more specifically discloses the following examples:

[0010] [Table 1]

[0011] European Patent No. 1795632(D2) discloses a semi-aromatic copolyamide comprising: (1) dicarboxylic acid units comprising at least one first dicarboxylic acid unit selected from the group consisting of terephthalic acid units and isophthalic acid units, wherein the proportion of the first dicarboxylic acid units is 60 mol % or more based on the total dicarboxylic acid units; and (2) diamine units comprising at least one first diamine unit selected from the group consisting of 2,2,4-trimethylhexanediamine units, 2,4,4-trimethylhexanediamine units, and 1,6-hexanediamine units, and at least one second diamine unit selected from the group consisting of 1,9-nonanediamine units and 2-methyl-1,8-octanediamine units, wherein the combined proportion of the first diamine units and the second diamine units is 60 mol % or more based on the total diamine units. Copolyamides B9 and B10 are based on the following components: diacid component: terephthalic acid (80 mol%) + isophthalic acid (20 mol%); diamine component: 2,2,4-trimethylhexanediamine (20 mol%) + 1,9-nonanediamine (40 mol%) + 2-methyl-1,8-octanediamine (40 mol%). D2 does not disclose a diamine component (A) as in the present invention. Summary of the Invention [Problem to be solved by the invention]

[0012] In the field of thermoplastic composites, particularly for automotive applications, there is an increasing demand for polymer resins that exhibit a combination of a wide processing window between the resin's melting point (Tm) and decomposition point (Tdeg), excellent crystallization rate, and high dimensional stability up to at least 80° C. (dry and wet conditions). Thus, the polymer resin must exhibit a high heat of fusion, a high glass transition temperature (Tg), and a melting point (Tm) that is high enough for heat resistance but below 300° C. to exhibit good processability.

[0013] Although a high Tg is beneficial for heat resistance and maintenance of mechanical properties up to high temperatures, more processable resins are also desired for the production of thermoplastic composites. This explains why, for a given Tg, the resins advantageously exhibit a limited Tm between 238°C and 300°C, preferably between 238°C and 290°C (excluding the value of 290°C), and a limited Tm / Tg ratio within the range defined above for a given Tg, so that the lower the Tm, the better.

[0014] Additionally, the polymer resin must exhibit water resistance, particularly dimensional stability in the presence of moisture and hot water resistance.

[0015] Additionally, there is an increasing need to use polymer resins that have a lower environmental footprint, which has led to a growing demand for polymer resins that exhibit a high biobased content as determined in accordance with ASTM D6866-22.

[0016] The polyamide of the present invention aims to solve these technical problems.

[0017] The present invention relates to a polyamide as disclosed in any one of claims 1 to 37. In particular, the present invention relates to a polyamide as disclosed in embodiment (E*).

[0018] The present invention also relates to a method for preparing the polyamides of the invention as disclosed in claim 38.

[0019] The present invention also relates to a thermoplastic composite material as disclosed in any one of claims 39-40.

[0020] More precise and detailed information on these topics is provided below. DETAILED DESCRIPTION OF THE INVENTION

[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 ranges are included (even open-ended ranges, such as those including "at least" or "most").

[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 ratio of diamines in the diamine component (A) is based on the total amount of diamines in the diamine component (A). The ratio of dicarboxylic acids in the dicarboxylic acid component (B) is based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B).

[0027] The present invention relates to a repeating unit (R PA ) a semi-aromatic copolyamide (PA) comprising The diamine component (A) is a) a first diamine (DA1) selected from the group consisting of 2,2,4-trimethyl-1,6-hexanediamine (2,2,4-TMD), 2,4,4-trimethyl-1,6-hexanediamine (2,4,4-TMD), and mixtures thereof; b) a second diamine (DA2) selected from the group consisting of 1,9-nonanediamine (C9), 1,10-decanediamine (C10), and mixtures thereof; comprising, consisting essentially of, or consisting of; the molar ratio DA1 / DA2 of the first diamine (DA1) to the second diamine (DA2) is 5 / 95 to 47 / 53, and the proportion of DA2 in the diamine component (A) is 53.0 mol % or more (≧53.0 mol %), this proportion being based on the total amount of diamines in the diamine component (A); The dicarboxylic acid component (B) is a) 70.0 to 95.0 mol% of terephthalic acid; b) 5.0 (this value is exclusive) to 30.0 mole % of a diacid (DI) selected from the group consisting of isophthalic acid, adipic acid (AA), azelaic acid, sebacic acid, dodecanedioic acid, brassylic acid, 1,4-cyclohexanedicarboxylic acid (CHDA), and mixtures thereof; comprising, consisting essentially of, or consisting of; These proportions in mole percent are based on the total amount of diacids in dicarboxylic acid component (B); This relates to semi-aromatic copolyamides (PA).

[0028] The polyamide (PA) of the present invention is formed by polycondensation of a diamine component (A) and a dicarboxylic acid component (B). This reaction is based on the condensation of a diamine with a dicarboxylic acid, resulting in the formation of an amide bond. Those skilled in the art will understand that 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 -NH2 / COOH ratio can be 0.9 to 1.1, preferably 0.95 to 1.05, and more preferably 0.98 to 1.02.

[0029] The repeating units of polyamide (PA) are typically the repeating units (R PA ) which is formed by polycondensation of a diamine component (A) and a dicarboxylic acid component (B). PA ) a semi-aromatic copolyamide (PA) in which The diamine component (A) is a) a first diamine (DA1) selected from the group consisting of 2,2,4-trimethyl-1,6-hexanediamine (2,2,4-TMD), 2,4,4-trimethyl-1,6-hexanediamine (2,4,4-TMD), and mixtures thereof; b) a second diamine (DA2) selected from the group consisting of 1,9-nonanediamine (C9), 1,10-decanediamine (C10), and mixtures thereof; comprising, consisting essentially of, or consisting of; the molar ratio DA1 / DA2 of the first diamine (DA1) to the second diamine (DA2) is 5 / 95 to 47 / 53, and the proportion of DA2 in the diamine component (A) is 53.0 mol % or more (≧53.0 mol %), this proportion being based on the total amount of diamines in the diamine component (A); The dicarboxylic acid component (B) is a) 70.0 to 95.0 mol% of terephthalic acid; b) 5.0 (this value is exclusive) to 30.0 mole % of a diacid (DI) selected from the group consisting of isophthalic acid, adipic acid (AA), azelaic acid, sebacic acid, dodecanedioic acid, brassylic acid, 1,4-cyclohexanedicarboxylic acid (CHDA), and mixtures thereof; comprising, consisting essentially of, or consisting of; It also relates to semi-aromatic copolyamides (PA) in which these proportions in mol % are based on the total amount of diacids in the dicarboxylic acid component (B).

[0030] Further details regarding the diamine component (A) and the dicarboxylic acid component (B) are provided below.

[0031] Diamine component (A) The diamine component (A) comprises, consists of, or consists essentially of a first diamine (DA1) selected from the group consisting of 2,2,4-trimethyl-1,6-hexanediamine (2,2,4-TMD), 2,4,4-trimethyl-1,6-hexanediamine (2,4,4-TMD), and mixtures thereof, and a second diamine (DA2) selected from the group consisting of 1,9-nonanediamine (C9), 1,10-decanediamine (C10), and mixtures thereof.

[0032] DA2 is the main or major diamine in diamine component (A). The proportion of DA2 is 53.0 mol % or more (≧53.0 mol %) based on the total amount of diamines in diamine component (A). More specifically, the proportion of DA2 is 53.0 to 95.0 mol % based on the total amount of diamines in diamine component (A). This proportion may be more specifically 60.0 to 95.0 mol %.

[0033] According to one embodiment, diamine component (A) comprises a first diamine (DA1) selected from the group consisting of 2,2,4-trimethyl-1,6-hexanediamine (2,2,4-TMD), 2,4,4-trimethyl-1,6-hexanediamine (2,4,4-TMD), and mixtures thereof; and a second diamine (DA2) selected from the group consisting of 1,9-nonanediamine (C9), 1,10-decanediamine (C10), and mixtures thereof. According to this embodiment, diamine component (A) may comprise 2-methyl-1,8-octanediamine (MODA), wherein the proportion of MODA in diamine component (A) is 10.0 mol% or less (≦10.0 mol%), preferably 5.0 mol% or less (≦5.0 mol%), the proportion in mol% being based on the total amount of diamines in diamine component (A).

[0034] According to another embodiment, the diamine component (A) consists essentially of or consists of a first diamine (DA1) and a second diamine (DA2).

[0035] In the context of the present invention, the expression "consisting essentially of" with respect to the diamine component means that diamine component (A) comprises DA1 and DA2 and may also contain up to 2.0 mol %, preferably up to 1.0 mol %, and more preferably up to 0.5 mol % of other diamines, this percentage in mol % being based on the total amount of diamines in diamine component (A). In other words, diamine component (A) consists of DA1, DA2, and up to 2.0 mol %, preferably up to 1.0 mol %, and more preferably up to 0.5 mol % of at least one diamine other than DA1 and other than DA2, this percentage in mol % being based on the total amount of diamines in diamine component (A).

[0036] DA1 is selected from the group consisting of 2,2,4-TMD, 2,4,4-TMD, and mixtures thereof. 2,2,4-TMD has the formula: [ka] 2,4,4-TMD is a diamine of the formula: [ka] DA1 is advantageously a combination of 2,2,4-TMD and 2,4,4-TMD.

[0037] DA2 is selected from the group consisting of 1,9-nonanediamine (C9), 1,10-decanediamine (C10), and mixtures thereof.

[0038] DA2 preferably comprises organic carbon derived from renewable resources as determined in accordance with ASTM D6866-20.

[0039] DA2 is preferably bio-based. The term "bio-based" as applied to a compound means that the compound is made from materials that contain carbon from renewable sources derived from living or once-living organisms, excluding materials buried in geological formations and / or fossilized materials, e.g., petroleum-based materials.

[0040] According to one embodiment (E1), DA2 is 1,9-nonanediamine, which is preferably bio-based (see also below), so that the polyamide (PA) exhibits a high bio-based content.

[0041] According to an advantageous embodiment (E2), DA2 is 1,10-decanediamine, which is preferably biobased (see also below), so that the polyamide (PA) exhibits a high biobased content.

[0042] Molar ratio DA1:DA2 In the context of the present disclosure, the molar ratio DA1 / DA2 of the first diamine (DA1) to the second diamine (DA2) is 5 / 95 to 47 / 53. More specifically, this molar ratio is: 5 / 95~40 / 60; or 15 / 85~47 / 53; or 15 / 85~37 / 63; or 18 / 82~47 / 53; or 8 / 92~37 / 63; or 25 / 75~35 / 65 It may be.

[0043] The diamine component (A) preferably does not contain hexamethylenediamine. The diamine component (A) preferably does not contain bis(aminoalkyl)cyclohexanediamines (such as 1,3-bis(aminomethyl)cyclohexane or 1,4-bis(aminomethyl)cyclohexane). The diamine component (A) preferably does not contain 2-methyl-1,8-octanediamine.

[0044] Dicarboxylic acid component (B) The dicarboxylic acid component (B) comprises 70.0 to 95.0 mole % of terephthalic acid and 5.0 (this value is exclusive) to 30.0 mole % of another diacid (DI) selected from the group consisting of isophthalic acid, adipic acid (AA), azelaic acid, sebacic acid, dodecanedioic acid, brassylic acid, 1,4-cyclohexanedicarboxylic acid (CHDA), and mixtures thereof, and these mole % ratios are based on the total amount of diacids in the dicarboxylic acid component (B).

[0045] When the other diacid (DI) has more than 8 carbon atoms, the proportion of the other diacid (DI) is preferably less than 20.0 mol %, more preferably less than 15.0 mol %.

[0046] When the other diacid (DI) contains 8 or more carbon atoms, the proportion of the other diacid is preferably 20.0 mol % or less, more preferably 15.0 mol % or less.

[0047] The other diacids (DI) may more particularly be selected from the group consisting of isophthalic acid, adipic acid (AA), 1,4-cyclohexanedicarboxylic acid (CHDA), and combinations of two or more of the aforementioned diacids.

[0048] The other diacid (DI) may be one of the diacids listed in Table I. Thus, the other diacid (DI) may be isophthalic acid or adipic acid (AA) or 1,4-cyclohexanedicarboxylic acid (CHDA). The other diacid (DI) is preferably isophthalic acid.

[0049] The proportion of terephthalic acid in the dicarboxylic acid component (B) may be preferably at least 80.0 mol%, preferably at least 83.0 mol%, more preferably at least 85.0 mol%, and may be at least 87.0 mol%.

[0050] The proportion of the other diacids (DI) in the dicarboxylic acid component (B) is strictly greater than (>) 5.0 mol %. The proportion of the other diacids (DI) in the dicarboxylic acid component (B) is preferably at most 20.0 mol %, preferably at most 17.0 mol %, more preferably at most 15.0 mol %. This proportion may be at most 13.0 mol %. Note that the other diacids (DI) may be a combination of two diacids, so the proportions indicated herein correspond to the total proportion of the diacids (DI).

[0051] All these proportions of terephthalic acid and other diacids (DI) in mole percent are based on the total amount of diacids in dicarboxylic acid component (B).

[0052] According to one embodiment, the dicarboxylic acid component (B) consists essentially of or consists of terephthalic acid and other diacids (DI). In the context of the present invention, the expression "consisting essentially of" with respect to the dicarboxylic acid component (B) means that the dicarboxylic acid component (B) comprises terephthalic acid and other diacids (DI), and may also contain up to 2.0 mol%, preferably up to 1.0 mol%, and more preferably up to 0.5 mol% of diacids other than terephthalic acid and other than DI, where this percentage in mol% is based on the total amount of diacids in the dicarboxylic acid component (B). In other words, the dicarboxylic acid component (B) consists of terephthalic acid, other diacids (DI), and up to 2.0 mol%, preferably up to 1.0 mol%, and more preferably up to 0.5 mol% of at least one diacid other than terephthalic acid and other than DI, where this percentage in mol% is based on the total amount of diacids in the dicarboxylic acid component (B).

[0053] Those skilled in the art will recognize that polycondensation of the above-defined monomers produces compounds of the following formulae, respectively: [ka] (wherein R1 is a divalent radical derived from DA1 or DA2, and R2 is a divalent radical derived from a diacid (DI)) PA1 ) and (R PA2For example, if the diacid (DI) is isophthalic acid, then a polyamide (PA) containing (R PA2 ) is expressed as follows: [ka]

[0054] Therefore, the present invention relates to the amount of repeating units (R PA1 ) and (R PA2 ) in the following proportions: 70.0 to 95.0 mol% (R PA1 ); 5.0 (this value is excluded) to 30.0 mol% (R PA2 ); (In the formula, R1 is a) a first diamine (DA1) as defined above; and b) a second diamine (DA2) as defined above; and is a divalent radical of a diamine corresponding to the combination of the molar ratio DA1 / DA2 of the first diamine (DA1) to the second diamine (DA2) is as defined herein; ·R2 is the divalent radical of a diacid (DI).

[0055] Repeating unit (R PA1 ) and (R PA2 ) is at least 95.0 mol %, preferably at least 99.0 mol %, and even more preferably at least 99.5 mol %.

[0056] The polyamide (PA) preferably does not contain any repeating units derived from lactams.The polyamide (PA) preferably does not contain any repeating units derived from hexamethylenediamine.

[0057] The polyamide (PA) of the present invention preferably does not contain repeat units derived from hexamethylenediamine or bis(aminoalkyl)cyclohexanediamines (e.g. 1,3-bis(aminomethyl)cyclohexane or 1,4-bis(aminomethyl)cyclohexane) or 2-methyl-1,8-octanediamine.

[0058] According to a preferred embodiment, the repeating units (R PA ) is a repeating unit (R PA1 ) and (R PA2 ) or consisting essentially of

[0059] Repeating unit (R PA1 ) percentage Those skilled in the art will appreciate that all details and embodiments relating to the proportions of terephthalic acid and diacid (DI) in the dicarboxylic acid component (B) provided herein are consistent with the repeating units (R PA1 ) and (R PA2 ) and understand that it can be converted into the corresponding percentage.

[0060] Repeating unit (R PA1 ) is 70.0 to 95.0 mol%. This proportion is preferably at least 80.0 mol%, preferably at least 83.0 mol%, more preferably at least 85.0 mol%. This proportion may be at least 87.0 mol%.

[0061] Repeating unit (R PA2 ) percentage Repeating unit (R PA2 The proportion of ) is 5.0 (this value is excluded) to 30.0 mol%. This proportion is preferably at most 20.0 mol%, preferably at most 17.0 mol%, more preferably at most 15.0 mol%. This proportion may be at most 13.0 mol%.

[0062] If the polyamide (PA) is based on a diacid having more than 8 carbon atoms, (R PA2) is preferably less than 20.0 mol %, more preferably less than 15.0 mol %.

[0063] Number average molecular weight (Mn) The polyamides (PA) of the present invention typically have a number-average molecular weight ("Mn") ranging from 1,000 g / mol to 40,000 g / mol, e.g., from 2,000 g / mol to 35,000 g / mol, from 4,000 to 30,000 g / mol, or from 5,000 g / mol to 20,000 g / mol. Mn can be determined using the following formula (1): Mn = 2,000,000 / [EG] (1), or more precisely, using known methods for measuring amine and acid end group concentrations, where [EG] is the percentage of end groups in the PA expressed in mmol / kg. The end groups in the polyamides (PA) are typically amine and / or acid moieties. However, if the polycondensation involves the addition of an end-capping agent, the amine end groups can be 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 fully or partially converted to amide end groups such as benzamide or acetamide, which end groups can be 1 It can be easily quantified by 1 H NMR.

[0064] Intrinsic viscosity (IV) The polyamide (PA) preferably exhibits an intrinsic viscosity (IV) of 0.50 to 1.70 dL / g.

[0065] The IV of the polyamide (PA) may be more specifically 0.70 to 1.00 dL / g or 0.80 to 1.00 dL / g, or more specifically 1.00 to 1.50 dL / g or 1.05 to 1.25 dL / g.

[0066] In this disclosure, intrinsic viscosity IV is measured according to ASTM D5336-22 using a phenol / trichloroethylene mixture (60 / 40 by weight).

[0067] terminal group 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) may be -NH2 or -COOH. However, if the polycondensation is accompanied by the addition of an end-capping agent, these end groups may be partially or entirely converted into amide end groups.

[0068] Amide end groups are of the formula -NH-C(=O)-R (wherein R is an alkyl, aryl, or cycloalkyl group) and / or -C(=O)-NH-R' (wherein R' is an alkyl or cycloalkyl group). R is more specifically a linear or branched C1-C 18 Alkyl group or C5-C 10 R' is a linear or branched C2-C cycloalkyl group. 18 It is an alkyl group.

[0069] 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.

[0070] The monocarboxylic acid (end-capping agent) is advantageously benzoic acid, cyclohexanoic acid, R-COOH (where R is a linear or branched C-C 18 R is a radical derived from an acid of formula R-COOH.

[0071] More specifically, the monocarboxylic acid (endcapping agent) can 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.

[0072] The monocarboxylic acid (endcapping agent) is more specifically represented by the formula CH3-(CH2) n -COOH (n is an integer from 0 to 16). In that case, the amide end group has the formula -NH-C(=O)-(CH2)n -CH3.

[0073] 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).

[0074] 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 radical derived from an amine of formula R'-NH2.

[0075] The primary amine (endcapping agent) is more specifically a compound of the formula CH3-(CH2) n’ -NH2 (n' is an integer from 2 to 18). In that case, the amide end group has the formula -C(=O)-NH-(CH2) n’ -CH3.

[0076] More specifically, the primary amine (endcapping agent) can 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.

[0077] The polyamide (PA) may contain a chain limiter, which is a monofunctional molecule capable of reacting with amine or carboxylic acid moieties. The chain limiter is more specifically acetic acid, propionic acid, benzoic acid, and / or C6-C8 12 It may also be a monoalkylamine.

[0078] The proportion of terminal groups is 1 Quantitation can be achieved by 1 H NMR or potentiometry.

[0079] Bio-ingredient content The polyamide (PA) typically exhibits a biocomponent content of at least 30.0%, preferably at least 33.0%, preferably at least 35.0 mol%, more preferably at least 36.0%, more preferably at least 37.0%, more preferably at least 38.0%, more preferably at least 39.0%, even more preferably at least 40.0%, and more preferably at least 45.0%, where the biocomponent content is expressed as the % of organic carbon derived from renewable resources as measured according to ASTM D6866-22.

[0080] Biocontent is defined as the % of organic carbon that comes from renewable sources. 14 It corresponds to the amount of C calculated from the C percent and then corrected for isotopic proportions.

[0081] Both the C9 diamine and the C10 diamine may be bio-based or derived from petroleum or natural gas.

[0082] [Table 2]

[0083] The polyamide (PA) disclosed herein is prepared from bio-based 1,9-nonanediamine (C9) and / or 1,10-decanediamine (C10), which allows for the production of polyamides (PA) with a high biocomponent content.

[0084] According to one embodiment, the polyamide (PA) disclosed herein is prepared from biobased 1,9-nonanediamine (C9) and / or 1,10-decanediamine (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 the % of organic carbon derived from renewable resources as measured according to ASTM D6866-22.

[0085] Biobased terephthalic acid can also be used to increase the biocomponent content. In this case, the biocomponent content, as defined above, can be at least 75.0%, or even at least 79.0%. Biobased terephthalic acid can be prepared from biobased furfural, for example, as disclosed 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).

[0086] Resistant to moisture absorption and water aging The polyamides (PA) of the present invention advantageously exhibit a water absorption of less than 5.0 wt. % at 23° C. The water absorption at 23° C. is determined by (i) preparing dry test specimens (water content less than 0.2 wt. %) molded according to ISO 527, (ii) immersing the test specimens in deionized water at 23° C. until a constant weight is reached, and (iii) calculating the water absorption using the following formula:

number

[0087] The polyamides (PA) of the present invention also exhibit resistance to hot water, as disclosed hereinafter, which test is carried out by placing the samples in hot water at 135° C. in a closed container for 200 hours.

[0088] The polyamide (PA) of the present invention advantageously exhibits a water absorption rate of less than 5.0% (≦5.0%) for 200 hours at 135° C. The water absorption rate for 200 hours at 135° C. is determined by a method comprising the following steps: (i) providing three samples molded in the shape of an ISO 527 Type IA tensile test bar in a dry state (water content less than 0.2% by weight); (ii) immersing the three samples in deionized water at 135° C. for 200 hours; (iii) determining the water absorption rate for each sample using the following formula:

number

[0089] The polyamides (PA) of the present invention advantageously exhibit an IV retention of at least 90.0%, preferably at least 95.0%, which is determined by a method comprising the steps of: (i) providing a sample in the shape of an ISO 527 Type IA tensile test bar in the dry state (water content less than 0.2% by weight); (ii) immersing the sample in deionized water at 135°C for 200 hours; (iii) determining the IV retention of the sample by the following formula: IV retention rate=IV after / IV before ×100 (In the formula, IV before and IV after is the intrinsic viscosity of the sample before and after the test).

[0090] 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, the details of which are set out below.

[0091] 1) Melting point (Tm) The polyamide exhibits a Tm of at least 238°C, preferably at least 240°C. The Tm may preferably be at least 250°C, preferably at least 260°C.

[0092] The Tm may be at least 265°C, or even at least 270°C.

[0093] The Tm is usually at most 300°C, or at most 290°C.

[0094] The Tm is preferably strictly less than (<290°C).

[0095] The Tm may be up to 280°C.

[0096] Tm may be from 238°C to 300°C, or from 240°C to 300°C.

[0097] The Tm may be 238% to 280%.

[0098] Tm can be measured by differential scanning calorimetry ("DSC") according to ASTM D3418, particularly using a heating and cooling rate of 20°C / min.

[0099] Tm can be measured by differential scanning calorimetry ("DSC") according to ASTM D3418 using a heating and cooling rate of 20°C / min. Each DSC test uses three scans: a first heat to 350°C, followed by a first cool to 0°C, followed by a second heat to 360°C. Tm is determined from the second heat.

[0100] Tm can be more specifically measured by the method described in the experimental section.

[0101] 2) Heat of fusion (Hm) Polyamide (PA) is semi-crystalline.

[0102] The polyamide (PA) exhibits a heat of fusion (Hm) of at least 30.0 J / g, preferably at least 35.0 J / g.

[0103] Hm may be up to 90.0 J / g or up to 80.0 J / g.

[0104] Hm may be 30.0 J / g to 90.0 J / g.

[0105] Hm can be measured by differential scanning calorimetry ("DSC") according to ASTM D3418, particularly using a heating and cooling rate of 20°C / min.

[0106] Hm can be measured by differential scanning calorimetry ("DSC") according to ASTM D3418 using a heating and cooling rate of 20°C / min. Each DSC test uses three scans: one heating to 350°C, followed by one cooling to 0°C, followed by a second heating to 360°C.

[0107] More specifically, Hm can be measured by the method described in the experimental section.

[0108] 3) Glass transition temperature (Tg) The polyamide exhibits a Tg of at least 100° C. The Tg of the polyamide (PA) may preferably be at least 105° C., preferably at least 110° C., preferably at least 115° C., preferably at least 120° C.

[0109] Polyamides (PA) typically exhibit a Tg of up to 140°C.

[0110] More specifically, Tg may be 100°C to 135°C.

[0111] Tg can be measured by differential scanning calorimetry ("DSC") according to ASTM D3418, particularly using a heating and cooling rate of 20°C / min.

[0112] Tg can be measured by differential scanning calorimetry ("DSC") according to ASTM D3418 using a heating and cooling rate of 20°C / min. Each DSC test uses three scans: a first heat to 350°C, followed by a first cool to 0°C, followed by a second heat to 360°C. Tg is determined from the second heat.

[0113] More specifically, Tg can be measured by the method described in the experimental section.

[0114] As detailed above, the polyamides (PA) of the present invention exhibit a combination of thermal properties. The present invention therefore more particularly relates to polyamides (PA) that exhibit the following combination of properties: Tm between 240°C and 300°C, preferably between 240°C and 290°C (the value of 290°C being excluded); a Tg of at least 115°C, preferably at least 120°C; A biocomponent content of at least 30.0%, preferably at least 33.0%, preferably at least 35.0 mol%, more preferably at least 37.0%, more preferably at least 40.0%, and even more preferably at least 45.0%.

[0115] The present invention more particularly also relates to polyamides (PA) that exhibit the following combination of properties: Tm of 240℃~300℃; Tg of at least 120°C; A biocomponent content of at least 33.0% or more, preferably at least 35.0 mol%, more preferably 37.0%, even more preferably at least 40.0%, and more preferably at least 45.0%.

[0116] 4)Tm / Tg ratio As mentioned above, polyamides (PA) exhibit a combination of thermal properties, and it is beneficial to have a definite Tm for a given Tg. Therefore, Tm / Tg is preferably definable according to the inequality in Equation 1 (eq.1), preferably according to the inequality in Equation 2 (eq.2): Tm / Tg<-0.0372×Tg(℃)+6.8402(eq.1) Tm / Tg<-0.0372×Tg(℃)+6.8002(eq.2).

[0117] None of the copolyamides of D1 (Table I) obey these two inequalities.

[0118] Embodiment (E*) According to a preferred embodiment (E*), the present invention provides a polymerizable composition comprising a repeating unit (R PA *) and a polyamide (PA*) - the diamine component (A) is a) a first diamine (DA1) selected from the group consisting of 2,2,4-trimethyl-1,6-hexanediamine (2,2,4-TMD), 2,4,4-trimethyl-1,6-hexanediamine (2,4,4-TMD), and mixtures thereof; b) a second diamine (DA2) selected from the group consisting of 1,9-nonanediamine (C9), 1,10-decanediamine (C10), and mixtures thereof; comprising, consisting essentially of, or consisting of; the proportion of the second diamine (DA2) in the diamine component (A) is 60.0 to 85.0 mol %, and the molar ratio DA1 / DA2 of the first diamine (DA1) to the second diamine (DA2) is 15 / 85 to 40 / 60; - the dicarboxylic acid component (B) is a) 82.0 to 94.0 mol% of terephthalic acid; b) 6.0 to 18.0 mol% of isophthalic acid; comprising, consisting essentially of, or consisting of; These proportions in mole percent are based on the total amount of diacids in dicarboxylic acid component (B); The following characteristics: Tm between 240°C and 290°C (the 290°C value is excluded); · Tg of 115℃~135℃; Optionally, a biocomponent content of at least 33.0%, preferably at least 35.0 mol%, and more preferably at least 37.0%; This relates to polyamide (PA*).

[0119] The present invention relates to a polyamide (PA) having a repeating unit (R PA1 ) and (R PA2 ): 82.0 to 94.0 mol% (R PA1 ) [ka] 6.0 to 18.0 mol% (R PA2 ) [ka] (In the formula: R1 is a) a first diamine (DA1) selected from the group consisting of 2,2,4-trimethyl-1,6-hexanediamine (2,2,4-TMD), 2,4,4-trimethyl-1,6-hexanediamine (2,4,4-TMD), and mixtures thereof; b) a second diamine (DA2) selected from the group consisting of 1,9-nonanediamine (C9), 1,10-decanediamine (C10), and mixtures thereof; and the molar ratio DA1 / DA2 of the first diamine (DA1) to the second diamine (DA2) is 15 / 85 to 40 / 60; The proportion of repeating units derived from DA2 is 60.0 to 85.0 mol %. Polyamide (PA*) consisting essentially of or consisting of: The following characteristics: Tm between 240°C and 290°C (the 290°C value is excluded); · Tg of 115℃~135℃; Optionally, a biocomponent content of at least 33.0%, preferably at least 35.0 mol%, and more preferably at least 37.0%; It also relates to polyamides (PA*) which exhibit:

[0120] The proportion of isophthalic acid in the dicarboxylic acid component (B) or the repeating unit (R PA2 ) may more specifically be 8.0 to 17.0 mol % or 8.0 to 12.0 mol %.

[0121] The polyamide (PA) and repeating units (R PA All embodiments, details and properties of the polyamide (PA*) and repeating units (R PA* ) is also applicable.

[0122] Preparation of polyamide (PA) and (PA*) The polyamides (PA) and (PA*) described herein can be prepared by any conventional method adapted to the synthesis of polyamides and polyphthalamides. The following details relate to polyamides (PA), but are of course also applicable to polyamides (PA*).

[0123] Polyamides (PA) are usually produced by polycondensation in the melt.

[0124] Polyamide (PA) can be prepared by heating a reaction mixture (RM) comprising or consisting of all the monomers (DA1, DA2, terephthalic acid, and DI) in the presence of less than 60% by weight, preferably less than 30% by weight, more preferably less than 20% by weight, preferably less than 10% by weight of water, preferentially without the addition of water.

[0125] As is well known in polycondensation, the reaction mixture contains the diamine and diacid in amounts such that the ratio of -COOH groups from the diacid to the ratio of -NH groups from the diamine is substantially equimolar. The amine / acid ratio can be comprised between 0.9 and 1.1, preferably between 0.95 and 1.05, and more preferably between 0.98 and 1.02.

[0126] The reaction mixture (RM) preferably comprises a catalyst, which may be selected from the group consisting of phosphorous acid, ortho-phosphoric acid, meta-phosphoric acid, alkali metal hypophosphites, such as sodium hypophosphite, and phenylphosphinic acid. A convenient catalyst used is phosphorous acid.

[0127] To control the molar mass, the reaction mixture (RM) may further comprise at least one chain limiting agent (endcapping agent) as disclosed above.

[0128] The temperature to which the reaction mixture (RM) is heated must be high enough to induce a reaction between the amine groups of the diamine component (A) and the carboxyl groups of the dicarboxylic acid component (B) and reduce the viscosity of the mixture. This temperature is usually at least 150°C, preferably at least 200°C. Polycondensation forms amide bonds and releases water as a by-product.

[0129] The temperature can be increased stepwise during the polycondensation, an example of which is given in Example 1 and can be followed for the preparation of polyamide (PA).

[0130] 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 stirrer is adjusted to provide sufficient stirring of the reaction mixture at the beginning of the polymerization and again when the polycondensation conversion is nearly complete.

[0131] The conditions disclosed in the experimental section can be advantageously used for the preparation of polyamides (PA).

[0132] Thermoplastic composite material (TPC) Polyamide (PA) or (PA*) is configured for use in the preparation of thermoplastic composites (TPC). The following details relate to polyamide (PA), but are also applicable to polyamide (PA*).

[0133] Thermoplastic composites (TPCs) are a polymer matrix comprising or consisting of (i) polyamide (PA) or (PA*) and (ii) optionally at least one plastic additive; and · Fibers embedded in a polymer matrix; Includes.

[0134] Thermoplastic composites comprise a polymer matrix and fibers, preferably adhesively or cohesively bonded to the matrix, which usually completely surrounds the fibers. The function of the fibers, held in place by the polymer matrix, is to improve the mechanical properties of the composite while minimizing its weight.

[0135] Typically, the proportion of fibres is at least 5.0% by weight, this proportion being given relative to the weight of the thermoplastic composite.

[0136] The polymer matrix comprises or consists of (i) the polyamide (PA) of the present invention and (ii) at least one optional plastic additive typically and preferably blended with the polyamide (PA). 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 ​​typically less than 20.0 wt. %, this proportion being based on the total weight of the polymer matrix.

[0137] Fibers typically exhibit high specific stiffness and strength values.

[0138] The fibers may be of inorganic type (for example glass fibers) or organic type (for example aramid fibers or carbon fibers), and it is also possible to use combinations of different fibers.

[0139] 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.

[0140] The thermoplastic composite materials are prepared by any of the techniques known to those skilled in the art, in particular as disclosed in Composites Manufacturing 1992, Vol. 3, No. 4 "Impregnation technology for thermoplastic matrix composites". These techniques are based on a first step in which the polymer composition (C), in particular in powder form, is brought into contact with the fibers, and a second step in which heat and pressure are applied to the product obtained at the end of step a). The impregnation technique disclosed in US Pat. No. 5,236,972 can be followed.

[0141] In step a), it is preferable that the thermoplastic composition is distributed uniformly and homogeneously around the fibers, in particular to reduce the amount of voids in the final thermoplastic composite, and for this purpose a Tm in the range of 240°C to 300°C, preferably 240°C to 290°C (excluding this value), is recommended.

[0142] Use of Thermoplastic Composites (TPC) The thermoplastic composites (TPCs) disclosed herein can be used for 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 as follows:

[0144] Raw materials used The following raw materials were used to prepare polymer samples: 1,9-diaminononane (from Solvay, derived from biobased oleic acid, purity >98.0%), 1,10-diaminodecane (from Solvay, derived from biobased castor oil, purity >98.0%), terephthalic acid (from Flint Hills Resources), isophthalic acid (from Flint Hills Resources), 2,2,4-trimethyl-1,6-hexanediamine (2,2,4-TMD), 2,4,4-trimethyl-1,6-hexanediamine (2,4,4-TMD), and mixtures thereof (from Evonik Industries), adipic acid (from Ascend Performance Materials), 1,4-cyclohexanedicarboxylic acid (from Sigma Aldrich), and phosphoric acid (from Sigma Aldrich).

[0145] Preparation of polyamide All copolyamides disclosed in Table I were prepared by polycondensation in an autoclave reactor equipped with a distillation line fitted with a pressure control valve. The preparation of all copolyamides in Table II followed the procedure detailed below for Ex1 (except for composition).

[0146] Example 1 Polyamide Ex1 was prepared by adding 4.89 g of 1,9-diaminononane, 0.64 g of a mixture of 2,2,4-trimethyl-1,6-hexanediamine and 2,4,4-trimethyl-1,6-hexanediamine, 5.02 g of terephthalic acid, 0.56 g of isophthalic acid, 5.48 g of deionized water, and 0.0037 g of phosphoric 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 25 minutes, then to 232°C and held for 25 minutes, then to 288°C and held for 25 minutes, and then to 321°C and held for 15 minutes. The evolved steam was slowly vented to maintain the internal pressure below 200 psig. After holding the temperature at 321°C for 15 minutes, the reactor pressure was slowly reduced to atmospheric pressure over 30 minutes. Fifteen minutes after the start of depressurization, the reactor was cooled to 302°C. After holding at 302°C for an additional 15 minutes, the reactor was continuously purged with N2 gas for 25 minutes after depressurization was terminated. The reactor was then cooled to room temperature, and the polymer was recovered from the reactor.

[0147] 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. Each DSC test used three scans: 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 are determined from the second heat.

[0148] All polyamides of Examples E1-E12, except for E1, E3, and E5, obey the inequalities of Eq. 1 and Eq. 2.

[0149] [Table 3]

[0150] [Table 4]

[0151] [Table 5]

Claims

1. A repeating unit (R ＰＡ ) a polyamide (PA) comprising The diamine component (A) is a) a first diamine (DA1) selected from the group consisting of 2,2,4-trimethyl-1,6-hexanediamine (2,2,4-TMD), 2,4,4-trimethyl-1,6-hexanediamine (2,4,4-TMD), and mixtures thereof; b) a second diamine (DA2) selected from the group consisting of 1,9-nonanediamine (C9), 1,10-decanediamine (C10), and mixtures thereof; Including; the molar ratio DA1 / DA2 of the first diamine (DA1) to the second diamine (DA2) is 5 / 95 to 47 / 53; the proportion of DA2 in the diamine component (A) is 53.0 mol% or more (≧53.0 mol%), and this proportion is based on the total amount of diamines in the diamine component (A); The dicarboxylic acid component (B) is c) 70.0 to 95.0 mol % of terephthalic acid; d) 5.0 (this value is excluded) to 30.0 mole % of another diacid (DI) selected from the group consisting of isophthalic acid, adipic acid (AA), azelaic acid, sebacic acid, dodecanedioic acid, brassylic acid, 1,4-cyclohexanedicarboxylic acid (CHDA), and mixtures thereof; Including; These proportions in mole percent are based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B). Polyamide (PA).

2. 2. Polyamide (PA) according to claim 1, wherein the diamine component (A) consists essentially of or consists of a first diamine (DA1) and a second diamine (DA2).

3. 3. Polyamide (PA) according to claim 1 or 2, wherein the diamine component (A) consists of a first diamine (DA1), a second diamine (DA2) and up to 2.0 mol %, preferably up to 1.0 mol %, more preferably up to 0.5 mol % of at least one diamine other than DA1 and other than DA2, said proportions in mol % being based on the total amount of diamines in the diamine component (A).

4. Polyamide (PA) according to any one of claims 1 to 3, wherein the dicarboxylic acid component (B) consists essentially of or consists of terephthalic acid and other diacids (DI).

5. 5. Polyamide (PA) according to any one of claims 1 to 4, wherein the dicarboxylic acid component (B) consists of terephthalic acid, other diacids (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 other than DI, said proportions in mol % being based on the total amount of diacids in the dicarboxylic acid component (B).

6. 6. The polyamide (PA) according to any one of claims 1 to 5, wherein, when the diamine component (A) contains 2-methyl-1,8-octanediamine (MODA), the proportion of MODA in the diamine component (A) is 10.0 mol% or less (≦10.0 mol%), preferably 5.0 mol% or less (≦5.0 mol%), and this proportion in mol% is based on the total amount of diamines in the diamine component (A).

7. A repeating unit (R ＰＡ ) a polyamide (PA) comprising The diamine component (A) is a) a first diamine (DA1) selected from the group consisting of 2,2,4-trimethyl-1,6-hexanediamine (2,2,4-TMD), 2,4,4-trimethyl-1,6-hexanediamine (2,4,4-TMD), and mixtures thereof; b) a second diamine (DA2) selected from the group consisting of 1,9-nonanediamine (C9), 1,10-decanediamine (C10), and mixtures thereof; consisting essentially of, or consisting of; the molar ratio DA1 / DA2 of the first diamine (DA1) to the second diamine (DA2) is 5 / 95 to 47 / 53; The dicarboxylic acid component (B) is c) 70.0 to 95.0 mol % of terephthalic acid; d) 5.0 (this value is excluded) to 30.0 mole % of another diacid (DI) selected from the group consisting of isophthalic acid, adipic acid (AA), azelaic acid, sebacic acid, dodecanedioic acid, brassylic acid, 1,4-cyclohexanedicarboxylic acid (CHDA), and mixtures thereof; consisting essentially of, or consisting of; These proportions in mole percent are based on the total amount of dicarboxylic acid in the dicarboxylic acid component (B); Polyamide (PA).

8. The repeating units (R ＰＡ１ ) and (R ＰＡ２ ) 【Chemical 1】 and the following proportions: 70.0 to 95.0 mol% of (R ＰＡ１ ); 5.0 (this value is excluded) to 30.0 mol % (R ＰＡ２ ); In particular, the polyamide (PA) according to any one of claims 1 to 7. (In the formula, ・R １ teeth, a) a first diamine (DA1) selected from the group consisting of 2,2,4-trimethyl-1,6-hexanediamine (2,2,4-TMD), 2,4,4-trimethyl-1,6-hexanediamine (2,4,4-TMD), and mixtures thereof; b) a second diamine (DA2) selected from the group consisting of 1,9-nonanediamine (C9), 1,10-decanediamine (C10), and mixtures thereof; is a divalent radical of a diamine corresponding to the combination of the molar ratio DA1 / DA2 of the first diamine (DA1) to the second diamine (DA2) is 5 / 95 to 47 / 53; ・R ２ is the divalent radical of a diacid (DI) selected from the group consisting of isophthalic acid, adipic acid (AA), azelaic acid, sebacic acid, dodecanedioic acid, brassylic acid, 1,4-cyclohexanedicarboxylic acid (CHDA), and mixtures thereof.

9. Repeating unit (R ＰＡ１ ) and (R ＰＡ２ 9. Polyamide (PA) according to claim 8, in which the total proportion of (a) and (b) is at least 95.0 mol%, preferably at least 99.0 mol%, more preferably at least 99.5 mol%.

10. The repeating unit of the polyamide (PA) is the repeating unit (R ＰＡ１ ) and (R ＰＡ２ 9. Polyamide (PA) according to claim 8, consisting essentially of or consisting of:

11. The repeating unit of the polyamide (PA) is the repeating unit (R ＰＡ 8. The polyamide of claim 1, consisting essentially of or consisting of:

12. 12. Polyamide (PA) according to any one of claims 1 to 11, wherein the diacid (DI) is selected from the group consisting of isophthalic acid, adipic acid (AA), 1,4-cyclohexanedicarboxylic acid (CHDA), and combinations of two or more of said diacids, preferably the diacid (DI) is isophthalic acid.

13. The molar ratio DA1 / DA2 is 5 / 95 to 40 / 60; or 15 / 85 to 47 / 53; or 15 / 85 to 37 / 63; or 18 / 82 to 47 / 53; or 8 / 92 to 37 / 63; or ・２５／７５～３５／６５ The polyamide (PA) according to any one of claims 1 to 12,

14. The proportion of terephthalic acid in the dicarboxylic acid component (B) or the repeating unit (R ＰＡ１ 14. Polyamide (PA) according to any one of claims 1 to 13, wherein the proportion of 2,3,4-trimethylsilyl 2 ...

15. The proportion of terephthalic acid in the dicarboxylic acid component (B) or the repeating unit (R ＰＡ１ 15. Polyamide (PA) according to any one of claims 1 to 14, wherein the proportion of hydroxybenzoates is at least 87.0 mol%.

16. The proportion of the diacid (DI) other than terephthalic acid in the dicarboxylic acid component (B), or the repeating unit (R ＰＡ２ 16. Polyamide (PA) according to any one of claims 1 to 15, wherein the proportion of 20.0 mol%, preferably at most 17.0 mol%, preferably at most 15.0 mol%.

17. The proportion of the diacid (DI) other than terephthalic acid in the dicarboxylic acid component (B), or the repeating unit (R ＰＡ２ 17. Polyamide (PA) according to any one of claims 1 to 16, in which the proportion of hydroxybenzoates is at most 13.0 mol%.

18. Repeating unit (R ＰＡ *) is formed by polycondensation of a diamine component (A) and a dicarboxylic acid component (B), The diamine component (A) is a) a first diamine (DA1) selected from the group consisting of 2,2,4-trimethyl-1,6-hexanediamine (2,2,4-TMD), 2,4,4-trimethyl-1,6-hexanediamine (2,4,4-TMD), and mixtures thereof; b) a second diamine (DA2) selected from the group consisting of 1,9-nonanediamine (C9), 1,10-decanediamine (C10), and mixtures thereof; comprising, consisting essentially of, or consisting of; the proportion of the second diamine (DA2) in the diamine component (A) is 60.0 to 85.0 mol %, and the molar ratio DA1 / DA2 of the first diamine (DA1) to the second diamine (DA2) is 15 / 85 to 40 / 60; the dicarboxylic acid component (B) is a) 82.0 to 94.0 mol % terephthalic acid; b) 6.0 to 18.0 mol % of isophthalic acid; comprising, consisting essentially of, or consisting of; These proportions in mole percent are based on the total amount of diacids in dicarboxylic acid component (B); The following characteristics: a melting point Tm between 240°C and 290°C (the value of 290°C being excluded); a glass transition temperature Tg of 115°C to 135°C; (Tm and Tg are measured by differential scanning calorimetry ("DSC") according to ASTM D3418, specifically using heating and cooling rates of 20°C / min.) Optionally, a biocomponent content of at least 33.0%, preferably at least 35.0 mol%, and more preferably at least 37.0% (Biocomponent content is expressed as the % of organic carbon derived from renewable resources as measured in accordance with ASTM D6866-22); A polyamide (PA), in particular a polyamide (PA) according to any one of claims 1 to 17, which exhibits

19. The repeating units are the following proportions of repeating units (R ＰＡ１ ) and (R ＰＡ２ ): 82.0 to 94.0 mol% of (R ＰＡ１ ) 【Chemistry 2】 6.0 to 18.0 mol% of (R ＰＡ２ ) 【Chemistry 3】 (In the formula, ・R １ teeth, a) a first diamine (DA1) selected from the group consisting of 2,2,4-trimethyl-1,6-hexanediamine (2,2,4-TMD), 2,4,4-trimethyl-1,6-hexanediamine (2,4,4-TMD), and mixtures thereof; b) a second diamine (DA2) selected from the group consisting of 1,9-nonanediamine (C9), 1,10-decanediamine (C10), and mixtures thereof; is a divalent radical of a diamine corresponding to the combination of the molar ratio DA1 / DA2 of the first diamine (DA1) to the second diamine (DA2) is 15 / 85 to 40 / 60; The proportion of repeating units derived from DA2 is 60.0 to 85.0 mol %. and having the following characteristics: a melting point Tm between 240°C and 290°C (the value of 290°C being excluded); a glass transition temperature Tg of 115°C to 135°C; (Tm and Tg are measured by differential scanning calorimetry ("DSC") according to ASTM D3418, specifically using heating and cooling rates of 20°C / min.) Optionally, a biocomponent content of at least 33.0%, preferably at least 35.0 mol%, and more preferably at least 37.0% (Biocomponent content is expressed as the % of organic carbon derived from renewable resources as measured in accordance with ASTM D6866-22); A polyamide (PA), in particular a polyamide (PA) according to any one of claims 1 to 18, which exhibits

20. 20. Polyamide (PA) according to any one of claims 1 to 19, exhibiting a biocomponent content of at least 30.0%, preferably at least 33.0%, preferably at least 35.0 mol%, more preferably at least 36.0%, even more preferably at least 37.0%, even more preferably at least 38.0%, even more preferably at least 39.0%, even more preferably at least 40.0%, and more preferably at least 45.0%, wherein the biocomponent content is expressed as % of organic carbon derived from renewable resources as measured according to ASTM D6866-22.

21. 21. Polyamide (PA) according to any one of claims 1 to 20, prepared from bio-based 1,9-nonanediamine (C9) and / or 1,10-decanediamine (C10), in particular from bio-based 1,9-nonanediamine (C9) and / or 1,10-decanediamine (C10) exhibiting a bio-component content of at least 99.0%, preferably at least 99.5%, preferably at least 99.9%, wherein the bio-component content is expressed as % of organic carbon derived from renewable resources, measured according to ASTM D6866-22.

22. 22. Polyamide (PA) according to any one of claims 1 to 21, exhibiting a melting point Tm of at least 238°C, preferably at least 240°C, preferably at least 250°C, or at least 260°C, wherein Tm is measured by differential scanning calorimetry ("DSC") according to ASTM D3418, in particular using a heating and cooling rate of 20°C / min.

23. Polyamide (PA) according to any one of claims 1 to 22, exhibiting a melting point Tm of at most 300°C or at most 290°C, Tm being measured by differential scanning calorimetry ("DSC") according to ASTM D3418, in particular using a heating and cooling rate of 20°C / min.

24. Polyamide (PA) according to any one of claims 1 to 23, which exhibits a melting point Tm strictly below (<290°C) or between 238°C and 280°C, Tm being measured by differential scanning calorimetry ("DSC") according to ASTM D3418, in particular using a heating and cooling rate of 20°C / min.

25. Polyamide (PA) according to any one of claims 1 to 24, which is semi-crystalline.

26. 26. Polyamide (PA) according to any one of claims 1 to 25, exhibiting a heat of fusion Hm of at least 30.0 J / g, preferably at least 35.0 J / g, Hm being measured by differential scanning calorimetry ("DSC") according to ASTM D3418, in particular using a heating and cooling rate of 20°C / min.

27. 27. Polyamide (PA) according to any one of the preceding claims, exhibiting a glass transition temperature (Tg) of at least 100°C, preferably at least 105°C, preferably at least 110°C, preferably at least 115°C, preferably at least 120°C, wherein Tg is measured by differential scanning calorimetry ("DSC") according to ASTM D3418, in particular using a heating and cooling rate of 20°C / min.

28. The following characteristics: a melting point Tm of 240°C to 300°C, preferably 240°C to 290°C (the value of 290°C being excluded); a glass transition temperature Tg of at least 115°C, preferably at least 120°C; (Tm and Tg are measured by differential scanning calorimetry ("DSC") according to ASTM D3418, specifically using heating and cooling rates of 20°C / min.) A biocomponent content of at least 30.0%, preferably at least 33.0%, preferably at least 35.0 mol%, more preferably at least 37.0%, more preferably at least 40.0%, and even more preferably at least 45.0% (Biocomponent content is expressed as the % of organic carbon derived from renewable resources as measured in accordance with ASTM D6866-22); Polyamide (PA) according to any one of claims 1 to 27, which exhibits:

29. The following characteristics: a melting point Tm of 240°C to 300°C; a glass transition temperature Tg of at least 120°C; (Tm and Tg are measured by differential scanning calorimetry ("DSC") according to ASTM D3418, specifically using heating and cooling rates of 20°C / min.) A biocomponent content of at least 33.0%, preferably at least 35.0%, more preferably at least 37.0%, even more preferably at least 40.0%, and more preferably at least 45.0% (Biocomponent content is expressed as the % of organic carbon derived from renewable resources as measured in accordance with ASTM D6866-22); Polyamide (PA) according to any one of claims 1 to 28, which exhibits:

30. Inequality of Equation 1 (eq. 1), preferably Equation 2 (eq. 2): Tm / Tg<-0.0372×Tg(℃)+6.8402(eq.1) Tm / Tg<-0.0372×Tg(℃)+6.8002(eq.2); The melting point Tm and the glass transition temperature Tg are expressed as follows: Polyamide (PA) according to any one of claims 1 to 29, wherein Tm and Tg are measured by differential scanning calorimetry ("DSC") according to ASTM D3418, in particular using heating and cooling rates of 20°C / min.

31. The end group of the polyamide (PA) is -NH ２ 31. Polyamide (PA) according to any one of claims 1 to 30, wherein the end groups are selected in the group consisting of -COOH and amide end groups of formula -NH-C(=O)-R, where R is an alkyl, aryl or cycloalkyl group, and / or of formula -C(=O)-NH-R', where R' is an alkyl or cycloalkyl group.

32. Polyamide (PA) according to any one of claims 1 to 31, exhibiting an intrinsic viscosity (IV) of 0.50 to 1.70 dL / g, IV measured according to ASTM D5336-22 using a phenol / trichloroethylene mixture (60 / 40 by weight).

33. IV is, ・0.70-1.00dL / g; 0.80 to 1.00 dL / g; or 1.00 to 1.50 dL / g; or ・1.05-1.25dL / g 33. Polyamide (PA) according to claim 32, wherein

34. The water absorption rate of the sample at 135°C for 200 hours is less than 5.0% (≦5.0%), and the water absorption rate at 135°C for 200 hours is determined by the following steps: (i) preparing three samples molded in the shape of an ISO 527 Type IA tensile test bar in a dry state (water content less than 0.2 wt.%); (ii) immersing the three samples in deionized water at 135°C for 200 hours; (iii) determining the water absorption rate of each sample using the following formula: [Equation 1] (In the formula, W ｂｅｆｏｒｅ is the weight of the original dry sample, and W ａｆｔｅｒ is the weight of the sample at the end of step (ii); (iv) calculating the water absorption as the arithmetic mean of the three water absorptions determined for the three samples; Polyamide (PA) according to any one of claims 1 to 33, determined by a method comprising:

35. A sample exhibiting an IV retention of at least 90.0%, preferably at least 95.0%, wherein the IV retention is determined by the following steps: (i) providing a sample molded in the shape of an ISO 527 Type IA tensile test bar in a dry state (water content less than 0.2 wt.%); (ii) immersing the sample in deionized water at 135°C for 200 hours; (iii) determining the IV retention of the sample by the following formula: IV retention rate = IV ａｆｔｅｒ / IV ｂｅｆｏｒｅ ×100 (In the formula, IV ｂｅｆｏｒｅ and IV ａｆｔｅｒ is the intrinsic viscosity of the sample before and after the test) Polyamide (PA) according to any one of claims 1 to 34, determined by a method comprising:

36. Polyamide (PA) according to any one of claims 1 to 35, wherein DA2 is 1,9-nonanediamine or DA2 is 1,10-decanediamine.

37. Polyamide (PA) according to any one of claims 1 to 36, which does not contain repeat units derived from hexamethylenediamine or bis(aminoalkyl)cyclohexanediamine or lactam or amino acid.

38. 38. A process for the preparation of a polyamide according to any one of claims 1 to 37, which consists in heating a reaction mixture (RM) comprising all the monomers (DA1, DA2, terephthalic acid and DI) in the presence of less than 60% by weight, preferably less than 30% by weight, preferably less than 20% by weight, preferably less than 10% by weight of water, preferentially without the addition of water.

39. A thermoplastic composite (TPC), comprising: a polymer matrix comprising or consisting of (i) a polyamide (PA) according to any one of claims 1 to 37, and (ii) optionally at least one plastics additive; and - Fibers embedded in a polymer matrix; A thermoplastic composite (TPC) comprising:

40. 40. The thermoplastic composite of claim 39, wherein the fibers are 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.

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