Polyamide comprising 9t units

Abstract

The invention relates to a polyamide (PA) having at least 50.0 mol% (of recurring units (RPA) formed from the condensation of a diamine component (A) and a dicarboxylic acid component (B), wherein the diamine component (A) consists of: at least 30.0 mol% of 1,9- nonanediamine (C9) of formula 2HN-(CH2)9-NH2; less than 1.0 mol%, preferably less than 0.5 mol% of 2-methyl-1,8-octanediamine; optionally one or more additional diamines and the dicarboxylic acid component (B) consists of at least 30.0 mol% of terephthalic acid; optionally at least one dicarboxylic acid of formula (II) HOOC-R2-COOH, different from terephthalic acid, where R2 is a C1-C16 divalent radical; and wherein polyamide (PA) comprises end-groups of formula –NH2 and / or –COOH and end-groups of formula (III) – C(=O)-NR3-(CH2)x-NR4R5, where x is an integer of from 1 to 10; R3, R4 and R5 are H or CH3, respectively and at least one of R3, R4 and R5 is CH3.

Description

POLYAMIDE COMPRISING 9T UNITSThis application claims priority of US provisional application N°63 / 550,922 filed on 7 February 2024 and European patent application N°24177586.5 filed on 23 May 2024, the content of which being entirely incorporated herein by reference for all purposes. In case of any incoherency between this application and one of the priority applications that would affect the clarity of a term or expression, it should be made reference to this application only.[TECHNICAL FIELD]

[0001] The present invention relates to a polyamide (PA) comprising 9T units, to a polyamide composition (PC) comprising said polyamide (PA) and to a process of preparation of said polyamide (PA).[BACKGROUND ART]

[0002] GB 1070416 (British Nylon Spinners) discloses a process for the manufacture of PPAs having a particular range of inherent viscosity by polycondensation of TPA and polymethylene diamine containing 7 to 16 carbon atoms, such as heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, etc. in the presence of an acid stabilizer.

[0003] US 5,670,608 (Kuraray Co. Ltd.) discloses a polyamide 9T (PA9T) comprising TPA and 1,9-nonanediamine as major components with a specific amount of 2- methyl-l,8-octanediamine. Said PA9T is characterized in having at least 10% of the terminal groups blocked and having excellent heat resistance, low water absorption and chemical resistance, as well as good dimensional stability.

[0004] US 2003 / 050376 (Kuraray Co. Ltd.) discloses a semi-aromatic polyamide comprising dicarboxylic acid units mainly composed of aromatic dicarboxylic acid units and diamine units mainly composed of aliphatic diamine units having 4 to 14 carbon atoms containing a particular range of terminal amino groups, characterized by good heat aging characteristics suited for various articles used at a high temperature environment, such as engine parts of an automobile. There is no disclosure of the presence of a molecule of formula (I) in DI.

[0005] CN 102701991 describes a process of preparation of 1,9-nonanediamine.

[0006] WO 2024 / 061921 (published 28 March 2024) discloses copolyamides with 9T units based on the use of a biobased nonanediamine. There is no information about the end-groups of the copolyamide.

[0007] CN 112920400 discloses copolyamides with 9T units.

[0008] WO 2024 / 061921 discloses a biobased polyamide but there is no mention of the specific end-groups of claim 1 in said application.

[0009] A polyamide is a family of polymers that frequently has been used as engineering plastics for a very wide range of applications. A polyamide composition is of significant commercial interest and may be used to produce automobile or electrical components, generally by injection molding, in view of weight reduction, ease in assembling parts and also its design flexibility.

[0010] Notably, the polyamides as represented by polyamide 6 (PA6) and polyamide 66 (PA66) have been widely used for various industrial uses, particularly as engineering plastics. Due to relatively low thermal stability mainly originated from their vulnerability to water absorption, however, there has been increasing demand for the development of a polyamide having better thermal stability and dimensional stability without compromising with other performances such as mechanical properties.

[0011] Certain applications require a polyamide composition which is capable of exhibiting excellent mechanical properties after thermal aging and a minimum distortion during injection molding. To meet such requirements, polyphthalamides (PPAs) formed from the reaction of at least aromatic dicarboxylic acids with aliphatic diamines were proposed. PPA may be semi-crystalline or amorphous depending on the actual combination of monomers used, among which semicrystalline PPAs are mostly based on polyamide 6T (PA6T) formed from the reaction of terephthalic acid (TP A) and 1,6-hexan ediamine, which has been known to have relatively low moisture absorption, good dimensional stability and excellent chemical resistance. Nonetheless, there exists a drawback of PA6T, i.e. high melting point which exceeds the decomposition point of the polyamide and hence cannot be easily melt molded. Accordingly, several approaches were made toproduce different aromatic polyamides via modification of monomers so as to decrease the melting temperature, without reducing the rate of crystallization which may result in the deterioration of other properties, such as rigidity under high temperatures, chemical resistance and dimensional stability.

[0012] In addition, biobased polymers are more and more sought after.

[0013] The polyamide of the invention aims at solving this technical problem.

[0014] These definitions apply to the present disclosure.

[0015] wt.% is a percentage by weight. Mol.% is a percentage by mole.

[0016] Unless otherwise stated, the proportions of recurring units in the polyamide are given in mol% and relative to the total proportion of recurring units in the polyamide.

[0017] When numerical ranges are given herein, unless otherwise indicated, the end-points of the ranges (even the open-ended ranges such as those comprising "at least", "at most", "lower than", etc) are included.

[0018] In the present application, unless otherwise indicated, any specific embodiment or technical feature relating to a subject-matter is applicable to another embodiment or technical feature of the same subject-matter or to another subject-matter.

[0019] The proportions of diamines in the diamine component (A) are based on the total amount of diamines in the diamine component (A). The proportions of carboxylic diacids in the dicarboxylic acid component (B) are based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B).

[0020] The proportions of recurring units in polyamide (PA) are expressed in mol% and are based on the total amount of recurring units in the polyamide (PA).

[0021] As used herein, the terminology ‘(Cn-Cm)’ in reference to an organic group, such as an alkyl wherein n and m are integers, respectively, indicates that the group may contain from n carbon atoms to m carbon atoms per group, n and m being included.

[0022] An hydrocarbon group is an organic group comprising only atoms of carbon and atoms of hydrogen.

[0023] A semi-crystalline polyamide is a polyamide which exhibits a heat of fusion (Hm) of at least 5.0 Joules per gram (J / g) measured by differential scanning calorimetry(DSC) according to ASTM D3418 at a heating rate of 20° C / min. An amorphous polyamide is a polyamide which exhibits a heat of fusion of less than 5.0 J / g, preferably of less than 3.0 J / g, and more preferably of less than 2.0 J / g as measured using DSC according to ASTM D3418 at a heating rate of 20 °C / min.

[0024] A dicarboxylic acid is an organic compound containing two carboxyl groups (-COOH).[SUMMARY]

[0025] The invention is set out in the appended claims.

[0026] The invention relates to a polyamide (PA) according to any one of claims 1-19.

[0027] The invention also relates to the process of preparation of polyamide (PA) as defined in claim 20.

[0028] The invention also relates to a polymer composition (PC) as defined in claim 21.

[0029] A first aspect of the present invention is directed to a polyamide (PA), the recurring units of which consist of:- at least 50.0 mol% (of recurring units (RPA) formed from the condensation of a diamine component (A) and a dicarboxylic acid component (B);- less than 50.0 mol% of recurring units (RPA*) of formula (II) (-NH-Alk- C(=O)-) derived from at least one lactam and / or at least one aminoacid where Aik designates a linear alkylene group; wherein:- the diamine component (A) consists of:■ at least 30.0 mol% of 1,9-nonanediamine (C9) of formula 2HN- (CH2)9-NH2;■ less than 1.0 mol%, preferably less than 0.5 mol% of 2-methyl- 1,8-octanediamine;■ optionally one or more additional diamines according to one of the two following embodiments: o according to a 1stembodiment, at least one diamine of formula (I) H2N-R1-NH2, where Ri is a C2-C20 divalent radical, different from the divalent radical derived from1.9-diaminononane, 1,10-diaminodecane and 2-methyl- 1,8-diaminooctane; o according to a 2ndembodiment, 1,10-diaminodecane in combination with at least one diamine of formula (I) H2N- R1-NH2, where Ri is a C2-C20 divalent radical, different from the divalent radical derived from 1,9-diaminononane,1.10-diaminodecane and 2-m ethyl- 1,8-diaminooctane;■ these proportions in mol% being based on the total amount of diamines in the diamine component (A);- the dicarboxylic acid component (B) consists of■ at least 30.0 mol% of terephthalic acid;■ optionally at least one dicarboxylic acid of formula (II) HOOC- R2-COOH, where R2 is a C1-C16 divalent radical, different from terephthalic acid;■ these proportions in mol% being based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B); and wherein polyamide (PA) comprises (i) end-groups of formula -NH2 and / or - COOH and (ii) end-groups of formula (III) -C(=O)-NR3-(CH2)x-NR4Rs, where x is an integer of from 1 to 10; R3, R4 and Rs are H or CH , respectively and at least one of R3, R4 and Rs is CH3.

[0030] A second aspect of the present invention is directed to a polymer composition (PC) comprising:(a) from 30.0 wt% to 100 wt% of at least one polyamide (PA) as disclosed herein;(b) from 0 wt% to 70.0 wt% of at least one reinforcing agent (RA); and(c) from 0 wt% to 30.0 wt% of at least one polymer additive (Add) different from RA, these proportions in wt% being relative to the total weight of the polymer composition (PC).

[0031] A third aspect of the present invention is directed to a process of preparation of a polyamide, notably polyamide (PA), by polycondensation of a monomer mixture (MM), comprising heating a reaction mixture (RM) which comprises or consists of:(a) a monomer mixture (MM) consisting of 1,9-nonanediamine (C9) and all the other monomers (if any) constituting the polyamide;(b) at least one diamine (DA) of formula (IV) NHR3-(CH2)x-NR4Rs; and(c) optionally a catalyst, notably selected in the group of phosphorous based compounds;(d) optionally water;(e) optionally at least one end-capping agent selected in the group consisting of end-capping agents of formula G-COOH, G-NH2 and combination thereof, G being a C1-C16 hydrocarbon group, preferably a C1-C12 hydrocarbon group, preferably a C1-C7 hydrocarbon group; wherein the proportion of diamine (DA) is between 0.01 and 2.50 mol%, this proportion in mol% being expressed relative to the content of 1,9-nonanediamine (C9).

[0032] A fourth aspect of the present invention pertains to an article or a thermoplastic composite comprising the polyamide (PA) or the polyamide composition (PC) as defined herein.

[0033] Details and precisions about all these subject-matters are now given below.[DETAILED DESCRIPTION OF THE INVENTION]

[0034] Polyamide (PA)

[0035] The recurring units of polyamide (PA) consist of recurring units (RPA) and (RPA*) (if any). The recurring units of polyamide (PA) are linked to one another by amide bonds.

[0036] Recurring units (RPA)

[0037] Recurring units (RPA) are formed from the condensation of the diamine component (A) and the dicarboxylic acid component (B). Those units are represented by formula (I) (-NH-Rai-NH-C(=O)-Ra2-C(=O)-) where Raiand Ra2 are the divalent radicals derived from respectively a diamine of formula 2HN-Rai-NH2 and the dicarboxylic acid of formula HOC(=O)-Ra2-C(=O)OH. For instance, the 9T units present in polyamide (PA) are of formula -NH-(CH2)9-NH-C(=O)-p-phenyl- C(=O)-, so that Raiis the alkylene group of formula -(CH2)9- and Ra2 is the paraphenylene group.

[0038] The proportion of (RPA) in polyamide (PA) is at least 50.0 mol% (> 50.0 mol%). The proportion of recurring units (RPA) is preferably at least 60.0 mol%, preferably at least 90.0 mol%, preferably at least 95.0 mol%, preferably at least 99.0 mol%. According to a preferred embodiment of the present disclosure, the recurring units of polyamide (PA) consist of the recurring units (RPA).

[0039] Details are now given about the diamine component (A) and the dicarboxylic acid component (B) that form those recurring units (RPA).

[0040] Diamine component (A)

[0041] The diamine component (A) consists of:■ at least 30.0 mol% of 1,9-nonanediamine (C9) of formula 2HN-(CH2)9-NH2;■ less than 1.0 mol%, preferably less than 0.5 mol% of 2-methyl-l,8- octanediamine, preferably less than 0.10 mol% of 2-methyl-l,8- octanediamine;■ optionally one or more additional diamines according to one of the two following embodiments: o according to a 1stembodiment, at least one diamine of formula (I) H2N-R1-NH2, where Ri is a C2-C20 divalent radical, different from the divalent radical derived from 1,9-diaminononane, 1,10- diaminodecane and 2-methyl-l,8-diaminooctane; o according to a 2ndembodiment, 1 , 10-diaminodecane in combination with at one least one diamine of formula (I) H2N-R1-NH2, where Ri is a C2-C20 divalent radical, different from the divalent radical derived from 1,9-diaminononane, 1,10-diaminodecane and 2- methyl-l,8-diaminooctane; o with the proviso that the proportion of diamine(s) of formula (I) in the diamine component (A), if present, is strictly higher than 1.0 mol% (> 1.0 mol%);■ these proportions in mol% being based on the total amount of diamines in the diamine component (A).

[0042] According to the 1stembodiment, the diamine component (A) consists of C9 and optionally at least one diamine of formula (I) H2N-R1-NH2, where Ri is a C2-C20 divalent radical which is different from the divalent radical derived from 1,9-diaminononane, 1,10-diaminodecane and 2-methyl-l,8-diaminooctane with the proviso that the proportion of diamine(s) of formula (I) in the diamine component (A), if present, is strictly higher than 1.0 mol% (> 1.0 mol%). To be clear, R1 is therefore not -NH-(CH2)9-NH- nor -NH-(CH2)IO-NH- nor -NH-CH2-CHMe- (CH2)e-NH. According to this embodiment, the diamine component (A) contains at least 2 diamines and the proportion of diamine(s) of formula (I) is > 1.0 mol%.

[0043] According to the 2ndembodiment, the diamine component (A) consists of C9, 1,10- diaminodecane (of formula NH2-(CH2)IO-NH2) and at one least one diamine of formula (I) H2N-RI-NH2, where Ri is a C2-C2o divalent radical, different from the divalent radical derived from 1,9-diaminononane, 1,10-diaminodecane and 2- methyl-l,8-diaminooctane, with the proviso that the proportion of diamine(s) of formula (I) in the diamine component (A), if present, is strictly higher than 1.0 mol% (> 1.0 mol%). According to this embodiment, the diamine component (A) contains at least 3 diamines and the proportion of diamine(s) of formula (I) is > 1.0 mol%.

[0044] The proportion of C9 in the diamine component (A) is at least 30.0 mol%. It is preferably at least 50.0 mol%.

[0045] The proportion of 2-methyl-l,8-octanediamine is between 0 mol% and 1.0 mol%.

[0046] According to an embodiment, the diamine component (A) consists of:■ 1,9-nonanediamine (C9) of formula2HN-(CH2)9-NH2;■ less than 1.0 mol%, preferably less than 0.5 mol% of 2-methyl-l,8- octanediamine preferably less than 0.10 mol% of 2-methyl-l,8- octanediamine.

[0047] Additional diamine (optional)

[0048] The diamine component (A) may comprise one or more additional diamines different from C9 and 2-methyl-l,8-octanediamine according to one of the two following embodiments.

[0049] According to a 1stembodiment, the additional diamine is at least one diamine of formula (I) H2N-RI-NH2, where Ri is a C2-C2o divalent radical, different from the divalent radical derived from 1,9-diaminononane, 1,10-diaminodecane and 2- methyl-l,8-diaminooctane. The diamine component (A) then consists of at least 30.0 mol% of 1,9-nonanediamine (C9); less than 1.0 mol%, preferably less than 0.5mol% of 2-methyl-l,8-octanediamine and at least one diamine of formula (I). The diamine component (A) may consist of at least 30.0 mol% of 1,9-nonanediamine (C9); less than 1.0 mol%, preferably less than 0.5 mol% of 2-methyl-l,8- octanediamine and one diamine of formula (I), the proportion of which is strictly higher than 1.0 mol% (> 1.0 mol%). The diamine component (A) may consist of at least 30.0 mol% of 1,9-nonanediamine (C9); less than 1.0 mol%, preferably less than 0.5 mol% of 2-methyl-l,8-octanedi amine and two or more diamines of formula (I), the proportion of these diamines of formula (I) being strictly higher than 1.0 mol% (> 1.0 mol%). 1,10-diaminodecane is the diamine of formula 2HN-(CH2)IO- NH2.

[0050] According to a 2ndembodiment, the additional diamine is the combination of 1,10- diaminodecane and at least one diamine of formula (I) H2N-R1-NH2, where Ri is a C2-C20 divalent radical, different from the divalent radical derived from 1,9- diaminononane, 1,10-diaminodecane and 2-methyl-l,8-diaminooctane. The diamine component (A) then consists of at least 30.0 mol% of 1,9-nonanediamine (C9); less than 1.0 mol%, preferably less than 0.5 mol% of 2-methyl-l,8- octanediamine; 1,10-diaminodecane and at least one diamine of formula (I). The diamine component (A) may consist of at least 30.0 mol% of 1,9-nonanediamine (C9); less than 1.0 mol%, preferably less than 0.5 mol% of 2-methyl-l,8- octanediamine; 1,10-diaminodecane and one diamine of formula (I), the proportion of which is strictly higher than 1.0 mol% (> 1.0 mol%). The diamine component (A) may consist of at least 30.0 mol% of 1,9-nonanediamine (C9); less than 1.0 mol%, preferably less than 0.5 mol% of 2-methyl-l,8-octanediamine; 1,10- diaminodecane and two or more diamines of formula (I), the proportion of these diamines of formula (I) being strictly higher than 1.0 mol% (> 1.0 mol%).

[0051] Ri may notably be selected from the group consisting of a linear or branched C2- Cis alkylene group different from -(CH2)9, -(CH2)io- and -(CH2)e-CHMe-CH2-; a C6-C30 cycloalkylene group; a C6-C30 arylene group; the divalent radical of 1,3- BAC, 1,4-BAC, MACM, PACM, IPDA, MXDA and PXDA which are the diamines of respectively formula:

[0052] The diamine of formula (I) may more particularly be selected in the group consisting of:- the diamines of formula 2HN-Alk-NH2 where Aik is a linear or branched C2-C18 alkylene group different from -(CH2)9-, -(CH2)IO- and -(CH2)e-CHMe-CH2-;1,3-BAC; 1,4-BAC; MACM; PACM, IPDA, MXDA, PXDA and combination thereof.

[0053] For both embodiments, the proportion of the additional diamine(s) in the diamine component (A) (if any) is strictly higher than 1.0 mol% (> 1.0 mol%).

[0054] The diamine of formula (I) is preferably not 2,2,4-trimethyl-l,6-hexanediamine (2,2,4-TMD), 2,4,4-trimethyl-l,6-hexanediamine (2,4,4-TMD) or a mixture of 2,2,4-TMD and 2,4,4-TMD.

[0055] Dicarboxylic acid component (B)

[0056] The dicarboxylic acid component (B) consists of■ at least 30.0 mol% of terephthalic acid;■ optionally at least one dicarboxylic acid of formula (II) HOOC-R2-COOH, different from terephthalic acid, where R2 is a C1-C16 divalent radical;■ these proportions in mol% being based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B);

[0057] R.2 may notably be selected from the group consisting of a linear or branched Ci- Ci6 linear or branched alkylene group; a Ce-Cio cycloalkylene group; a Ce-Cio arylene group different from para-phenylene.

[0058] The dicarboxylic acid of formula (II) may be more particularly selected in the group consisting of the diacids of formula HOOC-Alk-COOH where Aik is a linear or branched Ci-Cie linear or branched alkylene group; isophthalic acid; 1,4- cyclohexane dicarboxylic acid, 2,5-pyridinedicarboxylic acid, 2,4- pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, 2,2-bis(4-carboxyphenyl) propane, bis(4-carboxyphenyl) methane, 2,2-bis(4-carboxyphenyl) hexafluoropropane, 2,2-bis(4-carboxyphenyl) ketone, 4,4’-bis(4-carboxyphenyl) sulfone, 2, 2-bis(3 -carboxyphenyl) propane, bis(3-carboxyphenyl) methane, 2,2- bis(3-carboxyphenyl) hexafluoropropane, 2,2-bis(3-carboxyphenyl) ketone, bis(3- carb oxy phenoxy) benzene, naphthalene dicarboxylic acids, including 2,6- naphtahlene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,4-naphtalene dicarboxylic acid, 2,3-naphtalene dicarboxylic acid, 1,8 -naphthalene dicarboxylic acid and combination thereof.

[0059] The dicarboxylic acid of formula (II) may be more particularly selected in the group consisting of the diacids of formula HOOC-Alk-COOH where Aik is a linear or branched C1-C16 linear or branched alkylene group; isophthalic acid; 1,4- cyclohexane dicarboxylic acid and combination thereof.

[0060] The diacids may be selected in the group consisting of malonic acid, succinic acid, glutaric acid, adipic acid, 2,2-dimethyl-glutaric acid, 2,4,4-trimethyl adipic acid, pimelic acid, suberic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, 1,14-tetradecanedioic acid, 1,15-pentadecanedioic acid, 1,16-hexadecanedioic acid, 1,18-octadecanedioic acid and combination thereof.

[0061] The dicarboxylic acid of formula (II) may be any one of the diacid given in one of the lists above.

[0062] The proportion of terephthalic acid may be between 30.0 mol% and 100.0 mol%.

[0063] As the diamine component (A) contains 1,9-nonanediamine and the dicarboxylic acid component (B) contains terephthalic acid, polyamide (PA) comprises 9T recurring units of formula -NH-(CH2)9-NH-C(=O)-p-phenyl-C(=O)-.

[0064] According to an embodiment, the proportion of 9T units in polyamide (PA) is at least 50.0 mol%, preferably at least 60.0 mol%, preferably at least 80.0 mol%, preferably at least 90.0 mol%, preferably at least 95.0 mol%, preferably at least 99.0 mol%.

[0065] According to an embodiment, the proportion of 9T units in polyamide (PA) is between 50.0 mol% and 100 mol%, preferably between 80.0 mol% and 100 mol%.

[0066] According to an embodiment, the proportion of 9T units in polyamide (PA) is < 90.0 mol%, more particularly < 85.0 mol%.

[0067] According to an embodiment, the proportion of 9T units in polyamide (PA) is between 50.0 and 90.0 mol% (this value of 90.0 mol% not being included) or between 50.0 and 85.0 mol%.

[0068] According to an embodiment of the present disclosure, polyamide (PA) is a polyamide, the recurring units of which consist essentially of 9T units. The expression "consist essentially" means in the context of the recurring units that the recurring units consist of 9T units and up to 1.5 mol%, preferably up to 1.0 mol%, preferably up to 0.5 mol% of units different from 9T units.

[0069] According to an embodiment, polyamide (PA) is a homopolyamide with only 9T units.

[0070] According to another embodiment, polyamide (PA) is not (i) a polyamide of composition 9T / 9I or of composition 9T / 9.12 or of composition 9T / 6, where the proportion of 9T units in said polyamide is > 85.0 mol% or (ii) a polyamide derived from the condensation of a diamine component comprising 1,9-diaminononane (9) and 1,6-diaminohexane (6) and a dicarboxylic component comprising terephthalic acid (T) and decanedioic acid (10). For clarity, I designates isophthalic acid, 9.12 designates the recurring unit derived from the condensation of 1,9-diaminoamine and dodecanoic diacid and 6 designates caprolactam.

[0071] According to another embodiment, polyamide (PA) is not (i) a polyamide of composition 9T / 9I or of composition 9T / 9.12 or of composition 9T / 6 or (ii) a polyamide derived from the condensation of a diamine component comprising 1,9- diaminononane (9) and 1,6-diaminohexane (6) and a dicarboxylic component comprising terephthalic acid (T) and decanedioic acid (10). For clarity, I designatesisophthalic acid, 9.12 designates the recurring unit derived from the condensation of 1,9-diaminoamine and dodecanoic diacid and 6 designates caprolactam.

[0072] Recurring units (RPA*)

[0073] Polyamide (PA) may comprise recurring units (RPA*) of formula (II) (-NH-Alk- C(=O)-) derived from at least one lactam and / or at least one aminoacid where Aik designates a linear alkylene group. As can be seen, those units are different from units (RPA).

[0074] In formula (II), Aik designates an alkylene group of formula -(CH2)n- where n is an integer from 6 to 12.

[0075] According to an embodiment, recurring units (RPA*) are derived from a monomer selected in the group of 6-amino-hexanoic acid, 9-aminononanoic acid, 10- aminodecanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, azetidinone, pyrrolidone, piperidone, caprolactam, dodecane- 12-lactam and combination thereof. According to an embodiment, recurring units (RPA*) are derived from a monomer selected in the group of 11-aminoundecanoic acid, 12- aminododecanoic acid, caprolactam, dodecane- 12-lactam and combination thereof. According to an embodiment, (RPA*) are derived from 11-aminoundecanoic acid. According to an embodiment, (RPA*) are derived from dodecane- 12 -lactam.

[0076] The proportion of (RPA*) in polyamide (PA) is at most 50.0 mol% (< 50.0 mol%). The proportion of recurring units (RPA*) is preferably at most 40.0 mol%, preferably at most 10.0 mol%, preferably at most 5.0 mol%.

[0077] The polyamide having recurring units (RPA) formed from a diamine component (A) having the following composition is preferably excluded:- between 15.0 mol% and 25.0 mol% of 1,6-diaminohexane;- between 18.0 mol% and 30.0 mol% of a diamine selected in the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines;- between 50.0 mol% and 64.0 mol% of a diamine selected in the group consisting of l,3-bis(aminomethyl)cyclohexane, l,4-bis(aminomethyl)cyclohexane and a combination of said two diamines.

[0078] The polyamide having recurring units (RPA) formed from a diamine component (A) having the following composition is preferably excluded:- between 38.0 mol% and 54.0 mol% of 1,6-diaminohexane;- between 15.0 mol% and 40.0 mol% of a diamine selected in the group consisting of 1,9-diaminononane, 1,10-diaminodecane and a combination of said two diamines;- between 15.0 mol% and 40.0 mol% of a diamine selected in the group consisting of l,3-bis(aminomethyl)cyclohexane, l,4-bis(aminomethyl)cyclohexane and a combination of said two diamines.

[0079] The following polyamides are preferably excluded:- polyamide (PAI): having 100 mol% of recurring units formed from the condensation of a diamine component having 20 mol% of 1,6-diaminohexane; 20 mol% of 1,9-nonanediamine and 63 mol% of 1,3-BAC and a dicarboxylic acid component having 100 mol% of terephthalic acid;- polyamide (PA2): having 100 mol% of recurring units formed from the condensation of a diamine component having 50 mol% of 1,6-diaminohexane; 20 mol% of 1,9-nonanediamine and 30 mol% of 1,3-BAC and a dicarboxylic acid component having 100 mol% of terephthalic acid;- polyamide (PA3): having 100 mol% of recurring units formed from the condensation of a diamine component having 45 mol% of 1,6-diaminohexane; 35 mol% of 1,9-nonanediamine and 20 mol% of 1,3-BAC and a dicarboxylic acid component having 100 mol% of terephthalic acid.

[0080] End-groups of polyamide (PA)

[0081] Polyamide (PA) comprises (i) end-groups of formula -NH2 and / or -COOH and (ii) end-groups of formula (III) -C(=O)-NR3-(CH2)X-NR4R5, where x is an integer of from 1 to 10; R3, R4 and Rs are H or CH3, respectively and at least one of R3, R4 and Rs is CH3.

[0082] The end-groups of formula (III) present in polyamide (PA) stem from the presence of at least one diamine (DA) in the reaction mixture (RM) used for preparing polyamide (PA).

[0083] Said diamine (DA) may be present in the C9 diamine used or may be commercially available.

[0084] According to an embodiment, R3 = H and R4 & Rs = CH3.

[0085] According to another embodiment, R3, R4, Rs = CH3.

[0086] x is more particularly an integer from 6 to 10. x may take any value between 1 and 10 or between 6 and 10.

[0087] According to an embodiment, the proportion of end-groups of formula (III) is < 50.0 peq / g. This total proportion is typically at least 0.10 peq / g, more particularly at least 0.50 peq / g, more particularly at least 1.00 peq / g. This total proportion is typically between 0.10 peq / g and 50.0 peq / g or between 0.10 peq / g and 20.0 peq / g or between 0.10 peq / g and 15.0 peq / g.

[0088] For clarity, polyamide (PA) may comprise end-groups according to formula (III) and different by variable x and / or substituents R3, R4, Rs. For instance, the following amide end-groups could be present in polyamide (PA): -C(=O)-NMe- (CH2)9-NHMe and -C(=O)-NH-(CH2)9-NMe2. The proportion of end-groups of formula (III) described herein therefore corresponds to the total proportion of end- groups of formula (III).

[0089] The end-groups of polyamide (PA) preferably consist essentially of or consist of:- (i) end-groups of formula -NH2 and / or -COOH;- (ii) the end-groups of formula (III) -C(=O)-NR3-(CH2)x-NR4Rs as disclosed herein; and- (iii) optionally amide end-groups of formula -NH-C(=O)-G or -C(=O)- NH-G different from -C(=O)-NR3-(CH2)x-NR4Rs and where G is a C1-C16 hydrocarbon group, preferably a C1-C12 hydrocarbon group, preferably a C1-C7 hydrocarbon group.

[0090] Analysis of polyamide (PA) of the invention

[0091] The composition of polyamide (PA), the proportions of recurring units, notably (RPA), (RPA*), and end-groups in the polyamide (PA) can be determined byJH NMR spectroscopy (to this end, it is mentioned that the end-groups -NMeH and - NMe2 typically exhibit respectively a doublet at chemical shift of -2.91 ppm and a broad singlet at -2.97 ppm) They can also be determined after digestion (hydrolysis) of the polyamide (PA) and analysis of the mixture resulting from said digestion. The analysis is performed by the usual analytical techniques available to the skilled person. Gas chromatography (GC) and / or liquid chromatography (LC) can conveniently be used for this analysis. High-performance liquidchromatography (HPLC) is a convenient analytical technique for this analysis. See ACS Sustainable Chem. Eng. 2020, 8, 31, 11818-11826.

[0092] Isolation of the monomers after digestion (hydrolysis) of the polyamide (PA) makes it also possible to determine their biocontent.

[0093] The hydrolysis of the polyamide is preferably performed in acidic conditions: the sample of polyamide is mixed with a strong acid and the mixture is heated at a temperature higher than 150°C until digestion is complete. The resulting mixture is then cooled to room temperature, diluted with a solvent and the obtained mixture is analyzed by at least one analytical method.

[0094] The conditions of hydrolysis provided in the Experimental Section can be followed.

[0095] Thermal properties of the polyamide (PA)

[0096] Polyamide (PA) may be amorphous or semi-crystalline.

[0097] In another embodiment, the polyamide (PA) has a glass transition temperature (Tg), as measured according to ASTM D3418, of at least 60°C, preferably at least 70°C, more preferably at least 80°C, and / or of at most 220°C, preferably at most 200°C, more preferably at most 180°C. In a particular embodiment, the polyamide (PA) has a glass transition temperature (Tg), as measured according to ASTM D3418, of from 60°C to 160°C, preferably from 70°C to 140°C, more preferably from 80°C to 130°C.

[0098] In one embodiment, the polyamide exhibits a heat of fusion (Hm) of at least 5.0 J / g, preferably at least 7.0 J / g, more preferably at least 10.0 J / g, and / or of at most 100.0 J / g, preferably at most 90.0 J / g, more preferably at most 80.0 J / g. The heat of fusion is generally measured according to ASDM D3418. The method disclosed in the Examples may more particularly be followed.

[0099] Polyamide (PA) preferably exhibits a melting temperature (Tm) of at least 250°C, Tm being measured by DSC according to ASTM D3418.

[0100] Tgand Tmmay more preferably be measured with the method disclosed in the Experimental Section.

[0101] Inherent viscosity (IV) and intrinsic viscosity tn)

[0102] Polyamide (PA) preferably exhibits:an intrinsic viscosity r| lower than or equal to 2.0 dL / g measured according to ASTM D789, typically with the use of a mixture phenol / 1, 1,2,2- tetrachloroethane (60 / 40 wt. ratio); and / or an inherent viscosity IV lower than or equal to 1.3 dL / g, measured according to ASTMD5225 with the use of a mixture phenol / 1, 1, 2, 2-tetrachloroethane (60 / 40 wt. ratio).

[0103] IV is preferably at least 0.70 dL / g, measured according to ASTM D5225 with the use of a mixture phenol / 1, 1,2, 2-tetrachloroethane (60 / 40 wt. ratio).

[0104] This range of viscosity is preferable for injection moulding.

[0105] Molecular weight (Mn and Mw)

[0106] Polyamide (PA) preferably exhibits:- a number-average molecular weight (Mn) lower than or equal to 30,000 g / mol; and / or- a weight-average molecular weight (Mw) lower than or equal to 60,000 g / mol.

[0107] Mnand Mware determined by Size Exclusion Chromatography (SEC) coupled to a light scattering instrument or refractive index detector calibrated with the use of polystyrene standards.

[0108] Mn may also be by using the following equation (1): Mn = 2,000,000 / [EG] (1) wherein [EG] is the proportion of end-groups in the polyamide (PA) expressed in mmol / kg.

[0109] For the SEC, l,l,l,3,3,3-hexafhioropropan-2-ol (HFIP) + 0.05 mol / L potassium trifluoroacetate can be used as a solvent.

[0110] Preparation of polyamide (PA)

[0111] Polyamide (PA) is prepared by poly condensing the monomers constituting the polyamide.

[0112] The polyamide (PA) is prepared by polycondensing a monomer mixture (MM), the process comprising heating a reaction mixture (RM) comprising, consisting essentially of or consisting of:(a) the monomer mixture (MM) consisting of 1,9-nonanediamine (C9) and all the other monomers (if any) constituting the polyamide;(b) at least one diamine (DA) of formula (IV) NHR3-(CH2)X-NR4R5 where x, R3- Rs are as defined herein;(c) optionally a catalyst, notably selected in the group of phosphorous based compounds;(d) optionally water;(e) optionally at least one end-capping agent selected in the group consisting of end-capping agents of formula G-COOH, G-NH2 and combination thereof, G being as disclosed herein.

[0113] The diamine(s) according to formula (IV) lead to the end-groups of formula (III) present in polyamide (PA).

[0114] Components (a) and (b)

[0115] The monomer mixture (MM) comprises all the monomers constituting the polyamide (PA). Thus, the monomer mixture (MM) typically comprises or consists of the diamines of the diamine component (A), the dicarboxylic acids of the dicarboxylic acid component (B) and if any, the aminoacid(s) and / or the lactam(s).

[0116] In the reaction mixture (RM), the molar ratio [-COOH] from the dicarboxylic acids of the dicarboxylic acid component (B) and from the aminoacid(s) (if any) / [-NH2] from the diamines of the diamine component (A) and from the aminoacid(s) (if any) is preferably from 0.9 to 1.1, preferably from 0.95 to 1.07, more preferably 1.00 to 1.05.

[0117] Among the diamines of the diamine component (A), the diamine 1,9- nonanediamine (C9) of formula 2HN-(CH2)9-NH2 used for the preparation of the polyamide (see Experimental Section) is also present and contains at least one diamine (DA) of formula (IV) NHR3-(CH2)X-NR4R5. The proportion of diamine (DA) is between 0.01 and 2.50 mol%, more particularly between 0.010 and 0.500 mol%, more particularly between 0.010 and 0.100 mol%, this proportion being expressed relative to the content of 1,9-nonanediamine (C9). This molar proportion can be calculated by the following formula: NHR3-(CH2)X-NR4R5 / [1,9- nonanediamine + NHR3-(CH2)X-NR4R5] xlOO. This proportion may be determined according to classical analytical techniques, such as GC (Gas Chromatography) - QTOF (Quadrupole Time-Of-Flight). For the avoidance of doubt, several diamines (DA) according to formula (IV) may be present and the proportion is then determined by reference to all diamines (DA) present. Diamine (DA) leads to the end-groups of formula (III) in the polyamide (PA).

[0001] Moreover, diamine 1,9-nonanediamine (C9) is biobased The term ‘bio-based’ means in relation to a substance X that this substance X contains carbon of renewable origin, derived from living or once-living organisms, excluding materials embedded in geological formations and / or fossilized, for instance petroleum-based ones. The diamine C9 exhibits a biocontent of at least 95.0%, preferably at least 99.0%, preferably at least 99.9%, the biocontent being expressed as the % of organic carbon of renewable origin measured according to ASTM D6866-22.

[0002] As a consequence, polyamide (PA) exhibits a bio content of at least 6.0%, the biocontent being expressed as the % of organic carbon of renewable origin measured according to ASTM D6866-22.

[0003] The biocontent determined according to ASTM D6866-22 of polyamide (PA) may be > 50.0%. The biocontent may be between 50.0% (value of 50.0% excluded) and 100%.

[0118] Component (c)

[0119] The reaction mixture (RM) may also comprise a catalyst, notably selected in the group of phosphorous based compounds. The catalyst may more particularly be selected in the group consisting of phosphoric acid, phosphorous acid, hypophosphorous acid, sodium hypophosphite, sodium hypophosphate and sodium hypophosphinate, preferably phosphorous acid and / or sodium hypophosphite. In a preferred embodiment, the phosphorous compound is phosphorous acid.

[0120] Component (d)

[0121] The reaction mixture (RM) may also comprise water. The proportion of water in the reaction mixture (RM) is typically at most 50.0 wt%, preferably a most 30.0 wt%.

[0122] Component (e)

[0123] The reaction mixture (RM) may also at least one end-capping agent selected in the group consisting of end-capping agents of formula G-COOH, G-NH2 and combination thereof, G being as disclosed herein. An end-capping agent leads to end-groups in polyamide (PA).

[0124] An example of end-capping agent is a monocarboxylic acid G-COOH, such as acetic acid.

[0125] The reaction mixture (RM) is heated at a temperature which is high enough to induce the creation of amide bonds through the polycondensation. The temperature at which the reaction mixture (RM) is heated is at least 200°C. This temperature is typically at least Tg + 50°C and / or at least Tm + 20°C, Tg and Tmbeing respectively the glass transition temperature and the melting temperature of polyamide (PA).

[0126] The conditions provided in the Experimental Section can be followed to prepare the polyamide (PA) of the invention.

[0127] Polymer composition (PC)

[0128] The polymer composition (PC) comprises:(a) from 30.0 wt% to 100 wt% of at least one polyamide (PA) as disclosed herein;(b) from 0 wt% to 70.0 wt% of at least one reinforcing agent (RA); and(c) from 0 wt% to 30.0 wt% of at least one additive (Add) different from reinforcing agent (RA), wt% being relative to the total weight of the polymer composition (PC).

[0129] Component (b) is generally blended with component (a). Likewise, component (c) is generally blended with components (a) and (b).

[0130] The components (a)-(b)-(c) are generally blended together.

[0131] The reinforcing agent (RA) is notably selected from the group consisting of mineral fillers (e.g. talc, mica, kaolin, calcium carbonate, calcium silicate, magnesium carbonate), glass fibers, carbon fibers, synthetic polymeric fibers, aramid fibers, aluminum fibers, titanium fibers, magnesium fibers, boron carbide fibers, rock wool fibers, steel fibers, natural fibers (e.g. linen, hemp or cellulose), wollastonite, glass balls (e.g. hollow glass microspheres), glass flakes and any combination of two or more thereof.

[0132] The reinforcing agent (RA) may be any one of the reinforcing agents listed herein. Carbon fibers and / or glass fibers are most advantageously used in the polyamide composition of the present invention.

[0133] According to an embodiment, the proportion of RA is at least 1.0 wt%, preferably at least 5.0 wt%, preferably at least 10.0 wt% and / or of at most 50.0 wt%, preferably at most 45.0 wt%, more preferably at most 40.0 wt%, based upon the total weight of the polymer composition (PC).

[0134] The polymer additive (Add) is notably selected from the group consisting of plasticizers, colorants, pigments, antistatic agents, dyes, nucleating agents,antioxidants, polymer processing aids, anti-blocking additive, slip additives, antifogging additives, chemical blowing agents, nucleating agent, and any combination thereof.

[0135] The proportion of the additive(s) is typically at least 0.1 wt% and / or at most 25.0 wt%, more preferably at most 20.0 wt%, most preferably at most 15.0 wt%, based upon the total weight of the polymer composition (PC).

[0136] The polymer composition (PC) is prepared by a compounding method comprising a step in which the polymer(s) of the polymer composition (PC) is / are melted and mixed, possibly with the other components of the polymer composition (PC). Any equipment generally used for compounding may be used such as a melt mixer, such as a single screw extruder or a twin screw extruder; a single screw or twin screw kneader or a Banbury mixer. The compounding method may conveniently be performed with an extruder such as a single screw extruder or a twin screw extruder.

[0137] Articles and applications

[0138] Another aspect of the present invention provides an article or a composite made of or comprising the polyamide (PA) or the polyamide composition (PC).

[0139] In one embodiment, the article or the composite is used as an electrical component, an automotive component, a food-contact component, a medical device component, a plumbing component, an oil and gas component or an aerospace component.

[0140] In another particular embodiment, the article or the composite is an automotive component used in an automotive application, for example in air induction systems, cooling and heating systems, drivetrain systems and fuel systems. Examples of automotive components include, but are not limited to, components in thermal management systems (including, but not limited to, thermostat housings, water inlet / outlet valves, water pumps, water pump impellers, and heater cores and end caps), air management system components (including, but not limited to, turbocharger actuators, turbocharger by-pass valves, turbocharger hoses, EGR valves, CAC housings, exhaust gas recirculation systems, electronic controlled throttle valves, and hot air ducts), transmission components and launch device components (including, but not limited to, dual clutch transmissions, automated manual transmissions, continuously variable transmissions, automatic transmissions, torque convertors, dual mass flywheels, power takeoffs, clutchcylinders, seal rings, thrust washers, thrust bearings, needle bearings, and check balls), automotive electronic components, automotive lighting components (including, but not limited to, motor end caps, sensors, ECU housings, bobbins and solenoids, connectors, circuit protection / relays, actuator housings, Li-Ion battery systems, and fuse boxes), traction motor and power electronic components (including, but not limited to, battery packs), fuel and selective catalytic reduction (‘SCR) systems (including, but not limited to, SCR module housings and connectors, SCR module housings and connectors, fuel flanges, rollover valves, quick connects, filter housings, fuel rails, fuel delivery modules, fuel hoses, fuel pumps, fuel injector O-rings, and fuel hoses), fluid system components (e.g. fuels system components) (including, but not limited to inlet and outlet valves and fluid pump components), interior components (e.g. dashboard components, display components, and seating components), and structural and light-weighting components (e.g. gears and bearings, sunroofs, brackets and mounts, electrical battery housings, thermal management components, braking system elements, and pump and EGR systems).

[0141] The article or composite can be molded from the polymer composition (PC), by any process adapted to thermoplastics, e.g. extrusion, injection molding, blow molding, rotomolding, overmolding or compression molding. Preferred formation of an article or a composite includes a suitable melt-processing method such as injection molding or extrusion molding of the polyamide composition, injection molding being a preferred shaping method. The article or composite can be printed from the polymer composition (PC), by a process comprising a step of extrusion of the material, which is for example in the form of a filament, or comprising a step of laser sintering of the material, which is in this case in the form of a powder.

[0142] The polyamide (PA) or the polymer composition (PC) as defined herein can also be used for the preparation of a thermoplastic composite.[EXPERIMENTAL SECTION]

[0143] The invention will now be described with reference to the following examples, whose purpose is merely illustrative and not intended to limit the scope of the invention.

[0144] The raw materials used for the preparation of the polyamides are provided below:- bio-based 1,9-diaminononane from Solvay USA, LLC: this diamine is 6866ased and prepared from oleic acid.- mixture of 1,9-diaminononane and 2-m ethyl- 1,8-octanediamine (MOD A) (in 60 / 40 mol / mol): this mixture is commercially available from Kuraray Co. MODA is the diamine of formula:- terephthalic acid (TP A): commercially available from Cepsa;- phosphorous acid: commercially available from Sigma Aldrich.

[0145] Detection of diamine DA of formula RsHN- in the biobased 1,9-diaminononane (C9)

[0146] The 1,9-diaminononane (C9) as received contains at least one diamine (DA) of formula R3HN-(CH2)x-NR4Rs. This can be detected via GC (Gas Chromatography)- QTOF (Quadrupole Time-Of-Flight) using an Agilent 7890B instrument equipped with a capillary column (VF35 ms, 30m x 0.25 mm x 0.25pm) and an Agilent QTOF 7200B detector. MS (Mass Spectroscopy) detection was accomplished via electron ionization (70 eV) and chemical ionization (methane and ammonia). Scans were performed from 45 amu to 650 amu. The oven temperature program consisted of an initial 50°C hold for 1 min, a ramp at 20°C / min to 325°C, and a hold at 325°C for 10 min. The injector temperature was set to 280°C. Measurements were performed in split mode using helium as the carrier gas. Subsequently, the concentrations of the molecules present were quantified via GC- FID (Flame Ionization Detection) using an Agilent 7890A instrument equipped with the column and a FID detector. The same oven temperature program was utilized. Measurements were performed in split mode using helium as the carrier gas.

[0147] In the bio-based 1,9-diaminonane, 0.047 mol% of a diamine (DA) of formula (IV) having empirical formula of C11H26N2 was measured. The MS / MS fragmentation spectrum of the species at retention time of 9.7 min as provided in Fig. 1 / 1 makesit possible to identify the structure of said species (NH2-(CH2)9-NMe2) present in the biobased C9 as received. The two other monomers listed in the Table below did not make it possible to detect the diamine (DA) of formula (IV) with the used analytical technique.see ref#l 1381487 in catalog of ThermoScientific (https: / / www.fishersci.fr / shop / products / l-9-diaminononane-98-thermo- scientific / 11381487)

[0148] Preparation of polyamides

[0149] Inventive example El and comparative example CE1 were prepared in an autoclave reactor equipped with a distillate line fitted with a pressure control valve.

[0150] El was prepared by charging into the reactor 5.64 g of bio-based 1,9- diaminononane, 5.58 g of TPA, 5.53 g of deionized water, and 0.0037 g of phosphorous acid. The reactor was sealed, purged with N2 gas and heated to 175°C and held for 25 min, followed by heating to 235°C and holding for 30 min, followed by heating to 288°C and holding for 25 min, followed by heating to 335°C and holding for 50 min. The steam generated was slowly released to keep the internal pressure under 250 psig. Once the temperature was at 335 °C for 15 min, the reactor pressure was slowly reduced to atmospheric pressure over 30 min while maintaining the temperature at 335°C. After holding for an additional 20 min with N2 gas purging, the reactor was cooled to room temperature and the polyamide (9.49 g) as produced was retrieved from the reactor.

[0151] CE1 was prepared in the same manner as El, except that bio-based 1,9- nonanediamine was replaced by an equivalent molar content of the mixture of 1,9- nonanediamine and 2-methyl-l,8-octanediamine.

[0152] Table 1 below shows the mol% of diamines and dicarboxylic acids used in preparing El and CE1.Table 1* mol% relative to the total moles of diamines** mol% relative to the total moles of dicarboxylic acids

[0153] Test methods & Results♦ Melting point (Tm), glass transition temperature (Tg) and enthalpy of melting (Hm) (ASTM D3418): Tg, Tm, and Hmwere 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 up to 350°C, followed by a first cool down to 30°C, followed by a second heat up to 360°C. The Tg and the Tm were determined from the second heat up.♦ Intrinsic Viscosity (IV) was measured according to ASTM standard (see description), using a mixture of phenol and 1,1,2,2-tetrachloroethane (60:40 wt / wt) as a solvent.Table 2

[0154] Digestion of polyamides and determination of the composition of the polyamides (end-groups and proportions of monomers)

[0155] The digestion of the polyamide (PA) makes it possible to determine the proportions of monomers (diamine(s) and dicarboxylic acid(s)) present in polymerized form in the polyamide along with the end-groups.

[0156] The hydrolysis of a polyamide is performed in acidic conditions: mix the weighed sample (40-50 mg) with a strong acid (0.5 mL of HBr, 48 wt% in water) in an hydrolysis tube and after purging O2 with vacuum and adding N2 (cycle vacuum / N2: 3 times) heat the mixture at a temperature higher than 150°C (160°C) until digestion is complete (generally, a duration of at least 4 hours is needed). Then coolto room temperature. The mixture is diluted with a solvent (mixture acetonitrile / water with vol. ratio 2 / 1) and the obtained mixture is analyzed by LC- MS.

[0157] Conditions for LC-MS: column Atlantis Premier BEH Z-HILIC (2.1 mm x 100 mm x 1.7); mobile phase A: 25 mM ammonium formate, pH = 3.4; mobile phase B: acetonitrile; temperature of the column: 50°C; flow rate: 0.250 mL / min; injection volume: 2 pL; gradient as shown below:

[0158] The diamine (DA) was detected in the mixture after digestion for polyamide El but not for polyamide CE1. The proportion of the amide end-groups of formula (III) in polyamide El and corresponding to the diamine (DA) present in the biobased C9 was calculated to be 8.0 peq / g.

Claims

C L A I M SClaim 1. Polyamide (PA), the recurring units of which consist of:- at least 50.0 mol% of recurring units (RPA) formed from the condensation of a diamine component (A) and a dicarboxylic acid component (B);- less than 50.0 mol% of recurring units (RPA*) of formula (II) (-NH-Alk- C(=O)-) derived from at least one lactam and / or at least one aminoacid where Aik designates a linear alkylene group; the proportions of these recurring units being expressed in mol% and based on the total amount of recurring units in the polyamide (PA); wherein:- the diamine component (A) consists of:■ at least 30.0 mol% of 1,9-nonanediamine (C9) of formula2HN- (CH2)9-NH2;■ less than 1.0 mol%, preferably less than 0.5 mol% of 2-methyl-1,8-octanediamine;■ optionally one or more additional diamines according to one of the two following embodiments: o according to a 1stembodiment, at least one diamine of formula (I) H2N-RI-NH2, where Ri is a C2-C2o divalent radical, different from the divalent radical derived from1.9-diaminononane, 1,10-diaminodecane and 2-methyl- 1,8-diaminooctane; o according to a 2ndembodiment, 1,10-diaminodecane in combination with at least one diamine of formula (I) H2N- RI-NH2, where Ri is a C2-C2o divalent radical, different from the divalent radical derived from 1,9-diaminononane,1.10-diaminodecane and 2-m ethyl- 1,8-diaminooctane; o with the proviso that the proportion of the additional diamine(s) of formula (I) in the diamine component (A) is strictly higher than 1.0 mol% (> 1.0 mol%);■ these proportions in mol% being based on the total amount of diamines in the diamine component (A);- the dicarboxylic acid component (B) consists of■ at least 30.0 mol% of terephthalic acid;■ optionally at least one dicarboxylic acid of formula (II) HOOC- R2-COOH, different from terephthalic acid, where R2 is a C1-C16 divalent radical;■ these proportions in mol% being based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B); and wherein polyamide (PA) comprises end-groups of formula -NH2 and / or - COOH and end-groups of formula (III) -C(=O)-NR3-(CH2)x-NR4Rs, where x is an integer of from 1 to 10; R3, R4 and Rs are H or CH , respectively and at least one of R3, R4 and R5 is CH3, the proportion of said end-groups of formula (III) being notably at least 0.10 peq / g.Claim 2. Polyamide (PA) according to claim 1, wherein the proportion of recurring units (RPA) is at least 60.0 mol%, preferably at least 90.0 mol%, preferably at least 95.0 mol%, preferably at least 99.0 mol%.Claim 3. Polyamide (PA) according to claim 1, wherein the recurring units of polyamide (PA) consist of the recurring units (RPA).Claim 4. Polyamide (PA) according to claim 1 or 2, wherein the proportion of C9 in the diamine component (A) is at least 50.0 mol%.Claim 5. Polyamide (PA) according to any one of the preceding claims, wherein Ri is selected from the group consisting of a linear or branched C2-C18 alkylene group different from -(CH2)9, -(CH2)IO and -(CH2)e-CHMe-CH2-; a C6-C30 cycloalkylene group; a C6-C30 arylene group; the divalent radical of 1,3-BAC, 1,4-BAC, MACM, PACM or IPDA; preferably selected in the group consisting of the diamines of formula 2HN-Alk-NH2 where Aik is a C2-C18 alkylene group different from -(CH2)9, -(CH2)IO and -(CH2)6-CHMe-CH2-; 1,3-BAC; 1,4-BAC; MACM; PACM, IPDA, MXDA and PXDA.Claim 6. Polyamide (PA) according to any one of the preceding claims, wherein the diamine of formula (I) is selected in the group consisting of:- the diamines of formula 2HN-Alk-NH2 where Aik is a C2-C18 alkylene group different from -(CH2)9-, -(CH2)IO- and -(CH2)e-CHMe-CH2-;- 1,3-BAC; 1,4-BAC; MACM; PACM, IPDA, MXDA, PXDA and combination thereof.Claim 7. Polyamide (PA) according to any one of the preceding claims, wherein R2 is selected from the group consisting of a linear or branched C1-C16 alkylene group; a Ce-Cio cycloalkylene group; a Ce-Cio arylene group different from para-phenylene.Claim 8. Polyamide (PA) according to any one of the preceding claims, wherein the dicarboxylic acid of formula (II) is selected in the group consisting of the diacids of formula HOOC-Alk-COOH where Aik is a linear or branched Ci-C 16 linear or branched alkylene group; isophthalic acid; 1,4-cyclohexane dicarboxylic acid and combination thereof.Claim 9. Polyamide (PA) according to any one of the preceding claims, wherein:- the proportion of 9T units in polyamide (PA) is at least 50.0 mol%, preferably at least 60.0 mol%, preferably at least 80.0 mol%, preferably at least 90.0 mol%, preferably at least 95.0 mol%, preferably at least 99.0 mol%; or- the recurring units of polyamide (PA) consist essentially of 9T units.Claim 10. Polyamide (PA) according to any one of the preceding claims, wherein R3 = H and R4 & R5=CH3 or R3, R4, R5 = CH3.Claim 11. Polyamide (PA) according to any one of the preceding claims, wherein the end- groups of the polyamide (PA) consist of:- (i) end-groups of formula -NH2 and / or -COOH;- (ii) the end-groups of formula (III) -C(=O)-NR3-(CH2)x-NR4Rs; and- (iii) optionally amide end-groups of formula -NH-C(=O)-G or -C(=O)- NH-G different from -C(=O)-NR3-(CH2)x-NR4Rs and where G is a C1-C16 organic moiety, preferably a C1-C12 organic moiety.Claim 12. Polyamide (PA) according to any one of the preceding claims, wherein the polyamide (PA) exhibits a melting temperature (Tm) of at least 250°C, Tm being measured by DSC according to ASTM D3418.Claim 13. Polyamide (PA) according to any one of the preceding claims, wherein:- the diamine C9 exhibits a biocontent of at least 95.0%, preferably at least 99.0%, preferably at least 99.9%, the biocontent being expressed as the % of organic carbon of renewable origin measured according to ASTM D6866-22; and / or- the polyamide (PA) exhibits a bio content of at least 6.0%, preferably > 50.0%, the biocontent being expressed as the % of organic carbon of renewable origin measured according to ASTM D6866-22.Claim 14. Polyamide (PA) according to any one of the preceding claims, wherein polyamide (PA) is not (i) a polyamide of composition 9T / 9I or of composition 9T / 9.12 or of composition 9T / 6, where the proportion of 9T units in said three polyamides is > 85.0 mol% or (ii) a polyamide derived from the condensation of a diamine component comprising 1,9- diaminononane (9) and 1,6-diaminohexane (6) and a dicarboxylic component comprising terephthalic acid (T) and decanedioic acid (10).Claim 15. Polyamide (PA) according to any one of the preceding claims, wherein polyamide (PA) is not a polyamide of composition 9T / 9I or of composition 9T / 9.12 or of composition 9T / 6 or (ii) a polyamide derived from the condensation of a diamine component comprising 1,9-diaminononane (9) and 1,6-diaminohexane (6) and a di carboxylic component comprising terephthalic acid (T) and decanedioic acid (10).Claim 16. Polyamide (PA) according to any one of the preceding claims, wherein the proportion of end-groups of formula (III) is < 50.0 peq / g.Claim 17. Polyamide (PA) according to any one of the preceding claims, wherein the proportion of end-groups of formula (III) is between 0.10 peq / g and 50.0 peq / g or between 0.10 peq / g and 20.0 peq / g or between 0.10 peq / g and 15.0 peq / g.Claim 18. Polyamide (PA) according to any one of the preceding claims, exhibiting: an intrinsic viscosity r| lower than or equal to 2.0 dL / g measured according to ASTM D789, typically with the use of a mixture phenol / 1, 1,2,2- tetrachloroethane (60 / 40 wt. ratio); and / or an inherent viscosity IV lower than or equal to 1.3 dL / g, measured according to ASTMD5225 with the use of a mixture phenol / 1, 1, 2, 2-tetrachloroethane (60 / 40 wt. ratio).Claim 19. Polyamide (PA) according to any one of the preceding claims, exhibiting an inherent viscosity IV of at least 0.70 dL / g, measured according to ASTM D5225 with the use of a mixture phenol / 1, 1,2, 2-tetrachloroethane (60 / 40 wt. ratio).Claim 20. Process of preparation of a polyamide (PA) as disclosed in any one of claims 1- 19, comprising heating a reaction mixture (RM) comprising or consisting of:(a) the monomer mixture (MM) consisting of 1,9-nonanediamine (C9) and all the other monomers (if any) constituting the polyamide;(b) at least one diamine (DA) of formula (IV) NHR3-(CH2)x-NR4Rs;(c) optionally a catalyst, notably selected in the group of phosphorous based compounds;(d) optionally water;(e) optionally at least one end-capping agent selected in the group consisting of endcapping agents of formula G-COOH, G-NH2 and combination thereof, G being a Ci- Ci6 hydrocarbon group, preferably a C1-C12 hydrocarbon group, preferably a C1-C7 hydrocarbon group; wherein the proportion of diamine(s) (DA) is between 0.01 and 2.50 mol%, this proportion being expressed relative to the content of 1,9-nonanediamine (C9).Claim 21. Polymer composition (PC) comprising :(a) from 30.0 to 100 wt% of at least one polyamide (PA) as disclosed in any one of claims 1-19;(b) from 0 to 70.0 wt% of at least one reinforcing agent (RA); and(c) from 0 to 30.0 wt% of at least one additive (Add) different from reinforcing agent (RA), notably selected from the group consisting of plasticizers, colorants, pigments, antistatic agents, dyes, nucleating agents, antioxidants, polymer processing aids, anti-blocking additive, slip additives, antifogging additives, chemical blowing agents, nucleating agent, and any combination thereof; these proportions in wt% being relative to the total weight of the polymer composition (PC).

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