WO2025168646A1 - Electronic device component comprising a sustainable polyamide (pa) - Google Patents

Abstract

The invention relates to a copolyamide (PA) with 9T and 10T units, to a smart device component comprising a composition (PC) comprising the copolyamide (PA). The invention also relates to the use of said polymer composition (PC) or of said copolyamide (PA) for the preparation of a smart device component.

Description

ELECTRONIC DEVICE COMPONENT

COMPRISING A SUSTAINABLE POLYAMIDE (PA)

This application claims priority of US provisional application N° 63/550,915 filed on 7 February 2024 and European patent application N° 24177584.0 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.

[FIELD OF THE INVENTION]

[0001] The invention relates to a resin that can be used for the preparation of a smart device component. The invention relates to a copolyamide (PA) with 9T and 10T units, to a smart device component comprising a composition (PC) comprising the copolyamide (PA). The invention also relates to the use of said polymer composition (PC) or of said copolyamide (PA) for the preparation of a smart device component.

[BACKGROUND OF THE INVENTION]

[0002] In recent years, sustainable materials have attracted much interest. For instance, "Polyamides Based on the Renewable Monomer, 1, 13-Tridecane Diamine I: Synthesis and Characterization of Nylon 13T" of Bret J. Chisholm et al. and available at the following address: https://www.osti.gov/serylets/purl/1053189 discloses polyamide 13T based on a renewable monomer.

[0003] EP 4206268 discloses a monomer composition for synthesizing recycled plastic, which comprises terephthalic acid.

[0004] US 2013/225770 discloses a polyamide resin comprising an aliphatic diamine (A) comprising (al) a first aliphatic diamine monomer comprising a C4, C6, C8 or CIO aliphatic diamine or a combination thereof and (a2) a second aliphatic diamine monomer comprising a C12, C14, C16 or C18 aliphatic diamine or combination thereof and a dicarboxylic acid (B). Comparative example 5 of US 2013/225770 is a copolyamide 9T (30 mol%) / 10T (70 mol%) end-capped by benzoic acid and having an intrinsic viscosity of 0.84 dL/g, a melting temperature of 298°C and a crystallization temperature of 269°C.

[0005] US 2013/295308 discloses a polyamide comprising dicarboxylic acid units containing 50 to 100 mol% of terephthalic acid units and/or naphthalenedicarboxylic acid units; and diamine units containing 60 to 100 mol% of aliphatic diamine units having 4 to 18 carbon atoms, the polyamide having terminal amino groups NH2 in an amount of 5 to 60 pmol/g.

[0006] US 2017/037208 discloses a process of preparation of a thermoplastic composite. 9T / 10T copolyamide is mentioned without any specific composition.

[0007] Comparative example A4 of US 2017/037217 is a 9T (4.6 mol%) / 10T (95.4 mol%) copolyamide with end-groups based on stearic acid having a melting temperature of 314°C.

[0008] Example A5 of JP 2020/033548 is a 9T (5.0 mol%) / 10T (95.0 mol%) copolyamide with end-groups based on stearic acid having a melting temperature of 314°C.

[0009] WO 2022/180195 discloses a polyamide composition with improved shrinkage and warpage properties and excellent mechanical properties, comprising a combination of polyamides and glass fiber. The polyamide is different from the polyamide of the present invention.

[0010] CN 102260375 discloses a semi-aromatic polyamide based on a diamine component comprising 1,10-decanediamine and between 0 and 30 mol% of an aliphatic diamine having 8 or more carbon atoms.

[0011] JP 2018/070674 discloses a compound for LED comprising a polyamide and white pigment. Several 9T / 10T copolyamides are disclosed and all are end-capped by stearic acid:

[TECHNICAL PROBLEM]

[0012] Electronic devices, notably mobile electronic devices, comprise different small components, some of them being plastic components. Because of their size and because the electronic device is intended to be commercialized and used worldwide, the plastic components need to retain a dimensional stability in different environments (temperature, humidity).

[0013] In addition, because of their size, during their fabrication, the components should exhibit reduced shrinkage and reduced warpage. [0014] There is therefore a need for a polymer and a polymer composition exhibiting excellent thermal properties (a high glass transition temperature (Tg), a high melting temperature (Tm) lower than 300°C (<300°C), a high heat of fusion (Hm) and an adequate crystallization temperature (Tc)) that retain a dimensional stability in different environments (temperature, humidity) and exhibit a low coefficient of linear thermal expansion (CLTE) both in the machine direction (MD) and in the transverse direction (TD) and a low water uptake. The difference between MD and TD should also be reduced to avoid extra shrinkage in one dimension compared to another. The modulus should also be high.

[0015] Tm should be high but still be below 300°C for an easier processability.

[0016] A high heat of fusion and a low Tm-Tc are also sought after properties for said plastic components. Indeed, a high heat of fusion (or high crystallinity) leads to an enhanced chemical resistance during the preparation of the component and the electronic device which usually involve several processing steps during the preparation of the electronic device (polishing, solvent cleaning, use of adhesives,...) and to a higher density. It also leads to improved mechanical properties. A low Tm-Tc is beneficial to reduce the cycle time and maximize throughput in injection moulding (IM). Another benefit of having a reduced cycle time during preparation of the component is that the time at which the resin is left at elevated temperatures is reduced leading to decreased resin degradation.

[0017] Moreover, there is a need for a sustainable polymer and polymer composition.

[0018] The polymer and the polymer composition aim at solving this technical problem.

[BRIEF DISCLOSURE OF THE INVENTION]

[0019] The invention is notably disclosed in the appended set claims.

[0020] The invention relates to a copolyamide (PA) as defined in any one of claims 1-29.

[0021] The invention relates to a polymer composition (PC) as defined in claim 30 or 31.

[0022] The invention relates to the use as defined in any one of claims 32-33.

[0023] The invention relates to an electronic device, notably a mobile electronic device, as defined in claim 34 or 35.

[0024] The invention relates to component of an electronic device, notably of a mobile electronic device, as defined in claim 36 or 37.

[0025] More precisions and details relating to these subject-matters are herein provided. [0026] The invention relates to component of an electronic device, notably of a mobile electronic device, as defined in any notion of the set of notions or in any claim of the set of claims.

[0027] More precisions and details relating to these subject-matters are herein provided.

[DEFINITIONS]

[0028] wt% means % by weight. mol% means % by mole.

[0029] In all numerical ranges (also in those without upper or lower end points), unless otherwise indicated, the end-points are included.

[0030] 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.

[0031] As used herein, the terminology ‘(Cn-C_m)’ in reference to an organic group, 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.

[0032] An hydrocarbon group is an organic group comprising only atoms of carbon and atoms of hydrogen.

[0033] The proportions of diamines in the diamine component (A) are expressed in mol% and are based on the total amount of diamines in the diamine component (A). The proportions of dicarboxylic acids in the dicarboxylic acid component (B) are expressed in mol% and are based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B).

[0034] 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).

[0035] The recurring units of polyamide (PA) are linked to one another by amide bonds.

[0036] A dicarboxylic acid is an organic compound containing two carboxyl groups (-COOH).

[0037] The term "electronic device" is intended to denote a device that includes at least one electronic component, notably a battery and/or a screen to display information.

[0038] The term “mobile electronic device ” is intended to denote an electronic device that is designed to be conveniently transported and used in various locations. The mobile electronic device may be a mobile electronic phone, a personal digital assistant, a laptop computer, a tablet computer, a radio, a camera, a wearable computing device (e.g., a smart watch, smart glasses and the like), a calculator, a music player, a global positioning system receiver, a portable game console and console accessories or a hard drive. The mobile electronic device may more particularly be a laptop computer, a tablet computer, a mobile electronic phones or a wearable computing device, such as a watch or glasses.

[0039] C9 refers to 1,9-nonanediamine or to the alkylene radical derived therefrom; CIO: 1,10-decanediamine or to the alkylene radical derived therefrom.

[DETAILED DESCRIPTION OF THE INVENTION]

[0040] As a first aspect, the invention relates to a polyamide (PA), the recurring units (RPA) of which are formed from the condensation of a diamine component (A) and a dicarboxylic acid component (B), wherein

- the diamine component (A) consists essentially of or consists of:

■ between 18.0 and 95.0 mol% of 1,9-nonanediamine (C9) of formula ₂HN- (CH₂)₉-NH₂; and

■ between 5.0 and 82.0 mol% of 1,10-decanediamine (CIO) of formula ₂HN- (CH₂)IO-NH₂;

■ these proportions in mol% being based on the total amount of diamines in the diamine component (A);

- the dicarboxylic acid component (B) consists essentially of or consists of terephthalic acid and a di carboxylic acid (DI) selected in the group consisting of isophthalic acid, adipic acid and combination of these two dicarboxylic acids, with the following proportions:

■ between 85.0 and 99.9 mol.% of terephthalic acid; and

■ between 0.1 and 15.0 mol.% of dicarboxylic acid (DI) with the proviso that if the dicarboxylic acid component (B) contains isophthalic acid, the proportion of isophthalic acid is strictly higher than 2.0 mol% (> 2.0 mol%);

■ these proportions in mol% being based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B); wherein the polyamide (PA) exhibits a melting temperature (Tm) lower than or equal to 300.0°C (< 300.0°C), preferably lower than or equal to 295.0°C (< 295.0°C), Tm being measured by Differential Scanning Calorimetry (“DSC”) according to ASTM D3418; and wherein preferably:

■ the polyamide (PA) exhibits a biobased content of at least 45.0%; and/or

■ the 1,9-nonanediamine (C9) and the 1,10-decanediamine (CIO) both exhibit a biobased content of at least 90.0%;

■ the biobased content being expressed as the % of organic carbon of renewable origin measured according to ASTM D6866-22.

[0041] More particularly, the invention relates to a polyamide (PA), the recurring units (RPA) of which are formed from the condensation of a diamine component (A) and a dicarboxylic acid component (B), wherein

- the diamine component (A) consists essentially of or consists of:

■ between 18.0 and 95.0 mol% of 1,9-nonanediamine (C9) of formula ₂HN- (CH₂)₉-NH₂; and

■ between 5.0 and 82.0 mol% of 1,10-decanediamine (CIO) of formula ₂HN- (CH₂)IO-NH₂;

■ these proportions in mol% being based on the total amount of diamines in the diamine component (A);

- the dicarboxylic acid component (B) consists essentially of or consists of terephthalic acid and a di carboxylic acid (DI) selected in the group consisting of isophthalic acid, adipic acid and combination of these two dicarboxylic acids, with the following proportions:

■ between 85.0 and 99.9 mol.% of terephthalic acid; and

■ between 0.1 and 15.0 mol.% of dicarboxylic acid (DI) with the proviso that if the dicarboxylic acid component (B) contains isophthalic acid, the proportion of isophthalic acid is strictly higher than 2.0 mol% (> 2.0 mol%);

■ these proportions in mol% being based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B); wherein the polyamide (PA) exhibits a melting temperature (Tm) lower than or equal to 300.0°C (< 300.0°C), preferably lower than or equal to 295°C (< 295.0°C), Tm being measured by Differential Scanning Calorimetry (“DSC”) according to ASTM D3418; and wherein: ■ the polyamide (PA) exhibits a biobased content of at least 45.0%; and/or

■ the 1,9-nonanediamine (C9) and the 1,10-decanediamine (CIO) both exhibit a biobased content of at least 90.0%;

■ the biobased content being expressed as the % of organic carbon of renewable origin measured according to ASTM D6866-22.

[0042] The proportions of monomers indicated in the diamine component (A) and in the dicarboxylic acid component (B) can be translated and correspond to the proportions of monomers present in the polyamide (PA) after polycondensation.

[0043] Details about the diamine component (A) and the dicarboxylic acid component (B) are now provided below.

[0044] Diamine component (A)

[0045] The diamine component (A) consists essentially of or consists of between 18.0 and 82.0 mol% of 1,9-nonanediamine (C9) and between 18.0 and 82.0 mol% of 1,10- decanediamine (CIO). These proportions in mol% are based on the total amount of diamines in the diamine component (A).

[0046] The expression "consist essentially" means in the context of the invention in relation to the diamine component that the diamine component (A) consists of C9, CIO and up to 1.0 mol%, more preferably up to 0.5 mol%, of one or more diamines other than C9 and CIO, this proportion in mol% being based on the total amount of diamines in the diamine component (A).

[0047] The diamine other than C9 and CIO is preferably not 2-methyl-l,8-octanediamine (MODA) nor 1,8-diaminooctane (OMDA) nor 1,6-hexamethylenediamine nor BAC nor 2,2,4-trimethyl-l,6-hexanediamine (2,2,4-TMD) nor 2,4,4-trimethyl-l,6- hexanediamine (2,4,4-TMD).

[0048] According to an embodiment (e) of the present invention, the proportion of C9 is > 30.0 mol%, preferably > 50.0 mol%, preferably > 55.0 mol% and/or < 90.0 mol%.

[0049] The proportions of C9 and CIO are preferably the following:

■ between 50.0 and 95.0 mol% of 1,9-nonanediamine (C9); and

■ between 5.0 and 50.0 mol% of 1,10-decanediamine (CIO).

[0050] The proportions of C9 and CIO are preferably the following:

■ between 55.0 and 95.0 mol% of 1,9-nonanediamine (C9); and

■ between 5.0 and 45.0 mol% of 1,10-decanediamine (CIO).

[0051] According to a preferred embodiment (El), the proportions of C9 and CIO are preferably the following: ■ between 65.0 and 75.0 mol% of 1,9-nonanediamine (C9); and

■ between 25.0 and 35.0 mol% of 1,10-decanediamine (CIO); or the following:

■ between 68.0 and 72.0 mol% of 1,9-nonanediamine (C9); and

■ between 28.0 and 32.0 mol% of 1,10-decanediamine (CIO).

[0052] According to a preferred embodiment (E2), the proportions of C9 and CIO are preferably the following:

■ between 75.0 and 85.0 mol% of 1,9-nonanediamine (C9); and

■ between 15.0 and 25.0 mol% of 1,10-decanediamine (CIO); or the following:

■ between 78.0 and 82.0 mol% of 1,9-nonanediamine (C9); and

■ between 18.0 and 22.0 mol% of 1,10-decanediamine (CIO).

[0053] According to a preferred embodiment (E3), the proportions of C9 and CIO are preferably the following:

■ between 85.0 and 95.0 mol% of 1,9-nonanediamine (C9); and

■ between 5.0 and 15.0 mol% of 1,10-decanediamine (CIO); or the following:

■ between 88.0 and 92.0 mol% of 1,9-nonanediamine (C9); and

■ between 8.0 and 12.0 mol% of 1,10-decanediamine (CIO).

[0054] The following embodiment of the present invention relative to the proportions of C9 / CIO and combinable with the appended set of claims is also part of the present invention:

■ C9: between [value of C9 of the example of reference Ej in Table II - 3.0 mol%] and [value of C9 of the example of reference Ej in Table II + 3.0 mol%];

■ CIO: between [value of CIO of the example of reference Ej in Table II - 3.0 mol%] and [value of CIO of the example of reference Ej in Table II + 3.0 mol%];

■ where j is 1, 2, 3, 4 or 5.

[0055] The following embodiment of the present invention relative to the proportions of C9 / CIO and combinable with the appended set of claims is also part of the present invention: ■ C9: between [value of C9 of the example of reference Ej in Table II - 2.0 mol%] and [value of C9 of the example of reference Ej in Table II + 2.0 mol%];

■ CIO: between [value of CIO of the example of reference Ej in Table II - 2.0 mol%] and [value of CIO of the example of reference Ej in Table II + 2.0 mol%];

■ where j is 1, 2, 3, 4 or 5.

[0056] The following embodiment of the present invention relative to the proportions of C9 / CIO and combinable with the appended set of claims is also part of the present invention:

■ C9: between [value of C9 of the example of reference Ej in Table II - 1.0 mol%] and [value of C9 of the example of reference Ej in Table II + 1.0 mol%];

■ CIO: between [value of CIO of the example of reference Ej in Table II - 1.0 mol%] and [value of CIO of the example of reference Ej in Table II + 1.0 mol%];

■ where j is 1, 2, 3, 4 or 5.

[0057] For clarity, the % expressed (±3.0 mol%; ±2.0 mol% or ±1.0 mol%) are absolute %. This means that if one takes example E4 and the ±2.0 mol%, the proportions of C9 and CIO are: for C9, between [70.0 mol% - 2.0 mol% = 68.0 mol%] and [70.0 mol% ± 2.0 mol% = 72.0 mol%] and for CIO, between [30.0 mol% - 2.0 mol% = 28.0 mol%] and [30.0 mol% + 2.0 mol% = 32.0 mol%].

[0058] It is known that both C9 and CIO diamines are biobased or issued from petroleum or natural gas as is disclosed in the table below:

[0059] The polyamide (PA) is preferably prepared from biobased C9 and CIO diamines. As mentioned in ASTM D6866-22, the term biobased means that the carbon atoms of said molecules are organic carbon of renewable origin like agricultural, plant, animal, fungi, microorganisms, marine, or forestry materials living in a natural environment in equilibrium with the atmosphere. The term biobased notably means that these molecules are not derived from petroleum or natural gas.

[0060] According to a preferred embodiment, 1,9-nonanediamine (C9) and 1,10- decanediamine (CIO) both exhibit a biobased content of at least 90.0%, the biobased content being expressed as the % of organic carbon of renewable origin measured according to ASTM D6866-22. This biocontent is preferably at least 95.0%, preferably at least 99.0%, preferably at least 99.5%, preferably at least 99.9%.

[0061] Biobased C9 may be prepared according to the process disclosed in CN 109422656. [0062] Biobased CIO may be produced from sebacic acid by the route indicated above.

[0063] According to another preferred embodiment, the polyamide (PA) exhibits a biobased content of at least 45.0%, the biobased content being expressed as the % of organic carbon of renewable origin measured according to ASTM D6866-22. This biocontent is preferably at least 50.0%, preferably at least 52.0%.

[0064] Dicarboxylic acid component (B)

[0065] The dicarboxylic acid component (B) consists essentially of or consists of terephthalic acid and a di carboxylic acid (DI) selected in the group consisting of isophthalic acid, adipic acid and combination of these two dicarboxylic acids, with the following proportions:

■ between 85.0 and 99.9 mol.% of terephthalic acid; and ■ between 0.1 and 15.0 mol.% of dicarboxylic acid (DI) with the proviso that if the dicarboxylic acid component (B) contains isophthalic acid, the proportion of isophthalic acid is strictly higher than 2.0 mol% (> 2.0 mol%);

[0066] The proportion of dicarboxylic acid(s) (DI) is preferably between 5.0 and 15.0 mol% or between 7.0 and 13.0 mol% or between 8.0 and 12.0 mol% or between 9.0 and 11.0 mol%.

[0067] DI may be isophthalic acid.

[0068] DI may be adipic acid.

[0069] According to an embodiment, DI is recycled.

[0070] This expression "consist essentially" means in the context of the invention in relation to the dicarboxylic acid component that the dicarboxylic acid component (B) consists of terephthalic acid, of di carboxylic acid (DI) and up to 1.0 mol%, more preferably up to 0.5 mol%, more preferably up to 0.25 mol%, more preferably up to 0.10 mol%, more preferably up to 0.05 mol%, of one or more dicarboxylic acids other than terephthalic acid, isophthalic acid and adipic acid, this proportion in mol% being based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B).

[0071] According to an embodiment, terephthalic acid is biobased so as to further increase the biocontent of polyamide (PA). A biobased terephthalic acid may for instance be prepared from a biobased furfural 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). The bio content of polyamide (PA) as defined above may then be at least 95.0%, preferably at least 98.0 %. The bio content of the polyamide (PA) may be 100%.

[0072] According to an embodiment (E4), the terephthalic acid used is a recycled terephthalic acid (denoted herein "rT"). "Recycled terephthalic acid" means that this monomer is obtained through a depolymerization reaction of a (co)polyester comprising recurring units derived from terephthalic acid. The industry has developed several depolymerization process of polyesters, such as polyethylene terephthalate, comprising more than 50.0 mol% of the following recurring (RPE) units: where Aik denotes a C2-C6 linear or branched alkylene group. (RPE) may more particularly be the following:

[0073] The composition of the recycled terephthalic acid (rT) is typically the following:

- terephthalic acid (TP A);

- isophthalic acid (Impl): between 0 and 2.0 mol%, this proportion being calculated by formula IPA/(TPA+IPA) x 100 where TP A and IP A are the molar proportions of respectively terephthalic and isophthalic acid in rT;

- one or more organic impurities Imp2 selected from the group consisting of formic acid (FA) and acetic acid (AA), wherein the total proportion of impurities Imp2 is less than 300 pg/g of rT;

- one or more aromatic impurities Imp3 selected from the group consisting of 4- carboxybenzaldehyde (4-CBA), benzoic acid (BZA) and p-toluic acid (p-TA), wherein the total proportion of impurities Imp3 is less than 300 pg/g of rT; with the proviso that the recycled terephthalic acid contains at least one of the three impurities Impl, Imp2 or Imp3.

[0074] The proportion of isophthalic acid in rT is typically between 0.1 and 2.0 mol%. The proportion of isophthalic acid in rT may more particularly be lower than or equal to 1.0 mol% or lower than or equal to 0.50 mol%.The proportion of Impl in rT is typically between 1.0 and 300.0 pg/g.

[0075] rT may be prepared according to the teaching of EP 4206270 Al or US 2017/008826. Representative examples of compositions of rT are given in the table below:

FA: formic acid; 4-CBA: 4-carboxybenzaldehyde; BZA: benzoic acid; p-TA: p-toluic acid

[0076] Recurring units (RPA)

[0077] The recurring units (RPA) of the polyamide (PA) consist essentially or consist of the following units (RPAI) and (RPA?):

[0078] The invention also relates to a polyamide (PA), the recurring units of which consist essentially or consist of the units (RPAI) and (RPA2), with the following proportions of recurring units (RPAI) and (RPA2):

- (RPAI): between 85.0 and 98.0 mol.%;

- (RPA2): between 2.0 (value excluded) and 15.0 mol.%;

- the relative molar proportion of C9/C10 being between 18/82 and 95/5.

[0079] According to an embodiment, these proportions are preferably the following:

- (RPAI): between 85.0 and 95.0 mol.%;

- (RPA2): between 5.0 and 15.0 mol.%; or

- (RPAI): between 87.0 and 93.0 mol.%;

- (RPA2): between 7.0 and 13.0 mol.%.

[0080] In addition or alternatively, according to another embodiment, the relative molar proportion of C9/C10 is between 50/50 and 95/5 or between 55/45 and 95/5 or between 65/35 and 75/25 or between 75/25 and 85/15 or between 85/15 and 95/5.

[0081] The expression "consist essentially" means in the context of the invention in relation to the recurring units that the recurring units of polyamide (PA) consist of recurring units (RPAI)-(RPA2) and up to 1.0 mol%, more preferably up to 0.50 mol%, more preferably up to 0.25 mol%, more preferably up to 0.10 mol%, of recurring units other than recurring units (RPAI) and (RPA2), this proportion in mol% being based on the total amount of recurring units in the polyamide (PA).

[0082] The polyamide (PA) of the invention is preferably free of the following recurring units:

- the polyamide (PA) is preferably free or recurring units derived from 1,6- hexamethylene diamine. Preferably, the polyamide (PA) does not comprise recurring units derived from 1,6-hexam ethylene diamine; and/or

- the polyamide (PA) is preferably free of recurring units derived from 1,8- octanediamine. Preferably, the polyamide (PA) does not comprise recurring units derived from 1,8-octanediamine; and/or

- the polyamide (PA) is preferably free of recurring units derived from 2-methyl-l,8- octanediamine. Preferably, the polyamide (PA) does not comprise recurring units derived from 2-methyl- 1,8-octanediamine; and/or

- the polyamide (PA) is preferably free of recurring units derived from 1,8- octanediamine. Preferably, the polyamide (PA) does not comprise recurring units derived from 1,8-octanediamine; and/or

- the polyamide (PA) is preferably free of recurring units derived from m- xylylenediamine or p-xylylenediamine. Preferably, the polyamide (PA) does not comprise recurring units derived from m-xylylenediamine or p-xylylenediamine; and/or

- the polyamide (PA) is preferably free of recurring units derived from 1,3- bis(aminomethyl)cyclohexane or l,4-bis(aminomethyl)cyclohexane. Preferably, the polyamide (PA) does not comprise recurring units derived from 1,3- bis(aminomethyl)cyclohexane or l,4-bis(aminomethyl)cyclohexane; and/or

- the polyamide (PA) is preferably free of recurring units derived from 2,2,4-TMD or 2,4,4-TMD. Preferably, the polyamide (PA) does not comprise recurring units derived from derived from 2,2,4-TMD or 2,4,4-TMD. 2,2,4-TMD designates 2,2,4-trimethyl- 1,6-hexanediamine and 2,4,4-TMD designates 2,4,4-trimethyl-l,6-hexanediamine; and/or

- the polyamide (PA) is preferably free of recurring units derived from a lactam or from an amino-acid. Preferably, the polyamide (PA) preferably does not comprise recurring units derived from a lactam or from an amino-acid;

- the expression "free of recurring units X" means that the proportion of said recurring units X in the polyamide (PA) is lower than or equal to 1.0 mol% (< 1.0 mol%), preferably lower than or equal to 0.5 mol% (< 0.5 mol%), preferably lower than or equal to 0.25 mol% (< 0.25 mol%).

[0083] The composition of polyamide (PA) is determined with well-known analytical techniques. The composition of polyamide (PA), the proportions of recurring units and end-groups in the polyamide (PA) can be determined by ^JH NMR spectroscopy. 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 liquid chromatography (HPLC) is a convenient analytical technique for this analysis. See ACS Sustainable Chem. Eng. 2020, 8, 31, 11818-11826.

[0084] The end-groups may also be titrated by a potentiometric technique.

[0085] Isolation of the monomers after digestion (hydrolysis) of the polyamide (PA) makes it also possible to determine their biocontent.

[0086] 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.

[0087] The conditions of hydrolysis provided in the Experimental Section can be followed.

[0088] End-groups of the polyamide (PA) of the invention

[0089] The end-groups of the polyamide (PA) of the invention are selected in the group of - NH2, -COOH and amide end-groups. Indeed, the end-groups in the polyamide (PA) may be -NH2 or -COOH. Yet, when the polycondensation leading to the polyamide (PA) involves the presence of an end-capping agent, either present in one of the monomers or added to the reaction mixture (RM), these end-groups may be converted, partially or totally, into amide end-groups.

[0090] According to an embodiment, polyamide (PA) comprises end-groups of formula - NH2 and/or -COOH and amide end-groups.

[0091] According to an embodiment, polyamide (PA) comprises (i) end-groups of formula - NH2 and/or -COOH and (ii) amide end-groups of formula -NH-C(=O)-G or -C(=O)- NX-G where X is H or (Ci-C3)-alkyl group, notably Me, and G is a C1-C16 organic group, preferably a C1-C12 organic group, preferably a C1-C10 organic group. [0092] The end-groups of polyamide (PA) preferably consist essentially or consist of (i) end- groups of formula -NH2 and/or -COOH and (ii) amide end-groups of formula -NH- C(=O)-G or -C(=O)-NX-G where X is H or (Ci-C3)-alkyl group, notably Me, and G is a C1-C16 organic group, preferably a C1-C12 organic group, preferably a C1-C10 organic group.

[0093] The organic group G contains carbon and hydrogen atoms and may also contain at least one additional atom selected in the group of N atoms, O atoms and combination thereof. According to an embodiment, the organic group G contains only carbon, hydrogen, N and O atoms. According to another embodiment, the organic group G contains only carbon, hydrogen and N atoms. According to another embodiment, the organic group G is an hydrocarbon group.

[0094] According to a preferred embodiment, G is not aromatic.

[0095] According to a preferred embodiment, G is not a phenyl group or if G is a phenyl group, the proportion of the end-groups of formula -NH-C(=O)-Ph is lower than 1.95 mol%, this proportion being expressed relative to the proportion of -COOH and amide groups -NH-C(=O)- present in the polyamide (PA).

[0096] Details about the amide end-groups are now given. The amide end groups of polyamide (PA) may be more particularly:

■ of formula -NH-C(=O)-R where R is selected in the group consisting of Ci-Ce linear or branched alkyl groups; C5-C7 cycloalkyl groups optionally substituted by one or more Ci-Ce alkyl groups; Ce-Cs aromatic groups optionally substituted by one or more Ci-Ce alkyl groups and combination thereof; and/or

■ of formula -C(=O)-NX-R' where R' is selected in the group consisting of C2-C10 linear or branched alkyl groups optionally substituted by a group of formula - NR4R5 where R4 and R5 are independently H or (Ci-C3)-alkyl group, preferably H or Me; C5-C7 cycloalkyl groups substituted by one or more Ci-Ce alkyl groups; Ce- Cs aromatic groups substituted by one or more Ci-Ce alkyl groups and combinations thereof.

[0097] R may be a Ci-Ce linear or branched alkyl group. R may more particularly be a C1-C4 linear or branched alkyl group. R may more particularly be a methyl or ethyl group.

[0098] R may be a C5-C7 cycloalkyl group. R may more particularly be a cycloalkyl group.

[0099] R may be a Ce-Cs aromatic group optionally substituted by one or more Ci-Ce alkyl groups. R may more particularly be a phenyl group optionally substituted by one or more Ci-Ce alkyl groups, such as -Ph or -PI1-CH3. [00100] The amide end groups of formula-NH-C(=O)-G or of formula -NH-C(=O)-R result from the reaction of the end-groups -NH2 with a monocarboxylic acid (end-capping agent), notably of respectively formula GCOOH or RCOOH.

[00101] The monocarboxylic acid (end-capping agent) may advantageously be selected in the group consisting of benzoic acid; toluic acid; cyclohexanoic acid; R-COOH where R is a linear or branched C1-C5 alkyl group and combination of two or more of these acids. R is the radical derived from the acid of formula R-COOH.

[00102] The monocarboxylic acid (end-capping agent) may more particularly be selected in the group consisting of acetic acid, propanoic acid, butyric acid, valeric acid, 2- ethylhexanoic acid, cyclohexanoic acid, benzoic acid and combination of two or more of these acids.

[00103] The monocarboxylic acid (end-capping agent) is more particularly of formula CH3- (CH₂)_m-COOH where m is an integer between 0 and 4. The amide end groups are then of formula -NH-C(=O)-(CH₂)_m-CH₃.

[00104] The amide end groups of formula -C(=O)-NX-R' result from the reaction of the end- groups -COOH with an amine (end-capping agent).

[00105] The amine (end-capping agent) may advantageously be selected in the group consisting of the amines of formula R'-NXH where R' is a linear or branched C₂-Ce alkyl group. R' is the radical derived from the amine of formula R'-NH₂.

[00106] The amine (end-capping agent) is more particularly of formula CH3-(CH₂)_m'-NH₂ where m' is an integer between 2 and 6. The amide end groups are then of formula - C(=O)-NH-(CH₂)_m-CH₃.

[00107] The amine (end capping agent) may more particularly be selected in the group consisting of propyl amine, butylamine, pentylamine, hexylamine, 2- ethylhexylamine, and combination of two or more of these amines.

[00108] The proportion of the end groups are generally quantified by 'H NMR spectroscopy or by potentiometric techniques.

[00109] Properties of polyamide (PA) of the invention

[00110] The polyamide (PA) of the invention generally has a number average molecular weight ("Mn") ranging from 5,000 g/mol to 40,000 g/mol, for example from 5,000 g/mol to 20,000 g/mol, from 6,000 to 18,000 g/mol or from 7,000 g/mol to 15,000 g/mol. The range 6,000-18,000 g/mol is preferred. The range 7,000-15,000 g/mol is even more preferred. [00111] Mn can be determined using the following equation (1): Mn = 2,000,000 / [EG] (1) wherein [EG] is the proportion of end-groups in the PA expressed in mmol/kg. The proportion of the end groups are generally quantified by ^JH NMR spectroscopy or by potentiometric techniques.

[00112] 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. [00113] Mw is typically between 10,000 and 35,000 g/mol.

[00114] M_n and M_w can also be determined by Size Exclusion Chromatography (SEC) coupled to a light scattering instrument or refractive index detector calibrated with the use of polystyrene standards.

[00115] Polyamide (PA) preferably exhibits an inherent viscosity (IV) of at least 0.70 dL/g, the IV being measured according to ASTM D5225 with the use of a mixture phenol/l,l,2,2-tetrachloroethane (60/40 wt. ratio).

[00116] IV is generally between 0.70 and 1.30 dL/g (measured in the same conditions). IV may more particularly be between 0.75 and 1.20 dL/g, preferably between 0.80 and 1.15 dL/g.

[00117] Glass transition temperature (Tg)

[00118] The polyamide exhibits a Tg of at least 100°C. The Tg of the polyamide (PA) is preferably at least 105.0°C, preferably at least 108.0°C, preferably at least 109.0°C, preferably at least 110°C.

[00119] The polyamide (PA) generally exhibits a Tg of at most 130°C or at most 120°C.

[00120] The Tg may more particularly be between 100°C and 130°C or between 100°C and 120°C.

[00121] Tg is measured by Differential Scanning Calorimetry (“DSC”) according to ASTM D3418, notably using a heating and cooling rate of 20°C/min.

[00122] Tg can more particularly be measured as described in the experimental section.

[00123] Tg can be measured by Differential Scanning Calorimetry (“DSC”) according to ASTM D3418 using a heating and cooling rate of 20°C/min. Three scans are used for each DSC test: a first 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 is determined from the second heat up.

[00124] Melting temperature (Tm) [00125] The polyamide (PA) exhibits a Tm of lower than or equal to 300.0 °C (< 300.0°C). Tm may more particularly be lower than or equal to 298.0°C (< 298.0°C), preferably lower than or equal to 297.0°C (< 297.0°C), preferably lower than or equal to 296.0°C (< 296.0°C), preferably lower than or equal to 295.0°C (< 295.0°C).

[00126] According to an embodiment, Tm is strictly lower than 300°C (< 300°C).

[00127] Tm is generally at least 280°C. Tm is preferably at least 285°C.

[00128] The Tm may be between 280°C and 310°C or between 280°C and 298.0°C.

[00129] It is mentioned that it may be case that a polyamide exhibits more than one melting point. In this case, the Tm mentioned in the present application corresponds to the peak of melting point having the highest intensity.

[00130] Tm is measured by Differential Scanning Calorimetry (“DSC”) according to ASTM D3418, notably using a heating and cooling rate of 20°C/min.

[00131] Tm can more particularly be measured as described in the experimental section.

[00132] Tm can be measured by Differential Scanning Calorimetry (“DSC”) according to ASTM D3418 using a heating and cooling rate of 20°C/min. Three scans are used for each DSC test: a first heat up to 350°C, followed by a first cool down to 30°C, followed by a second heat up to 360°C. Tm is determined from the second heat up.

[00133] Crystallization temperature (Tc)

[00134] Polyamide (PA) exhibits a Tc of at most 265.0 °C or at most 260.0°C.

[00135] Tc is generally at least 240°C.

[00136] Tc is measured by Differential Scanning Calorimetry (“DSC”) according to ASTM D3418, notably using a heating and cooling rate of 20°C/min.

[00137] Tc can be measured by Differential Scanning Calorimetry (“DSC”) according to ASTM D3418 using a heating and cooling rate of 20°C/min. Three scans are used for each DSC test: a first heat up to 350°C, followed by a first cool down to 30°C, followed by a second heat up to 360°C. Tc is determined from the first cool down.

[00138] Tc can more particularly be measured as described in the experimental section.

[00139] The polyamide (PA) also exhibits a low A=(Tm - Tc). A is preferably lower than or equal to 42.0°C, preferably lower than or equal to 41.0°C, preferably lower than or equal to 40.0°C. A is generally at least 25.0°C or at least 30.0°C.

[00140] The polyamide (PA) also exhibits a high A*=(Tc - Tg). A* is preferably higher than or equal to 130.0°C. A* is generally at most 150.0°C.

[00141] Heat of fusion (Hm) [00142] The polyamide (PA) of the invention is semi -crystalline.

[00143] The polyamide (PA) exhibits a Hm of at least 60.0 J/g, preferably at least 65.0 J/g, preferably at least 70.0 J/g.

[00144] Hm is generally at most 85.0 J/g or at most 80.0 J/g.

[00145] Hm may be between 60.0 J/g and 85.0 J/g.

[00146] Hm is measured by Differential Scanning Calorimetry (“DSC”) according to ASTM D3418, notably using a heating and cooling rate of 20°C/min.

[00147] Hm can more particularly be measured as described in the experimental section.

[00148] Hm can be measured by Differential Scanning Calorimetry (“DSC”) according to ASTM D3418 using a heating and cooling rate of 20°C/min. Three scans are used for each DSC test: a first heat up to 350°C, followed by a first cool down to 30°C, followed by a second heat up to 360°C. The Hm is measured from the second heat up.

[00149] According to an embodiment of the invention, polyamide (PA) exhibits the following thermal properties:

Tm is > 280.0 and < 300.0°C; and

Tg is > 110°C; and

Hm is > 60.0 J/g; preferably A=(Tm - Tc) is < 42.0°C.

These properties render it suitable for the preparation of a component by injection moulding

[00150] Water uptake

[00151] The polyamide (PA) of the invention generally exhibits a water uptake at saturation at 90°C lower than 3.0 wt%, preferably lower than 2.7 wt%, wherein the water uptake is determined by providing a specimen shaped in the form of ASTM D638 Type V bar in its dry state (moisture content of less than 0.2 %wt), immersing the same in deionized water at 90°C, until reaching a constant weight. The water uptake is calculated according to the formula:

Water u pta k wherein Wbefore is the weight of the shaped specimen in its original dry state and Waiter is the weight of the shaped specimen after water uptake.

[00152] Process of preparation of the polyamide (PA)

[00153] The polyamide (PA) described herein can be prepared by any conventional method adapted to the synthesis of polyphthalamides. [00154] The polyamide (PA) is prepared by polycondensation by heating a reaction mixture (RM) comprising, consisting essentially of or consisting of:

- a mixture of monomers (MM) comprising, consisting essentially of or consisting of the diamine component (A) and the dicarboxylic acid component (B);

- optionally a catalyst, notably selected in the group consisting of phosphorous acid, ortho-phosphoric acid, meta-phosphoric acid, alkali-metal hypophosphite such as sodium hypophosphite and phenylphosphinic acid;

- optionally at least one capping agent;

- optionally water in a proportion which is preferably less than 80.0 wt.%, preferably less than 50.0 wt.% water, this proportion of water is based on the total weight of the reaction mixture (RM).

[00155] The C9 and CIO diamines used for the preparation of the polyamide (PA) are commercially available. The C9 may be derived from oleic acid.

[00156] As is well known in polycondensation, the reaction mixture (RM) comprises the above-referenced diamines and diacids in a quantity such that the proportion of - COOH groups from the dicarboxylic acids of the dicarboxylic acid component (B) and the proportion of -NH2 groups from the diamines of the diamine component (A) is substantially equimolar. This molar ratio [-COOH groups from the dicarboxylic acids of the dicarboxylic acid component (B)] / [-NH2 groups from the diamines of the diamine component (A)] is typically comprised between 0.9 and 1.1, preferentially between 0.95 and 1.05, even more preferentially between 0.98 and 1.02.

[00157] The reaction mixture (RM) generally comprises a catalyst. The catalyst may be selected in the group consisting of phosphorous acid, ortho-phosphoric acid, metaphosphoric acid, alkali-metal hypophosphite such as sodium hypophosphite and phenylphosphinic acid. A convenient catalyst used is phosphorous acid.

[00158] For control of the molar mass, the reaction mixture (RM) may also further comprise at least one end-capping agent as disclosed above.

[00159] The temperature at which the reaction mixture is heated must be high enough to induce the reaction between the amine groups and the carboxylic groups and to decrease the viscosity of the mixture. This temperature is generally at least 140°C, more particularly at least 200°C. The polycondensation results in the formation of the amide bonds and the release of water as a by-product. [00160] The temperature can be step-wise increased in the course of the polycondensation. An example of step-wise increase is given in example E4 and may be followed for the preparation of the polyamide of the invention.

[00161] The polycondensation is advantageously performed in a well stirred vessel equipped with means to remove the volatile products of the reaction. As the viscosity of the reaction mixture increases overtime, the stirrer is adapted to provide sufficient stirring to the reaction mixture at the beginning of the polymerization and when the conversion of the polycondensation is nearly complete.

[00162] The conditions disclosed in the experimental section may conveniently be used for the preparation of the polyamide (PA).

[00163] Polymer composition (PC)

[00164] The invention also relates to a polymer composition (PC) comprising or consisting of:

- at least one polyamide (PA) as disclosed herein;

- a component (c) blended with polyamide(s) (PA) and selected in the group consisting of reinforcing fillers (F), plastic additives (A), polyamides (PA*) and combinations of two or more of said components; where polyamide (PA*) is not a polyamide comprising 9T and 10T units.

[00165] According to an embodiment, polymer composition (PC) comprises or consists of:

- at least one polyamide (PA) as disclosed herein;

- at least one reinforcing filler (F);

- optionally at least one additive (A).

[00166] The proportion of polyamide(s) (PA) is typically at least 30.0 wt%, this proportion being relative to the total weight of composition (PC).

[00167] The proportion of component (c) or the total proportion (F)+(A) is typically at most 70.0 wt%, this proportion being relative to the total weight of composition (PC).

[00168] Polymer composition (PC) is prepared by a method comprising a step in which the components of the polymer composition (PC) are introduced into a mixer, such as single screw extruder or twin screw extruder, agitator, single screw or twin screw kneader or Banbury mixer wherein the polymeric component of the polymer composition (PC) is in the molten form. The mixer is conveniently an extruder.

[00169] Reinforcing filler! s) (F)

[00170] Component (c) may be at least one reinforcing filler (F).

[00171] The reinforcing filler (F) may be a fibrous or particulate reinforcing filler. [00172] A fibrous reinforcing filler is considered herein as a material having length, width and thickness, wherein the average length is significantly larger than both the width and thickness. Such a material has generally an aspect ratio, defined as the average ratio between the length and the largest of the width and thickness of at least 5, at least 10, at least 20 or at least 50.

[00173] The reinforcing filler (F) may be selected from mineral fillers (such as 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 and wollastonite.

[00174] According to an embodiment, the reinforcing filler (F) is glass fibers.

[00175] Plastic additive(s) (A)

[00176] Component (c) may be at least one plastic additive (A). A plastic additive (A) is not a reinforcing filler (F).

[00177] The plastic additive (A) is typically selected in the group consisting of tougheners, plasticizers, colorants, pigments, antistatic agents, dyes, lubricants, thermal stabilizers, light stabilizers, flame retardants, nucleating agents, antioxidants, UV absorbers, acid scavengers and combinations thereof.

[00178] Polyamide(s) (PA*)

[00179] Component (c) may be at least one polyamide (PA*) with the proviso that polyamide (PA*) is not a polyamide comprising 9T and 10T units.

[00180] Polyamide (PA*) is typically selected in the group of aliphatic polyamides and semiaromatic polyamides.

[00181] Use of the polyamide (PA) or the polymer composition (PC)

[00182] The invention also relates the use of the polyamide (PA) or the polymer composition (PC) for the preparation of a component of an electronic device, notably of a mobile electronic device.

[00183] Said component may more particularly be: a backbone, an antenna window, a fitting part, a snap fit part, a mutually moveable part, a functional element, an operating element, a tracking element, an adjustment element, a carrier element, a frame element, a switch, a connector, a cable, a housing or a speaker part.

[00184] A “backbone” refers to a structural component onto which other components of the device, such as electronics, microprocessors, screens, keyboards and keypads, antennas, battery sockets, and the like are mounted. [00185] The component can include at least one mounting hole or at least one fastening device. [00186] The article can be molded from the polyamide (PA) or the polyamide composition (PC) by any process adapted to thermoplastics, e.g., extrusion, injection molding, blow molding, rotomolding, overmolded or compression molding. Injection molding is a convenient technique of preparation of said article.

[00187] The invention also relates to an electronic device, notably a mobile electronic device, comprising the polyamide (PA) or the polymer composition (PC) as disclosed herein.

[00188] The invention also relates to a component of an electronic device, notably a mobile electronic device, comprising the polyamide (PA) or the polymer composition (PC) as disclosed herein.

[EXPERIMENTAL SECTION]

[00189] The present examples illustrate the invention.

[00190] Raw materials used [00191] The following raw materials were used to prepare the copolyamides:

Table I

[00192] All of the copolyamides disclosed in Table II were prepared in an autoclave reactor equipped with a distillate line fitted with a pressure control valve. The procedure detailed below for Ex 1 was followed (except for the compositions) for the preparation of all copolyamides.

[00193] Example 1 (El)

[00194] The polyamide El was prepared by charging into the reactor 4.89 g of 1,9- diaminononane, 0.69 g of 1,10-diaminodecane, 5.02 g of terephthalic acid, 0.56 g of isophthalic acid, 5.50 g of deionized water, and 0.0037 g of phosphorous acid. The reactor was sealed, purged with N2 gas three times. The reactor was heated to 177 °C and held for 25 min, followed by heating to 232 °C and holding for 35 min, followed by heating to 288 °C and holding for 25 min, followed by heating to 316 °C and holding for 15 min. The steam generated was slowly released to keep the internal pressure under 200 psig. Once the temperature was at 316 °C for 15 min, the reactor pressure was slowly reduced to atmospheric pressure over 30 min. After finishing the depressurization, N2 gas was used to continuously purge the reactor over 30 min. Afterwards, the reactor was cooled to room temeprature and the polymer was retrieved from the reactor.

[00195] Digestion of polyamides and determination of the composition of the polyamides (end-groups and proportions of monomers)

[00196] 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.

[00197] 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 cool to 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.

[00198] 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:

[00199] IV (inherent viscosity)

[00200] IV is measured according to ASTM D5225 with the use of a mixture phen ol/l, 1,2,2- tetrachloroethane (60/40 wt. ratio).

[00201] Thermal Performance [00202] Tg, Tm, Tc and Hm were measured by Differential Scanning Calorimetry (“DSC”) according to ASTM D3418 using a heating and cooling rate of 20 °C/min. Three scans were used for each DSC test: a first heat up to 350 °C, followed by a first cool down to 30 °C, followed by a second heat up to 360 °C. Tg, Tm and Hm were determined from the second heat up. Tc was determined from the first cool down. [00203] As can be seen with the results below, the polyamide of the invention exhibits the sought-after balance of properties mentioned in the introduction. In particular, in comparison to the polyamides of the comparatives examples, the polyamides according to the invention a high Tm but still lower than 300°C (<300°C), a high Tg & Hm and a good Tm-Tc that make them suitable for preparation of components by injection moulding.

27 SSPU 2024/002-WO-PCT

Table II

* proportions of the monomers are given in mol% relative to the diamines in the diamine component (A) and to the dicarboxylic acids in the dicarboxylic acic component (B). These proportions correspond and can be translated into the proportions of monomers in the polyamide after polycondensation

Claims

Claim 1. Polyamide (PA), the recurring units (RPA) of which are formed from the condensation of a diamine component (A) and a dicarboxylic acid component (B), wherein

- the diamine component (A) consists essentially of or consists of:

■ between 18.0 and 95.0 mol% of 1,9-nonanediamine (C9) of formula ₂HN- (CH₂)₉-NH₂; and

■ between 5.0 and 82.0 mol% of 1,10-decanediamine (CIO) of formula ₂HN- (CH₂)IO-NH₂;

■ these proportions in mol% being based on the total amount of diamines in the diamine component (A);

■ the expression "consist essentially" meaning that the diamine component (A) consists of the two diamines C9 and CIO and up to 1.0 mol%, more preferably up to 0.5 mol%, more preferably up to 0.25 mol%, more preferably up to 0.10 mol%, more preferably up to 0.05 mol%, of one or more diamines other than C9 and CIO, this proportion in mol% being based on the total amount of diamines in the diamine component (A);

- the dicarboxylic acid component (B) consists essentially of or consists of terephthalic acid and a di carboxylic acid (DI) selected in the group consisting of isophthalic acid, adipic acid and combination of these two dicarboxylic acids, with the following proportions:

■ between 85.0 and 99.9 mol.% of terephthalic acid; and

■ between 0.1 and 15.0 mol.% of dicarboxylic acid (DI) with the proviso that if the dicarboxylic acid component (B) contains isophthalic acid, the proportion of isophthalic acid is strictly higher than 2.0 mol% (> 2.0 mol%);

■ these proportions in mol% being based on the total amount of diacids in the dicarboxylic acid component (B);

■ the expression "consist essentially" meaning that the dicarboxylic acid component (B) consists of terephthalic acid, of DI and up to 1.0 mol%, more preferably up to 0.5 mol%, more preferably up to 0.25 mol%, more preferably up to 0.10 mol%, more preferably up to 0.05 mol%, of one or more dicarboxylic acids other than terephthalic acid, isophthalic acid and adipic acid, this proportion in mol% being based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B); wherein the polyamide (PA) exhibits a melting temperature (Tm) lower and equal to 300.0°C (< 300.0°C), preferably lower and equal to 295.0°C (< 295.0°C), Tm being measured by Differential Scanning Calorimetry (“DSC”) according to ASTM D3418; and wherein preferably:

■ the polyamide (PA) exhibits a biobased content of at least 45.0%; and/or

■ the 1,9-nonanediamine (C9) and the 1,10-decanediamine (CIO) both exhibit a biobased content of at least 90.0%;

■ the biobased content being expressed as the % of organic carbon of renewable origin measured according to ASTM D6866-22.

Claim 2. Polyamide (PA) according to claim 1, wherein the proportion of dicarboxylic acid(s) (DI) is between 5.0 and 15.0 mol% or between 7.0 and 13.0 mol% or between 8.0 and 12.0 mol% or between 9.0 and 11.0 mol%.

Claim 3. Polyamide (PA) according to claim 1 or 2, wherein terephthalic acid is a recycled terephthalic acid (rT) obtained through a depolymerization reaction of a (co)polyester comprising recurring units derived from terephthalic acid.

Claim 4. Polyamide (PA) according to claim 3, wherein the composition of the recycled terephthalic acid (rT) is the following:

- terephthalic acid (TP A);

- isophthalic acid (Impl): between 0 and 2.0 mol%, this proportion being calculated by formula IPA/(TPA+IPA) x 100 where TP A and IP A are the molar proportions of respectively terephthalic and isophthalic acid in rT;

- one or more organic impurities Imp2 selected from the group consisting of formic acid (FA) and acetic acid (AA), wherein the total proportion of impurities Imp2 is less than 300 pg/g of rT;

- one or more aromatic impurities Imp3 selected from the group consisting of 4- carboxybenzaldehyde (4-CBA), benzoic acid (BZA) and p-toluic acid (p-TA), wherein the total proportion of impurities Imp3 is less than 300 pg/g of rT; with the proviso that the recycled terephthalic acid contains at least one of the three impurities Impl, Imp2 or Imp3.

Claim 5. Polyamide (PA), notably according to any one of the preceding claims, the recurring units of which consist essentially or consist of the following units: where Ri is the alkylene of formula -(CH2)9- (C9) or -(CH2)IO- (CIO) with the following proportions of recurring units (RPAI) and (RPA2):

- (RPAI): between 85.0 and 98.0 mol.%;

- (RPA2): between 2.0 (value excluded) and 15.0 mol.%;

- the relative molar proportion of C9/C10 being between 18/82 and 95/5; wherein the polyamide (PA) exhibits a melting temperature (Tm) lower than and equal to 300.0°C (< 300.0°C), preferably lower than and equal to 295.0°C (< 295.0°C), Tm being measured by Differential Scanning Calorimetry (“DSC”) according to ASTM D3418; and wherein the polyamide (PA) preferably exhibits a biobased content of at least 45.0%, the biobased content being expressed as the % of organic carbon of renewable origin measured according to ASTM D6866-22; the expression "consist essentially" meaning that the recurring units of polyamide (PA) consist of the recurring units (RPAI)- RPA2) and up to 1.0 mol%, more preferably up to 0.50 mol%, more preferably up to 0.25 mol%, more preferably up to 0.10 mol%, of recurring units other than said recurring units, this proportion in mol% being based on the total amount of recurring units in the polyamide (PA).

Claim 6. Polyamide (PA) according to any one of the preceding claims, wherein the proportion of C9 is > 30.0 mol%, preferably > 50.0 mol%, preferably > 55.0 mol% and/or < 90.0 mol%.

Claim 7. Polyamide (PA) according to any one of the preceding claims, wherein the proportions of C9 and CIO are the following:

■ C9: > 50.0 mol% and < 95.0 mol%; and

■ CIO: > 5.0 mol% and < 50.0 mol%; or the following:

■ C9: > 55.0 mol% and < 95.0 mol%; and

■ CIO: > 5.0 mol% and < 45.0 mol%; or the following:

■ C9: > 55.0 mol% and < 90.0 mol%; and

■ CIO: > 10.0 mol% and < 45.0 mol%.

Claim 8. Polyamide (PA) according to any one of the preceding claims, wherein the proportions of C9 and CIO are the following:

■ between 50.0 and 95.0 mol% of C9; and

■ between 5.0 and 50.0 mol% of CIO; or

■ between 55.0 and 95.0 mol% of C9; and

■ between 5.0 and 45.0 mol% of CIO; or

■ between 65.0 and 75.0 mol% of C9; and

■ between 25.0 and 35.0 mol% of CIO. or

■ between 75.0 and 85.0 mol% of C9; and

■ between 15.0 and 25.0 mol% of CIO.

Claim 9. Polyamide (PA) according to any one of the preceding claims, wherein 1,9- nonanediamine (C9) and 1,10-decanediamine (CIO) both exhibit a biobased content of at least 95.0%, preferably at least 99.0%, preferably at least 99.5%, preferably at least 99.9%.

Claim 10. Polyamide according to any one of the preceding claims, exhibiting a biobased content of at least 50.0%, preferably at least 52.0%, the biobased content being expressed as the % of organic carbon of renewable origin measured according to ASTM D6866-22.

Claim 11. Polyamide according to any one of the preceding claims, wherein polyamide (PA) is free of recurring units derived from a lactam or from an amino-acid.

Claim 12. Polyamide (PA) according to any one of the preceding claims, wherein the end- groups of the polyamide (PA) are selected in the group of -NH2, -COOH and amide end- groups.

Claim 13. Polyamide (PA) according to any one of the preceding claims, wherein polyamide (PA) comprises end-groups of formula -NH2 and/or -COOH and amide end-groups of formula -NH-C(=O)-G or -C(=O)-NX-G where X is H or (Ci-C3)-alkyl group, notably Me, and G is a C1-C16 organic group, preferably a C1-C12 organic group, preferably a C1-C10 organic group.

Claim 14. Polyamide (PA) according to any one of the preceding claims, wherein the end- groups of polyamide (PA) consist essentially or consist of end-groups of formula -NH2 and/or -COOH and amide end-groups of formula -NH-C(=O)-G or -C(=O)-NX-G where X is H or (Ci-C3)-alkyl group, notably Me, and G is a C1-C16 organic group, preferably a C1-C12 organic group, preferably a C1-C10 organic group.

Claim 15. Polyamide (PA) according to claim 13 or 14, wherein G is an organic group which:

- contains carbon and hydrogen atoms and may also contain at least one additional atom selected in the group of N atoms, O atoms and combination thereof; or

- contains only carbon, hydrogen, N and O atoms; or

- contains only carbon, hydrogen and N atoms; or

- is an hydrocarbon group.

Claim 16. Polyamide (PA) according to any one of the preceding claims, having a number average molecular weight ("Mn") ranging: from 5,000 g/mol to 40,000 g/mol, or from 5,000 g/mol to 20,000 g/mol, or preferably from 6,000 to 18,000 g/mol; more preferably from 7,000 g/mol to 15,000 g/mol; Mn being determined 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 or by Size Exclusion Chromatography (SEC) coupled to a light scattering instrument or refractive index detector calibrated with the use of polystyrene standards.

Claim 17. Polyamide (PA) according to any one of the preceding claims, having a weightaverage molecular weight ("Mw") between 10,000 and 35,000 g/mol, Mw being determined by Size Exclusion Chromatography (SEC) coupled to a light scattering instrument or refractive index detector calibrated with the use of polystyrene standards.

Claim 18. Polyamide (PA) according to any one of the preceding claims, having an inherent viscosity (IV) of at least 0.70 dL/g, the IV being measured according to ASTM D5225 with the use of a mixture phenol/l,l,2,2-tetrachloroethane (60/40 wt. ratio).

Claim 19. Polyamide (PA) according to any one of the preceding claims, exhibiting a glass transition temperature (Tg) of at least 100°C, preferably at least 105.0°C, preferably at least 108.0°C, preferably at least 109.0°C, preferably at least 110°C, more particularly between 100 and 130°C, Tg being measured by Differential Scanning Calorimetry (“DSC”) according to ASTM D3418, notably using a heating and cooling rate of 20°C/min.

Claim 20. Polyamide (PA) according to any one of the preceding claims, exhibiting a melting temperature (Tm) which is: strictly lower than 300°C (< 300°C); or lower than or equal to 298.0°C (< 298.0°C), preferably lower than or equal to 297.0°C (< 297.0°C), preferably lower than or equal to 296.0°C (< 296.0°C), preferably lower than or equal to 295.0°C (< 295.0°C);

Tm being measured by Differential Scanning Calorimetry (“DSC”) according to ASTM D3418, notably using a heating and cooling rate of 20°C/min.

Claim 21. Polyamide (PA) according to any one of the preceding claims, exhibiting a melting temperature (Tm) which is at least 280°C, preferably at least 285°C, Tm being measured by Differential Scanning Calorimetry (“DSC”) according to ASTM D3418, notably using a heating and cooling rate of 20°C/min.

Claim 22. Polyamide (PA) according to any one of the preceding claims, exhibiting a crystallization temperature (Tc) of at most 265.0°C, Tc being measured by Differential Scanning Calorimetry (“DSC”) according to ASTM D3418, notably using a heating and cooling rate of 20°C/min.

Claim 23. Polyamide (PA) according to any one of the preceding claims, exhibiting a heat of fusion (Hm) which is:

- between 60.0 and 85.0 J/g; at least 60.0 J/g, preferably at least 65.0 J/g;

Hm being measured by Differential Scanning Calorimetry (“DSC”) according to ASTM D3418, notably using a heating and cooling rate of 20°C/min.

Claim 24. Polyamide (PA) according to any one of the preceding claims, exhibiting a heat of fusion (Hm) which is at least 70.0 J/g; Hm being measured by Differential Scanning Calorimetry (“DSC”) according to ASTM D3418, notably using a heating and cooling rate of 20°C/min.

Claim 25. Polyamide (PA) according to any one of the preceding claims, exhibiting the following thermal properties:

Tm is > 280.0 and < 300.0°C; and

Tg is > 110°C; and

Hm is > 60.0 J/g; preferably A=(Tm - Tc) is < 42.0°C.

Claim 26. Polyamide (PA) according to any one of the preceding claims, exhibiting:

- a difference A = (Tm - Tc) lower than or equal to 42.0°C, preferably lower than or equal to 41.0°C, preferably lower than or equal to 40.0°C; and/or

- a difference A* = (Tc - Tg) higher than or equal to 130.0°C;

Tm, Tc and Tg being measured by Differential Scanning Calorimetry (“DSC”) according to ASTM D3418, notably using a heating and cooling rate of 20°C/min.

Claim 27. Polyamide (PA) according to any one of the preceding claims, exhibiting a water uptake at saturation at 90°C lower than 3.0 wt%, preferably lower than 2.7 wt%, wherein the water uptake is determined by providing a specimen shaped according to ISO 527 in its dry state (moisture content of less than 0.2 %wt), immersing the same in deionized water at 90°C, until reaching a constant weight and according to formula:

Water u ptake wherei .n

Wbefore is the weight of the shaped specimen in its original dry state and Wafter is the weight of the shaped specimen after water uptake.

Claim 28. Polymer (PA) according to any one of the preceding claims, wherein the polyamide (PA) is prepared by polycondensing the monomers constituting the polyamide.

Claim 29. Polymer (PA) according to any one of the preceding claims, wherein the polyamide (PA) is prepared by by polycondensation by heating a reaction mixture (RM) comprising, consisting essentially of or consisting of:

- a mixture of monomers (MM) comprising, consisting essentially of or consisting of the diamine component (A) and the dicarboxylic acid component (B);

- optionally a catalyst, notably selected in the group consisting of phosphorous acid, ortho-phosphoric acid, meta-phosphoric acid, alkali-metal hypophosphite such as sodium hypophosphite and phenylphosphinic acid;

- optionally at least one capping agent;

- optionally water in a proportion which is preferably less than 80.0 wt.%, preferably less than 50.0 wt.% water, this proportion of water is based on the total weight of the reaction mixture (RM).

Claim 30. Polymer composition (PC) comprising or consisting of:

- at least one polyamide (PA) as disclosed in any one of claims 1-29;

- a component (c) blended with polyamide(s) (PA) and selected in the group consisting of reinforcing fillers (F), plastic additives (A), polyamides (PA*) and combinations of two or more of said components; where polyamide (PA*) is not a polyamide comprising 9T and 10T units.

Claim 31. Polymer composition (PC) according to claim 30, wherein the polymer composition (PC) comprises glass fibers and/or carbon fibers.

Claim 32. Use of the polyamide (PA) as defined in any one of claims 1-29 or the polymer composition (PC) as defined in claims 30 or 31 for the preparation of a component of an electronic device, notably of a mobile electronic device.

Claim 33. Use according to claim 32, wherein the component is a backbone, an antenna window, a fitting part, a snap fit part, a mutually moveable part, a functional element, an operating element, a tracking element, an adjustment element, a carrier element, a frame element, a switch, a connector, a cable, a housing or a speaker part.

Claim 34. Electronic device, notably a mobile electronic device, comprising at least one component made of or comprising the polyamide (PA) as defined in any one of claims 1-29 or the polymer composition (PC) as defined in claim 30 or 31.

Claim 35. Electronic device according to claim 34, wherein the component is a backbone, an antenna window, a fitting part, a snap fit part, a mutually moveable part, a functional element, an operating element, a tracking element, an adjustment element, a carrier element, a frame element, a switch, a connector, a cable, a housing or a speaker part.

Claim 36. Component of an electronic device, notably of a mobile electronic device, made of or comprising the polyamide (PA) as defined in any one of claims 1-29 or the polymer composition (PC) as defined in claim 30 or 31.

Claim 37. Component according to claim 36 which is a backbone, an antenna window, a fitting part, a snap fit part, a mutually moveable part, a functional element, an operating element, a tracking element, an adjustment element, a carrier element, a frame element, a switch, a connector, a cable, a housing or a speaker part.