Bio-based transparent polyamide

Abstract

Described herein is a polyamide (PA) that exhibits a glass transition temperature (Tg) of at least 170°C and includes repeating units formed by polycondensation of a diamine component (A) and a dicarboxylic acid component (B), wherein the diamine component (A) includes a) 48.0 to 95.0 mol % of MACM and b) 5.0 to 52.0 mol % of PACM, these percentages in mol % being based on the total amount of diamines in the diamine component (A); and the dicarboxylic acid component (B) includes c) 28.0 to 55.0 mol % of isophthalic acid and d) 45.0 to 72.0 mol % of a dicarboxylic acid (DA) selected from the group consisting of nonanedioic acid, decanedioic acid, and combinations thereof, these percentages in mol % being based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B).

Description

[Technical Field]

[0001] This application is a continuation of U.S. Patent Application No. 63 / 428201, filed November 28, 2022, and European Patent Application No. This application claims priority from U.S. Pat. No. 22306986.5, the contents of which are incorporated herein by reference in their entirety for all purposes. In the event of any discrepancy between this application and the two applications that would affect the clarity of terminology or wording, only this application shall be referenced.

[0002] The present invention relates to a bio-based transparent polyamide having steam resistance suitable for use in the manufacture of transparent articles. [Background technology]

[0003] Grilamid® TR90 and Rilsan® Clear G850 Rnew are two examples of transparent polyamides, but the glass transition temperatures of these two polyamides are below 200°C (TR90: 155°C, G850: 150°C), which can be a limitation in some applications.

[0004] U.S. Patent Application Publication No. 2005 / 272908 discloses a transparent polyamide as the condensation product of a) at least one diamine selected from the group consisting of aromatic diamines, arylaliphatic diamines, and cycloaliphatic diamines; and b) tetradecanedioic acid or a mixture comprising at least 50 mole % tetradecanedioic acid and at least one diacid selected from the group consisting of aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and cycloaliphatic dicarboxylic acids.

[0005] U.S. Pat. No. 5,696,202 discloses a polyamide having a Tg of 157° C. as a condensation product of dodecanedicarboxylic acid and bis(3-methyl-4-aminocyclohexyl)methane (MACM), and a polyamide as a condensation product of decanedioic acid and MACM.

[0006] EP 1595907 discloses transparent polyamides based on cycloaliphatic diamines but with low Tg.

[0007] U.S. Patent Application Publication No. 2010 / 022742(D1) discloses a transparent, high-temperature steam sterilizable copolyamide made from a) 35-42 mol% MACM (which can be replaced by up to 50% PACM); b) 35-42 mol% isophthalic acid (which can be replaced by up to 50% terephthalic acid); and c) 16-30 mol% laurinlactam. U.S. Patent Application Publication No. 2010 / 022742 also discloses a polyamide containing 23 mol% MACM, 27 mol% PACM, 34% isophthalic acid, and 16 mol% dodecanedioic acid. The polyamide described in claim 1 contains more than 42 mol% MACM.

[0008] US Pat. No. 9,453,106 discloses polyamides prepared using isophthalic acid and terephthalic acid.

[0009] U.S. Patent No. 6,277,911 discloses a transparent, amorphous polyamide prepared from at least one alkyl-substituted alicyclic diamine having 14 to 22 carbon atoms selected from the group consisting of 2,6-bis(aminomethyl)norbornane, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, bis(4-aminomethylcyclohexyl), diaminomethyl-tricyclodecane, 1,3-bis(aminomethyl)-dicyclohexane, bis(4-amino-3-methyl-2,2-ethylcyclohexyl)methane, bis(4-amino-3,5-diethylcyclohexyl)methane, and 2,2-bis-1,4-bis(aminomethyl)-dicyclohexane; at least one unbranched aliphatic dicarboxylic acid having 7 to 14 carbon atoms; and at least one aromatic dicarboxylic acid present in an amount of 20 mol% or less. The combination of MACM and PACM is not disclosed.

[0010] US Patent Application Publication No. 2022 / 0177649(D2) discloses a polyamide having the units AB / AC / D, wherein (A) is at least one cycloaliphatic diamine selected from MACM and PACM; (B) is at least one aromatic dicarboxylic acid selected from the group consisting of isophthalic acid, naphthalenedicarboxylic acid, and terephthalic acid; (C) is at least one aliphatic dicarboxylic acid selected from the group consisting of decanedioic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, and hexadecanedioic acid; and (D) is at least one lactam or one aminocarboxylic acid selected from the group consisting of laurolactam, undecanolactam, 12-aminododecanoic acid, and 11-aminoundecanoic acid.

[0011] EP 4067409 discloses the use of bisalicyclic monomers with a high renewable carbon index, in particular MACM.PACM / 12 polyamides with a broad range of MACM / PACM molar ratios from 5 / 95 to 95 / 5.

[0012] [Problem to be solved by the invention] Many items in everyday life (such as containers) require transparency and UV resistance. Some applications also require steam sterilizable polymers and articles made from these polymers that maintain their optical and mechanical properties (e.g., do not warp after steam exposure) after a sterilization cycle.

[0013] In recent years, consumer behavior has also been shifting towards more sustainable products, and this trend is also rapidly increasing for polymers, with the market demanding polymeric articles with a high bio-content.

[0014] Therefore, there is a need for sustainable polymers with high bio-content and polymer compositions containing said polymers that exhibit a combination of mechanical, thermal, and optical properties, even after steam sterilization, and that are UV resistant.

[0015] The polyamide and polymer compositions of the present invention aim to solve this technical problem.

[0016] BRIEF DISCLOSURE OF THE INVENTION The invention is set out in the following set of claims.

[0017] The present invention relates to a polyamide as disclosed in any one of claims 1 to 38.

[0018] The present invention also relates to a polymer composition as disclosed in any one of claims 39-46.

[0019] The invention also relates to the use as disclosed in claim 47 and to the container as disclosed in claim 47.

[0020] More precise and detailed information on these topics is provided below.

[0021] [Definition] These definitions apply to this disclosure.

[0022] wt% means weight %. mol% means mole %.

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

[0024] Where numerical ranges are given herein, the endpoints of the ranges are included (even open-ended ranges, such as those including "at least" or "most").

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

[0026] The proportion of diamine in diamine component (A) is expressed in mole % based on the total amount of diamine in diamine component (A). The proportion of dicarboxylic acid in dicarboxylic acid component (B) is expressed in mole % based on the total amount of dicarboxylic acid in dicarboxylic acid component (B).

[0027] The proportion of repeat units in the polyamide (PA) is expressed in mole % and is based on the total amount of repeat units in the polyamide (PA).

[0028] Dicarboxylic acids are organic compounds containing two carboxyl groups (-COOH). DETAILED DESCRIPTION OF THE INVENTION

[0029] The present invention relates to a polyamide (PA), in particular an amorphous polyamide, which exhibits a glass transition temperature (Tg) of at least 170°C and comprises repeating units formed from the polycondensation of a diamine component (A) and a dicarboxylic acid component (B), The diamine component (A) is a) 48.0 to 95.0 mol% MACM; b) 5.0 to 52.0 mol% of PACM; Including, These mole percent ratios are based on the total amount of diamine in diamine component (A); The dicarboxylic acid component (B) is c) 28.0 to 55.0 mol% isophthalic acid; d) 45.0 to 72.0 mole % of a dicarboxylic acid (DA) selected from the group consisting of nonanedioic acid, decanedioic acid, and combinations thereof; Including, These molar percentages are based on the total amount of dicarboxylic acid groups in the dicarboxylic acid component (B); Regarding polyamide (PA).

[0030] Embodiment (E1): In embodiment (E1), the dicarboxylic acid (DA) is decanedioic acid. This embodiment (E1) is applicable to any embodiment or detail of the present disclosure.

[0031] The invention according to this embodiment (E1) therefore provides a polyamide (PA), in particular an amorphous polyamide, which exhibits a glass transition temperature (Tg) of at least 170°C and comprises repeating units formed from the polycondensation of a diamine component (A) and a dicarboxylic acid component (B), The diamine component (A) is a) 48.0 to 95.0 mol% MACM; b) 5.0 to 52.0 mol% of PACM; Including, These mole percent ratios are based on the total amount of diamine in diamine component (A); The dicarboxylic acid component (B) is c) 28.0 to 55.0 mol% isophthalic acid; d) 45.0 to 72.0 mol% decanedioic acid; Including, These proportions in mole percent are based on the total amount of diacids in dicarboxylic acid component (B); It also relates to polyamides (PA).

[0032] The polyamide (PA) of the present invention is formed by polycondensation of a diamine (diamine component (A)) and a dicarboxylic acid (dicarboxylic acid component (B)). Those skilled in the art will understand that the ratio of -NH2 derived from the diamine component (A) and the ratio of -COOH derived from the dicarboxylic acid component (B) are substantially equimolar. Therefore, the molar ratio of -NH2 / COOH can be 0.9 to 1.1, preferably 0.95 to 1.05, and more preferably 0.98 to 1.02.

[0033] Thus, the polyamide (PA) disclosed in the present invention comprises the diamine of the diamine component (A) and the dicarboxylic acid of the dicarboxylic acid component (B) in a reacted form in the ratios indicated herein.

[0034] Further details regarding the diamine component (A) and the dicarboxylic acid component (B) are provided below.

[0035] Diamine component (A) The diamine component (A) is a) 48.0 to 95.0 mol% MACM; b) 5.0 to 52.0 mol% of PACM; Including, These proportions in mole percent are based on the total amount of diamines in the diamine component (A).

[0036] Combining MACM and PACM in the proportions indicated herein can result in polyamides that meet the requirements set forth above.

[0037] MACM, or 4,4'-methylenebis(2-methylcyclohexylamine), has the formula: [ka] It is a diamine. PACM, or 4,4'-methylenebiscyclohexylamine, has the formula: [ka] It is a diamine.

[0038] The PACM monomer used to prepare the polyamides (PA) of the present disclosure is typically in the form of a mixture of three isomers: (trans,trans)-4,4'-methylenebis[cyclohexylamine], (cis,trans)-4,4'-methylenebis[cyclohexylamine], and (cis,cis)-4,4'-methylenebis[cyclohexylamine]. See Macromolecules 1971, Vol. 4, No. 3, 347-350. Preferably, the PACM monomer used to prepare the polyamides (PA) of the present disclosure contains 15.0 to 25.0 mol % of (trans,trans)-4,4'-methylenebis[cyclohexylamine], based on the content of the three isomers. As an example, PACM 20, disclosed in the Experimental Section, exhibits a (trans,trans) proportion of approximately 20%.

[0039] The diamine component (A) preferably does not contain lactam.The diamine component (A) preferably does not contain hexamethylenediamine.

[0040] According to one embodiment, diamine component (A) consists essentially of or consists of MACM and PACM in the proportions indicated herein. In the context of the present invention, the term "consisting essentially of" with respect to the diamine component means that diamine component (A) comprises MACM and PACM and may also contain up to 2.0 mol %, preferably up to 1.0 mol %, and more preferably up to 0.5 mol % of other diamines, where this percentage in mol % is based on the total amount of diamines in diamine component (A). In other words, diamine component (A) consists of MACM, PACM, and up to 2.0 mol %, preferably up to 1.0 mol %, and more preferably up to 0.5 mol % of at least one diamine other than MACM and other than PACM, where this percentage in mol % is based on the total amount of diamines in diamine component (A).

[0041] Dicarboxylic acid component (B) The dicarboxylic acid component (B) is 28.0 to 55.0 mol% isophthalic acid, 45.0 to 72.0 mol % of a dicarboxylic acid (DA) selected from the group consisting of nonanedioic acid, decanedioic acid, and combinations thereof; Including, These proportions in mole percent are based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B).

[0042] According to one embodiment, the dicarboxylic acid (DA) is nonanedioic acid.

[0043] According to another embodiment (E1), the dicarboxylic acid (DA) is decanedioic acid (i.e., sebacic acid). According to this embodiment, the dicarboxylic acid component (B) is 28.0 to 55.0 mol% isophthalic acid, 45.0 to 72.0 mol % of decanedioic acid, Including, These proportions in mole percent are based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B).

[0044] Nonanedioic acid (or azelaic acid) is a diacid of the formula: HOOC-(CH2)7-COOH.

[0045] Decanedioic acid (or sebacic acid) is a diacid of the formula: HOOC-(CH2)8-COOH.

[0046] The dicarboxylic acid component (B) preferably does not contain terephthalic acid. The dicarboxylic acid component (B) preferably contains dodecanedioic acid (HOOC-(CH) 10 -COOH).

[0047] According to one embodiment, dicarboxylic acid component (B) consists essentially of or consists of isophthalic acid and dicarboxylic acid (DA). In the context of the present invention, the expression "consisting essentially of" with respect to dicarboxylic acid component (B) means that dicarboxylic acid component (B) consists of isophthalic acid, dicarboxylic acid (DA), and up to 2.0 mol %, preferably up to 1.0 mol %, and more preferably up to 0.5 mol % of at least one dicarboxylic acid other than isophthalic acid and dicarboxylic acid (DA), said percentages in mol % being based on the total amount of dicarboxylic acids in dicarboxylic acid component (B).

[0048] According to this embodiment and embodiment (E1), dicarboxylic acid component (B) consists of isophthalic acid, decanedioic acid, and up to 2.0 mol %, preferably up to 1.0 mol %, and more preferably up to 0.5 mol % of at least one diacid other than isophthalic acid and other than decanedioic acid, the proportions in mol % being based on the total amount of dicarboxylic acids in dicarboxylic acid component (B).

[0049] The aromatic content in polyamide (PA) is typically less than 11.0 wt. %, preferably less than 10.0 wt. The aromatic content corresponds to the weight of carbon and hydrogen atoms in the aromatic rings present in the polyamide (PA) polymer relative to the total weight of the polyamide (PA) polymer. Thus, in the case of a polyamide (PA) based on a diamine component (A) consisting of MACM and PACM and a dicarboxylic acid component (B) consisting of isophthalic acid and sebacic acid, the only carbon and hydrogen atoms that should be considered are those derived from isophthalic acid. For clarity, the aromatic content is based only on the polyamide (PA) polymer, and does not take into account the presence of other components, such as additives, that may be present in the polyamide (PA). A low aromatic content is beneficial to the UV resistance of the polyamide (PA).

[0050] Embodiment (E2): According to a preferred embodiment (E2), the polyamide (PA) comprises repeating units formed from the polycondensation of a diamine component (A) and a dicarboxylic acid component (B), The diamine component (A) is a) 85.0 to 95.0 mol% MACM; b) 5.0 to 15.0 mol% of PACM; comprising, consisting essentially of, or consisting of These mole percent ratios are based on the total amount of diamine in diamine component (A); The dicarboxylic acid component (B) is c) 45.0 to 55.0 mol% isophthalic acid; d) 45.0 to 55.0 mole % of a dicarboxylic acid (DA) selected from the group consisting of nonanedioic acid, decanedioic acid, and combinations thereof; comprising, consisting essentially of, or consisting of These proportions in mol % are based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B).

[0051] More specifically, the proportion of MACM can be 87.0 to 93.0 mol%, or 88.0 to 92.0 mol%, or 89.0 to 91.0 mol%, and / or the proportion of PACM can be 7.0 to 13.0 mol%, or 8.0 to 12.0 mol%, or 9.0 to 11.0 mol%.

[0052] The proportion of isophthalic acid can be 47.0 to 53.0 mol%, or 48.0 to 52.0 mol%, or 49.0 to 51.0 mol%, and / or the proportion of dicarboxylic acid (DA) can be 47.0 to 53.0 mol%, or 48.0 to 52.0 mol%, or 49.0 to 51.0 mol%.

[0053] The embodiment (E1) applies to the embodiment (E2).

[0054] Embodiment (E3): According to another preferred embodiment (E3), the polyamide (PA) comprises repeating units formed from the polycondensation of a diamine component (A) and a dicarboxylic acid component (B), The diamine component (A) is a) 88.0 to 92.0 mol% MACM; b) 8.0 to 12.0 mol% PACM; comprising, consisting essentially of, or consisting of These mole percent ratios are based on the total amount of diamine in diamine component (A); The dicarboxylic acid component (B) is c) 48.0 to 52.0 mol% isophthalic acid; d) 48.0 to 52.0 mole % of a dicarboxylic acid (DA) selected from the group consisting of nonanedioic acid, decanedioic acid, and combinations thereof; comprising, consisting essentially of, or consisting of These proportions in mol % are based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B).

[0055] The embodiment (E1) is applied to the embodiment (E3).

[0056] Repeating units in polyamide (PA) The present invention also relates to a polyamide (PA) according to claim 12.

[0057] Those skilled in the art will recognize that the repeating units (R PA1 ) and (R PA2 ) and (R PA1 ) is a compound of formula (I) [ka] and (R PA2 )teeth, [ka] and / or [ka] is expressed as In these formulas, the substituents X1 and X2 on the cyclohexane ring are both Me or both H, and the ratio of these substituents Me and H in the polyamide (PA) is 48.0 to 95.0 mol % Me, and 5.0 to 52.0 mol% H is.

[0058] Similarly, according to embodiment (E1), the skilled person will be able to understand how to obtain, by polycondensation of the monomers defined above, repeating units (R PA1 ) and (R PA2 ) and a polyamide (PA) containing: [ka] (In these formulas, the substituents X1 and X2 on the cyclohexane ring are both Me or both H, and the ratio of these substituents Me and H in the polyamide (PA) is 48.0 to 95.0 mol % Me, and 5.0 to 52.0 mol% H (It is).

[0059] These two units (R PA1 ) and (R PA2 ) contains a carbonyl -(C=O)- group and an -NH- group, and polyamide (PA) is a polymer with units linked by amide bonds.

[0060] (R PA1 ) is derived from isophthalic acid, and (R PA2 ) are derived from nonanedioic acid and / or decanedioic acid.

[0061] The percentages given herein for MACM and PACM apply to the percentages of the substituents Me and H, respectively. The percentages of the substituents are: 1 It can be measured by 1 H NMR.

[0062] The polyamide (PA) disclosed in the present disclosure preferably does not contain repeating units derived from lactams. The polyamide (PA) disclosed in the present disclosure preferably does not contain repeating units derived from hexamethylenediamine. The polyamide (PA) disclosed in the present disclosure preferably does not contain repeating units derived from terephthalic acid or dodecanedioic acid. The polyamide (PA) disclosed in the present disclosure preferably does not contain repeating units derived from amino acids.

[0063] According to a preferred embodiment, the repeating units of the polyamide (PA) of the present disclosure are the repeating units (R PA1 ) and (R PA2 ) or consisting essentially of

[0064] The expression "consisting essentially of" with respect to repeat units means that the repeat units of the polyamide (PA) consist essentially of repeat units (R PA1 ) and (R PA2 ) and up to 2.0 mol %, preferably up to 1.0 mol %, preferably up to 0.5 mol % of (R PA1 ) and (RPA2 ) and a repeating unit other than the repeating unit.

[0065] Repeating unit (R PA1 ) and (R PA2 ) percentage Repeating unit (R PA1 The proportion of ) is 28.0 to 55.0 mol %.

[0066] Repeating unit (R PA2 The proportion of ) is 45.0 to 72.0 mol %.

[0067] These percentages are given relative to the total amount of repeat units in the polyamide (PA).

[0068] In particular in Example (E3), all percentages given herein for isophthalic acid are based on the repeating unit (R PA1 Similarly, all percentages given herein for dicarboxylic acids (DA), especially in example (E3), apply equally to the proportions of repeating units (R PA2 ) proportions.

[0069] The present invention preferably comprises a repeating unit (R PA1 ) and (R PA2 ), in particular according to embodiment (E1), in which the following proportions are present: · 85.0-95.0 mol% Me; 5.0 to 15.0 mol% H; 45.0 to 55.0 mol% of repeating units (R PA1 ); 45.0 to 55.0 mol% of repeating units (R PA2 ); or the following percentages: · 88.0-92.0 mol% Me; 8.0-12.0 mol% H; 48.0 to 52.0 mol% of repeating units (R PA1 ); 48.0 to 52.0 mol% of repeating units (R PA2 ); It also relates to polyamides (PA) defined as

[0070] The polyamides (PA) of the present invention typically have a number average molecular weight ("Mn") of at least 10,000 g / mol. Mn may be at least 12,000 g / mol, and most preferably at least 14,000 g / mol. Mn is typically at most 20,000 g / mol, or at most 15,000 g / mol. Mn can be determined using the following formula (1): Mn = 2,000,000 / [EG] (1), where [EG] is the percentage of end groups in the PA expressed in mmol / kg. More precisely, there are known methods for measuring the percentage of amine and acid end groups.

[0071] The end groups of the polyamide (PA) are selected from the group consisting of -NH2, -COOH, and amide end groups. In fact, the end groups of the polyamide (PA) may be -NH2 or -COOH. However, when the polycondensation is accompanied by the addition of an end-capping agent selected from the group consisting of monocarboxylic acids, primary amines, and combinations thereof, these end groups may be partially or completely converted to amide end groups.

[0072] Amide end groups are of the formula -NH-C(=O)-R (wherein R is an alkyl, aryl, or cycloalkyl group) and / or -C(=O)-NH-R' (wherein R' is an alkyl or cycloalkyl group). R is more specifically a linear or branched C1-C 18 Alkyl group or C5-C 10 R' is more specifically a linear or branched C2-C cycloalkyl group. 18 It is an alkyl group.

[0073] Amide end groups of the formula -NH-C(=O)-R result from the reaction of the end group -NH2 with a monocarboxylic acid (endcapping agent) of the formula R-COOH.

[0074] The monocarboxylic acid (end-capping agent) is advantageously benzoic acid, cyclohexanoic acid, R-COOH (where R is a linear or branched C1-C 18 R is a radical derived from an acid of formula R-COOH.

[0075] More specifically, the monocarboxylic acid (endcapping agent) can be selected from the group consisting of acetic acid, propanoic acid, butyric acid, valeric acid, caproic acid, lauric acid, stearic acid, 2-ethylhexanoic acid, cyclohexanoic acid, benzoic acid, and combinations of two or more of these acids.

[0076] The monocarboxylic acid (endcapping agent) is more specifically represented by the formula CH3-(CH2) n -COOH (n is an integer from 0 to 17). In that case, the amide end group has the formula -NH-C(=O)-(CH2) n -CH3.

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

[0078] The primary amine (endcapping agent) is advantageously of the formula R'-NH2, where R' is a linear or branched C2-C 18 R' is a radical derived from an amine of formula R'-NH2.

[0079] The primary amine (endcapping agent) is more specifically a compound of the formula CH3-(CH2) n’ -NH2 (n' is an integer from 1 to 17), in which case the amide end group has the formula -C(=O)-NH-(CH2) n’ -CH3.

[0080] More specifically, the primary amine (endcapping agent) can be selected from the group consisting of propylamine, butylamine, pentylamine, hexylamine, 2-ethylhexylamine, n-octylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, stearylamine, cyclohexylamine, and combinations of two or more of these amines.

[0081] The proportion of terminal groups is 1 Quantitation can be achieved by 1 H NMR or potentiometry.

[0082] Bio content of polyamide (PA) The polyamide (PA) can preferably exhibit a bio-content of at least 20.0%, expressed as the percentage of organic carbon derived from renewable resources, measured according to ASTM D6866-22.

[0083] Nonanedioic acid (azelaic acid) and decanedioic acid (sebacic acid) may be derived from petroleum or natural gas. They may also be biobased as defined by ASTM D6866-22. A product is defined as "biobased" if it contains organic carbon derived from renewable sources such as agricultural products, plants, animals, fungi, microorganisms, marine organisms, or forest timber that live in the natural environment in equilibrium with the atmosphere.

[0084] This level of bio-content can be achieved through the use of bio-based nonanedioic acid (azelaic acid can be prepared from oleic acid: see “Azelaic acid: a bio-based building block for biodegradable polymers” Polymers (Basel). 2021 Nov 24;13(23):4091; DOI 10.3390 / polym13234091) and / or bio-based decanedioic acid (sebacic acid can be prepared from castor oil).

[0085] Biocontent is defined as the % of organic carbon that comes from renewable sources. 14 It corresponds to the amount of C calculated from the C percent and then corrected for isotopic proportions.

[0086] According to one embodiment, bio-based isophthalic acid can be used to prepare polyamide (PA). A method for preparing bio-based isophthalic acid is disclosed, for example, in WO 2014 / 144843. By using bio-based isophthalic acid, the bio-content of the polyamide (PA) can be at least 35.0%.

[0087] According to one embodiment, bio-based MACM and PACM can be used to prepare polyamides (PA). These diamines can be prepared from bio-based toluene and aniline by hydrogenation of the corresponding aromatic diamines according to EP 0618188 (see also EP 4067409). By using bio-based MACM and PACM, the bio-content of the polyamides (PA) can be at least 80.0%.

[0088] The bio-content of polyamide (PA) may be at least 90.0% and may reach 100%.

[0089] The bio content of the polyamide (PA) may be 20.0 to 100%, or 35.0 to 100%, or 80.0 to 100%.

[0090] According to one embodiment, the polyamide (PA) disclosed herein is prepared from biobased azelaic acid and / or sebacic acid exhibiting a bio-content of at least 99.0%, preferably at least 99.5%, preferably at least 99.9%, where the bio-content is expressed as the % of organic carbon derived from renewable resources as measured according to ASTM D6866-22.

[0091] According to another embodiment, the polyamide (PA) disclosed herein is prepared from MACM and / or PACM exhibiting a bio-content of at least 99.0%, preferably at least 99.5%, preferably at least 99.9%, where the bio-content is expressed as the % of organic carbon derived from renewable resources as measured according to ASTM D6866-22.

[0092] According to another embodiment, the polyamide (PA) disclosed herein is prepared from isophthalic acid exhibiting a bio-content of at least 99.0%, preferably at least 99.5%, preferably at least 99.9%, where the bio-content is expressed as the % of organic carbon derived from renewable resources as measured according to ASTM D6866-22.

[0093] Moisture absorption of polyamide (PA) Polyamide (PA) advantageously exhibits a water absorption of less than 5.0% by weight at 23° C. This water absorption may be less than 3.5% by weight.

[0094] The water absorption at 23°C is determined by (i) preparing dry (less than 0.2 wt. % moisture) test specimens molded according to ISO 527, (ii) immersing the test specimens in deionized water at 23°C until a constant weight is reached, and (iii) calculating the water absorption using the following formula:

number

[0095] Thermal and mechanical properties of the polyamides (PA) of the present disclosure As mentioned above, the polyamides (PA) of the present invention have surprisingly been found to exhibit a combination of thermal properties.

[0096] 1) Heat of fusion (Hm) Polyamide (PA) is amorphous.

[0097] Polyamides (PA) typically exhibit a heat of fusion (Hm) of at most 5.0 J / g, preferably at most 2.0 J / g.

[0098] Hm can be measured by differential scanning calorimetry ("DSC") according to ISO 11357 using heating and cooling rates of 20°C / min.

[0099] Hm can be more specifically measured as described in the experimental section.

[0100] Hm can be measured by differential scanning calorimetry ("DSC") according to ISO 11357 using a heating and cooling rate of 20°C / min. Each DSC test uses three scans: one heating to 320°C, followed by one cooling to -40°C, followed by a second heating to 320°C.

[0101] 2) Glass transition temperature (Tg) The polyamide (PA) exhibits a Tg of at least 170° C. The Tg of the polyamide (PA) may preferably be at least 190° C.

[0102] The Tg of the polyamide (PA), in particular of embodiment (E2) or (E3), is preferably at least 200°C, preferably at least 201°C.

[0103] The Tg of the polyamide (PA), especially of embodiment (E2) or (E3), is preferably 200.0°C or higher, preferably 201.0°C or higher.

[0104] Polyamides (PA) typically exhibit a Tg of up to 240°C, or even up to 220°C.

[0105] Therefore, Tg may be 200 to 240°C, or 201 to 240°C.

[0106] The glass transition temperature Tg as defined in the present invention is conveniently measured by differential scanning calorimetry ("DSC") according to ISO 11357, in particular using heating and cooling rates of 20°C / min.

[0107] Tg can be measured more specifically as described in the experimental section.

[0108] Tg can be measured by differential scanning calorimetry ("DSC") according to ISO 11357 using a heating and cooling rate of 20°C / min. Each DSC test uses three scans: a first heat to 320°C, followed by a first cool to -40°C, followed by a second heat to 320°C. Tg is determined from the second heat.

[0109] Mechanical and optical properties of the polyamides (PA) of the present disclosure Polyamides (PA) are also characterized by an optimized combination of mechanical and optical properties, which makes them suitable for the production of transparent objects, especially those in everyday life.

[0110] The polyamide (PA) may exhibit at least one of the following mechanical properties: a tensile modulus, measured in accordance with ASTM D638, of at least 2.0 GPa; and / or a tensile strength, measured in accordance with ASTM D638, of at least 80.0 MPa; and / or an elongation at break, measured in accordance with ASTM D638, of at least 12.0%; and / or ·Izod impact energy, measured in accordance with ASTM D256, of at least 65.0 J / m.

[0111] Polyamide (PA) also typically exhibits a transparency of at least 90.0%, preferably at least 95.0%, when measured according to ASTM D1003 on injection-molded specimens of 3.2 mm or 2.5 mm thickness.

[0112] Furthermore, polyamides (PA) also typically exhibit low haze: the haze of polyamides (PA), measured according to ASTM D1003 on injection-molded specimens of 3.2 mm or 2.5 mm thickness, is typically less than 8.0%, preferably less than 5.0%, and preferably less than 2.0%.

[0113] Preparation method of polyamide (PA) The polyamides (PA) described herein can be prepared by any conventional method compatible with the synthesis of polyamides and polyphthalamides.

[0114] Polyamides (PA) are usually prepared by polycondensation by heating a reaction mixture (RM) containing all the monomers (i.e., MACM, PACM, isophthalic acid, and dicarboxylic acids (DA) selected from the group consisting of azelaic acid, sebacic acid, and combinations thereof) in the presence of, preferably, less than 60% by weight, preferentially less than 30%, 20%, or 10% by weight of water, and preferentially without the addition of water. This proportion is given based on the total weight of the reaction mixture (RM). Polyamides (PA) are usually produced by polycondensation in the melt.

[0115] As is well known in polycondensation, the reaction mixture (RM) contains the diamine and diacid in amounts such that the proportion of -COOH groups from the diacid and the proportion of -NH2 groups from the diamine are substantially equimolar. The molar ratio of -COOH from the diacid of the dicarboxylic acid component (B) / -NH2 from the diamine of the diamine component (A) can be comprised between 0.9 and 1.1, preferentially between 0.95 and 1.05, and even more preferentially between 0.98 and 1.02.

[0116] The reaction mixture (RM) further preferably comprises a catalyst, which may be selected from the group consisting of phosphorous acid, ortho-phosphoric acid, meta-phosphoric acid, alkali metal hypophosphites, such as sodium hypophosphite, and phenylphosphinic acid, and combinations thereof. A convenient catalyst to use is sodium hypophosphite.

[0117] The reaction mixture (RM) may further comprise at least one endcapping agent as disclosed above, which can be used, inter alia, to control molecular weight.

[0118] According to one embodiment of the present disclosure, the reaction mixture (RM) comprises: a dicarboxylic acid (DA) selected from the group consisting of MACM, PACM, isophthalic acid, and azelaic acid, sebacic acid, and combinations thereof (preferably, the dicarboxylic acid (DA) is sebacic acid); an optional catalyst, in particular a catalyst selected from the group consisting of phosphorous acid, ortho-phosphoric acid, meta-phosphoric acid, alkali metal hypophosphites, such as sodium hypophosphite, and phenylphosphinic acid, and combinations thereof; optionally, at least one endcapping agent selected from the group consisting of monocarboxylic acids, primary amines, and combinations thereof; optionally, water in a proportion of less than 60% by weight, preferentially less than 30%, less than 20%, less than 10% by weight, based on the total weight of the reaction mixture (RM) (preferentially no water is added); It consists of:

[0119] The temperature to which the reaction mixture (RM) is heated must be high enough to induce a reaction between the amine and carboxyl groups of the monomers and reduce the viscosity of the mixture. This temperature is usually at least 200°C. Preferably, the temperature is above Tg + 80°C. Polycondensation forms amide bonds and releases water as a by-product.

[0120] The temperature can be increased stepwise during the polycondensation, an example of a stepwise increase is shown in Example 1.

[0121] The polycondensation is advantageously carried out in a well-stirred vessel equipped with means for removing volatile products of the reaction. Because the viscosity of the reaction mixture increases over time, the stirrer is adjusted to provide sufficient stirring of the reaction mixture at the beginning of the polymerization and again when the polycondensation conversion is nearly complete.

[0122] The conditions disclosed in the experimental section can be advantageously used for the preparation of polyamides (PA).

[0123] Polymer Composition (C) The present invention provides at least one polyamide (PA) as disclosed herein, at least one polymer additive selected from the group consisting of heat stabilizers, UV stabilizers, colorants, antistatic agents, and combinations of two or more of the foregoing additives; The present invention also relates to a polymer composition (C) containing:

[0124] More specifically, the polymer composition (C) contains at least one colorant and / or at least one UV stabilizer.

[0125] The polymer of the polymer composition (C) and the polymer additive are preferably blended.

[0126] The proportion of the polymer additive in the polymer composition (C) may be 0 to 10.0% by weight based on the total weight of the polymer composition (C), and this proportion is usually 0.5 to 10.0% by weight.

[0127] The polymer composition (C) may also contain or be blended with a polyamide different from the polyamide (PA).

[0128] The polymer composition (C) preferably exhibits the mechanical properties described above.Similarly, the polymer composition (C) preferably exhibits the optical properties described above.

[0129] The polymer composition (C) is prepared by a compounding method including the step of melting a polymer and mixing it with the other components of the polymer composition (C). Any equipment commonly used for compounding can be used, for example, a melt mixer such as a single-screw or twin-screw extruder, a single-screw or twin-screw kneader, or a Banbury mixer. The compounding method can be conveniently carried out using an extruder such as a single-screw or twin-screw extruder. The components other than the polyphthalamide can be incorporated into the polyphthalamide in a side feeder of the extruder.

[0130] Use of polyamide (PA) or polymer composition (C) The polyamides (PA) and the polymer compositions (C) can be used for the manufacture of articles, in particular transparent articles, in particular transparent articles for everyday use.

[0131] These articles can be manufactured from polyamide (PA) or polymer composition (C) by injection molding.

[0132] The polyamides (PA) and the polymer compositions (C) can be used for the production of decorative articles (particularly automotive interiors), sports goods (particularly ski boots and midsoles of sports shoes), toys, household items (particularly containers, plates, bowls, cans, beakers, baby bottles, drinking bottles, parts for kitchen appliances), parts for eyeglasses (particularly eyeglass frames or eyeglass side pieces, safety goggles), medical devices (particularly containers and syringes), parts for smartphones (particularly protective covers).

[0133] The polyamide (PA) and the polymer composition (C) can be used to manufacture containers, especially transparent containers. The present invention also relates to containers, especially transparent containers, manufactured from the polymer composition (C) disclosed herein. [Example]

[0134] This example demonstrates the synthesis, thermal performance, as well as the mechanical performance and sterilization resistance of the polyamides of the present invention.

[0135] Raw materials used in the preparation of the polyamide (PA) according to the invention The following monomers were used:

[0136] [Table 1]

[0137] Thermal Properties Thermal properties were measured by differential scanning calorimetry ("DSC") according to ISO 11357 using a heating and cooling rate of 20°C / min. Each DSC test uses three scans: a first heat to 320°C, followed by a first cool to -40°C, followed by a second heat to 320°C. The Tg is determined from the second heat.

[0138] Steam Sterilization Test The steam sterilization test consists of exposing polyamide samples to superheated steam for 100 cycles (134°C, 3 bar absolute pressure, 18 minutes per cycle). Clarity and warpage are assessed qualitatively after the test.

[0139] Preparation of Polyamides (PA) of Table I All copolyamides disclosed in Table I were prepared in an autoclave reactor equipped with a distillation line fitted with a pressure control valve. The preparation of all copolyamides followed the procedure detailed below for E1.

[0140] Example 1 (E1) Polyamide Ex1 was prepared according to the following recipe: a stainless steel autoclave equipped with a mechanical stirrer was charged with 113.48 g (0.47 mol) of MACM, 10.96 g (0.052 mol) of PACM20, 52.70 g (0.26 mol) of sebacic acid, 43.28 g (0.26 mol) of isophthalic acid, 1.6 g (5 wt %, 0.6 mmol) of aqueous phosphoric acid solution, and 10 g of deionized water. The autoclave was purged with nitrogen and then sealed. The temperature in the reactor was gradually increased to 290 °C while the pressure was adjusted to 11 bar. After reaching 290 °C, the pressure was gradually reduced to 1 bar while the temperature was further increased to 310 °C. The pressure was then further reduced to approximately 130 mbar, and the reaction mixture was held at 310 °C / 130 mbar for 15 minutes. The pressure was returned to 1 bar with nitrogen gas and the polymer was discharged as strands and pelletized.

[0141] [Table 2]

[0142] The transparency of the polyamide of Example E1 is maintained after 100 cycles of the steam test. Furthermore, only slight discoloration is observed after 100 cycles. The polyamide of Example E1 also exhibits a higher biobased content than Comparative Example CE1.

Claims

1. A polyamide (PA) exhibiting a glass transition temperature (Tg) of at least 170°C and containing repeating units formed by polycondensation of a diamine component (A) and a dicarboxylic acid component (B), The diamine component (A) is a) 48.0 to 95.0 mol % of a compound of the formula 【Chemistry 1】 MACM and b) 5.0 to 52.0 mol % of a compound of the formula 【Chemistry 2】 PACM and Including, These mole percent ratios are based on the total amount of diacids in the diamine component (A); The dicarboxylic acid component (B) is c) 28.0 to 55.0 mol% isophthalic acid; d) 45.0 to 72.0 mole % of a dicarboxylic acid (DA) selected from the group of nonanedioic acid (azelaic acid), decanedioic acid (sebacic acid), and combinations thereof; Including, These ratios in mole percent are based on the total amount of dicarboxylic acids in the dicarboxylic acid component (B); Tg is measured by differential scanning calorimetry ("DSC") according to ISO 11357; Polyamide (PA).

2. 2. Polyamide (PA) according to claim 1, wherein the dicarboxylic acid (DA) is decanedioic acid (sebacic acid).

3. The diamine component (A) is a) 85.0 to 95.0 mol % MACM; b) 5.0 to 15.0 mol % PACM; Including, The dicarboxylic acid component (B) is c) 45.0 to 55.0 mol % isophthalic acid; d) 45.0 to 55.0 mol % of a dicarboxylic acid (DA); Contains or or The diamine component (A) is a) 88.0 to 92.0 mol % MACM; b) 8.0 to 12.0 mol % PACM; Including, The dicarboxylic acid component (B) is c) 48.0 to 52.0 mol % isophthalic acid; d) 48.0 to 52.0 mol % of a dicarboxylic acid (DA); 3. Polyamide (PA) according to claim 1 or 2, comprising:

4. The ratio of MACM in the diamine component (A) is 87.0 to 93.0 mol%, or 88.0 to 92.0 mol%, or 89.0 to 91.0 mol% That is, and / or The proportion of PACM in the diamine component (A) is 7.0 to 13.0 mol%, or 8.0 to 12.0 mol%, or 9.0 to 11.0 mol% The polyamide (PA) according to any one of claims 1 to 3,

5. The polyamide (PA) according to any one of claims 1 to 4, wherein the diamine component (A) does not contain any lactam.

6. The polyamide (PA) according to any one of claims 1 to 5, wherein the diamine component (A) does not contain hexamethylenediamine.

7. 7. Polyamide (PA) according to any one of claims 1 to 6, wherein the diamine component (A) consists essentially of or consists of MACM and PACM, the expression "consisting essentially of" meaning, with respect to the diamine component, that component (A) consists of MACM, PACM and at most 2.0 mol %, preferably at most 1.0 mol %, and more preferably at most 0.5 mol % of at least one diamine other than MACM and other than PACM, said proportions in mol % being based on the total amount of diamines in the diamine component (A).

8. The ratio of isophthalic acid in the dicarboxylic acid component (B) is 47.0 to 53.0 mol%, or 48.0 to 52.0 mol%, or 49.0 to 51.0 mol% That is, and / or The ratio of the dicarboxylic acid (DA) in the dicarboxylic acid component (B) is 47.0 to 53.0 mol%, or 48.0 to 52.0 mol%, or 49.0 to 51.0 mol% The polyamide (PA) according to any one of claims 1 to 7,

9. The polyamide (PA) according to any one of claims 1 to 8, wherein the dicarboxylic acid component (B) does not contain terephthalic acid.

10. The polyamide (PA) according to any one of claims 1 to 9, wherein the dicarboxylic acid component (B) does not contain dodecanedioic acid.

11. 11. Polyamide (PA) according to any one of claims 1 to 10, wherein the dicarboxylic acid component (B) consists essentially of or consists of isophthalic acid and dicarboxylic acid (DA), the expression "consisting essentially of" meaning, with respect to the dicarboxylic acid component, that the dicarboxylic acid component (B) consists of isophthalic acid, dicarboxylic acid (DA) and at most 2.0 mol %, preferably at most 1.0 mol %, and more preferably at most 0.5 mol % of at least one dicarboxylic acid other than isophthalic acid and dicarboxylic acid (DA), said proportions in mol % being based on the total amount of the dicarboxylic acids in the dicarboxylic acid component (B).

12. Repeating unit (R ＰＡ１ ) and (R ＰＡ２ 12. Polyamide (PA) according to any one of claims 1 to 11, in particular comprising (R ＰＡ１ )but, 【Transformation 3】 (R ＰＡ２ )but, 【Chemistry 4】 and / or 【Transformation 5】 and preferably represented by (R ＰＡ２ ) is represented by (IIa), The substituent X on the cyclohexane ring of these formulas １ and X ２ are all Me or all H, and the ratio of these repeating units is ・(R ＰＡ１ ): 28.0 to 55.0 mol%; ・(R ＰＡ２ ): 45.0 to 72.0 mol%; and the ratio of these substituents Me and H in the polyamide (PA) is 48.0 to 95.0 mol % Me, and 5.0 to 52.0 mol% H Polyamide (PA).

13. The ratio of the substituents Me and H in the polyamide (PA) is 85.0 to 95.0 mol % Me; and 5.0 to 15.0 mol % H; 13. Polyamide (PA) according to claim 12, wherein

14. The proportion in the repeating units is ・(R ＰＡ１ ): 45.0 to 55.0 mol%; ・(R ＰＡ２ ): 45.0 to 55.0 mol%; 14. Polyamide (PA) according to claim 12 or 13, wherein

15. The polyamide (PA) according to any one of claims 1 to 14, which does not contain any repeating unit derived from a lactam or an amino acid.

16. The polyamide (PA) according to any one of claims 1 to 15, which does not contain any repeating units derived from hexamethylenediamine.

17. The polyamide (PA) according to any one of claims 1 to 16, which does not contain any repeating units derived from terephthalic acid.

18. The polyamide (PA) according to any one of claims 1 to 17, which does not contain any repeating units derived from dodecanedioic acid.

19. The repeating unit of the polyamide (PA) is a repeating unit (R ＰＡ１ ) and (R ＰＡ２ ), the expression "consisting essentially of" refers to said repeating units, and the repeating units of polyamide (PA) are those consisting essentially of repeating units (R ＰＡ１ ) and (R ＰＡ２ ) and up to 2.0 mol %, preferably up to 1.0 mol %, preferably up to 0.5 mol % of (R ＰＡ１ ) and other than (R ＰＡ２ The polyamide (PA) according to any one of claims 1 to 18, which means that it consists of repeating units other than .

20. 20. Polyamide (PA) according to any one of claims 1 to 19, which is amorphous and in particular exhibits a heat of fusion (Hm) of at most 5.0 J / g, preferably at most 2.0 J / g, Hm being measured by differential scanning calorimetry ("DSC") according to ISO 11357 using a heating and cooling rate of 20°C / min.

21. Polyamide (PA) according to any one of the preceding claims, exhibiting an aromatic content of less than 111.0% by weight, preferably less than 10.0% by weight.

22. Polyamide (PA) according to any one of the preceding claims, exhibiting a bio-content of at least 20.0%, said bio-content expressed as % of organic carbon derived from renewable resources measured according to ASTM D6866-22.

23. Polyamide (PA) according to any one of claims 1 to 22, exhibiting a Tg of at least 200°C, preferably at least 201°C, wherein the Tg is measured by differential scanning calorimetry ("DSC") according to ISO 11357, in particular using a heating and cooling rate of 20°C / min.

24. 24. Polyamide (PA) according to any one of claims 1 to 23, exhibiting a number average molecular weight ("Mn") of at least 10,000 g / mol, determined using the following formula (1): Mn = 2,000,000 / [EG] (1), where [EG] is the proportion of end groups in the PA expressed in mmol / kg.

25. Polyamide (PA) according to any one of the preceding claims, exhibiting a tensile modulus of at least 2.0 GPa measured according to ASTM D638.

26. Polyamide (PA) according to any one of the preceding claims, exhibiting a tensile strength, measured according to ASTM D638, of at least 80.0 MPa.

27. Polyamide (PA) according to any one of the preceding claims, exhibiting an elongation at break of at least 12.0%, measured according to ASTM D638.

28. Polyamide (PA) according to any one of the preceding claims, exhibiting an izod impact energy measured according to ASTM D256 of at least 65.0 J / m.

29. Polyamide (PA) according to any one of the preceding claims, exhibiting a transparency of at least 90.0%, preferably at least 95.0%, when measured according to ASTM D1003 on injection-molded specimens of 3.2 mm or 2.5 mm thickness.

30. Polyamide (PA) according to any one of the preceding claims, exhibiting a haze typically less than 8.0%, preferably less than 5.0%, preferably less than 2.0%, measured according to ASTM D1003 on injection-molded specimens of 3.2 mm or 2.5 mm thickness.

31. The terminal group in the polyamide is —NH ２ 31. Polyamide (PA) according to any one of claims 1 to 30, wherein the end groups are selected in the group of -COOH and amide end groups.

32. Polyamide (PA) according to claim 32, wherein the amide end groups are of the formula -NH-C(=O)-R, where R is an alkyl, aryl or cycloalkyl group, and / or -C(=O)-NH-R', where R' is an alkyl or cycloalkyl group.

33. 33. Polyamide (PA) according to any one of claims 1 to 32, wherein the PACM monomer used for preparing the polyamide (PA) comprises a proportion of (trans,trans)-4,4'-methylenebis[cyclohexylamine] of 15.0 to 25.0 mol %, this proportion being relative to the content of the three isomers.

34. It is prepared by polycondensation by heating a reaction mixture (RM) comprising all said monomers, said reaction mixture (RM) comprising in particular: a dicarboxylic acid (DA) selected from the group of MACM, PACM, isophthalic acid, and azelaic acid, sebacic acid, and combinations thereof (preferably, said dicarboxylic acid (DA) is sebacic acid); an optional catalyst, in particular a catalyst selected from the group consisting of phosphorous acid, ortho-phosphoric acid, meta-phosphoric acid, alkali metal hypophosphites, such as sodium hypophosphite, and phenylphosphinic acid, and combinations thereof; Optionally, at least one endcapping agent selected from the group of monocarboxylic acids, primary amines, and combinations thereof; optionally, water in a proportion of less than 60% by weight, preferentially less than 30%, less than 20%, less than 10% by weight, based on the total weight of said reaction mixture (RM) (preferentially no water is added); Polyamide (PA) according to any one of claims 1 to 33, comprising or consisting of:

35. Polyamide (PA) according to any one of claims 1 to 34, prepared from bio-based azelaic acid and / or sebacic acid exhibiting a bio-content of at least 99.0%, preferably at least 99.5%, preferably at least 99.9%, said bio-content expressed as % of organic carbon derived from renewable resources measured according to ASTM D6866-22.

36. Polyamide (PA) according to any one of claims 1 to 35, prepared from MACM and / or PACM exhibiting a bio-content of at least 99.0%, preferably at least 99.5%, preferably at least 99.9%, said bio-content expressed as % of organic carbon derived from renewable resources measured according to ASTM D6866-22.

37. Polyamide (PA) according to any one of the preceding claims, prepared from isophthalic acid exhibiting a bio-content of at least 99.0%, preferably at least 99.5%, preferably at least 99.9%, said bio-content expressed as % of organic carbon derived from renewable resources measured according to ASTM D6866-22.

38. A water absorption rate at 23°C of less than 5.0% by weight, preferably less than 3.5% by weight, wherein the water absorption rate at 23°C is determined by (i) preparing a dry test piece (water content less than 0.2% by weight) molded in accordance with ISO 527, (ii) immersing the test piece in deionized water at 23°C until a constant weight is reached, and (iii) measuring the water absorption rate at 23°C by the following formula: [Equation 1] (In the formula, W ｂｅｆｏｒｅ is the original dry weight of the molded specimen, and W ａｆｔｅｒ is the weight of the molded test piece after water absorption) The polyamide (PA) according to any one of claims 1 to 37, wherein the water absorption is determined by calculating the water absorption using:

39. - at least one polyamide (PA) according to any one of claims 1 to 38, at least one polymeric additive selected from the group consisting of heat stabilizers, UV stabilizers, colorants, antistatic agents, and combinations of two or more of the foregoing additives; A polymer composition (C) comprising: The polymer of the polymer composition (C) and the polymer additive are preferably blended; Polymer composition (C).

40. The polymer composition (C) according to claim 39, wherein the proportion of the polymer additive is 0.1 to 10.0% by weight.

41. 41. The polymer composition (C) of claim 39 or 40, exhibiting a tensile modulus of at least 2.0 GPa measured according to ASTM D638.

42. The polymer composition (C) according to any one of claims 39 to 41, exhibiting a tensile strength measured according to ASTM D638 of at least 80.0 MPa.

43. 43. The polymer composition (C) according to any one of claims 39 to 42, exhibiting an elongation at break of at least 12.0% measured according to ASTM D638.

44. The polymer composition (C) according to any one of claims 39 to 43, exhibiting an izod impact energy of at least 65.0 J / m measured according to ASTM D256.

45. 45. The polymer composition (C) according to any one of claims 39 to 44, exhibiting a transparency of at least 90.0%, preferably at least 95.0%, when measured according to ASTM D1003 on injection-molded specimens of 3.2 mm or 2.5 mm thickness.

46. 46. ​​The polymer composition (C) according to any one of claims 39 to 45, exhibiting a haze measured according to ASTM D1003 on injection-molded specimens of 3.2 mm or 2.5 mm thickness of less than 8.0%, preferably less than 5.0%, preferably less than 2.0%.

47. Use of a polyamide (PA) according to any one of claims 1 to 38 or a polymer composition according to any one of claims 39 to 46 for the manufacture of a transparent article.

48. Containers, in particular transparent containers, made from polyamides (PA) according to any one of claims 1 to 38 or polymer compositions (C) according to any one of claims 39 to 46.

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