Polyamides and corresponding polymer compositions and articles

Abstract

Described herein are amorphous, transparent, aliphatic polyamides (PA) formed from the polycondensation of monomers in a reaction mixture (RM) comprising a dicarboxylic acid component (DC) and a diamine component (DA). The dicarboxylic acid component (DC) comprises 25 mol% to 80 mol% 1,4-cyclohexanedicarboxylic acid ("1,4-CHDA") and 20 mol% to 75 mol% of a linear, aliphatic dicarboxylic acid selected from azelaic acid, sebacic acid, or a combination thereof. The diamine component (DA) comprises a cycloaliphatic diamine selected from the group consisting of isophoronediamine ("IPDA"); 4,4'-methylenebis(2-methylcyclohexylamine) ("MACM"); 4,4'-methylene-bis(cyclohexane) ("PACM"); 1,3-bis(aminomethyl)cyclohexane ("1,3-BAC"), bis(aminomethyl)norbornane ("BAMN"), and any combination of two or more thereof. Surprisingly, it has been found that polyamides (PA) have excellent optical clarity, improved UV stability and desirably high Tg while being bio-based (at least in part due to linear aliphatic dicarboxylic acids).

Description

[Technical field]

[0001] This application claims priority to European Patent Application No. 21305605.4, filed May 11, 2021, 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 this PCT application that would affect the clarity of the terms or wording, only this application should be referenced.

[0002] The present invention relates to polyamides that contain repeat units formed from azelaic acid or sebacic acid and have high glass transition temperatures and bio-content. The present invention further relates to polymer compositions and articles that contain the polyamides. [Background technology]

[0003] Given the widespread use of polyamides in many application settings, there is an ever-increasing industry demand to develop polyamides from renewable resources. For example, progress has been made in developing such polyamides based on dodecanoic acid, but such polyamides have a relatively low Tg and therefore are of limited suitability for high temperature applications.

[0004] CN107383369 discloses polyamides containing repeating units of aromatic acid (isophthalic acid). There is no mention of the Tg of this polyamide. JP2003-261766 discloses polyamides containing repeating units of aromatic acid (isophthalic acid). The Tg of this polyamide is not within the claimed range. DE1520924 does not disclose polyamides as claimed. US2965616 does not disclose amorphous polyamides. Summary of the Invention [Problem to be solved by the invention]

[0005] There is a need for high Tg polyamides that exhibit a good combination of optical clarity and UV stability and that can be biobased. The polyamides of the present invention aim to solve this technical problem.

[0006] The invention is defined in the attached set of claims. The object of the invention is therefore a polyamide as defined in any one of claims 1 to 24. The polyamide (PA), i.e. amorphous, aliphatic polyamide (PA), is Percentage of: - 25.0 to 80.0 mol% R PA1 ; - 20.0 to 75.0 mol% R PA2 , respectively, according to the following formula: [ka] [In the formula, - R1 is isophoronediamine ("IPDA"); 4,4'-methylenebis(2-methylcyclohexylamine) ("MACM"); 4,4'-methylene-bis-cyclohexylamine ("PACM"); 1,3-bis(aminomethyl)cyclohexane ("1,3-BAC"), bis(aminomethyl)norbornane ("BAMN"), 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4-methylcyclohexane-1,3-di amine, a divalent radical of a diamine selected from the group consisting of 2-methylcyclohexane-1,3-diamine, 1,8-diamino-p-menthane, 2,2-bis(4-aminocyclohexyl)propane ("PACP"), 4,4'-methanediylbis(2,6-dimethylcyclohexanamine), and any combination of two or more thereof; the diamine is more particularly selected from the group consisting of IPDA, MACM, PACM, 1,3-BAC, BAMN, and any combination of two or more thereof; - n is 7 or 8 Repeating unit R represented by PA1 and R PA2 Includes; And here, the polyamide (PA) has a glass transition temperature ("Tg") of 160°C to 260°C, preferably 160°C to 220°C.

[0007] Another object of the invention is a composition as defined in any one of claims 25 to 29. Another object of the invention is an article as defined in any one of claims 30 to 34. More precise and detailed specifications regarding these objects are now provided below. [Means for solving the problem]

[0008] In a first aspect, the present invention is directed to an amorphous, aliphatic polyamide (PA) comprising repeat units formed from the polycondensation of a reaction mixture (RM) comprising a dicarboxylic acid component (DC) and a diamine component (DA), the dicarboxylic acid component (DC) comprising 25 mol % to 80 mol % 1,4-cyclohexanedicarboxylic acid ("1,4-CHDA") and 20 mol % to 75 mol % of a linear, aliphatic dicarboxylic acid selected from the group consisting of azelaic acid (HOOC-(CH2)7-COOH), sebacic acid (HOOC-(CH2)8-COOH), and combinations thereof, where the mol % is based on the total moles of dicarboxylic acid in the dicarboxylic acid component (DA). The diamine component (DA) may be isophoronediamine ("IPDA"); 4,4'-methylenebis(2-methylcyclohexylamine) ("MACM"); 4,4'-methylene-bis-cyclohexylamine ("PACM"); 1,3-bis(aminomethyl)cyclohexane ("1,3-BAC"), bis(aminomethyl)norbornane ("BAMN"), 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, The polyamide (PA) comprises a cycloaliphatic diamine selected from the group consisting of 4-methylcyclohexane-1,3-diamine, 2-methylcyclohexane-1,3-diamine, 1,8-diamino-p-menthane, 2,2-bis(4-aminocyclohexyl)propane ("PACP"), 4,4'-methanediylbis(2,6-dimethylcyclohexanamine), and any combination of two or more thereof; where mol% is based on the total amount of diamine in the diamine component (DA). The polyamide (PA) has a glass transition temperature ("Tg") of 160°C to 260°C, preferably 160°C to 220°C, as measured according to ASTM D3418. The reaction mixture (RM) is free of tertiary amines, lactams, and amino acids. Moreover, when the cycloaliphatic dicarboxylic acid is PACM, the PACM comprises a trans-trans ratio of 30% or less. In some embodiments, the polyamide (PA) is transparent.

[0009] In some embodiments, the cycloaliphatic diamine is selected from the group consisting of IPDA, MACM, PACM, 1,3-BAC BAMN, and any combination of two or more thereof. In some embodiments, the dicarboxylic acid component (DC) consists essentially of 1,4-CHDA and a linear carboxylic acid. In some embodiments, the diamine component (DA) consists essentially of a cycloaliphatic diamine. In some embodiments, the concentration of the cycloaliphatic diamine is at least 80 mol %. In some embodiments, the polyamide (PA) has a bio-based carbon content of at least 20%.

[0010] In another aspect, the present invention is directed to a polymer composition (C) comprising a polyamide (PA) and a component selected from the group consisting of reinforcing agents, toughening agents, plasticizers, colorants, pigments, antistatic agents, dyes, lubricants, heat stabilizers, light stabilizers, flame retardants, nucleating agents, antioxidants, processing aids, and any combination of two or more thereof.

[0011] In some embodiments, the polymer composition (C) comprises a reinforcing agent selected from the group consisting of glass fibers and carbon fibers.

[0012] In some embodiments, the polymer composition (C) comprises a halogen-free flame retardant.

[0013] In another aspect, the present invention is directed to an article comprising the polyamide (PA) or the polymer composition (C), wherein the article is selected from the group consisting of sutures, hemodialysis membranes, vascular catheters, scaffolding, catheter balloons, wound dressings, respiratory masks, and medical tubing.

[0014] In another aspect, the present invention is directed to an article comprising a polyamide (PA) or polymer composition (C), the article being either a filament or a powder.

[0015] In another aspect, the present invention is directed to an article comprising the polyamide (PA) or the polymer composition (C), wherein the article is a portable electronic device component.

[0016] In another aspect, the present invention is directed to an article comprising the polyamide (PA) or the polymer composition (C), wherein the article is an automotive part.

[0017] In another aspect, the present invention is directed to an article comprising the polyamide (PA) or polymer composition (C), wherein the article is a cookware component. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] Described herein is an amorphous aliphatic polyamide (PA) formed from the polycondensation of monomers in a reaction mixture (RM) comprising a dicarboxylic acid component (DC) and a diamine component (DA). The dicarboxylic acid component (DC) comprises 25 mol% to 80 mol% of 1,4-cyclohexanedicarboxylic acid ("1,4-CHDA") and 20 mol% to 75 mol% of a linear, aliphatic dicarboxylic acid selected from azelaic acid, sebacic acid, or a combination thereof. The diamine component (DA) comprises a cycloaliphatic diamine selected from the group consisting of isophoronediamine ("IPDA"); 4,4'-methylenebis(2-methylcyclohexylamine) ("MACM"); 4,4'-methylene-bis-cyclohexane ("PACM"); 1,3-bis(aminomethyl)cyclohexane ("1,3-BAC"), bis(aminomethyl)norbornane ("BAMN"), and any combination of two or more thereof. Surprisingly, it has been found that polyamides (PA) are biobased (at least in part due to linear aliphatic dicarboxylic acids) and yet have superior optical clarity, improved UV stability and desirably high Tg compared to amorphous polyamides known in the art that are prepared from cycloaliphatic diamines, aromatic diacids and aliphatic linear long chain diacids containing at least 12 carbon atoms. As used herein, the term aliphatic also includes reference to cycloaliphatic unless otherwise specified.

[0019] The polyamides (PA) have a relatively high glass transition temperature ("Tg") so that they can be desirably incorporated into application settings in which the polyamides (PA) are exposed to elevated temperatures, as described in more detail below. The polyamides (PA) have a Tg of 160°C to 260°C. This relatively high Tg is due, at least in part, to the cyclic aliphatic dicarboxylic acids in the dicarboxylic acid component (DC) and to the absence of amino acids and lactams in the reaction mixture (RM). With regard to the linear aliphatic dicarboxylic acid, it not only provides the polyamide (PA) with a biobased content, but also mitigates the decrease in Tg before and / or after conditioning in a moist environment. That is, when the linear aliphatic dicarboxylic acid has less than 9 or more than 10 carbon atoms, the Tg of the resulting polyamide before and / or after conditioning in a moist environment is decreased compared to the corresponding reaction mixture (RM) in which the dicarboxylic acid (DC) contains a linear, aliphatic dicarboxylic acid having 9 or 10 carbon atoms. Similarly, polyamides containing repeat units formed from the polycondensation of a reaction mixture containing an amino acid, a lactam such as caprolactam, or a tertiary amine generally have increased moisture absorption compared to similar polyamides formed from a reaction mixture (RM) that does not contain such monomers. Thus, when present in an application setting exposed to the ambient environment, the increased moisture absorption leads to a decrease in Tg. Thus, the reaction mixture (RM) does not contain amino acids, lactams, and tertiary amines. As used herein and unless otherwise specified, "free" means that the concentration of the indicated monomer is less than 5 mol%, less than 3 mol%, less than 2 mol%, less than 1 mol%, less than 0.5 mol%, or less than 0.1 mol%, based on the total moles of the components in the reaction mixture (RM), the dicarboxylic acid component (DC), or the diamine component, as the case may be, that undergo polycondensation to form the polyamide (PA). For example, free of lactam means that the concentration of lactam is within the above ranges based on the total moles of monomers in the reaction mixture (RM). As another example, free of the indicated dicarboxylic acid means that the concentration of the indicated dicarboxylic acid, relative to the total moles of dicarboxylic acid in the dicarboxylic acid component (DC), is within the ranges given above.As yet another example, free of the indicated diamine means that the concentration of the indicated diamine, relative to the total moles of diamine in the diamine component (DA), is within the ranges given above.

[0020] Azelaic acid and sebacic acid provide polyamides (PA) with significant biobased content. In particular, azelaic acid can be produced from the ozonolysis of oleic acid, a naturally occurring fatty acid present in animal and vegetable fats and oils. Sebacic acid is also produced from biological sources. In particular, sebacic acid is produced from castor oil. Thus, not only does polyamide (PA) have a significant biobased content, but the biobased content also promotes an increase in the Tg of polyamide (PA), as described in detail above. The biobased content (also referred to herein as biobased carbon content) can be calculated as in the examples. In some embodiments, polyamide (PA) has a biobased carbon content of at least 15% or at least 20%.

[0021] Due to the combination of properties, notably because they are amorphous and transparent (e.g. have optical clarity), polyamides (PA) are well suited for applications such as cookware windows or containers where the ability to see through the material and at the same time good resistance to water / water vapor is required.

[0022] The polyamide (PA) of the present invention is aliphatic (especially cycloaliphatic), which is particularly important for ensuring UV resistance and limiting side reactions such as branching. That is, the reaction mixture (RM) does not contain aromatic monomers (monomers containing aryl groups) that polycondense to form repeat units in the polyamide (PA). That is, the concentration of aromatic monomers that polycondense to form repeat units in the polyamide (PA) is less than 5 mol%, less than 2 mol%, less than 1 mol%, or less than 0.5 mol%, relative to the total number of monomers in the reaction mixture (RM) that polycondense to form the polyamide (PA). In some such embodiments, the concentration of aromatic dicarboxylic acid monomers and aromatic diamine monomers in each dicarboxylic acid component (DC) and diamine component (DA), respectively, is less than 5 mol%, less than 2 mol%, less than 1 mol%, or less than 0.5 mol%.

[0023] According to an embodiment, the repeat units of the polyamide (PA) are substantially free of any aromatic moieties (eg aryl or benzene rings), more particularly free of any aromatic moieties.

[0024] In some embodiments, the reaction mixture (RM) consists essentially of or consists of the dicarboxylic acid component (DC) and the diamine (DA) component, as described above, in such embodiments, the total concentration of dicarboxylic acid and diamine in the reaction mixture (RM) is at least 95 mol%, at least 97 mol%, at least 98 mol%, at least 99 mol%, or at least 99.5 mol%, based on the total number of moles of monomers in the reaction mixture (RM) that are polycondensed to form the polyamide (PA).

[0025] In this application, any description is described in relation to a specific embodiment, but is applicable to and interchangeable with other embodiments of the present disclosure. When an element or component is said to be included in and / or selected from a list of recited elements or components, in the relevant embodiments expressly contemplated in this application, the element or component can be any one of the individual recited elements or components, or can also be selected from a group consisting of any two or more of the explicitly recited elements or components; any element or component recited in a list of elements or components can be omitted from such list; any recitation herein of a numerical range by endpoint should be understood to include all numbers incorporated within the recited range as well as the endpoints of the range and equivalents.

[0026] Dicarboxylic acid component (DC) The dicarboxylic acid component (DC) comprises all of the dicarboxylic acids in the reaction mixture (RM) including 25 mol % to 80 mol % 1,4-CHDA and 20 mol % to 75 mol % linear, aliphatic dicarboxylic acids selected from azelaic acid, sebacic acid, or combinations thereof. When referring to a concentration of dicarboxylic acid, it will be understood that the concentration is relative to the total number of moles of all dicarboxylic acids in the dicarboxylic acid component (DC) unless otherwise specified.

[0027] Concentration of 1,4-CHDA In some embodiments, the 1,4-CHDA concentration is 25 mol% to 80 mol% or 30 mol% to 80 mol%. In some embodiments, the 1,4-CHDA concentration is 25 mol% to 75 mol% or 30 mol% to 75 mol%. In some embodiments, the 1,4-CHDA concentration is 25 mol% to 60 mol% or 30 mol% to 60 mol%. In some embodiments, the 1,4-CHDA concentration is 25.0 mol% to 65.0 mol%.

[0028] In some embodiments, the 1,4-CHDA concentration is 45.0 mol% to 65.0 mol%. In this range of concentrations, the Tg can be at least 185° C. or even at least 195° C. The 1,4-CHDA concentration can be as defined in claim 17.

[0029] Those skilled in the art will appreciate that these concentrations given for 1,4-CHDA correspond to the repeating units R PA1 The repeating unit R in polyamide (PA) also corresponds to the ratio of PA1 The ratio may therefore be as defined in claim 18.

[0030] Concentration of linear, aliphatic dicarboxylic acids In some embodiments, the linear, aliphatic dicarboxylic acid concentration is from 20 mol% to 75 mol% or from 30 mol% to 75 mol%. In some embodiments, the linear, aliphatic dicarboxylic acid concentration is from 25 mol% to 60 mol% or from 30 mol% to 60 mol%. In some embodiments, the linear, aliphatic dicarboxylic acid concentration is from 35.0 mol% to 75.0 mol%. A person of ordinary skill in the art will recognize that additional linear, aliphatic dicarboxylic acid concentration ranges within the explicitly stated ranges above are contemplated and are within the present disclosure.

[0031] Those skilled in the art will appreciate that these concentrations for linear, aliphatic dicarboxylic acids correspond to the repeat units R PA2 Understand that the ratio also corresponds to the ratio of

[0032] In some embodiments, the dicarboxylic acid component (DC) consists essentially of or consists of 1,4-CHDA and linear, aliphatic dicarboxylic acids, in such embodiments, the total concentration of 1,4-CHDA and linear, aliphatic dicarboxylic acids is at least 95 mol%, at least 97 mol%, at least 98 mol%, at least 99 mol%, or at least 99.5 mol%.

[0033] The present invention therefore more particularly relates to a repeating unit R PA1 and R PA2 The present invention relates to a polyamide (PA) which essentially consists of or consists of:

[0034] Diamine component (DA) The diamine component (DA) comprises all diamines in the reaction mixture (RM), including alicyclic diamines selected from the group consisting of IPDA, MACM, PACM, 1,3-BAC, BAMN, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4-methylcyclohexane-1,3-diamine, 2-methylcyclohexane-1,3-diamine, 1,8-diamino-p-menthane, 2,2-bis(4-aminocyclohexyl)propane ("PACP"), 4,4'-methanediylbis(2,6-dimethylcyclohexanamine) and any combination of two or more thereof. Preferably, the alicyclic diamines are selected from the group consisting of IPDA, MACM, PACM, 1,3-BAC, BAMN and any combination of two or more thereof. Most preferably, the alicyclic diamines are selected from the group consisting of IPDA, MACM, PACM or any combination of two or more thereof.

[0035] According to a preferred embodiment (E), the diamine component (DA) comprises IPDA. According to this preferred embodiment (E), the diamine is IPDA or a combination of IPDA and at least one diamine selected in the group consisting of MACM, PACM, 1,3-BAC and BAMN, or a combination of IPDA and at least one diamine selected in the group consisting of MACM and PACM. Even more particularly, the diamine is IPDA or a combination of IPDA and MACM, or a combination of IPDA, MACM and PACM. According to this embodiment (E), the molar ratio IPDA / diamines other than IPDA in the reaction mixture (RM) may preferably be 50 / 50 to 100 / 0. According to this preferred embodiment (E), the polyamide exhibits a good combination of properties.

[0036] As mentioned above, polyamide (PA) is amorphous. Therefore, as long as the alicyclic diamine in the diamine component (DA) is PACM, the trans-trans isomer ratio is less than 30 mol% of the total content of isomers (including cis-cis, trans-trans, cis-trans) as measured by gas chromatography. When the trans-trans isomer ratio is 30 mol% or more, the resulting polyamide is generally semi-crystalline. The trans-trans isomer corresponds to the stereoisomer in which the cyclohexane substituents (i.e., -NH2 and -CH2-) are located on the opposite faces of the cyclohexane ring for both cyclohexane rings constituting the PACM molecule.

[0037] In some embodiments, the concentration of cycloaliphatic diamine is at least 75 mol%, at least 80 mol%, at least 85 mol%, at least 90 mol%, at least 95 mol%, or at least 99 mol%. In some embodiments, the diamine component (DA) consists essentially of cycloaliphatic diamine. In such embodiments, the cycloaliphatic diamine concentration is at least 95 mol%, at least 97 mol%, at least 98 mol%, at least 99 mol%, or at least 99.5 mol%. When referring to the concentration of diamine, it will be understood that the concentration is relative to the total number of moles of all diamines in the diamine component (DA) unless otherwise specified.

[0038] Polyamide (PA) of the present invention The polyamide (PA) is formed from the polycondensation of monomers in the diamine and dicarboxylic acid components, as described above. The polyamide (PA) can be represented by the following formulas: [ka] (wherein R1 is a divalent radical of a diamine selected from the group consisting of IPDA, MACM, PACM, 1,3-BAC, and BAMN, and n is 7 or 8.) The repeating unit R PA1 and R PA2For clarity, the diamine divalent radical is the divalent radical formed from removing two amines of the indicated diamine. Moreover, when the dicarboxylic acid component (DC) includes azelaic acid, n is 7, and when the dicarboxylic acid component (DC) includes sebacic acid, n is 8.

[0039] As mentioned above, the aliphatic dicarboxylic acid is selected from the group consisting of azelaic acid (HOOC-(CH2)7-COOH), sebacic acid (HOOC-(CH2)8-COOH), and combinations thereof. Thus, in the above formula, n can be 7. n can also be 8. It is also possible for the polyamide (PA) to contain repeat units with n=7 and repeat units with n=8.

[0040] According to a preferred embodiment (E), the repeating unit R PA1 and R PA2 contains a divalent radical of IPDA. According to this preferred embodiment (E), R1 is a divalent radical of IPDA or a combination of IPDA and at least one diamine selected from the group consisting of MACM, PACM, 1,3-BAC and BAMN or a combination of IPDA and at least one diamine selected from the group consisting of MACM and PACM. Even more particularly, R1 is a divalent radical of IPDA or a combination of IPDA and MACM or a combination of IPDA, MACM and PACM. According to embodiment (E), the molar ratio of divalent radicals of IPDA / divalent radicals of diamines other than IPDA may preferably be 50 / 50 to 100 / 0.

[0041] In some embodiments, the repeating unit R PA1 and R PA2is at least 50 mol%, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 97 mol%, at least 98 mol%, at least 99 mol%, or at least 99.5 mol%. When referring to mol% of a repeat unit, it will be understood that the concentration is relative to the total number of repeat units in the indicated polymer, unless otherwise specified. The present invention also more particularly relates to a repeat unit comprising a repeat unit R PA1 and R PA2 The present invention relates to a polyamide (PA) which essentially consists of or consists of:

[0042] In some embodiments, the repeat unit R PA1 Against R PA2 The ratio of the numbers is 2.3 to 0.4.

[0043] As explained in detail above, polyamide (PA) has a relatively high Tg. More specifically, polyamide (PA) has a Tg of 160°C to 260°C, preferably 160°C to 220°C. Tg can be at least 185°C, even at least 195°C. Tg can be measured according to ASTM D3418. Tg can be measured by DSC (differential scanning calorimetry), in particular by DSC measurement from 40°C to 320°C. The method disclosed in the examples can be used. The method consists in evaluating Tg by DSC from 40°C to 320°C, where after a first heating ramp, a first cooling and a second heating (all at 10°C / min), Tg is measured in the third heating (40°C / min).

[0044] Moreover, as explained above, the polyamide (PA) is amorphous. As used herein, an amorphous polyamide has a heat of fusion ("ΔH") of less than 5 Joules per gram ("J / g"), preferably less than 3 J / g, more preferably less than 2 J / g, and most preferably less than 1 J / g. f "). ΔH fcan be measured according to ASTM D3418 using a heating rate of 20° C. / min.

[0045] In some embodiments, the polyamide (PA) has a number average molecular weight ("Mn") in the range of 1,000 g / mol to 40,000 g / mol, e.g., 2,000 g / mol to 35,000 g / mol, 4,000 to 30,000 g / mol, or 5,000 g / mol to 20,000 g / mol. The number average molecular weight Mn can be measured by gel permeation chromatography (GPC) using ASTM D5296 with PMMA standard.

[0046] Method for preparing polyamide (PA) The polyamides (PA) described herein can be prepared by any conventional method compatible with the synthesis of polyamides and polyphthalamides. A convenient route for the preparation of polyamides (PA) is polycondensation, which involves heating the reaction mixture (RM) at a temperature T* at least greater than Tg+50°C.

[0047] Preferentially, the polyamide (PA) of the invention is prepared by reacting (by heating) the monomers in the presence of less than 30% by weight, preferentially less than 20% by weight and even more preferentially less than 10% by weight of water, up to a temperature T* of at least Tg+50°C, where the weight percentages are relative to the total weight of the reaction mixture.

[0048] T* is preferably at least 250°C, even at least 275°C.

[0049] The polycondensation is advantageously carried out in a well-stirred vessel such as a stirred reactor, extruder or kneader. The polycondensation is preferably carried out in a stirred reactor. The vessel is also advantageously equipped with means for removing volatile products of the reaction. Since the viscosity of the reaction mixture increases with time, the stirrer is adapted to provide sufficient stirring to the reaction mixture at the start of the polymerization and when the conversion of the polycondensation is nearly complete.

[0050] The conditions disclosed in Example 1 may be advantageously used for the preparation of the polyamides of the invention.

[0051] In some embodiments, the total number of moles of diamines in the reaction mixture is substantially equimolar to the total number of moles of dicarboxylic acid in the reaction mixture. As used herein, substantially equimolar means a value that is ±15% of the indicated number of moles. For example, in relation to the diamine and dicarboxylic acid concentrations in the reaction mixture, the total number of moles of diamines in the reaction mixture is ±15% of the total number of moles of dicarboxylic acid in the reaction mixture. The polyamide (PA) may contain a chain limiter, which is a monofunctional molecule that can react with an amine moiety or a carboxylic acid moiety and is used to control the molecular weight of the polyamide (PA). For example, the chain limiter (added to the reaction mixture) can be acetic acid, propionic acid, benzoic acid, and / or benzylamine.

[0052] Catalysts can also be used advantageously. Examples of catalysts are phosphorous acid, ortho-phosphoric acid, meta-phosphoric acid, alkali metal hypophosphites such as sodium hypophosphite, and phenylphosphinic acid. Stabilizers, such as phosphites, can also be used.

[0053] Polymer Composition (C) The polymer composition (C) comprises the polyamide (PA) of the invention. The polyamide (PA) may be present in the composition (C) in a total amount of more than 30% by weight, more than 35% by weight, more than 40% by weight or more than 45% by weight, based on the total weight of the polymer composition (C). This amount may be more than 50.0% by weight or even more than 60.0% by weight.

[0054] The polyamide (PA) may be present in composition (C) in a total amount of less than 99.95% by weight, less than 99% by weight, less than 95% by weight, less than 90% by weight, less than 80% by weight, less than 70% by weight or less than 60% by weight, based on the total weight of the polymer composition (C). The polyamide (PA) may for example be present in composition (C) in an amount ranging from 35 to 70% by weight, for example from 40 to 55% by weight, based on the total weight of the polymer composition (C).

[0055] Composition (C) may also include a component selected from the group consisting of reinforcing agents, toughening agents, plasticizers, colorants, pigments, antistatic agents, dyes, lubricants, heat stabilizers, light stabilizers, flame retardants, nucleating agents, antioxidants, processing aids, and any combination of two or more thereof.

[0056] A wide selection of reinforcing agents, also referred to as reinforcing fibers or fillers, may be added to the compositions according to the invention. They may be selected from fibrous reinforcing agents and particulate reinforcing agents. Fibrous reinforcing fillers are considered herein to be materials having a length, width and thickness, where the average length is significantly greater than both the width and thickness. Generally, such materials have an aspect ratio, defined as the average ratio between the length and the maximum width and thickness, of at least 5, at least 10, at least 20 or at least 50. In some embodiments, the reinforcing fibers (e.g., glass fibers or carbon fibers) have an average length of 3 mm to 50 mm. In some such embodiments, the reinforcing fibers have an average length of 3 mm to 10 mm, 3 mm to 8 mm, 3 mm to 6 mm, or 3 mm to 5 mm. In alternative embodiments, the reinforcing fibers have an average length of 10 mm to 50 mm, 10 mm to 45 mm, 10 mm to 35 mm, 10 mm to 30 mm, 10 mm to 25 mm or 15 mm to 25 mm. The average length of the reinforcing fibers can be considered as the average length of the reinforcing fibers prior to incorporation into the polymer composition (C) or it can be considered as the average length of the reinforcing fibers in the polymer composition (C).

[0057] The reinforcing fillers may be selected from mineral fillers (such as talc, mica, kaolin, calcium carbonate, calcium silicate, magnesium carbonate), glass fibres, carbon fibres, synthetic polymer fibres, aramid fibres, aluminium fibres, titanium fibres, magnesium fibres, boron carbide fibres, rock wool fibres, steel fibres and wollastonite.

[0058] Among the fibrous fillers, glass fibers are preferred; they include those described in Additives for Plastics Handbook, 2 ndExamples of suitable fillers include chopped strand A-, E-, C-, D-, S-, and R-glass fibers, as described in Chapter 5.2.3, pages 43-48 of the John Murphy, 1999 edition. Preferably, the filler is selected from fibrous fillers. It is more preferably a reinforcing fiber capable of withstanding high temperature applications.

[0059] The reinforcing agents may be present in composition (C) in a total amount of more than 15 wt%, more than 20 wt%, more than 25 wt%, or more than 30 wt%, based on the total weight of polymer composition (C). The reinforcing agents may be present in composition (C) in a total amount of less than 65 wt%, less than 60 wt%, less than 55 wt%, or less than 50 wt%, based on the total weight of polymer composition (C).

[0060] The reinforcing filler may for example be present in composition (C) in an amount ranging from 20 to 60% by weight, such as from 30 to 50% by weight, based on the total weight of polymer composition (C).

[0061] Composition (C) may also contain a toughening agent. Toughening agents generally exhibit a low Tg, for example below room temperature, below 0°C or even below -25°C. As a result of their low Tg, toughening agents are typically elastomeric at room temperature. Toughening agents may be functionalized polymer backbones.

[0062] The polymer backbone of the toughening agent may be selected from elastomeric backbones comprising polyethylene and their copolymers, such as ethylene-butene; ethylene-octene; polypropylene and their copolymers; polybutene; polyisoprene; ethylene-propylene-rubber (EPR); ethylene-propylene-diene monomer rubber (EPDM); ethylene-acrylate rubber; butadiene-acrylonitrile rubber, ethylene-acrylic acid (EAA), ethylene-vinyl acetate (EVA); acrylonitrile-butadiene-styrene rubber (ABS), block copolymer styrene ethylene butadiene styrene (SEBS); block copolymer styrene butadiene styrene (SBS); core-shell elastomers of the methacrylate-butadiene-styrene (MBS) type, or mixtures of one or more of the above.

[0063] When the toughening agent is functionalized, backbone functionalization can occur by copolymerization of monomers containing the functionalization or by grafting the polymer backbone with additional components.

[0064] Specific examples of functionalized toughening agents are, inter alia, terpolymers of ethylene, acrylic acid esters and glycidyl methacrylate, copolymers of ethylene, acrylic acid butyl ester and glycidyl methacrylate, ethylene-maleic anhydride copolymers, EPR grafted with maleic anhydride, styrene copolymers grafted with maleic anhydride, SEBS copolymers grafted with maleic anhydride, styrene-acrylonitrile copolymers grafted with maleic anhydride, and ABS copolymers grafted with maleic anhydride.

[0065] The toughening agents may be present in composition (C) in a total amount of more than 1 wt%, more than 2 wt%, or more than 3 wt%, based on the total weight of composition (C). The toughening agents may be present in composition (C) in a total amount of less than 30 wt%, less than 20 wt%, less than 15 wt%, or less than 10 wt%, based on the total weight of polymer composition (C).

[0066] The polymer composition (C) may also contain other conventional additives commonly used in the art, such as plasticizers, colorants, pigments (e.g., black pigments such as carbon black and nigrosine), antistatic agents, dyes, lubricants (e.g., linear low density polyethylene, calcium or magnesium stearate or sodium montanate), heat stabilizers, light stabilizers, flame retardants (e.g., halogen-free flame retardants), nucleating agents and antioxidants. Examples of halogen-free flame retardants include, but are not limited to, aluminum phosphinates.

[0067] Composition (C) may contain at least one halogen-free flame retardant, especially a phosphorus-based flame retardant. The phosphorus-based flame retardant may be selected from the group consisting of metal alkylphosphinates. An example of a metal alkylphosphinate is aluminum diethylphosphinate, such as that known under the trade name Exolit® from Clariant. Another example of a phosphorus-based flame retardant that ensures a good level of flame retardancy is disclosed below. [ka]

[0068] The polymer composition (C) may also comprise one or more other polymers, preferably polyamides different from the polyamide (PA) of the invention. Mention may be made, inter alia, of aliphatic polyamides, semi-aromatic polyamides and, more generally, semicrystalline or amorphous polyamides, such as polyamides obtained by polycondensation between aromatic or aliphatic saturated diacids and aliphatic saturated or aromatic primary diamines, lactams, amino acids or mixtures of these different monomers.

[0069] Preparation of polymer composition (C) The present invention further relates to a process for the preparation of a composition (C) as detailed above, said process comprising a step of melt-blending polyamide (PA) with certain components, such as fillers, reinforcing agents, stabilizers and any other optional additives.

[0070] Any melt blending method can be used to mix the polymeric and non-polymeric ingredients in the context of the present invention. For example, the polymeric and non-polymeric ingredients can be fed into a melt mixer, such as a single or twin screw extruder, a stirrer, a single or twin screw kneader, or a Banbury mixer, and the addition step can be simultaneous addition of all ingredients or batchwise gradual addition. When the polymeric and non-polymeric ingredients are added batchwise gradually, a portion of the polymeric and / or non-polymeric ingredients is added first and then melt mixed with the remaining polymeric and non-polymeric ingredients added thereafter until a well-mixed composition is obtained. When the reinforcing agent exhibits a long physical form (e.g., long fibers and continuous fibers), stretch extrusion or pultrusion can be used to prepare the reinforced composition.

[0071] Articles and uses The present invention also relates to articles comprising the polyamides (PA) of the present invention, and to articles comprising the copolymer compositions (C) described above, which may desirably be incorporated into healthcare applications, including, but not limited to, sutures, hemodialysis membranes, vascular catheters, scaffoldings (e.g., for ligament and tendon repair), catheter balloons, wound dressings, respiratory masks (e.g., face shield components), and medical tubing.

[0072] The articles may also be desirably incorporated into cookware components, including, but not limited to, coffee vending machine components, food serving containers, vacuum containers, and kitchenware.

[0073] The articles include, among others, portable electronic devices, LED packaging, oil and gas components, food contact components (including, but not limited to, food films and casings, baby bottles, drinking water bottles), electrical and electronic components (including, but not limited to, power plant components for computing, data systems and office equipment, and surface mount technology compatible connectors and contacts), medical device components (including, but not limited to, components for hearing aids and earphones, viewing windows for protective masks), consumer components (including, but not limited to, household appliances, optical eyeglass frames for prescription glasses and sunglasses, safety glasses, frames for sun protection lenses / spectacles lenses, cosmetic packaging, toothbrushes). It can be used in construction components (including but not limited to pipes, connectors, manifolds and valves for cooling and heating systems; boiler and metering components; gas system pipes and fittings; and electrical protection devices for mini circuit breakers, contactors, switches and sockets), industrial components, plumbing components (including but not limited to pipes, valves, fittings, manifolds, shower faucets and shower stop valves), automotive components, and aerospace components (including but not limited to interior cabin components).

[0074] The article may be, for example, a portable electronic device component. As used herein, a "portable electronic device" refers to an electronic device that is intended to be conveniently carried and used in a variety of locations. Portable electronic devices may include, but are not limited to, mobile phones, personal digital assistants ("PDAs"), laptop computers, tablet computers, wearable computing devices (e.g., smart watches, smart glasses, etc.), cameras, portable audio players, portable radios, global positioning system receivers, and portable game consoles.

[0075] The portable electronic device component may include, for example, a wireless antenna and composition (C). In this case, the wireless antenna may be a WiFi antenna or an RFID antenna. The portable electronic device component may also be an antenna housing. Further examples of portable electronic device components include, but are not limited to, micro-speakers, micro-switches, micro-receivers, connectors, camera modules, camera lens protectors, back housings, battery covers, chassis and frames.

[0076] In some embodiments, the portable electronic device component is an antenna housing. In some such embodiments, at least a portion of the wireless antenna is disposed on the polymer composition (C). Additionally or alternatively, at least a portion of the wireless antenna can be offset from (e.g., not in contact with) the polymer composition (C). In some embodiments, the device component can be an attachment component having a mounting hole or other fastening device (including, but not limited to, a snap-fit ​​connector between itself and another component of the portable electronic device, including, but not limited to, a circuit board, a microphone, a speaker, a display, a battery, a cover, a housing, an electrical or electronic connector, a hinge, a wireless antenna, a switch, or a switch pad). In some embodiments, the portable electronic device can be at least a portion of an input device.

[0077] Examples of oil and gas components include, but are not limited to, compressor rings, poppets, back-up seal rings, electrical connectors, labyrinth seals, motor end plates, bearings, bushings, suck rod guides and downhole tubing.

[0078] Examples of automotive parts include thermal management system components (including, but not limited to, thermostat housings, water inlet / outlet valves, water pumps, water pump impellers, and heater cores and end caps), air management system components (including, but not limited to, turbocharger actuators, turbocharger bypass valves, turbocharger hoses, EGR valves, CAC housings, exhaust gas recirculation systems, electronically controlled throttle valves, and hot air ducts), transmission components and launch gear components (including, but not limited to, dual clutch transmissions, automated manual transmissions, continuously variable transmissions, automatic transmissions, torque converters, dual mass flywheels, power take-offs, clutch cylinders, seal rings, thrust washers, thrust bearings, needle bearings, and check balls), automotive electronics components, automotive lighting components (including, but not limited to, motor end caps, sensors, ECU housings, bobbins and solenoids, connectors, circuit protection / relays, actuator housing ... fuel and selective catalytic reduction ("SCR") systems (including, but not limited to, SCR module housings and connectors, fuel flanges, rollover valves, quick connects, filter housings, fuel rails, fuel delivery modules, fuel hoses, fuel pumps, fuel injector O-rings, and fuel hoses); fluid system components (e.g., fuel system components) (including, but not limited to, inlet and outlet valves, and fluid pump components); interior components (e.g., dashboard components, display components, and seat components); and structural and lightweight components (e.g., gears and bearings, sunroofs, brackets and mounts, electric battery housings, thermal management components, braking system elements, and pumps and EGR systems).

[0079] The polyamides (PA), polymer compositions (C) and articles prepared therefrom may also be used as gas barrier materials for packaging applications, in single or multi-layer articles.

[0080] The polyamides (PA), the polymer compositions (C), and the articles prepared therefrom can also be used in automotive applications, for example in air induction systems, cooling and heating systems, drive and fuel systems, beams and structural supports, pans and covers.

[0081] Articles can be molded from the polyamide (PA) or polymer composition (C) of the present invention by any process suitable for thermoplastics, such as extrusion, injection molding, blow molding, rotational molding or compression molding. The polyamide (PA) and polymer composition (C) can also be used in overmolding preformed shapes to build hybrid structures. Articles can be printed from the polyamide (PA) or polymer composition (C) of the invention, for example by a process comprising a step of extrusion of the material in the form of a filament, or by a process comprising a step of laser sintering of the material, in which case the material is in powder form.

[0082] The present invention also provides a method for manufacturing a three-dimensional (3D) object with an additive manufacturing system, comprising the steps of: - providing a component material comprising a polyamide (PA) or a polymer composition (C) according to the invention, - Printing layers of a 3D object from this component material; The present invention relates to a method comprising the steps of:

[0083] The polyamide (PA) or polymer composition (C) can therefore also be in the form of threads or filaments used in 3D printing processes, for example fused filament manufacturing, also known as fused deposition modeling (FDM).

[0084] The polyamide (PA) or polymer composition (C) can also be in the form of a powder, for example a substantially spherical powder, used in 3D printing processes, for example selective laser sintering (SLS).

[0085] The polyamide (PA) or polymer composition (C) may also desirably be incorporated into a thermoplastic composite material (eg a tape) containing continuous glass or carbon fibres.

[0086] Use of polyamide (PA), composition (C) and articles The present invention relates to the use of the above-mentioned polyamide (PA), composition (C) or article, as described above, for manufacturing a portable electronic device component. The present invention also relates to the use of the above-mentioned polyamide (PA) or composition (C) for 3D printing an object.

[0087] To the extent that the disclosure of any patents, patent applications, and publications incorporated herein by reference conflicts with the statements of this application to the extent that it may render a term unclear, this statement shall control. EXAMPLES

[0088] This example demonstrates the synthesis, thermal and mechanical performance of polyamide. The raw materials used to form the samples are as follows: - IPDA (obtained from Aldrich) - 1,4-CHDA (obtained from Aldrich) - 1,6-hexanedioic acid (obtained from Aldrich) ("C6" in Table 1), also known as adipic acid. - 1,10-Decanedioic acid (obtained from Aldrich) ("C10" in Table 1), also known as sebacic acid. This monomer has 10 biobased carbon atoms. - 1,9-nonanedioic acid (obtained from Aldrich) ("C9" in Table 1), also known as azelaic acid. This monomer has 9 biobased carbon atoms. - 1,12-dodecanedioic acid (obtained from Aldrich) - 1,15-pentadecanedioic acid (obtained from Cathay) ("C15" in Table 1). - MACM (obtained from Aldrich) - PACM (obtained from Acros)

[0089] Polyamide synthesis This example demonstrates the synthesis of polyamides. Sample parameters for each reaction mixture are shown in Table 1. The biobased carbon content in a polymer is defined as the ratio of the number of biobased carbon atoms (derived from biobased monomers) divided by the total carbon atoms in the polymer (derived from biobased and non-biobased monomers).

[0090] [Table 1]

[0091] Example 1: 105.7 g (0.62 mol) of IPDA, 86.4 g (0.43 mol) of 1,10-decanedioic acid, 31.5 g (0.18 mol) of 1,4-CHDA, 4.1 g of an aqueous solution of sodium hypophosphite monohydrate (5% by weight, 2 mmol) and 30 g of deionized water were introduced into a stainless steel autoclave equipped with a mechanical stirrer. The autoclave was purged with nitrogen, then sealed and the temperature of the reactor was gradually increased up to 300° C. At the same time, the pressure was allowed to increase and reach a maximum of 11 bar, above which excess steam was distilled off. The pressure was then released and the autoclave was subjected to a vacuum (about 100 mbar) during 20 minutes. The resulting polymer was then discharged as a strand and pelletized.

[0092] Examples 2, 3, 4, 5 and all comparative examples CE1, CE2, CE3, CE4, CE5, CE6 and CE7 are prepared using the same procedure as Example 3, but using the appropriate monomer combinations and molar concentrations shown in Table 1.

[0093] thermal performance To demonstrate thermal performance, Tg was measured as described above. More specifically, for each sample, Tg was evaluated by DSC measurement from 40°C to 320°C. After the first heat ramp, first cool, and second heat (all at 10°C / min), Tg was measured at the third heat (40°C / min). Tg is listed in Table 1.

[0094] Comparison of E1 and E2 with CE1 and CE2 demonstrates that, unexpectedly, polyamides formed from the combination of at least a cycloaliphatic diamine (IPDA), CHDA and a C10 (1,10-decanedioic) diacid provided a Tg greater than 160° C. while simultaneously having a biobased carbon content of at least 20%. Similarly, comparison of E4 with CE3, CE4, CE5, CE6, and CE7 demonstrates that, unexpectedly, polyamides formed from the combination of at least a cycloaliphatic diamine (MACM), CHDA and a C9 diacid (1,9-nonanedioic acid) provided amorphous, transparent polyamides having a Tg>160° C. and a biobased carbon content of at least 20%.

[0095] Additionally, E4 and E5 unexpectedly demonstrate that polyamides formed from the combination of at least a cycloaliphatic diamine with CHDA and a C10 diacid (1,10-decanedioic acid), the resulting polyamides were amorphous, transparent polymers while having a Tg>180°C and a bio-based carbon content of at least 20%.

[0096] The above embodiments are intended to be illustrative and not limiting. Additional embodiments are within the concept of the present invention. In addition, while the present invention has been described with reference to specific embodiments, those skilled in the art will recognize that changes in form and detail may be made without departing from the spirit and scope of the present invention. Any incorporation by reference of the above documents is limited such that subject matter contrary to the express disclosure herein is not incorporated.

Claims

1. Percentage of: 25.0 to 80.0 mol% R ＰＡ１ ; 20.0 to 75.0 mol% R ＰＡ２ Then, the following formulas are used: 【Chemistry 1】 [In the formula: - R １ is a divalent radical of a diamine selected from the group consisting of isophoronediamine ("IPDA"); 4,4'-methylenebis(2-methylcyclohexylamine) ("MACM"); 4,4'-methylene-bis-cyclohexylamine ("PACM"); 1,3-bis(aminomethyl)cyclohexane ("1,3-BAC"), bis(aminomethyl)norbornane ("BAMN"), 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4-methylcyclohexane-1,3-diamine, 2-methylcyclohexane-1,3-diamine, 1,8-diamino-p-menthane, 2,2-bis(4-aminocyclohexyl)propane ("PACP"), 4,4'-methanediylbis(2,6-dimethylcyclohexanamine), and any combination of two or more thereof; - n is 7 or 8. The repeating unit R ＰＡ１ and R ＰＡ２ An amorphous polyamide (PA) comprising: The polyamide (PA) has a glass transition temperature ("Tg") of 160°C to 260°C, preferably 160°C to 220°C. Polyamide (PA).

2. - 25 mol % to 80 mol % of 1,4-cyclohexanedicarboxylic acid ("1,4-CHDA"), - 20 mol % to 75 mol % of a linear, aliphatic dicarboxylic acid selected from the group consisting of azelaic acid, sebacic acid and combinations thereof; where mol % is based on the total number of moles of dicarboxylic acid in the dicarboxylic acid component (DA); - alicyclic diamines selected from the group consisting of isophorone diamine ("IPDA"); 4,4'-methylenebis(2-methylcyclohexylamine) ("MACM"); 4,4'-methylene-bis-cyclohexylamine ("PACM"); 1,3-bis(aminomethyl)cyclohexane ("1,3-BAC"), bis(aminomethyl)norbornane ("BAMN"), 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4-methylcyclohexane-1,3-diamine, 2-methylcyclohexane-1,3-diamine, 1,8-diamino-p-menthane, 2,2-bis(4-aminocyclohexyl)propane ("PACP"), 4,4'-methanediylbis(2,6-dimethylcyclohexanamine) and any combination of two or more thereof. A diamine component (DA) containing An amorphous, aliphatic polyamide (PA) comprising repeat units formed from the polycondensation of a reaction mixture (RM) comprising: the total number of moles of diamine in said reaction mixture is preferably substantially equimolar to the total number of moles of dicarboxylic acid in said reaction mixture; The polyamide (PA) has a glass transition temperature ("Tg") of 160°C to 260°C, preferably 160°C to 220°C, as measured according to ASTM D3418; however: - said reaction mixture (RM) is free of tertiary amines, lactams and amino acids; and - if said cycloaliphatic dicarboxylic acid is PACM, said PACM contains a trans-trans ratio of less than or equal to 30% Subject to the condition Polyamide (PA).

3. The polyamide (PA) according to claim 1 or 2, wherein the alicyclic diamine is selected from the group consisting of IPDA, MACM, PACM, 1,3-BAC, BAMN and any combination of two or more thereof.

4. The following formulas are used: 【Chemistry 2】 [In the formula, R １ is a divalent radical of said diamine selected from the group consisting of IPDA, MACM, PACM, 1,3-BAC, BAMN, and any combination of two or more thereof, and n is 7 or 8. The repeating unit R ＰＡ１ and R ＰＡ２ The polyamide (PA) according to claim 2, comprising:

5. 3. Polyamide (PA) according to claim 2, wherein said dicarboxylic acid component (DC) consists essentially of or consists of said 1,4-CHDA and a linear carboxylic acid.

6. 3. Polyamide (PA) according to claim 2, wherein said diamine component (DA) consists essentially of or consists of said cycloaliphatic diamine.

7. 3. Polyamide (PA) according to claim 2, wherein the concentration of said cycloaliphatic diamine is at least 80 mol%.

8. 3. The polyamide (PA) according to claim 1 or 2, wherein the polyamide (PA) has a bio-based carbon content of at least 20%.

9. 3. The polyamide of claim 1 or 2, wherein the diamine is IPDA.

10. 3. The polyamide of claim 1, wherein the diamine is a combination of IPDA and at least one diamine selected from the group consisting of MACM, PACM, 1,3-BAC and BAMN.

11. 3. The polyamide of claim 1 or 2, wherein the diamine is a combination of IPDA and at least one diamine selected from the group consisting of MACM and PACM.

12. 3. The polyamide of claim 1 or 2, wherein the diamine is a combination of IPDA and MACM or a combination of IPDA, MACM and PACM.

13. Polyamide according to claim 9 in combination with claim 2, wherein the molar ratio IPDA / diamine other than IPDA in the reaction mixture (RM) is from 50 / 50 to 100 / 0.

14. Polyamide according to claim 9 in combination with claim 1, in which the molar ratio divalent radicals of IPDA / divalent radicals of said diamine other than IPDA is from 50 / 50 to 100 / 0.

15. Molar ratio R ＰＡ１ / R ＰＡ２ The polyamide according to claim 1 or 4, wherein the molar ratio is 0.4 to 2.

3.

16. 3. Polyamide (PA) according to claim 2, wherein the concentration of aromatic monomers in the reaction mixture (RM) which polycondense to form the repeat units in the polyamide (PA) is less than 5 mol%, preferably less than 2 mol%, preferably less than 1 mol% or preferably less than 0.5 mol%, relative to the total number of monomers in the reaction mixture which polycondense to form the polyamide (PA).

17. The concentration of 1,4-CHDA is - 25.0 mol% to 80.0 mol%; or 30.0 mol% to 80.0 mol%; or - 25.0 mol% to 75.0 mol%; or 30.0 mol% to 75.0 mol%; or 25.0 mol% to 60.0 mol%; or 30.0 mol% to 60.0 mol%; or 25.0 mol% to 65.0 mol%; or 45.0 mol% to 65.0 mol%; or - 25.0 mol% to 35.0 mol%; or - 45.0 mol% to 55.0 mol%; or - 55.0 mol% to 65.0 mol% 3. The polyamide (PA) according to claim 2,

18. Repeating unit (R ＰＡ１ ) is - 25.0 mol% to 80.0 mol%; or 30.0 mol% to 80.0 mol%; or - 25.0 mol% to 75.0 mol%; or 30.0 mol% to 75.0 mol%; or 25.0 mol% to 60.0 mol%; or 30.0 mol% to 60.0 mol%; or 25.0 mol% to 65.0 mol%; or 45.0 mol% to 65.0 mol%; or - 25.0 mol% to 35.0 mol%; or - 45.0 mol% to 55.0 mol%; or - 55.0 mol% to 65.0 mol% 5. Polyamide (PA) according to claim 1 or 4, wherein the percentage is based on the total number of repeat units in the polymer.

19. The repeating unit of the polyamide (PA) is the repeating unit R ＰＡ１ and R ＰＡ２ 5. Polyamide (PA) according to claim 1 or 4, consisting essentially of or consisting of:

20. 3. Polyamide (PA) according to claim 1 or 2, exhibiting a Tg of at least 185°C or at least 195°C.

21. A heat of fusion ("ΔH") of less than 5.0 Joules per gram ("J / g"), preferably less than 3.0 J / g, more preferably less than 2.0 J / g, and most preferably less than 1.0 J / g. ｆ 3. Polyamide (PA) according to claim 1 or 2, characterized in that

22. 3. Polyamide (PA) according to claim 1 or 2, having a number average molecular weight ("Mn") in the range of 1,000 g / mol to 40,000 g / mol, said number average molecular weight Mn being measured by gel permeation chromatography (GPC) using ASTM D5296 with PMMA standard.

23. 3. Polyamide (PA) according to claim 1 or 2, wherein the repeating units of the polyamide (PA) are substantially free of any aromatic moieties.

24. 3. Polyamide (PA) according to claim 1 or 2, wherein said repeating units do not contain any aromatic moieties.

25. - a polyamide (PA) according to claim 1 or 2, - a member selected from the group consisting of reinforcing agents, toughening agents, plasticizers, colorants, pigments, antistatic agents, dyes, lubricants, heat stabilizers, light stabilizers, flame retardants, nucleating agents, antioxidants, processing aids, and any combination of two or more thereof; The polymer composition (C) comprises, consists essentially of, or consists of:

26. 26. The polymer composition (C) of claim 25, comprising a reinforcing agent selected from the group consisting of glass fibers and carbon fibers.

27. 26. The polymer composition (C) of claim 25, comprising at least one reinforcing fiber or filler.

28. 26. The polymer composition (C) of claim 25, comprising a halogen-free flame retardant.

29. 26. The polymer composition (C) of claim 25, comprising at least one toughening agent.

30. The total amount of polyamide (PA) is - more than 30.0% by weight; or - greater than 35.0% by weight; or - greater than 40.0% by weight; or - greater than 45.0% by weight; or - greater than 50.0% by weight; or - more than 60.0% by weight; 26. The polymer composition (C) of claim 25, wherein said amount is based on the total weight of said polymer composition (C).

31. The total amount of polyamide (PA) is - less than 99.95% by weight; - less than 99.0% by weight; or - less than 95.0% by weight; or - less than 90.0% by weight; or - less than 80.0% by weight; 26. The polymer composition (C) of claim 25, wherein said amount is based on the total weight of said polymer composition (C).

32. 26. An article comprising a polyamide (PA) according to claim 1 or 2 or a polymer composition (C) according to claim 25, wherein the article is selected from the group consisting of sutures, hemodialysis membranes, vascular catheters, scaffolding, catheter balloons, wound dressings, respiratory masks, and medical tubing.

33. 26. An article comprising a polyamide (PA) according to claim 1 or 2 or a polymer composition (C) according to claim 25, said article being either a filament or a powder.

34. 26. An article comprising a polyamide (PA) according to claim 1 or 2 or a polymer composition (C) according to claim 25, wherein the article is a portable electronic device component.

35. 26. An article comprising a polyamide (PA) according to claim 1 or 2 or a polymer composition (C) according to claim 25, wherein the article is an automotive part.

36. 26. An article comprising a polyamide (PA) according to claim 1 or 2 or a polymer composition (C) according to claim 25, the article being a cookware component.

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