Polymer compositions containing polyamides and poly(arylene sulfides) and corresponding articles

Abstract

Described herein is a polymer composition (PC) comprising a polyamide (PA) and a poly(arylene sulfide) (PASP). The polyamide (PA) is a semi-aromatic polyamide derived from the polycondensation of an aliphatic diamine, a bis(aminoalkyl)cyclohexane, terephthalic acid, and, optionally, cyclohexanedicarboxylic acid. Surprisingly, it has been discovered that semi-aromatic polyamides derived from cycloaliphatic diamine bis(aminoalkyl)cyclohexanes or specific combinations of cycloaliphatic diamine bis(aminoalkyl)cyclohexanes and cycloaliphatic dicarboxylic acid cyclohexanedicarboxylic acid provide polymer compositions (PC) with improved retention of mechanical properties (e.g., tensile modulus and tensile strength) after aging in aqueous polyol solutions. Surprisingly, it has also been discovered that incorporating a nucleating agent into the polymer composition (PC) significantly improves tensile strength retention after aging. The polymer composition (PC) can be desirably incorporated into articles exposed to high temperatures and designed to transport or store polyol-based fluids, such as, but not limited to, engine coolants.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 63 / 021,103, filed May 7, 2020, and European Patent Application No. 63 / 021,103, filed June 8, 2020, the entire contents of each of which are incorporated herein by reference for all purposes.

[0002] The present invention relates to a polymer composition comprising a polyamide and a poly(arylene sulfide), which has excellent retention of mechanical properties after exposure to an aqueous polyol solution at elevated temperatures. The present invention also relates to a method for making the polymer composition and to articles incorporating the polymer composition. [Background technology]

[0003] Traditionally, semi-aromatic polyamides have been used to manufacture components exposed to engine coolants. Their high chemical resistance and desirable mechanical performance make them particularly suitable for engine coolant applications. However, such articles are typically placed in the engine compartment, where they are exposed to high temperatures. Over time, the mechanical performance of such articles deteriorates to undesirable levels.

[0004] One approach to achieving better mechanical performance retention is to use blends of semi-aromatic polyamides with poly(arylene sulfides), since poly(arylene sulfides) generally have improved resistance to hydrolysis at high temperatures compared to semi-aromatic polyamides. However, such solutions have not yet achieved the desired increase in mechanical performance retention. Summary of the Invention

[0005] In a first aspect, the present invention relates to a polymer composition (PC) comprising a polyamide (PA) and a poly(arylene sulfide) (PAS); the polyamide (PA) comprises 20 mol % to 95 mol % of C4-C 12The diamine component (A) contains an aliphatic diamine and 5 mol% to 80 mol% of a bis(aminoalkyl)cyclohexane, where these mol% are based on the total number of moles of each diamine in the diamine component; and a dicarboxylic acid component (B) contains 30 mol% to 100 mol% of terephthalic acid and 0 mol% to 70 mol% of cyclohexanedicarboxylic acid, where these mol% are based on the total number of moles of each dicarboxylic acid in the dicarboxylic acid component. In some embodiments, the bis(aminoalkyl)cyclohexane is 1,3-bis(aminomethyl)cyclohexane or 1,4-bis(aminomethyl)cyclohexane. In some embodiments, the dicarboxylic acid component (B) contains 1 mol% to 70 mol% of cyclohexanedicarboxylic acid, preferably 1,4-cyclohexanedicarboxylic acid, based on the total number of moles of each dicarboxylic acid in the dicarboxylic acid component. In some embodiments, the polymer composition (PC) further comprises 0.1 wt % to 1 wt % of a nucleating agent, based on the total weight of the polymer composition (PC). In some embodiments, the polymer composition (PC) comprises 5 wt % to 70 wt % of a reinforcing agent, based on the total weight of the polymer composition, preferably the reinforcing agent is glass fiber or carbon fiber, most preferably glass fiber.

[0006] In some embodiments, the polymer composition (PC) has at least 90% retention of tensile elasticity after 2000 hours aging in a 50:50 ethylene glycol:water solution at 130° C. In some embodiments, the polymer composition (PC) has at least 85% retention of tensile strength after 2000 hours aging in a 50:50 ethylene glycol:water solution at 130° C.

[0007] In another aspect, the present invention relates to an article comprising the polymer composition (PC), hi some embodiments, the article is selected from the group consisting of a fluid inlet port, a fluid outlet port, a fluid inlet valve, a fluid outlet valve, a fluid pump housing, a fluid pump impeller, a fluid hose connector, a fluid hose, a liquid reservoir, and a liquid valve. DETAILED DESCRIPTION OF THE INVENTION

[0008] Described herein is a polymer composition (PC) comprising a polyamide (PA) and a poly(arylene sulfide) (PASP). As described in detail below, the polyamide (PA) is a semi-aromatic polyamide derived from the polycondensation of an aliphatic diamine, a bis(aminoalkyl)cyclohexane, terephthalic acid, and, optionally, cyclohexanedicarboxylic acid. Surprisingly, it has been discovered that semi-aromatic polyamides derived from cycloaliphatic diamine bis(aminoalkyl)cyclohexanes or specific combinations of cycloaliphatic diamine bis(aminoalkyl)cyclohexanes and cycloaliphatic dicarboxylic acid cyclohexanedicarboxylic acids provide polymer compositions (PC) with improved retention of mechanical properties (e.g., tensile modulus and tensile strength) after aging in an aqueous polyol solution compared to similar semi-aromatic polyamides that do not contain cycloaliphatic diamine bis(aminoalkyl)cyclohexanes and cycloaliphatic dicarboxylic acid cyclohexanedicarboxylic acids. Surprisingly, it has also been discovered that incorporating a nucleating agent into the polymer composition (PC) significantly improves tensile strength retention after aging. For clarity, references to "aging" as used herein implicitly refer to thermal aging in aqueous polyol solutions. Due at least in part to the improved retention of mechanical properties after acquisition, the polymer compositions (PC) may be desirably incorporated into articles that are exposed to high temperatures during use and that are designed to carry or store polyol-based fluids, such as, but not limited to, engine coolants.

[0009] In this application, any description, even if made in connection with a particular embodiment, is applicable to and interchangeable with other embodiments of the present disclosure. Where an element or component is referred to as being included in and / or selected from a list of recited elements or components, in the relevant embodiments expressly contemplated by this application, the element or component can be any one of the individually recited elements or components, or can 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; and any recitation herein of numerical ranges by endpoints should be understood to include all numbers included within the recited ranges, as well as the endpoints of the ranges and their equivalents.

[0010] Unless specifically limited otherwise, the terms "alkyl" and derivative terms such as "alkoxy," "acyl," and "alkylthio," as used herein, include within their scope straight-chain, branched-chain, and cyclic moieties. Examples of alkyl groups are methyl, ethyl, 1-methylethyl, propyl, 1,1-dimethylethyl, and cyclopropyl. Unless specifically stated otherwise, each alkyl and aryl group may be unsubstituted or substituted with halogen, hydroxy, sulfo, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 acyl, formyl, cyano, C6-C6 alkyl, or C6-C6 alkylthio. 15 Aryloxy or C6-C 15 The term "halogen" or "halo" includes fluorine, chlorine, bromine, and iodine, with fluorine being preferred.

[0011] The term "aryl" refers to a phenyl, indanyl, or naphthyl group. An aryl group can contain one or more alkyl groups, in which case it is sometimes referred to as an "alkylaryl"; for example, it can be composed of a cycloaromatic group and two C1-C6 groups (e.g., methyl or ethyl). An aryl group can also contain one or more heteroatoms, such as N, O, or S, in which case it is sometimes referred to as a "heteroaryl" group; these heteroaromatic rings can be fused to other aromatic systems. Such heteroaromatic rings include, but are not limited to, furanyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, oxazolyl, thiazolyl, isothiazolyl, pyridyl, pyridazyl, pyrimidyl, pyrazinyl, and triazinyl ring structures. Aryl or heteroaryl substituents can be unsubstituted or substituted with halogen, hydroxy, C1-C6 alkoxy, sulfo, C1-C6 alkylthio, C1-C6 acyl, formyl, cyano, C6-C6 alkyl, or C6-C6 alkyl. 15 Aryloxy or C6-C 15 It may be substituted with one or more substituents selected from, but not limited to, aryl, provided that the substituents are sterically compatible and chemical bonding and strain energy rules are satisfied.

[0012] As mentioned above, it has been surprisingly discovered that polymer compositions (PC) retain improved mechanical properties after thermal aging in aqueous polyol solutions. Polyols are organic compounds containing at least two hydroxyl groups. Polyols of interest herein include, but are not limited to, ethylene glycol, propylene glycol, and diethylene glycol. Typically, engine coolants utilize aqueous polyol solutions with a water to polyol (e.g., ethylene glycol) weight ratio of 99.9 / 0.1 to 50:50. Mechanical property retention can be determined according to the following formula: 100*(X1 / X0). (where X1 is the value of a given mechanical property after aging and X0 is the value of the mechanical property before aging (e.g., as molded).) Aging can be performed by immersing the polymer composition (PC) in a 50:50 ethylene glycol:water solution at 130°C for 2000 hours.

[0013] In some embodiments, the polymer composition (PC) has a tensile modulus retention of at least 90%, at least 95%, at least 100%, or at least 101%. In some embodiments, the polymer composition (PC) has a tensile modulus retention of 120% or less, 115% or less, or 110% or less. In some embodiments, the polymer composition (PC) has a tensile modulus retention of 90% to 120%, 95% to 115%, 100% to 110%, or 101% to 110%. In some embodiments, the polymer composition (PC) has a tensile strength retention of at least 85% or at least 90%. In some embodiments, the polymer composition (PC) has a tensile strength retention of 110% or less, or 100% or less. In some embodiments, the polymer composition (PC) has a tensile strength retention of 85% to 110%, or 90% to 100%. Tensile modulus and tensile strength can be measured as described in the Examples section.

[0014] In some embodiments, the polymer composition (PC) has a tensile modulus after aging of at least 7 GPa, at least 10 GPa, or at least 13 GPa. In some embodiments, the polymer composition (PC) has a tensile modulus after aging of 25 GPa or less, 20 GPa or less, or 17 GPa or less. In some embodiments, the polymer composition (PC) has a tensile modulus after thermal aging of 7 GPa to 25 GPa, 10 GPa to 20 GPa, or 13 GPa to 17 GPa. In some embodiments, the polymer composition (PC) has a tensile strength after thermal aging of at least 120 MPa, at least 130 MPa, or at least 140 MPa. In some embodiments, the polymer composition (PC) has a tensile strength after thermal aging of 170 MPa or less, at least 160 MPa, or at least 150 MPa. In some embodiments, the polymer composition (PC) has a tensile strength after thermal aging of 120 MPa to 170 MPa, 130 MPa to 160 MPa, or 140 MPa to 150 MPa.

[0015] In some embodiments, the polymer composition (PC) has a tensile modulus before thermal aging of at least 7 GPa, at least 10 GPa, or at least 12 GPa. In some embodiments, the polymer composition (PC) has a tensile modulus before thermal aging of 20 GPa or less, 18 GPa or less, or 16 GPa or less. In some embodiments, the polymer composition (PC) has a tensile modulus before thermal aging of 7 GPa to 20 GPa, 10 GPa to 18 GPa, or 12 GPa to 16 GPa. In some embodiments, the polymer composition (PC) has a tensile strength before thermal aging of at least 120 MPa, at least 130 MPa, or at least 140 MPa. In some embodiments, the polymer composition (PC) has a tensile strength before thermal aging of 170 MPa or less, at least 160 MPa, or at least 150 MPa. In some embodiments, the polymer composition (PC) has a tensile strength before thermal aging of 120 MPa to 170 MPa, 130 MPa to 160 MPa, or 140 MPa to 150 MPa.

[0016] In some embodiments, the polymer composition (PC) has a flexural modulus before thermal aging of at least 5 GPa, at least 7 GPa, or at least 10 GPa. In some embodiments, the polymer composition (PC) has a flexural modulus before thermal aging of 20 GPa or less, 17 GPa or less, or 15 GPa or less. In some embodiments, the polymer composition (PC) has a flexural modulus before thermal aging of 5 GPa to 20 GPa, 7 GPa to 17 GPa, or 10 GPa to 15 GPa. In some embodiments, the polymer composition (PC) has a flexural strength before thermal aging of at least 170 MPa, at least 180 MPa, or at least 190 MPa. In some embodiments, the polymer composition (PC) has a flexural strength before thermal aging of 215 MPa or less, 210 MPa or less, or 200 MPa or less. In some embodiments, the polymer composition (PC) has a flexural strength before thermal aging of 170 MPa to 215 MPa, 180 MPa to 210 MPa, or 190 MPa to 200 MPa. Flexural modulus and flexural strength can be measured as described in the Examples section.

[0017] Polyamide (PA) The polymer composition (PC) contains a polyamide (PA). The polyamide (PA) contains: (1) 20 mol % to 95 mol % of C4 to C6 12 (2) a diamine component (A) containing an aliphatic diamine and 5 mol % to 80 mol % of a bis(aminoalkyl)cyclohexane, wherein these mol % are based on the total number of moles of each diamine monomer in the diamine component; and (3) a dicarboxylic acid component (B) containing 30 mol % to 100 mol % of terephthalic acid and 0 mol % to 70 mol %, preferably 1 mol % to 70 mol %, of cyclohexanedicarboxylic acid, wherein these mol % are based on the total number of moles of each dicarboxylic acid monomer in the dicarboxylic acid component; The polyamides described herein are derived from the polycondensation of monomers in a reaction mixture containing bis(aminoalkyl)cyclohexanes, or specific combinations of bis(aminoalkyl)cyclohexanes and cyclohexanedicarboxylic acids. Surprisingly, it has been discovered that the incorporation of bis(aminoalkyl)cyclohexanes, or specific combinations of bis(aminoalkyl)cyclohexanes and cyclohexanedicarboxylic acids, into semi-aromatic polyamides results in polymer compositions (PCs) with improved retention of mechanical properties. The polyamides described herein have a glass transition temperature ("Tg") of at least 145°C, a melting temperature ("Tm") of at least 295°C, and a heat of fusion ("ΔH") of at least 30 J / g. f ").

[0018] Diamine component (A) The diamine component (A) contains 20 mol % to 95 mol % of C4 to C 12 All diamines in the reaction mixture are included, including aliphatic diamines and 5 mole % to 80 mole % of bis(aminoalkyl)cyclohexanes. When referring to the concentration of monomers in diamine component (A), it is understood that the concentration is relative to the total number of moles of all diamines in diamine component (A), unless otherwise specified.

[0019] In some embodiments, C4 to C 12 The aliphatic diamine is represented by the formula: H2N-R1-NH2(1) (Wherein R'1 is C4 to C 12 Alkyl groups, preferably C6 to C 10 In some embodiments, the C4 to C6 alkyl group is 12The aliphatic diamine is selected from the group consisting of 1,4-diaminobutane (putrescine), 1,5-diaminopentane (cadaverine), 2-methyl-1,5-diaminopentane, hexamethylenediamine (or 1,6-diaminohexane), 3-methylhexamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 2,2,7,7-tetramethyloctamethylenediamine, 1,9-diaminononane, 2-methyl-1,8-diaminooctane, 5-methyl-1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane. Preferably, the aliphatic diamine is selected from the group consisting of C4 to C6 12 The aliphatic diamine is selected from the group consisting of 1,6-diaminohexane, 3-methylhexamethylenediamine, 2,2,4-trimethyl-hexamethylenediamine, 2,4,4-trimethyl-hexamethylenediamine, 1,9-diaminononane, 2-methyl-1,8-diaminooctane, 5-methyl-1,9-diaminononane, and 1,10-diaminodecane. Preferably, the aliphatic diamine is selected from the group consisting of C4 to C6 12 Aliphatic diamines are C5-C 10 It is an aliphatic diamine or a C5 to C9 aliphatic diamine. Most preferably, it is a C4 to C 12 The aliphatic diamine is 1,6-diaminohexane.

[0020] In some embodiments, C6 to C 12 The concentration of the aliphatic diamine is 25 mol% to 95 mol%, 30 mol% to 95 mol%, 35 mol% to 95 mol%, 40 mol% to 95 mol%, 45 mol% to 95 mol%, or 50 mol% to 95 mol%. 12 The concentration of the diamine is 20 mol% to 90 mol%, 25 mol% to 90 mol%, 30 mol% to 90 mol%, 35 mol% to 90 mol%, 40 mol% to 90 mol%, 45 mol% to 90 mol%, or 50 mol% to 90 mol%.

[0021] The bis(aminoalkyl)cyclohexane is represented by the formula: [ka] (Wherein, R2 and R3 are C1 to C 10 independently selected from alkyl; R i is selected at each position from the group consisting of alkyl, aryl, alkali or alkaline earth metal sulfonate, alkyl sulfonate, and quaternary ammonium; and i is an integer from 0 to 10. The -R3-NH2 group is disposed relative to the meta (1,3-) or para (1,4-) position. Preferably, i is 0, and R2 and R3 are both -CH2-. Most preferably, the bis(aminoalkyl)cyclohexane is selected from 1,3-bis(aminomethyl)cyclohexane ("1,3-BAC") and 1,4-bis(aminomethyl)cyclohexane ("1,4-BAC"). Of course, the bis(aminoalkyl)cyclohexane may be in either the cis or trans conformation. Thus, the diamine component (A) may contain only cis-bis(aminoalkyl)cyclohexane, only trans-bis(aminoalkyl)cyclohexane, or a mixture of cis- and trans-bis(aminoalkyl)cyclohexanes.

[0022] In some embodiments, the concentration of the bis(aminoalkyl)cyclohexane is 5 mol% to 75 mol%, 5 mol% to 70 mol%, 5 mol% to 65 mol%, 5 mol% to 60 mol%, 5 mol% to 55 mol%, or 5 mol% to 50 mol%. In some embodiments, the concentration of the bis(aminoalkyl)cyclohexane is 10 mol% to 75 mol%, 10 mol% to 70 mol%, 10 mol% to 65 mol%, 10 mol% to 60 mol%, 10 mol% to 55 mol%, or 10 mol% to 50 mol%, or 20 mol% to 40 mol%.

[0023] As noted above, in some embodiments, the diamine component (A) comprises one or more additional diamines. The additional diamines may be C4 to C6 12In some embodiments, one, more, or all of the additional diamines are represented by Formula (1), are different from each other, and are C4 to C6. 12 In some embodiments, each additional diamine is different from an aliphatic diamine. In some embodiments, each additional diamine is selected from the group consisting of 1,2 diaminoethane, 1,2-diaminopropane, propylene-1,3-diamine, 1,3 diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane, 2-methyl-1,5-diaminopentane, 1,6-diaminohexane, 3-methylhexamethylenediamine, 2,5 dimethylhexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 1 The diamine component is selected from the group consisting of 1,7-diaminoheptane, 1,8-diaminooctane, 2,2,7,7-tetramethyloctamethylenediamine, 1,9-diaminononane, 2-methyl-1,8-diaminooctane, 5-methyl-1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 2,5-bis(aminomethyl)tetrahydrofuran, and N,N-bis(3-aminopropyl)methylamine. This category also includes alicyclic diamines such as isophoronediamine, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, and bis-p-aminocyclohexylmethane. In some embodiments, the diamine component does not include alicyclic diamines other than bis(aminoalkyl)cyclohexane. As used herein, "free of a monomer (e.g., a bis(aminoalkyl)cyclohexane)" means that the concentration of the monomer in the corresponding component (e.g., a diamine component (A)) is less than 1 mol %, preferably less than 0.5 mol %, more preferably less than 0.1 mol %, even more preferably less than 0.05 mol %, and most preferably less than 0.01 mol %.

[0024] Dicarboxylic acid component (B) Dicarboxylic acid component (B) includes all dicarboxylic acids in the reaction mixture, including 30 mol% to 100 mol% terephthalic acid and 0 mol% to 70 mol%, preferably 1 mol% to 70 mol%, cyclohexanedicarboxylic acid. When referring to the concentration of monomers in dicarboxylic acid component (B), it will be understood that the concentration is relative to the number of moles of all dicarboxylic acids in dicarboxylic acid component (A), unless otherwise specified.

[0025] In some embodiments, the concentration of terephthalic acid is 35 mol% to 100 mol%, 35 mol% to 100 mol%, 40 mol% to 100 mol%, 45 mol% to 100 mol%, or 50 mol% to 100 mol. In some embodiments, the concentration of terephthalic acid is 30 mol% to 99 mol%, 35 mol% to 99 mol%, 40 mol% to 99 mol%, 45 mol% to 99 mol%, or 50 mol% to 99 mol. In some embodiments, the concentration of terephthalic acid is 30 mol% to 95 mol%, 35 mol% to 97 mol%, 40 mol% to 97 mol%, 45 mol% to 97 mol%, or 50 mol% to 97 mol.

[0026] Cyclohexanedicarboxylic acid is represented by the formula: [ka] (In the formula, R j is selected from the group consisting of alkyl, aryl, alkali or alkaline earth metal sulfonates, alkyl sulfonates, and quaternary ammonium; j is an integer from 0 to 10. The explicit -COOH group is positioned relative to the meta (1,3-) or para (1,4-) positions, preferably the para position. Preferably, the cyclohexanedicarboxylic acid is 1,4-cyclohexanedicarboxylic acid ("CHDA") (j is 0). Of course, the cyclohexanedicarboxylic acid may be in the cis or trans conformation. Thus, the dicarboxylic acid component (B) may contain only cis-cyclohexanedicarboxylic acid, only trans-cyclohexanedicarboxylic acid, or a mixture of cis- and trans-cyclohexanedicarboxylic acids.

[0027] In some embodiments, the concentration of cyclohexanedicarboxylic acid is between 1 mol% and 70 mol%, between 1 mol% and 65 mol%, between 1 mol% and 60 mol%, between 1 mol% and 55 mol%, or between 1 mol% and 50 mol%.

[0028] As noted above, in some embodiments, dicarboxylic acid component (B) comprises one or more additional dicarboxylic acids. Each additional dicarboxylic acid is different from the others and different from terephthalic acid and cyclohexanedicarboxylic acid. In some embodiments, one, more, or all of the additional dicarboxylic acids are represented by Formula (3), each different from the others and different from cyclohexanedicarboxylic acid.

[0029] In some embodiments, the one or more additional dicarboxylic acids are C4-C 12 The dicarboxylic acids are independently selected from the group consisting of aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and alicyclic dicarboxylic acids. 10 Examples of aliphatic dicarboxylic acids include, but are not limited to, succinic acid [HOOC-(CH2)2-COOH], glutaric acid [HOOC-(CH2)3-COOH], 2,2-dimethyl-glutaric acid [HOOC-C(CH3)2-(CH2)2-COOH], adipic acid [HOOC-(CH2)4-COOH], 2,4,4-trimethyl-adipic acid [HOOC-CH(CH3)-CH2-C(CH3)2-CH2-COOH], pimelic acid [HOOC-(CH2)5-COOH], suberic acid [HOOC-(CH2)6-COOH], azelaic acid [HOOC-(CH2)7-COOH], sebacic acid [HOOC-(CH2)8-COOH], 1,12-dodecanedioic acid [HOOC-(CH2) 10 -COOH].

[0030] Examples of desirable aromatic dicarboxylic acids include, but are not limited to, phthalic acids such as isophthalic acid (IA), naphthalenedicarboxylic acids (e.g., naphthalene-2,6-dicarboxylic acid), 4,4'-bibenzoic acid, 2,5-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, 2,2-bis(4-carboxyphenyl)propane, 2,2-bis(4-carboxyphenyl)hexafluoropropane, 2,2-bis(4-carboxyphenyl)ketone, 4,4'-bis(4-carboxyphenyl)sulfone, 2,2-bis(3-carboxyphenyl)propane, 2,2-bis(3-carboxyphenyl)hexafluoropropane, 2,2-bis(3-carboxyphenyl)ketone, and bis(3-carboxyphenoxy)benzene.

[0031] Examples of suitable alicyclic dicarboxylic acids include, but are not limited to, cyclopropane-1,2-dicarboxylic acid, 1-methylcyclopropane-1,2-dicarboxylic acid, cyclobutane-1,2-dicarboxylic acid, tetrahydrofuran-2,5-dicarboxylic acid, and 1,3-adamantanedicarboxylic acid.

[0032] In some embodiments where the polyamide (PA) comprises one or more additional dicarboxylic acids, the total concentration of the one or more additional dicarboxylic acids is 20 mole % or less.

[0033] Polyamide (PA) repeating unit The polyamide (PA) formed by polycondensation of the above-mentioned diamine component and dicarboxylic acid component monomers has a repeating unit R represented by the following formula: PA1 and R PA2 : [ka] Furthermore, when cyclohexanedicarboxylic acid is present in the dicarboxylic acid component (B), the repeating unit R PA3 and R PA4 : [ka] (In the formula, R1~R3, R i , R j , i, and j are as defined above). Those skilled in the art will recognize that repeating units R PA1 C4~C 12 Formed by polycondensation of aliphatic diamine and terephthalic acid, it has the repeating unit R PA3 C4~C 12 Formed by polycondensation of aliphatic diamine and cyclohexanedicarboxylic acid, the repeating unit R PA2 is formed from the polycondensation of bis(aminoalkyl)cyclohexane with terephthalic acid, and the repeating unit R PA4 It will be recognized that R is formed from the polycondensation of a bis(aminoalkyl)cyclohexane with a cyclohexanedicarboxylic acid. In some embodiments, R is —(CH)— m where m is 5 to 10, preferably 5 to 9, and most preferably 6. Additionally or alternatively, in some embodiments, R2 and R3 are both —CH2— and i and j are both zero. In some embodiments, the bis(aminealkyl)cyclohexane is 1,3-bis(aminomethyl)cyclohexane and the cyclohexanedicarboxylic acid is 1,4-cyclohexanedicarboxylic acid.

[0034] In some embodiments, the repeating unit R PA1 and R PA2 is 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%. In some embodiments where optional cyclohexanedicarboxylic acid is present in dicarboxylic acid component (B), the repeating unit R PA1 ~R PA4is 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 mole % 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.

[0035] Polyamide (PA) is a semi-crystalline polyamide. As used herein, a semi-crystalline polyamide has a heat of fusion ("ΔH") of at least 5 Joules per gram ("J / g"). f In some embodiments, the polyamides (PA) described herein have a ΔH of at least 30 J / g, or at least 35 J / g. f Additionally or alternatively, in some embodiments, the polyamide (PA) has a ΔH of 60 J / g or less, or 55 J / g or less. f In some embodiments, the polyamide (PA) has a ΔH of 30 J / g to 60 J / g, or 35 J / g to 60 J / g, or 30 J / g to 55 J / g, or 35 J / g to 55 J / g. f ΔH f can be measured according to ASTM D3418 using a heating rate of 20°C / min.

[0036] The polyamide (PA) has a Tg of at least 145° C., preferably at least 150° C. In some embodiments, the polyamide (PA) has a Tg of 190° C. or less, 180° C. or less, or 170° C. or less. In some embodiments, the polyamide (PA) has a Tg of 145° C. to 190° C., 145° C. to 180° C., 145° C. to 170° C., 150° C. to 190° C., 150° C. to 180° C., or 150° C. to 170° C. The Tg can be measured according to ASTM D3418.

[0037] The polyamide (PA) has a Tm of at least 295° C., preferably at least 300° C. In some embodiments, the polyamide (PA) has a Tm of 360° C. or less, 350° C. or less, or 340° C. or less. In some embodiments, the polyamide (PA) has a Tm of 295° C. to 360° C., 295° C. to 350° C., 295° C. to 340° C., 300° C. to 360° C., 300° C. to 350° C., or 300° C. to 340° C. Tm can be measured according to ASTM D3418.

[0038] In some embodiments, the polyamide (PA) has a number average molecular weight ("Mn") ranging from 1,000 g / mol to 40,000 g / mol, e.g., from 2,000 g / mol to 35,000 g / mol, from 4,000 to 30,000 g / mol, or from 5,000 g / mol to 20,000 g / mol. The number average molecular weight Mn can be measured by gel permeation chromatography (GPC) using ASTM D5296 with polystyrene standards.

[0039] The polyamides (PA) described herein can be prepared by any conventional method adapted to the synthesis of polyamides and polyphthalamides. Preferably, the polyamides (PA) are prepared by reacting (heating) the monomers in the presence of less than 60% by weight, preferentially less than 50% by weight, of water to a temperature of at least Tm+10°C, where Tm is the melting temperature of the polyamide (PA), where the weight percentages are relative to the total weight of the reaction mixture.

[0040] The polyamides (PA) described herein can be prepared, for example, by thermal polycondensation (also referred to as polycondensation or condensation) of aqueous solutions of monomers and comonomers. In one embodiment, the polyamides (PA) contain at least C4 to C6 copolymers in the reaction mixture. 12The polyamide (PA) is formed by reacting an aliphatic diamine, a bis(aminoalkyl)cyclohexane, terephthalic acid, and, if present in the dicarboxylic acid component (B), cyclohexanedicarboxylic acid. In some embodiments, the total number of moles of diamine 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 concentration of diamine and dicarboxylic acid in the reaction mixture, the total number of moles of diamine 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 capable of reacting 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 can be acetic acid, propionic acid, benzoic acid, and / or benzylamine. A catalyst can also be used. 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 may also be used.

[0041] Poly(arylene sulfide) (PASP) The polymer composition (PC) comprises a poly(arylene sulfide) (PASP). As used herein, a poly(arylene sulfide) comprises repeating units (R PAS ) refers to any polymer containing at least 50 mol % of: -[-Ar-S-]- where Ar is arylene. In some embodiments, the poly(arylene sulfide) (PASP) comprises at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 99 mol%, or at least 99.9 mol% of repeat units (R PAS )

[0042] In some embodiments, the repeating unit (R PAS ) is a group of expressions: [ka] (wherein R is, in each case, C1 to C 12 Alkyl groups, C7-C 24 Alkylaryl group, C7-C 24 Aralkyl groups, C6-C 24 Arylene groups and C6-C 18 aryloxy groups; T is selected from the group consisting of a bond, —CO—, —SO—, —O—, —C(CH), phenyl, and —CH—; k, at each occurrence, is an independently selected integer from 0 to 4; and l, at each occurrence, is an independently selected integer from 0 to 3.

[0043] In a preferred embodiment, k and l are zero in each case. Preferably, -Ar- is a repeating unit (R) corresponding to the repeating unit of either formula (8) or (9), more preferably formula (8) (polyphenylene sulfide). PAS )), and more preferably the repeating unit (R PAS ) is expressed as follows: [ka] is expressed by

[0044] In some embodiments, the repeating units (R PAS ) is 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 98 mol%, at least 99 mol%, or at least 99.9 mol%.

[0045] In some embodiments, the poly(arylene sulfide) (PASP) has a weight average molecular weight ("M") of at least 10,000 g / mol, at least 20,000 g / mol, at least 25,000 g / mol, at least 30,000 g / mol, or at least 35,000 g / mol. wIn some embodiments, the poly(arylene sulfide) (PASP) has an M of 150,000 g / mol or less, 100,000 g / mol or less, 90,000 g / mol or less, 85,000 g / mol or less, or 80,000 g / mol or less. w In some embodiments, the poly(arylene sulfide) (PASP) has an M of 10,000 g / mol to 150,000 g / mol, 20,000 g / mol to 100,000 g / mol, 25,000 g / mol to 90,000 g / mol, 30,000 g / mol to 85,000 g / mol, or 35,000 g / mol to 80,000 g / mol. w M w can be measured using gel permeation chromatography ("GPC") using a 4-chloronaphthalene standard.

[0046] Poly(arylene sulfide) (PASP) is semi-crystalline. Those skilled in the art will appreciate that if a polymer is amorphous, it will exhibit detectable T m It will be appreciated that, therefore, when a poly(arylene sulfide) (PASP) has a Tm, it refers to a semi-crystalline polymer. In some embodiments, the poly(arylene sulfide) (PASP) has a ΔH of at least 10 J / g, at least 20 J / g, at least, or at least 25 J / g. f In some embodiments, the poly(arylene sulfide) (PASP) has a ΔH of 90 J / g or less, 70 J / g or less, or 60 J / g or less. f In some embodiments, the poly(arylene sulfide) (PASP) has a ΔH of 10 J / g to 90 J / g or 20 J / g to 70 J / g. f It has.

[0047] In some embodiments, the poly(arylene sulfide) (PASP) has a melting temperature ("T") of at least 200°C, at least 220°C, at least 240°C, or at least 250°C. mIn some embodiments, the poly(arylene sulfide) (PASP) has a T of 350° C. or less, 320° C. or less, 300° C. or less, or 285° C. or less. m In some embodiments, the poly(arylene sulfide) (PASP) has a T of 200°C to 350°C, 220°C to 320°C, 240°C to 285°C, or 250°C to 300°C. m It has.

[0048] Polymer Composition (PC) The polymer composition (C) comprises a polyamide (PA) and a poly(arylene sulfide) (PASP). In some embodiments, the polymer composition may comprise one or more optional components selected from the group consisting of reinforcing agents and additives. The additives include, but are not limited to, toughening agents, plasticizers, colorants, pigments (e.g., black pigments such as carbon black and nigrosine), antistatic agents, dyes, lubricants (e.g., linear low-density polyethylene, calcium stearate, magnesium stearate, or sodium montanate), heat stabilizers, light stabilizers, flame retardants, nucleating agents, antioxidants, acid scavengers, and other processing aids.

[0049] In some embodiments, the polyamide (PA) concentration in the polymer composition (PC) is at least 5 wt % or at least 10 wt %. In some embodiments, the polyamide (PA) concentration in the polymer composition (PC) is 80 wt % or less or 70 wt % or less. In some embodiments, the polyamide (PA) concentration in the polymer composition (PC) is 5 wt % to 80 wt %, or 10 wt % to 70 wt %. In some embodiments, the poly(arylene sulfide) (PAS) concentration in the polymer composition (PC) is at least 5 wt % or at least 10 wt %. In some embodiments, the poly(arylene sulfide) (PAS) concentration in the polymer composition (PC) is 80 wt % or less or 70 wt % or less. In some embodiments, the poly(arylene sulfide) (PAS) concentration in the polymer composition (PC) is 5 wt % to 80 wt %, or 10 wt % to 70 wt %. As used herein, weight percent refers to the total weight of the polymer composition, unless otherwise specified. In some embodiments, the ratio of the weight of polyamide (PA) to the weight of poly(arylene sulfide) (PAS) is 3:1 to 1:3, 2.5:1 to 1:2.5, 2:1 to 1:2, 1.5:1 to 1:1.5, or 1:1.

[0050] In some embodiments, the polymer composition (PC) includes a reinforcing agent. A wide selection of reinforcing agents, also called reinforcing fibers or fillers, can be added to the polymer composition (PC). In some embodiments, the reinforcing agent is selected from mineral fillers (including, but not limited to, talc, mica, kaolin, calcium carbonate, calcium silicate, magnesium carbonate, etc.), glass fibers, carbon fibers, synthetic polymer fibers, aramid fibers, aluminum fibers, titanium fibers, magnesium fibers, boron carbide fibers, rock wool fibers, steel fibers, and wollastonite.

[0051] Generally, the reinforcing agent is a fibrous reinforcing agent or a particulate reinforcing agent. Fibrous reinforcing agent refers to a material having a length, width, and thickness in which the average length is significantly greater than both the width and the thickness. Generally, such materials have an aspect ratio, defined as the average ratio between the length and the largest of the width and thickness, of at least 5, at least 10, at least 20, or at least 50. In some embodiments, the fibrous reinforcing agent (e.g., glass fiber or carbon fiber) has an average length of 3 mm to 50 mm. In some such embodiments, the fibrous reinforcing agent has 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 fibrous reinforcing agent has 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 fibrous reinforcing agent can be interpreted as the average length of the fibrous reinforcing agent before incorporation into the polymer composition (PC), or it can be interpreted as the average length of the fibrous reinforcing agent in the polymer composition (PC).

[0052] Among fibrous reinforcing agents, glass fiber is preferred. Glass fiber is a silica-based glass compound containing several metal oxides that can be adjusted to yield various types of glass. The primary oxide is silica in the form of silica sand, while other oxides, such as calcium, sodium, and aluminum, are incorporated to lower the melting temperature and prevent crystallization. Glass fiber can be added as endless fibers or chopped glass fibers. Glass fibers generally have an equivalent diameter of 5 to 20 μm, preferably 5 to 15 μm, and more preferably 5 to 10 μm. All glass fiber types, such as A, C, D, E, M, S, R, and T glass fibers (as described in Additives for Plastics Handbook, 2nd ed., John Murphy, chapter 5.2.3, pages 43-48), or any mixture thereof or mixtures thereof, can be used.

[0053] E-, R-, S-, and T-glass fibers are well known in the art. They are described, inter alia, in Fiberglass and Glass Technology, Wallenberger, Frederick T.; Bingham, Paul A. (Eds.), 2010, XIV, chapter 5, pages 197-225. R-, S-, and T-glass fibers consist essentially of oxides of silicon, aluminum, and magnesium. In particular, they typically contain 62-75 wt. % SiO2, 16-28 wt. % Al2O3, and 5-14 wt. % MgO. On the other hand, R-, S-, and T-glass fibers contain less than 10 wt. % CaO.

[0054] In some embodiments, the glass fiber is a high modulus glass fiber. The high modulus glass fiber has a modulus of elasticity of at least 76, preferably at least 78, more preferably at least 80, and most preferably at least 82 GPa, as measured in accordance with ASTM D2343. Examples of high modulus glass fibers include, but are not limited to, S-, R-, and T-glass fibers. Commercially available sources of high modulus glass fibers are S-1 and S-2 glass fibers provided by Taishan and AGY, respectively.

[0055] The morphology of the glass fibers is not particularly limited. As noted above, the glass fibers may have a circular cross-section ("round glass fibers") or a non-circular cross-section ("flat glass fibers"). Non-limiting examples of suitable flat glass fibers include glass fibers having oval, elliptical, and rectangular cross-sections. In some embodiments in which the polymer composition comprises flat glass fibers, the flat glass fibers have a cross-sectional longest dimension of at least 15 μm, preferably at least 20 μm, more preferably at least 22 μm, and even more preferably at least 25 μm. Additionally or alternatively, in some embodiments, the cross-sectional longest dimension of the flat glass fibers is at most 40 μm, preferably at most 35 μm, more preferably at most 32 μm, and even more preferably at most 30 μm. In some embodiments, the cross-sectional diameter of the flat glass fibers is in the range of 15 to 35 μm, preferably 20 to 30 μm, and more preferably 25 to 29 μm. In some embodiments, the flat glass fibers have a cross-sectional minimum diameter of at least 4 μm, preferably at least 5 μm, more preferably at least 6 μm, and even more preferably at least 7 μm. Additionally or alternatively, in some embodiments, the cross-sectional minimum diameter of the flat glass fibers is at most 25 μm, preferably at most 20 μm, more preferably at most 17 μm, and even more preferably at most 15 μm. In some embodiments, the cross-sectional minimum diameter of the flat glass fibers is in the range of 5 to 20 μm, preferably 5 to 15 μm, and more preferably 7 to 11 μm.

[0056] In some embodiments, the aspect ratio of the flat glass fibers is at least 2, preferably at least 2.2, more preferably at least 2.4, and even more preferably at least 3. The aspect ratio is defined as the ratio of the longest diameter in a cross-section of the glass fiber to the shortest diameter in the same cross-section. Additionally or alternatively, in some embodiments, the aspect ratio of the flat glass fibers is at most 8, preferably at most 6, and more preferably at most 4. In some embodiments, the aspect ratio of the flat glass fibers is 2 to 6, preferably 2.2 to 4. In some embodiments in which the glass fibers are round glass fibers, the aspect ratio of the glass fibers is less than 2, preferably less than 1.5, more preferably less than 1.2, even more preferably less than 1.1, and most preferably less than 1.05. Of course, those skilled in the art will understand that, by definition, the aspect ratio cannot be less than 1, regardless of the morphology of the glass fiber (e.g., round or flat).

[0057] In some embodiments, the concentration of reinforcing agent (e.g., glass or carbon fiber) in the polymer composition (PC) is at least 5 wt%, at least 10 wt%, at least 15 wt%, or at least 20 wt%. In some embodiments, the concentration of reinforcing agent in the polymer composition (PC) is 70 wt% or less, 65 wt% or less, or 60 wt% or less. In some embodiments, the concentration of reinforcing agent in the polymer composition (PC) is 5 wt% to 70 wt%, 10 wt% to 70 wt%, 10 wt% to 65 wt%, 10 wt% to 60 wt%, 15 wt% to 60 wt%, or 20 wt% to 60 wt%.

[0058] Regarding additives, as described above, it has been surprisingly discovered that polymer compositions (PC) containing a nucleating agent have significantly improved tensile strength retention after thermal aging compared to polymer compositions (PC) without a nucleating agent. In some embodiments, the nucleating agent is selected from the group consisting of talc, metal carbonates (e.g., calcium carbonate and magnesium carbonate), boron nitride, titanium oxide, titanium dioxide, cellulose particles, poly(ether ether ketone), and nanocrystalline cellulose. In some embodiments, the concentration of the nucleating agent in the polymer composition (PC) is at least 0.1 wt %, at least 0.2 wt %, or at least 0.3 wt %. In some embodiments, the concentration of the nucleating agent in the polymer composition (PC) is 1 wt % or less, 0.8 wt % or less, or 0.7 wt % or less. In some embodiments, the concentration of the nucleating agent is 0.1 wt % to 1 wt %, 0.2 wt % to 0.8 wt %, or 0.3 wt % to 0.7 wt %.

[0059] In some embodiments, the polymer composition (PC) comprises a toughening agent. The toughening agent generally has a low Tg, for example, a Tg below room temperature, below 0°C, or even below -25°C. As a result of its low Tg, the toughening agent is typically elastomeric at room temperature. The toughening agent can be a functionalized polymer backbone.

[0060] The polymer backbone of the toughening agent may be selected from elastomeric backbones comprising polyethylene and copolymers thereof, such as ethylene-butene; ethylene-octene; polypropylene and copolymers thereof; 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.

[0061] If 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.

[0062] Specific examples of functionalized toughening agents are, inter alia, terpolymers of ethylene, acrylic esters and glycidyl methacrylate, copolymers of ethylene and butyl ester acrylate; copolymers of ethylene, butyl ester acrylate 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; ABS copolymers grafted with maleic anhydride.

[0063] In some embodiments, the concentration of the toughening agent in the polymer composition (PC) is at least 1 wt%, at least 1 wt%, or at least 3 wt%. In some embodiments, the concentration of the toughening agent in the polymer composition (PC) is 20 wt% or less, 15 wt% or less, or 10 wt% or less. In some embodiments, the concentration of the toughening agent in the polymer composition (PC) is 1 wt% to 20 wt%, 2 wt% to 15 wt%, or 3 wt% to 10 wt%.

[0064] In some embodiments, the halogen-free flame retardant is an organophosphorus compound selected from the group consisting of phosphine salts (phosphinates), diphosphine salts (diphosphinates), and condensation products thereof. Preferably, the organophosphorus compound is selected from the group consisting of phosphinates of formula (I), diphosphinates of formula (II), and condensation products thereof: [ka] (Wherein, R1 and R2 are the same or different, and each of R1 and R2 is hydrogen or a linear or branched C1-C6 alkyl group or an aryl group; R3 is a linear or branched C1-C6 alkyl group or an aryl group; 10 Alkylene group, C6-C 10 an arylene group, an alkyl-arylene group, or an aryl-alkylene group; M is selected from calcium ions, magnesium ions, aluminum ions, zinc ions, titanium ions, and combinations thereof; m is an integer of 2 or 3; n is an integer of 1 or 3; and x is an integer of 1 or 2).

[0065] Preferably, R1 and R2 are independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, and phenyl; R3 is selected from methylene, ethylene, n-propylene, isopropylene, n-butylene, tert-butylene, n-pentylene, n-octylene, n-dodecylene, phenylene, naphthylene, methylphenylene, ethylphenylene, tert-butylphenylene, methylnaphthylene, ethylnaphthylene, tert-butylnaphthylene, phenylmethylene, phenylethylene, phenylpropylene, and phenylbutylene; and M is selected from aluminum ions and zinc ions.

[0066] Phosphinate is preferred as the organic phosphorus compound.Suitable phosphinate is described in U.S. Patent No. 6,365,071, which is incorporated herein by reference.Particularly preferred phosphinates are aluminum phosphinate, calcium phosphinate, and zinc phosphinate.Excellent results have been obtained with aluminum phosphinate.Among aluminum phosphinates, aluminum ethylmethyl phosphinate and aluminum diethyl phosphinate, and combinations thereof are preferred.

[0067] In some embodiments, the polymer composition (PC), most preferably in embodiments incorporating a halogen-free flame retardant, further comprises an acid scavenger. Acid scavengers include, but are not limited to, silicone; silica; boehmite; metal oxides such as aluminum oxide, calcium oxide, iron oxide, titanium oxide, manganese oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromium oxide, tin oxide, antimony oxide, nickel oxide, copper oxide, and tungsten oxide; metal powders such as aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, tin, antimony, nickel, copper, and tungsten; and metal salts such as barium metaborate, zinc carbonate, magnesium carbonate, calcium carbonate, and barium carbonate. In some embodiments where the polymer composition (PC) includes an acid scavenger, the concentration of the acid scavenger is 0.01% to 5% by weight, 0.05% to 4% by weight, 0.08% to 3% by weight, 0.1% to 2% by weight, 0.1% to 1% by weight, 0.1% to 0.5% by weight, or 0.1% to 0.3% by weight.

[0068] In some embodiments, the total additive concentration in the polymer composition (PC) is at least 0.1 wt%, at least 0.2 wt%, or at least 0.3 wt%. In some embodiments, the total additive concentration in the polymer composition (PC) is 20 wt% or less, 15 wt% or less, 10 wt% or less, 7 wt% or less, or 5 wt% or less. In some embodiments, the total additive concentration in the polymer composition (PC) is 0.1 wt% to 20 wt%, 0.1 wt% to 15 wt%, 0.1 wt% to 10 wt%, 0.2 wt% to 7 wt%, or 0.3 wt% to 5 wt%.

[0069] In some embodiments, the polymer composition (PC) further comprises one or more additional polymers, in some such embodiments, at least one of the additional polymers is a semi-crystalline or amorphous polyamide, such as an aliphatic polyamide or a semi-aromatic polyamide, more typically a polyamide obtained by polycondensation between an aromatic or aliphatic saturated diacid and an aliphatic saturated or aromatic primary diamine, a lactam, an amino acid, or a mixture of these different monomers.

[0070] Preparation of polymer composition (PC) The present invention further relates to a method for making a polymer composition (PC), which method comprises melt blending a polyamide (PA), a poly(arylene sulfide) (PASP), and any optional ingredients (e.g., reinforcing agents and nucleating agents).

[0071] Any melt-blending method can be used to mix the polymeric and non-polymeric components involved in the present invention. For example, the polymeric and non-polymeric components can be fed into a melt mixer such as a single-screw or twin-screw extruder, a stirrer, a single-screw or twin-screw kneader, or a Banbury mixer. The addition process can be simultaneous addition of all components or batchwise stepwise addition. When the polymeric and non-polymeric ingredients are added gradually in a batchwise manner, 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 has a long physical form (e.g., long glass fibers and continuous fibers), stretch extrusion or pultrusion can be used to prepare the reinforced composition.

[0072] Articles and uses The present invention also relates to articles incorporating the polymer composition (PC). The polymer composition (PC) is desirably incorporated into any article that is exposed to high temperatures and aqueous polyol solutions during its intended use, at least in part due to improved mechanical retention after thermal aging.

[0073] In some embodiments, the article is selected from the group consisting of automotive parts, marine parts, and aerospace parts. In some embodiments, the article is selected from the group consisting of fluid inlet / outlet ports, fluid inlet / outlet valves, fluid pump housings, fluid pump impellers, fluid hose connectors, fluid hoses, fluid reservoirs, and fluid valves, and the fluid is an aqueous polyol solution, preferably an aqueous solution of ethylene glycol, propylene glycol, or diethylene glycol. The polymer composition (PC) is further advantageously incorporated into such articles when such articles are used in engine compartments (e.g., when exposed to high temperatures).

[0074] In some embodiments, articles are molded from polymer composition (PC) by any process suitable for thermoplastics, such as extrusion, injection molding, blow molding, rotational molding, or compression molding. Polymer composition (C) can also be used to overmold preformed shapes to build hybrid structures.

[0075] In some embodiments, the article is printed from the polymer composition (PC) by a process comprising a step of extrusion of the polymer composition (PC), for example in the form of a filament, or in this case by a process comprising a step of laser sintering of the polymer composition (PC) in the form of a powder.

[0076] The present invention also relates to a method of manufacturing a three-dimensional (3D) object in an additive manufacturing system, the method comprising providing a part material comprising a polymer composition (PC) and printing layers of the three-dimensional object from the part material.

[0077] Thus, the polymer composition (PC) can be in the form of a thread or filament used in a 3D printing process, such as fused filament manufacturing, also known as fused deposition modeling ("FDM").

[0078] The polymer composition (PC) can also be in powder form, for example in the form of a substantially spherical powder, for use in 3D printing processes, such as selective laser sintering ("SLS").

[0079] Polymer Compositions (PC) and Articles of Use The present invention relates to the use of the polymer composition (PC) or article for manufacturing an automotive, marine or aerospace part as described above. The present invention also relates to the use of the polymer composition (PC) for 3D printing an object. [Example]

[0080] This example demonstrates the synthesis, thermal performance, and mechanical performance of polyamides.

[0081] The raw materials used to form the samples are as follows: Poly(arylene sulfide): PPS (from Solvay Specialty Polymers USA, LLC) Polyamide 1 ("PA1"): PA6T / 6I / 66 (from Solvay Specialty Polymers USA, LLC; Tg = 125°C and Tm = 310°C), respectively Polyamide 2 ("PA2"): PA6, T / 1,3-BAC, T / 6, CHDA / 1,3-BAC, CHDA (Tg=165°C, Tm=330°C), synthesized from: - Hexamethylenediamine (70% by weight, from Ascend Performance Materials) - 1,3-bis(aminomethyl)cyclohexane (from Mitsubishi Gas Chemical Company) - Terephthalic Acid (from Flint Hills Resources) - 1,4-Cyclohexanedicarboxylic acid (from Eastman Chemical Company) Nucleating agent: Talc (Mistron Vapor, from Imerys) Reinforcing filler: Glass fiber: Chopped E-glass fiber (NEG 779H, from Nippon Electric Glass) Pigment: Black pigment. PLASBLACK® un2014 Black Pigment (from Cabot).

[0082] Example 1-PA 2 Synthesis of This example shows the polyamide 2 The synthesis of is demonstrated.

[0083] PA 2 was prepared in an autoclave reactor equipped with a distillation line and a pressure control valve. The reactor was charged with 498 g of 70% hexamethylenediamine, 165 g of 1,3-bis(aminomethyl)cyclohexane, 635 g of terephthalic acid, 20 g of 1,4-cyclohexanedicarboxylic acid, 355 g of deionized water, 7.2 g of glacial acetic acid, and 0.32 g of phosphoric acid. The reactor was sealed, purged with nitrogen, and heated to 260 °C. The evolved water vapor was slowly released to maintain an internal pressure of 120 psig. The temperature was increased to 335 °C. The reaction mixture was held at 335 °C for 60 minutes while the reactor pressure was reduced to atmospheric pressure. The polymer was removed from the reactor and used to prepare compound formulations.

[0084] Example 2 - Mechanical Performance This example demonstrates the mechanical performance of the polymer composition.

[0085] To demonstrate mechanical performance, polymeric compositions were formed by melt-blending polymer resins (PPS, PA1, or PA2) with various additives in an extruder. The polymeric compositions were then molded into test samples, and the mechanical properties (tensile and flexural properties) of the test samples were tested before ("as molded") and after ("post-aged") aging. Aging involved immersing the test samples in a 50:50 ethylene glycol:water solution at 130°C for 2000 hours. Tensile modulus, tensile strength, and tensile elongation were measured in accordance with ISO 527-2 on dumbbell-shaped ISO Type 1A tensile specimens with the following nominal dimensions: total length 170 mm, gauge length 75 mm, parallel section length 80 mm, parallel section width 10 mm, grip section width 20 mm, and thickness 4 mm. Flexural modulus, flexural strength, and flexural elongation were measured in accordance with ISO 178 on standard ISO flexural specimens with the following nominal dimensions: length 80 mm, width 10 mm, and thickness 4 mm. Sample parameters and tensile properties are shown in Tables 1 and 2, respectively. In the tables, "E" denotes an example and "CE" denotes a counterexample. All values ​​in Table 1 are reported in weight percent.

[0086] [Table 1]

[0087] [Table 2]

[0088] Referring to Table 2, the samples containing PA2 surprisingly showed not only increased tensile property retention after aging compared to the samples containing PA1, but also increased tensile property values. For example, E1 and E2 showed significantly increased percent retention of tensile modulus and strength compared to CE1 and CE2, respectively. Furthermore, after aging, E1 and E2 also showed increased tensile modulus and strength compared to CE1 and CE2.

[0089] Additionally, it was surprisingly found that samples containing a nucleating agent in addition to PA2 had increased tensile strength retention compared to samples containing PA2 without a nucleating agent. For example, E1 had an approximately 12% increase in tensile strength retention over CE1, while E2 had an approximately 17% increase in tensile strength retention over CE2.

[0090] The above-described 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 may be made in form and detail without departing from the spirit and scope of the present invention. Any incorporation by reference of the above documents is limited to not incorporating subject matter contrary to the express disclosure herein.

Claims

1. A polymer composition (PC), comprising: - polyamide (PA) in a concentration ranging from 5% to 80% by weight based on the total weight of said polymer composition (PC); - poly(arylene sulfide) (PAS) in a concentration of 5% to 80% by weight based on the total weight of said polymer composition (PC); Including, The polyamide (PA) 20 mol % to 95 mol % C ４ ~C １２ an aliphatic diamine, - 5 mol % to 80 mol % of bis(aminoalkyl)cyclohexanes, wherein these mole percentages are based on the total number of moles of each diamine in the diamine component; - 30 mol % to 99 mol % of terephthalic acid, - 1 mol % to 70 mol % of cyclohexanedicarboxylic acid, wherein the mole percentages are based on the total number of moles of each dicarboxylic acid in the dicarboxylic acid component. A polymer composition (PC) derived by polycondensation of monomers in a reaction mixture comprising:

2. Said C ４ ~C １２ 2. The polymer composition (PC) of claim 1, wherein the aliphatic diamine is selected from the group consisting of 1,4-diaminobutane, 1,5-diaminopentane, 2-methyl-1,5-diaminopentane, 1,6-diaminohexane, 3-methylhexamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,2,4-trimethyl-hexamethylenediamine, 2,4,4-trimethyl-hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 2,2,7,7-tetramethyloctamethylenediamine, 1,9-diaminononane, 2-methyl-1,8-diaminooctane, 5-methyl-1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane.

3. The polymer composition (PC) according to claim 1 or 2, wherein the bis(aminoalkyl)cyclohexane is 1,3-bis(aminomethyl)cyclohexane or 1,4-bis(aminomethyl)cyclohexane.

4. The polymer composition (PC) according to any one of claims 1 to 3, wherein the dicarboxylic acid component (B) comprises 1,4-cyclohexanedicarboxylic acid.

5. The polymer composition (PC) according to any one of claims 1 to 4, wherein said poly(arylene sulfide) is polyphenylene sulfide.

6. The polymer composition (PC) according to any one of claims 1 to 5, further comprising 0.1% to 1% by weight of a nucleating agent relative to the total weight of the polymer composition (PC).

7. The polymer composition (PC) according to any one of claims 1 to 6, further comprising 5 to 70% by weight of a reinforcing agent relative to the total weight of the polymer composition.

8. 8. A polymer composition (PC) according to claim 7, wherein said reinforcing agent is glass fibre or carbon fibre.

9. 9. The polymer composition (PC) according to any one of claims 1 to 8, wherein said polymer composition (PC) has a tensile elasticity retention of at least 85% after aging for 2000 hours in a 50:50 ethylene glycol:water solution at 130°C.

10. 10. The polymer composition (PC) according to any one of claims 1 to 9, wherein said polymer composition (PC) has at least 90% retention of tensile elasticity after aging for 2000 hours in a 50:50 ethylene glycol:water solution at 130°C.

11. 11. An article comprising the polymer composition of any one of claims 1 to 10, selected from the group consisting of a fluid inlet port, a fluid outlet port, a fluid inlet valve, a fluid outlet valve, a fluid pump housing, a fluid pump impeller, a fluid hose connector, a fluid hose, a liquid reservoir, and a liquid valve.

12. The article of claim 11 , wherein the article is contacted with an aqueous polyol solution.

13. 12. The article of claim 11, wherein the article is exposed to a temperature of at least 130°C.

Images