JPWO2020229318A5 - - Google Patents

Description

Cross-reference to related applications
This application is a US National Phase entry under US patent law of International Patent Application No. PCT/EP2020/062781 filed May 7, 2020. This application claims priority to U.S. Provisional Application No. 62/847409 filed May 14, 2019 and European Patent Application No. 19198924.3 filed September 23, 2019. and the entire contents of these applications are incorporated herein by reference for all purposes.

The present invention relates to polyamides with high thermal performance. The invention further relates to polymer compositions comprising polyamides and articles comprising polyamides or polymer compositions.

Thermal performance (glass transition temperature (“Tg”), melting temperature (“Tm”), and crystallinity (“ΔH _f ”)) are important factors in determining the application situations in which polyamides can be desirably used. Semi-aromatic polyamides have attracted much interest because of their relatively high melting temperature (“Tm”) and degree of crystallinity (“ΔH _f ”). The Tg of conventional polyamides is generally less than 150°C, which is sufficient for conventional application situations. However, new applications and markets expose polyamides to more severe thermal conditions, requiring Tg's of 150° C. and above. Although the introduction of cycloaliphatic repeat units into semi-aromatic polyamides has been successful in raising the Tg of the resulting polyamide, this undesirably lowers the Tm and ΔH _f or, in some cases, increases the At the cost of increasing the Tm to 370°C. In the former case, polyamides are limited to low temperature applications and have properties close to those of amorphous polyamides. In the latter case, polyamides cannot be properly melt processed, at least in part due to polymer degradation at melt processing temperatures and holding times. Thus, Tg and Tm are high enough for use in a wide range of application situations, desirably low enough for melt processing, and for reduced injection molding cycle time and high temperature mechanical properties, chemical resistance, heat deflection temperature, etc. There is a need to develop polyamides with sufficiently high ΔHf, which is desirable to improve the .

In a first aspect, the present invention contains (1) 20 mol% to 95 mol% of a _C4 - _C12 aliphatic diamine and 5 mol% to 80 mol% of a bis(aminoalkyl)cyclohexane, is relative to the total number of moles of all diamines in the diamine component; and (2) 30 to 99 mole percent terephthalic acid and 1 to 70 mole percent cyclohexanedicarboxylic acid. and wherein the molar percentages of these are relative to the total number of moles of all dicarboxylic acids in the dicarboxylic acid component (B); PA).

In some embodiments, the polyamide (PA) has a heat of fusion (“ΔH _f ”) of at least 30 J/g, measured according to ASTM D3418 using a heating rate of 20° C./min. In some embodiments, the polyamide (PA) has a glass transition temperature (“Tg”) of at least 145° C. measured according to ASTM D3418. In some embodiments, the polyamide (PA) has a melting temperature (“Tm”) of at least 295° C. measured according to ASTM D3418.

In a second aspect, the present invention relates to a process for producing a polyamide (PA) comprising, in a reaction mixture, at least a _C4 - _C12 aliphatic diamine, and It involves reacting a bis(aminoalkyl)cyclohexane, terephthalic acid and cyclohexanedicarboxylic acid.

In a third aspect, the present invention provides polyamides (PA), reinforcing agents, reinforcing agents, plasticizers, colorants, pigments, antistatic agents, dyes, lubricants, heat stabilizers, light stabilizers, flame retardants, It relates to a polymer composition (C) containing a nucleating agent and at least one component selected from the group consisting of antioxidants.

In a fourth aspect, the present invention relates to an article comprising the polymer composition (C), which article is a portable electronic device article or component, an electrical component, an electronic component, an automotive component, a food contact component, Piping components and oil and gas related components, continuous fiber reinforced thermoplastic composites, or 3D printed articles.

As used herein, (1) 20 mol % to 95 mol % of C ₄ -C ₁₂ aliphatic diamine and 5 mol % to 80 mol % of bis(aminoalkyl)cyclohexane, wherein mol % of these is diamine a diamine component (A) which is relative to the total number of moles of all diamine monomers in the component; A polyamide (PA) derived from the polycondensation of monomers in a reaction mixture containing a dicarboxylic acid component (B), wherein the mole % is relative to the total number of moles of all dicarboxylic acid monomers in the dicarboxylic acid component; . Surprisingly, the particular combination of bis(aminoalkyl)cyclohexane and cyclohexanedicarboxylic acid results in polyamide (PA) being an overall improvement over similar polyamides in which the cyclohexanedicarboxylic acid is replaced with an aromatic dicarboxylic acid. have been found to have excellent thermal performance. 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 _f ”) of at least 30 J/g. .

In this application, any description, even if described in relation to a particular embodiment, is applicable to and interchangeable with other embodiments of the disclosure. Where an element or component is included in and/or selected from a recited list of elements or components, in related embodiments expressly contemplated in the present application, the component or component is individually or may be selected from the group consisting of any two or more of the specifically recited elements or components; Any element or component may be omitted from such lists; any recitation herein of numerical ranges by endpoints includes all numbers within the recited range, as well as the range endpoints and equivalents. It should be understood that

Unless specifically limited otherwise, the terms "alkyl" and derivative terms such as "alkoxy", "acyl" and "alkylthio", as used herein, include straight-chain, branched-chain and cyclic Including part. Examples of alkyl groups are methyl, ethyl, 1-methylethyl, propyl, 1,1-dimethylethyl and cyclopropyl. Unless otherwise specifically stated, each alkyl and aryl group may be unsubstituted or halogen, hydroxy, sulfo, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ acyl, formyl , cyano, C ₆ -C ₁₅ aryloxy or C ₆ -C ₁₅ aryl, provided that the substituents are sterically compatible , provided that the chemical bonding and strain energy rules are satisfied. The term "halogen" or "halo" includes fluorine, chlorine, bromine and iodine, with fluorine being preferred.

The term "aryl" means a phenyl, indanyl, or naphthyl group. An aryl group may contain one or more alkyl groups, in which case it may also be referred to as an "alkylaryl", for example composed of a cycloaromatic group and two C ₁ -C ₆ groups (eg methyl or ethyl). can be Aryl groups may also contain one or more heteroatoms such as N, O or S, in which case they may also be referred to as "heteroaryl"; these heteroaromatic rings may 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 are unsubstituted or halogen, hydroxy, C ₁ -C ₆ alkoxy, sulfo, C ₁ -C ₆ alkylthio, C ₁ -C ₆ acyl, formyl, cyano, C ₆ -C may be substituted with one or more substituents selected from, but not limited to, C ₆ -C ₁₅ aryloxy or C 6 _{-C 15} aryl, provided that the substituents are sterically compatible, chemical bond and strain energy provided that the rules of

Diamine component (A)
Diamine Component (A) Component comprises all diamines in the reaction mixture, including 20 mol % to 95 mol % C ₄ -C ₁₂ aliphatic diamines and 5 mol % to 80 mol % bis(aminoalkyl)cyclohexane. include. When referring to concentrations of monomers in diamine component (A), it is understood that concentrations are relative to total moles of all diamines in diamine component (A) unless otherwise specified.

In some embodiments, the _C4 - _C12 aliphatic diamine is represented by the formula:
H ₂ N—R ₁ —NH ₂ , (1)
(wherein R ₁ is a C ₄ -C ₁₂ alkyl group, preferably a C ₆ -C ₁₀ alkyl group). In some embodiments, R ₁ is -(CH ₂ )- _m , where m is 4-12, preferably 5-11, most preferably 6. In some embodiments, the _C4 - _C12 aliphatic diamines are 1,4-diaminobutane (putrescine), 1,5-diaminopentane (cadaverine), 2-methyl-1,5-diaminopentane, hexamethylene Diamine (or 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- It is selected from the group consisting of 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane. Preferably, the _C4 - _C12 aliphatic diamine is 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 _C4 - _C12 aliphatic diamine is a C6 - _C10 aliphatic diamine or a _C5 - _C9 aliphatic _diamine . Most preferably, the _C4 - _C12 aliphatic diamine is 1,6-diaminohexane.

In some embodiments, the concentration of C4 _- C12 _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 %. In some embodiments, the concentration of C4 _- C12 _aliphatic 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 %.

（式中、Ｒ_２及びＲ_３はＣ_１～Ｃ_１０アルキルから独立して選択され；Ｒ_ｉは、各位置において、アルキル、アリール、アルカリ又はアルカリ土類金属スルホン酸塩、アルキルスルホン酸塩、及び四級アンモニウムからなる群から選択され；ｉは０～１０の整数である）。アミノアルキル基は、メタ位（１，３－）又はパラ位（１，４－）に相対的に配置される。好ましくは、ｉは０であり、Ｒ_２及びＲ_３は共に－ＣＨ_２－である。最も好ましくは、ビス（アミノアルキル）シクロヘキサンは、１，３－ビス（アミノメチル）シクロヘキサン（「１，３－ＢＡＣ」）及び１，４－ビス（アミノメチル）シクロヘキサン（「１，４－ＢＡＣ」）から選択される。当然、ビス（アミノアルキル）シクロヘキサンはシス配座であってもトランス配座であってもよい。したがって、ジアミン成分（Ａ）は、シス－ビス（アミノアルキル）シクロヘキサンのみ、トランス－ビス（アミノアルキル）シクロヘキサンのみ、又はシス－とトランス－のビス（アミノアルキル）シクロヘキサンの混合物を含むことができる。 Bis(aminoalkyl)cyclohexane is represented by the formula:

(wherein R ₂ and R ₃ are independently selected from C ₁ -C ₁₀ alkyl; R _i is at each position alkyl, aryl, alkali or alkaline earth metal sulfonate, alkyl sulfonate, and quaternary ammonium; i is an integer from 0 to 10). Aminoalkyl groups are relatively positioned at the meta (1,3-) or para (1,4-) positions. Preferably i is 0 and both R ₂ and R ₃ are -CH ₂ -. Most preferably, the bis(aminoalkyl)cyclohexanes are 1,3-bis(aminomethyl)cyclohexane (“1,3-BAC”) and 1,4-bis(aminomethyl)cyclohexane (“1,4-BAC”). ). Of course, the bis(aminoalkyl)cyclohexane can be in cis or trans configuration. Thus, diamine component (A) can comprise only cis-bis(aminoalkyl)cyclohexanes, only trans-bis(aminoalkyl)cyclohexanes, or a mixture of cis- and trans-bis(aminoalkyl)cyclohexanes.

In some embodiments, the concentration of 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 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 %.

As noted above, in some embodiments, diamine component (A) comprises one or more additional diamines. Additional diamines are different from _C4 - _C12 aliphatic diamines and different from bis(aminoalkyl)cyclohexanes. In some embodiments, one, more, or all of the additional diamines are represented by Formula (1) and are each different from each other and different from the C ₄ -C ₁₂ aliphatic diamine. In some embodiments, each additional diamine is 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-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, 1,12-diaminododecane, 1,13-diaminotridecane, 2,5-bis (Aminomethyl)tetrahydrofuran, and N,N-bis(3-aminopropyl)methylamine. Also included in this category are cycloaliphatic diamines such as isophoronediamine, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis-p-aminocyclohexylmethane. In some embodiments, the diamine component does not include cycloaliphatic diamines other than bis(aminoalkyl)cyclohexanes. As used herein, free of monomer (e.g. bis(aminoalkyl)cyclohexane) means that the concentration of monomer in the corresponding component (e.g. diamine component (A)) is less than 1 mol%, preferably less than 0.5 mol. %, more preferably less than 0.1 mol %, more preferably less than 0.05 mol %, most preferably less than 0.01 mol %.

Dicarboxylic acid component (B)
Dicarboxylic acid component (B) includes all dicarboxylic acids in the reaction mixture, including 30 mol % to 99 mol % terephthalic acid and 1 mol % to 70 mol % cyclohexanedicarboxylic acid. When referring to concentrations of monomers in the dicarboxylic acid component (B), it is understood that concentrations are relative to the number of moles of all dicarboxylic acids in the dicarboxylic acid component (A) unless otherwise specified. would be

In some embodiments, the concentration of terephthalic acid is 30 mol % to 99 mol %, 40 mol % to 99 mol %, 45 mol % to 99 mol %, 50 mol % to 99 mol %. In some embodiments, the concentration of terephthalic acid is 35 mol % to 97 mol %, 40 mol % to 97 mol %, 45 mol % to 97 mol %, 50 mol % to 97 mol % .

（式中、Ｒ_ｊは、アルキル、アリール、アルカリ又はアルカリ土類金属スルホン酸塩、アルキルスルホン酸塩、及び四級アンモニウムからなる群から選択され；ｊは０～１０の整数である）。明示的な－ＣＯＯＨ基は、メタ位（１，３－）又はパラ位（１，４－）、好ましくはパラ位に相対的に配置される。好ましくは、シクロヘキサンジカルボン酸は、１，４－シクロヘキサンジカルボン酸（「ＣＨＤＡ」）（ｊは０である）である。当然、シクロヘキサンジカルボン酸は、シス配座であってもトランス配座であってもよい。したがって、ジカルボン酸成分（Ｂ）は、シス－シクロヘキサンジカルボン酸のみ、トランス－シクロヘキサンジカルボン酸のみ、又はシス－とトランス－のシクロヘキサンジカルボン酸の混合物を含むことができる。 Cyclohexanedicarboxylic acid is represented by the formula:

(wherein 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 0-10). Explicit -COOH groups are relatively positioned in the meta (1,3-) or para (1,4-) positions, preferably in the para position. Preferably, the cyclohexanedicarboxylic acid is 1,4-cyclohexanedicarboxylic acid (“CHDA”) (where j is 0). Naturally, the cyclohexanedicarboxylic acid can be in the cis or trans configuration. Thus, the dicarboxylic acid component (B) can comprise only cis-cyclohexanedicarboxylic acid, only trans-cyclohexanedicarboxylic acid, or a mixture of cis- and trans-cyclohexanedicarboxylic acids.

The concentration of cyclohexanedicarboxylic acid is from 1 mol % to 70 mol %. In some embodiments, the concentration of cyclohexanedicarboxylic acid is 1 mol% to 65 mol%, 1 mol% to 60 mol%, 1 mol% to 55 mol%, or 1 mol% to 50 mol%.

As noted above, in some embodiments, dicarboxylic acid component (B) comprises one or more additional dicarboxylic acids. Each additional dicarboxylic acid is different from each other 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 each other and different from cyclohexanedicarboxylic acid.

In some embodiments, the one or more additional dicarboxylic acids are independently selected from the group consisting of _C4 - _C12 aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and cycloaliphatic dicarboxylic acids. Examples of desirable _C4 - _C10 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(CH ₃ ) ₂ -(CH ₂ ) ₂ -COOH], adipic acid [HOOC-(CH ₂ ) ₄ -COOH], 2,4,4-trimethyl-adipine 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-(CH ₂ ) ₇ -COOH], sebacic acid [HOOC-(CH ₂ ) ₈ -COOH], 1,12-dodecanedioic acid [HOOC-(CH ₂ ) ₁₀ -COOH] is mentioned.

Examples of desirable aromatic dicarboxylic acids include, but are not limited to, phthalic acids such as isophthalic acid (IA), naphthalenedicarboxylic acids (eg 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)hexafluoro Propane, 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, bis(3-carboxyphenoxy)benzene.

Examples of desirable cycloaliphatic 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.

In some embodiments in which the polyamide (PA) comprises one or more additional dicarboxylic acids, the total concentration of one or more additional dicarboxylic acids is 20 mol% or less.

（式中、Ｒ_１～Ｒ_３、Ｒ_ｉ、Ｒ_ｊ、ｉ及びｊは、上記で定義した通りである）の化合物から選択される。当業者であれば、繰り返し単位Ｒ_ＰＡ１がＣ_４～Ｃ_１２脂肪族ジアミンとテレフタル酸との重縮合から形成され、繰り返し単位Ｒ_ＰＡ２がＣ_４～Ｃ_１２脂肪族ジアミンとシクロヘキサンジカルボン酸との重縮合から形成され、繰り返し単位Ｒ_ＰＡ３がビス（アミノアルキル）シクロヘキサンとテレフタル酸との重縮合から形成され、繰り返し単位Ｒ_ＰＡ４がビス（アミノアルキル）シクロヘキサンとシクロヘキサンジカルボン酸との重縮合から形成されることを認識するであろう。好ましくは、Ｒ_ＰＡ２及びＲ_ＰＡ４は、それぞれ、以下の式で表される（式中、Ｒ _１ ～Ｒ _３ 、Ｒ _ｉ 、Ｒ _ｊ 、ｉ及びｊは、上記で定義した通りである）：

Polyamide (PA)
Polyamides (PA) formed from the polycondensation of the monomers in the diamine component and the dicarboxylic acid component described above contain repeating units R _PA1 to R _PA4 each represented by the formula:

wherein R ₁ -R ₃ , R _i , R _j , i and j are as defined above. Those skilled in the art will recognize that the repeating unit R _PA1 is formed from the polycondensation of a C ₄ -C ₁₂ aliphatic diamine and terephthalic acid, and the repeating unit R _PA2 is the polymerization of a C ₄ -C ₁₂ aliphatic diamine and cyclohexanedicarboxylic acid. condensation, with repeat unit _RPA3 formed from the polycondensation of bis(aminoalkyl)cyclohexane and terephthalic acid, and repeat unit _RPA4 formed from the polycondensation of bis(aminoalkyl)cyclohexane and cyclohexanedicarboxylic acid. will recognize that Preferably , R _{PA2 and} R _PA4 are each _represented by the _{formula :}

In some embodiments, R ₁ is —(CH ₂ ) _—m , where m is 4-12 , preferably 5-11 , most preferably 6. Additionally or alternatively, in some embodiments, both R ₂ and R ₃ are —CH ₂ — and i and j are both zero. Preferably, in all formulas (4) to (9), R ₁ is -(CH ₂ ) ₆ -, both R ₂ and R ₃ are -CH ₂ -, i and j are both zero .

In some embodiments, the total concentration of repeating units R _PA1 -R _PA4 in the polyamide (PA) 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%. It will be understood that when referring to mol % of repeat units, the concentrations are relative to the total number of repeat units in the indicated polymer unless otherwise specified.

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

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) is a have a Tg. Tg can be measured according to ASTM D3418.

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) is a have a Tm. Tm can be measured according to ASTM D3418.

Polyamides (PA) of the present invention are 1,000 g/mol to 40,000 g/mol, such as 2,000 g/mol to 35,000 g/mol, 4,000 to 30,000 g/mol, or It can have a number average molecular weight (“Mn”) ranging from ˜20,000 g/mole. Number average molecular weight Mn can be measured by gel permeation chromatography (GPC) using ASTM D5296 using polystyrene standards.

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

The polyamides (PA) described herein can be prepared, for example, by thermal polycondensation (also called polycondensation or condensation) of aqueous solutions of monomers and comonomers. In one embodiment, the polyamide (PA) is formed by reacting at least a _C4 - _C12 aliphatic diamine, a bis(aminoalkyl)cyclohexane, terephthalic acid, and cyclohexanedicarboxylic acid in a reaction mixture. be. 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 acids in the reaction mixture. As used herein, substantially equimolar means a value that is ±15% of the indicated number of moles. For example, relative to the concentration of diamine and dicarboxylic acid in the reaction mixture, the total moles of diamine in the reaction mixture is ±15% of the total moles of dicarboxylic acid in the reaction mixture. The reaction mixture may also contain a chain limiter, which is a monofunctional molecule capable of reacting with amine or carboxylic acid sites, used to control the molecular weight of the polyamide (PA). For example, the chain limiter may be acetic acid, propionic acid, benzoic acid, and/or benzylamine. Catalysts 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.

Polymer composition (C)
The polymer composition (C) comprises the polyamide (PA) of the invention as described above.

Polyamide (PA) is present in composition (C) in a total amount of greater than 30 wt%, greater than 35 wt%, greater than 40 wt%, or greater than 45 wt%, based on the total weight of polymer composition (C) can.

Polyamide (PA) is less than 99.95 wt%, less than 99 wt%, less than 95 wt%, less than 90 wt%, less than 80 wt%, less than 70 wt%, based on the total weight of the polymer composition (C) , or in a total amount of less than 60% by weight in composition (C).

Polyamide (PA) may be present in composition (C), for example, in an amount ranging from 35 to 70% by weight, such as from 40 to 55% by weight, based on the total weight of polymer composition (C).

Composition (C) contains reinforcing agents, reinforcing agents, plasticizers, colorants, pigments, antistatic agents, dyes, lubricants, heat stabilizers, light stabilizers, flame retardants, nucleating agents, antioxidants, and A component selected from the group consisting of other processing aids may also be included.

A wide variety of reinforcing agents (also called reinforcing fibers or fillers) may be added to the compositions according to the invention. They can be selected from fibrous and particulate reinforcing agents. A fiber reinforced filler is considered herein to be a material having a length, width and thickness whose average length is significantly greater than both the width and thickness. Generally, such materials have an aspect ratio defined as the average ratio between length and maximum width and thickness of at least 5, at least 10, at least 20, or at least 50. In some embodiments, reinforcing fibers (eg, 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 understood as the average length of the reinforcing fibers before being incorporated into the polymer composition (C) or as the average length of the reinforcing fibers in the polymer composition (C). be able to.

Reinforcing fillers include mineral fillers (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, carbonized It can be selected from boron fibres, rockwool fibres, steel fibres, and wollastonite.

Among fibrous fillers, glass fibers are preferred; these include additives for Plastics Handbook, 2nd edition, John Murphy, chapter 5.2. Included are A-, E-, C-, D-, S- and R-glass fibers that are chopped strands as described in 43-48. Preferably, the filler is selected from fibrous fillers. The fillers are more preferably reinforcing fibers that can withstand high temperature applications.

The reinforcing agent may be present in composition (C) in a total amount of greater than 15 wt%, greater than 20 wt%, greater than 25 wt%, or greater than 30 wt% based on the total weight of polymer composition (C). The reinforcing agent 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).

Reinforcing fillers may be present in composition (C), for example, in amounts ranging from 20 to 60% by weight, such as from 30 to 50% by weight, based on the total weight of polymer composition (C).

The composition (C) of the present invention may also contain toughening agents. Tougheners are generally low Tg polymers, eg, having a Tg below room temperature, below 0°C, or even below -25°C. As a result of their low Tg, tougheners are typically elastomeric at room temperature. The toughening agent can be a functionalized polymer backbone.

The polymer backbone of the toughening agent is polyethylene and their copolymers such as ethylene-butene; ethylene-octene; polypropylene and their copolymers; polybutene; (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); methacrylate-butadiene-styrene (MBS) type core-shell elastomers, or elastomer backbones comprising mixtures of one or more of the above.

If the toughening agent is functionalized, the functionalization of the backbone can result from copolymerization of monomers containing functional groups or grafting of the polymer backbone with additional components.

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 copolymer; EPR grafted with maleic anhydride; styrene copolymer grafted with maleic anhydride; SEBS copolymer grafted with maleic anhydride; styrene-acrylonitrile copolymer grafted with maleic anhydride; ABS copolymer grafted with maleic acid.

The toughening agents may be present in composition (C) in a total amount of greater than 1 wt%, greater than 2 wt%, or greater than 3 wt%, based on the total weight of composition (C). The toughening agent 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).

The polymer composition (C) contains 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 Other conventional additives commonly used in the art such as sodium montanate), heat stabilizers, light stabilizers, flame retardants, nucleating agents and antioxidants may also be included.

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

Preparation of Polymer Composition (C) The present invention further provides a process for producing a composition (C) as detailed above, said process comprising a polyamide (PA) and certain components, such as fillers. melt-blending the agent , toughening agent, stabilizing agent, and any other optional additives.

Any melt-blending method may be used to combine the polymeric and non-polymeric components in connection with the present invention. For example, the polymeric component and the non-polymeric component can be fed into a single or twin screw extruder, an agitator, a single or twin screw kneader, or a melt mixer such as a Banbury mixer, and the step of adding , simultaneous addition of all ingredients or batch-wise stepwise addition. When the polymeric component and non-polymeric component are added batchwise and gradually, a portion of the polymeric component and/or non-polymeric component is added first and then added thereafter until a well-mixed composition is obtained. It is melt mixed with the remaining polymeric and non-polymeric components. Stretch extrusion or pultrusion may be used to prepare the reinforced composition when the reinforcing agent exhibits long physical shapes such as long glass fibers and continuous fibers.

Articles and Uses The present invention also relates to articles comprising the polyamide (PA) of the invention and articles comprising the copolymer composition (C) described above.

The articles are particularly portable electronic devices, LED packaging, oil and gas related components, food contact components (including but not limited to food films and casings), electrical and electronic components (computer (including, but not limited to, power supply components for commercial applications, data systems and office equipment, and connectors and contacts compatible with surface mount technology), medical equipment components, construction related components (cooling and heating Pipes, connectors, manifolds and valves for systems; components of boilers and meters ; pipes and fittings of gas systems; and electrical protectors, contactors, switches and sockets for mini circuit breakers. ), industrial components, plumbing components (including but not limited to pipes, valves, fittings, manifolds, shower taps, and shower valves), automotive components, and aerospace components (inboard cabin configurations (including but not limited to elements).

The article can be, for example, a portable electronic device component. As used herein, "portable electronic device" means an electronic device intended to be conveniently carried and used in various locations. Portable electronic devices include 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, Non-limiting examples include global positioning system receivers and handheld game consoles.

Portable electronic device components can include, for example, radio antennas and the present composition (C). In this case, the radio antenna can be a WiFi antenna or an RFID antenna. A portable electronic device component can 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, back housings, battery covers, chassis, and frames.

In some embodiments the portable electronic device component is an antenna housing. In some such embodiments, at least a portion of the radio antenna is disposed on polymer composition (C). Additionally or alternatively, at least a portion of the radio antenna can be offset (eg, out of contact) with polymer composition (C). In some embodiments, device components include mounting holes or other fastening devices (theirselves, circuit boards, microphones, speakers, displays, batteries, covers, housings, electrical or electronic connectors, hinges, radio antennas, switches, etc.). , or a snap-fit connector between another component of the portable electronic device, including but not limited to a switch pad. can. In some embodiments, the portable electronic device can be at least part of the input device.

Examples of oil and gas related components include, but are not limited to, compressor rings, poppets, backup seal rings, electrical connectors, labyrinth seals, motor end plates, bearings, bushings, suck rod guides, and downhole tubes. is mentioned.

Examples of automotive parts include, but are not limited to, 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. etc.), 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 device components (including but not limited to dual clutch transmissions, automatic 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 electronic components, automotive lighting components (including but not limited to motor end caps, sensors, ECU housings, bobbins and solenoids, connectors, circuit protection/ relays, actuator housings, Li-ion battery systems, and fuse boxes), traction motors and power electronics components (including but not limited to battery packs), fuel and selective catalytic reduction (“SCR”) systems (limited to SCR module housings and connectors, SCR module housings and connectors, fuel flanges, rollover valves, quick connects, filter housings, fuel rails, fuel supply 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), internal components (e.g. dashboard components, displays components, seat components, etc.), and structural and lightweight components (e.g. gears and bearings, sunroofs, brackets and mounts, electric battery housings, thermal management components, braking system components, and pumps and EGR systems). mentioned.

Polyamides (PA), polymer compositions (C) and articles prepared therefrom can also be used as gas barrier materials for packaging applications in single or multilayer articles.

Polyamides (PA), polymer compositions (C), and articles made therefrom are used in automotive applications such as air intake systems, cooling and heating systems, drive and fuel systems, beams and structural supports, pans and covers. can also be used.

Articles can be formed from the polyamide (PA) or polymer composition (C) of the present invention by any process adapted to thermoplastics, such as extrusion, injection molding, blow molding, rotational molding or compression molding. Polyamide (PA) and polymer composition (C) can also be used in overmolding preformed shapes to build hybrid structures.

Articles are produced from the polyamide (PA) or polymer composition (C) of the invention by a process comprising the step of extruding the material, for example in the form of filaments, or by a process comprising the step of laser sintering the material (in this case The material is in powder form).

The present invention is a method of manufacturing a three-dimensional (3D) object with an additive manufacturing system, comprising:
- providing a component material comprising the polyamide (PA) or polymer composition (C) of the invention;
- printing layers of a three-dimensional object from this part material.

The polyamide (PA) or polymer composition (C) is therefore in the form of threads or filaments used in the process of 3D printing, e.g. fused filament manufacturing, also known as Fused Deposition Modeling (FDM). can also

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

Use of Polyamide (PA), Composition (C) and Articles The present invention provides the above polyamide (PA), composition (C), or Regarding the use of goods.

The invention also relates to the use of the above polyamide (PA) or composition (C) for 3D printing objects.

If the disclosure of any patent, patent application, or publication incorporated herein by reference contradicts the description in this application to the extent that it may obscure the terminology, this description shall control. .

This example demonstrates the synthetic, thermal performance of polyamides.

The raw materials used to form the samples are as follows:
- 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)
- isophthalic acid (from Flint Hills Resources)
- adipic acid (from Invista)
- 2,6-naphthalenedicarboxylic acid (from Indorama)
- Bibenzoic acid (from Sigma Aldrich)
- 5-hydroxyisophthalic acid (from Sigma Aldrich)
- acetic acid (from Sigma Aldrich)
- phosphoric acid (from Sigma Aldrich)

Polyamide Synthesis This example demonstrates the synthesis of polyamides.

All polyamides were prepared according to a similar method in an autoclave reactor equipped with a distillate line fitted with a pressure regulating valve. As an example, in the preparation of polyamide E1, a reactor was charged with 179.3 g of 70% hexamethylenediamine, 102.4 g of 1,3-bis(aminomethyl)cyclohexane, 266.4 g of terephthalic acid, 30.7 g of 1 ,4-cyclohexanedicarboxylic acid, 206 g deionized water, 2.2 g glacial acetic acid, and 0.2 g phosphoric acid. The reactor was sealed, purged with nitrogen and heated to 260°C. Generated steam was slowly released to maintain internal pressure at 120 psig. The temperature was raised to 320°C. The reaction mixture was held at 320° C. and the reaction pressure was reduced to atmospheric pressure. After holding for an additional 20 minutes, the polymer was discharged from the reactor.

A large quantity of polyamide was prepared using the following process (as an example here is the preparation of polyamide CE9). In a stirred batch vessel, 12.25 kg of deionized water, 28.7 kg of the diamine component consisting of 70% hexamethylenediamine, and 19.3 kg of terephthalic acid and 8.3 kg of isophthalic acid, a dicarboxylic acid. put the ingredients. The reactor was also charged with 13.1 g of phosphoric acid and 252 g of glacial acetic acid. A salt solution was obtained by heating the above mixture at 150°C. The contents are continuously pumped to a reactor zone maintained at about 180 psig and 220°C, then to a high pressure zone maintained at 300°C and then to a 100 psig tubular reactor heated to 350°C. pumped through. The melt was fed to a twin screw extruder equipped with a forward vacuum vent. The finished polymer was extruded through a strand die into a water bath and chopped into pellets.

Sample parameters are shown in Table 1. In Table 1, HMDA refers to hexamethylenediamine, TA refers to terephthalic acid, IA refers to isophthalic acid, AA refers to adipic acid, NDA refers to 2,6-naphthalenedicarboxylic acid, BBA refers to 4,4 '-biphenyldicarboxylic acid and HIA refers to 5-hydroxyisophthalic acid.

Thermal Performance To demonstrate thermal performance, Tm, Tg, and ΔH _f were measured as described above. The thermal test results are shown in Table 2.

Referring to Table 2, samples incorporating cycloaliphatic dicarboxylic acids had significantly improved overall thermal performance compared to samples containing aromatic dicarboxylic acids. In particular, each sample E1-E7 according to the invention has a Tg of at least 145° C., a Tm of at least 295° C., and a ΔH _f of at least 30 J/g. On the other hand, each Comparative Example (CE) other than CE7 has at least one of Tg, Tm, and ΔH _f less than 145° C., 295° C., and 30 J/g, respectively. For CE7, the Tm is well above 360° C. and cannot be melt processed (eg, injection molded) without degradation.

Furthermore, comparing E1 with CE3 and CE4, unexpectedly, the polyamides incorporating 1,4-CHDA showed overall have improved thermal performance as For example, E1 (containing 1,4-CHDA) had a Tg above 145°C, a Tm above 295°C, and a ΔH _f above 30 J/g. On the other hand, both CE3 (containing NDA) and CE4 (containing BBA) had a Tm below 295°C. As another example, E5 (containing 1,4-CHDA), like E1, had a Tg above 145°C, a Tm above 295°C, and a ΔH _f above 30 J/g. On the other hand, CE5 (containing NDA) had a Tg of less than 145°C and a Tm of less than 295°C, and CE6 (containing HIA) had a ΔH _f of less than 30 J/g. These examples demonstrate that using a bis(aminoalkyl)cyclohexane, the resulting polyamide surprisingly exhibits overall improved thermal performance compared to the corresponding polyamide in which the CHDA is replaced by an aromatic dicarboxylic acid. is shown to have

The above embodiments are intended to be illustrative and not limiting. Further embodiments are within the concept of the invention. Additionally, although the present invention has been described with reference to specific embodiments, workers skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the invention. Any incorporation by reference of documents above is limited such that no subject matter is incorporated that is contrary to the explicit disclosure herein.

Claims (15)

- a diamine component (A),
- 20 mol% to 95 mol% of a _C4 - _C12 aliphatic diamine;
- 5 mol% to 80 mol% of a bis(aminoalkyl)cyclohexane;
a diamine component (A), the mole percentages of which are relative to the total number of moles of all diamines in said diamine component; and - a dicarboxylic acid component (B),
- 30 mol% to 99 mol% terephthalic acid;
- 1 mol% to 70 mol% of cyclohexanedicarboxylic acid;
a dicarboxylic acid component (B), the mole % of which is relative to the total number of moles of all dicarboxylic acids in said dicarboxylic acid component;
Polyamides (PA) derived from the polycondensation of monomers in a reaction mixture containing The C ₄ -C ₁₂ aliphatic diamines are 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-diamino Polyamide (PA) according to claim 1, selected from the group consisting of undecane and 1,12-diaminododecane; preferably the C ₄ -C ₁₂ aliphatic diamine is 1,6-diaminohexane. Polyamide (PA) according to claim 1 or 2, wherein the bis(aminoalkyl)cyclohexane is 1,3-bis(aminomethyl)cyclohexane or 1,4-bis(aminomethyl)cyclohexane. Polyamide (PA) according to any one of the preceding claims, wherein the cyclohexanedicarboxylic acid is 1,4-cyclohexanedicarboxylic acid. 5. Any of claims 1-4, wherein the dicarboxylic acid component further comprises an additional dicarboxylic acid selected from the group consisting of _C4 - C12 aliphatic dicarboxylic acids, aromatic _dicarboxylic acids, and cycloaliphatic dicarboxylic acids. Polyamide (PA) according to claim 1. - _C4 - C12 _aliphatic dicarboxylic acids are succinic acid [HOOC-( _CH2 ) ₂ -COOH], glutaric acid [HOOC-( _CH2 ) ₃ -COOH], 2,2-dimethyl-glutaric acid [HOOC -C(CH ₃ ) ₂ -(CH ₂ ) ₂ -COOH], adipic acid [HOOC-(CH ₂ ) ₄ -COOH], 2,4,4-trimethyl-adipic acid [HOOC-CH(CH ₃ )- CH2 _- C( _CH3 ) ₂ - _CH2- COOH], pimelic acid [HOOC-( _CH2 ) ₅ -COOH], suberic acid [HOOC-( _CH2 ) _6- COOH ], azelaic acid [HOOC-( CH ₂ ) ₇ -COOH], sebacic acid [HOOC-(CH ₂ ) ₈ -COOH], 1,12-dodecanedioic acid [HOOC-(CH ₂ ) ₁₀ -COOH];
- said aromatic dicarboxylic acid is a phthalic acid such as isophthalic acid (IA), naphthalenedicarboxylic acid (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, selected from the group consisting of 2-bis(3-carboxyphenyl)ketone, bis(3-carboxyphenoxy)benzene;
- said alicyclic dicarboxylic acid is cyclopropane-1,2-dicarboxylic acid, 1-methylcyclopropane-1,2-dicarboxylic acid, cyclobutane-1,2-dicarboxylic acid, tetrahydrofuran-2,5-dicarboxylic acid, selected from the group consisting of 1,3-adamantanedicarboxylic acids;
Polyamide (PA) according to claim 5. _7. The polyamide (PA ). Polyamide (PA) according to any one of the preceding claims, having a glass transition temperature (“Tg”) of at least 145°C measured according to ASTM D3418. Polyamide (PA) according to any one of the preceding claims, having a melting temperature (“Tm”) of at least 295°C measured according to ASTM D3418. A method of making the polymer of any one of claims 1-9, wherein in the reaction mixture, at least the C ₄ -C ₁₂ aliphatic diamine, a bis(aminoalkyl)cyclohexane, and terephthalic acid are added. and cyclohexanedicarboxylic acid to form a polyamide (PA). - a polyamide (PA) according to any one of claims 1 to 9;
- selected from the group consisting of reinforcing agents, reinforcing agents, plasticizers, colorants, pigments, antistatic agents, dyes, lubricants, heat stabilizers, light stabilizers, flame retardants, nucleating agents and antioxidants at least one component;
A polymer composition (C) comprising: Polymer composition (C) according to claim 11, comprising 10% to 60% by weight of glass fibers or carbon fibers, based on the total weight of the polymer composition (C). Polymer composition (C) according to claim 11 or 12, comprising from 40% to 70% by weight of said polyamide (PA). Portable electronic device articles or components, electrical components, electronic components, automotive components, food contact components, plumbing components, and oil and gas related components, fiber reinforced thermoplastic composites or 3D printed articles , an article comprising the polymer composition (C) according to any one of claims 11-13. Portable electronics selected from the group consisting of mobile phones, personal digital assistants, laptop computers, tablet computers, wearable computing devices, cameras, portable audio players, portable radios, global positioning system receivers, and portable game consoles. 15. The article of claim 14, which is an article or component of a device.