Polymer compositions comprising a semi-aromatic polyamide and a poly(arylene sulfide) and articles of the same

Abstract

Disclosed herein are polymer compositions comprising a poly(arylene sulfide) polymer; a semi-aromatic polyamide in an amount from 5.0 wt% to 17.5 wt%, based on the total weight of the polymer composition; and a filler material in an amount from 55.0 wt% to 75.0 wt%, based on the total weight of the polymer composition. The filler material comprises Mg(OH)2, a phosphorous-based halogen-free flame retardant compound, and a reinforcing agent. The phosphorous-based halogen-free flame retardant compound can be present in an amount from 12.5 wt% to 25.0 wt%, based on the total weight of the polymer composition. The Mg(OH)2 can be present in an amount from 12.5 wt% to 25.0 wt%, based on the total weight of the polymer composition. The reinforcing agent can be present in an amount from 20.0 wt% to 37.5 wt%, based on the total weight of the polymer composition.

Description

POLYMER COMPOSITIONS COMPRISING A SEMI-AROMATIC POLYAMIDE AND A POLY(ARYLENE SULFIDE) AND ARTICLES OF THE SAMEREFERENCE TO RELATED APPLICATIONSThis application claims priority from US provisional application Nr. 63 / 568593, filed on March 22, 2024, and from European patent application Nr. 24172104.2, filed on April 24, 2024, the whole content of each of these applications being incorporated herein by reference for all purposes.FIELD OF THE DISCLOSURE

[0001] The present disclosure relates to polymer compositions including a polyamide and a poly(arylene sulfide) having a high comparative tracking index (CTI), good mechanical properties, and low density. The invention also relates to methods of making articles incorporating the polymer compositions.BACKGROUND

[0002] Semi-aromatic polyamides have traditionally been used for the manufacture of electrical components, especially in the area of surface mount technology devices. Good comparative tracking index (CTI) is an essential material property for the implementation of this technology. However, to obtain high CTI, poly(arylene sulfide) polymers are generally highly filled with metal hydroxide minerals and glass fillers that increase the density of the corresponding compound and hence its weight per unit volume. The high density is a disadvantage given the concerted effort to improve energy and performance efficiency of devices based on surface mount technology

[0003] Poly(arylene sulfide)-based compounds are good platforms for most surface mount technologies owing to their high retention of electrical properties upon exposure to high temperatures for a long period of time. In comparison to polyamides, poly(arylene sulfide)-based compounds have higher density. Therefore, any technology that decreases the density of their resultant high CTI compounds optimizes their energy efficiency in surface mount technologies.

[0004] The problem of providing poly(arylene sulfide) based compounds having high CTI, good mechanical properties, and relatively low density in comparison to conventional high CTI poly(arylene sulfide) based compounds is solved by the polymer composition of claims 1 to 13.BRIEF SUMMARY

[0005] Disclosed herein are polymer compositions comprising a poly(arylene sulfide) polymer, a semi-aromatic polyamide, and a filler material. The filler material comprises a phosphorous-based halogen-free flame retardant compound, Mg(OH)2 and a reinforcing agent. The semi-aromatic polyamide is present in the polymer composition in an amount from 5.0 wt% to 17.5 wt%, based on the total weight of the polymer composition. The phosphorous-based halogen-free flame retardant compound is present in an amount from 12.5 wt% to 25.0 wt%, based on the total weight of the polymer composition. Mg(OH)2 is present in an amount from 12.5 wt% to 25.0 wt%, based on the total weight of the polymer composition. The reinforcing agent is present in an amount from 20.0 wt% to 37.5 wt%, based on the total weight of the polymer composition.

[0006] The disclosed polymer compositions show relatively low density with corresponding high mechanical and CTI properties. The function of Mg(OH)2 in the formulation is primarily found to improve the CTI of the composition. Unexpectedly, the inclusion of the phosphorous-based halogen-free flame retardant compound in the filler material at the expense of the magnesium hydroxide leads to reduced density of the polymer composition without compromising the mechanical and CTI properties.

[0007] An object of the invention is accordingly the use of a phosphorous-based halogen- free flame retardant compound to reduce the density of a high CTI composition comprising a poly(arylene sulfide) polymer, a semi-aromatic polyamide, and a filler material.DETAILED DESCRIPTION

[0008] In the present application, any description, even if described in relation to a specific embodiment, is applicable to and interchangeable with other embodiments of thepresent disclosure, and each embodiment thus defined may be combined with another embodiment, unless otherwise indicated or clearly incompatible.

[0009] Where an element or component is said to be included in and / or selected from a list of recited elements or components, it should be understood that in related embodiments explicitly contemplated here, the element or component can also be any one of the individuals recited elements or components, or can also be selected from a group consisting of any two or more of the explicitly listed elements or components; any element or component recited in a list of elements or components may be omitted from such list.

[0010] Any recitation herein of numerical ranges by endpoints includes all numbers subsumed within the recited ranges as well as the endpoints of the range and equivalents.

[0011] The term “comprising” (or equivalents) includes “consisting essentially of,” and also “consisting of.”

[0012] As used herein, the term “consisting essentially of” or “essentially consisting” indicates that the referred to composition contains less than 5.0 wt%, typically less than 2.0 wt% or less than 1 .0 wt%, of any other ingredient.

[0013] The use of the singular “a” or “one” herein includes the plural unless specifically stated otherwise.

[0014] It should be understood that the elements, properties, and / or the characteristics of a (co)polymer, product or article, a process, or a use, described in the present specification, may be combined in all possible ways with the other elements, properties and / or characteristics of the (co)polymer, product or article, process or use, explicitly or implicitly, this being done without departing from the scope of the present description.

[0015] Should the disclosure of any patents, patent applications, and publications that are incorporated herein by reference conflict with the description of the present application to the extent that it may render a term unclear, the present description shall take precedence.

[0016] The Polymer CompositionThe presently disclosed polymer compositions comprise a poly(arylene sulfide) polymer; a semi-aromatic polyamide, in an amount from 5.0 wt% to 17.5 wt%, based on the total weight of the polymer composition; and a filler material. The filler material is generallypresent in an amount from 55.0 wt% to 75.0 wt%, based on the total weight of the polymer composition. The filler material comprises Mg(OH)2 in an amount from 12.5 wt% to 25.0 wt%, preferably from 15.0 wt% to 20.0 wt%; a phosphorous-based halogen-free flame retardant compound in an amount from 12.5 wt% to 25.0 wt%, preferably from 15.0 wt% to 20.0 wt%; and a reinforcing agent in an amount from 20.0 wt% to 37.5 wt%, preferably from 25.0 wt% to 35.0 wt%, all weights being based on the total weight of the polymer composition.

[0017] As noted above, it was surprisingly discovered that the inclusion of the phosphorous-based halogen-free flame-retardant compound provided for reduced density of the disclosed polymer compositions while still providing for mechanical and dielectric property retention. Specifically, the density of the disclosed polymer compositions can be reduced while the comparative tracking index (CTI) remains the same compared to polymer compositions with no halogen-free flame-retardant compound compound added. CTI and density can be measured as described in the Examples section.

[0018] The polymer composition can have a CTI of 400 V or more, 500 V or more, or 600 V or more. The polymer composition can have a CTI from 400 V to 800 V, from 450 V to 750 V, from 500 V to 700 V, or from 550 V to 650 V.

[0019] The density of the polymer composition can correspond to the specific gravity of the polymer composition for the sake of comparison. The polymer composition can have a specific gravity of 1 .70 or less, 1 .69 or less, 1 .68 or less. The polymer composition can have a specific gravity from 1 .61 to 1 .69, or from 1 .61 to 1 .68, or from 1 .62 to 1 .68, or from 1 .62 to 1 .69.

[0020] The Poly(Arylene Sulfide) Polymer

[0021] The presently disclosed polymer compositions comprise a poly(arylene sulfide) polymer, hereinafter referred to as “PAS polymer”. As used herein, a poly(arylene sulfide) polymer or PAS polymer, refers to any polymer including at least 50 mol% of a recurring unit (RPAS) having the following formula: -[-Ar-S-]-, where Ar is an arylene. The PAS polymer can have 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 recurring unit (RPAS).

[0022] The recurring unit (RPAS) is represented by a formula selected from the following group of formulae:where R, at each instance, is independently selected from the group consisting of a Ci- C12 alkyl group, a C7-C24 alkylaryl group, a C7-C24 aralkyl group, a C6-C24 arylene group, and a Ce-Cis aryloxy group; T is selected from the group consisting of a bond, -CO-, - SO2-, -O-, -C(CH3)2, phenyl and -CH2-; k, at each instance, is an independently selected integer from 0 to 4; and I, at each instance, is an independently selected integer from 0 to 3.

[0023] Alternatively, or in addition, k and I, at each instance, is zero. Preferably, -Ar- is represented by either Formula (1 ) or (2), more preferably Formula (1 ) (recurring unit (RPAS) corresponding to recurring units of polyphenylene sulfide), still more preferably, recurring unit (RPAS) is represented by the following formula:

[0024] The concentration of recurring unit (RPAS) in the PAS polymer 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%.

[0025] The PAS polymer can have a weight average molecular weight (“Mw”) 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. In some embodiments, the poly(arylene sulfide) (PASP) has an Mw of no more than 150,000 g / mol, no more than 100,000 g / mol, no more than 90,000 g / mol, no more than 85,000 g / mol, or no more than 80,000 g / mol. In some embodiments, the poly(arylene sulfide) (PASP) has an Mw of from 10,000 g / mol to 150,000 g / mol, from 20,000 g / mol to 100,000 g / mol, from 25,000 g / mol to 90,000 g / mol, from 30,000 g / mol to 85,000 g / mol, or from 35,000 g / mol to 80,000 g / mol. Mw can be measured with gel permeation chromatography (“GPC”) using a 4-chloronapthalene standard.

[0026] The PAS polymer can be semi-crystalline. The person of ordinary skill in the art will recognize that when a polymer is amorphous, it lacks a detectable Tm. Accordingly, when a PAS polymer has a Tm, the person of ordinary skill in the art will recognize that it refers to semi-crystalline polymer. The PAS polymer can also have a AHf of at least 10 J / g, at least 20 J / g, at least, or at least 25 J / g. Alternatively, or in addition, the PAS polymer can have a AHf of no more than 90 J / g, no more than 70 J / g or no more than 60 J / g. The PAS polymer can have a AHf of from 10 J / g to 90 J / g or from 20 J / g to 70 J / g.

[0027] The PAS polymer can have a melting temperature (“Tm”) of at least 200 °C, at least 220 °C, at least 240 °C, or at least 250 °C. Alternatively, or in addition, the PAS polymer can have a Tm of no more 350 °C, no more than 320 °C, no more than 300 °C, or no more than 285 °C. The PAS polymer can have a Tm of from 200 °C to 350 °C, from 220 °C to 320 °C, from 240 °C to 300 °C, or from 250 °C to 285 °C.

[0028] The PAS polymer can be present in the polymer composition in an amount from 10.0 wt% to 40.0 wt%, from 10.0 wt% to 35.0 wt%, from 10.0 wt% to 30.0 wt%, from 20.0 wt% to 40.0 wt%, even from 20.0 wt% to 30.0 wt%, based on the total weight of the polymer composition.

[0029] The Semi -Aromatic Polyamide Polymer

[0030] The presently disclosed polymer compositions comprise a semi-aromatic polyamide polymer, hereinafter referred to as “PA polymer”. The PA polymer comprisesrecurring units derived from: (1 ) a diamine component (A) comprising 20 mol% to 95 mol% of a C4 to C12 aliphatic diamine and 5 mol% to 80 mol% of a bis(aminoalkyl)cyclohexane, where mol% is relative to the total moles of each diamine monomer in the diamine component; and (2) a dicarboxylic acid component (B) comprising: 30 mol% to 100 mol% of terephthalic acid and 0 mol% to 70 mol%, preferably 1 mol% to 70 mol%, of a cyclohexane dicarboxylic acid, wherein mol% is relative to the total moles of each dicarboxylic acid monomer in the dicarboxylic acid component. The PA polymer may have a glass transition temperature (“Tg”) of at least 100 °C, a melting temperature (“Tm”) of at least 295 °C, and a heat of fusion (“AHf”) of at least 30 J / g.

[0031] The diamine component (A) includes all diamines in the reaction mixture, including 20 mol% to 95 mol% C4 to C12 aliphatic diamine and 5 mol% to 80 mol% of a bis(aminoalkyl)cyclohexane. When referring to the concentration of monomers in the diamine component (A), it will be understood that the concentration is relative to the total number of moles of all diamines in the diamine component (A), unless explicitly noted otherwise.

[0032] The C4 to C12 aliphatic diamine is represented by the following formula:H2N-R1-NH2, (4) where R1 is a C4 to C12 alkyl group, preferably a Ce to C10 alkyl group. In some embodiments, the C4 to C12 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-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. Preferably, the C4 to C12 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 C4 to C12 aliphatic diamine is a Cs to C10 aliphatic diamine or a Cs to C9 aliphatic diamine. Most preferably, the C4 to C12 aliphatic diamine is 1 ,6-diaminohexane.

[0033] The concentration of the Ce to C12 aliphatic diamine is from 25 mol% to 95 mol%, from 30 mol% to 95 mol%, from 35 mol% to 95 mol%, from 40 mol% to 95 mol%, from 45 mol% to 95 mol%, or from 50 mol% to 95 mol%. In some embodiments, concentration of the Ce to C12 diamine is from 20 mol% to 90 mol%, from 25 mol% to 90 mol%, from 30 mol% to 90 mol%, from 35 mol% to 90 mol%, from 40 mol% to 90 mol%, from 45 mol% to 90 mol%, or from 50 mol% to 90 mol%.

[0034] The bis(aminoalkyl)cyclohexane is represented by the following formula:where R2 and R3 are independently selected Ci to C10 alkyls; Ri, at each location, is selected from the group consisting of an alkyl, an aryl, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, and a quaternary ammonium; and i is an integer from 0 to 10. The -R3-NH2 groups are relatively positioned in the meta position (1 ,3-) or the para position (1 ,4-). 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 can be in a cis or trans conformation. Accordingly, the diamine component (A) can include only the cis-bis(aminoalkyl)cyclohexane, only trans- bis(aminoalkyl)cyclohexane or a mixture of cis- and trans- bis(aminoalkyl)cyclohexane.

[0035] The concentration of the bis(aminoalkyl)cyclohexane is from 5 mol% to 75 mol%, from 5 mol% to 70 mol%, from 5 mol% to 65 mol%, from 5 mol% to 60 mol%, from 5 mol% to 55 mol%, or from 5 mol% to 50 mol%. In some embodiments, the concentration of the bis(aminoalkyl)cyclohexane is from 10 mol% to 75 mol%, from 10 mol% to 70 mol%, from 10 mol% to 65 mol%, from 10 mol% to 60 mol%, from 10 mol% to 55 mol%, or from 10 mol% to 50 mol%, or from 20 mol% to 40 mol%.

[0036] The diamine component (A) includes one or more additional diamines. The additional diamines are distinct from the C4 to C12 aliphatic diamine and distinct from the bis(aminoalkyl)cyclohexane. In some embodiments, one, some, or all the additional diamines are represented by Formula (5), each distinct from each other and distinct from the C4 to C12 aliphatic diamine. In some embodiments, the 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-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. Included in this category are also cycloaliphatic diamine such as isophorone diamine, 1 ,3-diaminocyclohexane, 1 ,4-diaminocyclohexane, bis-p-aminocyclohexylmethane. In some embodiments, the diamine component is free of cycloaliphatic diamines others than the bis(aminoalkyl)cyclohexane. As used herein, free of a monomer (e.g. bis(aminoalkyl)cyclohexane) means that the concentration of the monomer in the corresponding component (e.g. the 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%, most preferably less than 0.01 mol%.

[0037] The dicarboxylic acid component (B) includes all dicarboxylic acids in the reaction mixture, including 30 mol% to 100 mol% of terephthalic acid and 0 mol% to 70 mol%, preferably from 1 mol% to 70 mol%, of a cyclohexanedicarboxylic acid. When referring to the concentration of monomers in the dicarboxylic acid component (B), it will be understood that the concentration is relative to number of moles of all dicarboxylic acids in the dicarboxylic acid component (A), unless explicitly noted otherwise.

[0038] The concentration of the terephthalic acid is from 35 mol% to 100 mol%, from 35 mol% to 100 mol%, from 40 mol% to 100 mol%, from 45 mol% to 100 mol%, or from 50 mol% to 100 mol%. In some embodiments, the concentration of the terephthalic acid is from 30 mol% to 99 mol%, from 35 mol% to 99 mol%, from 40 mol% to 99 mol%, from45 mol% to 99 mol% or from 50 mol% to 99 mol%. In some embodiments, the concentration of the terephthalic acid is from 30 mol% to 95 mol%, from 35 mol% to 97 mol%, from 40 mol% to 97 mol%, from 45 mol% to 97 mol% or from 50 mol% to 97 mol%.

[0039] The cyclohexanedicarboxylic acid is represented by the following formula:where Rj is selected from the group consisting of an alkyl, an aryl, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, and a quaternary ammonium; and j is an integer from 0 to 10. The explicit -COOH groups are relatively positioned in the meta position (1 ,3-) or the para position (1 ,4-), preferably the para position. Preferably, the cyclohexanedicarboxylic acid is 1 ,4-cyclohexanedicarboxylic acid (“CHDA”) (j is 0). Of course, the cyclohexanedicarboxylic acid can be in a cis or trans conformation. Accordingly, the dicarboxylic acid component (B) can include only the cis- cyclohexanedicarboxylic acid, only trans-cyclohexanedicarboxylic acid or a mixture of cisand trans-cyclohexanedicarboxylic acid.

[0040] The concentration of the cyclohexanedicarboxylic acid is from 1 mol% to 70 mol%, from 1 mol% to 65 mol%, from 1 mol%, to 60 mol%, from 1 mol% to 55 mol%, or from 1 mol% to 50 mol%.

[0041] The dicarboxylic acid component (B) includes one or more additional dicarboxylic acids. Each additional dicarboxylic acid is distinct from each other and distinct from the terephthalic acid and the cyclohexanedicarboxylic acid. In some embodiments, one, some, or all of the additional dicarboxylic acids are represented by Formula (6), each distinct from each other and distinct from the cyclohexanedicarboxylic acid.

[0042] The one or more additional dicarboxylic acids are independently selected from the group consisting of C4 to C12 aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and cycloaliphatic dicarboxylic acids. Examples of desirable C4 to C10 aliphatic dicarboxylicacids 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)^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)e-COOH], azelaic acid [HOOC-(CH2)7-COOH], sebacic acid[HOOC-(CH2)8-COOH], 1 ,12-dodecanedioic acid [HOOC-(CH2)IO-COOH],

[0043] Suitable examples of desirable aromatic dicarboxylic acids include, but are not limited to, phthalic acids, including 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, bis(3-carboxyphenoxy)benzene.

[0044] Examples of desirably 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, 1 ,3-adamantanedicarboxylic acid.

[0045] When the PA polymer includes one or more additional dicarboxylic acids, the total concentration of the one or more additional dicarboxylic acids is no more than 20 mol%.

[0046] The PA polymer formed from the polycondensation of the monomers in the diamine component and dicarboxylic acid component, as described above, includes recurring units RPAI and RPA2, represented by the following formulae, respectively:and, additionally, when the cyclohexanedicarboxylic acid is present in the dicarboxylic acid component (B), recurring units RPAS and RPA4 represented by the following formulae, respectively:where Ri to R3, Ri, Rj, i and j are as defined above. The person of ordinary skill in the art will recognize that recurring unit RPAI is formed from the polycondensation of the C4 to C12 aliphatic diamine with the terephthalic acid, recurring unit RPAS is formed from the polycondensation of the C4 to C12 aliphatic diamine with the cyclohexane dicarboxylic acid, recurring unit RPA2 is formed from the polycondensation of the bis(aminoalkyl)cyclohexane with the terephthalic acid, and recurring unit RPA4 is formed from the polycondensation of the bis(aminoalkyl)cyclohexane with the cyclohexanedicarboxylic acid. In some embodiments, Ri is -(CH2)-m, where m is from 5 to 10, preferably from 5 to 9, 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(aminoalkyl)cyclohexane is 1 ,3-bis(aminomethyl)cyclohexane and the cyclohexanedicarboxylic acid is 1 ,4-cyclohexane dicarboxylic acid.

[0047] The total concentration of recurring units RPAI and RPA2 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 someembodiments in which the optional cyclohexanedicarboxylic acid is present in the dicarboxylic acid component (B), the total concentration of recurring units RPAI to RPA4 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%. When referring to mol% of a recurring unit, it will be understood that the concentration is relative to the total number of recurring units in the indicated polymer, unless explicitly noted otherwise.

[0048] The PA polymers used in the inventive composition are semi-crystalline polyamides. As used herein, a semi-crystalline polyamide is a polyamide that has a heat of fusion (“AHf”) of at least 5 Joules per gram (“ J / g”). The PA polymer used in the inventive composition may conveniently have a AHf of at least 30 J / g, or at least 35 J / g. Alternatively, or in addition, the PA polymer has a AHf of no more than 60 J / g or no more than 55 J / g. The PA polymer can have a AHf of from 30 J / g to 60 J / g or from 35 J / g to 60 J / g, from 30 J / g to 55 J / g, or from 35 J / g to 55 J / g. AHf can be measured according to ASTM D3418 using a heating rate of 20 °C / m inute.

[0049] The PA polymer can have a Tg of at least 100 °C, at least 110 °C, at least 120 °C, at least 130°C, at least 140 °C, at least 145 °C, preferably at least 150 °C. Alternatively, or in addition, the semi-aromatic PA polymer can have a Tg of no more than 190 °C, no more than 180 °C, or no more than 170 °C The PA polymer can have a Tg of from 100 °C to 190 °C, from 120 °C to 180 °C, from 145 °C to 170 °C, from 150 °C to 190 °C, from 150 °C to 180 °C, or from 150 °C to 170 °C. Tg can be measured according to ASTM D3418.

[0050] The PA polymer can have a number average molecular weight ("Mn") ranging from 1 ,000 g / mol to 40,000 g / mol, for example 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 determined by gel permeation chromatography (GPC) using ASTM D5296 with polystyrene standards.

[0051] The PA polymer can be prepared by any conventional method adapted to the synthesis of polyamides and polyphthalamides. Preferentially, the PA polymer is prepared by reacting (by heating) the monomers in presence of less than 60 wt.% of water, preferentially less than 50 wt.%, up to a temperature of at least Tm+ 10 °C, Tmbeing themelting temperature of the semi-aromatic PA polymer, where wt.% is relative to the total weight of the reaction mixture.

[0052] The PA polymer described herein can for example be prepared by thermal polycondensation (also referred to as polycondensation or condensation) of aqueous solution of monomers and comonomers. In one embodiment, the polyamide (PA) is formed by reacting, in the reaction mixture, at least the C4 to C12 aliphatic diamine, the bis(aminoalkyl)cyclohexane, the terephthalic acid, and, if present in the dicarboxylic acid component (B), the cyclohexanedicarboxylic acid. 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, substantial equimolar denotes a value that is ± 15% of the indicated number of moles. For example, in the context of the diamine and dicarboxylic acid concentrations in the reaction mixture, total number of moles of diamines in the reaction mixture is ± 15% of the total number of moles of dicarboxylic acids in the reaction mixture. The PA polymer may contain a chain limiter, which is a monofunctional molecule capable of reacting with the amine or carboxylic acid moiety, and is used to control the molecular weight of the PA polymer. For example, the chain limiter can be acetic acid, propionic acid, benzoic acid and / or benzylamine. A catalyst can also be used. Examples of catalyst are phosphorous acid, ortho-phosphoric acid, meta-phosphoric acid, alkali-metal hypophosphite such as sodium hypophosphite and phenylphosphinic acid.

[0053] The PA polymer is present in the polymer composition in an amount from 5.0 wt% to 17.5 wt%, from 5.0 wt% to 17.0 wt%, from 5.0 wt% to 16.0 wt%, from 5.0 wt% to 15.0 wt%, from 6.0 wt% to 15.0 wt%, from 7.0 wt% to 15.0 wt%, from 8.0 wt% to 15.0 wt%, from 9.0 wt% to 15.0 wt%, from 10.0 wt% to 15.0 wt%, from 5.0 wt% to 14.0 wt%, from 5.0 wt% to 13.0 wt%, from 5.0 wt% to 12.0 wt%, from 5.0 wt% to 11 .0 wt%, or from 5.0 wt% to 10.0 wt%, based on the total weight of the polymer composition. The semiaromatic PA polymer being present in the polymer composition in an amount of 5.0 wt% or greater was found to advantageously increase the CTI of the polymer composition.

[0054] The Filler Material

[0055] The presently disclosed polymer compositions comprise a filler material comprising a halogen-free flame retardant compound, magnesium hydroxide, and areinforcing agent. The filler material is present in the polymer composition in an amount from 55.0 wt% to 75.0 wt%, from 56.0 wt% to 74.0 wt%, from 57.0 wt% to 73.0 wt%, from 58.0 wt% to 72.0 wt%, from 59.0 wt% to 71 .0 wt%, from 60.0 wt% to 70.0 wt%, from 61 .0 wt% to 69.0 wt%, from 62.0 wt% to 68.0 wt%, from 63.0 wt% to 67.0 wt%, or from 64.0 wt% to 66.0 wt%, based on the total weight of the polymer composition.

[0056] The expression “phosphorous-based halogen-free flame retardant compound” is used herein interchangeably with the expression “HFFR compound”.

[0057] Suitable phosphorous-based flame retardants can be a phosphine, a phosphinite, a phosphonite, a phosphite, a phosphine oxide, a phosphinate, a phosphonate, a phosphate, a phenoxyphosphazene, a melamine polyphosphate, or a combination thereof.The HFFR compound can be a material comprising phosphorous in an amount 24.5 wt% to 25.5 wt%, based on the total weight of the HFFR compound as measured according to wavelength dispersive X-ray fluorescence spectrometry..

[0058] Advantageously, the HFFR compound is an organophosphorous compound selected from the group consisting of phosphinic salts (phosphinates), diphosphinic salts (diphosphinates) and condensation products thereof. Preferably, the organophosphorous compound is selected from the group consisting of phosphinic salt (phosphinate) of the formula (11 ), a diphosphinic salt (diphosphinate) of the formula (12) and condensation products thereof:wherein, Ri , F are identical or different and each of Ri and R2 is a hydrogen or a linear or branched C1-C6 alkyl group or an aryl group; R3 is a linear or branched C1-C10 alkylene group, a C6-C10 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.

[0059] Preferably, Ri and R2are independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, and phenyl; Rs is selected from methylene, ethylene, n-propylene, isopropylene, n-butylene, tert-butylene, n pentylene, n-octylene, n-dodecylene, phenylene, naphthylene, methylphenylene, ethylphenylene, tertbutylphenylene, methylnaphthylene, ethylnaphthylene, tert-butylnaphthylene, phenylmethylene, phenylethylene, phenylpropylene, and phenylbutylene; and M is selected from aluminum and zinc ions.

[0060] Phosphinates are preferred as organophosphorous compound. Suitable phosphinates have been described in U.S. Pat. No. 6,365,071 , incorporated herein by reference. Particularly preferred phosphinates are aluminum phosphinates, calcium phosphinates, and zinc phosphinates. Excellent results were obtained with aluminum phosphinates. Among aluminum phosphinates, aluminium ethylmethylphosphinate and aluminium diethylphosphinate and combinations thereof are preferred.

[0061] The halogen-free flame retardant compound is present in an amount from 12.5 wt% to 25.0 wt%, preferably from 15.0 wt% to 20.0 wt%, based on the total weight of the polymer composition.

[0062] In general, reinforcing agents are fibrous reinforcing agents or particulate reinforcing agents. A fibrous reinforcing agent refers to a material having length, width and thickness, wherein the average length is significantly larger than both the width and thickness. Generally, such a material has 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 fibers, glass beads, or carbon fibers) has an average length of from 3 mm to 50 mm. In some such embodiments, the fibrous reinforcing agent has an average length of from 3 mm to 10 mm, from 3 mm to 8 mm, from 3 mm to 6 mm, or from 3 mm to 5 mm. Inalternative embodiments, fibrous reinforcing agent has an average length of from 10 mm to 50 mm, from 10 mm to 45 mm, from 10 mm to 35 mm, from 10 mm to 30 mm, from 10 mm to 25 mm or from 15 mm to 25 mm. The average length of the fibrous reinforcing agent can be taken as the average length of the fibrous reinforcing agent prior to incorporation into the polymer composition or can be taken as the average length of the fibrous reinforcing agent in the polymer composition.

[0063] The morphology of the glass fiber is not particularly limited. As noted above, the glass fiber can have a circular cross-section (“round glass fiber”) or a non-circular crosssection (“flat glass fiber”). Examples of suitable flat glass fibers include, but are not limited to, glass fibers having oval, elliptical and rectangular cross sections. In some embodiments in which the polymer composition includes a flat glass fiber, the flat glass fiber has a cross-sectional longest diameter of at least 15 pm, preferably at least 20 pm, more preferably at least 22 pm, still more preferably at least 25 pm. Additionally or alternatively, in some embodiments, the flat glass fiber has a cross-sectional longest diameter of at most 40 pm, preferably at most 35 pm, more preferably at most 32 pm, still more preferably at most 30 pm. In some embodiments, the flat glass fiber has a cross- sectional diameter was in the range of 15 to 35 pm, preferably of 20 to 30 pm and more preferably of 25 to 29 pm. In some embodiments, the flat glass fiber has a cross-sectional shortest diameter of at least 4 pm, preferably at least 5 pm, more preferably at least 6 pm, still more preferably at least 7 pm. Additionally or alternatively, in some embodiments, the flat glass fiber has a cross-sectional shortest diameter of at most 25 pm, preferably at most 20 pm, more preferably at most 17 pm, still more preferably at most 15 pm. In some embodiments, the flat glass fiber has a cross-sectional shortest diameter was in the range of 5 to 20 preferably of 5 to 15 pm and more preferably of 7 to 11 pm.

[0064] The flat glass fiber has an aspect ratio of at least 2, preferably at least 2.2, more preferably at least 2.4, still more preferably at least 3. The aspect ratio is defined as a ratio of the longest diameter in the cross-section of the glass fiber to the shortest diameter in the same cross-section. Additionally or alternatively, in some embodiments, the flat glass fiber has an aspect ratio of at most 8, preferably at most 6, more preferably of at most 4. In some embodiments, the flat glass fiber has an aspect ratio of from 2 to 6, and preferably, from 2.2 to 4. In some embodiments, in which the glass fiber is a round glassfiber, the glass fiber has an aspect ratio of less than 2, preferably less than 1.5, more preferably less than 1.2, even more preferably less than 1.1 , most preferably, less than 1.05. Of course, the person of ordinary skill in the art will understand that regardless of the morphology of the glass fiber (e.g. round or flat), the aspect ratio cannot, by definition, be less than 1.

[0065] The reinforcing agent may also be in the form of glass beads, including hollow glass beads. Hollow glass beads (also known as hollow glass microspheres or glass bubbles) are well known and notably are mentioned in Plastics Additives Handbook, Hanser, 4th edition, pages 537-538. The hollow glass beads that can be used in the inventive composition typically have a dimensional aspect ratio (short axis / long axis) of at least 0.9, preferably at least 0.95.

[0066] Examples of commercial hollow glass beads are available from 3MTM. A suitable example is iM16K (true density 0.46 g / cm3, crush strength 110 MPa).

[0067]

[0068] Magnesium hydroxide is relatively high-purity magnesium hydroxide including not less than 80% by weight of an inorganic substance expressed by the chemical formula Mg(OH)2. In terms of the tracking resistance CTI, the mechanical strength and the melt viscosity, suitably used is high-purity magnesium hydroxide preferably including not less than 70 wt% of the inorganic substance expressed by Mg(OH)2, not greater than 5 wt% of CaO and not greater than 1 wt% of chlorine content; more preferably including not less than 95 wt% of the inorganic substance expressed by Mg(OH)2, not greater than 1 wt% of CaO and not greater than 0.5 wt% of chlorine ; furthermore preferably including not less than 98 wt% of the inorganic substance expressed by Mg(OH)2, not greater than 0.1 wt% of CaO and not greater than 0.1 wt% of chlorine.

[0069] The magnesium hydroxide used according to the invention may be any form, such as granular form, flake form or fibrous form. In terms of, for example, the dispersibility, the granular form and the flake form are most preferable. The specific surface area is preferably not greater than 15 m2 / g and is more preferably not greater than 10 m2 / g. The specific surface area of greater than 15 m2 / g may affect the dispersibility of magnesium hydroxide and undesirably has adverse effects on the improvement of the tracking resistance and the mechanical strength. The “specific surface area” herein is a valuemeasured by the BET method using nitrogen as adsorbed gas. In the case of using magnesium hydroxide in the granular form or the flake form, suitable magnesium hydroxide has the average primary particle diameter in the range of 0.3 to 5 pm or preferably in the range of 0.3 to 3 pm in terms of the good balance among the improvement of the tracking resistance, the mechanical strength and the melt viscosity. The “average primary particle diameter” is a value measured by the laser diffraction scattering method. In the case of using magnesium hydroxide in the fibrous form, suitable magnesium hydroxide has the average fiber diameter in the range of 0.1 to 2 pm and the aspect ratio in the range of 20 to 60 or preferably the average fiber diameter in the range of 0.3 to 2 pm and the aspect ratio in the range of 30 to 50. The “aspect ratio” is a ratio of the long side dimension of a substance to the short side dimension.

[0070] The magnesium hydroxide can be present in an amount from 12.5 wt% to 25.0 wt%, preferably 15.0 wt% to 20.0 wt%, based on the total weight of the polymer composition. The magnesium hydroxide being present in an amount of approximately 46 wt% based on the combined weight of the filler material was found to provide an unexpectedly advantageous peak in mechanical property retention.

[0071] Articles and Applications

[0072] The present disclosure also relates to articles comprising the disclosed polymer compositions. At least in part due to the improved mechanical and dielectric property retention after heat aging, the presently disclosed polymer compositions are desirably incorporated into any article that is exposed elevated temperatures during their intended use.

[0073] The article is selected from the group consisting of automotive components, marine components, and aerospace components. In some embodiments, the article is selected from the group consisting of fluid in let / outlet ports, fluid in let / outlet valves, fluid pump housings, fluid pump impellers, fluid hose connectors, fluid hoses, fluid reservoirs and fluid valves. The polymer compositions are even further advantageously incorporated into such articles when such articles are used within engine bays (e.g. exposed to elevated temperatures).

[0074] The article can be molded from the polymer composition by any process adapted to thermoplastics, e.g., extrusion, injection molding, blow molding, rotomolding orcompression molding. The polymer composition may also be used in overmolding preformed shapes to build hybrid structures. Suitable examples of molded articles comprising the polymer composition include, but are not limited to, busbars, semiconductors, surface mount devices, printed circuit boards, electrical component circuit boards, and combinations thereof.

[0075] The present disclosure will be now described with reference to the following examples, whose purpose is merely illustrative and not limitative of the present disclosure.

[0076] Raw MaterialsPAS 1 : Ryton® QA200N having an MFR according to ASTM D1238 at 316°C / 5.0 kg of 80 to 120 g / 10 min obtained from Solvay Specialty Polymers USA;PAS 2: Ryton® QA321 N having an MFR according to ASTM D1238 at 316° C / 5.0 kg of 1300 to 1500 g / 10mins) obtained from Solvay Specialty Polymers USA;PPA: Amodel® PPA 9004, a 6T / 1 ,3-BACT / 6CHDA / 1 ,3-BACCHDA copolymer with an intrinsic viscosity of 0.8 to 1 .2 dl / g measured according to ASTM D2857 obtained from Solvay Specialty Polymers USA;HDPE: HDPE6007G was procured from Nexeo Plastics USA;HFFR: Exolit® 1400 a non-halogenated flame retardant based on organic phosphinates obtained from Clariant;Magnesium oxide: synthetic magnesium oxide Kisuma 5A;Glass fibers: DS 8800-P is a glass chopped strand obtained from 3B fiberglass.

[0077] Methods of Manufacture

[0078] The formulations shown in Table I were compounded using a conventional twin screw extruder on the ZSK 26. The compounding was carried out at 330 to 360 °C, screw speed of 200 rpm and a torque ranging from 35 to 80% of the extruder capacity. Samples were molded at higher temperature than is typical of PPS (360 to 370 °C at a mold temperature of 150 to 180 °C). Samples were molded into ISO multipurpose / tensile bars which were tested at room temperature according to ISO 527. The comparative trackingindex CTI was measured in accordance with IEC 60112. Density and specific gravity were measured according to ASTM D792.

[0079] Examples

[0080] The following Examples were prepared according to the above. Examples 1 and 2 were prepared with both HFFR compound and Mg(OH)2. Comparative Examples 1-4 were prepared without HFFR compound and with only Mg(OH)2. Comparative Examples 5 and 6 were prepared with HFFR compound but without Mg(OH)2. The formulations are presented in Table I, and the corresponding mechanical and dielectric properties are shown in Table II.Table I. Polymer compositions with varying concentrations of HFFR compound and Mg(OH)2 in the filler material.Table II. Mechanical and dielectric properties of polymer compositions with varying concentrations of HFFR compound and Mg(OH)2 in the filler material.

[0081] As can be seen in Table II, combining both HFFR compound and Mg(OH)2 in Examples 1 and 2 yielded samples maintained the high CTI values as Comparative Examples 3 and 4, which contain no HFFR compound. However, at the same time, the density and specific gravity of Examples 1 and 2 are reduced when compared to Comparative Examples 3 and 4, showing that Examples 1 and 2 attain reduced density compositions without a reduction in CTI. It should be appreciated by those of ordinary skill in the art that this result is unexpected.

[0082] Introducing more of the HFFR compound at the expense of the Mg(OH)2 unexpectedly increased the tensile elongation at break, as seen in Example 1 compared to Comparative Example 3 and in Example 2 compared to Comparative Example 4.

Claims

CLAIMSWhat is claimed is:1 . A polymer composition comprising: a poly(arylene sulfide) polymer; a semi-aromatic polyamide in an amount from 5.0 wt% to 17.5 wt%, preferably from 5.0 wt% to 15.0 wt%, based on the total weight of the polymer composition; and a filler material comprising:- Mg(OH)2 in an amount from 12.5 wt% to 25.0 wt%, preferably from 15.0 wt% to 20.0 wt%, based on the total weight of the polymer composition;- a phosphorous-based halogen-free flame retardant compound in an amount from12.5 wt% to 25.0 wt%, preferably from 15.0 wt% to 20.0 wt%, based on the total weight of the polymer composition; and- a reinforcing agent in an amount from 20.0 wt% to 37.5 wt%, preferably from 25.0 wt% to 35.0 wt%, based on the total weight of the polymer composition.

2. The polymer composition of Claim 1 , wherein the poly(arylene sulfide) polymer is present in the polymer composition in an amount from 10.0 wt% to 30.0 wt%, preferably from 20.0 wt% to 30.0 wt%, based on the total weight of the polymer composition.

3. The polymer composition of Claim 1 or 2, wherein the poly(arylene sulfide) polymer is polyphenylene sulfide.

4. The polymer composition of any of Claims 1 to 3, wherein the reinforcing agent is selected from the group consisting of glass fibers or glass beads, preferably glass fibers.

5. The polymer composition of any of Claims 1 to 4, wherein the semi-aromatic polyamide comprises recurring units derived from:- a diamine component (A) comprising 20 mol% to 95 mol% of a C4 to C12 aliphatic diamine and 5 mol% to 80 mol% of bis(aminoalkyl)cyclohexane, themol% being relative to the total moles of each diamine in the diamine component; and- a dicarboxylic acid component (B) comprising 30 mol% to 100 mol% of terephthalic acid and 0 mol% to 70 mol% of a cyclohexanedicarboxylic acid, the mol% being relative to the total moles of each dicarboxylic acid in the dicarboxylic acid component.

6. The polymer composition of Claim 5, wherein the C4 to C12 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; preferably the C4 to C12 aliphatic diamine is 1 ,6-diaminohexane.

7. The polymer composition of any of Claims 5 or 6, wherein the bis(aminoalkyl)cyclohexane is 1 ,3-bis(aminomethyl)cyclohexane or 1 ,4- bis(am inomethyl)cyclohexane.

8. The polymer composition of any of Claims 5 to 7, wherein the dicarboxylic acid component (B) comprises 1 mol% to 70 mol% of cyclohexanedicarboxylic acid, preferably 1 ,4-cyclohexanedicarboxylic acid, relative to the total moles of each dicarboxylic acid in the dicarboxylic acid component.

9. The polymer composition of any of Claims 1 to 8, wherein the phosphorous-based halogen-free flame retardant compound is selected from the group consisting ofa phosphine, a phosphinite, a phosphonite, a phosphite, a phosphine oxide, a phosphinate, a phosphonate, a phosphate, a phenoxyphosphazene, a melamine polyphosphate, or a combination thereof.

10. The polymer composition of any of Claims 1 to 9, wherein the phosphorous-based halogen-free flame retardant compound comprises phosphorous in an amount 24.5 wt% to 25.5 wt% , based on the total weight of the HFFR compound as measured according to wavelength dispersive X-ray fluorescence spectrometry.11 . The polymer composition of any of Claims 1 to 10, wherein the polymer composition has a comparative tracking index (CTI) of 400 V of more, or 500 V or more, or 600 V or more.

12. The polymer composition of any of Claims 1 to 11 , wherein the polymer composition has a specific gravity of 1 .70 or less, or 1 .69 or less, or 1 .68 or less.

13. A molded article comprising the polymer composition of any of Claims 1 to 12.

14. The molded article of Claim 13, wherein the molded article selected from the group consisting of: busbars, semiconductors, surface mount devices, printed circuit boards, electrical component circuit boards, and combinations thereof.

15. Use of a phosphorous-based halogen-free flame retardant compound to reduce the density of a high CTI composition comprising a poly(arylene sulfide) polymer, a semiaromatic polyamide, and a filler material.

Images