Polymer compositions comprising semi-aromatic polyamides and poly(arylene sulfide) and articles thereof

Abstract

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

Description

[0001] Citation of relevant applications

[0002] This application claims priority to U.S. Provisional Application No. 63 / 568593, filed March 22, 2024, and European Patent Application No. 24172104.2, filed April 24, 2024, the entire contents of each of these applications are incorporated herein by reference for all purposes. Technical Field

[0003] This disclosure relates to polymer compositions comprising polyamides and poly(aryl sulfides) having high comparative tracking index (CTI), good mechanical properties, and low density. The invention also relates to methods for manufacturing articles incorporating these polymer compositions. Background Technology

[0004] Semi-aromatic polyamides have traditionally been used to manufacture electrical components, particularly in surface mount technology (SMT) devices. A good comparative tracking index (CTI) is an essential material property for implementing this technology. However, to achieve a high CTI, poly(aryl sulfide) polymers are typically heavily filled with metal hydroxide minerals and glass fillers, which increases the density of the respective compounds and thus their weight per unit volume. This high density is a disadvantage considering the synergistic efforts made to improve the energy and performance efficiency of SMT-based devices.

[0005] Poly(aryl sulfide)-based compounds are a good platform for most surface mount technologies due to their high electrical property retention when exposed to high temperatures for extended periods. Compared to polyamides, poly(aryl sulfide)-based compounds have a higher density. Therefore, any technique that reduces the density of the resulting high CTI compound optimizes its energy efficiency in surface mount technologies.

[0006] The polymer composition as described in claims 1 to 13 solves the problem of providing a poly(aryl sulfide) based compound with high CTI, good mechanical properties and relatively low density compared to conventional high CTI poly(aryl sulfide) based compounds. Summary of the Invention

[0007] This document discloses a polymer composition comprising a poly(aryl sulfide) polymer, a semi-aromatic polyamide, and a filler material. The filler material comprises a phosphorus-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 of 5.0 wt% to 17.5 wt% based on the total weight of the polymer composition. The phosphorus-based halogen-free flame retardant compound is present in an amount of 12.5 wt% to 25.0 wt% based on the total weight of the polymer composition. Mg(OH)₂ is present in an amount of 12.5 wt% to 25.0 wt% based on the total weight of the polymer composition. The reinforcing agent is present in an amount of 20.0 wt% to 37.5 wt% based on the total weight of the polymer composition.

[0008] The disclosed polymer compositions exhibit relatively low density and correspondingly high mechanical and CTI properties. The role of Mg(OH)₂ in the formulation was found to primarily improve the CTI of the composition. Unexpectedly, incorporating a phosphorus-based halogen-free flame retardant compound into the filler material at the expense of magnesium hydroxide resulted in a decrease in the density of the polymer composition without compromising mechanical and CTI properties.

[0009] Therefore, the object of the present invention is the use of phosphorus-based halogen-free flame retardant compounds for reducing the density of high CTI compositions comprising poly(arylene sulfide) polymers, semi-aromatic polyamides, and filler materials. Detailed Implementation

[0010] In this application, any description of a particular embodiment is applicable to and interchangeable with other embodiments of this disclosure, and each embodiment defined theretherein may be combined with another embodiment unless otherwise specified or obviously incompatible.

[0011] When an element or component is referred to as being included in and / or selected from the list of enumerated elements or components, it should be understood that in the relevant embodiments explicitly considered herein, the element or component may also be any one of these enumerated individual elements or components, or may also be a group consisting of any two or more of the explicitly enumerated elements or components; any element or component listed in the list of elements or components may be omitted from such a list.

[0012] Any enumeration of numerical ranges by endpoints in this document includes all numbers contained within the enumerated range, as well as the endpoints and equivalents of that range.

[0013] The term “comprising” (or equivalent) includes “consistent with” as well as “comprises from”.

[0014] As used herein, the term “consisting essentially of / essentially consisting” indicates that the composition mentioned contains less than 5.0 wt%, typically less than 2.0 wt%, or less than 1.0 wt% of any other ingredient.

[0015] The singular “a” or “one” as used herein includes the plural, unless otherwise expressly indicated.

[0016] It should be understood that the elements, properties and / or characteristics of the (co)polymer, product or article, method or use described in this specification may be explicitly or implicitly combined with other elements, properties and / or characteristics of the (co)polymer, product or article, method or use in all possible ways without departing from the scope of this specification.

[0017] If any disclosure of any patent, patent application, or publication incorporated herein by reference conflicts with the description of this application to the extent that it may lead to ambiguity in terminology, then this description shall take precedence.

[0018] polymer composition

[0019] The polymer composition disclosed in this invention comprises: a poly(aryl sulfide) polymer; a semi-aromatic polyamide in an amount of 5.0 wt% to 17.5 wt% based on the total weight of the polymer composition; and a filler material. The filler material is typically present in an amount of 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 of 12.5 wt% to 25.0 wt%, preferably 15.0 wt% to 20.0 wt%; a phosphorus-based halogen-free flame retardant compound in an amount of 12.5 wt% to 25.0 wt%, preferably 15.0 wt% to 20.0 wt%; and a reinforcing agent in an amount of 20.0 wt% to 37.5 wt%, preferably 25.0 wt% to 35.0 wt%, all weights being based on the total weight of the polymer composition.

[0020] As described above, it was unexpectedly found that the inclusion of phosphorus-based halogen-free flame retardant compounds provided a reduced density for the disclosed polymer compositions while still maintaining high mechanical and dielectric property retention. Specifically, the density of the disclosed polymer compositions can be reduced compared to polymer compositions without the addition of halogen-free flame retardant compounds, while maintaining the same tracking index (CTI). CTI and density can be measured as described in the Examples section.

[0021] The polymer composition may have a CTI of 400 V or greater, 500 V or greater, or 600 V or greater. The polymer composition may have a CTI of 400 V to 800 V, 450 V to 750 V, 500 V to 700 V, or 550 V to 650 V.

[0022] For comparison purposes, the density of a polymer composition can correspond to its specific gravity. A polymer composition can have a specific gravity of 1.70 or less, 1.69 or less, or 1.68 or less. A polymer composition can have a specific gravity of 1.61 to 1.69, or 1.61 to 1.68, or 1.62 to 1.68, or 1.62 to 1.69.

[0023] Poly(arylene sulfide) polymer

[0024] The polymer compositions disclosed in this invention comprise poly(aryl sulfide) polymers, hereinafter referred to as "PAS polymers". As used herein, a poly(aryl sulfide) polymer or a PAS polymer refers to a polymer containing at least 50 mol% of repeating units (R) having the following formula. PAS Any polymer of the following composition: -[-Ar-S-]-, where Ar is an arylene group. PAS polymers may have repeating units (R) of 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%. PAS ).

[0025] Repeating unit (R) PAS The expression is represented by a group of the following formulas:

[0026] (1)

[0027] (2) and

[0028] (3)

[0029] R is independently chosen from the following groups in each case: C1-C 12 Alkyl, C7-C 24 Alkyl aryl, C7-C 24 Araneyl, C6-C 24 aryl and C6-C 18 Aryloxy group; T is selected from the group consisting of: bond, -CO-, -SO2-, -O-, -C(CH3)2, phenyl and -CH2-; k is an independently chosen integer from 0 to 4 in each case; and l is an independently chosen integer from 0 to 3 in each case.

[0030] Alternatively or additionally, k and l are zero in each case. Preferably, -Ar- is derived from the formula (1) or (2), more preferably, formula (1) represents (repeating unit (R) PAS (corresponding to the repeating unit of polyphenylene sulfide), and more preferably, the repeating unit (R) PAS It can be expressed by the following formula:

[0031] (11)

[0032] Repeating units (R) in PAS polymers PAS The concentration of ) 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%.

[0033] PAS polymers may have a weight-average molecular weight (“M”) of at least 10,000 g / mol, at least 20,000 g / mol, at least 25,000 g / mol, at least 30,000 g / mol, or at least 35,000 g / mol. w In some embodiments, the poly(arylene sulfide) (PASP) has an M value not exceeding 150,000 g / mol, not exceeding 100,000 g / mol, not exceeding 90,000 g / mol, not exceeding 85,000 g / mol, or not exceeding 80,000 g / mol. w In some embodiments, the poly(arylene sulfide) (PASP) has an M value of 10,000 g / mol to 150,000 g / mol, 20,000 g / mol to 100,000 g / mol, 25,000 g / mol to 90,000 g / mol, 30,000 g / mol to 85,000 g / mol, or 35,000 g / mol to 80,000 g / mol. w M w The 4-chloronaphthalene standard can be measured using gel permeation chromatography (“GPC”).

[0034] PAS polymers can be semi-crystalline. Those skilled in the art will recognize that when the polymer is amorphous, its undetectable T... m Therefore, when the PAS polymer has T mAt that time, those skilled in the art will recognize that it refers to a semi-crystalline polymer. The PAS polymer may also have a ΔH of at least 10 J / g, at least 20 J / g, at least, or at least 25 J / g. f Alternatively or additionally, the PAS polymer may have a ΔH value not exceeding 90 J / g, 70 J / g, or 60 J / g. f PAS polymers can have a ΔH of 10 J / g to 90 J / g or 20 J / g to 70 J / g. f .

[0035] PAS polymers may have a melt temperature of at least 200°C, at least 220°C, at least 240°C, or at least 250°C (“T”). m Alternatively or additionally, the PAS polymer may have a T value not exceeding 350°C, 320°C, 300°C, or 285°C. m PAS polymers can have a Tc of 200°C to 350°C, 220°C to 320°C, 240°C to 300°C, or 250°C to 285°C. m .

[0036] PAS polymers may be present in the polymer composition in amounts of 10.0 wt% to 40.0 wt%, 10.0 wt% to 35.0 wt%, 10.0 wt% to 30.0 wt%, 20.0 wt% to 40.0 wt%, or even 20.0 wt% to 30.0 wt% based on the total weight of the polymer composition.

[0037] semi-aromatic polyamide polymers

[0038] The polymer composition disclosed in this invention comprises a semi-aromatic polyamide polymer, hereinafter referred to as "PA polymer". The PA polymer comprises repeating units derived from: (1) a diamine component (A) comprising 20 mol% to 95 mol% of C4 to C64 polymers. 12The PA polymer comprises (1) an aliphatic diamine and 5 mol% to 80 mol% bis(aminoalkyl)cyclohexane, wherein 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% terephthalic acid and 0 mol% to 70 mol%, preferably 1 mol% to 70 mol% cyclohexanedicarboxylic acid, wherein mol% is relative to the total moles of each dicarboxylic acid monomer in the dicarboxylic acid component. The PA polymer has a glass transition temperature (“Tg”) of at least 100°C, a melting temperature (“Tm”) of at least 295°C, and a heat of fusion (“ΔH”) of at least 30 J / g. f (”).

[0039] Diamine component (A) comprises all the diamines in the reaction mixture, which contain 20 mol% to 95 mol% of C4 to C64. 12 Aliphatic diamines and 5 mol% to 80 mol% bis(aminoalkyl)cyclohexane. When referring to the concentration of monomers in diamine component (A), it should be understood that, unless otherwise explicitly stated, the concentration is relative to the total number of moles of all diamines in diamine component (A).

[0040] C4 to C 12 Aliphatic diamines are represented by the following formula:

[0041] H2N-R1-NH2, (4)

[0042] Where R1 is C4 to C 12 Alkyl, preferably C6 to C 10 Alkyl group. In some embodiments, C4 to C5 12 The 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, C4 to C5 are preferred. 12The 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, C4 to C5... 12 Aliphatic diamines are C5 to C6. 10 Aliphatic diamines or C5 to C9 aliphatic diamines. Most preferably, C4 to C9. 12 The aliphatic diamine is 1,6-diaminohexane.

[0043] C6 to C 12 The concentration of the aliphatic diamine is 25 mol% to 95 mol%, 30 mol% to 95 mol%, 35 mol% to 95 mol%, 40 mol% to 95 mol%, 45 mol% to 95 mol%, or 50 mol% to 95 mol%. In some embodiments, C6 to C 12 The concentration of the diamine is 20 mol% to 90 mol%, 25 mol% to 90 mol%, 30 mol% to 90 mol%, 35 mol% to 90 mol%, 40 mol% to 90 mol%, 45 mol% to 90 mol%, or 50 mol% to 90 mol%.

[0044] bis(aminoalkyl)cyclohexane is represented by the following formula:

[0045] (5),

[0046] R2 and R3 are independently chosen from C1 to C2. 10 Alkyl; R i At each position, the group consisting of alkyl, aryl, alkali metal or alkaline earth metal sulfonates, alkyl sulfonates, and quaternary ammonium groups is selected; and i is an integer from 0 to 10. The -R3-NH2 group is located relatively at the meta (1,3-) or para (1,4-) position. Preferably, i is 0, and both R2 and R3 are -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 cis or trans conformation. Therefore, the diamine component (A) can contain only cis-bis(aminoalkyl)cyclohexane, only trans-bis(aminoalkyl)cyclohexane, or a mixture of cis-bis(aminoalkyl)cyclohexane and trans-bis(aminoalkyl)cyclohexane.

[0047] 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%, or 20 mol% to 40 mol%.

[0048] The diamine component (A) contains one or more additional diamines. These additional diamines are different from C4 to C5. 12 Aliphatic diamines and different from bis(aminoalkyl)cyclohexane. In some embodiments, one, some, or all of these additional diamines are represented by formula (5), each being different from each other and different from C4 to C6. 12 Aliphatic diamines. In some embodiments, each additional diamine is selected from the group consisting of: 1,2-diaminoethane, 1,2-diaminopropane, propylene-1,3-diamine, 1,3-diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane, 2-methyl-1,5-diaminopentane, 1,6-diaminohexane, 3-methylhexamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,2,4-trimethyl-hexamethylenediamine, 2,4,4-trimethyl-hexamethylenediamine. Methyldiamine, 1,7-diaminoheptane, 1,8-diaminooctane, 2,2,7,7-tetramethyloctamethylenediamine, 1,9-diaminononane, 2-methyl-1,8-diaminooctane, 5-methyl-1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 2,5-bis(aminomethyl)tetrahydrofuran, and N,N-bis(3-aminopropyl)methylamine. This category also includes alicyclic diamines such as isophorone diamine, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, and bis-p-aminocyclohexylmethane. In some embodiments, the diamine component does not contain alicyclic diamines other than bis(aminoalkyl)cyclohexane. As used herein, "free of monomers (e.g., bis(aminoalkyl)cyclohexane)" means that the concentration of monomers 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%, even more preferably less than 0.05 mol%, and most preferably less than 0.01 mol%.

[0049] Dicarboxylic acid component (B) comprises all dicarboxylic acids in the reaction mixture, including 30 mol% to 100 mol% terephthalic acid and 0 mol% to 70 mol%, preferably 1 mol% to 70 mol% cyclohexanedicarboxylic acid. When referring to the concentration of monomers in dicarboxylic acid component (B), it should be understood that, unless otherwise explicitly stated, the concentration is relative to the total number of moles of dicarboxylic acids in dicarboxylic acid component (A).

[0050] The concentration of terephthalic acid is 35 mol% to 100 mol%, 35 mol% to 100 mol%, 40 mol% to 100 mol%, 45 mol% to 100 mol%, or 50 mol% to 100 mol%. In some embodiments, the concentration of terephthalic acid is 30 mol% to 99 mol%, 35 mol% to 99 mol%, 40 mol% to 99 mol%, 45 mol% to 99 mol%, or 50 mol% to 99 mol%. In some embodiments, the concentration of terephthalic acid is 30 mol% to 95 mol%, 35 mol% to 97 mol%, 40 mol% to 97 mol%, 45 mol% to 97 mol%, or 50 mol% to 97 mol%.

[0051] Cyclohexanedicarboxylic acid is represented by the following formula:

[0052] (6)

[0053] Where R j The group selected is from the group consisting of alkyl, aryl, alkali metal or alkaline earth metal sulfonates, alkyl sulfonates, and quaternary ammonium compounds; and j is an integer from 0 to 10. The visible -COOH group is relatively located at the meta (1,3-) or para (1,4-), preferably para. Preferably, cyclohexanedicarboxylic acid is 1,4-cyclohexanedicarboxylic acid (“CHDA”) (j is 0). Of course, cyclohexanedicarboxylic acid can be in either a cis or trans conformation. Therefore, the dicarboxylic acid component (B) can comprise only cis-cyclohexanedicarboxylic acid, only trans-cyclohexanedicarboxylic acid, or a mixture of cis-cyclohexanedicarboxylic acid and trans-cyclohexanedicarboxylic acid.

[0054] The concentration of cyclohexanedicarboxylic acid is 1 mol% to 70 mol%, 1 mol% to 65 mol%, 1 mol% to 60 mol%, 1 mol% to 55 mol%, or 1 mol% to 50 mol%.

[0055] The dicarboxylic acid component (B) comprises one or more additional dicarboxylic acids. Each additional dicarboxylic acid is different from each other and is different from terephthalic acid and cyclohexanedicarboxylic acid. In some embodiments, one, some or all of these additional dicarboxylic acids are represented by formula (6), and are each different from each other and are different from cyclohexanedicarboxylic acid.

[0056] The one or more additional dicarboxylic acids are independently selected from the group consisting of: C4 to C5. 12 Aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and alicyclic dicarboxylic acids. Desired C4 to C5... 10 Examples of aliphatic dicarboxylic acids include, but are not limited to, succinic acid [HOOC-(CH2)2-COOH], glutaric acid [HOOC-(CH2)3-COOH], 2,2-dimethyl-glutaric acid [HOOC-C(CH3)2-(CH2)2-COOH], adipic acid [HOOC-(CH2)4-COOH], 2,4,4-trimethyl-adipic acid [HOOC-CH(CH3)-CH2-C(CH3)2-CH2-COOH], pimelic acid [HOOC-(CH2)5-COOH], octanoic acid [HOOC-(CH2)6-COOH], azelaic acid [HOOC-(CH2)7-COOH], sebacic acid [HOOC-(CH2)8-COOH], and 1,12-dodecanoic acid [HOOC-(CH2)2-COOH]. 10 -COOH].

[0057] Suitable examples of desired aromatic dicarboxylic acids include, but are not limited to, phthalic acid (including isophthalic acid (IA)), naphthalenedicarboxylic acid (e.g., naphthal-2,6-dicarboxylic acid), 4,4'-biphenylcarboxylic 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)one, 4,4'-bis(4-carboxyphenyl)sulfone, 2,2-bis(3-carboxyphenyl)propane, 2,2-bis(3-carboxyphenyl)hexafluoropropane, 2,2-bis(3-carboxyphenyl)one, and bis(3-carboxyphenoxy)benzene.

[0058] Examples of desired alicyclic dicarboxylic acids include, but are not limited to, cyclopropane-1,2-dicarboxylic acid, 1-methylcyclopropane-1,2-dicarboxylic acid, cyclobutane-1,2-dicarboxylic acid, tetrahydrofuran-2,5-dicarboxylic acid, and 1,3-adamantanedicarboxylic acid.

[0059] When the PA polymer contains one or more additional dicarboxylic acids, the total concentration of the one or more additional dicarboxylic acids does not exceed 20 mol.

[0060] The PA polymer formed by the polycondensation of monomers in the diamine and dicarboxylic acid components as described above comprises repeating units R, each represented by the following formula. PA1 and R PA2 :

[0061] , and (7)

[0062] (8)

[0063] Furthermore, when cyclohexanedicarboxylic acid is present in the dicarboxylic acid component (B), the repeating unit R... PA3 and R PA4 They are represented by the following formulas respectively:

[0064] , (9) and

[0065] (10)

[0066] Among them, R1 to R3, R i R j i and j are as defined above. Those skilled in the art will recognize that the repeating unit R... PA1 From C4 to C 12 The condensation polymerization of aliphatic diamines and terephthalic acid forms a repeating unit R. PA3 From C4 to C 12 The condensation polymerization of aliphatic diamines and cyclohexanedicarboxylic acid forms a repeating unit R. PA2 It is formed by the condensation polymerization of bis(aminoalkyl)cyclohexane and terephthalic acid, and the repeating unit R PA4 It is formed by the condensation polymerization of bis(aminoalkyl)cyclohexane and cyclohexanedicarboxylic acid. In some embodiments, R1 is -(CH2)- m Where m is 5 to 10, preferably 5 to 9, and most preferably 6. Additionally or alternatively, in some embodiments, R2 and R3 are both -CH2-, and i and j are both zero. In some embodiments, bis(aminoalkyl)cyclohexane is 1,3-bis(aminomethyl)cyclohexane, and cyclohexanedicarboxylic acid is 1,4-cyclohexanedicarboxylic acid.

[0067] Repeating unit R PA1 and R PA2 The total concentration is at least 50 mol%, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 97 mol%, at least 98 mol%, at least 99 mol%, or at least 99.5 mol%. In some embodiments, where optionally cyclohexanedicarboxylic acid is present in the dicarboxylic acid component (B), the repeating unit R... PA1 To RPA4 The total concentration 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 the mol% of repeating units, it should be understood that the concentration is relative to the total number of repeating units in the indicated polymer, unless otherwise explicitly stated.

[0068] The PA polymer used in the compositions of this invention is a semi-crystalline polyamide. As used herein, a semi-crystalline polyamide is one having a heat of fusion ("ΔH") of at least 5 joules / gram ("J / g"). f The polyamide used in the compositions of this invention can conveniently have a ΔH of at least 30 J / g or at least 35 J / g. f Alternatively or additionally, the PA polymer has a ΔH of not more than 60 J / g or not more than 55 J / g. f PA polymers can have a ΔH of 30 J / g to 60 J / g, 35 J / g to 60 J / g, 30 J / g to 55 J / g, or 35 J / g to 55 J / g. f ΔH f The measurement can be performed using a heating rate of 20°C / min, according to ASTM D3418.

[0069] PA polymers may 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, and preferably at least 150°C. Alternatively or additionally, semi-aromatic PA polymers may have a Tg not exceeding 190°C, not exceeding 180°C, or not exceeding 170°C. PA polymers may have a Tg of 100°C to 190°C, 120°C to 180°C, 145°C to 170°C, 150°C to 190°C, 150°C to 180°C, or 150°C to 170°C. Tg may be measured according to ASTM D3418.

[0070] PA polymers can have a number-average molecular weight (“Mn”) ranging from 1,000 g / mol to 40,000 g / mol, for example 2,000 g / mol to 35,000 g / mol, 4,000 to 30,000 g / mol, or 5,000 g / mol to 20,000 g / mol. The number-average molecular weight Mn can be determined by gel permeation chromatography (GPC) using polystyrene standards according to ASTM D5296.

[0071] PA polymers can be prepared by any conventional method suitable for synthesizing polyamides and polyphthalamides. Preferably, the PA polymer is prepared by reacting monomers in the presence of less than 60 wt.% (preferably less than 50 wt.%) of water at a temperature of at least T. m Prepared by reacting (by heating) at a temperature of +10°C, T m It is the melting temperature of the semi-aromatic PA polymer, where wt.% is relative to the total weight of the reaction mixture.

[0072] The PA polymers described herein can be prepared, for example, by thermal polycondensation (also known as polycondensation or condensation) of aqueous solutions of monomers and comonomers. In one embodiment, polyamide (PA) is formed by: making at least C4 to C6 in a reaction mixture. 12 The reaction involves an aliphatic diamine, bis(aminoalkyl)cyclohexane, terephthalic acid, and cyclohexanedicarboxylic acid (if present in the dicarboxylic acid component (B)). In some embodiments, the total moles of the diamine in the reaction mixture are substantially equimolar to the total moles of the dicarboxylic acid in the reaction mixture. As used herein, substantially equimolar means a value indicating ±15% of the moles. For example, given the concentrations of the diamine and dicarboxylic acid in the reaction mixture, the total moles of the diamine in the reaction mixture are ±15% of the total moles of the dicarboxylic acid in the reaction mixture. The PA polymer may contain a chain limiting agent, 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 limiting agent may be acetic acid, propionic acid, benzoic acid, and / or benzylamine. A catalyst may also be used. Examples of catalysts are phosphorous acid, orthophosphoric acid, metaphosphoric acid, alkali metal hypophosphite such as sodium hypophosphite, and phenylphosphine.

[0073] The PA polymer is present in the polymer composition in amounts of 5.0 wt% to 17.5 wt%, 5.0 wt% to 17.0 wt%, 5.0 wt% to 16.0 wt%, 5.0 wt% to 15.0 wt%, 6.0 wt% to 15.0 wt%, 7.0 wt% to 15.0 wt%, 8.0 wt% to 15.0 wt%, 9.0 wt% to 15.0 wt%, 10.0 wt% to 15.0 wt%, 5.0 wt% to 14.0 wt%, 5.0 wt% to 13.0 wt%, 5.0 wt% to 12.0 wt%, 5.0 wt% to 11.0 wt%, or 5.0 wt% to 10.0 wt% based on the total weight of the polymer composition. It has been found that the presence of semi-aromatic PA polymers in the polymer composition at amounts of 5.0 wt% or greater advantageously improves the CTI of the polymer composition.

[0074] Filler material

[0075] The polymer composition disclosed in this invention comprises a filler material containing a halogen-free flame retardant compound, magnesium hydroxide, and a reinforcing agent. The filler material is present in the polymer composition in an amount based on the total weight of the polymer composition of 55.0 wt% to 75.0 wt%, 56.0 wt% to 74.0 wt%, 57.0 wt% to 73.0 wt%, 58.0 wt% to 72.0 wt%, 59.0 wt% to 71.0 wt%, 60.0 wt% to 70.0 wt%, 61.0 wt% to 69.0 wt%, 62.0 wt% to 68.0 wt%, 63.0 wt% to 67.0 wt%, or 64.0 wt% to 66.0 wt%.

[0076] The terms "phosphorus-based halogen-free flame retardant compounds" and "HFFR compounds" are used interchangeably in this document.

[0077] Suitable phosphorus-based flame retardants may be phosphine, phosphonates, phosphonites, phosphites, phosphine oxides, phosphonates, phosphonates, phosphates, phenoxyphosphazenes, melamine polyphosphates, or combinations thereof. The HFFR compound may be a phosphorus-containing material in an amount of 24.5 wt% to 25.5 wt% of the total weight of the HFFR-based compound, as measured by wavelength dispersive X-ray fluorescence spectroscopy.

[0078] Advantageously, the HFFR compound is an organophosphorus compound selected from the group consisting of: salts of hypophosphonic acid (hypophosphonates), salts of secondary phosphonic acid (secondary phosphonates), and their condensation products. Preferably, the organophosphorus compound is selected from the group consisting of: salts of hypophosphonic acid having formula (11), salts of secondary phosphonic acid having formula (12), and their condensation products.

[0079] (11)

[0080] (12)

[0081] Wherein, R1 and R2 are the same or different, and each of R1 and R2 is hydrogen or a straight-chain or branched C1-C6 alkyl or aryl group; R3 is a straight-chain or branched C1-C6 alkyl group. 10 Alkylene, C6-C 10 arylene, alkyl-arylene, or aryl-alkylene; 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.

[0082] Preferably, R1 and R2 are independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, and phenyl; R3 is selected from methylene, ethylene, n-propylene, isopropylene, n-butylene, tert-butylene, n-pentylene, n-octylene, n-dodecylene, phenylene, naphthylene, methylphenylene, ethylphenylene, tert-butylphenylene, methylnaphthylene, ethylnaphthylene, tert-butylnaphthylene, phenylmethylene, phenylethylene, phenylpropylene, and phenylbutylene; and M is selected from aluminum and zinc ions.

[0083] Phosphinates are preferred as organophosphorus compounds. Suitable phosphinates have been described in U.S. Patent No. 6,365,071, which is incorporated herein by reference. Particularly preferred phosphinates are aluminum phosphinate, calcium phosphinate, and zinc phosphinate. Excellent results have been obtained using aluminum phosphinate. Among aluminum phosphinates, ethylmethyl aluminum phosphinate and diethyl aluminum phosphinate, and combinations thereof, are preferred.

[0084] The halogen-free flame retardant compound is present in an amount of 12.5 wt% to 25.0 wt%, preferably 15.0 wt% to 20.0 wt%, based on the total weight of the polymer composition.

[0085] Typically, the reinforcing agent is a fibrous reinforcing agent or a particulate reinforcing agent. A fibrous reinforcing agent refers to a material having a length, width, and thickness, wherein the average length is significantly greater than both the width and thickness. Generally, such materials have an aspect ratio (defined as the average ratio between the length and the largest of the width and thickness) of at least 5, at least 10, at least 20, or at least 50. In some embodiments, the fibrous reinforcing agent (e.g., glass fiber, glass beads, or carbon fiber) has an average length of 3 mm to 50 mm. In some such embodiments, the fibrous reinforcing agent has an average length of 3 mm to 10 mm, 3 mm to 8 mm, 3 mm to 6 mm, or 3 mm to 5 mm. In alternative embodiments, the fibrous reinforcing agent has an average length of 10 mm to 50 mm, 10 mm to 45 mm, 10 mm to 35 mm, 10 mm to 30 mm, 10 mm to 25 mm, or 15 mm to 25 mm. The average length of the fibrous reinforcing agent can be the average length of the fibrous reinforcing agent before being incorporated into the polymer composition or it can be the average length of the fibrous reinforcing agent in the polymer composition.

[0086] The morphology of the glass fibers is not particularly limited. As noted above, glass fibers can have a circular cross-section (“circular glass fibers”) or a non-circular cross-section (“flat glass fibers”). 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 comprises flat glass fibers, the flat glass fibers have a longest cross-sectional diameter of at least 15 µm, preferably at least 20 µm, more preferably at least 22 µm, and even more preferably at least 25 µm. Additionally or alternatively, in some embodiments, the flat glass fibers have a longest cross-sectional diameter of up to 40 µm, preferably at most 35 µm, more preferably at most 32 µm, and even more preferably at most 30 µm. In some embodiments, the flat glass fibers have a cross-sectional diameter in the range of 15 to 35 µm, preferably 20 to 30 µm, and more preferably 25 to 29 µm. In some embodiments, the flat glass fibers have a shortest cross-sectional diameter of at least 4 µm, preferably at least 5 µm, more preferably at least 6 µm, and even more preferably at least 7 µm. Alternatively or additionally, in some embodiments, the flat glass fiber has a minimum cross-sectional diameter of up to 25 µm, preferably up to 20 µm, more preferably up to 17 µm, and even more preferably up to 15 µm. In some embodiments, the flat glass fiber has a minimum cross-sectional diameter in the range of 5 to 20 µm, preferably 5 to 15 µm, and more preferably 7 to 11 µm.

[0087] The flat glass fiber has an aspect ratio of at least 2, preferably at least 2.2, more preferably at least 2.4, and even more preferably at least 3. This aspect ratio is defined as the 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 up to 8, preferably up to 6, and more preferably up to 4. In some embodiments, the flat glass fiber has an aspect ratio of 2 to 6, and preferably 2.2 to 4. In some embodiments where the glass fiber is a round glass fiber, 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, and most preferably less than 1.05. Of course, those skilled in the art will understand that regardless of the shape of the glass fiber (e.g., round or flat), the aspect ratio cannot be less than 1 by definition.

[0088] The reinforcing agent can 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 are mentioned in particular in the Plastics Additives Handbook, Hanser, 4th edition, pp. 537-538. Hollow glass beads that can be used in the compositions of the present invention typically have an aspect ratio (short axis / long axis) of at least 0.9, preferably at least 0.95.

[0089] Examples of commercially available hollow glass beads are available from 3M™. A suitable example is iM16K (true density 0.46 g / cm³). 3 (Crushing strength 110 MPa).

[0090] Magnesium hydroxide is a relatively high-purity magnesium hydroxide containing not less than 80% by weight of inorganic matter represented by the chemical formula Mg(OH)2. For the purposes of tracking resistance (CTI), mechanical strength, and melt viscosity, high-purity magnesium hydroxide is appropriately used, preferably containing not less than 70 wt% of inorganic matter represented by Mg(OH)2, not more than 5 wt% of CaO, and not more than 1 wt% of chlorine; more preferably containing not less than 95 wt% of inorganic matter represented by Mg(OH)2, not more than 1 wt% of CaO, and not more than 0.5 wt% of chlorine; and even more preferably containing not less than 98 wt% of inorganic matter represented by Mg(OH)2, not more than 0.1 wt% of CaO, and not more than 0.1 wt% of chlorine.

[0091] The magnesium hydroxide used according to the present invention can be in any form, such as granular, flake, or fibrous. Granular and flake forms are most preferred, for example, in terms of dispersibility. The specific surface area is preferably not greater than 15 m². 2 / g, and more preferably not greater than 10 m 2 / g. Greater than 15 m 2The specific surface area per g can affect the dispersibility of magnesium hydroxide and undesirably have an adverse effect on improvements in tracking resistance and mechanical strength. The term "specific surface area" as used herein is a value measured using the BET method with nitrogen as the adsorbed gas. When using magnesium hydroxide in granular or flake form, suitable magnesium hydroxide has an average primary particle size in the range of 0.3 to 5 μm, or preferably 0.3 to 3 μm, for a good balance between improvements in tracking resistance, mechanical strength, and melt viscosity. The "average primary particle size" is a value measured by laser diffraction scattering. When using magnesium hydroxide in fibrous form, suitable magnesium hydroxide has an average fiber diameter in the range of 0.1 to 2 μm and an aspect ratio in the range of 20 to 60, or preferably an average fiber diameter in the range of 0.3 to 2 μm and an aspect ratio in the range of 30 to 50. "Aspect ratio" is the ratio of the long side dimension to the short side dimension of the material.

[0092] Magnesium hydroxide can be present in amounts 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. It was found that when magnesium hydroxide was present in an amount of approximately 46 wt% based on the combined weight of the filler materials, it provided a surprisingly favorable peak in terms of retention of mechanical properties.

[0093] Products and Applications

[0094] This disclosure also relates to articles comprising the disclosed polymer compositions. The polymer compositions disclosed herein are desirable for incorporation into any article exposed to elevated temperatures during its intended use, at least in part due to the improved retention of mechanical and dielectric properties after thermal aging.

[0095] The article is selected from the group consisting of automotive parts, marine parts, and aerospace parts. In some embodiments, the article is selected from the group consisting of: fluid inlet / outlet ports, fluid inlet / outlet valves, fluid pump housings, fluid pump impellers, fluid hose connections, fluid hoses, fluid reservoirs, and fluid valves. Polymer compositions are even more advantageously incorporated into such articles when they are used in engine compartments (e.g., exposed to elevated temperatures).

[0096] Articles can be molded from polymer compositions using any method suitable for thermoplastics (e.g., extrusion, injection molding, blow molding, rotational molding, or compression molding). Polymer compositions can also be used to overmolded preforms to construct hybrid structures. Suitable examples of molded articles comprising polymer compositions include, but are not limited to, busbars, semiconductors, surface-mount devices, printed circuit boards, electrical component circuit boards, and combinations thereof.

[0097] This disclosure will now be described with reference to the following examples, which are intended to be illustrative only and not to limit this disclosure.

[0098] raw material

[0099] PAS 1: Ryton® QA200N, which has an MFR of 80 to 120 g / 10min at 316°C / 5.0 kg according to ASTM D1238, and is available from Solvay Specialty Polymers USA;

[0100] PAS 2: Ryton® QA321N, which has an MFR of 1300 to 1500 g / 10 min at 316°C / 5.0 kg according to ASTM D1238, and is available from Solvay Specialty Polymers, Inc., USA.

[0101] PPA: Amodel® PPA 9004, 6T / 1,3-BACT / 6CHDA / 1,3-BACCHDA copolymer with an intrinsic viscosity of 0.8 to 1.2 dl / g as measured according to ASTM D2857, available from Solvay Specialty Polymers, Inc., USA;

[0102] HDPE: HDPE6007G was purchased from Nexeo Plastics USA.

[0103] HFFR: Exolit® 1400, a non-halogenated flame retardant based on organic phosphinates, available from Clariant.

[0104] Magnesium oxide: Synthetic magnesium oxide Kisuma 5A;

[0105] Glass fiber: DS 8800-P is chopped glass filament obtained from 3B Fiberglass.

[0106] Manufacturing method

[0107] The formulations shown in Table I were compounded on a ZSK 26 using a conventional twin-screw extruder. Compounding was performed at a screw speed of 200 rpm and a torque range of 35% to 80% of the extruder's capacity, from 330°C to 360°C. Samples were molded at temperatures higher than typical for PPS (360°C to 370°C, die temperature 150°C to 180°C). Samples were molded into ISO multipurpose / stretch bars and tested at room temperature according to ISO 527. The Comparative Tracking Index (CTI) was measured according to IEC 60112. Density and specific gravity were measured according to ASTM D792.

[0108] Example

[0109] The following examples were prepared based on the above description. Examples 1 and 2 were prepared using both the HFFR compound and Mg(OH)₂. Comparative Examples 1-4 were prepared without the HFFR compound and with only Mg(OH)₂. Comparative Examples 5 and 6 were prepared with the 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.

[0110] Table I. Polymer compositions of filler materials with different concentrations of HFFR compounds and Mg(OH)2.

[0111]

[0112] Table II. Mechanical and dielectric properties of polymer compositions of different concentrations of HFFR compound and Mg(OH)2 in filler materials.

[0113]

[0114] As can be seen in Table II, the samples produced in Examples 1 and 2 by combining both the HFFR compound and Mg(OH)₂ maintained the same high CTI values ​​as Comparative Examples 3 and 4, which did not contain the HFFR compound. However, at the same time, the density and specific gravity of Examples 1 and 2 decreased compared to Comparative Examples 3 and 4, showing that Examples 1 and 2 obtained compositions with reduced density without reducing the CTI. Those skilled in the art will understand that this result is unexpected.

[0115] As seen in Example 1 compared to Comparative Example 3 and Example 2 compared to Comparative Example 4, the introduction of more HFFR compounds at the expense of Mg(OH)2 unexpectedly improved the tensile elongation at break.

Claims

1. A polymer composition comprising: Poly(arylene sulfide) polymer; A semi-aromatic polyamide, in an amount of 5.0 wt% to 17.5 wt%, preferably 5.0 wt% to 15.0 wt%, based on the total weight of the polymer composition; and The filler material includes: -Mg(OH)2, in an amount of 12.5 wt% to 25.0 wt%, preferably 15.0 wt% to 20.0 wt%, based on the total weight of the polymer composition; - A phosphorus-based halogen-free flame retardant compound, in an amount of 12.5 wt% to 25.0 wt%, preferably 15.0 wt% to 20.0 wt%, based on the total weight of the polymer composition; and -A reinforcing agent, in an amount of 20.0 wt% to 37.5 wt%, preferably 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 of 10.0 wt% to 30.0 wt%, preferably 20.0 wt% to 30.0 wt%, based on the total weight of the polymer composition.

3. The polymer composition according to claim 1 or 2, wherein, The poly(arylene sulfide) polymer is polyphenylene sulfide.

4. The polymer composition according to any one 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 according to any one of claims 1 to 4, wherein, This semi-aromatic polyamide contains repeating units derived from the following: - 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, wherein the mol% is relative to the total moles of each diamine in the diamine component; and - Dicarboxylic acid component (B), which comprises 30 mol% to 100 mol% terephthalic acid and 0 mol% to 70 mol% cyclohexanedicarboxylic acid, where mol% is relative to the total number of 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... 12 The aliphatic diamine is 1,6-diaminohexane.

7. The polymer composition according to any one of claims 5 or 6, wherein, The bis(aminoalkyl)cyclohexane is 1,3-bis(aminomethyl)cyclohexane or 1,4-bis(aminomethyl)cyclohexane.

8. The polymer composition according to any one 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 molar number of each dicarboxylic acid in the dicarboxylic acid component.

9. The polymer composition according to any one of claims 1 to 8, wherein, The phosphorus-based halogen-free flame retardant compound is selected from the group consisting of: phosphine, hypophosphite, phosphite, phosphite oxide, hypophosphite, phosphonate, phosphate, phenoxyphosphazene, melamine polyphosphate, or combinations thereof.

10. The polymer composition according to any one of claims 1 to 9, wherein, The phosphorus-based halogen-free flame retardant compound contains 24.5 wt% to 25.5 wt% of phosphorus based on the total weight of the HFFR compound, as measured by wavelength dispersive X-ray fluorescence spectroscopy.

11. The polymer composition according to any one of claims 1 to 10, wherein, The polymer composition has a comparative tracking index (CTI) of 400 V or greater, or 500 V or greater, or 600 V or greater.

12. The polymer composition according to any one 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 as described in any one of claims 1 to 12.

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

15. Use of phosphorus-based halogen-free flame retardant compounds for reducing the density of high CTI compositions comprising poly(arylene sulfide) polymers, semi-aromatic polyamides, and filler materials.

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