Hydrolytically stable polyarylene sulfide compositions

Abstract

A polymeric composition is provided that includes 100 parts by weight of a polymeric matrix containing at least one polyarylene sulfide and about 30 to about 120 parts by weight of inorganic fibers. The polymeric composition exhibits an initial tensile strength and an aged tensile strength after exposure to a solution containing 50% by volume of deionized water and 50% by volume of ethylene glycol at a temperature of 135°C for 1,000 hours. The ratio of the aged tensile strength to the initial tensile strength is about 0.8 or greater.

Description

[Technical Field]

[0001] Related Applications

[0001] This application is based on and claims priority to U.S. Provisional Patent Application No. 63 / 428,140, ​​filed November 28, 2022, which is incorporated herein by reference. [Background technology]

[0002]

[0002] Electric vehicles, such as battery electric vehicles, plug-in hybrid electric vehicles, mild hybrid electric vehicles, or full hybrid electric vehicles, generally have an electric powertrain including an electric propulsion source (e.g., a battery) and a transmission. Plastic materials are often used in electric vehicles for various electronic components, such as high-voltage connectors, power conversion housings, battery assembly housings, inverters, bus bars, twisted cables, individual sense leads, wire crimps, grommet moldings, quick connectors, tees, interconnects, guide rails, and sealing rings (e.g., brushless DC sealing rings, battery cell sealing rings, etc.). Unfortunately, plastic materials often used for such components, especially when reinforced with glass fibers, exhibit poor mechanical properties (e.g., tensile strength and impact resistance) when exposed to moisture. This is particularly evident at elevated temperatures. Therefore, there is currently a need for polymer compositions that exhibit greater hydrolysis resistance at elevated temperatures. Summary of the Invention [Means for solving the problem]

[0003] According to one embodiment of the present invention, a polymeric composition is disclosed that includes 100 parts by weight of a polymeric matrix including at least one polyarylene sulfide and about 30 to about 120 parts by weight of inorganic fibers. The polymeric composition exhibits an initial tensile strength and an aged tensile strength after exposure to a solution containing 50% by volume of deionized water and 50% by volume of ethylene glycol at a temperature of 135°C for 1,000 hours. The ratio of the aged tensile strength to the initial tensile strength is about 0.8 or greater.

[0004]

[0004] Other features and aspects of the present invention are described in more detail below.

[0005] A full and enabling disclosure of the present invention, including the best mode thereof to one skilled in the art, is set forth more particularly in the remainder of the specification, including reference to the accompanying drawings, in which: [Brief explanation of the drawings]

[0005] [Figure 1]

[0006] 1 illustrates an electric vehicle that includes components into which the polymer compositions disclosed herein can be incorporated. [Figure 2]

[0007] 1 illustrates one embodiment of a busbar that can incorporate the polymer composition disclosed herein. [Figure 3]

[0008] 1 illustrates a battery assembly that may employ components that may incorporate the polymer compositions disclosed herein. [Figure 4]

[0009] 1 illustrates an electronic system that may include components into which the polymer compositions disclosed herein may be incorporated. [Figure 5]

[0010] 5 illustrates a current sensor that may be included in the electronic system of FIG. 4. [Figure 6]

[0011] 1 illustrates an inverter system that may be present in an electric vehicle that includes components into which the polymer compositions disclosed herein may be incorporated. [Figure 7]

[0012] 1 is a perspective view of one embodiment of a connector into which the polymer compositions disclosed herein can be incorporated. [Figure 8]

[0013] 8 is a plan view of the connector of FIG. 7, with the first connector portion and the second connector portion separated. [Figure 9]

[0014] 8 is a plan view of the connector of FIG. 7, with the first connector portion and the second connector portion mated. [Figure 10]

[0015] Examples of components into which the polymer compositions disclosed herein can be incorporated are provided. [Figure 11]

[0016] 1 illustrates additional components that can be incorporated into the polymer compositions disclosed herein. [Figure 12]

[0017] 1 illustrates a low temperature thermal loop that may include components into which the polymer compositions disclosed herein may be incorporated. [Figure 13]

[0018] 1 illustrates a high temperature thermal loop that may include components into which the polymer compositions disclosed herein may be incorporated. [Figure 14]

[0019] 1 illustrates one embodiment of a coolant pump that can incorporate the polymer compositions disclosed herein. DETAILED DESCRIPTION OF THE INVENTION

[0006]

[0020] Repeat use of reference characters in the present specification and drawings is intended to represent same or analogous features or elements of the invention.

[0021] Those skilled in the art will appreciate that this description is a description of exemplary embodiments only and is not intended to limit the broader aspects of the invention.

[0007]

[0022] Generally speaking, the present invention is directed to a polymer composition comprising a polymer matrix containing at least one polyarylene sulfide and inorganic fibers. By selectively controlling the specific properties and relative concentrations of the components of the composition, the inventors have discovered that the resulting composition can exhibit a unique combination of properties that allow it to be readily used in a wide range of product applications (e.g., electric vehicles) even at relatively small part thickness values, such as about 4 millimeters or less, in some embodiments, about 0.2 to about 3.2 millimeters, in some embodiments, about 0.4 to about 2.5 millimeters, and in some embodiments, about 0.8 to about 2 millimeters.

[0008]

[0023] The polymer composition may exhibit, for example, a tensile stress at break (i.e., strength) of about 100 MPa to about 300 MPa, in some embodiments about 120 MPa to about 250 MPa, in some embodiments about 130 to about 220 MPa, and in some embodiments about 140 to about 200 MPa; a tensile strain at break (i.e., elongation) of about 1% or more, in some embodiments about 1.2% to about 8%, and in some embodiments about 1.5% to about 5%; and / or a tensile modulus of about 15,000 MPa or less, in some embodiments about 1,000 MPa to about 12,000 MPa, and in some embodiments about 5,000 MPa to about 11,000 MPa. Tensile properties may be determined at a temperature of 23°C according to ISO 527:2019. The compositions may also exhibit a flexural strength of about 20 MPa or greater, in some embodiments from about 25 to about 200 MPa, in some embodiments from about 30 to about 150 MPa, and in some embodiments from about 35 to about 100 MPa, and / or a flexural modulus of about 10,000 MPa or less, in some embodiments from about 500 MPa to about 8,000 MPa, in some embodiments from about 1,000 MPa to about 6,000 MPa, and in some embodiments from about 1,500 MPa to about 5,000 MPa. Flexural properties may be determined at a temperature of 23°C according to ISO 178:2019. The polymer compositions may also exhibit high impact strength, which may provide enhanced flexibility to the resulting part. For example, the polymer compositions may exhibit a flexural modulus of about 2 kJ / m when determined at a temperature of 23°C according to ISO 179-1:2010. 2or more, in some embodiments, about 4 to about 40 kJ / m 2 and in some embodiments, from about 5 to about 20 kJ / m 2 It can exhibit a notched Charpy impact strength of 1000 MPa.

[0009]

[0024] In particular, the inventors have discovered that the polymer composition is not sensitive to the presence of an aqueous coolant at elevated temperatures. For example, the polymer composition can be contacted with a solution containing 50% by volume of dehydrated water and 50% by volume of ethylene glycol at temperatures above about 100°C, in some embodiments from about 110°C to about 200°C, and in some embodiments, from about 120°C to about 180°C (e.g., 135°C). Even when exposed to an aqueous coolant at such high temperatures, the mechanical properties (e.g., impact strength, tensile properties, etc.) can remain near or even within the above-mentioned ranges. The mechanical properties can also remain stable at such temperatures for substantial periods, such as from about 100 hours or more, in some embodiments, from about 200 hours to about 3,000 hours, and in some embodiments, from about 250 hours to about 2,000 hours (e.g., 250, 500, 1,000, 1,500, or 2,000 hours).

[0010]

[0025] For example, after "aging" in solution at 135°C for 1,000 hours, the ratio of the aged tensile strength to the initial tensile strength before aging may be about 0.8 or greater, in some embodiments about 0.85 or greater, and in some embodiments about 0.9 to 1.0; the ratio of the aged tensile elongation to the initial tensile elongation before aging may be about 0.7 or greater, in some embodiments about 0.75 or greater, and in some embodiments about 0.8 to 1.0; and / or the ratio of the aged tensile modulus to the initial tensile modulus before aging may be about 0.8 or greater, in some embodiments about 0.85 or greater, and in some embodiments about 0.9 to 1.2. For example, the tensile strength after aging in solution at 135°C for 1,000 hours, as determined at a temperature of about 23°C according to ISO 527:2019, may be about 80 MPa to about 300 MPa, in some embodiments about 125 MPa to about 250 MPa, in some embodiments about 130 to about 220 MPa, or in some embodiments about 140 to about 200 MPa. Similarly, the tensile elongation after aging in solution at 135°C for 1,000 hours, as determined at a temperature of about 23°C according to ISO 527:2019, may be, for example, about 0.7% or greater, in some embodiments about 1% to about 8%, in some embodiments about 1.2% to about 5%, or in some embodiments about 1.4% to about 4%, for example. After aging in solution at 135°C for 1,000 hours, the ratio of the aged notched Charpy impact strength to the initial impact strength before aging may also be about 0.6 or greater, in some embodiments about 0.7 or greater, and in some embodiments about 0.8 to 1.0. For example, the notched Charpy impact strength after aging in solution at 135°C for 1,000 hours may be about 1 kJ / m when determined at 23°C according to ISO Test No. 179-1:2010. 2 or greater, in some embodiments, about 2 kJ / m 2 or more, in some embodiments, about 4 to about 20 kJ / m 2 and in some embodiments, from about 5 to about 15 kJ / m 2 may be.

[0011]

[0026] The polymer composition may also exhibit good heat resistance and flame retardancy. The melting temperature of the composition may be, for example, from about 250°C to about 440°C, in some embodiments, from about 260°C to about 400°C, and in some embodiments, from about 280°C to about 380°C. Even at such melting temperatures, the ratio of temperature deflection under load ("DTUL") to melting temperature, which is an indicator of short-term heat resistance, may still remain relatively high. For example, the ratio may be in the range of from about 0.5 to about 1.00, in some embodiments, from about 0.6 to about 0.95, and in some embodiments, from about 0.65 to about 0.85. Particular DTUL values ​​may be, for example, greater than about 260°C, in some embodiments, from about 260°C to about 350°C, and in some embodiments, from about 265°C to about 320°C, as determined, for example, according to ISO 75:2013 at a load of 1.8 MPa. Such high DTUL values ​​enable, among other things, the use of high-speed, reliable surface mounting processes for mating the structure with other components in an electrical component. The flame retardant properties of the composition may also be characterized according to the procedure of Underwriter's Laboratory Bulletin 94, entitled "Tests for Flammability of Plastic Materials, UL 94." Several ratings may be applied based on the time to extinction (total burn time of a set of five test specimens) and the ability to resist dripping, as described in more detail below. According to this procedure, for example, a composition may exhibit a V0 rating for part thicknesses such as those listed above (e.g., about 0.4 to about 3.2 millimeters, e.g., 0.4, 0.8, or 1.6 millimeters), meaning that it has a total burn time of about 50 seconds or less. To achieve a V0 rating, the composition may also exhibit a total drip count of 0 fire particles to ignite cotton.

[0012]

[0027] Various embodiments of the present invention will now be described in more detail below. I. Polymer Composition A. Polymer matrix

[0028] The polymer matrix typically comprises about 40 wt% to about 90 wt%, in some embodiments about 45 wt% to about 90 wt%, and in some embodiments about 50 wt% to about 70 wt% of the polymer composition. The polymer matrix contains at least one polyarylene sulfide. For example, the polyarylene sulfide typically comprises about 50 wt% to 100 wt%, in some embodiments about 70 wt% to 100 wt%, and in some embodiments about 90 wt% to 100 wt% of the polymer matrix (e.g., 100 wt%).

[0013]

[0029] Polyarylene sulfides generally have repeat units of the formula: -[(Ar 1 ) n -X] m -[(Ar 2 ) i -Y] j -[(Ar 3 ) k -Z] l -[(Ar 4 ) o -W] p - (In the formula, Ar 1 , Ar 2 , Ar 3 , and Ar 4 are independently arylene units of 6 to 18 carbon atoms; W, X, Y, and Z are independently divalent linking groups selected from -SO2-, -S-, -SO-, -CO-, -O-, -C(O)O-, or alkylene or alkylidene groups of 1 to 6 carbon atoms, where at least one of the linking groups is -S-; n, m, i, j, k, l, o, and p are independently 0, 1, 2, 3, or 4, provided that their sum is greater than or equal to 2.

[0014]

[0030] Arylene unit Ar 1 , Ar 2 , Ar 3 , and Ar 4may be optionally substituted or unsubstituted. Advantageous arylene units are phenylene, biphenylene, naphthalene, anthracene, and phenanthrene. Polyarylene sulfides typically contain more than about 30 mol%, more than about 50 mol%, or more than about 70 mol% of arylene sulfide (-S-) units. For example, polyarylene sulfides may contain at least 85 mol% of sulfide bonds directly bonded to two aromatic rings. In a particular embodiment, polyarylene sulfides contain as their components the phenylene sulfide structure -(C6H4-S) n - (wherein n is an integer of 1 or greater).

[0015]

[0031] Synthetic techniques that can be used to prepare polyarylene sulfides are generally known in the art. For example, a process for producing polyarylene sulfides may include reacting a hydrosulfide ion-producing substance (e.g., an alkali metal sulfide) with a dihaloaromatic compound in an organic amide solvent. The alkali metal sulfide may be, for example, lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, or a mixture thereof. If the alkali metal sulfide is a hydrate or an aqueous mixture, it may be treated by a dehydration process prior to the polymerization reaction. The alkali metal sulfide may also be generated in situ. In addition, a small amount of alkali metal hydroxide may be included in the reaction to remove or react impurities, such as alkali metal polysulfides or alkali metal thiosulfates, that may be present in very small amounts together with the alkali metal sulfide (e.g., to convert the impurities into harmless substances).

[0016]

[0032] The dihaloaromatic compound may be, but is not limited to, o-dihalobenzene, m-dihalobenzene, p-dihalobenzene, dihalotoluene, dihalonaphthalene, methoxy-dihalobenzene, dihalobiphenyl, dihalobenzoic acid, dihalodiphenyl ether, dihalodiphenyl sulfone, dihalodiphenyl sulfoxide, or dihalodiphenyl ketone. The dihaloaromatic compound may be used alone or in any combination thereof. Specific exemplary dihaloaromatic compounds include, but are not limited to, p-dichlorobenzene, m-dichlorobenzene, o-dichlorobenzene, 2,5-dichlorotoluene, 1,4-dibromobenzene, 1,4-dichloronaphthalene, 1-methoxy-2,5-dichlorobenzene, 4,4'-dichlorobiphenyl, 3,5-dichlorobenzoic acid, 4,4'-dichlorodiphenyl ether, 4,4'-dichlorodiphenyl sulfone, 4,4'-dichlorodiphenyl sulfoxide, and 4,4'-dichlorodiphenyl ketone. The halogen atom may be fluorine, chlorine, bromine, or iodine, and the two halogen atoms in the same dihaloaromatic compound may be the same or different. In one embodiment, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, or a mixture of two or more of these compounds is used as the dihaloaromatic compound. As is known in the art, it is also possible to use a monohalo compound (not necessarily an aromatic compound) in combination with a dihaloaromatic compound to form an end group of the polyarylene sulfide or to control the polymerization reaction and / or the molecular weight of the polyarylene sulfide.

[0017]

[0033] Polyarylene sulfides can be homopolymers or copolymers. For example, selective combinations of dihaloaromatic compounds can produce polyarylene sulfide copolymers containing two or more different units. For example, when p-dichlorobenzene is used in combination with m-dichlorobenzene or 4,4'-dichlorodiphenyl sulfone, polyarylene sulfides of the formula:

[0018] [ka]

[0019] and a segment having the structure:

[0020] [ka]

[0021] or a segment having the structure:

[0022] [ka]

[0023] Polyarylene sulfide copolymers can be formed containing segments having the structure:

[0034] Polyarylene sulfides may be linear, semi-linear, branched or crosslinked. Linear polyarylene sulfides typically contain 80 mol % or more of the repeating unit -(Ar-S)-. Such linear polymers may also contain small amounts of branched or crosslinked units, but the amount of branched or crosslinked units is typically less than about 1 mol % of the total monomer units of the polyarylene sulfide. Linear polyarylene sulfide polymers are random copolymers or block copolymers containing the above repeating units. The semi-linear polyarylene sulfide may also have a crosslinked or branched structure introduced into the polymer in small amounts of one or more monomers having three or more reactive functional groups. For example, the monomer components used to form the semi-linear polyarylene sulfide include some polyhaloaromatic compounds having two or more halogen substituents per molecule, which can be used to prepare branched polymers. Such monomers can be represented by the formula R'X nwhere each X is selected from chlorine, bromine, and iodine; n is an integer from 3 to 6; R' is a polyvalent aromatic group of valence n that may have up to about four methyl substituents; and the total number of carbon atoms in R' is in the range of 6 to about 16. Examples of some polyhaloaromatic compounds substituted with more than two halogens per molecule that can be used to form semi-linear polyarylene sulfides include 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, 1,3-dichloro-5-bromobenzene, 1,2,4-triiodobenzene, 1,2,3,5-tetrabromobenzene, hexachlorobenzene, 1,3,5-trichloro-2,4,6-trimethylbenzene, 2,2',4,4'-tetrachlorobiphenyl, 2,2',5,5'-tetra-iodobiphenyl, 2,2',6,6'-tetrabromo-3,3',5,5'-tetramethylbiphenyl, 1,2,3,4-tetrachloronaphthalene, 1,2,4-tribromo-6-methylnaphthalene, and the like, and mixtures thereof.

[0024]

[0035] If desired, the polyarylene sulfide can be functionalized. For example, a disulfide compound containing a reactive functional group (e.g., carboxyl, hydroxyl, amine, etc.) can react with the polyarylene sulfide. Furthermore, functionalization of the polyarylene sulfide can provide bonding sites between any optional impact modifier and the polyarylene sulfide, which can improve the distribution of the impact modifier throughout the polyarylene sulfide and prevent phase separation. The disulfide compound can undergo chain scission reactions with the polyarylene sulfide during melt processing to reduce the overall melt viscosity. When used, the disulfide compound typically comprises from about 0.01 wt% to about 3 wt%, in some embodiments from about 0.02 wt% to about 1 wt%, and in some embodiments, from about 0.05 to about 0.5 wt% of the polymer composition. The ratio of the amount of polyarylene sulfide to the amount of disulfide compound may likewise be from about 1000:1 to about 10:1, from about 500:1 to about 20:1, or from about 400:1 to about 30:1. Suitable disulfide compounds are typically those having the following formula: R 3 -SSR 4

[0036] In the formula, R 3 and R 4 may be the same or different and are independently hydrocarbon groups containing 1 to about 20 carbon atoms. For example, R 3 and R 4 may be an alkyl, cycloalkyl, aryl, or heterocyclic group. In certain embodiments, R 3 and R 4 R is generally a non-reactive functional group such as phenyl, naphthyl, ethyl, methyl, propyl, etc. Examples of such compounds include diphenyl disulfide, naphthyl disulfide, dimethyl disulfide, diethyl disulfide, and dipropyl disulfide. 3 and R 4 may also contain reactive functional groups at the end groups of the disulfide compound. For example, R 3 and R 4At least one of the groups may contain a terminal carboxyl group, a hydroxyl group, a substituted or unsubstituted amino group, or a nitro group, etc. Exemplary compounds include, but are not limited to, 2,2'-diaminodiphenyl disulfide, 3,3'-diaminodiphenyl disulfide, 4,4'-diaminodiphenyl disulfide, dibenzyl disulfide, dithiosalicylic acid (or 2,2'-dithiobenzoic acid), dithioglycolic acid, α,α'-dithiodilactic acid, β,β'-dithiodilactic acid, 3,3'-dithiodipyridine, 4,4'-dithiomorpholine, 2,2'-dithiobis(benzothiazole), 2,2'-dithiobis(benzimidazole), 2,2'-dithiobis(benzoxazole), 2-(4'-morpholinodithio)benzothiazole, and the like, and mixtures thereof.

[0025]

[0037] The melt flow rate of the polyarylene sulfide incorporated into the composition may be from about 100 to about 800 grams per 10 minutes (“g / 10 min”), in some embodiments from about 200 to about 700 g / 10 min, and in some embodiments from about 300 to about 600 g / 10 min, as determined according to ISO 1133:2011 at a load of 5 kg and a temperature of 316° C.

[0026] B. Inorganic Fibers

[0038] Inorganic fibers are also used in polymer compositions to improve the thermal and mechanical properties of the composition. Inorganic fibers typically have a high degree of tensile strength relative to their mass. For example, the ultimate tensile strength of the fibers (determined according to ASTM D822 / D822M-13(2018)) is typically about 1,000 to about 15,000 megapascals ("MPa"), in some embodiments about 2,000 to about 10,000 MPa, and in some embodiments about 3,000 to about 6,000 MPa. Furthermore, fibers can have a variety of different sizes, although fibers of a particular size can help improve the mechanical properties of the resulting polymer composition. Inorganic fibers can have a nominal diameter of, for example, about 5 micrometers to about 40 micrometers, in some embodiments about 6 micrometers to about 30 micrometers, in some embodiments about 8 micrometers to about 20 micrometers, and in some embodiments about 9 micrometers to about 15 micrometers. The fibers (after compounding) can also have a relatively high aspect ratio (average length (μm) divided by nominal diameter (μm)), e.g., about 2 or greater, in some embodiments about 4 to about 100, in some embodiments about 5 to about 50, and in some embodiments about 8 to about 40 being particularly useful. Such fibers can, for example, have a volume-average length (after compounding) of about 10 micrometers or greater, in some embodiments about 25 micrometers or greater, in some embodiments about 50 micrometers or greater to about 800 micrometers or less, and in some embodiments about 60 micrometers to about 500 micrometers. The relative amount of fiber can also be selectively controlled to help achieve desired mechanical and thermal properties without adversely affecting other properties of the composition, such as its flowability. The inorganic fibers, for example, can comprise about 30 to about 120 parts by weight, in some embodiments about 40 to about 110 parts by weight, and in some embodiments about 50 to about 100 parts by weight, per 100 parts by weight of polymer matrix. For example, the inorganic fibers may comprise from about 20 wt% to about 60 wt%, in some embodiments from about 25 wt% to about 55 wt%, and in some embodiments, from about 30 wt% to about 50 wt% of the polymer composition.

[0027]

[0039] In addition to size, strength, and relative concentration, the composition of the inorganic fibers can also be selectively controlled to achieve better hydrolytic stability at high temperatures. Generally speaking, the inorganic fibers can be formed from materials that are generally insulating in nature, such as glass, ceramic (e.g., alumina or silica), etc. Glass fibers such as E-glass, E-CR glass, A-glass, C-glass, D-glass, AR-glass, R-glass, S1-glass, S2-glass, etc., and mixtures of any of the foregoing, are particularly suitable. Glass fibers that are generally boron-free (e.g., E-CR glass fibers) are particularly suitable. In certain embodiments, the glass fibers can include silica (SiO), alumina (AlO), and oxides of calcium and magnesium (e.g., CaO, MgO, etc.), but are generally boron-free, and optionally fluoride-free. For example, the glass fibers may contain boron at a concentration of about 1 wt% or less, in some embodiments about 0.5 wt% or less, and in some embodiments about 0.1 wt% or less (e.g., 0 wt%), based on the total weight of the glass fibers. Similarly, the glass fibers may contain fluoride at a concentration of about 0.5 wt% or less, in some embodiments about 0.2 wt% or less, and in some embodiments about 0.01 wt% or less (e.g., 0 wt%), based on the total weight of the glass fibers. The boron and fluoride concentrations can be measured by inductively coupled plasma optical emission spectroscopy. In the absence of boron oxide, the glass fibers may further contain titanium dioxide (TiO) to reduce melt viscosity. For example, the concentration of titanium in the glass fibers may be about 0.1 wt% to about 1 wt%, and in some embodiments, about 0.15 wt% to about 0.5 wt% of the total weight of the glass fibers. In addition to titanium dioxide, the glass fibers may further include potassium oxide (KO) and / or lithium oxide (LiO) as a fluxing agent. For example, the concentration of potassium in the glass fibers may be about 0.2 wt% to about 1 wt%, and in some embodiments, about 0.3 wt% to about 0.5 wt%, of the total weight of the glass fibers. The concentration of lithium in the glass fibers may also be about 0.1 wt% to about 1 wt%, and in some embodiments, about 0.2 wt% to about 0.5 wt% of the total weight of the glass fibers. The glass fibers may also have a relatively small amount of sodium oxide (NaO).For example, the concentration of sodium in the glass fibers may be about 0.1 wt% to about 1 wt%, and in some embodiments, about 0.2 wt% to about 0.5 wt% of the total weight of the glass fibers. The concentrations of titanium, potassium, lithium, and sodium can be measured by ICP-AES. In one particular embodiment, the glass fibers may contain silica in an amount of about 57.5 wt% to about 59.5 wt%, alumina in an amount of about 17 wt% to about 20 wt%, calcium oxide in an amount of about 11 wt% to about 13.5 wt%, magnesium oxide in an amount of about 8.5 wt% to about 12.5 wt%, and optional sodium oxide, potassium oxide, lithium oxide, and / or titanium oxide. Other oxides, such as iron oxide (Fe2O3), may also be used.

[0028]

[0040] If desired, inorganic fibers may contain a sizing composition coated thereon to help improve hydrolysis resistance. The sizing composition may include an organosilane compound capable of forming Si-O-Si covalent bonds between the glass fiber surface and silanols obtained by hydrolysis of the silane compound, as well as between adjacent silanol groups. The resulting covalent bonds may form crosslinked structures on the surface of the fibers, enhancing their resistance to hydrolysis. Such organosilane compounds may, for example, comprise from about 2 wt% to about 40 wt%, in some embodiments from about 2.5 wt% to about 20 wt%, and in some embodiments, from about 5 wt% to about 15 wt% of the solids content (i.e., excluding water) of the sizing composition. The organosilane compound may be, for example, any alkoxysilane known in the art, such as vinylalkoxysilane, epoxyalkoxysilane, aminoalkoxysilane, mercaptoalkoxysilane, and combinations thereof. In one embodiment, for example, the organosilane compound may be represented by the following general formula: R 5 -Si-(R 6 )3 [In the formula, R 5are sulfide groups (e.g., -SH), alkyl sulfides containing 1 to 10 carbon atoms (e.g., mercaptopropyl, mercaptoethyl, mercaptobutyl, etc.), alkenyl sulfides containing 2 to 10 carbon atoms, alkynyl sulfides containing 2 to 10 carbon atoms, amino groups (e.g., NH), aminoalkyls containing 1 to 10 carbon atoms (e.g., aminomethyl, aminoethyl, aminopropyl, aminobutyl, etc.); aminoalkenyls containing 2 to 10 carbon atoms, and aminoalkynyls containing 2 to 10 carbon atoms; R 6 is an alkoxy group of 1 to 10 carbon atoms, such as methoxy, ethoxy, and propoxy. may have.

[0029]

[0041] Aminosilane compounds are particularly suitable and can include monomeric or oligomeric (<6 units) silanes. Aminotrialkoxysilanes can be used in certain embodiments to form a three-dimensional network of Si-O-Si covalent bonds on or around the surface of the fibers. Aminodialkoxysilanes can also be used in certain embodiments to form hair-like structures on the surface of the fibers. While not required to form a three-dimensional crosslinked protective sheath around the fibers, dialkoxysilanes can nevertheless facilitate impregnation of fiber bundles with polymer melts and wetting of individual fibers, and can reduce the hydrophilicity of the fiber surface, believed to contribute to resistance to hydrolysis. Therefore, it may be desirable to use trialkoxysilanes, dialkoxysilanes, or mixtures thereof in the sizing composition. Specific examples of suitable aminosilanes include aminodialkoxysilanes such as γ-aminopropylmethyldiethoxysilane, N-β-(aminoethyl)-gamma-aminopropylmethyldimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-β-(aminoethyl)-γ-aminoisobutylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, and N-β-(aminoethyl)-γ-aminopropylmethyldiethoxysilane; γ-aminopropyltriethoxysilane, γ- Aminotrialkoxysilanes such as aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltriethoxysilane, diethylene-triaminopropyltrimethoxysilane, bis-(γ-trimethoxysilylpropyl)amine, N-phenyl-γ-aminopropyltrimethoxysilane, γ-amino-3,3-dimethylbutyltrimethoxysilane, γ-aminobutyltriethoxysilane, and the like; and mixtures of any of the foregoing.

[0030]

[0042] In addition to the organosilane compound, the sizing composition may also contain one or more functionalized compounds capable of crosslinking to form a three-dimensional polymer network, which can further enhance the hydrolysis resistance of the fibers. When used, such functionalized compounds may comprise from about 5 wt% to about 90 wt%, in some embodiments from about 10 wt% to about 80 wt%, and in some embodiments, from about 15 wt% to about 70 wt% of the solids content (i.e., excluding water) of the sizing composition. In one embodiment, for example, the functionalized compound may be a blocked isocyanate. As used herein, the term "blocked isocyanate" refers to an isocyanate in which one or more isocyanate groups of an organic polyisocyanate have reversibly reacted with a blocking agent. In this manner, the resulting blocked (partially or fully) isocyanate groups are stable to active hydrogen at ambient temperatures, but can be unblocked and therefore reactive with active hydrogen at elevated temperatures, such as, for example, temperatures from about 90°C to about 210°C, in some embodiments from about 105°C to about 180°C, and in some embodiments, from about 125°C to about 170°C. Representative examples of suitable organic polyisocyanates include aliphatic isocyanates (e.g., trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, butylidene diisocyanate, etc.); (alicyclic)aliphatic isocyanates (e.g., isophorone diisocyanate (IPDI), 4,4′-diisocyanato-dicyclohexylmethane (HMDI)), etc.); aromatic isocyanates (e.g., p-phenylene diisocyanate); aliphatic-aromatic isocyanates (e.g., 4,4′-diphenylenemethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate, etc.); and mixtures thereof. Representative examples of suitable blocking agents include, but are not limited to, oximes such as methyl ethyl ketoxime, acetone oxime, and cyclohexanone oxime; lactams such as epsilon-caprolactam; alcohols; malonic acid esters; alkyl acetoacetates, triazoles; pyrazoles; phenols; amines such as benzyl t-butylamine; and mixtures thereof.In one embodiment, the blocked isocyanate is a blocked cycloaliphatic polyisocyanate.

[0031]

[0043] The functionalized compounds may also include polymers containing anhydride and / or carboxylic acid functional groups. Examples of such polymers include copolymers of ethylene-maleic anhydride, butadiene-maleic anhydride, isobutylene-maleic anhydride, acrylate-maleic anhydride, polyacrylic acid, and the like. When used, such anhydride and / or carboxylic acid functionalized polymers may comprise from about 5 wt% to about 60 wt%, in some embodiments from about 10 wt% to about 40 wt%, and in some embodiments from about 15 wt% to about 30 wt% of the solids content (i.e., excluding water) of the sizing composition. Other functionalized polymers may also be used, alone or in combination with polymers containing anhydride and / or carboxylic acid functional groups. In certain embodiments, epoxy-functionalized polymers such as epoxy phenol novolac (EPN), epoxy cresol novolac (ECN), and the like may be used. When used, such epoxy-functionalized polymers may comprise from about 30 wt% to about 90 wt%, in some embodiments from about 40 wt% to about 80 wt%, and in some embodiments, from about 50 wt% to about 70 wt% of the solids content (i.e., excluding water) of the sizing composition. In certain embodiments, combinations of such functionalized polymers may also be used. Indeed, it is believed that a dense cross-linked sheath may be formed around the inorganic fibers by reaction of the epoxy groups with the maleic anhydride and / or carboxylic acid groups.

[0032]

[0044] In addition to the organosilane compound and the functionalized compound, the sizing composition may also contain a film-forming agent, which can help protect the fibers from damage during processing and promote compatibility of the fibers with the polymer matrix. Particularly suitable film-forming agents are polymers such as polyurethanes, (meth)acrylate polymers, epoxy resin emulsions (e.g., based on epoxy bisphenol A or epoxy bisphenol F), epoxy ester resins, epoxy urethane resins, polyamides, and the like, as well as mixtures of any of the foregoing. In a particular embodiment, for example, the film-forming agent can include a polymer that is further functionalized, such as the polymer containing the blocked isocyanate functionality described above. Examples of such functionalized film-forming agents include polyester- and polyether-based polyurethanes containing blocked isocyanates. When used, such film-forming agents can comprise from about 0.1 wt % to about 50 wt %, in some embodiments from about 1 wt % to about 40 wt %, and in some embodiments, from about 5 wt % to about 30 wt % of the solids content (i.e., excluding water) of the sizing composition. Other additives, such as pH adjusters, lubricants, antistatic agents, antifoaming agents, crosslinking agents, and the like, may also be used in the sizing composition.

[0033]

[0045] The sizing composition can be applied to the surface of inorganic fibers in a variety of different ways. For example, a sizing composition can be applied to fibers formed from bushings. The entire composition can be applied to the fibers in a single step, or one or more components of the sizing composition can be applied separately. In one embodiment, a two-step application process can be used, for example, where a polymer containing anhydride and / or carboxylic acid functionality is applied in the first step and a polymer containing epoxy functionality is applied in the second step. In this method, the polymers may be crosslinked together only after application to the fiber surface. The other components of the sizing composition can be applied separately or in combination with one or both polymers. Regardless of the particular process used, one or more solvents (e.g., water) can be added to the components of the sizing composition during application to aid in the coating process. Once coated, the fibers can be dried to remove the solvent. In this regard, the moisture content of the coated fibers is typically about 0.5 wt% or less, in some embodiments about 0.2 wt% or less, and in some embodiments about 0.1 wt% or less. Similarly, the amount of sizing composition used is typically from about 0.3 wt.% to about 1.2 wt.%, in some embodiments from about 0.4 wt.% to about 1 wt.%, and in some embodiments, from about 0.5 wt.% to about 0.8 wt.%, based on the total weight of the coated fiber.

[0034] C. Organosilane Compounds

[0046] In addition to the above components, the polymer composition may also contain various other optional components to help improve overall properties. In one embodiment, for example, an organosilane compound may be used in the polymer composition in an amount of, for example, about 0.1 to about 8 parts by weight, in some embodiments about 0.3 to about 5 parts by weight, and in some embodiments about 0.5 to about 3 parts by weight, per 100 parts by weight of polyarylene sulfide. For example, the organosilane compound may comprise about 0.01 wt % to about 3 wt %, in some embodiments about 0.02 wt % to about 2 wt %, and in some embodiments about 0.05 to about 1 wt % of the polymer composition.

[0035]

[0047] The organosilane compound may be the same or different from the organosilane compound optionally used in the sizing composition for the inorganic fibers. In one embodiment, for example, the organosilane compound may be an alkoxysilane, such as those described above. Some representative examples of alkoxysilane compounds that may be used include mercaptopropyltrimethyoxysilane, mercaptopropyltriethoxysilane, aminopropyltriethoxysilane, aminoethyltriethoxysilane, aminopropyltrimethoxysilane, aminoethyltrimethoxysilane, ethylenetrimethoxysilane, ethylenetriethoxysilane, ethynetrimethoxysilane, ethynetriethoxysilane, aminoethylaminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, or 3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltrieth ... Examples of suitable organosilane compounds include trimethoxysilane, N-methyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, bis(3-aminopropyl)tetramethoxysilane, bis(3-aminopropyl)tetraethoxydisiloxane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-diallylaminopropyltrimethoxysilane, γ-diallylaminopropyltrimethoxysilane, and combinations thereof. Particularly suitable organosilane compounds are 3-aminopropyltriethoxysilane and 3-mercaptopropyltrimethoxysilane.

[0036] D. Other Optional Ingredients

[0048] Although by no means required, an impact modifier may also be used in the polymer composition. If used, the impact modifier may comprise from about 1 to about 20 parts by weight, in some embodiments from about 2 to about 15 parts by weight, and in some embodiments, from about 5 to about 10 parts by weight, per 100 parts by weight of polyarylene sulfide. For example, the impact modifier may comprise from about 0.1 wt % to about 20 wt %, in some embodiments, from about 0.5 wt % to about 15 wt %, and in some embodiments, from about 1 wt % to about 10 wt % of the polymer composition.

[0037]

[0049] Examples of suitable impact modifiers include polyepoxides, polyurethanes, polybutadienes, acrylonitrile-butadiene-styrenes, polyamides, block copolymers (e.g., polyether-polyamide block copolymers), and mixtures thereof. In one embodiment, an "epoxy-functionalized" olefin copolymer containing an average of two or more epoxy functional groups per molecule is used. The copolymer generally contains olefinic monomer units derived from one or more α-olefins. Examples of such monomers include linear and / or branched α-olefins having 2 to 20 carbon atoms, typically 2 to 8 carbon atoms. Specific examples include ethylene, propylene, 1-butene; 3-methyl-1-butene; 3,3-dimethyl-1-butene; 1-pentene; 1-pentene having one or more methyl, ethyl, or propyl substituents; 1-hexene having one or more methyl, ethyl, or propyl substituents; 1-heptene having one or more methyl, ethyl, or propyl substituents; 1-octene having one or more methyl, ethyl, or propyl substituents; 1-nonene having one or more methyl, ethyl, or propyl substituents; ethyl-, methyl-, or dimethyl-substituted 1-decene; 1-dodecene, and styrene. Particularly desirable α-olefin monomers are ethylene and propylene. The copolymer may also contain epoxy-functional monomer units. One example of such units is an epoxy-functional (meth)acrylic monomer component. As used herein, the term "(meth)acrylic" includes acrylic and methacrylic monomers, as well as their salts or esters, such as acrylate and methacrylate monomers. For example, suitable epoxy-functional (meth)acrylic monomers can include, but are not limited to, those containing 1,2-epoxy groups, such as glycidyl acrylate and glycidyl methacrylate. Other suitable epoxy-functional monomers include allyl glycidyl ether, glycidyl ethacrylate, and glycidyl itaconate.Other suitable monomers may also be used to assist in achieving the desired molecular weight.

[0038]

[0050] Of course, the copolymer may also contain other monomer units known in the art. For example, another suitable monomer may be a non-epoxy-functional (meth)acrylic monomer. Examples of such (meth)acrylic monomers include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, s-butyl acrylate, i-butyl acrylate, t-butyl acrylate, n-amyl acrylate, i-amyl acrylate, isobornyl acrylate, n-hexyl acrylate, 2-ethylbutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, methylcyclohexyl acrylate, cyclopentyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl meth ... Examples of suitable copolymers include methyl, 2-hydroxyethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, i-propyl methacrylate, i-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, i-amyl methacrylate, s-butyl methacrylate, t-butyl methacrylate, 2-ethylbutyl methacrylate, methylcyclohexyl methacrylate, cinnamyl methacrylate, crotyl methacrylate, cyclohexyl methacrylate, cyclopentyl methacrylate, 2-ethoxyethyl methacrylate, isobornyl methacrylate, and the like, and combinations thereof. In a particular embodiment, for example, the copolymer may be a terpolymer formed from an epoxy-functional (meth)acrylic monomer component, an α-olefin monomer component, and a non-epoxy-functional (meth)acrylic monomer component. The copolymer may have, for example, the following structure:

[0039] [ka]

[0040] (wherein x, y, and z are 1 or greater) The copolymer may be poly(ethylene-co-butyl acrylate-co-glycidyl methacrylate) having the formula:

[0041]

[0051] The relative proportions of the monomer components can be selected to achieve a balance between epoxy reactivity and melt flow rate. More specifically, a high epoxy monomer content can result in good reactivity with the polyarylene sulfide, while too much can reduce the melt flow rate to the extent that the copolymer adversely affects the melt strength of the polymer blend. Thus, in most embodiments, the epoxy-functional (meth)acrylic monomer comprises from about 1 wt% to about 20 wt%, in some embodiments from about 2 wt% to about 15 wt%, and in some embodiments, from about 3 wt% to about 10 wt% of the copolymer. The α-olefin monomer can similarly comprise from about 55 wt% to about 95 wt%, in some embodiments from about 60 wt% to about 90 wt%, and in some embodiments, from about 65 wt% to about 85 wt% of the copolymer. Other monomer components (e.g., non-epoxy functional (meth)acrylic monomers), if used, may comprise from about 5 wt% to about 35 wt%, in some embodiments from about 8 wt% to about 30 wt%, and in some embodiments, from about 10 wt% to about 25 wt% of the copolymer. The resulting melt flow rates, as determined according to ASTM D1238-20 at a load of 2.16 kg and a temperature of 190°C, are typically from about 1 to about 30 grams per 10 minutes ("g / 10 min"), in some embodiments from about 2 to about 20 g / 10 min, and in some embodiments from about 3 to about 15 g / 10 min.

[0042]

[0052] If desired, additional impact modifiers may also be used in combination with the epoxy-functional impact modifier. For example, the additional impact modifier may include a block copolymer in which at least one phase is made of a material that is hard at room temperature but becomes fluid upon heating, and the other phase is a soft material, such as rubber, at room temperature. By way of example, the block copolymer may have an AB or ABA block copolymer repeat structure, where A represents the hard segment and B is the soft segment. Non-limiting examples of impact modifiers having an AB repeat structure include polyamide / polyether, polysulfone / polydimethylsiloxane, polyurethane / polyester, polyurethane / polyether, polyester / polyether, polycarbonate / polydimethylsiloxane, and polycarbonate / polyester. Triblock copolymers may similarly contain polystyrene as the hard segment and either polybutadiene, polyisoprene, or polyethylene-co-butylene as the soft segment. Similarly, styrene-butadiene repeat copolymers and polystyrene / polyisoprene repeat polymers may be used. In a particular embodiment, the block copolymer may have alternating blocks of polyamide and polyether. Such materials are commercially available, for example, from Atofina under the trade name PEBAX™. The polyamide blocks may be derived from copolymers of diacid and diamine components or may be prepared by homopolymerization of cyclic lactams. The polyether blocks may be derived from homo- or copolymers of ethylene oxide, propylene oxide, and cyclic ethers such as tetrahydrofuran.

[0043]

[0053] Siloxane polymers may also be used in the polymer composition. The siloxane polymer typically comprises about 0.05 to about 10 parts by weight, in some embodiments about 0.1 to about 8 parts by weight, and in some embodiments about 0.5 to about 5 parts by weight, per 100 parts by weight of polyarylene sulfide. For example, the siloxane polymer may comprise about 0.05 wt% to about 15 wt%, in some embodiments about 0.5 wt% to about 10 wt%, and in some embodiments about 1 wt% to about 8 wt% of the polymer composition.

[0044]

[0054] Siloxane polymers can improve the processing of the composition by, for example, providing better mold filling, internal lubrication, mold release, etc. Additionally, siloxane polymers are also believed to be less likely to migrate or diffuse to the surface of the composition, which further minimizes the possibility of phase separation and further aids in reducing impact energy. Siloxane polymers have high molecular weights, e.g., greater than about 100,000 grams / mole, in some embodiments greater than about 200,000 grams / mole, and in some embodiments, from about 500,000 grams / mole to about 2,000,000 grams / mole. Siloxane polymers have relatively high kinematic viscosities at 25° C., e.g., greater than about 10,000 centistokes, in some embodiments greater than about 30,000 centistokes, and in some embodiments, from about 50,000 to about 50×10. 6 Centistokes, e.g., approximately 1 x 10 6 ~50×10 6 The viscosity of the siloxane polymer can be determined according to ASTM D445-21.

[0045]

[0055] Any of a variety of high molecular weight siloxane polymers can generally be used in the polymer composition. High molecular weight siloxane polymers generally contain siloxane-based monomer residue repeat units. As used herein, "siloxane" refers to a polymer having the following structure:

[0046] [ka]

[0047] (In the formula, R 1 and R 2 represents a monomer residue repeat unit having ) which are independently hydrogen or hydrocarbyl moieties, known in silicone chemistry as the "M" group).

[0048]

[0056] The silicone is known in silicone chemistry as the "Q" group.

[0049] [ka]

[0050] or known in silicone chemistry as the "T" group

[0051] [ka]

[0052] It may also include branch points such as

[0057] As used herein, the term "hydrocarbyl" refers to a monovalent group formed by removing a hydrogen atom from a hydrocarbon (e.g., an alkyl group such as ethyl, or an aryl group such as phenyl). In one or more embodiments, the siloxane monomer residue may be either a dialkyl, diaryl, dialkaryl, or diaralkyl siloxane, having the same or different alkyl, aryl, alkaryl, or aralkyl moieties. In one embodiment, R 1 and R 2 Each of C1 to C 20 , C1~C 12 or C1-C6 alkyl (e.g., methyl, ethyl, propyl, butyl, etc.), aryl (e.g., phenyl), alkaryl, aralkyl, cycloalkyl (e.g., cyclopentyl), arylenyl, alkenyl, cycloalkenyl (e.g., cyclohexenyl), alkoxy (e.g., methoxy), etc., and combinations thereof. In various embodiments, R 1 and R 2may have the same or different number of carbon atoms. 1 and R 2 Each hydrocarbyl group in is a saturated and optionally linear alkyl group. In addition, the alkyl group in such an embodiment is a group that is present in the R 1 and R 2 can be identical for each of R 1 and R 2 Non-limiting examples of alkyl groups suitable for use in include methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, isobutyl, t-butyl, or a combination of two or more thereof.

[0053]

[0058] Additionally, the siloxane polymer may contain R groups such as vinyl groups, hydroxyl groups, hydrides, isocyanate groups, epoxy groups, acid groups, halogen atoms, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, alkenyloxy groups, alkoxyalkoxy groups, or aminoxy groups and combinations thereof. 1 and / or R 2 The polymer composition may contain a variety of end groups as groups. Additionally, the polymer composition may contain a mixture of two or more siloxane polymers.

[0054]

[0059] In some embodiments, high molecular weight siloxane polymers can be demonstrated by copolymerizing a plurality of siloxane polymers having low weight average molecular weights (e.g., molecular weights less than 100,000 grams / mole) with a polysiloxane linker. In one particular embodiment, for example, a resin can be formed by copolymerizing one or more low molecular weight siloxane polymers with a linear polydiorganosiloxane linker as described in U.S. Patent No. 6,072,012 (Juen et al.). The substantially linear polydiorganosiloxane linker can have the following general formula: (R 3 (3-p) R 4 p SiO 1 / 2 )(R 32SiO 2 / 2 ) x ((R 3 R 4 SiO 2 / 2 )(R 3 2SiO 2 / 2 ) x ) y (R 3 (3-p) R 4 p SiO 1 / 2 ) [In the formula, Each R 3 is independently a monovalent radical selected from the group consisting of alkyl, aryl, and arylalkyl groups; Each R 4 are independently monovalent radicals selected from the group consisting of hydrogen, hydroxyl, alkoxy, oximo, alkyloximo, and aryloximo groups, where at least two R 5 The groups are typically present in each molecule and are attached to different silicon atoms; p is 0, 1, 2, or 3; x ranges from 0 to 200, and in some embodiments, from 0 to 100; y ranges from 0 to 200, and in some embodiments, from 0 to 100. may have.

[0055]

[0060] In certain embodiments, the siloxane polymer may be provided in the form of a masterbatch comprising a carrier resin. The carrier resin may, for example, comprise from about 0.05 wt% to about 15 wt%, in some embodiments from about 0.1 wt% to about 10 wt%, and in some embodiments, from about 0.5 wt% to about 8 wt% of the polymer composition. Any of a variety of carrier resins may be used, such as polyolefins (e.g., ethylene polymers, propylene polymers), polyamides, and the like. In one embodiment, for example, the carrier resin is an ethylene polymer. Ethylene polymers are polymers of ethylene and C3-C6 20 α-olefin or C3-C 12The copolymer may also be a copolymer with an α-olefin, such as an α-olefin. Suitable α-olefins may be linear or branched (e.g., one or more C1-C3 alkyl branches or aryl groups). Specific examples include 1-butene; 3-methyl-1-butene; 3,3-dimethyl-1-butene; 1-pentene; 1-pentene having one or more methyl, ethyl, or propyl substituents; 1-hexene having one or more methyl, ethyl, or propyl substituents; 1-heptene having one or more methyl, ethyl, or propyl substituents; 1-octene having one or more methyl, ethyl, or propyl substituents; 1-nonene having one or more methyl, ethyl, or propyl substituents; ethyl-, methyl-, or dimethyl-substituted 1-decene; 1-dodecene; and styrene. Particularly desirable α-olefin comonomers are 1-butene, 1-hexene, and 1-octene. The ethylene content of such copolymers may range from 60 mol % to about 99 mol %, in some embodiments from about 80 mol % to about 98.5 mol %, and in some embodiments, from about 87 mol % to about 97.5 mol %. The α-olefin content may similarly range from about 1 mol % to about 40 mol %, in some embodiments from about 1.5 mol % to about 15 mol %, and in some embodiments, from about 2.5 mol % to about 13 mol %. The density of ethylene polymers may vary depending on the type of polymer used, but is generally from about 0.85 to about 0.96 grams per cubic centimeter (g / cm ). 3 ) range. Polyethylene "plastomer" is, for example, about 0.85 to about 0.91 g / cm 3 Similarly, "linear low density polyethylene" (LLDPE) may have a density ranging from about 0.91 to about 0.940 g / cm, as determined according to ASTM D792. 3 "Low density polyethylene" (LDPE) can have a density ranging from about 0.910 to about 0.940 g / cm 3 "High density polyethylene" (HDPE) can have a density ranging from about 0.940 to about 0.960 g / cm 3Some non-limiting examples of high molecular weight siloxane polymer masterbatches that can be used include, for example, MB50-001, MB50-002, MB50-313, MB50-314, and MB50-3 from Dow Corning. It is available under 21 trade names.

[0056]

[0061] The polymer composition may also contain a heat stabilizer. For example, the heat stabilizer may be a phosphite stabilizer, such as an organic phosphite. For example, suitable phosphite stabilizers include monophosphites and diphosphites, where diphosphites have a molecular structure that inhibits moisture absorption and / or has a relatively high spiro isomer content. For example, a diphosphite stabilizer having a spiro isomer content of greater than 90%, e.g., greater than 95%, e.g., greater than 98%, may be selected. Specific examples of such diphosphite stabilizers include, for example, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, mixtures thereof, and the like. When used, the heat stabilizer typically comprises from about 0.1 wt % to about 3 wt %, and in some embodiments, from about 0.2 wt % to about 2 wt %, of the composition.

[0057]

[0062] Nucleating agents can also be used to further enhance the crystallization properties of the composition.Examples of such nucleating agents include inorganic crystalline compounds such as boron-containing compounds (e.g., boron nitride, sodium tetraborate, potassium tetraborate, calcium tetraborate, etc.), alkaline earth metal carbonates (e.g., calcium magnesium carbonate), oxides (e.g., titanium oxide, aluminum oxide, magnesium oxide, zinc oxide, antimony trioxide, etc.), silicates (e.g., talc, sodium aluminum silicate, calcium silicate, magnesium silicate, etc.), alkaline earth metal salts (e.g., calcium carbonate, calcium sulfate, etc.). Boron nitride (BN) has been found to be particularly beneficial when used in the polymer compositions of the present invention. Boron nitride exists in a variety of crystalline forms (e.g., h-BN—hexagonal, c-BN—cubic or spharlerite, and w-BN—wurtzite), and generally any of these can be used in the present invention. The hexagonal form is particularly preferred due to its stability and softness.

[0058]

[0063] If desired, a crosslinking system can also be used in combination with any optional impact modifier to help further improve the strength and flexibility of the composition under a variety of different conditions. In such circumstances, a crosslinked product can be formed from a crosslinkable polymer composition containing a polyarylene sulfide together with one or more impact modifiers, a siloxane polymer, a filler, a crosslinking system, and other optional additives. When used, the crosslinking system, which can contain one or more crosslinking agents, typically accounts for about 0.1 to about 15 parts, in some embodiments about 0.2 to about 10 parts, and in some embodiments about 0.5 to about 5 parts, per 100 parts of polyarylene sulfide, and about 0.05 wt% to about 15 wt%, in some embodiments about 0.1 wt% to about 10 wt%, and in some embodiments about 0.2 wt% to about 5 wt% of the polymer composition. The use of such a crosslinking system can significantly improve the compatibility and distribution of the polyarylene sulfide and the impact modifier. For example, the impact modifier can be dispersed in the polymer composition in the form of discrete domains of nanoscale size. For example, the domains can have an average cross-sectional dimension of from about 1 to about 1000 nanometers, in some embodiments from about 5 to about 800 nanometers, and in some embodiments, from about 10 to about 500 nanometers. The domains can have a variety of different shapes, such as ellipsoidal, spherical, cylindrical, plate-like, tubular, etc. Such improved dispersion can result in better mechanical properties or allow equivalent mechanical properties to be achieved with less impact modifier.

[0059]

[0064] Any of a variety of different crosslinkers can generally be used in the crosslinking system. In one embodiment, for example, the crosslinking system may include a metal carboxylate. While not intending to be limited by theory, it is believed that the metal atom in the carboxylate may act as a Lewis acid, accepting electrons from oxygen atoms located in the functional groups (e.g., epoxy functional groups) of the impact modifier. Upon reaction with the carboxylate, the functional group becomes activated and can readily be attacked at either carbon atom in the three-membered ring via a nucleophilic substitution reaction, thereby forming crosslinks between the impact modifier chains. The metal carboxylate is typically a metal salt of a fatty acid. The metal cation used in the salt can vary but is typically a divalent metal such as calcium, magnesium, lead, barium, strontium, zinc, iron, cadmium, nickel, copper, tin, etc., and mixtures thereof. Zinc is particularly preferred. The fatty acid may generally be any saturated or unsaturated acid with a carbon chain length of about 8 to 22 carbon atoms, and in some embodiments, about 10 to about 18 carbon atoms. The acid may be substituted if desired. Suitable fatty acids include, for example, lauric acid, myristic acid, behenic acid, oleic acid, palmitic acid, stearic acid, ricinoleic acid, capric acid, neodecanoic acid, hydrogenated tallow fatty acid, hydroxystearic acid, hydrogenated castor oil fatty acid, erucic acid, coconut oil fatty acid, and the like, and mixtures thereof. The metal carboxylate typically comprises from about 0.05 wt% to about 5 wt%, in some embodiments from about 0.1 wt% to about 2 wt%, and in some embodiments, from about 0.2 wt% to about 1 wt% of the polymer composition.

[0060]

[0065] The crosslinking system can also employ crosslinkers that are "multifunctional" to the extent that they contain at least two reactive functional groups. Such multifunctional crosslinkers can act as weak nucleophiles capable of reacting with activated functional groups (e.g., epoxy functional groups) on the impact modifier. The multifunctional nature of such molecules allows them to crosslink two functional groups on the impact modifier, effectively acting as a curing agent. Multifunctional crosslinkers generally contain two or more reactively functional terminal moieties linked by bonds or non-polymeric (non-repeating) linking moieties. By way of example, crosslinkers can include diepoxides, multifunctional epoxides, diisocyanates, polyisocyanates, polyhydric alcohols, water-soluble carbodiimides, diamines, diols, diaminoalkanes, multifunctional carboxylic acids, diacid halides, and the like. Multifunctional carboxylic acids and amines are particularly suitable. Specific examples of polyfunctional carboxylic acid crosslinkers include, but are not limited to, isophthalic acid, terephthalic acid, phthalic acid, 1,2-di(p-carboxyphenyl)ethane, 4,4'-dicarboxydiphenyl ether, 4,4'-bisbenzoic acid, 1,4- or 1,5-naphthalenedicarboxylic acid, decahydronaphthalenedicarboxylic acid, norbornene dicarboxylic acid, bicyclooctane dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid (both cis and trans), 1,4-hexylene dicarboxylic acid, adipic acid, azelaic acid, dicarboxydodecanoic acid, succinic acid, maleic acid, glutaric acid, suberic acid, azelaic acid, and sebacic acid. Corresponding dicarboxylic acid derivatives, such as carboxylic acid diesters, carboxylic acid anhydrides, or carboxylic acid halides having 1 to 4 carbon atoms in the alcohol group, can also be used. In certain embodiments, aromatic dicarboxylic acids, such as isophthalic acid or terephthalic acid, are particularly suitable.

[0061]

[0066] When used, the multifunctional crosslinker typically comprises from about 50 wt% to about 95 wt%, in some embodiments from about 60 wt% to about 90 wt%, and in some embodiments, from about 70 wt% to about 85 wt% of the crosslinked system, while the metal carboxylate typically comprises from about 5 wt% to about 50 wt%, in some embodiments, from about 10 wt% to about 40 wt%, and in some embodiments, from about 15 wt% to about 30 wt% of the crosslinked system. For example, the multifunctional crosslinker may comprise from about 0.1 wt% to about 10 wt%, in some embodiments, from about 0.2 wt% to about 5 wt%, and in some embodiments, from about 0.5 wt% to about 3 wt% of the polymer composition. Of course, in certain embodiments, the composition may be entirely free of the multifunctional crosslinker, or the crosslinked system may be entirely free of the metal carboxylate.

[0062]

[0067] Still other ingredients that may be included in the composition include, for example, nucleating agents, particulate fillers (e.g., talc, mica, etc.), pigments (e.g., black pigments), colorants, antioxidants, stabilizers, surfactants, lubricants, and other materials added to enhance properties and processability.

[0063]

[0068] In one embodiment, for example, the polymer composition may contain a nucleating agent, such as boron-containing particles. When used, such particles may comprise from about 0.01 wt % to about 5 wt %, in some embodiments, from about 0.02 wt % to about 2 wt %, and in some embodiments, from about 0.05 wt % to about 1 wt % of the polymer composition. The boron-containing particles may exhibit surprisingly high graphitization indices, such as greater than about 4, greater than about 5, or greater than about 6, in some embodiments, from about 6 to about 10, and in some embodiments, from about 7 to about 9. The graphitization index (also commonly referred to as the graphite index) is a parameter that describes the structural quality of boron-containing particles. Boron-containing particles, such as boron nitride, exist in several crystalline forms, including hexagonal, which is similar in structure to graphite; cubic, which resembles diamond; and wurtzite, which is similar to lonsdaleite (also known as hexagonal diamond). After formation, the boron-containing particles may have different degrees of crystallinity. To measure this crystallinity, a structural figure of merit called the graphitization index has been developed. The graphitization index is derived from X-ray diffraction and is the ratio of the area under the [(100) + (101)] peak to the area under the (102) peak. The graphitization index describes the degree of order in the stacking of layers along the c-axis of the material. The graphitization index can vary widely, for example, from about 1 for well-ordered, highly crystalline particles to about 50 for so-called turbostratic particles, where the layers exhibit random rotation and translation around the normal.

[0064]

[0069] Along with low crystallinity, the boron-containing nucleating agent may also have a small particle size. For example, the nucleating agent may have an average particle size of less than about 10 micrometers, in some embodiments from about 0.5 to about 10 micrometers, in some embodiments from about 1 micrometer to about 9 micrometers, and in some embodiments from about 2 to about 8 micrometers, as determined, for example, according to precipitation, laser diffraction, or any other suitable technique. For example, particle size distribution may be determined according to standard test methods such as ASTM D4464 or ASTM B822. The nucleating agent may also have a large specific surface area. The specific surface area may be, for example, greater than 15 m / g, about 17 m / g, or greater than 15 m / g. 2 / g or approximately 19m 2In one embodiment, the specific surface area may be very large, for example, about 30 m 2 The specific surface area can be greater than 1 / g. The specific surface area is generally known in the art and can be determined according to standard methods, such as the physical gas adsorption (BET) method using nitrogen as the adsorbent gas, as described by Brunauer, Emmet, and Teller (J. Amer. Chem. Soc., vol. 60, February 1938, pp. 309-319). The combination of a small particle size and a large specific surface area can result in a boron-containing nucleating agent having an average particle size to specific surface area ratio of about 0.001 to about 1, e.g., about 0.01 to about 0.8, or about 0.02 to about 0.25. The nucleating agent particles can have any overall shape. For example, the nucleating agent can include high aspect ratio particles having an acicular or plate-like structure. The boron-containing nucleating agent may also be in the form of agglomerated particles, in which individual high aspect ratio particles are clumped together through weak chemical bonds, such as van der Waals forces, without any particular orientation or highly ordered pattern. Larger, non-agglomerated particles may also be used. For example, particles containing multiple stacked, plate-like primary particles and particles in which no primary structure is apparent, such as granular or crushed particles formed into large sintered bodies, may be used.

[0065]

[0070] Suitable boron-containing nucleating agents can include any boron-containing material generally known in the art that can provide the disclosed properties. Exemplary boron-containing nucleating agents include, but are not limited to, boron nitride, sodium tetraborate, potassium tetraborate, calcium tetraborate, and the like, and mixtures thereof. Boron nitride (BN) has been found to be particularly useful. Boron nitride exists in a variety of crystalline forms (e.g., h-BN—hexagonal, c-BN—cubic or spharlerite, and w-BN—wurtzite), and generally, any of these can be used in the present invention. The hexagonal form can be utilized in one embodiment due to its stability and softness.

[0066] II. Melt Processing

[0071] The method of combining the polyarylene sulfide, inorganic fibers, and other optional additives can vary as known in the art. For example, the materials can be fed simultaneously or sequentially to a melt-processing device that dispersively blends the materials. Batch and / or continuous melt-processing techniques can be used. For example, a mixer / kneader, Banbury mixer, Farrel continuous mixer, single-screw extruder, twin-screw extruder, roll mill, etc. can be utilized to blend and melt-process the materials. One particularly suitable melt-processing device is a co-rotating twin-screw extruder (e.g., a Leistritz co-rotating fully intermeshed twin-screw extruder). Such an extruder can include a feed section and a discharge section, providing a high-intensity distributive and dispersive mixer. For example, the components can be fed into the same or different feed sections of a twin-screw extruder and melt-blended to form a substantially homogeneous molten mixture. Melt-blending can occur under high shear / pressure and can be heated to ensure sufficient dispersion. For example, melt processing may occur at temperatures of from about 100° C. to about 500° C., and in some embodiments, from about 150° C. to about 300° C. Similarly, the apparent shear rate during melt processing may be from about 100 s -1 ~about 10,000 seconds -1 , in some embodiments, about 500 seconds -1 ~Approx. 1,500 seconds -1 Of course, other variables such as residence time during melt processing, which is inversely proportional to throughput rate, can also be controlled to achieve the desired degree of uniformity.

[0067]

[0072] If desired, one or more distributive and / or dispersive mixing elements may be used within the mixing section of the melt processing unit. Suitable distributive mixers include, for example, Saxon, Examples of suitable dispersion mixers include Dulmage and Cavity Transfer mixers. Similarly, suitable dispersion mixers include Blister Ring, Leroy / Maddock, and CRD mixers. As is well known in the art, mixers may be further enhanced by using pins in the barrel to fold and reorient the polymer melt, such as those used in Buss Kneader extruders, Cavity Transfer mixers, and Vortex Intermeshing Pin mixers. The screw speed can also be controlled to improve the properties of the composition. For example, the screw speed may be about 400 rpm or less, and in one embodiment, for example, about 200 rpm to about 350 rpm, or about 225 rpm to about 325 rpm. In one embodiment, compounding conditions can be balanced to provide a polymer composition exhibiting improved properties. For example, compounding conditions can include a screw design providing weak, medium, or strong screw conditions. For example, a system can have a weak-strength screw design with a single melting section in the downstream half of the screw for gentle melting and uniform distribution of the melt. A medium-strength screw design can have a more powerful dissolving section upstream of the filler feed barrel, focusing more powerful dispersing elements for uniform dissolution. Additionally, it can have a separate, gentler mixing section downstream to mix the filler. This mixing section is weaker than the weak-strength design, but can be more powerful overall, adding to the shear strength of the screw. A highly strong screw design can have the strongest shear strength of the three. The main dissolving section can consist of a long array of highly dispersive kneading blocks. The downstream mixing section can utilize a mix of distributive and focused dispersing elements to achieve uniform dispersion of all filler types. The shear strength of a highly strong screw design can be significantly higher than the other two designs. In one embodiment, the system can include a medium-to-strong screw design with a relatively moderate screw speed (e.g., about 200 rpm to about 300 rpm).

[0068]

[0073] The resulting polymer composition (before being formed into a molded part) may have a crystallization temperature of up to about 250° C., in some embodiments from about 100° C. to about 245° C., and in some embodiments, from about 150° C. to about 240° C. The polymer composition may be subjected to a temperature of about 310° C. and a shear rate of 400 s in accordance with ISO 11443:2021. -1 The composition may also exhibit a relatively low melt viscosity, for example, about 30 kP or less, in some embodiments about 20 kP or less, in some embodiments about 10 kP or less, in some embodiments about 5 kP or less, and in some embodiments, from about 2 to about 50 kP, as determined by

[0069] III. Molded Components

[0074] A variety of different components can be molded using the polymer compositions described herein. Furthermore, components can be molded from the polymer compositions using a variety of different techniques. Suitable techniques include, for example, injection molding, low-pressure injection molding, extrusion compression molding, gas injection molding, foam injection molding, low-pressure gas injection molding, low-pressure foam injection molding, gas extrusion compression molding, foam extrusion compression molding, extrusion molding, foam extrusion molding, compression molding, foam compression molding, and gas compression molding. For example, an injection molding system can be used, including a mold into which the polymer composition can be injected. The time in the injector can be controlled and optimized to prevent pre-solidification of the polymer matrix. Once the cycle time is reached and the barrel is filled for discharge, a piston can be used to inject the composition into the mold cavity. Compression molding systems can also be used. Similar to injection molding, shaping of the polymer composition into the desired article also occurs in the mold. The composition can be placed into a compression mold using any known technique, for example, by lifting it with an automated robotic arm. The temperature of the mold can be maintained at or above the solidification temperature of the polymer composition for the desired time to allow solidification. The molded article can then be solidified by lowering the temperature below the melting point. The resulting article can be demolded. The cycle time for each molding process can be adjusted to match the polymer composition to achieve sufficient bonding and enhance overall process productivity.

[0070] IV. Product Use

[0075] As previously mentioned, the disclosed polymer compositions are particularly beneficial for use in components of electric vehicles, such as battery-powered electric vehicles, fuel cell electric vehicles, plug-in hybrid electric vehicles (PHEVs), mild hybrid electric vehicles (MHEVs), and full hybrid electric vehicles (FHEVs). For example, referring to FIG. 1 , one embodiment of an electric vehicle 112 is shown that includes a powertrain 110. The powertrain 110 includes one or more electric machines connected to a transmission 116, which in turn is mechanically connected to a driveshaft 120 and drive wheels 122. Although by no means required, the transmission 116 in this particular embodiment is also connected to an engine 118; however, the description herein is equally applicable to purely electric vehicles. The electric machine 114 can operate as a motor or a generator to provide propulsion and deceleration capabilities. The powertrain 110 also includes a propulsion source, such as a battery assembly 124, that stores and supplies energy for use by the electric machine 114. Battery assembly 124 typically provides a high voltage current output (eg, DC current at a voltage between about 400 volts and about 800 volts) from one or more battery cell arrays, which may include one or more battery cells.

[0071]

[0076] The powertrain 110 may also contain at least one power electronics module 126, which is connected to the battery assembly 124 (also commonly referred to as a battery pack) and may contain power converters (e.g., converters, etc., and combinations thereof). The power electronics module 126 is typically electrically connected to the electric machine 114 and provides the ability to transfer electrical energy bidirectionally between the battery assembly 124 and the electric machine 114. For example, the battery assembly 124 may apply a DC voltage, while the electric machine 114 may require a three-phase AC voltage to function. The power electronics module 126 can convert the DC voltage to a three-phase AC voltage as needed by the electric machine 114. In a regeneration mode, the power electronics module 126 can convert the three-phase AC voltage from the electric machine 114, acting as a generator, to the DC voltage needed by the battery assembly 124. The battery assembly 124 may also provide energy for other vehicle electrical systems. For example, the powertrain may use a DC / DC converter to convert high-voltage DC power generated from the battery assembly 124 into a low-voltage DC supply compatible with other vehicle loads, such as a compressor and an electric heater. In a typical vehicle, the low-voltage system is electrically connected to an auxiliary battery 130 (e.g., a 12V battery). A battery energy control module (BECM) 133 may also be present in communication with the battery assembly 124 and may include an electronic monitoring system that acts as a controller for the battery assembly 124 and manages the temperature and state of charge of each battery cell. The battery assembly 124 may also have a temperature sensor 131, such as a thermistor or other thermometer. The temperature sensor 131 may be in communication with the BECM 133 to provide temperature data regarding the battery assembly 124. The temperature sensor 131 may be located on or near a battery cell within the traction battery 124. It is also contemplated that multiple temperature sensors 131 may be used to monitor the temperature of the battery cells.

[0072]

[0077] In certain embodiments, the battery assembly 124 may be recharged by an external power source 136, such as an electrical outlet. The external power source 136 may be electrically connected to an electric vehicle supply equipment (EVSE), which regulates and manages the transfer of electrical energy between the power source 136 and the vehicle 112. The EVSE 138 may have a charging connector 140 for plugging into a charging port 134 of the vehicle 112. The charging port 134 may be any type of port configured to transfer power from the EVSE 138 to the vehicle 112 and may be electrically connected to a charger or onboard power conversion module 132. The power conversion module 132 may condition the power provided by the EVSE 138 and provide the appropriate voltage and current levels to the battery assembly 124. The power conversion module 132 may interface with the EVSE 138 to coordinate the delivery of power to the vehicle 112.

[0073]

[0078] The polymer compositions described herein may be included in various components of the electric vehicle shown in FIG. 1 . For example, bus bars (an example of which is shown in FIG. 2 ) may be used to electrically connect the individual cells of the battery assembly 124. Referring to FIG. 3 , for example, the battery assembly 124 may include multiple battery cells 158. The battery cells 158 may be stacked in parallel to form a group of battery cells (sometimes referred to as a battery array). In one embodiment, the battery cells 158 are prismatic lithium-ion batteries. However, battery cells having other shapes (cylindrical, pouch, etc.) and / or chemistries (nickel-metal hydride, lead-acid, etc.) may alternatively be utilized within the scope of the present disclosure. Each battery cell 158 includes a positive terminal (denoted by a (+) symbol) and a negative terminal (denoted by a (-) symbol). The battery cells 158 are arranged such that the terminal of each battery cell 158 is positioned adjacent to the terminal of an adjacent battery cell 158 having the opposite polarity. As used herein, the terms "battery," "cell," and "battery cell" can be used interchangeably and can refer to any type of individual battery element used in a battery system. The batteries described herein typically include lithium-based batteries, but can also include a variety of chemistries and configurations, including iron phosphate, metal oxide, lithium-ion polymer, nickel-metal hydride, nickel-cadmium, nickel-based batteries (such as hydrogen, zinc, and cadmium), and any other battery type compatible with electric vehicles. For example, some embodiments may use the Panasonic® 6831NCR18650 battery cell, or some variations of the 18650 form factor, measuring 6.5 cm by 1.8 cm and weighing approximately 45 g.

[0074]

[0079] The manner in which a busbar connects to individual battery cells of a battery assembly 124, such as that shown in FIG. 3, can vary as is known in the art. Referring to FIG. 2, one embodiment of a busbar 10 is shown, including electrical conductors 12. The electrical conductors 12 include a conductive material 18, such as copper, aluminum, or an aluminum alloy, and may generally be in the form of a solid bar, a hollow tube, or the like. The busbar 10 includes connector portions 14 at either end configured to mate with the terminals of two or more batteries. An insulating portion 16 (e.g., a coating or molding compound) including a polymer composition described herein may cover a portion of the conductive material of the electrical conductors 12. To form the busbar 10, the insulating portion 16 may be applied to the surface of the conductive material 18. For example, a bar or tube of the conductive material 18 may be inserted into a preformed tube of insulating coating 16 (e.g., an extruded tube sized and cut to precise proportions), after which the busbar 10 can be shaped into any suitable form. In another embodiment, an insulating coating may be applied to the surface of the conductive material 18 in the melt and allowed to solidify on the surface of the conductive material where applied.

[0075]

[0080] Of course, the bus bars may be provided in any suitable shape and size. By way of example, the bus bars may be used as templates for uniformly positioning individual battery cells within each battery assembly produced. In such an embodiment, the bus bars may hold the individual batteries of the battery assembly 124 in place during the manufacturing process, allowing thermal padding or injection housing, which may be formed from the polymer compositions described herein, to be added without displacing the individual battery cells.

[0076]

[0081] Apart from bus bars, other components may also use the polymer composition of the present invention. As an example, FIG. 4 depicts a block diagram of the battery electronics of an electric vehicle 112. The illustrated battery electronics system includes a battery assembly 124 and a current sensor 142. As shown, the current sensor 142 is connected between the battery assembly 124 and a load / source 144. The current sensor 142 is connected to a load / source 144. The current sensor 142 may be configured to measure the current flowing from the battery assembly 124 to the load / source 144 when the load / source 144 is a load, such as the electric machine 114. Similarly, the current sensor 142 may be configured to measure the current flowing from the load / source 144 to the battery assembly 124 when the load / source 144 is a source, such as the external power source 136. The BECM 133 may be configured to enable operation of the current sensor 142. Additionally, the BECM 133 may be configured to read an output generated by the current sensor 142 indicative of the current flowing between the battery assembly 124 and the load / source 144.

[0077]

[0082] 5 shows one embodiment of a current sensor 142. The current sensor 142 may include a current input terminal 141 and a current output terminal 143 as well as a reference ground 145, a mains voltage (Voltage at common collector (VCC)) 146, and an output port 147. The current sensor 142 may also include a housing 148 comprising the described polymer composition that may house other components of the current sensor 142 (e.g., resistors, capacitors, converters, processing chips, etc.).

[0078]

[0083] Another component of an electric vehicle into which the described polymer compositions can be incorporated is an inverter system, an exemplary embodiment of which is shown in FIG. 6 . The system includes an inverter module 320 and an interconnection system 335. The interconnection system 335 includes an electromagnetic interference (EMI) core 330 and an EMI filter device 325. The inverter module 320 is coupled to the interconnection system 335 by a pair of bus bars 310. The EMI core 330 is located between the EMI filter device 325 and the inverter module 320 and is in communication with the bus bars 310. The EMI filter device 325 includes an EMI filter card 340 and a pair of bolts 350 and 352, including a positive terminal (+) bolt 350 and a negative terminal (-) bolt 352, for coupling to a power source, such as the battery assembly 124. The EMI core 330 is coupled to the bolts 350 and 352 by the bus bars 310. The EMI filter card 340 is also coupled between ground and the bus bars 310 via a pair of wires 334. The inverter module 320 includes a large number of transistors (not shown). The transistors in the inverter module 320 switch relatively quickly (e.g., 5-20 kHz). This switching tends to generate electrical switching noise. The electrical switching noise should ideally be contained within the inverter module 320 and prevented from entering other electrical systems to prevent interference with other electrical components in the vehicle.

[0079]

[0084] The inverter system may include several components into which the disclosed polymer compositions can be incorporated, such as, but not limited to, the EMI filter device 325 (e.g., as a housing and / or internal support structure), the EMI filter card 340, the busbar 310, and connectors used within the system. For example, an electrical connector including the polymer composition described herein may be used in the inverter system of FIG. 7 or in another portion of an electric vehicle. The electrical connector may generally include a first connector portion containing at least one electrical contact and an insulating member surrounding at least a portion of the connector portion. The insulating member may include a polymer composition of the present invention. The first connector portion may be configured to mate with an opposing second connector portion containing a receptacle for receiving the electrical contact. In such an embodiment, the second connector portion may include at least one receptacle configured to receive the electrical contact of the first connector portion and an insulating member surrounding at least a portion of the second connector portion. The insulating member of the second connector portion may also include a polymer composition of the present invention.

[0080]

[0085] 7, 8, and 9, one particular embodiment of a connector 200 for use in an electric vehicle, such as an electric vehicle powertrain, is shown. The connector 200 includes a first connector portion 202 and a second connector portion 204. The first connector portion 202 has a The first connector portion 202 may include one or more electrical pins 206, and the second connector portion 204 may include one or more receptacles 208 for receiving the electrical pins 206. A first insulating member 212 may extend from the bottom surface 203 of the first connector portion 202 to surround the pins 206, and similarly, a second insulating member 218 may extend from the bottom surface 201 of the second connector portion 204 to surround the receptacles 208. In certain cases, the sides of the first insulating member 212 may extend beyond the ends 203 of the electrical pins, and the sides of the second insulating member 218 may extend beyond the ends of the receptacles 208. The bottom surface 203 and / or first insulating member 212 of the first connector portion 202, and the bottom surface 201 and / or second insulating member 218 of the second connector portion 204 may be formed from the polymer composition of the present invention.

[0081]

[0086] Although by no means required, first connector portion 202 may also include an identification mark 210 secured to or defined by first protective member 212. Second connector portion 204 may also optionally define an alignment window 220 sized by identification mark 210 to more easily determine when the connector portions are fully mated. By way of example, identification mark 210 cannot be read unless blocking portion 221 covers a portion of identification mark 210. Optionally, second connector portion 204 may include a preliminary mark 224 located adjacent alignment window 220.

[0082]

[0087] Figures 10 and 11 show still other examples of components that can employ the polymer compositions of the present invention (such as spacers, connectors, insulators, and supports as shown in Figure 10) and components that can be formed from the polymer compositions. Components shown in Figure 11 that can incorporate the polymer compositions include quick connectors, tees, and interconnects (several are shown at the top of Figure 11); brushless DC motors (center left of Figure 11), such as motor sealing rings, housings, supports, etc.; guide rails (center right of Figure 11, with an additional example of a bus bar also shown in the image); and battery sealing rings (bottom of Figure 11).

[0083]

[0088] Systems that can use the polymer compositions of the present invention are by no means limited to electrical systems. For example, thermal management systems can also beneficially incorporate the polymer compositions. Thermal management systems for electric vehicles generally can include multiple different subsystems, such as, but not limited to, a powertrain subsystem, a refrigeration subsystem, a battery cooling subsystem, and a heating, ventilation, and air conditioning (HVAC) subsystem. In some embodiments, one or more subsystems of a thermal management system can be fluidly coupled to one another, thereby allowing a hot heat transfer medium to flow from a hot circuit to a cold circuit and allowing a cooler heat transfer medium to flow from the cold circuit to the hot circuit.

[0084]

[0089] For example, Figure 12 shows a first temperature control loop and Figure 13 shows a second temperature control loop found in an electric vehicle, each designed for a different subsystem and each including one or more components that can use the polymer composition of the present invention. For example, the first temperature control loop of a typical electric vehicle (Figure 12) can include a heat transfer medium (e.g., water, coolant, or a mixture thereof) pumped through the loop via a suitable pump 160 (e.g., an electric pump) and cooled via heat transfer with a coolant in a heat exchanger 162 (e.g., an energy storage system (ESS) heat exchanger) and a radiator / reservoir 164. In addition, the loop can include a heater 166 (e.g., a positive temperature coefficient (PTC) heater) that can ensure that the temperature of the system can be maintained within a preferred operating range regardless of the ambient temperature, and the battery assembly 124. The second temperature control loop (Figure 13) can also include a heat transfer medium that can be the same or different from the heat transfer medium of another subsystem. The heat transfer medium of the second temperature control loop may be pumped through a loop with a suitable pump 161, heat exchanger 162, and radiator reservoir 165. The high temperature control loop may be utilized for cooling the power electronics 167 and the electric machine 114 of the vehicle.

[0085]

[0090] One example of a component of a thermal management system that can incorporate the polymer composition of the present invention is a coolant pump, such as an electric pump, an example of which is shown in FIG. 14. As shown, electric pump 401 includes an electric motor 410 as a driving source and a hydraulic section 420 that generates coolant suction and discharge forces. Motor 410 and related components are held within motor housing 411. Hydraulic section 420 generally includes a volute casing 421 that includes a spiral flow space, an inlet 422, and an outlet 423, and an impeller (not shown) that is rotated by electric motor 410. Pump 401 has an interface that includes a mechanical seal (not shown) for sealing and separating the water flow space and the motor chamber. Typically, a mounting section 412 is provided on motor housing 411 for mounting pump 401 within a vehicle. Components of electric pump 401, such as the housing, casing, and interface, can incorporate the polymer composition of the present invention.

[0086]

[0091] The present invention may be better understood with reference to the following examples. [Example]

[0087] Test Method

[0092] Melt viscosity: Melt viscosity (Pa·s) is measured at a shear rate of 400 s in accordance with ISO11443:2021. -1 The melt viscosity may be determined using a Dynisco LCR7001 capillary rheometer at 100°C. The rheometer orifice (die) may have a diameter of 1 mm, a length of 20 mm, an L / D ratio of 20.1, and an entrance angle of 180°. The barrel diameter may be 9.55 mm + 0.005 mm, and the rod length was 233.4 mm. Melt viscosity is typically determined at a temperature of 310°C.

[0088]

[0093] Tensile modulus, tensile stress at break, and tensile strain at break: Tensile properties can be tested according to ISO 527-2 / 1A:2019 (technically equivalent to ASTM D638-14). Modulus and strength measurements can be performed on the same specimen sample, 80 mm long, 10 mm thick, and 4 mm wide. The test temperature can be 23°C, and the test speed can be 5 mm / min for tensile strength and tensile strain at break, and 1 mm / min for tensile modulus.

[0089]

[0094] Flexural Modulus and Flexural Stress: Flexural properties can be tested according to ISO 178:2019 (technically equivalent to ASTM D790-10). The test can be performed on a support span of 64 mm. The test can be performed at the center of an uncut ISO 3167 multipurpose bar. The test temperature can be 23°C, and the test speed can be 2 mm / min.

[0090]

[0095] Charpy Impact Strength: Charpy properties can be tested according to ISO 179-1:2010 (technically equivalent to ASTM D256-10, Method B). This test can be performed using Type 1 specimen dimensions (80 mm length, 10 mm width, and 4 mm thickness). Specimens may be cut from the center of a multipurpose bar using a single-tooth milling machine. The test temperature may be 23°C. For "notched" impact strength, this test can be performed using a Type A notch (0.25 mm base radius) and Type 1 specimen dimensions (80 mm length, 10 mm width, and 4 mm thickness).

[0091]

[0096] Hydrolysis Test: High-temperature hydrolysis tests can be performed using a 4-liter autoclave. The autoclave is equipped with an immersion heater and a temperature control system. The autoclave is first filled with a solution containing 50% by volume of deionized water and 50% by volume of ethylene glycol. A sample with a volume of 7.5 liters is then completely immersed in the solution. The autoclave is closed, and the solution is heated to 135°C, creating an internal pressure of approximately 2-3 bar. After testing for 1,000 hours, the autoclave is cooled to room temperature (approximately 23°C), the pressure is released, and the tensile bar set is retrieved for further testing.

[0092]

[0097] UL94: The test specimen is supported in a vertical position and a flame is applied to the bottom of the specimen. The flame is applied for 10 seconds, then removed, until the flame sterilization stops, at which point the flame is reapplied for another 10 seconds, then removed. Two sets of five test specimens are tested. The specimen dimensions are 125 mm long, 13 mm wide, and 0.8 mm thick. The two sets are conditioned before and after aging. For unaged tests, each thickness is tested after conditioning for 48 hours at 23°C and 50% relative humidity. For aged tests, five specimens of each thickness are tested after conditioning for 7 days at 70°C.

[0093] [Table 1]

[0094] Comparative Examples 1-2

[0098] Comparative Examples 1-2 were melt-mixed using a Coperion 32 mm co-rotating, fully intermeshed twin-screw extruder and contained various concentrations of polyarylene sulfide, glass fiber, silane coupling agent, nucleating agent, black pigment masterbatch, and lubricant (Glycolube). The glass fiber was E-glass fiber (fiber diameter 10 micrometers) obtained from Jushi Glass fibers.

[0095] [Table 2]

[0096]

[0099] Once formed, the resulting compositions were then injection molded and tested for the various properties mentioned above, with the results being set forth below.

[0097] [Table 3]

[0098] Examples 1 and 2

[0100] Examples 1-2 were melt-mixed using a Coperion 32 mm co-rotating, fully intermeshed twin-screw extruder and contained various concentrations of polyarylene sulfide, glass fiber, silane coupling agent, nucleating agent, and lubricant (Glycolube). The glass fiber was E-CR glass fiber (average fiber diameter 11 μm) obtained from 3B under the designation "DS 8800-11P."

[0099] [Table 4]

[0100]

[0101] Once formed, the resulting compositions were then injection molded and tested for the various properties mentioned above, with the results being set forth below.

[0101] [Table 5]

[0102]

[0102] These and other modifications and variations of the present invention may be practiced by those skilled in the art without departing from the spirit and scope of the present invention. In addition, it should be understood that aspects of the various embodiments may be interchanged both in whole or in part. Furthermore, those skilled in the art will appreciate that the foregoing description is by way of example only and is not intended to limit the invention as further described within the appended claims.

Claims

1. 1. A polymeric composition comprising: 100 parts by weight of a polymeric matrix comprising at least one polyarylene sulfide; and about 30 parts by weight to about 120 parts by weight of inorganic fibers, such as glass fibers; wherein the polymeric composition exhibits an initial tensile strength and an aged tensile strength after exposure to a solution containing 50% by volume of deionized water and 50% by volume of ethylene glycol at a temperature of 135°C for 1,000 hours, wherein the ratio of the aged tensile strength to the initial tensile strength is about 0.8 or greater, and the initial tensile strength and the aged tensile strength are determined at a temperature of 23°C in accordance with ISO 527:2019.

2. 10. The polymer composition of claim 1, wherein the aged tensile strength is from about 125 to about 250 MPa.

3. 10. The polymer composition of claim 1, wherein the polymer composition exhibits an initial tensile elongation and an aged tensile elongation after exposure to a solution containing 50% by volume deionized water and 50% by volume ethylene glycol at a temperature of 135°C for 1,000 hours, wherein the ratio of the aged tensile elongation to the initial tensile elongation is about 0.7 or greater, and wherein the initial tensile elongation and the aged tensile elongation are determined in accordance with ISO 527:2019 at a temperature of 23°C.

4. 4. The polymer composition of claim 3, wherein the aged tensile elongation is from about 1.2% to about 5%.

5. 2. The polymer composition of claim 1, wherein the polymer composition exhibits an initial notched Charpy impact strength and an aged notched Charpy impact strength after exposure to a solution containing 50% by volume of deionized water and 50% by volume of ethylene glycol at a temperature of 135°C for 1,000 hours, wherein the ratio of the aged notched Charpy impact strength to the initial notched Charpy impact strength is about 0.6 or greater, and wherein the initial notched Charpy impact strength and the aged notched Charpy impact strength are determined in accordance with ISO 179:2020 at a temperature of 23°C.

6. The aging notched Charpy impact strength is about 5 to about 15 kJ / m ２ 6. The polymer composition of claim 5, wherein

7. The polymer composition of claim 1 , wherein the polymer matrix comprises from about 40 wt % to about 90 wt % of the polymer composition.

8. 10. The polymer composition of claim 1, wherein the polyarylene sulfide is a polyphenylene sulfide such as a linear polyphenylene sulfide.

9. The polymer composition of claim 1, wherein the inorganic fibers have a diameter of about 5 to about 40 micrometers.

10. The polymer composition of claim 1 , wherein the inorganic fibers comprise generally boron-free glass fibers.

11. The polymer composition of claim 10, wherein the glass fibers are E-CR glass fibers.

12. 11. The polymer composition of claim 10, wherein the glass fibers contain silica in an amount from about 57.5 wt % to about 59.5 wt %, alumina in an amount from about 17 wt % to about 20 wt %, calcium oxide in an amount from about 11 wt % to about 13.5 wt %, and magnesium oxide in an amount from about 8.5 wt % to about 12.5 wt %.

13. 10. The polymer composition of claim 1, wherein the inorganic fibers are coated with a sizing composition optionally containing an alkoxysilane, a functionalized compound, a blocked isocyanate, a film former, or a combination thereof.

14. 14. The polymer composition of claim 13, wherein the functionalized compound comprises an anhydride and / or carboxylic acid functionalized polymer, an epoxy functionalized polymer, or a combination thereof.

15. 10. The polymer composition of claim 1, further comprising about 0.1 to about 8 parts by weight of an organosilane compound.

16. 16. An electric vehicle having a powertrain including at least one electric propulsion source and a transmission connected to the propulsion source through at least one power electronics module, the electric vehicle comprising the polymer composition of any of claims 1 to 15.

17. 17. The electric vehicle of claim 16, wherein the electric vehicle includes an electrical component comprising the polymer composition.

18. 18. The electric vehicle of claim 17, wherein the electrical components include bus bars, current sensors, inverter filters, electrical connectors, brushless DC motors, guide rings, battery cell sealing rings, or combinations thereof.

19. 18. The electric vehicle of claim 17, wherein the electrical component comprises a quick connector, a tee, an interconnector, or a combination thereof.

20. 17. The electric vehicle of claim 16, wherein the electric vehicle includes a thermal management system component that optionally includes a coolant pump comprising the polymer composition.

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