Thermally conductive polymer composition

Abstract

A polymeric composition is provided that includes an aromatic polyester and an inorganic filler, including inorganic particles and, optionally, inorganic fibers, dispersed within a polymeric matrix. The inorganic filler is present in an amount of about 60 parts by weight to about 200 parts by weight of the polymeric matrix, and the inorganic particles are present in an amount of about 40 parts by weight to about 200 parts by weight of the polymeric matrix. The polymeric composition exhibits an in-plane thermal conductivity of about 1.5 W / m·K or greater and a melt fray rate of about 0.1 to about 50 g / 10 min.

Description

[Technical Field]

[0001] Related Applications

[0001] This application is based on and claims priority to U.S. Provisional Patent Application No. 63 / 432,125, filed December 13, 2022, which is incorporated herein by reference. [Background technology]

[0002]

[0002] Electronic modules typically include electrical components (e.g., printed circuit boards, antenna elements, radio frequency devices, sensors, light detection and / or transmission elements (e.g., optical fibers), cameras, global positioning devices, etc.) housed within a housing structure that protects them from weather such as sunlight, wind, and moisture. Typically, such housings are formed from materials that allow the passage of electromagnetic signals (e.g., radio frequency signals or light). While these materials are suitable for some applications, they may nevertheless present problems in higher frequency ranges, such as those associated with LTE or 5G systems. Radar modules, for example, typically include one or more printed circuit boards with dedicated electrical components for handling radio frequency (RF) radar signals, digital signal processing tasks, etc. To ensure these components operate effectively at high frequencies, they are generally housed in a housing structure and then covered with a radio wave-transparent radome. Heat sinks (e.g., thermal pads) are commonly used on circuit boards to help draw heat away from the components. Unfortunately, the addition of such components can add a substantial amount of cost and weight to the resulting module, which is particularly detrimental as the automotive industry continues to require smaller and lighter components. Accordingly, there is currently a need for electronic modules that do not require the need for additional heat sinks. 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 a polymeric matrix comprising an aromatic polyester and an inorganic filler dispersed within the polymeric matrix, the inorganic filler including inorganic particles and, optionally, inorganic fibers. The inorganic filler is present in an amount of about 60 parts by weight to about 200 parts by weight of the polymeric matrix, and the inorganic particles are present in an amount of about 40 parts by weight to about 200 parts by weight of the polymeric matrix. The polymeric composition exhibits an in-plane thermal conductivity of about 1.5 W / m·K or greater, as determined in accordance with ASTM E1461-13(2022), and a melt fray rate of about 0.1 to about 50 g / 10 min, as determined in accordance with ISO 1133:2022, at a temperature of about 250°C and a load of 2.16 kg.

[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 is an enlarged perspective view of one embodiment of an electronic module in which the polymer composition of the present invention may be used. [Figure 2]

[0007] 1 illustrates one embodiment of a 5G system in which the polymer composition of the present invention can be used. DETAILED DESCRIPTION OF THE INVENTION

[0006]

[0008] 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.

[0009] Generally speaking, the present invention is directed to a polymer composition comprising an aromatic polyester and an inorganic filler dispersed within a polymer matrix comprising inorganic fibers, and optionally inorganic fibers (e.g., glass fibers). By selectively controlling the specific nature and relative concentrations of the components of the polymer composition, the inventors have discovered that the resulting composition can exhibit a unique combination of properties that enable 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, from about 0.2 to about 3.2 millimeters, in some embodiments, from about 0.4 to about 2.5 millimeters, and in some embodiments, from about 0.8 to about 2 millimeters.

[0007]

[0010] The polymeric compositions may, for example, exhibit an in-plane (or "flow") thermal conductivity of about 1.5 W / m·K or greater, in some embodiments about 2 W / m·K or greater, in some embodiments about 3 to about 8 W / m·K, and in some embodiments about 4 to about 6 W / m·K, as determined in accordance with ASTM E 1461-13(2022). Similarly, the polymeric compositions may exhibit a cross-plane (or "cross-flow") thermal conductivity of about 1 W / m·K or greater, in some embodiments about 2 W / m·K or greater, in some embodiments about 2.5 to about 8 W / m·K, and in some embodiments about 3 to about 6 W / m·K, as determined in accordance with ASTM E 1461-13(2022). The compositions may also exhibit through-plane thermal conductivities of about 0.2 W / m·K or greater, in some embodiments about 0.4 W / m·K or greater, in some embodiments about 0.5 to about 4 W / m·K, and in some embodiments about 0.6 to about 2 W / m·K, as determined in accordance with ASTM E 1461-13(2022). Such high thermal conductivity values ​​enable the compositions to create thermal paths for heat transfer from electrical components in which they are used. In this manner, "hot spots" can be quickly eliminated, and overall temperatures can be reduced during use. Notably, it has been discovered that such thermal conductivities can be achieved without the use of conventional materials with high intrinsic thermal conductivities. For example, polymer compositions generally may be free of fillers that have intrinsic thermal conductivities of 50 W / m·K or greater, in some embodiments, 100 W / m·K or greater, and in some embodiments, 150 W / m·K or greater. Such high intrinsic thermal conductivity materials can include, for example, boron nitride, aluminum nitride, magnesium silicon nitride, graphite (e.g., expanded graphite), silicon carbide, carbon nanotubes, zinc oxide, magnesium oxide, beryllium oxide, zirconium oxide, yttrium oxide, aluminum powder, and copper powder. While it is typically desirable to minimize the presence of such high intrinsic thermal conductivity materials, they may nevertheless be present in relatively small percentages in certain embodiments, such as about 10 wt % or less, in some embodiments about 5 wt % or less, and in some embodiments, from about 0.01 wt % to about 2 wt % of the polymer composition.

[0008]

[0011] While exhibiting good thermal conductivity, the compositions may still exhibit good flow characteristics as reflected by melt fray rates of about 0.5 to about 50 grams per 10 minutes (g / 10 min) or greater, in some embodiments about 1 to about 40 g / 10 min, in some embodiments about 2 to about 30 g / 10 min, and in some embodiments about 3 to about 20 g / 10 min, as determined according to ISO 1133:2022 at about 250°C and a 2.16 kilogram load. The polymer compositions may also exhibit high insulating properties, which may be characterized by a high comparative tracking index ("CTI"), such as, for example, about 400 volts or greater, in some embodiments about 450 volts or greater, in some embodiments about 500 volts or greater, in some embodiments about 550 volts or greater, in some embodiments about 580 volts or greater, and in some embodiments about 600 volts or greater, as determined according to IEC 60112:2020 at part thicknesses such as those described above (e.g., 3 millimeters).

[0009]

[0012] Despite having good flow characteristics and high insulating properties, the polymer composition may still maintain a high degree of strength, providing enhanced flexibility to the resulting component. The polymer composition may exhibit, for example, a tensile stress at break (i.e., strength) of about 10 MPa to about 300 MPa, in some embodiments about 20 MPa to about 200 MPa, and in some embodiments about 40 to about 100 MPa; a tensile strain at break (i.e., elongation) of about 0.3% or greater, in some embodiments about 0.4% to about 8%, and in some embodiments about 0.5% to about 5%; and / or a tensile modulus of about 5,000 MPa to about 30,000 MPa, in some embodiments about 6,000 MPa to about 25,000 MPa, and in some embodiments about 10,000 MPa to about 22,000 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 as determined at a temperature of 23°C according to ISO 179-1:2010. 2 or more, in some embodiments, about 5 to about 40 kJ / m 2 and in some embodiments, from about 10 to about 30 kJ / m 2 It can exhibit an unnotched Charpy impact strength of 1000 MPa.

[0010]

[0013] The polymer compositions may also be "hydrolysis resistant," meaning that they are not sensitive to the presence of saturated steam at a temperature of 121°C. In other words, even when exposed to steam at such high temperatures, the mechanical properties (e.g., impact strength, tensile properties, etc.) may remain near or even within the ranges described above. The mechanical properties may also remain stable at such temperatures for a substantial period of time, such as about 20 hours or more, in some embodiments, from about 50 hours to about 500 hours, and in some embodiments, from about 80 hours to about 200 hours (e.g., 96 or 168 hours). For example, after "aging" in contact with saturated steam at 121°C for 96 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. After aging in contact with saturated steam at 121°C for 96 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.

[0011]

[0014] The polymer composition may also exhibit good heat resistance and flame retardancy. The melting temperature of the composition may be, for example, about 150°C to about 300°C, in some embodiments about 180°C to about 280°C, and in some embodiments about 210°C to about 250°C (e.g., 225°C). Even at such melting temperatures, the ratio of temperature deflection under load ("DTUL"), an indicator of short-term heat resistance, to the melting temperature may remain relatively high. For example, the ratio may be in the range of about 0.5 to about 1.00, in some embodiments about 0.6 to about 0.95, and in some embodiments about 0.65 to about 0.9. Specific DTUL values, determined according to ISO 75:2013 at a load of, for example, 1.8 MPa, may be, for example, about 260°C or higher, in some embodiments about 120°C to about 300°C, and in some embodiments about 150°C to about 220°C. Such high DTUL values, among other things, enable the use of high-speed, reliable surface mounting processes for mating the structure with other electrical components. The flame-retardant properties of the composition may also be characterized according to the procedures 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 for 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 rating of at least V2 for component 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 flame burn time of about 250 seconds or less. To achieve a V0 rating, the composition may exhibit a total flame burn time of about 50 seconds or less and a total drip count of zero fire particles that ignite cotton.

[0012]

[0015] Various embodiments of the invention will now be described in more detail. I. Polymer Composition A. Polymer matrix

[0016] The polymer matrix typically comprises about 20 wt% to about 60 wt%, in some embodiments about 25 wt% to about 55 wt%, and in some embodiments about 30 wt% to about 50 wt% of the polymer composition. The polymer matrix contains at least one aromatic polyester. For example, the aromatic polyester 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]

[0017] Suitable aromatic polyesters include, for example, condensation products of at least one diol (e.g., aliphatic and / or cycloaliphatic) with at least one aromatic dicarboxylic acid, such as those having 4 to 20 carbon atoms, and in some embodiments, 8 to 14 carbon atoms. Suitable diols include, for example, neopentyl glycol, cyclohexanedimethanol, 2,2-dimethyl-1,3-propanediol, and carboxylic acids of the formula HO(CH2). n OH (where n is an integer from 2 to 10). Suitable aromatic dicarboxylic acids include, for example, isophthalic acid, terephthalic acid, 1,2-di(p-carboxyphenyl)ethane, 4,4'-dicarboxydiphenyl ether, and the like, and combinations thereof. Fused rings can also be present, such as in 1,4-, 1,5-, or 2,6-naphthalene-dicarboxylic acid. Specific examples of such aromatic polyesters include, for example, poly(ethylene terephthalate) (PET), poly(1,4-butylene terephthalate) (PBT), poly(1,3-propylene terephthalate) (PPT), poly(1,4-butylene 2,6-naphthalate) (PBN), poly(ethylene 2,6-naphthalate) (PEN), poly(1,4-cyclohexylene dimethylene terephthalate) (PCT), and mixtures of the foregoing.

[0014]

[0018] Derivatives and / or copolymers of aromatic polyesters (e.g., polyethylene terephthalate) can also be used. For example, in one embodiment, modified acids and / or diols can be used to form derivatives of such polymers. As used herein, the terms "modifying acid" and "modifying diol" are meant to define compounds that can form part of the acid and diol repeating units of a polyester, respectively, and can modify the polyester to reduce its crystallinity or render it amorphous. Examples of modifying acid components include, but are not limited to, isophthalic acid, phthalic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, suberic acid, 1,12-dodecanedioic acid, and the like. In practice, it is often preferable to use functional acid derivatives thereof, such as the dimethyl, diethyl, or dipropyl esters of the dicarboxylic acids. Anhydrides or acid halides of these acids can also be used, where practical. Examples of modified diol components include, but are not limited to, neopentyl glycol, 1,4-cyclohexanedimethanol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, Z,8-bis(hydroxymethyltricyclo-[ 5.2.1.0]-decane (wherein Z represents 3, 4, or 5); 1,4-bis(2-hydroxyethoxy)benzene, 4,4'-bis(2-hydroxyethoxy)diphenyl ether [bis-hydroxyethyl bisphenol A], 4,4'-bis(2-hydroxyethoxy)diphenyl sulfide [bis-hydroxyethyl bisphenol S], and diols containing one or more oxygen atoms in the chain, such as diethylene glycol, triethylene glycol, dipropylene glycol, and tripropylene glycol.Generally, these diols contain from 2 to 18 carbon atoms, and in some embodiments from 2 to 8. The alicyclic diols can be used in their cis or trans configuration, or as a mixture of both forms.

[0015]

[0019] In certain cases, aromatic polyesters may contain relatively small amounts of carboxyl end groups to help improve the hydrolysis resistance of the polymer composition. The aromatic polyester may, for example, contain carboxyl end groups in an amount less than about 20 mmol / kg, e.g., less than about 18 mmol / kg, e.g., less than about 15 mmol / kg, and typically greater than about 1 mmol / kg. The amount of carboxyl end groups can be minimized in polyester polymers using different techniques. For example, in one embodiment, the aromatic polyester can be contacted with an alcohol, e.g., benzyl alcohol, to reduce the amount of carboxyl end groups. Each kilogram of aromatic polyester resin may similarly contain less than 35 milliequivalents, preferably less than 30 milliequivalents, and more preferably less than 25 milliequivalents of carboxylic acid end groups. The milliequivalent amount of carboxylic acid end groups in semi-aromatic polyester resins can be determined by any number of known titration methods. For example, potentiometric titration can be used, in which the semi-aromatic polyester resin is dissolved in a suitable solvent and then titrated with a base, such as potassium hydroxide, to an inflection point or endpoint.

[0016]

[0020] Aromatic polyesters such as those described above typically have glass transition temperatures of from about 30°C to about 120°C, in some embodiments from about 40°C to about 110°C, and in some embodiments from about 50°C to about 100°C, as determined, for example, according to ISO 11357-2:2020. The aromatic polyesters may also have intrinsic viscosities of from about 0.1 dL / g to about 6 dL / g, in some embodiments from about 0.2 to about 5 dL / g, and in some embodiments from about 0.3 to about 1 dL / g, as determined, for example, according to ISO 1628-5:1998. Similarly, the melt filament rate of the aromatic polyesters may be from about 0.1 to about 50 grams per 10 minutes ("g / 10 min"), in some embodiments from about 1 to about 35 g / 10 min, and in some embodiments from about 5 to about 20 g / 10 min, as determined according to ISO 1133:2022 at about 250°C and a 2.16 kilogram load.

[0017] B. Inorganic fillers

[0021] The polymer composition also contains an inorganic filler dispersed within the polymer matrix. The inorganic filler generally comprises from about 60 to about 200 parts by weight, in some embodiments from about 75 to about 200 parts by weight, in some embodiments from about 90 to about 200 parts by weight, in some embodiments from about 100 to about 180 parts by weight, and in some embodiments from about 120 to about 160 parts by weight, per 100 parts by weight of the polymer matrix. The inorganic filler may, for example, comprise from about 40 wt% to about 80 wt%, in some embodiments from about 45 wt% to about 75 wt%, and in some embodiments from about 50 wt% to about 70 wt% of the polymer composition.

[0018]

[0022] The inorganic filler may be formed entirely of inorganic particles, or the filler may contain a combination of inorganic particles and inorganic fibers. When such fibers are used, they typically comprise from about 10 wt% to about 60 wt%, in some embodiments from about 15 wt% to about 55 wt%, and in some embodiments from about 20 wt% to about 50 wt% of the inorganic filler, while the inorganic particles comprise from about 40 wt% to about 90 wt%, in some embodiments from about 45 wt% to about 85 wt%, and in some embodiments from about 50 wt% to about 70 wt% of the inorganic filler. The inorganic particles may, for example, be present in an amount by weight greater than the inorganic fibers. Nevertheless, the total amount of inorganic particles is generally about 40 to about 200 parts by weight, in some embodiments about 50 to about 180 parts by weight, in some embodiments about 60 to about 160 parts by weight, per 100 parts by weight of polymer matrix, and also about 10 to about 80 parts by weight, in some embodiments about 15 to about 75 parts by weight, and in some embodiments about 20 to about 70 parts by weight of the polymer composition. If used, the total amount of inorganic fibers is generally about 10 to about 100 parts by weight, in some embodiments about 20 to about 90 parts by weight, and in some embodiments about 30 to about 80 parts by weight, per 100 parts by weight of polymer matrix, and also about 1 to about 50 parts by weight, in some embodiments about 5 to about 45 parts by weight, and in some embodiments about 10 to about 40 parts by weight of the polymer composition.

[0019]

[0023] Various inorganic particles can be used to help achieve the desired properties of the polymer composition. In one embodiment, by way of example, the particles can be formed from natural and / or synthetic metal silicates, such as talc, mica, halloysite, kaolinite, illite, montmorillonite, vermiculite, palygorskite, pyrophyllite, calcium silicate, aluminum silicate, wollastonite, and the like. Talc is particularly suitable for use in the polymer composition. The general formula: M(OH) a O bMetal hydroxide particles containing at least one metal hydroxide having the formula: where 0≦a≦3 (e.g., 1), b=(3−a) / 2, and M is a metal, such as magnesium, aluminum, etc., can also be used. Aluminum hydroxide particles are particularly suitable. In one embodiment, for example, the particles can exhibit a boehmite crystalline phase and the aluminum hydroxide can have the formula AlO(OH) (“aluminum oxide hydroxide”). In addition to metal silicates and / or metal hydroxides, metal oxide particles such as titanium dioxide, magnesium oxide, zinc oxide, or combinations thereof can also be used.

[0020]

[0024] The inorganic particles can be needle-shaped, ellipsoidal, platelet-shaped, spherical, granular, flake-shaped, and the like. In certain embodiments, the particles can have a microscale median particle size (D50) of about 1 to about 25 micrometers, in one embodiment about 2 to about 15 micrometers, and in some embodiments about 4 to about 10 micrometers, as determined by sedimentation analysis (e.g., Sedigraph 5120). Of course, smaller particles can be used in certain circumstances. For example, particles having a nanoscale median particle size (D50), e.g., about 50 to about 800 nanometers, in one embodiment about 150 to about 700 nanometers, and in some embodiments about 250 to about 500 nanometers, as determined by non-invasive backscattering (NIBS) techniques, can be used. If desired, the particles can also have a high specific surface area, e.g., about 1 square meter per gram (m 2 / g) ~ approx. 100m 2 / g, in some embodiments, about 1.5m 2 / g~about 50m 2 / g, in some embodiments, about 2m 2 / g ~ approx. 25m 2 / g. The surface area may be determined by the physical gas adsorption (BET) method (nitrogen as the adsorbed gas) according to DIN 66131:1993. The moisture content may also be relatively low, for example, about 5% or less, in some embodiments about 3% or less, and in some embodiments, about 0.1 to about 1%, when determined according to ISO 787-2:1981 at a temperature of 105°C.

[0021]

[0025] When used, inorganic fibers can further help 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 having 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.

[0022]

[0026] 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. The glass fibers may also 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.

[0023]

[0027] 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, and 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.

[0024]

[0028] 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.

[0025]

[0029] 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. % of the solids content (i.e., excluding water) of the sizing composition, in some embodiments, from about 10 wt. % to about 80 wt. %, and in some embodiments, from about 15 wt. % to about 70 wt. 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 been 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.

[0026]

[0030] 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.

[0027]

[0031] 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.

[0028]

[0032] 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.

[0029] C. Optical component

[0033] In addition to the above components, the polymer composition may also contain various other optical components that help improve its overall properties, such as flame retardants, heat stabilizers, light stabilizers, antioxidants, UV stabilizers, electromagnetic interference ("EMI") fillers, coupling agents, impact modifiers, pigments (e.g., black pigments), laser marking additives (e.g., carbon black), lubricants, flow promoters, hydrolysis resistant additives, and other materials added to enhance properties and processability.

[0030]

[0034] In certain embodiments, for example, it may be desirable to employ a flame retardant system. If employed, the flame retardant system may comprise from about 5 wt% to about 60 wt%, in some embodiments, from about 6 wt% to about 50 wt%, in some embodiments, from about 8 wt% to about 35 wt%, in some embodiments, from about 10 wt% to about 30 wt% of the polymer matrix, and from about 1 wt% to about 50 wt%, in some embodiments, from about 5 wt% to about 30 wt%, in some embodiments, from about 10 wt% to about 25 wt% of the overall polymer composition. The flame retardant system may include at least one low-halogen or halogen-free flame retardant. Such agents have a halogen (e.g., bromine, chlorine, and / or fluorine) content of about 1,500 parts per million ("ppm") by weight or less, in some embodiments, about 900 ppm or less, and in some embodiments, about 50 ppm or less. In certain embodiments, the flame retardant is completely halogen-free (i.e., 0 ppm). The particular properties of the halogen-free flame retardant can be selected to help achieve the desired flame retardant properties without adversely affecting the insulating performance (e.g., dielectric constant, dissipation factor, etc.) and mechanical properties of the polymer composition.

[0031]

[0035] The flame retardant system may, for example, contain one or more organophosphorus flame retardant compounds, such as phosphates, phosphate esters, phosphonate esters, phosphonate amines, phosphazenes, phosphinates, and the like, and mixtures thereof. The organophosphorus flame retardant compound may, for example, comprise from about 40 wt% to about 100 wt%, in some embodiments from about 50 wt% to about 95 wt%, and in some embodiments, from about 60 wt% to about 90 wt% of the flame retardant system. In certain embodiments, for example, the organophosphorus flame retardant may comprise from about 1 wt% to about 25 wt%, in some embodiments from about 5 wt% to about 20 wt%, and in some embodiments, from about 10 wt% to about 15 wt% of the overall polymer composition. One particularly suitable organophosphorus flame retardant may be a phosphinate, which may enhance the flame retardancy of the overall composition, especially in relatively thin sections, without adversely affecting mechanical and insulating properties. Such phosphinates are typically salts of phosphinic acids and / or diphosphinic acids, such as those of general formula (I) and / or formula (II):

[0032] [ka]

[0033] (In the formula, R7 and R8 are independently hydrogen or a substituted or unsubstituted linear, branched or cyclic hydrocarbon group having 1 to 6 carbon atoms (e.g., alkyl, alkenyl, alkynyl, aralkyl, aryl, alkaryl, etc.), particularly an alkyl group having 1 to 4 carbon atoms, such as a methyl, ethyl, n-propyl, isopropyl, n-butyl, or tert-butyl group; R9 is a substituted or unsubstituted straight-chain, branched, or cyclic C1-C 10 alkylene, arylene, arylalkylene, or alkylarylene groups, such as methylene, ethylene, n-propylene, isopropylene, n-butylene, tert-butylene, n-pentylene, n-octylene, n-dodecylene, phenylene, naphthylene, methylphenylene, ethylphenylene, tert-butylphenylene, methylnaphthylene, ethylnaphthylene, t-butylnaphthylene, phenylethylene, phenylpropylene, or phenylbutylene groups; Z is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K, and / or a protonated nitrogen base; y is 1 to 4, preferably 1 to 2 (e.g., 1); n is 1 to 4, preferably 1 to 2 (e.g., 1); m is 1 to 4, preferably 1 to 2 (e.g., 2). It has the following characteristics.

[0034]

[0036] Phosphinates can be prepared using any known technique, for example, by reacting phosphinic acid with a metal carbonate, metal hydroxide, or metal oxide in an aqueous solution. Particularly suitable phosphinates include metal salts of dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, methyl-n-propylphosphinic acid, methane-di(methylphosphinic acid), ethane-1,2-di(methylphosphinic acid), hexane-1,6-di(methylphosphinic acid), benzene-1,4-di(methylphosphinic acid), methylphenylphosphinic acid, diphenylphosphinic acid, hypophosphoric acid, and the like. The resulting salts are typically monomeric compounds; however, polymeric phosphinates can also be formed. Particularly suitable metal salts include Al and Zn. For example, one particularly suitable phosphinate is zinc diethylphosphinate. Another particularly suitable phosphinate is aluminum diethylphosphinate, for example, commercially available from Clariant under the trade name DEPAL™.

[0035]

[0037] Of course, other organic phosphorus flame retardants can also be used in the flame retardant system. For example, in one embodiment, monomeric and oligomeric phosphoric and phosphonic acid esters, such as tributyl phosphate, triphenyl phosphate, tricresyl phosphate, diphenyl cresyl phosphate, diphenyl octyl phosphate, diphenyl 2-ethyl cresyl phosphate, tri(isopropylphenyl)phosphate, resorcinol-bridged oligophosphates, bisphenol A phosphates (e.g., bisphenol A-bridged oligophosphate or bisphenol A bis(diphenyl phosphate)), and mixtures thereof can be used. Aryl phosphates, aryl phosphonites, aryl phosphonates, hypophosphites, phosphazenes, red phosphorus, and the like can also be used as suitable organic phosphorus flame retardants.

[0036]

[0038] In addition to the organophosphorus flame retardant, the flame retardant system may also contain a variety of other components. For example, in certain embodiments, the flame retardant system may include one or more organophosphorus synergists. The halogen (e.g., bromine, chlorine, and / or fluorine) content of such synergists is typically about 1,500 parts per million by weight ("ppm") or less, in some embodiments about 900 ppm or less, and in some embodiments about 50 ppm or less. In certain embodiments, the synergist is completely halogen-free (i.e., 0 ppm). When used, such organophosphorus synergists typically comprise from about 5 wt% to about 50 wt%, in some embodiments about 15 wt% to about 45 wt%, and in some embodiments about 20 wt% to about 40 wt% of the flame retardant system. In certain embodiments, for example, the organophosphorus synergist 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 total polymer composition. Examples of suitable organophosphorus synergists can include, for example, salts of phosphoric acid, such as phosphates, hydrogen phosphates, orthophosphates, pyrophosphates, phosphonites, phosphites, phosphonates, and the like, and combinations thereof.

[0037]

[0039] Cations used to form the phosphoric acid salts can include metal cations (e.g., Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K, etc., and combinations thereof); protonated nitrogen bases; or combinations of any of the foregoing (e.g., combinations of metals and protonated nitrogen bases). When metal cations are used, aluminum and zinc are particularly suitable, such as aluminum phosphite, zinc phosphite, aluminum phosphonate, zinc phosphonate, calcium phosphate, aluminum phosphate, zinc phosphate, titanium phosphate, iron phosphate, calcium hydrogen phosphate, calcium hydrogen phosphate dihydrate, magnesium hydrogen phosphate, titanium hydrogen phosphate, zinc hydrogen phosphate, aluminum phosphate, aluminum orthophosphate, aluminum hydrogen phosphate, aluminum dihydrogen phosphate, magnesium dihydrogen phosphate, calcium dihydrogen phosphate, zinc dihydrogen phosphate, zinc dihydrogen phosphate dihydrate, aluminum dihydrogen phosphate, calcium pyrophosphate, calcium dihydrogen pyrophosphate, magnesium pyrophosphate, zinc pyrophosphate, aluminum pyrophosphate, etc., and blends thereof. Suitable protonated nitrogen bases can also include substituted or unsubstituted ring structures having at least one nitrogen heteroatom (e.g., heterocyclic or heteroaryl group) in the ring structure and / or at least one nitrogen-containing functional group (e.g., amino, acylamino, etc.) substituted on a carbon atom and / or heteroatom of the ring structure. Examples of such heterocyclic groups include, for example, pyrrolidine, imidazoline, pyrazolidine, oxazolidine, isoxazolidine, thiazolidine, isothiazolidine, piperidine, piperazine, thiomorpholine, etc. Similarly, examples of heteroaryl groups can include, for example, pyrrole, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, triazole, furazan, oxadiazole, tetrazole, pyridine, diazine, oxazine, triazine, tetrazine, etc.If desired, the ring structure of the base may also be substituted with one or more functional groups, such as acyl, acyloxy, acylamino, alkoxy, alkenyl, alkyl, amino, aryl, aryloxy, carboxyl, carboxyl ester, cycloalkyl, hydroxyl, halo, haloalkyl, heteroaryl, heterocyclyl, etc. Substitution may occur at heteroatoms and / or carbon atoms of the ring structure. One suitable nitrogen base is melamine, which contains a 1,3,5 triazine ring structure substituted with an amino functional group at each of its three carbon atoms. Another suitable nitrogen base is piperazine, which is a six-membered ring structure containing two nitrogen atoms at opposite positions on the ring.

[0038]

[0040] In a particular embodiment, the organophosphorus synergist can be a salt containing only a protonated nitrogen base cation, such as an azine (e.g., melamine and / or piperazine) phosphate. Examples of such azine phosphates include melamine orthophosphate, melamine pyrophosphate, melamine polyphosphate, piperazine orthophosphate, piperazine pyrophosphate, piperazine polyphosphate, and blends thereof. An example of a melamine polyphosphate is available from BASF under the name MELAPUR® (e.g., MELAPUR® 200 or 200 / 70). In another embodiment, the organophosphorus synergist can be a salt containing a combination of a metal cation and a protonated nitrogen base cation, such as an azine (e.g., melamine and / or piperazine) metal phosphate. Examples of suitable azine metal phosphates include, for example, zinc melamine phosphate, magnesium melamine phosphate, calcium melamine phosphate, bismelamine zincodiphosphate, bismelamine aluminotriphosphate, (melamine)2Mg(HPO4)2, (melamine)2Ca(HPO4)2, (melamine)3Al(HPO4)3, (melamine)2Mg(P2O7), (melamine)2Ca(P2O7), (melamine)2Zn(P2O7), (melamine)3Al(P2O7). 3 / 2and the like, and blends thereof. Azine poly(metal phosphates), known as metal hydrogen phosphate or pyrophosphate metalates, can also be used, with anionic complexes having tetravalent or hexavalent metal atoms as coordination sites with bidentate hydrogen phosphate or pyrophosphate ligands. Examples of such poly(metal phosphates) include, for example, melamine poly(zinc phosphate) and / or melamine poly(magnesium phosphate).

[0039]

[0041] The flame retardant system may be formed entirely of organophosphorus flame retardants and / or synergists, such as those described above. However, in certain embodiments, it may be desirable to use additional compounds that help increase the effectiveness of the system. For example, inorganic compounds may be used in combination with the organophosphorus compounds as low-halogen char-forming and / or smoke suppressing agents. Suitable inorganic compounds (anhydrous or hydrated) include, for example, inorganic molybdates, such as zinc molybdate (e.g., available from Huber Engineered Materials under the trade name Kemgard®), calcium molybdate, ammonium octamolybdate, zinc molybdate-magnesium silicate, and the like. Other suitable inorganic compounds include inorganic borates, such as zinc borate (available from Rio Tento Minerals under the trade name Firebrake®); basic zinc(VI) chromate (zinc yellow), zinc chromite, zinc permanganate, silica, magnesium silicate, calcium silicate, calcium carbonate, titanium dioxide, magnesium(II) hydroxide, and the like. In certain embodiments, it may be desirable to use inorganic zinc compounds, such as zinc molybdate, zinc borate, etc., to enhance the overall performance of the composition. When used, such inorganic compounds (e.g., zinc borate) may comprise, for example, from about 1 wt % to about 20 wt %, in some embodiments from about 2 wt % to about 15 wt %, in some embodiments from about 3 wt % to about 10 wt %, and also 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 4 wt % of the overall polymer composition.

[0040]

[0042] The flame retardant system and / or the polymer composition itself generally have a relatively low content of halogens (i.e., bromine, fluorine, and / or chlorine), such as about 15,000 parts per million ("ppm") or less, in some embodiments about 10,000 ppm or less, in some embodiments about 5,000 ppm or less, in some embodiments about 200 ppm or less, and in some embodiments about 1 ppm to about 1,500 ppm. Nevertheless, in certain embodiments of the present invention, halogen-based flame retardants may still be used as optional components. Particularly suitable halogen-based flame retardants are fluoropolymers, such as polytetrafluoroethylene (PTFE), fluorinated ethylene polypropylene (FEP) copolymers, perfluoroalkoxy (PFA) resins, polychlorotrifluoroethylene (PCTFE) copolymers, ethylene-chlorotrifluoroethylene (ECTFE) copolymers, ethylene-tetrafluoroethylene (ETFE) copolymers, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), and copolymers, blends, and other combinations thereof. When used, such halogen-based flame retardants typically comprise no more than about 10 wt%, in some embodiments no more than about 5 wt%, and in some embodiments no more than about 1 wt% of the flame retardant system. Similarly, halogen-based flame retardants typically comprise no more than about 5 wt%, in some embodiments no more than about 1 wt%, and in some embodiments no more than about 0.5 wt% of the overall polymer composition.

[0041]

[0043] If desired, the polymer matrix may also contain a stabilizer system that helps maintain desired appearance and / or mechanical properties even after exposure to ultraviolet light and elevated temperatures. If used, the stabilizer system may comprise from about 0.1 wt % to about 5 wt %, in some embodiments from about 0.2 wt % to about 4 wt %, and in some embodiments, from about 0.4 wt % to about 3 wt % of the composition.

[0042]

[0044] The stabilizer system can include, for example, one or more antioxidants (e.g., sterically hindered phenol antioxidants, phosphite antioxidants, phosphonite antioxidants, thioester antioxidants, etc.), UV stabilizers, light stabilizers, heat stabilizers, etc., and combinations thereof. In one embodiment, for example, the stabilizer system can include a light stabilizer. For example, the stabilizer can include a hindered amine light stabilizer. When used, such light stabilizers can comprise from about 0.001 wt % to about 1 wt %, in some embodiments from about 0.01 wt % to about 0.5 wt %, and in some embodiments, from about 0.05 wt % to about 0.3 wt % of the total polymer composition. Hindered amine light stabilizers can be, for example, those having the following general structure:

[0043] [ka]

[0044] (In the formula, R1, R2, R3, and R5 are independently hydrogen, ether, ester, amine, amide, alkyl, alkenyl, alkynyl, aralkyl, cycloalkyl, and aryl groups, and the substituents may contain functional groups; examples of functional groups are alcohols, ketones, anhydrides, imines, siloxanes, ethers, carboxyl groups, aldehydes, esters, amides, imides, amines, nitriles, ethers, urethanes, or combinations thereof. The compound may contain one or more of the following compounds:

[0045] In certain embodiments, the hindered amine light stabilizer includes substituted piperidine compounds, such as alkyl-substituted piperidyl, piperidinyl, or piperazinone compounds, and substituted alkoxypiperidinyl compounds. Examples of such compounds include N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,3-benzenedicarboxamide (Nylostab® S-EED); 2,2,6,6-tetramethyl-4-piperidone; 2,2,6,6-tetramethyl-4-piperidinol; bis-(1,2,2,6,6-pentamethylpiperidyl)-(3',5'-di-tert-butyl-4'-hydroxybenzyl)butylmalonate. di-(2,2,6,6-tetramethyl-4-piperidyl) sebacate (Tinuvin® 770); oligomer of N-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol and succinic acid (Tinuvin® 622); oligomer of cyanuric acid and N,N-di(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine; bis-(2,2,6,6-tetramethyl-4-piperidinyl) succinate Bis-(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate (Tinuvin® 123); Bis-(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate (Tinuvin® 765); Tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate; N,N'-Bis-(2,2,6,6-tetramethyl-4-piperidyl)-hexane-1,6 -diamines (Chimasorb® T5); N-butyl-2,2,6,6-tetramethyl-4-piperidinaline; 2,2'-[(2,2,6,6-tetramethyl-piperidinyl)-imino]-bis-[ethanol]; poly((6-morpholine-5-triazine-2,4-diyl)(2,2,6,6-tetramethyl-4-piperidinyl)-iminohexamethylene-(2,2,6,6-tetramethyl-4-piperidinyl)-imino) (Chimasorb® UV 3346);5-(2,2,6,6-tetramethyl-4-piperidinyl)-2-cyclo-undecyl-oxazole) (Hostavin® N20); 1,1'-(1,2-ethane-di-yl)-bis-(3,3',5,5'-tetramethyl-piperazinone); polymethylpropyl-3-oxy-[4(2,2,6,6-tetramethyl)-piperidinyl]siloxane (Uvasil® 299); 1,2,3 ,4-Butane-tetracarboxylic acid-1,2,3-tris(1,2,2,6,6-pentamethyl-4-piperidinyl)-4-tridecyl ester; alpha-methylstyrene-N-(2,2,6,6-tetramethyl-4-piperidinyl)maleimide and N-stearylmaleimide copolymer; D-glucitol, 1,3:2,4-bis-O-(2,2,6,6-tetramethyl-4-piperidinylidene)-(HALS 7); 7-oxa-3,20-diazadispiro[5.1.11.2]-heneicosan-21-one-2,2,4,4-tetramethyl-20-(oxiranylmethyl) (Hostavin® N30); propanedioic acid, [(4-methoxyphenyl)methylene]-, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester (Sanduvor® PR 31); formamide, N,N'-1,6-hexanediylbis[N-(2,2,6,6-tetramethyl-4-piperidinyl) (Uvinul® 4050H); 1,3,5-triazine-2,4,6-trialine, N,N'''-[1,2-ethanediylbis[[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazin-2-yl]imino]-3,1-propanediyl]]-bis[N',N''-dibutyl-N',N''-bis(1,2,2,6,6-pentamethyl-4-piperidinyl) (Chimassorb® 119 MW2286; poly[[6-[(1,1,3,33-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)-imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino]] (Chimassorb® 944 MW 2000-3000);1,5-dioxaspiro(5,5)undecane-3,3-dicarboxylic acid, bis(2,2,6,6-tetramethyl-4-piperidinyl) ester (Cyasorb® UV-500); 1,5-dioxaspiro(5,5)undecane-3,3-dicarboxylic acid, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester (Cyasorb® UV-516); N-2, 2,6,6-Tetramethyl-4-piperidinyl-N-amino-oxamide;4-Acryloyloxy-1,2,2,6,6-pentamethyl-4-piperidine;1,5,8,12-Tetrakis[2',4'-bis(1'',2'',2'',6'',6''-pentamethyl-4''-piperidin-yl(butyl)amino)-1',3',5'-triazin-6'-yl]-1,5,8,12-tetrakis Lazadodecane; 3-Dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)-pyrrolidine-2,5-dione; 1,1'-(1,2-ethane-diyl)-bis-(3,3',5,5'-tetra-methyl-piperazinone) (Goodrite® 3034); 1,1',1''-(1,3,5-triazine-2,4,6-triyltris((cyclohexylimino)-2, 1-ethanediyl)tris(3,3,5,5-tetramethylpiperazinone) (Goodrite® 3150); 1,1',1''-(1,3,5-triazine-2,4,6-triyltris((cyclohexylimino)-2,1-ethanediyl)tris(3,3,4,5,5-tetramethylpiperazinone) (Goodrite® 3159); and the like.

[0046] In one particular embodiment, the hindered amine light stabilizer comprises an alkyl-substituted piperidyl compound. For example, the compound may be a di- or tricarboxylic acid (ester) amide, such as N,N'-bis(2,2,6,6-tetramethyl-4-piperdiyl)-1,3-benzenedicarboxamide (Nylostab® S-EED).

[0047] In addition to the light stabilizer, the stabilizer system may also include an antioxidant. When used, such antioxidants typically comprise from about 0.01 wt % to about 1 wt %, in some embodiments from about 0.05 wt % to about 0.8 wt %, and in some embodiments, from about 0.1 wt % to about 0.5 wt % of the total polymer composition. One type of suitable antioxidant is a sterically hindered phenolic antioxidant. Examples of such phenolic antioxidants include, for example, calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate) (Irganox® 1425); hexamethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate) (Irganox® 259); 1,2-bis(3,5,di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide (Irganox® 1024); phosphonic acid, (3,5-di-tert-butyl-4-hydroxybenzyl)-, dioctadecyl ester (Irganox® 1093); 1,3,5-trimethyl-2,4,6-tris(3' ,5'-di-tert-butyl-4'-hydroxybenzyl)benzene (Irganox® 1330); 2,4-bis(octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine (Irganox® 565); isooctyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox® 1135); octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox® 1076); 3,7-bis(1,1,3,3-tetramethylbutyl)-10H-phenothiazine (Irganox® LO 3); 2,2'-methylenebis(4-methyl-6-tert-butylphenol) monoacrylate (Irganox® 3052); 2-methyl-4,6-bis[(octylthio)methyl]phenol (Irganox® 1520); N,N'-trimethylenebis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide (Irganox® 1019);2,2'-Ethylidenebis[4,6-di-tert-butylphenol] (Irganox® 129); N,N'-(hexane-1,6-diyl)bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanamide) (Irganox® 1098); diethyl (3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate (Irganox® 1222); 4,4'-di-tert-octyldiphenylamine (Irganox® 5057); N-phenyl-1-naphthalenamine (Irganox® L 05); tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-6-methylphenylthio)-5-methylphenyl]phosphite (Hostanox® OSP 1); tetrakis[methylene-(3,5-di-tert-butyl-4-hydroxycinnamate)]methane (Irganox® 1010); and ethylene-bis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)-propionate (Irganox® 245);

[0048] Structure: [RP(OR1)2] m (1) (In the formula, R is a monovalent or polyvalent aliphatic, aromatic, or heteroaromatic organic group, such as a cyclohexyl, phenyl, phenylene, and / or biphenyl group; R1 is independently a compound of structure (II)

[0049] [ka]

[0050] or the two groups R1 are of the structure (III)

[0051] [ka]

[0052] forming a bridging group of During the ceremony, A is a direct bond, O, S, C 1~18 Alkylene (linear or branched), or C 1~18 alkylidene (linear or branched); R2 is independently C 1~12 Alkyl (linear or branched), C 1~12 Alkoxy, or C 5~12 is cycloalkyl; n is 0 to 5, in some embodiments 1 to 4, and in some embodiments 2 to 3; m is 1 to 4, in some embodiments 1 to 3, and in some embodiments 1 to 2 (e.g., 2). Phosphorus-containing antioxidants such as phosphonites having the formula:

[0053]

[0049] In accordance with the preceding claims, compounds are particularly preferred which are prepared via the Friedel-Crafts reaction of aromatic or heteroaromatic systems, such as benzene, biphenyl or diphenyl ether, with phosphorus trihalides, preferably phosphorus trichloride, in the presence of a Friedel-Crafts catalyst, such as aluminum chloride, zinc chloride, iron chloride, etc., and the subsequent reaction with phenols of structures (II) and (III). Also expressly encompassed within the present invention are mixtures of excess phosphorus trihalides and phosphites formed in a specific reaction sequence from the above-mentioned phenols.

[0054] In one particular embodiment, R1 is a group of structure (II). Among the compounds of this group, antioxidants of general structure (V) are particularly preferred:

[0055] [ka]

[0056] where n is as defined above. In one particular embodiment, by way of example, n in formula (V) is 1, and therefore the antioxidant is tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylene-diphosphonite.

[0057] Another suitable phosphorus-containing antioxidant is a phosphite antioxidant. The phosphite antioxidant can include a variety of different compounds, such as aryl monophosphites, aryl diphosphites, and the like, and mixtures thereof. For example, those having the following general structure (IX):

[0058] [ka]

[0059] (In the formula, R1, R2, R3, R4, R5, R6, R7, R8, R9, and R 10 are independently hydrogen, C1 to C 10 Alkyl, and C3-C 30 branched alkyl, e.g., selected from methyl, ethyl, propyl, isopropyl, butyl, or tertiary butyl moieties Aryl diphosphites having the formula:

[0060]

[0053] Examples of such aryl diphosphite compounds include, for example, bis(2,4-dicumylphenyl)pentaerythritol diphosphite (commercially available as Doverphos® S-9228) and bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite (commercially available as Ultranox® 626). Similarly, suitable aryl monophosphites include tris(2,4-di-tert-butylphenyl)phosphite (commercially available as Irgafos® 168); bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite (commercially available as Irgafos® 38); and the like.

[0061] Yet another suitable antioxidant is a thioester antioxidant. Particularly suitable thioester antioxidants for use in the present invention are thiocarboxylic acid esters, such as those having the following general structure: R 11 -O(O)(CH2) x -S-(CH2) y (O)OR 12 (In the formula, x and y are independently 1 to 10, in some embodiments 1 to 6, and in some embodiments 2 to 4 (e.g., 2); R 11 and R 12 are independently linear or branched C6-C 30 Alkyl, in some embodiments C 10 ~C 24 Alkyl, in some embodiments C 12 ~C 20 alkyl, for example, lauryl, stearyl, octyl, hexyl, decyl, dodecyl, oleyl, etc. It has the following characteristics.

[0062]

[0055] Specific examples of suitable thiocarboxylic acid esters include, for example, distearyl thiodipropionate (commercially available as Irganox® PS 800), 1,3-propanediyl ester; 3-lauryl thiopropionate (commercially available as AO-412S), dilauryl thiodipropionate (commercially available as Irganox® PS 802), di-2-ethylhexyl thiodipropionate, diisodecyl thiodipropionate, and the like.

[0063] The polymer composition may also contain one or more UV stabilizers. Suitable UV stabilizers include, for example, benzophenones (e.g., (2-hydroxy-4-(octyloxy)phenyl)phenyl, methanone (Chimassorb® 81), benzotriazoles (e.g., 2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole (Tinuvin® 234), 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole (Tinuvin® 329), 2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole (Tinuvin® 928)), triazines (e.g., 2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl) Examples of suitable UV stabilizers include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (Tinuvin® 770), sterically hindered amines (e.g., bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (Tinuvin® 770), or polymers of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethyl-4-piperidine (Tinuvin® 622)), and mixtures thereof. Benzophenones are particularly suitable for use in polymer compositions. When used, such UV stabilizers typically comprise from about 0.05 wt % to about 2 wt %, in some embodiments from about 0.1 wt % to about 1.5 wt %, and in some embodiments, from about 0.2 wt % to about 1.0 wt % of the composition.

[0064] In addition to the above components, the polymer matrix may also contain various other components. For example, if EMI shielding properties are desired, EMI fillers may be used. EMI fillers are generally formed from electrically conductive materials capable of providing the desired degree of electromagnetic interference shielding. In certain embodiments, for example, the material contains a metal, such as stainless steel, aluminum, zinc, iron, copper, silver, nickel, gold, chromium, etc., and alloys or mixtures thereof. EMI fillers may also have a variety of different forms, such as particles (e.g., iron powder), flakes (e.g., aluminum flakes, stainless steel flakes, etc.), or fibers. Particularly suitable EMI fillers are metal-containing fibers. In such embodiments, the fibers may be formed primarily from metal (e.g., stainless steel fibers), or the fibers may be formed from a core material coated with a metal. When a metal coating is used, the core material may be formed from a material that is either conductive or insulating in nature. For example, the core material may be formed from carbon, glass, or a polymer. One example of such a fiber is nickel-coated carbon fiber. In certain embodiments, for example, the resulting polymer compositions may exhibit an EMI shielding effectiveness ("SE") of about 40 decibels (dB) or greater, in some embodiments, about 45 dB or greater, in some embodiments, about 50 dB or greater, and in some embodiments, about 55 dB to about 200 dB, as determined according to ASTM D4935-18 at high frequencies such as 6 GHz. The EMI shielding effectiveness may remain stable over a high frequency range, e.g., about 700 MHz or greater, in some embodiments, about 1 GHz to about 100 GHz, and in some embodiments, about 2 GHz to about 18 GHz. The EMI shielding effectiveness may also be within a desired range for a variety of different part thicknesses, e.g., about 0.5 to about 10 millimeters, in some embodiments, about 0.8 to about 5 millimeters, and in some embodiments, about 1 to about 4 millimeters (e.g., 1 millimeter, 1.6 millimeters, or 3 millimeters). Within these high frequency and / or thickness ranges, for example, the average EMI shielding effectiveness may be about 40 dB or greater, in some embodiments about 45 dB or greater, and in some embodiments, from about 50 dB to about 200 dB.Similarly, the minimum EMI shielding effectiveness may be about 10 dB or greater, in some embodiments, about 15 dB or greater, and in some embodiments, about 20 dB to about 100 dB. The compositions may also have good EMI shielding effectiveness at lower frequencies, such as 200 MHz to 1.5 GHz. For example, within these lower frequency ranges and the thickness ranges described above, the average EMI shielding effectiveness may be about 50 dB or greater, in some embodiments, about 55 dB or greater, and in some embodiments, about 60 dB to about 200 dB.

[0065] Other additives can also be used to improve the hydrolysis resistance of the polymer composition. In some embodiments, for example, an epoxy component capable of reacting with the acid end groups of the aromatic polyester and having at least two epoxy functional groups per epoxy component molecule can be used. In one embodiment, the epoxy component can be at least one diphenol epoxy condensation polymer, including a condensation polymer of epichlorohydrin and a diphenol compound. Also preferred are 2,2-bis(p-glycidyl)(oxyphenyl)propane condensation products with 2,2-bis(p-hydroxyphenyl)propane and similar isomers. Commercially available diphenol epoxy condensation polymers include the EPON® 1000 resin series from Momentive Specialty Chemicals. Particularly suitable epoxy components contain at least two epoxy functional groups per epoxy component molecule, in some embodiments at least three epoxy functional groups, and in some embodiments at least four epoxy groups. The epoxy groups can contain glycidyl ethers, even more preferably glycidyl ethers of phenolic compounds. The epoxy component can be polymeric, oligomeric, or non-polymeric. An example of an epoxy component can be the tetraglycidyl ether of tetra(parahydroxyphenyl)ethane. An example of a commercially available epoxy component is Araldite® ECN 1299, available from Advanced Materials, Basel, Switzerland. Another example is EPON® 1031, available from Momentive Specialty Chemicals, Inc.Other epoxy components include epoxidized natural oils or fatty esters such as epoxidized soybean oil, epoxidized linseed / soybean oil, copolymers of styrene and glycidyl methacrylate, diglycidyl ethers of bisphenol A / bisphenol F, diglycidyl adducts of amines and amides, diglycidyl adducts of carboxylic acids, bis(3,4-epoxycyclohexylmethyl)adipate, vinylcyclohexene di-epoxide, epoxy phenol novolac and epoxy cresol novolac resins, epoxidized alkenes such as epoxidized alpha olefins, and epoxidized unsaturated fatty acids.

[0066] Impact modifiers may also be used in the polymer composition. When used, the impact modifier comprises from about 1 part by weight to about 50 parts by weight, in some embodiments from about 2 to about 40 parts by weight, and in some embodiments, from about 5 to about 30 parts by weight, per 100 parts by weight of the polymer matrix. 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.

[0067] To help impart the desired combination of softness, flexibility, and scratch resistance, the impact modifier can be a polymer containing a (meth)acrylic 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. The (meth)acrylic component can comprise, for example, from about 5 wt % to about 45 wt %, in some embodiments from about 10 wt % to about 42 wt %, and in some embodiments, from about 20 wt % to about 40 wt % of the impact modifier.

[0068] The (meth)acrylic component can be derived from one or more types of monomer components. In one embodiment, for example, the (meth)acrylic component can be derived in whole or in part from an "epoxy-functionalized" (meth)acrylic component. The term "epoxy-functionalized" generally means that the component contains, on average, two or more epoxy functional groups per molecule. For example, suitable epoxy-functionalized (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-functionalized monomers include allyl glycidyl ether, glycidyl methacrylate, and glycidyl itaconate. When used, the epoxy-functionalized (meth)acrylic monomer typically comprises from about 1 wt % to about 35 wt %, in some embodiments from about 2 wt % to about 20 wt %, and in some embodiments, from about 4 wt % to about 12 wt % of the impact modifier.

[0069]

[0062] Of course, non-epoxy-functionalized (meth)acrylic monomers can also be used. Examples of such (meth)acrylic monomers include methyl acrylate, ethyl acrylate, propyl acrylate (e.g., n-propyl acrylate, i-propyl acrylate, etc.), butyl acrylate (e.g., n-butyl acrylate, s-butyl acrylate, i-butyl acrylate, t-butyl acrylate, etc.), amyl acrylate (e.g., n-amyl acrylate, i-amyl acrylate, etc.), isobornyl acrylate, hexyl acrylate (e.g., n-hexyl acrylate), 2-ethylbutyl acrylate, 2-ethylhexyl acrylate, octyl acrylate (e.g., n-octyl acrylate), decyl acrylate (e.g., n-decyl acrylate), methylcyclohexyl acrylate, cyclopentyl acrylate, cyclohexyl acrylate, etc. Examples of the methacrylate include methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, propyl methacrylate (e.g., n-propyl methacrylate, i-propyl methacrylate, etc.), butyl methacrylate (e.g., n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, etc.), amyl methacrylate (e.g., n-amyl methacrylate, i-amyl methacrylate, etc.), hexyl methacrylate (e.g., n-hexyl 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. When used, non-epoxy functionalized (meth)acrylic monomers typically comprise from about 5 wt % to about 40 wt %, in some embodiments from about 10 wt % to about 35 wt %, and in some embodiments, from about 15 wt % to about 30 wt % of the impact modifier.

[0070] The impact modifier may also contain olefinic monomer units derived from one or more α-olefins. When used, such α-olefin monomers typically comprise from about 50 wt% to about 90 wt%, in some embodiments from about 60 wt% to about 85 wt%, and in some embodiments, from about 65 wt% to about 75 wt% of the copolymer. Examples of such monomers include, for example, linear and / or branched α-olefins having from 2 to 20 carbon atoms, typically from 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.

[0071] In one particular embodiment, for example, the impact modifier can be a random copolymer of an olefinic monomer (e.g., ethylene) and an epoxy-functionalized (meth)acrylic monomer (e.g., glycidyl methacrylate) or a non-epoxy-functionalized (meth)acrylic monomer. One commercially available example of such an impact modifier is Lotader® AX8840 (8 wt % glycidyl methacrylate and 92 wt % ethylene). In another embodiment, the impact modifier can be a terpolymer formed from an olefinic monomer (e.g., ethylene), an epoxy-functionalized (meth)acrylic monomer (e.g., glycidyl methacrylate), and a non-epoxy-functionalized (meth)acrylic monomer (e.g., butyl acrylate, methyl acrylate, butyl methacrylate, methyl methacrylate, etc.). Commercially available examples of such impact modifiers include Elvaloy® PTW (5 wt% glycidyl methacrylate, 28 wt% butyl acrylate, and 67 wt% ethylene), Lotader® AX8900 (8 wt% glycidyl methacrylate, 24 wt% methyl acrylate, 68 wt% ethylene), Lotader® AX8750 (5 wt% glycidyl methacrylate, 25 wt% butyl acrylate, and 70 wt% ethylene), and Lotader® AX8750T (5 wt% glycidyl methacrylate, 27 wt% butyl acrylate, and 68 wt% ethylene).

[0072] The resulting melt flow index of the impact modifier may vary, but is typically from about 1 to about 50 grams per 10 minutes ("g / 10 min"), in some embodiments from about 2 to about 40 g / 10 min, and in some embodiments from about 3 to about 25 g / 10 min, when determined according to ISO 1133-1:2022 at a load of 2.16 kg and a temperature of 190°C.

[0073] II. Melt Processing The method of combining the aromatic polyester, inorganic fiber, and various 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, mixers / kneaders, Banbury mixers, Farrel continuous mixers, single-screw extruders, twin-screw extruders, roll mills, and the like 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.

[0074] 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, those manufactured by 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 500 rpm or less, and in one embodiment, for example, about 200 rpm to about 450 rpm, or about 300 rpm to about 400 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 that provides 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).

[0075] III. Molded Components 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, the composition can be injected into the mold cavity using a piston. 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 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.

[0076]

[0059] Although not required, the resulting component may be laser marked as known in the art. Laser marking can be achieved by irradiating the component with a laser beam to decompose and sublimate specific laser marking additives, such as carbon black, contained in the polymer composition. Alternatively, a masking layer may be placed between the light source and the molded product so that the laser beam reaches only the area to be marked, and the entire surface is then irradiated with the laser beam. Examples of useful laser beams include Nd:YAG lasers and Nd:YVO4 lasers. In laser marking, the irradiation conditions of the laser beam are not particularly limited and can be appropriately adjusted according to the concentration of additives contained in the material used for the target molded product and the heat resistance of the resin. The irradiation conditions may be set so that the additive (e.g., carbon black) decomposes and sublimes, thereby discoloring the component.

[0077] IV. Product Use While the polymer compositions of the present invention can be used in a wide variety of potential product applications, they are particularly well-suited for use in electrical components, such as electronic modules. Such modules typically include a housing that receives one or more electrical components (e.g., printed circuit boards, antenna elements, radio frequency sensing elements, sensors, light sensing and / or transmitting elements (e.g., optical fiber), cameras, global positioning devices, etc.). The housing may, for example, include a base having sidewalls extending therefrom. A cover may also be supported on the sidewalls of the base to define an interior within which the electrical components are received and protected from the external environment. Regardless of the specific configuration of the module, composite materials may be used to form all or a portion of the housing and / or cover. In one embodiment, for example, composite materials may be used to form the base and sidewalls of the housing. The cover may be formed from the polymer composition of the present invention or from a different material. Notably, one benefit of the present invention is the elimination of traditional heat sinks from the module design, thereby reducing the weight and overall cost of the module. Nevertheless, in certain other embodiments, such heat sinks may be used. For example, the cover may in some cases include an additional metal component (eg, an aluminum plate).

[0078] Referring to FIG. 1 , by way of example, one particular embodiment of an electronic module 100 that can incorporate the composite material of the present invention is shown. The electronic module 100 includes a housing 102 that includes a sidewall 132 extending from a base 114. If desired, the housing 102 can also include a shroud 116 that can house an electrical connector (not shown). Regardless, a printed circuit board ("PCB") is received within the module 100 and attached to the housing 102. More specifically, the circuit board 104 includes holes 122 that align with and receive posts 110 located on the housing 102. The circuit board 104 has a first surface 118 on which electrical circuitry 121 is disposed to enable radio frequency operation of the module 100. For example, the RF circuitry 121 can include one or more antenna elements 120a and 120b. The circuit board 104 also has a second surface 119 opposite the first surface 118 that may optionally include other electrical components, such as components that enable digital electrical operation of the module 100 (e.g., a digital signal processor, semiconductor memory, input / output interface devices, etc.). Alternatively, such components may be provided on an additional printed circuit board. A cover 108 may also be used that is disposed on the circuit board 104 and attached to the housing 102 (e.g., sidewalls) by known techniques such as welding or adhesives to seal the electrical components therein. As indicated above, the polymer composition of the present invention may be used to form all or a portion of the cover 108 and / or housing 102. As noted above, because it has a high degree of thermal conductivity, a conventional heat sink may be eliminated.

[0079] The electronic module can be used in a wide variety of applications. For example, the electronic module can be used in an automotive vehicle (e.g., an electric vehicle, such as a battery-powered electric vehicle, a fuel cell electric vehicle, a plug-in hybrid electric vehicle (PHEV), a mild hybrid electric vehicle (MHEV), a full hybrid electric vehicle (FHEV), etc.). When used in an automotive application, for example, the electronic module can be used to sense the positioning of the vehicle relative to one or more three-dimensional objects. In this regard, the module can include radio frequency sensing components, light detection or optical components, cameras, antenna elements, etc., and combinations thereof. For example, the module can be a radio detection and detection (“radar”) module, a light detection and detection (“lidar”) module, a camera module, a global positioning module, etc., or it can be an integrated module that combines two or more of these components. Such modules may therefore employ a housing that receives one or more types of electrical components (e.g., printed circuit boards, antenna elements, radio frequency sensing devices, sensors, optical sensing and / or transmission elements (e.g., optical fibers), cameras, global positioning devices, etc.). In one embodiment, a lidar module may be formed that includes, for example, a fiber optic assembly for receiving and transmitting optical pulses, received within the housing / cover assembly in a manner similar to the embodiments discussed above. Similarly, radar modules typically include one or more printed circuit boards with dedicated electrical components for handling radio frequency (RF) radar signals, digital signal processing tasks, etc.

[0080]

[0063] The electronic module can also be used in 5G systems. For example, the electronic module can be an antenna module, such as a macrocell (base station), small cell, microcell, or repeater (femtocell). As used herein, "5G" generally refers to high-speed data communication over radio frequency signals. 5G networks and systems are capable of communicating data at much higher speeds than previous generation data communication standards (e.g., "4G," "LTE"). Various standards and specifications have been published to quantify the requirements for 5G communication. As an example, the International Telecommunication Union (ITU) published the International Mobile Telecommunications-2020 ("IMT-2020") standard in 2015. The IMT-2020 standard specifies various data transmission criteria (e.g., downlink and uplink data rates, latency, etc.) for 5G. The IMT-2020 standard defines uplink and downlink peak data rates as the minimum data rates for uploading and downloading data that 5G systems must support. The IMT-2020 standard sets the downlink peak data rate requirement at 20 Gbit / s and the uplink peak data rate at 10 Gbit / s. As another example, the 3rd Generation Partnership Project (3GPP) recently announced a new standard for 5G called "5G NR." In 2018, 3GPP published "Release 15," which defines the "first phase" of 5G NR standardization. 3GPP generally defines 5G frequency bands as "Frequency Band 1" (FR1), which includes frequencies below 6 GHz, and "Frequency Band 2" (FR2), which refers to the frequency bands in the 20-60 GHz range. However, as used herein, "5G frequencies" may refer to systems utilizing frequencies above 60 GHz, for example, in the ranges up to 80 GHz, up to 150 GHz, and up to 300 GHz.As used herein, "5G frequency" can refer to frequencies of about 1.8 GHz or higher, in some embodiments about 2.0 GHz or higher, in some embodiments about 3.0 GHz or higher, in some embodiments about 3 GHz to about 300 GHz or higher, in some embodiments about 4 GHz to about 80 GHz, in some embodiments about 5 GHz to about 80 GHz, in some embodiments about 20 GHz to about 80 GHz, and in some embodiments about 28 GHz to about 60 GHz.

[0081]

[0064] 5G antenna systems generally use high-frequency antennas and antenna arrays for 5G components, such as macrocells (base stations), small cells, microcells, or repeaters (femtocells), and / or other suitable components of a 5G system. The antenna elements / arrays and systems may satisfy or qualify as "5G" under standards published by 3GPP, such as Release 15 (2018), and / or the IMT-2020 standard. To achieve such high-speed data communications at high frequencies, the antenna elements and arrays generally use small feature sizes / spacings (e.g., fine pitch technology), which can improve antenna performance. For example, the feature sizes (spacing between antenna elements, width of antenna elements), etc., generally depend on the wavelength ("λ") (e.g., nλ / 4, where n is an integer) of the desired transmission and / or reception radio frequencies propagating through the substrate on which the antenna elements are formed. Additionally, beamforming and / or beamsteering can be used to facilitate reception and transmission (e.g., multiple-in-multiple-out (MIMO), massive MIMO) across multiple frequency bands or channels. High-frequency 5G antenna elements can have a variety of configurations. For example, 5G antenna elements can be or include coplanar waveguide elements, patch arrays (e.g., mesh grid patch arrays), or other suitable 5G antenna configurations. Antenna elements can be configured to provide MIMO, massive MIMO functionality, beamsteering, and the like. As used herein, "massive" MIMO functionality generally refers to providing a large number of transmission and reception channels by an antenna array, e.g., 8 transmit (Tx) and 8 receive (Rx) channels (abbreviated as 8x8). Massive MIMO functionality can be provided at 8x8, 12x12, 16x16, 32x32, 64x64, or more.

[0082] Antenna elements can be fabricated using a variety of manufacturing techniques. As an example, antenna elements and / or associated elements (e.g., ground elements, feed lines, etc.) can use fine-pitch technology. Fine-pitch technology generally refers to small or fine spacing between those components or leads. For example, feature sizes and / or spacings between antenna elements (or between antenna elements and ground planes) can be about 1,500 micrometers or less, in some embodiments 1,250 micrometers or less, in some embodiments 750 micrometers or less (e.g., center-to-center spacing of 1.5 mm or less), 650 micrometers or less, in some embodiments 550 micrometers or less, in some embodiments 450 micrometers or less, in some embodiments 350 micrometers or less, in some embodiments 250 micrometers or less, in some embodiments 150 micrometers or less, in some embodiments 100 micrometers or less, and in some embodiments 50 micrometers or less. However, it should be understood that smaller and / or larger feature sizes and / or spacings can also be used. As a result of such small feature sizes, antenna configurations and / or arrays can be achieved with a large number of antenna elements in a small footprint. For example, an antenna array can have an average antenna element concentration of more than 1,000 antenna elements per square centimeter, in some embodiments more than 2,000 antenna elements per square centimeter, in some embodiments more than 3,000 antenna elements per square centimeter, in some embodiments more than 4,000 antenna elements per square centimeter, in some embodiments more than 6,000 antenna elements per square centimeter, and in some embodiments more than about 8,000 antenna elements per square centimeter. Such a compact arrangement of antenna elements can provide a larger number of channels for MIMO functionality per unit area of ​​antenna area. For example, the number of channels can correspond to (e.g., be equal to or proportional to) the number of antenna elements.

[0083] 2 , for example, a 5G antenna system 100 may include a base station 102, one or more relay stations 104, one or more user computing devices 106, one or more Wi-Fi repeaters 108 (e.g., “femtocells”), and / or other suitable antenna components for a 5G antenna system 100. The relay stations 104 may be configured to facilitate communication with the base station 102 by the user computing devices 106 and / or other relay stations 104 by relaying or “repeat” signals between the base station 102 and the user computing devices 106 and / or relay stations 104. The base station 102 may include a MIMO antenna array 110 configured to receive and / or transmit radio frequency signals 112 to the relay stations 104, the Wi-Fi repeaters 108, and / or directly to the user computing devices 106. User computing devices 306 are not necessarily limited by the present invention and include devices such as 5G smartphones. The MIMO antenna array 110 may use beam steering to focus or direct the radio frequency signals 112 relative to the base station 104. For example, the MIMO antenna array 110 may be configured to adjust an elevation angle 114 relative to the XY plane and / or a heading angle 116 defined relative to the Z direction in the ZY plane. Similarly, one or more of the relay station 104, user computing device 106, and Wi-Fi repeater 108 may use beam steering to improve reception and / or transmission capabilities relative to the MIMO antenna array 110 by directionally adjusting the sensitivity and / or transmission of the devices 104, 106, and 108 relative to the MIMO antenna array 110 of the base station 102 (e.g., by adjusting one or both of the relative elevation angle and / or relative azimuth angle of each device).

[0084] Test Method Thermal Conductivity: As known in the art, the thermal diffusivity of a sample in various directions (in-plane, cross-plane, through-plane) can be first determined based on the laser flash method according to ASTM E1461-13(2022). The thermal conductivity (in-plane, cross-plane, and through-plane) can then be calculated using the following formula: Thermal Conductivity (W / m*K) = Cp*ρ*α, where Cp is the specific heat capacity of the sample (J / kgK) and ρ is the specific density of the sample (kg / m), determined according to ISO 11831-1:2019 (Method A). 3 ) and α is the thermal diffusion measurement (m 2 / s) can be calculated according to

[0085] 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 may be performed on identical specimen samples 80 mm long, 10 mm thick, and 4 mm wide. The test temperature may be 23°C, and the test speed may be 5 mm / min for tensile strength and tensile strain at break, and 1 mm / min for tensile modulus. For testing, the samples were first molded using a feed inlet temperature of 40-50°C, a heating zone 1 temperature of 250-260°C, a heating zone 2 temperature of 250-260°C, a heating zone 3 temperature of 250-260°C, a heating zone 4 temperature of 250-260°C, a nozzle temperature of 250-260°C, a mold temperature (static) of 80°C, and a mold temperature (moving) of 80°C.

[0086] 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.

[0087] 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).

[0088] Hydrolysis Resistance: Hydrolysis resistance can be measured using a "hydrolysis test," which can be performed by placing a test plaque in a pressure cooker at 121°C for a specified length of time, e.g., 96 or 168 hours. A pressure cooker uses moist heat in the form of saturated steam under pressure. The operating range of the pressure cooker is 15-21 psi (using a geared steam pressure gauge). The exposure time begins when the needle on the steam pressure gauge registers the above operating range (15-21 psi). During the test, the temperature can vary from 121°C to 127°C. After a predetermined amount of time, the mechanical properties of the test plaque can be measured and compared to the initial properties.

[0089] Electromagnetic Interference ("EMI") Shielding: EMI shielding effectiveness can be determined in accordance with ASTM D4935-18 in the frequency range of 1.5 GHz to 10 GHz (e.g., 5 GHz). The thickness of the test part can vary, for example, from 1 millimeter, 1.6 millimeters, or 3 millimeters. Testing can be performed using EM-2108 standard test equipment, which is a large cross-section coaxial transmission line and is available from various manufacturers, for example, Electro-Metrics. The measurement data relates to the shielding effectiveness due to plane waves (far-field EM waves) in which near-field values ​​for magnetic and electric fields can be interfered with.

[0090] Comparative Tracking Index ("CTI"): The comparative tracking index (CTI) can be determined in accordance with international standard IEC 60112-2020 and provides a quantitative indication of a composition's ability to act as an electrical insulator under moist and / or contaminated conditions. For testing, samples were first molded using a feed inlet temperature of 40-50°C, a heating zone 1 temperature of 260-270°C, a heating zone 2 temperature of 260-270°C, a heating zone 3 temperature of 270-280°C, a heating zone 4 temperature of 270-280°C, a nozzle temperature of 270-280°C, a mold temperature (static) of 120°C, and a mold temperature (moving) of 120°C. In determining a composition's CTI rating, two electrodes are placed on the molded specimen. A voltage difference is then established between the electrodes while 0.1% aqueous ammonium chloride solution is dropped onto the specimen. The maximum voltage that five specimens can withstand for the 50-drop test period without failing is determined. Test voltages range from 100 to 600 V in 25 V increments. The voltage value at which application of 50 drops of electrolyte causes a failure is the "comparative tracking index." The value provides an indication of the relative tracking resistance of the material. According to UL 746A, a nominal part thickness of 3 mm is considered representative of performance at other thicknesses.

[0091] 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.

[0092] [Table 1]

[0093] Comparative Example 1 Commercially available resin samples are formed from the components listed in the table below: PBT1 is polyethylene terephthalate (Celanex® JXK 1040) with a melt filament rate of 110 g / 10 min at 250° C. and a load of 2.16 kg, and PBT2 is polybutylene terephthalate (Celanex® JKX 1035) with a melt filament rate of 10 g / 10 min at 250° C. and a load of 2.16 kg.

[0094] [Table 2]

[0095]

[0075] The above samples are tested for mechanical properties and thermal conductivity as described herein, and the results are set forth below.

[0096] [Table 3]

[0097] Examples 1 to 3 Three resin samples are formed from the ingredients listed in the table below: Talc 1 has a median diameter of 7.5 μm, a 3.5 μm 2 The talc particles (Fabi HTP4) have a specific surface area (BET) of 1000 / g and a moisture content of 0.2% at 105°C.

[0098] [Table 4]

[0099]

[0077] The above samples are also tested for mechanical properties and thermal conductivity as described herein. The results are set forth below.

[0100] [Table 5]

[0101] Examples 4 to 7 Four resin samples are formed from the components listed in the table below. Impact modifier 1 is a copolymer of 84 wt % ethylene and 16 wt % ethyl acrylate (Elvaloy® 2116 AC) with a melt index of 1 g / 10 min at 190° C. and 2.16 kg. Impact modifier 2 is a copolymer of 8 wt % glycidyl methacrylate, 24 wt % methyl acrylate, 68 wt % ethylene (Lotader® AX8900) with a melt index of 6 g / 10 min at 190° C. and 2.16 kg. Impact modifier 3 is a copolymer of 8 wt % glycidyl methacrylate and 92 wt % ethylene (Lotader® AX8840) with a melt index of 5 g / 10 min at 190° C. and 2.16 kg.

[0102] [Table 6]

[0103]

[0079] The above samples are also tested for mechanical properties and thermal conductivity as described herein. The results are set forth below.

[0104] [Table 7]

[0105] Examples 8 to 11 Four resin samples are formed from the ingredients listed in the table below.

[0106] [Table 8]

[0107]

[0081] The above samples are also tested for mechanical properties and thermal conductivity as described herein. The results are set forth below.

[0108] [Table 9]

[0109]

[0082] 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: a polymeric matrix comprising an aromatic polyester; and an inorganic filler dispersed within the polymeric matrix, the inorganic filler comprising inorganic particles and optionally inorganic fibers, wherein the inorganic filler is present in an amount of from about 60 parts by weight to about 200 parts by weight per 100 parts by weight of the polymeric matrix; and the inorganic particles are present in an amount of from about 40 to about 200 parts by weight per 100 parts by weight of the polymeric matrix; and wherein the polymeric composition exhibits an in-plane thermal conductivity of greater than or equal to about 1.5 W / m·K, as determined in accordance with ASTM E1461-13(2022), and a melt fray rate of from about 0.1 to about 50 g / 10 min, as determined in accordance with ISO 1133:2022, at a temperature of about 250° C. and a load of 2.16 kg.

2. 10. The polymer composition of claim 1, exhibiting a cross-plane thermal conductivity of greater than or equal to about 1 W / m·K as determined according to ASTM E 1461-13(2022).

3. The polymer composition of claim 1 , wherein the polymer matrix comprises from about 30 wt % to about 70 wt % of the polymer composition.

4. 2. The polymer composition of claim 1, wherein the aromatic polyester is poly(ethylene terephthalate), poly(1,4-butylene terephthalate), poly(1,3-propylene terephthalate), poly(1,4-butylene 2,6-naphthalate), poly(ethylene 2,6-naphthalate), poly(1,4-cyclohexylene dimethylene terephthalate), or a combination thereof.

5. The polymer composition of claim 1 comprising glass fibers.

6. The polymer composition of claim 5 , wherein the glass fibers are coated with a sizing composition.

7. 7. The polymer composition of claim 6, wherein the coated glass fiber has a moisture content of about 0.5 wt% or less.

8. 10. The polymer composition of claim 1, wherein the inorganic particles comprise from about 20 wt% to about 70 wt% of the polymer composition.

9. The polymer composition of claim 1 , wherein the inorganic particles comprise metal silicate particles.

10. 10. The polymer composition of claim 9, wherein the metal silicate particles comprise talc.

11. The polymer composition of claim 1 , wherein the inorganic particles comprise metal hydroxide particles.

12. The polymer composition of claim 1 , wherein the inorganic particles comprise metal oxide particles.

13. The polymer composition of claim 1, wherein the inorganic fibers have a median diameter of about 1 to about 25 micrometers.

14. The inorganic particles have a particle size of from about 1 to about 100 m as determined in accordance with DIN 66131:1993 ２ 10. The polymer composition of claim 1, having a specific surface area of ​​about 100 / g and / or a moisture content of about 5% or less as determined according to ISO 787-2:1981 at a temperature of 105°C.

15. The polymer composition of claim 1 further comprising an impact modifier.

16. 10. The polymer composition of claim 1, which does not contain a filler having an intrinsic thermal conductivity of 100 W / m·K or greater.

17. An electronic module comprising a housing for receiving at least one electrical component, said housing comprising the polymer composition of claim 1.

18. 18. The electronic module of claim 17, which is a radar module or a lidar module.

19. The electronic module of claim 17 , wherein the electrical components include a camera.

20. 20. 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 including the electronic module of claim 18.

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