Thermoplastic compositions, methods for making same, and articles made therefrom

Abstract

The thermoplastic composition includes specific amounts of polyphenylene ether, a poly(phenylene ether)-poly(siloxane) block copolymer, a reinforcing filler, an organophosphate ester flame retardant, and an impact modifier including a hydrogenated block copolymer of an alkenyl aromatic and a conjugated diene. Methods for making the composition and articles including the composition are also disclosed.

Description

[Technical Field]

[0001] The present invention relates to thermoplastic compositions, methods for making same, and articles made therefrom.

[0002] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims priority to and the benefit of European Patent Application No. 22216851.0, filed December 28, 2022, the contents of which are hereby incorporated by reference in their entirety. [Background technology]

[0003] Poly(arylene ether)s are commercially attractive materials due to their unique combination of properties including, for example, high temperature resistance, dimensional and hydrolytic stability, and electrical properties. Summary of the Invention [Problem to be solved by the invention]

[0004] There is a continuing need in the art for poly(arylene ether) compositions that have low flammability, particularly for thin-wall applications. It would be further advantageous if, in addition to low flammability, the compositions also exhibited high mechanical strength, high heat resistance, and high impact strength. [Means for solving the problem]

[0005] The thermoplastic composition comprises 20 to 40 weight percent of a first poly(phenylene ether), 20 to 40 weight percent of a poly(phenylene ether)-poly(siloxane) block copolymer reaction product comprising a poly(phenylene ether)-poly(siloxane) block copolymer and a second poly(phenylene ether), 8 to 35 weight percent of a reinforcing filler, 10 to 20 weight percent of an organophosphate ester flame retardant, and optionally 1 to 15 weight percent of an impact modifier comprising a hydrogenated block copolymer of an alkenyl aromatic and a conjugated diene, wherein the weight percent of each component is based on the total weight of the composition.

[0006] Another aspect is a thermoplastic composition comprising a first poly(phenylene ether), a poly(phenylene ether)-poly(siloxane) block copolymer reaction product comprising a poly(phenylene ether)-poly(siloxane) block copolymer and a second poly(phenylene ether), a reinforcing filler, an organophosphate ester flame retardant, and optionally an impact modifier comprising a hydrogenated block copolymer of an alkenyl aromatic and a conjugated diene, wherein the thermoplastic composition comprises less than 1 weight percent hydrocarbon resin, and preferably, hydrocarbon resin is excluded from the thermoplastic composition, and wherein a molded sample of the composition exhibits the following: a 1.0 millimeter test bar a UL-94 flammability rating of V0 measured using a 0.75 millimeter test bar after conditioning for 48 hours at 23°C and for 168 hours at 70°C; a UL-94 flammability rating of V0 measured using a 0.5 millimeter test bar after conditioning for 48 hours at 23°C and for 168 hours at 70°C; a UL-94 flammability rating of V0 measured using a 0.3 millimeter test bar after conditioning for 48 hours at 23°C and for 168 hours at 70°C; and a tensile modulus of greater than or equal to 3500 MPa as determined in accordance with ASTM D638.

[0007] The method of making the composition comprises melt-mixing the components of the composition.

[0008] Articles comprising the compositions represent another aspect of the present disclosure.

[0009] These and other features are exemplified by the following detailed description. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present inventors have unexpectedly discovered that certain thermoplastic compositions can provide a desirable combination of properties. More specifically, a composition comprising a poly(phenylene ether)-poly(siloxane) block copolymer reaction product comprising a poly(phenylene ether)-poly(siloxane) block copolymer and a second poly(phenylene ether) in a particular amount, a reinforcing filler, an organophosphate ester flame retardant, and, optionally, an impact modifier comprising a hydrogenated block copolymer of an alkenyl aromatic and a conjugated diene, can provide a desirable combination of low flammability, high mechanical strength, high heat resistance, high impact strength, and hydrolysis resistance.

[0011] Accordingly, one aspect of the present disclosure is a thermoplastic composition. The thermoplastic composition comprises a first poly(phenylene ether). As used herein, a poly(phenylene ether) comprises repeating structural units according to formula (1): [ka] (1) In the formula, Z 1 Each event is independently a halogen, unsubstituted or substituted C 1-12 hydrocarbyl (provided that the hydrocarbyl group is not a tertiary hydrocarbyl), C1- 12 Hydrocarbylthio, C1- 12 Hydrocarbyloxy, or C2- 12 halohydrocarbyloxy (at least two carbon atoms separate the halogen atom and the oxygen atom), and Z 2 Each occurrence is independently hydrogen, halogen, unsubstituted or substituted C1- 12 hydrocarbyl (provided that the hydrocarbyl group is not a tertiary hydrocarbyl), C1- 12 Hydrocarbylthio, C1- 12 Hydrocarbyloxy, or C2- 12and halohydrocarbyloxy (at least two carbon atoms separate the halogen atom and the oxygen atom). As used herein, the term "hydrocarbyl," whether used by itself or as a prefix, suffix, or fragment of another term, refers to a residue containing only carbon and hydrogen. The residue can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It can also contain a combination of aliphatic, aromatic, straight-chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties. However, when a hydrocarbyl residue is described as substituted, it may optionally contain heteroatoms beyond the carbon and hydrogen members of the substituted residue. Thus, when specifically described as substituted, the hydrocarbyl residue can also contain one or more carbonyl groups, amino groups, hydroxyl groups, etc., or it can contain heteroatoms within the backbone of the hydrocarbyl residue. As an example, Z 1 may be a di-n-butylaminomethyl group formed by reaction of a terminal 3,5-dimethyl-1,4-phenyl group with the di-n-butylamine component of an oxidative polymerization catalyst.

[0012] In one embodiment, the first poly(phenylene ether) comprises 2,6-dimethyl-1,4-phenylene ether repeat units, i.e., repeat units according to formula (2): [ka] (2) 2,3,6-trimethyl-1,4-phenylene ether repeat units, or a combination thereof.

[0013] The first poly(phenylene ether) can include molecules having aminoalkyl-containing end groups, typically positioned ortho to the hydroxyl group. Tetramethyldiphenoquinone (TMDQ) end groups, typically obtained from a 2,6-dimethylphenol-containing reaction mixture in which tetramethyldiphenoquinone by-product is present, are also frequently present. The poly(phenylene ether) can exist in the form of a homopolymer, copolymer, graft copolymer, ionomer, or block copolymer, and combinations thereof.

[0014] In one embodiment, the first poly(phenylene ether) can have an intrinsic viscosity of 0.03 to 2 deciliters per gram (dl / g). For example, the poly(phenylene ether) can have an intrinsic viscosity of greater than 0.25 dl / g, or from 0.25 to 1.7 dl / g, specifically from 0.25 to 0.6 dl / g, more specifically from 0.25 to 0.4 dl / g, even more specifically from 0.35 to 0.50 dl / g, or from 0.4 to 0.6 dl / g, as measured using an Ubbelohde viscometer in chloroform at 25° C.

[0015] The first poly(phenylene ether) can be prepared by an oxidative polymerization method, in which the first poly(phenylene ether) is the product of oxidative polymerization of a monomer mixture that includes a monohydric phenol, and can be as described above.

[0016] The first poly(phenylene ether) may be present in the thermoplastic composition in an amount of 20 to 40 weight percent, based on the total weight of the composition. Within this range, the first poly(phenylene ether) may be present in an amount of 20 to 38 weight percent, or 21 to 39 weight percent, or 22 to 36 weight percent, or 22 to 35 weight percent, based on the total weight of the composition.

[0017] In addition to the first poly(phenylene ether), the thermoplastic composition includes a poly(phenylene ether)-poly(siloxane) block copolymer. As used herein, the term "poly(phenylene ether)-polysiloxane block copolymer" refers to a block copolymer comprising at least one poly(phenylene ether) block and at least one polysiloxane block. The poly(phenylene ether)-polysiloxane block copolymer can be prepared by oxidative copolymerization. In this method, the poly(phenylene ether)-polysiloxane block copolymer is the product of a process comprising oxidatively copolymerizing a monomer mixture comprising a monohydric phenol and a hydroxyaryl-terminated polysiloxane. In one embodiment, the monomer mixture comprises 70 to 99 parts by weight of the monohydric phenol and 1 to 30 parts by weight of the hydroxyaryl-terminated polysiloxane, based on the total weight of the monohydric phenol and the hydroxyaryl-terminated polysiloxane. The hydroxyaryl di-terminated polysiloxane can include a plurality of repeating units having the following structure: [ka] In the formula, R 8 Each event is independently hydrogen, C 1-12 Hydrocarbyl or C 1-12 is a halohydrocarbyl, and the two terminal units have the structure: [ka] In the formula, Y is hydrogen, C 1-12 Hydrocarbyl, C 1-12 hydrocarbyloxy, or halogen, and R 9 Each event is independently hydrogen, C 1-12 Hydrocarbyl or C 1-12 In one aspect, R is a halohydrocarbyl. 8 and R 9 Each occurrence of is methyl and Y is methoxy.

[0018] In one embodiment, the monohydric phenol comprises 2,6-dimethylphenol and the hydroxyaryl-terminated polysiloxane has the structure: [ka] where n is on average between 5 and 100, in particular between 30 and 60.

[0019] The oxidative copolymerization process produces poly(phenylene ether)-polysiloxane block copolymers as the desired product and poly(phenylene ether) (without incorporated polysiloxane blocks) as a by-product. Separation of the poly(phenylene ether) from the poly(phenylene ether)-polysiloxane block copolymer is not necessary. Thus, the poly(phenylene ether)-polysiloxane block copolymer can be used as a "reaction product" containing both poly(phenylene ether) and poly(phenylene ether)-polysiloxane block copolymer. Certain isolation procedures, such as precipitation from isopropanol, can ensure that the reaction product is essentially free of residual hydroxyaryl-terminated polysiloxane starting material. In other words, these isolation procedures ensure that essentially all of the polysiloxane content of the reaction product is in the form of poly(phenylene ether)-polysiloxane block copolymer. Detailed methods for forming poly(phenylene ether)-polysiloxane block copolymers are described in US Pat. Nos. 8,017,697 and 8,669,332 to Carrillo et al.

[0020] In one embodiment, the poly(phenylene ether)-polysiloxane block copolymer can provide, for example, 0.05 to 2 weight percent, specifically 0.1 to 1 weight percent, and more specifically 0.2 to 0.8 weight percent siloxane groups to the overall composition.

[0021] The composition comprises the poly(phenylene ether)-poly(siloxane) block copolymer reaction product in an amount of 20 to 40 weight percent, based on the total weight of the composition. Within this range, the first poly(phenylene ether) can each be present in an amount of 20 to 38 weight percent, or 21 to 39 weight percent, or 22 to 36 weight percent, or 22 to 35 weight percent, based on the total weight of the composition.

[0022] In one embodiment, the first poly(phenylene ether) and the poly(phenylene ether)-poly(siloxane) block copolymer reaction product can be present in a weight ratio of from 1.75:1 to 1:1.75, or from 1.5:1 to 1:1.5, or from 1.25:1 to 1:1.25, or from 1.1:1 to 1:1.1, or from 1.05:1 to 1:1.05.

[0023] In addition to the first poly(phenylene ether) and the poly(phenylene ether)-poly(siloxane) block copolymer, the thermoplastic composition further comprises a reinforcing filler.

[0024] Possible fillers or reinforcing agents include, for example, mica, clay, feldspar, quartz, quartzite, perlite, tripolites, diatomaceous earth, aluminum silicate (mullite), synthetic calcium silicate, fused quartz, fumed silica, sand, boron nitride powder, boron silicate powder, calcium sulfate, calcium carbonate (e.g., chalk, limestone, marble, and synthetic precipitated calcium carbonate), talc (including fibrous, modular, acicular, and lamellar talc), wollastonite, hollow or solid glass spheres, silicate spheres, cenospheres, aluminosilicates or (armospheres), kaolin, silicon carbide, alumina, boron carbide, iron, nickel, or copper whiskers, continuous and chopped carbon or glass fibers, molybdenum sulfide, sulfide Examples of fillers include zinc, barium titanate, barium ferrite, barium sulfate, barite, TiO2, aluminum oxide, magnesium oxide, particulate or fibrous aluminum, bronze, zinc, copper, or nickel, glass flakes, flaked silicon carbide, flaked aluminum diboride, flaked aluminum, steel flakes, natural fillers such as wood flour, fibrous cellulose, cotton, sisal, jute, starch, lignin, peanut shells, or rice husks, reinforcing organic fibrous fillers such as poly(ether ketone), polyimide, polybenzoxazole, poly(phenylene sulfide), polyester, polyethylene, aromatic polyamide, aromatic polyimide, polyetherimide, polytetrafluoroethylene, and poly(vinyl alcohol), and combinations thereof. Fillers and reinforcing agents can be coated with a layer of metallic material to promote electrical conductivity or surface treated with silane to improve adhesion and dispersibility in the polymer matrix.

[0025] In one aspect, the reinforcing filler can be a reinforcing fiber. Exemplary reinforcing fibers include glass fiber, carbon fiber, mineral fiber, or combinations thereof. In certain aspects, the reinforcing filler can include glass fiber.

[0026] The reinforcing filler may be present in the composition in an amount of 8 to 35 weight percent, based on the total weight of the thermoplastic composition. Within this range, the reinforcing fillers may each be present in an amount of 8 to 32 weight percent, or 10 to 30 weight percent, based on the total weight of the thermoplastic composition.

[0027] In addition to the first poly(phenylene ether), the poly(phenylene ether)-poly(siloxane) block copolymer, and the reinforcing filler, the thermoplastic composition further comprises an organophosphate flame retardant. Exemplary organophosphate compounds include phosphate esters containing phenyl groups, substituted phenyl groups, or a combination of phenyl and substituted phenyl groups, bis-aryl phosphate esters based on resorcinol, such as, for example, resorcinol bis(diphenyl phosphate), and those based on bisphenols, such as, for example, bisphenol A bis(diphenyl phosphate). In one embodiment, the organophosphate ester is selected from the following: tris(alkylphenyl)phosphate (e.g., CAS Reg. No. 89492-23-9 or CAS Reg. No. 78-33-1), resorcinol bis(diphenyl phosphate) (CAS Reg. No. 57583-54-7), bisphenol A bis(diphenyl phosphate) (CAS Reg. No. 181028-79-5), triphenyl phosphate (CAS Reg. No. 115-86-6), tris(isopropylphenyl)phosphate (e.g., CAS Reg. No. 68937-41-7), t-butylphenyl diphenyl phosphate (CAS Reg. No. 56803-37-3), bis(t-butylphenyl)phenyl phosphate (CAS Reg. No. 65652-41-7), tris(t-butylphenyl)phosphate (CAS Reg. No. 78-33-1), and combinations thereof.

[0028] In one embodiment, the organophosphate ester comprises a bis-aryl phosphate according to formula (7): [ka] (7) where R is independently C1- 12 is an alkylene group, and R 16 and R 17 is independently at each occurrence a C alkyl group; R 12 , R 13 , and R 15 is independently C1- 12 is a hydrocarbyl group, R 14 are independent and C1- 12 is a hydrocarbyl group, n is from 1 to 25, and s1 and s2 are independently integers equal to 0, 1, or 2. In one embodiment, OR 12 , OR 13 , OR 14 and OR 15 are independently derived from phenol, a monoalkylphenol, a dialkylphenol, or a trialkylphenol.

[0029] As will be readily recognized by those skilled in the art, bis-aryl phosphates are derived from bisphenols. Exemplary bisphenols include 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(4-hydroxy-3-methylphenyl)propane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dimethylphenyl)methane, and 1,1-bis(4-hydroxyphenyl)ethane. In one embodiment, the bisphenol comprises bisphenol A.

[0030] In one embodiment, the organophosphate ester comprises resorcinol bis-diphenyl phosphate, bis-phenol A bis-diphenyl phosphate, or a combination thereof.

[0031] The organophosphate ester may be present in the composition in an amount from 10 to 20 weight percent, based on the total weight of the composition. Within this range, the organophosphate ester may be present in an amount from 12 to 20 weight percent, or from 14 to 18 weight percent.

[0032] The thermoplastic composition optionally further comprises an impact modifier comprising a hydrogenated block copolymer of an alkenyl aromatic and a conjugated diene. For simplicity, this component is referred to as the "hydrogenated block copolymer." The hydrogenated block copolymer can comprise 10 to 90 weight percent poly(alkenyl aromatic) content and 90 to 10 weight percent hydrogenated poly(conjugated diene) content, based on the weight of the hydrogenated block copolymer. In one embodiment, the hydrogenated block copolymer is a low poly(alkenyl aromatic) hydrogenated block copolymer, in which the poly(alkenyl aromatic) content is 10 to less than 40 weight percent, or 20 to 35 weight percent, or 25 to 35 weight percent, or 30 to 35 weight percent, all based on the weight of the low poly(alkenyl aromatic) content hydrogenated block copolymer. In one embodiment, the hydrogenated block copolymer is a high poly(alkenyl aromatic content) hydrogenated block copolymer, wherein the poly(alkenyl aromatic) content is from 40 to 90 weight percent, or from 50 to 80 weight percent, or from 60 to 70 weight percent, all based on the weight of the high poly(alkenyl aromatic content) hydrogenated block copolymer.

[0033] In one embodiment, the hydrogenated block copolymer has a weight average molecular weight of 40,000 to 400,000 g / mol. Number average molecular weight and weight average molecular weight can be determined by gel permeation chromatography based on comparison to polystyrene standards. In one embodiment, the hydrogenated block copolymer has a weight average molecular weight of 200,000 to 400,000 g / mol, or 220,000 to 350,000 g / mol. In one embodiment, the hydrogenated block copolymer has a weight average molecular weight of 40,000 to 200,000 g / mol, or 40,000 to 180,000 g / mol, or 40,000 to 150,000 g / mol.

[0034] The alkenyl aromatic monomer used to prepare the hydrogenated block copolymer can have a structure according to formula (6): [ka] (6) In the formula, R 5 and R 6 are each independently a hydrogen atom, C 1-8 Alkyl group, or C 2-8 represents an alkenyl group, and R 7 and R 11 are each independently a hydrogen atom, C 1-8 represents an alkyl group, a chlorine atom, or a bromine atom, and R 8 , R 9 , and R 10 are each independently a hydrogen atom, C 1-8 Alkyl group or C 2-8 represents an alkenyl group, or R 8 and R 10 together with the central aromatic ring to form a naphthyl group, or R 9 and R 10 together with the central aromatic ring form a naphthyl group. Specific alkenyl aromatic monomers include, for example, styrene, chlorostyrenes such as p-chlorostyrene, methylstyrenes such as α-methylstyrene and p-methylstyrene, and t-butylstyrenes such as 3-t-butylstyrene and 4-t-butylstyrene. In one embodiment, the alkenyl aromatic monomer is styrene.

[0035] The conjugated dienes used to prepare the hydrogenated block copolymers are C 4-20 The conjugated diene may be a conjugated diene. Suitable conjugated dienes include, for example, 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and the like, and combinations thereof. In one embodiment, the conjugated diene is 1,3-butadiene, 2-methyl-1,3-butadiene, or a combination thereof. In one embodiment, the conjugated diene is 1,3-butadiene.

[0036] A hydrogenated block copolymer is a copolymer comprising (A) at least one block derived from an alkenyl aromatic compound and (B) at least one block derived from a conjugated diene, wherein the aliphatic unsaturation content in block (B) is at least partially reduced by hydrogenation. In one embodiment, the aliphatic unsaturation in the (B) block is reduced by at least 50 percent, or at least 70 percent. The arrangement of blocks (A) and (B) includes linear structures, graft structures, and radial teleblock structures with or without branching. Linear block copolymers include tapered linear structures and non-tapered linear structures. In one embodiment, the hydrogenated block copolymer has a tapered linear structure. In one embodiment, the hydrogenated block copolymer has a non-tapered linear structure. In one embodiment, the hydrogenated block copolymer comprises a (B) block containing random incorporation of alkenyl aromatic monomers. Linear block copolymer structures include diblock (AB block), triblock (ABA block or BAB block), tetrablock (ABAB block), and pentablock (ABABA block or BABAB block) structures, as well as linear structures containing a total of 6 or more (A) and (B) blocks, wherein the molecular weight of each (A) block can be the same or different from the other (A) blocks, and the molecular weight of each (B) block can be the same or different from the other (B) blocks. In one embodiment, the hydrogenated block copolymer is a diblock copolymer, a triblock copolymer, or a combination thereof.

[0037] In one embodiment, the hydrogenated block copolymer excludes residues of monomers other than alkenyl aromatic compounds and conjugated dienes. In one embodiment, the hydrogenated block copolymer is composed of blocks derived from alkenyl aromatic compounds and conjugated dienes. It does not contain grafts formed from these or any other monomers. It is also composed of carbon and hydrogen atoms, thus excluding heteroatoms. In one embodiment, the hydrogenated block copolymer contains one or more residues of an acid functionalizing agent, such as maleic anhydride. In one embodiment, the hydrogenated block copolymer comprises a polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer.

[0038] In one embodiment, the hydrogenated block copolymer is a polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer having a polystyrene content of 10 to 50 weight percent, or 20 to 40 weight percent, or 20 to 35 weight percent, or 25 to 35 weight percent, based on the weight of the polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer. In these embodiments, the polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer can optionally have a weight average molecular weight of 200,000 to 400,000 grams / mole, or 250,000 to 350,000 grams / mole, as determined by size exclusion chromatography using polystyrene standards.

[0039] Methods for preparing hydrogenated block copolymers are known in the art, and many hydrogenated block copolymers are commercially available. Exemplary commercially available hydrogenated block copolymers include polystyrene-poly(ethylene-propylene) diblock copolymers available from Kraton Performance Polymers Inc. as KRATON™ G1701 (having 37 weight percent polystyrene) and G1702 (having 28 weight percent polystyrene); polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymers available from Kraton Performance Polymers Inc. as KRATON™ G1641 (having 33 weight percent polystyrene), G1650 (having 30 weight percent polystyrene), G1651 (having 33 weight percent polystyrene), and G1654 (having 31 weight percent polystyrene); and polystyrene-poly(ethylene-ethylene / propylene)-polystyrene triblock copolymers available from Kuraray as SEPTON™ S4044, S4055, S4077, and S4099.Additional commercially available hydrogenated block copolymers include polystyrene-poly(ethylene-butylene)-polystyrene (SEBS) triblock copolymers available from Dynasol as CALPRENE™ H6140 (having 31 weight percent polystyrene), H6170 (having 33 weight percent polystyrene), H6171 (having 33 weight percent polystyrene), and H6174 (having 33 weight percent polystyrene) and from Kuraray as SEPTON™ 8006 (having 33 weight percent polystyrene) and 8007 (having 30 weight percent polystyrene); polystyrene-poly(ethylene-propylene)-polystyrene (SEPS) copolymers available from Kuraray as SEPTON™ 2006 (having 35 weight percent polystyrene) and 2007 (having 30 weight percent polystyrene); and Kraton Performance Polymers Oil-extended compounds of these hydrogenated block copolymers are available from Asahi Chemical Industry Co., Ltd. as KRATON™ G4609 (45% mineral oil, SEBS with 33 weight percent polystyrene) and G4610 (31% mineral oil, SEBS with 33 weight percent polystyrene), and from Asahi Chemical Industry Co., Ltd. as TUFTEC™ H1272 (36% oil, SEBS with 35 weight percent polystyrene). Mixtures of two or more hydrogenated block copolymers can be used. In one embodiment, the hydrogenated block copolymer comprises a polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer having a weight average molecular weight of at least 100,000 grams / mole, or from 200,000 to 400,000 grams / mole.

[0040] The composition comprises the hydrogenated block copolymer in an amount from 1 to 15 weight percent, based on the total weight of the composition. Within this range, the hydrogenated block copolymer amount can be from 1 to 10 weight percent, from 2 to 10 weight percent, or from 3 to 10 weight percent, or from 3 to 8 weight percent, or from 5 to 10 weight percent, or from 4 to 8 weight percent, or from 5 to 7 weight percent.

[0041] In one embodiment, impact modifiers other than the hydrogenated block copolymer can be minimized (i.e., present in an amount less than 1 weight percent) or can be eliminated from the thermoplastic composition, for example, homopolystyrene or high impact polystyrene can be eliminated from the composition.

[0042] The thermoplastic composition can optionally further comprise an additive composition. The additive composition includes one or more additives. The additives can be, for example, stabilizers, mold release agents, lubricants, processing aids, drip retardants, nucleating agents, UV blockers, dyes, pigments, antioxidants, antistatic agents, foaming agents, mineral oils, metal deactivators, antiblocking agents, or combinations thereof. In one embodiment, the additive composition can include antioxidants, lubricants, heat stabilizers, UV absorbing additives, plasticizers, anti-drippinning agents, mold release agents, antistatic agents, dyes, pigments, laser marking additives, radiation stabilizers, or combinations thereof. When present, such additives are typically used in a total amount of 0.1 to 10 weight percent, based on the total weight of the composition.

[0043] In one embodiment, the composition can include an anti-drip agent. Fluorinated polyolefins or polytetrafluoroethylene can be used as anti-drip agents. Anti-drip agents, such as fibril-forming or non-fibril-forming fluoropolymers, such as polytetrafluoroethylene (PTFE), can also be used. The anti-drip agent can be encapsulated by a rigid copolymer, such as styrene-acrylonitrile (SAN). PTFE encapsulated in SAN is known as TSAN. Encapsulated fluoropolymers can be produced by polymerizing the encapsulating polymer in the presence of the fluoropolymer, for example, in an aqueous dispersion. TSAN can offer a significant advantage over PTFE in that TSAN can be more easily dispersed in the composition. A suitable TSAN can include, for example, 50 wt% PTFE and 50 wt% SAN, based on the total weight of the encapsulated fluoropolymer. SAN can include, for example, 75 wt% styrene and 25 wt% acrylonitrile, based on the total weight of the copolymer. Alternatively, the fluoropolymer can be pre-blended in some manner with a second polymer, such as, for example, an aromatic polycarbonate resin or SAN, to form a cohesive material for use as a drip-proofing agent. Either method can be used to produce an encapsulated fluoropolymer.

[0044] The anti-drip agent can be added in the form of relatively large particles having a number average particle size of 0.3 to 0.7 mm, specifically 0.4 to 0.6 mm. The anti-drip agent can be used in an amount of 0.01 wt% to 5.0 wt%, based on the total weight of the composition.

[0045] The thermoplastic composition contains less than 1 weight percent of a hydrocarbon resin, based on the total weight of the thermoplastic composition. Preferably, the hydrocarbon resin can be excluded from the composition. As used herein, the term "hydrocarbon resin" refers to the following: aliphatic hydrocarbon resins, hydrogenated aliphatic hydrocarbon resins, aliphatic / aromatic hydrocarbon resins, hydrogenated aliphatic / aromatic hydrocarbon resins, cycloaliphatic hydrocarbon resins, hydrogenated cycloaliphatic resins, cycloaliphatic / aromatic hydrocarbon resins, hydrogenated cycloaliphatic / aromatic hydrocarbon resins, hydrogenated aromatic hydrocarbon resins, terpene resins, hydrogenated terpene resins, terpene-phenolic resins, rosin and rosin esters, hydrogenated rosin and rosin esters, and mixtures thereof. As used herein, "hydrogenated," when referring to a hydrocarbon resin, includes fully, substantially, and partially hydrogenated resins. Aromatic resins can include aromatic-modified aliphatic resins, aromatic-modified cycloaliphatic resins, and hydrogenated aromatic hydrocarbon resins, and can have an aromatic content of 1 to 30 weight percent. Any of the above resins can be grafted with an unsaturated ester or anhydride. In one embodiment, the composition can exclude hydrogenated aromatic hydrocarbon resins.

[0046] The composition can optionally minimize or exclude additional ingredients not specifically described herein. For example, the composition includes less than 5 weight percent, or less than 2 weight percent, or less than 1 weight percent, or less than 0.1 weight percent of a flame retardant synergist (e.g., a phosphazene). In one embodiment, the composition excludes a flame retardant synergist, such as a phosphazene. In one embodiment, the composition can exclude a thermoplastic polymer other than the polymer of the composition. In one embodiment, the composition can minimize or exclude homopolystyrene or rubber-modified polystyrene. In one embodiment, the composition can minimize or exclude tricalcium phosphate.

[0047] In a particular embodiment, a thermoplastic composition can comprise 20 to 38 weight percent of a first poly(phenylene ether), 20 to 38 weight percent of a poly(phenylene ether)-poly(siloxane) block copolymer reaction product comprising a poly(phenylene ether)-poly(siloxane) block copolymer and a second poly(phenylene ether), 8 to 32 weight percent of a reinforcing filler, 12 to 20 weight percent of an organophosphate ester flame retardant, and 2 to 10 weight percent of an impact modifier comprising a hydrogenated block copolymer of an alkenyl aromatic and a conjugated diene, wherein the weight percent of each component is based on the total weight of the composition, and the first poly(phenylene ether) and the poly(phenylene ether)-poly(siloxane) block copolymer reaction product are present in a weight ratio of 1.75:1 to 1:1.75. The first poly(phenylene ether) can include poly(2,6-dimethyl-1,4-phenylene ether) and have an intrinsic viscosity of 0.25 to 0.6 deciliters per gram as measured using an Ubbelohde viscometer in chloroform at 25°C. The reinforcing filler can include glass fiber. The hydrogenated block copolymer can include polystyrene-poly(ethylene-butylene)-polystyrene. The organophosphate flame retardant can include bis-phenol A bis-diphenyl phosphate.

[0048] Compositions according to the present disclosure can exhibit desirable combinations of properties. For example, molded samples of the composition can exhibit a UL-94 flammability rating of V0, measured using a 1.0 millimeter test bar after conditioning at 23°C for 48 hours and at 70°C for 168 hours; a UL-94 flammability rating of V0, measured using a 0.75 millimeter test bar after conditioning at 23°C for 48 hours and at 70°C for 168 hours; a UL-94 flammability rating of V0, measured using a 0.5 millimeter test bar after conditioning at 23°C for 48 hours and at 70°C for 168 hours; and a UL-94 flammability rating of V0, measured using a 0.3 millimeter test bar after conditioning at 23°C for 48 hours and at 70°C for 168 hours. Molded samples of the composition can further exhibit desirable mechanical properties, such as a tensile modulus of 3500 MPa or greater, as determined according to ASTM D638.

[0049] The compositions of the present disclosure can be prepared, for example, by melt-blending the components of the composition. The components of the composition can be mixed or blended using conventional equipment, such as a ribbon blender, a HENSCHEL™ mixer, a BANBURY™ mixer, a drum tumbler, etc., and the blended composition can then be melt-blended or melt-kneaded. Melt-blending or melt-kneading can be carried out using conventional equipment, such as a single-screw extruder, a twin-screw extruder, a multi-screw extruder, a co-kneader, etc. For example, the compositions can be prepared by melt-blending the components in a twin-screw extruder at a temperature of 270 to 310°C, or 280 to 300°C. The extrudate can be immediately quenched in a water bath and pelletized. The pellets so prepared can be one-quarter inch or less in length as desired. Such pellets can be used for subsequent molding, shaping, or forming.

[0050] Shaped, molded, or molded articles comprising the composition represent another aspect of the present disclosure. The composition can be molded into useful shaped articles by various methods, such as injection molding, extrusion, rotational molding, blow molding, and thermoforming. Some example articles include electric vehicle battery modules, battery housings, battery cases, battery cell frames, battery cell spacers, battery cell retainers, battery pack insulating films, bus bar holders, terminal covers, electrical or electronic components, thermosetting circuit breakers, fuser holders for electronic copiers, photovoltaic junction boxes, photovoltaic connectors, electrical connectors, automotive electrical connectors, electrical relays, charge couplers, appliance parts, automotive parts, portable devices, mobile parts, or stationary electrical components. In one aspect, the article is an extruded article, a molded article, a pultruded article, a thermoformed article, a foamed article, a layer in a multilayer article, a substrate for a coated article, or a substrate for a metallized article. In one aspect, the composition may be particularly useful in molded or extruded parts for electric vehicle battery components. For example, the compositions can be used in extruded parts for electric vehicle battery components, such as insulating sheets or films for electric vehicle battery components.

[0051] Electric vehicle battery components extruded from the compositions of the present disclosure represent another aspect of the present disclosure. The electric vehicle battery component can be an electric vehicle battery insulating sheet or film. The electric vehicle battery insulating sheet or film can be prepared by extruding the compositions of the present disclosure to provide the desired sheet or film. In one embodiment, the extruded film or sheet can have a UL-94 flammability rating of V0 measured using a 1.0 millimeter test bar after conditioning at 23°C for 48 hours and at 70°C for 168 hours, a UL-94 flammability rating of V0 measured using a 0.75 millimeter test bar after conditioning at 23°C for 48 hours and at 70°C for 168 hours, a UL-94 flammability rating of V0 measured using a 0.5 millimeter test bar after conditioning at 23°C for 48 hours and at 70°C for 168 hours, and a UL-94 flammability rating of V0 measured using a 0.3 millimeter test bar after conditioning at 23°C for 48 hours and at 70°C for 168 hours. The extruded film or sheet may optionally further exhibit one or both of a heat deflection temperature of 115°C or greater, measured on a 3.2 mm thick bar using a load of 1.82 MPa according to ASTM D648, and a comparative tracking resistance of PLC0, determined according to ASTM D3638. The battery insulation film may have a thickness of, for example, 50 to 1000 micrometers.

[0052] As described herein, the inventors have unexpectedly discovered that compositions containing specific amounts of the components described herein can provide certain advantageous properties. In particular, a combination of high mechanical strength, high heat resistance, high impact strength, and low flammability can be obtained, especially for thin-walled molded articles. Thus, the present disclosure provides significant improvements, particularly with respect to battery pack insulating films or sheets extruded from the compositions. [Example]

[0053] This disclosure is further illustrated by the following non-limiting examples.

[0054] The materials used in the examples below are listed in Table 1.

[0055] [Table 1]

[0056] The compositions were compounded using a Toshiba TEM-37BS twin-screw extruder. All ingredients were added at the feed throat of the extrudate, except for BPADP, which was added via a liquid feeder in zone 3, and glass fiber, which was added via a side feeder in zone 7. The extrudate was cooled in a water bath and pelletized. The pellets were conditioned at 120°C for 3 hours before being injection molded or extruded. The process parameters used are summarized in Table 2.

[0057] [Table 2]

[0058] Test articles were injection molded on a Toshiba UH1000-110 injection molding machine operating at barrel temperatures (feed throat to nozzle) of 290°C, 300°C, 300°C, and 290°C, and a mold temperature of 90°C.

[0059] The properties of the molded parts were tested according to the following standards:

[0060] Melt flow rate values, expressed in grams / 10 minutes, were determined according to ASTM D1238-10, Procedure B, at a temperature of 300° C. and a 5 kilogram load.

[0061] Heat deflection temperatures (HDT), expressed in °C, were determined according to ASTM D648 at 1.82 MPa or 0.45 MPa using bars having a thickness of 3.2 millimeters.

[0062] Notched Izod impact (NII) strength values, expressed in joules / meter, were determined according to ASTM D256-10 Method A at 23° C. using bar cross-section dimensions of 3.2 millimeters by 12.7 millimeters. Unnotched Izod impact values, expressed in joules / meter, were determined according to ASTM D4812 at 23° C. using bar cross-section dimensions of 3.2 millimeters by 12.7 millimeters.

[0063] Tensile properties were determined according to ASTM D638 at a sample thickness of 3.2 millimeters and a test speed of 5 millimeters / minute.

[0064] The flame retardancy of injection-molded flame bars was determined according to Underwriters Laboratory Bulletin 94, "Test for Flammability of Plastic Materials, UL94," 20 mm vertical flame test. Following this procedure, materials can be classified as HB, V0, UL94V1, V2, 5VA, and / or 5VB based on test results obtained on five samples, or three samples for the 5VB classification. Prior to testing, flame bars with thicknesses of 1.0, 0.75, 0.5, 0.3, and 0.2 mm were conditioned at 23°C and 50% relative humidity for at least 48 hours or at 70°C and 50% relative humidity for 168 hours. Sets of 10 to 20 flame bars were tested according to the UL94 20 mm vertical flame test. For each bar, a flame was applied to the bar for 10 seconds, then removed, and the time required for the bar to self-extinguish (first afterflame time, t1) was recorded. The flame was then reapplied for 10 seconds, removed, and the time required for the bar to self-extinguish (second afterflame time, t2) and post-flame glow time (afterglow time, t3) were recorded. To achieve a rating of V-0, the afterflame times t1 and t2 for each individual sample must be 10 seconds or less, the total afterflame time for all five samples (t1 + t2 for all five samples) must be 50 seconds or less, the second afterflame time + afterglow time (t2 + t3) for each individual sample must be 30 seconds or less, and the sample must not be able to flame and glow up to the holding clamp, and the cotton indicator cannot be ignited by particles or droplets of flame. To achieve a V-1 rating, the afterflame times t1 and t2 for each individual sample must be 30 seconds or less, and the total afterflame time for all five samples (t1 + t2 for all five samples) must be 250 seconds or less, and the second afterflame time plus afterglow time (t2 + t3) for each individual sample must be 60 seconds or less, and the sample cannot flame and glow up to the holding clamp, and the cotton indicator cannot be ignited by particles or droplets of flame.To achieve a V-2 rating, the afterflame times t1 and t2 for each individual sample must be 30 seconds or less, and the total afterflame time for all five samples (t1 + t2 for all five samples) must be 250 seconds or less, and the second afterflame time plus afterglow time (t2 + t3) for each individual sample must be 60 seconds or less, and the sample cannot flame and glow up to the holding clamp, but the cotton indicator can be ignited by particles or droplets of flame.

[0065] To obtain a 5VB rating, a flame is applied to a vertically fixed 5-inch (127 mm) x 0.5-inch (12.7 mm) test bar of the specified thickness with a dry, absorbent cotton pad placed 12 inches (305 mm) below the bar. The thickness of the test bar is determined with a vernier caliper to an accuracy of 0.1 mm. The flame is a 5-inch (127 mm) flame with a blue inner 1.58-inch (40 mm) cone. The flame is applied to the test bar for 5 seconds, with the tip of the blue cone hitting the bottom corner of the specimen. The flame is then removed for 5 seconds. The application and removal of the flame is repeated until the specimen has received five applications of the same flame. After the fifth application of the flame is removed, a timer (T-0) is started and the time the sample continues to flame (afterflame time) and the time the sample continues to glow after the afterflame has disappeared (afterglow time) are measured by stopping T-0 when the afterflame ceases, if there is no afterglow, and then stopping T-0 when the afterglow ceases. After five applications of the flame to the test bar, the combined afterflame and afterglow time must be 60 seconds or less, and there are no droplets that could ignite the cotton pad. The test is repeated on five identical bar samples. If one sample of the five does not comply with the time and / or no-droplet requirements, then a second set of five samples is tested in the same way. All samples in the second set of five samples must comply for a given thickness of material to achieve the 5VB standard.

[0066] To achieve a rating of 5VA, tests are conducted on both bar and plaque specimens. Procedure for Bars: The bar specimen is supported in a vertical position and a flame is applied to one of the specimen's lower corners at a 20° angle. The flame is applied for 5 seconds and removed for 5 seconds. The flame application and removal is repeated five times. Procedure for Plaques: The procedure for plaques is the same as for bars, except the plaque specimen is placed horizontally and the flame is applied to the center of the underside of the plaque. To achieve a rating of 5VA, the specimen must not have a flame or glow burn for more than 60 seconds after five flame applications. The specimen must not drip flame particles that would ignite the cotton. The plaque specimen must not show any burn-through (holes).

[0067] Hydrolytic stability was evaluated by placing tensile test bars in a hydrolysis chamber at 85°C and 85% relative humidity for 1000 hours. The samples were then removed from the chamber for characterization. Hydrolytic stability was evaluated by tensile modulus and tensile stress retention. ≥90% tensile modulus and tensile stress retention was characterized as "good." If at least one of tensile modulus or tensile stress retention was <90%, hydrolytic stability was characterized as "poor."

[0068] The compositions and properties are summarized in Table 3. The amount of each component is provided in weight percent based on the total weight of the composition.

[0069] [Table 3]

[0070] [Table 4]

[0071] As shown in Table 3, each of the compositions exhibited good dimensional stability and hydrolysis resistance. However, only Comparative Example 1, which contained only PPE as the matrix with 10% glass fiber, was able to achieve a V1 rating at 1 and 0.75 mm and a V2 rating at 0.5 and 0.3 mm. In Comparative Example 2, when the glass fiber content was increased to 30%, a V2 rating was achieved for all thicknesses ranging from 0.3 to 1 mm. Comparative Example 3, which contained 20% glass fiber with PPE-Si as the matrix, exhibited a V1 rating at all thicknesses tested. Thus, the comparative compositions failed to achieve a V0 rating at thicknesses of 1 mm or less. In addition, the comparative compositions did not achieve a "pass" rating for UL94 5VA or 5VB at a thickness of 1.5 mm.

[0072] In contrast, the compositions of Examples 1 to 4 demonstrate that the combination of PPE, PPE-Si, and glass fiber provides desirable flame resistance properties, particularly for thin-wall applications, while maintaining other mechanical properties. In particular, Example 1, containing PPE, PPE-Si, and 10% glass fiber, achieved a V0 rating at all thicknesses tested, ranging from 0.3 to 1 mm. A "pass" rating was also achieved at 1.5 mm for UL94 5VA. Increasing the glass fiber content to 20% as in Example 2 demonstrated similar flame resistance, and an increase in tensile modulus was also observed relative to the Example 1 composition. Further increasing the glass fiber content to 30% as in Example 3 demonstrated similar flame resistance, and a further increase in tensile modulus was also observed for both the Example 1 and Example 2 compositions. The composition of Example 4, similar to the Example 1 composition but further containing carbon black, demonstrated similar performance.

[0073] Table 3 further shows that in Comparative Examples 4 and 5, when the BPADP loading is reduced to less than 10 weight percent, the desired flame performance is not achieved at thicknesses of 1.0 mm or less.

[0074] Examples 6 through 12 in Table 3 further demonstrate that desirable combinations of properties can be obtained using other fillers, such as carbon fiber. The compositions of Examples 6-12 also suggest that impact modifiers may not be required.

[0075] Therefore, the combination of PPE and PPE-Si enabled desirable thin-wall flame resistance without sacrificing other properties. Thus, the present disclosure provides significant improvements. This disclosure further includes the following aspects.

[0076] Aspect 1: A thermoplastic composition comprising: 20 to 40 weight percent of a first poly(phenylene ether); 20 to 40 weight percent of a poly(phenylene ether)-poly(siloxane) block copolymer reaction product comprising a poly(phenylene ether)-poly(siloxane) block copolymer and a second poly(phenylene ether); 8 to 35 weight percent of a reinforcing filler; 10 to 20 weight percent of an organophosphate ester flame retardant; and optionally, 1 to 15 weight percent of an impact modifier comprising a hydrogenated block copolymer of an alkenyl aromatic and a conjugated diene, wherein the weight percent of each component is based on the total weight of the composition; and wherein the thermoplastic composition comprises less than 1 weight percent of a hydrocarbon resin; and preferably, the hydrocarbon resin is excluded from the thermoplastic composition.

[0077] Aspect 2: The thermoplastic composition of Aspect 1, wherein the first poly(phenylene ether) and the poly(phenylene ether)-poly(siloxane) block copolymer reaction product are present in a weight ratio of from 1.75:1 to 1:1.75, or from 1.5:1 to 1:1.5, or from 1.25:1 to 1:1.25, or from 1.1:1 to 1:1.1, or from 1.05:1 to 1:1.05.

[0078] Aspect 3: The thermoplastic composition of Aspect 1 or 2, wherein the first poly(phenylene ether) has an intrinsic viscosity of 0.25 deciliters per gram or greater, or from 0.25 to 0.6 deciliters per gram, or from 0.25 to 0.4 deciliters per gram, as measured in chloroform at 25° C. using an Ubbelohde viscometer; and preferably, the first poly(phenylene ether) comprises poly(2,6-dimethyl-1,4-phenylene ether).

[0079] Embodiment 4: The thermoplastic composition of any of Embodiments 1 to 3, wherein the reinforcing filler is a reinforcing fiber, preferably the reinforcing fiber comprises glass fiber, carbon fiber, mineral fiber, or a combination thereof.

[0080] Embodiment 5: The thermoplastic composition of any of embodiments 1 to 4, wherein the reinforcing filler comprises glass fiber or carbon fiber.

[0081] Embodiment 6: The thermoplastic composition of any of embodiments 1 to 5, wherein the impact modifier is present and the composition comprises a hydrogenated block copolymer comprising polystyrene-poly(ethylene-butylene)-polystyrene.

[0082] Aspect 7: The thermoplastic composition of any of Aspects 1 to 6, wherein the organophosphate ester flame retardant comprises resorcinol bis-diphenyl phosphate, bis-phenol A bis-diphenyl phosphate, resorcinol bis(di-2,6-dimethylphenyl) phosphate, an oligomeric phosphate ester, triphenyl phosphate, or a combination thereof, preferably bis-phenol A bis-diphenyl phosphate.

[0083] Embodiment 8: The thermoplastic composition of any of Embodiments 1 to 7, further comprising 0.1 to 10 weight percent of an additive composition.

[0084] Embodiment 9: The thermoplastic composition of embodiment 1, comprising: 20 to 38 weight percent of a first poly(phenylene ether), 20 to 38 weight percent of a poly(phenylene ether)-poly(siloxane) block copolymer reaction product comprising a poly(phenylene ether)-poly(siloxane) block copolymer and a second poly(phenylene ether), 8 to 32 weight percent of a reinforcing filler, 12 to 20 weight percent of an organophosphate ester flame retardant, and 2 to 10 weight percent of an impact modifier comprising a hydrogenated block copolymer of an alkenyl aromatic and a conjugated diene, the weight percent of each component being based on the total weight of the composition, and wherein the first poly(phenylene ether) and the poly(phenylene ether)-poly(siloxane) block copolymer reaction product are present in a weight ratio of 1.75:1 to 1:1.75.

[0085] Example 10: The thermoplastic composition of Example 9, wherein the first poly(phenylene ether) comprises poly(2,6-dimethyl-1,4-phenylene ether) and has an intrinsic viscosity of 0.25 to 0.6 deciliters per gram as measured using an Ubbelohde viscometer in chloroform at 25° C., the reinforcing filler comprises glass fiber or carbon fiber, the hydrogenated block copolymer comprises polystyrene-poly(ethylene-butylene)-polystyrene, and the organophosphate ester flame retardant comprises bis-phenol A bis-diphenyl phosphate.

[0086] Embodiment 11: The thermoplastic composition of any of Embodiments 1 to 10, wherein a molded sample of the composition exhibits: a UL-94 flammability rating of V0, measured using a 1.0 millimeter test bar after conditioning at 23°C for 48 hours and at 70°C for 168 hours; a UL-94 flammability rating of V0, measured using a 0.75 millimeter test bar after conditioning at 23°C for 48 hours and at 70°C for 168 hours; a UL-94 flammability rating of V0, measured using a 0.5 millimeter test bar after conditioning at 23°C for 48 hours and at 70°C for 168 hours; and a UL-94 flammability rating of V0, measured using a 0.3 millimeter test bar after conditioning at 23°C for 48 hours and at 70°C for 168 hours.

[0087] Aspect 12: The thermoplastic composition of any of Aspects 1 to 11, wherein a molded sample of the composition exhibits a tensile modulus of 3500 MPa or greater, as determined according to ASTM D638.

[0088] Embodiment 13: A method of making the composition of any of embodiments 1 to 12, comprising melt-mixing the components of the composition.

[0089] Embodiment 14: An article comprising the composition of any of embodiments 1 to 12.

[0090] Aspect 15: The article of aspect 14, wherein the article is an electric vehicle battery module, a battery housing, a battery case, a battery cell frame, a battery cell spacer, a battery cell retainer, a bus bar holder, a terminal cover, an electrical or electronic component, a thermosetting circuit breaker, a fuser holder for an electronic copier, a photovoltaic junction box, a photovoltaic connector, an electrical connector, an automotive electrical connector, an electrical relay, a charge coupler, an appliance component, an automotive component, a portable device, a mobile component, or a stationary electrical component.

[0091] Aspect 16: A thermoplastic composition comprising: a first poly(phenylene ether), a poly(phenylene ether)-poly(siloxane) block copolymer reaction product comprising a poly(phenylene ether)-poly(siloxane) block copolymer and a second poly(phenylene ether); a reinforcing filler; an organophosphate ester flame retardant; and optionally, an impact modifier comprising a hydrogenated block copolymer of an alkenyl aromatic and a conjugated diene, wherein the thermoplastic composition comprises less than 1 weight percent hydrocarbon resin, preferably, hydrocarbon resin is excluded from the thermoplastic composition, and wherein a molded sample of the composition exhibits the following: thermoplastic composition: 1.0 millimeter thickness; a UL-94 flammability rating of V0 measured using a 0.75 millimeter test bar after conditioning for 48 hours at 23°C and 168 hours at 70°C; a UL-94 flammability rating of V0 measured using a 0.5 millimeter test bar after conditioning for 48 hours at 23°C and 168 hours at 70°C; a UL-94 flammability rating of V0 measured using a 0.3 millimeter test bar after conditioning for 48 hours at 23°C and 168 hours at 70°C; and a tensile modulus of greater than 3500 MPa as determined in accordance with ASTM D638.

[0092] The compositions, methods, and articles may optionally comprise, consist of, or consist essentially of any suitable material, step, or ingredient disclosed herein. The compositions, methods, and articles may additionally, or alternatively, be formulated to be devoid of, or substantially free of, any material (or species), step, or ingredient that is not otherwise required to achieve the function or purpose of the compositions, methods, and articles.

[0093] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other. "Combinations" include blends, mixtures, alloys, reaction products, and the like. Terms such as "first," "second," and the like do not denote order, quantity, or importance; rather, they are used to distinguish one element from another. The terms "a," "an," or "the" do not denote a limitation of quantity and should be interpreted to encompass both the singular and the plural unless otherwise stated herein or clearly contradicted by context. "Or" means "and / or" unless expressly stated otherwise. Throughout the specification, reference to "one embodiment" means that a particular element described in connection with an embodiment is included in at least one embodiment described herein and may or may not be present in other embodiments. As used herein, the term "combinations thereof" includes one or more of the listed elements and is not limited, allowing for the presence of one or more similar elements not named. In addition, it should be understood that the described elements can be combined in any suitable manner in various embodiments.

[0094] Unless specified to the contrary herein, all test standards are the latest standards in effect as of the filing date of this application or, if priority is claimed, the filing date of the earliest priority application in which the test standard appears.

[0095] Unless otherwise defined, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if a term in this application contradicts or conflicts with a term in an incorporated reference, the term in this application shall take precedence over the conflicting term in the incorporated reference.

[0096] Compounds are described using standard nomenclature. For example, any position not substituted by any indicated group is understood to have its valence filled by the indicated bond or hydrogen atom. A dash ("-") that is not between two letters or symbols is used to indicate the point of attachment for a substituent. For example, -CHO is attached through the carbon of a carbonyl group.

[0097] As used herein, the term "hydrocarbyl," whether used alone or as a prefix, suffix, or fragment of another term, refers to a residue containing only carbon and hydrogen. The residue can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It can also contain a combination of aliphatic, aromatic, straight-chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties. However, when a hydrocarbyl residue is described as substituted, it may optionally contain heteroatoms in addition to the carbon and hydrogen members of the substituted residue. Thus, when specifically described as substituted, the hydrocarbyl residue can also contain one or more carbonyl groups, amino groups, hydroxyl groups, etc., or may contain heteroatoms within the backbone of the hydrocarbyl residue. The term "alkyl" refers to branched or straight-chain saturated aliphatic hydrocarbon groups, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, s-pentyl, and n- and s-hexyl. "Alkenyl" means a straight- or branched-chain, monovalent hydrocarbon group having at least one carbon-carbon double bond (e.g., ethenyl (-HC=CH2)). "Alkoxy" means an alkyl group linked through oxygen (i.e., alkyl-O-), such as methoxy, ethoxy, and sec-butyloxy groups. "Alkylene" means a straight- or branched-chain, saturated, divalent aliphatic hydrocarbon group (e.g., methylene (-CH2-) or propylene (-(CH2)3-)). "Cycloalkylene" means a divalent cyclic alkylene group, -C n H 2n-xwhere x is the number of hydrogens replaced by the cyclization(s). "Cycloalkenyl" refers to a monovalent group having one or more rings and one or more carbon-carbon double bonds within the rings, all ring members being carbon (e.g., cyclopentyl and cyclohexyl). "Aryl" refers to an aromatic hydrocarbon group containing the specified number of carbon atoms, e.g., phenyl, tropone, indanyl, or naphthyl. "Arylene" refers to a divalent aryl group. "Alkylarylene" refers to an arylene group substituted with an alkyl group. "Arylalkylene" refers to an alkylene group substituted with an aryl group (e.g., benzyl). The prefix "halo" refers to a group or compound containing one or more fluoro, chloro, bromo, or iodo substituents. Combinations of different halo atoms (e.g., bromo and fluoro) or only chloro atoms can be present. The prefix "hetero" means that the compound or group contains at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatoms), where the heteroatom(s) are each independently N, O, S, Si, or P. "Substituted" means that the compound or group contains, in place of a hydrogen, each independently, C 1-9 Alkoxy, C 1-9 Haloalkoxy, nitro (-NO2), cyano (-CN), C 1-6 Alkylsulfonyl (-S(=O)2-alkyl), C 6-12 Arylsulfonyl (-S(=O)2-aryl), thiol (-SH), thiocyano (-SCN), tosyl (CH3C6H4SO2-), C 3-12 Cycloalkyl, C 2-12 Alkenyl, C 5-12 Cycloalkenyl, C 6-12 Aryl, C 7-13 Aryl alkylene, C 4-12 Heterocycloalkyl, and C 3-12 Heteroaryl means substituted with at least one (e.g., 1, 2, 3, or 4) substituents, which may be heteroaryl, provided that the standard valence of the substituted atom is not exceeded. The number of carbon atoms indicated in the group excludes any substituents. For example, the group -CHCHCN is a C alkyl group substituted with a nitrile.

[0098] While particular embodiments have been described, presently unforeseen or unforeseen alternatives, modifications, variations, improvements, and substantial equivalents may occur to applicant or those skilled in the art. It is therefore intended that the appended claims, as filed and as they may be amended, shall embrace all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. 20 to 40 weight percent of a first poly(phenylene ether); 20 to 40 weight percent of a poly(phenylene ether)-poly(siloxane) block copolymer reaction product comprising a poly(phenylene ether)-poly(siloxane) block copolymer and a second poly(phenylene ether); 8 to 35 weight percent of a reinforcing filler; 10 to 20 weight percent of an organophosphate ester flame retardant; optionally, 1 to 15 weight percent of an impact modifier comprising a hydrogenated block copolymer of an alkenyl aromatic and a conjugated diene; A thermoplastic composition comprising: The weight percentage of each component is based on the total weight of the composition; and A thermoplastic composition, wherein the thermoplastic composition comprises less than 1 weight percent hydrocarbon resin, and preferably hydrocarbon resin is excluded from the thermoplastic composition.

2. 10. The thermoplastic composition of claim 1, wherein the first poly(phenylene ether) and the poly(phenylene ether)-poly(siloxane) block copolymer reaction product are present in a weight ratio of from 1.75:1 to 1:1.75, or from 1.5:1 to 1:1.5, or from 1.25:1 to 1:1.25, or from 1.1:1 to 1:1.1, or from 1.05:1 to 1:1.

05.

3. the first poly(phenylene ether) has an intrinsic viscosity of 0.25 deciliters per gram or greater, or from 0.25 to 0.6 deciliters per gram, or from 0.25 to 0.4 deciliters per gram, as measured in chloroform at 25° C. using an Ubbelohde viscometer; The thermoplastic composition of claim 1 or 2, wherein the first poly(phenylene ether) preferably comprises poly(2,6-dimethyl-1,4-phenylene ether).

4. 4. The thermoplastic composition of claim 1, wherein the reinforcing filler is a reinforcing fiber, preferably the reinforcing fiber comprises glass fiber, carbon fiber, mineral fiber, or a combination thereof.

5. 5. The thermoplastic composition of claim 1, wherein the reinforcing filler comprises glass fiber or carbon fiber.

6. 6. The thermoplastic composition of any one of claims 1 to 5, wherein the impact modifier is present and comprises a hydrogenated block copolymer comprising polystyrene-poly(ethylene-butylene)-polystyrene.

7. 7. The thermoplastic composition of any one of claims 1 to 6, wherein the organophosphate ester flame retardant comprises resorcinol bis-diphenyl phosphate, bis-phenol A bis-diphenyl phosphate, resorcinol bis(di 2,6-dimethylphenyl) phosphate, oligomeric phosphate ester, triphenyl phosphate, or a combination thereof, preferably bis-phenol A bis-diphenyl phosphate.

8. 8. The thermoplastic composition of claim 1, further comprising 0.1 to 10 weight percent of an additive composition.

9. 20 to 38 weight percent of a first poly(phenylene ether); 20 to 38 weight percent of a poly(phenylene ether)-poly(siloxane) block copolymer reaction product comprising a poly(phenylene ether)-poly(siloxane) block copolymer and a second poly(phenylene ether); 8 to 32 weight percent of a reinforcing filler; 12 to 20 weight percent of an organophosphate ester flame retardant; an impact modifier comprising 2 to 10 weight percent of a hydrogenated block copolymer of an alkenyl aromatic and a conjugated diene; 10. The thermoplastic composition of claim 1, comprising: The weight percentage of each component is based on the total weight of the composition; and A thermoplastic composition wherein the first poly(phenylene ether) and the poly(phenylene ether)-poly(siloxane) block copolymer reaction product are present in a weight ratio of 1.75:1 to 1:1.

75.

10. the first poly(phenylene ether) comprises poly(2,6-dimethyl-1,4-phenylene ether) and has an intrinsic viscosity of 0.25 to 0.6 deciliters per gram as measured using an Ubbelohde viscometer in chloroform at 25° C.; the reinforcing filler comprises glass fiber or carbon fiber; the hydrogenated block copolymer comprises polystyrene-poly(ethylene-butylene)-polystyrene; and 10. The thermoplastic composition of claim 9, wherein the organophosphate ester flame retardant comprises bis-phenol A bis-diphenyl phosphate.

11. 11. The thermoplastic composition of any one of claims 1 to 10, wherein a molded sample of the composition exhibits the following: UL-94 flammability rating of V0, measured using a 1.0 millimeter test bar after conditioning at 23°C for 48 hours and at 70°C for 168 hours; UL-94 flammability rating of V0, measured using a 0.75 millimeter test bar after conditioning at 23°C for 48 hours and at 70°C for 168 hours; A UL-94 flammability rating of V0, measured using a 0.5 millimeter test bar after conditioning at 23°C for 48 hours and at 70°C for 168 hours; and UL-94 flammability rating of V0 measured using a 0.3 mm test bar after conditioning at 23°C for 48 hours and at 70°C for 168 hours

12. 12. The thermoplastic composition of any one of claims 1 to 11, wherein a molded sample of the composition exhibits a tensile modulus of greater than or equal to 3500 MPa, as determined according to ASTM D638.

13. 13. A method of making the composition of any one of claims 1 to 12, comprising the step of melt-mixing the components of the composition.

14. 13. An article comprising the composition of any one of claims 1 to 12, optionally an electric vehicle battery module, a battery housing, a battery case, a battery cell frame, a battery cell spacer, a battery cell retainer, a bus bar holder, a terminal cover, an electrical or electronic component, a thermoset circuit breaker, a fuser holder for an electronic copier, a photovoltaic junction box, a photovoltaic connector, an electrical connector, an automotive electrical connector, an electrical relay, a charge coupler, an appliance component, an automotive component, a portable device, a mobile component, or a stationary electrical component.

15. a first poly(phenylene ether); and a poly(phenylene ether)-poly(siloxane) block copolymer reaction product comprising a poly(phenylene ether)-poly(siloxane) block copolymer and a second poly(phenylene ether); Reinforcing filler; an organic phosphate ester flame retardant; optionally, an impact modifier comprising a hydrogenated block copolymer of an alkenyl aromatic and a conjugated diene; A thermoplastic composition comprising: the thermoplastic composition comprises less than 1 weight percent hydrocarbon resin, preferably hydrocarbon resin is excluded from the thermoplastic composition; and A molded sample of the composition exhibits the following: Thermoplastic composition. UL-94 flammability rating of V0, measured using a 1.0 millimeter test bar after conditioning at 23°C for 48 hours and at 70°C for 168 hours; UL-94 flammability rating of V0, measured using a 0.75 millimeter test bar after conditioning at 23°C for 48 hours and at 70°C for 168 hours; UL-94 flammability rating of V0, measured using a 0.5 mm test bar after conditioning at 23°C for 48 hours and at 70°C for 168 hours; A UL-94 flammability rating of V0, measured using a 0.3 millimeter test bar after conditioning at 23°C for 48 hours and at 70°C for 168 hours; and Tensile modulus of 3500 MPa or greater, determined according to ASTM D638

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