Flame retardant thermoplastic compositions and articles thereof

Abstract

Thermoplastic compositions including a poly(arylene ether) composition, one or more hydrogenated block copolymers derived from an alkenyl aromatic monomer comprising styrene and a conjugated diene, an organophosphorus flame retardant, and optional components can have a UL94 5VA rating at a thickness of 1.5 mm or less, a UL94 5VB rating at a thickness of 1.5 mm or less, and a UL94 rating of V0 at a thickness of 1.5 mm or less, and a notched impact strength of at least 168 J / m at 23 °C according to ASTM D256, or a heat deflection temperature of 130 °C or greater when measured at a force of 0.45 megapascals according to ASTM D638, or a combination thereof.

Description

FLAME RETARDANT THERMOPLASTIC COMPOSITIONS AND ARTICLES THEREOFCROSS REFERENCE TO RELATED APPLICATIONThis application claims priority to EP 24188228.1, filed July 12, 2024, the entire contents of which are incorporated herein by reference.BACKGROUND

[0001] This disclosure relates to flame retardant thermoplastic compositions, methods of manufacture, and articles thereof.

[0002] Poly(arylene ethers) can improve dielectric performance, heat resistance, flame resistance and moisture absorption of materials, making them particularly well suited for a variety of applications, including electronic applications. However, because thermoplastic materials such as poly(arylene ethers) are less thermally conductive than metals, any heat generated in these materials is not easily dissipated (“heat dissipation”). For example, injunction boxes, where heat dissipation is crucial, the low thermal conductivity of thermoplastics can lead to overheating of electrical components, potentially reducing their lifespan and reliability. To that end, the industry trend is to decrease the wall thickness of the thermoplastic article to improve heat dissipation.

[0003] Some applications for poly(arylene ether) compositions require significant flame retardant capability. UL 94 is the standard for testing the flammability of plastic materials for parts in devices and appliances, and it includes several classifications, such as HB, V-0, V-l, V-2, 5VB, and 5VA. Among these, the UL 945VA rating is one of the most stringent, indicating that the material can withstand severe conditions without significant flame propagation. Conventional compositions including poly(arylene ethers) are currently used for photovoltaic junction boxes and connectors, in particular, poly(phenylene ether) / poly styrene blends (PPE / PS). Polystyrene is incorporated for improved processability, but the resulting blends fail to achieve a UL 945VA rating at a sample thickness of 1.5 mm.

[0004] Thus, there is a need for thermoplastic compositions including poly(arylene ethers) having a combination of high heat resistance. It would be a further advantage if the thermoplastic compositions had high impact strength and / or high flame retardance.BRIEF DESCRIPTION

[0005] In an aspect, a thermoplastic composition comprises: a poly(arylene ether) composition comprising a poly(arylene ether) and excluding a poly(arylene ether siloxane); an organophosphorus flame retardant present in an amount effective to provide at least 1.1 wt% phosphorus, based on the total weight of the composition; optionally, a polystyrene comprising greater than 98 wt%, preferably greater than 99 wt% repeating units derived from styrene; a hydrogenated block copolymer derived from an alkenyl aromatic monomer comprising styrene and a conjugated diene, optionally, less than 10 wt% of a rubber-modified polystyrene, or less than 10 wt% of a rubber-modified polystyrene; optionally, acolorant composition; and optionally, an additive composition, wherein the thermoplastic composition totals 100 wt%, wherein a sample of the thermoplastic composition has: a UL94 5VA rating at a thickness of 1.5 mm or less, and a UL945VB rating at a thickness of 1.5 mm or less, and a UL94 rating of VO at a thickness of 1.5 mm or less, an Nil of at least 168 Joules / meter (J / m) at 23 °C according to ASTM D256, or a heat deflection temperature (HDT) of 130 °C or greater when measured at a force of 0.45 megapascals according to ASTM D638, or a combination thereof.

[0006] In another aspect, a thermoplastic composition comprises: a poly(arylene ether) composition comprising a poly(arylene ether) and a poly(arylene ether siloxane); an organophosphorus flame retardant present in an amount effective to provide at least 0.9 wt% phosphorus, based on the total weight of the composition; optionally, a polystyrene comprising greater than 98 wt%, preferably greater than 99 wt% repeating units derived from styrene; a hydrogenated block copolymer derived from an alkenyl aromatic monomer comprising styrene and a conjugated diene, optionally, less than 10 wt% of a rubber-modified polystyrene, or less than 10 wt% of a rubber-modified polystyrene; optionally, a colorant composition; and optionally, an additive composition, wherein the thermoplastic composition totals 100 wt%, wherein a sample of the thermoplastic composition has: a UL94 5VA rating at a thickness of 1.5 mm or less, and a UL945VB rating at a thickness of 1.5 mm or less, and a UL94 rating of V0 at a thickness of 1.5 mm or less, and an Nil of at least 168 J / m according to ASTM D256, or an HDT of 130 °C or greater when measured at a force of 0.45 megapascals according to ASTM D638, or a combination thereof.

[0007] In an aspect, a method of manufacture comprises combining the above-described components to form a thermoplastic composition.

[0008] In another aspect, an article comprises the above-described thermoplastic compositions.

[0009] In yet another aspect, a method of manufacture of an article comprises molding, extruding, or shaping the above-described thermoplastic composition into an article.

[0010] The above described and other features are exemplified by the following detailed description.DETAILED DESCRIPTION

[0011] The inventors have discovered thermoplastic compositions that can have the desired combination of high heat resistance, high impact strength, and high flame retardance. The thermoplastic compositions include a poly(arylene ether) composition, one or more hydrogenated block copolymers derived from an alkenyl aromatic monomer comprising styrene and a conjugated diene, an organophosphorus flame retardant, and other optional components. The poly (arylene ether) compositions have a combination of high heat resistance, high impact strength, and high flame retardance: a UL94 5VA rating at a thickness of 1.5 mm or less, a UL94 5VB rating at a thickness of 1.5 mm or less, and a UL94 rating of V0 at a thickness of 1.5 mm or less, a notched impact strength of at least 168 J / m at 23 °C according to ASTM D256, or an HDT of 130 °C or greater when measured at a force of 0.45 megapascals according to ASTM D638, or a combination thereof.

[0012] The poly(arylene ether) composition may include a poly(arylene ether) and exclude a poly(arylene ether siloxane), or may include a combination of a poly(arylene ether) and a poly(arylene ether siloxane). The poly(arylene ether) and the poly(arylene ether siloxane) are derived from monomers including a monohydric phenol, or a monohydric phenol and a dihydric phenol. The monohydric phenol may have the following formula (1)wherein Z1is independently at each occurrence is halogen, unsubstituted or substituted C1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, or C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; and Z2is independently at each occurrence hydrogen, halogen, unsubstituted or substituted C1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, or C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atom.

[0013] In some aspects, the poly(arylene ether) and / or the poly(arylene ether siloxane) include repeating units derived from a monohydric phenol, and having the formula (la)wherein Qlais C1-C12 primary or secondary alkyl or cycloalkyl, preferably C1-C12 primary alkyl, more preferably Ci-Ce primary alkyl, even more preferably methyl; Qlbis halogen, C1-C12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1-C12 hydrocarbylthio, C1-C12 hydrocarbyloxy, or C2-C12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, preferably C1-C12 alkyl or C3-C12 cycloalkyl, more preferably Ci-Ce alkyl, even more preferably methyl. Each occurrence of Q2is independently hydrogen, halogen, unsubstituted or substituted C1-C12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1-C12 hydrocarbylthio, C1-C12 hydrocarbyloxy, or C2-C12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, preferably hydrogen; and e is 1 to 200, preferably 1 to 100; and y is 1 or 2, preferably 2. For example, Qlais methyl or cyclohexyl, and Qlbis halogen, unsubstituted C1-C12 alkyl provided that the alkyl group is not tertiary alkyl, or unsubstituted C1-C12 aryl.

[0014] Exemplary monohydric phenols include 2,6-dimethylphenol, 2-methylphenol, 2,5-dimethylphenol, 2-allyl-6-methylphenol, 2,3,6-trimethylphenol, 2-methyl-6-phenyl phenol,2-cyclohexyl-6-methylphenol, or a combination thereof. For example, the monohydric phenol may include 2,6-dimethylphenol.

[0015] In addition to repeating units derived from a monohydric phenol, poly(arylene ether) and / or the poly(arylene ether siloxane) may be derived from a dihydric phenol having the structure of formula (2)wherein each occurrence of Q1and Q2independently comprises halogen, unsubstituted or substituted Ci- 15 primary or secondary hydrocarbyl, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, or C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; each occurrence of Q3and Q4independently comprises hydrogen, halogen, unsubstituted or substituted C1-C15 primary or secondary hydrocarbyl, C1-C12 hydrocarbylthio, C1-12 hydrocarbyloxy, or C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; x and y have an average value, and are each independently 0-30, or 0-20, preferably 0-15, still more preferably 0- 10, even more preferably 0-8, provided that the sum of x and y is at least 2, preferably at least 3, more preferably at least 4.

[0016] In Formula (2), L may be of formula (3)wherein each occurrence of R3, R4, R5, and R6independently comprises hydrogen, halogen, unsubstituted or substituted C1-12 primary or secondary hydrocarbyl, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, or C2- 12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; w is 0 or 1; and Y iswherein each occurrence of R7independently comprises hydrogen or C1-12 hydrocarbyl, each occurrence of R8and R9independently comprises hydrogen, C1-12 hydrocarbyl, or R8and R9together form a C4-12 cyclohydrocarbylene with the carbon atom. In an aspect in formula (3), each of R3, R4, R5, and R6independently comprises hydrogen, halogen, unsubstituted or substituted Ci-e primary or secondary hydrocarbyl; and w is 0 or 1. In an aspect of formula (3), R3, R4, R5, and R6independently comprise hydrogen, halogen, or C1-C12 alkyl, more preferably hydrogen or Ci-Ce alkyl; and w is 0 or 1, preferably 1. When w is 0, the two aryl groups are connected by a single bond.

[0017] In addition to the poly(arylene ether), the thermoplastic compositions may include a poly(arylene ether siloxane). When present, the poly(arylene ether siloxane) may comprise a dihydric phenol having the structure of formula (2), wherein L in formula (2) may be of formula (4)wherein E is 6-100, or 11-80, or 11-60; and each occurrence of R independently comprises an unsubstituted or substituted C1-13 alkyl, C1-13 alkoxy, C3.6 cycloalkyl, C3.6 cycloalkoxy, Ce-i4 aryl, Ce-io aryloxy, C7-13 arylalkylene, or C7-13 alkylarylene. The foregoing groups can be fully or partially halogenated with fluorine, chlorine, bromine, or iodine, or a combination thereof. Further in formula (4), each p and q are independently 0 or 1; R1is a divalent C2-8 aliphatic group, and each occurrence of M independently comprises halogen, cyano, nitro, Ci-s alkylthio, Ci-s alkyl, Ci-s alkoxy, C2-8 alkenyl, C2-8 alkenyloxy, C3.8 cycloalkyl, C3.8 cycloalkoxy, Ce-io aryl, Ce-io aryloxy, C7-12 aralkyl, C7-12 aralkoxy, C7-12 alkylaryl, or C7-12 alkylaryloxy, wherein each n independently comprises 0, 1, 2, 3, or 4. Preferably in formula 4, E is 5-60; each occurrence of R independently comprises C1-6 alkyl, C3.6 cycloalkyl, or Ce-u aryl, more preferably methyl; p and q are each 1; R1is a divalent C2-8 aliphatic group, M is halogen, cyano, C1-4 alkyl, C1-4 alkoxy, Ce-io aryl, C7-12 aralkyl, or C7-12 alkylaryl, more preferably methyl or methoxy; and each n independently comprises 0, 1, or 2.

[0018] For example, L of Formula (2) may be derived from the dihydric phenol of formula (4a)wherein n is, on average, 5 to 100, specifically 10 to 60.

[0019] Poly(arylene ethers), for example, poly(phenylene ether), which optionally may be in the form of a copolymer of two or more monomers, for example a terpolymer, and the raw materials used to produce the poly(arylene ethers) may be, or may be formed from, renewable, sustainable, bio-circular, circular, lower carbon footprint feedstocks, upcycled, and / or post-consumer / post-industrial recycled materials, including pyrolysis oil (“py-oil”) .

[0020] Poly(arylene ethers) made from renewable sources may include, for example, a biocontent or PCR content of up to about 99.9%, about 1-99%, 5- 95%, 55-99%, or 80-99%, 1-50%, 1-25%, 1-15%, 1-10%, or 1-5%, based, e.g., on the monomer source. The poly(arylene ether) can be, e.g., anoligomer with as few as two repeating units to ultra-high molecular weight poly(arylene ethers). The weight average molecular weight of the poly(arylene ethers) in one non-limiting embodiment may range from 600 to 200,000 grams per mole, as determined by gel permeation chromatography. In another nonlimiting embodiment, the poly(arylene ethers) may have an intrinsic viscosity of up to 1.5 deciliters per gram (dl / g) as measured at 25°C in chloroform. Poly(arylene ethers) made from renewable sources may include material made by a mass balance approach and certified by regulatory bodies such as, for example, the ISCC Plus.

[0021] Poly(arylene ethers) in one embodiment may be prepared by oxidative polymerization of monomers in the presence of a polymerization catalyst in the presence of oxygen. Any of the components used in the polymerization reaction or their synthetic precursors, or the solvents used in the process, may be bio-sourced, bio-circular, or renewable raw materials. Such components and precursors include monomers (e.g., monohydric phenol, dihydric phenol and other comonomers), reagents, solvents, catalysts (e.g., a metal source, a secondary alkylene diamine ligand, a tertiary monoamine, and optionally a secondary monoamine or alternatively enzyme catalysts), gases (e.g., oxygen gas), or any combinations thereof. In some aspects, reaction components used in the polymerization of poly( arylene ethers) may be from sources as listed in the EU Renewable Energy Directive Annex IX.

[0022] Poly(arylene ethers) can be further processed, such as by redistribution, or any chemical derivatization, such as post-polymerization end-group capping or coupling, to make other materials that can transfer the sustainability characteristic to the new material. Such reagents and / or their synthetic precursors may be sustainable, bio-sourced, bio-circular, or renewable raw materials, upcycled, and / or post-consumer / post-industrial recycled materials, including pyrolysis oil (“py-oil”), to produce a poly(arylene ether).

[0023] Biosourced and sustainable materials may be derived from biomass sources or industrial sources such as waste (e.g., municipal waste). Biomass is a renewable organic material that comes from organic matter. Lignocellulosic biomass, the most abundant type of biomass and includes a wide variety of different biomass types including grasses, wood, energy crops, and agricultural and municipal wastes, is mostly composed of cellulose, hemicellulose, and lignin. Depolymerization of lignin, which is a phenolic polymer, can provide phenol. Solvents used in the production of monomers, such as methanol and acetone can be obtained from syngas, which is a product of the gasification of biomass.

[0024] Poly(arylene ether), such as a recycled poly(arylene ether) comprising an open- or closed-loop post-consumer recycled (“PCR”) poly(arylene ether), an open- or closed-loop post-industrial recycled (“PIR”) poly(arylene ether), or upcycled polyphenylene ether or a combination thereof may be used, provided that the desired property or combination of properties may be achieved. As used herein, the term “post-consumer recycle poly(arylene ether)” refers to a poly(arylene ether) that has reached the intended user or consumer and which has been collected or reclaimed after utilization by the end-user or consumer. Thus, for example, it is understood that that the term refers to a poly(arylene ether) material in whole or in part that would have otherwise been disposed of as waste, but has instead been collected andrecovered (reclaimed) as a material input, in lieu of a virgin material, for a recycling or manufacturing process. PCR-poly(arylene ether) is inclusive of material that has been reprocessed from collected or reclaimed material by means of a manufacturing process, (including e.g., purification, sorting, and pretreating) and made into a product or into a component for incorporation into a product. Such recycled poly(arylene ether)s can be further processed, for example, into the form of powders, ground materials, flakes, pellets or other form. As used herein, the term “post-industrial recycled poly(arylene ether)” refers to a poly(arylene ether) polymer or polymers that have never reached the end user and that is production waste arising during polymerization reactions, during further processing, or during manufacturing the resin or an article and includes materials such as, but not limited to, sprues from injection molding, startup material from injection molding or extrusion, extrusion scrap, molding scrap, edge trims from extruded sheets or films, and the like, including materials diverted from the waste stream during a manufacturing process for an article.

[0025] The poly(arylene ethers) and the poly( arylene ether siloxanes) can have an intrinsic viscosity of 0.25 to 1.5 deciliter per gram measured by Ubbelohde viscometer at 25 °C in chloroform. Within that range the intrinsic viscosity may be at least 0.2, at least 0.25, at least 0.3, or at least 0.37 dl / g and up to 1.4, up to 1.2, up to 1.0, 0.8, up to 0.6, or up to 0.55 dl / g as measured at 25°C in chloroform. A range for the intrinsic viscosity may include any of the foregoing limits.

[0026] The poly(arylene ether) composition is present in an amount from at least 60 wt%, based on the total thermoplastic composition. Within that range, the poly(arylene) may be present from at least 65 wt%, at least 70 wt%, or at least 75 wt% and up to 95 wt%, up to 90 wt%, or up to 85 wt%, each based on the total thermoplastic composition. A range for the poly(arylene ether) may include any combination of the foregoing limits.

[0027] When the thermoplastic compositions include a poly(arylene ether siloxane), the poly(arylene ether siloxane) may be present in an amount effective to provide up to 0.5 wt% siloxane units, based on the total weight of the thermoplastic composition. In some aspects, the poly(arylene ether siloxane) may be present up to 10 wt%, up to 8 wt%, or up to 5 wt%, based on the total thermoplastic composition.

[0028] The poly(arylene ether) having phenolic terminal groups can be formed by polymerization of monomers, for example, including a monohydric phenol, a dihydric phenol, or a combination thereof, by continuous addition of oxygen to a reaction mixture including the monomers, optionally a solvent, and a polymerization catalyst. The molecular oxygen (Oj) can be provided as air or pure oxygen. The polymerization catalyst can be a metal complex, i.e. a metal catalyst, including a transition metal cation, including cations from Group VIB, VIIB, VIIIB, or IB of the periodic table, or a combination thereof. The catalyst can include a metal cation such as chromium, manganese, cobalt, copper, or combination thereof and an anion such as chloride, bromide, iodide, sulfate, acetate, propionate, butyrate, laurate, palmitate, benzoate, or a combination of one or more of these anions, and optionally one or more charge-neutral ligands such as water, amines, phosphines, CO, or the like.Alternatively, a metal or metal oxide and an inorganic acid, organic acid, or an aqueous solution of such an acid can be combined to form a corresponding metal salt or hydrate in situ. For example, cuprous oxide and hydrobromic acid can be combined to generate cuprous bromide in situ.

[0029] Exemplary amine ligands can be, for example, a monoamine, an alkylene diamine, or a combination thereof. Monoamines include dialkylmonoamines (such as di-n-butylamine) and trialkylmonoamines (such as N,N-dimethylbutylamine).

[0030] In addition to the poly(arylene ether) composition, the thermoplastic compositions include a hydrogenated block copolymer of an alkenyl aromatic monomer comprising styrene and a conjugated diene. The alkenyl aromatic monomer used to prepare the hydrogenated block copolymer can have the structurewherein R1and R2each independently represent a hydrogen atom, a Ci-Cg alkyl group, or a Ci-Cg alkenyl group; R3and R7each independently represent a hydrogen atom or a Ci-Cg alkyl group; and R4, R5, and R6each independently represent a hydrogen atom, a Ci-Cg alkyl group, or a Ci-Cg alkenyl group, or R4and R5are taken together with the central aromatic ring to form a naphthyl group, or R5and R6are taken together with the central aromatic ring to form a naphthyl group. Specific alkenyl aromatic monomers include, for example, styrene, methylstyrenes such as alpha-methylstyrene and p-methylstyrene, and t-butylstyrenes such as 3 -t- butylstyrene and 4-t-butylstyrene (referred to as “styrene”). In some aspects, the alkenyl aromatic monomer is styrene.

[0031] The conjugated diene used to prepare the hydrogenated block copolymer can be a C4-C20 conjugated diene. Suitable conjugated dienes include, for example, 1,3-butadiene, 2-methyl-l,3- butadiene, 2-chloro-l,3-butadiene, 2,3-dimethyl-l,3-butadiene, 1,3 -pentadiene, 1,3-hexadiene, and combinations thereof. In some aspects, the conjugated diene is 1,3-butadiene, 2-methyl- 1,3 -butadiene, or a combination thereof. In some aspects, the conjugated diene is 1,3-butadiene.

[0032] The hydrogenated block copolymer is a copolymer comprising (A) at least one block derived from an alkenyl aromatic compound comprising styrene and (B) at least one block derived from a conjugated diene, in which the aliphatic unsaturated group content in the block (B) is at least partially reduced by hydrogenation. In some aspects, 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 a linear structure, a grafted structure, and a radial teleblock structure with or without a branched chain. Linear block copolymers include tapered linear structures and non-tapered linear structures. In some aspects, the hydrogenated block copolymer has a tapered linear structure. In some aspects, the hydrogenated blockcopolymer has a non-tapered linear structure. In some aspects, the hydrogenated block copolymer comprises a (B) block that comprises random incorporation of alkenyl aromatic monomer. Linear block copolymer structures include diblock (A-B block), triblock (A-B-A block or B-A-B block), tetrablock (A-B-A-B block), and pentablock (A-B-A-B-A block or B-A-B-A-B block) structures as well as linear structures containing 6 or more blocks in total of (A) and (B), wherein the molecular weight of each (A) block can be the same as or different from that of other (A) blocks, and the molecular weight of each (B) block can be the same as or different from that of other (B) blocks. In some aspects, the hydrogenated block copolymer is a diblock copolymer, a triblock copolymer, or a combination thereof.

[0033] In some aspects, the hydrogenated block copolymer consists of blocks derived from the alkenyl aromatic compound and the conjugated diene. It does not comprise grafts formed from these or any other monomers. It also consists of carbon and hydrogen atoms and therefore excludes heteroatoms. In other aspects, the hydrogenated block copolymer includes the residue of one or more acid functionalizing agents, such as maleic anhydride.

[0034] Methods for preparing hydrogenated block copolymers are known in the art and many hydrogenated block copolymers are commercially available. Illustrative commercially available hydrogenated block copolymers include the polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymers available from Kraton Performance Polymers Inc. as KRATON™ G1641 (having about 33 wt% polystyrene), G1650 (having about 30 wt% polystyrene), G1651 (having about 33 wt% polystyrene), and G1654 (having about 31 wt% polystyrene). Mixtures of two of more hydrogenated block copolymers can be used.

[0035] The hydrogenated block copolymer can have a styrene content of at least 20 wt%, or at least 25 wt%, based on the total weight of the hydrogenated block copolymer. Within that range, the hydrogenated block copolymer can have a styrene content of up to 60 wt%, or up to 50 wt%, or up to 40 wt%, based on the total weight of the hydrogenated block copolymer.

[0036] The hydrogenated block copolymer may be a single copolymer or a combination of copolymers. When the hydrogenated block copolymer is a single copolymer, it may have a weight average molecular weight of 200,000-400,000 g / mol, or 225,000-350,000 g / mol. When the hydrogenated block copolymer is a combination of copolymers, it may have an average weight average molecular weight of 200,000-400,000 g / mol, or 225,000-350,000 g / mol.

[0037] When the poly( arylene ether) composition includes a poly(arylene ether) and excludes a poly(arylene ether siloxane), then the hydrogenated block copolymer may be present at less than 6.2 wt%, or less than 6 wt%, or less than 5.5 wt%, each based on the total thermoplastic composition. The hydrogenated block copolymer may be present in an amount effective to provide less than 1.8 wt% styrene based on the total thermoplastic composition. Within that range, the hydrogenated block copolymer may be present in an amount effective to provide at least 1.0 wt%, at least 1.2 wt%, at least 1.4 wt%, or at least 1.5 wt% styrene units based on the total thermoplastic composition.

[0038] When the poly( arylene ether) composition includes a poly(arylene ether) and a poly(arylene ether siloxane), then the hydrogenated block copolymer may be present at less than 6.2 wt%, or less than 6 wt%, or less than 5.5 wt%, each based on the total thermoplastic composition. The hydrogenated block copolymer may be present in an amount effective to provide less than 1.8 wt% styrene based on the total thermoplastic composition. Within that range, the hydrogenated block copolymer may be present in an amount effective to provide at least 1.0 wt%, at least 1.2 wt%, at least 1.4 wt%, or at least 1.5 wt% styrene units based on the total thermoplastic composition.

[0039] When the thermoplastic composition includes a poly(arylene ether) and excludes a poly(arylene ether siloxane), then the ratio of the wt% of poly(arylene ether) to hydrogenated block copolymer may be at least 14.8:1. When the thermoplastic composition includes a poly(arylene ether) and a poly(arylene ether siloxane), then the ratio of the sum of the wt% of poly(arylene ether) and the poly(arylene ether siloxane) to the hydrogenated block copolymer may be at least 10:1, or at least 12:1.

[0040] In addition to the poly(arylene ether), the composition may include polystyrene comprising at least 90 wt% of repeating units derived from polymerization of styrene. In some aspects, the polystyrene comprises at least 95 wt%, specifically at least 98 wt%, of repeating units derived from polymerization of styrene. In some aspects, the polystyrene is a styrene homopolymer. The styrene homopolymer can be atactic, isotactic, or syndiotactic. Polystyrene can have a number average molecular weight of about 10,000 to about 200,000 g / mol, specifically about 30,000 to about 100,000 g / mol.

[0041] The polystyrene comprising at least 90 wt% of repeating units derived from polymerization of styrene may be minimized in the thermoplastic compositions. When the thermoplastic composition includes a poly(arylene ether) and not a poly(arylene ether siloxane), then polystyrene may be present up to 3 wt% based on the total weight of the composition. Within that range, polystyrene may be present up to 2.5 wt%, or up to 2.0 wt%, based on the total weight of the thermoplastic composition. When the thermoplastic composition includes a poly( arylene ether) and a poly( arylene ether siloxane), then polystyrene may be present up to 10 wt% based on the total weight of the composition. Within that range, polystyrene may be present up to 8 wt%, up to 5 wt%, up to 3 wt%, up to 2.5 wt%, or up to 2.0 wt%, based on the total weight of the thermoplastic composition.

[0042] Rubber-modified polystyrenes are sometimes referred to as “high-impact polystyrenes” or “HIPS”. Although HIPS has better impact resistance than a polystyrene including at least 90 wt% of repeating units derived from polymerization of styrene, it is flammable and burns readily. Given the desired flame test performance of the thermoplastic compositions, rubber-modified polystyrenes are preferably minimized or excluded. In some aspects, the thermoplastic compositions may include rubber- modified polystyrene in an amount of less than 10 wt%, 9 wt% or less, 5 wt% or less, 1 wt% or less, 0.5 wt% or less, 0.1 wt% or less, or 0.01 wt% or less, based on the total thermoplastic composition. In some aspects, the composition is free of rubber-modified polystyrene.

[0043] The thermoplastic compositions include an organophosphorus flame retardant. Organophosphorus flame retardants may include aromatic organophosphorus compounds that have atleast one organic aromatic group, the aromatic group can be a substituted or unsubstituted C3.30 group containing one or more of a monocyclic or polycyclic aromatic moiety (which can optionally contain with up to three heteroatoms (N, O, P, S, or Si)) and optionally further containing one or more nonaromatic moieties, for example alkyl, alkenyl, alkynyl, or cycloalkyl. The aromatic moiety of the aromatic group can be directly bonded to the phosphorus-containing group, or bonded via another moiety, for example an alkylene group. The aromatic moiety of the aromatic group can be directly bonded to the phosphorus-containing group, or bonded via another moiety, for example an alkylene group. In an aspect the aromatic group is the same as an aromatic group of the polycarbonate backbone, such as a bisphenol group (e.g., bisphenol A), a monoarylene group (e.g., a 1,3-phenylene or a 1,4- phenylene), or a combination comprising at least one of the foregoing.

[0044] The phosphorus-containing group can be a phosphate (P(=O)(OR)s), phosphite (P(OR)s), phosphonate (RP(=O)(OR)z), phosphinate (R2P(=O)(OR)), phosphine oxide (R3P(=O)), or phosphine (R3P), wherein each R in the foregoing phosphorus-containing groups can be the same or different, provided that at least one R is an aromatic group. A combination of different phosphorus- containing groups can be used. The aromatic group can be directly or indirectly bonded to the phosphorus, or to an oxygen of the phosphorus-containing group (i.e., an ester).

[0045] In an aspect the aromatic organophosphorus compound is a monomeric phosphate. Representative monomeric aromatic phosphates are of the formula (GO)3P=O, wherein each G is independently an alkyl, cycloalkyl, aryl, alkylarylene, or arylalkylene group having up to 30 carbon atoms, provided that at least one G is an aromatic group. Two of the G groups can be joined together to provide a cyclic group. In some aspects G corresponds to a monomer used to form the polycarbonate, e.g., resorcinol. Exemplary phosphates include phenyl bis(dodecyl) phosphate, phenyl bis(neopentyl) phosphate, phenyl bis(3,5,5'-trimethylhexyl) phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di(p- tolyl) phosphate, bis(2-ethylhexyl) p-tolyl phosphate, tritolyl phosphate, bis(2 -ethylhexyl) phenyl phosphate, tri(nonylphenyl) phosphate, bis(dodecyl) p-tolyl phosphate, dibutyl phenyl phosphate, 2- chloroethyl diphenyl phosphate, p-tolyl bis(2,5,5'-trimethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate, and the like. A specific aromatic phosphate is one in which each G is aromatic, for example, triphenyl phosphate, tricresyl phosphate, isopropylated triphenyl phosphate, and the like.

[0046] Di- or polyfunctional aromatic organophosphorus compounds are also useful, for example, compounds of the formulaswherein each G1is independently a C1-30 hydrocarbyl; each G2is independently a C1-30 hydrocarbyl or hydrocarbyloxy; Xais as defined in formula (3) or formula (4); each X is independently a bromine or chlorine; m is 0 to 4, and n is 1 to 30. In a specific aspect, Xais a single bond, methylene, isopropylidene,or 3,3,5-trimethylcyclohexylidene. Specific aromatic organophosphorus compounds are inclusive of acid esters of formula (9)wherein each R16is independently Ci-s alkyl, C5-6 cycloalkyl, Ce-zo aryl, or C7-12 arylalkylene, each optionally substituted by C1-12 alkyl, specifically by C1-4 alkyl and X is a mono- or poly-nuclear aromaticCe-so moiety or a linear or branched C2-30 aliphatic radical, which can be OH-substituted and can contain up to 8 ether bonds, provided that at least one R16or X is an aromatic group; each n is independently 0 or 1; and q is from 0.5 to 30. In some aspects each R16is independently Cu alkyl, naphthyl, phenyl(Ci. 4)alkylene, aryl groups optionally substituted by C 1 -4 alkyl; each X is a mono- or poly-nuclear aromatic Ce-so moiety, each n is 1; and q is from 0.5 to 30. In some aspects each R16is aromatic, e.g., phenyl; each X is a mono- or poly-nuclear aromatic Ce-so moiety, including a moiety derived from formula (2); n is one; and q is from 0.8 to 15. In other aspects, each R16is phenyl; X is cresyl, xylenyl, propylphenyl, or butylphenyl, one of the following divalent groupsor a combination comprising one or more of the foregoing; n is 1; and q is from 1 to 5, or from 1 to 2. In some aspects at least one R16or X corresponds to a monomer used to form the polycarbonate, e.g., bisphenol A, resorcinol, or the like. Aromatic organophosphorus compounds of this type include the bis(diphenyl) phosphate of hydroquinone, resorcinol bis(diphenyl phosphate) (RDP), and bisphenol A bis(diphenyl) phosphate (BPADP), and their oligomeric and polymeric counterparts.

[0047] The organophosphorus flame retardant containing a phosphorus-nitrogen bond can be a phosphazene, phosphonitrilic chloride, phosphorus ester amide, phosphoric acid amide, phosphonic acid amide, phosphinic acid amide, or tris(aziridinyl) phosphine oxide. These flame-retardant additives are commercially available. In an aspect, the organophosphorus flame retardant containing a phosphorusnitrogen bond is a phosphazene or cyclic phosphazene of the formulaswherein wl is 3 to 10,000; w2 is 3 to 25, or 3 to 7; and each Rwis independently a C1-12 alkyl, alkenyl, alkoxy, aryl, aryloxy, or polyoxyalkylene group. In the foregoing groups at least one hydrogen atom of these groups can be substituted with a group having an N, S, O, or F atom, or an amino group. Forexample, each Rwcan be a substituted or unsubstituted phenoxy, an amino, or a polyoxyalkylene group. Any given Rwcan further be a crosslink to another phosphazene group. Exemplary crosslinks include bisphenol groups, for example bisphenol A groups. Examples include phenoxy cyclotriphosphazene, octaphenoxy cyclotetraphosphazene decaphenoxy cyclopentaphosphazene, and the like. In an aspect, the phosphazene has a structure represented by the formula

[0048] Commercially available phenoxyphosphazenes having the aforementioned structures are LY202 manufactured and distributed by Lanyin Chemical Co., Ltd, FP-110 manufactured and distributed by Fushimi Pharmaceutical Co., Ltd, and SPB-100 manufactured and distributed by Otsuka Chemical Co., Ltd.

[0049] The organophosphorus flame retardant may include an oxaphosphorinoxide of the Formula (23) below.

[0050] In Formula (23), the phosphorous atom and one oxygen atom are part of a cyclic structure, for example, a five or six membered ring and q is at least two. Each Ar is independently Ce-is aryl, preferably benzene, which is optionally substituted with a Cushydrocarbyl group, or a CMS hydrocarbyloxy group (e.g., -O-hydrocarbyl). When n and p are each 0 and m is 1 (“mono-DOPO” type compounds), then R2is hydrogen, Ci-Cis alkyl, C3-10 cycloalkyl, (Ci-e alkyl)C3-io cycloalkyl, CMS aryl, (Ci-6 alkyl)Ce-i8 aryl, C3-12 heteroaryl, or (Ci-e alkyl)C3-i2 heteroaryl. In the foregoing groups at least one hydrogen atom of these groups may be substituted with a group having an N, S, O, or F atom. As used herein, “(Ci.6 alkyl)C3.io cycloalkyl” refers to a cycloalkyl group attached to an alkylene group, “(Ci-e alkyl)C6-is aryl” refers to an aryl group attached to an alkylene group, and “(C1-6 alkyl)C3-i2 heteroaryl” refers to a heteroaryl group attached to an alkylene group. In any of the alkyl or cycloalkyl groups of R2, any carbon-carbon single bond is optionally replaced by a carbon-carbon double or triple bond, and any methylene is optionally replaced by O, S, S(=O), C(=O), P(=O), or NR10, wherein R10is hydrogen or Ci-e alkyl, and any methylene is optionally substituted with a group having an N, S, O, or F atom.

[0051] In Formula (23), when n and p are each 1 or more and m is 0 (“Di-DOPO” type compounds), then X is Ci-Cis alkylidene, C3-10 cycloalkylidene, Ce-is arylene, C3-12 heteroarylene, a group derived from Formula (3), or a group represented by -L'-X'-L2-. The L1and L2linker groups are eachindependently a single bond, Ci-Cis alkylidene, or a C3-10 cycloalkylidene, where any carbon-carbon single bond is optionally replaced by a carbon-carbon double or triple bond, and any methylene is optionally replaced by O, S, S(=O), C(=O), P(=O), or NR10, wherein R10is hydrogen or C1-6 alkyl, and any methylene is optionally substituted with a group having an N, S, O, or F atom. X’ is Ci-Cis alkylidene, C3-10 cycloalkylidene, Ce-is arylene, C3-12 heteroarylene, or a group derived from Formula (3).

[0052] Specific examples of an oxaphosphorinoxide include 9,10-dihydro-9-oxo-10- phosphaphenanthrene-10-oxide, commercially available as from SANKO CO., LTD., under the trade name Sanko-HCA, 3-(6-oxidodibenzo[c,e][l,2]oxaphosphinin-6-yl)propenamide, and 6-[(l-oxido-2,6,7- trioxa-l-phosphabicyclo[2.2.2.]oct-4-yl)methoxy-6-oxide (23c, “DOPO-PEPA”). An exemplary Di- DOPO compound is HTP-6123G, commercially available from GUIZHOU YUANYI MINING GROUP CO.

[0053] When the poly( arylene ether) composition includes a poly(arylene ether) and excludes a poly(arylene ether siloxane), the organophosphorus flame retardant may present in an amount effective to provide at least 1.1 wt% phosphorus, or 1.1 -1.6 wt% phosphorus, based on the thermoplastic composition. The weight ratio of the hydrogenated block copolymer to phosphorus provided by the organophosphorus flame retardant may be less than 5.35: 1, 5.2: 1 or less, 5.0: 1 or less, 4.8: 1 or less, or 4.6: 1 or less, based on the thermoplastic composition.

[0054] When the poly( arylene ether) composition includes a poly(arylene ether) and a poly(arylene ether siloxane), then the organophosphorus flame retardant may present in an amount effective to provide at least 0.9 wt% phosphorus, or 0.9- 1.6 wt% phosphorus, based on the thermoplastic composition. The weight ratio of the hydrogenated block copolymer to phosphorus provided by the organophosphorus flame retardant may be any ratio where the desired properties are achieved. In some aspects, the ratio is less than 10:1, less than 8:1, less than 6:1, or less than 5.5:1, based on the thermoplastic composition.

[0055] Colorants such as pigment or dye additives can also be present. Useful pigments can include, for example, inorganic pigments such as metal oxides and mixed metal oxides such as zinc oxide, titanium dioxides, iron oxides, or the like; sulfides such as zinc sulfides, or the like; aluminates; sodium sulfo-silicates sulfates, chromates, or the like; carbon blacks; zinc ferrites; ultramarine blue; organic pigments such as azos, di-azos, quinacridones, perylenes, naphthalene tetracarboxylic acids, flavanthrones, isoindolinones, tetrachloroisoindolinones, anthraquinones, enthrones, dioxazines, phthalocyanines, and azo lakes; Pigment Red 101, Pigment Red 122, Pigment Red 149, Pigment Red 177, Pigment Red 179, Pigment Red 202, Pigment Violet 29, Pigment Blue 15, Pigment Blue 60, Pigment Green 7, Pigment Yellow 119, Pigment Yellow 147, Pigment Yellow 150, and Pigment Brown 24; or a combination thereof.

[0056] Dyes are generally organic materials and include coumarin dyes such as coumarin 460 (blue), coumarin 6 (green), nile red or the like; lanthanide complexes; hydrocarbon and substituted hydrocarbon dyes; polycyclic aromatic hydrocarbon dyes; scintillation dyes such as oxazole oroxadiazole dyes; aryl- or heteroaryl-substituted poly (Cj-g) olefin dyes; carbocyanine dyes; indanthrone dyes; phthalocyanine dyes; oxazine dyes; carbostyryl dyes; napthalenetetracarboxylic acid dyes; porphyrin dyes; bis(styryl)biphenyl dyes; acridine dyes; anthraquinone dyes; cyanine dyes; methine dyes; arylmethane dyes; azo dyes; indigoid dyes, thioindigoid dyes, diazonium dyes; nitro dyes; quinone imine dyes; aminoketone dyes; tetrazolium dyes; thiazole dyes; perylene dyes, perinone dyes; bis- benzoxazolylthiophene (BBOT); triarylmethane dyes; xanthene dyes; thioxanthene dyes; naphthalimide dyes; lactone dyes; fluorophores such as anti-stokes shift dyes which absorb in the near infrared wavelength and emit in the visible wavelength, or the like; luminescent dyes such as 7-amino-4- methylcoumarin; 3-(2'-benzothiazolyl)-7-diethylaminocoumarin; 2-(4-biphenylyl)-5-(4-t-butylphenyl)- 1,3,4-oxadiazole; 2,5-bis-(4-biphenylyl)-oxazole; 2,2'-dimethyl-p-quaterphenyl; 2,2-dimethyl-p- terphenyl; 3,5,3"",5""-tetra-t-butyl-p-quinquephenyl; 2,5 -diphenylfuran; 2,5-diphenyloxazole; 4,4'- diphenylstilbene; 4-dicyanomethylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran; 1 , 1 '-diethyl-2, 2'- carbocyanine iodide; 3,3'-diethyl-4,4',5,5'-dibenzothiatricarbocyanine iodide; 7-dimethylamino-l-methyl- 4-methoxy-8-azaquinolone-2; 7-dimethylamino-4-methylquinolone-2; 2-(4-(4-dimethylaminophenyl)- l,3-butadienyl)-3-ethylbenzothiazolium perchlorate; 3-diethylamino-7-diethyliminophenoxazonium perchlorate; 2-(l-naphthyl)-5 -phenyloxazole; 2, 2'-p-phenylen-bis(5 -phenyloxazole); rhodamine 700; rhodamine 800; pyrene, chrysene, rubrene, coronene, or the like; or a combination thereof.

[0057] The colorant composition may be present up to 5 wt% based on the thermoplastic composition. Within that range, the colorant composition may be present up to 2.5 wt%, or up to 1 wt%, based on the thermoplastic composition.

[0058] An additive composition can be used, comprising one or more additives selected to achieve a desired property, with the proviso that the additive(s) are also selected so as to not significantly adversely affect a desired properties (i.e., flame resistance, heat resistance, and impact resistance) of samples of the thermoplastic composition. Such additives can be mixed at a suitable time during the mixing of the components for forming the composition. Additives include fillers, reinforcing agents, antioxidants, heat stabilizers, light stabilizers, ultraviolet (UV) light stabilizers, plasticizers, lubricants, mold release agents, antistatic agents, colorants such as such as titanium dioxide, carbon black, and organic dyes, surface effect additives, radiation stabilizers, flame retardants, and anti-drip agents. In general, the additives are used in the amounts generally known to be effective. For example, the total amount of the additives can be 0.01 to 5 wt%, or 0.01 to 1 wt%, based on the total weight of the thermoplastic composition.

[0059] Anti-drip agents can also be used in the compositions, for example a fibril forming or non-fibril forming fluoropolymer such as polytetrafluoroethylene (PTFE). The anti-drip agent can be encapsulated by a rigid copolymer, for example styrene-acrylonitrile copolymer (SAN). PTFE encapsulated in SAN is known as TSAN. TSAN comprises 50 wt% PTFE and 50 wt% SAN, based on the total weight of the encapsulated fluoropolymer. The SAN can comprise, for example, 75 wt% styrene and 25 wt% acrylonitrile based on the total weight of the copolymer. The thermoplastic compositionsmay minimize or eliminate conventional anti-drip agents, in particular fluorinated anti-drip agents. In some aspects, the fluorinated anti-drip agent is present in an amount effective to provide 0.15 wt% or less added fluorine to the total thermoplastic composition. In some aspects, a fluorinated anti -drip agent is excluded from the thermoplastic compositions.

[0060] The thermoplastic compositions may have good heat resistance. The Heat Deflection Temperature (HDT) is a standardized measure used to evaluate a material's performance under load at elevated temperatures without significant deformation. For example, the thermoplastic compositions may have an HDT of 130 °C or greater when measured at a force of 0.45 megapascals determined on one- eighth inch (3.18 mm) bars according to ASTM D638. Within this range, the thermoplastic compositions may have an HDT of 130-170°C, or 130-160°C. In some aspects, the thermoplastic compositions may have an HDT of 132 °C or greater when measured at a force of 1.82 megapascals according to ASTM D638.

[0061] The thermoplastic compositions may have good impact resistance. Notched Izod Impact strength (Nil) was determined on one-eighth inch (3.18 mm) bars at 23 °C per ASTM D256-02. The thermoplastic compositions may have a Nil strength of at least 150 J / m (J / m). Within that range, the thermoplastic compositions may have a Nil strength of at least 175 J / m, at least 200 J / m.

[0062] The thermoplastic compositions may have a 5 VA and a 5VB flame test rating at a thickness of 1.5 mm following the procedure of Underwriter’s Laboratory Bulletin 94 entitled “Tests for Flammability of Plastic Materials for Parts in Devices and Appliances” (ISBN 0-7629-0082-2), Fifth Edition, Dated October 29, 1996, incorporating revisions through and including December 12, 2003. The 5VA and 5VB flame test ratings are designations used in the UL 94 standard for safety of flammability of plastic materials for parts in devices and appliances. For both 5VA and 5VB, no drips are allowed from the burning material. A 5VA flame test rating is the most stringent rating in the UL 94 standard. While the 5VB rating still indicates good flame-retardant properties, it is slightly less stringent than the 5 VA rating because it permits the formation of holes during flame exposure.

[0063] The thermoplastic compositions may have a V-0 rating at a thickness of 1.5 mm of less.

[0064] The thermoplastic compositions may have good weatherability. Good weatherability is evidenced by an fl rating according to the UL 746C test. Materials considered suitable for outdoor use have been subjected to ultraviolet (UV) light exposure and water immersion. UV exposure is performed by using either a twin-enclosed carbon weatherometer for 720 hours, or a xenon-arc weatherometer for 1000 hours. Water immersion testing is performed for 7 days at 70°C. Specimens are tested before and after exposure for flammability, mechanical impact and mechanical strength. Materials whose properties are not significantly degraded in any of these areas are considered to have passed and are suitable for outdoor use. In some aspects, samples of the thermoplastic compositions retain greater than 70% of the Nil after ultraviolet (UV) light exposure and water immersion as compared with the Nil before ultraviolet (UV) light exposure and water immersion. Within this range, samples may retain at least 75%,at least 80%, at least 85%, or at least 90% of the Nil before ultraviolet (UV) light exposure and water immersion.

[0065] The thermoplastic compositions may include low levels of halogens. In some aspects, the thermoplastic compositions include a calculated added bromine and chlorine content of the thermoplastic composition are each about 900 ppm or less and the calculated total added halogen content of the thermoplastic composition is about 1500 ppm or less; or the calculated added bromine, chlorine, and fluorine content of the thermoplastic composition are each about 900 ppm or less and the calculated total added bromine, chlorine, and fluorine content of the thermoplastic composition is about 1500 ppm or less.

[0066] The thermoplastic compositions may have ultra-low halogen content. As used herein, “ultra-low chlorine, bromine, or fluorine content” is defined as having a bromine, chlorine, or fluorine content of less than or equal to 100 ppm, less than or equal to 75 ppm, or less than or equal to 50 ppm, based on the total parts by weight of the composition. Preferably, the thermoplastic composition has a combined bromine, chlorine, and fluorine content of less than or equal to 100 ppm, less than or equal to 75 ppm, or less than or equal to 50 ppm, based on the total parts by weight of the composition.

[0067] The thermoplastic compositions can be manufactured by methods known in the art. For example, one method of manufacturing a thermoplastic composition comprises melt blending the components of the composition. More particularly, the powdered thermoplastic polymer components and other optional additives (including stabilizer packages, e.g., antioxidants, heat stabilizers, mold release agents, and the like) are first blended, in a HENSCHEL-Mixer® high speed mixer. Other low shear processes such as hand mixing can also accomplish this blending. The blend is then fed into the throat of an extruder via a hopper. Alternatively, one or more of the components can be incorporated into the composition by feeding directly into the extruder at the throat and / or downstream through a side stuffer. Alternatively, any desired additives can also be compounded into a masterbatch, in particular the white pigment, and combined with the remaining polymeric components at any point in the process. The extruder is generally operated at a temperature higher than that necessary to cause the composition to flow. The extrudate is immediately quenched in a water batch and pelletized. Such pellets can be used for subsequent molding, shaping, or forming. In specific embodiments, a method of manufacturing a thermoplastic composition comprises melting any of the above-described compositions to form the thermoplastic composition.

[0068] Shaped, formed, or molded articles comprising the compositions are also provided. In an aspect, an article is formed by extruding, casting, blow molding, or injection molding a melt of the thermoplastic composition. The article can be in the form of a film or sheet.

[0069] The articles may include automotive, electrical, and electronic components. In a particular aspects, the article comprises a photovoltaic micro-inverter, an optimizer, a junction box, a housing for an electrical component, or an automotive air conditioner electrical housing.

[0070] This disclosure is further illustrated by the following examples, which are non-limiting.EXAMPLES

[0071] The materials shown in Table 1 were used.Table 1

[0072] Typical compounding procedures are described as follows: The various formulations were prepared by direct dry -blending of the raw materials and pre-blended and then extruded using a twin-screw extruder. The composition was melt -kneaded, extruded, cooled through a water bath and pelletized. A typical extrusion profile is listed in Table 2.Table 2.

[0073] An Engel 45 molding machine was used to mold the test parts for standard physical property testing. The parameters are provided in Table 3.Table 3.

[0074] Sample preparation and testing methods are described in Table 4.Table 4.

[0075] Flammability tests were performed on samples at a thickness of 1.5 mm in accordance with the Underwriter’s Laboratory (UL) UL 94 standard. In some cases, a second set of 5 bars was tested to give an indication of the robustness of the rating. In this report the following definitions are used as shown in Table 5. Total flame-out-times for all 5 bars (FOT = tl + t2) were determined. V-ratings were obtained for every set of 5 bars.Table 5.

[0076] Flammability properties were also measured on bars 127 mm long by 12.7 mm wide by 1.5 mm thick, and on 150 mm x 150 mm plaques having a thickness of 1.5 mm according to Underwriter’s Laboratory Bulletin 94 “Tests for Flammability of Plastic Materials, UL 94”, 500 W (125 mm) Vertical Burning Flame Test. Results are expressed as performance class 5VA for 6 plaques and performance class 5VB for 10 bars.Examples 1-10

[0077] Table 6 shows the compositions for the following comparative examples and examples.Comparative examples are indicated with an asterisk. Table 7 shows the properties of the compositions ofExamples 1-10.Table 6.

[0078] Comparative Example 3, which omits SEBS, but included a significant amount of HIPS failed to provide a 5VA or 5VB flame test rating at 1.5 mm and the lowest impact resistance of all of the examples. Comparative Examples 1-2 include SEBS, but also fail to achieve a 5VA or 5VB flame test rating at 1.5 mm. Examples 5-8 include PPE and do not include PPE-Si. Each of Examples 5-8 achieved a 5VA and a 5VB flame test rating at 1.5 mm, with (see Example 8) and without (see Examples 5-7) polystyrene (GPPS). Comparing Example 7 and Comparative Example 1, the compositions differ in the amount of SEBS incorporated. Comparative Example 1 includes 6.2 wt%, which is an amount effective to provide 1.86-2.05 wt% styrene units, based on the thermoplastic composition. This demonstrates that 6.2 wt% of SEBS is too high an amount for those compositions that include PPE, but do not include PPE- Si. Examples 4, 9, and 10 include both PPE and PPE-Si and a higher wt% of SEBS is tolerated. Indeed, Examples 9-10 include 6.12 wt% of SEBS, which is comparable to Comparative Example 1. Despite this small difference, Examples 9-10, which include both PPE and PPE-Si achieve a 5VA flame test rating, whereas Comparative Example 1, which includes PPE and does not include PPE-Si does not achieve a 5VA flame test rating.

[0079] Aspect 1. A thermoplastic composition comprising: a poly(arylene ether) composition comprising a poly( arylene ether) and excluding a poly(arylene ether siloxane); an organophosphorus flame retardant present in an amount effective to provide at least 1.1 wt% phosphorus, based on the total weight of the composition; optionally, a polystyrene comprising greater than 98 wt%, preferably greater than 99 wt% repeating units derived from styrene; a hydrogenated block copolymer derived from an alkenyl aromatic monomer and a conjugated diene, optionally, less than 10 wt% of a rubber-modified polystyrene, or less than 10 wt% of a rubber-modified polystyrene; optionally, a colorant composition; and optionally, an additive composition, wherein the thermoplastic composition totals 100 wt%, wherein a sample of the thermoplastic composition has: a UL945VA rating at a thickness of 1.5 mm or less, and a UL94 5VB rating at a thickness of 1.5 mm or less, and a UL94 rating of V0 at a thickness of 1.5 mm or less, and a notched impact strength of at least 168 J / m at 23 °C according to ASTM D256, and an HDT of 130 °C or greater when measured at a force of 0.45 megapascals according to ASTM D638.

[0080] Aspect 2. A thermoplastic composition comprising: a poly(arylene ether) composition comprising a poly( arylene ether) and a poly( arylene ether siloxane); an organophosphorus flame retardant present in an amount effective to provide at least 0.9 wt% phosphorus, based on the total weight of the composition; optionally, a polystyrene comprising greater than 98 wt%, preferably greater than 99 wt% repeating units derived from styrene; a hydrogenated block copolymer derived from an alkenyl aromatic monomer and a conjugated diene, optionally, less than 10 wt% of a rubber-modified polystyrene, or less than 10 wt% of a rubber-modified polystyrene; optionally, a colorant composition; and optionally, an additive composition, wherein the thermoplastic composition totals 100 wt%, wherein a sample of the thermoplastic composition has: a UL945VA rating at a thickness of 1.5 mm or less, and a UL94 5VB rating at a thickness of 1.5 mm or less, and a UL94 rating of V0 at a thickness of 1.5 mm orless, and a notched impact strength of at least 168 J / m at 23 °C according to ASTM D256, and an HDT of 130 °C or greater when measured at a force of 0.45 megapascals according to ASTM D638.

[0081] Aspect 3. The thermoplastic composition of aspect 1 or aspect 2 comprising: at least 65 wt% of the poly(arylene ether) composition; the organophosphorus flame retardant; 0-5 wt% of the polystyrene comprising greater than 98 wt%, preferably greater than 99 wt% repeating units derived from styrene when the poly(arylene ether) composition comprises a poly(arylene ether) and excludes a poly(arylene ether siloxane); 0-10 wt% of the polystyrene comprising greater than 98 wt%, preferably greater than 99 wt% repeating units derived from styrene when the poly( arylene ether) composition comprises a poly(arylene ether) and a poly(arylene ether siloxane); 2-10 wt% of the hydrogenated block copolymer of the alkenyl aromatic monomer and the conjugated diene; 0 to less than 10 wt% of a rubber- modified polystyrene; 0-5 wt% of the colorant composition; and 0-10 wt% of the additive composition, wherein the poly(arylene ether) composition, the organophosphorus flame retardant, the polystyrene, the rubber-modified polystyrene, the hydrogenated block copolymer, the colorant composition, and the additive composition total 100 wt%.

[0082] Aspect 4. The thermoplastic composition of aspect 2 or aspect 3, wherein the poly(arylene ether siloxane) is present in an amount effective to provide less than 0.5 wt% siloxane content, based on the thermoplastic composition.

[0083] Aspect 5. The thermoplastic composition of aspect 1 or 3, wherein the hydrogenated block copolymer comprises a weight average molecular weight of at least 200,000 grams per mole and the ratio of the wt% of the poly(arylene ether) composition to the wt% of the hydrogenated block copolymer is at least 14.8: 1.

[0084] Aspect 6. The thermoplastic composition of aspect 1, 3, or 5, wherein the ratio of the wt% of the hydrogenated block copolymer to the wt% of phosphorus is less than 5.35:1, or 4: 1 and less than 5.35:1, from 4:1 to 5:1.

[0085] Aspect 7. The thermoplastic composition of aspect 6, wherein the ratio of the wt% of the hydrogenated block copolymer to the wt% of phosphorus is at least 4: 1.

[0086] Aspect 8. The thermoplastic composition of any of the preceding aspects, wherein the hydrogenated block copolymer is present in an amount effective to provide less than 1.8 wt% styrene based on the total thermoplastic composition.

[0087] Aspect 9. The thermoplastic composition of any one of the preceding aspects, wherein the thermoplastic composition comprises not more than 1 wt%, preferably not more than 0.1 wt% of rubber-modified polystyrene.

[0088] Aspect 10. The thermoplastic composition of any one of the preceding aspects, wherein the flame retardant is present in an amount effective to provide 1.6 wt% or less phosphorus.

[0089] Aspect 11. The thermoplastic composition of any one of the preceding aspects, wherein the organophosphorus flame retardant comprises the formulawherein R16, R17, R18and R19are each independently C1-8 alkyl, C5-6 cycloalkyl, Ce-2o aryl, or C7-12 arylalkylene, each optionally substituted by C1-12 alkyl, and X is a mono- or poly-nuclear aromatic Ce-so moiety or a linear or branched C2-30 aliphatic radical, each of which is optionally OH-substituted and optionally contain up to 8 ether bonds, provided that at least one of R16, R17, R18, R19, and X is aromatic, n is each independently 0 or 1, and q is from 0.5 to 30, and preferably wherein each of R16, R17, R18, and R19is phenyl, X is of the formulacombination thereof, each n is 1, and q is 1 to 5.

[0090] Aspect 12. The composition of aspect 1, wherein the organophosphorus flame retardant is of the formulawherein m is 1 or 2, and q is 1 to 5.

[0091] Aspect 13. The thermoplastic composition of any one of the preceding aspects wherein: the calculated added bromine and chlorine content of the thermoplastic composition are each about 900 ppm or less and the calculated total added halogen content of the thermoplastic composition is about 1500 ppm or less; or the calculated added bromine, chlorine, and fluorine content of the thermoplastic composition are each about 900 ppm or less and the calculated total added bromine, chlorine, and fluorine content of the thermoplastic composition is about 1500 ppm or less.

[0092] Aspect 14. An article comprising the thermoplastic composition of any one of the preceding aspects, preferably wherein the article comprises a photovoltaic micro-invertor, an optimizer, a junction box, a housing for an electrical component, or an automotive air conditioner electrical housing.

[0093] Aspect 15. A method for forming the article according to aspect 14, comprising molding, casting, or extruding the composition to provide the article.

[0094] The compositions, methods, and articles can alternatively comprise, consist of, or consist essentially of, any appropriate materials, steps, or components herein disclosed. The compositions, methods, and articles can additionally, or alternatively, be formulated so as to be devoid, or substantiallyfree, of any materials (or species), steps, or components, which are otherwise not necessary to the achievement of the function or objectives of the compositions, methods, and articles.

[0095] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other (e.g., ranges of “up to 25 wt%, or, more specifically, 5 wt% to 20 wt%”, is inclusive of the endpoints and all intermediate values of the ranges of “5 wt% to 25 wt%,” etc.). “Combinations” is inclusive of blends, mixtures, alloys, reaction products, and the like. The terms “first,” “second,” and the like, do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. The terms “a” and “an” and “the” do not denote a limitation of quantity and are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. “Or” means “and / or” unless clearly stated otherwise. Reference throughout the specification to “some embodiments”, “an embodiment”, and so forth, means that a particular element described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments. A “combination thereof’ is open and includes any combination comprising at least one of the listed components or properties optionally together with a like or equivalent component or property not listed

[0096] Unless specified to the contrary herein, all test standards are the most recent standard 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.

[0097] Unless defined otherwise, technical and scientific terms used herein have the same meaning as is commonly understood by one of 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 the present application contradicts or conflicts with a term in the incorporated reference, the term from the present application takes precedence over the conflicting term from the incorporated reference.

[0098] Compounds are described using standard nomenclature. For example, any position not substituted by any indicated group is understood to have its valency filled by a bond as indicated, or a hydrogen atom. A dash ("-") that is not between two letters or symbols is used to indicate a point of attachment for a substituent. For example, -CHO is attached through carbon of the carbonyl group.

[0099] As used herein, the term “hydrocarbyl,” whether used by itself, or as a prefix, suffix, or fragment of another term, refers to a residue that contains only carbon and hydrogen unless it is specifically identified as “substituted hydrocarbyl”. The hydrocarbyl residue can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It can also contain combinations of aliphatic, aromatic, straight chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties. When the hydrocarbyl residue is described as substituted, it can contain heteroatoms in addition to carbon and hydrogen. The term "alkyl" means a branched or straight chain, unsaturated aliphatic hydrocarbon group, e.g., 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 that is linked via an oxygen (i.e., alkyl-O-), for example 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, -CnFbn-x, wherein x is the number of hydrogens replaced by cyclization(s). “Cycloalkenyl” means a monovalent group having one or more rings and one or more carbon-carbon double bonds in the ring, wherein all ring members are carbon (e.g., cyclopentyl and cyclohexyl). "Aryl" means an aromatic hydrocarbon group containing the specified number of carbon atoms, such as phenyl, tropone, indanyl, or naphthyl. “Arylene” means a divalent aryl group. “Alkylarylene” means an arylene group substituted with an alkyl group. “Arylalkylene” means an alkylene group substituted with an aryl group (e.g., benzyl). The prefix "halo" means a group or compound including one more of a fluoro, chloro, bromo, or iodo substituent. A combination of different halo groups (e.g., bromo and fluoro), or only chloro groups can be present. The prefix “hetero” means that the compound or group includes at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatom(s)), wherein the heteroatom(s) is each independently N, O, S, Si, or P. “Substituted” means that the compound or group is substituted with at least one (e.g., 1, 2, 3, or 4) substituents that can each independently be a C1-9 alkoxy, a C1-9 haloalkoxy, a nitro (-NO2), a cyano (- CN), a C1-6 alkyl sulfonyl (-S(=O)2-alkyl), a Ce-i2 aryl sulfonyl (-S(=O)2-aryl)a thiol (-SH), a thiocyano (- SCN), a tosyl (CH3C6H4SO2-), a C3-12 cycloalkyl, a C2-12 alkenyl, a C5-12 cycloalkenyl, a Ce-i2 aryl, a C7-13 arylalkylene, a C4-12 heterocycloalkyl, and a C3-12 heteroaryl instead of hydrogen, provided that the substituted atom’s normal valence is not exceeded. The number of carbon atoms indicated in a group is exclusive of any substituents. For example -CH2CH2CN is a C2 alkyl group substituted with a nitrile.[000100] While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are or may be presently unforeseen may arise to applicants or others skilled in the art. Accordingly, the appended claims as filed and as they may be amended are intended to embrace all such alternatives, modifications variations, improvements, and substantial equivalents.

Claims

CLAIMSWhat is claimed is:

1. A thermoplastic composition comprising: a poly(arylene ether) composition comprising a poly(arylene ether) and excluding a poly(arylene ether siloxane); an organophosphorus flame retardant present in an amount effective to provide at least 1.1 wt% phosphorus, based on the total weight of the composition; optionally, a polystyrene comprising greater than 98 wt%, preferably greater than 99 wt% repeating units derived from styrene; less than 10 wt% of a rubber-modified polystyrene; a hydrogenated block copolymer derived from an alkenyl aromatic monomer comprising styrene and a conjugated diene, optionally, a colorant composition; and optionally, an additive composition, wherein the thermoplastic composition totals 100 wt%, wherein a sample of the thermoplastic composition has: a UL945VA rating at a thickness of 1.5 mm or less, and a UL945VB rating at a thickness of 1.5 mm or less, and a UL94 rating of VO at a thickness of 1.5 mm or less, and a notched impact strength of at least 168 J / m at 23 °C according to ASTM D256, and a heat deflection temperature of 130 °C or greater when measured at a force of 0.45 megapascals according to ASTM D638.

2. A thermoplastic composition comprising: a poly(arylene ether) composition comprising a poly(arylene ether) and a poly(arylene ether siloxane); an organophosphorus flame retardant present in an amount effective to provide at least 0.9 wt% phosphorus, based on the total weight of the composition; optionally, a polystyrene comprising greater than 98 wt%, preferably greater than 99 wt% repeating units derived from styrene; a hydrogenated block copolymer derived from an alkenyl aromatic monomer comprising styrene and a conjugated diene, less than 10 wt% of a rubber-modified polystyrene; optionally, a colorant composition; and optionally, an additive composition, wherein the thermoplastic composition totals 100 wt%, wherein a sample of the thermoplastic composition has:a UL945VA rating at a thickness of 1.5 mm or less, and a UL945VB rating at a thickness of 1.5 mm or less, and a UL94 rating of VO at a thickness of 1.5 mm or less, and a notched impact strength of at least 168 J / m at 23 °C according to ASTM D256, and a heat deflection temperature of 130 °C or greater when measured at a force of 0.45 megapascals according to ASTM D638.

3. The thermoplastic composition of claim 1 or claim 2 comprising: at least 65 wt% of the poly(arylene ether) composition; the organophosphorus flame retardant;0-5 wt% of the polystyrene comprising greater than 98 wt%, preferably greater than 99 wt% repeating units derived from styrene when the poly(arylene ether) composition comprises a poly(arylene ether) and excludes a poly(arylene ether siloxane);0-10 wt% of the polystyrene comprising greater than 98 wt%, preferably greater than 99 wt% repeating units derived from styrene when the poly(arylene ether) composition comprises a poly(arylene ether) and a poly( arylene ether siloxane);2-10 wt% of the hydrogenated block copolymer of the alkenyl aromatic monomer comprising styrene and the conjugated diene;0 to less than 10 wt% of a rubber-modified polystyrene;0-5 wt% of the colorant composition; and0-10 wt% of the additive composition, wherein the poly(arylene ether) composition, the organophosphorus flame retardant, the polystyrene, the hydrogenated block copolymer, the rubber-modified polystyrene, the colorant composition, and the additive composition total 100 wt%.

4. The thermoplastic composition of claim 2 or 3, wherein the poly(arylene ether siloxane) is present in an amount effective to provide less than 0.5 wt% siloxane content, based on the thermoplastic composition.

5. The thermoplastic composition of claim 1 or 3, wherein the hydrogenated block copolymer comprises a weight average molecular weight of at least 200,000 grams per mole and the ratio of the wt% of the poly(arylene ether) composition to the wt% of the hydrogenated block copolymer is at least 14.8:1.

6. The thermoplastic composition of any one of claims 1, 3, or 5, wherein the ratio of the wt% of the hydrogenated block copolymer to the wt% of phosphorus is less than 5.35:1.

7. The thermoplastic composition of claim 1, wherein the hydrogenated block copolymer comprises a weight average molecular weight of at least 200,000 grams per mole, the ratio of the wt% of the poly(arylene ether) composition to the wt% of the hydrogenated block copolymer is at least 14.8:1, and the ratio of the wt% of the hydrogenated block copolymer to the wt% of phosphorus is less than 5.35: 1.

8. The thermoplastic composition of any of the preceding claims, wherein the hydrogenated block copolymer is present in an amount effective to provide less than 1.8 wt% styrene based on the total thermoplastic composition.

9. The thermoplastic composition of any one of the preceding claims, wherein the thermoplastic composition comprises not more than 1 wt%, preferably not more than 0.1 wt% of rubber- modified polystyrene.

10. The thermoplastic composition of any one of the preceding claims, wherein the flame retardant is present in an amount effective to provide 1.6 wt% or less phosphorus, based on the total thermoplastic composition.

11. The thermoplastic composition of any one of the preceding claims, wherein the organophosphorus flame retardant comprises the formulawhereinR16, R17, R18and R19are each independently Ci-s alkyl, C5-6 cycloalkyl, Ce-zo aryl, or C7-12 arylalkylene, each optionally substituted by C1-12 alkyl, andX is a mono- or poly-nuclear aromatic Ce-so moiety or a linear or branched C2-30 aliphatic radical, each of which is optionally OH-substituted and optionally contain up to 8 ether bonds, provided that at least one of R16, R17, R18, R19, and X is aromatic, n is each independently 0 or 1, and q is from 0.5 to 30, andX is of the formulacombination thereof, each n is 1, and q is 1 to 5.

12. The composition of claim 1, wherein the organophosphorus flame retardant is of thewherein m is 1 or 2, and q is 1 to 5.

13. The thermoplastic composition of any one of the preceding claims wherein: the calculated added bromine and chlorine content of the thermoplastic composition are each about 900 ppm or less and the calculated total added halogen content of the thermoplastic composition is about 1500 ppm or less; or the calculated added bromine, chlorine, and fluorine content of the thermoplastic composition are each about 900 ppm or less and the calculated total added bromine, chlorine, and fluorine content of the thermoplastic composition is about 1500 ppm or less.

14. An article comprising the thermoplastic composition of any one of the preceding claims, preferably wherein the article comprises a photovoltaic micro-invertor, an optimizer, a junction box, a housing for an electrical component, or an automotive air conditioner electrical housing.

15. A method for forming the article according to claim 14, comprising molding, casting, or extruding the composition to provide the article.

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