Thermoplastic composition, articles prepared therefrom, and methods for manufacturing the same

Abstract

The thermoplastic composition comprises a specific amount of poly(phenylene ether), polyamide, impact modifier, conductive agent, bisphenoxyethanol fluorene, terpene phenol resin, novolac resin, or a combination thereof, a hydroxyl group-containing compound, and a compatibilizer, in weight percent relative to the total weight of the thermoplastic composition.

Description

Technical Field

[0001] This application relates to a thermoplastic composition, an article prepared therefrom, and a method for producing the same.

[0002] (Cross-reference to related applications) This application claims the priority of European Patent Application Publication No. 23178419.0 filed on June 9, 2023, the content of which is incorporated herein by reference in its entirety.

Background Art

[0003] Poly(phenylene ether) blended with polyamide can provide a composition having various properties such as heat resistance, chemical resistance, impact strength, hydrolysis stability, and dimensional stability. In some applications, it may be desirable to use a poly(phenylene ether) / polyamide composition having good conductivity, good melt flow, low water absorption, and good mechanical properties. Unfortunately, it can be difficult to achieve such a balance of desirable properties. For example, polyamide is a well-known thermoplastic polymer having properties such as high melt flow and excellent processability and chemical resistance. However, polyamide tends to absorb water over time, which can lead to warpage and poor retention of mechanical strength. A poly(phenylene ether) / polyamide blend may exhibit low hygroscopicity, but the melt flow is generally not sufficient for some applications. Other poly(phenylene ether) / polyamide blends may exhibit high melt flow, but may have higher water absorption than their lower melt flow counterparts.

Summary of the Invention

Problems to be Solved by the Invention

[0004] Therefore, there is still a need in this field for poly(phenylene ether) / polyamide compositions that exhibit a combination of high melt flow and low water absorption. Improving the conductivity of poly(phenylene ether) / polyamide compositions would be a further advantage. [Means for solving the problem]

[0005] The thermoplastic composition comprises 30 to 60 weight percent of poly(phenylene ether), 30 to 60 weight percent of polyamide, 1 to 20 weight percent of impact modifier, 0.1 to 10 weight percent of conductive agent, 1 to 10 weight percent of hydroxy-containing compound including bisphenoxyethanol fluorene, terpene phenol resin, novolac resin, or a combination thereof, and 0.01 to 10 weight percent of compatibilizer, where the weight percentages are relative to the total weight of the thermoplastic composition.

[0006] Another aspect of this disclosure is an article comprising a thermoplastic composition.

[0007] A method for producing a thermoplastic composition includes melt-blending the components of the composition.

[0008] The above features and other features are illustrated by the following embodiments for carrying out the invention. [Modes for carrying out the invention]

[0009] The inventors have advantageously discovered a composition that is particularly well-suited as a matrix resin for use in reinforced thermoplastics for automotive applications, for example. The compositions described herein can exhibit a desirable combination of high melt flow, low hygroscopicity, high heat resistance, and good impact performance.

[0010] Thus, an aspect of the present disclosure is a thermoplastic composition. The composition includes specific amounts of poly(phenylene ether), polyamide, impact modifier, conductive agent, hydroxy group-containing compound, and compatibilizer.

[0011] The composition includes poly(phenylene ether) (also referred to herein as "PPE"). The poly(phenylene ether) has a structure

Chemical formula

[0012] In one embodiment, poly(phenylene ether) has an intrinsic viscosity of 0.2 to 1 deciliter per gram, as measured by an Ubberohde viscometer in chloroform at 25°C. Within this range, the intrinsic viscosity of poly(phenylene ether) may be 0.2 to 0.6 deciliters per gram, or 0.25 to 0.5 deciliters per gram, or 0.3 to 0.5 deciliters per gram, or 0.33 to 0.46 deciliters per gram.

[0013] In certain embodiments, poly(phenylene ether) is poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.2 to 0.6 deciliters per gram, as measured by an Ubberohde viscometer in chloroform at 25°C. Within the range of 0.2 to 0.6 deciliters per gram, the intrinsic viscosity of poly(2,6-dimethyl-1,4-phenylene ether) may be 0.3 to 0.5 deciliters per gram, more preferably 0.33 to 0.46 deciliters per gram.

[0014] Poly(phenylene ether), which may optionally be a copolymer of two or more monomers, for example in the form of a terpolymer, and the raw materials used to produce poly(phenylene ether) may be renewable, sustainable, biocircular, circular, low-carbon footprint supply material, upcycled material, and / or recycled (including pyrolysis oils ("py oils")) or may be formed from them.

[0015] Poly(phenylene ether) produced from renewable resources may contain, for example, bio- or PCR-containing amounts of up to approximately 99.9%, approximately 1-99%, 5-95%, 55-99%, or 80-99%, 1-50%, 1-25%, 1-15%, 1-10%, or 1-5% relative to the monomer source. Poly(phenylene ether) may range from oligomers with only two repeating units to ultra-high molecular weight poly(phenylene ether). In one non-limiting embodiment, the weight-average molecular weight of poly(phenylene ether), as determined by gel permeation chromatography, may range from 600 to 200,000 grams per mole. In another non-limiting embodiment, poly(phenylene ether) may have an intrinsic viscosity of up to 1.5 deciliters per gram (dl / g), as measured in chloroform at 25°C. Poly(phenylene ether) produced from renewable resources may include materials produced using a mass balance approach and certified by regulatory bodies such as ISCC Plus.

[0016] In some embodiments, poly(phenylene ether) can be prepared by oxidative polymerization of monomers in the presence of a polymerization catalyst in the presence of oxygen. The components used in the polymerization reaction, their synthetic precursors, or the solvents used in the process may be of bio-derived, biocircular, or renewable raw materials. Such components and precursors include monomers (e.g., monovalent phenols, divalent phenols, and other comonomers), reagents, solvents, catalysts (e.g., metal sources, secondary alkylenediamine ligands, tertiary monoamines, and optionally secondary monoamines or alternatively enzyme catalysts), gases (e.g., oxygen gas), or any combination thereof. In some embodiments, the reaction components used in the polymerization of poly(phenylene ether) may be from sources listed in Annex IX of the EU Renewable Energy Directive.

[0017] Poly(phenylene ether) can be further processed by redistribution or any chemical derivatization such as end group capping or coupling after polymerization to produce other materials in which sustainable properties can be transferred to new materials. Such reagents and / or their synthetic precursors may be sustainable, bio-derived, biocircular, or renewable raw materials, upcycled, and / or post-consumer / post-industrial recycled materials (including pyrolysis oils ("py oils")) for the production of poly(phenylene ether).

[0018] Bio-derived and sustainable materials can originate from biomass sources or industrial sources such as waste (e.g., municipal waste). Biomass is a renewable organic material derived from organic matter. Lignocellulosic biomass is the most abundant type of biomass, encompassing a wide variety of different types of biomass, including grass, wood, energy crops, and agricultural and municipal waste, and is largely composed of cellulose, hemicellulose, and lignin. The depolymerization of lignin, a phenolic polymer, can yield phenol. Solvents used in the production of monomers such as methanol and acetone can be obtained from synthesis gas, a product of gasifying biomass.

[0019] Poly(phenylene ethers), such as open-loop or closed-loop consumer post-use recycled ("PCR") poly(phenylene ether), open-loop or closed-loop industrial post-use recycled ("PIR") poly(phenylene ether), or recycled poly(phenylene ether) including upcycled polyphenylene ether, or combinations thereof, may be used as long as the desired properties or combinations of properties can be achieved. As used herein, the term "consumer post-use recycled poly(phenylene ether)" means poly(phenylene ether) that has reached an intended user or consumer and has been collected or reclaimed after use by the end user or consumer. Thus, for example, this term is understood to mean all or part of a poly(phenylene ether) material that would otherwise be disposed of as waste but has instead been collected and reclaimed as a material input to replace virgin material for recycling or manufacturing processes. PCR-poly(phenylene ether) includes materials that have been reprocessed from collected or recovered and reused materials through a manufacturing process (including, for example, purification, sorting, and pretreatment) into a product or a component to be incorporated into a product. Such recycled poly(phenylene ether) can be further processed, for example, in the form of powder, pulverized material, flakes, pellets, or other forms. As used herein, the term “industrial post-use recycled poly(phenylene ether)” refers to poly(phenylene ether) polymers that have never reached an end user and are production waste generated during polymerization reactions, further processing, or the manufacture of resins or articles, and includes, but is not limited to, materials such as sprues from injection molding, starting materials from injection molding or extrusion, extrusion scrap, molding scrap, edge trim from extruded sheets or films, and includes materials diverted from waste flows during the manufacturing process of articles.

[0020] The composition contains poly(phenylene ether) in an amount of 30 to 60 weight percent of the total weight of the composition. Within this range, the amount of poly(phenylene ether) may be 30 to 55 weight percent, 30 to 50 weight percent, 32 to 50 weight percent, 35 to 50 weight percent, 35 to 49 weight percent, 35 to 48 weight percent, or 35 to 46 weight percent, respectively, based on the total weight of the composition.

[0021] In addition to poly(phenylene ether), the composition contains polyamides. Polyamides, also known as nylon, are polymers containing amide (i.e., -C(=O)NH-) linking groups, as described, for example, in U.S. Patent No. 4,970,272 by Gallucci. Possible polyamides include polyamide-6, polyamide-6,6, polyamide-6,10, polyamide-4,10, polyamide-5,10, polyamide-10,10, polyamide-9T, polyamide-6T, polyamide-10T, polyamide-6I, polyamide-MXD6, or combinations thereof. In some embodiments, the polyamide comprises polyamide-6, polyamide-6,6, or combinations thereof, preferably polyamide-6,6. In some embodiments, the polyamide comprises polyamide-6,10. Polyamides such as polyamide-6 and polyamide-6,6 are commercially available from several suppliers, and methods for their preparation are known. For example, polyamides can be obtained by several well-known processes, such as those described in Carothers' U.S. Patent Nos. 2,071,250, 2,071,251, 2,130,523, and 2,130,948, Hanford's U.S. Patent Nos. 2,241,322 and 2,312,966, and Bolton et al.'s U.S. Patent No. 2,512,606.

[0022] Polyamide can be virgin material or recycled or upcycled material. In some embodiments, the polyamide may be virgin material, excluding polyamide used in end-use parts. In some embodiments, the polyamide may be polyamide recovered at least partially from end-use parts. For example, the polyamide may be recycled polyamide after consumer use, recycled polyamide after industrial use, chemically recycled polyamide, or a combination thereof. In some embodiments, the polyamide may be a combination of virgin polyamide and recycled polyamide.

[0023] In some embodiments, the polyamide may be a biopolyamide. “Biopolyamide” is defined as a polyamide that is entirely or partially derived from renewable resources, such as plant or animal sources, as determined by the biocarbon content of the biopolyamide, as measured by ASTM D6866 (Standard Test Method for Determining the Biocarbon Content of Materials in the Natural Range Using Radiocarbon and Isotope Ratio Mass Spectrometry). ASTM D6866 provides three methods for measuring organic carbon derived from renewable raw materials, referred to as biocarbon. The percentages indicated for the polyamides of the present invention are preferably measured by mass spectrometry or liquid scintillation analysis as described in this Standard Test Method.

[0024] As a result, in the material 14 The presence of C, regardless of the amount present, provides information about the origin of the molecules that make it up, i.e., in the material. 14The presence of C indicates that a particular fraction originates from renewable raw materials and no longer from fossil-derived materials. Therefore, measurements performed by the methods described in the ASTM D6866 standard help distinguish monomers or starting reactants resulting from renewable materials from monomers or reactants resulting from fossil-derived materials. The term “bio-derived” means compounds, compositions, and / or other organic materials that are “isotopefully rich” in carbon-14 compared to petroleum sources, as determined by ASTM D6866. The term “biomass” means living and recently deceased biological materials, excluding organic materials converted by geological processes into components selected from the group consisting of petroleum, petrochemicals, and combinations thereof. The term “isotopefully rich” means that the carbon-14 to carbon-12 ratio in compounds, compositions, and / or other organic materials is higher than the carbon-14 to carbon-12 ratio from petroleum sources.

[0025] The following biopolyamides are commercially available and have varying levels of bio-derived carbon content, as measured by ASTM D6866. Polyamide 10T is a poly(decamethyleneterephthalamide) based on decanediamine to about 50%, and is a renewable raw material derived from castor beans. Polyamide 410 (PA410) is produced by polycondensation of tetramethylenediamine and sebacic acid, which is available from castor oil. PA410 contains 70 percent bio-derived carbon and is available from DSM under the trade name EcoPaXX(trademark). Polyamide 610 (PA610) is produced by polycondensation of hexamethylenediamine and sebacic acid, which is available from castor oil. PA610 contains at least 63 percent bio-derived carbon and is available from the following suppliers: BASF, trade name Ultramid Balance; Evonik, trade name Vestamid TerraHS; Dupont, trade name Zytel RS LC; EMS-Grivory, trade name Grilamid 2S; Rhodia, trade name Technyl eXten; and Akro Plastik, trade name Akromid S. Polyamide 1010 (PA1010) is produced by polycondensation of decamethylenediamine and sebacic acid, which is available from castor oil, and contains up to 100 percent bio-derived carbon depending on the source of decamethylenediamine. PA1010 is available from the following suppliers: EMS-Grivory, trade name Grilamid 1S; Evonik, trade name Vestamid Terra DS; and Dupont, trade name Zytel RS LC. Polyamide 1012 (PA1012) is produced by polycondensation of decamethylenediamine and dodecanoic acid. Both components are derivable from vegetable oils, and therefore PA1012 can contain more than 45 percent bio-derived carbon. PA1012 is available from Evonik under the trade name Vastamid TerraDD.

[0026] Polyamide may be present in an amount of 30 to 60 weight percent of the total weight of the composition. Within this range, polyamide may be present in an amount of 30 to 55 weight percent, or 30 to 50 weight percent, or 32 to 50 weight percent, or 34 to 55 weight percent, or 34 to 50 weight percent.

[0027] In addition to poly(phenylene ether) and polyamide, the composition contains impact modifiers. Suitable impact modifiers are typically high molecular weight elastomer materials derived from olefins, monovinyl aromatic monomers, acrylic and methacrylic acids and their ester derivatives, and conjugated dienes. Polymers formed from conjugated dienes may be fully or partially hydrogenated. The elastomer materials may be in the form of homopolymers or copolymers including random, block, radial block, graft, and core-shell copolymers. Impact modifiers can be used in combination.

[0028] In some embodiments, the impact modifier may include (i) an elastomeric (i.e., rubbery) polymer substrate having a Tg of less than 10°C, more preferably less than -10°C, or more preferably -40°C to -80°C, and (ii) an elastomer-modified graft copolymer comprising a rigid polymeric superstraight grafted onto the elastomeric polymer substrate. Suitable materials for use as the elastomer phase include, for example, conjugated diene rubbers, such as polybutadiene and polyisoprene, copolymers of conjugated dienes with less than 50% by weight of copolymerizable monomers, such as monovinyl compounds such as styrene, acrylonitrile, n-butyl acrylate, or ethyl acrylate, olefin rubbers such as ethylene propylene copolymer (EPR) or ethylene-propylene-diene monomer rubber (EPDM), ethylene-vinyl acetate rubber, silicone rubber, and elastomeric C 1~8 Alkyl (meth)acrylate, C 1~8Examples include elastomeric copolymers of alkyl (meth)acrylates with butadiene or styrene, or combinations thereof. Suitable materials for use as a rigid phase include, for example, monovinyl aromatic monomers such as styrene and alpha-methylstyrene, as well as acrylonitrile, acrylic acid, methacrylic acid, and C13 of acrylic acid and methacrylic acid. 1~6 Examples include monovinyl monomers such as esters, preferably methyl methacrylate.

[0029] Specific elastomer-modified graft copolymers include those formed from styrene-butadiene-styrene (SBS), styrene-butadiene rubber (SBR), styrene-ethylene-butadiene-styrene (SEBS), ABS (acrylonitrile-butadiene-styrene), acrylonitrile-ethylene-propylene-diene-styrene (AES), styrene-isoprene-styrene (SIS), methyl methacrylate-butadiene-styrene (MBS), styrene-acrylonitrile (SAN), and ethylene-propylene rubber grafted with maleic anhydride (commercially available from Exxon Chemicals Ltd as Exxelor® VA 1801).

[0030] In certain embodiments, the impact modifier comprises a hydrogenated block copolymer of an alkenyl aromatic monomer and a conjugated diene. For brevity, this component is referred to as the "hydrogenated block copolymer." The hydrogenated block copolymer may contain a poly(alkenyl aromatic) content of 10 to 90 weight percent and a hydrogenated poly(conjugated diene) content of 90 to 10 weight percent based on the weight of the hydrogenated block copolymer. In certain embodiments, the hydrogenated block copolymer is a low poly(alkenyl aromatic) content hydrogenated block copolymer in which the poly(alkenyl aromatic) content is 10 to less than 40 weight percent, specifically 20 to 35 weight percent, more specifically 25 to 35 weight percent, and even more specifically 25 to 30 weight percent, based on the weight of the low poly(alkenyl aromatic) content hydrogenated block copolymer. In other embodiments, the hydrogenated block copolymer is a high poly(alkenyl aromatic) content hydrogenated block copolymer in which the poly(alkenyl aromatic) content is 40 to 90 weight percent, specifically 50 to 80 weight percent, and more specifically 60 to 70 weight percent, relative to the weight of the high poly(alkenyl aromatic) content hydrogenated block copolymer. In certain embodiments, the hydrogenated block copolymer may have a poly(alkenyl aromatic) content of 28 to 37 weight percent.

[0031] In one embodiment, the hydrogenated block copolymer has a weight-average molecular weight of 40,000 to 400,000 grams per mole (g / mol or Dalton, Da). The number-average molecular weight and weight-average molecular weight can be determined by gel permeation chromatography based on comparison with a polystyrene standard. In one embodiment, the hydrogenated block copolymer has a weight-average molecular weight of 200,000 to 400,000 grams per mole, specifically 220,000 to 350,000 grams per mole. In another embodiment, the hydrogenated block copolymer has a weight-average molecular weight of 40,000 to 200,000 grams per mole, specifically 40,000 to 180,000 grams per mole, and more specifically 40,000 to 150,000 grams per mole.

[0032] Alkenyl aromatic monomers used to prepare hydrogenated block copolymers have a structure [ka] (In the formula, R 1 and R 2 Each of them is independently a hydrogen atom, C 1~8 Alkyl alkyl group, or C 2~8 Represents an alkenyl group, R 3 and R 7 These are, independently, hydrogen atoms and C 1~8 R represents an alkyl group, a chlorine atom, or a bromine atom, and 4 , R 5 , and R 6 These are, independently, hydrogen atoms and C 1~8 Alkyl alkyl group, or C 2~8 R represents an alkenyl group. 4 and R 5 It forms a naphthyl group together with the central aromatic ring, or R 5 and R 6 It may have a central aromatic ring that together forms a naphthyl group. Specific examples of alkenyl aromatic monomers include styrene, chlorostyrene such as p-chlorostyrene, methylstyrene such as alpha-methylstyrene and p-methylstyrene, and t-butylstyrene such as 3-t-butylstyrene and 4-t-butylstyrene. In one embodiment, the alkenyl aromatic monomer is styrene.

[0033] The conjugated dienes used to prepare hydrogenated block copolymers are C 4~20 It 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 combinations thereof. In some embodiments, the conjugated diene is 1,3-butadiene, 2-methyl-1,3-butadiene, or a combination thereof. In some embodiments, the conjugated diene is 1,3-butadiene.

[0034] Hydrogenated block copolymers are copolymers 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 content of aliphatic unsaturated groups in block (B) is at least partially reduced by hydrogenation. In some embodiments, the aliphatic unsaturation in block (B) is reduced by at least 50 percent, specifically at least 70 percent. The arrangements of blocks (A) and (B) include linear structures, graft structures, and radial teleblock structures with or without branched chains. Linear block copolymers include tapered linear structures and non-tapered linear structures. In some embodiments, hydrogenated block copolymers have tapered linear structures. In some embodiments, hydrogenated block copolymers have non-tapered linear structures. In some embodiments, hydrogenated block copolymers include block (B) which comprises random incorporation of alkenyl aromatic monomers. The linear block copolymer structure includes 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 six or more blocks of (A) and (B), wherein the molecular weight of each (A) block may be the same as or different from the molecular weight of other (A) blocks, and the molecular weight of each (B) block may be the same as or different from the molecular weight of other (B) blocks. In some embodiments, the hydrogenated block copolymer is a diblock copolymer, a triblock copolymer, or a combination thereof.

[0035] In some embodiments, the hydrogenated block copolymer does not contain monomer residues other than alkenyl aromatic compounds and conjugated dienes. In some embodiments, the hydrogenated block copolymer consists of blocks derived from alkenyl aromatic compounds and conjugated dienes. The hydrogenated block copolymer does not contain grafts formed from these monomers or any other monomers. The hydrogenated block copolymer also consists of carbon and hydrogen atoms and therefore does not contain heteroatoms. In some embodiments, the hydrogenated block copolymer contains residues of one or more acid-functionalizing agents, such as maleic anhydride. In some embodiments, the hydrogenated block copolymer includes polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer.

[0036] In some embodiments, the hydrogenated block copolymer is a polystyrene-poly(ethylene-propylene) diblock copolymer, a polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer, or a combination thereof. In some embodiments, the hydrogenated block copolymer is a polystyrene-poly(ethylene-propylene) diblock copolymer, a polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer, or a combination thereof, having a polystyrene content of 28 to 37 weight percent. In some embodiments, the hydrogenated block copolymer comprises a polystyrene-poly(ethylene-propylene) diblock copolymer and a polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer.

[0037] Methods for preparing hydrogenated block copolymers are well known in the art, and many hydrogenated block copolymers are commercially available. Examples of commercially available hydrogenated block copolymers include polystyrene-poly(ethylene-propylene) diblock copolymers available from Kraton Performance Polymers Inc. as KRATON® G1701 (having about 37 wt percent polystyrene) and G1702 (having about 28 wt percent polystyrene); polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymers available from Kraton Performance Polymers Inc. as KRATON® G1641 (having about 33 wt percent polystyrene), G1650 (having about 30 wt percent polystyrene), G1651 (having about 33 wt percent polystyrene), and G1654 (having about 31 wt percent polystyrene); and polystyrene-poly(ethylene-ethylene / propylene)-polystyrene triblock copolymers available from Kuraray Ltd. as SEPTON® S4044, S4055, S4077, and S4099.Further commercially available hydrogenated block copolymers include polystyrene-poly(ethylene-butylene)-polystyrene (SEBS) triblock copolymers available from Dynasol as CALPRENE® H6140 (containing approximately 31 wt percent polystyrene), H6170 (containing approximately 33 wt percent polystyrene), H6171 (containing approximately 33 wt percent polystyrene), and H6174 (containing approximately 33 wt percent polystyrene), and from Kuraray Co., Ltd. as SEPTON® 8006 (containing approximately 33 wt percent polystyrene) and 8007 (containing approximately 30 wt percent polystyrene); polystyrene-poly(ethylene-propylene)-polystyrene (SEPS) copolymers available from Kuraray Co., Ltd. as SEPTON® 2006 (containing approximately 35 wt percent polystyrene) and 2007 (containing approximately 30 wt percent polystyrene); and Kraton Performance Polymers. Examples include oil-expanded compounds of these hydrogenated block copolymers, available from KRATON® G4609 (containing approximately 45% mineral oil and having approximately 33% polystyrene by weight in SEBS) and G4610 (containing approximately 31% mineral oil and having approximately 33% polystyrene by weight in SEBS) from Inc., and available from Asahi Kasei Corporation as TUFTEC® H1272 (containing approximately 36% oil and having approximately 35% polystyrene by weight in SEBS). Mixtures of two or more hydrogenated block copolymers can be used.

[0038] In some embodiments, the hydrogenated block copolymer has a weight-average molecular weight of 40,000 to 400,000 grams (g / mol) per mole. The number-average molecular weight and weight-average molecular weight can be determined by gel permeation chromatography based on comparison with a polystyrene standard. In some embodiments, 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 some embodiments, 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.

[0039] The impact modifier may be present in an amount of 1 to 20 weight percent of the total weight of the composition. Within this range, the amount of impact modifier may be 3 to 20 weight percent, 3 to 15 weight percent, 5 to 20 weight percent, 5 to 15 weight percent, 5 to 13 weight percent, 8 to 15 weight percent, or 8 to 12 weight percent, respectively, of the total weight of the composition.

[0040] In certain embodiments, the impact modifier may include a hydrogenated block copolymer, which may be present in an amount of 1 to 20 weight percent of the total weight of the composition. Within this range, the amount of hydrogenated block copolymer may be 3 to 20 weight percent, or 3 to 15 weight percent, or 5 to 20 weight percent, or 5 to 15 weight percent, or 5 to 13 weight percent, or 8 to 15 weight percent, or 8 to 12 weight percent, respectively, of the total weight of the composition.

[0041] In addition to poly(phenylene ether), polyamide, and impact modifier, the composition further comprises a conductive agent. The conductive agent may be any agent that enhances the conductivity of the composition. Suitable conductive fillers may be fibrous, disc-shaped, spherical, or amorphous. Suitable conductive agents include, for example, graphite, conductive carbon black, conductive carbon fibers, metal fibers, metal particles, and particles of intrinsically conductive polymers. In some embodiments, the conductive agent may include carbon black, carbon fibers, carbon nanotubes, or a combination thereof.

[0042] Other conductive fillers that can be used include metal-coated carbon fibers, metal fibers, metal discs, metal particles, metal-coated talc, metal-coated disc-shaped fillers such as mica and kaolin. In some embodiments, preferred conductive fillers include carbon black, carbon fibers, carbon nanotubes, and mixtures thereof.

[0043] In some embodiments, the conductive filler may include carbon black. Carbon black may refer to an amorphous form of carbon having a high surface area-to-volume ratio. Furthermore, depending on the manufacturing conditions, carbon black may contain varying degrees of chemiadsorbed oxygen complexes (e.g., carboxylic acid groups, quinone groups, lactone groups, phenol groups, etc.) on its surface. Carbon black properties such as particle size, structure, and purity may vary depending on the type of carbon black selected. In some embodiments, carbon black may disperse well within the composition, maintain the integrity of its structure or network, and have a consistent particle size. Conductive carbon black as disclosed herein does not refer to carbon black intended for colorant purposes. As used herein, the term “conductive carbon black” refers to a specific carbon black having a particular surface area, oil absorption value (OAN), and other properties, as will be further discussed herein. Conductive carbon black has a larger surface area and OAN (e.g., is highly structured) compared to carbon black typically used as a colorant.

[0044] In some embodiments, the conductive carbon black useful in this disclosure may be furnace black, acetylene black, or extra conductive carbon black. Conductive carbon black such as furnace black or acetylene black may have a conductivity of, for example, 1 to 10 2 It may have a high volume resistivity in the range of Ω-cm. The useful conductive carbon black of this disclosure is at least 50 square meters (m²) per gram. 2 ( / g), for example, 50-1000m 2 The BET (Brunauer, Emmett, and Teller) specific surface area per gram may be shown.

[0045] In some embodiments, electrically conductive fillers may contain highly structured carbon black. Highly structured carbon black can offer higher viscosity, greater electrical conductivity, and easier dispersion. Measures of aggregate structure can be obtained from scanning electron microscopy (SEM) analysis and shape distribution from oil absorption values ​​(OAN). OAN is a measure of the liquid absorption capacity of carbon black. It is the number of cubic centimeters of dibutyl phthalate (DBP) or paraffin oil absorbed by 100 g of carbon black under specific conditions. The OAN value is proportional to the degree of aggregation of the carbon black structure. Test methods such as ASTM D 2414 and D 3493 can be used to determine the OAN. An OAN value of less than 100 ml per 100 grams (ml / 100 g) can be considered low-structured carbon and is typical for carbon black used as a black colorant, reinforcing additive, or UV absorber. OAN values ​​of 100 to 140 ml / 100g can be considered medium-level structured carbon black, primarily used for wire and cable insulation shielding and electrostatic discharge applications. OAN values ​​greater than 140 ml / 100g can be considered high-level structured carbon black, while OAN values ​​greater than 280 ml / 100g may be ultra-high-level structured carbon black.

[0046] In some embodiments, the conductive carbon black useful in the composition may exhibit an OAN of at least 100 ml / 100 g, or at least 150 ml / 100 g. In some embodiments, the disclosed composition may include a highly structured conductive carbon black having an OAN value of at least 140 ml / 100 g when tested according to ASTM D 2414 and / or D 3493. In some embodiments, the conductive carbon black may have a DBP oil absorption capacity of 80 to 500 ml / 100 g.

[0047] Exemplary conductive carbon black is available from Earache Europe or Imerys Graphite & Carbon Switzerland as ENSACO® 250G carbon powder.

[0048] In some embodiments, the composition may include electrically conductive carbon black having at least one dimension of a specific size. The electrically conductive carbon black may include powder having a specific particle size distribution. For example, the electrically conductive carbon black may have at least one dimension of less than 100 nm. However, these particles may aggregate together to have a specific structure, increasing the aggregate dimensions, which may be on the micrometer scale. In some embodiments, the electrically conductive carbon black may have a specific diameter. For example, the electrically conductive carbon black may have a primary particle diameter of 10 to 50 nm. In further examples, the conductive carbon black may have a primary particle size (or particle diameter) of 20 to 50 nm.

[0049] Exemplary conductive carbon blacks may include conductive carbon black having an average particle size of less than 200 nanometers, preferably less than 100 nanometers, and more preferably less than 50 nanometers. Preferred conductive carbon blacks may also include 200 nanometers. 2 Greater than / g, preferably 400m 2 Greater than / g, and more preferably 1000m 2 It may have a surface area greater than / g. Preferred conductive carbon black is also 40cm².3 / Greater than 100g, preferably 100cm 3 / Greater than 100g, more preferably 150cm 3 It may have a pore volume (dibutyl phthalate absorption) greater than 100g. Preferred conductive carbon black may also have less than 2% by weight of volatile matter. Particularly preferred carbon fibers include graphite or partially graphite vapor-grown carbon fibers having a diameter of 3.5 to 500 nanometers, preferably having a diameter of 3.5 to 70 nanometers, and more preferably having a diameter of 3.5 to 50 nanometers. Typical carbon fibers include, for example, the vapor-grown carbon fibers described in U.S. Patent Nos. 4,565,684 and 5,024,818 by Tibbetts et al., U.S. Patent No. 4,572,813 by Arakawa, U.S. Patent Nos. 4,663,230 and 5,165,909 by Tennent, U.S. Patent No. 4,816,289 by Komatsu et al., U.S. Patent No. 4,876,078 by Arakawa et al., U.S. Patent No. 5,589,152 by Tennent et al., and U.S. Patent No. 5,591,382 by Nahas et al.

[0050] An exemplary conductive carbon fiber may have a length of 0.25 inches (0.635 cm) and a diameter of 7 micrometers. Conductive carbon fibers may also include aggregates of fibers having an aspect ratio of at least 5 and an average diameter of 3.5 to 500 nanometers, as described in, for example, U.S. Patent Nos. 4,565,684 and 5,024,818 by Tibbetts et al., U.S. Patent No. 4,572,813 by Arakawa, U.S. Patent No. 4,663,230 and 5,165,909 by Tennent, U.S. Patent No. 4,816,289 by Komatsu et al., U.S. Patent No. 4,876,078 by Arakawa et al., U.S. Patent No. 5,589,152 by Tennent et al., and U.S. Patent No. 5,591,382 by Nahas et al. Exemplary graphite particles have an average particle size of 20–1,000 nanometers and 1–100 m 2 It can have a surface area of ​​ / g. Examples of intrinsically conductive polymers include polyaniline, polypyrrole, polyphenylene, and polyacetylene.

[0051] In certain embodiments, the conductive agent may include carbon nanotubes. The carbon nanotubes may be monolayered or multilayered. In certain embodiments, the carbon nanotubes may be multilayered. In certain embodiments, the carbon nanotubes may have an average diameter of 2 to 20 nanometers.

[0052] The conductive agent may be present in the composition in an amount of 0.1 to 10 weight percent of the total weight of the composition. Within this range, the conductive agent may be present in an amount of 0.5 to 8 weight percent, or 0.5 to 5 weight percent, or 0.6 to 2.5 weight percent, or 0.7 to 1.8 weight percent, or 0.8 to 1.2 weight percent, based on the total weight of the composition. In some embodiments, if the conductive agent is conductive carbon black, the conductive carbon black may be present in an amount of less than 2 weight percent, or less than 1.5 weight percent, or less than 1.2 weight percent, or 0.1 to 1.8 weight percent, or 0.1 to 1.2 weight percent, or 0.7 to 1.8 weight percent, or 0.8 to 1.2 weight percent, based on the total weight of the composition. In some embodiments, if the conductive agent is conductive carbon black, the conductive carbon black may be present in an amount of greater than 2 weight percent, or 2.2 to 10 weight percent, or 2.5 to 10 weight percent, or 3 to 10 weight percent, based on the total weight of the composition.

[0053] The thermoplastic composition further comprises a hydroxyl group-containing compound. The hydroxyl group-containing compound comprises or is selected from bisphenoxyethanol fluorene, terpene phenol resins, novolac resins, or combinations thereof. In some embodiments, the hydroxyl group-containing compound comprises bisphenoxyethanol fluorene. In some embodiments, the hydroxyl group-containing compound comprises a terpene phenol resin (i.e., a resin prepared from a terpene and a phenol compound). The terpene phenol resin may refer to a terpene phenol copolymer resin, which is a copolymer of a terpene and a phenol compound, and a phenol-modified terpene resin, which is a phenol-modified product of a terpene homopolymer or terpene copolymer (terpene resin, typically an unmodified terpene resin). Exemplary terpenes including terpene phenol resins include monoterpenes such as α-pinene, β-pinene, and limonene (including d-limonene, l-limonene, and d / l-limonene (dipentene)). In some embodiments, the terpene phenol resin has a hydroxyl value of 50 to 150 mg KOH / g. In some embodiments, the hydroxyl group-containing compound includes novolac resins. As used herein, novolac resins refer to oligomers and polymers derived from phenols and formaldehydes. Phenol-formaldehyde resins can be prepared by reacting at least one aldehyde with at least one phenol or substituted phenol in the presence of an acid or other catalyst, such that a molar excess of the phenol or substituted phenol is present. Suitable phenols and substituted phenols include phenol, o-cresol, m-cresol, p-cresol, thymol, ethylphenol, propylphenol, p-butylphenol, tert-butylcatechol, pentylphenol, hexylphenol, octaphenol, heptylphenol, nonylphenol, bisphenol-A, hydroxynaphthalene, resorcinol, bisphenol A, isoeugenol, o-methoxyphenol, 4,4'-dihydroxyphenyl-2,2-propane, isoamyl salicylate, benzyl salicylate, methyl salicylate, and 2,6-di-tert-butyl-p-cresol.Suitable aldehydes and aldehyde precursors include formaldehyde, paraformaldehyde, polyoxymethylene, and trioxane. Two or more aldehydes or phenols can be used in the preparation of the novolac resin. In one embodiment, the novolac resin has a phenol content of 0.1 to 3 weight percent based on the total weight of the novolac resin.

[0054] Hydroxyl group-containing compounds may be present in a thermoplastic composition in an amount of 1 to 10 weight percent of the total weight of the composition. Within this range, each hydroxyl group-containing compound may be present in an amount of 1 to 8 weight percent, or 1.2 to 7.8 weight percent, or 1.3 to 7.5 weight percent, or 1 to 7 weight percent, or 1.5 to 7 weight percent, or 1.5 to 6.5 weight percent of the total weight of the composition.

[0055] The composition further comprises a compatibilizer. As used herein, the term “compatibilizer” refers to a polyfunctional compound that interacts with poly(phenylene ether), polyamide, or both. This interaction may be chemical (e.g., grafting) and / or physical (e.g., affecting the surface characteristics of the dispersed phase). In either case, the resulting composition exhibits improved compatibility, as demonstrated in particular by improvements in impact strength, knit line strength of the molded article, or tensile elongation.

[0056] Examples of compatibilizers that can be used include liquid diene polymers, epoxy compounds, oxidized polyolefin waxes, quinones, organosilane compounds, polyfunctional compounds, functionalized poly(arylene ethers), and combinations thereof. Compatibilizers are further described in U.S. Patent No. 5,132,365 by Gallucci, and in U.S. Patents No. 6,593,411 and No. 7,226,963 by Koevoets et al.

[0057] In some embodiments, the compatibilizer includes a polyfunctional compound. There are typically three types of polyfunctional compounds that can be used as compatibilizers. The first type of polyfunctional compound has both (a) a carbon-carbon double bond or carbon-carbon triple bond and (b) at least one carboxylic acid, anhydride, amide, ester, imide, amino, epoxy, orthoester, or hydroxyl group in its molecule. Examples of such polyfunctional compounds include maleic acid, maleic anhydride, fumaric acid, glycidyl acrylate, itaconic acid, aconitic acid, maleimide, maleic acid hydrazide, reaction products obtained from diamines and maleic anhydride, maleic acid, fumaric acid, dichloromaleic anhydride, maleic acid amide, unsaturated dicarboxylic acids (e.g., acrylic acid, butenoic acid, methacrylic acid, ethyl acrylic acid, pentenoic acid, 10-hydroxy-2-decenoic acid, un10-hydroxy-2-decenoic acid, do10-hydroxy-2-decenoic acid, linoleic acid, etc.), esters of the aforementioned unsaturated carboxylic acids, acid amides or anhydrides, unsaturated alcohols (e.g., alkanols, clotyl alcohol, methyl vinylcarbinol, 4-penten-1-ol, 1,4-hexadiene-3-ol, 3-buten-1,4-diol, 2,5-dimethyl-3-hexen-2,5-diol, and formula C n H 2n -5OH, C n H 2n -7OH and C n H 2n Examples include -9OH alcohols (wherein n is a positive integer less than or equal to 30), unsaturated amines obtained by replacing the -OH group of the above unsaturated alcohol with an -NH2 group, functionalized diene polymers and copolymers, and combinations of one or more of the above. In some embodiments, the compatibilizer includes maleic anhydride, fumaric acid, or a combination thereof.

[0058] The second type of polyfunctional compatibilizer has both (a) a group represented by formula (OR) where R is hydrogen or an alkyl, aryl, acyl, or carbonyldioxy group, and (b) at least two groups, which may be the same or different, selected from carboxylic acids, acid halides, anhydrides, acid halide anhydrides, esters, orthoesters, amides, imides, aminos, and various salts thereof. Typical examples of compatibilizers in this group are aliphatic polycarboxylic acids, acid esters, and acid amides represented by the following formulas. (R I O) m R'(COOR II ) n (CONR III R IV ) s (In the formula, R' is a straight-chain or branched-chain saturated aliphatic hydrocarbon having 2 to 20, or more specifically, 2 to 10 carbon atoms, R I Each R is an alkyl, aryl, acyl, or carbonyldioxy group having hydrogen or 1 to 10, or more specifically 1 to 6, or even more specifically 1 to 4 carbon atoms, and each R II Each R is independently an alkyl or aryl group having hydrogen or 1 to 20, or more specifically 1 to 10, carbon atoms, and each R III and R IV R is independently an alkyl or aryl group having hydrogen or 1 to 10, more specifically 1 to 6, or even more specifically 1 to 4 carbon atoms, where m is equal to 1, (n+s) is 2 or greater, or more specifically 2 or 3, n and s are each 0 or greater, (ORI) is alpha or beta relative to the carbonyl group, and at least two carbonyl groups are separated by 2 to 6 carbon atoms. Clearly, R I , R II , R III , and R IV If each substituent has fewer than six carbon atoms, it cannot be an aryl molecule.

[0059] Suitable polycarboxylic acids include, for example, citric acid, malic acid, and agaricic acid, in various commercially available forms thereof, such as anhydrides and hydrated acids, as well as combinations containing one or more of the aforementioned. In some embodiments, the compatibilizer includes citric acid. Examples of esters useful herein include, for example, acetyl citrate, monostearyl citrate, and / or distearyl citrate. Suitable amides useful in the present invention include, for example, N,N'-diethylcitric acid amide, N-phenylcitric acid amide, N-dodecylenoic acid amide, N,N'-didodecylenoic acid amide, and N-dodecyl malic acid. Derivatives include salts with amines, as well as salts thereof including alkalis and alkali metal salts. Examples of suitable salts include calcium malate, calcium citrate, potassium malate, and potassium citrate.

[0060] A third type of polyfunctional compatibilizer has both (a) an acid halide group and (b) at least one carboxylic acid, anhydride, ester, epoxy, orthoester, or amide group, preferably a carboxylic acid or anhydride group, in its molecule. Examples of compatibilizers in this group include trimellitic anhydride chloride, chloroformylsuccinic anhydride, chloroformylsuccinic acid, chloroformylglutaric anhydride, chloroformylglutaric acid, chloroacetylsuccinic anhydride, chloroacetylsuccinic acid, trimellitic acid chloride, and chloroacetylglutaric acid. In one embodiment, the compatibilizer includes trimellitic anhydride chloride.

[0061] In certain embodiments, the compatibilizer may include maleic acid, maleic anhydride, citric acid, fumaric acid, or a combination thereof. In certain embodiments, the compatibilizer may include citric acid.

[0062] The compatibilizer may be present in the composition in an amount of 0.01 to 10 weight percent of the total weight of the composition. Within this range, the compatibilizer may be present in an amount of 0.01 to 5 weight percent, or 0.01 to 1.5 weight percent, or 0.1 to 10 weight percent, or 0.1 to 5 weight percent, or 0.2 to 1 weight percent, or 0.4 to 0.9 weight percent of the total weight of the composition.

[0063] The composition may optionally further include an additive composition containing one or more additives selected to achieve desired properties, provided that the additives are also selected so as not to significantly adversely affect the desired properties of the composition. The additive composition or individual additives may be mixed at a suitable point in the mixing of the components to form the composition. The additive composition may include flow modifiers, fillers (e.g., particulate polytetrafluoroethylene (PTFE), glass, carbon, minerals, or metals), antioxidants, heat stabilizers, light stabilizers, ultraviolet (UV) light stabilizers, UV absorbing additives, plasticizers, lubricants, release agents (e.g., mold release agents), antistatic agents, antifogging agents, antimicrobial agents, colorants (e.g., dyes or pigments), surface effect additives, radiation stabilizers, flame retardants, anti-dripping agents (e.g., PTFE-encapsulated styrene-acrylonitrile copolymer (TSAN)), or combinations thereof. Additives are used in amounts generally known to be effective. For example, the total amount of additive compositions (other than any impact modifiers, fillers, or reinforcing agents) may be 0.001 to 10 weight percent, 0.1 to 10 weight percent, or 0.01 to 5 weight percent, respectively, based on the total weight of polymers in the composition. In some embodiments, the composition may exclude additives not specifically disclosed herein.

[0064] In certain embodiments, the thermoplastic composition may include 32 to 50 weight percent of poly(phenylene ether), 34 to 55 weight percent of polyamide, 3 to 15 weight percent of an impact modifier comprising polystyrene-poly(ethylene-propylene) diblock copolymer and polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer, 0.5 to 5 weight percent of a conductive agent, 1 to 7.5 weight percent of a hydroxyl group-containing compound comprising bisphenoxyethanol fluorene, terpene phenol resin, novolac resin, or a combination thereof, and 0.1 to 3 weight percent of a compatibilizer.

[0065] In another specific embodiment, the poly(phenylene ether) comprises poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.33 to 0.46 deciliters per gram as measured by an Ubberohde viscometer in chloroform at 25°C, the polyamide comprises polyamide-6,6, the conductive agent comprises carbon nanotubes, and the compatibilizer comprises maleic acid, maleic anhydride, citric acid, fumaric acid, or a combination thereof, preferably citric acid.

[0066] In another specific embodiment, the thermoplastic composition comprises 32 to 50 weight percent poly(phenylene ether), 34 to 55 weight percent polyamide, 3 to 15 weight percent impact modifiers including polystyrene-poly(ethylene-propylene) diblock copolymer and polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer, 0.5 to 5 weight percent conductive agent, and 1 to 7.5 weight percent bisphenoxyethanol fluorene, terpene phenol resin, novolac resin, or a combination thereof. The compound may contain a droxy group-containing compound and 0.1 to 3 weight percent of a compatibilizer, where poly(phenylene ether) is poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.33 to 0.46 deciliters per gram as measured by an Ubbelohde viscometer in chloroform at 25°C, polyamide is polyamide-6,6, conductive agent is carbon nanotubes, and compatibilizer is maleic acid, maleic anhydride, citric acid, fumaric acid, or a combination thereof, preferably citric acid.

[0067] The relative amounts of each component can be adjusted to provide a desired combination of properties. As will be understood by those skilled in the art, the amounts of each component can be selected within the enumerated range so that their total weight is 100 percent.

[0068] The composition may optionally exclude or minimize components not specifically described herein. In some embodiments, the composition may exclude or minimize thermoplastic polymers other than poly(phenylene ether), polyamides, and impact modifiers (e.g., less than 5% by weight, or less than 1% by weight, or less than 0.1% by weight). In some embodiments, the composition may exclude or minimize homopolystyrene. In some embodiments, the composition may exclude or minimize rubber-modified polystyrene. In some embodiments, the composition may exclude or minimize impact modifiers other than hydrogenated block copolymers.

[0069] The compositions of this disclosure may exhibit one or more advantageous properties. For example, a molded sample of the composition may have a strength of 7 kilojoules per square meter (kJ / m²) as determined in accordance with ISO 180. 2 ) or more, or 10 kJ / m³ 2 The composition can exhibit the above notched Izod impact strength. The composition may exhibit a water absorption rate of less than 1%, or less than 0.9%, or less than 0.8%, or less than 0.75%, or less than 0.7%, or less than 0.6%, or less than 0.5%, or 0.01-0.75%, or 0.05-0.5%. The composition may exhibit a water absorption rate of 10 cubic centimeters per 10 minutes as determined according to ISO 1133. 3 (10 min) or larger than 12 cm 3 / More than 10 minutes, or 15cm 3 The composition may exhibit a melt volume flow rate greater than 10 minutes. The composition may exhibit a volume resistivity of less than 6000 ohms-cm (ohms-cm) or less than 5000 ohms-cm, for example, between 500 and 6000 ohms-cm or between 500 and 5000 ohms-cm. The above characteristics can be determined, for example, by the test standards and procedures further described in the following working examples.

[0070] The composition can generally be prepared by any method. In some embodiments, the composition can be prepared by melt-mixing the components of the composition. For example, the composition can be formed by combining the components of the composition. In some embodiments, the components of the composition can be dry-blended, and the dry blend can be added to the upstream port of an extruder. The dry blend can then be melt-mixed. In some embodiments, polyamide and, if present, any fillers can be added to the molten mixture using a separate downstream feeder. Typical melt-mixing temperatures can be 250–350°C. Molded articles can be formed from the composition, for example, by injection molding or extrusion. Exemplary methods for producing the composition are further described in the following working examples.

[0071] The composition may be useful for a variety of applications, particularly in automotive applications. Therefore, another aspect of the present disclosure is an article formed from one of the compositions in any of the above-described variations. Such articles include components used in the interiors of vehicles, including automobiles, aircraft, ships, trains, and subway cars. Specific articles include automotive parts, such as automotive body panels or service flaps.

[0072] Therefore, the compositions of this disclosure offer significant advantages with respect to certain properties, such as melt flow, water absorption, and impact strength. Compositions exhibiting this desirable balance of properties may be particularly useful for forming articles for various applications and for use in reinforced thermoplastic composite materials. Thus, significant advantages are provided by this disclosure.

[0073] This disclosure is further illustrated by the following non-limiting embodiments. [Examples]

[0074] The materials used in the following examples are listed in Table 1.

[0075] [Table 1]

[0076] The composition was compounded using a Toshiba Machine Co., Ltd. TEM50A compounding extruder. All components were added at the feed port, except for a pre-blended PA-66 / CNT masterbatch added downstream using a side feeder. Compounding was performed at a barrel temperature of 300°C, a screw rotation speed of 330 RPM, and a processing rate of 80 kg / h. Strands with a diameter of 3 mm were extruded through a die, cooled in a water bath, and then pelletized. The pellets were dried at 120°C for 4 hours and then injection molded. Test specimens were prepared using a 100-ton injection molding machine operating at a melting temperature of 280°C and a mold temperature of 80°C. The properties of the molded parts were tested according to the following standards summarized in Table 2.

[0077] [Table 2]

[0078] The water absorption rate was calculated according to the following formula: Weight increase (percent, %) = ((wet weight - dry weight) / dry weight) × 100.

[0079] The volume resistivity (SVR) value, expressed in ohms-centimeters, was determined at 23°C as follows: A tensile bar was formed according to ISO 3167-2002. Sharp, shallow cuts were made near each end of the narrow central portion of the bar. The bar was fractured in a brittle form at each cut, separating the narrow central portion with fractured ends having cross-sectional dimensions of 10 mm × 4 mm. To obtain fracture in a brittle form, the tensile bar was cooled, for example, in dry ice, in a -40°C freezer, or in liquid nitrogen. The length of the bar between the fractured ends was measured. The fractured ends of the sample were painted with conductive silver paint, and the paint was allowed to dry. Using a multimeter, electrodes were attached to each of the painted surfaces, and the resistance was measured with an applied voltage of 500 millivolts to 1000 millivolts. The volume resistivity value was obtained by multiplying the measured resistance by the fracture area on one side of the bar and dividing by the length of the bar. r = R × A / L (In the formula, r is the volume resistivity in ohms-centimeters, R is the measured resistance in ohms, A is the fracture area in square centimeters, and L is the sample length in centimeters.) This procedure was repeated for a total of five samples, and the results for the five samples were averaged to obtain the reported volume resistivity.

[0080] The composition and properties are summarized in Tables 3A, 3B, 3C, and 3D. The amount of each component is given as a weight percentage of the total weight of the composition.

[0081] [Table 3]

[0082] [Table 4]

[0083] [Table 5]

[0084] [Table 6]

[0085] As shown in Table 3 and by Comparative Examples 1-4, water absorption can be reduced by reducing the amount of polyamide (e.g., PA66) in the composition. However, the MVR is undesirably affected. The compositions of Examples 1-10 demonstrate that by adding BPEF or certain phenolic compounds, a reduction in water absorption can be achieved, the SVR can be improved, and the MVR can be maintained or improved compared to Comparative Example 1.

[0086] Furthermore, as shown in Table 3, phenolic resins with lower levels of phenolic residues (PhOH-2 compared to PhOH-1) were shown to provide improved conductivity along with reduced water absorption. Examples 21 and 26 demonstrate that by adding a small amount of PhOH-2 or PhOH-6 to a composition containing the same amount of PA as Comparative Example 1, the same level of water absorption can be obtained compared to compositions with less PA, but with improved mechanical properties and conductivity.

[0087] Therefore, this disclosure provides a significant improvement.

[0088] This disclosure further encompasses the following aspects:

[0089] Embodiment 1: A thermoplastic composition comprising 30 to 60 weight percent of poly(phenylene ether), 30 to 60 weight percent of polyamide, 1 to 20 weight percent of an impact modifier, 0.1 to 10 weight percent of a conductive agent, 1 to 10 weight percent of a hydroxyl group-containing compound comprising bisphenoxyethanol fluorene, terpene phenol resin, novolac resin, or a combination thereof, and 0.01 to 10 weight percent of a compatibilizer, wherein the weight percentage is relative to the total weight of the thermoplastic composition.

[0090] Embodiment 2: A thermoplastic composition according to Embodiment 1, characterized in that the poly(phenylene ether) comprises poly(2,6-dimethyl-1,4-phenylene ether), which preferably has an intrinsic viscosity of 0.33 to 0.46 deciliters per gram, as measured by an Ubbelohde viscometer in chloroform at 25°C.

[0091] Aspect 3: A thermoplastic composition according to Aspect 1 or 2, wherein the polyamide comprises polyamide-6, polyamide-6,6, polyamide-6,10, polyamide-4,10, polyamide-5,10, polyamide-10,10, polyamide-9T, polyamide-6T, polyamide-10T, polyamide-6I, polyamide-MXD6, or a combination thereof, preferably comprising polyamide-6,6, and optionally the polyamide being a biopolyamide, recycled polyamide, or upcycled polyamide.

[0092] Embodiment 4: A thermoplastic composition according to any one of Embodiments 1 to 3, wherein the impact modifier comprises a hydrogenated block copolymer, preferably the hydrogenated block copolymer comprises a polystyrene-poly(ethylene-propylene) diblock copolymer, a polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer, or a combination thereof, more preferably the hydrogenated block copolymer has a polystyrene content of 28 to 37 weight percent, and even more preferably the hydrogenated block copolymer comprises a polystyrene-poly(ethylene-propylene) diblock copolymer and a polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer.

[0093] Embodiment 5: A thermoplastic composition according to any one of Embodiments 1 to 4, characterized in that the conductive agent is conductive carbon black, Ketjenblack, carbon nanotubes, carbon fibers, graphite, metal fibers, metal particles, conductive polymer particles, metal-coated carbon fibers, or a combination thereof, or conductive carbon black, carbon fibers, carbon nanotubes, or a combination thereof.

[0094] Embodiment 6: A conductive thermoplastic composition according to any one of claims 1 to 5, wherein the conductive agent comprises at least 50 m 2A conductive thermoplastic composition characterized by containing conductive carbon black having a BET specific surface area of ​​ / g, an OAN value of at least 140 ml / 100g when tested according to ASTM D 2414 and / or D 3493, or both.

[0095] Embodiment 7: A thermoplastic composition according to any one of Embodiments 1 to 6, characterized in that the conductive agent comprises carbon nanotubes, preferably multi-walled carbon nanotubes having an average diameter of 2 to 20 nanometers.

[0096] Embodiment 8: A thermoplastic composition according to any one of Embodiments 1 to 7, characterized in that the hydroxyl group-containing compound comprises bisphenoxyethanolfluorene.

[0097] Embodiment 9: A thermoplastic composition according to any one of Embodiments 1 to 8, characterized in that the hydroxyl group-containing compound comprises a terpene phenol resin, and preferably the terpene phenol resin has a hydroxyl value of 50 to 150 mg KOH / g.

[0098] Embodiment 10: A thermoplastic composition according to any one of Embodiments 1 to 7, characterized in that the hydroxyl group-containing compound includes a novolac resin.

[0099] Embodiment 11: A thermoplastic composition according to any one of Embodiments 1 to 10, characterized in that the compatibilizer comprises maleic acid, maleic anhydride, citric acid, fumaric acid, or a combination thereof, preferably citric acid.

[0100] Embodiment 12: A thermoplastic composition according to any one of Embodiments 1 to 11, characterized in that it is a product obtained by melt-blending the components of the composition.

[0101] Embodiment 13: A composition according to any one of Embodiments 1 to 12, characterized by comprising: 32 to 50 weight percent of poly(phenylene ether); 34 to 55 weight percent of polyamide; 3 to 15 weight percent of an impact modifier comprising polystyrene-poly(ethylene-propylene) diblock copolymer and polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer; 0.5 to 5 weight percent of a conductive agent; 1 to 7.5 weight percent of a hydroxyl group-containing compound comprising bisphenoxyethanol fluorene, terpene phenol resin, novolac resin, or a combination thereof; and 0.1 to 3 weight percent of a compatibilizer.

[0102] Embodiment 14: A conductive thermoplastic composition according to Embodiment 13, characterized in that the poly(phenylene ether) comprises poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.33 to 0.46 deciliters per gram as measured by an Ubbelohde viscometer in chloroform at 25°C, the polyamide comprises polyamide-6,6, the conductive agent comprises carbon nanotubes, and the compatibilizer comprises maleic acid, maleic anhydride, citric acid, fumaric acid, or a combination thereof, preferably citric acid.

[0103] Embodiment 15: An article comprising the composition described in any one of Embodiments 1 to 14, preferably an exterior painted automotive component, an automotive body panel, or a service flap.

[0104] Embodiment 16: A method for producing a composition according to any one of Embodiments 1 to 14, characterized by comprising melt-blending the components of the composition.

[0105] Compositions, methods, and articles may, alternatively, include, consist of, or essentially consist of any suitable materials, steps, or components disclosed herein. Compositions, methods, and articles may, additionally or alternatively, be formulated to lack or substantially include any materials (or types), steps, or components that are unnecessary for achieving the function or purpose of the composition, method, and article.

[0106] All scope disclosed herein includes endpoints, which can be combined independently with one another. “Combinations” include blends, mixtures, alloys, reaction products, etc. Terms such as “first,” “second,” etc., do not indicate any order, quantity, or importance, but rather are used to distinguish one element from another. The terms “a,” “an,” and “the” do not indicate a limit on quantity and should be interpreted as encompassing both singular and plural unless otherwise indicated herein or unless the context clearly contradicts this. “Or” means “and / or” unless otherwise specified. Throughout this specification, references to “aspects” mean that a particular element described in relation to that aspect may be included in at least one aspect described herein and may or may not be present in other aspects. As used herein, the term “their combinations” includes one or more of the listed elements, is open, and allows for the presence of one or more similar elements not listed. Furthermore, it should be understood that the described elements may be combined in any suitable manner in various aspects.

[0107] It will be understood that the combined weight of all components of the composition is 100 weight percent in total.

[0108] Unless otherwise specified herein, all test standards are the most current standards in effect as of the filing date of this application, and, if priority is claimed, the most current standards in effect as of the filing date of the earliest priority application that describes such test standards.

[0109] Unless otherwise defined, technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art to which this application pertains. All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if any terminology in this application conflicts with or is inconsistent with any terminology in any of the cited references, the terminology from this application shall prevail over the conflicting terminology in the cited references.

[0110] 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 ("-") without a space between two letters or symbols is used to indicate a substituent bond. For example, -CHO is bonded via the carbonyl group's carbon.

[0111] As used herein, the term "hydrocarbyl" refers to a residue containing only carbon and hydrogen, whether used by itself or as a prefix, suffix, or component of another term. A residue may be aliphatic or aromatic, linear, cyclic, bicyclic, branched, saturated, or unsaturated. It may also contain combinations of aliphatic, aromatic, linear, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties. However, where a hydrocarbyl residue is described as substituted, it may optionally contain a heteroatom in addition to the carbon and hydrogen members of the substituted residue. Thus, where specifically described as substituted, a hydrocarbyl residue may also contain one or more carbonyl groups, amino groups, hydroxyl groups, etc., or it may contain a heteroatom within the hydrocarbyl residue's backbone. The term "alkyl" refers to a branched or straight-chain saturated aliphatic hydrocarbon group, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, s-pentyl, and n- and s-hexyl. "Alkenyl" refers to a straight or branched monovalent hydrocarbon group having at least one carbon-carbon double bond (e.g., ethenyl (-HC=CH2)). "Alkoxy" refers to an alkyl group linked via oxygen (i.e., alkyl-O-), such as methoxy, ethoxy, and sec-butyloxy groups. "Alkylene" refers to a straight or branched saturated divalent aliphatic hydrocarbon group (e.g., methylene (-CH2-) or propylene (-(CH2)3-)). "Cycloalkylene" refers to a divalent cyclic alkylene group, -C n H 2n-xThis means x is the number of hydrogens replaced by cyclization. "Cycloalkenyl" means a monovalent group having one or more rings and one or more carbon-carbon double bonds within the rings, where all ring members are carbon (e.g., cyclopentyl and cyclohexyl). "Aryl" means an aromatic hydrocarbon group containing a certain 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 containing one or more fluoro, chloro, bromo, or iodo substituents. Different combinations of halo atoms (e.g., bromo and fluoro), or only chloro atoms may be present. The prefix "hetero" means that a compound or group contains at least one heteroatom ring member (e.g., 1, 2, or 3 heteroatoms) (where each heteroatom is independently N, O, S, Si, or P). "Substituted" means that a compound or group contains, 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 Alkenil, C 5~12 Cycloalkenyl, C 6~12 Ariel, C 7~13 Arylalkylene, C 4~12 Heterocycloalkyl, and C 3~12This means that at least one (e.g., 1, 2, 3, or 4) substituents, which may be heteroaryl, are substituted in place of hydrogen, but not exceeding the normal valence of the substituted atom. The number of carbon atoms shown in the group is excluding any substituents. For example, -CH2CH2CN is a nitrile-substituted C2 alkyl group.

[0112] While specific embodiments have been described, alternative forms, modifications, variations, improvements, and substantial equivalents that are not anticipated or cannot be anticipated at present may arise for the applicant or others skilled in the art. Accordingly, the attached claims, which may be filed and amended, are intended to encompass all such alternative forms, modifications, variations, improvements, and substantial equivalents.

Claims

1. A conductive thermoplastic composition, 30-60 weight percent poly(phenylene ether), 30-60 weight percent polyamide, 1 to 20 weight percent of impact modifier, 0.1 to 10 weight percent of conductive agent, A hydroxyl group-containing compound comprising 1 to 10 weight percent of bisphenoxyethanol fluorene, terpene phenol resin, novolac resin, or a combination thereof, It contains 0.01 to 10 weight percent of a compatibilizer, A conductive thermoplastic composition characterized in that the weight percentage is relative to the total weight of the thermoplastic composition.

2. A conductive thermoplastic composition according to claim 1, characterized in that the poly(phenylene ether) comprises poly(2,6-dimethyl-1,4-phenylene ether), which preferably has an intrinsic viscosity of 0.33 to 0.46 deciliters per gram, as measured by an Ubbelohde viscometer in chloroform at 25°C.

3. A conductive thermoplastic composition according to claim 1 or 2, wherein the polyamide comprises polyamide-6, polyamide-6,6, polyamide-6,10, polyamide-4,10, polyamide-5,10, polyamide-10,10, polyamide-9T, polyamide-6T, polyamide-10T, polyamide-6I, polyamide-MXD6, or a combination thereof, preferably comprising polyamide-6,6, and optionally the polyamide is a biopolyamide, recycled polyamide, or upcycled polyamide.

4. A conductive thermoplastic composition according to any one of claims 1 to 3, wherein the impact modifier comprises a hydrogenated block copolymer, preferably the hydrogenated block copolymer comprises a polystyrene-poly(ethylene-propylene) diblock copolymer, a polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer, or a combination thereof, more preferably the hydrogenated block copolymer has a polystyrene content of 28 to 37 weight percent, and even more preferably the hydrogenated block copolymer comprises the polystyrene-poly(ethylene-propylene) diblock copolymer and the polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer.

5. A conductive thermoplastic composition according to any one of claims 1 to 4, wherein the conductive agent is conductive carbon black, Ketjenblack, carbon nanotubes, carbon fibers, graphite, metal fibers, metal particles, conductive polymer particles, metal-coated carbon fibers, or a combination thereof, A conductive thermoplastic composition characterized by comprising conductive carbon black, carbon fibers, carbon nanotubes, or a combination thereof.

6. A conductive thermoplastic composition according to any one of claims 1 to 5, wherein the conductive agent comprises at least 50 m ２ A conductive thermoplastic composition characterized by containing conductive carbon black having a BET specific surface area per g, an OAN value of at least 140 ml / 100 g when tested according to ASTM D 2414 and / or D 3493, or both.

7. A conductive thermoplastic composition according to any one of claims 1 to 6, characterized in that the conductive agent comprises carbon nanotubes, preferably multi-walled carbon nanotubes having an average diameter of 2 to 20 nanometers.

8. A conductive thermoplastic composition according to any one of claims 1 to 7, characterized in that the hydroxyl group-containing compound comprises the bisphenoxyethanol fluorene.

9. A conductive thermoplastic composition according to any one of claims 1 to 7, characterized in that the hydroxyl group-containing compound comprises the terpene phenol resin or the novolac resin, and preferably the terpene phenol resin has a hydroxyl value of 50 to 150 mg KOH / g.

10. A conductive thermoplastic composition according to any one of claims 1 to 9, characterized in that the compatibilizer comprises maleic acid, maleic anhydride, citric acid, fumaric acid, or a combination thereof, preferably citric acid.

11. A conductive thermoplastic composition according to any one of claims 1 to 10, characterized in that it is a product obtained by melt-blending the components of the composition.

12. A conductive thermoplastic composition according to any one of claims 1 to 11, 32 to 50 weight percent of the aforementioned poly(phenylene ether), 34 to 55 weight percent of the polyamide, The impact modifier comprises 3 to 15 weight percent of polystyrene-poly(ethylene-propylene) diblock copolymer and polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer, The conductive agent in an amount of 0.5 to 5 weight percent, A hydroxyl group-containing compound comprising 1 to 7.5 weight percent of bisphenoxyethanol fluorene, terpene phenol resin, novolac resin, or a combination thereof, A conductive thermoplastic composition characterized by comprising 0.1 to 3 weight percent of the compatibilizer.

13. A conductive thermoplastic composition according to claim 12, The aforementioned poly(phenylene ether) contains poly(2,6-dimethyl-1,4-phenylene ether), which has an intrinsic viscosity of 0.33 to 0.46 deciliters per gram, as measured by a Ubberohde viscometer in chloroform at 25°C. The polyamide comprises polyamide-6,6, The conductive agent includes carbon nanotubes, A conductive thermoplastic composition characterized in that the compatibilizer contains maleic acid, maleic anhydride, citric acid, fumaric acid, or a combination thereof, preferably citric acid.

14. An article comprising a conductive thermoplastic composition according to any one of claims 1 to 13, preferably a painted automotive exterior part, automotive body panel, or service flap.

15. A method for producing a conductive thermoplastic composition according to any one of claims 1 to 13, characterized by comprising melt-blending the components of the composition.

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