Composition, method for producing the same, article made therefrom, and reinforced thermoplastic composite material containing the composition

Abstract

A composition comprising specified amounts of a poly(phenylene ether), a first polyamide, a hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene, pentaerythritol tetrastearate, and bisphenoxyethanol fluorene is believed to be particularly suitable for use in reinforced thermoplastic compositions containing reinforcing carbon fillers.

Description

Technical Field

[0001] The present application relates to a composition, a method for producing the same, an article made therefrom, and a reinforced thermoplastic composite material containing the composition.

[0002] The present application claims the priority and the benefit of European Patent Application No. 20172451.5 filed on April 30, 2020, the entire content of which is incorporated herein by reference.

Background Art

[0003] In order to obtain a composition having various beneficial properties such as heat resistance, chemical resistance, impact strength, hydrolysis stability, and dimensional stability, polyamide is blended with polyphenylene ether. In some applications, it may be desirable to use a poly(phenylene ether) / polyamide composition having good melt flow, low water uptake, and good mechanical properties. Unfortunately, it can be difficult to achieve such a well-balanced combination of properties. For example, polyamide is a known thermoplastic polymer having properties such as high melt flow, excellent processability, and chemical resistance. However, polyamide has a tendency to absorb water over time, which may cause warping or a decrease in the retention of mechanical strength. Various poly(phenylene ether) / polyamide mixtures are known and can exhibit low water uptake, but the melt flow is generally not sufficient for some applications, such as as a matrix material for fiber-reinforced thermoplastic composites. Another poly(phenylene ether) / polyamide mixture can exhibit high melt flow, but may have higher water uptake than lower-melt-flow analogs.

Summary of the Invention

Problems to be Solved by the Invention

[0004] Accordingly, there is a need in the art for a polyphenylene ether / polyamide composition that exhibits a combination of high melt flow and low water uptake.

Means for Solving the Problems

[0005] A composition, comprising 10 to 65% by mass of poly(phenylene ether), 30 to 70% by mass of a first polyamide, 1 to 10% by mass of a hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene, and 0.5 to 10% by mass of bisphenoxyethanol fluorene, wherein the mass percentages of the respective components are based on the total mass of the composition, and the first polyamide is polyamide-6, polyamide-6,6, or a combination thereof.

[0006] A method for producing this composition, the production method including a step of melt-mixing the components of the composition.

[0007] Another aspect disclosed in the present application is an article made from this composition.

[0008] Examples of the above and other features will be described in the following detailed description.

Mode for Carrying Out the Invention

[0009] The inventor of the present invention has, advantageously, discovered a composition that is considered to be particularly suitable, for example, as a matrix resin used in carbon fiber reinforced thermoplastics for automobiles. The composition described in the present application can exhibit a favorable combination of high melt flow, low water absorption, high heat resistance, and good impact performance.

[0010] Accordingly, one aspect disclosed in the present application is a poly(phenylene ether) / polyamide composition. Specifically, this composition contains specific amounts of poly(phenylene ether), a first polyamide, a hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene, and bisphenoxyethanol fluorene.

[0011] This composition contains poly(phenylene ether) (also referred to as "PPE" in the text). The poly(phenylene ether) contains phenylene ether units represented by the following structural formula.

[0012] [Chemical formula] In the formula, Z 1 is, each occurrence independently, halogen, unsubstituted or substituted C 1~12 hydrocarbyl (provided that the hydrocarbyl group is not a tertiary hydrocarbyl), C 1~12 hydrocarbylthio, C 1~12 hydrocarbyloxy, or C 2~12 halohydrocarbyloxy (the halogen and oxygen atoms are separated by at least two carbon atoms), and Z 2 is, each occurrence independently, hydrogen, halogen, unsubstituted or substituted C 1~12 hydrocarbyl (provided that the hydrocarbyl group is not a tertiary hydrocarbyl), C 1~12 hydrocarbylthio, C 1~12 hydrocarbyloxy, or C 2~12 halohydrocarbyloxy (the halogen and oxygen atoms are separated by at least two carbon atoms). The poly(phenylene ether) can generally have a terminal group containing aminoalkyl at the ortho position with respect to the hydroxy group. As an example, Z 1 can be a di-n-butylaminomethyl group generated from the reaction of the di-n-butylamine component of the oxidative polymerization catalyst with the terminal 3,5-dimethyl-1,4-phenyl group. Further, what often exists is generally a tetramethyldiphenoquinone (TMDQ) terminal group obtained from a reaction mixture containing 2,6-dimethylphenol (in the presence of a tetramethyldiphenoquinone by-product). The poly(phenylene ether) can be in the form of a homopolymer, random copolymer, graft copolymer, or block copolymer, or further combinations thereof. In certain embodiments, the poly(phenylene ether) is a homopolymer, desirably poly(2,6-dimethyl-1,4-phenylene ether).

[0013] In one aspect, the poly(phenylene ether) has an intrinsic viscosity of from 0.2 to 1 deciliter / gram (dL / g) as measured at 25° C. in chloroform using an Ubbelohde viscometer. Within this range, the intrinsic viscosity of the poly(phenylene ether) can be from 0.2 to 0.6 dL / g, from 0.25 to 0.5 dL / g, from 0.3 to 0.5 dL / g, or from 0.35 to 0.5 dL / g.

[0014] In a specific aspect, the poly(phenylene ether) is poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of from 0.2 to 0.6 dL / g as measured at 25° C. in chloroform using an Ubbelohde viscometer. Within the range of from 0.2 to 0.6 dL / g, the intrinsic viscosity of the poly(2,6-dimethyl-1,4-phenylene ether) can be from 0.3 to 0.5 dL / g, more desirably from 0.35 to 0.5 dL / g.

[0015] The composition contains poly(phenylene ether) in an amount of from 10 to 65% by weight, based on the total weight of the composition. Within this range, the amount of PPE can be from 10 to 40% by weight, from 15 to 35% by weight, from 15 to 25% by weight, from 25 to 35% by weight, or from 20 to 40% by weight.

[0016] In addition to the poly(phenylene ether), the present composition includes a first polyamide. Polyamides (also known as nylons) are polymers containing amide (i.e., -C(=O)NH-) bonding groups, such as those described in U.S. Patent No. 4,970,272 by Gallucci. Polyamides that can be used as the first polyamide include polyamide-6, polyamide 6,6, or combinations thereof. Polyamide-6 and polyamide-6,6 are commercially available from many suppliers and their manufacturing methods are known. For example, polyamides can be obtained by many known methods, such as those described in U.S. Patent Nos. 2,071,250, 2,071,251, 2,130,523, and 2,130,948 by Carothers, U.S. Patent Nos. 2,241,322 and 2,312,966 by Hanford, and U.S. Patent No. 2,512,606 by Bolton et al.

[0017] The first polyamide can have a specific amine end group concentration. For example, the first polyamide can have an amine end group concentration of 40 to 115 milliequivalents / kg. In certain embodiments, the first polyamide can have an amine end group concentration of less than 75 milliequivalents / kg, such as 40 to 70 milliequivalents / kg. In certain embodiments, the first polyamide can have an amine end group concentration greater than 85 milliequivalents / kg, such as 90 to 115 milliequivalents / kg. The amine end group content can be determined by dissolving the polyamide in a suitable solvent and titrating with 0.01 N hydrochloric acid (HCl solution) using a suitable indicator method. The amount of amine end groups is calculated based on the amount of HCl solution added to the sample, the amount of HCl used in the blank, the molar concentration of the HCl solution, and the mass of the polyamide sample.

[0018] The amount of the first polyamide can be from 30 to 70% by mass based on the total mass of the composition. Within this range, the amount of the first polyamide can be from 60 to 70% by mass, from 50 to 65% by mass, from 50 to 60% by mass, from 40 to 55% by mass, from 30 to 50% by mass, or from 30 to 60% by mass. In certain embodiments, the first polyamide can be polyamide-6, and the amount of the first polyamide can be 50% by mass or less (i.e., from 30 to 50% by mass). In certain embodiments, the first polyamide can be polyamide-6,6, and the amount of the first polyamide can be 60% by mass or less (i.e., from 30 to 60% by mass).

[0019] In addition to the poly(phenylene ether) and the first polyamide, the composition includes a hydrogenated block copolymer of an alkenyl aromatic monomer and a conjugated diene. This component is referred to herein as the "hydrogenated block copolymer" for brevity. The hydrogenated block copolymer can include from 10 to 90% by mass of a poly(alkenyl aromatic compound) content and from 90 to 10% by mass of a hydrogenated poly(conjugated diene) content based on the mass of the hydrogenated block copolymer. In certain embodiments, the hydrogenated block copolymer is a hydrogenated block copolymer with a low poly(alkenyl aromatic compound) content, and its poly(alkenyl aromatic compound) content is less than 40% by mass, specifically from 20 to 35% by mass, more specifically from 25 to 35% by mass, and even more specifically from 25 to 30% by mass, based on the mass of the hydrogenated block copolymer with a low poly(alkenyl aromatic compound) content. In another embodiment, the hydrogenated block copolymer is a hydrogenated block copolymer with a high poly(alkenyl aromatic compound) content, and its poly(alkenyl aromatic compound) content is from 40 to 90% by mass, specifically from 50 to 80% by mass, and more specifically from 60 to 70% by mass, based on the mass of the hydrogenated block copolymer with a high poly(alkenyl aromatic compound) content.

[0020] In one embodiment, the mass average molecular weight of the hydrogenated block copolymer is from 40,000 to 400,000 grams per mole (g / mol or Daltons (Da)). The number average molecular weight and the mass average molecular weight can be determined by gel permeation chromatography by comparison with polystyrene standards. In one embodiment, the mass average molecular weight of the hydrogenated block copolymer is from 200,000 to 400,000 g / mol, specifically from 220,000 to 350,000 g / mol. In another embodiment, the mass average molecular weight of the hydrogenated block copolymer is from 40,000 to 200,000 g / mol, specifically from 40,000 to 180,000 g / mol, more specifically from 40,000 to 150,000 g / mol.

[0021] The alkenyl aromatic monomer used in the preparation of the hydrogenated block copolymer can have a structure represented by the following structural formula.

[0022]

Chemical formula

[0023] The conjugated diene used in the preparation of the hydrogenated block copolymer is C 4~20 It can 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, etc., and combinations thereof. In one embodiment, the conjugated diene is 1,3-butadiene, 2-methyl-1,3-butadiene, or a combination thereof. In one embodiment, the conjugated diene is 1,3-butadiene.

[0024] The hydrogenated block copolymer is a copolymer comprising (A) at least one block derived from an alkenyl aromatic compound and (B) at least one block derived from a conjugated diene, wherein the aliphatic unsaturation content in block (B) has been at least partially reduced by hydrogenation. In certain embodiments, the aliphatic unsaturation in block (B) is reduced by at least 50%, specifically by at least 70%. The sequences of blocks (A) and (B) include linear structures, graft structures, and branched or unbranched radial teleblock structures. Linear block copolymers include tapered linear structures and non-tapered linear structures. In certain embodiments, the hydrogenated block copolymer has a tapered linear structure. In certain embodiments, the hydrogenated block copolymer has a non-tapered linear structure. In certain embodiments, the hydrogenated block copolymer comprises a (B) block in which the alkenyl aromatic monomer is randomly incorporated. 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, and further include linear structures containing six or more blocks of (A) and (B) combined, wherein the molecular weight of each (A) block may be the same as or different from that of other (A) blocks, and the molecular weight of each (B) block may be the same as or different from that of other (B) blocks. In certain embodiments, the hydrogenated block copolymer is a diblock copolymer, a triblock copolymer, or a combination thereof.

[0025] In certain embodiments, the hydrogenated block copolymer does not contain residues of monomers other than alkenyl aromatic compounds and conjugated dienes. In certain embodiments, the hydrogenated block copolymer consists of blocks derived from alkenyl aromatic compounds and conjugated dienes. This does not include grafts formed from these or other monomers. Also, since it consists of carbon and hydrogen atoms, it does not contain heteroatoms. In certain embodiments, the hydrogenated block copolymer contains residues of one or more acid-functionalizing reagents such as maleic anhydride. In certain embodiments, the hydrogenated block copolymer includes a polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer.

[0026] In certain embodiments, the hydrogenated block copolymer is a polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer having a polystyrene content of 25 to 35% by weight based on the weight of the polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer. In such embodiments, the polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer can have a weight-average molecular weight of 240,000 to 300,000 g / mol as measured by size-exclusion chromatography using a polystyrene standard, if desired.

[0027] In certain embodiments, the hydrogenated block copolymer is a polystyrene-poly(ethylene-propylene) diblock copolymer. In certain embodiments, the hydrogenated block copolymer can include a polystyrene-poly(ethylene-propylene) diblock copolymer, a polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer, or a combination thereof. In a specific embodiment, the composition includes a combination of a polystyrene-poly(ethylene-propylene) diblock copolymer and a polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer. When the polystyrene-poly(ethylene-propylene) diblock copolymer is present, its styrene content can desirably be 30 to 45% by weight.

[0028] Methods for producing hydrogenated block copolymers are known in the art, and many hydrogenated block copolymers are commercially available. Representative commercially available hydrogenated block copolymers include polystyrene-poly(ethylene-propylene) diblock copolymers available from Kraton Performance Polymers Inc. as KRATON™ G1701 (containing about 37% by weight of polystyrene) and G1702 (containing about 28% by weight of polystyrene); polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymers available from Kraton Performance Polymers Inc. as KRATON™ G1641 (containing about 33% by weight of polystyrene), G1650 (containing about 30% by weight of polystyrene), G1651 (containing about 33% by weight of polystyrene), and G1654 (containing about 31% by weight of polystyrene); and polystyrene-poly(ethylene-ethylene / propylene)-polystyrene triblock copolymers available from Kuraray Co., Ltd. as SEPTON™ S4044, S4055, S4077, and S4099.Examples of other commercially available hydrogenated block copolymers include CALPRENE™ H6140 (containing about 31% by mass of polystyrene), H6170 (containing about 33% by mass of polystyrene), H6171 (containing about 33% by mass of polystyrene), and H6174 (containing about 33% by mass of polystyrene) from Dynasol; SEPTON™ 8006 (containing about 33% by mass of polystyrene) and 8007 (containing about 30% by mass of polystyrene) from Kuraray Co., Ltd.; polystyrene - poly(ethylene - butylene) - polystyrene (SEBS) triblock copolymers; SEPTON™ 2006 (containing about 35% by mass of polystyrene) and 2007 (containing about 30% by mass of polystyrene) from Kuraray Co., Ltd.; polystyrene - poly(ethylene - propylene) - polystyrene (SEPS) copolymers; and oil - extended compounds of these hydrogenated block copolymers available as KRATON™ G4609 (containing about 45% mineral oil and SEBS (containing about 33% by mass of polystyrene)) and G4610 (containing about 31% mineral oil and SEBS (containing about 33% by mass of polystyrene)) from Kraton Performance Polymers Inc., and TUFTEC™ H1272 (containing about 36% oil and SEBS (containing about 35% by mass of polystyrene)) from Asahi Kasei Corporation. Mixtures of two or more hydrogenated block copolymers can also be used.

[0029] In certain embodiments, the mass - average molecular weight of the hydrogenated block copolymer is from 40,000 to 400,000 g / mol. The number - average molecular weight and the mass - average molecular weight can be determined by gel permeation chromatography by comparison with polystyrene standards. In certain embodiments, the mass - average molecular weight of the hydrogenated block copolymer is from 200,000 to 400,000 g / mol or from 220,000 to 350,000 g / mol. In certain embodiments, the mass - average molecular weight of the hydrogenated block copolymer is from 40,000 to 200,000 g / mol, from 40,000 to 180,000 g / mol, or from 40,000 to 150,000 g / mol.

[0030] The amount of the hydrogenated block copolymer can be 1 to 10% by mass based on the total mass of the composition. Within this range, the amount of the hydrogenated block copolymer can be 1 to 8% by mass or 1 to 5% by mass.

[0031] In addition to the poly(phenylene ether), the first polyamide, and the hydrogenated block copolymer, the present composition further contains bisphenoxyethanol fluorene.

[0032] The content of bisphenoxyethanol fluorene in the present composition can be 0.5 to 10% by mass based on the total mass of the composition. Within this range, the amount of bisphenoxyethanol fluorene can be 0.5 to 7% by mass, 0.5 to 6% by mass, 0.5 to 5% by mass, or 1 to 5% by mass.

[0033] In certain embodiments, the present composition can further contain stearyl erucamide, if desired. When stearyl erucamide is present, its content in the composition can be 1 to 10% by mass based on the total mass of the composition. Within this range, the amount of stearyl erucamide can be 1 to 8% by mass, 1 to 7% by mass, 1 to 6% by mass, or 1 to 5% by mass.

[0034] In one aspect, the composition can further include a polystyrene homopolymer, if desired. As used herein, the term "polystyrene homopolymer" or "homopolystyrene" refers to a homopolymer of styrene. That is, residues of monomers other than styrene are not included in the homopolystyrene. The homopolystyrene can be atactic, syndiotactic, or isotactic. In one aspect, the homopolystyrene consists of atactic homopolystyrene. In one aspect, the homopolystyrene has a melt flow rate of from 1.5 to 10 g / 10 min, from 3 to 10 g / 10 min, or from 4 to 10 g / 10 min as measured at 200 °C and 5 kg load according to ASTM D1238 or ISO 1133. When the polystyrene homopolymer is present, its content in the composition can be from 1 to 30% by weight based on the total weight of the composition. Within this range, the amount of the polystyrene homopolymer can be from 5 to 30% by weight, from 5 to 25% by weight, from 5 to 20% by weight, or from 1 to 20% by weight.

[0035] The relative amounts of the components can be adjusted to obtain a desired combination of properties. As will be understood by those skilled in the art, the amounts of the components can be selected within the presented ranges such that the total is 100% by weight.

[0036] The composition can further include, if necessary, additional compositions, which include one or more additives selected to obtain desirable properties, and these additives are also selected so as not to unduly affect the desirable properties of the composition. The additional composition or individual additives can be incorporated at an appropriate time when mixing the components to produce the composition. Examples of additional compositions include flow modifiers, fillers (e.g., particulate polytetrafluoroethylene (PTFE), glass, carbon, minerals, or metals), antioxidants, heat stabilizers, light stabilizers, ultraviolet (UV) light stabilizers, UV absorbers, plasticizers, lubricants, release agents (such as mold release agents), antistatic agents, anti-fog agents, antibacterial agents, colorants (e.g., dyes or pigments), surface effect additives, radiation stabilizers, flame retardants, anti-drip agents (e.g., encapsulated polytetrafluoroethylene (PTFE) in styrene-acrylonitrile copolymer (TSAN)), or combinations thereof. Additives are used in amounts generally known to be effective. For example, the total amount of the additional composition (other than impact modifiers, fillers, or reinforcing agents) can be from 0.001 to 10 wt%, from 0.1 to 10 wt%, or from 0.01 to 5 wt% based on the total mass of the polymer in the composition. In certain embodiments, the composition can be made to exclude additives other than those specifically disclosed herein.

[0037] In certain embodiments, the composition can further include a pentaerythritol tetrastearate flow promoter. When pentaerythritol tetrastearate is present, its amount can be from 0.1 to 5 wt%. Within this range, the amount of pentaerythritol tetrastearate can be from 0.1 to 3 wt%, from 0.1 to 2 wt%, or from 0.1 to 1 wt%.

[0038] In a specific embodiment, the composition can include 20 to 40% by mass of poly(phenylene ether), 50 to 65% by mass of polyamide, and 1 to 10% by mass of a hydrogenated block copolymer. Specifically, the hydrogenated block copolymer can include a combination of a polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer and a polystyrene-poly(ethylene-propylene) diblock copolymer. In one embodiment, the poly(phenylene ether) can be poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.3 to 0.5 dL / g as measured at 25 °C in chloroform using an Ubbelohde viscometer.

[0039] In a specific embodiment, the composition includes 25 to 35% by mass of poly(phenylene ether), 50 to 60% by mass of polyamide, 1 to 10% by mass of a hydrogenated block copolymer, and 0.5 to 10% by mass of bisphenoxyethanol fluorene. In one embodiment, the hydrogenated block copolymer can include a combination of a polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer and a polystyrene-poly(ethylene-propylene) diblock copolymer. In one embodiment, the poly(phenylene ether) can be poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.3 to 0.5 dL / g as measured at 25 °C in chloroform using an Ubbelohde viscometer.

[0040] In a specific embodiment, the composition comprises 10 to 40% by mass of poly(phenylene ether), 40 to 55% by mass of polyamide, 1 to 10% by mass of a hydrogenated block copolymer, 1 to 5% by mass of stearyl erucamide, and 0.5 to 5% by mass of bisphenoxyethanol fluorene. In one embodiment, the hydrogenated block copolymer can include a polystyrene-poly(ethylene-propylene) diblock copolymer. In one embodiment, the poly(phenylene ether) can be poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.3 to 0.5 dL / g as measured at 25 °C in chloroform using an Ubbelohde viscometer.

[0041] In a specific embodiment, the composition comprises 15 to 25% by mass of poly(phenylene ether), 45 to 55% by mass of a first polyamide, 1 to 10% by mass of a hydrogenated block copolymer, 10 to 20% by mass of a polystyrene homopolymer, and 0.5 to 10% by mass of bisphenoxyethanol fluorene. In one embodiment, the hydrogenated block copolymer can include a combination of a polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer and a polystyrene-poly(ethylene-propylene) diblock copolymer. In one embodiment, the poly(phenylene ether) can be poly(2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.3 to 0.5 dL / g as measured at 25 °C in chloroform using an Ubbelohde viscometer.

[0042] The composition disclosed in the present application can exhibit one or more advantageous properties. For example, the composition has a 2 (kJ / m 2 ) greater than 5 kilojoules per meter 2 greater than 10 kJ / m 2It can have a notched Charpy impact strength greater than. This composition can have a water absorption rate of less than 1%, less than 0.9%, less than 0.8%, less than 0.75%, less than 0.7%, less than 0.6%, less than 0.5%, less than 0.5%, from 0.01 to 0.75%, or from 0.05 to 0.5%. This composition is 10 cm 3 / 10 minutes greater than, 12 cm 3 / 10 minutes greater than, or 15 cm 3 / 10 minutes greater melt volume flow rate. The aforementioned properties can be determined according to test criteria described in more detail in, for example, later examples.

[0043] This composition can contain 10 to 65% by mass of poly(phenylene ether), 30 to 70% by mass of a first polyamide, 1 to 10% by mass of a hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene, and 0.5 to 10% by mass of bisphenoxyethanol fluorene. The mass percentages of the respective components are based on the total mass of the composition. The first polyamide is polyamide-6, polyamide-6,6, or a combination thereof. The first polyamide can be polyamide-6, and its abundance can be 50% by mass or less. The first polyamide can be polyamide-6,6, and its abundance can be 60% by mass or less. The first polyamide can have an amine end group concentration of less than 75 meq / kg, desirably from 40 to 70 meq / kg, or an amine end group concentration greater than 85 meq / kg, desirably from 90 to 115 meq / kg. The hydrogenated block copolymer can be a polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer, a polystyrene-poly(ethylene-propylene) diblock copolymer, or a combination thereof. Desirably, the polystyrene-poly(ethylene-propylene) diblock copolymer can have a styrene content of 30 to 45% by mass. This composition can contain 0.1 to 10% by mass of one or more additives.

[0044] The present composition can generally be prepared by any method. In one embodiment, the present composition can be prepared by melt-mixing the components of the composition. For example, the present composition can be produced by combining the components of the composition. In one embodiment, the components of the composition can be dry-mixed and the dry mixture can be added from an inlet upstream of an extruder. Next, the dry mixture can be melt-mixed. In one embodiment, the polyamide and the filler (if present) can be added to the melt mixture using separate downstream supply devices. A typical melt-mixing temperature can be from 250 to 315 °C. From this composition, molded articles can be molded, for example, by injection molding or extrusion. Examples of the production method of the composition will be further described in the later examples.

[0045] The present composition is considered useful for various applications, particularly automotive applications. That is, another aspect disclosed in the present application is an article made from the various compositions described above. Such articles include components used inside vehicles such as automobiles, airplanes, ships, trains, subway cars, etc. Specific articles are automotive parts.

[0046] The composition disclosed in the present application is considered to be useful also as a constituent of a reinforced thermoplastic composite material, particularly a thermoplastic composite material reinforced with carbon fibers. Accordingly, the reinforced thermoplastic composite material can include the aforementioned composition and a reinforcing filler. Examples of the reinforcing filler include mica, clay, feldspar, quartz, silica, perlite, tripoli, diatomaceous earth, aluminum silicate (mullite), synthetic calcium silicate, fused silica, fumed silica, sand, boron nitride powder, boron-silicate powder, calcium sulfate, calcium carbonate (such as chalk, limestone, marble, synthetic precipitated calcium carbonate, etc.), talc (fibrous, modular, acicular, lamellar talc, etc.), wollastonite, hollow or solid glass spheres, silicate spheres, cenospheres, aluminosilicates, or (armospheres), kaolin, whiskers of silicon carbide, alumina, boron carbide, iron, nickel, or copper, continuous or ground carbon fibers or glass fibers, molybdenum disulfide, zinc sulfide, barium titanate, barium ferrite, barium sulfate, barite, TiO 2 2, aluminum oxide, magnesium oxide, granular or fibrous aluminum, bronze, zinc, copper, or nickel, glass flakes, flaky silicon carbide, flaky aluminum diboride, flaky aluminum, steel flakes, natural fillers (such as wood powder, fibrous cellulose, cotton, sisal hemp, jute, starch, lignin, ground nut shells, or rice husks, etc.), reinforcing organic fiber fillers (such as poly(ether ketone), polyimide, polybenzoxazole, poly(phenylene sulfide), polyester, polyethylene, aromatic polyamide, aromatic polyimide, polyetherimide, polytetrafluoroethylene, and poly(vinyl alcohol), etc.), and combinations thereof. The filler and the reinforcing agent may be coated with a metal material layer to enhance conductivity, or may be surface-treated with silanes to improve adhesion and dispersibility with the polymer matrix. In one aspect, the reinforcing filler is carbon fiber for reinforcement.

[0047] The reinforced thermoplastic composite can contain 20 to 80% by mass of this composition based on the total mass of the composite. Within this range, the amount of this composition can be at least 30% by mass, at least 40% by mass, at least 50% by mass, or at least 60% by mass. Also within this range, the amount of this composition can be at most 60% by mass, at most 50% by mass, at most 40% by mass, or at most 30% by mass. The reinforced thermoplastic composite can contain 20 to 80% by mass of a reinforcing filler (for example, reinforcing carbon fiber). Within this range, the amount of the reinforcing filler can be at least 30% by mass, at least 40% by mass, at least 50% by mass, or at least 60% by mass. Also within this range, the amount of the reinforcing filler can be at most 60% by mass, at most 50% by mass, at most 40% by mass, or at most 30% by mass.

[0048] Due to these results, the composition disclosed in the present application becomes significantly beneficial in certain properties, such as melt flow, water absorption, and impact strength. This composition showing well-balanced properties is considered particularly useful in the manufacture of articles for various applications and also in the use of reinforced thermoplastic composites. Thus, great advantages are obtained from the disclosure of the present application.

Examples

[0049] The disclosure of the present application will be further described in more detail with the following examples, but it is not limited thereto.

[0050] The materials used in the following examples are shown in Table 1.

[0051]

Table 1

[0052] The compositions of the following examples were kneaded once through a TEM-37BS 30 mm twin-screw extruder manufactured by Toshiba Machine Co., Ltd. All components except polyamide (except when clearly indicated) were added from the feed port of the extruder, and polyamide was added from the downstream feeding device. The temperature settings of the extruder were 240 - 270 - 290 - 290 - 290 - 290 - 290 - 290 - 290 °C (from the upstream to the downstream of the zones), and the mold temperature was 300 °C. The screw rotation speed was 350 revolutions per minute (rpm). The extrudate was cooled in a water bath and pelletized. After conditioning the pellets at 110 °C for 2 - 4 hours, injection molding or extrusion molding was performed.

[0053] Before molding the pellets, pre-drying was performed at 110 °C for 2 - 4 hours. The samples were molded using an 85-ton Dorn injection molding machine with temperature settings of 260 - 260 - 260 - 260 °C (from the feed port towards the nozzle) and a mold temperature of 70 °C.

[0054] The physical properties were measured using the ASTM or ISO test methods shown in Table 2. Unless otherwise specified, the test standards described in the text are the most recent standards as of the filing date. The tests were performed at room temperature (23 °C) unless otherwise instructed. All samples were tested as molded unless otherwise indicated in the table described below.

[0055]

Table 2

[0056] Various compositions and their corresponding physical properties are shown in the following table. For each composition, the amount of each component is shown in parts by weight (pbw) relative to the total mass of the composition, and the total may not be 100.

[0057] As comparative examples, the theoretical saturated moisture absorption, melt volume flow rate (MVR), and notched Charpy impact strength of PPE / PA-1 and PPE / PA-2 in air at 23°C and 50% relative humidity were shown. The results are shown in Table 3. The "theoretical water absorption rate" used in the text is defined as the saturated water absorption rate of polyamide in air (23°C / 50% RH) × the loading amount of polyamide.

[0058]

Table 3

[0059] As shown in Table 3, PPE / PA-2 has a lower theoretical saturated moisture absorption and a lower MVR than PPE / PA-1. This is because the polyamide content of PPE / PA-2 is lower than that of PPE / PA-1. With these comparative examples in mind, the inventors of the present invention considered obtaining a new poly(phenylene ether) / polyamide matrix resin having balanced performance, that is, showing a low water absorption rate while achieving a high melt flow.

[0060] [Examples 1-1 to 1-3] The compositions and properties of Examples 1-1 to 1-3 are shown in Table 4.

[0061]

Table 4

[0062] As shown in Table 4, increasing only the amount of polyamide present in the composition resulted in a high melt flow, but the water absorption rate also increased, which was not preferable. From Table 4, it can be seen that when using PPE with a low intrinsic viscosity as in Example 1-1, for example, the MVR slightly increases compared to Example 1-3. The notched Charpy impact strength was the same in these three examples. Comparing Examples 1-2 and 1-3, it can be seen that when using a polyamide with high fluidity as in Example 1-2, a high MVR can be obtained, but the water absorption rate also increases. Furthermore, the 5% weight loss temperature determined by TGA was lower in each of Examples 1-1 and 1-2 compared to Example 1-3.

[0063] [Examples 2-1 to 2-6] The compositions and properties of Examples 2-1 to 2-6 are shown in Table 5. In these examples, the effects of different polyamide loadings on melt flow, impact performance, and water absorption are investigated.

[0064]

Table 5

[0065] As can be seen from Table 5, Examples 2-1 to 2-3 contain polyamide-6 with loadings of 50, 60, and 55 pbw, respectively. Examples 2-4 to 2-6 contain polyamide-6,6 with loadings of 55, 60, and 65 pbw, respectively. The examples shown in Table 5 indicate that a decrease in polyamide loading leads to a lower water absorption rate and a lower MVR. When the polyamide-6 loading was decreased from 60 to 50 pbw (i.e., from Example 2-2 to 2-1), a decrease in the notched Charpy impact strength was observed. On the other hand, even when the polyamide-6,6 loading was decreased (i.e., Examples 2-4 to 2-6), little effect on the notched Charpy impact strength was seen. These examples suggest that, generally, reducing the polyamide loading is beneficial for suppressing the water absorption rate.

[0066] [Examples 3-1 to 3-8] The compositions and properties of Examples 3-1 to 3-8 are shown in Table 6. In these examples, the effects of a specific flow promoter, bisphenoxyethanol fluorene (BPEF), on melt flow, impact performance, and water absorption are investigated.

[0067]

Table 6

[0068] As shown in Table 6, Examples 3-1 and 3-5 have the same formulation as Examples 2-3 and 2-4 in the previous Table 5, and this is used as a baseline comparison for examining the effect of this specific flow promoter. Examples 3-2 to 3-4 and Examples 3-6 to 3-8 each contain 1, 2.5, and 5 pbw of the flow promoter, respectively.

[0069] From the examples shown in Table 6, it can be seen that the BPEF flow promoter is effective as a flow promoter for poly(phenylene ether) / polyamide compositions. As the loading amount of BPEF increases, the MVR increases and the water absorption rate decreases. It was also found that when using BPEF, the Charpy impact strength and the 5% weight loss temperature by TGA slightly decrease.

[0070] [Examples 4-1 to 4-5] The compositions and properties of Examples 4-1 to 4-5 are shown in Table 7. The aim of this test was to examine the effects of various combinations of polystyrene (PS-1) with a high melt flow rate and BPEF, and stearyl erucamide and BPEF.

[0071]

Table 7

[0072] The examples in Table 7 each achieved a higher MVR than the PPE / PA-1 and PPE / PA-2 comparatives shown in Table 3. The 5% weight loss temperature of each composition was higher than 400 °C. Examples 7-2 and 7-5 showed particularly good heat resistance as indicated by the Vicat softening temperature, i.e., these compositions are considered useful in auto-structural applications that need to withstand the high temperatures to which they are exposed during processing. Generally, it has been shown that by keeping the polyamide loading low and adding a flow promoter, a good balance of low water absorption, high melt flow, and heat resistance can be obtained.

[0073] As is apparent from the examples presented in the text, the above poly(phenylene ether) / polyamide compositions can exhibit a well-balanced performance of low water absorption, high melt flow, high heat resistance, and good impact strength.

[0074] The disclosure of the present application further includes the following aspects.

[0075] Aspect 1: A composition comprising 10 to 65% by mass of poly(phenylene ether), 30 to 70% by mass of a first polyamide, 1 to 10% by mass of a hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene, and 0.5 to 10% by mass of bisphenoxyethanol fluorene, wherein the mass percentages of the respective components are based on the total mass of the composition, and the first polyamide is polyamide-6, polyamide-6,6, or a combination thereof.

[0076] Aspect 2: The composition of Aspect 1, wherein the first polyamide is polyamide-6 and the amount of the first polyamide is 50% by mass or less, or the first polyamide is polyamide-6,6 and the amount of the first polyamide is 60% by mass or less.

[0077] Aspect 3: A composition according to Aspect 1 or 2, wherein the first polyamide has an amine end group concentration of less than 75 meq / kg, desirably from 40 to 70 meq / kg, or an amine end group concentration of greater than 85 meq / kg, desirably from 90 to 115 meq / kg.

[0078] Aspect 4: A composition according to any one of Aspects 1 to 3, wherein the hydrogenated block copolymer is a polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer, a polystyrene-poly(ethylene-propylene) diblock copolymer, or a combination thereof, and desirably, the polystyrene-poly(ethylene-propylene) diblock copolymer has a styrene content of from 30 to 45% by mass.

[0079] Aspect 5: A composition according to any one of Aspects 1 to 4, wherein the composition has a notched Charpy impact strength greater than 5 kJ / m 2 , a water absorption rate of less than 1%, and a melt volume flow rate greater than 10 cm 3 / 10 min, and exhibits one or more of these properties.

[0080] Aspect 6: A composition according to any one of Aspects 1 to 5, wherein the composition further contains 1 to 10% by mass of stearyl erucamide or 1 to 30% by mass of polystyrene homopolymer.

[0081] Aspect 7: A composition according to any one of Aspects 1 to 6, wherein the composition contains 15 to 25% by mass of poly(phenylene ether), 45 to 55% by mass of the first polyamide, 1 to 10% by mass of a hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene, 10 to 20% by mass of polystyrene homopolymer, and 0.5 to 5% by mass of bisphenoxyethanol fluorene, and the hydrogenated block copolymer includes a combination of a polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer and a polystyrene-poly(ethylene-propylene) diblock copolymer.

[0082] Aspect 8: A composition according to any one of Aspects 1 to 6, the composition comprising 25 to 35% by mass of poly(phenylene ether), 50 to 60% by mass of a first polyamide, 1 to 10% by mass of a hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene, and 0.5 to 10% by mass of bisphenoxyethanol fluorene, wherein the hydrogenated block copolymer comprises a combination of a polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer and a polystyrene-poly(ethylene-propylene) diblock copolymer.

[0083] Aspect 9: A composition according to any one of Aspects 1 to 6, the composition comprising 10 to 40% by mass of poly(phenylene ether), 40 to 55% by mass of a first polyamide, 1 to 10% by mass of a hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene, 1 to 5% by mass of stearyl erucamide, and 0.5 to 5% by mass of bisphenoxyethanol fluorene, wherein the hydrogenated block copolymer comprises a polystyrene-poly(ethylene-propylene) diblock copolymer.

[0084] Aspect 10: A composition according to any one of Aspects 1 to 9, the composition further comprising 0.1 to 10% by mass of one or more additives.

[0085] Aspect 11: A method for producing a composition according to any one of Aspects 1 to 10, the production method comprising the step of melting and mixing the components of the composition.

[0086] Aspect 12: An article made from a composition according to any one of Aspects 1 to 10, preferably, the article is an automotive part.

[0087] Aspect 13: A reinforced thermoplastic composite, the reinforced thermoplastic composite comprising 20 to 80% by mass of a composition according to any one of Aspects 1 to 10 and 20 to 80% by mass of reinforcing carbon fibers, where the % by mass is based on the total mass of the composite.

[0088] The compositions, methods, and articles can selectively comprise, consist of, or consist essentially of any suitable materials, steps, or components disclosed herein. The compositions, methods, and articles can additionally or selectively be configured to exclude or substantially exclude any materials (or species), steps, or components that are not necessarily required for the achievement of the functions or purposes of the compositions, methods, and articles.

[0089] All ranges disclosed herein include their endpoints, and the endpoints are combinable independently of each other. “Combinations” include blends, mixtures, alloys, reaction products, etc. The terms “first,” “second,” etc. do not indicate any order, quantity, or importance, but are used to distinguish one element from another. The terms “a,” “an,” and “the” do not indicate a limitation of quantity and should be construed to include both the singular and plural forms unless otherwise indicated or clearly contradicted by the context. “Or” means “and / or” unless otherwise expressly stated. References to “some aspects,” “an aspect,” etc. in the specification mean that a particular element described in connection with that aspect is included in at least one aspect described herein, but may or may not be present in other aspects. The term “combination thereof” as used herein includes one or more of the recited elements, is open-ended, and may include one or more similar elements not recited. Further, it is understood that the recited elements may be combined in any suitable manner in various aspects.

[0090] Unless otherwise specified in the text, all test criteria are the most recent criteria that are valid as of the filing date of this application, or, if a priority is claimed, as of the filing date of the earliest priority application in which the test criteria are described.

[0091] Unless otherwise defined, technical and scientific terms used in the text have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. All patents, patent applications, and other references cited are hereby incorporated by reference in their entirety. However, if the terms in this application conflict with or are inconsistent with the terms in the incorporated references, the terms of this application shall prevail over the conflicting terms from the incorporated references.

[0092] Compounds are described using standard nomenclature. For example, a position not substituted with any indicated group is assumed to have its valence filled with the indicated bond or a hydrogen atom. A dash (“-”) not flanked by two letters or symbols is used to indicate the position at which a substituent is attached. For example, -CHO is attached at the carbon of the carbonyl group.

[0093] As used herein, the term "hydrocarbyl" refers to a residue containing only carbon and hydrogen, whether used alone or as part of a prefix, suffix, or other term. This residue can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It can also include combinations of aliphatic, aromatic, straight-chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon groups. However, when a hydrocarbyl residue is said to be substituted, it may contain heteroatoms in addition to the carbon and hydrogen atoms that make up the substituent residue, if necessary. That is, more specifically, when substituted, the hydrocarbyl residue can also include one or more carbonyl groups, amino groups, hydroxyl groups, etc., or may contain heteroatoms within the backbone of the hydrocarbyl residue. The term "alkyl" means 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, n- and s-hexyl. "Alkenyl" means a branched or straight-chain, monovalent hydrocarbon group containing at least one carbon-carbon double bond (e.g., ethenyl (-HC=CH 2 ))). "Alkoxy" means an alkyl group bonded through oxygen (i.e., alkyl-O-), such as methoxy, ethoxy, sec-butyloxy group. "Alkylene" means a branched or straight-chain, saturated divalent aliphatic hydrocarbon group (e.g., methylene (-CH 2 -), propylene (-(CH 2 ) 3 -)). "Cycloalkylene" means a divalent cyclic alkylene group -C n H 2n-x(wherein x means the number of hydrogens replaced by cyclization). "Cycloalkenyl" means a monovalent group containing one or more rings and one or more carbon-carbon double bonds in the ring, and all ring members are carbon (e.g., cyclopentyl, cyclohexyl). "Aryl" means an aromatic hydrocarbon group containing the specified number of carbon atoms (e.g., phenyl, tropone, indanyl, 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 of fluoro, chloro, bromo, or iodo substituents. Combinations of different halo groups (e.g., bromo and fluoro), or only chloro groups may be present. The prefix "hetero" means a compound or group containing at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatoms), where the heteroatoms are each independently N, O, S, Si, or P. "Substituted" means that the compound or group, subject to the condition that it does not exceed the normal valence of the atom being substituted, has at least one (e.g., 1, 2, 3, or 4) substituents in place of hydrogen, each independently C 1~9 alkoxy, C 1~9 haloalkoxy, nitro (-NO 2 ), cyano (-CN), C 1~6 alkylsulfonyl (-S(=O) 2 -alkyl), C 6~12 arylsulfonyl (-S(=O) 2 -aryl), thiol (-SH), thiocyanato (-SCN), tosyl (CH 3 C 6 H 4 SO 2 -), C 3~12 cycloalkyl, C 2~12 alkenyl, C 5~12 cycloalkenyl, C 6~12 aryl, C 7~13 arylalkylene, C 4~12 heterocycloalkyl, and C 3~12It means that it can be a heteroaryl) and is substituted. The number of carbon atoms indicated for a group does not include substituents. For example, -CH 2 CH 2 CN is a C substituted with nitrile 2 alkyl group.

[0094] Although specific embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are not currently anticipated or are considered unanticipated may be devised by the applicant or other persons skilled in the art. Accordingly, the appended claims, as filed and as amenable to amendment, are intended to cover all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. A composition, wherein the composition comprises 10 to 65% by mass of poly(phenylene ether), 30 to 70% by mass of a first polyamide, 1 to 10% by mass of a hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene, 0.5 to 10% by mass of bisphenoxyethanol fluorene, and the mass % of each of the above components is based on the total mass of the composition, the first polyamide is polyamide-6, polyamide-6,6, or a combination thereof, and the first polyamide has an amine end group concentration of 40 to 70 milliequivalents / kg, the composition further comprises 1 to 10% by mass of stearyl erucamide, or 1 to 30% by mass of a polystyrene homopolymer, and the composition shows a notched Charpy impact strength greater than 5 kJ / m2 as measured by ISO 179, a water absorption rate of less than 0.5% as measured by ISO 62, and a melt volume flow rate greater than 15 cm3 / 10 min as measured by ISO 1133 at 280 °C, a load of 2.16 kg, and a residence time of 300 seconds, characterized in that the composition exhibits each of the above properties.

2. The composition according to claim 1, wherein the first polyamide is polyamide-6 and the amount of the first polyamide is 50% by mass or less, or the first polyamide is polyamide-6,6 and the amount of the first polyamide is 60% by mass or less, characterized in that the composition has the above features.

3. The composition according to any one of claims 1 to 2, wherein the hydrogenated block copolymer is a polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer, a polystyrene-poly(ethylene-propylene) diblock copolymer, or a combination thereof.

4. The composition according to any one of claims 1 to 3, wherein the composition comprises 15 to 25% by mass of poly(phenylene ether), 45 to 55% by mass of the first polyamide, 1 to 10% by mass of a hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene, 10 to 20% by mass of the polystyrene homopolymer, 0.5 to 5% by mass of bisphenoxyethanol fluorene, and The composition is characterized in that the hydrogenated block copolymer comprises a combination of a polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer and a polystyrene-poly(ethylene-propylene) diblock copolymer.

5. The composition according to any one of claims 1 to 3, wherein the composition comprises 25 to 35% by mass of poly(phenylene ether), 50 to 60% by mass of the first polyamide, 1 to 10% by mass of a hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene, 0.5 to 10% by mass of bisphenoxyethanol fluorene, and the hydrogenated block copolymer comprises a combination of a polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer and a polystyrene-poly(ethylene-propylene) diblock copolymer.

6. The composition according to any one of claims 1 to 3, wherein the composition comprises 10 to 40% by mass of poly(phenylene ether), 40 to 55% by mass of the first polyamide, 1 to 10% by mass of a hydrogenated block copolymer of an alkenyl aromatic compound and a conjugated diene, 1 to 5% by mass of stearyl erucamide, 0.5 to 5% by mass of bisphenoxyethanol fluorene, and the hydrogenated block copolymer comprises a polystyrene-poly(ethylene-propylene) diblock copolymer.

7. The composition according to any one of claims 1 to 6, wherein the composition further comprises 0.1 to 10% by mass of one or more additives.

8. A method for producing the composition according to any one of claims 1 to 7, characterized in that the production method comprises a step of melt-mixing the components of the composition.

9. An article made from the composition according to any one of claims 1 to 7.

10. A reinforced thermoplastic composite material, wherein the reinforced thermoplastic composite material comprises 20 to 80% by mass of the composition according to any one of claims 1 to 7, 20 to 80% by mass of carbon fibers for reinforcement, and the % by mass is based on the total mass of the composite material.

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