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

Abstract

A thermoplastic composition comprising specific amounts of a poly (phenylene ether) having an intrinsic viscosity of greater than 0.5-1.45 dl / g and a homopolystyrene. The composition may advantageously provide improved fatigue performance. The composition is particularly suitable for use in water-contacting articles.

Description

[0001] Cross Reference to Related Applications

[0002] This application claims priority to and the benefit of European application 23172564.9, filed May 10, 2023, the entire contents of which are incorporated herein by reference. BACKGROUND

[0003] Articles for water management are often subjected to temperature and pressure fluctuations. They must also be able to withstand damage from exposure to load or stress fluctuation cycles associated with pressure surges from turning on a faucet (i.e., the so-called “water hammer effect”) and temperature changes associated with hot water flowing into a cold water fitting or cold water flowing into a hot water fitting. Historically, copper metal has been the most commonly used material for hot water pipes and fittings. In recent years, certain plastics, such as polysulfone, aromatic polyamide, and polyether sulfone, have also been used for water management applications, but these plastic materials are quite expensive relative to other plastics.

[0004] Thus, there is an ongoing need for materials that exhibit a range of properties desirable for use in various water-contacting articles. SUMMARY

[0006] A thermoplastic composition comprising 30 to 85 weight percent of a first poly(phenylene ether) having an intrinsic viscosity greater than 0.5 to 1.45 deciliters per gram (dl / g) as measured in chloroform at 25°C using an Ubbelohde visclometer; and optionally a second poly(phenylene ether) having an intrinsic viscosity of 0.3 to 0.5 dl / g as measured in chloroform at 25°C using an Ubbelohde visclometer, provided that the weighted average of the intrinsic viscosities of the first poly(phenylene ether) and the second poly(phenylene ether) is greater than 0.5; and 15 to 70 weight percent of a homopolymer of styrene; wherein the weight percent of each component is based on the total weight of the composition.

[0007] A method of making the thermoplastic composition comprising melt-mixing the components of the composition; and optionally, extruding the composition.

[0008] An article comprising the thermoplastic composition represents another aspect of the present disclosure.

[0009] The above described and other features are exemplified by the following figures and detailed description. BRIEF DESCRIPTION OF DRAWINGS

[0010] The following figures represent exemplary embodiments.

[0011] Figure 1is a plot of poly(phenylene ether) intrinsic viscosity versus cycles to failure. DETAILED DESCRIPTION

[0013] The present inventors have discovered that by including a combination of a poly(phenylene ether) having an intrinsic viscosity greater than 0.5 to 1.45 dl / g and a homopolymer of styrene in particular amounts, a desirable combination of hydrolytic stability, fatigue resistance, and melt-volume flow rate can be achieved. One advantage is that it was unexpectedly discovered that the desired properties can be achieved without a reinforcing filler or a rubber-modified impact modifier (which can provide a lower density material and is more easily processed). The present invention thus provides a significant improvement.

[0014] Accordingly, a thermoplastic composition represents one aspect of the present disclosure. The thermoplastic composition includes a first poly(phenylene ether). A poly(phenylene ether) herein includes repeating structural units represented by formula (1)

[0015]

[0016] wherein Z 1 independently at each occurrence is halogen, unsubstituted or substituted C 1-12 hydrocarbyl, provided that the hydrocarbyl is not a tertiary hydrocarbyl, C 1-12 hydrocarbylthio, C 1-12 hydrocarbyloxy, or C 2-12 halohydrocarbyloxy wherein there are at least two carbon atoms between the halogen atom and the oxygen atom; Z 2 independently at each occurrence is hydrogen, halogen, unsubstituted or substituted C 1-12 hydrocarbyl, provided that the hydrocarbyl is not a tertiary hydrocarbyl, C 1-12 hydrocarbylthio, C 1-12 hydrocarbyloxy, or C 2-12 halohydrocarbyloxy wherein there are at least two carbon atoms between the halogen atom and the oxygen atom. Herein, the term "hydrocarbyl," whether used by itself, or as part of a larger term such as "hydrocarbyloxy," or "hydrocarbylthio," refers to a residue that contains only carbon and hydrogen. The residue can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It can also contain a combination of aliphatic, aromatic, straight-chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbyl moieties. However, when the hydrocarbyl residue is described as substituted, it can optionally contain heteroatoms in addition to the carbon and hydrogen members of the residue. Thus, when specifically described as substituted, the hydrocarbyl residue can also contain one or more carbonyl, amino, hydroxyl, etc., or it can contain heteroatoms within the backbone of the hydrocarbyl residue. For example, Z 1may be di-n-butylaminomethyl formed by reaction of the terminal 3,5-dimethyl-1,4- phenyl group with the di-n-butylamine component of the oxidative polymerization catalyst.

[0017] In one aspect, the first poly(phenylene ether) comprises 2,6-dimethyl-1,4- phenylene ether repeat units, i.e., repeat units according to formula (2)

[0018]

[0019] 2,3,6-trimethyl-1,4-phenylene ether repeat units, or combinations thereof.

[0020] The first poly(phenylene ether) can comprise molecules having terminal groups comprising an aminoalkyl group, which are typically located in the ortho position to the hydroxyl group. In addition, tetramethyl diphenylquinone (TMDQ) end groups are also often present, typically obtained from reaction mixtures containing 2,6-dimethylphenol in which the tetramethyl diphenylquinone byproduct occurs. The poly(phenylene ether) can be a homopolymer, a copolymer, a graft copolymer, an ionomer, or a block copolymer, and combinations thereof.

[0021] The first poly(phenylene ether) can have an intrinsic viscosity greater than 0.5 to 1.45 dl / g as measured in chloroform at 25°C using an Ubbelohde viscometer. Within this range, the first poly(phenylene ether) can have an intrinsic viscosity of 0.55 to 1.45 dl / g, or 0.6 to 1.45 dl / g, or 0.65 to 1.45 dl / g.

[0022] The thermoplastic composition can optionally comprise a second poly(phenylene ether) having an intrinsic viscosity less than the intrinsic viscosity of the first poly(phenylene ether). For example, the composition can optionally comprise a second poly(phenylene ether) having an intrinsic viscosity of 0.3 to 0.5 dl / g as measured in chloroform at 25°C using an Ubbelohde viscometer.

[0023] When present, the second poly(phenylene ether) can be present in combination with the first poly(phenylene ether) in an amount effective to provide a weighted average of the intrinsic viscosity of the first poly(phenylene ether) and the second poly(phenylene ether) greater than 0.5 dl / g, preferably greater than 0.5 to 1.45 dl / g, or 0.55 to 1.45 dl / g, or 0.6 to 1.45 dl / g, or 0.65 to 1.45 dl / g. For example, when present, the second poly(phenylene ether) can be present such that the weight ratio of the first poly(phenylene ether) to the second poly(phenylene ether) is 0.9:1 to 10:1, or 0.9:1 to 2:1, or 0.9:1 to 1.1:1. In one aspect, the weight ratio of the first poly(phenylene ether) to the second poly(phenylene ether) can be 1:1. In one aspect, when the second poly(phenylene ether) is present, it can be present in the composition in an amount equal to or less than the amount of the first poly(phenylene ether). In one aspect, no poly(phenylene ether) other than the first poly(phenylene ether) is included in the composition.

[0024] The first and second poly(phenylene ether)s can be prepared by an oxidative polymerization process. In this process, the poly(phenylene ether) is the product obtained by oxidative polymerization of a monomer mixture comprising a monohydric phenol, which can be as described above.

[0025] The combined content of the first poly(phenylene ether) and the second poly(phenylene ether), if present, in the composition can be 30 to 85 weight percent, or 30 to 75 weight percent, of the total weight of the composition. Within this range, the combined content of the first poly(phenylene ether) and the second poly(phenylene ether), if present, can be 30 to 70 weight percent, or 30 to 65 weight percent, or 35 to 70 weight percent, or 35 to 65 weight percent, or 40 to 70 weight percent, each based on the total weight of the composition.

[0026] In one aspect, the composition comprises a first poly(phenylene ether) and no other poly(phenylene ether) is present in the composition. The content of the first poly(phenylene ether) can be 30 to 85 weight percent, or 30 to 75 weight percent, based on the total weight of the composition. Within this range, the content of the first poly(phenylene ether) can be 30 to 70 weight percent, or 30 to 65 weight percent, or 35 to 70 weight percent, or 35 to 65 weight percent, or 40 to 70 weight percent, each based on the total weight of the composition. In one aspect, the content of the first poly(phenylene ether) can be 40 to 65 weight percent, or 45 to 63 weight percent, or 45 to 60 weight percent, or 50 to 59 weight percent.

[0027] In one aspect, the composition comprises a first poly(phenylene ether) and a second poly(phenylene ether). The combined content of the first poly(phenylene ether) and the second poly(phenylene ether) can be 30 to 85 weight percent, or 30 to 75 weight percent, based on the total weight of the composition. Within this range, the combined content of the first poly(phenylene ether) and the second poly(phenylene ether) can be 30 to 70 weight percent, or 30 to 65 weight percent, or 35 to 70 weight percent, or 35 to 65 weight percent, or 40 to 70 weight percent, each based on the total weight of the composition. In one aspect, the combined content of the first poly(phenylene ether) and the second poly(phenylene ether) can be 40 to 65 weight percent, or 45 to 60 weight percent, or 50 to 59 weight percent. In one aspect, the combined content of the first poly(phenylene ether) and the second poly(phenylene ether), if present, can be 30 to 50 weight percent, or 30 to 45 weight percent, or 32 to 42 weight percent.

[0028] When the composition comprises a first poly(phenylene ether) and a second poly(phenylene ether), the first poly(phenylene ether) and the second poly(phenylene ether) can each independently be present in an amount of 10 to 65 weight percent, based on the total weight of the composition, provided that the total amount of the first poly(phenylene ether) and the second poly(phenylene ether) is 30 to 85 weight percent, and the weight ratio of the first poly(phenylene ether) to the second poly(phenylene ether) is effective to provide a weighted average of the inherent viscosities of the poly(phenylene ether) components greater than 0.5 dl / g.

[0029] In addition to the first poly(phenylene ether) and optional second poly(phenylene ether) (collectively referred to as "poly(phenylene ether) component"), the thermoplastic composition includes a homopolystyrene. As used herein, the term "homopolystyrene" refers to a homopolymer of styrene, which can also be referred to as crystalline polystyrene. Thus, no residues of any monomer other than styrene are included in the homopolystyrene. The homopolystyrene can be atactic, syndiotactic, or isotactic. In one aspect, the homopolystyrene is atactic. The homopolystyrene can have a melt volume flow rate of 1.5 to 35 grams per 10 minutes (g / 10 min), or 1.5 to 30 g / 10 min, or 1.5 to 20 g / 10 min, or 1.5 to 10 g / 10 min, or 1.5 to 5 g / 10 min, all measured according to ISO 1133 at 200 °C and 5 kilogram (kg) load. The homopolystyrene can have a weight average molecular weight of 50,000 to 450,000 grams per mole (g / mol), as determined using gel permeation chromatography. In one aspect, the homopolystyrene is crystalline polystyrene having a melt volume flow rate of 1.5 to 5 g / 10 min, as measured according to ISO 1133 at 200 °C and 5 kg load.

[0030] The homopolystyrene is included in the composition in an amount of 15 to 70 weight percent, based on the total weight of the composition. Within this range, the homopolystyrene can be included in an amount of 15 to 60 weight percent, or 15 to 50 weight percent, or 15 to 45 weight percent, or 20 to 45 weight percent, or 25 to 43 weight percent, each based on the total weight of the composition.

[0031] In addition to the first poly(phenylene ether), the optional second poly(phenylene ether), and the homopolystyrene, the thermoplastic composition can also include a hydrogenated block copolymer of a conjugated diene and an alkenyl aromatic. For simplicity, this component is referred to as a "hydrogenated block copolymer." The hydrogenated block copolymer can include 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 one aspect, the hydrogenated block copolymer is a low poly(alkenyl aromatic content) hydrogenated block copolymer, where the poly(alkenyl aromatic) content is 10 to less than 40 weight percent, or 20 to 35 weight percent, or 25 to 35 weight percent, or 30 to 35 weight percent, all based on the weight of the low poly(alkenyl aromatic) content hydrogenated block copolymer. In one aspect, the hydrogenated block copolymer is a high poly(alkenyl aromatic content) hydrogenated block copolymer, where the poly(alkenyl aromatic) content is 40 to 90 weight percent, or 50 to 80 weight percent, or 60 to 70 weight percent, all based on the weight of the high poly(alkenyl aromatic) content hydrogenated block copolymer.

[0032] In one aspect, the hydrogenated block copolymer has a weight average molecular weight of 40,000 to 400,000 g / mol. Number average and weight average molecular weights can be determined by gel permeation chromatography and based on comparison to polystyrene standards. In one aspect, the hydrogenated block copolymer has a weight average molecular weight of 200,000 to 400,000 g / mol, or 220,000 to 350,000 g / mol. In one aspect, 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.

[0033] The alkenyl aromatic monomer used to make the hydrogenated block copolymer can have the structure shown in Formula (6)

[0034]

[0035] wherein R 5 and R 6 each independently represent a hydrogen atom, a C 1-8 alkyl group, or a C 2-8 alkenyl group; R 7 and R 11 each independently represent a hydrogen atom, a C 1-8 alkyl group, a chlorine atom, or a bromine atom; R 8 , R 9 and R 10 each independently represent a hydrogen atom, a C 1-8 alkyl group, or a C 2-8 alkenyl group, or R8 and R 10 together with the central aromatic ring form a naphthyl group, or R 9 and R 10 together with the central aromatic ring form a naphthyl group. Specific examples of alkenyl aromatic monomers include, for example, styrene, chlorostyrene (e.g., p-chlorostyrene), methylstyrene (e.g., α-methyl-styrene and p-methylstyrene), and t-butylstyrene (e.g., 3-t-butylstyrene and 4-t-butylstyrene). In one aspect, the alkenyl aromatic monomer is styrene.

[0036] The conjugated diene used to make the hydrogenated block copolymer can be a C 4-20 conjugated diene. Suitable conjugated dienes include, for example, 1,3-butadiene, 2-methyl- 1,3-butadiene, 2-chloro-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3- hexadiene, and the like, and combinations thereof. In one aspect, the conjugated diene is 1,3- butadiene, 2-methyl-1,3-butadiene, or a combination thereof. In one aspect, the conjugated diene is 1,3-butadiene.

[0037] 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 content of aliphatic unsaturation in block (B) is at least partially reduced by hydrogenation. In one aspect, the aliphatic unsaturation in block (B) is reduced by at least 50%, or at least 70%. Arrangements of blocks (A) and (B) include linear structures, graft structures, and radial teleblock structures with or without branching. Linear block copolymers include tapered linear structures and non-tapered linear structures. In one aspect, the hydrogenated block copolymer has a tapered linear structure. In one aspect, the hydrogenated block copolymer has a non-tapered linear structure. In one aspect, the hydrogenated block copolymer comprises a (B) block comprising randomly incorporated alkenyl aromatic monomers. Linear block copolymer structures include di-block (A-B block), tri-block (A-B-A block or B-A-B block), tetra-block (A-B-A-B block), and penta-block (A-B-A-B-A block or B-A-B-A-B block) structures, and linear structures comprising a sum of (A) and (B) blocks of 6 or more, wherein the molecular weight of each (A) block can be the same or different from other (A) blocks, and the molecular weight of each (B) block can be the same or different from other (B) blocks. In one aspect, the hydrogenated block copolymer is a di-block copolymer, a tri-block copolymer, or a combination thereof.

[0038] In one aspect, the hydrogenated block copolymer contains no monomer residues other than alkenyl aromatic compounds and conjugated dienes. In another aspect, the hydrogenated block copolymer consists of blocks derived from alkenyl aromatic compounds and conjugated dienes. It does not contain grafts formed from these or any other monomers. It also consists of carbon and hydrogen atoms and therefore contains no heteroatoms. In one aspect, the hydrogenated block copolymer contains residues of one or more acid functionalizing agents (e.g., maleic anhydride). In one aspect, the hydrogenated block copolymer comprises a polystyrene-poly(ethylene-butene)-polystyrene triblock copolymer.

[0039] In one aspect, the hydrogenated block copolymer is a polystyrene-poly(ethylene-butene)-polystyrene triblock copolymer, and its polystyrene content is 10–50% by weight, or 20–40% by weight, or 20–35% by weight, or 25–35% by weight, based on the weight of the polystyrene-poly(ethylene-butene)-polystyrene triblock copolymer. In these aspects, the polystyrene-poly(ethylene-butene)-polystyrene triblock copolymer optionally has a weight-average molecular weight of 200,000–400,000 g / mol, or 250,000–350,000 g / mol, determined by size exclusion chromatography using polystyrene standards.

[0040] 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 the polystyrene-poly(ethylene-propylene) diblock copolymer KRATON, offered by Kraton Performance Polymers Inc. TM G1701 (containing 37% polystyrene by weight) and G1702 (containing 28% polystyrene by weight); polystyrene-poly(ethylene-butene)-polystyrene triblock copolymers supplied by Kraton Performance Polymers Inc. TM G1641 (containing 33% polystyrene by weight), G1650 (containing 30% polystyrene by weight), G1651 (containing 33% polystyrene by weight), and G1654 (containing 31% polystyrene by weight); and the polystyrene-poly(ethylene-ethylene / propylene)-polystyrene triblock copolymer SEPTON supplied by Kuraray. TM S4044, S4055, S4077, and S4099. Other commercially available hydrogenated block copolymers include CALPRENE, a polystyrene-poly(ethylene-butene)-polystyrene (SEBS) triblock copolymer supplied by Dynasol. TMH6140 (31 wt% polystyrene), H6170 (33 wt% polystyrene), H6171 (33 wt% polystyrene), and H6174 (33 wt% polystyrene); and polystyrene-poly(ethylene-butylene)- polystyrene (SEBS) triblock copolymers SEPTON provided by Kuraray TM 8006 (33 wt% polystyrene) and 8007 (30 wt% polystyrene); polystyrene-poly(ethylene- propylene)-polystyrene (SEPS) copolymers SEPTON provided by Kuraray TM 2006 (35 wt% polystyrene) and 2007 (30 wt% polystyrene); and oil-extended compounds of these hydrogenated block copolymers, KRATON from Kraton Performance Polymers TM G4609 (containing 45% mineral oil, and SEBS with 33 wt% polystyrene) and G4610 (containing 31% mineral oil, and SEBS with 33% polystyrene); TUFTEC from Asahi TM H1272 (containing 36% oil, and SEBS with 35 wt% polystyrene). Mixtures of two or more hydrogenated block copolymers can also be used. In one aspect, the hydrogenated block copolymer comprises a polystyrene-poly(ethylene-butylene)-polystyrene triblock copolymer having a weight average molecular weight of at least 100,000 g / mol, or from 200,000 to 400,000 g / mol.

[0041] The hydrogenated block copolymer, if present, can be present in the composition in an amount of from 1 to 15 wt%, based on the total weight of the thermoplastic composition. Within this range, the hydrogenated block copolymer can be present in an amount of from 1 to 10 wt%, or from 1 to 8 wt%, or from 1 to 6 wt%, or from 1 to 5 wt%, or from 2 to 4 wt%, each based on the total weight of the thermoplastic composition.

[0042] The thermoplastic composition can also optionally include an additive composition including one or more additives selected to achieve desired properties, provided that the selection of these additives does not significantly adversely affect the desired properties of the thermoplastic composition. The additive composition or individual additives can be mixed at an appropriate time during the mixing of the components to form the composition. The additive composition can include an impact modifier, a flow modifier, an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet (UV) light stabilizer, a UV absorbing additive, a plasticizer, a lubricant, a release agent (e.g., a mold release agent), an antistatic agent, an antimisting agent, an antimicrobial agent, a colorant (e.g., a dye or a pigment), a surface effect additive, a radiation stabilizer, a flame retardant, an anti-dripping agent (e.g., a polytetrafluoroethylene (PTFE) coated styrene-acrylonitrile copolymer (TSAN)), or a combination thereof. For example, a combination of a mold release agent and an antioxidant can be used. Generally, the amount of additive used is typically an amount known to be effective. For example, the total amount of the additive composition (in addition to any impact modifier, filler, or reinforcing agent) can be 1 to 10 percent by weight of the total weight of the composition.

[0043] The thermoplastic composition can also optionally include a reinforcing agent. Possible fillers or reinforcing agents include, for example, mica, clay, feldspar, quartz, quartzite, 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, and synthetic precipitated calcium carbonate), talc (including fibrous, modular, needle shaped, and lamellar talc), wollastonite, hollow or solid glass spheres, silicate spheres, cenospheres, aluminosilicate or armospheres, kaolin, whiskers (silicon carbide, alumina, boron carbide, iron, nickel, or copper), continuous and chopped carbon or glass fibers, molybdenum sulfide, zinc sulfide, barium titanate, barium ferrite, barium sulfate, heavy spar, Ti02, alumina, magnesia, particulate or fibrous aluminum, bronze, zinc, copper, or nickel, glass flakes, flaked silicon carbide, flaked aluminum diboride, flaked aluminum, steel flakes, natural fillers such as wood flour, fibrous cellulose, cotton, sisal, jute, starch, lignin, ground nut shells, or rice hulls, and mixtures thereof.reinforcing organic fiber fillers (e.g., poly(ether ketone), polyimide, polybenzoxazole, poly(phenylene sulfide), polyester, polyethylene, aromatic polyamide, aromatic polyimide, polyetherimide, polytetrafluoroethylene, and poly(vinyl alcohol)), and combinations thereof. Fillers and reinforcing agents can be coated with a layer of metallic material to promote electrical conductivity, or surface treated to improve adhesion and dispersion with the polymer matrix.

[0044] In an aspect, the reinforcing filler can be a reinforcing fiber. Exemplary reinforcing fibers can include glass fibers, carbon fibers, mineral fibers, or combinations thereof. In a particular aspect, the reinforcing filler can include glass fibers.

[0045] When present, the reinforcing agent can be present in an amount of 5 to 55 weight percent, based on the total weight of the thermoplastic composition. Within this range, the reinforcing agent can be present in an amount of 10 to 40 weight percent, or 20 to 40 weight percent, or 25 to 35 weight percent, each based on the total weight of the composition.

[0046] In an aspect, the thermoplastic composition can have minimal or no reinforcing agent added. For example, the composition can include 5 weight percent or less, 3 weight percent or less, or 1 weight percent or less of a reinforcing agent. In an aspect, the thermoplastic composition can exclude a reinforcing agent. In an aspect, the composition can include 5 weight percent or less, 3 weight percent or less, or 1 weight percent or less of glass fibers. In an aspect, the thermoplastic composition can exclude glass fibers.

[0047] The thermoplastic composition can optionally exclude or minimize (i.e., be present in an amount of 5 weight percent or less, or 1 weight percent or less, or 0.1 weight percent or less) any component not specifically recited herein. For example, the thermoplastic composition can minimize or exclude any thermoplastic polymer other than the first poly(phenylene ether), the second poly(phenylene ether), the homopolystyrene, and the hydrogenated block copolymer. In an aspect, the composition can include less than 15 weight percent of rubber-modified polystyrene, or less than 10 weight percent of rubber-modified polystyrene. For example, the composition can include less than 5 weight percent or less than 1 weight percent of rubber-modified polystyrene. In an aspect, rubber-modified polystyrene can be excluded from the composition.

[0048] In one aspect, the total amount of the first poly(phenylene ether), the homopolystyrene, and the second poly(phenylene ether), if present, can be at least 50 weight percent of the total weight of the composition. For example, the total amount of the first poly(phenylene ether), the homopolystyrene, and the second poly(phenylene ether), if present, can be at least 60 weight percent, or at least 70 weight percent, or at least 80 weight percent, or at least 90 weight percent of the total weight of the composition. In one aspect, when no reinforcing filler is present in the composition, the total amount of the first poly(phenylene ether), the homopolystyrene, and the second poly(phenylene ether), if present, can be at least 75 weight percent, or at least 80 weight percent, or at least 85 weight percent, or at least 90 weight percent. In one aspect where the composition includes a reinforcing filler, the total amount of the first poly(phenylene ether), the homopolystyrene, and the second poly(phenylene ether), if present, can be at least 50 weight percent, or at least 55 weight percent, or at least 60 weight percent.

[0049] In one aspect, the thermoplastic composition can include 45 to 63 weight percent of the first poly(phenylene ether); 25 to 43 weight percent of the polystyrene; 1 to 5 weight percent of the hydrogenated block copolymer of a conjugated diene and an alkenyl aromatic; and 1 to 5 weight percent of the additive composition.

[0050] In one aspect, the thermoplastic composition can include 45 to 63 weight percent of the first poly(phenylene ether); 25 to 43 weight percent of the polystyrene; 1 to 5 weight percent of the hydrogenated block copolymer of a conjugated diene and an alkenyl aromatic; and 1 to 5 weight percent of the additive composition.

[0051] In one aspect, the thermoplastic composition can include 45 to 63 weight percent of the first poly(phenylene ether); 25 to 43 weight percent of the polystyrene; 1 to 5 weight percent of the hydrogenated block copolymer of a conjugated diene and an alkenyl aromatic; and 1 to 5 weight percent of the additive composition.

[0052] In one aspect, the thermoplastic composition can include 45 to 63 weight percent of the first poly(phenylene ether); 25 to 43 weight percent of the polystyrene; 1 to 5 weight percent of the hydrogenated block copolymer of a conjugated diene and an alkenyl aromatic; and 1 to 5 weight percent of the additive composition.

[0053] It is understood that the total of the amounts of each component in the composition sums to 100 weight percent. One of skill in the art, guided by the teachings herein, knows how to select the components within the given ranges to achieve a total weight of 100 weight percent.

[0054] The thermoplastic compositions of the present disclosure can provide a desirable combination of properties. For example, the number of cycles to failure of a molded sample of the composition measured according to the modified ASTM D7791 method using ISO 527 Type 1 test specimens at a stress of 25 MPa and a frequency of 10 Hz can be improved by at least 50%. In one aspect, a molded sample of the composition can withstand at least 100,000 cycles before failing at a stress of 25 MPa and a frequency of 10 Hz according to the modified ASTM D7791 method using ISO 527 Type 1 test specimens.

[0055] The compositions herein can be made by, for example, melt blending the components of the composition. The components of the composition can be mixed or blended using common equipment (e.g., ribbon blenders, HENSCHEL TM mixers, BANBURY TM mixers, drum tumblers, etc.) and the blended composition can then be melt blended or melt-kneaded. The melt blending or melt-kneading can be performed using common equipment (e.g., single screw extruders, twin screw extruders, multi-screw extruders, blending kneaders, etc.). For example, the present compositions can be prepared by melt blending the components in a twin screw extruder at a temperature of 270 to 350 °C or 280 to 340 °C. The extrudate can be immediately quenched in a water bath and pelletized. The pellets thus produced can be 0.635 cm (one quarter inch) or shorter as desired. Such pellets can be used in subsequent molding, shaping, or forming.

[0056] Shaped, formed or molded articles comprising the composition represent another aspect herein. The composition can be molded into useful formed articles by a variety of methods such as injection molding, extrusion, rotational molding, blow molding and thermoforming. The composition is particularly suitable for use in the fabrication of articles that come into contact with water. Exemplary articles can include faucets, hydraulic retarders, impellers, and other articles that must exhibit dimensional stability and mechanical strength when exposed to hot water. Articles can be prepared from the composition using fabrication methods known in the art such as, single and multi-layer foam extrusion, single and multi-layer sheet extrusion, injection molding, blow molding, extrusion, film extrusion, profile extrusion, pultrusion, compression molding, thermoforming, pressure molding, hydraulic molding, vacuum molding, foam molding, and the like. Combinations of the above article fabrication methods can be used.

[0057] As described herein, the present inventors have unexpectedly discovered that compositions comprising certain levels of the components described herein can provide certain advantageous properties. In particular, improved fatigue resistance can be obtained. Thus, significant improvements are provided herein, particularly in connection with articles that come into contact with water.

[0058] The present application is further illustrated by the following non-limiting examples. Example

[0059] The materials used in the following examples are shown in Table 1.

[0060] Table 1

[0061]

[0062] Each composition was compounded using a Coperion ZSK 25 mm twin-screw extruder. All components were added from the first feed port of the extruder, with the exception of ccPS which was added through the second feed port, and glass fiber (if present) which was added downstream. The extrudate was cooled in a water bath and pelletized. The pellets were conditioned at 100 °C for 2 hours prior to injection molding or extrusion forming. The process parameters used are summarized in Table 2.

[0063] Table 2

[0064]

[0065]

[0066] The test pieces were injection molded on an Engel 110T injection molding machine with barrel temperatures of 260°C, 270°C, and 290°C (from the feed inlet to the nozzle). The mold temperature was 80°C.

[0067] The properties of the molded parts were tested according to the following standards. Fatigue testing was performed at a stress level of 25 MPa and a frequency of 10 Hz according to ASTM D7791 on ISO-527 Type 1 tensile test bars. The number of cycles before failure was reported. If no failure occurred, the test ended after 1,000,000 cycles. Melt volumetric flow rate (MVR) was tested according to ISO 1133 at a load of 10 kg, a holding time of 300 seconds, and a temperature of 300 °C.

[0068] A summary of the compositions and their properties is shown in Table 3. The content of each component is expressed as a percentage by weight of the total weight of the composition.

[0069] Table 3

[0070]

[0071] * indicates a comparison example.

[0072] Table 3 (continued)

[0073]

[0074]

[0075] * indicates a comparison example.

[0076] As shown in Table 3, compositions containing higher molecular weight PPE exhibited significantly improved failure times under different loads at 10 Hz. For example, ... Figure 1 As shown, Comparative Examples E1-E7 demonstrate that at 25 MPa and 10 Hz, a PPE intrinsic viscosity of at least 0.50 dl / g is required to achieve at least 100,000 cycles. Example E9, using a 50:50 (w / w) combination of PPE with an intrinsic viscosity of 0.4 dl / g and PPE with an intrinsic viscosity of 1.40 dl / g, shows improved flowability but still achieves at least 100,000 cycles before failure. Examples E10 and E11 demonstrate that the PPE content in the composition can affect fatigue performance. The compositions of these examples provide more cycles before failure than those of Examples E4 and E5, which is attributed to the increased PPE content. Example E12, with a lower PPE content than the composition of Example E6, has fewer cycles before failure than E6 but still reaches the 100,000-cycle threshold.

[0077] The compositions of the present invention maintain an ideal combination of physical properties. Therefore, the present invention significantly improves the fatigue resistance of thermoplastic compositions.

[0078] The present application also encompasses the following aspects.

[0079] Aspect 1 : A thermoplastic composition comprising: 30 to 85 weight percent of a first poly(phenylene ether) having an intrinsic viscosity greater than 0.5 to 1.45 dl / g as measured in chloroform at 25°C using an Ubbelohde viscometer, and optionally a second poly(phenylene ether) having an intrinsic viscosity of 0.3 to 0.5 dl / g as measured in chloroform at 25°C using an Ubbelohde viscometer, provided that the weighted average of the intrinsic viscosities of the first poly(phenylene ether) and the second poly(phenylene ether) is greater than 0.5; and 15 to 70 weight percent of a homopolymer of styrene; wherein the weight percent of each component is based on the total weight of the composition.

[0080] Aspect 2: The thermoplastic composition of aspect 1, further comprising 1 to 15 weight percent of a hydrogenated block copolymer of a conjugated diene and an alkenyl aromatic hydrocarbon.

[0081] Aspect 3: The thermoplastic composition of aspect 1 or 2, further comprising 1 to 10 weight percent of an additive package, preferably the additive package comprises a release agent, an antioxidant, or a combination thereof.

[0082] Aspect 4: The thermoplastic composition of any of aspects 1 to 3, wherein the thermoplastic composition comprises 5 to 55 weight percent of a reinforcing filler, preferably glass fibers, based on the total weight of the composition.

[0083] Aspect 5: The thermoplastic composition of any of aspects 1 to 4, wherein the first poly(phenylene ether) has an intrinsic viscosity of 0.65 to 1.45 dl / g.

[0084] Aspect 6: The thermoplastic composition of any of aspects 1 to 4, wherein the thermoplastic composition comprises a first poly(phenylene ether) having an intrinsic viscosity greater than 0.5 to 1.45 dl / g and a second poly(phenylene ether) having an intrinsic viscosity of 0.3 to 0.5 dl / g.

[0085] Aspect 7: The thermoplastic composition of aspect 6, wherein the weight ratio of the first poly(phenylene ether) to the second poly(phenylene ether) is 0.9: 1 to 10: 1, or 0.9: 1 to 2: 1, or 0.9: 1 to 1.1 : 1.

[0086] Aspect 8: The thermoplastic composition of any of aspects 1 to 7, wherein the composition comprises less than 15 weight percent of a rubber-modified polystyrene, preferably the composition comprises less than 1 weight percent of a rubber-modified polystyrene, more preferably the composition does not comprise a rubber-modified polystyrene.

[0087] Aspect 9: The thermoplastic composition of aspect 1, comprising: 45 to 63 weight percent of the first poly(phenylene ether); 35 to 45 weight percent of the polystyrene; 1 to 5 weight percent of the hydrogenated block copolymer of a conjugated diene and an alkenyl aromatic; and 0.1 to 5 weight percent of the additive composition.

[0088] Aspect 10: The thermoplastic composition of aspect 1, comprising: 45 to 63 weight percent of a combination of a first poly(phenylene ether) and a second poly(phenylene ether); 35 to 45 weight percent of the polystyrene; 1 to 5 weight percent of the hydrogenated block copolymer of a conjugated diene and an alkenyl aromatic; and 0.1 to 5 weight percent of the additive composition.

[0089] Aspect 11: The thermoplastic composition of any of aspects 1 to 10, wherein a molded sample of the composition has at least a 50% increase in cycles to failure according to ASTM D7791 at a 25 MPa pressure and a 10 Hz frequency compared to a comparative composition that does not include the first poly(phenylene ether).

[0090] Aspect 12: A method of making the thermoplastic composition of any of aspects 1 to 11, the method comprising: melt mixing the components of the composition; and optionally, extruding the composition.

[0091] Aspect 13: An article comprising the thermoplastic composition of any of aspects 1 to 11.

[0092] Aspect 14: The article of aspect 13, wherein the article is a water-contacting article.

[0093] Aspect 15: The article of aspect 14, wherein the article is a water pipe or fitting, a hydro-block component, a water meter housing, a faucet, an impeller, or a pump housing.

[0094] The compositions, methods, and articles can alternatively comprise, consist of, or consist essentially of, any appropriate materials, steps, or components herein disclosed. The compositions, methods, and articles can additionally, or alternatively, be formulated so as to be devoid of, or substantially free of any materials (or species) not necessary for the function or intended goal of the compositions, methods, and articles.

[0095] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with the as the same ranges disclosed. The terms "comprises," "comprising," "includes," "including," "has," "having" and the like are not intended to exclude many embodiments from the scope of the present application. The term "consisting of" is intended to mean excluding any element not specified. The term "consisting essentially of" is intended to mean excluding any element not specified except for an impurity that is present in the application of the disclosed amount of that impurity. The term "about" means ± 10% of the indicated value. The use of "adapted to" and "configured to" herein are merely intended to convey structural adaptations and configured features with respect to the overall system and / or software in accordance with at least one embodiment. Likewise, the use of "based on" is intended to convey structural connections with respect to the overall system and / or software in accordance with at least one embodiment. The terms "first," "second," "third," "fourth,” etc. are not intended to denote any order, quantity, or importance, but are used to distinguish one element from another. The terms "a" and "an" and "the" and similar reference use in the context of the specification are to be construed to cover both the singular and the plural, unless otherwise indicated or clearly contradicted by the context. The term "or" as used in the context of this specification is to be construed as "and / or" unless otherwise indicated or clearly contradicted by the context. The use of the term "aspect" in the context of this specification is to be construed as a specific element described in association with that aspect contained in at least one aspect described herein, and can or can not be present in other aspects. The term "combinations thereof as used herein includes one or more of the listed elements and is open, allowing for the presence of one or more additional similar elements not specifically mentioned. Also, it should be understood that described elements can be combined in any suitable manner in the various aspects.

[0096] Unless otherwise stated, all test standards are the most recent standard in effect at the filing date of this application (or, if priority is claimed, the filing date of the earliest priority application in which the test standard arose).

[0097] Unless defined otherwise, technical and scientific terms used herein have the same meaning as is commonly understood by one of ordinary skill in the art to which this application belongs. All cited patents, patent applications, and other references are incorporated by reference in their entirety. However, if a term in the present application contradicts or conflicts with a term in the incorporated reference, the term from the present application prevails. The citation of any patent, patent application, or other references herein is not an admission that the patented applications, published applications, patents, or other references are prior art to the present application.

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

[0099] The term "hydrocarbyl," as used herein, whether used by itself, or as a prefix, suffix, or fragment of another term, refers to a residue containing only carbon and hydrogen. The residue can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It can also contain combinations of aliphatic, aromatic, straight- chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbyl moieties. However, when the hydrocarbyl residue is described as substituted, it can optionally contain heteroatoms in addition to the carbon and hydrogen members of the residue of the substituent. Thus, when specifically described as substituted, the hydrocarbyl residue can also contain one or more carbonyl, amino, hydroxyl, etc., groups, or it can contain heteroatoms within the backbone of the hydrocarbyl residue. The term "alkyl" refers to a branched or straight-chain saturated aliphatic hydrocarbyl group, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, s-pentyl, n-hexyl, and s-hexyl. "Alkenyl" refers to a straight-chain or branched-chain monovalent hydrocarbon radical having at least one carbon-carbon double bond (e.g., ethenyl (-HC=CH2)). "Alkoxy" refers to an alkyl group linked through an oxygen atom (i.e., alkyl-O-), for example, methoxy, ethoxy, and s-butyloxy. "Alkylene" refers to a straight-chain or branched-chain saturated divalent aliphatic hydrocarbyl group (e.g., methylene (-CH2-) or propylene (-(CH2)3-)). "Cycloalkylene" refers to a divalent cyclic alkylene group, -C n H 2n-x wherein x represents the number of hydrogen atoms that are cyclized. "Cycloalkenyl" refers to a monovalent group having one or more rings and one or more carbon-carbon double bonds in the ring, wherein all ring members are carbon (e.g., cyclopentyl and cyclohexyl). "Aryl" refers to an aromatic hydrocarbyl group containing the specified number of carbon atoms, for example, phenyl, cycloheptatrienone, indanyl, or naphthyl. "Arylene" refers to a divalent aryl group. "Alkylarylene" refers to an arylene group substituted with an alkyl group. "Arylalkylene" refers to an alkylene group substituted with an aryl group (e.g., benzyl). The prefix "halo" denotes a group or compound containing one or more halogen substituents, for example, fluorine, chlorine, bromine, or iodine. There can be a combination of different halogen atoms (e.g., bromine and fluorine), or there can be only chlorine atoms. The prefix "hetero" indicates that the compound or group has at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatoms), wherein each of the heteroatoms is independently N, O, S, Si, or P. "Substituted" means that the compound or group is substituted with at least one (e.g., 1, 2, 3, or 4) substituents in place of a hydrogen on the atom designated as being substituted, each of which is independently C 1-9 alkoxy, C 1-9 haloalkoxy, nitro (-NO2), cyano (-CN), C 1-6 alkylsulfonyl (-S(=O)2-alkyl), C 6-12Arylsulfonyl (-S(=O)2-aryl), mercapto (-SH), thiocyano (-SCN), toluenesulfonyl (CH3C6H4SO2-), C 3-12 cycloalkyl, C 2-12 alkenyl, C 5-12 Cycloalkenyl, C 6-12 Aryl, C 7-13 Aryl alkyl, C 4-12 Heterocyclic alkyl groups and C 3-12 Heteroaryl. The number of carbon atoms shown in the group does not include any substituents. For example, -CH2CH2CN indicates a C2 alkyl group substituted with a nitrile.

[0100] While specific embodiments have been described, the applicant or those skilled in the art may conceive of alternatives, modifications, variations, improvements, and substantially equivalents that are not currently foreseeable or may not have been foreseen. Therefore, the appended claims (both filed and potentially amended) are intended to cover all such alternatives, modifications, variations, improvements, and substantially equivalents.

Claims

1. A thermoplastic composition comprising: 30–85% by weight of the first poly(phenylene ether), having an intrinsic viscosity greater than 0.5–1.45 dL / g as measured by an Ubbelohde viscometer in chloroform at 25°C, and Optionally, a second poly(phenylene ether) having an intrinsic viscosity of 0.3–0.5 dL / g as measured by an Ubbelohde viscometer in chloroform at 25°C. The prerequisite is that the weighted average intrinsic viscosity of the first poly(phenylene ether) and the second poly(phenylene ether) is greater than 0.5 dL / g; and 15–70% by weight of homopolymer styrene; The weight percentages of each component are based on the total weight of the composition.

2. The thermoplastic composition of claim 1, further comprising 1 to 15% by weight of a hydrogenated block copolymer of a conjugated diene and an alkenyl aromatic hydrocarbon based on the total weight of the composition.

3. The thermoplastic composition of claim 1 or 2 further comprises 1 to 10% by weight of an additive composition based on the total weight of the composition, preferably the additive composition comprising a loosening agent, an antioxidant, or a combination thereof.

4. The thermoplastic composition of any one of claims 1 to 3, wherein the thermoplastic composition comprises 5 to 55% by weight of reinforcing filler, preferably glass fiber, based on the total weight of the composition.

5. The thermoplastic composition of any one of claims 1 to 4, wherein the first poly(phenylene ether) has an intrinsic viscosity of 0.65 to 1.45 dL / g.

6. The thermoplastic composition of any one of claims 1 to 5, wherein the thermoplastic composition comprises a first poly(phenylene ether) with an intrinsic viscosity greater than 0.5 to 1.45 dL / g and a second poly(phenylene ether) with an intrinsic viscosity of 0.3 to 0.5 dL / g.

7. The thermoplastic composition of claim 6, wherein the first poly(phenylene ether) and the second poly(phenylene ether) are present in a weight ratio of 0.9:1 to 10:1, or 0.9:1 to 2:1, or 0.9:1 to 1.1:

1.

8. The thermoplastic composition of any one of claims 1 to 7, wherein the composition comprises less than 15% by weight of rubber-modified polystyrene based on the total weight of the composition, preferably the composition comprises less than 1% by weight of rubber-modified polystyrene, more preferably the composition does not contain rubber-modified polystyrene.

9. The thermoplastic composition of claim 1, comprising: 45–63% by weight of the first poly(phenylene ether); 35–45% by weight of polystyrene; 1–5% by weight of hydrogenated block copolymers of conjugated dienes and alkenyl aromatics; and 0.1 to 5% by weight of additive composition, The percentage by weight is based on the total weight of the composition.

10. The thermoplastic composition of claim 1, comprising: A combination of 45–63% by weight of the first poly(phenylene ether) and the second poly(phenylene ether); 35–45% by weight of polystyrene; 1–5% by weight of hydrogenated block copolymers of conjugated dienes and alkenyl aromatics; and 0.1 to 5% by weight of additive composition, The percentage by weight is based on the total weight of the composition.

11. The thermoplastic composition of any one of claims 1 to 10, wherein the molded sample of the composition exhibits at least 50% more cycles before failure than a comparative composition excluding the first poly(phenylene ether) as shown by ASTM D7791 at a pressure of 25 MPa and a frequency of 10 Hz.

12. A method for preparing the thermoplastic composition according to any one of claims 1 to 11, comprising: The components of the composition are melt-mixed; as well as Optionally, the composition is extruded.

13. An article comprising the thermoplastic composition according to any one of claims 1 to 11.

14. The article of claim 13, wherein the article is an article that comes into contact with water.

15. The article of claim 14, wherein the article is a water pipe or fitting, a water resistance assembly, a water meter housing, a faucet, an impeller or a pump housing.

Images