Polyphenylene ether composition with excellent combustibility and dielectric properties

Abstract

Disclosed herein is a composition comprising: from about 35% to about 85% by weight of a polyphenylene ether component; from about 1% to about 55% by weight of a polystyrene component; and from about 5% to about 25% by weight of a flame retardant comprising an aromatic phosphate ester comprising a compound # imgabs0 # according to the formula # imgabs0 # wherein R may be independently unsubstituted at each occurrence or substituted by a C1-C12 hydrocarbyl group and at least one R is unsubstituted; the average value of n is 1 or greater, and wherein the combined weight percentage value of all the components is not more than 100 wt%, based on the total weight of the composition. The composition exhibits at least a V1 flame retardant rating at 1.5 mm as measured according to UL 94 and a dissipation factor of less than 0.002 when tested using a split dielectric resonator and a network analyzer.

Description

Technical Field

[0001] The present disclosure relates to materials containing polyphenylene ether, and in particular, to polyphenylene ether materials having improved combustion characteristics. Background Art

[0002] Dielectric properties are often critical to the effectiveness of thermoplastics in certain applications, especially for telecommunications applications, such as 5G networks. Low dielectric constant Dk and low dissipation factor Df materials provide radio frequency (RF) efficiency and therefore provide the desired properties of specified thermoplastic materials for such applications. Flame retardancy is also increasingly important in electronic applications. Therefore, materials for these applications should exhibit good dielectric properties and flame retardancy. Traditional thermoplastic material solutions for telecommunications applications, such as polyimide (PI) and liquid crystal polymer (LCP), have good flame retardancy, but dielectric properties are less than ideal. Polyphenylene ether resin (PPE) with low dielectric constant (Dk is about 2.6) and low dissipation factor (Df is about 0.0009) at 1.9 GHz is generally a suitable dielectric material for antenna applications in electronic devices. However, PPE is difficult to process. In order to alleviate the problem of poor processability, polystyrene (PS) is usually added to improve fluidity, but at the cost of loss of flammability. There remains a need in the art for thermoplastic compositions that balance flame retardancy, flow, and dielectric properties. Summary of the invention

[0003] The above and other deficiencies in the art are addressed using a thermoplastic composition comprising the following components: about 35% to about 85% by weight of a polyphenylene ether component; about 1% to about 55% by weight of a polystyrene component; and about 5% to about 25% by weight of a flame retardant comprising an aromatic phosphate according to Formula I, wherein the combined weight percentage values ​​of all components do not exceed 100% by weight and all weight percentage values ​​are based on the total weight of the composition. The composition may exhibit at least a V1 flame retardant rating at 1.5 mm as measured according to UL 94 (2021), and a dissipation factor of less than 0.002 when tested using a post-splitting dielectric resonator and a network analyzer. The above-described and other features are exemplified by the following detailed description, examples, and claims. BRIEF DESCRIPTION OF THE DRAWINGS

[0004] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate several aspects and, together with the description, serve to explain the principles of the disclosure.

[0005] Figure 1 Table 1 is presented, which shows a list of raw materials used to prepare comparative formulations and formulations of the invention. DETAILED DESCRIPTION

[0006] The present disclosure may be more readily understood by reference to the following detailed description of the desired embodiments and the examples contained therein. In the following specification and in the claims that follow, reference will be made to a number of terms having the following meanings. In addition, articles prepared according to any of the methods described herein are also within the scope of the present disclosure. For example, articles that may be prepared using the materials and methods of the present disclosure include articles in the electrical field, such as computers, antennas, and lighting articles.

[0007] Low dielectric constant Dk and low dissipation factor Df materials provide radio frequency (RF) efficiency and therefore provide the desired properties of a specified thermoplastic material for such applications for telecommunication applications, such as 5G networks. In recent years, flame retardancy has become increasingly important in electronic applications, especially for personal items such as tablets, laptops, and mobile phones. Materials for these applications need to exhibit good dielectric properties and flame retardancy.

[0008] Traditionally, polyimide (PI) thermoplastics are used for antennas, but the Dk and Df values ​​are relatively high, and moisture absorption can lead to poor reliability. Liquid crystal polymer (LCP) is another conventional thermoplastic material option, characterized by relatively high Dk and Df. And, although the dielectric properties are not ideal, both PI and LCP show good flame retardancy. Polyphenylene ether resin (PPE) with low dielectric constant (Dk is about 2.6) and low dissipation factor (Df is about 0.0009) is generally a suitable dielectric material for antenna applications in electronic devices. However, PPE is difficult to process. In order to alleviate the problem of poor processability, polystyrene (PS) is usually added to improve fluidity, but at the cost of loss of flammability. Conventional flame retardants used with PPE usually increase Dk and Df values, thereby offsetting the reduction in signal loss usually achieved by using PPE. However, the composition of the present disclosure provides a composition based on PPE, which can achieve low Dk and Df values ​​while also maintaining excellent flame retardancy and fluidity.

[0009] U.S. Patent No. US 7,371,790 discloses a polyphenylene ether composition comprising styrene and a phosphate flame retardant. However, these compositions do not solve the dielectric properties and flow characteristics as described herein, and are characterized by a polyolefin resin component. Japanese Patent Publication No. JP 2004137491 discloses a composition combined with polyphenylene ether, polystyrene and epoxy resin. These compositions do not solve the flow characteristics and other physical properties (e.g., heat distortion temperature) as described herein. Japanese Patent Publication No. JP 2017110072 discloses a combination of a resin based on polyphenylene ether and an aromatic condensed phosphate compound to improve flame retardancy. However, these compositions require additional components, including zirconium and hafnium compounds. Japanese Patent Publication No. JP 2019073600 A discloses a combination of a mixed resin based on polyphenylene ether with a styrene resin and an organic phosphorus compound to provide heat resistance, dimensional stability and acid resistance, etc. However, these compositions require additional components, including aluminum and carbon black, which alter the dielectric properties (which increase Dk and Df).

[0010] Chinese Patent Publication No. CN 113004675 discloses a dielectric material for 5G applications, which comprises PPE and a suitable phosphate flame retardant additive. Chinese Patent Publication No. CN 112143207 discloses a low dielectric constant PPE material comprising a halogen-free flame retardant additive. U.S. Patent No. US 8,791,181 discloses a composition comprising a combination of polyphenylene ether, high impact polystyrene and aromatic phosphate esters. Japanese Patent Publication No. JP 2003082224 discloses a composition exhibiting V0 flame retardant properties and comprising polyphenylene ether, polystyrene and aromatic phosphate flame retardant additives. However, the disclosures of these publications and / or patents do not achieve specific improvements in the dielectric and thermal properties (i.e., dissipation factor and heat deformation temperature) exhibited in the compositions of the present invention. European Patent Publication No. EP 0509506 discloses specific flame retardant compounds which are suitable for use in a very wide range of thermoplastic and thermoset materials due to their flame retardant properties, but does not mention the effect of the flame retardant compounds on certain dielectric properties.

[0011] Before disclosing and describing the compounds, compositions, articles, systems, devices and / or methods of the present invention, it should be understood that, unless otherwise specified, it is not limited to a specific synthesis method, or unless otherwise specified, it is not limited to a specific reactant, because these synthesis methods or reactants can obviously vary. It should also be understood that the terms used herein are only for describing specific aspects and are not intended to be limiting. The present disclosure encompasses various combinations of elements of the present disclosure, such as combinations of elements from dependent claims attached to the same independent claim.

[0012] Furthermore, it should be understood that any method described herein is not intended to be construed as requiring that its steps be performed in a specific order unless otherwise expressly stated. Therefore, in the event that a method claim does not actually list the order in which its steps are to be followed or does not otherwise specifically state in the claims or description that the steps should be limited to a specific order, no order is intended to be inferred in any respect. This applies to any possible non-express basis for interpretation, including: logical issues regarding the arrangement of steps or operational flow; plain meaning derived from grammatical organization or punctuation; and the number or type of embodiments described in the specification.

[0013] Thermoplastic composition

[0014] Various aspects of the present disclosure relate to thermoplastic compositions comprising at least: polyphenylene ether (PPE) (also known as polyphenylene oxide (PPO)), a polystyrene component, and a flame retardant or additive comprising an aromatic phosphate. Other aspects of the present disclosure relate to thermoplastic compositions comprising a polyphenylene ether component; a poly(phenylene ether)-polysiloxane block copolymer comprising a poly(phenylene ether) block and a polysiloxane block comprising an average of 20 to 80 siloxane repeating units; a polystyrene component; and a flame retardant comprising an aromatic phosphate.

[0015] The disclosed compositions exhibit improved flowability, flame retardancy, and dielectric properties. In some aspects, these properties are further improved when the composition comprises the following components: a polyphenylene ether component; a poly(phenylene ether)-polysiloxane block copolymer comprising a poly(phenylene ether) block and a polysiloxane block comprising an average of 20 to 80 siloxane repeating units; a polystyrene component; and a flame retardant comprising an aromatic phosphate. In various aspects, the present disclosure provides compositions that can be used to manufacture electronic devices, including antennas. The flame retardancy and dielectric properties and mechanical / physical properties of these materials have been evaluated.

[0016] Polyphenylene oxide

[0017] In various aspects, the disclosed compositions may include polyarylene ethers, such as polyphenylene oxide ("polyoxylphenylene"; PPO) or polyphenylene ether (PPE). PPE may describe a polymer containing optionally substituted benzene rings attached to oxygen (O), and may be used interchangeably with polyoxylphenylene or poly(2,6-dimethyl-p-phenylene oxide). In addition, the disclosed compositions may include specific combinations of PPE resins that impart a balance of certain properties to the composition. The polyphenylene oxide may be present in the form of a polyphenylene oxide resin. In other aspects, the polyphenylene oxide may be present in the form of a polyphenylene oxide copolymer.

[0018] Some aspects of the composition include polyphenylene oxide or polyphenylene oxide copolymers greater than 20 wt % to about 85 wt %. In some respects, poly(arylene ether) components, such as polyphenylene oxide components or polyphenylene oxide, can be present in an amount of about 35 wt % to about 85 wt %, or about 60 wt % to about 85 wt %, or about 70 wt % to about 85 wt %, based on the gross weight of the composition. According to various examples, the polyphenylene oxide component can be present in an amount of about 38 wt % to about 85 wt %, or about 40 wt % to about 85 wt %, or about 45 wt % to about 85 wt %, or about 50 wt % to about 85 wt %, or about 55 wt % to about 85 wt %, or about 56 wt % to about 85 wt %, or about 56 wt % to about 80 wt %.

[0019] In other aspects, the composition may include a poly(arylene) ether derivative, i.e., a poly(arylene ether)-polysiloxane block copolymer, such as a poly(phenylene ether)-polysiloxane copolymer reaction product. According to various aspects, the poly(arylene ether)-polysiloxane block copolymer reaction product may include: a poly(arylene ether) homopolymer and a poly(arylene ether)-polysiloxane block copolymer, the poly(arylene ether)-polysiloxane block copolymer comprising a poly(arylene ether) block and a polysiloxane block comprising an average of about 20 to about 80 siloxane repeating units. The poly(arylene ether)-polysiloxane block copolymer reaction product may include about 1 to about 30 weight percent siloxane repeating units and about 70 to about 99 weight percent arylene ether repeating units.

[0020] The poly(arylene ether)-polysiloxane block copolymer reaction product can be formed according to a method comprising oxidative copolymerization of a monomer mixture comprising a monohydric phenol and a hydroxyaryl-terminated polysiloxane. An important component of the composition of the present invention is a poly(arylene ether)-polysiloxane block copolymer reaction product (or referred to herein as a "reaction product") comprising a poly(arylene ether)-polysiloxane block copolymer and a poly(arylene ether) homopolymer. The poly(arylene ether)-polysiloxane block copolymer reaction product can be synthesized by oxidative polymerization of a mixture of a monohydric phenol and a hydroxyaryl-terminated polysiloxane. The oxidative polymerization produces a poly(arylene ether)-polysiloxane block copolymer as a desired product and a poly(arylene ether) homopolymer as a by-product. It is difficult and unnecessary to separate the poly(arylene ether) homopolymer from the poly(arylene ether)-polysiloxane block copolymer. Thus, the poly(arylene ether)-polysiloxane block copolymer is incorporated into the composition of the present invention in the form of a "poly(arylene ether)-polysiloxane block reaction product" comprising a poly(arylene ether) and a poly(arylene ether)-polysiloxane block copolymer.

[0021] The poly(arylene ether)-polysiloxane block copolymer may comprise a poly(arylene ether) block and a polysiloxane block. The poly(arylene ether) block is a polymerized residue of a monohydric phenol. In some embodiments, the poly(arylene ether) block comprises an arylene ether repeating unit having the following structure:

[0022]

[0023] where for each repeating unit, each Z 1 are independently halogen, unsubstituted or substituted C1-C 12 Hydrocarbon, provided that the hydrocarbon is not a tertiary hydrocarbon, C1-C 12 Hydroxylthio, C1-C 12 Hydroxyl or C2-C 12 haloalkyloxy, wherein at least two carbon atoms separate the halogen and oxygen atoms; and each Z 2 are independently hydrogen, halogen, unsubstituted or substituted C1-C 12 Hydrocarbon, provided that the hydrocarbon is not a tertiary hydrocarbon, C1-C 12 Hydroxylthio, C1-C 12 Hydroxyl or C2-C 12 A halogenated hydroxyl group wherein at least two carbon atoms separate the halogen and oxygen atoms. In some aspects, the poly(arylene ether) block comprises 2,6-dimethyl-1,4-phenylene ether repeating units, i.e., repeating units having the following structure:

[0024]

[0025] 2,3,6-trimethyl-1,4-phenylene ether repeating units, or combinations thereof.

[0026] The polysiloxane block can be the residue of a hydroxyaryl-terminated polysiloxane. In some aspects, the polysiloxane block can comprise repeating units having the following structure:

[0027]

[0028] Where R 1 and R 2 is independently hydrogen, C1-C 12 Hydrocarbon or C1-C 12 A halogenated hydrocarbon group; and the polysiloxane block further comprises a terminal unit having the following structure:

[0029]

[0030] Where Y is hydrogen, C1-C 12 Hydrocarbon, C1-C 12 alkoxy or halogen, and wherein R3 and R 4 is independently hydrogen, C1-C 12 Hydrocarbon or C1-C 12 In some embodiments, the polysiloxane repeating unit comprises a dimethylsiloxane (-Si(CH3)2O-) unit. In some embodiments, the polysiloxane block has the following structure:

[0031]

[0032] Where n is 20 to 60.

[0033] The hydroxyaryl-terminated polysiloxane may contain at least one hydroxyaryl end group. In some aspects, the hydroxyaryl-terminated polysiloxane has a single hydroxyaryl end group, in which case a poly(arylene ether)-polysiloxane diblock copolymer is formed. In other aspects, the hydroxyaryl-terminated polysiloxane has two hydroxyaryl end groups, in which case a poly(arylene ether)-polysiloxane diblock copolymer and / or a poly(arylene ether)-polysiloxane-poly(arylene ether) triblock copolymer is formed. The hydroxyaryl-terminated polysiloxane may also have a branched structure that allows for the presence of three or more hydroxyaryl end groups and the formation of corresponding branched copolymers.

[0034] In some aspects, the hydroxyaryl-terminated polysiloxane comprises an average of about 20 to about 80 siloxane repeating units, specifically about 25 to about 70 siloxane repeating units, more specifically about 30 to about 60 siloxane repeating units, more specifically about 35 to about 50 siloxane repeating units, more specifically about 40 to about 50 siloxane repeating units. The number of siloxane repeating units in the polysiloxane block is substantially unaffected by the copolymerization and separation conditions, and is therefore equivalent to the number of siloxane repeating units in the hydroxyaryl-terminated polysiloxane starting material. When not otherwise known, the average number of siloxane repeating units per hydroxyaryl-terminated polysiloxane molecule can be determined by nuclear magnetic resonance (NMR) methods.

[0035] In many aspects, poly (arylene ether) -polysiloxane block copolymer reaction product has a weight average molecular weight of at least 30,000 atomic mass units (amu). For example, when using gel permeation chromatography, when measured with polystyrene standards, the reaction product can have a weight average molecular weight of 30,000 to about 150,000amu, 35,000 to about 120,000amu, 40,000 to about 90,000amu or about 45,000 to about 70,000amu. In addition, the number average molecular weight of poly (arylene ether) -polysiloxane block copolymer reaction product is about 10,000 to about 50,000amu, or 10,000 to about 30,000amu, or about 14,000 to about 24,000amu.

[0036] In some embodiments, the poly(arylene ether)-polysiloxane block copolymer reaction product has an intrinsic viscosity of at least 0.3 deciliter per gram, or about 0.3 to about 0.5 deciliter per gram, measured in chloroform at 25°C.

[0037] Certain separation procedures can ensure that the polysiloxane content of the reaction product consists essentially of poly(arylene ether)-polysiloxane block copolymer and poly(arylene ether) homopolymer. After termination of the copolymerization reaction, the poly(arylene ether)-polysiloxane block copolymer reaction product can be isolated from solution using methods known in the art for isolating poly(arylene ether) from solution.

[0038] In some embodiments, the poly(arylene ether)-polysiloxane block copolymer reaction product incorporates greater than 75 weight percent of the hydroxyaryl-terminated polysiloxane starting material into the poly(arylene ether)-polysiloxane block copolymer. Specifically, the amount of hydroxyaryl-terminated polysiloxane incorporated into the poly(arylene ether)-polysiloxane block copolymer can be at least 80 weight percent, more specifically at least 85 weight percent, more specifically at least 90 weight percent, more specifically at least 95 weight percent. Additional details regarding the preparation, characterization, and properties of the poly(arylene ether)-polysiloxane block copolymer reaction product can be found in U.S. Pat. No. 8,017,697 and co-pending U.S. Pat. No. 8,669,332 to Carillo et al.

[0039] The poly(arylene ether)-polysiloxane block copolymer reaction product can comprise from about 1 to about 30 weight percent siloxane repeating units and from about 70 to about 99 weight percent arylene ether repeating units, based on the total weight of the reaction product. It is understood that the siloxane repeating units are derived from the hydroxyaryl terminated polysiloxane and the arylene ether repeating units are derived from the monohydric phenol. In some embodiments, for example, when the poly(arylene ether)-polysiloxane block copolymer reaction product is purified by precipitation in isopropanol, the siloxane repeating units consist primarily of residues of the hydroxyaryl terminated polysiloxane that have been incorporated into the poly(arylene ether)-polysiloxane block copolymer.

[0040] In some aspects, the reaction product can include about 1 to about 8 weight percent siloxane repeating units and about 12 to about 99 weight percent arylene ether repeating units, based on the total weight of the reaction product. Within these ranges, the amount of siloxane repeating units can be 2 to 7 weight percent, specifically 3 to 6 weight percent, more specifically 4 to 5 weight percent; and the amount of arylene ether repeating units can be 93 to 98 weight percent, specifically 94 to 97 weight percent, more specifically 95 to 96 weight percent.

[0041] In some aspects, the poly(arylene ether)-polysiloxane block copolymer reaction product comprises about 8 to about 30 weight percent siloxane repeating units and about 70 to about 92 weight percent arylene ether repeating units, based on the total weight of the reaction product. Within these ranges, the amount of siloxane repeating units can be about 10 to about 27 weight percent, specifically about 12 to about 24 weight percent, more specifically about 14 to about 22 weight percent, even more specifically about 16 to about 20 weight percent; and the amount of arylene ether repeating units can be about 74 to about 90 weight percent, specifically about 76 to about 88 weight percent, more specifically about 78 to about 86 weight percent, more specifically about 80 to about 84 weight percent. In other aspects, the poly(arylene ether)-polysiloxane block copolymer reaction product comprises about 15 to about 25 weight percent siloxane repeating units and about 75 to 85 weight percent arylene ether repeating units. Within the range of 15 to about 25 weight percent siloxane repeating units, the weight percent of siloxane repeating units can be about 16 to about 24 weight percent, specifically about 17 to about 22 weight percent, more specifically about 18 to about 20 weight percent. Within the range of about 75 to 85 weight percent, the weight percent of arylene ether repeating units can be about 76 to about 84 weight percent, specifically about 78 to about 83 weight percent, more specifically about 80 to about 82 weight percent.

[0042] In some embodiments, the poly(arylene ether)-polysiloxane block copolymer reaction product comprises 15 to about 25 weight % siloxane repeating units and about 75 to 85 weight % arylene ether repeating units. Within the range of 15 to about 25 weight % siloxane repeating units, the weight % of siloxane repeating units can be about 16 to about 24 weight %, specifically about 17 to about 22 weight %, even more specifically about 18 to about 20 weight %. Within the range of about 75 to 85 weight %, the weight % of arylene ether repeating units can be about 76 to about 84 weight %, specifically about 78 to about 83 weight %, more specifically about 80 to about 82 weight %. These repeating unit amounts are particularly suitable for thermoplastic compositions after precipitation from isopropanol, which substantially removes free hydroxyaryl-terminated polysiloxanes.

[0043] In some embodiments, the composition comprises a poly(arylene ether)-polysiloxane block copolymer reaction product in an amount of 8 wt % to about 50 wt %, the composition comprises about 10 to about 30 wt %, or about 10 wt % to about 35 wt %, or about 15 wt % to about 40 wt %, or about 6 wt % to about 40 wt % of the poly(arylene ether)-polysiloxane block copolymer reaction product, based on the total weight of the composition. According to various examples, the polyphenylene ether component may comprise a PPE resin and a poly(arylene ether)-polysiloxane block copolymer (PPE-Si). The PPE resin and PPE-Si may be present in an amount of about 38 wt % to about 85 wt %, or about 40 wt % to about 85 wt %, or about 45 wt % to about 85 wt %, or about 50 wt % to about 85 wt %, or about 55 wt % to about 85 wt %, or about 56 wt % to about 85 wt %, or about 56 wt % to about 80 wt %.

[0044] Flame retardants

[0045] In various aspects, the disclosed compositions can include a flame retardant additive, in particular, a phosphate-based flame retardant additive. The flame retardant additive is a halogen-free or halogen-free phosphate flame retardant.

[0046] According to various aspects of the present disclosure, the flame retardant additive may include an aromatic phosphate according to Formula I.

[0047]

[0048] R at each occurrence can independently be unsubstituted or substituted C1-C 12 A hydrocarbon group, and at least one R is unsubstituted; n has an average value of 1 or greater, and R' at each occurrence can be selected from

[0049] In another aspect, the flame retardant can comprise an aromatic phosphate according to Formula II.

[0050]

[0051] In Formula II, R or R1 at each occurrence may independently be unsubstituted or substituted C1-C 12 A hydrocarbon group, and at least one R or R1 is unsubstituted; the average value of n is 1 or greater, and R' at each occurrence can be selected from In other aspects, R at each occurrence is H and R1 is substituted C1-C 12 The average value of n is 1 or more, and R' can be selected from In one example, R1 is methyl.

[0052] In other aspects, the aromatic phosphate can comprise a compound according to Formula III.

[0053]

[0054] According to various aspects, the flame retardant additive includes an aromatic phosphate having a phosphorus content of 7%, at least 8%, or at least 8.7%. Furthermore, the aromatic phosphate may have a phosphorus content of less than 11%, less than 10.8%, or less than 10%. In other aspects, the melting temperature of the aromatic phosphate is greater than or equal to 80°C, greater than or equal to 85°C, or greater than or equal to 90°C. An example of a suitable aromatic phosphate is 1,3-phenylene diphosphate tetrakis (2,6-dimethylphenyl) ester. Such aromatic phosphates can be purchased from Daihachi Chemical Industry Co., Ltd. as PX-200.

[0055] Some aspects of the composition include 5 wt % to about 25 wt % of a flame retardant comprising an aromatic phosphate ester. For example, based on the total weight of the composition, the aromatic phosphate ester flame retardant can be present in an amount of 6 wt % to 22 wt %, 8 wt % to 20 wt %, 8 wt % to 15 wt %, or 6 wt % to 15 wt %, 6 wt % to 18 wt %, 8 wt % to 18 wt %, 5 wt % to 18 wt %, 5 wt % to 20 wt %, or 5 wt % to 22 wt %, 10 wt % to 22 wt %, 10 wt % to 20 wt %, 10 wt % to 15 wt %, or 10 wt % to 15 wt %, or 10 wt % to 18 wt %.

[0056] Polystyrene

[0057] In various aspects, the disclosed compositions can include polystyrene polymers. As used herein, the term "polystyrene" includes polymers prepared by bulk, suspension, and emulsion polymerization, which contain at least 25% by weight of polymer precursors having structural units derived from monomers of formula (I):

[0058]

[0059] wherein R is hydrogen, lower alkyl or halogen; Z is vinyl, halogen or lower alkyl; and p is 0 to about 5. These organic polymers include: homopolymers of styrene, chlorostyrene and vinyltoluene; random copolymers of styrene with one or more monomers such as acrylonitrile, butadiene, α-methylstyrene, ethylvinylbenzene, divinylbenzene and maleic anhydride; and rubber-modified polystyrenes, including blends and grafts, wherein the rubber is polybutadiene or a rubbery copolymer of about 98 to about 70 weight percent styrene and about 2 to about 30 weight percent diene monomer. Polystyrene is generally miscible with polyphenylene ether.

[0060] In some aspects, the composition can include general-purpose polystyrene. As an example, the polystyrene component is selected from the group consisting of general-purpose polystyrene (GPPS) and high-impact polystyrene (HIPS). The composition of the present invention can include a polystyrene component of about 0.5 wt % to about 55 wt %, about 1 wt % to about 55 wt %, 10 wt % to about 55 wt %, about 3 wt % to about 45 wt %, about 3 wt % to about 50 wt %, about 1 wt % to about 55 wt %, about 1 wt % to about 50 wt %, or about 0.3 wt % to about 52 wt %. In some instances, the polystyrene component is polystyrene, such as general-purpose polystyrene (GPPS). In other aspects, polystyrene is high-impact polystyrene (HIPS). The composition can be free of or substantially free of HIPS. In other instances, the composition can be free of or substantially free of GPPS.

[0061] Impact modifier

[0062] The compositions of the present disclosure may also include an impact modifier. The impact modifier may include a functionalized polyolefin ethylene-acrylate terpolymer, such as ethylene-acrylate-maleic anhydride (MAH) or glycidyl methacrylate (GMA). The functionalized rubbery polymer may optionally contain a monomer derived from an anhydride group in its backbone, such as a repeating unit of maleic anhydride. In another case, the functionalized rubbery polymer may contain an anhydride moiety grafted onto the polymer in a post-polymerization step.

[0063] In certain aspects, the impact modifier may include an elastomer-modified graft copolymer. The elastomer-modified graft copolymer may include a styrene-rubber copolymer. The styrene rubber copolymer may include styrene-butadiene-styrene (SBS), styrene-butadiene rubber (SBR), styrene-ethylene-butadiene-styrene (SEBS), styrene ethylene propylene styrene (SEPS), acrylonitrile-butadiene-styrene (ABS), acrylonitrile-ethylene-propylene-diene-styrene (AES), styrene-isoprene-styrene (SIS), methyl methacrylate-butadiene-styrene (MBS) and styrene-acrylonitrile (SAN). An exemplary SEBS impact modifier is a high-flow SEBS having a melt flow index greater than 3 g / 10 min at 230 ° C / 5 kg when tested according to ISO-1133.

[0064] As described above, in certain examples, the compositions disclosed herein include 0.01 wt % to 12 wt %, or about 0.1 wt % to about 10 wt % of an impact modifier. In other examples, the composition includes 0.1 wt % to 8 wt % of an impact modifier, or about 1 wt % to about 8 wt % of an impact modifier, or about 2 wt % to about 12 wt % of an impact modifier, or about 3 wt % to about 10 wt % of an impact modifier, or about 2 wt % to about 10 wt % of an impact modifier, or even about 2 wt % to about 6 wt % of an impact modifier.

[0065] additive

[0066] Composition can include various additives that are usually incorporated into this type of polymer composition, and the limiting condition is to select additives so as not to significantly adversely affect the desired characteristics (such as good compatibility) of thermoplastic composition. The additive can be mixed at the appropriate time during the period of mixing components to form the composition. Each based on the gross weight of the composition, the total amount of all additives in the resin combination can be, for example, 0.001 to 12 weight %. Suitable additives can include ultraviolet agents, ultraviolet stabilizers, heat stabilizers, antistatic agents, antimicrobial agents, anti-drip agents, radiation stabilizers, pigments, dyes, fibers, fillers, plasticizers, fibers, flame retardants, antioxidants, lubricants, wood, glass and metals, and combinations thereof.

[0067] The composite disclosed herein may include one or more other fillers. The filler may be selected to impart additional impact strength and / or provide additional properties that may be based on the final selected properties of the polymer composition. In some aspects, the composite may include a glass fiber filler. In other aspects, the composite may be free of or substantially free of glass fillers.

[0068] Other suitable fillers or reinforcing agents may include, for example, mica, clay, feldspar, quartz, quartzite, perlite, diatomite, diatomaceous earth, aluminum silicate (mullite), synthetic calcium silicate, fused silica, fumed silica, sand, boron nitride powder, boron silicate powder, calcium sulfate, calcium carbonate (e.g., chalk, limestone, marble, and synthetic precipitated calcium carbonate), talc (including fibrous, modular, acicular, and lamellar talc), wollastonite, hollow or solid glass spheres, silicate spheres, cenospheres, aluminosilicates or (armospheres), kaolin; whiskers of silicon carbide, aluminum oxide, boron carbide, iron, nickel, or copper; continuous and chopped carbon fibers. Fiber or glass fiber, molybdenum sulfide, zinc sulfide, barium titanate, barium ferrite, barium sulfate, barite, titanium dioxide, 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 flour, fibrous cellulose, cotton, sisal, jute, starch, lignin, ground peanut shells or rice husks; reinforcing organic fibrous fillers such as poly (ether ketone), polyimide, polybenzoxazole, poly (phenylene sulfide), polyester, polyethylene, aromatic polyamide, aromatic polyimide, polyetherimide, polytetrafluoroethylene and poly (vinyl alcohol), and combinations comprising at least one of the foregoing fillers or reinforcing agents. Fillers and reinforcing agents can be coated or surface treated with, for example, silanes to improve adhesion and dispersion with the polymer matrix. Fillers can generally be used in an amount of 1 to 200 parts by weight based on 100 parts by weight of the total composition.

[0069] The additive composition may include flow modifiers, reinforcing agents, antioxidants, heat stabilizers, light stabilizers, ultraviolet light stabilizers, ultraviolet absorbing additives, plasticizers, lubricants, mold release agents, antistatic agents, antifogging agents, antimicrobial agents, chain extenders, colorants, mold release agents, flow promoters, flow modifiers, surface effect additives, radiation stabilizers, flame retardants, anti-drip agents, or any combination thereof.

[0070] The heat stabilizer additive includes an organic phosphite (e.g., triphenyl phosphite, tri-(2,6-dimethylphenyl) phosphite, tri-(mixed mono-nonylphenyl and di-nonylphenyl) phosphite, etc.), a phosphonate (e.g., dimethylphenylphosphonate, etc.), a phosphate (e.g., trimethyl phosphate, etc.), or a combination comprising at least one of the foregoing heat stabilizers. The heat stabilizer can be a phosphite capable of being irgaphosic. TM 168 obtained tris (2, 4-di-tert-butylphenyl) phosphate. The heat stabilizer is generally used in an amount of 0.01 to 5 weight percent based on the total weight of the polymer in the composition.

[0071] There is considerable overlap between plasticizers, lubricants, and mold release agents, including, for example, glyceryl tristearate (GTS), phthalates (e.g., octyl-4,5-epoxy-hexahydrophthalate), tris-(octyloxycarbonylethyl) isocyanurate, tristearin, difunctional or polyfunctional aromatic phosphates (e.g., resorcinol tetraphenyl diphosphate (RDP), bis(diphenyl) phosphate of hydroquinone, and bis(diphenyl) phosphate of bisphenol A); poly-α-olefins; epoxidized soybean oil; silicones, including silicone oils (e.g., poly(dimethyldiphenylsiloxane)); esters, such as fatty acid esters (e.g., alkyl stearyl esters, such as methyl stearate, stearyl stearate, etc.), waxes (e.g., beeswax, montan wax, paraffin wax, etc.), or a combination comprising at least one of the foregoing plasticizers, lubricants, and mold release agents. These components are typically used in amounts of 0.01 to 5% by weight, based on the total weight of the polymer in the composition.

[0072] Light stabilizers, particularly ultraviolet (UV) absorbing additives, also known as UV stabilizers, include hydroxybenzophenones (e.g., 2-hydroxy-4-n-octyloxybenzophenone), hydroxybenzotriazines, cyanoacrylates, oxanilides, benzoxazinones (e.g., 2,2'-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one, available under the trade name CYASORB TM UV-3638 available from Cytec Industries Inc., Woodland, NJ), aryl salicylates, hydroxybenzotriazoles (e.g., 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, and 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol, available under the trade name CYASORB TM 5411 available from Cytec Industries, Inc., The Woodlands, N.J.) or a combination comprising at least one of the foregoing light stabilizers. The UV stabilizer may be present in an amount of 0.01 to 1 wt %, specifically 0.1 to 0.5 wt %, more specifically 0.15 to 0.4 wt %, based on the total weight of the polymer in the composition.

[0073] Antioxidant additives include organic phosphites such as tris(nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, distearylpentaerythritol diphosphite; alkylated monophenols or polyphenols; alkylation reaction products of polyphenols with dienes such as tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane; butylation reaction products of p-cresol or dicyclopentadiene; alkylated hydroquinones; hydroxylated thiodiphenyl ethers; alkylene-bisphenols; benzyl compounds; β-(3,5-di-tert-butyl-4 -hydroxyphenyl)-propionic acid esters with monohydric or polyhydric alcohols; esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid with monohydric or polyhydric alcohols; esters of thioalkyl or thioaryl compounds, such as distearyl thiopropionate, dilauryl thiopropionate, ditridecyl thiodipropionate, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate; amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid, or a combination comprising at least one of the foregoing antioxidants. The antioxidant is used in an amount of 0.01 to 0.1 parts by weight, based on 100 parts by weight of the total composition, excluding any filler.

[0074] Suitable flame retardants include organic compounds containing phosphorus, bromine and / or chlorine. For regulatory reasons, non-brominated and non-chlorinated phosphorus-containing flame retardants may be preferred in certain applications, such as organic phosphates and organic compounds containing phosphorus-nitrogen bonds.

[0075] Inorganic flame retardants may also be used, such as salts of C1-16 alkyl sulfonates, such as potassium perfluorobutanesulfonate (Rimar salt), potassium perfluorooctanesulfonate, tetraethylammonium perfluorohexanesulfonate, and potassium diphenylsulfonesulfonate; salts such as Na2CO3, K2CO3, MgCO3, CaCO3, and BaCO3, or fluoride anion complexes such as Li3AlF6, BaSiF6, KBF4, K3AlF6, KAlF4, K2SiF6, and / or Na3AlF6. When present, the inorganic flame retardant salt is present in an amount of 0.01 to 10 parts by weight, more specifically 0.02 to 1 part by weight, based on 100 parts by weight of the total composition excluding any filler.

[0076] Anti-drip agents can also be used in compositions, such as fluoropolymers that form fibrils or do not form fibrils, such as polytetrafluoroethylene (PTFE). Anti-drip agents can be encapsulated by rigid copolymers such as styrene-acrylonitrile copolymers (SAN). PTFE encapsulated in SAN is called TSAN. TSAN contains 50% by weight PTFE and 50% by weight SAN based on the total weight of the encapsulated fluoropolymer. SAN can contain, for example, 75% by weight ethylene and 25% by weight acrylonitrile based on the total weight of the copolymer. Anti-drip agents can be used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the total composition excluding any filler.

[0077] The resin composition can be formed by techniques known to those skilled in the art. For example, the components of the resin composition can be combined using extrusion and mixing techniques. The composition can be blended with the above ingredients by a variety of methods involving intimate mixing of the material with any other additives required in the formulation. Due to the availability of melt blending equipment in commercial polymer processing facilities, melt processing methods are generally preferred. Illustrative examples of equipment used in such melt processing methods include: co-rotating and counter-rotating extruders, single screw extruders, co-kneaders, disc stack processors, and various other types of extrusion equipment. It is preferred to minimize the melt temperature in the method of the present invention to avoid excessive degradation of the resin. It is generally necessary to maintain the melt temperature in the molten resin composition between about 230°C and about 350°C, but higher temperatures can be used, with the limitation that the residence time of the resin in the processing equipment remains short. In some aspects, the melt-processed composition leaves the processing equipment, such as an extruder, through a small exit hole in the mold. The resulting molten resin strands are cooled by passing the strands through a water bath. The cooled strands can be chopped into small pellets for packaging and further processing.

[0078] The composition can be manufactured by various methods, including batch or continuous techniques using kneaders, extruders, mixers, etc. For example, a twin-screw extruder can be used to form the composition into a melt blend. In some aspects, at least some components are added sequentially. For example, a poly(arylene ether) component, a polystyrene component, and an impact modifier component can be added to the extruder at the feed throat or in a feed section adjacent to the feed throat or in a feed section adjacent to the feed throat, and a filler component can be added to the extruder in a subsequent downstream feed section. Alternatively, the sequential addition of components can be completed by multiple extrusions. The composition can be prepared by pre-extruding the selected components, such as a poly(arylene ether) component, a polystyrene component, and an impact modifier component to produce a granular mixture. Then a second extrusion can be used to combine the pre-extruded components with the remaining components. The filler component can be added as part of a masterbatch or added directly. The extruder can be a two-leaf or three-leaf twin-screw extruder.

[0079] In one aspect, the present disclosure relates to plastic components, such as plastic components shaped, formed, or molded at least in part from the compositions described herein. Also provided is a plastic part comprising a resin composition formed according to the method for forming a resin composition disclosed herein.

[0080] Features and products

[0081] In various aspects, the disclosed compositions can have improved flame retardant properties while balancing good flowability, dielectric properties, and heat distortion temperature. The improved flame retardancy can be characterized by a V1 or V0 rating when tested according to UL94. The compositions exhibit low dielectric constants and dissipation factors.

[0082] Considering the improved FR performance and the low dielectric constant and dissipation factor, the disclosed composition is particularly suitable for applications related to RF efficiency that particularly require a low dissipation factor. For example, antennas and 5G applications. Therefore, the disclosed composition and the products formed therefrom can be used in electronic applications that require FR delay and low dielectric properties. The composition and the product can be particularly suitable as antenna dipoles for base station and radome applications. In some aspects, when tested using a post-splitting dielectric resonator and a network analyzer, the disclosed composition exhibits a dissipation factor of less than 0.003, less than 0.0025, less than 0.0022, less than 0.0020, less than 0.0019, less than 0.0018 or less than 0.0017. The composition can exhibit improved high heat resistance, characterized in that when tested according to ISO 75, the heat deformation temperature is higher than 100°C, higher than 105°C, higher than 110°C, higher than 115°C or higher than 120°C at 0.45 MPa (MPa). The formulation further comprising an impact modifier (e.g., SEBS) may exhibit a HDT of greater than 120°C, greater than 130°C, or greater than 132°C. The formulation may have a melt flow rate of greater than 20 g / 10 min, greater than 30 g / 10 min, greater than 40 g / 10 min, greater than 50 g / 10 min, or greater than 55 g / 10 min, measured at 300°C, 5 kg load according to ASTM D1238. The formulation may have a melt flow rate of greater than 10 cm, measured at 300°C, 5 kg load according to ISO 1133. 3 / 10min, greater than 15cm 3 / 10min, greater than 18cm 3 / 10min melt volume rate.

[0083] In various aspects, the present disclosure relates to articles comprising the compositions herein. The compositions can be molded into useful shaped articles by various means, such as injection molding, extrusion, rotational molding, blow molding, and thermoforming to form articles. The compositions can be used to make articles requiring materials with good flowability, good impact strength, and good dielectric properties. The advantageous features of the compositions disclosed herein can make them suitable for a range of uses.

[0084] Manufacturing method

[0085] Aspects of the present disclosure also relate to methods for preparing thermoplastic compositions. One or any of the aforementioned components described herein may first be dry blended with each other, or with any combination of the aforementioned components, and then fed into an extruder from one feeder or multiple feeders, or fed into an extruder separately from one feeder or multiple feeders. The fillers used in the present disclosure may also be first processed into a masterbatch and then fed into an extruder. The components may be fed into an extruder from a throat hopper or any side feeder.

[0086] The extruder used in the present disclosure can have a single screw, multiple screws, intermeshing co-rotating or counter-rotating screws, non-intermeshing co-rotating or counter-rotating screws, reciprocating screws, screws with pins, screws with screens, barrels with pins, rollers, plungers, helical rotors, co-kneaders, disc-pack processors, various other types of extrusion equipment, or a combination including at least one of the foregoing components.

[0087] The components may also be mixed together and then melt blended to form the thermoplastic composition. Melt blending of the components involves the use of shear forces, extensional forces, compression forces, ultrasonic energy, electromagnetic energy, thermal energy, or a combination comprising at least one of the foregoing forces or energy forms.

[0088] The barrel temperature on the extruder during compounding can be set to a temperature at which at least a portion of the polymer reaches a temperature greater than or equal to about the melting temperature if the resin is a semicrystalline organic polymer, or to a temperature at the flow point (e.g., glass transition temperature) if the resin is an amorphous resin.

[0089] If desired, the mixture including the above-mentioned components can undergo multiple blending and forming steps. For example, the thermoplastic composition can be first extruded and formed into pellets. The pellets can then be fed into a molding machine where the pellets can be formed into any desired shape or product. Alternatively, the thermoplastic composition produced from a single melt blender can be formed into sheets or strands and subjected to post-extrusion processes such as annealing, uniaxial or biaxial orientation.

[0090] In some aspects, the temperature of the melt in the method of the present invention can be kept as low as possible to avoid excessive thermal degradation of the components. In some aspects, the melt temperature is maintained between about 230°C and about 350°C, but higher temperatures can be used, with the limitation that the residence time of the resin in the processing equipment remains relatively short. In some aspects, the melt-processed composition leaves the processing equipment, such as an extruder, through a small exit hole in the mold. The resulting molten resin strands can be cooled by passing the strands through a water bath. The cooled strands can be cut into small pellets for packaging and further processing.

[0091] The method can further comprise processing compound to provide the plate with desired thickness.The plate can be extruded, injection molded, compression molded or injection-compression molded, and can have a thickness between about 0.5mm and 6mm.Other processes can also be applied to thin thermoplastic films, including, but not limited to, lamination, coextrusion, thermoforming or hot pressing.In such aspect, other layers (for example, other thermoplastic polymer layers, metal layers, etc.) of other materials can be combined with compound.The present disclosure encompasses various combinations of elements of the present disclosure, such as the combination of elements from the dependent claims attached to the same independent claim.

[0092] definition

[0093] It should also be understood that the terms used herein are only for describing specific aspects and are not intended to be limiting. As used in the specification and in the claims, the term "comprising" may include embodiments "consisting of" and "consisting essentially of". Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present disclosure belongs. In this specification and the claims that follow, reference will be made to many terms that shall be defined herein.

[0094] As used in the specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a thermoplastic polymer component" includes a mixture of two or more thermoplastic polymer components. As used herein, the term "combination" includes blends, mixtures, admixtures, reaction products, and the like.

[0095] Ranges can be expressed as one value (first value) to another value (second value) in this article. When such ranges are expressed, the range includes one or both of the first value and the second value in some aspects. Similarly, when a value is expressed as an approximation by using the antecedent 'about', it should be understood that a specific value forms another aspect. It should also be understood that the endpoints of each range are important relative to the other endpoint and independently of the other endpoint. It should also be understood that multiple values ​​are disclosed herein, and each value is also disclosed herein as "about" a specific value other than the value itself. For example, if the value "10" is disclosed, "about 10" is also disclosed. It should also be understood that each unit between two specific units is also disclosed. For example, if 10 and 15 are disclosed, 11, 12, 13 and 14 are also disclosed.

[0096] As used herein, the terms "about" and "at or about" mean that the amount or value in question can be a specified value, about a specified value, or about the same as a specified value. As used herein, it is generally understood that, unless otherwise indicated or inferred, the nominal value indicates a variation of ±10%. The term is intended to convey that similar values ​​promote equivalent results or effects described in the claims. That is, it is understood that the amount, size, formula, parameter and other quantities and characteristics are not and need not be exact, but can be approximated and / or larger or smaller as needed, thereby reflecting tolerances, conversion factors, rounding, measurement errors, etc. and other factors known to those skilled in the art. In general, the amount, size, formula, parameter or other quantity or characteristic is "about" or "approximately", whether or not it is explicitly stated as such. It should be understood that when "about" is used before a quantitative value, unless otherwise specifically stated, the parameter also includes the specific quantitative value itself.

[0097] As used herein, the term "optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event or circumstance occurs and instances where the event or circumstance does not occur. For example, the phrase "optionally other processes" means that other processes may or may not be included, and that the description includes methods that include and do not include other processes.

[0098] Disclosed are components for preparing the compositions of the present disclosure and the compositions themselves used in the methods disclosed herein.These materials and other materials are disclosed herein, and it should be understood that when the combinations, subsets, interactions, groups, etc. of these materials are disclosed, although it is impossible to explicitly disclose specific references to each individual and collective combination and arrangement of these compounds, each combination and arrangement is specifically considered and described herein.For example, unless specifically indicated to the contrary, if a specific compound is disclosed and discussed and the multiple modifications that can be performed to a plurality of molecules including the compound are discussed, each combination and arrangement of the compound and possible modifications are specifically expected.Therefore, if a class of molecules A, B and C and a class of molecules D, E and F are disclosed and the example of the combination molecule AD is disclosed, then even if each is not narrated individually, it is still individually and collectively covered, thereby meaning to be regarded as a disclosed combination AE, AF, BD, BE, BF, CD, CE and CF.Similarly, any subset or combination of these combinations is also disclosed.Therefore, for example, it is regarded as a subgroup of AE, BF and CE being disclosed. This concept applies to all aspects of the present application, including but not limited to steps in methods of making and using the compositions of the present disclosure. Thus, if there are various additional steps that can be performed, it should be understood that each of these additional steps can be performed with any specific aspect or combination of aspects of the methods of the present disclosure.

[0099] The parts by weight of a particular element or component in a composition or article mentioned in the description and conclusions represent the weight relationship between the element or component and any other elements or components in the composition or article expressed in parts by weight. Thus, in a compound containing 2 parts by weight of component X and 5 parts by weight of component Y, X and Y are present in a weight ratio of 2:5, and are present in said ratio regardless of whether the compound contains other components.

[0100] Unless specifically indicated to the contrary, weight percentages of components are based on the total weight of the formulation or composition in which the component is included.

[0101] Throughout the specification, the terms "residue" and "structural unit" are used synonymously with respect to components of a polymer.

[0102] As used herein, unless otherwise specified, the terms "weight percent," "weight %," and "wt. %" are used interchangeably to indicate the weight percent of a given component based on the total weight of a composition. That is, unless otherwise specified, all weight % values ​​are based on the total weight of the composition. It should be understood that the sum of the weight % values ​​of all components in a disclosed composition or formulation is 100.

[0103] Unless otherwise stated herein to the contrary, all test standards are the most recent standards in effect at the time this application was filed.

[0104] As used herein, the term "number average molecular weight" or "Mn" may be used interchangeably and refers to the statistical average molecular weight of all polymer chains in a sample and is defined by the formula:

[0105]

[0106] Among them, M i is the molecular weight of the chain, and N i The molecular weight of a polymer, such as a polycarbonate polymer, can be determined by methods well known to those of ordinary skill in the art using molecular weight standards, such as polycarbonate standards or polystyrene standards, preferably certified or traceable molecular weight standards. n .

[0107] As used herein, the term "weight average molecular weight" or "Mw" is used interchangeably and is defined by the following formula:

[0108]

[0109] Among them, M i is the molecular weight of the chain, and N i is the number of chains of the molecular weight. n In comparison, M w The molecular weight of a given chain is taken into account when determining the contribution to the molecular weight average. Thus, the greater the molecular weight of a given chain, the greater the contribution of that chain to the molecular weight average. w The M of a polymer, such as a polycarbonate polymer, can be determined by methods well known to those skilled in the art using molecular weight standards, such as polycarbonate standards or polystyrene standards, preferably certified or traceable molecular weight standards. w .

[0110] As used herein, the degree of polymerization, n, may describe the number of monomer units (or repeating units) in a given polymer molecule.

[0111] In one aspect, "substantially free" can be less than about 0.5 weight percent (wt%). In another aspect, substantially free can be less than about 0.1 wt%. In another aspect, substantially free can be less than about 0.01 wt%. In another aspect, substantially free can be less than about 100 ppm. In another aspect, substantially free can refer to an amount (if present) below a detectable level. In one aspect, the compositions of the present disclosure contain no or substantially no carbon filler or carbon-based filler.

[0112] Each material disclosed herein is commercially available and / or its production method is known to those skilled in the art. It should be understood that the compositions disclosed herein have certain functions. Some structural requirements for performing the disclosed functions are disclosed herein, and it should be understood that there are various structures that can perform the same functions associated with the disclosed structures, and these structures will generally achieve the same results.

[0113] Aspects of the Disclosure

[0114] In various aspects, the present disclosure relates to and includes at least the following aspects.

[0115] Aspect 1. A composition comprising: about 35 wt % to about 85 wt % of a polyphenylene ether component; about 1 wt % to about 55 wt % of a polystyrene component; and about 5 wt % to about 25 wt % of a flame retardant, the flame retardant comprising an aromatic phosphate ester, wherein the aromatic phosphate ester comprises a compound according to Formula I

[0116]

[0117] wherein R at each occurrence may independently be an unsubstituted or substituted C1-C12 hydrocarbon group, and at least one R is unsubstituted, wherein the combined weight percentage values ​​of all components do not exceed 100 weight percent, and all weight percentage values ​​are based on the total weight of the composition, and wherein the composition exhibits: a flame retardancy rating of at least V1 at 1.5 mm as measured according to UL 94(2021), and a dissipation factor of less than 0.002 when tested using a split dielectric resonator and a network analyzer.

[0118] Aspect 2. The composition of aspect 1, wherein the composition exhibits a heat distortion temperature (HDT) above 110°C, 115°C, or above 120°C when tested according to ISO 75 at 0.45 MPa.

[0119] Aspect 3. A composition comprising: about 35 wt % to about 85 wt % of a polyphenylene ether component; about 1 wt % to about 55 wt % of a polystyrene component; and about 5 wt % to about 25 wt % of a flame retardant, the flame retardant comprising an aromatic phosphate ester, wherein the aromatic phosphate ester comprises a compound according to Formula I

[0120]

[0121] wherein R at each occurrence may independently be unsubstituted or substituted C1-C 12A hydrocarbon group, and at least one R is unsubstituted, wherein the total weight percentage value of all components does not exceed 100 weight percent, and all weight percentage values ​​are based on the total weight of the composition, and wherein the composition exhibits: at least a V1 flame retardant rating at 1.5 mm measured according to UL 94 (2021); a heat deformation temperature (HDT) greater than 110°C, greater than 115°C, or greater than 120°C when tested at 0.45 MPa according to ISO 75; and a dissipation factor less than 0.002 when tested using a split dielectric resonator and a network analyzer.

[0122] Aspect 4. The composition of any one of aspects 1 to 3, wherein the polyphenylene ether component comprises poly(2,6-dimethyl-1,4-phenylene ether).

[0123] Aspect 5A. The composition of any of Aspects 1 to 4, wherein the polystyrene component comprises high impact polystyrene or general purpose polystyrene.

[0124] Aspect 5B. The composition of any of Aspects 1 to 4, wherein the polystyrene component comprises high impact polystyrene.

[0125] Aspect 6A. A composition according to any one of Aspects 1 to 5B, wherein R at each occurrence is H or a substituted C1-C 12 The average value of n is 1 or more, and R' can be selected from

[0126] Aspect 6B. A composition according to any one of aspects 1 to 5, wherein the aromatic phosphate comprises a compound according to formula II

[0127]

[0128] wherein R or R1 at each occurrence may independently be unsubstituted or substituted C1-C 12 A hydrocarbon group, and at least one R or R1 is unsubstituted; the average value of n is 1 or greater, and R' at each occurrence can be selected from

[0129] Aspect 7. A composition according to any one of aspects 1 to 6B, wherein the aromatic phosphate comprises a compound according to formula III

[0130]

[0131] Aspect 8. The composition according to any one of aspects 1 to 7, wherein the aromatic phosphate ester has a melting point between 80°C and 200°C.

[0132] Aspect 9. The composition according to any one of Aspects 1 to 7, further comprising an additive material selected from the group consisting of: metal deactivators; acid scavengers; antioxidants; colorants; dyes; flow promoters; impact modifiers; light stabilizers; lubricants; mold release agents; pigments; colorants, quenchers; heat stabilizers; ultraviolet (UV) absorbers; UV reflectors; UV stabilizers; flame retardants; and combinations thereof.

[0133] Aspect 10. The composition of aspect 9, comprising from about 0.01 wt % to about 3 wt % of an additive material, wherein the additive material comprises one or more of a metal passivator, an acid scavenger, a mold release agent, and an antioxidant.

[0134] Aspect 11. The composition of aspect 9 or 10, wherein the additive material comprises an impact modifier comprising a styrene rubber copolymer.

[0135] Aspect 12. The composition of any one of aspects 1 to 11, wherein the composition is substantially free of bisphenol A bis(diphenyl phosphate) BPADP, resorcinol bis(diphenyl phosphate) RDP, triphenyl phosphate TPP, or aluminum diethylphosphite.

[0136] Aspect 13. The composition of any one of aspects 1 to 12, wherein the composition is free of epoxy resin.

[0137] Aspect 14. The composition of any one of Aspects 1 to 13, wherein the composition exhibits a melt flow rate of at least 15 g / 10 min when tested at 300° C. and 5 kg load according to ASTM D1238, or at least 15 cm when tested at 300° C. and 5 kg load according to ISO 1133. 3 / 10min melt volume rate.

[0138] Aspect 15. The composition of any of aspects 1 to 14, further comprising a poly(phenylene ether)-polysiloxane block copolymer reaction product, and wherein the composition exhibits a VO flame retardancy rating measured according to UL 94 at 1.5 mm.

[0139] Aspect 16. The composition of aspect 15, wherein the poly(phenylene ether)-polysiloxane block copolymer reaction product comprises a poly(phenylene ether) and a poly(phenylene ether)-polysiloxane block copolymer, wherein the poly(phenylene ether)-polysiloxane block copolymer comprises a poly(phenylene ether) block and a polysiloxane block comprising an average of 20 to 80 siloxane repeating units; wherein the poly(phenylene ether)-polysiloxane block copolymer reaction product comprises 1 to 30 weight percent siloxane repeating units and 70 to 99 weight percent phenylene ether repeating units, based on the total weight of the poly(phenylene ether)-polysiloxane block copolymer reaction product.

[0140] Aspect 17. A composition comprising: about 30 wt % to about 85 wt % of a polyphenylene ether component; about 8 wt % to about 50 wt % of a poly(phenylene ether)-polysiloxane block copolymer reaction product; about 1 wt % to about 55 wt % of a polystyrene component; about 5 wt % to about 25 wt % of a flame retardant comprising an aromatic phosphate ester, wherein the combined weight percentage values ​​of all components do not exceed 100 wt %, and all weight percentage values ​​are based on the total weight of the composition, and wherein the composition exhibits: a flame retardancy rating of at least V0 at 1.5 mm as measured by UL 94 (2021); a heat deformation temperature (HDT) greater than 120° C. when tested at 0.45 MPa according to ISO75; and a dissipation factor less than 0.002 when tested using a split dielectric resonator and a network analyzer.

[0141] Aspect 18. An article formed from the composition of any one of aspects 1 to 17.

[0142] Aspect 19. The article according to aspect 18, wherein the article is an antenna or an antenna hiding housing.

[0143] Aspect 20. A method of forming an article, the method comprising: combining the following components to form a mixture: about 35 wt% to about 85 wt% of a polyphenylene ether component; about 1 wt% to about 55 wt% of a polystyrene component; and about 5 wt% to about 25 wt% of a flame retardant comprising an aromatic phosphate ester, wherein the combined weight percentage value of all components does not exceed 100 wt%, and all weight percentage values ​​are based on the total weight of the composition; and molding an article from the mixture, wherein the article exhibits: at least a V1 flame retardancy rating at 1.5 mm as measured according to UL 94 (2021), and a dissipation factor of less than 0.002 when tested using a post-splitting dielectric resonator and a network analyzer. Aspect 21. The method according to aspect 20, wherein the article exhibits a heat distortion temperature (HDT) greater than 120°C when tested at 0.45 MPa according to ISO 75.

[0144] Aspect 22. A composition comprising: about 35 wt % to about 85 wt % of a polyphenylene ether component; about 1 wt % to about 55 wt % of a polystyrene component; and about 5 wt % to about 25 wt % of a flame retardant, the flame retardant comprising an aromatic phosphate ester, wherein the aromatic phosphate ester comprises a compound according to Formula II

[0145]

[0146] and wherein R at each occurrence is H and R1 is substituted C1-C 12 The average value of n is 1 or more, and R' can be selected from

[0147] Examples

[0148] The following examples are shown to provide a complete disclosure and description of how to prepare and evaluate the compounds, compositions, articles, devices and / or methods required herein to those of ordinary skill in the art, and are intended to be used as examples rather than intended to limit the present disclosure. Efforts have been made to ensure the accuracy of numbers (e.g., amounts, temperatures, etc.), but some errors and deviations should be considered. Unless otherwise specified, parts are weight parts, temperatures are in ° C or at ambient temperature, and pressures are at or near atmospheric pressure. Unless otherwise specified, the percentage of the composition mentioned is weight %. There are many variations and combinations of mixing conditions, such as component concentrations, extruder designs, feed rates, screw speeds, temperatures, pressures, and other mixing ranges and conditions that can be used to optimize the product purity and yield obtained from the described process. Only reasonable and conventional experimental methods will be required to optimize such process conditions.

[0149] From Table 1( Figure 1 ) are used to prepare various PPE resins.

[0150] The compounding conditions are shown in Table 2. The formulations were compounded on a laboratory twin screw extruder (Toshiba TEM-37BS) where all components were added through a throat feeder except for RDP and BPADP which were added through a liquid feeder. Compounding was performed at a screw rotation of 300 revolutions per minute (rpm) with a throughput of 25-30 kilograms per hour (kg / h). Table 2 shows an overview of the compounding.

[0151] Table 2. Mixing conditions

[0152] Zone 1 Temperature ℃ 50 Zone 2 Temperature ℃ 150 Zone 3 Temperature ℃ 280 Zone 4 Temperature ℃ 280 Zone 5 Temperature ℃ 270 Zone 6 Temperature ℃ 280 Zone 7 Temperature ℃ 280 Zone 8 Temperature ℃ 290 Zone 9 Temperature ℃ 290 Zone 10 Temperature ℃ 290 Zone 11 Temperature ℃ 290 Zone 12 Temperature ℃ 290 Mold temperature ℃ 290

[0153] Injection molding was performed on a Sumitomo DEMAG SE180EV molding machine to form plaques for dielectric (Dk, Df) measurements, on a FANUC S-2000i 100A molding machine to form bars for heat deformation test (HDT) testing, and on a NESTALSYNERGY 1500K molding machine to form combustion bars. The molding conditions are shown in Table 3.

[0154] Table 3. Injection molding conditions

[0155]

[0156]

[0157] Test. Flammability was measured by vertical burning test on 1.5 mm thick burning rod according to UL94. Dielectric constant (Dk) / dissipation (Df) was measured at 1.9 GHz on 100×70×0.75 millimeter (mm) or 75×75×2 mm plates using SABIC method with QWED split dielectric resonator and Agilent PNA network analyzer. Melt flow rate (MFR) and melt volume rate (MVR) were measured at 300°C and 5 kg load according to ASTM D1238 and ISO1133, respectively. Heat deformation temperature (HDT) was determined on 4 mm thick rod using 0.45 MPa load according to ISO75.

[0158] The flammability test is carried out according to the procedure of Underwriter's Laboratory Bulletin 94 entitled "Tests for Flammability of Plastic Materials, UL 94 (2021)". It can be divided into several grades based on burning rate, extinguishing time, anti-drip ability and whether the dripping liquid is burning. The thickness of the rod is 0.8 mm or 1 mm. Based on the test results obtained for five samples, the material can be classified as UL 94HB (horizontal burning), V0, V1, V2, 5VA and / or 5VB according to this procedure; however, the compositions in this article are tested and classified only as V0, V1 and V2, and their respective standards are described as follows. These standards depend on the extinguishing time (FOT) and are sensitive to the dripping of the molten sample. If the molten sample does not ignite the underlying cotton wool (i.e., non-burning dripping, "NB"), it does not affect the flammability rating. In the case where the molten burning sample ignites the underlying cotton wool, this is indicated as burning dripping (BD). The five rods were tested for individual extinguishing time, with a FOT of 30 seconds or less being classified as UL94-V1 or UL94-V2. An individual FOT of less than 10 seconds is classified as UL94-V0.

[0159] The formulations are shown in Table 4. Comparative Examples CEx1-CEx5 each include a conventional flame retardant (BPADP, RDP, TPP, or DEPAL). Inventive Example Ex1 includes tetrakis(2,6-dimethylphenyl)-1,3-phenylene diphosphate.

[0160] Table 4. Combustibility, Dielectric Properties and Flowability

[0161]

[0162]

[0163] Table 4 shows that flammability is improved by incorporating all types of FR agents. Compared to all FR-containing comparative examples (CEx2-5), the Ex1 composition shows better FR properties (V1), as well as the lowest Df and the second lowest Dk. Without wishing to be bound by any particular theory, the good dielectric properties of Ex1 may be due to the special molecular structure of the FR agent, which provides greater steric hindrance than other phosphate FR agents. Although Ex1 and CEx5 have similar Dk, Ex-1 exhibits much higher fluidity than CEx5, which can facilitate molding processes for thin parts in electronic devices.

[0164] Other formulations including PPE-Si resins were prepared and are shown in Table 5.

[0165] Table 5. Comparative sample CEx6 and samples Ex2 to Ex5 of the present invention

[0166]

[0167] The formulations and properties in Table 5 show that flammability and flowability are further improved by increasing the 1,3-phenylene diphosphate tetrakis (2,6-dimethylphenyl) ester content, while the compounds still maintain low Dk, Df values. Adding PPE-Si can help achieve V0 at lower FR agent content. Ex2 to Ex5 also show high HDT values.

[0168] Table 6 presents other formulations and properties, demonstrating the dissipation factors observed when FR1 (tetrakis(2,6-dimethylphenyl)1,3-phenylene diphosphate) is replaced by an alternative aromatic phosphate ester FR2 (hydroquinone bis(diphenyl phosphate)). Comparative sample CEx7 replaces FR1 with FR2; comparative sample CEx8 replaces FR1 with FR2 and uses GPPS instead of SEBS. Sample Ex6 of the present invention includes FR1 and is characterized by including GPPS instead of SEBS.

[0169] Table 6. Comparative samples CEx7 and CEx8 and inventive sample Ex6.

[0170]

[0171]

[0172] As shown, Ex6 exhibits a dissipation factor of less than 0.002 while maintaining similar dielectric constant, HDT, flame retardancy, and flow. Without wishing to be bound by any particular theory, the methyl groups at the aromatic ring positions in FR1 appear to affect the properties of the composition, making the aromatic phosphate flame retardant additives FR1 and FR2 not readily interchangeable.

[0173] The above description is intended to be illustrative and not restrictive. For example, the examples described above (or one or more aspects thereof) may be used in combination with each other. Other embodiments may be used, such as after a person of ordinary skill in the art consults the above description. An abstract is provided to allow the reader to quickly determine the nature of the present technology disclosure. The abstract is submitted with the following understanding: it will not be used to interpret or limit the scope or meaning of the claims. In addition, in the above specific embodiments, various features may be grouped together to simplify the present invention. This situation should not be interpreted as an expectation that unclaimed public features are necessary for any claim. In fact, the subject matter of the invention may be less than all the features of a specific disclosed embodiment. Therefore, the following claims are hereby incorporated into the specific embodiments as examples or embodiments, wherein each claim itself is a separate embodiment, and it is considered that such embodiments may be combined with each other into various combinations or arrangements. The scope of the present disclosure should be determined with reference to the attached claims and the full range of equivalents given by these claims.

[0174] It will be apparent to those skilled in the art that various modifications and variations may be made to the present disclosure without departing from the scope or spirit of the present disclosure. Other embodiments of the present disclosure will be apparent to those skilled in the art from consideration of the description and practice of the present disclosure disclosed herein. It is intended that the description and examples be considered exemplary only, with the true scope and spirit of the present disclosure being specified by the following claims.

[0175] The patentable scope of the present disclosure is limited by the claims, and may include other examples that are thought of by a person skilled in the art. If these other examples have structural elements that are not different from the literal language of the claims, or if they include equivalent structural elements that are not substantially different from the literal language of the claims, they are intended to be within the scope of the claims. It should be understood that the compositions disclosed herein have certain functions. This paper discloses certain structural requirements for performing the disclosed functions, and it should be understood that there are various structures that can perform the same functions associated with the disclosed structures, and these structures will generally achieve the same results.

Claims

1. A composition comprising: from about 35% to about 85% by weight of a polyphenylene ether component; From about 1 wt % to about 55 wt % of a polystyrene component; and From about 5 weight percent to about 25 weight percent of a flame retardant, the flame retardant comprising an aromatic phosphate ester, wherein the aromatic phosphate ester comprises a compound according to Formula I wherein R at each occurrence may independently be unsubstituted or substituted C1-C 12 A hydrocarbon group, and at least one R is unsubstituted, wherein the combined weight percentage values ​​of all components do not exceed 100 weight percent, and all weight percentage values ​​are based on the total weight of the composition, and wherein the composition exhibits At least V1 flame retardancy rating at 1.5 mm as measured according to UL 94(2021), and When tested using a split dielectric resonator and a network analyzer, the dissipation factor is less than 0.

002.

2. The composition of claim 1, wherein the polyphenylene ether component comprises poly(2,6-dimethyl-1,4-phenylene ether).

3. The composition according to any one of claims 1 to 2, wherein the polystyrene component comprises high impact polystyrene or general purpose polystyrene.

4. The composition according to any one of claims 1 to 3, wherein the aromatic phosphate comprises a compound according to formula II 5. The composition of any one of claims 1 to 4, wherein the polyphenylene ether component is present in an amount of about 55 wt% to about 85 wt%.

6. The composition of any one of claims 1 to 4, wherein the polyphenylene ether component is present in an amount of about 60 wt% to about 85 wt%.

7. The composition of any one of claims 1 to 4, wherein the polyphenylene ether component is present in an amount of about 70 wt% to about 85 wt%.

8. The composition of any one of claims 1 to 7, wherein the aromatic phosphate has a melting point between 80°C and 200°C.

9. The composition of any one of claims 1 to 8, further comprising an additive material selected from the group consisting of: metal deactivators; acid scavengers; antioxidants; colorants; dyes; flow promoters; impact modifiers; light stabilizers; lubricants; mold release agents; pigments; colorants, quenchers; heat stabilizers; ultraviolet (UV) absorbers; UV reflectors; UV stabilizers; flame retardants; and combinations thereof.

10. The composition of claim 9 comprising from about 0.01 wt. % to about 3 wt. % of the additive material, the additive material comprising one or more of a metal passivator, an acid scavenger, a mold release agent, and an antioxidant.

11. The composition of any one of claims 1 to 10, wherein the composition is substantially free of bisphenol A bis(diphenyl phosphate) BPADP, resorcinol bis(diphenyl phosphate) RDP, triphenyl phosphate TPP, or aluminum diethylphosphite.

12. The composition of any one of claims 1 to 11, wherein the composition is free of epoxy resin.

13. The composition of any one of claims 1 to 12, further comprising a poly(phenylene ether)-polysiloxane block copolymer reaction product, and wherein the composition exhibits a VO flame retardancy rating at 1.5 mm as measured according to UL 94.

14. The composition of claim 13, wherein the poly(phenylene ether)-polysiloxane block copolymer reaction product comprises poly(phenylene ether) and poly(phenylene ether)-polysiloxane block copolymer, wherein the poly(phenylene ether)-polysiloxane block copolymer comprises a poly(phenylene ether) block and a polysiloxane block comprising an average of 20 to 80 siloxane repeating units, and The poly(phenylene ether)-polysiloxane block copolymer reaction product comprises 1 to 30 weight percent of siloxane repeating units and 70 to 99 weight percent of phenylene ether repeating units, based on the total weight of the poly(phenylene ether)-polysiloxane block copolymer reaction product.

15. A method of forming an article, the method comprising: a. Combine the following components to form a mixture: i. from about 35% to about 85% by weight of a polyphenylene ether component, ii. from about 1 wt % to about 55 wt % of a polystyrene component, and iii. about 5 wt % to about 25 wt % of a flame retardant, the flame retardant comprising an aromatic phosphate ester, wherein the aromatic phosphate ester comprises a compound according to formula I wherein R at each occurrence may independently be unsubstituted or substituted C1-C 12 A hydrocarbon group, and at least one R is unsubstituted, wherein the combined weight percentage values ​​of all components do not exceed 100 weight percent, and all weight percentage values ​​are based on the total weight of the composition; and b. molding an article from said mixture, wherein the article exhibits At least V1 flame retardancy rating at 1.5 mm as measured according to UL 94(2021), and When tested using a split dielectric resonator and a network analyzer, the dissipation factor is less than 0.002.

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