Flame-retardant PPS-based composition and molded article using the same

Abstract

A flame-retardant PPS-based composition comprising A) at least one polyphenylene sulfide polymer, B) at least one polyphenylsulfone polymer, C) at least one epoxy functional group-containing thermoplastic elastomer, and D) epoxy-modified polysiloxane. The PPS-based composition has a V-0 rating when using UL94V (2013) standard (thickness 0.8 mm). Articles containing or manufactured from such a flame-retardant PPS-based composition. Use of articles as components of electric vehicles. A method for cooling and / or operating a battery, comprising passing a heat transfer fluid through a flame-retardant heat transfer tube containing or manufactured from a flame-retardant PPS-based composition.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority under European Patent Application No. 23167551.3, filed on 12 April 2023, and the entire contents of this application are incorporated herein by reference for all purposes.

[0002] The present invention generally relates to flame-retardant PPS-based compositions and their use in the manufacture of flame-retardant molded articles, particularly extruded articles, overmolded components, and thin-walled molded articles, which can be appropriately used in automotive components and thermal management systems, especially components and systems used in electric vehicles. [Background technology]

[0003] In many applications, plastics are a crucial material in driving electric mobility. Due to their functional integration and lightweight properties, plastics offer significant advantages to automotive engineers in solving technical challenges that are nearly impossible to achieve with metals.

[0004] Because electric powertrains present different hazards than incinerated powertrains, new property requirements are imposed on plastics. In particular, a high level of safety is required against electrical failures that could lead to electric shock, electric arcs, and other sources of ignition. Since plastics are primarily flammable materials, special precautions must be taken to enhance the safety of electric vehicles and prevent the worst-case scenario of battery cell fire, also known as thermal runaway.

[0005] Batteries now need to provide greater instantaneous power output and have higher storage capacity than ever before. Currently, batteries with operating voltages of several hundred volts are known. To achieve the desired voltage and current, it is common to connect multiple individual battery cells in parallel and / or series.

[0006] While electric vehicle batteries are advancing to deliver more power and reduce the frequency of charging, one of the biggest challenges regarding battery safety is the ability to design an effective cooling system.

[0007] In a typical lithium-ion battery, temperatures exceeding 80°C in even a small part of its structure can trigger exothermic chemical reactions that cause further temperature increases in the battery, ultimately leading to complete battery destruction and posing a risk of fire and explosion.

[0008] For this reason, it is now common practice to incorporate a battery thermal management system (BTMS) into commercial battery assemblies, especially when battery safety, reliability, and lifespan are of critical concern. These BTMSs can be complex to varying degrees depending on the type of battery, however, one common element is the presence of a heat transfer fluid that exchanges heat with the battery, thereby heating or cooling it.

[0009] For battery thermal management, several heat transfer systems exist, including air cooling, liquid cooling, and direct refrigerant cooling. Among these, liquid cooling is the most commonly used system due to its convenient design and superior heat transfer performance.

[0010] Because this type of heat transfer system is already common in vehicles with conventional drive systems, i.e., internal combustion engines, the use of water or a water / ethylene glycol mixture as a heat transfer medium is widespread. A significant safety drawback of using this water-based heat transfer medium is its conductivity. For example, if the heat transfer circuit leaks as a result of an accident, the leaked water or water / ethylene glycol mixture can cause a short circuit. This could result in a fire or other emergency, potentially causing additional, and in some cases, serious damage to the vehicle. To mitigate this risk, components of the thermal management system must have high flame retardancy. Therefore, flame-retardant polymer compounds are required for e-mobility applications.

[0011] One conventional method for identifying the flame retardancy of plastic materials is a standard test developed by Underwriters Laboratory (USA), called UL94 (Vertical Flammability Test), or Standard for Safety of Flammability of Plastic Materials for Parts in Devices and Appliances testing. Preferably, components of thermal management systems used in electric vehicle batteries must meet the V-0 standard, which identifies plastic materials that "cannot burn and allow for non-igniting plastic drops in a vertical section within 10 seconds."

[0012] Polyphenylene sulfide (hereinafter sometimes abbreviated as "PPS") resin is an engineering plastic that possesses a good balance of properties such as heat resistance, chemical resistance, and flame retardancy. Therefore, PPS resin is an excellent polymer candidate for use in components of eV batteries, such as thermal management systems used in eV batteries.

[0013] In addition, due to its cost advantage over other engineering plastics, PPS resin is used as a highly versatile resin material in a wide range of applications, including automotive, housing equipment, and electrical and electronic applications.

[0014] However, PPS resin is brittle, and its toughness, expressed as tensile elongation in tensile tests, is lower compared to other engineering polymers.

[0015] For applications requiring toughness, a PPS resin composition containing α-olefin-glycidyl methacrylate copolymer has been developed, as described in Japanese Patent Publication No. 61-021156. In this composition, improvements in toughness and flexibility can be achieved by blending it with an olefin-based elastomer, which is a softer material than PPS resin.

[0016] However, the flame retardancy of such resin compositions containing PPS resin and olefinic elastomer described in JP-A-61-021156 has been evaluated in WO 2022 / 209848 A1 pamphlet. The flame retardancy of this resin composition is lower than that of PPS resin alone, and it has been observed that the flame retardancy significantly decreases when an olefinic elastomer is added to PPS. In WO 2022 / 209848 A1 pamphlet, a hypothesis has been proposed that although PPS resin alone has high flame retardancy, blending an olefinic elastomer with significantly inferior flame retardancy results in a decrease in the flame retardancy of the resulting blend composition. While this blend composition has the advantage of having flexibility and toughness, it has the problem that it does not exhibit the excellent flame retardancy inherent in PPS resin, and thus the development of its applications is limited.

[0017] Such findings have been confirmed by the applicant in relation to manufacturing cooling pipes from the enhanced PPS composition. PPS blended with thermoplastic elastomer ("TPE") achieved sufficient toughness and viscosity to enable the extrusion and thermoforming of pipes. However, introducing 10 wt% of TPE into PPS results in a material with insufficient flame retardancy. For example, the enhanced PPS material was not V-0 (UL94V (2013): vertical burning test, measured with a 1.6 mm thick specimen). Due to the low TPE content, the enhanced PPS material (PPS + TPE) had insufficient ductility, and the strain at break was only about 13%.

[0018] Therefore, there is a continuing need in the art for a flame-retardant PPS composition suitable for manufacturing articles intended for use in systems with a high fire risk, such as an eV battery for use in an electric vehicle (eV), particularly components of an eV battery's thermal management system. This article needs to have the highest flame retardancy grade V-0 based on UL94V (2013) (thickness 0.8 mm) and at the same time have the mechanical properties necessary to withstand the requirements during use. SUMMARY OF THE INVENTION

[0019] The present invention is as disclosed below and in the appended claims.

[0020] A first object of the present invention is · (A) at least one polyphenylene sulfide (PPS) polymer of 45 to 75% by weight, · (B) at least one polyphenylene sulfone (PPSU) polymer of 20 to 45% by weight, · (C) at least one epoxy-functional thermoplastic elastomer (TPE) of 4.5 to 12% by weight, · (D) at least one epoxy-modified polysiloxane ("pSiO") of 0.5 to 5% by weight, A polyphenylene sulfide-based composition containing, wherein the % by weight is based on the total weight of the PPS-based composition, and the total content of components (A), (B), (C), and (D) is 100% by weight or less based on the total weight of the PPS-based composition.

[0021] The polyphenylene sulfide-based composition of the present invention is a flame-retardant material having the highest flame-retardant grade V-0 based on UL94V (2013), measured with a test piece having a thickness of 1.0 mm or less, preferably a thickness of 0.8 mm.

[0022] A second object of the present invention is the use of the flame-retardant PPS-based composition according to the first object for producing a flame-retardant article, i.e., an article having a V-0 grade, and the V-0 flame-retardant grade is measured with a test piece having a thickness of 1.0 mm or less, preferably a thickness of 0.8 mm, based on the UL94V (2013) vertical burning test standard.

[0023] A third object of the present invention is an article comprising or manufactured from a flame-retardant PPS-based composition according to the first object. This article has a V-0 flame retardancy rating, which is measured on a test specimen with a thickness of 1.0 mm or less, preferably 0.8 mm, according to UL94V (2013). This article can be used as a component in automotive devices, such as components for electric vehicles (eVs) and / or thermal management systems (e.g., heat transfer tubes, magnet wires, busbars, bobbins, slot liners, slot wedges, power modules, etc.), particularly in eV batteries, electric motors, or generators, and / or components in the thermal management systems of eV batteries.

[0024] A fourth object of the present invention is a method for improving the flame retardancy grade of a V-1 grade PPS composition containing at least one polyphenyl sulfide, at least one polyphenyl sulfone, and at least one epoxy functional group-containing thermoplastic elastomer. This method comprises adding an epoxy-modified polysiloxane to a V-1 grade PPS composition to obtain a V-0 grade PPS composition of the present invention. The flame retardancy grades of V-0 and V-1 are measured based on UL94V (2013) using test specimens with a thickness of 1.0 mm or less, preferably 0.8 mm.

[0025] In this study, it was found that articles satisfying flame retardancy grade V-0, as measured by a test specimen with a thickness of 1.0 mm or less, preferably 0.8 mm, according to UL94V (2013), can be produced using a specific PPS-based composition containing at least one polyphenyl sulfide, at least one polyphenyl sulfone, at least one epoxy functional group-containing thermoplastic elastomer, and at least one epoxy-modified polysiloxane. These flame-retardant articles are preferably extruded components / parts and / or thin-walled molded components / parts intended for use in electric vehicles. These flame-retardant articles are particularly useful as components (e.g., tubular members such as heat transfer tubes, coated wires / cables such as magnet wires, busbars such as electric busbars, bobbins such as coil bobbins, slot liners, slot wedges, power modules, etc.) for automobiles and thermal management systems, especially in eV batteries, electric motors or generators, and / or thermal management systems for eV batteries.

[0026] Various aspects, advantages, and features of the present invention will be more readily understood and recognized by referring to the detailed description and examples.

[0027] definition In the following specification and claims, several terms are used, and these terms are defined as having the following meanings: The terms "a," "an," or "the" mean "one or more" or "at least one" unless otherwise specified, and are interchangeable; The term "and / or" used in phrases of the form "A and / or B" means A only, B only, or A and B together; Even if described in relation to a particular embodiment, any description is applicable to and interchangeable with other embodiments of this disclosure, and each embodiment as thus defined may be combined with other embodiments unless otherwise indicated or obviously incompatible; Where it is said that an element or component is included in and / or selected from a list of enumerated elements or components, in the relevant embodiments expressly considered herein, the element or component may also be any one of the individual enumerated elements or components, or may be selected from any group of two or more of the expressly enumerated elements or components; it should be understood that any element or component enumerated in a list of elements or components may be omitted from such list; Any enumeration of numerical ranges by endpoints in this specification includes all numbers, endpoints, and equivalents contained within the enumerated range; The term “contains” (or “includes”) includes “essentially consists of” (or “essentially consists of”) and also “consists of” (or “consists of”); In this specification, the term “comprise” is synonymous with “including,” “containing,” or “characterized by,” and is intended to be comprehensive or non-restrictive, without excluding additional, unlisted elements or processes; In this specification, the term "consisting essentially of" includes, in addition to the specified materials or processes, those that do not essentially affect the composition, process, method of the described manufacture, or the basic characteristics or function of the article; In this specification, the term "consisting of" excludes any elements, processes, or components not specified; The term “consisting essentially of” in relation to compositions, articles, components, processes, or methods is intended to mean that additional elements, steps, or features not expressly described herein and not essentially affecting the basic and novel characteristics of such compositions, articles, components, processes, or methods may be included in such embodiments; and typically, with respect to the compositions of the present invention, “consisting essentially of” means that the content of components not expressly described herein is less than 1% by weight, or less than 0.5% by weight, or less than 0.1% by weight, or less than 0.05% by weight, or even less than 0.01% by weight, where the weight percentage is based on the total weight of the PPS-based composition; The approximate expressions used throughout this specification and in the claims may be applied to modify quantitative expressions that may vary within an acceptable range without altering the underlying function; therefore, values ​​modified by terms such as “approximately” or “substantially” should not be limited to specified exact values, and in at least some cases, the approximate expression may correspond to the precision of the instrument used to measure that value; The terms "optional" or "optionally" mean that the components, steps, or circumstances of a method described thereafter may or may not be present, and that description includes the cases in which the components, steps, or circumstances of a method may or may not be present; The scope limitations in this specification and the claims as a whole may be combined and / or replaced, and unless otherwise indicated by context or word, such scope shall be specified and include all sub-scopes contained therein; It should be understood that the elements, properties, and / or characteristics of the polymers, compositions, products or articles, processes, methods, or uses described herein may be combined in any possible way, expressly or implicitly, with other elements, properties, and / or characteristics of the polymers, compositions, products or articles, processes, methods, or uses without departing from the scope of this specification; The term "recurring unit" refers to the smallest repeating unit of a polymer chain; the term "recurring unit" is synonymous with the terms "repeating unit" and "structural unit"; The proportion of repeating units in a polymer is expressed as a mole percentage relative to the total molar amount of repeating units in the polymer.

[0028] If any disclosure of a patent, patent application, or publication incorporated herein by reference conflicts with any description in this application to such an extent that it obscures certain terms, the description herein shall prevail. [Modes for carrying out the invention]

[0029] Flame-retardant PPS-based composition Flame-retardant PPS-based compositions, (A) 45-75% by weight of at least one PPS polymer, (B) 20-45% by weight of at least one PPSU polymer, (C) At least one type of TPE in an amount of 4.5 to 12% by weight, (D) 0.5 to 5% by weight of at least one epoxy-modified polysiloxane, It contains, The aforementioned weight percentage is based on the total weight of the PPS-based composition. The total content of components (A), (B), (C), and (D) is 100% by weight or less based on the total weight of the PPS-based composition.

[0030] Preferably, the flame-retardant PPS-based composition is (A) 45-70% by weight of at least one PPS polymer, (B) 22-43% by weight of at least one PPSU polymer, (C) 5-11% by weight of at least one type of TPE, (D) 0.6 to 4% by weight of at least one epoxy-modified polysiloxane, It contains, The aforementioned weight percentage is based on the total weight of the PPS-based composition. The total content of components (A), (B), (C), and (D) is 100% by weight or less based on the total weight of the PPS-based composition.

[0031] More preferably, the flame-retardant PPS-based composition is (A) 50-65% by weight of at least one type of PPS polymer, (B) 23-40% by weight of at least one type of PPSU polymer, (C) 6-10% by weight of at least one type of TPE, (D) 0.7 to 3% by weight of at least one epoxy-modified polysiloxane, It contains, The aforementioned weight percentage is based on the total weight of the PPS-based composition. The total content of components (A), (B), (C), and (D) is 100% by weight or less based on the total weight of the PPS-based composition.

[0032] More preferably, the flame-retardant PPS-based composition is (A) 50-65% by weight of at least one type of PPS polymer, (B) 27-38% by weight of at least one type of PPSU polymer, (C) 7-10% by weight of at least one type of TPE, (D) 1-2% by weight of at least one epoxy-modified polysiloxane, It contains, The aforementioned weight percentage is based on the total weight of the PPS-based composition. The total content of components (A), (B), (C), and (D) is 100% by weight or less based on the total weight of the PPS-based composition.

[0033] More preferably, a flame-retardant PPS-based composition, (A) At least one PPS polymer in an amount of 45-75% by weight, or 47-70% by weight, or 50-65% by weight, (B) At least one PPSU polymer in an amount of 20-45% by weight, or 22-43% by weight, or 23-40% by weight, or 27-38% by weight, (C) At least one type of TPE in an amount of 4.5-12% by weight, or 5-11% by weight, or 6-10% by weight, (D) 0.5-5% by weight, or 0.6-4% by weight, or 0.7-3% by weight, or 1-2% by weight of at least one epoxy-modified polysiloxane, • At least one additive (E) in an optional amount of up to 10% by weight, • At least one other resin (F) in less than 15% by weight, which is different from components (A), (B), (C), (D), and (E), It contains, The aforementioned weight percentage is based on the total weight of the PPS-based composition. The total content of components (A), (B), (C), (D), (E), and (F) is 100% by weight based on the total weight of the PPS-based composition.

[0034] The PPS-based composition of the present invention has a flame retardancy rating of V-0 based on the UL94V (2013) vertical combustion test, measured on a test specimen with a thickness of 1.0 mm or less, preferably 0.8 mm.

[0035] The PPS-based composition of the present invention is preferably halogen-free, which means that no halogen-containing components are used in the PPS-based composition.

[0036] The flame-retardant PPS-based composition of the present invention preferably does not contain phosphorus-based flame retardants, halogen-based flame retardants, inorganic flame retardants, or any combination thereof.

[0037] The PPS-based composition of the present invention more preferably does not contain a flame retardant.

[0038] Components (C) and (D) and optional components (E) and (F) in the PPS-based composition of the present invention are not flame retardants.

[0039] The PPS-based composition of the present invention may contain a polymer (F) different from components (A), (B), (C), (D), and (E), but it is preferable that the PPS-based composition of the present invention does not contain any other polymers different from components (A), (B), (C), (D), and (E).

[0040] In particular, the PPS-based compositions of the present invention preferably do not contain poly(etherimide) ("PEI") polymers; the expressions "poly(etherimide)" and / or "polymer (PEI)" mean repeating units (R) comprising at least 50 mol% of the total moles in the polymer, at least one aromatic ring, at least one imide group in itself and / or its amide acid form, and at least one ether group. PEI This refers to polymers containing repeating units (R). PEI ) may optionally further contain at least one amide group not included in the form of the imide group amide acid.

[0041] In addition to having a flame retardancy rating of V-0, the PPS-based composition preferably exhibits a fracture strain of more than 30% (measured at room temperature (23°C) according to ISO 527-2).

[0042] Considering a base composition (without pSiO) containing PPS polymer, PPSU polymer, and TPE, it was observed that the addition of epoxy-modified polysiloxane did not adversely affect the fracture strain of the resulting PPS-based composition.

[0043] Ingredient (A): Polyphenylene sulfide (PPS) polymer A PPS-based composition comprises at least one polyphenylene sulfide polymer, referred to throughout this specification as "PPS" or "PPS polymer."

[0044] In its broadest definition, PPS polymers can be produced from substituted and / or unsubstituted phenylene sulfide groups.

[0045] According to this specification, PPS polymers are defined as repeating units (R) represented by formula (1). PPS This refers to any polymer containing at least 50 mol% of (mol% is based on the total number of moles of repeating units in the PPS polymer): [ka] (In the formula, R is independently selected from the group consisting of halogens, C1-C12 alkyl groups, C7-C24 alkylaryl groups, C7-C24 aralkyl groups, C6-C24 arylene groups, C1-C12 alkoxy groups, and C6-C18 aryloxy groups, and i is independently 0 or an integer from 1 to 4).

[0046] According to equation (1), the repeating unit (R PPS The aromatic ring of ) may contain 1 to 4 radical groups R. If i is 0, the corresponding aromatic ring does not contain any groups R.

[0047] The PPS polymer preferably has repeating units represented by formula (1') (R PPS ), that is, any polymer containing at least 50 mol% of the repeating unit of equation (1) where i is 0: [ka]

[0048] According to one embodiment of the present invention, the PPS polymer contains repeating units (R) represented by formula (1) or (1') of the formula (1) and of the formula (1') PPS ) is the case. Mole percent is based on the total number of moles of repeating units in the PPS polymer.

[0049] The PPS polymer may or may not be acid-washed. In some embodiments, the PPS polymer is an acetic acid-washed PPS polymer.

[0050] According to one embodiment of the present invention, the PPS polymer has 100 mol% of repeating units represented by the repeating unit (R) of formula (1) or (1'). PPS ) is the PPS polymer. According to this embodiment, the PPS polymer is a repeating unit (R) represented by formula (1'). PPS ) becomes essentially.

[0051] Suitable PPS polymers are commercially available from Solvay Specialty Polymers USA, LLC under the trade name Ryton® PPS. In relation to this application, PPS products beginning with the prefix "QA," such as QA200N, under the Ryton® brand refer to acid-washed PPS.

[0052] The melt flow rate of PPS (at 316°C, with a load of 5 kg, in accordance with ASTM D1238, Procedure B) may be 50 to 400 g / 10 min, for example, 60 to 300 g / 10 min, or 70 to 200 g / 10 min. For example, Ryton® PPS QA220N and QA200N have melt flow rates of 160 g / 10 min and 100 g / 10 min, respectively. Ryton® PPS QC220N, QC210N, and QC200N have melt flow rates of 175 g / 10 min, 135 g / 10 min, and 100 g / 10 min, respectively.

[0053] The melt flow rate (MFR), also known as the melt flow index (MFI) as used herein, is used to characterize polymer melts. It is an indirect measure of molecular weight, meaning that a high MFR corresponds to a low molecular weight. At the same time, the melt flow rate is also a measure of the ability of the material melt to flow under pressure. The melt flow rate is inversely proportional to the viscosity of the polymer melt. When the MFI or MFR is low, the melt viscosity and melt flow resistance are high.

[0054] The PPS-based composition contains at least one PPS polymer in an amount of at least 45% by weight, at least 47% by weight, or at least 50% by weight, based on the total weight of the PPS-based composition.

[0055] The PPS-based composition contains at least one PPS polymer in an amount of up to 75 wt%, up to 70 wt%, up to 65 wt%, or up to 60 wt% based on the total weight of the PPS-based composition.

[0056] Preferably, the PPS-based composition contains at least one PPS polymer in an amount ranging from 45 to 75 wt% or 50 to 65 wt% based on the total weight of the PPS-based composition.

[0057] Component (B): polyphenylsulfone (PPSU) polymer The PPS-based composition contains at least one polyphenylsulfone (PPSU) polymer (hereinafter referred to as "PPSU" or "PPSU polymer").

[0058] As used herein, the PPSU polymer refers to a polymer containing at least 50 mol% of a repeating unit (RPPSU) represented by Formula (2):

Chemical formula

[0059] According to one embodiment of the present disclosure, at least 60 mol% (based on the total number of moles of repeating units in the PPSU polymer), at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, or at least 99 mol%, or all of the repeating units in the PPSU polymer are the repeating unit (R PPSU ) represented by Formula (2).

[0060] PPSU polymers can be prepared by known methods and are commercially available, in particular, from Solvay Specialty Polymers USA, LLC as RADEL® PPSU. Suitable PPSU polymers can be selected from, but are not limited to, Radel® R-5500NT, R-5700NT, R-5800NT, and R-5900NT.

[0061] The melt flow rate of PPSU polymer (at 365°C, under a load of 5 kg, in accordance with ASTM D1238) may be 5 to 40 g / 10 min, for example, 5 to 35 g / 10 min, 10 to 40 g / 10 min, 10 to 30 g / 10 min, 12 to 40 g / 10 min, 20 to 40 g / 10 min, or 10 to 35 g / 10 min. For example, Radel® PPSU R-5500NT, R-5700NT, R-5800NT, and R-5900NT have melt flow rates of 12 to 17 g / 10 min, 34 to 40 g / 10 min, 20 to 28 g / 10 min, and 26 to 36 g / 10 min, respectively.

[0062] The PPS-based composition contains at least 20% by weight, for example, at least 22% by weight, at least 25% by weight, at least 27% by weight, or at least 29% by weight, of the total weight of the PPS-based composition, in the amount of at least one PPSU polymer.

[0063] The PPS-based composition contains at least one PPSU polymer in an amount of up to 45% by weight, for example, up to 43% by weight, up to 40% by weight, or up to 38% by weight, based on the total weight of the PPS-based composition.

[0064] The PPS-based composition contains at least one PPSU polymer in an amount ranging from 20 to 45% by weight, for example, 22 to 43% by weight, 25 to 40% by weight, or 27 to 38% by weight, based on the total weight of the PPS-based composition.

[0065] Ingredient (C): Epoxy functional group-containing thermoplastic elastomer (TPE) The PPS-based composition contains at least one epoxy functional group-containing thermoplastic elastomer (hereinafter referred to as "TPE").

[0066] In relation to the present invention, "elastomer" is defined as a polymer-based material that exhibits (1) a low glass transition temperature (Tg), i.e., less than 25°C, and even less than 0°C, and (2) a low modulus of elasticity (Young's modulus), i.e., less than 200 MPa, and even less than 100 MPa.

[0067] The term "epoxy functional group" is used herein in accordance with its usual meaning; that is, it refers to a functional group containing an oxygen atom that is bonded by a single bond to two adjacent carbon atoms, thereby forming a three-membered epoxide ring.

[0068] The polymer backbone of TPE can be selected from an elastomer backbone containing polyethylene and its copolymers, such as ethylene-butene; ethylene-octene; polypropylene and its copolymers; polybutene; polyisoprene; ethylene-propylene-rubber (EPR); ethylene-propylene-diene monomer rubber (EPDM); ethylene-acrylate rubber; butadiene-acrylonitrile rubber, ethylene-acrylic acid (EAA), ethylene-vinyl acetate (EVA); acrylonitrile-butadiene-styrene rubber (ABS), block copolymer styrene-ethylene butadiene styrene (SEBS); block copolymer styrene-butadiene styrene (SBS); methacrylate-butadiene styrene (MBS) type core-shell elastomers, or a mixture of one or more of the above.

[0069] The TPE used in PPS-based compositions contains epoxy functional groups. Functionalization of the main chain can be achieved by copolymerization of epoxy functional group-containing monomers, or by grafting the polymer main chain with further epoxy functional group-containing components.

[0070] Specific examples of TPEs include poly(ethylene-co-glycidyl methacrylate) copolymer, poly(ethylene-co-methyl(meth)acrylate-co-glycidyl acrylate) copolymer, poly(ethylene-co-n-butyl acrylate-co-glycidyl acrylate) copolymer, and copolymers of styrene and glycidyl(meth)acrylate. Notable non-limiting examples of commercially available TPEs suitable for the heat transfer tubes of the present invention include, for example, Arkema (Bristol, PA, USA) Lotader® AX8900 and Lotader® AX8840, which are poly(ethylene-co-alkylacrylate-co-glycidylacrylate) terpolymer (containing structural units derived from 67 wt% ethylene, 25 wt% methyl acrylate, and 8 wt% glycidyl methacrylate) and poly(ethylene-co-glycidyl methacrylate) copolymer (containing structural units derived from 92 wt% ethylene and 8 wt% glycidyl methacrylate), respectively, or similarly, Sumitomo Chemical Co., Ltd.'s Igetabond® BF-E (containing structural units derived from 88 wt% ethylene and 12 wt% glycidyl methacrylate), which is a poly(ethylene-co-glycidyl methacrylate) copolymer. Another suitable example of a TPE is commercially available from Dow Inc. (Midland, MI, USA) under the trade name Paraloid® EXL2314, which is a core-shell type acrylate polymer consisting of a core made primarily of cross-linked poly(n-butyl acrylate) rubber and a shell made primarily of poly(methyl methacrylate)-poly(glycidyl methacrylate) copolymer.

[0071] Particularly suitable TPEs are selected from the group consisting of poly(ethylene-co-glycidyl methacrylate) copolymer, poly(ethylene-co-methyl(meth)acrylate-co-glycidyl acrylate) copolymer, poly(ethylene-co-n-butyl acrylate-co-glycidyl acrylate) copolymer, and copolymer of styrene and glycidyl(meth)acrylate, preferably selected from poly(ethylene-co-glycidyl methacrylate) copolymer and / or poly(ethylene-co-methyl(meth)acrylate-co-glycidyl acrylate) copolymer, and more preferably selected from poly(ethylene-co-glycidyl methacrylate) copolymer.

[0072] Favorable results were obtained with Igetabond® BF-E, a poly(ethylene-co-glycidyl methacrylate) copolymer (containing structural units derived from 88% by weight of ethylene and 12% by weight of glycidyl methacrylate), manufactured by Sumitomo Chemical Co., Ltd.

[0073] The PPS-based composition preferably includes TPE having a melt flow rate of less than 10 g / 10 min, for example, less than 7 g / 10 min, less than 6 g / 10 min, less than 5 g / 10 min, or less than 4 g / 10 min (ASTM D1238, 190°C, load 2.16 kg).

[0074] The PPS-based composition contains at least one TPE in an amount of at least 4.5% by weight, at least 5% by weight, at least 6% by weight, at least 7% by weight, or at least 8% by weight, based on the total weight of the PPS-based composition.

[0075] The PPS-based composition contains at least one TPE in an amount of up to 12% by weight, up to 11.5% by weight, up to 11% by weight, up to 10.5% by weight, or up to 10% by weight, based on the total weight of the PPS-based composition.

[0076] The PPS-based composition preferably contains at least one TPE in an amount ranging from 4.5 to 12% by weight, preferably 5 to 11%, 6 to 10%, or 7 to 10% by weight, based on the total weight of the PPS-based composition.

[0077] Component (D): Epoxy-modified polysiloxane (pSiO) The PPS-based composition contains at least one epoxy-modified polysiloxane.

[0078] In relation to the present invention, "polysiloxane" is defined as a silicone polymer compound containing siloxane oxygen-silicon bonds (Si-O-Si) in its main chain structure. Each Si atom in the siloxane bond typically has two organic groups usually selected from alkyl groups, vinyl groups, and / or phenyl groups. The two organic groups may be the same or different from each other.

[0079] Epoxy-modified polysiloxane (D) comprises at least one polysiloxane containing at least one epoxy functional group. The term "epoxy functional group" is used herein in its usual sense; that is, a functional group containing an oxygen atom bonded by a single bond to two adjacent carbon atoms, thereby forming a three-membered epoxide ring.

[0080] Epoxy-modified polysiloxanes (D) typically contain at least 70 mol% of siloxane repeating units (Rs) represented by general formula (3), based on the total number of moles of repeating units in the polysiloxane (D): [ka] (In formula (3), R1 and R2 are independently a C1-C3 alkyl group and / or a phenyl group, and n is an integer between 2 and 100, or 2 and 70, or 2 and 60).

[0081] The epoxy-modified polysiloxane (D) preferably contains at least 80 mol%, at least 85 mol%, at least 90 mol%, or at least 93 mol% of the repeating units (Rs) of formula (3), where the mol% is based on the total number of moles of repeating units in the polysiloxane (D). Substantially all repeating units of the polysiloxane (D) may consist of the same siloxane repeating units (Rs) represented by formula (3).

[0082] Preferably, each of R1 and R2 in formula (3) is independently selected from a methyl group, an ethyl group, and / or a phenyl group, and more preferably independently selected from a methyl group and a phenyl group.

[0083] In particular, epoxy-modified polysiloxane (D) contains at least 70 mol% of the following formulas (3a), (3b), or (3c), based on the total number of moles of repeating units in the polysiloxane (D): [ka] It contains a siloxane repeating unit (Rs) represented by one of the following: More preferably, the system contains a siloxane repeating unit (Rs) represented by formula (3a).

[0084] The epoxy-modified polysiloxane (D) preferably contains at least 80 mol%, at least 85 mol%, at least 90 mol%, or at least 93 mol% of repeating units (Rs) represented by formula (3), (3a), (3b), or (3c), where the mol% is based on the total number of moles of repeating units in the polysiloxane (D). Substantially all of the repeating units of the polysiloxane (D) may consist of the same siloxane repeating units (Rs) represented by formula (3a), (3b), or (3c), preferably the units (Rs) represented by formula (3a) or (3c), more preferably the units (Rs) represented by formula (3a).

[0085] Particularly suitable epoxy-modified polysiloxanes (D) are poly(dimethylsiloxanes) (hereinafter sometimes referred to as "PDMS") containing at least 80 mol%, at least 85 mol%, at least 90 mol%, or at least 93 mol% of siloxane repeating units (Rs) represented by formula (3a), where the mol% is based on the total number of moles of repeating units in the polysiloxane (D).

[0086] If the epoxy-modified polysiloxane (D) is a copolymer containing one or more additional units different from the siloxane repeating units (Rs), the epoxy-modified polysiloxane (D) preferably contains up to 20 mol%, up to 15 mol%, up to 10 mol%, or up to 7 mol%, of the other units different from the siloxane repeating units (Rs), where the mol% is based on the total number of moles of units in the polysiloxane (D).

[0087] The epoxy-modified polysiloxane (D), preferably epoxy-modified PDMS, may be a single-ended functional silicone polymer, a double-ended functional polysiloxane, or a polyfunctional epoxy-modified polysiloxane having at least one terminal functional group and / or a pendant epoxy functional group. That is, the epoxy-modified polysiloxane (D) may have one epoxy functional group at only one end, one epoxy functional group at each end, at least one epoxy functional group on one or more side chains, or any combination thereof.

[0088] When the epoxy-modified polysiloxane (D) has one or more pendant epoxy functional groups, the polysiloxane (D) is composed of one or more epoxy-modified siloxane units (R) represented by general formula (4) or (5). EM It may also include: [ka] (Here, In formulas (4) and (5), R2 is a C1-C3 alkyl group or a phenyl group; • R3 in equations (4) and (5) is given by equation (6): -(CH2) k -O-CH2- (6) It is a linking group represented by, In the formula, k is an integer between 1 and 10, preferably between 2 and 8, more preferably between 3 and 6, and most preferably between 3; (In equations (4) and (5), m varies between 1 and 10, or between 1 and 7, or between 1 and 6).

[0089] In the unit (REM) of formula (4) or (5), R2 is preferably a methyl group or a phenyl group, and more preferably a methyl group.

[0090] In the linking group R3 represented by formula (6), -(CH2) k - The first carbon atom of the group is the unit (R EM The carbon atoms in the main chain Si in s) are covalently bonded, and the carbon atoms of the -O-CH2- group are covalently bonded to the pendant epoxy functional group.

[0091] In formulas (4) and (5), R3 is preferably formula (6a): -(CH2)3-O-CH2- (6a) It is represented as follows.

[0092] Epoxy-modified polysiloxane (D) contains only one epoxy-modified siloxane unit of formula (4) or (5) (R) in the polymer chain. EM It may contain s). Alternatively, the epoxy-modified polysiloxane (D) may contain two or more epoxy-modified siloxane units of formula (4) or (5) (R EM s) may be included, and these units may be continuous with each other (i.e., may form an epoxy-modified polysiloxane block), or may be randomly arranged in the main chain of epoxy-modified polysiloxane (D). Two or more epoxy-modified siloxane units (R EM When s) is used, those epoxy-modified siloxane units (R EM s) has the same formula represented by formula (4) or (5).

[0093] Epoxy-modified polysiloxane (D) contains at least one epoxy-modified siloxane unit (R EM In the case of a copolymer containing s) and siloxane repeating units (Rs), the epoxy-modified polysiloxane (D) preferably comprises up to 20 mol%, up to 15 mol%, up to 10 mol%, or up to 7 mol% of units (Rs). EM s) is included, and the mol% is the unit (R) in polysiloxane (D). EM This is based on the total number of moles of (s) and (Rs). Preferably, in such embodiments, the epoxy-modified polysiloxane (D) copolymer is based on the unit (R EM It consists only of (s) and (Rs).

[0094] If the epoxy-modified polysiloxane (D) contains at least one terminal epoxy functional group, preferably two terminal epoxy functional groups, the epoxy-modified polysiloxane (D) may contain one epoxy functional group at only one end of the polymer chain (single-end epoxy functionalization), or it may contain epoxy functional groups at each of the two ends of the polymer chain (double-end epoxy functionalization).

[0095] One or both terminal epoxy functional groups in polysiloxane (D) can be represented by at least one of the following formulas (7) and (8): [ka] (In the formula, R3 is given by formula (6):-(CH2) k Represented as -O-CH2-, In the formula, k is an integer between 1 and 10, preferably between 2 and 8, more preferably between 3 and 6, and most preferably between 3.

[0096] If the epoxy-modified polysiloxane (D) has two terminal epoxy functional groups, both terminal epoxy functional groups have the same formula selected from formulas (7) and (8) described herein, preferably the same formula (7).

[0097] If epoxy-modified polysiloxane (D) has only one terminal epoxy functional group, the other terminal group is: -(CH2) k -O-CH3 or -(CH2) k It can be represented as -O-CH2-CH3, In the formula, k is an integer between 1 and 10, preferably between 2 and 8, more preferably between 3 and 6, and most preferably between 3.

[0098] In such cases, epoxy-modified polysiloxane (D) is given by formula (9) or (10): [ka] It can be represented by at least one of the following: In formulas (9) and (10), R1 and R2 are independently a C1-C3 alkyl group and / or a phenyl group; • R3 in equations (9) and (10) is given by equation (6): -(CH2) k -O-CH2- (6) It is a linking group represented by, In the formula, k is an integer between 1 and 10, preferably between 2 and 8, more preferably between 3 and 6, and most preferably between 3; n is an integer between 2 and 100, or between 2 and 70, or between 2 and 60.

[0099] In formulas (9) and (10), R1 and R2 are preferably independently selected from a methyl group, an ethyl group, and / or a phenyl group, and more preferably independently selected from a methyl group and a phenyl group.

[0100] In formulas (9) and (10), R3 is preferably formula (6a): -(CH2)3-O-CH2- (6a) It is represented as follows.

[0101] In particularly suitable embodiments, the epoxy-modified polysiloxane (D) is a poly(dimethylsiloxane) (PDMS) having one or more pendant and / or terminal epoxy functional groups represented by at least one of formulas (7) and (8).

[0102] In particularly suitable embodiments, the epoxy-modified polysiloxane (D) may be a poly(dimethylsiloxane) or poly(phenylmethylsiloxane) having two terminal epoxy functional groups represented by at least one of formulas (7) and (8) (double-ended functionalization).

[0103] In more specific and suitable embodiments, the epoxy-modified polysiloxane (D) may be a poly(dimethylsiloxane) "PDMS" having two terminal epoxy functional groups represented by the same formula selected from formulas (7) and (8), for example, represented by formula (11) or (12) (double-ended functionalization): [ka] (In the formula, n is an integer between 2 and 100, preferably between 2 and 70, and more preferably between 2 and 60).

[0104] In particular, favorable results were obtained with the double-ended epoxy-modified PDMS represented by formula (11).

[0105] In another suitable embodiment, the epoxy-modified polysiloxane (D) may be a poly(dimethylsiloxane) having a side-chain epoxy functional group represented by formula (13): [ka] (In the formula, n is an integer between 2 and 100, or between 2 and 70, or between 2 and 60. m is a number such that the ratio of m / (m+n) is at most 1 / 3, at most 0.25, at most 0.2, at most 0.15, or at most 0.1, and / or at least 0.01, or at least 0.02.

[0106] In equation (13), m is preferably a number such that the ratio of m / (m+n) is between 0.01 and 0.1, or between 0.02 and 0.07.

[0107] It should be understood that the epoxy-modified polysiloxane (D) may also be a polyfunctional epoxy-modified silicone having both terminal epoxy functional groups and pendant epoxy functional groups. In such cases, the polyfunctional epoxy-modified polysiloxane (D) may have at least one epoxy-modified siloxane unit (R EM s) comprises a siloxane repeating unit (R) and at least one terminal group represented by formula (7) or (8).

[0108] Commercially available epoxy-modified polysiloxanes suitable for component (D) are available from Shin-Etsu Chemical Co., Ltd. and Gelest.

[0109] Examples of epoxy-modified PDMS represented by formula (11), which has epoxy groups at both ends, include Shin-Etsu Chemical Co., Ltd.'s KF-105 (molecular weight 490 g / mol; viscosity 15 cSt); X-22-163A (molecular weight 1000 g / mol; viscosity 30 cSt); X-22-163B (molecular weight 1200 g / mol; viscosity 60 cSt); X-22-163C (molecular weight 2700 g / mol; viscosity 120 cSt); and Gelest's DMS-E9 (molecular weight 363 g / mol; viscosity 8-11 cSt; 5.5 eq / kg epoxy); DMS-E11 (molecular weight 500-600 g / mol; viscosity 12-18 cSt; 1.9-2.2 eq / kg epoxy); DMS-E9 (molecular weight 363 g / mol; viscosity 8-11 cSt; 5.5 eq / kg epoxy). Epoxy); DMS-E12 (molecular weight 1000-1400 g / mol; viscosity 20-35 cSt; 1.6-1.9 eq / kg epoxy); DMS-E21 (molecular weight 4500-5000 g / mol; viscosity 100-140 cSt; 0.35-0.45 eq / kg epoxy).

[0110] An example of an epoxy-modified PDMS represented by formula (12), in which both ends are alicyclic epoxy silicone, is Gelest's DMS-EC13 (molecular weight 900-1000 g / mol; viscosity 25-35 cSt; 1.9-2.0 eq / kg epoxy), which is an epoxycyclohexylethyl-terminated PDMS.

[0111] Dimethylsiloxane repeating units (Rs) and epoxy-modified siloxane units (R EM An example of an epoxy-modified PDMS represented by formula (13), which is a copolymer consisting of s), is ECM-227 ([2-3% (epoxycyclohexylethyl)methylsiloxane]-dimethylsiloxane copolymer) available from Gelest. Another example of an epoxy-end-type PDMS with epoxy side chains is X-22-9002 (viscosity 900 cSt) available from Shin-Etsu Chemical Co., Ltd.

[0112] The epoxy-modified polysiloxane (D) should have a weight-average molecular weight of at least 200 g / mol, at least 300 g / mol, at least 350 g / mol, or at least 400 g / mol, as determined by gel permeation chromatography.

[0113] The epoxy-modified polysiloxane (D) should have a molecular weight of up to 5000 g / mol, up to 4800 g / mol, up to 4500 g / mol, up to 4000 g / mol, up to 3000 g / mol, up to 2000 g / mol, up to 1200 g / mol, or up to 1000 g / mol, as determined by gel permeation chromatography.

[0114] Preferably, the epoxy-modified polysiloxane (D) has a molecular weight of 200 g / mol to 5000 g / mol, 300 g / mol to 4000 g / mol, or 350 g / mol to 3000 g / mol, as determined by gel permeation chromatography.

[0115] The epoxy-modified polysiloxane (D) should have a viscosity of at least 8 cSt, at least 10 cSt, at least 11 cSt, or at least 12 cSt.

[0116] The epoxy-modified polysiloxane (D) should have a viscosity of up to 150 cSt, up to 120 cSt, or up to 100 cSt.

[0117] The PPS-based composition of the present invention contains at least 0.5% by weight, or at least 0.6% by weight, for example, at least 0.7% by weight, of at least one epoxy-modified polysiloxane (D) based on the total weight of the PPS-based composition.

[0118] The PPS-based composition of the present invention may contain at least one epoxy-modified polysiloxane (D) in an amount of 6% by weight or less, for example, less than 5% by weight, less than 4.5% by weight, less than 4% by weight, less than 3.5% by weight, less than 3% by weight, less than 2.5% by weight, or less than 2% by weight, based on the total weight of the PPS-based composition.

[0119] Preferably, the PPS-based composition of the present invention may contain at least one epoxy-modified polysiloxane (D) in an amount ranging from 0.5 to 5% by weight, for example, 0.6 to 4% by weight, 0.7 to 3% by weight, 0.8 to 2.5% by weight, or 1 to 2% by weight, based on the total weight of the PPS-based composition.

[0120] Optional components (E): Additives The PPS-based composition according to the present invention may further contain at least one additive (E), such as antioxidants, light stabilizers, ultraviolet stabilizers, heat stabilizers, processing aids, nucleating agents, lubricants, flame retardants, smoke inhibitors, antistatic agents, antiblocking agents, mold release agents, and colorants (e.g., pigments, dyes). Preferably, flame retardants are excluded from this list.

[0121] An optional additive (E) is neither component (C) nor component (D).

[0122] Additive (E), which is different from components (A), (B), (C), and (D), may be added to and blended into the PPS-based composition according to the present invention, to the extent that it does not impair the effects of the present invention.

[0123] If present, one or more additives (E) are typically included in the PPS-based composition in amounts of up to 10% by weight, more specifically up to 8% by weight, or up to 5% by weight, relative to the total weight of the PPS-based composition. The additives are usually present in amounts of at least 0.5% by weight, for example, at least 0.8% by weight, or at least 1% by weight, relative to the total weight of the PPS-based composition.

[0124] One or more colorants, such as dyes and / or pigments, may be particularly desirable additives (E) in the PPS composition to provide white, black, or colored articles. The pigments may be black pigments such as carbon black or nigrosine, white pigments such as zinc oxide, zinc sulfide, lithopone, antimony white, and titanium dioxide (rutile or anatase type, preferably rutile type), and / or colored pigments. The pigments are usually present in an amount of 0 to 6% by weight, preferably 0.05 to 5% by weight, and particularly 0.1 to 3% by weight, based on the total weight of the PPS composition.

[0125] A coloring additive (E) containing carbon black powder may be included in the PPS-based composition. The preferred concentration of carbon black in the PPS-based composition can be 0.05% to 3% by weight, or 0.1% to 1% by weight, or 0.2% to 0.5% by weight, based on the total weight of the PPS-based composition.

[0126] Such carbon black powder can be added to PPS-based compositions in the form of a masterbatch further containing a polymer carrier. Such a masterbatch is commonly referred to as a "carbon black concentrate." The carbon black concentrate may contain 5-70% by weight, or 10-40% by weight, or 10-35% by weight of carbon black, based on the total weight of the carbon black concentrate. Carbon black concentrates with a pH of 1 pph to 10 pph can be added to PPS-based compositions, where "pph" refers to parts per 100 parts of the total weight of the PPS-based composition.

[0127] The lubricant can be selected from linear low-density polyethylene, calcium stearate or magnesium stearate, or sodium montanoate, or any combination thereof, preferably calcium stearate or magnesium stearate, more preferably calcium stearate. The preferred concentration of the lubricant in the PPS-based composition can be 0.05% to 3% by weight, or 0.1% to 1% by weight, or 0.2% to 0.8% by weight, based on the total weight of the PPS-based composition.

[0128] One or more antioxidants may also be desirable additives (E) in the PPS-based composition. Antioxidants can improve the thermal and photostability of the PPS-based composition. For example, antioxidants that are heat stabilizers can improve the thermal stability of the PPS-based composition during manufacturing (or in high-temperature application settings) by enabling the polymer to be processed at high temperatures while helping to prevent polymer degradation. Desired antioxidants include, but are not limited to, copper salts (e.g., CuO and Cu2O), alkali metal halides (including, but not limited to, combinations of alkali metal halides such as CuI / KI, CuI, KI, and KBr), hindered phenols, hindered amine photostabilizers ("HALS") (e.g., tertiary amine photostabilizers), and organic or inorganic phosphorus-containing stabilizers (e.g., sodium hypophosphite or manganese hypophosphite).

[0129] Examples of release agents as additive (E) include, but are not limited to, metal stearate, stearyl stearate, pentaerythritol tetrastearate, beeswax, montan wax, paraffin wax, or any combination thereof.

[0130] Since the PPS-based compositions of the present invention, comprising components (A), (B), (C), and (D), are flame-retardant, it is generally not necessary to add further flame retardants to such compositions.

[0131] However, if the PPS-based composition contains at least one flame retardant as additive (E), the flame retardant can be selected from the group consisting of phosphorus-based flame retardants, halogen-based flame retardants, inorganic flame retardants, and any combination thereof. In such cases, the flame retardant added as additive (E) to the PPS-based composition is preferably a halogen-free flame retardant. The halogen-free flame retardant can be an organophosphorus compound selected from the group consisting of phosphinates, diphosphinates, and their condensation products.

[0132] The flame-retardant PPS-based composition of the present invention may not contain phosphorus-based flame retardants.

[0133] The flame-retardant PPS-based composition of the present invention may not contain halogen-based flame retardants.

[0134] The flame-retardant PPS-based composition of the present invention may not contain an inorganic flame retardant.

[0135] More preferably, a flame retardant is excluded from additive (E). That is, the flame-retardant PPS-based composition of the present invention, which contains components (A) to (D) and optional components (E) to (F), does not contain a flame retardant.

[0136] Optional component (F): Other resins The PPS-based composition according to the present invention may be blended with an optional resin (F) different from components (A), (B), (C), (D), and optional (E), as long as the effects of the present invention are not impaired.

[0137] Other specific examples of resin (F) include, but are not limited to, polyamide, polyamide elastomer, polybutylene terephthalate, polyethylene terephthalate, polyester elastomer, polyetherimide, polyketone, liquid crystal polymer, polyetherketone, polyetheretherketone, ethylene-tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene-perfluoro(alkyl vinyl ether) copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), ethylene-tetrafluoroethylene-hexafluoropropylene copolymer, polyvinylidene fluoride (PVDF), and polychlorotrifluoroethylene (PCTFE). The amount of such resin (F) added is preferably less than 15% by weight, preferably less than 10% by weight, more preferably less than 8% by weight, even more preferably less than 6% by weight, even more preferably less than 4% by weight, or less than 2% by weight, or less than 1% by weight, where the weight percentage is based on the total weight of the PPS-based composition.

[0138] In addition, as a lower limit, it is preferable that the PPS-based composition contains no resin (F) at all, that is, the content of resin (F) different from components (A), (B), (C), (D), and optionally (E) is 0% by weight.

[0139] The PPS-based composition of the present invention preferably does not contain poly(etherimide) (PEI) polymer. The expressions "poly(etherimide)" and / or "polyetherimide" refer to a polymer containing at least 50 mol% of the total moles in the polymer, repeating units (R) comprising at least one aromatic ring, at least one imide group in itself and / or its amide acid form, and at least one ether group. PEI This refers to polymers containing repeating units (R). PEI ) may optionally further contain at least one amide group not included in the form of the imide group amide acid.

[0140] Method for producing PPS-based compositions The PPS-based composition according to the present invention can be manufactured using methods well known in the art.

[0141] For example, a PPS-based composition is produced by melt-blending components (A), (B), (C), and (D), as well as optional components (E) and / or (F). Any suitable melt-blending method can be used to mix the components of the composition of the present invention. For example, all components can be fed into a melt mixer such as a single-screw or twin-screw extruder, a stirrer, a single-screw or twin-screw kneader, a Brabender mixer, or a Banbury mixer. The components may all be added to the melt mixer at once, or they may be added gradually in batches. If the components are added gradually in batches, some of the components may be added first and then melt-blended with the remaining components to be added until a well-mixed PPS-based composition is obtained.

[0142] The temperature used for melt blending can be between 320 and 350°C.

[0143] All embodiments described herein in relation to the PPS-based compositions of the present invention are also applicable herein with necessary modifications.

[0144] Use of epoxy-modified polysiloxane (D) to improve the flame retardancy of a V-1 grade PPS composition containing components (A), (B), and (C). Further embodiments of the present invention include: • Component (A): at least one polyphenylene sulfide polymer ("PPS") • Component (B): at least one polyphenylsulfone polymer ("PPSU"), and • Component (C): Thermoplastic elastomer containing at least one epoxy functional group ("TPE") A method for improving the flame retardancy of a V-1 grade PPS-based composition containing, A certain amount of component (D): epoxy-modified polysiloxane is added to a V-1 grade PPS-based composition. (A) 45-75% by weight of at least one PPS polymer, (B) 20-45% by weight of at least one PPSU polymer, (C)4.5-12% by weight of epoxy functional group-containing thermoplastic elastomer (TPE), (D) 0.5-5% by weight of epoxy-modified polysiloxane, This includes obtaining a V-0 grade PPS-based composition containing [the specified substance]. The aforementioned weight percentage is based on the total weight of the V-0 grade PPS-based composition. The total amount of components (A), (B), (C), and (D) is 100% by weight or less, based on the total weight of the V-0 grade PPS composition. The flame retardancy grades V-0 and V-1 are measured based on UL94V(2013) using test specimens with a thickness of 1.0 mm or less, preferably 0.8 mm. It is a method.

[0145] Such methods are applicable to any embodiment of the PPS-based composition of the present invention and any of the various embodiments of components (A) to (D) described herein.

[0146] In a particular embodiment, • Component (A): At least one type of PPS polymer, • Ingredient (B): At least one type of PPSU polymer, • Component (C): Thermoplastic elastomer containing at least one epoxy functional group ("TPE") • Optional component (E): at least one additive (E), and • Optional component (F): Another resin (F) different from components (A), (B), (C), (D), and (E). In order to improve the flame retardancy of a V-1 grade PPS-based composition containing, The method involves adding a certain amount of component (D): at least one epoxy-modified polysiloxane to a V-1 grade PPS-based composition. (A): At least one PPS polymer in an amount of 45-75% by weight, or 47-70% by weight, or 50-65% by weight, (B): At least one PPSU polymer in an amount of 20-45% by weight, or 22-43% by weight, or 23-40% by weight, or 27-38% by weight, (C): At least one type of TPE in an amount of 4.5-12% by weight, or 5-11% by weight, or 6-10% by weight, (D): 0.5-5% by weight, or 0.6-4% by weight, or 0.7-3% by weight, or 1-2% by weight of at least one epoxy-modified polysiloxane, • At least one optional additive (E) in a maximum of 10% by weight, • Less than 15% by weight of at least one other optional resin (F) different from components (A), (B), (C), (D), and (E), This includes obtaining a V-0 grade PPS-based composition consisting of the following: The aforementioned weight percentage is based on the total weight of the V-0 grade PPS-based composition. The total amount of components (A), (B), (C), (D), (E), and (F) is 100% by weight or less based on the total weight of the V-0 grade PPS composition. The flame retardancy grades V-0 and V-1 are measured based on UL94V(2013) using test specimens with a thickness of 1.0 mm or less, preferably 0.8 mm.

[0147] All the embodiments described above and the various embodiments of components (A) to (F) in relation to the PPS-based compositions of the present invention are also applicable herewith necessary modifications.

[0148] Use of PPS-based compositions for manufacturing articles Another aspect of the present invention provides the use of a PPS-based composition for manufacturing articles.

[0149] Such use is applicable to any embodiment of the PPS-based composition of the present invention, as well as to any of the various embodiments of components (A) to (D) and optional components (E) and (F) described herein.

[0150] The PPS-based compositions described in detail above can be processed to obtain molded articles by conventional melting techniques, particularly extrusion molding, injection molding, overmolding, and / or compression molding, preferably by extrusion molding and / or overmolding.

[0151] The temperature used for molding, preferably extrusion molding, can be 320-340°C.

[0152] Goods The present invention further relates to articles, preferably molded articles, that contain or are manufactured therefrom, the PPS-based composition of the present invention.

[0153] All embodiments described herein in relation to the PPS-based compositions of the present invention and various components (A) to (F) are also applicable herein with necessary modifications.

[0154] Advantageously, the articles of the present invention have a V-0 grade, as measured by a test specimen with a thickness of 1.0 mm or less, preferably 0.8 mm, based on the UL94V(2013) standard test.

[0155] Articles of the present invention can be formed by extrusion molding, injection molding, overmolding, and / or compression molding, preferably by extrusion molding or overmolding.

[0156] The molded articles of the present invention are preferably flame-retardant extruded articles, overmolded coatings, multilayer articles, and / or thin-walled molded articles. "Thin-walled" molded articles have a wall thickness of up to 2 mm, up to 1.5 mm, or up to 1 mm, and preferably 0.8 mm or more.

[0157] The article may be substantially two-dimensional, for example, in the form of a part such as a film, sheath, or sheet, where one dimension (thickness or height) is significantly smaller than the other two characteristic dimensions (width and length).

[0158] Alternatively, the article may be provided as a three-dimensional part that extends substantially into three dimensions of space, for example, in the form of a complexly shaped part having concave or convex portions, which may include undercuts or inserts.

[0159] Molded products obtained by extrusion molding include round bars, square bars, sheets, films, tubes, and pipes. More specific applications include electrical insulation materials for water heater motors, air conditioner motors, and drive motors; film capacitors, speaker diaphragms, magnetic tapes for recording; printed circuit board materials; peripheral components for printed circuit boards; seamless belts; semiconductor packages; semiconductor transport trays; process / release films; protective films; automotive film sensors; wire cable insulation tapes for lithium-ion batteries; insulating washers for lithium-ion batteries; heat transfer tubes for eV batteries; piping for chemicals; piping for automotive fuels; hot water piping for urban air mobility; cooling water piping; piping for chemicals and fuels; hot water piping; chemical piping for chemical plants; piping for ultrapure water and ultrapure solvents; automotive piping; piping for CFCs and supercritical carbon dioxide refrigerants; and workpiece holding rings for polishing equipment. In addition, examples include busbars, busbar holders, wire harnesses, and control devices for hybrid vehicles, electric vehicles, fuel cell vehicles, and railways; coated molded parts for motor coil windings in power generation equipment; bobbins, slot liners, and slot wedges for electric motors and generators; heat-resistant wires and cables for home appliances; flat cables used for wiring in automobiles, etc.; wires such as magnet wires, insulated wires / cables; signal converters for communications, transmission, high frequency, acoustics, measurement, etc.; and coated molded parts for windings of automotive transformers.

[0160] Applications of molded products obtained by injection molding include generators, electric motors, transformers, current transformers, voltage regulators, rectifiers, inverters, relays, power contacts, switches, circuit breakers, knife switches, and other poles. Other applications include rods, electrical component cabinets, sensors, LED lamps, connectors, sockets, resistors, relay cases, small switches, bobbins such as coil bobbins, capacitors, variable capacitor cases, optical pickups, oscillators, various terminal boards, converters, plugs, printed circuit boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystal displays, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, and computer-related components; electrical components such as VTR components, TV components, irons, hair dryers, rice cooker components, microwave oven components, audio components, audio equipment components (audio equipment, laserdiscs (registered trademark), and compact discs, etc.), lighting components, refrigerator components, air conditioner components, and typewriter components and word processor components, representing household / office electrical product components. Typical examples include office computer parts, telephone parts, facsimile parts, photocopier parts, cleaning jigs, motor parts, lighters, typewriters, and more.Mechanical parts: Microscopes, binoculars, cameras, watches, other optical instruments and precision machinery parts; alternator terminals, alternator connectors, IC regulators, potentiometer bases for dimmers, exhaust gas valves, fuel-related parts, exhaust systems, various pipes and ducts for intake systems, turbo ducts, intake nozzle snorkels, intake manifolds, fuel pumps, engine coolant joints, carburetor bodies, carburetor spacers, exhaust gas sensors, coolant sensors, oil temperature sensors, brake pad wear sensors, throttle position sensors, crankshaft position sensors, airflow meters, brake pad wear sensors, thermostat bases for air conditioners, heater hot air flow control valves, radiator motor brackets Examples include seat holders, water pump impellers, turbine vanes, wiper motor related parts, distributors, starter switches, starter relays, transmission wire harnesses, window washer nozzles, air conditioning panel switchboards, fuel-related solenoid valve coils, fuse connectors, horn terminals, electrical component insulating plates, stepper motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, crash pads, insulating locks, ignition system cases, and other automotive and vehicle-related parts; mobile phones, smartphones, laptops, tablet computers, video cameras, hybrid vehicles, and gaskets for secondary batteries can also be examples.

[0161] Preferred molded products include, but are not limited to, tubular members such as heat transfer tubes for eV batteries, busbars such as electric busbars, bobbins such as coil bobbins, slot liners, slot wedges, coated wires or cables such as magnet wires, and / or power modules.

[0162] Slot liners are components of electric machinery such as electric motors and generators, providing an electrical insulation barrier between the electric windings and the stator. These components are cut from a film and molded to fit within the slots of the motor or generator.

[0163] A slot wedge is a slot closure used to hold the stator windings within the slots.

[0164] The bobbin may be a support for a coil or electrical winding.

[0165] In the case of sheathed wires and cables, PPS-based compositions can be used to form a coating around conductive wires or cables for protective and sheathing purposes. The PPS-based composition can be extruded around the conductive wire or cable using a sheathing apparatus to form a protective coating on the outer surface of the wire / cable. For example, magnet wires usable in electric motors are generally conductive wires (preferably made of copper) covered with a polymer sheath. Such polymer coatings can be manufactured from flame-retardant PPS-based compositions.

[0166] Electric busbars are commonly used in electric motors and eV power electronics. Preferably, they include a metal rod overmolded with a thermoplastic resin that provides electrical insulation and scratch resistance. In such cases, the metal rod is overmolded with a flame-retardant PPS-based composition to form the busbar.

[0167] Power modules provide a physical housing for multiple power components. Such physical housings can be manufactured from flame-retardant PPS-based compositions. Power modules are used in power conversion equipment such as industrial motor drives, embedded motor drives, uninterruptible power supplies, AC-DC power supplies, and welding machine power supplies.

[0168] In particular, the PPS-based composition of the present invention achieves an excellent V-0 flame retardancy rating and also exhibits good mechanical properties such as elongation at break, making it suitable for the manufacture of hollow tubular members.

[0169] Tubular members that can be used to transport liquids or gases, and in a particular embodiment to transport cooling fluids, can be formed from PPS-based compositions. For example, tubular members including tubes, hoses, pipes, and conduits can be formed from PPS-based compositions. In one embodiment, for example, PPS-based compositions can be used to form extruded hollow members.

[0170] Therefore, the article of the present invention may contain or consist of the PPS-based composition detailed above. Such a tube is preferably a heat transfer tube.

[0171] Advantageously, the tube of the present invention, preferably the heat transfer tube, has a V-0 rating as determined according to the UL94V (2013) standard when measured on a test specimen with a thickness of 0.8 mm.

[0172] The tubular member of the present invention, preferably a heat transfer tube, can be manufactured using any suitable method known in the art. The tube of the present invention, preferably a heat transfer tube, is typically manufactured by extrusion. It is preferable that the entire length of the tube is extrudeable and / or that it is extruded in a single extrusion process.

[0173] The tubular member of the present invention, preferably a heat transfer tube, is preferably having a substantially constant cross-section along its entire length. The tubular member (heat transfer tube) preferably has a circular cross-section.

[0174] The tubular member of the present invention, preferably a heat transfer tube, is hollow so that a fluid can flow through it. When the tubular member is a hollow heat transfer tube, the fluid is a heat transfer fluid.

[0175] Preferably, the hollow heat transfer tube of the present invention has an inner surface layer that is in direct contact with the heat transfer fluid. This inner surface layer is preferably manufactured from the PPS-based composition detailed above.

[0176] In a preferred embodiment, the hollow tubular member of the present invention, preferably the hollow heat transfer tube, is manufactured entirely from the flame-retardant PPS-based composition detailed above.

[0177] In another embodiment, the tubular member containing the PPS-based composition may be a multilayer tubular member. The multilayer tubular member may contain two, four, or more different layers. The PPS-based composition can be incorporated into one or more layers of the multilayer tubular member, for example, an inner layer, an outer layer, and / or one or more intermediate layers sandwiched between the inner and outer layers, preferably an inner layer.

[0178] For example, at least the inner layer includes a PPS-based composition that exhibits suitable mechanical properties over a wide temperature range and is substantially inert to the fluid carried within or flowing through the tubular member. In such a case, the outer layer or an optional intermediate layer may include the same or a different PPS-based composition as the inner layer.

[0179] Alternatively, if at least one layer is manufactured from a PPS-based composition, the other layers of the multilayer tubular member may be formed from different materials. For example, in one embodiment, the intermediate layer may be formed from a fiber-reinforced material such as a fiber-reinforced resin composite. For example, a polymer woven mat can be used to form an intermediate layer that has high resistance to mechanical attack.

[0180] When manufacturing a layer from a PPS-based composition, the thickness of the layer may typically be in the range of 0.7 to 5.0 mm, 0.8 to 5.0 mm, or even 1.0 to 5.0 mm. Alternatively, the thickness of the layer may be in the range of 0.7 to 2 mm, 0.8 to 1.5 mm, or even 0.8 to 1 mm.

[0181] Multilayer tubular members can be manufactured by conventional methods such as co-extrusion, dry lamination, sandwich lamination, co-extrusion coating, preferably co-extrusion or co-extrusion coating. For example, in the formation of a two-layer tubular member, a PPS-based composition and another polymer composition can be supplied separately to two different extruders. The separate extruded melts from these two extruders can then be introduced into a single die under pressure. While generating two different tubular melt flows, these melt flows can be combined in the die such that the melt flow of the PPS-based composition forms the inner layer and the melt flow of the different polymer composition forms the outer layer, and the combined melt flow can be co-extruded from the die to manufacture a two-layer tubular member.

[0182] Naturally, any known tubing method, including blow molding, can be employed. For example, in one embodiment, one or more layers of a multilayer tubular member can be formed from a continuous tape, such as a fiber-reinforced tape or ribbon formed by a pultrusion method. The tape can be wound to form the layers of the tubular member or multilayer tubular member, according to known practices widely known in the art.

[0183] If the tubular component is a heat transfer tube used in a thermal management system, the dimensions of the tube are not limited and are determined by the dimensions of the thermal management system.

[0184] The tubular member, preferably a heat transfer tube, of the present invention may have a diameter in the range of 5 to 50 mm, and more particularly in the range of 5 to 30 mm. The wall thickness of the tubular member, preferably a heat transfer tube, may typically be in the range of 0.7 to 5.0 mm, 0.8 to 5.0 mm, and more particularly in the range of 1.0 to 5.0 mm. Alternatively, the wall thickness of the tubular member, preferably a heat transfer tube, may typically be in the range of 0.8 to 2 mm, 0.8 to 1.5 mm, and more particularly in the range of 0.8 to 1 mm. The tubular member, preferably a heat transfer tube, of the present invention may have a length from 10 cm to several meters, for example, up to 2 m.

[0185] Use of items Another aspect of the present invention is a thermal management system comprising heat transfer tubes according to the present invention. The thermal management system further comprises a heat transfer fluid. The heat transfer fluid is contained within the heat transfer tubes. Preferably, the heat transfer fluid passes through (flows through) the inside of the heat transfer tubes. The heat transfer fluid can be selected from the group consisting of water, water / ethylene glycol mixtures, chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HFCs), and (per)fluoropolyethers (PFPEs). In a preferred embodiment of the present invention, the heat transfer fluid is selected from the group consisting of water or water / ethylene glycol mixtures. In a particular embodiment, the heat transfer fluid can be selected from the group consisting of chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HFCs), and (per)fluoropolyethers (PFPEs). The thermal management system according to claim 8 further comprises a heat transfer fluid contained within the heat transfer tubes.

[0186] In one embodiment of the present invention, the thermal management system is a battery thermal management system (hereinafter referred to as "BTMS") which is a thermal management system for controlling the temperature of a battery system, preferably a rechargeable battery system.

[0187] While BTMS can be more complex depending on the application, a BTMS typically has at least the function of cooling the battery when the battery temperature is too high and heating the battery when the battery temperature is too low, using a heat transfer fluid flowing through cooling tubes of the present invention that exchange heat with the battery. Other common features of a BTMS include an insulation system to reduce the influence of the external environment on the battery temperature and a ventilation system to facilitate the dissipation of hazardous gases that may occur within the battery pack.

[0188] Typically, the heat transfer fluid is circulated by a pump within a closed system comprising a heat transfer tube of the present invention, which is thermally in contact with the battery, and a second system having the function of heating and / or cooling the heat transfer fluid to a desired temperature. This second system may include any combination of a cooling system and a heating system, or a combination of heating and cooling functions within a heat pump. The circulating heat transfer fluid absorbs heat from or releases heat to the battery, and then it is circulated within the second system to return the heat transfer fluid to the desired temperature. To varying degrees, sophisticated control systems may exist that control the instantaneous temperature of the heat transfer fluid and the battery temperature to optimize the temperature of the heat transfer fluid at each instant.

[0189] Accordingly, another aspect of the present invention is a method for controlling the temperature inside a battery, comprising the step of circulating a heat transfer fluid within a closed system including a heat transfer tube of the present invention, wherein the system is in thermal contact with the battery and a second system having the function of heating and / or cooling the fluid to a desired temperature.

[0190] An additional aspect of the present invention is a method for operating a battery, which includes the step of controlling the temperature of the battery as defined above.

[0191] Batteries, including the BTMS detailed above, can be used in any application where rechargeable batteries may be used. Notable non-limiting examples of such applications include, for example, automobiles, electric bicycles, and urban mobility vehicles such as buses.

[0192] The embodiments described above are illustrative and not limiting. Further embodiments are within the concept of the present invention. In addition, although the present invention is described in relation to specific embodiments, those skilled in the art will recognize that modifications in form and detail can be made without departing from the spirit and scope of the invention. [Examples]

[0193] The present invention will be described below in relation to the following embodiments, the object of which is merely illustrative and not intended to limit the scope of the invention. As used in these embodiments, "Ex" means an embodiment of the present invention, and "CE" means a counterexample.

[0194] raw materials PPS polymer: Ryton® QA200N obtained from Solvay Specialty Polymers USA, LLC; acid-washed PPS with a melt flow rate of 100 g / 10 min at a temperature of 316°C and a load of 5 kg (ASTM D1238).

[0195] PPSU-1 polymer: Radel® R-5500NT obtained from Solvay Specialty Polymers USA, LLC; has a melt flow rate of 12-17 g / 10 min at 365°C and a load of 5 kg (ASTM D1238).

[0196] PPSU-2 polymer: Radel® R-5800NT obtained from Solvay Specialty Polymers USA, LLC; has a melt flow rate of 20-28 g / 10 min at 365°C and a load of 5 kg (ASTM D1238).

[0197] TPE: Igetabond® BF-E is an epoxy functional group-containing elastomer commercially available from Sumitomo Chemical Co., Ltd., having a melt flow rate of 3 g / 10 min (JIS K7210-1, 190°C, 21.2 N) and a Tg of -26°C; it is a poly(ethylene-co-glycidyl methacrylate) copolymer containing structural units derived from 88% by weight ethylene and 12% by weight glycidyl methacrylate.

[0198] KF-105: An epoxy-modified PDMS commercially available from Shin-Etsu Chemical Co., Ltd. This is a double-terminated epoxy polysiloxane represented by formula (11) with a molecular weight of 490 g / mol, where n is a value such that the viscosity at 25°C is 15 cSt.

[0199] Basic procedure for preparing the composition The PPSU polymer (PPSU-1 or PPSU-2) was first dried in an oven at 135°C for at least 5 hours.

[0200] Next, polymer components (A) to (D): PPS, PPSU, TPE, and PDMS were mixed homogenously in a vibrating shaker for 2 to 3 minutes to obtain a dry blend. The dry blend was then placed in a gravitational feeder and supplied to a twin-screw extruder (Clextral D32), where it was melted and extruded. The temperature during extrusion of the PPS-based composition was in the range of 320°C to 350°C.

[0201] The molten flow was cooled and supplied to the pelletizer.

[0202] The pellets were collected and kept in a sealed plastic bucket until they were ready for use in injection molding.

[0203] test The following test methods were used to evaluate the flame retardancy of PPS-based compositions.

[0204] UL94V (2013): Flame retardancy was evaluated using 0.8 mm thick test specimens according to the UL94V vertical combustion test procedure described in Underwriters Laboratory (USA)'s "Test for Flammability of Plastic Materials for Parts in Devices and Appliances," 6th Edition, March 28, 2013.

[0205] The ignition source used was a 50-watt test flame, and the test specimen was exposed to it twice for short periods. During this process, the burning time and the amount of burning particles dripped were evaluated using a cotton indicator placed beneath the test specimen.

[0206] For V-2 grade, combustion must cease within 30 seconds on the vertical test specimen, and the dripping of combustion particles is acceptable.

[0207] For V-1 grade, particle dripping is acceptable as long as combustion stops within 30 seconds on the vertical test specimen and no ignition occurs.

[0208] For V-0 grade, particle dripping is acceptable as long as combustion stops within 10 seconds on the vertical test specimen and no ignition occurs.

[0209] The test standards for UL94V (2013) (vertical combustion test, flame: 50W) are summarized in Table 1.

[0210] [Table 1]

[0211] Some of the compositions are detailed in Table 2, and all percentages listed therein are weight-based, calculated relative to the total weight of the PPS-based composition.

[0212] [Table 2]

[0213] Thin-walled small parts (0.8 mm) were manufactured using injection molding with compositions CE1, E2, CE3, and E4 in a Billion injection molding machine at a temperature range of 320 to 340°C.

[0214] The flame retardancy results, evaluated based on UL94V(2013) for five test specimens of thin-walled parts for each of the CE1, E2, CE3, and E4 compositions, are summarized in Table 3 below.

[0215] [Table 3] Reference compositions CE1 and CE3 (without epoxy-modified PDMS: KF-105), which include PPS, PPSU, and TPE, showed a V-1 rating, whereas compositions E2 and E4 of the present invention (with epoxy-modified PDMS: KF-105) unexpectedly provide materials that meet the V-0 rating according to the UL94V (2013) flame retardancy standard, as measured in thin test specimens with a thickness of 0.8 mm.

[0216] In addition to improved flame retardancy, it was observed that adding epoxy-modified PDMS (KF-105) to PPS-based compositions E2 and E4 did not adversely affect the fracture strain compared to those obtained with reference compositions CE1 and CE3 (without KF-105).

[0217] Extrusion of pipes The tubes can be manufactured using the PPS-based compositions of Examples E2 and E4 in Table 2 as follows: After drying the PPS-based composition at 90°C for 4 hours, place it in an extruder. Set the barrel extruder temperature to 320-340°C.

[0218] The tube is extruded using a calibration bath. The resulting tube should have a good surface appearance and a regular shape. The tube preferably has an outer diameter of 16 mm, a wall thickness of 5 mm to 0.8 mm, and a total length of 10 cm to several meters, for example, up to 1 to 2 meters.

[0219] All patent applications and publications cited herein are incorporated by reference to the extent that they provide exemplary, procedural, or other details that complement what is described herein. If any patent, patent application, or publication cited herein by reference conflicts with the description in this application to such an extent that it obscures certain terminology, the description in this application shall prevail. Any reference to public documents shall be limited to not referencing subject matter that contradicts the express disclosure herein.

[0220] Preferred embodiments of the present invention have been shown and described, but modifications thereof can be made by those skilled in the art without departing from the teachings of the present invention. The embodiments described herein are illustrative and not limiting. Accordingly, the scope of protection is not limited by the descriptions described above, but is limited only by the following claims, which encompass all equivalents of the subject matter of the claims. Each and every claim is incorporated herein by reference as an embodiment of the present invention.

Claims

1. A flame-retardant PPS-based composition, (A) 45 to 75% by weight of at least one polyphenylene sulfide polymer (hereinafter referred to as "PPS polymer"), (B) 20 to 45% by weight of at least one polyphenylsulfone polymer (hereinafter referred to as "PPSU polymer"), (C) 4.5 to 12% by weight of at least one epoxy functional group-containing thermoplastic elastomer (hereinafter referred to as "TPE"), (D) 0.5 to 5% by weight of epoxy-modified polysiloxane, A flame-retardant PPS-based composition containing, The aforementioned weight percentage is based on the total weight of the PPS-based composition, A flame-retardant PPS-based composition in which the total content of components (A), (B), (C), and (D) is 100% by weight or less based on the total weight of the PPS-based composition.

2. The PPS-based composition is - At least 47% by weight, or at least 50% by weight, - Up to 70% by weight, up to 65% by weight, or up to 60% by weight It contains an amount of at least one type of PPS polymer, The flame-retardant PPS-based composition according to claim 1, wherein the weight percentage is based on the total weight of the PPS-based composition.

3. The flame-retardant PPS composition according to claim 1 or 2, wherein the PPS composition comprises 50 to 65% by weight of at least one PPS polymer based on the total weight of the PPS composition.

4. The PPS polymer contains at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, or at least 99 mol%, of the repeating units (R) represented by formula (1') based on the total number of moles of repeating units in the PPS polymer. ＰＰＳ A flame-retardant PPS-based composition according to any one of claims 1 to 3, comprising ). 【Chemistry 1】

5. The PPS-based composition is - At least 22% by weight, at least 25% by weight, at least 27% by weight, or at least 29% by weight, - Maximum 43% by weight, maximum 40% by weight, or maximum 38% by weight It contains an amount of at least one type of PPSU polymer, The flame-retardant PPS-based composition according to any one of claims 1 to 4, wherein the weight percentage is based on the total weight of the PPS-based composition.

6. The PPS polymer contains at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, or at least 99 mol% of the repeating units of formula (2) (R ＰＰＳＵ A flame-retardant PPS-based composition according to any one of claims 1 to 5, comprising ). 【Chemistry 2】

7. The PPS-based composition is - At least 4.5% by weight, at least 5% by weight, at least 6% by weight, at least 7% by weight, or at least 8% by weight, ・Maximum 11% by weight, max. 10.5% by weight, max. 10% by weight It contains at least one type of TPE in an amount of, The flame-retardant PPS-based composition according to any one of claims 1 to 6, wherein the weight percentage is relative to the total weight of the PPS-based composition.

8. The flame-retardant PPS-based composition according to any one of claims 1 to 7, wherein the TPE is selected from the group consisting of poly(ethylene-co-glycidyl methacrylate) copolymer, poly(ethylene-co-methyl (meth)acrylate-co-glycidyl acrylate) copolymer, poly(ethylene-co-n-butyl acrylate-co-glycidyl acrylate) copolymer, and copolymer of styrene and glycidyl (meth)acrylate, preferably selected from poly(ethylene-co-glycidyl methacrylate) copolymer and / or poly(ethylene-co-methyl (meth)acrylate-co-glycidyl acrylate) copolymer, and more preferably selected from poly(ethylene-co-glycidyl methacrylate) copolymer.

9. The flame-retardant PPS composition according to any one of claims 1 to 8, wherein the epoxy-modified polysiloxane contains siloxane repeating units (Rs) represented by any of the following formulas (3a), (3b), or (3c), preferably siloxane repeating units (Rs) represented by the following formula (3a), in an amount of at least 70 mol%, at least 80 mol%, at least 85 mol%, at least 90 mol%, or at least 93 mol%, based on the total number of moles of repeating units in the polysiloxane. 【Transformation 3】 (In the formula, n is an integer between 2 and 100, or between 2 and 70, or between 2 and 60).

10. The epoxy-modified polysiloxane has at least one pendant epoxy functional group, and the epoxy-modified polysiloxane (D) has at least one epoxy-modified siloxane unit (R) represented by general formula (4) or (5). ＥＭ A flame-retardant PPS composition according to any one of claims 1 to 9, further comprising s): 【Chemistry 4】 (Here, - R in equations (4) and (5) ２ is a C1-C3 alkyl group or a phenyl group; - R in equations (4) and (5) ３ Equation (6): -(CH) ２ ) ｋ -O-CH ２ - (6) It is a linking group represented by, In the formula, k is an integer between 1 and 10, preferably between 2 and 8, more preferably between 3 and 6, and most preferably between 3; (In equations (4) and (5), m is an integer between 1 and 10.)

11. The flame-retardant PPS composition according to any one of claims 1 to 10, wherein the epoxy-modified polysiloxane has at least one terminal epoxy functional group, preferably two terminal epoxy functional groups, and the terminal epoxy functional group in the polysiloxane is represented by one of the following formulas (7) and (8): 【Transformation 5】 (wherein, R ３ is represented by formula (6): -(CH ２ ) ｋ -O-CH ２ - (6), and In the formula, k is an integer between 1 and 10, preferably between 2 and 8, more preferably between 3 and 6, and most preferably between 3.

12. The flame-retardant PPS composition according to any one of claims 1 to 11, wherein the epoxy-modified polysiloxane is represented by one of the following formulas (9) and (10): 【Transformation 6】 (Here, - R in equations (9) and (10) １ , R ２ Each of these is independently a C1-C3 alkyl group and / or a phenyl group; - R in equations (9) and (10) ３ Equation (6): -(CH) ２ ) ｋ -O-CH ２ - (6) It is a linking group represented by, In the formula, k is an integer between 1 and 10, preferably between 2 and 8, more preferably between 3 and 6, and most preferably between 3; (n varies between 2 and 100, or between 2 and 70, or between 2 and 60).

13. The flame-retardant PPS-based composition according to claim 12, wherein the epoxy-modified polysiloxane is a poly(dimethylsiloxane) (PDMS) having one or more pendant and / or terminal epoxy functional groups represented by at least one of formulas (7) and (8).

14. The flame-retardant PPS-based composition according to claim 12, wherein the epoxy-modified polysiloxane is a poly(dimethylsiloxane) or poly(phenylmethylsiloxane) having two terminal epoxy functional groups represented by the same formula (7) or (8).

15. The epoxy-modified polysiloxane is - At least 300 g / mol, at least 350 g / mol, or at least 400 g / mol, - Maximum 5000 g / mol, maximum 4000 g / mol, maximum 3000 g / mol, maximum 2000 g / mol, or maximum 1000 g / mol A flame-retardant PPS-based composition according to any one of claims 1 to 14, having a molecular weight of [molecular weight].

16. The flame-retardant PPS composition according to any one of claims 1 to 15, further comprising in an amount not exceeding 10% by weight of at least one additive (E) selected from the group consisting of antioxidants, light stabilizers, ultraviolet stabilizers, heat stabilizers, processing aids, nucleating agents, lubricants, flame retardants, smoke suppressants, antistatic agents, antiblocking agents, mold release agents, and colorants (e.g., pigments, dyes).

17. A flame-retardant PPS-based composition according to any one of claims 1 to 16, which does not contain a flame retardant.

18. A flame-retardant PPS-based composition according to any one of claims 1 to 17, having a flame retardancy rating of V-0 as measured with a 0.8 mm thick test specimen based on the UL94V standard.

19. A method for improving the flame retardancy of a V-1 grade PPS-based composition comprising at least one polyphenylene sulfide polymer ("PPS polymer"), at least one polyphenyl sulfone polymer ("PPSU polymer"), and at least one epoxy functional group-containing thermoplastic elastomer ("TPE"), This includes adding a certain amount of epoxy-modified polysiloxane (D) to the V-1 grade PPS-based composition to obtain a V-0 grade PPS-based composition. The V-0 rated flame-retardant PPS-based composition is A) 45 to 75% by weight of at least one of the PPS polymers, B) 20 to 45% by weight of at least one of the PPSU polymers, C) 4.5 to 12% by weight of at least one of the above TPEs, D) 0.5 to 5% by weight of the epoxy-modified polysiloxane, It contains, The aforementioned weight percentage is based on the total weight of the V-0 grade PPS composition. The total amount of components (A), (B), (C), and (D) is 100% by weight or less based on the total weight of the V-0 grade flame-retardant PPS composition. A method for determining the flame retardancy grades of V-0 and V-1 based on UL94V (2013) using test specimens with a thickness of 1.0 mm or less, preferably 0.8 mm.

20. A molded article comprising the PPS-based composition described in any one of claims 1 to 18, or manufactured from the PPS-based composition.

21. A molded article according to claim 20, selected from the group consisting of tubular members such as heat transfer tubes, coated wires or cables such as magnet wires, slot liners, bobbins such as coil bobbins, slot wedges, power modules, and busbars.

22. A molded article according to claim 20 or 21, which is formed by extrusion molding.

23. A molded article according to any one of claims 20 to 22, wherein the tubular member is hollow so that a fluid can flow through it.

24. A molded article according to any one of claims 20 to 23, comprising a multilayer tubular member having two or more layers, wherein at least one layer is manufactured from a PPS-based composition according to any one of claims 1 to 18.

25. The molded article according to any one of claims 20 to 24, wherein the tubular member has a substantially constant cross-section, preferably a circular cross-section, along its entire length.

26. The molded article according to claim 26, wherein the diameter is in the range of 5 to 50 mm and the wall thickness is in the range of 0.5 to 5.0 mm.

27. A heat transfer tube, a molded article according to any one of claims 20 to 26.

28. A thermal management system comprising a tubular member according to any one of claims 21 to 27.

29. The thermal management system according to claim 28, wherein the tubular member is a heat transfer tube containing a heat transfer fluid.

30. The thermal management system according to claim 29, wherein the heat transfer fluid is selected from the group consisting of water, a water / ethylene glycol mixture, chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HFCs), and (per)fluoropolyethers (PFPEs).

31. An apparatus comprising a thermal management system according to any one of claims 28 to 30, wherein the heat transfer fluid in the thermal management system exchanges heat with the apparatus.

32. The apparatus according to claim 31, wherein the battery is preferably a rechargeable battery.

33. A device comprising the battery according to claim 32, which is an electric vehicle.

34. A method for controlling the temperature inside a battery, comprising the step of circulating a heat transfer fluid in a closed system including a tubular member as described in any one of claims 23 to 27, wherein the system is in thermal contact with the battery and a second system having the function of heating and / or cooling the heat transfer fluid to a desired temperature.

35. A method for operating a battery, comprising a method for controlling the temperature inside the battery as described in claim 32.

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