PPS-based flame retardant composition and molded article using same

Abstract

A flame retardant composition based on PPS comprising: A) at least one polyphenylene sulfide polymer; b) at least one polyphenylsulfone polymer, C) at least one thermoplastic elastomer containing epoxy functional groups, and D) an epoxy-modified polysiloxane. The PPS-based composition has a V-0 rating using the UL 94 V (2013) standard (0.8 mm thickness). An article of manufacture comprising or made from such a PPS-based flame retardant composition. Use of the article as a component of an electric vehicle. A method of cooling and / or operating a battery, the method comprising passing a heat transfer fluid in a flame retardant heat transfer tube comprising or made from the PPS-based flame retardant composition.

Description

[0001] Cross-references to related applications This application claims priority to a prior European patent application filed on 12 April 2023 in Europe under number 23167551.3, the entire contents of which are incorporated herein by reference for all purposes. Technical Field

[0002] The present invention generally relates to a PPS-based flame-retardant composition and its use in the manufacture of flame-retardant molded articles (particularly extruded molded articles, overmolded parts and thin-walled molded articles) which can be suitably used in automotive parts and thermal management systems (particularly for parts and systems in electric vehicles). Background Technology

[0003] In many applications, plastics are key materials driving the development of electric mobility. Due to their functional integration and lightweight properties, plastics offer numerous benefits to automotive engineers in addressing technical challenges that metals may struggle to handle.

[0004] Because electric powertrains pose different hazards than combustion-powered systems, new performance requirements are placed on plastics. In particular, there is a need for enhanced safety against electrical failures that could lead to electric shock, arcing, and other potential ignition sources. Since plastics are largely flammable, special precautions must be taken to improve the safety of electric vehicles and prevent the worst-case scenario of battery cell fires (so-called thermal runaway).

[0005] Batteries must provide increasingly larger instantaneous power and have high energy storage capacity. Batteries with operating voltages of several hundred volts are now known. To achieve the desired voltage and current, multiple individual battery cells are typically connected together in parallel and / or series.

[0006] While advancements have been made in electric vehicle batteries, enabling them to deliver more power and requiring less frequent charging, one of the biggest challenges to battery safety remains the ability to design effective cooling systems.

[0007] For a typical Li-ion battery, when the temperature exceeds 80°C, even if it is only in a part of its structure, an exothermic chemical reaction may begin. This leads to a further increase in the battery temperature, eventually causing the battery to completely collapse, with the risk of fire and explosion.

[0008] Therefore, integrating battery thermal management systems (BTMS) into commercial battery modules has become standard practice, especially when battery safety, reliability, and lifespan are critical concerns. These BTMS can be more or less complex, depending on the type of battery; however, a common element is the presence of a heat transfer fluid that exchanges heat with the battery to heat or cool it.

[0009] Several heat transfer systems exist for battery thermal management, such as air cooling, liquid cooling, and direct refrigerant cooling. Among these, liquid cooling is the most commonly used system due to its convenient design and good heat transfer performance.

[0010] Water or water / glycol mixtures are commonly used as heat transfer media because this type of heat transfer system is already prevalent in vehicles with conventional drives (i.e., those with internal combustion engines). A key safety drawback of using this water-based heat transfer medium is its electrical conductivity. In the event of a leak in the heat transfer circuit, for example due to an accident, the escaping water or water / glycol mixture can cause a short circuit. This can then lead to fires and other emergencies, which in turn can cause additional, and sometimes considerable, damage to the vehicle. To mitigate this risk, components of the thermal management system should possess high flame-retardant properties. This is why flame-retardant polymer compounds are sought in electric mobility applications.

[0011] A common method for identifying the flame retardancy of plastic materials involves a standard test developed by Underwriters Laboratories (USA) known as UL 94 V (Vertical Burning Test), a standard test for the flammability safety of plastic materials used in equipment and appliance parts. Preferably, components used in thermal management systems for batteries in electric vehicles should meet the standard V-0 rating, which identifies plastic materials whose "burning on a vertical section ceases within 10 seconds, allowing for non-burning plastic drippings."

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

[0013] Furthermore, 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, such as automotive, housing equipment, electrical and electronic applications.

[0014] However, PPS resin is brittle, and its toughness, expressed as elongation at break in tensile tests, is lower than that of other engineering polymers.

[0015] For applications requiring toughness, as described in JP S6121156 A, PPS resin compositions containing α-olefin-glycidyl methacrylate copolymers have been developed. In such compositions, improvements in both toughness and flexibility can be achieved by blending with an olefin-based elastomer (which is a softer material than PPS resin).

[0016] However, the flame retardancy of the resin composition comprising PPS resin and an olefin-based elastomer described in JP S6121156 A was evaluated in WO 2022209848 A1. It was observed that the flame retardancy of this resin composition was lower than that of PPS resin alone, and the flame retardancy decreased significantly when the olefin-based elastomer was added to PPS. In WO2022209848 A1, it was assumed that although PPS resin alone has high flame retardancy, blending with an olefin-based elastomer, which has significantly poor flame retardancy, reduces the flame retardancy of the resulting blend composition. While this blend composition has the advantages of flexibility and toughness, it does not exhibit the excellent flame retardancy inherent in PPS resin, and therefore faces limitations in application development.

[0017] The applicant confirmed this observation in the context of manufacturing cooling tubes from toughened PPS compositions. PPS formulated with a thermoplastic elastomer (“TPE”) achieves sufficient toughness and viscosity to allow for tube extrusion and thermoforming. However, introducing 10 wt% TPE into PPS results in a material with poor flame retardancy. For example, the toughened PPS material is not V-0 (measured using UL 94 V (2013): Vertical Burning Test, on a sheet with a thickness of 1.6 mm). Due to the low TPE content, the toughened PPS material (PPS+TPE) exhibits poor ductility, with a fracture deformation rate of only about 13%.

[0018] Therefore, there is a persistent need in the art for a PPS flame-retardant composition suitable for manufacturing articles intended for use in systems susceptible to fire hazards, such as components in eV batteries used in electric vehicles (“eV”), and particularly components in the thermal management systems of eV batteries. The article should have the highest flame retardant rating V-0 according to UL 94 V (2013) (0.8 mm thickness), while simultaneously possessing the necessary mechanical properties to withstand curing during use. Summary of the Invention

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

[0020] The first object of the present invention is a polyphenylene sulfide-based composition comprising: - (A) 45 to 75 wt% of at least one polyphenylene sulfide (PPS) polymer, - (B) 20 to 45 wt% of at least one polyphenylsulfone (PPSU) polymer, - (C) 4.5 to 12 wt% of at least one thermoplastic elastomer (TPE) containing epoxy functional groups, and - (D) 0.5 to 5 wt% of at least one epoxy-modified polysiloxane (“pSiO”), The wt% is based on the total weight of the PPS-based composition. The combined content of components (A), (B), (C) and (D) is 100 wt% 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 rating V-0 as measured according to UL 94 V (2013) on a test piece having a thickness of 1.0 mm or less, preferably 0.8 mm.

[0022] A second object of the present invention is the use of the PPS-based flame-retardant composition according to the first object in the manufacture of flame-retardant articles, which means articles having a V-0 rating, wherein the flame retardancy rating V-0 is measured in a test piece having a thickness of 1.0 mm or less, preferably 0.8 mm, according to the UL 94 V (2013) vertical burning test standard.

[0023] A third object of the invention is an article comprising or made from a PPS-based flame-retardant composition according to the first object. The article has a V-0 rating, wherein the flame-retardant rating V-0 is measured according to UL 94 V (2013) in a test piece having a thickness of 1.0 mm or less, preferably 0.8 mm. The article can be a component (e.g., heat transfer tube, magnet wire, busbar, winding spool, slot liner, slot wedge, power module, etc.) for automotive equipment (such as for electric vehicles (eV) and / or for thermal management systems), particularly for components in eV batteries, electric motors, or generators and / or for thermal management systems of eV batteries.

[0024] A fourth object of the present invention is a method for improving the flame retardancy rating of a V-1 grade PPS composition comprising at least one polyphenylene sulfide, at least one polyphenylene sulfone, and at least one thermoplastic elastomer containing an epoxy functional group. This method comprises adding an epoxy-modified polysiloxane to the V-1 grade PPS composition to obtain a V-0 grade PPS-based composition of the present invention, wherein the V-0 and V-1 flame retardancy ratings are measured according to UL 94 V (2013) on a test piece having a thickness of 1.0 mm or less, preferably 0.8 mm.

[0025] It has been found that certain PPS-based compositions comprising at least one polyphenylene sulfide, at least one polyphenylene sulfone, at least one thermoplastic elastomer containing epoxy functional groups, and at least one epoxy-modified polysiloxane can be used to manufacture articles that meet a flame retardancy rating of V-0 as measured according to UL 94 V (2013) in a test piece having a thickness of 1.0 mm or less, preferably 0.8 mm. Flame-retardant articles are preferably intended for use in extruded molded parts and / or thin-walled molded parts in electric vehicles. Flame-retardant articles are particularly suitable for use in automotive and thermal management systems, especially in eV batteries, electric motors, or generators, and / or in eV battery thermal management systems (e.g., tubular components such as heat transfer tubes, coated wires / cables such as magnet wires, busbars such as electrical busbars, winding spools such as coil winding spools, slot liners, slot wedges, power modules, etc.).

[0026] By referring to the specific implementation methods and examples, the various aspects, advantages, and features of the present invention will be more easily understood and appreciated.

[0027] definition In the following description and claims, reference will be made to numerous terms which shall be defined to have the following meanings: - Unless otherwise stated, the terms "a / an" or "the" mean "one / a or more / multiple" or "at least one / a" and are used interchangeably; - The term "and / or" used in phrases in the form of "A and / or B" means A alone, B alone, or A and B together; Even if any description of a particular embodiment applies to and is interchangeable with other embodiments of this disclosure, and each embodiment defined theretherein may be combined with another embodiment, unless otherwise specified or clearly incompatible; - When an element or component is referred to as being included in and / or selected from the list of enumerated elements or components, it should be understood that in the relevant embodiments explicitly considered herein, the element or component may also be any one of these enumerated individual elements or components, or may also be a group consisting of any two or more of the explicitly enumerated elements or components; any element or component listed in the list of elements or components may be omitted from this list. - Any enumeration of numerical ranges by endpoints in this document includes all numbers contained within the enumerated range, as well as the endpoints and equivalents of that range; - The term "comprising" or "comprise" includes "consisting essentially of" or "consisting of" and "consisting of". - As used in this article, the term " Includes "Synonymous with "including", "containing" or "characterized in", it is intended to be inclusive or open-ended and does not exclude additional, unlisted elements or steps; - As used herein, the term “consistently of” includes the specified materials or steps that do not materially affect the essential properties or functions of the described composition, process, method or article of manufacture. - As used herein, the term "composed of" does not include any unspecified element, step, or component; - The term "consisting essentially of" or "consists essentially" in relation to a composition, article, component, process, or method is intended to mean any additional elements, steps, or features that may not be explicitly described herein and will not materially affect the essential and novel features of such a composition, article, component, process, or method may be included in such embodiments; generally, "consisting essentially of" in relation to a composition of the present invention means that the content of one or more components not explicitly provided in the specification is less than 1 wt.%, or less than 0.5 wt.%, or less than 0.1 wt.%, or less than 0.05 wt.%, or even less than 0.01 wt.%, where wt% is based on the total weight of the PPS-based composition; As used throughout this specification and claims, approximate language may be applied to modify any quantitative representation that may be permissibly altered without changing its underlying function; therefore, a value modified by one or more terms (such as “about” and “substantially”) is not limited to the specified precise value. In at least some instances, approximate language may correspond to the precision of the instrument used to measure the value; - The terms "optional" or "optionally" mean that the component or method step or condition described below may or may not occur, and the description includes instances where the component or method step or condition occurs and instances where it does not occur; - Throughout this specification and claims, scope limitations may be combined and / or interchanged, and such scopes are identified and include all sub-scopes contained herein, unless the context or language indicates otherwise; - It should be understood that the elements, properties and / or characteristics of the polymers, compositions, products or articles, processes, methods or uses described in this specification may be explicitly or implicitly combined with other elements, properties and / or characteristics of the polymers, compositions, products or articles, processes, methods or uses in all possible ways without departing from the scope of this specification. - The term "recurring unit" refers to the smallest repeating unit in a polymer chain. The term "recurring unit" is synonymous with the terms "repeating unit" and "structural unit"; and - The proportion of repeating units in a polymer is given in mol.% relative to the total molar amount of repeating units in the polymer.

[0028] If any disclosure of any patent, patent application, or publication incorporated herein by reference conflicts with the description of this application to the extent that it may make the terminology unclear, then this description shall take precedence. Detailed Implementation

[0029] PPS-based flame retardant compositions The PPS-based flame retardant composition comprises: - (A) 45 to 75 wt% of at least one PPS polymer, - (B) 20 to 45 wt% of at least one PPSU polymer, - (C) 4.5 to 12 wt% of at least one TPE, and - (D) 0.5 to 5 wt% of at least one epoxy-modified polysiloxane, The wt% is based on the total weight of the PPS-based composition. The combined content of components (A), (B), (C) and (D) is 100 wt% or less based on the total weight of the PPS-based composition.

[0030] Preferably, the PPS-based flame retardant composition comprises: - (A) 47 to 70 wt% of at least one PPS polymer, - (B) 22 to 43 wt% of at least one PPSU polymer, - (C) 5 to 11 wt% of at least one TPE, and - (D) 0.6 to 4 wt% of at least one epoxy-modified polysiloxane, The wt% is based on the total weight of the PPS-based composition. The combined content of components (A), (B), (C) and (D) is 100 wt% or less based on the total weight of the PPS-based composition.

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

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

[0033] Even more preferably, the PPS-based flame retardant composition comprises the following: - (A) 45% to 75 wt%, or 47% to 70 wt%, or 50% to 65 wt%, or 50% to 65 wt% of at least one PPS polymer, - (B) 20% to 45 wt%, or 22% to 43 wt%, or 23% to 40 wt%, or 27% to 38 wt% of at least one PPSU polymer, - (C) 4.5% to 12 wt%, or 5% to 11 wt%, or 6% to 10 wt%, or 7% to 10 wt% of at least one TPE, - (D) 0.5% to 5 wt%, or 0.6% to 4 wt%, or 0.7% to 3 wt%, or 1% to 2 wt% of at least one epoxy-modified polysiloxane, - Optionally up to 10 wt% of at least one additive (E), and - Optionally less than 15 wt% of at least one other resin (F) different from components (A), (B), (C), (D) and (E), The wt% is based on the total weight of the PPS-based composition. The combined content of components (A), (B), (C), (D), (E) and (F) is based on a total weight of 100 wt% of the PPS-based composition.

[0034] The PPS-based composition of the present invention has a flame retardancy of V-0 as measured according to the UL 94 V (2013) vertical burning test on a test piece having a thickness of 1.0 mm or less, preferably 0.8 mm.

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

[0036] The PPS-based flame retardant 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 any flame retardant.

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

[0039] Although the PPS-based compositions of the present invention may contain a polymer (F) that is different from components (A), (B), (C), (D) and (E), it is preferred that the PPS-based compositions of the present invention do not contain another polymer that is different from components (A), (B), (C), (D) and (E).

[0040] In particular, the PPS-based compositions of the present invention preferably do not contain a poly(etherimide) (“PEI”) polymer; the terms “poly(etherimide)” and / or “polymer (PEI)” indicate the presence of at least 50 mol.% repeating units (R) based on the total molar percentage of the polymer. PEI Polymers comprising repeating units containing at least one aromatic ring, at least one imide group (as is and / or in its amide acid form), and at least one ether group. Repeating unit (R)PEI It may optionally further include at least one amide group, which is not included in the form of an amide acid of an imide group.

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

[0042] It was observed that when considering base compositions containing PPS polymers, PPSU polymers, and TPE (without pSiO), the addition of epoxy-modified polysiloxanes did not negatively affect the fracture deformation rate of the resulting PPS-based compositions.

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

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

[0045] According to the present invention, the PPS polymer represents a polymer containing at least 50 mol% of repeating units (R) represented by formula (1). PPS Any polymer of PPS (mol% is based on the total number of repeating units in the PPS polymer): (1), R is independently selected from the group consisting of: halogen, C1-C12 alkyl, C7-C24 alkylaryl, C7-C24 aralkyl, C6-C24 arylene, C1-C12 alkoxy and C6-C18 aryloxy, and i is independently an integer from 0 to 4.

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

[0047] The PPS polymer is preferably composed of at least 50 mol% of repeating units (R) represented by formula (1'). PPS (i.e., any polymer having a repeating unit of equation (1) where i is 0): (1').

[0048] According to an embodiment of the present invention, the PPS polymer comprises at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, or at least 99 mol% of repeating units in the PPS polymer being repeating units (R) represented by formula (1) or (1'). PPS The mol% figure is based on the total number of repeating units in the PPS polymer.

[0049] The PPS polymer can be acid-washed or non-acid-washed. In some embodiments, the PPS polymer is an acetic acid-washed PPS polymer.

[0050] According to embodiments of the present invention, the PPS polymer is such that 100 mol% of the repeating units are repeating units (R) represented by formula (1) or (1'). PPS According to this embodiment, the PPS polymer is essentially composed of repeating units (R) represented by formula (1'). PPS Composition.

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

[0052] The melt flow rate of PPS (according to ASTM D1238 at 316°C and 5 kg weight, Procedure B) can be 50 to 400 g / 10 min, such as 60 to 300 g / 10 min or 70 to 200 g / 10 min. For example, Ryton® PPS QA220N and QA 200N have melt flow rates of 160 g / 10 min and 100 g / 10 min, respectively. Ryton® PPS QC220N, QC 210N, and QC 200N have melt flow rates of 175 g / 10 min, 135 g / 10 min, and 100 g / 10 min, respectively.

[0053] As used in this article, melt flow rate (MFR), also known as melt flow index (MFI), 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. Simultaneously, melt flow rate is a measure of a material melt's ability to flow under pressure. Melt flow rate is inversely proportional to the viscosity of the polymer melt. If the MFI or MFR is low, its melt viscosity and melt flow resistance are high.

[0054] The PPS-based composition comprises at least 45 wt%, at least 47 wt%, or at least 50 wt% of the total weight of the PPS-based composition, of at least one PPS polymer.

[0055] The PPS-based composition comprises 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% of the total weight of the PPS-based composition.

[0056] Preferably, the PPS-based composition comprises at least one PPS polymer in an amount ranging from 45 to 75 wt% or 50 to 65 wt% of 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, referred to below as "PPSU" or "PPSU polymer".

[0058] As used herein, PPSU polymer means containing at least 50 mol% of repeating units (R) represented by equation (2). PPSU Any polymer: (2), This mol% figure is based on the total number of repeating units in the PPSU polymer.

[0059] According to the embodiments disclosed herein, 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 repeating units (R) represented by formula (2). PPSU ).

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

[0061] The melt flow rate of PPSU polymer (at 365°C and 5 kg by weight, according to ASTM D1238) can be 5 to 40 g / 10 min, such as 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-5500 NT, R-5700 NT, R-5800 NT, and R-5900 NT have melt flow rates of 12-17 g / 10 min, 34-40 g / 10 min, 20-28 g / 10 min, and 26-36 g / 10 min, respectively.

[0062] The PPS-based composition comprises at least 20 wt%, such as at least 22 wt%, at least 25 wt%, at least 27 wt%, or at least 29 wt% of the total weight of the PPS-based composition, of at least one PPSU polymer.

[0063] The PPS-based composition comprises at least one PPSU polymer in an amount of up to 45 wt%, such as up to 43 wt%, up to 40 wt%, or up to 38 wt%, based on the total weight of the PPS-based composition.

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

[0065] Component (C): Thermoplastic elastomer (TPE) containing epoxy functional groups PPS-based compositions comprise at least one thermoplastic elastomer containing epoxy functional groups, referred to herein as "TPE".

[0066] In the context of this invention, "elastomer" is defined as a polymer material exhibiting the following characteristics: (1) a low glass transition temperature (Tg), i.e., a glass transition temperature below 25°C or even below 0°C, and (2) a low modulus (Young's modulus), i.e., a modulus below 200 MPa or even below 100 MPa.

[0067] The term "epoxy functional group" is used here in its usual sense, meaning a functional group that contains an oxygen atom connected to two adjacent carbon atoms by a single bond, thereby forming a three-membered epoxide ring.

[0068] The polymer backbone of TPE can be selected from elastomer backbones, which include 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 mixtures of one or more of the above.

[0069] The TPE used in PPS-based compositions contains epoxy functional groups. The functionalization of the backbone can be achieved by copolymerization of monomers containing epoxy functional groups or by grafting a polymer backbone with another component containing epoxy functional groups.

[0070] Specific examples of TPEs include poly(ethylene-co-glycidyl methacrylate) copolymers, poly(ethylene-co-(methyl methacrylate)-co-glycidyl methacrylate) copolymers, poly(ethylene-co-butyl methacrylate-co-glycidyl methacrylate) copolymers, and copolymers of styrene and (methyl) methacrylate. Notable, non-limiting examples of commercially available TPEs suitable for the heat transfer tubes of this invention are, for example, Lotader® AX8900 and Lotader® AX8840 from Arkema (Bristol, PA, USA), which are poly(ethylene-co-alkyl acrylate-co-glycidyl acrylate) terpolymers (containing structural units derived from 67 wt% ethylene, 25 wt% methyl acrylate, and 8 wt% glycidyl methacrylate) and poly(ethylene-co-glycidyl methacrylate) copolymers (containing structural units derived from 92 wt% ethylene and 8 wt% glycidyl methacrylate), respectively; or Igetabond® BF-E from Sumitomo Chemical, which is also a poly(ethylene-co-glycidyl methacrylate) copolymer (containing structural units derived from 88 wt% ethylene and 12 wt% glycidyl methacrylate). Another example of a suitable TPE is that traded under the name Paraaloid. TMEXL 2314 is commercially available from Dow Inc. (Midland, MI, USA). It is a core-shell type acrylate-based polymer comprising a core mainly composed of cross-linked poly(n-butyl acrylate) rubber and a shell mainly composed of poly(methyl methacrylate)-poly(glycidyl methacrylate) copolymer.

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

[0072] Favorable results have been obtained using Igetabond® BF-E from Sumitomo Chemical Co., Ltd., which is a poly(ethylene-co-glycidyl methacrylate) copolymer (containing structural units derived from 88 wt% ethylene and 12 wt% glycidyl methacrylate).

[0073] The PPS-based composition preferably contains TPE having a melt flow rate of less than 10 g / 10 min, such as 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, at 190°C and 2.16 kg load).

[0074] The PPS-based composition comprises at least 4.5 wt%, at least 5 wt%, at least 6 wt%, at least 7 wt%, or at least 8 wt% of the total weight of the PPS-based composition, or at least at least 8 wt% of at least one TPE.

[0075] The PPS-based composition comprises at least one TPE in an amount of up to 12 wt%, up to 11.5 wt%, up to 11 wt%, up to 10.5 wt%, or up to 10 wt% of 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 wt%, preferably 5 to 11 wt%, 6 to 10 wt%, or 7 to 10 wt% of 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 the context of this invention, "polysiloxane" is defined as a silicone-based polymer compound containing siloxane-oxy-silicon bonds (Si-O-Si) in its main chain structure. Each Si atom in the siloxane bond typically carries two organic groups, usually selected from alkyl, vinyl, and / or phenyl groups. The two organic groups may be the same as or different from each other.

[0079] Epoxy-modified polysiloxanes (D) include at least one polysiloxane containing at least one epoxy functional group. The term "epoxy functional group" is used herein in its usual sense, meaning a functional group containing an oxygen atom connected to two adjacent carbon atoms by a single bond, 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 molar number of repeating units in the polysiloxane (D): (3) In formula (3), each of R1 and R2 is independently a C1-C3 alkyl and / or phenyl; and n is an integer from 2 to 100, or from 2 to 70, or from 2 to 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 repeating units (Rs) having formula (3), where the mol% is based on the total number of moles of repeating units in the polysiloxane (D). Essentially 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 methyl, ethyl and / or phenyl, more preferably independently selected from methyl and phenyl.

[0083] Specifically, the epoxy-modified polysiloxane (D) contains at least 70 mol% of a siloxane repeating unit (Rs) represented by any one of the following formulas (3a), (3b) or (3c), based on the total molar number of repeating units in the polysiloxane (D): More preferably, it contains a repeating siloxane 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). Essentially all repeating units of the polysiloxane (D) may be composed of the same siloxane repeating units (Rs) represented by formula (3a), (3b), or (3c), preferably units (Rs) represented by formula (3a) or (3c), and more preferably units (Rs) represented by formula (3a).

[0085] Particularly suitable epoxy-modified polysiloxanes (D) are poly(dimethylsiloxane) (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 repeating siloxane units (Rs) represented by formula (3a), wherein the mol% is based on the total number of moles of repeating units in the polysiloxane (D).

[0086] When the epoxy-modified polysiloxane (D) is a copolymer containing one or more additional units different from the repeating siloxane unit (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 other units different from the repeating siloxane unit (Rs), said mol% being based on the total number of moles of units in the polysiloxane (D).

[0087] The epoxy-modified polysiloxane (D), preferably the epoxy-modified PDMS, can be a mono-functionalized silicone polymer, a bi-functionalized polysiloxane, or a polyfunctionalized epoxy-modified polysiloxane having at least one terminal and / or side epoxy functionalization. That is, the epoxy-modified polysiloxane (D) can contain an epoxy functional group at only one end, an epoxy functional group at each of the two ends, at least one epoxy functional group on one or more side chains, or any combination thereof.

[0088] When an epoxy-modified polysiloxane (D) has one or more side epoxy functional groups, the polysiloxane (D) may further contain one or more epoxy-modified siloxane units (R) represented by general formula (4) or (5). EM s): in - R2 in formulas (4) and (5) is a C1-C3 alkyl or phenyl; - R3 in formulas (4) and (5) is the linking group represented by formula (6): –(CH2) k –O–CH2– (6), Where k is an integer from 1 to 10, preferably from 2 to 8, more preferably from 3 to 6, and most preferably 3; and - m in equations (4) and (5) varies from 1 to 10, or from 1 to 7, or from 1 to 6.

[0089] In the unit (R) with equation (4) or (5) EM In s), R2 is preferably methyl or phenyl, more preferably methyl.

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

[0091] In equations (4) and (5), R3 is preferably represented by equation (6a): –(CH2)3–O–CH2– (6a).

[0092] The epoxy-modified polysiloxane (D) can contain only one epoxy-modified siloxane unit (R) having formula (4) or (5) in the polymer chain. EM Alternatively, the epoxy-modified polysiloxane (D) may comprise two or more epoxy-modified siloxane units (R) having formula (4) or (5). EM s), which can be continuous with each other (i.e., forming epoxy-modified polysiloxane blocks) or can be randomly placed in the main chain of epoxy-modified polysiloxane (D). When more than one epoxy-modified siloxane unit (R) is used EM When s), the epoxy-modified siloxane unit (R) EM s) have the same expression represented by equation (4) or (5).

[0093] When the epoxy-modified polysiloxane (D) is a siloxane unit (R) containing at least one epoxy-modified unit... EMWhen the epoxy-modified polysiloxane (D) is a copolymer of s) and siloxane repeating units (Rs), the epoxy-modified polysiloxane (D) preferably contains at most 20 mol%, at most 15 mol%, at most 10 mol%, or at most 7 mol% of units (Rs). EM s), the mol% is based on the unit (R) in polysiloxane (D). EM The total molar number of (Rs) and (Rs). Preferably, in this embodiment, the epoxy-modified polysiloxane (D) copolymer consists only of units (Rs). EM It consists of (s) and (Rs).

[0094] When 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 (terminus) of the polymer chain (single-terminal epoxy functionalization) or contain an epoxy functional group at each of the two ends (terminus) of the polymer chain (double-terminal epoxy functionalization).

[0095] One or both terminal epoxy functional groups of the polysiloxane (D) can be represented by at least one of the following formulas (7) and (8): R3 is represented by equation (6): –(CH2) k –O–CH2–, Where k is an integer from 1 to 10, preferably from 2 to 8, more preferably from 3 to 6, and most preferably 3.

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

[0097] When the epoxy-modified polysiloxane (D) has only one terminal epoxy functional group, the other terminal group can be represented by the following... –(CH2) k –O–CH3 or –(CH2) k –O–CH2–CH3, Where k is an integer from 1 to 10, preferably from 2 to 8, more preferably from 3 to 6, and most preferably 3.

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

[0099] In formulas (9) and (10), each of R1 and R2 is preferably selected independently from methyl, ethyl and / or phenyl, more preferably independently from methyl and phenyl.

[0100] In equations (9) and (10), R3 is preferably represented by equation (6a): –(CH2)3–O–CH2–(6a).

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

[0103] In a more particularly suitable embodiment, the epoxy-modified polysiloxane (D) may be a poly(dimethylsiloxane) "PDMS" (double-terminated functionalized) having two terminal epoxy functional groups represented by the same formula selected from formulas (7) and (8), such as that represented by formula (11) or (12): Where n is an integer from 2 to 100, preferably from 2 to 70, and more preferably from 2 to 60.

[0104] PDMS modified with di-terminal epoxy groups, represented by formula (11), has yielded particularly favorable results.

[0105] In other suitable embodiments, the epoxy-modified polysiloxane (D) can be a poly(dimethylsiloxane) having side-chain epoxy functional groups as represented by formula (13): in - n is an integer from 2 to 100, or from 2 to 70, or from 2 to 60; and - m such that the ratio of m / (m+n) can be 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 preferably makes the ratio of m / (m+n) 0.01 to 0.1 or 0.02 to 0.07.

[0107] It should be understood that the epoxy-modified polysiloxane (D) can be a multifunctional epoxy-modified silicone having both terminal and side epoxy functionalization. In such an example, the multifunctional epoxy-modified polysiloxane (D) comprises at least one epoxy-modified siloxane unit (R). EM s), siloxane repeating unit (Rs) and at least one end group represented by formula (7) or (8).

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

[0109] Examples of epoxy-modified PDMS with dual-terminated epoxy groups, represented by formula (11), are KF-105 (molecular weight 490 g / mol; viscosity 15 cSt) from Shin-Etsu Corporation; 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 DMS-E9 (molecular weight 363 g / mol; viscosity 8-11 cSt; 5.5 eq / kg epoxy groups) from Gates Corporation; DMS-E11 (molecular weight 500-600 g / mol; viscosity 12-18 cSt; 1.9-2.2 eq / kg epoxy groups); DMS-E9 (molecular weight 363 g / mol; viscosity 8-11 cSt; 5.5 eq / kg epoxy groups) from Gates Corporation. DMS-E12 (molecular weight 1000-1400 g / mol; viscosity 20-35 cSt; 1.6-1.9 eq / kg epoxy group); DMS-E21 (molecular weight 4500-5000 g / mol; viscosity 100-140 cSt; 0.35-0.45 eq / kg epoxy group).

[0110] An example of epoxy-modified PDMS representing a bi-terminated alicyclic epoxy silicone, as represented by formula (12), is DMS-EC13 from Gates Corporation (molecular weight 900-1000 g / mol; viscosity 25-35 cSt; 1.9-2.0 eq / kg epoxy group), which is an epoxycyclohexylethyl-terminated PDMS.

[0111] Formula (13) represents a siloxane unit composed of a dimethylsiloxane repeating unit (Rs) and an epoxy-modified siloxane unit (R). EM An example of epoxy-modified PDMS of copolymers consisting of s) is ECM-227, available from Geist Corporation, which is a [2%-3% (epoxycyclohexylethyl)methylsiloxane]-dimethylsiloxane copolymer. Another example of epoxy-terminated PDMS also having epoxy side chains is X-22-9002 (viscosity 900 cSt), available from Shin-Etsu Corporation.

[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, or 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 comprises at least 0.5 wt%, or at least 0.6 wt%, such as at least 0.7 wt%, of the total weight of the PPS-based composition as a whole at least one epoxy-modified polysiloxane (D).

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

[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 wt%, for example 0.6 to 4 wt%, 0.7 to 3 wt%, 0.8 to 2.5 wt%, or 1 to 2 wt% of the total weight of the PPS-based composition.

[0120] Optional component (E): one or more additives The PPS-based compositions according to the invention may further comprise at least one additive (E), including but not limited to antioxidants, light stabilizers, UV stabilizers, heat stabilizers, processing aids, nucleating agents, lubricants, flame retardants, smoke suppressants, antistatic agents, anti-blocking agents, mold release agents, and colorants (e.g., pigments, dyes). Preferably, flame retardants are omitted from this list.

[0121] 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 and blended into the PPS-based composition according to the invention to a degree that does not impair the effects of the invention.

[0123] When present, one or more additives (E) are typically included in the PPS-based composition in an amount typically up to 10 wt%, or even up to 8 wt%, or up to 5 wt%, relative to the total weight of the PPS-based composition. The additives are generally present in an amount of at least 0.5 wt%, for example at least 0.8 wt%, or at least 1 wt%, relative to the total weight of the PPS-based composition.

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

[0125] Colorant additives (E) containing carbon black powder can be included in PPS-based compositions. The preferred concentration of carbon black in the PPS-based composition can be from 0.05 wt.% to 3 wt.%, or 0.1 wt.% to 1 wt.%, or 0.2 wt.% to 0.5 wt.% of the total weight of the PPS-based composition.

[0126] This carbon black powder can be added to PPS-based compositions in the form of a masterbatch, which further comprises a polymer carrier. This masterbatch is commonly referred to as "…". carbon black concentrate The carbon black concentrate may contain 5 to 70 wt.%, 10 to 40 wt.%, or 10 to 35 wt.% of carbon black based on the total weight of the carbon black concentrate. A carbon black concentrate of 1 to 10 pph may be added to a PPS-based composition, where “pph” means parts per hundred based on the total weight of the PPS-based composition.

[0127] Suitable lubricants as additives (E) may be selected from linear low-density polyethylene, calcium stearate or magnesium stearate or sodium lignite, 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 may be from 0.05 wt.% to 3 wt.%, or 0.1 wt.% to 1 wt.%, or 0.2 wt.% to 0.8 wt.% of the total weight of the PPS-based composition.

[0128] One or more antioxidants may also be desired additives (E) in PPS-based compositions. Antioxidants can improve the thermal and light stability of PPS-based compositions. For example, antioxidants acting as heat stabilizers can improve the thermal stability of PPS-based compositions during manufacturing (or in high-temperature application environments), for example, by making the polymer processable 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 (e.g., CuI, KI, and KBr, including combinations of alkali metal halides, such as, but not limited to, CuI / KI), hindered phenols, hindered amine light stabilizers (“HALS”) (e.g., tertiary amine light stabilizers), and organic or inorganic phosphorus-containing stabilizers (e.g., sodium hypophosphite or manganese hypophosphite).

[0129] Exemplary release agents as additives (E) include, but are not limited to, metal stearates, stearyl stearate, pentaerythritol tetrastearate, beeswax, lignite wax, paraffin wax, etc., or any combination thereof.

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

[0131] Nevertheless, when a PPS-based composition contains at least one flame retardant as an 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 an example, the flame retardant added as an 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 salts of hypophosphonic acids (phosphonates), salts of secondary phosphonic acids (secondary phosphonates), and their condensation products.

[0132] The phosphorus-based flame retardant can be omitted from the PPS-based flame retardant composition of the present invention.

[0133] Halogen-based flame retardants can be omitted from the PPS-based flame retardant compositions of the present invention.

[0134] Inorganic flame retardants can be omitted from the PPS-based flame retardant compositions of the present invention.

[0135] More preferably, additive (E) does not include flame retardants. That is, no flame retardants are present in the PPS-based flame retardant compositions of the present invention comprising components (A)-(D) and any optional components (E)-(F).

[0136] Optional component (F): Other resins An optional resin (F), different from components (A), (B), (C), (D) and optional (E), may be added to and blended into the PPS-based composition according to the invention to a degree that does not impair the effects of the invention.

[0137] Specific examples of other resins (F) include, but are not limited to, polyamides, polyamide elastomers, polybutylene terephthalate, polyethylene terephthalate, polyester elastomers, polyetherimides, polyketides, liquid crystal polymers, polyetherketones, polyetheretherketones, ethylene-tetrafluoroethylene copolymers (ETFE), tetrafluoroethylene-perfluoro(alkyl vinyl ether) copolymers (PFA), tetrafluoroethylene-hexafluoropropylene copolymers (FEP), ethylene-tetrafluoroethylene-hexafluoropropylene copolymers, polyvinylidene fluoride (PVDF), and polychlorotrifluoroethylene (PCTFE). The amount of such resin (F) added is preferably less than 15 wt%, preferably less than 10 wt%, more preferably less than 8 wt%, even more preferably less than 6 wt%, and even more preferably less than 4 wt%, less than 2 wt%, or less than 1 wt%, based on the total weight of the PPS-based composition.

[0138] Furthermore, as a lower limit, it is preferred that the PPS-based composition does not contain any resin (F), that is, the content of resin (F) different from components (A), (B), (C), (D) and optional (E) is 0 wt%.

[0139] The PPS-based compositions of the present invention preferably do not contain a poly(etherimide) (PEI) polymer. The designation "poly(etherimide)" and / or "polyetherimide" indicates the presence of at least 50 mol.% repeating units (R) based on the total molar percentage of the polymer. PEI Polymers comprising repeating units containing at least one aromatic ring, at least one imide group (as is and / or in its amide acid form), and at least one ether group. Repeating unit (R) PEI It may optionally further include at least one amide group, which is not included in the form of an amide acid of an imide group.

[0140] Method for preparing PPS-based compositions The PPS-based composition of the present invention can be prepared using methods well known in the art.

[0141] For example, PPS-based compositions are prepared by melt blending components (A), (B), (C), and (D) and any optional component (E) and / or (F). Any suitable melt blending method can be used to combine the components of the compositions 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. These components can be added to the melt mixer all at once or gradually in batches. When adding the components gradually in batches, a portion of the component can be added first and then melt-blended with the remaining portions of the subsequently added components until a fully blended PPS-based composition is obtained.

[0142] The temperature for melt blending can be from 320°C to 350°C.

[0143] All embodiments described herein relating to the PPS-based compositions of the present invention After necessary modifications Both apply here.

[0144] Application of epoxy-modified polysiloxane (D) for improving the flame retardancy of V-1 grade PPS-based compositions comprising components (A), (B), and (C). Another aspect of the present invention is a method for improving the flame retardancy of a V-1 grade PPS-based composition, the V-1 grade PPS-based composition comprising... - Component (A): At least one polyphenylene sulfide polymer (“PPS”), - Component (B): at least one polyphenylsulfone polymer (“PPSU”), and - Component (C): At least one thermoplastic elastomer (“TPE”) containing epoxy functional groups, The method includes adding a certain amount of component (D): epoxy-modified polysiloxane to the V-1 grade PPS-based composition to obtain a V-0 grade PPS-based composition comprising: - (A) 45 to 75 wt% of at least one PPS polymer, - (B) 20 to 45 wt% of at least one PPSU polymer, - (C) 4.5 to 12 wt% of at least one thermoplastic elastomer (TPE) containing epoxy functional groups, and - (D) 0.5 to 5 wt% epoxy-modified polysiloxane, The wt% is the total weight of the PPS-based composition based on V-0 grade. The combined amounts of components (A), (B), (C), and (D) are 100 wt% or less based on the total weight of the PPS-based composition of V-0 grade. The V-0 and V-1 flame retardancy ratings are measured according to UL 94 V (2013) on a test piece with a thickness of 1.0 mm or less, preferably 0.8 mm.

[0145] Such a method is applicable to any of the embodiments of the PPS-based compositions of the present invention and any of the various embodiments of components (A)-(D) described herein.

[0146] In a specific embodiment, a PPS-based composition for improving the flame retardancy of a V-1 grade composition comprises: - Component (A): At least one PPS polymer, - Component (B): At least one PPSU polymer, - Component (C): At least one thermoplastic elastomer (TPE) containing epoxy functional groups. - Optional component (E): at least one additive (E), and - Optional component (F): another resin (F) different from components (A), (B), (C), (D) and (E); The method involves adding a certain amount of component (D) to the V-1 grade PPS-based composition: at least one epoxy-modified polysiloxane, to obtain a V-0 grade PPS-based composition comprising the following: - (A): 45% to 75 wt%, or 47% to 70 wt%, or 50% to 65 wt%, or 50% to 65 wt% of at least one PPS polymer. - (B): 20% to 45 wt%, or 22% to 43% wt%, or 23% to 40% wt%, or 27% to 38% wt% of at least one PPSU polymer. - (C): 4.5% to 12 wt%, or 5% to 11 wt%, or 6% to 10 wt%, or 7% to 10 wt% of at least one TPE, - (D): 0.5% to 5 wt%, or 0.6% to 4 wt%, or 0.7% to 3 wt%, or 1% to 2 wt% of at least one epoxy-modified polysiloxane, - Optionally up to 10 wt% of at least one additive (E), and - Optionally less than 15 wt% of at least one other resin (F) different from components (A), (B), (C), (D) and (E), The wt% is the total weight of the PPS-based composition based on V-0 grade. The combined content of components (A), (B), (C), (D), (E), and (F) is based on a total weight of 100 wt% for a V-0 grade PPS-based composition. The V-0 and V-1 flame retardancy ratings are measured according to UL 94 V (2013) on a test piece with a thickness of 1.0 mm or less, preferably 0.8 mm.

[0147] All embodiments described above relating to the various embodiments of the PPS-based compositions and components (A)-(F) of the present invention After necessary modifications Both apply here.

[0148] Use of PPS-based compositions in the manufacture of articles Another aspect of the present invention provides the use of PPS-based compositions in the manufacture of articles.

[0149] This application applies to any of the embodiments of the PPS-based compositions of the present invention and any of the various embodiments of components (A)-(D) and optional components (E) and (F) described herein.

[0150] The PPS-based compositions detailed above can be processed using conventional melt processing techniques to provide molded articles, notably including extrusion molding, injection molding, overmolding, and / or compression molding, with extrusion molding and / or overmolding being preferred.

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

[0152] Products The present invention further relates to an article, preferably a molded article, comprising or made of the PPS-based composition of the present invention.

[0153] Any of the embodiments described herein relating to the PPS-based compositions and their various components (A)-(F) of the present invention After necessary modifications Both apply here.

[0154] Advantageously, the articles of the present invention have a V-0 rating measured in a test piece having a thickness of 1.0 mm or less, preferably 0.8 mm, according to UL 94 V (2013) standard.

[0155] The 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 molded articles, coated molded articles, multilayer articles, and / or thin-walled molded articles. "Thin-walled" molded articles have a wall thickness of at most 2 mm or less, at most 1.5 mm, or at most 1 mm, and preferably at least 0.8 mm.

[0157] Articles can be in the form of articles that are essentially two-dimensional, such as parts in which one dimension (thickness or height) is significantly smaller than the other two characteristic dimensions (width and length), such as membranes, sheaths, and sheets.

[0158] Alternatively, the article can be provided as a three-dimensional part, for example, extending substantially in three dimensions of space in a similar manner, including in the form of a part with a complex geometry, such as having concave or convex portions, possibly including undercuts, inserts, etc.

[0159] Molded products obtained through extrusion molding include round bars, square bars, sheets, films, tubes, and pipes. More specific applications include electrical insulation for water heater motors, air conditioner motors, and drive motors; materials, film capacitors, speaker diaphragms, and recording magnetic tapes; printed circuit board materials, printed circuit board peripheral components, seamless tapes, semiconductor packaging, semiconductor transport pallets, process / release films, protective films, membrane sensors for automobiles, wire and cable insulation tapes for lithium-ion batteries, insulating gaskets for lithium-ion batteries, heat transfer tubes for eV batteries, chemical tubes, automotive fuel lines, urban air travel hot water pipes, cooling water pipes, chemicals, fuel lines, hot water pipes, chemical pipes for chemical plants, pipes for ultrapure water and ultrapure solvents, automotive pipes, pipes for CFCs and supercritical carbon dioxide refrigerants, and workpiece retaining rings for polishing equipment. In addition, busbars, busbar supports, cable bundles and controls (such as those for hybrid vehicles, electric vehicles, and fuel cell vehicles), rail transit systems, coated molded parts for motor coil windings in power generation equipment, winding spools, slot liners, and slot wedges for motors or generators, heat-resistant wires and cables for household appliances, and flat cables for wiring in automobiles, etc. Examples of coated molded parts include wires, coated wires / cables such as magnetron wire, signal transformers for communication, transmission, high-frequency, audio, measurement, etc., and coated molded parts for on-board transformer windings.

[0160] Applications of injection-molded products include generators, motors, transformers, current transformers, voltage regulators, rectifiers, inverters, relays, power contacts, switches, circuit breakers, knife switches, and other terminals. Electrical equipment parts, such as rods, appliance cabinets, sensors, LED lights, connectors, sockets, resistors, relay boxes, small switches, winding spools (e.g., coil winding spools), capacitors, variable condenser boxes, optical pickups, oscillators, various terminal blocks, transformers, plugs, printed circuit boards, tuners, speakers, microphones, headphones, small motors, magnetic head mounts, power modules, semiconductors, LCDs, FDD brackets, FDD chassis, motor brush holders, parabolic antennas, computer-related parts, etc.; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, audio parts, audio equipment parts such as audio equipment, laser discs (registered trademark) and optical discs, lighting parts, refrigerator parts, air conditioner parts, typewriters, parts for household / office electrical products, word processor parts, etc. Representative products include office computer parts, telephone parts, fax machine parts, copier parts, cleaning fixtures, motor parts, writing instruments, typewriters, etc. Mechanical parts include: microscopes, binoculars, cameras, clocks, and other optical equipment and precision mechanical parts; alternator terminals, alternator connectors, IC regulators, dimmer potentiometer bases, fuel-related exhaust valves, exhaust systems, various pipes and ducts for intake systems, turbine ducts, intake nozzle vent pipes, intake manifolds, fuel pumps, engine coolant connectors, carburetor bodies, carburetor gaskets, exhaust sensors, coolant sensors, oil temperature sensors, brake pad wear sensors, throttle position sensors, crankshaft position sensors, air flow meters, air conditioner thermostat bases, and heating system components. Examples of automotive and vehicle-related parts include flow control valves, radiator motor brush holders, water pump impellers, turbine blades, wiper motor components, distributors, starter switches, starter relays, transmission cable harnesses, windshield washer nozzles, air conditioning panel switchboards, fuel-related solenoid valve coils, fuse connectors, horn terminals, electrical component insulation boards, stepper motor rotors, lamp holders, lamp reflectors, lamp covers, brake pistons, solenoid winding spools, engine oil filters, protective gaskets, insulating locks, ignition device housings, and other automotive and vehicle-related parts, as well as mobile phones, smartphones, laptops, tablets, cameras, hybrid vehicles, and secondary battery gaskets.

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

[0162] A slot liner is a component in an electric motor, such as a motor or generator, that provides an electrical insulation barrier between the electrical windings and the stator. This component is cut from a membrane and shaped to fit into the slot of the motor or generator.

[0163] A slot wedge is a slot closure used to hold the stator winding in the slot.

[0164] A winding drum can be a support for a coil or electrical winding.

[0165] For coated wires or cables, PPS-based compositions can be used to form a coating around conductive wires or cables for protective and encapsulating purposes. PPS-based compositions can be extruded around conductive wires or cables using a sheathing machine to form a protective coating on the outer surface of the wire / cable. For example, the magnet wires used in electric motors are typically conductive wires (preferably made of copper) coated with a polymer sheath. This polymer coating can be made from a PPS-based flame-retardant composition.

[0166] Electrical busbars are commonly used in electric motors and eV power electronic devices. They preferably comprise metal bars coated with a thermoplastic compound that provides electrical insulation and scratch resistance. In such examples, molded metal strips are coated with a PPS-based flame-retardant composition to form the busbar.

[0167] Power modules provide a physical barrier for multiple electrical components. This physical barrier can be made from a PPS-based flame-retardant composition. Power modules are used in power conversion devices such as industrial motor drivers, embedded motor drivers, uninterruptible power supplies (UPS), AC-DC power supplies, and welding power supplies.

[0168] In particular, since 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, it is suitable for manufacturing tubular components with a hollow shape.

[0169] Tubular components, which can be used to carry liquids or gases, and in one particular embodiment to carry cooling fluids, can be formed from PPS-based compositions. For example, tubular components including pipes, hoses, tubes, conduits, etc., can be formed from PPS-based compositions. In one embodiment, for example, the PPS-based composition can be used to form extruded hollow components.

[0170] Therefore, the articles of the present invention may be tubes or pipes comprising or composed of PPS-based compositions as detailed above. Such tubes are preferably heat transfer tubes.

[0171] Advantageously, the tube of the present invention, preferably the heat transfer tube, has a V-0 rating as determined according to the UL 94 V (2013) standard (when measured on a test piece with a thickness of 0.8 mm).

[0172] The tubular components, preferably heat transfer tubes, of the present invention can be manufactured using any suitable method known in the art. The tubes, preferably heat transfer tubes, of the present invention are typically manufactured by extrusion. Suitably, the entire length of the tube is extrudable and / or extruded in a single extrusion process.

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

[0174] The tubular component of the present invention, preferably a heat transfer tube, is hollow to allow fluid to flow through it. When the tubular component is a hollow heat transfer tube, the fluid is a heat transfer fluid.

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

[0176] In a preferred embodiment, the hollow tubular component of the present invention, preferably a hollow heat transfer tube, is integrally made of the PPS-based flame-retardant composition as detailed above.

[0177] In other embodiments, the tubular member incorporating the PPS-based composition may be a multilayer tubular member. A multilayer tubular member may include two, four, or more distinct layers. The PPS-based composition may be incorporated into one or more layers of the tubular member, such as into an inner layer, an outer layer, and / or into one or more intermediate layers sandwiched between the inner and outer layers, preferably into the inner layer.

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

[0179] Alternatively, when at least one layer is made of a PPS-based composition, the other layers of the multilayer tubular member can be formed of different materials. For example, in one embodiment, the intermediate layer can be formed of 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 is highly resistant to mechanical shock.

[0180] When the layer is made from a PPS-based composition, the layer thickness can 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 layer thickness can 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 components can be manufactured using conventional methods, such as co-extrusion, dry lamination, sandwich lamination, and co-extrusion coating, preferably co-extrusion or co-extrusion coating. For example, in forming a bilayer tubular component, a PPS-based composition and different polymer compositions can be fed separately into two different extruders. The individual extruded melts from these two extruders can then be introduced under pressure into a single die. 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 compositions forms the outer layer, and the thus combined melt flows are co-extruded from the die to produce a bilayer tubular component.

[0182] Of course, any known tube forming 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 strip (e.g., a fiber-reinforced strip or tape formed according to a pultrusion forming method). The strip can be wrapped to form the tubular member or layers of a multilayer tubular member according to known practices generally known in the art.

[0183] When tubular components are heat transfer tubes used in a thermal management system, the size of the tubes is not limited, and they are sized by the thermal management system.

[0184] The tubular component, preferably a heat transfer tube, of the present invention can have a diameter ranging from 5 to 50 mm, or even from 5 to 30 mm. The wall thickness of the tubular component, preferably a heat transfer tube, is typically ranging from 0.7 to 5.0 mm, 0.8 to 5.0 mm, or even from 1.0 to 5.0 mm. Alternatively, the wall thickness of the tubular component, preferably a heat transfer tube, is typically ranging from 0.8 to 2 mm, 0.8 to 1.5 mm, or even from 0.8 to 1 mm. The tubular component, preferably a heat transfer tube, of the present invention can have a length ranging from 10 cm to several meters (e.g., up to 2 m).

[0185] Uses of the product Another aspect of the present invention is a thermal management system comprising a heat transfer tube according to the invention. The thermal management system further comprises a heat transfer fluid. The heat transfer fluid is contained within the heat transfer tube. The heat transfer fluid preferably flows within the heat transfer tube. The heat transfer fluid may be selected from the group consisting of water, water / ethylene glycol mixtures, chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HFCs), and (per)fluorinated polyethers (PFPEs). In a preferred embodiment of the invention, the heat transfer fluid is selected from the group consisting of water or water / ethylene glycol mixtures. In some embodiments, the heat transfer fluid may be selected from the group consisting of chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HFCs), and (per)fluorinated polyethers (PFPEs). The thermal management system of claim 8 further comprises the heat transfer fluid contained within the heat transfer tube.

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

[0187] BTMS can be more or less complex, depending on the application, but at a minimum, BTMS has the function of cooling the battery when the temperature is too high and heating the battery when the temperature is too low, typically using a heat transfer fluid that exchanges heat with the battery flowing within the cooling pipes of the present invention. Other common features of BTMS are an insulation system that reduces the influence of the external environment on the battery temperature, and a ventilation system that helps dissipate harmful gases that may be generated within the battery pack.

[0188] Typically, the heat transfer fluid is circulated within a closed system by a pump. This closed system includes the heat transfer tube of the present invention, which is in thermal contact with a 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 refrigeration system and a heating system, or heating and cooling functions may be combined in a heat pump. The circulating heat transfer fluid absorbs heat from or releases heat to the battery and then circulates in the second system to return the heat transfer fluid to the desired temperature. A more or less complex control system may exist that controls the instantaneous temperature of the heat transfer fluid and the battery temperature to optimize the temperature of the heat transfer fluid at each moment.

[0189] Therefore, another aspect of the present invention is a method for controlling the temperature in a battery, the method comprising the step of circulating a heat transfer fluid within a closed system including the 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] Another aspect of the invention is a method for operating a battery, the method comprising the steps of controlling the temperature of the battery as defined above.

[0191] Batteries including BTMS, as detailed above, can be used in all applications where rechargeable batteries can be used. Notable, non-limiting examples of such applications include, for example, urban motor vehicles such as cars, electric bicycles, buses, etc.

[0192] The above embodiments are intended to be illustrative and not restrictive. Additional embodiments are within the scope of the inventive concept. Furthermore, although the invention has been described with reference to specific embodiments, those skilled in the art will recognize that changes in form and detail may be made without departing from the spirit and scope of the invention.

[0193] Example The invention will now be described with reference to the following examples, which are merely illustrative and not intended to limit the scope of the invention. As used in the examples, "Ex" indicates an exemplary embodiment of the invention, and "CEx" indicates a counterexample.

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

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

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

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

[0198] KF-105: Epoxy-modified PDMS available from Shin-Etsu Corporation, which is a bi-epoxy-terminated polysiloxane represented by formula (11) with a molecular weight of 490 g / mol, wherein n makes the viscosity at 25°C 15 cSt.

[0199] General procedures for preparing compositions First, dry the PPSU polymer (PPSU-1 or PPSU-2) in an oven at 135°C for at least 5 hours.

[0200] The dry blends were then achieved by mixing polymer components (A) through (D): PPS, PPSU, TPE, and PDMS were continuously vibrated in a vibratory oscillator for 2–3 minutes to ensure homogeneity. The dry blends were then placed in a gravity feeder and fed into a twin-screw extruder (Clextral D32) for melting and extrusion. The temperature range during extrusion of the PPS-based compositions was 320°C to 350°C.

[0201] The melt stream is cooled and fed into the granulator.

[0202] Collect the granules and store them in sealed plastic buckets until they are used for injection molding.

[0203] test The following test methods are used to evaluate the flame retardancy of PPS-based compositions. UL 94 V (2013): According to Underwriters Laboratories (USA), 6th edition, March 28, 2013. For equipment Flammability testing of plastic materials for appliance parts The standard UL 94 V vertical burning test procedure evaluates the flame retardancy of a sample with a thickness of 0.8 mm.

[0204] The ignition source used was a 50-watt test flame, and the sample was briefly exposed to this flame twice. During this process, the burning time and the dripping of burning particles were evaluated using a cotton indicator placed under the sample.

[0205] For the V-2 rating, combustion on the vertical specimen ceases within 30 seconds, and burning particles are allowed to drip off.

[0206] For the V-1 grade, combustion on the vertical specimen ceases within 30 seconds, and droplets are allowed as long as the particles are not burning.

[0207] For the V-0 rating, combustion on the vertical specimen must cease within 10 seconds; droplets are permitted as long as the particles are not burning.

[0208] The UL 94 V (2013) (vertical burning test, flame: 50 W) test standard is summarized in Table 1.

[0209] Table 1 Table 2 details a variety of compositions, where all percentages are by weight relative to the total weight of the PPS-based compositions.

[0210] Table 2 Composition CE1 E2 CE3 E4 PPS 57% 55.5% 57% 55.5% PPSU-1 33% 33% - - PPSU-2 - - 33% 33% TPE 10% 10% 10% 10% KF-105 - 1.5% 1.5% For compositions CE1, E2, CE3 and E4, thin small parts (0.8 mm) are manufactured by injection molding on a Billion injection molding machine at a temperature ranging from 320°C to 340°C.

[0211] For each composition CE1, E2, CE3 and E4, the flame retardancy results of the five thin-walled part samples evaluated according to UL 94 V (2013) are summarized in Table 3 below.

[0212] Table 3 Composition CE1 E2 CE3 E4 Thickness (mm) 0.8 0.8 0.8 0.8 Longest T1(s) 9 5 11.8 6.2 Longest T2(s) 8 6 6 3.7 T1 + T2(s) for all 5 samples 51 35 46.5 20.7 Afterglow + T2(s) 22 19 Burned to the clamp 0 0 Ignite the cotton 0 0 Rating V-1 V-0 V-1 V-0 Compared to reference compositions CE1 and CE3, which contain PPS, PPSU, and TPE (PDMS without epoxy group modification: KF-105) and exhibit a V-1 rating, compositions E2 and E4 of the present invention (containing epoxy group modified PDMS: KF-105) unexpectedly produce materials that meet the V-0 rating measured on thin specimens with a thickness of 0.8 mm according to the UL 94 V (2013) flammability standard.

[0213] In addition to improved flame retardancy, no negative impact on the fracture deformation rate was observed when epoxy-modified PDMS (KF-105) was added to PPS-based compositions E2 and E4, compared to the fracture deformation rate obtained with reference compositions CE1 and CE3 (without KF-105).

[0214] Tube extrusion The PPS-based compositions of Examples E2 and E4 in Table 2 can be used to prepare the tubes as follows: The PPS-based compositions are dried at 90°C for 4 hours and then loaded into an extruder. The barrel extruder temperature is set between 320°C and 340°C.

[0215] Use a calibration bath to extrude tubes. The resulting tubes should have a good surface appearance and a regular shape. These tubes preferably have 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 (e.g., up to 1 to 2 meters).

[0216] All disclosures of patent applications and publications cited herein are incorporated herein by reference to the extent that they provide exemplary, procedural, or other detailed supplements to those presented herein. If any disclosure of a patent, patent application, or publication incorporated herein by reference conflicts with the description of this application to the extent that it may make the terminology unclear, this description shall prevail. Any inclusion of documents by reference is limited such that no subject matter contrary to the explicit disclosure herein is incorporated.

[0217] Although preferred embodiments of the invention have been shown and described, modifications can be made by those skilled in the art without departing from the teachings of the invention. The embodiments described herein are merely exemplary and non-limiting. Therefore, the scope of protection is not limited by the foregoing description, but only by the following claims, which include all equivalents of the subject matter of the claims. Each claim is incorporated herein by reference as an embodiment of the invention.

Claims

1. A PPS-based flame retardant composition comprising: - (A) 45 to 75 wt% of at least one polyphenylene sulfide polymer (hereinafter referred to as "PPS polymer"), - (B) 20 to 45 wt% of at least one polyphenylene sulfone polymer (hereinafter referred to as "PPSU polymer"), - (C) 4.5 to 12 wt% of at least one thermoplastic elastomer containing epoxy functional groups (hereinafter "TPE"), - (D) 0.5 to 5 wt% epoxy-modified polysiloxane, The wt% is based on the total weight of the PPS-based composition. The combined amount of components (A), (B), (C) and (D) is 100 wt% or less based on the total weight of the PPS-based composition.

2. The PPS-based flame retardant composition as described in claim 1, wherein, The PPS-based composition comprises at least one PPS polymer in the following amounts: - At least 47 wt%, or at least 50 wt%, and - Up to 70 wt%, up to 65 wt%, or up to 60 wt%. The wt% is based on the total weight of the PPS-based composition.

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

4. The PPS-based flame-retardant composition according to any one of claims 1 to 3, wherein, The PPS polymer comprises at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, or at least 99 mol% of repeating units (R) represented by formula (1') based on the total molar percentage of repeating units in the PPS polymer. PPS ): (1’)。 5. The PPS-based flame-retardant composition according to any one of claims 1 to 4, wherein, The PPS-based composition contains the following amounts of at least one PPSU polymer: - At least 22 wt%, at least 25 wt%, at least 27 wt%, or at least 29 wt%, and - Up to 43 wt%, up to 40 wt%, or up to 38 wt%. The wt% is based on the total weight of the PPS-based composition.

6. The PPS-based flame-retardant composition according to any one of claims 1 to 5, wherein, The PPSU polymer contains at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, or at least 99 mol% of repeating units (R) having formula (2) based on the total molar percentage of repeating units in the PPSU polymer. PPSU ): (2)。 7. The PPS-based flame-retardant composition according to any one of claims 1 to 6, wherein, The PPS-based composition contains at least one TPE in the following amounts: - At least 4.5 wt%, at least 5 wt%, at least 6 wt%, at least 7 wt%, or at least 8 wt%, and - Up to 11 wt%, up to 10.5 wt%, up to 10 wt%. The wt% is relative to the total weight of the PPS-based composition.

8. The PPS-based flame retardant 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 methacrylate-co-glycidyl methacrylate) copolymer, poly(ethylene-co-n-butyl acrylate-co-glycidyl methacrylate) copolymer, and copolymers of styrene and (methyl) methacrylate, preferably selected from poly(ethylene-co-glycidyl methacrylate) copolymer and / or poly(ethylene-co-(methyl methacrylate-co-glycidyl methacrylate) copolymer; more preferably selected from poly(ethylene-co-glycidyl methacrylate) copolymer.

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

10. The PPS-based flame retardant composition according to any one of claims 1 to 9, wherein, The epoxy-modified polysiloxane has at least one side epoxy functional group, and wherein the epoxy-modified polysiloxane (D) further contains at least one epoxy-modified siloxane unit (R) represented by general formula (4) or (5). EM s): in - R2 in formulas (4) and (5) is a C1-C3 alkyl or phenyl; - R3 in equations (4) and (5) is the linking group represented by equation (6): –(CH2) k –O–CH2– (6), Where k is an integer from 1 to 10, preferably from 2 to 8, more preferably from 3 to 6, and most preferably 3; and - In equations (4) and (5), m is an integer from 1 to 10.

11. The PPS-based flame retardant 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 wherein the terminal epoxy functional group in the polysiloxane is represented by one of the following formulas (7) and (8): R3 is represented by equation (6): –(CH2) k –O–CH2– (6), Where k is an integer from 1 to 10, preferably from 2 to 8, more preferably from 3 to 6, and most preferably 3.

12. The PPS-based flame retardant 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): in: - Each of R1 and R2 in formulas (9) and (10) is independently a C1-C3 alkyl and / or phenyl; - R3 in equations (9) and (10) is the linking group represented by equation (6): –(CH2) k –O–CH2– (6) Where k is an integer from 1 to 10, preferably from 2 to 8, more preferably from 3 to 6, and most preferably 3; and - n varies from 2 to 100, or from 2 to 70, or from 2 to 60.

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

14. The PPS-based flame retardant composition of 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 PPS-based flame retardant composition according to any one of claims 1 to 14, wherein, The epoxy-modified polysiloxane has the following molecular weight: - At least 300 g / mol, at least 350 g / mol, or at least 400 g / mol, and - Up to 5000 g / mol, up to 4000 g / mol, up to 3000 g / mol, up to 2000 g / mol, or up to 1000 g / mol.

16. The PPS-based flame retardant composition according to any one of claims 1 to 15, further comprising an amount not exceeding 10 wt% of at least one additive (E), the additive being selected from the group consisting of: antioxidants, light stabilizers, UV 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. The PPS-based flame retardant composition according to any one of claims 1 to 16, wherein, The flame retardant is not present in this PPS-based flame retardant composition.

18. The PPS-based flame retardant composition according to any one of claims 1 to 17, having a flame retardancy of V-0 as measured in a test piece having a thickness of 0.8 mm according to UL94 standards.

19. A method for improving the flame retardancy of a V-1 grade PPS-based composition, the V-1 grade PPS-based composition comprising at least one polyphenylene sulfide polymer ("PPS polymer"), at least one polyphenylene sulfone polymer ("PPSU polymer"), and at least one thermoplastic elastomer ("TPE") containing epoxy functional groups. The method involves 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 flame-retardant composition. The V-0 rated PPS-based flame retardant composition comprises: - A) 45 to 75 wt% of the at least one PPS polymer, - B) 20 to 45 wt% of the at least one PPSU polymer, - C) 4.5 to 12 wt% of the at least one TPE, - D) 0.5 to 5 wt% of this epoxy-modified polysiloxane, The wt% is based on the total weight of the PPS-based flame retardant composition of the V-0 rating. The combined amounts of components (A), (B), (C), and (D) are 100 wt% or less based on the total weight of the PPS-based flame retardant composition for V-0 rating. The V-0 and V-1 flame retardancy ratings are measured according to UL 94 V (2013) on a test piece with a thickness of 1.0 mm or less, preferably 0.8 mm.

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

21. The molded article of claim 20, selected from the group consisting of: tubular components such as heat transfer tubes, coated wires or cables such as magnet wires, slot liner, winding bobbins such as coil winding bobbins, slot wedges, power modules, and busbars.

22. The molded article as claimed in claim 20 or 21, which is formed by extrusion molding.

23. The molded article as claimed in any one of claims 20-22, wherein it is a hollow tubular member that allows fluid to flow through it.

24. The molded article of any one of claims 20-23, wherein the multilayer tubular member comprises two or more layers, wherein at least one layer is made of the PPS-based composition of any one of claims 1-18.

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

26. The molded article of claim 26, wherein, The tubular member has a diameter ranging from 5 to 50 mm and a wall thickness ranging from 0.5 to 5.0 mm.

27. The molded article as claimed in any one of claims 20-26, wherein it is a heat transfer tube.

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

29. The thermal management system as described in claim 28, wherein, The tubular component is a heat transfer tube containing a heat transfer fluid housed therein.

30. The thermal management system as described in claim 29, wherein, The heat transfer fluid is selected from the group consisting of: water, water / ethylene glycol mixtures, chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HFCs), and (per)fluorinated polyethers (PFPEs).

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

32. The device of claim 31, wherein the device is a battery, preferably a rechargeable battery.

33. An apparatus comprising the battery as described in claim 32, wherein the apparatus is an electric vehicle.

34. A method for controlling temperature in a battery, the method comprising the step of circulating a heat transfer fluid within a closed system comprising a tubular member as claimed in any one of claims 23 to 27, wherein, The system is in thermal contact with the battery and the second system, the 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, the method comprising controlling the temperature in the battery as claimed in claim 32.

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