Poly(arylene sulfide) composition and use thereof

Abstract

The present invention relates to a composition comprising a poly(arylene sulfide) polymer and at least one impact modifier, and to its use for the manufacture of a barrier layer in articles adapted for the storage and transportation of gases, in particular hydrogen. The invention further relates to such articles, such as containers and more preferably pressure vessels, comprising such a barrier layer.

Description

SSPU 2024 / 045DescriptionPoly(arylene sulfide) composition and use thereofCross reference to related patent application

[0001] This patent application claims priorities filed on 20 December 2024 in the United States of America with Nr. 63 / 737485 and filed on 20 January 2025 in Europe with Nr. 25152729.7, the whole content of each of these application being incorporated herein for all purposes.Technical field

[0002] The present invention relates to a composition comprising a poly(arylene sulfide) polymer and at least one impact modifier, and to its use for the manufacture of a barrier layer in articles adapted for the storage and transportation of gases, in particular hydrogen. The invention further relates to such articles, such as containers and more preferably pressure vessels, comprising such a barrier layer.Background

[0003] To achieve levels of decarbonisation required to meet the Intergovernmental Panel on Climate Change target of preventing global warming greater than 1.5 °C above pre-industrial levels, strong global action to reduce carbon emissions is being undertaken. Hydrogen, in particular the so-called “green hydrogen”, that is hydrogen produced using clean energy sources, as an energy carrier has been identified as suitable for meeting these climate objectives. A key challenge to enabling the use of hydrogen, particularly in weight-critical aerospace and automotive environments, is storing it with high volumetric and gravimetric density.

[0004] Despite its popularity, the storage of hydrogen as a gas is challenging as it is the lightest element and must be held at very high pressure (i.e. , 350-700 bar) to achieve practical densities. The storage or transportation of large volumes of highly compressed hydrogen requires a shift from the use of metal containers or piping to lighter materials, such as polymeric materials.

[0005] Pressure vessels characterized by high gas barrier properties have been used for storing various gasses such as oxygen, carbon dioxide, nitrogen, argon, LPG (liquefied petroleum gas), methane, hydrogen, over a long period of time.SSPU 2024 / 045

[0006] Pressure vessels comprising a non-structural layer, or liner, surrounded with a structural fiber reinforced composite material for containing the fluid or gas under pressure are known. The liner acts as a barrier between the fluid or gas and the fiber reinforced composite material, thus preventing leaks and / or other degradations of the structure of the fiber reinforced composite material. The use of structural fiber reinforced composite materials comprising a thermoplastic polymer matrix, rather than a thermoset one, is advantageous to facilitate recycling of the pressure vessel.

[0007] However, it is known from the literature that the use of a plastic liner may provide issues due to the blistering effect, occurring when the tank rapidly depressurizes or when exposed to multiple hydrogen cycles, which leads to hydrogen leakage from the tank, which is highly undesired. Reference is made for example to T.A. Yersak et al. , “Predictive model for depressurization- induced blistering of type IV tank liners for hydrogen storage", International Journal of Hydrogen Energy, Volume 42, Issue 48, 30 November 2017, Pages 28910-28917 and to M.C. Kane, “Permeability, solubility, and interaction of hydrogen in polymers- an assessment of materials for hydrogen transport’ 2008.

[0008] WO 2024 / 126470 (in the name of Solvay Specialty Polymers USA, LLC) discloses a multilayer structure comprising at least one gas barrier layer [layer (BL)] and at least one composite layer [layer (CL)], in contact with the at least one layer (BL), wherein layer (BL) comprises a poly(arylene sulfide) polymer and layer (CL) comprises continuous reinforcing fibers and a poly(arylene sulfide) polymer. Such multilayer structure was submitted to a dynamic cycling test to detect blistering between the liner and the fiber reinforced layers for blistering at a pressure > 44 MPa and to a static blistering test wherein the exposure time was 48 hours.

[0009] US 2013 / 273288 (in the name of Ticona LLC.) discloses, among the others, a composition comprising a polyarylene sulfide, Lotader® 4720 as impact modifier, which is a random terpolymer of ethylene, ethyl acrylate and maleic anhydride. However, this document does not comprise examples of an impact modifier that is a terpolymer of ethylene, acrylate ester and glycidyl methacrylate.

[0010] The Applicant perceived that the need still exists to develop articles for the transport and storage of hydrogen and gasses in general, in particular pressure vessels, which show high performance qualities in terms of impermeability to the stored gas.Summary of the inventionSSPU 2024 / 045

[0011] The Applicant faced the problem of providing a composition suitable for the manufacture of articles, such as containers and more preferably pressure vessels, such composition providing very low permeability to gases, in particular to hydrogen, and showing a reduced blistering effect even when exposed to conditions more severe than those disclosed in WO 2024 / 126470 mentioned above.

[0012] The Applicant surprisingly found that the composition according to the present invention can be used to manufacture articles, including containers and more preferably vessels such as pressure vessels, which have very low permeability to gases, in particular to hydrogen, and which show a limited or null blistering effect, when tested under both static and dynamic conditions and especially at low temperatures (such as at -40°C).

[0013] Even more, the composition according to the present invention showed good mechanical properties at low temperature (including at -40°C) while having a viscosity suitable for being manufactured via traditional manufacturing methods, such as injection or blow molding or extrusion. In other words, composition (Cl) of the present invention remains ductile and has good mechanical properties over a very broad range of temperatures.Disclosure of the invention

[0014] As used in the present description and in the following claims:- the use of parentheses around symbols or numbers identifying the formulae, for example in expressions like “composition (Cl)”, etc., has the mere purpose of better distinguishing the symbol or number from the rest of the text and, hence, said parenthesis can also be omitted;- any description, even though described in relation to a specific embodiment, is applicable to and interchangeable with other embodiments of the present disclosure;- any recitation herein of numerical ranges by endpoints includes all numbers subsumed within the recited ranges as well as the endpoints of the range and equivalents;- the indeterminate article “a” in an expression like “a polyamide polymer”, is intended to mean “one or more”, or “at least one” unless indicated otherwise;- the term “alkyl”, as well as derivative terms such as “alkoxy”, “acyl” and “alkylthio”, as used herein, include within their scope straight chain, branched chain and cyclic moieties. Examples of alkyl groups are methyl, ethyl, 1 methylethyl, propyl, 1 ,1-SSPU 2024 / 045 dimethylethyl, and cyclo-propyl. Unless specifically stated otherwise, each alkyl and aryl group may be unsubstituted or substituted with one or more substituents selected from but not limited to halogen, hydroxy, sulfo, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 acyl, formyl, cyano, C6-C15 aryloxy or C6-C15 aryl, provided that the substituents are sterically compatible and the rules of chemical bonding and strain energy are satisfied;- the term “halogen” or “halo” includes fluorine, chlorine, bromine and iodine, with fluorine being preferred;- the term “aryl” refers to a phenyl, indanyl or naphthyl group. The aryl group may comprise one or more alkyl groups, and are called sometimes in this case “alkylaryl”; for example may be composed of a cyclo-aromatic group and two C1-C6 groups (e.g. methyl or ethyl). The aryl group may also comprise one or more heteroatoms, e.g. N, O or S, and are sometimes called “heteroaryl” groups; these heteroaromatic rings may be fused to other aromatic systems. The aryl or heteroaryl substituents may be unsubstituted or substituted with one or more substituents selected from but not limited to halogen, hydroxy, C1-C6 alkoxy, sulfo, C1-C6 alkylthio, C1-C6 acyl, formyl, cyano, C6-C15 aryloxy or C6-C15 aryl, provided that the substituents are sterically compatible and the rules of chemical bonding and strain energy are satisfied.- the proportions of repeating units in a polymer are given relative to the total moles of repeating units in the polymer;- the concentration of repeating units in “percent by mol” or “mol%” or “% by mol” refers to the concentration of a given type of repeating unit relative to the total number of repeating units in the polymer, unless explicitly stated otherwise.

[0015] In a first aspect, the present invention relates to a composition [composition (Cl)] comprising:- at least one poly(arylene sulfide) polymer having melt flow rate of at most 200 g / 10 min and of at least 2 g / 10 min, the melt flow rate being the value measured in an extrusion plastomer at 315.6°C using a weight of 5 kg and a 0.21 cm x 0.80 cm die after a 5 minute equilibration period, according to ASTM D1238, procedure B, and- at least one impact modifier selected from terpolymers of ethylene, acrylic ester and glycidyl methacrylate, in an amount from 2.5 to less than 22.0 wt.% based on the total weight of composition (Cl).SSPU 2024 / 045

[0016] In a second aspect, the present invention relates to an article comprising composition (Cl) of the present invention.

[0017] As described in more detail in the following description, said article is not particularly limited.

[0018] In a preferred embodiment, said article is a multilayer article, which comprises at least one first layer comprising composition (Cl) of the present invention and at least one second layer, said second layer being in contact with said at least one first layer.

[0019] According to a preferred embodiment, said multilayer article is a vessel [vessel (V)].

[0020] More preferably, said vessel (V) comprises a first layer comprising composition (Cl) of the present invention and at least one second layer comprising a polymer matrix and reinforcing fibers.

[0021] In a further aspect, the present invention relates to at least one compressed gas contained in said vessel (V), wherein said at least one compressed gas is in contact with said layer (BL).

[0022] Furthermore, the present invention relates to a method for the manufacture of said vessel (V) and to the use of vessel (V) in vehicles or for the transportation of gas(es).

[0023] Indeed, surprisingly, the composition of the present invention is such that it is capable of providing an article that - thanks to its reduced hydrogen permeability and reduced moisture absorption and desorption - is suitable for use in the storage or transportation of compressed gas, in particular hydrogen.

[0024] Composition (Cl)

[0025] Preferably, said poly(arylene sulfide) polymer comprises at least 50.0 mol% of a recurring unit (RPAS) having at least one aromatic ring bonded to a sulfur atom.

[0026] Preferably, the amount of said recurring unit (RPAS) is at least 60.0 mol%, at least 70.0 mol%, at least 80.0 mol%, at least 90.0 mol%, at least 95.0 mol%, at least 97.0 mol%, at least 98.0 mol%, at least 99.0 mol% or at least 99.9 mol%.

[0027] As used herein, mol% is relative to the total number of recurring units in the poly(arylene sulfide) polymer, unless explicitly noted otherwise.

[0028] Preferably, said recurring unit (RPAS) is represented by a formula selected from the following formulae (1) to (3):SSPU 2024 / 045whereinR is, at each instance, independently selected from the group consisting of a C1-C12 alkyl group, a C7-C24 alkylaryl group, a C7-C24 aralkyl group, a C6-C24 arylene group, and a C6-C18 aryloxy group;T is selected from the group consisting of a bond, -CO-, -SO2-, -O-, -C(CH3)2, phenyl and -CH2-; i is , at each instance, independently 0 or an integer from 1 to 4; and j, is , at each instance, independently 0 or an integer from 1 to 3.

[0029] For sake of clarity, when i or j is zero, the corresponding aromatic rings are unsubstituted.

[0030] Preferably, such poly(arylene sulfide) polymer is a poly(phenylene sulfide) polymer [PPS polymer],

[0031] The expression “poly(phenylene sulfide)” or PPS, is used to refer to a poly(arylene sulfide) polymer where the recurring unit (RPAS) is represented by formula (1).SSPU 2024 / 045

[0032] More preferably, recurring unit (RPAS) is represented by formula (1-a):(1-a) wherein Rj as is defined above.

[0033] Most preferably in formula (1-a) i is 0.

[0034] Said PPS polymer may be acid washed or not acid washed.

[0035] Preferably, said PPS polymer is acetic acid washed PPS polymer.

[0036] More preferably, the PPS polymer is such that at least 90.0 mol% of the recurring units are recurring units of formula (1-a) in which i is 0.

[0037] Even more preferably, the PPS polymer consists essentially of recurring units of formula (1-a) in which i is 0.

[0038] Preferably, the PPS polymer has a melt flow rate of at most 200 g / 10 min, more preferably of at most 195 g / 10 min, even more preferably of at most 190 g / 10 min and still more preferably of at most 185 g / 10 min. According to a preferred embodiment, the PPS polymer has a melt flow rate of at most 150 g / 10 min, more preferably of at most 135 g / 10 min.

[0039] Preferably, the PPS has a melt flow rate of at least 4 g / 10 min, more preferably of at least 10 g / 10 min, even more preferably of at least 15 g / 10 min and still more preferably of at least 25 g / 10 min.

[0040] In the present specification, the melt flow rate of PPS polymer refers to the value measured in an extrusion plastomer at 316 °C using a weight of 5 kg and a 0.21 cm x 0.80 cm die after a 5 minute equilibration period, according to ASTM D1238, procedure B.

[0041] Advantageously, the melt flow rate (at 316°C and 5 kg) of the PPS polymer is from 50 to 175 g / 10 min, more preferably from 60 to 150 g / 10 min.

[0042] For sake of clarity, when two or more PPS polymers are used as ingredients in the composition, the overall melt flow rate of the two or more PPS polymers is at most 200 g / 10 min, more preferably at most 195 g / 10 min. Preferably when two or more PPS polymers are used as ingredients in the composition, the overall melt flow rate provided by the two or more PPS polymers is of at least 1 g / 10 min, more preferably of at least 5 g / 10 min. The melt flow rate is calculated as disclosed above.SSPU 2024 / 045

[0043] Advantageously, when two or more PPS polymers are used as ingredients in the composition, the overall melt flow rate (at 316°C and 5 kg) of the two or more PPS polymers is from 50 to 175 g / 10 min, more preferably from 60 to 150 g / 10 min.

[0044] Suitable PPS polymers are commercially available under the trade name Ryton® PPS from Solvay Specialty Polymers USA, LLC.

[0045] Preferably, said poly(arylene sulfide)polymer is in an amount from 50 wt.% to 98.5 wt.% based on the total weight of composition (Cl), more preferably from 70 wt.% to 97.5 wt.% and even more preferably from 75 wt.% to 95 wt.%.

[0046] Preferably, said at least one impact modifier is in an amount from at least 3.5 wt.%, more preferably from at least 4.5 wt.%, at least 5.0 wt.%, at least 7.5 wt.% and even more preferably at least 10.0 wt.%, such as at least 11.0 wt.% and at least 12.5 wt.% based on the total weight of composition (Cl).

[0047] Preferably, said at least one impact modifier is in an amount up to 20.0 wt.% more preferably up to 19.5 wt.% and even more preferably up to 18.0 wt.% based on the total weight of composition (Cl).

[0048] Advantageously, said at least one impact modifier is commercially available from Arkema (Bristol, PA, USA) under the trade name Lotader® AX8900, or from Sumitomo Chemical (JP) under the trade name Igetabond™ BF-7M.

[0049] Composition (Cl) according to the present invention can comprise additional ingredients.

[0050] Suitable additional ingredients are selected in the group comprising stabilizers; antioxidants, such as ultraviolet light stabilizers and heat stabilizers; processing aids; nucleating agents; lubricants; flame retardants; smoke-suppressing agents; antistatic agents; anti-blocking agents; colorants; and pigments, such as carbon black.

[0051] When present, each of said additional ingredients is preferably present in an amount from 0.1 wt. to about 5 wt.% based on the total weight of the composition (Cl).

[0052] The total amount of additives may be 20.0 wt.% or less, even 10.0 wt.% or less with respect to the total weight of said composition (Cl). When present the one or more additives is at least 0.5 wt.%, even at least 0.7 wt.%, relative to the total weight of composition (Cl).

[0053] The article

[0054] The article of the present invention comprises either a monolayer or a multilayer.

[0055] When the article of the present invention is a monolayer, said monolayer comprises composition (Cl) as above defined.SSPU 2024 / 045

[0056] The article according to the present invention is not limited and can be suitable for use in a wide variety of application settings, such as automotive components, battery housings, aerospace components, oil and gas drilling components, a component for Smart Devices, a medical housing or component for medical devices, an Urban Air Mobility device, and an electronic device.

[0057] With respect to automotive applications, the article can be integrated into automotive components including, but not limited to, pans (e.g. oil pans), panels (e.g. exterior body panels, including but not limited to quarter panels, trunk, hood; and interior body panels, including but not limited to, door panels and dash panels), side-panels, mirrors, bumpers, bars (e.g., torsion bars and sway bars), rods, suspensions components (e.g., suspension rods, leaf springs, suspension arms), turbo charger components (e.g. housings, volutes, compressor wheels and impellers) and housings for battery components.

[0058] The article of the present invention can also be desirably integrated into aerospace components, oil and gas drilling components (e.g. downhole drilling tubes, chemical injection tubes, subsea umbilicals and hydraulic control lines) and mobile electronic device components, as well as geothermal applications and carbon capture utilization and storage (CCSU).

[0059] Notable non-limiting examples of articles are hoses, pipes, tubes, joints, tanks, reservoirs or hollow containers such as vessels and more preferably pressure vessels.

[0060] According to a preferred embodiment, the article of the present invention is a multilayer article comprising at least one first layer comprising composition (Cl) as defined above and at least one second layer, wherein said second layer is in direct contact with said at least one first layer.

[0061] Advantageously, said at least a first layer provides a barrier to the permeation of gases.

[0062] Preferably, said at least a first layer does not contain any continuous reinforcing layer.

[0063] Preferably, said at least a second layer contains a continuous reinforcing layer.

[0064] As disclosed above, more preferably the multilayer article of the present invention can be integrated into automotive components including, but not limited to, pans (e.g. oil pans), panels (e.g. exterior body panels, including but not limited to quarter panels, trunk, hood; and interior body panels, including but not limited to, doorSSPU 2024 / 045 panels and dash panels), side-panels, mirrors, bumpers, bars (e.g., torsion bars and sway bars), rods, suspensions components (e.g., suspension rods, leaf springs, suspension arms), turbo charger components (e.g. housings, volutes, compressor wheels and impellers) and housings for battery components.

[0065] The multilayer article of the present invention can also be desirably integrated into aerospace components, oil and gas drilling components (e.g. downhole drilling tubes, chemical injection tubes, undersea umbilicals and hydraulic control lines) and mobile electronic device components, as well as geothermal applications and carbon capture utilization and storage (CCSLI).

[0066] Notable non-limiting examples of multilayer articles are hoses, pipes, tubes, joints, tanks, reservoirs, or, in general, containers such as vessels and more preferably pressure vessels.

[0067] The hose for compressed hydrogen is used as a hose for charging a fuel-cell vehicle or the like with hydrogen from a hydrogen station. Since the hose for compressed hydrogen is subject to repeated temperature changes (heat cycles) from -40°C or lower to 90°C or higher due to charging and discharging of high-pressure hydrogen, it is required to have high heat cycle resistance, pressure cycle resistance as well as flexibility.

[0068] The hose for high-pressure hydrogen is a hose comprising or consisting of the multilayer structure as defined above.

[0069] More preferably, the multilayer article of the present invention is a hollow container or a system for the transportation of a fluid, in particular a pressurized gas. Both said hollow container and said system for the transportation of a fluid are referred to in the present description and in the following claims with the term “vessel” [vessel (V)].

[0070] Vessel (V) of the present invention preferably comprises said first layer comprising composition (Cl) of the present invention, which is also referred to as barrier layer [layer (BL)], and said at least one second layer comprising a polymer matrix and reinforcing fibers, which is referred to as composite layer [layer (CL)].

[0071] Layer (BL) represents the internal layer (also referred to as ‘liner’) of the article, while layer (CL) represents the external layer of the article of the present invention.

[0072] Said at least one layer (BL) does not contain any continuous reinforcing fiber.

[0073] Preferably, said at least one layer (BL) has a thickness which provides the required value of gas permeation required for the application. Layer (BL) preferably has a thickness of at least 100 microns, generally at least 250 microns. Layer (BL) maySSPU 2024 / 045 have a thickness of up to 10.0 mm, even 8.5 mm, 7.5 mm. Layer (BL) may have a thickness of 100 microns to 10.0 mm, generally from 250 microns to 10.0 mm, even from 300 microns to 8.5 mm, still from 500 microns to 6.0 mm.

[0074] The polymer matrix in said layer (CL) may comprise either a thermoplastic polymer or a thermoset polymer.

[0075] Thermoplastic polymers suitable as polymer matrix in layer (CL) are selected from the group comprising, more preferably consisting of: polyamides, in particular comprising an aromatic and / or cycloaliphatic structure; polyesters, such as poly(butylene terephthalate); poly(aryl ether ketone) polymers, in particular poly(ether ether ketone) (PEEK), poly(ether ketone ketone ketone) (PEEKK), poly(ether ketone ether ketone ketones) (PEKEKK); polyimides, in particular polyetherimides (PEI) or polyamide-imides; polysulfones, in particular polyarylsulfones such as polyphenylsulfones (PPSU), polyethersulfones (PES), poly(aryl sulfide)polymers, in particular PPS as defined above.

[0076] Preferred thermoplastic polymers are selected from the group comprising, more preferably consisting of polyamides, poly(aryl ether ketone) polymers and poly(aryl sulfide) polymers.

[0077] When the thermoplastic polymer is selected from PPS, such a PPS can be the same or different from the PPS polymer in layer (BL).

[0078] Thermoset materials suitable as polymer matrix in layer (CL) are selected from the group comprising, preferably consisting of: epoxy-resins.

[0079] Layer (CL) comprises continuous reinforcing fibers. As used herein, the expression “continuous reinforcing fiber” refers to a fiber having a length, in the longest dimension, of at least 5 mm.

[0080] In some embodiments, the continuous reinforcing fiber has a length, in the longest dimension, of at least 1 cm, at least 25 cm or at least 50 cm. The length of the continuous reinforcing fiber is dependent on the shape and size of the finished part.

[0081] Preferably, the continuous reinforcing fiber is selected from the group comprising, more preferably consisting of: glass fiber, carbon fibers, aluminum fiber, metallic fibers, ceramic fiber, titanium fiber, magnesium fiber, boron carbide fibers, rock wool fiber, steel fiber, aramid fiber and natural fiber (e.g. cotton, linen and wood).

[0082] More preferably, the continuous reinforcing fiber is selected from the group consisting of glass fiber, carbon fiber, aramid fiber, and ceramic fiber.

[0083] Advantageously, the continuous reinforcing fiber is carbon fiber.SSPU 2024 / 045

[0084] In some embodiments, layer (CL) may include one or more additional continuous reinforcing fibers, each distinct in compositions and as described above.

[0085] Overall, the continuous reinforcing fibers constitute at least 5.0% of the total volume of layer (CL). Typically, the continuous reinforcing fibers are at least 10.0%, at least 15.0%, even at least 20.0% of the total volume of layer (CL). The continuous reinforcing fibers are no more than 80.0%, no more than 75.0%, even no more than 70.0% of the total volume of layer (CL). The continuous reinforcing fibers may conveniently represent from 20.0% to 75.0%, from 25.0% to 70.0%, from 25.0% to 65.0% and even from 30.0% to 60.0% of the total volume of layer (CL).

[0086] The polymer matrix represents the remainder of the volume of said layer (CL).

[0087] The continuous reinforcing fibers in layer (CL) are generally aligned along a single direction. Generally aligned fibers are oriented such that at least 70%, at least 80%, at least 90% or at least 95% of the fibers have a direction that is within 30 degrees, within 25 degrees, within 20 degrees, within 15 degrees, or within 10 degrees along the direction of the other fibers.

[0088] In certain embodiments the continuous reinforcing fibers in layer (CL) may be arranged at an angle the ones with respect to the others. The continuous reinforcing fibers might be arranged as a woven fabric or a layered fabric or any combination of one or more.

[0089] Layer (CL) can be fabricated by methods well known in the art. In general, the method of fabrication includes a step of impregnation of the continuous reinforcing fibers with a polymer matrix or a precursor of the polymer matrix when the polymer is a thermosetting polymer, and subsequent cooling or drying to form a layer (CL).

[0090] When more than one layer (CL) is present, each layer (CL) may be the same or different.

[0091] Layer (CL) has a thickness which is usually between 100 microns and 500 microns. The thickness is adapted to provide the required structural resistance to the vessel.

[0092] The multilayer structure comprises two, three, four, five, six, seven, eight, nine, ten, 50, 80, 100 or even more layers (CL) consisting of the thermoplastic composite material, such as 200 or 300 layers.

[0093] The multilayer structure may additionally comprise one or more layers that are free of continuous reinforcing fibers.

[0094] Vessel (V) of the present invention is preferably selected from: a hollow container for containing a gas, preferably a pressurized gas (also referred to as a ‘pressureSSPU 2024 / 045 vessel’), a pipe, a hose or a piping system for the transportation of a gas, in particular a pressurized gas.

[0095] The vessel (V) of the invention, being a specific multilayer structure as defined above, comprises at least one layer (BL) as defined above and at least one layer (CL) as defined above.

[0096] The vessel (V) of the invention is preferably a Type IV vessel, which is a vessel comprising an internal barrier layer, or liner, and one or more than one layer consisting of a thermoplastic or thermoset composite material.

[0097] In said vessel (V) of Type IV, the liner forms the interior surface of the vessel, in contact with the gas. Local reinforcement of the dome can be done by Automated Fiber Placement (AFP). Also the volume % of fibers and the nature of the fibers used may vary from one layer to the next, typically from the inner to the outer surface of the vessel (V) or between the helicoidal and hoop layers.

[0098] The vessel (V) comprises a hollow body and at least one boss. A boss is known by a person skilled in the art and it refers to the opening in which a closure is attached which allows flow of gas or fluid in and out the vessel. A boss is usually made of metal. The boss could alternatively be made of a polymeric material, for instance selected in the group comprising MXD6, PPA 9T, PPA 10 T, PPS or mixtures thereof, including short fiber compounds, long fiber compounds as well as composites having continuous fibers.

[0099] The hollow body may have any shape suitable for the storage of a gas, in particular of a gas under pressure.

[0100] The shape of the hollow body is determined by the desired use. It is usually but not exclusively cylindrical; it typically has a diameter of between 10.0 cm and 1.00 m. In certain conventional embodiments, the vessel (V) has a cylindrical shape and a boss is placed at the end. Often, a vessel (V) has two bosses at each end of the cylindrical shape.

[0101] The length of a hollow body also depends on the end use and may for example be between 50.0 cm and up to lengths as large as 10.0 m. These higher lengths are usually employed for gas transport. As an example, for vessels in trucks the length is usually between 1.0 m and 3.0 m.

[0102] The vessel (V) of the invention may have an internal volume between 3.5 dm3and 10.0 m3, even from 5.0 dm3to 5.0 m3. The internal volume of the vessel (V) may beSSPU 2024 / 045 at least 10.0 dm3, even at least 15.0 dm3. The internal volume may be up to 0.5 m3, even up to 1.0 m3, up to 5.0 m3, even up to 10.0 m3.

[0103] The vessel (V) may be prepared according to any method known in the art.

[0104] The vessel (V) of the invention provides a high barrier to hydrogen, it has low moisture absorption and desorption, good mechanical properties, while having outstanding resistance to the blistering effect.

[0105] The vessel (V) according to the invention exhibits a nominal pressure of at least 2.5 MPa, typically at least 20.0 MPa, even at least 30.0 MPa. The nominal pressure may be up to 70.0 MPa, 100 MPa, even 150.00 MPa and more. Advantageously, the vessel of the invention has a nominal pressure of 20.0 to 70.0 MPa.

[0106] A burst pressure of at least 157.5 MPa may be reached for the storage of hydrogen gas with a vessel (V) according to the invention. Vessels for the storage of compressed hydrogen typically require nominal pressures of 35.0 MPa or 70.0 MPa. Burst pressures, measured according to ECE R134, are typically up to 78.8 MPa and 157.5 MPa, respectively.

[0107] A further object of the invention relates to at least one compressed gas in vessel (V) of the present invention as defined above, wherein layer (BL) is in contact with the compressed gas.

[0108] Said compressed gas is advantageously selected from the group consisting of hydrogen, oxygen, nitrogen, argon, helium, methane, propane, compressed natural gas, CO2 and ammonia.

[0109] The gas is typically at a pressure of at least 5.0 MPa, preferably at least 10.0 MPa. Depending on the gas, the pressure may be up to 150.0 MPa.

[0110] A further object of the invention is a vehicle comprising vessel (V) as defined above or the compressed gas contained in the vessel (V) as defined above.

[0111] Said vehicle is preferably selected from a car, a truck, a train, a ship, an urban mobility vehicle, an airplane, a helicopter or any other vehicle that could be powered using the conversion of a gas into energy by any means.

[0112] The embodiments above are intended to be illustrative and not limiting. Additional embodiments are within the inventive concepts. In addition, although the present invention is described with reference to particular embodiments, those skilled in the art will recognize that changes can be made in form and detail without departing from the spirit and scope of the invention.SSPU 2024 / 045

[0113] Should the disclosure of any patents, patent applications, and publications which are incorporated herein by reference conflict with the description of the present application to the extent that it may render a term unclear, the present description shall take precedence.

[0114] The present invention will be now described in more detail with reference to the following examples, whose purpose is merely illustrative and not intended to limit the scope of the disclosure.

[0115] EXAMPLES

[0116] MaterialsPPS-1 (Ryton(R) PPS with MFR range 70-130 g / 10 min)PPS-2C (Ryton(R) PPS with MFR range 5-7 g / 10 min)PPS-3C (mixture of 30.7 wt.% Ryton(R) PPS with MFR range 170-230 g / 10 min and 42.3 wt.% Ryton(R) PPS with MFR range 130-185 g / 10 min)Additive package (Surlyn™ 9320 - zinc ionomer of ethylene acid acrylic terpolymer; PIGM Carbon black; lrganox(R)1010 Pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate)Stabilizer (lrganox(R)1010)Impact modifier (IM-1) Lotader(R) AX8900 Ethylene-Acrylic Ester-Glycidyl Methacrylate terpolymer, Tm = 65 °CImpact modifier (IM-2C) Lotader(R) AX8840 Ethylene-Glycidyl Methacrylate copolymer, Tm = 104 °C

[0117] The melt flow rate (MFR) of PPS-1 and PPS-2 was measured in an extrusion plastomer at 316 °C using a weight of 5 kg and a 0.21 cm x 0.80 cm die after a 5 minute equilibration period, according to ASTM D1238, procedure B.

[0118] Compositions of the invention and of comparison were prepared by mixing the ingredients in the amounts provided in Table 1.Table 1SSPU 2024 / 045(*) of comparison

[0119] Mechanical properties were evaluated and the results are reported in Table 2.

[0120] As shown in the following Table 2, Example 2C of comparison comprising PPS-2 has insufficient strain at break as well as too low viscosity and hence was not further tested for hydrogen permeation and blistering.

[0121] H2 Permeation coefficient determination

[0122] Samples for hydrogen permeation testing were prepared by injection molding as described herein after.

[0123] Plaques measuring 100 mm x100 mm x 3.2 mm were molded using the following approximate temperature conditions on the barrel and mold: rear zone: 330 °C middle zone: 330 °C front zone: 330 °C nozzle: 330 °C mold: 155 °C

[0124] PPS molded samples were annealed at 140°C during 8 hours.

[0125] Samples of 90 x 90 mm were cut and mounted on a cell so as to form a barrier between two chambers. An epoxy glue was put around the sheets to minimize side permeation.

[0126] The test was performed by conditioning the cell both at 55°C and at 85°C. One chamber contained the test gas (H2) and the other chamber was purged with a sweep gas (synthetic air). The feed side was pressurized with H2 and during theSSPU 2024 / 045 measurement, the concentration of H2 in the sweep gas flow was measured, typically with an electrochemical H2 sensor.Permeation coefficient (P) is calculated according to the equation 1 (Eq. 1):P = (C D d / A pp).(T° p / T p°) [Eq. 1] wherein:P =permeation coefficient (Ncm3 mm / m2 daybar)C = penetrant concentration (ppm)D = sweep gas flow rate (mL / min) d = sample thickness (mm)A = testing area in contact with the gas (m2) pp = penetrant partial pressure (bar)T = ambient temperature (K) p = ambient pressure (bar)T° = standard temperature (273.15 K) p° = standard pressure (1.013 bar)

[0127] Further normalization is done to standard temperature and pressure, i.e.273.15 K and 1.013 bar.

[0128] Plate samples were tested under the following conditions:Condition 0: as such, no thermal treatment 85°C);Condition 1 : after 5 thermal cycles as follows 30 minutes at - 65 °C and 30 minutes at 100 °C.

[0129] The results are reported in Table 2.

[0130] Blistering test

[0131] The samples of the invention and of comparison were submitted to a dynamic cycling test (or cyclic blistering test) to detect surface modifications.

[0132] ISO 527 1A tensile bars were introduced in the testing apparatus and submitted to repeated pressurization and depressurization cycles as follows:° condition to 50 ± 2 °C° perform 250 cycles0pressurize to > 87.5 MPa hold at > 87.5 MPa for 24.8 minSSPU 2024 / 045° depressurize to < 0.5 MPa at ca. 1,000 MPa / hr° hold at < 0.5 MPa for 24.8 min° depressurize to ambient pressures° remove samples from pressure vessel and report surface modifications (blisters).

[0133] Static blistering tests were performed under the following conditions:° Condition to 23 ± 2 °C° Pressurize to 87.5 MPa° Soak for 168 hours (exposure)° Depressurize to ambient pressure as fast as possible (target: < 5s)

[0134] The results are reported in Table 2.Table 2SSPU 2024 / 045(*) of comparison

[0135] The results reported in Table 2 above showed that the composition of the present invention was superior in terms of resistance to blistering, while showing good hydrogen permeability, viscosity and mechanical properties.

Claims

SSPU 2024 / 045Claims1. A composition [composition (Cl)] comprising:- at least one poly(arylene sulfide) polymer having melt flow rate of at most 200 g / 10 min and of at least 2 g / 10 min, the melt flow rate being the value measured in an extrusion plastomer at 315.6°C using a weight of 5 kg and a 0.21 cm x 0.80 cm die after a 5 minute equilibration period, according to ASTM D1238, procedure B, and- at least one impact modifier selected from terpolymers of ethylene, acrylic ester and glycidyl methacrylate, said at least one impact modifier being in an amount from 2.5 to less than 22.0 wt.% based on the total weight of said composition (Cl).

2. The composition (Cl) according to Claim 1 , wherein said poly(arylene sulfide) polymer comprises at least 50.0 mol% of a recurring unit (RPAS) having at least one aromatic ring bonded to a sulfur atom.

3. The composition (Cl) according to Claims 1 or 2, wherein the amount of said recurring unit (RPAS) is at least 60.0 mol%, at least 70.0 mol%, at least 80.0 mol%, at least 90.0 mol%, at least 95.0 mol%, at least 97.0 mol%, at least 98.0 mol%, at least 99.0 mol% or at least 99.9 mol% based on the total number of recurring units in the poly(arylene sulfide) polymer.

4. The composition (Cl) according to any one of Claims 1 to 3, wherein said recurring unit (RPAS) is represented by a formula selected from the following formulae (1) to (3):SSPU 2024 / 045whereinR is, at each instance, independently selected from the group consisting of a C1-C12 alkyl group, a C7-C24 alkylaryl group, a C7-C24 aralkyl group, a C6- C24 arylene group, and a C6-C18 aryloxy group;T is selected from the group consisting of a bond, -CO-, -SO2-, -O-, -C(CH3)2, phenyl and -CH2-; i is , at each instance, independently 0 or an integer from 1 to 4; and j is , at each instance, independently 0 or an integer from 1 to 3.

5. The composition (Cl) according to any one of Claims 1 to 4, wherein said recurring unit (RPAS) is represented by formula (1-a):(1-a) whereinR is, at each instance, independently selected from the group consisting of a C1-C12 alkyl group, a C7-C24 alkylaryl group, a C7-C24 aralkyl group, a C6- C24 arylene group, and a C6-C18 aryloxy group; and i is , at each instance, independently 0 or an integer from 1 to 4.SSPU 2024 / 0456. The composition (Cl) according to any one of Claims 1 to 5, wherein said poly(arylene sulfide) polymer has a melt flow rate:- of at most 200 g / 10 min, more preferably of at most 195 g / 10 min, even more preferably of at most 190 g / 10 min and still more preferably of at most 185 g / 10 min; and / or- of at least 4 g / 10 min, more preferably of at least 10 g / 10 min, even more preferably of at least 15 g / 10 min and still more preferably of at least 25 g / 10 min; wherein the melt flow rate of said poly(arylene sulfide polymer) refers to the value measured in an extrusion plastomer at 316 °C using a weight of 5 kg and a 0.21 cm x 0.80 cm die after a 5 minute equilibration period, according to ASTM D1238, procedure B.

7. The composition (Cl) according to any one of Claims 1 to 6, wherein said poly(arylene sulfide)polymer is in an amount from 50 wt.% to 98.5 wt.% based on the total weight of composition (Cl), more preferably from 70 wt.% to 97.5 wt.% and even more preferably from 75 wt.% to 95 wt.%.

8. The composition (Cl) according to any one of Claims 1 to 7, wherein said at least one impact modifier is in an amount from 3.5 to less than 20.0 wt.% based on the total weight of composition (Cl), more preferably from 4.5 to 19.5 wt.% and even more preferably from 5.0 to 18.0 wt.%.

9. An article comprising composition (Cl) according to any one of Claims 1 to 8.

10. The article according to Claim 9, said article being selected from an automotive component, an aerospace component, an oil and gas drilling component, a mobile electronic device component, a geothermal component and a component in a device for carbon capture utilization and storage (CCSU).11 . The article according to any one of Claims 9 to 10, said article being selected from hose, pipe, tube, joint, tank, reservoir, hollow container such as a vesselSSPU 2024 / 045 and more preferably a pressure vessel.

12. The article according to any one of Claims 9 to 11 , said article being a multilayer article comprising at least one first layer comprising composition (Cl) according to any one of Claims 1 to 8 and at least one second layer, said second layer being in contact with said at least one first layer.

13. The article according to Claim 12, wherein said multilayer article is selected from hose, pipe, tube, joint, tank, reservoir, hollow container such as a vessel and more preferably a pressure vessel.

14. The article according to Claim 12, wherein said multilayer article is a vessel [vessel (V)] comprising at least one first layer comprising composition (Cl) according to any one of Claims 1 to 8 [layer (BL)] and at least one second layer comprising a polymer matrix and reinforcing fibers [layer (CL)].

15. At least one compressed gas contained in vessel (V) according to Claim 13, wherein said at least one compressed gas is in contact with said layer (BL).

16. A vehicle comprising:- the vessel (V) according to Claim 13 or- the at least one compressed gas contained in the vessel (V) according to Claim 14.

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