Containers for the storage of gas

Abstract

Container for storage and transport of gases.The container is particularly suitable for storage and transport of compressed gases in vehicles.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 63 / 387309, filed December 14, 2022, and European Patent Application Publication No. 23158668.6, filed February 27, 2023, the entire contents of each of which are incorporated herein by reference for all purposes.

[0002] The present invention relates to a container for the storage and transport of gases. The present invention further relates to a method for manufacturing the container and to the gas stored in the container. [Background technology]

[0003] Pressure vessels characterized by high gas barrier properties have been used for long-term storage of various gases, such as oxygen, carbon dioxide, nitrogen, argon, LPG (liquefied petroleum gas), methane, and hydrogen. Pressure vessels are known that include a nonstructural layer, or liner, surrounded by a structural fiber-reinforced composite material for containing a fluid or gas under pressure. The liner acts as a barrier between the fluid or gas and the fiber-reinforced composite material, thus preventing leakage and / or other degradation of the fiber-reinforced composite material's structure. The use of structural fiber-reinforced composite materials with a thermoplastic polymer matrix, rather than a thermosetting polymer matrix, is advantageous for facilitating the recycling of pressure vessels.

[0004] Pressure vessels comprising a polyamide-based liner and an outer layer that is a composite material containing continuous fibers and a polyamide resin impregnated into the continuous fibers are disclosed, for example, in EP 3225888 A1, EP 3390016 A1, and WO 21152254 A1.

[0005] However, there remains a need to develop pressure vessels, particularly pressure vessels for the transport and storage of hydrogen, that combine high performance qualities in terms of impermeability to the stored gas with mechanical properties. Summary of the Invention

[0006] The inventors have found that low hydrogen permeability and good mechanical properties can be obtained by a container comprising a barrier layer or liner that combines a priori opposing properties: a high glass transition temperature and a high hydrogen permeation barrier on the one hand, and a low melting temperature and good ductility at low temperatures on the other.

[0007] The first object of the present invention is to - glass transition temperature of at least 65 ° C; - melting temperature of at most 320°C; - an elongation at break at -40°C of at least 2.5% when measured according to ISO 527-2 using ISO 1BA specimens at a test speed of 5 mm / min; and - Maximum 500Ncm 3 .mm / m 2 Hydrogen permeability coefficient at 85°C in .d.bar The container comprises at least one barrier layer, [layer (BL)], comprising at least one thermoplastic polymer, [thermoplastic polymer (TP)], characterized by:

[0008] The container advantageously comprises at least one barrier layer, [layer (BL)], as defined above, and at least one composite layer, [layer (CL)], in contact with the at least one barrier layer, wherein layer (CL) comprises continuous reinforcing fibers and a polymer matrix. The polymer matrix can be either thermoplastic or thermosetting. Layer (BL) represents the inner layer, or liner, of the container, while layer (CL) represents the outer layer of the container.

[0009] The vessel is a pressure vessel, i.e. a vessel for the storage of gas under pressure.

[0010] A second object of the present invention is a compressed gas in the container of the first object, wherein the layer (BL) is in contact with the compressed gas. Further objects of the present invention are a method for producing the container, as well as the use of the container in a vehicle or in gas transportation in general. DETAILED DESCRIPTION OF THE INVENTION

[0011] In this application: - any description, even if made in relation to a particular embodiment, is applicable to and interchangeable with other embodiments of the present disclosure; - When an element or component is said to be included in and / or selected from a list of enumerated elements or components, in the relevant embodiments expressly contemplated herein, the element or component can also be any one of the individually enumerated elements or components, or can be selected from a group consisting of any two or more of the explicitly enumerated elements or components; it is to be understood that any element or component enumerated in a list of elements or components can be omitted from such list; - any recitation herein of numerical ranges by endpoints includes all numbers subsumed within the recited range, as well as the endpoints of the range, and equivalents thereof; - the indefinite article "a" in expressions such as "a polyamide polymer" is intended to mean "one or more" or "at least one", unless otherwise specified; - The use of parentheses "()" around the name, symbol or number of a compound, e.g., "layer (BL)", has the sole purpose of better distinguishing that name, symbol or number from the rest of the text; therefore, said parentheses may also be omitted.

[0012] Unless otherwise specifically stated, the terms "alkyl," and 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-dimethylethyl, and cyclopropyl. Unless otherwise specifically stated, 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 the substituents are sterically compatible and chemical bonding and strain energy rules are satisfied. The term "halogen" or "halo" includes fluorine, chlorine, bromine, and iodine, with fluorine being preferred.

[0013] The term "aryl" refers to a phenyl, indanyl, or naphthyl group. An aryl group may contain one or more alkyl groups, in which case it may be referred to as an "alkylaryl"; for example, it may be composed of a cyclo-aromatic group and two C1-C6 groups (e.g., methyl or ethyl). An aryl group may also contain one or more heteroatoms, such as N, O, or S, and may be referred to as a "heteroaryl" group; these heteroaromatic rings may be fused to other aromatic systems. An aryl or heteroaryl substituent 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 chemical bonding and strain energy rules are met.

[0014] Layer (BL) A first object of the present invention is a container comprising at least one barrier layer, [layer (BL)], which is designed to provide a barrier to the permeation of gases.

[0015] The layer (BL) does not contain any continuous reinforcing fibers.

[0016] Layer (BL) is - glass transition temperature of at least 65 ° C; - melting temperature of at most 320°C; - an elongation at break at -40°C of at least 2.5% when measured according to ISO 527-2 using ISO 1BA specimens at a test speed of 5 mm / min; and - Maximum 500Ncm 3 .mm / m 2 Hydrogen permeability coefficient at 85°C in .d.bar The thermoplastic polymer (TP) comprises at least one thermoplastic polymer, characterized by:

[0017] Glass transition temperatures and melting temperatures are measured using differential scanning calorimetry (DSC) according to ASTM D3418 in a second thermal scan using heating and cooling rates of 20°C / min.

[0018] The thermoplastic polymer (TP) advantageously has a glass transition temperature of at least 65°C, even at least 75°C, preferably at least 80°C. The glass transition temperature is greater than 80°C, even greater than 85°C. The glass transition temperature may be as high as 180°C, generally up to 170°C, and in some cases as high as 160°C. The glass transition temperature of the thermoplastic polymer (TP) is advantageously between 65°C and 180°C, even between 80°C and 170°C, between 85°C and 165°C, or even between greater than 85°C and 160°C.

[0019] The thermoplastic polymer (TP) advantageously has a melting temperature of at most 320°C, even at most 315°C, in some cases at most 310°C. The melting temperature is generally at least 200°C, generally at least 220°C. The melting temperature of the thermoplastic polymer is advantageously between 200°C and 310°C, even between 220°C and 305°C, in some cases between 220°C and 280°C.

[0020] The thermoplastic polymer (TP) in the layer (BL) advantageously exhibits an elongation at break at -40°C of at least 2.5%. The elongation at break at -40°C may be at least 3.0%, preferably at least 3.5%. Tensile properties, including elongation at break, are measured according to ISO 527-2 using ISO 1BA specimens at a test speed of 5 mm / min.

[0021] The container of the present invention can be advantageously used for the storage and transport of hydrogen.

[0022] Thermoplastic polymers (TP) have a maximum strength of 500 Ncm 3 .mm / m 2 .d.bar, max. 480Ncm 3 .mm / m 2 .d.bar, preferably at most 450Ncm 3 .mm / m 2 .d.bar, preferably at most 350Ncm 3 .mm / m 2 Figure 1 shows the hydrogen permeability coefficient at 85°C in 10.5 dbar. The lower the permeability coefficient, the better the barrier properties of the container. Hence, the hydrogen permeability coefficient at 85°C of thermoplastic polymers can be as low as zero, but typically is greater than 1 Ncm. 3 .mm / m 2 Even as low as .d.bar and even 10Ncm 3 .mm / m 2 It can be as low as .d.bar.

[0023] Hydrogen permeability coefficients are determined by measuring the permeation of hydrogen at 85°C and 1 MPa pressure through molded plaques of thermoplastic polymers (TP) that have been annealed for 2 hours at a temperature 20°C above their glass transition temperature. Detailed methods for the measurements are described in the experimental section of this specification.

[0024] The thermoplastic polymer (TP) may be selected from the group consisting of poly(arylene sulfide) polymers and semi-aromatic polyamides.

[0025] The thermoplastic polymer (TP) may be selected from poly(arylene sulfide) polymers. Poly(arylene sulfide) polymers typically contain at least 50.0 mol% of repeat units (R PAS In some embodiments, the repeating unit (R PAS ) 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%. As used herein, mol% is relative to the total number of repeat units in the poly(arylene sulfide) polymer, unless otherwise specified.

[0026] Repeating unit (R PAS ) is a formula for the following group: [ka] (In the formula: - R is, in each case, C1 to C 12 Alkyl groups, C7-C 24 Alkylaryl group, C7-C 24 Aralkyl groups, C6-C 24 Arylene groups and C6-C 18 aryloxy groups; - T is selected from the group consisting of a bond, -CO-, -SO2-, -O-, -C(CH3)2, phenyl, and -CH2-; - i, in each occurrence, is independently 0 or an integer from 1 to 4; j, in each occurrence, is independently 0 or an integer from 1 to 3. is represented by a formula selected from:

[0027] For clarity, when i or j is zero, the corresponding aromatic ring is unsubstituted.

[0028] Preferably, the poly(arylene sulfide) polymer has a melt flow rate of at most 700 g / 10 min, more preferably at most 500 g / 10 min. Preferably, the poly(arylene sulfide) has a melt flow rate of at least 1 g / 10 min, more preferably at least 5 g / 10 min. As used herein, the melt flow rate of any poly(arylene sulfide) polymer refers to the value measured on an extruded plastomer at 315.6°C using a 5 kg weight and a 0.21 cm x 0.80 cm die after a 5-minute equilibration period according to ASTM D1238, Procedure B.

[0029] According to one embodiment of the present invention, the poly(arylene sulfide) polymer is poly(phenylene sulfide) (hereinafter referred to as "PPS"). The expression "poly(phenylene sulfide)" or PPS refers to a polymer having a repeating unit (R PAS ) is used to refer to the poly(arylene sulfide) polymer represented by formula (1). More preferably, the repeating unit (R PAS ) is expressed by equation (4): [ka] It is expressed as:

[0030] Most preferably, in the PPS, the repeating unit (R PAS ) is expressed by equation (4) where i=0.

[0031] The PPS may be acid washed or non-acid washed, hi some embodiments, the PPS is acetic acid washed PPS.

[0032] In a preferred embodiment, the PPS polymer is such that at least 90.0 mol % of the repeat units are repeat units of formula (4) where i = 0. The PPS polymer may consist essentially of repeat units of formula (4) where i = 0.

[0033] The melt flow rate of PPS (at 316°C and 5 kg) is typically from 5 to 200 g / 10 min, for example from 7 to 180 g / 10 min.

[0034] A suitable PPS is commercially available from Solvay Specialty Polymers USA, LLC under the trade name Ryton® PPS.

[0035] The thermoplastic polymer (TP) may alternatively be selected from the group consisting of semi-aromatic polyamides. The expression "semi-aromatic polyamide" refers to a polyamide comprising repeat units derived from at least one aromatic monomer and at least one aliphatic monomer. The aromatic monomer may be a diamine, a diacid, or an amino acid.

[0036] In some embodiments, the semi-aromatic polyamide may include repeat units derived from an aromatic diamine.

[0037] The semi-aromatic polyamide may contain at least 50 mol %, typically at least 70 mol %, of repeat units derived from aromatic diamines, based on the total amount of diamine units in the polyamide.

[0038] Preferably, the semi-aromatic polyamide comprises repeat units derived from an aromatic diamine having from 6 to 18 carbon atoms.

[0039] Examples of suitable C6 to C18 aromatic diamines include, but are not limited to, m-phenylenediamine (MPD), p-phenylenediamine (PPD), 3,4'-diaminodiphenyl ether (3,4'ODA), 4,4'-diaminodiphenyl ether (4,4'-ODA), p-xylylenediamine (PXD), and m-xylylenediamine (MXD).

[0040] Notable, non-limiting examples of suitable polyamides containing aromatic diamines include polyamides containing repeating units of the formula MXDZ, where Z represents a unit derived from a linear or branched, aliphatic or cycloaliphatic diacid having z carbon atoms, where z is an integer equal to or greater than 6, and MXD is m-xylylenediamine. Z is preferably selected from aliphatic diacids having 6 to 16 carbon atoms. Notable, non-limiting examples are adipic acid, sebacic acid, or dodecanedioic acid. More preferably, Z is adipic acid.

[0041] In some embodiments, the semi-aromatic polyamide may further comprise repeat units of the formula PXDZ, where PXD represents units derived from p-xylylenediamine and Z is as defined above.

[0042] In a particular embodiment, the semi-aromatic polyamide is a polyamide of formula A / MXDZ, where A is a repeating unit derived from at least one of the following: an amino acid, i.e., a molecule containing a primary carboxylic acid and a primary amine, a lactam, or a unit of formula (Ca diamine).(Cb diacid), where "a" represents the number of carbon atoms in the diamine, "b" represents the number of carbon atoms in the diacid, and "a" and "b" are, independently of one another, integers from 4 to 36, advantageously from 6 to 18. The component (Ca diamine) is preferably selected from the group consisting of linear or branched aliphatic diamines, cycloaliphatic diamines, and alkylaromatic diamines. Examples are, for example, hexamethylenediamine, decanediamine, dodecanediamine, and MXD.

[0043] The component (Cb diacid) is preferably selected from the group consisting of linear or branched aliphatic diacids, cycloaliphatic diacids and aromatic diacids, examples being, for example, adipic acid, sebacic acid or dodecanedioic acid or 3-(aminomethyl)benzoic acid (3-AMBa).

[0044] In an advantageous embodiment, units A or Z can be derived from renewable materials. Non-limiting examples of suitable polyamides of this type are PA MXD6, PA MXD10.

[0045] In another embodiment, the semi-aromatic polyamide comprises repeat units derived from an aromatic diacid.

[0046] In a preferred embodiment, the semi-aromatic polyamide comprises repeating units of formula XT, where X represents units derived from a linear or branched, aliphatic or cycloaliphatic diamine having x carbon atoms, where x is an integer greater than or equal to 6, and T represents units derived from terephthalic acid. In formula XT, X may advantageously represent units derived from a linear or branched, aliphatic or cycloaliphatic diamine having x carbon atoms, where x is selected from 6, 7, 8, 10, 11, 12, 13, 14, 15, 16.

[0047] Semi-aromatic polyamides comprise at least 50 mol %, typically at least 70 mol %, or even at least 90 mol % of repeat units of formula XT.

[0048] The semi-aromatic polyamide may comprise two or more repeat units of formula XT, where each unit X is derived from a different diamine as defined above. Alternatively, the semi-aromatic polyamide may comprise, in addition to repeat units of formula XT, repeat units of formula X'T, where X' represents a unit derived from a linear or branched, aliphatic or cycloaliphatic diamine having x' carbon atoms, where x' is an integer less than 6.

[0049] In some embodiments, the semi-aromatic polyamide may further comprise repeat units of formula XI, where I represents units derived from isophthalic acid and X is as defined above.

[0050] The units X in formula XT, or, if present, the units XI, are derived from a linear or branched, aliphatic or cycloaliphatic diamine having x carbon atoms, where x is greater than or equal to 6 and less than or equal to 36, advantageously between 8 and 18, or even equal to 8, 10, 11, 12, 14, 16. The units X are preferably derived from an aliphatic diamine selected from the group consisting of 1,8-octanediamine, 2-methyl-1,8-octanediamine (Me8), 1,10-decanediamine, 1,12-dodecanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 5-methyl-1,9-nonanediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, isophoronediamine, and mixtures thereof. In a preferred embodiment of the present invention, the units X are from the group of aliphatic diamines consisting of 1,8-octanediamine, 1,10-decanediamine, 1,12-dodecanediamine and mixtures thereof. More preferably, the units X are from the group of aliphatic diamines consisting of 1,10-decanediamine, 1,12-dodecanediamine and mixtures thereof.

[0051] In certain embodiments, the aliphatic diamines can be derived from renewable sources. Notable non-limiting examples of such diamines are 1,10-decanediamine and 1,12-dodecanediamine, which can be derived from, for example, castor oil.

[0052] Notable non-limiting examples of suitable polyamides containing only repeat units of the formula XT or XT / X'T are PA 6T, PA 8T, PA 10T, PA 11T, PA 12T, PA 6T / 9T, PA 9T / 10T, PA 9T / 11T, PA 9T / 12T, PA 6T / 10T, PA 6T / 11T, PA 6T / 12T, PA 10T / 11T, PA 10T / 12T, PA 11T / 12T.

[0053] In a particular embodiment, the semi-aromatic polyamide is a copolyamide of formula Y / XT, where XT is as defined above and Y is a repeating unit derived from at least one of the following: an amino acid, i.e., a molecule containing a primary carboxylic acid and a primary amine, a lactam or a unit of formula (Cn diamine)(Cm diacid), where "n" represents the number of carbon atoms in the diamine, "m" represents the number of carbon atoms in the diacid, and "n" and "m" are, independently of one another, integers from 4 to 36, advantageously from 6 to 18. The component (Cn diamine) is preferably selected from the group consisting of linear or branched aliphatic diamines, cycloaliphatic diamines and alkylaromatic diamines. The component (Cm diacid) is preferably selected from the group consisting of linear or branched aliphatic diacids, cycloaliphatic diacids and aromatic diacids.

[0054] In advantageous embodiments, the unit Y in the formula Y / XT can be derived from renewable materials. Notable non-limiting examples of diacids or amino acids derived from renewable sources are those derived from furfural, such as sebacic acid or 3-(aminomethyl)benzoic acid (3-AMBa).

[0055] Notable non-limiting examples of suitable copolyamides comprising repeating units of formula XT as defined above are, for example, PA 6T / 6I, PA 6T / 66, PA 6T / 6I / 66, PA 10 / 6T, PA 10 / 9T, PA 10 / 10T, PA 10 / 11T, PA 10 / 12T, PA 11 / 6T, PA 11 / 9T, PA 11 / 10T, PA 11 / 11T, PA 11 / 12T, PA 12 / 6T, PA 12 / 9T, PA 12 / 10T, PA 12 / 11T, PA 12 / 12T, PA 610 / 6T, PA 612 / 6T, PA 910 / 6T, PA 912 / 6T, PA 1010 / 6T, PA 1012 / 6T, PA 610 / 9T, PA 612 / 9T, PA 910 / 9T, PA 912 / 9T, PA 1010 / 9T, PA 1012 / 9T, PA 610 / 10T, PA 612 / 10T, PA 910 / 10T, PA 912 / 10T, PA 1010 / 10T, PA 1012 / 10T, PA 610 / 12T, PA 612 / 12T, PA 910 / 12T, PA 912 / 12T, PA 1010 / 12T, PA 11 / 6T / 9T, PA 11 / 6T / 10T, PA 11 / 6T / 11T, PA 11 / 6T / 12T, PA 11 / 9T / 10T, PA 11 / 9T / 11T, PA 11 / 9T / 12T, PA The polyamide is selected from the group consisting of PA 11 / 10T / 11T, PA 11 / 10T / 12T, PA 11 / 11T / 12T, PA 12 / 6T / 10T, PA 12 / 6T / 11T, PA 12 / 6T / 12T, 12 / 9T / 10T, PA 12 / 9T / 11T, PA 12 / 9T / 12T, PA 12 / 10T / 11T, PA 12 / 10T / 12T, PA 12 / 11T / 12T, PA MXDT / 10T, PA MPMDT / 10T, PA BACT / 10T, PA BACT / 6T, PA BACT / 10T / 6T, PA 11 / BACT, and PA 11 / BACT / 10T.

[0056] The semi-aromatic polyamide may advantageously be selected from the group consisting of PA 6T / 66, PA 6T / 6I / 66, PA 9T / 10T.

[0057] The layer (BL) has a thickness that provides the necessary value of gas permeability required for the application. The layer (BL) typically has a thickness of at least 100 microns, generally at least 250 microns. The layer (BL) may have a thickness of up to 10.0 mm, even 8.5 mm, or even 7.5 mm. The layer (BL) may have a thickness of 100 microns to 10.0 mm, generally 250 microns to 10.0 mm, even 300 microns to 8.5 mm, or even 500 microns to 6.0 mm.

[0058] The layer (BL) may comprise one or more thermoplastic polymers (TP) and, optionally, one or more additives commonly used in the formulation of thermoplastic polymers.

[0059] Non-limiting examples of suitable additives are antioxidants (e.g., UV stabilizers and heat stabilizers), chain extenders, processing aids, nucleating agents, lubricants, flame retardants, smoke suppressants, antistatic agents, antiblocking agents, colorants, and pigments.

[0060] The total amount of additives may be up to 20.0 wt.%, or even up to 10.0 wt.%, relative to the total weight of the layer (BL). When present, the amount of one or more additives is at least 0.1 wt.%, or even at least 0.5 wt.%, relative to the total weight of the thermoplastic polymer (TP).

[0061] The layer (BL) may comprise one or more thermoplastic polymers (TP) and impact modifiers.

[0062] Suitable impact modifiers are, for example, functionalized polyolefins having a glass transition temperature of less than 25° C.

[0063] The polymer backbone of the impact modifier may be selected from elastomeric backbones comprising polyethylene and copolymers thereof, such as ethylene-butene; ethylene-octene; polypropylene and copolymers thereof; 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); core-shell elastomers of the methacrylate-butadiene-styrene (MBS) type, or mixtures of one or more of the above.

[0064] If the impact modifier is functionalized, the backbone functionalization can occur by copolymerization of monomers containing the functionalization or by grafting the polymer backbone with additional components.

[0065] Specific examples of functionalized impact modifiers are, inter alia, terpolymers of ethylene, acrylic esters and glycidyl methacrylate, copolymers of ethylene and acrylic acid butyl ester; copolymers of ethylene, acrylic acid butyl ester and glycidyl methacrylate; ethylene-maleic anhydride copolymers; EPR grafted with maleic anhydride; styrene copolymers grafted with maleic anhydride; SEBS copolymers grafted with maleic anhydride; styrene-acrylonitrile copolymers grafted with maleic anhydride; ABS copolymers grafted with maleic anhydride.

[0066] Functionalized polyolefin impact modifiers are available from commercial sources, including maleated polypropylene and ethylene-propylene copolymers available as Exxelor® PO, and maleic anhydride-functionalized ethylene-propylene copolymer rubbers containing about 0.6 weight percent pendant succinic anhydride groups, such as Exxelor® VA 1801 from ExxonMobil Chemical Company; acrylate-modified polyethylenes available as Surlyn®, such as Surlyn® 9920, an acrylic or methacrylic acid-modified polyethylene from Dow Inc.; maleic anhydride-modified SEBS block copolymers, such as Kraton® FG1901X, an SEBS grafted with about 2 weight percent maleic anhydride, available from Kraton Polymers; and maleic anhydride-functionalized EPDM terpolymer rubbers, such as Royaltuf® 498, a 1% maleic anhydride-functionalized EPDM, available from SI Group.

[0067] Other desirable functionalized impact modifiers include, but are not limited to, ethylene-higher alpha-olefin polymers and ethylene-higher alpha-olefin-diene polymers grafted with or copolymerized with reactive carboxylic acids or their derivatives, such as, for example, acrylic acid, methacrylic acid, maleic anhydride, or their esters. Suitable higher alpha-olefins include, but are not limited to, C3 to C8 alpha-olefins, such as, for example, propylene, 1-butene, 1-hexene, and styrene.

[0068] Among the reactive impact modifiers, mention may be made of random terpolymers of ethylene, acrylic acid esters and glycidyl methacrylate, which are commercially available from Arkema (Bristol, PA, USA) under the trade name Lotader® AX8900. Another example of the aforementioned reactive impact modifier is available under the trade name Paraloid. TMAvailable commercially from Dow Inc. (Midland, MI, USA) under the designation EXL 2314, it is a core-shell acrylate-based impact modifier consisting primarily of a core made of crosslinked poly(n-butyl acrylate) rubber and having a shell phase made primarily of poly(methyl methacrylate)-poly(glycidyl methacrylate) copolymer.

[0069] In the second embodiment, the layer (BL) comprises 1.0 to 25.0 wt. % of at least one impact modifier, based on the total weight of the layer (BL). The impact modifier may be at least 2.0 wt. %, or at least 3.0 wt. %, or even at least 5.0 wt. % of the total weight of the layer (BL). The impact modifier is typically not more than 20.0 wt. %, not more than 15.0 wt. %, not more than 12.0 wt. %, or even not more than 10.0 wt. Suitable ranges may be, for example, 1.0 to 15.0 wt. %, or even 1.0 to 12.0 wt. %, or even 2.0 to 10.0 wt. %.

[0070] In a second embodiment, the layer (BL) may further comprise additives as detailed above, the total amount of which may be up to 20.0 wt.%, or even up to 10.0 wt.%, relative to the total weight of the layer (BL) and / or at least 0.1 wt.%, or even at least 0.5 wt.%, relative to the total weight of the layer (BL).

[0071] When more than one layer (BL) is present in the container of the present invention, each layer (BL) may comprise the same or a different thermoplastic polymer (TP).

[0072] Layer (CL) The container of the present invention comprises at least one barrier layer, [layer (BL)], as defined above, and it may comprise at least one composite layer, [layer (CL)], in contact with the at least one barrier layer, wherein layer (CL) comprises continuous reinforcing fibers and a polymer matrix.

[0073] Layer (BL) represents the inner layer, or liner, of the container, while layer (CL) represents the outer layer of the container.

[0074] The polymer matrix in layer (CL) can be either a thermoplastic polymer or a thermosetting polymer.

[0075] Among the suitable thermoplastic polymers suitable as the polymer matrix in layer (CL) there may be mentioned polyamides, in particular those containing aromatic and / or alicyclic structures, polyesters such as poly(butylene terephthalate), poly(aryl ether ketone) polymers as defined above, in particular poly(ether ether ketone) (PEEK), poly(ether ketone ketone) (PEEKK), poly(ether ketone ketone ether ketone) (PEKEKK), polyimides, in particular polyetherimide (PEI) or polyamide-imide, polysulfones, in particular polyarylsulfones such as polyphenylsulfone (PPSU), polyethersulfone (PES), poly(arylsulfide) polymers; in particular PPS as defined above.

[0076] Preferred thermoplastic polymers may be selected from the group consisting of polyamides, poly(aryl ether ketone) polymers and poly(aryl sulfide) polymers.

[0077] Among suitable thermosetting materials for the polymer matrix in layer (CL) there may be mentioned epoxy resins.

[0078] Layer (CL) comprises continuous reinforcing fibers. As used herein, the expression "continuous reinforcing fibers" refers to fibers having a length, in their longest dimension, of at least 5 mm.

[0079] In some embodiments, the continuous reinforcing fibers have a length in their longest dimension of at least 1 cm, at least 25 cm, or at least 50 cm. The length of the continuous reinforcing fibers depends on the shape and size of the finished part.

[0080] The continuous reinforcing fibers are selected from the group consisting of glass fibers, carbon fibers, aluminum fibers, metal fibers, ceramic fibers, titanium fibers, magnesium fibers, boron carbide fibers, rock wool fibers, steel fibers, aramid fibers, and natural fibers (e.g., cotton, linen, and wood). Preferably, the continuous reinforcing fibers are selected from the group consisting of glass fibers, carbon fibers, aramid fibers, and ceramic fibers. Advantageously, the continuous reinforcing fibers are carbon fibers.

[0081] In some embodiments, layer (CL) may include one or more additional continuous reinforcing fibers, each having a different composition and as described above.

[0082] Overall, the continuous reinforcing fibers constitute at least 5.0% of the total volume of the layer (CL). Typically, the continuous reinforcing fibers are at least 10.0%, at least 15.0%, or even at least 20.0% of the total volume of the layer (CL). The continuous reinforcing fibers are not more than 80.0%, not more than 75.0%, or even not more than 70.0% of the total volume of the layer (CL). The continuous reinforcing fibers may advantageously represent 20.0% to 75.0%, 25.0% to 70.0%, 25.0% to 65.0%, or even 30.0% to 60.0% of the total volume of the layer (CL). The polymer matrix represents the remainder of the volume of the layer (CL).

[0083] The continuous reinforcing fibers in a layer (CL) are generally aligned along a single direction. Generally, the 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, 25 degrees, 20 degrees, 15 degrees, or 10 degrees of the direction of the other fibers.

[0084] In certain embodiments, the continuous reinforcing fibers in a layer (CL) may be arranged at an angle relative to one another. The continuous reinforcing fibers may be arranged as a woven fabric or a layered fabric, or any combination of one or more.

[0085] The layer (CL) can be manufactured by methods known in the art, and generally involves impregnating continuous reinforcing fibers with a polymer matrix or a precursor to a polymer matrix if the polymer is a thermosetting polymer, followed by cooling or drying to form the layer (CL).

[0086] When more than one layer (CL) is present, each layer (CL) may be the same or different.

[0087] The layer (CL) has a thickness that is usually between 100 microns and 500 microns, the thickness being adapted to provide the required structural resistance for the container.

[0088] container The term "vessel" is used herein to refer to a hollow vessel. The vessel of the present invention is in particular a hollow vessel for containing a gas, preferably a gas under pressure.

[0089] Layer (BL) represents the only or inner layer of the container that comes into contact with the gas being transported or stored, hereinafter referred to as the "liner." Layer (CL) represents the outer layer of the container, if present.

[0090] The container may include one layer (BL) and one or more layers (CL). In one aspect of this embodiment, if more layers (CL) are present, they have the same composition. The layers (CL) may be 2, 3, 5, 10, 50, and even up to 100 or more, such as 200 or 300.

[0091] The vessel is preferably a pressure vessel, ie a vessel suitable for the storage and transport of gases under pressure.

[0092] The vessel, or preferably a pressure vessel, comprises a hollow body and at least one boss. A boss is known to those skilled in the art and refers to an opening to which a closure is attached that allows gas or fluid flow into and out of the vessel. The boss is usually made of metal.

[0093] The hollow body may have any shape suitable for the storage of gas, in particular gas under pressure.

[0094] In certain conventional embodiments, the container has a cylindrical shape and the bosses are located at the ends. Often the container has two bosses, one at each end of the cylindrical shape.

[0095] The shape of the hollow body is determined by the desired application. It is usually, but not exclusively, cylindrical; it typically has a diameter of 10.0 cm to 1.00 m.

[0096] The length of the hollow body also depends on the end use and can be, for example, up to lengths as large as 50.0 cm to 10.0 m. These longer lengths are typically used for gas transport. For example, for containers in trucks, the length is typically 1.0 m to 3.0 m.

[0097] The container of the present invention is 3.5 dm 3 ~5.0m 3 , and even 5.0dm 3 ~1.0m 3 The internal volume of the container may be at least 10.0 dm 3 , and at least 15.0 dm 3 The internal volume can be 1.0m 3 Below that, 0.5m 3 It could be.

[0098] The container comprises a hollow body which may consist only of one or more layers (BL). Alternatively, the container may comprise, from the inside to the outside of the container: at least one layer (BL), or liner, as defined above, and at least one structural composite layer, a layer (CL), as defined above, in contact with the at least one layer (BL). The layer (BL) is in contact with the gas contained in the container.

[0099] The liner is intended to provide a barrier between the fluid or gas and the layer (CL) to prevent leakage. Typically, the layer (CL) is provided around the liner to provide mechanical properties, such as burst pressure resistance.

[0100] The container may be prepared according to any method known in the art.

[0101] For example, the liner may be prepared by blow molding, tube extrusion, injection molding and welding and / or rotomolding. The layer (CL), if present, may then be applied onto the outer surface of the liner by wrapping a tape or towpreg comprising continuous reinforcing fibers and a polymer matrix around the hollow body made of the liner.

[0102] Other manufacturing processes, such as those known in the art for the manufacture of pressure vessels, can be used to manufacture the vessels of the present invention.

[0103] The container of the present invention is characterized by good hydrogen barrier and mechanical properties.

[0104] The container according to the invention exhibits a nominal pressure of at least 2.5 MPa, typically at least 20.0 MPa, or even at least 30.0 MPa. The nominal pressure may be up to 70.0 MPa, 100 MPa, or even 150.00 MPa or more. Advantageously, the container according to the invention has a nominal pressure of 20.0 to 70.0 MPa.

[0105] A burst pressure of at least 157.5 MPa can be achieved for storage of hydrogen gas in a container according to the invention. Containers for storage of compressed hydrogen typically require a nominal pressure of 35.0 MPa or 70.0 MPa. Burst pressures, measured in accordance with ECE R134, are typically no greater than 78.8 MPa and 157.5 MPa, respectively.

[0106] A further object of the present invention is a compressed gas in a container comprising the multilayer structure of the first object, wherein layer (BL) is in contact with a compressed gas, advantageously selected from the group consisting of hydrogen, oxygen, nitrogen, argon, helium, methane, propane, compressed natural gas, CO2 and ammonia.

[0107] 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.

[0108] A third object of the invention is therefore a compressed gas contained in a vessel in which the layer (BL) is in contact with the compressed gas, the gas being 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 present invention is a vehicle containing a container or compressed gas contained within the container.

[0111] The vehicle may be a car, truck, train, ship, urban mobility vehicle, airplane, helicopter, or any other vehicle that can be powered using the conversion of gas into energy by any means.

[0112] The above-described embodiments are intended to be illustrative and not limiting. Further embodiments are within the concept of the present invention. Additionally, while the present invention has been described with reference to specific embodiments, those skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the invention. [Example]

[0113] raw materials PA1: Amodel® 1004 PA 6T / 6I / 66 copolymer commercially available from Solvay Specialty Polymer USA, LLC

[0114] PA2: Amodel® ET 1000 HS NT, an impact-modified PA 6T / 6I / 66 copolymer commercially available from Solvay Specialty Polymer USA, LLC

[0115] PA12 is Grilamid® L25NZ impact modified PA12 available from EMS Chemie.

[0116] PA6 is a nylon manufactured by UBE Industries TM It is 1218IU.

[0117] Tensile test Tensile properties were measured according to ISO 527-2 using specimens meeting the requirements of ISO 1BA at a test speed of 5 mm / min and at the temperatures indicated. The specimens were annealed for 2 hours at 20°C above their glass transition temperature to ensure full crystallinity before tensile testing.

[0118] Determination of H2 permeability coefficient Samples for hydrogen permeation testing were prepared as follows: The polymer was dried overnight at 107°C in a desiccant drying oven with a -40°C dew point to ensure the material was dry before injection molding into plates. Following the polymer supplier's recommended injection molding processing guidelines, the material was injection molded into 10 cm x 10 cm x 0.32 cm plates using a 250-ton Sumitomo SE 250 EV-A HD all-electric injection molding machine. The molding machine was equipped with a 45 mm screw size with a maximum screw speed of 250 rpm and a maximum shot capacity of 0.34 dm3. The machine had a maximum shot size of 21 cm, and the maximum injection pressure was 215 MPa. The plates were annealed for 2 hours at 20°C above their glass transition temperature to ensure full crystallinity before hydrogen permeation testing.

[0119] The sample was mounted in a sealed chamber and checked to ensure that the chamber was leak-tight by applying hydrogen at 1 MPa to the feed side. The chamber was then conditioned at the temperature of the test. H was supplied to the feed side at 1 MPa. Synthetic air was supplied to the permeate side at a controlled throughput rate, and H was measured using a calibrated Inficon Sentrac H Leak Detector until a stable value for H was obtained to ensure steady state.

[0120] The permeability coefficient was calculated taking into account the thickness of the sample, the exposed surface, the flow rate and pressure of the carrier gas, and the results are shown in Table 1.

[0121] [Table 1]

[0122] The combination of the above properties allows for the design of thinner liners with excellent hydrogen barrier properties without compromising the mechanical properties of the container.

Claims

1. A container comprising at least one barrier layer, [layer (BL)], comprising at least one thermoplastic polymer, [thermoplastic polymer (TP)], wherein the at least one thermoplastic polymer, [thermoplastic polymer (TP)] a glass transition temperature of at least 65°C; - a melting temperature of at most 320°C; - an elongation at break at -40°C of at least 2.5% when measured according to ISO 527-2 using test specimens according to ISO 1BA at a test speed of 5 mm / min; and - Maximum 500 Ncm ３ mm / m ２ Hydrogen permeability coefficient at 85°C in .d.bar A container characterized by:

2. Container according to claim 1, wherein said thermoplastic polymer (TP) has a glass transition temperature above 80°C and not above 180°C.

3. The thermoplastic polymer (TP) has the following properties: a melting temperature of 200°C to 315°C; an elongation at break at -40°C of at least 3.0%; and a temperature of 1 to 400 Ncm ３ mm / m ２ 3. The container according to claim 1 or 2, having at least one hydrogen permeability coefficient of 0.1 MPa at 85°C and a hydrogen permeability coefficient of 0.1 MPa at 85°C.

4. Container according to any one of claims 1 to 3, wherein the thermoplastic polymer (TP) is selected from the group consisting of poly(arylene sulfide) polymers and semi-aromatic polyamides.

5. 5. The container according to any one of claims 1 to 4, wherein the thermoplastic polymer (TP) is a semi-aromatic polyamide selected from the group consisting of semi-aromatic polyamides comprising repeating units of the formula XT, where T is terephthalic acid and X represents units derived from a linear or branched, aliphatic or cycloaliphatic diamine having x carbon atoms, where x is selected from 6, 7, 8, 10, 11, 12, 13, 14, 15, 16.

6. Container according to any one of claims 1 to 5, wherein the thermoplastic polymer (TP) is selected from PA 6T / 66 and PA 6T / 6I / 66.

7. Container according to any one of claims 1 to 4, wherein said thermoplastic polymer (TP) is poly(phenylene sulfide).

8. 8. Container according to any one of the preceding claims, wherein layer (BL) comprises a thermoplastic polymer (TP) and from 1% to 25% by weight of said at least one impact modifier relative to the total weight of said layer (BL).

9. Container according to any one of claims 1 to 8, comprising at least one layer (BL) and at least one composite layer [layer (CL)] in contact with said at least one layer (BL), said layer (CL) comprising continuous reinforcing fibres and a thermoplastic or thermosetting polymer matrix.

10. 10. The container according to claim 9, wherein the continuous reinforcing fibers are selected from the group consisting of glass fibers, carbon fibers, aramid fibers, and ceramic fibers, preferably in an amount of 20% to 75% relative to the total volume of the layer (CL).

11. Container according to any one of claims 1 to 10, wherein said layer (BL) represents an inner layer of said container and said layer (CL) represents an outer layer of said container.

12. below: - diameter between 10.0 cm and 1.0 m; - a length of 50.0 cm to 10.0 m; and - 3.5 dm ３ ~5.0m ３ The internal volume of Container according to any one of claims 1 to 11 in the form of a hollow body having one or more of:

13. Compressed gas contained in a vessel according to any one of claims 1 to 12, said compressed gas being in contact with a layer (BL).

14. Hydrogen, oxygen, nitrogen, argon, helium, methane, propane, compressed natural gas, CO ２ 14. The compressed gas of claim 13, selected from the group consisting of: ammonia.

15. A vehicle comprising a container according to any one of claims 1 to 12 or a compressed gas according to claim 13 or 14.

16. Use of a container according to any one of claims 1 to 12 for storing or transporting compressed gases.

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