Multilayer structure for transporting or storing hydrogen - Patents.com

Abstract

A multi-layer structure intended for the transport, distribution and storage of hydrogen, comprising, from the inside to the outside, at least one leak-proof layer (1) and at least one composite reinforcing layer (2), The innermost composite reinforcing layer is wrapped around the outermost adjacent leak-proof layer (1), The leak-proof layer is at least one aliphatic polyamide thermoplastic polymer P1i (i = 1 to n, n is the number of semi-crystalline leak-proof layers) whose Tm, measured according to ISO11357-3:2013, is greater than 200°C, except for polyether block amides (PEBA); The polyamide thermoplastic polymer is a polyamide having an average of 7 to 9 carbon atoms per nitrogen atom; up to 30% by weight of an impact modifier, based on the total weight of the composition; A composition comprising a plasticizer in an amount of up to 1.5% by weight based on the total weight of the composition, the composition is devoid of a nucleating agent; the at least one polyamide thermoplastic polymer of each leak-proof layer can be the same or different; at least one of said composite reinforcing layers consists of a fibrous material in the form of continuous fibres impregnated with a composition mainly comprising at least one polymer P2j, 1. A multi-layer structure, wherein said structure is devoid of a layer made of a polyamide polymer, said layer made of a polyamide polymer being outermost and adjacent to an outermost layer of a composite reinforcement.

Description

[Technical field]

[0001] This patent application relates to composite multi-layer structures for the transport, distribution or storage of hydrogen, in particular for the distribution or storage of hydrogen, and processes for their manufacture. [Background technology]

[0002] Hydrogen tanks are currently a subject of great interest on the part of numerous manufacturers, especially in the automotive sector. One of the objectives pursued is to provide less polluting vehicles. Thus, the aim is for electric or hybrid vehicles equipped with batteries to gradually replace thermal vehicles such as gasoline or diesel vehicles. In practice, the battery turns out to be a relatively complex component of the vehicle. Depending on the location of the battery in the vehicle, it may be necessary to protect it from impacts and the external environment, which may be of extreme temperatures and variable humidity. Also, any risk of fire must be avoided.

[0003] Furthermore, in order not to damage the battery cells and preserve its lifespan, it is important that its operating temperature does not exceed 55°C. Conversely, in winter, for example, it may be necessary to increase the battery temperature to optimize its operation.

[0004] Furthermore, electric vehicles still suffer from several problems today, namely the range of the batteries, the use of rare earth metals in these batteries, which are not exhaustible resources, charging times that are much longer than the period for filling the tank, and problems with electricity production in various countries to make the batteries rechargeable.

[0005] Hydrogen is therefore an alternative to electric batteries, as it can be converted into electricity by fuel cells and thus power electric vehicles.

[0006] Hydrogen tanks generally consist of a metal liner (or leakproof layer) that must prevent hydrogen permeation. One type of tank envisaged is called Type IV and is based on a thermoplastic liner around which a composite is wrapped.

[0007] Their basic principle is the separation of two essential functions, leaktightness and mechanical strength, in order to manage them independently of each other. In this type of tank, a liner (or leaktight covering) made of thermoplastic resin is combined with a reinforcing structure made of fibers (glass, aramid, carbon), also known as reinforcing coverings or layers, which allows it to operate at much higher pressures while reducing its weight and avoiding the risk of explosive destruction in the event of a severe external attack.

[0008] The liner must exhibit certain basic characteristics: Can be transformed by extrusion blow molding, rotational molding, injection molding or extrusion, Low hydrogen permeability (because the permeability of the liner is the key factor limiting hydrogen loss in the tank); Good mechanical (fatigue) properties at low temperatures (-40 to -70°C); Heat resistance at 120℃.

[0009] This is due to the need to increase the filling speed of the hydrogen tank, which must be approximately equivalent to the filling speed of a gasoline tank for a thermal engine (about 3 to 5 minutes), but this increase in speed leads to greater heating of the tank, which then reaches temperatures of about 100 °C.

[0010] The performance quality and safety assessment of hydrogen tanks can be determined in European reference laboratories (GasTeF: Hydrogen Tank Test Facility) as described by Galassi et al. (World Hydrogen Energy Conference 2012, Onboard Compressed Hydrogen Storage: Fast Filling Experiments and Simulations, Energy Procedia, 29, (2012) 192-200).

[0011] Type IV generation 1 tanks used liners based on high density polyethylene (HDPE).

[0012] However, HDPE presents the disadvantage of having an excessively low melting point and a high hydrogen permeability, which represents a problem for modern requirements regarding thermal resistance and does not allow the filling speed of the tank to be increased.

[0013] Over the years, liners based on polyamide PA6 or PA66 have been developed.

[0014] Nevertheless, PA6 and PA66 exhibit the disadvantages of poor cold resistance and high water absorption.

[0015] Liners made of PA12 have also been developed which exhibit good impact strength, but PA12 exhibits the drawback of having an excessively high hydrogen permeability.

[0016] EP 3112421 A1 describes a polyamide resin composition for moldings intended for high pressure hydrogen, the composition comprising: The present invention comprises a polyamide 6 resin (A) and a polyamide resin (B) having a melting point that is 20°C or lower higher than the melting point of the polyamide 6 resin (A) as determined by DSC, and a cooling crystallization point that is higher than the cooling crystallization point of the polyamide 6 resin (A) as determined by DSC.

[0017] French patent application FR 2 923 575 describes a tank for storing fluids under high pressure, comprising, at each axial end, an end metal cap, a liner surrounding said cap and a structural layer made of fibres impregnated with a thermosetting resin surrounding said liner.

[0018] EP 3222668 A1 describes a polyamide resin composition for molded articles intended for high-pressure hydrogen, the composition comprising a polyamide resin (A) comprising units derived from hexamethylenediamine and units derived from an aliphatic dicarboxylic acid of 8 to 12 carbon atoms, and an ethylene / α-olefin copolymer (B) modified with an unsaturated carboxylic acid and / or one of its derivatives.

[0019] US Patent Application Publication No. 2014 / 008373 describes a light storage cylinder for highly compressed gas, the cylinder having a liner surrounded by a stress layer, the liner comprising: a first inner layer of impact modified polyamide (PA) in contact with the gas; an outer thermoplastic layer in contact with the stress layer; and an adhesive tie layer between the first inner layer of impact modified PA and the outer thermoplastic layer.

[0020] WO 1855491 describes a component for the transport of hydrogen, exhibiting a three-layer structure, the inner layer of which consists of PA11, 15% to 50% impact modifier and 1% to 3% plasticizer or a composition devoid of plasticizer, exhibiting barrier properties against hydrogen, good flexibility and low temperature durability. However, this structure is suitable for pipes for the transport of hydrogen, but not for pipes for the storage of hydrogen.

[0021] Thus, one is still optimizing the matrix of the composite, on the one hand, to optimize its high-temperature mechanical strength, and on the other hand, the materials constituting the leakproof covering, to optimize its processing temperature. Thus, a possible change in the composition of the materials constituting the leakproof covering produced must not be reflected by a significant increase in the manufacturing temperature of this liner (extrusion blow molding, injection molding, rotational molding, etc.) compared to what is practiced today.

[0022] Furthermore, the impact strength, water absorption and hydrogen permeability of the material that constitutes the leakproof coating should also be optimized.

[0023] These different problems are solved by providing a multi-layer structure according to the invention, which is intended for the transport, distribution or storage of hydrogen.

[0024] Throughout this specification, the terms "liner" and "leakproof covering" have the same meaning.

[0025] The present invention therefore relates to a multi-layer structure intended for the transport, distribution and storage of hydrogen, comprising, from the inside to the outside, at least one leak-proof layer (1) and at least one composite reinforcing layer (2), The innermost composite reinforcing layer is wrapped around the outermost adjacent leak-proof layer (1), The leak-proof layer is at least one aliphatic polyamide thermoplastic polymer P1i (i = 1 to n, n is the number of semi-crystalline leak-proof layers) whose Tm, measured according to ISO11357-3:2013, is greater than 200°C, except for polyether block amides (PEBA); The polyamide thermoplastic polymer is a polyamide having an average of 7 to 9 carbon atoms per nitrogen atom; up to 30% by weight of impact modifiers, in particular up to 15% by weight of impact modifiers, in particular up to 9% by weight of impact modifiers, based on the total weight of the composition; A composition comprising a plasticizer in an amount of up to 1.5% by weight based on the total weight of the composition, the composition is devoid of a nucleating agent; the at least one polyamide thermoplastic polymer of each leak-proof layer can be the same or different; at least one of said composite reinforcing layers consists of a fibrous material in the form of continuous fibres impregnated with at least one polymer P2j (j=1 to m, m being the number of reinforcing layers), in particular with a composition comprising predominantly an epoxy or epoxy-based resin or a resin based on polyisocyanates, in particular polyisocyanurates, The present invention relates to a multi-layer structure, wherein the structure is devoid of a layer made of a polyamide polymer, and wherein the layer made of a polyamide polymer is outermost and adjacent to the outermost layer of a composite reinforcement.

[0026] The inventors have therefore unexpectedly found that the use of a polyamide thermoplastic polymer having an average number of carbon atoms per nitrogen atom between 7 and 9, with a limited proportion of impact modifiers and plasticizers for the leakproof layer, with a different polymer for the matrix of the composite, in particular an epoxy or epoxy-based resin or a resin based on polyisocyanates, in particular polyisocyanurates, and wrapping said composite on the leakproof layer, makes it possible to obtain a compromise in particular with regard to impact strength, hydrogen permeability and water absorption, in comparison with a polyamide thermoplastic polymer having an average number of carbon atoms per nitrogen atom less than 7 and more than 9, and therefore makes it possible to obtain a structure suitable for the transport, distribution or storage of hydrogen, in particular for increased maximum use temperatures, which may range up to 120° C., and therefore allows an increase in the filling speed of the tank.

[0027] The term "multilayer structure" is to be understood to mean a tank which comprises or consists of several layers, i.e. several leakproof layers and several reinforcing layers, or one leakproof layer and several reinforcing layers, or several leakproof layers and one reinforcing layer, or one leakproof layer and one reinforcing layer.

[0028] Thus, multi-layer structures are understood to exclude pipes or tubes.

[0029] In one embodiment, PA6 and PA66 are excluded from the composition of the leakproof layer.

[0030] In one embodiment, the multi-layer structure comprises two layers: a leakproof layer and a reinforcing layer.

[0031] The leakproof layer is the innermost layer relative to the composite reinforcing layer, which is the outermost layer.

[0032] The tank may be a tank for mobile storage of hydrogen, i.e. on a truck for the transportation of hydrogen, on a car for transporting hydrogen and for example supplying hydrogen for fuel cells, on a train for supplying hydrogen or on a drone for supplying hydrogen, but it may also be a tank for fixed storage of hydrogen on site in order to distribute hydrogen to vehicles.

[0033] Advantageously, the leakproof layer (1) is leakproof to hydrogen at 23° C., i.e., the hydrogen permeability at 23° C. is less than 100 cc.mm / m at 23° C. and 0% relative humidity (RH). 2 is less than .24h.atm.

[0034] The transmittance is (cc.mm / m 2 It can also be expressed in units of .24h.Pa.

[0035] In that case the transmittance must be multiplied by 101325.

[0036] In one embodiment, copolymers of ethylene and α-olefins are excluded from the impact modifiers of the leakproof layer composition.

[0037] In another embodiment, the leakproof layer comprises: a composition mainly comprising at least one aliphatic polyamide thermoplastic polymer P1i (i=1 to n, n being the number of semi-crystalline leak-proof layers, the Tm of which, measured according to ISO11357-3:2013, is greater than 200° C., except for polyether block amide (PEBA)); The polyamide thermoplastic polymers are polyamides exhibiting an average number of carbon atoms per nitrogen atom of between 7 and 9, with the exception of PA610.

[0038] In yet another embodiment, the leakproof layer comprises: a composition mainly comprising at least one aliphatic polyamide thermoplastic polymer P1i (i=1 to n, n being the number of semi-crystalline leak-proof layers, the Tm of which, measured according to ISO11357-3:2013, is greater than 200° C., except for polyether block amide (PEBA)); The polyamide thermoplastic polymer is a polyamide exhibiting an average number of carbon atoms per nitrogen atom of 7 to 9, with the exception of PA610; Copolymers of ethylene and alpha-olefins are excluded from the impact modifiers.

[0039] The composite reinforcing layer is wrapped around the leakproof layer, for example by strips (or tapes or rovings) of polymer-impregnated fibers deposited by filament winding.

[0040] If several layers are present, the polymers are different.

[0041] If the polymer of the reinforcing layer is the same, there may be several layers, but advantageously there is only one reinforcing layer, which then presents at least one complete wrap around the leakproof layer.

[0042] This fully automated process, well known to those skilled in the art, makes it possible to select, layer by layer, the winding angle that gives the final structure the ability to withstand internal pressure loads.

[0043] If several leak barrier layers are present, only the innermost one is in direct contact with hydrogen.

[0044] If there is only one leakproof layer and one composite reinforcing layer, thus resulting in a two-layer multi-layer structure, then these two layers may be in direct contact with each other and adhere to each other, especially due to the wrapping of the composite reinforcing layer on the leakproof layer.

[0045] If there are several leak barrier layers and / or several composite reinforcement layers, then the outermost layer of the leak barrier layer, and thus the opposite layer in contact with hydrogen, may or may not be bonded to the innermost layer of the composite reinforcement.

[0046] The other composite reinforcing layers may or may not be bonded to each other.

[0047] The other leakproof layers may or may not be adhered to each other.

[0048] Advantageously, there is only one leakproof layer and one reinforcing layer, which are not bonded to each other.

[0049] Advantageously, there is only one leakproof layer and one reinforcing layer, which are not bonded to one another and the reinforcing layer consists of a fibrous material in the form of continuous fibres impregnated with at least one polymer P2j, in particular an epoxy or epoxy-based resin, or a composition which mainly comprises a resin based on polyisocyanates, in particular polyisocyanurates.

[0050] In one embodiment there is only one leakproof layer and one reinforcing layer, which are not bonded to each other and the reinforcing layer consists of a fibrous material in the form of continuous fibres impregnated with a composition which mainly comprises polymer P2j, which is an epoxy or epoxy-based resin or a resin based on polyisocyanates, in particular polyisocyanurates.

[0051] The expression "epoxy-based" is used throughout this specification to mean that the epoxide constitutes at least 50% by weight of the matrix.

[0052] About the leak barrier and thermoplastic polymer P1i There may be one or more leakproof layers.

[0053] Each of said layers consists of a composition mainly comprising at least one thermoplastic polymer P1i, i corresponding to the number of layers present, i being between 1 and 10, in particular between 1 and 5, in particular between 1 and 3, preferentially i=1.

[0054] The term "predominantly" means that said at least one polymer is present in an amount of more than 50% by weight relative to the total weight of the composition.

[0055] Advantageously, said at least one main polymer is present in an amount of more than 60% by weight, in particular more than 70% by weight, in particular more than 80% by weight and more particularly 90% or more by weight relative to the total weight of the composition.

[0056] The composition may also contain up to 30% by weight of impact modifiers and / or plasticizers and / or additives, relative to the total weight of the composition.

[0057] The additives, excluding the nucleating agent, can be selected from another polymer, an antioxidant, a heat stabilizer, a UV absorber, a light stabilizer, a lubricant, an inorganic filler, a flame retardant, a colorant, carbon black and a carbon-based nanofiller; in particular, the additives, excluding the nucleating agent, are selected from an antioxidant, a heat stabilizer, a UV absorber, a light stabilizer, a lubricant, an inorganic filler, a flame retardant, a colorant, carbon black and a carbon-based nanofiller.

[0058] Said other polymer may be another semi-crystalline thermoplastic polymer or a different polymer, in particular EVOH (ethylene / vinyl alcohol).

[0059] Advantageously, said composition comprises mainly said thermoplastic polymer P1i, from 0% to 30% by weight of impact modifier, in particular from 0% to less than 15% by weight of impact modifier, in particular from 0% to 9% by weight of impact modifier, from 0% to 1.5% by weight of plasticizer and from 0% to 5% by weight of additives, the sum of the components of the composition being equal to 100%.

[0060] Advantageously, said composition consists mainly of said thermoplastic polymer P1i, from 0% to 30% by weight of impact modifier, in particular from 0% to less than 15% by weight of impact modifier, in particular from 0% to 9% by weight of impact modifier, from 0% to 1.5% by weight of plasticizer and from 0% to 5% by weight of additives, the sum of the components of the composition being equal to 100%.

[0061] The at least one primary polymer of each layer may be the same or different.

[0062] In one embodiment, only one predominant polymer is present in the leakproof layer that is not bonded to at least the composite reinforcement layer.

[0063] In one embodiment, the composition comprises from 0.1% to 30% by weight, in particular from 0.1% to less than 15% by weight, in particular from 0.1% to 9% by weight of impact modifier relative to the total weight of the composition.

[0064] In another embodiment, the composition comprises from 1% to 30% by weight, in particular from 1% to less than 15% by weight, in particular from 1% to 9% by weight of impact modifier relative to the total weight of the composition.

[0065] In particular, the composition comprises from 2% to 30% by weight, in particular from 2% to less than 15% by weight, in particular from 2% to 9% by weight, of impact modifier relative to the total weight of the composition.

[0066] In particular, the composition comprises from 3% to 30% by weight, in particular from 3% to less than 15% by weight, in particular from 3% to 9% by weight, of impact modifier relative to the total weight of the composition.

[0067] In particular, the composition comprises from 4% to 30% by weight, in particular from 4% to less than 15% by weight, in particular from 4% to 9% by weight, of impact modifier relative to the total weight of the composition.

[0068] In particular, the composition comprises from 5% to 30% by weight, in particular from 5% to less than 15% by weight, in particular from 5% to 9% by weight, of impact modifier relative to the total weight of the composition.

[0069] In one embodiment, the composition is devoid of plasticizers.

[0070] In another embodiment, the composition comprises from 0.1% to 30% by weight, in particular from 0.1% to less than 15% by weight, in particular from 0.1% to 9% by weight, of an impact modifier relative to the total weight of the composition, and the composition is devoid of a plasticizer.

[0071] In yet another embodiment, the composition comprises from 0.1% to 30% by weight, in particular from 0.1% to less than 15% by weight, in particular from 0.1% to 9% by weight of impact modifier, and from 0.1% to 1.5% by weight of plasticizer, relative to the total weight of the composition.

[0072] Thermoplastic polymer P1i A semi-crystalline thermoplastic polymer or thermoplastic resin is understood to mean a material which is generally solid at normal temperature, which softens during temperature increase, in particular after passing its glass transition temperature (Tg), which exhibits clear melting upon passing its "melting point" (Tm), and which becomes solid again during temperature decrease below its crystallization point.

[0073] Tg, Tc and Tm are determined by differential scanning calorimetry (DSC) according to standards 11357-2:2013 and 11357-3:2013, respectively.

[0074] The number average molecular weight Mn of said semicrystalline polyamide thermoplastic polymer is preferably in the range of 10 000 to 85 000, in particular 10 000 to 60 000, preferentially 10 000 to 50 000 and even more preferentially 12 000 to 50 000. These Mn values ​​are determined in m-cresol according to standard ISO 307:2007, but by changing the solvent (using m-cresol instead of sulfuric acid and the temperature being 20° C.) it is possible to correspond to an intrinsic viscosity of 0.8 or more.

[0075] The nomenclature used to define polyamides is described in standard ISO 1874-1:2011 "Plastics - Polyamide (PA) molding and extrusion materials - Part 1: Nomenclature", in particular page 3 (Tables 1 and 2) and is well known to the person skilled in the art.

[0076] The polyamide may be a homopolyamide or a copolyamide or a mixture thereof.

[0077] Advantageously, said polymer P1i is an aliphatic polyamide chosen from PA410, PA412, PA510, PA512, PA610 and PA612.

[0078] In one embodiment, said polymer P1i is an aliphatic polyamide selected from PA410, PA412, PA510, PA512 and PA612.

[0079] Advantageously, each leakproof layer is made of a composition comprising the same type of polyamide.

[0080] If welding is required, there are various methods that make it possible to weld elements made of polyamide thermoplastic polymers: thus, contact, ultrasonic, infrared, application of vibrations, rotation to weld one element to the other, or heated blades with or without laser welding may be used.

[0081] About impact modifiers The impact modifier can be any polymer with a lower modulus than the resin that exhibits good adhesion with the matrix to dissipate crack energy.

[0082] The impact modifier advantageously consists of a polymer, in particular a polyolefin, exhibiting a flexural modulus of less than 100 MPa, measured according to standard ISO 178, and having a Tg (measured according to standard 11357-2 at the inflection point of the DSC thermogram) of less than 0° C.

[0083] In one embodiment, PEBA is excluded from the definition of impact modifier.

[0084] The polyolefins of the impact modifier may be functionalized or unfunctionalized, or may be a mixture of at least one functionalized and / or at least one unfunctionalized. For simplicity, the polyolefins are designated (B) and functionalized polyolefins (B1) and unfunctionalized polyolefins (B2) are described below.

[0085] The non-functionalized polyolefins (B2) are conventionally homopolymers or copolymers of α-olefins or diolefins, such as, for example, ethylene, propylene, 1-butene, 1-octene or butadiene. By way of example, mention may be made of: - polyethylene homopolymers and copolymers, in particular LDPE, HDPE, LLDPE (linear low density polyethylene), VLDPE (very low density polyethylene) and metallocene polyethylene; propylene homopolymers or copolymers, - ethylene / α-olefin, such as ethylene / propylene, EPR (short for ethylene / propylene rubber) and ethylene / propylene / diene (EPDM), copolymers; - styrene / ethylene-butene / styrene (SEBS), styrene / butadiene / styrene (SBS), styrene / isoprene / styrene (SIS) or styrene / ethylene-propylene / styrene (SEPS) block copolymers; - Copolymers of ethylene and at least one product chosen from salts or esters of unsaturated carboxylic acids, such as alkyl (meth)acrylates (for example methyl acrylate), or vinyl esters of saturated carboxylic acids, such as vinyl acetate (EVA), the proportion of comonomer being capable of reaching 40% by weight.

[0086] The functionalized polyolefins (B1) may be polymers of α-olefins having reactive units (functional groups), such as acid, anhydride or epoxy functional groups. Examples include the aforementioned polyolefins (B2) grafted or copolymerized or trimerized with unsaturated epoxides, such as glycidyl (meth)acrylate, or with carboxylic acids or the corresponding salts or esters, such as (meth)acrylic acid (the latter can be fully or partially neutralized, for example, by metals such as Zn), or with carboxylic anhydrides, such as maleic anhydride. The functionalized polyolefins are, for example, PE / EPR mixtures, the weight ratio of which may vary within a wide range, for example from 40 / 60 to 90 / 10, said mixtures being cografted, depending on the degree of grafting, for example with 0.01% by weight to 5% by weight of anhydride, in particular maleic anhydride.

[0087] The functionalized polyolefins (B1) can be chosen from the following (co)polymers grafted with maleic anhydride or with glycidyl methacrylate, the degree of grafting being, for example, between 0.01% and 5% by weight: PE, PP, copolymers of ethylene with propylene, butene, hexene or octene, for example containing 35% to 80% by weight of ethylene, - ethylene / α-olefin, such as ethylene / propylene, EPR (short for ethylene / propylene rubber) and ethylene / propylene / diene (EPDM), copolymers; - styrene / ethylene-butene / styrene (SEBS), styrene / butadiene / styrene (SBS), styrene / isoprene / styrene (SIS) or styrene / ethylene-propylene / styrene (SEPS) block copolymers; - copolymers of ethylene and vinyl acetate (EVA) containing up to 40% by weight of vinyl acetate; - copolymers of ethylene and alkyl (meth)acrylates, containing up to 40% by weight of alkyl (meth)acrylates; -Copolymers of ethylene, vinyl acetate (EVA) and alkyl (meth)acrylates containing up to 40% by weight of comonomer.

[0088] The functionalized polyolefin (B1) can also be chosen from ethylene / propylene copolymers, with a predominance in propylene, grafted with maleic anhydride and then condensed with a monoaminated polyamide (or polyamide oligomer) (products described in EP-A-0 342 066).

[0089] The functionalized polyolefin (B1) may be a copolymer or terpolymer of at least the following units: (1) ethylene, (2) an alkyl (meth)acrylate or a saturated carboxylic acid vinyl ester, and (3) an anhydride, such as maleic anhydride or (meth)acrylic anhydride, or an epoxy, such as glycidyl (meth)acrylate.

[0090] As examples of the latter type of functionalized polyolefins, the following copolymers may be mentioned, in which ethylene preferably represents at least 60% by weight and the termonomers (functional groups) represent, for example, 0.1% to 10% by weight of the copolymer: - ethylene / alkyl (meth)acrylate / (meth)acrylic acid or maleic anhydride or glycidyl methacrylate copolymers, -ethylene / vinyl acetate / maleic anhydride or glycidyl methacrylate copolymers, - Ethylene / vinyl acetate or alkyl (meth)acrylate / (meth)acrylic acid or maleic anhydride or glycidyl methacrylate copolymers.

[0091] In the preceding copolymers, the (meth)acrylic acid can be salified with Zn or Li.

[0092] The term "alkyl (meth)acrylate" in (B1) or (B2) denotes C1-C8 alkyl methacrylates and acrylates, and may be selected from methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, methyl methacrylate and ethyl methacrylate.

[0093] Furthermore, the above-mentioned polyolefins (B1) can also be crosslinked by any suitable process or agent (diepoxy, diacid, peroxide, etc.), and the term "functionalized polyolefin" also includes mixtures of the above-mentioned polyolefins with difunctional reactants such as diacids, dianhydrides, diepoxy, etc. that can react with these polyolefins, or mixtures of at least two functionalized polyolefins that can react with each other.

[0094] The above-mentioned copolymers (B1) and (B2) can be copolymerized randomly or in a block manner and exhibit a linear or branched structure.

[0095] The molecular weight, MFI index and density of these polyolefins can also vary within wide limits that will be appreciated by those skilled in the art. MFI is the abbreviation for Melt Flow Index. It is measured according to standard ASTM 1238.

[0096] The non-functionalized polyolefin (B2) is advantageously chosen from homopolymers or copolymers of polypropylene and any homopolymer of ethylene or copolymers of ethylene with comonomers of higher α-olefin type such as butene, hexene, octene or 4-methyl-1-pentene. Mention may be made, for example, of PP, high density PE, medium density PE, linear low density PE, low density PE or very low density PE. These polyethylenes are known to those skilled in the art as being produced according to the "radical" process, according to catalysis of the "Ziegler" type or, more recently, according to "metallocene" catalysis.

[0097] The functionalized polyolefin (B1) is advantageously selected from any polymer comprising α-olefin units and units with reactive polar functional groups, such as epoxy, carboxylic acid or carboxylic anhydride functional groups. Examples of such polymers may include terpolymers of ethylene, alkyl acrylate and maleic anhydride or glycidyl methacrylate, such as the Lotader® products of the Applicant Company, or polyolefins grafted with maleic anhydride, such as the Orevac® products of the Applicant Company, as well as terpolymers of ethylene, alkyl acrylate and (meth)acrylic acid. Mention may also be made of polypropylene homopolymers or copolymers grafted with carboxylic anhydrides and then condensed with polyamides or monoaminated oligomers of polyamides.

[0098] Advantageously, the constituent composition of the leakproof layer is devoid of polyether block amide (PEBA), thus in this embodiment PEBA is excluded from the impact modifiers.

[0099] Advantageously, said transparent composition is devoid of core-shell particles or core-shell polymers.

[0100] The term "core-shell particle" should be understood to mean a particle whose first layer forms the core and whose second or any subsequent layers form the respective shell.

[0101] The core-shell particles can be obtained by a multi-stage process comprising at least two stages, such a process being described, for example, in US 2009 / 0149600 or EP 0722961.

[0102] In one embodiment, ethylene / α-olefin interpolymers are excluded from the impact modifiers.

[0103] About plasticizers The plasticizer may be any plasticizer commonly used in polyamide-based compositions.

[0104] Advantageously, plasticizers are used that exhibit good thermal stability, so that no fumes are formed during the stages of mixing the various polymers and transformation of the resulting composition.

[0105] In particular, this plasticizer can be chosen from: benzenesulfonamide derivatives, such as n-butylbenzenesulfonamide (BBSA), the ortho and para isomers of ethyltoluenesulfonamide (ETSA), N-cyclohexyltoluenesulfonamide and N-(2-hydroxypropyl)benzenesulfonamide (HP-BSA); Esters of hydroxybenzoic acid such as 2-ethylhexyl parahydroxybenzoate (EHPB) and 2-hexyldecyl parahydroxybenzoate (HDPB); Esters or ethers of tetrahydrofurfuryl alcohol, such as oligoethyleneoxy-tetrahydrofurfuryl alcohol, and Esters of citric acid or hydroxymalonic acid, for example oligoethyleneoxymalonate.

[0106] A preferred plasticizer is n-butylbenzenesulfonamide (BBSA).

[0107] Another more particularly preferred plasticizer is N-(2-hydroxypropyl)benzenesulfonamide (HP-BSA), since the latter presents the advantage of preventing the formation of deposits in the extrusion screw and / or die during the stage of deformation by extrusion ("die roll").

[0108] Quite obviously, mixtures of plasticizers may be used.

[0109] Composite reinforcement layer and polymer P2j The polymer P2j may be a thermoplastic or a thermosetting polymer.

[0110] There may be one or more composite reinforcing layers.

[0111] Each of said layers consists of fibrous material in the form of continuous fibers impregnated with a composition mainly comprising at least one thermoplastic or thermosetting polymer P2j, j corresponding to the number of layers present.

[0112] j is 1 to 10, in particular 1 to 5, in particular 1 to 3, preferentially j=1.

[0113] The term "predominantly" means that said at least one polymer is present in an amount of more than 50% by weight relative to the total weight of the composition and matrix of the composite.

[0114] Advantageously, said at least one main polymer is present in an amount of more than 60% by weight, in particular more than 70% by weight, in particular more than 80% by weight and more particularly 90% or more by weight relative to the total weight of the composition.

[0115] The composition may also include impact modifiers and / or additives.

[0116] The additives, except for the nucleating agent, may be selected from antioxidants, heat stabilizers, UV absorbers, light stabilizers, lubricants, inorganic fillers, flame retardants, plasticizers and colorants.

[0117] Advantageously, said composition consists mainly of said thermoplastic polymer P2j and of 0% to 15% by weight of impact modifier, in particular of 0% to 12% by weight of impact modifier and of 0% to 5% by weight of additive, the sum of the components of the composition being equal to 100% by weight.

[0118] The at least one primary polymer of each layer may be the same or different.

[0119] In one embodiment, only one predominant polymer is present in the composite reinforcing layer that is not adhered to the at least one leakproof layer.

[0120] In one embodiment, each reinforcing layer comprises the same type of polymer, in particular an epoxy or epoxy-based resin, or a resin based on a polyisocyanate, in particular a polyisocyanurate.

[0121] Polymer P2j Thermoplastic polymer P2j The term "thermoplastic resin" or "thermoplastic polymer" is generally understood to mean a material that is solid at room temperature, can be semi-crystalline or amorphous, in particular semi-crystalline, softens during temperature increase, in particular after passing its glass transition temperature (Tg), flows at higher temperatures if amorphous, or can exhibit a clear melting point once passing its "melting point" (Tm), if semi-crystalline, and becomes solid again during temperature decrease below its crystallization point Tc (in the case of semi-crystalline materials) or below its glass transition temperature (in the case of amorphous materials).

[0122] Tg, Tc and Tm are determined by differential scanning calorimetry (DSC) according to standards 11357-2:2013 and 11357-3:2013, respectively.

[0123] The number average molecular weight Mn of said thermoplastic polymer is preferably in the range of 10 000 to 40 000, preferably 10 000 to 30 000. These Mn values ​​are determined in m-cresol according to standard ISO 307:2007, but by changing the solvent (using m-cresol instead of sulfuric acid, the temperature is 20° C.) it is possible to correspond to an intrinsic viscosity of 0.8 or more.

[0124] As examples of semi-crystalline thermoplastic polymers suitable for the present invention, mention may be made of: Copolymers, such as polyamides containing aromatic and / or alicyclic structures, including polyamide-polyether or polyester copolymers; Polyaryletherketone (PAEK), Polyetheretherketone (PEEK), Polyetherketoneketone (PEKK), Polyetherketoneetherketoneketone (PEKEKK), Polyimides, in particular polyetherimides (PEI) or polyamide-imides, Polysulfones (PSU), in particular polyarylsulfones, such as polyphenylsulfone (PPSU), Polyethersulfone (PES).

[0125] Semicrystalline polymers are more particularly preferred, especially polyamides and their semicrystalline copolymers.

[0126] The nomenclature used to define polyamides is described in standard ISO 1874-1:2011 "Plastics - Polyamide (PA) molding and extrusion materials - Part 1: Nomenclature", in particular page 3 (Tables 1 and 2) and is well known to the person skilled in the art.

[0127] The polyamide may be a homopolyamide or a copolyamide or a mixture thereof.

[0128] Advantageously, the semicrystalline polyamide is a semiaromatic polyamide, in particular of formula X / YAr as described in EP 1 505 099, in particular of formula A / XT, in which A is chosen from units resulting from amino acids, units resulting from lactams and units corresponding to formula (Ca diamine).(Cb diacid), a represents the number of carbon atoms of the diamine and b represents the number of carbon atoms of the diacid, a and b each being between 4 and 36, advantageously between 9 and 18, the (Ca diamine) units being chosen from linear or branched aliphatic diamines, cycloaliphatic diamines and alkylaromatic diamines, and the (Cb diacid) units being chosen from linear or branched aliphatic diacids, cycloaliphatic diacids and aromatic diacids. XT denotes units resulting from the polycondensation of Cx diamines with terephthalic acid, x representing the number of carbon atoms of the Cx diamine, x being from 5 to 36, advantageously from 9 to 18, in particular polyamides of the formula A / 5T, A / 6T, A / 9T, A / 10T or A / 11T, A being as defined above, in particular PA MPMDT / 6T, PA11 / 10T, PA 5T / 10T, PA 11 / BACT, PA 11 / 6T / 10T, PA MXDT / 10T, PA MPMDT / 10T, PA BACT / 10T, PA BACT / 6T, PA BACT / 10T / 6T, PA 11 / BACT / 6T, PA 11 / MPMDT / 6T, PA 11 / MPMDT / 10T, PA 11 / BACT / 10T, PA a polyamide selected from 11 / MXDT / 10T or 11 / 5T / 10T; T corresponds to terephthalic acid, MXD corresponds to m-xylylenediamine, MPMD corresponds to methylpentamethylenediamine and BAC corresponds to bis(aminomethyl)cyclohexane. The semi-aromatic polyamides defined above exhibit in particular a Tg of greater than or equal to 80° C.

[0129] Thermosetting polymer P2j Thermosetting polymers include epoxy or epoxy-based resins, polyesters, vinyl esters, polyisocyanates, especially polyisocyanurates, and polyurethanes, or mixtures thereof, in particular epoxy or epoxy-based resins or resins based on polyisocyanates, in particular polyisocyanurates.

[0130] Advantageously, each composite reinforcing layer consists of a composition comprising the same type of polymer, in particular an epoxy or epoxy-based resin or a resin based on a polyisocyanate, in particular a polyisocyanurate.

[0131] The composition comprising the polymer P2j may be transparent to radiation suitable for welding.

[0132] In another embodiment, the wrapping of the composite reinforcing layer around the leakproof layer is performed without any subsequent welding.

[0133] About Structures Thus, the multi-layer structure includes at least one leakproof layer and at least one composite reinforcing layer wrapped around the leakproof layer and which may or may not be bonded to each other.

[0134] Advantageously, the leakproof layer and the reinforcing layer are not adhesive to each other and each consist of a composition comprising a different polymer.

[0135] Nevertheless, the different polymers may be of the same type.

[0136] The multi-layer structure may include up to 10 leakproof layers of different nature and up to 10 composite reinforcing layers.

[0137] Said multi-layer structure is not necessarily symmetrical and may therefore contain more leakproof layers than composite layers or vice versa, but it is quite clear that layers and reinforcing layers cannot alternate.

[0138] Advantageously, said multi-layer structure comprises 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 leakproof layers and 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 composite reinforcing layers.

[0139] Advantageously, said multi-layer structure comprises 1, 2, 3, 4 or 5 leakproof layers and 1, 2, 3, 4 or 5 composite reinforcing layers.

[0140] Advantageously, said multi-layer structure comprises one, two or three leakproof layers and one, two or three composite reinforcing layers.

[0141] Advantageously, they are each of a composition comprising a different polymer.

[0142] Advantageously, they consist of compositions comprising a polyamide corresponding to the polyamide P1i and an epoxy or epoxy-based resin or a resin based on a polyisocyanate, in particular a polyisocyanurate P2j, respectively.

[0143] In one embodiment, the multilayer structure comprises only one leakproof layer and several reinforcing layers, with adjacent reinforcing layers wrapped around the leakproof layers and other reinforcing layers wrapped around directly adjacent reinforcing layers.

[0144] In another embodiment, the multi-layer structure comprises only one reinforcing layer and several leakproof layers, the reinforcing layer being wrapped around the adjacent leakproof layers.

[0145] In one advantageous embodiment, the multi-layer structure comprises only one leakproof layer and only one composite reinforcing layer, the reinforcing layer being wrapped around the leakproof layer.

[0146] Therefore, all combinations of these two layers are within the scope of the present invention, provided that at least the innermost composite reinforcement layer is wrapped around the outermost adjacent leakproof layer, and the other layers are either bonded or unbonded to each other.

[0147] Advantageously, in said multilayer structure, each leakproof layer consists of the same type of polymer P1i, in particular a composition comprising a polyamide.

[0148] The expression "polymer of the same type" should be understood to mean, for example, polyamides which may be the same or different polyamides depending on the layers.

[0149] Advantageously, said polymer P1i is a polyamide and said polymer P2j is an epoxy or epoxy-based resin or a resin based on polyisocyanates, in particular polyisocyanurates.

[0150] Advantageously, the polyamide P1i is the same for all the leakproof layers.

[0151] Advantageously, said polymer P1i is an aliphatic polyamide chosen from PA410, PA412, PA510, PA512, PA610 and PA612.

[0152] In one embodiment, said polymer P1i is an aliphatic polyamide selected from PA410, PA412, PA510, PA512 and PA612.

[0153] Advantageously, in said multilayer structure, each reinforcing layer consists of a composition comprising the same type of polymer P2j, in particular an epoxy or epoxy-based resin or a resin based on a polyisocyanate, in particular a polyisocyanurate.

[0154] Advantageously, the polyamide P2j is the same for all reinforcing layers.

[0155] Advantageously, in said multilayer structure, each leakproof layer consists of a composition comprising the same type of polymer P1i, in particular a polyamide, and each reinforcing layer consists of a composition comprising the same type of polymer P2j, in particular an epoxy or epoxy-based resin or a resin based on a polyisocyanate, in particular a polyisocyanurate.

[0156] Advantageously, said polymer P1i is an aliphatic polyamide selected from PA410, PA412, PA510, PA512, PA610 and PA612, and said polymer P2j is a semi-aromatic polyamide selected in particular from PA MPMDT / 6T, PA11 / 10T, PA 11 / BACT, PA 5T / 10T, PA 11 / 6T / 10T, PA MXDT / 10T, PA MPMDT / 10T, PA BACT / 10T, PA BACT / 6T, PA BACT / 10T / 6T, PA 11 / BACT / 6T, PA 11 / MPMDT / 6T, PA 11 / MPMDT / 10T, PA 11 / BACT / 10T and PA 11 / MXDT / 10T.

[0157] In one embodiment, said polymer P1i is an aliphatic polyamide selected from PA410, PA412, PA510, PA512 and PA612, and said polymer P2j is a semi-aromatic polyamide selected in particular from PA MPMDT / 6T, PA11 / 10T, PA 11 / BACT, PA 5T / 10T, PA 11 / 6T / 10T, PA MXDT / 10T, PA MPMDT / 10T, PA BACT / 10T, PA BACT / 6T, PA BACT / 10T / 6T, PA 11 / BACT / 6T, PA 11 / MPMDT / 6T, PA 11 / MPMDT / 10T, PA 11 / BACT / 10T and PA 11 / MXDT / 10T.

[0158] In one embodiment, the multilayer structure consists of only one reinforcing layer and only one leakproof layer in which the polymer P1i is an aliphatic polyamide selected from PA410, PA412, PA510, PA512, PA610 and PA612 and the polymer P2j is a semi-aromatic polyamide selected in particular from PA MPMDT / 6T, PA11 / 10T, PA 11 / BACT, PA 5T / 10T, PA 11 / 6T / 10T, PA MXDT / 10T, PA MPMDT / 10T, PA BACT / 10T, PA BACT / 6T, PA BACT / 10T / 6T, PA 11 / BACT / 6T, PA 11 / MPMDT / 6T, PA 11 / MPMDT / 10T, PA 11 / BACT / 10T and PA 11 / MXDT / 10T.

[0159] In one embodiment, the multilayer structure consists of only one reinforcing layer and only one leakproof layer in which the polymer P1i is an aliphatic polyamide selected from PA410, PA412, PA510, PA512 and PA612 and the polymer P2j is a semi-aromatic polyamide selected in particular from PA MPMDT / 6T, PA11 / 10T, PA 11 / BACT, PA 5T / 10T, PA 11 / 6T / 10T, PA MXDT / 10T, PA MPMDT / 10T, PA BACT / 10T, PA BACT / 6T, PA BACT / 10T / 6T, PA 11 / BACT / 6T, PA 11 / MPMDT / 6T, PA 11 / MPMDT / 10T, PA 11 / BACT / 10T and PA 11 / MXDT / 10T.

[0160] In yet another embodiment, the multilayer structure consists of only one reinforcing layer and only one leakproof layer, in which said polymer P1i is an aliphatic polyamide selected from PA410, PA412, PA510, PA512, PA610 and PA612, and said polymer P2j is an epoxy or epoxy-based resin or a resin based on polyisocyanates, in particular polyisocyanurates.

[0161] In another embodiment, the multilayer structure consists of only one reinforcing layer and only one leakproof layer, in which said polymer P1i is an aliphatic polyamide selected from PA410, PA412, PA510, PA512 and PA612, and said polymer P2j is an epoxy or epoxy-based resin or a resin based on polyisocyanates, in particular polyisocyanurates.

[0162] Advantageously, said multilayer structure further comprises at least one outer layer of fibrous material consisting of continuous glass fibres impregnated with a transparent amorphous polymer, said layer being the outermost layer of said multilayer structure.

[0163] The outer layer is a second reinforcing but transparent layer that allows for imprinting on the structure.

[0164] In one embodiment, the leak-proof layer is formed as follows from the inside to the outside: A layer (a) consisting of the composition defined above, Optionally, a bonding layer; a barrier layer against hydrogen, in particular made of a fluoropolymer, in particular made of PVDF, or made of EVOH, preferably made of EVOH; Optionally, a bonding layer; and a layer (b) consisting of the composition defined above.

[0165] Barrier layer The expression "barrier layer" indicates a layer having properties of low permeability and good hydrogen resistance, i.e. the barrier layer slows down the passage of hydrogen to other layers of the structure or even to the outside of the structure. A barrier layer is therefore a layer that makes it possible, first of all, not to lose too much hydrogen to the atmosphere by diffusion, thereby avoiding explosion and fire problems.

[0166] These barrier materials can be polyamides with a low carbon content, i.e. polyamides with an average number of carbon atoms (C) relative to the nitrogen atoms (N) less than 9, which are preferably semi-crystalline and have a high melting point, polyphthalamides, and / or also non-polyamide barrier materials, such as highly crystalline polymers, such as copolymers of ethylene and vinyl alcohol (hereinafter indicated as EVOH), in fact functionalized fluorinated materials, such as functionalized polyvinylidene fluoride (PVDF), functionalized copolymers of ethylene and tetrafluoroethylene (ETFE), functionalized copolymers of ethylene, tetrafluoroethylene and hexafluoropropylene (EFEP), functionalized polyphenylene sulfide (PPS) or functionalized polybutylene naphthalate (PBN). If these polymers are not functionalized, it is possible to add an intermediate layer of a binder to ensure good adhesion within the MLT structure.

[0167] Among these barrier materials, EVOH, especially those most abundant in vinyl alcohol comonomer, and those impact modified, are particularly advantageous as they make it possible to produce stronger structures.

[0168] The expression "barrier layer" means, in other words, that the barrier layer is substantially impermeable to hydrogen, in particular that the hydrogen permeability at 23°C and 0% relative humidity (RH) is less than 100 cc.mm / m 2 Less than 24h.atm, especially 75cc.mm / m 2 is less than .24h.atm.

[0169] The transmittance is (cc.mm / m 2 It can also be expressed in units of .24h.Pa.

[0170] In that case the transmittance must be multiplied by 101325.

[0171] About fiber materials As regards the constituent fibres of said fibre materials, these are in particular fibres of inorganic, organic or vegetable origin.

[0172] Advantageously, said fibrous material may or may not be sized.

[0173] The fibrous material may thus contain up to 3.5% by weight of organic material (thermosetting or thermoplastic type) called size.

[0174] Among the fibers of inorganic origin, mention may be made, for example, of carbon fibers, glass fibers, basalt or base-based fibers, silica fibers or silicon carbide fibers. Among the fibers of organic origin, mention may be made, for example, of fibers based on thermoplastic or thermosetting polymers, such as semi-aromatic polyamide fibers, aramid fibers, polyester fibers or polyolefin fibers. Preferably, they are based on amorphous thermoplastic polymers and exhibit a glass transition temperature Tg that is higher than the Tg of the constituent thermoplastic polymers or polymer blends of the pre-impregnated matrix, if the polymer or blend is amorphous, or higher than the Tm of the constituent thermoplastic polymers or polymer blends of the pre-impregnated matrix, if the polymer or blend is semi-crystalline. Advantageously, they are based on semi-crystalline thermoplastic polymers and exhibit a melting point Tm that is higher than the Tg of the constituent thermoplastic polymers or polymer blends of the pre-impregnated matrix, if the polymer or blend is amorphous, or higher than the Tm of the constituent thermoplastic polymers or polymer blends of the pre-impregnated matrix, if the polymer or blend is semi-crystalline. Thus, there is no risk of the constituent organic fibers of the fiber material melting during impregnation with the thermoplastic matrix of the final composite. Among the fibres of vegetable origin, mention may be made of natural fibres based on flax, hemp, lignin, bamboo, silk, especially spider silk, sisal and other cellulose fibres, especially viscose fibres, which may be used pure, treated or coated with a coating layer to promote adhesion and impregnation of the thermoplastic polymer matrix.

[0175] The textile material may also be a fabric knitted or woven with the fibers.

[0176] It can also accommodate fibers having supporting threads.

[0177] These constituent fibers can be used alone or as a mixture. Thus, organic fibers can be mixed with inorganic fibers to form a pre-impregnated fibrous material pre-impregnated with a thermoplastic polymer powder.

[0178] The organic fiber rovings can have several basis weights. In addition, they can take on several shapes. The constituent fibers of the fiber material can also be in the form of a mixture of these reinforcing fibers of various shapes. The fibers are continuous fibers.

[0179] Preferably, the fibre material is selected from glass fibres, carbon fibres, basalt or basalt-based fibres or mixtures thereof, in particular carbon fibres.

[0180] It is used in the form of a roving or several rovings.

[0181] According to another aspect, the invention relates to a process for the manufacture of a multilayer structure as defined above, characterized in that it comprises a step of preparation of the leakproof layer by extrusion blow moulding, rotational moulding, injection moulding or extrusion.

[0182] In one embodiment, said method for manufacturing a multi-layer structure comprises a step of filament winding of a reinforcing layer as defined above around a leakproof layer as defined above.

[0183] All the characteristics detailed above also apply to the process. [Brief description of the drawings]

[0184] [Figure 1] Figure 1 presents the notched Charpy impact (kJ / m2) of five liners at 23°C and -40°C according to ISO 179-1:2010: from left to right, PA12, PA612, PA610, PA6 and PA66 (for each liner: left histogram: 23°C, right histogram: -40°C). [Diagram 2] FIG. 1 presents, from left to right, hydrogen permeability (cc.mm / m2.d.atm) at 23° C. for PA12, PA6, PA610 and PA612 liners. [Diagram 3]Figure 2 presents the hydrogen permeability (cc.mm / m2.d.atm) at 23°C of liners of PA610 with different percentages of impact modifier (Lotader® 4700 (50%) + Lotader® AX8900 (25%) + Lucalene® 3110 (25%) mixture): from left to right: PA610 without impact modifier, PA610 with 8% impact modifier, PA610 with 12% impact modifier and PA610 with 15% impact modifier. [Figure 4] FIG. 1 shows the water absorption rate at 23° C. and 100% relative humidity. EXAMPLES

[0185] In all embodiments, the tank is obtained by rotational moulding of a leakproof layer (liner) at a temperature adapted to the properties of the thermoplastic resin used.

[0186] For composite reinforcements made with epoxy or epoxy-based resins or resins based on polyisocyanates, especially polyisocyanurates, a wet filament winding process is then used, which consists of winding fibers previously pre-impregnated with a liquid epoxy bath or a liquid epoxy-based bath around the liner, which is then polymerized in a tank oven for 2 hours.

[0187] In all other cases, a textile material pre-impregnated with a thermoplastic resin (tape) is subsequently used. This tape is deposited by filament winding by a robot including laser heating with a power of 1500 W at a speed of 12 m / min, and there is no polymerization stage.

[0188] Example 1: Charpy notched impact at -40°C according to ISO 179-1:2010 A liner with more than 9 carbons per nitrogen atom (PA12), two liners with less than 7 carbons per nitrogen atom (PA6 and PA66), and two liners with 7–9 carbons per nitrogen atom (PA610 and PA612) were prepared by rotational molding as described above.

[0189] These five liners were tested with Charpy notched impact at -40°C and the results are shown in Figure 1.

[0190] The impact resistance of PA610 and PA612 liners compares favorably with that of PA6 and PA66.

[0191] Example 2: Permeability of PA12, PA612, PA610 and PA6 liners without impact modifiers A liner with more than 9 carbons per nitrogen atom (PA12), a liner with less than 7 carbons per nitrogen atom (PA6), and two liners with 7 to 9 carbons per nitrogen atom (PA610 and PA612) were prepared by rotational molding and tested for hydrogen permeability at 23 °C.

[0192] This consists of sweeping the top surface of the film with the test gas (hydrogen) and measuring by gas chromatography the flux diffusing through the lower film swept with a carrier gas: nitrogen.

[0193] The experimental conditions are shown in Table 1: [Table 1]

[0194] The results are shown in FIG. 2 and show that liners made from both PA610 and PA612 exhibit much lower hydrogen permeation rates than the liner made from PA12.

[0195] FIG. 3 shows the effect of the impact modifier on the hydrogen permeability of the PA610 liner.

[0196] Example 3: Water absorption rate Specimens of PA6, PA66, PA610, PA612 and PA12 are immersed in demineralized water at 23 ° C. Every day (except weekends), the samples are removed from the water, wiped, weighed and reintroduced into the water. Once the mass has stabilized (reached a plateau), the value is transferred to a graph. This value corresponds to the maximum mass of water that these products can absorb at 23 ° C.

[0197] FIG. 4 shows that the water absorption rates of PA612 and PA610 are much lower than those of PA6 and PA66.

[0198] The liners made of PA6, PA610, PA612 and PA12 were covered with a composite casing; the latter was produced by winding T700SC31E carbon fiber (from Toray) impregnated with epoxy resin. The assembly was heated at 110 °C for 5 hours to ensure the hardening of the epoxy resin. The tank was then cut and analyzed. The PA6 liner exhibits air bubbles on the outer surface (the surface in contact with the composite structure). The liners made of PA610, PA612 and PA12 do not exhibit any defects.

[0199] Example 4 The Type IV hydrogen storage tank consisted of a reinforcement made of epoxy (Tg120°C) / T700SC31E carbon fiber (from Toray) composite and a leak-proof layer made of PA612.

[0200] Pressure cycle tests are carried out on the tank at -40°C. Pressure is applied via glycol or silicone oil and cycles of 20 to 875 bar are applied in accordance with Regulation (EC) No. 79 / 2009 until 100 cycles or tank failure (a deviation from Regulation EC79 which requires 45000 cycles).

[0201] Following these cycles, the tank is emptied and the immersed tank is subjected to a hydrogen pressure test. No leaks are observed. An internal inspection of the tank reveals no discernible cracks.

[0202] Example 5 (counterexample): The type IV hydrogen storage tank consisted of a reinforcement made of epoxy (Tg120°C) / T700SC31E carbon fiber (from Toray) composite and a leak-proof layer made of PA12. Same test done with same result: no cracks

[0203] Example 6: A type IV hydrogen storage tank was constructed with a reinforcement made of epoxy (Tg 120° C.) / T700SC31E carbon fiber (from Toray) composite and a leakproof layer made of PA6.

[0204] The same pressure cycle test is performed for only two cycles. After two cycles, the tank is emptied and a hydrogen pressure test is performed on the submerged tank. A stream of gas bubbles is observed, an indication of tank failure. Observation of the inside of the tank confirms this failure.

[0205] These tests show that liners made with PA6 are much less resistant than liners made with PA612 or PA12.

[0206] The four figures 1 to 4 show that PA610 and PA612 offer the best compromise in terms of impact strength, permeability and water absorption compared to PA12, PA6 and PA66.

[0207] Thus, liners made of PA610 or PA612 make it possible to offer a good compromise between mechanical strength and barrier properties against hydrogen while reducing the water absorption.

Claims

1. A multilayer structure intended for the transport, distribution, and storage of hydrogen, comprising, from the inside outwards, at least one leak-proof layer (1) and at least one composite reinforcement layer (2), wherein the innermost composite reinforcement layer is wound around the outermost adjacent leak-proof layer, wherein the leak-proof layer comprises mainly a composition consisting of at least one aliphatic polyamide thermoplastic polymer P1i (i = 1 to n, n being the number of semi-crystalline leak-proof layers, the Tm of which, measured according to ISO 11357-3:2013, is greater than 200 °C, excluding polyether block amide (PEBA)), said polyamide thermoplastic polymer being a polyamide having an average number of carbon atoms per nitrogen atom of 7 to 9), a maximum of 30% by weight, in particular a maximum of less than 15% by weight, in particular a maximum of 9% by weight, of an impact modifier, based on the total weight of the composition, a maximum of 1.5% by weight of a plasticizer, based on the total weight of the composition, said composition being devoid of a nucleating agent, said at least one polyamide thermoplastic polymer of each leak-proof layer being able to be the same or different, wherein at least one of said composite reinforcement layers consists of a fibrous material in the form of continuous fibers impregnated with a composition mainly comprising at least one polymer P2j (j = 1 to m, m being the number of reinforcement layers), in particular an epoxy or epoxy-based resin or a polyisocyanate, in particular a resin based on polyisocyanurate, said structure being a multilayer structure lacking a layer made of the outermost polyamide polymer adjacent to the outermost layer of the composite reinforcement.

2. The multilayer structure according to claim 1, characterized in that copolymers of ethylene and α-olefins are excluded from the impact modifier.

3. The multilayer structure according to claim 1, characterized in that each reinforcement layer comprises the same type of polymer, in particular an epoxy or epoxy-based resin or a polyisocyanate, in particular a resin based on polyisocyanurate.

4. The multilayer structure according to claim 1, characterized by presenting only one leak-proof layer and only one reinforcement layer.

5. The multilayer structure according to claim 1, characterized in that said polymer P1i is an aliphatic polyamide selected from PA410, PA412, PA510, PA512, PA610, and PA612, in particular from PA410, PA412, PA510, PA512, and PA612.

6. The multilayer structure according to claim 1, characterized in that the polymer P2j is a resin based on epoxy or epoxy resin or polyisocyanate, particularly polyisocyanurate.

7. The multilayer structure consists of only one reinforcing layer and only one leak-proof layer. In this layer, the polymer P1i is an aliphatic polyamide selected from PA410, PA412, PA510, PA512, PA610 and PA612, particularly from PA410, PA412, PA510, PA512 and PA612. The multilayer structure according to claim 5 or 6, characterized in that the polymer P2j is a resin based on epoxy or epoxy resin or polyisocyanate, particularly polyisocyanurate.

8. The multilayer structure according to claim 1, characterized in that the fiber material of the composite reinforcing layer is selected from glass fiber, carbon fiber, basalt or basalt-based fiber, or a mixture thereof, particularly carbon fiber.

9. The structure according to claim 1, further comprising at least one outer layer made of a fiber material produced from continuous glass fibers impregnated with a transparent amorphous polymer, the layer being the outermost layer of the multilayer structure.

10. The leak-proof layer, from the inside to the outside, layer (a) consisting of the composition defined in claim 1, optionally, a bonding layer, particularly a hydrogen barrier layer made of a fluoropolymer, particularly made of PVDF, or made of EVOH, preferably made of EVOH, optionally, a bonding layer, layer (b) consisting of the composition defined in claim 1. The multilayer structure according to claim 1.

11. A method for manufacturing the multilayer structure defined in claim 1, characterized in that it includes a step of preparing the leak-proof layer by extrusion blow molding, rotational molding, injection molding or extrusion.

12. A method for manufacturing the multilayer structure defined in claim 11, characterized in that it includes a step of filament winding the reinforcing layer according to claim 1 around the leak-proof layer defined in claim 1.

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