Multilayer structure for transporting or storing hydrogen

Abstract

The present invention provides a multilayer structure intended for transporting, distributing, or storing hydrogen. [Solution] A multilayer structure comprising at least one sealing layer (1) and at least one composite reinforcing layer (2) from the inside out, wherein the innermost composite reinforcing layer is wound around the outermost layer adjacent to the sealing layer, the sealing layer mainly comprises at least one semicrystalline long-chain polyamide thermoplastic polymer P1i (i=1 to n, where n is the number of sealing layers), its Tm is greater than 160°C, and except for one polyether block amide (PEBA), it contains up to 50% by weight of an impact resistance modifier and up to 1.5% by weight of a plasticizer based on the total weight of the composition, and does not contain a nucleating agent, and at least one of the composite reinforcing layers is made 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, where m is the number of reinforcing layers), epoxy resin or epoxy-based resin.

Description

Technical Field

[0001] This patent application relates to multilayer composite structures for transporting, distributing or storing hydrogen, particularly for distributing or storing hydrogen, and to methods for producing such structures.

Background Art

[0002] Hydrogen tanks are currently attracting a great deal of attention from a number of manufacturers, particularly in the automotive sector. One of the required goals is to propose further low-emission vehicles. Therefore, it is aimed that electric or hybrid vehicles including batteries will gradually replace internal combustion engine vehicles, such as gasoline or diesel vehicles. Batteries have been found to be relatively complex vehicle components. Depending on the positioning of the battery in the vehicle, the battery may need to protect it from impacts and from the external environment which can be at very high temperatures and variable humidity. It may also be necessary to avoid any risk of fire.

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

[0004] Furthermore, electric vehicles still suffer from several problems today, namely battery range, the use of rare earth metals in these batteries, non-renewable resources, charging times much longer than the time taken to fill a tank, and the problem of electricity generation to enable battery charging in various countries.

[0005] Therefore, hydrogen is an alternative to electric batteries since hydrogen can be converted into electricity by a fuel cell and thus supply power to an electric vehicle.

[0006] Hydrogen tanks typically consist of a metal liner (or sealing layer) that must protect hydrogen from permeation. One type of tank that is conceivable is called Type IV, which is based on a thermoplastic liner with a composite wrapped around it.

[0007] The fundamental principle is to separate the two essential functions of sealing and mechanical strength and manage them independently of each other. In this type of tank, the liner (or sealing sheath), made of thermoplastic resin, is combined with a reinforcing structure made of fibers (glass, aramid, carbon), also known as a reinforcing sheath or layer, which allows it to operate at much higher pressures while reducing weight and avoiding the risk of explosion in the event of a severe external attack.

[0008] Liner has a certain principle characteristic: Potential conversion methods include extrusion blow molding, rotational molding, injection molding, or extrusion. Low hydrogen permeability, or in fact, the permeability of the liner, is a crucial factor in limiting hydrogen leakage from the tank. Good mechanical properties (fatigue) at low temperatures (-40 to -70°C) Heat resistance at 120°C It must have.

[0009] In practice, it is necessary to increase the filling rate of the hydrogen tank, which should be roughly equivalent to that of a fuel tank for an internal combustion engine (about 3 to 5 minutes). However, this increase in rate causes the tank to overheat more significantly, then reach a temperature of about 100°C.

[0010] The performance and safety of hydrogen tanks can be evaluated at the Reference European Laboratory (GasTeF: Hydrogen Tank Test Facility), as described by Galassi et al. (World hydrogen energy conference 2012, Onboard compressed hydrogen storage: fast filing experiments and simulations, Energy Procedia 29 (2012), pp. 192-200).

[0011] The first generation of Type IV tanks used high-density polyethylene (HDPE) based liners.

[0012] However, HDPE has the disadvantage of having too low a melting point and too high a hydrogen permeability, which presents a problem in terms of heat resistance, preventing an increase in tank filling speed.

[0013] Polyamide PA6-based liners have been under development for many years.

[0014] Nevertheless, PA6 has the disadvantage of having low resistance to cold.

[0015] Application EP3112421 relates to a polyamide resin composition for molded articles intended for use with high-pressure hydrogen, This document describes a composition comprising a polyamide 6 resin (A), and a polyamide resin (B) having a melting point that is not higher than the melting point of polyamide 6 resin (A) + 20°C, as determined, for example by DSC, and a cooling crystallization temperature that is higher than the cooling crystallization temperature of polyamide 6 resin (A), as determined, for example by DSC.

[0016] French patent application FR2923575 describes a tank for storing fluid under high pressure, comprising metal end pieces at each of its ends along its axis, wherein a liner surrounds the end pieces, and a structural layer made of thermosetting resin-impregnated fibers surrounds the liner.

[0017] Application EP3222668 describes a polyamide resin composition for molded articles intended for use with high-pressure hydrogen, comprising a polyamide resin (A) containing units derived from hexamethylenediamine and units derived from an aliphatic dicarboxylic acid having 8 to 12 carbon atoms, and an ethylene / α-olefin copolymer (B) modified with one of the unsaturated carboxylic acids and / or derivatives thereof.

[0018] Application US2014 / 008373 relates to a lightweight storage cylinder for high-pressure compressed gas, having a liner surrounded by a restraining layer, The line, First inner layer of impact-resistant modified polyamide (PA) that comes into contact with gas, A thermoplastic outer layer in contact with the restraining layer, and This document describes a cylinder that includes an adhesive bonding layer between a first impact-resistant improved PA inner layer and an outer thermoplastic layer.

[0019] WO18155491 describes a hydrogen transport component having a three-layer structure, the inner layer comprising PA11, 15 to 50% impact modifier, and 1 to 3% plasticizer, or a composition lacking plasticizer, the composition having hydrogen barrier properties, good flexibility at low temperatures, and durability. However, this structure is suitable for pipes for transporting hydrogen, but not for storing hydrogen.

[0020] Therefore, on the one hand, it is necessary to optimize the matrix of the composite so as to optimize the mechanical strength of the composite matrix at high temperatures, and on the other hand, it is still necessary to optimize the materials including the sealing sheath so as to optimize the operating temperature of the sealing sheath. Thus, any change in the choice of materials of the composition including the sealing liner that is carried out should not cause a significant increase in the manufacturing temperature of this liner (extrusion blow molding, injection molding, rotational molding, etc.) compared to those practiced today. [Overview of the project]

[0021] These problems are solved by providing the multilayer structure of the present invention intended to transport, distribute or store hydrogen.

[0022] Throughout this specification, the terms "liner" and "sealing sheath" have the same meaning.

[0023] The present invention is thus a multilayer structure intended for the transport, distribution or storage of hydrogen, comprising, from the inside to the outside, at least one sealing layer (1) and at least one composite reinforcing layer (2), the innermost said composite reinforcing layer being wound around the outermost adjacent said sealing layer (1), said sealing layer(s) consisting mainly of a composition which comprises at least one semi-crystalline thermoplastic polymer P1i, where i = 1 to n and n is the number of sealing layers, and its Tm, measured according to ISO 11357-3:2013, is above 160 °C, in particular above 170 °C, and comprises long-chain polyamide thermoplastic polymers P1i, excluding polyether block amides (PEBA), up to 50% by weight, in particular less than 15% by weight, in particular up to 12% by weight, of an impact modifier, relative to the total weight of the composition, comprises up to 1.5% by weight of a plasticizer, relative to the total weight of the composition, said composition being devoid of a nucleating agent, said at least one polyamide thermoplastic polymer of each sealing layer may 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, where j = 1 to m and m is the number of reinforcing layers, in particular a composition comprising an epoxy resin or an epoxy-based resin, said structure relates to a multilayer structure lacking an outermost layer and adjacent to the outermost layer of polyamide polymer composite reinforcement.

[0024] The inventors have therefore unexpectedly found that by using a long-chain semi-crystalline polyamide thermoplastic polymer containing limited proportions of impact modifiers and plasticizers in the sealing layer, and a different polymer, particularly epoxy resin or epoxy-based resin, in the matrix of the composite, the composite, when wrapped around the sealing layer, can achieve a structure suitable for transporting, distributing, or storing hydrogen, particularly an increase in the maximum temperature of use that can reach up to 120°C, and thus an increase in the tank filling rate. [Brief explanation of the drawing]

[0025] [Figure 1] This diagram shows the notched Charpy impact test at -40°C according to ISO 179-1:2010 for four types of liners: PA11, PA12, PA6, and PA66 from left to right. [Figure 2] This figure shows the hydrogen permeability of liner PA12 and HDPE at 23°C. This is expressed in cc.mm / m² / 24h.atm. It may also be expressed in cc.25μ / m² / 24h.Pa. The permeability must then be multiplied by 101325. [Figure 3] This figure shows the notched Charpy impact at -40°C according to ISO 179-1:2010 for liners PA11 and PA12. In the histogram, PA11 is on the left and PA12 is on the right. The first group corresponds to 0% plasticizer, the second group to 7% plasticizer, and the last group to 12% plasticizer. [Modes for carrying out the invention]

[0026] A "multilayered" tank should be understood to include, or consist of, several layers, namely several sealing layers and several reinforcing layers, or one sealing layer and several reinforcing layers, or several sealing layers and one reinforcing layer, or one sealing layer and one reinforcing layer.

[0027] A multilayer structure is therefore understood to exclude pipes or tubes.

[0028] Polyether block amides (PEBA) are copolymers having amide units (Ba1) and polyether units (Ba2), wherein the amide unit (Ba1) is a unit obtained from at least one amino acid, or a unit obtained from at least one lactam, or: - A polycondensation of at least one diamine, wherein the diamine is preferably selected from linear or branched aliphatic diamines, or mixtures thereof. - A polycondensation of at least one carboxylic acid diacid, wherein the diacid is preferably selected from linear or branched aliphatic diacids, or mixtures thereof, and corresponds to an aliphatic repeating unit selected from the units XY obtained from the polycondensation. The diamine and the diacid each contain 4 to 36 carbon atoms, preferably 6 to 18 carbon atoms. The polyether unit (Ba2) is derived in particular from at least one polyalkylene ether polyol, in particular from a polyalkylene ether diol.

[0029] Nucleating agents are known to those skilled in the art, and the term refers to substances that, when incorporated into a polymer, form nuclei for the growth of crystals in a molten polymer.

[0030] These can be selected from, for example, microtalc, carbon black, silica, titanium dioxide, and nanoclay.

[0031] In one embodiment, PA6 and PA610 are excluded from the composition.

[0032] The phrase "the structure lacking an outermost layer and adjacent to an outermost layer of polyamide polymer composite reinforcement" means that the structure lacks a layer of polyamide polymer that is placed on the outermost composite reinforcement layer.

[0033] In one embodiment, the multilayer structure consists of two layers, a sealing layer, and a reinforcing layer.

[0034] The sealing layer(s) are the innermost layer relative to the outermost layer, which is the composite reinforcing layer.

[0035] The tank may be for mobile storage of hydrogen, i.e., on a truck for transporting hydrogen, on a vehicle for transporting hydrogen and supplying hydrogen-based fuel cells, for example, 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 at a base for distributing hydrogen to vehicles.

[0036] Advantageously, the sealing layer (1) does not leak hydrogen at 23°C, meaning that the hydrogen permeability at 23°C is 500 cc.mm / m at 23°C under 0% relative humidity (RH). 2 It is less than .24h.atm.

[0037] In one embodiment, the sealing layer(s) mainly comprises at least one semicrystalline thermoplastic polymer P1i, i=1 to n, where n is the number of sealing layers, and its Tm is greater than 160°C, more specifically greater than 170°C, as measured according to ISO 11357-3:2013, and consists of a composition that excludes polyether block amide (PEBA) and PA11.

[0038] The composite reinforcement layer(s) are wrapped around the sealing layer by polymer-impregnated fiber ribbons (or tapes or rovings), which are deposited, for example, by filament winding.

[0039] If several layers are present, the polymers will be different.

[0040] If the polymer of the reinforcing layer is identical, several layers may be present, but advantageously, a single reinforcing layer is present, and this reinforcing layer has at least one full wrap around the sealing layer.

[0041] This fully automated process, well known to those skilled in the art, makes it possible to select a winding angle for each layer that will give the final structure the ability to withstand internal pressure loads.

[0042] If several sealing layers are present, only the innermost layer of the sealing layer will be in direct contact with hydrogen.

[0043] When there is only one sealing layer and one composite reinforcement layer, a multilayer structure of two layers is thus formed, and these two layers can be in direct contact with each other and adhere to each other, especially since the composite reinforcement layer is wrapped around the sealing layer.

[0044] If several sealing layers and / or several composite reinforcement layers are present, the outermost layer of the sealing layer, and thus the layer opposite to the layer in contact with hydrogen, may or may not be bonded to the innermost layer of the composite reinforcement.

[0045] Other composite reinforcement layers may or may not be bonded to each other.

[0046] Other sealing layers may or may not be bonded to each other.

[0047] Advantageously, there is only one sealing layer and one reinforcing layer, and they do not adhere to each other.

[0048] Advantageously, there is a single sealing layer and a single reinforcing layer that are not bonded to each other, and the reinforcing layer consists mainly of a fibrous material in the form of continuous fibers impregnated with a composition mainly comprising at least one polymer P2j, more specifically an epoxy resin or epoxy-based resin.

[0049] In one embodiment, there is only one sealing 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 fibers impregnated with a composition mainly containing polymer P2j, which is an epoxy resin or epoxy-based resin.

[0050] The term "epoxy-based" throughout this specification means that epoxy is equivalent to at least 50% by weight of the matrix.

[0051] Regarding sealing layers (multiple layers are possible) and thermoplastic polymer P1i One or more sealing layers may be present.

[0052] Each of the aforementioned layers mainly comprises at least one thermoplastic polymer P1i, where i is a composition corresponding to the number of layers present. i is 1 to 10, more specifically 1 to 5, particularly 1 to 3, and preferably i=1.

[0053] The term "primarily" means that at least one of the polymers is present in an amount exceeding 50% by weight of the total weight of the composition.

[0054] Advantageously, the at least one dominant polymer is present in an amount of more than 60% by weight, more specifically more than 70% by weight, more specifically more than 80% by weight, and more specifically 90% by weight or more, based on the total weight of the composition.

[0055] The composition may also include up to 50% by weight of impact modifiers and / or plasticizers and / or additives relative to the total weight of the composition.

[0056] The additives, excluding the nucleating agent, may be selected from other polymers, antioxidants, heat stabilizers, UV absorbers, light stabilizers, lubricants, inorganic fillers, flame retardants, dyes, carbon black, and carbonaceous nanofillers. In particular, the additives, excluding the nucleating agent, may be selected from antioxidants, heat stabilizers, UV absorbers, light stabilizers, lubricants, inorganic fillers, flame retardants, dyes, carbon black, and carbonaceous nanofillers.

[0057] The other polymer may be another semicrystalline thermoplastic polymer or a different polymer, in particular EVOH (ethylene vinyl alcohol).

[0058] Advantageously, the composition mainly comprises the thermoplastic polymer P1i, 0 to 50% by weight of an impact modifier, particularly 0 to less than 15% of an impact modifier, more specifically 0 to 12% of an impact modifier, 0 to 1.5% of a plasticizer, and 0 to 5% by weight of an additive, the totality of the components of the composition being equal to 100%.

[0059] Advantageously, the composition mainly consists of the thermoplastic polymer P1i, 0 to 50% by weight of an impact modifier, particularly 0 to less than 15% of an impact modifier, more specifically 0 to 12% of an impact modifier, 0 to 1.5% of a plasticizer, and 0 to 5% by weight of an additive, and the total amount of the constituent components of the composition is equal to 100%.

[0060] The at least one dominant polymer in each layer may be the same or different.

[0061] In one embodiment, a single dominant polymer is present in at least a sealing layer that does not adhere to the composite reinforcement layer.

[0062] In one embodiment, the composition comprises 0.1 to 50% by weight of an impact modifier, particularly 0.1 to less than 15% by weight, and more specifically 0.1 to 12% by weight of an impact modifier, based on the total weight of the composition.

[0063] In one embodiment, the composition lacks a plasticizer.

[0064] In another embodiment, the composition comprises 0.1 to 50% by weight of an impact modifier, particularly 0.1 to less than 15% by weight, and more specifically 0.1 to 12% by weight of an impact modifier, relative to the total weight of the composition, and the composition lacks a plasticizer.

[0065] In yet another embodiment, the composition comprises, with respect to the total weight of the composition, 0.1 to 50% by weight of an impact modifier, particularly 0.1 to less than 15% by weight, more specifically 0.1 to 12% by weight of an impact modifier, and 0.1 to 1.5% by weight of a plasticizer.

[0066] In another embodiment, the composition lacks an impact-resistant modifier.

[0067] Advantageously, the composition contains 0.1 to 1.5% by weight of a plasticizer based on the total weight of the composition, and the composition lacks an impact resistance modifier.

[0068] In another embodiment, the composition lacks an impact-resistant modifier and a plasticizer.

[0069] In this last embodiment, the composition mainly comprises the thermoplastic polymer P1i and 0 to 5% by weight of additives, more specifically 0.1 to 5% of additives, and the totality of the components of the composition is equal to 100%.

[0070] In this case, the dominant thermoplastic polymer P1i is mixed with another polyamide.

[0071] Advantageously, the composition mainly consists of the thermoplastic polymer P1i and 0 to 5% by weight of additives, more specifically 0.1 to 5% of additives, and the total amount of the constituent components of the composition is equal to 100%.

[0072] Advantageously, the composition mainly consists of the thermoplastic polymer P1i, 0 to 5% by weight of additives, more specifically 0.1 to 5% of additives, and the total amount of the constituent components of the composition is equal to 100%.

[0073] In this case, the dominant thermoplastic polymer P1i is mixed with another polyamide.

[0074] Advantageously, the composition comprises the thermoplastic polymer P1i and 0 to 5% of additives, more specifically 0.1 to 5% of additives, and the total amount of the constituent components of the composition is equal to 100%.

[0075] Thermoplastic polymer P1i Thermoplastic or semi-crystalline thermoplastic polymers refer to materials that are generally solid at ambient temperature. They soften as the temperature rises, specifically after passing the glass transition temperature (Tg), and may exhibit a sharp transition when they pass what is called the melting point (Tm). When the temperature drops below the crystallization temperature, they become solid again.

[0076] Tg, Tc, and Tm are determined by differential scanning calorimetry (DSC) in accordance with standards 11357-2:2013 and 11357-3:2013, respectively.

[0077] The number-average molecular weight (Mn) of the semicrystalline polyamide thermoplastic polymer is preferably in the range of 10,000 to 85,000, particularly 10,000 to 60,000, preferably 10,000 to 50,000, and even more preferably 12,000 to 50,000. These Mn values ​​can correspond to an intrinsic viscosity of 0.8 or higher when determined in m-cresol according to standard ISO 307:2007, but by changing the solvent (using m-cresol instead of sulfuric acid at a temperature of 20°C).

[0078] The nomenclature is used to define polyamides as described in ISO standard 1874-1:2011 "Plastiques - Materiaux polyamides(PA) pour moulage et extrusion - Partie 1: Designation", particularly on page 3 (Tables 1 and 2), and is well known to those skilled in the art.

[0079] Polyamides may be homopolyamides, copolyamides, or mixtures thereof.

[0080] In one embodiment, the thermoplastic polymer is a long-chain aliphatic polyamide, that is, a polyamide having an average number of carbon atoms of 8.5 or more, preferably more than 9, and more specifically more than 10, per nitrogen atom.

[0081] In detail, long-chain aliphatic polyamides are: Polyamide 11 (PA11), polyamide 12 (PA12), polyamide 1010 (PA1010), polyamide 1012 (PA1012), polyamide 1212 (PA1012), or mixtures thereof, or copolyamides thereof, more specifically selected from PA11 and PA12.

[0082] More specifically, polyamide 11 (PA11), polyamide 12 (PA12), polyamide 1012 (PA1012), polyamide 1212 (PA1012), or mixtures thereof, or copolyamides thereof, in particular PA11 and PA12.

[0083] In one embodiment, the long-chain aliphatic polyamide is: Polyamide 12 (PA12), polyamide 1010 (PA1010), polyamide 1012 (PA1012), polyamide 1212 (PA1012), or mixtures thereof, or copolyamides thereof, more specifically selected from PA12.

[0084] In another embodiment, the long-chain aliphatic polyamide is: Polyamide 12 (PA12), polyamide 1012 (PA1012), polyamide 1212 (PA1012), or mixtures thereof, or copolyamides thereof, more specifically selected from PA12.

[0085] Advantageously, the semicrystalline thermoplastic polymer is a long-chain semi-aromatic semicrystalline polyamide, i.e., a polyamide having an average number of carbon atoms of more than 8.5, preferably more than 9, and more specifically more than 10 per nitrogen atom, and a melting point of 240°C to less than 280°C.

[0086] In detail, the long-chain semi-aromatic semi-crystalline polyamides are selected from polyamides 11 / 5T, 11 / 6T, or 11 / 10T, and MXDT / 10T. <PMDT / 10TおよびBACT / 10T。

[0087] Advantageously, each sealing layer consists of a composition containing the same type of polyamide.

[0088] When welding is required, there are various methods for welding components made of polyamide thermoplastic polymers. Therefore, contact or non-contact heating blades, ultrasonic welding, infrared welding, vibration, rotation of one component to be welded against another, or even laser welding may be used.

[0089] Regarding impact resistance modifiers The impact modifier may be any impact modifier, as long as it is a polymer that has a coefficient lower than that of the resin and has good adhesion to the matrix in order to dissipate crack energy.

[0090] The impact resistance modifier is advantageously comprised of a polymer, more specifically a polyolefin, having a flexural modulus of less than 100 MPa and a Tg (inflection point of a DSC thermogram, measured according to standard 11357-2) below 0°C, as measured according to standard ISO 178.

[0091] In one embodiment, PEBA is excluded from the definition of an impact modifier.

[0092] The polyolefins used as impact modifiers may be functionalized or unfunctionalized, or may be a mixture of at least one functionalized polyolefin and / or at least one unfunctionalized polyolefin. For simplicity, polyolefins are denoted as (B), functionalized polyolefins as (B1), and unfunctionalized polyolefins as (B2) below.

[0093] Unfunctionalized polyolefins (B2) are classically homopolymers or copolymers of alpha-olefins or diolefins, such as ethylene, propylene, 1-butene, 1-octene, and butadiene. Examples include: - Polyethylene, specifically LDPE, HDPE, LLDPE (linear low-density polyethylene), VLDPE (very low-density polyethylene), and metallocene polyethylene homopolymers and copolymers. - Propylene homopolymer or copolymer, - Ethylene / alpha-olefin copolymers, such as ethylene / propylene, EPR (abbreviation for ethylene-propylene-rubber), and ethylene / propylene / diene (EPDM), - Styrene / ethylene-butene / styrene (SEBS), styrene / butadiene / styrene (SBS), styrene / isoprene / styrene (SIS), styrene / ethylene-propylene / styrene (SEPS) block copolymers, - A copolymer in which the proportion of comonomers of ethylene and at least one product selected from salts or esters of unsaturated carboxylic acids, such as alkyl (meth)acrylates (e.g., methyl acrylate), or vinyl esters of saturated carboxylic acids, such as vinyl acetate (EVA), can reach 40% by weight.

[0094] Functionalized polyolefins (B1) can be polymers of alpha-olefins having reaction units (functional groups), such reaction units being acids, anhydrides, or epoxy functional groups. For example, the aforementioned polyolefins (B2) can be mentioned, which are grafted, copolymerized, or ternary polymerized by unsaturated epoxides, e.g., glycidyl (meth)acrylate, or by carboxylic acids or their corresponding salts or esters, e.g., (meth)acrylic acid (which can be completely or partially neutralized by metals, e.g., Zn), or even by carboxylic acid anhydrides, e.g., maleic anhydride. Functionalized polyolefins are, for example, PE / EPR mixtures, the ratio of which to weight can vary widely, e.g., from 40 / 60 to 90 / 10, and the mixtures are co-grafted with anhydrides, particularly maleic anhydride, according to graft rates of, for example, 0.01 to 5% by weight.

[0095] The functionalized polyolefin (B1) may be selected from the following (co)polymers grafted with maleic anhydride or glycidyl methacrylate, with grafting rates of, for example, 0.01 to 5% by weight: - Copolymers containing, for example, 35 to 80% by weight of ethylene, PE, PP, ethylene and propylene, butene, hexene or octene, - Ethylene / alpha-olefin copolymers, such as ethylene / propylene, EPR (abbreviation for ethylene-propylene-rubber), and ethylene / propylene / diene (EPDM), - Styrene / ethylene-butene / styrene (SEBS), styrene / butadiene / styrene (SBS), styrene / isoprene / styrene (SIS), styrene / ethylene-propylene / styrene (SEPS) block copolymers, - Ethylene and vinyl acetate copolymer (EVA) containing up to 40% by weight of vinyl acetate, - Ethylene and alkyl (meth)acrylate copolymers containing up to 40% by weight of alkyl (meth)acrylate, - Ethylene and vinyl acetate (EVA) and alkyl (meth)acrylate copolymers containing up to 40% by weight of comonomers.

[0096] Functionalized polyolefins (B1) can also be selected from ethylene / propylene copolymers (products described in EP-A-0,342,066) with monoamine polyamides (or polyamide oligomers) condensed with propylene, mainly grafted with maleic anhydride.

[0097] Functionalized polyolefin (B1) may also be a coat or terpolymer of at least the following units: (1) ethylene, (2) an alkyl (meth)acrylate or vinyl ester of a saturated carboxylic acid, and (3) an anhydride, such as maleic anhydride or (meth)acrylic acid, or an epoxy, such as glycidyl (meth)acrylate.

[0098] Examples of the latter type of functionalized polyolefin include the following copolymers, where ethylene is preferably equivalent to at least 60% by weight, and ter monomers (functional groups) are equivalent to, for example, 0.1 to 10% by weight of the copolymer: - Ethylene / alkyl (meth)acrylate / (meth)acrylic acid or maleic anhydride or glycidyl methacrylate copolymer, - Ethylene / vinyl acetate / maleic anhydride or glycidyl methacrylate copolymer, - Ethylene / vinyl acetate or alkyl (meth)acrylate / (meth)acrylic acid or maleic anhydride or glycidyl methacrylate copolymer.

[0099] In the copolymers mentioned above, (meth)acrylic acid can be chlorided with Zn or Li.

[0100] The term “alkyl(meth)acrylate” in (B1) or (B2) refers to C1 to C8 alkyl methacrylates and acrylates, and may be selected from methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethyl-hexyl acrylate, cyclohexyl acrylate, methyl methacrylate and ethyl methacrylate.

[0101] Furthermore, the previously cited polyolefin (B1) may also be crosslinked by any suitable method or agent (diepoxy, diacid, peroxide), and the term functionalized polyolefin also includes the previously cited polyolefin and a mixture of difunctional reagents that can react with them, such as diacids, dianhydrides, and diepoxys, or a mixture of at least two functionalized polyolefins that can react together.

[0102] The copolymers (B1) and (B2) mentioned above can be copolymerized by statistical or sequential methods and have linear or branched structures.

[0103] The molecular weight, MFI index, and density of these polyolefins may also vary widely, as those skilled in the art are aware. MFI, an abbreviation for melt flow index, is a measure of fluidity in the molten state. It is measured according to standard ASTM 1238.

[0104] Advantageously, the non-functionalized polyolefin (B2) is selected from polypropylene homopolymers or copolymers, any ethylene homopolymer or copolymer, and higher alpha-olefin comonomers, such as butene, hexene, octene, or 4-methyl-1-pentene. Examples include PP, high-density PE, medium-density PE, linear low-density PE, low-density PE, and very low-density PE. It is known to those skilled in the art that these polyethylenes are produced by the "free radical" method, the "Ziegler" catalyst method, or more recently, by a "metallocene" catalyst.

[0105] Advantageously, the functionalized polyolefin (B1) is selected from any polymer comprising alpha-olefin units and units having polar reactive functional groups such as epoxy, carboxylic acid, or carboxylic acid anhydride functional groups. Examples of such polymers include terpolymers of ethylene, alkyl acrylate, and maleic anhydride or glycidyl methacrylate, such as Lotader® from the applicant, or polyolefins grafted with maleic anhydride, such as Orevac® from the applicant, as well as terpolymers of ethylene, alkyl acrylate, and (meth)acrylic acid. Homopolymers or copolymers of polypropylene grafted with carboxylic acid anhydrides and then condensed with polyamide or monoamine polyamide oligomers may also be mentioned.

[0106] Advantageously, the composition constituting the sealing layer(s) lacks polyether block amide (PEBA). In this embodiment, PEBA is therefore excluded from the impact resistance modifier.

[0107] Advantageously, the permeable composition lacks core-shell particles or core-shell polymers.

[0108] A core-shell particle should be understood as a particle in which the first layer forms the nucleus, and all subsequent layers form their respective shells.

[0109] Core-shell particles are obtained by a method having several steps, including at least two steps. Such methods are described, for example, in documents US2009 / 0149600 or EP0,722,961.

[0110] Regarding plasticizers The plasticizer may be one commonly used in polyamide-based compositions.

[0111] Advantageously, a plasticizer with good thermal stability is used so as not to form fumes during the steps of mixing different polymers and transforming the resulting composition.

[0112] In detail, this plasticizer is Benzenesulfonamide derivatives, such as n-butylbenzenesulfonamide (BBSA), ethyltoluenesulfonamide (ETSA), N-cyclohexyltoluenesulfonamide, and ortho and para isomers of N-(2-hydroxypropyl)benzenesulfonamide (HP-BSA), Hydroxybenzoate esters, for example, 2-ethylhexyl p-hydroxybenzoate (EHPB) and 2-decylhexyl p-hydroxybenzoate (HDPB), Esters or ethers of tetrahydrofurfuryl alcohol, for example, oligoethyleneoxytetrahydrofurfuryl alcohol, Esters of citric acid or hydroxymalonic acid, such as oligoethylene oxymalonate It can be selected from the following.

[0113] The preferred plasticizer is n-butylbenzenesulfonamide (BBSA).

[0114] Another, and more specifically, preferred, plasticizer is N-(2-hydroxypropyl)benzenesulfonamide (HP-BSA). In fact, the latter has the advantage of preventing the formation of deposits ("die smears") in the extrusion screw and / or die during the extrusion conversion step.

[0115] Of course, it is possible to use a mixture of plasticizers.

[0116] Regarding composite reinforcement layers and polymer P2j Polymer P2j may be a thermoplastic polymer or a thermosetting polymer.

[0117] One or more composite reinforcement layers may be present.

[0118] Each of the aforementioned layers consists of a fibrous material in the form of continuous fibers impregnated with a composition mainly comprising at least one thermoplastic polymer P2j, where j corresponds to the number of layers present.

[0119] j ranges from 1 to 10, more specifically from 1 to 5, and especially from 1 to 3, with j=1 being the preferred value.

[0120] The term "primarily" means that at least one of the polymers is present in an amount greater than 50% by weight of the total weight of the matrix of the composition and the composite.

[0121] Advantageously, the at least one dominant polymer is present in an amount of more than 60% by weight, particularly more than 70% by weight, more specifically more than 80% by weight, and more specifically 90% by weight or more, based on the total weight of the composition.

[0122] The composition may further comprise impact resistance modifiers and / or additives.

[0123] Apart from nucleating agents, additives may be selected from antioxidants, heat stabilizers, UV absorbers, light stabilizers, lubricants, inorganic fillers, flame retardants, plasticizers, and dyes.

[0124] Advantageously, the composition mainly consists of the thermoplastic polymer P2j, 0 to 15% by weight of an impact modifier, more specifically 0 to 12% by weight of an impact modifier, and 0 to 5% by weight of an additive, with the total amount of the constituent components of the composition equal to 100% by weight.

[0125] The at least one dominant polymer in each layer may be the same or different.

[0126] In one embodiment, a single dominant polymer is present in at least the composite reinforcement layer and does not adhere to the sealing layer.

[0127] In one embodiment, each reinforcing layer comprises the same type of polymer, more specifically, an epoxy resin or epoxy-based resin.

[0128] Polymer P2j Thermoplastic polymer P2j Thermoplastics, or thermoplastic polymers, generally refer to materials that are solid at ambient temperature. These can be semi-crystalline or amorphous, more specifically semi-crystalline, and they soften as the temperature rises, more specifically after passing the glass transition temperature (Tg). If amorphous, they flow at higher temperatures, or if semi-crystalline, they may exhibit a sharp transition when passing the so-called melting point (Tm). They become solid again when the temperature drops below the crystallization temperature Tc (for semi-crystalline materials) and below the glass transition temperature (for amorphous materials).

[0129] Tg, Tc, and Tm are determined by differential scanning calorimetry (DSC) in accordance with standards 11357-2:2013 and 11357-3:2013, respectively.

[0130] The number-average molecular weight (Mn) of the thermoplastic polymer is preferably in the range of 10,000 to 40,000, and more preferably in the range of 10,000 to 30,000. These Mn values ​​can correspond to an intrinsic viscosity of 0.8 or higher when determined in m-cresol according to standard ISO 307:2007, but by changing the solvent (using m-cresol instead of sulfuric acid at a temperature of 20°C).

[0131] Examples of suitable semi-crystalline thermoplastic polymers in the present invention include: Copolymers, such as polyamide-polyether copolymers, and more specifically polyamides, including aromatic and / or alicyclic structures, polyester, Polyaryl ether ketone (PAEK), Polyetheretherketone (PEEK), Polyetherketone (PEKK), Polyetherketone etherketone ketone (PEKEKK), Polyimide, more specifically polyetherimide (PEI) or polyamide-imide, Polylylsulfone (PSU), more specifically polyallylsulfone, for example, polyphenylsulfone (PPSU), Contains polyethersulfone (PES).

[0132] Semicrystalline polymers, specifically polyamides and their semicrystalline copolymers, are more preferably used.

[0133] The nomenclature is used to define polyamides as described in ISO standard 1874-1:2011 "Plastiques - Materiaux polyamides(PA) pour moulage et extrusion - Partie 1: Designation", particularly on page 3 (Tables 1 and 2), and is well known to those skilled in the art.

[0134] Polyamides may be homopolyamides, copolyamides, or mixtures thereof.

[0135] Advantageously, semicrystalline polyamides are semi-aromatic polyamides, particularly semi-aromatic polyamides of formula X / YAr as described in EP1505099, specifically semi-aromatic polyamides of formula A / XT (wherein A is a unit obtained from an amino acid, a unit obtained from a lactam, and the formula (Ca diamine)(Cb diacid), where a represents the number of carbon atoms in the diamine and b represents the number of carbon atoms in the diacid, and a and b are each selected from units between 4 and 36, preferably between 9 and 18), where the unit (Ca diamine) is selected from linear or branched aliphatic diamines, alicyclic diamines and alkyl aromatic diamines, and the unit (Cb diacid) is a unit selected from linear or branched aliphatic diacids, alicyclic diacids and aromatic diacids. XT represents a unit obtained from the polycondensation of Cx diamine and terephthalic acid, where x represents the number of carbon atoms in the Cx diamine, and x is between 5 and 36, preferably between 9 and 18, and has formulas A / 5T, A / 6T, A / 9T, A / 10T or A / 11T, in particular, where A is a polyamide as defined above, and in detail polyamides include 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 The chainring can be selected from either 11 / MXDT / 10T or 11 / 5T / 10T.

[0136] 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 have a Tg of 80°C or higher.

[0137] Thermosetting polymer P2j The thermosetting polymer is selected from epoxy resins or epoxy-based resins, polyesters, vinyl esters, and polyurethanes, or mixtures thereof, more specifically from epoxy resins or epoxy-based resins.

[0138] Advantageously, each composite reinforcing layer consists of a composition comprising the same type of polymer, more specifically, an epoxy resin or epoxy-based resin.

[0139] The composition containing the polymer P2j is radiation-permeable, making it suitable for welding.

[0140] In another embodiment, the composite reinforcement layer is wrapped around the sealing layer without any subsequent welding.

[0141] Regarding the structure The multilayer structure thus includes a sealing layer and at least one composite reinforcing layer wrapped around the sealing layer, which may or may not be bonded to each other.

[0142] Advantageously, the sealing layer and the reinforcing layer do not adhere to each other and consist of compositions containing different polymers, respectively.

[0143] However, the aforementioned different polymers may be of the same type.

[0144] Therefore, if one of the two composite reinforcement and sealing layers to be welded is made of a composition containing an aliphatic polyamide, then the other layer is made of a composition containing a polyamide that is not aliphatic, but for example, a semi-aromatic polyamide, so that it has a high Tg polymer as the matrix of the composite reinforcement.

[0145] The multilayer structure may include up to 10 sealing layers and up to 10 composite reinforcing layers having different properties.

[0146] Advantageously, the structure lacks a binder or adhesive layer between the sealing layers, or between the composite reinforcing layers, or even between the outermost sealing layer and the innermost composite reinforcing layer.

[0147] It is clear that the aforementioned multilayer structure is not necessarily symmetrical, and therefore may contain more sealing layers than the composite layer, or vice versa, but that the layers and reinforcing layers cannot be replaced.

[0148] Advantageously, the multilayer structure includes 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 sealing layers and 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 composite reinforcing layers.

[0149] Advantageously, the multilayer structure includes one, two, three, four, or five sealing layers and one, two, three, four, or five composite reinforcing layers.

[0150] Advantageously, the multilayer structure includes one, two, or three sealing layers and one, two, or three composite reinforcing layers.

[0151] Advantageously, these consist of compositions each containing a different polymer.

[0152] Advantageously, these consist of compositions comprising a polyamide corresponding to polyamide P1i and an epoxy or epoxy resin P2j, respectively.

[0153] In one embodiment, the multilayer structure includes one sealing layer and several reinforcing layers, wherein adjacent reinforcing layers are wound around the sealing layer, and other reinforcing layers are wound directly around adjacent reinforcing layers.

[0154] In another embodiment, the multilayer structure includes a single reinforcing layer and several sealing layers, the reinforcing layer being wound around adjacent sealing layers.

[0155] In one advantageous embodiment, the multilayer structure comprises a single sealing layer and a single composite reinforcing layer, the reinforcing layer being wound around the sealing layer.

[0156] All combinations of these two types of layers are therefore within the scope of the present invention, provided that at least the innermost composite reinforcing layer is wrapped around the adjacent outermost sealing layer, and the other layers are either bonded to each other or not.

[0157] Advantageously, in the multilayer structure, each sealing layer is composed of a composition containing the same type of polymer P1i, more specifically, a polyamide.

[0158] The phrase "polymer of the same type" means, for example, polyamides that may be the same or different polyamides depending on the layer.

[0159] Advantageously, the polymer P1i is a polyamide, and the polymer P2j is an epoxy or epoxy resin.

[0160] Advantageously, the polyamide P1i is identical in all sealing layers.

[0161] Advantageously, the polymer P1i is a long-chain aliphatic polyamide, more specifically PA1010, PA1012, PA1212, PA11, PA12, and especially PA11 or PA12.

[0162] Advantageously, the polyamide P1i is a long-chain semi-aromatic polyamide, specifically PA11 / 5T, PA11 / 6T, or PA11 / 10T. In this case, obviously, the ratio of 11 must be carefully selected so that the Tm of the polymer is lower than 280°C, preferably 265°C.

[0163] Advantageously, in the multilayer structure, each reinforcing layer is composed of a polymer P2j of the same type, more specifically an epoxy resin or epoxy-based resin.

[0164] Advantageously, the polyamide P2j is identical in all reinforcing layers.

[0165] Advantageously, in the multilayer structure, each sealing layer is made of a composition containing the same type of polymer P1i, more specifically a polyamide, and each reinforcing layer is made of a composition containing the same type of polymer P2j, specifically epoxy or epoxy resin.

[0166] Advantageously, the polymer P1i is a long-chain aliphatic polyamide, more particularly PA1010, PA1012, PA1212, PA11, PA12, especially PA11 or PA12, and the polymer P2j is a semi-aromatic polyamide, more particularly selected from PA MPMDT / 6T, PA11 / 10T, PA11 / BACT, PA5T / 10T, PA11 / 6T / 10T, PA MXDT / 10T, PA MPMDT / 10T, PA BACT / 10T, PA BACT / 6T, PA BACT / 10T / 6T, PA11 / BACT / 6T, PA11 / MPMDT / 6T, PA11 / MPMDT / 10T, PA11 / BACT / 10T, PA and 11 / MXDT / 10T.

[0167] In one embodiment, the multilayer structure consists of a single reinforcing layer and a single sealing layer, wherein the polymer P1i is a long-chain aliphatic polyamide, more specifically PA1010, PA1012, PA1212, PA11, PA12, and especially PA11 or PA12, and the polymer P2j is a semi-aromatic polyamide, more specifically selected from PA MPMDT / 6T, PA PA11 / 10T, PA11 / BACT, PA11 / 6T / 10T, PA MXDT / 10T, PA MPMDT / 10T, PA BACT / 10T, PA BACT / 6T, PA BACT / 10T / 6T, PA11 / BACT / 6T, PA11 / MPMDT / 6T, PA11 / MPMDT / 10T, PA11 / BACT / 10T, and PA11 / MXDT / 10T.

[0168] In another embodiment, the multilayer structure comprises a single reinforcing layer and a single sealing layer, wherein the polymer P1i is a long-chain aliphatic polyamide, more specifically PA1010, PA1012, PA1212, PA11, PA12, and especially PA11 or PA12, and the polymer P2j is a semi-aromatic polyamide, more specifically selected from PA MPMDT / 6T, PA PA11 / 10T, PA11 / BACT, PA11 / 6T / 10T, PA MXDT / 10T, PA MPMDT / 10T, PA BACT / 10T, PA BACT / 6T, PA BACT / 10T / 6T, PA11 / BACT / 6T, PA11 / MPMDT / 6T, PA11 / MPMDT / 10T, PA11 / BACT / 10T, and PA11 / MXDT / 10T.

[0169] In yet another embodiment, the multilayer structure consists of a single reinforcing layer and a single sealing layer, wherein the polymer P1i is a long-chain aliphatic polyamide, more specifically PA1010, PA1012, PA1212, PA11, PA12, or a semi-aromatic polyamide, more specifically selected from polyamide 11 / 5T or 11 / 6T or 11 / 10T, MXDT / 10T, MPMDT / 10T, and BACT / 10T, more specifically PA11 or PA12, and the polymer P2j is an epoxy or epoxy-based resin.

[0170] In another embodiment, the multilayer structure consists of a single reinforcing layer and a single sealing layer, wherein the polymer P1i is a long-chain aliphatic polyamide, particularly PA1010, PA1012, PA1212, PA12, or a semi-aromatic polyamide, particularly selected from polyamide 11 / 5T or 11 / 6T or 11 / 10T, MXDT / 10T, MPMDT / 10T, and BACT / 10T, particularly PA12, and the polymer P2j is an epoxy or epoxy-based resin.

[0171] Advantageously, the multilayer structure further comprises at least one outer layer made of a fibrous material consisting of continuous glass fibers impregnated with a permeable amorphous polymer, the outermost layer of the multilayer structure.

[0172] The aforementioned outer layer is a second reinforcing layer, but it is permeable, which allows text to be placed on the structure.

[0173] The aforementioned outer layer does not, in any way, correspond to a layer placed on the outermost composite reinforcement layer of a polyamide polymer whose structure lacks those mentioned above.

[0174] Regarding fibrous materials The fibers that make up the aforementioned fibrous material are, in detail, inorganic, organic, or plant fibers.

[0175] Advantageously, the fibrous material may or may not be sized.

[0176] The fibrous material may therefore contain up to 3.5% by weight of an organic material (of the thermosetting or thermoplastic resin type), which is called sizing.

[0177] Inorganic fibers include, for example, carbon fibers, glass fibers, basalt or basalt-based fibers, silica fibers, or silicon carbide fibers. Organic fibers include thermoplastic or thermosetting polymer-based fibers, such as semi-aromatic polyamide fibers, aramid fibers, or polyolefin fibers. Preferably, these are amorphous thermoplastic polymer-based, and if the thermoplastic polymer mixture is amorphous, they have a Tg higher than the glass transition temperature Tg of the polymer or thermoplastic polymer mixture constituting the pre-impregnation matrix, or if the thermoplastic polymer mixture is semi-crystalline, they have a Tg higher than the Tm of the polymer or thermoplastic polymer mixture constituting the pre-impregnation matrix. Advantageously, these are semi-crystalline thermoplastic polymer-based, and if the thermoplastic polymer mixture is amorphous, they have a melting temperature Tm higher than the Tg of the polymer or thermoplastic polymer mixture constituting the pre-impregnation matrix, or if the thermoplastic polymer mixture is semi-crystalline, they have a melting temperature Tm higher than the Tm of the polymer or thermoplastic polymer mixture constituting the pre-impregnation matrix. Therefore, there is no risk of melting during impregnation by the thermoplastic matrix of the final composite in the organic fibers constituting the fibrous material. Plant fibers include natural linen, hemp, lignin, bamboo, silk, spider silk in particular, sisal hemp, and other cellulose fibers, in particular viscose. These plant fibers may be used alone, treated with a coating layer, or coated to promote adhesion and impregnation of a thermoplastic polymer matrix.

[0178] Textile materials can be cloth, string, or woven fabrics made from fibers.

[0179] This could be considered equivalent to a fiber that uses a supporting thread.

[0180] These component fibers can be used individually or in mixtures. Therefore, organic fibers can be mixed with inorganic fibers to pre-impregnate them with thermoplastic polymer powder, forming a pre-impregnated fibrous material.

[0181] Organic fiber yarns can have several basis weights. These can further have several shapes. The component fibers of a fibrous material can also take the form of a mixture of these reinforcing fibers having different shapes. The fibers are continuous fibers.

[0182] Preferably, the fibrous material is selected from glass fibers, carbon fibers, basalt fibers or basalt-based fibers, or mixtures thereof, and more specifically from carbon fibers.

[0183] This is used in the form of one roving or several rovings.

[0184] In another aspect, the present invention relates to a method for producing the above-defined multilayer structure, characterized by comprising the step of producing a sealing layer by extrusion blow molding, rotational molding, injection molding and / or extrusion.

[0185] In one embodiment, the method for generating a multilayer structure includes the step of filament winding a reinforcing layer defined above around a sealing layer defined above.

[0186] All the characteristics detailed above also apply to methods. [Examples]

[0187] In all examples, the tank is obtained by rotational molding of the sealing layer (liner) at a temperature suitable for the properties of the thermoplastic resin used.

[0188] For composite reinforcements made of epoxy resin or epoxy-based resin, a wet filament winding method is then used, which involves winding fibers around the liner, which have been previously pre-impregnated in a liquid epoxy bath or epoxy-based liquid bath. The reservoir is then polymerized in an oven for 2 hours.

[0189] In all other cases, a fibrous material previously impregnated with thermoplastic resin (tape) is used. This tape is deposited by filament winding using a 1500W laser heater robot at a speed of 12 m / min, with no polymerization step.

[0190] Example 1 Notched Charpy impact at -40°C according to ISO 179-1:2010. Two types of long-chain liners belonging to PA11 and PA12, as well as two types of short-chain liners, were manufactured by rotational molding as shown above.

[0191] These four types of liners were subjected to notched Charpy impact tests at -40°C, and the results are shown in Figure 1.

[0192] The cold resistance of the long-chain liner was significantly superior to that of the short-chain PA6 and PA66 liners.

[0193] Example 2 Permeability of PA11 and PA12 (Arkema), and HDPE (Marlex® HMN TR-942 (Chevron Phillips)) liners Two types of long-chain liners, the first PA11 (Arkema) and the second PA12 (Arkema), along with an HDPE liner, were fabricated by rotational molding, and their hydrogen permeability was tested at 23°C.

[0194] This involves sweeping the upper surface of the film using a test gas (hydrogen) and measuring the flow diffusing through the lower part of the film by gas-phase chromatography, with the sweep being performed using nitrogen as the carrier gas.

[0195] The experimental conditions are presented in Table 1. [Table 1] TIFF2026076158000002.tif77170

[0196] The results are shown in Figure 2, indicating that both the PA11 and PA12 liners have significantly lower permeability than the HDPE liners.

[0197] Example 3 Effect of plasticizer (N-butylbenzenesulfonamide: BBSA) ratio on notched Charpy impact at -40°C, according to ISO 179-1:2010. Two types of liners, PA11 and PA12, containing 7% or 12% plasticizer (BBSA) relative to the total weight of the composition, without plasticizer, were manufactured by rotational molding.

[0198] These liners were subjected to notched Charpy impact tests at -40°C according to ISO 179-1:2010, and the results are shown in Figure 3.

[0199] Plasticizers have harmful effects when cold, which weakens the structure, and the permeability increases to 50% with 7% BBSA.

[0200] Example 4 The effect of the ratio of impact resistance modifiers (composed of "LT cocktail" having the following composition: lotader® 4700 (50%) + lotader® AX8900 (25%) + Lucalene® 3110 (25%)) on the hydrogen permeability of liner PA12. The hydrogen permeability of PA12 liners without plasticizers, and with and without impact modifiers, was tested and is reported in Table 2. [Table 2] TIFF2026076158000003.tif32170

[0201] Penetration is (cc.25μ / m 2 It can also be expressed as 0.24hPa.

[0202] The permeability must then be 101,325 times greater.

[0203] The results indicate that the ratio of impact-resistant modifiers affects hydrogen permeability.

[0204] The higher the proportion of impact-resistant additive, the greater the penetration.

[0205] Example 5 A Type IV hydrogen storage tank consisting of T700SC31E (Toray) carbon fiber epoxy composite reinforcement (Tg120℃) and a PA11 sealing layer.

[0206] The operating temperature is sufficient for rapid tank filling, specifically within 3 to 5 minutes.

[0207] Example 6 (Counterexample) A Type IV hydrogen storage tank constructed with T700SC31E (Toray) carbon fiber epoxy composite reinforcement (Tg120℃) and an HDPE sealing layer.

[0208] The operating temperature is too low for rapid tank filling, specifically for 3 to 5 minutes.

[0209] Example 7 Type IV hydrogen storage tank, T700SC31E (Toray), consisting of carbon fiber epoxy composite reinforcement, BACT / 10T, and PA12 sealing layers. The selected BACT / 10T composition has a melting temperature Tm of 283°C, a crystallization temperature Tc of 250°C, and a glass transition temperature of 164°C.

[0210] Tg, Tc, and Tm are determined by differential scanning calorimetry (DSC) in accordance with standards 11357-2:2013 and 11357-3:2013, respectively.

[0211] The BACT / 10T PA-based complex does not have long crosslinks, but it has a high Tg matrix of the 8h type at 140°C.

[0212] Therefore, after the fibers are removed, the tank is complete, saving 8 hours of process time.

Claims

1. A multilayer structure for transporting, distributing, or storing hydrogen, comprising at least one sealing layer (1) and at least one composite reinforcing layer (2) from the inside out, The innermost composite reinforcing layer is wrapped around the outermost adjacent sealing layer (1), The sealing layer is made of a composition, and the composition is The composition comprises, in an amount of more than 50% by weight, semi-crystalline, at least one semi-crystalline long-chain polyamide thermoplastic polymer P1i, where i = 1 to n, where n is the number of sealing layers, and Tm is greater than 160°C, more specifically greater than 170°C, as measured according to ISO 11357-3:2013. The long-chain polyamide thermoplastic polymer has an average number of more than 9 carbon atoms per nitrogen atom, Excluding polyether block amide (PEBA), An impact-resistant modifier up to 50% by weight, particularly an impact-resistant modifier up to less than 15% by weight, and more specifically, an impact-resistant modifier up to 12% by weight, relative to the total weight of the composition. up to 1.5% by weight of plasticizer relative to the total weight of the composition. Includes, The aforementioned composition lacks a nucleating agent, In each sealing layer, at least one dominant polyamide thermoplastic polymer may be the same or different. At least one of the composite reinforcing layers is a fibrous material in the form of continuous fibers impregnated with a composition comprising at least one polymer P2j in an amount exceeding 50% by weight relative to the total weight of the composition, where j = 1 to m, and m is the number of reinforcing layers, and more specifically a composition comprising epoxy resin or epoxy-based resin. The aforementioned structure is a multilayer structure lacking a polyamide polymer layer, wherein the polyamide polymer layer is the outermost layer and adjacent to the outermost layer of composite reinforcement.

2. The multilayer structure according to claim 1, characterized in that each sealing layer contains the same type of polyamide.

3. The multilayer structure according to claim 1 or 2, characterized in that each reinforcing layer contains the same type of polymer, more specifically, an epoxy resin or epoxy-based resin.

4. The multilayer structure according to claim 3, characterized in that each sealing layer contains the same type of polyamide, and each reinforcing layer contains the same type of polymer, more specifically epoxy resin or epoxy-based resin.

5. A multilayer structure according to any one of claims 1 to 4, characterized by having a single sealing layer and a single reinforcing layer.

6. The multilayer structure according to any one of claims 1 to 5, characterized in that the polymer P1i is a long-chain aliphatic polyamide, more particularly PA1010, PA1012, PA1212, PA11, PA12, especially PA11 or PA12, or semi-aromatic, more particularly selected from polyamide 11 / 5T or 11 / 6T or 11 / 10T, MXDT / 10T, MPMDT / 10T and BACT / 10T.

7. The multilayer structure according to any one of claims 1 to 6, characterized in that the polymer P2j is an epoxy resin or an epoxy-based resin.

8. The multilayer structure according to claim 6 or 7, characterized in that the multilayer structure comprises a single reinforcing layer and a single sealing layer, the polymer P1i is a long-chain aliphatic polyamide, more specifically PA1010, PA1012, PA1212, PA11, PA12, or a semi-aromatic polyamide, more specifically selected from polyamide 11 / 5T or 11 / 6T or 11 / 10T, MXDT / 10T, MPMDT / 10T, and BACT / 10T, more specifically PA11 or PA12, and the polymer P2j is epoxy or an epoxy resin.

9. The multilayer structure according to any one of claims 1 to 8, characterized in that the fibrous material of the composite reinforcing layer is selected from glass fibers, carbon fibers, basalt fibers or basalt-based fibers, or mixtures thereof, more particularly from carbon fibers.

10. The multilayer structure according to any one of claims 1 to 9, wherein the structure further comprises at least one outer layer made of a fibrous material consisting of continuous glass fibers impregnated with a permeable amorphous polymer, and the layer is the outermost layer of the multilayer structure.

11. A method for producing a multilayer structure according to any one of claims 1 to 10, characterized by comprising the step of producing a sealing layer by extrusion blow molding, rotational molding, injection molding and / or extrusion.

12. A method for producing the multilayer structure according to claim 11, characterized by comprising the step of filament winding the reinforcing layer according to claim 1 around the sealing layer according to claim 1.

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