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JP-2026076158-A - Multilayer structure for transporting or storing hydrogen

JP2026076158AJP 2026076158 AJP2026076158 AJP 2026076158AJP-2026076158-A

Abstract

[Problem] To provide 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 comprises 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. [Selection Diagram] Figure 1

Inventors

  • デュフォール， ニコラス
  • ダン， パトリック
  • グピル， アントワーヌ

Assignees

  • アルケマ フランス

Dates

Publication Date
20260511
Application Date
20251224
Priority Date
20200128

Claims (12)

  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. The composition contains up to 1.5% by weight of a plasticizer, 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, an 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 a semi-aromatic polyamide, more particularly selected from polyamide 11/5T, 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-based resin.
  9. The multilayer structure according to any one of claims 1 to 8, characterized in that the fibrous material of the composite reinforcement layer is selected from glass fibers, carbon fibers, basalt fibers, or basalt-based fibers, or mixtures thereof, particularly 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.

Description

This patent application relates to a multilayer composite structure for transporting, distributing, or storing hydrogen, and more particularly to a method for producing such a structure. Hydrogen tanks are currently attracting considerable attention from numerous manufacturers, particularly in the automotive sector. One of the desired goals is to propose even lower-emission vehicles. Therefore, the aim is for electric or hybrid vehicles, including batteries, to gradually replace internal combustion engine vehicles, such as gasoline or diesel vehicles. Batteries are known to be relatively complex vehicle components. Depending on the battery's location in the vehicle, it may need to be protected from impact and from external environments that can be extremely high in temperature and variable humidity. Avoiding any risk of fire may also be necessary. Furthermore, it is crucial that their operating temperatures do not exceed 55°C to avoid damaging the battery cells and extend their lifespan. Conversely, in winter, for example, it may be necessary to raise the battery temperature to optimize battery operation. Furthermore, electric vehicles still suffer from several problems today, namely battery range, the use of rare earth metals in these batteries, the limited availability of resources, charging times that are far longer than the time it takes to refill the tank, and the challenges of generating the electricity needed to charge the batteries in various countries. Therefore, hydrogen can be converted into electricity by fuel cells, and thus supply power to electric vehicles, making it a substitute for electric batteries. Hydrogen tanks typically consist of a metal liner (or sealing layer) that must protect hydrogen from permeation. One type of tank is called Type IV, which is based on a thermoplastic liner with a composite layer wrapped around it. 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 consisting of fibers (glass, aramid, carbon), also known as a reinforcing sheath or layer. This allows it to operate at much higher pressures while reducing weight and avoiding the risk of explosion in the event of severe external impact. Liner has a certain principle characteristic: Hydrogen permeability, which is unlikely to be converted by extrusion blow molding, rotational molding, injection molding, or extrusion, is actually a crucial factor in limiting hydrogen leakage from tanks. Good mechanical properties (fatigue) at low temperatures (-40 to -70°C) It must be heat resistant up to 120°C. In practice, it is necessary to increase the hydrogen tank filling rate, which should be roughly equivalent to that of an internal combustion engine fuel tank (approximately 3 to 5 minutes). However, this increase in rate causes the tank to overheat significantly, reaching a temperature of approximately 100°C. 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 filling experiments and simulations, Energy Procedia 29 (2012), pp. 192-200). The first-generation Type IV tanks used a high-density polyethylene (HDPE) based liner. However, HDPE has the drawbacks of having too low a melting point and too high a hydrogen permeability. This presents a problem in terms of heat resistance, requiring new requirements and preventing an increase in tank filling speed. Polyamide PA6-based liners have been under development for many years. Nevertheless, PA6 has the disadvantage of having low resistance to cold. 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. French patent application FR2923575 describes a tank for storing fluid under high pressure, comprising metal end pieces at each of its axial ends, wherein a liner surrounds the end pieces, and a structural layer made of thermosetting resin-impregnated fibers surrounds the liner. 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) mo