Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
  • C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/50—Phosphorus bound to carbon only
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/02—Fibres or whiskers
  • C08K7/04—Fibres or whiskers inorganic
  • C08K7/06—Elements
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K9/00—Use of pretreated ingredients
  • C08K9/08—Ingredients agglomerated by treatment with a binding agent
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
  • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
  • F17C1/00—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge
  • F17C1/16—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge constructed of plastics materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/04—Carbon
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
  • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
  • F17C2203/00—Vessel construction, in particular walls or details thereof
  • F17C2203/01—Reinforcing or suspension means
  • F17C2203/011—Reinforcing means
  • F17C2203/012—Reinforcing means on or in the wall, e.g. ribs
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
  • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
  • F17C2203/00—Vessel construction, in particular walls or details thereof
  • F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
  • F17C2203/0602—Wall structures; Special features thereof
  • F17C2203/0604—Liners
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
  • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
  • F17C2203/00—Vessel construction, in particular walls or details thereof
  • F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
  • F17C2203/0634—Materials for walls or layers thereof
  • F17C2203/0658—Synthetics
  • F17C2203/066—Plastics
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
  • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
  • F17C2203/00—Vessel construction, in particular walls or details thereof
  • F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
  • F17C2203/0634—Materials for walls or layers thereof
  • F17C2203/0658—Synthetics
  • F17C2203/0663—Synthetics in form of fibers or filaments
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
  • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
  • F17C2203/00—Vessel construction, in particular walls or details thereof
  • F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
  • F17C2203/0634—Materials for walls or layers thereof
  • F17C2203/0658—Synthetics
  • F17C2203/0663—Synthetics in form of fibers or filaments
  • F17C2203/0673—Polymers
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
  • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
  • F17C2203/00—Vessel construction, in particular walls or details thereof
  • F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
  • F17C2203/0634—Materials for walls or layers thereof
  • F17C2203/0658—Synthetics
  • F17C2203/0675—Synthetics with details of composition
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
  • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
  • F17C2209/00—Vessel construction, in particular methods of manufacturing
  • F17C2209/21—Shaping processes
  • F17C2209/2109—Moulding
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
  • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
  • F17C2209/00—Vessel construction, in particular methods of manufacturing
  • F17C2209/21—Shaping processes
  • F17C2209/2154—Winding
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
  • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
  • F17C2209/00—Vessel construction, in particular methods of manufacturing
  • F17C2209/23—Manufacturing of particular parts or at special locations
  • F17C2209/232—Manufacturing of particular parts or at special locations of walls
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
  • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
  • F17C2221/00—Handled fluid, in particular type of fluid
  • F17C2221/01—Pure fluids
  • F17C2221/012—Hydrogen
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
  • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
  • F17C2223/00—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel
  • F17C2223/01—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel characterised by the phase
  • F17C2223/0107—Single phase
  • F17C2223/0123—Single phase gaseous, e.g. CNG, GNC
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
  • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
  • F17C2223/00—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel
  • F17C2223/03—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel characterised by the pressure level
  • F17C2223/035—High pressure (>10 bar)
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
  • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
  • F17C2223/00—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel
  • F17C2223/03—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel characterised by the pressure level
  • F17C2223/036—Very high pressure (>80 bar)
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
  • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
  • F17C2260/00—Purposes of gas storage and gas handling
  • F17C2260/01—Improving mechanical properties or manufacturing
  • F17C2260/011—Improving strength
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
  • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
  • F17C2270/00—Applications
  • F17C2270/01—Applications for fluid transport or storage
  • F17C2270/0102—Applications for fluid transport or storage on or in the water
  • F17C2270/0105—Ships
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
  • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
  • F17C2270/00—Applications
  • F17C2270/01—Applications for fluid transport or storage
  • F17C2270/0165—Applications for fluid transport or storage on the road
  • F17C2270/0168—Applications for fluid transport or storage on the road by vehicles
  • F17C2270/0171—Trucks
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
  • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
  • F17C2270/00—Applications
  • F17C2270/01—Applications for fluid transport or storage
  • F17C2270/0165—Applications for fluid transport or storage on the road
  • F17C2270/0168—Applications for fluid transport or storage on the road by vehicles
  • F17C2270/0173—Railways
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
  • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
  • F17C2270/00—Applications
  • F17C2270/01—Applications for fluid transport or storage
  • F17C2270/0165—Applications for fluid transport or storage on the road
  • F17C2270/0168—Applications for fluid transport or storage on the road by vehicles
  • F17C2270/0176—Buses
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
  • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
  • F17C2270/00—Applications
  • F17C2270/01—Applications for fluid transport or storage
  • F17C2270/0165—Applications for fluid transport or storage on the road
  • F17C2270/0168—Applications for fluid transport or storage on the road by vehicles
  • F17C2270/0178—Cars
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
  • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
  • F17C2270/00—Applications
  • F17C2270/01—Applications for fluid transport or storage
  • F17C2270/0165—Applications for fluid transport or storage on the road
  • F17C2270/0184—Fuel cells
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
  • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
  • F17C2270/00—Applications
  • F17C2270/01—Applications for fluid transport or storage
  • F17C2270/0186—Applications for fluid transport or storage in the air or in space
  • F17C2270/0189—Planes
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/30—Hydrogen technology
  • Y02E60/32—Hydrogen storage

Definitions

• the present invention relates to the field of the manufacture of type IV pressure vessels, made of composite material, for the storage of gaseous hydrogen, for both fixed and mobile applications, such as, for example, storage infrastructures for hydrogen, transport of hydrogen for refueling, hydrogen rail vehicles, hydrogen buses, trucks, planes, boats and other hydrogen vehicles, and hydrogen cars.
• Hydrogen tanks for automotive applications, buses, trucks, trains, planes, boats, are already available but they do not yet meet all the expectations of manufacturers in the perspective of mass production of systems operating on hydrogen. This is true with regard to the manufacture of H 2 tanks but also for the deployment and use of fuel cell means of transport.
• Type IV composite pressure vessels for on-board hydrogen gas storage is only about 10% to 30% of the cost of the storage system, mass production capability is a major challenge for automotive integrators.
• the stage of polymerization (or hardening) of the matrix of the composite material ensuring the resistance to high pressure is the main stage which limits, today, the manufacturing speed of the tank.
• the composite material matrix of composite pressure vessels is usually an epoxy matrix.
• the polymerization time (or hardening) of the composite matrices for type IV tanks must be considerably reduced.
• the duration of the curing (or curing) process for a 700 bar pressure vessel is approximately 12-16 hours, which is too long for mass production as required. for the automotive industry.
• the present invention proposes a new composition for the composite material which takes into account the technical and regulatory constraints related to high-pressure composite tanks for the storage of on-board hydrogen.
• the present invention relates to a composition (C) comprising
• the hardener is an ionic liquid containing a phosphonium cation of formula P(R 1 R 2 R 3 R 4 ) + in which R 1 , R 2 , R 3 and R 4 , identical or different, represent an atom of hydrogen, an alkyl radical having 1 to 18 carbon atoms, an aryl radical having 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted.
• the type IV high-pressure tank made of composite material, consists of an internal shell made of polymer material, called bladder or liner in English, most often thermoplastic, with metal connectors, called bases or bosses in English, to one or at both ends.
• the bases ensure the connection of the tank with the storage system.
• the liner seals against hydrogen.
• This assembly is covered with a structuring composite material, providing structuring to the internal pressure, usually comprising a thermosetting matrix, most often an epoxy resin, and a reinforcement most often based on long fibers, for example, carbon or of glass.
• the present invention therefore aims to support the development of on-board storage systems for gaseous hydrogen (CGH 2 compressed gaseous hydrogen in English, CPV Composite Pressure Vessel) in pressurized tanks which are improved, in order to anticipate the future massive deployment of the aforementioned technologies, in particular by focusing on the composition of the composite material of the tank, and more specifically on the resin and its polymerization reaction which has a strong impact on the production rates over periods of more than 10 hours in general.
• gaseous hydrogen CGH 2 compressed gaseous hydrogen in English, CPV Composite Pressure Vessel
• the composition of the invention is particularly advantageous because it has a rapid polymerization (or hardening) in comparison with the compositions based on epoxy matrices used today, and this in particular thanks to the use of ionic phosphorus liquids as hardener.
• the duration of polymerization (or hardening) of the epoxy matrix in a composition according to the invention is less than 12 hours, less than 10 hours, in particular less than 8 hours, and more particularly less than 6 hours.
• Another object of the invention is a semi-finished product called a semi-finished product or towpreg in English, characterized in that it comprises
• F a bundle of fibers (F) selected from carbon, glass, aramid, silicon carbide, organic fibers and
• volumetric content of (F) is between 40 and 70% and that of (C) is between 30 and 60%.
• the bundle of fibers can be in the form of a sheet or aggregate of nonwoven bulk fibers, or in woven form.
• the semi-finished product or towpreg can be polymerized after the fibers (F) have been impregnated with the composition (C).
• the semi-finished product or towpreg may optionally be wound around a spool after the fibers (F) have been impregnated with the composition (C) and the polymerization (or hardening) thereof.
• Composition (C) and the semi-finished product or tow preg according to the invention can be used for the manufacture of type IV pressure tanks, made of composite material, for the on-board storage of gaseous hydrogen, in particular for applications at both stationary and mobile, such as hydrogen storage infrastructure, transport of hydrogen for refueling, hydrogen rail vehicles, buses, trucks, planes, ships and other hydrogen, and hydrogen cars.
• a subject of the invention is also the use of a composition (C) or of a semi-finished product, according to the invention, for the manufacture of a hydrogen tank, in particular a pressurized tank, of type IV , in composite material, for the on-board storage of gaseous hydrogen.
• Another object of the invention is a structure, made of composite material, comprising a semi-finished product or polymerized towpreg.
• the structure is a pressure vessel.
• the tank is a pressure tank, type IV, for the on-board storage of gaseous hydrogen.
• a subject of the invention is also a process for manufacturing a hydrogen tank, in particular a pressurized tank, of type IV, comprising a step of forming the desired shape of an unpolymerized composition according to the invention, followed by a stage of polymerization of this composition brought to the desired shape.
• a manufacturing process, according to the invention, of a hydrogen tank, in particular a pressurized tank, of type IV comprises a step of desired shaping of a composition according to the invention already polymerized.
• Yet another manufacturing process, according to the invention, of a hydrogen tank, in particular a pressurized tank, of type IV, comprises a step of desired shaping of the semi-finished product according to the invention, followed by a stage of polymerization of this shaped semi-finished product.
• the present invention relates to a composition (C) characterized in that it comprises
• the hardener is an ionic liquid containing a phosphonium cation of formula P(R 1 R 2 R 3 R 4 ) + in which R 1 , R 2 , R 3 and R 4 , identical or different, represent an atom of hydrogen, an alkyl radical having 1 to 18 carbon atoms, an aryl radical having 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted.
• alkyl within the meaning of the present invention, means a linear, branched or cyclic, saturated, optionally substituted, carbon radical comprising 1 to 18 carbon atoms, for example, 1 to 14 carbon atoms, for example 1 to 12 carbon atoms, for example 1 to 6 carbon atoms.
• saturated, linear or branched alkyl mention may be made, for example, of the methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl (C 11 ), dodecanyl (or dodecyl (C 12 ) radicals.
• cyclic alkyl mention may be made of the cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicylco[2,1,1]hexyl, bicyclo[2,2,1]heptyl radicals.
• aryl means a mono- or poly-cyclic aromatic substituent having 6 to 20 carbon atoms, for example, 6 to 10 carbon atoms. By way of indication, mention may be made of the phenyl, benzyl, naphthyl and phenanthrenyl groups.
• Alkyl and aryl radicals may be optionally substituted with one or more hydroxyl groups (-OH), one or more alkoxy groups (-O-alkyl); one or more aryloxy (-O-aryl) groups; one or more halogen atoms selected from fluorine, chlorine, bromine and iodine atoms; with alkyl, and aryl as defined in the context of the present invention.
• R 1 , R 2 , R 3 and R 4 identical or different, represent
• alkyl radical chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl dodecyl, tridecyl, tetradecyl, and their branched isomers,
• aryl radical chosen from phenyl, benzyl,
• alkyl and aryl radicals being optionally substituted.
• the phosphonium cation can be chosen from PH 4 + , P(CH 3 ) 4 + , P(Ph) 4 + , P(CH 3 )(Ph) 3 + , P(CH 2 OH) 4 + .
• the phosphonium cation can also be from PH 4 + , P(CH 3 ) 4 + , P(Ph) 4 + , P(CH 3 )(Ph) 3 + , P(CH 2 OH) 4 + , P(C 6 H 13 ) 3 (C 14 H 29 ) + .
• the phosphonium cation is trihexyl(tetradecyl)phosphonium or P(C 6 H 13 ) 3 (C 14 H 29 ) + .
• the ionic liquid contains a dicyanamide (C 2 N 3 ) - anion.
• composition (C) comprises 10 to 30 parts by mass of ionic liquid, per 100 parts by mass of epoxy resin present in the composition.
• composition (C) can be polymerized under the action of temperature depending on the desired application and the desired characteristics. Those skilled in the art will know how to choose and adapt these conditions.
• the composition comprises an ionic liquid which contains a phosphinate anion of formula (PO 2 R 5 R 6 ) - in which R 5 and R 6 , identical or different, represent a hydrogen atom, a alkyl radical having 1 to 18 carbon atoms, an aryl radical having 6 to 20 carbon atoms, said alkyl and aryl radicals being optionally substituted.
• R 5 and R 6 identical or different, represent
• alkyl radical chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and their branched isomers
• aryl radical chosen from phenyl, benzyl,
• alkyl and aryl radicals being optionally substituted.
• the phosphinate anion can be chosen from (PO 2 H 2 ) - , (PO 2 (CH 3 ) 2 ) - , (PO 2 (C 7 H 30 ) 2 ) - , (PO 2 Ph 2 ) - .
• the phosphinate anion can also be chosen from (PO 2 H 2 ) - , (PO 2 (CH 3 ) 2 ) - , (PO 2 (C 7 H 30 ) 2 ) - , (PO 2 Ph 2 ) - , the bis(2,4,4-trimethylpentyl)phosphinate or (PO 2 (CH 2 -CH(CH 3 )-CH 2 -C(CH 3 ) 3 ) 2 ) - .
• the composition comprises 5 to 20 parts by mass of ionic liquid, per 100 parts by mass of epoxy resin present in the composition.
• the epoxy resin (A) present in the composition can be, for example, of the bisphenol type, such as bisphenol A, bisphenol B, bisphenol F, bisphenol S, ortho-, meta-, para-cresol novolac.
• the epoxy resin (A) has a viscosity of between 1 Pa.s and 150 kPa.s at a temperature of between 20°C and 25°C.
• the epoxy resin (A) can be, for example, a resin with a viscosity of 16.9 kPa.s (+/- 20%) at 25°C and 113.0 kPa.s at 20°C.
• the viscosity is measured at a temperature between 20° C. and 25° C., using an ARES rheometer apparatus, from the company TA® instruments Brookfield LV DV I+ from the company BROOKFIELD ENGINEERING LABORATORIES, INC.
• the ARES rheometer uses a plane/plane geometry with 25 mm (upper geometry) and 40 mm (lower geometry) aluminum discs.
• the composition is deposited hot (60° C.) on the geometries then cooled to a temperature of between 20° C. and 25° C. to carry out the viscosity measurement.
• the “DFS” Dynamic Frequency Sweep (strain controlled) 1-100 rad/s test is carried out with a strain of approximately 1%.
• the viscosity measurement is taken for a frequency of 1 rad/s.
• composition according to the invention can be prepared by a mixture of components (A) and (B) as indicated in the examples.
• the method consists in mixing an epoxy resin (A) and an ionic liquid (B) as defined above, until a homogeneous composition is obtained, at a temperature which avoids the initiation of the polymerization of (A).
• the composition can be prepared in a simple (glass) reactor equipped with a stirring blade and under air.
• the temperature can be controlled by a heating plate and a silicone oil bath.
• Continuous mixing is a process of continuously metering ingredients directly into the mixing zone and therefore generating a continuous stream of mixed product at the outlet of the mixer. This principle guarantees perfect control of the meeting point of the ingredients and therefore a unique distribution quality for the mixed product.
• the product obtained is therefore in the form of a homogeneous mixture.
• Any continuous mixer known to those skilled in the art may be suitable for the manufacture of the composition.
• ionic liquids as hardeners in a composition according to the invention allows crosslinking via a catalytic mechanism and not an addition.
• ionic liquids make it possible to reduce the quantity of polymerization (or hardening) agent necessary for the complete crosslinking of the epoxy matrix (ie 20-50 parts per 100 parts resin or phr, for standard amine systems).
• the ionic liquid under the effect of the temperature, will allow the opening of the oxirane ring by the nucleophilic attack of the anion on the ⁇ carbon of this function.
• a second so-called propagation step consists of the homopolymerization of the alkoxide units formed on the oxirane rings.
• Another object of the invention is a semi-finished product also called a semi-finished product or towpreg in English, characterized in that it comprises
• F a bundle of fibers (F) selected from carbon, glass, aramid, silicon carbide, organic fibers and
• volumetric content of (F) is between 40 and 70% and that of (C) is between 30 and 60%.
• organic fibers fibers based on carbon and hydrogen. They can be natural (cellulose, silk, linen), derived from cellulose (cellulose acetate, etc.), synthetic (polyester, polyethylene, etc.).
• the bundle of fibers can be in the form of a sheet or aggregate of nonwoven bulk fibers, or in woven form.
• the reinforcing fiber bundle preferably comprises 1,000 to 70,000 filaments having a diameter of 3 to 100 ⁇ m.
• the fibers (D) are carbon fibers.
• the semi-finished product also called a semi-finished product or towpreg in English, as its name suggests, is an intermediate product, intended to be used for the manufacture of structures in composite material, such as, for example, pressure vessels of the type IV in composite material, in particular after hot molding.
• the semi-finished product or towpreg can be manufactured by a continuous production process comprising the steps of
• composition (C) comprising the resin (A) and the ionic liquid (B) to a temperature between 40 and 60°C, and
• the continuous production is carried out without interruption, by a continuous flow of composition and fibers (F), and is concentrated in a single place.
• the final product here the semi-finished product or towpreg, is unloaded without interrupting the process.
• the continuous impregnation of the bundle of fibers (F) by the composition (C) takes place at a temperature which can range from 20°C to 80°C.
• the duration of this impregnation can range from a few seconds to a few minutes, for example, 10 seconds to 5 minutes.
• step (ii) the impregnated fibers are cooled to a temperature below 30°C.
• step (ii) the impregnation of the bundle of fibers (F) by the composition (C) on can be done in several ways, by methods well known to those skilled in the art, including by spraying, by immersion or transfer.
• the semi-finished product or towpreg can be stored as is.
• the semi-finished product can also be rolled up, for example around a reel.
• the semi-finished product can be used for filament winding on a polymer bladder or liner, in particular a polyethylene or polyamide bladder or liner.
• the bladder can be that of a tank, for example a hydrogen tank, in particular a tank, under pressure, of type IV, in composite material, for the on-board storage of gaseous hydrogen.
• the invention also relates to the use of a composition (C) according to the invention, or of a semi-finished product or towpreg according to the invention, for the manufacture of a hydrogen tank, in particular a tank, under pressure, type IV, made of composite material, for the on-board storage of gaseous hydrogen, in particular for both fixed and mobile applications, such as, for example, hydrogen storage infrastructures, hydrogen transport for refueling, hydrogen rail vehicles, buses, trucks, planes, boats and other hydrogen vehicles, and hydrogen cars.
• a composition (C) according to the invention or of a semi-finished product or towpreg according to the invention, for the manufacture of a hydrogen tank, in particular a tank, under pressure, type IV, made of composite material, for the on-board storage of gaseous hydrogen, in particular for both fixed and mobile applications, such as, for example, hydrogen storage infrastructures, hydrogen transport for refueling, hydrogen rail vehicles, buses, trucks, planes, boats and other hydrogen vehicles, and hydrogen cars.
• the invention also relates to a process for manufacturing a hydrogen tank, in particular a pressurized tank, of type IV, comprising a step of desired shaping of a composition (C) according to the invention.
• the composition (C) is introduced unpolymerized into a mold having the desired size and shape of the hydrogen reservoir to be obtained and then is polymerized.
• the already polymerized composition (C) is brought into the desired size and shape of the hydrogen tank, for example by machining.
• Another object of the invention is a structure, made of composite material, comprising a semi-finished product or polymerized towpreg.
• the polymerization can be done by the polymerization methods known to those skilled in the art, for example under the action of temperature.
• the structure is a pressure vessel.
• the tank is a pressure tank, type IV, for the on-board storage of gaseous hydrogen.
• the polymerized towpreg is rolled up on a polymer bladder or liner, in particular a polyethylene bladder or liner.
• the polymerized towpreg is rolled up on a polymer bladder or liner, in particular a polyamide bladder or liner.
• the tank is a pressure tank, type IV, for the on-board storage of gaseous hydrogen.
• the invention also relates to a process for manufacturing a hydrogen tank, in particular a pressurized tank, of type IV, comprising a step of shaping the desired semi-finished product according to the invention, followed by a stage of polymerization of the semi-finished product according to claim 9, shaped.
• composition (C) according to the invention has a rapid cure (only a few hours) during the manufacture of composite tanks under type IV pressure for the on-board storage of gaseous hydrogen.
• the rapid curing of the composition is essentially due to the use of the ionic liquid as a hardener.
• composition of the invention comprises an epoxy resin (A) because this type of thermosetting polymer is the most commonly used for the manufacture of pressure tanks for the on-board storage of hydrogen.
• tow-preg in English by the thermofusible or hot-melt method. in English, by impregnation of carbon fiber bundles/sheets, for example.
• This semi-finished product or tow-preg which can be in coil form, is then used to manufacture the tanks. Once deposited around the bladder or liner, most often by filament winding, the epoxy matrix is then polymerized most often in an oven or tunnel oven. The tanks thus obtained can be approved according to the criteria of the regulations currently in force (406 2010, R134).
• the SR 1228 resin marketed by the Sicomin company, is of the hot-melt type (or hot-melt in English) and has a viscosity of 113 kPa.s at 20°C.
• Sicomin SR 1228 resin is semi-solid and non-crystalline at room temperature (20°C - 25°C). Therefore, it is necessary to heat it to use it at around 50°C.
• the resin is introduced into a thermostatically controlled reactor and then the ionic liquid Cyphos ® LI 105 (trihexyl (tetradecyl) phosphonium dicyanamide), marketed by the company Strem Chemicals, is added at a level of 15 parts by weight or pp or phr in English (15 parts Cyphos ® LI 105 for 100 parts of SR 1228 resin). The mixture is stirred for about 30 minutes at 60°C.
• Cyphos ® LI 105 trihexyl (tetradecyl) phosphonium dicyanamide
• composition according to the invention is obtained and can be used for impregnating reinforcing fibers.
• the composition is sprayed continuously onto a wick of TORAYCA T720 carbon fiber from the company Toray® at a temperature of between 60 and 80° C. maximum.
• the wick impregnated with the composition can then be rolled up in the form of a semi-finished product or tow-preg and left to cool as it is. Storage should be in a clean, dry area, away from light, up to a temperature of 20°C. Under these conditions, and depending on the ionic liquid used, the invention makes it possible to guarantee a duration of use of the semi-product or tow-preg of at least two weeks and up to more than four weeks.
• the curing cycles proposed for the polymerization of a composition as prepared above are 5 hours with a polymerization step lasting 0.5 hours at 100°C, then 1.5 hours at 120°C, then 2 hours at 130°C .
• compositions according to the invention can be used for the preparation of tow-preg which can be used within 2 to 4 weeks for filament winding applications for type IV hydrogen tanks. These compositions respond to the problem of curing times by offering polymerization times on thick composite (> 30 mm) of less than 5 hours.
• these compositions can be used with both PE (polyethylene) and PA (polyamide) liners, the two main polymer materials used for the manufacture of hydrogen tanks.
• PE polyethylene
• PA polyamide

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• General Engineering & Computer Science (AREA)
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• 2021
  • 2021-11-17 FR FR2112167A patent/FR3129153B1/fr active Active
• 2022
  • 2022-11-16 JP JP2024529166A patent/JP2024541387A/ja active Pending
  • 2022-11-16 KR KR1020247016261A patent/KR20240141158A/ko active Pending
  • 2022-11-16 WO PCT/EP2022/082161 patent/WO2023088977A1/fr not_active Ceased
  • 2022-11-16 US US18/709,986 patent/US20250002638A1/en active Pending
  • 2022-11-16 EP EP22818336.4A patent/EP4433521A1/fr active Pending

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