EP4097387A1 - Multilayer structure for transporting or storing hydrogen - Google Patents

Multilayer structure for transporting or storing hydrogen

Info

Publication number
EP4097387A1
EP4097387A1 EP21708270.0A EP21708270A EP4097387A1 EP 4097387 A1 EP4097387 A1 EP 4097387A1 EP 21708270 A EP21708270 A EP 21708270A EP 4097387 A1 EP4097387 A1 EP 4097387A1
Authority
EP
European Patent Office
Prior art keywords
weight
layer
composition
polymer
multilayer structure
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21708270.0A
Other languages
German (de)
French (fr)
Inventor
Nicolas Dufaure
Patrick Dang
Antoine GOUPIL
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Arkema France SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Arkema France SA filed Critical Arkema France SA
Publication of EP4097387A1 publication Critical patent/EP4097387A1/en
Pending legal-status Critical Current

Links

Classifications

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    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0078—Composite solid storage mediums, i.e. coherent or loose mixtures of different solid constituents, chemically or structurally heterogeneous solid masses, coated solids or solids having a chemically modified surface region
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    • B32B38/08—Impregnating
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    • B29C53/58—Winding and joining, e.g. winding spirally helically
    • B29C53/60—Winding and joining, e.g. winding spirally helically using internal forming surfaces, e.g. mandrels
    • B29C53/602—Winding and joining, e.g. winding spirally helically using internal forming surfaces, e.g. mandrels for tubular articles having closed or nearly closed ends, e.g. vessels, tanks, containers
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C—CHEMISTRY; METALLURGY
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    • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
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    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
    • 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
    • F17C2203/0602—Wall structures; Special features thereof
    • F17C2203/0612—Wall structures
    • F17C2203/0614—Single wall
    • F17C2203/0619—Single wall with two layers
    • 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
    • F17C2203/0675—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
    • 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
    • F17C2223/036—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
    • 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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P90/00—Enabling technologies with a potential contribution to greenhouse gas [GHG] emissions mitigation
    • Y02P90/45—Hydrogen technologies in production processes

Definitions

  • TITLE MULTI-LAYER STRUCTURE FOR THE TRANSPORT OR STORAGE OF
  • the present patent application relates to composite multilayer structures for the transport, distribution or storage of hydrogen, in particular for the distribution or storage of hydrogen, and their manufacturing process.
  • Hydrogen tanks are a subject that is currently attracting a lot of interest from many manufacturers, especially in the automotive field.
  • One of the goals is to offer vehicles that pollute less and less.
  • electric or hybrid vehicles comprising a battery aim to gradually replace thermal vehicles, such as gasoline or diesel vehicles.
  • thermal vehicles such as gasoline or diesel vehicles.
  • the battery is a relatively complex component of the vehicle.
  • the electric vehicle still suffers today from several problems, namely the autonomy of the battery, the use in these rare earth batteries whose resources are not inexhaustible, recharging times much longer than the durations. tank filling, as well as a problem of electricity production in the different countries to be able to recharge the batteries.
  • Hydrogen therefore represents an alternative to the electric battery since hydrogen can be transformed into electricity by means of a fuel cell and thus power electric vehicles.
  • Hydrogen tanks generally consist of a metal casing (liner or sealing layer) which must prevent the permeation of hydrogen.
  • liner or sealing layer One of the types of tanks being considered, called Type IV, is based on a thermoplastic liner around which a composite is wrapped.
  • thermoplastic resin liner or sealing sheath
  • a reinforcing structure made up of fibers (glass, aramid, carbon). called sheath or reinforcing layer which allow to work at much higher pressures while reducing the mass and avoiding the risk of explosive rupture in the event of severe external attacks.
  • the permeability of the liner is indeed a key factor in limiting hydrogen losses from the tank;
  • the first generation of type IV tanks used a liner based on high density polyethylene (HDPE).
  • HDPE high density polyethylene
  • HDPE has the drawback of having too low a melting temperature and high hydrogen permeability, which is a problem with the new thermal withstand requirements and does not allow the filling speed of the tank to be increased. tank.
  • PA6 polyamide
  • International application WO 2016/166326 describes a method of manufacturing an internal shell of a type IV composite tank delimiting an internal cavity intended to receive a pressurized fluid and comprising at least one metal base, and a subsequent step of depositing, on the outer surface of the inner shell, a fibrous material to form the outer shell of the reservoir.
  • thermoplastic material being a material chosen from the group consisting of a modified nylon 6 and nylon 11.
  • French application FR2923575 describes a reservoir for storing fluid under high pressure comprising at each of its ends along its axis a nozzle metal end, a liner enveloping said end caps and a structural layer of fiber impregnated with thermosetting resin enveloping said liner.
  • the matrix of the composite in order to optimize its mechanical resistance at high temperature and on the other hand the material composing the sealing sheath, in order to optimize its processing temperature.
  • the possible modification of the composition of the material composing the sealing sheath, which will be made, must not result in a significant increase in the manufacturing temperature (extrusion-blow molding, injection, rotomoulding, etc.) of this liner, compared to what is practiced today.
  • the present invention therefore relates to a multilayer structure intended for the transport, distribution and storage of hydrogen, comprising, from the inside to the outside, a sealing layer (1) and at least one composite reinforcing layer.
  • thermoplastic polyamide PA11 polymer comprising a limited proportion of impact modifier and plasticizer, for the sealing layer, with a different polymer for the matrix of the composite and in particular a epoxy resin or epoxy-based, wound on the waterproofing layer, made it possible to obtain a structure suitable for the transport, distribution or storage of hydrogen and in particular an increase in the maximum temperature of use up to 120 ° C, thus increasing the tank filling speed.
  • thermoplastic polymer PA11 (or polyamide 11) is marketed by the company Arkema and is obtained in particular from the polycondensation of 11-amino undecanoic acid.
  • multilayer structure is meant a tank comprising or made up of several layers, namely a waterproofing layer and several reinforcing layers, or a waterproofing layer and a reinforcing layer.
  • the multilayer structure is therefore meant to the exclusion of a pipe or tube.
  • Poly ether block amide are copolymers with amide units (Ba1) and polyether units (Ba2), said amide unit (Ba1) corresponding to an aliphatic repeating unit chosen from a unit obtained from at least one amino acid or a unit obtained from at least one lactam, or an XY unit obtained from polycondensation:
  • diamine being preferably chosen from a linear or branched aliphatic diamine or a mixture thereof, and
  • dicarboxylic acid being preferably chosen from: a linear or branched aliphatic dicacid, or a mixture of these, said diamine and said dicacid comprising from 4 to 36 carbon atoms, advantageously from 6 to 18 carbon atoms; said polyether units (Ba2) being in particular derived from at least one polyalkylene ether polyol, in particular a polyalkylene ether diol.
  • Nucleating agents are known to those skilled in the art and refer to a substance which, when incorporated into a polymer, forms nuclei for crystal growth in the molten polymer.
  • They can be chosen, for example, from micro talc, carbon black, silica, titanium dioxide and nanoclays.
  • PA6 is excluded from said composition.
  • said multilayer structure consists of two layers, a sealing layer and a reinforcing layer.
  • the waterproofing layer is the innermost layer relative to the composite reinforcement layers which are the outermost layers.
  • the tank can be a tank for the mobile storage of hydrogen, i.e. on a truck for the transport of hydrogen, on a car for the transport of hydrogen and the supply of hydrogen d '' a fuel cell for example, on a train for the supply of hydrogen or on a drone for the supply of hydrogen, but it can also be a stationary storage tank for hydrogen in a station for the distribution of hydrogen to vehicles.
  • the sealing layer (1) is impermeable to hydrogen at 23 ° C, that is to say that the permeability to hydrogen at 23 ° C is less than 500 cc.mm/m2. 24h. .atm at 23 ° C under 0% relative humidity (RH).
  • the composite reinforcing layer (s) is (are) wound (s) around the waterproofing layer by means of tapes (or tapes or rovings) of fibers impregnated with polymer which are deposited, for example, by filament winding.
  • the polymers are different.
  • the polymers of the reinforcing layers are identical, there may be several layers present, but advantageously, only one reinforcing layer is present and which then has at least one complete winding around the waterproofing layer.
  • the other composite reinforcement layers may or may not also adhere to each other.
  • a waterproofing layer and a reinforcing layer are present and do not adhere to each other.
  • a sealing layer made of PA11 and a reinforcing layer are present and do not adhere to each other and the reinforcing layer consists of a fibrous material in the form of continuous fibers impregnated with a composition. mainly comprising at least one polymer P2j, in particular an epoxy resin or an epoxy-based resin.
  • a waterproofing layer and a reinforcing layer are present and do not adhere to each other and the reinforcing layer consists of a fibrous material in the form of continuous fibers impregnated with a composition mainly comprising a P2j polymer which is an epoxy or epoxy-based resin.
  • epoxy-based throughout the description means that the epoxy represents at least 50% by weight of the matrix.
  • the waterproofing layer consists of a composition comprising predominantly at least one thermoplastic polymer PA11.
  • said at least one polymer is present in more than 50% by weight relative to the total weight of the composition and of the matrix.
  • said at least one majority polymer is present at more than 60% by weight, in particular at more than 70% by weight, particularly at more than 80% by weight, more particularly greater than or equal to 90% by weight 90% by weight, relative to the total weight of the composition and the matrix.
  • Said composition can also comprise impact modifiers of up to 15% by weight relative to the total weight of the composition and / or a plasticizer and / or additives.
  • the additives can be selected from another polymer, an antioxidant, a heat stabilizer, a UV absorber, a light stabilizer, a lubricant, an inorganic filler, a flame retardant, a colorant, carbon black and carbonaceous nanofillers, with the exception of a nucleating agent, in particular the additives are chosen from an antioxidant, a heat stabilizer, a UV absorber, a light stabilizer, a lubricant, an inorganic filler, a flame retardant, a colorant, carbon black and carbonaceous nanofillers, except for a nucleating agent.
  • Said other polymer can be another semi-crystalline thermoplastic polymer or a different polymer and in particular an EVOH (Ethylene vinyl alcohol).
  • EVOH Ethylene vinyl alcohol
  • said composition comprises mainly said thermoplastic polymer PA11, from 0 to less than 15% of impact modifier, in particular from 0 to 12% of impact modifier, from 0 to 1.5% of plasticizer and from 0 to 5% by weight additives, the sum of the constituents of the composition being equal to 100%.
  • said composition comprises said thermoplastic polymer PA11, from 0 to less than 15% of impact modifier, in particular from 0 to 12% of impact modifier, from 0 to 1.5% of plasticizer and from 0 to 5% by weight of 'additives, the sum of the constituents of the composition being equal to 100%.
  • said composition consists of said thermoplastic polymer PA11 predominantly, from 0 to less than 15% by weight of impact modifier, in particular from 0 to 12% by weight of impact modifier, from 0 to 1.5% by weight of plasticizer and from 0 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition consists of said thermoplastic polymer PA11, from 0 to less than 15% by weight of impact modifier, in particular from 0 to 12% by weight of impact modifier, from 0 to 1.5% by weight of plasticizer and of 0 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition comprises said thermoplastic polymer PA11 predominantly, from 0.1 to less than 15% of impact modifier, in particular from 0.1 to 12% of impact modifier, from 0 to 1.5% of plasticizer and from 0 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition comprises said thermoplastic polymer PA11, from 0.1 to less than 15% of impact modifier, in particular from 0.1 to 12% of impact modifier, from 0 to 1.5% of plasticizer and from 0 to 5 % by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition consists of said thermoplastic polymer PA11 predominantly, from 0.1 to less than 15% by weight of impact modifier, in particular from 0.1 to 12% by weight of impact modifier, from 0 to 1.5% by weight. weight of plasticizer and from 0 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition consists of said thermoplastic polymer PA11, from 0.1 to less than 15% by weight of impact modifier, in particular from 0.1 to 12% by weight of impact modifier, from 0 to 1.5% by weight of plasticizer and from 0 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition comprises mainly said thermoplastic polymer PA11, from 0.1 to less than 15% of impact modifier, in particular from 0.1 to 12% of impact modifier, from 0.1 to 1.5% of plasticizer and of 0 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition comprises said thermoplastic polymer PA11, from 0.1 to less than 15% of impact modifier, in particular from 0.1 to 12% of impact modifier, from 0 to 1.5% of plasticizer and from 0 to 5 % by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition consists mainly of said thermoplastic polymer PA11, from 0.1 to less than 15% by weight of impact modifier, in particular from 0.1 to 12% by weight of impact modifier, from 0.1 to 1.5% by weight of impact modifier, in particular from 0.1 to 12% by weight of impact modifier, from 0.1 to 1.5. % by weight of plasticizer and from 0 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition consists of said thermoplastic polymer PA11, from 0.1 to less than 15% by weight of impact modifier, in particular from 0.1 to 12% by weight of impact modifier, from 0.1 to 1.5% by weight of plasticizer and from 0 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition comprises said thermoplastic polymer PA11 predominantly, from 0.1 to less than 15% of impact modifier, in particular from 0.1 to 12% of impact modifier, from 0.1 to 1.5% of plasticizer and of 0.1 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition comprises said thermoplastic polymer PA11, from 0.1 to less than 15% of impact modifier, in particular from 0.1 to 12% of impact modifier, from 0 to 1.5% of plasticizer and 0.1 at 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition consists mainly of said thermoplastic polymer PA11, from 0.1 to less than 15% by weight of impact modifier, in particular from 0.1 to 12% by weight of impact modifier, from 0.1 to 1.5% by weight of impact modifier, in particular from 0.1 to 12% by weight of impact modifier, from 0.1 to 1.5. % by weight of plasticizer and from 0.1 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition consists of said thermoplastic polymer PA11, from 0.1 to less than 15% by weight of impact modifier, in particular from 0.1 to 12% by weight of impact modifier, from 0.1 to 1.5% by weight of plasticizer and from 0.1 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition comprises an impact modifier from 0.1 to less than 15% by weight, in particular from 0.1 to 12% by weight of impact modifier, in particular from 5 to 12% by weight relative to the total weight of the composition.
  • said composition is devoid of impact modifier.
  • said composition therefore comprises said thermoplastic polymer PA11 predominantly, from 0 to 1.5% of plasticizer and from 0.1 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100 %.
  • said composition therefore comprises said thermoplastic polymer PA11, from 0 to 1.5% of plasticizer and from 0.1 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition consists mainly of said thermoplastic polymer PA11, from 0 to 1.5% of plasticizer and from 0.1 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • the majority PA11 is mixed with another polyamide.
  • said composition consists of said thermoplastic polymer PA11, from 0 to 1.5% of plasticizer and from 0.1 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition is devoid of plasticizer.
  • said composition therefore comprises said thermoplastic polymer PA11 predominantly, from 0.1 to less than 15% of impact modifier, in particular from 0.1 to 12% of impact modifier and from 0.1 to 5% in weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition therefore comprises said thermoplastic polymer PA11, from 0.1 to less than 15% of impact modifier, in particular from 0.1 to 12% of impact modifier and from 0.1 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition consists predominantly of said thermoplastic polymer PA11, from 0.1 to less than 15% of impact modifier, in particular from 0.1 to 12% of impact modifier and from 0.1 to 5% by weight of additives. , the sum of the constituents of the composition being equal to 100%.
  • the majority PA11 is mixed with another polyamide.
  • said composition consists of said thermoplastic polymer PA11, from 0.1 to less than 15% of impact modifier, in particular from 0.1 to 12% of impact modifier and from 0.1 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition is devoid of impact modifier and plasticizer.
  • said composition therefore comprises said thermoplastic polymer PA11 predominantly and from 0.1 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition therefore comprises said thermoplastic polymer PA11 and from 0.1 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition consists of said thermoplastic polymer PA11 predominantly and from 0.1 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • the majority PA11 is mixed with another polyamide.
  • said composition consists of said thermoplastic polymer PA11 and from 0.1 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
  • said composition comprises an impact modifier of 0.1 to less than 15% by weight, in particular from 0.1 to 12% by weight, in particular from 5 to 12% by weight of impact modifier and said composition is devoid of plasticizer relative to the total weight of the composition.
  • said composition comprises an impact modifier from 0.1 to less than 15% by weight, in particular from 0.1 to 12% by weight of impact modifier, in particular from 5 to 12% by weight and from 0.1 to 1.5% by weight of plasticizer relative to the total weight of the composition.
  • the number-average molecular mass Mn of said thermoplastic polyamide PA11 polymer is preferably in a range going from 10,000 to 85,000, in particular from 10,000 to 60,000, preferably from 10,000 to 50,000, even more preferably from 12,000 to 50,000. These Mn values may correspond to inherent viscosities greater than or equal to 0.8 as determined in m-cresol according to standard ISO 307: 2007 but by changing the solvent (use of m-cresol instead of sulfuric acid and the temperature being 20 ° C).
  • Polyamide PA11 is a homopolyamide but it would not be departing from the scope of the invention if the constituent composition of the waterproofing layer included a copolyamide based on PA11 in which the PA11 unit is predominant, that is to say greater than 50% by weight, in particular greater than 60% by weight, greater than 70% by weight, greater than 80% by weight, greater than 90% by weight, relative to the total of the units of said copolyamide or a mixture thereof .
  • the polyamide PA11 is a homopolyamide.
  • the impact modifier can be any impact modifier from the moment when a polymer of lower modulus than that of the resin, exhibiting good adhesion with the matrix, so as to dissipate the cracking energy.
  • the impact modifier is advantageously constituted by a polymer having a flexural modulus of less than 100 MPa measured according to the ISO 178 standard and of Tg less than 0 ° C (measured according to the 11357-2 standard at the inflection point of the DSC thermogram ), in particular a polyolefin.
  • PEBAs are excluded from the definition of impact modifiers.
  • the polyolefin of the impact modifier can be functionalized or non-functionalized or be a mixture of at least one functionalized and / or at least one non-functionalized.
  • polystyrene resin For simplicity, the polyolefin has been designated by (B) and functionalized polyolefins (B1) and unfunctionalized polyolefins (B2) have been described below.
  • An unfunctionalized polyolefin (B2) is conventionally a homopolymer or copolymer of alpha olefins or diolefins, such as, for example, ethylene, propylene, butene-1, octene-1, butadiene.
  • alpha olefins or diolefins such as, for example, ethylene, propylene, butene-1, octene-1, butadiene.
  • LDPE low density polyethylene
  • HDPE high density polyethylene
  • LLDPE linear low density polyethylene, or linear low density polyethylene
  • VLDPE very low density polyethylene, or very low density polyethylene
  • metallocene polyethylene metallocene polyethylene
  • ethylene / alpha-olefin copolymers such as ethylene / propylene, EPR (abbreviation of ethylene-propylene-rubber) and ethylene / propylene / diene (EPDM).
  • EPR abbreviation of ethylene-propylene-rubber
  • EPDM ethylene / propylene / diene
  • SEBS ethylene-butene / styrene
  • SBS styrene / butadiene / styrene
  • SIS styrene / isoprene / styrene
  • SEPS styrene / ethylene-propylene / styrene
  • the functionalized polyolefin (B1) can be a polymer of alpha olefins having reactive units (the functionalities); such reactive units are acid, anhydride or epoxy functions.
  • polyolefins (B2) grafted or co- or ter polymerized with unsaturated epoxides such as glycidyl (meth) acrylate, or with carboxylic acids or the corresponding salts or esters such as (meth) acrylic acid (the latter being able to be totally or partially neutralized by metals such as Zn, etc.) or alternatively by carboxylic acid anhydrides such as maleic anhydride.
  • a functionalized polyolefin is for example a PE / EPR mixture, the weight ratio of which can vary widely, for example between 40/60 and 90/10, said mixture being co-grafted with an anhydride, in particular maleic anhydride, according to a degree of grafting, for example from 0.01 to 5% by weight.
  • the functionalized polyolefin (B1) can be chosen from the following (co) polymers, grafted with maleic anhydride or glycidyl methacrylate, in which the degree of grafting is for example from 0.01 to 5% by weight:
  • - ethylene / alpha-olefin copolymers such as ethylene / propylene, EPR (abbreviation of ethylene-propylene-rubber) and ethylene / propylene / diene (EPDM).
  • EPR abbreviation of ethylene-propylene-rubber
  • EPDM ethylene / propylene / diene
  • SEBS ethylene-butene / styrene
  • SBS styrene / butadiene / styrene
  • SIS isoprene / styrene
  • SEPS styrene / ethylene-propylene / styrene
  • alkyl (meth) acrylate copolymers containing up to 40% by weight of alkyl (meth) acrylate;
  • the functionalized polyolefin (B1) can also be chosen from ethylene / propylene copolymers predominantly in propylene grafted with maleic anhydride then condensed with mono-amine polyamide (or a polyamide oligomer) (products described in EP-A-0342066) .
  • the functionalized polyolefin (B1) can also be a co- or ter polymer of at least the following units: (1) ethylene, (2) alkyl (meth) acrylate or vinyl ester of saturated carboxylic acid and (3) anhydride such as maleic anhydride or (meth) acrylic acid or epoxy such as glycidyl (meth) acrylate.
  • (meth) acrylic acid can be salified with Zn or Li.
  • alkyl (meth) acrylate in (B1) or (B2) denotes methacrylates and acrylates of C1 to C8 alkyl, and may be chosen from methyl acrylate, ethyl acrylate , n-butyl acrylate, isobutyl acrylate, ethyl-2-hexyl acrylate, cyclohexyl acrylate, methyl methacrylate and ethyl methacrylate.
  • the aforementioned polyolefins (B1) can also be crosslinked by any suitable process or agent (diepoxy, diacid, peroxide, etc.); the term functionalized polyolefin also includes mixtures of the aforementioned polyolefins with a difunctional reagent such as as diacid, dianhydride, diepoxy, etc. capable of reacting with these or mixtures of at least two functionalized polyolefins capable of reacting with each other.
  • a difunctional reagent such as as diacid, dianhydride, diepoxy, etc.
  • copolymers mentioned above, (B1) and (B2) can be copolymerized in a random or block fashion and have a linear or branched structure.
  • the molecular weight, the MFI number, the density of these polyolefins can also vary to a large extent, which will be appreciated by those skilled in the art.
  • MFI short for Melt Flow Index, is the melt flow index. It is measured according to standard ASTM 1238.
  • the unfunctionalized polyolefins (B2) are chosen from homopolymers or copolymers of polypropylene and any homopolymer of ethylene or copolymer of ethylene and of a comonomer of higher alpha olefinic type. such as butene, hexene, octene or 4-methyl 1-Pentene.
  • PPs high density PE, medium density PE, linear low density PE, low density PE, very low density PE.
  • polyethylenes are known to those skilled in the art as being produced according to a “radical” process, according to a “Ziegler” type catalysis or, more recently, according to a so-called “metallocene” catalysis.
  • the functionalized polyolefins (B1) are chosen from any polymer comprising alpha olefinic units and units bearing polar reactive functions such as epoxy, carboxylic acid or carboxylic acid anhydride functions.
  • polymers mention may be made of the ter polymers of ethylene, of alkyl acrylate and of maleic anhydride or of glycidyl methacrylate, such as Lotader® from the Applicant or polyolefins grafted with l.
  • maleic anhydride such as Orevac® from the Applicant as well as ter polymers of ethylene, of alkyl acrylate and of (meth) acrylic acid.
  • Mention may also be made of homopolymers or copolymers of polypropylene grafted with a carboxylic acid anhydride and then condensed with polyamides or mono-amino polyamide oligomers.
  • said constituent composition of said sealant layer or layers is devoid of polyether block amide (PEBA).
  • PEBAs are therefore excluded from the impact modifiers.
  • said transparent composition is devoid of core-shell particles or “core-shell” core-shell polymers.
  • core-shell particle it is necessary to understand a particle of which the first layer forms the core and the second or all of the following layers form the respective shell.
  • the core-shell particle can be obtained by a multi-step process comprising at least two steps. Such a method is described for example in documents US2009 / 0149600 or EP0722961. Regarding the plasticizer
  • the plasticizer can be a plasticizer commonly used in compositions based on polyamide (s).
  • a plasticizer which has good thermal stability so that no fumes are formed during the stages of mixing the various polymers and of processing the composition obtained.
  • this plasticizer can be chosen from: benzene sulfonamide derivatives such as n-butyl benzene sulfonamide (BBSA), ortho and para isomers of ethyl toluene sulfonamide (ETSA), N-cyclohexyl toluene sulfonamide and N- (2-hydroxypropyl) benzenesulfonamide (HP-BSA), esters of hydroxybenzoic acids such as 2-ethylhexyl para-hydroxybenzoate
  • BBSA n-butyl benzene sulfonamide
  • ETSA ethyl toluene sulfonamide
  • HP-BSA N- (2-hydroxypropyl) benzenesulfonamide
  • esters of hydroxybenzoic acids such as 2-ethylhexyl para-hydroxybenzoate
  • EHPB 2-decylhexyl para-hydroxybenzoate
  • HDPB 2-decylhexyl para-hydroxybenzoate
  • esters or ethers of tetrahydrofurfuryl alcohol such as oligoethyleneoxy-tetrahydrofurfurylalcohol
  • esters of citric acid or hydroxymalonic acid such as oligoethylene oxymalonate.
  • a preferred plasticizer is n-butyl benzene sulfonamide (BBSA).
  • Another more particularly preferred plasticizer is N- (2-hydroxy-propyl) benzene sulfonamide (HP-BSA).
  • HP-BSA N- (2-hydroxy-propyl) benzene sulfonamide
  • the polymer P2j can be a thermoplastic polymer or a thermosetting polymer.
  • One or more composite reinforcement layers may or may be present.
  • the term “predominantly” means that said at least one polymer is present in more than 50% by weight relative to the total weight of the composition and of the matrix of the composite.
  • said at least one major polymer is present at more than 60% by weight, in particular at more than 70% by weight, particularly at more than 80% by weight, more particularly greater than or equal to 90% by weight, relative to the weight total composition
  • Said composition can also comprise impact modifiers and / or additives.
  • the additives can be selected from an antioxidant, a heat stabilizer, a UV absorber, a light stabilizer, a lubricant, an inorganic filler, a flame retardant, a plasticizer and a colorant, except for a nucleating agent.
  • said composition consists of said thermoplastic polymer P2j predominantly, from 0 to 15% by weight of impact modifier, in particular from 0 to 12% by weight of impact modifier, from 0 to 5% by weight of additives, the sum of constituents of the composition being equal to 100% by weight.
  • Said at least one majority polymer of each layer may be identical or different.
  • a single major polymer is present at least in the composite reinforcing layer and which does not adhere to the waterproofing layer.
  • each reinforcing layer comprises the same type of polymer, in particular an epoxy or epoxy-based resin.
  • thermoplastic or thermoplastic polymer
  • Tg temperature of glass transition
  • Tf melting temperature
  • Tg, Te and Tf are determined by differential scanning calorimetry (DSC) according to standard 11357-2: 2013 and 11357-3: 2013 respectively.
  • the number average molecular weight Mn of said thermoplastic polymer is preferably in a range of 10,000 to 40,000, preferably 10,000 to 30,000. These Mn values may correspond to inherent viscosities greater than or equal to 0.8 as determined in the m-cresol according to ISO 307: 2007 but changing the solvent (use of m-cresol instead of sulfuric acid and the temperature being 20 ° C).
  • polyamides in particular comprising an aromatic and / or cycloaliphatic structure
  • copolymers for example polyamide-polyethers, polyesters, copolymers, polyaryletherketones (PAEK), polyetherether ketones (PEEK), polyetherketone ketones (PEKK), polyetherketoneetherketone ketones (PEKEKK), polyimides in particular polyetherimides (PEI) or polyamide-imides (in particular PSU )sulfones, polylsulfones polyarylsulfones such as polyphenyl sulfones
  • PAEK polyaryletherketones
  • PEEK polyetherether ketones
  • PEKK polyetherketone ketones
  • PEKEKK polyetherketoneetherketone ketones
  • PEI polyetherimides
  • PSU polyamide-imides
  • PPSU polyethersulfones
  • semi-crystalline polymers are more particularly preferred, and in particular polyamides and their semi-crystalline copolymers.
  • the polyamide can be a homopolyamide or a copolyamide or a mixture thereof.
  • the semi-crystalline polyamides are semi-aromatic polyamides, in particular a semi-aromatic polyamide of formula X / YAr, as described in EP1505099, in particular a semi-aromatic polyamide of formula A / XT in which A is chosen from a unit obtained from an amino acid, a unit obtained from a lactam and a unit corresponding to the formula (diamine in Ca).
  • (Cb diacid) with a representing the number of carbon atoms of the diamine and b representing the number of carbon atoms of the diacid, a and b each being between 4 and 36, advantageously between 9 and 18, the unit (Ca diamine) being chosen from aliphatic, linear or branched diamines, cycloaliphatic diamines and alkylaromatic diamines and the unit (Cb diacid) being chosen from aliphatic, linear or branched diacids, cycloaliphatic diacids and aromatic diacids ;
  • XT denotes a unit obtained from the polycondensation of a Cx diamine and terephthalic acid, with x representing the number of carbon atoms of the Cx diamine, x being between 5 and 36, advantageously between 9 and 18, in particular a polyamide of formula A / 5T, A / 6T, A / 9T, A / 10T or A / 11 T, A being as defined above, in particular a polyamide chosen from a PA MPMDT / 6T, one PA11 / 10T, one PA 5T / 10T, one PA 11 / BACT, one PA 11 / 6T / 10T, one PA MXDT / 10T, one PA MPMDT / 10T, one PA BACT / 10T, one PA BACT / 6T, PA BACT / 10T / 6T, one PA 11 / BACT / 6T, PA 11 / MPMDT / 10T, PA 11 / B
  • T corresponds to terephthalic acid
  • MXD corresponds to m-xylylenediamine
  • MPMD corresponds to methylpentamethylene diamine
  • BAC corresponds to bis (aminomethyl) cyclohexane.
  • Said semi-aromatic polyamides defined above have in particular a Tg greater than or equal to 80 ° C.
  • thermosetting polymers are chosen from epoxy or epoxy-based resins, polyesters, vinyl esters and polyurethanes, or a mixture of these, in particular epoxy or epoxy-based resins.
  • each composite reinforcing layer consists of a composition comprising the same type of polymer, in particular an epoxy or epoxy-based resin.
  • Said composition comprising said polymer P2j may be transparent to radiation suitable for welding.
  • the winding of the composite reinforcing layer around the waterproofing layer is carried out in the absence of any subsequent welding.
  • Said multilayer structure therefore comprises a waterproofing layer and at least one composite reinforcing layer which is wrapped around the waterproofing layer and which may or may not adhere to each other.
  • sealing and reinforcing layers do not adhere to each other and consist of compositions which respectively comprise different polymers.
  • said different polymers can be of the same type.
  • the waterproofing layer consisting of a composition comprising an aliphatic polyamide PA11
  • the reinforcing layer (s) is (are) or consists of a composition comprising a polyamide which is not aliphatic and which is by example a semi-aromatic polyamide so as to have a high tg polymer as the matrix of the composite reinforcement.
  • Said multilayer structure can include up to 10 composite reinforcement layers of different types.
  • said multilayer structure comprises a sealing layer and one, two, three, four, five, six, seven, eight, nine or ten layers of composite reinforcement.
  • said multilayer structure comprises a waterproofing layer and one, two, three, four or five composite reinforcement layers.
  • said multilayer structure comprises a waterproofing layer and one two or three composite reinforcement layers.
  • compositions which respectively comprise different polymers consist of compositions which respectively comprise polyamides corresponding to polyamides PA11 and an epoxy resin or epoxy resin P2j.
  • said multilayer structure comprises a single waterproofing layer and several reinforcing layers, said adjacent reinforcing layer being wrapped around said waterproofing layer and the other reinforcing layers being wrapped around the reinforcing layer. directly adjacent.
  • said multilayer structure comprises a single waterproofing layer and a single composite reinforcing layer, said reinforcing layer being wrapped around said waterproofing layer.
  • each reinforcing layer consists of a composition comprising the same type of polymer P2j, in particular an epoxy or epoxy-based resin.
  • the P2j polyamide is identical for all the reinforcing layers.
  • the sealing layer consists of a composition comprising a polyamide PA11 and each reinforcing layer consists of a composition comprising the same type of polymer P2j, in particular an epoxy resin. or epoxy based.
  • the sealing layer consists of a composition comprising a polyamide PA11 and each reinforcing layer consists of a composition comprising the same type of polymer P2j, said polymer P2j being a semi-aromatic polyamide, in particular chosen from a PA MPMDT / 6T, a PA PA11 / 10T, a PA 11 / BACT, a PA 5T / 10T, a PA 11 / 6T / 10T, a PA MXDT / 10T, a PA MPMDT / 10T, one PA BACT / 10T, one PA BACT / 6T, PA BACT / 10T / 6T, one PA 11 / BACT / 6T, PA 11 / MPMDT / 6T, PA 11 / MPMDT / 10T, PA 11 / BACT / 10T and a PA 11 / MXDT / 10T.
  • said multilayer structure consists of a single sealing layer and a single reinforcing layer in which said polymer P2j is a semi-aromatic polyamide, in particular chosen from a PA MPMDT / 6T, a PA11 / 10T, one PA 11 / BACT, one PA 5T / 10T, one PA 11 / 6T / 10T, one PA MXDT / 10T, one PA MPMDT / 10T, one PA BACT / 10T, one PA BACT / 6T, PA BACT / 10T / 6T, one PA 11 / BACT / 6T, PA 11 / MPMDT / 6T, PA 11 / MPMDT / 10T, PA 11 / BACT / 10T and one PA 11 / MXDT / 10T.
  • the multilayer structure consists of a single sealing layer and a single reinforcing layer in which said polymer P2j is an epoxy or epoxy-based resin.
  • said multilayer structure further comprises at least one outer layer made of a continuous fiberglass fibrous material impregnated with a transparent amorphous polymer, said layer being the outermost layer of said multilayer structure.
  • Said outer layer is a second but transparent reinforcing layer which makes it possible to put an inscription on the structure.
  • Said outer layer in no way corresponds to the layer located above the outermost composite reinforcing layer of polyamide polymer, the structure of which is not mentioned above.
  • constituent fibers of said fibrous material they are in particular fibers of mineral, organic or plant origin.
  • said fibrous material can be sized or not sized.
  • Said fibrous material can therefore comprise up to 3.5% by weight of an organic material (thermosetting or thermoplastic resin type) called sizing.
  • fibers of mineral origin mention may be made of carbon fibers, glass fibers, basalt or basalt-based fibers, silica fibers, or silicon carbide fibers, for example.
  • fibers of organic origin mention may be made of fibers based on a thermoplastic or thermosetting polymer, such as semi-aromatic polyamide fibers, aramid fibers or polyolefin fibers, for example.
  • they are based on an amorphous thermoplastic polymer and have a glass transition temperature Tg greater than the Tg of the polymer or mixture of thermoplastic polymer constituting the pre-impregnation matrix when the latter is amorphous, or greater than the Tm of the polymer or mixture of thermoplastic polymer constituting the prepreg matrix when the latter is semi-crystalline.
  • they are based on a semi-crystalline thermoplastic polymer and have a melting point Tm greater than the Tg of the polymer or mixture of thermoplastic polymer constituting the prepreg matrix when the latter is amorphous, or greater than the Tm. of the polymer or mixture of thermoplastic polymer constituting the prepreg matrix when the latter is semi-crystalline.
  • the organic fibers constituting the fibrous material during impregnation with the thermoplastic matrix of the final composite.
  • the fibers of plant origin mention may be made of natural fibers with base of flax, hemp, lignin, bamboo, silk, in particular spider silk, sisal, and other cellulose fibers, in particular viscose. These fibers of plant origin can be used pure, treated or else coated with a coating layer, with a view to facilitating the adhesion and the impregnation of the thermoplastic polymer matrix.
  • the fibrous material can also be fabric, braided or woven with fibers.
  • organic fibers can be mixed with mineral fibers to be pre-impregnated with thermoplastic polymer powder and to form the pre-impregnated fibrous material.
  • the rovings of organic fibers can have several grammages. They can also have several geometries.
  • the fibers constituting the fibrous material can also be in the form of a mixture of these reinforcing fibers of different geometries. Fibers are continuous fibers.
  • the fibrous material is chosen from glass fibers, carbon fibers, basalt or basalt-based fibers, or a mixture of these, in particular carbon fibers.
  • It is used as a wick or several wicks.
  • the present invention relates to a method of manufacturing a multilayer structure as defined above, characterized in that it comprises a step of preparing the sealing layer by extrusion blow molding, by rotational molding, by injection and / or extrusion.
  • said method of manufacturing a multilayer structure comprises a step of filament winding of the reinforcing layer as defined above around the sealing layer as defined above.
  • Figure 1 shows the notched Charpy impact at -40 ° C according to ISO 179-1: 2010 of four liners: from left to right PA11, PA12, PA6 and PA66.
  • Figure 2 shows the hydrogen permeability at 23 ° C of PA12 and HDPE liners.
  • the permeability must then be multiplied by 101325.
  • Figure 3 shows the notched Charpy shock at -40 ° C according to ISO 179-1: 2010 for PA11 and PA12 liners: for each group of histograms, 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.
  • the tanks are obtained by rotational molding of the sealing layer (liner) at a temperature suited to the nature of the thermoplastic resin used.
  • a wet filament winding process is then used which consists in winding fibers around the liner, which fibers are pre-impregnated in an epoxy bath. liquid or a liquid epoxy-based bath. The reservoir is then polymerized in an oven for 2 hours.
  • thermoplastic resin a fibrous material impregnated with the thermoplastic resin (tape) is used.
  • This tape is deposited by filament winding using a robot comprising a 1500W power laser heater at a speed of 12m / min and there is no polymerization step.
  • Example 1 Notched Charpy shock at -40 ° C according to ISO 179-1: 2010
  • Two long chain liners of PA11 and PA12 and two short chain liners were prepared by rotational molding as above.
  • the cold resistance of the PA1 liner is very much better than that of the long chain liner PA12 and the short chain liners PA6 and PA66.
  • Two long chain liners one in PA11 (Arkema) and the second in PA12 (Arkema) and one liner in HDPE were prepared by rotational molding and the hydrogen permeability at 23 ° C was tested.
  • Example 3 influence of the proportion of plasticizer (N-butyl benzene sulfonamide: BBSA) on the notched Charpy impact at -40 ° C according to ISO 179-1: 2010
  • Two liners PA11 and PA12 without plasticizer or comprising 7 or 12% plasticizer (BBSA) relative to the total weight of the composition were prepared by rotational molding.
  • LT cocktail having the following composition: lotader® 4700 (50%) + lotader® AX8900 (25%) + lucalene® 3110 (25%)) on the liner's hydrogen permeability PA11.
  • the permeability can also be expressed in (cc.25p / m 2 .24h.Pa). The permeability must then be multiplied by 101325. The results show that the proportion of impact modifier influences the permeability to hydrogen.
  • Type IV hydrogen storage tank composed of an epoxy composite reinforcement (Tg 120 ° C) T700SC31E carbon fibers (produced by Toray) and a waterproofing layer of PA11.
  • the operating temperature is sufficient for rapid filling of the tank, especially in 3 to 5 minutes.
  • Type IV hydrogen storage tank composed of an epoxy composite reinforcement (Tg 120 ° C) T700SC31E carbon fibers (produced by Toray) and an HDPE waterproofing layer.
  • the operating temperature is too low for rapid filling of the tank, especially in 3 to 5 minutes.
  • Example 7 Type IV hydrogen storage tank, composed of a reinforcement of BACT / 10T carbon fiber T700SC31 E composite (produced by Toray) and a waterproofing layer of PA11.
  • the BACT / 10T type composition chosen has a melting point, Tm, of 283 ° C, a crystallization temperature, Te, of 250 ° C and a glass transition temperature of 164 ° C.
  • Tg, Te and Tf are determined by differential scanning calorimetry (DSC) according to standard 11357-2: 2013 and 11357-3: 2013 respectively.
  • a PA BACT / 10T-based composite exhibits a high Tg matrix, but without having long crosslinking, of the 8h type at 140 ° C.

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Abstract

The invention relates to a multilayer structure for transporting, distributing and storing hydrogen, comprising, from the inside to the outside, a sealing layer (1) and at least one composite reinforcement layer (2), said innermost composite reinforcement layer being wound around said sealing layer (1), said sealing layer consisting of a composition predominantly comprising: a polyamide thermoplastic polymer PA11, up to less than 15% by weight of impact modifier, in particular up to 12% by weight of impact modifier relative to the total weight of the composition, up to 1.5% by weight of plasticizer relative to the total weight of the composition, said composition being devoid of nucleating agent and of polyether block amide (PEBA), and at least one of said composite reinforcement layers consisting of a fibrous material in the form of continuous fibers, which is impregnated with a composition predominantly comprising at least one polymer P2j, (j = 1 to m, m being the number of reinforcement layers), in particular an epoxy or epoxide-based resin, said structure being devoid of an outermost layer and, adjacent to the outermost layer, of a composite reinforcement layer of polyamide polymer.

Description

DESCRIPTION DESCRIPTION
TITRE : STRUCTURE MULTICOUCHE POUR LE TRANSPORT OU LE STOCKAGE DETITLE: MULTI-LAYER STRUCTURE FOR THE TRANSPORT OR STORAGE OF
L’HYDROGENE HYDROGEN
[Domaine technique] [Technical area]
La présente demande de brevet concerne des structures multicouches composites pour le transport, la distribution ou le stockage de l’hydrogène, en particulier pour la distribution ou le stockage de l’hydrogène, et leur procédé de fabrication. The present patent application relates to composite multilayer structures for the transport, distribution or storage of hydrogen, in particular for the distribution or storage of hydrogen, and their manufacturing process.
[Technique antérieure] [Prior art]
Les réservoirs d’hydrogène représentent un sujet qui attire actuellement beaucoup d’intérêt de la part de nombreux industriels, notamment dans le domaine automobile. L’un des buts recherché est de proposer des véhicules de moins en moins polluants. Ainsi, les véhicules électriques ou hybrides comportant une batterie visent à remplacer progressivement les véhicules thermiques, tels que les véhicules à essence ou bien à gasoil. Or, il s’avère que la batterie est un constituant du véhicule relativement complexe. Selon l’emplacement de la batterie dans le véhicule, il peut être nécessaire de la protéger des chocs et de l’environnement extérieur, qui peut être à des températures extrêmes et à une humidité variable. Il est également nécessaire d’éviter tout risque de flammes. Hydrogen tanks are a subject that is currently attracting a lot of interest from many manufacturers, especially in the automotive field. One of the goals is to offer vehicles that pollute less and less. Thus, electric or hybrid vehicles comprising a battery aim to gradually replace thermal vehicles, such as gasoline or diesel vehicles. However, it turns out that the battery is a relatively complex component of the vehicle. Depending on the location of the battery in the vehicle, it may be necessary to protect it from impact and the external environment, which can be extreme temperatures and varying humidity. It is also necessary to avoid any risk of flames.
De plus, il est important que sa température de fonctionnement n’excède pas 55°C pour ne pas détériorer les cellules de la batterie et préserver sa durée de vie. A l’inverse, par exemple en hiver, il peut être nécessaire d’élever la température de la batterie de manière à optimiser son fonctionnement. In addition, it is important that its operating temperature does not exceed 55 ° C so as not to damage the battery cells and preserve its lifespan. Conversely, for example in winter, it may be necessary to raise the temperature of the battery in order to optimize its operation.
Par ailleurs, le véhicule électrique souffre encore aujourd’hui de plusieurs problèmes à savoir l’autonomie de la batterie, l’utilisation dans ces batteries de terre rares dont les ressources ne sont pas inépuisables, des temps de recharge beaucoup plus long que les durées de remplissage de réservoir, ainsi qu’un problème de production d’électricité dans les différents pays pour pouvoir recharger les batteries. In addition, the electric vehicle still suffers today from several problems, namely the autonomy of the battery, the use in these rare earth batteries whose resources are not inexhaustible, recharging times much longer than the durations. tank filling, as well as a problem of electricity production in the different countries to be able to recharge the batteries.
L’hydrogène représente donc une alternative à la batterie électrique puisque l’hydrogène peut être transformé en électricité au moyen d’une pile à combustible et alimenter ainsi les véhicules électriques. Hydrogen therefore represents an alternative to the electric battery since hydrogen can be transformed into electricity by means of a fuel cell and thus power electric vehicles.
Les réservoirs à hydrogène sont généralement constitués d'une enveloppe (liner ou couche d’étanchéité) métallique qui doit empêcher la perméation de l'hydrogène. L’un des types de réservoirs envisagés, appelé Type IV, est basé sur un liner thermoplastique autour duquel est enroulé un composite. Hydrogen tanks generally consist of a metal casing (liner or sealing layer) which must prevent the permeation of hydrogen. One of the types of tanks being considered, called Type IV, is based on a thermoplastic liner around which a composite is wrapped.
Leur principe de base est de séparer les deux fonctions essentielles que sont l'étanchéité et la tenue mécanique pour les gérer l'une indépendamment de l'autre. Dans ce type de réservoir on associe liner (ou gaine d’étanchéité) en résine thermoplastique à une structure de renforcement constituée de fibres (verre, aramide, carbone) encore dénommée gaine ou couche de renfort qui permettent de travailler à des pressions beaucoup plus élevées tout en réduisant la masse et en évitant les risques de rupture explosive en cas d’agressions externes sévères. Their basic principle is to separate the two essential functions of sealing and mechanical strength in order to manage them one independently of the other. In this type of tank, a thermoplastic resin liner (or sealing sheath) is combined with a reinforcing structure made up of fibers (glass, aramid, carbon). called sheath or reinforcing layer which allow to work at much higher pressures while reducing the mass and avoiding the risk of explosive rupture in the event of severe external attacks.
Les liners doivent présenter certaines caractéristiques de base : Liners should have some basic characteristics:
La possibilité d’être transformé par extrusion soufflage, rotomoulage, injection, ou extrusion The possibility of being transformed by extrusion blow molding, rotational molding, injection, or extrusion
Une faible perméabilité à l’hydrogène, la perméabilité du liner est en effet un facteur clé pour limiter les pertes d’hydrogène du réservoir ; Low hydrogen permeability, the permeability of the liner is indeed a key factor in limiting hydrogen losses from the tank;
De bonnes propriétés mécaniques (fatigue) à basses températures (-40 à -70°C) ; Good mechanical properties (fatigue) at low temperatures (-40 to -70 ° C);
Une tenue thermique à 120°C. Thermal resistance at 120 ° C.
En effet, il est nécessaire d’augmenter la vitesse de remplissage du réservoir d’hydrogène qui doit être environ équivalente à celle d’un réservoir à essence pour moteur thermique (environ 3 à 5 minutes) mais cette augmentation de vitesse provoque un échauffement du réservoir plus importante qui atteint alors une température d’environ 100°C. Indeed, it is necessary to increase the filling speed of the hydrogen tank which must be approximately equivalent to that of a gasoline tank for a heat engine (approximately 3 to 5 minutes) but this increase in speed causes the heating of the fuel tank. larger tank which then reaches a temperature of around 100 ° C.
L’évaluation des performances et de la sécurité des réservoirs d’hydrogène peut être déterminée dans un laboratoire de référence Européen (GasTeF : installation de test des réservoirs d’hydrogène) tel que décrit dans Galassi et al. (Word hydrogen energy conférence 2012, Onboard compressed hydrogen storage : fast filing experiments and simulations, Energy Procedia 29, (2012) 192-200). The evaluation of the performance and safety of hydrogen tanks can be determined in a European reference laboratory (GasTeF: hydrogen tank test facility) as described in Galassi et al. (Word hydrogen energy conference 2012, Onboard compressed hydrogen storage: fast filing experiments and simulations, Energy Procedia 29, (2012) 192-200).
La première génération de réservoirs de type IV utilisait un liner sur base polyéthylène haute densité (HDPE). The first generation of type IV tanks used a liner based on high density polyethylene (HDPE).
Cependant, HDPE présente le défaut d’avoir une température de fusion trop basse et une perméabilité à l’hydrogène élevée, ce qui représente un problème avec les nouvelles exigences en matière de tenue thermique et ne permet pas d’augmenter la vitesse de remplissage du réservoir. However, HDPE has the drawback of having too low a melting temperature and high hydrogen permeability, which is a problem with the new thermal withstand requirements and does not allow the filling speed of the tank to be increased. tank.
Depuis plusieurs années, des liners sur base polyamide PA6 se sont développés. Néanmoins, le PA6 présente le désavantage d’avoir une faible tenue à froid. For several years, liners based on polyamide PA6 have been developed. However, PA6 has the disadvantage of having poor cold resistance.
La demande internationale WO 2016/166326 décrit un procédé de fabrication d'une coque interne d'un réservoir composite de type IV délimitant une cavité interne destinée à accueillir un fluide sous pression et comprenant au moins une embase métallique, et une une étape ultérieure de dépôt, sur la surface externe de la coque interne, d'un matériau fibreux pour former l'enveloppe externe du réservoir. International application WO 2016/166326 describes a method of manufacturing an internal shell of a type IV composite tank delimiting an internal cavity intended to receive a pressurized fluid and comprising at least one metal base, and a subsequent step of depositing, on the outer surface of the inner shell, a fibrous material to form the outer shell of the reservoir.
La demande internationale W095/22030 décrit un liner de réservoir haute pression en matériau thermoplastique, ledit matériau thermoplastique étant un matériau choisi dans le groupe constitué d'un nylon modifié 6 et nylon 11. International application WO95 / 22030 describes a high pressure tank liner made of thermoplastic material, said thermoplastic material being a material chosen from the group consisting of a modified nylon 6 and nylon 11.
La demande française FR2923575 décrit un réservoir pour le stockage de fluide sous haute pression comportant à chacune de ses extrémités le long de son axe un embout métallique d'extrémité, un liner enveloppant lesdits embouts et une couche structurelle en fibre imprégnée de résine thermodurcissable enveloppant ledit liner. French application FR2923575 describes a reservoir for storing fluid under high pressure comprising at each of its ends along its axis a nozzle metal end, a liner enveloping said end caps and a structural layer of fiber impregnated with thermosetting resin enveloping said liner.
La demande internationale W018155491 décrit un composant de transport d’hydrogène présentant une structure tricouche dont la couche interne est une composition constituée de PA11 , de 15 à 50% d’un modifiant choc et de 1 à 3% de plastifiant ou dépourvue de plastifiant qui présente des propriétés barrière à l’hydrogène, une bonne flexibilité et durabilité à faible température. Cependant, cette structure est adaptée à des tuyaux pour le transport de l’hydrogène mais pas pour le stockage de l’hydrogène. International application WO18155491 describes a hydrogen transport component having a three-layer structure, the inner layer of which is a composition consisting of PA11, 15 to 50% of an impact modifier and 1 to 3% of plasticizer or without plasticizer which exhibits hydrogen barrier properties, good flexibility and low temperature durability. However, this structure is suitable for pipes for transporting hydrogen but not for storing hydrogen.
Ainsi, il reste à optimiser d’une part, la matrice du composite de façon à optimiser sa résistance mécanique à haute température et d’autre part le matériau composant la gaine d’étanchéité, de façon à optimiser sa température de mise en oeuvre. Ainsi, la modification éventuelle de la composition du matériau composant la gaine d’étanchéité, qui sera faite ne doit pas se traduire par une augmentation significative de la température de fabrication (extrusion-soufflage, injection, rotomoulage...) de ce liner, par rapport à ce qui se pratique aujourd’hui. Thus, it remains to optimize on the one hand, the matrix of the composite in order to optimize its mechanical resistance at high temperature and on the other hand the material composing the sealing sheath, in order to optimize its processing temperature. Thus, the possible modification of the composition of the material composing the sealing sheath, which will be made, must not result in a significant increase in the manufacturing temperature (extrusion-blow molding, injection, rotomoulding, etc.) of this liner, compared to what is practiced today.
Ces problèmes sont résolus par la fourniture d’une structure multicouche de la présente invention destinée au transport, à la distribution ou au stockage de l’hydrogène Dans toute cette description, les termes « liner » et « gaine d’étanchéité » ont la même signification. These problems are solved by providing a multilayer structure of the present invention intended for the transport, distribution or storage of hydrogen. Throughout this description, the terms "liner" and "sealing sheath" have the same. meaning.
La présente invention concerne donc une structure multicouche destinée au transport, à la distribution et au stockage de l’hydrogène, comprenant, de l’intérieur vers l’extérieur, une couche d’étanchéité (1) et au moins une couche de renfort composite (2), ladite couche de renfort composite la plus interne étant enroulée autour de la dite couche d’étanchéité (1), ladite couche d’étanchéité étant constituée d’une composition comprenant majoritairement : un polymère thermoplastique polyamide PA11 , jusqu’à moins de 15% en poids de modifiant choc, en particulier jusqu’à 12% en poids de modifiant choc par rapport au poids total de la composition, jusqu’à 1,5% en poids de plastifiant par rapport au poids total de la composition, ladite composition étant dépourvue d’agent nucléant et de polyéther block amide (PEBA), et au moins l’une des dites couches de renfort composite étant constituée d’un matériau fibreux sous forme de fibres continues imprégné par une composition comprenant majoritairement au moins un polymère P2j, (j=1 à m, m étant le nombre de couches de renfort), en particulier une résine époxyde ou à base d’époxyde, ladite structure étant dépourvue d’une couche la plus extérieure et adjacente à la couche la plus extérieure de renfort composite en polymère polyamide. Les Inventeurs ont donc trouvé de manière inattendue que l’utilisation d’un polymère thermoplastique polyamide PA11, comprenant une proportion de modifiant choc et de plastifiant limitée, pour la couche d’étanchéité, avec un polymère différent pour la matrice du composite et notamment une résine époxyde ou à base d’époxyde, enroulé sur la couche d’étanchéité, permettait l’obtention d’une structure adaptée au transport, à la distribution ou au stockage de l’hydrogène et notamment une augmentation de la température maximale d’utilisation pouvant aller jusqu’à 120°C, permettant ainsi d’augmenter la vitesse de remplissage des réservoirs. The present invention therefore relates to a multilayer structure intended for the transport, distribution and storage of hydrogen, comprising, from the inside to the outside, a sealing layer (1) and at least one composite reinforcing layer. (2), said innermost composite reinforcing layer being wound around said sealing layer (1), said sealing layer consisting of a composition mainly comprising: a thermoplastic polyamide PA11 polymer, up to less from 15% by weight of impact modifier, in particular up to 12% by weight of impact modifier relative to the total weight of the composition, up to 1.5% by weight of plasticizer relative to the total weight of the composition, said composition being devoid of nucleating agent and of polyether block amide (PEBA), and at least one of said composite reinforcing layers consisting of a fibrous material in the form of continuous fibers impregnated with a composition comprising mainly ent at least one polymer P2j, (j = 1 to m, m being the number of reinforcing layers), in particular an epoxy or epoxy-based resin, said structure being devoid of an outermost layer and adjacent to the outermost layer of composite reinforcement in polyamide polymer. The inventors have therefore unexpectedly found that the use of a thermoplastic polyamide PA11 polymer, comprising a limited proportion of impact modifier and plasticizer, for the sealing layer, with a different polymer for the matrix of the composite and in particular a epoxy resin or epoxy-based, wound on the waterproofing layer, made it possible to obtain a structure suitable for the transport, distribution or storage of hydrogen and in particular an increase in the maximum temperature of use up to 120 ° C, thus increasing the tank filling speed.
Le polymère thermoplastique PA11 (ou polyamide 11) est commercialisé par la société Arkema et est issu notamment de la polycondensation d’acide amino-11 undécanoïque. Par « structure multicouche » il faut entendre un réservoir comprenant ou constitué de plusieurs couches, à savoir une couche d’étanchéité et plusieurs couches de renfort, ou une couche d’étanchéité et une couche de renfort. The thermoplastic polymer PA11 (or polyamide 11) is marketed by the company Arkema and is obtained in particular from the polycondensation of 11-amino undecanoic acid. By "multilayer structure" is meant a tank comprising or made up of several layers, namely a waterproofing layer and several reinforcing layers, or a waterproofing layer and a reinforcing layer.
La structure multicouche s’entend donc à l’exclusion d’un tuyau ou d’un tube. The multilayer structure is therefore meant to the exclusion of a pipe or tube.
Les poly ether block amide (PEBA) sont des copolymères à motifs amides (Ba1) et motifs polyéthers (Ba2) ledit motif amide (Ba1 ) correspondant à un motif répétitif aliphatique choisi parmi un motif obtenu à partir d'au moins un aminoacide ou un motif obtenu à partir d'au moins un lactame, ou un motif X.Y obtenu à partir de la polycondensation : Poly ether block amide (PEBA) are copolymers with amide units (Ba1) and polyether units (Ba2), said amide unit (Ba1) corresponding to an aliphatic repeating unit chosen from a unit obtained from at least one amino acid or a unit obtained from at least one lactam, or an XY unit obtained from polycondensation:
- d'au moins une diamine, ladite diamine étant choisie préférentiellement parmi une diamine aliphatique linéaire ou ramifiée ou un mélange de celles-ci, et - at least one diamine, said diamine being preferably chosen from a linear or branched aliphatic diamine or a mixture thereof, and
- d'au moins un diacide carboxylique, ledit diacide étant choisi préférentiellement parmi : un diacide aliphatique linéaire ou ramifié, ou un mélange de ceux-ci, ladite diamine et ledit diacide comprenant de 4 à 36 atomes de carbone, avantageusement de 6 à 18 atomes de carbone ; lesdits motifs polyéthers (Ba2) étant notamment issus d’au moins un polyalkylène éther polyol, notamment un polyalkylène éther diol. - at least one dicarboxylic acid, said dicarboxylic acid being preferably chosen from: a linear or branched aliphatic dicacid, or a mixture of these, said diamine and said dicacid comprising from 4 to 36 carbon atoms, advantageously from 6 to 18 carbon atoms; said polyether units (Ba2) being in particular derived from at least one polyalkylene ether polyol, in particular a polyalkylene ether diol.
Les agents nucléants sont connus de l'homme du métier et se réfère à une substance qui, lorsqu'elle est incorporée dans un polymère, forme des noyaux pour la croissance de cristaux dans le polymère fondu. Nucleating agents are known to those skilled in the art and refer to a substance which, when incorporated into a polymer, forms nuclei for crystal growth in the molten polymer.
Ils peuvent être choisis par exemple parmi le micro talc, le noir de carbone, la silice, le dioxyde de titane et les nano-argiles. They can be chosen, for example, from micro talc, carbon black, silica, titanium dioxide and nanoclays.
Dans un mode de réalisation, le PA6 est exclu de ladite composition. In one embodiment, PA6 is excluded from said composition.
L’expression « ladite structure étant dépourvue d’une couche la plus extérieure et adjacente à la couche la plus extérieure de renfort composite en polymère polyamide » signifie que la structure est dépourvue d’une couche en polymère polyamide située au- dessus de la couche de renfort composite la plus extérieure. Dans un mode de réalisation, ladite structure multicouche est constituée de deux couches, une couche d’étanchéité et une couche de renfort. The expression "said structure being devoid of an outermost layer and adjacent to the outermost layer of composite reinforcement of polyamide polymer" means that the structure is devoid of a layer of polyamide polymer situated above the layer. outermost composite reinforcement. In one embodiment, said multilayer structure consists of two layers, a sealing layer and a reinforcing layer.
La couche d’étanchéité est la couche la plus interne par rapport aux couches de renfort composites qui sont les couches les plus externes. The waterproofing layer is the innermost layer relative to the composite reinforcement layers which are the outermost layers.
Le réservoir peut être un réservoir pour le stockage mobile de l’hydrogène, c’est-à-dire sur un camion pour le transport de l’hydrogène, sur une voiture pour le transport de l’hydrogène et l’alimentation en hydrogène d’une pile à combustible par exemple, sur un train pour l’alimentation en hydrogène ou sur un drone pour l’alimentation en hydrogène, mais il peut être également un réservoir de stockage stationnaire de l’hydrogène en station pour la distribution d’hydrogène à des véhicules. The tank can be a tank for the mobile storage of hydrogen, i.e. on a truck for the transport of hydrogen, on a car for the transport of hydrogen and the supply of hydrogen d '' a fuel cell for example, on a train for the supply of hydrogen or on a drone for the supply of hydrogen, but it can also be a stationary storage tank for hydrogen in a station for the distribution of hydrogen to vehicles.
Avantageusement, la couche d’étanchéité (1) est étanche à l’hydrogène à 23°C, c’est-à- dire que la perméabilité à l’hydrogène à 23°C est inférieure à 500 cc.mm/m2.24h.atm à 23°C sous 0% d’humidité relative (RH). Advantageously, the sealing layer (1) is impermeable to hydrogen at 23 ° C, that is to say that the permeability to hydrogen at 23 ° C is less than 500 cc.mm/m2. 24h. .atm at 23 ° C under 0% relative humidity (RH).
La ou les couches de renfort composite est (sont) enroulée(s) autour de la couche d’étanchéité au moyen de rubans (ou tapes ou rovings) de fibres imprégnés de polymère qui sont déposés par exemple, par enroulement filamentaire. The composite reinforcing layer (s) is (are) wound (s) around the waterproofing layer by means of tapes (or tapes or rovings) of fibers impregnated with polymer which are deposited, for example, by filament winding.
Lorsque plusieurs couches sont présentes, les polymères sont différents. When multiple layers are present, the polymers are different.
Lorsque les polymères des couches de renfort sont identiques, il peut y avoir présence de plusieurs couches mais avantageusement, une seule couche de renfort est présente et qui présente alors au moins un enroulement complet autour de la couche d’étanchéité.When the polymers of the reinforcing layers are identical, there may be several layers present, but advantageously, only one reinforcing layer is present and which then has at least one complete winding around the waterproofing layer.
Ce procédé totalement automatisé, bien connu de l’homme du métier permet, couche par couche, de choisir les angles d’enroulement qui vont donner à la structure finale son aptitude à résister au chargement de pression interne. This fully automated process, well known to those skilled in the art, makes it possible, layer by layer, to choose the winding angles which will give the final structure its ability to withstand internal pressure loading.
Lorsque seules une couche d’étanchéité et une couche de renfort composite sont présentes, conduisant donc à une structure multicouche à deux couches, alors ces deux couches peuvent adhérer l’une à l’autre, en contact direct l’une avec l’autre, notamment en raison de l’enroulement de la couche de renfort composite sur la couche d’étanchéité. Lorsqu’une couche d’étanchéité est présente et/ou plusieurs couches de renfort composite, alors la couche la couche d’étanchéité peut adhérer ou non à la couche la plus interne desdites de renfort composite. When only a waterproofing layer and a composite reinforcing layer are present, thus leading to a multilayer structure with two layers, then these two layers can adhere to each other, in direct contact with each other , in particular due to the winding of the composite reinforcing layer on the waterproofing layer. When a waterproofing layer is present and / or several composite reinforcement layers, then the waterproofing layer may or may not adhere to the innermost layer of said composite reinforcement.
Les autres couches de renfort composite peuvent également adhérer ou non entre elles. Avantageusement, seules une couche d’étanchéité et une couche de renfort sont présentes et n’adhèrent pas entre elles. The other composite reinforcement layers may or may not also adhere to each other. Advantageously, only a waterproofing layer and a reinforcing layer are present and do not adhere to each other.
Avantageusement, seules une couche d’étanchéité en PA11 et une couche de renfort sont présentes et n’adhèrent pas entre elles et la couche de renfort est constituée d’un matériau fibreux sous forme de fibres continues imprégné par une composition comprenant majoritairement au moins un polymère P2j, en particulier une résine époxyde ou à base d’époxyde. Advantageously, only a sealing layer made of PA11 and a reinforcing layer are present and do not adhere to each other and the reinforcing layer consists of a fibrous material in the form of continuous fibers impregnated with a composition. mainly comprising at least one polymer P2j, in particular an epoxy resin or an epoxy-based resin.
Dans un mode de réalisation, seules une couche d’étanchéité et une couche de renfort sont présentes et n’adhèrent pas entre elles et la couche de renfort est constituée d’un matériau fibreux sous forme de fibres continues imprégné par une composition comprenant majoritairement un polymère P2j qui est une résine époxyde ou à base d’époxyde. In one embodiment, only a waterproofing layer and a reinforcing layer are present and do not adhere to each other and the reinforcing layer consists of a fibrous material in the form of continuous fibers impregnated with a composition mainly comprising a P2j polymer which is an epoxy or epoxy-based resin.
L’expression à base d’époxyde dans toute la description signifie que l’époxyde représente au moins 50% en poids de la matrice. The term epoxy-based throughout the description means that the epoxy represents at least 50% by weight of the matrix.
S’agissant de la couche d’étanchéité Regarding the waterproofing layer
La couche d’étanchéité est constituée d’une composition comprenant majoritairement au moins un polymère thermoplastique PA11. The waterproofing layer consists of a composition comprising predominantly at least one thermoplastic polymer PA11.
Le terme « majoritairement » signifie que ledit au moins un polymère est présent à plus de 50% en poids par rapport au poids total de la composition et de la matrice. Avantageusement, ledit au moins un polymère majoritaire est présent à plus de 60% en poids notamment à plus de 70% en poids, particulièrement à plus de 80% en poids, plus particulièrement supérieur ou égal à 90% en poids 90% en poids, par rapport au poids total de la composition et de la matrice. The term “predominantly” means that said at least one polymer is present in more than 50% by weight relative to the total weight of the composition and of the matrix. Advantageously, said at least one majority polymer is present at more than 60% by weight, in particular at more than 70% by weight, particularly at more than 80% by weight, more particularly greater than or equal to 90% by weight 90% by weight, relative to the total weight of the composition and the matrix.
Ladite composition peut également comprendre des modifiants choc jusqu’à 15% en poids par rapport au poids total de la composition et/ou un plastifiant et/ou des additifs.Said composition can also comprise impact modifiers of up to 15% by weight relative to the total weight of the composition and / or a plasticizer and / or additives.
Les additifs peuvent être choisis parmi un autre polymère, un antioxydant, un stabilisant à la chaleur, un absorbeur d’UV, un stabilisant à la lumière, un lubrifiant, une charge inorganique, un agent ignifugeant, un colorant, du noir de carbone et des nanocharges carbonées, à l’exception d’un agent nucléant, en particulier les additifs sont choisis parmi un antioxydant, un stabilisant à la chaleur, un absorbeur d’UV, un stabilisant à la lumière, un lubrifiant, une charge inorganique, un agent ignifugeant, un colorant, du noir de carbone et des nanocharges carbonées, à l’exception d’un agent nucléant. The additives can be selected from another polymer, an antioxidant, a heat stabilizer, a UV absorber, a light stabilizer, a lubricant, an inorganic filler, a flame retardant, a colorant, carbon black and carbonaceous nanofillers, with the exception of a nucleating agent, in particular the additives are chosen from an antioxidant, a heat stabilizer, a UV absorber, a light stabilizer, a lubricant, an inorganic filler, a flame retardant, a colorant, carbon black and carbonaceous nanofillers, except for a nucleating agent.
Ledit autre polymère peut être un autre polymère thermoplastique semi-cristallin ou un polymère différent et notamment un EVOH (Ethylène vinyle alcool). Said other polymer can be another semi-crystalline thermoplastic polymer or a different polymer and in particular an EVOH (Ethylene vinyl alcohol).
Avantageusement, ladite composition comprend ledit polymère thermoplastique PA11 majoritairement, de 0 à moins de 15% de modifiant choc, en particulier de 0 à 12% de modifiant choc, de 0 à 1 ,5% de plastifiant et de 0 à 5% en poids d’additifs, la somme des constituants de la composition étant égale à 100%. Advantageously, said composition comprises mainly said thermoplastic polymer PA11, from 0 to less than 15% of impact modifier, in particular from 0 to 12% of impact modifier, from 0 to 1.5% of plasticizer and from 0 to 5% by weight additives, the sum of the constituents of the composition being equal to 100%.
Avantageusement, ladite composition comprend ledit polymère thermoplastique PA11, de 0 à moins de 15% de modifiant choc, en particulier de 0 à 12% de modifiant choc, de 0 à 1 ,5% de plastifiant et de 0 à 5% en poids d’additifs, la somme des constituants de la composition étant égale à 100%. Avantageusement, ladite composition est constituée dudit polymère thermoplastique PA11 majoritairement, de 0 à moins de 15% en poids de modifiant choc, en particulier de 0 à 12% en poids de modifiant choc, de 0 à 1 ,5% en poids de plastifiant et de 0 à 5% en poids d’additifs, la somme des constituants de la composition étant égale à 100%. Avantageusement, ladite composition est constituée dudit polymère thermoplastique PA11 , de 0 à moins de 15% en poids de modifiant choc, en particulier de 0 à 12% en poids de modifiant choc, de 0 à 1 ,5% en poids de plastifiant et de 0 à 5% en poids d’additifs, la somme des constituants de la composition étant égale à 100%. Avantageusement, ladite composition comprend ledit polymère thermoplastique PA11 majoritairement, de 0,1 à moins de 15% de modifiant choc, en particulier de 0,1 à 12% de modifiant choc, de 0 à 1,5% de plastifiant et de 0 à 5% en poids d’additifs, la somme des constituants de la composition étant égale à 100%. Advantageously, said composition comprises said thermoplastic polymer PA11, from 0 to less than 15% of impact modifier, in particular from 0 to 12% of impact modifier, from 0 to 1.5% of plasticizer and from 0 to 5% by weight of 'additives, the sum of the constituents of the composition being equal to 100%. Advantageously, said composition consists of said thermoplastic polymer PA11 predominantly, from 0 to less than 15% by weight of impact modifier, in particular from 0 to 12% by weight of impact modifier, from 0 to 1.5% by weight of plasticizer and from 0 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%. Advantageously, said composition consists of said thermoplastic polymer PA11, from 0 to less than 15% by weight of impact modifier, in particular from 0 to 12% by weight of impact modifier, from 0 to 1.5% by weight of plasticizer and of 0 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%. Advantageously, said composition comprises said thermoplastic polymer PA11 predominantly, from 0.1 to less than 15% of impact modifier, in particular from 0.1 to 12% of impact modifier, from 0 to 1.5% of plasticizer and from 0 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
Avantageusement, ladite composition comprend ledit polymère thermoplastique PA11, de 0,1 à moins de 15% de modifiant choc, en particulier de 0,1 à 12% de modifiant choc, de 0 à 1 ,5% de plastifiant et de 0 à 5% en poids d’additifs, la somme des constituants de la composition étant égale à 100%. Advantageously, said composition comprises said thermoplastic polymer PA11, from 0.1 to less than 15% of impact modifier, in particular from 0.1 to 12% of impact modifier, from 0 to 1.5% of plasticizer and from 0 to 5 % by weight of additives, the sum of the constituents of the composition being equal to 100%.
Avantageusement, ladite composition est constituée dudit polymère thermoplastique PA11 majoritairement, de 0,1 à moins de 15% en poids de modifiant choc, en particulier de 0,1 à 12% en poids de modifiant choc, de 0 à 1,5% en poids de plastifiant et de 0 à 5% en poids d’additifs, la somme des constituants de la composition étant égale à 100%. Avantageusement, ladite composition est constituée dudit polymère thermoplastique PA11 , de 0,1 à moins de 15% en poids de modifiant choc, en particulier de 0,1 à 12% en poids de modifiant choc, de 0 à 1 ,5% en poids de plastifiant et de 0 à 5% en poids d’additifs, la somme des constituants de la composition étant égale à 100%. Avantageusement, ladite composition comprend ledit polymère thermoplastique PA11 majoritairement, de 0,1 à moins de 15% de modifiant choc, en particulier de 0,1 à 12% de modifiant choc, de 0,1 à 1,5% de plastifiant et de 0 à 5% en poids d’additifs, la somme des constituants de la composition étant égale à 100%. Advantageously, said composition consists of said thermoplastic polymer PA11 predominantly, from 0.1 to less than 15% by weight of impact modifier, in particular from 0.1 to 12% by weight of impact modifier, from 0 to 1.5% by weight. weight of plasticizer and from 0 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%. Advantageously, said composition consists of said thermoplastic polymer PA11, from 0.1 to less than 15% by weight of impact modifier, in particular from 0.1 to 12% by weight of impact modifier, from 0 to 1.5% by weight of plasticizer and from 0 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%. Advantageously, said composition comprises mainly said thermoplastic polymer PA11, from 0.1 to less than 15% of impact modifier, in particular from 0.1 to 12% of impact modifier, from 0.1 to 1.5% of plasticizer and of 0 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
Avantageusement, ladite composition comprend ledit polymère thermoplastique PA11, de 0,1 à moins de 15% de modifiant choc, en particulier de 0,1 à 12% de modifiant choc, de 0 à 1 ,5% de plastifiant et de 0 à 5% en poids d’additifs, la somme des constituants de la composition étant égale à 100%. Advantageously, said composition comprises said thermoplastic polymer PA11, from 0.1 to less than 15% of impact modifier, in particular from 0.1 to 12% of impact modifier, from 0 to 1.5% of plasticizer and from 0 to 5 % by weight of additives, the sum of the constituents of the composition being equal to 100%.
Avantageusement, ladite composition est constituée dudit polymère thermoplastique PA11 majoritairement, de 0,1 à moins de 15% en poids de modifiant choc, en particulier de 0,1 à 12% en poids de modifiant choc, de 0,1 à 1 ,5% en poids de plastifiant et de 0 à 5% en poids d’additifs, la somme des constituants de la composition étant égale à 100%. Avantageusement, ladite composition est constituée dudit polymère thermoplastique PA11 , de 0,1 à moins de 15% en poids de modifiant choc, en particulier de 0,1 à 12% en poids de modifiant choc, de 0,1 à 1,5% en poids de plastifiant et de 0 à 5% en poids d’additifs, la somme des constituants de la composition étant égale à 100%. Avantageusement, ladite composition comprend ledit polymère thermoplastique PA11 majoritairement, de 0,1 à moins de 15% de modifiant choc, en particulier de 0,1 à 12% de modifiant choc, de 0,1 à 1,5% de plastifiant et de 0,1 à 5% en poids d’additifs, la somme des constituants de la composition étant égale à 100%. Advantageously, said composition consists mainly of said thermoplastic polymer PA11, from 0.1 to less than 15% by weight of impact modifier, in particular from 0.1 to 12% by weight of impact modifier, from 0.1 to 1.5% by weight of impact modifier, in particular from 0.1 to 12% by weight of impact modifier, from 0.1 to 1.5. % by weight of plasticizer and from 0 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%. Advantageously, said composition consists of said thermoplastic polymer PA11, from 0.1 to less than 15% by weight of impact modifier, in particular from 0.1 to 12% by weight of impact modifier, from 0.1 to 1.5% by weight of plasticizer and from 0 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%. Advantageously, said composition comprises said thermoplastic polymer PA11 predominantly, from 0.1 to less than 15% of impact modifier, in particular from 0.1 to 12% of impact modifier, from 0.1 to 1.5% of plasticizer and of 0.1 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
Avantageusement, ladite composition comprend ledit polymère thermoplastique PA11, de 0,1 à moins de 15% de modifiant choc, en particulier de 0,1 à 12% de modifiant choc, de 0 à 1 ,5% de plastifiant et de 0,1 à 5% en poids d’additifs, la somme des constituants de la composition étant égale à 100%. Advantageously, said composition comprises said thermoplastic polymer PA11, from 0.1 to less than 15% of impact modifier, in particular from 0.1 to 12% of impact modifier, from 0 to 1.5% of plasticizer and 0.1 at 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
Avantageusement, ladite composition est constituée dudit polymère thermoplastique PA11 majoritairement, de 0,1 à moins de 15% en poids de modifiant choc, en particulier de 0,1 à 12% en poids de modifiant choc, de 0,1 à 1 ,5% en poids de plastifiant et de 0,1 à 5% en poids d’additifs, la somme des constituants de la composition étant égale à 100%. Avantageusement, ladite composition est constituée dudit polymère thermoplastique PA11 , de 0,1 à moins de 15% en poids de modifiant choc, en particulier de 0,1 à 12% en poids de modifiant choc, de 0,1 à 1,5% en poids de plastifiant et de 0,1 à 5% en poids d’additifs, la somme des constituants de la composition étant égale à 100%. Advantageously, said composition consists mainly of said thermoplastic polymer PA11, from 0.1 to less than 15% by weight of impact modifier, in particular from 0.1 to 12% by weight of impact modifier, from 0.1 to 1.5% by weight of impact modifier, in particular from 0.1 to 12% by weight of impact modifier, from 0.1 to 1.5. % by weight of plasticizer and from 0.1 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%. Advantageously, said composition consists of said thermoplastic polymer PA11, from 0.1 to less than 15% by weight of impact modifier, in particular from 0.1 to 12% by weight of impact modifier, from 0.1 to 1.5% by weight of plasticizer and from 0.1 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
Dans un mode de réalisation, ladite composition comprend un modifiant choc de 0,1 à moins de 15% en poids, en particulier de 0,1 à 12% en poids de modifiant choc, notamment de 5 à 12% en poids par rapport au poids total de la composition. In one embodiment, said composition comprises an impact modifier from 0.1 to less than 15% by weight, in particular from 0.1 to 12% by weight of impact modifier, in particular from 5 to 12% by weight relative to the total weight of the composition.
Dans un mode de réalisation, ladite composition est dépourvue de modifiant choc. In one embodiment, said composition is devoid of impact modifier.
Dans ce mode de réalisation, ladite composition comprend donc ledit polymère thermoplastique PA11 majoritairement, de 0 à 1 ,5% de plastifiant et de 0,1 à 5% en poids d’additifs, la somme des constituants de la composition étant égale à 100%. Avantageusement, ladite composition comprend donc ledit polymère thermoplastique PA11, de 0 à 1,5% de plastifiant et de 0,1 à 5% en poids d’additifs, la somme des constituants de la composition étant égale à 100%. In this embodiment, said composition therefore comprises said thermoplastic polymer PA11 predominantly, from 0 to 1.5% of plasticizer and from 0.1 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100 %. Advantageously, said composition therefore comprises said thermoplastic polymer PA11, from 0 to 1.5% of plasticizer and from 0.1 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
Avantageusement, ladite composition est constituée dudit polymère thermoplastique PA11 majoritairement, de 0 à 1,5% de plastifiant et de 0,1 à 5% en poids d’additifs, la somme des constituants de la composition étant égale à 100%. Advantageously, said composition consists mainly of said thermoplastic polymer PA11, from 0 to 1.5% of plasticizer and from 0.1 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
Dans ce cas, le PA11 majoritaire est en mélange avec un autre polyamide. Avantageusement, ladite composition est constituée dudit polymère thermoplastique PA11 , de 0 à 1 ,5% de plastifiant et de 0,1 à 5% en poids d’additifs, la somme des constituants de la composition étant égale à 100%. Dans un mode de réalisation, ladite composition est dépourvue de plastifiant. In this case, the majority PA11 is mixed with another polyamide. Advantageously, said composition consists of said thermoplastic polymer PA11, from 0 to 1.5% of plasticizer and from 0.1 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%. In one embodiment, said composition is devoid of plasticizer.
Dans ce mode de réalisation, ladite composition comprend donc ledit polymère thermoplastique PA11 majoritairement, de 0,1 à moins de 15% de modifiant choc, en particulier de 0,1 à 12% de modifiant choc et de 0,1 à 5% en poids d’additifs, la somme des constituants de la composition étant égale à 100%. In this embodiment, said composition therefore comprises said thermoplastic polymer PA11 predominantly, from 0.1 to less than 15% of impact modifier, in particular from 0.1 to 12% of impact modifier and from 0.1 to 5% in weight of additives, the sum of the constituents of the composition being equal to 100%.
Avantageusement, ladite composition comprend donc ledit polymère thermoplastique PA11, de 0,1 à moins de 15% de modifiant choc, en particulier de 0,1 à 12% de modifiant choc et de 0,1 à 5% en poids d’additifs, la somme des constituants de la composition étant égale à 100%. Advantageously, said composition therefore comprises said thermoplastic polymer PA11, from 0.1 to less than 15% of impact modifier, in particular from 0.1 to 12% of impact modifier and from 0.1 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
Avantageusement, ladite composition est constituée dudit polymère thermoplastique PA11 majoritairement, de 0,1 à moins de 15% de modifiant choc, en particulier de 0,1 à 12% de modifiant choc et de 0,1 à 5% en poids d’additifs, la somme des constituants de la composition étant égale à 100%. Advantageously, said composition consists predominantly of said thermoplastic polymer PA11, from 0.1 to less than 15% of impact modifier, in particular from 0.1 to 12% of impact modifier and from 0.1 to 5% by weight of additives. , the sum of the constituents of the composition being equal to 100%.
Dans ce cas, le PA11 majoritaire est en mélange avec un autre polyamide. Avantageusement, ladite composition est constituée dudit polymère thermoplastique PA11, de 0,1 à moins de 15% de modifiant choc, en particulier de 0,1 à 12% de modifiant choc et de 0,1 à 5% en poids d’additifs, la somme des constituants de la composition étant égale à 100%. In this case, the majority PA11 is mixed with another polyamide. Advantageously, said composition consists of said thermoplastic polymer PA11, from 0.1 to less than 15% of impact modifier, in particular from 0.1 to 12% of impact modifier and from 0.1 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
Dans encore un autre mode de réalisation, ladite composition est dépourvue de modifiant choc et de plastifiant. In yet another embodiment, said composition is devoid of impact modifier and plasticizer.
Dans cet autre mode de réalisation, ladite composition comprend donc ledit polymère thermoplastique PA11 majoritairement et de 0,1 à 5% en poids d’additifs, la somme des constituants de la composition étant égale à 100%. In this other embodiment, said composition therefore comprises said thermoplastic polymer PA11 predominantly and from 0.1 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
Avantageusement, ladite composition comprend donc ledit polymère thermoplastique PA11 et de 0,1 à 5% en poids d’additifs, la somme des constituants de la composition étant égale à 100%. Advantageously, said composition therefore comprises said thermoplastic polymer PA11 and from 0.1 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
Avantageusement, ladite composition est constituée dudit polymère thermoplastique PA11 majoritairement et de 0,1 à 5% en poids d’additifs, la somme des constituants de la composition étant égale à 100%. Advantageously, said composition consists of said thermoplastic polymer PA11 predominantly and from 0.1 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
Dans ce cas, le PA11 majoritaire est en mélange avec un autre polyamide. Avantageusement, ladite composition est constituée dudit polymère thermoplastique PA11 et de 0,1 à 5% en poids d’additifs, la somme des constituants de la composition étant égale à 100%. In this case, the majority PA11 is mixed with another polyamide. Advantageously, said composition consists of said thermoplastic polymer PA11 and from 0.1 to 5% by weight of additives, the sum of the constituents of the composition being equal to 100%.
Dans un autre mode de réalisation, ladite composition comprend un modifiant choc de 0,1 à moins de 15% en poids, en particulier de 0,1 à 12% en poids, notamment de 5 à 12% en poids de modifiant choc et ladite composition est dépourvue de plastifiant par rapport au poids total de la composition. Dans encore un autre mode de réalisation, ladite composition comprend un modifiant choc de 0,1 à moins de 15% en poids, en particulier de 0,1 à 12% en poids de modifiant choc, notamment de 5 à 12% en poids et de 0,1 à 1 ,5% en poids de plastifiant par rapport au poids total de la composition. In another embodiment, said composition comprises an impact modifier of 0.1 to less than 15% by weight, in particular from 0.1 to 12% by weight, in particular from 5 to 12% by weight of impact modifier and said composition is devoid of plasticizer relative to the total weight of the composition. In yet another embodiment, said composition comprises an impact modifier from 0.1 to less than 15% by weight, in particular from 0.1 to 12% by weight of impact modifier, in particular from 5 to 12% by weight and from 0.1 to 1.5% by weight of plasticizer relative to the total weight of the composition.
Polymère thermoplastique PA11 PA11 thermoplastic polymer
La masse moléculaire moyenne en nombre Mn dudit polymère thermoplastique polyamide PA11 est de préférence dans une plage allant de 10000 à 85000, notamment de 10000 à 60000, préférentiellement de 10000 à 50000, encore plus préférentiellement de 12000 à 50000. Ces valeurs Mn peuvent correspondre à des viscosités inhérentes supérieures ou égales à 0,8 telle que déterminées dans le m-crésol selon la norme ISO 307:2007 mais en changeant le solvant (utilisation du m-crésol à la place de l’acide sulfurique et la température étant de 20°C). The number-average molecular mass Mn of said thermoplastic polyamide PA11 polymer is preferably in a range going from 10,000 to 85,000, in particular from 10,000 to 60,000, preferably from 10,000 to 50,000, even more preferably from 12,000 to 50,000. These Mn values may correspond to inherent viscosities greater than or equal to 0.8 as determined in m-cresol according to standard ISO 307: 2007 but by changing the solvent (use of m-cresol instead of sulfuric acid and the temperature being 20 ° C).
La nomenclature utilisée pour définir les polyamides est décrite dans la norme ISO 1874- 1 :2011 "Plastiques - Matériaux polyamides (PA) pour moulage et extrusion - Partie 1 : Désignation", notamment en page 3 (tableaux 1 et 2) et est bien connue de l’homme du métier. The nomenclature used to define polyamides is described in standard ISO 1874-1: 2011 "Plastics - Polyamide materials (PA) for molding and extrusion - Part 1: Designation", in particular on page 3 (tables 1 and 2) and is indeed known to those skilled in the art.
Le polyamide PA11 est un homopolyamide mais on ne sortirait pas du cadre de l’invention si la composition constitutive de la couche d’étanchéité comprenait un copolyamide à base de PA11 dans lequel le motif PA11 et majoritaire, c’est-à-dire supérieur à 50% en poids, notamment supérieur à 60% en poids, supérieur à 70% en poids, supérieur à 80% en poids, supérieur à 90% en poids, par rapport au total des motifs dudit copolyamide ou un mélange de ceux-ci. Polyamide PA11 is a homopolyamide but it would not be departing from the scope of the invention if the constituent composition of the waterproofing layer included a copolyamide based on PA11 in which the PA11 unit is predominant, that is to say greater than 50% by weight, in particular greater than 60% by weight, greater than 70% by weight, greater than 80% by weight, greater than 90% by weight, relative to the total of the units of said copolyamide or a mixture thereof .
Avantageusement, le polyamide PA11 est un homopolyamide. Advantageously, the polyamide PA11 is a homopolyamide.
S’agissant du modifiant choc Regarding the impact modifier
Le modifiant choc peut être tout modifiant choc à partir du moment où un polymère de module inférieur à celui de la résine, présentant une bonne adhésion avec la matrice, de manière à dissiper l’énergie de fissuration. The impact modifier can be any impact modifier from the moment when a polymer of lower modulus than that of the resin, exhibiting good adhesion with the matrix, so as to dissipate the cracking energy.
Le modifiant choc est avantageusement constitué par un polymère présentant un module de flexion inférieur à 100 MPa mesuré selon la norme ISO 178 et de Tg inférieure à 0°C (mesurée selon la norme 11357-2 au niveau du point d’inflexion du thermogramme DSC), en particulier une polyoléfine. The impact modifier is advantageously constituted by a polymer having a flexural modulus of less than 100 MPa measured according to the ISO 178 standard and of Tg less than 0 ° C (measured according to the 11357-2 standard at the inflection point of the DSC thermogram ), in particular a polyolefin.
Dans un mode de réalisation, les PEBA sont exclus de la définition des modifiants choc.In one embodiment, PEBAs are excluded from the definition of impact modifiers.
La polyoléfine du modifiant choc peut être fonctionnalisée ou non fonctionnalisée ou être un mélange d'au moins une fonctionnalisée et/ou d'au moins une non fonctionnalisée.The polyolefin of the impact modifier can be functionalized or non-functionalized or be a mixture of at least one functionalized and / or at least one non-functionalized.
Pour simplifier on a désigné la polyoléfine par (B) et on a décrit ci- dessous des polyoléfines fonctionnalisées (B1) et des polyoléfines non fonctionnalisées (B2). Une polyoléfine non fonctionnalisée (B2) est classiquement un homo polymère ou copolymère d'alpha oléfines ou de dioléfines, telles que par exemple, éthylène, propylène, butène-1, octène-1 , butadiène. A titre d'exemple, on peut citer : For simplicity, the polyolefin has been designated by (B) and functionalized polyolefins (B1) and unfunctionalized polyolefins (B2) have been described below. An unfunctionalized polyolefin (B2) is conventionally a homopolymer or copolymer of alpha olefins or diolefins, such as, for example, ethylene, propylene, butene-1, octene-1, butadiene. By way of example, we can cite:
- les homo polymères et copolymères du polyéthylène, en particulier LDPE, HDPE, LLDPE(linear low density polyéthylène, ou polyéthylène basse densité linéaire), VLDPE(very low density polyéthylène, ou polyéthylène très basse densité) et le polyéthylène métallocène . - polyethylene homopolymers and copolymers, in particular LDPE, HDPE, LLDPE (linear low density polyethylene, or linear low density polyethylene), VLDPE (very low density polyethylene, or very low density polyethylene) and metallocene polyethylene.
-les homopolymères ou copolymères du propylène. the homopolymers or copolymers of propylene.
- les copolymères éthylène/alpha-oléfine tels qu'éthylène/propylène, les EPR(abréviation d'éthylène-propylene-rubber) et éthylène/propylène/diène (EPDM). - ethylene / alpha-olefin copolymers such as ethylene / propylene, EPR (abbreviation of ethylene-propylene-rubber) and ethylene / propylene / diene (EPDM).
- les copolymères blocs styrène/éthylène-butène/styrène (SEBS), styrène/butadiène/styrène (SBS), styrène/isoprène/ styrène (SIS), styrène/éthylène- propylène/styrène (SEPS). - styrene / ethylene-butene / styrene (SEBS), styrene / butadiene / styrene (SBS), styrene / isoprene / styrene (SIS), styrene / ethylene-propylene / styrene (SEPS) block copolymers.
- les copolymères de l'éthylène avec au moins un produit choisi parmi les sels ou les esters d'acides carboxyliques insaturés tel que le (méth)acrylate d'alkyle (par exemple acrylate de méthyle), ou les esters vinyliques d'acides carboxyliques saturés tel que l'acétate de vinyle (EVA), la proportion de comonomère pouvant atteindre 40% en poids. La polyoléfine fonctionnalisée (B1) peut être un polymère d'alpha oléfines ayant des motifs réactifs (les fonctionnalités) ; de tels motifs réactifs sont les fonctions acides, anhydrides, ou époxy. À titre d'exemple, on peut citer les polyoléfines précédentes (B2) greffées ou co- ou ter polymérisées par des époxydes insaturés tels que le (méth)acrylate de glycidyle, ou par des acides carboxyliques ou les sels ou esters correspondants tels que l'acide (méth)acrylique (celui-ci pouvant être neutralisé totalement ou partiellement par des métaux tels que Zn, etc.) ou encore par des anhydrides d'acides carboxyliques tels que l'anhydride maléique. Une polyoléfine fonctionnalisée est par exemple un mélange PE/EPR, dont le ratio en poids peut varier dans de larges mesures, par exemple entre 40/60 et 90/10, ledit mélange étant co-greffé avec un anhydride, notamment anhydride maléique, selon un taux de greffage par exemple de 0,01 à 5% en poids. - copolymers of ethylene with at least one product chosen from salts or esters of unsaturated carboxylic acids such as alkyl (meth) acrylate (for example methyl acrylate), or vinyl esters of carboxylic acids saturated such as vinyl acetate (EVA), the proportion of comonomer being up to 40% by weight. The functionalized polyolefin (B1) can be a polymer of alpha olefins having reactive units (the functionalities); such reactive units are acid, anhydride or epoxy functions. By way of example, mention may be made of the preceding polyolefins (B2) grafted or co- or ter polymerized with unsaturated epoxides such as glycidyl (meth) acrylate, or with carboxylic acids or the corresponding salts or esters such as (meth) acrylic acid (the latter being able to be totally or partially neutralized by metals such as Zn, etc.) or alternatively by carboxylic acid anhydrides such as maleic anhydride. A functionalized polyolefin is for example a PE / EPR mixture, the weight ratio of which can vary widely, for example between 40/60 and 90/10, said mixture being co-grafted with an anhydride, in particular maleic anhydride, according to a degree of grafting, for example from 0.01 to 5% by weight.
La polyoléfine fonctionnalisée (B1) peut être choisie parmi les (co)polymères suivants, greffés avec anhydride maléique ou méthacrylate de glycidyle, dans lesquels le taux de greffage est par exemple de 0,01 à 5% en poids : The functionalized polyolefin (B1) can be chosen from the following (co) polymers, grafted with maleic anhydride or glycidyl methacrylate, in which the degree of grafting is for example from 0.01 to 5% by weight:
- du PE, du PP, des copolymères de l'éthylène avec propylène, butène, hexène, ou octène contenant par exemple de 35 à 80% en poids d'éthylène ; - PE, PP, copolymers of ethylene with propylene, butene, hexene or octene containing, for example, from 35 to 80% by weight of ethylene;
- les copolymères éthylène/alpha-oléfine tels qu'éthylène/propylène, les EPR(abréviation d'éthylène-propylene-rubber) et éthylène/propylène/diène (EPDM). - les copolymères blocs styrène/éthylène-butène/styrène (SEBS), styrène/butadiène/styrène (SBS), styrène/isoprène/ styrène (SIS), styrène/éthylène- propylène/styrène (SEPS). - ethylene / alpha-olefin copolymers such as ethylene / propylene, EPR (abbreviation of 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.
- des copolymères éthylène et acétate de vinyle (EVA), contenant jusqu'à 40% en poids d'acétate de vinyle ; - ethylene and vinyl acetate (EVA) copolymers, containing up to 40% by weight of vinyl acetate;
- des copolymères éthylène et (méth)acrylate d'alkyle, contenant jusqu'à 40% en poids de (méth)acrylate d'alkyle ; - ethylene and alkyl (meth) acrylate copolymers, containing up to 40% by weight of alkyl (meth) acrylate;
- des copolymères éthylène et acétate de vinyle (EVA) et (méth)acrylate d'alkyle, contenant jusqu'à 40% en poids de comonomères. - copolymers of ethylene and vinyl acetate (EVA) and (meth) acrylate, containing up to 40% by weight of comonomers.
La polyoléfine fonctionnalisée (B1) peut être aussi choisie parmi les copolymères éthylène/propylène majoritaires en propylène greffés par de l'anhydride maléique puis condensés avec du polyamide (ou un oligomère de polyamide) mono aminé (produits décrits dans EP-A-0342066). The functionalized polyolefin (B1) can also be chosen from ethylene / propylene copolymers predominantly in propylene grafted with maleic anhydride then condensed with mono-amine polyamide (or a polyamide oligomer) (products described in EP-A-0342066) .
La polyoléfine fonctionnalisée (B1) peut aussi être un co- ou ter polymère d'au moins les motifs suivants : (1) éthylène, (2) (méth)acrylate d'alkyle ou ester vinylique d'acide carboxylique saturé et (3) anhydride tel que anhydride maléique ou acide (méth)acrylique ou époxy tel que (méth)acrylate de glycidyle. The functionalized polyolefin (B1) can also be a co- or ter polymer of at least the following units: (1) ethylene, (2) alkyl (meth) acrylate or vinyl ester of saturated carboxylic acid and (3) anhydride such as maleic anhydride or (meth) acrylic acid or epoxy such as glycidyl (meth) acrylate.
A titre d'exemple de polyoléfines fonctionnalisées de ce dernier type, on peut citer les copolymères suivants, où l'éthylène représente de préférence au moins 60% en poids et où le ter monomère (la fonction) représente par exemple de 0,1 à 10% en poids du copolymère : By way of example of functionalized polyolefins of the latter type, mention may be made of the following copolymers, where ethylene preferably represents at least 60% by weight and where the ter monomer (the function) represents for example from 0.1 to 10% by weight of the copolymer:
- les copolymères éthylène/(méth)acrylate d'alkyle / acide (méth)acrylique ou anhydride maléique ou méthacrylate de glycidyle ; - ethylene / (meth) acrylate / (meth) acrylic acid or maleic anhydride or glycidyl methacrylate copolymers;
- les copolymères éthylène/acétate de vinyle/anhydride maléique ou méthacrylate de glycidyle ; - ethylene / vinyl acetate / maleic anhydride or glycidyl methacrylate copolymers;
- les copolymères éthylène/acétate de vinyle ou (méth)acrylate d'alkyle / acide (méth)acrylique ou anhydride maléique ou méthacrylate de glycidyle. - ethylene / vinyl acetate or (meth) acrylate / (meth) acrylic acid or maleic anhydride or glycidyl methacrylate copolymers.
Dans les copolymères qui précèdent, l'acide (méth)acrylique peut être salifié avec Zn ou Li. In the above copolymers, (meth) acrylic acid can be salified with Zn or Li.
Le terme "(méth)acrylate d'alkyle" dans (B1) ou (B2) désigne les méthacrylates et les acrylates d'alkyle en C1 à C8, et peut être choisi parmi l'acrylate de méthyle, l'acrylate d'éthyle, l'acrylate de n-butyle, l'acrylate d'iso butyle, l'acrylate d'éthyl-2-hexyle, l'acrylate de cyclohexyle, le méthacrylate de méthyle et le méthacrylate d'éthyle. The term "alkyl (meth) acrylate" in (B1) or (B2) denotes methacrylates and acrylates of C1 to C8 alkyl, and may be chosen from methyl acrylate, ethyl acrylate , n-butyl acrylate, isobutyl acrylate, ethyl-2-hexyl acrylate, cyclohexyl acrylate, methyl methacrylate and ethyl methacrylate.
Par ailleurs, les polyoléfines précitées (B1) peuvent aussi être réticulées par tout procédé ou agent approprié (diépoxy, diacide, peroxyde, etc.) ; le terme polyoléfine fonctionnalisée comprend aussi les mélanges des polyoléfines précitées avec un réactif difonctionnel tel que diacide, dianhydride, diépoxy, etc. susceptible de réagir avec celles-ci ou les mélanges d'au moins deux polyoléfines fonctionnalisées pouvant réagir entre elles. Furthermore, the aforementioned polyolefins (B1) can also be crosslinked by any suitable process or agent (diepoxy, diacid, peroxide, etc.); the term functionalized polyolefin also includes mixtures of the aforementioned polyolefins with a difunctional reagent such as as diacid, dianhydride, diepoxy, etc. capable of reacting with these or mixtures of at least two functionalized polyolefins capable of reacting with each other.
Les copolymères mentionnés ci-dessus, (B1 ) et (B2), peuvent être copolymérisés de façon statistique ou séquencée et présenter une structure linéaire ou ramifiée. The copolymers mentioned above, (B1) and (B2), can be copolymerized in a random or block fashion and have a linear or branched structure.
Le poids moléculaire, l'indice MFI, la densité de ces polyoléfines peuvent aussi varier dans une large mesure, ce que l'homme de l'art appréciera. MFI, abréviation de Melt Flow Index, est l'indice de fluidité à l'état fondu. On le mesure selon la norme ASTM 1238. Avantageusement les polyoléfines (B2) non fonctionnalisées sont choisies parmi les homopolymères ou copolymères du polypropylène et tout homo polymère de l’éthylène ou copolymère de l’éthylène et d’un comonomère de type alpha oléfinique supérieur tel que le butène, l’hexène, l’octène ou le 4-méthyl 1-Pentène. On peut citer par exemple les PP, les PE de haute densité, PE de moyenne densité, PE basse densité linéaire, PE basse densité, PE de très basse densité. Ces polyéthylènes sont connus par l’Homme de l’Art comme étant produits selon un procédé « radicalaire », selon une catalyse de type « Ziegler » ou, plus récemment, selon une catalyse dite « métallocène ». The molecular weight, the MFI number, the density of these polyolefins can also vary to a large extent, which will be appreciated by those skilled in the art. MFI, short for Melt Flow Index, is the melt flow index. It is measured according to standard ASTM 1238. Advantageously, the unfunctionalized polyolefins (B2) are chosen from homopolymers or copolymers of polypropylene and any homopolymer of ethylene or copolymer of ethylene and of a comonomer of higher alpha olefinic type. such as butene, hexene, octene or 4-methyl 1-Pentene. Mention may be made, for example, of PPs, high density PE, medium density PE, linear low density PE, low density PE, very low density PE. These polyethylenes are known to those skilled in the art as being produced according to a "radical" process, according to a "Ziegler" type catalysis or, more recently, according to a so-called "metallocene" catalysis.
Avantageusement les polyoléfines fonctionnalisées (B1 ) sont choisies parmi tout polymère comprenant des motifs alpha oléfiniques et des motifs porteurs de fonctions réactives polaires comme les fonctions époxy, acide carboxylique ou anhydride d’acide carboxylique. A titre d’exemples de tels polymères, on peut citer les ter polymères de l’éthylène, d’acrylate d’alkyle et d’anhydride maléique ou de méthacrylate de glycidyle comme les Lotader® de la Demanderesse ou des polyoléfines greffées par de l’anhydride maléique comme les Orevac® de la Demanderesse ainsi que des ter polymères de l’éthylène, d’acrylate d’alkyle et d’acide (meth) acrylique. On peut citer aussi les homopolymères ou copolymères du polypropylène greffés par un anhydride d'acide carboxylique puis condensés avec des polyamides ou des oligomères mono aminés de polyamide. Advantageously, the functionalized polyolefins (B1) are chosen from any polymer comprising alpha olefinic units and units bearing polar reactive functions such as epoxy, carboxylic acid or carboxylic acid anhydride functions. As examples of such polymers, mention may be made of the ter polymers of ethylene, of alkyl acrylate and of maleic anhydride or of glycidyl methacrylate, such as Lotader® from the Applicant or polyolefins grafted with l. maleic anhydride such as Orevac® from the Applicant as well as ter polymers of ethylene, of alkyl acrylate and of (meth) acrylic acid. Mention may also be made of homopolymers or copolymers of polypropylene grafted with a carboxylic acid anhydride and then condensed with polyamides or mono-amino polyamide oligomers.
Avantageusement, ladite composition constitutive de ladite ou desdites couches d’étanchéité est dépourvue de polyéther block amide (PEBA). Dans ce mode de réalisation, les PEBA sont donc exclus des modifiants choc. Advantageously, said constituent composition of said sealant layer or layers is devoid of polyether block amide (PEBA). In this embodiment, the PEBAs are therefore excluded from the impact modifiers.
Avantageusement, ladite composition transparente est dépourvue de particules cœur- écorce ou polymères cœur-écorce « core-shell ». Advantageously, said transparent composition is devoid of core-shell particles or “core-shell” core-shell polymers.
Par particule cœur-écorce, il faut comprendre une particule dont la première couche forme le cœur et la deuxième ou toutes les couches suivantes forment les écorces respectives. By core-shell particle, it is necessary to understand a particle of which the first layer forms the core and the second or all of the following layers form the respective shell.
La particule cœur-écorce « core-shell » peut-être obtenu par un procédé à plusieurs étapes comprenant au moins deux étapes. Un tel procédé est décrit par exemple dans les documents US2009/0149600 ou EP0722961. S’agissant du plastifiant The core-shell particle can be obtained by a multi-step process comprising at least two steps. Such a method is described for example in documents US2009 / 0149600 or EP0722961. Regarding the plasticizer
Le plastifiant peut être un plastifiant couramment utilisé dans les compositions à base de polyamide(s). The plasticizer can be a plasticizer commonly used in compositions based on polyamide (s).
Avantageusement, on utilise un plastifiant qui présente une bonne stabilité thermique afin qu'il ne se forme pas de fumées lors des étapes de mélange des différents polymères et de transformation de la composition obtenue. Advantageously, a plasticizer is used which has good thermal stability so that no fumes are formed during the stages of mixing the various polymers and of processing the composition obtained.
En particulier, ce plastifiant peut être choisi parmi : les dérivés du benzène sulfonamide tels que le n-butyl benzène sulfonamide (BBSA), les isomères ortho et para de l’éthyl toluène sulfonamide (ETSA), le N-cyclohexyl toluène sulfonamide et le N-(2-hydroxypropyl) benzène sulfonamide (HP-BSA), les esters d’acides hydroxybenzoïques tels que le para-hydroxybenzoate d'éthyl-2 hexyleIn particular, this plasticizer can be chosen from: benzene sulfonamide derivatives such as n-butyl benzene sulfonamide (BBSA), ortho and para isomers of ethyl toluene sulfonamide (ETSA), N-cyclohexyl toluene sulfonamide and N- (2-hydroxypropyl) benzenesulfonamide (HP-BSA), esters of hydroxybenzoic acids such as 2-ethylhexyl para-hydroxybenzoate
(EHPB) et le para-hydroxybenzoate de décyl-2 hexyle (HDPB), les esters ou éthers du tétrahydrofurfuryl alcool comme l’oligoéthylèneoxy- tétrahydrofurfurylalcool, et les esters de l’acide citrique ou de l’acide hydroxymalonique, tels que l’oligoéthylèneoxymalonate. (EHPB) and 2-decylhexyl para-hydroxybenzoate (HDPB), esters or ethers of tetrahydrofurfuryl alcohol such as oligoethyleneoxy-tetrahydrofurfurylalcohol, and esters of citric acid or hydroxymalonic acid, such as oligoethylene oxymalonate.
Un plastifiant préféré est le n-butyl benzène sulfonamide (BBSA). A preferred plasticizer is n-butyl benzene sulfonamide (BBSA).
Un autre plastifiant plus particulièrement préféré est le N-(2-hydroxy-propyl) benzène sulfonamide (HP-BSA). Ce dernier présente en effet l'avantage d'éviter la formation de dépôts au niveau de la vis et/ou de la filière d'extrusion ("larmes de filières"), lors d'une étape de transformation par extrusion. Another more particularly preferred plasticizer is N- (2-hydroxy-propyl) benzene sulfonamide (HP-BSA). The latter in fact has the advantage of avoiding the formation of deposits at the level of the screw and / or of the extrusion die (“die tears”), during a step of transformation by extrusion.
On peut bien évidemment utiliser un mélange de plastifiants. It is of course possible to use a mixture of plasticizers.
S’agissant de la couche de renfort composite et du polymère P2j Le polymère P2j peut être un polymère thermoplastique ou un polymère thermodurcissable. Regarding the composite reinforcing layer and the polymer P2j The polymer P2j can be a thermoplastic polymer or a thermosetting polymer.
Une ou plusieurs couches de renfort composite peut ou peuvent être présente(s). One or more composite reinforcement layers may or may be present.
Chacune desdites couches est constituée d’un matériau fibreux sous forme de fibres continues imprégné par une composition comprenant majoritairement au moins un polymère thermoplastique P2j, j correspondant au nombre de couches présentes j est compris de 1 à 10, en particulier de 1 à 5, notamment de 1 à 3, préférentiellement j = 1. Each of said layers consists of a fibrous material in the form of continuous fibers impregnated with a composition mainly comprising at least one thermoplastic polymer P2j, j corresponding to the number of layers present j is from 1 to 10, in particular from 1 to 5, in particular from 1 to 3, preferably j = 1.
Le terme « majoritairement » signifie que ledit au moins un polymère est présent à plus de 50% en poids par rapport au poids total de la composition et de la matrice du composite. Avantageusement, ledit au moins un polymère majoritaire est présent à plus de 60% en poids notamment à plus de 70% en poids, particulièrement à plus de 80% en poids, plus particulièrement supérieur ou égal à 90% en poids, par rapport au poids total de la composition, Ladite composition peut également comprendre des modifiants choc et/ou des additifs. Les additifs peuvent être choisis parmi un antioxydant, un stabilisant à la chaleur, un absorbeur d’UV, un stabilisant à la lumière, un lubrifiant, une charge inorganique, un agent ignifugeant, un plastifiant et un colorant, à l’exception d’un agent nucléant. Avantageusement, ladite composition est constituée dudit polymère thermoplastique P2j majoritairement, de 0 à 15% en poids de modifiant choc, en particulier de 0 à 12% en poids de modifiant choc, de 0 à 5% en poids d’additifs, la somme des constituants de la composition étant égale à 100% en poids. The term “predominantly” means that said at least one polymer is present in more than 50% by weight relative to the total weight of the composition and of the matrix of the composite. Advantageously, said at least one major polymer is present at more than 60% by weight, in particular at more than 70% by weight, particularly at more than 80% by weight, more particularly greater than or equal to 90% by weight, relative to the weight total composition, Said composition can also comprise impact modifiers and / or additives. The additives can be selected from an antioxidant, a heat stabilizer, a UV absorber, a light stabilizer, a lubricant, an inorganic filler, a flame retardant, a plasticizer and a colorant, except for a nucleating agent. Advantageously, said composition consists of said thermoplastic polymer P2j predominantly, from 0 to 15% by weight of impact modifier, in particular from 0 to 12% by weight of impact modifier, from 0 to 5% by weight of additives, the sum of constituents of the composition being equal to 100% by weight.
Ledit au moins un polymère majoritaire de chaque couche peut être identique ou différent. Dans un mode de réalisation, un seul polymère majoritaire est présent au moins dans la couche de renfort composite et qui n’adhère pas à la couche d’étanchéité. Said at least one majority polymer of each layer may be identical or different. In one embodiment, a single major polymer is present at least in the composite reinforcing layer and which does not adhere to the waterproofing layer.
Dans un mode de réalisation, chaque couche de renfort comprend le même type de polymère, en particulier une résine époxyde ou à base d’époxyde. In one embodiment, each reinforcing layer comprises the same type of polymer, in particular an epoxy or epoxy-based resin.
Polymère P2j P2j polymer
Polymère thermoplastique P2j P2j thermoplastic polymer
On entend par thermoplastique, ou polymère thermoplastique, un matériau généralement solide à température ambiante, pouvant être semi-cristallin ou amorphe, en particulier semi-cristallin et qui se ramollit lors d’une augmentation de température, en particulier après passage de sa température de transition vitreuse (Tg) et s’écoule à plus haute température lorsqu’il est amorphe, ou pouvant présenter une fusion franche au passage de sa température dite de fusion (Tf) lorsqu’il est semi-cristallin, et qui redevient solide lors d’une diminution de température en dessous de sa température de cristallisation, Te, (pour un semi-cristallin) et en dessous de sa température de transition vitreuse (pour un amorphe). The term thermoplastic, or thermoplastic polymer, is understood to mean a material which is generally solid at room temperature, which may be semi-crystalline or amorphous, in particular semi-crystalline and which softens during an increase in temperature, in particular after passing its temperature of glass transition (Tg) and flows at a higher temperature when it is amorphous, or may present a clear melting at the passage of its so-called melting temperature (Tf) when it is semi-crystalline, and which becomes solid again during 'a decrease in temperature below its crystallization temperature, Te, (for a semi-crystalline) and below its glass transition temperature (for an amorphous).
La Tg, Te et la Tf sont déterminées par analyse calorimétrique différentielle (DSC) selon la norme 11357-2 :2013 et 11357-3 :2013 respectivement. Tg, Te and Tf are determined by differential scanning calorimetry (DSC) according to standard 11357-2: 2013 and 11357-3: 2013 respectively.
La masse moléculaire moyenne en nombre Mn dudit polymère thermoplastique est de préférence dans une plage allant de 10000 à 40000, de préférence de 10000 à 30000. Ces valeurs Mn peuvent correspondre à des viscosités inhérentes supérieures ou égales à 0,8 telle que déterminées dans le m-crésol selon la norme ISO 307:2007 mais en changeant le solvant (utilisation du m-crésol à la place de l’acide sulfurique et la température étant de 20°C). The number average molecular weight Mn of said thermoplastic polymer is preferably in a range of 10,000 to 40,000, preferably 10,000 to 30,000. These Mn values may correspond to inherent viscosities greater than or equal to 0.8 as determined in the m-cresol according to ISO 307: 2007 but changing the solvent (use of m-cresol instead of sulfuric acid and the temperature being 20 ° C).
Comme exemples de polymères thermoplastiques semi-cristallins convenables dans la présente invention, on peut citer : les polyamides, en particulier comprenant une structure aromatique et/ou cycloaliphatique, y compris les copolymères par exemple les copolymères polyamides- polyéthers, polyesters, les polyaryléthercétones (PAEK), les polyétheréther cétones (PEEK), les polyéthercétone cétones (PEKK), les polyéthercétoneéthercétone cétones (PEKEKK), les polyimides en particulier les polyétherimides (PEI) ou les polyamide-imides, les polylsulfones (PSU) en particulier les polyarylsulfones tels que les polyphényl sulfonesAs examples of semi-crystalline thermoplastic polymers suitable in the present invention, mention may be made of: polyamides, in particular comprising an aromatic and / or cycloaliphatic structure, including copolymers, for example polyamide-polyethers, polyesters, copolymers, polyaryletherketones (PAEK), polyetherether ketones (PEEK), polyetherketone ketones (PEKK), polyetherketoneetherketone ketones (PEKEKK), polyimides in particular polyetherimides (PEI) or polyamide-imides (in particular PSU )sulfones, polylsulfones polyarylsulfones such as polyphenyl sulfones
(PPSU), les polyéthersulfones (PES). les polymères semi-cristallins sont plus particulièrement préférés, et en particulier les polyamides et leurs copolymères semi-cristallins. (PPSU), polyethersulfones (PES). semi-crystalline polymers are more particularly preferred, and in particular polyamides and their semi-crystalline copolymers.
La nomenclature utilisée pour définir les polyamides est décrite dans la norme ISO 1874- 1 :2011 "Plastiques - Matériaux polyamides (PA) pour moulage et extrusion - Partie 1 : Désignation", notamment en page 3 (tableaux 1 et 2) et est bien connue de l’homme du métier. The nomenclature used to define polyamides is described in standard ISO 1874-1: 2011 "Plastics - Polyamide materials (PA) for molding and extrusion - Part 1: Designation", in particular on page 3 (tables 1 and 2) and is indeed known to those skilled in the art.
Le polyamide peut être un homopolyamide ou un copolyamide ou un mélange de ceux-ci. Avantageusement, les polyamides semi-cristallins sont des polyamide semi-aromatiques, notamment un polyamide semi-aromatique de formule X/YAr, tel que décrits dans EP1505099, notamment un polyamide semi-aromatique de formule A/XT dans laquelle A est choisi parmi un motif obtenu à partir d'un aminoacide, un motif obtenu à partir d’un lactame et un motif répondant à la formule (diamine en Ca). (diacide en Cb), avec a représentant le nombre d’atomes de carbone de la diamine et b représentant le nombre d’atome de carbone du diacide, a et b étant chacun compris entre 4 et 36, avantageusement entre 9 et 18, le motif (diamine en Ca) étant choisi parmi les diamines aliphatiques, linéaires ou ramifiés, les diamines cycloaliphatiques et les diamines alkylaromatiques et le motif (diacide en Cb) étant choisi parmi les diacides aliphatiques, linéaires ou ramifiés, les diacides cycloaliphatiques et les diacides aromatiques; The polyamide can be a homopolyamide or a copolyamide or a mixture thereof. Advantageously, the semi-crystalline polyamides are semi-aromatic polyamides, in particular a semi-aromatic polyamide of formula X / YAr, as described in EP1505099, in particular a semi-aromatic polyamide of formula A / XT in which A is chosen from a unit obtained from an amino acid, a unit obtained from a lactam and a unit corresponding to the formula (diamine in Ca). (Cb diacid), with a representing the number of carbon atoms of the diamine and b representing the number of carbon atoms of the diacid, a and b each being between 4 and 36, advantageously between 9 and 18, the unit (Ca diamine) being chosen from aliphatic, linear or branched diamines, cycloaliphatic diamines and alkylaromatic diamines and the unit (Cb diacid) being chosen from aliphatic, linear or branched diacids, cycloaliphatic diacids and aromatic diacids ;
X.T désigne un motif obtenu à partir de la polycondensation d'une diamine en Cx et de l’acide téréphtalique, avec x représentant le nombre d’atomes de carbone de la diamine en Cx, x étant compris entre 5 et 36, avantageusement entre 9 et 18, notamment un polyamide de formule A/5T, A/6T, A/9T, A/10T ou A/11 T, A étant tel que défini ci-dessus, en particulier un polyamide choisi parmi un PA MPMDT/6T, un PA11/10T, un PA 5T/10T, un PA 11/BACT, un PA 11/6T/10T, un PA MXDT/10T, un PA MPMDT/10T, un PA BACT/10T, un PA BACT/6T, PA BACT/10T/6T, un PA 11/BACT/6T, PA 11/MPMDT/6T, PA 11/MPMDT/10T, PA 11/BACT/10T, un PA 11/MXDT/10T, un 11/5T/10T. XT denotes a unit obtained from the polycondensation of a Cx diamine and terephthalic acid, with x representing the number of carbon atoms of the Cx diamine, x being between 5 and 36, advantageously between 9 and 18, in particular a polyamide of formula A / 5T, A / 6T, A / 9T, A / 10T or A / 11 T, A being as defined above, in particular a polyamide chosen from a PA MPMDT / 6T, one PA11 / 10T, one PA 5T / 10T, one PA 11 / BACT, one PA 11 / 6T / 10T, one PA MXDT / 10T, one PA MPMDT / 10T, one PA BACT / 10T, one PA BACT / 6T, PA BACT / 10T / 6T, one PA 11 / BACT / 6T, PA 11 / MPMDT / 6T, PA 11 / MPMDT / 10T, PA 11 / BACT / 10T, one PA 11 / MXDT / 10T, one 11 / 5T / 10T.
T correspond à l’acide téréphtalique, MXD correspond à la m-xylylène diamine, MPMD correspond à la méthylpentaméthylène diamine et BAC correspond au bis(aminométhyl)cyclohexane. Lesdits polyamides semi-aromatiques ci-dessus définis présentent notamment une Tg supérieure ou égal à 80°C. T corresponds to terephthalic acid, MXD corresponds to m-xylylenediamine, MPMD corresponds to methylpentamethylene diamine and BAC corresponds to bis (aminomethyl) cyclohexane. Said semi-aromatic polyamides defined above have in particular a Tg greater than or equal to 80 ° C.
Polymère thermodurcissable P2j P2j thermosetting polymer
Les polymères thermodurcissables sont choisis parmi les résines époxydes ou à base d’époxyde, les polyesters, les vinylesters et polyuréthannes, ou un mélange de ceux-ci en particulier les résines époxyde ou à base d’époxyde. The thermosetting polymers are chosen from epoxy or epoxy-based resins, polyesters, vinyl esters and polyurethanes, or a mixture of these, in particular epoxy or epoxy-based resins.
Avantageusement, chaque couche de renfort composite est constituée d’une composition comprenant le même type de polymère, en particulier une résine époxyde ou à base d’époxyde. Advantageously, each composite reinforcing layer consists of a composition comprising the same type of polymer, in particular an epoxy or epoxy-based resin.
Ladite composition comprenant ledit polymère P2j peut être transparente à un rayonnement adapté à la soudure. Said composition comprising said polymer P2j may be transparent to radiation suitable for welding.
Dans un autre mode de réalisation, l’enroulement de la couche de renfort composite autour de la couche d’étanchéité est effectué en l’absence de toute soudure ultérieure. In another embodiment, the winding of the composite reinforcing layer around the waterproofing layer is carried out in the absence of any subsequent welding.
S’agissant de la structure Regarding the structure
Ladite structure multicouche comprend donc une couche d’étanchéité et au moins une couche de renfort composite qui est enroulée autour de la couche d’étanchéité et qui peuvent adhérer ou non entre elles. Said multilayer structure therefore comprises a waterproofing layer and at least one composite reinforcing layer which is wrapped around the waterproofing layer and which may or may not adhere to each other.
Avantageusement, lesdites couches d’étanchéité et de renfort n’adhèrent pas entre elles et sont constituées de compositions qui comprennent respectivement des polymères différents. Advantageously, said sealing and reinforcing layers do not adhere to each other and consist of compositions which respectively comprise different polymers.
Néanmoins, lesdits polymères différents peuvent être du même type. However, said different polymers can be of the same type.
Ainsi, la couche d’étanchéité étant constituée d’une composition comprenant un polyamide aliphatique PA11 , alors la ou les couches de renfort est ou sont constituée(s) d’une composition comprenant un polyamide qui n’est pas aliphatique et qui est par exemple un polyamide semi-aromatique de façon à disposer d’un polymère de haute tg comme matrice du renfort composite. Thus, the waterproofing layer consisting of a composition comprising an aliphatic polyamide PA11, then the reinforcing layer (s) is (are) or consists of a composition comprising a polyamide which is not aliphatic and which is by example a semi-aromatic polyamide so as to have a high tg polymer as the matrix of the composite reinforcement.
Ladite structure multicouche peut comprendre jusqu’à 10 couches de renfort composite de natures différentes. Said multilayer structure can include up to 10 composite reinforcement layers of different types.
Avantageusement, ladite structure multicouche comprend une couche d’étanchéité et une, deux, trois, quatre, cinq, six, sept, huit, neuf ou dix couches de renfort composite. Avantageusement, ladite structure multicouche comprend une couche d’étanchéité et une, deux, trois, quatre ou cinq couches de renfort composite. Advantageously, said multilayer structure comprises a sealing layer and one, two, three, four, five, six, seven, eight, nine or ten layers of composite reinforcement. Advantageously, said multilayer structure comprises a waterproofing layer and one, two, three, four or five composite reinforcement layers.
Avantageusement, ladite structure multicouche comprend une couche d’étanchéité et une deux ou trois couches de renfort composite. Advantageously, said multilayer structure comprises a waterproofing layer and one two or three composite reinforcement layers.
Avantageusement, elles sont constituées de compositions qui comprennent respectivement des polymères différents. Avantageusement, elles sont constituées de compositions qui comprennent respectivement des polyamides correspondant aux polyamides PA11 et une résine époxyde ou à base d’époxyde P2j. Advantageously, they consist of compositions which respectively comprise different polymers. Advantageously, they consist of compositions which respectively comprise polyamides corresponding to polyamides PA11 and an epoxy resin or epoxy resin P2j.
Dans un mode de réalisation, ladite structure multicouche comprend une seule couche d’étanchéité et plusieurs couches de renfort, ladite couche de renfort adjacente étant enroulée autour de ladite couche d’étanchéité et les autres couches de renfort étant enroulées autour de la couche de renfort directement adjacente. In one embodiment, said multilayer structure comprises a single waterproofing layer and several reinforcing layers, said adjacent reinforcing layer being wrapped around said waterproofing layer and the other reinforcing layers being wrapped around the reinforcing layer. directly adjacent.
Dans un mode de réalisation avantageux, ladite structure multicouche comprend une seule couche d’étanchéité et une seule couche de renfort composite, ladite couche de renfort étant enroulée autour de ladite couche d’étanchéité. In an advantageous embodiment, said multilayer structure comprises a single waterproofing layer and a single composite reinforcing layer, said reinforcing layer being wrapped around said waterproofing layer.
Toutes les combinaisons de ces deux couches sont donc dans la portée de l’invention, à la condition qu’au moins ladite couche de renfort composite la plus interne soit enroulée autour de ladite couche d’étanchéité, les autres couches adhérant ou non entre elles ou non. All the combinations of these two layers are therefore within the scope of the invention, provided that at least said innermost composite reinforcing layer is wound around said waterproofing layer, the other layers adhering or not to each other. or not.
Avantageusement, ledit polymère P2j est une résine époxyde ou à base d’époxyde. Avantageusement, dans ladite structure multicouche, chaque couche de renfort est constituée d’une composition comprenant le même type de polymère P2j, en particulier une résine époxyde ou à base d’époxyde. Advantageously, said P2j polymer is an epoxy resin or an epoxy-based resin. Advantageously, in said multilayer structure, each reinforcing layer consists of a composition comprising the same type of polymer P2j, in particular an epoxy or epoxy-based resin.
Avantageusement, le polyamide P2j est identique pour toutes les couches de renfort.Advantageously, the P2j polyamide is identical for all the reinforcing layers.
Dans un mode de réalisation, dans ladite structure multicouche, la couche d’étanchéité est constituée d’une composition comprenant un polyamide PA11 et chaque couche de renfort est constituée d’une composition comprenant le même type de polymère P2j, en particulier une résine époxyde ou à base d’époxyde. In one embodiment, in said multilayer structure, the sealing layer consists of a composition comprising a polyamide PA11 and each reinforcing layer consists of a composition comprising the same type of polymer P2j, in particular an epoxy resin. or epoxy based.
Dans un mode de réalisation, dans ladite structure multicouche, la couche d’étanchéité est constituée d’une composition comprenant un polyamide PA11 et chaque couche de renfort est constituée d’une composition comprenant le même type de polymère P2j, ledit polymère P2j étant un polyamide semi-aromatique, en particulier choisi parmi un PA MPMDT/6T, un PA PA11/10T, un PA 11/BACT, un PA 5T/10T, un PA 11/6T/10T, un PA MXDT/10T, un PA MPMDT/10T, un PA BACT/10T, un PA BACT/6T, PA BACT/10T/6T, un PA 11/BACT/6T, PA 11/MPMDT/6T, PA 11/MPMDT/10T, PA 11/ BACT/10T et un PA 11/MXDT/10T. In one embodiment, in said multilayer structure, the sealing layer consists of a composition comprising a polyamide PA11 and each reinforcing layer consists of a composition comprising the same type of polymer P2j, said polymer P2j being a semi-aromatic polyamide, in particular chosen from a PA MPMDT / 6T, a PA PA11 / 10T, a PA 11 / BACT, a PA 5T / 10T, a PA 11 / 6T / 10T, a PA MXDT / 10T, a PA MPMDT / 10T, one PA BACT / 10T, one PA BACT / 6T, PA BACT / 10T / 6T, one PA 11 / BACT / 6T, PA 11 / MPMDT / 6T, PA 11 / MPMDT / 10T, PA 11 / BACT / 10T and a PA 11 / MXDT / 10T.
Dans un mode de réalisation, ladite structure multicouche est constituée d’une seule couche d’étanchéité et d’une seule couche de renfort dans laquelle ledit polymère P2j est un polyamide semi-aromatique, en particulier choisi parmi un PA MPMDT/6T, un PA11/10T, un PA 11/BACT, un PA 5T/10T, un PA 11/6T/10T, un PA MXDT/10T, un PA MPMDT/10T, un PA BACT/10T, un PA BACT/6T, PA BACT/10T/6T, un PA 11/BACT/6T, PA 11/MPMDT/6T, PA 11/MPMDT/10T, PA 11/ BACT/10T et un PA 11/MXDT/10T. Dans un encore autre mode de réalisation, la structure multicouche, est constituée d’une seule couche d’étanchéité et d’une seule couche de renfort dans laquelle ledit polymère P2j est une résine époxyde ou à base d’époxyde. In one embodiment, said multilayer structure consists of a single sealing layer and a single reinforcing layer in which said polymer P2j is a semi-aromatic polyamide, in particular chosen from a PA MPMDT / 6T, a PA11 / 10T, one PA 11 / BACT, one PA 5T / 10T, one PA 11 / 6T / 10T, one PA MXDT / 10T, one PA MPMDT / 10T, one PA BACT / 10T, one PA BACT / 6T, PA BACT / 10T / 6T, one PA 11 / BACT / 6T, PA 11 / MPMDT / 6T, PA 11 / MPMDT / 10T, PA 11 / BACT / 10T and one PA 11 / MXDT / 10T. In yet another embodiment, the multilayer structure consists of a single sealing layer and a single reinforcing layer in which said polymer P2j is an epoxy or epoxy-based resin.
Avantageusement, ladite structure multicouche comprend de plus au moins une couche externe constituée d’un matériau fibreux en fibre de verre continue imprégné d’un polymère amorphe transparent, ladite couche étant la couche plus externe de ladite structure multicouche. Advantageously, said multilayer structure further comprises at least one outer layer made of a continuous fiberglass fibrous material impregnated with a transparent amorphous polymer, said layer being the outermost layer of said multilayer structure.
Ladite couche externe est une seconde couche de renfort mais transparente qui permet de pouvoir mettre une inscription sur la structure. Said outer layer is a second but transparent reinforcing layer which makes it possible to put an inscription on the structure.
Ladite couche externe ne correspond en aucun cas à la couche située au-dessus de la couche de renfort composite la plus extérieure en polymère polyamide dont la structure est dépourvue citée ci-dessus. Said outer layer in no way corresponds to the layer located above the outermost composite reinforcing layer of polyamide polymer, the structure of which is not mentioned above.
S’agissant du matériau fibreux Regarding the fibrous material
Concernant les fibres de constitution dudit matériau fibreux, ce sont notamment des fibres d’origine minérale, organique ou végétale. Regarding the constituent fibers of said fibrous material, they are in particular fibers of mineral, organic or plant origin.
Avantageusement, ledit matériau fibreux peut être ensimé ou non ensimé. Advantageously, said fibrous material can be sized or not sized.
Ledit matériau fibreux peut donc comprendre jusqu'à 3,5% en poids d’un matériau de nature organique (type résine thermodurcissable ou thermoplastique) dénommé ensimage. Said fibrous material can therefore comprise up to 3.5% by weight of an organic material (thermosetting or thermoplastic resin type) called sizing.
Parmi les fibres d’origine minérale, on peut citer les fibres de carbone, les fibres de verre, les fibres de basalte ou à base de basalte, les fibres de silice, ou les fibres de carbure de silicium par exemple. Parmi les fibres d’origine organique, on peut citer les fibres à base de polymère thermoplastique ou thermodurcissable, telles que des fibres de polyamides semi-aromatiques, des fibres d’aramide ou des fibres en polyoléfines par exemple. De préférence, elles sont à base de polymère thermoplastique amorphe et présentent une température de transition vitreuse Tg supérieure à la Tg du polymère ou mélange de polymère thermoplastique de constitution de la matrice de pré-imprégnation lorsque ce dernier est amorphe, ou supérieure à la Tf du polymère ou mélange de polymère thermoplastique de constitution de la matrice de pré-imprégnation lorsque ce dernier est semi-cristallin. Avantageusement, elles sont à base de polymère thermoplastique semi- cristallin et présentent une température de fusion Tf supérieure à la Tg du polymère ou mélange de polymère thermoplastique de constitution de la matrice de pré-imprégnation lorsque ce dernier est amorphe, ou supérieure à la Tf du polymère ou mélange de polymère thermoplastique de constitution de la matrice de pré-imprégnation lorsque ce dernier est semi-cristallin. Ainsi, il n’y a aucun risque de fusion pour les fibres organiques de constitution du matériau fibreux lors de l’imprégnation par la matrice thermoplastique du composite final. Parmi les fibres d’origine végétale, on peut citer les fibres naturelles à base de lin, de chanvre, de lignine, de bambou, de soie notamment d’araignée, de sisal, et d’autres fibres cellulosiques, en particulier de viscose. Ces fibres d’origine végétale peuvent être utilisées pures, traitées ou bien enduites d’une couche d’enduction, en vue de faciliter l’adhérence et l’imprégnation de la matrice de polymère thermoplastique.Among the fibers of mineral origin, mention may be made of carbon fibers, glass fibers, basalt or basalt-based fibers, silica fibers, or silicon carbide fibers, for example. Among the fibers of organic origin, mention may be made of fibers based on a thermoplastic or thermosetting polymer, such as semi-aromatic polyamide fibers, aramid fibers or polyolefin fibers, for example. Preferably, they are based on an amorphous thermoplastic polymer and have a glass transition temperature Tg greater than the Tg of the polymer or mixture of thermoplastic polymer constituting the pre-impregnation matrix when the latter is amorphous, or greater than the Tm of the polymer or mixture of thermoplastic polymer constituting the prepreg matrix when the latter is semi-crystalline. Advantageously, they are based on a semi-crystalline thermoplastic polymer and have a melting point Tm greater than the Tg of the polymer or mixture of thermoplastic polymer constituting the prepreg matrix when the latter is amorphous, or greater than the Tm. of the polymer or mixture of thermoplastic polymer constituting the prepreg matrix when the latter is semi-crystalline. Thus, there is no risk of fusion for the organic fibers constituting the fibrous material during impregnation with the thermoplastic matrix of the final composite. Among the fibers of plant origin, mention may be made of natural fibers with base of flax, hemp, lignin, bamboo, silk, in particular spider silk, sisal, and other cellulose fibers, in particular viscose. These fibers of plant origin can be used pure, treated or else coated with a coating layer, with a view to facilitating the adhesion and the impregnation of the thermoplastic polymer matrix.
Le matériau fibreux peut également être un tissu, tressé ou tissé avec des fibres. The fibrous material can also be fabric, braided or woven with fibers.
Il peut également correspondre à des fibres avec des fils de maintien. It can also correspond to fibers with retaining threads.
Ces fibres de constitution peuvent être utilisées seules ou en mélanges. Ainsi, des fibres organiques peuvent être mélangées aux fibres minérales pour être pré-imprégnées de poudre polymère thermoplastique et former le matériau fibreux pré-imprégné. These constitution fibers can be used alone or in mixtures. Thus, organic fibers can be mixed with mineral fibers to be pre-impregnated with thermoplastic polymer powder and to form the pre-impregnated fibrous material.
Les mèches de fibres organiques peuvent avoir plusieurs grammages. Elles peuvent en outre présenter plusieurs géométries. Les fibres de constitution du matériau fibreux peuvent en outre se présenter sous forme d’un mélange de ces fibres de renfort de différentes géométries. Les fibres sont des fibres continues. The rovings of organic fibers can have several grammages. They can also have several geometries. The fibers constituting the fibrous material can also be in the form of a mixture of these reinforcing fibers of different geometries. Fibers are continuous fibers.
De préférence le matériau fibreux est choisi parmi les fibres de verre, les fibres de carbone, les fibres de basalte ou à base de basalte, ou un mélange de celles-ci, en particulier les fibres de carbone. Preferably, the fibrous material is chosen from glass fibers, carbon fibers, basalt or basalt-based fibers, or a mixture of these, in particular carbon fibers.
Il est utilisé sous forme d’une mèche ou de plusieurs mèches. It is used as a wick or several wicks.
Selon un autre aspect, la présente invention concerne un procédé de fabrication d’une structure multicouche telle que définie ci-dessus, caractérisé en ce qu’il comprend une étape de préparation de la couche d’étanchéité par extrusion soufflage, par rotomoulage, par injection et/ou par extrusion. According to another aspect, the present invention relates to a method of manufacturing a multilayer structure as defined above, characterized in that it comprises a step of preparing the sealing layer by extrusion blow molding, by rotational molding, by injection and / or extrusion.
Dans un mode de réalisation, ledit procédé de fabrication d’une structure multicouche comprend une étape d’enroulement filamentaire de la couche de renfort telle que définie ci-dessus autour de la couche de d’étanchéité telle que définie ci-dessus. In one embodiment, said method of manufacturing a multilayer structure comprises a step of filament winding of the reinforcing layer as defined above around the sealing layer as defined above.
Toutes les caractéristiques détaillée ci-dessus s’appliquent également au procédé. All of the features detailed above also apply to the process.
Brève description des figures. Brief description of the figures.
La figure 1 présente le choc Charpy entaillé à -40°C selon ISO 179-1 :2010 de quatre liners :de gauche à droite PA11, PA12, PA6 et PA66. Figure 1 shows the notched Charpy impact at -40 ° C according to ISO 179-1: 2010 of four liners: from left to right PA11, PA12, PA6 and PA66.
La figure 2 présente la perméabilité à l’hydrogène à 23°C de liners PA12 et HDPE. Figure 2 shows the hydrogen permeability at 23 ° C of PA12 and HDPE liners.
Elle est exprimée en cc.mm/m2.24h.atm. Elle peut être exprimée en cc.25p/m2.24h.Pa.It is expressed in cc.mm/m 2 .24h.atm. It can be expressed in cc.25p / m 2 .24h.Pa.
La perméabilité doit alors être multipliée par 101325. The permeability must then be multiplied by 101325.
La figure 3 présente le choc Charpy entaillé à -40°C selon ISO 179-1 :2010 de liners PA11 et PA12 : pour chaque groupe d’histogrammes, PA11 est à gauche et PA12 est à droite. Le premier groupe correspond à 0% de plastifiant, le second groupe à 7% de plastifiant et le dernier groupe à 12% de plastifiant. Figure 3 shows the notched Charpy shock at -40 ° C according to ISO 179-1: 2010 for PA11 and PA12 liners: for each group of histograms, 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.
EXEMPLES Dans tous les exemples, les réservoirs sont obtenus par rotomoulage de la couche d’étanchéité (liner) à une température adaptée à la nature de la résine thermoplastique utilisée. EXAMPLES In all the examples, the tanks are obtained by rotational molding of the sealing layer (liner) at a temperature suited to the nature of the thermoplastic resin used.
Dans le cas du renfort composite en résine époxyde ou à base d’époxyde, on utilise ensuite un procédé d’enroulement filamentaire voie humide qui consiste à enrouler des fibres autour du liner, lesquelles fibres étant préalablement pré-imprégnée dans un bain d’époxyde liquide ou un bain à base d’époxyde liquide. Le réservoir est ensuite polymérisé en étuve pendant 2h. In the case of the epoxy resin or epoxy-based composite reinforcement, a wet filament winding process is then used which consists in winding fibers around the liner, which fibers are pre-impregnated in an epoxy bath. liquid or a liquid epoxy-based bath. The reservoir is then polymerized in an oven for 2 hours.
Dans tous les autres cas, on utilise ensuite un matériau fibreux préalablement imprégné par la résine thermoplastique (tape). Cette tape est déposée par enroulement filamentaire au moyen d’un robot comportant un chauffage laser de puissance 1500W à la vitesse de 12m/min et il n’y a pas d’étape de polymérisation. In all other cases, then a fibrous material impregnated with the thermoplastic resin (tape) is used. This tape is deposited by filament winding using a robot comprising a 1500W power laser heater at a speed of 12m / min and there is no polymerization step.
Exemple 1 : Choc Charpy entaillé à -40°C selon ISO 179-1 :2010 Example 1: Notched Charpy shock at -40 ° C according to ISO 179-1: 2010
Deux liners à longue chaîne en PA11 et PA12 et deux liners à chaîne courte ont été préparés par rotomoulage comme ci-dessus. Two long chain liners of PA11 and PA12 and two short chain liners were prepared by rotational molding as above.
Ces quatre liners ont été testés en choc Charpy entaillé à -40°C et les résultats sont présentés dans la figure 1. These four liners were notched Charpy shock tested at -40 ° C and the results are shown in Figure 1.
La tenue à froid du liner PA1 lest très nettement supérieure à celles du liner à longue chaîne PA12 et des liners à courte chaîne PA6 et PA66. The cold resistance of the PA1 liner is very much better than that of the long chain liner PA12 and the short chain liners PA6 and PA66.
Exemple 2: Example 2:
Perméabilité de liners PA 11 et PA12 (Arkema) et HDPE (Marlex® HMN TR-942 (Chevron Phillips)) Permeability of PA 11 and PA12 (Arkema) and HDPE (Marlex® HMN TR-942 (Chevron Phillips) liners)
Deux liners à longue chaîne : un en PA11 (Arkema) et le deuxième en PA12 (Arkema) et un liner en HDPE ont été préparés par rotomoulage et la perméabilité à l’hydrogène à 23°C a été testée. Two long chain liners: one in PA11 (Arkema) and the second in PA12 (Arkema) and one liner in HDPE were prepared by rotational molding and the hydrogen permeability at 23 ° C was tested.
Cela consiste à balayer la face supérieure du film par le gaz d'essai (Hydrogène) et à mesurer par chromatographie en phase gazeuse le flux qui diffuse à travers le film dans la partie inférieure, balayée par le gaz vecteur : l’Azote This consists of sweeping the upper face of the film with the test gas (Hydrogen) and of measuring by gas chromatography the flow which diffuses through the film in the lower part, swept by the carrier gas: nitrogen
Les conditions expérimentales sont présentées dans le tableau 1 : The experimental conditions are presented in Table 1:
[Tableaux 1] [Tables 1]
Les résultats sont présentés en figure 2 et montrent que le liner en PA11 présente une perméabilité très inférieure à celle d’un liner longue chaîne en PA12 et d’un liner HDPE. Exemple 3 : influence de la proportion de plastifiant (N-butyl benzène sulfonamide : BBSA) sur le choc Charpy entaillé à -40°C selon ISO 179-1 :2010 The results are presented in Figure 2 and show that the PA11 liner has a much lower permeability than a long chain PA12 liner and an HDPE liner. Example 3: influence of the proportion of plasticizer (N-butyl benzene sulfonamide: BBSA) on the notched Charpy impact at -40 ° C according to ISO 179-1: 2010
Deux liners PA11 et PA12 sans plastifiant ou comprenant 7 ou 12% de plastifiant (BBSA) par rapport au poids total de la composition ont été préparés par rotomoulage. Two liners PA11 and PA12 without plasticizer or comprising 7 or 12% plasticizer (BBSA) relative to the total weight of the composition were prepared by rotational molding.
Ces liners ont été testés en choc Charpy entaillé à -40°C selon ISO 179-1 :2010 et les résultats sont présentés dans la figure 3. Le plastifiant a un effet délétère à froid plus prononcé pour le PA12 que le PA11 , il fragilise la structure du PA12 et augmente la perméabilité, notamment de 50% avec 7% de BBSA. These liners were tested in notched Charpy impact at -40 ° C according to ISO 179-1: 2010 and the results are presented in figure 3. The plasticizer has a more pronounced cold deleterious effect for PA12 than PA11, it weakens the structure of PA12 and increases the permeability, in particular by 50% with 7% BBSA.
Exemple 4 Example 4
Influence de la proportion de modifiant choc (« cocktail LT » présentant la composition suivante : lotader® 4700 (50%) + lotader® AX8900 (25%) + lucalène® 3110 (25%)) sur la perméabilité à l’hydrogène de liner PA11. Influence of the proportion of impact modifier (“LT cocktail” having the following composition: lotader® 4700 (50%) + lotader® AX8900 (25%) + lucalene® 3110 (25%)) on the liner's hydrogen permeability PA11.
La perméabilité à l’hydrogène de liner en PA11 , sans plastifiant et en présence ou non de modifiant choc a été testée et est reporté sur le tableau 2. The permeability to hydrogen of the PA11 liner, without plasticizer and in the presence or absence of impact modifier was tested and is reported in Table 2.
[Tableaux 2] [Tables 2]
La perméabilité peut également être exprimée en (cc.25p/m2.24h.Pa). La perméabilité doit alors être multipliée par 101325. Les résultats montrent que le la proportion de modifiant choc influe sur la perméabilité à l’hydrogène. The permeability can also be expressed in (cc.25p / m 2 .24h.Pa). The permeability must then be multiplied by 101325. The results show that the proportion of impact modifier influences the permeability to hydrogen.
Plus la proportion de modifiant choc est importante, plus la perméabilité augmente. Exemple 5 The greater the proportion of impact modifier, the more the permeability increases. Example 5
Réservoir de stockage d’hydrogène de type IV, composé d’un renfort en composite époxyde (Tg 120°C) fibres de carbone T700SC31E (produite parToray) et d’une couche d’étanchéité en PA11. Type IV hydrogen storage tank, composed of an epoxy composite reinforcement (Tg 120 ° C) T700SC31E carbon fibers (produced by Toray) and a waterproofing layer of PA11.
La température d’utilisation est suffisante pour un remplissage rapide du réservoir, notamment en 3 à 5 minutes. The operating temperature is sufficient for rapid filling of the tank, especially in 3 to 5 minutes.
Exemple 6 (contre exemple) : Example 6 (counter example):
Réservoir de stockage d’hydrogène de type IV, composé d’un renfort en composite époxyde (Tg 120°C) fibres de carbone T700SC31E (produite parToray) et d’une couche d’étanchéité en HDPE. Type IV hydrogen storage tank, composed of an epoxy composite reinforcement (Tg 120 ° C) T700SC31E carbon fibers (produced by Toray) and an HDPE waterproofing layer.
La température d’utilisation est trop faible pour un remplissage rapide du réservoir notamment en 3 à 5 minutes. The operating temperature is too low for rapid filling of the tank, especially in 3 to 5 minutes.
Exemple 7 : Réservoir de stockage d’hydrogène de type IV, composé d’un renfort en composite BACT/10T fibres de carbone T700SC31 E (produite par Toray) et d’une couche d’étanchéité en PA11. Example 7: Type IV hydrogen storage tank, composed of a reinforcement of BACT / 10T carbon fiber T700SC31 E composite (produced by Toray) and a waterproofing layer of PA11.
La composition de type BACT/10T choisie présente une température de fusion, Tf, de 283°C, une température de cristallisation, Te, de 250°C et une température de transition vitreuse de 164°C. The BACT / 10T type composition chosen has a melting point, Tm, of 283 ° C, a crystallization temperature, Te, of 250 ° C and a glass transition temperature of 164 ° C.
La Tg, la Te et la Tf sont déterminées par analyse calorimétrique différentielle (DSC) selon la norme 11357-2 :2013 et 11357-3 :2013 respectivement. Tg, Te and Tf are determined by differential scanning calorimetry (DSC) according to standard 11357-2: 2013 and 11357-3: 2013 respectively.
Un composite à base PA BACT/10T présente une matrice à haute Tg, mais sans avoir de réticulation longue, du type 8h à 140°C. A PA BACT / 10T-based composite exhibits a high Tg matrix, but without having long crosslinking, of the 8h type at 140 ° C.
Par conséquent, après la dépose de fibre, le réservoir est fini, ce qui permet de gagner 8h de temps de process. Consequently, after the fiber removal, the tank is finished, which saves 8 hours of process time.

Claims

REVENDICATIONS
1. Structure multicouche destinée au transport, à la distribution et au stockage de l’hydrogène, comprenant, de l’intérieur vers l’extérieur, une couche d’étanchéité (1) et au moins une couche de renfort composite (2), ladite couche de renfort composite la plus interne étant enroulée autour de la dite couche d’étanchéité (1), ladite couche d’étanchéité étant constituée d’une composition comprenant majoritairement : un polymère thermoplastique polyamide PA11 , jusqu’à moins de 15% en poids de modifiant choc, en particulier jusqu’à 12% en poids de modifiant choc par rapport au poids total de la composition, jusqu’à 1,5% en poids de plastifiant par rapport au poids total de la composition, ladite composition étant dépourvue d’agent nucléant et de polyéther block amide (PEBA), et au moins l’une des dites couches de renfort composite étant constituée d’un matériau fibreux sous forme de fibres continues imprégné par une composition comprenant majoritairement au moins un polymère P2j, j=1 à m, m étant le nombre de couches de renfort, en particulier une résine époxyde ou à base d’époxyde, ladite structure étant dépourvue d’une couche la plus extérieure et adjacente à la couche la plus extérieure de renfort composite en polymère polyamide. 1. Multilayer structure intended for the transport, distribution and storage of hydrogen, comprising, from the inside to the outside, a waterproofing layer (1) and at least one composite reinforcing layer (2), said innermost composite reinforcing layer being wound around said sealing layer (1), said sealing layer consisting of a composition mainly comprising: a thermoplastic polyamide PA11 polymer, up to less than 15% in weight of impact modifier, in particular up to 12% by weight of impact modifier relative to the total weight of the composition, up to 1.5% by weight of plasticizer relative to the total weight of the composition, said composition being devoid of nucleating agent and polyether block amide (PEBA), and at least one of said composite reinforcing layers consisting of a fibrous material in the form of continuous fibers impregnated with a composition mainly comprising at least one polymer P2j, j = 1 to m , m being the number of reinforcing layers, in particular an epoxy or epoxy-based resin, said structure being devoid of an outermost layer and adjacent to the outermost layer of composite reinforcement of polyamide polymer.
2. Structure multicouche selon l’une des revendications 1, caractérisée en ce que chaque couche de renfort comprend le même type de polymère, en particulier une résine époxyde ou à base d’époxyde. 2. Multilayer structure according to one of claims 1, characterized in that each reinforcing layer comprises the same type of polymer, in particular an epoxy resin or based on epoxy.
3. Structure multicouche selon l’une des revendications 1 ou 2, caractérisée en ce qu’elle présente une seule couche de renfort. 3. Multilayer structure according to one of claims 1 or 2, characterized in that it has a single reinforcing layer.
4. Structure multicouche selon l’une des revendications 1 ou 2, caractérisée en ce que ledit polymère P2j est une résine époxyde ou à base d’époxyde. 4. Multilayer structure according to one of claims 1 or 2, characterized in that said polymer P2j is an epoxy resin or based on epoxy.
5. Structure multicouche selon l’une des revendications 3 ou 4, caractérisée en ce que ladite structure multicouche est constituée d’une seule couche de renfort et ledit polymère P2j est une résine époxyde ou à base d’époxyde. 5. Multilayer structure according to one of claims 3 or 4, characterized in that said multilayer structure consists of a single reinforcing layer and said polymer P2j is an epoxy resin or based on epoxy.
6. Structure multicouche selon l’une des revendications 1 à 5, caractérisée en ce que le matériau fibreux de la couche de renfort composite est choisi parmi les fibres de verre, les fibres de carbone, les fibres de basalte ou à base de basalte, ou un mélange de celles-ci, en particulier les fibres de carbone. 6. Multilayer structure according to one of claims 1 to 5, characterized in that the fibrous material of the composite reinforcing layer is chosen from fibers of glass, carbon fibers, basalt or basalt-based fibers, or a mixture thereof, in particular carbon fibers.
7. Structure multicouche selon l’une des revendications 1 à 6, caractérisée en ce que ladite structure comprend de plus au moins une couche externe constituée d’un matériau fibreux en fibre de verre continue imprégné d’un polymère amorphe transparent, ladite couche étant la couche plus externe de ladite structure multicouche. 7. Multilayer structure according to one of claims 1 to 6, characterized in that said structure further comprises at least one outer layer consisting of a continuous fiberglass fibrous material impregnated with a transparent amorphous polymer, said layer being the outermost layer of said multilayer structure.
8. Procédé de fabrication d’une structure multicouche telle que définie dans l’une des revendications 1 à 7, caractérisé en ce qu’il comprend une étape de préparation de la couche d’étanchéité par extrusion soufflage, par rotomoulage, par injection et/ou par extrusion. 8. A method of manufacturing a multilayer structure as defined in one of claims 1 to 7, characterized in that it comprises a step of preparing the sealing layer by extrusion blow molding, by rotational molding, by injection and / or by extrusion.
9. Procédé de fabrication d’une structure multicouche selon la revendication 8, caractérisé en ce qu’il comprend une étape d’enroulement filamentaire de la couche de renfort telle que définie dans la revendication 1 autour de la couche d’étanchéité telle que définie dans la revendication 1. 9. A method of manufacturing a multilayer structure according to claim 8, characterized in that it comprises a step of filament winding of the reinforcing layer as defined in claim 1 around the sealing layer as defined. in claim 1.
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