Classifications

• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
  • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
  • F16L9/00—Rigid pipes
  • F16L9/12—Rigid pipes of plastics with or without reinforcement
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B1/00—Layered products having a non-planar shape
  • B32B1/08—Tubular products
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
  • B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
  • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
  • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
  • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
• • 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
  • F17C13/00—Details of vessels or of the filling or discharging of vessels
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
  • F17D—PIPE-LINE SYSTEMS; PIPE-LINES
  • F17D1/00—Pipe-line systems
  • F17D1/02—Pipe-line systems for gases or vapours
  • F17D1/04—Pipe-line systems for gases or vapours for distribution of gas
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2250/00—Layers arrangement
  • B32B2250/24—All layers being polymeric
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
  • B32B2260/02—Composition of the impregnated, bonded or embedded layer
  • B32B2260/021—Fibrous or filamentary layer
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
  • B32B2260/04—Impregnation, embedding, or binder material
  • B32B2260/046—Synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
  • B32B2262/10—Inorganic fibres
  • B32B2262/101—Glass fibres
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
  • B32B2262/10—Inorganic fibres
  • B32B2262/106—Carbon fibres, e.g. graphite fibres
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
  • B32B2307/558—Impact strength, toughness
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/724—Permeability to gases, adsorption
  • B32B2307/7242—Non-permeable
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/726—Permeability to liquids, absorption
  • B32B2307/7265—Non-permeable
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2597/00—Tubular articles, e.g. hoses, pipes
• • 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
  • 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
  • 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
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
  • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
  • F17C2270/00—Applications
  • F17C2270/01—Applications for fluid transport or storage
  • F17C2270/0165—Applications for fluid transport or storage on the road
  • F17C2270/0184—Fuel cells

Definitions

• TITLE MULTILAYER TUBULAR STRUCTURE WITH LOW EXTRACTIBLE RATES FOR HYDROGEN TRANSPORT
• the invention relates to a multilayer tubular structure having a low level of extractables and its use for transporting hydrogen.
• the invention relates more particularly to the tubes present within a motor vehicle. These tubes can for example be intended for the transport of hydrogen to supply a fuel cell.
• Hydrogen is a subject that is currently attracting a lot of interest from many manufacturers, particularly in the automotive field.
• One of the goals sought is to offer less and less polluting vehicles.
• 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. Depending on where the battery is located in the vehicle, it may need to be protected from impact and the external environment, which may be extreme temperatures and varying humidity. It is also necessary to avoid any risk of flames.
• 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, recharge times much longer than the durations tank filling, as well as a problem of electricity production in the various 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 or hydrogen transport pipes generally consist of a metallic or thermoplastic envelope (liner or sealing layer) which must prevent the permeation of hydrogen.
• the liner or sealing sheath in thermoplastic resin is associated with a reinforcing structure made up of fibers (glass, aramid, carbon) also called sheath or reinforcing layer which makes it possible 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 hydrogen transport pipe must minimize the permeation of hydrogen.
• the fuel cell is very sensitive to various contaminants which degrade its performance and its durability.
• a hydrogen transport pipe used with a fuel cell must not only have the basic characteristics listed above but also the hydrogen after contact with the sealing layer of said tank and/or pipe must not contain only a minimum of contaminants extracted from said sealing layer.
• This dual problem is resolved by providing a multilayer structure of the present invention intended for the transport of hydrogen.
• the present invention relates to a multilayer tubular structure (MLT) intended for the transport of hydrogen comprising, from the outside to the inside, at least one barrier layer (1) and at least one inner layer (2) located below the barrier layer, said inner layer (2) or all the layers (2) and any other layers located below the barrier layer, containing on average from 0 to 1.5% by weight of plasticizer relative respectively to the total weight of the composition of the layer (2) or the total weight of all the compositions of the layers (2) and any other layers located below the barrier layer, said inner layer (2) having a rate of extractable less than or equal to 3% by weight, in particular less than 2% by weight of the sum of the constituents of said composition, said inner layer (2) mainly comprising at least one polyamide of the aliphatic type or consisting of more than 75% of patterns has liphatic, said aliphatic polyamide being chosen from:
• A having an average number of carbon atoms per nitrogen atom denoted CA comprised from 4 to 8.5, advantageously from 4 to 7;
• polyamide noted C having an average number of carbon atoms per nitrogen atom noted Ce comprised from 9 to 18, advantageously from 10 to 18; provided that when said inner layer (2) comprises at least three polyamides, at least one of said polyamides A, B or C is excluded.
• all the layers (2) and any other layers located below the barrier layer means all the layers present located below the barrier layer.
• the inventors have therefore found that the absence or at least a very small proportion of plasticizer in the inner layer or layers, that is to say located (s) under the barrier layer, makes it possible to greatly reduce the proportion of contaminants present in hydrogen and extracted from said inner layer (2) after contact of hydrogen therewith, and the total proportion of said contaminants extracted in hydrogen, being less than or equal to 3% by weight, in particular less than 2 % by weight of the sum of the constituents of said composition.
• the level of extractables is determined according to the CSA/ANSI CHMC 2:19 standard.
• the level of extractables is determined by filling said tubular structure with FAM-B type alcoholyzed gasoline at 60°C for 96 hours, said tubular structure then being emptied of its container, said container being filtered in a beaker and left to evaporate, the evaporation residue then being weighed and corresponding to the rate of extractables.
• the rate of extractables is determined the rate of extractables is determined according to the CSA / ANSI CHMC 2:19 standard or by filling said tubular structure with alcoholic gasoline type FAM-B at 60° C., for 96 hours, said tubular structure then being emptied of its container, said container being filtered in a beaker and left to evaporate, the evaporation residue then being weighed and corresponding to the level of extractables.
• the multilayer structures of the invention therefore have good hydrogen permeability and low extraction of volatile organic compounds (VOCs).
• said inner layer (2) satisfying a test for contaminants present in hydrogen and extracted from said inner layer (2) by hydrogen means that the proportion of contaminants present in the hydrogen and originating from the interior (2) after contact with hydrogen, whether it is a tank or a pipe, does not exceed the limit values preventing proper operation of the fuel cell.
• CSA/ANSI CHMC 2:19 provides details on the procedure used to determine volatile components in the headspace of a polymer when exposed to hydrogen during service.
• the test equipment should include the following: a) a cryofocus to pre-concentrate the gas samples; b) a gas chromatograph using a suitable column, connected in series with a suitable mass-selective detector; c) headspace vials (40 ml), septa, ring closures and vial sealant; (d) an analytical balance capable of weighing up to 60.0001 g; and e) a convection oven capable of maintaining a temperature of 70 ⁇ 5°C.
• the hydrogen gas for conditioning must be of known composition and purity, as described below.
• the temperature at which hydrogen transmission rate measurements are made should be controlled to within ⁇ 1°C.
• the test pressure must remain constant within 1% of the test value.
• test procedure is described in the ISO 14687:2019 standard in paragraph 5.6.
• contaminant is understood in the broad sense of the term from the moment when said contaminant is extracted from said sealing layer by hydrogen and is not already present in the hydrogen which is introduced into said multilayer structure to operate the fuel cell of the vehicle, for example due to the process for obtaining hydrogen.
• the term contaminant covers metallic cations such as K + , Cu 2+ , Ni 2+ and Fe 3+ which can be produced by stabilizers used in polyamides, organic or metallic stabilizers as such, plasticizers , oligomers, in particular caprolactam and its cyclic dimer 1,8-diazacyclotetradecane-2,7-dione (DCDD), volatile organic compounds such as NH3, NOx, SOx, N2, benzoic compounds, 03, water absorbed by the polyamide after manufacture of the sealing layer, fatty substances such as oil.
• metallic cations such as K + , Cu 2+ , Ni 2+ and Fe 3+ which can be produced by stabilizers used in polyamides, organic or metallic stabilizers as such, plasticizers , oligomers, in particular caprolactam and its cyclic dimer 1,8-diazacyclotetradecane-2,7-dione (DCDD), volatile organic compounds such as NH3, NOx, SOx, N2, benzo
• Volatile organic compounds therefore exclude all the other materials mentioned in the list above.
• the total proportion of said contaminants extracted in hydrogen is less than or equal to 3% by weight, in particular less than 2% by weight of the sum of the constituents of said composition. Consequently, this total proportion of said extracted contaminants does not take into account the proportion of contaminants that would come from the hydrogen preparation process or from any other source.
• the total proportion of said contaminants extracted in hydrogen is comprised from 0.01% to 3%, in particular from 0.01% to 2%, more particularly from 0.01% to 1%, in particular from 0, 01% to 0.5% by weight.
• the extracted contaminants are chosen from plasticizers, stabilizers, oligomers, water, a fatty substance, volatile organic compounds and a mixture thereof.
• the proportion by weight of each individual contaminant extracted is less than or equal to 1%.
• the constitution of the extracted contaminants is as follows: up to 1% of plasticizers, up to 0.5% of stabilizers, up to 1% of oligomers, up to 0 .5% water, up to 0.5% fatty substances, and up to 0.5% volatile organic compounds, the sum of the extracted contaminants being less than or equal to 3%, in particular less than 2% by weight of the sum of the constituents of said composition.
• the total proportion of said contaminants extracted in hydrogen is comprised from 0.01% to 3%, in particular from 0.01% to 2%, more particularly from 0, 01% to 1%, in particular from 0.01% to 0.5% by weight. More advantageously, in this embodiment of this first variant, the proportion by weight of each individual contaminant extracted is less than or equal to 1%.
• the extracted contaminants are chosen from stabilizers, water, oil, volatile organic compounds and a mixture thereof.
• the proportion by weight of each individual contaminant extracted is less than or equal to 0.5%.
• the constitution of the extracted contaminants is as follows: up to 0.5% of stabilizers, up to 0.5% of water, up to 0.5% of fatty substances , and up to 0.5% of volatile organic compounds, the sum of the contaminants being less than or equal to 2% by weight of the sum of the constituents of said composition.
• the total proportion of said contaminants extracted in hydrogen is comprised from 0.01% to 2%, more particularly from 0.01% to 1%, in particular from 0.01 % to 0.5% by weight.
• the proportion by weight of each individual contaminant extracted is less than or equal to 0.5%.
• barrier layer designates a layer having characteristics of low permeability and good resistance to hydrogen, that is to say that the barrier layer slows down the passage of hydrogen, in the other layers of the structure. or even outside the structure.
• the barrier layer is therefore a layer that allows above all not to lose too much hydrogen in the atmosphere by diffusion, thus making it possible to avoid problems of explosion and ignition.
• the barrier layer (1) is impermeable to hydrogen at 23° C., that is to say that the permeability to hydrogen at 23° C. is less than 100 cc.mm/m2.24h.atm at 23°C under 0% relative humidity (RH).
• the permeability can also be expressed in (cc.mm/m 2 .24h.Pa).
• the permeability must then be multiplied by 101325.
• barrier materials can be low-carbon polyamides, that is to say whose average number of carbon atoms (C) relative to the nitrogen atom (N) is less than 9, preferably semi- crystalline materials with a high melting point, polyphthalamides (PPA) and/or also non-polyamide barrier materials such as highly crystalline polymers such as the copolymer of ethylene and vinyl alcohol (denoted EVOH below), or even fluorinated materials functionalized such as functionalized polyvinylidene fluoride (PVDF), functionalized ethylene and tetrafluoroethylene copolymer (ETFE), functionalized ethylene, tetrafluoroethylene and hexafluoropropylene copolymer (EFEP), polyphenylene sulfide (PPS ) functionalized, functionalized polybutylene naphthalate (PBN). If these polymers are not functionalized, then an intermediate layer of binder can be added to ensure good adhesion within the MLT structure.
• PVDF functionalized polyviny
• said barrier layer (1) said barrier layer is chosen from an EVOH layer, a fluoropolymer layer, in particular PVDF and a PPA layer.
• the EVOHs are particularly interesting, in particular those richest in vivnyl alcohol comonomer as well as those modified shocks because they make it possible to produce less fragile structures.
• the present invention relates to a multilayer tubular structure (MLT) as defined above, in which the barrier layer (1) is an EVOH layer.
• the present invention relates to a multilayer tubular structure (MLT) as defined above, in which the EVOH is an EVOH comprising up to 27% ethylene.
• MHT multilayer tubular structure
• the present invention relates to a multilayer tubular structure (MLT) as defined above, in which the EVOH is an EVOH comprising an impact modifier.
• MHT multilayer tubular structure
• the present invention relates to a multilayer tubular structure (MLT) as defined above, in which the barrier layer (1) is a polyphthalamide (PPA) layer.
• MLT multilayer tubular structure
• PPA polyphthalamide
• PPA means a composition mainly based on a polyamide comprising a majority of units which comprise at least one aromatic monomer, in particular polyphthalamide of copolyamide type 6.T/x (where x denotes one or more comonomers) such as Zytel HTN from Dupont, such as Grivory HT from Ems, such as Amodel from Solvay, such as Genestar from Kuraray, such as PPA compositions based on coPA6T/61, coPA6T/66, coPA6T/6, C0PA6T/6I/66, PPA9T, coPPA9T/x, PPA10T, coPPA10T/x.
• x denotes one or more comonomers
• Zytel HTN from Dupont
• Grivory HT from Ems
• Ems such as Amodel from Solvay
• PPA9T coPPA9T/x
• PPA10T coPPA10T/x.
• polyamide also denoted PA, refers to:
• copolymers or copolyamides, based on different amide units, such as for example copolyamide 6/12 with amide units derived from lactam-6 and lactam-12,
• copolyamides when the polyamide is the majority constituent.
• copolyamides comprising not only amide units (which will be the majority, hence the fact that they are to be considered as copolyamides in the broad sense), but also units of a non-amide nature, for example ether units .
• the best-known examples are PEBAs or polyether-block-amides, and their variants copolyamide-ester-ether, copolyamide-ether, copolyamide ester. Among these, let us mention PEBA-12 where the polyamide units are the same as those of PA12, PEBA-6.12 where the polyamide units are the same as those of PA6.12.
• Homopolyamides, copolyamides and alloys are also distinguished by their number of carbon atoms per nitrogen atom, knowing that there are as many nitrogen atoms as there are amide groups (-CO-NH-).
• a high-carbon polyamide is a polyamide with a high ratio of carbon atoms (C) relative to the nitrogen atom (N).
• These are polyamides with approximately at least 9 carbon atoms per nitrogen atom, such as for example polyamide-9, polyamide-12, polyamide-1 1, polyamide-10.10 (PA10.10), copolyamide 12 /10.T, copolyamide 1 1/10.T, polyamide-12.T, polyamide-6.12 (PA6.12).
• T stands for terephthalic acid.
• a low-carbon polyamide is a polyamide with a low ratio of carbon atoms (C) compared to the nitrogen atom (N).
• C carbon atoms
• N nitrogen atom
• polyamides with approximately less than 9 carbon atoms per nitrogen atom such as for example polyamide-6, polyamide-6.6, polyamide-4.6, copolyamide-6.T/6.6, copolyamide 6.I /6.6, copolyamide 6.T/6.I/6.6, polyamide 9.T. I represents isophthalic diacid.
• PA6.12 is a PA with 9 carbon atoms per nitrogen atom, in other words a PA in C9.
• the PA6.13 is in C9.5.
• the number of carbon atoms per nitrogen atom is calculated according to the same principle. The calculation is carried out in molar proportion of the various amide units. In the case of a copolyamide having units of non-amide type, the calculation is carried out solely on the part of amide units.
• PEBA-12 which is a block copolymer of amide 12 units and ether units
• the average number of carbon atoms per nitrogen atom will be 12, as for PA12; for PEBA-6.12, it will be 9, as for PA6.12.
• high-carbon polyamides such as polyamide PA12 or 1 1 adhere with difficulty to an EVOH polymer, to a low-carbon polyamide such as polyamide PA6, or else on an alloy of PA6 polyamide and polyolefin (such as, for example, an Orgalloy® marketed by the company Arkema).
• one of the inner layers has a proportion of plasticizer greater than 1.5% by weight but in this case, the proportion of plasticizer beyond 1.5 % is compensated by the thickness of the layer which is then much thinner so that the average value of plasticizer present in all of the inner layers does not exceed 1.5%.
• the proportion of plasticizer in this layer can then be up to 15% but its thickness does not then exceed 10% of the total thickness of the tube, preferably it does not exceed 100 ⁇ m.
• This much thinner layer can be either directly in contact with the barrier layer, or the innermost layer which is then in contact with the hydrogen.
• said inner layer (2) mainly comprising at least one aliphatic-type polyamide means that said aliphatic-type polyamide is present in a proportion of more than 50% by weight in the layer (2).
• Aliphatic type polyamide is linear and not cycloaliphatic type.
• said majority aliphatic-type polyamide of the layer(s) (2) also mainly comprises aliphatic units, namely more than 50% of aliphatic units.
• said polyamide of the majority aliphatic type of the layer or layers (2) consists of more than 75% of aliphatic units, preferably said polyamide of the majority aliphatic type of the layer or layers (2) is totally aliphatic.
• said inner layer (2) or each of the layers (2) and any other layers located below the barrier layer contains from 0 to 1.5% by weight of plasticizer relative respectively to the total weight of the composition of the layer (2) or to the total weight of each of the compositions of the layers (2) and of the other possible layers located below the barrier layer.
• said inner layer (2) or each of the layers (2) and any other layers located below the barrier layer is ( are) devoid of plasticizer.
• all the layers located under the barrier layer are completely devoid of plasticizer and constitute one of the preferred structures of the invention.
• the PA12 is excluded from the definition of the polyamide C of the layer (2) or layers (2) present.
• the polyamide of the inner layer (2) is a composition based on a chosen polyamide from A, B or C as defined above, in particular PA6, PA66, PA6/66, PA11, PA610, PA612, PA1012, the corresponding copolyamides and mixtures of said polyamides or copolyamides, the polyamides obtained from a lactam being advantageously washed
• the polyamide of the outer layer (3) is a polyamide chosen from B or C as defined above, in particular PA 11, PA12, PA610, PA612, PA1012, the corresponding copolyamides and mixtures said polyamides or copolyamides, the polyamides obtained from a lactam being advantageously washed.
• the present invention relates to a multilayer tubular structure (MLT) as defined below, in which the polyamide of the inner layer (2) or of at least one of the other layers (2) is a conductive polyamide.
• MKT multilayer tubular structure
• the conductive layer is the one which is the most internally, that is to say in contact with the hydrogen.
• the polyamide of the inner layer (2) is a composition based on a polyamide chosen from A, B or C as defined above, in particular PA6, PA66, PA6/66, PA11, PA610, PA612, PA1012, the corresponding copolyamides and mixtures of said polyamides or copolyamides, the polyamides obtained from a lactam being advantageously washed.
• the present invention relates to a multilayer tubular structure (MLT) as defined above, in which at least one more outer layer (3) located above the barrier layer is present, the said layer external (3) mainly comprising at least one polyamide of the aliphatic type or consisting of more than 75% of aliphatic units, in particular said aliphatic polyamide having an average number of carbon atoms per nitrogen atom of between 9.5 and 18, advantageously from 11 to 18.
• MMT multilayer tubular structure
• said outer layer (3) mainly comprising at least one aliphatic-type polyamide means that said aliphatic-type polyamide is present in a proportion of more than 50% by weight in the layer (3).
• Aliphatic type polyamide is linear and not cycloaliphatic type.
• said majority aliphatic-type polyamide of the layer(s) (3) also mainly comprises aliphatic units, namely more than 50% of aliphatic units.
• said polyamide of the majority aliphatic type of the layer or layers (3) consists of more than 75% of aliphatic units, preferably said polyamide of the majority aliphatic type of the layer or layers (3) is totally aliphatic.
• said majority aliphatic-type polyamide of the layer or layers (2) and of the layer or layers (3) also mainly comprises aliphatic units, namely more than 50% of aliphatic units.
• said polyamide of the majority aliphatic type of the layer or layers (2) and of the layer or layers (3) consists of more than 75% of aliphatic units, preferably said polyamide of the majority aliphatic type of the layer or layers ( 2) and the layer or layers (3) is completely aliphatic.
• the present invention relates to a multilayer tubular structure (MLT) as defined above, in which said outer layer (3) comprises from 0 to 15% of plasticizer relative to the total weight of the composition of the layer (3) , or in which all of the outer layers comprise on average from 0 to 5% of plasticizer.
• MKT multilayer tubular structure
• one of the outer layers has a high proportion of plasticizer such as at 15% by weight but in this case, the proportion of plasticizer is compensated by the thickness of the layer which is then much thinner so that the average value of plasticizer present in all of the inner layers does not exceed 5%.
• the proportion of plasticizer in this layer can then be up to 15% but its thickness does not exceed 20% of the total thickness of the tube, preferably it does not exceed 200 ⁇ m.
• the present invention relates to a multilayer tubular structure (MLT) comprising a layer (3) as defined above, in which at least one second outer layer (3') located above the barrier layer is present, and preferably located above layer (3), said layer (3') being plasticized, said plasticizer being in particular present in a proportion of 1.5% to 15% by weight relative to the total weight of the composition of said layer, the thickness of said layer (3') preferably represents up to 20% of the total thickness of the tubular structure, in particular up to 200 ⁇ m.
• MLT multilayer tubular structure
• Layer (3') comprises, like layer (3), predominantly an aliphatic-type polyamide, that is to say that said aliphatic-type polyamide is present in a proportion of more than 50% by weight in layer (3') .
• Aliphatic type polyamide is linear and not cycloaliphatic type.
• said majority aliphatic-type polyamide of the layer or layers (3′) also mainly comprises aliphatic units, namely more than 50% of aliphatic units.
• said polyamide of the majority aliphatic type of the layer or layers (3') consists of more than 75% of aliphatic units, preferably said polyamide of the majority aliphatic type of the layer or layers (3') is totally aliphatic.
• the present invention relates to a multilayer tubular structure (MLT), in which the layer(s) (3) comprise(s) up to 1.5% by weight of plasticizer, per relative to the total weight of the composition of said layer or of all the compositions of the layers (3).
• the multilayer tubular structure comprises a single layer (3) and is devoid of plasticizer.
• the multilayer tubular structure comprises a single layer (3) and a single layer (2), the layers (2) and (3) being devoid of plasticizer.
• the present invention relates to a multilayer tubular structure (MLT), in which the level of plasticizer of all the layers located above the barrier layer is at most 5% by weight relative to the total weight. compositions of all layers above the barrier layer.
• MLT multilayer tubular structure
• the present invention relates to a multilayer tubular structure (MLT), in which the layer (3') is the outermost and is the only plasticized one, the layer(s) (3) being devoid of plasticizer.
• MLT multilayer tubular structure
• the proportion of plasticizer can represent up to 15% by weight of the total weight of the composition of the layer (3').
• the multilayer tubular structure (MLT) consists of four layers, from the outside to the inside (3')//(3)//(1)//(2), the layer (3') being the only plasticized in proportions as defined above, the layer (3) and the layer (2) being devoid of plasticizer.
• the layer (3′) is the outermost and the polyamide of the latter is a long-chain polyamide, i.e. an average number of carbon atoms per nitrogen atom denoted Ce, including 9.5 to 18, layer (3) is located between the barrier layer and layer (3') and the polyamide of this layer (3) is a short-chain polyamide, i.e. an average number of carbon atoms per nitrogen atom noted Ca comprised from 4 to 9.
• layer (3') has a thickness of between 100 and 200 ⁇ m
• layer (3) has a thickness of at least 200 ⁇ m
• layer (1) has a thickness of 100 to 200pm.
• the layer (3′) is the outermost and the polyamide of the latter is a long-chain polyamide, i.e. an average number of carbon atoms per nitrogen atom denoted Ce, including 9.5 to 18, layer (3) is located between the barrier layer and layer (3') and the polyamide of this layer (3) is a short-chain polyamide, i.e.
• the multilayer tubular structure (MLT) consists of five layers from the outside to the inside (3')//(3)//(1)//(2)//(2'), the layer (3') being the only one plasticized in proportions as defined above, layer (3) and layers (2) and (2') being devoid of plasticizer, layer (2') being a polyamide such as defined for layer (2) but different from that of layer (2).
• This type of structure makes it possible to increase the elongation at break under very low humidity conditions) without over-stiffening the structure.
• the preferred tubular structures are those containing the least possible plasticizer, and preferably the least plasticizer in the innermost layers, that is to say closest to the fluid. These structures can be the following:
• MTT Multilayer tubular structure
• MMT Multilayer tubular structure
• MMT Multilayer tubular structure
• MKT Multilayer tubular structure
• MLT Multilayer tubular structure
• MMT Multilayer tubular structure
• the present invention relates to a multilayer tubular structure (MLT) as defined above, in which at least one layer (4) is present, said layer (4) containing no more than 15% by weight of plasticizer, preferably no more than 1.5% by weight of plasticizer, relative to the total weight of the constituents of the layer (4), advantageously the layer (4) is devoid of plasticizer, said layer (4) mainly comprising at least one polyamide of the aliphatic type or consisting of more than 75% of aliphatic units, said aliphatic polyamide being chosen from: - a polyamide denoted A having an average number of carbon atoms per nitrogen atom denoted CA comprised from 4 to 8.5, advantageously from 4 to 7;
• a polyamide noted C having an average number of carbon atoms per nitrogen atom noted CC comprised from 9 to 18, advantageously from 10 to 18; provided that when said layer (4) comprises at least three polyamides, at least one of said polyamides A, B or C is excluded, said layer (4) being located between the barrier layer (1) and the inner layer (2 ) and/or between the outer layer (3) and the barrier layer (1); or said layer (4) is a binder layer whose thickness represents up to 15% of the structure (MLT).
• Layer (4) when it is not a binder layer is an aliphatic-type polyamide as defined for layers (2), (3) and (3').
• the tubular structure of the invention is a four-layer structure consisting of the following layers from the outside inwards: (3)//(4)//(1)//(2), the layer ( 3) being plasticized up to 15% as above and thin and the layer (4) when it is different from the binder layer as defined above is devoid of plasticizer as well as the layer (2).
• the tubular structure of the invention is a four-layer structure consisting of the following layers from the outside inwards: (3)//(1)//(4)//(2), the layer ( 3) being plasticized up to 15% by weight as above and preferably thin and the layer (4) when it is different from the binder layer, as defined above, is devoid of plasticizer as well as the layer (2).
• this layer (3) plasticized up to 15% by weight must not be too thin otherwise the barrier layer is too little in the center and the MLT structure may not be good enough in shock.
• Another layer (2') and/or a layer (3') can also be present in these two types of four-layer structures.
• Said layer (4) can also be a binder as described, in particular in patents EP 1452307 and EP1 162061, EP 1216826 and EP0428833.
• the binder layer is intended to be interposed between two layers which do not or hardly adhere to each other.
• the binder can be, for example, but without being limited thereto, a composition based on 50% copolyamide 6/12 (ratio 70/30 by mass) of Mn 16000, and 50% copolyamide 6/12 ( of ratio 30/70 by mass) of Mn 16000, a composition based on PP (polypropylene) grafted with maleic anhydride, known under the name of Admer QF551A from Mitsui, a composition based on PA610 (from Mn 30000, and as defined elsewhere) and from 36% of PA6 (from Mn 28000) and from 1.2% of organic stabilizers (consisting of 0.8% of Lowinox 44B25 phenol from the Great Lakes company, 0.2% of Irgafos 168 phosphite from the Ciba company, 0.2% of Tinuvin 312 anti-UV from the Ciba company), a composition based on PA612 (from Mn 29000, and as defined elsewhere) and 36% PA6 (from Mn 28000, and as
• the present invention relates to a multilayer tubular structure (MLT) as defined above, in which a layer (4') is present, said layer (4') mainly comprising at least one polyamide of aliphatic or consisting of more than 75% of aliphatic units, said aliphatic polyamide being chosen from:
• A having an average number of carbon atoms per nitrogen atom denoted CA comprised from 4 to 8.5, advantageously from 4 to 7;
• a polyamide noted C having an average number of carbon atoms per nitrogen atom noted CC comprised from 9 to 18, advantageously from 10 to 18; provided that when said layer (4') comprises at least three polyamides, at least one of said polyamides A, B or C is excluded, or said layer (4') is a binder layer whose thickness represents up to at 15% of the structure (MLT), said at least polyamide of said layer (4') possibly being identical to or different from said polyamide of layer (4); said layer (4') being located between the outer layer (3) and the barrier layer (1) and said binder layer (4) being located between the barrier layer (1) and the inner layer (2).
• the layer (4') may or may not contain a plasticizer.
• it is devoid of plasticizer, like layer (2) and layer (4), layer (3) being plasticized but thin as defined above.
• the present invention relates to a multilayer tubular structure (MLT) as defined above, in which the polyamide of the inner layer (2) or the polyamide of the outer layer (3) is a polyamide totally aliphatic, preferably the polyamide of the inner layer (2) and the polyamide of the outer layer (3) are totally aliphatic polyamides.
• MMT multilayer tubular structure
• the polyamide of layer (4) and/or (4') is a mixture of a polyamide having an average number of carbon atoms per atom nitrogen of 10 or more and a polyamide having an average number of carbon atoms per nitrogen atom of 6 or less, for example PA12 and PA6 and an anhydride functionalized (co)polyolefin.
• the polyamide of layer (4) and/or (4') is chosen from binary mixtures: PA6 and PA12, PA6 and PA612, PA6 and PA610 , PA12 and PA612, PA12 and PA610, PA1010 and PA612, PA1010 and PA610, PA1012 and PA612, PA1012 and PA610, and ternary mixtures: PA6, PA610 and PA12; PA6, PA612 and PA12; PA6, PA614 and PA12.
• the present invention relates to a multilayer tubular structure (MLT) as defined above, in which a second barrier layer (5) is present, said second barrier layer (5) being adjacent or not to the first barrier layer (1) and located below said barrier layer (1).
• MLT multilayer tubular structure
• This second barrier layer is different from the first barrier layer (1).
• the present invention relates to a multilayer tubular structure (MLT) as defined above, in which the barrier layer (1) is an EVOH layer and the second barrier layer (5) is an PPA or fluorinated polymer, in particular of the ETFE, EFEP, CPT type.
• the barrier layer (1) is an EVOH layer and the second barrier layer (5) is a PPA layer.
• the present invention relates to a multilayer tubular structure (MLT) as defined above, in which the barrier layer (1) is an EVOH layer and the second barrier layer (5) is an PPP.
• MLT multilayer tubular structure
• the present invention relates to a multilayer tubular structure (MLT) as defined above, in which the barrier layer (1) is an EVOH layer and the second barrier layer (5) is an fluorinated polymer, in particular of the ETFE, EFEP, CPT type.
• the polyamide of the outer layer (3) is a polyamide chosen from B or C as defined above, in particular PA 11, PA12, PA610 , PA612, PA1012, the corresponding copolyamides and mixtures of said polyamides or copolyamides, the polyamides obtained from a lactam being advantageously washed.
• the present invention relates to a multilayer tubular structure (MLT) as defined above, in which at least one of the layers (2), (3), (3'), (4) and ( 4') comprises at least one impact modifier and/or at least one additive.
• MLT multilayer tubular structure
• the impact modifier or additive is not a plasticizer.
• the layers (2) and (3) comprise at least one impact modifier and/or at least one additive.
• the layers (2), (3) and (3') comprise at least one impact modifier and/or at least one additive.
• the layers (2), (3), (3') and (4) comprise at least one impact modifier and/or at least one additive.
• the layers (2), (3), (3'), (4) and (4') comprise at least one impact modifier and/or at least one additive.
• the present invention relates to a multilayer tubular structure (MLT) as defined above, in which the structure comprises three layers in the following order (3)//(1)//(2) , layers (3) and/or (2) not containing more than 1.5% by weight of plasticizer, relative to the total weight of the composition of each layer, in particular layer (3) and/or (2 ) is (are) devoid of plasticizer.
• MLT multilayer tubular structure
• the present invention relates to a multilayer tubular structure (MLT) as defined above, in which the structure comprises four layers in the following order (3')//(3)//(1 )//(2), layer (3') being as defined above, layer (2) and/or (3) not containing more than 1.5% by weight of plasticizer, relative to the weight total of the composition of each layer, in particular layer (2) and/or (3) is (are) devoid of plasticizer.
• MLT multilayer tubular structure
• the present invention relates to a multilayer tubular structure (MLT) as defined above, in which the structure comprises five layers in the following order:
• the layer (1) is an EVOH layer
• the layer (5) is a PPA layer
• the layer (1) is an EVOH layer
• the layer (5) is a PPA layer
• layer (3) is as defined in claim 3, layer (2) and (4) are not containing no more than 1.5% by weight of plasticizer, relative to the total weight of the composition of each layer, in particular layer (2) and/or (4) is (are) devoid of plasticizer, the layer (4') comprising plasticizer, in particular layer (4') is devoid of plasticizer.
• the present invention relates to a multilayer tubular structure (MLT) as defined above, in which the structure comprises the layers in the following order:
• the layer (2) and (4) not containing more than 1.5% by weight of plasticizer, relative to the total weight of the composition of each layer, in particular the layer (2) and/or (4) is ( are) devoid of plasticizer, the layer (4') comprising plasticizer, in particular the layer (4') is devoid of plasticizer.
• said layer (3') of the above six-layer structure is plasticized, said plasticizer being in particular present in a proportion of 1.5% to 15% by weight relative to the total weight of the composition of said layer.
• the thickness of said layer (3') preferably represents up to 20% of the total thickness of the tubular structure, in particular up to 200 ⁇ m, in particular the layer (3') is the outermost and is the only plasticized, the (or the) layer (s) (3) being devoid (s) of plasticizer.
• the present invention relates to a multilayer structure as defined above, characterized in that it comprises a polyamide connection at one and/or the other of its ends, said connection being welded to said structure.
• the welding can be carried out for example by means of a laser.
• the polyamide is chosen from an aliphatic polyamide as defined above and a semi-aromatic polyamide, 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 (Ca-diamine).
• (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 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/11T, A being as defined above, in particular a polyamide chosen from a PA MPMDT/6T, a PA11 /1 OT, PA 5T/1 OT, PA 11 /BACT, PA 11 Z6T/1 OT, PA MXDT/10T, PA MPMDT/10T, PA BACT/10T, PA BACT/6T, PA BACT/6T/6T, one PA 11/BACT/6T, PA 11/MPMDT/6T, PA 11/MPMDT/10T, PA 1 1/BACT/10T, one PA 1 1/MXDT/10T, one 11/5T /10T.
• T stands for terephthalic acid
• MXD stands for m-xylylene diamine
• MPMD stands for methylpentamethylene diamine
• BAC stands for bis(aminomethyl)cyclohexane.
• PA12 is excluded from the aliphatic polyamide constituting said fitting.
• the aliphatic polyamide of said coupling is chosen from PA6, PA66, PA6/66, PA11, PA610, PA612, PA1012, in particular PA11.
• said fitting consists of a polyamide composition as defined above, said composition being a fiber-filled composition.
• the fibers are of mineral, organic or vegetable origin.
• 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.
• the fibers of organic origin mention may be made of fibers based on thermoplastic or thermosetting polymer, such as semi-aromatic polyamide fibers, aramid fibers or polyolefin fibers for example.
• the fibers are glass and/or carbon fibers.
• the present invention relates to the use of a multilayer tubular structure MLT, as defined above, for the transport of hydrogen.
• compositions were prepared according to techniques well known to those skilled in the art for forming the inner layer (2) of the structures of the invention (Table 1).
• compositions of the invention are 11 to I2: compositions of the invention
• PA11 is a polyamide 11 of Mn (number molecular mass) 45000.
• the melting temperature is 190° C., its melting enthalpy cb is 56 J/g.
• PA11/10T Rilsan HT (Arkema)
• Plasticizer BBSA (n-butyl benzene sulfonamide)
• Multilayer pipes are produced by coextrusion.
• An industrial McNeil multilayer extrusion line is used, equipped with 5 extruders, connected to a multilayer extrusion head with spiral mandrels.
• the screws used are single extrusion screws with screw profiles adapted to polyamides.
• the extrusion line includes:
• a vacuum tank with an adjustable vacuum level In this tank circulates water maintained at 20 ° C in general, in which is immersed a gauge allowing to conform the tube in its final dimensions.
• the diameter of the gauge is adapted to the dimensions of the tube to be produced, typically from 8.5 to 10 mm for a tube with an external diameter of 8 mm and a thickness of 1 mm; • a succession of cooling tanks in which water is kept at around 20°C, allowing the tube to be cooled along the length of its journey from the head to the draw bench;
• the 5-extruder configuration is used to produce tubes ranging from 2 layers to 5 layers. In the case of structures whose number of layers is less than 5, several extruders are then fed with the same material.
• an additional extruder is connected and a spiral mandrel is added to the existing head, in order to produce the internal layer, in contact with the hydrogen.
• the extruded materials Before the tests, in order to ensure the best tube properties and good extrusion quality, it is checked that the extruded materials have a residual moisture content before extrusion of less than 0.08%. Otherwise, an additional stage of drying the material is carried out before the tests, generally in a vacuum dryer, overnight at 80°C.
• the tubes which meet the characteristics described in this patent application, were sampled after stabilization of the extrusion parameters, the dimensions of the targeted tubes no longer changing over time.
• the diameter is controlled by a laser diameter gauge installed at the end of the line.
• the line speed is typically 20m/min. It generally varies between 5 and 100m/min.
• the screw speed of the extruders depends on the thickness of the layer and the diameter of the screw as is known to those skilled in the art.
• the temperatures of the extruders and the tools must be adjusted so as to be sufficiently higher than the melting temperature of the compositions under consideration, so that they remain in the molten state, thus avoiding they solidify and block the machine.
• the amount of extractables was determined and the barrier properties were evaluated.
• Table 3 shows the tests used and the classification of the results.
• the instantaneous permeability is zero during the induction period, then it gradually increases to an equilibrium value which corresponds to the steady-state permeability value. This value obtained in steady state is considered to be the permeability of the material.
• Multi-layer structure with sealing layer based on composition-11 ⁇ 0.5%
• Multi-layer structure with sealing layer based on composition-12 ⁇ 0.5%
• Multilayer structure with waterproofing layer based on composition-13 ⁇ 0.5%
• Multilayer structure with waterproofing layer based on composition-14 ⁇ 0.5%
• Multi-layer structure with sealing layer based on composition-15 ⁇ 0.5%
• Multilayer structure with sealing layer based on composition-CI >3%
• Multilayer structure with sealing layer based on composition-C2 >3%
• PA12-TL denotes a composition based on polyamide 12 of Mn (number molecular weight) 35,000, containing 6% of plasticizer BBSA (benzyl butyl sulfonamide), and 6% of anhydride functionalized EPR Exxelor VA1801 (Exxon company), and 1.2% organic stabilizers (consisting of 0.8% Lowinox 44B25 phenol from the Great Lakes company, 0.2% Irgafos 168 phosphite from the Ciba company, 0.2% Tinuvin 312 anti-UV from the Ciba company). The melting point of this composition is 175°C.
• PA12-NoPlast PA12-TL without the plasticizer (the latter is replaced by the same % in PA12)
• PA11-TL denotes a composition based on polyamide 11 of Mn (number molecular weight) 29,000, containing 5% of BBSA (benzyl butyl sulfonamide) plasticizer, 6% of impact modifier type ethylene/ethyl acrylate/anhydride in mass ratio 68.5/30/1.5 (MFI 6 at 190°C under 2.16 kg), and 1.2% organic stabilizers (consisting of 0.8% Lowinox 44B25 phenol from Great Lakes, 0.2% phosphite Irgafos 168 from Ciba, 0.2% anti-UV Tinuvin 312 from Ciba). The melting point of this composition is 185°C.
• BBSA benzyl butyl sulfonamide
• PA1 1 -NoPlast PA11 -TL without plasticizer (the latter is replaced by PA1 1 )
• PA610-TL PA610 + 12% EPR1 impact modifier + organic stabilizer + 10% plasticizer
• PA610-NoPlast PA610-TL without the plasticizer (the latter is replaced by PA610)
• PA612-TL PA612 + 12% EPR1 impact modifier + organic stabilizer + 9% plasticizer
• PA612-NoPlast PA612-TL without the plasticizer (the latter is replaced by PA612)
• PA6-TL PA6 + 12% EPR1 impact modifier + organic stabilizer + 12% plasticizer
• PA6-NoPlast PA6-TL without the plasticizer (the latter is replaced by PA6)
• PA12 Polyamide 12 of Mn (molecular mass in number) 35000. The melting temperature is 178°C, its melting enthalpy cb is 54kJ/m2
• PA11 Polyamide 1 1 of Mn (molecular mass in number) 29000. The melting temperature is 190°C, its melting enthalpy cb is 56kJ/m2 • PA610: Polyamide 6.10 of Mn (molecular mass in number) 30000. The melting temperature is 223 °C, its enthalpy ce fusion is 61 kJ/m2
• PA612 Polyamide 6.12 of Mn (molecular mass in number) 29000. The melting temperature is 218°C, its enthalpy ce fusion is 67kJ/m2
• PA6 Polyamide 6 of Mn (molecular mass in number) 28000. The melting temperature is 220°C, its enthalpy of fusion is 68kJ/m2
• EPR1 Refers to an EPR functionalized by an anhydride function reactive group (at 0.5-1% by mass), of MFI 9 (at 230° C., under) 10 kg, of the Exxellor VA1801 type from the company Exxon.
• Organic stabilizer 1.2% organic stabilizers consisting of 0.8% phenol (Lowinox 44B25 from the Great Lakes company), 0.2% phosphite (Irgafos 168 from the Ciba company, 0.2% anti-UV (Tinuvin 312 from the Ciba company).
• PPA10T coPA10.T/6T of molar ratio 60/40 T fusion 280°C + 18% EPR1 + stab orga
• PA1 1cond-noplast PA1 1 of Mn 15000 + 9%EPR1 + 22% carbon black type Ensaco 200
• Binder Composition based on 43.8% PA612 (t.q defined elsewhere), 25% PA6 (t.q defined elsewhere) and 20% impact modifier type EPR1, and 1.2% organic stabilizers (consisting of 0.8% phenol Lowinox 44B25 from the company Great Lakes, 0.2% phosphite Irgafos 168 from the company Ciba, 0.2% anti-UV Tinuvin 312 from the company Ciba), and 10% plasticizer BBSA (benzyl butyl sulfonamide).
• Binder-NoPlast Composition based on 48.8% PA612 (tq defined elsewhere), 30% PA6 (tq defined elsewhere), and 20% impact modifier type EPR1, and 1.2% organic stabilizers (consisting of 0.8% Lowinox 44B25 phenol from Great Lakes, 0.2% Irgafos 168 phosphite from Ciba, 0.2% Tinuvin 312 anti-UV from Ciba).
• Binder2 Composition based on 43.8% PA610 (tq defined elsewhere), 25% PA6 (tq defined elsewhere) and 20% EPR1 type impact modifier, and 1.2% organic stabilizers (consisting of 0.8 % of Lowinox 44B25 phenol from Great Lakes, 0.2% Irgafos 168 phosphite from Ciba, 0.2% Tinuvin 312 anti-UV from Ciba, and 10% plasticizer BBSA (benzyl butyl sulfonamide ).
• Binder2-NoPlast Composition based on 48.8% PA610 (t.q defined elsewhere), 30% PA6 (t.q defined elsewhere), and 20% impact modifier type EPR1, and 1.2% organic stabilizers ( consisting of 0.8% Lowinox 44B25 phenol from Great Lakes, 0.2% Irgafos 168 phosphite from Ciba, 0.2% Tinuvin 312 anti-UV from Ciba).
• EVOH 32% ethylene EVOH, type EVAL FP101 B (Eval company)
• EVOH24 EVOH with 24% ethylene, type EVAL M100B (Eval company)
• EVOHhi 27% ethylene impact modified EVOH, type EVAL LA170B (Eval company)
• PPA10T/6T coPA10.T/6.T with 40% mol of 6.
• T (of MFI 300°C, 5kg 8, and of melting T°C 280°C) + 15% of EPRI + stab orga
• EFEPc functionalized and conductive EFEP type Neoflon RP5000AS from Daikin
• Binder PA610 + PA6 Refers to a composition based on PA612 (from Mn 29000, and as defined elsewhere) and 36% PA6 (from Mn 28000, and as defined elsewhere) and 1.2% organic stabilizers (consisting of 0.8 % Lowinox 44B25 phenol from Great Lakes, 0.2% Irgafos 168 phosphite from Ciba, 0.2% Tinuvin 312 anti-UV from Ciba).
• the structures having layers devoid of plasticizer located under the barrier and in particular in contact with hydrogen show excellent results on the extractables test and much better than the counter-examples in which the layer in contact with hydrogen is plasticized. .

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• Engineering & Computer Science (AREA)
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• General Engineering & Computer Science (AREA)
• Laminated Bodies (AREA)
• Wrappers (AREA)
• Rigid Pipes And Flexible Pipes (AREA)

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• 2021
  • 2021-09-27 FR FR2110144A patent/FR3127435B1/fr active Active
• 2022
  • 2022-09-22 US US18/695,922 patent/US20240384816A1/en active Pending
  • 2022-09-22 CN CN202280075428.5A patent/CN118234617A/zh active Pending
  • 2022-09-22 EP EP22197191.4A patent/EP4155068B1/fr active Active
  • 2022-09-22 WO PCT/FR2022/051783 patent/WO2023047057A1/fr not_active Ceased
  • 2022-09-22 JP JP2024518881A patent/JP2024536101A/ja active Pending
  • 2022-09-22 KR KR1020247013632A patent/KR20240078430A/ko active Pending

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