WO2022069826A1 - Structure multicouche pour le stockage de l'hydrogene - Google Patents
Structure multicouche pour le stockage de l'hydrogene Download PDFInfo
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- WO2022069826A1 WO2022069826A1 PCT/FR2021/051665 FR2021051665W WO2022069826A1 WO 2022069826 A1 WO2022069826 A1 WO 2022069826A1 FR 2021051665 W FR2021051665 W FR 2021051665W WO 2022069826 A1 WO2022069826 A1 WO 2022069826A1
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Definitions
- TITLE MULTILAYER STRUCTURE FOR HYDROGEN STORAGE [Technical field]
- This patent application relates to composite multilayer structures for the storage of hydrogen, and their method of manufacture.
- Hydrogen tanks are 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 generally consist of a metal envelope (liner or sealing layer) which must prevent the permeation of hydrogen.
- a metal envelope liner or sealing layer
- 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 make it possible to work at much higher pressures. all in 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 defect of having a too low melting temperature and a high hydrogen permeability, which represents a problem with the new requirements in terms of thermal resistance and does not allow to increase the filling speed of the tank.
- PA6 polyamide
- WO2018155491 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, 1 to 3% of plasticizer or devoid of plasticizer, and which has hydrogen barrier properties, good flexibility and durability at low temperature.
- this structure is suitable for pipes for the transport of hydrogen but not for the storage of hydrogen and, moreover, this composition has a viscosity that is too progressive to be stable for transformation by extrusion blow molding, a transformation technology which can generate very high melt residence times (up to 20 minutes) at high temperature within the accumulation blocks.
- the matrix of the composite so as to optimize its mechanical resistance at high temperature and on the other hand the material composing the sealing sheath, so as to optimize its implementation temperature.
- the change possible composition of the material making up the sealing sheath which will be made, must not result in a significant increase in the manufacturing temperature (extrusion-blow molding, injection, rotational molding, etc.) of this liner, compared to this which is practiced today.
- the present invention therefore relates to a multilayer structure intended for the storage of hydrogen, comprising, from the inside outwards, at least one sealing layer (1) and at least one composite reinforcement layer (2), said innermost composite reinforcing layer being wrapped around said outermost adjacent sealing layer (1), at least said innermost sealing layer consisting of a composition comprising, relative to the total weight of the composition : has. 20.5 to 99.845% by weight of at least one polyamide; b. 0.005 to 0.5% by weight of at least one catalyst; vs. 0.05 to 1% by weight of at least one heat stabilizer; d. 0.1 to 3% by weight of at least one oligo- or poly-carbodiimide; e. 0 to 1.5% by weight of at least one plasticizer, f.
- said structure is devoid of nucleating agent.
- said structure does not have an outermost layer adjacent to the outermost layer of composite reinforcement made of polyamide polymer.
- said structure is devoid of nucleating agent and is devoid of an outermost layer and adjacent to the outermost layer of composite reinforcement made of polyamide polymer.
- a semi-crystalline long-chain polyamide thermoplastic polymer comprising a limited proportion of impact modifier and plasticizer, a catalyst, a heat stabilizer and an oligo- or poly-carbodiimide allowed not only to obtain compositions for the layer sealants, which have good viscosities, that is to say viscosities in the molten state that are sufficiently high to be able to be transformed, in particular by extrusion-blow molding, without however increasing the viscosity in solution, in other words the viscosity inherent, said viscosity in the molten state being moreover sufficiently stable during the transformation, in particular for extrusion blow molding.
- multilayer structure is meant a tank comprising or consisting of several layers, namely several sealing layers and several reinforcing layers, or one sealing layer and several reinforcing layers, or several sealing layers and a reinforcing layer or a sealing layer and a reinforcing layer.
- the multilayer structure is therefore understood to exclude a pipe or a tube.
- said multilayer structure consists of two layers, a sealing layer and a reinforcing layer.
- the sealing layer or layers are the innermost layers compared to the composite reinforcement layers which are the outermost layers.
- the tank can be a tank for mobile hydrogen storage, i.e. on a truck for transporting hydrogen, on a car for transporting hydrogen and supplying hydrogen to a fuel cell for example, on a train for hydrogen supply or on a drone for hydrogen supply, but it can also be a stationary hydrogen storage tank in a station for hydrogen distribution 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 reinforcement layer(s) is (are) wound around the sealing 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 outermost layer of said sealing layers, and therefore opposite the layer in contact with the hydrogen, may or may not adhere to the innermost layer of said composite reinforcement.
- the other layers of composite reinforcement may also adhere or not to each other.
- the other sealing layers may or may not adhere to each other.
- a sealing layer and a reinforcing layer are present and do not adhere to each other.
- the reinforcement 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 or epoxy-based resin.
- a sealing layer and a reinforcement layer are present and do not adhere to each other and the reinforcement 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 specification means that the epoxy constitutes at least 50% by weight of the matrix.
- One or more sealing layers may be present.
- From 1 to 10 layers may be present, in particular from 1 to 5, in particular from 1 to 3, preferentially only 1 sealing layer is present.
- At least said innermost sealing layer consists of a composition comprising, relative to the total weight of the composition: a. 20.5 to 99.845% by weight of at least one polyamide; b. 0.005 to 0.5% by weight of at least one catalyst; vs. 0.05 to 1% by weight of at least one heat stabilizer; d. 0.1 to 3% by weight of at least one oligo- or poly-carbodiimide; e. 0 to 1.5% by weight of at least one plasticizer, f. 0 to less than 15% by weight of at least one polyolefin; g. 0 to 30% of at least one additive, the sum of constituents a to g representing 100% by weight.
- said composition consists of: a. 20.5 to 99.845% by weight of at least one polyamide; b. 0.005 to 0.5% by weight of at least one catalyst; vs. 0.05 to 1% by weight of at least one heat stabilizer; d. 0.1 to 3% by weight of at least one oligo- or poly-carbodiimide; e. 0 to 1.5% by weight of at least one plasticizer, f. 0 to less than 15% by weight of at least one polyolefin; g. 0 to 30% of at least one additive, the sum of constituents a to g representing 100% by weight.
- the catalyst is a mixture of:
- catalyst designates a polycondensation catalyst such as an inorganic or organic acid.
- the proportion by weight of catalyst is between about 50 ppm to about 5000 ppm, in particular from about 100 to about 3000 ppm relative to the total weight of the composition.
- the catalyst is chosen from phosphoric acid (H3PO4), phosphorous acid (H3PO3), hypophosphorous acid (H3PO2), or a mixture thereof.
- the proportion by weight of catalyst is between about 50 ppm to about 5000 ppm, in particular from about 100 to about 3000 ppm relative to the total weight of the composition and said catalyst is chosen from phosphoric acid (H3PO4 ), phosphorous acid (H3PO3), hypophosphorous acid (H3PO2), or a mixture thereof.
- the catalyst is chosen from phosphoric acid (H3PO4), phosphorous acid (H3PO3) in a proportion of approximately 100 to approximately 3000 ppm.
- This stabilizer can be an organic stabilizer or more generally a combination of organic stabilizers, such as a primary antioxidant of the phenol type (for example of the type of that of irganox 245 or 1098 or 1010 from the company Ciba), a secondary antioxidant of the phosphite and even possibly other stabilizers such as a HALS, which means Hindered Amine Light Stabilizer or hindered amine type light stabilizer (for example Tinuvin 770 from the company Ciba), a phenol phosphite type antioxidant such as ANOXONDB TL89, a anti-UV (for example Tinuvin 312 from Ciba), a phenolic or phosphorus-based stabilizer. It is also possible to use antioxidants of the type amine such as Naugard 445 from the company Crompton or even polyfunctional stabilizers such as Nylostab S-EED from the company Clariant.
- a primary antioxidant of the phenol type for example of the type of that of irganox 2
- This stabilizer can also be an inorganic stabilizer, such as a copper-based stabilizer.
- a copper-based stabilizer By way of example of such inorganic stabilizers, mention may be made of copper halides and acetates. Incidentally, one can possibly consider other metals such as silver, but these are known to be less effective. These copper-based compounds are typically associated with alkali metal halides, particularly potassium.
- the heat stabilizer is an organic stabilizer.
- the heat stabilizer is in a proportion of about 0.05% to about 1%, in particular from about 0.05% to about 0.3% by weight relative to the total weight of the composition.
- the proportion by weight of catalyst is between about 50 ppm to about 5000 ppm, in particular from about 100 to about 3000 ppm relative to the total weight of the composition
- the thermal stabilizer is in a proportion of about 0, 0.05% to approximately 1%, in particular from approximately 0.05% to approximately 0.3% by weight relative to the total weight of the composition
- said catalyst being chosen from phosphoric acid (H3PO4), acid phosphorous (H3PO3), hypophosphorous acid (H3PO2), or a mixture of these.
- the catalyst is chosen from phosphoric acid (H3PO4), phosphorous acid (H3PO3) in a proportion of approximately 100 to approximately 3000 ppm.
- Carbodiimide is a conventionally known carbodiimide oligomer and polymer and can be prepared by polymerization of diisocyanates.
- NCO end group reagents may include a CH, NH or OH reactive compound, for example esters of malonic acid, caprolactam, alcohols or phenols.
- mixtures of mono- and diisocyanates can be polymerized to obtain oligo- or polycarbodiimides containing essentially unreactive end groups.
- the carbodiimide used is an oligo or polycarbodiimide of general formula:
- the oligo- or polycarbodiimide can be a homopolymer or a copolymer, for example a copolymer of 2,4-diisocyanato-1,3,5-triisopropylbenzene and 1,3-diisocyanato-3,4-diisopropylbenzene.
- the oligo- or polycarbodiimide can also be chosen from those described in US 5,360,888.
- Suitable oligo and polycarbodiimides can be obtained from commercially available sources such as Rhein Chemie, Raschig or Ziko.
- the proportion by weight of oligo- or poly-carbodiimide used is between approximately 0.1 and approximately 3%, in particular from 0.5 to 2%, in particular approximately equal to 1% relative to the total weight of the composition.
- the oligo- or poly-carbodiimide is chosen from Stabilizers, in particular Stabilizer® 9000, Stabaxol®, in particular a stabaxol® P, in particular Stabaxol® P100 or Stabaxol® P400, or a mixture of those -this.
- the present invention therefore relates to the structure defined above comprising an innermost sealing layer consisting of a composition comprising, relative to the total weight of the composition, at least one catalyst, at least one heat stabilizer, and at least an oligo- or poly-carbodiimide in a proportion of approximately 0.1 to approximately 3%, in particular of 0.5 to 2%, in particular approximately equal to 1% by weight relative to the total weight of the composition, with a matrix comprising at least one thermoplastic polymer, in particular a polyamide, the said oligo- or poly-carbodiimide being chosen from a Stabilizer, in particular Stabilizer® 9000, a Stabaxol®, in particular a stabaxol® P, in particular Stabaxol® P100 or Stabaxol ® P400, or a mixture of these and, where appropriate, at least one plasticizer up to 1.5% by weight and/or at least one polyolefin up to 15% by weight.
- a Stabilizer in particular Stabilizer® 9000
- the proportion by weight of catalyst comprised from approximately 50 ppm to approximately 5000 ppm, in particular from approximately 100 to approximately 3000 ppm relative to the total weight of the composition, and the oligo- or poly-carbodiimide is in proportion from approximately 0.1 to approximately 3%, in particular from 0.5 to 2%, in particular approximately equal to 1% by weight relative to the total weight of the composition, with a matrix comprising at least one thermoplastic polymer, in particular a polyamide, said catalyst being chosen from phosphoric acid (H3PO4), phosphorous acid (H3PO3), hypophosphorous acid (H3PO2), or a mixture thereof and said oligo- or poly-carbodiimide being chosen from a Stabilize, in particular the Stabilizer® 9000, a Stabaxol®, in particular a Stabaxol® P, in particular Stabaxol® P100 or Stabaxol® P400, or a mixture of these.
- a Stabilize in particular the Stabilizer® 9000
- the catalyst is chosen from phosphoric acid (H3PO4), phosphorous acid (H3PO3) in a proportion of approximately 100 to approximately 3000 ppm.
- the heat stabilizer is in a proportion of about 0.05% to about 1%, in particular from about 0.05% to about 0.3% by weight relative to the total weight of the composition
- the oligo - or poly-carbodiimide is in a proportion of approximately 0.1 to approximately 3%, in particular from 0.5 to 2%, in particular approximately equal to 1% by weight relative to the total weight of the composition, and said oligo- or polycarbodiimide being chosen from a Stabilizer, in particular Stabilizer® 9000, a Stabaxol®, in particular a stabaxol® P, in particular Stabaxol® P100 or Stabaxol® P400, or a mixture of these.
- the proportion by weight of catalyst comprised from approximately 50 ppm to approximately 5000 ppm, in particular from approximately 100 to approximately 3000 ppm relative to the total weight of the composition
- the heat stabilizer is in a proportion of approximately 0.05 % to approximately 1%, in particular from approximately 0.05% to approximately 0.3% by weight relative to the total weight of the composition
- the oligo- or poly-carbodiimide is in a proportion of approximately 0.1 to approximately 3%, in particular from 0.5 to 2%, in particular approximately equal to 1% by weight relative to the total weight of the composition
- said catalyst being chosen from phosphoric acid (H3PO4), phosphorous acid ( H3PO3), hypophosphorous acid (H3PO2), or a mixture thereof
- said oligo- or poly-carbodiimide being chosen from a Stabilizer, in particular Stabilizer® 9000, a Stabaxol®, in particular a stabaxol® P, in in particular Stabaxol® P100 or Stabaxol
- the catalyst is chosen from phosphoric acid (H3PO4), phosphorous acid (H3PO3) in a proportion of approximately 100 to approximately 3000 ppm.
- H3PO4 phosphoric acid
- H3PO3 phosphorous acid
- Additives can be selected from other polymer, UV absorber, light stabilizer, lubricant, inorganic filler, flame retardant, colorant, carbon black and carbon nanofillers, except for a nucleating agent, in particular the additives are chosen from a UV absorber, a light stabilizer, a lubricant, an inorganic filler, a flame retardant, a colorant, carbon black and carbon nanofillers, at the exception of a nucleating agent.
- Said other polymer may be another semi-crystalline thermoplastic polymer or a different polymer and in particular an EVOH (ethylene vinyl alcohol).
- EVOH ethylene vinyl alcohol
- a single polyamide is present at least in the sealing layer which does not adhere to the composite reinforcement layer.
- polyamide is in particular a semi-crystalline, in particular aliphatic or semi-aromatic, in particular aliphatic, polyamide.
- si-crystalline polyamide means a material that is generally solid at room temperature, and which softens when the temperature rises, in particular after passing its glass transition temperature (Tg), and which may exhibit a sharp melting on passing of its so-called melting temperature (Tf), and which becomes solid again when the temperature drops below its crystallization 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 semi-crystalline polyamide is preferably in a range ranging 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 at inherent viscosities greater than or equal to 0.8 as determined in 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).
- the polyamide can be a homopolyamide or a copolyamide or a mixture thereof.
- said polyamide is an aliphatic polyamide, in particular with a long chain, that is to say a polyamide having an average number of carbon atoms per nitrogen atom greater than 8.5, preferably greater than to 9, in particular greater than 10.
- the long-chain aliphatic polyamide is chosen from:
- PA10 Polyamide 10
- PA11 Polyamide 11
- PA12 Polyamide 12
- PA1010 Polyamide 1010
- PA1012 Polyamide 1012
- PA1012 Polyamide 1212
- PA1012 Polyamide 1212
- PA11 polyamide 11
- PA12 polyamide 12
- PA1012 polyamide 1012
- PA1012 polyamide 1212
- PA1012 polyamide 1212
- the long-chain aliphatic polyamide is chosen from: polyamide 12 (PA12), polyamide 1010 (PA1010), polyamide 1012 (PA1012), polyamide 1212 (PA1012), or a mixture of these ci or a copolyamide thereof, in particular PA12.
- the long-chain aliphatic polyamide is chosen from: polyamide 12 (PA12), polyamide 1012 (PA1012), polyamide 1212 (PA1012), or a mixture of these or a copolyamide of these, in particular PA12.
- said semi-crystalline polyamide thermoplastic polymer is a semi-aromatic semi-crystalline polyamide, in particular with a long chain, that is to say a polyamide having an average number of carbon atoms per carbon atom. nitrogen greater than 8.5, preferably greater than 9, in particular greater than 10, and a melting temperature of between 240°C to less than 280°C.
- the long-chain semi-crystalline semi-aromatic polyamide is chosen from polyamide 11/5T or 11/6T or 11/1 OT, MXDT/10T, MPMDT/10T and BACT/1 OT.
- each sealing layer consists of a composition comprising the same type of polyamide.
- welding elements made of polyamide thermoplastic polymer.
- it can be used heating blades with or without contact, ultrasound, infrared, application of vibrations, rotation of one element to be welded against another or even laser welding.
- PEBAs are excluded from the definition of polyolefins.
- the polyolefin can be functionalized or non-functionalized or be a mixture of at least one functionalized and/or at least one non-functionalized.
- the polyolefin has been designated by (B) and functionalized polyolefins (B1) and non-functionalized polyolefins (B2) have been described below.
- a non-functionalized 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 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 styrene/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 possibly being totally or partially neutralized by metals such as Zn, etc.) or else by carboxylic acid anhydrides such as maleic anhydride.
- unsaturated epoxides such as glycidyl (meth)acrylate
- carboxylic acids or the corresponding salts or esters such as (meth)acrylic acid (the latter possibly being totally or partially neutralized by metals such as Zn, etc.) or else 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 of 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 styrene/ethylene-butene/styrene
- SBS styrene/butadiene/styrene
- SIS styrene/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 with a majority of propylene grafted with maleic anhydride then condensed with monoamino 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 saturated carboxylic acid vinyl ester and (3) anhydride such as maleic anhydride or (meth)acrylic acid or epoxy such as glycidyl (meth)acrylate.
- the ethylene preferably represents at least 60% by weight and in which the ter monomer (the function) represents, for example, from 0.1 to 10% by weight of the copolymer: - ethylene/(meth)acrylate/(meth)acrylic acid or maleic anhydride or glycidyl methacrylate copolymers;
- the (meth)acrylic acid can be salified with Zn or Li.
- alkyl (meth)acrylate in (B1) or (B2) denotes alkyl methacrylates and acrylates C1 to C8, and can be selected from methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, ethyl-2-hexyl acrylate, l cyclohexyl acrylate, methyl methacrylate and ethyl methacrylate.
- the aforementioned polyolefins (B1) can also be crosslinked by any appropriate process or agent (diepoxy, diacid, peroxide, etc.); the term functionalized polyolefin also includes mixtures of the aforementioned polyolefins with a difunctional reagent such 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 diacid, dianhydride, diepoxy, etc.
- copolymers mentioned above, (B1) and (B2) can be randomly or block copolymerized and have a linear or branched structure.
- MFI molecular weight
- density of these polyolefins can also vary to a large extent, which those skilled in the art will appreciate.
- MFI short for Melt Flow Index, is the Melt Flow Index. It is measured according to the ASTM 1238 standard.
- the non-functionalized polyolefins (B2) are chosen from polypropylene homopolymers or copolymers and any homopolymer of ethylene or copolymer of ethylene and a comonomer of the higher alpha olefinic type such as butene, hexene, octene or 4-methyl 1 -pentene. Mention may be made, for example, of PP, 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.
- the functionalized polyolefins (B1) are chosen from any polymer comprising alpha-olefin units and units carrying polar reactive functions such as epoxy, carboxylic acid or carboxylic acid anhydride functions.
- polymers mention may be made of ter-polymers of ethylene, alkyl acrylate and maleic anhydride or glycidyl methacrylate such as the Applicant's Lotader® or polyolefins grafted with maleic anhydride such as Orevac® from the company SK Chemicals as well as ter polymers of ethylene, alkyl acrylate and (meth)acrylic acid. Mention may also be made of homopolymers or copolymers polypropylene grafted with a carboxylic acid anhydride and then condensed with polyamides or monoamino polyamide oligomers.
- said constituent composition of said sealing layer(s) is devoid of polyether block amide (PEBA).
- PEBAs are therefore excluded from the polyolefins.
- 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 steps of mixing the various polymers and of converting 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) benzene sulfonamide (HP-BSA), hydroxybenzoic acid esters such as 2-ethylhexyl para-hydroxybenzoate (EHPB) and 2-decylhexyl para-hydroxybenzoate (HDPB), tetrahydrofurfuryl alcohol esters or ethers, such as oligoethyleneoxytetrahydrofurfurylalcohol, and citric acid or hydroxymalonic acid esters, such as oligoethyleneoxymalonate.
- BBSA n-butyl benzene sulfonamide
- ESA eth
- a preferred plasticizer is n-butyl benzene sulfonamide (BBSA).
- Another more particularly preferred plasticizer is N-(2-hydroxy-propyl)benzenesulfonamide (HP-BSA).
- HP-BSA N-(2-hydroxy-propyl)benzenesulfonamide
- said composition of said at least one innermost sealing layer comprises at least one polyolefin, in a proportion of 1% to less than 15% by weight, in particular from 1% to 12% by weight, in particular from 1% to 10% by weight, relative to the total weight of the composition.
- said composition is devoid of plasticizer.
- said composition of said at least one innermost sealing layer comprises at least one polyolefin, in a proportion of 1% to less than 15% by weight, in particular from 1% to 12% by weight, in particular from 1% to 10% by weight, relative to the total weight of the composition and said composition is devoid of plasticizer
- said composition of said at least one innermost sealing layer comprises at least one polyolefin, in a proportion of 1% to less than 15% by weight, in particular from 1% to 12% by weight, in particular from 1% to 10% by weight, relative to the total weight of the composition and from 0.1 to 1.5% by weight of plasticizer relative to the total weight of the composition.
- the polymer P2j can be a thermoplastic polymer or a thermosetting polymer.
- One or more layers of composite reinforcement may be present.
- the term “predominantly” means that said at least one polymer is present at more than 50% by weight relative to the total weight of the composition and of the matrix of the composite.
- 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, relative to the weight composition total,
- Said composition can also comprise impact modifiers and/or additives.
- the impact modifiers are advantageously made up of a polymer having a flexural modulus of less than 100 MPa measured according to the ISO 178 standard and a Tg of less than 0° C. (measured according to the 11357-2 standard at the level of the inflection bridge of the DSC thermogram ), in particular a polyolefin.
- the polyolefin is as defined above.
- the additives of said composition of the composite reinforcement layer can be chosen from an antioxidant, a heat stabilizer, a UV absorber, a light stabilizer, a lubricant, an inorganic filler, a flame retardant, a plasticizer and a dye, with the exception of a nucleating agent.
- said composition consists of said thermoplastic polymer P2j mainly, 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.
- each layer can be identical or different.
- a single majority polymer is present at least in the composite reinforcement layer and which does not adhere to the sealing layer.
- each reinforcement layer comprises the same type of polymer, in particular an epoxy or epoxy-based resin.
- Thermoplastic or thermoplastic polymer is understood to mean a material which is generally solid at ambient temperature, which may be semi-crystalline or amorphous, in particular semi-crystalline and which softens when the temperature rises, in particular after passing from its temperature of glass transition (Tg) and flows at a higher temperature when it is amorphous, or which can present a frank melting on passing its so-called melting temperature (Tf) when it is semi-crystalline, and which becomes solid again when 'a decrease in temperature below its crystallization temperature, Te, (for a semi-crystalline) and below its glass transition temperature (for an amorphous).
- 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 mass Mn of said thermoplastic polymer when it corresponds to a polyamide is preferably in a range going from 10,000 to 40,000, preferably from 10,000 to 30,000.
- Mn values can correspond to inherent viscosities greater than or equal to 0.8 as determined in 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)
- suitable semi-crystalline thermoplastic polymers in the present invention include: polyamides, in particular comprising an aromatic and/or cycloaliphatic structure, including copolymers, for example polyamide-polyether copolymers, polyesters, polyaryletherketones (PAEK ), polyetherether ketones (PEEK), polyetherketone ketones (PEKK), polyetherketoneetherketone ketones (PEKEKK), polyimides in particular polyetherimides (PEI) or polyamide-imides, polylsulfones (PSU) in particular polyarylsulfones such as polyphenyl sulfones (PPSU), polyether sulfones (PES).
- 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 (diamine in Ca) being chosen from aliphatic diamines, linear or branched, cycloaliphatic diamines and alkylaromatic diamines and the unit (diacid in Cb) being chosen from aliphatic diacids, linear or branched, 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/11 T, A being as defined above, in particular a polyamide chosen from a PA MPMDT/6T, PA11/10T, PA 5T/10T, PA 11/BACT, PA 11/6T/10T, PA MXDT/10T, PA MPMDT/10T, PA BACT/10T, PA BACT/6T, PA BACT/10T/6T, 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.
- PA MPMDT/6T PA11/10T, PA 5T/10T, PA 11/BACT, PA 11
- T stands for terephthalic acid
- MXD stands for m-xylylene diamine
- MPMD stands for methylpentamethylene diamine
- BAC stands for bis(aminomethyl)cyclohexane.
- Said semi-aromatic polyamides defined above have in particular a Tg greater than or equal to 80°C.
- stable in transformation means that the viscosity in the molten state does not evolve by more than 70% as a function of time, and precisely between 1 minute (time necessary to melt the product) and at least 30 minutes , in particular between 1 minute and 30 minutes.
- the melt viscosity of said composition of said innermost sealing layer is substantially constant for up to 20 minutes.
- substantially constant is meant that the viscosity in the molten state does not change in a proportion of more than 20% up to 20 minutes, between 1 minute and at least 5 minutes, in particular between 1 minute and 5 minutes.
- said composition also exhibits resistance to thermo-oxidation.
- resistance to thermo-oxidation is characterized by the half-life (in hours) of the materials. It corresponds to the time after which the ISO 527-2 1 BA specimens, aged in air at 140°C, lost half their initial elongation at break measured according to ISO 527-2 (2012).
- the resistance to thermoxidation is at least 80 days, in particular 100 days.
- said composition has a melt viscosity of approximately 13,000 to approximately 23,000 Pa.s, as determined by oscillatory rheology at 270° C. as defined above.
- the melt viscosity is determined by oscillatory rheology at 270°C at 10 rad/sec under nitrogen sweep with 5% strain and a shear of 10 sec-1 on a Physica MCR301 apparatus between two parallel planes of 25 mm in diameter.
- the inherent viscosity is determined according to ISO 307-2007 but in m-cresol instead of sulfuric acid, the temperature being 20°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 reinforcement 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 can be transparent to radiation suitable for welding.
- the winding of the composite reinforcement layer around the sealing layer is carried out in the absence of any subsequent welding.
- Said multilayer structure therefore comprises at least one sealing layer and at least one layer of composite reinforcement which is wound around the sealing 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. Nevertheless, said different polymers may be of the same type.
- one of the two composite waterproofing and reinforcement layers consists of a composition comprising an aliphatic polyamide
- the other layer consists of a composition comprising a polyamide which is not aliphatic and which is for example a semi-aromatic polyamide so as to have a high Tg polymer as the matrix of the composite reinforcement.
- Said multilayer structure can comprise up to 10 layers of sealing and up to 10 layers of composite reinforcement of different natures. It is obvious that said multilayer structure is not necessarily symmetrical and that it can therefore comprise more sealing layers than composite layers or vice versa, but there cannot be an alternation of layers and reinforcement layer.
- said multilayer structure comprises one, two, three, four, five, six, seven, eight, nine or ten sealing layers and one, two, three, four, five, six, seven, eight, nine or ten of composite reinforcement.
- said multilayer structure comprises one, two, three, four or five layers of sealing and one, two, three, four or five layers of composite reinforcement.
- said multilayer structure comprises one, two or three layers of sealing and one two or three layers of composite reinforcement.
- compositions which respectively comprise different polymers consist of compositions which respectively comprise different polymers.
- compositions which respectively comprise polyamides, in particular semi-crystalline polyamides, in particular aliphatic or aromatic, and an epoxy or epoxy-based resin P2j .
- said multilayer structure comprises a single sealing layer and several reinforcing layers, said adjacent reinforcing layer being wrapped around said sealing layer and the other reinforcing layers being wrapped around the reinforcing layer directly adjacent.
- said multilayer structure comprises a single reinforcing layer and several sealing layers, said reinforcing layer being wrapped around said adjacent sealing layer.
- said multilayer structure comprises a single sealing layer and a single composite reinforcement layer, said reinforcement layer being wrapped around said sealing layer.
- each sealing layer consists of a composition comprising the same type of polyamide, in particular a semi-crystalline, in particular aliphatic, in particular long-chain or semi-aromatic, in particular long-chain polyamide. chain.
- polyamide which can be an identical or different polyamide according to the layers.
- said polyamide is a semi-crystalline, in particular aliphatic, in particular long-chain, polyamide or a semi-aromatic, in particular long-chain, polyamide and said polymer P2j is an epoxy or epoxy-based resin.
- said polyamide is a semi-crystalline polyamide, in particular aliphatic, in particular long-chain, and said polymer P2j is an epoxy or epoxy-based resin.
- said polyamide is a semi-aromatic polyamide, in particular with a long chain, and said polymer P2j is an epoxy or epoxy-based resin.
- said polyamide is identical for all the sealing layers.
- said semi-crystalline polyamide is a long-chain aliphatic polyamide, in particular PA1010, PA 1012, PA 1212, PA11, PA12, in particular PA11 or PA12.
- the polyamide is a long-chain semi-aromatic polyamide, in particular PA 11/5T, PA 11/6T or PA 11/1 OT.
- the Amino 11 level in the copolyamide must be chosen judiciously so that the Tm of said polymers is less than 280°C, preferably 266°C.
- each reinforcing layer consists of a composition comprising the same type of polymer P2j, in particular an epoxy or epoxy-based resin.
- each sealing layer consists of a composition comprising the same type of polyamide, in particular a semi-crystalline polyamide and each reinforcing layer consists of a composition comprising the same type of polymer P2j , in particular an epoxy or epoxy-based resin.
- said polyamide is a long-chain aliphatic semi-crystalline polyamide, in particular PA1010, PA 1012, PA 1212, PA11, PA12, in particular PA 11 or PA12 and said polymer P2j is a semi-aromatic semi-crystalline polyamide, in particular chosen from a PA MPMDT/6T, a PA1 1/1 OT, a PA 1 1/BACT, a PA 5T/10T, a PA 1 1/6T/10T, a PA MXDT/10T, a PA MPMDT/10T, one PA BACT/1 OT, one PA BACT/6T, PA BACT/10T/6T, one PA 11/BACT/6T, PA 1 1/MPMDT/6T, PA 1 1/MPMDT/10T, PA 1 1/ BACT/ 1 OT, an AP and 1 1/MXDT/1 OT.
- PA MPMDT/6T a semi-aromatic semi-crystalline polyamide
- said multilayer structure consists of a single reinforcing layer and a single sealing layer in which said polyamide is a long-chain aliphatic semi-crystalline polyamide, in particular PA1010, PA 1012, PA 1212, PA11, PA12, in particular PA 11 or PA12 and said polymer P2j is a semi-aromatic polyamide, in particular chosen from a PA MPMDT/6T, a PA1 1/1 OT, a PA 1 1/BACT, a PA 5T/ 10T, a PA 1 1/6T/10T, a PA MXDT/10T, a PA MPMDT/10T, a PA BACT/1 OT, a PA BACT/6T, PA BACT/10T/6T, PA 1 1/BACT/6T, PA 11/MPMDT/6T, PA 11/MPMDT/1 OT,
- PA 11/ BACT/10T and a PA 1 1/MXDT/10T PA 11/ BACT/10T and a PA 1 1/MXDT/10T.
- the multilayer structure consists of a single reinforcing layer and a single sealing layer in which said polymer P1 i is a long-chain aliphatic semi-crystalline polyamide, in particular PA1010 , PA 1012, PA 1212, PA1 1 , PA12, or semi-crystalline semi-aromatic, in particular chosen from polyamide 1 1/5T or 1 1/6T or 1 1/1 OT, MXDT/10T, MPMDT /10T and BACT/10T, in particular PA 11 or PA12 and said polymer P2j is an epoxy or epoxy-based resin.
- said polymer P1 i is a long-chain aliphatic semi-crystalline polyamide, in particular PA1010 , PA 1012, PA 1212, PA1 1 , PA12, or semi-crystalline semi-aromatic, in particular chosen from polyamide 1 1/5T or 1 1/6T or 1 1/1 OT, MXDT/10T, MPMDT /10T and BACT/10T, in particular PA 11 or PA12 and said polymer P2j
- said multilayer structure further comprises at least one outer layer consisting of a fibrous material of continuous fiberglass impregnated with a transparent amorphous polymer, said layer being the outermost layer of said multilayer structure.
- Said outer layer is a second reinforcement but transparent layer which makes it possible to put an inscription on the structure.
- these fibers forming said fibrous material are in particular fibers of mineral, organic or plant origin.
- said fibrous material can be sized or not sized.
- Said fibrous material may therefore comprise up to 3.5% by weight of a material of organic nature (thermosetting or thermoplastic resin type) called size.
- 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 higher than the Tg of the polymer or mixture of thermoplastic polymer constituting the pre-impregnation matrix when the latter is amorphous, or higher than the Tm polymer or mixture of thermoplastic polymer constituting the pre-impregnation matrix when the latter is semi-crystalline.
- they are based on a semi-crystalline thermoplastic polymer and have a melting point Tf higher than the Tg of the polymer or thermoplastic polymer mixture constituting the pre-impregnation matrix when the latter is amorphous, or higher than the Tm polymer or mixture of thermoplastic polymer constituting the pre-impregnation matrix when the latter is semi-crystalline.
- the organic fibers of constitution fibrous material during impregnation by the thermoplastic matrix of the final composite.
- the fibers of plant origin mention may be made of natural fibers based on flax, hemp, lignin, bamboo, sisal, and other cellulosic fibers, in particular viscose. These fibers of plant origin can be used pure, treated or even coated with a coating layer, in order to facilitate adhesion and impregnation of the thermoplastic polymer matrix.
- the fibrous material can also be a fabric, braided or woven with fibers.
- building fibers can be used alone or in mixtures.
- organic fibers can be mixed with mineral fibers to be pre-impregnated with thermoplastic polymer powder and form the pre-impregnated fibrous material.
- Organic fiber rovings can have several grammages. They may also have several geometries.
- the fibers making up the fibrous material may also be in the form of a mixture of these reinforcing fibers of different geometries.
- the fibers are continuous fibers.
- the fibrous material is chosen from glass fibres, carbon fibres, basalt or basalt-based fibres, or a mixture of these, in particular carbon fibres.
- It is used in the form of a wick or several wicks.
- the present invention relates to a method for 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 or by half-shell injection.
- said method of manufacturing a multilayer structure comprises a step of filament winding of the reinforcement layer as defined above around the sealing layer as defined above.
- the tanks are obtained by rotational molding of the sealing layer (liner) at a temperature adapted to the nature of the thermoplastic resin used.
- the polyamide used is Rilsan®PA11 (BESNO marketed by the company Arkema), the thermal stabilizer is ANOX® NDB TL89: organic stabilizer of the phenol phosphite type marketed by the company Chemtura.
- the carbodiimide used is Stabiliser® 9000 (Poly-(1,3,5-triisopropylphenylene-2,4-carbodiimide) marketed by the company Raschig.
- the catalyst used is H3PO3 or H3PO4.
- BBSA n-butyl benzene sulfonamide marketed by the company PROVIRON
- EXXELOR VA 1801 polyolefin (copolymer of ethylene - propylene functionalized maleic anhydride) marketed by Exxon.
- Example 1 Evaluation of the compositions of the invention: Viscosity in the molten state and Thermal resistance at 140°C.
- the proportions indicated are percentages by weight relative to the total weight of the composition.
- Example 2 Comparison of the properties of the compositions according to the invention with the comparative composition 1
- Liners in PA1 1 with the comparative composition 1 and comparative 2 and the compositions of the invention 1 and 2 were prepared by rotational molding.
- the permeability to hydrogen is determined according to the following protocol: it consists of sweeping the upper face of the film with the test gas (Hydrogen) and measuring by gas phase chromatography the flux which diffuses through the film in the part lower, swept by the carrier gas: Nitrogen
- the cold resistance of PA11 liners without plasticizer or with 1.5% plasticizer is superior to those of PA11 liner with 6% plasticizer or 12% plasticizer.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US18/246,743 US20230356514A1 (en) | 2020-10-01 | 2021-09-28 | Multi-layer structure for storing hydrogen |
MX2023003270A MX2023003270A (es) | 2020-10-01 | 2021-09-28 | Estructura de multiples capas para almacenamiento de hidrogeno. |
JP2023520125A JP2023543906A (ja) | 2020-10-01 | 2021-09-28 | 水素を貯蔵するための多層構造 |
KR1020237014070A KR20230079128A (ko) | 2020-10-01 | 2021-09-28 | 수소를 저장하기 위한 다층 구조물 |
CA3192554A CA3192554A1 (fr) | 2020-10-01 | 2021-09-28 | Structure multicouche pour le stockage de l'hydrogene |
CN202180067980.5A CN116406326A (zh) | 2020-10-01 | 2021-09-28 | 用于储氢的多层结构体 |
EP21798078.8A EP4221975A1 (fr) | 2020-10-01 | 2021-09-28 | Structure multicouche pour le stockage de l'hydrogene |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR2010031 | 2020-10-01 | ||
FR2010031A FR3114768B1 (fr) | 2020-10-01 | 2020-10-01 | Structure multicouche pour le transport ou le stockage de l’hydrogene |
Publications (1)
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WO2022069826A1 true WO2022069826A1 (fr) | 2022-04-07 |
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PCT/FR2021/051665 WO2022069826A1 (fr) | 2020-10-01 | 2021-09-28 | Structure multicouche pour le stockage de l'hydrogene |
Country Status (9)
Country | Link |
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US (1) | US20230356514A1 (fr) |
EP (1) | EP4221975A1 (fr) |
JP (1) | JP2023543906A (fr) |
KR (1) | KR20230079128A (fr) |
CN (1) | CN116406326A (fr) |
CA (1) | CA3192554A1 (fr) |
FR (1) | FR3114768B1 (fr) |
MX (1) | MX2023003270A (fr) |
WO (1) | WO2022069826A1 (fr) |
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US5360888A (en) | 1992-04-30 | 1994-11-01 | Rhein Chemie Rheinau Gmbh | Hydrolysis-stable polyamides |
EP1505099A2 (fr) | 2003-08-05 | 2005-02-09 | Arkema | Polymides semi aromatiques souples à faible reprise en humidité |
GB2489610A (en) * | 2011-04-01 | 2012-10-03 | Dynetek Ind Ltd | Multilayer liner for a high-pressure gas cylinder |
FR3027907A1 (fr) * | 2014-11-05 | 2016-05-06 | Arkema France | Composition a base de polymere thermoplastique visqueuse et stable a la transformation, sa preparation et ses utilisations |
EP3112421A1 (fr) * | 2015-02-27 | 2017-01-04 | Toray Industries, Inc. | Composition de résine polyamide pour article moulé destiné à être en contact avec de l'hydrogène haute pression, et article moulé obtenu à partir de celle-ci |
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WO2018155491A1 (fr) | 2017-02-24 | 2018-08-30 | 株式会社ブリヂストン | Élément de transport d'hydrogène |
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US5534594A (en) | 1994-12-05 | 1996-07-09 | Rohm And Haas Company | Preparation of butadiene-based impact modifiers |
WO2006057777A1 (fr) | 2004-11-22 | 2006-06-01 | Arkema Inc. | Composition de resine thermoplastique rendue antichoc |
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2020
- 2020-10-01 FR FR2010031A patent/FR3114768B1/fr active Active
-
2021
- 2021-09-28 CA CA3192554A patent/CA3192554A1/fr active Pending
- 2021-09-28 MX MX2023003270A patent/MX2023003270A/es unknown
- 2021-09-28 KR KR1020237014070A patent/KR20230079128A/ko unknown
- 2021-09-28 EP EP21798078.8A patent/EP4221975A1/fr active Pending
- 2021-09-28 JP JP2023520125A patent/JP2023543906A/ja active Pending
- 2021-09-28 WO PCT/FR2021/051665 patent/WO2022069826A1/fr unknown
- 2021-09-28 US US18/246,743 patent/US20230356514A1/en active Pending
- 2021-09-28 CN CN202180067980.5A patent/CN116406326A/zh active Pending
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EP3112421A1 (fr) * | 2015-02-27 | 2017-01-04 | Toray Industries, Inc. | Composition de résine polyamide pour article moulé destiné à être en contact avec de l'hydrogène haute pression, et article moulé obtenu à partir de celle-ci |
EP3309438A1 (fr) * | 2015-06-09 | 2018-04-18 | The Yokohama Rubber Co., Ltd. | Tuyau de dstribution d'hydrogène |
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Also Published As
Publication number | Publication date |
---|---|
CN116406326A (zh) | 2023-07-07 |
CA3192554A1 (fr) | 2022-04-07 |
MX2023003270A (es) | 2023-04-12 |
US20230356514A1 (en) | 2023-11-09 |
FR3114768A1 (fr) | 2022-04-08 |
JP2023543906A (ja) | 2023-10-18 |
KR20230079128A (ko) | 2023-06-05 |
FR3114768B1 (fr) | 2023-09-29 |
EP4221975A1 (fr) | 2023-08-09 |
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