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
  • F16L11/00—Hoses, i.e. flexible pipes
  • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
• • 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
  • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
  • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber 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
  • B32B27/06—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
  • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
  • B32B27/286—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysulphones; polysulfides
• • 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
  • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (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
  • B32B27/30—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
  • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (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
• • 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
• • 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
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/02—Physical, chemical or physicochemical properties
  • B32B7/027—Thermal properties
• • 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
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
• • 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
  • B32B2250/00—Layers arrangement
  • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
• • 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
  • B32B2270/00—Resin or rubber layer containing a blend of at least two different 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
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/30—Properties of the layers or laminate having particular thermal properties
  • B32B2307/304—Insulating
• • 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
  • B32B2307/554—Wear resistance
• • 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
  • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
• • 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
  • B32B2307/732—Dimensional properties
• • 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
  • B32B2323/00—Polyalkenes
  • B32B2323/04—Polyethylene
  • B32B2323/043—HDPE, i.e. high density polyethylene
• • 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
  • B32B2457/00—Electrical equipment
  • B32B2457/10—Batteries
• • 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
  • B32B2457/00—Electrical equipment
  • B32B2457/18—Fuel cells
• • 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
• • 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
  • B32B2605/00—Vehicles
  • B32B2605/08—Cars
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/30—Hydrogen technology
  • Y02E60/50—Fuel cells

Definitions

• the present invention relates to a single-layer or multi-layer tubular structure for transporting a cooling liquid, said tube being intended for fuel cell cooling.
• the fuel cell is an electrochemical energy generator allowing the direct transformation of the chemical energy of a fuel (hydrogen for example) into electrical energy. Thermal control of this battery is important to guarantee good performance and a good lifespan. The most efficient and economical system remains heat exchange by fluid.
• the heat transfer fluid will circulate within the cells.
• the fluid must therefore be dielectric so as not to disrupt the performance of the battery or even deteriorate it.
• the fluid must also not contain chemical elements (oligomer, additives) which could pollute the cells.
• the tubular structure which will transport the fuel cell coolant must not alter said coolant, in particular its dielectric conductivity. It must also not release oligomers and/or ions into said cooling liquid and it must have very good resistance to contact with the heat transfer fluid.
• Patent US2019/0285203A1 describes a five-layer tubular structure and in particular HDPE/binder/PA6/binder/HDPE as a cooling pipe for a motor vehicle.
• TPV thermoplastic vulcanizate
• Application US2007148388A1 describes engine coolant pipes containing at least two layers: an outer layer consisting of a mass of polyamide and an inner layer consisting of a mass of polypropylene, which contains at least 50% by weight of polypropylene, the polypropylene being a multi-phase copolymer of propene and ethene.
• EP 3670172A1 describes a multilayer pipe comprising at least one inner layer made of polypropylene (PP) and at least one outer layer made of polyphthalamide (PPA).
• PP polypropylene
• PPA polyphthalamide
• a single-layer or multi-layer tubular structure for transporting a cooling liquid having a dielectric conductivity of less than 30 pS/cm and comprising at least one internal layer (I) comprising at least one polymer thermoplastic as defined above allowed the cooling of fuel cells while avoiding the release of oligomers and/or ions into said cooling liquid.
• tubular structure and the terms “tube” or “pipe” have the same meaning and can be used in place of each other.
• Said coolant is any heat transfer liquid, in particular a coolant based on water and additives.
• glycol water in particular based on water with propylene glycol or ethylene glycol.
• Electrical or dielectric conductivity expressed in micro siemens per centimeter characterizes the ability of a material or a solution to let electrical charges move freely and therefore allow the passage of an electric current. It is measured on the cooling liquid with magnetic stirring at room temperature after aging for 168 hours at 80°C of said single-layer or multilayer tubular structure in contact with said cooling liquid by means of a calibrated conductivity meter with automatic temperature compensation ( HORIBA LAQUA-EC220K model equipped with a HORIBA 35523G0E0042 probe).
• thermoplastic polymer of the inner layer (I) Regarding the thermoplastic polymer of the inner layer (I)
• TPV thermoplastic vulcanizate
• FPS fluoropolymer
• PPS polyphenylene sulfide
• PPA polyphthalamide
• the internal layer (I) consists essentially of polyolefin, thermoplastic vulcanizate (TPV), fluoropolymer, polyphenylene sulfide (PPS) or polyphthalamide (PPA).
• TPV thermoplastic vulcanizate
• fluoropolymer fluoropolymer
• PPS polyphenylene sulfide
• PPA polyphthalamide
• the internal layer (I) may in particular also include additives or conventional additives in addition to said thermoplastic.
• additives mention may be made in particular of those chosen from a catalyst, an antioxidant, a thermal stabilizer, a UV stabilizer, a light stabilizer, a lubricant, a filler, a plasticizer, a flame retardant, a nucleating agent, a colorant, an electrical conductive agent, a thermal conductive agent, an impact modifier or a mixture thereof.
• the inner layer suitably consists of at least 90% by weight, preferably at least 92% by weight, more preferably at least 95% by weight and most preferably at least 98% by weight of polyolefin, thermoplastic vulcanizate (TPV), fluoropolymer, polyphenylene sulfide (PPS) or polyphthalamide (PPA).
• TPV thermoplastic vulcanizate
• PPS polyphenylene sulfide
• PPA polyphthalamide
• thermoplastic polymer of the internal layer (I) is a polyolefin chosen from functionalized, non-functionalized polyolefins and a mixture of the two.
• polyolefin has been designated by (B) and functionalized polyolefins (Bl) 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, 1-butene, 1-octene, butadiene.
• alpha olefins or diolefins such as for example ethylene, propylene, 1-butene, 1-octene, butadiene.
• LDPE low density polyethylene
• HDPE high density polyethylene
• LLDPE linear low density polyethylene, or linear low density polyethylene
• VLDPE very low density polyethylene, or very low density polyethylene
• metallocene polyethylene metallocene polyethylene
• ethylene/alpha-olefin copolymers such as ethylene/propylene, EPR (abbreviation of ethylene-propylene-rubber) and ethylene/propylene/diene (EPDM),
• EPR abbreviation of ethylene-propylene-rubber
• EPDM ethylene/propylene/diene
• the functionalized polyolefin (Bl) may be a polymer of alpha olefins having reactive units (the functionalities); such reactive units are acid, anhydride, or epoxy functions.
• the functionalities are acid, anhydride, or epoxy functions.
• 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 grafting rate for example of 0.01 to 5% by weight.
• the functionalized polyolefin (Bl) can be chosen from the following (co)polymers, grafted with maleic anhydride or glycidyl methacrylate, in which the grafting rate is for example 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 block copolymers
• SBS styrene/butadiene/styrene
• SIS styrene/isoprene/styrene
• SEPS styrene/ethylene-propylene/styrene
• EVA vinyl acetate copolymers
• alkyl (meth)acrylate copolymers containing up to 40% by weight of alkyl (meth)acrylate;
• the functionalized polyolefin (Bl) can also be chosen from ethylene/propylene copolymers with a majority of propylene grafted with maleic anhydride then condensed with monoamine polyamide (or a polyamide oligomer) (products described in EP-A-0342066) .
• the functionalized polyolefin (Bl) can also be a co- or ter polymer of at least the following units: (1) ethylene, (2) alkyl (meth)acrylate or vinyl ester of saturated carboxylic acid and (3) anhydride such as maleic anhydride or (meth)acrylic or epoxy acid such as glycidyl (meth)acrylate.
• ethylene preferably represents at least 60% by weight and where the ter monomer (the function) represents for example from 0.1 to 10% by weight of the copolymer:
• the (meth)acrylic acid can be salified with Zn or Li.
• (meth)alkyl acrylate designates C1 to C8 alkyl methacrylates and acrylates, and can be chosen from methyl acrylate, ethyl acrylate , n-butyl acrylate, iso-butyl acrylate, ethyl-2-hexyl acrylate, cyclohexyl acrylate, methyl methacrylate and ethyl methacrylate.
• the aforementioned polyolefins (Bl) 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, (Bl) and (B2) can be copolymerized randomly or block-wise and have a linear or branched structure.
• MFI melt flow index
• the non-functionalized polyolefins (B2) are chosen from homopolymers or copolymers of polypropylene and any homopolymer of ethylene or copolymer of ethylene and a higher alpha olefin type comonomer such as butene, hexene, octene or 4-methyl 1-Pentene.
• PP high density PE
• medium density PE linear low density PE
• low density PE very low density PE.
• These polyethylenes are known by 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 “metlocene” catalysis.
• the functionalized polyolefins (Bl) are chosen from any polymer comprising alpha olefinic 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 Lotader® (SK functional polymer) or polyolefins grafted by maleic anhydride such as Orevac® (SK functional polymer) as well as ter polymers of ethylene, alkyl acrylate and (meth)acrylic acid.
• SK functional polymer polyolefins grafted by maleic anhydride
• Orevac® SK functional polymer
• the polyolefin is non-functionalized.
• the non-functionalized polyolefin is chosen from a polyethylene and a polypropylene, in particular a polyethylene, in particular a high density polyethylene (HDPE).
• a polyethylene in particular a high density polyethylene (HDPE).
• HDPE high density polyethylene
• thermoplastic polymer of the internal layer (I) is a thermoplastic vulcanizate (TPV).
• Thermoplastic vulcanizate is a mechanical mixture of an olefinic thermoplastic polymer with a polyethylene or polypropylene matrix, in particular with a polypropylene matrix, and a vulcanized elastomer such as a vulcanized PP/EPDM (ethylene propylene diene monomer) mixture.
• TPV Thermoplastic vulcanizate
• thermoplastic polymer of the internal layer (I) is a fluoropolymer.
• Fluorinated polymer is a polymer whose repeating unit is a fluorocarbon.
• E ethylene
• P propylene
• VDF vinylidene fluoride
• TFE tetrafluoroethylene
• HFP hexafluoropropylene
• PPVE perfluoropropylvinyl ether
• PMVE perfluoromethyl vinyl ether
• CTFE chlorotrifluoroethylene
• the fluoropolymer is chosen from poly(vinylidene fluoride) (PVDF), polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), ethylene tetrafluoroethylene (ETFE), a terpolymer of tetrafluoroethylene, ethylene, and hexafluoropropylene (EFEP), a copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether, and mixtures thereof, including ethylene tetrafluoroethylene (ETFE).
• PVDF poly(vinylidene fluoride)
• PTFE polytetrafluoroethylene
• PCTFE polychlorotrifluoroethylene
• EFE ethylene tetrafluoroethylene
• EEP ethylene tetrafluoroethylene
• EEP ethylene tetrafluoroethylene
• thermoplastic polymer of the internal layer (I) is a polyphenylene sulfide (PPS).
• Polyphenylene sulfide is a thermostable semi-crystalline polymer.
• thermoplastic polymer of the internal layer (I) is a polyphthalamide (PPA).
• the polyphthalamide may be a homopolyamide or a copolyamide.
• XAr designates a unit obtained from the polycondensation of a diamine
• the diamine can be linear or branched.
• it is linear.
• Said at least one C6-C36 diamine 1,11-undecamethylenediamine, 1,12-dodecamethylediamine, 1,13-tridecamethylenediamine, 1,14-tetradecamethylenediamine, 1,16-hexadecamethylenediamine and 1,18-octadecamethylenediamine, octadecenediamine, eicosanediamine, docosanediamine and diamines obtained from fatty acids.
• said at least one diamine 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine, 1,13-tridecamethylenediamine, 1,14-tetradecamethylenediamine, 1,16-hexadecamethylenediamine and 1,18-octadecamethylenediamine.
• said at least one diamine decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine.
• said at least one diamine decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine.
• the diamine being advantageously chosen from terephthalic acid (noted T), isophthalic acid (noted I) and 2,6 naphthalene dicarboxylic acid (noted N) or their mixtures, in particular it is chosen from terephthalic acid (noted T), isophthalic acid (noted I) or their mixtures.
• MXDY designates a unit obtained from the polycondensation of the diamine metaxylylene diamine (MXD) and at least one aliphatic dicarboxylic acid Y.
• Said at least one dicarboxylic acid Y in C6 to C36 may be chosen from adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, and diacids obtained from fatty acids.
• the diacid can be linear or branched. Advantageously, it is linear.
• said at least one dicarboxylic acid Y is C6 to C18 and is chosen from adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid.
• said at least one dicarboxylic acid Y is C6 to C12 and is chosen from adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid.
• said at least one dicarboxylic acid Y is CIO to C12 and is chosen from sebacic acid, undecanedioic acid, dodecanedioic acid.
• said aliphatic semi-crystalline polyamide is obtained from the polycondensation of at least one diamine
• said aliphatic semi-crystalline polyamide is obtained from the polycondensation of a single diamine X with a single dicarboxylic acid Y.
• polyphthalamide is chosen from PA5T, PA6T, PA9T, PA10T, PA11T, PA12T, MXD6, MXD10, MXD12.
• the C9 diamine comprises a diamine unit, containing 60 mole % or more of a 1,9-nonanediamine unit and/or a 2-methyl-1,8-octanediamine unit relative to all diamine units at C9.
• (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 motif (Ca diamine) being chosen from aliphatic, linear or branched diamines, cycloaliphatic diamines and alkylaromatic diamines and the motif (Cb diacid) being chosen from linear or branched aliphatic diacids, cycloaliphatic diacids and aromatic diacids ;
• X.T designates 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, and 18, in particular a polyamide of formula A/5T, A/6T, A/9T, A/10T, A/11T or A/12T, A being as defined above, in particular a polyamide chosen from a PA 5T /10T, a PA11/10T, a PA MPMDT/6T, a PA MXDT/6T, a PA MXDT/10T, a PA MPMDT/10T, a PA BACT/6T, a PA BACT/10T, a PA 11/BACT, a PA 11/6T/10T, PA BACT/10T/6T, a PA 11/BACT/6T, PA 11/MPMDT/6T, PA 11/MPMDT/10T, PA 11/BACT/10T, a PA 11/MXDT/ 6T, one PA 11/MXDT/10T, one 11/5T
• T is terephthalic acid
• MXD is m-xylylene diamine
• MPMD is methylpentamethylene diamine
• BAC is bis(aminomethyl)cyclohexane.
• thermoplastic polymer of the internal layer (I) is a polyphthalamide (PPA) chosen from PA9T, PA6T, PA11/10T, PA12/10T, PA11/12T, PA 12/12T, PA610/10T, PA612/10T , PA1010/10T, PA1012/10T, PA1212/10T, PA610/12T, PA612/12T, PA1010/12T, PA 1012/12T and the PA1212/12T, in particular the PA11/10T and the PA11/12T.
• PPA polyphthalamide
• Tubular structure of the invention can be single-layer or multi-layer and it is used for transporting a cooling liquid, and said tube being intended for fuel cell cooling.
• single-layer or multi-layer it comprises at least one layer (I) which comprises at least one thermoplastic polymer chosen from a polyolefin, a thermoplastic vulcanizate (TPV), a fluoropolymer, a polyphenylene sulfide (PPS) and a polyphthalamide (PPA), and said coolant having a dielectric conductivity less than 30 pS/cm, as determined after aging for 168 hours at 80°C of said single-layer or multilayer tubular structure in contact with said coolant.
• TPV thermoplastic vulcanizate
• PPS polyphenylene sulfide
• PPA polyphthalamide
• it comprises at least one layer (I) which comprises at least one thermoplastic polymer chosen from a non-functionalized polyolefin, a thermoplastic vulcanizate (TPV), a fluoropolymer, a polyphenylene sulfide (PPS) and a polyphthalamide (PPA), and said coolant having a dielectric conductivity less than 30 pS/cm, as determined after aging for 168 hours at 80°C of said single-layer or multilayer tubular structure in contact with said coolant.
• TPV thermoplastic vulcanizate
• PPS polyphenylene sulfide
• PPA polyphthalamide
• it comprises at least one layer (I) which comprises at least one thermoplastic polymer chosen from a non-functionalized polyolefin, a thermoplastic vulcanizate (TPV), a fluoropolymer chosen from ETFE, a polyphenylene sulfide ( PPS) and a polyphthalamide (PPA), and said cooling liquid having a dielectric conductivity less than 30 pS/cm, as determined after aging for 168 hours at 80°C of said monolayer or multilayer tubular structure in contact with said cooling liquid. cooling.
• TPV thermoplastic vulcanizate
• ETFE a fluoropolymer chosen from ETFE
• PPS polyphenylene sulfide
• PPA polyphthalamide
• it comprises at least one layer (I) which comprises at least one thermoplastic polymer chosen from a non-functionalized polyolefin, a thermoplastic vulcanizate (TPV), a polyphenylene sulfide (PPS) and a polyphthalamide (PPA) , and said cooling liquid having a dielectric conductivity less than 30 pS/cm, as determined after aging for 168 hours at 80°C of said single-layer or multilayer tubular structure in contact with said cooling liquid.
• TPV thermoplastic vulcanizate
• PPS polyphenylene sulfide
• PPA polyphthalamide
• said structure is single-layer and layer (I) is therefore in contact with the cooling liquid.
• said structure is multilayer and layer (I) is therefore the internal layer which is in contact with the cooling liquid.
• said structure is multilayer and it comprises an external layer (II) comprising at least one thermoplastic polymer, in particular a polyamide.
• said structure is multilayer and it comprises an external layer (II) consisting of at least one thermoplastic polymer, in particular a polyamide.
• said structure is two-layer and is therefore made up of layers (ll)//(l) from the outside towards the inside.
• said internal layer (I) consists of at least said one thermoplastic polymer chosen from a polyolefin, a thermoplastic vulcanizate (TPV), a fluoropolymer, a polyphenylene sulfide (PPS) and a polyphthalamide (PPA).
• TPV thermoplastic vulcanizate
• PPS polyphenylene sulfide
• PPA polyphthalamide
• said outer layer (II) consists of at least said one thermoplastic polymer, in particular a polyamide.
• said internal layer (I) consists of at least said one thermoplastic polymer chosen from a polyolefin, a thermoplastic vulcanizate (TPV), a fluoropolymer, a polyphenylene sulfide (PPS) and a polyphthalamide (PPA) and said layer external (II) consists of at least said one thermoplastic polymer, in particular a polyamide.
• TPV thermoplastic vulcanizate
• PPS polyphenylene sulfide
• PPA polyphthalamide
• the outer layer (II) may in particular also include additives or conventional additives in addition to said thermoplastic.
• additives mention may in particular be made of those chosen from a catalyst, an antioxidant, a heat stabilizer, a UV stabilizer, a light stabilizer, a lubricant, a filler, a plasticizer, a flame retardant, a nucleating agent, a dye. , an electrical conductive agent, a thermal conductive agent, an impact modifier or a mixture thereof.
• the outer layer (II) suitably consists of at least 90% by weight, preferably at least 92% by weight, more preferably at least 95% by weight and most preferably at least 98%. by weight of thermoplastic polymer, in particular a polyamide.
• said tubular structure releases a quantity of ions into said cooling liquid less than or equal to 700 mg/kg of ions, more particularly less than or equal to 500 mg/kg, in particular less than or equal to 300 mg/kg, in particular less than or equal to 100 mg/kg, the quantity of ions released being determined on a single-layer tube of 8x1 mm2 by inductively coupled plasma mass spectrometry (ICP-MS) or by ion chromatography comprising said liquid cooling.
• ICP-MS inductively coupled plasma mass spectrometry
• the polyamide (PA) may be a homopolyamide or a copolyamide or a mixture thereof.
• the polyamide is chosen from semi-crystalline aliphatic polyamides, cycloaliphatic polyamides, and semi-aromatic polyamides (polyphthalamides or PPA).
• the polyamide of layer (II) is chosen from a semi-crystalline aliphatic polyamide having an average number of carbon atoms per nitrogen atom of C4 to C15 and a semi-aromatic polyamide (PPA).
• PPA semi-aromatic polyamide
• semi-crystalline polyamide means a material that is generally solid at room temperature, and which softens upon an increase in temperature, in particular after passing its glass transition temperature (Tg), and which may present a clear melting upon passage. 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 mass Mn of said semi-crystalline polyamide is preferably in a range going from 10,000 to 85,000, in particular from 10,000 to 60,000, preferably from 10,000 to 50,000, even more preferably from 12,000 to 50,000.
• Mn values can correspond at inherent viscosities greater than or equal to 0.8 as determined in m-cresol according to standard ISO 307:2007 but by changing the solvent (use of m-cresol in place of sulfuric acid and the temperature being 20°C).
• polyamide includes both homopolyamides and copolyamides.
• Said at least one aliphatic semi-crystalline polyamide is obtained from the polycondensation of at least one lactam, or from the polycondensation of at least one amino acid, or from the polycondensation of at least one diamine at least one dicarboxylic acid Y or mixtures thereof.
• said at least one lactam can be chosen from a C8 to C18 lactam, preferably CIO to C18, more preferably CIO at C12.
• a C8 to C18 lactam includes decanolactam, undecanolactam, and lauryllactam.
• said at least one aliphatic semi-crystalline polyamide is obtained from the polycondensation of at least one lactam, it can therefore comprise a single lactam or several lactams.
• said at least one aliphatic semi-crystalline polyamide is obtained from the polycondensation of a single lactam and said lactam is chosen from lauryllactam and undecanolactam, advantageously lauryllactam.
• said at least one amino acid can be chosen from a C8 to C18 amino acid, preferably CIO to C18, more preferably CIO at C12.
• a C8 to C18 amino acid is in particular 9-aminononanoic acid, 10-aminodecanoic acid, 10-aminoundecanoic acid, 12-aminododecanoic acid and 11-aminoundecanoic acid as well as its derivatives, in particular the acid N-heptyl-ll-aminoundecanoic.
• said at least one aliphatic semi-crystalline polyamide is obtained from the polycondensation of at least one amino acid, it can therefore comprise a single amino acid or several amino acids.
• said aliphatic semi-crystalline polyamide is obtained from the polycondensation of a single amino acid and said amino acid is chosen from 10-aminodecanoic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid, advantageously 11-aminoundecanoic acid.
• the polyamide of layer (II) is chosen from a semi-crystalline aliphatic polyamide having an average number of carbon atoms per nitrogen atom of C4 to C15 and a semi-aromatic polyamide (PPA) .
• polyamide of layer (II) is a semi-crystalline aliphatic polyamide which has an average number of carbon atoms per nitrogen atom from C8 to C15, in particular from C9 to C15, in particular from CIO to 15.
• the semi-crystalline aliphatic polyamide of layer (II) is chosen from PA610, PA612, PA614, PA618, PA1010, PA1012, PA1014, PA1018, PA1210, PA1212, PA1214, PA1218, PAU and PA12, in particular PA612, PA614, PA618, PA1010, PA1012, PA1014, PA1018, PA1210, PA1212, PA1214, PA1218, PAU and PA12, in particular PA614, PA618, PA1010, PA1012, PA1014, PA1018, PA1210, PA1212, PA1214, PA1218, PAU and PA12.
• the semi-crystalline aliphatic polyamide of layer (II) is chosen from PAU and PA12.
• said structure is multilayer and it comprises an outer layer (II) comprising at least one thermoplastic polymer, in particular a polyamide and a binder layer (III) located between said inner layer (I ) and said outer layer (II).
• an outer layer (II) comprising at least one thermoplastic polymer, in particular a polyamide and a binder layer (III) located between said inner layer (I ) and said outer layer (II).
• said structure is three-layer and is therefore made up of layers (I l)//binder//(l) from the outside towards the inside.
• said internal layer (I) consists of at least said one thermoplastic polymer chosen from a polyolefin, a thermoplastic vulcanizate (TPV), a fluoropolymer, a polyphenylene sulfide (PPS) and a polyphthalamide (PPA).
• said outer layer (II) consists of at least said one thermoplastic polymer, in particular a polyamide.
• said internal layer (I) consists of at least said one thermoplastic polymer chosen from a polyolefin, a thermoplastic vulcanizate (TPV), a fluoropolymer, a polyphenylene sulfide (PPS) and a polyphthalamide (PPA) and said layer external (II) consists of at least said one thermoplastic polymer, in particular a polyamide.
• TPV thermoplastic vulcanizate
• PPS polyphenylene sulfide
• PPA polyphthalamide
• the internal layer (I) has a thickness representing from 5% to 95% of the total thickness of said structure.
• the outer layer (II) has a thickness of at least 5% of the total thickness of said structure.
• the internal layer (I) has a thickness of 5 to 95% of the total thickness of said structure and the external layer (II) has a thickness at least 5% of the total thickness of said structure.
• Said binder layer may comprise a binder as described, in particular in patents EP 1452307 and EP1162061, EP 1216826 and EP0428833.
• the binder layer is intended to be inserted between two layers which do not or have difficulty adhering to each other.
• the binder can be for example, but not limited to these, a composition based on 50% copolyamide 6/12 (70/30 ratio 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 the company Mitsui, a composition based on PA610 ( of Mn 30000, and as defined elsewhere) and 36% of PA6 (of Mn 28000) and 1.2% of organic stabilizers (consisting of 0.8% of Lowinox® 44B25 phenol from the company Great Lakes, of 0.2% of phosphite Irgafos® 168 from the company BASF, 0.2% anti-UV Tinuvin® 312 from the company BASF), a composition based on PA612 (of Mn 29000, and as defined elsewhere) and 36% of PA6 ( of Mn 28000, and as
• multilayer tubular structure of the invention could comprise other layers, provided that layer (I) is always the internal layer and that layer (II) is always the external layer and that there is has adhesion between the different layers.
• said tubular structure has a quantity of soluble and insoluble extractables released into said cooling liquid less than lg/m 2 , after aging for 1200 hours at 80°C of said tubular structure multilayer in contact with said cooling liquid.
• the present invention relates to a tubular structure as defined above, for fuel cell cooling.
• Multilayer tubes are made by coextrusion.
• a McNeil industrial 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 suitable for polyamides.
• the extrusion line includes:
• the internal diameter of the die and the external diameter of the punch are chosen according to the structure to be produced and the materials which compose it, as well as the dimensions of the tube and the line speed;
• - a vacuum tank with an adjustable depression level. Water circulates in this tank, generally maintained at 20°C, into which a gauge is immersed to conform the tube to 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 the water is maintained at around 20°C, allowing the tube to be cooled along the route from the head to the draw bench;
• the 5 extruder configuration is used to produce tubes ranging from 2 layers to 5 layers.
• 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 fluid.
• the tubes which meet the characteristics described in this patent application, were taken, after stabilization of the extrusion parameters, the dimensions of the targeted tube 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 considered, so that they remain in the molten state, thus avoiding that they solidify and block the machine.
• ETFE EP7000 (Daikin Chemicals)
• PA9T Genestar N1001D (Kuraray)
• Binder 1 Orevac® 18342N (SK functional polymers)
• Binder2 Orevac® 18729 (SK functional polymers)
• HDPE Lupolen®4261 AIM (LyondelIBasell)
• PP SABIC®PP 4935 (Sabie)
• Table 2 shows the tests used and the classification of the results.

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• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• General Engineering & Computer Science (AREA)
• Physics & Mathematics (AREA)
• Thermal Sciences (AREA)
• Laminated Bodies (AREA)
• Fuel Cell (AREA)
• Rigid Pipes And Flexible Pipes (AREA)

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• 2022
  • 2022-07-07 FR FR2206953A patent/FR3137605B1/fr active Active
• 2023
  • 2023-07-06 WO PCT/FR2023/051039 patent/WO2024009042A1/fr not_active Ceased
  • 2023-07-06 JP JP2024572734A patent/JP2025524393A/ja active Pending
  • 2023-07-06 KR KR1020257003635A patent/KR20250036836A/ko active Pending
  • 2023-07-06 EP EP23752004.4A patent/EP4551397A1/de active Pending
  • 2023-07-06 CN CN202380052126.0A patent/CN119546459A/zh active Pending

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