Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such 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
  • B32B1/00—Layered products having a non-planar shape
  • B32B1/08—Tubular products
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/13—Phenols; Phenolates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/15—Heterocyclic compounds having oxygen in the ring
  • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
  • C08K5/1535—Five-membered rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/17—Amines; Quaternary ammonium compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/43—Compounds containing sulfur bound to nitrogen
  • C08K5/435—Sulfonamides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/52—Phosphorus bound to oxygen only
  • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
  • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino-carboxylic acids or of polyamines and polycarboxylic acids
• • H—ELECTRICITY
  • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
  • H02K—DYNAMO-ELECTRIC MACHINES
  • H02K1/00—Details of the magnetic circuit
  • H02K1/06—Details of the magnetic circuit characterised by the shape, form or construction
  • H02K1/22—Rotating parts of the magnetic circuit
  • H02K1/27—Rotor cores with permanent magnets
• • 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
  • B32B2250/03—3 layers
• • 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
  • B32B2272/00—Resin or rubber layer comprising scrap, waste or recycling material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
  • B32B2307/558—Impact strength, toughness
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/704—Crystalline
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/726—Permeability to liquids, absorption
  • B32B2307/7265—Non-permeable
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2597/00—Tubular articles, e.g. hoses, pipes
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0016—Plasticisers

Definitions

• ELV end-of-life motor vehicle
• a large quantity of vehicle parts are recoverable and recyclable, in the form of used spare parts or raw materials.
• Parts intended for reuse (headlights, indicators, engine, radiator, starter, hood, fenders, doors, etc.) are dismantled and stored for resale.
• Carcasses and non-recyclable parts are crushed for recovery or landfill.
• European Directive 2000/53 / EC relating to end-of-life vehicles has set a rate of reuse and recovery of 95% by weight per vehicle from 2015.
• the 95% reused and recovered are subject to:
• Energy recovery use of waste (oils, tires, plastics, etc.) as means of energy production, by direct incineration with or without other waste; Material recovery: Reuse or reuse: new use of a part which retains the same use and is not transformed, or Recycling: operation aimed at introducing materials from waste into the production cycle, as a total or partial replacement of a virgin material.
• a motor vehicle contains a large number of pipes, in particular pipes intended for transporting fluids such as air, oil (for example for cooling the automatic gearbox "TOC, Transmission Oil Coder), 'water, a urea solution, a glycol-based coolant, a fuel such as gasoline, in particular bio-gasoline or diesel, in particular bio-diesel, or hydrogen.
• fluids such as air, oil (for example for cooling the automatic gearbox "TOC, Transmission Oil Coder), 'water, a urea solution, a glycol-based coolant, a fuel such as gasoline, in particular bio-gasoline or diesel, in particular bio-diesel, or hydrogen.
• These pipes can be monolayer and / or multilayer tubular structures and or in particular based on polyamide (s).
• polyamide polyamide
• the tubes especially under the engine cover, are placed in a severe thermo-oxidative environment due to the heat given off by the engine, which can typically reach 150 ° C and the presence of air and therefore oxygen.
• Each increase in temperature of 10 ° C typically results in a halving of the life of the tubes as well as the degradation of certain additives of said tubes such as stabilizers.
• a pipe for transporting a fuel for example a polyamide pipe which contains a plasticizer, has lost most of its plasticizer when it reaches the end of its life and the polyamide constituting it initially present is depolymerized and / or degraded and has lost most of its stabilizers, which prohibits its safe reuse.
• the present invention therefore relates to a multilayer tubular structure (MLT) intended for the transport of automotive fluids, in particular air, oil, water, a urea solution, a cooling liquid based on glycol, or a fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel, or hydrogen, comprising at least three layers: at least a layer (1) consisting of a composition predominantly comprising at least one semi-crystalline aliphatic polyamide, said composition consisting of at least 50% of recycled material originating from a single-layer and / or multi-layer tube having been intended for the transport of automotive fluids, in particular as defined above, said tube consisting of a composition which predominantly comprises at least one polyamide, at least one layer (2) consisting of a composition comprising predominantly at least one semi-crystalline aliphatic polyamide and optionally at least one impact modifier, and when the layer (2) consists of a composition comprising predominantly at least one semi-aliphatic polyamide -crystalline which is PA12 and / or PA612
• a polyamide-based layer consisting of at least 50% recycled material, in particular embedded between a polyamide-based layer and a barrier layer made of non-recycled material, allowed the constitution of 'a multilayer tubular structure comprising at least three layers capable of transporting an automotive fluid in particular air, oil, water, urea solution, glycol-based coolant, or a fuel such as gasoline, in particular bio-gasoline or diesel, in particular bio-diesel, or hydrogen, whatever the type of fluid initially transported by the single-layer and / or multi-layer tube recycled component of the embedded layer.
• the present invention relates to a multilayer tubular structure (MLT) intended for the transport of automotive fluids, in particular air, oil, water, a urea solution, a liquid.
• cooling agent based on glycol, or a fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel, or hydrogen, comprising at least three layers: at least one layer (1) consisting of a composition predominantly comprising at least one semi-crystalline aliphatic polyamide, said composition consisting of at least 50% of recycled material originating from a single-layer and / or multi-layer tube having initially transported automotive fluids, in particular as defined above, said tube consisting of a composition which mainly comprises at least one polyamide, at least one layer (2) consisting of a composition mainly comprising at least polyamide semi-crystalline aliphatic acid and optionally at least one impact modifier, and when the layer (2) consists of a composition mainly comprising at least one semi-crystalline aliphatic polyamide which is PA12 and / or PA61
• the single-layer and / or multi-layer tube having initially transported automobile fluids from which the recycled material originates is therefore a used tube which has already transported said fluid for at least several months, in particular several years.
• the single-layer and / or multi-layer tube that initially transported fluids is therefore to the exclusion of a virgin tube.
• fluid denotes a gas or a liquid used in the automobile, in particular air, oil, water, a urea solution, a glycol-based coolant, or a fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel, or hydrogen.
• said fluid denotes fuels, in particular gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio diesel.
• gasoline denotes a mixture of hydrocarbons obtained from the distillation of petroleum to which additives or alcohols such as methanol and ethanol may be added, the alcohols possibly being the major components in certain cases.
• alcoholic gasoline refers to gasoline to which methanol or ethanol has been added. It also designates a gasoline of type E95 which does not contain any petroleum distillation product.
• polyamide based means at least 50% by weight of polyamide in the diaper.
• composition comprising predominantly at least one polyamide .
• said layer (2) consists of a composition mainly comprising at least one semi-crystalline aliphatic polyamide and at least one impact modifier in a proportion of 3 to 45% by weight relative to the total weight of the composition. .
• barrier layer designates a layer having characteristics of low permeability and of good resistance to the various constituents of automotive fluids, in particular to air, to oil, to water, to a solution of. urea, to a coolant glycol-based, or a fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel, or hydrogen, it is that is to say that the barrier layer slows down the passage of said fluid, and in particular fuel, both for its polar components (such as ethanol) and for its non-polar components (hydrocarbons) in the other layers of the structure or even at the exterior of the structure.
• the barrier layer is therefore a layer making it possible above all not to lose too much, in particular gasoline in the atmosphere by diffusion, thus making it possible to avoid atmospheric pollution.
• Layer (1) consists of a composition comprising predominantly at least one semi-crystalline aliphatic polyamide, said composition consisting of at least 50% of recycled material originating from a single-layer and / or multi-layer tube having been intended for transport. automotive fluids.
• polyamide denotes both a homopolyamide and a copolyamide.
• polyamides within the meaning of the invention throughout the description denotes polyamides which have a melting point (Tm) and an enthalpy of fusion DH> 25 J / g, in particular> 40 J / g, in particular> 45J / g, as well as a glass transition temperature (Tg) as determined by DSC according to ISO 11357-1: 2016 and ISO 11357-2 and 3: 2013, at a heating rate of 20K / min.
• Tm melting point
• Tg glass transition temperature
• Said at least one semi-crystalline aliphatic 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 Xa with at least one dicarboxylic acid Yb.
• said at least one semi-crystalline aliphatic polyamide when obtained from the polycondensation of at least one lactam, said at least one lactam can be chosen from a C6 to C18 lactam, preferably C10 to C18, more preferably C10 to C12.
• a C6 to C12 lactam is in particular caprolactam, decanolactam, undecanolactam, and lauryllactam.
• said at least one semi-crystalline aliphatic 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 semi-crystalline aliphatic polyamide is obtained from the polycondensation of a single lactam and said lactam is chosen from lauryllactam and unecanolactam, advantageously lauryllactam.
• said at least one semi-crystalline aliphatic polyamide is obtained from the polycondensation of at least one amino acid
• said at least one amino acid can be chosen from a C6 to C18 amino acid, preferably C10 to C18, more preferably C10 to C12.
• a C6 to C12 amino acid is in particular 6-aminohexanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 10-aminoundecanoic acid, 12-aminododecanoic acid and 11-aminoundecanoic acid as well as its derivatives, in particular N-heptyl-11-aminoundecanoic acid.
• said at least one semi-crystalline aliphatic 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 semi-crystalline aliphatic polyamide is obtained from the polycondensation of a single amino acid and said amino acid is chosen from 11-aminoundecanoic acid and 12-aminododecanoic acid, advantageously 11-aminoundecanoic acid.
• said at least one semi-crystalline aliphatic polyamide is obtained from the polycondensation of at least one C4-C36, preferably C5-C18, preferably C5-C12, more preferably C10-C12 diamine Xa, with at least one diacid Yb at C4-C36, preferably C6-C18, preferably C6-C12, more preferably C10-C12, then said at least one diamine at Xa is an aliphatic diamine and said at least one diacid Yb is an aliphatic diacid.
• the diamine can be linear or branched.
• it is linear.
• Said at least one C4-C36 diamine Xa may in particular be chosen from 1,4-butanediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylèdiamine, 1, 10- decamethylèdiamine, 1, 11-undecamethylèdiamine, 1,12-dodecamethylèdiamine, 1, 13-tridecamethylèdiamine, 1, 14-tetradecamethylèdiamine, 1, 16-hexadecamethylèdiamine and 1 , 18-octadecamethylediamine, octadecenediamine, eicosanediamine, docosanediamine and diamines obtained from fatty acids.
• said at least one Xa diamine is C5-C18 and chosen from 1, 5-pentamethylenediamine, 1, 6-hexamethylenediamine, 1, 7-heptamethylenediamine, 1, 8-octamethylenediamine, 1, 9-nonamethylenediamine, 1, 10-decamethylèdiamine,
• said at least one C5 to C12 diamine Xa is in particular chosen from 1, 5-pentamethylenediamine, 1, 6-hexamethylenediamine, 1, 7-heptamethylenediamine, 1, 8-octamethylenediamine, 1, 9- nonamethylèdiamine, 1, 10-decamethylèdiamine, 1, 11-undecamethylèdiamine, 1, 12-dodecamethylèdiamine.
• said at least one C6 to C12 diamine Xa is in particular chosen from 1, 6-hexamethylenediamine, 1, 7-heptamethylenediamine, 1, 8-octamethylenediamine, 1, 9-nonamethylenediamine, 1, 10- decamethylèdiamine, 1, 11- undecamethylèdiamine, 1, 12-dodecamethylèdiamine.
• the diamine Xa used is C10 to C12, in particular chosen from 1, 10-decamethylèdiamine, 1, 11-undécamethylèdiamine, 1, 12-dodecamethylèdiamine.
• Said at least one C4 to C36 dicarboxylic acid Yb can be chosen from succinic acid, glutaric acid, 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.
• it is linear.
• said at least one dicarboxylic acid Yb 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 Yb is C6 to C12 and is chosen from adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid and dodecanedioic acid.
• said at least one dicarboxylic acid Yb is C10 to C12 and is chosen from sebacic acid, undecanedioic acid and dodecanedioic acid.
• said aliphatic semi-crystalline polyamide is obtained from the polycondensation of at least one diamine Xa with at least one dicarboxylic acid Yb, it can therefore comprise a single diamine or several diamines and a single dicarboxylic acid or several dicarboxylic acids.
• said semi-crystalline aliphatic polyamide is obtained from the polycondensation of a single diamine Xa with a single dicarboxylic acid Yb.
• the expression "predominantly comprising at least one polyamide of aliphatic type” means that said composition of the layer (1) comprises at least 50% by weight of at least one aliphatic polyamide relative to the total weight of said composition.
• said composition of the layer (1) comprises at least 60% by weight, in particular at least 70% by weight, in particular at least 80% by weight, more particularly at least 90% by weight of at least one aliphatic polyamide relative to the total weight of said composition.
• Said composition of the layer (1) consists of at least 50% of recycled material originating from a single-layer and / or multi-layer tube which has been intended for the transport of automotive fluids.
• the “at least one major polyamide” of said composition corresponds in its entirety to what is called “at least 50% of recycled material” or that at least 50% by weight of all the constituents of the composition. are of recycled origin coming from single-layer pipe, or from multilayer pipe, or from a mixture of single-layer and multilayer pipe.
• the recycled material can come from a single-layer and / or multi-layer tube, said single-layer and / or multi-layer tubes having been intended for the transport of automotive fluid.
• Said tube is therefore a used tube, that is to say that it has been used for at least one year for the transport of said fluid defined above.
• Said single-layer tube consists of a composition comprising a semi-crystalline aliphatic polyamide and optionally impact modifiers and / or additives and / or plasticizers and / or antistatic fillers.
• Said multilayer tube comprises at least one layer consisting of a composition comprising a semi-crystalline aliphatic polyamide and optionally impact modifiers and / or additives. It can therefore comprise other layers made up of a thermoplastic polymer other than a semi-crystalline aliphatic polyamide, such as for example a polypropylene, a semi-aromatic polyamide or a polyethylene vinyl alcohol (EVOH). It is obvious that the single-layer tube can also be a mixture of single-layer tubes, that is to say for example two types of single-layer tubes each consisting of a different semi-crystalline aliphatic polyamide, for example a PA11 and a PA12 .
• the multilayer pipe can also be a mixture of different types of multilayer pipe, provided that at least one of the layers of one of the types of multilayer pipe is made of a semi-crystalline aliphatic polyamide.
• Said single-layer and / or multi-layer tube which was intended for the transport of automobile fluid and which is therefore used can undergo several different treatments in order to be able to be recycled:
• the ground particles can be ground and recompounded, that is to say that after grinding, the ground particles are fed into an extruder, in particular of the co-rotating twin-screw type, or of the co-kneader type (Buss), where they are remixed. by merger.
• the molten material comes out of the extruder in rods which are cooled and cut into granules;
• the ground particles can be ground and recompounded and reformulated, that is to say that after grinding, the ground particles are fed into an extruder, as defined above where they are remixed by melting with the addition of at least one compound. chosen from a semi-crystalline aliphatic polyamide, of recycled origin or not, of at least one impact modifier, a plasticizer, an additive and antistatic fillers.
• the molten material comes out of the extruder in rods which are cooled and cut into granules.
• the single-layer and / or multi-layer tube which has been intended for transporting automotive fluid undergoes a washing and / or cleaning step before grinding.
• the crushed tube undergoes a washing and / or cleaning step after crushing.
• the single-layer and / or multilayer tube which has been intended for the transport of fluid for an automobile undergoes a washing and / or cleaning step before grinding and is then crushed and it then optionally undergoes, before recompounding, a washing and / or step. cleaning after grinding.
• the cleaning step can be carried out for example under vacuum.
• the Tm of the predominantly aliphatic semi-crystalline polyamide of layer (1) is ⁇ 225 ° C, in particular ⁇ 200 ° C, as determined according to ISO 11357-3: 2013, at a heating rate of 20K / min .
• said composition of the layer (1) is devoid of plasticizer and / or impact modifier and said recycled material comes from a tube chosen from among a crushed tube, a crushed and recompounded tube and a crushed, recompounded tube. and reworded.
• said composition of the layer (1) comprises at least one compound chosen from plasticizer, an impact modifier and an additive, and said recycled material is chosen from a crushed tube, then recompounded and reformulated.
• said tube is a single-layer tube and / or a multilayer tube.
• the fluid transported by said monolayer and / or multilayer tube is different from that of said multilayer tubular structure (MLT).
• MLT multilayer tubular structure
• said multi-layer tubular structure may be intended to transport gasoline or, if the single-layer and / or multi-layer tube has transported a fluid such as alcoholic gasoline, said tubular structure (MLT) may be intended to transport diesel.
• the fluid transported by said monolayer and / or multilayer tube is the same as that of said multilayer tubular structure (MLT).
• the tubular structure (MLT) may be intended to transport gasoline provided that the gasoline of the single-layer and / or multi-layer tube and said multilayer tubular structure (MLT) is the same, for example, alcoholic gasoline.
• the recycled material comes from a single-layer tube consisting of a composition comprising only a PA11.
• said composition of the layer (1) comprises at least 60% by weight, in particular at least 70% by weight, in particular at least 80% by weight, in particular at least 90% by weight, more particularly in less 95% recycled material. In another embodiment, said composition of the layer (1) consists of 100% by weight of recycled material.
• said tube which was intended for transporting fluid for an automobile is single-layer or multilayer and simply ground and the composition of the layer (1) resulting from said recycling consists of: at least 61% by weight, in particular of 96% to 99% by weight, in particular from 96% to 98% by weight, of at least one semi-crystalline aliphatic polyamide denoted C having an average number of carbon atoms per nitrogen atom denoted Ce ranging from 6 to 18, preferably 8 to 12; 0 to 2% of at least one plasticizer, 0 to 2% by weight of at least one additive, in particular a stabilizer; the sum of the constituents being equal to 100%.
• the semi-crystalline aliphatic polyamide denoted C is chosen from PA612, PA1012, PA1010, PA11 and PA12, in particular PA11.
• said tube was intended for transporting fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel.
• fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel.
• the semi-crystalline aliphatic polyamide denoted C is chosen from PA612, PA1012, PA1010, PA11 and PA12, in particular PA11 and said tube was intended for transporting fuel such as gasoline, especially alcoholic gasoline, bio-gasoline or diesel, especially bio diesel.
• said tube which was intended for transporting automobile fluid is single-layer.
• said tube which was intended for transporting fluid for an automobile is single-layer or multilayer, crushed and recompounded and the composition of the layer (1) resulting from said recycling consists of: at least 61% by weight, in particular from 96% to 99% by weight, in particular from 96% to 98% by weight, of at least one semi-crystalline aliphatic polyamide denoted C having an average number of carbon atoms per nitrogen atom denoted Ce comprised of 6 to 18, preferably 8 to 12; from 0 to 2% of at least one plasticizer, from 0 to 2% by weight of at least one additive, in particular a stabilizer; the sum of the constituents being equal to 100%.
• the semi-crystalline aliphatic polyamide denoted C is chosen from PA612, PA1012, PA1010, PA11 and PA12, in particular PA11.
• said tube was intended for transporting fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel.
• the semi-crystalline aliphatic polyamide denoted C is chosen from PA612, PA1012, PA1010, PA11 and PA12, in particular PA11 and said tube was intended for transporting fuel such as gasoline, especially alcoholic gasoline, bio-gasoline or diesel, especially bio diesel.
• said tube which was intended for transporting automobile fluid is single-layer.
• said tube which was intended for transporting fluid for an automobile is single-layer or multilayer, crushed, recompounded and reformulated and the composition of the layer (1) resulting from said recycling and reformulated consists of: at least 58.5 % by weight of at least one semi-crystalline aliphatic polyamide denoted C having an average number of carbon atoms per nitrogen atom denoted Ce ranging from 6 to 18, advantageously from 8 to 12; from 6 to 14% of at least one plasticizer, in particular from 6 to 8%; from 0.5 to 1.5% by weight of at least one additive, in particular a stabilizer; the sum of the constituents being equal to 100%.
• the semi-crystalline aliphatic polyamide denoted C is chosen from PA612, PA1012, PA1010, PA11 and PA12, in particular PA11.
• said tube was intended for transporting fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel.
• the semi-crystalline aliphatic polyamide denoted C is chosen from PA612, PA1012, PA1010, PA11 and PA12, in particular PA11 and said tube was intended for transporting fuel such as gasoline, especially alcoholic gasoline, bio-gasoline or diesel, especially bio diesel.
• said tube which was intended for transporting automobile fluid is single-layer.
• said tube which was intended for the transport of fluid for an automobile is single-layer or multilayer, crushed, recompounded and reformulated and the composition of the layer (1) resulting from said recycling and reformulated consists of: at least 58% in weight of at least one semi-crystalline aliphatic polyamide denoted C having an average number of carbon atoms per nitrogen atom denoted Ce ranging from 6 to 18, advantageously from 8 to 12; from 6 to 14% of at least one plasticizer, in particular from 6 to 8%; from 1 to 2% by weight of at least one additive, in particular a stabilizer and a catalyst; the sum of the constituents being equal to 100%.
• the semi-crystalline aliphatic polyamide denoted C is chosen from PA612, PA1012, PA1010, PA11 and PA12, in particular PA11.
• said tube was intended for transporting fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel.
• the semi-crystalline aliphatic polyamide denoted C is chosen from PA612, PA1012, PA1010, PA11 and PA12, in particular PA11 and said tube was intended for transporting fuel such as gasoline, especially alcoholic gasoline, bio-gasoline or diesel, especially bio diesel.
• said tube which was intended for transporting automobile fluid is single-layer.
• the composition is degassed during the compounding, even more advantageously the degassing is located just after the melting zone, and before the zone for introducing a plasticizer such as BBSA or the like.
• the semi-crystalline aliphatic polyamide denoted C is chosen from PA612, PA1012, PA1010, PA11 and PA12, in particular PA11.
• said tube was intended for transporting fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel.
• the semi-crystalline aliphatic polyamide denoted C is chosen from PA612, PA1012, PA1010, PA11 and PA12, in particular PA11 and said tube was intended for transporting fuel such as gasoline, especially alcoholic gasoline, bio-gasoline or diesel, especially bio diesel.
• said tube which was intended for transporting automobile fluid is single-layer.
• said tube which was intended for transporting fluid for an automobile is single-layer or multilayer, crushed, recompounded and reformulated and the composition of the layer (1) resulting from said recycling and reformulated consists of: at least 55% in weight, in particular from 55% to 99% by weight, in particular from 55% to 98% by weight, of at least one semi-crystalline aliphatic polyamide denoted C having an average number of carbon atoms per nitrogen atom denoted This included from 6 to 18, advantageously from 8 to 12; from 0 to 45% by weight of at least one impact modifier, in particular from 1 to 45% by weight of at least one impact modifier, in particular from 2 to 45% by weight of at least one impact modifier, the sum of the constituents being equal to 100%.
• the semi-crystalline aliphatic polyamide denoted C is chosen from PA612, PA1012, PA1010, PA11 and PA12, in particular PA11.
• said tube was intended for transporting fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel.
• the semi-crystalline aliphatic polyamide denoted C is chosen from PA612, PA1012, PA1010, PA11 and PA12, in particular PA11 and said tube was intended for transporting fuel such as gasoline, especially alcoholic gasoline, bio-gasoline or diesel, especially bio diesel.
• said tube which was intended for transporting automobile fluid is single-layer.
• said tube which was intended for transporting fluid for an automobile is single-layer or multilayer, crushed, recompounded and reformulated and the composition of the layer (1) resulting from said recycling and reformulated consists of: at least 50% of weight of at least one semi-crystalline aliphatic polyamide denoted C having an average number of carbon atoms per nitrogen atom denoted Ce ranging from 6 to 18, advantageously from 8 to 12; from 0 to 43.5% by weight of at least one impact modifier, in particular from 1 to 43.5% by weight of at least one impact modifier, in particular from 2 to 43.5% by weight of at least an impact modifier, from 6 to 14% of at least one plasticizer, in particular from 6 to 8%; from 0.5 to 1.5% by weight of at least one additive, in particular a stabilizer; the sum of the constituents being equal to 100%.
• the semi-crystalline aliphatic polyamide denoted C is chosen from PA612, PA1012, PA1010, PA11 and PA12, in particular PA11.
• said tube was intended for transporting fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel.
• the semi-crystalline aliphatic polyamide denoted C is chosen from PA612, PA1012, PA1010, PA11 and PA12, in particular PA11 and said tube was intended for transporting fuel such as gasoline especially alcoholic gasoline, bio-gasoline or diesel, in particular bio diesel.
• said tube which was intended for transporting automobile fluid is single-layer.
• said tube which was intended for transporting fluid for an automobile is single-layer or multilayer, crushed, recompounded and reformulated and the composition of the layer (1) resulting from said recycling and reformulated consists of: at least 50% of weight of at least one semi-crystalline aliphatic polyamide denoted C having an average number of carbon atoms per nitrogen atom denoted Ce ranging from 6 to 18, advantageously from 8 to 12; from 0 to 43% by weight of at least one impact modifier, in particular from 1 to 43% by weight of at least one impact modifier, in particular from 2 to 38% by weight of at least one impact modifier, of 6 at 14% of at least one plasticizer, in particular from 6 to 8%; from 1 to 2% by weight of at least one additive, in particular a stabilizer and a catalyst; the sum of the constituents being equal to 100%.
• the semi-crystalline aliphatic polyamide denoted C is chosen from PA612, PA1012, PA1010, PA11 and PA12, in particular PA11.
• said tube was intended for transporting fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel.
• the semi-crystalline aliphatic polyamide denoted C is chosen from PA612, PA1012, PA1010, PA11 and PA12, in particular PA11 and said tube was intended for transporting fuel such as gasoline, especially alcoholic gasoline, bio-gasoline or diesel, especially bio diesel.
• said tube which was intended for transporting automobile fluid is single-layer.
• the semi-crystalline aliphatic polyamide denoted C is chosen from PA612, PA1012, PA1010, PA11 and PA12, in particular PA11.
• said tube was intended for transporting fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular bio-diesel.
• the semi-crystalline aliphatic polyamide denoted C is chosen from PA612, PA1012, PA1010, PA11 and PA12, in particular PA11 and said tube was intended for transporting fuel such as gasoline, especially alcoholic gasoline, bio-gasoline or diesel, especially bio diesel.
• said tube which was intended for transporting automobile fluid is single-layer.
• the impact modifier is advantageously constituted by a polymer having a flexural modulus of less than 100 MPa measured according to the ISO 178: 2010 standard, determined at 23 ° C with relative humidity: RH50%, and of Tg less than 0 ° C (measured according to standard 11357-2: 2013 at the inflection point of the DSC thermogram, at a heating rate of 20K / min), in particular a polyolefin.
• the polyolefin of the impact modifier can be functionalized or non-functionalized or be a mixture of at least one functionalized and / or at least one non-functionalized.
• the polyolefin has been designated by (B) and functionalized polyolefins (B1) and unfunctionalized polyolefins (B2) have been described below.
• An unfunctionalized polyolefin (B2) is conventionally a homopolymer or copolymer of alpha olefins or diolefins, such as, for example, ethylene, propylene, butene-1, octene-1, butadiene.
• alpha olefins or diolefins such as, for example, ethylene, propylene, butene-1, octene-1, butadiene.
• LDPE low density polyethylene
• HDPE high density polyethylene
• LLDPE linear low density polyethylene, or linear low density polyethylene
• VLDPE very low density polyethylene, or very low density polyethylene
• metallocene polyethylene metallocene polyethylene
• ethylene / alpha-olefin copolymers such as ethylene / propylene, EPR (abbreviation of ethylene-propylene-rubber) and ethylene / propylene / diene (EPDM).
• EPR abbreviation of ethylene-propylene-rubber
• EPDM ethylene / propylene / diene
• SEBS ethylene-butene / styrene
• SBS styrene / butadiene / styrene
• SIS 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.
• 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 degree of grafting, for example from 0.01 to 5% by weight.
• the functionalized polyolefin (B1) can be chosen from the following (co) polymers, grafted with maleic anhydride or glycidyl methacrylate, in which the degree of grafting is for example from 0.01 to 5% by weight:
• ethylene / alpha-olefin copolymers such as ethylene / propylene, EPR (abbreviation of ethylene-propylene-rubber) and ethylene / propylene / diene (EPDM).
• EPR abbreviation of ethylene-propylene-rubber
• EPDM ethylene / propylene / diene
• SEBS ethylene-butene / styrene
• SBS styrene / butadiene / styrene
• SIS isoprene / styrene
• SEPS styrene / ethylene-propylene / styrene
• alkyl (meth) acrylate copolymers containing up to 40% by weight of alkyl (meth) acrylate;
• the functionalized polyolefin (B1) can also be chosen from ethylene / propylene copolymers predominantly in propylene grafted with maleic anhydride then condensed with mono-amine polyamide (or a polyamide oligomer) (products described in EP-A-0342066) .
• the functionalized polyolefin (B1) can also be a co- or ter polymer of at least the following units: (1) ethylene, (2) alkyl (meth) acrylate or vinyl ester of saturated carboxylic acid and (3) anhydride such as maleic anhydride or (meth) acrylic acid or epoxy such as glycidyl (meth) acrylate.
• (meth) acrylic acid can be salified with Zn or Li.
• alkyl (meth) acrylate in (B1) or (B2) denotes methacrylates and acrylates of C1 to C8 alkyl, and may be chosen from methyl acrylate, ethyl acrylate , n-butyl acrylate, isobutyl acrylate, ethyl-2-hexyl acrylate, cyclohexyl acrylate, methyl methacrylate and ethyl methacrylate.
• the aforementioned polyolefins (B1) can also be crosslinked by any suitable process or agent (diepoxy, diacid, peroxide, etc.); the term functionalized polyolefin also includes mixtures of the above 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 copolymerized in a random or block fashion and have a linear or branched structure.
• the molecular weight, the MFI number, the density of these polyolefins can also vary to a large extent, which will be appreciated by those skilled in the art.
• MFI short for Melt Flow Index, is the melt flow index. It is measured according to standard ASTM 1238.
• the unfunctionalized polyolefins (B2) are chosen from homopolymers or copolymers of polypropylene and any homopolymer of ethylene or copolymer of ethylene and of a comonomer of higher alpha olefinic type. such as butene, hexene, octene or 4-methyl 1-Pentene.
• PPs high density PE, medium density PE, linear low density PE, low density PE, very low density PE.
• polyethylenes are known to those skilled in the art as being produced according to a “radical” process, according to a “Ziegler” type catalysis or, more recently, according to a so-called “metallocene” catalysis.
• the functionalized polyolefins (B1) are chosen from any polymer comprising alpha olefinic units and units bearing polar reactive functions such as epoxy, carboxylic acid or carboxylic acid anhydride functions.
• polymers mention may be made of the ter polymers of ethylene, of alkyl acrylate and of maleic anhydride or of glycidyl methacrylate, such as Lotader® from the Applicant or polyolefins grafted with l.
• maleic anhydride such as Orevac® from the Applicant as well as ter polymers of ethylene, of alkyl acrylate and of (meth) acrylic acid.
• Mention may also be made of homopolymers or copolymers of polypropylene grafted with a carboxylic acid anhydride and then condensed with polyamides or mono-amino polyamide oligomers.
• the additives optionally used in the compositions of the invention are the conventional additives used in polyamides well known to those skilled in the art and are described in particular in EP 2098580.
• catalysts are selected from a catalyst, an antioxidant, a heat stabilizer, a UV absorber, a light stabilizer, a lubricant, an inorganic filler, a flame retardant, a nucleating agent and a dye, fibers. reinforcement, a wax and their mixtures.
• catalyst denotes a polycondensation catalyst such as an inorganic or organic acid.
• the proportion by weight of catalyst is from 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 of these.
• the stabilizer can be a UV stabilizer, an organic stabilizer or more generally a combination of organic stabilizers, such as an antioxidant of the phenol type (for example of the type of that of irganox® 245 or 1098 or 1010 of the company Ciba-BASF), an antioxidant of the phosphite type (for example irgafos® 126 and irgafos® 168 from the company Ciba-BASF) and even possibly other stabilizers such as a HALS, which means Hindered Amine Light Stabilizer or light stabilizer of the hindered amine type (for example Tinuvin® 770 from the company Ciba-BASF), an anti-UV (for example Tinuvin® 312 from the company Ciba) or a phosphorus-based stabilizer. It is also possible to use antioxidants of amine type such as Naugard® 445 from the company Crompton or else polyfunctional stabilizers such as Nylostab® S-EED from the company
• 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, in particular potassium.
• the plasticizers are, by way of example, the plasticizers are chosen from benzene sulfonamide derivatives, such as n-butyl benzene sulfonamide (BBSA); ethyl toluene sulfonamide or N-cyclohexyl toluene sulfonamide; esters of hydroxybenzoic acids, such as 2-ethylhexyl parahydroxybenzoate and 2-decyl-hexyl parahydroxybenzoate; esters or ethers of tetrahydrofurfuryl alcohol, such as oligoethyleneoxytetrahydrofurfurylalcohol; and esters of citric acid or hydroxy-malonic acid, such as oligoethyleneoxy malonate.
• BBSA n-butyl benzene sulfonamide
• esters of hydroxybenzoic acids such as 2-ethylhexyl parahydroxybenzoate and 2-decyl-he
• the additives when they are present in the composition are advantageously present from 1 to 20% by weight, in particular from 5 to 15% by weight, in particular from 5 to 12% by weight.
• antistatic charges are advantageously present from 1 to 20% by weight, in particular from 5 to 15% by weight, in particular from 5 to 12% by weight.
• the antistatic fillers are for example chosen from carbon black, graphite, carbon fibers, carbon nanotubes, in particular carbon black and carbon nanotubes,
• polysemi-crystalline polyamide and “aliphatic” have the same definition as for layer (1).
• Said at least one semi-crystalline aliphatic polyamide is obtained in the same way as described above for layer (1).
• said layer (2) is devoid of impact modifier.
• the semi-crystalline aliphatic polyamide which is PA12 or PA612 or PA1010 is excluded from the composition which constitutes layer (2).
• said layer (2) comprises from 3 to 45% by weight of at least one impact modifier, in particular from 5 to 20% by weight of at least one impact modifier.
• the composition of said layer (2) comprises a PA11, a PA12 or a PA612 and from 3 to 45% by weight of an impact modifier, in particular from 5 to 20% by weight of an impact modifier.
• the barrier layer slows down the passage of said fluid, and in particular fuel, both for its polar components (such as ethanol) and for its non-polar components (hydrocarbons) in the other layers of the structure or even outside. of the structure. It is therefore made up based on barrier materials which can be polyphthalamides (PPA) and / or also non-polyamide barrier materials such as very crystalline polymers such as the copolymer of ethylene and vinyl alcohol (noted EVOH below.
• PPA polyphthalamides
• EVOH very crystalline polymers
• PVDF functionalized polyvinylidene fluoride
• ETFE functionalized copolymer of ethylene and tetrafluoroethylene
• EFEP functionalized copolymer of ethylene, tetrafluoroethylene and hexafluoropropylene
• PPS functionalized polysulfide
• PBN functionalized polynaphthalate
• the EVOHs are particularly advantageous, in particular the richest in vinyl alcohol comonomer as well as those modified impact because they make it possible to produce less fragile structures, as well as polyphthalamides, in particular coPA6T, PA9T and its copolymers, PA10T and its copolymers or PPAs based on meta-xylylenediamine (MXD) such as MXD6 or MXD10 which can also be impact modified.
• MXD meta-xylylenediamine
• the barrier layer therefore consists of a composition based on at least one of the above barrier materials, that is to say a composition comprising at least 50% of said barrier material.
• composition can therefore also comprise impact modifiers which are as defined above.
• said layer (1) is located between a layer (2) and the barrier layer.
• said barrier layer is the layer in contact with the transported fluid.
• the composition of said layer (2) comprises a PA11, a PA12 or a PA612 and the recycled material comes from a single-layer tube consisting of a composition comprising only a PA11, in particular the composition of the layer (1) is made from 100% recycled material.
• the composition of said layer (2) comprises a PA11, a PA12 or a PA612
• the recycled material comes from a single-layer tube consisting of a composition comprising only a PA11, in particular the composition of the layer (1) is consisting of 100% recycled material and the composition of said layer (2 ') comprises a PA11, a PA12 or a PA612.
• the composition of said layer (2) comprises a PA11, a PA12 or a PA612 and from 3 to 45% by weight of at least one impact modifier, in particular from 5 to 20% by weight of at least one modifier.
• impact and the recycled material comes from a single-layer tube consisting of a composition comprising only a PA11, in particular the composition of the layer (1) consists of 100% recycled material.
• the composition of said layer (2) comprises a PA11, a PA12 or a PA612 and from 3 to 45% by weight of at least one impact modifier, in particular from 5 to 20% by weight of at least one impact modifier and the recycled material comes from a single-layer tube consisting of a composition comprising only one PA11, in particular the composition of the layer (1) consists of 100% recycled material and the composition of said barrier layer comprises a compound chosen from EVOH, impact modified or not, in particular impact modified, and a PPA chosen from PA9T, MXD6, impact modified or not, and MXD10.
• multilayer tubular structure In a first variant of the multilayer tubular structure (MLT), it consists of three layers (2) // (1) // barrier.
• MLT multilayer tubular structure
• at least a second layer (2) is present, said layer (2) being the innermost layer in contact with the fluid.
• the MLT is therefore made up of four layers (2) // (1) // barrier // (2) with from the outside to the inside: an outer layer (2), a layer (1), a barrier layer and an inner layer (2) in contact with the automotive fluid.
• the second internal layer (2) meets the same definition as above but may be identical to or different from the external layer (2).
• the MLT is therefore made up of five layers (2) // (1) // barrier // binder (3) // (2).
• said layer (1) represents at least 10%, in particular at least 30%, in particular at least 50% of the total thickness of said multilayer tubular structure (MLT).
• said layer (1) represents at least 60%, in particular at least 70% of the total thickness of said multilayer tubular structure (MLT).
• said composition of said layer (1) is devoid of polyamides denoted A and B and said composition of said layer (2) comprises selected polyamides among those denoted E, F and a mixture of these.
• said composition of said layer (1) comprises polyamides chosen from those denoted A, B and a mixture thereof, and said composition of said layer (2) is devoid of polyamides denoted E and F.
• said composition of said layer (1) comprises polyamides selected from those noted A, B and a mixture thereof
• said composition of said layer (2) comprises polyamides selected from those noted E, F and a mixture thereof.
• said composition of said layer (1) is devoid of polyamides denoted A and B and said composition of said layer (2) is devoid of of polyamides denoted E and F.
• the layer (1) comes from a single-layer recycled tube.
• the layer (1) comes from a single-layer recycled tube and only said composition of said layer (1) comprises at least one impact modifier.
• the layer (1) comes from a single-layer recycled tube and said composition of said layer (1) as well as said compositions of the layer or layers (2) comprise at least one impact modifier. .
• the layer (1) comes from a recycled multilayer tube.
• the layer (1) comes from a multilayer recycled tube and only said composition of said layer (1) comprises at least one impact modifier.
• the layer (1) comes from a multilayer recycled tube and said composition of said layer (1) as well as said compositions of the layer or layers (2) comprise at least one impact modifier. .
• said multilayer tubular is intended for the transport of fluids chosen from a fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular gasoline. bio-diesel.
• a fuel such as gasoline, in particular alcoholic gasoline, bio-gasoline or diesel, in particular gasoline. bio-diesel.
• the binder is described in particular in patents EP1452307 and EP1162061, EP1216826, EP0428833 and EP3299165.
• the binder layer is intended to be interposed between two layers which do not adhere with difficulty to each other.
• the binder can be for example, but without being limited to these, a composition based on 50% of copolyamide 6/12 (of ratio 70/30 by mass) of Mn 16000, and of 50% of 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 (from Mn 30,000, and as defined elsewhere) and 36% PA6 (from Mn 28000) and 1.2% organic stabilizers (consisting of 0.8% of Lowinox 44B25 phenol from Great Lakes, 0.2% of Irgafos 168 phosphite from the company Ciba, 0.2% anti-UV Tinuvin 312 from the
• PA11 Polyamide 11 of Mn (number molecular mass) 29,000. The melting point is 190 ° C, its enthalpy of fusion is 56kJ / m2. The composition of this PA11 comprises 0.25% (+/- 0.05%) of H3PO4.
• PA12 Polyamide 12 of Mn (number molecular mass) 35000. The melting point is 178 ° C, its enthalpy of fusion is 54kJ / m2
• PA12-B Polyamide 12 of Mn (number molecular mass) 41000. The melting point is 178 ° C, its enthalpy of fusion is 54kJ / m2
• PA1012 Polyamide 1012 of Mn (number molecular mass) 27000. The melting point is 190 ° C, its enthalpy of fusion is 57kJ / m2
• PA612 Polyamide 612 of Mn (number molecular mass) 29000. The melting point is 218 ° C, its enthalpy of fusion is 67kJ / m2
• PA610 Polyamide 610 of Mn (number molecular mass) 30000. The melting point is 223 ° C, its enthalpy of fusion is 61kJ / m2
• PA6 Polyamide 6 of Mn (number molecular mass) 28000. The melting point is 220 ° C, its enthalpy of fusion is 68kJ / m2
• the melting temperature and the enthalpy of fusion were determined according to ISO 11357-3: 2013.
• stabilizer stabilizer consisting of 80% of Lowinox 44B25 phenol from Great Lakes, 20% of Irgafos 168 phosphite from Ciba BBSA: BBSA plasticizer (benzyl butyl sulfonamide),
• Imod generically designates a polyolefin or other impact modifier such as, among others, PEBA (polyether-block-amide), core-shells, silicones, etc.
• PEBA polyether-block-amide
• core-shells core-shells
• silicones etc.
• Imodl denotes an EPR functionalized with a reactive anhydride functional group (at 0.5-1% by mass), of MFI 9 (at 230 ° C., under) 10 kg, of the Exxellor VA1801 type from the company Exxon.
• Mod2 impact modifier of the ethylene / ethyl acrylate / anhydride type in 68.5 / 30 / 1.5 mass ratio and MFI 6 at 190 ° C under 2.16 kg.
• lmod3 impact modifier of the ethylene / butyl acrylate / anhydride type in 79/18/3 mass ratio and MFI 5 at 190 ° C under 2.16 kg.
• compositions were used to manufacture the tubes according to the invention:
• compositions called "recy”, “recy2” and “recy3" used for layer (1) of the tubes of the invention or counterexample tubes protocols for simulating an aged tube were used:
• Protocol A The tube is (artificially) aged according to an easily reproducible model protocol which consists of placing it in air (in the presence of oxygen) at 150 ° C for 96 hours (4 days), in order to thermo-oxidize it .
• This aging model is representative of the average thermo-oxidation that the tubes undergo in 10 years of service in a vehicle next to a hot engine.
• This tube aged according to this protocol (PA11-recy) was crushed and the granules obtained were used for the manufacture of the recycled layer (1) of Example 9 and compared to a tube (Example 10) whose layer (1) ) recycled comes from granules of a tube of PA11 PL (PA11-recy-car) which comes from a gasoline line of a Toyota brand car, having 10 years of age, and which has been reground.
• protocol A is representative of a regrind gasoline tube. Specific protocols used during the (re) compounding of the aged tube.
• the crushed tube After aging, the crushed tube can in certain cases be recompounded according to two protocols:
• Protocol B the regrind tube is recompounded on a Coperion / Werner 40mm twin-screw extruder, 70kgh, 300rpm, setpoint 270 ° C, with a degassing of -100mmHg.
• Protocol B2 the regrind tube is recompounded on a Coperion / Werner 40mm twin-screw extruder, 70kgh, 300rpm, 270 ° C setpoint, with a strong degassing of -660mmHg.
• compositions used for the preparation of the tubes of the invention are as follows:
• PA11 PL PA11 + 7% BBSA + 1% stabilizer
• PA12PL PA12 + 12% BBSA + 1% stabilizer
• PA11 PL-recy tube of PA11 PL aged according to protocol A, regrind, to be then recycled.
• PA11 PL-recy2 tube of PA11 PL aged according to protocol A, regrind, recompounded according to protocol B2, with during this recompounding addition of 7% BBSA + 0.5% stabilizer, to be then recycled
• PA11 PL-recy + 50% PA12PL-recy a 50/50 mixture of granules of PA11 PL-recy and PA12PL-recy.
• PA12PL-recy PA12PL tube aged according to protocol A, regrind, to be then recycled.
• PA12imod1 PA12 + 6% imodl + 8% BBSA + 1% stabilizer
• PA1012PL4 PA1012 + 12% BBSA + 1% stabilizer
• 1012-recy tube of PA1012PL4 aged according to protocol A, regrind, to be then recycled
• 11 NX3 PA11 + imod2 10% + PA610 5% + PA6 5% + BBSA 4% + stabilizer 1%
• 11NX3-recy2 11NX3 tube aged according to protocol A, regrind, recompounded according to protocol B2, recompounding with strong degassing, with during this recompounding addition of 3% BBSA and 0.5% stabilizer.
• PA11-recyNX3 tube of PA11 PL aged according to protocol A, regrind, recompounded according to protocol B2, with during this recompounding addition of imod2 10% + PA610 5% + PA6 5% + BBSA 4% + stabilizer 1%, to be subsequently recycled
• PA12HIPHL PA12 + 6% imodl + 10% BBSA + 1% stabilizer
• PA12HIP-recy3 tube of PA12HIPHL aged according to protocol A, regrind, recompounded according to protocol B, with during this recompounding addition of 6% imod1, 9% BBSA and 1% stabilizer; and then being intended for recycling.
• PA12HI2 PA12-B + 10% imod1 + 5% BBSA + 1% stabilizer
• PA12HI2-recy2 tube of PA12HI2 aged according to protocol A, reground, recompounded according to protocol B, with during this recompounding addition of 5% of BBSA and 0.5% stabilizer, to be recycled afterwards.
• OHhi shock modified EVOH, marketed under the name EVAL LA170B by the company Eval-Kuraray
• EVOH32 32% ethylene EVOH, marketed by the company Eval under the name Eval FP101 B
• PPA9T type 50/50 (9T / 9T)
• coPPA9T shock modified Genestar grade N1001DU83 / 02.
• MXD6hi shock modified MXD6 composition (sold under the name Ixef BXT-2000 by Solvay. Its melting point is 237 ° C.
• compositions are manufactured by conventional compounding in a Coperion 40 type co-rotating twin-screw extruder, at 300rpm, at 270 ° C (or at 300 ° C when the ingredients have a melting point above 260 ° C).
• Multilayer pipes of the invention The layers are described from the outside to the inside, followed by their respective thicknesses indicated as%; the tubes are of dimension 8 * 1 mm Preparation of multilayer structures (tubes):
• Multilayer pipes are produced by coextrusion.
• a Maillefer industrial multilayer extrusion line is used, equipped with 5 extruders, connected to a multilayer extrusion head with spiral mandrels.
• the extrusion line comprises: a die-punch assembly, located at the end of the coextrusion head; 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 of which it is made, as well as the dimensions of the tube and the line speed; a vacuum tank with an adjustable vacuum level. In this tank circulates water generally maintained at 20 ° C, in which is immersed a gauge allowing the tube to conform to its final dimensions.
• the diameter of the gauge is adapted to the dimensions of the tube to be produced, typically 8.5 to 10 mm for a tube with an external diameter of 8 mm and a thickness of 1 mm; a succession of cooling tanks in which water is maintained at around 20 ° C, allowing the tube to be cooled along the path from the head to the draw bench; a diameter measurer; a draw bench.
• the 5 extruder configuration is used to make tubes ranging from 2 layers to 5 layers (and also single layer tubes). In the case of structures with a number of layers less than 5, several extruders are then supplied with the same material.
• the extruded materials Before testing, in order to ensure the best tube properties and good extrusion quality, it is checked that the extruded materials have a residual moisture level before extrusion of less than 0.08%. Otherwise, an additional step of drying the material is carried out before the tests, generally in a vacuum dryer, for 1 night at 80 ° C.
• the tubes which meet the characteristics described in the present patent application, were taken, after stabilization of the extrusion parameters, the dimensions of the tubes concerned no longer changing over time.
• the diameter is controlled by a laser diameter measurer 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 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 point of the compositions considered, so that they remain in the molten state, thus avoiding they solidify and block the machine.
• Flex. designates the flexural modulus measured according to IS0178 at 23 ° C on a tube conditioned at equilibrium in a climate of 50% humidity and at 23 ° C
• Shock refers to the VW-40 ° C type shock, VW standard TL524352010
• shock performance that can be qualified as "very bad”, which corresponds to> 75%
• Old. it is about durability, in other words it indicates the resistance of the tube to oxidative aging in hot air.
• the tube is aged in air at 150 ° C, then it is shocked with a shock according to standard DIN 73378, this shock being carried out at -40 ° C, the corresponding half-life (in hours) is indicated. at the end of which 50% of the tubes tested break. A qualitative comment accompanies this value.
• thermo-oxidative aging resistance to thermo-oxidative aging
• the value given relates to the weakest interface, that is to say the least adherent of the multilayer, where there is therefore the greatest risk of detachment.
• the peeling is carried out at the interface by subjecting one of the parts to a traction at an angle of 90 ° and at a speed of 50 mm / min according to the following method.
• a strip of tube 9mm wide is taken by cutting. This strip is therefore in the shape of a tile and still has all the layers of the original tube.
• the strip, and therefore the interface is for its part maintained at 90 degrees with respect to the direction of traction.
• All.% This is the elongation at break achieved according to the ISO R527 standard except that it is measured on a tube with a diameter of 8 mm and a thickness of 1 mm.

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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)
• Mechanical Engineering (AREA)
• Power Engineering (AREA)
• Laminated Bodies (AREA)
• Rigid Pipes And Flexible Pipes (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 2020
  • 2020-05-19 FR FR2005006A patent/FR3110583B1/fr active Active
• 2021
  • 2021-05-18 WO PCT/FR2021/050856 patent/WO2021234263A1/fr not_active Ceased
  • 2021-05-18 KR KR1020227043207A patent/KR20230013046A/ko active Pending
  • 2021-05-18 CN CN202180036140.2A patent/CN115667401A/zh active Pending
  • 2021-05-18 EP EP21732468.0A patent/EP4153683A1/fr active Pending
  • 2021-05-18 US US17/999,127 patent/US12109786B2/en active Active
  • 2021-05-18 JP JP2022570114A patent/JP2023526802A/ja active Pending

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