Multilayer tubular structure intended for transporting a heat-transfer fluid

Abstract

The present invention relates to a multilayer tubular structure (MLT) intended for transporting a heat-transfer fluid, said multilayer tubular structure comprising: - at least one layer (1) comprising a composition (1) comprising mostly at least one long-chain polyamide (PA) having 10 to 15 carbon atoms per nitrogen atom and comprising at least 50% of aliphatic units relative to the sum of the units present in said long-chain polyamide; - at least one layer (2) located beneath said layer (1) comprising a composition (2) comprising mostly at least one polyamide containing 4 to 9 carbon atoms per nitrogen atom; - at least one layer (3) comprising a composition (3) comprising mostly a hydrophobic polymer, in particular a polypropylene or a polyethylene; and - a layer (4) comprising either a composition (4) comprising a PA6, a PA66 or a mixture thereof, from 5 to 50% by weight of at least one polyolefin, up to 2% by weight of at least one plasticiser and up to 2% by weight of an additive relative to the total weight of said composition (4) or a composition (4') comprising mostly at least one C8-C14 aliphatic polyamide, said layer (4) being in contact with said fluid being transported, and the thickness of said layer(s) (2) representing at least 70% of the total thickness of the tube.

Description

[0001] DESCRIPTION

[0002] TITLE: MULTILAYER TUBULAR STRUCTURE INTENDED FOR THE TRANSPORT OF A

[0003] HEAT TRANSFER FLUID

[0004] [Technical field]

[0005] The present patent application relates to a multi-layer tubular (MLT) structure intended for the transport of a heat transfer fluid and its use for the transport of heat transfer fluid, in particular refrigerant fluid chosen from hydrocarbon compounds, hydrofluorocarbons, ethers, hydrofluoroethers, CO2, NH3, SO2 and fluoroolefins, in particular R134, R-1234yf or R-1234ze, in particular R-1234yf or R-1234ze in the field of automotive air conditioning.

[0006] [Earlier technique]

[0007] Tubular structures for the transport of heat transfer fluid in the field of automotive air conditioning require two opposing properties which are respectively water permeability and hot burst (125°C) which must be greater than 83 bars.

[0008] Thus, long-chain polyamides allow the first property to be respected, which therefore makes the use of short-chain polyamides unsuitable for this first property.

[0009] However, these same short-chain polyamides provide resistance to hot bursting, which makes the use of long-chain polyamides unsuitable for this second property.

[0010] Furthermore, the European F-Gas Directive plans a gradual phase-out from the market of refrigerant gases with high global warming potential, expressed in GWP (Global Warning Potential). From 100% in 2015, the quantity of hydrofluorocarbon (HFC) refrigerants with high GWP index must decrease to 63% between 2018 and 2020 before reaching 21% in 2030.

[0011] Since January 2017, new motor vehicles sold in Europe must be fitted as original equipment with air conditioning running on R1234yf.

[0012] This standard is currently only valid at European level, but should soon be extended to other geographical areas such as the USA.

[0013] Air conditioning circuit elements, and in particular multi-layer tubular structures, must also:

[0014] - be impermeable to the fluids transported and therefore have barrier properties with respect to these fluids (and in particular to fluorocarbon refrigerant compounds such as R134, R-1234yf or R-1234ze), as well as to water and oxygen. The term barrier properties means that the structure is almost impermeable to the fluids in automotive air conditioning lines and therefore allows almost no emission of air conditioning line fluids into the atmosphere. - have chemical resistance to the fluids transported, as well as to compressor oils, water and oxygen, in order to avoid excessive degradation over the long term;

[0015] - not only have sufficient mechanical strength (in particular burst strength) but also sufficient flexibility in the case where the two ends of the tube are connected to parts that can move relative to each other (in particular in automotive air conditioning, where the constraints of size and mounting under the hood require the tubular structures to be bent) and allow vibration damping;

[0016] - have satisfactory thermal resistance, taking into account that the fluids transported may be at a high temperature, and that the temperature of the environment may also be high (in particular in automotive air conditioning, the parts concerned may be located near the engine) and in particular ZnCI2.

[0017] Current lines consist of one part in aluminum, and another in rubber with reinforcing braid and barrier layer.

[0018] Thermoplastic tubular solutions are therefore being considered to replace current lines in order to reduce the weight of vehicles.

[0019] Thus, international application WO2020 / 1 15420 describes, among other things, a multi-layer tubular structure of aliphatic polyamides for the transport of refrigerant fluid.

[0020] International application WO2017 / 103466 describes multi-layer tubular structures for transporting refrigerant. The mechanical properties are provided by a layer consisting of a mixture of semi-crystalline thermoplastic and continuous fibers.

[0021] International application WO2014 / 125219 describes tubular structures comprising at least one layer consisting of a composition comprising a copolyamide of formula X / 10.T / Y. The proportion of X units being from 0.4 to 0.8 mole per one mole of semi-aromatic units 10.Y

[0022] Hutchinson also marketed air conditioning lines made of an alloy of PA6 and PA66, but these lines encountered significant problems, in particular excessive water permeability which led to corrosion of the compressors.

[0023] Tl Fluid Systems has also developed a solution consisting of a layer of PA612 and a layer of PA11 / 10T in-house.

[0024] Evonik offers PA610 and PA612 grades for making single-layer air conditioning lines.

[0025] Apart from the transport of refrigerant, patents EP2098580, EP2098365, WO 2014 / 114766, WO 2017 / 121961 describe thermoplastic tubular structures for the transport of gasoline and in particular alcoholic gasoline. However, none of these technical solutions meet all the needs expressed by car manufacturers.

[0026] The present invention therefore relates to a multi-layer tubular structure (MLT) intended for the transport of a heat transfer fluid, said multi-layer tubular structure comprising:

[0027] - at least one layer (1) comprising a composition (1) comprising predominantly at least one long-chain polyamide (PA) having from 10 to 15 carbon atoms per nitrogen atom and comprising at least 50% of aliphatic units relative to the sum of the units present in said long-chain polyamide,

[0028] - at least one layer (2) located below said layer (1) comprising a composition (2) predominantly comprising at least one polyamide having from 4 to 9 carbon atoms per nitrogen atom, said polyamide comprising at least 50% of aliphatic units relative to the sum of the units present in said polyamide, in particular said composition (2) comprising up to 12% by weight of polyolefins, in particular up to 6% by weight of polyolefin, relative to the total weight of said composition (2), and up to 2% by weight of at least one plasticizer relative to the total weight of said composition (2),

[0029] - at least one layer (3) comprising a composition (3) mainly comprising a hydrophobic polymer, in particular a polypropylene or a polyethylene, in particular said layer (3) being located below said layer (2) or between said layer (1) and said layer (2),

[0030] - a layer (4) comprising either a composition (4) comprising a PA6, a PA66 or a mixture thereof, from 5 to 50% by weight of at least one polyolefin, in particular functionalized, preferably from 10 to 40% by weight of at least one polyolefin, up to 2% by weight of at least one plasticizer and up to 2% by weight of an additive relative to the total weight of said composition (4) or a composition (4') comprising predominantly at least one C8-C14 aliphatic polyamide, said layer (4) in contact with said transported fluid, and the thickness of said layer(s) (2) representing at least 70% of the total thickness of the tube.

[0031] The inventors therefore unexpectedly found that the multilayer tubular structure of the invention comprising at least four layers made it possible to meet all the needs expressed by automobile manufacturers, namely barrier properties to the refrigerant fluid and in particular to R1234yf provided by a PA6 modified with a polyolefin or a PA having from eight to fourteen carbon atoms per nitrogen atom), low water permeability properties provided by the hydrophobic polymer whereas the PAs have a water permeability which is too high compared to the requirements of the application,hot bursting resistance properties provided by short and medium chain PAs (four to nine carbon atoms per nitrogen atom) and which allow a compromise between weight and mechanical performance to be obtained and finally ZnCl2 resistance properties provided by long chain PAs in the external layer and which ensure good resistance to stress cracking.,

[0032] According to one embodiment, the multilayer tubular structures of the invention advantageously have barrier properties to the refrigerant fluid and in particular to R1234yf meeting classification C according to the GMW 14319 standard.

[0033] According to one embodiment, the multilayer tubular structures of the invention advantageously have resistance to zinc chloride corresponding to classification 1 (the external surface of the tubes is intact (no cracks) and the burst pressure is unchanged) according to the protocol described in the examples.

[0034] According to one embodiment, the multilayer tubular structures of the invention advantageously have a bursting stress at 125°C greater than or equal to 12MPa according to DIN 53758 SAE J3062, as described in the examples.

[0035] According to one embodiment, the multilayer tubular structures of the invention advantageously have a water permeability of less than 23 g / m2.24h according to the material test method D45 1720 PSA PEUGEOT CITROEN as described in the examples.

[0036] Regarding layer (1) and composition (1):

[0037] The expression “comprising predominantly at least one polyamide…” means that the polyamide(s) is(are) present in the composition (1) in a proportion by weight greater than 50% relative to the total weight of the composition.

[0038] The term polyamide refers to both homopolyamide and copolyamide.

[0039] The nomenclature used to define polyamides is described in ISO 1874-1:2011 "Plastics - Polyamide (PA) materials for molding and extrusion - Part 1: Designation", particularly on page 3 (tables 1 and 2) and is well known to those skilled in the art. Homopolyamide can be obtained from the polycondensation of lactam units, amino acid units or XY units, X being a diamine and Y a dicarboxylic acid (or diacid), provided that the homopolyamide has 10 to 15 carbon atoms per nitrogen atom.

[0040] The diamine can be linear or branched aliphatic, or cycloaliphatic, preferably it is linear or branched aliphatic, in particular linear.

[0041] The dicarboxylic acid can be aliphatic or cycloaliphatic, preferably aliphatic. Therefore, the lactams and amino acids used to obtain homopolyamides must have an average number of carbon atoms (C) per nitrogen atom (N) of 10 to 15.

[0042] Advantageously, the lactams and amino acids are C11 and C12.

[0043] In the case of homopolyamides obtained from the polycondensation of XY units, the number of atoms per nitrogen atom is calculated by the average of the numbers of carbon atoms present in the unit resulting from diamine X and in the unit resulting from diacid Y.

[0044] Therefore, the diamine (X) may be C4 to C36, in particular C6 to C18, in particular C4 to C12 and the dicarboxylic acid (Y) may be C4 to C36, in particular C6 to C18, in particular C6 to C12, provided that the average number of carbon atoms present in the unit derived from the diamine X and in the unit derived from the diacid Y is from 10 to 15. Advantageously, the diamine is chosen from 2-methyl-1,5-pentanediamine, 1,6-hexamethylenediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4- trimethylhexamethylenediamine, 1,10-decanediamine, 1,11-undecanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,16-hexadecanediamine and 1,18-octadecanediamine.

[0045] Advantageously, the diamine is chosen from 1,10-decanediamine and 1,12-dodecanediamine.

[0046] Advantageously, the dicarboxylic acid is chosen from sebacic acid and dodecanedioic acid.

[0047] Advantageously, the diamine is chosen from 1,10-decanediamine and 1,12-dodecanediamine and the dicarboxylic acid is chosen from sebacic acid, undecanedioic acid and dodecanedioic acid.

[0048] In the case of copolyamides, the number of carbon atoms per nitrogen atom is calculated according to the same principle as for a homopolyamide. The calculation is carried out in molar proportion to the different amide units.

[0049] Therefore, the lactams and amino acids used to obtain the copolyamides can have an average number of carbon atoms (C) per nitrogen atom (N) ranging from 6 to 15.

[0050] The diamines X and diacids Y used in the copolyamides may be aromatic diamines and / or diacids provided that said polyamide of composition (1) comprises at least 50% of aliphatic units relative to the sum of the units present in said polyamide. In one embodiment, said at least one polyamide of composition (1) comprises at least 60% of aliphatic units relative to the sum of the units present in said polyamide.

[0051] In another embodiment, said at least one polyamide of composition (1) comprises at least 70% of aliphatic units relative to the sum of the units present in said polyamide.

[0052] In another embodiment, said at least one polyamide of composition (1) comprises at least 80% of aliphatic units relative to the sum of the units present in said polyamide.

[0053] In another embodiment, said at least one polyamide of composition (1) comprises at least 90% of aliphatic units relative to the sum of the units present in said polyamide.

[0054] In another embodiment, said at least one polyamide of composition (1) comprises 100% of aliphatic units relative to the sum of the units present in said polyamide.

[0055] Advantageously, said at least one polyamide of composition (1) consists solely of aliphatic units.

[0056] In one embodiment, said composition (1) mainly comprises a single polyamide and therefore said single polyamide is present in the composition in a proportion by weight greater than 50% relative to the total weight of the composition.

[0057] In one embodiment, said polyamide of composition (1) comprises at least 60% of aliphatic units relative to the sum of the units present in said polyamide.

[0058] In another embodiment, said polyamide of composition (1) comprises at least 70% of aliphatic units relative to the sum of the units present in said polyamide. In another embodiment, said polyamide of composition (1) comprises at least 80% of aliphatic units relative to the sum of the units present in said polyamide. In another embodiment, said polyamide of composition (1) comprises at least 90% of aliphatic units relative to the sum of the units present in said polyamide. In another embodiment, said polyamide of composition (1) comprises 100% of aliphatic units relative to the sum of the units present in said polyamide. Said polyamide of composition (1) therefore consists solely of aliphatic units.

[0059] In one embodiment, said layer (1) consists of a composition (1) comprising predominantly at least one long-chain polyamide having from 10 to 15 carbon atoms per nitrogen atom and comprising at least 50% of aliphatic units relative to the sum of the units present in said long-chain polyamide. In one embodiment, said at least one polyamide of the composition (1) comprises at least 60% of aliphatic units relative to the sum of the units present in said polyamide.

[0060] In another embodiment, said at least one polyamide of composition (1) comprises at least 70% of aliphatic units relative to the sum of the units present in said polyamide.

[0061] In another embodiment, said at least one polyamide of composition (1) comprises at least 80% of aliphatic units relative to the sum of the units present in said polyamide.

[0062] In another embodiment, said at least one polyamide of composition (1) comprises at least 90% of aliphatic units relative to the sum of the units present in said polyamide.

[0063] In another embodiment, said at least one polyamide of composition (1) comprises 100% aliphatic units relative to the sum of the units present in said polyamide. Said polyamide is therefore made up solely of aliphatic units.

[0064] In one embodiment, said layer (1) consists of a composition (1) comprising mainly a single polyamide and therefore said single polyamide is present in the composition in a proportion by weight greater than 50% relative to the total weight of the composition.

[0065] In one embodiment, said polyamide of composition (1) comprises at least 60% of aliphatic units relative to the sum of the units present in said polyamide.

[0066] In another embodiment, said polyamide of composition (1) comprises at least 70% of aliphatic units relative to the sum of the units present in said polyamide. In another embodiment, said polyamide of composition (1) comprises at least 80% of aliphatic units relative to the sum of the units present in said polyamide. In another embodiment, said polyamide of composition (1) comprises at least 90% of aliphatic units relative to the sum of the units present in said polyamide. In another embodiment, said polyamide of composition (1) comprises 100% of aliphatic units relative to the sum of the units present in said polyamide. Said polyamide of composition (1) therefore consists solely of aliphatic units.

[0067] Advantageously, in all the embodiments defined above for the composition (1) of the layer (1), the lactam is chosen from lauryllactam, the amino acid is chosen from aminoundecanoic acid, the diamine is chosen from 1,8-octanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 1,10-decanediamine, 1,11-undecanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,12-dodecanediamine and the dicarboxylic acid is chosen from suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid.

[0068] More preferably, the lactam is lauryllactam, the amino acid is aminoundecanoic acid, the diamine is selected from 1,10-decanediamine and 1,12-dodecanediamine and the dicarboxylic acid is selected from sebacic acid and dodecanedioic acid.

[0069] Said composition (1) may also comprise at least one polyolefin.

[0070] Said composition (1) can therefore comprise, in addition to said at least one polyamide, at least one polyolefin.

[0071] The polyolefin may be functionalized or non-functionalized or be a mixture of at least one functionalized and / or at least one non-functionalized. For simplicity, the polyolefin has been designated (B) and functionalized polyolefins (B1) and non-functionalized polyolefins (B2) have been described below.

[0072] A non-functionalized polyolefin (B2) is typically a homopolymer or copolymer of alpha olefins or diolefins, such as, for example, ethylene, propylene, butene-1, octene-1, butadiene. Examples include:

[0073] - homopolymers and copolymers of polyethylene, in particular LDPE, HDPE, PE-RT LLDPE (linear low density polyethylene), VLDPE (very low density polyethylene) and metallocene polyethylene.

[0074] - homopolymers or copolymers of propylene.

[0075] - ethylene / alpha-olefin copolymers such as ethylene / propylene, EPR (abbreviation of ethylene-propylene-rubber) and ethylene / propylene / diene (EPDM).

[0076] - styrene / ethylene-butene / styrene (SEBS), styrene / butadiene / styrene (SBS), styrene / isoprene / styrene (SIS), styrene / ethylene-propylene / styrene (SEPS) block copolymers.

[0077] - copolymers of ethylene with at least one product chosen from salts or esters of unsaturated carboxylic acids such as alkyl (meth)acrylate (for example methyl acrylate), or vinyl esters of saturated carboxylic acids such as vinyl acetate (EVA), the proportion of comonomer being able to reach 40% by weight.

[0078] The functionalized polyolefin (B1) may be a polymer of alpha olefins having reactive units (the functionalities); such reactive units are acid, anhydride, or epoxy functions. As an example, mention may be made of the preceding polyolefins (B2) grafted or co- or terpolymerized by unsaturated epoxides such as glycidyl (meth)acrylate, or by carboxylic acids or the corresponding salts or esters such as (meth)acrylic acid (the latter being able to be neutralized totally or partially by metals such as Zn, etc.) or by carboxylic acid anhydrides such as maleic anhydride. A functionalized polyolefin is, for example, a PE / EPR blend, the weight ratio of which can vary widely, for example between 40 / 60 and 90 / 10, said blend being co-grafted with an anhydride, in particular maleic anhydride, according to a grafting rate of, for example, 0.01 to 5% by weight.

[0079] The functionalized polyolefin (B1) can be chosen from the following (co)polymers, grafted with maleic anhydride or glycidyl methacrylate, in which the grafting rate is for example from 0.01 to 5% by weight:

[0080] - PE, PP, copolymers of ethylene with propylene, butene, hexene, or octene containing for example 35 to 80% by weight of ethylene;

[0081] - ethylene / alpha-olefin copolymers such as ethylene / propylene, EPR (abbreviation of ethylene-propylene-rubber) and ethylene / propylene / diene (EPDM).

[0082] - styrene / ethylene-butene / styrene (SEBS), styrene / butadiene / styrene (SBS), styrene / isoprene / styrene (SIS), styrene / ethylene-propylene / styrene (SEPS) block copolymers.

[0083] - ethylene and vinyl acetate (EVA) copolymers, containing up to 40% by weight of vinyl acetate;

[0084] - ethylene and alkyl (meth)acrylate copolymers, containing up to 40% by weight of alkyl (meth)acrylate;

[0085] - ethylene vinyl acetate (EVA) and alkyl (meth)acrylate copolymers, containing up to 40% by weight of comonomers.

[0086] The functionalized polyolefin (B1) can also be chosen from ethylene / propylene copolymers with a majority of propylene grafted with maleic anhydride then condensed with mono-amine polyamide (or a polyamide oligomer) (products described in EP-A-0342066).

[0087] The functionalized polyolefin (B1) may also be a co- or terpolymer of at least the following units: (1) ethylene, (2) alkyl (meth)acrylate or saturated carboxylic acid vinyl ester and (3) anhydride such as maleic anhydride or (meth)acrylic acid or epoxy such as glycidyl (meth)acrylate.

[0088] As examples of functionalized polyolefins of the latter type, the following copolymers may be mentioned, where ethylene preferably represents at least 60% by weight and where the ter monomer (the function) represents, for example, from 0.1 to 10% by weight of the copolymer:

[0089] - ethylene / alkyl (meth)acrylate / (meth)acrylic acid or maleic anhydride or glycidyl methacrylate copolymers;

[0090] - ethylene / vinyl acetate / maleic anhydride or glycidyl methacrylate copolymers;

[0091] - ethylene / vinyl acetate or alkyl (meth)acrylate / (meth)acrylic acid or maleic anhydride or glycidyl methacrylate copolymers.

[0092] In the above copolymers, (meth)acrylic acid may be salified with Zn or Li. The term "alkyl (meth)acrylate" in (B1) or (B2) refers to C1-C8 alkyl methacrylates and acrylates, and may be selected from methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, methyl methacrylate and ethyl methacrylate.

[0093] Furthermore, the aforementioned polyolefins (B1) can also be crosslinked by any suitable process or agent (diepoxy, diacid, peroxide, etc.); the term functionalized polyolefin also includes mixtures of the aforementioned polyolefins with a difunctional reagent such as diacid, dianhydride, diepoxy, etc. capable of reacting with them or mixtures of at least two functionalized polyolefins capable of reacting with each other.

[0094] The above-mentioned copolymers, (B1) and (B2), can be copolymerized in a random or block manner and have a linear or branched structure.

[0095] The molecular weight, MFI index, and density of these polyolefins can also vary widely, as those skilled in the art will appreciate. MFI, short for Melt Flow Index, is the melt flow index. It is measured according to ASTM 1238.

[0096] Advantageously, the non-functionalized polyolefins (B2) are chosen from homopolymers or copolymers of polypropylene and any homopolymer of ethylene or copolymer of ethylene and a comonomer of higher alpha olefin type such as butene, hexene, octene or 4-methyl 1-pentene. Examples that may be mentioned are PP, high density PE, medium density PE, linear low density PE, low density PE, very low density PE. These polyethylenes are known to those skilled in the art as being produced according to a “radical” process, according to a “Ziegler” type catalysis or, more recently, according to a so-called “metallocene” catalysis.

[0097] Advantageously, the functionalized polyolefins (B1) 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. Examples of such polymers include terpolymers of ethylene, alkyl acrylate and maleic anhydride or glycidyl methacrylate such as Lotader® (SK functional polymer) or polyolefins grafted with maleic anhydride such as Orevac® (SK functional polymer) from the Applicant as well as terpolymers of ethylene, alkyl acrylate and (meth)acrylic acid. Homopolymers or copolymers of polypropylene grafted with a carboxylic acid anhydride and then condensed with polyamides or monoamine oligomers of polyamide may also be mentioned.

[0098] Advantageously, the polyolefin is an impact modifier. 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 a relative humidity: RH50%, and a Tg of less than 0°C (measured according to the 1 1357-2:2013 standard at the inflection point of the DSC thermogram).

[0099] Advantageously, said composition (1) comprises up to 40% by weight of at least one polyolefin.

[0100] Advantageously, said composition (1) comprises at least 3% by weight of at least one polyolefin, in particular at least 6% by weight of at least one polyolefin, in particular from 6 to 20% by weight, in particular from 10 to 12% by weight of at least one polyolefin, relative to the total weight of said composition (1).

[0101] Said composition (1) may also comprise at least one plasticizer.

[0102] Said composition (1) can therefore comprise, in addition to said at least one polyamide, at least one plasticizer.

[0103] For example, the plasticizers are selected from benzene sulfonamide derivatives, such as n-butyl benzene sulfonamide (BBSA); ethyl toluene sulfonamide or N-cyclohexyl toluene sulfonamide; hydroxybenzoic acid esters, such as ethyl-2-hexyl parahydroxybenzoate and decyl-2-hexyl parahydroxybenzoate; tetrahydrofurfuryl alcohol esters or ethers, such as oligoethyleneoxytetrahydrofurfuryl alcohol; and citric acid or hydroxymalonic acid esters, such as oligoethyleneoxy malonate.

[0104] It would not be outside the scope of the invention to use a mixture of plasticizers.

[0105] Advantageously, said composition (1) comprises up to 8% by weight of at least one plasticizer relative to the weight of said composition (1).

[0106] In another embodiment, said composition (1) is free of plasticizer.

[0107] Said composition (1) may also comprise an additive.

[0108] The additives optionally used in the compositions of the invention are the conventional additives used in polyamides and well known to those skilled in the art and are in particular described in EP 2098580.

[0109] For example, they include an antistatic filler selected from carbon black, graphite, carbon fibers, carbon nanotubes, especially carbon black and carbon nanotubes, an antioxidant, a heat stabilizer, a UV absorber, a light stabilizer, a lubricant, an inorganic filler, a flame retardant, a nucleating agent and a colorant, reinforcing fibers, a wax and mixtures thereof.

[0110] For example, the stabilizer may be a UV stabilizer, an organic stabilizer or more generally a combination of organic stabilizers, such as a phenol-type antioxidant (for example of the type of irganox® 245 or 1098 or 1010 from Ciba-BASF), a phosphite-type antioxidant (for example irgafos® 126 and irgafos® 168 from Ciba-BASF) and possibly other stabilizers such as a HALS, which stands for Hindered Amine Light Stabilizer (for example Tinuvin® 770 from Ciba-BASF), a UV stabilizer (for example Tinuvin® 312 from Ciba) or a phosphorus-based stabilizer. It is also possible to use amine-type antioxidants such as Naugard® 445 from Crompton or polyfunctional stabilizers such as Nylostab® S-EED from Clariant.

[0111] This stabilizer can also be a mineral stabilizer, such as a copper-based stabilizer. Examples of such mineral stabilizers include copper halides and acetates. Alternatively, other metals such as silver may be considered, but these are known to be less effective. These copper-based compounds are typically combined with alkali metal halides, particularly potassium.

[0112] In one embodiment, said composition (1) comprises by weight:

[0113] - 60% to 100% of at least one long-chain C10 to C15 polyamide as defined above;

[0114] - 0 to 30% of at least one polyolefin;

[0115] - 0 to 8% of at least one plasticizer;

[0116] - 0 to 2% of at least one additive, the total being 100% by weight.

[0117] In another embodiment, said composition (1) comprises by weight:

[0118] - 60% to 97% of at least one long-chain C10 to C15 polyamide as defined above;

[0119] - 3 to 30% of at least one polyolefin;

[0120] - 0 to 8% of at least plasticizer;

[0121] - 0 to 2% of at least one additive, the total being 100% by weight.

[0122] In another embodiment, said composition (1) comprises by weight:

[0123] - 70% to 94% of at least one long-chain C10 to C15 polyamide as defined above;

[0124] - 6 to 20% of at least one polyolefin;

[0125] - 0 to 8% of at least plasticizer;

[0126] - 0 to 2% of at least one additive, the total being 100% by weight.

[0127] Advantageously, said composition (1) is free of plasticizer and said composition (1) comprises by weight:

[0128] - 50% to 100% of at least one long-chain C10 to C15 polyamide as defined above;

[0129] - 0 to 40% of at least one polyolefin,

[0130] - from 0 to 8% of a plasticizer,

[0131] - 0 to 2% of at least one additive, the total being 100% by weight.

[0132] More advantageously, said composition (1) comprises by weight: - 60% to 97% of at least one long-chain C10 to C15 polyamide as defined above;

[0133] - 3 to 30% of at least one polyolefin;

[0134] - from 0 to 8% of a plasticizer,

[0135] - 0 to 2% of at least one additive, the total being 100% by weight.

[0136] Even more advantageously, said composition (1) comprises by weight:

[0137] - 70% to 94% of at least one long-chain C10 to C15 polyamide as defined above;

[0138] - 6 to 20% of at least one polyolefin;

[0139] - from 0 to 8% of a plasticizer,

[0140] - 0 to 2% of at least one additive, the total being 100% by weight.

[0141] In particular, said composition (1) comprises by weight:

[0142] - 78% to 90% of at least one long-chain C10 to C15 polyamide as defined above;

[0143] - 10 to 12% of at least one polyolefin;

[0144] - from 0 to 8% of a plasticizer,

[0145] - 0 to 2% of at least one additive, the total being 100% by weight.

[0146] The present invention also covers the different embodiments of the composition (1) in which the term “comprising” is replaced by the term “consisting of”

[0147] It is obvious that the different compositions (1) comprising or not at least one polyolefin and / or at least one plasticizer and / or at least one additive refer to all the embodiments described above.

[0148] In one embodiment, said at least one polyamide of the layer (1) of the tubular structure defined above is chosen from PA11, PA12, PA1010, PA1012, PA1210 and PA1212.

[0149] The layer (1) of the tubular structure defined above may be the outermost layer. Advantageously, said layer (1) of the tubular structure defined above is the outermost layer of said structure.

[0150] Advantageously, said structure (1) comprises a single layer (1).

[0151] Regarding layer (2) and composition (2):

[0152] The expression “comprising predominantly at least one polyamide…” is as defined above for layer (1).

[0153] The term polyamide refers to both homopolyamide and copolyamide in the same way.

[0154] Homopolyamide can be obtained from the polycondensation of lactam units, amino acid units or XY units, X being a diamine and Y a dicarboxylic acid (or diacid), provided that the homopolyamide has 4 to 9 carbon atoms per nitrogen atom.

[0155] The diamine can be linear or branched aliphatic, or cycloaliphatic, preferably it is linear or branched aliphatic, in particular linear.

[0156] The dicarboxylic acid can be aliphatic or cycloaliphatic, preferably it is aliphatic.

[0157] Therefore, the lactams and amino acids used to obtain homopolyamides must have an average number of carbon atoms (C) per nitrogen atom (N) of 4 to 9.

[0158] Advantageously, lactams and amino acids are C6.

[0159] In the case of homopolyamides obtained from the polycondensation of XY units, the number of atoms per nitrogen atom is calculated by the average of the numbers of carbon atoms present in the unit resulting from diamine X and in the unit resulting from diacid Y.

[0160] Therefore, the diamine (X) may be C4 to C14, in particular C4 to C12, in particular C4 to C10 and the dicarboxylic acid (Y) may be C4 to C14, in particular C4 to C12, in particular C4 to C10, provided that the average number of carbon atoms present in the unit derived from the diamine X and in the unit derived from the diacid Y is from 4 to 9. Advantageously, the diamine is chosen from butanediamine, pentanediamine, 2-methyl-1,5-pentanediamine, 1,6-hexamethylenediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 1,10-decanediamine, 1,11-undecanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, especially 1,6-hexamethylenediamine.

[0161] Advantageously, the dicarboxylic acid is chosen from succinic acid, pentanedioic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, in particular sebacic acid and dodecanedioic acid.

[0162] Advantageously, the diamine is chosen from butanediamine, pentanediamine, 2-methyl-1,5-pentanediamine, 1,6-hexamethylenediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 1,10-decanediamine, 1,11-undecanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, in particular 1,6-hexamethylenediamine, and the dicarboxylic acid is selected from succinic acid, pentanedioic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, in particular sebacic acid and dodecanedioic acid.

[0163] The diamines X and diacids Y used in the copolyamides may be aromatic diamines and / or diacids provided that said polyamide of composition (2) comprises at least 50% of aliphatic units relative to the sum of the units present in said polyamide.

[0164] In one embodiment, said at least one polyamide of composition (2) comprises at least 60% of aliphatic units relative to the sum of the units present in said polyamide.

[0165] In another embodiment, said at least one polyamide of composition (2) comprises at least 70% of aliphatic units relative to the sum of the units present in said polyamide.

[0166] In another embodiment, said at least one polyamide of composition (2) comprises at least 80% of aliphatic units relative to the sum of the units present in said polyamide.

[0167] In another embodiment, said at least one polyamide of composition (2) comprises at least 90% of aliphatic units relative to the sum of the units present in said polyamide.

[0168] In another embodiment, said at least one polyamide of the composition (2) comprises 100% aliphatic units relative to the sum of the units present in said polyamide. Said at least one polyamide is therefore made up solely of aliphatic units. In one embodiment, said composition (2) comprises mainly a single polyamide and therefore said single polyamide is present in the composition in a proportion by weight greater than 50% relative to the total weight of the composition.

[0169] In one embodiment, said polyamide of said composition (2) comprises at least 60% of aliphatic units relative to the sum of the units present in said polyamide. In another embodiment, said polyamide of said composition (2) comprises at least 70% of aliphatic units relative to the sum of the units present in said polyamide.

[0170] In another embodiment, said polyamide of said composition (2) comprises at least 80% of aliphatic units relative to the sum of the units present in said polyamide.

[0171] In another embodiment, said polyamide of said composition (2) comprises at least 90% of aliphatic units relative to the sum of the units present in said polyamide. In another embodiment, said polyamide of said composition (2) comprises 100% of aliphatic units relative to the sum of the units present in said polyamide. Said polyamide of said composition (2) is therefore made up solely of aliphatic units.

[0172] In one embodiment, said layer (2) consists of a composition (2) mainly comprising at least one long-chain polyamide having from 4 to 9 carbon atoms per nitrogen atom and comprising at least 50% of aliphatic units relative to the sum of the units present in said long-chain polyamide.

[0173] In one embodiment, said at least one polyamide of said composition (2) comprises at least 60% of aliphatic units relative to the sum of the units present in said polyamide.

[0174] In another embodiment, said at least one polyamide of said composition (2) comprises at least 70% of aliphatic units relative to the sum of the units present in said polyamide.

[0175] In another embodiment, said at least one polyamide of said composition (2) comprises at least 80% of aliphatic units relative to the sum of the units present in said polyamide.

[0176] In another embodiment, said at least one polyamide of said composition (2) comprises at least 90% of aliphatic units relative to the sum of the units present in said polyamide.

[0177] In another embodiment, said at least one polyamide of said composition (2) comprises 100% aliphatic units relative to the sum of the units present in said polyamide. Said polyamide of said composition (2) is therefore made up solely of aliphatic units.

[0178] In one embodiment, said layer (2) consists of a composition (2) comprising mainly a single polyamide and therefore said single polyamide is present in the composition in a proportion by weight greater than 50% relative to the total weight of the composition.

[0179] In one embodiment, said polyamide of said composition (2) comprises at least 60% of aliphatic units relative to the sum of the units present in said polyamide. In another embodiment, said polyamide of said composition (2) comprises at least 70% of aliphatic units relative to the sum of the units present in said polyamide.

[0180] In another embodiment, said polyamide of said composition (2) comprises at least 80% of aliphatic units relative to the sum of the units present in said polyamide. In another embodiment, said polyamide of said composition (2) comprises at least 90% of aliphatic units relative to the sum of the units present in said polyamide.

[0181] In another embodiment, said polyamide of said composition (2) comprises 100% of aliphatic units relative to the sum of the units present in said polyamide. Said polyamide is therefore made up solely of aliphatic units.

[0182] Advantageously, in all the embodiments defined above for the composition (2) of the layer (2), the lactam is caprolactam, the amino acid is aminohexanoic acid, the diamine is chosen from 2-methyl-1,5-pentanediamine, 1,6-hexamethylenediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 1,10-decanediamine and the dicarboxylic acid is chosen from adipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid.

[0183] More preferably, the lactam is caprolactam, the amino acid is aminohexanoic acid, the diamine is selected from 2-methyl-1,5-pentanediamine, 1,6-hexamethylenediamine, 1,10-decanediamine and 1,12-dodecanediamine and the dicarboxylic acid is selected from adipic acid, sebacic acid and dodecanedioic acid. In one embodiment, the lactam is caprolactam, the amino acid is aminohexanoic acid, the diamine is selected from 2-methyl-1,5-pentanediamine, 1,6-hexamethylenediamine, 1,10-decanediamine and 1,12-dodecanediamine and the dicarboxylic acid is selected from adipic acid, sebacic acid and dodecanedioic acid. Advantageously, said polyamide of said composition (2) comprises at least 60% of aliphatic units relative to the sum of the units present in said polyamide.

[0184] More advantageously, said polyamide of said composition (2) comprises at least 60% of aliphatic units relative to the sum of the units present in said polyamide and said long-chain polyamide of said composition (1) comprises at least 60% of aliphatic units relative to the sum of the units present in said long-chain polyamide. Advantageously, said composition (2) is free of polyamide(s) other than aliphatic.

[0185] More advantageously, said polyamide of said composition (2) is made up of aliphatic units.

[0186] In one embodiment, said polyamide of said composition (2) consists of aliphatic units and said long-chain polyamide of said composition (1) consists of aliphatic units. Advantageously, said composition (2) and said composition (1) are free of polyamide(s) other than aliphatic.

[0187] Said composition (2) may also comprise at least one plasticizer in a proportion by weight of up to 2% relative to the total weight of the composition.

[0188] The plasticizer is as defined for composition (1).

[0189] Said composition (2) may also comprise at least one additive.

[0190] In one embodiment, the additive is in a proportion by weight of up to 2% relative to the total weight of the composition.

[0191] The additive is as defined for composition (1).

[0192] In one embodiment, said composition (2) comprises by weight:

[0193] - 84% to 100%, in particular 90% to 100%, of at least one C4 to C9 polyamide as defined above;

[0194] - 0 to 12% of at least one polyolefin, in particular 0 to 6% of at least one polyolefin;

[0195] - 0 to 2% of at least one plasticizer;

[0196] - 0 to 2% of at least one additive, the total being 100% by weight.

[0197] In another embodiment, said composition (2) is free of polyolefin and comprises by weight:

[0198] - 96% to 100% of at least one C4 to C9 polyamide as defined above;

[0199] - 0 to 2% of at least plasticizer;

[0200] - 0 to 2% of at least one additive, the total being 100% by weight.

[0201] Advantageously, said composition (2) is free of plasticizer and said composition (2) comprises by weight:

[0202] - 86% to 100% of at least one C4 to C9 polyamide as defined above, in particular from 92 to 100% by weight;

[0203] - 0 to 12% of at least one polyolefin, in particular 0 to 6% of at least one polyolefin;

[0204] - 0 to 2% of at least one additive, the total being 100% by weight.

[0205] It is obvious that the different compositions (2) comprising or not at least one polyolefin and / or at least one plasticizer and / or at least one additive refer to all the embodiments described above for the composition (2).

[0206] In one embodiment, said at least one polyamide of the layer (2) of the tubular structure defined above is chosen from PA6, PA66, PA6 / 66, PA610, PA410, PA412 and PA612.

[0207] Regarding the layer (3) and the composition (3) Said layer (3) comprising a composition (3) predominantly comprising a hydrophobic polymer, in particular a polypropylene or a polyethylene, in particular said layer (3) being located below said layer (2) or between said layer (1) and said layer (2). This means that the composition (3) comprises more than 50% by weight of hydrophobic polymer, in particular a polypropylene or a polyethylene, relative to its total weight.

[0208] According to one embodiment, the composition (3) may comprise at least 60% by weight, for example at least 70% by weight, for example at least 80% by weight, or even 100% by weight, of hydrophobic polymer, in particular a polypropylene or a polyethylene, relative to its total weight.

[0209] According to one embodiment, the layer (3) mainly comprises a composition (3), that is to say comprises more than 50% by weight, relative to its total weight, of a composition (3).

[0210] According to one embodiment, the layer (3) may comprise at least 60% by weight, for example at least 70% by weight, for example at least 80% by weight, or even 100% by weight, of composition (3).

[0211] The term "hydrophobic polymer" means a polymer that is a barrier or partially a barrier to water. It can be an apolar polymer, a charged polymer in which water diffusion will be slower, for example a polyamide such as PA11 charged with graphene.

[0212] More particularly, a polymer is considered hydrophobic within the meaning of the invention when its solubility coefficient relative to polar interactions (5p) is less than or equal to 5 MPa 1 / 2 and its solubility coefficient relative to hydrogen bonds (5h) is less than or equal to 5 MPa 1 / 2 according to HANSEN solubility parameters (HANSEN SOLUBILITY PARAMETERS - A User's Handbook - Second Edition - Charles M.).

[0213] The hydrophobic polymer may be non-functionalized, as described in (B2) above, or functionalized as described in B1 above.

[0214] In one embodiment, the hydrophobic polymer is selected from polypropylene and polyethylene.

[0215] The solubility coefficient relative to polar interactions (5p) of polypropylene is less than 5 MPa 1 / 2 and its solubility coefficient relative to hydrogen bonds (5h) is less than 5 MPa 1 / 2 according to the HANSEN solubility parameters as defined above. Polypropylene is therefore a hydrophobic polymer within the meaning of the present invention.

[0216] The solubility coefficient relative to polar interactions (5p) of polyethylene is less than 5 MPa 1 / 2 and its solubility coefficient relative to hydrogen bonds (5h) is less than 5 MPa 1 / 2 according to the HANSEN solubility parameters as defined above. Polyethylene is therefore a hydrophobic polymer within the meaning of the present invention.

[0217] Ethylene vinyl alcohol (or EvOH) is not considered a hydrophobic polymer for the purposes of the present invention.

[0218] The solubility coefficient relative to polar interactions (5p) of ethylene vinyl alcohol is greater than 5 MPa 1 / 2 (it is between 10 and 15) and its solubility coefficient relative to hydrogen bonds (5h) is greater than 5 MPa 1 / 2 (it is between 10 and 15) according to the HANSEN solubility parameters as defined previously.

[0219] In another embodiment, said polypropylene or said polyethylene is crosslinked. Advantageously, said hydrophobic polymer of the layer (3) is chosen from a grafted polypropylene, preferably grafted with maleic anhydride, and a grafted high-density polyethylene (HDPE), preferably grafted with maleic anhydride.

[0220] In one embodiment, the MFI of the polypropylene or polyethylene is from 0.5 to 10 g / 10 min.

[0221] MFI, short for Melt Flow Index, is the melt flow index. It is measured according to ASTM 1238 to 230. 0 C under 2.16kg

[0222] Regarding layer (4) and composition (4)

[0223] Said layer (4) is internal and in contact with said transported fluid.

[0224] The layer (4) comprises a composition (4) comprising a PA6, a PA66 or a mixture thereof, from 5 to 50% by weight of at least one polyolefin, in particular functionalized, preferably from 10 to 40% by weight of at least one polyolefin, up to 2% by weight of at least one plasticizer and up to 2% by weight of an additive relative to the total weight of said composition or a composition (4') predominantly comprising at least one polyamide having from 8 to 14 carbon atoms per nitrogen atom and at least 20%, preferably at least 25% by weight of at least one polyolefin relative to the total weight of said composition (4').

[0225] In one embodiment, said composition (4) comprises:

[0226] - from 50 to 95% by weight of PA6, PA66 or a mixture thereof,

[0227] - from 5 to 50% by weight of at least one polyolefin, in particular functionalized, preferably from 10 to 40% by weight

[0228] - from 0 to 2% by weight of at least one plasticizer,

[0229] - from 0 to 2% by weight of at least one additive.

[0230] In another embodiment, said composition (4) comprises:

[0231] - from 60 to 90% of PA6, PA66 or a mixture of these,

[0232] - from 10 to 40% by weight of at least one polyolefin, in particular functionalized, - from 0 to 2% by weight of at least one plasticizer,

[0233] - from 0 to 2% by weight of at least one additive.

[0234] In a variant of these two embodiments, said composition (4) is made up of the elements defined above for these two embodiments.

[0235] The plasticizers and additives of composition (4) are as defined for composition (1)-

[0236] The term polyamide of composition (4') designates in the same way both a homopolyamide and a copolyamide.

[0237] Homopolyamide can be obtained from the polycondensation of lactam units, amino acid units or XY units, X being a diamine and Y a dicarboxylic acid (or diacid), provided that the homopolyamide has 8 to 14 carbon atoms per nitrogen atom.

[0238] The diamine can be linear or branched aliphatic, or cycloaliphatic, preferably it is linear or branched aliphatic, in particular linear.

[0239] The dicarboxylic acid can be aliphatic or cycloaliphatic, preferably it is aliphatic.

[0240] Therefore, the lactams and amino acids used to obtain homopolyamides must have an average number of carbon atoms (C) per nitrogen atom (N) of 8 to 14.

[0241] Advantageously, the lactams and amino acids are C11 and C12.

[0242] In the case of homopolyamides obtained from the polycondensation of XY units, the number of atoms per nitrogen atom is calculated by the average of the numbers of carbon atoms present in the unit resulting from diamine X and in the unit resulting from diacid Y.

[0243] Therefore, the diamine (X) may be C4 to C36, in particular C6 to C18, in particular C4 to C12 and the dicarboxylic acid (Y) may be C4 to C36, in particular C6 to C18, in particular C6 to C12, provided that the average number of carbon atoms present in the unit derived from the diamine X and in the unit derived from the diacid Y is from 10 to 15. Advantageously, the diamine is chosen from 2-methyl-1,5-pentanediamine, 1,6-hexamethylenediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4- trimethylhexamethylenediamine, 1,10-decanediamine, 1,11-undecanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,16-hexadecanediamine and 1,18-octadecanediamine.

[0244] Advantageously, the diamine is chosen from 1,10-decanediamine and 1,12-dodecanediamine. Advantageously, the dicarboxylic acid is chosen from sebacic acid and dodecanedioic acid.

[0245] Advantageously, the diamine is chosen from 1,10-decanediamine and 1,12-dodecanediamine and the dicarboxylic acid is chosen from sebacic acid, undecanedioic acid and dodecanedioic acid.

[0246] In the case of copolyamides, the number of carbon atoms per nitrogen atom is calculated according to the same principle as for a homopolyamide. The calculation is carried out in molar proportion to the different amide units.

[0247] Therefore, the lactams and amino acids used to obtain the copolyamides can have an average number of carbon atoms (C) per nitrogen atom (N) ranging from 6 to 15.

[0248] The diamines X and diacids Y used in the copolyamides may be aromatic diamines and / or diacids provided that said polyamide of composition (4') comprises at least 50% of aliphatic units relative to the sum of the units present in said polyamide.

[0249] In one embodiment, said at least one polyamide of the composition (4') comprises at least 60% of aliphatic units relative to the sum of the units present in said polyamide.

[0250] In another embodiment, said at least one polyamide of the composition (4') comprises at least 70% of aliphatic units relative to the sum of the units present in said polyamide.

[0251] In another embodiment, said at least one polyamide of the composition (4') comprises at least 80% of aliphatic units relative to the sum of the units present in said polyamide.

[0252] In another embodiment, said at least one polyamide of the composition (4') comprises at least 90% of aliphatic units relative to the sum of the units present in said polyamide.

[0253] In another embodiment, said at least one polyamide of the composition (4') comprises 100% aliphatic units relative to the sum of the units present in said polyamide. Said at least one polyamide of the composition (4') is therefore made up solely of aliphatic units.

[0254] In one embodiment, said composition (4') mainly comprises a single polyamide and therefore said single polyamide is present in the composition in a proportion by weight greater than 50% relative to the total weight of the composition.

[0255] In one embodiment, said polyamide of composition (4') comprises at least 60% aliphatic units relative to the sum of the units present in said polyamide. In another embodiment, said polyamide of composition (4') comprises at least 70% aliphatic units relative to the sum of the units present in said polyamide. In another embodiment, said polyamide of composition (4') comprises at least 80% aliphatic units relative to the sum of the units present in said polyamide. In another embodiment, said polyamide of composition (4') comprises at least 90% aliphatic units relative to the sum of the units present in said polyamide. In another embodiment, said polyamide of composition (4') comprises 100% aliphatic units relative to the sum of the units present in said polyamide. Said polyamide of composition (4') therefore consists solely of aliphatic units.

[0256] In one embodiment, said layer (4) consists of a composition (4') mainly comprising at least one long-chain polyamide having from 8 to 14 carbon atoms per nitrogen atom and comprising at least 50% of aliphatic units relative to the sum of the units present in said long-chain polyamide.

[0257] In one embodiment, said at least one polyamide of the composition (4') comprises at least 60% of aliphatic units relative to the sum of the units present in said polyamide.

[0258] In another embodiment, said at least one polyamide of the composition (4') comprises at least 70% of aliphatic units relative to the sum of the units present in said polyamide.

[0259] In another embodiment, said at least one polyamide of the composition (4') comprises at least 80% of aliphatic units relative to the sum of the units present in said polyamide.

[0260] In another embodiment, said at least one polyamide of the composition (4') comprises at least 90% of aliphatic units relative to the sum of the units present in said polyamide.

[0261] In another embodiment, said at least one polyamide of the composition (4') comprises 100% aliphatic units relative to the sum of the units present in said polyamide. Said polyamide is therefore made up solely of aliphatic units.

[0262] In one embodiment, said layer (4) consists of a composition (4') comprising mainly a single polyamide and therefore said single polyamide is present in the composition in a proportion by weight greater than 50% relative to the total weight of the composition.

[0263] In one embodiment, said polyamide of composition (4') comprises at least 60% of aliphatic units relative to the sum of the units present in said polyamide.

[0264] In another embodiment, said polyamide of composition (4') comprises at least 70% of aliphatic units relative to the sum of the units present in said polyamide. In another embodiment, said polyamide of composition (4') comprises at least 80% of aliphatic units relative to the sum of the units present in said polyamide. In another embodiment, said polyamide of composition (4') comprises at least 90% of aliphatic units relative to the sum of the units present in said polyamide. In another embodiment, said polyamide of composition (4') comprises 100% of aliphatic units relative to the sum of the units present in said polyamide. Said polyamide of composition (1) therefore consists solely of aliphatic units.

[0265] Advantageously, in all the embodiments defined above for the composition (4') of the layer (4), the lactam is chosen from lauryllactam, the amino acid is chosen from aminoundecanoic acid, the diamine is chosen from 1,8-octanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 1,10-decanediamine, 1,11-undecanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,12-dodecanediamine and the dicarboxylic acid is chosen from suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid.

[0266] More preferably, the lactam is lauryllactam, the amino acid is aminoundecanoic acid, the diamine is selected from 1,10-decanediamine and 1,12-dodecanediamine and the dicarboxylic acid is selected from sebacic acid and dodecanedioic acid.

[0267] Said composition (4') of the layer (4) comprises at least 20% by weight, preferably at least 25% by weight of at least one polyolefin.

[0268] The polyolefin is as defined for composition (1).

[0269] Said composition (4') may also comprise at least one plasticizer and / or at least one additive.

[0270] The plasticizer and additive are as defined above.

[0271] In one embodiment, said composition (4') comprises by weight:

[0272] - 54% to 80% of at least one C8 to C14 polyamide as defined above, in particular 54% to 75%;

[0273] - 20 to 40%, preferably 25 to 40% of at least one polyolefin;

[0274] - 0 to 4% of at least plasticizer;

[0275] - 0 to 2% of at least one additive, the total being 100% by weight.

[0276] The plasticizers and additives of composition (4') are as defined for composition (1)-

[0277] Tubular structure: The tubular structure may comprise at least one layer (1), at least one layer (2), at least one layer (3) and an inner layer (4).

[0278] The present invention also relates to a multi-layer tubular structure (MLT) intended for the transport of a heat transfer fluid, said multi-layer tubular structure comprising:

[0279] - at least one layer 1 comprising a composition 1 comprising predominantly at least one long-chain polyamide (PA) having from 10 to 15 carbon atoms per nitrogen atom and comprising at least 50% of aliphatic units relative to the sum of the units present in said long-chain polyamide,

[0280] - at least one layer 2 located below said layer 1 comprising a composition 2 comprising predominantly at least one polyamide having from 4 to 9 carbon atoms per nitrogen atom, said polyamide comprising at least 50% of aliphatic units relative to the sum of the units present in said polyamide, in particular said composition 2 comprising up to 12% by weight of polyolefins, in particular up to 6% by weight of polyolefin, relative to the total weight of said composition 2, and up to 2% by weight of at least one plasticizer relative to the total weight of said composition 2,

[0281] - at least one layer 3 comprising a composition 3 comprising mainly a hydrophobic polymer, in particular a polypropylene or a polyethylene, in particular said layer 3 being located below said layer 2 or between said layer 1 and said layer 2,

[0282] - a layer 4 comprising either a composition 4 comprising a PA6, a PA66 or a mixture thereof, from 5 to 50% by weight of at least one polyolefin, in particular functionalized, preferably from 10 to 40% by weight of at least one polyolefin, up to 2% by weight of at least one plasticizer and up to 2% by weight of an additive relative to the total weight of said composition 4 or a composition 4' comprising predominantly at least one C8-C14 aliphatic polyamide, said layer 4 in contact with said transported fluid,

[0283] - a layer 5 being present between said layer 3 and said layer 4, said layer 5 comprising a composition 2 and the thicknesses of said layer(s) 2 and 5 representing at least 70% of the total thickness of the tube.

[0284] In one embodiment, the thickness of said layer (2) represents in particular up to 90% of the total thickness of the tube, in particular up to 80% of the total thickness of the tube.

[0285] In one embodiment, said multilayer tubular structure as defined above is characterized in that said layer (2) is free of plasticizer. In another embodiment, said multilayer tubular structure as defined above is characterized in that said layer (2) and said layer (1) are free of plasticizer.

[0286] In yet another embodiment, said multilayer tubular structure as defined above is characterized in that all the layers present in said structure are free of plasticizer.

[0287] In one embodiment, said structure comprises a layer (5) between said layer (3) and said layer (4), said layer (5) comprising a composition (2) and the thicknesses of said layer(s) (2) and (5) representing at least 80% of the total thickness of the tube.

[0288] Layers (2) and (5) can be the same or different.

[0289] In one embodiment, said multilayer tubular structure defined above is characterized in that said layer (1) is the outermost layer of said multilayer tubular structure.

[0290] According to a first variant, said tubular structure is characterized in that it consists of four layers (1) / / (2) / / (3) / / (4) or (1) / / (3) / / (2) / / (4).

[0291] According to a second variant, said tubular structure is characterized in that it consists of five layers (1 ) / / (2) / / (3) / / (5) / / (4) or (1 ) / / (3) / / (2) / / (5) / / (4).

[0292] In one embodiment, the multilayer tubular structure as defined above is characterized in that the heat transfer fluid is a refrigerant chosen from hydrocarbon compounds, hydrofluorocarbons, ethers, hydrofluoroethers, CO2, NH3, SO2 and fluoroolefins.

[0293] In one embodiment, the heat transfer fluid is a refrigerant selected from CO2, fluoropropenes, fluoropropanes and fluoroethanes; preferably from 1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, 1,2,3,3,3-pentafluoropropene, 1,1,3,3-tetrafluoropropene, 3,3,3-trifluoropropene, 2,3,3-trifluoropropene, 1,1,1,2-tetrafluoroethane, 1,1,2,2-tetrafluoroethane, pentafluoroethane, difluoromethane, 1,1-difluoroethane, 1,1,1,2,3,3,3-heptafluoropropane, 1,1,1,trifluoropropane, 1,1,1,3,3,3-hexafluoropropane, 1,1,1,3,3-pentafluoropropane, 1,1,1,3,3-pentafluorobutane, trifluoroiodomethane and mixtures thereof.

[0294] In one embodiment, the heat transfer fluid is a refrigerant selected from 1,3,3,3-tetrafluoropropene (1234ze) and 2,3,3,3-tetrafluoropropene (1234yf), in particular the heat transfer fluid is 2,3,3,3-tetrafluoropropene (1234yf).

[0295] Advantageously, the refrigerant fluid contains a lubricant, preferably chosen from mineral oils, silicone oils, paraffins of natural origin, naphthenes, synthetic paraffins, alkylbenzenes, poly-alpha olefins, polyalkylene glycols, polyol esters and / or polyvinyl ethers; the lubricant being more particularly preferably a polyalkylene glycol or a polyol ester.

[0296] According to another aspect, the present invention relates to the use of a multilayer tubular structure as defined above, for the transport of a heat transfer fluid, in particular a refrigerant chosen from hydrocarbon compounds, hydrofluorocarbons, ethers, hydrofluoroethers, CO2, NH3, SO2 and fluoroolefins, in particular R134, R-1234yf or R-1234ze, in particular R-1234yf or R-1234ze in the field of automotive air conditioning.

[0297] According to yet another aspect, the present invention relates to the use of a multilayer tubular structure as defined above, to satisfy an extractables test, said test consisting in particular of filling said multilayer tubular structure MLT with forane and heating the assembly to 60°C for 96 hours, then emptying it by filtering it into a beaker, then allowing the filtrate from the beaker to evaporate at room temperature to finally weigh this residue, the proportion of which must be less than or equal to approximately 6g / m2 of internal tube surface and the proportion of residue on the filter after filtration being less than or equal to 1 g / m 2 , preferably less than or equal to 0.5 g / m 2 .

[0298] In other words, the present invention relates to the use of a multilayer tubular structure as defined above, to reduce the proportion of soluble and insoluble compound released by a tubular structure, as defined above, after contacting said multilayer tubular structure MLT with forane, said proportion of compound released being determined by an extractables test, said test consisting in particular of filling said multilayer tubular structure MLT with forane and heating the assembly to 60°C for 96 hours, then emptying it by filtering it into a beaker, then allowing the filtrate from the beaker to evaporate at room temperature to finally weigh this residue, the proportion of which must be less than or equal to approximately 6 g / m2 of internal tube surface and the proportion of residue on the filter after filtration being less than or equal to 1 g / m 2 , preferably less than or equal to 0.5 g / m 2 .

[0299] Said tubular structure therefore makes it possible to reduce the proportion of soluble and insoluble compound after contact with the forane compared to the structures of the prior art.

[0300] EXAMPLES

[0301] The present invention will now be illustrated by means of examples without being limited to them.

[0302] The following structures were prepared by extrusion: 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.

[0303] The screws used are single-screw extrusions with screw profiles adapted to polyamides. In addition to the 5 extruders and the multi-layer extrusion head, the extrusion line includes: a die-punch assembly, located at the end of the co-extrusion head; the inner diameter of the die and the outer diameter of the punch are chosen according to the structure to be produced and the materials that 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 8.8 to 11 mm for a tube with an internal diameter of 6 mm and a thickness of 1.3 mm; a succession of cooling tanks in which water is maintained at around 20°C, allowing the tube to be cooled along the route from the head to the drawing bench; a diameter gauge; a drawing bench.

[0304] The 5-extruder configuration is used to produce tubes ranging from 2 layers to 5 layers. For structures with fewer than 5 layers, multiple extruders are fed with the same material.

[0305] In the case of structures with 6 layers, an additional extruder is connected and a spiral mandrel is added to the existing head, in order to create the internal layer, in contact with the fluid.

[0306] 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 content before extrusion of less than 0.08%. Otherwise, an additional step of drying the material is carried out before testing, generally in a vacuum dryer, for 1 night at 80°C.

[0307] The tubes, which meet the characteristics described in this patent application, were taken after stabilization of the extrusion parameters, the target tube dimensions no longer changing over time. The diameter is controlled by a laser diameter meter installed at the end of the line.

[0308] Generally, the line speed is typically 20m / min. It generally varies between 5 and 100m / min.

[0309] 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. Generally, the temperatures of the extruders and the tools (head and connector) must be adjusted so as to be sufficiently higher than the melting temperature of the compositions in question, so that they remain in the molten state, thus preventing them from solidifying and blocking the machine.

[0310] Tubular structures with the following polymers:

[0311] P1: PA6 + 35% by weight of Orevac® IM 800 (HDPE modified maleic anhydride (SK Functional Polymer))

[0312] P2: PA1 1 Rilsan® BESN Black TL P024 (Arkema)

[0313] P3: PA612 + 20% by weight of Orevac® IM 800 (HDPE modified maleic anhydride (SK Functional Polymer))

[0314] P4: PP-g-MAH (maleic anhydride grafted polypropylene) Admer QB509E (Mitsui)

[0315] P5: HDPE-g-MAH (maleic anhydride grafted high-density polyethylene) obtained by making a mixture of 93% by weight of XRT70 PERT Type II (Total Energy) and 7% by weight of Orevac OE25 (SK Functional Polymers)

[0316] P6: EVOH Eval 171 B (Kuraray)

[0317] P7: PA6 + 10% by weight of Orevac ® IM 800 (HDPE modified maleic anhydride (SK Functional Polymer)) were tested on different parameters presented in Table 1.

[0318] [Table 1] CE 1 to 7: Counter examples

[0319] The counterexamples either have excessive water permeability, i.e. have a flow greater than or equal to 23 g / m 2.24h, either a bursting stress that is too low, i.e. a stress lower than 12 MPa, or are not barriers to the R1234yf flow, i.e. have a classification A or B, or have low resistance to contact with Zinc Chloride, i.e. have a classification 2 or 3.

[0320] EU to EI4: Example according to the invention

[0321] Only the four-layer structures according to the invention present a good compromise on the four evaluated criteria such as burst pressure greater than 12MPa, barrier properties to air conditioning fluid (R1234yf) (classification C), resistance to zinc chloride (classification 1) and water permeability with a flow lower than 23 g / m2.24h compared to the counter-examples which do not allow to combine good performances on the 4 evaluation criteria. The tests used are detailed in Table 2.

[0322] [Table 2]

Claims

CLAIMS Multilayer tubular structure (MLT) intended for the transport of a heat transfer fluid, said multilayer tubular structure comprising: - at least one layer (1) comprising a composition (1) predominantly comprising at least one long-chain polyamide (PA) having 10 to 15 carbon atoms per nitrogen atom and comprising at least 50% aliphatic motifs relative to the sum of motifs present in said long-chain polyamide, - at least one layer (2) situated below said layer (1) comprising a composition (2) predominantly comprising at least one polyamide having 4 to 9 carbon atoms per nitrogen atom, said polyamide comprising at least 50% aliphatic motifs relative to the sum of motifs present in said polyamide, in particular said composition (2) comprising up to 12% by weight of polyolefins, in particular up to 6% by weight of polyolefin, relative to the total weight of said composition (2), and up to 2% by weight of at least one plasticizer relative to the total weight of said composition (2), - at least one layer (3) comprising a composition (3) predominantly comprising a hydrophobic polymer, in particular a polypropylene or a polyethylene, in particular said layer (3) being situated below said layer (2) or between said layer (1) and said layer (2), - a layer (4) comprising either a composition (4) comprising a PA6, a PA66 or a mixture thereof, of 5 to 50% by weight of at least one polyolefin, in particular functionalized, preferably of 10 to 40% by weight of at least one polyolefin, up to 2% by weight of at least one plasticizer and up to 2% by weight of an additive relative to the total weight of said composition (4) or a composition (4') comprising predominantly at least one C8-C14 aliphatic polyamide, said layer (4) in contact with said transported fluid, and the thickness of said layer(s) (2) representing at least 70% of the total thickness of the tube. Multilayer tubular structure according to claim 1, characterized in that a layer (5) is present between said layer (3) and said layer (4), said layer (5) comprising a composition (2) and the thicknesses of said layer(s) (2) and (5) representing at least 80% of the total thickness of the tube. A multilayer tubular structure according to claim 1 or 2, characterized in that said layer (1) is the outermost layer of said multilayer tubular structure. A multilayer tubular structure according to any one of claims 1 to 3, characterized in that said composition (1) comprises up to 40% by weight of at least one polyolefin. A multilayer tubular structure according to any one of claims 1 to 4, characterized in that said composition (1) comprises at least 3% by weight of at least one polyolefin, in particular at least 6% by weight of at least one polyolefin, in particular 10 to 12% by weight of at least one polyolefin, relative to the total weight of said composition (1). A multilayer tubular structure according to any one of claims 1 to 5, said composition (1) comprising up to 8% by weight of at least one plasticizer relative to the weight of said composition (1), in particular layer (1) being free of plasticizer.A multilayer tubular structure according to any one of claims 1 to 6, characterized in that the heat transfer fluid is a refrigerant selected from hydrocarbon compounds, hydrofluorocarbons, ethers, hydrofluoroethers, CO2, NH3, SO2, and fluoroolefins. A multilayer tubular structure according to claim 7, characterized in that the heat transfer fluid is a refrigerant selected from CO2, fluoropropenes, fluoropropanes, and fluoroethanes; preferably from the. 1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, 1,2,3,3,3-pentafluoropropene, 1,1,3,3-tetrafluoropropene, 3,3,3-trifluoropropene, 2,3,3-trifluoropropene, 1,1,1,2-tetrafluoroethane, 1,1,2,2-tetrafluoroethane, pentafluoroethane, difluoromethane, 1,1-difluoroethane, 1,1,1,2,3,3,3-heptafluoropropane, 1,1,1-trifluoropropane, 1,1,1,3,3,3-hexafluoropropane, 1.1.1.3.3-pentafluoropropane, 1,1,1,3,3-pentafluorobutane, trifluoroiodomethane and mixtures comprising these. Multilayer tubular structure according to claim 7 or 8, characterized in that the heat transfer fluid is a refrigerant selected from the 1,3,3,3-tetrafluoropropene (1234ze) and 2,3,3,3-tetrafluoropropene (1234yf), in particular the heat transfer fluid is 2,3,3,3-tetrafluoropropene (1234yf). Multilayer tubular structure according to any one of claims 7 to 9, characterized in that the refrigerant contains a lubricant, preferably selected from mineral oils, silicone oils, natural paraffins, naphthenes, synthetic paraffins, alkylbenzenes, poly-alpha olefins, polyalkylene glycols, polyol esters and / or polyvinyl ethers; the lubricant being more particularly preferably a polyalkylene glycol or a polyol ester. Multilayer tubular structure according to any one of claims 1 to 10, characterized in that said at least one polyamide of the layer (1) is selected from PA11, PA12, PA1010, PA1210 and PA1212.A multilayer tubular structure according to any one of claims 1 to 11, characterized in that said at least one polyamide of layer (2) is selected from PA6, PA66, PA6 / 66, PA610, PA410, PA412, and PA612. A multilayer tubular structure according to any one of claims 1 to 12, characterized in that said at least one hydrophobic polymer of layer (3) is selected from a grafted polypropylene, preferably grafted maleic anhydride, and a grafted high-density polyethylene (HDPE), preferably grafted maleic anhydride. A multilayer tubular structure according to any one of claims 1 to 13, characterized in that it consists of four layers (1) / (2) / (3) / (4) or (1) / (3) / (2) / (4). Multilayer tubular structure according to any one of claims 1 to 13, characterized in that it consists of five layers (1 ) / / (2) / / (3) / / (5) / / (4) or (1 ) / / (3) / / (2) / / (5) / / (4).Use of a multilayer tubular structure as defined in any one of claims 1 to 15, for the transport of a heat transfer fluid, in particular a refrigerant selected from hydrocarbon compounds, hydrofluorocarbons, ethers, hydrofluoroethers, CO2, NH3, SO2 and fluoroolefins. in particular R134a, R-1234yf or R-1234ze, especially R-1234yf or R-1234ze in the field of automotive air conditioning. Use of a multilayer tubular structure according to any one of claims 1 to 15, to satisfy an extractables test, said test consisting in particular of filling said MLT multilayer tubular structure with forane and heating the assembly at 60 °C for 96 hours, then emptying it by filtering it into a beaker, then allowing the filtrate from the beaker to evaporate at room temperature and finally weighing this residue, the proportion of which must be less than or equal to approximately 6 g / m² of internal tube surface area and the proportion of residue on the filter after filtration being less than or equal to 1 g / m² 2 , preferably less than or equal to 0.5 g / m³ 2 .

Images