FR2876771A1 - Multi-layer tube, useful for the transport of gasoline, comprises: an external polyamide layer; and an interior layer of a composition - Google Patents

Abstract

Multi-layer tube (I) comprises: an external polyamide layer (Ia); and an interior layer (Ib) of a composition (comprising: mixture (A) (5-30 wt.%) containing polyethylene carrying epoxy group and an impact modifier (elastomers and very low density polyethylene); and mixture (B) (95-70 wt.%) comprising a fluorinated polymer (1-60 wt.%) and a functionalized fluorinated polymer). Multi-layer tube (I) comprises (radially directed from exterior towards interior): an external polyamide layer (Ia); and an interior layer (Ib) of a composition (comprising: mixture (A) (5-30 wt.%) containing polyethylene carrying epoxy group and an impact modifier (elastomers and very low density polyethylene) (functionalized as whole or part); and mixture (B) (95-70 wt.%) comprising a fluorinated polymer (1-60 wt.%) and a functionalized fluorinated polymer), where the layers are successive and adhere to one another in their respective contact zone.

Description

2876771 1

  FIELD OF THE INVENTION The present invention relates to a multilayer tube based on polyamide and fluoropolymer for the transfer of fluids.

  By way of example of tubes for the transfer of fluid, mention may be made of tubes for gasoline, and in particular for bringing gasoline from the tank to the engine of automobiles. By way of other examples of fluid transfer, mention may be made of the fluids used in the fuel cell, the CO2 system for cooling and air conditioning, the hydraulic systems and the cooling circuit. air conditioning and power transfers at medium pressure.

  For reasons of safety and preservation of the environment, car manufacturers impose on these tubes both mechanical characteristics such as bursting resistance and flexibility with good resistance to cold shocks (-40 C). as well as at high temperature (125 ° C.), and also a very low permeability to hydrocarbons and their additives, in particular alcohols such as methanol and ethanol. These tubes must also have good resistance to fuels and engine lubricating oils. These tubes are manufactured by coextrusion of the different layers according to the usual techniques of thermoplastics.

  The invention is particularly useful for transporting gasoline.

  the prior art and the technical problem Among the characteristics of the specification of the gasoline tubes, five are particularly difficult to obtain jointly in a simple way: - cold shock resistance (-40 C), the tube does not break , - resistance to fuels - resistance to high temperature (125 C), - very low permeability to gasoline, - good dimensional stability of the tube when used with gasoline.

  2876771 2 In multi-layer pipes of various structures, the cold impact resistance remains unpredictable before the standardized cold impact resistance tests have been carried out.

  EP 558373 discloses a tube for transporting gasoline respectively comprising a polyamide outer layer, a binder layer and an inner layer in contact with the gasoline and consisting of fluoropolymer. The permeability to gasoline is excellent but the impact resistance is not sufficient.

  Patents EP 696301, EP 740754 and EP 726926 disclose tubes for transporting gasoline respectively comprising a polyamide outer layer, a binder layer, a PVDF (polyvinylidene fluoride) layer, a binder layer and an inner layer. polyamide in contact with gasoline.

  Other polyamide and PVDF-based gasoline transport tubes are disclosed in US 5,472,784, US 5,474,822, US 5,500,263, US 5,510,160, US 5,512,342 and US 5,554. 426.

  In these tubes of the prior art complex compositions are described to ensure the adhesion of polyamide and PVDF.

  EP 1 104 526 discloses a tube having in its radial direction, from the inside to the outside, a so-called inner layer, based on a fluorinated resin (or polymer) and intended to come into contact with a circulating fluid. characterized in that the inner layer is formed of a mixture comprising a semicrystalline thermoplastic fluorinated resin (eg PVDF) and a triblock copolymer ABC, the three blocks A, B, and C being connected together in that order, each block being either a homopolymer or a copolymer obtained from two or more monomers, block A being connected to block B and block B to block C by means of a covalent bond or an intermediate molecule connected to one of these blocks by a covalent bond and to the other block by another covalent bond, and in that: the block A is compatible with the fluororesin, the block B is incompatible with the fluororesin and is incompatible with the block A, 2876 771 3 -the block C is incompatible with the fluororesin, the block A and the block B, the outer layer of the tube being made of polyamide.

  This PVDF-based layer resists shock while remaining a barrier to gasoline. However, it remains to ensure adhesion to the polyamide layer.

  We have now found a particularly impermeable and impermeable fluoropolymer composition which can adhere directly to substrates such as a polyamide. The composition has excellent resistance to solvents, such as alcoholic essences and a very low permeability.

Brief description of the invention

  The present invention relates to a multilayer tube comprising in its radial direction from the outside to the inside: an outer layer (1) of polyamide, an inner layer (2) of a composition comprising, the total being 100%: 5 to 30% by weight of a mixture (A) comprising: a polyethylene bearing epoxy functions, an impact modifier selected from elastomers and very low density polyethylenes, said impact modifier being wholly or partly functionalized at 70% by weight of a mixture (B) comprising: a fluorinated polymer (B1), a functionalized fluoropolymer (B2), the proportion of (B2) is between 1 and 60% by weight of (A) + (B), the layers being successive and adhering to each other in their respective contact zone. The inner layer is the layer in contact with the transported fluid.

  According to a form of the invention the inner layer (2) contains an electroconductive material producing a surface resistivity preferably less than 106 S2.

  According to another form of the invention, the inner layer (2) contains essentially no electroconductive material and the tube comprises a layer (2a) disposed on the side of the layer (2), this layer may be based on A) and (B) as the layer (2) but additionally contains an electroconductive material producing a surface resistivity preferably less than 106 Q. This layer (2a) can also be a mixture of a fluorinated polymer (B1) and a shock modifier and additionally contains an electroconductive material producing a surface resistivity of preferably less than 106 Ω. An advantage of these structures is that the layer in contact with the transported fluid (eg automobile gasoline) does not contain or very few products (eg oligomers or plasticizer) that can pass into gasoline. To quantify this property, an extraction liquid (for example methanol or ethanol or even octane) is circulated in a closed circuit in the tube at temperatures of the order of 40 ° C. or 60 ° C. measure how much the extraction liquid has been charged and this measurement is repeated several hours in succession until a stable value is obtained. This measurement can also be made by dipping the material of the inner layer in the form of granules into the extraction liquid and stirring. It is considered that the inner layer is clean if the extraction liquid has not loaded more than 5%, preferably 4% and preferably 3%, by weight of products extracted from the inner layer.

  According to another form the invention relates to a multilayer tube comprising in its radial direction from the outside to the inside: an outer layer (1) of polyamide, a layer (2) of a composition comprising, the total being 100% 0 to 30% by weight of a mixture (A) comprising: a polyethylene bearing epoxy functions, an impact modifier selected from elastomers and very low density polyethylenes, said impact modifier being wholly or partly functionalized, at 70 % by weight of a mixture (B) comprising: optionally a fluorinated polymer (B1), a functionalized fluoropolymer (B2), the proportion of (B2) is between 10 and 100% by weight of (A) + (B), preferably 30 to 90% and preferably 40 to 75%.

  an inner layer (3) of polyamide, the layers being successive and adhering to each other in their respective contact zone. The inner layer is the layer in contact with the transported fluid.

  According to one form of the invention, the inner layer (3) contains an electroconductive material producing a surface resistivity of preferably less than 106 Ω. According to another embodiment of the invention, the inner layer (3) contains essentially no electroconductive material and the tube comprises a layer (3a) disposed on the side of the layer (3), this layer is made of polyamide but also contains an electroconductive material producing a surface resistivity of preferably less than 10 to 10. Advantageously, the polyamide 15 of the layer (3a) is the same as that of the layer (3).

  According to one advantageous form, the polyamide of the outer layer (1) is an amine-terminated polyamide or comprising more amine terminations than acid terminations.

  According to an advantageous form there is disposed between the outer layer (1) and the layer (2) an amino-terminated polyamide layer or comprising more amine terminations than acid terminations.

  According to another form one can combine these two previous forms.

  These tubes may have an outside diameter of 6 to 110 mm and a thickness of the order of 0.5 to 5 mm.

  Advantageously, the gasoline tube according to the invention has an outside diameter ranging from 6 to 12 mm, a total thickness of 0.22 mm to 2.5 mm. In the tubes having an inner layer (2) or (2a) the thickness of the outer layer (1) is between 30 and 95% of the thickness of the tube. In the tubes having an inner layer (3) or (3a) the thickness of the outer layer (1) is between 25 and 50% of the thickness of the tube.

  The tube of the present invention is very little permeable to gasoline, particularly to hydrocarbons and their additives, in particular alcohols such as methanol and ethanol or even ethers such as MTBE or ETBE. These tubes also have good resistance to fuels and engine lubricating oils.

  This tube has very good mechanical properties at low or high temperature.

  The invention also relates to the use of these tubes for transporting gasoline.

  Detailed description of the invention

  The tubes having an inner layer (2) or (2a) based on fluoropolymer are first described.

  With regard to the polyamide of the outer layer (1), mention may be made of PA II and PAl2.

  Mention may also be made of those of formula XY / Z or 6.Y2 / Z in which: X denotes the residues of an aliphatic diamine having from 6 to 10 carbon atoms, Y denotes the residues of an aliphatic dicarboxylic acid having from 10 to 10 carbon atoms; at 14 carbon atoms, Y2 denotes the residues of an aliphatic dicarboxylic acid having from 15 to 20 carbon atoms, Z denotes at least one unit selected from the residues of a lactam, the residues of an alpha-omega amino carboxylic acid , the X1.Y1 unit in which X1 denotes the residues of an aliphatic diamine and Y1 denotes the remains of an aliphatic dicarboxylic acid, the weight ratios Z / (X + Y + Z) and Z / (6 + Y2 +) Z) being between 0 and 15%.

  By way of example, mention may be made of PA 6.10 (hexamethylene diamine and sebacic acid units), PA 6.12 (hexamethylene diamine and dodecanedioic acid units) and PA 10.10 (1,10-decanediamine and sebacic acid units).

  Mention may also be made of polyamides of formula X / Y, Ar in which: Y denotes the residues of an aliphatic diamine having from 8 to 20 carbon atoms, wherein Ar denotes the residues of an aromatic dicarboxylic acid, X denotes either the residues of the aminoundecanoic acid NH 2 - (CH 2) 10 -COOH, the lactam 12 or the corresponding amino acid or the unit Y, x the condensation of the diamine with an aliphatic diacid (x) having between 8 and 20 carbon atoms is still the unit Y, the rest of the condensation of the diamine with isophthalic acid, X / Y, Ar designates for example: - the 11/10, which results from the condensation of the aminoundecanoic acid, 1,10-decanediamine and terephthalic acid, - 12/12, which results from the condensation of lactam 12, 1,12-dodecanediamine and terephthalic acid, , 10/10, which results from the condensation of sebacic acid, 1,10-decanediamine and terephthalic acid, the 10.1 / 10, T which results from the condensation of isophthalic acid, 1,10-decanediamine and terephthalic acid.

  The inherent viscosity of the polyamide of the outer layer (1) can be between 1 and 2 and preferably between 1.2 and 1.8. The inherent viscosity is measured at 20 ° C for a concentration of 0.5% in metacresol. The polyamide of the outer layer (1) may contain from 0 to 30% by weight of at least one product chosen from plasticizers and impact modifiers for 100 to 70% of polyamide, respectively. This polyamide may contain the usual anti-UV additives, stabilizers, antioxidants, flame retardants, etc. With regard to the mixture (A) and first of the polyethylene carrying epoxy functions it may be a polyethylene on which epoxy functional groups or a copolymer of ethylene and an unsaturated epoxide have been grafted. .

  Examples of copolymers of ethylene and an unsaturated epoxide include ethylene copolymers of an alkyl (meth) acrylate and an unsaturated epoxide or copolymers of ethylene, a saturated carboxylic acid vinyl ester and an unsaturated epoxide. The amount of epoxide can be up to 15% by weight of the copolymer and the amount of ethylene of at least 50% by weight. Advantageously, the proportion of epoxide is between 2 and 12% by weight. Advantageously, the proportion of alkyl (meth) acrylate is between 0 and 40% by weight and preferably between 5 and 35% by weight.

  Advantageously, it is a copolymer of ethylene of an alkyl (meth) acrylate and an unsaturated epoxide.

  Preferably the alkyl (meth) acrylate is such that the alkyl has 1 to 10 carbon atoms.

  The MFI (melt flow index) can be for example between 0.1 and 50 (g / 10 min at 190 ° C. under 2.16 kg).

  Examples of alkyl acrylate or methacrylate which can be used are in particular methyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylate and the like. 2-ethylhexyl. Examples of unsaturated epoxides that may be used include: aliphatic glycidyl esters and ethers such as glycidyl allyl glycidyl ether, vinyl glycidyl ether, maleate and itaconate, glycidyl acrylate and methacrylate, and esters and alicyclic glycidyl ethers such as 2-cyclohexene-glycidyl ether, cyclohexene-4,5-diglycidylcarboxylate, cyclohexene-4-glycidyl carboxylate, 5-norbornene-2-methyl-2-glycidyl carboxylate and endocisbicyclo (2,2,1) -5-heptene-2,3-diglycidyl dicarboxylate.

  As regards the mixture (A) and now the impact modifier and first elastomers include block polymers SBS, SIS, SEBS, and elastomers ethylene / propylene (EPR) or ethylene / propylene / diene (EPDM). As for the very low density polyethylenes are for example metallocenes of density for example between 0.860 and 0.900. Acrylic elastomers are not recommended because they cause permeability to gasoline. Acrylic elastomers are elastomers based on at least one monomer chosen from acrylonitrile, alkyl (meth) acrylate and core shell (core shell). As regards the bark core copolymer, it is in the form of fine particles having an elastomer core and at least one thermoplastic bark (most often made of PMMA), the particle size is generally less than 1 μm and advantageously included between 50 and 300 nm. It would not be outside the scope of the invention using these acrylic elastomers but it is to the detriment of permeability to gasoline. For example, 1 to 3 parts of acrylic elastomers can be used for 5 to 10 parts of the other impact modifiers.

  Advantageously, an ethylene / propylene (EPR) or ethylene / propylene / diene (EPDM) elastomer is used. The functionalization may be provided by grafting or copolymerization with an unsaturated carboxylic acid. It would not depart from the scope of the invention using a functional derivative of this acid. Examples of unsaturated carboxylic acid are those having 2 to 20 carbon atoms such as acrylic, methacrylic, maleic, fumaric and itaconic acids. Functional derivatives of these acids include, for example, anhydrides, ester derivatives, amide derivatives, imide derivatives and metal salts (such as alkali metal salts) of unsaturated carboxylic acids.

  Unsaturated dicarboxylic acids having 4 to 10 carbon atoms and their functional derivatives, particularly their anhydrides, are particularly preferred grafting monomers. These grafting monomers comprise, for example, maleic, fumaric, itaconic, citraconic, allylsuccinic, cyclohex-4-ene-1,2-dicarboxylic, 4-methylcyclohex-4-ene-1,2-dicarboxylic, and bicyclo (2.2 , I) -hept-5-ene-2,3-dicarboxylic acid, x-methylbicyclo (2,2,1) -hept-5-ene-2,3-dicarboxylic acid, maleic, itaconic, citraconic, allylsuccinic, cyclohex anhydrides 4-ene1,2-dicarboxylic, 4-methylenecyclohex-4-ene-1,2-dicarboxylic, bicyclo (2,2,1) hept-5-ene-2,3-dicarboxylic, and x-methylbicyclo (2, 2.1) hept-5-ene-2,2-dicarboxylic acid. Maleic anhydride is advantageously used.

  Various known methods can be used to graft a grafting monomer onto a polymer. For example, this can be done by heating the polymers at elevated temperature, about 150 to about 300 ° C, in the presence or absence of a solvent with or without a radical generator. The amount of the grafting monomer may be suitably selected but is preferably from 0.01 to 10%, more preferably from 600 to 2% based on the weight of the polymer to which the graft is attached.

  As regards the functionalized fluoropolymer (B2) and firstly the fluoropolymer is denoted as any polymer having in its chain at least one monomer chosen from compounds containing a vinyl group capable of opening to polymerize and which contains, directly attached to this vinyl group, at least one fluorine atom, a fluoroalkyl group or a fluoroalkoxy group.

  By way of example of monomer, mention may be made of vinyl fluoride; vinylidene fluoride (VDF); trifluoroethylene (VF3); chlorotrifluoroethylene (CTFE); 1,2-difluoroethylene; tetrafluoroethylene (TFE); hexafluoropropylene (HFP); perfluoro (alkyl vinyl) ethers such as perfluoro (methyl vinyl) ether (PMVE), perfluoro (ethyl vinyl) ether (PEVE) and perfluoro (propyl vinyl) ether (PPVE); The fluoropolymer may be a homopolymer or a copolymer, it may also include non-fluorinated monomers such as ethylene.

  By way of example, the fluorinated polymer is chosen from: homo- and copolymers of vinylidene fluoride (VDF) preferably containing at least 50% by weight of VDF, the copolymer being chosen from chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP), trifluoroethylene (VF3) and tetrafluoroethylene (TFE), homo- and copolymers of trifluoroethylene (VF3), copolymers, and especially terpolymers, combining the residues of the chlorotrifluoroethylene (CTFE), tetrafluoroethylene (TFE) units , hexafluoropropylene (HFP) and / or ethylene and optionally VDF and / or VF3 units.

  Copolymers of ethylene and tetrafluoroethylene (ETFE) may also be mentioned.

  Advantageously, the fluoropolymer is polyvinylidene fluoride (PVDF) homopolymer or copolymer. Preferably the PVDF contains, in weight, at least 50% VDF, more preferably at least 75% and more preferably at least 85%. The comonomer is advantageously the HFP. Advantageously, the PVDF has a viscosity ranging from 100 Pas to 2000 Pas, the viscosity being measured at 230 C, at a shear rate of 100 using a capillary rheometer. Indeed, these PVDF are well suited to extrusion and injection. Preferably, the PVDF has a viscosity ranging from 300 Pa.s to 1200 Pa.s, the viscosity being measured at 230 C, at a shear rate of 100s -1 using a capillary rheometer.

  By way of example of functionalized fluoropolymer, mention may be made of that grafted with an unsaturated monomer. it can be manufactured according to a grafting process in which: a) the melt fluoropolymer is mixed with the unsaturated monomer; b) the mixture obtained in a) is formed into films, plates, granules or c) the products of step b) are subjected, in the absence of air, advantageously to a photon (-y) or electronic radiation ((3) in a dose of between 1 and 15 Mrad, d ) the product obtained in c) is optionally treated to remove all or part of the unsaturated monomer which has not been grafted onto the fluoropolymer.

  As regards the unsaturated grafting monomer, examples that may be mentioned include carboxylic acids and their derivatives, acid chlorides, isocyanates, oxazolines, epoxides, amines or hydroxides. Examples of unsaturated carboxylic acids are those having 2 to 20 carbon atoms such as acrylic, methacrylic, maleic, fumaric and itaconic acids. Functional derivatives of these acids include, for example, anhydrides, ester derivatives, amide derivatives, imide derivatives and metal salts (such as alkali metal salts) of unsaturated carboxylic acids. Mention may also be made of undecylenic acid and zinc undecylenate.

  Unsaturated dicarboxylic acids having 4 to 10 carbon atoms and their functional derivatives, particularly their anhydrides, are particularly preferred grafting monomers.

  Step a) is carried out in any mixing device such as extruders or kneaders used in the thermoplastics industry.

  With regard to the proportions of the fluoropolymer and the unsaturated monomer, the proportion of fluoropolymer is advantageously, by weight, from 90 to 99.9% for 0.1 to 10% of unsaturated monomer, respectively. Preferably, the proportion of fluoropolymer is from 95 to 99.9% for 0.1 to 5% of unsaturated monomer, respectively.

  At the end of step a), it is found that the mixture of the fluoropolymer and the unsaturated monomer lost about 10 to 50% of the unsaturated monomer introduced at the beginning of step a). This proportion depends on the volatility and the nature of the unsaturated monomer. In fact, the monomer has been degassed in the extruder or mixer and is recovered in the vent circuits.

  With regard to step c), the products recovered after step b) are advantageously packaged in polyethylene bags and the air is removed and they are closed. During this grafting step, it is preferable to avoid the presence of oxygen. A nitrogen or argon sweep of the fluoropolymer / graftable compound mixture is therefore possible to remove oxygen.

  As for the irradiation method, it is possible to use without distinction electron irradiation better known under the name beta irradiation and photon irradiation better known under the name gamma irradiation. Advantageously the dose is between 2 and 6 Mrad and preferably between 3 and 5 Mrad. This results in a grafting of the unsaturated monomer by 0.1 to 5% by weight (that is to say that the unsaturated grafted monomer corresponds to 0.1 to 5 parts for 99.9 to 95 parts of fluoropolymer ), preferably from 0.5 to 5%, preferably from 0.5 to 1.5%; more preferably 0.7 to 1.5%; more preferably 0.8 to 1.5%; more preferably from 0.9 to 1.5% more preferably from 1 to 1.5%. The grafted unsaturated monomer content is dependent on the initial content of the unsaturated monomer in the fluoropolymer / unsaturated monomer mixture to be irradiated. It also depends on the effectiveness of the grafting, and therefore the duration and energy of the irradiation.

  Regarding step d), the ungrafted monomer and the residues liberated by the grafting, in particular HF, can be removed by any means. The proportion of grafted monomer relative to the monomer present at the beginning of step c) is between 50 and 100%. It can be washed with inert solvents with respect to the fluoropolymer and grafted functions. For example when grafting maleic anhydride can be washed with chlorobenzene. It can also be more easily degassed by evacuating, possibly simultaneously applying a heating, the product recovered in step c). This operation can be performed according to techniques known to those skilled in the art. It is also possible to dissolve the modified fluoropolymer in a suitable solvent such as, for example, N-methylpyrrolidone, and then to precipitate the polymer in a non-solvent, for example in water or in an alcohol.

  By way of example of a functionalized fluoropolymer, mention may also be made of that grafted with an unsaturated monomer but by a radical route. The unsaturated monomer may be chosen from those mentioned above. This method is less effective than irradiation grafting, more than 0.8% of unsaturated monomer can not be grafted and there is a risk of degrading the fluoropolymer. However, this product may be suitable for simple conditions of use.

  This is one of the advantages of this irradiation grafting process that higher graft unsaturated monomer contents can be obtained than with conventional grafting methods using a radical initiator. Thus, typically, with the irradiation grafting method, it is possible to obtain contents greater than 1% (1 part of unsaturated monomer per 99 parts of the fluoropolymer), or even greater than 1.5%, whereas with a conventional grafting process in an extruder, the content is of the order of 0.2 to 0.8%. On the other hand, the grafting by irradiation takes place cold, typically at temperatures below 100 C, or even 70 C, so that the mixture of the fluorinated polymer and the unsaturated monomer is not in the molten state as for a conventional grafting process in an extruder. An essential difference is therefore that, in the case of a semicrystalline fluorinated polymer (as for PVDF for example), the grafting takes place in the amorphous phase and not in the crystalline phase while homogeneous grafting occurs. in the case of an extruder grafting. The unsaturated monomer is therefore not distributed identically on the chains of the fluoropolymer in the case of irradiation grafting and in the case of grafting in an extruder. The modified fluorinated product therefore has a different distribution of the graftable compound on the chains of the fluoropolymer compared to a product which would be obtained by grafting in an extruder.

  By way of example of functionalized fluoropolymer, mention may also be made of those in which a functional monomer or a functional element is incorporated during the polymerization. Such functionalized fluoropolymers are described in US Patents 5,415,958, US 6,680,124, US 6,703,465 and US Patent Application 2004-0191440. As regards the fluoropolymer (B1), it can be chosen from among the same

  polymers than (B2). (B1) may be the same polymer as (B2) but not functionalized or different.

  As regards the proportions of (A) are advantageously from 5 to 10% for respectively 95 to 90% of (B). The proportion of polyethylene carrying epoxy functions may be from 1 to 2 parts per 5 parts of the impact modifier. The proportion of (B2) is advantageously between 35 and 60%, preferably between 45 and 55% by weight of (A) + (B).

  With regard to the preparation of the compositions of the invention they may be prepared by melt blending of the components according to the usual techniques of thermoplastics.

  The mixtures of (A) and (B) may additionally contain at least one additive chosen from: dyes; pigments; antioxidants; flame retardants; UV stabilizers; nanofillers; nucleating agents.

  As regards the inner layer (2) containing an electroconductive material, mention may be made, for example, of carbon black, carbon fibers and carbon nanotubes. It is advantageous to use a carbon black chosen from those having a BET specific surface area, measured according to ASTM D3037-89, of from 5 to 200 m 2 / g, and a DBP absorption, measured according to the ASTM D 2414-90 standard, of 50 to 300 ml / 100 g. The proportion of black is advantageously by weight of 10 to 30% for respectively 90 to 70% of the other constituents and preferably 12 to 23% for 88 to 77% of the other constituents, respectively. These carbon blacks are described in the patent application WO 99-33908.

  With regard to the inner layer (2a) containing an electroconductive material, it may consist of the mixture of (A) and (B) as the layer (2) and contains the electroconductive material. The proportions of (A) and (B) and the nature of the constituents of (A) and (B) may be the same or different from those of layer (2). It may also be a mixture of a fluorinated polymer (B1) and a shock modifier and additionally contains an electroconductive material producing a surface resistivity preferably of less than 106 S2. The impact modifier can be chosen from those mentioned in the mixture (A) including acrylic elastomers. It can be made entirely of acrylic elastomers (preferably core shells), indeed this layer does not have to be a barrier to gasoline this function being provided by the layer (2). If the impact modifier is not an acrylic elastomer or is a mixture of an acrylic elastomer and for example an EPR, this EPR is advantageously functionalized. To facilitate compatibilization with (El) it is recommended to add functionalized polymer (B2). The fluorinated polymer 2876771 16 (B1) may be the same as that of the layer (2) or be different. It is also possible to add functionalized fluoropolymer (B2) which may be the same as that of layer (2) or be different. Advantageously (B1) and (B2) are PVDF homopolymers or copolymers. The proportion of black is advantageously by weight of 10 to 30% for respectively 90 to 70% of the other constituents and preferably 12 to 23% for 88 to 77% of the other constituents, respectively. The proportion of impact modifier is advantageously from 1 to 40% by weight of the impact modifier assembly, fluoropolymer (BI) and optionally (B2). This proportion is preferably 5 to 35% by weight of the impact modifier, fluoropolymer (BI) and optionally (B2).

  With regard to the form of the invention in which the tube comprises an inner layer (3), the polyamide of the outer layer (1) may be chosen from the polyamides of the outer layer (1) described above.

  With regard to the layer (2), the nature of the constituents of (A) and (B) is the same as that described above. The proportions of (A) are advantageously from 5 to 30% for respectively 95 to 70% of (B). The proportions of (A) are preferably 5 to 10% for respectively 95 to 90% of (B). The proportion of polyethylene carrying epoxy functions may be from 1 to 2 parts per 5 parts of the impact modifier. The proportion of (B2) is advantageously between 35 and 60%, preferably between 45 and 55% by weight of (A) + (B).

  The polyamide of the inner layer (3) may be chosen from the polyamides mentioned for the outer layer, the PA 6, the PA 6 and polyolefin PA 6 matrix and polyolefin dispersed phase mixtures.

  In the PA 6 and polyolefin PA 6 and polyolefin dispersed phase mixtures, the term polyolefin refers to both homopolymers and copolymers, thermoplastics as well as elastomers. It is for example copolymers of ethylene and an alphaolefin. These polyolefins may be LLDPEs, PEs, EPRs of EPDMs. They can be functionalized in whole or in part. The dispersed phase may be a mixture of one or more non-functionalized polyolefins and one or more functionalized polyolefins. Advantageously, the matrix PA 6 represents 50 to 85% by weight for respectively 50 to 15% of dispersed phase. Preferably the matrix PA 6 represents 55 to 80% by weight for respectively 45 to 20% of dispersed phase.

  In a preferred form, the PA 6 and polyolefin PA 6 matrix mixtures comprise, the total being 100%: 50 to 90% (advantageously 60 to 80%) of PA 6, 1 to 30% (advantageously 10 to 25%) of HDPE, at 30% (advantageously 10 to 20%) of at least one polymer P1 selected from impact modifiers and polyethylenes, at least one of HDPE and P1 being functionalized in whole or in part.

  Advantageously, the impact modifier is chosen from elastomers and very low density polyethylenes.

  As regards the impact modifier and first elastomers include block polymers SBS, SIS, SEBS, and elastomers ethylene / propylene (EPR) or ethylene / propylene / diene (EPDM). As for the very low density polyethylenes are for example metallocenes of density for example between 0.860 and 0.900.

  Advantageously, an ethylene / propylene (EPR) or ethylene / propylene / diene (EPDM) elastomer is used. The functionalization may be provided by grafting or copolymerization with an unsaturated carboxylic acid.

  It would not depart from the scope of the invention using a functional derivative of this acid. Examples of unsaturated carboxylic acid are those having 2 to 20 carbon atoms such as acrylic, methacrylic, maleic, fumaric and itaconic acids. Functional derivatives of these acids include, for example, anhydrides, ester derivatives, amide derivatives, imide derivatives and metal salts (such as alkali metal salts) of unsaturated carboxylic acids.

  Unsaturated dicarboxylic acids having 4 to 10 carbon atoms and their functional derivatives, particularly their anhydrides, are particularly preferred grafting monomers. Maleic anhydride is advantageously used.

  The proportion of functionalized PERD and / or functionalized P1 with respect to the whole functionalized or non-functionalized HDPE and functionalised or non-functionalized P1 may be included (by weight) between 0 and 70%, advantageously between 5 and 60% and preferably between 20 and 60%.

  The mixtures of PA 6 and polyolefin matrix PA 6 may be prepared by mixing the various constituents in the molten state in the usual apparatus of the thermoplastic polymer industry.

  According to a first form of these PA 6 and PA 6 polyolefin mixtures, the HDPE is not grafted and P1 is a mixture of a grafted elastomer and an ungrafted elastomer.

  According to another form of these mixtures of PA 6 and polyolefin matrix PA 6 HDPE is not grafted and P1 is a graft polyethylene eventually mixed with an elastomer.

  With regard to the inner layer (3) or (3a) containing an electroconductive material, there may be mentioned, for example, carbon black, carbon fibers and carbon nanotubes. It is advantageous to use a carbon black chosen from those having a BET specific surface area, measured according to ASTM D3037-89, of from 5 to 200 m 2 / g, and a DBP absorption, measured according to the ASTM D 2414-90 standard, of 50 to 300 ml / 100 g. The proportion of black is advantageously by weight of 16 to 30% for respectively 84 to 70%. other constituents and preferably from 17 to 23% for respectively 83 to 77% of the other constituents. These carbon blacks are described in the patent application WO 99-33908.

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Examples

  The following polymers were used: Kynar ADX 120: PVDF functional homopolymer grafted with maleic anhydride from the company ATOFINA and MVI (Melt Volume Index) (melt volume melt index) 7 cm3 / 10 min (230 C, 5 kg).

  Kynar 740: PVDF homopolymer of the company ATOFINA and MVI (Melt Volume Index) 1 cm3 / 10 min (230 C, 5kg).

  LOTADER 8840: copolymer of ethylene and glycidyl methacrylate from the company ATOFINA and MVI (Melt Volume Index) 5 cc / 10 min (190 C 2.16 kg). It contains 92% ethylene and 8% glycidyl methacrylate by weight.

  EXXELOR VA 1803: EPR elastomer grafted with maleic anhydride, MFI 3 g / 10 min (230 C-2.16 kg).

  Rilsan MA4411: plasticized and impact modified polyamide 12 from the company ATOFINA Polyamide 12 conductor: composition similar to Rilsan MA4411 but also comprising 20% carbon black (to the detriment of polyamide 12)

Example 1

  In the Werner 40 extruder, a mixture of Kynar 740 (38% by weight), with 50% Kynar ADX 120, 2% LOTADER 8840 and 10% EXXELOR VA 1803 is produced at 230 C. This mixture is once performed has a nodular type morphology with an average dispersed phase size of less than 5 μm.

  A bilayer tube of 1 mm thickness and 8 mm outer diameter made of an outer layer of Rilsan MA4411 (800 μm) and the preceding PVDF alloy in an inner layer (200 μm) was extruded on a McNeil line at 230 ° C.

  The peel force required to separate the inner layer from the outer layer at 50 mm / min is 50 N / cm.

  This tube passes the shock at -40 C of SAEJ 2260.

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Example 2

  A three-layer tube having a thickness of 1 mm and an outer diameter of 8 mm and consisting of an outer layer of Rilsan MA4411 (400 μm), an intermediate layer of ADX120 (200 μm) and an inner layer of polyamide 12 are extruded on a McNeil line at 230 ° C. driver (400pm).

  The peel force necessary to separate the inner or outer layer of the grafted PVDF layer at 50 mm / min is 50 N / cm.

  This tube passes the shock at -40 C of SAEJ 2260.

  The surface resistivity measured on the tube according to SAEJ2260 10 is less than 10A6 ohms.sq This tube has a CE10 permeability at 40 C below 5g / (m2.day). CE10 gasoline contains: 45% isooctane, 45% toluene and 10% by volume ethanol.

Claims (15)

  A multilayer pipe comprising in its radial direction from the outside to the inside: an outer layer (1) of polyamide, an inner layer (2) of a composition comprising, the total being 100%: 5 to 30% by weight a mixture (A) comprising: a polyethylene bearing epoxy functional groups, an impact modifier selected from elastomers and very low density polyethylenes, said impact modifier being wholly or partly functionalized, at 70% by weight of a mixture (B) comprising: a fluorinated polymer (BI), a functionalized fluoropolymer (B2), the proportion of (B2) is between 1 and 60% by weight of (A) + (B), the layers being successive and adhering between them in their respective contact area.   2 tube according to claim 1 wherein the inner layer (2) contains an electroconductive material.   3 tube according to claim 1 wherein the inner layer (2) contains substantially no electroconductive material and the tube comprises a layer (2a) disposed on the side of the layer (2), this layer is based on (A) and (B) as the layer (2) but additionally contains an electroconductive material.   4 tube according to claim 1 wherein the inner layer (2) contains substantially no electroconductive material and the tube comprises a layer (2a) disposed on the side of the layer (2), this layer is a mixture of a fluoropolymer (BI) and a shock modifier and additionally contains an electroconductive material producing a surface resistivity of preferably less than 106 sZ.   Multilayer tube comprising in its radial direction from the outside to the inside: an outer layer (1) of polyamide, a layer (2) of a composition comprising, the total being 100%: 0 to 30% by weight of a mixture (A) comprising: a polyethylene bearing epoxy functions, an impact modifier selected from elastomers and very low density polyethylenes, said impact modifier being wholly or partly functionalized, at 70% by weight of a mixture (B ) comprising: optionally a fluorinated polymer (B1), a functionalized fluoropolymer (B2), the proportion of (B2) is between 10 and 100% by weight of (A) + (B), an inner layer (3) in polyamide, the layers being successive and adhering to each other in their respective contact zone.   6. The tube of claim 5 wherein the proportions of (A) are 5 to 30% for respectively 95 to 70% of (B).   Tube according to claim 5 or 6 wherein the inner layer (3) contains an electroconductive material.   8 tube according to claim 5 or 6 wherein the inner layer (3) contains substantially no electroconductive material and the tube comprises a layer (3a) disposed on the side of the layer (3), this layer is polyamide as the layer (3) but additionally contains an electroconductive material.   Tube according to any one of the preceding claims wherein the polyamide of the outer layer (1) is an amine terminated polyamide or comprising more amine terminations than acid termini.   Tube according to any one of the preceding claims wherein there is disposed between the outer layer (1) and the layer (2) an amino-terminated polyamide layer or comprising more amine terminations than acid terminations.   Tube according to any one of the preceding claims wherein the impact modifier of the mixture (A) is a maleic anhydride grafted EPR or an maleic anhydride grafted EPDM.   Tube according to any one of the preceding claims, in which the functionalized fluoropolymer (B2) is a PVDF homopolymer or copolymer grafted with maleic anhydride.   The tube of any preceding claim wherein the fluoropolymer (B1) is a PVDF homopolymer or copolymer.   Tube according to any one of claims 1 to 4 and 6 to 13 wherein the proportions of (A) are 5 to 10% for respectively 95 to 90% of (B).   Tube according to any one of the preceding claims wherein the proportion of polyethylene carrying epoxy functions is 1 to 2 parts per 5 parts of the impact modifier.   Tube according to any one of the preceding claims wherein the proportion of (B2) in the mixtures of (A) and (B) is between 35 and 60% by weight of (A) + (B).   The tube of claim 16 wherein the proportion of (B2) in the mixtures of (A) and (B) is from 45 to 55% by weight of (A) + (B).   18 Use of the tubes according to any one of the preceding claims for the transport of gasoline.