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    • 专利摘要:
    The present invention relates to a multilayer tubular structure MLT for the transport of fluids, in particular gasoline, comprising from the inside to the outside at least one barrier inner layer (1) and at least one outer layer (2) located at the above the barrier layer, said outer layer (2) or all the layers (2) and any other layers above the barrier layer, containing on average from 0 to 5% of plasticizer with respect to the weight total of the composition of the layer (2), or in which the set of outer layers, located above the barrier layer, comprise on average from 0 to 5% of plasticizer, said outer layer (2) comprising predominantly at least one aliphatic type polyamide or consisting of more than 75% of aliphatic units, said aliphatic polyamide being chosen from: a polyamide noted A having an average number of carbon atoms per nitrogen atom noted CA c between 4 and 8.5, advantageously between 4 and 7; a polyamide denoted B and an average number of carbon atoms per nitrogen atom noted Ce of between 7 and 10, advantageously between 7.5 and 9.5; a polyamide noted C having an average number of carbon atoms per nitrogen atom noted Ce between 9 and 18, advantageously between 10 and 18; provided that when said outer layer (2) comprises at least three polyamides, at least one of said polyamides A, B or C is excluded.
    公开号:FR3046827A1
    申请号:FR1650339
    申请日:2016-01-15
    公开日:2017-07-21
    发明作者:Thibaut Montanari；Christelle Recoquille；Bertrand Verbauwhede
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    The invention relates to a multilayer structure, in particular in the form of a tube, and its use for transporting fluids, in particular gasoline-type fuel. especially alcoholic, especially for motor vehicles. The invention relates more particularly to the tubes present within an engine. These tubes may for example be intended for transporting fuels, in particular between the tank and the engine, the cooling circuit, the hydraulic system, or for the air conditioning circuit or the transport of urea mixture and water .
    For the transport of gasoline and in particular of bio-gasoline, many criteria must be met, in particular good barrier properties (for reasons of environmental protection), cold shock, pressure resistance, etc.
    For reasons of safety and preservation of the environment, particularly with the arrival of new bio-fuels, car manufacturers require the above-mentioned tubes to have particular mechanical characteristics, as well as characteristics of very low permeability and good resistance to corrosion. different constituents of fuels, which vary by country (hydrocarbons, additives, alcohols such as methanol and ethanol, alcohols may be major components in some cases), engine lubricating oils and other chemicals likely to be encountered in this environment (acid batteries, brake fluids, coolants, metal salts such as calcium chloride or zinc).
    The characteristics of the specifications commonly required by car manufacturers for a tube to be considered satisfactory are cumulatively the following: - good and durable adhesion between the layers, if the tube is a multilayer tube, especially after being exposed to fuel ; good integrity of the connections (tubes with connections) after fuel circulation, that is to say leading to no leakage; good dimensional stability of the tube, when used with gasoline; good resistance to cold shocks (from -30 ° C to -40 ° C), so that the tube does not break; good heat resistance (about 150 ° C.), so that the tube does not deform; good resistance to aging in a hot oxidizing medium (for example: hot air from the engine compartment, from 100 to 150 ° C.); good resistance to fuels and their degradation products and especially with high levels of peroxide; very low permeability to fuels, and more particularly good barrier properties to biofuels, both for its polar components (such as ethanol) and for its non-polar components (hydrocarbons); good flexibility of the tube to facilitate the assembly including the fuel supply pipe; - good resistance to ZnCl2 (for example, in winter, when the roads are salty, the outside of the tube being exposed to this environment).
    In addition, the desired tubes must avoid the following disadvantages: if the tube is a multilayer tube, the delamination of the layers, including internal, especially during the insertion of connection (which can lead to leaks); excessive swelling of the tube after aging in gasoline / diesel systems (including for biodiesels or bio-gasolines), which can lead to leaks or problems of positioning under the vehicle. Recently a new problem has emerged, namely the excess extractable material of the multilayer pipe after prolonged contact with the alcoholic gasoline. These extractables are likely to block or plug the injectors of the engines of vehicles. Automakers, and in particular Volkswagen, have put in place new criteria for the selection of tubes that can carry gasoline, particularly alcoholic, in motor vehicles, which are more severe than before. Thus, the new test developed by the various manufacturers including Volkswagen consists in determining the proportion of extractables of a fuel transport tube after contacting the interior of the latter with hot alcoholic gasoline. for several hours and weighing the evaporation residue of the gasoline contained inside the tube corresponding to extractables. The test tube can then be used for the transport of gasoline only if the proportion of extractables as low as possible, in particular less than or equal to 6g / m2 (internal tube surface). At present, there are two types of tubes, monolayer and multilayer tubes, that is to say made of one or more layers of polymer. For gasoline transport in particular, the use of multilayer pipe comprising a barrier layer tends to become generalized for ecological reasons.
    Conventionally, the tubes used are manufactured by mono-extrusion, if it is a single-layer tube, or by coextrusion of the different layers, if it is a multilayer tube, according to the techniques usual processing of thermoplastics.
    The structures (MLT) for the transport of gasoline typically consist of a barrier layer such as PPA, surmounted by a PA layer (at least one layer) and possibly comprising layers of binders in the case where the adhesion, between the other layers, proves insufficient.
    Thus patent EP 2098580 describes in particular tubes having a barrier of PPA and at least one layer of polyamide, plasticized or not, located above the barrier layer. Nevertheless, this type of structure as well as other MLTs known to those skilled in the art is no longer suitable for the new extractible test mentioned above.
    The present invention intends to solve this new problem by a particular arrangement and constitution of the layers of the multilayer structure.
    The present invention relates to a multilayer tubular structure MLT for the transport of fluids, in particular gasoline, comprising from the inside to the outside at least one barrier inner layer (1) and at least one outer layer (2) located at the above the barrier layer, said outer layer (2) or all the layers (2) and any other layers above the barrier layer, containing on average from 0 to 5% of plasticizer with respect to the weight total of the composition of the layer (2), or in which the set of outer layers, located above the barrier layer, comprise on average from 0 to 5% of plasticizer, said outer layer (2) comprising predominantly at least one aliphatic type polyamide or consisting of more than 75% of aliphatic units, said aliphatic polyamide being chosen from: a polyamide noted A having an average number of carbon atoms per nitrogen atom e noted Ca between 4 and 8.5, preferably between 4 and 7; a polyamide denoted B and an average number of carbon atoms per nitrogen atom noted Cb of between 7 and 10, advantageously between 7.5 and 9.5; a polyamide noted C having an average number of carbon atoms per nitrogen atom noted Ce between 9 and 18, advantageously between 10 and 18; provided that when said outer layer (2) comprises at least three polyamides, at least one of said polyamides A, B or C is excluded.
    It would not be departing from the scope of the invention if the object intended for the transport of fluid was also used for storing fluids.
    The term "fluid" denotes a gas used in the automobile or a liquid, in particular a liquid and especially an oil, a brake fluid, a urea solution, a glycol-based coolant, fuels, in particular light fuels likely to pollute, advantageously fuels except diesel, including gasoline or LPG, especially gasoline and more particularly alcoholic gasoline. Air, nitrogen and oxygen are excluded from the definition of the gas.
    The term "gasoline" refers to a mixture of hydrocarbons derived from the distillation of petroleum to which additives or alcohols such as methanol and ethanol can be added, the alcohols being in some cases major components. The term "alcoholic spirit" refers to a species in which methanol or ethanol has been added. It also refers to an E95 type gasoline that does not contain any petroleum distillate. The term "barrier layer" designates a layer having characteristics of low permeability and good resistance to the various constituents of the fluids, especially from fuels, that is to say that the barrier layer slows down the passage of the fluid, in particular the fuel, both for its polar components (such as ethanol) and for its nonpolar components (hydrocarbons) in the other layers of the structure or even outside the structure. The barrier layer is therefore a layer that above all makes it possible not to lose gasoline in the atmosphere by diffusion, thus avoiding atmospheric pollution. These barrier materials may be polyphthalamides and / or functionalized fluorinated materials such as the functionalized ethylene tetrafluoroethylene (ETFE) copolymer, the functionalized ethylene tetrafluoroethylene and hexafluoropropylene (EFEP) copolymer, a copolymer tetrafluoroethylene-perfluoro (alkyivinylether) -chlorotrifluoroethylene (CPT). If these polymers are not functionalized, then an intermediate layer of binder can be added to ensure good adhesion within the MLT structure.
    Among the PPPAs, coPA6T, PA9T and its copolymers, PA10T and its copolymers, MXD6 and its copolymers are particularly interesting. The expression "said outer layer (2) comprising predominantly at least one aliphatic type polyamide" means that said aliphatic type polyamide is present in a proportion of more than 50% by weight in the layer (2). The aliphatic type polyamide is linear and is not cycloaliphatic type.
    Advantageously, said predominant aliphatic type polyamide of the layer or layers (2) also mainly comprises aliphatic units, ie more than 50% of aliphatic units.
    Advantageously, said predominant aliphatic type polyamide of the layer or layers (2) consists of more than 75% of aliphatic units, preferably said aliphatic type majority polyamide or the layers (2) is completely aliphatic.
    The inventors have therefore found that the absence or at least a small proportion of plasticizer in the outer layer or layers, that is to say situated above the barrier layer, makes it possible to greatly reduce the proportion of extractables as determined by a test as defined above and in particular by a test which consists of filling a tubular structure of FAM-B type alcoholic essence and heating the assembly to 60 ° C for 96 hours, then to empty it by filtering it in a beaker, then let the filtrate of the beaker evaporate at room temperature to finally weigh this residue whose proportion must be less than or equal to about 6g / m2 of inner tube surface. The FAM alcoholic spirit is described in DIN 51604-1: 1982, DIN 51604-2: 1984 and DIN 51604-3: 1984.
    Briefly, FAM alcoholic essence is first prepared with a mixture of 50% toluene, 30% isooctane, 15% di-isobutylene and 5% ethanol and then FAM B is prepared by mixing 84.5% FAM A with 15% methanol and 0.5% water.
    In total, FAB consists of 42.3% toluene, 25.4% isooctane, 12.7% di-isobutylene, 4.2% ethanol, 15% methanol and 0.5% methanol. water.
    According to the present application, the term "polyamide", also denoted PA, refers to: homopolymers, copolymers, or copolyamides, based on different amide units, such as for example copolyamide 6/12 with amide units derived from lactam -6 and lactam-12, - polyamide alloys, since the polyamide is the major constituent.
    There is also a class of copolyamides in the broad sense which, although not preferred, is within the scope of the invention. These are copolyamides comprising not only amide units (which will be the majority, hence the fact that they are to be considered as copolyamides in the broad sense), but also non-amide-type units, for example ether units. . The best known examples are PEBA or polyether-block-amide, and their copolyamide-ester-ether, copolyamide-ether, copolyamide ester variants. Among these are PEBA-12 where the polyamide units are the same as those of PA12, PEBA-6.12 where the polyamide units are the same as those of PA6.12.
    Homopolyamides, copolyamides and alloys can also be distinguished by their number of carbon atoms per nitrogen atom, given that there are as many nitrogen atoms as there are amide groups (-CO-NH-).
    A highly carbonated polyamide is a polyamide with a high carbon content (C) relative to the nitrogen atom (N). These are the polyamides with approximately at least 9 carbon atoms per nitrogen atom, such as for example polyamide-9, polyamide-12, polyamide-11, polyamide-10.10 (PA10.10), copolyamide 12 / 10.T, copolyamide 11 / 10.T, polyamide-12.T, polyamide-6.12 (PA6.12). T represents terephthalic acid.
    The nomenclature used to define polyamides is described in ISO 1874-1: 1992 "Plastics - Polyamides (PA) for molding and extrusion - Part 1: Designation", in particular on page 3 (Tables 1 and 2) and is well known to those skilled in the art.
    A low carbon polyamide is a polyamide with a low carbon content (C) relative to the nitrogen atom (N). These are polyamides with about less than 9 carbon atoms per nitrogen atom, such as for example polyamide-6, polyamide-6.6, polyamide-4.6, copolyamide-6.T / 6.6, copolyamide 6.I /6.6, copolyamide 6.T / 6.I / 6.6, polyamide 9.T. I represents isophthalic diacid.
    In the case of a homopolyamide of PA-XY type, with X denoting a unit obtained from a diamine and Y denoting a unit obtained from a diacid, the number of carbon atoms per nitrogen atom is the average of the numbers of carbon atoms present in the unit derived from diamine X and in the unit derived from diacid Y. Thus PA6.12 is a PA with 9 carbon atoms per nitrogen atom, ie a PA in C9. PA6.13 is in C9.5.
    In the case of copolyamides, the number of carbon atoms per nitrogen atom is calculated according to the same principle. The calculation is carried out using the molar prorata of the different amide units. In the case of a copolyamide having non-amide type units, the calculation is carried out solely on the amide units part. Thus, for example, PEBA-12, which is a block copolymer of amide units 12 and ether units, the average number of carbon atoms per nitrogen atom will be 12, as for PA12; for PEBA-6.12, it will be 9, as for PA6.12.
    Thus, highly carbonaceous polyamides, such as polyamide PA12 or 11, hardly adhere to a low carbon (co) PAXT such as coPA6T / x, to a low carbon polyamide such as polyamide PA6, or to an alloy of polyamide PA6 and polyolefin ( as, for example, an Orgalloy® marketed by Arkema).
    However, it is observed that the pipe structures currently proposed are unsatisfactory for a dedicated use of biofuels, the requirements of the specifications of the vehicle manufacturers mentioned above can not all be simultaneously fulfilled.
    Biofuels are not only from petroleum but include a proportion of polar products such as alcohols of plant origin, such as ethanol or methanol, of at least 3%. This rate can go up to 85% or even 95%.
    In addition, the fuel flow temperature tends to rise due to new engines (more confined, operating at higher temperatures).
    Advantageously, the present invention relates to a multilayer tubular structure (MLT) as defined above, wherein said outer layer (2) comprises from 0 to 1.5% of plasticizer relative to the total weight of the composition of the layer ( 2).
    In the case where several layers (2) are present, it is possible that one of the outer layers has a significant proportion of plasticizer such as 15% by weight but in this case, the proportion of plasticizer is compensated by the thickness of the layer which is then much thinner so that the average value of plasticizer present in the set of inner layers does not exceed 5%. The proportion of plasticizer in this layer can then be up to 15% but its thickness does not exceed 20% of the total thickness of the tube, preferably it does not exceed 200pm.
    Advantageously, the present invention relates to a multilayer tubular structure (MLT) comprising a layer (2) as defined above, in which at least one second outer layer (2 ') situated above the barrier layer is present, and preferably located above the layer (2), said layer (2 ') being plasticized, said plasticizer being in particular present in a proportion of 1.5% to 15% by weight relative to the total weight of the composition of said layer, the thickness of said layer (2 ') preferably represents up to 20% of the total thickness of the tubular structure, in particular up to 200 μm.
    The layer (2 ') comprises, just as the layer (2), for the most part, an aliphatic type polyamide, that is to say that said aliphatic type polyamide is present in a proportion of more than 50% by weight in the layer (2') . The aliphatic type polyamide is linear and is not cycloaliphatic type.
    Advantageously, said majority aliphatic type polyamide of the layer or layers (2 ') also comprises mainly aliphatic units, ie more than 50% of aliphatic units.
    Advantageously, said predominant aliphatic type polyamide of the layer or layers (2 ') consists of more than 75% of aliphatic units, preferably said aliphatic type majority polyamide or the layers (2') is completely aliphatic.
    In another embodiment, the present invention relates to a multilayer tubular structure (MLT), wherein the layer (s) (2) comprises (include) up to 1.5% by weight of plasticizer, by relative to the total weight of the composition of said layer or of all the compositions of the layers (2).
    Advantageously, the multilayer tubular structure (MLT) comprises a single layer (2) and is devoid of plasticizer.
    In another embodiment, the present invention relates to a multilayer tubular structure (MLT) in which the plasticizer content of all the layers above the barrier layer is at most 5% by weight relative to the total weight. compositions of all layers above the barrier layer.
    In another embodiment, the present invention relates to a multilayer tubular structure (MLT), wherein the layer (2 ') is the outermost and is the only one plasticized, the layer (s) (2) being devoid of plasticizer.
    The proportion of plasticizer may represent up to 15% by weight of the total weight of the composition of the layer (2 '). The greater the proportion of plasticizer, the more the layer (2 ') will be thin with a thickness of said layer (2') which preferably represents up to 20% of the total thickness of the tubular structure, in particular up to at 200pm.
    Advantageously, the multilayer tubular structure (MLT) consists of three layers, from the outside to the inside (2 ') // (2) // (1), the layer (2') being the only one plasticized in proportions as defined above, the layer (2) being free of plasticizer.
    A multilayer tubular structure (MLT) consisting of three layers from the outside to the inside (2 ') // (2) // (1) has the advantage of having an elongation at break at t = 0 when the structure is very dry with a very low humidity content of 0 and 30% relative humidity, which is very good and especially better than a structure whose layers (2 ') and (2) are devoid of plasticizer .
    Advantageously, in this last embodiment, the layer (2 ') is the outermost and the polyamide of the latter is a long-chain polyamide, ie an average number of carbon atoms per nitrogen atom noted Ce understood 9.5 to 18, the layer (2) is situated between the barrier layer and the layer (2 ') and the polyamide of this layer (2) is a short-chain polyamide, ie an average number of carbon atoms per atom of nitrogen noted Ca included from 4 to 9.
    Advantageously, in this last embodiment, the layer (2 ') has a thickness of 100 to 200 μm, the layer (2) has a thickness of at least 200 μm, and the layer (1) has a thickness of 100 to 300PM.
    Advantageously, in this last embodiment, the layer (2 ') is the outermost and the polyamide of the latter is a long-chain polyamide, ie an average number of carbon atoms per nitrogen atom noted Ce understood 9.5 to 18, the layer (2) is situated between the barrier layer and the layer (2 ') and the polyamide of this layer (2) is a short-chain polyamide, ie an average number of carbon atoms per atom of nitrogen noted from 4 to 9, the layer (2 ') to a thickness of 100 to 200pm, the layer (2) has a thickness of at least 200 to 400 pm, the layer (1) has a thickness of from 100 to 300pm.
    Whatever the number of layers, the preferred tubular structures are those containing the least possible plasticizer in the outer layers, that is to say the less close to the fluid. These structures can be the following:
    Multilayer tubular structure (MLT) containing not more than 1.5% plasticizer, in the first 50% of its thickness from the barrier layer in contact with the fluid.
    Multilayer tubular structure (MLT) containing not more than 1.5% plasticizer, in the first 75% of its thickness from the barrier layer in contact with the fluid.
    Multilayer tubular structure (MLT) containing not more than 1.5% plasticizer, in the first 85% of its thickness from the barrier layer in contact with the fluid.
    Multilayer tubular structure (MLT) devoid of plasticizer, in the first 50% of its thickness from the barrier layer in contact with the fluid.
    Multilayer tubular structure (MLT) devoid of plasticizer, in the first 75% of its thickness from the barrier layer in contact with the fluid.
    Multilayer tubular structure (MLT) devoid of plasticizer, in the first 85% of its thickness from the barrier layer in contact with the fluid.
    In another embodiment, the present invention relates to a multilayer tubular structure (MLT) as defined above, in which at least one layer (3) is present, said layer (3) containing not more than 15% by weight of plasticizer, preferably not more than 1.5% by weight of plasticizer, relative to the total weight of the constituents of the layer (3), advantageously the layer (3) is devoid of plasticizer, said layer (3) comprising predominantly at least one aliphatic type polyamide or consisting of more than 75% of aliphatic units, said aliphatic polyamide being selected from - a polyamide noted A having an average number of carbon atoms per nitrogen atom noted CA from 4 to 8.5, advantageously from 4 to 7 - - a polyamide denoted B and an average number of carbon atoms per nitrogen atom of CB denoted from 7 to 10, advantageously from 7.5 to 9.5; a polyamide noted C having an average number of carbon atoms per nitrogen atom denoted CC of from 9 to 18, advantageously from 10 to 18; provided that when said layer (3) comprises at least three polyamides, at least one of said polyamides A, B or C is excluded, said layer (3) being located between the outer layer (2) and the barrier layer (1 ); or said layer (3) is a binder layer whose thickness represents up to 15% of the structure (MLT).
    The layer (3) when it is not a binder layer is an aliphatic type polyamide as defined for the layers (2) and (2 ').
    Advantageously, the tubular structure of the invention is a three-layer structure consisting of the exterior to the interior of the following layers; (2) // (3) // (1), the layer (2) being plasticized to 5% as above and thin, the layer (3) comprising plasticizer, or the layer (3) when it is different from the binder layer as defined above is devoid of plasticizer. However, this layer (2) plasticized to 5% by weight should not be too thin otherwise the barrier layer is too little in the center and the MLT structure may not be good enough shock. On the other hand, it can be very fine if there is a thick extra layer (unplasticized) between the layer (2) and the layer (1), so that the layer (1) is not too off-center.
    Another layer (2 ') may also be present in this three-layer structure.
    The said layer (3) may also be a binder as described, in particular in patents EP 1452307 and EP1162061, EP 1216826 and EP0428833.
    It is implicit that layers (2) and (1) adhere to each other. The binder layer is intended to be interposed between two layers that do not adhere or with difficulty between them.
    The binder can be, for example, but not limited thereto, a composition based on 50% of copolyamide 6/12 (ratio 70/30 by weight) of Mn 16000, and 50% of copolyamide 6/12 ( of 30/70 by weight) of Mn 16000, a composition based on PP (polypropylene) grafted with maleic anhydride, known under the name Admer QF551A from Mitsui, a composition based on PA610 (from Mn 30000, and as defined elsewhere) and 36% PA6 (Mn 28000) and 1.2% organic stabilizers (consisting of 0.8% phenol Lowinox 44B25 from Great Lakes Company, 0, 2% Irgafos 168 phosphite from Ciba, 0.2% Tinuvin 312 anti-UV from Ciba), a composition based on PA612 (Mn 29,000, and as defined elsewhere) and from % PA6 (from Mn 28,000, and as defined elsewhere) and 1.2% organic stabilizers (consisting of 0.8% phenol Lowinox 44B25 from the company Great Lakes, 0.2% phosphite Irgafos 168 of the company Ciba, 0.2% anti-UV Tinuvin 312 from Ciba), a composition based on PA610 (Mn 30000, and as defined elsewhere) and 36% PA12 (Mn 35000, and as defined elsewhere) and 1.2% of organic stabilizers (consisting of 0.8% phenol Lowinox 44B25 from Great Lakes, 0.2% phosphite Irgafos 168 from Ciba, 0, 2% anti-UV Tinuvin 312 Ciba), a composition based on 40% PA6 (Mn 28,000, and as defined elsewhere), 40% PA12 (Mn 35,000, and as defined moreover) and 20% functionalized EPR Exxelor VA1801 (Exxon company) and 1.2% organic stabilizers (consisting of 0.8% phenol Lowinox 44B25 from Great Lakes Company, 0.2% phosphite Irgafos 168 from Ciba, 0.2% anti-UV Tinuvin 312 from Ciba) or a composition based on 40% PA610 (Mn 30000, and as defined elsewhere), 40% PA6 (from Mn 28000, and as defined by elsewhere) and 20% impact modifier type ethylene / ethyl acrylate / anhydride in weight ratio 68.5 / 30 / 1.5 (MFI 6 at 190 ° C under 2.16 kg), and 1.2% of organic stabilizers (consisting of 0.8% phenol Lowinox 44B25 Great Lakes company, 0.2% phosphite Irgafos 168 Ciba company, 0.2% anti-UV Tinuvin 312 Ciba).
    In an advantageous embodiment, the present invention relates to a multilayer tubular structure (MLT) as defined above, in which the barrier layer (1) is a layer of polyphthalamide (PPA) or fluoropolymer, in particular of ETFE type , EFEP, CPT.
    The term PPA signifies a composition based predominantly on a polyamide comprising a majority of units which comprise at least one aromatic monomer, in particular polyphthalamide of copolyamide type type 6.T / x (where x denotes one or more comonomers) such as Zytel HTN from Dupont, such as Grivory HT from Ems, such as Amodel from Solvay, such as Genestar from Kuraray, such as pPA compositions based on coPA6T / 6l, COPA6T / 66, COPA6T / 6 , coPA6T / 61/66, PPA9T, coPPA9T / x, PPA10T, coPPA10T / x.
    Advantageously, in the multilayer tubular structure (MLT) as defined above, the polyamide of the outer layer (2) is a polyamide chosen from B or C as defined above, in particular PA 11, PA12, PA610, PA612, PA1012, the corresponding copolyamides and the mixtures of said polyamides or copolyamides, the polyamides obtained from a lactam being advantageously washed.
    In another embodiment, the present invention relates to a multilayer tubular structure (MLT) as defined below, wherein the PPA or fluoropolymer of the barrier layer (1) is conductive.
    Advantageously, in the multilayer tubular structure (MLT) as defined above, the polyamide of the layer (3) is a mixture of a polyamide having an average number of carbon atoms per nitrogen atom of 10 or more and a polyamide having an average number of carbon atoms per nitrogen atom of 6 or less, for example PA12 and PA6 and an anhydride functionalized (co) polyolefin.
    Advantageously, in the multilayer tubular structure (MLT) as defined above, the polyamide of the layer (3) is chosen from the binary mixtures: PA6 and PA12, PA6 and PA612, PA6 and PA610, PA12 and PA612, PA12 and PA610, PA1010 and PA612, PA1010 and PA610, PA1012 and PA612, PA1012 and PA610, and ternary mixtures: PA6, PA610 and PA12; PA6, PA612 and PA12; PA6, PA614 and PA12.
    In another embodiment, the present invention relates to a multilayer tubular structure (MLT) as defined above, wherein at least one of the layers (2), (2 ') and (3) comprises at least one impact modifier and / or at least one additive.
    It is obvious that the impact modifier or the additive is not a plasticizer.
    Advantageously, the layers (2) and (2 ') comprise at least one impact modifier and / or at least one additive.
    Advantageously, the layers (2) and (3) comprise at least one impact modifier and / or at least one additive.
    Advantageously, the layers (2), (2 ') and (3) comprise at least one Choc modifier and / or at least one additive.
    In another embodiment, the present invention relates to a multilayer tubular structure (MLT) as defined above, wherein the structure comprises two layers in the following order (2) // (1), the layer (2) ) containing not more than 1.5% by weight of plasticizer, relative to the total weight of the composition of each layer, in particular the layer (2) is devoid of plasticizer.
    In another embodiment, the present invention relates to a multilayer tubUlaifO structure (MLT) as defined above, wherein the structure comprises three layers in the following order (2 ') // (2) // (1). ), the layer (2 *) being as defined above, the layer (2) containing not more than 1.5% by weight of plasticizer, relative to the total weight of the composition of each layer, in particular the layer (2) is devoid of plasticizer.
    According to another embodiment, the present invention relates to a multilayer tubular structure (MLT) as defined above, in which the structure comprises the layers in the following order: (2 ') // (2) // ( 3) // (1) in which the layers (2) and (2 ') are as defined above, the layer (3) containing not more than 1.5% by weight of plasticizer, relative to the weight total of the composition of each layer, the layer (3) comprising the plasticizer or the layer (3) being devoid of plasticizer.
    In particular, said layer (2 ') of the above four-layer structure is plasticized, said plasticizer being in particular present in a proportion of 1.5% to 15% by weight relative to the total weight of the composition of said layer. the thickness of said layer (2 ') is preferably up to 20% of the total thickness of the tubular structure, in particular up to 200 μm, in particular the layer (2') is the outermost and is the only plasticized, the (or) layer (s) (2) being devoid of (s) plasticizer.
    According to another aspect, the present invention relates to the use of a multilayer tubular structure MLT, as defined above, for the transport of fluids, in particular gasoline.
    According to yet another aspect, the present invention relates to the use of a MLT multilayer tubular structure as defined above, to satisfy an extractables test, said test consisting in particular of filling said MLT multilayer tubular structure with alcoholic essence. type FAM-B and heat the whole at 60 ° C for 96 hours, then empty it by filtering it in a beaker, then let the filtrate of the beaker evaporate at room temperature to finally weigh this residue whose proportion must be less than or equal to approximately 6g / m2 of internal tube surface.
    All the variants described for the MLT multilayer tubular structure apply here for the use of said MLT multilayer tubular structure to satisfy said extractables test.
    An extractable value of less than or equal to about 6 g / m 2 of internal tube surface indicates that the extractable fraction is very small and thus will not clog the injectors.
    EXAMPLES The invention will now be described in more detail with the aid of the following examples which are not limiting.
    The following structures were prepared by extrusion:
    The multilayer tubes are made by coextrusion. A McNeil multi-layer extrusion industrial line equipped with extruders connected to a spiral mandrel multilayer extrusion head is used.
    The screws used are single screw extruders having screw profiles adapted to polyamides. In addition, extruders and the multilayer extrusion head, the extrusion line comprises: • a die-punch assembly, located at the end of the coextrusion head; the internal 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 tube dimensions and line speed; • a vacuum container with an adjustable vacuum level. In this tray circulates water maintained at 20 ° C in general, which is immersed in a caliber to conform the tube in its final dimensions. The diameter of the template is adapted to the dimensions of the tube to be produced, typically from 8.5 to 10 mm for a tube with an external diameter of 8 mm and a thickness of 1 mm; • a succession of cooling tanks in which water is maintained at 20 ° C, to cool the tube along the path of the head to the draft bench; • a diameter meter; • a draw bench.
    The extruder configuration is used to make the tubes from 2 layers to 5 layers. In the case of structures whose number of layers is less than 5, several extruders are then fed with the same material. Before the tests, in order to ensure the best tube properties and a good extrusion quality, it is verified that the extruded materials have a residual moisture content before extrusion of less than 0.08%. In the opposite case, an additional step of drying the material is carried out before the tests, generally in a vacuum dryer, overnight at 80 ° C.
    The tubes, which meet the characteristics described in this patent application, were taken after stabilization of the extrusion parameters, the dimensions of the tube referred to no longer changing over time. The diameter is controlled by a laser diameter meter installed at the end of the line. Generally, the line speed is typically 20m / min. It usually varies between 5 and 100m / min.
    The screw speed of the extruders depends on the thickness of the layer and the diameter of the screw as is known to those skilled in the art.
    In general, the temperature of the extruders and tools (head and coupling) must be adjusted so as to be sufficiently greater than the melting temperature of the compositions in question, so that they remain in the molten state, thus avoiding that they solidify and block the machine.
    The tubular structures were tested on different parameters (Table I). The amount of extractives was determined, the barrier properties were evaluated as well as the shock and burst. Table II indicates the tests used and the classification of the results.
    TABLE I
    (i) Bursting is the bursting after at least 96 h with FAM-B bio-gasoline inside, so we look for a value high enough to hold the pressure.
    Compositions PA12-TL: denotes a composition based on polyamide 12 of Mn (number-average molecular mass) 35000, containing 6% of plasticizer BBSA (benzyl butyl sulphonamide), and 6% of EPR functionalised anhydride Exxelor VA1801 (Exxon company), and 1.2% of organic stabilizers consisting of 0.8% phenol (Lowinox 44B25 from Great Lakes), 0.2% phosphite (Irgafos 168 from Ciba, 0.2% anti-UV (Tinuvin 312) Ciba) The melting temperature of this composition is 175 ° C. PA12-NoPlast = PA12-TL without the plasticizer (the latter is replaced by the same PA 12) PA12: Polyamide 12 of Mn (number-average molecular weight) ) 35000. EPR1: Refers to an EPR functionalized with an anhydride functional group (0.5-1% by weight), MFI 9 (at 230 ° C., sub) 10kg, Exxelor type VA1801 from Exxon.
    Organic stabilizer = 1.2% of organic stabilizers consisting of 0.8% phenol (Lowinox 44B25 from Great Lakes), 0.2% phosphite (Irgafos 168 from Ciba, 0.2% anti-UV (Tinuvin 312) Ciba company).
    Plasticizer = BBSA (benzyl butyl sulfonamide). PPA10T = coPA10.T / 6.T molar ratio 60/40 T fusion 280 ° C + 18% EPR1 + stab orga PPA10T / 6T = COPA10.T / 6.T with 40% mol of 6.T (from MFI 300 ° C, 5kg = 8, and Melting T ° C 280 ° C) + 15% EPRI + stab orga EFEPc = Functional EFEP and Daukin type Neoflon RP5000AS conductor
    The structures having plasticizer-free layers above the barrier in contact with the fluid exhibit excellent results on the extractables test and are much better than counterexamples in which the outer layer is plasticized or those in which double barrier is present.
    权利要求:
    Claims (17)
    [1" id="c-fr-0001]
    Multilayer tubular structure MLT intended for the transport of fluids, in particular gasoline, comprising from inside to outside at least one inner barrier cup (1) and at least one outer cup (2) situated above the barrier layer, said outer layer (2) of all the layers (2) and any other layers above the barrier layer, containing on average from 0 to 5% of plasticizer relative to the total weight of the composition of the layer (2), or in which all the outer layers, situated above the barrier layer, comprise on average from 0 to 5% of plasticizer, said outer layer (2) comprising predominantly at least one polyamide of aliphatic type or consisting of more than 75% of aliphatic units, said aliphatic polyamide being selected from: - a polyamide noted A having an average number of carbon atoms per nitrogen atom noted Ca between 4 and 8.5 preferably between 4 and 7; a polyamide denoted B and an average number of carbon atoms per nitrogen atom noted Cb of between 7 and 10, advantageously between 7.5 and 9.5; a polyamide noted C having an average number of carbon atoms per nitrogen atom noted Ce between 9 and 18, advantageously between 10 and 18; provided that when said outer layer (2) comprises at least three polyamides, at least one of said polyamides A, B or C is excluded.
    [2" id="c-fr-0002]
    2. multilayer tubular structure (MLT) according to claim 1, wherein said outer layer (2) comprises from 0 to 1.5% plasticizer relative to the total weight of the composition of the layer (2).
    [3" id="c-fr-0003]
    Multilayer tubular structure (MLT) according to claim 1 or 2, wherein at least one second outer layer (2 ') above the barrier layer is present, and preferably located above the layer (2). ), said cup (2 ') being plasticized, said plasticizer being in particular present in a proportion of 1.5% to 15% by weight relative to the total weight of the composition of said layer, the thickness of said layer (2 ') preferably represents up to 20% of the total thickness of the tubular structure, in particular up to 200 μm.
    [4" id="c-fr-0004]
    4. multilayer tubular structure (MLT) according to claim 3, wherein the layer (2 ') is the outermost and is the only plasticized, the (or) layer (s) (2) being devoid of plasticizer (s) .
    [5" id="c-fr-0005]
    5. multilayer tubular structure (MLT) according to one of claims 1 to 4, wherein at least one layer (3) is present, said layer (3) containing not more than 15% by weight of plasticizer, preferably not more than 1.5% by weight of plasticizer, relative to the total weight of the constituents of the layer (3), advantageously the layer (3) is devoid of plasticizer, said layer (3) comprising predominantly at least one aliphatic type polyamide or consisting of more than 75% of aliphatic units, said aliphatic polyamide being chosen from: a polyamide noted A having an average number of carbon atoms per nitrogen atom noted Ca inclusive of 4 to 8.5, advantageously of 4 to 7: - a polyamide noted B and an average number of carbon atoms per nitrogen atom noted Ce from 7 to 10, preferably from 7.5 to 9.5; a polyamide denoted C having an average number of carbon atoms per nitrogen atom, denoted Ce comprising from 9 to 18, advantageously from 10 to 18; provided that when said layer (3) comprises at least three polyamides, at least one of said polyamides A, B or G is excluded, said layer (3) being located between the outer layer (2) and the barrier layer (1 ); or said layer (3) is a binder layer whose thickness represents up to 15% of the structure (MLT).
    [6" id="c-fr-0006]
    6. multilayer tubular structure (MLT) according to one of claims 1 to 5, the polyamide of the outer layer (2) is a completely aliphatic polyamide.
    [7" id="c-fr-0007]
    7. Multilayer tubular structure (MLT) according to one of claims 1 to 6, wherein the barrier layer (1) is a layer of PPA or fluoropolymer, in particular of the type ETFE, EFEP, CPT.
    [8" id="c-fr-0008]
    8. multilayer tubular structure (MLT) according to one of claims 1 to 7, wherein the polyamide of the outer layer (2) is a polyamide selected from B or C as defined in claim 1, in particular PA 11, PA12, PA610, PA612, PA1012, the corresponding copolyamides and the mixtures of said polyamides or copolyamides, the polyamides obtained from a lactam being advantageously washed.
    [9" id="c-fr-0009]
    9. Multilayer tubular structure (MLT) according to one of claims 1 to 8, wherein the PPA or the fluoropolymer of the barrier layer (1) is conductive.
    [10" id="c-fr-0010]
    10. Multilayer tubular structure (MLT) according to one of claims 5 to 9, wherein the polyamide of the layer (3) is selected from the binary mixtures: PA6 and PA12, PA6 and PA612, PA6 and PA610, PA12 and PA612 , PA12 and PA610, PA1010 and PA612, PA101Q and PA610, PA1012 and PA612, PA1012 and PA610, and ternary mixtures: PA6, PA610 and PA12; PA6, PA612 and PA12; PA6, PA614 and PA12.
    [11" id="c-fr-0011]
    11. multilayer tubular structure (MLT) according to one of claims 5 to 10, wherein at least one of the layers (2) or (3) comprises at least one impact modifier and / or at least one additive.
    [12" id="c-fr-0012]
    Multilayer tubular structure (MLT) according to one of Claims 1 to 11, in which the structure comprises two layers in the following order (2) // (1), the layer (2) containing not more than 1 , 5% by weight of plasticizer, relative to the total weight of the composition of each layer, in particular the layer (2) is devoid of plasticizer.
    [13" id="c-fr-0013]
    Multilayer tubular structure (MLT) according to one of claims 3 to 12, wherein the structure comprises three layers in the following order (2 ') // (2) // (1), the layer (2') ) being as defined in claim 2, the layer (2) containing not more than 1.5% by weight of plasticizer, relative to the total weight of the composition of each layer, in particular the layer (2) is devoid of plasticizer.
    [14" id="c-fr-0014]
    Multilayer tubular structured structure (MLT) according to one of Claims 5 to 13, in which the structure comprises three layers in the following order: (2) // (3) // (1), the layer (3) comprising plasticizer, or the layer (3) when different from the binder layer is free of plasticizer.
    [15" id="c-fr-0015]
    The multilayer tubular structure (MLT) according to one of claims 5 to 14, wherein the structure comprises the layers in the following order: (2 ') // (2) // (3) // (1) the layer (3) comprising plasticizer, or the layer (3) is devoid of plasticizer.
    [16" id="c-fr-0016]
    16. Use of a MLT multilayer tubular structure, as defined in one of claims i to 15, for the transport of fluids, in particular gasoline.
    [17" id="c-fr-0017]
    17. Use of a MLT multilayer tubular structure, as defined in one of the awakenings 1 to 15, to satisfy an extractables test, said test consisting in particular of filling said MLT multilayer tubular structure of alcoholic essence type FAM- B and heat the whole at 60 ° C for 96 hours, then empty it by filtering it in a beaker, then let the filtrate of the beaker evaporate at room temperature to finally weigh this residue whose proportion must be lower or equal to about 6g / m 2 of internal tube surface.
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    同族专利:
    公开号 | 公开日
    CN111730917A|2020-10-02|
    JP2018515358A|2018-06-14|
    WO2017121962A1|2017-07-20|
    CN107405895B|2020-11-03|
    JP6788601B2|2020-11-25|
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    KR20170117558A|2017-10-23|
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    US11161319B2|2021-11-02|
    CN111730918A|2020-10-02|
    FR3046827B1|2018-05-25|
    US20180099473A1|2018-04-12|
    EP3259132A1|2017-12-27|
    KR102028268B1|2019-10-02|
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    法律状态:
    2016-12-15| PLFP| Fee payment|Year of fee payment: 2 |
    2017-07-21| PLSC| Publication of the preliminary search report|Effective date: 20170721 |
    2017-12-11| PLFP| Fee payment|Year of fee payment: 3 |
    2019-12-16| PLFP| Fee payment|Year of fee payment: 5 |
    2020-12-10| PLFP| Fee payment|Year of fee payment: 6 |
    2021-12-17| PLFP| Fee payment|Year of fee payment: 7 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1650339A|FR3046827B1|2016-01-15|2016-01-15|MULTILAYER TUBULAR STRUCTURE HAVING IMPROVED RESISTANCE TO EXTRACTION IN BIO-GASOLINE AND USE THEREOF|
    FR1650339|2016-01-15|FR1650339A| FR3046827B1|2016-01-15|2016-01-15|MULTILAYER TUBULAR STRUCTURE HAVING IMPROVED RESISTANCE TO EXTRACTION IN BIO-GASOLINE AND USE THEREOF|
    US15/558,365| US11161319B2|2016-01-15|2017-01-12|Multilayer tubular structure having better resistance to extraction in biofuel and use thereof|
    KR1020177026017A| KR102028268B1|2016-01-15|2017-01-12|Multilayer tubular structure having improved resistance to extraction in biogasoline and use thereof|
    EP17712188.6A| EP3259132B1|2016-01-15|2017-01-12|Multilayer tubular structure having improved resistance to extraction in biogasoline and use thereof|
    PCT/FR2017/050067| WO2017121962A1|2016-01-15|2017-01-12|Multilayer tubular structure having improved resistance to extraction in biogasoline and use thereof|
    JP2017548957A| JP6788601B2|2016-01-15|2017-01-12|Use of multi-layer tubular structures with improved elution resistance into biofuels and the multi-layer tubular structures|
    CN201780001029.3A| CN107405895B|2016-01-15|2017-01-12|Multilayer tubular structure with improved resistance to extraction in biogasoline and use thereof|
    CN202010633149.9A| CN111730917A|2016-01-15|2017-01-12|Multilayer tubular structure with improved resistance to extraction in biogasoline and use thereof|
    CN202010633162.4A| CN111730918A|2016-01-15|2017-01-12|Multilayer tubular structure with improved resistance to extraction in biogasoline and use thereof|
    JP2020117551A| JP2020189490A|2016-01-15|2020-07-08|Multilayer tubular structure having improved resistance to extraction in biofuel and use thereof|
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