Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B1/00—Layered products having a non-planar shape
  • B32B1/08—Tubular products
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
  • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
  • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
  • F16L11/00—Hoses, i.e. flexible pipes
  • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
  • F16L11/045—Hoses, i.e. flexible pipes made of rubber or flexible plastics with four or more layers without reinforcement
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2597/00—Tubular articles, e.g. hoses, pipes
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
  • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
  • F16L11/00—Hoses, i.e. flexible pipes
  • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
  • F16L2011/047—Hoses, i.e. flexible pipes made of rubber or flexible plastics with a diffusion barrier layer

Definitions

• the present invention relates to a polyamide antistatic multilayer pipe for the transfer of fluids.
• tubes for the transfer of fluid By way of example of tubes for the transfer of fluid, mention may be made of the tubes for gasoline, and in particular for bringing gasoline from the tank to the engine of automobiles.
• fluid transfer mention may be made of the fluids used in the fuel cell, the CO 2 system for cooling and air conditioning, the hydraulic systems and the cooling circuit. , air conditioning and power transfers at medium pressure. The circulation of these fluids can generate electrostatic charges, the accumulation of which can lead to an electric shock. This is important for fluids that can ignite easily like gasoline.
• the present invention more particularly relates to conductive tubes based on polyamides for the transport of gasoline and in particular, to bring the essence of the tank of an automobile to the engine.
• the patent application EP 1036967 describes a multilayer tube based on polyamides, characterized in that it comprises in its radial direction from the inside towards the outside:
• an inner layer formed of a polyamide or a mixture of polyamide and polyolefin with a polyamide matrix, this layer having a dispersed charge of electroconductive carbon black producing a surface resistivity of less than
• this layer not comprising electroconductive carbon black or an electrically significant amount of this carbon black
• the conductive inner layer contains 60 to 70 parts of polyamide, 5 to 15 parts of a compatibilizer and the complement to 100% of HDPE (high density polyethylene) as well as carbon black.
• the patent application EP 1036968 describes a multilayer tube based on polyamides, characterized in that it comprises in its radial direction from the inside to the outside:
• P 1 and P 3 may be identical or different, the layers (1), (2a) (2) and (3) being successive and adhering to each other in their respective contact zone.
• the conductive inner layer contains 60 to 70 parts of polyamide, 5 to 15 parts of a compatibilizer and the complement to 100% of HDPE (high density polyethylene) as well as carbon black.
• the patent application US 2002/0142118 describes a gas tube comprising going from the outside to the inside: an outer layer of PA 6.12, a binder layer based on polyamide polyamine, a layer of EVOH and an inner layer of PA 6 in contact with the gasoline.
• the PA layer 6 may be conductive; no details are given on its composition.
• the present invention relates to a multilayer tube of the above type, successively comprising in its radial direction from the outside to the inside: an outer layer (1) of polyamide 11 or 12,
• the inner layer (5) in contact with the transported fluid comprises by weight, the total being 100%:
• PA 6 from 40 to 65% (advantageously from 45 to 60%) of PA 6, from 0 to 20%, advantageously from 1 to 20% (preferentially from 5 to
• HDPE 15%) of HDPE, from 10 to 30% (advantageously 15 to 25%) of at least one polymer P1 chosen from impact modifiers and polyethylenes, at least one of HDPE and P1 being functionalized in whole or in part,
• Such an inner layer composition (5) makes it possible to produce a multilayer tube which not only perfectly meets the requirements of the specifications of the gasoline tubes as stated above, but which also has electroconductive properties while retaining cold ductility properties.
• the multilayer pipe according to the invention simultaneously has very good conductive and mechanical properties; it is observed in particular that no breakage of multilayer pipes occurs during impact tests at -40 ° C.
• the PA-based inner layer 6 in contact with the transported fluid comprises by weight, the total being 100%:
• These proportions of electroconductive material in the composition of the inner layer comprised between 5 and 30% by weight, advantageously between 15 and 30%, preferably between 17 and 24% and even more preferably between 20 and 24%, make it possible to obtain a surface resistivity of less than 10 6 ⁇ , the value required for an electroconductive multilayer pipe.
• the surface resistivity can also be expressed in Ohm / square (Ohm / square), this unit has the dimension of Ohms.
• These tubes may have an outside diameter of 6 to 10 mm and a thickness of the order of 0.5 to 5 mm.
• the gasoline tube according to the invention has an outside diameter ranging from 6 to 12 mm, a total thickness of 0.8 mm to 2.5 mm.
• the thickness of the outer layer (1) is between 25 and 60% of the thickness of the tube.
• the thickness of all the layers (4) and (5) represents 30 to 50% of the thickness of the tube. If the layer (4) is present, the thickness of the layer (5) advantageously represents 5 to 20% of the thickness of the set of layers (4) and (5).
• the tube of the present invention is very little permeable to gasoline, in particular hydrocarbons and their additives, such as 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. This tube has excellent electrical properties before and after contact with gasoline. This tube meets the SAE standard J1645 in particular.
• the invention also relates to the use of these tubes for transporting gasoline.
• the polyamide of the outer layer (1) its inherent viscosity may be between 1 and 2 and advantageously between 1, 2 and 1.8. The inherent viscosity is measured at 20 ° C for a concentration of 0.5% in meta-cresol.
• 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 additives, such as anti-UV, stabilizers, antioxidants, flame retardants, etc.
• the polyamide of the outer layer (1) may contain at least one product chosen from plasticizers, impact modifiers and catalysed or uncatalyzed polyamides.
• plasticizer it is chosen from benzene sulphonamide derivatives, such as n-butyl benzene sulphonamide (BBSA), ethyl toluene sulfonamide or N-cyclohexyl toluene sulfonamide; esters of hydroxy-benzoic acids, such as 2-ethylhexyl parahydroxybenzoate and 2-decyl hexyl parahydroxybenzoate; esters or ethers of tetrahydrofurfuryl alcohol, such as oligoethyleneoxytetrahydrofurfurylalcohol; esters of citric acid or of hydroxy-malonic acid, such as oligoethyleneoxy malonate.
• BBSA n-butyl benzene sulphonamide
• esters of hydroxy-benzoic acids such as 2-ethylhexyl parahydroxybenzoate and 2-decyl hexyl parahydroxybenzoate
• BBSA n-butyl benzene sulfonamide
• polyolefins As regards the impact modifier, mention may be made, for example, of polyolefins, crosslinked polyolefins and elastomers EPR, EPDM, SBS and SEBS, these elastomers being graftable to facilitate their compatibilization with polyamide, polyamide block copolymers and polyether blocks.
• These polyamide block and polyether block copolymers are known per se; they are also designated by the name PEBA (polyether block amide) and sold by the applicant under the name PEBAX®.
• Acrylic elastomers can also be mentioned, for example those of the NBR, HNBR or X-NBR type.
• Polyolefins useful as impact modifiers are, for example, ethylene-alkyl (meth) acrylate-maleic anhydride copolymers (or glycidyl methacrylate). They are sold by the plaintiff under the name of Lotader®.
• the catalyzed polyamide it is a polyamide containing a polycondensation catalyst such as a mineral or organic acid, for example phosphoric acid.
• the catalyst can be added to the polyamide after it has been prepared by any method, or simply, and it is preferred, to be the remainder of the catalyst used for its preparation. Polymerization and / or depolymerization reactions may be very substantially carried out during the mixing of this catalyzed polyamide and the polyamide of the outer layer.
• the amount of catalyst may be between 5 ppm and 15000 ppm of phosphoric acid relative to the catalyzed polyamide.
• the amount of catalyst can be up to 3000 ppm and advantageously between 50 and 1000 ppm.
• the contents will be different and can be chosen suitably according to the usual polycondensation techniques of polyamides.
• the proportion of plasticizer may be (by weight) between 0 and 15%
• the polyamide of the outer layer is PA 12. If catalyzed polyamide is added in this polyamide, then this catalyzed polyamide is advantageously PA 1 1.
• compositions of the outer layer they may be prepared by melt blending of the constituents according to the usual techniques of thermoplastics.
• the outer layer may also include usual additives polyamides such as UV stabilizers, antioxidants, pigments, flame retardants.
• layer (2) of binder is meant any product for adhesion of the layers together.
• grafted polyolefins and copolyamides may be mentioned.
• copolyamide 6/12 which is a copolyamide of caprolactam and lauryllactam.
• the proportions of caprolactam and lauryllactam can vary from 20 to 80% of caprolactam for 80 to 20% of lauryllactam respectively.
• it is a mixture of a 6/12 copolyamide rich in 6 and a 6/12 copolyamide rich in 12.
• copolyamide 6/12 results from the condensation of caprolactam with lauryllactam.
• 6 refers to the motifs derived from caprolactam
• 12 refers to the motifs derived from lauryllactam. It would not be outside the scope of the invention if caprolactam was replaced in whole or in part by aminocaproic acid; likewise, lauryllactam could be replaced in whole or in part by aminododecanoic acid.
• These copolyamides may include other reasons, provided that the ratios of proportions of 6 and 12 are respected.
• the copolyamide rich in 6 comprises 50 to 90% by weight of 6 for respectively 50 to 10% of 12.
• the copolyamide rich in 12 comprises 50 to 90% by weight of 12 for respectively 50 to 10% of 6.
• the proportions of the 6-rich copolyamide and the 12-rich copolyamide can be, by weight, 30/70 to 70/30 and, preferably,
• copolyamide mixtures may also comprise up to 30 parts by weight of other (co) polyamides or grafted polyolefins per 100 parts of the 6-rich and 12-rich copolyamides.
• copolyamides have a melting temperature (DIN 53736B standard) of between 60 and 200 ° C. and their relative viscosity in solution can be between 1, 3 and 2.2 (DIN 53727 standard, solvent m-cresol, concentration
• 2002/01421 18 whose content is incorporated in the present application.
• They are polyamines polyamines prepared from polyamines having at least 4 nitrogen atoms and either lactams or a mixture of diamines and diacids. These polyamines polyamines can be mixed with polyamides such as PA 12, PA 6.12 and possibly impact modifiers such as EPR and grafted EPR.
• This binder layer may contain stabilizers. According to one form of the invention, this binder layer may contain at least one impact modifier. This impact modifier can be chosen from the impact modifiers described above for the outer layer (1).
• the EVOH copolymer is also called saponified ethylene-vinyl acetate copolymer.
• the saponified ethylene-vinyl acetate copolymer to be used according to the present invention is a copolymer having an ethylene content of 20 to 70 mol%, preferably 25 to 45 mol%, the degree of saponification of its vinyl acetate component. not less than 95 mol%.
• melt flow index ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ / 10 minutes.
• MFI abbreviation for "MeIt Flow Index” designates the melt flow index.
• this saponified copolymer may contain small proportions of other comonomer ingredients, including ⁇ -olefins such as propylene, isobutene, ⁇ -octene, ⁇ -dodecene, ⁇ -octadecene, etc., unsaturated carboxylic acids or their salts, partial alkyl esters, complete alkyl esters, nithles, amides and anhydrides of said acids, and unsaturated sulfonic acids or their salts.
• ⁇ -olefins such as propylene, isobutene, ⁇ -octene, ⁇ -dodecene, ⁇ -octadecene, etc.
• unsaturated carboxylic acids or their salts unsaturated carboxylic acids or their salts
• partial alkyl esters partial alkyl esters, complete alkyl esters, nithles, amides and anhydrides of said acids, and unsatur
• the EVOH layer may consist of EVOH-based mixtures.
• EVOH-based blends they are such that EVOH forms the matrix, ie it represents at least 40% by weight of the mixture and preferably at least 50%.
• the other constituents of the mixture are chosen from polyolefins, polyamides, impact modifiers, optionally functionalized.
• the impact modifier can be chosen from elastomers, copolymers of ethylene and an olefin having from 4 to 10 carbon atoms (for example ethylene-octene copolymers) and very low density polyethylenes. Examples of elastomers include EPR and EPDM.
• EPR abbreviation for Ethylene Propylene Rubber
• EPDM ethylene-propylene-diene monomer elastomers
• mixtures comprising, by weight, 50 to 95% of EVOH for respectively 50 to 5% of grafted EPR, advantageously 60 to 95% of EVOH for respectively 40 to 5% of EPR.
• compositions comprising: 50 to 95% by weight of an EVOH copolymer,
• the layer (4) it may be PA 6 or a mixture of PA 6 and PA polyolefin matrix 6 and polyolefin dispersed phase.
• PA 6 and PA 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 PE, EPR EPDM. 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.
• the matrix PA 6 represents 50 to 85% by weight for respectively 50 to 15% of dispersed phase.
• the matrix PA 6 represents 55 to 80% by weight for respectively 45 to 20% of dispersed phase.
• the mixtures of PA 6 and polyolefin matrix PA 6 comprise by weight, the total being 100%: 50 to 90% (advantageously 60 to 80%) of PA 6,
• the impact modifier is chosen from elastomers and very low density polyethylenes.
• SBS SBS, SIS, SEBS block polymers and ethylene / propylene elastomers.
• EPR ethylene / propylene / diene
• EPDM ethylene / propylene / diene
• very low density polyethylenes they are, for example, metallocenes with a density of, for example, between 0.860 and 0.900.
• 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.
• unsaturated carboxylic acid examples include 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.
• the proportion of all of the functionalized HDPE and functionalized P1 with respect to the entire functionalized and non-functionalized HDPE and functionalized and non-functionalized P1 may be comprised (by weight) of between 1 and 80%, advantageously between 5 and 70% and preferably between 20 and 70%. Otherwise expressed, the proportion of HDPE and P1 which are functionalized relative to the total amount of HDPE and P1 may be comprised (by weight) of between 1 and 80%, advantageously between 5 and 70% and preferably between 20 and 70%. .
• 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 polyolefin PA 6 matrix blends, the HDPE is not grafted and P1 is a mixture of a grafted elastomer and an ungrafted elastomer.
• the HDPE is not grafted and P1 is a grafted polyethylene optionally mixed with an elastomer.
• MI 1 denoting O the flow index at 190 ° C under a load of 10 kg
• M1 2 the index under a load of 2.16 kg
• (A2) may be selected from EPR, VLDPE, ethylene / alkyl (meth) acrylate copolymers or ethylene / alkyl (meth) acrylate / maleic anhydride copolymers.
• the Ml 10 / Ml 2 ratio is less than 35 and preferably between 22 and 33.
• the MI 20 of the mixture (A) of the polymers (A1) and (A2) co-grafted is less than 24, MI 20 denoting the melt index at 190 ° C under a load of 21 6 kg.
• the layer (4) may contain stabilizers and one or more plasticizers.
• the polymer P1 has already been described in the layer (4) above.
• the polymer P1 of the layer (5) and that of the layer (4) may be identical or different.
• the proportions of HDPE and functionalized P1 with respect to the total amount of HDPE and P1 can be chosen within the ranges of values mentioned for the layer (4) above.
• an electroconductive material there may be mentioned 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 / 100g. These carbon blacks are described in the patent application WO 99-33908, the content of which is incorporated in the present application.
• the layer (5) may contain stabilizers and one or more plasticizers.
• compositions (5) Five inner layer compositions (5) were prepared. The various compounds entering into each of the compositions are detailed in the table below.
• Carbon black is supplied by Timcal under the name "Ensaco 250 Granular”.
• the DBP absorption is 190 ml / g and the BET surface is about 65 m 2 / g.
• the compatibilizer is a maleic anhydride grafted ethylene copolymer.
• the tubes 1 to 5 are identical to each other, with the exception of the composition of the inner layer, as described in Ex. 1 to 5 respectively.
• the binder is a mixture of (i) 40% by weight of 6/12 copolyamide with 40% of 6 unit and (ii) 60% of 6/12 copolyamide with 70% of 6 unit.
• EVOH denotes a copolymer EVOH with 32mol% of ethylene sold under the name Soarnol® DC3203F by Nippon Goshei.
• the layer (4) consists of a mixture of 65% of PA 6, 15% of HDPE and 20% of grafted EPR also comprising antioxidants.
• the resistivity is much lower than 10 6 ohms, this is not the case for the tube 4 which comprises only a low weight percentage of carbon black (4 % by weight of the total composition).
• the tubes 1 to 3 in accordance with the invention pass the impact test at -40 ° C. of the GM standard (General Motors) and the VW (Volkswagen) standard, unlike the tube 5.

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• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• General Engineering & Computer Science (AREA)
• Laminated Bodies (AREA)
• Rigid Pipes And Flexible Pipes (AREA)

Applications Claiming Priority (3)

Publications (1)

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Family Applications (1)

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• 2005
  • 2005-10-18 FR FR0510582A patent/FR2892173B1/fr not_active Expired - Fee Related
• 2006
  • 2006-10-17 US US12/090,756 patent/US20090314375A1/en not_active Abandoned
  • 2006-10-17 CN CN2006800439205A patent/CN101312824B/zh not_active Expired - Fee Related
  • 2006-10-17 EP EP06841983A patent/EP1937465A1/fr not_active Withdrawn
  • 2006-10-17 KR KR1020087009419A patent/KR20080056228A/ko not_active Application Discontinuation
  • 2006-10-17 WO PCT/FR2006/051041 patent/WO2007057584A1/fr active Application Filing
  • 2006-10-17 JP JP2008536098A patent/JP2009511311A/ja not_active Withdrawn
  • 2006-10-17 BR BRPI0617667-4A patent/BRPI0617667A2/pt not_active IP Right Cessation

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