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
  • B32B27/06—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
  • 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
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal 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
  • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
• • 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
  • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
• • 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
  • B32B27/32—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
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
• • 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
  • B32B2323/00—Polyalkenes
  • B32B2323/04—Polyethylene
• • 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
  • B32B2327/00—Polyvinylhalogenides
• • 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
  • B32B2329/00—Polyvinylalcohols, polyvinylethers, polyvinylaldehydes, polyvinylketones or polyvinylketals
  • B32B2329/04—Polyvinylalcohol
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
  • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
  • Y10T428/1379—Contains vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit
  • Y10T428/1383—Vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit is sandwiched between layers [continuous layer]

Definitions

• the present invention relates to a multilayer tube comprising a layer of a functionalized fluoropolymer, at least one layer of a polyolefin and at least one layer of a barrier polymer.
• the polyolefin may be a polyethylene, especially high density polyethylene (HDPE) or crosslinked polyethylene (PEX noted).
• the tube can be used for transporting different fluids.
• the invention also relates to the uses of this tube.
• Polyolefins especially polyethylenes, are widely used thermoplastics because they have good mechanical properties, they are transformed and allow to weld the tubes together easily.
• Polyolefins are widely used for the manufacture of tubes for the transport of water or city gas. When the gas is under a high pressure (> 10 bar or more), it is necessary for the polyolefin to be mechanically resistant to the stresses exerted by the gas under pressure.
• Polyethylene can be subjected to an aggressive chemical medium.
• additives or aggressive chemicals for example ozone, chlorinated derivatives used for the purification of water such as bleach
• Water additives can damage the polyolefin over time.
• an important issue today is to be able to eliminate the maximum of germs, bacteria or microorganisms by raising the temperature of the water (> 70 ° C) circulating in the tubes.
• the action of water additives on the polyolefin is then all the more powerful.
• a problem to be solved by the invention is therefore to have a plastic tube which comprises a layer of polyolefin, especially polyethylene, and which has good chemical resistance vis-à-vis the transported fluid.
• the tube must in particular be resistant to chemical additives that are used in the treatment of water, especially when the water is hot.
• the tube has barrier properties.
• Barrier means that the tube brakes the migration to the transported fluid of contaminants present in the external medium or contaminants (such as antioxidants or polymerization residues) present in the polyolefin.
• Barrier also means that the tube slows the migration of oxygen or additives present in the fluid transported to the polyolefin layer.
• the tube has good mechanical properties, in particular good impact resistance and that the layers adhere well to each other (no delamination).
• the multilayer pipe must additionally have good adhesion between the layers (i.e. there is no delamination) so that it retains mechanical stability over time.
• the Applicant has developed a multilayer tube comprising at least one polyolefin layer which solves the problems posed.
• EP 1484346 published December 08, 2004 describes multilayer structures comprising a fluoropolymer grafted by irradiation.
• the structures can be in the form of bottles, tanks, containers or pipes.
• the structure of the multilayer tube according to the invention does not appear in this document.
• EP 1541343 published June 08, 2005 discloses a multilayer structure based on a fluoropolymer modified by radiation grafting for storing or transporting chemicals. In this chemical application, we mean products that are corrosive or dangerous, or products that we want to maintain purity.
• the structure of the multilayer tube according to the invention does not appear in this document.
• the invention relates to a multilayer pipe as described in claim 1 as well as to uses of the pipe in the transport of different fluids.
• the invention is also more generally related to a multilayer structure associating the same layers Ci to C 7 , this structure being in the form of hollow body, container, bottle, ...
• Figure 1 shows a sectional view of a multilayer pipe 1 according to the invention.
• This is the cylindrical tube of Example 1 having the following concentric layers, referenced from 2 to 6.
• layer 2 layer of PVDF
• layer 3 functionalized PVDF layer
• layer 4 EVOH layer
• layer 5 functionalized polyolefin layer
• layer 6 layer of PEX.
• the layers are arranged against each other in the order indicated 2 * 6.
• the innermost layer is the PVDF layer, the outermost layer is the PEX layer.
• the functionalized fluoropolymer is a fluorinated polymer bearing at least one functional group chosen from the following groups: carboxylic acid, carboxylic acid salt, carbonate, carboxylic acid anhydride, epoxide, carboxylic acid ester, silyl, alkoxysilane, carboxylic acid amide, hydroxy, isocyanate.
• the functional group is introduced into the fluoropolymer either by copolymerization or by grafting a monomer carrying a functional group as defined.
• the functionalized fluoropolymer may be obtained by copolymerizing a fluorinated monomer with at least one monomer carrying a functional group and optionally at least one other comonomer.
• the functionalized polymer may be a PVDF comprising monomeric units of VDF and monoesterified unsaturated diacid or vinylene carbonate as described in US 5415958.
• Another example of a functionalized fluoropolymer is that of a PVDF comprising monomeric units of VDF and itaconic or citraconic anhydride as described in US 6703465 B2.
• the functionalized fluoropolymer is prepared by an emulsion, suspension or solution process.
• the functionalized fluoropolymer may also be obtained by irradiation grafting of an unsaturated monomer (described below) on a fluoropolymer. In this case, we will speak for simplification of fluoropolymer grafted by irradiation.
• irradiated grafted fluoropolymer this is obtained by a method of grafting by irradiation of at least one unsaturated monomer on a fluorinated polymer (described below). We will speak for simplification of fluoropolymer grafted by irradiation.
• the fluoropolymer is premixed with the unsaturated monomer by all known melt blending techniques of the prior art.
• the mixing step is carried out in any mixing device such as extruders or kneaders used in the thermoplastics industry.
• an extruder will be used to form the mixture into granules.
• the grafting takes place on a mixture (in the mass) and not on the surface of a powder as described for example in US Pat. No. 5,576,106.
• the mixture of the fluorinated polymer and the unsaturated monomer is irradiated (beta beta or gamma gamma irradiation) in the solid state using an electronic or photonic source under an irradiation dose of between 10 and 200 kGray, preferably between 10 and 150 kGray.
• the mixture may for example be packaged in polythene bags, the air is removed and the bags are closed.
• the dose is between 2 and 6 Mrad and preferably between 3 and 5 Mrad. Irradiation with a cobalt-60 bomb is particularly preferred.
• the unsaturated monomer content which is grafted is 0.1 to 5% by weight (i.e., the unsaturated grafted monomer corresponds to 0.1 to 5 parts for 99.9 to 95 parts by weight).
• fluoropolymer preferably from 0.5 to 5%, preferably from 0.9 to 5%.
• the grafted unsaturated monomer content is dependent on the initial content of the unsaturated monomer in the fluoropolymer blend. unsaturated monomer to be irradiated. It also depends on the effectiveness of the grafting, and therefore the duration and energy of the irradiation.
• the unsaturated monomer which has not been grafted, as well as the residues released by the grafting, in particular the HF, can then optionally be removed. This last step may be necessary if the ungrafted unsaturated monomer is likely to hinder adhesion or for toxicology problems.
• This operation can be performed according to techniques known to those skilled in the art. Vacuum degassing may be applied, possibly by applying heating at the same time.
• 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, or else washing the fluoropolymer modified with a solvent inert with respect to the fluoropolymer and graft functions.
• a suitable solvent such as, for example, N-methylpyrrolidone
• a non-solvent for example in water or in an alcohol
• washing the fluoropolymer modified with a solvent inert for example, when grafting maleic anhydride, it can be washed with chlorobenzene.
• the grafting by irradiation takes place at "cold", typically at temperatures below 100 ° C., or even 50 ° C., so that the mixture of the fluorinated polymer and the unsaturated monomer is not at the same temperature.
• molten state as for a conventional grafting process in extruder.
• An essential difference is therefore that, in the case of a semi-crystalline fluorinated polymer (as is the case with PVDF for example), the grafting takes place in the amorphous phase and not in the crystalline phase, whereas homogeneous grafting takes place in the case of grafting in extruder in the molten state.
• the unsaturated monomer therefore does not distribute 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 unsaturated monomer on the fluoropolymer chains compared to a product that would be obtained by grafting into an extruder.
• the fluoropolymer modified by radiation grafting has the very good chemical resistance and the oxidation, as well as the good thermomechanical behavior, of the fluoropolymer before its modification.
• this denotes 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.
• PFBE perfluorobutyl ethylene
• the fluoropolymer may be a homopolymer or a copolymer, it may also include non-fluorinated monomers such as ethylene.
• the fluorinated polymer is chosen from:
• VDF vinylidene fluoride
• CTFE chlorotrifluoroethylene
• HFP hexafluoropropylene
• VF 3 trifluoroethylene
• TFE tetrafluoroethylene
• VF 3 trifluoroethylene
• CTFE chlorotrifluoroethylene
• TFE tetrafluoroethylene
• HFP hexafluoropropylene
• the fluoropolymer is a homo- or copolymer PVDF.
• This fluoropolymer indeed has a good chemical resistance, especially to UV and chemicals, and it is easily converted (more easily than PTFE or ETFE-type copolymers).
• the PVDF contains, by weight, at least 50% of VDF, more preferably at least 75% and more preferably at least 85%.
• the comonomer is advantageously 1 HFP.
• the PVDF has a viscosity ranging from 100 Pa.s to 3000 Pa.s, the viscosity being measured at 23O 0 C, at a shear rate of 100 s "1 using a capillary rheometer.
• these PVDFs are well suited to extrusion and injection, preferably PVDF has a viscosity of 300 Pa.s at 1200 Pa.s, the viscosity being measured at 23O 0 C, at a shear rate of 100 s "1 using a capillary rheometer.
• PVDF marketed under the trademark KYNAR ® 710 or 720 are perfectly suited for this formulation.
• Unsaturated carboxylic acids having 4 to 10 carbon atoms and their functional derivatives, particularly their anhydrides, are particularly preferred unsaturated monomers.
• unsaturated monomers are methacrylic acid, acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, undecylenic acid, allylsuccinic acid, and the like.
• cyclohex-4-ene-1,2-dicarboxylic acid 4-methyl-cyclohex-4-ene-1,2-dicarboxylic acid, bicyclo (2,2,1) hept-5-ene 2,3-dicarboxylic acid, x-methylbicyclo (2,2,1-hept-5-ene-2,3-dicarboxylic acid, zinc, calcium or sodium undecylenate, maleic anhydride, itaconic anhydride, citraconic anhydride, dichloromaleic anhydride, difluoromaleic anhydride, itaconic anhydride, crotonic anhydride, glycidyl acrylate or methacrylate, allyl glycidyl ether, vinyl silanes such as vinyl trimethoxysilane, vinyl triethoxysilane, vinyl triacetoxysilane, ⁇ - methacryloxypropyltrimethoxysilane.
• unsaturated monomers include C 1 -C 8 alkyl esters or glycidyl ester derivatives of unsaturated carboxylic acids such as methyl acrylate, methyl methacrylate, ethyl acrylate, methacrylate and the like.
• amide derivatives of unsaturated carboxylic acids such as acrylamide, methacrylamide, maleic monoamide, maleic diamide, maleic N - monoethylamide, N, N - diethylamide maleic, N - maleic monobutylamide, N 1 N - dibutylamide maleic, furamic monoamide, furamic diamide, fumaric N-monoethylamide, N, N-diethylamide fumaric, fumaric N-monobutylamide and N, N-dibutylamide furamic; imide derivatives of unsaturated carboxylic acids such as maleimide, N-butylmale
• maleic anhydride as well as zinc, calcium and sodium undecylenates are good graftable compounds because they have little tendency to homopolymerize or even to give rise to crosslinking.
• maleic anhydride is used. This monomer indeed offers the following advantages:
• the proportion of fluoropolymer is, by weight, between 80 to 99.9% for respectively 0.1 to 20% of unsaturated monomer.
• the proportion of fluorinated polymer is from 90 to 99% for 1 to 10% of unsaturated monomer, respectively.
• the term refers to a polymer comprising predominantly ethylene and / or propylene units. It may be a polyethylene, homo- or copolymer, the comonomer being chosen from propylene, butene, hexene or octene. It may also be a polypropylene, homo- or copolymer, the comonomer being chosen from ethylene, butene, hexene or octene.
• the polyethylene may be in particular high density polyethylene (HDPE), low density (LDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE).
• the polyethylene can be obtained using a Ziegler-Natta, Phillips or metallocene catalyst or by the high-pressure process.
• Polypropylene is iso- or syndiotactic polypropylene. It can also be a crosslinked polyethylene (denoted PEX). PEX has better non-crosslinked PEs with better mechanical properties (including good crack resistance) and better chemical resistance.
• the crosslinked polyethylene may be, for example, a polyethylene comprising hydrolysable silane groups (as described in applications WO 01/53367 or US 20040127641 A1) which has then been crosslinked after reaction between them silane groups.
• the reaction of silane groups Si-OR between them leads to Si-O-Si bonds which connect the polyethylene chains to each other.
• the content of hydrolysable silane groups may be at least 0.1 hydrolysable silane groups per 100 units -CH 2 - (determined by infrared analysis).
• Polyethylene can also be crosslinked by means of radiation, for example gamma radiation. It may also be a polyethylene crosslinked using a radical initiator of the peroxide type. It is therefore possible to use a PEX of type A (crosslinking using a radical initiator), type B (crosslinking with silane groups) or type C (crosslinking by irradiation).
• bimodal polyethylene that is to say composed of a mixture of polyethylenes having different average molecular weights as taught in WO 00/60001.
• bimodal polyethylene makes it possible to obtain a very interesting compromise of impact and stress-cracking resistance as well as good rigidity and good resistance to pressure.
• polyethylene which has good resistance to slow crack propagation (SCG) and rapid propagation can be advantageously used.
• SCG slow crack propagation
• RCP crack
• the grade HDPE XS 10 B marketed by TOTAL PETROCHEMICALS has good crack resistance (slow or fast).
• HDPE containing hexene as a comonomer, having a density of 0.959 g / cm 3 (ISO 1183), an MI-5 of 0.3 dg / min (ISO 1133), an HLMI of 8 dg / min (ISO 1133), a long-lasting hydrostatic resistance of 11.2 MPa according to ISO / DIS 9080, resistance to slow crack propagation on notched pipes greater than 1000 hours according to ISO / DIS 13479.
• this term refers to a copolymer of ethylene and at least one unsaturated polar monomer. This is preferably chosen from:
• C 1 -C 6 alkyl (meth) acrylates especially methyl, ethyl, propyl, butyl, 2-ethylhexyl, isobutyl or cyclohexyl (meth) acrylate;
• unsaturated carboxylic acids their salts and their anhydrides, in particular acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride and citraconic anhydride;
• unsaturated epoxides in particular aliphatic glycidyl esters and ethers such as glycidyl allyl glycidyl ether, vinyl glycidyl ether, maleate and itaconate, glycidyl acrylate and methacrylate, as well as alicyclic glycidyl esters and ethers;
• vinyl esters of saturated carboxylic acids in particular vinyl acetate or vinyl propionate.
• the functionalized polyolefin may be obtained by copolymerization of ethylene and at least one unsaturated polar monomer selected from the above list.
• the functionalized polyolefin may be a copolymer of ethylene and a polar monomer from the above list or a terpolymer of ethylene and two unsaturated polar monomers selected from the above list.
• the copolymerization takes place at high pressures higher than 1000 bar according to the so-called high-pressure process.
• the functional polyolefin obtained by copolymerization comprises, by weight, from 50 to 99.9% of ethylene, preferably from 60 to 99.9%, even more preferably from 65 to 99% and from 0.1 to 50%, preferably from 0.1 to 40%, more preferably 1 to 35% of at least one polar monomer from the above list.
• the functionalized polyolefin is a copolymer of ethylene and an unsaturated epoxide, preferably glycidyl (meth) acrylate, and optionally a (C 1 -C 8 ) alkyl (meth) acrylate or an ester vinylic acid saturated carboxylic acid.
• the content of unsaturated epoxide, in particular glycidyl (meth) acrylate, is between 0.1 and 50%, advantageously between 0.1 and 40%, preferably between 1 and 35% and even more preferably between 1 and 20%. %.
• This may include for example, functionalized polyolefins sold by Arkema under the references Lotader ® AX8840 (8 weight% glycidyl methacrylate, 92% weight of ethylene, 5 melt- index according to ASTM D1238), Lotader ® AX8900 ( 8% by weight of glycidyl methacrylate, 25% methyl acrylate weight, 67% weight of ethylene, melt-index 6 according to ASTM D1238), Lotader ® AX8950 (9% by weight of glycidyl methacrylate, 15% by weight of methyl acrylate, 76% by weight of ethylene, melt-index 85 according to ASTM D1238).
• the functionalized polyolefin may also be a copolymer of ethylene and an unsaturated carboxylic acid anhydride, preferably maleic anhydride, and optionally a C 1 -C 6 alkyl (meth) acrylate or a vinyl ester of saturated carboxylic acid.
• the maleic anhydride content especially maleic anhydride, is between 0.1 and 50%, advantageously between 0.1 and 40%, preferably between 1 and 35% and even more preferably between 1 and 10%.
• This may include for example, functionalized polyolefins sold by Arkema under the references Lotader ® 2210 (2.6% weight of maleic anhydride, 6 weight% butyl acrylate and 91, 4% weight of ethylene, melt-index 3 according to ASTM D1238), Lotader ® 3340 (3% by weight of maleic anhydride, 16 weight% butyl acrylate and 81% weight of ethylene, melt index of 5 according to ASTM-D 1238), Lotader ® 4720 (0.3% by weight of maleic anhydride, 30% by weight of ethyl acrylate and 69.7% weight of ethylene, melt-index according to ASTM D1238 7), Lotader ® 7500 (2.8% weight of maleic anhydride, 20% by weight of butyl acrylate and 77.2% by weight of ethylene, melt-index 70 according to ASTM D1238), Orevac ® 9309, Orevac ® 9314, Orevac ® 9307Y, Or
• the term "functionalized polyolefin” also refers to a polyolefin on which is grafted by radical means an unsaturated polar monomer from the above list. The grafting takes place in an extruder or in solution in the presence of a radical initiator.
• radical initiators examples include t-butyl hydroperoxide, cumene hydroperoxide, di-isopropylbenzene hydroperoxide, di-t-butylperoxide, t-butyl- cumyl peroxide, dicumyl peroxide, 1,3-bis- (t-butylperoxy-isopropyl) benzene, benzoyl peroxide, iso-butyryl-peroxide, bis-3,5,5-trimethylhexanoyl -peroxide or methyl-ethyl-ketone-peroxide.
• the grafting of an unsaturated polar monomer on a polyolefin is known to those skilled in the art, for more details, reference may be made for example to EP 689505, US 5235149, EP 658139, US 6750288 B2, US6528587 B2.
• the polyolefin on which the unsaturated polar monomer is grafted may be a polyethylene, in particular high density polyethylene (HDPE) or low density polyethylene (LDPE), linear low density polyethylene (LLDPE) or very low density polyethylene (VLDPE).
• the polyethylene can be obtained using a Ziegler-Natta, Phillips or metallocene catalyst or by the high-pressure process.
• the polyolefin may also be a polypropylene, especially an iso- or syndiotactic polypropylene. It may also be a copolymer of ethylene and propylene type EPR, or a terpolymer of ethylene, a propylene and a diene type EPDM. It may, for example, functionalized polyolefins sold by Arkema under the references OREVAC ® 18302, 18334, 18350, 18360, 18365, 18370, 18380, 18707, 18729, 18732, 18750, 18760, PP-C, CA100.
• the polymer on which the unsaturated polar monomer is grafted may also be a copolymer of ethylene and at least one unsaturated polar monomer chosen from: C 1 -C 8 alkyl (meth) acrylates, especially methyl, ethyl, propyl, butyl, 2-ethylhexyl, isobutyl or cyclohexyl (meth) acrylate;
• vinyl esters of saturated carboxylic acids in particular vinyl acetate or vinyl propionate.
• the multilayer pipe comprises (in order from the inside to the outside of the pipe):
• a layer Ci comprising at least one fluorinated polymer
• a layer C2 comprising at least one functionalized fluoropolymer, optionally mixed with at least one fluorinated polymer;
• a barrier layer C 3 comprising a barrier polymer chosen from EVOH or a mixture based on EVOH, PGA or PDMK;
• a layer C 4 of an adhesion binder • a C 5 layer comprising at least one polyolefin, optionally blended with at least one functionalized polyolefin;
• barrier layer C 6 Optionally a barrier layer C 6 ;
• a layer C 7 comprising at least one polyolefin, optionally mixed with at least one functionalized polyolefin.
• the inner layer that is in contact with the circulating fluid is either the layer Ci or the layer C 2 .
• All the layers of the tube are preferably concentric.
• the tube is preferably cylindrical.
• the layers are arranged against each other in the indicated order (ie for example that the layer C 3 is in contact with the layer C 2 and the layer C 4 ) and the layers adhere to each other in their respective contact zone.
• the layer Ci is optional and comprises at least one fluorinated polymer.
• the fluoropolymer is a homo- or copolymer PVDF or a copolymer based on VDF and EFFE-type TFE.
• this layer is present in the case where the fluid is water.
• This layer comprises at least one fluoropolymer functionalized optionally mixed with a fluoropolymer.
• the functionalized fluoropolymer serves as a binder between the layer Ci and the layer C 3 .
• the layer C 2 is advantageously directly attached to the layer Ci.
• the functionalized fluoropolymer is a fluoropolymer grafted by irradiation.
• the functionalized fluoropolymer of the layer C 2 may be used alone or mixed with a fluoropolymer.
• the mixture comprises, by weight, from 1 to 99%, advantageously from 10 to 90%, preferably from 10 to 50%, of functionalized fluoropolymer for 99 to 1%, preferably 90 to 10%, preferably 50 to 90%, of fluoropolymer.
• the functionalized fluoropolymer and the fluoropolymer are of the same nature.
• it may be a radiation-modified PVDF and an unmodified PVDF.
• a fluorinated polymer which is flexible, that is to say having a tensile modulus of between 50 and 1000 MPa (measured according to ISO R 527 at 23 0 C), advantageously between 100 and 750 MPa. and preferably between 200 and 600 MPa.
• the viscosity of the flexible fluorinated polymer measured by capillary rheometer at 230 ° C.
• the crystallization temperature of the flexible fluorinated polymer is between 50 and 120 ° C., preferably between 85 and 100 ° C.
• the fluorinated polymer flexible is a PVDF copolymer, more particularly a copolymer of VDF and HFP.
• the viscosity of the functionalised fluoropolymer is between 100 and 1500 Pa.s, advantageously between 200 and 1000 Pa.s and preferably between 500 and 1000. Not.
• the functionalized fluoropolymer is a radiation-grafted PVDF obtained from a PVDF comprising by weight at least 80%, advantageously at least 90%, preferably at least 95%, even more preferably at least 98% VDF. .
• the radiation-grafted PVDF is obtained from a PVDF homopolymer (i.e., containing 100% VDF).
• a particularly preferred mixture thus comprises a PVDF homopolymer grafted by irradiation and a VDF-HFP copolymer having a tensile modulus of between 200 and 600 MPa, a crystallization temperature of between 85 and 100 ° C. and a viscosity of between 500 and 1000 Pa. s.
• the barrier layer Ca is the barrier layer Ca
• C 3 The function of C 3 is to brake or prevent the migration of molecules from the inside to the outside (for example of a fuel transfer tube) or from the outside towards the inside of the vehicle.
• the multilayer structure for example a water or gas transport tube.
• the layer C 3 comprises a barrier polymer which is chosen from EVOH or a mixture based on EVOH, poly (glycolic acid) (PGA) or polydimethyl ketene (PDMK).
• a barrier polymer which is chosen from EVOH or a mixture based on EVOH, poly (glycolic acid) (PGA) or polydimethyl ketene (PDMK).
• EVOH is also called saponified ethylene-vinyl acetate copolymer. It is a copolymer having an ethylene content of 10 to 70 mol%. Preferably, good barrier properties are obtained when the ethylene content is between 25 and 60 mol%. Preferably, the degree of saponification of its vinyl acetate component is at least 85 mol%, preferably at least 90%, more preferably at least 95%. The contents of ethylene and the degree of saponification can be determined, for example, by NMR. EVOH is a good barrier to oxygen. Advantageously, the EVOH has a melt index between 0.5 and 100 g / 10 min (230 ° C., 2.26 kg), preferably between 5 and 30.
• the EVOH may contain small amounts of other comonomer ingredients, including alpha-olefins such as propylene, isobutene, alpha-octene, unsaturated carboxylic acids or their salts, partial alkyl esters, complete alkyl esters ,. .. It is also possible to combine two types of EVOH to improve barrier and / or mechanical properties.
• EVOH is an effective barrier material for many molecules as shown in Table I which compares several grades of EVOH (as a function of ethylene content) to oriented PP or PET.
• EVOH forms the matrix, i.e., at least 40% by weight of the blend and preferably at least 50%.
• Polydimethyletene can be obtained by the pyrolysis of isobutyric anhydride as contemplated in the applications FR 2851562 and FR 2851562 which are incorporated herein by reference.
• a process for producing polydimethylenetene is as follows: a) a mixture comprising from 1 to 50% by volume of idobutyric anhydride per 99 to 50% of an inert gas is preheated at atmospheric pressure between 300 and 34O 0 C, b) then this mixture is brought to a temperature between 400 and 55O 0 C for a time between 0.05 and 10 s to obtain a mixture of dimethyletene, inert gas, isobutyric acid and isobutyric anhydride having unreacted, (c) the preceding stream is cooled to separate dimethyletene and the inert gas from isobutyric alcohol and isobutyric anhydride; (d) dimethyletene is absorbed in a saturated or unsaturated, aliphatic or
• This polymer can be manufactured by heating at a temperature of between 120 and 25O 0 C 1,4-dioxane-2,5-dione in the presence of a catalyst such as a tin salt, such as SnCU.
• a catalyst such as a tin salt, such as SnCU.
• the polymerization is carried out in bulk or in a solvent.
• the AMP may contain the following other reasons (2) to (6):
• R 2 (4) wherein k is an integer of 2 to 10 and R 1 and R 2 are each independently of one another H or C 1 -C 10 alkyl;
• EVOH OR an EVOH-based blend is the preferred barrier polymer.
• the layer C 4 which is arranged between the layers C 3 and C 5 has the function of reinforcing the adhesion between these two layers. It comprises an adhesion binder that is to say a polymer whose function is to improve the adhesion between these two layers.
• the adhesion binder comprises at least one functionalized polyolefin, optionally mixed with at least one polyolefin.
• the layer C 4 comprises at least one functionalized polyolefin optionally mixed with at least one polyolefin.
• the mixture comprises, by weight, from 1 to 100%, advantageously from 10 to 100%, preferably from 50 to 100%, of at least one functionalized polyolefin for 0 to 99%, advantageously 0 to 90%, preferably from 0 to 50%, of at least one polyolefin.
• the polyolefin which is used for mixing with the functionalized polyolefin is preferably a polyethylene because these two polymers have good compatibility.
• the layer C 4 may also comprise a mixture of two or more functionalized polyolefins.
• it may be a mixture of a copolymer of ethylene and an unsaturated epoxide and optionally an alkyl (meth) acrylate and a copolymer of ethylene and of an alkyl (meth) acrylate.
• the functionalized polyolefin of layer C 4 preferably has functions capable of reacting with functions that are on EVOH, PGA or PDMK.
• a functionalized polyolefin carrying anhydride and / or acid functional groups may be suitable in particular in the presence of EVOH. It is for example a copolymer:
• an unsaturated carboxylic acid anhydride preferably maleic anhydride, or an unsaturated carboxylic acid, preferably (meth) acrylic acid, and
• a C 1 -C 8 alkyl (meth) acrylate or a saturated carboxylic acid vinyl ester optionally, a C 1 -C 8 alkyl (meth) acrylate or a saturated carboxylic acid vinyl ester.
• It may also be a polyolefin or a copolymer of ethylene and at least one unsaturated polar monomer chosen from:
• C 1 -C 8 alkyl (meth) acrylates especially methyl, ethyl, propyl, butyl, 2-ethylhexyl, isobutyl or cyclohexyl (meth) acrylate; the vinyl esters of saturated carboxylic acids, in particular vinyl acetate or vinyl propionate, on which an unsaturated carboxylic acid anhydride or an unsaturated carboxylic acid has been grafted by a radical route.
• the layer C 5 comprises at least one polyolefin optionally mixed with at least one functionalized polyolefin. More specifically, the mixture comprises, by weight, from 1 to 100%, advantageously from 10 to 100%, preferably from 50 to 100%, of at least one polyolefin for respectively from 0 to 99%, advantageously from 0 to 90%, preferably from 0 to 50%, of at least one functionalized polyolefin.
• the layer C 5 does not comprise a functionalized polyolefin and the polyolefin used is preferably a polyethylene, and advantageously a PEX.
• the barrier layer CR The barrier layer CR
• the function of C 6 is identical to that of C 3 .
• the two barrier layers make it possible to obtain a barrier structure that is more effective and / or has barrier properties with respect to a larger number of molecules.
• the barrier layer C 6 may comprise: EVOH OR a mixture based on EVOH;
• PDMK Polydimethyl ketene
• the barrier layer C 6 is a metal sheath.
• the metal sheath also has the function of reinforcing the mechanical strength of the tube. Another advantage of using a metal sheath is to be able to bend or deform the tube without it returning to its original position under the effect of the mechanical stresses generated by the thermoplastic polymer layers.
• the metal may be steel, copper or aluminum or an alloy of aluminum. It is preferably aluminum or an alloy of aluminum for reasons of corrosion resistance and flexibility.
• the metal sheath is manufactured according to one of the methods known to those skilled in the art. It will be possible to refer in particular to the following documents which describe methods for producing plastic / metal composite tubes: US Pat. No. 6,822,205, EP 0581208 A1, EP 0639411 B1 and EP 0823867.
• a layer comprising an adhesion binder is advantageously disposed between the layer C 5 and the barrier layer Ce and / or between the barrier layer Ce and the optional layer C 7 .
• the adhesion binder is, for example, a functionalized polyolefin carrying anhydride and / or acid functional groups. It is for example a copolymer:
• an unsaturated carboxylic acid anhydride preferably maleic anhydride, or an unsaturated carboxylic acid, preferably (meth) acrylic acid, and
• a C 1 -C 8 alkyl (meth) acrylate or a saturated carboxylic acid vinyl ester optionally, a C 1 -C 8 alkyl (meth) acrylate or a saturated carboxylic acid vinyl ester.
• It may also be a polyolefin or a copolymer of ethylene and at least one unsaturated polar monomer chosen from:
• C 1 -C 6 alkyl (meth) acrylates especially methyl, ethyl, propyl, butyl, 2-ethylhexyl, isobutyl or cyclohexyl (meth) acrylate;
• the vinyl esters of saturated carboxylic acids in particular vinyl acetate or vinyl propionate, on which an unsaturated carboxylic acid anhydride or an unsaturated carboxylic acid has been grafted by a radical route.
• the adhesion binder is a polyolefin to which an unsaturated carboxylic acid anhydride or an unsaturated carboxylic acid, preferably maleic anhydride, is radically grafted. It can be a polyethylene onto which is grafted (meth) acrylic acid or maleic anhydride or a polypropylene on which is grafted with (meth) acrylic acid or maleic anhydride.
• the tube may optionally comprise a layer C 7 comprising at least one polyolefin, optionally mixed with a functionalized polyolefin.
• the polyolefins used in layers C 5 and C 7 may be the same or different.
• the function of the C 7 polyolefin layer is to mechanically protect the tube.
• the layer C 7 does not comprise a functionalized polyolefin and the polyolefin used is preferably a polyethylene, and advantageously a PEX.
• each of the layers of the multilayer tube in particular the polyolefin layer or layers, contained additives usually used in admixture with thermoplastics, for example antioxidants, lubricating agents, colorants, carbon black.
• the tube may also comprise other layers, such as for example a thermal insulation layer around the multilayer tube.
• the multilayer tube comprises (in order from the inside to the outside of the tube): • optionally a layer Ci comprising at least one PVDF homo- or copolymer; A layer C2 comprising at least one PVDF onto which has been grafted by irradiation an unsaturated carboxylic acid anhydride, preferably maleic anhydride, optionally in admixture with at least one compatible PVDF homo- or copolymer compatible; A layer C 3 comprising at least one EVOH;
• a layer C4 comprising an adhesion binder
• a C 5 layer comprising at least one polyethylene, preferably a PEX;
• the invention can be extended to other forms of multilayer structures.
• the invention relates more generally to a multilayer structure comprising (in order from the inside to the outside) the layers Ci to C 7 as described, each layer being arranged against the other in the order indicated.
• This multilayer structure may be in the form of hollow body, container, bottle, ... It may be for example a fuel tank.
• extrusion blow molding or blow molding
• injection blow molding is used.
• the layers Ci, C2, C3, C4 and C 6 each have a thickness between 0.01 and 30 mm, advantageously between 0.05 and 20 mm, preferably between 0.05 and 10 mm.
• the layers C 5 and C 7 preferably each have a thickness of between 0.01 and 10000 mm, advantageously between 0.5 and 2000 mm, preferably between 0.5 and 1000 mm.
• the tubes without metal sheath are manufactured by coextrusion.
• the polyolefin of the layer C 5 and / or of the optional layer C 7 is a PEX of type B (crosslinking by silane groups)
• the extrusion is first extruded. uncrosslinked polyolefin.
• Crosslinking is performed by then dipping the extruded tubes into hot water pools.
• the polyolefin of the layer C 5 and / or of the optional layer C 7 is a PEX of type A (crosslinking using a radical initiator)
• the crosslinking is carried out using a radical initiator which activates thermally during extrusion.
• the tubes with metal sheath are manufactured after coextrusion of the layers C 1 to C 5 , and the optional layer of adhesion binder between the layer C 6 and the layer C 5 , then a metal strip is wound around the layers and obtained.
• the longitudinal edges may be welded together to form a longitudinal seam. It is then possible, if this is intended, to extrude the other layers, that is to say the optional layer C 7 and if the layer C 7 is present, optionally a layer of adhesion binder between the layer C 6 and the layer C 7 .
• the multilayer pipe can be used for transporting different fluids.
• the tube is suitable for the transport of water, especially hot water, especially the transport of hot water network.
• the tube may be used for the transport of hot heating water (temperature above 60 ° C., or even 90 ° C.).
• An interesting example of application is the radiant floor heating (radiant floor) in which the tube used to convey hot water is placed under the floor or the floor. The water is heated by a boiler and conveyed through the tube.
• Another example is that in which the tube is used to convey hot water to a radiator.
• the tube can therefore be used for radiant water heating systems.
• the invention also relates to a network heating system comprising the tube of the invention.
• the chemical resistance of the tube is adapted to a water containing chemical additives (generally in small quantities, less than 1%) which can alter the polyolefins, especially polyethylene, especially when hot.
• chemical additives may be oxidizing agents such as chlorine and hypochlorous acid, chlorinated derivatives, bleach, ozone, etc.
• the circulating water is potable water, water for medical or pharmaceutical applications or a biological fluid
• a layer of unmodified fluoropolymer as a layer in contact with water (layer Ci).
• Microorganisms bacteria, germs, molds, ...) have little tendency to develop on a fluoropolymer, especially on PVDF.
• the layer in contact with the water or the biological liquid is a layer of unmodified fluoropolymer that a fluoropolymer layer modified to prevent the migration of ungrafted (free) unsaturated monomer in the water. water or body fluid.
• the barrier properties of the tube make it suitable for the transport of water in contaminated soil by slowing the migration of contaminants to the transported fluid. Barrier properties are also useful to prevent the migration of oxygen into the water (DIN 4726), which can be detrimental in the case where the tube is used to carry hot water for heating (the presence of oxygen is a source of corrosion of the steel or iron parts of the heating system). It is also desired to slow down the migration of the contaminants present in the polyolefin layer (antioxidants, polymerization residues, etc.) towards the transported fluid.
• the multilayer pipe can be used for transporting chemicals, especially those capable of chemically degrading polyolefins.
• the multilayer pipe may also be used for transporting a gas, in particular a gas under pressure.
• a gas in particular a gas under pressure.
• the polyolefin is a polyethylene PE80 type or a PE100, it is especially suitable for holding at pressures greater than 10 bar, or even greater than 20 bar, or even greater than 30 bar.
• the gas can be of different nature. It can be for example:
• a gaseous hydrocarbon for example town gas, a gaseous alkane, especially ethane, propane, butane, a gaseous alkene, especially ethylene, propylene, butene
• a gaseous alkane especially ethane, propane, butane
• a gaseous alkene especially ethylene, propylene, butene
• oxygen • a gas that is corrosive or likely to degrade polyethylene or polypropylene.
• a gas that is corrosive or likely to degrade polyethylene or polypropylene may be an acid or corrosive gas, such as H 2 S or HCl or HF.
• the optional layer Ci or the layer C 2 are resistant to these gases because they are fluorinated polymers.
• the fluoropolymer of the layers Ci and C 2 is PVDF because it is particularly resistant. It is possible that the cryogen condenses at certain points of the air conditioning circuit and is liquid. The multilayer pipe can therefore also apply to the case where the cryogenic gas has condensed in liquid form.
• the fluid can also be a fuel, for example a gasoline
• the multilayer pipe can also be used for transporting a fuel, for example a gasoline, especially a gasoline containing an alcohol.
• the gasoline may be for example gasoline M15 (15% methanol, 42.5% toluene and 42.5% iso octane), Fuel C (50% toluene, 50% isooctane), CE10 (10% of ethanol and 90% of a mixture containing 45% toluene and 45% of isooctane, it can also be MTBE. [Examples]
• PEX The PEX layer was obtained from a mixture containing 95% BORPEX ME-2510 grade and 5% MB-51 grade sold by BOREALIS.
• KYNAR ® 2750-10 PVDF sold by Arkema, of melt flow 20 g / 10 min (23O 0 C, 5 kg) and melting temperature of about 135 0 C.
• KYNAR ® 720 PVDF homopolymer from Arkema, of melt flow 20 g / 10 min (23O 0 C, 5 kg) and melting temperature of about 17O 0 C.
• KYNAR ® 710 PVDF homopolymer from Arkema, of melt flow 25 g / 10 min (23O 0 C, 5 kg) and melting temperature of about 17O 0 C.
• PVDF-1 KYNAR ® 710 on which has been radiation-grafted maleic anhydride.
• the grafting was carried out by mixing in a twin screw extruder KYNAR ® 710 with 2 wt% maleic anhydride. The mixture is granulated and then bagged in sealed aluminum bags, then the bags and their mixture are irradiated under 3 Mrad with a cobalt-60 bomb for 17 hours. The product is recovered and degassed in vacuo to remove the residual non-grafted maleic anhydride. The content of maleic anhydride grafted is 1% (infrared spectroscopy).
• the MFR of PVDF-1 is 15 g / 10 min (230 ° C., 5 kg).
• OREVAC ® 18303s polyethylene grafted with maleic anhydride having an MFI of 2 (19O 0 C, 2.16kg) and a melting point of 124 0 C.
• SOARNOL ® 2903 DT EVOH marketed by the company NIPPON GOHSEI containing 29 mol% of ethylene, having an MFI of 3.2 (21O 0 C, 2.16 kg), a melting point equal to about 188 0 C and a crystallization temperature of about 163 ° C. It has an oxygen permeability of 0.4 this 20 ⁇ m / m 2 day atm at 20 ° C
• Tube PEX outer layer (800 ⁇ m) / OREVAC ® (50 ⁇ m) / SOARNOL 2903 DT
• a tube is prepared by coextruding in the outer order of the tube to the inside of the tube the following layers: 800 microns of the mixture ME-2510 / MB-51, 50 microns of OREVAC ® 18303s, 50 ⁇ m of EVOH, 50 ⁇ m of a mixture containing 70% by weight of Kynar Flex ® 2750-10 and 30% by weight of PVDF-1 and finally 100 ⁇ m of KYNAR ® 720.
• the tube is coextruded with a head temperature close to 24O 0 C and a line speed of 15 m / minute.
• the tubes thus obtained are then placed in a pool heated to 70 ° C. for 1 day to crosslink the PE.
• the KYNAR ® 720 layer is the inner layer and the PEX layer is the outer layer.
• the adhesion obtained by circumferential peeling is 55 N / cm at the interface EVOH / OREVAC ® .
• No adhesion value is measurable between the mixture (PVDF-1 + 2750-10) and EVOH because the adhesion is excellent and the interface can not be primed.
• Tube PEX outer layer (800 .mu.m) / Orevac ® (50 .mu.m) / SOARNOL 2903 DT (50 .mu.m) / [50% KYNARFLEX ® + 50% PVDF-1] (50 .mu.m) / KYNAR ® 720 CO uc h e internal (100 ⁇ m)
• a tube extruder for coextrusion type 5 Mc Neil layers a tube is prepared by coextruding the outside inwards 800 .mu.m mixture ME-2510 / MB-51, 50 .mu.m Orevac ® 18303s, 50 .mu.m EVOH, 50 microns of a mixture containing 50% by weight of Kynar Flex ® 2750-10 and 50% by weight of PVDF-1 and finally 100 .mu.m KYNAR ® 720.
• the tube is co-extruded with an adjacent head temperature 24O 0 C and a line speed of 15 m / minute.
• the tubes thus obtained are then placed in a pool heated to 70 ° C. for 1 day to crosslink the PE.
• the KYNAR ® 720 layer is the inner layer and the PEX layer is the outer layer.
• the adhesion obtained by circumferential peeling is 57 N / cm at the interface EVOH / OREVAC ® .
• No adhesion value is measurable between the mixture (PVDF-1 + 2750-10) and EVOH because the adhesion is excellent and the interface can not be primed.
• Tube PEX outer layer (800 ⁇ m) / OREVAC ® (50 ⁇ m) / SOARNOL 2903 DT
• a tube is prepared by coextruding the outside inwards 800 microns of polyethylene, 50 microns of Orevac ® 18303s, 50 .mu.m EVOH, 50 .mu.m of a mixture containing 30% by weight of Kynar Flex ® 2750-10 and 70% by weight of PVDF-1 and finally 100 .mu.m KYNAR ® 720.
• the tube is co-extruded with an adjacent head temperature of 24O 0 C and a speed of line of 15 m / minute.
• the tubes thus obtained are then placed in a pool heated to 70 ° C. for 1 day to crosslink the PE.
• the KYNAR ® 720 layer is the inner layer and the PEX layer is the outer layer.
• the adhesion obtained by circumferential peeling is 56 N / cm at the interface EVOH / OREVAC ® , no adhesion value is measurable between the mixture (PVDF-1 + 2750-10) and the EVOH because the membership is excellent and the interface can not be primed.

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• 2005
  • 2005-11-24 FR FR0511906A patent/FR2893696B1/fr not_active Expired - Fee Related
• 2006
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