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
• • 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
• • 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]
• • 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]
• • 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]
  • Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
  • Y10T428/1393—Multilayer [continuous layer]
• • 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
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers

Definitions

• the invention relates to a multilayer structure comprising a layer of a barrier polymer and a layer of a polyolefin which may take the form of a film, tube, pipe, container or reservoir.
• a barrier polymer In the case of a tube, pipe, container or tank, it can be used for the transfer of fluids such as a fuel (eg gasoline).
• the barrier polymer can be reinforced on impact.
• Polyolefins are often used for the manufacture of structures such as tubes, pipes or containers, but for many uses, they have barrier properties, for example vis-à-vis various fuels (gasoline, diesel, alcoholic spirits, alcohol ..) often very insufficient. This is why it is common to associate with a polyolefin layer a layer of a barrier polymer such as EVOH. In contact with a fuel (whether in contact with the innermost or outermost layer), the polyolefin has a tendency to swell, which tends to affect the mechanical properties of the structure as well as its dimensional stability. The structure must also withstand cold shocks and maintain good mechanical strength at high temperatures.
• the Applicant has developed a multilayer structure which responds to the problems posed, that is to say which in particular:
• EP 1537989 and EP 1541343 describe a multilayer structure based on fluorinated polymer onto which has been grafted by irradiation an unsaturated monomer.
• the pipe comprises a layer of the modified fluoropolymer and a layer of a polyolefin. There is no mention of EVOH.
• EP 1637319 discloses a multilayer structure comprising a barrier polymer layer and a binder layer comprising an epoxy functional polyethylene and a viscous polymer.
• the barrier polymer may be a PVDF onto which has been grafted by irradiation an unsaturated monomer. There is no mention of EVOH.
• a flexible tube comprising an inner layer of a fluoropolymer, an intermediate layer of a thermoplastic polymer such as PE or PA and an outer layer of a fluoropolymer.
• An adhesion binder layer may be disposed between the at least one fluoropolymer layer (s) and the thermoplastic polymer layer.
• the invention relates to a multilayer structure reinforced with a cold impact comprising a layer of a fuel barrier polymer and a layer of a polyolefin.
• It can be in the form of a film, tube, pipe, container or tank.
• a tube, pipe, container or tank thanks to its barrier properties, it can be used to store or transfer a fuel.
• the subject of the invention is a multilayer structure comprising (from inside to outside): a layer C1 comprising at least one functionalized fluorinated polymer, optionally mixed with at least one compatible fluorinated polymer; A layer C2 comprising at least one adhesion binder;
• a layer C3 comprising at least one polyolefin, preferably a polyethylene
• a layer C4 comprising at least one adhesion binder;
• a barrier layer C5 comprising at least one barrier polymer of EVOH, optionally reinforced on impact; the layers being arranged against each other in the order indicated.
• polyethylene is a polyethylene or a polypropylene.
• polyethylene includes homo- or copolymers of ethylene. It may be, for example, a HDPE, an LLDPE or an LDPE. It may also be a polyethylene obtained by monosite catalysis (for example of the metallocene type), for example an ethylene-octene copolymer of the ENGAGE ® type.
• polypropylene includes homo- or copolymers of propylene. It may be an iso- or syndiotactic polypropylene.
• polyolefin also includes copolymers of the type EPR (Ethylene-Propylene Rubber) or EPDM (Ethylene-Propylene-Diene-Monomer).
• a polyethylene of the PE type 100 ie a PE which, when it is formed into a tube of specific dimensions, withstands a test pressure for a period of 5000 hours, will be chosen.
• PE 100 a polyethylene of the PE type 100, ie a PE which, when it is formed into a tube of specific dimensions, withstands a test pressure for a period of 5000 hours.
• ISO 1167, ISO 9080 and ISO 12162 A definition of PE 100 is also found in international application WO 2000060001. This type of PE has good mechanical strength and has little tendency to swell in the presence of fuel, especially gasoline.
• PFBE perfluorobutyl ethylene
• the fluoropolymer may be a homopolymer or a copolymer, it may also include non-fluorinated monomers such as ethylene or propylene.
• the fluorinated polymer is chosen from: the homo- and copolymers of vinylidene fluoride (PVDF) preferably containing at least 50% by weight of VDF, the copolymer being chosen from chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP), trifluoroethylene (VF 3 ) and tetrafluoroethylene (TFE); copolymers of TFE and ethylene (ETFE); homo- and copolymers of trifluoroethylene (VF3); copolymers, and especially terpolymers, combining the residues of the chlorotrifluoroethylene (CTFE), tetrafluoroethylene (TFE) units, hexafluoropropylene (HFP) and / or ethylene and optionally
• the fluoropolymer is a homo- or copolymer PVDF.
• This fluorinated polymer indeed has good chemical resistance, especially to UV and chemical products, and it is easily transformed by extrusion
• 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 4,000 Pa. S, preferably 300 to 1200 Pa. S, the viscosity being measured at 230 0 C, at a shear gradient of 100 s "1 at With the aid of a capillary rheometer, these PVDFs are well suited to extrusion and injection molding.
• the functionalized fluoropolymer is a fluorinated polymer bearing at least one polar group chosen from the following chemical groups: carboxylic acid, carboxylic acid salt, carbonate, carboxylic acid anhydride, epoxide carboxylic acid ester, silyl, alkoxysilane, carboxylic acid amide, hydroxy, isocyanate. It is a copolymer comprising at least one fluorinated monomer and at least one unsaturated monomer bearing a polar group as defined. The function of the polar group is to improve the adhesion of the fluoropolymer.
• the term "functionalized" designates more generally in the present application for a polymer the fact that it carries a polar group as defined.
• the functionalized fluoropolymer can be obtained by the copolymerization either by the grafting of an unsaturated polar monomer.
• the functionalized fluoropolymer may be obtained by copolymerizing at least one fluorinated monomer with at least one unsaturated polar monomer (described below) and optionally at least one other comonomer.
• the polymer functionalized may be a PVDF comprising monomeric units of VDF and a monoesterified unsaturated diacid or vinylene carbonate as described in US 5415958.
• Another example of functionalized fluoropolymer is that of a PVDF comprising monomeric units VDF and itaconic or citraconic anhydride as described in US 6703465 B2.
• the functionalized fluoropolymer may be prepared by an emulsion, suspension or solution process.
• the functionalized fluoropolymer may also be obtained by radical grafting of at least one unsaturated polar monomer (described below) on a fluorinated polymer.
• the grafting can be carried out in the molten state in the presence of a radical initiator.
• a radical initiator for example, in the international application WO 2001081077, Example 5 describes the preparation of an ETFE on which is grafted maleic anhydride. The grafting is carried out in the molten state at 300 ° C. in an extruder in the presence of tert-butyl hydroperoxide.
• the grafting can also be obtained by irradiation of a solid state mixture of a fluorinated polymer and an unsaturated polar monomer.
• the fluoropolymer is premixed in melt with the unsaturated polar monomer.
• the melt blending techniques known from the prior art can be used, for example by means of an extruder or a kneader.
• 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 polar 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 content of unsaturated polar monomer which is grafted is, by weight, between 0.1 and 5% (that is to say that the unsaturated polar monomer grafted corresponds to 0.1 to 5 parts for 99.9 to 95%).
• parts of fluoropolymer preferably from 0.5 to 5%, preferably from 0.9 to 5%. This content depends on the initial content of the unsaturated polar monomer in the mixture to be irradiated. It also depends on the effectiveness of the grafting, and therefore the duration and energy of the irradiation.
• the unsaturated polar monomer which has not been grafted, as well as the residues liberated by the grafting, in particular the HF, can then optionally be removed. This last step may be necessary if the ungrafted unsaturated polar 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.
• a suitable solvent such as, for example, N-methylpyrrolidone
• a non-solvent for example in water or in an alcohol
• washing the grafted fluoropolymer by irradiation with a solvent inert with respect to the fluoropolymer and graft functions for example, when grafting maleic anhydride, it can be washed with chlorobenzene.
• the proportion of fluoropolymer is, by weight, between 80 to 99.9% for respectively 0.1 to 20% of unsaturated polar monomer.
• the proportion of fluorinated polymer is from 90 to 99% for 1 to 10% of unsaturated polar monomer, respectively.
• the fluoropolymer grafted by irradiation has the very good chemical resistance and oxidation, as well as the good thermomechanical behavior, of the fluoropolymer before its modification.
• the functionalized polyolefin it is preferably a copolymer of ethylene and / or propylene and at least one unsaturated polar monomer.
• the unsaturated polar monomer is chosen from: C 1 -C 6 alkyl (meth) acrylates, especially methyl, ethyl, propyl, butyl, 2-ethylhexyl or isobutyl (meth) acrylate cyclohexyl; unsaturated carboxylic acids, their salts and their anhydrides, in particular acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride and citraconic anhydride; unsaturated epoxides, especially aliphatic glycidyl esters and ethers such as glycidyl allyl glycidyl ether, vinyl glycidyl ether, maleate and itaconate, glycidyl acrylate and methacrylate, as well
• vinyl esters of saturated carboxylic acids especially vinyl acetate, vinyl propionate or vinyl butyrate.
• copolymer is broadly defined as described, for example, in the NUPAC nomenclature guide of E. S. Wilks or in IUPAC. Basic definitions of terms relating to polymers, Pure Appl. Chem. 40, 477-491 (1974). It also includes graft copolymers.
• 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 (described for example in documents FR-A-2498609, EP-A-0 174 244 or EP-A-0 177 378).
• 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 may comprise ethylene and an unsaturated epoxide, preferably glycidyl (meth) acrylate, and optionally a C 1 -C 5 alkyl (meth) acrylate or a saturated carboxylic acid vinyl ester.
• unsaturated epoxide especially 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%. .
• LOTADER AX8840 8% glycidyl methacrylate, 92% ethylene, melt index of 5 according to ASTM D1238)
• LOTADER AX8900 (8). % of glycidyl methacrylate, 25% of methyl acrylate, 67% of ethylene, melt index of 6 according to ASTM D1238)
• LOTADER AX8950 10% glycidyl methacrylate, 15% methyl acrylate, 76% ethylene, melt index of 85 according to ASTM D1238).
• the functionalized polyolefin may also comprise ethylene and an unsaturated acid anhydride, preferably maleic anhydride, and optionally a C 1 -C 5 alkyl (meth) acrylate or a saturated carboxylic acid vinyl ester.
• the anhydride content of unsaturated acid, in particular 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%.
• It may be, for example, functionalized polyolefins marketed by ARKEMA under the references LOTADER 2210 (2.6% maleic anhydride, 6% butyl acrylate and 91.4% ethylene, melt index).
• 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 polyolefin is chosen from the previous 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-tert-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).
• Polyethylene can be obtained using a Ziegler-Natta or Phillips or metallocene-type catalyst or by the high-pressure process.
• the polyolefin may also be a polypropylene, especially an iso- or syndiotactic polypropylene. It may be, for example, functionalized polyolefins marketed 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 5) alkyl (meth) acrylates especially methyl, ethyl, propyl, butyl, 2-ethylhexyl, isobutyl or cyclohexyl (meth) acrylate; vinyl esters of saturated carboxylic acids, especially vinyl acetate or vinyl propionate. It may be for example functionalized polyolefins marketed by ARKEMA under the references OREVAC 18211, 18216 or 18630.
• alkoxysilane carboxylic acid amide
• 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, crotonic anhydride, glycidyl acrylate or methacrylate, allyl glycidyl ether, vinyl silanes such as vinyl trimethoxysilane, vinyl triethoxysilane, vinyl triacetoxysilane, ⁇ -methacryloxypropyltrimethoxysilane.
• unsaturated polar 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, N-monoethylamide maleic, N, N-diethylamide maleic, N-monobutylamide maleic, N, N-dibutylamide maleic, fumaric monoamide, fumaric diamide, fumaric N-monoethylamide, N, N-diethylamide fumaric, fumaric N-monobutylamide and N, N-dibutylamide fumaric; imide derivatives of unsaturated carboxylic acids such as maleimide, N-butylmale
• maleic anhydride is used.
• This monomer indeed offers the following advantages: it is solid and can be easily introduced with the fluoropolymer granules before melt blending,
• barrier polymer refers to a polymer which has a low permeability vis-à-vis the species and in particular alcoholic essences. Its permeability is preferably less than 150 g.mm / m 2 .day for gasoline M15 at 60 ° C.
• barrier polymers are as follows:
• PPS poly (phenylene sulfide)
• PBN butylene polynaphthalate
• PBT polybutylterephthalate
• polyamide MDX6 poly (glycolic acid) (PGA).
• the EVOH denotes a saponified ethylene-vinyl acetate copolymer comprising from 20 to 70 mol%, advantageously from 25 to 60 mol%, preferably from 25 to 40 mol% of ethylene.
• 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 proton NMR.
• the EVOH has a melt flow index of between 0.5 and 100, preferably between 5 and 30 g / 10 min (230 ° C., 2.26 kg).
• 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, etc. It is also possible to combine two types of EVOH to improve the barrier and / or mechanical properties.
• alpha-olefins such as propylene, isobutene, alpha-octene, unsaturated carboxylic acids or their salts, partial alkyl esters, complete alkyl esters, etc. It is also possible to combine two types of EVOH to improve the barrier and / or mechanical properties.
• the impact-strengthened barrier polymer it is a mixture comprising at least one barrier polymer and at least one impact modifier.
• the proportion of impact modifier is, by weight, between 1 and 35% for respectively 65 to 99% of barrier polymer.
• the function of the impact modifier is to increase the impact resistance of the barrier polymer.
• Another function is to improve the deformation of the multilayer structure, especially cold. The tube can thus be deformed without cracking, especially during an impact (eg of the type described in UL-971 "Nonmetallic Underground Piping For Flammable Liquids").
• the impact modifier can be selected from: a) functionalized ethylene- (meth) acrylate copolymers; b) elastomers, preferably EPR, EPDM and NBR, these elastomers can be functionalized; c) S-B-S block copolymers, linear or star, optionally hydrogenated (they are then designated S-EB-S), these copolymers can be functionalized.
• the functions can be provided by an unsaturated monomer bearing at least one acid, acid anhydride or epoxide function.
• the amount of the unsaturated monomer may be up to 15% by weight of the copolymer and the amount of ethylene of at least 50% by weight.
• the alkyl (meth) acrylate is such that alkyl has 2 to 10 carbon atoms.
• the alkyl (meth) acrylate may be chosen from methyl methacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate and 2-ethylhexyl acrylate.
• the melt index can range, for example, from 0.1 to 50 g / 10 min (at 190 ° C. under 2.16 kg).
• the alkyl (meth) acrylate is such that the alkyl has 2 to 10 carbon atoms.
• the melt index can range, for example, from 0.1 to 50 g / 10 min (at 190 ° C. under 2.16 kg).
• alkyl acrylate or methacrylate examples include methyl methacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate and 2-ethylhexyl acrylate.
• unsaturated epoxides examples include: aliphatic glycidyl esters and ethers such as glycidyl allyl glycidyl ether, vinyl glycidyl ether, maleate and itaconate, glycidyl acrylate and methacrylate, and esters and alicyclic glycidyl ethers such as 2-cyclohexene-1-glycidyl ether, cyclohexene-4,5-diglycidylcarboxylate, cyclohexene-4-glycidyl carboxylate, 5-norbornene-2-methyl-2-glycidyl carboxylate and endocis-bicyclo (2 , 2, 1) -5-heptene-2,3-diglycidyl dicarboxylate.
• aliphatic glycidyl esters and ethers such as glycidyl allyl glycidyl ether, vinyl glycidy
• SBS triblocks are described in ULLMANN'S encyclopedia of industrial chemistry Vol.A26, pages 655-659.
• SBS triblocks linear copolymers in which each block is connected to the another by means of a covalent bond or an intermediate molecule connected to one of the blocks by a covalent bond and to the other block by another covalent bond.
• Block S comprises at least 80% of at least one vinylaromatic compound such as, for example, styrene, alpha-methylstyrene and vinyltoluene.
• the monomer used to synthesize the elastomeric B block may be a diene chosen from butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-phenyl-1,3 butadiene.
• B is advantageously chosen from poly (dienes), especially poly (butadiene), poly (isoprene) and their random copolymers, or else from partially or completely hydrogenated poly (dienes).
• polybutadienes those with the lowest glass transition temperature (Tg), for example 1,4-polybutadiene of Tg (around -90 ° C.) lower than that of polybutadiene-1,2, are advantageously used. (to 0 0 C).
• Tg glass transition temperature
• the B blocks can also be partially or totally hydrogenated. This hydrogenation is carried out according to the usual techniques.
• the blocks B consist predominantly of polybutadiene-1,4.
• the linear S-B-S triblock has a number-average molar mass which may be between 10,000 g / mol and 500,000 g / mol, preferably between 20000 and 200000 g / mol.
• the S-B-S triblock advantageously consists of a mass fraction in B of between 5 and 95% and preferably between 15 and 85%.
• triblocks S-B-S include those star.
• the term "triblock” is not consistent with the number of blocks but the term "star S-B-S triblocks" is clear to the skilled person.
• star triblocks mention may be made of those of formula:
• n 1, 2 or 3 and Si and Bi are blocks.
• Si blocks represent polymerized styrene and Bi blocks of polymerized butadiene, polymerized isoprene or a mixture of butadiene and polymerized isoprene.
• the blocks Bi can be hydrogenated (it is then for example S-EB-S).
• Y denotes a polyfunctional entity derived for example from polyfunctional coupling agents which is used in the manufacture of star block copolymers. Such agents as well as these block copolymers are described in US 3639521.
• Preferred star block copolymers contain 15 to 45% by weight and more preferably 25 to 35% styrene units.
• the molar mass is at least 140,000 and more preferably at least 160,000 g / mol.
• star-block polymers are those described in EP 451920. These copolymers are based on styrene and isoprene, the molar mass of the polystyrene blocks is at least 12000 and the polystyrene content is 35% (weight). at most of the total mass of the block copolymer.
• the preferred linear block copolymers have a molecular weight of between 70000 and 145000 and contain 12 to 35% by weight of polystyrene.
• Particularly preferred block linear block copolymers are those based on styrene and isoprene described in the European patent.
• copolymers have polystyrene blocks of molar mass between 14000 and 16000 and a polystyrene content of between 25 and 35% by weight of the block copolymer.
• the molar mass is between 80000 and 145000 and better between 100000 and 145000.
• linear SBS triblocks and star SB-S triblocks.
• These linear SBS triblock or star are commercially available under the trademarks ® FINAPRENE, Finaclear ®, Kraton ® and STYROLUX ®.
• VOH reinforced or not on impact An example of EVOH of interest for the invention is the grade SOARNOL DC 3203 F marketed by the company NIPPON-GOHSEI. This grade has the following characteristics: ethylene content (mol%): melt index (210 ° C., 2.16 kg): 3.2 g / 10 min melting point: 183 ° C. crystallization temperature: 160 ° C. oxygen permeability: 0.5 this 20 ⁇ m / m 2 day atm
• An example of impact-enhanced EVOH is obtained by mixing 80% (by weight) SOARNOL DT 2903 marketed by Nippon Gohsei and 20% maleic EPR Exxelor VA 1803 marketed by Exxon-Mobil chemical.
• the SOARNOL DT 2903 has the following characteristics: ethylene content (mol%): 29 Melt Index (210 0 C, 2.16 kg): 3.2 g / 10 min Melting temperature: 188 ° C crystallization temperature: 163 ° C oxygen permeability: 0.4 this 20 ⁇ m / m 2 day atm
• Another example of impact-enhanced EVOH includes:
• a functionalized shock modifier content 1 to 30%, preferably an ethylene-propylene copolymer on which has been grafted with maleic anhydride (mRPE), a polyolefin on which maleic anhydride has been grafted, or a copolymer of ethylene, ethyl acrylate and maleic anhydride;
• mRPE maleic anhydride
• PE unfunctionalized polyolefin
• PP PP, EPR
• a polyamide or a copolyamide or mixture dispersing finely in the EVOH for example PA6.
• a layer C1 comprising at least one functionalized fluoropolymer, optionally mixed with at least one compatible fluorinated polymer;
• a layer C2 comprising at least one adhesion binder;
• a layer C3 comprising at least one polyolefin, preferably a polyethylene
• a layer C4 comprising at least one adhesion binder
• a barrier layer C5 comprising at least one barrier polymer, optionally reinforced on impact; the layers being arranged against each other in the order indicated.
• C1 The function of C1 is to chemically protect the other layers.
• C1 also has a barrier function.
• the proportion by weight of functionalized fluoropolymer ranges from 1 to 99%, preferably from 50 to 90%, for 99 to 1% compatible fluoropolymer, preferably from 50 to 10%.
• the adhesion binder of C2 comprises at least one thermoplastic polymer carrying chemical functions which react with the unsaturated polar monomer of the functionalized fluoropolymer (hereinafter, to simplify, will be referred to as "reactive chemical functions"").
• the functionalized fluoropolymer carries acid and / or anhydride functions
• the polymer of the C2 bonding binder may carry epoxide or hydroxyl functions.
• the functionalized fluoropolymer carries of epoxide and / or hydroxy functions
• the polymer of the C2 adhesion binder may carry acid and / or anhydride functions.
• the adhesion binder (and therefore in particular the thermoplastic polymer) of C2 must also preferably be compatible with the polyolefin.
• the polymer carrying the reactive chemical functions is preferably chosen from functionalized polyolefins.
• the polyolefin of C3 is a polyethylene
• the thermoplastic polymer carrying reactive functional groups a polyethylene onto which has been grafted an unsaturated polar monomer. It may also be a copolymer of ethylene and an unsaturated polar monomer and optionally an alkyl (meth) acrylate.
• the polyolefin of C3 is a polypropylene, it is possible to use a polypropylene onto which has been grafted an unsaturated polar monomer.
• the polymer carrying the reactive chemical functions may optionally be mixed with a compatible and viscous polyolefin to form the C2 adhesion binder.
• Viscous polyolefin is understood to mean a polyolefin having a melt index between 0.1 and 1 g / 10 min (190 ° C., 2.16 kg). The Applicant has thus found that with certain mixtures, it is possible to obtain a very strong adhesion between C1 and C3 (hence a peel force between these layers of between 10 and 100 N / cm) and also to avoid defects. extrusion (eg extrusion waves).
• An example of such an adhesion binder comprises, by weight, from 1 to 80%, advantageously from 10 to 50%, preferably from 10 to 40%, of at least one polymer carrying reactive chemical functions and from 99 to 20%, advantageously from 90 to 50%, preferably from 90 to 60% of at least one compatible polyolefin having a melt index of between 0.1 and 1 g / 10 min (190 ° C., 2.16 kg).
• the function of C4 is to promote membership between C3 and C5.
• the C4 adhesion binder comprises at least one thermoplastic polymer carrying chemical functions which react with the functions present on the C5 barrier polymer and / or possibly those present on the impact modifier of the C5 barrier polymer.
• the thermoplastic polymer of C4 may be a polyethylene functionalized with carboxylic acid anhydride groups, preferably maleic anhydride.
• it may be a polyethylene on which has been grafted maleic anhydride.
• the C4 bonding binder must also preferably be compatible with the polyolefin.
• the polymer carrying the reactive chemical functions is preferably chosen from functionalized polyolefins.
• the polyolefin of C3 is a polyethylene
• the thermoplastic polymer carrying reactive functional groups a polyethylene onto which has been grafted an unsaturated polar monomer. It may also be a copolymer of ethylene and an unsaturated polar monomer and optionally an alkyl (meth) acrylate.
• the polyolefin of C3 is a polypropylene, it is possible to use a polypropylene onto which has been grafted an unsaturated polar monomer.
• C4 can be omitted if the thermoplastic polymer carrier reactive chemical functional groups is mixed with the polyolefin C3.
• the multilayer structure then comprises in order (from inside to outside):
• a layer C1 comprising at least one functionalized fluoropolymer, optionally mixed with at least one compatible fluorinated polymer;
• a layer C2 comprising at least one adhesion binder;
• a layer C3 comprising at least one polyolefin, preferably a polyethylene, mixed with a thermoplastic polymer carrier of chemical functions which react with the functions present on the C5 barrier polymer and / or optionally on those present on the impact modifier of the C5 barrier polymer;
• a barrier layer C5 comprising at least one barrier polymer, optionally reinforced on impact; the layers being arranged against each other in the order indicated.
• the proportion by weight of the thermoplastic polymer ranges from 0.1 to 50%, advantageously from 1 to 50%, respectively from 99.9 to 50%, advantageously from 99 to 50% of polyolefin.
• a layer C'1 comprising at least one functionalized fluorinated polymer, optionally mixed with at least one compatible fluorinated polymer;
• a barrier layer C'2 comprising at least one barrier polymer, optionally reinforced on impact;
• a layer C'3 comprising at least one polyolefin, preferably a polyethylene, mixed with a thermoplastic polymer carrying chemical functions which react with the functions present on the barrier polymer (s) and / or possibly on those present on the impact modifier of the barrier polymer of C'2 and C'4;
• a barrier layer C'4 comprising at least one barrier polymer, optionally reinforced on impact; the layers being arranged against each other in the order indicated.
• layer C'1 It has the same characteristics as those detailed for C1.
• the unsaturated polar monomer of the functionalized fluoropolymer reacts with the chemical functions of the barrier polymer of C'2 and possibly on those of the shock modifier of C'2.
• the deformation resistance of a tube-like multilayer structure is improved when the C'2 barrier polymer is impact-reinforced.
• the impact resistance of the tube is also improved when the barrier polymer of C'4 is reinforced at impact.
• the functionalized fluoropolymer is a functionalized PVDF;
• the fluoropolymer which is optionally mixed with the functionalized fluoropolymer is a PVDF;
• the polyolefin of C3 or C'3 is a polyethylene
• the C4 adhesion binder is a thermoplastic polymer carrying chemical functions which react with the functions present on the C5 barrier polymer and / or optionally on those present on the impact modifier of the C5 barrier polymer;
• the barrier polymer of C5, C'2 and C'4 is an EVOH
• thermoplastic polymer of C2, C3, C4, C'3 is a functionalized polyolefin.
• the functionalized fluoropolymer is a PVDF onto which has been grafted by irradiation an acid anhydride, preferably maleic anhydride.
• This fluoropolymer extrudates very well and also has excellent adhesion.
• the combination of a PVDF and EVOH makes the multilayer structure barrier to a large number of molecules, making it usable for many different fuel types.
• EVOH also has a good compromise permeability / coextrusion ability with respect to other barrier polymers (eg PPS).
• An example of a multilayer structure includes (from inside to outside):
• a layer comprising a PVDF on which has been grafted by irradiation of maleic anhydride, optionally in admixture with a compatible PVDF;
• a layer comprising an adhesion binder A layer comprising a polyethylene;
• a layer comprising a polyethylene on which maleic anhydride has been grafted
• Another example of a multilayer structure includes (from inside to outside):
• a layer comprising a polyethylene
• a layer comprising a polyethylene on which maleic anhydride has been grafted
• PVDF can be a homo- or a copolymer.
• the adhesion binder is a polyethylene carrying chemical functions which react with maleic anhydride. It is preferably a polyethylene carrying epoxide functions.
• the polyethylene is a PE 100.
• the multilayer structure comprises (from inside outwards):
• a barrier layer C * 1 comprising at least one barrier polymer, optionally reinforced on impact;
• a layer C * 2 comprising at least one adhesion binder;
• a layer C * 3 comprising at least one polyolefin
• a CM layer comprising at least one adhesion binder
• a barrier layer C * 5 comprising at least one barrier polymer, optionally reinforced on impact; the layers being arranged against each other in the order indicated.
• the adhesion binder C * 2 and / or CM preferably comprises a thermoplastic polymer carrying chemical functions that react with those of the barrier polymer and / or optionally those of the impact modifier.
• the thermoplastic polymer is further compatible with the polyolefin.
• the barrier polymer is an EVOH
• thermoplastic polymer of C * 2 and CM is a functionalized polyolefin.
• An example of a multilayer structure includes (from inside to outside):
• a layer comprising a polyethylene
• a layer comprising a polyethylene on which maleic anhydride has been grafted
• a layer comprising an EVOH reinforced with the impact; the layers being arranged against each other in the order indicated.
• each of the layers may optionally comprise one or more additives chosen from dyes and / or pigments, antioxidants, anti-UV agents, flame retardants, mineral fillers,
• each of the layers can be made conductive by means of a conductive filler capable of discharging electrical charges such as carbon black or carbon nanotubes. It is more particularly the layer in contact with the fluid to be transferred or stored.
• the resistivity of the conductive layer is less than 10 6 ⁇ .cm.
• the layers C3 or C'3 or C * 3 which comprise the polyolefin have a thickness ranging from 1 to 10 mm so as to provide the structure with overall rigidity, good mechanical strength and also withstand the hydrostatic pressure.
• the other layers have a thickness that can preferably range from 25 to 1000 ⁇ m.
• the multilayer structure can be in the form of a film, tube, pipe, container or tank.
• the layer in contact with the fluid to be transported or stored is the layer C1, C'1 or C * 1 or the layer of the fluoropolymer which is arranged against C1 or C'1.
• This structure has a permeability less than or equal to 1 g / m 2 day according to the UL-971 standard.
• the multilayer structure and the polymer blends are made using known techniques of plastics processing.
• an extruder is used to make the mixtures.
• To manufacture a tube or a pipe one can use the coextrusion technique which relies on the use of as many extruders as there are superimposed layers.
• a tank or a hollow body it is possible to use the blow molding of hollow bodies.
• the multilayer structure in the form of tube, pipe, container or tank has interesting barrier properties vis-à-vis various fuels (gasoline, diesel, alcoholic spirits, alcohol ...) for storing or transferring a fuel.
• This may for example be the supply tube of the fuel tank to the engine or in a service station, the fuel supply tube of the storage tank to the vehicle or to the fuel dispenser.
• the fuel can be a gasoline, a diesel or an alcoholic gasoline currently developed in some countries such as Brazil (Flexfuel type, biodiesel comprising a high content of methanol and / or ethanol).
• gasoline transport tubes both mechanical characteristics such as bursting resistance and flexibility with good resistance to cold shocks ( -40 0 C) and at high temperature (125 ° C), and also a very low permeability to hydrocarbons and their additives, especially alcohols such as methanol and ethanol.
• These tubes must also have good resistance to fuels and engine lubricating oils.
• five are particularly difficult to obtain jointly in a simple way:
• EVOH SOARNOL ® DT 2903 from NIPPON-GOHSEI EVOH shock: EVOH reinforced with impact by the EPR maléisé.
• Lotader ® 8840 glycidyl methacrylate copolymer (8% by weight) and ethylene (92 wt%), melt index of 6 (190 0 C, 2.16 kg)
• Orevac ® 18334 polyethylene grafted with maleic anhydride, d melt index of 1 (190 ° C, 2.16 kg)
• PVDF-1 KYNAR ® 720 on which has been grafted maleic anhydride by irradiation (see below); melt flow index of 13 (230 0 C, 5 kg), diluted to 30% by weight of KYNAR ® 720 ungrafted (70% unmodified KYNAR KYNAR + 30% modified).
• PE-100 marketed by BOREALIS (melt flow index of 0.3 to 190 ° C. under 2.16 kg)
• EXXELOR VA 1803 ® sold by Exxon-Mobil Chemicals, melt flow index of 3 under 2.16 kg at 230 ° C.
• KYNAR ® 720 is formed by first mixing in a molten state KYNAR ® 720 (homopolymer volume flow rate in the molten state of 10 cm 3/10 min at 230 0 C under 5 kg) with 2% by weight of maleic anhydride. The mixture is prepared using a twin-screw extruder at 230 ° C. and 150 rpm at a flow rate of 10 kg / h.
• Grafting on the KYNAR FLEX ® 2750 is formed by first mixing all melt KYNAR ® 2750 (copolymer with a melt index in volume melt of 10 cm 3/10 min at 230 0 C under 5 kg) with 2% by weight of maleic anhydride. The mixture is prepared using a twin-screw extruder at 230 ° C and 150 rpm at a rate of 10 kg / hr. After the extrusion step, 1.95% maleic anhydride remains in the product, the remainder being lost during the extrusion step. The product thus prepared and bagged in sealed aluminum bags. These bags are then irradiated under 2 Mrad with a Cobalt bomb.
• a grafting rate of 40% is determined, this rate is verified after a solubilization precipitation step.
• KYNAR FLEX ® grafted with maleic anhydride is then placed under vacuum overnight at 130 ° C. to evacuate residual maleic anhydride and hydrofluoric acid released during irradiation. This product is then diluted by mixing 50% of this product in 50% of
• Example 1 5-layer structure according to the 1 st form on an extruder type Mc Neil, coextruding a tube of 5 layers of 50 mm in outer diameter and 40 mm internal diameter. The following layers are from inside to outside: PVDF-1 (300 ⁇ m);
• OREVAC 18334 (50 ⁇ m);
• This coextrusion is carried out with a head temperature of 240 ° C.
• the adhesion measured is greater than 30 N / cm between each of the layers.
• the tube has an M15 permeability at 28 ° C of 0.1 g / m 2 / day and an M85 permeability of 0.08 g / m 2 / day. This tube is tested during a drop mass experiment (1.8 m height, -30 0 C, mass of 0.5 kg), no apparent crack can be observed while 10 tubes were tested.
• Example 2 4-layer structure according to the variant of the 1 st form The tube is performed under the same conditions as for Example 1. The four layers are the following with the inside to the outside:
• PVDF-1 (300 ⁇ m);
• the adhesion measured is greater than 30 N / cm between each of the layers.
• the tube exhibits a permeability to M15 (at 28 ° C. of 0.15 g / m 2 day and an M85 permeability of 0.12 g / m 2 day)
• the tube is tested during a mass drop experiment (1.8 m height, -30 0 C, mass of 0.5 kg), no apparent crack can be observed while 10 tubes were tested.
• Example 3 4-layer structure according to the 2nd form
• the tube is made under the same conditions as for example 1.
• the 4 layers are as follows with from inside to outside:
• PVDF-1 300 ⁇ m
• - EVOH shock 300 ⁇ m
• the adhesion measured is greater than 30 N / cm between each of the layers.
• the tube has an M15 permeability at 28 ° C of 0.08 g / m 2 / day and an M85 permeability of 0.05 g / m 2 / day. This tube is tested during a drop mass experiment (1.8 m height, -30 0 C, mass of 0.5 kg), no apparent crack can be observed while 10 tubes were tested.
• Example 4 4-layer structure according to the 2nd form
• the tube is made under the same conditions as for example 1.
• the 4 layers are as follows with from inside to outside:
• PVDF-2 (300 ⁇ m); - EVOH shock (300 ⁇ m);
• the adhesion measured is greater than 30 N / cm between each of the layers.
• the tube has an M15 permeability at 28 ° C of 0.12 g / m 2 day and an M85 permeability of 0.08 g / m 2 / day. This tube is tested during a drop mass experiment (1.8 m height, -30 0 C, mass of 0.5 kg), no apparent crack can be observed while 10 tubes were tested.
• Example 5 5-layer structure according to the 3rd form
• the tube is made under the same conditions as for example 1.
• the 5 layers are as follows with from inside to outside: - EVOH shock (300 ⁇ m);
• OREVAC 18334 (50 ⁇ m);
• OREVAC 18334 50 ⁇ m
• - EVOH shock 300 ⁇ m
• the adhesion measured is greater than 30 N / cm between each of the layers.
• the tube has an M15 permeability at 28 ° C of 0.17 g / m 2 / day and an M85 permeability of 0.14 g / m 2 / day. This tube is tested during a drop mass experiment (1.8 m height, -30 0 C, mass of 0.5 kg), no apparent crack can be observed while 10 tubes were tested.

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• 2007
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