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EP1651437A2 - Multilayer structure comprising a modified impact evoh layer - Google Patents

Multilayer structure comprising a modified impact evoh layer

Info

Publication number
EP1651437A2
EP1651437A2 EP04786248A EP04786248A EP1651437A2 EP 1651437 A2 EP1651437 A2 EP 1651437A2 EP 04786248 A EP04786248 A EP 04786248A EP 04786248 A EP04786248 A EP 04786248A EP 1651437 A2 EP1651437 A2 EP 1651437A2
Authority
EP
European Patent Office
Prior art keywords
layer
polyamide
evoh
polyolefin
structure according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP04786248A
Other languages
German (de)
French (fr)
Inventor
Gaelle Bellet
Nicolas Amouroux
Thibaut Montanari
Benoît BRULE
Anthony Bonnet
Fabrice Chopinez
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Arkema France SA
Arkema SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Arkema France SA, Arkema SA filed Critical Arkema France SA
Publication of EP1651437A2 publication Critical patent/EP1651437A2/en
Withdrawn legal-status Critical Current

Links

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
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/21—Anti-static
    • 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
    • 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
    • B32B2377/00—Polyamides
    • 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
    • B32B2439/00—Containers; Receptacles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Ethene-propene or ethene-propene-diene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • 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]
    • Y10T428/31725—Of polyamide
    • Y10T428/3175—Next to addition polymer from unsaturated monomer[s]

Definitions

  • the present invention relates to a multilayer structure comprising a layer of shock modified EVOH. It can comprise the following successive layers: a layer of polyamide or HDPE (high density polyethylene), a layer of binder, the layer of shock modified EVOH, optionally a layer of binder, a layer (1) of polyamide or of mixture polyamide and polyolefin or polyolefin.
  • This last layer (1) of polyamide or mixture of polyamide and polyolefin or polyolefin may contain fillers to make it antistatic.
  • These structures in which the polyamide or HDPE layer is the outer layer and the polyamide or polyamide and polyolefin or polyolefin blend layer is the inner layer in contact with the fluid (gasoline), are useful for make tanks, containers, bottles and tubes. They can be manufactured by coextrusion or by coextrusion blow molding. The advantage of these structures is that they are a barrier to many products.
  • One particularly useful use relates to tubes for transporting petrol and in particular for bringing petrol from the tank of an automobile to the engine.
  • Another particularly useful use relates to petrol tanks for automobiles.
  • Patent EP 1122061 described a structure successively comprising: a first layer of high density polyethylene (HDPE), a layer of binder, a second layer of EVOH or of a mixture based on EVOH, possibly a third layer of polyamide (A) or a mixture of polyamide (A) and polyolefin (B). In this patent, three mixtures based on EVOH are described.
  • HDPE high density polyethylene
  • B polyolefin
  • the first mixture relates to compositions comprising (by weight): - 55 to 99.5 parts of EVOH copolymer, - 0.5 to 45 parts of polypropylene and compatibilizer, their proportions being such that the ratio of the amount of polypropylene to the amount of compatibilizer is between 1 and 5.
  • the second mixture relates to compositions comprising: - 50 to 98% by weight of an EVOH copolymer - 1 to 50% by weight of a polyethylene -1 to 15% by weight of a compatibilizer consisting of a mixture of a LLDPE or metallocene polyethylene and a polymer chosen from elastomers, very low density polyethylenes and metallocene polyethylenes, the mixture being cografted by an unsaturated carboxylic acid or a functional derivative of this acid.
  • a compatibilizer consisting of a mixture of a LLDPE or metallocene polyethylene and a polymer chosen from elastomers, very low density polyethylenes and metallocene polyethylenes
  • the third mixture relates to compositions comprising: - 50 to 98% by weight of an EVOH copolymer - 1 to 50% by weight of an ethylene - (meth) acrylate copolymer, - 1 to 15% by weight of a compatibilizer resulting from the reaction (i) of a copolymer of ethylene and of an unsaturated monomer X grafted or copolymerized with (ii) a copolyamide.
  • the patents EP 1243831, EP 1314758, EP 1314759 and EP 1331091 describe multilayer pipes comprising an EVOH layer which may consist of a mixture based on EVOH identical to the mixtures described in patent EP 1122061 cited above. These EVOH-based mixtures are insufficient for large shocks. [Brief description of the invention]
  • the present invention relates to a multilayer structure comprising the following successive layers: a layer of polyamide or of HDPE (high density polyethylene), a layer of binder, a layer of impact modified EVOH, optionally a layer of binder, a layer (1) of polyamide or of mixture of polyamide and of polyolefin or of polyolefin, the latter layer possibly containing fillers to make it antistatic, and such that the layer of shock-modified EVOH is a mixture based on EVOH and at least one impact modifier chosen from: a) functionalized ethylene- (meth) acrylate copolymers, b) products resulting from the reaction (i) of a copolymer of ethylene and of an unsaturated monomer X grafted or copolymerized with (ii ) a polyamide, c) mixtures of a) and b), d) polyamides, preferably PA 6, e) mixtures of a) and d), f) elastomers, preferably
  • the proportion of impact modifier is comprised, by weight, between 1 and 35% for respectively 99 to 65% of EVOH.
  • the present invention also relates to devices for transferring or storing fluids and more particularly pipes, tanks, chutes, bottles and containers made up of the above structure.
  • the layer (1) of polyamide or of mixture of polyamide and of polyolefin or of polyolefin is in direct contact with the fluid contained or transported.
  • These devices can be manufactured by the usual techniques in the thermoplastic polymer industry such as coextrusion and extrusion blow molding. The thicknesses of these devices have been described in the prior art.
  • the layer (1) is not antistatic and a layer (2) is added arranged on the side of the layer (1), this layer (2) contains fillers to make it antistatic.
  • This layer (2) can be constituted like the layer (1) of polyamide or of mixture of polyamide and of polyolefin or of polyolefin.
  • the layers (1) and (2) can be of the same nature, for example both in polyamide or in a mixture of polyamide and polyolefin or in polyolefin. They can also be different, for example one is made of polyolefin and the other is made of polyamide or any other combination.
  • a binder is placed between layers (1) and (2). In this form of the invention where there is a layer (1) and a layer (2) it is the layer (2) which is in contact with the fluid contained or transported.
  • the functions can be an acid, an acid anhydride or an unsaturated epoxide.
  • the amount of unsaturated carboxylic anhydride can be up to 15% by weight of the copolymer and the amount of ethylene at least 50% by weight.
  • it is an ethylene copolymer of an alkyl (meth) acrylate and an unsaturated carboxylic anhydride.
  • the alkyl (meth) acrylate is such that the alkyl has 2 to 10 carbon atoms.
  • the alkyl (meth) acrylate can be chosen from methyl methacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2- acrylate. ethylhexyl.
  • the MFI can for example be between 0.1 and 50 (g / 10 min at 190 ° C. under 2.16 kg).
  • it is an ethylene copolymer of an alkyl (meth) acrylate and an unsaturated epoxide.
  • the alkyl (meth) acrylate is such that the alkyl has 2 to 10 carbon atoms.
  • the MFI (melt flow index) of (A) can for example be between 0.1 and 50 (g / 10 min at 190 ° C. under 2.16 kg).
  • alkyl acrylate or methacrylate which can be used are in particular methyl methacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate.
  • unsaturated epoxides which can be used are in particular: - aliphatic glycidyl esters and ethers such as allyl glycidyl ether, vinyl glycidyl ether, glycidyl itaconate and maleate, glycidyl acrylate and methacrylate, and - esters and alicyclic glycidyl ethers such as 2-cyclohexene-1-glycidylether, 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 allyl glycidyl ether, vinyl
  • graft copolymer with polyamide blocks consisting of a polyolefin trunk and at least one polyamide graft in which: the grafts are attached to the trunk by the remains of an unsaturated monomer (X) having a function capable of reacting with an amino-terminated polyamide, the residues of the unsaturated monomer (X) are fixed to the trunk by grafting or copolymerization from its double bond.
  • the graft copolymer with polyamide blocks it can be obtained by reaction of an amino-terminated polyamide with the remains of an unsaturated monomer X fixed by grafting or copolymerization on a polyolefin backbone.
  • This monomer X can for example be an unsaturated epoxide or an unsaturated carboxylic acid anhydride.
  • the unsaturated carboxylic acid anhydride can be chosen, for example, from maleic anhydrides, itaconic, citraconic, allylsuccinic, cyclohex-4-ene-1, 2-dicarboxylic, 4 - methylene cyclohex-4-ene 1, 2-dicarboxylic, bicyclo (2,2,1) hept-5-ene 2,3- dicarboxylic, and x— methylbicyclo (2,2,1) hept-5-ene-2,2-dicarboxylic.
  • Maleic anhydride is advantageously used.
  • a polyolefin is defined as a homopolymer or copolymer of alpha olefins or of diolefins, such as, for example, ethylene, propylene, butene-1, octene-1, butadiene.
  • the copolymers of ethylene and of X that is to say those in which X is not grafted, these are copolymers of ethylene, of X and optionally of another monomer.
  • the ethylene-maleic anhydride and ethylene - (meth) acrylate - maleic anhydride copolymers are used. These copolymers comprise from 0.2 to 10% by weight of maleic anhydride, from 0 to 40% and preferably 5 to 40% by weight of alkyl (meth) acrylate. Their MFI is between 5 and 100 (190 ° C - 2.16 kg). The alkyl (meth) acrylates have already been described above. The melting temperature is between 60 and 100 ° C.
  • polyamide means the condensation products: of one or more amino acids, such as aminocaproic, amino-7-heptanoic, amino-11-undecanoic and amino-12-dodecanoic acids or several lactams such as caprolactam, oenantholactam and lauryllactam; - one or more diamine salts or mixtures such as hexamethylene diamine, dodecamethylenediamine, metaxylylenediamine, bis-p aminocyclohexylmethane and trimethylhexamethylene diamine with diacids such as isophthalic, terephthalic, adipic, azelaic, sebacic and dodecanedicarboxylic: - or mixtures of several monomers which leads to copolyamides.
  • amino acids such as aminocaproic, amino-7-heptanoic, amino-11-undecanoic and amino-12-dodecanoic acids or several lactams such as caprolactam, oen
  • PA 6 PA 11, PA 12, copolyamide with patterns 6 and patterns 11 (PA 6/11), copolyamide with patterns 6 and patterns 12 (PA 6/12), and copolyamide based are advantageously used.
  • PA 6 PA 11, PA 12, copolyamide with patterns 6 and patterns 11 (PA 6/11), copolyamide with patterns 6 and patterns 12 (PA 6/12), and copolyamide based are advantageously used.
  • PA 6 / 6-6 hexamethylenediamine and adipic acid
  • the advantage of copolyamides is that one can thus choose the melting point of the grafts.
  • the grafts are homopolymers consisting of residues of caprolactam, amino-11-undecanoic acid or dodecalactam or copolyamides consisting of residues chosen from at least two of the three
  • the degree of polymerization can vary within wide proportions, depending on its value it is a polyamide or a polyamide oligomer. In the rest of the text, the two expressions will be used interchangeably for the plugins.
  • the polyamide For the polyamide to have a monoamine termination, it suffices to use a chain limiter of formula R 1 —NHR 2 in which:
  • R is hydrogen or a linear or branched alkyl group containing up to 20 carbon atoms
  • R2 is a group having up to 20 linear or branched alkyl or alkenyl carbon atoms, a saturated or unsaturated cycloaliphatic radical, an aromatic radical or a combination of the preceding.
  • the limiter can for example be laurylamine or oleylamine.
  • the polyamide with an amino end has a molar mass of between 1000 and 5000 g / mole and preferably between 2000 and 4000.
  • the amino acid or lactam monomers preferred for the synthesis of the monoamine oligomer according to the invention are chosen from caprolactam, amino-11-undecanoic acid or dodecalactam.
  • Preferred monofunctional polymerization limiters are laurylamine and oleylamine.
  • the polycondensation defined above is carried out according to the usually known methods, for example at a temperature generally understood between 200 and 300 ° C, under vacuum or under an inert atmosphere, with stirring of the reaction mixture.
  • the average chain length of the oligomer is determined by the initial molar ratio between the polycondensable monomer or the lactam and the monofunctional polymerization limiter. For the calculation of the average chain length, there is usually one molecule of chain limiter for an oligomer chain.
  • the addition of the polyamide monoamine oligomer to the polyolefin trunk containing X is carried out by reaction of an amino function of the oligomer with X.
  • Advantageously X carries an anhydride or acid function, thus creating amide bonds or imide.
  • the addition of the amino-terminated oligomer is carried out on the polyolefin trunk containing X, preferably in the molten state. It is thus possible, in an extruder, to knead the oligomer and the trunk at a temperature generally between 230 and 250 ° C.
  • the average residence time of the molten material in the extruder can be between 15 seconds and 5 minutes, and preferably between 1 and 3 minutes.
  • the yield of this addition is evaluated by selective extraction of the free polyamide oligomers, that is to say those which have not reacted to form the graft copolymer with final polyamide blocks.
  • the preparation of such amino-terminated polyamides as well as their addition to a polyolefin trunk containing X is described in patents US 3,976,720, US 3,963,799, US 5,342,886 and FR 2,291,225.
  • each block is linked to the other by means of a covalent bond or to an intermediate molecule linked to one of the blocks by a covalent bond and to the other block by another covalent bond
  • the block M consists of MMA monomers optionally copolymerized with other monomers and comprises at least 50% by weight of methyl methacrylate (MMA)
  • block B is incompatible with EVOH and with block M
  • block S is incompatible with block B and block M and its Tg or its melting temperature Tf is higher than the Tg of B.
  • the triblock SBM M consists of methyl methacrylate monomers or contains at least 50 % by mass of methyl methacrylate, preferably at least 75% by mass of methyl methacrylate.
  • the other monomers constituting the block M can be acrylic monomers or not, be reactive or not.
  • reactive functions mention may be made of: oxirane functions, amine functions, carboxy functions.
  • the reactive monomer can be (meth) acrylic acid or any other hydrolyzable monomer leading to these acids.
  • the other monomers which can constitute the block M there may be mentioned by way of nonlimiting example glycidyl methacrylate tertiary butyl methacrylate.
  • Advantageously M consists of at least 60% syndiotactic PMMA.
  • the Tg of B is less than 0 ° C and preferably less than - 40 ° C.
  • the monomer used to synthesize the elastomeric block B can 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), in particular poly (butadiene), poly (isoprene) and their random copolymers, or alternatively from poly (dienes) partially or completely hydrogenated.
  • polybutadienes those with the lowest Tg are advantageously used, for example polybutadiene-1, 4 of Tg (around -90 ° C.) lower than that of polybutadiene-1, 2. (around 0 ° C).
  • B blocks can also be hydrogenated. This hydrogenation is carried out according to the usual techniques.
  • the monomer used to synthesize the elastomeric block B can also be an alkyl (meth) acrylate, the following Tg are obtained in brackets according to the name of the acrylate: ethyl acrylate (-24 ° C), l butyl acrylate, (-54 ° C), 2-ethylhexyl acrylate (-85 ° C), hydroxyethyl acrylate (-15 ° C) and 2-ethylhexyl methacrylate (-10 ° C ).
  • acrylate is used butyl.
  • the acrylates are different from those of block M to respect the condition of incompatible B and M.
  • the blocks B consist mainly of polybutadiene-1, 4.
  • the Tg or Tf of S is advantageously greater than 23 ° C and preferably greater than 50 ° C.
  • blocks S that may be mentioned are those which derive from vinyl aromatic compounds such as, for example, styrene, ⁇ -methyl styrene, vinyltoluene.
  • the SBM triblock is a polystyrene-polybutadiene-PMMA.
  • the SBM triblock has a number-average molar mass which can be between 10,000 g / mol and 500,000 g / mol, preferably between 20,000 and 200,000 g / mol.
  • the SBM triblock advantageously has the following composition expressed as a mass fraction, the total being 100%: M: between 10 and 80% and preferably between 15 and 70%.
  • SBM triblocks can be mixed with SB diblocs.
  • the S and B blocks have the same properties as the S and B blocks of the SBM triblock, they are incompatible and they consist of the same monomers and optionally comonomers as the S blocks and B blocks of the SBM triblock. That is to say that the blocks S of the diblock SB consist of monomers chosen from the same family as the family of monomers available for the blocks S of the triblock SBM.
  • blocks B of the SB diblock consist of monomers chosen from the same family as the family of monomers available for blocks B of the SBM triblock.
  • the dibloc SB has a number-average molar mass which can be between 10,000 g / mol and 500,000 g / mol, preferably between 20,000 and 200,000 g / mol.
  • the SB diblock advantageously consists of a mass fraction of B of between 5 and 95% and preferably between 15 and 85%.
  • the mixture of triblock SBM and diblock SB advantageously comprises between 5 and 80% of diblock SB for respectively 95 to 20% of triblock SBM.
  • the advantage of these compositions is that it is not necessary to purify the SBM at the end of its synthesis. Indeed, SBMs are generally prepared from SBs and the reaction often leads to a mixture of SBs and SBMs which are then separated in order to have SBMs.
  • SBM triblock copolymers can be produced by anionic polymerization, for example according to the methods described in patent applications EP 524,054 and EP 749,987. They can also be produced by controlled radical polymerization. These triblock copolymers S-
  • SBS triblocks are described in ULLMANN'S encyclopedia of industrial chemistry Vol A 26, pages 655 - 659.
  • SBS triblocks mention may be made of the linear lines in which each block is connected to the other at by means of a covalent bond or of an intermediate molecule linked to one of the blocks by a covalent bond and to the other block by another covalent bond.
  • the S and B blocks have the same properties as the S and B blocks of the SBM triblock, they are incompatible and they consist of the same monomers and possibly comonomers as the S blocks and the B blocks of the SBM triblock.
  • the blocks S of the triblock S-BS consist of monomers chosen from the same family as the family of monomers available for the blocks S of the triblock SBM.
  • the blocks B of the SBS triblock consist of monomers chosen from the same family as the family of monomers available for the blocks B of the S-BM triblock.
  • the blocks S and B can be identical or different from the other blocks S and B present in the other block copolymers.
  • the linear SBS triblock has a number-average molar mass which can be between 10,000 g / mol and 500,000 g / mol, preferably between 20,000 and 200,000 g / mol.
  • the SBS triblock is advantageously made up of a mass fraction in B of between 5 and 95% and preferably between 15 and 85%.
  • SBS triblocks one can cite those in star.
  • the term "triblock” does not agree with the number of blocks but the term "star SBS triblocks" is clear to those skilled in the art.
  • star triblocks include those of formula:
  • n 1, 2 or 3 and S-
  • S-i represent polymerized styrene and blocks B-] of polymerized butadiene, polymerized isoprene or a mixture of butadiene and polymerized isoprene.
  • can be hydrogenated (in this case, for example, S-EB-S).
  • Y is a polyfunctional entity originating for example from polyfunctional coupling agents which are used in the manufacture of star block copolymers. Such agents as well as these block copolymers are described in US
  • Preferred star block copolymers contain 15 to
  • styrene units 45% by weight and better 25 to 35% of styrene units.
  • the molar mass is at least 140,000 and better still at least 160,000.
  • Particularly preferred star block polymers are those described in EP 451920. These copolymers are based on styrene and isoprene, the molar mass of the blocks polystyrene is at least 12,000 and the polystyrene content is 35% (weight) at most of the total mass of the block copolymer.
  • Preferred linear block copolymers have a molecular weight between 70,000 and
  • Copolymers linear blocks particularly preferred blocks are those based on styrene and isoprene described in the European patent
  • EP 451919 These copolymers have polystyrene blocks with a molar mass between 14,000 and 16,000 and a polystyrene content of between 25 and 35% by weight of the block copolymer. The molar mass is between 80,000 and 145,000 and better between 100,000 and 145,000. It is also possible to use a mixture of linear S-B-S triblocks and star S-B-S triblocks. These linear or star S-B-S triblocks are commercially available under the brands Finaprène®, Finaclear®, Kraton® and Styrolux®.
  • the polyamide can be chosen from semi-aromatic or semi-cycloaliphatic PAs and aliphatic polyamides.
  • the aliphatic polyamides can be chosen from PA 11, PA
  • the aliphatic polyamides resulting from the condensation of an aliphatic diamine having from 6 to 12 carbon atoms and from an aliphatic diacid having from 9 to 12 carbon atoms and the copolyamides 11/12 having either more than 90% of units 11 or more than 90% of units 12.
  • aliphatic polyamides resulting from the condensation of an aliphatic diamine having 6 to 12 carbon atoms and an aliphatic diacid having 9 to 12 carbon atoms may include: PA 6-12 resulting from the condensation of hexamethylene diamine and 1,12-dodecanedioic acid, PA 9-12 resulting from the condensation of C9 diamine and acid 1,12 - dodecanedioic, PA 10-10 resulting from the condensation of diamine in C10 and of acid 1, 10-decanedioic, PA 10-12 resulting from the condensation of diamine in C9 and of acid 1, 12 - dodecanedioic.
  • copolyamides 11/12 having either more than 90% of units 11 or more than 90% of units 12, they result from the condensation of amino 1-undecanoic acid with lauryllactam (or alpha omega amino acid C12 ).
  • this polyamide it is also possible to add copolymers with polyamide blocks and polyether blocks and / or plasticizers.
  • the polyamide and the polyamide of the mixture of polyamide and of polyolefin can be chosen from the polyamides mentioned above but also from PA6, PA 6-6 or PA 6 / 6-6.

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Abstract

The invention relates to a multilayer structure comprising the following successive layers: a polyamide or HDPE (high-density polyethylene) layer, a binder layer, a modified impact EVOH layer, possibly a binder layer, a polyamide or a mixture of polyamide and polyolefine or polyolefine layer which can contain charges, thereby making it antistatic. The modified impact EVOH layer is embodied in the form of a mixture based on EVOH and at least one type of modifier selected amongst: a) alkyl ethylene-(meth) acrylate functionalised copolymers, b) products obtained by a reaction (i) of an ethylene copolymer and an unsaturated graft or copolymerised with polyamide (ii) X monomer, c) a) and b) mixtures, d) polyamides, preferably PA 6, e) a) and d) mixtures, f) elastomers, preferably EPR, EPDM and NBR, which can be functionalised, g) S-B-M triblocs, h) triblocs consisting of a poly(butyl acrylate) bloc between two PMMA blocs, and I) S-B-S linear bloc or possibly star-shaped hydrogenated copolymers (then they are designated by S-EB-S).

Description

STRUCTURE MULTICOUCHE COMPRENANT UNE COUCHE D'EVOH MODIFIÉ CHOC [Domaine de l'invention] La présente invention concerne une structure multicouche comprenant une couche d'EVOH modifié choc. Elle peut comprendre les couches successives suivantes: une couche de polyamide ou de HDPE (polyéthylène haute densité), une couche de liant, la couche d'EVOH modifié choc, éventuellement une couche de liant, une couche (1 ) de polyamide ou de mélange de polyamide et de polyoléfine ou de polyoléfine. MULTILAYER STRUCTURE COMPRISING A SHOCK MODIFIED EVOH LAYER [Field of the Invention] The present invention relates to a multilayer structure comprising a layer of shock modified EVOH. It can comprise the following successive layers: a layer of polyamide or HDPE (high density polyethylene), a layer of binder, the layer of shock modified EVOH, optionally a layer of binder, a layer (1) of polyamide or of mixture polyamide and polyolefin or polyolefin.
Cette dernière couche (1) de polyamide ou de mélange de polyamide et de polyoléfine ou de polyoléfine peut contenir des charges pour la rendre antistatique. Ces structures, dans lesquelles la couche de polyamide ou de HDPE est la couche extérieure et la couche de polyamide ou de mélange de polyamide et de polyoléfine ou de polyoléfine est la couche intérieure en contact avec le fluide (l'essence), sont utiles pour faire des réservoirs, des conteneurs, des bouteilles et des tubes. Elles peuvent être fabriquées par coextrusion ou par coextrusion soufflage. L'intérêt de ces structures est qu'elles sont barrière à de nombreux produits. Une utilisation particulièrement utile concerne des tubes pour le transport d'essence et en particulier pour amener l'essence du réservoir d'une automobile jusqu'au moteur. Une autre utilisation particulièrement utile concerne des réservoirs d'essence pour les automobiles.This last layer (1) of polyamide or mixture of polyamide and polyolefin or polyolefin may contain fillers to make it antistatic. These structures, in which the polyamide or HDPE layer is the outer layer and the polyamide or polyamide and polyolefin or polyolefin blend layer is the inner layer in contact with the fluid (gasoline), are useful for make tanks, containers, bottles and tubes. They can be manufactured by coextrusion or by coextrusion blow molding. The advantage of these structures is that they are a barrier to many products. One particularly useful use relates to tubes for transporting petrol and in particular for bringing petrol from the tank of an automobile to the engine. Another particularly useful use relates to petrol tanks for automobiles.
[l'art antérieur et le problème technique] Pour des raisons de sécurité et de préservation de l'environnement les constructeurs d'automobiles imposent aux tubes de transport d'essence à la fois des caractéristiques mécaniques comme la résistance à l'éclatement et la flexibilité avec une bonne tenue aux chocs à froid (-40°C) ainsi qu'à température élevée (125°C), et également une très faible perméabilité aux hydrocarbures et à leurs additifs, en particulier les alcools comme le méthanol et l'éthanol. Ces tubes doivent aussi avoir une bonne tenue aux carburants et aux huiles de lubrification du moteur. Ces tubes sont fabriqués par coextrusion des différentes couches selon les techniques habituelles des thermoplastiques. Parmi les caractéristiques du cahier des charges de ces tubes, cinq sont particulièrement difficiles à obtenir conjointement de façon simple : - tenue aux chocs à froid (-40°C), le tube ne se brise pas, - tenue aux carburants - tenue à température élevée (125°C), - très faible perméabilité à l'essence, - une bonne stabilité dimensionnelle du tube en utilisation avec de l'essence.[the prior art and the technical problem] For safety and environmental reasons, automobile manufacturers impose on petrol transport tubes both mechanical characteristics such as burst strength and flexibility with good resistance to cold shock (-40 ° C) as well as at high temperature (125 ° C), and also very low permeability to hydrocarbons and their additives, in particular alcohols such as methanol and ethanol. These tubes must also have good resistance to motor fuels and lubricating oils. These tubes are produced by coextrusion of the different layers according to the usual techniques of thermoplastics. Among the characteristics of the specifications of these tubes, five are particularly difficult to obtain jointly in a simple way: - resistance to cold shocks (-40 ° C), the tube does not break, - resistance to fuels - resistance to temperature high (125 ° C), - very low permeability to petrol, - good dimensional stability of the tube when used with petrol.
Dans les tubes multicouches de structures diverses, la tenue aux chocs à froid reste imprévisible avant d'avoir réalisé les tests normes de résistance aux chocs à froid. On a découvert que dans une structure comprenant les couches successives suivantes: une couche de polyamide ou de HDPE (polyéthylène haute densité), une couche de liant, une couche d'EVOH, éventuellement une couche de liant, une couche de polyamide ou de mélange de polyamide et de polyoléfine ou de polyoléfine, soumise à des chocs ou d'autres contraintes mécaniques équivalentes les fissures naissaient dans la couche d'EVOH et se propageaient dans toute la structure. On a aussi découvert que si on modifiait la couche d'EVOH en y ajoutant une quantité suffisante d'un modifiant choc alors, au cours d'un choc, il pouvait encore y avoir initiation de fissures dans cette couche mais qu'il n'y avait plus assez d'énergie pour propager la ou les fissures dans les autres couches et donc la structure résistait aux chocs. Le brevet EP 1122061 a décrit une structure comprenant successivement : une première couche de polyéthylène haute densité (HDPE), une couche de liant, une deuxième couche d'EVOH ou d'un mélange à base d'EVOH, éventuellement une troisième couche de polyamide (A) ou d'un mélange de polyamide (A) et de polyoléfine (B). Dans ce brevet sont décrits trois mélanges à base d'EVOH. Le premier mélange concerne des compositions comprenant (en poids) : - 55 à 99,5 parties de copolymère EVOH, - 0,5 à 45 parties de polypropylène et de compatibilisant, leurs proportions étant telles que le rapport de la quantité de polypropylène sur la quantité de compatibilisant est compris entre 1 et 5.In multilayer pipes of various structures, the resistance to cold impact remains unpredictable before having carried out the standard tests of resistance to cold impact. It has been discovered that in a structure comprising the following successive layers: a layer of polyamide or of HDPE (high density polyethylene), a layer of binder, a layer of EVOH, optionally a layer of binder, a layer of polyamide or of mixture polyamide and polyolefin or polyolefin, subjected to shocks or other equivalent mechanical stresses the cracks originated in the EVOH layer and propagated throughout the structure. We also discovered that if we modified the EVOH layer by adding a sufficient amount of a shock modifier then, during a shock, there could still be initiation of cracks in this layer but that it does not there was more than enough energy to propagate the crack (s) in the other layers and therefore the structure was resistant to shocks. Patent EP 1122061 described a structure successively comprising: a first layer of high density polyethylene (HDPE), a layer of binder, a second layer of EVOH or of a mixture based on EVOH, possibly a third layer of polyamide (A) or a mixture of polyamide (A) and polyolefin (B). In this patent, three mixtures based on EVOH are described. The first mixture relates to compositions comprising (by weight): - 55 to 99.5 parts of EVOH copolymer, - 0.5 to 45 parts of polypropylene and compatibilizer, their proportions being such that the ratio of the amount of polypropylene to the amount of compatibilizer is between 1 and 5.
Le deuxième mélange concerne des compositions comprenant : - 50 à 98 % en poids d'un copolymère EVOH - 1 à 50 % en poids d'un polyéthylène -1 à 15 % en poids d'un compatibilisant constitué d'un mélange d'un polyéthylène LLDPE ou metallocène et d'un polymère choisi parmi les élastomères, les polyéthylènes de très basse densité et les polyéthylènes métallocenes, le mélange étant cogreffe par un acide carboxylique insaturé ou un dérivé fonctionnel de cet acide. Le troisième mélange concerne des compositions comprenant : - 50 à 98 % en poids d'un copolymère EVOH - 1 à 50 % en poids d'un copolymère éthylène - (méth)acrylate d'alkyle, - 1 à 15 % en poids d'un compatibilisant résultant de la réaction (i) d'un copolymère de l'éthylène et d'un monomère insaturé X greffé ou copolymérisé avec (ii) un copolyamide. Les brevets EP 1243831, EP 1314758, EP 1314759 et EP 1331091 décrivent des tuyaux multicouches comprenant une couche d'EVOH pouvant être constituée d'un mélange à base d'EVOH identique aux mélanges décrits dans le brevet EP 1122061 cité plus haut. Ces mélanges à base d'EVOH sont insuffisants pour les chocs importants. [Brève description de l'invention]The second mixture relates to compositions comprising: - 50 to 98% by weight of an EVOH copolymer - 1 to 50% by weight of a polyethylene -1 to 15% by weight of a compatibilizer consisting of a mixture of a LLDPE or metallocene polyethylene and a polymer chosen from elastomers, very low density polyethylenes and metallocene polyethylenes, the mixture being cografted by an unsaturated carboxylic acid or a functional derivative of this acid. The third mixture relates to compositions comprising: - 50 to 98% by weight of an EVOH copolymer - 1 to 50% by weight of an ethylene - (meth) acrylate copolymer, - 1 to 15% by weight of a compatibilizer resulting from the reaction (i) of a copolymer of ethylene and of an unsaturated monomer X grafted or copolymerized with (ii) a copolyamide. The patents EP 1243831, EP 1314758, EP 1314759 and EP 1331091 describe multilayer pipes comprising an EVOH layer which may consist of a mixture based on EVOH identical to the mixtures described in patent EP 1122061 cited above. These EVOH-based mixtures are insufficient for large shocks. [Brief description of the invention]
La présente invention concerne une structure multicouche comprenant les couches successives suivantes: une couche de polyamide ou de HDPE (polyéthylène haute densité), une couche de liant, une couche d'EVOH modifié choc, éventuellement une couche de liant, une couche (1 ) de polyamide ou de mélange de polyamide et de polyoléfine ou de polyoléfine, cette dernière couche pouvant contenir des charges pour la rendre antistatique, et telle que la couche d'EVOH modifié choc est un mélange à base d'EVOH et d'au moins un modifiant choc choisi parmi : a) les copolymères éthylène- (méth)acrylate d'alkyle fonctionalisés, b) les produits résultant de la réaction (i) d'un copolymère de Péthylène et d'un monomère insaturé X greffé ou copolymérisé avec (ii) un polyamide, c) les mélanges de a) et b), d) les polyamides, de préférence le PA 6, e) les mélanges de a) et d), f) les élastomères, de préférence les EPR, EPDM et NBR, ces élastomères pouvant être fonctionnalisés, g) les triblocs S-B-M, h) les triblocs constitués d'un bloc en poly(acrylate de butyle) entre deux blocs en PMMA, i) les copolymères à blocs S-B-S linéaires ou en étoile éventuellement hydrogénés (ils sont alors désignés par S-EB-S).The present invention relates to a multilayer structure comprising the following successive layers: a layer of polyamide or of HDPE (high density polyethylene), a layer of binder, a layer of impact modified EVOH, optionally a layer of binder, a layer (1) of polyamide or of mixture of polyamide and of polyolefin or of polyolefin, the latter layer possibly containing fillers to make it antistatic, and such that the layer of shock-modified EVOH is a mixture based on EVOH and at least one impact modifier chosen from: a) functionalized ethylene- (meth) acrylate copolymers, b) products resulting from the reaction (i) of a copolymer of ethylene and of an unsaturated monomer X grafted or copolymerized with (ii ) a polyamide, c) mixtures of a) and b), d) polyamides, preferably PA 6, e) mixtures of a) and d), f) elastomers, preferably EPR, EPDM and NBR , these elastomers being able to be functional alized, g) SBM triblocks, h) triblocks consisting of a poly (butyl acrylate) block between two PMMA blocks, i) copolymers with linear or star SBS blocks, possibly hydrogenated (they are then designated by S -EB-S).
Avantageusement la proportion de modifiant choc est comprise, en poids, entre 1 et 35% pour respectivement 99 à 65% d'EVOH. La présente invention concerne aussi des dispositifs de transfert ou de stockage de fluides et plus particulièrement des tuyaux, des réservoirs, des goulottes, des bouteilles et des conteneurs constitués de la structure ci dessus. Dans ces dispositifs, avantageusement, la couche (1 ) de polyamide ou de mélange de polyamide et de polyoléfine ou de polyoléfine est en contact direct avec le fluide contenu ou transporté. Ces dispositifs peuvent être fabriqués par les techniques habituelles de l'industrie des polymères thermoplastiques telles que la coextrusion et l'extrusion soufflage. Les épaisseurs de ces dispositifs ont été décrits dans l'art antérieur. Selon une autre forme de l'invention la couche (1) n'est pas antistatique et on ajoute une couche (2) disposée du coté de la couche (1), cette couche (2) contient des charges pour la rendre antistatique. Cette couche (2) peut être constituée comme la couche (1) de polyamide ou de mélange de polyamide et de polyoléfine ou de polyoléfine. Les couches (1) et (2) peuvent être de même nature, par exemple toutes les deux en polyamide ou en mélange de polyamide et de polyoléfine ou en polyoléfine. Elles peuvent aussi être différentes, par exemple l'une est en polyoléfine et l'autre en polyamide ou toute autre combinaison. Éventuellement un liant est disposé entre les couches (1) et (2). Dans cette forme de l'invention ou il existe une couche (1 ) et une couche (2) c'est la couche (2) qui est en contact avec le fluide contenu ou transporté.Advantageously, the proportion of impact modifier is comprised, by weight, between 1 and 35% for respectively 99 to 65% of EVOH. The present invention also relates to devices for transferring or storing fluids and more particularly pipes, tanks, chutes, bottles and containers made up of the above structure. In these devices, advantageously, the layer (1) of polyamide or of mixture of polyamide and of polyolefin or of polyolefin is in direct contact with the fluid contained or transported. These devices can be manufactured by the usual techniques in the thermoplastic polymer industry such as coextrusion and extrusion blow molding. The thicknesses of these devices have been described in the prior art. According to another form of the invention, the layer (1) is not antistatic and a layer (2) is added arranged on the side of the layer (1), this layer (2) contains fillers to make it antistatic. This layer (2) can be constituted like the layer (1) of polyamide or of mixture of polyamide and of polyolefin or of polyolefin. The layers (1) and (2) can be of the same nature, for example both in polyamide or in a mixture of polyamide and polyolefin or in polyolefin. They can also be different, for example one is made of polyolefin and the other is made of polyamide or any other combination. Optionally a binder is placed between layers (1) and (2). In this form of the invention where there is a layer (1) and a layer (2) it is the layer (2) which is in contact with the fluid contained or transported.
[Description détaillée de l'invention][Detailed description of the invention]
S'agissant de a) les fonctions peuvent être un acide , un anhydride d'acide ou un époxyde insaturé. La quantité d'anhydre carboxylique insaturé peut être jusqu'à 15 % en poids du copolymère et la quantité d'éthylène d'au moins 50 % en poids. Par exemple c'est un copolymère de l'éthylène d'un (meth)acrylate d'alkyle et d'un anhydride carboxylique insaturé. De préférence le (meth)acrylate d'alkyle est tel que l'alkyle possède 2 à 10 atomes de carbone.As regards a) the functions can be an acid, an acid anhydride or an unsaturated epoxide. The amount of unsaturated carboxylic anhydride can be up to 15% by weight of the copolymer and the amount of ethylene at least 50% by weight. For example, it is an ethylene copolymer of an alkyl (meth) acrylate and an unsaturated carboxylic anhydride. Preferably the alkyl (meth) acrylate is such that the alkyl has 2 to 10 carbon atoms.
Le (méth)acrylate d'alkyle peut être choisi parmi le methacrylate de méthyle, l'acrylate d'éthyle, l'acrylate de n-butyle, l'acrylate d'isobutyle, l'acrylate de 2- éthylhexyle. Le MFI peut être par exemple entre 0,1 et 50 (g/10 min à 190°C sous 2,16 kg). Par exemple c'est un copolymère de l'éthylène d'un (meth)acrylate d'alkyle et d'un époxyde insaturé. De préférence le (meth)acrylate d'alkyle est tel que l'alkyle possède 2 à 10 atomes de carbone. Le MFI (indice de fluidité à l'état fondu) de (A) peut être par exemple entre 0,1 et 50 (g/10 min à 190°C sous 2,16 kg). Des exemples d'acrylate ou methacrylate d'alkyle utilisables sont notamment le methacrylate de méthyle, l'acrylate d'éthyle, l'acrylate de n-butyle, l'acrylate d'isobutyle, l'acrylate de 2-éthylhexyle. Des exemples d'époxydes insaturés utilisables sont notamment : - les esters et éthers de glycidyle aliphatiques tels que l'allylglycidyléther, le vinylglycidyléther, le maléate et l'itaconate de glycidyle, l'acrylate et le methacrylate de glycidyle, et - les esters et éthers de glycidyle alicycliques tels que le 2-cyclohexène- l-glycidyléther, le cyclohexène-4,5-diglycidylcarboxylate, le cyclohexène-4- glycidyl carboxylate, 5-norbornène-2-méthyl-2-glycidyl carboxylate et endocis- bicyclo(2,2,1 )-5-heptène-2,3-diglycidyl dicarboxylate.The alkyl (meth) acrylate can be chosen from methyl methacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2- acrylate. ethylhexyl. The MFI can for example be between 0.1 and 50 (g / 10 min at 190 ° C. under 2.16 kg). For example, it is an ethylene copolymer of an alkyl (meth) acrylate and an unsaturated epoxide. Preferably the alkyl (meth) acrylate is such that the alkyl has 2 to 10 carbon atoms. The MFI (melt flow index) of (A) can for example be between 0.1 and 50 (g / 10 min at 190 ° C. under 2.16 kg). Examples of alkyl acrylate or methacrylate which can be used are in particular methyl methacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate. Examples of unsaturated epoxides which can be used are in particular: - aliphatic glycidyl esters and ethers such as allyl glycidyl ether, vinyl glycidyl ether, glycidyl itaconate and maleate, glycidyl acrylate and methacrylate, and - esters and alicyclic glycidyl ethers such as 2-cyclohexene-1-glycidylether, 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.
S'agissant de b) c'est par exemple un copolymère greffé à blocs polyamide constitué d'un tronc en polyoléfine et d'au moins un greffon en polyamide dans lequel: les greffons sont attachés au tronc par les restes d'un monomère insaturé (X) ayant une fonction capable de réagir avec un polyamide à extrémité aminé, les restes du monomère insaturé (X) sont fixés sur le tronc par greffage ou copolymérisation depuis sa double liaison. S'agissant du copolymère greffé à blocs polyamides il peut être obtenu par réaction d'un polyamide à extrémité aminé avec les restes d'un monomère insaturé X fixé par greffage ou copolymérisation sur un tronc en polyoléfine. Ce monomère X peut être par exemple un époxyde insaturé ou un anhydride d'acide carboxylique insaturé. L'anhydride d'acide carboxylique insaturé peut être choisi par exemple parmi les anhydrides maléique, itaconique, citraconique, allylsuccinique, cyclohex-4-ène-1 ,2-dicarboxylique, 4 — méthylènecyclohex-4-ène-1 ,2-dicarboxylique, bicyclo(2,2,1 )hept-5-ène-2,3- dicarboxylique, et x— méthylbicyclo(2,2,1)hept-5-ène-2,2-dicarboxylique. On utilise avantageusement l'anhydride maleique. On ne sortirait pas du cadre de l'invention en remplaçant tout ou partie de l'anhydride par un acide carboxylique insaturé tel que par exemple l'acide (meth)acrylique. Des exemples d'époxydes insaturés ont été cités plus haut. S'agissant du tronc en polyoléfine, on définit une polyoléfine comme un homo polymère ou copolymère d'alpha oléfines ou de dioléfines, telles que par exemple, éthylène, propylène, butène-1 , octène-1 , butadiène. S'agissant des copolymères de l'éthylène et de X c'est-à-dire ceux dans lesquels X n'est pas greffé il s'agit des copolymères de l'éthylène, de X et éventuellement d'un autre monomère. On utilise avantageusement les copolymères éthylène-anhydride maleique et éthylène - (méth)acrylate d'alkyle - anhydride maleique. Ces copolymères comprennent de 0,2 à 10 % en poids d'anhydride maleique, de 0 à 40 % et de préférence 5 à 40 % en poids de (méth)acrylate d'alkyle. Leur MFI est compris entre 5 et 100 (190°C - 2,16 kg). Les (méth)acrylates d'alkyle ont déjà été décrits plus haut. La température de fusion est comprise entre 60 et 100 °C . S'agissant du polyamide à extrémité aminé on entend par polyamide les produits de condensation : - d'un ou plusieurs aminoacides, tels les acides aminocaproïques, amino- 7-heptanoïque, amino-11-undécanoïque et amino-12-dodécanoïque d'un ou plusieurs lactames tels que le caprolactame, oenantholactame et lauryllactame; - d'un ou plusieurs sels ou mélanges de diamines telles l'hexaméthylène- diamine, la dodécaméthylènediamine, la métaxylylènediamine, le bis-p aminocyclohexylméthane et la triméthylhexaméthylène diamine avec des diacides tels que les acides isophtalique, téréphtalique, adipique, azélaïque, subérique, sébacique et dodécanedicarboxylique : - ou des mélanges de plusieurs monomères ce qui conduit à des copolyamides. On peut utiliser des mélanges de polyamides ou des copolyamides. On utilise avantageusement le PA 6, le PA 11 , le PA 12, le copolyamide à motifs 6 et motifs 11 (PA 6/11), le copolyamide à motifs 6 et motifs 12 (PA 6/12), et le copolyamide à base de caprolactame, hexaméthylènediamine et acide adipique (PA 6/6-6). L'avantage des copolyamides est qu'on peut ainsi choisir la température de fusion des greffons. Avantageusement les greffons sont des homopolymères constitués de restes de caprolactame, d'acide amino-11-undecanoïque ou de dodecalactame ou des copolyamides constitués de restes choisis parmi au moins deux des trois monomères précédents. Le degré de polymérisation peut varier dans de larges proportions, selon sa valeur c'est un polyamide ou un oligomère de polyamide. Dans la suite du texte on utilisera indifféremment les deux expressions pour les greffons. Pour que le polyamide ait une terminaison monoamine il suffit d'utiliser un limiteur de chaîne de formule R1 —N H R 2 dans laquelle :As regards b) it is for example a graft copolymer with polyamide blocks consisting of a polyolefin trunk and at least one polyamide graft in which: the grafts are attached to the trunk by the remains of an unsaturated monomer (X) having a function capable of reacting with an amino-terminated polyamide, the residues of the unsaturated monomer (X) are fixed to the trunk by grafting or copolymerization from its double bond. As regards the graft copolymer with polyamide blocks, it can be obtained by reaction of an amino-terminated polyamide with the remains of an unsaturated monomer X fixed by grafting or copolymerization on a polyolefin backbone. This monomer X can for example be an unsaturated epoxide or an unsaturated carboxylic acid anhydride. The unsaturated carboxylic acid anhydride can be chosen, for example, from maleic anhydrides, itaconic, citraconic, allylsuccinic, cyclohex-4-ene-1, 2-dicarboxylic, 4 - methylene cyclohex-4-ene 1, 2-dicarboxylic, bicyclo (2,2,1) hept-5-ene 2,3- dicarboxylic, and x— methylbicyclo (2,2,1) hept-5-ene-2,2-dicarboxylic. Maleic anhydride is advantageously used. It would not be departing from the scope of the invention to replace all or part of the anhydride with an unsaturated carboxylic acid such as for example (meth) acrylic acid. Examples of unsaturated epoxides have been cited above. As regards the polyolefin backbone, a polyolefin is defined as a homopolymer or copolymer of alpha olefins or of diolefins, such as, for example, ethylene, propylene, butene-1, octene-1, butadiene. As regards the copolymers of ethylene and of X, that is to say those in which X is not grafted, these are copolymers of ethylene, of X and optionally of another monomer. Advantageously, the ethylene-maleic anhydride and ethylene - (meth) acrylate - maleic anhydride copolymers are used. These copolymers comprise from 0.2 to 10% by weight of maleic anhydride, from 0 to 40% and preferably 5 to 40% by weight of alkyl (meth) acrylate. Their MFI is between 5 and 100 (190 ° C - 2.16 kg). The alkyl (meth) acrylates have already been described above. The melting temperature is between 60 and 100 ° C. As regards the amino-terminated polyamide, the term polyamide means the condensation products: of one or more amino acids, such as aminocaproic, amino-7-heptanoic, amino-11-undecanoic and amino-12-dodecanoic acids or several lactams such as caprolactam, oenantholactam and lauryllactam; - one or more diamine salts or mixtures such as hexamethylene diamine, dodecamethylenediamine, metaxylylenediamine, bis-p aminocyclohexylmethane and trimethylhexamethylene diamine with diacids such as isophthalic, terephthalic, adipic, azelaic, sebacic and dodecanedicarboxylic: - or mixtures of several monomers which leads to copolyamides. Mixtures of polyamides or copolyamides can be used. PA 6, PA 11, PA 12, copolyamide with patterns 6 and patterns 11 (PA 6/11), copolyamide with patterns 6 and patterns 12 (PA 6/12), and copolyamide based are advantageously used. of caprolactam, hexamethylenediamine and adipic acid (PA 6 / 6-6). The advantage of copolyamides is that one can thus choose the melting point of the grafts. Advantageously, the grafts are homopolymers consisting of residues of caprolactam, amino-11-undecanoic acid or dodecalactam or copolyamides consisting of residues chosen from at least two of the three preceding monomers. The degree of polymerization can vary within wide proportions, depending on its value it is a polyamide or a polyamide oligomer. In the rest of the text, the two expressions will be used interchangeably for the plugins. For the polyamide to have a monoamine termination, it suffices to use a chain limiter of formula R 1 —NHR 2 in which:
R-| est l'hydrogène ou un groupement alkyle linéaire ou ramifié contenant jusqu'à 20 atomes de carbone,R | is hydrogen or a linear or branched alkyl group containing up to 20 carbon atoms,
R2 est un groupement ayant jusqu'à 20 atomes de carbone alkyle ou alcenyle linéraire ou ramifié, un radical cycloaliphatique saturé ou non, un radical aromatique ou une combinaison des précédents. Le limiteur peut être par exemple la laurylamine ou l'oleylamine. Avantageusement le polyamide à extrémité aminé a une masse molaire comprise entre 1000 et 5000 g/mole et de préférence entre 2000 et 4000. Les monomères amino-acides ou lactames préférés pour la synthèse de l'oligomère monoaminé selon l'invention sont choisis parmi le caprolactame, l'acide amino-11-undécanoïque ou le dodecalactame. Les limitateurs monofonctionnels de polymérisation préférés sont la laurylamine et l'oleylamine. La polycondensation définie ci-dessus s'effectue selon les procédés habituellement connus, par exemple à une température comprise en général entre 200 et 300 °C, sous vide ou sous atmosphère inerte, avec agitation du mélange réactionnel. La longueur de chaîne moyenne de l'oligomère est déterminée par le rapport molaire initial entre le monomère polycondensable ou le lactame et le limitateur monofonctionnel de polymérisation. Pour le calcul de la longueur de chaîne moyenne, on compte habituellement une molécule de limitateur de chaîne pour une chaîne d'oligomère. L'addition de l'oligomère monoaminé de polyamide sur le tronc de polyoléfine contenant X s'effectue par réaction d'une fonction aminé de l'oligomère avec X. Avantageusement X porte une fonction anhydride ou acide, on crée ainsi des liaisons amides ou imides. On réalise l'addition de l'oligomère à extrémité aminé sur le tronc de polyoléfine contenant X de préférence à l'état fondu. On peut ainsi, dans une extrudeuse, malaxer l'oligomère et le tronc à une température généralement comprise entre 230 et 250 °C. Le temps de séjour moyen de la matière fondue dans l'extrudeuse peut être compris entre 15 secondes et 5 minutes, et de préférence entre 1 et 3 minutes. Le rendement de cette addition est évalué par extraction sélective des oligomères de polyamide libres c'est-à-dire ceux qui n'ont pas réagi pour former le copolymère greffé à blocs polyamides final. La préparation de tels polyamides à extrémité aminé ainsi que leur addition sur un tronc de polyoléfine contenant X est décrite dans les brevets US 3976720, US 3963799, US 5342886 et FR 2291225.R2 is a group having up to 20 linear or branched alkyl or alkenyl carbon atoms, a saturated or unsaturated cycloaliphatic radical, an aromatic radical or a combination of the preceding. The limiter can for example be laurylamine or oleylamine. Advantageously, the polyamide with an amino end has a molar mass of between 1000 and 5000 g / mole and preferably between 2000 and 4000. The amino acid or lactam monomers preferred for the synthesis of the monoamine oligomer according to the invention are chosen from caprolactam, amino-11-undecanoic acid or dodecalactam. Preferred monofunctional polymerization limiters are laurylamine and oleylamine. The polycondensation defined above is carried out according to the usually known methods, for example at a temperature generally understood between 200 and 300 ° C, under vacuum or under an inert atmosphere, with stirring of the reaction mixture. The average chain length of the oligomer is determined by the initial molar ratio between the polycondensable monomer or the lactam and the monofunctional polymerization limiter. For the calculation of the average chain length, there is usually one molecule of chain limiter for an oligomer chain. The addition of the polyamide monoamine oligomer to the polyolefin trunk containing X is carried out by reaction of an amino function of the oligomer with X. Advantageously X carries an anhydride or acid function, thus creating amide bonds or imide. The addition of the amino-terminated oligomer is carried out on the polyolefin trunk containing X, preferably in the molten state. It is thus possible, in an extruder, to knead the oligomer and the trunk at a temperature generally between 230 and 250 ° C. The average residence time of the molten material in the extruder can be between 15 seconds and 5 minutes, and preferably between 1 and 3 minutes. The yield of this addition is evaluated by selective extraction of the free polyamide oligomers, that is to say those which have not reacted to form the graft copolymer with final polyamide blocks. The preparation of such amino-terminated polyamides as well as their addition to a polyolefin trunk containing X is described in patents US 3,976,720, US 3,963,799, US 5,342,886 and FR 2,291,225.
S'agissant des triblocs g) On peut citer les triblocs S-B-M dans lesquels : chaque bloc est relié à l'autre au moyen d'une liaison covalente ou d'une molécule intermédiaire reliée à l'un des blocs par une liaison covalente et à l'autre bloc par une autre liaison covalente, le bloc M est constitué de monomères MMA éventuellement copolymérisés avec d'autres monomères et comprend au moins 50% en poids de methacrylate de méthyle(MMA), le bloc B est incompatible avec l'EVOH et avec le bloc M, le bloc S est incompatible avec le bloc B et le bloc M et sa Tg ou sa température de fusion Tf est supérieure à la Tg de B. S'agissant du tribloc S-B-M M est constitué de monomères de methacrylate de méthyle ou contient au moins 50% en masse de methacrylate de méthyle, de préférence au moins 75% en masse de methacrylate de méthyle. Les autres monomères constituant le bloc M peuvent être des monomères acryliques ou non, être réactifs ou non. A titre d'exemples non limitatif de fonctions réactives on peut citer : les fonctions oxiranes, les fonctions aminés, les fonctions carboxy. Le monomère réactif peut être l'acide (meth)acrylique ou tout autre monomère hydrolysable conduisant à ces acides. Parmi les autres monomères pouvant constituer le bloc M on peut citer à titre d'exemple non limitatif le methacrylate de glycidyle le methacrylate de tertiobutyle. Avantageusement M est constitué de PMMA syndiotactique à au moins 60%. Avantageusement la Tg de B est inférieure à 0°C et de préférence inférieure à - 40°C. Le monomère utilisé pour synthétiser le bloc B élastomérique peut être un diène choisi parmi le butadiène, l'isoprène, le 2,3-diméthyl-1 ,3-butadiène, le 1 ,3-pentadiène, le 2-phényl-1 ,3-butadiène. B est choisi avantageusement parmi les poly(diènes) notamment poly(butadiène), poly(isoprène) et leurs copolymères statistiques, ou encore parmi les poly(diènes) partiellement ou totalement hydrogénés. Parmi les polybutadiènes on utilise avantageusement ceux dont la Tg est la plus faible, par exemple le polybutadiène-1 ,4 de Tg ( vers -90° C) inférieure à celle du polybutadiène-1 ,2. (vers 0° C). Les blocs B peuvent aussi être hydrogénés. On effectue cette hydrogénation selon les techniques habituelles. Le monomère utilisé pour synthétiser le bloc B élastomérique peut être aussi un (meth)acrylate d'alkyle, on obtient les Tg suivantes entre parenthèses suivant le nom de l'acrylate: l'acrylate d'éthyle (-24°C), l'acrylate de butyle, (- 54°C), l'acrylate de 2-éthylhexyle (-85°C), l'acrylate d'hydroxyéthyle (-15°C) et le methacrylate de 2-éthylhexyle (-10°C). On utilise avantageusement l'acrylate de butyle. Les acrylates sont différents de ceux du bloc M pour respecter la condition de B et M incompatibles. De préférence les blocs B sont constitués en majorité de polybutadiène- 1 ,4 . La Tg ou la Tf de S est avantageusement supérieure à 23°C et de préférence supérieure à 50°C. A titre d'exemple de blocs S on peut citer ceux qui dérivent de composés vinylaromatiques tels que par exemple le styrène, l'α- méthyl styrène, le vinyltoluène. Avantageusement le tribloc S-B-M est un polystyrène-polybutadiène- PMMA. Le tribloc S-B-M a une masse molaire moyenne en nombre qui peut être comprise entre 10000 g/mol et 500000 g/mol, de préférence comprise entre 20000 et 200000 g/mol. Le tribloc S-B-M avantageusement a la composition suivante exprimée en fraction massique, le total étant 100% : M : entre 10 et 80% et de préférence entre 15 et 70%. B : entre 2 et 80% et de préférence entre 5 et 70%. S : entre 10 et 88% et de préférence entre 15 et 85%. Les triblocs S-B-M peuvent être en mélange avec des diblocs S-B. S'agissant du dibloc S-B les blocs S et B ont les mêmes propriétés que les blocs S et B du tribloc S-B-M ils sont incompatibles et ils sont constitués des mêmes monomères et éventuellement comonomères que les blocs S et les blocs B du tribloc S-B-M. C'est à dire que les blocs S du dibloc S-B sont constitués de monomères choisis dans la même famille que la famille des monomères disponibles pour les blocs S du tribloc S-B-M. De même les blocs B du dibloc S-B sont constitués de monomères choisis dans la même famille que la famille des monomères disponibles pour les blocs B du tribloc S-B-M. Le dibloc S-B a une masse molaire moyenne en nombre qui peut être comprise entre 10000 g/mol et 500000 g/mol, de préférence comprise entre 20000 et 200000 g/mol. Le dibloc S-B est avantageusement constitué d'une fraction massique en B comprise entre 5 et 95% et de préférence entre 15 et 85%. Le mélange de tribloc S-B-M et de dibloc S-B comprend avantageusement entre 5 et 80% de dibloc S-B pour respectivement de 95 à 20% de tribloc S-B-M. De plus l'avantage de ces compositions est qu'il n'est pas nécessaire de purifier le S-B-M à l'issue de sa synthèse. En effet les S-B-M sont en général préparés à partir des S-B et la réaction conduit souvent à un mélange de S-B et S-B-M qu'on sépare ensuite pour disposer de S-B-M. Ces copolymères triblocs S-B-M peuvent être fabriqués par polymérisation anionique par exemple selon les procédés décrits dans les demandes de brevet EP 524.054 et EP 749.987. Ils peuvent aussi être fabriqués par polymérisation radicalaire contrôlée. Ces copolymères triblocs S-With regard to the triblocks g) Mention may be made of the SBM triblocks in which: each block is linked to the other by means of a covalent bond or to an intermediate molecule linked to one of the blocks by a covalent bond and to the other block by another covalent bond, the block M consists of MMA monomers optionally copolymerized with other monomers and comprises at least 50% by weight of methyl methacrylate (MMA), block B is incompatible with EVOH and with block M, block S is incompatible with block B and block M and its Tg or its melting temperature Tf is higher than the Tg of B. With regard to the triblock SBM M consists of methyl methacrylate monomers or contains at least 50 % by mass of methyl methacrylate, preferably at least 75% by mass of methyl methacrylate. The other monomers constituting the block M can be acrylic monomers or not, be reactive or not. By way of nonlimiting examples of reactive functions, mention may be made of: oxirane functions, amine functions, carboxy functions. The reactive monomer can be (meth) acrylic acid or any other hydrolyzable monomer leading to these acids. Among the other monomers which can constitute the block M, there may be mentioned by way of nonlimiting example glycidyl methacrylate tertiary butyl methacrylate. Advantageously M consists of at least 60% syndiotactic PMMA. Advantageously, the Tg of B is less than 0 ° C and preferably less than - 40 ° C. The monomer used to synthesize the elastomeric block B can 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), in particular poly (butadiene), poly (isoprene) and their random copolymers, or alternatively from poly (dienes) partially or completely hydrogenated. Among the polybutadienes, those with the lowest Tg are advantageously used, for example polybutadiene-1, 4 of Tg (around -90 ° C.) lower than that of polybutadiene-1, 2. (around 0 ° C). B blocks can also be hydrogenated. This hydrogenation is carried out according to the usual techniques. The monomer used to synthesize the elastomeric block B can also be an alkyl (meth) acrylate, the following Tg are obtained in brackets according to the name of the acrylate: ethyl acrylate (-24 ° C), l butyl acrylate, (-54 ° C), 2-ethylhexyl acrylate (-85 ° C), hydroxyethyl acrylate (-15 ° C) and 2-ethylhexyl methacrylate (-10 ° C ). Advantageously, acrylate is used butyl. The acrylates are different from those of block M to respect the condition of incompatible B and M. Preferably, the blocks B consist mainly of polybutadiene-1, 4. The Tg or Tf of S is advantageously greater than 23 ° C and preferably greater than 50 ° C. Examples of blocks S that may be mentioned are those which derive from vinyl aromatic compounds such as, for example, styrene, α-methyl styrene, vinyltoluene. Advantageously, the SBM triblock is a polystyrene-polybutadiene-PMMA. The SBM triblock has a number-average molar mass which can be between 10,000 g / mol and 500,000 g / mol, preferably between 20,000 and 200,000 g / mol. The SBM triblock advantageously has the following composition expressed as a mass fraction, the total being 100%: M: between 10 and 80% and preferably between 15 and 70%. B: between 2 and 80% and preferably between 5 and 70%. S: between 10 and 88% and preferably between 15 and 85%. SBM triblocks can be mixed with SB diblocs. As regards the SB diblock, the S and B blocks have the same properties as the S and B blocks of the SBM triblock, they are incompatible and they consist of the same monomers and optionally comonomers as the S blocks and B blocks of the SBM triblock. That is to say that the blocks S of the diblock SB consist of monomers chosen from the same family as the family of monomers available for the blocks S of the triblock SBM. Likewise, blocks B of the SB diblock consist of monomers chosen from the same family as the family of monomers available for blocks B of the SBM triblock. The dibloc SB has a number-average molar mass which can be between 10,000 g / mol and 500,000 g / mol, preferably between 20,000 and 200,000 g / mol. The SB diblock advantageously consists of a mass fraction of B of between 5 and 95% and preferably between 15 and 85%. The mixture of triblock SBM and diblock SB advantageously comprises between 5 and 80% of diblock SB for respectively 95 to 20% of triblock SBM. In addition, the advantage of these compositions is that it is not necessary to purify the SBM at the end of its synthesis. Indeed, SBMs are generally prepared from SBs and the reaction often leads to a mixture of SBs and SBMs which are then separated in order to have SBMs. These SBM triblock copolymers can be produced by anionic polymerization, for example according to the methods described in patent applications EP 524,054 and EP 749,987. They can also be produced by controlled radical polymerization. These triblock copolymers S-
B-M sont décrits dans le brevet WO 29772.B-M are described in patent WO 29772.
S'agissant de i) Des triblocs S-B-S sont décrits dans ULLMANN'S encyclopedia of industrial chemistry Vol A 26, pages 655 - 659. A titre d'exemple de triblocs S-B-S on peut citer les linéaires dans lesquels chaque bloc est relié à l'autre au moyen d'une liaison covalente ou d'une molécule intermédiaire reliée à l'un des blocs par une liaison covalente et à l'autre bloc par une autre liaison covalente. Les blocs S et B ont les mêmes propriétés que les blocs S et B du tribloc S-B-M ils sont incompatibles et ils sont constitués des mêmes monomères et éventuellement comonomères que les blocs S et les blocs B du tribloc S-B-M. C'est à dire que les blocs S du tribloc S- B-S sont constitués de monomères choisis dans la même famille que la famille des monomères disponibles pour les blocs S du tribloc S-B-M. De même les blocs B du tribloc S-B-S sont constitués de monomères choisis dans la même famille que la famille des monomères disponibles pour les blocs B du tribloc S- B-M. Les blocs S et B peuvent être identiques ou différents des autres blocs S et B présents dans les autres copolymères blocs. Le tribloc S-B-S linéaire a une masse molaire moyenne en nombre qui peut être comprise entre 10000 g/mol et 500000 g/mol, de préférence comprise entre 20000 et 200000 g/mol. Le tribloc S-B-S est avantageusement constitué d'une fraction massique en B comprise entre 5 et 95% et de préférence entre 15 et 85%. A titre d'autre exemple de triblocs S-B-S on peut citer ceux en étoile. Le terme "tribloc" n'est pas en accord avec le nombre de blocs mais le terme "triblocs S-B-S en étoile" est clair pour l'homme de métier. A titre d'exemple de triblocs en étoile on peut citer ceux de formule :With regard to i) SBS triblocks are described in ULLMANN'S encyclopedia of industrial chemistry Vol A 26, pages 655 - 659. As an example of SBS triblocks, mention may be made of the linear lines in which each block is connected to the other at by means of a covalent bond or of an intermediate molecule linked to one of the blocks by a covalent bond and to the other block by another covalent bond. The S and B blocks have the same properties as the S and B blocks of the SBM triblock, they are incompatible and they consist of the same monomers and possibly comonomers as the S blocks and the B blocks of the SBM triblock. That is to say that the blocks S of the triblock S-BS consist of monomers chosen from the same family as the family of monomers available for the blocks S of the triblock SBM. Likewise, the blocks B of the SBS triblock consist of monomers chosen from the same family as the family of monomers available for the blocks B of the S-BM triblock. The blocks S and B can be identical or different from the other blocks S and B present in the other block copolymers. The linear SBS triblock has a number-average molar mass which can be between 10,000 g / mol and 500,000 g / mol, preferably between 20,000 and 200,000 g / mol. The SBS triblock is advantageously made up of a mass fraction in B of between 5 and 95% and preferably between 15 and 85%. As another example of SBS triblocks one can cite those in star. The term "triblock" does not agree with the number of blocks but the term "star SBS triblocks" is clear to those skilled in the art. Examples of star triblocks include those of formula:
dans laquelle n vaut 1 , 2 ou 3 et S-| et B-] représentent des blocs. Les blocswhere n is 1, 2 or 3 and S- | and B-] represent blocks. Blocks
S-i représentent du styrène polymérisé et les blocs B-] du butadiène polymérisé, de l'isoprène polymérisé ou un mélange de butadiène et d'isoprène polymérisé. Les blocs B-| peuvent être hydrogénés (il s'agit alors par exemple des S-EB-S).S-i represent polymerized styrene and blocks B-] of polymerized butadiene, polymerized isoprene or a mixture of butadiene and polymerized isoprene. The blocks B- | can be hydrogenated (in this case, for example, S-EB-S).
Y est une entité polyfonctionnelle provenant par exemple d'agents de couplage polyfonctionnels qu'on utilise dans la fabrication des copolymères blocs en étoile. De tels agents ainsi que ces copolymères blocs sont décrits dans USY is a polyfunctional entity originating for example from polyfunctional coupling agents which are used in the manufacture of star block copolymers. Such agents as well as these block copolymers are described in US
3639521. Des copolymères blocs en étoile préférés contiennent 15 à3639521. Preferred star block copolymers contain 15 to
45 % en poids et mieux 25 à 35 % de motifs styrène. La masse molaire est d'au moins 140 000 et mieux d'au moins 160 000. Des polymères blocs en étoile particulièrement préférés sont ceux décrits dans EP 451920. Ces copolymères sont à base de styrène et d'isoprène, la masse molaire des blocs polystyrène est d'au moins 12000 et la teneur en polystyrène est de 35 % (poids) au plus de la masse totale du copolymère bloc. Les copolymères blocs linéaires préférés ont une masse molaire entre 70000 et45% by weight and better 25 to 35% of styrene units. The molar mass is at least 140,000 and better still at least 160,000. Particularly preferred star block polymers are those described in EP 451920. These copolymers are based on styrene and isoprene, the molar mass of the blocks polystyrene is at least 12,000 and the polystyrene content is 35% (weight) at most of the total mass of the block copolymer. Preferred linear block copolymers have a molecular weight between 70,000 and
145000 et contiennent 12 à 35 % en poids de polystyrène. Des copolymères blocs linéaires blocs particulièrement préférés sont ceux à base de styrène et d'isoprène décrits dans le brevet européen145,000 and contain 12 to 35% by weight of polystyrene. Copolymers linear blocks particularly preferred blocks are those based on styrene and isoprene described in the European patent
EP 451919. Ces copolymères ont des blocs polystyrène de masse molaire entre 14000 et 16000 et une teneur en polystyrène comprise entre 25 et 35 % en poids du copolymère bloc. La masse molaire est entre 80000 et 145000 et mieux entre 100000 et 145000. On peut aussi utiliser un mélange de triblocs S-B-S linéaires et de triblocs S-B-S en étoile. Ces triblocs S-B-S linéaires ou en étoile sont disponibles dans le commerce sous les marques Finaprène®, Finaclear®, Kraton® et Styrolux®.EP 451919. These copolymers have polystyrene blocks with a molar mass between 14,000 and 16,000 and a polystyrene content of between 25 and 35% by weight of the block copolymer. The molar mass is between 80,000 and 145,000 and better between 100,000 and 145,000. It is also possible to use a mixture of linear S-B-S triblocks and star S-B-S triblocks. These linear or star S-B-S triblocks are commercially available under the brands Finaprène®, Finaclear®, Kraton® and Styrolux®.
S'agissant de la couche de polyamide ou de HDPE plus précisément le polyamide peut être choisi parmi les PA semi-aromatiques ou semi- cycloaliphatiques et les polyamides aliphatiques. Les polyamides aliphatiques peuvent être choisis parmi le PA 11 , le PAAs regards the polyamide or HDPE layer more specifically, the polyamide can be chosen from semi-aromatic or semi-cycloaliphatic PAs and aliphatic polyamides. The aliphatic polyamides can be chosen from PA 11, PA
12, les polyamides aliphatiques résultant de la condensation d'une diamine aliphatique ayant de 6 à 12 atomes de carbone et d'un diacide aliphatique ayant de 9 à 12 atomes de carbone et les copolyamides 11/12 ayant soit plus de 90% de motifs 11 soit plus de 90% de motifs 12. A titre d'exemple de polyamides aliphatiques résultant de la condensation d'une diamine aliphatique ayant de 6 à 12 atomes de carbone et d'un diacide aliphatique ayant de 9 à 12 atomes de carbone on peut citer : le PA 6-12 résultant de la condensation de l'hexaméthylène diamine et de l'acide 1 ,12-dodecanedioïque, le PA 9-12 résultant de la condensation de la diamine en C9 et de l'acide 1 ,12- dodecanedioïque, le PA 10-10 résultant de la condensation de la diamine en C10 et de l'acide 1 ,10-decanedioïque, le PA 10-12 résultant de la condensation de la diamine en C9 et de l'acide 1 ,12- dodecanedioïque. Quant aux copolyamides 11/12 ayant soit plus de 90% de motifs 11 soit plus de 90% de motifs 12, ils résultent de la condensation de l'acide amino 1-undecanoïque avec le lauryllactame (ou l'alpha oméga amino acide en C12). Dans ce polyamide on peut ajouter aussi des copolymères à blocs polyamides et blocs polyéthers et/ou des plastifiants.12, the aliphatic polyamides resulting from the condensation of an aliphatic diamine having from 6 to 12 carbon atoms and from an aliphatic diacid having from 9 to 12 carbon atoms and the copolyamides 11/12 having either more than 90% of units 11 or more than 90% of units 12. As an example of aliphatic polyamides resulting from the condensation of an aliphatic diamine having 6 to 12 carbon atoms and an aliphatic diacid having 9 to 12 carbon atoms, may include: PA 6-12 resulting from the condensation of hexamethylene diamine and 1,12-dodecanedioic acid, PA 9-12 resulting from the condensation of C9 diamine and acid 1,12 - dodecanedioic, PA 10-10 resulting from the condensation of diamine in C10 and of acid 1, 10-decanedioic, PA 10-12 resulting from the condensation of diamine in C9 and of acid 1, 12 - dodecanedioic. As for copolyamides 11/12 having either more than 90% of units 11 or more than 90% of units 12, they result from the condensation of amino 1-undecanoic acid with lauryllactam (or alpha omega amino acid C12 ). In this polyamide, it is also possible to add copolymers with polyamide blocks and polyether blocks and / or plasticizers.
S'agissant de la couche (1) et de la couche (2) le polyamide et le polyamide du mélange de polyamide et de polyoléfine peuvent être choisis parmi les polyamides cités plus haut mais aussi parmi le PA6, le PA 6-6 ou le PA 6/6-6. With regard to layer (1) and layer (2), the polyamide and the polyamide of the mixture of polyamide and of polyolefin can be chosen from the polyamides mentioned above but also from PA6, PA 6-6 or PA 6 / 6-6.

Claims

Revendicationsclaims
1 Structure multicouche comprenant les couches successives suivantes: • une couche de polyamide ou de HDPE (polyéthylène haute densité), • une couche de liant, • une couche d'EVOH modifié choc, • éventuellement une couche de liant, • une couche (1) de polyamide ou de mélange de polyamide et de polyoléfine ou de polyoléfine, cette dernière couche pouvant contenir des charges pour la rendre antistatique, et telle que la couche d'EVOH modifié choc est un mélange à base d'EVOH et d'au moins un modifiant choc choisi parmi : a) les copolymères éthylène- (méth)acrylate d'alkyle fonctionalisés, b) les produits résultant de la réaction (i) d'un copolymère de l'éthylène et d'un monomère insaturé X greffé ou copolymérisé avec (ii) un polyamide, c) les mélanges de a) et b), d) les polyamides, de préférence le PA 6, e) les mélanges de a) et d), f) les élastomères, de préférence les EPR, EPDM et NBR, ces élastomères pouvant être fonctionnalisés, g) les triblocs S-B-M, h) les triblocs constitués d'un bloc en poly(acrylate de butyle) entre deux blocs en PMMA, i) les copolymères à blocs S-B-S linéaires ou en étoile éventuellement hydrogénés (ils sont alors désignés par S-EB-S).1 Multilayer structure comprising the following successive layers: • a layer of polyamide or HDPE (high density polyethylene), • a layer of binder, • a layer of impact-modified EVOH, • possibly a layer of binder, • a layer (1 ) of polyamide or of mixture of polyamide and of polyolefin or of polyolefin, the latter layer possibly containing fillers to make it antistatic, and such that the layer of shock-modified EVOH is a mixture based on EVOH and at least an impact modifier chosen from: a) ethylene-functionalized alkyl (meth) acrylate copolymers, b) the products resulting from the reaction (i) of a copolymer of ethylene and of an unsaturated monomer X grafted or copolymerized with (ii) a polyamide, c) mixtures of a) and b), d) polyamides, preferably PA 6, e) mixtures of a) and d), f) elastomers, preferably EPR, EPDM and NBR, these elastomers being able to be functionalized, g) the s SBM triblocks, h) triblocks consisting of a poly (butyl acrylate) block between two PMMA blocks, i) linear or star SBS block copolymers, possibly hydrogenated (they are then designated by S-EB-S ).
2 Structure selon la revendication 1 dans laquelle la proportion de modifiant choc est comprise, en poids, entre 1 et 35% pour respectivement 99 à 65% d'EVOH. 3 Structure selon la revendication 1 ou 2 dans laquelle la couche (1 ) est en contact avec le fluide contenu ou transporté.2 Structure according to claim 1 in which the proportion of impact modifier is comprised, by weight, between 1 and 35% for respectively 99 to 65% of EVOH. 3 Structure according to claim 1 or 2 wherein the layer (1) is in contact with the fluid contained or transported.
4 Structure selon l'une quelconque des revendications 1 à 3 dans laquelle la couche (1 ) n'est pas antistatique et on ajoute une couche (2) disposée du coté de la couche (1 ), cette couche (2) contenant des charges pour la rendre antistatique.4 Structure according to any one of claims 1 to 3 wherein the layer (1) is not antistatic and a layer (2) is added disposed on the side of the layer (1), this layer (2) containing fillers to make it antistatic.
5 Structure selon la revendication 4 dans laquelle la couche (2) est constituée de polyamide ou de mélange de polyamide et de polyoléfine ou de polyoléfine.5 Structure according to claim 4 wherein the layer (2) consists of polyamide or mixture of polyamide and polyolefin or polyolefin.
6 Structure selon la revendication 4 ou 5 dans laquelle une couche de liant est disposée entre les couches (1 ) et (2).6 Structure according to claim 4 or 5 wherein a binder layer is disposed between the layers (1) and (2).
7 Structure selon l'une quelconque des revendications 4 à 6 dans laquelle la couche (2) est en contact avec le fluide contenu ou transporté.7 Structure according to any one of claims 4 to 6 wherein the layer (2) is in contact with the fluid contained or transported.
8 Dispositifs de transfert ou de stockage de fluides et plus particulièrement des tuyaux, des réservoirs, des goulottes, des bouteilles et des conteneurs constitués de la structure selon l'une quelconque des revendications précédentes. 8 Devices for transferring or storing fluids and more particularly pipes, reservoirs, chutes, bottles and containers made up of the structure according to any one of the preceding claims.
EP04786248A 2003-08-05 2004-08-02 Multilayer structure comprising a modified impact evoh layer Withdrawn EP1651437A2 (en)

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CN1845821A (en) 2006-10-11
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BRPI0413274A (en) 2006-10-10
US20050058845A1 (en) 2005-03-17

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