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—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
• • 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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