EP4363191A1

EP4363191A1 - Blow molding compositions based on branched polyamides and uses thereof

Info

Publication number: EP4363191A1
Application number: EP22743850.4A
Authority: EP
Inventors: Thomas PRENVEILLE; Marjorie MARCOURT; Bertrand VERBAUWHEDE; Regis Cipriani
Original assignee: Arkema France SA
Current assignee: Arkema France SA
Priority date: 2021-06-28
Filing date: 2022-06-24
Publication date: 2024-05-08
Also published as: FR3124516A1; MX2023014617A; CA3221469A1; CN117580700A; WO2023275463A1; JP2024524894A; KR20240026512A

Abstract

The present invention relates to a blow-molding or extrusion composition, especially for blow molding, the composition comprising by weight: (a) from 88 to 99.95%, especially from 89 to 99.9%, more especially from 93 to 99.9% of at least one semi-crystalline aliphatic polyamide having a carbon number per nitrogen atom greater than or equal to 7, especially greater than or equal to 8; (b) from 0.05% to 10%, especially from 0.1 to 9%, more especially from 0.1 to 5% by weight of at least one branching agent selected from among the polyepoxies, polyanhydrides and polyisocyanates, especially the maleic polyanhydrides and the polyepoxies; (c) from 0 to 2%, especially from 0.1 to 2% of at least one additive; the composition having, after compounding, a melt viscosity from 10,000 to 300,000 Pa·s, preferably from 15,000 to 220,000 Pa·s, as measured in plane-to-plane geometry according to the standard ISO 6721-10:2015 at a temperature of 250°C, a frequency of 0.292 rad/s and a deformation of 2%, the sum of the components (a) + (b) + (c) being 100% by weight.

Description

DESCRIPTION

TITLE: BLOW MOLDING COMPOSITIONS BASED ON BRANCHED POLYAMIDES AND THEIR

USES

[Technical area]

The present invention relates to blow molding or extrusion compositions, in particular blow molding compositions, based on branched polyamide and their use for the preparation of single-layer or multi-layer tubular structures intended for the transport, distribution or storage of hydrogen and the process for preparing said structures.

[Prior art]

One of the aims sought in the automobile field is to offer less and less polluting vehicles. Thus, electric or hybrid vehicles comprising a battery aim to gradually replace thermal vehicles, such as gasoline or diesel vehicles. However, it turns out that the battery is a relatively complex constituent of the vehicle. Depending on where the battery is located in the vehicle, it may need to be protected from impact and the external environment, which may be extreme temperatures and varying humidity. It is also necessary to avoid any risk of flames.

In addition, it is important that its operating temperature does not exceed 55°C so as not to damage the cells of the battery and preserve its lifespan. Conversely, for example in winter, it may be necessary to raise the temperature of the battery so as to optimize its operation.

Moreover, the electric vehicle still suffers today from several problems, namely battery autonomy, the use in these batteries of rare earths whose resources are not inexhaustible, as well as a problem of electricity production in different countries to be able to recharge the batteries.

Hydrogen therefore represents an alternative to the electric battery since hydrogen can be transformed into electricity by means of a fuel cell and thus power electric vehicles.

Nevertheless, the storage of hydrogen is technically difficult and costly due to its very low molar mass and its very low liquefaction temperature, especially when it comes to mobile storage. However, to be effective, storage must be carried out in small volumes, which requires maintaining the hydrogen under high pressure, given the temperatures at which the vehicles are used. This is the case, in particular, of fuel cell hybrid road vehicles for which the aim is to have a range of the order of 600 to 700 km, or even less for essentially urban uses in addition to an electric base on batteries. Hydrogen tanks generally consist of a metal envelope (liner) which must prevent the permeation of hydrogen. This first casing must itself be protected by a second casing (in general made of composite materials) intended to withstand the internal pressure of the reservoir (for example, 700 bars) and resistant to possible shocks or sources of heat. The valve system must also be safe.

Application EP 0495363 relates to polyamide compositions based on a polyamide alloy (PA) and special olefin-acid anhydride copolymers and their use for the production of shaped hollow bodies.

However, the exemplified compositions are too fluid to allow large reservoirs to be extruded.

These structures are also based on polyamide 6 (PA 6) (poor resistance to zinc chloride and fragile when cold) and are therefore not compatible with reservoir applications for automotive fluids such as hydrogen.

International application WO20027031 relates to a composition based on polyamide 6 (PA6), impact modifier and metal halide.

As above, these structures are based on PA 6 (poor resistance to zinc chloride and fragile when cold) and therefore are not compatible with reservoir applications for automotive fluids such as hydrogen.

Application FR2996556 relates to a liner for the storage of gas, in particular compressed natural gas (CNG), methane or hydrogen comprising a composition based on branched polyamide and impact modifier.

The compositions exemplified are based on PA6 and therefore present the same problems as above. In addition, the compositions contain too much impact modifier, which creates a risk of cavitation (blistering).

Application CA3101967 relates to polyamide compositions for blow molding based on PA 6 and impact modifier and consequently they present the same problems as above.

Application EP1352934 describes metal surfaces coated with a layer based on polyamide consisting of a mixture of polyamide and of a polyolefin functionalized with an unsaturated carboxylic acid anhydride.

Application US2005/228145 describes a transparent multilayer structure comprising a first layer of polyamide consisting of a mixture of polyamide and of a polyolefin functionalized with maleic anhydride.

Application FR3078132 describes a flexible tubular structure comprising a layer comprising a mixture of polyamide and of a polyolefin functionalized with an anhydride. Application EP2649130 describes a liner for storing gas comprising a composition comprising a mixture of polyamide and of a polyolefin functionalized with an anhydride.

It is therefore necessary to provide compositions that overcome the problems presented above and the present invention therefore relates to a composition for blow molding or extrusion, in particular blow molding, comprising by weight: a) from 88 to 99.95% , in particular from 89 to 99.9%, in particular from 93 to 99.9% of at least one semi-crystalline aliphatic polyamide having a number of carbon per nitrogen atom greater than or equal to 7, in particular greater than or equal to 8, b) from 0.05% to 10%, in particular from 0.1 to 9%, in particular from 0.1 to 5% by weight of at least one branching agent chosen from polyepoxy, polyanhydrides and polyisocyanates, in particular maleic polyanhydrides and polyepoxy, c) from 0 to 2% of at least one additive, in particular from 0.1 to 2%, the composition exhibiting after compounding a melt viscosity of between 10,000 at 300,000 Pa.s, preferably from 15,000 to 220,000 Pa.s, as measured in plane-plane geometry according to standard 6721-10:201 5 at a temperature of 250° C., a frequency of 0.292 rad/s and a deformation of 2%, the sum of the constituents a)+b)+c) being 100% by weight.

The inventors have therefore unexpectedly found that the use of particular semi-crystalline aliphatic polyamides with a particular range of branching agent and the presence or absence of additives makes it possible to obtain compositions which, after compounding, have a viscosity at molten state in a range allowing extrusion-blow molding or extrusion, in particular extrusion-blow molding for the constitution of a monolayer or multilayer tubular structure intended for the transport, distribution or storage of hydrogen.

Another advantage of the compositions of the invention is the good dimensional stability, that is to say low water uptake, good resistance to zinc chloride.

By "monolayer or multilayer tubular structure" is meant a reservoir comprising or consisting of one or more layers.

The monolayer or multilayer structure in the present invention also designates a pipe or a tube intended for transporting hydrogen to the tank or from the tank to the fuel cell and which comprises or consists of one or more layers.

In one embodiment, non-functionalized impact modifiers are excluded from said composition.

In another embodiment, non-functionalized impact modifiers and low-functionalized impact modifiers are excluded from said composition. By low-functionalized impact modifier, is meant an impact modifier having an equivalent weight per reactive function greater than 10,000 g/mol, advantageously greater than 6000 g/mol.

In yet another embodiment, functionalized or non-functionalized impact modifiers are excluded from said composition.

In yet another embodiment, non-functionalized elastomers are excluded from said composition.

In yet another embodiment, plasticizers are excluded from said composition.

Regarding the optionally excluded impact modifier

By the expression “impact modifier”, is meant a polymer with a modulus lower than that of the resin, exhibiting good adhesion with the matrix, so as to dissipate the cracking energy.

The impact modifier is advantageously made up of a polymer having a flexural modulus of less than 100 MPa measured according to the ISO 178 standard and a Tg of less than 0° C. (measured according to the 11357-2 standard at the level of the inflection point of the DSC thermogram ), in particular a polyolefin.

The polyolefin of the impact modifier can be functionalized or non-functionalized or be a mixture of at least one functionalized and/or at least one non-functionalized. For simplicity, the polyolefin has been designated by (B) and functionalized polyolefins (B1) and non-functionalized polyolefins (B2) have been described below.

A non-functionalized polyolefin (B2) is conventionally a homopolymer or copolymer of alpha olefins or diolefins, such as, for example, ethylene, propylene, butene-1, octene-1, butadiene. By way of example, we can cite:

- homopolymers and copolymers of polyethylene, in particular LDPE, HDPE, LLDPE (linear low density polyethylene, or linear low density polyethylene), VLDPE (very low density polyethylene, or very low density polyethylene) and metallocene polyethylene.

-the homopolymers or copolymers of propylene.

- ethylene/alpha-olefin copolymers such as ethylene/propylene, EPR (abbreviation of ethylene-propylene-rubber) and ethylene/propylene/diene (EPDM).

- styrene/ethylene-butene/styrene (SEBS), styrene/butadiene/styrene (SBS), styrene/isoprene/styrene (SIS), styrene/ethylene-propylene/styrene (SEPS) block copolymers.

- copolymers of ethylene with at least one product chosen from salts or esters of unsaturated carboxylic acids such as alkyl (meth)acrylate (for example methyl acrylate), or vinyl esters of carboxylic acids saturated such as vinyl acetate (EVA), the proportion of comonomer possibly reaching 40% by weight. The functionalized polyolefin (B1) can be a polymer of alpha olefins having reactive units (the functionalities); such reactive units are acid, anhydride or epoxy functions. By way of example, mention may be made of the preceding polyolefins (B2) grafted or co- or ter-polymerized with unsaturated epoxides such as glycidyl (meth)acrylate, or with carboxylic acids or the corresponding salts or esters such as (meth)acrylic acid (the latter possibly being totally or partially neutralized by metals such as Zn, etc.) or else by carboxylic acid anhydrides such as maleic anhydride. A functionalized polyolefin is, for example, a PE/EPR mixture, the weight ratio of which can vary widely, for example from 40/60 to 90/10, said mixture being co-grafted with an anhydride, in particular maleic anhydride, according to a degree of grafting for example from 0.01 to 5% by weight, advantageously from 2.8 to 5% by weight.

The functionalized polyolefin (B1) can be chosen from the following (co)polymers, grafted with maleic anhydride or glycidyl methacrylate, in which the degree of grafting is for example from 0.01 to 5% by weight:

- PE, PP, copolymers of ethylene with propylene, butene, hexene, or octene containing for example from 35 to 80% by weight of ethylene;

- ethylene and vinyl acetate (EVA) copolymers, containing up to 40% by weight of vinyl acetate;

- ethylene and alkyl (meth)acrylate copolymers, containing up to 40% by weight of alkyl (meth)acrylate;

- ethylene and vinyl acetate (EVA) and alkyl (meth)acrylate copolymers, containing up to 40% by weight of comonomers.

The functionalized polyolefin (B1) can also be chosen from ethylene/propylene copolymers with a majority of propylene grafted with maleic anhydride then condensed with monoamine polyamide (or a polyamide oligomer) (products described in EP-A-0342066) .

The functionalized polyolefin (B1) can also be a co- or ter-polymer of at least the following units: (1) ethylene, (2) alkyl (meth)acrylate or saturated carboxylic acid vinyl ester and (3) anhydride such as maleic anhydride or (meth)acrylic acid or epoxy such as glycidyl (meth)acrylate. By way of example of functionalized polyolefins of this last type, mention may be made of the following copolymers, in which the ethylene preferably represents at least 60% by weight and in which the ter monomer (the function) represents, for example, from 0.1 to 13% by weight of the copolymer:

- ethylene/(meth)acrylate/(meth)acrylic acid or maleic anhydride or glycidyl methacrylate copolymers;

- ethylene/vinyl acetate/maleic anhydride or glycidyl methacrylate copolymers;

- ethylene/vinyl acetate or alkyl (meth)acrylate/(meth)acrylic acid or maleic anhydride or glycidyl methacrylate copolymers.

In the above copolymers, the (meth)acrylic acid can be salified with Zn or Li.

The term "alkyl (meth)acrylate" in (B1) or (B2) denotes C1 to C8 alkyl methacrylates and acrylates, and may be chosen from methyl acrylate, ethyl acrylate , n-butyl acrylate, isobutyl acrylate, ethyl-2-hexyl acrylate, cyclohexyl acrylate, methyl methacrylate and ethyl methacrylate.

Furthermore, the aforementioned polyolefins (B1) can also be crosslinked by any appropriate process or agent (diepoxy, diacid, peroxide, etc.); the term functionalized polyolefin also includes mixtures of the aforementioned polyolefins with a difunctional reagent such as diacid, dianhydride, diepoxy, etc. capable of reacting with these or mixtures of at least two functionalized polyolefins capable of reacting with each other.

The copolymers mentioned above, (B1) and (B2), can be randomly or block copolymerized and have a linear or branched structure.

The molecular weight, the MFI index, the density of these polyolefins can also vary to a large extent, which those skilled in the art will appreciate. MFI, short for Melt Flow Index, is the Melt Flow Index. It is measured according to the ASTM 1238 or ISO 1133:2011 standard. Advantageously, the non-functionalized polyolefins (B2) are chosen from polypropylene homopolymers or copolymers and any homopolymer of ethylene or copolymer of ethylene and a comonomer of the higher alpha olefinic type such as butene, hexene, octene or 4-methyl 1-pentene. Mention may be made, for example, of PP, high-density PE, medium-density PE, linear low-density PE, low-density PE, very low-density PE. These polyethylenes are known to those skilled in the art as being produced according to a “radical” process, according to a catalysis of the “Ziegler” type or, more recently, according to a so-called “metallocene” catalysis.

Advantageously, the functionalized polyolefins (B1) are chosen from any polymer comprising alpha olefin units and units carrying polar reactive functions such as epoxy, carboxylic acid or carboxylic acid anhydride functions. As examples of such polymers, mention may be made of the terpolymers of ethylene, of alkyl acrylate and maleic anhydride or glycidyl methacrylate such as Lotader ^® from SK global Chemical or polyolefins grafted with maleic anhydride such as Orevac ^® from SK global Chemical as well as terpolymers of ethylene, acrylate alkyl and (meth)acrylic acid. Mention may also be made of polypropylene homopolymers or copolymers grafted with a carboxylic acid anhydride and then condensed with polyamides or monoamino polyamide oligomers. Regarding the semi-crystalline aliphatic polyamide

The blow molding or extrusion composition, in particular blow molding, comprises from 88 to 99.95%, in particular from 89 to 99.8% of at least one semi-crystalline aliphatic polyamide having a carbon number per nitrogen atom greater than or equal to 7, in particular greater than or equal to 8.

The nomenclature used to define polyamides is described in standard ISO 1874-1:2011 "Plastics - Polyamide (PA) materials for molding and extrusion - Part 1: Designation", in particular on page 3 (tables 1 and 2) and is well known to those skilled in the art.

The polyamide can be a homopolyamide or a copolyamide or a mixture thereof. The expression "semi-crystalline", within the meaning of the invention, denotes a (co)polyamide which has a melting point (Tm) in DSC according to standard ISO 11357-3:2013, and an enthalpy of crystallization during the cooling step at a speed of 20 K/min in DSC measured according to standard ISO 11357-3 of 2013 greater than 20 J/g, preferably greater than 30 J/g.

Said semi-crystalline aliphatic polyamide is derived from a repeating unit obtained by polycondensation: of at least one C9 to C18 amino acid, preferably CIO to C18, more preferably CIO to C12, or at least one C9 lactam to C18, preferentially in CIO to C18, more preferentially in CIO to C12, or of at least one diamine Ca in C4-C36, preferentially C6-C18, preferentially C6-C12, more preferentially C10-C12, with at least one acid C4-C36, preferably C6-C18, preferably C6-C12, more preferably C10-C12 dicarboxylic acid Cb, or a mixture thereof, provided that the number of carbon atoms per nitrogen atom of the repeating unit is greater than or equal to 7, in particular greater than or equal to 8.

A C9 to C18 amino acid is in particular 9-aminononanoic acid, 10-aminodecanoic acid, 10-aminoundecanoic acid, 12-aminododecanoic acid and 11-aminoundecanoic acid as well as its derivatives, in particular acid N-heptyl-ll-aminoundecanoic acid.

A C9 to C18 lactam is in particular lauryllactam. Said at least one C4-C36 diamine Ca can be chosen in particular from 1,4-butanediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine, 1,13-tridecamethylenediamine, 1,14-tetradecamethylenediamine, 1,16-hexadecamethylenediamine and 1, 18-octadecamethylenediamine, octadecenediamine, eicosanediamine, docosanediamine and diamines obtained from fatty acids.

Advantageously, said at least one diamine Ca is C6-C18 and chosen from 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 1,10-decamethylenediamine , 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine, 1,13-tridecamethylenediamine, 1,14-tetradecamethylenediamine, 1,16-hexadecamethylenediamine and 1,18-octadecamethylenediamine.

Said at least one Cb C4 to C36 dicarboxylic acid may be chosen from succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, octadecanediamine, eicosanediamine, docosanediamine and diamines obtained from fatty acids . Advantageously, said at least one Cb dicarboxylic acid is C6 to C18 and is chosen from adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid.

In one embodiment, said semi-crystalline aliphatic polyamide is chosen from PA610, PA612, PA 614, PA 10, PAU and PA12, in particular PA610, PA612 and PAU.

In one embodiment, said semi-crystalline aliphatic polyamide is a mixture of two semi-crystalline aliphatic polyamides having a number of carbon per nitrogen atom greater than or equal to 7, in particular greater than or equal to 8, in a range of proportion by weight of 5/95 to 95/5.

Advantageously, the polyamide has a concentration at the end of the amine chains of 5 to 60 peq/g, very advantageously between 10 and 50 peq/g.

Advantageously, the polyamide has a concentration at the end of the acid chains comprised from 5 to 60 peq/g, very advantageously from 10 to 50 peq/g.

The ends of the amine chains are measured according to the following method: a sample of polyamide is dissolved in metacresol. Then, this sample is assayed by potentiometry with a 0.02N perchloric acid solution. The ends of acid chains are measured according to the following method. A sample of polyamide is dissolved in benzyl alcohol. Then, this sample is assayed by potentiometry with a solution of tetrabutylammonium hydroxide at 0.02N.

In one embodiment, the MFI of said polyamide or of said polyamide blend ranges from 0.01 to 10, advantageously from 0.01 to 5 g/10 min at 235° C., 5 kg.

The polyamide according to the invention has an inherent viscosity in m-cresol greater than 1.45, advantageously greater than 1.55, very advantageously greater than 1.6 as determined according to standard ISO 307:2007 but using m -cresol instead of sulfuric acid, a temperature of 20°C and a concentration of 0.5% by weight.

Regarding the branching agent

The branching agent is present in the composition from 0.05% to 10%, in particular from 0.1 to 9%, in particular from 0.1 to 5% by weight and is chosen from polyepoxy, polyanhydrides, and polyisocyanates in particular maleic polyanhydrides and polyepoxy.

In one embodiment, the branching agent is present in the composition at 0.1 to 2% by weight.

The branching agent may be an impact modifier, in particular a polyolefin functionalized or different from an impact modifier.

Advantageously, it is different from the impact modifier. That is to say, it has a Tg greater than -30°C, very advantageously greater than 0°C.

Advantageously, the equivalent weight per reactive function of the branching agent is comprised from 100 to 10000 g/mol, advantageously from 120 to 6000 g/mol, more advantageously from 140 to 3300 g/mol.

In one embodiment, said branching agent has an average functionality in terms of epoxy, anhydride or isocyanate functions of between 1.8 and 200, preferably between 2.1 and 150.

In yet another embodiment, the molar mass of the branching agents is between 300 and 120,000 g/mol, preferably between 400 and 100,000 g/mol.

The molar mass is measured by gas chromatography (GPC).

The equivalent weight per reactive functions of the branching agents is measured as follows: Isocyanates: The equivalent weight per isocyanate function is measured according to the AFNOR standard referenced NF T52-132.

Epoxides: The equivalent weight per epoxy function is measured according to standard ASTM D1652-11 (2019).

Maleic anhydride: The mass content of maleic anhydride is measured by FTIR using the method of De Roovers et al. [J Polym Sci, Part A: Polym Chem 1995;33:829] The equivalent weight is often given by the supplier on the TDS.

The average functionality is calculated by dividing the molar mass measured by GPC by the average equivalent weight.

The polyepoxy can be copolymers made from glycidyl maleic anhydride (GMA) or any other monomer comprising an epoxy function.

Examples of commercial polyepoxy are, for example, ^Xibond® 920 marketed by Polyscope or ^Joncryl® ADR 4400 marketed by BASF or ^lotader® AX 8900 marketed by SK Chemical.

The polyanhydrides can be copolymers comprising a copolymerized or grafted anhydride, such as maleic anhydride or itaconic anhydride.

In particular, the polyanhydrides are maleic polyanhydrides.

The other monomer of the copolymers comprising a copolymerized anhydride can be a vinyl aromatic monomer, such as styrene or styrenes in which the aromatic ring contains a halogen or an alkyl substituent.

In one embodiment, the other monomer of the copolymers comprising a copolymerized anhydride can be a vinyl monomer, such as ethylene or octadecene.

In particular, maleic polyanhydrides are copolymers of styrene and maleic anhydride.

Examples of commercial maleic polyanhydrides are for example Xibond ^® 125 (copolymer of styrene and maleic anhydride) marketed by Polyscope or Orevac IM 800 marketed by SK Chemicals or PA 18 (copolymer of 1-octadecene and anhydride maleic acid) marketed by Chevron Phillips Chemical Company.

The polyisocyanates are preferably oligomers of isocyanates such as isocyanurates or allophanates.

Examples of commercial polyisocyanates are for example Desmodur 3300 marketed by Covestro.

Regarding the additive

The additives may be present up to 2% by weight relative to the total weight of the composition, in particular they are present from 0.1 to 2% by weight relative to the total weight of the composition. The additive can be chosen from a catalyst, an antioxidant, a heat stabilizer, a UV stabilizer, a light stabilizer, a lubricant, a flame retardant, a nucleating agent, a chain extender and a colorant.

In one embodiment, the additive is selected from catalyst, antioxidant, heat stabilizer, UV stabilizer, light stabilizer, lubricant, flame retardant, chain extender, and colorant. The term “catalyst” denotes a polycondensation catalyst such as an inorganic or organic acid.

Advantageously, the proportion by weight of catalyst is comprised from approximately 50 ppm to approximately 5000 ppm, in particular from approximately 100 to approximately 3300 ppm relative to the total weight of the composition.

Advantageously, the catalyst is chosen from phosphoric acid (H3P04), phosphorous acid (H3P03), hypophosphorous acid (H3P02), or a mixture of these.

The antioxidant can in particular be an antioxidant based on a copper complex of 0.05 to 5% by weight, preferably 0.05 to 1% by weight, preferably 0.1 to 1%.

The expression copper complex denotes in particular a complex between a monovalent or divalent salt of copper with an organic or inorganic acid and an organic ligand. Advantageously, the copper salt is chosen from cupric salts (Cu(II)) of hydrogen halide, cuprous salts (Cu(II)) of hydrogen halide and salts of aliphatic carboxylic acids.

In particular, the copper salts are chosen from CuCl, CuBr, Cul, CuCN, CuCl2, Cu(OAc)2, cupric stearate.

Copper complexes are in particular described in US3505285.

Said copper-based complex may further comprise a ligand chosen from phosphines, in particular triphenylphosphines, mercaptobenzimidazole, EDTA, acetylacetonate, glycine, ethylene diamine, oxalate, diethylene diamine, triethylene tetraamine, pyridine, tetrabromobisphenyl-A, tetrabisphenyl-A derivatives, such as epoxy derivatives, and chloro dimethanedibenzo(a,e)cyclooctene derivatives and mixtures thereof. diphosphone and dipyridyl or their mixtures, in particular triphenylphosphine and/or mercaptobenzimidazole.

Phosphines refer to alkylphosphines, such as tributylphosphine or arylphosphines such as triphenylphosphine (TPP).

Advantageously, said ligand is triphenylphosphine.

Examples of complexes as well as their preparation are described in patent CA 02347258. Advantageously, the amount of copper in the composition of the invention is between 10 ppm to 1000 ppm by weight, especially from 50 to 150 ppm relative to the total weight of the composition.

Advantageously, said copper-based complex further comprises a halogenated organic compound.

The halogenated organic compound can be any halogenated organic compound. Advantageously, said halogenated organic compound is a bromine-based compound and/or an aromatic compound.

Advantageously, said aromatic compound is chosen in particular from decabromediphenyl, decabromodiphenyl ether, bromo or chlorostyrene oligomers and polydibromostyrene. Advantageously, said halogenated organic compound is a bromine-based compound.

Said halogenated organic compound is added to the composition in a proportion of 50 to 30,000 ppm by weight of halogen relative to the total weight of the composition, in particular from 100 to 10,000 in particular from 500 to 1500 ppm.

Advantageously, the copper:halogen molar ratio is comprised from 1:1 to 1:3000, in particular from 1:2 to 1:100.

In particular, said ratio is comprised from 1:1.5 to 1:15.

Advantageously, the copper complex antioxidant.

The thermal stabilizer can be an organic stabilizer or more generally a combination of organic stabilizers, such as a primary antioxidant of the phenol type (for example of the type of that of irganox 245 or 1098 or 1010 from the company Ciba), a secondary antioxidant of phosphite type.

The UV stabilizer can be a HALS, which means Hindered Amine Light Stabilizer or an anti-UV (for example Tinuvin 312 from the company Ciba).

The light stabilizer can be of the hindered amine type (for example Tinuvin 770 from the company Ciba), a phenolic or phosphorus-based stabilizer.

The lubricant can be a fatty acid type lubricant such as stearic acid.

The flame retardant may be a halogen-free flame retardant, as described in US 2008/0274355 and in particular a phosphorus-based flame retardant, for example a metal salt chosen from a metal salt of phosphinic acid, in particular salts dialkyl phosphinate, in particular diethyl phosphinate aluminum salt or diethyl phosphinate aluminum, a metal salt of diphosphinic acid, a mixture of flame retardant agent based on aluminum phosphinate and a nitrogen synergist or a mixture of an aluminum phosphinate-based flame retardant and a phosphorus synergist, a polymer containing at least one metal salt of phosphinic acid, in particular on an ammonium base, such as an ammonium polyphosphate, sulfamate or pentaborate, or on a melamine base such as melamine, melamine salts, melamine pyrophosphates and melamine cyanurates, or on a cyanuric acid base, further a polymer containing at least one metal salt of diphosphinic acid or red phosphorus, antimony oxide, zinc oxide, iron oxide, magnesium oxide or metal borates such as zinc borate, or phosphazenes, phospham or phosphooxynitride or a mixture of these. They can also be halogenated flame retardants such as brominated or polybrominated polystyrene, brominated polycarbonate or brominated phenol.

The nucleating agent can be silica, alumina, clay or talc, in particular talc.

Examples of suitable chain regulators are monoamines, monocarboxylic acids, diamines, triamines, dicarboxylic acids, tricarboxylic acids, tetraamines, tetracarboxylic acids and, oligoamines or oligocarboxylic acids having respectively in each case 5 to 8 amino or carboxy groups and in particular dicarboxylic acids, tricarboxylic acids or a mixture of dicarboxylic acids and tricarboxylic acids. By way of example, it is possible to use dodecanedicarboxylic acid in the form of the dicarboxylic acid and trimellitic acid as the tricarboxylic acid.

Regarding the composition

Throughout the description, all percentages are given by weight.

The blow molding or extrusion composition, in particular blow molding, comprises by weight: a) from 88 to 99.95%, in particular from 89 to 99.9%, in particular from 93 to 99.9% of at least one semi-crystalline aliphatic polyamide having a number of carbon per nitrogen atom greater than or equal to 7, in particular greater than or equal to 8, b) from 0.05% to 10%, in particular from 0.1 to 9%, in particular from 0.1 to 5% by weight of at least one branching agent chosen from polyepoxy, polyanhydrides and polyisocyanates, in particular maleic polyanhydrides and polyepoxy. c) from 0 to 2% of at least one additive, in particular from 0.1 to 2%, the composition having, after compounding, a viscosity in the molten state of between 10,000 and 300,000 Pa.s, preferentially from 15,000 to 220,000 Pa.s, as measured in plane-plane geometry according to ISO 6721-10:2015 at a temperature of 250°C, a frequency of 0.292 rad/s and a deformation of 2%, the sum of the constituents a) + b) + c) making 100% by weight.

In one embodiment, the blow molding or extrusion composition, in particular blow molding, consists by weight of: a) from 88 to 99.95%, in particular from 89 to 99.9%, in particular from 93 to 99.9% of at least one semi-crystalline aliphatic polyamide having a carbon number per nitrogen atom greater than or equal to 7, in particular greater than or equal to 8, b) from 0.05% to 10%, in particular from 0.1 to 9%, especially from 0.1 to 5% by weight of at least one branching agent chosen from polyepoxy, polyanhydrides and polyisocyanates, in particular polymaleic anhydrides and polyepoxy. c) from 0 to 2% of at least one additive, in particular from 0.1 to 2%, the composition having, after compounding, a viscosity in the molten state of between 10,000 and 300,000 Pa.s, preferentially from 15,000 to 220,000 Pa.s, as measured in plane-plane geometry according to ISO 6721-10:2015 at a temperature of 250°C, a frequency of 0.292 rad/s and a deformation of 2%, the sum of the constituents a) + b) + c) making 100% by weight.

In one embodiment, said composition comprises: a) from 88 to 99.95% of at least one semi-crystalline aliphatic polyamide having a number of carbon per nitrogen atom greater than or equal to 7, in particular greater than or equal to 8, b) from 0.05% to 10% by weight of at least one branching agent chosen from polyepoxy, polyanhydrides and polyisocyanates, in particular polymaleic anhydrides and polyepoxy, the composition having, after compounding, a viscosity of the molten state comprised from 10,000 to 300,000 Pa.s, preferably from 15,000 to 220,000 Pa.s, as measured in plane-plane geometry according to standard ISO 6721-10:2015 at a temperature of 250°C, a frequency of 0.292 rad/s and a deformation of 2%, the sum of the constituents a) + b) making 100% by weight.

Advantageously in this embodiment, said composition consists of: a) from 88 to 99.95% of at least one semi-crystalline aliphatic polyamide having a number of carbon per nitrogen atom greater than or equal to 7, in particular greater than or equal to 8, b) from 0.05% to 10% by weight of at least one branching agent chosen from polyepoxy, polyanhydrides and polyisocyanates, in particular polymaleic anhydrides and polyepoxy, the composition having after compounding a melt viscosity of from 10,000 to 300,000 Pa.s, preferably from 15,000 to 220,000 Pa.s, as measured in plane-plane geometry according to standard ISO 6721-10:2015 at a temperature of 250°C, a frequency of 0.292. rad/s and a deformation of 2%, the sum of the constituents a) + b) making 100% by weight.

In another embodiment, said composition comprises: a) from 88 to 99.85% of at least one semi-crystalline aliphatic polyamide having a number of carbon per nitrogen atom greater than or equal to 7, in particular greater than or equal to 8, b) from 0.05% to 10% by weight of at least one branching agent chosen from polyepoxy, polyanhydrides and polyisocyanates, in particular maleic polyanhydrides and polyepoxy c) from 0.1 to 2% of at least one additive, the composition having, after compounding, a viscosity in the molten state of between 10,000 and 300,000 Pa.s, preferably from 15,000 to 220,000 Pa.s, as measured in plane-plane geometry at a temperature of 250° C., a frequency of 0.292 rad/s and a strain of 2%, the sum of the constituents a) + b) + c) making 100% by weight.

Advantageously in this embodiment, said composition consists of: a) from 88 to 99.85% of at least one semi-crystalline aliphatic polyamide having a number of carbon per nitrogen atom greater than or equal to 7, in particular greater than or equal to 8, b) from 0.05% to 10% by weight of at least one branching agent chosen from polyepoxy, polyanhydrides and polyisocyanates, in particular maleic polyanhydrides and polyepoxy, c) from 0, 1 to 2% of at least one additive, the composition exhibiting, after compounding, a viscosity in the molten state of between 10,000 and 300,000 Pa.s, preferably from 15,000 to 220,000 Pa.s, as measured in plane-plane geometry according to ISO 6721-10:2015 at a temperature of 250°C, a frequency of 0.292 rad/s and a deformation of 2%, the sum of the constituents a) + b) + c) making 100% by weight.

In a first variant, said composition comprises: a) from 89 to 99.9% of at least one semi-crystalline aliphatic polyamide having a number of carbon per nitrogen atom greater than or equal to 7, in particular greater than or equal to 8, b) from 0.1 to 9%, by weight of at least one branching agent chosen from polyepoxy, polyanhydrides and polyisocyanates, in particular maleic polyanhydrides and polyepoxy, c) from 0 to 2% of at least one additive, in particular from 0.1 to 2%, the composition exhibiting, after compounding, a viscosity in the molten state of between 10,000 and 300,000 Pa.s, preferably from 15,000 to 220,000 Pa.s, as measured by plane-plane geometry according to ISO 6721-10:2015 at a temperature of 250°C, a frequency of 0.292 rad/s and a deformation of 2%, the sum of the constituents a) + b) + c) being 100% in weight.

In one embodiment of this first variant, said composition comprises: a) from 89 to 99.9% of at least one semi-crystalline aliphatic polyamide having a number of carbon per nitrogen atom greater than or equal to 7, in in particular greater than or equal to 8, b) from 0.1 to 9%, by weight of at least one branching agent chosen from polyepoxy, polyanhydrides and polyisocyanates, in particular polymaleic anhydrides and polyepoxy, the composition having after compounding a viscosity in the molten state of between 10,000 and 300,000 Pa.s, preferably between 15,000 and 220,000 Pa.s, as measured in plane-plane geometry according to standard ISO 6721-10:2015 at a temperature of 250° C, a frequency of 0.292 rad/s and a deformation of 2%, the sum of constituents a) + b) making 100% by weight.

Advantageously, in this embodiment of this first variant, the composition consists of: a) from 89 to 99.9% of at least one semi-crystalline aliphatic polyamide having a number of carbon per nitrogen atom greater than or equal to 7, in particular greater than or equal to 8, b) from 0.1 to 9%, by weight of at least one branching agent chosen from polyepoxy, polyanhydrides and polyisocyanates, in particular maleic polyanhydrides and polyepoxy, composition having, after compounding, a viscosity in the molten state of between 10,000 and 300,000 Pa.s, preferably from 15,000 to 220,000 Pa.s, as measured in plane-plane geometry according to standard ISO 6721-10:2015 at a temperature of 250° C., a frequency of 0.292 rad/s and a deformation of 2%, the sum of the constituents a)+b) making 100% by weight.

In another embodiment of this first variant, said composition comprises: a) from 89 to 99.8% of at least one semi-crystalline aliphatic polyamide having a number of carbon per nitrogen atom greater than or equal to 7, in particular greater than or equal to 8, b) from 0.1 to 9%, by weight of at least one branching agent chosen from polyepoxy, polyanhydrides and polyisocyanates, in particular maleic polyanhydrides and polyepoxy, c) of 0.1 to 2% of at least one additive, the composition exhibiting, after compounding, a viscosity in the molten state comprised from 10,000 to 300,000 Pa.s, preferably from 15,000 to 220,000 Pa.s, as measured in plane geometry - plan according to ISO 6721-10:2015 at a temperature of 250°C, a frequency of 0.292 rad/s and a deformation of 2%, the sum of the constituents a) + b) + c) making 100% by weight .

Advantageously, in this other embodiment of this first variant, the composition consists of: a) from 89 to 99.8% of at least one semi-crystalline aliphatic polyamide having a higher number of carbon per nitrogen atom or equal to 7, in particular greater than or equal to 8, b) from 0.1 to 9%, by weight of at least one branching agent chosen from polyepoxy, polyanhydrides and polyisocyanates, in particular maleic polyanhydrides and polyepoxy , c) from 0.1 to 2% of at least one additive, the composition having, after compounding, a viscosity in the molten state of between 10,000 and 300,000 Pa.s, preferably from 15,000 to 220,000 Pa.s, such as measured in plane-plane geometry according to standard ISO 6721-10:2015 at a temperature of 250°C, a frequency of 0.292 rad/s and a deformation of 2%, the sum of the constituents a) + b) + c) being 100% by weight. In a second variant, said composition comprises: a) from 93 to 99.9% of at least one semi-crystalline aliphatic polyamide having a number of carbon per nitrogen atom greater than or equal to 7, in particular greater than or equal to 8, b) from 0.1 to 5% by weight of at least one branching agent chosen from polyepoxy, polyanhydrides and polyisocyanates, in particular maleic polyanhydrides and polyepoxy, c) from 0 to 2% of au least one additive, in particular from 0.1 to 2%, the composition exhibiting, after compounding, a viscosity in the molten state of between 10,000 and 300,000 Pa.s, preferably from 15,000 to 220,000 Pa.s, as measured in plane geometry - plan according to ISO 6721-10:2015 at a temperature of 250°C, a frequency of 0.292 rad/s and a deformation of 2%, the sum of the constituents a) + b) + c) making 100% by weight .

In one embodiment of this second variant, said composition comprises: a) from 93 to 99.9% of at least one semi-crystalline aliphatic polyamide having a number of carbon per nitrogen atom greater than or equal to 7, in in particular greater than or equal to 8, b) from 0.1 to 5% by weight of at least one branching agent chosen from polyepoxy, polyanhydrides and polyisocyanates, in particular polymaleic anhydrides and polyepoxy, the composition having after compounding a melt viscosity of from 10,000 to 300,000 Pa.s, preferably from 15,000 to 220,000 Pa.s, as measured in plane-plane geometry according to standard ISO 6721-10:2015 at a temperature of 250°C, a frequency of 0.292 rad/s and a deformation of 2%, the sum of the constituents a) + b) making 100% by weight.

Advantageously, in this embodiment of this second variant, said composition consists of: a) from 93 to 99.9% of at least one semi-crystalline aliphatic polyamide having a number of carbon per nitrogen atom greater than or equal to to 7, in particular greater than or equal to 8, b) from 0.1 to 5% by weight of at least one branching agent chosen from polyepoxy, polyanhydrides and polyisocyanates, in particular maleic polyanhydrides and polyepoxy, composition having, after compounding, a viscosity in the molten state of between 10,000 and 300,000 Pa.s, preferably from 15,000 to 220,000 Pa.s, as measured in plane geometry according to standard ISO 6721-10:2015 at a temperature of 250 °C, a frequency of 0.292 rad/s and a deformation of 2%, the sum of the constituents a) + b) making 100% by weight.

In another embodiment of this second variant, said composition comprises: a) from 93 to 99.8% of at least one semi-crystalline aliphatic polyamide having a number of carbon per nitrogen atom greater than or equal to 7, in particular greater than or equal to 8, b) from 0.1 to 5% by weight of at least one branching agent chosen from polyepoxy, polyanhydrides and polyisocyanates, in particular polymaleic anhydrides and polyepoxy, c) from 0.1 to 2% of au least one additive, the composition exhibiting, after compounding, a viscosity in the molten state of between 10,000 and 300,000 Pa.s, preferably from 15,000 to 220,000 Pa.s, as measured in plane-plane geometry according to standard ISO 6721-10: 2015 at a temperature of 250°C, a frequency of 0.292 rad/s and a deformation of 2%, the sum of the constituents a) + b) + c) being 100% by weight.

Advantageously, in this other embodiment of this second variant, said composition consists of: a) from 93 to 99.8% of at least one semi-crystalline aliphatic polyamide having a number of carbon per nitrogen atom greater than or equal to 7, in particular greater than or equal to 8, b) from 0.1 to 5% by weight of at least one branching agent chosen from polyepoxy, polyanhydrides and polyisocyanates, in particular polymaleic anhydrides and polyepoxy, c) from 0.1 to 2% of at least one additive, the composition exhibiting, after compounding, a viscosity in the molten state of between 10,000 and 300,000 Pa.s, preferably from 15,000 to 220,000 Pa.s, as measured in plane-plane geometry according to ISO 6721-10:2015 at a temperature of 250°C, a frequency of 0.292 rad/s and a deformation of 2%, the sum of the constituents a) + b) + c) being 100% in weight.

In a third variant, said composition comprises: a) from 98 to 99.9% of at least one semi-crystalline aliphatic polyamide having a number of carbon per nitrogen atom greater than or equal to 7, in particular greater than or equal to 8, b) from 0.1 to 2% by weight of at least one branching agent chosen from polyepoxy, polyanhydrides and polyisocyanates, in particular maleic polyanhydrides and polyepoxy, c) from 0 to 2% of au least one additive, in particular from 0.1 to 2%, the composition exhibiting, after compounding, a viscosity in the molten state of between 10,000 and 300,000 Pa.s, preferably from 15,000 to 220,000 Pa.s, as measured in plane geometry - plan according to ISO 6721-10:2015 at a temperature of 250°C, a frequency of 0.292 rad/s and a deformation of 2%, the sum of the constituents a) + b) + c) making 100% by weight .

In one embodiment of this third variant, said composition comprises: a) from 98 to 99.9% of at least one semi-crystalline aliphatic polyamide having a number of carbon per nitrogen atom greater than or equal to 7, in individual greater than or equal to 8, b) from 0.1 to 2% by weight of at least one branching agent chosen from polyepoxy, polyanhydrides and polyisocyanates, in particular polymaleic anhydrides and polyepoxy, the composition having, after compounding, a viscosity in the molten state ranging from 10,000 to 300,000 Pa.s, preferably from 15,000 to 220,000 Pa.s, as measured in plane-plane geometry according to standard ISO 6721-10:2015 at a temperature of 250°C, a frequency of 0.292 rad/s and a deformation of 2%, the sum of the constituents a) + b) making 100% by weight.

Advantageously, in this embodiment of this third variant, said composition consists of: a) from 98 to 99.9% of at least one semi-crystalline aliphatic polyamide having a number of carbon per nitrogen atom greater than or equal to to 7, in particular greater than or equal to 8, b) from 0.1 to 2% by weight of at least one branching agent chosen from polyepoxy, polyanhydrides and polyisocyanates, in particular maleic polyanhydrides and polyepoxy, composition having, after compounding, a viscosity in the molten state of between 10,000 and 300,000 Pa.s, preferably from 15,000 to 220,000 Pa.s, as measured in plane-plane geometry according to standard ISO 6721-10:2015 at a temperature of 250° C., a frequency of 0.292 rad/s and a deformation of 2%, the sum of the constituents a)+b) making 100% by weight.

In another embodiment of this third variant, said composition comprises: a) from 96 to 99.8% of at least one semi-crystalline aliphatic polyamide having a number of carbon per nitrogen atom greater than or equal to 7, in particular greater than or equal to 8, b) from 0.1 to 2% by weight of at least one branching agent chosen from polyepoxy, polyanhydrides and polyisocyanates, in particular maleic polyanhydrides and polyepoxy, c) from 0 , 1 to 2% of at least one additive, the composition having, after compounding, a viscosity in the molten state comprised from 10,000 to 300,000 Pa.s, preferably from 15,000 to 220,000 Pa.s, as measured in plane-plane geometry according to ISO 6721-10:2015 at a temperature of 250°C, a frequency of 0.292 rad/s and a deformation of 2%, the sum of the constituents a) + b) + c) making 100% by weight.

Advantageously, in this other embodiment of this third variant, said composition consists of: a) from 96 to 99.8% of at least one semi-crystalline aliphatic polyamide having a higher number of carbon per nitrogen atom or equal to 7, in particular greater than or equal to 8, b) from 0.1 to 2% by weight of at least one branching agent chosen from polyepoxy, polyanhydrides and polyisocyanates, in particular polymaleic anhydrides and polyepoxy, c) from 0.1 to 2% of at least one additive, the composition exhibiting, after compounding, a viscosity in the molten state of between 10,000 and 300,000 Pa.s, preferably from 15,000 to 220,000 Pa.s, as measured in plane-plane geometry according to ISO 6721-10:2015 at a temperature of 250°C, a frequency of 0.292 rad/s and a deformation of 2%, the sum of the constituents a) + b) + c) being 100% in weight.

In all the variants and embodiments of the compositions described above: the MVR (volume melt index) as determined according to ISO 1133:2011 with a weight of 21.6 Kg and at a temperature of 275°C is included from 2 to 25 cm ³ /10 min, advantageously from 5 to 20 cm 3 /10 min, very advantageously comprised from 6 to 18 cm ³ /10 min.

In all the variants and embodiments of the compositions described above:

The R of the composition is comprised from 0 to 5, advantageously from 0 to 0.1 g/10 min at 235° C., 1 kg according to ISO 1133: 2011.

The branching agent and the polyamide are linked by means of a covalent bond, advantageously the branching agent and the polyamide are linked by an amide, ester or urea function.

Advantageously at least 5% by weight, very advantageously at least 15% by weight of the polyamide is covalently linked to the branching agent, the ratio of the viscosities in the molten state as measured in plane-plane geometry at 0.292 rad. s 7292 rad.s ¹ of said compositions is between 10 and 200, advantageously between 25 and 150. This ratio makes it possible to determine the degree of branching of the polyamide of said composition. The higher the ratio, the more the polyamide is connected in the composition. Consequently, the polyamide must be fluid at 292 rad.s ¹ and viscous at 0.292 rad.s ¹ ; the viscosity at 292 rad.s −1 is between 400 and 2000 and preferably between 600 and 1550;

The rheotensive force at 250° C. of the composition after compounding is between 22 mN and 200 mN, in particular between 25 mN and 150 mN; this force determines the melt strength of the polyamide, the greater the force, the less the polyamide flows;

The Rheotens force can for example be determined using a Rheotens 71.97 apparatus from Gottfert. A Rheotens device is a device fitted with toothed wheels capable of pulling on a rod at the outlet of a Rheotester 2000 capillary rheometer from Gottfert: shear at the level of the capillary 100s-l die of L/D=30 and D=1mm temperature 250 ° C, distance between exit of the rod and axis of the toothed wheels 105mm, acceleration of the wheels 2.4mm/s ² the swelling rate at the exit of the extruder of the composition after compounding, is greater than 1.15, preferably greater than 1, 2 . The swelling rate is carried out according to the procedure: a 25 cm tubular parison is extruded using an extrusion blow molding line equipped with an accumulator. The expulsion speed is fixed at 0.1m/s, the temperature of the extrudate is checked manually using a thermal probe. The measurement of the diameter of the parison is carried out 10 cm below the die. 5 measurements are taken to obtain an average. The temperature is chosen according to the flow characteristics of the polymer to limit the creep of the parison as much as possible.

The behavior of the parison makes it possible to analyze the capacity of the material to counterbalance the effect of gravity. Under its weight, a parison extruded horizontally or vertically will creep, thus modifying its dimensions. The hold of the vertical parison of the composition after compounding is between 15 and 50 s, in particular from 20 to 45 s. These measurements were taken as follows: a parison weighing 1.2 kg and 190 mm long is extruded with an expulsion speed set at 0.1 m/s. The time required for the length of the parison to increase by 40% by creep is measured. A long time will be representative of a viscous material. The temperature is chosen according to the flow characteristics of the polymer to limit the creep of the parison as much as possible.

Decompression tests under Hydrogen have shown that a quantity of impact modifier in the composition of the material less than or equal to 10% by weight makes it possible to avoid and limit cavitation mechanisms (blistering). The sample undergoes a rise in pressure from 1 to 40 MPa with a speed of lMPa.min-1, the latter is maintained at 40 MPa for 7 days so that it reaches a saturated state. The decompression phase is carried out with a speed of 5 MPa.min-1. The samples are observed under a scanning electron microscope in order to observe any cavitations.

The compositions according to the invention are resistant to decompression tests under hydrogen.

According to a second aspect, the present invention relates to a single-layer or multi-layer tubular structure intended for the transport, distribution or storage of hydrogen, comprising at least one sealing layer (1) comprising a composition as defined above.

In one embodiment of this second aspect, said structure is intended for transporting hydrogen, said sealing layer having a total proportion of contaminants present in the hydrogen and extracted from said sealing layer after contact with the hydrogen therewith, less than or equal to 3% by weight, in particular less than 2% by weight of the sum of the constituents of the composition of said sealing layer, the total proportion of contaminants being determined according to a contaminant test as defined in CSA/ANSI CH MC 2:19.

Said sealing layer is therefore in contact with the hydrogen. In another embodiment of this second aspect, said structure further comprises at least one composite reinforcement layer (2), said innermost composite reinforcement layer being welded or not, to said outermost adjacent sealing layer .

Said composite reinforcing layer is therefore above said sealing layer which is in contact with the hydrogen.

The number of composite reinforcement layers is between 1 and m.

The composite reinforcement layer may consist of a fibrous material in the form of continuous fibers impregnated with a composition mainly comprising at least one polymer P2j, j=1 to m, m being the number of reinforcement layers, in particular an epoxy resin or epoxy-based or a resin based on polyisocyanates, in particular polyisocyanurates,

Polymer P2j:

The polymer P2j can be thermoplastic or thermosetting.

Thermoplastic polymer P2j:

Thermoplastic or thermoplastic polymer is understood to mean a material which is generally solid at room temperature, which may be semi-crystalline or amorphous, in particular semi-crystalline and which softens during an increase in temperature, in particular after passing from its temperature of glass transition (Tg) and flows at a higher temperature when it is amorphous, or which can present a frank melting on passing its so-called melting temperature (Tf) when it is semi-crystalline, and which becomes solid again when 'a decrease in temperature below its crystallization temperature, Te, (for a semi-crystalline) and below its glass transition temperature (for an amorphous).

Tg, Te and Tf are determined by differential scanning calorimetry (DSC) according to standard 11357-2:2013 and 11357-3:2013 respectively.

The number-average molecular mass Mn of said thermoplastic polymer is preferably in a range extending from 10,000 to 40,000, preferably from 10,000 to 30,000. These Mn values may correspond to inherent viscosities greater than or equal to 0.8 as determined in the m-cresol according to the ISO 307:2007 standard but changing the solvent (use of m-cresol instead of sulfuric acid and the temperature being 20°C).

Examples of suitable semi-crystalline thermoplastic polymers in the present invention include: polyamides, in particular comprising an aromatic and/or cycloaliphatic structure, including copolymers, for example polyamide-polyether copolymers, polyesters, polyaryletherketones (PAEK ), polyetherether ketones (PEEK), polyetheretherketone ketones (PEKK), polyetherketoneetherketoneketones (PEKEKK), polyimides in particular polyetherimides (PEI) or polyamide-imides, polylsulfones (PSU) in particular polyarylsulfones such as polyphenylsulfones (PPSU), polyethersulfones (PES). semi-crystalline polymers are more particularly preferred, and in particular polyamides and their semi-crystalline copolymers.

The polyamide can be a homopolyamide or a copolyamide or a mixture thereof. Advantageously, the semi-crystalline polyamides are semi-aromatic polyamides, in particular a semi-aromatic polyamide of formula X/YAr, as described in EP1505099, in particular a semi-aromatic polyamide of formula A/XT in which A is chosen from a unit obtained from an amino acid, a unit obtained from a lactam and a unit corresponding to the formula (diamine in Ca). (Cb diacid), with a representing the number of carbon atoms of the diamine and b representing the number of carbon atoms of the diacid, a and b each being comprised from 4 to 36, advantageously from 9 to 18, the unit (Ca diamine) being chosen from aliphatic, linear or branched diamines, cycloaliphatic diamines and alkylaromatic diamines and the unit (Cb diacid) being chosen from aliphatic, linear or branched diacids, cycloaliphatic diacids and aromatic diacids ;

X.T denotes a unit obtained from the polycondensation of a Cx diamine and terephthalic acid, with x representing the number of carbon atoms of the Cx diamine, x being between 5 and 36, advantageously 9 to 18, in particular a polyamide of formula A/5T, A/6T, A/9T, A/10T or A/11T, A being as defined above, in particular a polyamide chosen from a PA MPMDT/6T, a PA11/10T, PA 5T/10T, PA 11/BACT, PA 11/6T/10T, PA MXDT/10T, PA MPMDT/10T, PA BACT/10T, PA BACT/6T, PA BACT /10T/6T, one PA 11/BACT/6T, PA 11/MPMDT/6T, PA 11/MPMDT/10T, PA 11/BACT/10T, one PA 11/MXDT/10T, one 11/5T/10T.

T stands for terephthalic acid, MXD stands for m-xylylene diamine, MPMD stands for methylpentamethylene diamine and BAC stands for bis(aminomethyl)cyclohexane. Said semi-aromatic polyamides defined above have in particular a Tg greater than or equal to 80°C.

P2j thermosetting polymer:

The thermosetting polymers are chosen from epoxy or epoxy-based resins, polyesters, vinyl esters, resins based on polyisocyanates, in particular polyisocyanurates, and polyurethanes, or a mixture of these in particular epoxy or epoxy-based resins or a resin based on polyisocyanates, in particular polyisocyanurates. Advantageously, each composite reinforcement layer consists of a composition comprising the same type of polymer, in particular an epoxy or epoxy-based resin or a resin based on polyisocyanates, in particular polyisocyanurates.

Said composition comprising said polymer P2j can be transparent to radiation suitable for welding.

As regards the fibers forming said fibrous material, these are in particular fibers of mineral, organic or vegetable origin.

Advantageously, said fibrous material can be sized or not sized.

Said fibrous material can therefore comprise up to 3.5% by weight of a material of organic nature (thermosetting or thermoplastic resin type) called size.

Among the fibers of mineral origin, mention may be made of carbon fibers, glass fibers, basalt or basalt-based fibers, silica fibers, or silicon carbide fibers for example. Among the fibers of organic origin, mention may be made of fibers based on a thermoplastic or thermosetting polymer, such as semi-aromatic polyamide fibers, aramid fibers, polyester fibers or polyolefin fibers for example. Preferably, they are based on an amorphous thermoplastic polymer and have a glass transition temperature Tg higher than the Tg of the polymer or mixture of thermoplastic polymer constituting the pre-impregnation matrix when the latter is amorphous, or higher than the Tm polymer or mixture of thermoplastic polymer constituting the pre-impregnation matrix when the latter is semi-crystalline. Advantageously, they are based on a semi-crystalline thermoplastic polymer and have a melting point Tf higher than the Tg of the polymer or thermoplastic polymer mixture constituting the pre-impregnation matrix when the latter is amorphous, or higher than the Tm polymer or mixture of thermoplastic polymer constituting the pre-impregnation matrix when the latter is semi-crystalline. Thus, there is no risk of melting for the organic fibers forming the fibrous material during impregnation by the thermoplastic matrix of the final composite. Among the fibers of plant origin, mention may be made of natural fibers based on flax, hemp, lignin, bamboo, silk, in particular spider silk, sisal, and other cellulosic fibers, in particular viscose. These fibers of plant origin can be used pure, treated or even coated with a coating layer, in order to facilitate adhesion and impregnation of the thermoplastic polymer matrix.

The fibrous material can also be a fabric, braided or woven with fibers.

It can also match fibers with holding threads. These building fibers can be used alone or in mixtures. Thus, organic fibers can be mixed with mineral fibers to be pre-impregnated with thermoplastic polymer powder and form the pre-impregnated fibrous material.

Organic fiber rovings can have several grammages. They may also have several geometries. The fibers making up the fibrous material may also be in the form of a mixture of these reinforcing fibers of different geometries. The fibers are continuous fibers.

Preferably, the fibrous material is chosen from glass fibres, carbon fibres, basalt or basalt-based fibres, or a mixture of these, in particular carbon fibres.

It is used in the form of a wick or several wicks.

According to a third aspect, the present invention relates to the use of 0.05% to 10%, in particular from 0.1 to 9% by weight, of at least one branching agent chosen from polyepoxy, polyanhydrides and polyisocyanates, in particular maleic polyanhydrides and polyepoxy, with 88 to 99.95%, in particular from 89 to 99.9% of at least one semi-crystalline aliphatic polyamide having a number of carbon per nitrogen atom greater than or equal to 7, in particular greater than or equal to 8, and optionally an additive for the constitution of a composition for blow molding or extrusion, in particular for blow molding, as defined above, whose viscosity in the molten state after compounding is between 10,000 to 300,000 Pa.s, preferably from 15,000 to 220,000 Pa.s, as measured in plane-plane geometry according to standard ISO 6721-10:2015 at a temperature of 250° C., a frequency of 0.292 rad/s and a strain of 2%.

By “mono or multilayer tubular structure” is therefore meant a tank comprising or consisting of one or more layers, namely a sealing layer and optionally one or more reinforcing layers, or several sealing layers and optionally several layers reinforcement, or several sealing layers and a reinforcing layer or else a sealing layer and a reinforcing layer.

The monolayer or multilayer tubular structure in the present invention also designates a pipe or a tube intended for the transport of hydrogen from the tank to the fuel cell and which comprises or consists of one or more layers, as defined above. .

All the characteristics defined above for the first aspect concerning the composition are valid for this third aspect.

According to a fourth aspect, the present invention relates to a process for preparing a composition for blow molding or extrusion, in particular blow molding, such as defined above, characterized in that it comprises a step of compounding said composition.

All the characteristics defined above for the first aspect concerning the composition are valid for this fourth aspect.

The compounding step is carried out in a special way so that the alloys have melt viscosities of between 10,000 and 300,000 Pa.s, preferably from 15,000 to 220,000 Pa.s, as measured in plane geometry according to ISO 6721-10. :2015 at a temperature of 250°C, a frequency of 0.292 rad/s and a strain of 2%.

These viscosities can for example be obtained by compounding at a temperature of the molten polymer greater than 280° C., preferably greater than 300° C. by increasing the residence time in the compounder. This branching reaction is advantageously catalyzed with, for example, phosphonium salts or hindered amines. The average residence time being advantageously from 20 seconds to 10 minutes, more advantageously from 45 seconds to 6 minutes.

In one embodiment, said compounding is carried out at a temperature of the molten polymer greater than 280° C., preferably greater than 300° C. with an average residence time ranging from 20 seconds to 10 minutes, very advantageously from 45 seconds to 6 minutes .

According to a fifth aspect, the present invention relates to a process for preparing a single-layer or multi-layer tubular structure as defined above, characterized in that it comprises a step of blow-molding or extrusion, in particular blow-molding , of a composition as defined above.

In one embodiment of this fifth aspect, the method comprises a prior step of compounding a composition as defined above.

The prior compounding step is in particular carried out as defined above.

All the characteristics defined above for the first aspect concerning the composition are valid for this fifth aspect.

EXAMPLES

The comparative compositions (CEI to CE4) and of the invention (C11 to CI6) in Table 2 below were prepared by compoudage under the following conditions:

The alloys were fabricated using a 40 mm ZSK twin-screw extruder (Coperion). The barrel temperature was set at 280°C and the screw speed was 300 rpm with a throughput of 60 kg/h.

The PA6 used is a polyamide 6 having a concentration at the end of the acid chain of 25 peq/g and a concentration at the end of the amine chain of 22 peq/g. The PA610 used is a polyamide 610 having a concentration of acid chain ends of 27 peq/g and a concentration of amine chain ends of 19 peq/g.

The PA612 used is a polyamide 612 having a concentration of acid chain ends of 22 peq/g and a concentration of amine chain ends of 20 peq/g.

The PAU used is a phosphoric acid-catalyzed polyamide 11 having a concentration of acid chain ends of 30 peq/g and a concentration of amine chain ends of 33 peq/g.

The Joncryl ADR 4400 is from BASF.

The Xibond 125 is from Polyscope.

The Lotader 3410 is from SK functional polymer.

Anox NBD TL 89 stabilizer is from SI group.

The melt viscosity was measured using an Ares G2 Rotational Rheometer equipped with a 25mm plane-plane geometry at a temperature of 250°C, at 0.292 rad/s (dwell time before launch 5 min under nitrogen, deformation of 2%, scanning from 628rad/s to 0.062rad/s and 3 points per decade, taking of a point over 3 cycles, gap of 1.5mm )

The Rheotens force is determined using a Rheotens 71.97 apparatus from Gottfert. A Rheotens device is a device fitted with toothed wheels capable of pulling on a rod at the outlet of a Rheotester 2000 capillary rheometer from Gottfert shear at the level of the capillary lOOs-1 die of L/D=30 and D=1mm temperature 250° C, distance between rod outlet and axis of the toothed wheels 105mm, acceleration of the wheels 2.4mm/s ² The water uptake is determined either in an oven under a controlled atmosphere at 100% Rh or in water, in all cases after saturation at 70°C and the measurement of this water uptake is made by weighing the sample at 23°C, for regular sampling times, spaced out by several days, until a state of equilibrium is observed , which is reached when the mass of the sample becomes constant (within the uncertainty of the measurement) for three consecutive sampling times. In the case of conditioning in water, the equilibrium reached corresponds to the water saturation of the polymer, at a temperature of 70°C.

MFI, short for Melt Flow Index, was measured according to ISO 1133:2011.

Liners with a thickness of 2 mm according to the compositions of the invention were prepared by blow molding and the hydrogen permeability at 15° C. was tested.

This consists of sweeping the upper face of the film with the test gas (Hydrogen) and measuring by gas phase chromatography the flux which diffuses through the film in the lower part, swept by the carrier gas: Nitrogen

The experimental conditions are presented in Table 1:

[Table 1]

Device Coupling LYSSY GPM500 / GC

The results obtained are then compared to the requirements of the CSA/ANSI CHMC 2.19 standard described in table 2 “material compatibility qualification rating”:

[Table 2]

The compositions of the invention and the comparative compositions were tested on several parameters. The results are detailed in Table 3. [Table 3]

The results show that the use of a branching agent in a particular range and of a polyamide with an average number of carbon atoms per nitrogen atom greater than or equal to 7 makes it possible to obtain compositions presenting the best compromise. on the various characteristics such as the rheotensive force, the water uptake, the viscosity at 0.292 rad/s and the hydrogen permeability.

All the compositions according to the invention have an MFI equal to 0, which means that nothing flows into the machine.

Claims

1. Blow molding or extrusion composition, in particular blow molding, comprising by weight: a) from 88 to 99.95%, in particular from 89 to 99.9%, in particular from 93 to 99.9% of at least one semi-crystalline aliphatic polyamide having a number of carbon per nitrogen atom greater than or equal to 7, in particular greater than or equal to 8, b) from 0.05% to 10%, in particular from 0.1 to 9%, in particular from 0.1 to 5% by weight of at least one branching agent chosen from polyepoxy, polyanhydrides and polyisocyanates, in particular polymaleic anhydrides and polyepoxy, c) from 0 to 2% d at least one additive, in particular from 0.1 to 2%, the composition having, after compounding, a viscosity in the molten state of between 10,000 and 300,000 Pa.s, preferably from 15,000 and 220,000 Pa.s, as measured in plane-plane geometry according to ISO 6721-10:2015 at a temperature of 250°C, a frequency of 0.292 rad/s and a deformation of 2%, the sum of the constituents a) + b) + c) fai healthy 100% by weight.

2. Blow molding or extrusion composition, in particular blow molding composition, according to claim 1, characterized in that said compounding is carried out at a temperature of the molten polymer greater than 280°C, preferably greater than 300°C with an average residence time comprised from 20 seconds to 10 minutes, very advantageously from 45 seconds to 6 minutes.

3. Blow molding or extrusion composition, in particular blow molding composition, according to claim 1 or 2, characterized in that the impact modifiers are excluded from the said composition.

4. Blow molding or extrusion composition, in particular blow molding composition, according to one of claims 1 to 3, characterized in that said branching agent has an average functionality in terms of epoxy, anhydride or isocyanate functions of between 1.8 to 200, preferably from 2.1 to 150.

5. Blow molding or extrusion composition, in particular blow molding composition, according to claim 4, characterized in that said branching agent has an average equivalent weight of epoxy, anhydride or isocyanate functions of from 100 to 10,000 g/mol, preferentially from 120 to 6000 g/mol, in particular from 140 to 3300 g/mol.

6. Blow molding or extrusion composition, in particular blow molding composition, according to one of claims 1 to 5, characterized in that the rheotensive force of the composition after compounding is between 22 mN and 200 mN, in particular ranging from 25 mN to 150 mN.

7. Blow molding or extrusion composition, in particular blow molding, according to one of claims 1 to 6, characterized in that said semi-crystalline aliphatic polyamide is chosen from PA610, PA612, PA 614 , PA 10, PAU and PA12, in particular PA610, PA612 and PAU.

8. Monolayer or multilayer tubular structure intended for the transport, distribution or storage of hydrogen, in particular hydrogen, comprising at least one sealing layer (1) comprising a composition as defined in one of claims 1 at 7.

9. Monolayer or multilayer tubular structure according to claim 8, characterized in that said sealing layer has a total proportion of contaminants present in the hydrogen and extracted from said sealing layer after contact of the hydrogen therewith. , less than or equal to 3% by weight, in particular less than 2% by weight of the sum of the constituents of the composition of said sealing layer, the total proportion of contaminants being determined according to a contaminant test as defined in the CSA/ANSI CHMC 2:19 standard.

10. Monolayer or multilayer tubular structure according to claim 8 or 9, characterized in that it further comprises at least one composite reinforcement layer (2), said innermost composite reinforcement layer being welded or not, to said layer outermost adjacent seal.

11. Use of 0.05% to 10%, in particular from 0.1 to 9% by weight of at least one branching agent chosen from polyepoxy, polyanhydrides and polyisocyanates, in particular polymaleic anhydrides and polyepoxy, with 88 to 99.95%, in particular 89 to 99.9% of at least one semi-crystalline aliphatic polyamide having a number of carbon per nitrogen atom greater than or equal to 7, in particular greater than or equal to 8, and optionally an additive for the constitution of a blow molding or extrusion composition, in particular blow molding, as defined in one of claims 1 to 7, the viscosity of which in the molten state after compounding is between 10,000 and 300,000 Pa.s, preferably between 15,000 and 220,000 Pa.s, as measured in plane-plane geometry according to the ISO standard 6721-10:2015 at a temperature of 250°C, a frequency of 0.292 rad/s and a strain of 2%.

12. Process for preparing a composition for blow molding or extrusion, in particular blow molding, as defined in one of claims 1 to 7, characterized in that it comprises a step of compounding said composition.

13. Process for preparing a single-layer or multi-layer tubular structure as defined in claim 8, characterized in that it comprises a step of blow molding or extrusion, in particular blow molding, of a composition such as defined in one of claims 1 to 5.

14. Process for the preparation of a monolayer or multilayer tubular structure according to claim 11, characterized in that it comprises a prior step of compounding a composition as defined in one of claims 1 to 7.