Monomaterial objects, especially recyclable objects, and their recycling

Abstract

The present invention relates in particular to a monomaterial object that is recyclable, that consists mainly of long-chain polyamide, and that comprises at least two elements: at least one element consists of at least one extruded or extrusion blow-molded part intended for transporting, distributing and / or storing fluids, comprising at least one layer of at least 30% by weight, relative to the total weight of said first element, of a first composition comprising at least one homopolyamide or one copolyamide, said at least one homopolyamide or one copolyamide of said first composition having a C / N ratio greater than or equal to 8; - a monomaterial object, wherein at least a second element consists of at least one injection-molded part and is made of a second composition comprising at least 30% by weight, relative to the total weight of said second element, of at least one homopolyamide or at least one copolyamide as defined above for said first composition, said first element and said second element being capable of at least partially adhering to one another.

Description

[Technical Field]

[0001] The present invention relates to a mono-material object, which is in particular recyclable and comprises at least two elements, to a method for its production and a method for recycling it, and to the compositions and their use thus obtained in the production of objects, in particular mono-material objects.

[0002] Through a circular economy, it is possible to reduce waste generation, depletion of the earth's resources, and environmental impact. Particular attention is now being paid to manufacturing objects from materials that have sufficient properties to allow them to be used for high performance applications after recycling, as well as for lower performance applications such as street furniture or roads.

[0003] To facilitate the recycling of components that allow the transport, distribution and / or storage of fluids in different means of transport (cars, trucks, drones, etc.), equipment manufacturers want to eco-design their products to improve their recyclability (connectors that consist mostly of polyamide, tubing that consists mostly of polyamide, etc.).

[0004] Patent EP 3081109 B1 proposes a sports shoe in which the upper part and the sole are mainly, or even completely, made from the same thermoplastic substrate in order to facilitate recycling.

[0005] Patent application WO 2020 / 201370 A1 proposes a method for recycling sports shoes, in which the shoes are crushed and then melted. Like the previous document, this document focuses on thermoplastic polyurethanes (TPU).

[0006] Patent application US 2017 / 0151470 A1 relates to a ball, in particular a soccer ball, and to methods for producing and recycling the ball, which consists of a bladder, a middle layer and an outer layer, the bladder and the two layers consisting predominantly by weight of a material from a first material class selected from polyurethane, polyvinyl chloride, polyethylene, polyamide and polypropylene.

[0007] International patent application WO 2021 / 148148 A1 relates to a lined garment comprising an outer layer, an inner layer and a lining between the two layers.

[0008] Each layer contains a predominant amount of material from the same family of thermoplastic polymers, in particular recycled polyesters or virgin polymers selected from thermoplastic polyurethanes (TPU), polyamides (PA), polyethylene terephthalate (PET) or polybutylene terephthalate (PBT). Polyesters have the disadvantage of being very sensitive to hydrolysis. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] European Patent No. 3081109 [Patent Document 2] International Publication No. 2020 / 201370 [Patent Document 3] US Patent Application Publication No. 2017 / 0151470 [Patent Document 4] International Publication No. 2021 / 148148

[0010] All of these patent applications mentioned above deal only with sports shoes, sports balls or articles of clothing, and not with components that allow the transport, distribution and / or storage of fluids in different vehicles.

[0011] The object of the present invention is therefore to propose a mono-material object which is in particular recyclable and which, when recycled, makes it possible to obtain a composition which can be used for the manufacture of objects, in particular mono-material objects, or for the manufacture of systems for transporting, distributing and / or storing fluids.

[0012] In particular, in the case of systems for transporting, distributing and / or storing fluids, especially devices equipped with thermal or electric engines, such as airplanes, drones, aircraft, trucks or automobiles, separating the various elements that make up said systems (in particular pipes, tanks and connectors or other injection-molded parts) for the purposes of sorting and possible recycling is generally laborious and / or expensive. These separation and sorting steps, which must be performed manually by an operator, currently do not make it possible to recycle these materials quantitatively and therefore in an economically viable way.

[0013] Therefore, the need to separate and sort these different elements is currently a major obstacle to their recycling.

[0014] The present invention aims to solve this problem by providing a specific single-material element that makes it possible to overcome these difficulties.

[0015] The invention therefore relates in particular to a monomaterial object, which is recyclable, consists mainly of long-chain polyamide and comprises at least two elements: - at least one first element consists of at least one extruded or extrusion-blow moulded part, in particular chosen from tubes and tanks, intended for transporting, distributing and / or storing fluids, and comprises at least one layer made of a first composition comprising, by weight, at least 30% by weight, in particular at least 50% by weight, in particular at least 70% by weight and more in particular at least 90% by weight, relative to the total weight of the first element, of at least one homopolyamide or at least one copolyamide, the at least one homopolyamide or at least one copolyamide of the first composition having a C / N ratio of 8 or more, in particular 9 or more and in particular 10 or more, The at least one homopolyamide and the at least one copolyamide may, independently of one another, comprise at least one C4-C 36 Units obtained from the polycondensation of amino acids, at least one C4-C 36 units resulting from the polycondensation of lactams, and at least one diamine, said diamine being selected from linear or branched aliphatic diamines, cycloaliphatic diamines and semi-aryl aliphatic diamines, or mixtures thereof; with at least one dicarboxylic acid, said diacid being selected from aliphatic diacids, alicyclic diacids and aromatic diacids or mixtures thereof; represents a repeat unit selected from XY units resulting from polycondensation, and the diamine and the diacid contain from 4 to 36 carbon atoms, preferably from 6 to 18 carbon atoms; - at least one second element consists of at least one injection-molded part, in particular chosen from connectors, and consists of a second composition comprising at least 30% by weight, in particular at least 50% by weight, in particular at least 70% by weight, more in particular at least 90% by weight, of at least one homopolyamide or at least one copolyamide as defined above for the first composition, relative to the total weight of the second element; The first and second elements relate to a single material object that can be at least partially adhered to one another.

[0016] The term "single material object" should be understood to mean an object that consists mainly of the same material, in this case long chain polyamide.

[0017] More precisely, the term "mono-material object" should be understood to mean an object comprising at least two elements, each consisting of a composition comprising at least one polymer matrix, said polymer matrix comprising predominantly, to a degree greater than 50% by weight relative to its total weight, at least one long-chain polyamide as defined according to the invention.

[0018] For the purposes of the present invention, a single-material object may in particular be an object comprising at least two elements, each element being single-material, i.e. each element consisting mainly of the same material as defined in accordance with the present invention.

[0019] The term "polymer matrix" is intended to indicate that portion of the composition consisting solely of polymer, ie, non-polymeric fillers and additives are excluded therefrom.

[0020] Preferably, said polymer matrix comprises at least 60% by weight, preferably at least 80% by weight, preferably at least 90% by weight, advantageously at least 95% by weight, or even 100% by weight, of at least one long-chain polyamide as defined according to the invention.

[0021] According to one embodiment, a "single-material object" for the purposes of the present invention is an object comprising at least two elements, at least one of which, and preferably each of which, for more than 50% by weight relative to its total weight, consists of a composition predominantly comprising at least one long-chain polyamide as defined according to the present invention.

[0022] Preferably, at least one element, preferably each element, consists of a composition comprising at least 80% by weight, preferably at least 90% by weight, advantageously at least 95% by weight, or even 100% by weight, of at least one long-chain polyamide as defined according to the invention.

[0023] According to one embodiment, the monomaterial object of the invention is an object comprising at least two elements, at least one of which, preferably each of which, consists, relative to its total weight, of a composition comprising less than 20% by weight, preferably less than 10% by weight, for example less than 5% by weight, for example less than 3% by weight, in particular 0% by weight, of short-chain polyamide, i.e. polyamide having a C / N ratio strictly less than 8, in particular less than or equal to 7, in particular less than or equal to 6.

[0024] According to one embodiment, the mono-material object of the invention comprises, relative to its total weight, less than 20% by weight, preferably less than 10% by weight, for example less than 5% by weight, for example less than 3% by weight, in particular 0% by weight, of short-chain polyamides, i.e. polyamides having a C / N ratio strictly less than 8, in particular less than or equal to 7, in particular less than or equal to 6.

[0025] The expression "mono-material object, particularly recyclable and consisting mainly of long-chain polyamides" means, for example, that the object consists of a single material family and contains 50% by weight or more of long-chain polyamides having a C / N ratio, i.e., an average number of carbon atoms per nitrogen atom, of 8 or more, in particular 9 or more, in particular 10 or more.

[0026] According to one embodiment, the first element of the monolithic object of the invention may consist of at least one extruded or extrusion blow-molded part intended for transporting, distributing and / or storing fluids, selected from tubes and tanks, said tubes or tanks may comprise from 1 to 5 layers.

[0027] In one embodiment, the tube or tank comprises only polyamide layers.

[0028] According to one embodiment, the first element of the single material object of the invention comprises at least 60% by weight, in particular at least 70% by weight, in particular 80% by weight, advantageously 90% by weight, more advantageously 100% by weight of long-chain polyamide.

[0029] If the first element of the single material object of the present invention comprises less than 100% by weight of a long-chain polyamide, the remainder up to 100% is made of another polyamide, which may or may not have long chains, or another polymer, such as EVOH (ethylene-vinyl alcohol).

[0030] Advantageously, the monomaterial object of the invention comprises at least 60% by weight, in particular at least 70% by weight, especially 80% by weight, advantageously 90% by weight, more advantageously 100% by weight of long-chain polyamide.

[0031] If the object comprises less than 100% by weight of a long-chain polyamide, the remainder to 100% is made of another polyamide, which may or may not have long chains, or another polymer, such as EVOH (ethylene-vinyl alcohol).

[0032] In one embodiment, copolyamides bearing amide units (Ba1) and polyether units (Ba2) are excluded from said first composition.

[0033] In another embodiment, copolyamides bearing amide units (Ba1) and polyether units (Ba2) are excluded from said second composition.

[0034] In yet another embodiment, copolyamides bearing amide units (Ba1) and polyether units (Ba2) are excluded from said first composition and said second composition.

[0035] Advantageously, said single material object as defined above is selected from car, truck, aircraft and drone parts.

[0036] The term "fluid" refers to air, oil (e.g. for cooling automatic gearboxes ("TOC", transmission oil coolers)), water, urea solutions, refrigerants, in particular R1234yf, glycol-based coolants, fuels such as gasoline, in particular biogasoline or diesel, in particular biodiesel, hydrogen or coolants, in particular battery or fuel cell coolants.

[0037] In one embodiment, the fluid is a coolant, in particular a battery or fuel cell coolant.

[0038] In another embodiment, the fluid is hydrogen.

[0039] According to one embodiment, the second element of the single-material object of the invention may consist of at least one injection-molded part intended to transport, distribute and / or store fluids, selected from connectors.

[0040] According to one embodiment, the single material object of the present invention may be a system for transporting, distributing and / or storing fluids, in particular a system for a device equipped with a thermal or electric engine, such as an airplane, drone, aircraft, truck or car.

[0041] It may in particular be a system combining at least one pipe with at least one connector, preferably a system combining at least one pipe with two connectors, said connectors allowing the assembly of said pipes.

[0042] It may also be a system combining at least one tank with at least one connector, preferably a system combining at least one tank with at least one connector and at least one pipe, said connector allowing the assembly of said pipe and said tank.

[0043] According to one embodiment, the single-material object of the present invention may be a system for transporting, distributing and / or storing fluids, in particular a system for a device equipped with a thermal engine or an electric engine, such as an airplane, drone, aircraft, truck or car, which combines at least one first element consisting of at least one extrusion or extrusion blow molded part as defined in accordance with the present invention and at least one second element consisting of at least one injection molded part as defined in accordance with the present invention, preferably at least two second elements consisting of at least one injection molded part as defined in accordance with the present invention.

[0044] In particular, the single-material object of the present invention may be a system for transporting, distributing and / or storing fluids, in particular for devices equipped with a thermal engine or an electric engine, such as an airplane, drone, aircraft, truck or car, which combines N first elements consisting of at least one extruded or extrusion blow molded part as defined in accordance with the present invention with at least N+1 second elements consisting of at least one injection molded part as defined in accordance with the present invention, where N is an integer greater than or equal to 1, in particular an integer greater than or equal to 2, for example 1 to 100.

[0045] Regarding the long-chain homopolyamides and long-chain copolyamides of the first and second component compositions: The nomenclature used to define polyamides is described in standard ISO 1874-1:2011 "Plastics - Polyamide (PA) moulded and extruded materials - Part 1: Designation", in particular on page 3 (Tables 1 and 2) and is well known to those skilled in the art.

[0046] Said long-chain homopolyamides and copolyamides (also known for the purposes of the present invention simply as "long-chain polyamides") are polyamides having a C / N ratio, i.e. the average number of carbon atoms per nitrogen atom, of 8 or more, in particular 9 or more, and especially 10 or more.

[0047] In a first variant of the invention, the repeating unit is a unit resulting from the polycondensation of at least one C4-C36 amino acid (or aminocarboxylic acid).

[0048] Advantageously, said aminocarboxylic acid contains 9 to 12 carbon atoms. It may therefore be chosen from 9-aminononanoic acid (designated 9), 10-aminodecanoic acid (designated 10), 11-aminoundecanoic acid (designated 11) and 12-aminododecanoic acid (designated 12). Advantageously, the aminocarboxylic acid is 11-aminoundecanoic acid.

[0049] In a second variant of the invention, the repeating units are units resulting from the polycondensation of at least one C4-C36 lactam.

[0050] Advantageously, the lactam contains 9 to 12 carbon atoms. It may therefore be chosen from decanolactam (designated 10), undecanolactam (designated 11) and laurolactam or lauryllactam (designated 12). Advantageously, the lactam is lauryllactam.

[0051] However, it is entirely conceivable to use mixtures of two or more aminocarboxylic acids, mixtures of two or more lactams, and also mixtures of one, two or more aminocarboxylic acids with one, two or more lactams.

[0052] More particularly preferably, the repeat units are derived from a single aminocarboxylic acid or a single lactam.

[0053] Repeating unit XY In another variation, the repeating unit is a unit XY.

[0054] The repeating unit XY is a unit obtainable from the polycondensation of at least one diamine with at least one dicarboxylic acid, wherein the diamine is selected from linear or branched aliphatic diamines, cycloaliphatic diamines and semi-arylaliphatic diamines, or mixtures thereof, and the diacid is selected from aliphatic diacids, cycloaliphatic diacids and aromatic diacids, or mixtures thereof.

[0055] The molar ratio of diamine to dicarboxylic acid is preferentially stoichiometric.

[0056] The diamine contains from 4 to 36 carbon atoms, advantageously from 6 to 18 carbon atoms.

[0057] According to one embodiment, the diamine contains from 6 to 12 carbon atoms.

[0058] When the diamine used to prepare the repeat unit XY is an aliphatic diamine having a linear backbone, the linear backbone may, where appropriate, contain one or more methyl and / or ethyl substituents. In this latter configuration, it is referred to as a "branched aliphatic diamine." When the backbone contains no substituents, the aliphatic diamine is referred to as a "linear aliphatic diamine."

[0059] The aliphatic diamines used to provide this repeat unit XY, whether or not they contain methyl and / or ethyl substituents on the backbone, contain from 4 to 36 carbon atoms, advantageously from 6 to 18 carbon atoms, especially from 9 to 18 carbon atoms.

[0060] When this diamine is a linear aliphatic diamine, it corresponds to the formula HN-(CH)-NH and may be selected, for example, from butanediamine, pentanediamine, hexanediamine, heptanediamine, octanediamine, nonanediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, hexadecanediamine, octadecanediamine and octadecenediamine. All of the linear aliphatic diamines just mentioned may be biobased within the meaning of standard ASTM D6866.

[0061] When the diamine is a branched aliphatic diamine, it may be, inter alia, 2-methylpentanediamine, 2-methyl-1,8-octanediamine or (2,2,4- or 2,4,4-)trimethylenehexanediamine.

[0062] Alicyclic diamines include, for example, bis(3,5-dialkyl-4-aminocyclohexyl)methane, bis(3,5-dialkyl-4-aminocyclohexyl)ethane, bis(3,5-dialkyl-4-aminocyclohexyl)propane, bis(3,5-dialkyl-4-aminocyclohexyl)butane, bis(3-methyl-4-aminocyclohexyl)methane or 3'-dimethyl-, commonly referred to as "BMACM" or "MACM" (and hereinafter designated B). It may be selected from 4,4'-diaminodicyclohexylmethane, p-bis(aminocyclohexyl)methane, commonly referred to as "PACM" (and hereinafter designated as P), isopropylidenedi(cyclohexylamine), commonly referred to as "PACP", isophoronediamine (hereinafter designated as IPD), and 2,6-bis(aminomethyl)norbornane, commonly referred to as "BAMN", or bis(aminomethyl)cyclohexane, commonly known as "BAC".

[0063] A non-exhaustive list of these cycloaliphatic diamines is given in the publication "Cycloaliphatic Amines" (Encyclopedia of Chemical Technology, Kirk-Othmer, 4th edition (1992), pp. 386-405).

[0064] When the diamine is a semi-arylaliphatic diamine, it is selected, for example, from 1,3-xylylenediamine and 1,4-xylylenediamine.

[0065] The dicarboxylic acids contain from 4 to 36 carbon atoms, advantageously from 6 to 18 carbon atoms, especially from 6 to 12 carbon atoms.

[0066] When the dicarboxylic acid is aliphatic, it may be selected from linear or branched aliphatic dicarboxylic acids.

[0067] When the dicarboxylic acid is aliphatic and linear, it may be selected from succinic acid (4), pentanedioic acid (5), adipic acid (6), heptanedioic acid (7), octanedioic acid (8), azelaic acid (9), sebacic acid (10), undecanedioic acid (11), dodecanedioic acid (12), brassicic acid (13), tetradecanedioic acid (14), hexadecanedioic acid (16), octadecanedioic acid (18), octadecenedioic acid (18), eicosanedioic acid (20), docosanedioic acid (22) and fatty acid dimers containing 36 carbons.

[0068] The aforementioned fatty acid dimers are dimerized fatty acids obtained by oligomerization or polymerization of unsaturated monobasic fatty acids with long hydrocarbon chains, such as linoleic acid or oleic acid, as described inter alia in EP 0471566.

[0069] When the dicarboxylic acid is aromatic, it may be selected from terephthalic acid (denoted T), isophthalic acid (denoted I) and naphthalene acid (denoted N).

[0070] In one embodiment, the first component composition and the second component composition each consist of a single homopolyamide.

[0071] In another embodiment, the homopolyamide of the first part composition and the second part composition is an aliphatic semi-crystalline homopolyamide.

[0072] For the purposes of the present invention, the term "semicrystalline homopolyamide" refers to a material that is generally solid at room temperature, that can soften during temperature increase, especially after passing its glass transition temperature (Tg), that can melt suddenly when passing its "melting temperature" (Tm), and that becomes solid again when the temperature falls below its crystallization temperature.

[0073] For the purposes of the present invention, a semicrystalline homopolyamide has a melting temperature (Tm) according to standard ISO11357-3:2013 by DSC and a crystallization enthalpy during a cooling step at a rate of 20 K / min according to standard ISO11357-3 of 2013 that is greater than 25 J / g, preferably greater than 40 J / g.

[0074] Tg, Tc and Tm are determined by differential scanning calorimetry (DSC) according to standards 11357-2:2013 and 11357-3:2013, respectively.

[0075] The number average molecular weight Mn of said semicrystalline homopolyamide is preferably in the range extending from 10,000 to 85,000, in particular from 10,000 to 60,000, preferentially from 10,000 to 50,000 and even more preferentially from 12,000 to 50,000.

[0076] In a first variant, the first and second compositions of the two components are different.

[0077] The term "different" should be understood to mean that the homopolyamide or copolyamide of the first composition is different from that of the second composition, or alternatively, the homopolyamide or copolyamide is the same, but in this case the compositions differ by constituents other than the polyamide.

[0078] Advantageously, in the latter case, only one of the two compositions contains a filler, the other does not contain any.

[0079] The term "fillers" includes glass beads, fibers such as glass and carbon fibers, talc, carbon black, and carbon nanotubes.

[0080] Preferably, the injection molded part comprises glass or carbon fibre or glass beads.

[0081] In one embodiment, the injection molded part includes conductive fillers, especially carbon black or carbon nanotubes (CNTs).

[0082] In another embodiment, the extruded and injection molded parts include conductive fillers, especially carbon black or carbon nanotubes (CNTs).

[0083] In a second variant, the first composition and the second composition comprise the same polyamide.

[0084] Advantageously, the first composition and the second composition comprise the same polyamide, in particular PA11, PA12, PA1010, PA1012, PA610 and PA612.

[0085] In a third variant, the monomaterial body consists mainly of long-chain aliphatic polyamides or of a mixture of elements consisting of long-chain aliphatic polyamides and semi-aromatic polyamides.

[0086] In a fourth variant, at least 10% by weight, in particular at least 30% by weight, of the units constituting the at least one homopolyamide or the at least one copolyamide of the first composition and of the second composition are identical.

[0087] In one embodiment of these four variants, the long chain homopolyamide is It is selected from polyamide 11 (PA11), polyamide 12 (PA12), polyamide 1010 (PA1010), polyamide 1012 (PA1012), polyamide 1212 (PA1212), polyamide 612 (PA612), polyamide 610 (PA610) or mixtures or copolyamides thereof, in particular PA11, PA12, PA610 and PA612.

[0088] Regarding copolyamides (PEBA) bearing amide units (Ba1) and polyether units (Ba2) The following definitions apply both to PEBAs that are optionally excluded from the compositions of the first and second components, and to PEBAs that may be present in the compositions of the first, second, and third components, as defined below.

[0089] Polyether block amide (PEBA) is a copolymer comprising amide units (Ba1) and polyether units (Ba2), the amide units (Ba1) being aliphatic repeating units selected from units derived from at least one amino acid or units derived from at least one lactam, or XY units, the XY units being: at least one diamine, said diamine being preferentially chosen from linear or branched aliphatic diamines, or mixtures thereof, - corresponding to the XY unit resulting from the polycondensation of at least one dicarboxylic acid, said diacid being preferentially chosen from linear or branched aliphatic diacids or mixtures thereof, said diamine and said diacid containing from 4 to 36 carbon atoms, advantageously from 6 to 18 carbon atoms, Said polyether units (Ba2) are derived in particular from at least one polyalkylene ether polyol, in particular a polyalkylene ether diol.

[0090] PEBAs result, inter alia, from the copolycondensation of polyamide blocks having reactive ends with polyether blocks having reactive ends, such as, inter alia: 1) A polyamide block carrying a diamine chain end and a polyoxyalkylene block carrying a dicarboxylic acid chain end. 2) Polyamide blocks carrying dicarboxylic acid chain ends and polyoxyalkylene blocks carrying diamine chain ends, obtained by cyanoethylation and hydrogenation of aliphatic α,ω-dihydroxylated polyoxyalkylene blocks, called polyalkylene ether diols (polyether diols). 3) polyamide blocks carrying dicarboxylic acid chain ends and polyether diols, the resulting product being, in this particular case, a polyetheresteramide. The copolymers of the invention are advantageously of this type.

[0091] Polyamide blocks carrying dicarboxylic acid chain ends result, for example, from the condensation of polyamide precursors in the presence of chain-length limiting dicarboxylic acids.

[0092] Polyamide blocks bearing diamine chain ends result, for example, from the condensation of polyamide precursors in the presence of chain-length limiting diamines.

[0093] Polymers having polyamide and polyether blocks may also contain randomly distributed units. These polymers can be prepared by the simultaneous reaction of precursors of the polyether and polyamide blocks.

[0094] For example, it is possible to react a polyether diol, a polyamide precursor, and a chain-length limited diacid, resulting in a polymer that essentially has polyether and polyamide blocks of highly variable length, but also randomly reacted different reagents, which are randomly (statistically) distributed along the polymer chain.

[0095] It is also possible to react polyether diamines, polyamide precursors, and chain-length limited diacids, resulting in polymers with essentially polyether and polyamide blocks of highly variable length, but also randomly reacted various reagents, which are randomly (statistically) distributed along the polymer chain.

[0096] Amide unit (Ba1): The amide unit (Ba1) corresponds to the aliphatic repeat unit defined above.

[0097] Advantageously, the amide unit (Ba1) is selected from polyamide 11, polyamide 12, polyamide 610, polyamide 612, polyamide 1010, polyamide 910, polyamide 613, polyamide 514, polyamide 109, polyamide 1011, polyamide 516, polyamide 615, polyamide 913, polyamide 129, polyamide 1012, and in particular polyamide 11.

[0098] More advantageously, the amide units (Ba1) are chosen from polyamide 11 and polyamide 12, in particular polyamide 11.

[0099] Polyether unit (Ba2): The polyether units are derived from, inter alia, at least one polyalkylene ether polyol, in other words, the polyether units are formed from at least one polyalkylene ether polyol. In this embodiment, the term "at least one polyalkylene ether polyol" means that the polyether units consist exclusively of alcohol chain ends and therefore cannot be polyetherdiamine triblock type compounds.

[0100] Therefore, the compositions of the present invention do not contain polyether diamine triblocks.

[0101] Advantageously, the polyether units (Ba2) are chosen from polyethylene glycol (PEG), polypropylene glycol (PPG), polytrimethylene glycol (PO3G), polytetramethylene glycol (PTMG) and mixtures thereof or copolymers thereof, in particular PTMG.

[0102] The number average molecular weight (Mn) of the polyether blocks is advantageously between 200 and 4000 g / mol, preferably between 250 and 2500 g / mol, in particular between 300 and 1100 g / mol. PEBA can be prepared via the following process, in which: in a first step, the polyamide blocks (Ba1) are lactam(s), or amino acid(s), or by polycondensation of diamine(s) and dicarboxylic acid(s), and, where appropriate, comonomers selected from lactams and α,ω-aminocarboxylic acids, in the presence of a chain limiting agent selected from dicarboxylic acids, and then In a second step, the polyamide blocks (Ba1) obtained are reacted with polyether blocks (Ba2) in the presence of a catalyst.

[0103] The two-stage general preparation method for the copolymers of the invention is known and is described, for example, in French patent FR 2 846 332 and European patent EP 1 482 011.

[0104] The reaction to form block (Ba1) is usually carried out at 180-300°C, preferably 200-290°C, with the pressure in the reactor set to between 5 and 30 bar and maintained for about 2-3 hours. The pressure is slowly reduced to return the reactor to atmospheric pressure, and then excess water is distilled off, for example, over 1-2 hours.

[0105] Once the polyamide bearing carboxylic acid end groups has been prepared, the polyether and catalyst are added. The polyether, like the catalyst, can be added in one or more portions. In an advantageous embodiment, the polyether is added first, and the reaction between the OH end groups of the polyether and the COOH end groups of the polyamide begins, resulting in the formation of ester bonds and the elimination of water. As much water as possible is removed from the reaction medium by distillation, and then the catalyst is introduced to complete the linkage of the polyamide and polyether blocks. This second step is carried out under stirring, preferably under a vacuum of at least 15 mmHg (2000 Pa), at a temperature such that the reagents and the resulting copolymer are in molten form. For example, this temperature can be between 100 and 400°C, more commonly between 200 and 300°C. The reaction is monitored by measuring the torque exerted by the molten polymer on the stirrer or by measuring the power consumed by the stirrer. The end of the reaction is determined by the target torque or power value.

[0106] It is also possible to add one or more molecules as antioxidants at the point during the synthesis deemed most advantageous, for example Irganox® 1010 or Irganox® 245. All monomers can be added at the beginning, i.e. in a single step, lactam(s), or amino acid(s), or bringing about the polycondensation of diamine(s) and dicarboxylic acid(s) and, where appropriate, other polyamide comonomer(s), - in the presence of a chain limiting agent selected from dicarboxylic acids, - (Ba2) in the presence of (polyether) blocks, It is also possible to consider a PEBA preparation process in the presence of a catalyst for the reaction between the flexible (Ba2) block and the (Ba1) block.

[0107] Advantageously, said dicarboxylic acid is used as a chain limiter and is introduced in excess relative to the stoichiometry of the diamine(s).

[0108] Advantageously, derivatives of metals selected from the group consisting of titanium, zirconium and hafnium, or strong acids such as phosphoric acid, hypophosphorous acid or boric acid are used as catalysts.

[0109] The polycondensation can be carried out at a temperature of 240 to 280°C.

[0110] Generally speaking, known copolymers bearing ether and amide units consist of semi-crystalline linear aliphatic polyamide blocks (for example, Pebax from Arkema).

[0111] In one embodiment, the copolyamide carrying amide units (Ba1) and polyether units (Ba2) has a density, determined according to ISO 1183-3:1999, greater than or equal to 1, in particular greater than or equal to 1.01, especially greater than or equal to 1.02.

[0112] In one embodiment, polyetheramines are excluded from the polyether units (Ba2).

[0113] For single-material objects It consists of at least two elements: said at least one first element, defined herein as (E1), and said at least one second element, defined herein as (E2).

[0114] In a first variant, it consists of the two elements: E1 / E2.

[0115] Element E1 can be at least partially joined to element E2, in particular E1 and E2 are at least partially adhered, and especially E1 and E2 are completely joined, in particular by adhesive.

[0116] In a second variant, it consists of more than two elements: E1 / (E1)n / E2 / (E2)m, where n and m are between 0 and 50, in particular between 3 and 50 elements, in particular between 5 and 30 elements, in particular between 10 and 30 elements, and when n=0, m is greater than 0, and when m=0, n is greater than 0.

[0117] Of course, when two elements E1 or two elements E2 are side by side, they can be at least partially adhered to each other.

[0118] According to one embodiment, E1 and / or E2, preferably E1 and E2, may be intended for the transport, distribution and / or storage of fluids, in particular for devices equipped with a thermal or electric engine, such as an airplane, a drone, an aircraft, a truck or a car.

[0119] E1 may be selected from pipes and tanks, among others.

[0120] E2 may be, among other things, a connector.

[0121] The present invention is directed to protecting a system that combines at least one pipe or tank with at least one connector.

[0122] According to one embodiment, the single material object of the present invention may be a system combining at least one pipe and at least one connector, preferably a system combining at least two pipes and one connector, said connector allowing the assembly of said pipes.

[0123] According to one embodiment, the single material object of the present invention may be a system combining at least two pipes and at least three connectors, preferably a system combining at least three pipes and four connectors, said connectors allowing the assembly of said pipes.

[0124] It may also be a system combining at least one tank with at least one connector, preferably a system combining at least one tank with at least one connector and at least one pipe, said connector allowing the assembly of said pipe and said tank.

[0125] Systems combining at least two pipes, preferably at least three pipes, at least three connectors, preferably at least four connectors, and optionally at least one tank are also covered by the present invention.

[0126] In one embodiment, the homopolyamides or copolyamides of components E1 and E2 comprise the same monomers, for example at least 10% by weight, advantageously at least 30% of the same monomers relative to the sum of the constituents of said homopolyamide or copolyamide.

[0127] In another embodiment, the single material object defined above is characterized in that at least 10% by weight, in particular at least 30% by weight, of the units constituting the at least one homopolyamide or the at least one copolyamide of the first composition and of the second composition are identical, in particular said units are PA11, PA12, PA1010, PA1012, PA610 and 612 units.

[0128] In yet another embodiment, the monomaterial object defined above is characterized in that the difference in C / N between the at least one homopolyamide or at least one copolyamide of the first composition and the at least one homopolyamide or at least one copolyamide of the second composition is less than or equal to 3, in particular less than or equal to 2, and especially less than or equal to 1.

[0129] In another embodiment, the single material object defined above is characterized in that the at least one homopolyamide or the at least one copolyamide of the first composition and the at least one homopolyamide or the at least one copolyamide of the second composition comprise monomers with the same C / N.

[0130] The term "monomer" should be understood to mean a basic building block such as a lactam, an amino acid, or a combination of a diamine and a dicarboxylic acid as defined above.

[0131] In one embodiment, the monomers are the same in each composition.

[0132] In a third variant, the single material object may consist of more than two elements, i.e. at least three elements, wherein said at least one first element, here defined as (E1), said at least one second element, here defined as (E2), and said third element, here defined as E3.

[0133] Said single material object comprising at least a third element consists of a third composition comprising at least one homopolyamide or at least one copolyamide as defined above, or at least one copolyamide comprising amide units (Ba1) and polyether units (Ba2), or a mixture thereof.

[0134] The third element can be an extruded or extrusion blow molded part or an injection molded part.

[0135] In one embodiment, it consists of three elements: E1 / E2 / E3 or E1 / E3 / E2 or E3 / E1 / E2.

[0136] Element E1 can be at least partially joined to element E2, in particular E1 and E2 are at least partially adhered, and especially E1 and E2 are completely adhered, in particular by means of an adhesive.

[0137] Element E2 can be at least partially joined to element E3, in particular E2 and E3 are at least partially adhered, especially E2 and E3 are completely adhered, in particular by means of an adhesive.

[0138] Element E1 can be at least partially joined to element E3, in particular E1 and E3 are at least partially adhered, and especially E1 and E3 are completely adhered, in particular by means of an adhesive.

[0139] It would not go outside the context of the invention if at least one other element E1 and / or E2 and / or E3 is present in said single material body.

[0140] In a fourth variant, the single material object may consist of more than three elements, i.e. at least four elements, consisting of the at least one first element, here defined as (E1), the at least one second element, here defined as (E2), the third element, here defined as E3, and the fourth element, here defined as E4.

[0141] The third element can be an extruded or extrusion blow molded part or an injection molded part.

[0142] The fourth element can be an extruded or extrusion blow molded part or an injection molded part.

[0143] In one embodiment, it consists of four elements: E1 / E2 / E3 / E4 and all possible combinations of arrangements of these four elements.

[0144] Each element may be at least partially joined to the subsequent element, in particular each element is at least partially adhered, and especially each element is completely joined.

[0145] Each element may be of non-recycled or at least partially recycled origin.

[0146] The term "at least partially recycled" means that there is at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% recycled composition in the element, and the recycled composition itself comprises at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90% long chain homopolyamide or copolyamide.

[0147] In one embodiment, when the single material is composed of three or more components, the composition of said third component comprises at least one long chain homopolyamide or at least one long chain copolyamide.

[0148] In another embodiment, when the single material consists of three or more components, the composition of said third component (E3) comprises at least one copolyamide carrying amide units (Ba1) and polyether units (Ba2).

[0149] In yet another embodiment, when the single material is composed of three or more components, the composition of said third component comprises a blend of at least one long-chain homopolyamide or at least one long-chain copolyamide with at least one copolyamide bearing amide units (Ba1) and polyether units (Ba2).

[0150] In another embodiment, the composition of the first component (E1) comprises a single long-chain homopolyamide or at least one long-chain copolyamide.

[0151] In another embodiment, the composition of the second component (E2) comprises a single long-chain homopolyamide or at least one long-chain copolyamide.

[0152] In another embodiment, the composition of the third element (E3), when present, comprises a single long-chain homopolyamide or at least one long-chain copolyamide.

[0153] In another embodiment, the composition of the third element (E3), if present, comprises a single copolyamide bearing amide units (Ba1) and polyether units (Ba2).

[0154] In another embodiment, the composition of the first component (E1) comprises a single long-chain homopolyamide or at least one long-chain copolyamide, and the composition of the second component (E2) comprises a single long-chain homopolyamide or at least one long-chain copolyamide.

[0155] In another embodiment, the composition of the first component (E1) comprises a single long-chain homopolyamide or at least one long-chain copolyamide, the composition of the second component (E2) comprises a single long-chain homopolyamide or at least one long-chain copolyamide, and the composition of the third component (E3), if present, comprises a single long-chain homopolyamide or at least one long-chain copolyamide.

[0156] In another embodiment, the composition of the first component (E1) comprises a single long-chain homopolyamide or at least one long-chain copolyamide, the composition of the second component (E2) comprises a single long-chain homopolyamide or at least one long-chain copolyamide, and the composition of the third component (E3), if present, comprises a single copolyamide bearing amide units (Ba1) and polyether units (Ba2).

[0157] As indicated above, the first and second elements may be at least partially bonded to one another. When they are at least partially bonded to one another, the first and second elements are bonded to one another by welding, firtree groove and mortise joints, clipping, or gluing with a non-polyamide adhesive at a content ranging from 0.01% to 10% by weight, in particular from 0.1% to 4% by weight, relative to the total mass of the object, or one is introduced into the other.

[0158] Said adhesive may be a polyurethane, acrylic, acrylonitrile, polyester, polyisoprene, polybutadiene or vinyl adhesive, preferably chosen from polyurethane, acrylic and polyester adhesives, advantageously it corresponds to a polyurethane adhesive.

[0159] According to another aspect, the present invention relates to a method for manufacturing a single material object as defined above, comprising the steps of: providing a first component consisting of a first composition comprising, by weight, at least 30% by weight, in particular at least 50% by weight, in particular at least 70% by weight, in particular at least 90% by weight, of at least one long-chain homopolyamide or at least one long-chain copolyamide, relative to the total weight of the first component, as defined above, providing a second component consisting of a second composition comprising, by weight, at least 30% by weight, in particular at least 50% by weight, in particular at least 70% by weight, in particular at least 90% by weight, of at least one long-chain homopolyamide or at least one long-chain copolyamide, relative to the total weight of the second component, as defined above, Assembling elements of an object, by welding or adhesives, as appropriate, to form a finished or semi-finished object.

[0160] According to one embodiment, the method for manufacturing a single-material object as defined above may comprise a step consisting in particular of assembling, where appropriate, the elements of the object by welding, or by firtree groove and mortise joints, by clipping or by joining with a non-polyamide adhesive, to form a finished or semi-finished object.

[0161] In one embodiment, the method defined above comprises, before assembly, the additional step of providing a third element consisting of a third composition, which comprises at least 30% by weight, in particular at least 50% by weight, in particular at least 70% by weight, in particular at least 90% by weight, by weight, relative to the total weight of the third element, of at least one long-chain homopolyamide or at least one long-chain copolyamide, or at least one copolyamide carrying amide units (Ba1) and polyether units (Ba2), or a mixture of the two, as defined above.

[0162] In another embodiment, the method defined above comprises, prior to assembly, an additional step of providing a fourth element after providing the third element, consisting of a fourth composition comprising, by weight, relative to the total weight of the third element, as defined above, at least 30%, in particular at least 50%, in particular at least 70%, in particular at least 90% of at least one long-chain homopolyamide or at least one long-chain copolyamide, or at least one copolyamide carrying amide units (Ba1) and polyether units (Ba2), or a mixture of the two.

[0163] In yet another embodiment, the method defined above comprises, before assembly, an additional step of providing n elements after providing a fourth element, consisting of a composition n comprising at least 30% by weight, in particular at least 50% by weight, in particular at least 70% by weight, in particular at least 90% by weight, by weight, relative to the total weight of the third element, of at least one long-chain homopolyamide or at least one long-chain copolyamide, or at least one copolyamide carrying amide units (Ba1) and polyether units (Ba2), or a mixture of the two, as defined above.

[0164] In another embodiment, the method defined above comprises at least one additional step after assembly.

[0165] The additional step after assembly may be that of initial commissioning by mounting on the vehicle and storing, dispensing or transporting the desired fluid.

[0166] According to another aspect, the present invention relates to a method for recycling an object as defined above, comprising the steps of: (a) preparing a used object; (b) optionally separating components of the object that cannot be recycled by said method; (c) optionally washing the used object from step (a) or (b); (d) optionally, a step of first crushing the used object of step (a) or (b), or of step (c) if the washing of step (c) has been carried out, to obtain a first crushed object; (e) optionally washing the primary grind if the washing step of step (c) was not performed; (f) grinding the used objects from steps (a) and / or (b) and / or (c) and / or (d) and / or (e) to obtain a primary grind or, if primary grinding was performed in step (d), a secondary grind; (g) optionally, heating the ground material from step (f) until melted and granulating; (h) optionally compounding and granulating; (i) extrusion or injection molding to produce an object; The present invention relates to a method comprising the steps of:

[0167] The first and / or second grinding may be carried out before or after washing.

[0168] Cleaning (or decontamination) is necessary when transporting, distributing or storing liquid fluids, but not when transporting, distributing or storing gases such as hydrogen or air.

[0169] Cleaning is carried out by compressed air treatment, in particular under pressure, or by hot water or steam treatment of the structure.

[0170] Washing with compressed air makes it possible to remove non-polymer particles such as soil, sand or dust from the used object.

[0171] Washing with hot water or steam makes it possible to at least partially dissolve and remove the water-soluble substances of the used object and to obtain the other constituents of the used object.

[0172] The temperature of the hot water or steam is 70°C to 150°C, particularly 70°C to 120°C.

[0173] The hot water may have a pH between 1 and 12.

[0174] The compounding step (h) makes it possible to add impact modifiers and / or fillers and / or additives and / or plasticizers depending on the properties of the product in steps (f) or (g) after analysis of the product.

[0175] If step (h) is carried out, the material obtained after said step (h) is in the form of granules for subsequent extrusion or injection molding.

[0176] The term "used object" means an object that is no longer new and that is or has been used, and does not in any way mean a post-industrial object that has never been used or that will be recycled without having been used.

[0177] In another embodiment, the present invention relates to a recycling method as defined above, also comprising the following steps: (j) adding fresh material to the ground material of the spent object before or after step (f) or after step (g);

[0178] The term "new materials" refers both to other polymers, especially other polyamides, especially polyamides with C / N<8, and to fillers, additives, etc.

[0179] According to yet another aspect, the present invention relates to a recycled polyamide composition obtainable via the process defined above.

[0180] According to yet another aspect, the present invention provides a composition comprising, by weight: 15% to 100%, in particular 30% to 100%, advantageously 50% to 99% of recycled polyamide obtained from the above-defined bodies, 0 to 70% virgin polyamides selected from homopolyamides, in particular having a C / N ratio of 8 or more, in particular 9 or more, in particular 10 or more, copolyamides, in particular having a C / N ratio of 8 or more, in particular 9 or more, in particular 10 or more, and PEBA, wherein the virgin polyamides are advantageously homopolyamides, in particular having a C / N ratio of 8 or more, in particular 9 or more, in particular 10 or more, 0 to 65%, in particular 0 to 35%, of virgin or recycled fillers obtained from the above-defined objects; 0-30% impact modifier; 0-5% additives and Including, The recycled polyamide has a molar ratio of functional groups resulting from oxidation reactions selected from primary amide functional groups, nitriles, chain end methyl groups, alkenes, formamides, imides, carboxylic acids and alcohols, and mixtures thereof, greater than the molar ratio of amide functional groups in the same polyamide constituting the never-used object. It relates to a composition.

[0181] In particular, according to the present invention, functional groups resulting from oxidation reactions may be present in the recycled polyamide of the present invention in a molar ratio to secondary amide functional groups that is at least 10% greater, such as at least 100% greater, such as at least 150% greater, such as at least 300% greater, than that of the same virgin polyamide elastomer.

[0182] When a single material object is used, new species such as imide functional groups, carboxylic acids, primary amides and alcohols, arising from oxidation mechanisms, especially of the amide functional groups and / or of the methylene alpha to the amide functional groups, are found in the polyamide that makes up the pipe, connector or tank.

[0183] The functional groups are found as a result of UV radiation or heat, or as a result of reaction with compounds that the object comes into contact with, such as gasoline, sunscreen, lubricants, etc.

[0184] The functional groups can be detected by infrared or NMR spectroscopy.

[0185] Therefore, 1700~1740cm -1 The absorption band of imide is 1680-1720cm -1 The absorption band at 3580-3670 cm -1 The absorption band corresponds to the alcohol functional group of the carboxylic acid.

[0186] 3580~3670cm -1 The absorption band at 1000 nm corresponds to the free alcohol functional group.

[0187] The amide functional group is primarily identified by the 3100-3500 cm band corresponding to the NH group of the amide. -1 and 1560-1640cm -1 Secondly, the pair of absorption bands at 1650-1700 cm correspond to the carbonyl group of the amide. -1 It is characterized by an absorption band

[0188] In a first variant, the composition comprises, by weight: 50% to 70% recycled polyamide from single-material objects as defined above; 30% to 50% virgin polyamide, the virgin polyamide being chosen from homopolyamides, in particular long-chain homopolyamides, copolyamides, in particular long-chain copolyamides, and PEBA, advantageously the virgin polyamide being a homopolyamide; 0-30% impact modifier, 0-5%, especially 0.1%-5% additives, The sum of the components equals 100%.

[0189] In a second variant, the composition comprises, by weight: 30% to 50% recycled polyamide from single material objects as defined above; 0-65% virgin polyamide, the virgin polyamide being selected from homopolyamides, in particular long-chain homopolyamides, copolyamides, in particular long-chain copolyamides, and PEBA, advantageously the virgin polyamide being a homopolyamide, in particular a long-chain homopolyamide; 0-30% impact modifier; 5% to 65%, especially 5% to 35% filler; 0-5%, especially 0.1%-5% additives; The sum of the components equals 100%.

[0190] In a third variant, the composition comprises, by weight: 60% to 80% recycled polyamide from single material objects as defined above; 0-20% virgin polyamide, the virgin polyamide being selected from homopolyamides, in particular long-chain homopolyamides, copolyamides, in particular long-chain copolyamides, and PEBA, advantageously the virgin polyamide being a homopolyamide, in particular a long-chain homopolyamide; 0-30% impact modifier; 20% to 40% filler, 0-5%, especially 0.1%-5% additives, The sum of the components equals 100%.

[0191] In a fourth variant, the composition comprises, by weight: 40% to 60% recycled polyamide from single material objects as defined above; 0-20% virgin polyamide, the virgin polyamide being selected from homopolyamides, in particular long-chain homopolyamides, copolyamides, in particular long-chain copolyamides, and PEBA, advantageously the virgin polyamide being a homopolyamide, in particular a long-chain homopolyamide; 0-30% impact modifier; 40% to 60% filler, 0-5%, especially 0.1%-5% additives; The sum of the components equals 100%.

[0192] In one embodiment, in the above compositions of this other aspect and its four variations, the term "comprising" is replaced with the term "consisting of."

[0193] These four variants and the compositions of their embodiments are particularly suitable for the embodiment in which the single-material object defined above is characterized in that only one of the two compositions contains a filler, and the other does not.

[0194] In one embodiment, the molar ratio of functional groups resulting from the oxidation reaction to secondary amide functional groups is 0.0001 to 0.3.

[0195] The concentration can be measured by proton NMR in deuterated dichloromethane with the addition of HFIP (hexafluoroisopropanol) to dissolve the polyamide.

[0196] In a first variant, the molar ratio of imide functions to secondary amide functions is between 0.0005 and 0.02, in particular between 0.001 and 0.08, and in particular between 0.005 and 0.05.

[0197] In one embodiment of this first variant, the molar ratio of imide functions to secondary amide functions is between 1 / 1000 and 1 / 100, in particular between 1 / 1000 and 1 / 300, in particular between 1 / 1000 and 1 / 500, in particular between 1 / 1000 and 1 / 750.

[0198] In another embodiment of this first variant, the molar ratio of imide functional groups to secondary amide functional groups is between 1 / 750 and 1 / 20, in particular between 1 / 750 and 1 / 50, in particular between 1 / 750 and 1 / 100, in particular between 1 / 750 and 1 / 300, in particular between 1 / 750 and 1 / 500.

[0199] In yet another embodiment of this first variant, said molar ratio of imide functions to secondary amide functions ranges from 1 / 500 to 1 / 20, in particular from 1 / 500 to 1 / 100, in particular from 1 / 750 to 1 / 300.

[0200] In yet another embodiment of this first variant, the molar ratio of imide functions to secondary amide functions ranges from 1 / 300 to 1 / 20, in particular from 1 / 300 to 1 / 50, in particular from 1 / 300 to 1 / 100.

[0201] In a second variant, said molar ratio of carboxylic acid functions ranges from 0.0005 to 0.02, in particular from 0.001 to 0.08, and in particular from 0.005 to 0.05.

[0202] In one embodiment of this second variant, said molar ratio of carboxylic acid functions to secondary amide functions ranges from 1 / 5000 to 1 / 20, in particular from 1 / 3000 to 1 / 25, especially from 1 / 3000 to 1 / 50 and very advantageously from 1 / 500 to 1 / 15.

[0203] In one embodiment of this second variant, the molar ratio of carboxylic acid functions to secondary amide functions ranges from 1 / 1000 to 1 / 100, in particular from 1 / 500 to 1 / 100, in particular from 1 / 400 to 1 / 100, more in particular from 1 / 300 to 1 / 100.

[0204] In a third variant, said molar ratio of alcohol functions ranges from 0.0005 to 0.02, in particular from 0.001 to 0.08, and in particular from 0.005 to 0.05.

[0205] In one embodiment of this third variant, said molar ratio of alcohol functions to secondary amide functions ranges from 1 / 1000 to 1 / 20, advantageously from 1 / 1000 to 1 / 25, and very advantageously from 1 / 200 to 1 / 50.

[0206] In one embodiment of this third variant, the molar ratio of alcohol functional groups to secondary amide functional groups ranges from 1 / 1000 to 1 / 200, in particular from 1 / 1000 to 1 / 300, in particular from 1 / 1000 to 1 / 400, more in particular from 1 / 1000 to 1 / 500.

[0207] In a fourth variant, the molar ratio of primary amide functions to secondary amide functions ranges from 0.0005 to 0.02, in particular from 0.001 to 0.08 and in particular from 0.005 to 0.05.

[0208] In one embodiment of this fourth variant, the molar ratio of primary amide functional groups to secondary amide functional groups is in the range of 1 / 500 to 1 / 15, in particular 1 / 400 to 1 / 15, in particular 1 / 300 to 1 / 15, more in particular 1 / 200 to 1 / 15, in particular 1 / 100 to 1 / 15.

[0209] In a fifth variant, the molar ratio of nitrile functions to secondary amide functions ranges from 0.0005 to 0.02, in particular from 0.001 to 0.08 and in particular from 0.005 to 0.05.

[0210] In a sixth variant, the molar ratio of chain-end methyl functions to secondary amide functions ranges from 0.0005 to 0.02, in particular from 0.001 to 0.08, and in particular from 0.005 to 0.05.

[0211] Of course, depending on the single material objects used and the exposures to which they have been exposed, there may be more than one functional group resulting from the oxidation reaction.

[0212] The composition also advantageously comprises the residue of a stabilizer selected from phenols, quinones, stilbene quinones and phosphites.

[0213] The recycled polyamide advantageously comprises alkyl chain ends with a carbon number (between 1 and 18) greater than that of the virgin PA. Advantageously, the content of alkyl chain ends is between 1 ppm and 0.5%.

[0214] According to another aspect, the present invention relates to the use of a composition as defined above for the manufacture of an object, in particular a monomaterial object.

[0215] Said mono-material object thus produced from a used mono-material object can itself be recycled at least once, in particular 1 to 10 times, according to the method of the invention.

[0216] According to another aspect, the present invention relates to the use of a composition as defined above for the manufacture of an object, in particular a monomaterial object.

[0217] According to another aspect, the invention relates to the use of a single material object as defined above for the manufacture of a system for transporting, distributing and / or storing fluids, in particular a system for a device equipped with a thermal or electric engine, such as an airplane, a drone, an aircraft, a truck or a car.

[0218] In one embodiment, the fluid is selected from hydrogen and a coolant. [Example]

[0219] The examples in Tables 1, 2 and 3 below are milled and then granulated using a twin screw extruder.

[0220] [Table 1]

[0221] [Table 2]

[0222] [Table 3]

[0223] Injection molded parts 1, 2, 3, 4, 5 and 6 are connectors.

[0224] Extrusion parts 1, 2, 3, 4, 5 and 6 are single-wall tubes for transporting coolant. PA 11 BESNO TL: Arkema PA 11 KNO: Arkema Orevac IM 800: SK Functional Polymers Stabilizers: 0.5% Lowinox 44B25 (SI Group) and 0.2% Irgafos 168 (BASF) HDPE: High density polyethylene 5502: Total Energies PA 6 Ultramid B27: BASF Glass fiber: CS 7928: LANXESS Germany GMBH

[0225] The objects CE1, IE1, CE2, IE2, CE3 and IE3 were crushed to a size less than 30 mm and then compounded in an 18 mm twin screw extruder at a flow rate of 5 kg / h and a temperature of 280°C to obtain granules for evaluating the properties obtained during the second life of the material.

[0226] The granules thus obtained were then injection moulded using a Battenfeld BA800CDC press to produce ISO 527 1A test specimens and ISO 179 impact bars. The following parameters were applied during injection molding:

[0227] - Barrel temperature: 270℃ - Nozzle temperature: 290℃ - Mold temperature: 40℃ - Cycle time: 60 seconds

[0228] The impact strength was determined on five 80 mm × 10 mm × 4 mm V-notched specimens at a temperature of −30°C ± 2°C for dry samples according to standard ISO 179-1:2010 / 1eA (Charpy impact).

[0229] The elongation at break was measured on test specimens according to standard ISO 527 1A.

[0230] The results are shown in Tables 4 and 5.

[0231] [Table 4]

[0232] [Table 5]

[0233] The above examples show that better properties are obtained after recycling of objects according to the invention, and that said objects can therefore be recycled to produce new, high performance objects.

[0234] Furthermore, evaluation of low temperature impact strength shows that the articles of the present invention have better properties after recycling.

[0235] Examples CE1 and IE1 contain an impact modifier (Orevac IM800) and are particularly indicated for applications requiring low temperature impact resistance.

[0236] Examples CE2 and IE2 contain glass fibers and are particularly suitable when pressure resistance is required.

[0237] Examples CE3 and IE3 make it possible to reach a compromise between impact resistance, elongation at break and a fairly high tensile modulus (compared to CE1 and IE1).

[0238] In all three cases, the composition according to the invention makes it possible to achieve better properties and therefore greater durability of the object.

Claims

1. A monomaterial object, particularly recyclable, consisting mainly of long-chain polyamide and comprising at least two of the following elements: at least one first element consists of at least one extruded or extrusion blow-molded part, in particular chosen from tubes and tanks, intended for the transport, distribution and / or storage of fluids, and comprises at least one layer consisting of at least 30% by weight, in particular at least 50%, in particular at least 70%, more in particular at least 90% by weight, relative to the total weight of said first element, of a first composition comprising at least one homopolyamide or at least one copolyamide, said at least one homopolyamide or at least one copolyamide of said first composition having a C / N ratio of 8 or more, in particular 9 or more, in particular 10 or more, The at least one homopolyamide and the at least one copolyamide may, independently of one another, comprise at least one C ４ -C ３６ Units resulting from the polycondensation of amino acids, at least one C ４ -C ３６ units resulting from the polycondensation of lactams, and at least one diamine, said diamine being selected from linear or branched aliphatic diamines, cycloaliphatic diamines and semi-arylaliphatic diamines, or mixtures thereof; with at least one dicarboxylic acid, the diacid being selected from aliphatic diacids, cycloaliphatic diacids, and aromatic diacids or mixtures thereof; represents a repeat unit selected from XY units obtained from polycondensation, said diamine and said diacid contain from 4 to 36, preferably from 6 to 18, carbon atoms; at least one second element consists of at least one injection-molded part and is made of at least 30% by weight, in particular at least 50%, in particular at least 70%, more in particular at least 90% by weight, relative to the total weight of said second element, of a second composition comprising at least one homopolyamide or at least one copolyamide as defined above for the first composition, The single material object, wherein the first element and the second element are capable of being at least partially bonded to one another.

2. 10. The single-material object of claim 1, wherein the single-material object is selected from an automobile part, a truck part, an aircraft part, and a drone part.

3. 3. A single-material object according to claim 1 or 2, characterized in that the first composition and the second composition are different.

4. A single-material object according to any one of claims 1 to 3, characterized in that only one of the two compositions contains a filler, the other of which is free of fillers.

5. 5. A monomaterial object according to any one of claims 1 to 4, characterized in that it consists mainly of aliphatic long-chain polyamides or of a mixture of elements consisting of aliphatic long-chain polyamides and semi-aromatic long-chain polyamides.

6. 6. The single-material object according to claim 1, wherein the first composition and the second composition comprise the same polyamide, in particular PA11, PA12, PA1010, PA1012, PA610 or PA612.

7. 6. A single material object according to any one of claims 1 to 5, characterized in that at least 10% by weight, in particular at least 30% by weight, of the units constituting the at least one homopolyamide or the at least one copolyamide of the first composition and of the second composition are identical, in particular said units are PA11, PA12, PA1010, PA1012, PA610 and PA612 units.

8. 6. A single-material object according to any one of claims 1 to 5, characterized in that the difference in C / N between the at least one homopolyamide or at least one copolyamide of the first composition and the at least one homopolyamide or at least one copolyamide of the second composition is 3 or less, in particular 2 or less, in particular 1 or less.

9. 6. A single material object according to any one of claims 1 to 5, characterized in that the at least one homopolyamide or the at least one copolyamide of a first composition and the at least one homopolyamide or the at least one copolyamide of a second composition comprise monomers having the same C / N ratio.

10. 10. The single material object of claim 9, wherein the monomer is the same in each composition.

11. 11. A single-material object according to any one of claims 1 to 10, characterized in that the first and second elements are joined to each other or introduced one into the other by welding, firtree groove and mortise joint, clip fastening or gluing with a non-polyamide adhesive with a content ranging from 0.01% to 10% by weight, in particular from 0.1% to 4% by weight, relative to the total mass of the object.

12. 12. A single-material object according to any one of claims 1 to 11, characterized in that it comprises at least one third element consisting of a third composition comprising at least one homopolyamide or at least one copolyamide as defined in claim 1, or at least one copolyamide comprising amide units (Ba1) and polyether units (Ba2), or a mixture thereof.

13. 13. A single-material object according to claim 12, characterized in that it comprises up to 50 elements, in particular 3 to 50 elements, more particularly 5 to 30 elements, in particular 10 to 30 elements.

14. A method for producing a single material object according to any one of claims 1 to 13, comprising the steps of: providing a first component consisting of a first composition as defined above, comprising at least 30%, in particular at least 50%, in particular at least 70%, more in particular at least 90% by weight of at least one long-chain homopolyamide or at least one long-chain copolyamide, relative to the total weight of the first component; providing a second component consisting of a second composition comprising at least 30%, in particular at least 50%, in particular at least 70%, more in particular at least 90% by weight of at least one long-chain homopolyamide or at least one long-chain copolyamide, relative to the total weight of the second component, as defined above; assembling the elements of the object, if necessary by welding or adhesive, to form a finished or semi-finished object; A method comprising the steps of:

15. A method for recycling an object as defined in any one of claims 1 to 13, comprising the following steps: (a) providing a spent object; (b) optionally separating components of the object that cannot be recycled by said method; (c) optionally washing the used object from step (a) or (b); (d) optionally, a step of primarily crushing the used object of step (a) or (b), or of step (c) if the washing of step (c) has been carried out, to obtain a primarily crushed object; (e) optionally washing the primary grind if the washing of step (c) was not performed; (f) grinding the used objects from steps (a) and / or (b) and / or (c) and / or (d) and / or (e) to obtain a primary grind or, if primary grinding was performed in step (d), a secondary grind, (g) optionally, heating the ground material from step (f) until molten and granulating; (h) optionally compounding and granulating; (i) making an object by extrusion or injection molding; A method comprising the steps of:

16. moreover, (j) adding fresh material to the ground up spent object before or after step (f) or after step (g); 16. The recycling method of claim 15, comprising:

17. A recycled polyamide composition obtainable by the method according to claims 15-16.

18. By weight, 15% to 100%, in particular 30% to 100%, advantageously 50% to 99% of recycled polyamide obtained from the object according to any one of claims 1 to 13; 0 to 70% virgin polyamide selected from homopolyamides having a C / N ratio of 8 or more, 9 or more, in particular 10 or more, copolyamides having a C / N ratio of 8 or more, in particular 9 or more, in particular 10 or more, and PEBA, said virgin polyamides being advantageously homopolyamides having a C / N ratio of 8 or more, in particular 9 or more, in particular 10 or more, 0 to 65%, preferably 0 to 35%, of virgin or recycled fillers obtained from the body according to any one of claims 1 to 8; 0-30% impact modifier; 0-5% additives; Including, The recycled polyamide has a molar ratio of functional groups resulting from oxidation reactions selected from primary amide functional groups, nitriles, chain end methyl groups, alkenes, formamides, imides, carboxylic acids and alcohols, and mixtures thereof, greater than the molar ratio of amide functional groups in the same polyamide comprising the virgin object that has never been used.

19. 19. The composition according to claim 18, wherein the molar ratio of functional groups resulting from an oxidation reaction to secondary amide functional groups is between 0.0001 and 0.

3.

20. 20. Composition according to claim 18 or 19, characterized in that the molar ratio of imide functional groups ranges from 0.0005 to 0.02, in particular from 0.001 to 0.08, in particular from 0.005 to 0.

05.

21. 21. Composition according to any one of claims 18 to 20, characterized in that the molar ratio of carboxylic acid functions to secondary amide functions is between 0.0005 and 0.02, in particular between 0.001 and 0.08, in particular between 0.005 and 0.

05.

22. 22. Composition according to any one of claims 18 to 21, characterized in that the molar ratio of alcohol functional groups to secondary amide functional groups is between 0.0005 and 0.02, in particular between 0.001 and 0.08, in particular between 0.005 and 0.

05.

23. 23. Composition according to any one of claims 18 to 22, characterized in that the molar ratio of primary amide functional groups to secondary amide functional groups is between 0.0005 and 0.02, in particular between 0.001 and 0.08, in particular between 0.005 and 0.

05.

24. 24. Composition according to any one of claims 18 to 23, characterized in that the molar ratio of nitrile functional groups to secondary amide functional groups is between 0.0005 and 0.02, in particular between 0.001 and 0.08, in particular between 0.005 and 0.

05.

25. 25. Composition according to any one of claims 18 to 24, characterized in that the molar ratio of chain-end methyl functions to secondary amide functions is between 0.0005 and 0.02, in particular between 0.001 and 0.08, in particular between 0.005 and 0.

05.

26. Use of a composition according to any one of claims 17 to 25 for the manufacture of an object, in particular a mono-material object.

27. Use of a single material object according to any one of claims 1 to 13 for manufacturing a system for transporting, distributing or storing fluids, in particular a system for devices with a thermal or electric engine, such as an airplane, a drone, an aircraft, a truck or a car.

28. 28. Use of a single material object according to claim 27, characterized in that the fluid is selected from hydrogen and coolants.

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